WorldWideScience

Sample records for alkali halide crystals

  1. Dislocation unpinning model of acoustic emission from alkali halide crystals

    Indian Academy of Sciences (India)

    B P Chandra; Anubha S Gour; Vivek K Chandra; Yuvraj Patil

    2004-06-01

    The present paper reports the dislocation unpinning model of acoustic emission (AE) from alkali halide crystals. Equations are derived for the strain dependence of the transient AE pulse rate, peak value of the AE pulse rate and the total number of AE pulse emitted. It is found that the AE pulse rate should be maximum for a particular strain of the crystals. The peak value of the AE pulse rate should depend on the volume and strain rate of the crystals, and also on the pinning time of dislocations. Since the pinning time of dislocations decreases with increasing strain rate, the AE pulse rate should be weakly dependent on the strain rate of the crystals. The total number of AE should increase linearly with deformation and then it should attain a saturation value for the large deformation. By measuring the strain dependence of the AE pulse rate at a fixed strain rate, the time constant $_{\\text{s}}$ for surface annihilation of dislocations and the pinning time $_{\\text{p}}$ of the dislocations can be determined. A good agreement is found between the theoretical and experimental results related to the AE from alkali halide crystals.

  2. The Effect of Radiation "Memory" in Alkali-Halide Crystals

    Science.gov (United States)

    Korovkin, M. V.; Sal'nikov, V. N.

    2017-01-01

    The exposure of the alkali-halide crystals to ionizing radiation leads to the destruction of their structure, the emergence of radiation defects, and the formation of the electron and hole color centers. Destruction of the color centers upon heating is accompanied by the crystal bleaching, luminescence, and radio-frequency electromagnetic emission (REME). After complete thermal bleaching of the crystal, radiation defects are not completely annealed, as the electrons and holes released from the color centers by heating leave charged and locally uncompensated defects. Clusters of these "pre centers" lead to electric microheterogeneity of the crystal, the formation of a quasi-electret state, and the emergence of micro-discharges accompanied by radio emission. The generation of REME associated with residual defectiveness, is a manifestation of the effect of radiation "memory" in dielectrics.

  3. An optical criterion to obtain miscible mixed crystals in alkali halides

    OpenAIRE

    2008-01-01

    This work gives a novel criterion to predict the formation of alkali halide solid solutions and discusses some results obtained in the development of ternary and quaternary miscible crystalline dielectric mixtures of alkali halides. These mixtures are miscible in any concentration of their components. The miscibility of these mixed crystals is quite related to the F center through the behavior observed in the spectral position of the optical absorption F band as a function of the lattice cons...

  4. Thermoluminescence response of a mixed ternary alkali halide crystals exposed to gamma rays

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez M, R.; Perez S, R. [Universidad de Sonora, Departamento de Investigacion en Fisica, Apdo. Postal 5-088, 83190 Hermosillo, Sonora (Mexico); Vazquez P, G.; Riveros, H. [UNAM, Instituto de Fisica, Apdo. Postal 20-364, 01000 Mexico D. F. (Mexico); Gonzalez M, P., E-mail: mijangos@cifus.uson.mx [ININ, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico)

    2014-08-15

    Ionic crystals, mainly alkali halide crystals have been the subject of intense research for a better understanding of the luminescence properties of defects induced by ionizing radiation. The defects in crystals can be produced in appreciable concentration due to elastic stresses, radiation, and addition of impurities. These defects exhibit remarkable thermoluminescence properties. This work is concerned with the Tl properties of a ternary alkali halide crystal after being irradiated with gamma and beta rays. It has been found that the Tl glow peak of the crystal follows a rule of average associated to the Tl Temperatures of the components of the mixture, similarly to the response of europium doped binary mixed crystals KCl{sub x}KBr{sub 1-x} and KBr{sub x}RbBr{sub 1-x}. (Author)

  5. Correlation between deformation bleaching and mechanoluminescence in coloured alkali halide crystals

    Indian Academy of Sciences (India)

    B P Chandra; M Ramrakhiani; P Sahu; A M Rastogi

    2000-02-01

    The present paper reports the correlation between deformation bleaching of coloration and mechanoluminescence (ML) in coloured alkali halide crystals. When the -centre electrons captured by moving dislocations are picked up by holes, deep traps and other compatible traps, then deformation bleaching occurs. At the same time, radiative recombination of dislocation captured electrons with the holes gives rise to the mechanoluminescence. Expressions are derived for the strain dependence of the density of colour centres in deformed crystals and also for the number of colour centres bleached. So far as strain, temperature, density of colour centres, a and volume dependence are concerned, there exists a correlation between the deformation bleaching and ML in coloured alkali halide crystals. From the strain dependence of the density of colour centres in deformed crystals, the value of coefficient of deformation bleaching is determined and it is found to be 1.93 and 2.00 for KCl and KBr crystals, respectively. The value of $(D + \\mathcal{X})$ is determined from the strain dependence of the ML intensity and it is found to be 2.6 and 3.7 for KCl and KBr crystals, respectively. This gives the value of coefficient of deformation generated compatible traps $\\mathcal{X}$ to be 0.67 and 1.7 for KCl and KBr crystals, respectively.

  6. Rapid yet accurate first principle based predictions of alkali halide crystal phases using alchemical perturbation

    CERN Document Server

    Solovyeva, Alisa

    2016-01-01

    We assess the predictive power of alchemical perturbations for estimating fundamental properties in ionic crystals. Using density functional theory we have calculated formation energies, lattice constants, and bulk moduli for all sixteen iso-valence-electronic combinations of pure pristine alkali halides involving elements $A \\in \\{$Na, K, Rb, Cs$\\}$ and $X \\in \\{$F, Cl, Br, I$\\}$. For rock salt, zincblende and cesium chloride symmetry, alchemical Hellmann-Feynman derivatives, evaluated along lattice scans of sixteen reference crystals, have been obtained for all respective 16$\\times$15 combinations of reference and predicted target crystals. Mean absolute errors (MAE) are on par with density functional theory level of accuracy for energies and bulk modulus. Predicted lattice constants are less accurate. NaCl is the best reference salt for alchemical estimates of relative energies (MAE $<$ 40 meV/atom) while alkali fluorides are the worst. By contrast, lattice constants are predicted best using NaF as a re...

  7. Skylab experiments on semiconductors and alkali halides. [single crystal growth

    Science.gov (United States)

    Lundquist, C. A.

    1974-01-01

    The space processing experiments performed during the Skylab missions included one on single crystal growth of germanium selenide and telluride, one on pure and doped germanium crystals, two on pure and doped indium antimonide, one on gallium-indium-antimony systems, and one on a sodium chloride-sodium fluoride eutectic. In each experiment, three ampoules of sample were processed in the multipurpose electric furnace within the Skylab Materials Processing Facility. All were successful in varying degrees and gave important information about crystal growth removed from the effects of earth surface gravity.

  8. THEORY OF PLASTICO ML IN γ–IRRADIATED ALKALI HALIDE CRYSTALS

    Directory of Open Access Journals (Sweden)

    NAMITA RAJPUT

    2011-06-01

    Full Text Available The present paper reports the results of some theoretical approach made to the studies of mechanoluminescence (ML in coloured alkali halide crystals. It is shown that moving dislocations produced during plastic deformation of crystalline materials cause light emission due to several processes like mechanical or electrostatic interaction of dislocations with defect centres, the dielectric breakdown of adsorbed gaseous molecules by the surface accumulated dislocation charges, the generation of holes during decay of mobile dislocations on the surfaces of crystals, etc. On the basis of rate equations, expressions are derived for the rise and decay of ML intensity at a given strain rate. The estimated values of ML intensities for different crystals are found to be comparable with the experimentally observed values. The expression derived are able to explain the dependence of ML intensity on several parameters like strain-rate, defect centre density, temperature, applied stress, crystal- size etc.

  9. Non-linear composition dependence of the conductivity parameters in alkali halides mixed crystals

    Energy Technology Data Exchange (ETDEWEB)

    Zardas, Georgios E., E-mail: gzardas@phys.uoa.g [Department of Solid State Physics, Faculty of Physics, University of Athens, Panepistimiopolis, 157 84 Zografos (Greece)

    2009-06-01

    Since mixed alkali halides were found to have applications in optical, optoelectronic and electronic devices, a strong interest has recently expressed for the study of their physical properties. Here, we discuss the experimental finding that a maximum conductivity enhancement with respect to pure constituents is obtained at a certain composition. We show that this composition can be predicted from the bulk properties of the end members.

  10. Infrared spectra of FHF - in alkali halides

    Science.gov (United States)

    Chunnilall, C. J.; Sherman, W. F.

    1982-03-01

    The bifluoride ion, FHF -, has been substitutionally isolated within single crystal samples of several different alkali halides. Infrared spectra of these crystals have been studied for sample temperatures down to 8K when half-bandwidths of less than 1 cm -1 have been observed. (Note that at room temperature ν 3 is observed to have a half-bandwidth of about 40 cm -1). The frequency shifts and half-bandwidth changes caused by cooling are considered together with the frequency shifts caused by pressures up to 10 k bar. The low temperature spectra clearly indicate that FHF - is a linear symmetrical ion when substitutionally isolated within alkali halides of either the NaCl or CsCl structure.

  11. Alkali metal and alkali earth metal gadolinium halide scintillators

    Energy Technology Data Exchange (ETDEWEB)

    Bourret-Courchesne, Edith; Derenzo, Stephen E.; Parms, Shameka; Porter-Chapman, Yetta D.; Wiggins, Latoria K.

    2016-08-02

    The present invention provides for a composition comprising an inorganic scintillator comprising a gadolinium halide, optionally cerium-doped, having the formula A.sub.nGdX.sub.m:Ce; wherein A is nothing, an alkali metal, such as Li or Na, or an alkali earth metal, such as Ba; X is F, Br, Cl, or I; n is an integer from 1 to 2; m is an integer from 4 to 7; and the molar percent of cerium is 0% to 100%. The gadolinium halides or alkali earth metal gadolinium halides are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

  12. Influence of small dozes ultra-violet radiation on motion of dislocation in alkali-halide crystals

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    The purpose of this work was research into influence of ultra-violet radiation on size of run of regional and screw dislocations in beams of dislocation sockets, formed at indentation surface of alkali-halide crystals. In experiments it was used crystals NaCl, with the quantitative maintenance of impurity 10-2 -10-3weight%, the wave length of UV-radiation λ=250 nanometers, the sizes of samples 10mm× 20mm× 2mm,temperature of samples was constant T=290 K.It is established that indentation and the simultaneous irradiation of samples a ultraviolet is increases size of run of head dispositions in dislocation sockets..It is marked, that influence UV-radiation nonequivalence for various times of an exposition. At small times (till 5 minutes) the size of run grows. The length of beams increases on ~ 50 %. At the further increase in time of influence of a ultraviolet the length of beams is reduced till the sizes corresponding stressing without an irradiation (Figs. 1, 2, 3). The effect is observed on dislocation beams of regional and screw orientations and most expressed at small loadings (in our experiments-10 grams) (Fig. 3).Observable effects are explained from positions dislocation-exciton interactions. At UV-radiation exciton cooperates with the charged step on a disposition, causing movement of a step along a disposition on one internuclear distance. Due to this interaction overcoming by a disposition of a grid of stoppers is facilitated.Big times of endurance cause a relaxation of pressure directly in a print that provides convertible movement of dispositions in area of a print and as consequence, reduction of length of beams of dislocation sockets.

  13. Temperature dependence of pulse-induced mechanoluminescence excitation in coloured alkali halide crystals

    Indian Academy of Sciences (India)

    Namita Rajput; S Tiwari; B P Chandra

    2004-12-01

    In practice, the relative efficiencies of different crystals are often determined under identical conditions of temperature and excitation. If the temperature of a crystal is increased or decreased with respect to room temperature, luminescence efficiency may get increased or decreased according to the composition of the crystal. When coloured crystals of NaCl, NaBr, KCl and KBr are excited by pulse-induced excitation at different temperatures, the mechanoluminescence (ML) intensity increases with temperature. The ML intensity of first peak, ml, second peak, _m2 and the total ML intensity, T, initially increase with temperature and then tend to attain an optimum value for a particular temperature of crystals. The ratio, m2/ml, is found to increase with increasing temperature of the crystals. The expression derived on the basis of rate equations, are able to explain the temperature dependence of ML intensity on several parameters.

  14. Thermoluminescence of alkali halides and its implications

    Energy Technology Data Exchange (ETDEWEB)

    Gartia, R.K., E-mail: rkgartia02@yahoo.in [Physics Department, Manipur University, Imphal 795003 (India); Rey, L. [Aerial-CRT-parc d' Innovation, B.P. 40443, F-67412 Illkirch Cedex (France); Tejkumar Singh, Th. [Physics Department, Manipur University, Imphal 795003 (India); Basanta Singh, Th. [Luminescence Dating Laboratory, Manipur University, Imphal 795003 (India)

    2012-03-01

    Trapping levels present in some alkali halides namely NaCl, KCl, KBr, and KI are determined by deconvolution of the thermoluminescence (TL) curves. Unlike most of the studies undertaken over the last few decades, we have presented a comprehensive picture of the phenomenon of TL as an analytical technique capable of revealing the position of the trapping levels present in the materials. We show that for all practical purposes, TL can be described involving only the three key trapping parameters, namely, the activation energy (E), the frequency factor (s), and the order of kinetics (b) even for complex glow curves having a number of TL peaks. Finally, based on these, we logically infer the importance of TL in development and characterization of materials used in dosimetry, dating and scintillation.

  15. Study of alkali halide/FHF - systems at 10 - 290 K, 0 - 8 kBAR

    Science.gov (United States)

    Chunnilall, C. J.; Sherman, W. F.; Wilkinson, G. R.

    1984-03-01

    The bifluoride ion FHF -, (and FDF -), has been substitutionally isolated within single crystal samples of several alkali halides. Infrared and Raman spectra of these crystals have been studied at variable temperature and pressure. The infrared absorptions are strong, whereas the Raman is weak. At low temperatures the bands are very sharp with halfwidths less than 1 cm -1. On applying pressure, ν3 increases in frequency whereas ν2 decreases. On reducing temperature, ν3 decreases in frequency whereas ν2 increases. Hence the effect of volume contraction is overridden in the temperature dependent case. The deuterated spectra confirm that the bifluoride ion is well isolated within the alkali halide matrix.

  16. Relation between the electroforming voltage in alkali halide-polymer diodes and the bandgap of the alkali halide

    Energy Technology Data Exchange (ETDEWEB)

    Bory, Benjamin F.; Wang, Jingxin; Janssen, René A. J.; Meskers, Stefan C. J., E-mail: s.c.j.meskers@tue.nl [Molecular Materials and Nanosystems and Institute for Complex Molecular Systems, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (Netherlands); Gomes, Henrique L. [Instituto de Telecomunicações, Av. Rovisco, Pais 1, 1049-001 Lisboa, Portugal and Universidade do Algarve, Campus de Gambelas, 8005-139 Faro (Portugal); De Leeuw, Dago M. [Max-Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany and King Abdulaziz University, Jeddah (Saudi Arabia)

    2014-12-08

    Electroforming of indium-tin-oxide/alkali halide/poly(spirofluorene)/Ba/Al diodes has been investigated by bias dependent reflectivity measurements. The threshold voltages for electrocoloration and electroforming are independent of layer thickness and correlate with the bandgap of the alkali halide. We argue that the origin is voltage induced defect formation. Frenkel defect pairs are formed by electron–hole recombination in the alkali halide. This self-accelerating process mitigates injection barriers. The dynamic junction formation is compared to that of a light emitting electrochemical cell. A critical defect density for electroforming is 10{sup 25}/m{sup 3}. The electroformed alkali halide layer can be considered as a highly doped semiconductor with metallic transport characteristics.

  17. "Textbook" adsorption at "nontextbook" adsorption sites: halogen atoms on alkali halide surfaces.

    Science.gov (United States)

    Li, Bo; Michaelides, Angelos; Scheffler, Matthias

    2006-07-28

    Density-functional theory and second order Møller-Plesset perturbation theory calculations indicate that halogen atoms bond preferentially to halide substrate atoms on a series of alkali halide surfaces, rather than to the alkali atoms as might be anticipated. An analysis of the electronic structures in each system reveals that this novel adsorption mode is stabilized by the formation of textbook two-center three-electron covalent bonds. The implications of these findings to, for example, nanostructure crystal growth, are briefly discussed.

  18. A new mechanism for radiation damage processes in alkali halides

    NARCIS (Netherlands)

    Dubinko, V.I.; Turkin, A.A.; Vainshtein, D.I.; Hartog, H.W. den

    1999-01-01

    We present a theory of radiation damage formation in alkali halides based on a new mechanism of dislocation climb, which involves the production of VF centers (self-trapped hole neighboring a cation vacancy) as a result of the absorption of H centers of dislocation lines. We consider the evolution o

  19. Alkali halide microstructured optical fiber for X-ray detection

    Energy Technology Data Exchange (ETDEWEB)

    DeHaven, S. L., E-mail: stanton.l.dehaven@nasa.gov, E-mail: russel.a.wincheski@nasa.gov; Wincheski, R. A., E-mail: stanton.l.dehaven@nasa.gov, E-mail: russel.a.wincheski@nasa.gov [NASA Langley Research Center, Hampton, VA 23681 (United States); Albin, S., E-mail: salbin@nsu.edu [Norfolk State University, Norfolk, VA 23504 (United States)

    2015-03-31

    Microstructured optical fibers containing alkali halide scintillation materials of CsI(Na), CsI(Tl), and NaI(Tl) are presented. The scintillation materials are grown inside the microstructured fibers using a modified Bridgman-Stockbarger technique. The x-ray photon counts of these fibers, with and without an aluminum film coating are compared to the output of a collimated CdTe solid state detector over an energy range from 10 to 40 keV. The photon count results show significant variations in the fiber output based on the materials. The alkali halide fiber output can exceed that of the CdTe detector, dependent upon photon counter efficiency and fiber configuration. The results and associated materials difference are discussed.

  20. Alkali Halide Microstructured Optical Fiber for X-Ray Detection

    Science.gov (United States)

    DeHaven, S. L.; Wincheski, R. A.; Albin, S.

    2014-01-01

    Microstructured optical fibers containing alkali halide scintillation materials of CsI(Na), CsI(Tl), and NaI(Tl) are presented. The scintillation materials are grown inside the microstructured fibers using a modified Bridgman-Stockbarger technique. The x-ray photon counts of these fibers, with and without an aluminum film coating are compared to the output of a collimated CdTe solid state detector over an energy range from 10 to 40 keV. The photon count results show significant variations in the fiber output based on the materials. The alkali halide fiber output can exceed that of the CdTe detector, dependent upon photon counter efficiency and fiber configuration. The results and associated materials difference are discussed.

  1. Optical and Spectral Studies on β Alanine Metal Halide Hybrid Crystals

    Science.gov (United States)

    Sweetlin, M. Daniel; Selvarajan, P.; Perumal, S.; Ramalingom, S.

    2011-10-01

    We have synthesized and grown β alanine metal halide hybrid crystals viz. β alanine cadmium chloride (BACC), an amino acid transition metal halide complex crystal and β alanine potassium chloride (BAPC), an amino acid alkali metal halide complex crystal by slow evaporation method. The grown crystals were found to be transparent and have well defined morphology. The optical characteristics of the grown crystals were carried out with the help of UV-Vis Spectroscopy. The optical transmittances of the spectrums show that BAPC is more transparent than BACC. The Photoluminescence of the materials were determined by the Photoluminescent Spectroscopy

  2. Analysis and modeling of alkali halide aqueous solutions

    DEFF Research Database (Denmark)

    Kim, Sun Hyung; Anantpinijwatna, Amata; Kang, Jeong Won;

    2016-01-01

    A new model is proposed for correlation and prediction of thermodynamic properties of electrolyte solutions. In the proposed model, terms of a second virial coefficient-type and of a KT-UNIFAC model are used to account for a contribution of binary interactions between ion and ion, and water and ion...... on calculations for various electrolyte properties of alkali halide aqueous solutions such as mean ionic activity coefficients, osmotic coefficients, and salt solubilities. The model covers highly nonideal electrolyte systems such as lithium chloride, lithium bromide and lithium iodide, that is, systems...

  3. Structure and Bonding in Small Neutral Alkali-Halide Clusters

    CERN Document Server

    Aguado, A; López, J M; Alonso, J A

    1997-01-01

    The structural and bonding properties of small neutral alkali-halide clusters (AX)n, with n less than or equal to 10, A=Li, Na, K, Rb and X=F, Cl, Br, I, are studied using the ab initio Perturbed Ion (aiPI) model and a restricted structural relaxation criterion. A trend of competition between rock-salt and hexagonal ring-like isomers is found and discussed in terms of the relative ionic sizes. The main conclusion is that an approximate value of r_C/r_A=0.5 (where r_C and r_A are the cationic and anionic radii) separates the hexagonal from the rock-salt structures. The classical electrostatic part of the total energy at the equilibrium geometry is enough to explain these trends. The magic numbers in the size range studied are n= 4, 6 and 9, and these are universal since they occur for all alkali-halides and do not depend on the specific ground state geometry. Instead those numbers allow for the formation of compact clusters. Full geometrical relaxations are considered for (LiF)n (n=3-7) and (AX)_3 clusters, an...

  4. Modeling and investigation of heavy oxide and alkali-halide scintillators for potential use in neutron and gamma detection systems

    OpenAIRE

    Cadiente, Jeremy S.

    2015-01-01

    Approved for public release; distribution is unlimited Heavy inorganic oxide and alkali-halide crystals, which previous experimental research has indicated to have fast neutron detection efficiencies well over 40%, were investigated for potential use as highly efficient gamma-neutron radiation detectors. The Monte Carlo N-Particle radiation transport code (MCNP) was used to characterize the radiation interactions in a candidate set of crystals, including Bismuth Germanate (BGO), Lead Tungs...

  5. Strong Turbulence in Alkali Halide Negative Ion Plasmas

    Science.gov (United States)

    Sheehan, Daniel

    1999-11-01

    Negative ion plasmas (NIPs) are charge-neutral plasmas in which the negative charge is dominated by negative ions rather than electrons. They are found in laser discharges, combustion products, semiconductor manufacturing processes, stellar atmospheres, pulsar magnetospheres, and the Earth's ionosphere, both naturally and man-made. They often display signatures of strong turbulence^1. Development of a novel, compact, unmagnetized alkali halide (MX) NIP source will be discussed, it incorporating a ohmically-heated incandescent (2500K) tantulum solenoid (3cm dia, 15 cm long) with heat shields. The solenoid ionizes the MX vapor and confines contaminant electrons, allowing a very dry (electron-free) source. Plasma densities of 10^10 cm-3 and positive to negative ion mass ratios of 1 Fusion 4, 91 (1978).

  6. The Structure and Thermodynamics of Alkali Halide Vapors.

    Science.gov (United States)

    Hartley, John George

    A comprehensive set of electron diffraction experiments were performed on 16 of the alkali halides in the vapor phase. A 40kev electron beam was scattered from the vapor effusing out of the nozzle of a temperature controlled gas cell. The resulting data were analyzed at the University of Edinburgh with the program ED80. This resulted in values for the bond lengths of monomers and the dimers, the bond angle of the dimers and the monomer-dimer ratios. In several cases, it was possible to further refine the data to obtain information on the mean amplitudes of vibration. As a check on the accuracy of the results, the monomer bond distances obtained by electron diffraction were compared to values obtained previously by microwave spectroscopy. The average monomer bond length r_{a} is corrected to obtain the equilibrium bond distance r_{e}. This value is then compared to the value of r_{e } obtained from microwave spectroscopy and found to be in excellent agreement. The bond lengths and angles of the dimers were compared against model calculations. While no one model was found to accurately predict the dimer structure parameters of all of the alkali halides, the Rittner model of Gowda et al was found to accurately predict the structure of six of the dimers. Thermodynamical calculations were performed on the model data which resulted in theoretical curves of the monomer-dimer ratios. Comparison of these curves with the experimental monomer-dimer ratio permits an evaluation of the model vibration frequencies. The enthalpy of formation of the dimer, Delta H_sp{2}{f}(298) is examined with regard to the size of the variation necessary to bring about agreement of the experimental and model monomer-dimer ratios.

  7. "Textbook" adsorption at "nontextbook" adsorption sites: Halogen atoms on alkali halide surfaces

    OpenAIRE

    Li, B.; Michaelides, A.; Scheffler, M.

    2006-01-01

    Density-functional theory (DFT) and second order Møller-Plesset perturbation theory calculations indicate that halogen atoms bond preferentially to halide substrate atoms on a series of alkali halide surfaces, rather than to the alkali atoms as might be anticipated. An analysis of the electronic structures in each system reveals that this novel adsorption mode is stabilized by the formation of textbook two-center three-electron covalent bonds. The implications of these findings to, for exampl...

  8. Anharmonic properties of potassium halide crystals

    OpenAIRE

    RAJU, Krishna Murti

    2011-01-01

    An effort has been made to obtain the anharmonic properties of potassium halides starting from primary physical parameters viz. nearest neighbor distance and hardness parameters assuming long- and short- range potentials at elevated temperatures. The elastic energy density for a deformed crystal can be expanded as power series of strains for obtaining coefficients of quadratic, cubic and quartic terms which are known as the second, third and fourth order elastic constants respectively...

  9. Epitaxial Growth of a Methoxy-Functionalized Quaterphenylene on Alkali Halide Surfaces

    DEFF Research Database (Denmark)

    Balzer, Frank; Sun, Rong; Parisi, Jürgen

    2015-01-01

    The epitaxial growth of the methoxy functionalized para-quaterphenylene (MOP4) on the (001) faces of the alkali halides NaCl and KCl and on glass is investigated by a combination of lowenergy electron diffraction (LEED), polarized light microscopy (PLM), atomic force microscopy (AFM), and X...

  10. Correlation between standard enthalpy of formation, structural parameters and ionicity for alkali halides

    Directory of Open Access Journals (Sweden)

    Nasar Abu

    2013-01-01

    Full Text Available The standard enthalpy of formation (ΔHo has been considered to be an interesting and useful parameter for the correlation of various properties of alkali halides. The interrelation between ΔHo and structural parameters for the halides of Li, Na, K and Rb has been thoroughly analyzed. When cationic component element is kept constant in a homologous series of alkali halides, the negative value of ΔHo has been observed to decrease linearly with increase of interionic distance (d and accordingly following empirical equation ΔHo = α + βd (where α and β are empirical constants has been established. However, for common anionic series of alkali halides an opposite nonlinear trend has been observed with the exception of common fluorides. The correlation study on the standard enthalpy of formation has been extended in term of radius ratio and also discussed in the light of ionization energy of the metal, electron affinity of the halogen, size of the ions, ionic character of bond and lattice energy of the compound.

  11. Famed Bulgarian physicists. I. St. Petroff's Goettingen research of the photostimulated interconversions of color centers in alkali halides: the discovery of the photostimulated aggregation

    CERN Document Server

    Georgiev, Mladen

    2008-01-01

    This essay tells briefly of the life and work of one of the most successful scientists originating from a Balkan settlement whose name and popularity have greatly exceeded its realm. The word is of a discovery during WWII of the photostimulated aggregation of the F centers (else alkali atoms) dissolved from the vapor into an alkali halide crystal. Using optical absorption techniques while a grantee of Humboldt's Foundation in Goettingen, Germany between 1943-1944, he found new absorption bands pertaining to small-size F center aggregates and followed their interconversions. A primary photochemical solid state reaction was evidenced for the first time leading to nanoscale products.

  12. Refined potentials for rare gas atom adsorption on rare gas and alkali-halide surfaces

    Science.gov (United States)

    Wilson, J. W.; Heinbockel, J. H.; Outlaw, R. A.

    1985-01-01

    The utilization of models of interatomic potential for physical interaction to estimate the long range attractive potential for rare gases and ions is discussed. The long range attractive force is calculated in terms of the atomic dispersion properties. A data base of atomic dispersion parameters for rare gas atoms, alkali ion, and halogen ions is applied to the study of the repulsive core; the procedure for evaluating the repulsive core of ion interactions is described. The interaction of rare gas atoms on ideal rare gas solid and alkali-halide surfaces is analyzed; zero coverage absorption potentials are derived.

  13. Reactions between cold methyl halide molecules and alkali-metal atoms.

    Science.gov (United States)

    Lutz, Jesse J; Hutson, Jeremy M

    2014-01-07

    We investigate the potential energy surfaces and activation energies for reactions between methyl halide molecules CH3X (X = F, Cl, Br, I) and alkali-metal atoms A (A = Li, Na, K, Rb) using high-level ab initio calculations. We examine the anisotropy of each intermolecular potential energy surface (PES) and the mechanism and energetics of the only available exothermic reaction pathway, CH3X + A → CH3 + AX. The region of the transition state is explored using two-dimensional PES cuts and estimates of the activation energies are inferred. Nearly all combinations of methyl halide and alkali-metal atom have positive barrier heights, indicating that reactions at low temperatures will be slow.

  14. Theory of metal atom-water interactions and alkali halide dimers

    Science.gov (United States)

    Jordan, K. D.; Kurtz, H. A.

    1982-01-01

    Theoretical studies of the interactions of metal atoms with water and some of its isoelectronic analogs, and of the properties of alkali halides and their aggregates are discussed. Results are presented of ab initio calculations of the heats of reaction of the metal-water adducts and hydroxyhydrides of Li, Be, B, Na, Mg, and Al, and of the bond lengths and angles an; the heats of reaction for the insertion of Al into HF, H2O, NH3, H2S and CH3OH, and Be and Mg into H2O. Calculations of the electron affinities and dipole moments and polarizabilities of selected gas phase alkali halide monomers and dimers are discussed, with particular attention given to results of calculations of the polarizability of LiF taking into account electron correlation effects, and the polarizability of the dimer (LiF)2.

  15. Optical/IR Characteristics of Alkali Halide Aerosol Clouds over the Ocean.

    Science.gov (United States)

    2014-09-26

    Continues) 19 ABSTRACT (Continue on reverse if necessary and identify by block number) --- Artificial fogs grown on hygroscopic alkali halide...the cruise fell into one of two catagories: 1) elevated clouds or 2) surface fog banks. Both types of clouds have the potential of being useful for...8217 TABLE VI Computed Transmission Through Cloud #8 (from Size Distribution) (250 Meters Thick Cloud) Wavel ength i crons) 0.55 3.5 10.6 Rel

  16. Thermodynamic reactivity, growth and characterization of mercurous halide crystals

    Science.gov (United States)

    Singh, N. B.; Gottlieb, M.; Henningsen, T.; Hopkins, R. H.; Mazelsky, R.; Singh, M.; Glicksman, M. E.; Paradies, C.

    1992-01-01

    Thermodynamic calculations were carried out for the Hg-X-O system (X = Cl, Br, I) to identify the potential sources of contamination and relative stability of oxides and oxy-halide phases. The effect of excess mercury vapor pressure on the optical quality of mercurous halide crystal was studied by growing several mercurous chloride crystals from mercury-rich composition. The optical quality of crystals was examined by birefringence interferometry and laser scattering studies. Crystals grown in slightly mercury-rich composition showed improved optical quality relative to stoichiometric crystals.

  17. Calculation of Interaction Parameters from Immiscible Phase Diagram of Alkali Metal or Alkali Earth Metal-Halide System by Means of Subregular Solution Model

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    In this paper, the interaction parameters in the subregular solution model, λ1 and λ2, are regarded as a linear function of temperature, T. Therefore, the molar excess Gibbs energy of A-B binary system may be reexpressed as follows: The calculation of the model parameters, λ11, λ12, λ21 and λ22, was carried out numerically from the phase diagrams for 11 alkali metal-alkali halide or alkali earth metal-halide systems.In addition, artificial neural network trained by known data has been used to predict the values of these model parameters. The predicted results are in good agreement with the.calculated ones. The applicability of the subregular solution model to the alkali metal-alkali halide or alkali earth metal-halide systems were tested by comparing the available experimental composition along the boundary of miscibility gap with the calculated ones which were obtained by using genetic algorithm. The good agreement between the calculated and experimental results across the entire liquidus is valid evidence in support of the model.

  18. Far Infrared Optical Spectroscopy of Alkali Halide-Polymer Composites

    Science.gov (United States)

    McWhirter, J. T.; Broderick, S. D.; Rodriguez, G. A.

    1998-03-01

    Composite samples of small (dimension polytetrafluoroethylene) have been prepared. The far infrared optical spectra of these samples are presented, spanning a temperature range of 300 to thermal expansion, using published values for the mode Gruneisen parameter and the temperature dependence of the lattice thermal coefficient. In contrast, the linewidth (phonon lifetime) of the composite samples is roughly twice as large as that observed for thin film and bulk crystals, and has a much stronger temperature dependence as well.

  19. Metal Hydride and Alkali Halide Opacities in Extrasolar Giant Planets and Cool Stellar Atmospheres

    Science.gov (United States)

    Weck, Philippe F.; Stancil, Phillip C.; Kirby, Kate; Schweitzer, Andreas; Hauschildt, Peter H.

    2006-01-01

    The lack of accurate and complete molecular line and continuum opacity data has been a serious limitation to developing atmospheric models of cool stars and Extrasolar Giant Planets (EGPs). We report our recent calculations of molecular opacities resulting from the presence of metal hydrides and alkali halides. The resulting data have been included in the PHOENIX stellar atmosphere code (Hauschildt & Baron 1999). The new models, calculated using spherical geometry for all gravities considered, also incorporate our latest database of nearly 670 million molecular lines, and updated equations of state.

  20. Enthalpic Interaction for α-Amino Acid with Alkali Metal Halides in Water

    Institute of Scientific and Technical Information of China (English)

    LU,Yan(卢雁)

    2004-01-01

    The studies of the enthalpic interaction parameters, hxy, hxyy and hxxv, of alkali metal halides with glycine,α-alanine and α-aminobutyric acid were published. Synthetic considering of the results of the studies, some interesting behaviors of the interaction between alkali metal halides and the α-amino acids have been found. The values of hxy will increase with the increase of the number of carbon atoms in alkyl side chain of amino acid molecules and decrease with the increase of the radius of the ions. The increasing of the salt's effect on the hydrophobic hydration structure as the radii of anion is more obvious than as that of cation. The value of hxxy will regularly decrease with the increase of the number of carbon atoms in the alkyl chain of amino acids and linear increase with the increase of the radius. But the relation of hxxy with the radius of cations is not evident. The value of hxyy will increase with the increase of the radii of the ions. As the increase of the number of carbon atoms of amino acids, hxyy is decreas for the ions which have lager size and there is a maximum value at α-alanine for the ions which have small size. The behaviors of the interaction mentioned above were further discussed in view of electrostatic and structural interactions.

  1. Alkali Metal Halide Salts as Interface Additives to Fabricate Hysteresis-Free Hybrid Perovskite-Based Photovoltaic Devices.

    Science.gov (United States)

    Wang, Lili; Moghe, Dhanashree; Hafezian, Soroush; Chen, Pei; Young, Margaret; Elinski, Mark; Martinu, Ludvik; Kéna-Cohen, Stéphane; Lunt, Richard R

    2016-09-07

    A new method was developed for doping and fabricating hysteresis-free hybrid perovskite-based photovoltaic devices by using alkali metal halide salts as interface layer additives. Such salt layers introduced at the perovskite interface can provide excessive halide ions to fill vacancies formed during the deposition and annealing process. A range of solution-processed halide salts were investigated. The highest performance of methylammonium lead mixed-halide perovskite device was achieved with a NaI interlayer and showed a power conversion efficiency of 12.6% and a hysteresis of less than 2%. This represents a 90% improvement compared to control devices without this salt layer. Through depth-resolved mass spectrometry, optical modeling, and photoluminescence spectroscopy, this enhancement is attributed to the reduction of iodide vacancies, passivation of grain boundaries, and improved hole extraction. Our approach ultimately provides an alternative and facile route to high-performance and hysteresis-free perovskite solar cells.

  2. Indirect NMR spin-spin coupling constants in diatomic alkali halides.

    Science.gov (United States)

    Jaszuński, Michał; Antušek, Andrej; Demissie, Taye B; Komorovsky, Stanislav; Repisky, Michal; Ruud, Kenneth

    2016-12-28

    We report the Nuclear Magnetic Resonance (NMR) spin-spin coupling constants for diatomic alkali halides MX, where M = Li, Na, K, Rb, or Cs and X = F, Cl, Br, or I. The coupling constants are determined by supplementing the non-relativistic coupled-cluster singles-and-doubles (CCSD) values with relativistic corrections evaluated at the four-component density-functional theory (DFT) level. These corrections are calculated as the differences between relativistic and non-relativistic values determined using the PBE0 functional with 50% exact-exchange admixture. The total coupling constants obtained in this approach are in much better agreement with experiment than the standard relativistic DFT values with 25% exact-exchange, and are also noticeably better than the relativistic PBE0 results obtained with 50% exact-exchange. Further improvement is achieved by adding rovibrational corrections, estimated using literature data.

  3. X-ray Scintillation in Lead Halide Perovskite Crystals

    OpenAIRE

    Birowosuto, M. D.; Cortecchia, D.; Drozdowski, W.; K. Brylew; Łachmański, W.; A. Bruno; Soci, C.

    2016-01-01

    Current technologies for X-ray detection rely on scintillation from expensive inorganic crystals grown at high-temperature, which so far has hindered the development of large-area scintillator arrays. Thanks to the presence of heavy atoms, solution-grown hybrid lead halide perovskite single crystals exhibit short X-ray absorption length and excellent detection efficiency. Here we compare X-ray scintillator characteristics of three-dimensional (3D) MAPbI3 and MAPbBr3 and two-dimensional (2D) (...

  4. Molecular Modeling and Monte Carlo Simulation of Concentrated Aqueous Alkali Halide Solutions at 25 C.

    Science.gov (United States)

    Llano-Restrepo, Mario Andres

    A study of concentrated aqueous alkali halide solutions is made at the molecular level, through modeling and computer simulation of their structural and thermodynamic properties. It is found that the HNC approximation is the best integral equation theory to predict such properties within the framework of the primitive model (PM). The intrinsic limitations of the PM in describing ionic association and hydration effects are addressed and discussed in order to emphasize the need for explicitly including the water molecules in the treatment of aqueous electrolyte solutions by means of a civilized model (CM). As a step toward developing a CM as simple as possible, it is shown that a modified version of the SPC model of liquid water in which the Lennard-Jones interaction between intermolecular oxygen sites is replaced by a hard core interaction, is still successful enough to predict the degree of hydrogen bonding of real water. A simple civilized model (SCM) (in which the ions are treated as hard spheres interacting through Coulombic potentials and the water molecules are simulated using the simplified SPC model) is introduced in order to study the changes in the structural features of various aqueous alkali halide solutions upon varying both the concentration and the size of the ions. Both cations and anions are found to be solvated by the water molecules at expense of a breakdown in the hydrogen-bonded water network. Hydration numbers are reported for the first time for NaBr and KBr, and the first simulation -based estimates for LiBr, NaI and KI are also obtained. In several cases, values of the hydration numbers based on the SCM are found to be in excellent agreement with available experimental results obtained from x-ray diffraction measurements. Finally, it is shown that a neoprimitive model (NPM) can be developed by incorporating some of the structural features seen in the SCM into the short-range part of the PM interionic potential via a shielded square well whose

  5. Physics of solid and liquid alkali halide surfaces near the melting point

    Science.gov (United States)

    Zykova-Timan, T.; Ceresoli, D.; Tartaglino, U.; Tosatti, E.

    2005-10-01

    This paper presents a broad theoretical and simulation study of the high-temperature behavior of crystalline alkali halide surfaces typified by NaCl(100), of the liquid NaCl surface near freezing, and of the very unusual partial wetting of the solid surface by the melt. Simulations are conducted using two-body rigid-ion Born-Mayer-Huggins-Fumi-Tosi (BMHFT) potentials, with full treatment of long-range Coulomb forces. After a preliminary check of the description of bulk NaCl provided by these potentials, which seems generally good even at the melting point, we carry out a new investigation of solid and liquid surfaces. Solid NaCl(100) is found in this model to be very anharmonic and yet exceptionally stable when hot. It is predicted by a thermodynamic integration calculation of the surface free energy that NaCl(100) should be a well-ordered, nonmelting surface, metastable even well above the melting point. By contrast, the simulated liquid NaCl surface is found to exhibit large thermal fluctuations and no layering order. In spite of that, it is shown to possess a relatively large surface free energy. The latter is traced to a surface entropy deficit, reflecting some kind of surface short-range order. We show that the surface short-range order is most likely caused by the continuous transition of the bulk ionic melt into the vapor, made of NaCl molecules and dimers rather than of single ions. Finally, the solid-liquid interface free energy is derived through Young's equation from direct simulation of partial wetting of NaCl(100) by a liquid droplet. The resulting interface free energy is large, in line with the conspicuous solid-liquid 27% density difference. A partial wetting angle near 50° close to the experimental value of 48° is obtained in the process. It is concluded that three elements, namely, the exceptional anharmonic stability of the solid (100) surface, the molecular short-range order at the liquid surface, and the costly solid-liquid interface, all

  6. X-ray Scintillation in Lead Halide Perovskite Crystals

    Science.gov (United States)

    Birowosuto, M. D.; Cortecchia, D.; Drozdowski, W.; Brylew, K.; Lachmanski, W.; Bruno, A.; Soci, C.

    2016-11-01

    Current technologies for X-ray detection rely on scintillation from expensive inorganic crystals grown at high-temperature, which so far has hindered the development of large-area scintillator arrays. Thanks to the presence of heavy atoms, solution-grown hybrid lead halide perovskite single crystals exhibit short X-ray absorption length and excellent detection efficiency. Here we compare X-ray scintillator characteristics of three-dimensional (3D) MAPbI3 and MAPbBr3 and two-dimensional (2D) (EDBE)PbCl4 hybrid perovskite crystals. X-ray excited thermoluminescence measurements indicate the absence of deep traps and a very small density of shallow trap states, which lessens after-glow effects. All perovskite single crystals exhibit high X-ray excited luminescence yields of >120,000 photons/MeV at low temperature. Although thermal quenching is significant at room temperature, the large exciton binding energy of 2D (EDBE)PbCl4 significantly reduces thermal effects compared to 3D perovskites, and moderate light yield of 9,000 photons/MeV can be achieved even at room temperature. This highlights the potential of 2D metal halide perovskites for large-area and low-cost scintillator devices for medical, security and scientific applications.

  7. Silicon halide-alkali metal flames as a source of solar grade silicon

    Science.gov (United States)

    Olson, D. B.; Miller, W. J.; Gould, R. K.

    1980-01-01

    The feasibility of using continuous high-temperature reactions of alkali metals and silicon halides to produce silicon in large quantities and of suitable purity for use in the production of photovoltaic solar cells was demonstrated. Low pressure experiments were performed demonstrating the production of free silicon and providing experience with the construction of reactant vapor generators. Further experiments at higher reagent flow rates were performed in a low temperature flow tube configuration with co-axial injection of reagents and relatively pure silicon was produced. A high temperature graphite flow tube was built and continuous separation of Si from NaCl was demonstrated. A larger scaled well stirred reactor was built. Experiments were performed to investigate the compatability of graphite based reactor materials of construction with sodium. At 1100 to 1200 K none of these materials were found to be suitable. At 1700 K the graphites performed well with little damage except to coatings of pyrolytic graphite and silicon carbide which were damaged.

  8. Epitaxial growth of a methoxy-functionalized quaterphenylene on alkali halide surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Balzer, F., E-mail: fbalzer@mci.sdu.dk [University of Southern Denmark, Mads Clausen Institute, Alsion 2, DK-6400 Sønderborg (Denmark); Sun, R. [University of Southern Denmark, Mads Clausen Institute, Alsion 2, DK-6400 Sønderborg (Denmark); Parisi, J. [University of Oldenburg, Energy and Semiconductor Research Laboratory, Institute of Physics, Carl-von-Ossietzky-Str. 9-11, D-26111 Oldenburg (Germany); Rubahn, H.-G. [University of Southern Denmark, Mads Clausen Institute, Alsion 2, DK-6400 Sønderborg (Denmark); Lützen, A. [University of Bonn, Kekulé Institute of Organic Chemistry and Biochemistry, Gerhard-Domagk-Str. 1, D-53121 Bonn (Germany); Schiek, M. [University of Oldenburg, Energy and Semiconductor Research Laboratory, Institute of Physics, Carl-von-Ossietzky-Str. 9-11, D-26111 Oldenburg (Germany)

    2015-12-31

    The epitaxial growth of the methoxy functionalized para-quaterphenylene (MOP4) on the (001) faces of the alkali halides NaCl and KCl and on glass is investigated by a combination of low energy electron diffraction (LEED), polarized light microscopy (PLM), atomic force microscopy (AFM), and X-ray diffraction (XRD). Both domains from upright molecules as well as fiber-like crystallites from lying molecules form. Neither a wetting layer from lying molecules nor widespread epitaxial fiber growth on the substrates is detected. Our results focus on the upright standing molecules, which condense into a thin film phase with an enlarged layer spacing compared to the bulk phase. - Highlights: • Growth of a methoxy-functionalized para-phenylene on dielectric surfaces is investigated. • Low-energy electron diffraction and X-ray diffraction techniques are employed for structural characterization. • Epitaxial growth of upright molecules only is documented. • Polarized optical microscopy together with atomic force microscopy complements the findings.

  9. Alkali halide solutions under thermal gradients: soret coefficients and heat transfer mechanisms.

    Science.gov (United States)

    Römer, Frank; Wang, Zilin; Wiegand, Simone; Bresme, Fernando

    2013-07-11

    We report an extensive analysis of the non-equilibrium response of alkali halide aqueous solutions (Na(+)/K(+)-Cl(-)) to thermal gradients using state of the art non-equilibrium molecular dynamics simulations and thermal diffusion forced Rayleigh scattering experiments. The coupling between the thermal gradient and the resulting ionic salt mass flux is quantified through the Soret coefficient. We find the Soret coefficient is of the order of 10(-3) K(-1) for a wide range of concentrations. These relatively simple solutions feature a very rich behavior. The Soret coefficient decreases with concentration at high temperatures (higher than T ∼ 315 K), whereas it increases at lower temperatures. In agreement with previous experiments, we find evidence for sign inversion in the Soret coefficient of NaCl and KCl solutions. We use an atomistic non-equilibrium molecular dynamics approach to compute the Soret coefficients in a wide range of conditions and to attain further microscopic insight on the heat transport mechanism and the behavior of the Soret coefficient in aqueous solutions. The models employed in this work reproduce the magnitude of the Soret coefficient, and the general dependence of this coefficient with temperature and salt concentration. We use the computer simulations as a microscopic approach to establish a correlation between the sign and magnitude of the Soret coefficients and ionic solvation and hydrogen bond structure of the solutions. Finally, we report an analysis of heat transport in ionic solution by quantifying the solution thermal conductivity as a function of concentration. The simulations accurately reproduce the decrease of the thermal conductivity with increasing salt concentration that is observed in experiments. An explanation of this behavior is provided.

  10. Size distributions and geometries of alkali halide nanoclusters probed using ESI FT-ICR mass spectrometry and quantum chemistry

    Science.gov (United States)

    Lemke, K.; Sadjadi, S.; Seward, T.

    2010-12-01

    The structures and energetic properties of ionic alkali metal halide clusters play a significant role in our understanding of aqueous geochemical processes such as salt dissolution, precipitation and neutralization reactions. Mass spectrometric and quantum chemical studies of such systems offer new opportunities to study the size-dependent evolution of cluster structures, the occurrence of magic number species as well as their fundamental properties. The work here presents new results for the stability, abundance and structure of pure [Na(NaClm)]+ , [K(KCl)m]+ and mixed [Na(NaCl)p(KCl)q]+ metal halide clusters with mQB3 and G4 methods and comment on the onset of the doubly charged cluster series. FT-ICR mass spectra for [Na(NaCl)n]+ clusters generated from 1mM NaCl in 20%H2O 80% acetonitrile in positive ion mode.

  11. X-ray Scintillation in Lead Halide Perovskite Crystals

    CERN Document Server

    Birowosuto, M D; Drozdowski, W; Brylew, K; Lachmanski, W; Bruno, A; Soci, C

    2016-01-01

    Current technologies for X-ray detection rely on scintillation from expensive inorganic crystals grown at high-temperature, which so far has hindered the development of large-area scintillator arrays. Thanks to the presence of heavy atoms, solution-grown hybrid lead halide perovskite single crystals exhibit short X-ray absorption length and excellent detection efficiency. Here we compare X-ray scintillator characteristics of three-dimensional (3D) MAPbI3 and MAPbBr3 and two-dimensional (2D) (EDBE)PbCl4 hybrid perovskite crystals. X-ray excited thermoluminescence measurements indicate the absence of deep traps and a very small density of shallow trap states, which lessens after-glow effects. All perovskite single crystals exhibit high X-ray excited luminescence yields of >120,000 photons/MeV at low temperature. Although thermal quenching is significant at room temperature, the large exciton binding energy of 2D (EDBE)PbCl4 significantly reduces thermal effects compared to 3D perovskites, and moderate light yie...

  12. Low-Energy Grazing Ion-Scattering From Alkali-Halide Surfaces: A Novel Approach To C-14 Detection

    Science.gov (United States)

    Meyer, F. W.; Galutschek, E.; Hotchkis, M.

    2009-03-01

    Carbon-14 labeled compounds are widely used in the pharmaceutical industry, e.g., as tracers to determine the fate of these compounds in vivo. Conventional accelerator mass spectrometry (AMS) is one approach that offers sufficiently high sensitivity to avoid radiological waste and contamination issues in such studies, but requires large, expensive facilities that are usually not solely dedicated to this task. At the ORNL Multicharged Ion Research Facility (MIRF) we are exploring a small size, low cost alternative to AMS for biomedical 14C tracer studies that utilizes ECR-ion-source-generated keV-energy-range multicharged C beams grazingly incident on an alkali halide target, where efficient negative ion production by multiple electron capture takes place. By using C ion charge states of +3 or higher, the molecular isobar interference at mass 14, e.g. 12CH2 and 13CH, is eliminated. The negatively charged ions in the beam scattered from the alkali halide surface are separated from other scattered charge states by two large acceptance (˜15 msr) stages of electrostatic analysis. The N-14 isobar interference is thus removed, since N does not support a stable negative ion. Initial results for C-14 detection obtained using C-14 enriched CO2 from ANSTO will be described.

  13. The optical properties of alkali nitrate single crystals

    Science.gov (United States)

    Anan'ev, Vladimir; Miklin, Mikhail

    2000-08-01

    Absorption of non-polarized light by a uniaxial crystal has been studied. The degree of absorption polarization has been calculated as a function of the ratio of optical densities in the region of low and high absorbances. This function is proposed for analysis of the qualitative and quantitative characteristics of uniaxial crystal absorption spectra. Non-polarized light spectra of alkali nitrate single crystals, both pure and doped with thallium, have been studied. It is shown that the absorption band at 300 nm is due to two transitions, whose intensities depend on temperature in various ways. There is a weak band in a short wavelength range of the absorption spectrum of potassium nitrate crystal, whose intensity increases with thallium doping. The band parameters of alkali nitrate single crystals have been calculated. Low-energy transitions in the nitrate ion have been located.

  14. Temperature-dependent solubilities and mean ionic activity coefficients of alkali halides in water from molecular dynamics simulations

    Science.gov (United States)

    Mester, Zoltan; Panagiotopoulos, Athanassios Z.

    2015-07-01

    The mean ionic activity coefficients of aqueous KCl, NaF, NaI, and NaCl solutions of varying concentrations have been obtained from molecular dynamics simulations following a recently developed methodology based on gradual insertions of salt molecules [Z. Mester and A. Z. Panagiotopoulos, J. Chem. Phys. 142, 044507 (2015)]. The non-polarizable ion models of Weerasinghe and Smith [J. Chem. Phys. 119, 11342 (2003)], Gee et al. [J. Chem. Theory Comput. 7, 1369 (2011)], Reiser et al. [J. Chem. Phys. 140, 044504 (2014)], and Joung and Cheatham [J. Phys. Chem. B 112, 9020 (2008)] were used along with the extended simple point charge (SPC/E) water model [Berendsen et al., J. Phys. Chem. 91, 6269 (1987)] in the simulations. In addition to the chemical potentials in solution used to obtain the activity coefficients, we also calculated the chemical potentials of salt crystals and used them to obtain the solubility of these alkali halide models in SPC/E water. The models of Weerasinghe and Smith [J. Chem. Phys. 119, 11342 (2003)] and Gee et al. [J. Chem. Theory Comput. 7, 1369 (2011)] provide excellent predictions of the mean ionic activity coefficients at 298.15 K and 1 bar, but significantly underpredict or overpredict the solubilities. The other two models generally predicted the mean ionic activity coefficients only qualitatively. With the exception of NaF for which the solubility is significantly overpredicted, the model of Joung and Cheatham predicts salt solubilities that are approximately 40%-60% of the experimental values. The models of Reiser et al. [J. Chem. Phys. 140, 044504 (2014)] make good predictions for the NaCl and NaI solubilities, but significantly underpredict the solubilities for KCl and NaF. We also tested the transferability of the models to temperatures much higher than were used to parametrize them by performing simulations for NaCl at 373.15 K and 1 bar, and at 473.15 K and 15.5 bar. All models overpredict the drop in the values of mean ionic

  15. Organometallic halide perovskite single crystals having low deffect density and methods of preparation thereof

    KAUST Repository

    Bakr, Osman M.

    2016-02-18

    The present disclosure presents a method of making a single crystal organometallic halide perovskites, with the formula: AMX3, wherein A is an organic cation, M is selected from the group consisting of: Pb, Sn, Cu, Ni, Co, Fe, Mn, Pd, Cd, Ge, and Eu, and X is a halide. The method comprises the use of two reservoirs containing different precursors and allowing the vapor diffusion from one reservoir to the other one. A solar cell comprising said crystal is also disclosed.

  16. Viscometric and thermodynamic studies of interactions in ternary solutions containing sucrose and aqueous alkali metal halides at 293.15, 303.15 and 313.15 K

    Indian Academy of Sciences (India)

    Reena Gupta; Mukhtar Singh

    2005-05-01

    Viscosities and densities of sucrose in aqueous alkali metal halide solutions of different concentrations in the temperature range 293.15 to 313.15 K have been measured. Partial molar volumes at infinite dilution ($V_{2}^{0}$) of sucrose determined from apparent molar volume ($\\phi_v$) have been utilized to estimate partial molar volumes of transfer ($V^{0}_{2,tr}$) for sucrose from water to alkali metal halide solutions. The viscosity data of alkali metal halides in purely aqueous solutions and in the presence of sucrose at different temperatures (293.15, 303.15 and 313.5 K) have been analysed by the Jones-Dole equation. The nature and magnitude of solute-solvent and solute-solute interactions have been discussed in terms of the values of limiting apparent molar volume ($\\phi^{0}_{v}$), slope ($S_{v}$) and coefficients of the Jones-Dole equation. The structuremaking and structure-breaking capacities of alkali metal halides in pure aqueous solutions and in the presence of sucrose have been ascertained from temperature dependence of $\\phi^{0}_{v}$.

  17. Development of processes for the production of solar grade silicon from halides and alkali metals, phase 1 and phase 2

    Science.gov (United States)

    Dickson, C. R.; Gould, R. K.; Felder, W.

    1981-01-01

    High temperature reactions of silicon halides with alkali metals for the production of solar grade silicon are described. Product separation and collection processes were evaluated, measure heat release parameters for scaling purposes and effects of reactants and/or products on materials of reactor construction were determined, and preliminary engineering and economic analysis of a scaled up process were made. The feasibility of the basic process to make and collect silicon was demonstrated. The jet impaction/separation process was demonstrated to be a purification process. The rate at which gas phase species from silicon particle precursors, the time required for silane decomposition to produce particles, and the competing rate of growth of silicon seed particles injected into a decomposing silane environment were determined. The extent of silane decomposition as a function of residence time, temperature, and pressure was measured by infrared absorption spectroscopy. A simplistic model is presented to explain the growth of silicon in a decomposing silane enviroment.

  18. Understanding the Cubic Phase Stabilization and Crystallization Kinetics in Mixed Cations and Halides Perovskite Single Crystals.

    Science.gov (United States)

    Xie, Li-Qiang; Chen, Liang; Nan, Zi-Ang; Lin, Hai-Xin; Wang, Tan; Zhan, Dong-Ping; Yan, Jia-Wei; Mao, Bing-Wei; Tian, Zhong-Qun

    2017-03-08

    The spontaneous α-to-δ phase transition of the formamidinium-based (FA) lead halide perovskite hinders its large scale application in solar cells. Though this phase transition can be inhibited by alloying with methylammonium-based (MA) perovskite, the underlying mechanism is largely unexplored. In this Communication, we grow high-quality mixed cations and halides perovskite single crystals (FAPbI3)1-x(MAPbBr3)x to understand the principles for maintaining pure perovskite phase, which is essential to device optimization. We demonstrate that the best composition for a perfect α-phase perovskite without segregation is x = 0.1-0.15, and such a mixed perovskite exhibits carrier lifetime as long as 11.0 μs, which is over 20 times of that of FAPbI3 single crystal. Powder XRD, single crystal XRD and FT-IR results reveal that the incorporation of MA(+) is critical for tuning the effective Goldschmidt tolerance factor toward the ideal value of 1 and lowering the Gibbs free energy via unit cell contraction and cation disorder. Moreover, we find that Br incorporation can effectively control the perovskite crystallization kinetics and reduce defect density to acquire high-quality single crystals with significant inhibition of δ-phase. These findings benefit the understanding of α-phase stabilization behavior, and have led to fabrication of perovskite solar cells with highest efficiency of 19.9% via solvent management.

  19. Solubility of alkali metal halides in the ionic liquid [C4C1im][OTf].

    Science.gov (United States)

    Kuzmina, O; Bordes, E; Schmauck, J; Hunt, P A; Hallett, J P; Welton, T

    2016-06-28

    The solubilities of the metal halides LiF, LiCl, LiBr, LiI, NaF, NaCl, NaBr, NaI, KF, KCl, KBr, KI, RbCl, CsCl, CsI, were measured at temperatures ranging from 298.15 to 378.15 K in the ionic liquid 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([C4C1im][OTf]). Li(+), Na(+) and K(+) salts with anions matching the ionic liquid have also been investigated to determine how well these cations dissolve in [C4C1im][OTf]. This study compares the influence of metal cation and halide anion on the solubility of salts within this ionic liquid. The highest solubility found was for iodide salts, and the lowest solubility for the three fluoride salts. There is no outstanding difference in the solubility of salts with matching anions in comparison to halide salts. The experimental data were correlated employing several phase equilibria models, including ideal mixtures, van't Hoff, the λh (Buchowski) equation, the modified Apelblat equation, and the non-random two-liquid model (NRTL). It was found that the van't Hoff model gave the best correlation results. On the basis of the experimental data the thermodynamic dissolution parameters (ΔH, ΔS, and ΔG) were determined for the studied systems together with computed gas phase metathesis parameters. Dissolution depends on the energy difference between enthalpies of fusion and dissolution of the solute salt. This demonstrates that overcoming the lattice energy of the solid matrix is the key to the solubility of inorganic salts in ionic liquids.

  20. Ca-Fe and Alkali-Halide Alteration of an Allende Type B CAI: Aqueous Alteration in Nebular or Asteroidal Settings

    Science.gov (United States)

    Ross, D. K.; Simon, J. I.; Simon, S. B.; Grossman, L.

    2012-01-01

    Ca-Fe and alkali-halide alteration of CAIs is often attributed to aqueous alteration by fluids circulating on asteroidal parent bodies after the various chondritic components have been assembled, although debate continues about the roles of asteroidal vs. nebular modification processes [1-7]. Here we report de-tailed observations of alteration products in a large Type B2 CAI, TS4 from Allende, one of the oxidized subgroup of CV3s, and propose a speculative model for aqueous alteration of CAIs in a nebular setting. Ca-Fe alteration in this CAI consists predominantly of end-member hedenbergite, end-member andradite, and compositionally variable, magnesian high-Ca pyroxene. These phases are strongly concentrated in an unusual "nodule" enclosed within the interior of the CAI (Fig. 1). The Ca, Fe-rich nodule superficially resembles a clast that pre-dated and was engulfed by the CAI, but closer inspection shows that relic spinel grains are enclosed in the nodule, and corroded CAI primary phases interfinger with the Fe-rich phases at the nodule s margins. This CAI also contains abundant sodalite and nepheline (alkali-halide) alteration that occurs around the rims of the CAI, but also penetrates more deeply into the CAI. The two types of alteration (Ca-Fe and alkali-halide) are adjacent, and very fine-grained Fe-rich phases are associated with sodalite-rich regions. Both types of alteration appear to be replacive; if that is true, it would require substantial introduction of Fe, and transport of elements (Ti, Al and Mg) out of the nodule, and introduction of Na and Cl into alkali-halide rich zones. Parts of the CAI have been extensively metasomatized.

  1. Tunable Crystal-to-Crystal Phase Transition in a Cadmium Halide Chain Polymer

    Directory of Open Access Journals (Sweden)

    Ulli Englert

    2011-07-01

    Full Text Available The chain polymer [{Cd(μ-X2py2}1∞] (X = Cl, Br; py = pyridine undergoes a fully reversible phase transition between a monoclinic low-temperature and an orthorhombic high-temperature phase. The transformation can be directly monitored in single crystals and can be confirmed for the bulk by powder diffraction. The transition temperature can be adjusted by tuning the composition of the mixed-halide phase: Transition temperatures between 175 K up to the decomposition of the material at ca. 350 K are accessible. Elemental analysis, ion chromatography and site occupancy refinements from single-crystal X-ray diffraction agree with respect to the stoichiometric composition of the samples.

  2. A study on the electrochemical behaviour of polypyrrole films in concentrated aqueous alkali halide electrolytes

    DEFF Research Database (Denmark)

    Jafeen, M. J. M.; Careem, M.A.; Skaarup, Steen

    2014-01-01

    deposited on gold-coated quartz crystals by electropolymerization and simultaneous cyclic voltammetry and electrochemical quartz crystal microbalance techniques were used. During the first redox cycle, while large water movement is observed along with the counter ions in dilute electrolytes, such water...

  3. Refractive Index of Alkali Halides and Its Wavelength and Temperature Derivatives.

    Science.gov (United States)

    1975-05-01

    P. and Schaller, D., " Refractometric Measurements on Crystals and Comparison of Isomorphic Salts With Noble Gas Resembling and Non-Resembling Cations...P. and Heigl, A., " Refractometric Measurements on Crystals," Z. Kristallogr., 77, 84-121, 1931. 88. Wulff, P., "An Interferometric Method to

  4. Mechanism for rapid growth of organic-inorganic halide perovskite crystals

    Science.gov (United States)

    Nayak, Pabitra K.; Moore, David T.; Wenger, Bernard; Nayak, Simantini; Haghighirad, Amir A.; Fineberg, Adam; Noel, Nakita K.; Reid, Obadiah G.; Rumbles, Garry; Kukura, Philipp; Vincent, Kylie A.; Snaith, Henry J.

    2016-11-01

    Optoelectronic devices based on hybrid halide perovskites have shown remarkable progress to high performance. However, despite their apparent success, there remain many open questions about their intrinsic properties. Single crystals are often seen as the ideal platform for understanding the limits of crystalline materials, and recent reports of rapid, high-temperature crystallization of single crystals should enable a variety of studies. Here we explore the mechanism of this crystallization and find that it is due to reversible changes in the solution where breaking up of colloids, and a change in the solvent strength, leads to supersaturation and subsequent crystallization. We use this knowledge to demonstrate a broader range of processing parameters and show that these can lead to improved crystal quality. Our findings are therefore of central importance to enable the continued advancement of perovskite optoelectronics and to the improved reproducibility through a better understanding of factors influencing and controlling crystallization.

  5. Dipole-driven self-organization of zwitterionic molecules on alkali halide surfaces

    Directory of Open Access Journals (Sweden)

    Laurent Nony

    2012-03-01

    Full Text Available We investigated the adsorption of 4-methoxy-4′-(3-sulfonatopropylstilbazolium (MSPS on different ionic (001 crystal surfaces by means of noncontact atomic force microscopy. MSPS is a zwitterionic molecule with a strong electric dipole moment. When deposited onto the substrates at room temperature, MSPS diffuses to step edges and defect sites and forms disordered assemblies of molecules. Subsequent annealing induces two different processes: First, at high coverage, the molecules assemble into a well-organized quadratic lattice, which is perfectly aligned with the directions of the substrate surface (i.e., rows of equal charges and which produces a Moiré pattern due to coincidences with the substrate lattice constant. Second, at low coverage, we observe step edges decorated with MSPS molecules that run along the direction. These polar steps most probably minimize the surface energy as they counterbalance the molecular dipole by presenting oppositely charged ions on the rearranged step edge.

  6. Thermoluminescence in alkali halides irradiated at 80K; Termoluminiscencia en haluros alcalinos irradiados a 80K

    Energy Technology Data Exchange (ETDEWEB)

    Jimenez de Castro, M.

    1978-07-01

    The thermoluminescence, the thermally stimulated currents and the thermal stability of the F centres induced in pure NaCl and KC1 crystals by X irradiation at 80K have been studied in detail, In the range between 80 and 300K. The thermoluminescent processes induced by illumination at 80K with F light in samples previously irradiated at room temperature has also been studied. It has been clearly observed the existence of thermoluminescent processes due to electrons and holes thermally released from traps, in which the F centres are not involved. The existence of hole-F centre recombination has not been observed. There are several thermoluminescent processes in both materials which are scribed to the recombination of F centres with mobile interstitial halogen atoms thermally released from traps, which are likely monovalent impurities in this temperature interval. The light emitting stage in these processes is originated by the formation of self trapped excitons. (Author) 66 refs.

  7. Experimental study on crystallization kinetics of alkali feldspar under high T-P conditions

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    In the granite-NaF-H2O system, there exists a nucleation lag in the course of alkali feldspar crystallization indicated by experiments on crystallization kinetics. The nucleation lag time is about 18 h at 700℃ and about 6 h at 650℃. Meanwhile, both nucleation rate and crystal-growth rate of alkali feldspar are not constant during the crystallization process, but vary with crystal- lization time. Here we suggest that the lag time should be taken into account in the calculation formula of nucleation rate and crystal-growth rate to obtain more reliable parameters.

  8. Solution growth of single crystal methylammonium lead halide perovskite nanostructures for optoelectronic and photovoltaic applications.

    Science.gov (United States)

    Fu, Yongping; Meng, Fei; Rowley, Matthew B; Thompson, Blaise J; Shearer, Melinda J; Ma, Dewei; Hamers, Robert J; Wright, John C; Jin, Song

    2015-05-01

    Understanding crystal growth and improving material quality is important for improving semiconductors for electronic, optoelectronic, and photovoltaic applications. Amidst the surging interest in solar cells based on hybrid organic-inorganic lead halide perovskites and the exciting progress in device performance, improved understanding and better control of the crystal growth of these perovskites could further boost their optoelectronic and photovoltaic performance. Here, we report new insights on the crystal growth of the perovskite materials, especially crystalline nanostructures. Specifically, single crystal nanowires, nanorods, and nanoplates of methylammonium lead halide perovskites (CH3NH3PbI3 and CH3NH3PbBr3) are successfully grown via a dissolution-recrystallization pathway in a solution synthesis from lead iodide (or lead acetate) films coated on substrates. These single crystal nanostructures display strong room-temperature photoluminescence and long carrier lifetime. We also report that a solid-liquid interfacial conversion reaction can create a highly crystalline, nanostructured MAPbI3 film with micrometer grain size and high surface coverage that enables photovoltaic devices with a power conversion efficiency of 10.6%. These results suggest that single-crystal perovskite nanostructures provide improved photophysical properties that are important for fundamental studies and future applications in nanoscale optoelectronic and photonic devices.

  9. Molecular dynamics simulations of the dynamic and energetic properties of alkali and halide ions using water-model-specific ion parameters.

    Science.gov (United States)

    Joung, In Suk; Cheatham, Thomas E

    2009-10-01

    The dynamic and energetic properties of the alkali and halide ions were calculated using molecular dynamics (MD) and free energy simulations with various different water and ion force fields including our recently developed water-model-specific ion parameters. The properties calculated were activity coefficients, diffusion coefficients, residence times of atomic pairs, association constants, and solubility. Through calculation of these properties, we can assess the validity and range of applicability of the simple pair potential models and better understand their limitations. Due to extreme computational demands, the activity coefficients were only calculated for a subset of the models. The results qualitatively agree with experiment. Calculated diffusion coefficients and residence times between cation-anion, water-cation, and water-anion showed differences depending on the choice of water and ion force field used. The calculated solubilities of the alkali-halide salts were generally lower than the true solubility of the salts. However, for both the TIP4P(EW) and SPC/E water-model-specific ion parameters, solubility was reasonably well-reproduced. Finally, the correlations among the various properties led to the following conclusions: (1) The reliability of the ion force fields is significantly affected by the specific choice of water model. (2) Ion-ion interactions are very important to accurately simulate the properties, especially solubility. (3) The SPC/E and TIP4P(EW) water-model-specific ion force fields are preferred for simulation in high salt environments compared to the other ion force fields.

  10. Homoepitaxial Growth of Metal Halide Crystals Investigated by Reflection High-Energy Electron Diffraction

    Science.gov (United States)

    Chen, Pei; Kuttipillai, Padmanaban S.; Wang, Lili; Lunt, Richard R.

    2017-01-01

    We report the homoepitaxial growth of a metal halide on single crystals investigated with in situ reflection high-energy electron diffraction (RHEED) and ex situ atomic force microscopy (AFM). Epitaxial growth of NaCl on NaCl (001) is explored as a function of temperature and growth rate which provides the first detailed report of RHEED oscillations for metal halide growth. Layer-by-layer growth is observed at room temperature accompanied by clear RHEED oscillations while the growth mode transitions to an island (3D) mode at low temperature. At higher temperatures (>100 °C), RHEED oscillations and AFM data indicate a transition to a step-flow growth mode. To show the importance of such metal halide growth, green organic light-emitting diodes (OLEDs) are demonstrated using a doped NaCl film with a phosphorescent emitter as the emissive layer. This study demonstrates the ability to perform in situ and non-destructive RHEED monitoring even on insulating substrates and could enable doped single crystals and crystalline substrates for a range of optoelectronic applications. PMID:28071732

  11. Crystal and electronic structures of substituted halide perovskites based on density functional calculation and molecular dynamics

    Science.gov (United States)

    Takaba, Hiromitsu; Kimura, Shou; Alam, Md. Khorshed

    2017-03-01

    Durability of organo-lead halide perovskite are important issue for its practical application in a solar cells. In this study, using density functional theory (DFT) and molecular dynamics, we theoretically investigated a crystal structure, electronic structure, and ionic diffusivity of the partially substituted cubic MA0.5X0.5PbI3 (MA = CH3NH3+, X = NH4+ or (NH2)2CH+ or Cs+). Our calculation results indicate that a partial substitution of MA induces a lattice distortion, resulting in preventing MA or X from the diffusion between A sites in the perovskite. DFT calculations show that electronic structures of the investigated partially substituted perovskites were similar with that of MAPbI3, while their bandgaps slightly decrease compared to that of MAPbI3. Our results mean that partial substitution in halide perovskite is effective technique to suppress diffusion of intrinsic ions and tune the band gap.

  12. Crystallization Behaviour and Nanostructuring in Alkali Niobiosilicate Glasses

    Institute of Scientific and Technical Information of China (English)

    E.Fanelli; P.Pernice; M.Xiao; A.Aronne; V.N.Sigacv

    2011-01-01

    23K2O·27Nb2O5·50SiO2 (KNS), 13K2O·10Na2O·27Nb2C5·50SiO2 (KNaNS) and 15K2O·12Li2O·27Nb2O5· 46SiO2 (KLiNS) transparent glasses were synthesized by melt-quenching technique, and studied by differential thermal analysis (DTA), X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) to reveal the effect of the devitrification behaviour on transparent nanostructure.Just above the glass transition temperature Tg in the KNS glass, an unidentified phase was formed, while in KNaNS and KLiNS, mixed-alkali niobate phases with tungsten bronze structure were obtained by bulk crystallization.Heat treatments at Tg performed on the KNS glass resulted in the transparent nanostructure with second order harmonic generation (SHG) activity.Heat treatment for 10 h on KNaNS and KLiNS decreased the first DTA exothermic peaks (at least 24℃), indicating the bulk nucleation, which was confirmed by the DTA in comparison with the powdered as-quenched samples.KNaNS and KLiNS showed similar XRD profiles as the K3Li2Nb5O15 crystal with the five most intense peaks at 22.7, 29.4, 32.3, 46.3 and 52.0 deg.HRTEM micrograph showed clear-cut nano-sized circular domains and spherical nanocrystals dispersed into the amorphous matrix.

  13. Polarizabilities and Shielding Factors of Ions in Cesium Halide Crystals with the Cesium Chloride Structure

    Science.gov (United States)

    Mahbubar, Rahman; Michihiro, Yoshitaka; Nakamura, Koichi; Kanashiro, Tatsuo

    2001-08-01

    The calculated results of the polarizabilities and the quadrupole shielding factor of the ions in cesium halide crystals with the cesium chloride structure are presented. The calculation is done on the basis of the self-consistent field local density approximation and the modified Sternheimer equation. The crystalline potential is treated by the spherical solid model. The size effect is seen in the values of the polarizabilities and the quadrupole shielding factor. The values of the polarizabilities and the quadrupole shielding factor of cesium ion show only slight change in different crystals. The values of chlorine ion show significant reduction and the amount of the reduction is different in the different crystals. The effect of the crystalline environment on the electron states is discussed.

  14. Capacitance of the double electrical layer on the copper-group metals in molten alkali metal halides

    Science.gov (United States)

    Kirillova, E. V.; Stepanov, V. P.

    2016-08-01

    The electrochemical impedance is measured to study the capacitance of the double electrical layer of metallic Au, Ag, and Cu as a function of potential and temperature in nine molten salts, namely, the chlorides, bromides, and iodides of sodium, potassium, and cesium. The C- E curve of a gold electrode has an additional minimum in the anodic branch. This minimum for silver is less pronounced and is only observed at low ac signal frequencies in cesium halides. The additional minimum is not detected for copper in any salt under study. This phenomenon is explained on the assumption that the adsorption of halide anions on a positively charged electrode surface has a predominantly chemical rather than an electrostatic character. The specific adsorption in this case is accompanied by charge transfer through the interface and the formation of an adsorbent-adsorbate covalent bond.

  15. Growth of high quality mercurous halide single crystals by physical vapor transport method for AOM and radiation detection applications

    Science.gov (United States)

    Amarasinghe, Priyanthi M.; Kim, Joo-Soo; Chen, Henry; Trivedi, Sudhir; Qadri, Syed B.; Soos, Jolanta; Diestler, Mark; Zhang, Dajie; Gupta, Neelam; Jensen, Janet L.; Jensen, James

    2016-09-01

    Single crystals of mercurous halide were grown by physical vapor transport method (PVT). The orientation and the crystalline quality of the grown crystals were determined using high resolution x-ray diffraction (HRXRD) technique. The full width at half maximum (FWHM) of the grown mercurous bromide crystals was measured to be 0.13 degrees for (004) reflection, which is the best that has been achieved so far for PVT grown mercurous halide single crystals. The extended defects of the crystals were also analyzed using high resolution x-ray diffraction topography. Preliminary studies were carried out to evaluate the performance of the crystals on acousto-optic modulator (AOM) and gamma-ray detector applications. The results indicate the grown mercurous halide crystals are excellent materials for acousto-optic modulator device fabrication. The diffraction efficiencies of the fabricated AOM device with 1152 and 1523 nm wavelength lasers polarizing parallel to the acoustic wave were found to be 35% and 28%, respectively. The results also indicate the grown crystals are a promising material for gamma-ray detector application with a very high energy resolution of 1.86% FWHM.

  16. Analysis of Interatomic Separation-Pressure Relations for Alkali Halides and Periclase(MgO)%碱卤化合物和MgO的离子间距-压强关系分析

    Institute of Scientific and Technical Information of China (English)

    刘泉; 陈立溁

    2005-01-01

    A new method for the determination of interatomic separation-pressure relations is investigated and applied for alkali halides and MgO crystals. The method is developed by using Hildebrand approximation and an ionic model based on Harrison's treatment of overlap repulsive potential which takes into account the interactions up to second neighbors. The van der Waals dipole-dipole and dipole-quadrupole interactions calculated by more accurate methods are also included in the present work. It is found that the new method yield satisfactory results in agreement with the available experimental data.%给出了一种新的方法来决定固体的离子间距与压强的关系,并将这种方法应用到碱卤化合物和MgO晶体.这种新方法的理论基础是利用Hildebrand近似、并运用Harrison的处理方法来考虑排斥能,即考虑离子间的相互作用直到次临近离子.还利用了更精确的方法来计算偶极子-偶极子和偶极子-四极子之间的相互作用.利用这种新方法得到的结果和实验结果吻合得很好.

  17. Crystallization of methyl ammonium lead halide perovskites: implications for photovoltaic applications.

    Science.gov (United States)

    Tidhar, Yaron; Edri, Eran; Weissman, Haim; Zohar, Dorin; Hodes, Gary; Cahen, David; Rybtchinski, Boris; Kirmayer, Saar

    2014-09-24

    Hybrid organic/lead halide perovskites are promising materials for solar cell fabrication, resulting in efficiencies up to 18%. The most commonly studied perovskites are CH3NH3PbI3 and CH3NH3PbI3-xClx where x is small. Importantly, in the latter system, the presence of chloride ion source in the starting solutions used for the perovskite deposition results in a strong increase in the overall charge diffusion length. In this work we investigate the crystallization parameters relevant to fabrication of perovskite materials based on CH3NH3PbI3 and CH3NH3PbBr3. We find that the addition of PbCl2 to the solutions used in the perovskite synthesis has a remarkable effect on the end product, because PbCl2 nanocrystals are present during the fabrication process, acting as heterogeneous nucleation sites for the formation of perovskite crystals in solution. We base this conclusion on SEM studies, synthesis of perovskite single crystals, and on cryo-TEM imaging of the frozen mother liquid. Our studies also included the effect of different substrates and substrate temperatures on the perovskite nucleation efficiency. In view of our findings, we optimized the procedures for solar cells based on lead bromide perovskite, resulting in 5.4% efficiency and Voc of 1.24 V, improving the performance in this class of devices. Insights gained from understanding the hybrid perovskite crystallization process can aid in rational design of the polycrystalline absorber films, leading to their enhanced performance.

  18. First-principles study of the local structure and crystal field of Yb2+ in sodium and potassium halides

    Institute of Scientific and Technical Information of China (English)

    Wen Jun; Duan Chang-Kui; Yin Min; Yu.V.Orlovskii; Xia Shang-Da; Zhang Yong-Fan

    2012-01-01

    The local coordination structures around the doping Yb2+ ions in sodium and potassium halides were calculated by using the first-principles supercell model.Both the cases with and without the charge compensation vacancy in the local environment of the doping Yb2+ were calculated to study the effect of the doping on the local coordination structures of Yb2+.Using the calculated local structures,we obtained the crystal-field parameters for the Yb2+ ions doped in sodium and potassium halides by a method based on the combination of the quantum-chemical calculations and the effective Hamiltonian method.The calculated crystal-field parameters were analyzed and compared with the fitted results.

  19. Electrochemical Doping of Halide Perovskites with Ion Intercalation.

    Science.gov (United States)

    Jiang, Qinglong; Chen, Mingming; Li, Junqiang; Wang, Mingchao; Zeng, Xiaoqiao; Besara, Tiglet; Lu, Jun; Xin, Yan; Shan, Xin; Pan, Bicai; Wang, Changchun; Lin, Shangchao; Siegrist, Theo; Xiao, Qiangfeng; Yu, Zhibin

    2017-01-24

    Halide perovskites have recently been investigated for various solution-processed optoelectronic devices. The majority of studies have focused on using intrinsic halide perovskites, and the intentional incoporation of dopants has not been well explored. In this work, we discovered that small alkali ions, including lithium and sodium ions, could be electrochemically intercalated into a variety of halide and pseudohalide perovskites. The ion intercalation caused a lattice expansion of the perovskite crystals and resulted in an n-type doping of the perovskites. Such electrochemical doping improved the conductivity and changed the color of the perovskites, leading to an electrochromism with more than 40% reduction of transmittance in the 450-850 nm wavelength range. The doped perovskites exhibited improved electron injection efficiency into the pristine perovskite crystals, resulting in bright light-emitting diodes with a low turn-on voltage.

  20. Atomic forces between noble gas atoms, alkali ions, and halogen ions for surface interactions

    Science.gov (United States)

    Wilson, J. W.; Outlaw, R. A.; Heinbockel, J. H.

    1988-01-01

    The components of the physical forces between noble gas atoms, alkali ions, and halogen ions are analyzed and a data base developed from analysis of the two-body potential data, the alkali-halide molecular data, and the noble gas crystal and salt crystal data. A satisfactory global fit to this molecular and crystal data is then reproduced by the model to within several percent. Surface potentials are evaluated for noble gas atoms on noble gas surfaces and salt crystal surfaces with surface tension neglected. Within this context, the noble gas surface potentials on noble gas and salt crystals are considered to be accurate to within several percent.

  1. Detection of gamma photons using solution-grown single crystals of hybrid lead halide perovskites

    Science.gov (United States)

    Yakunin, Sergii; Dirin, Dmitry N.; Shynkarenko, Yevhen; Morad, Viktoriia; Cherniukh, Ihor; Nazarenko, Olga; Kreil, Dominik; Nauser, Thomas; Kovalenko, Maksym V.

    2016-09-01

    The decay of the majority of radioactive isotopes involves the emission of gamma (γ) photons with energies of ˜50 keV to 10 MeV. Detectors of such hard radiation that are low-cost, highly sensitive and operate at ambient temperatures are desired for numerous applications in defence and medicine, as well as in research. We demonstrate that 0.3-1 cm solution-grown single crystals (SCs) of semiconducting hybrid lead halide perovskites (MAPbI3, FAPbI3 and I-treated MAPbBr3, where MA = methylammonium and FA = formamidinium) can serve as solid-state gamma-detecting materials. This possibility arises from a high charge-carrier mobility-lifetime (μτ) product of 1.0-1.8 × 10-2 cm2 V-1, a low dark carrier density of 109-1011 cm-3 (refs 3,4), a low density of charge traps of 109-1010 cm-3 (refs 4,5) and a high absorptivity of hard radiation by the lead and iodine atoms. We demonstrate the utility of perovskite detectors for testing the radiopurity of medical radiotracer compounds such as 18F-fallypride. Energy-resolved sensing at room temperature is presented using FAPbI3 SCs and an 241Am source.

  2. Effect of radiation-induced emission of Schottky defects on the formation of colloids in alkali halides

    NARCIS (Netherlands)

    Dubinko, [No Value; Vainshtein, DI; Den Hartog, HW

    2003-01-01

    Formation of vacancy clusters in irradiated crystals is considered taking into account radiation-induced Schottky defect emission (RSDE) from extended defects. RSDE acts in the opposite direction compared with Frenkel pair production, and it results in the radiation-induced recovery processes. In th

  3. Crystal structures of halohydrin hydrogen-halide-lyases from Corynebacterium sp. N-1074.

    Science.gov (United States)

    Watanabe, Fumiaki; Yu, Fujio; Ohtaki, Akashi; Yamanaka, Yasuaki; Noguchi, Keiichi; Yohda, Masafumi; Odaka, Masafumi

    2015-12-01

    Halohydrin hydrogen-halide-lyase (H-Lyase) is a bacterial enzyme that is involved in the degradation of halohydrins. This enzyme catalyzes the intramolecular nucleophilic displacement of a halogen by a vicinal hydroxyl group in halohydrins to produce the corresponding epoxides. The epoxide products are subsequently hydrolyzed by an epoxide hydrolase, yielding the corresponding 1, 2-diol. Until now, six different H-Lyases have been studied. These H-Lyases are grouped into three subtypes (A, B, and C) based on amino acid sequence similarities and exhibit different enantioselectivity. Corynebacterium sp. strain N-1074 has two different isozymes of H-Lyase, HheA (A-type) and HheB (B-type). We have determined their crystal structures to elucidate the differences in enantioselectivity among them. All three groups share a similar structure, including catalytic sites. The lack of enantioselectivity of HheA seems to be due to the relatively wide size of the substrate tunnel compared to that of other H-Lyases. Among the B-type H-Lyases, HheB shows relatively high enantioselectivity compared to that of HheBGP1 . This difference seems to be due to amino acid replacements at the active site tunnel. The binding mode of 1, 3-dicyano-2-propanol at the catalytic site in the crystal structure of the HheB-DiCN complex suggests that the product should be (R)-epichlorohydrin, which agrees with the enantioselectivity of HheB. Comparison with the structure of HheC provides a clue for the difference in their enantioselectivity.

  4. Inorganic Lead Halide Perovskite Single Crystals: Phase-Selective Low-Temperature Growth, Carrier Transport Properties, and Self-Powered Photodetection

    KAUST Repository

    Saidaminov, Makhsud I.

    2016-12-06

    A rapid, low-temperature, and solution-based route is developed for growing large-sized cesium lead halide perovskite single crystals under ambient conditions. An ultralow minority carrier concentration was measured in CsPbBr3 (≈108 holes per cm3, much lower than in any other lead halide perovskite and crystalline silicon), which enables to realize self-powered photodetectors with a high ON/OFF ratio (105).

  5. Structure and Growth Control of Organic-Inorganic Halide Perovskites for Optoelectronics: From Polycrystalline Films to Single Crystals.

    Science.gov (United States)

    Chen, Yani; He, Minhong; Peng, Jiajun; Sun, Yong; Liang, Ziqi

    2016-04-01

    Recently, organic-inorganic halide perovskites have sparked tremendous research interest because of their ground-breaking photovoltaic performance. The crystallization process and crystal shape of perovskites have striking impacts on their optoelectronic properties. Polycrystalline films and single crystals are two main forms of perovskites. Currently, perovskite thin films have been under intensive investigation while studies of perovskite single crystals are just in their infancy. This review article is concentrated upon the control of perovskite structures and growth, which are intimately correlated for improvements of not only solar cells but also light-emitting diodes, lasers, and photodetectors. We begin with the survey of the film formation process of perovskites including deposition methods and morphological optimization avenues. Strategies such as the use of additives, thermal annealing, solvent annealing, atmospheric control, and solvent engineering have been successfully employed to yield high-quality perovskite films. Next, we turn to summarize the shape evolution of perovskites single crystals from three-dimensional large sized single crystals, two-dimensional nanoplates, one-dimensional nanowires, to zero-dimensional quantum dots. Siginificant functions of perovskites single crystals are highlighted, which benefit fundamental studies of intrinsic photophysics. Then, the growth mechanisms of the previously mentioned perovskite crystals are unveiled. Lastly, perspectives for structure and growth control of perovskites are outlined towards high-performance (opto)electronic devices.

  6. Structure and Growth Control of Organic–Inorganic Halide Perovskites for Optoelectronics: From Polycrystalline Films to Single Crystals

    Science.gov (United States)

    Chen, Yani; He, Minhong; Peng, Jiajun; Sun, Yong

    2016-01-01

    Recently, organic–inorganic halide perovskites have sparked tremendous research interest because of their ground‐breaking photovoltaic performance. The crystallization process and crystal shape of perovskites have striking impacts on their optoelectronic properties. Polycrystalline films and single crystals are two main forms of perovskites. Currently, perovskite thin films have been under intensive investigation while studies of perovskite single crystals are just in their infancy. This review article is concentrated upon the control of perovskite structures and growth, which are intimately correlated for improvements of not only solar cells but also light‐emitting diodes, lasers, and photodetectors. We begin with the survey of the film formation process of perovskites including deposition methods and morphological optimization avenues. Strategies such as the use of additives, thermal annealing, solvent annealing, atmospheric control, and solvent engineering have been successfully employed to yield high‐quality perovskite films. Next, we turn to summarize the shape evolution of perovskites single crystals from three‐dimensional large sized single crystals, two‐dimensional nanoplates, one‐dimensional nanowires, to zero‐dimensional quantum dots. Siginificant functions of perovskites single crystals are highlighted, which benefit fundamental studies of intrinsic photophysics. Then, the growth mechanisms of the previously mentioned perovskite crystals are unveiled. Lastly, perspectives for structure and growth control of perovskites are outlined towards high‐performance (opto)electronic devices.

  7. Electrolytic systems and methods for making metal halides and refining metals

    Energy Technology Data Exchange (ETDEWEB)

    Holland, Justin M.; Cecala, David M.

    2015-05-26

    Disclosed are electrochemical cells and methods for producing a halide of a non-alkali metal and for electrorefining the halide. The systems typically involve an electrochemical cell having a cathode structure configured for dissolving a hydrogen halide that forms the halide into a molten salt of the halogen and an alkali metal. Typically a direct current voltage is applied across the cathode and an anode that is fabricated with the non-alkali metal such that the halide of the non-alkali metal is formed adjacent the anode. Electrorefining cells and methods involve applying a direct current voltage across the anode where the halide of the non-alkali metal is formed and the cathode where the non-alkali metal is electro-deposited. In a representative embodiment the halogen is chlorine, the alkali metal is lithium and the non-alkali metal is uranium.

  8. Potassium self-diffusion in a K-rich single-crystal alkali feldspar

    Science.gov (United States)

    Hergemöller, Fabian; Wegner, Matthias; Deicher, Manfred; Wolf, Herbert; Brenner, Florian; Hutter, Herbert; Abart, Rainer; Stolwijk, Nicolaas A.

    2016-12-01

    The paper reports potassium diffusion measurements performed on gem-quality single-crystal alkali feldspar in the temperature range from 1169 to 1021 K. Natural sanidine from Volkesfeld, Germany was implanted with ^{43}K at the ISOLDE/CERN radioactive ion-beam facility normal to the ( 001) crystallographic plane. Diffusion coefficients are well described by the Arrhenius equation with an activation energy of 2.4 eV and a pre-exponential factor of 5 × 10^{-6} m^2/s, which is more than three orders of magnitude lower than the ^{22}Na diffusivity in the same feldspar and the same crystallographic direction. State-of-the-art considerations including ionic conductivity data on the same crystal and Monte Carlo simulations of diffusion in random binary alloy structures point to a correlated motion of K and Na through the interstitialcy mechanism.

  9. Solid State Synthesis and Crystal Structure of K3SI

    Institute of Scientific and Technical Information of China (English)

    ZHAO Zhen-Qian; LIU Xi; CHEN Wen-Tong; LI Yan; WU A-Qing; ZENG Hui-Yi; GUO Guo-Cong; HUANG Jin-Shun

    2006-01-01

    A new ternary alkali metal chalcogenide halide, K3SI, has been synthesized by solid state reaction method and structurally characterized by X-ray crystallography. The crystal belongs to hexagonal, space group P63cm with a = 11.699(1), c = 5.8279(9) (A), Mr = 276.26, V = 690.8(1)(A)3, Z = 6, Dc = 3.985 g/cm3, F(000) = 756, μ= 9.913 mm-1, S = 1.004, R = 0.0719 and wR = 0.2204. The title compound is the first example containing S anion in the ternary alkali metal chalcogenide halides family M3QX (M = alkali metal, Q = chalcogenide, X = halide), which crystallizes in the hexagonal anti-perovskite structure type.

  10. Structural systematic and crystal chemistry of novel borates with REE, Pb, Sr, and alkali metals

    Energy Technology Data Exchange (ETDEWEB)

    Belokoneva, E.L. [Moscow State Univ., Moscow (Russian Federation). Dept. of Crystallography and Crystal Chemistry

    2013-11-01

    Crystal structures of novel borates with REE, Pb, Sr and alkali metals were analyzed using classical fundamental buildings blocks approach. It is demonstrated that hexa-, penta-, tetra-, tri- and diborates subdivisions in systematic are real families of structures with the common peculiarities. According to the symmetrical way and the degree of FBB condensation structural-generic rows exist in every of subdivisions. Mega- or polyborates subdivision is valid for the structures with the different types of simplest FBB. In all new complex borates it is possible to separate FBB of equal or different types which are presented in isolated form or are connected into chains, layers or frameworks, and to find unexpected correlation between structures. The possibility to recognize and to visualize in this approach the polarity or non-polarity of the structural units and correspondingly the polarity or nonpolarity of the structures in the whole is very important for the conclusion on structure-properties relation. (orig.)

  11. Radiation processes in crystal solid solutions

    CERN Document Server

    Gladyshev, Gennadi

    2012-01-01

    This is a monograph explaining processes occurring in two classes of crystal solids (metal alloys and doped alkali halide) under irradiation by various types of radiation (alpha, beta, gamma, X-radiations, ions). This e-book is a useful reference for advanced readers interested in the physics of radiation and solid state physics.

  12. Synthesis,Crystal and Band Structures,and Optical Properties of Mercury Pnictide Halide Hg19As10Br18

    Institute of Scientific and Technical Information of China (English)

    ZOU Jian-Ping; ZHANG Long-Zhu; ZENG Gui-Sheng; LUO Xu-Biao; PENG Qiang

    2011-01-01

    A mercury pnictide halide semiconductor Hg19As10Br18(1) has been prepared by the solid-state reaction and structurally characterized by single-crystal X-ray diffraction analysis.Compound 1 crystallizes in triclinic,space group P with a = 11.262(4),b = 11.352(4),c = 12.309(5) ,α = 105.724(2),β = 105.788(4),γ = 109.0780(10)° and V = 1314.3(8) 3.The structure of 1 is composed of parallel perovskite-like layers bridged by the linearly coordinated Br atoms to form a three-dimensional framework.The optical properties were investigated in terms of the diffuse reflectance spectrum.The electronic band structure along with density of states(DOS) calculated by DFT method indicates that compound 1 is a semiconductor with an indirect band gap,and that the optical absorption is mainly originated from the charge transitions from Br-4p and As-4p to the Hg-6s states.

  13. Preparation and Single-Crystal X-Ray Structures of Four Related Mixed-Ligand 4-Methylpyridine Indium Halide Complexes

    Science.gov (United States)

    Hepp, Aloysius F.; Clark, Eric B.; Schupp, John D.; Williams, Jennifer N.; Duraj, Stan A.; Fanwick, Philip E.

    2013-01-01

    We describe the structures of four related indium complexes obtained during synthesis of solid-state materials precursors. Indium adducts of halides and 4-methylpyridine, InX3(pic)3 (X = Cl, Br; pic = 4-methylpyridine) consist of octahedral molecules with meridional (mer) geometry. Crystals of mer-InCl3(pic)3 (1) are triclinic, space group P1(bar) (No. 2), with a = 9.3240(3), b = 13.9580(6), c = 16.7268 (7) A, alpha = 84.323(2), beta = 80.938(2), gamma = 78.274(3)Z = 4, R = 0.035 for 8820 unique reflections. Crystals of mer-InBr3(pic)3 (2) are monoclinic, space group P21/n (No. 14), with a = 15.010(2), b = 19.938(2), c = 16.593(3), beta = 116.44(1)Z = 8, R = 0.053 for 4174 unique reflections. The synthesis and structures of related compounds with phenylsulfide (chloride) (3) and a dimeric complex with bridging hydroxide (bromide) (4) coordination is also described. Crystals of trans-In(SC6H5)Cl2(pic)3 (3) are monoclinic, space group P21/n (No. 14), with a = 9.5265(2), b = 17.8729(6), c = 13.8296(4), beta = 99.7640(15)Z = 4, R = 0.048 for 5511 unique reflections. Crystals of [In(mu-OH)Br2(pic)22 (4) are tetragonal, space group = I41cd (No. 110) with a = 19.8560(4), b = 19.8560(4), c = 25.9528(6), Z = 8, R = 0.039 for 5982 unique reflections.

  14. Crystallization Dynamics of Organolead Halide Perovskite by Real-Time X-ray Diffraction.

    Science.gov (United States)

    Miyadera, Tetsuhiko; Shibata, Yosei; Koganezawa, Tomoyuki; Murakami, Takurou N; Sugita, Takeshi; Tanigaki, Nobutaka; Chikamatsu, Masayuki

    2015-08-12

    We analyzed the crystallization process of the CH3NH3PbI3 perovskite by observing real-time X-ray diffraction immediately after combining a PbI2 thin film with a CH3NH3I solution. A detailed analysis of the transformation kinetics demonstrated the fractal diffusion of the CH3NH3I solution into the PbI2 film. Moreover, the perovskite crystal was found to be initially oriented based on the PbI2 crystal orientation but to gradually transition to a random orientation. The fluctuating characteristics of the crystallization process of perovskites, such as fractal penetration and orientational transformation, should be controlled to allow the fabrication of high-quality perovskite crystals. The characteristic reaction dynamics observed in this study should assist in establishing reproducible fabrication processes for perovskite solar cells.

  15. Role of the crystallization substrate on the photoluminescence properties of organo-lead mixed halides perovskites

    OpenAIRE

    2014-01-01

    We have fabricated CH3NH3PbI3−xClx perovskite thin films crystallized in situ on substrates of different natures (e.g., porosity, wettability) and investigated their photoluminescence properties. We observe that the crystallization time and thin film structure are strongly influenced by the chemical nature and porosity of the substrate. Moreover, we find that the mesoporous scaffold can tune the emissive properties of the semiconducting compound both in terms of spectral region and dynamics. ...

  16. Retrograde solubility of formamidinium and methylammonium lead halide perovskites enabling rapid single crystal growth

    KAUST Repository

    Saidaminov, Makhsud I.

    2015-10-20

    Here we show the retrograde solubility of various hybrid perovskites through the correct choice of solvent(s) and report their solubility curves. Retrograde solubility enables to develop inverse temperature crystallization of FAPbX3 (FA = HC(NH2)2+, X = Br−/I−). FAPbI3 crystals exhibit a 1.4 eV bandgap – considerably narrower than their polycrystalline counterparts.

  17. Role of the crystallization substrate on the photoluminescence properties of organo-lead mixed halides perovskites

    Science.gov (United States)

    De Bastiani, Michele; D'Innocenzo, Valerio; Stranks, Samuel D.; Snaith, Henry J.; Petrozza, Annamaria

    2014-08-01

    We have fabricated CH3NH3PbI3-xClx perovskite thin films crystallized in situ on substrates of different natures (e.g., porosity, wettability) and investigated their photoluminescence properties. We observe that the crystallization time and thin film structure are strongly influenced by the chemical nature and porosity of the substrate. Moreover, we find that the mesoporous scaffold can tune the emissive properties of the semiconducting compound both in terms of spectral region and dynamics. In particular, perovskite crystallites grown in the nanometre size porous scaffold present a shorter-living and blue-shifted emission with respect to the perovskite crystals which are free to grow without any constraints.

  18. Role of the crystallization substrate on the photoluminescence properties of organo-lead mixed halides perovskites

    Directory of Open Access Journals (Sweden)

    Michele De Bastiani

    2014-08-01

    Full Text Available We have fabricated CH3NH3PbI3−xClx perovskite thin films crystallized in situ on substrates of different natures (e.g., porosity, wettability and investigated their photoluminescence properties. We observe that the crystallization time and thin film structure are strongly influenced by the chemical nature and porosity of the substrate. Moreover, we find that the mesoporous scaffold can tune the emissive properties of the semiconducting compound both in terms of spectral region and dynamics. In particular, perovskite crystallites grown in the nanometre size porous scaffold present a shorter-living and blue-shifted emission with respect to the perovskite crystals which are free to grow without any constraints.

  19. The radiation defect accumulation in scintillative crystals of caesium halides under intense electron beam irradiation

    CERN Document Server

    Galiy, P V

    1999-01-01

    The characteristics of defect accumulation and radiolysis at CsI crystals under mean energies of electron irradiation at wide dose rates and ranges of doses have been investigated by such methods: thermostimulated exoelectron emission (TSEE), Auger electron spectroscopy (AES) and optical absorption spectroscopy (OAS). The limit dose rates and absorbed doses of electron irradiation that lead to defects accumulation at room temperature in crystals volume and also surface stoichiometry violation have been evaluated. The doses of electron irradiation that lead to CsI radiolysis, with caesium coagulation in metallic phase have been determined. Some quasi periodic connection of such process with irradiation dose was observed.

  20. Systematic hardness measurements on single crystals and polycrystalline blanks of cesium halides

    Indian Academy of Sciences (India)

    D B Sirdeshmukh; P Geeta Krishna; K G Subhadra

    2002-06-01

    Vickers and knoop hardness measurements were carried out on CsBr and CsI single crystals. Polycrystalline blanks of CsCl, CsBr and CsI were prepared by melting and characterized by X-ray diffraction. Vickers hardness measurements were carried out on these blanks. The hardness values were correlated with the lattice constant and the Schottky defect formation energy.

  1. Alkali-ions diffusion, mullite formation, and crystals dissolution during sintering of porcelain bodies: Microstructural approach

    DEFF Research Database (Denmark)

    Leonelli, C.; Kamseu, E.; Boccaccini, Dino

    2009-01-01

    The effect of alkali-silicate glassy matrix as replacement for feldspar in soft and hard porcelain compositions was studied. SEM and X-ray diffraction analysis were used to evidence phase evolution. For each composition, the influence of soaking time was evaluated. The difference in chemical...... composition (amount of alkali and alumina) between the two types of porcelain studied influenced the final microstructure: density, pore size and shape, and mullite content. Quartz dissolution was more important in soft porcelain where the mullitization was limited by the low amount of alumina compared...... to hard porcelain. Replacing the feldspar by alkali-silicate glassy matrices with similar chemical composition, the amount of secondary mullite and mechanical properties increased in both soft and hard compositions....

  2. Broad Wavelength Tunable Robust Lasing from Single-Crystal Nanowires of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, I).

    Science.gov (United States)

    Fu, Yongping; Zhu, Haiming; Stoumpos, Constantinos C; Ding, Qi; Wang, Jue; Kanatzidis, Mercouri G; Zhu, Xiaoyang; Jin, Song

    2016-08-23

    Lead halide perovskite nanowires (NWs) are emerging as a class of inexpensive semiconductors with broad bandgap tunability for optoelectronics, such as tunable NW lasers. Despite exciting progress, the current organic-inorganic hybrid perovskite NW lasers suffer from limited tunable wavelength range and poor material stability. Herein, we report facile solution growth of single-crystal NWs of inorganic perovskite CsPbX3 (X = Br, Cl) and their alloys [CsPb(Br,Cl)3] and a low-temperature vapor-phase halide exchange method to convert CsPbBr3 NWs into perovskite phase CsPb(Br,I)3 alloys and metastable CsPbI3 with well-preserved perovskite crystal lattice and NW morphology. These single crystalline NWs with smooth end facets and subwavelength dimensions are ideal Fabry-Perot cavities for NW lasers. Optically pumped tunable lasing across the entire visible spectrum (420-710 nm) is demonstrated at room temperature from these NWs with low lasing thresholds and high-quality factors. Such highly efficient lasing similar to what can be achieved with organic-inorganic hybrid perovskites indicates that organic cation is not essential for light emission application from these lead halide perovskite materials. Furthermore, the CsPbBr3 NW lasers show stable lasing emission with no measurable degradation after at least 8 h or 7.2 × 10(9) laser shots under continuous illumination, which are substantially more robust than their organic-inorganic counterparts. The Cs-based perovskites offer a stable material platform for tunable NW lasers and other nanoscale optoelectronic devices.

  3. Differential calorimeter and temperature controller for stored energy measurements in irradiated alkali halides; Calorimetro diferencial y controlador de temperatura para medidas de energia almacenada en haluros alcalinos irradiados

    Energy Technology Data Exchange (ETDEWEB)

    Delgado Martinez, L.

    1977-07-01

    The design and performance of a simple temperature-controlled differential calorimeter are presented. This system allows to measure radiation-induced stored energy in insulators, above room temperature with a differential thermal analysis method. With platelets of KC1 single crystals, the base lines obtained for T{sub 2} T{sub 1} (with T{sub 2}: irradiated sample temperature and T{sub 1}: reference sample temperature) show a smooth drift less of 0,2 degree centigree in the interval from 25 to 400 degree centigree. The discrepancy between two consecutive base lines is less than {+-} 0,02 degree centigree which implies a calorimeter sensitivity of about {+-}0,004 cal/g. This sensitivity allows to measure stored energy release in samples with a color center concentration low enough to be directly measured with a spectrophotometer so that a search for correlations among the features of the stored energy spectrum and the color center annealing can be made. (Author) 13 refs.

  4. Exciton luminescence in BaFCl crystal

    Energy Technology Data Exchange (ETDEWEB)

    Radzhabov, E

    1998-05-01

    The luminescence spectra and decay characteristics of both 5.45 and 3.4 eV bands in BaFCl oxygen-free crystals were investigated at 5-300 K temperature range using vacuum ultraviolet excitation as well as X-ray excitation. The similarities with excitons in alkali halides allow us to consider both excitons in BaFCl as on-center excitons and strong off-center excitons.

  5. Synthesis and Crystal Structure of A New Armed-tetraazacrown Ether and Its Liquid Membrane Transport of Alkali Metal Cations

    Institute of Scientific and Technical Information of China (English)

    马淑兰; 朱文祥; 董淑静; 郭倩玲; 佘远斌

    2003-01-01

    A new tetra-N-substituted tetraazacrown ether derivative, 4,7,13,16-tetra ( 2-cyanobenzyl)-1, 10-dioxa-4, 7, 13, 16-tetraazacy-dooctademne, C44H48N8O2, has been synthesized and struc-turally characterized. It crystallizes in the monoclinic system,Slmeegroup P21/c with a = 1.1176(3) nm, b =2.1906(7) nm,c=0.8430(3)nm, V=2.0132(10)nm3, β = 102.740(5)°,Z=4, Dc= 1.189 g/cm3, final R1=0.0460, wR2=0.0803.The liquid membrane transports of alkali metal cations using the new macrocyde as the ion-carrier were also studied. Com-pared with some macrocyclic ligands, our newly synthesized lig.and showed a good selectivity ratio for Na Na+/Li+.

  6. Crystal structures of five 1-alkyl-4-aryl-1,2,4-triazol-1-ium halide salts

    Directory of Open Access Journals (Sweden)

    Marites A. Guino-o

    2015-06-01

    Full Text Available The asymmetric units for the salts 4-(4-fluorophenyl-1-isopropyl-1,2,4-triazol-1-ium iodide, C11H13FN3+·I−, (1, 1-isopropyl-4-(4-methylphenyl-1,2,4-triazol-1-ium iodide, C12H16N3+·I−, (2, 1-isopropyl-4-phenyl-1,2,4-triazol-1-ium iodide, C11H14N3+·I−, (3, and 1-methyl-4-phenyl-1,2,4-triazol-1-ium iodide, C9H10N3+·I−, (4, contain one cation and one iodide ion, whereas in 1-benzyl-4-phenyl-1,2,4-triazol-1-ium bromide monohydrate, C15H14N3+·Br−·H2O, (5, there is an additional single water molecule. There is a predominant C—H...X(halide interaction for all salts, resulting in a two-dimensional extended sheet network between the triazolium cation and the halide ions. For salts with para-substitution on the aryl ring, there is an additional π–anion interaction between a triazolium carbon and iodide displayed by the layers. For salts without the para-substitution on the aryl ring, the π–π interactions are between the triazolium and aryl rings. The melting points of these salts agree with the predicted substituent inductive effects.

  7. Mixed alkali and alkaline-earth borate Li2Sr4B12O23 single crystal

    Science.gov (United States)

    Reshak, A. H.

    2015-10-01

    A comprehensive theoretical investigation of the electronic band structure, density of states, electron charge density distribution and the optical properties for mixed alkali and alkaline-earth borate Li2Sr4B12O23 (LSBO) single crystals were performed. The experimental geometrical structure was optimized by minimizing the forces acting on each atom. Calculations were performed using the full potential linear augmented plane wave plus local orbitals (FPLAPW + lo) method within the local density approximation (LDA), generalized gradient approximation (GGA) and the recently modified Becke-Johnson potential (mBJ). Our calculations show that LSBO crystal is a direct band gap semiconductor. The calculated band gap is 4.64 eV (LDA), 4.92 eV (GGA) and 5.51 eV (mBJ). An earlier calculation using the CASTEP code within LDA obtained a band gap of about 4.66 eV. To overcome the well-known LDA underestimation of the energy gap we have used GGA and mBJ . We find that mBJ succeed by large amount in bringing the calculated bond lengths in good agreement with the experimental data. Also we found that using mBJ to calculate the optical properties gives a birefringence of about 0.068 (at λ = 586.5 nm) in excellent agreement with the experimental data (0.068 at λ = 586.5 nm). Therefore, we believe that the mBJ calculations reported here show excellent agreement with the experimental data.

  8. High-Pressure Single-Crystal Structures of 3D Lead-Halide Hybrid Perovskites and Pressure Effects on their Electronic and Optical Properties.

    Science.gov (United States)

    Jaffe, Adam; Lin, Yu; Beavers, Christine M; Voss, Johannes; Mao, Wendy L; Karunadasa, Hemamala I

    2016-04-27

    We report the first high-pressure single-crystal structures of hybrid perovskites. The crystalline semiconductors (MA)PbX3 (MA = CH3NH3 (+), X = Br(-) or I(-)) afford us the rare opportunity of understanding how compression modulates their structures and thereby their optoelectronic properties. Using atomic coordinates obtained from high-pressure single-crystal X-ray diffraction we track the perovskites' precise structural evolution upon compression. These structural changes correlate well with pressure-dependent single-crystal photoluminescence (PL) spectra and high-pressure bandgaps derived from density functional theory. We further observe dramatic piezochromism where the solids become lighter in color and then transition to opaque black with compression. Indeed, electronic conductivity measurements of (MA)PbI3 obtained within a diamond-anvil cell show that the material's resistivity decreases by 3 orders of magnitude between 0 and 51 GPa. The activation energy for conduction at 51 GPa is only 13.2(3) meV, suggesting that the perovskite is approaching a metallic state. Furthermore, the pressure response of mixed-halide perovskites shows new luminescent states that emerge at elevated pressures. We recently reported that the perovskites (MA)Pb(Br x I1-x )3 (0.2 < x < 1) reversibly form light-induced trap states, which pin their PL to a low energy. This may explain the low voltages obtained from solar cells employing these absorbers. Our high-pressure PL data indicate that compression can mitigate this PL redshift and may afford higher steady-state voltages from these absorbers. These studies show that pressure can significantly alter the transport and thermodynamic properties of these technologically important semiconductors.

  9. Studies on crystal structures, optical and electrical properties of viologen cation salts of d10 metal halide anions

    Science.gov (United States)

    Du, Haijuan; Li, Yaru; Xu, Manman; Niu, Yunyin; Hou, Hongwei

    2017-04-01

    Construction of viologen cation salts of d10 metal halide anions (inorganic-organic hybrid materials) with semiconducting properties via supramolecular design and aggregate enable the hybrid materials multifunctionality. Our interest focused on the use of the viologen derivatives as the building units because they were redox-active units and more suited to yield new generation of multifunctional networks. In the present investigation, three new inorganic-organic hybrid semiconductors {[bbpyb]·[AgBr3]}n (1) [1, 3-PMBP][Zn2Cl5.1Br0.9] (2) and [1, 3-PMBP][Zn2Br6] (3) (bbpyb = 1,1″-(1,4-butanediyl)bis[4,4‧-bipyridinium]bis[bromide], 1,3-PMBP = 1,1″-[1,3-phenylene-bis(methylene)]bis-4,4‧-bipyridinium-bisbromide) were synthesized. More importantly, great efforts were devoted to investigate their properties, such as optical and electrical properties. 1-3 exhibited photochromism, which can be ascribed to the intermolecular charge transfer to yield radicals. Fabricating the appropriate inorganic and organic units controllably within photosensitive materials at a molecular level is critical for the development of new photochromic inorganic-organic hybrids.

  10. Effects of the Indirect Ionic Interaction on the Diffusion of the Cation in the Silver Halide Crystals with the Rock-Salt Structure

    Science.gov (United States)

    Michihiro, Yoshitaka; Itsuki, Kazuya; Endou, Shigeki; Isono, Masaya; Nakamura, Koichi; Ohno, Takashi

    2013-07-01

    The contributions from the indirect ionic interaction to the activation energy for the diffusion of the cation by the vacancy mechanism are evaluated for the silver and sodium halide crystals with the rock-salt structure. The coupling constants of the indirect ionic interaction for the cations are calculated by the self-consistent field treatment of the local density approximation and the spherical solid model. The coupling constant of the indirect ionic interaction for Ag+ in AgBr is almost one order of magnitude larger than that for Na+ in NaBr. The strong indirect ionic interaction caused by the induced polarization of Ag+ in AgBr leads to the drastic decrease in the activation energy for the diffusion of Ag+. The difference between the strength of the indirect ionic interaction by Ag+ in AgBr and that by Na+ in NaBr reasonably explains the difference between the experimental activation energy for the diffusion of Ag+ in AgBr and that of Na+ in NaBr. The similar trend is also seen in AgCl and NaCl. These facts indicate that the strong non-central forces due to the indirect ionic interaction play an important role in the diffusion of Ag+.

  11. He atom-surface scattering: Surface dynamics of insulators, overlayers and crystal growth

    Energy Technology Data Exchange (ETDEWEB)

    1992-01-01

    Investigations in this laboratory have focused on the surface structure and dynamics of ionic insulators and on epitaxial growth onto alkali halide crystals. In the later the homoepitaxial growth of NaCl/NaCl(001) and the heteroepitaxial growth of KBr/NaCl(001), NaCl/KBr(001) and KBr/RbCl(001) have been studied by monitoring the specular He scattering as a function of the coverage and by measuring the angular and energy distributions of the scattered He atoms. These data provide information on the surface structure, defect densities, island sizes and surface strain during the layer-by-layer growth. The temperature dependence of these measurements also provides information on the mobilities of the admolecules. He atom scattering is unique among surface probes because the low-energy, inert atoms are sensitive only to the electronic structure of the topmost surface layer and are equally applicable to all crystalline materials. It is proposed for the next year to exploit further the variety of combinations possible with the alkali halides in order to carry out a definitive study of epitaxial growth in the ionic insulators. The work completed so far, including measurements of the Bragg diffraction and surface dispersion at various stages of growth, appears to be exceptionally rich in detail, which is particularly promising for theoretical modeling. In addition, because epitaxial growth conditions over a wide range of lattice mismatches is possible with these materials, size effects in growth processes can be explored in great depth. Further, as some of the alkali halides have the CsCl structure instead of the NaCl structure, we can investigate the effects of the heteroepitaxy with materials having different lattice preferences. Finally, by using co-deposition of different alkali halides, one can investigate the formation and stability of alloys and even alkali halide superlattices.

  12. Calc-alkali rocks derived from tholeiite magma in Hakone volcano; pyroxene crystallization trends and pyroxene geothermometry to estimate the magma temperature

    Science.gov (United States)

    Ishii, T.

    2012-12-01

    Calc-alkali rocks are widely distributed in the island arcs. The several models of their magma-genesis were proposed by many geoscientists (e.g. Kuno 1950, Osborn 1959, Sakuyama 1981, Tatsumi 2011) on the bases of precise petrological investigations. Crystallization trends of rock forming minerals (pyroxene, feldspar etc.) in the individual lava flow of the hydrous tholeiitic magma are represented by chemical zoning from phenocryst through microphenocryst to the groundmass in each lava. Those trends indicate degassing (or dehydrating) trends of erupted lava (Ishii 1991). Crystallization trend of minerals of hydrous magma in the subvolcanic magma reservoir is represented by core of phenocrysts throughout lava-flow strata in each volcano. Those trends indicate water-enrichment (or hydrating) trend in the magma reservoir. On the bases of the detailed analyses of the pyroxene crystallization sequences as well as estimated magmatic temperatures using pyroxene geothermometer, for calc-alkali rocks from the Central Cone (CC) in the Hakone volcano, the following working hypothesis is suggested, i.e. those calc-alkali rocks are induced by magma mixing between high temperature (about 1120 Degree Centigrade) tholeiite magma and low temperature (about 970 Degree Centigrade) magma, the latter is originated from fractional crystallization of the primitive high temperature hydras island-arc tholeiite magma within magma reservoir under closed environment for water. Reference Ishii, T., 1991. Lava-flow and subvolcanic magma reservoir composition trends in the Ca-poor pyroxenes of Hakone Volcano, Japan. Jour. Petrol., 32, 429-450 Kuno, H., 1950. Petrology of Hakone volcano and the adjacent areas, Japan. Bull. Geol. Soc. Am., 61, 957-1019. Sakuyama, M., 1981. Petrological study of the Myoko and Kurohime volcanoes, Japan: crystallization sequence and evidence for magma mixing. Jour. Petrol., 22, 553-583. Osborn, E. F., 1959. Role of oxygen pressure in the crystallization and

  13. Analysis of the physical atomic forces between noble gas atoms, alkali ions and halogen ions

    Science.gov (United States)

    Wilson, J. W.; Heinbockel, J. H.; Outlaw, R. A.

    1986-01-01

    The physical forces between atoms and molecules are important in a number of processes of practical importance, including line broadening in radiative processes, gas and crystal properties, adhesion, and thin films. The components of the physical forces between noble gas atoms, alkali ions, and halogen ions are analyzed and a data base for the dispersion forces is developed from the literature based on evaluations with the harmonic oscillator dispersion model for higher order coefficients. The Zener model of the repulsive core is used in the context of the recent asymptotic wave functions of Handler and Smith; and an effective ionization potential within the Handler and Smith wave functions is defined to analyze the two body potential data of Waldman and Gordon, the alkali-halide molecular data, and the noble gas crystal and salt crystal data. A satisfactory global fit to this molecular and crystal data is then reproduced by the model to within several percent. Surface potentials are evaluated for noble gas atoms on noble gas and salt crystal surfaces with surface tension neglected. Within this context, the noble gas surface potentials on noble gas and salt crystals are considered to be accurate to within several percent.

  14. Theoretical and experimental study of the Stark effect in the ground state of alkali atoms in helium crystals

    OpenAIRE

    2007-01-01

    This thesis work describes a detailed study of the Stark interaction in the ground state of cesium atoms trapped in a solid helium matrix. The motivation for the investigation of electric field effects on alkali species implanted in solid helium is related to the original main goal of our experimental activities, i.e., the measurement of a permanent atomic electric dipole moment (EDM). The existence of an atomic EDM simultaneously violates the discrete symmetries of time reversal (T) and pari...

  15. He atom-surface scattering: Surface dynamics of insulators, overlayers and crystal growth. Progress report, May 1, 1991--April 30, 1992

    Energy Technology Data Exchange (ETDEWEB)

    1992-05-01

    Investigations in this laboratory have focused on the surface structure and dynamics of ionic insulators and on epitaxial growth onto alkali halide crystals. In the later the homoepitaxial growth of NaCl/NaCl(001) and the heteroepitaxial growth of KBr/NaCl(001), NaCl/KBr(001) and KBr/RbCl(001) have been studied by monitoring the specular He scattering as a function of the coverage and by measuring the angular and energy distributions of the scattered He atoms. These data provide information on the surface structure, defect densities, island sizes and surface strain during the layer-by-layer growth. The temperature dependence of these measurements also provides information on the mobilities of the admolecules. He atom scattering is unique among surface probes because the low-energy, inert atoms are sensitive only to the electronic structure of the topmost surface layer and are equally applicable to all crystalline materials. It is proposed for the next year to exploit further the variety of combinations possible with the alkali halides in order to carry out a definitive study of epitaxial growth in the ionic insulators. The work completed so far, including measurements of the Bragg diffraction and surface dispersion at various stages of growth, appears to be exceptionally rich in detail, which is particularly promising for theoretical modeling. In addition, because epitaxial growth conditions over a wide range of lattice mismatches is possible with these materials, size effects in growth processes can be explored in great depth. Further, as some of the alkali halides have the CsCl structure instead of the NaCl structure, we can investigate the effects of the heteroepitaxy with materials having different lattice preferences. Finally, by using co-deposition of different alkali halides, one can investigate the formation and stability of alloys and even alkali halide superlattices.

  16. Crystal Structure and Topological Aspects of the High-Temperature Phases of the Alkali-metal Oxalates M-2 C2O4(M= K,Rb, Cs)

    Energy Technology Data Exchange (ETDEWEB)

    Dinnebier,R.; Vensky, S.; Jensen, M.; Hanson, J.

    2005-01-01

    The high-temperature phases of the alkali-metal oxalates M{sub 2}[C{sub 2}O{sub 4}] (M=K, Rb, Cs), and their decomposition products M{sub 2}[CO{sub 3}] (M=K, Rb, Cs), were investigated by fast, angle-dispersive X-ray powder diffraction with an image-plate detector, and also by simultaneous differential thermal analysis (DTA)/thermogravimetric analysis (TGA)/mass spectrometry (MS) and differential scanning calorimetry (DSC) techniques. The following phases, in order of decreasing temperature, were observed and crystallographically characterized (an asterisk denotes a previously unknown modification): *{alpha}-K{sub 2}[C{sub 2}O{sub 4}], *{alpha}-Rb{sub 2}[C{sub 2}O{sub 4}], *{alpha}-Cs{sub 2}[C{sub 2}O{sub 4}], {alpha}-K{sub 2}[CO{sub 3}], *{alpha}-Rb{sub 2}[CO{sub 3}], and *{alpha}-Cs{sub 2}[CO{sub 3}] in space group P6{sub 3}/mmc; *{beta}-Rb{sub 2}[C{sub 2}O{sub 4}], *{beta}-Cs{sub 2}[C{sub 2}O{sub 4}], *{beta}-Rb{sub 2}[CO{sub 3}], and *{beta}-Cs{sub 2}[CO{sub 3}] in Pnma; {gamma}-Rb{sub 2}[C{sub 2}O{sub 4}], {gamma}-Cs[C{sub 2}O{sub 4}], {gamma}-Rb{sub 2}[CO{sub 3}], and {gamma}-Cs{sub 2}[CO{sub 3}] in P2{sub 1}/c; and {delta}-K{sub 2}[C{sub 2}O{sub 4}] and {delta}-Rb{sub 2}[C{sub 2}O{sub 4}] in Pbam. With respect to the centers of gravity of the oxalate and carbonate anions, respectively, the crystal structures of all known alkali-metal oxalates and carbonates belong to the AlB{sub 2} family, and adopt either the AlB{sub 2} or the Ni{sub 2}In arrangement depending on the size of the cation and the temperature. Despite the different sizes and constitutions of the carbonate and oxalate anions, the high-temperature phases of the alkali-metal carbonates M{sub 2}[CO{sub 3}] (M=K, Rb, Cs), exhibit the same sequence of basic structures as the corresponding alkali-metal oxalates. The topological aspects and order-disorder phenomena at elevated temperature are discussed.

  17. Influence of halide composition on the structural, electronic, and optical properties of mixed CH3NH3Pb (I1-xBrx) 3 perovskites calculated using the virtual crystal approximation method

    Science.gov (United States)

    Jong, Un-Gi; Yu, Chol-Jun; Ri, Jin-Song; Kim, Nam-Hyok; Ri, Guk-Chol

    2016-09-01

    Extensive studies have demonstrated the promising capability of the organic-inorganic hybrid halide perovskite CH3NH3PbI3 in solar cells with a high power conversion efficiency exceeding 20%. However, the intrinsic as well as extrinsic instabilities of this material remain the major challenge to the commercialization of perovskite-based solar cells. Mixing halides is expected to resolve this problem. Here, we investigate the effect of chemical substitution in the position of the halogen atom on the structural, electronic, and optical properties of mixed halide perovskites CH3NH3Pb (I1-xBrx) 3 with a pseudocubic phase using the virtual crystal approximation method within density functional theory. With an increase of Br content x from 0.0 to 1.0, the lattice constant decreases in proportion to x with the function of a (x )=6.420 -0.333 x (Å), while the band gap and the exciton binding energy increase with the quadratic function of Eg(x ) =1.542 +0.374 x +0.185 x2 (eV) and the linear function of Eb(x ) =0.045 +0.057 x (eV), respectively. The photoabsorption coefficients are also calculated, showing a blueshift of the absorption onsets for higher Br contents. We calculate the phase decomposition energy of these materials and analyze the electronic charge density difference to estimate the material stability. Based on the calculated results, we suggest that the best match between efficiency and stability can be achieved at x ≈0.2 in CH3NH3Pb (I1-xBrx) 3 perovskites.

  18. Fabrication of La2Ti2O7 crystals using an alkali-metal molybdate flux growth method and their nitridability to form LaTiO2N crystals under a high-temperature NH3 atmosphere.

    Science.gov (United States)

    Hojamberdiev, Mirabbos; Yamaguchi, Akiko; Yubuta, Kunio; Oishi, Shuji; Teshima, Katsuya

    2015-04-06

    Flux growth is a promising method that allows one to control over the crystalline phase, crystal shape, crystal size, and crystal surface through the selection of a suitable flux. In this work, lanthanum titanate (La2Ti2O7) crystals with different morphologies were grown using the Na2MoO4, K2MoO4, NaCl, and mixed NaCl + K2MoO4 (molar ratio = 3:7) fluxes, and their nitridability to form LaTiO2N crystals under a high-temperature NH3 atmosphere was also investigated. The effects of the solute concentration and cooling rate on the growth of the La2Ti2O7 crystals were also studied. The X-ray diffraction results revealed that the {100} plane was dominant in the La2Ti2O7 platelet crystals grown using the alkali-metal molybdate fluxes. When the solute concentration was increased from 1 to 20 mol %, the average size of the crystals decreased without considerable alteration of the overall crystal morphology. The La2Ti2O7 crystals with the preferred ⟨010⟩ and ⟨001⟩ growth directions along the b and c axes were grown using the Na2MoO4 and K2MoO4 fluxes, respectively. Compared to the Na2MoO4 flux, the K2MoO4 flux did not show a cooling-rate-dependent effect on the growth of the La2Ti2O7 crystals. It was found that conversion of the La2Ti2O7 crystals to the LaTiO2N crystals was strongly dependent on the flux used to grow the precursor La2Ti2O7 crystals. That is, the La2Ti2O7 crystals grown using the K2MoO4 and NaCl fluxes were nearly completely converted into the LaTiO2N crystals, while conversion of the La2Ti2O7 crystals grown using the Na2MoO4 and mixed NaCl + K2MoO4 fluxes to the LaTiO2N crystals seemed to be not completed yet even after nitridation at 950 °C for 15 h using NH3 because of the larger crystal size and the presence of unintentional impurities (sodium and molybdenum from the flux) in the La2Ti2O7 crystal lattice. Nevertheless, the LaTiO2N crystals fabricated by nitriding the La2Ti2O7 crystals grown using the K2MoO4 and NaCl fluxes should be suitable for

  19. Bio-conventional bleaching of kadam kraft-AQ pulp by thermo-alkali-tolerant xylanases from two strains of Coprinellus disseminatus for extenuating adsorbable organic halides and improving strength with optical properties and energy conservation.

    Science.gov (United States)

    Lal, Mohan; Dutt, Dharm; Tyagi, C H

    2012-04-01

    Two novel thermo-alkali-tolerant crude xylanases namely MLK-01 (enzyme-A) and MLK-07 (enzyme-B) from Coprinellus disseminatus mitigated kappa numbers of Anthocephalus cadamba kraft-AQ pulps by 32.5 and 34.38%, improved brightness by 1.5 and 1.6% and viscosity by 5.75 and 6.47% after (A)XE(1) and (B)XE(1)-stages, respectively. The release of reducing sugars and chromophores was the highest during prebleaching of A. cadamba kraft-AQ pulp at enzyme doses of 5 and 10 IU/g, reaction times 90 and 120 min, reaction temperatures 75 and 65°C and consistency 10% for MLK-01 and MLK-07, respectively. MLK-07 was more efficient than MLK01 in terms of producing pulp brightness, improving mechanical strength properties and reducing pollution load. MLK-01 and MLK-07 reduced AOX by 19.51 and 42.77%, respectively at 4% chlorine demands with an increase in COD and colour due to removal of lignin carbohydrates complexes. A. cadamba kraft-AQ pulps treated with xylanases from MLK-01 to MLK-07 and followed by CEHH bleaching at half chlorine demand (2%) showed a drastic reduction in brightness with slight improvement in mechanical strength properties compared to pulp bleached at 4% chlorine demand. MLK-01 reduced AOX, COD and colour by 43.83, 39.03 and 27.71% and MLK-07 by 38.34, 40.48 and 30.77%, respectively at half chlorine demand compared to full chlorine demand (4%). pH variation during prebleaching of A. cadamba kraft-AQ pulps with strains MLK-01 and MLK-07 followed by CEHH bleaching sequences showed a decrease in pulp brightness, AOX, COD and colour with an increase in mechanical strength properties, pulp viscosity and PFI revolutions to get a beating level of 35 ± 1 °SR at full chlorine demand.

  20. The Pressure induced by salt crystallization in confinement

    Science.gov (United States)

    Desarnaud, J.; Bonn, D.; Shahidzadeh, N.

    2016-08-01

    Salt crystallization is a major cause of weathering of rocks, artworks and monuments. Damage can only occur if crystals continue to grow in confinement, i.e. within the pore space of these materials, thus generating mechanical stress. We report the direct measurement, at the microscale, of the force exerted by growing alkali halide salt crystals while visualizing their spontaneous nucleation and growth. The experiments reveal the crucial role of the wetting films between the growing crystal and the confining walls for the development of the pressure. Our results suggest that the measured force originates from repulsion between the similarly charged confining wall and the salt crystal separated by a ~1.5 nm liquid film. Indeed, if the walls are made hydrophobic, no film is observed and no repulsive forces are detected. We also show that the magnitude of the induced pressure is system specific explaining why different salts lead to different amounts of damage to porous materials.

  1. Fast light of CsI(Na) crystals

    Institute of Scientific and Technical Information of China (English)

    SUN Xi-Lei; FANG Jian; XIE Yu-Guang; AN Zheng-Hua; WANG Zhi-Gang; XUE Zhen; ZHANG Ai-Wu; LU Qi-Wen; NING Fei-Peng; GEYong-Shuai; LIU Ying-Biao; LU Jun-Guang; HU Tao; ZHOU Li; CAO Jun; WANG Yi-Fang; ZHAN Liang; YU Bo-Xiang; CAI Xiao

    2011-01-01

    The responses of different common alkali halide crystals to alpha-rays and gamma-rays are tested in this research.It is found that only CsI(Na) crystals have significantly different waveforms between alpha and gamma scintillations,while others do not exhibit this phenomena.The rise time of the fast light is about 5 ns and the decay time is 17±12 ns.It is suggested that the fast light of CsI(Na) crystals arises from the recombination of free electrons with self-trapped holes of the host crystal CsI.Self-absorption limits the emission of fast light of CsI(T1) and NaI(T1) crystals.

  2. Recent advances in technetium halide chemistry.

    Science.gov (United States)

    Poineau, Frederic; Johnstone, Erik V; Czerwinski, Kenneth R; Sattelberger, Alfred P

    2014-02-18

    Transition metal binary halides are fundamental compounds, and the study of their structure, bonding, and other properties gives chemists a better understanding of physicochemical trends across the periodic table. One transition metal whose halide chemistry is underdeveloped is technetium, the lightest radioelement. For half a century, the halide chemistry of technetium has been defined by three compounds: TcF6, TcF5, and TcCl4. The absence of Tc binary bromides and iodides in the literature was surprising considering the existence of such compounds for all of the elements surrounding technetium. The common synthetic routes that scientists use to obtain binary halides of the neighboring elements, such as sealed tube reactions between elements and flowing gas reactions between a molecular complex and HX gas (X = Cl, Br, or I), had not been reported for technetium. In this Account, we discuss how we used these routes to revisit the halide chemistry of technetium. We report seven new phases: TcBr4, TcBr3, α/β-TcCl3, α/β-TcCl2, and TcI3. Technetium tetrachloride and tetrabromide are isostructural to PtX4 (X = Cl or Br) and consist of infinite chains of edge-sharing TcX6 octahedra. Trivalent technetium halides are isostructural to ruthenium and molybdenum (β-TcCl3, TcBr3, and TcI3) and to rhenium (α-TcCl3). Technetium tribromide and triiodide exhibit the TiI3 structure-type and consist of infinite chains of face-sharing TcX6 (X = Br or I) octahedra. Concerning the trichlorides, β-TcCl3 crystallizes with the AlCl3 structure-type and consists of infinite layers of edge-sharing TcCl6 octahedra, while α-TcCl3 consists of infinite layers of Tc3Cl9 units. Both phases of technetium dichloride exhibit new structure-types that consist of infinite chains of [Tc2Cl8] units. For the technetium binary halides, we studied the metal-metal interaction by theoretical methods and magnetic measurements. The change of the electronic configuration of the metal atom from d(3) (Tc

  3. Synthesis, crystal structures and reactivity of copper(I) amidate complexes with aryl halides: insight into copper(I)-catalyzed Goldberg reaction.

    Science.gov (United States)

    Liu, Xinfang; Zhang, Songlin; Ding, Yuqiang

    2012-05-21

    In this paper, copper(I) amidate complexes (2-3), proposed intermediates in copper-catalyzed Goldberg reaction, have been prepared and characterized by elemental analysis, IR, (1)H NMR and X-ray crystallography. Ancillary ligand bis(diphenylphosphino)ferrocene (dppf) has contributed greatly to the stability of the copper-amidate complexes due to its strong chelating ability and weak intermolecular interactions. Thermal gravimetric analyses are carried out to determine the thermal competency of complexes 2-3 as the intermediates of the high-temperature Goldberg reactions. Reaction of complexes 2 and 3 with aryl halides generates the N-arylation products 5-8, accompanied by the formation of a copper(I) complex Cu(dppf)X (X = I or Br) 4, which has been determined by LC-MS analysis. These results provide new evidence for the mechanism of copper(I)-catalyzed Goldberg reaction.

  4. Crystal and molecular structures of alkali oxalates: first proof of a staggered oxalate anion in the solid state.

    Science.gov (United States)

    Dinnebier, Robert E; Vensky, Sascha; Panthöfer, Martin; Jansen, Martin

    2003-03-10

    The molecular and crystal structures of solvent-free potassium, rubidium, and cesium oxalates have been determined ab initio from high-resolution synchrotron and X-ray laboratory powder patterns. In the case of potassium oxalate K(2)C(2)O(4) (a = 10.91176(7) A, b = 6.11592(4) A, c = 3.44003(2) A, orthorhombic, Pbam, Z = 2), the oxalate anion is planar, whereas in cesium oxalate Cs(2)C(2)O(4) (a = 6.62146(5) A, b = 11.00379(9) A, c = 8.61253(7) A, beta = 97.1388(4) degrees, monoclinic, P2(1)/c, Z = 4) it exhibits a staggered conformation. For rubidium oxalate at room temperature, two polymorphs exist, one (beta-Rb(2)C(2)O(4)) isotypic to potassium oxalate (a = 11.28797(7) A, b = 6.29475(4) A, c = 3.62210(2) A, orthorhombic, Pbam, Z = 2) and the other (alpha-Rb(2)C(2)O(4)) isotypic to cesium oxalate (a = 6.3276(1) A, b = 10.4548(2) A, c = 8.2174(2) A, beta = 98.016(1) degrees, monoclinic, P2(1)/c, Z = 4). The potassium oxalate structure can be deduced from the AlB(2) type, and the cesium oxalate structure from the Hg(99)As type, respectively. The relation between the two types of crystal structures and the reason for the different conformations of the oxalate anion are discussed.

  5. Electronic and Ionic Transport Dynamics in Organolead Halide Perovskites.

    Science.gov (United States)

    Li, Dehui; Wu, Hao; Cheng, Hung-Chieh; Wang, Gongming; Huang, Yu; Duan, Xiangfeng

    2016-07-26

    Ion migration has been postulated as the underlying mechanism responsible for the hysteresis in organolead halide perovskite devices. However, the electronic and ionic transport dynamics and how they impact each other in organolead halide perovskites remain elusive to date. Here we report a systematic investigation of the electronic and ionic transport dynamics in organolead halide perovskite microplate crystals and thin films using temperature-dependent transient response measurements. Our study reveals that thermally activated ionic and electronic conduction coexist in perovskite devices. The extracted activation energies suggest that the electronic transport is easier, but ions migrate harder in microplates than in thin films, demonstrating that the crystalline quality and grain boundaries can fundamentally modify electronic and ionic transport in perovskites. These findings offer valuable insight on the electronic and ionic transport dynamics in organolead halide perovskites, which is critical for optimizing perovskite devices with reduced hysteresis and improved stability and efficiency.

  6. Cs7Sm11[TeO3]12Cl16 and Rb7Nd11[TeO3]12Br16, the new tellurite halides of the tetragonal Rb6LiNd11[SeO3]12Cl16 structure type

    OpenAIRE

    Dmitri O. Charkin; Black, Cameron; Downie, Lewis James; Sklovsky, Dmitry E.; Peter S. Berdonosov; Olenev, Andrei V.; Zhou, Wuzong; Lightfoot, Philip; Dolgikh, Valery A.

    2015-01-01

    The authors thank the Russian Foundation for Basic Researches for the support of this work under Grants No. 14-03-00604_a and 12-03-92604-KO_a. The X-ray study of compound II was made possible due to M.V. Lomonosov Moscow State University Programm of Development. PL thanks the University of St Andrews and EPSRC for DTA Studentships to CB and LJD. Two new rare-earth – alkali – tellurium oxide halides were synthesized by a salt flux technique and characterized by single-crystal X-ray diffrac...

  7. Characteristics of the fast electron emission produced during the cleavage of crystals

    Indian Academy of Sciences (India)

    B P Chandra; N L Patel; S S Rahangdale; R P Patel; V K Patle

    2003-01-01

    The present paper reports the fast electron emission produced during the cleavage of alkali halide crystals and models the dynamics of the process. The mechano-emission arises as a result of the ionization of surface traps at the expense of the energy which is released in the annihilation of the defects which are formed during cleavage. The slow electrons which appear upon the ionization of surface traps are subsequently accelerated in the field of negatively charged segment of the freshly cleaved surface. Considering the basic mechanism of fast electron emission, expressions are derived which are able to explain satisfactorily the temporal, thermal, charge, surface, coloration, water adsorption and other characteristics of the fast electron emission produced during the cleavage of crystals. The decay time of the charges on the newly created surfaces, and the velocity of cracks can be determined from the measurements of fast electron emission produced during the cleavage of crystals. It is shown that two types of diffusing centres are responsible for the charge relaxation and thereby for the emission of fast electrons produced during the cleavage of alkali halide crystals.

  8. Impact of the organic halide salt on final perovskite composition for photovoltaic applications

    KAUST Repository

    Moore, David T.

    2014-08-01

    The methylammonium lead halide perovskites have shown significant promise as a low-cost, second generation, photovoltaic material.Despite recent advances, however, there are still a number of fundamental aspects of their formation as well as their physical and electronic behavior that are not well understood. In this letter we explore the mechanism by which these materials crystallize by testing the outcome of each of the reagent halide salts. We find that components of both salts, lead halide and methylammonium halide, are relatively mobile and can be readily exchanged during the crystallization process when the reaction is carried out in solution or in the solid state. We exploit this fact by showing that the perovskite structure is formed even when the lead salt\\'s anion is a non-halide, leading to lower annealing temperature and time requirements for film formation. Studies into these behaviors may ultimately lead to improved processing conditions for photovoltaic films. © 2014 Author(s).

  9. Impact of the organic halide salt on final perovskite composition for photovoltaic applications

    Directory of Open Access Journals (Sweden)

    David T. Moore

    2014-08-01

    Full Text Available The methylammonium lead halide perovskites have shown significant promise as a low-cost, second generation, photovoltaic material. Despite recent advances, however, there are still a number of fundamental aspects of their formation as well as their physical and electronic behavior that are not well understood. In this letter we explore the mechanism by which these materials crystallize by testing the outcome of each of the reagent halide salts. We find that components of both salts, lead halide and methylammonium halide, are relatively mobile and can be readily exchanged during the crystallization process when the reaction is carried out in solution or in the solid state. We exploit this fact by showing that the perovskite structure is formed even when the lead salt's anion is a non-halide, leading to lower annealing temperature and time requirements for film formation. Studies into these behaviors may ultimately lead to improved processing conditions for photovoltaic films.

  10. Cold ablation driven by localized forces in alkali halides

    NARCIS (Netherlands)

    Hada, Masaki; Zhang, Dongfang; Pichugin, Kostyantyn; Hirscht, Julian; Kochman, Micha A.; Hayes, Stuart A.; Manz, Stephanie; Gengler, Regis Y. N.; Wann, Derek A.; Seki, Toshio; Moriena, Gustavo; Morrison, Carole A.; Matsuo, Jiro; Sciaini, German; Miller, R. J. Dwayne

    2014-01-01

    Laser ablation has been widely used for a variety of applications. Since the mechanisms for ablation are strongly dependent on the photoexcitation level, so called cold material processing has relied on the use of high-peak-power laser fluences for which nonthermal processes become dominant; often r

  11. Extended temperature dependence of elastic constants in cubic crystals.

    Science.gov (United States)

    Telichko, A V; Sorokin, B P

    2015-08-01

    To extend the theory of the temperature dependence of the elastic constants in cubic crystals beyond the second- and third-order elastic constants, the fourth-order elastic constants, as well as the non-linearity in the thermal expansion temperature dependence, have been taken into account. Theoretical results were represented as temperature functions of the effective elastic constants and compared with experimental data for a number of cubic crystals, such as alkali metal halides, and elements gold and silver. The relations obtained give a more accurate description of the experimental temperature dependences of second-order elastic constants for a number of cubic crystals, including deviations from linear behavior. A good agreement between theoretical estimates and experimental data has been observed.

  12. Nanosized alkali-metal-doped ethoxotitanate clusters.

    Science.gov (United States)

    Chen, Yang; Trzop, Elzbieta; Makal, Anna; Sokolow, Jesse D; Coppens, Philip

    2013-05-06

    The synthesis and crystallographic characterization of alkali-metal-doped ethoxotitanate clusters with 28 and 29 Ti atoms as well as a new dopant-free Ti28 cluster are presented. The light-metal-doped polyoxotitanate clusters in which the alkali-metal atom is the critical structure-determining component are the largest synthesized so far. Calculations show that doping with light alkali atoms narrows the band gap compared with the nondoped crystals but does not introduce additional energy levels within the band gap.

  13. Photoionization in alkali lasers.

    Science.gov (United States)

    Knize, R J; Zhdanov, B V; Shaffer, M K

    2011-04-11

    We have calculated photoionization rates in alkali lasers. The photoionization of alkali atoms in the gain medium of alkali lasers can significantly degrade the laser performance by reducing the neutral alkali density and with it the gain. For a ten atmosphere Rb laser and a Cs exciplex laser, the photoionization induced alkali atom loss rates are greater than 10(5) sec(-1). These high loss rates will quickly deplete the neutral alkali density, reducing gain, and may require fast, possibly, supersonic flow rates to sufficiently replenish the neutral medium for CW operation.

  14. Making and Breaking of Lead Halide Perovskites.

    Science.gov (United States)

    Manser, Joseph S; Saidaminov, Makhsud I; Christians, Jeffrey A; Bakr, Osman M; Kamat, Prashant V

    2016-02-16

    A new front-runner has emerged in the field of next-generation photovoltaics. A unique class of materials, known as organic metal halide perovskites, bridges the gap between low-cost fabrication and exceptional device performance. These compounds can be processed at low temperature (typically in the range 80-150 °C) and readily self-assemble from the solution phase into high-quality semiconductor thin films. The low energetic barrier for crystal formation has mixed consequences. On one hand, it enables inexpensive processing and both optical and electronic tunability. The caveat, however, is that many as-formed lead halide perovskite thin films lack chemical and structural stability, undergoing rapid degradation in the presence of moisture or heat. To date, improvements in perovskite solar cell efficiency have resulted primarily from better control over thin film morphology, manipulation of the stoichiometry and chemistry of lead halide and alkylammonium halide precursors, and the choice of solvent treatment. Proper characterization and tuning of processing parameters can aid in rational optimization of perovskite devices. Likewise, gaining a comprehensive understanding of the degradation mechanism and identifying components of the perovskite structure that may be particularly susceptible to attack by moisture are vital to mitigate device degradation under operating conditions. This Account provides insight into the lifecycle of organic-inorganic lead halide perovskites, including (i) the nature of the precursor solution, (ii) formation of solid-state perovskite thin films and single crystals, and (iii) transformation of perovskites into hydrated phases upon exposure to moisture. In particular, spectroscopic and structural characterization techniques shed light on the thermally driven evolution of the perovskite structure. By tuning precursor stoichiometry and chemistry, and thus the lead halide charge-transfer complexes present in solution, crystallization

  15. Making and Breaking of Lead Halide Perovskites

    KAUST Repository

    Manser, Joseph S.

    2016-02-16

    A new front-runner has emerged in the field of next-generation photovoltaics. A unique class of materials, known as organic metal halide perovskites, bridges the gap between low-cost fabrication and exceptional device performance. These compounds can be processed at low temperature (typically in the range 80–150 °C) and readily self-assemble from the solution phase into high-quality semiconductor thin films. The low energetic barrier for crystal formation has mixed consequences. On one hand, it enables inexpensive processing and both optical and electronic tunability. The caveat, however, is that many as-formed lead halide perovskite thin films lack chemical and structural stability, undergoing rapid degradation in the presence of moisture or heat. To date, improvements in perovskite solar cell efficiency have resulted primarily from better control over thin film morphology, manipulation of the stoichiometry and chemistry of lead halide and alkylammonium halide precursors, and the choice of solvent treatment. Proper characterization and tuning of processing parameters can aid in rational optimization of perovskite devices. Likewise, gaining a comprehensive understanding of the degradation mechanism and identifying components of the perovskite structure that may be particularly susceptible to attack by moisture are vital to mitigate device degradation under operating conditions. This Account provides insight into the lifecycle of organic–inorganic lead halide perovskites, including (i) the nature of the precursor solution, (ii) formation of solid-state perovskite thin films and single crystals, and (iii) transformation of perovskites into hydrated phases upon exposure to moisture. In particular, spectroscopic and structural characterization techniques shed light on the thermally driven evolution of the perovskite structure. By tuning precursor stoichiometry and chemistry, and thus the lead halide charge-transfer complexes present in solution, crystallization

  16. Milk-alkali syndrome

    Science.gov (United States)

    ... this page: //medlineplus.gov/ency/article/000332.htm Milk-alkali syndrome To use the sharing features on this page, please enable JavaScript. Milk-alkali syndrome is a condition in which there ...

  17. Deciphering Halogen Competition in Organometallic Halide Perovskite Growth.

    Science.gov (United States)

    Yang, Bin; Keum, Jong; Ovchinnikova, Olga S; Belianinov, Alex; Chen, Shiyou; Du, Mao-Hua; Ivanov, Ilia N; Rouleau, Christopher M; Geohegan, David B; Xiao, Kai

    2016-04-20

    Organometallic halide perovskites (OHPs) hold great promise for next-generation, low-cost optoelectronic devices. During the chemical synthesis and crystallization of OHP thin films, a major unresolved question is the competition between multiple halide species (e.g., I(-), Cl(-), Br(-)) in the formation of the mixed-halide perovskite crystals. Whether Cl(-) ions are successfully incorporated into the perovskite crystal structure or, alternatively, where they are located is not yet fully understood. Here, in situ X-ray diffraction measurements of crystallization dynamics are combined with ex situ TOF-SIMS chemical analysis to reveal that Br(-) or Cl(-) ions can promote crystal growth, yet reactive I(-) ions prevent them from incorporating into the lattice of the final perovskite crystal structure. The Cl(-) ions are located in the grain boundaries of the perovskite films. These findings significantly advance our understanding of the role of halogens during synthesis of hybrid perovskites and provide an insightful guidance to the engineering of high-quality perovskite films, essential for exploring superior-performing and cost-effective optoelectronic devices.

  18. Finding New Perovskite Halides via Machine learning

    Directory of Open Access Journals (Sweden)

    Ghanshyam ePilania

    2016-04-01

    Full Text Available Advanced materials with improved properties have the potential to fuel future technological advancements. However, identification and discovery of these optimal materials for a specific application is a non-trivial task, because of the vastness of the chemical search space with enormous compositional and configurational degrees of freedom. Materials informatics provides an efficient approach towards rational design of new materials, via learning from known data to make decisions on new and previously unexplored compounds in an accelerated manner. Here, we demonstrate the power and utility of such statistical learning (or machine learning via building a support vector machine (SVM based classifier that uses elemental features (or descriptors to predict the formability of a given ABX3 halide composition (where A and B represent monovalent and divalent cations, respectively, and X is F, Cl, Br or I anion in the perovskite crystal structure. The classification model is built by learning from a dataset of 181 experimentally known ABX3 compounds. After exploring a wide range of features, we identify ionic radii, tolerance factor and octahedral factor to be the most important factors for the classification, suggesting that steric and geometric packing effects govern the stability of these halides. The trained and validated models then predict, with a high degree of confidence, several novel ABX3 compositions with perovskite crystal structure.

  19. Finding New Perovskite Halides via Machine learning

    Science.gov (United States)

    Pilania, Ghanshyam; Balachandran, Prasanna V.; Kim, Chiho; Lookman, Turab

    2016-04-01

    Advanced materials with improved properties have the potential to fuel future technological advancements. However, identification and discovery of these optimal materials for a specific application is a non-trivial task, because of the vastness of the chemical search space with enormous compositional and configurational degrees of freedom. Materials informatics provides an efficient approach towards rational design of new materials, via learning from known data to make decisions on new and previously unexplored compounds in an accelerated manner. Here, we demonstrate the power and utility of such statistical learning (or machine learning) via building a support vector machine (SVM) based classifier that uses elemental features (or descriptors) to predict the formability of a given ABX3 halide composition (where A and B represent monovalent and divalent cations, respectively, and X is F, Cl, Br or I anion) in the perovskite crystal structure. The classification model is built by learning from a dataset of 181 experimentally known ABX3 compounds. After exploring a wide range of features, we identify ionic radii, tolerance factor and octahedral factor to be the most important factors for the classification, suggesting that steric and geometric packing effects govern the stability of these halides. The trained and validated models then predict, with a high degree of confidence, several novel ABX3 compositions with perovskite crystal structure.

  20. Correlation of annealing time with crystal structure, composition, and electronic properties of CH3NH3PbI3-xClx mixed-halide perovskite films.

    Science.gov (United States)

    Ralaiarisoa, Maryline; Busby, Yan; Frisch, Johannes; Salzmann, Ingo; Pireaux, Jean-Jacques; Koch, Norbert

    2016-12-21

    Using 3D imaging with time-of-flight secondary ion mass spectrometry (ToF-SIMS) complemented by grazing-incidence X-ray diffraction (GIXRD), we spatially resolve changes in both the composition and structure of CH3NH3I3-xClx perovskite films on conducting polymer substrates at different annealing stages, in particular, before and after complete perovskite crystallization. The early stage of annealing is characterized by phase separation throughout the entire film into domains with perovskite and domains with a dominating chloride-rich phase. After sufficiently long annealing, one single perovskite phase of homogeneous composition on the (lateral) micrometer scale is observed, along with pronounced film texture. This composition evolution is accompanied by diffusion of chloride from the perovskite layer towards the conducting polymer substrate, and even accumulation there. Photoelectron spectroscopy analysis further shows that perovskite films become increasingly n-type with annealing time and upon full conversion, which correlates with the change of film composition. Our results accentuate the importance of chloride for the formation of crystalline and textured films, which are crucial for enhancing the PV performance of perovskite-based solar cells.

  1. Nickel(II) complexes of N2S2 donor set ligand and halide/pseudohalides: Synthesis, crystal structure, DNA and bovine/human serum albumin interaction

    Indian Academy of Sciences (India)

    Animesh Patra; Biplab Mondal; Buddhadeb Sen; Ennio Zangrando; Pabitra Chattopadhyay

    2015-11-01

    A series of neutral hexacoordinated nickel(II) complexes of formula [NiII (L)X2] (where L = 3,4-bis(2-pyridylmethylthio)toluene with tetradentate N2S2 donor set and X = chloride (1), azide (2), cyanate (3) and isothiocyanate anion (4)) have been synthesized and isolated in pure form. The complexes were characterized by physicochemical and spectroscopic methods along with detailed structural characterization of 1,2 and 3 by single crystal X-ray diffraction analyses. The structural study showed that the nickel(II) ion has a distorted octahedral geometry being chelated by the tetradentate N2S2 ligand and bound to cis- located choride or pseudohalide anions. In dimethylformamide solution the complexes showed quasi-reversible NiII/NiIII redox couples in cyclic voltammograms with E1/2 values of +0.723, +0.749, +0.768 and +0.868 V for 1, 2, 3 and 4, respectively. The study of interaction of the complexes with calf thymus DNA, bovine serum albumin (BSA) and human serum albumin (HSA) using spectroscopic and physicochemical tools clearly indicates that the complexes interact with DNA via groove binding mode.

  2. Multiphased (NaCl){sub x}(KCl){sub y-x}(KBr){sub 1-y} single crystals: ac conductivity activation energy versus bulk properties

    Energy Technology Data Exchange (ETDEWEB)

    Katsika-Tsigourakou, Vassiliki, E-mail: vkatsik@phys.uoa.g [Department of Solid State Physics, Faculty of Physics, University of Athens, Panepistimiopolis, 157 84 Zografos (Greece)

    2009-11-01

    The ac electrical measurements have been just reported for alkali halide mixed crystals that were melt grown from NaCl, KCl and KBr starting materials. They showed a nonlinear variation of all the electrical parameters with the bulk composition. In this short paper, we show that these mixed systems, depending on their major constituent, are classified into three categories in each of which, the activation energy for the ac conductivity increases linearly with BOMEGA, where B is the isothermal bulk modulus and OMEGA the mean volume per atom. In addition, the resulting three straight lines are formed to have almost the same slope.

  3. How specific halide adsorption varies hydrophobic interactions.

    Science.gov (United States)

    Stock, Philipp; Müller, Melanie; Utzig, Thomas; Valtiner, Markus

    2016-03-11

    Hydrophobic interactions (HI) are driven by the water structure around hydrophobes in aqueous electrolytes. How water structures at hydrophobic interfaces and how this influences the HI was subject to numerous studies. However, the effect of specific ion adsorption on HI and hydrophobic interfaces remains largely unexplored or controversial. Here, the authors utilized atomic force microscopy force spectroscopy at well-defined nanoscopic hydrophobic interfaces to experimentally address how specific ion adsorption of halide ions as well as NH4 (+), Cs(+), and Na(+) cations alters interaction forces across hydrophobic interfaces. Our data demonstrate that iodide adsorption at hydrophobic interfaces profoundly varies the hydrophobic interaction potential. A long-range and strong hydration repulsion at distances D > 3 nm, is followed by an instability which could be explained by a subsequent rapid ejection of adsorbed iodides from approaching hydrophobic interfaces. In addition, the authors find only a weakly pronounced influence of bromide, and as expected no influence of chloride. Also, all tested cations do not have any significant influence on HI. Complementary, x-ray photoelectron spectroscopy and quartz-crystal-microbalance with dissipation monitoring showed a clear adsorption of large halide ions (Br(-)/I(-)) onto hydrophobic self-assembled monolayers (SAMs). Interestingly, iodide can even lead to a full disintegration of SAMs due to specific and strong interactions of iodide with gold. Our data suggest that hydrophobic surfaces are not intrinsically charged negatively by hydroxide adsorption, as it was generally believed. Hydrophobic surfaces rather interact strongly with negatively charged large halide ions, leading to a surface charging and significant variation of interaction forces.

  4. Hall Determination of Atomic Radii of Alkali Metals

    Science.gov (United States)

    Houari, Ahmed

    2008-01-01

    I will propose here an alternative method for determining atomic radii of alkali metals based on the Hall measurements of their free electron densities and the knowledge of their crystal structure. (Contains 2 figures.)

  5. Crystal structures and topological aspects of the high-temperature phases and decomposition products of the alkali-metal oxalates M2[C2O4] (M=K, Rb, Cs).

    Science.gov (United States)

    Dinnebier, Robert E; Vensky, Sascha; Jansen, Martin; Hanson, Jonathan C

    2005-02-04

    The high-temperature phases of the alkali-metal oxalates M2[C2O4] (M = K, Rb, Cs), and their decomposition products M2[CO3] (M = K, Rb, Cs), were investigated by fast, angle-dispersive X-ray powder diffraction with an image-plate detector, and also by simultaneous differential thermal analysis (DTA)/thermogravimetric analysis (TGA)/mass spectrometry (MS) and differential scanning calorimetry (DSC) techniques. The following phases, in order of decreasing temperature, were observed and crystallographically characterized (an asterisk denotes a previously unknown modification): *alpha-K2[C2O4], *alpha-Rb2[C2O4], *alpha-Cs2[C2O4], alpha-K2[CO3], *alpha-Rb2[CO3], and *alpha-Cs2[CO3] in space group P6(3)/mmc; *beta-Rb2[C2O4], *beta-Cs2[C2O4], *beta-Rb2[CO3], and *beta-Cs2[CO3] in Pnma; gamma-Rb2[C2O4], gamma-Cs[C2O4], gamma-Rb2[CO3], and gamma-Cs2[CO3] in P2(1)/c; and delta-K2[C2O4] and delta-Rb2[C2O4] in Pbam. With respect to the centers of gravity of the oxalate and carbonate anions, respectively, the crystal structures of all known alkali-metal oxalates and carbonates belong to the AlB2 family, and adopt either the AlB2 or the Ni2In arrangement depending on the size of the cation and the temperature. Despite the different sizes and constitutions of the carbonate and oxalate anions, the high-temperature phases of the alkali-metal carbonates M2[CO3] (M = K, Rb, Cs), exhibit the same sequence of basic structures as the corresponding alkali-metal oxalates. The topological aspects and order-disorder phenomena at elevated temperature are discussed.

  6. Research Update: Physical and electrical characteristics of lead halide perovskites for solar cell applications

    Directory of Open Access Journals (Sweden)

    Simon A. Bretschneider

    2014-04-01

    Full Text Available The field of thin-film photovoltaics has been recently enriched by the introduction of lead halide perovskites as absorber materials, which allow low-cost synthesis of solar cells with efficiencies exceeding 16%. The exact impact of the perovskite crystal structure and composition on the optoelectronic properties of the material are not fully understood. Our progress report highlights the knowledge gained about lead halide perovskites with a focus on physical and optoelectronic properties. We discuss the crystal and band structure of perovskite materials currently implemented in solar cells and the impact of the crystal properties on ferroelectricity, ambipolarity, and the properties of excitons.

  7. Infrared Spectroscopic Study of Vibrational Modes in Methylammonium Lead Halide Perovskites.

    Science.gov (United States)

    Glaser, Tobias; Müller, Christian; Sendner, Michael; Krekeler, Christian; Semonin, Octavi E; Hull, Trevor D; Yaffe, Omer; Owen, Jonathan S; Kowalsky, Wolfgang; Pucci, Annemarie; Lovrinčić, Robert

    2015-08-06

    The organic cation and its interplay with the inorganic lattice underlie the exceptional optoelectronic properties of organo-metallic halide perovskites. Herein we report high-quality infrared spectroscopic measurements of methylammonium lead halide perovskite (CH3NH3Pb(I/Br/Cl)3) films and single crystals at room temperature, from which the dielectric function in the investigated spectral range is derived. Comparison with electronic structure calculations in vacuum of the free methylammonium cation allows for a detailed peak assignment. We analyze the shifts of the vibrational peak positions between the different halides and infer the extent of interaction between organic moiety and the surrounding inorganic cage. The positions of the NH3(+) stretching vibrations point to significant hydrogen bonding between the methylammonium and the halides for all three perovskites.

  8. The first pseudo-ternary thiocyanate containing two alkali metals. Synthesis and single-crystal structure of LiK{sub 2}[SCN]{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Reckeweg, Olaf; DiSalvo, Francis J. [Cornell Univ., Ithaca, NY (United States). Baker Lab.

    2016-04-01

    A procedure was empirically developed to prepare the compound LiK{sub 2}[SCN]{sub 3}, which forms colorless, transparent, very fragile, and extremely hygroscopic thin rectangular plates. Its unique crystal structure was determined by single-crystal X-ray diffraction. LiK{sub 2}[SCN]{sub 3} adopts the orthorhombic space group Pna2{sub 1} (no. 33, Z = 4) with the cell parameters a = 1209.32(9), b = 950.85(9), and c = 849.95(6) pm.

  9. Nonlinear refractive index of optical crystals

    Science.gov (United States)

    Adair, Robert; Chase, L. L.; Payne, Stephen A.

    1989-02-01

    The nonlinear refractive indices (n2) of a large number of optical crystals have been measured at a wavelength near one micrometer with use of nearly degenerate three-wave mixing. The measurements are compared with the predictions of an empirical formula derived by Boling, Glass, and Owyoung. This formula, which relates n2 to the linear refractive index and its dispersion, is shown to be accurate to within about 30% for materials with nonlinear indices ranging over 3 orders of magnitude. Measurements for a number of binary oxide and fluoride crystals have been analyzed under the assumption that the hyperpolarizability of the anion is much larger than that of the cation. It is found that the hyperpolarizability of oxygen varies by a factor of 10, and that of fluorine varies by a factor of 7, depending on the size of the coordinating cation. This behavior is similar to that of the linear polarizability, although the hyperpolarizability is much more sensitive than the linear polarizability to the identity of the cation. The measured halide ion hyperpolarizabilities for several alkali-halide crystals are in reasonable agreement with recent self-consistent calculations. A semiempirical model was proposed by Wilson and Curtis to account for the dependence of the linear anionic polarizability on the radius of the cation. This model also accounts quite well for the variation of the hyperpolarizability of both fluorine and oxygen, except for cation partners that have filled or unfilled d-electron shells. The nonlinear indices of a number of complex oxides (i.e., those with more than one cation) have been calculated from the partial hyperpolarizabilities deduced from the data for the binary oxides. The calculated and measured values of n2 agree to within an average error of 13%.

  10. Synthesis, Crystal Structure, and Nonlinear Optical Properties of a New Alkali and Alkaline Earth Metal Carbonate RbNa5Ca5(CO38

    Directory of Open Access Journals (Sweden)

    Qiaoling Chen

    2016-12-01

    Full Text Available A new nonlinear optical (NLO material, RbNa5Ca5(CO38, has been synthesized by the hydrothermal method. The crystal structure is established by single-crystal X-ray diffraction. RbNa5Ca5(CO38 crystallizes in the hexagonal crystal system with space group P63mc (No. 186. The structure of RbNa5Ca5(CO38 can be described as the adjacent infinite [CaCO3]∞ layers lying in the a-b plane bridged through standing-on-edge [CO3] groups by sharing O atoms (two-fold coordinated to build a framework with four types of tunnels running through the b-axis. The Rb, Na, and [Na0.67Ca0.33] atoms reside in these tunnels, respectively. The measurement of second harmonic generation (SHG indicated that RbNa5Ca5(CO38 is a phase-matchable material, which had SHG responses of approximately 1×KH2PO4 (KDP. Meanwhile, the results from the UV-VIS diffuse reflectance spectroscopy study of the powder samples indicated that the UV cut-off edges of RbNa5Ca5(CO38 is about 203 nm.

  11. Crystal structures of hydrates of simple inorganic salts. III. Water-rich aluminium halide hydrates: AlCl3 · 15H2O, AlBr3 · 15H2O, AlI3 · 15H2O, AlI3 · 17H2O and AlBr3 · 9H2O.

    Science.gov (United States)

    Schmidt, Horst; Hennings, Erik; Voigt, Wolfgang

    2014-09-01

    Water-rich aluminium halide hydrate structures are not known in the literature. The highest known water content per Al atom is nine for the perchlorate and fluoride. The nonahydrate of aluminium bromide, stable pentadecahydrates of aluminium chloride, bromide and iodide, and a metastable heptadecahydrate of the iodide have now been crystallized from low-temperature solutions. The structures of these hydrates were determined and are discussed in terms of the development of cation hydration spheres. The pentadecahydrate of the chloride and bromide are isostructural. In AlI(3) · 15H2O, half of the Al(3+) cations are surrounded by two complete hydration spheres, with six H2O in the primary and 12 in the secondary. For the heptadecahydrate of aluminium iodide, this hydration was found for every Al(3+).

  12. Synthesis, Crystal Structure, Vibrational Spectroscopy and Thermal Behavior of the First Alkali Metal Hydrated Hexaborate: K2[B6O9(OH)2

    Institute of Scientific and Technical Information of China (English)

    LI,Hong-Juan; LIU,Zhi-Hong; SUN,Li-Mei

    2007-01-01

    New hydrated potassium hexaborate K2[B6O9(OH)2] has been synthesized under mild solvothermal conditions.The structure was determined by single-crystal X-ray diffraction and further characterized by FT-IR, Raman spectra and DTA-TG. It crystallizes in the monoclinic system with space group P21/n, a=0.9036(2) nm, b=0.66052(18)nm, c= 1.5997(4) nm, β=91.862(4)°, V=0.9543(4) nm3 and Z=4. Its crystal structure consists of K-O polyhedra and 1-D stepped polyborate chains constructed by new [B6O9(OH)2]2- fundamental building blocks. 1-D polyborate chains contain 3,8-membered boron rings. Adjacent chains are further linked via H-bonding interactions into 2-D layers. The K+ cations reside not only between the layers but also in the 8-membered boron rings of the chains,compensating the negative charges of the borate chains and holding the layers together into the 3-D structure through bonding with oxygen atoms of the chains.

  13. Self-Correction of Lanthanum-Cerium Halide Gamma Spectra (pre-print)

    Energy Technology Data Exchange (ETDEWEB)

    Ding Yuan, Paul Guss, and Sanjoy Mukhopadhyay

    2009-04-01

    Lanthanum-cerium halide detectors generally exhibit superior energy resolutions for gamma radiation detection compared with conventional sodium iodide detectors. However, they are also subject to self-activities due to lanthanum-138 decay and contamination due to beta decay in the low-energy region and alpha decay in the high-energy region. The detector’s self-activity and crystal contamination jointly contribute a significant amount of uncertainties to the gamma spectral measurement and affect the precision of the nuclide identification process. This paper demonstrates a self-correction procedure for self-activity and contamination reduction from spectra collected by lanthanum-cerium halide detectors. It can be implemented as an automatic self-correction module for the future gamma radiation detector made of lanthanum-cerium halide crystals.

  14. Halogen versus halide electronic structure

    Institute of Scientific and Technical Information of China (English)

    Willem-Jan; van; Zeist; F.Matthias; Bickelhaupt

    2010-01-01

    Halide anions X-are known to show a decreasing proton affinity(PA),as X descends in the periodic table along series F,Cl,Br and I.But it is also well-known that,along this series,the halogen atom X becomes less electronegative(or more electropositive).This corresponds to an increasing energy of the valence np atomic orbital(AO) which,somewhat contradictorily,suggests that the electron donor capability and thus the PA of the halides should increase along the series F,Cl,Br,I.To reconcile these contradictory observations,we have carried out a detailed theoretical analysis of the electronic structure and bonding capability of the halide anions X-as well as the halogen radicals X-,using the molecular orbital(MO) models contained in Kohn-Sham density functional theory(DFT,at SAOP/TZ2P as well as OLYP/TZ2P levels) and ab initio theory(at the HF/TZ2P level).We also resolve an apparent intrinsic contradiction in Hartree-Fock theory between orbital-energy and PA trends.The results of our analyses are of direct relevance for understanding elementary organic reactions such as nucleophilic substitution(SN2) and base-induced elimination(E2) reactions.

  15. Alkali and Halogen Chemistry in Volcanic Gases on Io

    CERN Document Server

    Schaefer, L

    2004-01-01

    We use chemical equilibrium calculations to model the speciation of alkalis and halogens in volcanic gases emitted on Io. The calculations cover wide temperature (500-2000 K) and pressure (10^-6 to 10^+1 bars) ranges, which overlap the nominal conditions at Pele (T = 1760 K, P = 0.01 bars). About 230 compounds of 11 elements (O, S, Li, Na, K, Rb, Cs, F, Cl, Br, I) are considered. We predict the major alkali and halogen species in a Pele-like volcanic gas and the major alklai and halogen condensates. We also model disequilibrium chemistry of the alkalis and halogens in the volcanic plume. Based on this work and our prior modeling for Na, K, and Cl in a volcanic plume, we predict the major loss processes for the alkali halide gases are photolysis and/or condensation onto grains. On the basis of elemental abundances and photochemical lifetimes, we recommend searching for gaseous KCl, NaF, LiF, LiCl, RbF, RbCl, CsF, and CsCl around volcanic vents during eruptions. Based on abundance considerations and observation...

  16. Crystal structures and hydrogen bonding in the isotypic series of hydrated alkali metal (K, Rb and Cs complexes with 4-aminophenylarsonic acid

    Directory of Open Access Journals (Sweden)

    Graham Smith

    2017-02-01

    Full Text Available The structures of the alkali metal (K, Rb and Cs complex salts with 4-aminophenylarsonic acid (p-arsanilic acid manifest an isotypic series with the general formula [M2(C6H7AsNO32(H2O3], with M = K {poly[di-μ3-4-aminophenylarsonato-tri-μ2-aqua-dipotassium], [K2(C6H7AsNO32(H2O3], (I}, Rb {poly[di-μ3-4-aminophenylarsonato-tri-μ2-aqua-dirubidium], [Rb2(C6H7AsNO32(H2O3], (II}, and Cs {poly[di-μ3-4-aminophenylarsonato-tri-μ2-aqua-dirubidium], [Cs2(C6H7AsNO32(H2O3], (III}, in which the repeating structural units lie across crystallographic mirror planes containing two independent and different metal cations and a bridging water molecule, with the two hydrogen p-arsanilate ligands and the second water molecule lying outside the mirror plane. The bonding about the two metal cations in all complexes is similar, one five-coordinate, the other progressing from five-coordinate in (I to eight-coordinate in both (II and (III, with overall M—O bond-length ranges of 2.694 (5–3.009 (7 (K, 2.818 (4–3.246 (4 (Rb and 2.961 (9–3.400 (10 Å (Cs. The additional three bonds in (II and (III are the result of inter-metal bridging through the water ligands. Two-dimensional coordination polymeric structures with the layers lying parallel to (100 are generated through a number of bridging bonds involving the water molecules (including hydrogen-bonding interactions, as well as through the arsanilate O atoms. These layers are linked across [100] through amine N—H...O hydrogen bonds to arsonate and water O-atom acceptors, giving overall three-dimensional network structures.

  17. Recent advances in tailoring the aggregation of heavier alkaline earth metal halides, alkoxides and aryloxides from non-aqueous solvents.

    Science.gov (United States)

    Fromm, Katharina M

    2006-11-21

    This overview on one of the subjects treated in our group deals with the synthesis and study of low-dimensional polymer and molecular solid state structures formed with alkaline earth metal ions in non-aqueous solvents. We have chosen several synthetic approaches in order to obtain such compounds. The first concept deals with the "cutting out" of structural fragments from a solid state structure of a binary compound, which will be explained with reference to BaI2. Depending on the size and concentration of oxygen donor ligands, used as chemical scissors on BaI2, three-, two-, one- and zero-dimensional derived adducts of BaI2 are obtained, comparable to a structural genealogy tree for BaI2. A second part deals with the supramolecular approach for the synthesis of low dimensional polymeric compounds based on alkaline earth metal iodides, obtained by the combination of metal ion coordination with hydrogen bonding between the cationic complexes and their anions. Certain circumstances allow rules to be established for the prediction of the dimensionality of a given compound, contributing to the fundamental problem of structure prediction in crystal engineering. A third section describes a synthetic approach for generating pure alkaline earth metal cage compounds as well as alkali and alkaline earth mixed metal clusters. A first step deals with different molecular solvated alkaline earth metal iodides which are investigated as a function of the ligand size in non-aqueous solvents. These are then reacted with some alkali metal compound in order to partially or totally eliminate alkali iodide and to form the targeted clusters. These unique structures of ligand stabilized metal halide, hydroxide and/or alkoxide and aryloxide aggregates are of interest as potential precursors for oxide materials and as catalysts. Approaches to two synthetic methods of the latter, sol-gel and (MO)CVD (metal-organic chemical vapour deposition), are investigated with some of our compounds. (D

  18. Tris(bipyridineMetal(II-Templated Assemblies of 3D Alkali-Ruthenium Oxalate Coordination Frameworks: Crystal Structures, Characterization and Photocatalytic Activity in Water Reduction

    Directory of Open Access Journals (Sweden)

    Alla Dikhtiarenko

    2016-02-01

    Full Text Available A series of 3D oxalate-bridged ruthenium-based coordination polymers with the formula of {[ZII(bpy3][MIRu(C2O43]}n (ZII = Zn2+ (1, Cu2+ (3, 4, Ru2+ (5, 6, Os2+ (7, 8; MI = Li+, Na+; bpy = 2,2’-bipyridine and {[ZnII(bpy3](H2O[LiRu(C2O43]}n (2 has been synthesized at room temperature through a self-assembly reaction in aqueous media and characterized by single-crystal and powder X-ray diffraction, elemental analysis, infrared and diffuse reflectance UV–Vis spectroscopy and thermogravimetric analysis. The crystal structures of all compounds comprise chiral 3D honeycomb-like polymeric nets of the srs-type, which possess triangular anionic cages where [ZII(bpy3]2+ cationic templates are selectively embedded. Structural analysis reveals that the electronic configuration of the cationic guests is affected by electrostatic interaction with the anionic framework. Moreover, the MLCT bands gaps values for 1–8 can be tuned in a rational way by judicious choice of [ZII(bpy3]2+ guests. The 3D host-guest polymeric architectures can be used as self-supported heterogeneous photocatalysts for the reductive splitting of water, exhibiting photocatalytic activity for the evolution of H2 under UV light irradiation.

  19. ALKALI RESISTANT CATALYST

    DEFF Research Database (Denmark)

    2008-01-01

    The present invention concerns the selective removal of nitrogen oxides (NOx) from gasses. In particular, the invention concerns a process, a catalyst and the use of a catalyst for the selective removal of nitrogen oxides in the presence of ammonia from gases containing a significant amount...... of alkali metal and/or alkali-earth compounds which process comprises using a catalyst combined of (i) a formed porous superacidic support, said superacidic support having an Hammett acidity stronger than Ho=-12, and (ii) a metal oxide catalytic component deposited on said superacidic support selected from...

  20. Local structure of alkalis in mixed-alkali borate glass to elucidate the origin of mixed-alkali effect

    Directory of Open Access Journals (Sweden)

    Yomei Tokuda

    2015-12-01

    Full Text Available We report the structural analysis of Na+ and Cs+ in sodium cesium borate crystals and glasses using 23Na and 133Cs magic-angle spinning nuclear magnetic resonance (MAS NMR spectroscopy. The composition dependence of NMR spectra of the borate was similar to that of the silicate: (1 the peak position of cesium borate crystals shifted to upfield for structures with larger Cs+ coordination numbers, (2 the MAS NMR spectra of xNa2O-yCs2O-3B2O3 (x = 0, 0.25, 0.5, 0.75, 1.0, x + y = 1 glass showed that the average coordination number (CN of both the alkali cations decreases with increasing Cs+/(Na+ + Cs+ ratio. However, the degree of decrement in borates is much smaller than that in silicates. We have considered that the small difference in CN is due to 4-coordinated B, because it is electrically compensated by the alkali metal ions resulting in the restriction of having various coordinations of O to alkali metal.

  1. Perspectives on organolead halide perovskite photovoltaics

    Science.gov (United States)

    Hariz, Alex

    2016-07-01

    A number of photovoltaic technologies have been developed for large-scale solar-power production. The single-crystal first-generation photovoltaic devices were followed by thin-film semiconductor absorber layers layered between two charge-selective contacts, and more recently, by nanostructured or mesostructured solar cells that utilize a distributed heterojunction to generate charge carriers and to transport holes and electrons in spatially separated conduits. Even though a number of materials have been trialed in nanostructured devices, the aim of achieving high-efficiency thin-film solar cells in such a manner as to rival the silicon technology has yet to be attained. Organolead halide perovskites have recently emerged as a promising material for high-efficiency nanoinfiltrated devices. An examination of the efficiency evolution curve reveals that interfaces play a paramount role in emerging organic electronic applications. To optimize and control the performance in these devices, a comprehensive understanding of the contacts is essential. However, despite the apparent advances made, a fundamental theoretical analysis of the physical processes taking place at the contacts is still lacking. However, experimental ideas, such as the use of interlayer films, are forging marked improvements in efficiencies of perovskite-based solar cells. Furthermore, issues of long-term stability and large-area manufacturing have some way to go before full commercialization is possible.

  2. 四川平武富碱型绿柱石晶体的晶格缺陷与生长机制%CRYSTAL DEFECT AND GROWTH MECHANISM OF ALKALI-RICH BERYL CRYSTAL FROM PINGWU,SICHUAN,CHIAN

    Institute of Scientific and Technical Information of China (English)

    亓利剑; 裴景成; 石国华; 罗永安; 周开灿

    2001-01-01

    在低饱和度、碱性、气成—热液条件下形成的四川平武绿柱石宝石晶体,具有特征的扁平板状几何外形。在绿柱石晶体的{0001}、{1010}、{1121}面上,普遍发育螺旋位错、束合螺旋位错、层错及接触双晶,它们共同构成了绿柱石晶体生长的主要台阶源。微分干涉显微镜、扫描电镜和透射电镜研究结果证实,由填隙变形、位错滑移和水解弱化等综合作用,直接导致绿柱石硅氧四面体六方环结构和铍氧四面体结构的局部畸变,并相应引起多面体体积、化学键力、键合能及晶面的法向生长速率发生变化,从而决定了该区绿柱石晶体生长的形态。由绿柱石晶体中的线缺陷(螺旋位错)、面缺陷(层错、双晶)及点缺陷(空位、包裹体)的协同作用,是导致四川平武扁平板状绿柱石晶体形成的主要原因。%The beryl crystal from Pingwu County,Sichuan Province that occurred on the low-saturation,alkaline and pneumatogenic—thermal conditions,is characterized by the flat tabular shape.On the crystal surfaces of the beryl crystal at {0001},{1010},{1121} occur universally screw dislocation,constriction screw dislocation,stacking fault,and contact twin that serve as the major step-like source for the growth of beryl crystal.The research results obtained through differential interference microscope,scanning electron microscope,and transmission electron microscope show that the comprehensive effects of interstitial deformation,dislocation sliding and hydrolytic weakening lead directly to the local deformation of the silica tetrahedral hexagonal ring-like structure and the beryllium oxide tetragonal structure,and at the same time to the change in polyhedral volume,chemical bond force,bonding energy,and in the normal growth rate of the crystal face.These changes determine the morphology of the beryl crystal growth in this zone.The formation of the flat

  3. The calcium-alkali syndrome

    OpenAIRE

    Arroyo, Mariangeli; Fenves, Andrew Z.; Emmett, Michael

    2013-01-01

    The milk-alkali syndrome was a common cause of hypercalcemia, metabolic alkalosis, and renal failure in the early 20th century. It was caused by the ingestion of large quantities of milk and absorbable alkali to treat peptic ulcer disease. The syndrome virtually vanished after introduction of histamine-2 blockers and proton pump inhibitors. More recently, a similar condition called the calcium-alkali syndrome has emerged as a common cause of hypercalcemia and alkalosis. It is usually caused b...

  4. Epitaxial Halide Perovskite Lateral Double Heterostructure.

    Science.gov (United States)

    Wang, Yiping; Chen, Zhizhong; Deschler, Felix; Sun, Xin; Lu, Toh-Ming; Wertz, Esther A; Hu, Jia-Mian; Shi, Jian

    2017-03-28

    Epitaxial III-V semiconductor heterostructures are key components in modern microelectronics, electro-optics, and optoelectronics. With superior semiconducting properties, halide perovskite materials are rising as promising candidates for coherent heterostructure devices. In this report, spinodal decomposition is proposed and experimentally implemented to produce epitaxial double heterostructures in halide perovskite system. Pristine epitaxial mixed halide perovskites rods and films were synthesized via van der Waals epitaxy by chemical vapor deposition method. At room temperature, photon was applied as a knob to regulate the kinetics of spinodal decomposition and classic coarsening. By this approach, halide perovskite double heterostructures were created carrying epitaxial interfaces and outstanding optical properties. Reduced Fröhlich electron-phonon coupling was discovered in coherent halide double heterostructure, which is hypothetically attributed to the classic phonon confinement effect widely existing in III-V double heterostructures. As a proof-of-concept, our results suggest that halide perovskite-based epitaxial heterostructures may be promising for high-performance and low-cost optoelectronics, electro-optics, and microelectronics. Thus, ultimately, for practical device applications, it may be worthy to pursue these heterostructures via conventional vapor phase epitaxy approaches widely practised in III-V field.

  5. Alkali Aggregate Reaction in Alkali Slag Cement Mortars

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    By means of "Mortar Bar Method",the ratio of cement to aggregate was kept as a constant 1∶2.25,the water-cement ratio of the mixture was 0.40,and six prism specimens were prepared for each batch of mixing proportions with dimensions of 10×10×60mm3 at 38±2℃ and RH≥95%, the influences of content and particle size of active aggregate, sort and content of alkali component and type of slag on the expansion ratios of alkali-activated slag cement(ASC) mortars due to alkali aggregate reaction(AAR) were studied. According to atomic absorption spectrometry,the amount of free alkali was measured in ASC mortars at 90d.The results show above factors affect AAR remarkably,but no dangerous AAR will occur in ASC system when the amount of active aggregate is below 15% and the mass fraction of alkali is not more than 5% (Na2O).Alkali participated in reaction as an independent component, and some hydrates containing alkali cations were produced, free alkalis in ASC system can be reduced enormously.Moreover,slag is an effective inhibitor, the possibility of generating dangerous AAR in ASC system is much lower at same conditions than that in ordinary Portland cement system.

  6. Natural Alkali Shifts to the Methanol Business

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    @@ Inner Mongolia Yuanxing Natural Alkali Co., Ltd. (Natural Alkali SZ: 000683) established in 1997 is a large chemical enterprise with new energy as its leading business and natural gas chemicals and natural alkali chemicals as the supplement business.

  7. Double-Diffusive Convection During Growth of Halides and Selenides

    Science.gov (United States)

    Singh, N. B.; Su, Ching-Hua; Duval, Walter M. B.

    2015-01-01

    Heavy metal halides and selenides have unique properties which make them excellent materials for chemical, biological and radiological sensors. Recently it has been shown that selenohalides are even better materials than halides or selenides for gamma-ray detection. These materials also meet the strong needs of a wide band imaging technology to cover ultra-violet (UV), midwave infrared wavelength (MWIR) to very long wavelength infrared (VLWIR) region for hyperspectral imager components such as etalon filters and acousto-optic tunable filters (AO). In fact AOTF based imagers based on these materials have some superiority than imagers based on liquid crystals, FTIR, Fabry-Perot, grating, etalon, electro-optic modulation, piezoelectric and several other concepts. For example, broadband spectral and imagers have problems of processing large amount of information during real-time observation. Acousto-Optic Tunable Filter (AOTF) imagers are being developed to fill the need of reducing processing time of data, low cost operation and key to achieving the goal of covering long-wave infrared (LWIR). At the present time spectral imaging systems are based on the use of diffraction gratings are typically used in a pushbroom or whiskbroom mode. They are mostly used in systems and acquire large amounts of hyperspectral data that is processed off-line later. In contrast, acousto-optic tunable filter spectral imagers require very little image processing, providing new strategies for object recognition and tracking. They are ideally suited for tactical situations requiring immediate real-time image processing. But the performance of these imagers depends on the quality and homogeneity of acousto-optic materials. In addition for many systems requirements are so demanding that crystals up to sizes of 10 cm length are desired. We have studied several selenides and halide crystals for laser and AO imagers for MWIR and LWIR wavelength regions. We have grown and fabricated crystals of

  8. Band gap expansion, shear inversion phase change behaviour and low-voltage induced crystal oscillation in low-dimensional tin selenide crystals.

    Science.gov (United States)

    Carter, Robin; Suyetin, Mikhail; Lister, Samantha; Dyson, M Adam; Trewhitt, Harrison; Goel, Sanam; Liu, Zheng; Suenaga, Kazu; Giusca, Cristina; Kashtiban, Reza J; Hutchison, John L; Dore, John C; Bell, Gavin R; Bichoutskaia, Elena; Sloan, Jeremy

    2014-05-28

    In common with rocksalt-type alkali halide phases and also semiconductors such as GeTe and SnTe, SnSe forms all-surface two atom-thick low dimensional crystals when encapsulated within single walled nanotubes (SWNTs) with diameters below ∼1.4 nm. Whereas previous density functional theory (DFT) studies indicate that optimised low-dimensional trigonal HgTe changes from a semi-metal to a semi-conductor, low-dimensional SnSe crystals typically undergo band-gap expansion. In slightly wider diameter SWNTs (∼1.4-1.6 nm), we observe that three atom thick low dimensional SnSe crystals undergo a previously unobserved form of a shear inversion phase change resulting in two discrete strain states in a section of curved nanotube. Under low-voltage (i.e. 80-100 kV) imaging conditions in a transmission electron microscope, encapsulated SnSe crystals undergo longitudinal and rotational oscillations, possibly as a result of the increase in the inelastic scattering cross-section of the sample at those voltages.

  9. Crystal Electrostatic Energy

    CERN Document Server

    Ivanchin, Alexander

    2010-01-01

    It has been shown that to calculate the parameters of the electrostatic field of the ion crystal lattice it sufficient to take into account ions located at a distance of 1-2 lattice spacings. More distant ions make insignificant contribution. As a result, the electrostatic energy of the ion lattice in the alkaline halide crystal produced by both positive and negative ions is in good agreement with experiment when the melting temperature and the shear modulus are calculated. For fcc and bcc metals the ion lattice electrostatic energy is not sufficient to obtain the observed values of these parameters. It is possible to resolve the contradiction if one assumes that the electron density is strongly localized and has a crystal structure described by the lattice delta - function. As a result, positive charges alternate with negative ones as in the alkaline halide crystal. Such delta-like localization of the electron density is known as a model of nearly free electrons.

  10. Photonic Nanostructures Patterned by Thermal Nanoimprint Directly into Organo-Metal Halide Perovskites.

    Science.gov (United States)

    Pourdavoud, Neda; Wang, Si; Mayer, André; Hu, Ting; Chen, Yiwang; Marianovich, André; Kowalsky, Wolfgang; Heiderhoff, Ralf; Scheer, Hella-Christin; Riedl, Thomas

    2017-03-01

    Photonic nanostructures are created in organo-metal halide perovskites by thermal nanoimprint lithography at a temperature of 100 °C. The imprinted layers are significantly smoothened compared to the initially rough, polycrystalline layers and the impact of surface defects is substantially mitigated upon imprint. As a case study, 2D photonic crystals are shown to afford lasing with ultralow lasing thresholds at room temperature.

  11. Atomic Resolution Imaging of Halide Perovskites.

    Science.gov (United States)

    Yu, Yi; Zhang, Dandan; Kisielowski, Christian; Dou, Letian; Kornienko, Nikolay; Bekenstein, Yehonadav; Wong, Andrew B; Alivisatos, A Paul; Yang, Peidong

    2016-12-14

    The radiation-sensitive nature of halide perovskites has hindered structural studies at the atomic scale. We overcome this obstacle by applying low dose-rate in-line holography, which combines aberration-corrected high-resolution transmission electron microscopy with exit-wave reconstruction. This technique successfully yields the genuine atomic structure of ultrathin two-dimensional CsPbBr3 halide perovskites, and a quantitative structure determination was achieved atom column by atom column using the phase information of the reconstructed exit-wave function without causing electron beam-induced sample alterations. An extraordinarily high image quality enables an unambiguous structural analysis of coexisting high-temperature and low-temperature phases of CsPbBr3 in single particles. On a broader level, our approach offers unprecedented opportunities to better understand halide perovskites at the atomic level as well as other radiation-sensitive materials.

  12. Harmonic dynamical behaviour of thallous halides

    Indian Academy of Sciences (India)

    Sarvesh K Tiwari; L J Shukla; K S Upadhyaya

    2010-05-01

    Harmonic dynamical behaviour of thallous halides (TlCl and TlBr) have been studied using the new van der Waals three-body force shell model (VTSM), which incorporates the effects of the van der Waals interaction along with long-range Coulomb interactions, three-body interactions and short-range second neighbour interactions in the framework of rigid shell model (RSM). Phonon dispersion curves (PDC), variations of Debye temperature with absolute temperature and phonon density of state (PDS) curves have been reported for thallous halides using VTSM. Comparison of experimental values with those of VTSM and TSM are also reported in the paper and a good agreement between experimental and VTSM values has been found, from which it may be inferred that the incorporation of van der Waals interactions is essential for the complete harmonic dynamical behaviour of thallous halides.

  13. Low-threshold amplified spontaneous emission and lasing from colloidal nanocrystals of caesium lead halide perovskites

    Science.gov (United States)

    Yakunin, Sergii; Protesescu, Loredana; Krieg, Franziska; Bodnarchuk, Maryna I.; Nedelcu, Georgian; Humer, Markus; de Luca, Gabriele; Fiebig, Manfred; Heiss, Wolfgang; Kovalenko, Maksym V.

    2015-08-01

    Metal halide semiconductors with perovskite crystal structures have recently emerged as highly promising optoelectronic materials. Despite the recent surge of reports on microcrystalline, thin-film and bulk single-crystalline metal halides, very little is known about the photophysics of metal halides in the form of uniform, size-tunable nanocrystals. Here we report low-threshold amplified spontaneous emission and lasing from ~10 nm monodisperse colloidal nanocrystals of caesium lead halide perovskites CsPbX3 (X=Cl, Br or I, or mixed Cl/Br and Br/I systems). We find that room-temperature optical amplification can be obtained in the entire visible spectral range (440-700 nm) with low pump thresholds down to 5+/-1 μJ cm-2 and high values of modal net gain of at least 450+/-30 cm-1. Two kinds of lasing modes are successfully observed: whispering-gallery-mode lasing using silica microspheres as high-finesse resonators, conformally coated with CsPbX3 nanocrystals and random lasing in films of CsPbX3 nanocrystals.

  14. Theory of hydrogen migration in organic-inorganic halide perovskites.

    Science.gov (United States)

    Egger, David A; Kronik, Leeor; Rappe, Andrew M

    2015-10-12

    Solar cells based on organic-inorganic halide perovskites have recently been proven to be remarkably efficient. However, they exhibit hysteresis in their current-voltage curves, and their stability in the presence of water is problematic. Both issues are possibly related to a diffusion of defects in the perovskite material. By using first-principles calculations based on density functional theory, we study the properties of an important defect in hybrid perovskites-interstitial hydrogen. We show that differently charged defects occupy different crystal sites, which may allow for ionization-enhanced defect migration following the Bourgoin-Corbett mechanism. Our analysis highlights the structural flexibility of organic-inorganic perovskites: successive iodide displacements, combined with hydrogen bonding, enable proton diffusion with low migration barriers. These findings indicate that hydrogen defects can be mobile and thus highly relevant for the performance of perovskite solar cells.

  15. Upgrading platform using alkali metals

    Energy Technology Data Exchange (ETDEWEB)

    Gordon, John Howard

    2017-01-17

    A method for removing sulfur, nitrogen or metals from an oil feedstock. The method involves reacting the oil feedstock with an alkali metal and a radical capping substance. The alkali metal reacts with the metal, sulfur or nitrogen content to form one or more inorganic products and the radical capping substance reacts with the carbon and hydrogen content to form a hydrocarbon phase. The inorganic products may then be separated out from the hydrocarbon phase.

  16. Upgrading platform using alkali metals

    Energy Technology Data Exchange (ETDEWEB)

    Gordon, John Howard

    2014-09-09

    A process for removing sulfur, nitrogen or metals from an oil feedstock (such as heavy oil, bitumen, shale oil, etc.) The method involves reacting the oil feedstock with an alkali metal and a radical capping substance. The alkali metal reacts with the metal, sulfur or nitrogen content to form one or more inorganic products and the radical capping substance reacts with the carbon and hydrogen content to form a hydrocarbon phase. The inorganic products may then be separated out from the hydrocarbon phase.

  17. Role of Dispersive Interactions in Determining Structural Properties of Organic-Inorganic Halide Perovskites: Insights from First-Principles Calculations.

    Science.gov (United States)

    Egger, David A; Kronik, Leeor

    2014-08-07

    A microscopic picture of structure and bonding in organic-inorganic perovskites is imperative to understanding their remarkable semiconducting and photovoltaic properties. On the basis of a density functional theory treatment that includes both spin-orbit coupling and dispersive interactions, we provide detailed insight into the crystal binding of lead-halide perovskites and quantify the effect of different types of interactions on the structural properties. Our analysis reveals that cohesion in these materials is characterized by a variety of interactions that includes important contributions from both van der Waals interactions among the halide atoms and hydrogen bonding. We also assess the role of spin-orbit coupling and show that it causes slight changes in lead-halide bonding that do not significantly affect the lattice parameters. Our results establish that consideration of dispersive effects is essential for understanding the structure and bonding in organic-inorganic perovskites in general and for providing reliable theoretical predictions of structural parameters in particular.

  18. Effect of Alkali Treatment on the Structure and Catalytic Properties of ZSM-5 Zeolite

    Institute of Scientific and Technical Information of China (English)

    Zi Yun LI; Xin SUN; Qiang XIAO; Shou He XIANG

    2005-01-01

    Catalytic properties of ZSM-5 zeolite samples pretreated with NaOH solution have been investigated. The samples are characterized by XRD, SEM, chemical analysis, and N2 adsorption.The results indicate that mesopores are created in ZSM-5 crystals under alkali treatment without change the microporous structure and acidic strength of the zeolite, but the crystallinity is greatly decreased under severe treatment. IR indicates that the concentration of silanol is greatly enriched by alkali treatment. The etherification activities of ZSM-5 zeolites are greatly increased by alkali-treatment. The noticeably improved catalytic activity of treated samples is ascribed to the formation of mesopores and greatly enriched silanol group.

  19. Trace Element Geochemistry of Hannuoba Ultramafic Inclusion—bearing Alkali Basalts

    Institute of Scientific and Technical Information of China (English)

    支霞臣

    1990-01-01

    Presented in this paper are the trace element abundances of 16 samples of Hannuoba ultramafic inclusion-bearing aldali basalts,which were determined by instrumental neutron activation analysis and X-ray fluorescence spectrometry.The Petrogenesis of the alkali basalt suite has been modeled by batch partial melting and and Rayleigh fractional crystallization processes,The geochemical characteristics of the mantle source from where alkali basalts were derived are described in terms of variations in trace element abundances of the alkali basalt suite.

  20. Pathways of birnessite formation in alkali medium

    Institute of Scientific and Technical Information of China (English)

    FENG Xionghan; TAN Wenfeng; LIU Fan; HUANG Qiaoyun; LIU Xiangwen

    2005-01-01

    Birnessite is a common weathering and oxidation product of manganese-bearing rocks. An O2 oxidation procedure of Mn(OH)2 in the alkali medium has been used to synthesize birnessite. Fast and powder X-ray diffraction (XRD), transmission electron microscopy (TEM), electron diffraction (ED), energy dispersed X-ray analysis (EDAX), infrared spectroscopy (IR) techniques and chemical composition analysis, Eh-pH equilibrium diagram approaches were employed to investigate the reaction process and pathways of birnessite formation. Results showed that the process of the birnessite formation could be divided into four stages: (1) formation stage for hausmannite and feitknechtite, (2) stage of transformation of hausmannite and feitknechtite to buserite, (3) buserite crystal growing stage, and (4) stage of conversion of buserite into birnessite. Mn(OH)2 was mainly present as amorphous state only for a short initial time of oxidation reaction. In the oxidation process, buserite formed following two pathways by recrystallization after dissolution of the intermediates, and the transformations of the minerals depended on the Eh determined by the dissolved O2 concentration on their surfaces. The results are fundamental in further exploration on the mechanism of birnessite formation in the alkali medium. A great practical significance would also be expected with respect to the areas of material sciences.

  1. Heteroepitaxial strain in alkali halide thin films: KCl on NaCl

    DEFF Research Database (Denmark)

    Baker, J.; Lindgård, Per-Anker

    1999-01-01

    We have pet-formed Monte Carlo simulations of the properties of a NaCl (001) surface covered by full or partial layers of KCl, for coverages up to 5 monolayers (ML). A wide variety of structures of the film is found. For integer ML coverages we find the continuous, so-called floating mode rumple...... structure, as was previously found in the KBr/NaCl system. However, for a coverage of similar to 2.1 ML, we find a discrete structure of periodicity 3:4 of small regularly spaced KCl pyramids. It has the same scattering characteristics as the structure observed by Henzler et al. [Phys. Rev. B 52, 17 060...... (1995)], but it is two-dimensional modulated, rather than the rowlike stacking fault structure proposed by Henzler et al. Also, at a coverage of similar to 0.8 ML there is a stable 3:4 structure. Other structures are found at intermediate coverages, corresponding to regular arrays of dislocation lines...

  2. Interaction of the model alkyltrimethylammonium ions with alkali halide salts: an explicit water molecular dynamics study

    Directory of Open Access Journals (Sweden)

    M. Druchok

    2013-01-01

    Full Text Available We present an explicit water molecular dynamics simulation of dilute solutions of model alkyltrimethylammonium surfactant ions (number of methylene groups in the tail is 3, 5, 8, 10, and 12 in mixture with NaF, NaCl, NaBr, and NaI salts, respectively. The SPC/E model is used to describe water molecules. Results of the simulation at 298 K are presented in form of the radial distribution functions between nitrogen and carbon atoms of CH2 groups on the alkyltrimethylammonium ion, and the counterion species in the solution. The running coordination numbers between carbon atoms of surfactants and counterions are also calculated. We show that I- counterion exhibits the highest, and F- the lowest affinity to "bind" to the model surfactants. The results are discussed in view of the available experimental and simulation data for this and similar solutions.

  3. THE EFFECT OF ALKALI METAL HALIDES ON THE STRUCTURE OF GLYCEROL FROM VISCOSITY B COEFFICIENT MEASUREMENTS

    Directory of Open Access Journals (Sweden)

    A HAMMADI

    2002-12-01

    Full Text Available Viscosity B‑coefficients in glycerol obtained at 25 °C for many salts by a rearrangement in the Jones‑Dole expression are compared with those calculated applying existing theories, based on the model of hard‑charged spheres moving in a solvent continuum. Specific agreement between theory and experiment was not generally good. While the results show that Einstein’s relation can be applied to large aqueous ions, provided that the true volume‑fraction of the ions in solution can be ascertained; this expression does not lead to accurate B‑values in glycerol. For the ion‑size dependence of the B‑coefficient in aqueous solutions, Clark’s theoretical predictions agree with experiments qualitatively, in the case of glycerol, however, the model shows limitations even for small ions, for which the dielectric friction theory is expected to be applicable. Finally, all the above theories give a positive B‑coefficient, while experimental evidences showed that B could be negative.

  4. Raman scattering and quantum confinement in heavily electron-irradiated alkali halides

    NARCIS (Netherlands)

    Shtyrkov, E.I.; Klimovitskii, A.; Hartog, H.W. den; Vainshtein, D.I.

    2002-01-01

    In this paper we will study the properties of several unusual Raman scattering peaks in heavily irradiated NaCl with vast amounts of colloidal sodium and chlorine precipitates. It appears that the laser excitation light interacts with both the electronic and vibration systems of the Na colloids, whi

  5. Dimensional reductions from 2-D Nb 4P 2S 21 to 1-D ANb 2PS 10 ( A=Na, K, Rb, Cs, Tl) and to 0-D Tl 5[Nb 2S 4C l8]Cl using halide molten salts

    Science.gov (United States)

    Bang, Hyunjin; Kim, Youngmee; Kim, Seri; Kim, Sung-Jin

    2008-08-01

    We found new synthetic routes to obtain 1-D quaternary thiophosphate compounds and a 0-D molecular complex containing a Nb 2S 4 core from a 2-D ternary thiophosphate, Nb 4P 2S 21. When Nb 4P 2S 21 was reacted with alkali metal halides ( ACl; A=Na, K, Rb, Cs) or TlCl at 500-700 °C, the -S-S-S- bridges in 2-D Nb 2PS 10-S-S 10PNb 2 were excised to form a 1-D chain, and cations were inserted between the chains to form ANb 2PS 10 ( A=Na, K, Rb, Cs, Tl). We also found that thallium chloride (TlCl) is an excellent reagent for further excision, and it substitutes chloride ligands for the sulfur ligands of 2-D Nb 4P 2S 21 to form the molecular complex Tl 5[Nb 2S 4Cl 8]Cl. Crystal data for TlNb 2PS 10: monoclinic, Pn, a=6.9452(11) Å, b=7.3761(12) Å, 12.873(2) Å, β=104.472(3)°, and Z=2. Crystal data for Tl 5[Nb 2S 4Cl 8]Cl: orthorhombic, Immm, a=7.001(5) Å, b=9.509(7) Å, c=15.546(11) Å, and Z=2.

  6. Lanthanide-halide based humidity indicators

    Science.gov (United States)

    Beitz, James V.; Williams, Clayton W.

    2008-01-01

    The present invention discloses a lanthanide-halide based humidity indicator and method of producing such indicator. The color of the present invention indicates the humidity of an atmosphere to which it is exposed. For example, impregnating an adsorbent support such as silica gel with an aqueous solution of the europium-containing reagent solution described herein, and dehydrating the support to dryness forms a substance with a yellow color. When this substance is exposed to a humid atmosphere the water vapor from the air is adsorbed into the coating on the pore surface of the silica gel. As the water content of the coating increases, the visual color of the coated silica gel changes from yellow to white. The color change is due to the water combining with the lanthanide-halide complex on the pores of the gel.

  7. Chiral Alkyl Halides: Underexplored Motifs in Medicine

    Directory of Open Access Journals (Sweden)

    Bálint Gál

    2016-11-01

    Full Text Available While alkyl halides are valuable intermediates in synthetic organic chemistry, their use as bioactive motifs in drug discovery and medicinal chemistry is rare in comparison. This is likely attributable to the common misconception that these compounds are merely non-specific alkylators in biological systems. A number of chlorinated compounds in the pharmaceutical and food industries, as well as a growing number of halogenated marine natural products showing unique bioactivity, illustrate the role that chiral alkyl halides can play in drug discovery. Through a series of case studies, we demonstrate in this review that these motifs can indeed be stable under physiological conditions, and that halogenation can enhance bioactivity through both steric and electronic effects. Our hope is that, by placing such compounds in the minds of the chemical community, they may gain more traction in drug discovery and inspire more synthetic chemists to develop methods for selective halogenation.

  8. The influence of halides in polyoxotitanate cages; dipole moment, splitting and expansion of d-orbitals and electron-electron repulsion.

    Science.gov (United States)

    Hanf, Schirin; Matthews, Peter D; Li, Ning; Luo, He-Kuan; Wright, Dominic S

    2017-01-03

    Metal-doped polyoxotitanate (M-POT) cages have been shown to be efficient single-source precursors to metal-doped titania [TiO2(M)] (state-of-the-art photocatalytic materials) as well as molecular models for the behaviour of dopant metal ions in bulk titania. Here we report the influence halide ions have on the optical and electronic properties of a series of halide-only, and cobalt halide-'doped' POT cages. In this combined experimental and computational study we show that halide ions can have several effects on the band gaps of halide-containing POT cages, influencing the dipole moment (hole-electron separation) and the structure of the valance band edge. Overall, the band gap behaviour stems from the effects of increasing orbital energy moving from F to I down Group 17, as well as crystal-field splitting of the d-orbitals, the potential effects of the Nephelauxetic influence of the halides and electron-electron repulsion.

  9. Process for recovering alkali metals and sulfur from alkali metal sulfides and polysulfides

    Energy Technology Data Exchange (ETDEWEB)

    Gordon, John Howard; Alvare, Javier

    2016-10-25

    Alkali metals and sulfur may be recovered from alkali monosulfide and polysulfides in an electrolytic process that utilizes an electrolytic cell having an alkali ion conductive membrane. An anolyte solution includes an alkali monosulfide, an alkali polysulfide, or a mixture thereof and a solvent that dissolves elemental sulfur. A catholyte includes molten alkali metal. Applying an electric current oxidizes sulfide and polysulfide in the anolyte compartment, causes alkali metal ions to pass through the alkali ion conductive membrane to the catholyte compartment, and reduces the alkali metal ions in the catholyte compartment. Liquid sulfur separates from the anolyte solution and may be recovered. The electrolytic cell is operated at a temperature where the formed alkali metal and sulfur are molten.

  10. A negative ion source for alkali ions

    NARCIS (Netherlands)

    Vermeer, A.; Zwol, N.A. van

    1980-01-01

    An ion source is described which delivers negative alkali ions. With this source, which consists of a duoplasmatron and a charge exchange canal with alkali vapour, negative Li, Na and K ions are produced. The oven in which alkali metals are evaporated can reach temperatures up to 575°C.

  11. Alkali binding in hydrated Portland cement paste

    NARCIS (Netherlands)

    Chen, W.; Brouwers, H.J.H.

    2010-01-01

    The alkali-binding capacity of C–S–H in hydrated Portland cement pastes is addressed in this study. The amount of bound alkalis in C–S–H is computed based on the alkali partition theories firstly proposed by Taylor (1987) and later further developed by Brouwers and Van Eijk (2003). Experimental data

  12. Lanthanide doped strontium-barium cesium halide scintillators

    Science.gov (United States)

    Bizarri, Gregory; Bourret-Courchesne, Edith; Derenzo, Stephen E.; Borade, Ramesh B.; Gundiah, Gautam; Yan, Zewu; Hanrahan, Stephen M.; Chaudhry, Anurag; Canning, Andrew

    2015-06-09

    The present invention provides for a composition comprising an inorganic scintillator comprising an optionally lanthanide-doped strontium-barium, optionally cesium, halide, useful for detecting nuclear material.

  13. Structure and Chemistry in Halide Lead-Tellurite Glasses

    Energy Technology Data Exchange (ETDEWEB)

    McCloy, John S.; Riley, Brian J.; Lipton, Andrew S.; Windisch, Charles F.; Washton, Nancy M.; Olszta, Matthew J.; Rodriguez, Carmen P.

    2013-02-11

    A series of TeO2-PbO glasses were fabricated with increasing fractions of mixed alkali, alkaline earth, and lanthanide chlorides. The glass and crystal structure was studied with Raman spectroscopy, nuclear magnetic resonance (NMR), X-ray diffraction, and electron microscopy. As the chloride fraction increased, the medium-range order in the glass decreased up to a critical point (~14 mass% of mixed chlorides), above which the glasses became phase-separated. Resulting phases are a TeO2/PbO-rich phase and a crystalline phase rich in alkali chlorides. The 125Te NMR indicates, contrary to previous studies, that Te site distribution did not change with increased concentrations of M+, M2+, and M3+ cations, but rather is controlled by the Te/Pb molar ratio. The 207Pb NMR shows that two Pb species exist and their relative concentration changes nearly linearly with addition of the mixed chlorides, indicating that the additives to the TeO2-PbO glass are accommodated by changing the Pb species. The 23Na and 35Cl NMR indicate that Na and Cl are distributed in the single-phase glass phase up to the critical point, and at higher concentrations partition to crystalline phases. Transmission electron microscopy shows that the sample at the critical point contains ~10 nm seed nuclei that increase in size and concentration with exposure to the electron beam.

  14. ACCUMULATION OF ALKALIS IN THE RECYCLING FILTRATE OF THE PHOSPHOGYPSUM PULPS

    Directory of Open Access Journals (Sweden)

    ANTANAS KAZILIUNAS

    2011-12-01

    Full Text Available Sodium and potassium combinations existing in phosphogypsum are highly soluble and remain in the filtrate, their amount increasing with each recycle. It has been determined that the amount of alkalis in the recycling filtrate depends on an amount of alkalis in uncleaned phosphogypsum, a number of recycles in the filtrate, the technology of the phosphogypsum pulp preparation and an amount of soluble phosphates. New phosphate formations composed in an acid medium (pH = 4.5-5 are well crystalized crystals. They do not alter the filtrability of the phosphogypsum pulp. The new combinations formed in an alkaline medium (pH = 7-11 are colloidal. They settle down on the surface of the hard particles and make the filtration of the phosphogypsum pulp complicated. The filtrated phosphogypsum is more humid which causes the growth of the amount of alkalis carried out together with moisture and thus the lower alkali concentration is observed in the recycling filtrate. In the discussed case, the larger amount of soluble phosphates of uncleaned phosphogypsum is formed the larger amount of the colloidal particles in the neutralized phosphogypsum pulp which results in complicated filtration. In all the cases, the alkali concentration in the recycling filtrate approaches the maximum degree which would take place if alkalis existing in uncleaned phosphogypsum were thawed in humidity of cleaned phosphogypsum.

  15. Lead-Free Halide Double Perovskites via Heterovalent Substitution of Noble Metals.

    Science.gov (United States)

    Volonakis, George; Filip, Marina R; Haghighirad, Amir Abbas; Sakai, Nobuya; Wenger, Bernard; Snaith, Henry J; Giustino, Feliciano

    2016-04-07

    Lead-based halide perovskites are emerging as the most promising class of materials for next-generation optoelectronics; however, despite the enormous success of lead-halide perovskite solar cells, the issues of stability and toxicity are yet to be resolved. Here we report on the computational design and the experimental synthesis of a new family of Pb-free inorganic halide double perovskites based on bismuth or antimony and noble metals. Using first-principles calculations we show that this hitherto unknown family of perovskites exhibits very promising optoelectronic properties, such as tunable band gaps in the visible range and low carrier effective masses. Furthermore, we successfully synthesize the double perovskite Cs2BiAgCl6, perform structural refinement using single-crystal X-ray diffraction, and characterize its optical properties via optical absorption and photoluminescence measurements. This new perovskite belongs to the Fm3̅m space group and consists of BiCl6 and AgCl6 octahedra alternating in a rock-salt face-centered cubic structure. From UV-vis and photoluminescence measurements we obtain an indirect gap of 2.2 eV.

  16. Lanthanum halide scintillators for time-of-flight 3-D pet

    Science.gov (United States)

    Karp, Joel S.; Surti, Suleman

    2008-06-03

    A Lanthanum Halide scintillator (for example LaCl.sub.3 and LaBr.sub.3) with fast decay time and good timing resolution, as well as high light output and good energy resolution, is used in the design of a PET scanner. The PET scanner includes a cavity for accepting a patient and a plurality of PET detector modules arranged in an approximately cylindrical configuration about the cavity. Each PET detector includes a Lanthanum Halide scintillator having a plurality of Lanthanum Halide crystals, a light guide, and a plurality of photomultiplier tubes arranged respectively peripherally around the cavity. The good timing resolution enables a time-of-flight (TOF) PET scanner to be developed that exhibits a reduction in noise propagation during image reconstruction and a gain in the signal-to-noise ratio. Such a PET scanner includes a time stamp circuit that records the time of receipt of gamma rays by respective PET detectors and provides timing data outputs that are provided to a processor that, in turn, calculates time-of-flight (TOF) of gamma rays through a patient in the cavity and uses the TOF of gamma rays in the reconstruction of images of the patient.

  17. Water Content of Lunar Alkali Fedlspar

    Science.gov (United States)

    Mills, R. D.; Simon, J. I.; Wang, J.; Alexander, C. M. O'D.; Hauri, E. H.

    2016-01-01

    Detection of indigenous hydrogen in a diversity of lunar materials, including volcanic glass, melt inclusions, apatite, and plagioclase suggests water may have played a role in the chemical differentiation of the Moon. Spectroscopic data from the Moon indicate a positive correlation between water and Th. Modeling of lunar magma ocean crystallization predicts a similar chemical differentiation with the highest levels of water in the K- and Th-rich melt residuum of the magma ocean (i.e. urKREEP). Until now, the only sample-based estimates of water content of KREEP-rich magmas come from measurements of OH, F, and Cl in lunar apatites, which suggest a water concentration of water content of the magma ocean would have water contents of 320 ppm for the bulk Moon and 1.4 wt % for urKREEP from plagioclase in ferroan anorthosites. Results and interpretation: NanoSIMS data from granitic clasts from Apollo sample 15405,78 show that alkali feldspar, a common mineral in K-enriched rocks, can have approx. 20 ppm of water, which implies magmatic water contents of approx. 1 wt % in the high-silica magmas. This estimate is 2 to 3 orders of magnitude higher than that estimated from apatite in similar rocks. However, the Cl and F contents of apatite in chemically similar rocks suggest that these melts also had high Cl/F ratios, which leads to spuriously low water estimates from the apatite. We can only estimate the minimum water content of urKREEP (+ bulk Moon) from our alkali feldspar data because of the unknown amount of degassing that led to the formation of the granites. Assuming a reasonable 10 to 100 times enrichment of water from urKREEP into the granites produces an estimate of 100-1000 ppm of water for the urKREEP reservoir. Using the modeling of and the 100-1000 ppm of water in urKREEP suggests a minimum bulk silicate Moon water content between 2 and 20 ppm. However, hydrogen loss was likely very significant in the evolution of the lunar mantle. Conclusions: Lunar granites

  18. Nanowire Lasers of Formamidinium Lead Halide Perovskites and Their Stabilized Alloys with Improved Stability.

    Science.gov (United States)

    Fu, Yongping; Zhu, Haiming; Schrader, Alex W; Liang, Dong; Ding, Qi; Joshi, Prakriti; Hwang, Leekyoung; Zhu, X-Y; Jin, Song

    2016-02-10

    The excellent intrinsic optoelectronic properties of methylammonium lead halide perovskites (MAPbX3, X = Br, I), such as high photoluminescence quantum efficiency, long carrier lifetime, and high gain coupled with the facile solution growth of nanowires make them promising new materials for ultralow-threshold nanowire lasers. However, their photo and thermal stabilities need to be improved for practical applications. Herein, we report a low-temperature solution growth of single crystal nanowires of formamidinium lead halide perovskites (FAPbX3) that feature red-shifted emission and better thermal stability compared to MAPbX3. We demonstrate optically pumped room-temperature near-infrared (∼820 nm) and green lasing (∼560 nm) from FAPbI3 (and MABr-stabilized FAPbI3) and FAPbBr3 nanowires with low lasing thresholds of several microjoules per square centimeter and high quality factors of about 1500-2300. More remarkably, the FAPbI3 and MABr-stabilized FAPbI3 nanowires display durable room-temperature lasing under ∼10(8) shots of sustained illumination of 402 nm pulsed laser excitation (150 fs, 250 kHz), substantially exceeding the stability of MAPbI3 (∼10(7) laser shots). We further demonstrate tunable nanowire lasers in wider wavelength region from FA-based lead halide perovskite alloys (FA,MA)PbI3 and (FA,MA)Pb(I,Br)3 through cation and anion substitutions. The results suggest that formamidinium lead halide perovskite nanostructures could be more promising and stable materials for the development of light-emitting diodes and continuous-wave lasers.

  19. Effect of alkali and heat treatments for bioactivity of TiO{sub 2} nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Seo young, E-mail: mast6269@nate.com [Dept. of Dental Biomaterials and Institute of Bio degradable material, Institute of Oral Bioscience and BK21 plus project, School of Dentistry, Chonbuk National University, Jeonju, 561-756 (Korea, Republic of); Kim, Yu kyoung, E-mail: yk0830@naver.com [Dept. of Dental Biomaterials and Institute of Bio degradable material, Institute of Oral Bioscience and BK21 plus project, School of Dentistry, Chonbuk National University, Jeonju, 561-756 (Korea, Republic of); Park, Il song, E-mail: ilsong@jbnu.ac.kr [Division of Advanced Materials Engineering, Research Center for Advanced Materials Development and Institute of Biodegradable Materials, Chonbuk National University, Jeonju 561-756 (Korea, Republic of); Jin, Guang chun, E-mail: jingc88@126.com [Oral Medical College, Beihua University, Jilin City 132013 (China); Bae, Tae sung, E-mail: bts@jbnu.ac.kr [Dept. of Dental Biomaterials and Institute of Bio degradable material, Institute of Oral Bioscience and BK21 plus project, School of Dentistry, Chonbuk National University, Jeonju, 561-756 (Korea, Republic of); Lee, Min ho, E-mail: mh@jbnu.ac.kr [Dept. of Dental Biomaterials and Institute of Bio degradable material, Institute of Oral Bioscience and BK21 plus project, School of Dentistry, Chonbuk National University, Jeonju, 561-756 (Korea, Republic of)

    2014-12-01

    Highlights: • TiO{sub 2} nanotubes formed via anodization were treated by alkali and heat. • The surface roughness was increased after alkali treatment (p < 0.05). • After alkali and heat treatment, the wettability was better than before treatment. • Alkali treated TiO{sub 2} nanotubes were shown higher HAp formation in SBF. • Heat treatment affected on the attachment of cells for alkali treated nanotubes. - Abstract: In this study, for improving the bioactivity of titanium used as an implant material, alkali and heat treatments were carried out after formation of the nanotubes via anodization. Nanotubes with uniform length, diameter, and thickness were formed by anodization. The alkali and heat-treated TiO{sub 2} nanotubes were covered with the complex network structure, and the Na compound was generated on the surface of the specimens. In addition, after 5 and 10 days of immersion in the SBF, the crystallized OCP and HAp phase was significantly increased on the surface of the alkali-treated TiO{sub 2} nanotubes (PNA) and alkali and heat-treated TiO{sub 2} nanotubes (PNAH) groups. Cell proliferation was decreased due to the formation of amorphous sodium titanate (Na{sub 2}TiO{sub 3}) layer on the surface of the PNA group. However, anatase and crystalline sodium titanate were formed on the surface of the PNAH group after heat treatment at 550 °C, and cell proliferation was improved. Thus, PNA group had higher HAp forming ability in the simulated body fluid. Additional heat treatment affected on enhancement of the bioactivity and the attachment of osteoblasts for PNA group.

  20. Research Update: Luminescence in lead halide perovskites

    Science.gov (United States)

    Srimath Kandada, Ajay Ram; Petrozza, Annamaria

    2016-09-01

    Efficiency and dynamics of radiative recombination of carriers are crucial figures of merit for optoelectronic materials. Following the recent success of lead halide perovskites in efficient photovoltaic and light emitting technologies, here we review some of the noted literature on the luminescence of this emerging class of materials. After outlining the theoretical formalism that is currently used to explain the carrier recombination dynamics, we review a few significant works which use photoluminescence as a tool to understand and optimize the operation of perovskite based optoelectronic devices.

  1. Research Update: Luminescence in lead halide perovskites

    Directory of Open Access Journals (Sweden)

    Ajay Ram Srimath Kandada

    2016-09-01

    Full Text Available Efficiency and dynamics of radiative recombination of carriers are crucial figures of merit for optoelectronic materials. Following the recent success of lead halide perovskites in efficient photovoltaic and light emitting technologies, here we review some of the noted literature on the luminescence of this emerging class of materials. After outlining the theoretical formalism that is currently used to explain the carrier recombination dynamics, we review a few significant works which use photoluminescence as a tool to understand and optimize the operation of perovskite based optoelectronic devices.

  2. Nanoscale investigation of organic - inorganic halide perovskites

    Science.gov (United States)

    Cacovich, S.; Divitini, G.; Vrućinić, M.; Sadhanala, A.; Friend, R. H.; Sirringhaus, H.; Deschler, F.; Ducati, C.

    2015-10-01

    Over the last few years organic - inorganic halide perovskite-based solar cells have exhibited a rapid evolution, reaching certified power conversion efficiencies now surpassing 20%. Nevertheless the understanding of the optical and electronic properties of such systems on the nanoscale is still an open problem. In this work we investigate two model perovskite systems (based on iodine - CH3NH3PbI3 and bromine - CH3NH3PbBr3), analysing the local elemental composition and crystallinity and identifying chemical inhomogeneities.

  3. Positron-alkali atom scattering

    Science.gov (United States)

    Mceachran, R. P.; Horbatsch, M.; Stauffer, A. D.; Ward, S. J.

    1990-01-01

    Positron-alkali atom scattering was recently investigated both theoretically and experimentally in the energy range from a few eV up to 100 eV. On the theoretical side calculations of the integrated elastic and excitation cross sections as well as total cross sections for Li, Na and K were based upon either the close-coupling method or the modified Glauber approximation. These theoretical results are in good agreement with experimental measurements of the total cross section for both Na and K. Resonance structures were also found in the L = 0, 1 and 2 partial waves for positron scattering from the alkalis. The structure of these resonances appears to be quite complex and, as expected, they occur in conjunction with the atomic excitation thresholds. Currently both theoretical and experimental work is in progress on positron-Rb scattering in the same energy range.

  4. New alkali metal diphosphates how materials to preserve the security of the environment: CsNaCu(P2O7), Rb2Cu(P2O7) and CsNaCo(P2O7) synthesis and crystal structure determination

    Science.gov (United States)

    Chernyatieva, Anastasiya; Filatova, Alyona; Spiridonova, Dariya; Krivovichev, Sergey

    2013-04-01

    In this work we describe preliminary results of the synthesis and of a crystal-chemical study of synthetic phosphates with transition metals. Due to the increasing requirements for environmental safety specialists from various industries, we are searching for sustainable forms of immobilization of hazardous waste during storage. We are also developing a component-based waste for new materials. In our continued exploratory synthesis of compounds containing transition-metals, we were able to produce the new diphosphate phases CsNaCu(P2O7), Rb2Cu(P2O7) and CsNaCo(P2O7). A crystal chemical study has allowed us to identify new phosphates. Crystals of CsNaCu(P2O7) (Phase 1) is orthorhombic, crystallizes in space group Pmn21, with a = 5.147(8), b = 15.126(2), c = 9.717(2) Å, V = 756.20 Å3, R1 = 0.066 and Rb2Cu(P2O7) (Phase 2) is orthorhombic as well, crystallizes in space group Pmcn, with a = 5.183(8), b = 10.096(1), c = 15.146(3) Å, V = 793.55 Å3, R1 = 0.063, they have been obtained by high-temperature reaction of RbNO3, CsNO3, Cu(NO3)2, NaOH and (NH4)4P2O7. Synthetic crystals of the phosphate of copper and rubidium were studied in detail by us on the structures of Rb2Cu(P2O7) and Rb2Cu3(P2O7)2 - new alkali metal copper diphosphates (CHERNYATIEVA et al., 2008). Here we report the synthesis, the structure and the properties of the title compounds and we compare these phases with the previously discovered K2CuP2O7 (ELMAADI et al., 1995) and CsNaMnP2O7 (HUANG et al., 1998). These structures crystallize in other space groups, although their structures are also based on 2-D layers, formed by P2O7 groups combined with polyhedra of the transition metals (CHERNYATIEVA et al., 2012). A crystal chemical study has allowed us to identify even new diphosphates CsNaCu(P2O7) (Phase 3). Crystals of CsNaCoP2O7 is monoclinic, space group P 21/n, with a = 7,424(2), b = 7,648(1), c = 12,931(3)Å, β = 90,71(2)° , V = 734.2(3) Å3 and R1 = 0.060. The structure is based framework of Co

  5. Robust quantum anomalous Hall effect in ferromagnetic transition metal halides

    CERN Document Server

    Huang, Chengxi; Wu, Haiping; Deng, Kaiming; Jena, Puru; Kan, Erjun

    2016-01-01

    The quantum anomalous Hall (QAH) effect is a novel topological spintronic phenomenon arising from inherent magnetization and spin-orbit coupling. Various theoretical and experimental efforts have been devoted in search of robust intrinsic QAH insulators. However, up to now, it has only been observed in Cr or V doped (Bi,Sb)2Te3 film in experiments with very low working temperature. Based on the successful synthesis of transition metal halides, we use first-principles calculations to predict that RuI3 monolayer is an intrinsic ferromagnetic QAH insulator with a topologically nontrivial global band gap of 11 meV. This topologically nontrivial band gap at the Fermi level is due to its crystal symmetry, thus the QAH effect is robust. Its Curie temperature, estimated to be ~360 K using Monte-Carlo simulation, is above room temperature and higher than most of two-dimensional ferromagnetic thin films. We also discuss the manipulation of its exchange energy and nontrivial band gap by applying in-plane strain. Our wor...

  6. Silver nanoparticles from silver halide photography to plasmonics

    CERN Document Server

    Tani, Tadaaki

    2015-01-01

    This book provides systematic knowledge and ideas on nanoparticles of Ag and related materials. While Ag and metal nanoparticles are essential for plasmonics, silver halide (AgX) photography relies to a great extent on nanoparticles of Ag and AgX which have the same crystal structure and have been studied extensively for many years. This book has been written to combine the knowledge of nanoparticles of Ag and related materials in plasmonics and AgX photography in order to provide new ideas for metal nanoparticles in plasmonics. Chapters 1–3 of this book describe the structure and formation of nanoparticles of Ag and related materials. Systematic descriptions of the structure and preparation of Ag, Au, and noble-metal nanoparticles for plasmonics are followed by and related to those of nanoparticles of Ag and AgX in AgX photography. Knowledge of the structure and preparation of Ag and AgX nanoparticles in photography covers nanoparticles with widely varying sizes, shapes, and structures, and formation proce...

  7. Quantum anomalous Hall effect in ferromagnetic transition metal halides

    Science.gov (United States)

    Huang, Chengxi; Zhou, Jian; Wu, Haiping; Deng, Kaiming; Jena, Puru; Kan, Erjun

    2017-01-01

    The quantum anomalous Hall (QAH) effect is a novel topological spintronic phenomenon arising from inherent magnetization and spin-orbit coupling. Various theoretical and experimental efforts have been devoted in search of intrinsic QAH insulators. However, up to now, it has only been observed in Cr or V doped (Bi,Sb ) 2T e3 film in experiments with very low working temperature. Based on the successful synthesis of transition metal halides, we use first-principles calculations to predict that the Ru I3 monolayer is an intrinsic ferromagnetic QAH insulator with a topologically nontrivial global band gap of 11 meV. This topologically nontrivial band gap at the Fermi level is due to its crystal symmetry, thus the QAH effect is robust. Its Curie temperature, estimated to be ˜360 K using Monte Carlo simulation, is above room temperature and higher than most two-dimensional ferromagnetic thin films. The inclusion of Hubbard U in the Ru-d electrons does not affect this result. We also discuss the manipulation of its exchange energy and nontrivial band gap by applying in-plane strain. Our work adds an experimentally feasible member to the QAH insulator family, which is expected to have broad applications in nanoelectronics and spintronics.

  8. Intriguing Optoelectronic Properties of Metal Halide Perovskites.

    Science.gov (United States)

    Manser, Joseph S; Christians, Jeffrey A; Kamat, Prashant V

    2016-11-09

    A new chapter in the long and distinguished history of perovskites is being written with the breakthrough success of metal halide perovskites (MHPs) as solution-processed photovoltaic (PV) absorbers. The current surge in MHP research has largely arisen out of their rapid progress in PV devices; however, these materials are potentially suitable for a diverse array of optoelectronic applications. Like oxide perovskites, MHPs have ABX3 stoichiometry, where A and B are cations and X is a halide anion. Here, the underlying physical and photophysical properties of inorganic (A = inorganic) and hybrid organic-inorganic (A = organic) MHPs are reviewed with an eye toward their potential application in emerging optoelectronic technologies. Significant attention is given to the prototypical compound methylammonium lead iodide (CH3NH3PbI3) due to the preponderance of experimental and theoretical studies surrounding this material. We also discuss other salient MHP systems, including 2-dimensional compounds, where relevant. More specifically, this review is a critical account of the interrelation between MHP electronic structure, absorption, emission, carrier dynamics and transport, and other relevant photophysical processes that have propelled these materials to the forefront of modern optoelectronics research.

  9. Performance characterization of rigid polyurethane foam with refined alkali lignin and modified alkali lignin

    Institute of Scientific and Technical Information of China (English)

    LIU Zhi-ming; YU Fei; FANG Gui-zhen; YANG Hui-jun

    2009-01-01

    The two kinds of rigid polyurethane (PU) foams were prepared with respectively adding the refined alkali lignin and alkali lignin modified by 3-chloro-1,2-epoxypropane to be instead of 15% of the polyether glycol in weight. The indexes of mechanical performance, apparent density, thermal stability and aging resistance were separately tested for the prepared PU foams. The results show that the mechanical property, thermal insulation and thermal stability for PU foam with modified alkali lignin are excellent among two kinds of PU foams and control samples. The additions of the refined alkali lignin and modified alkali lignin to PU foam have little effect on the natural aging or heat aging resistance except for decreasing hot alkali resistance apparently. Additionally, the thermal conductivity of modified alkali lignin PU foam is lowest among two kinds of PU foams and control samples. The alkali lignin PU foam modified by 3-chloro-1,2-epoxypropane could be applied in the heat preservation field.

  10. Geochemical Trace of Silicon Isotopes of Intrusions and Ore Veins Related to Alkali-rich Porphyry Deposits in Western Yunnan, China

    Institute of Scientific and Technical Information of China (English)

    LIU Xianfan; YANG Zhengxi; LIU Jiaduo; WU Dechao; ZHANG Chenjiang; LI Youguo

    2004-01-01

    Western Yunnan is the well-known polymetallic province in China. It is characterized by copper-gold mineralization related to Cenozoic alkali-rich porphyry. This paper analyzes the silicon isotope data obtained from four typical alkali-rich porphyry deposits based on the dynamic fractionation principle of silicon isotope. The study shows that the ore materials should originate mainly from alkali-rich magmas, together with silicon-rich mineralizing fluids.The process of mineralization was completed by auto-metasomatism, i.e. silicon-rich mineralizing fluids (including alkali-rich porphyry and wall-rock strata) replaced and altered the country rocks and contaminated with crustal rocks during the crystallization of alkali-rich magmas. Such a process is essentially the continuance of the metasomatism of mantle fluids in crust's mineralization. This provides important evidence of silicon isotopic geochemistry for better understanding the mineralization of the Cenozoic alkali-rich porphyry polymetallic deposits

  11. Photophysics of Hybrid Lead Halide Perovskites: The Role of Microstructure.

    Science.gov (United States)

    Srimath Kandada, Ajay Ram; Petrozza, Annamaria

    2016-03-15

    Since the first reports on high efficiency, solution processed solar cells based on hybrid lead halide perovskites, there has been an explosion of activities on these materials. Researchers with interests spanning the full range from conventional inorganic to emerging organic and hybrid optoelectronic technologies have been contributing to the prolific research output. This has led to solar cell power conversion efficiencies now exceeding 20% and the demonstration of proofs of concept for electroluminescent and lasing devices. Hybrid perovskites can be self-assembled by a simple chemical deposition of the constituent units, with the possibility of integrating the useful properties of organic and inorganic compounds at the molecular scale within a single crystalline material, thus enabling a fine-tuning of the electronic properties. Tellingly, the fundamental properties of these materials may make us think of a new, solution processable, GaAs-like semiconductor. While this can be true to a first approximation, hybrid perovskites are intrinsically complex materials, where the presence of various types of interactions and structural disorder may strongly affect their properties. In particular, a clear understanding and control of the relative interactions between the organic and inorganic moieties is of paramount importance to properly disentangle their innate physics. In this Account we review our recent studies which aim to clarify the relationship between structural and electronic properties from a molecular to mesoscopic level. First we identify the markers for local disorder at the molecular level by using Raman spectroscopy as a probe. Then, we exploit such a tool to explore the role of microstructure on the absorption and luminescence properties of the semiconductor. Finally we address the controversy surrounding electron-hole interactions and excitonic effects. We show that in hybrid lead-halide perovskites dielectric screening also depends on the local

  12. Conformer of the peroxynitrite ion formed under photolysis of crystalline alkali nitrates – cis or trans?

    Science.gov (United States)

    Pak, V. Kh; Anan’ev, V. A.; Dyagileva, E. P.; Lyrshchikov, S. Yu; Miklin, M. B.; Rezvova, M. A.

    2017-01-01

    The optical and infrared reflectance spectra of the crystalline powders prepared by co-crystallization of caesium nitrate, nitrite, and peroxynitrite from alkali solution have been studied. We find that the trans conformer forms under photolysis of crystalline pure caesium nitrate. Under its dissolution the trans conformer transforms to the cis conformer.

  13. Barium halide nanocrystals in fluorozirconate based glass ceramics for scintillation application

    Energy Technology Data Exchange (ETDEWEB)

    Selling, J.

    2007-07-01

    Europium (Eu)-activated barium halide nanocrystals in fluorozirconate based glass ceramics represent a promising class of Xray scintillators. The scintillation in these glass ceramics is mainly caused by the emission of divalent Eu incorporated in hexagonal BaCl{sub 2} nanocrystals which are formed in the glass matrix upon appropriate annealing. Experiments with cerium (Ce)-activated fluorozironate glass ceramics showed that Ce is an interesting alternative. In order to get a better understanding of the scintillation mechanism in Eu- or Ce-activated barium halide nanocrystals, an investigation of the processes in the corresponding bulk material is essential. The objective of this thesis is the investigation of undoped, Eu-, and Ce-doped barium halides by X-ray excited luminescence (XL), pulse height, and scintillation decay spectra. That will help to figure out which of these crystals has the most promising scintillation properties and would be the best nanoparticles for the glass ceramics. Furthermore, alternative dopants like samarium (Sm) and manganese (Mn) were also investigated. Besides the above-mentioned optical investigation electron paramagnetic resonance (EPR) and Moessbauer measurements were carried out in order to complete the picture of Eu-doped barium halides. The EPR data of Eu-doped BaI{sub 2} is anticipated to yield more information about the crystal field and crystal structure that will help to understand the charge carrier process during the scintillation process. The main focus of the Moessbauer investigations was set on the Eu-doped fluorochlorozirconate glass ceramics. The results of this investigation should help to improve the glass ceramics. The Eu{sup 2+}/Eu{sup 3+} ratio in the glass ceramics should be determined and optimize favor of the Eu{sup 2+}. We also want to distinguish between Eu{sup 2+} in the glass matrix and Eu{sup 2+} in the nanocrystals. For a better understanding of Moessbauer spectroscopy on Eu also measurements on Eu in a

  14. Formation of reactive halide species by myeloperoxidase and eosinophil peroxidase.

    Science.gov (United States)

    Spalteholz, Holger; Panasenko, Oleg M; Arnhold, Juergen

    2006-01-15

    The formation of chloro- and bromohydrins from 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine following incubation with myeloperoxidase or eosinophil peroxidase in the presence of hydrogen peroxide, chloride and/or bromide was analysed by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry. These products were only formed below a certain pH threshold value, that increased with increasing halide concentration. Thermodynamic considerations on halide and pH dependencies of reduction potentials of all redox couples showed that the formation of a given reactive halide species in halide oxidation coupled with the reduction of compound I of heme peroxidases is only possible below a certain pH threshold that depends on halide concentration. The comparison of experimentally derived and calculated data revealed that Cl(2), Br(2), or BrCl will primarily be formed by the myeloperoxidase-H(2)O(2)-halide system. However, the eosinophil peroxidase-H(2)O(2)-halide system forms directly HOCl and HOBr.

  15. The unexpected properties of alkali metal iron selenide superconductors

    Energy Technology Data Exchange (ETDEWEB)

    Dagotto, Elbio R [ORNL

    2013-01-01

    The iron-based superconductors that contain FeAs layers as the fundamental building block in the crystal structures have been rationalized in the past using ideas based on the Fermi surface nesting of hole and electron pockets when in the presence of weak Hubbard U interactions. This approach seemed appropriate considering the small values of the magnetic moments in the parent compounds and the clear evidence based on photoemission experiments of the required electron and hole pockets. However, recent results in the context of alkali metal iron selenides, with generic chemical composition AxFe2ySe2 (A alkali metal element), have challenged those previous ideas since at particular compositions y the low-temperature ground states are insulating and display antiferromagnetic order with large iron magnetic moments. Moreover, angle-resolved photoemission studies have revealed the absence of hole pockets at the Fermi level in these materials. The present status of this exciting area of research, with the potential to alter conceptually our understanding of the ironbased superconductors, is here reviewed, covering both experimental and theoretical investigations. Other recent related developments are also briefly reviewed, such as the study of selenide two-leg ladders and the discovery of superconductivity in a single layer of FeSe. The conceptual issues considered established for the alkali metal iron selenides, as well as several issues that still require further work, are discussed.

  16. Temperature Sensitive Optical Phenomena in Heavy Metal Halide Films.

    Science.gov (United States)

    1979-01-08

    Heavy - metal halides such as Pb!2 and HgI2 exhibit a strongly tempera- ture dependent absorption edge at visible frequencies. The shift in the absorption...AOb9 537 ROCKWELL INTERNATIONAL ANAHEIM CA ELECTRONICS RESEAR—— ETC FIG L u G TEMPERATURE SENSITIVE OPTICAL PHENOMENA IN HEAVY METAL HALIDE F—— ETC (U...PHENOMENA IN HEAVY METAL HALIDE F — ET C( U) ,JAN 79 J D MC*LLEN, D M HEINZ. F S STEARNS DAAK7O— 77—C—01 6 5 UNCLASSIFIED C79 1501 _ _ U SB

  17. Superconductivity in alkali-doped fullerene nanowhiskers

    Science.gov (United States)

    Takeya, Hiroyuki; Konno, Toshio; Hirata, Chika; Wakahara, Takatsugu; Miyazawa, Kun'ichi; Yamaguchi, Takahide; Tanaka, Masashi; Takano, Yoshihiko

    2016-09-01

    Superconductivity in alkali metal-doped fullerene nanowhiskers (C60NWs) was observed in K3.3C60NWs, Rb3.0C60NWs and Cs2.0Rb1.0C60NWs with transition temperatures at 17, 25 and 26 K, respectively. Almost full shielding volume fraction (~80%) was observed in K3.3C60NWs when subjected to thermal treatment at 200 °C for a duration of 24 h. In contrast, the shielding fraction of Rb3.0C60NWs and Cs2.0Rb1.0C60NWs were calculated to be 8% and 6%, respectively. Here we report on an extensive investigation of the superconducting properties of these AC60NWs (A  =  K3.3, Rb3.0 and Cs2.0Rb1.0). These properties are compared to the ones reported on the corresponding conventional (single-crystal or powder) K-doped fullerene. We also evaluated the critical current densities of these C60NWs using the Bean model under an applied magnetic field up to 50 kOe.

  18. Unraveling the Role of Monovalent Halides in Mixed-Halide Organic-Inorganic Perovskites.

    Science.gov (United States)

    Deepa, Melepurath; Ramos, F Javier; Shivaprasad, S M; Ahmad, Shahzada

    2016-03-16

    The performance of perovskite solar cells is strongly influenced by the composition and microstructure of the perovskite. A recent approach to improve the power conversion efficiencies utilized mixed-halide perovskites, but the halide ions and their roles were not directly studied. Unraveling their precise location in the perovskite layer is of paramount importance. Here, we investigated four different perovskites by using X-ray photoelectron spectroscopy, and found that among the three studied mixed-halide perovskites, CH3 NH3 Pb(I0.74 Br0.26 )3 and CH3 NH3 PbBr3-x Clx show peaks that unambiguously demonstrate the presence of iodide and bromide in the former, and bromide and chloride in the latter. The CH3 NH3 PbI3-x Clx perovskite shows anomalous behavior, the iodide content far outweighs that of the chloride; a small proportion of chloride, in all likelihood, resides deep within the TiO2 /absorber layer. Our study reveals that there are many distinguishable structural differences between these perovskites, and that these directly impact the photovoltaic performances.

  19. Structural analysis of alkali cations in mixed alkali silicate glasses by 23Na and 133Cs MAS NMR

    Directory of Open Access Journals (Sweden)

    T. Minami

    2014-12-01

    Full Text Available We report the structural analysis of Na+ and Cs+ in sodium cesium silicate glasses by using 23Na and 133Cs magic-angle spinning nuclear magnetic resonance (MAS NMR spectroscopy. In the NMR spectra of cesium silicate crystals, the peak position shifted to higher magnetic field for structures with larger Cs+ coordination numbers and to lower magnetic field for smaller Cs+ coordination numbers. The MAS NMR spectra of xNa2O-yCs2O-2SiO2 (x = 0, 0.2, 0.33, 0.5, 0.66, 0.8, 1.0; x + y = 1 glass reveal that the average coordination number of both the alkali cations decreases with increasing Cs+/(Na+ + Cs+ ratio. In addition, the coordination number of Na+ in xNa2O-yCs2O-2SiO2 glass is smaller than that of Cs+. This difference between the average coordination numbers of the alkali cations is considered to be one structural reason of the mixed alkali effect.

  20. Tellurium halide IR fibers for remote spectroscopy

    Science.gov (United States)

    Zhang, Xhang H.; Ma, Hong Li; Blanchetiere, Chantal; Le Foulgoc, Karine; Lucas, Jacques; Heuze, Jean; Colardelle, P.; Froissard, P.; Picque, D.; Corrieu, G.

    1994-07-01

    The new family of IR transmitting glasses, the TeX glasses, based on the association of tellurium and halide (Cl, Br, or I) are characterized by a wide optical window extending from 2 to 18 micrometers and a strong stability towards devitrification. Optical fibers drawn from these glasses exhibit low losses in the 7 - 10 micrometers range (less than 1 dB/m for single index fibers, 1 - 2 dB/m for fibers having a core-clad structure). The TeX glass fibers have been used in a remote analysis set-up which is mainly composed of a FTIR spectrometer coupled with a HgCdTe detector. This prototype system permits qualitative and quantitative analysis in a wide wavelength region lying from 3 to 13 micrometers , covering the fundamental absorption of more organic species. The evolution of a lactic and an alcoholic fermentation has been monitored by means of this set-up.

  1. Metal halide perovskites for energy applications

    Science.gov (United States)

    Zhang, Wei; Eperon, Giles E.; Snaith, Henry J.

    2016-06-01

    Exploring prospective materials for energy production and storage is one of the biggest challenges of this century. Solar energy is one of the most important renewable energy resources, due to its wide availability and low environmental impact. Metal halide perovskites have emerged as a class of semiconductor materials with unique properties, including tunable bandgap, high absorption coefficient, broad absorption spectrum, high charge carrier mobility and long charge diffusion lengths, which enable a broad range of photovoltaic and optoelectronic applications. Since the first embodiment of perovskite solar cells showing a power conversion efficiency of 3.8%, the device performance has been boosted up to a certified 22.1% within a few years. In this Perspective, we discuss differing forms of perovskite materials produced via various deposition procedures. We focus on their energy-related applications and discuss current challenges and possible solutions, with the aim of stimulating potential new applications.

  2. Purification and characterization of an extracellular, thermo-alkali-stable, metal tolerant laccase from Bacillus tequilensis SN4.

    Science.gov (United States)

    Sondhi, Sonica; Sharma, Prince; Saini, Shilpa; Puri, Neena; Gupta, Naveen

    2014-01-01

    A novel extracellular thermo-alkali-stable laccase from Bacillus tequilensis SN4 (SN4LAC) was purified to homogeneity. The laccase was a monomeric protein of molecular weight 32 KDa. UV-visible spectrum and peptide mass fingerprinting results showed that SN4LAC is a multicopper oxidase. Laccase was active in broad range of phenolic and non-phenolic substrates. Catalytic efficiency (kcat/Km) showed that 2, 6-dimethoxyphenol was most efficiently oxidized by the enzyme. The enzyme was inhibited by conventional inhibitors of laccase like sodium azide, cysteine, dithiothreitol and β-mercaptoethanol. SN4LAC was found to be highly thermostable, having temperature optimum at 85°C and could retain more than 80% activity at 70°C for 24 h. The optimum pH of activity for 2, 6-dimethoxyphenol, 2, 2'-azino bis[3-ethylbenzthiazoline-6-sulfonate], syringaldazine and guaiacol was 8.0, 5.5, 6.5 and 8.0 respectively. Enzyme was alkali-stable as it retained more than 75% activity at pH 9.0 for 24 h. Activity of the enzyme was significantly enhanced by Cu2+, Co2+, SDS and CTAB, while it was stable in the presence of halides, most of the other metal ions and surfactants. The extracellular nature and stability of SN4LAC in extreme conditions such as high temperature, pH, heavy metals, halides and detergents makes it a highly suitable candidate for biotechnological and industrial applications.

  3. Role of Microstructure in the Electron-Hole Interaction of Hybrid Lead-Halide Perovskites

    Science.gov (United States)

    Frost, Jarvist M.; Barker, Alex J.; De Bastiani, Michele; Gandini, Marina; Marras, Sergio; Lanzani, Guglielmo; Walsh, Aron; Petrozza, Annamaria

    2015-01-01

    Solar cells based on hybrid inorganic-organic halide perovskites have demonstrated high power conversion efficiencies in a range of architectures. The existence and stability of bound electron-hole pairs in these materials, and their role in the exceptional performance of optoelectronic devices, remains a controversial issue. Here we demonstrate, through a combination of optical spectroscopy and multiscale modeling as a function of the degree of polycrystallinity and temperature, that the electron-hole interaction is sensitive to the microstructure of the material. The long-range order is disrupted by polycrystalline disorder and the variations in electrostatic potential found for smaller crystals suppress exciton formation, while larger crystals of the same composition demonstrate an unambiguous excitonic state. We conclude that fabrication procedures and morphology strongly influence perovskite behaviour, with both free carrier and excitonic regimes possible, with strong implications for optoelectronic devices. PMID:26442125

  4. Role of Microstructure in the Electron-Hole Interaction of Hybrid Lead-Halide Perovskites.

    Science.gov (United States)

    Grancini, Giulia; Srimath Kandada, Ajay Ram; Frost, Jarvist M; Barker, Alex J; De Bastiani, Michele; Gandini, Marina; Marras, Sergio; Lanzani, Guglielmo; Walsh, Aron; Petrozza, Annamaria

    2015-10-01

    Solar cells based on hybrid inorganic-organic halide perovskites have demonstrated high power conversion efficiencies in a range of architectures. The existence and stability of bound electron-hole pairs in these materials, and their role in the exceptional performance of optoelectronic devices, remains a controversial issue. Here we demonstrate, through a combination of optical spectroscopy and multiscale modeling as a function of the degree of polycrystallinity and temperature, that the electron-hole interaction is sensitive to the microstructure of the material. The long-range order is disrupted by polycrystalline disorder and the variations in electrostatic potential found for smaller crystals suppress exciton formation, while larger crystals of the same composition demonstrate an unambiguous excitonic state. We conclude that fabrication procedures and morphology strongly influence perovskite behaviour, with both free carrier and excitonic regimes possible, with strong implications for optoelectronic devices.

  5. Role of microstructure in the electron-hole interaction of hybrid lead halide perovskites

    Science.gov (United States)

    Grancini, Giulia; Srimath Kandada, Ajay Ram; Frost, Jarvist M.; Barker, Alex J.; de Bastiani, Michele; Gandini, Marina; Marras, Sergio; Lanzani, Guglielmo; Walsh, Aron; Petrozza, Annamaria

    2015-10-01

    Organic-inorganic metal halide perovskites have demonstrated high power conversion efficiencies in solar cells and promising performance in a wide range of optoelectronic devices. The existence and stability of bound electron-hole pairs in these materials and their role in the operation of devices with different architectures remains a controversial issue. Here we demonstrate, through a combination of optical spectroscopy and multiscale modelling as a function of the degree of polycrystallinity and temperature, that the electron-hole interaction is sensitive to the microstructure of the material. The long-range order is disrupted by polycrystalline disorder and the variations in electrostatic potential found for smaller crystals suppress exciton formation, while larger crystals of the same composition demonstrate an unambiguous excitonic state. We conclude that fabrication procedures and morphology strongly influence perovskite behaviour, with both free carrier and excitonic regimes possible, with strong implications for optoelectronic devices.

  6. Novel Silver Cobaltacarborane Complexes with a Linearly Bridging Halide

    Energy Technology Data Exchange (ETDEWEB)

    Park, Hyun Seo; Bae, Hye Jin; Do, Youngkyu [KAIST, Daejeon (Korea, Republic of); Park, Youngwhan [LG Chem/Research Park, Daejeon (Korea, Republic of); Go, Min Jeong; Lee, Junseong [Chonnam National Univ., Gwangju (Korea, Republic of)

    2013-10-15

    The structural versatility of halides mainly originates from their coordinating abilities of adopting a bridging bond between two or more metal atoms, as well as a terminal bond. Moreover, a halide bridging bond angle is so flexible that thermodynamic stability can be endowed with proper geometry, which conceptually varies from acute to right, obtuse, and linear. In spite of innumerable reports on molecular metal halides, examples of the linearly bridging fashion are very scarce. The reason for the rarity of the linear M. X. M arrangement can be easily explained by the VSEPR (Valence Shell Electron Pair Repulsion) concept. The linear M. X. M formation has only been achieved by adopting a macrocyclic chelate ligand, which is structurally demanding, so that the VSEPR repulsions among lone-pair electrons on the halide atom could be overcome.

  7. Isothermal equation of state of a lithium fluoride single crystal

    Energy Technology Data Exchange (ETDEWEB)

    Kim, K.Y.

    1975-01-01

    An isothermal equation of state of a LiF single crystal was determined from length change measurements of the specimen as a function of hydrostatic pressure up to approximately 7 kbars at 28 to 41/sup 0/C. The length change was measured with an accuracy of approximately 500 A by using a Fabry Perot type He--Ne laser interferometer for a 1-m long specimen at temperatures constant to less than 0.002/sup 0/C. Several two- and three-parameter equations of state were used in analyzing the measured pressure-volume data. The computer fit for each equation of state determines not only the value of its parameters but also the standard deviations associated with them and one dependent variable, either pressure or volume. With the parameters determined, the equations of state are extrapolated to approximately 5 megabars in order to see discrepancies. Using the Born model of ionic solids, two equations of state were derived both from a power law potential and from an exponential form for the repulsive energy of alkali metal halides and used to fit the pressure-volume data of a LiF single crystal. They are also extrapolated to approximately 5 megabars. The Birch's two-parameter equation and the Grover, Getting, and Kennedy equation are indistinguishable from the two equations of state derived from the Born model for pressures approximately equal to or less than 800 kbars within +-20 kbars. The above four equations of state also fit closely the Pagannone and Drickamer static compression data, the Christian shock wave data, and the Kormer et al. shock wave data. The isothermal bulk modulus and its first pressure derivative at atmospheric pressure and 28.83/sup 0/C are 664.5 +- 0.5 kbars and 5.40 +- 0.18, respectively, in close agreement with those values ultrasonically measured by R. A. Miller and C. S. Smith. (auth)

  8. Structural and chemical analysis of gadolinium halides encapsulated within WS2 nanotubes

    Science.gov (United States)

    Anumol, E. A.; Enyashin, Andrey N.; Batra, Nitin M.; Costa, Pedro M. F. J.; Deepak, Francis Leonard

    2016-06-01

    The hollow cavities of nanotubes serve as templates for the growth of size- and shape-confined functional nanostructures, giving rise to novel materials and properties. In this work, considering their potential application as MRI contrast agents, gadolinium halides are encapsulated within the hollow cavities of WS2 nanotubes by capillary filling to obtain GdX3@WS2 nanotubes (where X = Cl, Br or I and @ means encapsulated in). Aberration corrected scanning/transmission electron microscopy (S/TEM) and spectroscopy is employed to understand the morphology and composition of the GdI3@WS2 nanotubes. The three dimensional morphology is studied with STEM tomography but understanding the compositional information is non-trivial due to the presence of multiple high atomic number elements. Therefore, energy dispersive X-ray spectroscopy (EDS) tomography was employed revealing the three dimensional chemical composition. Molecular dynamics simulations of the filling procedure shed light into the mechanics behind the formation of the confined gadolinium halide crystals. The quasi-1D system employed here serves as an example of a TEM-based chemical nanotomography method that could be extended to other materials, including beam-sensitive soft materials.The hollow cavities of nanotubes serve as templates for the growth of size- and shape-confined functional nanostructures, giving rise to novel materials and properties. In this work, considering their potential application as MRI contrast agents, gadolinium halides are encapsulated within the hollow cavities of WS2 nanotubes by capillary filling to obtain GdX3@WS2 nanotubes (where X = Cl, Br or I and @ means encapsulated in). Aberration corrected scanning/transmission electron microscopy (S/TEM) and spectroscopy is employed to understand the morphology and composition of the GdI3@WS2 nanotubes. The three dimensional morphology is studied with STEM tomography but understanding the compositional information is non-trivial due to the

  9. International Symposium on Halide Glasses (2nd) (Extended Abstracts).

    Science.gov (United States)

    1983-08-05

    method in which Pyrex 7740 is the standard material. These results will be compared with our earlier results on a fluorozirconate glass ( ZBLAN glass ...AliS 215 INTERNATIONAL SYMPOSIUM ON HALIDE GLASSES 12ND) 1/1 (EXTENDED ABSTRACTS) (U) RENSSELAER POLY’TECHNIC INST TROY NY DEPT OF MATERIALS ENGINEE...Classification) Second International Symposium on Halide Glasses (Extended Abstracts) (U) 12. PERSONAL AUTHOR(S) Cornelius T. Moynihan Chairman 13a

  10. Synthesis of methyl halides from biomass using engineered microbes.

    Science.gov (United States)

    Bayer, Travis S; Widmaier, Daniel M; Temme, Karsten; Mirsky, Ethan A; Santi, Daniel V; Voigt, Christopher A

    2009-05-13

    Methyl halides are used as agricultural fumigants and are precursor molecules that can be catalytically converted to chemicals and fuels. Plants and microorganisms naturally produce methyl halides, but these organisms produce very low yields or are not amenable to industrial production. A single methyl halide transferase (MHT) enzyme transfers the methyl group from the ubiquitous metabolite S-adenoyl methionine (SAM) to a halide ion. Using a synthetic metagenomic approach, we chemically synthesized all 89 putative MHT genes from plants, fungi, bacteria, and unidentified organisms present in the NCBI sequence database. The set was screened in Escherichia coli to identify the rates of CH(3)Cl, CH(3)Br, and CH(3)I production, with 56% of the library active on chloride, 85% on bromide, and 69% on iodide. Expression of the highest activity MHT and subsequent engineering in Saccharomyces cerevisiae results in productivity of 190 mg/L-h from glucose and sucrose. Using a symbiotic co-culture of the engineered yeast and the cellulolytic bacterium Actinotalea fermentans, we are able to achieve methyl halide production from unprocessed switchgrass (Panicum virgatum), corn stover, sugar cane bagasse, and poplar (Populus sp.). These results demonstrate the potential of producing methyl halides from non-food agricultural resources.

  11. Origins and Mechanisms of Hysteresis in Organometal Halide Perovskites.

    Science.gov (United States)

    Li, Cheng; Guerrero, Antonio; Zhong, Yu; Huettner, Sven

    2017-02-23

    Inorganic-organic organometal halide perovskites, such as CH3NH3PbI3 or CsPbI3, etc., are an unprecedented rising star in the field of photovoltaics since 2009, owing to its exceptionally high power conversion efficiency (PCE) and simple fabrication processability. Despite its relatively short history of development, intensive investigations have been concentrating on this material, ranging from crystal structure analysis and photophysical characterization, to performance optimization and device integration, etc. Yet, applied in photovoltaic devices, this material is suffering from hysteresis, that is, the difference of the current-voltage (I-V) curve during sweeping in two directions (from short-circuit towards open-circuit and vice versa). This behavior may significantly impede the large-scale commercial application. This Review will focus on the recent theoretical and experimental efforts to reveal the origin and mechanism of hysteresis. The proposed origins include (1) ferroelectric polarization, (2) charge trapping/detrapping and (3) ion migration. Among them, recent evidences consistently support that ion migration plays a key role for the hysteretic behavior in perovskite solar cells (PSC). Hence, this Review will summarize the recent results on ion migration, such as the migrating ion species, activation energy measurement, capacitive characterization and internal electrical field modulation, etc. In addition, this Review will also present the devices with alleviation/elimination of hysteresis by incorporating either large size grains or phenyl-C61-butyric acid methyl ester (PCBM) molecules. In a different application, the hysteretic property has been utilized in photovoltaic and memristive switching devices. In sum, by examining above three possible mechanisms, it is concluded that the origin of hysteresis of PSCs is associated with a combination of effects, both ion/defect migration and charge trapping/detrapping. This strong interaction between ion

  12. Molten salt phase diagram evaluation by pattern recognition:Part Ⅰ Divalent rare earth halide and alkali metal halide binary systems

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    At present CALPHAD (CALculation of PHAse Diagram) technique is not capable of predicting whether there exists intermediate compound, much less predicting the formulae, the number, and the melting congruence of intermediate compounds. To solve this problem, a new approach called the phase diagram evaluation by pattern recognition (PDEPR) was improved. The micro-parameters, such as the radius and the electronegativity of the element, were used as original features and then they were transformed and spanned to the different features in multi-dimensional space.Then a set of classifying functions were obtained to predict the information of intermediate compounds in REX2-AX systems (RE-rare earth element; A-Li, Na, K, Rb, and Cs; X F, Cl, Br, and 1). It is comparatively important for the design of materials.

  13. Zintl cluster chemistry in the alkali-metal-gallium systems

    Energy Technology Data Exchange (ETDEWEB)

    Henning, Robert [Iowa State Univ., Ames, IA (United States)

    1998-03-27

    Previous research into the alkali-metal-gallium systems has revealed a large variety of networked gallium deltahedra. The clusters are analogues to borane clusters and follow the same electronic requirements of 2n+2 skeletal electrons for closo-deltahedra. This work has focused on compounds that do not follow the typical electron counting rules. The first isolated gallium cluster was found in Cs8Ga11. The geometry of the Ga117- unit is not deltahedral but can be described as a penta-capped trigonal prism. The reduction of the charge from a closo-Ga1113- to Ga117- is believed to be the driving force of the distortion. The compound is paramagnetic because of an extra electron but incorporation of a halide atom into the structure captures the unpaired electron and forms a diamagnetic compound. A second isolated cluster has been found in Na10Ga10Ni where the tetra-capped trigonal prismatic gallium is centered by nickel. Stabilization of the cluster occurs through Ni-Ga bonding. A simple two-dimensional network occurs in the binary K2Ga3 Octahedra are connected through four waist atoms to form a layered structure with the potassium atoms sitting between the layers. Na30.5Ga60-xAgx is nonstoichiometric and needs only a small amount of silver to form (x ~ 2-6). The structure is composed of three different clusters which are interconnected to form a three-dimensional structure. The RbGa3-xAux system is also nonstoichiometric with a three-dimensional structure composed of Ga8 dodecahedra and four-bonded gallium atoms. Unlike Na30.5Ga60-xAgx, the RbGa3 binary is also stable. The binary is formally a Zintl phase but the ternary is not. Some chemistry in the alkali-metal-indium system also has been explored. A new potassium-indium binary

  14. High effective silica fume alkali activator

    Indian Academy of Sciences (India)

    Vladimír Živica

    2004-04-01

    Growing demands on the engineering properties of cement based materials and the urgency to decrease unsuitable ecologic impact of Portland cement manufacturing represent significant motivation for the development of new cement corresponding to these aspects. One category represents prospective alkali activated cements. A significant factor influencing their properties is alkali activator used. In this paper we present a new high effective alkali activator prepared from silica fume and its effectiveness. According to the results obtained this activator seems to be more effective than currently used activators like natrium hydroxide, natrium carbonate, and water glass.

  15. Dissolution Process of Palladium in Hydrochloric Acid: A Route via Alkali Metal Palladates

    Science.gov (United States)

    Kasuya, Ryo; Miki, Takeshi; Morikawa, Hisashi; Tai, Yutaka

    2015-12-01

    To improve the safety of the Pd recovery processes that use toxic oxidizers, dissolution of Pd in hydrochloric acid with alkali metal palladates was investigated. Alkali metal palladates were prepared by calcining a mixture of Pd black and alkali metal (Li, Na, and K) carbonates in air. Almost the entire amount of Pd was converted into Li2PdO2 after calcination at 1073 K (800 °C) using Li2CO3. In contrast, PdO was obtained by calcination at 1073 K (800 °C) using Na and K carbonates. Our results indicated that Li2CO3 is the most active reagent among the examined alkali metal carbonates for the formation of palladates. In addition, dissolution of the resulting Li2PdO2 in HCl solutions was evaluated under various conditions. In particular, Li2PdO2 rapidly dissolved in diluted (0.1 M) HCl at ambient temperature. Solubility of Pd of Li2PdO2 was found to be 99 pct or larger after dissolution treatment at 353 K (80 °C) for 5 minutes; in contrast, PdO hardly dissolved in 0.1 M HCl. The dissolution mechanism of Li2PdO2 in HCl was also elucidated by analysis of crystal structures and particulate properties. Since our process is completely free from toxic oxidizers, the dissolution process via alkali metal palladates is much safer than currently employed methods.

  16. DELIGNIFICATION OF SUGARCANE BAGASSE WITH ALKALI AND PERACETIC ACID AND CHARACTERIZATION OF THE PULP

    Directory of Open Access Journals (Sweden)

    Ting Zhang

    2010-06-01

    Full Text Available Sugarcane bagasse was delignified with alkali and peracetic acid in a two-stage process to obtain pulps with high yield and low kappa number. The experimental results indicated that alkali pretreatment prior to peracetic acid (PAA delignification could significantly reduce PAA loading by partially removing lignin and swelling the fibers. An optimum condition for the two-stage delignification was obtained for pulping of sugarcane bagasse. The pulps were further characterized by chemical composition analysis, strength property tests, Fourier Transform Infrared Spectroscopy (FTIR, X-Ray Diffraction (XRD, and Thermal Gravimetric Analysis (TGA. It was found that the alkali-PAA process could be conducted under milder conditions with resulting higher pulping selectivity, higher degree of polymerization (DP, and superior mechanical properties of pulps, compared to the kraft pulping process. Both kraft pulps and alkali-PAA pulp had similar FTIR spectra, XRD spectra, and TGA (DTG curves. However, further analysis indicated that the alkali-PAA pulp had higher infrared crystallization index and cellulose crystallinity.

  17. Structural and Chemical Analysis of Gadolinium Halides Encapsulated within WS 2 Nanotubes

    KAUST Repository

    Anumol, E A

    2016-05-18

    The hollow cavities of nanotubes could serve as templates for the growth of size- and shape-confined functional nanostructures, giving rise to novel materials and properties. In this work, considering their potential application as MRI contrast agents, gadolinium halides are encapsulated within the hollow cavities of inorganic nanotubes of WS2 by capillary filling to obtain GdX3@WS2 nanotubes (where X = Cl, Br or I and @ means encapsulated in). Aberration corrected scanning/transmission electron microscopy (S/TEM) and spectroscopy is employed to understand the morphology and composition of the GdI3@WS2 nanotubes. The three dimensional morphology is studied with STEM tomography but understanding the compositional information is a non-trivial matter due to the presence of multiple high atomic number elements. Therefore, energy dispersive X-ray spectroscopy (EDS) tomography was employed revealing the three dimensional chemical composition. Molecular dynamics simulations of the filling procedure shed light into the mechanics behind the formation of the confined gadolinium halide crystals. The quasi-1D system employed here serves as an example of a TEM-based chemical nanotomography method that could be extended to other materials, including beam-sensitive soft materials.

  18. All Inorganic Halide Perovskites Nanosystem: Synthesis, Structural Features, Optical Properties and Optoelectronic Applications.

    Science.gov (United States)

    Li, Xiaoming; Cao, Fei; Yu, Dejian; Chen, Jun; Sun, Zhiguo; Shen, Yalong; Zhu, Ying; Wang, Lin; Wei, Yi; Wu, Ye; Zeng, Haibo

    2017-03-01

    The recent success of organometallic halide perovskites (OHPs) in photovoltaic devices has triggered lots of corresponding research and many perovskite analogues have been developed to look for devices with comparable performance but better stability. Upon the preparation of all inorganic halide perovskite nanocrystals (IHP NCs), research activities have soared due to their better stability, ultrahigh photoluminescence quantum yield (PL QY), and composition dependent luminescence covering the whole visible region with narrow line-width. They are expected to be promising materials for next generation lighting and display, and many other applications. Within two years, a lot of interesting results have been observed. Here, the synthesis of IHPs is reviewed, and their progresses in optoelectronic devices and optical applications, such as light-emitting diodes (LEDs), photodetectors (PDs), solar cells (SCs), and lasing, is presented. Information and recent understanding of their crystal structures and morphology modulations are addressed. Finally, a brief outlook is given, highlighting the presently main problems and their possible solutions and future development directions.

  19. Crystal structures of new alkali metal-rich oxometallates. Rubidium aluminate tetrahydroxide, Rb{sub 9}(AlO{sub 4})(OH){sub 4}, rubidium orthogallate, Rb{sub 5}GaO{sub 4}, cesium bis-chromate(IV) oxide, Cs{sub 10}(CrO{sub 4}){sub 2}O, and cesium diindate, Cs{sub 8}In{sub 2}O{sub 7}

    Energy Technology Data Exchange (ETDEWEB)

    Bender, Johannes; Wohlfarth, Andreas; Hoch, Constantin [Max-Planck-Institut fuer Festkoerperforschung, Stuttgart (Germany)

    2010-12-15

    Several new alkali metal oxometallates with anions built up from tetrahedral [MO{sub 4}] units were obtained in reactions aimed at the formation of alkali metal suboxometallates or by thermally decomposing the latter. Rubidium orthoaluminate tetrahydroxide Rb{sub 9}(AlO{sub 4})(OH){sub 4} crystallizes with a new structure type (space group P2{sub 1}/c, a = 13.116(1), b = 6.9266(5), c = 18.934(2) A, {beta} = 92.05(1) , V = 1719.0(3) A{sup 3}, Z = 4, R1 = 0.0352) and contains orthoaluminate anions [AlO{sub 4}]{sup 5-} and isolated hydroxide anions. Rubidium orthogallate Rb{sub 5}GaO{sub 4} crystallizes with the Na{sub 5}GaO{sub 4} structure type (space group Pbca, a = 6.9318(5), b = 21.309(2), c = 11.740(1) A, V = 1734.2(3) A{sup 3}, Z = 8, R1 = 0.0423) with isolated orthogallate anions [GaO{sub 4}]{sup 5-}. Cesium chromate oxide Cs{sub 10}(CrO{sub 4}){sub 2}O adopts the Cs{sub 10}(GeO{sub 4}){sub 2}O structure type (space group P2{sub 1}/c, a = 12.903(1), b = 11.4523(8), c = 19.074(3) A, {beta} = 127.903(8) , V = 2223.9(4) A{sup 3}, Z = 4, R1 = 0.0326) with orthochromate(IV) anions [CrO{sub 4}]{sup 4-} and isolated oxide anions. In all orthometallates the anions [MO{sub 4}]{sup n-} deviate only slightly from ideal tetrahedral symmetry. Cesium diindate Cs{sub 8}In{sub 2}O{sub 7} crystallizes with the Cs{sub 8}Fe{sub 2}O{sub 7} structure type (space group P2{sub 1}/c, a = 7.4307(6), b = 18.6181(14), c = 7.2639(6) A {beta} = 119.225(8) , V = 877.0(1) A{sup 3}, Z = 2, R1 = 0.0349). A single-crystal structure investigation at r.t. has shown linear diindate units, but the temperature dependence of the libration angles from TLS studies for the bridging oxygen atom suggests a slightly bent and dynamically disordered diindate anion. (orig.)

  20. The Renaissance of Halide Perovskites and Their Evolution as Emerging Semiconductors.

    Science.gov (United States)

    Stoumpos, Constantinos C; Kanatzidis, Mercouri G

    2015-10-20

    The recent re-emergence of the halide perovskites, of the type AMX3, derives from a sea-changing breakthrough in the field of photovoltaics that has led to a whole new generation of solar devices with remarkable power conversion efficiency. The success in the field of photovoltaics has led to intense, combined research efforts to better understand these materials both from the fundamental chemistry and physics points of view and for the improvement of applied functional device engineering. This groundswell of activity has breathed new life into this long-known but largely "forgotten" class of perovskites. The impressive achievements of halide perovskites in photovoltaics, as well as other optoelectronic applications, stem from an unusually favorable combination of optical and electronic properties, with the ability to be solution processed into films. This defines them as a brand new class of semiconductors that can rival or exceed the performance of the venerable classes of III-V and II-IV semiconductors, which presently dominate the industries of applied optoelectronics. Our aim in this Account is to highlight the basic pillars that define the chemistry of the halide perovskites and their unconventional electronic properties through the prism of structure-property relationships. We focus on the synthetic requirements under which a halide perovskite can exist and emphasize how the synthetic conditions can determine the structural integrity and the bulk properties of the perovskites. Then we proceed to discuss the origins of the optical and electronic phenomena, using the perovskite crystal structure as a guide. Some of the most remarkable features of the perovskites dealt with in this Account include the evolution of a unique type of defect, which gives rise to superlattices. These can enhance or diminish the fluorescence properties of the perovskites. For example, the exotic self-doping ability of the Sn-based perovskites allows them to adopt electrical

  1. Relaxation of quadrupole orientation in an optically pumped alkali vapour

    Energy Technology Data Exchange (ETDEWEB)

    Bernabeu, E.; Tornos, J.

    1985-04-01

    The relaxation of quadrupole orientation (alignment) in an optically pumped alkali vapour is theoretically studied by taking into account the relaxation processes by alkali-buffer gas, alkali-alkali with spin exchange and alkali-cell wall (diffusion process) collisions. The relaxation transients of the quadrupole orientation are obtained by introducing a first-order weak-pumping approximation (intermediate pumping) less restrictive than the usually considered (zeroth order) one.

  2. Milk Alkali and Hydrochlorothiazide: A Case Report

    Directory of Open Access Journals (Sweden)

    Babar Parvez

    2011-01-01

    Full Text Available Hypercalcemia is a relatively common clinical problem in both outpatient and inpatient settings. Primary pathophysiology is the entry of calcium that exceeds its excretion into urine or deposition in bone into circulation. Among a wide array of causes of hypercalcemia, hyperparathyroidism and malignancy are the most common, accounting for greater than 90 percent of cases. Concordantly, there has been a resurgence of milk-alkali syndrome associated with the ingestion of large amounts of calcium and absorbable alkali, making it the third leading cause of hypercalcemia (Beall and Scofield, 1995 and Picolos et al., 2005. This paper centers on a case of over-the-counter calcium and alkali ingestion for acid reflux leading to milk alkali with concordant use of thiazide diuretic for hypertension.

  3. Two Dimensional Organometal Halide Perovskite Nanorods with Tunable Optical Properties.

    Science.gov (United States)

    Aharon, Sigalit; Etgar, Lioz

    2016-05-11

    Organo-metal halide perovskite is an efficient light harvester in photovoltaic solar cells. Organometal halide perovskite is used mainly in its "bulk" form in the solar cell. Confined perovskite nanostructures could be a promising candidate for efficient optoelectronic devices, taking advantage of the superior bulk properties of organo-metal halide perovskite, as well as the nanoscale properties. In this paper, we present facile low-temperature synthesis of two-dimensional (2D) lead halide perovskite nanorods (NRs). These NRs show a shift to higher energies in the absorbance and in the photoluminescence compared to the bulk material, which supports their 2D structure. X-ray diffraction (XRD) analysis of the NRs demonstrates their 2D nature combined with the tetragonal 3D perovskite structure. In addition, by alternating the halide composition, we were able to tune the optical properties of the NRs. Fast Fourier transform, and electron diffraction show the tetragonal structure of these NRs. By varying the ligands ratio (e.g., octylammonium to oleic acid) in the synthesis, we were able to provide the formation mechanism of these novel 2D perovskite NRs. The 2D perovskite NRs are promising candidates for a variety of optoelectronic applications, such as light-emitting diodes, lasing, solar cells, and sensors.

  4. Halide Perovskites: Poor Man's High-Performance Semiconductors.

    Science.gov (United States)

    Stoumpos, Constantinos C; Kanatzidis, Mercouri G

    2016-07-01

    Halide perovskites are a rapidly developing class of medium-bandgap semiconductors which, to date, have been popularized on account of their remarkable success in solid-state heterojunction solar cells raising the photovoltaic efficiency to 20% within the last 5 years. As the physical properties of the materials are being explored, it is becoming apparent that the photovoltaic performance of the halide perovskites is just but one aspect of the wealth of opportunities that these compounds offer as high-performance semiconductors. From unique optical and electrical properties stemming from their characteristic electronic structure to highly efficient real-life technological applications, halide perovskites constitute a brand new class of materials with exotic properties awaiting discovery. The nature of halide perovskites from the materials' viewpoint is discussed here, enlisting the most important classes of the compounds and describing their most exciting properties. The topics covered focus on the optical and electrical properties highlighting some of the milestone achievements reported to date but also addressing controversies in the vastly expanding halide perovskite literature.

  5. Thermoluminescence and F centers of manganese doped NaCl and NaCl-CKl crystals exposed to gamma radiation

    Energy Technology Data Exchange (ETDEWEB)

    Somera, L.; Cruz Z, E.; Roman L, J. [UNAM, Instituto de Ciencias Nucleares, Circuito Exterior, Ciudad Universitaria, 04510 Mexico D. F. (Mexico); Hernandez A, J. M.; Murrieta S, H., E-mail: ecruz@nucleares.unam.mx [UNAM, Instituto de Fisica, Circuito Exterior, Ciudad Universitaria, 04510 Mexico D. F. (Mexico)

    2015-10-15

    Alkali halides crystals doped with rare earths or transition metals have been widely studied due to the luminescence properties. In particular, NaCl and KCl single crystals present thermally stimulated luminescence (Tl) after gamma irradiation. The NaCl and the NaCl KCl mixed crystal doped with manganese (MnCl{sub 2}) impurity were grown by using the Czochralski method. The emission characteristic of Mn{sup 2+} was observed at 543 nm. The crystals were exposed between 0.02 and 10 kGy gamma dose from {sup 60}Co irradiator. Optical absorption at room temperature shows the peaked band at 452 nm corresponding to the manganese impurity. The F bands, was ascribed to the electron trapped in the anion vacancy in the lattice, were obtained at 452 nm and 455 nm belonging to NaCl:Mn and NaCl KCl:Mn, respectively. The F band increases as the doses increase and it was bleaching by the UV light at 470 nm. The glow curves of the samples show the first glow peak between 92-103 degrees C, while the second main peak was observed at 183 degrees C for the undoped NaCl and at 148 and 165 degrees C for the NaCl:Mn and NaCl-KCl:Mn, respectively. The main peak was slowly bleaching when the irradiated sample was illuminated with F (470 nm) light. Optical bleaching confirms that the F center has an important participation in the thermoluminescent response. The glow curves structure from the thermal bleaching suggests the participation of different kind of traps. Also, the kinetics parameters such as activation energy (E), frequency factor (s) and the kinetic order (b) were investigated. (Author)

  6. Unconventional superconductivity in electron-doped layered metal nitride halides MNX (M = Ti, Zr, Hf; X = Cl, Br, I)

    Energy Technology Data Exchange (ETDEWEB)

    Kasahara, Yuichi, E-mail: ykasahara@scphys.kyoto-u.ac.jp [Department of Physics, Kyoto University, Kyoto 606-8502 (Japan); Kuroki, Kazuhiko, E-mail: kuroki@phys.sci.osaka-u.ac.jp [Department of Physics, Osaka University, Toyonaka, Osaka 560-0043 (Japan); Yamanaka, Shoji, E-mail: syamana@hiroshima-u.ac.jp [Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, Higashi-Hiroshima, Hiroshima 739-8527 (Japan); Taguchi, Yasujiro, E-mail: y-taguchi@riken.jp [RIKEN Center for Emergent Matter Science (CEMS), Wako 351-0198 (Japan)

    2015-07-15

    In this review, we present a comprehensive overview of superconductivity in electron-doped metal nitride halides MNX (M = Ti, Zr, Hf; X = Cl, Br, I) with layered crystal structure and two-dimensional electronic states. The parent compounds are band insulators with no discernible long-range ordered state. Upon doping tiny amount of electrons, superconductivity emerges with several anomalous features beyond the conventional electron–phonon mechanism, which stimulate theoretical investigations. We will discuss experimental and theoretical results reported thus far and compare the electron-doped layered nitride superconductors with other superconductors.

  7. Halide-Dependent Electronic Structure of Organolead Perovskite Materials

    KAUST Repository

    Buin, Andrei

    2015-06-23

    © 2015 American Chemical Society. Organometal halide perovskites have recently attracted tremendous attention both at the experimental and theoretical levels. These materials, in particular methylammonium triiodide, are still limited by poor chemical and structural stability under ambient conditions. Today this represents one of the major challenges for polycrystalline perovskite-based photovoltaic technology. In addition to this, the performance of perovskite-based devices is degraded by deep localized states, or traps. To achieve better-performing devices, it is necessary to understand the nature of these states and the mechanisms that lead to their formation. Here we show that the major sources of deep traps in the different halide systems have different origin and character. Halide vacancies are shallow donors in I-based perovskites, whereas they evolve into a major source of traps in Cl-based perovskites. Lead interstitials, which can form lead dimers, are the dominant source of defects in Br-based perovskites, in line with recent experimental data. As a result, the optimal growth conditions are also different for the distinct halide perovskites: growth should be halide-rich for Br and Cl, and halide-poor for I-based perovskites. We discuss stability in relation to the reaction enthalpies of mixtures of bulk precursors with respect to final perovskite product. Methylammonium lead triiodide is characterized by the lowest reaction enthalpy, explaining its low stability. At the opposite end, the highest stability was found for the methylammonium lead trichloride, also consistent with our experimental findings which show no observable structural variations over an extended period of time.

  8. High-Purity Hybrid Organolead Halide Perovskite Nanoparticles Obtained by Pulsed-Laser Irradiation in Liquid

    KAUST Repository

    Amendola, Vincenzo

    2016-11-17

    Nanoparticles of hybrid organic-inorganic perovskites have attracted a great deal of attention due to their variety of optoelectronic properties, their low cost, and their easier integration into devices with complex geometry, compared with microcrystalline, thin-film, or bulk metal halides. Here we present a novel one-step synthesis of organolead bromide perovskite nanocrystals based on pulsed-laser irradiation in a liquid environment (PLIL). Starting from a bulk CHNHPbBr crystal, our PLIL procedure does not involve the use of high-boiling-point polar solvents or templating agents, and runs at room temperature. The resulting nanoparticles are characterized by high crystallinity and are completely free of any microscopic product or organic coating layer. We also demonstrate the straightforward inclusion of laser-generated perovskite nanocrystals in a polymeric matrix to form a nanocomposite with single- and two-photon luminescence properties.

  9. Excitons versus free charges in organo-lead tri-halide perovskites

    Science.gov (United States)

    D'Innocenzo, Valerio; Grancini, Giulia; Alcocer, Marcelo J. P.; Kandada, Ajay Ram Srimath; Stranks, Samuel D.; Lee, Michael M.; Lanzani, Guglielmo; Snaith, Henry J.; Petrozza, Annamaria

    2014-04-01

    Excitonic solar cells, within which bound electron-hole pairs have a central role in energy harvesting, have represented a hot field of research over the last two decades due to the compelling prospect of low-cost solar energy. However, in such cells, exciton dissociation and charge collection occur with significant losses in energy, essentially due to poor charge screening. Organic-inorganic perovskites show promise for overcoming such limitations. Here, we use optical spectroscopy to estimate the exciton binding energy in the mixed-halide crystal to be in the range of 50 meV. We show that such a value is consistent with almost full ionization of the exciton population under photovoltaic cell operating conditions. However, increasing the total photoexcitation density, excitonic species become dominant, widening the perspective of this material for a host of optoelectronic applications.

  10. Lattice dynamics and the nature of structural transitions in organolead halide perovskites

    Energy Technology Data Exchange (ETDEWEB)

    Comin, Riccardo; Crawford, Michael K.; Said, Ayman H.; Herron, Norman; Guise, William E.; Wang, Xiaoping; Whitfield, Pamela S.; Jain, Ankit; Gong, Xiwen; McGaughey, Alan J. H.; Sargent, Edward H.

    2016-09-09

    Organolead halide perovskites are a family of hybrid organic-inorganic compounds whose remarkable optoelectronic properties have been under intensive scrutiny in recent years. Here we use inelastic x-ray scattering to study low-energy lattice excitations in single crystals of methylammonium lead iodide and bromide perovskites. Our findings confirm the displacive nature of the cubic-to-tetragonal phase transition, which is further shown, using neutron and x-ray diffraction, to be close to a tricritical point. Lastly, we detect quasistatic symmetry-breaking nanodomains persisting well into the high-temperature cubic phase, possibly stabilized by local defects. These findings reveal key structural properties of these materials, and also bear important implications for carrier dynamics across an extended temperature range relevant for photovoltaic applications.

  11. Alkali-metalated forms of thiacalix[4]arenes.

    Science.gov (United States)

    Zeller, Jürgen; Radius, Udo

    2006-11-13

    The alkali metal salts [TCALi4] (1), [TCANa4] (2), and [TCALK4] (3) of fully deprotonated p-tert-butyltetrathiacalix[4]arene (H(4)TCA) are readily available from the reactions of thiacalix[4]arene and n-BuLi, NaH, or KH as deprotonating reagents. Crystals of the sodium salts 2 and the potassium salt 3 suitable for X-ray diffraction were obtained in the form of the pyridine solvates [(TCA)2Na8.8py] (2.8py) and [(TCA)2K(8).8py] (3.8py). These molecules are dimers in the solid state but are structurally not related. In addition, the reaction of H(4)TCA and lithium hydroxide afforded the structurally characterized complex [(TCA)Li5(OH).4THF] (4). The molecular structure of 4 as well as the structures of 2.8py and 3.8py reveal a close relationship to the corresponding alkali metal salts of the calix[4]arenes.

  12. Periodic DFT approaches to crystalline alkali metal azides

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The energy bands, electronic structures andrelationship between structures and properties of the crys-talline alkali metal azides, LiN3, α-NaN3 and KN3, are investigated at the DFT-B3LYP level. The crystalline bulks arepredicted to be insulator, speculated from their band gaps ofca. 0.23-0.25 a.u. and from their level frontier bands. Theatomic overlaps and electron densities show that the metalsand the azides are combined by ionic bonds. The crystal lat-tice energies, being corrected for the basis set superpositionerrors, are -852.30, -771.45 and - 614.78 kJ @ mol-1 for LiN3,α-NaN3 and KN3 respectively. These values are similar tothose by Gray's approximate method. The frontier crystalorbital mainly consists of the atomic orbital of the terminalnitrogen of azides. The contribution of the metallic orbital tothe LUMO is very small. The electron transition from theHOMO to the LUMO is difficult to occur. Hence all the al-kali metal azides are expected to be insensitive explosives,according to the "principle of easiest electron transition".

  13. Novel, inorganic composites using porous, alkali-activated, aluminosilicate binders

    Science.gov (United States)

    Musil, Sean

    Geopolymers are an inorganic polymeric material composed of alumina, silica, and alkali metal oxides. Geopolymers are chemical and fire resistant, can be used as refractory adhesives, and are processed at or near ambient temperature. These properties make geopolymer an attractive choice as a matrix material for elevated temperature composites. This body of research investigated numerous different reinforcement possibilities and variants of geopolymer matrix material and characterized their mechanical performance in tension, flexure and flexural creep. Reinforcements can then be chosen based on the resulting properties to tailor the geopolymer matrix composites to a specific application condition. Geopolymer matrix composites combine the ease of processing of polymer matrix composites with the high temperature capability of ceramic matrix composites. This study incorporated particulate, unidirectional fiber and woven fiber reinforcements. Sodium, potassium, and cesium based geopolymer matrices were evaluated with cesium based geopolymer showing great promise as a high temperature matrix material. It showed the best strength retention at elevated temperature, as well as a very low coefficient of thermal expansion when crystallized into pollucite. These qualities made cesium geopolymer the best choice for creep resistant applications. Cesium geopolymer binders were combined with unidirectional continuous polycrystalline mullite fibers (Nextel(TM) 720) and single crystal mullite fibers, then the matrix was crystallized to form cubic pollucite. Single crystal mullite fibers were obtained by the internal crystallization method and show excellent creep resistance up to 1400°C. High temperature flexural strength and flexural creep resistance of pollucite and polycrystalline/single-crystal fibers was evaluated at 1000-1400°C.

  14. The effects of halide anions on the dielectric response of potassium halide solutions in visible, UV and far UV region.

    Science.gov (United States)

    Shagieva, F M; Boinovich, L B

    2013-06-07

    Based on the experimentally measured dispersion of refractive indices, we studied the effects of halide anions on the dielectric response of potassium halide solutions in the visible, UV and far UV regions. It was shown that a specific ion effect according to the Hofmeister series is clearly demonstrated for the visible range of spectra. For the near-, mid-, and far UV ranges of spectra, the specific ion effect essentially depends on solution concentration and temperature. The influence of ions on the behavior of dynamic dielectric permittivity of a solution is discussed on the basis of ion/water and ion/ion electrostatic and electrodynamic interactions and hydration shell structure.

  15. Kinetic Studies of the Solvolysis of Two Organic Halides

    Science.gov (United States)

    Duncan, J. A.; Pasto, D. J.

    1975-01-01

    Describes an undergraduate organic chemistry laboratory experiment which utilizes the solvolysis of organic halides to demonstrate first and second order reaction kinetics. The experiment also investigates the effect of a change of solvent polarity on reaction rate, common-ion and noncommon-ion salt effects, and the activation parameters of a…

  16. Methyl halide emissions from savanna fires in southern Africa

    Science.gov (United States)

    Andreae, M. O.; Atlas, E.; Harris, G. W.; Helas, G.; de Kock, A.; Koppmann, R.; Maenhaut, W.; Manø, S.; Pollock, W. H.; Rudolph, J.; Scharffe, D.; Schebeske, G.; Welling, M.

    1996-10-01

    The methyl halides, methyl chloride (CH3Cl), methyl bromide (CH3Br), and methyl iodide (CH3I), were measured in regional air samples and smoke from savanna fires in southern Africa during the Southern Africa Fire-Atmosphere Research Initiative-92 (SAFARI-92) experiment (August-October 1992). All three species were significantly enhanced in the smoke plumes relative to the regional background. Good correlations were found between the methyl halides and carbon monoxide, suggesting that emission was predominantly associated with the smoldering phase of the fires. About 90% of the halogen content of the fuel burned was released to the atmosphere, mostly as halide species, but a significant fraction (3-38%) was emitted in methylated form. On the basis of comparison with the composition of the regional background atmosphere, emission ratios to carbon dioxide and carbon monoxide were determined for the methyl halide species. The emission ratios decreased in the sequence CH3Cl > CH3Br > CH3I. Extrapolation of these results in combination with data from other types of biomass burning, e.g. forest fires, suggests that vegetation fires make a significant contribution to the atmospheric budget of CH3Cl and CH3Br. For tropospheric CH3I, on the other hand, fires appear to be a minor source. Our results suggest that pyrogenic emissions of CH3Cl and CH3Br need to be considered as significant contributors to stratospheric ozone destruction.

  17. Advances and Promises of Layered Halide Hybrid Perovskite Semiconductors

    NARCIS (Netherlands)

    Pedesseau, Laurent; Sapori, Daniel; Traore, Boubacar; Robles, Roberto; Fang, Hong-Hua; Loi, Maria Antonietta; Tsai, Hsinhan; Nie, Wanyi; Blancon, Jean-Christophe; Neukirch, Amanda; Tretiak, Sergei; Mohite, Aditya D.; Katan, Claudine; Even, Jacky; Kepenekian, Mikael

    2016-01-01

    Layered halide hybrid organic inorganic perovskites (HOP) have been the subject of intense investigation before the rise of three-dimensional (3D) HOP and their impressive performance in solar cells. Recently, layered HOP have also been proposed as attractive alternatives for photostable solar cells

  18. Students' Understanding of Alkyl Halide Reactions in Undergraduate Organic Chemistry

    Science.gov (United States)

    Cruz-Ramirez de Arellano, Daniel

    2013-01-01

    Organic chemistry is an essential subject for many undergraduate students completing degrees in science, engineering, and pre-professional programs. However, students often struggle with the concepts and skills required to successfully solve organic chemistry exercises. Since alkyl halides are traditionally the first functional group that is…

  19. Semiempirical and DFT Investigations of the Dissociation of Alkyl Halides

    Science.gov (United States)

    Waas, Jack R.

    2006-01-01

    Enthalpy changes corresponding to the gas phase heats of dissociation of 12 organic halides were calculated using two semiempirical methods, the Hartree-Fock method, and two DFT methods. These calculated values were compared to experimental values where possible. All five methods agreed generally with the expected empirically known trends in the…

  20. On the Boiling Points of the Alkyl Halides.

    Science.gov (United States)

    Correia, John

    1988-01-01

    Discusses the variety of explanations in organic chemistry textbooks of a physical property of organic compounds. Focuses on those concepts explaining attractive forces between molecules. Concludes that induction interactions play a major role in alkyl halides and other polar organic molecules and should be given wider exposure in chemistry texts.…

  1. Iron-catalysed Negishi coupling of benzyl halides and phosphates.

    Science.gov (United States)

    Bedford, Robin B; Huwe, Michael; Wilkinson, Mark C

    2009-02-01

    Iron-based catalysts containing either 1,2-bis(diphenylphosphino)benzene or 1,3-bis(diphenylphosphino)propane give excellent activity and good selectivity in the Negishi coupling of aryl zinc reagents with a range of benzyl halides and phosphates.

  2. One-dimensional organic lead halide perovskites with efficient bluish white-light emission

    Science.gov (United States)

    Yuan, Zhao; Zhou, Chenkun; Tian, Yu; Shu, Yu; Messier, Joshua; Wang, Jamie C.; van de Burgt, Lambertus J.; Kountouriotis, Konstantinos; Xin, Yan; Holt, Ethan; Schanze, Kirk; Clark, Ronald; Siegrist, Theo; Ma, Biwu

    2017-01-01

    Organic-inorganic hybrid metal halide perovskites, an emerging class of solution processable photoactive materials, welcome a new member with a one-dimensional structure. Herein we report the synthesis, crystal structure and photophysical properties of one-dimensional organic lead bromide perovskites, C4N2H14PbBr4, in which the edge sharing octahedral lead bromide chains [PbBr4 2-]∞ are surrounded by the organic cations C4N2H14 2+ to form the bulk assembly of core-shell quantum wires. This unique one-dimensional structure enables strong quantum confinement with the formation of self-trapped excited states that give efficient bluish white-light emissions with photoluminescence quantum efficiencies of approximately 20% for the bulk single crystals and 12% for the microscale crystals. This work verifies once again that one-dimensional systems are favourable for exciton self-trapping to produce highly efficient below-gap broadband luminescence, and opens up a new route towards superior light emitters based on bulk quantum materials.

  3. One-dimensional organic lead halide perovskites with efficient bluish white-light emission

    Science.gov (United States)

    Yuan, Zhao; Zhou, Chenkun; Tian, Yu; Shu, Yu; Messier, Joshua; Wang, Jamie C.; van de Burgt, Lambertus J.; Kountouriotis, Konstantinos; Xin, Yan; Holt, Ethan; Schanze, Kirk; Clark, Ronald; Siegrist, Theo; Ma, Biwu

    2017-01-01

    Organic-inorganic hybrid metal halide perovskites, an emerging class of solution processable photoactive materials, welcome a new member with a one-dimensional structure. Herein we report the synthesis, crystal structure and photophysical properties of one-dimensional organic lead bromide perovskites, C4N2H14PbBr4, in which the edge sharing octahedral lead bromide chains [PbBr4 2−]∞ are surrounded by the organic cations C4N2H14 2+ to form the bulk assembly of core-shell quantum wires. This unique one-dimensional structure enables strong quantum confinement with the formation of self-trapped excited states that give efficient bluish white-light emissions with photoluminescence quantum efficiencies of approximately 20% for the bulk single crystals and 12% for the microscale crystals. This work verifies once again that one-dimensional systems are favourable for exciton self-trapping to produce highly efficient below-gap broadband luminescence, and opens up a new route towards superior light emitters based on bulk quantum materials. PMID:28051092

  4. Modeling and Investigation of Heavy Oxide and Alkali-Halide Scintillators for Potential Use in Neutron and Gamma Detection Systems

    Science.gov (United States)

    2015-06-01

    scintillators, MCNP, detection efficiency, neutron detection 15. NUMBER OF PAGES 71 16. PRICE CODE 17. SECURITY CLASSIFICATION OF REPORT...have unusually high detection efficiency of fast neutrons as a result of inelastic scattering [4]. Much work has been done both at NPS and the... events . Detection systems currently being used to detect radioactive material (RM) rely on bulky assemblies consisting of components such as organic

  5. Selection of non-adsorbing alkali components

    Energy Technology Data Exchange (ETDEWEB)

    Lee, S.H.D.; Natesan, K.; Swift, W.M.

    1992-11-01

    This project consists of three phases of laboratory experimental study. In phase I (screening), eight candidate materials, 304SS (serves as a base material for comparison), Hastelloy C-276, Hastelloy X, Haynes No. 188, Allonized 304SS, Pt-coated 304SS, and ceramic-coated 304SS, will be subjected to atmospheric TGA study under the simulated PFBC (oxidizing) environment with and without alkali vapor doping. Each candidate material will be evaluated for its resistance toward alkali-vapor capture. In addition, a post-test metallographic characterization of the sample will be performed to obtain a better understanding of the alkali capture mechanism and material behavior. The material(s) with little or no alkali-vapor adsorption will be selected as the promising material(s) for the Phase II study. In Phase II, the promising material(s) will be further tested in the TGA under elevated pressure to simulate the PFBC environment (in terms of temperature, pressure, and gas composition). The effect of pressure on the extent of alkali-vapor adsorption will be evaluated, and the test samples will be metallographically characterized. The most promising candidate material(s) will be identified and recommended for further tesfing in the actual PFBC environment. In Phase III, four materials will be selected from the eight candidate materials screened in the PFBC environment and will be evaluated for their alkali-vapor capture by atmospheric TGA under the coal gasification fuel gas (reducing) environment. The tested samples will also be metallographically characterized. The most promising material(s) will be identified and recommended for further testing in the actual coal gasification environment.

  6. Selection of non-adsorbing alkali components

    Energy Technology Data Exchange (ETDEWEB)

    Lee, S.H.D.; Natesan, K.; Swift, W.M.

    1992-01-01

    This project consists of three phases of laboratory experimental study. In phase I (screening), eight candidate materials, 304SS (serves as a base material for comparison), Hastelloy C-276, Hastelloy X, Haynes No. 188, Allonized 304SS, Pt-coated 304SS, and ceramic-coated 304SS, will be subjected to atmospheric TGA study under the simulated PFBC (oxidizing) environment with and without alkali vapor doping. Each candidate material will be evaluated for its resistance toward alkali-vapor capture. In addition, a post-test metallographic characterization of the sample will be performed to obtain a better understanding of the alkali capture mechanism and material behavior. The material(s) with little or no alkali-vapor adsorption will be selected as the promising material(s) for the Phase II study. In Phase II, the promising material(s) will be further tested in the TGA under elevated pressure to simulate the PFBC environment (in terms of temperature, pressure, and gas composition). The effect of pressure on the extent of alkali-vapor adsorption will be evaluated, and the test samples will be metallographically characterized. The most promising candidate material(s) will be identified and recommended for further tesfing in the actual PFBC environment. In Phase III, four materials will be selected from the eight candidate materials screened in the PFBC environment and will be evaluated for their alkali-vapor capture by atmospheric TGA under the coal gasification fuel gas (reducing) environment. The tested samples will also be metallographically characterized. The most promising material(s) will be identified and recommended for further testing in the actual coal gasification environment.

  7. On dewetting of thin films due to crystallization (crystallization dewetting).

    Science.gov (United States)

    Habibi, Mehran; Rahimzadeh, Amin; Eslamian, Morteza

    2016-03-01

    Drying and crystallization of a thin liquid film of an ionic or a similar solution can cause dewetting in the resulting thin solid film. This paper aims at investigating this type of dewetting, herein termed "crystallization dewetting", using PbI2 dissolved in organic solvents as the model solution. PbI2 solid films are usually used in X-ray detection and lead halide perovskite solar cells. In this work, PbI2 films are fabricated using spin coating and the effect of major parameters influencing the crystallization dewetting, including the type of the solvent, solution concentration, drying temperature, spin speed, as well as imposed vibration on the substrate are studied on dewetting, surface profile and coverage, using confocal scanning laser microscopy. Simplified hydrodynamic governing equations of crystallization in thin films are presented and using a mathematical representation of the process, it is phenomenologically demonstrated that crystallization dewetting occurs due to the absorption and consumption of the solution surrounding a growing crystal. Among the results, it is found that a low spin speed (high thickness), a high solution concentration and a low drying temperature promote crystal growth, and therefore crystallization dewetting. It is also shown that imposed vibration on the substrate can affect the crystal size and crystallization dewetting.

  8. Rb-Sr Isotopic Systematics of Alkali-Rich Fragments in the Yamato-74442 LL-Chondritic Breccia

    Science.gov (United States)

    Yokoyama, T.; Misawa, K.; Okano, O.; Shih, C.-Y.; Nyquist, L. E.; Simo, J. I.; Tappa, M. J.; Yoneda, S.

    2012-01-01

    Alkali-rich igneous fragments were identified in the brecciated LL-chondrites, Kr henberg (LL5)], Bhola (LL3-6) and Yamato (Y)-74442 (LL4), and show characteristic fractionation patterns of alkaline elements. The K-Rb-Cs-rich fragments in Kr henberg, Bhola, and Y-74442 are very similar in mineralogy and petrography (olivine + pyroxene + glass), suggesting that they could have come from related precursor materials. We have undertaken Rb-Sr isotopic studies on alkali-rich fragments in Y-74442 to precisely determine their crystallization ages and the isotopic signatures of their precursor material(s).

  9. Synthesis and Characterization of Novel Ternary and Quaternary Alkali Metal Thiophosphates

    KAUST Repository

    Alahmary, Fatimah S.

    2014-05-01

    The ongoing development of nonlinear optical (NLO) crystals such as coherent mid-IR sources focuses on various classes of materials such as ternary and quaternary metal chalcophosphates. In case of thiophosphates, the connection between PS4-tetrahedral building blocks and metals gives rise to a broad structural variety where approximately one third of all known ternary (A/P/S) and quaternary (A/M/P/S) (A = alkali metal, M = metal) structures are acentric and potential nonlinear optical materials. The molten alkali metal polychalcophosphate fluxes are a well-established method for the synthesis of new ternary and quaternary thiophosphate and selenophosphate compounds. It has been a wide field of study and investigation through the last two decades. Here, the flux method is used for the synthesis of new quaternary phases containing Rb, Ag, P and S. Four new alkali metal thiophosphates, Rb4P2S10, RbAg5(PS4), Rb2AgPS4 and Rb3Ag9(PS4)4, have been synthesized successfully from high purity elements and binary starting materials. The new compounds were characterized by single crystal and powder X-ray diffraction, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), ultraviolet-visible (UV-VIS), Raman spectroscopy, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). These compounds show interesting structural variety and physical properties. The crystal structures feature 3D anionic framework built up of PS4 tetrahedral units and charge balanced by Ag and alkali metal cations. All prepared compounds are semiconductors with band gap between 2.3 eV to 2.6 eV and most of them are thermally stable up to 600ºC.

  10. Purification and characterization of an extracellular, thermo-alkali-stable, metal tolerant laccase from Bacillus tequilensis SN4.

    Directory of Open Access Journals (Sweden)

    Sonica Sondhi

    Full Text Available A novel extracellular thermo-alkali-stable laccase from Bacillus tequilensis SN4 (SN4LAC was purified to homogeneity. The laccase was a monomeric protein of molecular weight 32 KDa. UV-visible spectrum and peptide mass fingerprinting results showed that SN4LAC is a multicopper oxidase. Laccase was active in broad range of phenolic and non-phenolic substrates. Catalytic efficiency (kcat/Km showed that 2, 6-dimethoxyphenol was most efficiently oxidized by the enzyme. The enzyme was inhibited by conventional inhibitors of laccase like sodium azide, cysteine, dithiothreitol and β-mercaptoethanol. SN4LAC was found to be highly thermostable, having temperature optimum at 85°C and could retain more than 80% activity at 70°C for 24 h. The optimum pH of activity for 2, 6-dimethoxyphenol, 2, 2'-azino bis[3-ethylbenzthiazoline-6-sulfonate], syringaldazine and guaiacol was 8.0, 5.5, 6.5 and 8.0 respectively. Enzyme was alkali-stable as it retained more than 75% activity at pH 9.0 for 24 h. Activity of the enzyme was significantly enhanced by Cu2+, Co2+, SDS and CTAB, while it was stable in the presence of halides, most of the other metal ions and surfactants. The extracellular nature and stability of SN4LAC in extreme conditions such as high temperature, pH, heavy metals, halides and detergents makes it a highly suitable candidate for biotechnological and industrial applications.

  11. Application of the Melting Electrodes in Metal Halide Lamps%熔融电极在金卤灯中的应用

    Institute of Scientific and Technical Information of China (English)

    朱惠冲; 周文华

    2012-01-01

    对石英和陶瓷金卤灯电极放电端部预先进行熔融处理,可以使其晶相结构更加致密、均匀,达到耐轰击的效果。通过试验验证。熔融电极达到了大幅提升金卤灯光通维持率和寿命、减轻金卤灯配套电感镇流器产生频闪等效果。%Melting the discharge end of electrode could make the crystal structure of electrode used for metal lamp more compact and homogeneous thereby enhance the bombardment resistance. Test demonstration shows could not only improve the lumen maintenance and lifetime of metal halide lamp greatly, but also reduce the effect during the operation with magnetic ballasts. halide that it strobe

  12. Positronium impact ionization of Alkali atoms

    CERN Document Server

    Ghosh, D

    2015-01-01

    Target ionization processes of alkali atoms by Positronium impact are investigated. Calculations are performed in the frame work of model potential formalism using the Coulomb distorted eikonal approximation. Interesting qualitative features are noted both in the scattered Ps and the ejected electron distributions in differential as well as double differential levels of the collision cross sections.

  13. Subtask 6.6 - SiAION Coatings for Alkali-Resistant Silicon Nitride. Topical report

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-02-25

    The efficiency of a gas turbine can be improved by increasing operating temperature. Construction materials should both meet high strength requirements and exhibit hot alkali corrosion resistance. Structural ceramics based on silicon nitride are promising candidates for high temperature engineering applications because of their high strength and good resistance to corrosion. Their performance varies significantly with the mechanical properties of boundary phases which, in turn, depend on their chemical composition, thickness of the amorphous phase, and the deformation process. To make silicon nitride ceramics tough, SiAlON ceramics were developed with controlled crystallization of the amorphous grain boundary phase. Crystallization of the grain boundary glass improves the high temperature mechanical properties of silicon nitride ceramics. Thus, the knowledge of silicon oxynitride ceramics corrosion behavior in Na{sub 2}SO{sub 4} becomes important for engineers in designing appropriate part for turbines working at high temperatures. So far there has been no report concerning alkali attack on SiAlON ceramics in the presence of SO{sub 2} and chlorine in flue gas. The goal of this project was to investigate alkali corrosion of SiAlON-Y structural ceramics under combustion conditions in the presence of sodium derived components.

  14. Difference of coordination between alkali- and alkaline-earth-metal ions to a symmetrical α,α',δ,δ'-tetramethylcucurbit[6]uril.

    Science.gov (United States)

    Chen, Wen-Jian; Yu, Da-Hai; Xiao, Xin; Zhang, Yun-Qian; Zhu, Qian-Jiang; Xue, Sai-Feng; Tao, Zhu; Wei, Gang

    2011-08-01

    To explore differences in coordination between alkali- and alkaline-earth-metal ions and cucurbit[n]urils, a water-soluble α,α',δ,δ'-tetramethylcucurbit[6]uril (TMeQ[6]) was used to synthesize a series of complexes and their supramolecular assemblies, based on the coordination of TMeQ[6] with alkali- and alkaline-earth-metal ions. The complexes and corresponding supramolecular assemblies were structurally characterized by single-crystal X-ray diffraction. Unlike cucurbituril (Q[6]), which formed the metal-Q[6] polymers based on the direct coordination of carbonyl oxygen atoms to the alkali-metal ions, TMeQ[6] formed metal-TMeQ[6] polymers based on the direct coordination of carbonyl oxygen atoms with the alkaline-earth-metal ions rather than the alkali-metal ions.

  15. New sulfido antimonates of the heavy alkali metals. Synthesis, crystal structure and chemical bonding of (K/Rb/Cs){sub 3}SbS{sub 3} and Cs{sub 3}SbS{sub 4} . H{sub 2}O; Neue Sulfido-Antimonate der schweren Alkalimetalle. Synthese, Kristallstruktur und chemische Bindung von (K/Rb/Cs){sub 3}SbS{sub 3} und Cs{sub 3}SbS{sub 4} . H{sub 2}O

    Energy Technology Data Exchange (ETDEWEB)

    Schindler, Lisa V.; Schwarz, Michael; Roehr, Caroline [Freiburg Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie

    2013-12-15

    The new sulfido antimonates(III) (Rb/Cs){sub 3}SbS{sub 3} were prepared from the alkali metal sulfides Rb{sub 2}S/Cs{sub 2}S{sub 2} and elemental antimony and sulfur or Sb{sub 2}S{sub 3} at reaction temperatures of about 700 C. The known isotypic potassium compound was similarly synthesized from the elements. The structures of the light-yellow crystals were refined using single-crystal X-ray data. Both compounds are isotypic to the respective Na salt forming the Na{sub 3}AsS{sub 3} structure type (cubic, space group P2{sub 1}3, K/Rb/Cs: a = 947.21(7)/982.28(5)/1025.92(5) pm, Z = 4, R1 = 0.0159/0.0560/0.0582). The {psi}-tetrahedral SbS{sub 3}{sup 3-} anions with Sb-S bond lengths of 242 pm are arranged in a cubic face centered packing, in which the three crystallographically different A{sup +} cations occupy the tetrahedral and octahedral voids, overall exhibiting a distorted octahedral sulfur coordination. The chemical bonding and the characteristics of the stereochemically active lone electron pair have been investigated by means of FP-LAPW band structure calculations. Needle-shaped crystals of the monohydrate of the antimony(V) salt Cs{sub 3}SbS{sub 4} . H{sub 2}O were obtained from a suspension of Sb{sub 2}O{sub 3}, CsOH and elemental sulfur. Cs{sub 3}SbS{sub 4} . H{sub 2}O crystallizes in a new structure type (monoclinic, space group P2{sub 1}/c, a = 987.17(10), b = 994.83(7), c = 1600.46(14) pm, {beta} = 126.895(8) , Z = 4, R1 = 0.0234). As expected, the Sb-S distances (233.1-234.7 pm) in the nearly ideally tetrahedral anion SbS{sub 4}{sup 3-} are considerably shorter than in the antimonates(III) but match the bond lengths in the anhydrous sulfido antimonate(V) Cs{sub 3}SbS{sub 4}. Due to their similar fcc-like anion packing and the stereochemically active lone electron pair of Sb in the antimonates(III), the whole series of compounds A{sub 3}Sb{sup III,V}S{sub 3/4} shows a uniform structure relation, which is elucidated using crystallographic group

  16. Chemical Reactivity Perspective into the Group 2B Metals Halides.

    Science.gov (United States)

    Özen, Alimet Sema; Akdeniz, Zehra

    2016-06-30

    Chemical reactivity descriptors within the conceptual density functional theory can be used to understand the nature of the interactions between two monomers of the Group 2B metal halides. This information might be valuable in the development of adequate force law parameters for simulations in the liquid state. In this study, MX2 monomers and dimers, where M = Zn, Cd, Hg and X = F, Cl, Br, I, were investigated in terms of chemical reactivity descriptors. Relativistic effects were taken into account using the effective core potential (ECP) approach. Correlations were produced between global and local reactivity descriptors and dimerization energies. Results presented in this work represent the first systematic investigation of Group 2B metal halides in the literature from a combined point of view of both relativistic effects and chemical reactivity descriptors. Steric effects were found to be responsible for the deviation from the chemical reactivity principles. They were introduced into the chemical reactivity descriptors such as local softness.

  17. Facile Preparation of Silver Halide Nanoparticles as Visible Light Photocatalysts

    Directory of Open Access Journals (Sweden)

    Linfan Cui

    2015-07-01

    Full Text Available In this study, highly efficient silver halide (AgX-based photocatalysts were successfully fabricated using a facile and template-free direct-precipitation method. AgX nanoparticles, which included silver chloride (AgCl, silver bromide (AgBr and silver iodide (AgI, were synthesized using different potassium halides and silver acetate as reactive sources. The size distribution of the AgX nanopar‐ ticles was determined by the reaction time and ratio of the reagents, which were monitored by UV-vis spectra. The as- prepared AgX nanoparticles exhibited different photoca‐ talytic properties. This shows the differences for the photodegradation of methyl orange and Congo red dyes. In addition, the AgCl nanoparticle-based photocatalyst exhibited the best photocatalytic property among all three types of AgX nanoparticles that are discussed in this study. Therefore, it is a good candidate for removing organic pollutants.

  18. Radioluminescence of synthetic quartz related to alkali ions

    Energy Technology Data Exchange (ETDEWEB)

    Martini, M., E-mail: m.martini@unimib.it [Dipartimento di Scienza dei Materiali, Universita degli Studi di Milano Bicocca, Via Cozzi 53, I-20125 Milano (Italy); INFN-Sezione di Milano Bicocca, Via Cozzi 53, I-20125 Milano (Italy); Fasoli, M. [Dipartimento di Scienza dei Materiali, Universita degli Studi di Milano Bicocca, Via Cozzi 53, I-20125 Milano (Italy); Galli, A. [Dipartimento di Scienza dei Materiali, Universita degli Studi di Milano Bicocca, Via Cozzi 53, I-20125 Milano (Italy); Istituto di Fotonica e Nanostrutture, IFN-CNR (Italy); Villa, I. [Dipartimento di Scienza dei Materiali, Universita degli Studi di Milano Bicocca, Via Cozzi 53, I-20125 Milano (Italy); Guibert, P. [IRAMAT-CRP2A (Institut de recherche sur les Archeomateriaux), UMR no. 5060, CNRS-Universite Bordeaux III, F-33607 Pessac (France)

    2012-04-15

    The radioluminescence (RL) of synthetic quartzes (GEMMA Quartz and Crystal Company) has been measured at room temperature. Some samples were treated by electrodiffusion ('sweeping') in order to change the concentrations of alkali ions, mainly Li{sup +} and Na{sup +}, which in quartz are known to be linked to Al ions, substitutional for Si ions. The RL emission spectra show evidence of a role of alkali ions in affecting some specific emissions. All the spectra could be analysed as composed of four bands in the blue and UV region. Specifically, the well known blue emission at around 470 nm was seen to be composed by two bands at 430 nm (2.86 eV) and at 485 nm (2.53 eV). Effects of irradiation, during the RL measurements, were clearly seen only in the 'Li swept in' sample, namely an increase in the 485 nm band intensity and a decrease in the 430 nm band one. The previously reported UV emission was detected at 355 nm (3.44 eV) in all the samples, being the most intense band in the 'swept out' sample. A further UV emission was detected at 315 nm (3.94 eV), more intense in untreated samples. Possible assignments of the detected emission bands are discussed in relation to the defects of quartz, specifically focusing on the Al centres that are most affected by sweeping procedures. - Highlights: Black-Right-Pointing-Pointer Contribution to the understanding of relationships between defects in quartz and luminescence emissions. Black-Right-Pointing-Pointer Role of charge compensators at substitutional Al sites in the optical properties of quartz. Black-Right-Pointing-Pointer Evidence of the double nature of the 'blue emission' (around 470 nm).

  19. Influence of the Print Run on Silver Halide Printing Plates

    Directory of Open Access Journals (Sweden)

    Tomislav Cigula

    2010-09-01

    Full Text Available The most common printing technique today is lithography. The difference between printing and nonprinting areason a printing plate is accomplished by opposite physical and chemical properties of those areas (MacPhee, 1998.The printing areas are made of photoactive layer that attracts oil and chemical substances with oil solvent – printinginks. The nonprinting areas are made of aluminium-oxide which attracts water based substances – the fountainsolution.There are many of various types of photoactive layer which are used for production of offset printing plates, amongothers is silver halide layer. The usage of the silver halide technology in the graphic reproduction is not a novelty.The filmmaking phase is based on the usage of the silver halide as the photographically active ingredient, for instance,AgBr (silver bromide. The new, digital plate making technology (Computer to Plate, CtP eliminates thefilmmaking phase and therefore enables control of the printing plate’s exposure made by computer. CtP technologyeliminates the filmmaking phase, but it also results with the reduction of needed material quantities and requiredtime for the production (Limburg, 1994; Seydel, 1996.In this paper the basis of the graphic reproduction by using the silver halide digital printing plates was described.The changes of the AgX copying layer and the surface of the aluminium base in the printing process have beenobserved. The surface characteristics were determined by measuring the relevant surface roughness parameters. Inaddition, measurements of coverage values on the prints, detailed at smaller print run, were conducted.Results showed that surface changes on the printing plate are changing during printing process and that thesechanges influence transfer of the printing ink on the printing substrate. These measurements proved to be of greatinterest in the graphic reproduction as they enable us to determine consistency of the printing plates during theprinting

  20. Symmetry-Based Tight Binding Modeling of Halide Perovskite Semiconductors

    OpenAIRE

    Boyer-Richard, Soline; Katan, Claudine; Traoré, Boubacar; Scholz, Reinhard; Jancu, Jean-Marc; Even, Jacky

    2016-01-01

    International audience; On the basis of a general symmetry analysis, this paper presents an empirical tight-binding (TB) model for the reference Pm-3m perovskite cubic phase of halide perovskites of general formula ABX3. The TB electronic band diagram, with and without spin orbit coupling effect of MAPbI3 has been determined based on state of the art density functional theory results including many body corrections (DFT+GW). It affords access to various properties, including distorted structu...

  1. Oxidative alkoxylation of phosphine in alcohol solutions of copper halides

    Science.gov (United States)

    Polimbetova, G. S.; Borangazieva, A. K.; Ibraimova, Zh. U.; Bugubaeva, G. O.; Keynbay, S.

    2016-08-01

    The phosphine oxidation reaction with oxygen in alcohol solutions of copper (I, II) halides is studied. Kinetic parameters, intermediates, and by-products are studied by means of NMR 31P-, IR-, UV-, and ESR- spectroscopy; and by magnetic susceptibility, redox potentiometry, gas chromatography, and elemental analysis. A reaction mechanism is proposed, and the optimum conditions are found for the reaction of oxidative alkoxylation phosphine.

  2. Organolead Halide Perovskites for Low Operating Voltage Multilevel Resistive Switching.

    Science.gov (United States)

    Choi, Jaeho; Park, Sunghak; Lee, Joohee; Hong, Kootak; Kim, Do-Hong; Moon, Cheon Woo; Park, Gyeong Do; Suh, Junmin; Hwang, Jinyeon; Kim, Soo Young; Jung, Hyun Suk; Park, Nam-Gyu; Han, Seungwu; Nam, Ki Tae; Jang, Ho Won

    2016-08-01

    Organolead halide perovskites are used for low-operating-voltage multilevel resistive switching. Ag/CH3 NH3 PbI3 /Pt cells exhibit electroforming-free resistive switching at an electric field of 3.25 × 10(3) V cm(-1) for four distinguishable ON-state resistance levels. The migration of iodine interstitials and vacancies with low activation energies is responsible for the low-electric-field resistive switching via filament formation and annihilation.

  3. Lamp-Ballast Compatibility Index for Efficient Ceramic Metal Halide Lamp Operation

    OpenAIRE

    Sourish Chatterjee

    2013-01-01

    Development of energy efficient products and exploration of energy saving potential are major challenges for present day’s technology. Ceramic Metal Halide lamp is the latest improved version of metal halide lamp that finds its wide applications in indoor commercial lighting especially in retail shop lighting. This lamp shows better performance in terms of higher lumen per watt and colour constancy in comparison to conventional metal halide lamp. The inherent negative incremental impedance of...

  4. Fluorescent Properties of Manganese Halide Benzothiazole Inorganic-Organic Hybrids.

    Science.gov (United States)

    Yu, Hui; Mei, YingXuan; Wei, ZhenHong; Mei, GuangQuan; Cai, Hu

    2016-11-01

    The reaction of manganese (II) halides MnX2 and benzothiazole (btz) in the concentrated acids HX (X = Cl, Br) at 80 °C resulted in the formation of two inorganic-organic hybrid complexes: [(btz)2(MnX4)]·2H2O (X = Cl, 1; X = Br, 2). Both compounds showed green luminescence and exhibited moderate quantum yields of 43.17 % for 1 and 26.18 % for 2, which were directly originated from the tetrahedral coordination of Mn(2+) ion. Two organic - inorganic hybrids [(btz)2(MnX4)]·2H2O based on MnCl2, benzothiazole and halide acids emitted green light with the moderate quantum efficiencies when excited by 365 nm light. Graphical abstract Two organic-inorganic hybrids [(btz)2(MnX4)]·2H2O based on MnCl2, benzothiazole and halide acids emitted green light with the moderate quantum efficiencies when excited by 365 nm light.

  5. Iodomethane-Mediated Organometal Halide Perovskite with Record Photoluminescence Lifetime.

    Science.gov (United States)

    Xu, Weidong; McLeod, John A; Yang, Yingguo; Wang, Yimeng; Wu, Zhongwei; Bai, Sai; Yuan, Zhongcheng; Song, Tao; Wang, Yusheng; Si, Junjie; Wang, Rongbin; Gao, Xingyu; Zhang, Xinping; Liu, Lijia; Sun, Baoquan

    2016-09-07

    Organometallic lead halide perovskites are excellent light harvesters for high-efficiency photovoltaic devices. However, as the key component in these devices, a perovskite thin film with good morphology and minimal trap states is still difficult to obtain. Herein we show that by incorporating a low boiling point alkyl halide such as iodomethane (CH3I) into the precursor solution, a perovskite (CH3NH3PbI3-xClx) film with improved grain size and orientation can be easily achieved. More importantly, these films exhibit a significantly reduced amount of trap states. Record photoluminescence lifetimes of more than 4 μs are achieved; these lifetimes are significantly longer than that of pristine CH3NH3PbI3-xClx films. Planar heterojunction solar cells incorporating these CH3I-mediated perovskites have demonstrated a dramatically increased power conversion efficiency compared to the ones using pristine CH3NH3PbI3-xClx. Photoluminescence, transient absorption, and microwave detected photoconductivity measurements all provide consistent evidence that CH3I addition increases the number of excitons generated and their diffusion length, both of which assist efficient carrier transport in the photovoltaic device. The simple incorporation of alkyl halide to enhance perovskite surface passivation introduces an important direction for future progress on high efficiency perovskite optoelectronic devices.

  6. Influence of alkali and alkaline earth ions on the -alkylation of the lower rim phenolic-OH groups of -tert-butyl-calix[4]arene to result in amide-pendants: Template action of K+ and the structure of K+ bound tetra-amide derivative crystallized with a -tert-butylcalix[4]arene anion

    Indian Academy of Sciences (India)

    Amjad Ali; Chebrolu P Rao; Philippe Guionneau

    2008-03-01

    Role of alkali and alkaline earth ions on the formation of calix[4]arene-amide derivatives through -alkylation of the lower rim phenolic-OH groups in general and template action of K+ in particular have been explored. Na+ and K+ ions among alkali, and Ca2+ and Sr2+ ions among alkaline earth have shown tetra-amide derivatives bound to metal ion species. Among all these, potassium salts act as template and yields a K+ bound tetra-amide derivative where the charge is counter balanced by a calix[4] arene-monoanion and the product is crystallographically characterized. Change in the amide precursor used in these -alkylation reactions has no effect on the type of the amide derivative formed. Also demonstrated is a direct one-step reaction for the preparation of 1,3-di-amide derivative in high yield and low reaction period using CsHCO3.

  7. Systematic analysis of the unique band gap modulation of mixed halide perovskites.

    Science.gov (United States)

    Kim, Jongseob; Lee, Sung-Hoon; Chung, Choong-Heui; Hong, Ki-Ha

    2016-02-14

    Solar cells based on organic-inorganic hybrid metal halide perovskites have been proven to be one of the most promising candidates for the next generation thin film photovoltaic cells. Mixing Br or Cl into I-based perovskites has been frequently tried to enhance the cell efficiency and stability. One of the advantages of mixed halides is the modulation of band gap by controlling the composition of the incorporated halides. However, the reported band gap transition behavior has not been resolved yet. Here a theoretical model is presented to understand the electronic structure variation of metal mixed-halide perovskites through hybrid density functional theory. Comparative calculations in this work suggest that the band gap correction including spin-orbit interaction is essential to describe the band gap changes of mixed halides. In our model, both the lattice variation and the orbital interactions between metal and halides play key roles to determine band gap changes and band alignments of mixed halides. It is also presented that the band gap of mixed halide thin films can be significantly affected by the distribution of halide composition.

  8. Experimental versus expected halide-ion size differences; structural changes in three series of isotypic bismuth chalcogenide halides.

    Science.gov (United States)

    Keller, Egbert; Krämer, Volker

    2006-06-01

    Experimentally determined halide-ion size differences are compared with expected size differences in the three series of isotypic bismuth chalcogenide halide compounds, KBi(6)O(9)X (X = Cl, Br and I), BiOX (X = F, Cl, Br and I) and BiSX (X = Cl, Br and I). The strong deviations observed can be assigned to steric strain caused by the heterogeneity of the bond-valence pattern and (for BiOX) to anion-anion repulsion and a change in the connectivity scheme. Some special features of the BiOF structure and the question of "isotypism" within the BiOX series are briefly discussed. Structural changes within the BiSX series are analysed.

  9. Crystallization In High Level Waste (HLW) Glass Melters: Operational Experience From The Savannah River Site

    Energy Technology Data Exchange (ETDEWEB)

    Fox, K. M.

    2014-02-27

    observed in any of the pour stream glass samples. Spinel was observed at the bottom of DWPF Melter 1 as a result of K-3 refractory corrosion. Issues have occurred with accumulation of spinel in the pour spout during periods of operation at higher waste loadings. Given that both DWPF melters were or have been in operation for greater than 8 years, the service life of the melters has far exceeded design expectations. It is possible that the DWPF liquidus temperature approach is conservative, in that it may be possible to successfully operate the melter with a small degree of allowable crystallization in the glass. This could be a viable approach to increasing waste loading in the glass assuming that the crystals are suspended in the melt and swept out through the riser and pour spout. Additional study is needed, and development work for WTP might be leveraged to support a different operating limit for the DWPF. Several recommendations are made regarding considerations that need to be included as part of the WTP crystal tolerant strategy based on the DWPF development work and operational data reviewed here. These include: Identify and consider the impacts of potential heat sinks in the WTP melter and glass pouring system; Consider the contributions of refractory corrosion products, which may serve to nucleate additional crystals leading to further accumulation; Consider volatilization of components from the melt (e.g., boron, alkali, halides, etc.) and determine their impacts on glass crystallization behavior; Evaluate the impacts of glass REDuction/OXidation (REDOX) conditions and the distribution of temperature within the WTP melt pool and melter pour chamber on crystal accumulation rate; Consider the impact of precipitated crystals on glass viscosity; Consider the impact of an accumulated crystalline layer on thermal convection currents and bubbler effectiveness within the melt pool; Evaluate the impact of spinel accumulation on Joule heating of the WTP melt pool; and

  10. Removal of Retired Alkali Metal Test Systems

    Energy Technology Data Exchange (ETDEWEB)

    Brehm, W. F.; Church, W. R.; Biglin, J. W.

    2003-02-26

    This paper describes the successful effort to remove alkali metals, alkali metal residues, and piping and structures from retired non-radioactive test systems on the Hanford Site. These test systems were used between 1965 and 1982 to support the Fast Flux Test Facility and the Liquid Metal Fast Breeder Reactor Program. A considerable volume of sodium and sodium-potassium alloy (NaK) was successfully recycled to the commercial sector; structural material and electrical material such as wiring was also recycled. Innovative techniques were used to safely remove NaK and its residues from a test system that could not be gravity-drained. The work was done safely, with no environmental issues or significant schedule delays.

  11. Synthesis and characterization of the 1.1 adducts of copper(I) halides with bidentate N,N′-bis(benzophenone)-1,2-diiminoethane Schiff base: Crystal structures of [Cu(bz2en)2][CuX2] (X = Br, I) complexes

    NARCIS (Netherlands)

    Kia, Reza; Mirkhani, Valiollah; Harkema, Sybolt; Hummel, van Gerrit J.

    2007-01-01

    1:1 adducts of N,N′-bis(benzophenone)-1,2-diiminoethane (bz2en) with copper(I) chloride, bromide and iodide, [Cu(bz2en)2][CuX2] (X = Cl, Br, and I), have been synthesized and the structures of the solid bromide and iodide adducts were determined by X-ray crystallography from single-crystal data. The

  12. Pyrolysis characteristic of kenaf studied with separated tissues, alkali pulp, and alkali li

    Directory of Open Access Journals (Sweden)

    Yasuo Kojima

    2015-12-01

    Full Text Available To estimate the potential of kenaf as a new biomass source, analytical pyrolysis was performed using various kenaf tissues, i.e., alkali lignin and alkali pulp. The distribution of the pyrolysis products from the whole kenaf was similar to that obtained from hardwood, with syringol, 4-vinylsyringol, guaiacol, and 4-vinylguaiacol as the major products. The phenols content in the pyrolysate from the kenaf core was higher than that from the kenaf cuticle, reflecting the higher lignin content of the kenaf core. The ratios of the syringyl and guaiacyl compounds in the pyrolysates from the core and cuticle samples were 2.79 and 6.83, respectively. Levoglucosan was the major pyrolysis product obtained from the kenaf alkali pulp, although glycol aldehyde and acetol were also produced in high yields, as previously observed for other cellulosic materials. Moreover, the pathways for the formation of the major pyrolysis products from alkali lignin and alkali pulp were also described, and new pyrolysis pathways for carbohydrates have been proposed herein. The end groups of carbohydrates bearing hemiacetal groups were subjected to ring opening and then they underwent further reactions, including further thermal degradation or ring reclosing. Variation of the ring-closing position resulted in the production of different compounds, such as furans, furanones, and cyclopentenones.

  13. Sulfate Resistance of Alkali Activated Pozzolans

    OpenAIRE

    Bondar, Dali

    2015-01-01

    The consequence of sulfate attack on geopolymer concrete, made from an alkali activated natural pozzolan (AANP) has been studied in this paper. Changes in the compressive strength, expansion and capillary water absorption of specimens have been investigated combined with phases determination by means of X-ray diffraction. At the end of present investigation which was to evaluate the performance of natural alumina silica based geopolymer concrete in sodium and magnesium sulfate solution, the l...

  14. Effect of Mineral Admixtures on Alkali-Silica Reaction

    Institute of Scientific and Technical Information of China (English)

    ZHANG Chengzhi; WANG Aiqin

    2008-01-01

    The influence of silica fume,slag and fly ash on alkali-silica reaction under the condition of 70℃ is studied.The results show that silica,slag and fly ash may inhibit alkali-silica reaction only under suitable content.When the content is less than 10%,silica fume does not markedly influence the expansion of alkali-silica reaction.When the content is 15%-20%,silica fume only may delay the expansion of alkali-silica reaction.When the content is 30%-70%,slag may only delay the expansion of alkali-silica reaction,but cannot inhibit the expansion of alkali-silica reaction.When the content is 10%,fly ash does not markedly influence the expansion of alkali-silica reaction.When the content is 20%-30%,fly ash may only delay the expansion of alkali-silica reaction,but cannot inhibit the expansion of alkali-silica reaction.When the content is over 50%,it is possible that fly ash can inhibit effectively alkali-silica reaction.

  15. Infrared Spectra of Simple Inorganic Ion Pairs in Solid Solution: A Physical Inorganic Chemistry Experiment.

    Science.gov (United States)

    Miller, Philip J.; Tong, William G.

    1980-01-01

    Presents a physical inorganic experiment in which large single crystals of the alkali halides doped with divalent ion impurities are prepared easily. Demonstrates the ion pairing of inorganic ions in solid solution. (CS)

  16. Crystal structure from one-electron theory

    DEFF Research Database (Denmark)

    Skriver, H. L.

    1985-01-01

    by the theory, the predicted crystal structures are in accord with experiment in all cases except 79Au. In addition, they have investigated the effect of pressure upon the alkali metals (3Li, 11Na, 37Rb, 55Cs) and selected lanthanide metals (57La, 58Ce, 71Lu) and actinide metals (90Th, 91Pa). In these cases...

  17. Ion Pairing in Alkali Nitrate Electrolyte Solutions.

    Science.gov (United States)

    Xie, Wen Jun; Zhang, Zhen; Gao, Yi Qin

    2016-03-10

    In this study, we investigate the thermodynamics of alkali nitrate salt solutions, especially the formation of contact ion pairs between alkali cation and nitrate anion. The ion-pairing propensity shows an order of LiNO3 activity coefficients and suggest that the empirical "law of matching water affinity" is followed by these alkali nitrate salt solutions. The spatial patterns of contact ion pairs are different in the three salt solutions studied here: Li(+) forms the contact ion pair with only one oxygen of the nitrate while Na(+) and K(+) can also be shared by two oxygens of the nitrate. In reproducing the salt activity coefficient using Kirkwood-Buff theory, we find that it is essential to include electronic polarization for Li(+) which has a high charge density. The electronic continuum correction for nonpolarizable force field significantly improves the agreement between the calculated activity coefficients and their experimental values. This approach also improves the performance of the force field on salt solubility. From these two aspects, this study suggests that electronic continuum correction can be a promising approach to force-field development for ions with high charge densities.

  18. Water in the hydration shell of halide ions has significantly reduced Fermi resonance and moderately enhanced Raman cross section in the OH stretch regions.

    Science.gov (United States)

    Ahmed, Mohammed; Singh, Ajay K; Mondal, Jahur A; Sarkar, Sisir K

    2013-08-22

    Water in the presence of electrolytes plays an important role in biological and industrial processes. The properties of water, such as the intermolecular coupling, Fermi resonance (FR), hydrogen-bonding, and Raman cross section were investigated by measuring the Raman spectra in the OD and OH stretch regions in presence of alkali halides (NaX; X = F, Cl, Br, I). It is observed that the changes in spectral characteristics by the addition of NaX in D2O are similar to those obtained by the addition of H2O in D2O. The spectral width decreases significantly by the addition of NaX in D2O (H2O) than that in the isotopically diluted water. Quantitative estimation, on the basis of integrated Raman intensity, revealed that the relative Raman cross section, σ(H)/σ(b) (σ(H) and σ(b) are the average Raman cross section of water in the first hydration shell of X(-) and in bulk, respectively), in D2O and H2O is higher than those in the respective isotopically diluted water. These results suggest that water in the hydration shell has reduced FR and intermolecular coupling compared to those in bulk. In the isotopically diluted water, the relative Raman cross section increases with increase in size of the halide ions (σ(H)/σ(b) = 0.6, 1.1, 1.5, and 1.9 for F(-), Cl(-), Br(-), and I(-), respectively), which is assignable to the enhancement of Raman cross section by charge transfer from halide ions to the hydrating water. Nevertheless, the experimentally determined σ(H)/σ(b) is lower than the calculated values obtained on the basis of the energy of the charge transfer state of water. The weak enhancement of σ(H)/σ(b) signifies that the charge transfer transition in the hydration shell of halide ions causes little change in the OD (OH) bond lengths of hydrating water.

  19. Thermalization of different alkali and alkali-earth elements at the TRI{mu}P facility

    Energy Technology Data Exchange (ETDEWEB)

    Shidling, P.D., E-mail: P.Shidling@rug.n [Kernfysisch Versneller Instituut, University of Groningen, Zernikelaan 25, 9747 AA Groningen (Netherlands); Giri, G.S.; Hoek, D.J. van der; Jungmann, K.; Kruithof, W.L.; Onderwater, C.J.G.; Santra, B.; Sohani, M.; Versolato, O.O.; Willmann, L.; Wilschut, H.W. [Kernfysisch Versneller Instituut, University of Groningen, Zernikelaan 25, 9747 AA Groningen (Netherlands)

    2010-10-01

    Radioactive isotopes produced by the in-flight method are converted into low-energy ions with a thermal ionizer (TI) ion catcher, the operation of which is based on a hot cavity ion source. The extraction efficiency of the TI for different alkali and alkali-earth elements has been studied and compared to a model based on diffusion only. The model describes the stationary limit, i.e. the extraction efficiency, as well as the dynamic response of the TI output when the primary beam is switched on and off.

  20. 40 CFR 721.530 - Substituted aliphatic acid halide (generic name).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted aliphatic acid halide... Specific Chemical Substances § 721.530 Substituted aliphatic acid halide (generic name). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance substituted...

  1. Palladium-catalyzed cross-coupling reactions of allylic halides and acetates with indium organometallics.

    Science.gov (United States)

    Rodríguez, David; Pérez Sestelo, José; Sarandeses, Luis A

    2004-11-12

    The palladium(0)-catalyzed cross-coupling reaction of allylic halides and acetates with indium organometallics is reported. In this synthetic transformation, triorganoindium compounds and tetraorganoindates (aryl, alkenyl, and methyl) react with cinnamyl and geranyl halides and acetates to afford the S(N)2 product regioselectively and in good yield. The reaction proceeds with net inversion of the stereochemical configuration.

  2. Spinodal Decomposition-Enabled Halide Perovskite Double Heterostructure with Reduced Fr\\"ohlich Electron-Phonon Coupling

    OpenAIRE

    Wang, Yiping; Chen, Zhizhong; Deschler, Felix; Sun, Xin; Lu, Toh-Ming; Wertz, Esther; Hu, Jia-Mian; Shi, Jian

    2016-01-01

    Epitaxial III-V semiconductor heterostructures are key components in modern microelectronics, electro-optics and optoelectronics. With superior semiconducting properties, halide perovskite materials are rising as promising candidates for coherent heterostructure devices. In this report, spinodal decomposition is proposed and experimentally implemented to produce epitaxial double heterostructures in halide perovskite system. Pristine epitaxial mixed halide perovskites rods and films were synth...

  3. Alkali cation specific adsorption onto fcc(111) transition metal electrodes.

    Science.gov (United States)

    Mills, J N; McCrum, I T; Janik, M J

    2014-07-21

    The presence of alkali cations in electrolyte solutions is known to impact the rate of electrocatalytic reactions, though the mechanism of such impact is not conclusively determined. We use density functional theory (DFT) to examine the specific adsorption of alkali cations to fcc(111) electrode surfaces, as specific adsorption may block catalyst sites or otherwise impact surface catalytic chemistry. Solvation of the cation-metal surface structure was investigated using explicit water models. Computed equilibrium potentials for alkali cation adsorption suggest that alkali and alkaline earth cations will specifically adsorb onto Pt(111) and Pd(111) surfaces in the potential range of hydrogen oxidation and hydrogen evolution catalysis in alkaline solutions.

  4. Optical Properties of Photovoltaic Organic-Inorganic Lead Halide Perovskites.

    Science.gov (United States)

    Green, Martin A; Jiang, Yajie; Soufiani, Arman Mahboubi; Ho-Baillie, Anita

    2015-12-03

    Over the last several years, organic-inorganic lead halide perovskites have rapidly emerged as a new photovoltaic contender. Although energy conversion efficiency above 20% has now been certified, improved understanding of the material properties contributing to these high performance levels may allow the progression to even higher efficiency, stable cells. The optical properties of these new materials are important not only to device design but also because of the insight they provide into less directly accessible properties, including energy-band structures, binding energies, and likely impact of excitons, as well as into absorption and inverse radiative recombination processes.

  5. Dissociative electron capture by. pi. -allyliron tricarbonyl halide molecules

    Energy Technology Data Exchange (ETDEWEB)

    Nekrasov, Y.S.; Avakyan, N.P.; Khvostenko, V.I.; Kritskaya, I.I.; Maurodiev, V.K.; Mazunov, V.A.

    1985-12-20

    Result are given for a study of dissociative electron impact by complexes (I)-(III), C/sub 3/H/sub 5/Fe (CO)/sub 3/ /SUP X/ , where X - C1 (I), Br (II), and of -allyliron tricarbonyl halides upon dissociative electron capture. The mechanisms for the formation of C/sub 3/H/sub 5/Fe (CO)/sup -//sub 3/ anions in the gas phase and under electrochemical reduction conditions on a dropping mercury electrode were shown to differ. A predominant effect was proposed for solvation factors on the electrochemical reduction in the condensed phase.

  6. Dynamic disorder, phonon lifetimes, and the assignment of modes to the vibrational spectra of methylammonium lead halide perovskites

    CERN Document Server

    Leguy, Aurélien M A; Frost, Jarvist M; Skelton, Jonathan; Brivio, Federico; Rodríguez-Martínez, Xabier; Weber, Oliver J; Pallipurath, Anuradha; Alonso, M Isabel; Campoy-Quiles, Mariano; Weller, Mark T; Nelson, Jenny; Walsh, Aron; Barnes, Piers R F

    2016-01-01

    We present Raman and terahertz absorbance spectra of methylammonium lead halide single crystals (MAPbX3, X = I, Br, Cl) at temperatures between 80 and 370 K. These results show good agreement with density-functional-theory phonon calculations.1 Comparison of experimental spectra and calculated vibrational modes enables confident assignment of most of the vibrational features between 50 and 3500 cm-1. Reorientation of the methylammonium cations, unlocked in their cavities at the orthorhombic-to-tetragonal phase transition, plays a key role in shaping the vibrational spectra of the different compounds. Calculations show that these dynamics effects split Raman peaks and create more structure than predicted from the independent harmonic modes. This explains the presence of extra peaks in the experimental spectra that have been a source of confusion in earlier studies. We discuss singular features, in particular the torsional vibration of the C-N axis, which is the only molecular mode that is strongly influenced b...

  7. A Initio Studies of Polarisabilities of Ions in Crystals.

    Science.gov (United States)

    Tole, Philip

    Available from UMI in association with The British Library. This thesis is concerned with the ab initio calculation of polarisabilities of ions in crystals. For a binary salt the Clausius-Mossotti equation relates the refractive index to the in-crystal polarisability of the ion-pair. However, there is no experimental means of separating the sum into anion and cation components. Theoretical models which use isolated ion polarisabilities to do this are physically unrealistic and have met with little success. A much better model has been developed using ab initio all-electron CHF calculations. The in-crystal environment is represented by a 'molecular' cluster embedded in a point-charge lattice. The physical features important to the success of the model are the nearest-neighbour overlap compression and the isotropic part of the electrostatic potential arising from the point -charge lattice. Calculations on simple first row alkali halides show the cation to be independent of these forces whereas the anion becomes, smaller, more bound and less polarisable in the crystal. When corrections for correlation are added the agreement with Clausius-Mossotti polarisabilities is at the 5% level or better. This implies a reduction in polarisability by factors of up to 2 with respect to the free ion. The polarisabilities for the anions in LiF, NaF, KF, LiCl, NaCl, KCl, LiBr, NaBr, KBr, CaF _2, BeO, MgO, CaO, Li_2O, Na_2O, K_2O, BeS, CaS, Li_2S, Na_2 S and K_2S were calculated. Anion polarisability is found to vary with lattice parameter but hardly at all with coordination number. Calculations on Be_2C show that in-crystal compression is sufficient to stabilise even C^{4 -}, which has a polarisability of over 20 au. Anions at the surface of LiF and MgO were also modelled. Because anisotropic overlap and electrostatic factors tend to cancel, the ion in 5-, 4- and 3-coordinate surface sites has a polarisability only a few per cent greater than in the bulk solid. Implications for

  8. The structure of alkali silicate gel by total scattering methods

    KAUST Repository

    Benmore, C.J.

    2010-06-01

    The structure of the alkali silicate gel (ASR) collected from the galleries of Furnas Dam in Brazil was determined by a pair distribution function (PDF) analysis of high energy X-ray diffraction data. Since this method is relatively new to concrete structure analysis a detailed introduction on the PDF method is given for glassy SiO2. The bulk amorphous structure of the dam material is confirmed as no Bragg peaks are observed in the scattered intensity. The real space results show that the local structure of the amorphous material is similar to kanemite (KHSi2O5:3H2O) however the long range layer structure of the crystal is broken up in the amorphous state, so that ordering only persists of the length scale of a few polyhedra. The silicate layer structure is a much more disordered than predicted by molecular dynamics models. The X-ray results are consistent with the molecular dynamics model of Kirkpatrick et al. (2005) [1] which predicts that most of the water resides in pores within the amorphous network rather than in layers. The total scattering data provide a rigorous basis against which other models may also be tested. © 2010.

  9. NQR and X-ray crystal structure studies of cadmium halide complexes: [C(NH{sub 2}){sub 3}]CdI{sub 3} and [4-ClC{sub 6}H{sub 5}NH{sub 3}]{sub 3}CdBr{sub 5}

    Energy Technology Data Exchange (ETDEWEB)

    Gesing, Thorsten M.; Lork, Enno [Bremen Univ. (Germany). MAPEX Center for Material and Processes; Terao, Hiromitsu [Tokushima Univ. (Japan). Faculty of Integrated Arts and Sciences; Ishihara, Hideta [Saga Univ. (Japan). Faculty of Culture and Education

    2016-05-01

    The crystal structures of [C(NH{sub 2}){sub 3}]CdI{sub 3} (1) and [4-ClC{sub 6}H{sub 5}NH{sub 3}]{sub 3}CdBr{sub 5} (2) have been determined at 100 K: monoclinic, Cc, a = 828.75(3) pm, b = 1615.31(5) pm, c = 810.64(3) pm, and β = 106.5820(10) for 1; monoclinic, P2{sub 1}/c, a = 1486.93(5) pm, b = 794.31(3) pm, c = 2290.59(7) pm, and β = 99.6830(10) for 2. The structure of 1 has an infinite chain of anions consisting of [CdI{sub 4}] tetrahedra sharing two corners. The structure of 2 has an infinite chain of anions consisting of [CdBr{sub 6}] octahedra sharing two corners in cis positions. In both structures, isolated cations are connected to the anion chains through weak hydrogen bonds Cd-X..H to result in three-dimensional network structures. In accordance with the crystal structures, three {sup 127}I (m = ±1/2 <-> m = ±3/2), five {sup 81}Br, and three {sup 35}Cl nuclear quadrupole resonance (NQR) lines were observed for 1 and 2. The NQR spectra reflect the anion chain structures and their weak hydrogen bonds. The MO calculations of the models [Cd{sub 5}I{sub 16}]{sup 6-} for 1 and [Cd{sub 3}Br{sub 16}]{sup 10-} for 2 estimate only about half the values for the NQR frequencies but give accurate electric field gradient directions.

  10. Synthesis, structural and spectral studies of five- and six-coordinate adducts of organotin(IV) halides containing dibenzylsulfoxide (DBSO) as ligand. The crystal structures of fac-[MeSnCl{sub 3}(dbso){sub 2}] and trans-[Ph{sub 2}SnCl{sub 2}(dbso){sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Sousa, Gerimario F. de [Universidade de Brasilia (UnB), DF (Brazil). Inst. de Quimica], e-mail: gfreitas@unb.br; Sabino, Jose R.; Vencato, Ivo [Universidade Federal do Goias (UFGO), Goiania, GO (Brazil). Inst. de Fisica; Filgueiras, Carlos A. L. [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Inst. de Quimica; Ardisson, Jose D. [Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG), Belo Horizonte, MG (Brazil). Lab. de Fisica Aplicada

    2009-07-01

    The reaction of the ambidentate ligand dibenzylsulfoxide (dbso) with Me{sub 2}SnCl{sub 2} in 1:1 molar ratio leads to the formation of the five-coordinate adduct [Me{sub 2}SnCl{sub 2}(dbso)], whereas the same reaction conditions with Ph{sub 2}SnCl{sub 2} provide the six-coordinate adduct trans-[Ph{sub 2}SnCl{sub 2}(dbso){sub 2}]. On the other hand, the reaction with {sup {pi}}Bu{sub 2}SnCl{sub 2} forms the dimeric adduct [{l_brace}{sup {pi}}Bu{sub 2}SnCl{sub 2}(dbso){r_brace}{sub 2}], which probably possesses octahedral tin(IV) nuclei and bridging chlorides. The adducts [MeSnCl{sub 3}(dbso){sub 2}] and [Ph{sub 3}SnCl(dbso)] were also prepared and included in the study. All complexes were studied by microanalysis and IR, NMR ({sup 1}H, {sup 13}C and {sup 119}Sn) and Moessbauer spectroscopies to investigate their structural properties. The six-coordinate species fac-[MeSnCl{sub 3}(dbso){sub 2}] and trans-[Ph{sub 2}SnCl{sub 2}(dbso){sub 2}] were also studied by single crystal X-ray diffractometry. These compounds crystallize in the orthorhombic, Pbcn, and monoclinic space group P2{sub 1}/c, respectively, as discrete neutral molecules with the tin(IV) atom in a distorted octahedral geometry and the two dbso ligands in cis and trans positions, respectively. (author)

  11. (abstract) Fundamental Mechanisms of Electrode Kinetics and Alkali Metal Atom Transport at the Alkali Beta'-Alumina/Porous Electrode/Alkali Metal Vapor Three Phase Boundary

    Science.gov (United States)

    Williams, R. M.; Jeffries-Nakamura, B.; Ryan, M. A.; Underwood, M. L.; O'Connor, D.; Kisor, A.; Kikkert, S. K.

    1993-01-01

    The mechanisms of electrode kinetics and mass transport of alkali metal oxidation and alkali metal cation reduction at the solid electrolyte/porous electrode boundary as well as alkali metal transport through porous metal electrodes has important applications in optimizing device performance in alkali metal thermal to electric converter (AMTEC) cells which are high temperature, high current density electrochemical cells. Basic studies of these processes also affords the opportunity to investigate a very basic electrochemical reaction over a wide range of conditions; and a variety of mass transport modes at high temperatures via electrochemical techniques. The temperature range of these investigations covers 700K to 1240K; the alkali metal vapor pressures range from about 10(sup -2) to 10(sup 2) Pa; and electrodes studied have included Mo, W, Mo/Na(sub 2)MoO(sub 4), W/Na(sub 2)WO(sub 4), WPt(sub x), and WRh(sub x) (1.0 alkali metal vapor and alkali metal vapor/solid electrolyte/vapor cells have been used to characterize the reaction and transport processes. We have previously reported evidence of ionic, free molecular flow, and surface transport of sodium in several types of AMTEC electrodes.

  12. Organic-inorganic hybrid lead halide perovskites for optoelectronic and electronic applications.

    Science.gov (United States)

    Zhao, Yixin; Zhu, Kai

    2016-02-07

    Organic and inorganic hybrid perovskites (e.g., CH(3)NH(3)PbI(3)), with advantages of facile processing, tunable bandgaps, and superior charge-transfer properties, have emerged as a new class of revolutionary optoelectronic semiconductors promising for various applications. Perovskite solar cells constructed with a variety of configurations have demonstrated unprecedented progress in efficiency, reaching about 20% from multiple groups after only several years of active research. A key to this success is the development of various solution-synthesis and film-deposition techniques for controlling the morphology and composition of hybrid perovskites. The rapid progress in material synthesis and device fabrication has also promoted the development of other optoelectronic applications including light-emitting diodes, photodetectors, and transistors. Both experimental and theoretical investigations on organic-inorganic hybrid perovskites have enabled some critical fundamental understandings of this material system. Recent studies have also demonstrated progress in addressing the potential stability issue, which has been identified as a main challenge for future research on halide perovskites. Here, we review recent progress on hybrid perovskites including basic chemical and crystal structures, chemical synthesis of bulk/nanocrystals and thin films with their chemical and physical properties, device configurations, operation principles for various optoelectronic applications (with a focus on solar cells), and photophysics of charge-carrier dynamics. We also discuss the importance of further understanding of the fundamental properties of hybrid perovskites, especially those related to chemical and structural stabilities.

  13. Adsorption of alkali, alkaline-earth, and 3d transition metal atoms on silicene

    Science.gov (United States)

    Sahin, H.; Peeters, F. M.

    2013-02-01

    The adsorption characteristics of alkali, alkaline-earth, and transition metal adatoms on silicene, a graphene-like monolayer structure of silicon are analyzed by means of first-principles calculations. In contrast to graphene, interaction between the metal atoms and the silicene surface is quite strong due to its highly reactive buckled hexagonal structure. In addition to structural properties, we also calculate the electronic band dispersion, net magnetic moment, charge transfer, work function, and dipole moment of the metal adsorbed silicene sheets. Alkali metals, Li, Na, and K, adsorb to hollow sites without any lattice distortion. As a consequence of the significant charge transfer from alkalis to silicene, metalization of silicene takes place. Trends directly related to atomic size, adsorption height, work function, and dipole moment of the silicene/alkali adatom system are also revealed. We found that the adsorption of alkaline-earth metals on silicene is entirely different from their adsorption on graphene. The adsorption of Be, Mg, and Ca turns silicene into a narrow gap semiconductor. Adsorption characteristics of eight transition metals Ti, V, Cr, Mn, Fe, Co, Mo, and W are also investigated. As a result of their partially occupied d orbital, transition metals show diverse structural, electronic, and magnetic properties. Upon the adsorption of transition metals, depending on the adatom type and atomic radius, the system can exhibit metal, half-metal, and semiconducting behavior. For all metal adsorbates, the direction of the charge transfer is from adsorbate to silicene, because of its high surface reactivity. Our results indicate that the reactive crystal structure of silicene provides a rich playground for functionalization at nanoscale.

  14. Sodium-metal halide and sodium-air batteries.

    Science.gov (United States)

    Ha, Seongmin; Kim, Jae-Kwang; Choi, Aram; Kim, Youngsik; Lee, Kyu Tae

    2014-07-21

    Impressive developments have been made in the past a few years toward the establishment of Na-ion batteries as next-generation energy-storage devices and replacements for Li-ion batteries. Na-based cells have attracted increasing attention owing to low production costs due to abundant sodium resources. However, applications of Na-ion batteries are limited to large-scale energy-storage systems because of their lower energy density compared to Li-ion batteries and their potential safety problems. Recently, Na-metal cells such as Na-metal halide and Na-air batteries have been considered to be promising for use in electric vehicles owing to good safety and high energy density, although less attention is focused on Na-metal cells than on Na-ion cells. This Minireview provides an overview of the fundamentals and recent progress in the fields of Na-metal halide and Na-air batteries, with the aim of providing a better understanding of new electrochemical systems.

  15. Tunable Near-Infrared Luminescence in Tin Halide Perovskite Devices.

    Science.gov (United States)

    Lai, May L; Tay, Timothy Y S; Sadhanala, Aditya; Dutton, Siân E; Li, Guangru; Friend, Richard H; Tan, Zhi-Kuang

    2016-07-21

    Infrared emitters are reasonably rare in solution-processed materials. Recently, research into hybrid organo-lead halide perovskite, originally popular in photovoltaics,1-3 has gained traction in light-emitting diodes (LED) due to their low-cost solution processing and good performance.4-9 The lead-based electroluminescent materials show strong colorful emission in the visible region, but lack emissive variants further in the infrared. The concerns with the toxicity of lead may, additionally, limit their wide-scale applications. Here, we demonstrate tunable near-infrared electroluminescence from a lead-free organo-tin halide perovskite, using an ITO/PEDOT:PSS/CH3NH3Sn(Br1-xIx)3/F8/Ca/Ag device architecture. In our tin iodide (CH3NH3SnI3) LEDs, we achieved a 945 nm near-infrared emission with a radiance of 3.4 W sr(-1) m(-2) and a maximum external quantum efficiency of 0.72%, comparable with earlier lead-based devices. Increasing the bromide content in these tin perovskite devices widens the semiconductor bandgap and leads to shorter wavelength emissions, tunable down to 667 nm. These near-infrared LEDs could find useful applications in a range of optical communication, sensing and medical device applications.

  16. Two-Dimensional Halide Perovskites: Tuning Electronic Activities of Defects.

    Science.gov (United States)

    Liu, Yuanyue; Xiao, Hai; Goddard, William A

    2016-05-11

    Two-dimensional (2D) halide perovskites are emerging as promising candidates for nanoelectronics and optoelectronics. To realize their full potential, it is important to understand the role of those defects that can strongly impact material properties. In contrast to other popular 2D semiconductors (e.g., transition metal dichalcogenides MX2) for which defects typically induce harmful traps, we show that the electronic activities of defects in 2D perovskites are significantly tunable. For example, even with a fixed lattice orientation one can change the synthesis conditions to convert a line defect (edge or grain boundary) from electron acceptor to inactive site without deep gap states. We show that this difference originates from the enhanced ionic bonding in these perovskites compared with MX2. The donors tend to have high formation energies and the harmful defects are difficult to form at a low halide chemical potential. Thus, we unveil unique properties of defects in 2D perovskites and suggest practical routes to improve them.

  17. Fragmentation mechanism and energetics of some alkyl halide ions

    Energy Technology Data Exchange (ETDEWEB)

    Rosenstock, H.M.; Buff, R.; Ferreira, M.A.; Lias, S.G.; Parr, A.C.; Stockbauer, R.L.; Holmes, J.L.

    1982-05-05

    Halogen loss from iodoethane, 1-bromopropane, 2-bromopropane, 1-iodopropane, and 2-iodopropane has been studied by means of electron-ion coincidence techniques and by observation of metastable transition. Analysis of the breakdown curves and the study of residence times gave the zero-kelvin thresholds for halogen loss and indicated the size of the kinetic shift. The fragmentation onset for iodoethane was located in a Franck-Condon gap. The zero-kelvin thresholds for the propyl halides were found to lie at or just above the upper spin-orbit level of the parent ion. All of the propyl halides exhibited a unimolecular metastable transition. At fragmentation onset the 2-halopropane ions have negligible fragment kinetic energy while the 1-halopropane produce secondary propyl ions wih 100-200 meV of kinetic energy. It was established that a potential barrier must be surmounted in this fragmentation-isomerization process and analysis suggests a dynamic mechanism other than conventional QET, for example, weak couplings of vibrational modes. Analysis of the 2-halopropane fragmentation thresholds leads to an accurate, absolute value for the proton affinity of propylene, 751.4 +/- 2.9 kJ/mol at room temperature. This value reconciles some differences inherent in the proton affinity scale based on various relative measurements.

  18. Syntheses and Structures of Alkali Metal Rare Earth Polyphosphates CsLn(PO3)4 (Ln = La, Ce)

    Institute of Scientific and Technical Information of China (English)

    ZHU Jing; CHENG Wen-Dan; ZHANG Hao; WU Dong-Sheng; ZHAO Dan

    2008-01-01

    Alkali metal-rare earth polyphosphates, CsLn(PO3)4 (Ln = La, Ce), were synthesized by the high temperature solution reaction and studied by single-crystal X-ray diffraction technique. They crystallize in the monoclinic space group P21 (Z = 2) and feature infinite PO4 spiral chains linked with neighboring CsO10 and LnO8 polyhedra. In addition, theoretically calculated energy band structure and density of states (DOS) by the density functional theory(DFT) predict that the solid-state compound CsLa(PO3)4 possesses insulative character.

  19. High-Order Dispersion Coefficients for Alkali-metal Atoms

    Institute of Scientific and Technical Information of China (English)

    KANG Shuai; DING Chi-Kun; CHEN Chang-Yong; WU Xue-Qing

    2013-01-01

    High-order dispersion coefficients C9,C11,C12,and C13 for the ground-state alkali-metals were calculated by combining the l-dependent model potential of alkali-metal atoms and linear variation method based on B-spline basis functions.The results were compared.

  20. Durability of Alkali Activated Blast Furnace Slag

    Science.gov (United States)

    Ellis, K.; Alharbi, N.; Matheu, P. S.; Varela, B.; Hailstone, R.

    2015-11-01

    The alkali activation of blast furnace slag has the potential to reduce the environmental impact of cementitious materials and to be applied in geographic zones where weather is a factor that negatively affects performance of materials based on Ordinary Portland Cement. The scientific literature provides many examples of alkali activated slag with high compressive strengths; however research into the durability and resistance to aggressive environments is still necessary for applications in harsh weather conditions. In this study two design mixes of blast furnace slag with mine tailings were activated with a potassium based solution. The design mixes were characterized by scanning electron microscopy, BET analysis and compressive strength testing. Freeze-thaw testing up to 100 freeze-thaw cycles was performed in 10% road salt solution. Our findings included compressive strength of up to 100 MPa after 28 days of curing and 120 MPa after freeze-thaw testing. The relationship between pore size, compressive strength, and compressive strength after freeze-thaw was explored.

  1. Laser Spectroscopy of bi-alkali molecules

    Science.gov (United States)

    Dutta, Sourav; Altaf, A.; Lorenz, J.; Elliott, D.; Chen, Yong

    2010-03-01

    We report a study of laser spectroscopy of bi-alkali molecules, such as Li2, Rb2 and LiRb (work is in progress). We have constructed a dual-species (Li/Rb) heat pipe oven with a side viewport. The molecular fluorescence is excited by a dye laser with Rh6G dye (operating between 564 nm and 610 nm) and various home-made diode lasers (operating near 635 nm and 665 nm). The fluorescence is recorded using a .5ex1 -.1em/ -.15em.25ex4 m monochromator with a 0.1 nm (˜ 3 cm-1) spectral resolution. Transitions to the X^1σg^+ in Li2 and Rb2 have been measured and studies on LiRb are in progress. Molecular parameters, such as force constant, may be obtained from the analysis of the data (which agree with previously known values to within ˜ 3%). Using the known values of dissociation energy De and harmonic frequency φe for the alkali dimers, we also demonstrate that simple calculations with Morse potential approximation can be used to estimate the molecular transition wavelengths to within a few (1-3) nanometers from the experimentally measured values. Such information will aid in creating cold molecules via photoassociation in a dual species magneto-optical trap (LiRb in our case).

  2. Characterization of alkali-metal and alkaline-earth nitrates by vibrational spectroscopy

    Directory of Open Access Journals (Sweden)

    Martínez, S.

    1992-09-01

    Full Text Available Infrared spectra of sodium and potassium alkaline-metal nitrates and magnesium and calcium alkali-earth nitrates in solid phase had been recorded in order to assign the fundamental bands. The influence of the dispersal médium (alkaline halide, employed in the solid sample preparation have been discussed. The quantitative measurements of the band in ten sities at 1387 cm-1 (present in the I.R. spectra of the four nitrates in KBr médium allowed us to determine the Lambert-Beer law slopes for each compound. These values are differents (bearing in mind experimental random errors, so we have could to affirm the nonexistence of solid solution between the nitrate and the alkaline halide médium. The L-B law obtained by us can be used for the Identification differentiation and quantitative analysis of these nitrates in solid phase, even if they are present in a very low concentration.

    Se ha realizado la asignación de los espectros infrarrojo (IR de los nitratos alcalinos, sódico y potásico, y de los alcalinotérreos, magnésico y cálcico, en estado sólido. Se ha visto la influencia del medio dispersante (haluro alcalino, utilizado en la preparación de la muestra sólida. El estudio cuantitativo de la absorbencia de la banda a 1.387 cm-1 (presente en los espectros IR de los cuatro nitratos en medio KBr permite determinar las pendientes de la Ley de Lambert-Beer Se comprueba que dichas pendientes son diferentes lo que conduce a poder afirmar que no se produce disolución sólida entre el KBr y el nitrato alcalino o alcalinotérreo. La determinación de la ley de Lambert-Beer permite la identificación y el análisis cualitativo y cuantitativo por espectroscopia IR de estos nitratos cuando están presentes en bajas concentraciones en muestras sólidas.

  3. IRMPD Action Spectroscopy of Alkali Metal Cation-Cytosine Complexes: Effects of Alkali Metal Cation Size on Gas Phase Conformation

    NARCIS (Netherlands)

    Yang, B.; Wu, R.R.; Polfer, N.C.; Berden, G.; Oomens, J.; Rodgers, M.T.

    2013-01-01

    The gas-phase structures of alkali metal cation-cytosine complexes generated by electrospray ionization are probed via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical calculations. IRMPD action spectra of five alkali metal cation-cytosine complexes exhibit both simi

  4. Photophysical behavior and fluorescence quenching by halides of quinidine dication: Steady state and time resolved study

    Energy Technology Data Exchange (ETDEWEB)

    Joshi, Neeraj Kumar; Tewari, Neeraj; Arora, Priyanka; Rautela, Ranjana; Pant, Sanjay [Photophysics Laboratory, Department of Physics, DSB Campus, Kumaun University, Nainital 263002, Uttarakhand (India); Joshi, Hem Chandra, E-mail: hem_sup@yahoo.co.uk [Institute for Plasma Research, Laser Diagnostics Division, Bhat, Near Indira Bridge, Gandhinagar 382428, Gujarat (India)

    2015-02-15

    The fluorescence quenching of quinidine in acidified aqueous solution by various halides (Cl{sup −}, Br{sup −} and I{sup −}) was studied using steady state and time resolved fluorescence techniques. The quenching process was characterized by Stern–Volmer (S–V) plots. Possibility of conformers (one is not quenched by halide and the other is quenched) is invoked to explain the observed results. - Highlights: • Fluorescence quenching of quinidine in acidified aqueous solution by halides. • Various quenching parameters have been estimated. • Possibility of conformers is invoked to explain the observed results.

  5. Energetics of the ruthenium-halide bond in olefin metathesis (pre)catalysts

    KAUST Repository

    Falivene, Laura

    2013-01-01

    A DFT analysis of the strength of the Ru-halide bond in a series of typical olefin metathesis (pre)catalysts is presented. The calculated Ru-halide bond energies span the rather broad window of 25-43 kcal mol-1. This indicates that in many systems dissociation of the Ru-halide bond is possible and is actually competitive with dissociation of the labile ligand generating the 14e active species. Consequently, formation of cationic Ru species in solution should be considered as a possible event. © 2013 The Royal Society of Chemistry.

  6. Crystallographic and Fluorescence Studies of the Interaction of Haloalkane Dehalogenase with Halide Ions. Studies with Halide Compounds Reveal a Halide Binding Site in the Active Site

    NARCIS (Netherlands)

    VERSCHUEREN, KHG; Kingma, Jacob; ROZEBOOM, HJ; KALK, KH; JANSSEN, DB; DIJKSTRA, BW

    1993-01-01

    Haloalkane dehalogenase from Xanthobacter autotrophicus GJ10 catalyzes the conversion of 1,2-dichloroethane to 2-chloroethanol and chloride without use of oxygen or cofactors. The active site is situated in an internal cavity, which is accesible from the solvent, even in the crystal. Crystal structu

  7. Size-dependent one-photon- and two-photon-pumped amplified spontaneous emission from organometal halide CH3NH3PbBr3 perovskite cubic microcrystals.

    Science.gov (United States)

    Zhang, Zhen-Yu; Wang, Hai-Yu; Zhang, Yan-Xia; Li, Kai-Jiao; Zhan, Xue-Peng; Gao, Bing-Rong; Chen, Qi-Dai; Sun, Hong-Bo

    2017-01-18

    In the past few years, organometal halide light-emitting perovskite thin films and colloidal nanocrystals (NCs) have attracted significant research interest in the field of highly purified illuminating applications. However, knowledge of photoluminescence (PL) characteristics, such as amplified spontaneous emission (ASE) of larger-sized perovskite crystals, is still relatively scarce. Here, we presented room-temperature size-dependent spontaneous emission (SE) and ASE of the organometal halide CH3NH3PbBr3 perovskite cubic microcrystals pumped through one-photon-(1P) and two-photon-(2P) excitation paradigms. The results showed that the optical properties of SE and ASE were sensitively dependent on the sizes of perovskite microcrystals irrespective of whether 1P or 2P excitation was used. Moreover, by comparing the spectral results of 1P- and 2P-pumped experiments, 2P pumping was found to be an effective paradigm to reduce thresholds by one order of magnitude. Finally, we carried out fluences-dependent time-resolved fluorescence dynamics experiments to study the underlying effects of these scale-dependent SE and ASE. We found that the photoluminescence (PL) recombination rates sensitively became faster with increasing carriers' densities, and that the ASE pumped from larger-sized CH3NH3PbBr3 perovskite cubic microcrystals showed faster lifetimes. This work shows that micro-sized perovskite cubic crystals could be the ideal patterns of perovskite materials for realizing ASE applications in the future.

  8. In vitro Biological Effects of Ti2448 Alloy Modified by Micro-arc Oxidation and Alkali Heatment

    Institute of Scientific and Technical Information of China (English)

    Xue Han; Hongchen Liu; Dongsheng Wang; Shujun Li; Rui Yang; Xiaojie Tao; Xiaohong Jiang

    2011-01-01

    The purpose of this study was to test the hypothesis that the combination of micro-arc oxidation and alkali heatment (MAH) would improve the cytocompatibility of a newly designed Ti-24Nb-4Zr-8Sn alloy. In this study, commercially pure titanium (cp Ti) and Ti-24Nb-4Zr-8Sn were used. Surface modification of Ti-24Nb-4Zr-8Sn by a two-step treatment of micro-arc oxidation (MAO) and alkali heatment was reported. Surface characterizations were performed by scanning electron microscopy (SEM), thin film X-ray diffraction (TF-XRD)and X-ray photoelectron spectroscopy (XPS). The MAH layer consisted of finer crystals and possessed a higher degree of crystallity and stability than the MAO layer. A biocompatibility study on treated and untreated Ti24Nb-4Zr-8Sn in comparison with cp Ti was carried out to investigate the effect of the different surfaces on the bone integration property in vitro. The cellular assays revealed that the MAO and MAH layer favored the initial adhesion of MC3T3-E1 cells and that the growth rate of MC3T3-E1 cells on MAH layer was significantly higher than that on the conventional MAO-treated layer after 3-day and 5-day incubation, demonstrating the greater potential of the hybrid treatment of micro-arc oxidation followed with alkali heatment as a novel surface modification method for implanting materials.

  9. Interactions between halide anions and a molecular hydrophobic interface.

    Science.gov (United States)

    Rankin, Blake M; Hands, Michael D; Wilcox, David S; Fega, K Rebecca; Slipchenko, Lyudmila V; Ben-Amotz, Dor

    2013-01-01

    Interactions between halide ions (fluoride and iodide) and t-butyl alcohol (TBA) dissolved in water are probed using a recently developed hydration-shell spectroscopic technique and theoretical cluster and liquid calculations. High ignal-to-noise Raman spectroscopic measurements are combined with multivariate curve resolution (Raman-MCR) to reveal that while there is little interaction between aqueous fluoride ions and TBA, iodide ions break down the tetrahedral hydration-shell structure of TBA and produce a red-shift in its CH stretch frequency, in good agreement with the theoretical effective fragment potential (EFP) molecular dynamics simulations and hybrid quantum/EFP frequency calculations. The results imply that there is a significantly larger probability of finding iodide than fluoride in the first hydration shell of TBA, although the local iodide concentration is apparently not as high as in the surrounding bulk aqueous NaI solution.

  10. Fast Photoconductive Responses in Organometal Halide Perovskite Photodetectors.

    Science.gov (United States)

    Wang, Fei; Mei, Jingjing; Wang, Yunpeng; Zhang, Ligong; Zhao, Haifeng; Zhao, Dongxu

    2016-02-03

    Inorganic semiconductor-based photodetectors have been suffering from slow response speeds, which are caused by the persistent photoconductivity of semiconductor materials. For realizing high speed optoelectronic devices, the organometal halide perovskite thin films were applied onto the interdigitated (IDT) patterned Au electrodes, and symmetrical structured photoconductive detectors were achieved. The detectors were sensitive to the incident light signals, and the photocurrents of the devices were 2-3 orders of magnitude higher than dark currents. The responsivities of the devices could reach up to 55 mA W(1-). Most importantly, the detectors have a fast response time of less than 20 μs. The light and bias induced dipole rearrangement in organometal perovskite thin films has resulted in the instability of photocurrents, and Ag nanowires could quicken the process of dipole alignment and stabilize the photocurrents of the devices.

  11. Recent progress and challenges of organometal halide perovskite solar cells

    Science.gov (United States)

    Yang, Liyan; Barrows, Alexander T.; Lidzey, David G.; Wang, Tao

    2016-02-01

    We review recent progress in the development of organometal halide perovskite solar cells. We discuss different compounds used to construct perovskite photoactive layers, as well as the optoelectronic properties of this system. The factors that affect the morphology of the perovskite active layer are explored, e.g. material composition, film deposition methods, casting solvent and various post-treatments. Different strategies are reviewed that have recently emerged to prepare high performing perovskite films, creating polycrystalline films having either large or small grain size. Devices that are constructed using meso-superstructured and planar architectures are summarized and the impact of the fabrication process on operational efficiency is discussed. Finally, important research challenges (hysteresis, thermal and moisture instability, mechanical flexibility, as well as the development of lead-free materials) in the development of perovskite solar cells are outlined and their potential solutions are discussed.

  12. Enhanced Quantum Efficiency From Hybrid Cesium Halide/Copper Photocathode

    Energy Technology Data Exchange (ETDEWEB)

    Kong, Lingmei; Joly, Alan G.; Droubay, Timothy C.; Gong, Yu; Hess, Wayne P.

    2014-04-28

    The quantum efficiency of Cu is found to increase dramatically when coated by a CsI film and then irradiated by a UV laser. Over three orders of magnitude quantum efficiency enhancement at 266 nm is observed in CsI/Cu(100), indicating potential application in future photocathode devices. Upon laser irradiation, a large work function reduction to a value less than 2 eV is also observed, significantly greater than for similarly treated CsBr/Cu(100). The initial QE enhancement, prior to laser irradiation, is attributed to interface interaction, surface cleanliness and the intrinsic properties of the Cs halide film. Further QE enhancement following activation is attributed to formation of inter-band states and Cs metal accumulation at the interface induced by laser irradiation.

  13. Quasielastic neutron scattering study of silver selenium halides

    CERN Document Server

    Major, A G; Barnes, A C; Howells, W S

    2002-01-01

    Both silver chalcogenides (Ag sub 2 S, Ag sub 2 Se, and Ag sub 2 Te) and silver halides (AgCl, AgBr, and AgI) are known to be fast-ion solids in which the silver ions can diffuse quickly in a sublattice formed by the other ions. To clarify whether mixtures of these materials (such as Ag sub 3 SeI) possess comparable properties and whether a systematic dependence on the cation-to-anion ratio can be observed, some of these mixtures were studied by quasielastic neutron scattering both in the solid and the liquid phases. To identify the diffusion mechanisms and constants, a new data-analysis method based on a two-dimensional maximum-likelihood fit is proposed. This method has the potential to give more reliable information on the diffusion mechanism than the traditional Bayesian method. (orig.)

  14. Two-photon pumped lead halide perovskite nanowire lasers

    CERN Document Server

    Gu, Zhiyuan; Sun, Wenzhao; Li, Jinakai; Liu, Shuai; Song, Qinghai; Xiao, Shumin

    2015-01-01

    Solution-processed lead halide perovskites have shown very bright future in both solar cells and microlasers. Very recently, the nonlinearity of perovskites started to attract considerable research attention. Second harmonic generation and two-photon absorption have been successfully demonstrated. However, the nonlinearity based perovskite devices such as micro- & nano- lasers are still absent. Here we demonstrate the two-photon pumped nanolasers from perovskite nanowires. The CH3NH3PbBr3 perovskite nanowires were synthesized with one-step solution self-assembly method and dispersed on glass substrate. Under the optical excitation at 800 nm, two-photon pumped lasing actions with periodic peaks have been successfully observed at around 546 nm. The obtained quality (Q) factors of two-photon pumped nanolasers are around 960, and the corresponding thresholds are about 674?J=cm2. Both the Q factors and thresholds are comparable to conventional whispering gallery modes in two-dimensional polygon microplates. Ou...

  15. Giant photostriction in organic-inorganic lead halide perovskites

    Science.gov (United States)

    Zhou, Yang; You, Lu; Wang, Shiwei; Ku, Zhiliang; Fan, Hongjin; Schmidt, Daniel; Rusydi, Andrivo; Chang, Lei; Wang, Le; Ren, Peng; Chen, Liufang; Yuan, Guoliang; Chen, Lang; Wang, Junling

    2016-04-01

    Among the many materials investigated for next-generation photovoltaic cells, organic-inorganic lead halide perovskites have demonstrated great potential thanks to their high power conversion efficiency and solution processability. Within a short period of about 5 years, the efficiency of solar cells based on these materials has increased dramatically from 3.8 to over 20%. Despite the tremendous progress in device performance, much less is known about the underlying photophysics involving charge-orbital-lattice interactions and the role of the organic molecules in this hybrid material remains poorly understood. Here, we report a giant photostrictive response, that is, light-induced lattice change, of >1,200 p.p.m. in methylammonium lead iodide, which could be the key to understand its superior optical properties. The strong photon-lattice coupling also opens up the possibility of employing these materials in wireless opto-mechanical devices.

  16. Alkali-activated cementitious materials: Mechanisms, microstructure and properties

    Science.gov (United States)

    Jiang, Weimin

    The goal of this study was to examine the activation reaction, microstructure, properties, identify the mechanisms of activation, and achieve an enhanced understanding of activation processes occurring during the synthesis of alkali activated cementitious materials (AAC). The discussions classify the following categories. (1) alkali activated slag cement; (2) alkali activated portland-slag cement; (3) alkali activated fly ash-slag cement; (4) alkali activated pozzolana-lime cement; (5) alkali activated pozzolana cement. The activators involved are NaOH, KOH; Nasb2SOsb4;\\ Nasb2COsb3;\\ CaSOsb4, and soluble silicate of sodium and potassium. The effect of alkali activation on the microstructure of these materials were analyzed at the micro-nanometer scale by SEM, EDS, ESEM, and TEM. Also sp{29}Si and sp{27}Al MAS-NMR, IR, Raman, TGA, and DTA were performed to characterize the phase in these systems. Slag, fly ash, silica fume, as well as blended cements containing mixtures of these and other components were characterized. A set of ordinary portland cement paste samples served as a control. This study confirmed that AAC materials have great potential because they could generate very early high strength, greater durability and high performance. Among the benefits to be derived from this research is a better understanding of the factors that control concrete properties when using AAC materials, and by controlling the chemistry and processing to produce desired microstructures and properties, as well as their durability.

  17. Controlled in-situ dissolution of an alkali metal

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Jeffrey Donald; Dooley, Kirk John; Tolman, David Donald

    2012-09-11

    A method for the controllable dissolution of one or more alkali metals from a vessel containing a one or more alkali metals and/or one or more partially passivated alkali metals. The vessel preferably comprising a sodium, NaK or other alkali metal-cooled nuclear reactor that has been used. The alkali metal, preferably sodium, potassium or a combination thereof, in the vessel is exposed to a treatment liquid, preferably an acidic liquid, more preferably citric acid. Preferably, the treatment liquid is maintained in continuous motion relative to any surface of unreacted alkali metal with which the treatment liquid is in contact. The treatment liquid is preferably pumped into the vessel containing the one or more alkali metals and the resulting fluid is extracted and optionally further processed. Preferably, the resulting off-gases are processed by an off-gas treatment system and the resulting liquids are processed by a liquid disposal system. In one preferred embodiment, an inert gas is pumped into the vessel along with the treatment liquid.

  18. Bright light-emitting diodes based on organometal halide perovskite.

    Science.gov (United States)

    Tan, Zhi-Kuang; Moghaddam, Reza Saberi; Lai, May Ling; Docampo, Pablo; Higler, Ruben; Deschler, Felix; Price, Michael; Sadhanala, Aditya; Pazos, Luis M; Credgington, Dan; Hanusch, Fabian; Bein, Thomas; Snaith, Henry J; Friend, Richard H

    2014-09-01

    Solid-state light-emitting devices based on direct-bandgap semiconductors have, over the past two decades, been utilized as energy-efficient sources of lighting. However, fabrication of these devices typically relies on expensive high-temperature and high-vacuum processes, rendering them uneconomical for use in large-area displays. Here, we report high-brightness light-emitting diodes based on solution-processed organometal halide perovskites. We demonstrate electroluminescence in the near-infrared, green and red by tuning the halide compositions in the perovskite. In our infrared device, a thin 15 nm layer of CH3NH3PbI(3-x)Cl(x) perovskite emitter is sandwiched between larger-bandgap titanium dioxide (TiO2) and poly(9,9'-dioctylfluorene) (F8) layers, effectively confining electrons and holes in the perovskite layer for radiative recombination. We report an infrared radiance of 13.2 W sr(-1) m(-2) at a current density of 363 mA cm(-2), with highest external and internal quantum efficiencies of 0.76% and 3.4%, respectively. In our green light-emitting device with an ITO/PEDOT:PSS/CH3NH3PbBr3/F8/Ca/Ag structure, we achieved a luminance of 364 cd m(-2) at a current density of 123 mA cm(-2), giving external and internal quantum efficiencies of 0.1% and 0.4%, respectively. We show, using photoluminescence studies, that radiative bimolecular recombination is dominant at higher excitation densities. Hence, the quantum efficiencies of the perovskite light-emitting diodes increase at higher current densities. This demonstration of effective perovskite electroluminescence offers scope for developing this unique class of materials into efficient and colour-tunable light emitters for low-cost display, lighting and optical communication applications.

  19. Phase space investigation of the lithium amide halides

    Energy Technology Data Exchange (ETDEWEB)

    Davies, Rosalind A. [Hydrogen Storage Chemistry Group, School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Hydrogen and Fuel Cell Group, School of Chemical Engineering, University of Birmingham, Edgbaston B15 2TT (United Kingdom); Hewett, David R.; Korkiakoski, Emma [Hydrogen Storage Chemistry Group, School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Thompson, Stephen P. [Diamond Light Source, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0QX (United Kingdom); Anderson, Paul A., E-mail: p.a.anderson@bham.ac.uk [Hydrogen Storage Chemistry Group, School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom)

    2015-10-05

    Highlights: • The lower limits of halide incorporation in lithium amide have been investigated. • The only amide iodide stoichiometry observed was Li{sub 3}(NH{sub 2}){sub 2}I. • Solid solutions were observed in both the amide chloride and amide bromide systems. • A 46% reduction in chloride content resulted in a new phase: Li{sub 7}(NH{sub 2}){sub 6}Cl. • New low-chloride phase maintained improved H{sub 2} desorption properties of Li{sub 4}(NH{sub 2}){sub 3}Cl. - Abstract: An investigation has been carried out into the lower limits of halide incorporation in lithium amide (LiNH{sub 2}). It was found that the lithium amide iodide Li{sub 3}(NH{sub 2}){sub 2}I was unable to accommodate any variation in stoichiometry. In contrast, some variation in stoichiometry was accommodated in Li{sub 7}(NH{sub 2}){sub 6}Br, as shown by a decrease in unit cell volume when the bromide content was reduced. The amide chloride Li{sub 4}(NH{sub 2}){sub 3}Cl was found to adopt either a rhombohedral or a cubic structure depending on the reaction conditions. Reduction in chloride content generally resulted in a mixture of phases, but a new rhombohedral phase with the stoichiometry Li{sub 7}(NH{sub 2}){sub 6}Cl was observed. In comparison to LiNH{sub 2}, this new low-chloride phase exhibited similar improved hydrogen desorption properties as Li{sub 4}(NH{sub 2}){sub 3}Cl but with a much reduced weight penalty through addition of chloride. Attempts to dope lithium amide with fluoride ions have so far proved unsuccessful.

  20. Influence of alkali metal doping on surface properties and catalytic activity/selectivity of CaO catalysts in oxidative coupling of methane

    Institute of Scientific and Technical Information of China (English)

    V.H.Rane; S.T.Chaudhari; V.R.Choudhary

    2008-01-01

    Surface properties (viz. surface area, basicity/base strength distribution, and crystal phases) of alkali metal doped CaO (alkali metal/Ca = 0.1 and 0.4) catalysts and their catalytic activity/selectivity in oxidative coupling of methane (OCM) to higher hydrocarbons at different reaction conditions (viz. temperature, 700 and 750 ℃; CH4/O2 ratio, 4.0 and 8.0 and space velocity, 5140-20550 cm3·g-1·h-1) have been investigated. The influence of catalyst calcination temperature on the activity/selectivity has also been investigated. The surface properties (viz. surface area, basicity/base strength distribution) and catalytic activity/selectivity of the alkali metal doped CaO catalysts are strongly influenced by the alkali metal promoter and its concentration in the alkali metal doped CaO catalysts. An addition of alkali metal promoter to CaO results in a large decrease in the surface area but a large increase in the surface basicity (strong basic sites) and the C2+ selectivity and yield of the catalysts in the OCM process. The activity and selectivity are strongly influenced by the catalyst calcination temperature. No direct relationship between surface basicity and catalytic activity/selectivity has been observed. Among the alkali metal doped CaO catalysts, Na-CaO (Na/Ca = 0.1, before calcination) catalyst (calcined at 750 ℃), showed best performance (C2+selectivity of 68.8% with 24.7% methane conversion), whereas the poorest performance was shown by the Rb-CaO catalyst in the OCM process.

  1. Variable charge and electrical double layer of mineral-water interfaces: silver halides versus metal (hydr)oxides.

    Science.gov (United States)

    Hiemstra, Tjisse

    2012-11-01

    Classically, silver (Ag) halides have been used to understand thermodynamic principles of the charging process and the corresponding development of the electrical double layer (EDL). A mechanistic approach to the processes on the molecular level has not yet been carried out using advanced surface complexation modeling (SCM) as applied to metal (hydr)oxide interfaces. Ag halides and metal (hydr)oxides behave quite differently in some respect. The location of charge in the interface of Ag halides is not a priori obvious. For AgI(s), SCM indicates the separation of interfacial charge in which the smaller silver ions are apparently farther away from the surface than iodide. This charge separation can be understood from the surface structure of the relevant crystal faces. Charge separation with positive charge above the surface is due to monodentate surface complex formation of Ag(+) ions binding to I sites located at the surface. Negative surface charge is due to the desorption of Ag(+) ions out of the lattice. These processes can be described with the charge distribution (CD) model. The MO/DFT optimized geometry of the complex is used to estimate the value of the CD. SCM reveals the EDL structure of AgI(s), having two Stern layers in series. The inner Stern layer has a very low capacitance (C(1) = 0.15 ± 0.01 F/m(2)) in comparison to that of metal (hydr)oxides, and this can be attributed to the strong orientation of the (primary) water molecules on the local electrostatic field of the Ag(+) and I(-) ions of the surface (relative dielectric constant ε(r) ≈ 6). Depending on the extent of water ordering, mineral surfaces may in principle develop a second Stern layer. The corresponding capacitance (C(2)) will depend on the degree of water ordering that may decrease in the series AgI (C(2) = 0.57 F/m(2)), goethite (C(2) = 0.74 F/m(2)), and rutile (C(2) = ∞), as discussed. The charging principles of AgI minerals iodargyrite and miersite may also be applied to minerals

  2. Main-Group Halide Semiconductors Derived from Perovskite: Distinguishing Chemical, Structural, and Electronic Aspects.

    Science.gov (United States)

    Fabini, Douglas H; Labram, John G; Lehner, Anna J; Bechtel, Jonathon S; Evans, Hayden A; Van der Ven, Anton; Wudl, Fred; Chabinyc, Michael L; Seshadri, Ram

    2017-01-03

    Main-group halide perovskites have generated much excitement of late because of their remarkable optoelectronic properties, ease of preparation, and abundant constituent elements, but these curious and promising materials differ in important respects from traditional semiconductors. The distinguishing chemical, structural, and electronic features of these materials present the key to understanding the origins of the optoelectronic performance of the well-studied hybrid organic-inorganic lead halides and provide a starting point for the design and preparation of new functional materials. Here we review and discuss these distinguishing features, among them a defect-tolerant electronic structure, proximal lattice instabilities, labile defect migration, and, in the case of hybrid perovskites, disordered molecular cations. Additionally, we discuss the preparation and characterization of some alternatives to the lead halide perovskites, including lead-free bismuth halides and hybrid materials with optically and electronically active organic constituents.

  3. Palladium-catalyzed Cascade Cyclization-Coupling Reaction of Benzyl Halides with N,N-Diallylbenzoylamide

    Institute of Scientific and Technical Information of China (English)

    Yi Min HU; Yu ZHANG; Jian Lin HAN; Cheng Jian ZHU; Yi PAN

    2003-01-01

    A novel type of palladium-catalyzed cascade cyclization-coupling reaction has been found. Reaction of N, N-diallylbenzoylamide 1 with benzyl halides 2 afforded the corresponding dihydropyrroles 3 in moderate to excellent yields.

  4. NEW THIO S2- ADDUCTS WITH ANTIMONY (III AND V HALIDE: SYNTHESIS AND INFRARED STUDY

    Directory of Open Access Journals (Sweden)

    HASSAN ALLOUCH

    2013-12-01

    Full Text Available Five new S2- adducts with SbIII and SbV halides have been synthesized and studied by infrared. Discrete structures have been suggested, the environment around the antimony being tetrahedral, trigonal bipyramidal or octahedral.

  5. Growth and Characterization of PDMS-Stamped Halide Perovskite Single Microcrystals

    NARCIS (Netherlands)

    Khoram, P.; Brittman, S.; Dzik, W.I.; Reek, J.N.H.; Garneett, E.C.

    2016-01-01

    Recently, halide perovskites have attracted considerable attention for optoelectronic applications, but further progress in this field requires a thorough understanding of the fundamental properties of these materials. Studying perovskites in their single-crystalline form provides a model system for

  6. Influence of alkalis from different sources than cement in the evolution of alkali-silica reaction

    Directory of Open Access Journals (Sweden)

    Olague, C.

    2003-12-01

    Full Text Available A bibliographical revision of the existent literature allows showing symptoms of alkali-silica reaction (ASR in highways, and the practical and economic method uranyl acetate to confirm the presence of ASR. The existence of reaction in concrete pavements of Chihuahua City was verified by a visual observation of patterns cracks, examination of gel deposits and the presence of reactive materials. Considering that the cement used to construct this pavements with problems of ASR, was low alkalis cement, the research was devoted to study the influence of alkalis coming from different sources than cement in the evolution of reaction such as: a aggregates: gravel and sand, b mix water, c additives and d minerals additions The initial classification of cements like high and low alkalis concerned to ASR must be revised for accept the fact that there is not a unique maximum limit alkalis of cement under which the expansible reactivity cannot occur.

    Una revisión bibliográfica de la literatura existente permite mostrar las manifestaciones de reacción álcali-sílice (RAS en estructuras de carreteras y el método práctico y económico de acetato de uranilo para confirmar la presencia de RAS. La existencia de la reacción en pavimentos de hormigón de la ciudad de Chihuahua se pudo confirmar tras la observación visual de modelos de grietas, estudios de depósitos de gel y existencia de fuentes de materiales reactivos. Considerando que el cemento utilizado para construir los tramos de pavimento con problemas de RAS, era un cemento bajo en álcalis, se enfocó la investigación al estudio de la influencia de los álcalis provenientes de fuentes distintas al cemento en la evolución de la reacción tales como: a áridos gruesos y finos, b agua de mezclado, c aditivos y d adiciones minerales El concepto inicial de clasificación de cementos altos y bajos en álcalis con respecto a la RAS debe ser revisado para aceptar el hecho de que no hay un solo

  7. Pi resonance of chemisorbed alkali atoms on noble metals.

    Science.gov (United States)

    Borisov, A G; Sametoglu, V; Winkelmann, A; Kubo, A; Pontius, N; Zhao, J; Silkin, V M; Gauyacq, J P; Chulkov, E V; Echenique, P M; Petek, H

    2008-12-31

    We have performed a joint experimental and theoretical study of the unoccupied electronic structure of alkali adsorbates on the (111) surfaces of Cu and Ag. Combining angle- and time-resolved two-photon photoemission spectroscopy with wave packet propagation calculations we show that, along with the well known sigma resonance oriented along the surface normal, there exist long-lived alkali-localized resonances oriented parallel to the surface (pi symmetry). These new resonances are stabilized by the projected band gap of the substrate and emerge primarily from the mixing of the p and d Rydberg orbitals of the free alkali atom modified by the interaction with the surface.

  8. Important role of alkali atoms in A4C60

    OpenAIRE

    Gunnarsson, O.; Erwin, S. C.; Koch, E.; Martin, R. M.

    1997-01-01

    We show that hopping via the alkali atoms plays an important role for the t1u band of A4C60 (A=K, Rb), in strong contrast to A3C60. Thus the t1u band is broadened by more than 40 % by the presence of the alkali atoms. The difference between A4C60 and A3C60 is in particular due to the less symmetric location of the alkali atoms in A4C60.

  9. Trace Element Geochemistry of Tertiary Continental Alkali Basalts from the Liuhe—Yizheng Area,Jiangsu Province,China

    Institute of Scientific and Technical Information of China (English)

    支霞臣

    1991-01-01

    Reported in this paper are the chemical compositions and trace element (REE,Ba,Rb,Sr,Nb,Zr,Ni,Cr,V,Ga,Y,Sc,Zn,Cu,etc)abundances of Tertiary continental alkali basalts from the Liube-yizheng area,Jiangsu Province,China.The olivine basalt,alkali olivine basalt and basanite are all derived from evolved melts which were once af-fected by different degrees of fractional crystallization of olivine and clinopyroxene(1:2)under high pres-sures.The initial melts were derived from the garnet lherzolite-type mantle source through low-degree par-tial melting.The mantle source has been affected by recent mantle-enrichment events(e.g.mantle metasomatism),resulting in incompatible trace element enrichment and long-term depletion of radiogenic isotopic compositions of Sr and Nd.

  10. Arsine oxidation with heteropoly acid in the presence of halide ions

    Energy Technology Data Exchange (ETDEWEB)

    Dorfman, Ya.A.; Aleshkova, M.M.; Doroshkevich, D.M.; Kel' man, I.V. (AN Kazakhskoj SSR, Alma-Ata. Inst. Organicheskogo Kataliza i Ehlektrokhimii)

    1984-12-01

    Kinetics and mechanism of arsine oxidation by phosphomolybdovanadium heteropoly acid are studied in the presense of halide ions as catalysts. It is established that intrasphere arsine oxidation in an intermediate V(5) complex with AsH/sub 3/ and halide-ion is a limiting stage of the proposed mechanism. The quantum-chemical calculation of the electronic structure of intermediate complexes, which supports the above mechanism is carried out. The method of theoretical estimation of the activation energy is proposed.

  11. Spectroscopic Investigation of Indium Halides as Substitutes of Mercury in Low Pressure Discharges for Lighting Applications

    OpenAIRE

    Briefi, Stefan

    2012-01-01

    Low pressure discharges with indium halides as radiator are discussed as substitutes for hazardous mercury in conventional fluorescent lamps. In this work, the applicability of InBr and InCl in a low pressure discharge light source is investigated. The aim is to identify and understand the physical processes which determine the discharge characteristics and the efficiency of the generated near-UV emission of the indium halide molecule and of the indium atom which is created due to dissociatio...

  12. Unique properties of halide perovskites as possible origins of the superior solar cell performance.

    Science.gov (United States)

    Yin, Wan-Jian; Shi, Tingting; Yan, Yanfa

    2014-07-16

    Halide perovskites solar cells have the potential to exhibit higher energy conversion efficiencies with ultrathin films than conventional thin-film solar cells based on CdTe, CuInSe2 , and Cu2 ZnSnSe4 . The superior solar-cell performance of halide perovskites may originate from its high optical absorption, comparable electron and hole effective mass, and electrically clean defect properties, including point defects and grain boundaries.

  13. On halide derivatives of rare-earth metal(III) oxidomolybdates(VI) and -tungstates(VI)

    Energy Technology Data Exchange (ETDEWEB)

    Schleid, Thomas; Hartenbach, Ingo [Stuttgart Univ. (Germany). Inst. for Inorganic Chemistry

    2016-11-01

    Halide derivatives of rare-earth metal(III) oxidomolybdates(VI) have been investigated comprehensively over the last decade comprising the halogens fluorine, chlorine, and bromine. Iodide-containing compounds are so far unknown. The simple composition REXMoO{sub 4} (RE=rare-earth element, X=halogen) is realized for X=F almost throughout the complete lanthanide series as well as for yttrium. While ytterbium and lutetium do not form any fluoride derivative, for lanthanum, only a fluoride-deprived compound with the formula La{sub 3}FMo{sub 4}O{sub 16} is realized. Moreover, molybdenum-rich compounds with the formula REXMo{sub 2}O{sub 7} are also known for yttrium and the smaller lanthanoids. For X=Cl the composition REClMoO{sub 4} is known for yttrium and the whole lanthanide series, although, four different structure types were identified. Almost the same holds for X=Br, however, only two different structure types are realized in this class of compounds. In the case of halide derivatives of rare-earth metal(III) oxidotungstates(VI) the composition REXWO{sub 4} is found for chlorides and bromides only, so far. Due to the similar size of Mo{sup 6+} and W{sup 6+} cations, the structures found for the tungstates are basically the same as for the molybdates. With the larger lanthanides, the representatives for both chloride and bromide derivates exhibit similar structural motifs as seen in the molybdates, however, the crystal structure cannot be determined reliably. In case of the smaller lanthanoids, the chloride derivatives are isostructural with the respective molybdates, although the existence ranges differ slightly. The same is true for rare-earth metal(III) bromide oxidotungstates(VI).

  14. Mechanistic Aspects of Aryl-Halide Oxidative Addition, Coordination Chemistry, and Ring-Walking by Palladium.

    Science.gov (United States)

    Zenkina, Olena V; Gidron, Ori; Shimon, Linda J W; Iron, Mark A; van der Boom, Milko E

    2015-11-01

    This contribution describes the reactivity of a zero-valent palladium phosphine complex with substrates that contain both an aryl halide moiety and an unsaturated carbon-carbon bond. Although η(2) -coordination of the metal center to a C=C or C≡C unit is kinetically favored, aryl halide bond activation is favored thermodynamically. These quantitative transformations proceed under mild reaction conditions in solution or in the solid state. Kinetic measurements indicate that formation of η(2) -coordination complexes are not nonproductive side-equilibria, but observable (and in several cases even isolated) intermediates en route to aryl halide bond cleavage. At the same time, DFT calculations show that the reaction with palladium may proceed through a dissociation-oxidative addition mechanism rather than through a haptotropic intramolecular process (i.e., ring walking). Furthermore, the transition state involves coordination of a third phosphine to the palladium center, which is lost during the oxidative addition as the C-halide bond is being broken. Interestingly, selective activation of aryl halides has been demonstrated by adding reactive aryl halides to the η(2) -coordination complexes. The product distribution can be controlled by the concentration of the reactants and/or the presence of excess phosphine.

  15. Preliminary Study on Synthesis of Organolead Halide with Lead Derived from Solder Wire

    Science.gov (United States)

    Pratiwi, P.; Rahmi, G. N.; Aimon, A. H.; Iskandar, F.; Abdullah, M.; Nuryadin, B. W.

    2016-08-01

    Organolead halide has attracted great attention for application in perovskite solar cells due to its high power conversion efficiency (PCE) of up to 20.1%. One of the most common perovskite materials is lead based reagent. In this research, we have synthesized organolead halide with lead extracted from solder wire. In the preparation procedure, first PbCl2 and PbI2 are produced by reacting lead from the solder wire with NaCl and KI, which are used as the basic substance for the perovskite material. Then, in order to get perovskite solution, the powders are reacted with methylamine iodide (MAI) in dimethylformamide (DMF) using a solution based method. Further, the spin coating method is used to fabricate perovskite thin film. The XRD peak results agreed with JCPDS Powder Diffraction of PbCl2 and PbI2. Based on FTIR, the transmittance spectra of the organolead mixed halide that was prepared using solder wire lead exhibited absorption peaks identical to organolead mixed halide using commercial lead. The UV-Vis absorbance spectra of the organolead mixed halide from solder wire lead also exhibited the same absorption ability as from commercial lead. Morever, EDS measurement showed that the element composition of the perovskite thin film using lead from solder wire identical to that from commercial lead. This indicates that solder wire lead is suitable enough for organolead halide material synthesis.

  16. The effect of low solubility organic acids on the hygroscopicity of sodium halide aerosols

    Science.gov (United States)

    Miñambres, L.; Méndez, E.; Sánchez, M. N.; Castaño, F.; Basterretxea, F. J.

    2014-10-01

    In order to accurately assess the influence of fatty acids on the hygroscopic and other physicochemical properties of sea salt aerosols, hexanoic, octanoic or lauric acid together with sodium halide salts (NaCl, NaBr and NaI) have been chosen to be investigated in this study. The hygroscopic properties of sodium halide sub-micrometre particles covered with organic acids have been examined by Fourier-transform infrared spectroscopy in an aerosol flow cell. Covered particles were generated by flowing atomized sodium halide particles (either dry or aqueous) through a heated oven containing the gaseous acid. The obtained results indicate that gaseous organic acids easily nucleate onto dry and aqueous sodium halide particles. On the other hand, scanning electron microscopy (SEM) images indicate that lauric acid coating on NaCl particles makes them to aggregate in small clusters. The hygroscopic behaviour of covered sodium halide particles in deliquescence mode shows different features with the exchange of the halide ion, whereas the organic surfactant has little effect in NaBr particles, NaCl and NaI covered particles experience appreciable shifts in their deliquescence relative humidities, with different trends observed for each of the acids studied. In efflorescence mode, the overall effect of the organic covering is to retard the loss of water in the particles. It has been observed that the presence of gaseous water in heterogeneously nucleated particles tends to displace the cover of hexanoic acid to energetically stabilize the system.

  17. The effect of low solublility organic acids on the hygroscopicity of sodium halide aerosols

    Science.gov (United States)

    Miñambres, L.; Méndez, E.; Sánchez, M. N.; Castaño, F.; Basterretxea, F. J.

    2014-02-01

    In order to accurately assess the influence of fatty acids on the hygroscopic and other physicochemical properties of sea salt aerosols, hexanoic, octanoic or lauric acid together with sodium halide salts (NaCl, NaBr and NaI) have been chosen to be performed in this study. The hygroscopic properties of sodium halide submicrometer particles covered with organic acids have been examined by Fourier-transform infrared spectroscopy in an aerosol flow cell. Covered particles were generated by flowing atomized sodium halide particles (either dry or aqueous) through a heated oven containing the gaseous acid. The obtained results indicate that gaseous organic acids easily nucleate onto dry and aqueous sodium halide particles. On the other hand, Scanning Electron Microscopy (SEM) images indicate that lauric acid coating on NaCl particles makes them to aggregate in small clusters. The hygroscopic behaviour of covered sodium halide particles in deliquescence mode shows different features with the exchange of the halide ion: whereas the organic covering has little effect in NaBr particles, NaCl and NaI covered particles change their deliquescence relative humidities, with different trends observed for each of the acids studied. In efflorescence mode, the overall effect of the organic covering is to retard the loss of water in the particles. It has been observed that the presence of gaseous water in heterogeneously nucleated particles tends to displace the cover of hexanoic acid to energetically stabilize the system.

  18. Structure and electronic properties of alkali-C60 nanoclusters.

    Science.gov (United States)

    Rabilloud, Franck

    2010-07-08

    I investigated the structural and electronic properties of both Na(n)C(60) and Li(n)C(60) (n alkali atoms over the C(60) surface is analyzed. The hypotheses for either an homogeneous coating of the C(60) surface by the alkali atoms or the growth of an alkali droplet not wetting the fullerene surface are discussed. Lithium atoms are found to coat homogeneously the fullerene on the C(60) surface via pentagonal sites, contrary to sodium atoms, which prefer to form 4-atom islands on the surface. The charge transfer, the energetics, and the dipole moments are discussed in relation with available results. The adsorption of alkali atoms on the C(60) surface considerably enhances the capacity of C(60) to accept electrons. The arrangement of lithium atoms seems more favorable for the hydrogen storage than that of sodium atoms.

  19. Electric field-induced softening of alkali silicate glasses

    Energy Technology Data Exchange (ETDEWEB)

    McLaren, C.; Heffner, W.; Jain, H. [Department of Materials Science and Engineering, Lehigh University, Bethlehem, Pennsylvania 18015 (United States); Tessarollo, R.; Raj, R. [Department of Mechanical Engineering, University of Colorado at Boulder, Boulder, Colorado 80309 (United States)

    2015-11-02

    Motivated by the advantages of two-electrode flash sintering over normal sintering, we have investigated the effect of an external electric field on the viscosity of glass. The results show remarkable electric field-induced softening (EFIS), as application of DC field significantly lowers the softening temperature of glass. To establish the origin of EFIS, the effect is compared for single vs. mixed-alkali silicate glasses with fixed mole percentage of the alkali ions such that the mobility of alkali ions is greatly reduced while the basic network structure does not change much. The sodium silicate and lithium-sodium mixed alkali silicate glasses were tested mechanically in situ under compression in external electric field ranging from 0 to 250 V/cm in specially designed equipment. A comparison of data for different compositions indicates a complex mechanical response, which is observed as field-induced viscous flow due to a combination of Joule heating, electrolysis and dielectric breakdown.

  20. A Novel Eco-Alkali Chemistry in Newspaper Flotation Deinking

    Directory of Open Access Journals (Sweden)

    Ivana Plazonic

    2013-01-01

    Full Text Available Performance and efficiency of fresh offset-printed daily Croatian newspaper deinked by novel chemistry, named Eco-alkali, were investigated in this study. Eco-alkali is naturally gained alkali prepared from domestic by-product wood fly ash collected after hardwood ignition. Brightness, opacity and effective residual ink concentration (ERIC as optical properties were evaluated for the deinked pulp before and after flotation. Lingering ink particles and their total surface area were measured by image analysis method. Experimental results are compared to the pulp deinked with worldwide accepted method INGEDE Method 11 using identical steps through the whole deinking process. The findings obtained from present work, especially removing particle efficiency results before flotation, indicated that eco-alkali have potential to be used in flotation deinking of newspapers.

  1. Acid/alkali gated photochromism of two diarylperfluorocyclopentenes

    Institute of Scientific and Technical Information of China (English)

    CHEN; ZiHui; ZHAO; ShengMin; LI; ZhongYu; ZHANG; Zhi; ZHANG; FuShi

    2007-01-01

    Two novel diarylfuorocyclopentenes, which underwent gated photochromism, were synthesized. It was found that the photochromic property of these diarylethenes could be switched by alternative addition of acids/alkalis, which could provide a new design strategy toward chemical threshold photoreaction.

  2. Pressure-structure relationships in the 10 K layered carbide halide superconductor Y2C2I2.

    Science.gov (United States)

    Ahn, Kyungsoo; Kremer, Reinhard K; Simon, Arndt; Marshall, William G; Muñoz, Alfonso

    2016-09-21

    The electronic structures of the 10 K layered yttrium carbide halide superconductor Y2C2I2 is characterized by bands of low dispersion and narrow peak-valley features in the electronic density of states at the Fermi level. In order to investigate to what extent the superconducting properties can be modified by external pressure we have studied the pressure dependence of the superconducting critical temperature and the crystal structure of Y2C2I2 to pressures of 7.4 GPa. Up to ~2.5 GPa we observe an increase of T c from 10 K to about 12 K. A structural phase transition from a 1s to a 3s stacking variant occurs at about 2.5 GPa above which T c rapidly decreases to a value of ~7.5 K at 7.5 GPa. Density functional calculations corroborate the structural phase transition to occur at a critical cell volume of ~270 Å(3) corresponding to a pressure of ~2.4 GPa, in good agreement with the experimental findings. The pressure dependence of T c and inter-atomic distances and angles are discussed with respect to the results of density functional calculations of the electronic and crystal structure.

  3. Pressure-structure relationships in the 10 K layered carbide halide superconductor Y2C2I2

    Science.gov (United States)

    Ahn, Kyungsoo; Kremer, Reinhard K.; Simon, Arndt; Marshall, William G.; Muñoz, Alfonso

    2016-09-01

    The electronic structures of the 10 K layered yttrium carbide halide superconductor Y2C2I2 is characterized by bands of low dispersion and narrow peak-valley features in the electronic density of states at the Fermi level. In order to investigate to what extent the superconducting properties can be modified by external pressure we have studied the pressure dependence of the superconducting critical temperature and the crystal structure of Y2C2I2 to pressures of 7.4 GPa. Up to ~2.5 GPa we observe an increase of T c from 10 K to about 12 K. A structural phase transition from a 1s to a 3s stacking variant occurs at about 2.5 GPa above which T c rapidly decreases to a value of ~7.5 K at 7.5 GPa. Density functional calculations corroborate the structural phase transition to occur at a critical cell volume of ~270 Å3 corresponding to a pressure of ~2.4 GPa, in good agreement with the experimental findings. The pressure dependence of T c and inter-atomic distances and angles are discussed with respect to the results of density functional calculations of the electronic and crystal structure.

  4. Near atomically smooth alkali antimonide photocathode thin films

    CERN Document Server

    Feng, Jun; Nasiatka, James; Schubert, Susanne; Smedley, John; Padmore, Howard

    2016-01-01

    Nano-roughness limits the emittance of electron beams that can be generated by high efficiency photocathodes, such as the thermally reacted alkali antimonide thin films. However there is an urgent need for photocathodes that can produce an order of magnitude or more lower emittance than present day systems in order to increase the transverse coherence width of the electron beam. In this paper we demonstrate a method for producing alkali antimonide cathodes with near atomic smoothness with high reproducibility.

  5. Estimating the hydration enthalpies of neutral alkali metal atoms.

    Science.gov (United States)

    Stace, A J

    2006-10-26

    Using existing data on the ionization energies of alkali metal atoms in small clusters of water, a thermodynamic cycle is proposed from which the hydration enthalpies of the neutral metal atoms can be estimated. Where comparisons are possible, the results are in reasonable agreement with those obtained using both experimental and ab initio methods. Application of the thermodynamic cycle to neutral alkali metal atoms solvated in ammonia yields solvation enthalpies that are significantly lower than those obtained for water.

  6. Alkali promotion of N-2 dissociation over Ru(0001)

    DEFF Research Database (Denmark)

    Mortensen, Jens Jørgen; Hammer, Bjørk; Nørskov, Jens Kehlet

    1998-01-01

    Using self-consistent density functional calculations, we show that adsorbed Na and Cs lower the barrier for dissociation of N2 on Ru(0001). Since N2 dissociation is a crucial step in the ammonia synthesis reaction, we explain in this way the experimental observation that alkali metals promote...... the ammonia synthesis reaction over Ru catalysts. We also show that the origin of this effect is predominantly a direct electrostatic attraction between the adsorbed alkali atoms and the dissociating molecule....

  7. Photoemission spectroscopy study of a multi-alkali photocathode

    CERN Document Server

    Ettema, A R H

    2000-01-01

    In this paper a photoemission study of the highest core levels of the elements and the electron escape barrier (work function) in a multi-alkali photocathode are presented. The core levels indicate that the alkali atoms are in an oxidized state and therefore the compound Na sub 2 KSb can be regarded as an ionic semiconductor. The measured escape barrier of the Cs sub 2 O surface layer is determined as 2.3 eV.

  8. Alkali absorption and citrate excretion in calcium nephrolithiasis

    Science.gov (United States)

    Sakhaee, K.; Williams, R. H.; Oh, M. S.; Padalino, P.; Adams-Huet, B.; Whitson, P.; Pak, C. Y.

    1993-01-01

    The role of net gastrointestinal (GI) alkali absorption in the development of hypocitraturia was investigated. The net GI absorption of alkali was estimated from the difference between simple urinary cations (Ca, Mg, Na, and K) and anions (Cl and P). In 131 normal subjects, the 24 h urinary citrate was positively correlated with the net GI absorption of alkali (r = 0.49, p < 0.001). In 11 patients with distal renal tubular acidosis (RTA), urinary citrate excretion was subnormal relative to net GI alkali absorption, with data from most patients residing outside the 95% confidence ellipse described for normal subjects. However, the normal relationship between urinary citrate and net absorbed alkali was maintained in 11 patients with chronic diarrheal syndrome (CDS) and in 124 stone-forming patients devoid of RTA or CDS, half of whom had "idiopathic" hypocitraturia. The 18 stone-forming patients without RTA or CDS received potassium citrate (30-60 mEq/day). Both urinary citrate and net GI alkali absorption increased, yielding a significantly positive correlation (r = 0.62, p < 0.0001), with the slope indistinguishable from that of normal subjects. Thus, urinary citrate was normally dependent on the net GI absorption of alkali. This dependence was less marked in RTA, confirming the renal origin of hypocitraturia. However, the normal dependence was maintained in CDS and in idiopathic hypocitraturia, suggesting that reduced citrate excretion was largely dietary in origin as a result of low net alkali absorption (from a probable relative deficiency of vegetables and fruits or a relative excess of animal proteins).

  9. Microstructured hydroxyl environments and Raman spectroscopy in selected basic transition-metal halides

    Institute of Scientific and Technical Information of China (English)

    Liu Xiao-Dong; Meng Dong-Dong; Hagihala Masato; Zheng Xu-Guang

    2011-01-01

    Raman vibrational spectra of the selected basic(hydroxyl OH and deuteroxyl OD)transition-metal halides,geometrically frustrated material series α-,β-,γ-Cu2(OH)3Cl,α-Cu2(OH)3Br,β-Ni2(OH)3Cl,β-Co2(OH)3Cl,β-Co2(OH)3Br,γ-Cu2(OD)3Cl,and β-Co2(OD)3Cl are measured at room temperature and analysed to investigate the relationship between the microstructured OH environments and their respective Raman spectra.Among these selected samples,the last two are used to determine the OH stretching vibration region(3600 cm-1-3300 cm-1)and OH bending vibration region(1000 cm-1-600 cm-1)of OH systems in the spectra.Through the comparative analysis of the distances d(metal-O),d(O-halogen),and d(OH),the strong metal-O interaction and trimeric hydrogen bond(C3υ,Cs,or C1 symmetry)are found in every material,but both determine simultaneously an ultimate d(OH),and therefore an OH stretching vibration frequency.According to the approximately linear relationship between the OH stretching vibration frequency and d(OH),some unavailable d(OH)are guessed and some doubtful d(OH)are suggested to be corrected.In addition,it is demonstrated in brief that the OH bending vibration frequency is also of importance to check the more detailed crystal microstructure relating to the OH group.

  10. Absorption spectra of alkali-C₆₀ nanoclusters.

    Science.gov (United States)

    Rabilloud, Franck

    2014-10-28

    We investigate the absorption spectra of alkali-doped C60 nanoclusters, namely C60Nan, C60Kn, and C60Lin, with n = 1, 2, 6, 12, in the framework of the time-dependent density-functional theory (TDDFT). We study the dependence of the absorption spectra on the nature of the alkali. We show that in few cases the absorption spectra depend on the arrangement of the alkali atoms over the fullerene, though sometimes the absorption spectra do not allow us to distinguish between different configurations. When only one or two alkali atoms are adsorbed on the fullerene, the optical response of alkali-doped C60 is similar to that of the anion C60(-) with a strong response in the UV domain. In contrast, for higher concentration of alkali, a strong optical response is predicted in the visible range, particularly when metal-metal bonds are formed. The weak optical response of the I(h)-symmetry C60Li12 is proposed to be used as a signature of its structure.

  11. Alkali-metal azides interacting with metal-organic frameworks.

    Science.gov (United States)

    Armata, Nerina; Cortese, Remedios; Duca, Dario; Triolo, Roberto

    2013-01-14

    Interactions between alkali-metal azides and metal-organic framework (MOF) derivatives, namely, the first and third members of the isoreticular MOF (IRMOF) family, IRMOF-1 and IRMOF-3, are studied within the density functional theory (DFT) paradigm. The investigations take into account different models of the selected IRMOFs. The mutual influence between the alkali-metal azides and the π rings or Zn centers of the involved MOF derivatives are studied by considering the interactions both of the alkali-metal cations with model aromatic centers and of the alkali-metal azides with distinct sites of differently sized models of IRMOF-1 and IRMOF-3. Several exchange and correlation functionals are employed to calculate the corresponding interaction energies. Remarkably, it is found that, with increasing alkali-metal atom size, the latter decrease for cations interacting with the π-ring systems and increase for the azides interacting with the MOF fragments. The opposite behavior is explained by stabilization effects on the azide moieties and determined by the Zn atoms, which constitute the inorganic vertices of the IRMOF species. Larger cations can, in fact, coordinate more efficiently to both the aromatic center and the azide anion, and thus stabilizing bridging arrangements of the azide between one alkali-metal and two Zn atoms in an η(2) coordination mode are more favored.

  12. Two-phase alkali-metal experiments in reduced gravity

    Energy Technology Data Exchange (ETDEWEB)

    Antoniak, Z.I.

    1986-06-01

    Future space missions envision the use of large nuclear reactors utilizing either a single or a two-phase alkali-metal working fluid. The design and analysis of such reactors require state-of-the-art computer codes that can properly treat alkali-metal flow and heat transfer in a reduced-gravity environment. A literature search of relevant experiments in reduced gravity is reported on here, and reveals a paucity of data for such correlations. The few ongoing experiments in reduced gravity are noted. General plans are put forth for the reduced-gravity experiments which will have to be performed, at NASA facilities, with benign fluids. A similar situation exists regarding two-phase alkali-metal flow and heat transfer, even in normal gravity. Existing data are conflicting and indequate for the task of modeling a space reactor using a two-phase alkali-metal coolant. The major features of past experiments are described here. Data from the reduced-gravity experiments with innocuous fluids are to be combined with normal gravity data from the two-phase alkali-metal experiments. Analyses undertaken here give every expectation that the correlations developed from this data base will provide a valid representation of alkali-metal heat transfer and pressure drop in reduced gravity.

  13. CHEMICAL AND THERMAL STABILITY OF RICE HUSKS AGAINST ALKALI TREATMENT

    Directory of Open Access Journals (Sweden)

    Bwire S. Ndazi

    2008-11-01

    Full Text Available Chemical and thermal stability of rice husks against alkali treatment with 2 to 8% w/v NaOH are presented and discussed in this paper. The thermal stability of the rice husks was examined by using a thermal gravimetric analysis instrument. Chemical stability was evaluated by examining the organic components of rice husks using proximate analysis. The results indicated that the proportion of lignin and hemicellulose in rice husks treated with NaOH ranging from 4 to 8% decreased significantly by 96% and 74%, respectively. The thermal stability and final degradation temperatures of the alkali-treated rice husks were also lowered by 24-26°C due to degradation of hemicellulose and lignin during alkali treatment. Absence of the onset degradation zones in the alkali-treated rice husks was a further indication that hemicellulose and other volatile substances degraded during alkali treatment. This leads to a conclusion that alkali treatment of rice husks with more than 4% NaOH causes a substantial chemical degradation of rice husks, which subsequently decreases their thermal stability.

  14. Vibrations of alkali metal overlayers on metal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Rusina, G G; Eremeev, S V; Borisova, S D [Institute of Strength Physics and Materials Science SB RAS, 634021, Tomsk (Russian Federation); Echenique, P M; Chulkov, E V [Donostia International Physics Center (DIPC), 20018 San Sebastian/Donostia, Basque Country (Spain); Benedek, G [Dipartimento di Scienza dei Materiali, Universita di Milano-Bicocca, Via Cozzi 53, 20125 Milano (Italy)], E-mail: rusina@ispms.tsc.ru

    2008-06-04

    We review the current progress in the understanding of vibrations of alkalis adsorbed on metal surfaces. The analysis of alkali vibrations was made on the basis of available theoretical and experimental results. We also include in this discussion our recent calculations of vibrations in K/Pt(111) and Li(Na)/Cu(001) systems. The dependence of alkali adlayer localized modes on atomic mass, adsorption position and coverage as well as the dependence of vertical vibration frequency on the substrate orientation is discussed. The square root of atomic mass dependence of the vertical vibration energy has been confirmed by using computational data for alkalis on the Al(111) and Cu(001) substrates. We have confirmed that in a wide range of submonolayer coverages the stretch mode energy remains nearly constant while the energy of in-plane polarized modes increases with the increase of alkali coverage. It was shown that the spectrum of both stretch and in-plane vibrations can be very sensitive to the adsorption position of alkali atoms and substrate orientation.

  15. Vibrations of alkali metal overlayers on metal surfaces

    Science.gov (United States)

    Rusina, G. G.; Eremeev, S. V.; Echenique, P. M.; Benedek, G.; Borisova, S. D.; Chulkov, E. V.

    2008-06-01

    We review the current progress in the understanding of vibrations of alkalis adsorbed on metal surfaces. The analysis of alkali vibrations was made on the basis of available theoretical and experimental results. We also include in this discussion our recent calculations of vibrations in K/Pt(111) and Li(Na)/Cu(001) systems. The dependence of alkali adlayer localized modes on atomic mass, adsorption position and coverage as well as the dependence of vertical vibration frequency on the substrate orientation is discussed. The square root of atomic mass dependence of the vertical vibration energy has been confirmed by using computational data for alkalis on the Al(111) and Cu(001) substrates. We have confirmed that in a wide range of submonolayer coverages the stretch mode energy remains nearly constant while the energy of in-plane polarized modes increases with the increase of alkali coverage. It was shown that the spectrum of both stretch and in-plane vibrations can be very sensitive to the adsorption position of alkali atoms and substrate orientation.

  16. Alkali and heavy metal emissions of the PCFB-process; Alkali- ja raskasmetallipaeaestoet PCFB-prosessista

    Energy Technology Data Exchange (ETDEWEB)

    Kuivalainen, R.; Eriksson, T.; Lehtonen, P. [Foster Wheeler Energia Oy, Karhula (Finland)

    1997-10-01

    Pressurized Circulating Fluidized Bed (PCFB) combustion technology has been developed in Karhula R and D Center since 1986. As part of the development, 10 MW PCFB test facility was built in 1989. The test facility has been used for performance testing with different coal types through the years 1990-1995 in order to gain data for design and commercialization of the high-efficiency low-emission PCFB combustion technology. The main object of the project was to measure vapor phase Na and K concentrations in the PCFB flue gas after hot gas filter and investigate the effects of process conditions and sorbents on alkali release. The measurements were performed using plasma assisted method of TUT Laboratory of Plasma Technology and wet absorption method of VTT Energy. The measurements were carried out during three test campaigns at PCFB Test Facility in Karhula. In autumn 1995 both VTT and TUT methods were used. The measurements of the following test period in spring 1996 were performed by VTT, and during the last test segment in autumn 1996 TUT method was in use. During the last test period, the TUT instrument was used as semi-continuous (3 values/minute) alkali analyzer for part of the time. The measured Na concentrations were below 30 ppb(w) in all measured data points. The results of K were below 10 ppb(w). The accuracies of the both methods are about +50 % at this concentration range. The scatter of the data covers the effects of different process variables on the alkali emission. The measured emissions are at the same order of magnitude as the guideline emission limits estimated by gas turbine manufacturers

  17. Superconductivity in alkali-metal-doped picene.

    Science.gov (United States)

    Mitsuhashi, Ryoji; Suzuki, Yuta; Yamanari, Yusuke; Mitamura, Hiroki; Kambe, Takashi; Ikeda, Naoshi; Okamoto, Hideki; Fujiwara, Akihiko; Yamaji, Minoru; Kawasaki, Naoko; Maniwa, Yutaka; Kubozono, Yoshihiro

    2010-03-04

    Efforts to identify and develop new superconducting materials continue apace, motivated by both fundamental science and the prospects for application. For example, several new superconducting material systems have been developed in the recent past, including calcium-intercalated graphite compounds, boron-doped diamond and-most prominently-iron arsenides such as LaO(1-x)F(x)FeAs (ref. 3). In the case of organic superconductors, however, no new material system with a high superconducting transition temperature (T(c)) has been discovered in the past decade. Here we report that intercalating an alkali metal into picene, a wide-bandgap semiconducting solid hydrocarbon, produces metallic behaviour and superconductivity. Solid potassium-intercalated picene (K(x)picene) shows T(c) values of 7 K and 18 K, depending on the metal content. The drop of magnetization in K(x)picene solids at the transition temperature is sharp (<2 K), similar to the behaviour of Ca-intercalated graphite. The T(c) of 18 K is comparable to that of K-intercalated C(60) (ref. 4). This discovery of superconductivity in K(x)picene shows that organic hydrocarbons are promising candidates for improved T(c) values.

  18. Bioinorganic Chemistry of the Alkali Metal Ions.

    Science.gov (United States)

    Kim, Youngsam; Nguyen, Thuy-Tien T; Churchill, David G

    2016-01-01

    The common Group 1 alkali metals are indeed ubiquitous on earth, in the oceans and in biological systems. In this introductory chapter, concepts involving aqueous chemistry and aspects of general coordination chemistry and oxygen atom donor chemistry are introduced. Also, there are nuclear isotopes of importance. A general discussion of Group 1 begins from the prevalence of the ions, and from a comparison of their ionic radii and ionization energies. While oxygen and water molecule binding have the most relevance to biology and in forming a detailed understanding between the elements, there is a wide range of basic chemistry that is potentially important, especially with respect to biological chelation and synthetic multi-dentate ligand design. The elements are widely distributed in life forms, in the terrestrial environment and in the oceans. The details about the workings in animal, as well as plant life are presented in this volume. Important biometallic aspects of human health and medicine are introduced as well. Seeing as the elements are widely present in biology, various particular endogenous molecules and enzymatic systems can be studied. Sodium and potassium are by far the most important and central elements for consideration. Aspects of lithium, rubidium, cesium and francium chemistry are also included; they help in making important comparisons related to the coordination chemistry of Na(+) and K(+). Physical methods are also introduced.

  19. Alternative alkali resistant deNOx catalysts

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Kristensen, Steffen Buus; Due-Hansen, Johannes;

    2012-01-01

    Alternative alkali resistant deNOx catalysts were prepared using three different supports ZrO2, TiO2 and Mordenite zeolite. The majority of the catalysts were prepared by incipient wetness impregnation of a commercial support, with vanadium, copper or iron precursor, one catalyst was prepared...... by onepot sol–gel method. All catalysts were characterized by BET, XRPD and NH3-TPD. Initial SCR activities of 8 out of 9 catalysts showed higher NO conversion at least at one temperature in the temperature range 300–500 ◦C compared to the conventional V2O5-WO3/TiO2 catalyst. After potassium poisoning (100......–130 µmol of K/g of catalyst) the relative drop in SCR activity and acidity was lower for all the alternative catalysts compared to the industrial V2O5-WO3/TiO2 catalyst. Furthermore, Cu/MOR and Nano-V2O5/Sul-TiO2 catalysts showed 8–16 times higher SCR activities than the conventional even after high...

  20. Alkali-aggregate reactivity of typical siliceious glass and carbonate rocks in alkali-activated fly ash based geopolymers

    Science.gov (United States)

    Lu, Duyou; Liu, Yongdao; Zheng, Yanzeng; Xu, Zhongzi; Shen, Xiaodong

    2013-08-01

    For exploring the behaviour of alkali-aggregate reactivity (AAR) in alkali-activated geopolymeric materials and assessing the procedures for testing AAR in geopolymers, the expansion behaviour of fly ash based geopolymer mortars with pure silica glass and typical carbonate rocks were studied respectively by curing at various conditions, i.e. 23°C and 38°C with relative humidity over 95%, immersed in 1M NaOH solution at 80°C. Results show that, at various curing conditions, neither harmful ASR nor harmful ACR was observed in geopolymers with the criteria specified for OPC system. However, with the change of curing conditions, the geopolymer binder and reactive aggregates may experience different reaction processes leading to quite different dimensional changes, especially with additional alkalis and elevated temperatures. It suggests that high temperature with additional alkali for accelerating AAR in traditional OPC system may not appropriate for assessing the alkali-aggregate reactivity behaviour in geopolymers designed for normal conditions. On the other hand, it is hopeful to control the dimensional change of geopolymer mortar or concrete by selecting the type of aggregates and the appropriate curing conditions, thus changing the harmful AAR in OPC into beneficial AAR in geopolymers and other alkali-activated cementitious systems.

  1. Interactions and low energy collisions between an alkali ion and an alkali atom of different nucleus

    CERN Document Server

    Rakshit, Arpita; Berriche, Hamid; Deb, Bimalendu

    2015-01-01

    We study theoretically interaction potentials and low energy collisions between different alkali atoms and alkali ions. Specifically, we consider systems like X + Y$^{+}$, where X(Y$^{+})$ is either Li(Cs$^+$) or Cs((Li$^+$), Na(Cs$^+$) or Cs(Na$^+$) and Li(Rb$^+$) or Rb(Li$^+$). We calculate the molecular potentials of the ground and first two excited states of these three systems using pseudopotential method and compare our results with those obtained by others. We calculate ground-state scattering wave functions and cross sections of these systems for a wide range of energies. We find that, in order to get convergent results for the total scattering cross sections for energies of the order $1$ K, one needs to take into account at least 60 partial waves. In the low energy limit ($< 1 \\mu$K), elastic scattering cross sections exhibit Wigner law threshold behavior while in the high energy limit the cross sections go as $E^{-1/3}$. We discuss qualitatively the possibilities of forming cold molecular ion by ...

  2. Hydrogen storage over alkali metal hydride and alkali metal hydroxide composites

    Institute of Scientific and Technical Information of China (English)

    Pei Yu; Yong Shen Chua; Hujun Cao; Zhitao Xiong; Guotao Wu; Ping Chen

    2014-01-01

    Alkali metal hydroxide and hydride composite systems contain both protic (H bonded with O) and hydridic hydrogen. The interaction of these two types of hydrides produces hydrogen. The enthalpy of dehydrogenation increased with the increase of atomic number of alkali metals, i.e.,-23 kJ/molH2 for LiOH-LiH, 55.34 kJ/molH2 for NaOH-NaH and 222 kJ/molH2 for KOH-KH. These thermodynamic calculation results were consistent with our experimental results. H2 was released from LiOH-LiH system during ball milling. The dehydrogenation temperature of NaOH-NaH system was about 150◦C; whereas KOH and KH did not interact with each other during the heating process. Instead, KH decomposed by itself. In these three systems, NaOH-NaH was the only reversible hydrogen storage system, the enthalpy of dehydrogenation was about 55.65 kJ/molH2 , and the corresponding entropy was ca. 101.23 J/(molH2 ·K), so the temperature for releasing 1.0 bar H2 was as high as 518◦C, showing unfavorable thermodynamic properties. The activation energy for hydrogen desorption of NaOH-NaH was found to be 57.87 kJ/mol, showing good kinetic properties.

  3. Coordination Chemistry Dictates the Structural Defects in Lead Halide Perovskites.

    Science.gov (United States)

    Rahimnejad, Sara; Kovalenko, Alexander; Forés, Sergio Martí; Aranda, Clara; Guerrero, Antonio

    2016-09-19

    We show the influence of species present in precursor solution during formation of lead halide perovskite materials on the structural defects of the films. The coordination of lead by competing solvent molecules and iodide ions dictate the type of complexes present in the films. Depending on the processing conditions all PbIS5 (+) , PbI2 S4, PbI3 S3 (-) , PbI4 S2 (2-) , PbI5 S2 (3-) , PbI6 (4-) and 1D (Pb2 I4 )n chains are observed by absorption measurements. Different parameters are studied such as polarity of the solvent, concentration of iodide ions, concentration of solvent molecules and temperature. It is concluded that strongly coordinating solvents will preferentially form species with a low number of iodide ions and less coordinative solvents generate high concentration of PbI6 (-) . We furthermore propose that all these plumbate ions may act as structural defects determining electronic properties of the photovoltaic films.

  4. Magnetic properties of nickel halide hydrates including deuteration effects

    Science.gov (United States)

    DeFotis, G. C.; Van Dongen, M. J.; Hampton, A. S.; Komatsu, C. H.; Trowell, K. T.; Havas, K. C.; Davis, C. M.; DeSanto, C. L.; Hays, K.; Wagner, M. J.

    2017-01-01

    Magnetic measurements on variously hydrated nickel chlorides and bromides, including deuterated forms, are reported. Results include locations and sizes of susceptibility maxima, Tmax and χmax, ordering temperatures Tc, Curie constants and Weiss theta in the paramagnetic regime, and primary and secondary exchange interactions from analysis of low temperature data. For the latter a 2D Heisenberg model augmented by interlayer exchange in a mean-field approximation is applied. Magnetization data to 16 kG as a function of temperature show curvature and hysteresis characteristics quite system dependent. For four materials high field magnetization data to 70 kG at 2.00 K are also obtained. Comparison is made with theoretical relations for spin-1 models. Trends are apparent, primarily that Tmax of each bromide hydrate is less than for the corresponding chloride, and that for a given halide nD2O (n=1 or 2) deuterates exhibit lesser Tmax than do nH2O hydrates. A monoclinic unit cell determined from powder X-ray diffraction data on NiBr2·2D2O is different from and slightly larger than that of NiBr2·2H2O. This provides some rationale for the difference in magnetic properties between these.

  5. Symmetry-Based Tight Binding Modeling of Halide Perovskite Semiconductors.

    Science.gov (United States)

    Boyer-Richard, Soline; Katan, Claudine; Traoré, Boubacar; Scholz, Reinhard; Jancu, Jean-Marc; Even, Jacky

    2016-10-06

    On the basis of a general symmetry analysis, this paper presents an empirical tight-binding (TB) model for the reference Pm-3m perovskite cubic phase of halide perovskites of general formula ABX3. The TB electronic band diagram, with and without spin orbit coupling effect of MAPbI3 has been determined based on state of the art density functional theory results including many body corrections (DFT+GW). It affords access to various properties, including distorted structures, at a significantly reduced computational cost. This is illustrated with the calculation of the band-to-band absorption spectrum, the variation of the band gap under volumetric strain, as well as the Rashba effect for a uniaxial symmetry breaking. Compared to DFT approaches, this empirical model will help to tackle larger issues, such as the electronic band structure of large nanostructures, including many-body effects, or heterostructures relevant to perovskite device modeling suited to the description of atomic-scale features.

  6. Advances and Promises of Layered Halide Hybrid Perovskite Semiconductors.

    Science.gov (United States)

    Pedesseau, Laurent; Sapori, Daniel; Traore, Boubacar; Robles, Roberto; Fang, Hong-Hua; Loi, Maria Antonietta; Tsai, Hsinhan; Nie, Wanyi; Blancon, Jean-Christophe; Neukirch, Amanda; Tretiak, Sergei; Mohite, Aditya D; Katan, Claudine; Even, Jacky; Kepenekian, Mikaël

    2016-11-22

    Layered halide hybrid organic-inorganic perovskites (HOP) have been the subject of intense investigation before the rise of three-dimensional (3D) HOP and their impressive performance in solar cells. Recently, layered HOP have also been proposed as attractive alternatives for photostable solar cells and revisited for light-emitting devices. In this review, we combine classical solid-state physics concepts with simulation tools based on density functional theory to overview the main features of the optoelectronic properties of layered HOP. A detailed comparison between layered and 3D HOP is performed to highlight differences and similarities. In the same way as the cubic phase was established for 3D HOP, here we introduce the tetragonal phase with D4h symmetry as the reference phase for 2D monolayered HOP. It allows for detailed analysis of the spin-orbit coupling effects and structural transitions with corresponding electronic band folding. We further investigate the effects of octahedral tilting on the band gap, loss of inversion symmetry and possible Rashba effect, quantum confinement, and dielectric confinement related to the organic barrier, up to excitonic properties. Altogether, this paper aims to provide an interpretive and predictive framework for 3D and 2D layered HOP optoelectronic properties.

  7. Emission Enhancement and Intermittency in Polycrystalline Organolead Halide Perovskite Films

    Directory of Open Access Journals (Sweden)

    Cheng Li

    2016-08-01

    Full Text Available Inorganic-organic halide organometal perovskites have demonstrated very promising performance for opto-electronic applications, such as solar cells, light-emitting diodes, lasers, single-photon sources, etc. However, the little knowledge on the underlying photophysics, especially on a microscopic scale, hampers the further improvement of devices based on this material. In this communication, correlated conventional photoluminescence (PL characterization and wide-field PL imaging as a function of time are employed to investigate the spatially- and temporally-resolved PL in CH3NH3PbI3−xClx perovskite films. Along with a continuous increase of the PL intensity during light soaking, we also observe PL blinking or PL intermittency behavior in individual grains of these films. Combined with significant suppression of PL blinking in perovskite films coated with a phenyl-C61-butyric acid methyl ester (PCBM layer, it suggests that this PL intermittency is attributed to Auger recombination induced by photoionized defects/traps or mobile ions within grains. These defects/traps are detrimental for light conversion and can be effectively passivated by the PCBM layer. This finding paves the way to provide a guideline on the further improvement of perovskite opto-electronic devices.

  8. Hysteresis, Stability, and Ion Migration in Lead Halide Perovskite Photovoltaics.

    Science.gov (United States)

    Miyano, Kenjiro; Yanagida, Masatoshi; Tripathi, Neeti; Shirai, Yasuhiro

    2016-06-16

    Ion migration has been suspected as the origin of various irreproducible and unstable properties, most notably the hysteresis, of lead halide perovskite photovoltaic (PV) cells since the early stage of the research. Although many evidence of ionic movement have been presented both numerically and experimentally, a coherent and quantitative picture that accounts for the observed irreproducible phenomena is still lacking. At the same time, however, it has been noticed that in certain types of PV cells, the hysteresis is absent or at least within the measurement reproducibility. We have previously shown that the electronic properties of hysteresis-free cells are well represented in terms of the conventional inorganic semiconductors. The reproducibility of these measurements was confirmed typically within tens of minutes under the biasing field of -1 V to +1.5 V. In order to probe the effect of ionic motion in the hysteresis-free cells, we extended the time scale and the biasing rage in the electronic measurements, from which we conclude the following: (1) From various evidence, it appears that ion migration is inevitable. However, it does not cause detrimental effects to the PV operation. (2) We propose, based on the quantitative characterization, that the degradation is more likely due to the chemical change at the interfaces between the carrier selective layers and perovskite rather than the compositional change of the lead iodide perovskite bulk. Together, they give much hope in the use of the lead iodide perovskite in the use of actual application.

  9. Electron-phonon coupling in hybrid lead halide perovskites.

    Science.gov (United States)

    Wright, Adam D; Verdi, Carla; Milot, Rebecca L; Eperon, Giles E; Pérez-Osorio, Miguel A; Snaith, Henry J; Giustino, Feliciano; Johnston, Michael B; Herz, Laura M

    2016-05-26

    Phonon scattering limits charge-carrier mobilities and governs emission line broadening in hybrid metal halide perovskites. Establishing how charge carriers interact with phonons in these materials is therefore essential for the development of high-efficiency perovskite photovoltaics and low-cost lasers. Here we investigate the temperature dependence of emission line broadening in the four commonly studied formamidinium and methylammonium perovskites, HC(NH2)2PbI3, HC(NH2)2PbBr3, CH3NH3PbI3 and CH3NH3PbBr3, and discover that scattering from longitudinal optical phonons via the Fröhlich interaction is the dominant source of electron-phonon coupling near room temperature, with scattering off acoustic phonons negligible. We determine energies for the interacting longitudinal optical phonon modes to be 11.5 and 15.3 meV, and Fröhlich coupling constants of ∼40 and 60 meV for the lead iodide and bromide perovskites, respectively. Our findings correlate well with first-principles calculations based on many-body perturbation theory, which underlines the suitability of an electronic band-structure picture for describing charge carriers in hybrid perovskites.

  10. Electron-phonon coupling in hybrid lead halide perovskites

    Science.gov (United States)

    Wright, Adam D.; Verdi, Carla; Milot, Rebecca L.; Eperon, Giles E.; Pérez-Osorio, Miguel A.; Snaith, Henry J.; Giustino, Feliciano; Johnston, Michael B.; Herz, Laura M.

    2016-05-01

    Phonon scattering limits charge-carrier mobilities and governs emission line broadening in hybrid metal halide perovskites. Establishing how charge carriers interact with phonons in these materials is therefore essential for the development of high-efficiency perovskite photovoltaics and low-cost lasers. Here we investigate the temperature dependence of emission line broadening in the four commonly studied formamidinium and methylammonium perovskites, HC(NH2)2PbI3, HC(NH2)2PbBr3, CH3NH3PbI3 and CH3NH3PbBr3, and discover that scattering from longitudinal optical phonons via the Fröhlich interaction is the dominant source of electron-phonon coupling near room temperature, with scattering off acoustic phonons negligible. We determine energies for the interacting longitudinal optical phonon modes to be 11.5 and 15.3 meV, and Fröhlich coupling constants of ~40 and 60 meV for the lead iodide and bromide perovskites, respectively. Our findings correlate well with first-principles calculations based on many-body perturbation theory, which underlines the suitability of an electronic band-structure picture for describing charge carriers in hybrid perovskites.

  11. Elusive Presence of Chloride in Mixed Halide Perovskite Solar Cells.

    Science.gov (United States)

    Colella, Silvia; Mosconi, Edoardo; Pellegrino, Giovanna; Alberti, Alessandra; Guerra, Valentino L P; Masi, Sofia; Listorti, Andrea; Rizzo, Aurora; Condorelli, Guglielmo Guido; De Angelis, Filippo; Gigli, Giuseppe

    2014-10-16

    The role of chloride in the MAPbI3-xClx perovskite is still limitedly understood, albeit subjected of much debate. Here, we present a combined angle-resolved X-ray photoelectron spectroscopy (AR-XPS) and first-principles DFT modeling to investigate the MAPbI3-xClx/TiO2 interface. AR-XPS analyses carried out on ad hoc designed bilayers of MAPbI3-xClx perovskite deposited onto a flat TiO2 substrate reveal that the chloride is preferentially located in close proximity to the perovskite/TiO2 interface. DFT calculations indicate the preferential location of chloride at the TiO2 interface compared to the bulk perovskite due to an increased chloride-TiO2 surface affinity. Furthermore, our calculations clearly demonstrate an interfacial chloride-induced band bending, creating a directional "electron funnel" that may improve the charge collection efficiency of the device and possibly affecting also recombination pathways. Our findings represent a step forward to the rationalization of the peculiar properties of mixed halide perovskite, allowing one to further address material and device design issues.

  12. Effects of Process Parameters on the Characteristics of Mixed-Halide Perovskite Solar Cells Fabricated by One-Step and Two-Step Sequential Coating.

    Science.gov (United States)

    Ahmadian-Yazdi, Mohammad Reza; Zabihi, Fatemeh; Habibi, Mehran; Eslamian, Morteza

    2016-12-01

    In this paper, two-step sequential spin-dip and spin-spin coating, as well as one-step spin coating, methods are used to fabricate methylammonium lead mixed-halide perovskites to study the effect of process parameters, including the choice of the solvent, annealing temperature, spin velocity, and dipping time on the characteristics of the perovskite film. Our results show that using a mixture of DMF and DMSO, with volume ratio of 1:1, as the organic solvents for PbCl2 results in the best mixed-halide perovskite because of the effective coordination between DMSO and PbCl2. Surface dewetting due to two effects, i.e., crystallization and thin liquid film instability, is observed and discussed, where an intermediate spin velocity of about 4000 rpm is found suitable to suppress dewetting. The perovskite film fabricated using the one-step method followed by anti-solvent treatment shows the best perovskite conversion in XRD patterns, and the planar device fabricated using the same method exhibited the highest efficiency among the employed methods. The perovskite layer made by sequential spin-dip coating is found thicker with higher absorbance, but the device shows a lower efficiency because of the challenges associated with perovskite conversion in the sequential method. The one-step deposition method is found easier to control and more promising than the sequential deposition methods.

  13. Effects of Process Parameters on the Characteristics of Mixed-Halide Perovskite Solar Cells Fabricated by One-Step and Two-Step Sequential Coating

    Science.gov (United States)

    Ahmadian-Yazdi, Mohammad Reza; Zabihi, Fatemeh; Habibi, Mehran; Eslamian, Morteza

    2016-09-01

    In this paper, two-step sequential spin-dip and spin-spin coating, as well as one-step spin coating, methods are used to fabricate methylammonium lead mixed-halide perovskites to study the effect of process parameters, including the choice of the solvent, annealing temperature, spin velocity, and dipping time on the characteristics of the perovskite film. Our results show that using a mixture of DMF and DMSO, with volume ratio of 1:1, as the organic solvents for PbCl2 results in the best mixed-halide perovskite because of the effective coordination between DMSO and PbCl2. Surface dewetting due to two effects, i.e., crystallization and thin liquid film instability, is observed and discussed, where an intermediate spin velocity of about 4000 rpm is found suitable to suppress dewetting. The perovskite film fabricated using the one-step method followed by anti-solvent treatment shows the best perovskite conversion in XRD patterns, and the planar device fabricated using the same method exhibited the highest efficiency among the employed methods. The perovskite layer made by sequential spin-dip coating is found thicker with higher absorbance, but the device shows a lower efficiency because of the challenges associated with perovskite conversion in the sequential method. The one-step deposition method is found easier to control and more promising than the sequential deposition methods.

  14. Alkali norite, troctolites, and VHK mare basalts from breccia 14304

    Science.gov (United States)

    Goodrich, Cyrena Anne; Taylor, G. Jeffrey; Keil, Klaus; Kallemeyn, Gregory W.; Warren, Paul H.

    1986-09-01

    Twelve clasts were separated from breccia 14304 for consortium study: six pristine highlands rocks, two mare basalts, and four nonpristine highlands rocks. The pristine highlands rocks include representatives of the magnesian troctolite-anorthosite and alkali suites, the two most common subgroups of the Mg suite found at the Apollo 14 site. Two troctolite clasts have olivine (~Fo 90) and plagioclase (~An 94) compositions similar to one group of Apolo 14 troctolites. One also contains spinel (Mg' 66-85). Incompatible element abundances in one are similar to those of 14305 troctolites, although the HREE (heavy rare earth elements) pattern is distinct among Apollo 14 troctolites. A dunite clast (~Fo 89) may be an unrepresentative piece of a troctolite. Alkali lithologies include an alkali anorthosite and an alkali norite, which is a rock type not previously described. The alkali norite has a pristine igneous texture and contains inverted pigeonite (Mg' 64), plagioclase (An82), K-feldspar, ternary feldspar, REE-rich phosphates, and silica. It resembles alkali gabbronorites from Apollo 14 and 67975 in mineralogy and mineral compositions. Alkali lithologies and phosphate-bearing magnesian anorthosites from Apollo 14 may have formed from Mg-rich magmas that assimilated various amounts of material rich in P and REE. This material could be a fractionated derivative of urKREEP. another pristine clast from 14304 is an Mg-gabbronorite. The two mare basalt clasts are very high potassium (VHK) basalts. They have 4 mg/g K and K/La ratios of 580 and 700. The parent magmas of VHK basalts could have formed from typical low-Ti, high-Al basaltic magmas by assimilation of K-rich material. This material could also be a fractionated derivative or urKREEP. Nonpristine 14304 clasts include melt-textured anorthosites and an augite-rich poikilitic melt rock. The latter is probably polymict, but its major component must be an Mg-suite gabbro.

  15. Molecular photons interfaced with alkali atoms.

    Science.gov (United States)

    Siyushev, Petr; Stein, Guilherme; Wrachtrup, Jörg; Gerhardt, Ilja

    2014-05-01

    Future quantum communication will rely on the integration of single-photon sources, quantum memories and systems with strong single-photon nonlinearities. Two key parameters are crucial for the single-photon source: a high photon flux with a very small bandwidth, and a spectral match to other components of the system. Atoms or ions may act as single-photon sources--owing to their narrowband emission and their intrinsic spectral match to other atomic systems--and can serve as quantum nonlinear elements. Unfortunately, their emission rates are still limited, even for highly efficient cavity designs. Single solid-state emitters such as single organic dye molecules are significantly brighter and allow for narrowband photons; they have shown potential in a variety of quantum optical experiments but have yet to be interfaced with other components such as stationary memory qubits. Here we describe the optical interaction between Fourier-limited photons from a single organic molecule and atomic alkali vapours, which can constitute an efficient quantum memory. Single-photon emission rates reach up to several hundred thousand counts per second and show a high spectral brightness of 30,000 detectable photons per second per megahertz of bandwidth. The molecular emission is robust and we demonstrate perfect tuning to the spectral transitions of the sodium D line and efficient filtering, even for emitters at ambient conditions. In addition, we achieve storage of molecular photons originating from a single dibenzanthanthrene molecule in atomic sodium vapour. Given the large set of molecular emission lines matching to atomic transitions, our results enable the combination of almost ideal single-photon sources with various atomic vapours, such that experiments with giant single-photon nonlinearities, mediated, for example, by Rydberg atoms, become feasible.

  16. Crystals in crystals

    DEFF Research Database (Denmark)

    Christensen, Claus H.; Schmidt, I.; Carlsson, A.;

    2005-01-01

    A major factor governing the performance of catalytically active particles supported on a zeolite carrier is the degree of dispersion. It is shown that the introduction of noncrystallographic mesopores into zeolite single crystals (silicalite-1, ZSM-5) may increase the degree of particle dispersion...... of the zeolite particles, particularly after thermal treatment. When using mesoporous zeolites, the particles were evenly distributed throughout the mesopore system of the zeolitic support, even after calcination, leading to nanocrystals within mesoporous zeolite single crystals....

  17. Si- and alkali-rich melt inclusions in minerals of mantle peridotites from eastern China: Implication for lithospheric evolution

    Institute of Scientific and Technical Information of China (English)

    FAN; Qicheng; SUI; Jianli; XU; Ping; LI; Ni; SUN; Qian; WANG; Tuanhua

    2006-01-01

    Minerals of spinel- and garnet-facies mantle xenoliths entrained in Cenozoic basalts from eastern China (North China, Northeastern China and Southeastern China coastal area) contains lots of melt inclusions. Studies on these melt inclusions show that the glass inclusions are rich in SiO2 (60%―68%) and alkalis (K2O+Na2O=5%―11%, especially for K2O) as well as volatiles such as H2O and CO2 (2%―7%), which belong to dacites and andesites of the high-K calcic alkali series rocks with few shoshonites. High Al and Ca diopside in melt inclusion is the product of melt crystallization at high temperature and pressure, rather than the product of devitrification. Results show that these K-rich (in general K2O>3%) intermediate-acidic silicate melt inclusions have characteristics of continent without a genetical link to host basalts and their phenocrystic minerals. Thus, these trapped melt inclusions represent melts of Mesozoic lithospheric mantle-crust interaction and imply that the continental lithospheric mantle beneath eastern China had undergone fragmentation and recreation processes during the Mesozoic and Cenozoic periods. This result undoubtly provides important implication for the evolution of sub-continental lithosphere beneath eastern China. We propose that these Si- and alkalis-rich melts should be responsible for the mantle chemical heterogeneity underneath eastern China.

  18. Exhaustive thin-layer cyclic voltammetry for absolute multianalyte halide detection.

    Science.gov (United States)

    Cuartero, Maria; Crespo, Gastón A; Ghahraman Afshar, Majid; Bakker, Eric

    2014-11-18

    Water analysis is one of the greatest challenges in the field of environmental analysis. In particular, seawater analysis is often difficult because a large amount of NaCl may mask the determination of other ions, i.e., nutrients, halides, and carbonate species. We demonstrate here the use of thin-layer samples controlled by cyclic voltammetry to analyze water samples for chloride, bromide, and iodide. The fabrication of a microfluidic electrochemical cell based on a Ag/AgX wire (working electrode) inserted into a tubular Nafion membrane is described, which confines the sample solution layer to less than 15 μm. By increasing the applied potential, halide ions present in the thin-layer sample (X(-)) are electrodeposited on the working electrode as AgX, while their respective counterions are transported across the perm-selective membrane to an outer solution. Thin-layer cyclic voltammetry allows us to obtain separated peaks in mixed samples of these three halides, finding a linear relationship between the halide concentration and the corresponding peak area from about 10(-5) to 0.1 M for bromide and iodide and from 10(-4) to 0.6 M for chloride. This technique was successfully applied for the halide analysis in tap, mineral, and river water as well as seawater. The proposed methodology is absolute and potentially calibration-free, as evidenced by an observed 2.5% RSD cell to cell reproducibility and independence from the operating temperature.

  19. Permeation of halide anions through phospholipid bilayers occurs by the solubility-diffusion mechanism

    Science.gov (United States)

    Paula, S.; Volkov, A. G.; Deamer, D. W.

    1998-01-01

    Two alternative mechanisms are frequently used to describe ionic permeation of lipid bilayers. In the first, ions partition into the hydrophobic phase and then diffuse across (the solubility-diffusion mechanism). The second mechanism assumes that ions traverse the bilayer through transient hydrophilic defects caused by thermal fluctuations (the pore mechanism). The theoretical predictions made by both models were tested for halide anions by measuring the permeability coefficients for chloride, bromide, and iodide as a function of bilayer thickness, ionic radius, and sign of charge. To vary the bilayer thickness systematically, liposomes were prepared from monounsaturated phosphatidylcholines (PC) with chain lengths between 16 and 24 carbon atoms. The fluorescent dye MQAE (N-(ethoxycarbonylmethyl)-6-methoxyquinolinium bromide) served as an indicator for halide concentration inside the liposomes and was used to follow the kinetics of halide flux across the bilayer membranes. The observed permeability coefficients ranged from 10(-9) to 10(-7) cm/s and increased as the bilayer thickness was reduced. Bromide was found to permeate approximately six times faster than chloride through bilayers of identical thickness, and iodide permeated three to four times faster than bromide. The dependence of the halide permeability coefficients on bilayer thickness and on ionic size were consistent with permeation of hydrated ions by a solubility-diffusion mechanism rather than through transient pores. Halide permeation therefore differs from that of a monovalent cation such as potassium, which has been accounted for by a combination of the two mechanisms depending on bilayer thickness.

  20. Influence of Halide Solutions on Collagen Networks: Measurements of Physical Properties by Atomic Force Microscopy

    Science.gov (United States)

    Kempe, André; Lackner, Maximilian

    2016-01-01

    The influence of aqueous halide solutions on collagen coatings was tested. The effects on resistance against indentation/penetration on adhesion forces were measured by atomic force microscopy (AFM) and the change of Young's modulus of the coating was derived. Comparative measurements over time were conducted with halide solutions of various concentrations. Physical properties of the mesh-like coating generally showed large variability. Starting with a compact set of physical properties, data disperse after minutes. A trend of increase in elasticity and permeability was found for all halide solutions. These changes were largest in NaI, displaying a logical trend with ion size. However a correlation with concentration was not measured. Adhesion properties were found to be independent of mechanical properties. The paper also presents practical experience for AFM measurements of soft tissue under liquids, particularly related to data evaluation. The weakening in physical strength found after exposure to halide solutions may be interpreted as widening of the network structure or change in the chemical properties in part of the collagen fibres (swelling). In order to design customized surface coatings at optimized conditions also for medical applications, halide solutions might be used as agents with little impact on the safety of patients.

  1. Palladium-catalyzed reductive homocoupling of aromatic halides and oxidation of alcohols.

    Science.gov (United States)

    Zeng, Minfeng; Du, Yijun; Shao, Linjun; Qi, Chenze; Zhang, Xian-Man

    2010-04-16

    Palladium-catalyzed reductive homocoupling of aromatic halides can be performed in alcohol solutions without any auxiliary reducing reagents. Pd(dppf)Cl(2) [dppf = 1,1'-bis(diphenylphosphino)ferrocene] has been shown as the most effective catalyst among the palladium catalysts screened for the model reductive homocoupling of iodobenzene in alcoholic solutions. The reduction of iodobenzene is stoichiometrically coupled with the oxidation of solvent alcohol (3-pentanol). The X-ray photoelectron spectroscopic (XPS) studies clearly indicate that the oxidation of solvent alcohol molecules is involved with the in situ regeneration of the reductive Pd(0)(dppf) active species, indicating that the solvent alcohol also reacts as a reducing reagent for the reductive homocoupling of aromatic halides. Elimination of the external reducing reagents will simplify the product separation and purification. Base is essential for the success of the Pd(dppf)Cl(2)-catalyzed redox reaction as 2 molar equiv of base is needed to neutralize the acid byproduct formed. Biaryls are the predominant products for the Pd(dppf)Cl(2)-catalyzed reductions of the unsubstituted aromatic halides in 3-pentanol solution, whereas the dehalogenation products are predominant for the Pd(dppf)Cl(2)-catalyzed reductions of the substituted aromatic halides. The reaction mechanisms have been discussed for the palladium-mediated concomitant reduction of aromatic halides and oxidation of alcohols without any auxiliary reductants and oxidants.

  2. Nature of the Charge Localized Between Alkali Adatoms and Metal Substrates

    OpenAIRE

    Wertheim, G. K.; Riffe, D. Mark; Citrin, P. H.

    1994-01-01

    Two previously unappreciated features in photoemission spectra from alkali atoms adsorbed on W(110), namely, the sign of the alkali-induced surface-atom core-level shift of the substrate at low coverage and the very large alkali shallow core-hole lifetime width at all coverages, show that the alkali-substrate interaction is not well described by a transfer of alkali charge. Instead, both features point to the formation of a charge cloud between the alkali adatom and substrate that is d...

  3. First structural evidence for multiple alkali metals between sandwich decks in a metallocene.

    Science.gov (United States)

    Jeletic, Matthew; Perras, Frédéric A; Gorelsky, Serge I; Le Roy, Jennifer J; Korobkov, Ilia; Bryce, David L; Murugesu, Muralee

    2012-07-14

    A tetralithio salt (1) derived by treating 1,4-bis(trimethylsilyl)-cyclooctatriene with (n)BuLi serves as the first structural evidence for a multi-alkali metallocene. Single-crystal XRD confirms two Li(+) each asymmetrically bind to η(3) and η(4) between two COT'' rings and two Li(+) terminally bind to η(3). Solid-state NMR studies confirm the presence of two distinct lithium ion sites while the solution NMR studies suggest the formation of an (COT'' dianion) ion-pair in solution. Further treating of the tetralithio salt with NaCl leads to linear sodium polymeric chains. Therefore, simply changing the ionic radius changes the molecular structure.

  4. Isomorphism of anhydrous tetrahedral halides and silicon chalcogenides: energy landscape of crystalline BeF2, BeCl2, SiO2, and SiS2.

    Science.gov (United States)

    Zwijnenburg, Martijn A; Corà, Furio; Bell, Robert G

    2008-08-20

    We employ periodic density functional theory calculations to compare the structural chemistry of silicon chalcogenides (silica, silicon sulfide) and anhydrous tetrahedral halides (beryllium fluoride, beryllium chloride). Despite the different formal oxidation states of the elements involved, the divalent halides are known experimentally to form crystal structures similar to known SiX2 frameworks; the rich polymorphic chemistry of SiO2 is however not matched by divalent halides, for which a very limited number of polymorphs are currently known. The calculated energy landscapes yield a quantitative match between the relative polymorphic stability in the SiO2/BeF2 pair, and a semiquantitative match for the SiS2/BeCl2 pair. The experimentally observed polymorphs are found to lie lowest in energy for each composition studied. For the two BeX2 compounds studied, polymorphs not yet synthesized are predicted to lie very low in energy, either slightly above or even in between the energy of the experimentally observed polymorphs. The experimental lack of polymorphism for tetrahedral halide materials thus does not appear to stem from a lack of low-energy polymorphs but more likely is the result of a lack of experimental exploration. Our calculations further indicate that the rich polymorphic chemistry of SiO2 can be potentially matched, if not extended, by BeF2, provided that milder synthetic conditions similar to those employed in zeolite synthesis are developed for BeF2. Finally, our work demonstrates that both classes of materials show the same behavior upon replacement of the 2p anion with the heavier 3p anion from the same group; the thermodynamic preference shifts from structures with large rings to structures with larger fractions of small two and three membered rings.

  5. Multi-photon processes in alkali metal vapors

    Science.gov (United States)

    Gai, Baodong; Hu, Shu; Li, Hui; Shi, Zhe; Cai, Xianglong; Guo, Jingwei; Tan, Yannan; Liu, Wanfa; Jin, Yuqi; Sang, Fengting

    2015-02-01

    Achieving population inversion through multi-photon cascade pumping is almost always difficult, and most laser medium work under 1-photon excitation mechanism. But for alkali atoms such as cesium, relatively large absorption cross sections of several low, cascading energy levels enable them properties such as up conversion. Here we carried out research on two-photon excitation alkali fluorescence. Two photons of near infrared region are used to excite alkali atoms to n 2 D5/2, n 2 D3/2 or higher energy levels, then the blue fluorescence of (n+1) 2 P3/2,(n+1) 2 P1/2-->n 2 S1/2 are observed. Different pumping paths are tried and by the recorded spectra, transition routes of cesium are deducted and concluded. Finally the possibility of two-photon style DPALs (diode pumped alkali laser) are discussed, such alkali lasers can give output wavelengths in the shorter end of visual spectroscopy (400-460 nm) and are expected to get application in underwater communication and material laser processing.

  6. Utilization of Mineral Wools as Alkali-Activated Material Precursor

    Directory of Open Access Journals (Sweden)

    Juho Yliniemi

    2016-04-01

    Full Text Available Mineral wools are the most common insulation materials in buildings worldwide. However, mineral wool waste is often considered unrecyclable because of its fibrous nature and low density. In this paper, rock wool (RW and glass wool (GW were studied as alkali-activated material precursors without any additional co-binders. Both mineral wools were pulverized by a vibratory disc mill in order to remove the fibrous nature of the material. The pulverized mineral wools were then alkali-activated with a sodium aluminate solution. Compressive strengths of up to 30.0 MPa and 48.7 MPa were measured for RW and GW, respectively, with high flexural strengths measured for both (20.1 MPa for RW and 13.2 MPa for GW. The resulting alkali-activated matrix was a composite-type in which partly-dissolved fibers were dispersed. In addition to the amorphous material, sodium aluminate silicate hydroxide hydrate and magnesium aluminum hydroxide carbonate phases were identified in the alkali-activated RW samples. The only crystalline phase in the GW samples was sodium aluminum silicate. The results of this study show that mineral wool is a very promising raw material for alkali activation.

  7. CRYSTAL POLYMORPHISM IN 1-BUTYL-3-METHYLIMIDAZOLIUM HALIDES: SUPPORTING IONIC LIQUID FORMATION THROUGH INHIBITION OF CRYSTALLIZATION. (R828257)

    Science.gov (United States)

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  8. Cohesion energy calculations for ternary ionic novel crystals

    Energy Technology Data Exchange (ETDEWEB)

    Vazquez P, G.; Cabrera, E. [Instituto de Fisica, Universidad Nacional Autonoma de Mexico, A.P. 20-364, 01000 Mexico D.F. (Mexico); Mijangos, R.R. [Centro de Investigacion en Fisica, Universidad de Sonora, A.P. 5-88, 83190 Hermosillo, Sonora (Mexico); Valdez, E. [Escuela Nacional de Estudios Profesionales Acatlan, Universidad Nacional Autonoma de Mexico, Santa Cruz Acatlan, Naucalpan (Mexico); Duarte, C. [Departamento de Geologia, Universidad de Sonora, 83000 Hermosillo, Sonora (Mexico)

    2001-07-01

    The present work calculates the value of the link energy of a crystalline ternary structure newly formed by alkali halides. The ternary structure prepared with different concentrations of KCl{sub x}KBrRbCl{sub 2} maintains a very good miscibility and stability. The calculation is based on the use of a generalization of the Vegard law (which generally is valid for binary compounds) for calculating the values of the lattice constant and the repulsive m exponent. The value of the lattice parameter given by X-ray diffractometry agrees with the close approximation of the calculated value of the method used. It also compares the value of energy cohesion obtained by the Born expression with more complex approximations. (Author)

  9. All-Vacuum-Deposited Stoichiometrically Balanced Inorganic Cesium Lead Halide Perovskite Solar Cells with Stabilized Efficiency Exceeding 11.

    Science.gov (United States)

    Chen, Chien-Yu; Lin, Hung-Yu; Chiang, Kai-Ming; Tsai, Wei-Lun; Huang, Yu-Ching; Tsao, Cheng-Si; Lin, Hao-Wu

    2017-03-01

    Vacuum-sublimed inorganic cesium lead halide perovskite thin films are prepared and integrated in all-vacuum-deposited solar cells. Special care is taken to determine the stoichiometric balance of the sublimation precursors, which has great influence on the device performance. The mixed halide devices exhibit exceptional stabilized power conversion efficiency (11.8%) and promising thermal and long-term stabilities.

  10. Homocoupling of aryl halides in flow: Space integration of lithiation and FeCl3 promoted homocoupling

    Directory of Open Access Journals (Sweden)

    Aiichiro Nagaki

    2011-08-01

    Full Text Available The use of FeCl3 resulted in a fast homocoupling of aryllithiums, and this enabled its integration with the halogen–lithium exchange reaction of aryl halides in a flow microreactor. This system allows the homocoupling of two aryl halides bearing electrophilic functional groups, such as CN and NO2, in under a minute.

  11. Designing mixed metal halide ammines for ammonia storage using density functional theory and genetic algorithms

    DEFF Research Database (Denmark)

    Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich J.

    2014-01-01

    Metal halide ammines have great potential as a future, high-density energy carrier in vehicles. So far known materials, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, are not suitable for automotive, fuel cell applications, because the release of ammonia is a multi-step reaction, requiring too much heat...... to be supplied, making the total efficiency lower. Here, we apply density functional theory (DFT) calculations to predict new mixed metal halide ammines with improved storage capacities and the ability to release the stored ammonia in one step, at temperatures suitable for system integration with polymer...... electrolyte membrane fuel cells (PEMFC). We use genetic algorithms (GAs) to search for materials containing up to three different metals (alkaline-earth, 3d and 4d) and two different halides (Cl, Br and I) – almost 27000 combinations, and have identified novel mixtures, with significantly improved storage...

  12. Solubility and permeability of steroids in water in the presence of potassium halides.

    Science.gov (United States)

    Messner, M; Loftsson, T

    2010-02-01

    Water forms a network of hydrogen bonded water molecules that gives liquid water unique physicochemical properties. Ions that affect the network structure, e.g. potassium halides, are known to either increase or decrease aqueous solubilities of drugs. Most biological membranes consist of hydrophilic exterior and a lipophilic interior. Mathematically they can be treated as two-layer membranes, i.e. a hydrophilic water layer that is referred to as unstirred water layer (UWL) and a lipophilic membrane. The purpose of this study was to investigate if and then how ions affect drug permeation through the UWL. The effects of potassium halides on the solubility and permeability of dexamethasone and hydrocortisone was investigated. The potassium halides had either increasing or decreasing effect on their aqueous solubility but did not have any effect on their permeability through UWL.

  13. Purcell effect in an organic-inorganic halide perovskite semiconductor microcavity system

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jun; Wang, Yafeng; Hu, Tao; Wu, Lin; Shen, Xuechu; Chen, Zhanghai, E-mail: lujian@fudan.edu.cn, E-mail: zhanghai@fudan.edu.cn [State Key Laboratory of Surface Physics, Key Laboratory of Micro and Nano Photonic Structures (Ministry of Education), Department of Physics, Collaborative Innovation Center of Advanced Microstructures, Fudan University, Shanghai 200433 (China); Cao, Runan; Xu, Fei [Department of Physics, Shanghai University, Shanghai 200444 (China); Da, Peimei; Zheng, Gengfeng [Laboratory of Advanced Materials, Department of Chemistry, Fudan University, Shanghai 200433 (China); Lu, Jian, E-mail: lujian@fudan.edu.cn, E-mail: zhanghai@fudan.edu.cn [State Key Laboratory of Surface Physics, Key Laboratory of Micro and Nano Photonic Structures (Ministry of Education), Department of Physics, Collaborative Innovation Center of Advanced Microstructures, Fudan University, Shanghai 200433 (China); Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210 (China)

    2016-01-11

    Organic-inorganic halide perovskite semiconductors with the attractive physics properties, including strong photoluminescence (PL), huge oscillator strengths, and low nonradiative recombination losses, are ideal candidates for studying the light-matter interaction in nanostructures. Here, we demonstrate the coupling of the exciton state and the cavity mode in the lead halide perovskite microcavity system at room temperature. The Purcell effect in the coupling system is clearly observed by using angle-resolved photoluminescence spectra. Kinetic analysis based on time-resolved PL reveals that the spontaneous emission rate of the halide perovskite semiconductor is significantly enhanced at resonance of the exciton energy and the cavity mode. Our results provide the way for developing electrically driven organic polariton lasers, optical devices, and on-chip coherent quantum light sources.

  14. Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions.

    Science.gov (United States)

    Akkerman, Quinten A; D'Innocenzo, Valerio; Accornero, Sara; Scarpellini, Alice; Petrozza, Annamaria; Prato, Mirko; Manna, Liberato

    2015-08-19

    We demonstrate that, via controlled anion exchange reactions using a range of different halide precursors, we can finely tune the chemical composition and the optical properties of presynthesized colloidal cesium lead halide perovskite nanocrystals (NCs), from green emitting CsPbBr3 to bright emitters in any other region of the visible spectrum, and back, by displacement of Cl(-) or I(-) ions and reinsertion of Br(-) ions. This approach gives access to perovskite semiconductor NCs with both structural and optical qualities comparable to those of directly synthesized NCs. We also show that anion exchange is a dynamic process that takes place in solution between NCs. Therefore, by mixing solutions containing perovskite NCs emitting in different spectral ranges (due to different halide compositions) their mutual fast exchange dynamics leads to homogenization in their composition, resulting in NCs emitting in a narrow spectral region that is intermediate between those of the parent nanoparticles.

  15. Holographic optical elements recorded in silver halide sensitized gelatin emulsions. Part I. Transmission holographic optical elements.

    Science.gov (United States)

    Kim, J M; Choi, B S; Kim, S I; Kim, J M; Bjelkhagen, H I; Phillips, N J

    2001-02-10

    Silver halide sensitized gelatin (SHSG) holograms are similar to holograms recorded in dichromated gelatin (DCG), the main recording material for holographic optical elements (HOE's). The drawback of DCG is its low sensitivity and limited spectral response. Silver halide materials can be processed in such a way that the final hologram will have properties like a DCG hologram. Recently this technique has become more interesting since the introduction of new ultra-high-resolution silver halide emulsions. An optimized processing technique for transmission HOE's recorded in these materials is introduced. Diffraction efficiencies over 90% can be obtained for transmissive diffraction gratings. Understanding the importance of the selective hardening process has made it possible to obtain results similar to conventional DCG processing. The main advantage of the SHSG process is that high-sensitivity recording can be performed with laser wavelengths anywhere within the visible spectrum. This simplifies the manufacturing of high-quality, large-format HOE's.

  16. Purcell effect in an organic-inorganic halide perovskite semiconductor microcavity system

    Science.gov (United States)

    Wang, Jun; Cao, Runan; Da, Peimei; Wang, Yafeng; Hu, Tao; Wu, Lin; Lu, Jian; Shen, Xuechu; Xu, Fei; Zheng, Gengfeng; Chen, Zhanghai

    2016-01-01

    Organic-inorganic halide perovskite semiconductors with the attractive physics properties, including strong photoluminescence (PL), huge oscillator strengths, and low nonradiative recombination losses, are ideal candidates for studying the light-matter interaction in nanostructures. Here, we demonstrate the coupling of the exciton state and the cavity mode in the lead halide perovskite microcavity system at room temperature. The Purcell effect in the coupling system is clearly observed by using angle-resolved photoluminescence spectra. Kinetic analysis based on time-resolved PL reveals that the spontaneous emission rate of the halide perovskite semiconductor is significantly enhanced at resonance of the exciton energy and the cavity mode. Our results provide the way for developing electrically driven organic polariton lasers, optical devices, and on-chip coherent quantum light sources.

  17. Solvolysis of benzoyl halides in water/NH4DEHP/isooctane microemulsions.

    Science.gov (United States)

    García-Río, L; Hervella, P; Rodríguez-Dafonte, P

    2006-08-29

    A study was carried out on the solvolysis reactions of different benzoyl halides in microemulsions of water/NH4DEHP/isooctane, where NH4DEHP is ammonium bis(2-ethylhexyl) phosphate. Because of the low solubility of benzoyl halides in water, they are distributed between the continuous medium and the interface of the microemulsion, where the reaction takes place. The application of the pseudophase model has allowed us to obtain the distribution constants and the rate constants at the interface for the benzoyl halides. Reaction mechanisms and the changes in these mechanisms in terms of the water content of the microemulsion have been determined on the basis of kinetic data. The influence of the substituent and the leaving group on the reaction rate has been investigated. A comparison of kinetic results with those previously obtained in water/AOT/isooctane microemulsions allows a kinetic evaluation of the change in the microemulsion properties with the surfactant.

  18. Catalysis by desolvation: the catalytic prowess of SAM-dependent halide-alkylating enzymes.

    Science.gov (United States)

    Lohman, Danielle C; Edwards, David R; Wolfenden, Richard

    2013-10-02

    In the biological fixation of halide ions, several enzymes have been found to catalyze alkyl transfer from S-adenosylmethionine to halide ions. It proves possible to measure the rates of reaction of the trimethylsulfonium ion with I(-), Br(-), Cl(-), F(-), HO(-), and H2O in water at elevated temperatures. Comparison of the resulting second-order rate constants, extrapolated to 25 °C, with the values of k(cat)/K(m) reported for fluorinase and chlorinase indicates that these enzymes enhance the rates of alkyl halide formation by factors of 2 × 10(15)- and 1 × 10(17)-fold, respectively. These rate enhancements, achieved without the assistance of cofactors, metal ions, or general acid-base catalysis, are the largest that have been reported for an enzyme that acts on two substrates.

  19. Maternal exposure to alkali, alkali earth, transition and other metals: Concentrations and predictors of exposure.

    Science.gov (United States)

    Hinwood, A L; Stasinska, A; Callan, A C; Heyworth, J; Ramalingam, M; Boyce, M; McCafferty, P; Odland, J Ø

    2015-09-01

    Most studies of metals exposure focus on the heavy metals. There are many other metals (the transition, alkali and alkaline earth metals in particular) in common use in electronics, defense industries, emitted via combustion and which are naturally present in the environment, that have received limited attention in terms of human exposure. We analysed samples of whole blood (172), urine (173) and drinking water (172) for antimony, beryllium, bismuth, cesium, gallium, rubidium, silver, strontium, thallium, thorium and vanadium using ICPMS. In general most metals concentrations were low and below the analytical limit of detection with some high concentrations observed. Few factors examined in regression models were shown to influence biological metals concentrations and explained little of the variation. Further study is required to establish the source of metals exposures at the high end of the ranges of concentrations measured and the potential for any adverse health impacts in children.

  20. NMR and Nqr Study of Atomic Order in Alkali Borate Glasses.

    Science.gov (United States)

    Gravina, Samuel John

    A modified Robinson oscillator circuit was built for the detection of nuclear quadrupole resonance (NQR) in the 200 to 10,000 kHz region. The circuit demonstrates near ideal performance with the detected noise limited only by the sample temperature. The use of computer controlled data acquisition and a carefully designed sample probe allows for the use of an integrating time constant of up to 6 hours. This spectrometer has been used to detect ^{10}B and ^{11 }B NQR in lithium and sodium borate glasses and crystals. In pure boron oxide glass two distinct boron sites are found. By comparing this experiment with previous NMR and Raman spectroscopy studies, one of the sites, which comprises 85% of the total boron, can be attributed to boron atoms in boroxol rings. As sodium is added to the glass the abundance of boroxol rings decreases. At 20 mol% sodium oxide less than 2% of the boron atoms are found in boroxol rings. The dipole-dipole interaction between lithium cations and four-coordinated boron atoms (B_4 units) has been measured. It is found that every B_4 unit has one lithium cation next to it at an average distance of 2.82 A. A comparison with lithium borate crystals shows that diborate groups do not occur in significant quantities. Both high field and low field NMR studies of the boron quadrupole interaction in a B_4 unit also show that diborate groups are not found in the glass. A ^{23}Na and ^6Li NMR MASS study of lithium and sodium borate glasses shows that ^{23 }Na chemical shifts can distinguish sodium cations bound to non-bridging oxygens from sodium cations bound to bridging oxygens. The chemical shifts measured in lithium-sodium borate glasses are identical to those measured in lithium borate or sodium borate glasses, indicating similar alkali-oxygen coordination. A significant narrowing of the ^6Li NMR spectrum in a mixed alkali glass can be understood as a decrease in the entropy of the lithium cations. This result is consistent with the weak

  1. Characterization of alkali-modified soy protein concentrate

    Directory of Open Access Journals (Sweden)

    Barać Miroljub B.

    2005-01-01

    Full Text Available To study the influence of the preparation mode, including mild alkali modification, of soy protein concentrate on soluble protein content and composition, some of its nutritive and functional properties were investigated. Soy protein concentrate prepared by aqueous alcohol leaching was modified in mild alkaline solutions (pH 8.0 at 40, 50 and 60° C for 60 minutes and compared with two principal types of commercial soy protein concentrate. Soluble protein content, composition and properties of soy protein concentrate, as well as their potential use are essentially determined by the preparation mode. Limited mild alkali hydrolysis increased protein solubility by 40-71%, while emulsion stability was increased by 18-56%. Major storage soybean proteins exhibited different stability to alcohol denaturation and mild alkali modification. The most susceptible were acidic -A3 - and -A5- subunits of glycinin.

  2. Orbital Feshbach Resonance in Alkali-Earth Atoms.

    Science.gov (United States)

    Zhang, Ren; Cheng, Yanting; Zhai, Hui; Zhang, Peng

    2015-09-25

    For a mixture of alkali-earth atomic gas in the long-lived excited state ^{3}P_{0} and the ground state ^{1}S_{0}, in addition to nuclear spin, another "orbital" index is introduced to distinguish these two internal states. In this Letter we propose a mechanism to induce Feshbach resonance between two atoms with different orbital and nuclear spin quantum numbers. Two essential ingredients are the interorbital spin-exchange process and orbital dependence of the Landé g factors. Here the orbital degrees of freedom plays a similar role as the electron spin degree of freedom in magnetic Feshbach resonance in alkali-metal atoms. This resonance is particularly accessible for the ^{173}Yb system. The BCS-BEC crossover in this system requires two fermion pairing order parameters, and displays a significant difference compared to that in an alkali-metal system.

  3. Oscillation Frequencies for Simultaneous Trapping of Heteronuclear Alkali Atoms

    CERN Document Server

    Kaur, Kiranpreet; Arora, Bindiya

    2016-01-01

    We investigate oscillation frequencies for simultaneous trapping of more than one type of alkali atoms in a common optical lattice. For this purpose, we present numerical results for magic trapping conditions, where the oscillation frequencies for two different kind of alkali atoms using laser lights in the wavelength range 500-1200 nm are same. These wavelengths will be of immense interest for studying static and dynamic properties of boson-boson, boson-fermion, fermion-fermion, and boson-boson-boson mixtures involving different isotopes of Li, Na, K, Rb, Cs and Fr alkali atoms. In addition to this, we were also able to locate a magic wavelength around 808.1 nm where all the three Li, K, and Rb atoms are found to be suitable for oscillating at the same frequency in a common optical trap.

  4. Properties of Hooked Steel Fibers Reinforced Alkali Activated Material Concrete

    Directory of Open Access Journals (Sweden)

    Faris M. A.

    2016-01-01

    Full Text Available In this study, alkali activated material was produced by using Class F fly ash from Manjung power station, Lumut, Perak, Malaysia. Fly ash then was activated by alkaline activator which is consisting of sodium silicate (Na2SiO3 and sodium hydroxide (NaOH. Hooked end steel fibers were added into the alkali activated material system with percentage vary from 0 % – 5 %. Chemical compositions of fly ash were first analyzed by using x-ray fluorescence (XRF. All hardened alkali activated material samples were tested for density, workability, and compression after 28 days. Results show a slight increase of density with the addition of steel fibers. However, the workability was reduced with the addition of steel fibers content. Meanwhile, the addition of steel fibers shows the improvement of compressive strength which is about 19 % obtained at 3 % of steel fibers addition.

  5. Formation and Stability of High-Spin Alkali Clusters

    Science.gov (United States)

    Schulz, C. P.; Claas, P.; Schumacher, D.; Stienkemeier, F.

    2004-01-01

    Helium nanodroplet isolation has been applied to agglomerate alkali clusters at temperatures of 380mK. The very weak binding to the surface of the droplets allows a selection of only weakly bound, high-spin states. Here we show that larger clusters of alkali atoms in high-spin states can be formed. The lack of strong bonds from pairing electrons makes these systems nonmetallic, vanderWaals like complexes of metal atoms. We find that sodium and potassium readily form such clusters containing up to 25atoms. In contrast, this process is suppressed for rubidium and cesium. Apparently, for these heavy alkalis, larger high-spin aggregates are not stable and depolarize spontaneously upon cluster formation.

  6. Neuropsychiatric manifestations of alkali metal deficiency and excess

    Energy Technology Data Exchange (ETDEWEB)

    Yung, C.Y.

    1984-01-01

    The alkali metals from the Group IA of the periodic table (lithium, sodium, potassium, rubidium, cesium and francium) are reviewed. The neuropsychiatric aspects of alkali metal deficiencies and excesses (intoxications) are described. Emphasis was placed on lithium due to its clinical uses. The signs and symptoms of these conditions are characterized by features of an organic brain syndrome with delirium and encephalopathy prevailing. There are no clinically distinctive features that could be reliably used for diagnoses. Sodium and potassium are two essential alkali metals in man. Lithium is used as therapeutic agent in bipolar affective disorders. Rubidium has been investigated for its antidepressant effect in a group of psychiatric disorders. Cesium is under laboratory investigation for its role in carcinogenesis and in depressive illness. Very little is known of francium due to its great instability for experimental study.

  7. Low-frequency Raman scattering in alkali tellurite glasses

    Indian Academy of Sciences (India)

    Angelos G Kalampounias

    2008-10-01

    Raman scattering has been employed to study the alkali-cation size dependence and the polarization characteristics of the low-frequency modes for the glass-forming tellurite mixtures, 0.1M2O–0.9TeO2 (M = Na, K, Rb and Cs). The analysis has shown that the Raman coupling coefficient alters by varying the type of the alkali cation. The addition of alkali modifier in the tellurite network leads to the conversion of the TeO4 units to TeO3 units with a varying number of non-bridging oxygen atoms. Emphasis has also been given to the lowfrequency modes and particular points related to the low-frequency Raman phenomenology are discussed in view of the experimental findings.

  8. Alkali control of high-grade metamorphism and granitization

    Directory of Open Access Journals (Sweden)

    Oleg G. Safonov

    2014-09-01

    Full Text Available We review petrologic observations of reaction textures from high-grade rocks that suggest the passage of fluids with variable alkali activities. Development of these reaction textures is accompanied by regular compositional variations in plagioclase, pyroxenes, biotite, amphibole and garnet. The textures are interpreted in terms of exchange and net-transfer reactions controlled by the K and Na activities in the fluids. On the regional scale, these reactions operate in granitized, charnockitized, syenitized etc. shear zones within high-grade complexes. Thermodynamic calculations in simple chemical systems show that changes in mineral assemblages, including the transition from the hydrous to the anhydrous ones, may occur at constant pressure and temperature due only to variations in the H2O and the alkali activities. A simple procedure for estimating the activity of the two major alkali oxides, K2O and Na2O, is implemented in the TWQ software. Examples of calculations are presented for well-documented dehydration zones from South Africa, southern India, and Sri Lanka. The calculations have revealed two end-member regimes of alkalis during specific metamorphic processes: rock buffered, which is characteristic for the precursor rocks containing two feldspars, and fluid-buffered for the precursor rocks without K-feldspar. The observed reaction textures and the results of thermodynamic modeling are compared with the results of available experimental studies on the interaction of the alkali chloride and carbonate-bearing fluids with metamorphic rocks at mid-crustal conditions. The experiments show the complex effect of alkali activities in the fluid phase on the mineral assemblages. Both thermodynamic calculations and experiments closely reproduce paragenetic relations theoretically predicted by D.S. Korzhinskii in the 1940s.

  9. Copper(I) halide complexes of 2,2,5,5-tetramethyl-imidazolidine-4-thione: Synthesis, structures, luminescence, thermal stability and interaction with DNA.

    Science.gov (United States)

    Anastasiadou, D; Psomas, G; Lalia-Kantouri, M; Hatzidimitriou, A G; Aslanidis, P

    2016-11-01

    Five neutral mononuclear copper(I) halide complexes containing 2,2,5,5-tetramethylimidazolidine-4-thione (tmimdtH) and triphenylphosphane (PPh3) or tri-o-tolylphosphane (totp) have been prepared and structurally characterized by X-ray single-crystal analysis. The complexes containing PPh3 adopt the usual distorted tetrahedral geometry, while the presence of the bulkier totp forces the formation of three-coordinated trigonal planar species. The interaction of the compounds with calf-thymus DNA was monitored directly via UV-vis spectroscopy, DNA-viscosity measurements and indirectly via its competition with ethidium bromide for DNA studied by fluorescence emission spectroscopy. Intercalation was revealed as the most possible mode of binding. Furthermore, luminescent properties and thermal stabilities of the complexes were investigated.

  10. The influence of trapping centres on the photoelectron decay in silver halide

    Institute of Scientific and Technical Information of China (English)

    Li Xiao-Wei; Zhang Rong-Xiang; Liu Rong-Juan; Yang Shao-Peng; Han Li; Fu Guang-Sheng

    2006-01-01

    Photoelectron is the foundation of latent image formation, the decay process of photoelectrons is influenced by all kinds of trapping centres in silver halide. By analysing the mechanism of latent image formation it is found that electron trap, hole trap, and one kind of recombination centre where free electron and trapped hole recombine are the main trapping centres in silver halide. Different trapping centres have different influences on the photoelectron behaviour. The effects of all kinds of typical trapping centres on the decay of photoelectrons are systematically investigated by solving the photoelectron decay kinetic equations. The results are in agreement with those obtained in the microwave absorption dielectric spectrum experiment.

  11. The silver ions contribution into the cytotoxic activity of silver and silver halides nanoparticles

    Science.gov (United States)

    Klimov, A. I.; Zherebin, P. M.; Gusev, A. A.; Kudrinskiy, A. A.; Krutyakov, Y. A.

    2015-11-01

    The biocidal action of silver nanoparticles capped with sodium citrate and silver halides nanoparticles capped with non-ionic surfactant polyoxyethylene(20)sorbitan monooleate (Tween 80®) against yeast cells Saccharomyces cerevisiae was compared to the effect produced by silver nitrate and studied through the measurement of cell loss and kinetics of K+ efflux from the cells. The cytotoxicity of the obtained colloids was strongly correlated with silver ion content in the dispersions. The results clearly indicated that silver and silver halides nanoparticles destroyed yeast cells through the intermediate producing of silver ions either by dissolving of salts or by oxidation of silver.

  12. Visible-Light-Promoted Trifluoromethylthiolation of Styrenes by Dual Photoredox/Halide Catalysis.

    Science.gov (United States)

    Honeker, Roman; Garza-Sanchez, R Aleyda; Hopkinson, Matthew N; Glorius, Frank

    2016-03-18

    Herein, we report a new visible-light-promoted strategy to access radical trifluoromethylthiolation reactions by combining halide and photoredox catalysis. This approach allows for the synthesis of vinyl-SCF3 compounds of relevance in pharmaceutical chemistry directly from alkenes under mild conditions with irradiation from household light sources. Furthermore, alkyl-SCF3-containing cyclic ketone and oxindole derivatives can be accessed by radical-polar crossover semi-pinacol and cyclization processes. Inexpensive halide salts play a crucial role in activating the trifluoromethylthiolating reagent towards photoredox catalysis and aid the formation of the SCF3 radical.

  13. High-Efficiency Flexible Solar Cells Based on Organometal Halide Perovskites.

    Science.gov (United States)

    Wang, Yuming; Bai, Sai; Cheng, Lu; Wang, Nana; Wang, Jianpu; Gao, Feng; Huang, Wei

    2016-06-01

    Flexible and light-weight solar cells are important because they not only supply power to wearable and portable devices, but also reduce the transportation and installation cost of solar panels. High-efficiency organometal halide perovskite solar cells can be fabricated by a low-temperature solution process, and hence are promising for flexible-solar-cell applications. Here, the development of perovskite solar cells is briefly discussed, followed by the merits of organometal halide perovskites as promising candidates as high-efficiency, flexible, and light-weight photovoltaic materials. Afterward, recent developments of flexible solar cells based on perovskites are reviewed.

  14. A mild and efficient procedure for the synthesis of ethers from various alkyl halides

    Directory of Open Access Journals (Sweden)

    Mosstafa Kazemi

    2013-10-01

    Full Text Available A simple, mild and practical procedure has been developed for the synthesis of symmetrical and unsymmetrical ethers by using DMSO, TBAI in the presence of K2CO3. We extended the utility of Potassium carbonate as an efficient base for the preparation of ethers. A wide range of alkyl aryl and dialkyl ethers are synthezied from treatment of aliphatic alcohols and phenols with various alkyl halides in the prescence of efficient base Potassium carbonate. Secondary alkyl halides were easily converted to corresponding ethers in releatively good yields . This is a mild, simple and practical procedure for the preparation of ethers in high yields and suitable times under mild condition.

  15. Vibrational energy relaxation of liquid aryl-halides X-C6H5 (X = F, Cl, Br, I).

    Science.gov (United States)

    Pein, Brandt C; Seong, Nak-Hyun; Dlott, Dana D

    2010-10-07

    Anti-Stokes Raman spectroscopy was used to probe vibrational energy dynamics in liquid ambient-temperature aryl-halides, X-Ph (X = F, Cl, Br, I; -Ph = C(6)H(5)), following IR excitation of a 3068 cm(-1) CH-stretching transition. Five ring vibrations and two substituent-dependent vibrations were monitored in each aryl-halide. Overall, the vibrational relaxation (VR) lifetimes in aryl-halides were shorter than those in normal benzene (H-Ph). The aryl-halide CH-stretch lifetimes increased in the order F, Cl, Br, I, ranging from 2.5 to 3.4 ps, compared with 6.2 ps in H-Ph. The aryl-halide energy transfer processes were similar overall with four exceptions. Three of the four exceptions could be explained as a result of faster VR of midrange vibrations (1000-1600 cm(-1)) in the heavier aryl-halides. The fourth appeared to result from a coincidental resonance in chlorobenzene that does not occur in the other aryl-halides. Among the aryl-halides, the decay of CH-stretching excitations (∼3070 cm(-1)) was slower in the heavier species, but the decay of midrange vibrations was faster in the heavier species. This seeming contradiction could be explained if VR depended primarily on the density of states (DOS) of the lower tiers of vibrational excitations. The DOS for the first few (1-4) tiers is similar for all aryl-halides in the CH-stretch region, but DOS increases with increasing halide mass in the midrange region.

  16. A hidden history of heartburn: The milk-alkali syndrome.

    Science.gov (United States)

    Swaminathan, Krishnan

    2011-02-01

    Milk-alkali syndrome was once considered to be of historic interest and a rare cause of hypercalcemia. Currently, it should be an important consideration in the differential diagnosis of hypercalcemia, after malignancies and primary hyperparathyroidism. The resurgence is in part due to the easy availability of over the counter (OTC) calcium preparations. We describe a 50-year-old man who presented with severe hypercalcemia on two occasions associated with renal failure and metabolic alkalosis. Extensive investigations during the first admission failed to unravel a specific cause of hypercalcemia but a thorough history during his subsequent admission helped to confirm the diagnosis of milk-alkali syndrome.

  17. MINERALOGICAL FEATURES OF ULTRAMAFIC HYPOXENOLITHS IN ALKALI-RICH PORPHYRY

    Institute of Scientific and Technical Information of China (English)

    LIU Xianfan; YANG Zhengxi; LIU Jiaduo; ZHANG Chengjiang; WU Dechao; LI Youguo

    2003-01-01

    Ultramafic hypoxenoliths found in the alkali-rich porphyry in the Liuhe Village, Heqing, Yunnan,China, are of great significance in understanding the origin and evolution of the porphyry. This paper discusses the mineralogical features of the hypoxenoliths. It shows that the xenoliths are characterized by the upper mantle rocks modified to certain extent by the enriched mantle fluid metasomatism in the mantle environment, with the enriched mantle property of Iow-degree partial melting. This constitutes the important mineralogical evidence for the petrogenesis and mineralization of alkali-rich porphyry.

  18. Assessment of concrete bridge decks with alkali silica reactions

    DEFF Research Database (Denmark)

    Eriksen, Kirsten; Jansson, Jacob; Geiker, Mette Rica

    2008-01-01

    Based on investigations of concrete from an approximately 40 years old bridge a procedure to support the management of maintenance and repair of alkali silica damaged bridges is proposed. Combined petrography and accelerated expansion testing were undertaken on cores from the Bridge at Skovdiget......, Bagsværd, Denmark to provide information on the damage condition as well as the residual reactivity of the concrete. The Danish Road Directory’s guidelines for inspection and assessment of alkali silica damaged bridges will be briefly presented, and proposed modifications will be describe...

  19. Upgrading of petroleum oil feedstocks using alkali metals and hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Gordon, John Howard

    2014-09-09

    A method of upgrading an oil feedstock by removing heteroatoms and/or one or more heavy metals from the oil feedstock composition. This method reacts the oil feedstock with an alkali metal and an upgradant hydrocarbon. The alkali metal reacts with a portion of the heteroatoms and/or one or more heavy metals to form an inorganic phase separable from the organic oil feedstock material. The upgradant hydrocarbon bonds to the oil feedstock material and increases the number of carbon atoms in the product. This increase in the number of carbon atoms of the product increases the energy value of the resulting oil feedstock.

  20. Interplay of Cation Ordering and Ferroelectricity in Perovskite Tin Iodides: Designing a Polar Halide Perovskite for Photovoltaic Applications

    Energy Technology Data Exchange (ETDEWEB)

    Gou, Gaoyang; Young, Joshua; Liu, Xian; Rondinelli, James M.

    2016-09-28

    Owing to its ideal semiconducting band gap and good carrier transport properties, the fully inorganic perovskite CsSnI3 has been proposed as a visible-light absorber for photovoltaic (PV) applications. However, compared to the organic inorganic lead halide perovskite CH3NH3PbI3, CsSnI3 solar cells display very low energy conversion efficiency. In this work, we propose a potential route to improve the PV properties of CsSnI3. Using first-principles calculations, we examine the crystal structures and electronic properties of CsSnI3, including its structural polymorphs. Next, we purposefully order Cs and Rb cations on the A site to create the double perovskite (CsRb)Sn2I6. We find that a stable ferroelectric polarization arises from the nontrivial coupling between polar displacements and octahedral rotations of the SnI6 network. These ferroelectric double perovskites are predicted to have energy band gaps and carrier effective masses similar to those of CsSnI3. More importantly, unlike nonpolar CsSnI3, the electric polarization present in ferroelectric (CsRb)Sn2I6 can effectively separate the photoexcited carriers, leading to novel ferroelectric PV materials with,potentially enhanced energy conversion efficiency.

  1. Inhibition of a structural phase transition in one-dimensional organometal halide perovskite nanorods grown inside porous silicon nanotube templates

    Science.gov (United States)

    Arad-Vosk, N.; Rozenfeld, N.; Gonzalez-Rodriguez, R.; Coffer, J. L.; Sa'ar, A.

    2017-02-01

    One-dimensional organo-metal halide perovskite (C H3N H3Pb I3 ) nanorods whose diameter and length are dictated by the inner size of porous silicon nanotube templates have been grown, characterized, and compared to bulk perovskites in the form of microwires. We have observed a structural phase transition for bulk perovskites, where the crystal structure changes from tetragonal to orthorhombic at about 160 K, as opposed to small diameter one-dimensional perovskite nanorods, of the order of 30-70 nm in diameter, where the phase transition is inhibited and the dominant phase remains tetragonal. Two major experimental techniques, infrared absorption spectroscopy and photoluminescence, were utilized to probe the temperature dependence of the perovskite phases over the 4-300 K temperature range. Yet, different characteristics of the phase transition were measured by the two spectroscopic methods and explained by the presence of small, tetragonal inclusions embedded in the orthorhombic phase. The inhibition of the phase transition is attributed to the large surface area of these one-dimensional perovskite nanorods, which gives rise to a large stress that, in turn, prevents the formation of the orthorhombic phase. The absence of phase transition enables the measurement of the tetragonal bandgap energy down to low temperatures.

  2. Improvement of enantioselectivity of the B-type halohydrin hydrogen-halide-lyase from Corynebacterium sp. N-1074.

    Science.gov (United States)

    Watanabe, Fumiaki; Yu, Fujio; Ohtaki, Akashi; Yamanaka, Yasuaki; Noguchi, Keiichi; Odaka, Masafumi; Yohda, Masafumi

    2016-09-01

    Halohydrin hydrogen-halide-lyase (H-Lyase) is a bacterial enzyme involved in the degradation of halohydrins. This enzyme catalyzes the intramolecular nucleophilic displacement of a halogen by a vicinal hydroxyl group in halohydrins, producing the corresponding epoxides. The H-Lyases have been classified into A, B and C subtypes based on amino acid sequence similarities. These enzymes have attracted much attention as industrial catalysts in the synthesis of chiral chemicals from prochiral halohydrins. In the present study, we constructed mutants of B-type H-Lyase from Corynebacterium sp. N-1074 (HheB) displaying higher enantioselectivity by structure-based site-directed mutagenesis and random mutagenesis. A triple mutant of HheB exhibited 98.5% enantioselectivity, the highest ever reported, toward (R)-4-chloro-3-hydroxy-butyronitrile production, with the yield reaching approximately two-fold that of the wild-type enzyme. We discuss the structural basis of the high enantioselectivity and productivity of the mutant by comparing the crystal structures of the mutant HheB and the wild-type enzyme in complex with or without the substrate analogue.

  3. IRMPD action spectroscopy of alkali metal cation-cytosine complexes: effects of alkali metal cation size on gas phase conformation.

    Science.gov (United States)

    Yang, Bo; Wu, R R; Polfer, N C; Berden, G; Oomens, J; Rodgers, M T

    2013-10-01

    The gas-phase structures of alkali metal cation-cytosine complexes generated by electrospray ionization are probed via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical calculations. IRMPD action spectra of five alkali metal cation-cytosine complexes exhibit both similar and distinctive spectral features over the range of ~1000-1900 cm(-1). The IRMPD spectra of the Li(+)(cytosine), Na(+)(cytosine), and K(+)(cytosine) complexes are relatively simple but exhibit changes in the shape and shifts in the positions of several bands that correlate with the size of the alkali metal cation. The IRMPD spectra of the Rb(+)(cytosine) and Cs(+)(cytosine) complexes are much richer as distinctive new IR bands are observed, and the positions of several bands continue to shift in relation to the size of the metal cation. The measured IRMPD spectra are compared to linear IR spectra of stable low-energy tautomeric conformations calculated at the B3LYP/def2-TZVPPD level of theory to identify the conformations accessed in the experiments. These comparisons suggest that the evolution in the features in the IRMPD action spectra with the size of the metal cation, and the appearance of new bands for the larger metal cations, are the result of the variations in the intensities at which these complexes can be generated and the strength of the alkali metal cation-cytosine binding interaction, not the presence of multiple tautomeric conformations. Only a single tautomeric conformation is accessed for all five alkali metal cation-cytosine complexes, where the alkali metal cation binds to the O2 and N3 atoms of the canonical amino-oxo tautomer of cytosine, M(+)(C1).

  4. 40 CFR 721.4663 - Fluorinated carboxylic acid alkali metal salts.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fluorinated carboxylic acid alkali... Specific Chemical Substances § 721.4663 Fluorinated carboxylic acid alkali metal salts. (a) Chemical... fluorinated carboxylic acid alkali metal salts (PMNs P-95-979/980/981) are subject to reporting under...

  5. Formation of alkali-metal nanoparticles in alkali-silicate glasses under electron irradiation and thermal processing

    Science.gov (United States)

    Bochkareva, E. S.; Sidorov, A. I.; Ignat'ev, A. I.; Nikonorov, N. V.; Podsvirov, O. A.

    2017-02-01

    Experiments and numerical simulation show that the irradiation of alkali-containing glasses using electrons at an energy of 35 keV and the subsequent thermal processing at a temperature above the vitrification point lead to the formation of spherical metal (lithium, sodium, and potassium) nanoparticles with oxide sheaths that exhibit plasmon resonances in the visible spectral range. Glasses containing two alkali metals exhibit mutual effect of metals on the formation of nanoparticles with two compositions due to the difference of ion radii and mobilities of metal ions.

  6. Synthesis and reactivity of trigonal copper(I) compounds, crystal structure of bis(tetrahydropyrimidine-2-thione)copper(I) bromide

    NARCIS (Netherlands)

    Akrivos, PD; Karagiannidis, P; Herrema, J; Luic, M; KojicProdic, B

    1995-01-01

    Reaction of monovalent copper halides with excess tetrahydropyrimidine-2-thione (thpmtH(2)) in acetonitrile results in the formation of three-coordinate monomer products of formula Cu(thpmtH(2))(2)X. The crystal and molecular structure of the bromo complex is reported and discussed with respect to a

  7. Crystallization Kinetics of Organic–Inorganic Trihalide Perovskites and the Role of the Lead Anion in Crystal Growth

    KAUST Repository

    Moore, David T.

    2015-02-18

    © 2015 American Chemical Society. Methylammonium lead halide perovskite solar cells continue to excite the research community due to their rapidly increasing performance which, in large part, is due to improvements in film morphology. The next step in this progression is control of the crystal morphology which requires a better fundamental understanding of the crystal growth. In this study we use in situ X-ray scattering data to study isothermal transformations of perovskite films derived from chloride, iodide, nitrate, and acetate lead salts. Using established models we determine the activation energy for crystallization and find that it changes as a function of the lead salt. Further analysis enabled determination of the precursor composition and showed that the primary step in perovskite formation is removal of excess organic salt from the precursor. This understanding suggests that careful choice of the lead salt will aid in controlling crystal growth, leading to superior films and better performing solar cells.

  8. Crystallization kinetics of organic-inorganic trihalide perovskites and the role of the lead anion in crystal growth.

    Science.gov (United States)

    Moore, David T; Sai, Hiroaki; Tan, Kwan W; Smilgies, Detlef-M; Zhang, Wei; Snaith, Henry J; Wiesner, Ulrich; Estroff, Lara A

    2015-02-18

    Methylammonium lead halide perovskite solar cells continue to excite the research community due to their rapidly increasing performance which, in large part, is due to improvements in film morphology. The next step in this progression is control of the crystal morphology which requires a better fundamental understanding of the crystal growth. In this study we use in situ X-ray scattering data to study isothermal transformations of perovskite films derived from chloride, iodide, nitrate, and acetate lead salts. Using established models we determine the activation energy for crystallization and find that it changes as a function of the lead salt. Further analysis enabled determination of the precursor composition and showed that the primary step in perovskite formation is removal of excess organic salt from the precursor. This understanding suggests that careful choice of the lead salt will aid in controlling crystal growth, leading to superior films and better performing solar cells.

  9. Powder X-ray diffraction study af alkali alanates

    DEFF Research Database (Denmark)

    Cao, Thao; Mosegaard Arnbjerg, Lene; Jensen, Torben René

    for mobile applications, new materials with high gravimetric and volumetric storage capacity of hydrogen have to be developed. Alkali alanates are promising for hydrogen storage materials. Sodium alanate stores hydrogen reversibly at moderate conditions when catalysed with, e.g. titanium, whereas potassium...

  10. Effect of Pozzolanic Reaction Products on Alkali-silica Reaction

    Institute of Scientific and Technical Information of China (English)

    WEI Fengyan; LAN Xianghui; LV Yinong; XU Zhongzi

    2006-01-01

    The effect of fly ash on controlling alkali-silica reaction (ASR) in simulated alkali solution was studied. The expansion of mortar bars and the content of Ca(OH)2 in cement paste cured at 80 ℃ for 91 d were measured. Transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) were employed to study the microstructure of C-S-H. TEM/energy dispersive spectroscopy (EDS) was then used to determine the composition of C-S-H. The pore structure of the paste was analyzed by mercury intrusion porosimetry (MIP). The results show that the contents of fly ash of 30% and 45% can well inhibit ASR. And the content of Ca(OH)2 decreases with the increase of fly ash. That fly ash reacted with Ca(OH)2 to produce C-S-H with a low Ca/Si molar ratio could bind more Na+ and K+ ions, and produce a reduction in the amount of soluble alkali available for ASR. At the same time, the C-S-H produced by pozzolanic reaction converted large pores to smaller ones (gel pores smaller than 10 nm) to densify the pore structure. Perhaps that could inhibit alkali transport to aggregate for ASR.

  11. Chlor-Alkali Industry: A Laboratory Scale Approach

    Science.gov (United States)

    Sanchez-Sanchez, C. M.; Exposito, E.; Frias-Ferrer, A.; Gonzalez-Garaia, J.; Monthiel, V.; Aldaz, A.

    2004-01-01

    A laboratory experiment for students in the last year of degree program in chemical engineering, chemistry, or industrial chemistry is presented. It models the chlor-alkali process, one of the most important industrial applications of electrochemical technology and the second largest industrial consumer of electricity after aluminium industry.

  12. Influence of temperature on alkali stress adaptation in Listeria monocytogenes

    Science.gov (United States)

    Listeria monocytogenes cells may induce alkali stress adaptation when exposed to sublethal concentrations of alkaline cleaners and sanitizers that may be frequently used in the food processing environment. In the present study, the effect of temperature on the induction and the stability of such alk...

  13. Assesment of Alkali Resistance of Basalt Used as Concrete Aggregates

    Directory of Open Access Journals (Sweden)

    al-Swaidani Aref M.

    2015-11-01

    Full Text Available The objective of this paper is to report a part of an ongoing research on the influence of using crushed basalt as aggregates on one of durability-related properties of concrete (i.e. alkali-silica reaction which is the most common form of Alkali-Aggregate Reaction. Alkali resistance has been assessed through several methods specified in the American Standards. Results of petrographic examination, chemical test (ASTM C289 and accelerated mortar bar test (ASTM C1260 have particularly been reported. In addition, the weight change and compressive strength of 28 days cured concrete containing basaltic aggregates were also reported after 90 days of exposure to 10% NaOH solution. Dolomite aggregate were used in the latter test for comparison. The experimental results revealed that basaltic rocks quarried from As-Swaida’a region were suitable for production of aggregates for concrete. According to the test results, the studied basalt aggregates can be classified as innocuous with regard to alkali-silica reaction. Further, the 10% sodium hydroxide attack did not affect the compressive strength of concrete.

  14. The role of NH3 and hydrocarbon mixtures in GaN pseudo-halide CVD: a quantum chemical study.

    Science.gov (United States)

    Gadzhiev, Oleg B; Sennikov, Peter G; Petrov, Alexander I; Kachel, Krzysztof; Golka, Sebastian; Gogova, Daniela; Siche, Dietmar

    2014-11-01

    The prospects of a control for a novel gallium nitride pseudo-halide vapor phase epitaxy (PHVPE) with HCN were thoroughly analyzed for hydrocarbons-NH3-Ga gas phase on the basis of quantum chemical investigation with DFT (B3LYP, B3LYP with D3 empirical correction on dispersion interaction) and ab-initio (CASSCF, coupled clusters, and multireference configuration interaction including MRCI+Q) methods. The computational screening of reactions for different hydrocarbons (CH4, C2H6, C3H8, C2H4, and C2H2) as readily available carbon precursors for HCN formation, potential chemical transport agents, and for controlled carbon doping of deposited GaN was carried out with the B3LYP method in conjunction with basis sets up to aug-cc-pVTZ. The gas phase intermediates for the reactions in the Ga-hydrocarbon systems were predicted at different theory levels. The located π-complexes Ga…C2H2 and Ga…C2H4 were studied to determine a probable catalytic activity in reactions with NH3. A limited influence of the carbon-containing atmosphere was exhibited for the carbon doping of GaN crystal in the conventional GaN chemical vapor deposition (CVD) process with hydrocarbons injected in the gas phase. Our results provide a basis for experimental studies of GaN crystal growth with C2H4 and C2H2 as auxiliary carbon reagents for the Ga-NH3 and Ga-C-NH3 CVD systems and prerequisites for reactor design to enhance and control the PHVPE process through the HCN synthesis.

  15. In Situ Transmission Electron Microscopy Study of Electron Beam-Induced Transformations in Colloidal Cesium Lead Halide Perovskite Nanocrystals

    Science.gov (United States)

    2017-01-01

    An increasing number of studies have recently reported the rapid degradation of hybrid and all-inorganic lead halide perovskite nanocrystals under electron beam irradiation in the transmission electron microscope, with the formation of nanometer size, high contrast particles. The nature of these nanoparticles and the involved transformations in the perovskite nanocrystals are still a matter of debate. Herein, we have studied the effects of high energy (80/200 keV) electron irradiation on colloidal cesium lead bromide (CsPbBr3) nanocrystals with different shapes and sizes, especially 3 nm thick nanosheets, a morphology that facilitated the analysis of the various ongoing processes. Our results show that the CsPbBr3 nanocrystals undergo a radiolysis process, with electron stimulated desorption of a fraction of bromine atoms and the reduction of a fraction of Pb2+ ions to Pb0. Subsequently Pb0 atoms diffuse and aggregate, giving rise to the high contrast particles, as previously reported by various groups. The diffusion is facilitated by both high temperature and electron beam irradiation. The early stage Pb nanoparticles are epitaxially bound to the parent CsPbBr3 lattice, and evolve into nonepitaxially bound Pb crystals upon further irradiation, leading to local amorphization and consequent dismantling of the CsPbBr3 lattice. The comparison among CsPbBr3 nanocrystals with various shapes and sizes evidences that the damage is particularly pronounced at the corners and edges of the surface, due to a lower diffusion barrier for Pb0 on the surface than inside the crystal and the presence of a larger fraction of under-coordinated atoms. PMID:28122188

  16. Fabrication of large-volume, low-cost ceramic lanthanum halide scintillators for gamma ray detection : final report for DHS/DNDO/TRDD project TA-01-SL01.

    Energy Technology Data Exchange (ETDEWEB)

    Boyle, Timothy J.; Ottley, Leigh Anna M.; Yang, Pin; Chen, Ching-Fong; Sanchez, Margaret R.; Bell, Nelson Simmons

    2008-10-01

    This project uses advanced ceramic processes to fabricate large, optical-quality, polycrystalline lanthanum halide scintillators to replace small single crystals produced by the conventional Bridgman growth method. The new approach not only removes the size constraint imposed by the growth method, but also offers the potential advantages of both reducing manufacturing cost and increasing production rate. The project goal is to fabricate dense lanthanum halide ceramics with a preferred crystal orientation by applying texture engineering and solid-state conversion to reduce the thermal mechanical stress in the ceramic and minimize scintillation light scattering at grain boundaries. Ultimately, this method could deliver the sought-after high sensitivity and <3% energy resolution at 662 keV of lanthanum halide scintillators and unleash their full potential for advanced gamma ray detection, enabling rapid identification of radioactive materials in a variety of practical applications. This report documents processing details from powder synthesis, seed particle growth, to final densification and texture development of cerium doped lanthanum bromide (LaBr{sub 3}:Ce{sup +3}) ceramics. This investigation demonstrated that: (1) A rapid, flexible, cost efficient synthesis method of anhydrous lanthanum halides and their solid solutions was developed. Several batches of ultrafine LaBr{sub 3}:Ce{sup +3} powder, free of oxyhalide, were produced by a rigorously controlled process. (2) Micron size ({approx} 5 {micro}m), platelet shape LaBr{sub 3} seed particles of high purity can be synthesized by a vapor phase transport process. (3) High aspect-ratio seed particles can be effectively aligned in the shear direction in the ceramic matrix, using a rotational shear-forming process. (4) Small size, highly translucent LaBr{sub 3} (0.25-inch diameter, 0.08-inch thick) samples were successfully fabricated by the equal channel angular consolidation process. (5) Large size, high density

  17. Reversible Halide Exchange Reaction of Organometal Trihalide Perovskite Colloidal Nanocrystals for Full-Range Band Gap Tuning.

    Science.gov (United States)

    Jang, Dong Myung; Park, Kidong; Kim, Duk Hwan; Park, Jeunghee; Shojaei, Fazel; Kang, Hong Seok; Ahn, Jae-Pyung; Lee, Jong Woon; Song, Jae Kyu

    2015-08-12

    In recent years, methylammonium lead halide (MAPbX3, where X = Cl, Br, and I) perovskites have attracted tremendous interest caused by their outstanding photovoltaic performance. Mixed halides have been frequently used as the active layer of solar cells, as a result of their superior physical properties as compared to those of traditionally used pure iodide. Herein, we report a remarkable finding of reversible halide-exchange reactions of MAPbX3, which facilitates the synthesis of a series of mixed halide perovskites. We synthesized MAPbBr3 plate-type nanocrystals (NCs) as a starting material by a novel solution reaction using octylamine as the capping ligand. The synthesis of MAPbBr(3-x)Clx and MAPbBr(3-x)Ix NCs was achieved by the halide exchange reaction of MAPbBr3 with MACl and MAI, respectively, in an isopropyl alcohol solution, demonstrating full-range band gap tuning over a wide range (1.6-3 eV). Moreover, photodetectors were fabricated using these composition-tuned NCs; a strong correlation was observed between the photocurrent and photoluminescence decay time. Among the two mixed halide perovskite series, those with I-rich composition (x = 2), where a sole tetragonal phase exists without the incorporation of a cubic phase, exhibited the highest photoconversion efficiency. To understand the composition-dependent photoconversion efficiency, first-principles density-functional theory calculations were carried out, which predicted many plausible configurations for cubic and tetragonal phase mixed halides.

  18. A Simple Empirical Analysis of the Enthalpies of Formation of Lanthanide Halides and Oxides.

    Science.gov (United States)

    Smith, Derek W.

    1986-01-01

    Proposes a simple and general method whereby the lattice energies of lanthanide(II) and (IV) compounds are derived directly from those found experimentally for the corresponding lanthanide(III) compounds. The method is applicable to all lanthanide halides and oxides and involves calculations which can be easily and quickly performed by students.…

  19. Regioselective chlorination and bromination of unprotected anilines under mild conditions using copper halides in ionic liquids

    Directory of Open Access Journals (Sweden)

    Han Wang

    2012-05-01

    Full Text Available By using ionic liquids as solvents, the chlorination or bromination of unprotected anilines at the para-position can be achieved in high yields with copper halides under mild conditions, without the need for potentially hazardous operations such as supplementing oxygen or gaseous HCl.

  20. Concentration dependence of halide fluxes and selectivity of the anion pathway in toad skin

    DEFF Research Database (Denmark)

    Harck, A F; Larsen, Erik Hviid

    1986-01-01

    mV (apical bath negative). The active sodium currents were eliminated by replacing external Na+ with K+. With [Cl-]o varying between 1.45 mM and 110 mM (gluconate substitution) and [I-]o = 3 mM, the total clamping current (y) and the sum of halide currents (x), estimated from flux measurements, were...

  1. Vibrational spectra of discrete UO22+ halide complexes in the gas phase

    NARCIS (Netherlands)

    Groenewold, G. S.; van Stipdonk, M. J.; Oomens, J.; de Jong, W. A.; Gresham, G. L.; McIlwain, M. E.

    2010-01-01

    The intrinsic binding of halide ions to the metal center in the uranyl molecule is a topic of ongoing research interest in both the actinide separations and theoretical communities. Investigations of structure in the condensed phases are frequently obfuscated by solvent interactions that can alter l

  2. Synthesis of Cyclic Carbonates from CO2 and Epoxides Catalyzed by Hexaalkylguanidinium Halides

    Institute of Scientific and Technical Information of China (English)

    DUAN Hai-feng; LI Sheng-hai; LIN Ying-jie; XIE Hai-bo; ZHANG Suo-bo; WANG Zong-mu

    2004-01-01

    Hexaalkylguanidinium halides exhibit an efficient catalytic activity in the synthesis of cyclic carbonates from epoxides and carbon dioxide. By this method cyclic carbonates can be obtained in a high yield and a high selectivity at a low temperature and atmospheric pressure. This procedure is easy for the product isolation and recycling of the catalyst.

  3. Halomethane production in plants: Structure of the biosynthetic SAM-dependent halide methyltransferase from Arabidopsis thaliana**

    Science.gov (United States)

    Schmidberger, Jason W.; James, Agata B.; Edwards, Robert; Naismith, James H.; O’Hagan, David

    2012-01-01

    A product structure of the halomethane producing enzyme in plants (Arabidopsis thaliana) is reported and a model for presentation of chloride/bromide ion to the methyl group of S-adenosyl-L-methionine (SAM) is presented to rationalise nucleophilic halide attack for halomethane production, gaseous natural products that are produced globally. PMID:20376845

  4. REPLACEMENT OF TRYPTOPHAN RESIDUES IN HALOALKANE DEHALOGENASE REDUCES HALIDE BINDING AND CATALYTIC ACTIVITY

    NARCIS (Netherlands)

    KENNES, C; PRIES, F; KROOSHOF, GH; BOKMA, E; Kingma, Jacob; JANSSEN, DB

    1995-01-01

    Haloalkane dehalogenase catalyzes the hydrolytic cleavage of carbon-halogen bonds in short-chain haloalkanes. Two tryptophan residues of the enzyme (Trp125 and Trp175) form a halide-binding site in the active-site cavity, and were proposed to play a role in catalysis. The function of these residues

  5. Homocoupling of benzyl halides catalyzed by POCOP-nickel pincer complexes

    KAUST Repository

    Chen, Tao

    2012-08-01

    Two types of POCOP-nickel(II) pincer complexes were prepared by mixing POCOP pincer ligands and NiX 2 in toluene at reflux. The resulting nickel complexes efficiently catalyze the homocoupling reactions of benzyl halides in the presence of zinc. The coupled products were obtained in excellent to quantitative yields. © 2012 Elsevier Ltd. All rights reserved.

  6. The Role of Excitons on Light Amplification in Lead Halide Perovskites.

    Science.gov (United States)

    Lü, Quan; Wei, Haohan; Sun, Wenzhao; Wang, Kaiyang; Gu, Zhiyuan; Li, Jiankai; Liu, Shuai; Xiao, Shumin; Song, Qinghai

    2016-12-01

    The role of excitons on the amplifications of lead halide perovskites has been explored. Unlike the photoluminescence, the intensity of amplified spontaneous emission is partially suppressed at low temperature. The detailed analysis and experiments show that the inhibition is attributed to the existence of exciton and a quantitative model has been built to explain the experimental observations.

  7. Enhancement of Exciton Emission in Lead Halide-Based Layered Perovskites by Cation Mixing.

    Science.gov (United States)

    Era, Masanao; Komatsu, Yumeko; Sakamoto, Naotaka

    2016-04-01

    Spin-coated films of a lead halide, PbX: X = I and Br, layered perovskites having cyclohexenylethyl ammonium molecule as an organic layer, which were mixed with other metal halide-based layered perovskites consisting of various divalent metal halides (for example, Ca2, Cdl2, FeI2, SnBr2 and so on), were prepared. The results of X-ray diffraction measurements exhibited that solid solution formation between PbX-based layered perovskite and other divalent metal halide-based layered perovskites was observed up to very high molar concentration of 50 molar% in the mixed film samples when divalent cations having ionic radius close to that of Pb2+ were employed. In the solid solution films, the exciton emission was much enhanced at room temperature. Exciton emission intensity of Pbl-based layered perovskite mixed with Cal-based layered perovskite (20 molar%) is about 5 times large that of the pristine Pbl-based layered perovskite, and that of PbBr-based layered perovskite mixed with SnBr-based layered perovskite (20 molar%) was also about 5 times large that of the pristine PbBr-based layered perovskite at room temperature.

  8. Palladium-catalyzed Coupling between Aryl Halides and Trimethylsilylacetylene Assisted by Dimethylaminotrimethyltin

    Institute of Scientific and Technical Information of China (English)

    Cai Liangzhen; Yang Dujuan; Sun Zhonghua; Tao Xiaochun; Cai Lisheng; Pike Victor W

    2011-01-01

    Palladium-catalyzed coupling between aryl halides, especially less reactive ones or N-heteroaryls, and trimethylsilylacetylene in the presence of dimethylaminotrimethyltin generated the coupled products in high yields. The reaction does not need CuI and base as auxiliary agents.

  9. Direct synthesis of diaryl sulfides by copper-catalyzed coupling of aryl halides with aminothiourea

    Institute of Scientific and Technical Information of China (English)

    Xiang Mei Wu; Wei Ya Hu

    2012-01-01

    An efficient and simple protocol of copper-catalyzed C-S bond formation between aryl halides and inexpensive and commercially available aminothiourea is reported.A variety of symmetrical diaryl sulfides can be synthesized in good to excellent yields up to 94% with the advantage of avoiding foul-smelling thiols.

  10. 78 FR 51463 - Energy Conservation Program: Energy Conservation Standards for Metal Halide Lamp Fixtures

    Science.gov (United States)

    2013-08-20

    ... August 20, 2013 Part V Department of Energy 10 CFR Part 431 Energy Conservation Program: Energy... Energy Conservation Program: Energy Conservation Standards for Metal Halide Lamp Fixtures AGENCY: Office... rulemaking (NOPR) and public meeting. SUMMARY: The Energy Policy and Conservation Act of 1975 (EPCA),...

  11. 75 FR 5544 - Energy Conservation Program: Energy Conservation Standards for Metal Halide Lamp Fixtures: Public...

    Science.gov (United States)

    2010-02-03

    ...; ] DEPARTMENT OF ENERGY 10 CFR Part 431 RIN 1904-AC00 Energy Conservation Program: Energy Conservation Standards...: Any comments submitted must identify the Framework Document for energy conservation standards for... energy conservation standards for metal halide lamp fixtures. The notice provided for the submission...

  12. Non-conventional halide oxidation pathways : oxidation by imidazole triplet and surface specific oxidation by ozone

    Science.gov (United States)

    Ammann, Markus; Corral-Arroyo, Pablo; Aellig, Raphael; Orlando, Fabrizio; Lee, Ming-Tao; Artiglia, Luca

    2016-04-01

    Oxidation of halide ions (chloride, bromide, iodide) are the starting point of halogen release mechanisms out of sea water, marine aerosol or other halide containing continental aerosols. Slow oxidation of chloride and bromide by ozone in the bulk aqueous phase is of limited relevance. Faster surface specific oxidation has been suggested based on heterogeneous kinetics experiments. We provide first insight into very efficient bromide oxidation by ozone at the aqueous solution - air interface by surface sensitive X-ray photoelectron spectroscopy indicating significant build-up of an oxidized intermediate at the surface within millisecond time scales. The second source of oxidants in the condensed we have considered is the absorption of light by triplet forming photosensitizers at wavelengths longer than needed for direct photolysis and radical formation. We have performed coated wall flow tube experiments with mixtures of citric acid (CA) and imidazole-2-carboxaldehyde (IC) to represent secondary organic material rich marine aerosol. The halide ions bromide and iodide have been observed to act as efficient electron donors leading to their oxidation, HO2 formation and finally release of molecular halogen compounds. The photosensitization of imidazole-2-carboxaldehyde (IC) involves a well-known mechanism where the triplet excited state of IC is reduced by citric acid to a reduced ketyl radical that reacts with halide ions. A competition kinetics approach has been used to evaluate the rate limiting steps and to assess the significance of this source of halogens to the gas phase.

  13. Can Ferroelectric Polarization Explain the High Performance of Hybrid Halide Perovskite Solar Cells?

    NARCIS (Netherlands)

    Sherkar, Tejas; Koster, L. Jan Anton

    2016-01-01

    The power conversion efficiency of photovoltaic cells based on the use of hybrid halide perovskites, CH3NH3PbX3 (X = Cl, Br, I), now exceeds 20%. Recently, it was suggested that this high performance originates from the presence of ferroelectricity in the perovskite, which is hypothesized to lower c

  14. Effect of Anti-freezing Admixtures on Alkali-silica Reaction in Mortars

    Institute of Scientific and Technical Information of China (English)

    LIU Junzhe; LI Yushun; LV Lihua

    2005-01-01

    The influence of anti-freezing admixture on the alkali aggregate reaction in mortar was analyzed with accelerated methods. It is confirmed that the addition of sodium salt ingredients of anti-freezing admixture accelerates the alkali silica reaction to some extent, whereas calcium salt ingredient of anti-freezing admixture reduces the expansion of alkali silica reaction caused by high alkali cement. It is found that the addition of the fly ash considerably suppresses the expansion of alkali silica reaction induced by the anti-freezing admixtures.

  15. Barium iodide and strontium iodide crystals and scintillators implementing the same

    Energy Technology Data Exchange (ETDEWEB)

    Payne, Stephen A.; Cherepy, Nerine; Pedrini, Christian; Burger, Arnold

    2016-09-13

    In one embodiment, a crystal includes at least one metal halide; and an activator dopant comprising ytterbium. In another general embodiment, a scintillator optic includes: at least one metal halide doped with a plurality of activators, the plurality of activators comprising: a first activator comprising europium, and a second activator comprising ytterbium. In yet another general embodiment, a method for manufacturing a crystal suitable for use in a scintillator includes mixing one or more salts with a source of at least one dopant activator comprising ytterbium; heating the mixture above a melting point of the salt(s); and cooling the heated mixture to a temperature below the melting point of the salts. Additional materials, systems, and methods are presented.

  16. Synthesis, Structure and Luminescent Properties of Polymeric Copper(Ⅰ) Halide Complexes Bearing Phosphine and N-donor Bridging Ligands

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Three polymeric copper(Ⅰ) halide complexes bearing phosphine and N-donor bridging ligands, [(PPh3)2Cu2(μ-Br)2(μ-4,4'-bipy)]∞ 1 (bipy=bipyridine), [(PPh3)2Cu2(μ-Br)2(μ-bpe)]∞ 2 (bpe=trans-1,2-bis(4-pyridyl)ethene) and [(PPh3)2Cu2(μ-Cl)2(μ-bpe)]∞ 3, were synthesized by the multilayer diffusion method, and the structures were refined by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group P-1 with a=9.122(3), b=9.322(3), c=13.201(4) (A),α=106.440(4), β=105.965(5), γ=94.167(5)°, V=1021.3(6) (A), Mr=967.62, Z=1,Dc=1.573 g/cm3, F(000)=486,μ=3.111 mm-1, the final R=0.0383 and wR=0.0960 for 2792observed reflections (I > 2σ(Ⅰ)). Complex 2 crystallizes in triclinic, space group P-1 with a=9.420(3), b=10.209(4), c=12.407(4)(A), α=104.136(6), β=108.132(5), γ=95.338(6)°, V=1081.0(7)(A), Mr=496.83, Z=2, Dc=1.526 g/cm3, F(000)=500,μ=2.941 mm-1, the final R=0.0445 and wR=0.1117 for 3251 observed reflections (I> 2σ(Ⅰ)). Complex 3 crystallizes in triclinic,space group P-1 with a=8.32(1), b=11.53(2), c=13.94(3)(A), α=109.57(3), β=93.85(3), γ=97.28(3)°, V=1242(4)(A)3, Mr=1074.59, Z=1, Dc=1.436 g/cm3, F(000)=548,μ=1.279 mm-1,the final R=0.0786 and wR=0.1586 for 2266 observed reflections (I > 2σ(Ⅰ)). The complexes exhibit intensive solid-state photoluminescence tentatively assigned to an admixture of triplet intraligand (IL) and metal-to-ligand charge-transfer (MLCT) excited state.

  17. Effects of Alloying on the Optical Properties of Organic-Inorganic Lead Halide Perovskite Thin Films

    Energy Technology Data Exchange (ETDEWEB)

    Ndione, Paul F.; Li, Zhen; Zhu, Kai

    2016-09-07

    Complex refractive index and dielectric function spectra of organic-inorganic lead halide perovskite alloy thin films are presented, together with the critical-point parameter analysis (energy and broadening) of the respective composition. Thin films of methylammonium lead halide alloys (MAPbI3, MAPbBr3, MAPbBr2I, and MAPbBrI2), formamidinium lead halide alloys (FAPbI3, FAPbBr3, and FAPbBr2I), and formamidinium cesium lead halide alloys [FA0.85Cs0.15PbI3, FA0.85Cs0.15PbBrI2, and FA0.85Cs0.15Pb(Br0.4I0.6)3] were studied. The complex refractive index and dielectric functions were determined by spectroscopic ellipsometry (SE) in the photon energy range of 0.7-6.5 eV. Critical point energies and optical transitions were obtained by lineshape fitting to the second-derivative of the complex dielectric function data of these thin films as a function of alloy composition. Absorption onset in the vicinity of the bandgap, as well as critical point energies and optical band transition shift toward higher energies as the concentration of Br in the films increases. Cation alloying (Cs+) has less effect on the optical properties of the thin films compared to halide mixed alloys. The reported optical properties can help to understand the fundamental properties of the perovskite materials and also be used for optimizing or designing new devices.

  18. An alkali-free barium borosilicate viscous sealing glass for solid oxide fuel cells

    Science.gov (United States)

    Hsu, Jen-Hsien; Kim, Cheol-Woon; Brow, Richard K.; Szabo, Joe; Crouch, Ray; Baird, Rob

    2014-12-01

    An alkali-free, alkaline earth borosilicate glass (designated G102) has been developed as a viscous sealant for use with solid oxide fuel cells (SOFCs). The glass possesses the requisite viscosity, electrical resistivity, and thermal and chemical stability under SOFC operating conditions to act as a reliable sealant. Sandwich seals between aluminized stainless steel and a YSZ/NiO-YSZ bilayer survived 148 thermal cycles (800 °C to room temperature) in both oxidizing and reducing atmospheres at a differential pressure of ∼3.4 kPa (0.5 psi) without failure. For sandwich seals that were held at 800 °C for up to 2280 h in air, G102 resisted crystallization, there were limited interactions at the G102/YSZ interface, but BaAl2Si2O8 crystals formed at the glass/metal interface because of the reaction between the glass and the aluminized steel. Sandwich seals that were intentionally cracked by thermal shock resealed to became hermetic upon reheating to temperatures as low as 744 °C.

  19. Stability of alkali-metal hydrides: effects of n-type doping

    Science.gov (United States)

    Olea Amezcua, Monica Araceli; de La Peña Seaman, Omar; Rivas Silva, Juan Francisco; Heid, Rolf; Bohnen, Klaus-Peter

    Metal hydrides could be considered ideal solid-state hydrogen storage systems, they have light weight and high hydrogen volumetric densities, but the hydrogen desorption process requires excessively high temperatures due to their high stability. Efforts have been performed to improve their dehydrogenation properties, based on the introduction of defects, impurities and doping. We present a systematic study of the n-type (electronic) doping effects on the stability of two alkali-metal hydrides: Na1-xMgxH and Li1-xBexH. These systems have been studied within the framework of density functional perturbation theory, using a mixed-basis pseudopotential method and the self-consistent version of the virtual crystal approximation to model the doping. The full-phonon dispersions are analyzed for several doping content, paying special attention to the crystal stability. It is found a doping content threshold for each system, where they are close to dynamical instabilities, which are related to charge redistribution in interstitial zones. Applying the quasiharmonic approximation, the vibrational free energy, the linear thermal expansion and heat capacities are obtained for both hydrides systems and are analyzed as a function of the doping content. This work is partially supported by the VIEP-BUAP 2016 and CONACYT-México (No.221807) projects.

  20. What is moving in hybrid halide perovskite solar cells?

    OpenAIRE

    Frost, Jarvist M.; Walsh, Aron

    2016-01-01

    Conspectus Organic–inorganic semiconductors, which adopt the perovskite crystal structure, have perturbed the landscape of contemporary photovoltaics research. High-efficiency solar cells can be produced with solution-processed active layers. The materials are earth abundant, and the simple processing required suggests that high-throughput and low-cost manufacture at scale should be possible. While these materials bear considerable similarity to traditional inorganic semiconductors, there are...

  1. Crystallization In High Level Waste (HLW) Glass Melters: Operational Experience From The Savannah River Site

    Energy Technology Data Exchange (ETDEWEB)

    Fox, K. M.

    2014-02-27

    observed in any of the pour stream glass samples. Spinel was observed at the bottom of DWPF Melter 1 as a result of K-3 refractory corrosion. Issues have occurred with accumulation of spinel in the pour spout during periods of operation at higher waste loadings. Given that both DWPF melters were or have been in operation for greater than 8 years, the service life of the melters has far exceeded design expectations. It is possible that the DWPF liquidus temperature approach is conservative, in that it may be possible to successfully operate the melter with a small degree of allowable crystallization in the glass. This could be a viable approach to increasing waste loading in the glass assuming that the crystals are suspended in the melt and swept out through the riser and pour spout. Additional study is needed, and development work for WTP might be leveraged to support a different operating limit for the DWPF. Several recommendations are made regarding considerations that need to be included as part of the WTP crystal tolerant strategy based on the DWPF development work and operational data reviewed here. These include: Identify and consider the impacts of potential heat sinks in the WTP melter and glass pouring system; Consider the contributions of refractory corrosion products, which may serve to nucleate additional crystals leading to further accumulation; Consider volatilization of components from the melt (e.g., boron, alkali, halides, etc.) and determine their impacts on glass crystallization behavior; Evaluate the impacts of glass REDuction/OXidation (REDOX) conditions and the distribution of temperature within the WTP melt pool and melter pour chamber on crystal accumulation rate; Consider the impact of precipitated crystals on glass viscosity; Consider the impact of an accumulated crystalline layer on thermal convection currents and bubbler effectiveness within the melt pool; Evaluate the impact of spinel accumulation on Joule heating of the WTP melt pool; and

  2. Process for carbonaceous material conversion and recovery of alkali metal catalyst constituents held by ion exchange sites in conversion residue

    Science.gov (United States)

    Sharp, David W.

    1980-01-01

    In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced, alkali metal constituents are recovered for the particles by contacting or washing them with an aqueous solution containing calcium or magnesium ions in an alkali metal recovery zone at a low temperature, preferably below about 249.degree. F. During the washing or leaching process, the calcium or magnesium ions displace alkali metal ions held by ion exchange sites in the particles thereby liberating the ions and producing an aqueous effluent containing alkali metal constituents. The aqueous effluent from the alkali metal recovery zone is then recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

  3. Generation and characterization of alkali metal clusters in Y-FAU zeolites. An ESR and MAS NMR spectroscopic study

    Science.gov (United States)

    Hannus, István; Béres, Attila; Nagy, János B.; Halász, János; Kiricsi, Imre

    1997-06-01

    Charged and neutral metal clusters of various compositions and sizes can be prepared by controlling the alkali metal content by the decomposition of alkali azides and the composition of the host zeolite by ion-exchange. ESR signals show that electron transfer from alkali metal atoms to alkali metal cations does occur, but in a direction opposite to that predicted by the gas-phase thermochemistry. Alkali metal clusters proved to be very active basic catalytic centers.

  4. A composite light-harvesting layer from photoactive polymer and halide perovskite for planar heterojunction solar cells

    Science.gov (United States)

    Wang, Heming; Rahaq, Yaqub; Kumar, Vikas

    2016-07-01

    A new route for fabrication of photoactive materials in organic-inorganic hybrid solar cells is presented in this report. Photoactive materials by blending a semiconductive conjugated polymer with an organolead halide perovskite were fabricated for the first time. The composite active layer was then used to make planar heterojunction solar cells with the PCBM film as the electron-acceptor. Photovoltaic performance of solar cells was investigated by J-V curves and external quantum efficiency spectra. We demonstrated that the incorporation of the conjugated photoactive polymer into organolead halide perovskites did not only contribute to the generation of charges, but also enhance stability of solar cells by providing a barrier protection to halide perovskites. It is expected that versatile of conjugated semi-conductive polymers and halide perovskites in photoactive properties enables to create various combinations, forming composites with advantages offered by both types of photoactive materials.

  5. An Efficient Synthesis of Diaryl Ethers by Coupling Aryl Halides with Substituted Phenoxytrimethylsilane in the Presence of TBAF

    Institute of Scientific and Technical Information of China (English)

    Jian Kui ZHAO; Yan Guang WANG

    2003-01-01

    A general synthesis of diaryl ethers via coupling of aryl halides with substitutedphenoxytrimethylsilane in the presence of TBAF is described. The protocol is simple and mild,and gives good to excellent yields.

  6. Spectral Features and Charge Dynamics of Lead Halide Perovskites: Origins and Interpretations.

    Science.gov (United States)

    Sum, Tze Chien; Mathews, Nripan; Xing, Guichuan; Lim, Swee Sien; Chong, Wee Kiang; Giovanni, David; Dewi, Herlina Arianita

    2016-02-16

    Lead halide perovskite solar cells are presently the forerunner among the third generation solution-processed photovoltaic technologies. With efficiencies exceeding 20% and low production costs, they are prime candidates for commercialization. Critical insights into their light harvesting, charge transport, and loss mechanisms have been gained through time-resolved optical probes such as femtosecond transient absorption spectroscopy (fs-TAS), transient photoluminescence spectroscopy, and time-resolved terahertz spectroscopy. Specifically, the discoveries of long balanced electron-hole diffusion lengths and gain properties in halide perovskites underpin their significant roles in uncovering structure-function relations and providing essential feedback for materials development and device optimization. In particular, fs-TAS is becoming increasingly popular in perovskite characterization studies, with commercial one-box pump-probe systems readily available as part of a researcher's toolkit. Although TAS is a powerful probe in the study of charge dynamics and recombination mechanisms, its instrumentation and data interpretation can be daunting even for experienced researchers. This issue is exacerbated by the sensitive nature of halide perovskites where the kinetics are especially susceptible to pump fluence, sample preparation and handling and even degradation effects that could lead to disparate conclusions. Nonetheless, with end-users having a clear understanding of TAS's capabilities, subtleties, and limitations, cutting-edge work with deep insights can still be performed using commercial setups as has been the trend for ubiquitous spectroscopy instruments like absorption, fluorescence, and transient photoluminescence spectrometers. Herein, we will first briefly examine the photophysical processes in lead halide perovskites, highlighting their novel properties. Next, we proceed to give a succinct overview of the fundamentals of pump-probe spectroscopy in relation

  7. Coherent coupling of alkali atoms by random collisions

    CERN Document Server

    Katz, Or; Firstenberg, Ofer

    2015-01-01

    Random spin-exchange collisions in warm alkali vapor cause rapid decoherence and act to equilibriate the spin state of the atoms. In contrast, here we demonstrate experimentally and theoretically a coherent coupling of one alkali specie to another specie, mediated by these random collisions. We show that, the minor specie (potassium) inherits the magnetic properties of the dominant specie (rubidium), including its lifetime (T1), coherence time (T2), gyromagnetic ratio, and SERF magnetic-field threshold. We further show that this coupling can be completely controlled by varying the strength of the magnetic field. Finally, we explain these phenomena analytically by modes-mixing of the two species via spin-exchange collisions.

  8. Alkali-helium snowball complexes formed on helium nanodroplets.

    Science.gov (United States)

    Müller, S; Mudrich, M; Stienkemeier, F

    2009-07-28

    We systematically investigate the formation and stability of snowballs formed by femtosecond photoionization of small alkali clusters bound to helium nanodroplets. For all studied alkali species Ak = (Na,K,Rb,Cs) we observe the formation of snowballs Ak(+)He(N) when multiply doping the droplets. Fragmentation of clusters Ak(N) upon ionization appears to enhance snowball formation. In the case of Na and Cs we also detect snowballs Ak(2) (+)He(N) formed around Ak dimer ions. While the snowball progression for Na and K is limited to less than 11 helium atoms, the heavier atoms Rb and Cs feature wide distributions at least up to Ak(+)He(41). Characteristic steps in the mass spectra of Cs-doped helium droplets are found at positions consistent with predictions on the closure of the first shell of helium atoms around the Ak(+) ion based on variational Monte Carlo simulations.

  9. Coherent coupling of alkali atoms by random collisions.

    Science.gov (United States)

    Katz, Or; Peleg, Or; Firstenberg, Ofer

    2015-09-11

    Random spin-exchange collisions in warm alkali vapor cause rapid decoherence and act to equilibrate the spin state of the atoms in the vapor. In contrast, here we demonstrate experimentally and theoretically a coherent coupling of one alkali species to another species, mediated by these random collisions. We show that the minor species (potassium) inherits the magnetic properties of the dominant species (rubidium), including its lifetime (T_{1}), coherence time (T_{2}), gyromagnetic ratio, and spin-exchange relaxation-free magnetic-field threshold. We further show that this coupling can be completely controlled by varying the strength of the magnetic field. Finally, we explain these phenomena analytically by mode mixing of the two species via spin-exchange collisions.

  10. Penetration of alkali atoms throughout a graphene membrane: theoretical modeling.

    Science.gov (United States)

    Boukhvalov, D W; Virojanadara, C

    2012-03-07

    Theoretical studies of penetration of various alkali atoms (Li, Na, Rb, Cs) throughout a graphene membrane grown on a silicon carbide substrate are reported and compared with recent experimental results. Results of first principles modeling demonstrate a rather low (about 0.8 eV) energy barrier for the formation of temporary defects in the carbon layer required for the penetration of Li at a high concentration of adatoms, a higher (about 2 eV) barrier for Na, and barriers above 4 eV for Rb and Cs. Experiments prove migration of lithium adatoms from the graphene surface to the buffer layer and SiC substrate at room temperature, sodium at 100 °C and impenetrability of the graphene membrane for Rb and Cs. Differences between epitaxial and free-standing graphene for the penetration of alkali ions are also discussed.

  11. Polarizabilities and hyperpolarizabilities of the alkali metal atoms

    Energy Technology Data Exchange (ETDEWEB)

    Fuentealba, P. (Chile Univ., Santiago (Chile). Departamento de Fisica and Centro de Mecanica Cuantica Aplicada (CMCA)); Reyes, O. (Chile Univ., Santiago (Chile). Dept. de Fisica)

    1993-08-14

    The electric static dipole polarizability [alpha], quadrupole polarizability C, dipole-quadrupole polarizability B, and the second dipole hyperpolarizability [gamma] have been calculated for the alkali metal atoms in the ground state. The results are based on a pseudopotential which is able to incorporate the very important core-valence correlation effect through a core polarization potential, and, in an empirical way, the main relativistic effects. The calculated properties compare very well with more elaborated calculations for the Li atom, excepting the second hyperpolarizability [gamma]. For the other atoms, there is neither theoretical nor experimental information about most of the higher polarizabilities. Hence, the results of this paper should be seen as a first attempt to give a complete account of the series expansion of the interaction energy of an alkali metal atom and a static electric field. (author).

  12. Density functional study of ferromagnetism in alkali metal thin films

    Indian Academy of Sciences (India)

    Prasenjit Sen

    2010-04-01

    Electronic and magnetic structures of (1 0 0) films of K and Cs, having thicknesses of one to seven layers, are calculated within the plane-wave projector augmented wave (PAW) formalism of the density functional theory (DFT), using both local spin density approximation (LSDA) and the PW91 generalized gradient approximation (GGA). Only a six-layer Cs film is found to have a ferromagnetic (FM) state which is degenerate with a paramagnetic (PM) state within the accuracy of these calculations. These results are compared with those obtained from calculations on a finite-thickness uniform jellium model (UJM), and it is argued that within LSDA or GGA, alkali metal thin films cannot be claimed to have an FM ground state. Relevance of these results to the experiments on transition metal-doped alkali metal thin films and bulk hosts are also discussed.

  13. PREPARATION OF HOLLOW LATEX PARTICLES BY ALKALI-ACID TREATMENT

    Institute of Scientific and Technical Information of China (English)

    郝冬梅; 王新灵; 朱卫华; 唐小真; 刘成岑; 施凯

    2001-01-01

    Hollow polymer latex particles were prepared by seeded emulsion polymerization. A seed latex consisting of styrene (St), butyl acrylate(BA) copolymer was first prepared, and seeded terpolymerization of St-BA-MA(methacrylic acid) were then carried out in the absence of surfactant. Final latex was treated by a two-step treatment under alkaline and acidic conditions, thus, the particles with hollow structure were obtained. We discussed the effects of pH value, temperature and time in alkali and acid treatment processes on hollow structure within the polymer latex particles and amount of carboxylic group on particle surface. The results show that the hollow polymer latex particles with the largest hollow size can be obtained under a certain condition (pH12.5, 90°C, 3 h in alkali treatment stage and pH2.5, 85°C, 3 h in acid treatment stage).

  14. Positronium-alkali atom scattering at medium energies

    Energy Technology Data Exchange (ETDEWEB)

    Chakraborty, Ajoy [Laban Hrad Vidyapith, AD-369, Salt Lake City, Kolkata 700 064 (India); Basu, Arindam [Department of Physics, Maheshtala College, Chandannagar, South 24 Parganas, Kolkata 700 140 (India); Sarkar, Nirmal K [Sodepur Chandrachur Vidyapith, 1, Desh Bandhu Nagar, Sodepur, 743 174 (India); Sinha, Prabal K [Department of Physics, Bangabasi College, 19, Raj Kumar Chakravorty Sarani, Kolkata 700 009 (India)

    2004-04-28

    We investigate the scattering of orthopositronium (o-Ps) atom off different atomic alkali targets (Na to Cs) at low and medium energies (up to 120 eV). Projectile-elastic and target-elastic close-coupling models have been employed to investigate the systems in addition to the static-exchange model. Elastic, excitation and total cross sections have been reported for all four systems. The magnitude of the alkali excitation cross section increases with increasing atomic number of the target atom while the position of the peak value shifts towards lower incident energies. The magnitudes of the Ps excitation and ionization cross sections increase steadily with atomic number with no change in the peak position. The reported results show regular behaviour with increasing atomic number of the target atom. Scattering parameters for the Ps-Rb and Ps-Cs systems are being reported for the first time.

  15. Research Update: Challenges for high-efficiency hybrid lead-halide perovskite LEDs and the path towards electrically pumped lasing

    OpenAIRE

    Guangru Li; Michael Price; Felix Deschler

    2016-01-01

    Hybrid lead-halide perovskites have emerged as promising solution-processed semiconductor materials for thin-film optoelectronics. In this review, we discuss current challenges in perovskite LED performance, using thin-film and nano-crystalline perovskite as emitter layers, and look at device performance and stability. Fabrication of electrically pumped, optical-feedback devices with hybrid lead halide perovskites as gain medium is a future challenge, initiated by the demonstration of optical...

  16. Solubility of 1:1 Alkali Nitrates and Chlorides in Near-Critical and Supercritical Water : 1 Alkali Nitrates and Chlorides in Near-Critical and Supercritical Water

    NARCIS (Netherlands)

    Leusbrock, Ingo; Metz, Sybrand J.; Rexwinkel, Glenn; Versteeg, Geert F.

    2009-01-01

    To increase the available data oil systems containing supercritical water and inorganic compounds, all experimental setup was designed to investigate the solubilities of inorganic compounds Ill supercritical water, In this work, three alkali chloride salts (LiCl, NaCl, KCl) and three alkali nitrate

  17. A hidden history of heartburn: The milk-alkali syndrome

    OpenAIRE

    2011-01-01

    Milk-alkali syndrome was once considered to be of historic interest and a rare cause of hypercalcemia. Currently, it should be an important consideration in the differential diagnosis of hypercalcemia, after malignancies and primary hyperparathyroidism. The resurgence is in part due to the easy availability of over the counter (OTC) calcium preparations. We describe a 50-year-old man who presented with severe hypercalcemia on two occasions associated with renal failure and metabolic alkalosis...

  18. Efficient potassium diode pumped alkali laser operating in pulsed mode.

    Science.gov (United States)

    Zhdanov, Boris V; Rotondaro, Matthew D; Shaffer, Michael K; Knize, Randall J

    2014-07-14

    This paper presents the results of our experiments on the development of an efficient hydrocarbon free diode pumped alkali laser based on potassium vapor buffered by He gas at 600 Torr. A slope efficiency of more than 50% was demonstrated with a total optical conversion efficiency of 30%. This result was achieved by using a narrowband diode laser stack as the pump source. The stack was operated in pulsed mode to avoid limiting thermal effects and ionization.

  19. Composition and thermodynamic properties of dense alkali metal plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Gabdullin, M.T. [NNLOT, al-Farabi Kazakh National University, 71 al-Farabi Str., Almaty 050035 (Kazakhstan); Ramazanov, T.S.; Dzhumagulova, K.N. [IETP, al-Farabi Kazakh National University, 71 al-Farabi Str., Almaty 050035 (Kazakhstan)

    2012-04-15

    In this work composition and thermodynamic properties of dense alkali metal plasmas (Li, Na) were investigated. Composition was derived by solving the Saha equations with corrections due to nonideality. The lowering of the ionization potentials was calculated on the basis of pseudopotentials by taking screening and quantum effects into account (copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  20. Engineering Properties of Alkali-Activated Fly Ash Concrete

    OpenAIRE

    2006-01-01

    This paper reports the results of experimental research on certain engineering properties of a new (portland cement-free) concrete made with alkali-activated fly ash. Laboratory tests were conducted to determine its (bending and compression) mechanical strength, modulus of elasticity, bond strength, and shrinkage. The results show that mortar and concrete made with portland cement-free activated fly ash develop a high mechanical strength in short periods of time, have a moderate modulus of el...