Oxygen vacancies in oxides studied by annihilation of mono-energetic positrons

Energy Technology Data Exchange (ETDEWEB)

Hugenschmidt, Christoph; Pikart, Philip [ZWE FRM II, Technische Universitaet Muenchen, Lichtenbergstrasse 1, 85747 Garching (Germany); Physik-Department E21, Technische Universitaet Muenchen, James-Franck-Strasse, 85748 Garching (Germany); Schreckenbach, Klaus [Physik-Department E21, Technische Universitaet Muenchen, James-Franck-Strasse, 85748 Garching (Germany)

2009-07-01

Oxygen vacancies play a fundamental role for the material properties of various oxides, e.g. charge carrier density in high-Tc superconductors, magnetic properties of diluted magnetic semiconductors or paramagnetic properties of SiO{sub 2}. In this study, open volume defects in (metal) oxides are investigated by Doppler-broadening spectroscopy (DBS) of the positron annihilation. More detailed information about the chemical surrounding at the positron annihilation site is gained by additional coincident DBS experiments, where a signature of positrons annihilating with electrons from oxygen is observed. The mono-energetic positron beam at NEPOMUC was used which allows depth dependent measurements, and hence the investigation of thin oxide layers. Recent results for metallic oxides such as ZnO are presented and compared with various non-metallic oxides such as amorphous and crystalline SiO{sub 2}, oxygen terminated Si-surface, and ice. The role of neutral and charged oxygen vacancies and the application of the positron annihilation technique to study oxygen vacancies will be discussed.

Electro-oxidation of water on hematite: Effects of surface termination and oxygen vacancies investigated by first-principles

DEFF Research Database (Denmark)

Hellman, Anders; Iandolo, Beniamino; Wickman, Bjorn

2015-01-01

The oxygen evolution reaction on hydroxyl- and oxygen-terminated hematite was investigated using first-principle calculations within a theoretical electrochemical framework. Both pristine hematite and hematite containing oxygen vacancies were considered. The onset potential was determined to be 1...... on hematite occurs on the oxygen-terminated hematite, containing oxygen vacancies. (C) 2015 Elsevier B.V. All rights reserved....

Effects of hydration and oxygen vacancy on CO2 adsorption and activation on beta-Ga2O3(100).

Science.gov (United States)

Pan, Yun-xiang; Liu, Chang-jun; Mei, Donghai; Ge, Qingfeng

2010-04-20

The effects of hydration and oxygen vacancy on CO(2) adsorption on the beta-Ga(2)O(3)(100) surface have been studied using density functional theory slab calculations. Adsorbed CO(2) is activated on the dry perfect beta-Ga(2)O(3)(100) surface, resulting in a carbonate species. This adsorption is slightly endothermic, with an adsorption energy of 0.07 eV. Water is preferably adsorbed molecularly on the dry perfect beta-Ga(2)O(3)(100) surface with an adsorption energy of -0.56 eV, producing a hydrated perfect beta-Ga(2)O(3)(100) surface. Adsorption of CO(2) on the hydrated surface as a carbonate species is also endothermic, with an adsorption energy of 0.14 eV, indicating a slightly repulsive interaction when H(2)O and CO(2) are coadsorbed. The carbonate species on the hydrated perfect surface can be protonated by the coadsorbed H(2)O to a bicarbonate species, making the CO(2) adsorption exothermic, with an adsorption energy of -0.13 eV. The effect of defects on CO(2) adsorption and activation has been examined by creating an oxygen vacancy on the dry beta-Ga(2)O(3)(100) surface. The formation of an oxygen vacancy is endothermic, by 0.34 eV, with respect to a free O(2) molecule in the gas phase. Presence of the oxygen vacancy promoted the adsorption and activation of CO(2). In the most stable CO(2) adsorption configuration on the dry defective beta-Ga(2)O(3)(100) surface with an oxygen vacancy, one of the oxygen atoms of the adsorbed CO(2) occupies the oxygen vacancy site, and the CO(2) adsorption energy is -0.31 eV. Water favors dissociative adsorption at the oxygen vacancy site on the defective surface. This process is spontaneous, with a reaction energy of -0.62 eV. These results indicate that, when water and CO(2) are present in the adsorption system simultaneously, water will compete with CO(2) for the oxygen vacancy sites and impact CO(2) adsorption and conversion negatively.

Unraveling the facet-dependent and oxygen vacancy role for ethylene hydrogenation on Co{sub 3}O{sub 4} (110) surface: A DFT+U study

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yong-Chao; Pan, Lun; Lu, Jinhui; Song, Jiajia; Li, Zheng; Zhang, Xiangwen; Wang, Li [Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, Tianjin University (China); Collaborative Innovative Center of Chemical Science and Engineering (Tianjin), Tianjin 300072 (China); Zou, Ji-Jun, E-mail: jj_zou@tju.edu.cn [Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, Tianjin University (China); Collaborative Innovative Center of Chemical Science and Engineering (Tianjin), Tianjin 300072 (China)

2017-04-15

Highlights: • The mechanism of ethylene hydrogenation on perfect and oxygen defective Co{sub 3}O{sub 4}(110) is investigated by using DFT + U. • Oxygen vacancy promotes ethylene hydrogenation thermodynamically and kinetically. • The Co3O4 (110) facet is more active than the (111) one for ethylene hydrogenation. - Abstract: Crystal facet engineering and defect engineering are both critical strategies to improve the catalytic hydrogenation performance of catalyst. Herein, ethylene hydrogenation on the perfect and oxygen defective Co{sub 3}O{sub 4}(110) surfaces has been studied by using periodic density functional theory calculations. The results are compared with that on Co{sub 3}O{sub 4}(111) surface to clarify the problem of which facet for Co{sub 3}O{sub 4} is more reactive, and to illuminate the role of oxygen vacancy. The low oxygen vacancy formation energy suggests that Co{sub 3}O{sub 4}(110) surface with defective site is easily formed. The whole mechanism of H{sub 2} dissociation and stepwise hydrogenation of ethylene to ethane is examined, and the most favorable pathway is heterolytic dissociation of H{sub 2} follows two stepwise hydrogenation of ethylene process. The results show that ethyl hydrogenation to ethane on perfect Co{sub 3}O{sub 4}(110) surface is the rate limiting step with an activation energy of 1.19 eV, and the presence of oxygen vacancy strongly reduces the activation energies of main elementary steps, and the activation energy of rate limiting step is only 0.47 eV. Compared with that on Co{sub 3}O{sub 4}(111), ethylene hydrogenation is preferred on Co{sub 3}O{sub 4}(110) surface. Therefore, Co{sub 3}O{sub 4} with exposed (110) facet is predicted as an excellent catalyst for ethylene hydrogenation.

Simultaneous modulation of surface composition, oxygen vacancies and assembly in hierarchical Co3O4 mesoporous nanostructures for lithium storage and electrocatalytic oxygen evolution

DEFF Research Database (Denmark)

Sun, Hongyu; Zhao, Yanyan; Mølhave, Kristian

2017-01-01

in superior electrochemical properties when used as the anode materials for lithium-ion batteries and as an electrocatalyst for the oxygen evolution reaction. The excellent electrochemical performance is attributed to the synergistic effects of novel hierarchical morphology, crystal structure of the active...... materials, the improvement of intrinsic conductivity and inner surface area induced by the oxygen vacancies. The present strategy not only provides a facile method to assemble novel hierarchical architectures, but also paves a way to control surface structures (chemical composition and crystal defects...

Tracking Oxygen Vacancies in Thin Film SOFC Cathodes

Science.gov (United States)

Leonard, Donovan; Kumar, Amit; Jesse, Stephen; Kalinin, Sergei; Shao-Horn, Yang; Crumlin, Ethan; Mutoro, Eva; Biegalski, Michael; Christen, Hans; Pennycook, Stephen; Borisevich, Albina

2011-03-01

Oxygen vacancies have been proposed to control the rate of the oxygen reduction reaction and ionic transport in complex oxides used as solid oxide fuel cell (SOFC) cathodes [1,2]. In this study oxygen vacancies were tracked, both dynamically and statically, with the combined use of scanned probe microscopy (SPM) and scanning transmission electron microscopy (STEM). Epitaxial films of La 0.8 Sr 0.2 Co O3 (L SC113) and L SC113 / LaSrCo O4 (L SC214) on a GDC/YSZ substrate were studied, where the latter showed increased electrocatalytic activity at moderate temperature. At atomic resolution, high angle annular dark field STEM micrographs revealed vacancy ordering in L SC113 as evidenced by lattice parameter modulation and EELS studies. The evolution of oxygen vacancy concentration and ordering with applied bias and the effects of bias cycling on the SOFC cathode performance will be discussed. Research is sponsored by the of Materials Sciences and Engineering Division, U.S. DOE.

Molecular dynamics simulations of ferroelectric domain formation by oxygen vacancy

Science.gov (United States)

Zhu, Lin; You, Jeong Ho; Chen, Jinghong; Yeo, Changdong

2018-05-01

An oxygen vacancy, known to be detrimental to ferroelectric properties, has been investigated numerically for the potential uses to control ferroelectric domains in films using molecular dynamics simulations based on the first-principles effective Hamiltonian. As an electron donor, an oxygen vacancy generates inhomogeneous electrostatic and displacement fields which impose preferred polarization directions near the oxygen vacancy. When the oxygen vacancies are placed at the top and bottom interfaces, the out-of-plane polarizations are locally developed near the interfaces in the directions away from the interfaces. These polarizations from the interfaces are in opposite directions so that the overall out-of-plane polarization becomes significantly reduced. In the middle of the films, the in-plane domains are formed with containing 90° a 1/a 2 domain walls and the films are polarized along the [1 1 0] direction even when no electric field is applied. With oxygen vacancies placed at the top interface only, the films exhibit asymmetric hysteresis loops, confirming that the oxygen vacancies are one of the possible sources of ferroelectric imprint. It has been qualitatively demonstrated that the domain structures in the imprint films can be turned on and off by controlling an external field along the thickness direction. This study shows qualitatively that the oxygen vacancies can be utilized for tuning ferroelectric domain structures in films.

Oxygen vacancies as active sites for water dissociation on rutile TiO₂(110)

DEFF Research Database (Denmark)

Schaub, R.; Thostrup, P.; Lopez, Nuria

2001-01-01

to dissociate H2O through the transfer of one proton to a nearby oxygen atom, forming two hydroxyl groups for every vacancy. The amount of water dissociation is limited by the density of oxygen vacancies present on the clean surface exclusively. The dissociation process sets in as soon as molecular water...

Photocatalytic Conversion of Nitrogen to Ammonia with Water on Surface Oxygen Vacancies of Titanium Dioxide.

Science.gov (United States)

Hirakawa, Hiroaki; Hashimoto, Masaki; Shiraishi, Yasuhiro; Hirai, Takayuki

2017-08-09

Ammonia (NH 3 ) is an essential chemical in modern society. It is currently manufactured by the Haber-Bosch process using H 2 and N 2 under extremely high-pressure (>200 bar) and high-temperature (>673 K) conditions. Photocatalytic NH 3 production from water and N 2 at atmospheric pressure and room temperature is ideal. Several semiconductor photocatalysts have been proposed, but all suffer from low efficiency. Here we report that a commercially available TiO 2 with a large number of surface oxygen vacancies, when photoirradiated by UV light in pure water with N 2 , successfully produces NH 3 . The active sites for N 2 reduction are the Ti 3+ species on the oxygen vacancies. These species act as adsorption sites for N 2 and trapping sites for the photoformed conduction band electrons. These properties therefore promote efficient reduction of N 2 to NH 3 . The solar-to-chemical energy conversion efficiency is 0.02%, which is the highest efficiency among the early reported photocatalytic systems. This noble-metal-free TiO 2 system therefore shows a potential as a new artificial photosynthesis for green NH 3 production.

Molecular dynamics simulations of oxygen vacancy diffusion in SrTiO3

International Nuclear Information System (INIS)

Schie, Marcel; Marchewka, Astrid; Waser, Rainer; Müller, Thomas; De Souza, Roger A

2012-01-01

A classical force-field model with partial ionic charges was applied to study the behaviour of oxygen vacancies in the perovskite oxide strontium titanate (SrTiO 3 ). The dynamical behaviour of these point defects was investigated as a function of temperature and defect concentration by means of molecular dynamics (MD) simulations. The interaction between oxygen vacancies and an extended defect, here a Σ3(111) grain boundary, was also examined by means of MD simulations. Analysis of the vacancy distribution revealed considerable accumulation of vacancies in the envelope of the grain boundary. The possible clustering of oxygen vacancies in bulk SrTiO 3 was studied by means of static lattice calculations within the Mott-Littleton approach. All binary vacancy-vacancy configurations were found to be energetically unfavourable.

Molecular dynamics simulations of oxygen vacancy diffusion in SrTiO3.

Science.gov (United States)

Schie, Marcel; Marchewka, Astrid; Müller, Thomas; De Souza, Roger A; Waser, Rainer

2012-12-05

A classical force-field model with partial ionic charges was applied to study the behaviour of oxygen vacancies in the perovskite oxide strontium titanate (SrTiO(3)). The dynamical behaviour of these point defects was investigated as a function of temperature and defect concentration by means of molecular dynamics (MD) simulations. The interaction between oxygen vacancies and an extended defect, here a Σ3(111) grain boundary, was also examined by means of MD simulations. Analysis of the vacancy distribution revealed considerable accumulation of vacancies in the envelope of the grain boundary. The possible clustering of oxygen vacancies in bulk SrTiO(3) was studied by means of static lattice calculations within the Mott-Littleton approach. All binary vacancy-vacancy configurations were found to be energetically unfavourable.

Oxygen vacancies dependent phase transition of Y{sub 2}O{sub 3} films

Energy Technology Data Exchange (ETDEWEB)

Yu, Pengfei; Zhang, Kan [Department of Materials Science, State Key Laboratory of Superhard Materials, and Key Laboratory of Automobile Materials, MOE, Jilin University, Changchun 130012 (China); Huang, Hao [Titanium Alloys Lab. Beijing Institute of Aeronautical Materials, Beijing 81-15 100095 (China); Wen, Mao, E-mail: Wenmao225@jlu.edu.cn [Department of Materials Science, State Key Laboratory of Superhard Materials, and Key Laboratory of Automobile Materials, MOE, Jilin University, Changchun 130012 (China); Li, Quan; Zhang, Wei; Hu, Chaoquan [Department of Materials Science, State Key Laboratory of Superhard Materials, and Key Laboratory of Automobile Materials, MOE, Jilin University, Changchun 130012 (China); Zheng, Weitao, E-mail: WTZheng@jlu.edu.cn [Department of Materials Science, State Key Laboratory of Automotive Simulation and Control and Key Laboratory of Automobile Materials, MOE, Jilin University, Changchun 130012 (China)

2017-07-15

Highlights: • Oxygen vacancies for Y{sub 2}O{sub 3} films increase monotonously with increasing T{sub s}. • Oxygen vacancies can promote the nucleation of monoclinic phase. • That monoclinic phase with oxygen deficiency is not thermodynamic stable at high temperature. • Phase transition from monoclinic to oxygen defective occurs at high concentrations of oxygen vacancies. • High hardness just appears in Y{sub 2}O{sub 3} films with mixed phase configurations. - Abstract: Y{sub 2}O{sub 3} films have great application potential in high-temperature metal matrix composite and nuclear engineering, used as interface diffusion and reaction barrier coating owing to their excellent thermal and chemical stability, high melting point and extremely negative Gibbs formation energy, and thus their structural and mechanical properties at elevated temperature are especially important. Oxygen vacancies exist commonly in yttrium oxide (Y{sub 2}O{sub 3}) thin films and act strongly on the phase structure and properties, but oxygen vacancies dependent phase transition at elevated temperature has not been well explored yet. Y{sub 2}O{sub 3} thin films with different oxygen vacancy concentrations have been achieved by reactive sputtering through varying substrate temperature (T{sub s}), in which oxygen vacancies increase monotonously with increasing T{sub s}. For as-deposited Y{sub 2}O{sub 3} films, oxygen vacancies present at high T{sub s} can promote the nucleation of monoclinic phase, meanwhile, high T{sub s} can induce the instability of monoclinic phase. Thus their competition results in forming mixed phases of cubic and monoclinic at high T{sub s}. During vacuum annealing at 1000 °C, a critical oxygen vacancy concentration is observed, below which phase transition from monoclinic to cubic takes place, and above which phase transfer from monoclinic to the oxygen defective phase (ICDD file no. 39-1063), accompanying by stress reversal from compressive to tensile and

Interaction of oxygen vacancies in yttrium germanates

KAUST Repository

Wang, Hao

2012-01-01

Forming a good Ge/dielectric interface is important to improve the electron mobility of a Ge metal oxide semiconductor field-effect transistor. A thin yttrium germanate capping layer can improve the properties of the Ge/GeO 2 system. We employ electronic structure calculations to investigate the effect of oxygen vacancies in yttrium-doped GeO 2 and the yttrium germanates Y 2Ge 2O 7 and Y 2GeO 5. The calculated densities of states indicate that dangling bonds from oxygen vacancies introduce in-gap states, but the system remains insulating. However, yttrium-doped GeO 2 becomes metallic under oxygen deficiency. Y-doped GeO 2, Y 2Ge 2O 7 and Y 2GeO 5 are calculated to be oxygen substoichiometric under low Fermi energy conditions. The use of yttrium germanates is proposed as a way to effectively passivate the Ge/dielectric interface. This journal is © 2012 the Owner Societies.

Contributions of oxygen vacancies and titanium interstitials to band-gap states of reduced titania

Science.gov (United States)

Li, Jingfeng; Lazzari, Rémi; Chenot, Stéphane; Jupille, Jacques

2018-01-01

The spectroscopic fingerprints of the point defects of titanium dioxide remain highly controversial. Seemingly indisputable experiments lead to conflicting conclusions in which oxygen vacancies and titanium interstitials are alternately referred to as the primary origin of the Ti 3 d band-gap states. We report on experiments performed by electron energy loss spectroscopy whose key is the direct annealing of only the very surface of rutile TiO2(110 ) crystals and the simultaneous measurement of its temperature via the Bose-Einstein loss/gain ratio. By surface preparations involving reactions with oxygen and water vapor, in particular, under electron irradiation, vacancy- and interstitial-related band-gap states are singled out. Off-specular measurements reveal that both types of defects contribute to a unique charge distribution that peaks in subsurface layers with a common dispersive behavior.

Correlated lifetimes of free paraexcitons and excitons trapped at oxygen vacancies in cuprous oxide

International Nuclear Information System (INIS)

Koirala, Sandhaya; Naka, Nobuko; Tanaka, Koichiro

2013-01-01

We have studied transients of luminescence due to free excitons and excitons trapped at oxygen vacancies in cuprous oxide. We find that both trapped and free paraexcitons have lifetime dependent on temperature and on the oxygen concentration. By using samples containing much less copper vacancies relative to oxygen vacancies, we find out the direct correlation between the free paraexciton lifetime and trapped exciton lifetime. - Highlights: ► We have investigated trapping of free excitons at oxygen vacancies in cuprous oxide. ► Lifetimes of free and trapped excitons exhibit correlative temperature dependence. ► Four-level model with the activation energy of 33 meV well explains the observation. ► Comparison is made using the four samples with different vacancy concentrations. ► We clarified the crucial role of the oxygen vacancy in shortening the lifetimes.

Ultrafast atomic layer-by-layer oxygen vacancy-exchange diffusion in double-perovskite LnBaCo2O5.5+δ thin films.

Science.gov (United States)

Bao, Shanyong; Ma, Chunrui; Chen, Garry; Xu, Xing; Enriquez, Erik; Chen, Chonglin; Zhang, Yamei; Bettis, Jerry L; Whangbo, Myung-Hwan; Dong, Chuang; Zhang, Qingyu

2014-04-22

Surface exchange and oxygen vacancy diffusion dynamics were studied in double-perovskites LnBaCo2O5.5+δ (LnBCO) single-crystalline thin films (Ln = Er, Pr; -0.5 atoms in the LnBCO thin films is taking the layer by layer oxygen-vacancy-exchange mechanism. The first principles density functional theory calculations indicate that hydrogen atoms are present in LnBCO as bound to oxygen forming O-H bonds. This unprecedented oscillation phenomenon provides the first direct experimental evidence of the layer by layer oxygen vacancy exchange diffusion mechanism.

Spin-dependent recombination involving oxygen-vacancy complexes in silicon

OpenAIRE

Franke, David P.; Hoehne, Felix; Vlasenko, Leonid S.; Itoh, Kohei M.; Brandt, Martin S.

2014-01-01

Spin-dependent relaxation and recombination processes in $\\gamma$-irradiated $n$-type Czochralski-grown silicon are studied using continuous wave (cw) and pulsed electrically detected magnetic resonance (EDMR). Two processes involving the SL1 center, the neutral excited triplet state of the oxygen-vacancy complex, are observed which can be separated by their different dynamics. One of the processes is the relaxation of the excited SL1 state to the ground state of the oxygen-vacancy complex, t...

The role of Ar plasma treatment in generating oxygen vacancies in indium tin oxide thin films prepared by the sol-gel process

Energy Technology Data Exchange (ETDEWEB)

Hwang, Deuk-Kyu [Department of Materials Science and Engineering, Yonsei University, 50 Yonsei-ro, Seoul, 03722 (Korea, Republic of); Misra, Mirnmoy; Lee, Ye-Eun [Department of BioNano Technology, Gachon University, 1342 Seong-nam dae-ro, Seong-nam si, Gyeonggi-do, 13120 (Korea, Republic of); Baek, Sung-Doo [Department of Materials Science and Engineering, Yonsei University, 50 Yonsei-ro, Seoul, 03722 (Korea, Republic of); Myoung, Jae-Min, E-mail: jmmyoung@yonsei.ac.kr [Department of Materials Science and Engineering, Yonsei University, 50 Yonsei-ro, Seoul, 03722 (Korea, Republic of); Lee, Tae Il, E-mail: t2.lee77@gachon.ac.kr [Department of BioNano Technology, Gachon University, 1342 Seong-nam dae-ro, Seong-nam si, Gyeonggi-do, 13120 (Korea, Republic of)

2017-05-31

Highlights: • Indium tin oxide thin film with about 41 nm thickness was obtained by the sol-gel process. • Thin film exhibited low resistivity. • Sheet resistance of thin film decreases with Ar plasma treatment time. • Ar plasma treatment on thin film does not alter the crystal structure and optical properties of the ITO thin-film. • There is no significant change in oxygen vacancies after 20 min of plasma treatment. - Abstract: Argon (Ar) plasma treatment was carried out to reduce the sheet resistance of indium tin oxide (ITO) thin films. The Ar plasma treatment did not cause any significant changes to the crystal structure, surface morphology, or optical properties of the ITO thin films. However, an X-ray photoelectron spectroscopy study confirmed that the concentration of oxygen vacancies in the film dramatically increased with the plasma treatment time. Thus, we concluded that the decrease in the sheet resistance was caused by the increase in the oxygen vacancy concentration in the film. Furthermore, to verify how the concentration of oxygen vacancies in the film increased with the Ar plasma treatment time, cumulative and continuous plasma treatments were conducted. The oxygen vacancies were found to be created by surface heating via the outward thermal diffusion of oxygen atoms from inside the film.

Oxygen Vacancies versus Fluorine at CeO 2 (111) : A Case of Mistaken Identity?

NARCIS (Netherlands)

Kullgren, J.; Wolf, M.J.; Castleton, C.W.M.; Mitev, P.; Briels, Willem J.; Hermansson, K.

2014-01-01

We propose a resolution to the puzzle presented by the surface defects observed with STM at the (111) surface facet of CeO 2 single crystals. In the seminal paper of Esch et al. [Science 309, 752 (2005)] they were identified with oxygen vacancies, but the observed behavior of these defects is

Bonding of gold nanoclusters to oxygen vacancies on rutile TiO2(110)

DEFF Research Database (Denmark)

Lopez, Nuria; schaub, R.; Thostrup, P.

2003-01-01

Through an interplay between scanning tunneling microscopy (STM) and density functional theory (DFT) calculations, we show that bridging oxygen vacancies are the active nucleation sites for Au clusters on the rutile TiO2(110) surface. We find that a direct correlation exists between a decrease in...

The interaction of impurity oxygen in silicon with vacancies

International Nuclear Information System (INIS)

Aslanyan, A.A.; Babayan, S.A.; Eritsyan, G.N.; Kholodar, G.A.; Melkonyan, R.A.; Vinetskij, V.L.

1981-01-01

Silicon specimens irradiated with 50 MeV electrons, containing along with isolated oxygen atoms more complicated oxy-quasi-molecules of SiOsub(n) (n=1,2,3,...) type are investigated. At isochronal and isothermal annealing in the temperature range 300-350 deg C, besides the reaction of vacancy capturing by oxygen atoms with formation of A-centres, there occur more complicated reactions with participation of vacancies, A-centres, oxygen containing quasi-molecules, and a variety of sinks. The kinetics of the processing taking place at irradiation and annealing was studied with respect to the measurement of IR absorption spectra in the region 1-16 μm. A model is suggested to describe the observed processes that differ qualitatively from those taking place in specimens containing completely dissociated oxygen [ru

Inhomogeneous Oxygen Vacancy Distribution in Semiconductor Gas Sensors: Formation, Migration and Determination on Gas Sensing Characteristics.

Science.gov (United States)

Liu, Jianqiao; Gao, Yinglin; Wu, Xu; Jin, Guohua; Zhai, Zhaoxia; Liu, Huan

2017-08-10

The density of oxygen vacancies in semiconductor gas sensors was often assumed to be identical throughout the grain in the numerical discussion of the gas-sensing mechanism of the devices. In contrast, the actual devices had grains with inhomogeneous distribution of oxygen vacancy under non-ideal conditions. This conflict between reality and discussion drove us to study the formation and migration of the oxygen defects in semiconductor grains. A model of the gradient-distributed oxygen vacancy was proposed based on the effects of cooling rate and re-annealing on semiconductive thin films. The model established the diffusion equations of oxygen vacancy according to the defect kinetics of diffusion and exclusion. We described that the steady-state and transient-state oxygen vacancy distributions, which were used to calculate the gas-sensing characteristics of the sensor resistance and response to reducing gases under two different conditions. The gradient-distributed oxygen vacancy model had the applications in simulating the sensor performances, such as the power law, the grain size effect and the effect of depletion layer width.

Inhomogeneous Oxygen Vacancy Distribution in Semiconductor Gas Sensors: Formation, Migration and Determination on Gas Sensing Characteristics

Directory of Open Access Journals (Sweden)

Jianqiao Liu

2017-08-01

Full Text Available The density of oxygen vacancies in semiconductor gas sensors was often assumed to be identical throughout the grain in the numerical discussion of the gas-sensing mechanism of the devices. In contrast, the actual devices had grains with inhomogeneous distribution of oxygen vacancy under non-ideal conditions. This conflict between reality and discussion drove us to study the formation and migration of the oxygen defects in semiconductor grains. A model of the gradient-distributed oxygen vacancy was proposed based on the effects of cooling rate and re-annealing on semiconductive thin films. The model established the diffusion equations of oxygen vacancy according to the defect kinetics of diffusion and exclusion. We described that the steady-state and transient-state oxygen vacancy distributions, which were used to calculate the gas-sensing characteristics of the sensor resistance and response to reducing gases under two different conditions. The gradient-distributed oxygen vacancy model had the applications in simulating the sensor performances, such as the power law, the grain size effect and the effect of depletion layer width.

Hydroxyl-dependent Evolution of Oxygen Vacancies Enables the Regeneration of BiOCl photocatalyst

KAUST Repository

Wu, Sujuan

2017-05-02

Photoinduced oxygen vacancies (OVs) are widely investigated as a vital point defect in wide-band-gap semiconductors. Still, the formation mechanism of OVs remains unclear in various materials. To elucidate the formation mechanism of photoinduced OVs in bismuth oxychloride (BiOCl), we synthesized two surface hydroxyl discrete samples in light of the discovery of the significant variance of hydroxyl groups before and after UV light exposure. It is noted that OVs can be obtained easily after UV light irradiation in the sample with surface hydroxyl groups, while variable changes were observed in samples without surface hydroxyls. Density functional theory (DFT) calculations reveal that the binding energy of Bi-O is drastically influenced by surficial hydroxyl groups, which is intensely correlated to the formation of photoinduced OVs. Moreover, DFT calculations reveal that the adsorbed water molecules are energetically favored to dissociate into separate hydroxyl groups at the OV sites via proton transfer to a neighboring bridging oxygen atom, forming two bridging hydroxyl groups per initial oxygen vacancy. This result is consistent with the experimental observation that the disappearance of photoinduced OVs and the recovery of hydroxyl groups on the surface of BiOCl after exposed to a H2O(g)-rich atmosphere, and finally enables the regeneration of BiOCl photocatalyst. Here, we introduce new insights that the evolution of photoinduced OVs is dependent on surface hydroxyl groups, which will lead to the regeneration of active sites in semiconductors. This work is useful for controllable designs of defective semiconductors for applications in photocatalysis and photovoltaics.

Promoted Fixation of Molecular Nitrogen with Surface Oxygen Vacancies on Plasmon-Enhanced TiO2 Photoelectrodes.

Science.gov (United States)

Li, Chengcheng; Wang, Tuo; Zhao, Zhi-Jian; Yang, Weimin; Li, Jian-Feng; Li, Ang; Yang, Zhilin; Ozin, Geoffrey A; Gong, Jinlong

2018-02-19

A hundred years on, the energy-intensive Haber-Bosch process continues to turn the N 2 in air into fertilizer, nourishing billions of people while causing pollution and greenhouse gas emissions. The urgency of mitigating climate change motivates society to progress toward a more sustainable method for fixing N 2 that is based on clean energy. Surface oxygen vacancies (surface O vac ) hold great potential for N 2 adsorption and activation, but introducing O vac on the very surface without affecting bulk properties remains a great challenge. Fine tuning of the surface O vac by atomic layer deposition is described, forming a thin amorphous TiO 2 layer on plasmon-enhanced rutile TiO 2 /Au nanorods. Surface O vac in the outer amorphous TiO 2 thin layer promote the adsorption and activation of N 2 , which facilitates N 2 reduction to ammonia by excited electrons from ultraviolet-light-driven TiO 2 and visible-light-driven Au surface plasmons. The findings offer a new approach to N 2 photofixation under ambient conditions (that is, room temperature and atmospheric pressure). © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Understanding Oxygen Vacancy Formation, Interaction, Transport, and Strain in SOFC Components via Combined Thermodynamics and First Principles Calculations

Science.gov (United States)

Das, Tridip

Understanding of the vacancy formation, interaction, increasing its concentration and diffusion, and controlling its chemical strain will advance the design of mixed ionic and electronic conductor (MIEC) materials via element doping and strain engineering. This is especially central to improve the performance of the solid oxide fuel cell (SOFC), an energy conversion device for sustainable future. The oxygen vacancy concentration grows exponentially with the temperature at dilute vacancy concentration but not at higher concentration, or even decreases due to oxygen vacancy interaction and vacancy ordered phase change. This limits the ionic conductivity. Using density functional theory (DFT), we provided fundamental understanding on how oxygen vacancy interaction originates in one of the typical MIEC, La1-xSrxFeO3-delta (LSF). The vacancy interaction is determined by the interplay of the charge state of multi-valence ion (Fe), aliovalent doping (La/Sr ratio), the crystal structure, and the oxygen vacancy concentration and/or nonstoichiometry (delta). It was found excess electrons left due to the formation of a neutral oxygen vacancy get distributed to Fe directly connected to the vacancy or to the second nearest neighboring Fe, based on crystal field splitting of Fe 3d orbital in different Fe-O polyhedral coordination. The progressively larger polaron size and anisotropic shape changes with increasing Sr-content resulted in increasing oxygen vacancy interactions, as indicated by an increase in the oxygen vacancy formation energy above a critical delta threshold. This was consistent with experimental results showing that Sr-rich LSF and highly oxygen deficient compositions are prone to oxygen-vacancy-ordering-induced phase transformations, while Sr-poor and oxygen-rich LSF compositions are not. Since oxygen vacancy induced phase transformations, cause a decrease in the mobile oxygen vacancy site fraction (X), both delta and X were predicted as a function of

The Effect of Acceptor and Donor Doping on Oxygen Vacancy Concentrations in Lead Zirconate Titanate (PZT).

Science.gov (United States)

Slouka, Christoph; Kainz, Theresa; Navickas, Edvinas; Walch, Gregor; Hutter, Herbert; Reichmann, Klaus; Fleig, Jürgen

2016-11-22

The different properties of acceptor-doped (hard) and donor-doped (soft) lead zirconate titanate (PZT) ceramics are often attributed to different amounts of oxygen vacancies introduced by the dopant. Acceptor doping is believed to cause high oxygen vacancy concentrations, while donors are expected to strongly suppress their amount. In this study, La 3+ donor-doped, Fe 3+ acceptor-doped and La 3+ /Fe 3+ -co-doped PZT samples were investigated by oxygen tracer exchange and electrochemical impedance spectroscopy in order to analyse the effect of doping on oxygen vacancy concentrations. Relative changes in the tracer diffusion coefficients for different doping and quantitative relations between defect concentrations allowed estimates of oxygen vacancy concentrations. Donor doping does not completely suppress the formation of oxygen vacancies; rather, it concentrates them in the grain boundary region. Acceptor doping enhances the amount of oxygen vacancies but estimates suggest that bulk concentrations are still in the ppm range, even for 1% acceptor doping. Trapped holes might thus considerably contribute to the charge balancing of the acceptor dopants. This could also be of relevance in understanding the properties of hard and soft PZT.

The Effect of Acceptor and Donor Doping on Oxygen Vacancy Concentrations in Lead Zirconate Titanate (PZT

Directory of Open Access Journals (Sweden)

Christoph Slouka

2016-11-01

Full Text Available The different properties of acceptor-doped (hard and donor-doped (soft lead zirconate titanate (PZT ceramics are often attributed to different amounts of oxygen vacancies introduced by the dopant. Acceptor doping is believed to cause high oxygen vacancy concentrations, while donors are expected to strongly suppress their amount. In this study, La3+ donor-doped, Fe3+ acceptor-doped and La3+/Fe3+-co-doped PZT samples were investigated by oxygen tracer exchange and electrochemical impedance spectroscopy in order to analyse the effect of doping on oxygen vacancy concentrations. Relative changes in the tracer diffusion coefficients for different doping and quantitative relations between defect concentrations allowed estimates of oxygen vacancy concentrations. Donor doping does not completely suppress the formation of oxygen vacancies; rather, it concentrates them in the grain boundary region. Acceptor doping enhances the amount of oxygen vacancies but estimates suggest that bulk concentrations are still in the ppm range, even for 1% acceptor doping. Trapped holes might thus considerably contribute to the charge balancing of the acceptor dopants. This could also be of relevance in understanding the properties of hard and soft PZT.

Significant room-temperature ferromagnetism in porous ZnO films: The role of oxygen vacancies

Energy Technology Data Exchange (ETDEWEB)

Hou, Xue; Liu, Huiyuan [College of Physics Science & Information Engineering, Hebei Normal University, Shijiazhuang 050024 (China); Key Laboratory of Advanced Films of Hebei Province, Shijiazhuang 050024 (China); Sun, Huiyuan, E-mail: huiyuansun@126.com [College of Physics Science & Information Engineering, Hebei Normal University, Shijiazhuang 050024 (China); Key Laboratory of Advanced Films of Hebei Province, Shijiazhuang 050024 (China); Liu, Lihu; Jia, Xiaoxuan [College of Physics Science & Information Engineering, Hebei Normal University, Shijiazhuang 050024 (China); Key Laboratory of Advanced Films of Hebei Province, Shijiazhuang 050024 (China)

2015-10-15

Graphical abstract: - Highlights: • Porous ZnO films were deposited on porous anodic alumina substrates. • Significant ferromagnetism (FM) has been observed in porous ZnO films (110 emu/cm{sup 3}). • The strong magnetic anisotropy was observed in the porous ZnO films. • The origin of FM is attributed to the oxygen vacancy with a local magnetic moment. - Abstract: Pure porous ZnO films were prepared by direct current reactive magnetron sputtering on porous anodic alumina substrates. Remarkably large room-temperature ferromagnetism was observed in the films. The highest saturation moment along the out-of-plane direction was about 110 emu/cm{sup 3}. Experimental and theoretical results suggested that the oxygen vacancies and the unique porous structure of the films are responsible for the large ferromagnetism. There are two modes of coupling between oxygen vacancies in the porous ZnO films: (i) exchange interactions directly between the oxygen vacancies and (ii) with the mediation of conduction electrons. In addition, it was found that the magnetic moment of ZnO films can be changed by tuning the concentration of oxygen vacancies. These observations may be useful in the development of ZnO-based spintronics devices.

Vacancy clusters at nanoparticle surfaces

Energy Technology Data Exchange (ETDEWEB)

Xu, J.; Moxom, J.; Somieski, B.; White, C.W. [Oak Ridge National Lab., TN (United States); Mills, A.P. Jr. [Bell Labs., Lucent Technologies, Murray Hill, NJ (United States); Suzuki, R.; Ishibashi, S. [Electrotechnical Lab., Tsukuba, Ibaraki (Japan); Ueda, A.; Henderson, D. [Physics Dept., Fisk Univ., Nashville, TN (United States)

2001-07-01

We detect vacancy clusters at Au nanoparticle surfaces using a combination of positron lifetime spectroscopy, 1- detector, and 2-detector measurements of Doppler broadening of annihilation radiation. Gold nanoparticles are formed by MeV implantation of gold ions into MgO (100) followed by annealing. Clusters of two Mg and two O vacancies (v{sub 4}) are attached to the gold nanoparticle surfaces within the projected range (R{sub p}). (orig.)

Vacancy clusters at nanoparticle surfaces

International Nuclear Information System (INIS)

Xu, J.; Moxom, J.; Somieski, B.; White, C.W.; Mills, A.P. Jr.; Suzuki, R.; Ishibashi, S.; Ueda, A.; Henderson, D.

2001-01-01

We detect vacancy clusters at Au nanoparticle surfaces using a combination of positron lifetime spectroscopy, 1- detector, and 2-detector measurements of Doppler broadening of annihilation radiation. Gold nanoparticles are formed by MeV implantation of gold ions into MgO (100) followed by annealing. Clusters of two Mg and two O vacancies (v 4 ) are attached to the gold nanoparticle surfaces within the projected range (R p ). (orig.)

Anisotropic chemical strain in cubic ceria due to oxygen-vacancy-induced elastic dipoles.

Science.gov (United States)

Das, Tridip; Nicholas, Jason D; Sheldon, Brian W; Qi, Yue

2018-06-06

Accurate characterization of chemical strain is required to study a broad range of chemical-mechanical coupling phenomena. One of the most studied mechano-chemically active oxides, nonstoichiometric ceria (CeO2-δ), has only been described by a scalar chemical strain assuming isotropic deformation. However, combined density functional theory (DFT) calculations and elastic dipole tensor theory reveal that both the short-range bond distortions surrounding an oxygen-vacancy and the long-range chemical strain are anisotropic in cubic CeO2-δ. The origin of this anisotropy is the charge disproportionation between the four cerium atoms around each oxygen-vacancy (two become Ce3+ and two become Ce4+) when a neutral oxygen-vacancy is formed. Around the oxygen-vacancy, six of the Ce3+-O bonds elongate, one of the Ce3+-O bond shorten, and all seven of the Ce4+-O bonds shorten. Further, the average and maximum chemical strain values obtained through tensor analysis successfully bound the various experimental data. Lastly, the anisotropic, oxygen-vacancy-elastic-dipole induced chemical strain is polarizable, which provides a physical model for the giant electrostriction recently discovered in doped and non-doped CeO2-δ. Together, this work highlights the need to consider anisotropic tensors when calculating the chemical strain induced by dilute point defects in all materials, regardless of their symmetry.

A Unifying Perspective on Oxygen Vacancies in Wide Band Gap Oxides.

Science.gov (United States)

Linderälv, Christopher; Lindman, Anders; Erhart, Paul

2018-01-04

Wide band gap oxides are versatile materials with numerous applications in research and technology. Many properties of these materials are intimately related to defects, with the most important defect being the oxygen vacancy. Here, using electronic structure calculations, we show that the charge transition level (CTL) and eigenstates associated with oxygen vacancies, which to a large extent determine their electronic properties, are confined to a rather narrow energy range, even while band gap and the electronic structure of the conduction band vary substantially. Vacancies are classified according to their character (deep versus shallow), which shows that the alignment of electronic eigenenergies and CTL can be understood in terms of the transition between cavity-like localized levels in the large band gap limit and strong coupling between conduction band and vacancy states for small to medium band gaps. We consider both conventional and hybrid functionals and demonstrate that the former yields results in very good agreement with the latter provided that band edge alignment is taken into account.

Simulation of the Atomic and Electronic Structure of Oxygen Vacancies and Polyvacancies in ZrO2

Science.gov (United States)

Perevalov, T. V.

2018-03-01

Cubic, tetragonal, and monoclinic phases of zirconium oxide with oxygen vacancies and polyvacancies are studied by quantum chemical modeling of the atomic and electronic structure. It is demonstrated that an oxygen vacancy in ZrO2 may act as both an electron trap and a hole one. An electron added to the ZrO2 structure with an oxygen vacancy is distributed between two neighboring Zr atoms and is a bonding orbital by nature. It is advantageous for each subsequent O vacancy to form close to the already existing ones; notably, one Zr atom has no more than two removed O atoms related to it. Defect levels from oxygen polyvacancies are distributed in the bandgap with preferential localization in the vicinity of the oxygen monovacancy level.

Interaction of oxygen with zirconia surface

International Nuclear Information System (INIS)

Ivankiv, L.I.; Ketsman, I.V.

1999-01-01

The influence of surface heat treatment, electron (50-800) eV irradiation and UV (180-300) nM illumination of adsorption system on the state of oxygen adsorbed on zirconia surface have been investigated. On the basis of experimental results obtained by investigation of photon emission accompanying oxygen adsorption (AL) and TPD data existence of adsorption sites on the surface is suggested on which irreversible dissociative adsorption of oxygen occurs. These very sites are associated with emission processes Conclusion is made that the only type of adsorption sites connected with anion vacancy is present on zirconia surface and this is its charge state that determines the state of adsorbed oxygen. One of the important mechanisms by which the electron and UV photon excitation affects the adsorption interaction is the change of the charge state of the adsorption site

Synthesis of surface oxygen-deficient BiPO{sub 4} nanocubes with enhanced visible light induced photocatalytic activity

Energy Technology Data Exchange (ETDEWEB)

Shi, Bingtao; Yin, Haoyong; Li, Tao; Gong, Jianying; Lv, Shumei; Nie, Qiulin, E-mail: yhy@hdu.edu.cn [College of Materials & Environmental Engineering, Hangzhou Dianzi University, Hangzhou (China)

2017-05-15

The visible light driven BiPO{sub 4} nanocubes with sufficient surface oxygen deficiency were fabricated by a hydrothermal process and subsequently ultrasonic assistant Fe reduction process. The products were characterized by XRD, DRS, XPS, SEM and TEM which showed that the BiPO{sub 4} had cuboid-like shape with a smooth surface and clear edges and the oxygen vacancies were successfully introduced on the surface of the BiPO{sub 4} nanocubes. The as prepared oxygen-deficient BiPO{sub 4} nanocubes showed greatly enhanced visible light induced photocatalytic activity in degradation of Rhodamine B. The enhanced photocatalytic performance and expanded visible light response of BiPO{sub 4} may be due to the introduction of surface oxygen vacancies which can generate the oxygen vacancies mid-gap states lower to the conduction band of BiPO{sub 4}. (author)

Modeling of the structure and properties of oxygen vacancies in amorphous silica

International Nuclear Information System (INIS)

Mukhopadhyay, Sanghamitra; Sushko, Peter V.; Stoneham, A. Marshall; Shluger, Alexander L.

2004-01-01

We used an embedded cluster method to predict and characterize possible structural types of neutral and positively charged oxygen vacancies in amorphous silica. Defects were treated at 70 different oxygen sites of continuous random network amorphous structure generated using classical molecular dynamics. The neutral vacancies are characterized by a wide distribution of formation energies and structural parameters. Our modeling predicts the two major structural types of positively charged vacancies (E ' centers): dimer and dangling bond centers. The local structure of both types of centers depends on the medium range structure of the surrounding amorphous network. The majority of the dangling bond centers are unpuckered. We used structural 'fingerprints' derived from similar calculations of oxygen vacancy type centers in quartz and from experiment to find two other structural types of dangling bond centers: the puckered configuration and the back-projected configuration of E ' centers. In each case we find a distribution of both structural and EPR parameters. However, the average values of the EPR parameters for all dangling bond configurations are very similar. The structural criteria which favor the formation of different types of centers in the original amorphous structure are formulated in terms of the average Si-O distance of oxygen ion with its two neighboring silicon ions

Pinning by oxygen vacancies in high-Tc superconductors

International Nuclear Information System (INIS)

Chudnovsky, E.M.

1990-01-01

It is shown that recent data of Murray et al. on spatial correlations in flux lattices of Bi-Sr-Ca-Cu-O (BSCCO) may be explained if one assumes that 1% of oxygen atoms in CuO 2 layers are missing. This estimate, being in remarkable agreement with that deduced by Kes and van der Beek from ac-susceptibility measurements, provides strong confidence that oxygen vacancies are the major source of pinning in BSCCO

Defective TiO2 with oxygen vacancies: synthesis, properties and photocatalytic applications

Science.gov (United States)

Pan, Xiaoyang; Yang, Min-Quan; Fu, Xianzhi; Zhang, Nan; Xu, Yi-Jun

2013-04-01

Titanium dioxide (TiO2), as an important semiconductor metal oxide, has been widely investigated in the field of photocatalysis. The properties of TiO2, including its light absorption, charge transport and surface adsorption, are closely related to its defect disorder, which in turn plays a significant role in the photocatalytic performance of TiO2. Among all the defects identified in TiO2, oxygen vacancy is one of the most important and is supposed to be the prevalent defect in many metal oxides, which has been widely investigated both by theoretical calculations and experimental characterizations. Here, we give a short review on the existing strategies for the synthesis of defective TiO2 with oxygen vacancies, and the defect related properties of TiO2 including structural, electronic, optical, dissociative adsorption and reductive properties, which are intimately related to the photocatalytic performance of TiO2. In particular, photocatalytic applications with regard to defective TiO2 are outlined. In addition, we offer some perspectives on the challenge and new direction for future research in this field. We hope that this tutorial minireview would provide some useful contribution to the future design and fabrication of defective semiconductor-based nanomaterials for diverse photocatalytic applications.Titanium dioxide (TiO2), as an important semiconductor metal oxide, has been widely investigated in the field of photocatalysis. The properties of TiO2, including its light absorption, charge transport and surface adsorption, are closely related to its defect disorder, which in turn plays a significant role in the photocatalytic performance of TiO2. Among all the defects identified in TiO2, oxygen vacancy is one of the most important and is supposed to be the prevalent defect in many metal oxides, which has been widely investigated both by theoretical calculations and experimental characterizations. Here, we give a short review on the existing strategies for the

Oxygen vacancies: The origin of n -type conductivity in ZnO

Science.gov (United States)

Liu, Lishu; Mei, Zengxia; Tang, Aihua; Azarov, Alexander; Kuznetsov, Andrej; Xue, Qi-Kun; Du, Xiaolong

2016-06-01

Oxygen vacancy (VO) is a common native point defect that plays crucial roles in determining the physical and chemical properties of metal oxides such as ZnO. However, fundamental understanding of VO is still very sparse. Specifically, whether VO is mainly responsible for the n -type conductivity in ZnO has been still unsettled in the past 50 years. Here, we report on a study of oxygen self-diffusion by conceiving and growing oxygen-isotope ZnO heterostructures with delicately controlled chemical potential and Fermi level. The diffusion process is found to be predominantly mediated by VO. We further demonstrate that, in contrast to the general belief of their neutral attribute, the oxygen vacancies in ZnO are actually +2 charged and thus responsible for the unintentional n -type conductivity as well as the nonstoichiometry of ZnO. The methodology can be extended to study oxygen-related point defects and their energetics in other technologically important oxide materials.

Segregation and Migration of the Oxygen Vacancies in the 3 (111) Tilt Grain Boundaries of Ceria

Energy Technology Data Exchange (ETDEWEB)

Yuan, Fenglin [Univ. of Tennessee, Knoxville, TN (United States); Liu, Bin [Univ. of Tennessee, Knoxville, TN (United States); Zhang, Yanwen [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Weber, William J. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

2016-03-01

In nanocrystalline materials, defect-grain boundary (GB) interaction plays a key role in determining the structure stability, as well as size-dependent ionic, electronic, magnetic and chemical properties. In this study, we systematically investigated using density functional theory segregation and migration of oxygen vacancies at the Σ3 [110] / (111) grain boundary of ceria. Three oxygen layers near the GB are predicted to be segregation sites for oxygen vacancies. Moreover, the presence of oxygen vacancies stabilizes this tilt GB at a low Fermi level and/or oxygen poor conditions. An atomic strain model was proposed to rationalize layer dependency of the relaxation energy for +2 charged oxygen vacancy. The structural origin of large relaxation energies at layers 1 and 2 was determined to be free-volume space that induces ion relaxation towards the GB. Our results not only pave the way for improving the oxygen transport near GBs of ceria, but also provide important insights into engineering the GB structure for better ionic, magnetic and chemical properties of nanocrystalline ceria.

Strain-induced oxygen vacancies in ultrathin epitaxial CaMnO3 films

Science.gov (United States)

Chandrasena, Ravini; Yang, Weibing; Lei, Qingyu; Delgado-Jaime, Mario; de Groot, Frank; Arenholz, Elke; Kobayashi, Keisuke; Aschauer, Ulrich; Spaldin, Nicola; Xi, Xiaoxing; Gray, Alexander

Dynamic control of strain-induced ionic defects in transition-metal oxides is considered to be an exciting new avenue towards creating materials with novel electronic, magnetic and structural properties. Here we use atomic layer-by-layer laser molecular beam epitaxy to synthesize high-quality ultrathin single-crystalline CaMnO3 films with systematically varying coherent tensile strain. We then utilize a combination of high-resolution soft x-ray absorption spectroscopy and bulk-sensitive hard x-ray photoemission spectroscopy in conjunction with first-principles theory and core-hole multiplet calculations to establish a direct link between the coherent in-plane strain and the oxygen-vacancy content. We show that the oxygen vacancies are highly mobile, which necessitates an in-situ-grown capping layer in order to preserve the original strain-induced oxygen-vacancy content. Our findings open the door for designing and controlling new ionically active properties in strongly-correlated transition-metal oxides.

Oxygen vacancy defects in Ta{sub 2}O{sub 5} showing long-range atomic re-arrangements

Energy Technology Data Exchange (ETDEWEB)

Guo, Yuzheng; Robertson, John [Engineering Department, Cambridge University, Cambridge CB2 1PZ (United Kingdom)

2014-03-17

The structure, formation energy, and energy levels of the various oxygen vacancies in Ta{sub 2}O{sub 5} have been calculated using the λ phase model. The intra-layer vacancies give rise to unusual, long-range bonding rearrangements, which are different for each defect charge state. The 2-fold coordinated intra-layer vacancy is the lowest cost vacancy and forms a deep level 1.5 eV below the conduction band edge. The 3-fold intra-layer vacancy and the 2-fold inter-layer vacancy are higher cost defects, and form shallower levels. The unusual bonding rearrangements lead to low oxygen migration barriers, which are useful for resistive random access memory applications.

In Situ Observation of Oxygen Vacancy Dynamics and Ordering in the Epitaxial LaCoO3 System.

Science.gov (United States)

Jang, Jae Hyuck; Kim, Young-Min; He, Qian; Mishra, Rohan; Qiao, Liang; Biegalski, Michael D; Lupini, Andrew R; Pantelides, Sokrates T; Pennycook, Stephen J; Kalinin, Sergei V; Borisevich, Albina Y

2017-07-25

Vacancy dynamics and ordering underpin the electrochemical functionality of complex oxides and strongly couple to their physical properties. In the field of the epitaxial thin films, where connection between chemistry and film properties can be most clearly revealed, the effects related to oxygen vacancies are attracting increasing attention. In this article, we report a direct, real-time, atomic level observation of the formation of oxygen vacancies in the epitaxial LaCoO 3 thin films and heterostructures under the influence of the electron beam utilizing scanning transmission electron microscopy (STEM). In the case of LaCoO 3 /SrTiO 3 superlattice, the formation of the oxygen vacancies is shown to produce quantifiable changes in the interatomic distances, as well as qualitative changes in the symmetry of the Co sites manifested as off-center displacements. The onset of these changes was observed in both the [100] pc and [110] pc orientations in real time. Additionally, annular bright field images directly show the formation of oxygen vacancy channels along [110]pc direction. In the case of 15 u.c. LaCoO 3 thin film, we observe the sequence of events during beam-induced formation of oxygen vacancy ordered phases and find them consistent with similar processes in the bulk. Moreover, we record the dynamics of the nucleation, growth, and defect interaction at the atomic scale as these transformations happen. These results demonstrate that we can track dynamic oxygen vacancy behavior with STEM, generating atomic-level quantitative information on phase transformation and oxygen diffusion.

Sn doped TiO{sub 2} nanotube with oxygen vacancy for highly efficient visible light photocatalysis

Energy Technology Data Exchange (ETDEWEB)

Li, Jinliang; Xu, Xingtao [Engineering Research Center for Nanophotonics & Advanced Instrument, Ministry of Education, Shanghai Key Laboratory of Magnetic Resonance, School of Physics and Materials Science, Department of Physics, East China Normal University, Shanghai 200062 (China); Liu, Xinjuan [Institute of Coordination Bond Metrology and Engineering, College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018 (China); Yu, Caiyan; Yan, Dong; Sun, Zhuo [Engineering Research Center for Nanophotonics & Advanced Instrument, Ministry of Education, Shanghai Key Laboratory of Magnetic Resonance, School of Physics and Materials Science, Department of Physics, East China Normal University, Shanghai 200062 (China); Pan, Likun, E-mail: lkpan@phy.ecnu.edu.cn [Engineering Research Center for Nanophotonics & Advanced Instrument, Ministry of Education, Shanghai Key Laboratory of Magnetic Resonance, School of Physics and Materials Science, Department of Physics, East China Normal University, Shanghai 200062 (China)

2016-09-15

Sn doped TiO{sub 2} nanotube with oxygen vacancy (V{sub o}-Sn−TiO{sub 2}) was successfully synthesized via a facile hydrothermal process and subsequent annealing in nitrogen atmosphere. The morphology, structure and photocatalytic performance of V{sub o}-Sn−TiO{sub 2} in the degradation of nitrobenzene were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, UV–vis absorption spectroscopy, nitrogen adsorption-desorption and electrochemical impedance spectra, respectively. The inner diameter, outer diameter and specific surface area of V{sub o}-Sn−TiO{sub 2} are about 5 nm, 15 nm and 235.54 m{sup 2} g{sup −1}, respectively. The experimental results show that the V{sub o}-Sn−TiO{sub 2} exhibits excellent photocatalytic performance with a maximum degradation rate of 92% in 300 min for nitrobenzene and 94% in 100 min for Rhodamine B and corresponding mineralization rates of 68% and 70% under visible light irradiation. The improved photocatalytic performance is ascribed to the enhanced light absorption and specific surface area as well as the reduced electron-hole pair recombination with the presence of oxygen vacancy and Sn doping in the TiO{sub 2} nanotube. - Highlights: • Photocatalysis is an environmental-friendly technology for nitrobenzene removal. • Sn doped TiO{sub 2} nanotube with oxygen vacancy is fabricated for the first time. • It exhibits excellent photocatalytic performance in degradation of nitrobenzene. • A high degradation rate of 92% is achieved under visible light irradiation.

Introduction of oxygen vacancies and fluorine into TiO2 nanoparticles by co-milling with PTFE

International Nuclear Information System (INIS)

Senna, Mamoru; Šepelák, Vladimir; Shi, Jianmin; Bauer, Benjamin; Feldhoff, Armin; Laporte, Vincent; Becker, Klaus-Dieter

2012-01-01

Solid-state processes of introducing oxygen vacancies and transference of fluorine to n-TiO 2 nanoparticles by co-milling with poly(tetrafluoroethylene) (PTFE) powder were examined by diffuse reflectance spectroscopy (DRS) of UV, visual, near- and mid-IR regions, thermal analyses (TG-DTA), energy-dispersive X-ray spectroscopy (EDXS), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD). The broad absorption peak at around 8800 cm −1 (1140 nm) was attributed to the change in the electronic states, viz. electrons trapped at the oxygen vacancies (Vo) and d–d transitions of titanium ions. Incorporation of fluorine into n-TiO 2 was concentrated at the near surface region and amounted to ca. 40 at% of the total fluorine in PTFE, after co-milling for 3 h, as confirmed by the F1s XPS spectrum. The overall atomic ratio, F/Ti, determined by EDXS was 0.294. By combining these analytical results, a mechanism of the present solid state processes at the boundary between PTFE and n-TiO 2 was proposed. The entire process is triggered by the partial oxidative decomposition of PTFE. This is accompanied by the abstraction of oxygen atoms from the n-TiO 2 lattices. Loss of the oxygen atoms results in the formation of the diverse states of locally distorted coordination units of titania, i.e. TiO 6−n Vo n , located at the near surface region. This leads subsequent partial ligand exchange between F and O, to incorporate fluorine preferentially to the near surface region of n-TiO 2 particles, where local non-crystalline states predominate. - Graphical abstract: Scheme of the reaction processes: (a) pristine mixture, (b) oxygen abstraction from TiO 2 and (c) fluorine migration from PTFE to TiO 2 . Highlights: Transfer of fluorine from PTFE to n-TiO 2 in a dry solid state process was confirmed. ► 40% of F in PTFE was incorporated to the near surface region of n-TiO 2 nanoparticles. ► The transfer process is

Density functional study of NO adsorption on undefected and oxygen defective Au–BaO(1 0 0) surfaces

Energy Technology Data Exchange (ETDEWEB)

Añez, Rafael, E-mail: ranez@ivic.gob.ve [Laboratorio de Química Física y Catálisis Computacional, Centro de Química, Instituto Venezolano de Investigaciones Científicas, Apartado, 21827 Caracas (Venezuela, Bolivarian Republic of); Sierraalta, Aníbal; Bastardo, Anelisse [Laboratorio de Química Física y Catálisis Computacional, Centro de Química, Instituto Venezolano de Investigaciones Científicas, Apartado, 21827 Caracas (Venezuela, Bolivarian Republic of); Coll, David [Laboratorio de Físico Química Teórica de Materiales, Centro de Química, Instituto Venezolano de Investigaciones Científicas, Apartado, 21827 Caracas (Venezuela, Bolivarian Republic of); Garcia, Belkis [Instituto Universitario de Tecnología de Valencia IUTVAL, Valencia, Edo. Carabobo (Venezuela, Bolivarian Republic of)

2014-07-01

A periodic density functional approach has been used in order to explore the interaction of NO with undoped and Au doped BaO(1 0 0) surface. Due to oxygen vacancies increase the interaction between the doping metal and the surface, F{sub S} and F{sub S}{sup +} vacancies were studied and compared with the results obtained on the undefected doped BaO(1 0 0). Our results indicate that the high basicity of the BaO surface, besides the electron density changes produced by the oxygen vacancies, modify considerably how the Au atom interacts with the surface increasing the ionic character of the interaction. F{sub S} vacancy shows to be a promise center to activate de NO bond on the BaO(1 0 0) surface.

Controlled oxygen vacancy induced p-type conductivity in HfO{sub 2-x} thin films

Energy Technology Data Exchange (ETDEWEB)

Hildebrandt, Erwin; Kurian, Jose; Mueller, Mathis M.; Kleebe, Hans-Joachim; Alff, Lambert [Institute of Materials Science, Technische Universitaet Darmstadt, 64287 Darmstadt (Germany); Schroeder, Thomas [IHP, 15236 Frankfurt/Oder (Germany)

2011-09-12

We have synthesized highly oxygen deficient HfO{sub 2-x} thin films by controlled oxygen engineering using reactive molecular beam epitaxy. Above a threshold value of oxygen vacancies, p-type conductivity sets in with up to 6 times 10{sup 21} charge carriers per cm{sup 3}. At the same time, the band-gap is reduced continuously by more than 1 eV. We suggest an oxygen vacancy induced p-type defect band as origin of the observed behavior.

Correlating oxygen vacancies and phase ratio/interface with efficient photocatalytic activity in mixed phase TiO2

International Nuclear Information System (INIS)

Verma, Ranjana; Samdarshi, S.K.

2015-01-01

Graphical abstract: The correlation of interfacial behavior and oxygen vacancies in mixed phase titania nanoparticles on their performance as photocatalyst has been investigated to explain the impact of photoactivity under UV and visible irradiation compared to pristine counterparts. The defects at the junction effectively reduce the band gap as well decrease the carrier recombination to enhance the photocatalytic activity. - Highlights: • Pristine and mixed phases (A/R ratio) TiO 2 synthesized by sol gel route. • Photoactivity variation has been correlated with the changes in the phase ratio. • Enhanced UV and visible activity attributable to oxygen vacancy present at the interface. • Role of A/R ratio and oxygen vacancy in the photoactivity of mixed TiO 2 depicted through a model. - Abstract: The photocatalytic activity is a result of the synergy of a succession of phenomena-photogeneration, separation, and participation of the charge carriers in redox reaction at the catalyst surface. While the extent of photogeneration is assessable in terms of absorption spectrum (band gap), the redox reaction can be correlated to specific surface area. However the respective change in the photocatalytic activity has not been rationally and consistently correlated with the above mentioned parameters. A satisfactory explanation of suppression of recombination based on separation of carriers due to differential mobility/diffusivity in the material phase(s) and/or intrinsic potential barrier exists but its correlation with common identifiable parameter/characteristics is still elusive. This paper attempts to address this issue by correlating the carrier separation with the phase ratio (phase interface) in mixed phase titania and generalizing it with the presence of oxygen vacancy at the phase interface. It essentially appears to complete the quest for identifiable parameters in the sequence of phenomena, which endow a photocatalyst with an efficient activity level. It has

Adsorption and magnetism of bilayer graphene on the MnO polar surface with oxygen vacancies in the interface: First principles study

Science.gov (United States)

Ilyasov, Victor V.; Ershov, Igor V.; Popova, Inna G.; Pham, Khang D.; Nguyen, Chuong V.

2018-05-01

In this paper, we investigate systematically the structural, electronic, magnetic and adsorption properties of Bernal-stacked bilayer graphene on MnO(111) surface terminated by an oxygen atom, as a function of nonstoichiometric composition of the BLG/MnOx(111) interface. For additional functionalization of the BLG/MnOx(111) system, we also studied the adsorption properties of oxygen adsorbed on the BLG/MnOx(111) interface. Our results showed that the BLG is bound to the MnOx(111) substrate by the weak interaction for both spin-up and spin-down. Furthermore, we found that BLG adsorbed on the MnOx(111) substrate with a reduced oxygen symmetry in the interface is accompanied with a downshift of the Fermi level, which identifies the band structure of BLG as a p-type semiconductor. Upon interaction between BLG and MnOx(111) substrate, a forbidden gap of about 350 meV was opened between its bonding and antibonding π bands. A forbidden gap and the local magnetic moments in bilayer graphene can be controlled by changing the oxygen nonstoichometry or by oxygen adsorption. Additionally, magnetism has been predicted in the bilayer graphene adsorbed on the polar MnOx(111) surface with oxygen vacancies in the BLG/MnOx(111) interface, and its nature has also been discussed in this work. These results showed that the adsorption of bilayer graphene on the MnO(111) substrate can be used for developing novel generation of electronic and spintronic devices.

Spin-dependent recombination involving oxygen-vacancy complexes in silicon

Science.gov (United States)

Franke, David P.; Hoehne, Felix; Vlasenko, Leonid S.; Itoh, Kohei M.; Brandt, Martin S.

2014-05-01

Spin-dependent relaxation and recombination processes in γ-irradiated n-type Czochralski-grown silicon are studied using continuous wave (cw) and pulsed electrically detected magnetic resonance (EDMR). Two processes involving the SL1 center, the neutral excited triplet state of the oxygen-vacancy complex, are observed which can be separated by their different dynamics. One of the processes is the relaxation of the excited SL1 state to the ground state of the oxygen-vacancy complex, the other a charge transfer between 31P donors and SL1 centers forming close pairs, as indicated by electrically detected electron double resonance. For both processes, the recombination dynamics is studied with pulsed EDMR techniques. We demonstrate the feasibility of true zero-field cw and pulsed EDMR for spin-1 systems and use this to measure the lifetimes of the different spin states of SL1 also at vanishing external magnetic field.

Hydrogen peroxide reduction in the oxygen vacancies of ZnO nanotubes

International Nuclear Information System (INIS)

Peyghan, Ali Ahmadi; Laeen, Shima Parizad; Aslanzadeh, Saeed Amir; Moradi, Morteza

2014-01-01

The adsorption of a H 2 O 2 molecule on the pristine and O-vacancy defected ZnO nanotubes was investigated by means of density functional calculations. It was found that the molecule prefers to attach to two zinc atoms of the tube from its two oxygen atoms with the adsorption energy of 254.1 kJ/mol. Attachment of the H 2 O 2 to the wall of the tube does not have any significant influence on its highest occupied molecular orbital/lowest unoccupied molecular orbital gap (E g ). The presence of oxygen vacancy defect causes a decrease in the E g of the tube and, as a consequence, may cause an increase in the conductivity of the tube. The zinc atoms of the defect are more reactive toward H 2 O 2 reduction to H 2 O than perfect ones with the adsorption energy of 617.4 kJ/mol. During the adsorption process, the H 2 O 2 was reoriented in such a way that its O atom has diffused into vacancy site, so that O-O and O-H bonds of the molecule were dissociated and an H 2 O is formed. Thus, we think that ZnO-NTs may be a candidate for electrochemical reduction and detection of H 2 O 2 . - Highlights: • H 2 O 2 adsorption on pristine and O-vacancy defected ZnO nanotubes was studied by DFT. • H 2 O 2 does not have any significant influence on the gap of the tube. • Presence of oxygen vacancy defect causes a decrease in the gap of the tube. • ZnO nanotubes may be a candidate for electrochemical reduction and detection of H 2 O 2

Control of oxygen vacancies and Ce+3 concentrations in doped ceria nanoparticles via the selection of lanthanide element

International Nuclear Information System (INIS)

Shehata, N.; Meehan, K.; Hudait, M.; Jain, N.

2012-01-01

The effect of lanthanides that have positive association energies with oxygen vacancies, such as samarium and neodymium, and the elements with negative association energies, such as holmium and erbium, on ionization state of cerium and, consequentially, the oxygen vacancy concentration in doped ceria nanoparticles are investigated in this article. Structural and optical characterizations of the doped and undoped ceria nanoparticles, synthesized using chemical precipitation, are carried out using transmission electron microscopy, X-ray diffractometry, optical absorption spectroscopy, and fluorescence spectroscopy. It is deduced that the negative association energy dopants decrease the conversion of Ce +4 into Ce +3 and, hence, scavenge the oxygen vacancies, evidenced by the observed increase in the allowed direct bandgap, decrease in the integrated fluorescence intensity, and increased the size of doped nanoparticles. The opposite trends are obtained when the positive association dopants are used. It is concluded that the determining factor as to whether a lanthanide dopant in ceria acts as a generator or scavenger of oxygen vacancies in ceria nanoparticles is the sign of the association energy between the element and the oxygen vacancies. The ability to tailor the ionization state of cerium and the oxygen vacancy concentration in ceria has applications in a broad range of fields, which include catalysis, biomedicine, electronics, and environmental sensing.

First-principles studies on vacancy-modified interstitial diffusion mechanism of oxygen in nickel, associated with large-scale atomic simulation techniques

International Nuclear Information System (INIS)

Fang, H. Z.; Shang, S. L.; Wang, Y.; Liu, Z. K.; Alfonso, D.; Alman, D. E.; Shin, Y. K.; Zou, C. Y.; Duin, A. C. T. van; Lei, Y. K.; Wang, G. F.

2014-01-01

This paper is concerned with the prediction of oxygen diffusivities in fcc nickel from first-principles calculations and large-scale atomic simulations. Considering only the interstitial octahedral to tetrahedral to octahedral minimum energy pathway for oxygen diffusion in fcc lattice, greatly underestimates the migration barrier and overestimates the diffusivities by several orders of magnitude. The results indicate that vacancies in the Ni-lattice significantly impact the migration barrier of oxygen in nickel. Incorporation of the effect of vacancies results in predicted diffusivities consistent with available experimental data. First-principles calculations show that at high temperatures the vacancy concentration is comparable to the oxygen solubility, and there is a strong binding energy and a redistribution of charge density between the oxygen atom and vacancy. Consequently, there is a strong attraction between the oxygen and vacancy in the Ni lattice, which impacts diffusion

Oxygen vacancy-induced ferromagnetism in un-doped ZnO thin films

Science.gov (United States)

Zhan, Peng; Wang, Weipeng; Liu, Can; Hu, Yang; Li, Zhengcao; Zhang, Zhengjun; Zhang, Peng; Wang, Baoyi; Cao, Xingzhong

2012-02-01

ZnO films became ferromagnetic when defects were introduced by thermal-annealing in flowing argon. This ferromagnetism, as shown by the photoluminescence measurement and positron annihilation analysis, was induced by the singly occupied oxygen vacancy with a saturated magnetization dependent positively on the amount of this vacancy. This study clarified the origin of the ferromagnetism of un-doped ZnO thin films and provides possibly an alternative way to prepare ferromagnetic ZnO films.

Evidence for oxygen vacancy or ferroelectric polarization induced switchable diode and photovoltaic effects in BiFeO3 based thin films

International Nuclear Information System (INIS)

Guo Yiping; Guo Bing; Dong Wen; Li Hua; Liu Hezhou

2013-01-01

The diode and photovoltaic effects of BiFeO 3 and Bi 0.9 Sr 0.1 FeO 3−δ polycrystalline thin films were investigated by poling the films with increased magnitude and alternating direction. It was found that both electromigration of oxygen vacancies and polarization flipping are able to induce switchable diode and photovoltaic effects. For the Bi 0.9 Sr 0.1 FeO 3−δ thin films with high oxygen vacancy concentration, reversibly switchable diode and photovoltaic effects can be observed due to the electromigration of oxygen vacancies under an electric field much lower than its coercive field. However, for the pure BiFeO 3 thin films with lower oxygen vacancy concentration, the reversibly switchable diode and photovoltaic effect is hard to detect until the occurrence of polarization flipping. The switchable diode and photovoltaic effects can be explained well using the concepts of Schottky-like barrier-to-Ohmic contacts resulting from the combination of oxygen vacancies and polarization. The sign of photocurrent could be independent of the direction of polarization when the modulation of the energy band induced by oxygen vacancies is large enough to offset that induced by polarization. The photovoltaic effect induced by the electromigration of oxygen vacancies is unstable due to the diffusion of oxygen vacancies or the recombination of oxygen vacancies with hopping electrons. Our work provides deep insights into the nature of diode and photovoltaic effects in ferroelectric films, and will facilitate the advanced design of switchable devices combining spintronic, electronic, and optical functionalities. (paper)

Effects of oxygen vacancies on the structural and optical properties of β-Ga2O3.

Science.gov (United States)

Dong, Linpeng; Jia, Renxu; Xin, Bin; Peng, Bo; Zhang, Yuming

2017-01-09

The structural, electronic, and optical properties of β-Ga 2 O 3 with oxygen vacancies are studied by employing first-principles calculations based on density function theory. Based on the defects formation energies, we conclude the oxygen vacancies are most stable in their fully charge states. The electronic structures and optical properties of β-Ga 2 O 3 are calculated by Generalized Gradient Approximation + U formalisms with the Hubbard U parameters set 7.0 eV and 8.5 eV for Ga and O ions, respectively. The calculated bandgap is 4.92 eV, which is consistent with the experimental value. The static real dielectric constants of the defective structures are increased compared with the intrinsic one, which is attributed to the level caused by the Ga-4s states in the bandgap. Extra peaks are introduced in the absorption spectra, which are related to Ga-4s and O-2p states. Experimentally, β-Ga 2 O 3 films are deposited under different O 2 volume percentage with ratio-frequency magnetron sputtering method. The measured results indicate that oxygen vacancies can induce extra emission peaks in the photoluminescence spectrum, the location of these peaks are close to the calculated results. Extra O 2 can increase the formation energies of oxygen vacancies and thus reduce oxygen vacancies in β-Ga 2 O 3 .

High temperature thermoelectric properties of strontium titanate thin films with oxygen vacancy and niobium doping

KAUST Repository

Sarath Kumar, S. R.; Barasheed, Abeer Z.; Alshareef, Husam N.

2013-01-01

We report the evolution of high temperature thermoelectric properties of SrTiO3 thin films doped with Nb and oxygen vacancies. Structure-property relations in this important thermoelectric oxide are elucidated and the variation of transport properties with dopant concentrations is discussed. Oxygen vacancies are incorporated during growth or annealing in Ar/H2 above 800 K. An increase in lattice constant due to the inclusion of Nb and oxygen vacancies is found to result in an increase in carrier density and electrical conductivity with simultaneous decrease in carrier effective mass and Seebeck coefficient. The lattice thermal conductivity at 300 K is found to be 2.22 W m-1 K-1, and the estimated figure of merit is 0.29 at 1000 K. © 2013 American Chemical Society.

High temperature thermoelectric properties of strontium titanate thin films with oxygen vacancy and niobium doping

KAUST Repository

Sarath Kumar, S. R.

2013-08-14

We report the evolution of high temperature thermoelectric properties of SrTiO3 thin films doped with Nb and oxygen vacancies. Structure-property relations in this important thermoelectric oxide are elucidated and the variation of transport properties with dopant concentrations is discussed. Oxygen vacancies are incorporated during growth or annealing in Ar/H2 above 800 K. An increase in lattice constant due to the inclusion of Nb and oxygen vacancies is found to result in an increase in carrier density and electrical conductivity with simultaneous decrease in carrier effective mass and Seebeck coefficient. The lattice thermal conductivity at 300 K is found to be 2.22 W m-1 K-1, and the estimated figure of merit is 0.29 at 1000 K. © 2013 American Chemical Society.

Surface oxygen vacancy and oxygen permeation flux limits of perovskite ion transport membranes

KAUST Repository

Hunt, Anton; Dimitrakopoulos, Georgios; Ghoniem, Ahmed F.

2015-01-01

© 2015 Elsevier B.V. The mechanisms and quantitative models for how oxygen is separated from air using ion transport membranes (ITMs) are not well understood, largely due to the experimental complexity for determining surface exchange reactions

Chemisorption of oxygen and subsequent reactions on low index surfaces of β-Mo₂C

DEFF Research Database (Denmark)

Shi, Xue Rong; Wang, Shengguang; Wang, Jianguo

2016-01-01

to the carbon vacancy were identified. We examined the effect of oxygen coverage on the morphology of β-Mo2C by plotting the equilibrium crystal shape. Thermodynamic effect of temperature and reactant or product pressure on the CO/CO2 desorption were investigated. The CO/CO2 desorption is more favorable...... at the saturated oxygen coverage than the low oxygen coverage thermodynamically. The subsequent oxygen diffusion to the carbon vacancy after CO/CO2 desorption may happen depending on the surfaces and oxygen coverage....

Oxygen vacancy doping of hematite analyzed by electrical conductivity and thermoelectric power measurements

Science.gov (United States)

Mock, Jan; Klingebiel, Benjamin; Köhler, Florian; Nuys, Maurice; Flohre, Jan; Muthmann, Stefan; Kirchartz, Thomas; Carius, Reinhard

2017-11-01

Hematite (α -F e2O3 ) is known for poor electronic transport properties, which are the main drawback of this material for optoelectronic applications. In this study, we investigate the concept of enhancing electrical conductivity by the introduction of oxygen vacancies during temperature treatment under low oxygen partial pressure. We demonstrate the possibility of tuning the conductivity continuously by more than five orders of magnitude during stepwise annealing in a moderate temperature range between 300 and 620 K. With thermoelectric power measurements, we are able to attribute the improvement of the electrical conductivity to an enhanced charge-carrier density by more than three orders of magnitude. We compare the oxygen vacancy doping of hematite thin films with hematite nanoparticle layers. Thereby we show that the dominant potential barrier that limits charge transport is either due to grain boundaries in hematite thin films or due to potential barriers that occur at the contact area between the nanoparticles, rather than the potential barrier within the small polaron hopping model, which is usually applied for hematite. Furthermore, we discuss the transition from oxygen-deficient hematite α -F e2O3 -x towards the magnetite F e3O4 phase of iron oxide at high density of vacancies.

Modulation of resistive switching characteristics for individual BaTiO3 microfiber by surface oxygen vacancies

Science.gov (United States)

Miao, Zhilei; Chen, Lei; Zhou, Fang; Wang, Qiang

2018-01-01

Different from traditional thin-film BaTiO3 (BTO) RRAM device with planar structure, individual microfiber-shaped RRAM device, showing promising application potentials in the micro-sized non-volatile memory system, has not been investigated so far to demonstrate resistive switching behavior. In this work, individual sol-gel BTO microfiber has been formed using the draw-bench method, followed by annealing in different atmospheres of air and argon, respectively. The resistive switching characteristics of the individual BTO microfiber have been investigated by employing double-probe SEM measurement system, which shows great convenience to test local electrical properties by modulating the contact sites between the W probes and the BTO microfiber. For the sample annealed in air, the average resistive ON/OFF ratio is as high as 108, enhanced about four orders in comparison with the counterpart that annealed in Argon. For the sample annealed in argon ambience, the weakened resistive ON/OFF ratio can be attributed to the increased presence of oxygen vacancies in the surface of BTO fibers, and the underlying electrical conduction mechanisms are also discussed.

Influence of surface vacancy defects on the carburisation of Fe 110 surface by carbon monoxide

Energy Technology Data Exchange (ETDEWEB)

Chakrabarty, Aurab, E-mail: aurab.chakrabarty@qatar.tamu.edu; Bouhali, Othmane [Texas A& M University at Qatar, P.O. Box 23874, Doha (Qatar); Mousseau, Normand [Département de Physique and RQMP, Université de Montréal, Case Postale 6128, Succursale Centre-Ville, Montréal (QC) H3C 3J7 (Canada); Becquart, Charlotte S. [UMET, UMR CNRS 8207, ENSCL, Université Lille I, 59655 Villeneuve d’Ascq cédex (France); El-Mellouhi, Fedwa, E-mail: felmellouhi@qf.org.qa [Qatar Environment and Energy Research Institute, Hamad Bin Khalifa University, P.O. Box 5825 Doha (Qatar)

2016-07-28

Adsorption and dissociation of gaseous carbon monoxide (CO) on metal surfaces is one of the most frequently occurring processes of carburisation, known as primary initiator of metal dusting corrosion. Among the various factors that can significantly influence the carburisation process are the intrinsic surface defects such as single surface vacancies occurring at high concentrations due to their low formation energy. Intuitively, adsorption and dissociation barriers of CO are expected to be lowered in the vicinity of a surface vacancy, due to the strong attractive interaction between the vacancy and the C atom. Here the adsorption energies and dissociation pathways of CO on clean and defective Fe 110 surface are explored by means of density functional theory. Interestingly, we find that the O adatom, resulting from the CO dissociation, is unstable in the electron-deficit neighbourhood of the vacancy due to its large electron affinity, and raises the barrier of the carburisation pathway. Still, a full comparative study between the clean surface and the vacancy-defected surface reveals that the complete process of carburisation, starting from adsorption to subsurface diffusion of C, is more favourable in the vicinity of a vacancy defect.

Deep vs shallow nature of oxygen vacancies and consequent n -type carrier concentrations in transparent conducting oxides

Science.gov (United States)

Buckeridge, J.; Catlow, C. R. A.; Farrow, M. R.; Logsdail, A. J.; Scanlon, D. O.; Keal, T. W.; Sherwood, P.; Woodley, S. M.; Sokol, A. A.; Walsh, A.

2018-05-01

The source of n -type conductivity in undoped transparent conducting oxides has been a topic of debate for several decades. The point defect of most interest in this respect is the oxygen vacancy, but there are many conflicting reports on the shallow versus deep nature of its related electronic states. Here, using a hybrid quantum mechanical/molecular mechanical embedded cluster approach, we have computed formation and ionization energies of oxygen vacancies in three representative transparent conducting oxides: In2O3 ,SnO2, and ZnO. We find that, in all three systems, oxygen vacancies form well-localized, compact donors. We demonstrate, however, that such compactness does not preclude the possibility of these states being shallow in nature, by considering the energetic balance between the vacancy binding electrons that are in localized orbitals or in effective-mass-like diffuse orbitals. Our results show that, thermodynamically, oxygen vacancies in bulk In2O3 introduce states above the conduction band minimum that contribute significantly to the observed conductivity properties of undoped samples. For ZnO and SnO2, the states are deep, and our calculated ionization energies agree well with thermochemical and optical experiments. Our computed equilibrium defect and carrier concentrations, however, demonstrate that these deep states may nevertheless lead to significant intrinsic n -type conductivity under reducing conditions at elevated temperatures. Our study indicates the importance of oxygen vacancies in relation to intrinsic carrier concentrations not only in In2O3 , but also in SnO2 and ZnO.

Trapping of oxygen vacancies on twin walls of CaTiO3: a computer simulation study

International Nuclear Information System (INIS)

Calleja, Mark; Dove, Martin T; Salje, Ekhard K H

2003-01-01

We have studied the atomic structure of [001] 90 deg. rotation twin walls in orthorhombic CaTiO 3 (symmetry Pbnm) at low temperature (10 K) and their effects on oxygen vacancies. The wall thickness was found to be 2.3 nm at T || T c and it was found that it is energetically favourable for such vacancies to reside in the wall, particularly when bridging titania ions in the (001) plane. The binding energy of an oxygen vacancy in the wall with respect to the bulk is calculated to be ≤ 1.2 eV

Ferromagnetism and half metallicity induced by oxygen vacancies in the double perovskite BaSrNiWO{sub 6}: DFT study

Energy Technology Data Exchange (ETDEWEB)

Aharbil, Y. [Laboratoire de Chimie Physique des Matériaux LCPM, Faculté des Sciences Ben M' Sik, Casablanca (Morocco); Labrim, H. [Unité Science de la Matière/DERS/Centre National de l’Energie, des Sciences et des Techniques Nucléaires (CNESTEN), Rabat (Morocco); Benmokhtar, S.; Haddouch, M. Ait [Laboratoire de Chimie Physique des Matériaux LCPM, Faculté des Sciences Ben M' Sik, Casablanca (Morocco); Bahmad, L., E-mail: bahmad@fsr.ac.ma [Mohammed V University in Rabat, Laboratoire de Magnétisme et Physique des Hautes Energies L.M.P.H.E. URAC-12, B.P. 1014, Rabat (Morocco); Belhaj, A. [LIRST, Département de Physique, Faculté Poly-disciplinaire, Université Sultan Moulay Slimane, Béni Mellal (Morocco); Ez-Zahraouy, H.; Benyoussef, A. [Mohammed V University in Rabat, Laboratoire de Magnétisme et Physique des Hautes Energies L.M.P.H.E. URAC-12, B.P. 1014, Rabat (Morocco)

2016-11-01

Using the spin polarized density functional theory (DFT) and exploring the Plane-Wave Self-Consistent Field (PWscf) code implemented in Quantum-ESPRESSO package, we investigate the effect of the Oxygen vacancies (V{sub O}) and the Oxygen interstitial (O{sub i}) on the double perovskite BaSrNiWO{sub 6}. This deals with the magnetic ordering and the electronic structure in such a pure sample exhibiting the insulating anti-ferromagnetic (AFM) state. This study shows that the presence of oxygen deficient defects converts the insulating to half metal with ferromagnetic or anti-ferromagnetic states. The magnetic ordering in BaSrNiWO{sub 6−δ} depends on the position of the Oxygen vacancy in the unit cell. However, it has been shown that the Oxygen interstitial preserves the anti-ferromagnetic propriety. We have computed the formation energies of different positions of the Oxygen vacancy (V{sub O}) and the Oxygen interstitial (O{sub i}) in the BaSrNiWO{sub 6} compound. We showed that the formation of V{sub O} is easier and vice versa for the O{sub i} formation. The obtained results reveal(V{sub O}) and the Oxygen interstitial (O{sub i}) that the anti-ferromagnetic can be converted to ferromagnetic in the double perovskite BaSrNiWO{sub 6} induced by Oxygen vacancies V{sub O}. - Highlights: • We have studied the ferromagnetism and Half Metallicity in Double Perovskite BaSrNiWO{sub 6}. • We have applied the Ab-inito calculations using the DFT approach. • We showed the effects induced by Oxygen Vacancies and Oxygen interstitial. • We found that the magnetic ordering in BaSrNiWO{sub 6−δ} depends on the position of the Oxygen vacancy in the unit cell.

First principle simulations on the effects of oxygen vacancy in HfO2-based RRAM

Directory of Open Access Journals (Sweden)

Yuehua Dai

2015-01-01

Full Text Available HfO2-based resistive random access memory (RRAM takes advantage of oxygen vacancy (V o defects in its principle of operation. Since the change in resistivity of the material is controlled by the level of oxygen deficiency in the material, it is significantly important to study the performance of oxygen vacancies in formation of conductive filament. Excluding effects of the applied voltage, the Vienna ab initio simulation package (VASP is used to investigate the orientation and concentration mechanism of the oxygen vacancies based on the first principle. The optimal value of crystal orientation [010] is identified by means of the calculated isosurface plots of partial charge density, formation energy, highest isosurface value, migration barrier, and energy band of oxygen vacancy in ten established orientation systems. It will effectively influence the SET voltage, forming voltage, and the ON/OFF ratio of the device. Based on the results of orientation dependence, different concentration models are established along crystal orientation [010]. The performance of proposed concentration models is evaluated and analyzed in this paper. The film is weakly conductive for the samples deposited in a mixture with less than 4.167at.% of V o contents, and the resistive switching (RS phenomenon cannot be observed in this case. The RS behavior improves with an increase in the V o contents from 4.167at.% to 6.25at.%; nonetheless, it is found difficult to switch to a stable state. However, a higher V o concentration shows a more favorable uniformity and stability for HfO2-based RRAM.

Identification of the gallium vacancy-oxygen pair defect in GaN

International Nuclear Information System (INIS)

Son, N. T.; Hemmingsson, C. G.; Janzen, E.; Paskova, T.; Evans, K. R.; Usui, A.; Morishita, N.; Ohshima, T.; Isoya, J.; Monemar, B.

2009-01-01

Cation vacancies like V Ga , V Al and their complexes with oxygen are predicted to be abundant in III-nitrides and to play an important role in nonradiative recombination. Appearing in triple or double negatively charged states, they are not paramagnetic and have not so far been detected by magnetic resonance even under illumination. In this Brief Report, we demonstrate an efficient way to make cation vacancy defects in GaN detectable by electron paramagnetic resonance and present our identification of the V Ga O N pair in GaN which is the model material for the III-nitrides and their alloys.

Microstructure evolution characteristics induced by oxygen vacancy generation in anatase TiO2 based resistive switching devices

Science.gov (United States)

Liu, Chen; Gao, Bin; Huang, Peng; Kang, Jinfeng

2017-03-01

In this work, first principle calculations are employed to study the microstructure characteristics of the anatase TiO2 resistive switching material associated with the generation of oxygen vacancy (V o) based nanofilaments during the switching process. The calculations indicate that both the magnéli phase Ti4O7 and V o-defect phase of anatase TiO2 may be formed with the generation of oxygen vacancies during the forming and SET processes. Based on the calculations, a new physical insight is proposed to clarify the microstructure evolution characteristics of the anatase TiO2 resistive switching material and the correlation with resistive switching behaviors. During the forming or SET process, the anatase TiO2 is first excited to a transition state with the generation of oxygen vacancies, then fully relaxes to a stable V o-defect state. This V o-defect state may either recover to the original state with the recombination of the oxygen vacancies, which causes the reversible resistive switching behavior, or further transform to a much more stable state—the magnéli phase Ti4O7, through a phase transition process with the generation of many more oxygen vacancies. The phase transition from V o- defective anatase phase to magnéli phase Ti4O7 causes the failure of the resistive switching due to the significantly reduced possibility of the reversible phase transition from the magnéli phase to the anatase phase, compared with the possibility of the recombination from the V o-defective anatase.

Direct observation of oxygen-vacancy-enhanced polarization in a SrTiO{sub 3}-buffered ferroelectric BaTiO{sub 3} film on GaAs

Energy Technology Data Exchange (ETDEWEB)

Qiao, Qiao [Department of Physics, University of Illinois at Chicago, Chicago, Illinois 60607 (United States); Department of Physics and Astronomy, Vanderbilt University, Nashville, Tennessee 37240 (United States); Materials Science and Technology Department, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States); Zhang, Yuyang [Department of Physics and Astronomy, Vanderbilt University, Nashville, Tennessee 37240 (United States); Materials Science and Technology Department, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States); Contreras-Guerrero, Rocio; Droopad, Ravi [Ingram School of Engineering, Texas State University, San Marcos, Texas 78666 (United States); Pantelides, Sokrates T. [Department of Physics and Astronomy, Vanderbilt University, Nashville, Tennessee 37240 (United States); Materials Science and Technology Department, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States); Department of Electrical Engineering and Computer Science, Vanderbilt University, Nashville, Tennessee 37240 (United States); Pennycook, Stephen J. [Department of Materials Science and Engineering, National University of Singapore, Singapore 117575 (Singapore); Ogut, Serdar; Klie, Robert F. [Department of Physics, University of Illinois at Chicago, Chicago, Illinois 60607 (United States)

2015-11-16

The integration of functional oxide thin-films on compound semiconductors can lead to a class of reconfigurable spin-based optoelectronic devices if defect-free, fully reversible active layers are stabilized. However, previous first-principles calculations predicted that SrTiO{sub 3} thin films grown on Si exhibit pinned ferroelectric behavior that is not switchable, due to the presence of interfacial vacancies. Meanwhile, piezoresponse force microscopy measurements have demonstrated ferroelectricity in BaTiO{sub 3} grown on semiconductor substrates. The presence of interfacial oxygen vacancies in such complex-oxide/semiconductor systems remains unexplored, and their effect on ferroelectricity is controversial. Here, we use a combination of aberration-corrected scanning transmission electron microscopy and first-principles density functional theory modeling to examine the role of interfacial oxygen vacancies on the ferroelectric polarization of a BaTiO{sub 3} thin film grown on GaAs. We demonstrate that interfacial oxygen vacancies enhance the polar discontinuity (and thus the single domain, out-of-plane polarization pinning in BaTiO{sub 3}), and propose that the presence of surface charge screening allows the formation of switchable domains.

Oxygen vacancy induced fast lithium storage and efficient organics photodegradation over ultrathin TiO{sub 2} nanolayers grafted graphene sheets

Energy Technology Data Exchange (ETDEWEB)

Xie, Yu, E-mail: xieyu_121@163.com [Nanchang Hangkong University, Department of Material Chemistry, Nanchang, Jiangxi Province (China); Hu, Dongsheng [Nanchang Hangkong University, Department of Material Chemistry, Nanchang, Jiangxi Province (China); Liu, Lianjun, E-mail: liul@uwm.edu [University of Wisconsin-Milwaukee, Mechanical Engineering Department, Milwaukee, WI (United States); Zhou, Panpan; Xu, Jiangwei; Ling, Yun [Nanchang Hangkong University, Department of Material Chemistry, Nanchang, Jiangxi Province (China)

2016-11-15

Highlights: • Oxygen vacancy is tailored by adjusting the treatment conditions. • Unltrathin TiO{sub 2} nanolayers are grafted on the graphene sheets. • Oxygen vacancy is located on the surface of TiO{sub 2}/graphene treated by H{sub 2}. • Improved lithium storage and organic pollutants removal efficiency. - Abstract: In this work we have developed a unique structure of ultrathin (5 nm) TiO{sub 2} nanolayers grafted graphene nanosheets (TiO{sub 2}/G) and integrated oxygen vacancy (V{sub O}) into TiO{sub 2} to enhance its lithium storage and photocatalytic performances. The defective TiO{sub 2}/G was synthesized by a solvothermal and subsequent thermal treatment method. When treated in a H{sub 2} atmosphere, the resulting TiO{sub 2-x}/G(H{sub 2}) has lower crystallinity, smaller crystal size, richer surface V{sub O}, higher surface area, larger pore volume, and lower charge transfer resistance than that reduced by NaBH{sub 4} solid, i.e., TiO{sub 2-x}/G(NaBH{sub 4}). More importantly, the surface V{sub O} in the TiO{sub 2-x}/G(H{sub 2}) could remarkably inhibit the recombination of photogenerated electron-hole pairs compared with the bulk Vo in the TiO{sub 2-x}/G(NaBH{sub 4}). As a result, the combination of all the factors contributed to the superiority of TiO{sub 2-x}/G(H{sub 2}), which demonstrated not only 70% higher specific capacity, longer cycling performance (1000 cycles) and better rate capability for lithium-ion battery, but also higher photocatalytic activity and 1.5 times faster degradation rate for organic pollutants removal than TiO{sub 2-x}/G(NaBH{sub 4}). The findings in this work will benefit the fundamental understanding of TiO{sub 2}/G surface chemistry and advance the design and preparation of functional materials for energy storage and water treatment.

Interaction of hydrogen and oxygen with bulk defects and surfaces of metals

International Nuclear Information System (INIS)

Besenbacher, F.

1994-05-01

The thesis deals with the interaction of hydrogen with defects in metals and the interaction of hydrogen and oxygen with metal surfaces studied by ion-beam techniques and scanning tunneling microscopy (STM), respectively. The first part of the thesis discusses the interaction of hydrogen with simple defects in transition metals. The trap-binding enthalpies and the lattice location of hydrogen trapped to vacancies have been determined, and an extremely simple and versatile picture of the hydrogen-metal interaction has evolved, in which the trap strength is mainly determined by the local electron density. Any dilution of the lattice will lead to a trap, vacancies and voids being the strongest trap. It is found that hydrogen trapped to vacancies in fcc metals is quantum-mechanically delocalized, and the excitation energies for the hydrogen in the vacancy potential are a few MeV only. The interaction of hydrogen with metal surfaces is studied by the transmission channeling (TC) technique. It is found that hydrogen chemisorbs in the highest-coordinated sites on the surfaces, and that there is a direct relationship between the hydrogen-metal bond length and the coordination number for the hydrogen. In the final part of the thesis the dynamics of the chemisorption process for oxygen and hydrogen on metal surfaces is studied by STM, a fascinating and powerful technique for exploring the atomic-scale realm of surfaces. It is found that there is a strong coupling between the chemisorption process and the distortion of the metal surface. The adsorbates induce a surface reconstruction, i.e. metal-metal bond breaks and metal-adsorbate bounds form. Whereas hydrogen interacts weakly with the metals and induces reconstructions where only nnn metals bonds are broken, oxygen interacts strongly with the metal, and the driving force for the O-induced reconstructions appears to be the formation of low-coordinated metal-O rows, formed by breaking of nn metal bonds. Finally it is shown

Clustering and segregation of small vacancy clusters near tungsten (0 0 1) surface

Science.gov (United States)

Duan, Guohua; Li, Xiangyan; Xu, Yichun; Zhang, Yange; Jiang, Yan; Hao, Congyu; Liu, C. S.; Fang, Q. F.; Chen, Jun-Ling; Luo, G.-N.; Wang, Zhiguang

2018-01-01

Nanoporous metals have been shown to exhibit radiation-tolerance due to the trapping of the defects by the surface. However, the behavior of vacancy clusters near the surface is not clear which involves the competition between the self-trapping and segregation of small vacancy clusters (Vn) nearby the surface. In this study, we investigated the energetic and kinetic properties of small vacancy clusters near tungsten (0 0 1) surface by combining molecular statics (MS) calculations and object Kinetic Monte Carlo (OKMC) simulations. Results show that vacancies could be clustered with the reduced formation energy and migration energy of the single vacancy around a cluster as the respective energetic and kinetic driving forces. The small cluster has a migration energy barrier comparable to that for the single vacancy; the migration energy barriers for V1-5 and V7 are 1.80, 1.94, 2.17, 2.78, 3.12 and 3.11 eV, respectively. Clusters and become unstable near surface (0 0 1) and tend to dissociate into the surface. At the operation temperature of 1000 K, the single vacancy, V2, 2 V 3 V3 and V4 were observed to segregate to the surface within a time of one hour. Meanwhile, larger clusters survived near the surface, which could serve as nucleating center for voids near the surface. Our results suggest that under a low radiation dose, surface (0 0 1) could act as a sink for small vacancy clusters, alleviating defect accumulation in the material under a low radiation dose. We also obtained several empirical expressions for the vacancy cluster formation energy, binding energy, and trapping radius as a function of the number of vacancies in the cluster.

Oxygen dosing the surface of SrTiO{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Dudy, L.; Scheiderer, P.; Schuetz, P.; Gabel, J.; Buchwald, M.; Sing, M.; Claessen, R. [Physikalisches Institut, Universitaet Wuerzburg (Germany); Denlinger, J.D. [Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, 94270 (United States); Schlueter, C.; Lee, T.L. [Diamond Light Source Ltd., Didcot, Oxfordshire (United Kingdom)

2015-07-01

The highly mobile two-dimensional electron system (2DES) on the surface of the insulating SrTiO{sub 3}(STO) offers exciting perspectives for advanced material design. This 2DES resides in a depletion layer caused by oxygen deficiency of the surface. With photoemission spectroscopy, we monitor the appearance of quasi-particle weight (QP) at the Fermi energy and oxygen vacancy induced states in the band gap (IG). Both, QP and IG weight, increase and decrease respectively upon exposure to extreme ultraviolet (XUV) light and in-situ oxygen dosing. By a proper adjustment of oxygen dosing, any intermediate state can be stabilized providing full control over the charge carrier density. From a comparison of the charge carrier concentrations obtained from an analysis of core-level spectra and the Fermi-surface volume, we conclude on a spatially inhomogeneous surface electronic structure with at least two different phases.

Evidence of oxygen vacancy and possible intermediate gap state in layered α-MoO{sub 3} single-crystal nanobelts

Energy Technology Data Exchange (ETDEWEB)

Chen, C.Z., E-mail: tcccz@shu.edu.cn; Li, Y.; Tang, X.D.

2016-01-15

Multilayered meso-structured MoO{sub 3} nanobelts have been synthesized by thermally oxidizing a molybdenum chip in a reduced oxygen atmosphere, with a view to disclosing the existence of oxygen vacancy and understanding the mechanism behind the influence of oxygen vacancy on the electronic structure of molybdenum oxides. Based on the measurements from X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscope (SEM) and transmission electron microscope (TEM), it is found that the as-grown sample is single-crystal α-MoO{sub 3} with a (001) preferred orientation, which shows an irregular belt-like morphology being composed of some ~20 nm single-crystal thin layers. The present sample includes a lot of oxygen vacancies in the lattice, as evidenced by the considerably reduced coordination number of the central Mo atoms from X-ray absorption spectra (XAS) as well as the red shift of the main Raman peaks. The existence of the oxygen vacancies are further tested by the photoluminescence (PL) results as the main emission peak shows an obvious red shift with the corresponding optical band gap reduced to 2.3 eV. Very importantly, an extra emission positioned at 738 nm (1.68 eV) is believed to originate from the recombination of the electrons from the intermediate band (IB) to the valence band (VB), and the formation of the IB in the gap is also caused by oxygen-ion vacancies.

Effect of oxygen vacancies on the electronic and optical properties of tungsten oxide from first principles calculations

Science.gov (United States)

Mehmood, Faisal; Pachter, Ruth; Murphy, Neil R.; Johnson, Walter E.; Ramana, Chintalapalle V.

2016-12-01

In this work, we investigated theoretically the role of oxygen vacancies on the electronic and optical properties of cubic, γ-monoclinic, and tetragonal phases of tungsten oxide (WO3) thin films. Following the examination of structural properties and stability of the bulk tungsten oxide polymorphs, we analyzed band structures and optical properties, applying density functional theory (DFT) and GW (Green's (G) function approximation with screened Coulomb interaction (W)) methods. Careful benchmarking of calculated band gaps demonstrated the importance of using a range-separated functional, where results for the pristine room temperature γ-monoclinic structure indicated agreement with experiment. Further, modulation of the band gap for WO3 structures with oxygen vacancies was quantified. Dielectric functions for cubic WO3, calculated at both the single-particle, essentially time-dependent DFT, as well as many-body GW-Bethe-Salpeter equation levels, indicated agreement with experimental data for pristine WO3. Interestingly, we found that introducing oxygen vacancies caused appearance of lower energy absorptions. A smaller refractive index was indicated in the defective WO3 structures. These predictions could lead to further experiments aimed at tuning the optical properties of WO3 by introducing oxygen vacancies, particularly for the lower energy spectral region.

First-Principles Study on the Structural and Electronic Properties of N Atoms Doped-Rutile TiO2 of Oxygen Vacancies

Directory of Open Access Journals (Sweden)

Zhong-Liang Zeng

2015-01-01

Full Text Available For the propose of considering the actual situation of electronic neutral, a simulation has been down on the basis of choosing the position of dual N and researching the oxygen vacancy. It is found that the reason why crystal material gets smaller is due to the emergence of impurity levels. By introducing the oxygen vacancy to the structure, the results show that while the oxygen vacancy is near the two nitrogen atoms which have a back to back position, its energy gets the lowest level and its structure gets the most stable state. From its energy band structure and density, the author finds that the impurity elements do not affect the migration of Fermi level while the oxygen vacancy has been increased. Instead of that, the conduction band of metal atoms moves to the Fermi level and then forms the N-type semiconductor material, but the photocatalytic activity is not as good as the dual N-doping state.

Oxygen-Vacancy Abundant Ultrafine Co3O4/Graphene Composites for High-Rate Supercapacitor Electrodes.

Science.gov (United States)

Yang, Shuhua; Liu, Yuanyue; Hao, Yufeng; Yang, Xiaopeng; Goddard, William A; Zhang, Xiao Li; Cao, Bingqiang

2018-04-01

The metal oxides/graphene composites are one of the most promising supercapacitors (SCs) electrode materials. However, rational synthesis of such electrode materials with controllable conductivity and electrochemical activity is the topical challenge for high-performance SCs. Here, the Co 3 O 4 /graphene composite is taken as a typical example and develops a novel/universal one-step laser irradiation method that overcomes all these challenges and obtains the oxygen-vacancy abundant ultrafine Co 3 O 4 nanoparticles/graphene (UCNG) composites with high SCs performance. First-principles calculations show that the surface oxygen vacancies can facilitate the electrochemical charge transfer by creating midgap electronic states. The specific capacitance of the UCNG electrode reaches 978.1 F g -1 (135.8 mA h g -1 ) at the current densities of 1 A g -1 and retains a high capacitance retention of 916.5 F g -1 (127.3 mA h g -1 ) even at current density up to 10 A g -1 , showing remarkable rate capability (more than 93.7% capacitance retention). Additionally, 99.3% of the initial capacitance is maintained after consecutive 20 000 cycles, demonstrating enhanced cycling stability. Moreover, this proposed laser-assisted growth strategy is demonstrated to be universal for other metal oxide/graphene composites with tuned electrical conductivity and electrochemical activity.

Oxygen vacancy effects in HfO2-based resistive switching memory: First principle study

Directory of Open Access Journals (Sweden)

Yuehua Dai

2016-08-01

Full Text Available The work investigated the shape and orientation of oxygen vacancy clusters in HfO2-base resistive random access memory (ReRAM by using the first-principle method based on the density functional theory. Firstly, the formation energy of different local Vo clusters was calculated in four established orientation systems. Then, the optimized orientation and charger conductor shape were identified by comparing the isosurface plots of partial charge density, formation energy, and the highest isosurface value of oxygen vacancy. The calculated results revealed that the [010] orientation was the optimal migration path of Vo, and the shape of system D4 was the best charge conductor in HfO2, which effectively influenced the SET voltage, formation voltage and the ON/OFF ratio of the device. Afterwards, the PDOS of Hf near Vo and total density of states of the system D4_010 were obtained, revealing the composition of charge conductor was oxygen vacancy instead of metal Hf. Furthermore, the migration barriers of the Vo hopping between neighboring unit cells were calculated along four different orientations. The motion was proved along [010] orientation. The optimal circulation path for Vo migration in the HfO2 super-cell was obtained.

Atomic and molecular oxygen adsorbed on (111) transition metal surfaces: Cu and Ni

Energy Technology Data Exchange (ETDEWEB)

López-Moreno, S., E-mail: sinlopez@uacam.mx [Centro de Investigación en Corrosión, Universidad Autónoma de Campeche, Av. Héroe de Nacozari 480, Campeche, Campeche 24029 (Mexico); Romero, A. H. [Physics Department, West Virginia University, Morgantown, West Virginia 26506-6315 (United States)

2015-04-21

Density functional theory is used to investigate the reaction of oxygen with clean copper and nickel [111]-surfaces. We study several alternative adsorption sites for atomic and molecular oxygen on both surfaces. The minimal energy geometries and adsorption energies are in good agreement with previous theoretical studies and experimental data. From all considered adsorption sites, we found a new O{sub 2} molecular precursor with two possible dissociation paths on the Cu(111) surface. Cross barrier energies for the molecular oxygen dissociation have been calculated by using the climbing image nudge elastic band method, and direct comparison with experimental results is performed. Finally, the structural changes and adsorption energies of oxygen adsorbed on surface when there is a vacancy nearby the adsorption site are also considered.

Atomic and molecular oxygen adsorbed on (111) transition metal surfaces: Cu and Ni

Science.gov (United States)

López-Moreno, S.; Romero, A. H.

2015-04-01

Density functional theory is used to investigate the reaction of oxygen with clean copper and nickel [111]-surfaces. We study several alternative adsorption sites for atomic and molecular oxygen on both surfaces. The minimal energy geometries and adsorption energies are in good agreement with previous theoretical studies and experimental data. From all considered adsorption sites, we found a new O2 molecular precursor with two possible dissociation paths on the Cu(111) surface. Cross barrier energies for the molecular oxygen dissociation have been calculated by using the climbing image nudge elastic band method, and direct comparison with experimental results is performed. Finally, the structural changes and adsorption energies of oxygen adsorbed on surface when there is a vacancy nearby the adsorption site are also considered.

Atomic and molecular oxygen adsorbed on (111) transition metal surfaces: Cu and Ni

International Nuclear Information System (INIS)

López-Moreno, S.; Romero, A. H.

2015-01-01

Density functional theory is used to investigate the reaction of oxygen with clean copper and nickel [111]-surfaces. We study several alternative adsorption sites for atomic and molecular oxygen on both surfaces. The minimal energy geometries and adsorption energies are in good agreement with previous theoretical studies and experimental data. From all considered adsorption sites, we found a new O 2 molecular precursor with two possible dissociation paths on the Cu(111) surface. Cross barrier energies for the molecular oxygen dissociation have been calculated by using the climbing image nudge elastic band method, and direct comparison with experimental results is performed. Finally, the structural changes and adsorption energies of oxygen adsorbed on surface when there is a vacancy nearby the adsorption site are also considered

Zinc vacancy and oxygen interstitial in ZnO revealed by sequential annealing and electron irradiation

Science.gov (United States)

Knutsen, K. E.; Galeckas, A.; Zubiaga, A.; Tuomisto, F.; Farlow, G. C.; Svensson, B. G.; Kuznetsov, A. Yu.

2012-09-01

By combining results from positron annihilation and photoluminescence spectroscopy with data from Hall effect measurements, the characteristic deep level emission centered at ˜1.75 eV and exhibiting an activation energy of thermal quenching of 11.5 meV is associated with the zinc vacancy. Further, a strong indication that oxygen interstitials act as a dominating acceptor is derived from the analysis of charge carrier losses induced by electron irradiation with variable energy below and above the threshold for Zn-atom displacement. We also demonstrate that the commonly observed green emission is related to an extrinsic acceptorlike impurity, which may be readily passivated by oxygen vacancies.

Oxygen vacancy formation and migration in Sr- and Mg-doped LaGaO3: a density functional theory study

International Nuclear Information System (INIS)

Zhang Jie; Liang Er-Jun; Sun Qiang; Jia Yu

2012-01-01

Oxygen vacancy formation and migration in La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3−δ (LSGM) with various crystal symmetries (cubic, rhombohedral, orthorhombic, and monoclinic) are studied by employing first-principles calculations based on density functional theory (DFT). It is shown that the cubic LSGM has the smallest band gap, oxygen vacancy formation energy, and migration barrier, while the other three structures give rise to much larger values for these quantities, implying the best oxygen ion conductivity of the cubic LSGM among the four crystal structures. In our calculations, one oxygen vacancy migration pathway is considered in the cubic and rhombohedral structures due to all the oxygen sites being equivalent in them, while two vacancy migration pathways with different migration barriers are found in the orthorhombic and monoclinic symmetries owing to the existence of nonequivalent O 1 and O 2 oxygen sites. The migration energies along the migration pathway linking the two O 2 sites are obviously lower than those along the pathway linking the O 1 and O 2 sites. Considering the phase transitions at high temperatures, the results obtained in this paper can not only explain the experimentally observed different behaviours of the oxygen ionic conductivity of LSGM with different symmetries, but also predict the rational crystal structures of LSGM for solid oxide fuel cell applications. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

Stability of V₂O₅ Supported on Titania in the Presence of Water, Bulk Oxygen Vacancies, and Adsorbed Oxygen Atoms

DEFF Research Database (Denmark)

Kristoffersen, Henrik Høgh; Neilson, Hunter L.; Buratto, Steven K.

2017-01-01

). In the case of oxidative dehydrogenation of alkanes and methanol, the reaction produces water, oxygen vacancies, and hydrogen atoms bound to the surface. For this article we use density functional theory to examine how the presence of these species on the surface affects a V2O5 cluster, which we assume......A catalyst consisting of vanadium oxide submonolayers supported on rutile titanium dioxide is used for a variety of reactions. One important question is the difference between the activity of monomeric clusters (having one vanadium atom) and polymeric clusters (having more than one vanadium atom...

The interplay between dopants and oxygen vacancies in the magnetism of V-doped TiO2

KAUST Repository

Grau-Crespo, Ricardo

2011-08-03

Density functional theory calculations indicate that the incorporation of V into Ti lattice positions of rutile TiO2 leads to magnetic V 4 + species, but the extension and sign of the coupling between dopant moments confirm that ferromagnetic order cannot be reached via low-concentration doping in the non-defective oxide. Oxygen vacancies can introduce additional magnetic centres, and we show here that one of the effects of vanadium doping is to reduce the formation energies of these defects. In the presence of both V dopants and O vacancies all the spins tend to align with the same orientation. We conclude that V doping favours the ferromagnetic behaviour of TiO2 not only by introducing spins associated with the dopant centres but also by increasing the concentration of oxygen vacancies with respect to the pure oxide. © 2001 IOP Publishing Ltd.

The interplay between dopants and oxygen vacancies in the magnetism of V-doped TiO2

KAUST Repository

Grau-Crespo, Ricardo; Schwingenschlö gl, Udo

2011-01-01

Density functional theory calculations indicate that the incorporation of V into Ti lattice positions of rutile TiO2 leads to magnetic V 4 + species, but the extension and sign of the coupling between dopant moments confirm that ferromagnetic order cannot be reached via low-concentration doping in the non-defective oxide. Oxygen vacancies can introduce additional magnetic centres, and we show here that one of the effects of vanadium doping is to reduce the formation energies of these defects. In the presence of both V dopants and O vacancies all the spins tend to align with the same orientation. We conclude that V doping favours the ferromagnetic behaviour of TiO2 not only by introducing spins associated with the dopant centres but also by increasing the concentration of oxygen vacancies with respect to the pure oxide. © 2001 IOP Publishing Ltd.

The effect of carbon and boron on the accumulation of vacancy-oxygen complexes in silicon

International Nuclear Information System (INIS)

Akhmetov, V.D.; Bolotov, V.V.

1980-01-01

By means of IR-absorption measurements the dose dependencies of the concentrations of vacancy-oxygen complexes (VO), interstitial oxygen atoms (Osub(I)), substitutional carbon atoms (Csub(S)) and interstitial carbon-oxygen complexes (Csub(I)Osub(I)) in n- and p-type silicon irradiated with 1.1 MeV electrons have been investigated. The observed increase of the production rate of VO-complexes with the rise of carbon and boron atoms concentrations (these impurities act as sinks for silicon interstitial atoms) has been explained in terms of annihilation of the vacancies and interstitials on the oxygen atoms. The results obtained show that boron atoms are more effective sinks than carbon atoms for the interstitial silicon atoms. That seems to be connected not only with the higher probability of boron injection into interstitial position but also with the further capture of interstitial silicon atoms on the interstitial boron, i.e. with the interstitial cluster formation. (author)

Effect of oxygen vacancy distribution on the thermoelectric properties of La-doped SrTiO3 epitaxial thin films

KAUST Repository

Sarath Kumar, S. R.; Abutaha, Anas I.; Hedhili, Mohamed N.; Alshareef, Husam N.

2012-01-01

A detailed study of the role of oxygen vacancies in determining the effective mass and high temperature (300–1000 K) thermoelectricproperties of La-doped epitaxial SrTiO3 thin films is presented. It is observed that at intermediate temperatures, a transition from degenerate to non-degenerate behavior is observed in the Seebeck coefficient, but not electrical conductivity, which is attributed to heterogeneous oxygen non-stoichiometry. Heikes formula is found to be invalid for the films with oxygen vacancies. By fitting the spectroscopic ellipsometry (SE) data, obtained in the range 300–2100 nm, using a Drude-Lorentz dispersion relation with two Lorentz oscillators, the electrical and optical properties of the films are extracted. Using the excellent agreement between the transport properties extracted from SE modeling and direct electrical measurements, we demonstrate that an increase in concentration of oxygen vacancies results in a simultaneous increase of both carrier concentration and electron effective mass, resulting in a higher power factor.

Effect of oxygen vacancy distribution on the thermoelectric properties of La-doped SrTiO3 epitaxial thin films

KAUST Repository

Sarath Kumar, S. R.

2012-12-03

A detailed study of the role of oxygen vacancies in determining the effective mass and high temperature (300–1000 K) thermoelectricproperties of La-doped epitaxial SrTiO3 thin films is presented. It is observed that at intermediate temperatures, a transition from degenerate to non-degenerate behavior is observed in the Seebeck coefficient, but not electrical conductivity, which is attributed to heterogeneous oxygen non-stoichiometry. Heikes formula is found to be invalid for the films with oxygen vacancies. By fitting the spectroscopic ellipsometry (SE) data, obtained in the range 300–2100 nm, using a Drude-Lorentz dispersion relation with two Lorentz oscillators, the electrical and optical properties of the films are extracted. Using the excellent agreement between the transport properties extracted from SE modeling and direct electrical measurements, we demonstrate that an increase in concentration of oxygen vacancies results in a simultaneous increase of both carrier concentration and electron effective mass, resulting in a higher power factor.

Roles of grain boundary and oxygen vacancies in Ba{sub 0.6}Sr{sub 0.4}TiO{sub 3} films for resistive switching device application

Energy Technology Data Exchange (ETDEWEB)

Yan, Xiaobing, E-mail: xiaobing-yan@126.com, E-mail: mseyanx@nus.edu.sg [Key Laboratory of Digital Medical Engineering of Hebei Province, College of Electron and Information Engineering, Hebei University, Baoding 071002 (China); Department of Materials Science and Engineering, National University of Singapore, Singapore, Singapore 117576 (Singapore); Li, Yucheng; Zhao, Jianhui; Li, Yan [Key Laboratory of Digital Medical Engineering of Hebei Province, College of Electron and Information Engineering, Hebei University, Baoding 071002 (China); Bai, Gang [College of Electronic Science and Engineering, Nanjing University of Posts and Telecommunications, Nanjing 210023 (China); Zhu, Siqi [Key Laboratory of Optoelectronic Information and Sensing Technologies of Guangdong Higher Education Institutes, Jinan University, Guangzhou 510632 (China)

2016-01-18

Oxygen vacancies are widely thought to be responsible for resistive switching (RS) effects based on polycrystalline oxides films. It is also well known that grain boundaries (GB) serve as reservoirs for accumulating oxygen vacancies. Here, Ar gas was introduced to enlarge the size of GB and increase the quantity of oxygen vacancies when the Ba{sub 0.6}Sr{sub 0.4}TiO{sub 3} (BST) films were deposited by pulse laser deposition technique. The experimental results indicate that the RS properties of the device exhibits better in the Ar-introduced BST films than in the O{sub 2}-grown BST films. High resolution transmission electron microscopy images show that an amorphous region GB with large size appears between two lattice planes corresponding to oxygen vacancies defects in the Ar-introduced BST. Fourier-transform infrared reflectivity spectroscopy results also reveal highly accumulated oxygen vacancies in the Ar-introduced BST films. And we propose that the conduction transport of the cell was dominantly contributed from not ions migration of oxygen vacancies but the electrons in our case according to the value of activation energies of two kinds of films.

Identification and quantification of oxygen vacancies in CeO{sub 2} nanocrystals and their role in formation of F-centers

Energy Technology Data Exchange (ETDEWEB)

Jaffari, G.Hassnain, E-mail: hassnain@qau.edu.pk [Department of Physics, Quaid-i-Azam University Islamabad (Pakistan); Imran, Ali [Department of Physics, Quaid-i-Azam University Islamabad (Pakistan); Bah, M. [Department of Materials Science and Engineering, University of Delaware, 19716, Newark, DE (United States); Ali, Awais; Bhatti, Arshad S. [Centre for Micro and Nano Devices, Department of Physics, COMSATS Institute of Information Technology, Park Road, Islamabad, 44000 (Pakistan); Qurashi, Umar Saeed [Department of Physics, Quaid-i-Azam University Islamabad (Pakistan); Ismat Shah, S. [Department of Materials Science and Engineering, University of Delaware, 19716, Newark, DE (United States); Department of Physics, University of Delaware, 19716, Newark, DE (United States)

2017-02-28

Highlights: • Detail crystal and electronic structural analysis was employed to quantify oxygen vacancies. • The Raman F{sub 2g} mode shifted towards lower wave number, exhibiting mode softening with broader and asymmetric peak. • Observation of absorption edge revealed presence of 4f band within the band gap. • PL emission studies revealed presence of F-centers with corresponding energy level located below 4f band. • Transitions associated by the F-center are mainly associated with 4f{sup 0} to 4f{sup 1}, F{sup ++} to 4f{sup 1} and 4f{sup 0} to F{sup +}. - Abstract: In this work we present synthesis and extensive characterization of Cerium oxide (CeO{sub 2}) nanocrystals. Comparison between the properties of as-prepared and air annealed nanoparticles has been carried out, with a goal to clearly identify the effect of oxygen vacancies on crystal, electronic and band structure. Detail crystal and electronic structural analysis was employed to quantify oxygen vacancies. Structural analysis confirmed that the formation of single phase cubic Fluorite structure for both as-prepared and annealed samples. Crystal and electronic structural studies confirmed that Ce ions exists in two oxidation states, Ce{sup +3} and Ce{sup +4}. Concentration of oxygen vacancies was larger in as-synthesis nanocrystal. A drastic decrease in oxygen vacancy concentration was observed for the sample annealed in air at 550 °C. For the as-prepared sample, the Raman allowed F{sub 2g} mode shifted towards lower wavenumber, exhibiting mode softening with broader and asymmetric peak. Observation of absorption edge revealed presence of 4f band within the band gap. Absorption with different band edge, confirmed different energy position of 4f level for the sample possessing oxygen vacancies. Blue shift of the band edge for as-prepared sample has been discussed in terms of increase in lattice parameter, formation of Ce{sup +3} ions, quantum confinement effect etc. Photoluminescence emission

Enhanced oxygen vacancy diffusion in Ta2O5 resistive memory devices due to infinitely adaptive crystal structure

Science.gov (United States)

Jiang, Hao; Stewart, Derek A.

2016-04-01

Metal oxide resistive memory devices based on Ta2O5 have demonstrated high switching speed, long endurance, and low set voltage. However, the physical origin of this improved performance is still unclear. Ta2O5 is an important archetype of a class of materials that possess an adaptive crystal structure that can respond easily to the presence of defects. Using first principles nudged elastic band calculations, we show that this adaptive crystal structure leads to low energy barriers for in-plane diffusion of oxygen vacancies in λ phase Ta2O5. Identified diffusion paths are associated with collective motion of neighboring atoms. The overall vacancy diffusion is anisotropic with higher diffusion barriers found for oxygen vacancy movement between Ta-O planes. Coupled with the fact that oxygen vacancy formation energy in Ta2O5 is relatively small, our calculated low diffusion barriers can help explain the low set voltage in Ta2O5 based resistive memory devices. Our work shows that other oxides with adaptive crystal structures could serve as potential candidates for resistive random access memory devices. We also discuss some general characteristics for ideal resistive RAM oxides that could be used in future computational material searches.

Using Dopants to Tune Oxygen Vacancy Formation in Transition Metal Oxide Resistive Memory.

Science.gov (United States)

Jiang, Hao; Stewart, Derek A

2017-05-17

Introducing dopants is an important way to tailor and improve electronic properties of transition metal oxides used as high-k dielectric thin films and resistance switching layers in leading memory technologies, such as dynamic and resistive random access memory (ReRAM). Ta 2 O 5 has recently received increasing interest because Ta 2 O 5 -based ReRAM demonstrates high switching speed, long endurance, and low operating voltage. However, advances in optimizing device characteristics with dopants have been hindered by limited and contradictory experiments in this field. We report on a systematic study on how various metal dopants affect oxygen vacancy formation in crystalline and amorphous Ta 2 O 5 from first principles. We find that isoelectronic dopants and weak n-type dopants have little impact on neutral vacancy formation energy and that p-type dopants can lower the formation energy significantly by introducing holes into the system. In contrast, n-type dopants have a deleterious effect and actually increase the formation energy for charged oxygen vacancies. Given the similar doping trend reported for other binary transition metal oxides, this doping trend should be universally valid for typical binary transition metal oxides. Based on this guideline, we propose that p-type dopants (Al, Hf, Zr, and Ti) can lower the forming/set voltage and improve retention properties of Ta 2 O 5 ReRAM.

Oxygen Evolution at Hematite Surfaces: The Impact of Structure and Oxygen Vacancies on Lowering the Overpotential

NARCIS (Netherlands)

Zhang, X.; Klaver, P.; van Santen, R.; van de Sanden, M. C. M.; Bieberle, A.

2016-01-01

Simulations of the oxygen evolution reaction (OER) are essential for understanding the limitations of water splitting. Most research has focused so far on the OER at flat metal oxide surfaces. The structure sensitivity of the OER has, however, recently been highlighted as a promising research

First-principles simulations of the leakage current in metal-oxide-semiconductor structures caused by oxygen vacancies in HfO2 high-K gate dielectric

International Nuclear Information System (INIS)

Mao, L.F.; Wang, Z.O.

2008-01-01

HfO 2 high-K gate dielectric has been used as a new gate dielectric in metal-oxide-semiconductor structures. First-principles simulations are used to study the effects of oxygen vacancies on the tunneling current through the oxide. A level which is nearly 1.25 eV from the bottom of the conduction band is introduced into the bandgap due to the oxygen vacancies. The tunneling current calculations show that the tunneling currents through the gate oxide with different defect density possess the typical characteristic of stress-induced leakage current. Further analysis shows that the location of oxygen vacancies will have a marked effect on the tunneling current. The largest increase in the tunneling current caused by oxygen vacancies comes about at the middle oxide field when defects are located at the middle of the oxide. (copyright 2008 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Study of the movement of oxygen vacancies in the orthorhombic phase of YBa2Cu3O7-x by positron Doppler broadening spectroscopy

International Nuclear Information System (INIS)

Hong Zhang; Xiao-Gan Wang; Yao-Xian Fu

1988-01-01

The positron annihilation Doppler spectroscopy is used to monitor the movement of oxygen vacancy of YBa 2 Cu 3 O 7-x and an activation energy of (0.80 ± 0.10) eV for migration of oxygen vacancy in orthorhombic phase is obtained. (author)

Defect chemistry modelling of oxygen-stoichiometry, vacancy concentrations, and conductivity of (La1-xSrx)(y)MnO3 +/-delta

DEFF Research Database (Denmark)

Poulsen, F.W.

2000-01-01

model, based on delocalised electrons, electron holes and all B-ions being trivalent is given in Appendix A. The sequential mathematical method allows us to calculate the high temperature oxygen partial pressure dependent properties of (La1-xSrx)(y)MnO3+/-delta in a unified manner irrespective...... are calculated by the small polaron model containing only ionic species - the B-ion may be Mn-B' (Mn2+), Mn-B(x) (Mn3+), and Mn-B(Mn4+). The A/B-ratio = y greatly influences the oxygen stoichiometry, oxygen ion vacancy- and cation vacancy concentrations and the total conductivity. Calculations are given...

Oxygen vacancy and Moessbauer parameters of Fe doped tin oxides

International Nuclear Information System (INIS)

Nomura, K.; Mudarra Navarro, A.M.; Errico, L.; Rodriguez Torres, C.E.

2013-01-01

It is not clear what the local environment of Fe ions included in rutile structure is. In order to clarify this point, Moessbauer parameters of 57 Fe doped SnO 2 are compared with the results of ab initio calculation taking into account different configurations of iron and oxygen vacancy in the rutile structure of SnO 2 . Calculations were performed using the LAPW+lo method (Wien2k); RMT x Kmax = 7, A mesh of 50 k-points at IBZ, 2x2x2 super cell of SnO 2 . (J.P.N.)

Density functional study on the heterogeneous oxidation of NO over α-Fe_2O_3 catalyst by H_2O_2: Effect of oxygen vacancy

International Nuclear Information System (INIS)

Song, Zijian; Wang, Ben; Yu, Jie; Ma, Chuan; Zhou, Changsong; Chen, Tao; Yan, Qianqian; Wang, Ke; Sun, Lushi

2017-01-01

Highlights: • NO and H_2O_2 adsorption on perfect and oxygen defect α-Fe_2O_3 (0 0 1) surface were studied by DFT calculations. • H_2O_2 shows high chemical reactivity for its adsorption on oxygen defect α-Fe_2O_3 (0 0 1) surface. • Oxygen vacancy plays an important role of the catalytic oxidation of NO by H_2O_2 over the α-Fe_2O_3 catalyst surfaces. • Mechanism of NO oxidation over α-Fe_2O_3 (0 0 1) surface by H_2O_2 was explained. - Abstract: Catalytic oxidation with H_2O_2 is a promising method for NOx emission control in coal-fired power plants. Hematite-based catalysts are attracting increased attention because of their surface redox reactivity. To elucidate the NO oxidation mechanism on α-Fe_2O_3 surfaces, density functional theory (DFT) calculations were conducted by investigating the adsorption characteristics of nitric oxide (NO) and hydrogen peroxide (H_2O_2) on perfect and oxygen defect α-Fe_2O_3 (0 0 1) surfaces. Results show that NO was molecularly adsorbed on two kinds of surfaces. H_2O_2 adsorption on perfect surface was also in a molecular form; however, H_2O_2 dissociation occurred on oxygen defect α-Fe_2O_3 (0 0 1) surface. The adsorption intensities of the two gas molecules in perfect α-Fe_2O_3 (0 0 1) surface followed the order NO > H_2O_2, and the opposite was true for the oxygen defect α-Fe_2O_3 (0 0 1). Oxygen vacancy remarkably enhanced the adsorption intensities of NO and H_2O_2 and promoted H_2O_2 decomposition on catalyst surface. As an oxidative product of NO, HNO_2 was synthesized when NO and H_2O_2 co-adsorbed on the oxygen defect α-Fe_2O_3 (0 0 1) surface. Analyses of Mulliken population, electron density difference, and partial density of states showed that H_2O_2 decomposition followed the Haber–Weiss mechanism. The trends of equilibrium constants suggested that NO adsorption on α-Fe_2O_3 (0 0 1) surface was more favorable at low than at high temperatures, whereas H_2O_2 adsorption was favorable between 375 and

Oxygen vacancy induces self-doping effect and metalloid LSPR in non-stoichiometric tungsten suboxide synergistically contributing to the enhanced photoelectrocatalytic performance of WO3-x/TiO2-x heterojunction.

Science.gov (United States)

Huang, Weicheng; Wang, Jinxin; Bian, Lang; Zhao, Chaoyue; Liu, Danqing; Guo, Chongshen; Yang, Bin; Cao, Wenwu

2018-06-27

A WO3-x/TiO2-x nanotube array (NTA) heterojunction photoanode was strategically designed to improve photoelectrocatalytic (PEC) performance by establishing a synergistic vacancy-induced self-doping effect and localized surface plasmon resonance (LSPR) effect of metalloid non-stoichiometric tungsten suboxide. The WO3-x/TiO2-x NTA heterojunction photoanode was synthesized through a successive process of anodic oxidation to form TiO2 nanotube arrays, magnetron sputtering to deposit metalloid WO3-x, and post-hydrogen reduction to engender oxygen vacancy in TiO2-x as well as crystallization. On the merits of such a synergistic effect, WO3-x/TiO2-x shows higher light-harvesting ability, stronger photocurrent response, and resultant improved photoelectrocatalytic performance than the contrast of WO3-x/TiO2, WO3/TiO2 and TiO2, confirming the importance of oxygen vacancies in improving PEC performance. Theoretical calculation based on density functional theory was applied to investigate the electronic structural features of samples and reveal how the oxygen vacancy determines the optical property. The carrier density tuning mechanism and charge transfer model were considered to be associated with the synergistic effect of self-doping and metalloid LSPR effect in the WO3-x/TiO2-x NTA.

Understanding cation ordering and oxygen vacancy site preference in Ba3CaNb2O9 from first-principles

Science.gov (United States)

Ding, Hepeng; Virkar, Anil; Liu, Feng

2014-03-01

We investigate the physical mechanism underlying the formation of the B-site cation ordering and the oxygen vacancy site selection in Ba3CaNb2O9 using density functional theory calculations. We found that either cation site exchange or oxygen vacancy formation induces negligible lattice strain. This implies that the ionic radius plays an insignificant role in governing these two processes. Furthermore, the electrostatic interactions are found dominant in the ordering of mixed valence species on one or more sites, the ionic bond strength is identified as the dominant force in governing both the 1:2 B-site cation ordering along the direction and the oxygen vacancy site preference in Ba3CaNb2O9. Specifically, the cation ordering can be rationalized by the increased mixing bonding energy of the Ca-O-Nb bonds over the Ca-O-Ca and Nb-O-Nb bonds, i.e., 1/2(Ca-O-Ca + Nb-O-Nb) Grant Number DE-SC0001061 as a flow through from the University of South Carolina.

Atomic geometry and STM simulations of a TiO.sub.2./sub.(110) surface upon formation of an oxygen vacancy and hydroxyl group

Czech Academy of Sciences Publication Activity Database

Mutombo, Pingo; Kiss, A.M.; Berkó, A.; Cháb, Vladimír

2008-01-01

Roč. 16, - (2008), 025007/1-025007/9 ISSN 0965-0393 R&D Projects: GA AV ČR IAA1010413 Grant - others:MŠMT(CZ) 9/2004 KONTAKT Institutional research plan: CEZ:AV0Z10100521 Source of funding: V - iné verejné zdroje Keywords : vacance * Oxygen * OH group * STM Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.388, year: 2008

Oxygen vacancy induced magnetization switching in Fe{sub 3}O{sub 4} epitaxial ultrathin films on GaAs(100)

Energy Technology Data Exchange (ETDEWEB)

Huang, Zhaocong, E-mail: zhaocong.huang@gmail.com [Department of Physics, Southeast University, Nanjing 211189 (China); Spintronics and Nanodevice Laboratory, Department of Electronics, University of York, York YO10 5DD (United Kingdom); School of Electronic Science and Engineering, Southeast University, Nanjing 210096 (China); Chen, Qian; Zhai, Ya, E-mail: yazhai@seu.edu.cn, E-mail: jlwang@seu.edu.cn; Wang, Jinlan, E-mail: yazhai@seu.edu.cn, E-mail: jlwang@seu.edu.cn [Department of Physics, Southeast University, Nanjing 211189 (China); Xu, Yongbing [Spintronics and Nanodevice Laboratory, Department of Electronics, University of York, York YO10 5DD (United Kingdom); Wang, Baoping [School of Electronic Science and Engineering, Southeast University, Nanjing 210096 (China)

2015-05-04

The magnetic and transport properties of half metallic Fe{sub 3}O{sub 4}, which are sensitive to the stoichiometry, are the key issue for applications in spintronics. An anomalous enlargement of the saturation magnetic moment is found in a relatively thick sample of epitaxial Fe{sub 3}O{sub 4} film by post-growth oxidation method. The investigation of the thickness dependence of magnetic moment suggests that the enhanced magnetism moment may come from the existence of oxygen vacancies. First-principles calculations reveal that with oxygen vacancies in Fe{sub 3}O{sub 4} crystal the spin of Fe ions in the tetrahedron site near the vacancy is much easier to switch parallel to the Fe ions in the octahedron site by temperature disturbance, supported by the temperature dependence of magnetic moment of Fe{sub 3}O{sub 4} films in experiment.

Zinc Vacancy Formation and its Effect on the Conductivity of ZnO

Science.gov (United States)

Khan, Enamul; Weber, Marc; Langford, Steve; Dickinson, Tom

2010-03-01

Exposing single crystal ZnO to 193-nm ArF excimer laser radiation can produce metallic zinc nanoparticles along the surface. The particle production mechanism appears to involve interstitial-vacancy pair formation in the near-surface bulk. Conductivity measurements made with one probe inside the laser spot and the other outside show evidence for rectifying behavior. Positron annihilation spectroscopy confirms the presence of Zn vacancies. We suggest that Zn vacancies are a possible source of p-type behavior in irradiated ZnO. Quadrupole mass spectroscopy shows that both oxygen and zinc are emitted during irradiation. Electron-hole pair production has previously been invoked to account for particle desorption from ZnO during UV illumination. Our results suggest that preexisting and laser-generated defects play a critical role in particle desorption and Zn vacancy formation.

Living on the edge : STM studies of the creation, diffusion and annihilation of surface vacancies

NARCIS (Netherlands)

Schoots, Koen

2007-01-01

This thesis describes an STM study of the creation, diffusion and annihilation of missing atoms, so-called surface vacancies, in the Cu(100) surface. Because of the extremely high mobility of surface vacancies in combination with their extremely low density, we have been forced to use tracer

Oxygen vacancies induced enhancement of photoconductivity of La0.5Sr0.5CoO3 - δ thin film

Science.gov (United States)

Gao, R. L.; Fu, C. L.; Cai, W.; Chen, G.; Deng, X. L.; Yang, H. W.; Sun, J. R.; Zhao, Y. G.; Shen, B. G.

2014-09-01

Effects of light and electrical current on the electrical transport properties and photovoltaic properties of oxygen-stoichiometric La0.5Sr0.5CoO3 and oxygen-deficient La0.5Sr0.5CoO3 - δ films prepared by pulsed laser deposition have been investigated. Oxygen-deficient films annealed in a vacuum show an obvious increase of resistance and lattice parameter. Besides, a direct correlation between the magnitude of the photoconductivity and oxygen vacancies in La0.5Sr0.5CoO3 - δ films has been observed. The light illumination causes a resistance drop to show the photoconductivity effect. Moreover, the photoconductivity can be remarkably enhanced by increasing the electrical current, that is, it exhibits current-enhanced photoconductivity (CEPC) effect. Oxygen deficiency in the annealed film leads to the formation of a structural disorder in the Co-O-Co conduction channel due to the accumulated oxygen vacancies and hence is believed to be responsible for the increase in higher photoconductivity. These results may be important for practical applications in photoelectric devices.

Oxygen vacancy tuned Ohmic-Schottky conversion for enhanced performance in β-Ga{sub 2}O{sub 3} solar-blind ultraviolet photodetectors

Energy Technology Data Exchange (ETDEWEB)

Guo, D. Y.; Wu, Z. P.; An, Y. H.; Guo, X. C.; Chu, X. L.; Sun, C. L.; Tang, W. H., E-mail: whtang@bupt.edu.cn [School of Science, Beijing University of Posts and Telecommunications, Beijing 100876 (China); State Key Laboratory of Information Photonics and Optical Communications, Beijing University of Posts and Telecommunications, Beijing 100876 (China); Li, L. H. [Physics Department, The State University of New York at Potsdam, Potsdam, New York 13676-2294 (United States); Li, P. G., E-mail: pgli@zstu.edu.cn [School of Science, Beijing University of Posts and Telecommunications, Beijing 100876 (China); Center for Optoelectronics Materials and Devices, Department of Physics, Zhejiang Sci-Tech University, Hangzhou, 310018 Zhejiang (China)

2014-07-14

β-Ga{sub 2}O{sub 3} epitaxial thin films were deposited using laser molecular beam epitaxy technique and oxygen atmosphere in situ annealed in order to reduce the oxygen vacancy. Metal/semiconductor/metal structured photodetectors were fabricated using as-grown film and annealed film separately. Au/Ti electrodes were Ohmic contact with the as-grown films and Schottky contact with the annealed films. In compare with the Ohmic-type photodetector, the Schottky-type photodetector takes on lower dark current, higher photoresponse, and shorter switching time, which benefit from Schottky barrier controlling electron transport and the quantity of photogenerated carriers trapped by oxygen vacancy significant decreasing.

Oxygen vacancy induced by La and Fe into ZnO nanoparticles to modify ferromagnetic ordering

International Nuclear Information System (INIS)

Verma, Kuldeep Chand; Kotnala, R.K.

2016-01-01

We reported long-range ferromagnetic interactions in La doped Zn 0.95 Fe 0.05 O nanoparticles that mediated through lattice defects or vacancies. Zn 0.92 Fe 0.05 La 0.03 O (ZFLaO53) nanoparticles were synthesized by a sol–gel process. X-ray fluorescence spectrum of ZFLaO53 detects the weight percentage of Zn, Fe, La and O. X-ray diffraction shows the hexagonal Wurtzite ZnO phase. The Rietveld refinement has been used to calculate the lattice parameters and the position of Zn, Fe, La and O atoms in the Wurtzite unit cell. The average size of ZFLaO53 nanoparticles is 99 nm. The agglomeration type product due to OH ions with La results into ZnO nanoparticles than nanorods that found in pure ZnO and Zn 0.95 Fe 0.05 O sample. The effect of doping concentration to induce Wurtzite ZnO structure and lattice defects has been analyzed by Raman active vibrational modes. Photoluminescence spectra show an abnormal emission in both UV and visible region, and a blue shift at near band edge is formed with doping. The room temperature magnetic measurement result into weak ferromagnetism but pure ZnO is diamagnetic. However, the temperature dependent magnetic measurement using zero-field and field cooling at dc magnetizing field 500 Oe induces long-range ferromagnetic ordering. It results into antiferromagnetic Neel temperature of ZFLaO53 at around 42 K. The magnetic hysteresis is also measured at 200, 100, 50 and 10 K measurement that indicate enhancement in ferromagnetism at low temperature. Overall, the La doping into Zn 0.95 Fe 0.05 O results into enhanced antiferromagnetic interaction as well as lattice defects/vacancies. The role of the oxygen vacancy as the dominant defects in doped ZnO must form Bound magnetic polarons has been described. - Graphical abstract: The long-range ferromagnetic order in Zn 0.92 Fe 0.05 La 0.03 O nanoparticles at low temperature measurements involves oxygen vacancy as the medium of magnetic interactions. - Highlights: • The La and Fe doping

Switchable diode effect in oxygen vacancy-modulated SrTiO{sub 3} single crystal

Energy Technology Data Exchange (ETDEWEB)

Pan, Xinqiang; Shuai, Yao; Wu, Chuangui; Luo, Wenbo; Sun, Xiangyu; Zeng, Huizhong; Bai, Xiaoyuan; Gong, Chaoguan; Jian, Ke; Zhang, Wanli [University of Electronic Science and Technology of China, State Key Laboratory of Electronic Thin Films and Integrated Devices, Chengdu (China); Zhang, Lu; Guo, Hongliang [University of Electronic Science and Technology of China, The Center for Robotics, Chengdu (China); Tian, Benlang [26th Institute of China Electronics Technology Group Corporation, Chongqing (China)

2017-09-15

SrTiO{sub 3} (STO) single crystal wafer was annealed in vacuum, and co-planar metal-insulator-metal structure of Pt/Ti/STO/Ti/Pt were formed by sputtering Pt/Ti electrodes onto the surface of STO after annealing. The forming-free resistive switching behavior with self-compliance property was observed in the sample. The sample showed switchable diode effect, which is explained by a simple model that redistribution of oxygen vacancies (OVs) under the external electric field results in the formation of n-n{sup +} junction or n{sup +}-n junction (n donated n-type semiconductor; n{sup +} donated heavily doped n-type semiconductor). The self-compliance property is also interpreted by the formation of n-n{sup +}/n{sup +}-n junction caused by the migration of the OVs under the electric field. (orig.)

Simple method to enhance positive bias stress stability of In-Ga-Zn-O thin-film transistors using a vertically graded oxygen-vacancy active layer.

Science.gov (United States)

Park, Ji Hoon; Kim, Yeong-Gyu; Yoon, Seokhyun; Hong, Seonghwan; Kim, Hyun Jae

2014-12-10

We proposed a simple method to deposit a vertically graded oxygen-vacancy active layer (VGA) to enhance the positive bias stress (PBS) stability of amorphous indium gallium zinc oxide (a-IGZO) thin-film transistors (TFTs). We deposited a-IGZO films by sputtering (target composition; In2O3:Ga2O3:ZnO = 1:1:1 mol %), and the oxygen partial pressure was varied during deposition so that the front channel of the TFTs was fabricated with low oxygen partial pressure and the back channel with high oxygen partial pressure. Using this method, we were able to control the oxygen vacancy concentration of the active layer so that it varied with depth. As a result, the turn-on voltage shift following a 10 000 s PBS of optimized VGA TFT was drastically improved from 12.0 to 5.6 V compared with a conventional a-IGZO TFT, without a significant decrease in the field effect mobility. These results came from the self-passivation effect and decrease in oxygen-vacancy-related trap sites of the VGA TFTs.

A Facile Approach to Prepare Black TiO2 with Oxygen Vacancy for Enhancing Photocatalytic Activity

Science.gov (United States)

Chen, Shihao; Xiao, Yang; Hu, Zhengfa; Zhao, Hui; Xie, Wei

2018-01-01

Black TiO2 has triggered worldwide research interest due to its excellent photocatalytic properties. However, the understanding of its structure–property relationships and a more effective, facile and versatile method to produce it remain great challenges. We have developed a facile approach to synthesize black TiO2 nanoparticles with significantly improved light absorption in the visible and infrared regions. The experimental results show that oxygen vacancies are the major factors responsible for black coloration. More importantly, our black TiO2 nanoparticles have no Ti3+ ions. These oxygen vacancies could introduce localized states in the bandgap and act as trap centers, significantly decreasing the electron–hole recombination. The photocatalytic decomposition of both rhodamine B and methylene blue demonstrated that, under ultraviolet light irradiation, better photocatalytic performance is achieved with our black TiO2 nanoparticles than with commercial TiO2 nanoparticles. PMID:29659500

Electronic structure and optical properties of N vacancy and O filling on n-GaN (0001) surface

Science.gov (United States)

Lu, Feifei; Liu, Lei; Xia, Sihao; Diao, Yu; Feng, Shu

2018-06-01

In the X-ray photoelectron spectroscopy experiment, we observed that the valence band spectrum of the n-GaN (0001) surface appeared a bump near 1.9 eV after Ar etching and the N/Ga ratio became smaller, while the bump disappeared upon exposure to air. In order to analyze this phenomenon theoretically, we mainly study the electronic structure and optical properties of n-GaN (0001) surface with N vacancy and filled with O atom based on the first principles of density functional theory. The results suggest that the n-GaN (0001) surface exhibits semi-metallic property. The introduction of N vacancy reduces the n-type conductivity, whereas the filling of O atom enhances conductivity. The density of state near -1.9eV shows a good agreement between the clean n-type surface and the O-atom-filled surface, while the N vacancy surface has a higher density of states, which is similar to the experimentally observed phenomenon. It is also found that the existence of N vacancy reduces the photoemission properties of the n-GaN (0001) surface and the filling of O atom alleviates the defect caused by vacancy. This study shows that N vacancy increases the doping difficulty of n-type GaN films, however, the filling of O atom may compensate for the diminished photoelectric properties induced by N vacancy and be conducive to prepare high-performance optoelectronic devices with the contact of n-GaN and metal.

Kinetics and Mechanisms of Oxygen Surface Exchange on La0.6Sr0.4FeO3-delta Thin Films

DEFF Research Database (Denmark)

Mosleh, Majid; Søgaard, Martin; Hendriksen, Peter Vang

2009-01-01

and oxygen partial pressure [i.e., the incorporation reaction has the same reaction enthalpy (H0=−105 KJ/mol) and entropy (S0=−75.5 J/mol/K) as found for bulk material]. The thin film shows smaller apparent electrical conductivity than reported for bulk. This is due to imperfections in the film, which...... is not totally dense and contains closed porosity. Electrical conductivity relaxation was used to determine the surface exchange coefficient and its dependence on the temperature and oxygen partial pressure. Relaxation curves showed a good fit to a simple exponential decay. The vacancy surface exchange...... coefficient (kV) determined from Kchem shows a slope (log kV vs log PO2) between 0.51 and 0.85. It is further found that kV is proportional to the product of the oxygen partial pressure and the vacancy concentration (kVPO2). Different reaction mechanisms that can account for the observed PO2 and -dependence...

Surface Reduced CeO2 Nanowires for Direct Conversion of CO2 and Methanol to Dimethyl Carbonate: Catalytic Performance and Role of Oxygen Vacancy

Directory of Open Access Journals (Sweden)

Zhongwei Fu

2018-04-01

Full Text Available Ultralong 1D CeO2 nanowires were synthesized via an advanced solvothermal method, surface reduced under H2 atmosphere, and first applied in direct synthesis of dimethyl carbonate (DMC from CO2 and CH3OH. The micro morphologies, physical parameters of nanowires were fully investigated by transmission electron microscopy (TEM, X-ray diffraction (XRD, N2 adsorption, X-ray photoelectron spectrum (XPS, and temperature-programmed desorption of ammonia/carbon dioxide (NH3-TPD/CO2-TPD. The effects of surface oxygen vacancy and acidic/alkaline sites on the catalytic activity was explored. After reduction, the acidic/alkaline sites of CeO2 nanowires can be dramatically improved and evidently raised the catalytic performance. CeO2 nanowires reduced at 500 °C (CeO2_NW_500 exhibited notably superior activity with DMC yield of 16.85 mmol gcat−1. Furthermore, kinetic insights of initial rate were carried out and the apparent activation energy barrier of CeO2_NW_500 catalyst was found to be 41.9 kJ/mol, much tiny than that of CeO2_NW catalyst (74.7 KJ/mol.

Ultrathin FeOOH nanolayers with abundant oxygen vacancies on BiVO{sub 4} photoanodes for efficient water oxidation

Energy Technology Data Exchange (ETDEWEB)

Zhang, Beibei [State Key Laboratory for Oxo Synthesis and Selective Oxidation, National Engineering Research Center for Fine Petrochemical Intermediates, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou (China); State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province, and College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou (China); Wang, Lei; Zhang, Yajun; Bi, Yingpu [State Key Laboratory for Oxo Synthesis and Selective Oxidation, National Engineering Research Center for Fine Petrochemical Intermediates, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou (China); Ding, Yong [State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province, and College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou (China)

2018-02-19

Photoelectrochemical (PEC) water splitting is a promising method for storing solar energy in the form of hydrogen fuel, but it is greatly hindered by the sluggish kinetics of the oxygen evolution reaction (OER). Herein, a facile solution impregnation method is developed for growing ultrathin (2 nm) highly crystalline β-FeOOH nanolayers with abundant oxygen vacancies on BiVO{sub 4} photoanodes. These exhibited a remarkable photocurrent density of 4.3 mA cm{sup -2} at 1.23 V (vs. reversible hydrogen electrode (RHE), AM 1.5 G), which is approximately two times higher than that of amorphous FeOOH fabricated by electrodeposition. Systematic studies reveal that the excellent PEC activity should be attributed to their ultrathin crystalline structure and abundant oxygen vacancies, which could effectively facilitate the hole transport/trapping and provide more active sites for water oxidation. (copyright 2018 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Magnetism, Spin Texture, and In-Gap States: Atomic Specialization at the Surface of Oxygen-Deficient SrTiO_{3}.

Science.gov (United States)

Altmeyer, Michaela; Jeschke, Harald O; Hijano-Cubelos, Oliver; Martins, Cyril; Lechermann, Frank; Koepernik, Klaus; Santander-Syro, Andrés F; Rozenberg, Marcelo J; Valentí, Roser; Gabay, Marc

2016-04-15

Motivated by recent spin- and angular-resolved photoemission (SARPES) measurements of the two-dimensional electronic states confined near the (001) surface of oxygen-deficient SrTiO_{3}, we explore their spin structure by means of ab initio density functional theory (DFT) calculations of slabs. Relativistic nonmagnetic DFT calculations display Rashba-like spin winding with a splitting of a few meV and when surface magnetism on the Ti ions is included, bands become spin-split with an energy difference ∼100  meV at the Γ point, consistent with SARPES findings. While magnetism tends to suppress the effects of the relativistic Rashba interaction, signatures of it are still clearly visible in terms of complex spin textures. Furthermore, we observe an atomic specialization phenomenon, namely, two types of electronic contributions: one is from Ti atoms neighboring the oxygen vacancies that acquire rather large magnetic moments and mostly create in-gap states; another comes from the partly polarized t_{2g} itinerant electrons of Ti atoms lying further away from the oxygen vacancy, which form the two-dimensional electron system and are responsible for the Rashba spin winding and the spin splitting at the Fermi surface.

A quantum-chemical study of oxygen-vacancy defects in PbTiO3 crystals

International Nuclear Information System (INIS)

Stashans, Arvids; Serrano, Sheyla; Medina, Paul

2006-01-01

Investigation of an oxygen vacancy and F center in the cubic and tetragonal lattices of PbTiO 3 crystals is done by means of quantum-chemical simulations. Displacements of defect-surrounding atoms, electronic and optical properties, lattice relaxation energies and some new effects due to the defects presence are reported and analyzed. A comparison with similar studies is made and conclusions are drawn on the basis of the obtained results

The modulation of oxygen vacancies by the combined current effect and temperature cycling in La0.7Sr0.3CoO3 film

Science.gov (United States)

Li, J.; Wang, J.; Kuang, H.; Zhao, Y. Y.; Qiao, K. M.; Liu, Y.; Hu, F. X.; Sun, J. R.; Shen, B. G.

2018-05-01

Modulating the oxygen defect concentration has been accepted as an effective method to obtain high catalytic activity in perovskite cobaltites. However, controllably modifying the oxygen vacancy is still a challenge in this type of materials, which strongly obstructs their application. Here, we report a successful oxygen vacancies modulation in the La0.7Sr0.3CoO3 (LSCO) film by using combined current effect and temperature cycling. The temperature dependent transport properties of the LSCO/LAO film were investigated. The results revealed that the resistance of the film keeps increasing under the repeated measurements. It was found that the accumulation of the oxygen vacancy by current effect transforms the Co4+ ion into Co3+ ion, which results in the enhancement of the resistance and thus the transport switching behavior. Moreover, the resistance in the cooling process was found to be much higher than that in previous cooling and heating processes, which indicates that the oxygen escapes more quickly in the high temperature region. On the other hand, our analysis indicates that the CoO6 distortion may contribute to the switching of transport behaviors in the low temperature region. Our work provides an effective and controllable way to modulate oxygen defect in the perovskite-type oxides.

Ab initio atomic thermodynamics investigation on oxygen defects in the anatase TiO{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Cheng, Zhijun [College of Science, University of Shanghai for Science and Technology, Shanghai 200093 (China); Liu, Tingyu, E-mail: liutyyxj@163.com [College of Science, University of Shanghai for Science and Technology, Shanghai 200093 (China); Yang, Chenxing; Gan, Haixiu [College of Science, University of Shanghai for Science and Technology, Shanghai 200093 (China); Chen, Jianyu [Key Laboratory of Materials for High Power Laser, Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800 (China); Zhang, Feiwu [Nanochemistry Research Institute, Curtin University, GPO Box U1987, Perth, WA 6845 (Australia)

2013-01-05

Highlights: Black-Right-Pointing-Pointer Three typical oxygen defects under the different annealing conditions have been studied. Black-Right-Pointing-Pointer The oxygen vacancy is easier to form at the surface than in the bulk. Black-Right-Pointing-Pointer The adsorption of O{sub 2} whose orientation is parallel to the surface should be more favorable. Black-Right-Pointing-Pointer The reduction reaction may firstly undertake at the surface during the annealing treatment. Black-Right-Pointing-Pointer The interstitial oxygen has important contribution to lead to the reduction of the band gap. - Abstract: In the framework of the ab initio atomic thermodynamics, the preliminary analysis of the oxygen defects in anatase TiO{sub 2} has been done by investigating the influence of the annealing treatment under representative conditions on three typical oxygen defects, that is, oxygen vacancy, oxygen adsorption and oxygen interstitial. Our results in this study agree well with the related experimental results. The molecular species of the adsorbed O{sub 2} is subject to the ratio of the number of the O{sub 2} to that of the vacancy, as well as to the initial orientation of O{sub 2} relative to the surface (101). Whatever the annealing condition is, the oxygen vacancy is easier to form at the surface than in the bulk indicating that the reduction reaction may firstly undertake at the surface during the annealing treatment, which is consistent with the phase transformation experiments. The molecular ion, peroxide species, caused by the interstitial oxygen has important contribution to the top of the valence band and lead to the reduction of the band gap.

Synergistic effect of oxygen vacancy and nitrogen doping on enhancing the photocatalytic activity of Bi{sub 2}O{sub 2}CO{sub 3} nanosheets with exposed {0 0 1} facets for the degradation of organic pollutants

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yafei [School of Physics and Information Technology, Shaanxi Normal University, Xi’an 710062 (China); Zhu, Gangqiang, E-mail: zgq2006@snnu.edu.cn [School of Physics and Information Technology, Shaanxi Normal University, Xi’an 710062 (China); Hojamberdiev, Mirabbos [School of Physics and Information Technology, Shaanxi Normal University, Xi’an 710062 (China); Department of Natural and Mathematic Sciences, Turin Polytechnic University in Tashkent, Kichik Halqa Yo’li 17, Tashkent 100095 (Uzbekistan); Gao, Jianzhi [School of Physics and Information Technology, Shaanxi Normal University, Xi’an 710062 (China); Hao, Jing [Xi' an Rejee Industry Development Co., Ltd., Xi’an 710016 (China); Zhou, Jianping; Liu, Peng [School of Physics and Information Technology, Shaanxi Normal University, Xi’an 710062 (China)

2016-05-15

Highlights: • Nitrogen-doped Bi{sub 2}O{sub 2}CO{sub 3} flower-like microstructures were synthesized by hydrothermal method. • Surface oxygen vacancy were obtained by irradiating the nitrogen-doped Bi{sub 2}O{sub 2}CO{sub 3} with UV light. • Photocatalytic activity was studied by degrading Rhodamine B. • A synergistic effect between oxygen vacancy and nitrogen doping in Bi{sub 2}O{sub 2}CO{sub 3}. - Abstract: Single-crystalline bare Bi{sub 2}O{sub 2}CO{sub 3} (BOC) nanosheets with exposed {0 0 1} facets and nitrogen-doped Bi{sub 2}O{sub 2}CO{sub 3} (NBOC) flower-like microstructures were synthesized by a simple hydrothermal method. The nitrogen-doped Bi{sub 2}O{sub 2}CO{sub 3} flower-like microstructures with oxygen vacancy (UV-NBOC) were obtained by irradiating the NBOC microstructures with UV light for 2 h in ethanol. The UV–vis diffuse reflectance spectra showed that the NBOC and UV-NBOC nanosheets exhibit an obvious red shift in light absorption band compared with the pure BOC nanosheets. Rhodamine B (RhB) was chosen as a model organic pollutant to verify the influence of oxygen vacancy and nitrogen doping on the photocatalytic activity of Bi{sub 2}O{sub 2}CO{sub 3} under simulated solar light irradiation. Judging from the kinetics of RhB photodegradation over the synthesized samples, a synergistic effect between oxygen vacancy and nitrogen doping was found with a remarkable increase (more than 10 and 2 times) in the photocatalytic activity of UV-NBOC compared with BOC and NBOC, respectively. Moreover, the UV-NBOC also exhibited an excellent cyclability and superior photocatalytic activity toward degradation of other organic pollutants (methylene blue, Congo red, Bisphenol A) under simulated solar light irradiation.

Vacancy-Mediated Magnetism in Pure Copper Oxide Nanoparticles

Science.gov (United States)

2010-01-01

Room temperature ferromagnetism (RTF) is observed in pure copper oxide (CuO) nanoparticles which were prepared by precipitation method with the post-annealing in air without any ferromagnetic dopant. X-ray photoelectron spectroscopy (XPS) result indicates that the mixture valence states of Cu1+ and Cu2+ ions exist at the surface of the particles. Vacuum annealing enhances the ferromagnetism (FM) of CuO nanoparticles, while oxygen atmosphere annealing reduces it. The origin of FM is suggested to the oxygen vacancies at the surface/or interface of the particles. Such a ferromagnet without the presence of any transition metal could be a very good option for a class of spintronics. PMID:20671775

Hydrogen isotope in erbium oxide: Adsorption, penetration, diffusion, and vacancy trapping

International Nuclear Information System (INIS)

Mao, Wei; Chikada, Takumi; Suzuki, Akihiro; Terai, Takayuki; Matsuzaki, Hiroyuki

2015-01-01

Highlights: • H adsorption on cubic Er 2 O 3 surface results in electron transfer from H to the surface. • The H penetration energy of at least 1.6 eV is required for cubic Er 2 O 3 surface. • The dominated mechanisms of H diffusion in bulk Er 2 O 3 are elucidated. • H diffusion near or at vacancies in Er 2 O 3 is an exothermic reaction. - Abstract: In this study, we report results using first-principles density functional theory calculations for four critical aspects of the interaction: H adsorption on Er 2 O 3 surface, surface-to-subsurface penetration of H into Er 2 O 3 , bulk diffusion of H in Er 2 O 3 , and trapping of H at vacancies. We identify surface stable adsorption positions and find that H prefers to transfer electrons to the surfaces and form covalent bonds with the nearest neighboring four oxygen atoms. For low surface coverage of H as in our case (0.89 × 10 14 H/cm 2 ), a penetration energy of at least 1.60 eV is required for cubic Er 2 O 3 surfaces. Further, the H diffusion barrier between the planes defined by Er 2 O 3 units along the favorable <1 1 1> direction is found to be very small – 0.16 eV – whereas higher barriers of 0.41 eV and 1.64 eV are required for diffusion across the planes, somewhat higher than the diffusion energy barrier of 0.20 eV observed experimentally at 873 K. In addition, we predict that interstitial H is exothermically trapped when it approaches a vacancy with the vacancy defect behaving as an electron trap since the H-vacancy defect is found to be more stable than the intrinsic defect

Oxygen vacancy effect on photoluminescence of KNb3O8 nanosheets

Science.gov (United States)

Li, Rui; Liu, Liying; Ming, Bangming; Ji, Yuhang; Wang, Ruzhi

2018-05-01

Fungus-like potassium niobate (KNb3O8) nanosheets have been synthesized on indium-doped tin oxide (ITO) glass substrates by a simple and environmental friendly two-step hydrothermal process. The prepared samples have been characterized by using X-ray Diffraction (XRD), Field Emission Scanning Electron Microscope (FESEM), High Resolution Transmission Electron Microscope (HRTEM), Fourier Transform Infra-Red Spectroscopy (FTIR), Raman Spectroscopy and X-ray Photoelectron Spectroscopy (XPS). Furthermore, the photoluminescence (PL) of KNb3O8 nanosheets have been systematically studied. The results showed that the PL spectrum is between 300 and 645 nm with a 325 nm light excitation, which is divided into some sub-peaks. It is different from the perfect KNb3O8 nanosheets whose PL emission peaks located at near 433 nm. It should be originated from the effect of the oxygen (O) vacancies in the KNb3O8 nanosheets, which the PLs peaks can be found at about 490 nm and 530 nm by different position of O vacancy. The experimental results are in accordance with the first-principles calculations. Our results may present a feasible clue to estimate the defect position in KNb3O8 by the shape analysis of its spectrum of PLs.

Density functional study on the heterogeneous oxidation of NO over α-Fe{sub 2}O{sub 3} catalyst by H{sub 2}O{sub 2}: Effect of oxygen vacancy

Energy Technology Data Exchange (ETDEWEB)

Song, Zijian, E-mail: szj22zc15@163.com [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, 430074, Wuhan (China); Wang, Ben, E-mail: benwang@hust.edu.cn [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, 430074, Wuhan (China); Yu, Jie, E-mail: yujie@hust.edu.cn [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, 430074, Wuhan (China); Ma, Chuan, E-mail: machuan628@163.com [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, 430074, Wuhan (China); Zhou, Changsong, E-mail: zhouchangsong@hust.edu.cn [School of Energy and Mechanical Engineering, Nanjing Normal University, 210042, Nanjing (China); Chen, Tao, E-mail: chentao_hust@foxmail.com [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, 430074, Wuhan (China); Yan, Qianqian [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, 430074, Wuhan (China); Wang, Ke, E-mail: m201570959@hust.edu.cn [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, 430074, Wuhan (China); Sun, Lushi, E-mail: sunlushi@hust.edu.cn [State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, 430074, Wuhan (China)

2017-08-15

Highlights: • NO and H{sub 2}O{sub 2} adsorption on perfect and oxygen defect α-Fe{sub 2}O{sub 3} (0 0 1) surface were studied by DFT calculations. • H{sub 2}O{sub 2} shows high chemical reactivity for its adsorption on oxygen defect α-Fe{sub 2}O{sub 3} (0 0 1) surface. • Oxygen vacancy plays an important role of the catalytic oxidation of NO by H{sub 2}O{sub 2} over the α-Fe{sub 2}O{sub 3} catalyst surfaces. • Mechanism of NO oxidation over α-Fe{sub 2}O{sub 3} (0 0 1) surface by H{sub 2}O{sub 2} was explained. - Abstract: Catalytic oxidation with H{sub 2}O{sub 2} is a promising method for NOx emission control in coal-fired power plants. Hematite-based catalysts are attracting increased attention because of their surface redox reactivity. To elucidate the NO oxidation mechanism on α-Fe{sub 2}O{sub 3} surfaces, density functional theory (DFT) calculations were conducted by investigating the adsorption characteristics of nitric oxide (NO) and hydrogen peroxide (H{sub 2}O{sub 2}) on perfect and oxygen defect α-Fe{sub 2}O{sub 3} (0 0 1) surfaces. Results show that NO was molecularly adsorbed on two kinds of surfaces. H{sub 2}O{sub 2} adsorption on perfect surface was also in a molecular form; however, H{sub 2}O{sub 2} dissociation occurred on oxygen defect α-Fe{sub 2}O{sub 3} (0 0 1) surface. The adsorption intensities of the two gas molecules in perfect α-Fe{sub 2}O{sub 3} (0 0 1) surface followed the order NO > H{sub 2}O{sub 2}, and the opposite was true for the oxygen defect α-Fe{sub 2}O{sub 3} (0 0 1). Oxygen vacancy remarkably enhanced the adsorption intensities of NO and H{sub 2}O{sub 2} and promoted H{sub 2}O{sub 2} decomposition on catalyst surface. As an oxidative product of NO, HNO{sub 2} was synthesized when NO and H{sub 2}O{sub 2} co-adsorbed on the oxygen defect α-Fe{sub 2}O{sub 3} (0 0 1) surface. Analyses of Mulliken population, electron density difference, and partial density of states showed that H{sub 2}O{sub 2} decomposition

Vacancy Clusters on Surfaces of Au Nanoparticles Embedded in MgO

International Nuclear Information System (INIS)

Xu, Jun; Mills, A. P. Jr.; Ueda, A.; Henderson, D. O.; Suzuki, R.; Ishibashi, S.

1999-01-01

MeV implantation of gold ions into MgO(100) followed by annealing is a method to form gold nanoparticles for obtaining modified optical properties. We show from variable-energy positron spectroscopy that clusters of 2 Mg and 2 O vacancies (v 4 ) are attached to the gold nanoparticle surfaces within the projected range (R p ) . We also find that v 4 vacancy clusters are created at depths less than R p , and extend into the region greater than R p due to damage induced by knock-on collisions. (c) 1999 The American Physical Society

Vacancy defects in epitaxial La0.7Sr0.3MnO3 thin films probed by a slow positron beam

International Nuclear Information System (INIS)

Jin, S W; Zhou, X Y; Wu, W B; Zhu, C F; Weng, H M; Wang, H Y; Zhang, X F; Ye, B J; Han, R D

2004-01-01

Vacancy defects in epitaxial La 0.7 Sr 0.3 MnO 3 (LSMO) thin films on LaAlO 3 substrates were detected using a variable energy positron beam. The line-shape S parameter of the epitaxial thin films deposited at different oxygen pressures was measured as a function of the implanting positron energy E. Our results show that the S parameter of the films changes non-monotonically with their deposition oxygen pressures. For the films deposited at lower oxygen pressures, the increase in S value in the films is attributed to the increase in oxygen vacancies and/or related defect-V O complexes, and for those deposited at higher oxygen pressures, the larger S parameter of the films is caused by the grain boundaries and/or metallic ion vacancies. The surface morphology of the films was also characterized to analyse the open volume defects in the LSMO films

Dissociation and diffusion of hydrogen on defect-free and vacancy defective Mg (0001) surfaces: A density functional theory study

Energy Technology Data Exchange (ETDEWEB)

Han, Zongying [College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266590 (China); Union Research Center of Fuel Cell, School of Chemical and Environmental Engineering, China University of Mining and Technology, Beijing 100083 (China); Chen, Haipeng [College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266590 (China); College of Mechanical and Electronic Engineering, Shandong University of Science and Technology, Qingdao 266590 (China); Zhou, Shixue, E-mail: zhoushixue66@163.com [College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266590 (China); College of Mechanical and Electronic Engineering, Shandong University of Science and Technology, Qingdao 266590 (China)

2017-02-01

Highlights: • Clarify the effect of vacancy defect on H{sub 2} dissociation on Mg (0001) surface. • Demonstrate the effects of vacancy defect on H atom diffusion. • Reveal the minimum energy diffusion path of H atom from magnesium surface into bulk. - Abstract: First-principles calculations with the density functional theory (DFT) have been carried out to study dissociation and diffusion of hydrogen on defect-free and vacancy defective Mg (0001) surfaces. Results show that energy barriers of 1.42 eV and 1.28 eV require to be overcome for H{sub 2} dissociation on defect-free and vacancy defective Mg (0001) surfaces respectively, indicating that reactivity of Mg (0001) surface is moderately increased due to vacancy defect. Besides, the existence of vacancy defect changes the preferential H atom diffusion entrance to the subsurface and reduces the diffusion energy barrier. An interesting remark is that the minimum energy diffusion path of H atom from magnesium surface into bulk is a spiral channel formed by staggered octahedral and tetrahedral interstitials. The diffusion barriers computed for H atom penetration from the surface into inner-layers are all less than 0.70 eV, which is much smaller than the activation energy for H{sub 2} dissociation on the Mg (0001) surface. This suggests that H{sub 2} dissociation is more likely than H diffusion to be rate-limiting step for magnesium hydrogenation.

Efficient Visible Light Nitrogen Fixation with BiOBr Nanosheets of Oxygen Vacancies on the Exposed {001} Facets.

Science.gov (United States)

Li, Hao; Shang, Jian; Ai, Zhihui; Zhang, Lizhi

2015-05-20

Even though the well-established Haber-Bosch process has been the major artificial way to "fertilize" the earth, its energy-intensive nature has been motivating people to learn from nitrogenase, which can fix atmospheric N2 to NH3 in vivo under mild conditions with its precisely arranged proteins. Here we demonstrate that efficient fixation of N2 to NH3 can proceed under room temperature and atmospheric pressure in water using visible light illuminated BiOBr nanosheets of oxygen vacancies in the absence of any organic scavengers and precious-metal cocatalysts. The designed catalytic oxygen vacancies of BiOBr nanosheets on the exposed {001} facets, with the availability of localized electrons for π-back-donation, have the ability to activate the adsorbed N2, which can thus be efficiently reduced to NH3 by the interfacial electrons transferred from the excited BiOBr nanosheets. This study might open up a new vista to fix atmospheric N2 to NH3 through the less energy-demanding photochemical process.

Decrease of oxygen vacancy by Zn-doped for improving solar-blind photoelectric performance in β-Ga2O3 thin films

Science.gov (United States)

Guo, Daoyou; Qin, Xinyuan; Lv, Ming; Shi, Haoze; Su, Yuanli; Yao, Guosheng; Wang, Shunli; Li, Chaorong; Li, Peigang; Tang, Weihua

2017-11-01

Highly (201) oriented Zn-doped β-Ga2O3 thin films with different dopant concentrations were grown on (0001) sapphire substrates by radio frequency magnetron sputtering. With the increase of Zn dopant concentration, the crystal lattice expands, the energy band gap shrinks, and the oxygen vacancy concentration decreases. Both the metal semiconductor metal (MSM) structure photodetectors based on the pure and Zn-doped β-Ga2O3 thin films exhibit solar blind UV photoelectric property. Compared to the pure β-Ga2O3 photodetector, the Zn-doped one exhibits a lower dark current, a higher photo/dark current ratio, a faster photoresponse speed, which can be attributed to the decreases of oxygen vacancy concentration.[Figure not available: see fulltext.

Tailored TiO2(110) surfaces and their reactivity

International Nuclear Information System (INIS)

Pang, C L; Bikondoa, O; Humphrey, D S; Papageorgiou, A C; Cabailh, G; Ithnin, R; Chen, Q; Muryn, C A; Onishi, H; Thornton, G

2006-01-01

Electron bombardment from a filament as well as voltage pulses from a scanning tunnelling microscope tip have been employed to modify the surface of TiO 2 (110). Individual H atoms are selectively desorbed with electrical pulses of +3 V from the scanning tunnelling microscope tip, whilst leaving the oxygen vacancies intact. This allows us to distinguish between oxygen vacancies and hydroxyl groups, which have a similar appearance in scanning tunnelling microscopy images. This then allows the oxygen vacancy-promoted dissociation of water and O 2 to be followed with the microscope. Electrical pulses between +5 and +10 V induce local TiO 2 (110)1 x 2 reconstructions centred around the pulse. As for electron bombardment of the surface, relatively low fluxes increase the density of oxygen vacancies whilst higher fluxes lead to the 1 x 2 and other 1 x n reconstructions

First-principles investigations of electronic and magnetic properties of SrTiO3 (001) surfaces with adsorbed ethanol and acetone molecules

Science.gov (United States)

Adeagbo, Waheed A.; Fischer, Guntram; Hergert, Wolfram

2011-05-01

First-principles methods based on density functional theory are used to investigate the electronic and magnetic properties of molecular interaction of the TiO2 terminated SrTiO3 (100) surface with ethanol or acetone. Both the perfect surface and the surface with an oxygen or a titanium vacancy in the top layer are considered. Ethanol and acetone are preferentially adsorbed molecularly via their respective oxygen atom on top of the Ti atom on the perfect surface. In case of an oxygen vacancy the adsorption of ethanol or acetone occurs directly on top of the vacancy and does not significantly affect the magnetism caused by the vacancy. In the case of a titanium vacancy both adsorbates occupy positions above Ti atoms. During this adsorption process the ethanol molecule dissociates into a CH3CO radical and three hydrogen atoms. The latter form hydroxide bonds with three of the four dangling oxygen bonds around the Ti vacancy and any magnetic moment induced by the Ti vacancy is annihilated. Thus the ethanol and acetone have a different impact on the surface magnetism of the SrTiO3 (100) surface.

Vacancy-type defects induced by grinding of Si wafers studied by monoenergetic positron beams

Energy Technology Data Exchange (ETDEWEB)

Uedono, Akira; Yoshihara, Nakaaki [Division of Applied Physics, Faculty of Pure and Applied Science, University of Tsukuba, Tsukuba, Ibaraki 305-8573 (Japan); Mizushima, Yoriko [Devices and Materials Labs Fujitsu Laboratories Ltd., Atsugi, Kanagawa 243-0197 (Japan); ICE Cube Center, Tokyo Institute of Technology, Yokohama 226-8503 (Japan); Kim, Youngsuk [ICE Cube Center, Tokyo Institute of Technology, Yokohama 226-8503 (Japan); Disco Corporation, Ota, Tokyo 143-8580 (Japan); Nakamura, Tomoji [Devices and Materials Labs Fujitsu Laboratories Ltd., Atsugi, Kanagawa 243-0197 (Japan); Ohba, Takayuki [ICE Cube Center, Tokyo Institute of Technology, Yokohama 226-8503 (Japan); Oshima, Nagayasu; Suzuki, Ryoichi [Research Institute of Instrumentation Frontier, National Institute of Advanced Industrial Science and Technology, Tsukuba, Ibaraki 305-8568 (Japan)

2014-10-07

Vacancy-type defects introduced by the grinding of Czochralski-grown Si wafers were studied using monoenergetic positron beams. Measurements of Doppler broadening spectra of the annihilation radiation and the lifetime spectra of positrons showed that vacancy-type defects were introduced in the surface region (<98 nm), and the major defect species were identified as (i) relatively small vacancies incorporated in dislocations and (ii) large vacancy clusters. Annealing experiments showed that the defect concentration decreased with increasing annealing temperature in the range between 100 and 500°C. After 600–700°C annealing, the defect-rich region expanded up to about 170 nm, which was attributed to rearrangements of dislocation networks, and a resultant emission of point defects toward the inside of the sample. Above 800°C, the stability limit of those vacancies was reached and they started to disappear. After the vacancies were annealed out (900°C), oxygen-related defects were the major point defects and they were located at <25 nm.

A quantum-chemical study of oxygen-vacancy defects in PbTiO{sub 3} crystals

Energy Technology Data Exchange (ETDEWEB)

Stashans, Arvids [Laboratorio de Fisica, Escuela de Electronica y Telecomunicaciones, Universidad Tecnica Particular de Loja, Apartado 11-01-608, Loja (Ecuador)]. E-mail: arvids@utpl.edu.ec; Serrano, Sheyla [Centro de Investigacion en Fisica de Materia Condensada, Corporacion de Fisica Fundamental y Aplicada, Apartado 17-12-637, Quito (Ecuador); Escuela de Ingenierias, Universidad Politecnica Salesiana, Campus Sur, Rumichaca s/n y Moran Valverde, Apartado 17-12-536, Quito (Ecuador); Medina, Paul [Centro de Investigacion en Fisica de Materia Condensada, Corporacion de Fisica Fundamental y Aplicada, Apartado 17-12-637, Quito (Ecuador)

2006-05-31

Investigation of an oxygen vacancy and F center in the cubic and tetragonal lattices of PbTiO{sub 3} crystals is done by means of quantum-chemical simulations. Displacements of defect-surrounding atoms, electronic and optical properties, lattice relaxation energies and some new effects due to the defects presence are reported and analyzed. A comparison with similar studies is made and conclusions are drawn on the basis of the obtained results.

Detection of oxygen vacancy defect states in capacitors with ultrathin Ta2O5 films by zero-bias thermally stimulated current spectroscopy

International Nuclear Information System (INIS)

Lau, W.S.; Leong, L.L.; Han, Taejoon; Sandler, Nathan P.

2003-01-01

Defect state D (0.8 eV) was experimentally detected in Ta 2 O 5 capacitors with ultrathin (physical thickness 2 O 5 films using zero-bias thermally stimulated current spectroscopy and correlated with leakage current. Defect state D can be more efficiently suppressed by using N 2 O rapid thermal annealing (RTA) instead of using O 2 RTA for postdeposition annealing and by using TiN instead of Al for top electrode. We believe that defect D is probably the first ionization level of the oxygen vacancy deep double donor. Other important defects are Si/O-vacancy complex single donors and C/O-vacancy complex single donors

Hydrogen isotope in erbium oxide: Adsorption, penetration, diffusion, and vacancy trapping

Energy Technology Data Exchange (ETDEWEB)

Mao, Wei, E-mail: mao@nuclear.jp [Department of Nuclear Engineering and Management, School of Engineering, The University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, Tokyo 113-8656 (Japan); The University Museum, The University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, Tokyo 113-0032 (Japan); Chikada, Takumi [Department of Chemistry, Graduate School of Science, Shizuoka University, 836 Ohya, Suruga-ku, Shizuoka 422-8529 (Japan); Suzuki, Akihiro [Nuclear Professional School, School of Engineering, The University of Tokyo, 2-22, Shirakata-shirane, Tokai, Naka 319-1188, Ibaraki (Japan); Terai, Takayuki [Department of Nuclear Engineering and Management, School of Engineering, The University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, Tokyo 113-8656 (Japan); Matsuzaki, Hiroyuki [The University Museum, The University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, Tokyo 113-0032 (Japan)

2015-03-15

Highlights: • H adsorption on cubic Er{sub 2}O{sub 3} surface results in electron transfer from H to the surface. • The H penetration energy of at least 1.6 eV is required for cubic Er{sub 2}O{sub 3} surface. • The dominated mechanisms of H diffusion in bulk Er{sub 2}O{sub 3} are elucidated. • H diffusion near or at vacancies in Er{sub 2}O{sub 3} is an exothermic reaction. - Abstract: In this study, we report results using first-principles density functional theory calculations for four critical aspects of the interaction: H adsorption on Er{sub 2}O{sub 3} surface, surface-to-subsurface penetration of H into Er{sub 2}O{sub 3}, bulk diffusion of H in Er{sub 2}O{sub 3}, and trapping of H at vacancies. We identify surface stable adsorption positions and find that H prefers to transfer electrons to the surfaces and form covalent bonds with the nearest neighboring four oxygen atoms. For low surface coverage of H as in our case (0.89 × 10{sup 14} H/cm{sup 2}), a penetration energy of at least 1.60 eV is required for cubic Er{sub 2}O{sub 3} surfaces. Further, the H diffusion barrier between the planes defined by Er{sub 2}O{sub 3} units along the favorable <1 1 1> direction is found to be very small – 0.16 eV – whereas higher barriers of 0.41 eV and 1.64 eV are required for diffusion across the planes, somewhat higher than the diffusion energy barrier of 0.20 eV observed experimentally at 873 K. In addition, we predict that interstitial H is exothermically trapped when it approaches a vacancy with the vacancy defect behaving as an electron trap since the H-vacancy defect is found to be more stable than the intrinsic defect.

Application of Electron Structure Calculations to the Migration of Oxygen through a Perovskite Membrane

Science.gov (United States)

Wood, Douglas A.

The focus of this thesis is the application of electron structure calculations, particularly density functional theory, to the analysis of the process by which oxygen is able to migrate through a perovskite crystal. This property creates the possibility of using perovskite membranes to separate oxygen from air. This could be applied to the generation of syngas directly from natural gas without the need for a separate air separation unit. A perovskite has the nominal formula ABO3 where A is a rare earth type cation and B is a transition type cation. The structure consists of the B cations arranged in a cube with the A cation in the center. The oxygen ions are located at the midpoint of each B-B cube edge and form an octahedron centered on each B cation. Any real perovskite crystal will contain a certain fraction of vacancies at the oxygen sites. Oxygen migrates through the crystal by jumping from a neighboring site to the vacancy. The permeability of the crystal is thus a function of the concentration of vacancies and the activation energy of the jump from a neighboring site to the vacancy. These properties can be modified by adding dopants for the A and B cations. The literature contains a substantial amount of experimental work on the effect of such dopants. The overall migration process can be divided into components (i) the concentration of oxygen vacancies, (ii) the activation energy for a neighboring on-site oxygen atom to jump to the vacant site, (iii) the concentration of surface vacancies, and (iv) the processes by which oxygen ions transfer back and forth between the perovskite surface and the contiguous vapor space. Using SrTiO3 and LaCoO3 as model compounds, DFT calculations have been used to (i) calculate various properties of the perovskite crystal, (ii) estimate the activation energy of a jump between an occupied oxygen site and an adjacent vacant oxygen site, (iii) predict the effects of various dopants at the A and B site and (iv) analyze the

Extended x-ray absorption fine structure spectroscopy and x-ray absorption near edge spectroscopy study of aliovalent doped ceria to correlate local structural changes with oxygen vacancies clustering

Energy Technology Data Exchange (ETDEWEB)

Shirbhate, S. C.; Acharya, S. A., E-mail: saha275@yahoo.com [Department of Physics, Rashtrasant Tukadoji Maharaj Nagpur University, Nagpur 440033 (India); Yadav, A. K. [Atomic and molecular Physics Division, Bhabha Atomic Research Centre, Mumbai 400085 (India)

2016-04-04

This study provides atomic scale insight to understand the role of aliovalent dopants on oxygen vacancies clustering and dissociation mechanism in ceria system in order to enhance the performance of oxy-ion conductor. Dopants induced microscale changes in ceria are probed by extended X-ray absorption fine structure spectroscopy, X-ray absorption near edge spectra, and Raman spectroscopy. The results are explored to establish a correlation between atomic level structural changes (coordination number, interatomic spacing) → formation of dimer and trimer type cation-oxygen vacancies defect complex (intrinsic and extrinsic) → dissociation of oxygen vacancies from defect cluster → ionic conductivity temperature. It is a strategic approach to understand key physics of ionic conductivity mechanism in order to reduce operating temperature of electrolytes for intermediate temperature (300–450 °C) electrochemical devices for the first time.

Optical studies of cobalt implanted rutile TiO2 (110) surfaces

International Nuclear Information System (INIS)

Joshi, Shalik Ram; Padmanabhan, B.; Chanda, Anupama; Mishra, Indrani; Malik, V.K.; Mishra, N.C.; Kanjilal, D.; Varma, Shikha

2016-01-01

Highlights: • The present study displays formation of nanostructures after Co implantation on TiO 2 surfaces. • Preferential sputtering leads to the creation of oxygen vacancies on the surface. • A large enhancement in visible light absorbance (nearly 5 times compared to pristine) is observed. • Creation of self-organized nanostructures and Ti 3+ oxygen vacancies promote photoabsorption. • Formation of Co-nanoclusters and Co–Ti–O phase play concerted role in enhancing photo-absorption. - Abstract: Present study investigates the photoabsorption properties of single crystal rutile TiO 2 (110) surfaces after they have been implanted with low fluences of cobalt ions. The surfaces, after implantation, demonstrate fabrication of nanostructures and anisotropic nano-ripple patterns. Creation of oxygen vacancies (Ti 3+ states), development of cobalt nano-clusters as well as band gap modifications have also been observed. Results presented here demonstrate that fabrication of self organized nanostructures, upon implantation, along with the development of oxygen vacancies and ligand field transitions of cobalt ion promote the enhancement of photo-absorbance in both UV (∼2 times) and visible (∼5 times) regimes. These investigations on nanostructured TiO 2 surfaces can be important for photo-catalysis.

Electronic structure of vacancies and vacancy clusters in simple metals

International Nuclear Information System (INIS)

Manninen, M.; Nieminen, R.M.

1978-05-01

The self-consistent density functional approach has been applied in a study of electronic properties of vacancies and vacancy clusters in simple metals. The electron density profiles and potentials have been obtained for spherical voids of varying size. The formation energies and residual resistivities have been calculated for vacancies using both perturbational and variational inclusion of discrete lattice effects. The relation of the void properties to the plane surface ones is studied, and the inadequacy of the jellium-based methods to high-index faces is demonstrated. (author)

Spin properties of dense near-surface ensembles of nitrogen-vacancy centers in diamond

Science.gov (United States)

Tetienne, J.-P.; de Gille, R. W.; Broadway, D. A.; Teraji, T.; Lillie, S. E.; McCoey, J. M.; Dontschuk, N.; Hall, L. T.; Stacey, A.; Simpson, D. A.; Hollenberg, L. C. L.

2018-02-01

We present a study of the spin properties of dense layers of near-surface nitrogen-vacancy (NV) centers in diamond created by nitrogen ion implantation. The optically detected magnetic resonance contrast and linewidth, spin coherence time, and spin relaxation time, are measured as a function of implantation energy, dose, annealing temperature, and surface treatment. To track the presence of damage and surface-related spin defects, we perform in situ electron spin resonance spectroscopy through both double electron-electron resonance and cross-relaxation spectroscopy on the NV centers. We find that, for the energy (4 -30 keV) and dose (5 ×1011-1013ions/cm 2 ) ranges considered, the NV spin properties are mainly governed by the dose via residual implantation-induced paramagnetic defects, but that the resulting magnetic sensitivity is essentially independent of both dose and energy. We then show that the magnetic sensitivity is significantly improved by high-temperature annealing at ≥1100 ∘C . Moreover, the spin properties are not significantly affected by oxygen annealing, apart from the spin relaxation time, which is dramatically decreased. Finally, the average NV depth is determined by nuclear magnetic resonance measurements, giving ≈10 -17 nm at 4-6 keV implantation energy. This study sheds light on the optimal conditions to create dense layers of near-surface NV centers for high-sensitivity sensing and imaging applications.

The role of Co impurities and oxygen vacancies in the ferromagnetism of Co-doped SnO2: GGA and GGA+U studies

International Nuclear Information System (INIS)

Wang Hongxia; Yan Yu; Mohammed, Y. Sh.; Du Xiaobo; Li Kai; Jin Hanmin

2009-01-01

The electronic structure and ferromagnetic stability of Co-doped SnO 2 are studied using the first-principle density functional method within the generalized gradient approximation (GGA) and GGA+U schemes. The addition of effective U Co transforms the ground state of Co-doped SnO 2 to insulating from half-metallic and the coupling between the nearest neighbor Co spins to weak antimagnetic from strong ferromagnetic. GGA+U Co calculations show that the pure substitutional Co defects in SnO 2 cannot induce the ferromagnetism. Oxygen vacancies tend to locate near Co atoms. Their presence increases the magnetic moment of Co and induces the ferromagnetic coupling between two Co spins with large Co-Co distance. The calculated density of state and spin density distribution calculated by GGA+U Co show that the long-range ferromagnetic coupling between two Co spins is mediated by spin-split impurity band induced by oxygen vacancies. More charge transfer from impurity to Co-3d states and larger spin split of Co-3d and impurity states induced by the addition of U Co enhance the ferromagnetic stability of the system with oxygen vacancies. By applying a Coulomb U O on O 2 s orbital, the band gap is corrected for all calculations and the conclusions derived from GGA+U Co calculations are not changed by the correction of band gap.

Migration mechanisms and diffusion barriers of vacancies in Ga2O3

Science.gov (United States)

Kyrtsos, Alexandros; Matsubara, Masahiko; Bellotti, Enrico

2017-06-01

We employ the nudged elastic band and the dimer methods within the standard density functional theory (DFT) formalism to study the migration of the oxygen and gallium vacancies in the monoclinic structure of β -Ga2O3 . We identify all the first nearest neighbor paths and calculate the migration barriers for the diffusion of the oxygen and gallium vacancies. We also identify the metastable sites of the gallium vacancies which are critical for the diffusion of the gallium atoms. The migration barriers for the diffusion of the gallium vacancies are lower than the migration barriers for oxygen vacancies by 1 eV on average, suggesting that the gallium vacancies are mobile at lower temperatures. Using the calculated migration barriers we estimate the annealing temperature of these defects within the harmonic transition state theory formalism, finding excellent agreement with the observed experimental annealing temperatures. Finally, we suggest the existence of percolation paths which enable the migration of the species without utilizing all the migration paths of the crystal.

An Unusual Strong Visible-Light Absorption Band in Red Anatase TiO2 Photocatalyst Induced by Atomic Hydrogen-Occupied Oxygen Vacancies.

Science.gov (United States)

Yang, Yongqiang; Yin, Li-Chang; Gong, Yue; Niu, Ping; Wang, Jian-Qiang; Gu, Lin; Chen, Xingqiu; Liu, Gang; Wang, Lianzhou; Cheng, Hui-Ming

2018-02-01

Increasing visible light absorption of classic wide-bandgap photocatalysts like TiO 2 has long been pursued in order to promote solar energy conversion. Modulating the composition and/or stoichiometry of these photocatalysts is essential to narrow their bandgap for a strong visible-light absorption band. However, the bands obtained so far normally suffer from a low absorbance and/or narrow range. Herein, in contrast to the common tail-like absorption band in hydrogen-free oxygen-deficient TiO 2 , an unusual strong absorption band spanning the full spectrum of visible light is achieved in anatase TiO 2 by intentionally introducing atomic hydrogen-mediated oxygen vacancies. Combining experimental characterizations with theoretical calculations reveals the excitation of a new subvalence band associated with atomic hydrogen filled oxygen vacancies as the origin of such band, which subsequently leads to active photo-electrochemical water oxidation under visible light. These findings could provide a powerful way of tailoring wide-bandgap semiconductors to fully capture solar light. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxygen vacancies enabled enhancement of catalytic property of Al reduced anatase TiO{sub 2} in the decomposition of high concentration ozone

Energy Technology Data Exchange (ETDEWEB)

Ding, Yanhua; Zhang, Xiaolei [Shanghai Institute of Technology, Shanghai 200235 (China); Chen, Li [East China Normal University, Shanghai 200062 (China); Wang, Xiaorui [Shanghai Institute of Technology, Shanghai 200235 (China); Zhang, Na, E-mail: nzhang@sit.edu.cn [Shanghai Institute of Technology, Shanghai 200235 (China); Liu, Yufeng [Shanghai Institute of Technology, Shanghai 200235 (China); Fang, Yongzheng, E-mail: fyz1003@sina.com [Shanghai Institute of Technology, Shanghai 200235 (China)

2017-06-15

The catalytic decomposition of gaseous ozone (O{sub 3}) is investigated using anatase TiO{sub 2} (A-TiO{sub 2}) and Aluminum-reduced A-TiO{sub 2} (ARA-TiO{sub 2}) at high concentration and high relative humidity (RH) without light illumination. Compared with the pristine A-TiO{sub 2}, the ARA-TiO{sub 2} sample possesses a unique crystalline core-amorphous shell structure. It is proved to be an excellent solar energy “capture” for solar thermal collectors due to lots of oxygen vacancies. The results indicate that the overall decomposition efficiency of O{sub 3} without any light irradiation has been greatly improved from 4.8% on A-TiO{sub 2} to 100% on ARA-TiO{sub 2} under the RH=100% condition. The ozone conversion over T500/ARA-TiO{sub 2} catalyst is still maintained at 95% after a 72 h test under the reaction condition of 18.5 g/m{sup 3} ozone initial concentration, and RH=90%. The results can be explained that T500/ARA-TiO{sub 2} possesses the largest amorphous contour, the lowest crystallinity, the most surface-active Ti{sup 3+}/T{sup i4+}couples, and the most oxygen vacancies. This result opens a new door to widen the application of TiO{sub 2} in the thermal-catalytic field. - Graphical abstract: The anatase-TiO{sub 2} with various oxidation states and oxygen vacancies have been obtained by aluminum-reduction, and the decomposition efficiency of O{sub 3} has been greatly improved from 4.8% to 100% without irradiation under the RH=100% condition. - Highlights: • The decomposition of gaseous ozone over Al reduced TiO2 (ARA-TiO{sub 2}) is firstly reported. • The decomposition efficiency is up to 100% without any light irradiation on ARA-TiO{sub 2} under RH=100% condition. • The ozone conversion is maintained at 95% after a 72 h test, when C{sub inlet}=18.5 g/m{sup 3} and RH=90%.

Ordering of vacancies on Si(001)

NARCIS (Netherlands)

Zandvliet, Henricus J.W.

1997-01-01

Missing dimer vacancies are always present on the clean Si(001) surface. The vacancy density can be increased by ion bombardment (Xe+, Ar+), etching (O2, Br2, I2, etc.) or Ni contamination. The equilibrium shape at low vacancy concentrations (<0.2¿0.3 monolayers) of these vacancy islands is

Experimental evidence for fast cluster formation of chain oxygen vacancies in YBa2Cu3O7-d being at the origin of the fishtail anomaly

OpenAIRE

Erb, Andreas; Manuel, Alfred A.; Dhalle, Marc; Marti, Frank; Genoud, Jean-Yves; Revaz, Bernard; Junod, Alain; Vasumathi, Dharmavaram; Ishibashi, Shoji; Shukla, Abhay; Walker, Eric; Fischer, Oystein; Fluekiger, Rene; Pozzi, Riccardo; Mali, Mihael

1998-01-01

We report on three different and complementary measurements, namely magnetisation measurements, positron annihilation spectroscopy and NMR measurements, which give evidence that the formation of oxygen vacancy clusters is on the origin of the fishtail anomaly in YBa2Cu3O7-d. While in the case of YBa2Cu3O7.0 the anomaly is intrinsically absent, it can be suppressed in the optimally doped state where vacancies are present. We therefore conclude that the single vacancies or point defects can not...

Dissociation of N{sub 2}O on anatase TiO{sub 2} (001) surface – The effect of oxygen vacancy and presence of Ag cluster

Energy Technology Data Exchange (ETDEWEB)

Sowmiya, M.; Senthilkumar, K., E-mail: ksenthil@buc.edu.in

2016-12-15

Highlights: • This study elucidates the dissociation of N{sub 2}O on anatase TiO{sub 2} (001) surface. • N{sub 2}O is decomposed into N{sub 2} and O on reduced TiO{sub 2} even in the presence of Ag cluster. • Excess charge in reduced TiO{sub 2} surface is transferred to the adsorbed N{sub 2}O molecule. • The vibrational frequency analysis also performed to study the dissociation of N{sub 2}O. • Anatase TiO{sub 2} with oxygen vacancies is a suitable catalyst for decomposition of N{sub 2}O. - Abstract: The increase in concentration of nitrous oxide (N{sub 2}O) in the atmosphere is one of the major contributors to the greenhouse effect, ozone depletion and climate change. Therefore, it is important to decompose harmful N{sub 2}O molecule into harmless N{sub 2}. In the present work, we have studied the decomposition of N{sub 2}O on anatase TiO{sub 2} (001) surface using first principle calculations. The results indicates that the N{sub 2}O molecule is physisorbed on perfect TiO{sub 2} surface without any dissociation, and is dissociated into N{sub 2} and oxygen on the reduced TiO{sub 2} surface. In addition, it has been found that the interaction between N{sub 2}O and TiO{sub 2} is augmented by the presence of Ag cluster on anatase (001) surface. On the basis of Bader charge analysis and electron density difference plot, it has been found that the excess charge in the reduced anatase TiO{sub 2} (001) surface is transferred to the adsorbed N{sub 2}O molecule, which results the weakening of N–O bond of N{sub 2}O followed by the decomposition of N{sub 2}O into N{sub 2} and O. Vibrational frequency analysis also performed to confirm the decomposition of N{sub 2}O molecule. From the pathway for N{sub 2}O dissociation on reduced TiO{sub 2} and Ag/TiO{sub 2} surfaces, it has been observed that the dissociation reaction of N{sub 2}O on TiO{sub 2} surface is highly exothermic with activation energy barrier of 0.25 eV. The results presented in this work show that the

Oxygen vacancy induced two-dimensional electron system in disordered-crystalline LaAlO{sub 3}/KTaO{sub 3} heterostructures

Energy Technology Data Exchange (ETDEWEB)

Zapf, Michael; Gabel, Judith; Scheiderer, Philipp; Dudy, Lenart; Sing, Michael; Claessen, Ralph [Physikalisches Institut and Roentgen Center for Complex Material Systems (RCCM), Universitaet Wuerzburg (Germany); Schlueter, Christoph; Lee, Tien-Lin [Diamond Light Source Ltd., Didcot (United Kingdom)

2016-07-01

Two-dimensional electron systems (2DESs) in oxide heterostructures based on SrTiO{sub 3} are considered to be a promising platform for future microelectronic technology. A variety of interesting properties such as ferromagnetism, resistive switching and superconductivity are linked to interfacial n-doping involving oxygen vacancies. The introduction of a high Z-cation with large spin-orbit coupling like Ta offers an exciting new parameter. We report on a new oxygen vacancy induced 2DES located at the interface of disordered LaAlO{sub 3} and crystalline KTaO{sub 3}, which exhibits remarkably high electron mobilities and charge carrier concentrations. The number of charge carriers can be readily manipulated by the film thickness and irradiation with intense X-rays. Our synchrotron-based hard X-ray photoemission experiments provide a direct probe of the Ta 5d charge carriers at the buried interface to obtain information on the charge carrier density, its depth distribution, and the band structure.

Detection of the ODMR signal of a nitrogen vacancy centre in nanodiamond in propagating surface plasmons

Science.gov (United States)

Al-Baiaty, Zahraa; Cumming, Benjamin P.; Gan, Xiaosong; Gu, Min

2018-02-01

We demonstrate that the optically detected magnetic resonance (ODMR) signal of a nitrogen vacancy (NV) centre can be coupled to propagating surface plasmons for the detection of the NV centre spin states, and of external magnetic fields. By coupling the spin dependent luminescence signal of a NV centre in a nanodiamond (ND) to a chemically synthesized silver nanowire, we demonstrate the readout of the ODMR signal as a reduction in the surface plasmon polariton intensity, with improved contrast in comparison to the emission from the NV centre. Furthermore, on the application of a permanent magnetic field from zero to 13 G, we demonstrate that the Zeeman splitting of the magnetic spin states of the nitrogen vacancy centre ground states can also be detected in the coupled surface plasmons. This is an important step in the development of a compact on-chip information processing system utilizing the nitrogen vacancy in nanodiamond as an on-chip source with efficient magnetometry sensing properties.

High-performance gas sensing achieved by mesoporous tungsten oxide mesocrystals with increased oxygen vacancies

KAUST Repository

Wang, Dong

2013-01-01

The inner structure of W18O49 mesocrystals was observed by electron microscopy with the help of ultramicrotomy and focused ion beam techniques. The results showed that these mesocrystals contain irregular mesopores formed through partial fusion of self-assembled nanowires, and consequently have long-range structural ordering in one dimension and short-range ordering in the other two dimensions. The W18O 49 mesocrystals exhibit superior performance in gas sensing applications, which is considered to be associated with the presence of more oxygen vacancy sites in the unique mesoporous structure. © 2013 The Royal Society of Chemistry.

Oxygen vacancy rich Cu2O based composite material with nitrogen doped carbon as matrix for photocatalytic H2 production and organic pollutant removal.

Science.gov (United States)

Lu, Lele; Xu, Xinxin; Yan, Jiaming; Shi, Fa-Nian; Huo, Yuqiu

2018-02-06

A nitrogen doped carbon matrix supported Cu 2 O composite material (Cu/Cu2O@NC) was fabricated successfully with a coordination polymer as precursor through calcination. In this composite material, Cu 2 O particles with a size of about 6-10 nm were dispersed evenly in the nitrogen doped carbon matrix. After calcination, some coordinated nitrogen atoms were doped in the lattice of Cu 2 O and replace oxygen atoms, thus generating a large number of oxygen vacancies. In Cu/Cu2O@NC, the existence of oxygen vacancies has been confirmed by electron spin resonance (ESR) and X-ray photoelectron spectroscopy (XPS). Under visible light irradiation, Cu/Cu2O@NC exhibits excellent H 2 production with the rate of 379.6 μmol h -1 g -1 . Its photocatalytic activity affects organic dyes, such as Rhodamine B (RhB) and methyl orange (MO). In addition to photocatalysis, Cu/Cu2O@NC also exhibits striking catalytic activity in reductive conversion of 4-nitrophenol to 4-aminophenol with in presence of sodium borohydride (NaBH 4 ). The conversion efficiency reaches almost 100% in 250 s with the quantity of Cu/Cu2O@NC as low as 5 mg. The outstanding H 2 production and organic pollutants removal are attributed to the oxygen vacancy. We expect that Cu/Cu2O@NC will find its way as a new resource for hydrogen energy as well as a promising material in water purification.

Positronic probe of vacancy defects on surfaces of Au nanoparticles embedded in MgO

International Nuclear Information System (INIS)

Xu, Jun; Moxom, J.; Somieski, B.; White, C. W.; Mills, A. P.; Suzuki, R.; Ishibashi, S.

2001-01-01

Clusters of four atomic vacancies were found in Au nanoparticle-embedded MgO by positron lifetime spectroscopy [Phys. Rev. Lett. 83, 4586 (1999)]. These clusters were also suggested to locate at the surface of Au nanoparticles by one-detector measurements of Doppler broadening of annihilation radiation. In this work we provide evidence, using two-detector coincidence experiments of Doppler broadening (2D-DBAR), to clarify that these vacancy clusters reside on the surfaces of Au nanoparticles. This work also demonstrates a method for identifying defects at nanomaterials interfaces: a combination of both positron lifetime spectroscopy, which tells the type of the defects, and 2D-DBAR measurements, which reveals chemical environment of the defects

Positronic probe of vacancy defects on surfaces of Au nanoparticles embedded in MgO

Science.gov (United States)

Xu, Jun; Moxom, J.; Somieski, B.; White, C. W.; Mills, A. P., Jr.; Suzuki, R.; Ishibashi, S.

2001-09-01

Clusters of four atomic vacancies were found in Au nanoparticle-embedded MgO by positron lifetime spectroscopy [Phys. Rev. Lett. 83, 4586 (1999)]. These clusters were also suggested to locate at the surface of Au nanoparticles by one-detector measurements of Doppler broadening of annihilation radiation. In this work we provide evidence, using two-detector coincidence experiments of Doppler broadening (2D-DBAR), to clarify that these vacancy clusters reside on the surfaces of Au nanoparticles. This work also demonstrates a method for identifying defects at nanomaterials interfaces: a combination of both positron lifetime spectroscopy, which tells the type of the defects, and 2D-DBAR measurements, which reveals chemical environment of the defects.

Manipulating multiple order parameters via oxygen vacancies: The case of E u0.5B a0.5Ti O3 -δ

Science.gov (United States)

Li, Weiwei; He, Qian; Wang, Le; Zeng, Huizhong; Bowlan, John; Ling, Langsheng; Yarotski, Dmitry A.; Zhang, Wenrui; Zhao, Run; Dai, Jiahong; Gu, Junxing; Shen, Shipeng; Guo, Haizhong; Pi, Li; Wang, Haiyan; Wang, Yongqiang; Velasco-Davalos, Ivan A.; Wu, Yangjiang; Hu, Zhijun; Chen, Bin; Li, Run-Wei; Sun, Young; Jin, Kuijuan; Zhang, Yuheng; Chen, Hou-Tong; Ju, Sheng; Ruediger, Andreas; Shi, Daning; Borisevich, Albina Y.; Yang, Hao

2017-09-01

Controlling functionalities, such as magnetism or ferroelectricity, by means of oxygen vacancies (VO) is a key issue for the future development of transition-metal oxides. Progress in this field is currently addressed through VO variations and their impact on mainly one order parameter. Here we reveal a mechanism for tuning both magnetism and ferroelectricity simultaneously by using VO. Combining experimental and density-functional theory studies of E u0.5B a0.5Ti O3 -δ , we demonstrate that oxygen vacancies create T i3 +3 d1 defect states, mediating the ferromagnetic coupling between the localized Eu 4 f7 spins, and increase an off-center displacement of Ti ions, enhancing the ferroelectric Curie temperature. The dual function of Ti sites also promises a magnetoelectric coupling in the E u0.5B a0.5Ti O3 -δ .

Oxygen vacancies at the spinel/perovskite γ-Al{sub 2}O{sub 3}/SrTiO{sub 3} heterointerface probed by resonant photoelectron spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Schuetz, Philipp; Pfaff, Florian; Zapf, Michael; Gabel, Judith; Dudy, Lenart; Berner, Goetz; Sing, Michael; Claessen, Ralph [Physikalisches Institut and Roentgen Center for Complex Material Systems (RCCM), Universitaet Wuerzburg (Germany); Chen, Yunzhong; Pryds, Nini [Department of Energy Conversion and Storage, Technical University of Denmark, Risoe (Denmark); Schlueter, Christoph; Lee, Tien-Lin [Diamond Light Source Ltd., Harwell Science and Innovation Campus, Didcot (United Kingdom)

2016-07-01

The spinel/perovskite heterointerface between the band insulators γ-Al{sub 2}O{sub 3} and SrTiO{sub 3} hosts a two-dimensional electron system (2DES) with exceptionally high electron mobility. Soft x-ray resonant photoelectron spectroscopy at the Ti L absorption edge is used to probe the Ti 3d derived interface states. Marked differences in the resonance behavior are found for the SrTiO{sub 3} valence band and the different interface states, which are observed in the band gap of SrTiO{sub 3}. A comparison to X-ray absorption spectra of Ti 3d{sup 0} and Ti 3d{sup 1} systems reveals the presence of different types of electronic states with Ti 3d character, i.e., oxygen vacancy induced, trapped in-gap states and itinerant states contributing to the 2DES. Exposure to low doses of oxygen during irradiation allows for the reversible manipulation of the oxygen stoichiometry, thus revealing the presence of an oxygen vacancy-induced state, which is characteristic for this spinel/perovskite interface.

Is the surface oxygen exchange rate linked to bulk ion diffusivity in mixed conducting Ruddlesden-Popper phases?

Science.gov (United States)

Tomkiewicz, Alex C; Tamimi, Mazin A; Huq, Ashfia; McIntosh, Steven

2015-01-01

The possible link between oxygen surface exchange rate and bulk oxygen anion diffusivity in mixed ionic and electronic conducting oxides is a topic of great interest and debate. While a large body of experimental evidence and theoretical analyses support a link, observed differences between bulk and surface composition of these materials are hard to reconcile with this observation. This is further compounded by potential problems with simultaneous measurement of both parameters. Here we utilize separate techniques, in situ neutron diffraction and pulsed isotopic surface exchange, to examine bulk ion mobility and surface oxygen exchange rates of three Ruddlesden-Popper phases, general form A(n-1)A(2)'B(n)O(3n+1), A(n-1)A(2)'B(n)X(3n+1); LaSrCo(0.5)Fe(0.5)O(4-δ) (n = 1), La(0.3)Sr(2.7)CoFeO(7-δ) (n = 2) and LaSr3Co(1.5)Fe(1.5)O(10-δ) (n = 3). These measurements are complemented by surface composition determination via high sensitivity-low energy ion scattering. We observe a correlation between bulk ion mobility and surface exchange rate between materials. The surface exchange rates vary by more than one order of magnitude with high anion mobility in the bulk of an oxygen vacancy-rich n = 2 Ruddlesden-Popper material correlating with rapid oxygen exchange. This is in contrast with the similar surface exchange rates which we may expect due to similar surface compositions across all three samples. We conclude that experimental limitations lead to inherent convolution of surface and bulk rates, and that surface exchange steps are not likely to be rate limiting in oxygen incorporation.

Colossal positive magnetoresistance in surface-passivated oxygen-deficient strontium titanite

KAUST Repository

David, Adrian

2015-05-15

Modulation of resistance by an external magnetic field, i.e. magnetoresistance effect, has been a long-lived theme of research due to both fundamental science and device applications. Here we report colossal positive magnetoresistance (CPMR) (>30,000% at a temperature of 2 K and a magnetic field of 9 T) discovered in degenerate semiconducting strontium titanite (SrTiO3) single crystals capped with ultrathin SrTiO3/LaAlO3 bilayers. The low-pressure high-temperature homoepitaxial growth of several unit cells of SrTiO3 introduces oxygen vacancies and high-mobility carriers in the bulk SrTiO3, and the three-unit-cell LaAlO3 capping layer passivates the surface and improves carrier mobility by suppressing surface-defect-related scattering. The coexistence of multiple types of carriers and inhomogeneous transport lead to the emergence of CPMR. This unit-cell-level surface engineering approach is promising to be generalized to others oxides, and to realize devices with high-mobility carriers and interesting magnetoelectronic properties.

Excitation of nanowire surface plasmons by silicon vacancy centers in nanodiamonds

DEFF Research Database (Denmark)

Kumar, Shailesh; Davydov, Valery A.; Agafonov, Viatcheslav N.

2017-01-01

Silicon vacancy (SiV) centers in diamonds have emerged as a very promising candidate for quantum emitters due to their narrow emission line resulting in their indistinguishability. While many different quantum emitters have already been used for the excitation of various propagating plasmonic modes......, the corresponding exploitation of SiV centers has remained so far uncharted territory. Here, we report on the excitation of surface plasmon modes supported by silver nanowires using SiV centers in nanodiamonds. The coupling of SiV center fluorescence to surface plasmons is observed, when a nanodiamond situated...

Theoretical study of the influence of cation vacancies on the catalytic properties of vanadium antimonate

International Nuclear Information System (INIS)

Messina, S.; Juan, A.; Larrondo, S.; Irigoyen, B.; Amadeo, N.

2008-01-01

We have theoretically studied the influence of antimony and vanadium cation vacancies in the electronic structure and reactivity of vanadium antimonate, using molecular orbital methods. From the analysis of the electronic properties of the VSbO 4 crystal structure, we can infer that both antimony and vanadium vacancies increase the oxidation state of closer V cations. This would indicate that, in the rutile-type VSbO 4 phase the Sb and V cations defects stabilize the V in a higher oxidation state (V 4+ ). Calculations of the adsorption energy for different toluene adsorption geometries on the VSbO 4 (1 1 0) surface have also been performed. The oxidation state of Sb, V and O atoms and the overlap population of metal-oxygen bonds have been evaluated. Our results indicate that the cation defects influence in the toluene adsorption reactions is slight. We have computed different alternatives for the reoxidation of the VSbO 4 (1 1 0) surface active sites which were reduced during the oxygenated products formation. These calculations indicate that the V cations in higher oxidation state (V 4+ ) are the species, which preferentially incorporate lattice oxygen to the reduced Sb cations. Thus, the cation defects would stabilize the V 4+ species in the VSbO 4 structure, determining its ability to provide lattice oxygen as a reactant

Surface modification of mixed-phase hydrogenated TiO{sub 2} and corresponding photocatalytic response

Energy Technology Data Exchange (ETDEWEB)

Samsudin, Emy Marlina [Nanotechnology and Catalysis Research Center, University of Malaya, 50603 Kuala Lumpur (Malaysia); Hamid, Sharifah Bee Abd, E-mail: sharifahbee@um.edu.my [Nanotechnology and Catalysis Research Center, University of Malaya, 50603 Kuala Lumpur (Malaysia); Juan, Joon Ching; Basirun, Wan Jefrey [Nanotechnology and Catalysis Research Center, University of Malaya, 50603 Kuala Lumpur (Malaysia); Kandjani, Ahmad Esmaeiljadeh [Centre of Advanced Materials and Industrial Chemistry, RMIT University, Melbourne 3001 (Australia)

2015-12-30

Graphical abstract: - Highlights: • Grayish-blue hydrogenated TiO{sub 2} powder with surface disorders. • Extension of photons absorption covering infrared region. • Presence of surface Ti{sup 3+} and oxygen vacancies facilitates photocatalytic activity. • Fewer formation of charge traps for hydrogenated TiO{sub 2}. • Superior photo-kinetics performance of hydrogenated TiO{sub 2}. - Abstract: Preparation of highly photo-activated TiO{sub 2} is achievable by hydrogenation at constant temperature and pressure, with controlled hydrogenation duration. The formation of surface disorders and Ti{sup 3+} is responsible for the color change from white unhydrogenated TiO{sub 2} to bluish-gray hydrogenated TiO{sub 2}. This color change, together with increased oxygen vacancies and Ti{sup 3+} enhanced the solar light absorption from UV to infra-red region. Interestingly, no band gap narrowing is observed. The photocatalytic activity in the UV and visible region is controlled by Ti{sup 3+} and oxygen vacancies respectively. Both Ti{sup 3+} and oxygen vacancies increases the electron density on the catalyst surface thus facilitates ·OH radicals formation. The lifespan of surface photo-excited electrons and holes are also sustained thus prevents charge carrier recombination. However, excessive amount of oxygen vacancies deteriorates the photocatalytic activity as it serves as charge traps. Hydrogenation of TiO{sub 2} also promotes the growth of active {0 0 1} facets and facilitates the photocatalytic activity by higher concentration of surface OH radicals. However, the growth of {0 0 1} facets is small and insignificant toward the overall photo-kinetics. This work also shows that larger role is played by Ti{sup 3+} and oxygen vacancies rather than the surface disorders created during the hydrogenation process. It also demonstrates the ability of hydrogenated TiO{sub 2} to absorb wider range of photons even though at a similar band gap as unhydrogenated TiO{sub 2}. In

Density functional study the interaction of oxygen molecule with defect sites of graphene

Energy Technology Data Exchange (ETDEWEB)

Qi Xuejun [State Key Laboratory of Coal Combustion, Wuhan 430074 (China); Guo Xin, E-mail: guoxin@mail.hust.edu.cn [State Key Laboratory of Coal Combustion, Wuhan 430074 (China); Zheng Chuguang [State Key Laboratory of Coal Combustion, Wuhan 430074 (China)

2012-10-15

Highlights: Black-Right-Pointing-Pointer The defect sites existed on the graphite surface create active sites and enhance the reactivity of carbonaceous material. Black-Right-Pointing-Pointer Oxygen molecule more favor chemisorbed on the graphene surface contains defect sites than the perfect surface. Black-Right-Pointing-Pointer The single active oxygen atom adsorbed on the defect surfaces, it completely insert into the surface. - Abstract: The present article reports a theoretical study of oxygen interacted with graphene surface containing defect sites on the atomic level by employing the density functional theory combined with the graphene cluster model. It was founded that oxygen molecule prefers to be chemisorbed on the graphene surface containing defect sites compared to the perfect surface. The adsorption energy of O{sub 2} on the double defect site is about 2.5 times as large as that on the perfect graphene surface. Moreover, the oxygen molecule interacts with S-W defect site gives rise to stable epoxy structure, which pulling the carbon atom outward from the original site in the direction perpendicular to the surface. If the oxygen molecule is adsorbed on the single vacancy site, two C-O bonds are formed on the graphene surface. However, when the oxygen molecule is chemisorbed on the double vacancy site, the oxygen atoms substitute the missing carbon atom's position in the carbon plane and form a hexagonal structure on the graphene network. The results indicate that single active oxygen atom approaches the defect site, it's completely adsorbed in the plane and high energy is released. In all cases, the interaction of an oxygen atom with defect surface involves an exothermic process. The defect site creates active sites on the surface of graphene and produces catalytic effects during the process of oxidation of carbonaceous materials.

Mixed oxygen ion/electron-conducting ceramics for oxygen separation

Energy Technology Data Exchange (ETDEWEB)

Stevenson, J.W.; Armstrong, T.R.; Armstrong, B.L. [Pacific Northwest National Lab., Richland, WA (United States)

1996-08-01

Mixed oxygen ion and electron-conducting ceramics are unique materials that can passively separate high purity oxygen from air. Oxygen ions move through a fully dense ceramic in response to an oxygen concentration gradient, charge-compensated by an electron flux in the opposite direction. Compositions in the system La{sub 1{minus}x}M{sub x}Co{sub 1{minus}y{minus}z}Fe{sub y}N{sub z}O{sub 3{minus}{delta}}, perovskites where M=Sr, Ca, and Ba, and N=Mn, Ni, Cu, Ti, and Al, have been prepared and their electrical, oxygen permeation, oxygen vacancy equilibria, and catalytic properties evaluated. Tubular forms, disks, and asymmetric membrane structures, a thin dense layer on a porous support of the same composition, have been fabricated for testing purposes. In an oxygen partial gradient, the passive oxygen flux through fully dense structures was highly dependent on composition. An increase in oxygen permeation with increased temperature is attributed to both enhanced oxygen vacancy mobility and higher vacancy populations. Highly acceptor-doped compositions resulted in oxygen ion mobilities more than an order of magnitude higher than yttria-stabilized zirconia. The mixed conducting ceramics have been utilized in a membrane reactor configuration to upgrade methane to ethane and ethylene. Conditions were established to balance selectivity and throughput in a catalytic membrane reactor constructed from mixed conducting ceramics.

Magnetoresistance Versus Oxygen Deficiency in Epi-stabilized SrRu1 - x Fe x O3 - δ Thin Films

Science.gov (United States)

Dash, Umasankar; Acharya, Susant Kumar; Lee, Bo Wha; Jung, Chang Uk

2017-03-01

Oxygen vacancies have a profound effect on the magnetic, electronic, and transport properties of transition metal oxide materials. Here, we studied the influence of oxygen vacancies on the magnetoresistance (MR) properties of SrRu1 - x Fe x O3 - δ epitaxial thin films ( x = 0.10, 0.20, and 0.30). For this purpose, we synthesized highly strained epitaxial SrRu1 - x Fe x O3 - δ thin films with atomically flat surfaces containing different amounts of oxygen vacancies using pulsed laser deposition. Without an applied magnetic field, the films with x = 0.10 and 0.20 showed a metal-insulator transition, while the x = 0.30 thin film showed insulating behavior over the entire temperature range of 2-300 K. Both Fe doping and the concentration of oxygen vacancies had large effects on the negative MR contributions. For the low Fe doping case of x = 0.10, in which both films exhibited metallic behavior, MR was more prominent in the film with fewer oxygen vacancies or equivalently a more metallic film. For semiconducting films, higher MR was observed for more semiconducting films having more oxygen vacancies. A relatively large negative MR ( 36.4%) was observed for the x = 0.30 thin film with a high concentration of oxygen vacancies ( δ = 0.12). The obtained results were compared with MR studies for a polycrystal of (Sr1 - x La x )(Ru1 - x Fe x )O3. These results highlight the crucial role of oxygen stoichiometry in determining the magneto-transport properties in SrRu1 - x Fe x O3 - δ thin films.

Effect of oxygen vacancy induced by pulsed magnetic field on the room-temperature ferromagnetic Ni-doped ZnO synthesized by hydrothermal method

Energy Technology Data Exchange (ETDEWEB)

Zhong, Min [Shanghai University, Laboratory for Microstructures, School of Materials Science and Engineering, 149 Yanchang Road, 200072 Shanghai (China); Li, Ying, E-mail: liying62@shu.edu.cn [Shanghai University, Laboratory for Microstructures, School of Materials Science and Engineering, 149 Yanchang Road, 200072 Shanghai (China); Tariq, Muhammad; Hu, Yemin; Li, Wenxian; Zhu, Mingyuan; Jin, Hongmin [Shanghai University, Laboratory for Microstructures, School of Materials Science and Engineering, 149 Yanchang Road, 200072 Shanghai (China); Li, Yibing [School of Chemistry, The University of New South Wales, Sydney, NSW, 2052 (Australia)

2016-08-05

Room temperature ferromagnetic 2% Ni doped ZnO rods were synthesized by high pulsed magnetic field-assisted hydrothermal method. A detailed study on the effect of high pulsed magnetic field on morphology, structural and magnetic properties of the ZnO rods has been carried out systematically by varying the intensity of field from 0 to 4 T. X-ray diffraction, Energy-dispersive spectroscopy measurements, and Raman spectra analysis suggest that all the samples have hexagonal wurtzite structure without detectable impurity. Field emission scanning electron microscopy images indicate that the particle size of samples decrease with increasing intensity of field. High resolution transmission electron microscopy observation ensures that the Ni ions addition do not change the wurtzite host matrix. X-ray photoelectron spectroscopy confirms the incorporation of Ni elements as divalent state and the dominant presence of oxygen vacancies in samples fabricated under 4 T pulsed magnetic field. Hysteresis loops demonstrate that the saturation magnetization increased regularly with the mounting magnetic field. On the framework of bound magnetic polaron model, the rising content of oxygen vacancies, as donor defect, lead to the stronger ferromagnetism in samples with pulsed magnetic field. Our findings provide a new insight for tuning the defect density by precisely controlling the intensity of field in order to get the desired magnetic behavior at room temperature. - Graphical abstract: This figure shows the magnetization versus magnetic field curves for 2%Ni doped ZnO as prepared with 0, 1, 2, 3 and 4 T pulsed magnetic field at 290 K. For 0 T sample, no ferromagnetic response is observed. But all the samples synthesized with field were well-defined hysteresis loops. The saturation magnetization estimated from the hysteresis loop come out to be ∼0.0024, 0.0023, 0.0036 and 0.0061 emu/g for 1 T, 2 T, 3 T and 4 T samples, respectively. As shown in the curves, the room

Room-temperature vacancy migration in crystalline Si from an ion-implanted surface layer

DEFF Research Database (Denmark)

Larsen, Arne Nylandsted; Christensen, Carsten; Petersen, Jon Wulff

1999-01-01

Migration of vacancies in crystalline, n-type silicon at room temperature from Ge+-implanted (150 keV, 5×109–1×1011 cm–2) surface layers was studied by tracing the presence of P–V pairs (E centers) in the underlying layer using deep level transient spectroscopy (DLTS). Under the conditions we have......–Et[approximate]0.15 eV that has donor character. It is argued that the center associated with this line is most probably the P2–V complex; it anneals at about 550 K. A lower limit of the RT-diffusion coefficient of the doubly charged, negative vacancy is estimated to be 4×10–11 cm2/s. ©1999 American Institute...

Density functional theory study of the adsorption and dissociation of O{sub 2} on CuO(1 1 1) surface

Energy Technology Data Exchange (ETDEWEB)

Sun, Shujuan, E-mail: sunshujuan@hebut.edu.cn [School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130 (China); Li, Chunyu [Science and Technology Innovation Center, Datang Technologies Industry Group Company Limited, Beijing (China); Zhang, Dongsheng [School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130 (China); Wang, Yanji, E-mail: yjwang@hebut.edu.cn [School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130 (China)

2015-04-01

Highlights: • The dissociation mechanisms of O{sub 2} on the CuO(1 1 1) surface have been obtained. • The energy barriers and reaction energies are calculated. • The presence of oxygen vacancy can obviously improve the catalytic activity of CuO. - Abstract: Density functional theory (DFT) have been performed to investigate the adsorption and dissociation of O{sub 2} on the perfect and oxygen-deficient CuO(1 1 1) surfaces. The calculated results indicate that the bridge site of two Cu{sub sub} atoms is the most favorable site for O adsorption on the perfect CuO(1 1 1) surface. But on the oxygen-deficient CuO(1 1 1) surface, the O atom adsorbed on O{sub vacancy} site after optimization. On the perfect and oxygen-deficient CuO(1 1 1) surfaces, the O{sub 2} are all paralleling to the surface after optimization. Possible dissociation pathways of molecularly adsorbed O{sub 2} on the two surfaces are identified. The calculated results suggest that the presence of oxygen vacancy exhibits a strong chemical reactivity towards the dissociation of O{sub 2} and can obviously improve the catalytic activity of CuO.

Enhancement of oxygen vacancies and solar photocatalytic activity of zinc oxide by incorporation of nonmetal

International Nuclear Information System (INIS)

Patil, Ashokrao B.; Patil, Kashinath R.; Pardeshi, Satish K.

2011-01-01

B-doped ZnO and N-doped ZnO powders have been synthesized by mechanochemical method and characterized by TG–DTA, XRD, SEM–EDX, XPS, UV–visible and photoluminescence (PL) spectra. X-ray diffraction data suggests the hexagonal wurtzite structure for modified ZnO crystallites and the incorporation of nonmetal expands the lattice constants of ZnO. The room temperature PL spectra suggest more number of oxygen vacancies exist in nonmetal-doped ZnO than that of undoped zinc oxide. XPS analysis shows the substitution of some of the O atoms of ZnO by nonmetal atoms. Solar photocatalytic activity of B-doped ZnO, N-doped ZnO and undoped ZnO was compared by means of oxidative photocatalytic degradation (PCD) of Bisphenol A (BPA). B-doped ZnO showed better solar PCD efficiency as compare to N-doped ZnO and undoped ZnO. The PCD of BPA follows first order reaction kinetics. The detail mechanism of PCD of Bisphenol A was proposed with the identification of intermediates such as hydroquinone, benzene-1,2,4-triol and 4-(2-hydroxypropan-2-yl) phenol. - Graphical Abstract: B-doped ZnO and N-doped ZnO synthesized by mechanochemical method were characterized by various techniques. Solar photocatalytic degradation of Bisphenol-A is in the order of B-ZnO>N-ZnO>ZnO. Highlights: ► B-doped ZnO and N-doped ZnO powders have been synthesized by mechanochemical method. ► PL spectra suggest oxygen vacancies are in order of B-doped ZnO>N-doped ZnO>ZnO. ► Solar PCD efficiency is in order of B-doped ZnO>N-doped ZnO>ZnO for Bisphenol A.

Zinc Vacancy-Induced Room-Temperature Ferromagnetism in Undoped ZnO Thin Films

Directory of Open Access Journals (Sweden)

Hongtao Ren

2012-01-01

Full Text Available Undoped ZnO thin films are prepared by polymer-assisted deposition (PAD and treated by postannealing at different temperatures in oxygen or forming gases (95%  Ar+5% H2. All the samples exhibit ferromagnetism at room temperature (RT. SQUID and positron annihilation measurements show that post-annealing treatments greatly enhance the magnetizations in undoped ZnO samples, and there is a positive correlation between the magnetization and zinc vacancies in the ZnO thin films. XPS measurements indicate that annealing also induces oxygen vacancies that have no direct relationship with ferromagnetism. Further analysis of the results suggests that the ferromagnetism in undoped ZnO is induced by Zn vacancies.

Vacancy identification in Co+ doped rutile TiO2 crystal with positron annihilation spectroscopy

International Nuclear Information System (INIS)

Ma Minyang; Qin Xiubo; Wang Baoyi; Wu Weiming

2013-01-01

Background: Room temperature Diluted Magnetic Semiconductor (DMS) is a critical path in the study of spin-electronic devices, but there are many disputes in the intrinsic properties and origin of the room temperature ferromagnetism. Positron annihilation spectroscopy (PAS) is a powerful technique for evaluating vacancy-type defects. Purpose: We aim to establish the relationship between the defect structure and ferromagnetism of the materials by analyzing the parameters of positron annihilation. Methods: Co-doped rutile TiO 2 films were synthesized by ion implantation and extensively studied by variable energy positron annihilation Doppler broadening spectroscopy (DBS) and coincidence Doppler broadening (CDB) measurements with variable energy slow positron beam for identification of the vacancies. Results: The results of DBS showed that a newly formed type of vacancy could be concluded by the S-W plot and the CDB results indicated that the oxygen vacancy (Vo) complex Ti-Co-Vo and/or Ti-Vo were formed with Co ions implantation and the vacancy concentration increased with increasing dopant dose. Conclusion: We identify that the generation of Ti-Vo and/or Ti-Co-Vo vacancy complex are induced by the existence of excess Ti 3d electrons around the oxygen vacancy. (authors)

Oxygen vacancy-induced room-temperature ferromagnetism in D—D neutron irradiated single-crystal TiO2 (001) rutile

Science.gov (United States)

Xu, Nan-Nan; Li, Gong-Ping; Pan, Xiao-Dong; Wang, Yun-Bo; Chen, Jing-Sheng; Bao, Liang-Man

2014-10-01

Remarkable room temperature ferromagnetism in pure single-crystal rutile TiO2 (001) samples irradiated by D—D neutron has been investigated. By combining X-ray diffraction and positron annihilation lifetime, the contracted lattice has been clearly identified in irradiated TiO2, where Ti4+ ions can be easily reduced to the state of Ti3+. As there were no magnetic impurities that could contaminate the samples during the whole procedure, some Ti3+ ions reside on interstitial or substituted sites accompanied by oxygen vacancies should be responsible for the ferromagnetism.

High-temperature equilibrium vacancy formation in ceramic materials studied by positron annihilation

International Nuclear Information System (INIS)

Forster, M.; Claudy, W.; Hermes, H.; Major, J.; Schaefer, H.E.; Koch, M.; Maier, K.; Stoll, H.

1992-01-01

Positron lifetime measurements were used in order to study thermal vacancy formation in NiO, YBa 2 Cu 3 O 7-δ , α-Al 2 O 3 , MgO and 6H-SiC at high temperatures. In NiO two increases of the positron trapping rate at 450K and 1200K (po 2 =10 5 Pa) are attributed to the change of charge of neutral extrinsic Ni-vacancies (c ≅ 10 -4 ) into a negative charge state and to the nonstochiometric formation of charged Ni-vacancies at high temperatures. In YBa 2 Cu 3 O 7-δ the oxygen loss or uptake at T > 680K with an activation enthalpy of 1.03eV can be studied by the variation of the positron lifetime with temperature and oxygen partial pressure. In α-Al 2 O 3 the positrons are annihilated from the delocalized free state between 1000K and 2250K and no positron trapping of thermally formed vacancies was detected which may be understood in terms of the theoretically predicted low concentrations of thermal vacancies. In MgO and 6H-SiC positron lifetime measurements were performed up to temperatures of about 2000K

Photoluminescence and Raman studies for the confirmation of oxygen vacancies to induce ferromagnetism in Fe doped Mn:ZnO compound

Energy Technology Data Exchange (ETDEWEB)

Das, J., E-mail: jayashree304@gmail.com [Department of Physics, Silicon Institute of Technology, Bhubaneswar 751024, Odisha (India); Department of Physics, College of Science, Engineering and Technology, University of South Africa, Johannesburg 1710 (South Africa); Mishra, D.K. [Department of Physics, College of Science, Engineering and Technology, University of South Africa, Johannesburg 1710 (South Africa); Department of Physics, Institute of Technical Education and Research, Siksha ‘O’ Anusandhan University, Khandagiri Square, Bhubaneswar 751030, Odisha (India); Srinivasu, V.V. [Department of Physics, College of Science, Engineering and Technology, University of South Africa, Johannesburg 1710 (South Africa); Sahu, D.R. [Amity Institute of Nanotechnology, Amity University, Noida (India); Roul, B.K. [Institute of Materials Science, Planetarium Building, Acharya Vihar, Bhubaneswar, Odisha (India)

2015-05-15

With a motivation to compare the magnetic property, we synthesised undoped, transition metal (TM) Mn doped and (Mn:Fe) co-doped ZnO ceramics in the compositions ZnO, Zn{sub 0.98}Mn{sub 0.02}O and Zn{sub 0.96}(Mn{sub 0.02}Fe{sub 0.02})O. Systematic investigations on the structural, microstructural, defect structure and magnetic properties of the samples were performed. Low temperature as well as room temperature ferromagnetism has been observed for all our samples, however, enhanced magnetisation at room temperature has been noticed when ZnO is co-doped with Fe along with Mn. Particularly the sample with the composition Zn{sub 0.96}Mn{sub 0.02}Fe{sub 0.02}O showed a magnetisation value more than double of the sample with composition Zn{sub 0.98}Mn{sub 0.02}O, indicating long range strong interaction between the magnetic impurities leading to higher ferromagnetic ordering. Raman and PL studies reveal presence of higher defects in form of oxygen vacancy clusters created in the sample due to Fe co doping. PL study also reveals enhanced luminescence efficiency in the co doped sample. Temperature dependent magnetisation study of this sample shows the spin freezing temperature around 39 K indicating the presence of small impurity phase of Mn{sub 2−x}Zn{sub x}O{sub 3} type. Electron Spin Resonance signal obtained supports ferromagnetic state in the co doped sample. Enhancement of magnetisation is attributed to interactions mediated by magnetic impurities through large number of oxygen vacancies created by Fe{sup 3+} ions forming bound magnetic polarons (BMP) and facilitating long range ferromagnetic ordering in the co- doped system. - Highlights: • Comparison of magnetic property of ZnO, Zn{sub 0.98}Mn {sub 0.02}O and Zn{sub 0.96}(Mn{sub 0.02}Fe{sub 0.02})O. • Observation of enhanced magnetisation at room temperature in (Mn,Fe) doped ZnO. • Raman and PL studies reveal presence of higher oxygen vacancy clusters. • Electron Spin Resonance signal supports

Electronic properties and surface reactivity of SrO-terminated SrTiO3 and SrO-terminated iron-doped SrTiO3.

Science.gov (United States)

Staykov, Aleksandar; Tellez, Helena; Druce, John; Wu, Ji; Ishihara, Tatsumi; Kilner, John

2018-01-01

Surface reactivity and near-surface electronic properties of SrO-terminated SrTiO 3 and iron doped SrTiO 3 were studied with first principle methods. We have investigated the density of states (DOS) of bulk SrTiO 3 and compared it to DOS of iron-doped SrTiO 3 with different oxidation states of iron corresponding to varying oxygen vacancy content within the bulk material. The obtained bulk DOS was compared to near-surface DOS, i.e. surface states, for both SrO-terminated surface of SrTiO 3 and iron-doped SrTiO 3 . Electron density plots and electron density distribution through the entire slab models were investigated in order to understand the origin of surface electrons that can participate in oxygen reduction reaction. Furthermore, we have compared oxygen reduction reactions at elevated temperatures for SrO surfaces with and without oxygen vacancies. Our calculations demonstrate that the conduction band, which is formed mainly by the d-states of Ti, and Fe-induced states within the band gap of SrTiO 3 , are accessible only on TiO 2 terminated SrTiO 3 surface while the SrO-terminated surface introduces a tunneling barrier for the electrons populating the conductance band. First principle molecular dynamics demonstrated that at elevated temperatures the surface oxygen vacancies are essential for the oxygen reduction reaction.

Investigation of the oxygen-vacancy (A-center) defect complex profile in neutron irradiated high resistivity silicon junction particle detectors

International Nuclear Information System (INIS)

Li, Zheng; Kraner, H.W.; Verbitskaya, E.; Eremin, V.; Ivanov, A.; Rubinelli, F.A.; Fonash, S.J.

1992-02-01

Distributions of the A-center (oxygen-vacancy) in neutron silicon detectors have been studied using Deep Level Transient Spectroscopy. A-centers have been found to be nearly uniformly distributed in the silicon water depth for medium resistivity (0.1 - 0.2 kΩ-cm) silicon detectors. A positive filling pulse was needed to detect the A-centers in high resistivity (>4 kΩ-cm) silicon detectors, and this effect was found to be dependent on the oxidation temperature. A discussion of this effect is presented. 16 refs

Room temperature alcohol sensing by oxygen vacancy controlled TiO2 nanotube array

International Nuclear Information System (INIS)

Hazra, A.; Dutta, K.; Bhowmik, B.; Bhattacharyya, P.; Chattopadhyay, P. P.

2014-01-01

Oxygen vacancy (OV) controlled TiO 2 nanotubes, having diameters of 50–70 nm and lengths of 200–250 nm, were synthesized by electrochemical anodization in the mixed electrolyte comprising NH 4 F and ethylene glycol with selective H 2 O content. The structural evolution of TiO 2 nanoforms has been studied by field emission scanning electron microscopy. Variation in the formation of OVs with the variation of the structure of TiO 2 nanoforms has been evaluated by photoluminescence and X-ray photoelectron spectroscopy. The sensor characteristics were correlated to the variation of the amount of induced OVs in the nanotubes. The efficient room temperature sensing achieved by the control of OVs of TiO 2 nanotube array has paved the way for developing fast responding alcohol sensor with corresponding response magnitude of 60.2%, 45.3%, and 36.5% towards methanol, ethanol, and 2-propanol, respectively.

Charge doping and large lattice expansion in oxygen-deficient heteroepitaxial WO3

Science.gov (United States)

Mattoni, Giordano; Filippetti, Alessio; Manca, Nicola; Zubko, Pavlo; Caviglia, Andrea D.

2018-05-01

Tungsten trioxide (WO3) is a versatile material with widespread applications ranging from electrochromics and optoelectronics to water splitting and catalysis of chemical reactions. For technological applications, thin films of WO3 are particularly appealing, taking advantage from a high surface-to-volume ratio and tunable physical properties. However, the growth of stoichiometric crystalline thin films is challenging because the deposition conditions are very sensitive to the formation of oxygen vacancies. In this paper, we show how background oxygen pressure during pulsed laser deposition can be used to tune the structural and electronic properties of WO3 thin films. By performing x-ray diffraction and low-temperature electrical transport measurements, we find changes in the WO3 lattice volume of up to 10% concomitantly with a resistivity drop of more than five orders of magnitude at room temperature as a function of increased oxygen deficiency. We use advanced ab initio calculations to describe in detail the properties of the oxygen vacancy defect states and their evolution in terms of excess charge concentration. Our results depict an intriguing scenario where structural, electronic, optical, and transport properties of WO3 single-crystal thin films can all be purposely tuned by controlling the oxygen vacancy formation during growth.

Vacancy identification in Co+ doped rutile TiO2 crystal with positron annihilation spectroscopy

Science.gov (United States)

Qin, X. B.; Zhang, P.; Liang, L. H.; Zhao, B. Z.; Yu, R. S.; Wang, B. Y.; Wu, W. M.

2011-01-01

Co-doped rutile TiO2 films were synthesized by ion implantation. Variable energy positron annihilation Doppler broadening spectroscopy and coincidence Doppler broadening measurements were performed for identification of the vacancies. A newly formed type of vacancy can be concluded by the S-W plot and the CDB results indicated that the oxygen vacancy (VO) complex Ti-Co-VO and/or Ti-VO are formed with Co ions implantation and the vacancy concentration is increased with increase of dopant dose.

Magnetoresistance Versus Oxygen Deficiency in Epi-stabilized SrRu1 - x Fe x O3 - δ Thin Films.

Science.gov (United States)

Dash, Umasankar; Acharya, Susant Kumar; Lee, Bo Wha; Jung, Chang Uk

2017-12-01

Oxygen vacancies have a profound effect on the magnetic, electronic, and transport properties of transition metal oxide materials. Here, we studied the influence of oxygen vacancies on the magnetoresistance (MR) properties of SrRu 1 - x Fe x O 3 - δ epitaxial thin films (x = 0.10, 0.20, and 0.30). For this purpose, we synthesized highly strained epitaxial SrRu 1 - x Fe x O 3 - δ thin films with atomically flat surfaces containing different amounts of oxygen vacancies using pulsed laser deposition. Without an applied magnetic field, the films with x = 0.10 and 0.20 showed a metal-insulator transition, while the x = 0.30 thin film showed insulating behavior over the entire temperature range of 2-300 K. Both Fe doping and the concentration of oxygen vacancies had large effects on the negative MR contributions. For the low Fe doping case of x = 0.10, in which both films exhibited metallic behavior, MR was more prominent in the film with fewer oxygen vacancies or equivalently a more metallic film. For semiconducting films, higher MR was observed for more semiconducting films having more oxygen vacancies. A relatively large negative MR (~36.4%) was observed for the x = 0.30 thin film with a high concentration of oxygen vacancies (δ = 0.12). The obtained results were compared with MR studies for a polycrystal of (Sr 1 - x La x )(Ru 1 - x Fe x )O 3 . These results highlight the crucial role of oxygen stoichiometry in determining the magneto-transport properties in SrRu 1 - x Fe x O 3 - δ thin films.

Enhanced room temperature ferromagnetism in electrodeposited Co-doped ZnO nanostructured thin films by controlling the oxygen vacancy defects

Energy Technology Data Exchange (ETDEWEB)

Simimol, A. [Nanomaterials Research Lab, Surface Engineering Division, CSIR-National Aerospace Laboratories, Post Bag No. 1779, Bangalore 560017 (India); Department of Physics, National Institute of Technology Calicut, Calicut 673601 (India); Anappara, Aji A. [Department of Physics, National Institute of Technology Calicut, Calicut 673601 (India); Greulich-Weber, S. [Department of Physics, Nanophotonic Materials, Faculty of Science, University of Paderborn, 33095 Paderborn (Germany); Chowdhury, Prasanta [Nanomaterials Research Lab, Surface Engineering Division, CSIR-National Aerospace Laboratories, Post Bag No. 1779, Bangalore 560017 (India); Barshilia, Harish C., E-mail: harish@nal.res.in

2015-06-07

We report the growth of un-doped and cobalt doped ZnO nanostructures fabricated on FTO coated glass substrates using electrodeposition method. A detailed study on the effects of dopant concentration on morphology, structural, optical, and magnetic properties of the ZnO nanostructures has been carried out systematically by varying the Co concentration (c.{sub Co}) from 0.01 to 1 mM. For c.{sub Co }≤ 0.2 mM, h-wurtzite phase with no secondary phases of Co were present in the ZnO nanostructures. For c.{sub Co} ≤ 0.2 mM, the photoluminescence spectra exhibited a decrease in the intensity of ultraviolet emission as well as band-gap narrowing with an increase in dopant concentration. All the doped samples displayed a broad emission in the visible range and its intensity increased with an increase in Co concentration. It was found that the defect centers such as oxygen vacancies and zinc interstitials were the source of the visible emission. The X-ray photoelectron spectroscopy studies revealed, Co was primarily in the divalent state, replacing the Zn ion inside the tetrahedral crystal site of ZnO without forming any cluster or secondary phases of Co. The un-doped ZnO nanorods exhibited diamagnetic behavior and it remained up to a c.{sub Co} of 0.05 mM, while for c.{sub Co }> 0.05 mM, the ZnO nanostructures exhibited ferromagnetic behavior at room temperature. The coercivity increased to 695 G for 0.2 mM Co-doped sample and then it decreased for c.{sub Co }> 0.2 mM. Our results illustrate that up to a threshold concentration of 0.2 mM, the strong ferromagnetism is due to the oxygen vacancy defects centers, which exist in the Co-doped ZnO nanostructures. The origin of strong ferromagnetism at room temperature in Co-doped ZnO nanostructures is attributed to the s-d exchange interaction between the localized spin moments resulting from the oxygen vacancies and d electrons of Co{sup 2+} ions. Our findings provide a new insight for tuning the

Positron annihilation study of vacancy-type defects in fast-neutron-irradiated MgO·nAl2O3

Science.gov (United States)

Rahman, Abu Zayed Mohammad Saliqur; Li, Zhuoxin; Cao, Xingzhong; Wang, Baoyi; Wei, Long; Xu, Qiu; Atobe, Kozo

2014-09-01

The positron lifetimes of fast-neutron-irradiated MgO·nAl2O3 single crystals were measured to investigate the formation of cation vacancies. Al monovacancy was possibly observed in samples irradiated by fast neutrons at ultra-low temperatures. Additionally, vacancy-oxygen complex centers were possibly observed in samples irradiated at higher temperatures and fast neutron fluences. Coincidence Doppler broadening (CDB) spectra were measured to obtain information regarding the vicinity of vacancy-type defects. A peak at approximately 11 × 10-3 m0c was observed, which may be due to the presence of oxygen atoms in the neighborhood of the vacancies.

The surface chemistry of metal-oxygen interactions

DEFF Research Database (Denmark)

Stokbro, Kurt; Baroni, Stefano

1997-01-01

We report on a computational study of the clean and oxygen-covered Rh(110) surface, based on density-functional theory within the local-density approximation. We have used plane-wave basis sets and Vanderbilt ultra-soft pseudopotentials. For the clean surface, we present results for the equilibrium...... structure, surface energy and surface stress of the unreconstructed and (1 x 2) reconstructed structures. For the oxygen-covered surface we have performed a geometry optimization at 0.5, 1, and 2 monolayer oxygen coverages, and we present results for the equilibrium configurations, workfunctions and oxygen...

High temperature oxidation of metals: vacancy injection and consequences on the mechanical properties

International Nuclear Information System (INIS)

Perusin, S.

2004-11-01

The aim of this work is to account for the effects of the high temperature oxidation of metals on their microstructure and their mechanical properties. 'Model' materials like pure nickel, pure iron and the Ni-20Cr alloy are studied. Nickel foils have been oxidised at 1000 C on one side only in laboratory air, the other side being protected from oxidation by a reducing atmosphere. After the oxidation treatment, the unoxidized face was carefully examined by using an Atomic Force Microscope (AFM). Grain boundaries grooves were characterised and their depth were compared to the ones obtained on the same sample heat treated in the reducing atmosphere during the same time. They are found to be much deeper in the case of the single side oxidised samples. It is shown that this additional grooving is directly linked to the growth of the oxide scale on the opposite side and that it can be explained by the diffusion of the vacancies produced at the oxide scale - metal interface, across the entire sample through grain boundaries. Moreover, the comparison between single side oxidised samples and samples oxidised on both sides points out that voids in grain boundaries are only observed in this latter case proving the vacancies condensation in the metal when the two faces are oxidised. The role of the carbon content and the sample's geometry on this phenomenon is examined in detail. The diffusion of vacancies is coupled with the transport of oxygen so that a mechanism of oxygen transport by vacancies is suggested. The tensile tests realised at room temperature on nickel foils (bamboo microstructure) show that the oxide scale can constitute a barrier to the emergence of dislocations at the metal surface. Finally, the Ni-20Cr alloy is tested in tensile and creep tests between 25 and 825 C in oxidising or reducing atmospheres. (author)

Multi-scale modeling of interaction between vacancies and alloying elements in ferritic alloys

International Nuclear Information System (INIS)

Barouh, Caroline

2015-01-01

This PhD thesis is devoted to the study of interaction between vacancies and alloying elements in Oxide Dispersion Strengthened (ODS) steels, which are promising candidate materials for future nuclear reactors. This work is based on multi-scale modeling of a simplified system composed by oxygen, yttrium and titanium atoms and vacancies in an α-iron lattice. We particularly focused on the role of vacancies which are created in excess during the fabrication of these steels. The stability and mobility of vacancy-solute clusters have been examined using ab initio calculations for oxygen, on one hand, which has been systematically compared to carbon and nitrogen, interstitial solutes frequently present in iron-based materials, and, on the other hand, for substitutional solutes: titanium and yttrium. The three interstitial solutes show very similar energetic and kinetic behaviors. The impact of small mobile vacancy-solute clusters has been verified using a cluster dynamics model based on our ab initio results. It has been thus demonstrated that with over-saturation of vacancies, diffusion of interstitial solutes may be accelerated, while substitutional solutes do not become necessarily faster. These conclusions are consistent with existing experimental observations. All these results have been then used to complete our understanding of nano-clusters formation mechanisms. It appeared that the relative mobility of yttrium and titanium, as well as the number of potential nuclei to form nanoparticles strongly depend on the total vacancy concentration in the system. (author) [fr

Effects of grain boundaries at the electrolyte/cathode interfaces on oxygen reduction reaction kinetics of solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Choi, Min Gi; Koo, Ja Yang; Ahn, Min Woo; Lee, Won Young [Dept. of Mechanical Engineering, Sungkyunkwan University, Suwon (Korea, Republic of)

2017-04-15

We systematically investigated the effects of grain boundaries (GBs) at the electrolyte/cathode interface of two conventional electrolyte materials, i.e., yttria-stabilized zirconia (YSZ) and gadolinia-doped ceria (GDC). We deposited additional layers by pulsed laser deposition to control the GB density on top of the polycrystalline substrates, obtaining significant improvements in peak power density (two-fold for YSZ and three-fold for GDC). The enhanced performance at high GB density in the additional layer could be ascribed to the accumulation of oxygen vacancies, which are known to be more active sites for oxygen reduction reactions (ORR) than grain cores. GDC exhibited a higher enhancement than YSZ, due to the easier formation, and thus higher concentration, of oxygen vacancies for ORR. The strong relation between the concentration of oxygen vacancies and the surface exchange characteristics substantiated the role of GBs at electrolyte/cathode interfaces on ORR kinetics, providing new design parameters for highly performing solid oxide fuel cells.

Migration of O vacancies in α-quartz: The effect of excitons and electron holes

International Nuclear Information System (INIS)

Song, Jakyoung; Corrales, L. Rene; Kresse, Georg; Jonsson, Hannes

2001-01-01

We have used density-functional theory and the nudged elastic-band method to calculate migration pathways and estimated the activation energy for the diffusion of oxygen vacancies in α-quartz. While the energy barrier for the diffusion of a neutral vacancy is very high, 4.1 eV, the binding of a triplet-state exciton to the vacancy lowers the barrier to 1.7 eV and the attachment of a hole lowers the barrier to 1.9 eV, making the vacancy mobile at commonly used annealing temperatures

Ionized zinc vacancy mediated ferromagnetism in copper doped ZnO thin films

Directory of Open Access Journals (Sweden)

Shi-Yi Zhuo

2012-03-01

Full Text Available This paper reports the origin of ferromagnetism in Cu-doped ZnO thin films. Room-temperature ferromagnetism is obtained in all the thin films when deposited at different oxygen partial pressure. An obviously enhanced peak corresponding to zinc vacancy is observed in the photoluminescence spectra, while the electrical spin resonance measurement implies the zinc vacancy is negative charged. After excluding the possibility of direct exchange mechanisms (via free carriers, we tentatively propose a quasi-indirect exchange model (via ionized zinc vacancy for Cu-doped ZnO system.

Wide-range tunable bandgap in Bi1−xCaxFe1−yTiyO3−δ nanoparticles via oxygen vacancy induced structural modulations at room temperature

International Nuclear Information System (INIS)

Mocherla, Pavana S V; Sudakar, C; Gautam, Sanjeev; Chae, Keun Hwa; Rao, M S Ramachandra

2015-01-01

We demonstrate that oxygen vacancies (V O ) produced by aliovalent (Ca 2+ ) doping in BiFeO 3 (BCFO) and associated structural changes due to V O ordering result in systematic alteration of the bandgap (E g ) over a wide range from 1.5 eV to 2.3 eV. By contrast, the change in the bandgap of a Ca 2+ and Ti 4+ co-doped BiFeO 3 (BCFTO) system, wherein the V O formation is suppressed, is negligible. These contrastive results strongly confirm the role of oxygen vacancies in altering the bandgap of BCFO. Irrespective of doping, microstrain, which is found to be large (0.3 to 1.2%) below a critical size (d c ∼ 60 nm) also produces a small, yet linear change in the bandgap (E g from 2.0 to 2.3 eV). The cubic phase stabilizes gradually in BCFO for x > 0.1 through an orthorhombic phase (for 0.05 < x < 0.1), whereas it directly transforms for x > 0.1 in BCFTO. This change in BCFO at 300 K suggests a high-pressure-like (or high-temperature-like) effect of the oxygen vacancies and dopants on the structure. Systematic variations in the relative intensities and peak positions of Fe d–d transitions in BCFO reveal the local changes in Fe–O–Fe coordination. These results along with XANES and HRTEM studies substantiate the observed structural changes. (paper)

Low-temperature positron lifetime and Doppler-broadening measurements for single-crystal nickel oxide containing cation vacancies

International Nuclear Information System (INIS)

Waber, J.T.; Snead, C.L. Jr.; Lynn, K.G.

1985-01-01

Lifetime and Doppler-broadening measurements for positron annihilation in substoichiometric nickelous oxide have been made concomitantly from liquid-helium to room temperature. The concentration of cation vacancies is readily controlled by altering the ambient oxygen pressure while annealing the crystals at 1673 0 K. It was found that neither of the three lifetimes observed or their relative intensities varied significantly with the oxygen pressure, and the bulk rate only increased slightly when the specimen was cooled from room to liquid-helium temperatures. These results are interpreted as indicating that some of the positrons are trapped by the existing cation vacancies and a smaller fraction by vacancy clusters

Vacancy defect and defect cluster energetics in ion-implanted ZnO

Science.gov (United States)

Dong, Yufeng; Tuomisto, F.; Svensson, B. G.; Kuznetsov, A. Yu.; Brillson, Leonard J.

2010-02-01

We have used depth-resolved cathodoluminescence, positron annihilation, and surface photovoltage spectroscopies to determine the energy levels of Zn vacancies and vacancy clusters in bulk ZnO crystals. Doppler broadening-measured transformation of Zn vacancies to vacancy clusters with annealing shifts defect energies significantly lower in the ZnO band gap. Zn and corresponding O vacancy-related depth distributions provide a consistent explanation of depth-dependent resistivity and carrier-concentration changes induced by ion implantation.

Room temperature alcohol sensing by oxygen vacancy controlled TiO{sub 2} nanotube array

Energy Technology Data Exchange (ETDEWEB)

Hazra, A.; Dutta, K.; Bhowmik, B.; Bhattacharyya, P., E-mail: pb-etc-besu@yahoo.com [Nano-Thin Films and Solid State Gas Sensor Devices Laboratory, Department of Electronics and Telecommunication Engineering, Indian Institute of Engineering Science and Technology (IIEST), Shibpur, Howrah (India); Chattopadhyay, P. P. [Department of Metallurgy and Materials Engineering, Indian Institute of Engineering Science and Technology (IIEST), Shibpur, Howrah (India)

2014-08-25

Oxygen vacancy (OV) controlled TiO{sub 2} nanotubes, having diameters of 50–70 nm and lengths of 200–250 nm, were synthesized by electrochemical anodization in the mixed electrolyte comprising NH{sub 4}F and ethylene glycol with selective H{sub 2}O content. The structural evolution of TiO{sub 2} nanoforms has been studied by field emission scanning electron microscopy. Variation in the formation of OVs with the variation of the structure of TiO{sub 2} nanoforms has been evaluated by photoluminescence and X-ray photoelectron spectroscopy. The sensor characteristics were correlated to the variation of the amount of induced OVs in the nanotubes. The efficient room temperature sensing achieved by the control of OVs of TiO{sub 2} nanotube array has paved the way for developing fast responding alcohol sensor with corresponding response magnitude of 60.2%, 45.3%, and 36.5% towards methanol, ethanol, and 2-propanol, respectively.

Sr{sub 2}MgMoO{sub 6−δ} thin films fabricated using pulsed-laser deposition with high concentrations of oxygen vacancies

Energy Technology Data Exchange (ETDEWEB)

Shigematsu, K. [Department of Chemistry, The University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan); Chikamatsu, A., E-mail: chikamatsu@chem.s.u-tokyo.ac.jp; Fukumura, T. [Department of Chemistry, The University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan); JST-CREST, Bunkyo-ku, Tokyo 113-0033 (Japan); Toyoda, S. [Department of Materials Science and Engineering, Kyoto University, Yoshida-honmachi, Kyoto 606-8501 (Japan); Ikenaga, E. [JASRI/SPring-8, Mikazuki-cho, Hyogo 679-5198 (Japan); Hasegawa, T. [Department of Chemistry, The University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan); JST-CREST, Bunkyo-ku, Tokyo 113-0033 (Japan); Kanagawa Academy of Science and Technology (KAST), Kawasaki, Kanagawa 213-0012 (Japan)

2014-06-30

We fabricated epitaxial thin films of oxygen-vacant Sr{sub 2}MgMoO{sub 6−δ} using pulsed laser deposition. The films showed low resistivity of the order of 10{sup −2} Ω cm at 300 K. X-ray diffraction analyses revealed that Mg and Mo ions in the Sr{sub 2}MgMoO{sub 6−δ} films were considerably disordered, compared to those in bulk Sr{sub 2}MgMoO{sub 6−δ}. The proportion of oxygen vacancies estimated through hard x-ray photoemission measurements was as large as 0.37, and correlated well with the Mg/Mo ordering.

Vacancy-induced ferromagnetism in ZnO probed by spin-polarized positron annihilation spectroscopy

Science.gov (United States)

Maekawa, Masaki; Abe, Hiroshi; Miyashita, Atsumi; Sakai, Seiji; Yamamoto, Shunya; Kawasuso, Atsuo

2017-04-01

We investigated the ferromagnetism of ZnO induced by oxygen implantation by using spin-polarized positron annihilation spectroscopy together with magnetization measurements. The magnetization measurements showed the appearance of ferromagnetism after oxygen implantation and its disappearance during post-implantation annealing at temperatures above 573 K. The Doppler broadening of annihilation radiation (DBAR) spectrum showed asymmetry upon field reversal after oxygen implantation. The obtained differential DBAR spectrum between positive and negative magnetic fields was well-explained with a theoretical calculation considering zinc vacancies. The disappearance of the field-reversal asymmetry of the DBAR spectrum as a result of annealing agreed with the observations of ferromagnetism by magnetization measurements. These results suggest the radiation-induced zinc vacancies to be the source of the observed ferromagnetism of ZnO.

High density nitrogen-vacancy sensing surface created via He{sup +} ion implantation of {sup 12}C diamond

Energy Technology Data Exchange (ETDEWEB)

Kleinsasser, Ed E., E-mail: edklein@uw.edu [Department of Electrical Engineering, University of Washington, Seattle, Washington 98195-2500 (United States); Stanfield, Matthew M.; Banks, Jannel K. Q. [Department of Physics, University of Washington, Seattle, Washington 98195-1560 (United States); Zhu, Zhouyang; Li, Wen-Di [HKU-Shenzhen Institute of Research and Innovation (HKU-SIRI), Shenzhen 518000 (China); Department of Mechanical Engineering, The University of Hong Kong, Pokfulam, Hong Kong (China); Acosta, Victor M. [Department of Physics and Astronomy, Center for High Technology Materials, University of New Mexico, Albuquerque, New Mexico 87106 (United States); Watanabe, Hideyuki [Correlated Electronics Group, Electronics and Photonics Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 5, 1-1-1, Higashi, Tsukuba, Ibaraki 305-8565 (Japan); Itoh, Kohei M. [School of Fundamental Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522 (Japan); Fu, Kai-Mei C., E-mail: kaimeifu@uw.edu [Department of Electrical Engineering, University of Washington, Seattle, Washington 98195-2500 (United States); Department of Physics, University of Washington, Seattle, Washington 98195-1560 (United States)

2016-05-16

We present a promising method for creating high-density ensembles of nitrogen-vacancy centers with narrow spin-resonances for high-sensitivity magnetic imaging. Practically, narrow spin-resonance linewidths substantially reduce the optical and RF power requirements for ensemble-based sensing. The method combines isotope purified diamond growth, in situ nitrogen doping, and helium ion implantation to realize a 100 nm-thick sensing surface. The obtained 10{sup 17 }cm{sup −3} nitrogen-vacancy density is only a factor of 10 less than the highest densities reported to date, with an observed 200 kHz spin resonance linewidth over 10 times narrower.

Identification of vacancy defect complexes in transparent semiconducting oxides ZnO, In2O3 and SnO2

International Nuclear Information System (INIS)

Makkonen, Ilja; Korhonen, Esa; Prozheeva, Vera; Tuomisto, Filip

2016-01-01

Positron annihilation spectroscopy, when combined with supporting high-quality modeling of positron states and annihilation in matter, is a powerful tool for detailed defect identification of vacancy-type defects in semiconductors and oxides. Here we demonstrate that the Doppler broadening of the positron annihilation radiation is a very sensitive means for observing the oxygen environment around cation vacancies, the main open-volume defects trapping positrons in measurements made for transparent semiconducting oxides. Changes in the positron annihilation signal due to external manipulation such as irradiation and annealing can be correlated with the associated changes in the sizes of the detected vacancy clusters. Our examples for ZnO, In 2 O 3 and SnO 2 demonstrate that oxygen vacancies in oxides can be detected directly using positron annihilation spectroscopy when they are complexed with cation vacancies. (paper)

Identification of vacancy defect complexes in transparent semiconducting oxides ZnO, In2O3 and SnO2

Science.gov (United States)

Makkonen, Ilja; Korhonen, Esa; Prozheeva, Vera; Tuomisto, Filip

2016-06-01

Positron annihilation spectroscopy, when combined with supporting high-quality modeling of positron states and annihilation in matter, is a powerful tool for detailed defect identification of vacancy-type defects in semiconductors and oxides. Here we demonstrate that the Doppler broadening of the positron annihilation radiation is a very sensitive means for observing the oxygen environment around cation vacancies, the main open-volume defects trapping positrons in measurements made for transparent semiconducting oxides. Changes in the positron annihilation signal due to external manipulation such as irradiation and annealing can be correlated with the associated changes in the sizes of the detected vacancy clusters. Our examples for ZnO, In2O3 and SnO2 demonstrate that oxygen vacancies in oxides can be detected directly using positron annihilation spectroscopy when they are complexed with cation vacancies.

Synthesis and oxygen vacancy related NO{sub 2} gas sensing properties of ZnO:Co nanorods arrays gown by a hydrothermal method

Energy Technology Data Exchange (ETDEWEB)

Zou, Changwei, E-mail: qingyihaiyanas@163.com; Liang, Feng; Xue, Shuwen

2015-10-30

Highlights: • Co doped ZnO:Co nanorods were grown by hydrothermal method. • The NO{sub 2} response reaches a maximum value of 88 at 210 °C. • The stability of NO{sub 2} on ZnO is enhanced with the presence of V{sub O}. - Abstract: Highly ordered Co doped ZnO:Co nanorods arrays with Co concentrations of 1.6, 1.9 and 3.1 at% were uniformly grown on FTO glass substrate by hydrothermal method. The X-ray diffraction patterns of the undoped and Co doped ZnO nanorods revealed characteristic peaks of (1 0 0), (0 0 2), (1 0 1), (1 0 3) and (1 1 2), corresponding to the hexagonal wurtzite phase of ZnO. For ZnO:Co nanorods with Co concentrations of 3.1 at%, the NO{sub 2} response reached a maximum value of 88 at temperature of 210 °C. However, the response of ZnO:Co nanorods with Co concentrations of 3.1 at% decreased from 82 to 29 with the increasing of O{sub 2} annealing temperature from 0 to 700 °C. As confirmed by the XPS, PL, Raman and I–V results, the oxygen vacancies and electron concentrations were the dominating effects and an oxygen vacancy mediated NO{sub 2} sensing mechanism was presented and discussed.

Spin polarized electronic states and spin textures at the surface of oxygen-deficient SrTiO3

Science.gov (United States)

Jeschke, Harald O.; Altmeyer, Michaela; Rozenberg, Marcelo; Gabay, Marc; Valenti, Roser

We investigate the electronic structure and spin texture at the (001) surface of SrTiO3 in the presence of oxygen vacancies by means of ab initio density functional theory (DFT) calculations of slabs. Relativistic non-magnetic DFT calculations exhibit Rashba-like spin winding with a characteristic energy scale ~ 10 meV. However, when surface magnetism on the Ti ions is included, bands become spin-split with an energy difference ~ 100 meV at the Γ point. This energy scale is comparable to the observations in SARPES experiments performed on the two-dimensional electronic states confined near the (001) surface of SrTiO3. We find the spin polarized state to be the ground state of the system, and while magnetism tends to suppress the effects of the relativistic Rashba interaction, signatures of it are still clearly visible in terms of complex spin textures. We gratefully acknowledge financial support from the Deutsche Forschungsgemeinschaft through grants SFB/TR 49 and FOR 1346.

Interplay of Cu and oxygen vacancy in optical transitions and screening of excitons in ZnO:Cu films

International Nuclear Information System (INIS)

Darma, Yudi; Rusydi, Andrivo; Seng Herng, Tun; Marlina, Resti; Fauziah, Resti; Ding, Jun

2014-01-01

We study room temperature optics and electronic structures of ZnO:Cu films as a function of Cu concentration using a combination of spectroscopic ellipsometry, photoluminescence, and ultraviolet-visible absorption spectroscopy. Mid-gap optical states, interband transitions, and excitons are observed and distinguishable. We argue that the mid-gap states are originated from interactions of Cu and oxygen vacancy (Vo). They are located below conduction band (Zn4s) and above valence band (O2p) promoting strong green emission and narrowing optical band gap. Excitonic states are screened and its intensities decrease upon Cu doping. Our results show the importance of Cu and Vo driving the electronic structures and optical transitions in ZnO:Cu films

Interplay of Cu and oxygen vacancy in optical transitions and screening of excitons in ZnO:Cu films

Science.gov (United States)

Darma, Yudi; Seng Herng, Tun; Marlina, Resti; Fauziah, Resti; Ding, Jun; Rusydi, Andrivo

2014-02-01

We study room temperature optics and electronic structures of ZnO:Cu films as a function of Cu concentration using a combination of spectroscopic ellipsometry, photoluminescence, and ultraviolet-visible absorption spectroscopy. Mid-gap optical states, interband transitions, and excitons are observed and distinguishable. We argue that the mid-gap states are originated from interactions of Cu and oxygen vacancy (Vo). They are located below conduction band (Zn4s) and above valence band (O2p) promoting strong green emission and narrowing optical band gap. Excitonic states are screened and its intensities decrease upon Cu doping. Our results show the importance of Cu and Vo driving the electronic structures and optical transitions in ZnO:Cu films.

Study of surface by ion scattering with simultaneous formation of inner shell vacancies

International Nuclear Information System (INIS)

Zinov'ev, A.N.

2002-01-01

The program on modeling the atomic particles scattering, making it possible to account for the change in the particles charge state in each collision act with an account of the additional ionization, is developed. It is shown, that the additional ionization of the departing particles due to the decay of vacancies in the inner shells increases the accuracy of the surface composition analysis. The algorithm of deriving from the experimental data the information on the dependence of the particles neutralization probability on the distance from the surface is proposed and the conclusion is made on the necessity of accounting for the recharge process for neutralization of the ions with the q>2 [ru

In Operando Self-Healing of Perovskite Electrocatalysts: A Case Study of SrCoO3 for the Oxygen Evolution Reaction

KAUST Repository

Tahini, Hassan A.; Tan, Xin; Schwingenschlö gl, Udo; Smith, Sean C.

2017-01-01

Perovskites are promising catalysts for oxygen evolution reactions (OER); among them, SrCoO3 is one of the best for these reactions. We study the O* intermediates and the role of surface oxygen vacancies of SrCoO3 during OER. A self-healing mechanism is proposed in which O* are incorporated into the surface to recover the redox capabilities of the material.

In Operando Self-Healing of Perovskite Electrocatalysts: A Case Study of SrCoO3 for the Oxygen Evolution Reaction

KAUST Repository

Tahini, Hassan A.

2017-01-24

Perovskites are promising catalysts for oxygen evolution reactions (OER); among them, SrCoO3 is one of the best for these reactions. We study the O* intermediates and the role of surface oxygen vacancies of SrCoO3 during OER. A self-healing mechanism is proposed in which O* are incorporated into the surface to recover the redox capabilities of the material.

Vacancy-induced magnetism in BaTiO3(001) thin films based on density functional theory.

Science.gov (United States)

Cao, Dan; Cai, Meng-Qiu; Hu, Wang-Yu; Yu, Ping; Huang, Hai-Tao

2011-03-14

The origin of magnetism induced by vacancies on BaTiO(3)(001) surfaces is investigated systematically by first-principles calculations within density-functional theory. The calculated results show that O vacancy is responsible for the magnetism of the BaO-terminated surface and the magnetism of the TiO(2)-terminated surface is induced by Ti vacancy. For the BaO-terminated surface, the magnetism mainly arises from the unpaired electrons that are localized in the O vacancy basin. In contrast, for the TiO(2)-terminated surface, the magnetism mainly originates from the partially occupied O-2p states of the first nearest neighbor O atoms surrounding the Ti vacancy. These results suggest the possibility of implementing magneto-electric coupling in conventional ferroelectric materials.

Vacancy supersaturations produced by high-energy ion implantation

International Nuclear Information System (INIS)

Venezia, V.C.; Eaglesham, D.J.; Jacobson, D.C.; Gossmann, H.J.

1998-01-01

A new technique for detecting the vacancy clusters produced by high-energy ion implantation into silicon is proposed and tested. This technique takes advantage of the fact that metal impurities, such as Au, are gettered near one-half of the projected range (1/2 R p ) of MeV implants. The vacancy clustered region produced by a 2 MeV Si + implant into silicon has been labeled with Au diffused in from the front surface. The trapped Au was detected by Rutherford backscattering spectrometry (RBS) to profile the vacancy clusters. Cross section transmission electron microscopy (XTEM) analysis shows that the Au in the region of vacancy clusters is in the form of precipitates. By annealing MeV implanted samples prior to introduction of the Au, changes in the defect concentration within the vacancy clustered region were monitored as a function of annealing conditions

On the electronic, structural, and thermodynamic properties of Au supported on α-Fe{sub 2}O{sub 3} surfaces and their interaction with CO

Energy Technology Data Exchange (ETDEWEB)

Nguyen, Manh-Thuong, E-mail: manhth.nguyen@gmail.com; Gebauer, Ralph [The Abdus Salam International Centre for Theoretical Physics, Strada Costiera 11, 34151 Trieste (Italy); Farnesi Camellone, Matteo, E-mail: mfarnesi@sissa.it [CNR-IOM DEMOCRITOS, Istituto Officina dei Materiali, Consiglio Nazionale delle Ricerche and SISSA Scuola Internazionale di Studi Superiori Avanzati, Via Bonomea 265, I-34136 Trieste (Italy)

2015-07-21

Extensive first principles calculations are carried out to investigate Au monomers and dimers supported on α-Fe{sub 2}O{sub 3}(0001) surfaces in terms of structure optimizations, electronic structure analyses, and ab initio thermodynamics calculations of surface phase diagrams. All computations rely on density functional theory in the generalized gradient approximation (Perdew-Burke-Ernzerhof (PBE)) and account for on-site Coulomb interactions via inclusion of a Hubbard correction (PBE+U). The relative stability of Au monomers/dimers on the stoichiometric termination of α-Fe{sub 2}O{sub 3}(0001) decorated with various vacancies (multiple oxygen vacancies, iron vacancy, and mixed iron-oxygen vacancies) has been computed as a function of the oxygen chemical potential. The charge rearrangement induced by Au at the oxide contact is analyzed in detail and discussed. On one hand, ab initio thermodynamics predicts that under O-rich conditions, structures obtained by replacing a surface Fe atom with a Au atom are thermodynamically stable over a wide range of temperatures. On the other hand, the complex of a CO molecule on a Au atom substituting surface Fe atoms is thermodynamically stable only in a much more narrow range of values of the O chemical potential under O-rich conditions. In the case of a Au dimer, under O-rich conditions, supported Au atoms at an O-Fe di-vacancy are more stable. However, upon CO adsorption, the complex of a CO molecule and 2 Au atoms located at a single Fe vacancy is more favorable.

Quasi-two-dimensional electron gas at the epitaxial alumina/SrTiO{sub 3} interface: Control of oxygen vacancies

Energy Technology Data Exchange (ETDEWEB)

Kormondy, Kristy J.; Posadas, Agham B.; Demkov, Alexander A., E-mail: demkov@physics.utexas.edu [Department of Physics, University of Texas at Austin, Austin, Texas 78712 (United States); Ngo, Thong Q.; Ekerdt, John G. [Department of Chemical Engineering, University of Texas at Austin, Austin, Texas 78712 (United States); Lu, Sirong; Smith, David J.; McCartney, Martha R. [Department of Physics, Arizona State University, Tempe, Arizona 85287 (United States); Goble, Nicholas; Gao, Xuan P. A. [Department of Physics, Case Western Reserve University, Cleveland, Ohio 44106 (United States); Jordan-Sweet, Jean [IBM T.J. Watson Research Center, Yorktown Heights, New York 10598 (United States)

2015-03-07

In this paper, we report on the highly conductive layer formed at the crystalline γ-alumina/SrTiO{sub 3} interface, which is attributed to oxygen vacancies. We describe the structure of thin γ-alumina layers deposited by molecular beam epitaxy on SrTiO{sub 3} (001) at growth temperatures in the range of 400–800 °C, as determined by reflection-high-energy electron diffraction, x-ray diffraction, and high-resolution electron microscopy. In situ x-ray photoelectron spectroscopy was used to confirm the presence of the oxygen-deficient layer. Electrical characterization indicates sheet carrier densities of ∼10{sup 13 }cm{sup −2} at room temperature for the sample deposited at 700 °C, with a maximum electron Hall mobility of 3100 cm{sup 2}V{sup −1}s{sup −1} at 3.2 K and room temperature mobility of 22 cm{sup 2}V{sup −1}s{sup −1}. Annealing in oxygen is found to reduce the carrier density and turn a conductive sample into an insulator.

Luminescence properties of engineered nitrogen vacancy centers in a close surface proximity

Czech Academy of Sciences Publication Activity Database

Petráková, V.; Nesládek, M.; Taylor, Andrew; Fendrych, František; Cígler, Petr; Ledvina, Miroslav; Vacík, Jiří; Štursa, Jan; Kučka, Jan

2011-01-01

Roč. 208, č. 9 (2011), s. 2051-2056 ISSN 1862-6300 R&D Projects : GA AV ČR KAN200100801; GA AV ČR KAN301370701; GA AV ČR(CZ) KAN400480701; GA MŠk(CZ) LD11076 EU Projects : European Commission(XE) 245122 - DINAMO Grant - others:GA MŠk(CZ) LD11078; European RD projects (XE) 238201-MATCON Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z10100520; CEZ:AV0Z10480505 Keywords : diamond * luminescence properties * nitrogen-vacancy * surface proximity Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.463, year: 2011

Effect of low-damage inductively coupled plasma on shallow nitrogen-vacancy centers in diamond

Energy Technology Data Exchange (ETDEWEB)

Fávaro de Oliveira, Felipe; Momenzadeh, S. Ali; Wang, Ya; Denisenko, Andrej, E-mail: a.denisenko@physik.uni-stuttgart.de [3. Institute of Physics, Research Center SCoPE and IQST, University of Stuttgart, 70569 Stuttgart (Germany); Konuma, Mitsuharu [Max Planck Institute for Solid State Research, 70569 Stuttgart (Germany); Markham, Matthew; Edmonds, Andrew M. [Element Six Innovation, Harwell Oxford, Didcot, Oxfordshire OX11 0QR (United Kingdom); Wrachtrup, Jörg [3. Institute of Physics, Research Center SCoPE and IQST, University of Stuttgart, 70569 Stuttgart (Germany); Max Planck Institute for Solid State Research, 70569 Stuttgart (Germany)

2015-08-17

Near-surface nitrogen-vacancy (NV) centers in diamond have been successfully employed as atomic-sized magnetic field sensors for external spins over the last years. A key challenge is still to develop a method to bring NV centers at nanometer proximity to the diamond surface while preserving their optical and spin properties. To that aim we present a method of controlled diamond etching with nanometric precision using an oxygen inductively coupled plasma process. Importantly, no traces of plasma-induced damages to the etched surface could be detected by X-ray photoelectron spectroscopy and confocal photoluminescence microscopy techniques. In addition, by profiling the depth of NV centers created by 5.0 keV of nitrogen implantation energy, no plasma-induced quenching in their fluorescence could be observed. Moreover, the developed etching process allowed even the channeling tail in their depth distribution to be resolved. Furthermore, treating a {sup 12}C isotopically purified diamond revealed a threefold increase in T{sub 2} times for NV centers with <4 nm of depth (measured by nuclear magnetic resonance signal from protons at the diamond surface) in comparison to the initial oxygen-terminated surface.

Surface Characterization and Electrochemical Oxidation of Metal Doped Uranium Dioxide

Energy Technology Data Exchange (ETDEWEB)

Lee, Jeongmook; Kim, Jandee; Youn, Young-Sang; Kim, Jong-Goo; Ha, Yeong-Keong; Kim, Jong-Yun [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

2016-10-15

Trivalent element in UO{sub 2} matrix makes the oxygen vacancy from loss of oxygen for charge compensation. Tetravalent element alters lattice parameter of UO{sub 2} due to diameter difference between the tetravalent element and replaced U. These structural changes have significant effect on not only relevant fuel performance but also the kinetics of fuel oxidation. Park and Olander explained the stabilization of Ln (III)-doped UO{sub 2} against oxidation based on oxygen potential calculations. In this work, we have been investigated the effect of Gd{sup 3+} and Th{sup 4+} doping on the UO{sub 2} structure with Raman spectroscopy and X-ray diffraction to characterize the surface structure of nuclear fuel material. For Gd doped UO{sub 2}, its electrochemical oxidation behaviors are also investigated. The Gd and Th doped uranium dioxide solid solution pellets with various doping level were investigated by XRD, Raman spectroscopy, SEM, electrochemical experiments to investigate surface structure and electro chemical oxidation behaviors. The lattice parameter evaluated from XRD spectra indicated the formation of solid solutions. Raman spectra showed the existence of the oxygen vacancy. SEM images showed the grain structure on the surface of Gd doped uranium dioxide depending on doping level and oxygen-to-metal ratio.

Strain Relaxation and Vacancy Creation in Thin Platinum Films

International Nuclear Information System (INIS)

Gruber, W.; Chakravarty, S.; Schmidt, H.; Baehtz, C.; Leitenberger, W.; Bruns, M.; Kobler, A.; Kuebel, C.

2011-01-01

Synchrotron based combined in situ x-ray diffractometry and reflectometry is used to investigate the role of vacancies for the relaxation of residual stress in thin metallic Pt films. From the experimentally determined relative changes of the lattice parameter a and of the film thickness L the modification of vacancy concentration and residual strain was derived as a function of annealing time at 130 deg. C. The results indicate that relaxation of strain resulting from compressive stress is accompanied by the creation of vacancies at the free film surface. This proves experimentally the postulated dominant role of vacancies for stress relaxation in thin metal films close to room temperature.

An oxygen-vacancy-rich Z-scheme g-C3N4/Pd/TiO2 heterostructure for enhanced visible light photocatalytic performance

Science.gov (United States)

Guo, Yanru; Xiao, Limin; Zhang, Min; Li, Qiuye; Yang, Jianjun

2018-05-01

An oxygen-vacancy-rich Z-scheme g-C3N4/Pd/TiO2 ternary nanocomposite was fabricated using nanotubular titanic acid as precursors via a simple photo-deposition of Pd nanoparticles and calcination process. The prepared nanocomposites were investigated by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and UV-visible diffuse reflectance spectroscopy, respectively. For g-C3N4/TiO2 binary nanocomposites, at the optimal content of g-C3N4 (2%), the apparent photocatalytic activity of 2%g-C3N4/TiO2 was 9 times higher than that of pure TiO2 under visible-light illumination. After deposition of Pd (1 wt%) at the contact interface between g-C3N4 and TiO2, the 2%g-C3N4/Pd/TiO2 ternary nanocomposites demonstrated the highest visible-light-driven photocatalytic activity for the degradation of gaseous propylene, which was 16- and 2-fold higher activities than pure TiO2 and 2%g-C3N4/TiO2, respectively. The mechanism for the enhanced photocatalytic performance of the g-C3N4/Pd/TiO2 photo-catalyst is proposed to be based on the efficient separation of photo-generated electron-hole pairs through Z-scheme system, in which uniform dispersity of Pd nanoparticles at contact interface between g-C3N4 and TiO2 and oxygen vacancies promote charge separation.

Effect of oxygen vacancy and dopant concentration on the magnetic properties of high spin Co2+ doped TiO2 nanoparticles

International Nuclear Information System (INIS)

Choudhury, B.; Choudhury, A.; Maidul Islam, A.K.M.; Alagarsamy, P.; Mukherjee, M.

2011-01-01

Co doped TiO 2 nanoparticles have been synthesized by a simple sol-gel route taking 7.5, 9.5 and 10.5 mol% of cobalt concentration. Formation of nanoparticles is confirmed by XRD and TEM. Increase in d-spacing occurs for (0 0 4) and (2 0 0) peak with increase in impurity content. Valence states of Co and its presence in the doped material is confirmed by XPS and EDX. The entire vacuum annealed samples show weak ferromagnetism. Increased magnetization is found for 9.5 mol% but this value again decreases for 10.5 mol% due to antiferromagnetic interactions. A blocking temperature of 37.9 K is obtained, which shows shifting to high temperature as the dopant concentration is increased. The air annealed sample shows only paramagnetic behavior. Temperature dependent magnetic measurements for the air annealed sample shows antiferromagnetic behavior with a Curie-Weiss temperature of -16 K. Here we report that oxygen vacancy and cobalt aggregates are a key factor for inducing ferromagnetism-superparamagnetism in the vacuum annealed sample. Appearance of negative Curie-Weiss temperature reveals the presence of antiferromagnetic Co 3 O 4 , which is the oxidation result of metallic Co or cobalt clusters present on the host TiO 2 . - Research highlights: → Oxygen vacancy induces ferromagnetism in cobalt doped anatase TiO2 nanoparticles. → On air annealing the sample loses ferromagnetism giving rise to paramagnetism. → Saturation magnetization decreases at higher doping concentration. → Blocking of magnetic moment occurs due to the presence of cobalt clusters.

Mobility and stability of large vacancy and vacancy-copper clusters in iron: An atomistic kinetic Monte Carlo study

Energy Technology Data Exchange (ETDEWEB)

Castin, N., E-mail: ncastin@sckcen.be [Studiecentrum voor Kernenergie - Centre d' Etudes de l' energie Nucleaire (SCK-CEN), Nuclear Materials Science Institute, Unit Structural Materials Modelling and Microstructure-Boeretang 200, B2400 Mol (Belgium); Pascuet, M.I., E-mail: pascuet@cnea.gov.ar [Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET), Av. Rivadavia 1917, C1033AAJ Buenos Aires (Argentina); Malerba, L. [Studiecentrum voor Kernenergie - Centre d' Etudes de l' energie Nucleaire (SCK-CEN), Nuclear Materials Science Institute, Unit Structural Materials Modelling and Microstructure-Boeretang 200, B2400 Mol (Belgium)

2012-10-15

The formation of Cu-rich precipitates under irradiation is a major cause for changes in the mechanical response to load of reactor pressure vessel steels. In previous works, it has been shown that the mechanism under which precipitation occurs is governed by diffusion of vacancy-copper (VCu) complexes, also in the absence of irradiation. Coarse-grained computer models (such as object kinetic Monte Carlo) aimed at simulating irradiation processes in model alloys or steels should therefore explicitly include the mobility of Cu precipitates, as a consequence of vacancy hops at their surface. For this purpose, in this work we calculate diffusion coefficients and lifetimes for a large variety of VCu complexes. We use an innovative atomistic model, where vacancy migration energies are calculated with little approximations, taking into account all effects of static relaxation and long-range chemical interaction as predicted by an interatomic potential. Our results show that, contrary to what intuition might suggest, saturation in vacancies tend to slow down the transport of Cu atoms.

Mobility-electron density relation probed via controlled oxygen vacancy doping in epitaxial BaSnO3

Directory of Open Access Journals (Sweden)

Koustav Ganguly

2017-05-01

Full Text Available The recently discovered high room temperature mobility in wide band gap semiconducting BaSnO3 is of exceptional interest for perovskite oxide heterostructures. Critical open issues with epitaxial films include determination of the optimal dopant and understanding the mobility-electron density (μ-n relation. These are addressed here through a transport study of BaSnO3(001 films with oxygen vacancy doping controlled via variable temperature vacuum annealing. Room temperature n can be tuned from 5 × 1019 cm−3 to as low as 2 × 1017 cm−3, which is shown to drive a weak- to strong-localization transition, a 104-fold increase in resistivity, and a factor of 28 change in μ. The data reveal μ ∝ n0.65 scaling over the entire n range probed, important information for understanding mobility-limiting scattering mechanisms.

Simulation of vacancy migration energy in Cu under high strain

International Nuclear Information System (INIS)

Sato, K.; Yoshiie, T.; Satoh, Y.; Xu, Q.; Kiritani, M.

2003-01-01

The activation energy for the migration of vacancies in Cu under high strain was calculated by computer simulation using static methods. The migration energy of vacancies was 0.98 eV in the absence of deformation. It varied with the migration direction and stress direction because the distance between a vacancy and its neighboring atoms changes by deformation. For example, the migration energy for the shortest migration distance was reduced to 9.6 and 39.4% of its initial value by 10% compression and 20% elongation, respectively, while that for the longest migration distance was raised to 171.7 by 20% elongation. If many vacancies are created during high-speed deformation, the lowering of migration energy enables vacancies to escape to sinks such as surfaces, even during the shorter deformation period. The critical strain rate above which the strain rate dependence of vacancy accumulation ceases to exist increases with the lowering of vacancy migration energy

Positron annihilation study of vacancy-type defects in fast-neutron-irradiated MgO·nAl2O3

International Nuclear Information System (INIS)

Rahman, Abu Zayed Mohammad Saliqur; Li, Zhuoxin; Cao, Xingzhong; Wang, Baoyi; Wei, Long; Xu, Qiu; Atobe, Kozo

2014-01-01

Highlights: •Detection of Al monovacancy by positron lifetime spectroscopy in fast neutron-irradiated MgO·nAl 2 O 3 (n=2). •Concentration of defects is also estimated for Al monovacancy. •O atom peak was observed by using coincidence Doppler broadening spectroscopy. -- Abstract: The positron lifetimes of fast-neutron-irradiated MgO·nAl 2 O 3 single crystals were measured to investigate the formation of cation vacancies. Al monovacancy was possibly observed in samples irradiated by fast neutrons at ultra-low temperatures. Additionally, vacancy-oxygen complex centers were possibly observed in samples irradiated at higher temperatures and fast neutron fluences. Coincidence Doppler broadening (CDB) spectra were measured to obtain information regarding the vicinity of vacancy-type defects. A peak at approximately 11 × 10 −3 m 0 c was observed, which may be due to the presence of oxygen atoms in the neighborhood of the vacancies

Interaction of nitrogen with vacancy defects in N+-implanted ZnO studied using a slow positron beam

International Nuclear Information System (INIS)

Chen, Z.Q.; Maekawa, M.; Kawasuso, A.; Suzuki, R.; Ohdaira, T.

2005-01-01

ZnO crystals were implanted with N + , O + , and Al + , and co-implanted with O + /N + and Al + /N + ions. Positron annihilation measurements indicate introduction of vacancy clusters upon implantation. In the N + -implanted and Al + /N + co-implanted samples, these vacancy clusters are only partially annealed at 800 deg. C, as compared with their entire recovery in the O + - and Al + -implanted samples at 800-900 deg. C, suggesting a strong interaction between nitrogen and vacancy clusters. However, in the O + /N + co-implanted sample, most vacancy clusters disappear at 800 deg. C. Probably oxygen scavenges nitrogen to enhance the annealing of the vacancy clusters. Upon further annealing at 1000-1100 deg. C, nitrogen also forms stable complexes with thermally generated vacancies. These nitrogen-related vacancy complexes need high-temperature annealing at 1200-1250 deg. C to be fully removed

The influence of excess vacancy generation on the diffusion of ion implanted phosphorus into silicon

International Nuclear Information System (INIS)

Bakowski, A.

1985-01-01

The diffusion of ion implanted phosphorus in silicon has been studied. It was found that the diffusion coefficient is not only dependent on the phosphorus surface concentration (the concentration effect) but also on the conditions at the silicon surface (the surface effect). The phosphorus diffusion coefficient is considerably lower when the silicon surface during annealing is covered with a CVD oxide layer. It is suggested that excess vacancies generated at the surface are reponsible for both the concentration and surface effects. Enhanced phosphorus diffusion is attributed to the disturbance of thermodynamic equilibrium in the crystal through phosphorus-vacancy part formation by vacancies introduced into silicon at the surface. On the basis of the data presented, it can be concluded that two mechanisms for excess vacancy generation are involved. Assuming that phosphorus diffuses via E-centers, calculations of the concentration profiles and the diffusion coefficient were performed for different concentrations and surface conditions. (orig.)

Passivation of interstitial and vacancy mediated trap-states for efficient and stable triple-cation perovskite solar cells

Science.gov (United States)

Mahmud, Md Arafat; Elumalai, Naveen Kumar; Upama, Mushfika Baishakhi; Wang, Dian; Gonçales, Vinicius R.; Wright, Matthew; Xu, Cheng; Haque, Faiazul; Uddin, Ashraf

2018-04-01

The current work reports the concurrent passivation of interstitial and oxygen vacancy mediated defect states in low temperature processed ZnO electron transport layer (ETL) via Ultraviolet-Ozone (UVO) treatment for fabricating highly efficient (maximum efficiency: 16.70%), triple cation based MA0.57FA0.38Rb0.05PbI3 (MA: methyl ammonium, FA: formamidinium, Rb: rubidium) perovskite solar cell (PSC). Under UV exposure, ozone decomposes to free atomic oxygen and intercalates into the interstitial and oxygen vacancy induced defect sites in the ZnO lattice matrix, which contributes to suppressed trap-assisted recombination phenomena in perovskite device. UVO treatment also reduces the content of functional hydroxyl group on ZnO surface, that increases the inter-particle connectivity and grain size of perovskite film on UVO treated ZnO ETL. Owing to this, the perovskite film atop UVO treated ZnO film exhibits reduced micro-strain and dislocation density values, which contribute to the enhanced photovoltaic performance of PSC with modified ZnO ETL. The modified PSCs exhibit higher recombination resistance (RRec) ∼40% compared to pristine ZnO ETL based control devices. Adding to the merit, the UVO treated ZnO PSC also demonstrates superior device stability, retaining about 88% of its initial PCE in the course of a month-long, systematic degradation study.

Mechanism of formation of a zone without vacancy pores along a surface under electron irradiation of a metal in the high-volt electron microscope

International Nuclear Information System (INIS)

Golubov, S.I.; Konobeev, Yu.V.; Ryabov, V.A.

1981-01-01

Formation mechanism of zones free of vacancy pores near the vacant surface of a metal preliminary irradiated at a high neutron dose when irradiating with electrons in a high-voltage electron microscope has been suggested. It was assumed to explain experimentally observed values of width and time of such zone formation that interstitial atoms are reflected from foil surface while boundary serves as an ideal sink for the vacancies. The carried out calculation of stationary equations of vacancy and interstitial diffusion with the mentioned boundary condition has shown that determination of a stable zone width is possible only in assumption on a variable in a depth of dislocation density. Theoretical evaluations of a zone width being in good agreement with an experiment and with the results of numerical calculations have been obtained in negligence of recombination of point defects as well as for the case of total reflection of interstitials. Discussed are different mechanisms of weak capture of proper interstitial atoms diffusing to it with the metal surface [ru

Evaluation of the energetics of copper-vacancy clusters in Fe

Energy Technology Data Exchange (ETDEWEB)

Morishita, Kazunori, E-mail: morishita@iae.kyoto-u.ac.jp; Nakasuji, Toshiki; Ruan, Xiaoyong

2017-02-15

Highlights: • Thermodynamics evaluation of the nucleation process of copper-vacancy clusters in Fe is performed. • Nucleation free energy of copper-vacancy clusters in Fe is formulated. • With this energetics, two different nucleation paths of clusters are found as a function of the damage rate. - Abstract: A theoretical study is conducted to evaluate the nucleation free energy of copper-vacancy clusters in Fe as a function of the numbers of copper atoms and of vacancies in a cluster. Using this free energy value, cluster nucleation processes during irradiation are investigated. The results clearly show that there are two different types of cluster nucleation paths on the free energy surface; one is the formation of empty voids by jumping over the ridge of the free energy surface, and the other corresponds to a path for the formation of copper clusters by going around the ridge. The dependence of easy nucleation paths on the damage rate is discussed.

Effect of heat treatment on surface hydrophilicity-retaining ability of titanium dioxide nanotubes

Science.gov (United States)

Sun, Yu; Sun, Shupei; Liao, Xiaoming; Wen, Jiang; Yin, Guangfu; Pu, Ximing; Yao, Yadong; Huang, Zhongbing

2018-05-01

The aim of this study is to investigate the effect of different annealing temperature and atmosphere on the surface wettability retaining properties of titania nanotubes (TNs) fabricated by anodization. The TNs morphology, crystal phase composition and surface elemental composition and water contact angle (WCA) were investigated by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and contact angle instrument, respectively. After the samples annealed at 200 °C, 450 °C, 850 °C have been stored in air for 28 days, the WCAs increase to 31.7°, 21.1° and 110.5°, respectively. The results indicate that crystal phase composition of TNs plays an important role in surface wettability. Compared with the WCA (21.1°) of the samples annealed in air after 28 days, the WCA of samples annealed in oxygen-deficient atmosphere is lower, suggesting the contribution of oxygen vacancy in the enhanced hydrophilicity-retaining ability. Our study demonstrates that the surface hydrophilicity-retaining ability of TNs is related to the ordered nanotubular structure, crystal structure, the amount of surface hydroxyl group and oxygen vacancy defects.

Benign Synthesis of Black Microspheres of Anatase TiO2 with Paramagnetic Oxygen Vacancies through NH3 Treatment.

Science.gov (United States)

Maqbool, Qysar; Srivastava, Aasheesh

2017-10-09

Coloured TiO 2 is coveted for its ability to extract energy from the visible region of electromagnetic spectrum. Here a facile synthesis of black anatase titania microspheres (B-TiO 2 ) through a two-step process is reported. In the first step, amorphous white TiO 2 microspheres (W-TiO 2 ) are obtained by hydrolysing titanium tetraisopropoxide by ammonia vapours in ethanol. In the second step, the W-TiO 2 is thermally annealed at 500 °C to obtain B-TiO 2 . The diffuse reflectance analysis showed that B-TiO 2 absorbs across visible spectrum with absorption extending well into NIR region. Raman scattering together with EPR analysis showed compelling evidence of the existence of oxygen deficiency within the crystal in B-TiO 2 that induces black colouration in the sample. The defects present in the black anatase sample were confirmed to be single-electron-trapped (or paramagnetic) oxygen vacancies (V o ⋅) by XPS and EPR studies. The magnetic susceptibility studies showed existence of antiferromagnetic interactions between these unpaired electron spins. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen vacancies facilitate hydrogen transport kinetics in sodium hydride nanocrystallites

NARCIS (Netherlands)

Singh, S.; Eijt, S.W.H.

2008-01-01

We report ab initio calculations based on density-functional theory, of the vacancy-mediated hydrogen migration energy in bulk NaH and near the NaH(001) surface. The estimated rate of the vacancy mediated hydrogen transport, obtained within a hopping diffusion model, is consistent with the reaction

Enhanced diffusion of dopants in vacancy supersaturation produced by MeV implantation

International Nuclear Information System (INIS)

Venezia, V.C.; Univ. of North Texas, Denton, TX; Haynes, T.E.; Agarwal, A.; Lucent Technologies, Murray Hill, NJ; Gossmann, H.J.; Eaglesham, D.J.

1997-04-01

The diffusion of Sb and B markers has been studied in vacancy supersaturations produced by MeV Si implantation in float zone (FZ) silicon and bonded etch-back silicon-on-insulator (BESOI) substrates. MeV Si implantation produces a vacancy supersaturated near-surface region and an interstitial-rich region at the projected ion range. Transient enhanced diffusion (TED) of Sb in the near surface layer was observed as a result of a 2 MeV Si + , 1 x 10 16 /cm 2 , implant. A 4x larger TED of Sb was observed in BESOI than in FZ silicon, demonstrating that the vacancy supersaturation persists longer in BESOI than in FZ. B markers in samples with MeV Si implant showed a factor of 10x smaller diffusion relative to markers without the MeV Si + implant. This data demonstrates that a 2 MeV Si + implant injects vacancies into the near surface region

Sc and Nb Dopants in SrCoO3 Modulate Electronic and Vacancy Structures for Improved Water Splitting and SOFC Cathodes

KAUST Repository

Tahini, Hassan A.; Tan, Xin; Zhou, Wei; Zhu, Zhonghua; Schwingenschlö gl, Udo; Smith, Sean C.

2017-01-01

SrCoO3 is a promising material in the field of electrocatalysis. Difficulties in synthesising the material in its cubic phase have been overcome by doping it with Sc and Nb ions [Mater. Horiz.2015, 2, 495–501]. Using ab initio calculations and special quasi random structures we undertake a systematic study of these dopants in order to elucidate the effect of doping on electronic structure of the SrCoO3 host and the formation of oxygen vacancies. We find that while the overall electronic structure of SrCoO3 is preserved, increasing the Sc fraction leads to a decrease of electrical conductivity, in agreement with earlier experimental work. For low Sc and Nb doping fractions we find that the oxygen vacancy formation increases relative to undoped SrCoO3. However, as the dopants concentration is increased the vacancy formation energy drops significantly, indicating a strong tendency to accommodate high concentration of oxygen vacancies and hence non-stoichiometry. This is explained based on the electronic instabilities caused by the presence of Sc ions which weakens the B-O interactions as well as the increased degree of electron delocalization on the oxygen sublattice. Sc dopants also shift the p-band centre closer to the Fermi level, which can be associated with experimentally reported improvements in oxygen evolution reactions. These findings provide crucial baseline information for the design of better electrocatalysts for oxygen evolution reactions as well as fuel-cell cathode materials.

Sc and Nb Dopants in SrCoO3 Modulate Electronic and Vacancy Structures for Improved Water Splitting and SOFC Cathodes

KAUST Repository

Tahini, Hassan A.

2017-01-12

SrCoO3 is a promising material in the field of electrocatalysis. Difficulties in synthesising the material in its cubic phase have been overcome by doping it with Sc and Nb ions [Mater. Horiz.2015, 2, 495–501]. Using ab initio calculations and special quasi random structures we undertake a systematic study of these dopants in order to elucidate the effect of doping on electronic structure of the SrCoO3 host and the formation of oxygen vacancies. We find that while the overall electronic structure of SrCoO3 is preserved, increasing the Sc fraction leads to a decrease of electrical conductivity, in agreement with earlier experimental work. For low Sc and Nb doping fractions we find that the oxygen vacancy formation increases relative to undoped SrCoO3. However, as the dopants concentration is increased the vacancy formation energy drops significantly, indicating a strong tendency to accommodate high concentration of oxygen vacancies and hence non-stoichiometry. This is explained based on the electronic instabilities caused by the presence of Sc ions which weakens the B-O interactions as well as the increased degree of electron delocalization on the oxygen sublattice. Sc dopants also shift the p-band centre closer to the Fermi level, which can be associated with experimentally reported improvements in oxygen evolution reactions. These findings provide crucial baseline information for the design of better electrocatalysts for oxygen evolution reactions as well as fuel-cell cathode materials.

Study of the oxygen and substrate bias effects on the defect structure of reactive sputter-deposited SnOx films

International Nuclear Information System (INIS)

Misheva, M.; Nancheva, N.; Docheva, P.; Hadjijska, P.; Djourelov, N.; Elenkov, D.

1999-01-01

The effects of oxygen and substrate bias on the defect structure of reactive sputter-deposited SnOx films were investigated. Samples were analysed using transmission electron microscopy (TEM), transmission electron diffraction (TED), X-ray diffraction (XRD) and positron annihilation spectroscopy (PAS). The oxygen played an important role in the film growth and surface morphology. TEM, TED and XRD showed that increasing of the oxygen partial pressure leads to the formation of films with different crystal phases. The void sizes also depended on oxygen partial pressure. The positron lifetimes and their relative intensities depended on the void concentration, the partial annealing of the vacancies and oxidation of SnO to SnOx. This investigation also showed that the mechanical strength of the films obtained at negative substrate bias is higher and the concentration of vacancy defects is smaller, than in the films, prepared without substrate bias. (author)

Effect of oxygen vacancies on magnetic and transport properties of Sr2IrO4

Science.gov (United States)

Dwivedi, Vinod Kumar; Mukhopadhyay, Soumik

2018-05-01

Iridates have recently attracted growing interest because of their potential for realizing various interesting phases like interaction driven Mott-type insulator and magnetically driven Slater-type. In this paper, we present the magnetic and electrical transport properties of polycrystalline Sr2IrO4 synthesized by solid state reaction route. We find a ferromagnetic transition at 240 K. The Curie-Weiss law behavior hold good above the magnetic transition temperature TMag = 240 K with a small effective paramagnetic magnetic moment μeff = 0.25 µB/f.u. and a Curie-Weiss temperature, θCW = +100 K. Zero field cooled (ZFC) magnetization shows a gradual dcrease below 150 K, while same for field cooled (FC) below 50 K. Interestingly, below temperatures, ⁓ 10 K, a sharp increase in ZFC and FC magnetization can be seen. A temperature dependent resistivity reveals insulating behavior followed by power law mechanism. The sintering of sample in air leads to the very low value of resistivity is likely related to Sr or oxygen vacancies.

Electric-Field Control of Oxygen Vacancies and Magnetic Phase Transition in a Cobaltite/Manganite Bilayer

Science.gov (United States)

Cui, B.; Song, C.; Li, F.; Zhong, X. Y.; Wang, Z. C.; Werner, P.; Gu, Y. D.; Wu, H. Q.; Saleem, M. S.; Parkin, S. S. P.; Pan, F.

2017-10-01

Manipulation of oxygen vacancies (VO ) in single oxide layers by varying the electric field can result in significant modulation of the ground state. However, in many oxide multilayers with strong application potentials, e.g., ferroelectric tunnel junctions and solid-oxide fuel cells, understanding VO behavior in various layers under an applied electric field remains a challenge, owing to complex VO transport between different layers. By sweeping the external voltage, a reversible manipulation of VO and a corresponding fixed magnetic phase transition sequence in cobaltite/manganite (SrCoO3 -x/La0.45Sr0.55MnO3 -y ) heterostructures are reported. The magnetic phase transition sequence confirms that the priority of electric-field-induced VO formation or annihilation in the complex bilayer system is mainly determined by the VO formation energies and Gibbs free-energy differences, which is supported by theoretical analysis. We not only realize a reversible manipulation of the magnetic phase transition in an oxide bilayer but also provide insight into the electric-field control of VO engineering in heterostructures.

Electron diffraction study of the sillenites Bi12SiO20, Bi25FeO39 and Bi25InO39: Evidence of short-range ordering of oxygen-vacancies in the trivalent sillenites

Directory of Open Access Journals (Sweden)

Craig A. Scurti

2014-08-01

Full Text Available We present an electron diffraction study of three sillenites, Bi12SiO20, Bi25FeO39, and Bi25InO39 synthesized using the solid-state method. We explore a hypothesis, inspired by optical studies in the literature, that suggests that trivalent sillenites have additional disorder not present in the tetravalent compounds. Electron diffraction patterns of Bi25FeO39 and Bi25InO39 show streaks that confirm deviations from the ideal sillenite structure. Multi-slice simulations of electron-diffraction patterns are presented for different perturbations to the sillenite structure - partial substitution of the M site by Bi3+, random and ordered oxygen-vacancies, and a frozen-phonon model. Although comparison of experimental data to simulations cannot be conclusive, we consider the streaks as evidence of short-range ordered oxygen-vacancies.

Hexagonal perovskites with cationic vacancies. 29. Structure of Ba/sub 4/ScReWvacantO/sub 12/ - on the function of octahedral cationic vacancies in perovskite stacking polytypes

Energy Technology Data Exchange (ETDEWEB)

Kemmler-Sack, S; Herrmann, M [Tuebingen Univ. (Germany, F.R.). Lehrstuhl fuer Anorganische Chemie 2

1981-09-01

The hexagonal perovskite stacking polytype Ba/sub 4/ScReWvacantO/sub 12/ crystallizes in a rhombohedral 12 L structure (space group R-3m; sequence (hhcc)/sub 3/). The refined, intensity related R' value is 6.6%. The octahedral net consists of blocks of three face connected octahedra with a central vacancy, in the two outer positions the rhenium and tungsten atoms are located; these units are linked via common corners by single octahedra, occupied with scandium. The construction principles of hexagonal oxygen perovskites with octahedral, cationic vacancies are reported.

Characterization of oxygen vacancies and their migration in Ba-doped Pb(Zr0.52Ti0.48)O3 ferroelectrics

Science.gov (United States)

Zhang, M. F.; Wang, Y.; Wang, K. F.; Zhu, J. S.; Liu, J.-M.

2009-03-01

We investigate in detail the migration kinetics of oxygen vacancies (OVs) in Ba-doped Pb(Zr0.52Ti0.48)O3 (PZT) ferroelectrics by complex impedance spectroscopy. The temperature dependent dc-electrical conductivity σdc suggests that Ba doping into PZT can lower significantly the density of OVs, leading to the distinctly decreased σdc and slightly enhanced activation energy U for the migration of OVs, thus benefiting the polarization fatigue resistance. Furthermore, the polarization fluctuation induced by the relaxation of OVs is reduced by the Ba doping. The Cole-Cole fitting to the dielectric loss manifests strong correlation among OVs, and the migration of OVs appears to be a collective behavior.

A first-principles study of oxygen vacancy induced changes in structural, electronic and magnetic properties of La{sub 2/3}Sr{sub 1/3}MnO{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Li, Jia [Division of Materials Science, Nanyang Technological University, Singapore, 639798 (Singapore); Sun, Lizhong [Division of Materials Science, Nanyang Technological University, Singapore, 639798 (Singapore); Laboratory for Quantum Engineering and Micro-Nano Energy Technology, Xiangtan University, Xiangtan, Hunan, 411105 (China); Shenai, Prathamesh M.; Wang, Junling [Division of Materials Science, Nanyang Technological University, Singapore, 639798 (Singapore); Zheng, Hang [Department of Physics, Shanghai Jiao Tong University, 800 Dong Chuan Road, Shanghai, 200240 (China); Zhao, Yang, E-mail: YZhao@ntu.edu.sg [Division of Materials Science, Nanyang Technological University, Singapore, 639798 (Singapore)

2015-11-15

We have systematically assessed the influence of oxygen vacancy defects on the structural, electronic and magnetic properties of La{sub 2/3}Sr{sub 1/3}MnO{sub 3} via first-principles calculations using the bare GGA as well as the GGA + U formalism. The on-site Coulombic repulsion parameter U for Mn 3d orbital in the latter has been determined by the linear response theory. It is revealed that the introduction of the vacancy defects causes prominent structural changes in the microenvironment of a defect including the distortions of MnO{sub 6} octahedra. In contrast to the general notion, the GGA + U formalism is found to yield significantly more prominent structural changes than the bare GGA method. The octahedral distortion leads to a strengthening or weakening of the hybridization between Mn 3d and O 2p orbitals depending upon an increase or decrease, respectively, in the Mn–O distances as compared to the pristine system. The magnetic moments of the Mn atoms located in three typical sites of the vacancy-containing supercell are all larger than those in the pristine system. This enhancement for the Mn atoms located in the first- and third-nearest neighboring MnO{sub 6} octahedra of the vacancy defect originates from the electron transfer from 4s/3p to 3d orbitals. On the other hand, for the Mn atom located in the first-nearest neighboring site of the vacancy it is attributed to the increased total number of electrons in 3d orbitals due to the absence of one Mn–O bond. Furthermore, we have characterized the O-vacancy defect as a hole-type defect that forms a negative charge center, attracting electrons. - Highlights: • GGA + U calculations reveal effect of O-vacancy on properties of La{sub 1−1/3}Sr{sub 1/3}MnO{sub 3.} • Value of U = 5.9 eV calculated for Mn 3d orbitals from the linear response theory. • O-vacancy causes prominent distortions of MnO{sub 6} octahedra. • Octahedral distortions modulate electronic and magnetic properties of LSMO. �

Giant thermally-enhanced electrostriction and polar surface phase in L a2M o2O9 oxygen ion conductors

Science.gov (United States)

Li, Qian; Lu, Teng; Schiemer, Jason; Laanait, Nouamane; Balke, Nina; Zhang, Zhan; Ren, Yang; Carpenter, Michael A.; Wen, Haidan; Li, Jiangyu; Kalinin, Sergei V.; Liu, Yun

2018-04-01

Ferroelectrics possess spontaneous electric polarization at macroscopic scales which nonetheless imposes strict limitations on the material classes. Recent discoveries of untraditional symmetry-breaking phenomena in reduced material dimensions have indicated feasibilities to extend polar properties to broader types of materials, potentially opening up the freedom for designing materials with hybrid functionalities. Here, we report the unusual electromechanical properties of L a2M o2O9 (LAMOX) oxygen ion conductors, systematically investigated at both bulk and surface length levels. We first observed giant electrostriction effects in L a2M o2O9 bulk ceramics that are thermally enhanced in concert with their low-energy oxygen-vacancy hopping dynamics. Moreover, while no clear bulk polarization was detected, the surface phases of LAMOX were found to be manifestly polar, likely originating from the coupling between the intrinsic structural flexibilities with strain gradients (i.e., flexoelectricity) and/or chemical heterogeneities present in the materials. These findings identify L a2M o2O9 as a promising electromechanical material system and suggest that the flexible structural and chemical configurations in ionically active materials could enable fundamentally different venues to accommodate electric polarization.

Late Archean Surface Ocean Oxygenation (Invited)

Science.gov (United States)

Kendall, B.; Reinhard, C.; Lyons, T. W.; Kaufman, A. J.; Anbar, A. D.

2009-12-01

Oxygenic photosynthesis must have evolved by 2.45-2.32 Ga, when atmospheric oxygen abundances first rose above 0.001% present atmospheric level (Great Oxidation Event; GOE). Biomarker evidence for a time lag between the evolution of cyanobacterial oxygenic photosynthesis and the GOE continues to be debated. Geochemical signatures from sedimentary rocks (redox-sensitive trace metal abundances, sedimentary Fe geochemistry, and S isotopes) represent an alternative tool for tracing the history of Earth surface oxygenation. Integrated high-resolution chemostratigraphic profiles through the 2.5 Ga Mt. McRae Shale (Pilbara Craton, Western Australia) suggest a ‘whiff’ of oxygen in the surface environment at least 50 M.y. prior to the GOE. However, the geochemical data from the Mt. McRae Shale does not uniquely constrain the presence or extent of Late Archean ocean oxygenation. Here, we present high-resolution chemostratigraphic profiles from 2.6-2.5 Ga black shales (upper Campbellrand Subgroup, Kaapvaal Craton, South Africa) that provide the earliest direct evidence for an oxygenated ocean water column. On the slope beneath the Campbellrand - Malmani carbonate platform (Nauga Formation), a mildly oxygenated water column (highly reactive iron to total iron ratios [FeHR/FeT] ≤ 0.4) was underlain by oxidizing sediments (low Re and Mo abundances) or mildly reducing sediments (high Re but low Mo abundances). After drowning of the carbonate platform (Klein Naute Formation), the local bottom waters became anoxic (FeHR/FeT > 0.4) and intermittently sulphidic (pyrite iron to highly reactive iron ratios [FePY/FeHR] > 0.8), conducive to enrichment of both Re and Mo in sediments, followed by anoxic and Fe2+-rich (ferruginous) conditions (high FeT, FePY/FeHR near 0). Widespread surface ocean oxygenation is suggested by Re enrichment in the broadly correlative Klein Naute Formation and Mt. McRae Shale, deposited ~1000 km apart in the Griqualand West and Hamersley basins

Surface interaction of polyimide with oxygen ECR plasma

International Nuclear Information System (INIS)

Naddaf, M.; Balasubramanian, C.; Alegaonkar, P.S.; Bhoraskar, V.N.; Mandle, A.B.; Ganeshan, V.; Bhoraskar, S.V.

2004-01-01

Polyimide (Kapton-H), was subjected to atomic oxygen from an electron cyclotron resonance plasma. An optical emission spectrometer was used to characterize the atomic oxygen produced in the reactor chamber. The energy of the ions was measured using a retarding field analyzer, placed near the substrate. The density of atomic oxygen in the plasma was estimated using a nickel catalytic probe. The surface wettability of the polyimide samples monitored by contact angle measurements showed considerable improvement when treated with plasma. X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopic studies showed that the atomic oxygen in the plasma is the main specie affecting the surface chemistry and adhesion properties of polyimide. The improvement in the surface wettability is attributed to the high degree of cross-linking and large concentration of polar groups generated in the surface region of polyimide, after plasma treatment. The changes in the surface region of polyimide were observed by atomic force microscopic analysis

Surface interaction of polyimide with oxygen ECR plasma

Science.gov (United States)

Naddaf, M.; Balasubramanian, C.; Alegaonkar, P. S.; Bhoraskar, V. N.; Mandle, A. B.; Ganeshan, V.; Bhoraskar, S. V.

2004-07-01

Polyimide (Kapton-H), was subjected to atomic oxygen from an electron cyclotron resonance plasma. An optical emission spectrometer was used to characterize the atomic oxygen produced in the reactor chamber. The energy of the ions was measured using a retarding field analyzer, placed near the substrate. The density of atomic oxygen in the plasma was estimated using a nickel catalytic probe. The surface wettability of the polyimide samples monitored by contact angle measurements showed considerable improvement when treated with plasma. X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopic studies showed that the atomic oxygen in the plasma is the main specie affecting the surface chemistry and adhesion properties of polyimide. The improvement in the surface wettability is attributed to the high degree of cross-linking and large concentration of polar groups generated in the surface region of polyimide, after plasma treatment. The changes in the surface region of polyimide were observed by atomic force microscopic analysis.

Surface Segregation in YSZ

DEFF Research Database (Denmark)

Bay, Lasse; Zachau-Christiansen, Birgit; Jacobsen, Torben

1998-01-01

The space charge layer formed due to segregation of yttria and oxygen ion vacancies in YSZ is described by a simple model. Effects of impurities segregation are omitted.......The space charge layer formed due to segregation of yttria and oxygen ion vacancies in YSZ is described by a simple model. Effects of impurities segregation are omitted....

Effects of recoil-implanted oxygen on depth profiles of defects and annealing processes in P{sup +}-implanted Si studied using monoenergetic positron beams

Energy Technology Data Exchange (ETDEWEB)

Uedono, Akira; Moriya, Tsuyoshi; Tanigawa, Shoichiro [Tsukuba Univ., Ibaraki (Japan). Inst. of Materials Science; Kitano, Tomohisa; Watanabe, Masahito; Kawano, Takao; Suzuki, Ryoichi; Ohdaira, Toshiyuki; Mikado, Tomohisa

1996-04-01

Effects of oxygen atoms recoiled from SiO{sub 2} films on depth profiles of defects and annealing processes in P{sup +}-implanted Si were studied using monoenergetic positron beams. For an epitaxial Si specimen, the depth profile of defects was found to be shifted toward the surface by recoil implantation of oxygen atoms. This was attributed to the formation of vacancy-oxygen complexes and a resultant decrease in the diffusion length of vacancy-type defects. The recoiled oxygen atoms stabilized amorphous regions introduced by P{sup +}-implantation, and the annealing of these regions was observed after rapid thermal annealing (RTA) at 700degC. For a Czochralski-grown Si specimen fabricated by through-oxide implantation, the recoiled oxygen atoms introduced interstitial-type defects upon RTA below the SiO{sub 2}/Si interface, and such defects were dissociated by annealing at 1000degC. (author)

Dislocation behavior of surface-oxygen-concentration controlled Si wafers

International Nuclear Information System (INIS)

Asazu, Hirotada; Takeuchi, Shotaro; Sannai, Hiroya; Sudo, Haruo; Araki, Koji; Nakamura, Yoshiaki; Izunome, Koji; Sakai, Akira

2014-01-01

We have investigated dislocation behavior in the surface area of surface-oxygen-concentration controlled Si wafers treated by a high temperature rapid thermal oxidation (HT-RTO). The HT-RTO process allows us to precisely control the interstitial oxygen concentration ([O i ]) in the surface area of the Si wafers. Sizes of rosette patterns, generated by nano-indentation and subsequent thermal annealing at 900 °C for 1 h, were measured for the Si wafers with various [O i ]. It was found that the rosette size decreases in proportion to the − 0.25 power of [O i ] in the surface area of the Si wafers, which were higher than [O i ] of 1 × 10 17 atoms/cm 3 . On the other hand, [O i ] of lower than 1 × 10 17 atoms/cm 3 did not affect the rosette size very much. These experimental results demonstrate the ability of the HT-RTO process to suppress the dislocation movements in the surface area of the Si wafer. - Highlights: • Surface-oxygen-concentration controlled Si wafers have been made. • The oxygen concentration was controlled by high temperature rapid thermal oxidation. • Dislocation behavior in the surface area of the Si wafers has been investigated. • Rosette size decreased with increasing of interstitial oxygen atoms. • The interstitial oxygen atoms have a pinning effect of dislocations at the surface

Fabrication and characterization of cubic Ba{sub 0.5}Sr{sub 0.5}Co{sub 0.8}Fe{sub 0.2}O{sub 3−δ} perovskite for a novel “star-shaped” oxygen membrane with a developed surface

Energy Technology Data Exchange (ETDEWEB)

Borhan, Adrian Iulian [Institute of Power Engineering, Ceramic Department CEREL, Research Institute, 1 Techniczna St., 36-040 Boguchwała (Poland); Gromada, Magdalena, E-mail: gromada@cerel.pl [Institute of Power Engineering, Ceramic Department CEREL, Research Institute, 1 Techniczna St., 36-040 Boguchwała (Poland); Samoila, Petrisor [Petru Poni Institute of Macromolecular Chemistry, 41A, Gr. Ghica Voda Alley, 700487 Iasi (Romania); Gherca, Daniel [Alexandru Ioan Cuza University of Iasi, Faculty of Chemistry, 11 Carol 1 Boulevard, R-700506 Iasi (Romania)

2016-07-15

Highlights: • Innovative fabrication technology was elaborated for BSCF membrane with developed surface. • The tool for membranes forming with developed surface was designed and executed. • As a result of forming process, membranes with “star shape” design were obtained. • Concentration of oxygen vacancies in BSCF increases considerably with temperature. • The small polaron hopping depends on the oxygen stoichiometry deviation. - Abstract: Ba{sub 0.5}Sr{sub 0.5}Co{sub 0.8}Fe{sub 0.2}O{sub 3−δ} (BSCF), a material which can be used for the fabrication of oxygen membranes with developed surfaces, was synthesized by a solid state method. The most important material properties which have influence on the oxygen membrane usability were investigated. An innovative fabrication technology was developed for the preparation of oxygen membranes with developed surfaces by using vacuum extrusion. The tool to form membranes on a vacuum worm press was designed and executed. These allowed the formation, for the first time, of a novel “star shaped” architecture for an oxygen membrane, enabling the use of a higher effective surface for oxygen production. Comprehensive studies on structural and microstructural properties, apparent density and porosity, water absorbability, oxygen stoichiometry, thermal expansion and electrical conductivity of the BSCF membrane were performed. The results obtained demonstrated the potential application of “star-shaped” oxygen membranes in oxy-fuel combustion technology.

Physical properties and band structure of reactive molecular beam epitaxy grown oxygen engineered HfO{sub 2{+-}x}

Energy Technology Data Exchange (ETDEWEB)

Hildebrandt, Erwin; Kurian, Jose; Alff, Lambert [Institute of Materials Science, Technische Universitaet Darmstadt, 64287 Darmstadt (Germany)

2012-12-01

We have conducted a detailed thin film growth structure of oxygen engineered monoclinic HfO{sub 2{+-}x} grown by reactive molecular beam epitaxy. The oxidation conditions induce a switching between (111) and (002) texture of hafnium oxide. The band gap of oxygen deficient hafnia decreases with increasing amount of oxygen vacancies by more than 1 eV. For high oxygen vacancy concentrations, defect bands form inside the band gap that induce optical transitions and p-type conductivity. The resistivity changes by several orders of magnitude as a function of oxidation conditions. Oxygen vacancies do not give rise to ferromagnetic behavior.

High-throughput DFT calculations of formation energy, stability and oxygen vacancy formation energy of ABO3 perovskites

Science.gov (United States)

Emery, Antoine A.; Wolverton, Chris

2017-10-01

ABO3 perovskites are oxide materials that are used for a variety of applications such as solid oxide fuel cells, piezo-, ferro-electricity and water splitting. Due to their remarkable stability with respect to cation substitution, new compounds for such applications potentially await discovery. In this work, we present an exhaustive dataset of formation energies of 5,329 cubic and distorted perovskites that were calculated using first-principles density functional theory. In addition to formation energies, several additional properties such as oxidation states, band gap, oxygen vacancy formation energy, and thermodynamic stability with respect to all phases in the Open Quantum Materials Database are also made publicly available. This large dataset for this ubiquitous crystal structure type contains 395 perovskites that are predicted to be thermodynamically stable, of which many have not yet been experimentally reported, and therefore represent theoretical predictions. The dataset thus opens avenues for future use, including materials discovery in many research-active areas.

Positron annihilation study of vacancy-type defects in fast-neutron-irradiated MgO·nAl{sub 2}O{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Rahman, Abu Zayed Mohammad Saliqur, E-mail: zayed82000@yahoo.com [Key Laboratory of Nuclear Analytical Techniques, Institute of High Energy Physics, Chinese Academy of Sciences, 19B Yuquanlu Shijingshan District, Beijing 100049 (China); Li, Zhuoxin; Cao, Xingzhong; Wang, Baoyi; Wei, Long [Key Laboratory of Nuclear Analytical Techniques, Institute of High Energy Physics, Chinese Academy of Sciences, 19B Yuquanlu Shijingshan District, Beijing 100049 (China); Xu, Qiu [Reactor Research Institute, Kyoto University 2, Asashiro-Nishi, Kumatori-cho, Sennan-gun, Osaka 590-0494 (Japan); Atobe, Kozo [Nuclear Safety Technology Center, 9-15, 1-chome, Utsubohonmachi, Nishi Ku, Osaka 550-0004 (Japan)

2014-09-15

Highlights: •Detection of Al monovacancy by positron lifetime spectroscopy in fast neutron-irradiated MgO·nAl{sub 2}O{sub 3}(n=2). •Concentration of defects is also estimated for Al monovacancy. •O atom peak was observed by using coincidence Doppler broadening spectroscopy. -- Abstract: The positron lifetimes of fast-neutron-irradiated MgO·nAl{sub 2}O{sub 3} single crystals were measured to investigate the formation of cation vacancies. Al monovacancy was possibly observed in samples irradiated by fast neutrons at ultra-low temperatures. Additionally, vacancy-oxygen complex centers were possibly observed in samples irradiated at higher temperatures and fast neutron fluences. Coincidence Doppler broadening (CDB) spectra were measured to obtain information regarding the vicinity of vacancy-type defects. A peak at approximately 11 × 10{sup −3} m{sub 0}c was observed, which may be due to the presence of oxygen atoms in the neighborhood of the vacancies.

Oxygen Transport Membranes

Energy Technology Data Exchange (ETDEWEB)

S. Bandopadhyay

2008-08-30

small polaron conduction mechanism. Scanning transmission electron microscopy (STEM) and electron energy loss spectroscopy (EELS) were used to develop strategies to detect and characterize vacancy creation, dopant segregations and defect association in the oxygen conducting membrane material. The pO{sub 2} and temperature dependence of the conductivity, non-stoichiometry and thermal-expansion behavior of compositions with increasing complexity of substitution on the perovskite A and B sites were studied. Studies with the perovskite structure show anomalous behavior at low oxygen partial pressures (<10{sup -5} atm). The anomalies are due to non-equilibrium effects and can be avoided by using very strict criteria for the attainment of equilibrium. The slowness of the oxygen equilibration kinetics arises from two different mechanisms. In the first, a two phase region occurs between an oxygen vacancy ordered phase such as brownmillerite SrFeO{sub 2.5} and perovskite SrFeO{sub 3-x}. The slow kinetics is associated with crossing the two phase region. The width of the miscibility gap decreases with increasing temperature and consequently the effect is less pronounced at higher temperature. The preferred kinetic pathway to reduction of perovskite ferrites when the vacancy concentration corresponds to the formation of significant concentrations of Fe{sup 2+} is via the formation of a Ruddlesden-Popper (RP) phases as clearly observed in the case of La{sub 0.5}Sr{sub 0.5}FeO{sub 3-x} where LaSrFeO{sub 4} is found together with Fe. In more complex compositions, such as LSFTO, iron or iron rich phases are observed locally with no evidence for the presence of discrete RP phase. Fracture strength of tubular perovskite membranes was determined in air and in reducing atmospheric conditions. The strength of the membrane decreased with temperature and severity of reducing conditions although the strength distribution (Weibull parameter, m) was relatively unaltered. Surface and volume

Charge Dynamics in near-Surface, Variable-Density Ensembles of Nitrogen-Vacancy Centers in Diamond.

Science.gov (United States)

Dhomkar, Siddharth; Jayakumar, Harishankar; Zangara, Pablo R; Meriles, Carlos A

2018-06-13

Although the spin properties of superficial shallow nitrogen-vacancy (NV) centers have been the subject of extensive scrutiny, considerably less attention has been devoted to studying the dynamics of NV charge conversion near the diamond surface. Using multicolor confocal microscopy, here we show that near-surface point defects arising from high-density ion implantation dramatically increase the ionization and recombination rates of shallow NVs compared to those in bulk diamond. Further, we find that these rates grow linearly, not quadratically, with laser intensity, indicative of single-photon processes enabled by NV state mixing with other defect states. Accompanying these findings, we observe NV ionization and recombination in the dark, likely the result of charge transfer to neighboring traps. Despite the altered charge dynamics, we show that one can imprint rewritable, long-lasting patterns of charged-initialized, near-surface NVs over large areas, an ability that could be exploited for electrochemical biosensing or to optically store digital data sets with subdiffraction resolution.

Surface acoustic wave oxygen pressure sensor

Science.gov (United States)

Oglesby, Donald M. (Inventor); Upchurch, Billy T. (Inventor); Leighty, Bradley D. (Inventor)

1994-01-01

A transducer for the measurement of absolute gas-state oxygen pressure from pressures of less than 100 Pa to atmospheric pressure (1.01 x 10(exp 5) Pa) is based on a standard surface acoustic wave (SAW) device. The piezoelectric material of the SAW device is coated with a compound which will selectively and reversibly bind oxygen. When oxygen is bound by the coating, the mass of the coating increases by an amount equal to the mass of the bound oxygen. Such an increase in the mass of the coating causes a corresponding decrease in the resonant frequency of the SAW device.

Nature of oxygen donors and radiation defects in oxygen-doped germanium

International Nuclear Information System (INIS)

Fukuoka, Noboru; Atobe, Kozo; Honda, Makoto; Matsuda, Koji.

1991-01-01

The nature of oxygen donors and radiation defects in oxygen-doped germanium were studied through measurements of the infrared absorption spectrum, deep level transient spectroscopy spectrum and carrier concentration. It is revealed that a new donor is not formed in oxygen-doped germanium. An A-center (interstitial oxygen-vacancy pair) forms a complex with a thermal donor in its annealing stage at 60degC-140degC. The introduction rate of defects by 1.5 MeV electron irradiation was enhanced in thermal-donor-doped samples. (author)

Study on the surface electronic properties of Li-containing solids

Energy Technology Data Exchange (ETDEWEB)

Matsuura, Fumio; Suzuki, Atsushi; Yamaguchi, Kenji; Yamawaki, M [Tokyo Univ. (Japan)

1998-03-01

The electronic state of Li{sub 2}O surface will be modified by absorption and/or desorption of chemically-active species, such as H{sub 2} and H{sub 2}O. The reactions induced by these species will involve some point defects in the solid. Whereas the high temperature Kelvin probe has proven to be quite effective in obtaining information on the surface reactions between gas and solid, an attempt is being made to incorporate numerical calculation to obtain further information which may not be easily done by experiments. The code employed in the present study is `CRYSTAL`, which employs a self-consistent-field Hartree-Fock method. As a preliminary study, we tried to calculate the change of Fermi Energy as a function of the density of oxygen vacancy. The results revealed that the greater the density of oxygen vacancy, the larger the Fermi Energy of Li{sub 2}O, which was consistent with the experimental results obtained by high temperature Kelvin probe. (author)

Controlling electron transfer processes on insulating surfaces with the non-contact atomic force microscope.

Science.gov (United States)

Trevethan, Thomas; Shluger, Alexander

2009-07-01

We present the results of theoretical modelling that predicts how a process of transfer of single electrons between two defects on an insulating surface can be induced using a scanning force microscope tip. A model but realistic system is employed which consists of a neutral oxygen vacancy and a noble metal (Pt or Pd) adatom on the MgO(001) surface. We show that the ionization potential of the vacancy and the electron affinity of the metal adatom can be significantly modified by the electric field produced by an ionic tip apex at close approach to the surface. The relative energies of the two states are also a function of the separation of the two defects. Therefore the transfer of an electron from the vacancy to the metal adatom can be induced either by the field effect of the tip or by manipulating the position of the metal adatom on the surface.

Hydrogen Adsorption on Ga2O3 Surface: A Combined Experimental and Computational Study

Energy Technology Data Exchange (ETDEWEB)

Pan, Yun-xiang; Mei, Donghai; Liu, Chang-jun; Ge, Qingfeng

2011-05-03

In the present work, hydrogen adsorption on the Ga2O3 surfaces was investigated using Fourier transform infrared spectroscopy (FTIR) measurements and periodic density functional theory (DFT) calculations. Both the FTIR and DFT studies suggest that H2 dissociates on the Ga2O3 surfaces, producing OH and GaH species. The FTIR bands at 3730, 3700, 3630 and 3600 cm-1 are attributed to the vibration of the OH species whereas those at 2070 and 1990 cm-1 to the GaH species. The structures of the species detected in experiments are established through a comparison with the DFT calculated stretching frequencies. The O atom of the experimentally detected OH species is believed to originate from the surface O3c atom. On the other hand, the H atom that binds the coordinately unsaturated Ga atom results in the experimentally detected GaH species. Dissociation of H2 on the perfect Ga2O3 surface, with the formation of both OH and GaH species, is endothermic and has an energy barrier of 0.90 eV. In contrast, H2 dissociation on the defective Ga2O3 surface with oxygen vacancies, which mainly produces GaH species, is exothermic, with an energy barrier of 0.61 eV. Accordingly, presence of the oxygen vacancies promotes H2 dissociation and production of GaH species on the Ga2O3 surfaces. Higher temperatures are expected to favor oxygen vacancy creation on the Ga2O3 surfaces, and thereby benefit the production of GaH species. This analysis is consistent with the FTIR results that the bands assigned to GaH species become stronger at higher temperatures. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

Role of CO2 in the oxy-dehydrogenation of ethylbenzene to styrene on the CeO2(111) surface

Science.gov (United States)

Fan, Hong-Xia; Feng, Jie; Li, Wen-Ying; Li, Xiao-Hong; Wiltowski, Tomasz; Ge, Qing-Feng

2018-01-01

The role of CO2 in the ethylbenzene oxy-dehydrogenation to styrene on the CeO2(111) surface was thoroughly investigated by the density functional theory (DFT) calculations. Results show that the first Csbnd H bond of ethylbenzene is activated via the oxo-insertion with a barrier of 1.70 eV, resulting in a 2-phenylethyl species and an H atom adsorbed on two-adjacent-lattice oxygen. The H adatom forms a hydroxyl-like species (denoted as O*H). The subsequent dehydrogenation to styrene can be assisted by either the next lattice oxygen (pathway R1) or the O*H species (pathway R2). The two pathways have almost the same activation energy (0.84 eV for R1 and 0.85 eV for R2), forming a new O*H and desorbing a H2O molecule while leaving an oxygen vacancy on the surface, respectively. In the presence of CO2, it will react with O*H through the reverse water gas shift reaction with an activation barrier of 0.98 eV and reaction energy of 0.30 eV. The reverse water gas shift reaction helps to clear the H adatoms from the lattice oxygen, thereby competing with styrene formation via pathway R2. However, the activation energy following the reverse water gas shift mechanism is 0.13 eV higher than that of styrene formation via pathway R2. Therefore, the formation of oxygen vacancy cannot be inhibited, while CO2 can react with the surface oxygen vacancy to produce CO with a high activation energy of 2.10 eV.

Tuning the electronic structure of SrTiO3/SrFeO3−x superlattices via composition and vacancy control

Directory of Open Access Journals (Sweden)

Robert F. Berger

2014-04-01

Full Text Available Using density functional theory-based calculations, we explore the effects of oxygen vacancies and epitaxial layering on the atomic, magnetic, and electronic structure of (SrTiO3n(SrFeO3−x1 superlattices. While structures without oxygen vacancies (x = 0 possess small or non-existent band gaps and ferromagnetic ordering in their iron layers, those with large vacancy concentrations (x = 0.5 have much larger gaps and antiferromagnetic ordering. Though the computed gaps depend numerically on the delicate energetic balance of vacancy ordering and on the value of Hubbard U eff used in the calculations, we demonstrate that changes in layering can tune the band gaps of these superlattices below that of SrTiO3 (3.2 eV by raising their valence band maxima. This suggests the possibility that these superlattices could absorb in the solar spectrum, and could serve as water-splitting photocatalysts.

Impact of Surface Functionalization on the Quantum Coherence of Nitrogen-Vacancy Centers in Nanodiamonds.

Science.gov (United States)

Ryan, Robert G; Stacey, Alastair; O'Donnell, Kane M; Ohshima, Takeshi; Johnson, Brett C; Hollenberg, Lloyd C L; Mulvaney, Paul; Simpson, David A

2018-04-18

Nanoscale quantum probes such as the nitrogen-vacancy (NV) center in diamonds have demonstrated remarkable sensing capabilities over the past decade as control over fabrication and manipulation of these systems has evolved. The biocompatibility and rich surface chemistry of diamonds has added to the utility of these probes but, as the size of these nanoscale systems is reduced, the surface chemistry of diamond begins to impact the quantum properties of the NV center. In this work, we systematically study the effect of the diamond surface chemistry on the quantum coherence of the NV center in nanodiamonds (NDs) 50 nm in size. Our results show that a borane-reduced diamond surface can on average double the spin relaxation time of individual NV centers in nanodiamonds when compared to thermally oxidized surfaces. Using a combination of infrared and X-ray absorption spectroscopy techniques, we correlate the changes in quantum relaxation rates with the conversion of sp 2 carbon to C-O and C-H bonds on the diamond surface. These findings implicate double-bonded carbon species as a dominant source of spin noise for near surface NV centers. The link between the surface chemistry and quantum coherence indicates that through tailored engineering of the surface, the quantum properties and magnetic sensitivity of these nanoscale systems may approach that observed in bulk diamond.

Synergistic effect of single-electron-trapped oxygen vacancies and carbon species on the visible light photocatalytic activity of carbon-modified TiO2

International Nuclear Information System (INIS)

Wang, Xiaodong; Xue, Xiaoxiao; Liu, Xiaogang; Xing, Xing; Li, Qiuye; Yang, Jianjun

2015-01-01

Carbon-modified TiO 2 (CT) nanoparticles were prepared via a two-step method of heat treatment without the resorcinol-formaldehyde (RF) polymer. As-prepared CT nanoparticles were characterized by means of X-ray diffraction (XRD), UV–Vis diffuse reflectance spectroscopy (UV–Vis/DRS), transmission electron microscopy (TEM), N 2 adsorption–desorption isotherms, thermal analysis (TA), electron spin resonance (ESR), and X-ray photoelectron spectroscopy (XPS). The visible light photocatalytic activities were evaluated on the basis of the degradation of methyl orange (MO). The synergistic effect of single-electron-trapped oxygen vacancies (SETOVs) and the carbon species on the visible light photocatalytic activities of the CT nanoparticles were discussed. It was found that the crystalline phase, the morphology, and particle size of the CT nanoparticles depended on the second heat-treatment temperature instead of the first heat-treatment temperature. The visible light photocatalytic activities were attributed to the synergistic effect of SETOVs and the carbon species, and also depended on the specific surface area of the photocatalysts. - Highlights: • Carbon-modified TiO 2 particles have been prepared without RF polymer. • The visible light photocatalytic activities of the particles have been evaluated. • The band gap energy structure of the carbon-modified TiO 2 has been proposed. • Synergistic effect of SETOVs and carbon species has been discussed. • The activities also depend on the specific surface area of the catalysts

Role of oxygen defects on the magnetic properties of ultra-small Sn1-xFexO2 nanoparticles

Science.gov (United States)

Dodge, Kelsey; Chess, Jordan; Eixenberger, Josh; Alanko, Gordon; Hanna, Charles B.; Punnoose, Alex

2013-05-01

Although the role of oxygen defects in the magnetism of metal oxide semiconductors has been widely discussed, it is been difficult to directly measure the oxygen defect concentration of samples to verify this. This work demonstrates a direct correlation between the photocatalytic activity of Sn1-xFexO2 nanoparticles and their magnetic properties. For this, a series of ˜2.6 nm sized, well characterized, single-phase Sn1-xFexO2 crystallites with x = 0-0.20 were synthesized using tin acetate, urea, and appropriate amounts of iron acetate. X-ray photoelectron spectroscopy confirmed the concentration and 3+ oxidation state of the doped Fe ions. The maximum magnetic moment/Fe ion, μ, of 1.6 × 10-4 μB observed for the 0.1% Fe doped sample is smaller than the expected spin-only contribution from either high or low spin Fe3+ ions, and μ decreases with increasing Fe concentration. This behavior cannot be explained by the existing models of magnetic exchange. Photocatalytic studies of pure and Fe-doped SnO2 were used to understand the roles of doped Fe3+ ions and of the oxygen vacancies and defects. The photocatalytic rate constant k also showed an increase when SnO2 nanoparticles were doped with low concentrations of Fe3+, reaching a maximum at 0.1% Fe, followed by a rapid decrease of k for further increase in Fe%. Fe doping presumably increases the concentration of oxygen vacancies, and both Fe3+ ions and oxygen vacancies act as electron acceptors to reduce e--h+ recombination and promote transfer of electrons (and/or holes) to the nanoparticle surface, where they participate in redox reactions. This electron transfer from the Fe3+ ions to local defect density of states at the nanoparticle surface could develop a magnetic moment at the surface states and leads to spontaneous ferromagnetic ordering of the surface shell under favorable conditions. However, at higher doping levels, the same Fe3+ ions might act as recombination centers causing a decrease of both k and

Perfect alignment and preferential orientation of nitrogen-vacancy centers during chemical vapor deposition diamond growth on (111) surfaces

International Nuclear Information System (INIS)

Michl, Julia; Zaiser, Sebastian; Jakobi, Ingmar; Waldherr, Gerald; Dolde, Florian; Neumann, Philipp; Wrachtrup, Jörg; Teraji, Tokuyuki; Doherty, Marcus W.; Manson, Neil B.; Isoya, Junichi

2014-01-01

Synthetic diamond production is a key to the development of quantum metrology and quantum information applications of diamond. The major quantum sensor and qubit candidate in diamond is the nitrogen-vacancy (NV) color center. This lattice defect comes in four different crystallographic orientations leading to an intrinsic inhomogeneity among NV centers, which is undesirable in some applications. Here, we report a microwave plasma-assisted chemical vapor deposition diamond growth technique on (111)-oriented substrates, which yields perfect alignment (94% ± 2%) of as-grown NV centers along a single crystallographic direction. In addition, clear evidence is found that the majority (74% ± 4%) of the aligned NV centers were formed by the nitrogen being first included in the (111) growth surface and then followed by the formation of a neighboring vacancy on top. The achieved homogeneity of the grown NV centers will tremendously benefit quantum information and metrology applications

The effect of electron localization on the electronic structure and migration barrier of oxygen vacancies in rutile.

Science.gov (United States)

Zhu, Linggang; Hu, Qing-Miao; Yang, Rui

2014-02-05

By applying the on-site Coulomb interaction (Hubbard term U) to the Ti d orbital, the influence of electron localization on the electronic structure as well as the transport of oxygen vacancies (VO) in rutile was investigated. With U = 4.5 eV, the positions of defect states in the bandgap were correctly reproduced. The unbonded electrons generated by taking out one neutral oxygen atom are spin parallel and mainly localized on the Ti atoms near VO, giving rise to a magnetic moment of 2 μB, in agreement with the experimental finding. With regard to the migration barrier of VO, surprisingly, we found that U = 4.5 eV only changed the value of the energy barrier by ±0.15 eV, depending on the diffusion path. The most probable diffusion path (along [110]) is the same as that calculated by using the traditional GGA functional. To validate the GGA + U method itself, a hybrid functional with a smaller supercell was used, and the trend of the more probable diffusion path was not changed. In this regard, the traditional GGA functional might still be reliable in the study of intrinsic-defect transportation in rutile. Analyzing the atomic distortion and density of states of the transition states for different diffusion paths, we found that the anisotropy of the diffusion could be rationalized according to the various atomic relaxations and the different positions of the valence bands relative to the Fermi level of the transition states.

Diffusion of oxygen in uranium dioxide: A first-principles investigation

International Nuclear Information System (INIS)

Gupta, Florence; Brillant, Guillaume; Pasturel, Alain

2010-01-01

Results of ab initio density-functional theory calculations of the migration energies of oxygen vacancies and interstitials in stoichiometric UO 2 are reported. The diffusion of oxygen vacancies in UO 2 is found to be highly anisotropic, and the [1 0 0] direction is energetically favored. The atomic relaxations play an important role in reducing the migration barriers. Within the generalized gradient approximation (GGA), we find that the migration energies of the preferred vacancies and interstitials paths are, respectively, 1.18 and 1.09 eV. With the inclusion of the Hubbard U parameter to account for the 5f electron correlations in GGA+U, the vacancy migration energy is lowered to 1.01 eV while the interstitial migration energy increases slightly to 1.13 eV. We find, however, that the correlation effects have a drastic influence on the mechanism of interstitial migration through the stabilization of Willis-type clusters. Indeed, in contrast to GGA, in GGA+U there is an inversion of the migration path with the so-called 'saddle-point' position being lower in energy than the usual starting position. Thus while the migration barriers are nearly the same in GGA and GGA+U, the mechanisms are completely different. Our results clearly indicate that both vacancies and interstitials contribute almost equally to the diffusion of oxygen in UO 2 .

Observation and control of blinking nitrogen-vacancy centres in discrete nanodiamonds.

Science.gov (United States)

Bradac, C; Gaebel, T; Naidoo, N; Sellars, M J; Twamley, J; Brown, L J; Barnard, A S; Plakhotnik, T; Zvyagin, A V; Rabeau, J R

2010-05-01

Nitrogen-vacancy colour centres in diamond can undergo strong, spin-sensitive optical transitions under ambient conditions, which makes them attractive for applications in quantum optics, nanoscale magnetometry and biolabelling. Although nitrogen-vacancy centres have been observed in aggregated detonation nanodiamonds and milled nanodiamonds, they have not been observed in very small isolated nanodiamonds. Here, we report the first direct observation of nitrogen-vacancy centres in discrete 5-nm nanodiamonds at room temperature, including evidence for intermittency in the luminescence (blinking) from the nanodiamonds. We also show that it is possible to control this blinking by modifying the surface of the nanodiamonds.

Insight into the effect of screw dislocations and oxygen vacancy defects on the optical nonlinear refraction response in chemically grown ZnO/Al2O3 films

Science.gov (United States)

Agrawal, Arpana; Saroj, Rajendra K.; Dar, Tanveer A.; Baraskar, Priyanka; Sen, Pratima; Dhar, Subhabrata

2017-11-01

We report the effect of screw dislocations and oxygen vacancy defects on the optical nonlinear refraction response of ZnO films grown on a sapphire substrate at various oxygen flow rates using the chemical vapor deposition technique. The nonlinear refraction response was investigated in the off-resonant regime using a CW He-Ne laser source to examine the role of the intermediate bandgap states. It has been observed that the structural defects strongly influence the optical nonlinearity in the off-resonant regime. Nonlinearity has been found to improve as the oxygen flow rate is lowered from 2 sccm to 0.3 sccm. From photoluminescence studies, we observe that the enhanced defect density of the electronic defect levels due to the increased concentration of structural defects (with the decrease in the oxygen flow rate) is responsible for this improved optical nonlinearity along with the thermal effect. This suggests that defect engineering is an effective way to tailor the nonlinearity of ZnO films and their utility for optoelectronic device applications.

Exchange and Dzyaloshinskii-Moriya interactions in bulk FeGe: Effects of atomic vacancies

Science.gov (United States)

Loh, G. C.; Gan, C. K.

2017-05-01

We examine the effects of atomic vacancies on the (1) spin interaction, and (2) electronic character in the cubic B20 chiral magnet FeGe. For the former, Heisenberg exchange and Dzyaloshinskii-Moriya (DM) interactions are studied. The latter is done via a particular Wannier flavor of the Hamiltonian in the form of maximally-localized Wannier functions (MLWFs). Using first-principles calculations based on full-potential linearized augmented plane-wave (FLAPW)-based density functional theory (DFT), the spin order of bulk FeGe, in its pristine form, and with a Fe (Fe75%Ge100%) or Ge vacancy (Fe100%Ge75%) is investigated. Despite the presence of vacancies, the ground state of FeGe remains helimagnetic, i.e. spin spirals in FeGe are fairly robust. The energetic stability of FeGe increases in the presence of the vacancies. The spiral size is increased by approximately 40%, suggesting that vacancies can be introduced to manipulate the chiral order. The vacancies lift the band degeneracy in the valence manifold of the Wannier-interpolated band structures. Only the spin-down Fermi surfaces are substantially different between the pristine and defective FeGe; it is electron-like in the pristine case, but largely hole-like in the defective ones. The Ge vacancy splits the Fermi surface more than the Fe vacancy. The Heisenberg exchange between nearest Fe pairs is ferromagnetic in pristine FeGe. This Fe-Fe interaction remains ferromagnetic, albeit a slight decrease in strength, in the presence of a Fe vacancy. In contrast, a Ge vacancy in FeGe induces anti-ferromagnetism between nearest Fe pairs. By including spin-orbit coupling effects, we find that the DM interaction of defective FeGe is reversed in sign, and it is more uniform in strength along the three highly symmetric directions, relative to that in pristine FeGe. All in all, the versatility of FeGe makes it an excellent functional material, especially in data storage and spintronics applications.

Oxygen permeation modelling of perovskites

NARCIS (Netherlands)

van Hassel, Bart A.; van Hassel, B.A.; Kawada, Tatsuya; Sakai, Natsuko; Yokokawa, Harumi; Dokiya, Masayuki; Bouwmeester, Henricus J.M.

1993-01-01

A point defect model was used to describe the oxygen nonstoichiometry of the perovskites La0.75Sr0.25CrO3, La0.9Sr0.1FeO3, La0.9Sr0.1CoO3 and La0.8Sr0.2MnO3 as a function of the oxygen partial pressure. Form the oxygen vacancy concentration predicte by the point defect model, the ionic conductivity

Investigation of oxygen plasma treatment on the device performance of solution-processed a-IGZO thin film transistors

International Nuclear Information System (INIS)

Pu, Haifeng; Zhou, Qianfei; Yue, Lan; Zhang, Qun

2013-01-01

We reported the impact of oxygen plasma treatment on solution-processed amorphous indium gallium zinc oxide (a-IGZO) thin film transistors (TFTs). Plasma-treated devices showed higher mobility, larger on/off current ratio, but a monotonically increased SS with plasma treatment time as well. The phenomenon was mainly due to two components in oxygen plasma, atomic oxygen and O 2 + , according to the photoluminescence (PL) measurement. Atomic oxygen reacted with oxygen vacancies in channel layer resulting in an improved mobility, and O 2 + tends to aggregated at the surface acting as trapping states simultaneously. Our study suggests that moderate oxygen plasma treatment can be adopted to improve the device performance, while O 2 + should be eliminated to obtain good interfacial states.

An oxygen pressure sensor using surface acoustic wave devices

Science.gov (United States)

Leighty, Bradley D.; Upchurch, Billy T.; Oglesby, Donald M.

1993-01-01

Surface acoustic wave (SAW) piezoelectric devices are finding widespread applications in many arenas, particularly in the area of chemical sensing. We have developed an oxygen pressure sensor based on coating a SAW device with an oxygen binding agent which can be tailored to provide variable sensitivity. The coating is prepared by dissolving an oxygen binding agent in a toluene solution of a copolymer which is then sprayed onto the surface of the SAW device. Experimental data shows the feasibility of tailoring sensors to measure the partial pressure of oxygen from 2.6 to 67 KPa (20 to 500 torr). Potential applications of this technology are discussed.

Radiation-induced defects in LiAlO{sub 2} crystals: Holes trapped by lithium vacancies and their role in thermoluminescence

Energy Technology Data Exchange (ETDEWEB)

Holston, M.S.; McClory, J.W.; Giles, N.C. [Department of Engineering Physics, Air Force Institute of Technology, Wright-Patterson Air Force Base, OH 45433 (United States); Halliburton, L.E., E-mail: Larry.Halliburton@mail.wvu.edu [Department of Physics and Astronomy, West Virginia University, Morgantown, WV 26506 (United States)

2015-04-15

Electron paramagnetic resonance (EPR) is used to identify the primary hole trap in undoped lithium aluminate (LiAlO{sub 2}) crystals. Our interest in this material arises because it is a candidate for radiation detection applications involving either optically stimulated luminescence (OSL) or thermoluminescence (TL). During an x-ray irradiation at room temperature, holes are trapped at oxygen ions adjacent to lithium vacancies. Large concentrations of these lithium vacancies are introduced into the crystal during growth. With the magnetic field along the [001] direction, the EPR spectrum from these trapped-hole centers consists of eleven lines, evenly spaced but with varying intensities, caused by nearly equal hyperfine interactions with two {sup 27}Al nuclei (I=5/2, 100% abundant). The g matrix is determined from the angular dependence of the EPR spectrum and has principal values of 2.0130, 2.0675, and 2.0015. These g shifts strongly support the model of a hole in a p orbital on an oxygen ion. The adjacent lithium vacancy stabilizes the hole on the oxygen ion. A sequence of pulsed thermal anneals above room temperature shows that the EPR spectrum from the holes trapped adjacent to the lithium vacancies disappears in the 90–120 °C range. The thermal decay of these hole centers directly correlates with an intense TL peak near 105 °C. Signals at lower magnetic field in the 9.4 GHz EPR spectra suggest that the electron trap associated with this TL peak at 105 °C may be a transition-metal-ion impurity, most likely Fe, located at a cation site. Additional less intense TL peaks are observed near 138, 176, and 278 °C. - Highlights: • Undoped LiAlO{sub 2} crystals are irradiated at room temperature with x-rays. • EPR is used to identify holes trapped at oxygen ions adjacent to lithium vacancies. • Thermal decay of the EPR spectrum correlates with an intense TL peak at 105 °C.

Experimental identification of nitrogen-vacancy complexes in nitrogen implanted silicon

Science.gov (United States)

Adam, Lahir Shaik; Law, Mark E.; Szpala, Stanislaw; Simpson, P. J.; Lawther, Derek; Dokumaci, Omer; Hegde, Suri

2001-07-01

Nitrogen implantation is commonly used in multigate oxide thickness processing for mixed signal complementary metal-oxide-semiconductor and System on a Chip technologies. Current experiments and diffusion models indicate that upon annealing, implanted nitrogen diffuses towards the surface. The mechanism proposed for nitrogen diffusion is the formation of nitrogen-vacancy complexes in silicon, as indicated by ab initio studies by J. S. Nelson, P. A. Schultz, and A. F. Wright [Appl. Phys. Lett. 73, 247 (1998)]. However, to date, there does not exist any experimental evidence of nitrogen-vacancy formation in silicon. This letter provides experimental evidence through positron annihilation spectroscopy that nitrogen-vacancy complexes indeed form in nitrogen implanted silicon, and compares the experimental results to the ab initio studies, providing qualitative support for the same.

Memristive behaviour of Si-Al oxynitride thin films: the role of oxygen and nitrogen vacancies in the electroforming process

Science.gov (United States)

Blázquez, O.; Martín, G.; Camps, I.; Mariscal, A.; López-Vidrier, J.; Ramírez, J. M.; Hernández, S.; Estradé, S.; Peiró, F.; Serna, R.; Garrido, B.

2018-06-01

The resistive switching properties of silicon-aluminium oxynitride (SiAlON) based devices have been studied. Electrical transport mechanisms in both resistance states were determined, exhibiting an ohmic behaviour at low resistance and a defect-related Poole‑Frenkel mechanism at high resistance. Nevertheless, some features of the Al top-electrode are generated during the initial electroforming, suggesting some material modifications. An in-depth microscopic study at the nanoscale has been performed after the electroforming process, by acquiring scanning electron microscopy and transmission electron microscopy images. The direct observation of the devices confirmed features on the top electrode with bubble-like appearance, as well as some precipitates within the SiAlON. Chemical analysis by electron energy loss spectroscopy has demonstrated that there is an out-diffusion of oxygen and nitrogen ions from the SiAlON layer towards the electrode, thus forming silicon-rich paths within the dielectric layer and indicating vacancy change to be the main mechanism in the resistive switching.

Thickness independent reduced forming voltage in oxygen engineered HfO{sub 2} based resistive switching memories

Energy Technology Data Exchange (ETDEWEB)

Sharath, S. U., E-mail: sharath@oxide.tu-darmstadt.de; Kurian, J.; Komissinskiy, P.; Hildebrandt, E.; Alff, L. [Institute of Materials Science, Technische Universität Darmstadt, 64287 Darmstadt (Germany); Bertaud, T.; Walczyk, C.; Calka, P. [IHP, Im Technologiepark 25, 15236 Frankfurt Oder (Germany); Schroeder, T. [IHP, Im Technologiepark 25, 15236 Frankfurt Oder (Germany); Brandenburgische Technische Universität, Konrad-Zuse-Strasse 1, 03046 Cottbus (Germany)

2014-08-18

The conducting filament forming voltage of stoichiometric hafnium oxide based resistive switching layers increases linearly with layer thickness. Using strongly reduced oxygen deficient hafnium oxide thin films grown on polycrystalline TiN/Si(001) substrates, the thickness dependence of the forming voltage is strongly suppressed. Instead, an almost constant forming voltage of about 3 V is observed up to 200 nm layer thickness. This effect suggests that filament formation and switching occurs for all samples in an oxidized HfO{sub 2} surface layer of a few nanometer thickness while the highly oxygen deficient thin film itself merely serves as a oxygen vacancy reservoir.

A statistical correlation investigation for the role of surface spins to the spin relaxation of nitrogen vacancy centers

Energy Technology Data Exchange (ETDEWEB)

Song, Xuerui; Zhang, Jian; Feng, Fupan; Wang, Junfeng; Zhang, Wenlong; Lou, Liren; Zhu, Wei; Wang, Guanzhong, E-mail: gzwang@ustc.edu.cn [Hefei National Laboratory for Physical Science at Microscale, and Department of Physics, University of Science and Technology of China, Hefei, Anhui, 230026 (China)

2014-04-15

We investigated the influence of spins on surface of nanodiamonds (NDs) to the longitudinal relaxation time (T{sub 1}) and transverse relaxation time (T{sub 2}) of nitrogen vacancy (NV) centers in ND. A spherical model of the NDs was suggested to account for the experimental results of T{sub 1} and T{sub 2}, and the density of surface spins was roughly estimated based on the statistical analysis of experimental results of 72 NDs containing a single NV center. For NDs studied here, the T{sub 1} of NV center inside is highly dependent to the surface spins of the NDs. However, for the T{sub 2} of NV center, intrinsic contributions must be much pronounced than that by surface spins. In other words, T{sub 1} of an NV center in NDs is more sensitive to the change of the surface spin density than T{sub 2}.

A statistical correlation investigation for the role of surface spins to the spin relaxation of nitrogen vacancy centers

Directory of Open Access Journals (Sweden)

Xuerui Song

2014-04-01

Full Text Available We investigated the influence of spins on surface of nanodiamonds (NDs to the longitudinal relaxation time (T1 and transverse relaxation time (T2 of nitrogen vacancy (NV centers in ND. A spherical model of the NDs was suggested to account for the experimental results of T1 and T2, and the density of surface spins was roughly estimated based on the statistical analysis of experimental results of 72 NDs containing a single NV center. For NDs studied here, the T1 of NV center inside is highly dependent to the surface spins of the NDs. However, for the T2 of NV center, intrinsic contributions must be much pronounced than that by surface spins. In other words, T1 of an NV center in NDs is more sensitive to the change of the surface spin density than T2.

Size Dependence of Doping by a Vacancy Formation Reaction in Copper Sulfide Nanocrystals

Energy Technology Data Exchange (ETDEWEB)

Elimelech, Orian [The Institute of Chemistry and The Center for Nanoscience and Nanotechnology, The Hebrew University of Jerusalem, Jerusalem 91904 Israel; Liu, Jing [Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook NY 11794 USA; Plonka, Anna M. [Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook NY 11794 USA; Frenkel, Anatoly I. [Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook NY 11794 USA; Banin, Uri [The Institute of Chemistry and The Center for Nanoscience and Nanotechnology, The Hebrew University of Jerusalem, Jerusalem 91904 Israel

2017-07-19

Doping of nanocrystals (NCs) is a key, yet underexplored, approach for tuning of the electronic properties of semiconductors. An important route for doping of NCs is by vacancy formation. The size and concentration dependence of doping was studied in copper(I) sulfide (Cu2S) NCs through a redox reaction with iodine molecules (I2), which formed vacancies accompanied by a localized surface plasmon response. X-ray spectroscopy and diffraction reveal transformation from Cu2S to Cu-depleted phases, along with CuI formation. Greater reaction efficiency was observed for larger NCs. This behavior is attributed to interplay of the vacancy formation energy, which decreases for smaller sized NCs, and the growth of CuI on the NC surface, which is favored on well-defined facets of larger NCs. This doping process allows tuning of the plasmonic properties of a semiconductor across a wide range of plasmonic frequencies by varying the size of NCs and the concentration of iodine. Controlled vacancy doping of NCs may be used to tune and tailor semiconductors for use in optoelectronic applications.

Origin and enhancement of spin polarized current in diluted magnetic oxides by oxygen vacancies

Energy Technology Data Exchange (ETDEWEB)

Chou, Hsiung, E-mail: hchou@mail.nsysu.edu.tw; Yang, Kung-Shang; Tsao, Yao-Chung; Dwivedi, G. D.; Lin, Cheng-Pang [Department of Physics, National Sun Yat-Sen University, 70, Lienhai Road, Gushan District, Kaohsiung 804, Taiwan (China); Sun, Shih-Jye [Department of Applied Physics, National Kaohsiung University, 700, Gaoxiongdaxue Rd., Nanzi District, Kaohsiung 811, Taiwan (China); Lin, L. K.; Lee, S. F. [Institute of Physics, Academia Sinica, 128 Academia Road, Section 2, Nankang, Taipei 115, Taiwan (China)

2016-04-04

Spin polarized current (SPC) is a crucial characteristic of diluted magnetic oxides due to the potential application of oxides in spintronic devices. However, most research has been focused on ferromagnetic properties rather than polarization of electric current, because direct measurements are difficult and the origin of SPC has yet to be fully understood. The method to increase the SPC percentage is beyond practical consideration at present. To address this problem, we focus on the role of oxygen vacancies (V{sub O}) on SPC, which are controlled by growing the Co-doped ZnO thin-films at room temperature in a reducing atmosphere [Ar + (1%–30%)H{sub 2}]. We found that the conductivity increases with an increase of V{sub O} via two independent channels: the variable range hopping (VRH) within localized states and the itinerant transport in the conduction band. The point contact Andreev reflection measurements at 4.2 K, where the electric conduction is governed only by the VRH mechanism, prove that the current flowing in the VRH hopping channel is SPC. The percentage of SPC increases with the introduction of V{sub O} and increase in its concentration. The transport measurement shows that by manipulating V{sub O}, one can control the percentage of VRH hopping conduction such that it can even dominate room temperature conduction. The highest achieved SPC ratio at room temperature was 80%.

Positron annihilation studies on the behaviour of vacancies in LaAlO3/SrTiO3 heterostructures

Science.gov (United States)

Yuan, Guoliang; Li, Chen; Yin, Jiang; Liu, Zhiguo; Wu, Di; Uedono, Akira

2012-11-01

The formation and diffusion of vacancies are studied in LaAlO3/SrTiO3 heterostructures. Oxygen vacancies (VOS) appear easily in the SrTiO3 substrate during LaAlO3 film growth at 700 °C and 10-4 Pa oxygen pressure rather than at 10-3-10-1 Pa, thus the latter two-dimensional electron gas should come from the polarity discontinuity at the (LaO)+/(TiO2)0 interface. For SrTiO3-δ/LaAlO3/SrTiO3, high-density VOS of the SrTiO3-δ film can pass through the LaAlO3 film and then diffuse to 1.7 µm depth in the SrTiO3 substrate, suggesting that LaAlO3 has VOS at its middle-deep energy levels within the band gap. Moreover, high-density VOS may combine with a strontium/titanium vacancy (VSr/Ti) to form VSr/Ti-O complexes in the SrTiO3 substrate at 700 °C.

Thermodynamic, electronic, and magnetic properties of intrinsic vacancy defects in antiperovskite Ca3SnO

Science.gov (United States)

Batool, Javaria; Alay-e-Abbas, Syed Muhammad; Amin, Nasir

2018-04-01

The density functional theory based total energy calculations are performed to examine the effect of charge neutral and fully charged intrinsic vacancy defects on the thermodynamic, electronic, and magnetic properties of Ca3SnO antiperovskite. The chemical stability of Ca3SnO is evaluated with respect to binary compounds CaO, CaSn, and Ca2Sn, and the limits of atomic chemical potentials of Ca, Sn, and O atoms for stable synthesis of Ca3SnO are determined within the generalized gradient approximation parametrization scheme. The electronic properties of the pristine and the non-stoichiometric forms of this compound have been explored and the influence of isolated intrinsic vacancy defects (Ca, Sn, and O) on the structural, bonding, and electronic properties of non-stoichiometric Ca3SnO are analyzed. We also predict the possibility of achieving stable ferromagnetism in non-stoichiometric Ca3SnO by means of charge neutral tin vacancies. From the calculated total energies and the valid ranges of atomic chemical potentials, the formation energetics of intrinsic vacancy defects in Ca3SnO are evaluated for various growth conditions. Our results indicate that the fully charged calcium vacancies are thermodynamically stable under the permissible Sn-rich condition of stable synthesis of Ca3SnO, while tin and oxygen vacancies are found to be stable under the extreme Ca-rich condition.

Energy investigations on the mechanical properties of magnesium alloyed by X = C, B, N, O and vacancy

KAUST Repository

Wu, Xiaozhi

2013-10-25

The generalized stacking fault (GSF) energies and surface energies of magnesium and its alloys with alloying atoms X = C, B, N, O and vacancy have been investigated using the first-principles methods. It is found that the predominant reducing effects of the alloying atoms and vacancy on the stacking fault energy are resulted from the position of them in the 1st layer near the slip plane. The stacking fault energies are nearly the same as the pure magnesium while the alloying atoms and vacancy are placed in the 2nd, 3rd, 4th, 5th and 6th layers. It has been shown that O strongly reduces the GSF energy of Mg. The alloying atoms C, B and N increase the surface energy, but O and vacancy reduce the surface energy of Mg. The ductilities of Mg and Mg alloys have been discussed based on the Rice criterion by using the ratio between surface energy and unstable stacking fault energy. © 2013 Higher Education Press and Springer-Verlag Berlin Heidelberg.

Hafnium carbide formation in oxygen deficient hafnium oxide thin films

Energy Technology Data Exchange (ETDEWEB)

Rodenbücher, C. [Forschungszentrum Jülich GmbH, Peter Grünberg Institute (PGI-7), JARA-FIT, 52425 Jülich (Germany); Hildebrandt, E.; Sharath, S. U.; Kurian, J.; Komissinskiy, P.; Alff, L. [Technische Universität Darmstadt, Institute of Materials Science, 64287 Darmstadt (Germany); Szot, K. [Forschungszentrum Jülich GmbH, Peter Grünberg Institute (PGI-7), JARA-FIT, 52425 Jülich (Germany); University of Silesia, A. Chełkowski Institute of Physics, 40-007 Katowice (Poland); Breuer, U. [Forschungszentrum Jülich GmbH, Central Institute for Engineering, Electronics and Analytics (ZEA-3), 52425 Jülich (Germany); Waser, R. [Forschungszentrum Jülich GmbH, Peter Grünberg Institute (PGI-7), JARA-FIT, 52425 Jülich (Germany); RWTH Aachen, Institute of Electronic Materials (IWE 2), 52056 Aachen (Germany)

2016-06-20

On highly oxygen deficient thin films of hafnium oxide (hafnia, HfO{sub 2−x}) contaminated with adsorbates of carbon oxides, the formation of hafnium carbide (HfC{sub x}) at the surface during vacuum annealing at temperatures as low as 600 °C is reported. Using X-ray photoelectron spectroscopy the evolution of the HfC{sub x} surface layer related to a transformation from insulating into metallic state is monitored in situ. In contrast, for fully stoichiometric HfO{sub 2} thin films prepared and measured under identical conditions, the formation of HfC{sub x} was not detectable suggesting that the enhanced adsorption of carbon oxides on oxygen deficient films provides a carbon source for the carbide formation. This shows that a high concentration of oxygen vacancies in carbon contaminated hafnia lowers considerably the formation energy of hafnium carbide. Thus, the presence of a sufficient amount of residual carbon in resistive random access memory devices might lead to a similar carbide formation within the conducting filaments due to Joule heating.

First-principles study of native defects in bulk Sm2CuO4 and its (001) surface structure

Science.gov (United States)

Zheng, Fubao; Zhang, Qinfang; Meng, Qiangqiang; Wang, Baolin; Song, Fengqi; Yunoki, Seiji; Wang, Guanghou

2018-04-01

Using the first-principles calculations based on the density functional theory, we have studied the bulk defect formation and surface structures of Sm2CuO4. To ensure the accuracy of calculations, the spin order of Cu atoms is rechecked and it is the well-known nearest-neighbor antiferromagnetic ground state, which can be attributed to the hole-mediated superexchange through the strong pdσ hybridization interaction between Cu dx2-y2 electron and the neighboring oxygen px (or py) electron. Under each present experimental condition, the Sm vacancy has a very high formation energy and is unlikely to be stable. The Cu vacancy is a shallow acceptor, which is preferred under O-rich conditions, whereas the O vacancy is a donor and energetically favorable under O-poor conditions. To construct its (001) surface structure, CuOO, CuO, and Cu terminated surfaces are found to be most favorable under different experimental conditions. The stable surface structures are always accompanied by significant surface atomic reconstructions and electron charge redistribution, which are intimately correlated to each other.

A first-principles study of oxygen adsorption on Ir(111) surface

Energy Technology Data Exchange (ETDEWEB)

Gao, Hengjiao, E-mail: gaohengjiao@163.com; Xiong, Yuqing, E-mail: xiongyq@hotmail.com; Liu, Xiaoli, E-mail: shantianzi@126.com; Zhao, Dongcai, E-mail: zhaodongc@163.com; Feng, Yudong, E-mail: yudong_feng@sina.com; Wang, Lanxi, E-mail: wanglanxi@live.com; Wang, Jinxiao, E-mail: coldwind716@gmail.com

2016-12-15

Highlights: • Adsorption of oxygen on Ir(111) surface was studied by density functional theory. • The most stable adsorption site was determined by adsorption energy calculation. • Adsorption of oxygen at bridge and top site on Ir surface was the most stable ones. • Interaction of O 2p and Ir 5d orbits is relatively strong and formed hybridization. - Abstract: In order to understand deposition mechanism of iridium thin film by atomic layer deposition, the adsorption of oxygen on Ir(111) surface was studied by use of density functional theory and a periodical slab model. By calculating the adsorption energy and structure of oxygen at four adsorption sites (top, bridge, fcc-hollow and hcp-hollow) on Ir(111) surface, the most stable adsorption site was determined. On this basis, the banding mechanism of O and Ir atoms was studied by density of states of oxygen and iridium atoms. Oxygen adsorbed at hcp(parallel) site on Ir(111) surface was the most stable one according to the adsorption energy calculation results. Orbital charge analysis indicate that charge transferred from 5p and 5d orbit to 2p orbit of adsorbed O atoms, and 6s orbit of iridium atoms. Meanwhile, density of state study indicated that adsorption of oxygen on Ir(111) surface is mainly due to the interaction between 2p orbit of O atoms and 5d orbit of iridium atoms.

Rapid decay of vacancy islands at step edges on Ag(111): step orientation dependence

International Nuclear Information System (INIS)

Shen, Mingmin; Thiel, P A; Jenks, Cynthia J; Evans, J W

2010-01-01

Previous work has established that vacancy islands or pits fill much more quickly when they are in contact with a step edge, such that the common boundary is a double step. The present work focuses on the effect of the orientation of that step, with two possibilities existing for a face centered cubic (111) surface: A- and B-type steps. We find that the following features can depend on the orientation: (1) the shapes of islands while they shrink; (2) whether the island remains attached to the step edge; and (3) the rate of filling. The first two effects can be explained by the different rates of adatom diffusion along the A- and B-steps that define the pit, enhanced by the different filling rates. The third observation-the difference in the filling rate itself-is explained within the context of the concerted exchange mechanism at the double step. This process is facile at all regular sites along B-steps, but only at kink sites along A-steps, which explains the different rates. We also observe that oxygen can greatly accelerate the decay process, although it has no apparent effect on an isolated vacancy island (i.e. an island that is not in contact with a step).

Electron diffraction study of the sillenites Bi{sub 12}SiO{sub 20}, Bi{sub 25}FeO{sub 39} and Bi{sub 25}InO{sub 39}: Evidence of short-range ordering of oxygen-vacancies in the trivalent sillenites

Energy Technology Data Exchange (ETDEWEB)

Scurti, Craig A.; Arenas, D. J. [Department of Physics, University of North Florida, Jacksonville, FL 32224 (United States); Auvray, Nicolas [Department of Physics, University of North Florida, Jacksonville, FL 32224 (United States); Laboratoire de Nanotechnologie et d’Instrumentation Optique - UMR CNRS 6279, Université Technologie de Troyes, 12 rue Marie Curie, Troyes 10010 (France); Lufaso, Michael W. [Department of Chemistry, University of North Florida, Jacksonville, FL 32224 (United States); Takeda, Seiji [The Institute of Scientific and Industrial Research, Osaka University, 8-1 Mihogaoka, Ibaraki, Osaka 567-0047 (Japan); Kohno, Hideo [School of Environmental Science and Engineering, Kochi University of Technology, Tosayamada, Kami, Kochi 782-8502 Japan (Japan)

2014-08-15

We present an electron diffraction study of three sillenites, Bi{sub 12}SiO{sub 20}, Bi{sub 25}FeO{sub 39}, and Bi{sub 25}InO{sub 39} synthesized using the solid-state method. We explore a hypothesis, inspired by optical studies in the literature, that suggests that trivalent sillenites have additional disorder not present in the tetravalent compounds. Electron diffraction patterns of Bi{sub 25}FeO{sub 39} and Bi{sub 25}InO{sub 39} show streaks that confirm deviations from the ideal sillenite structure. Multi-slice simulations of electron-diffraction patterns are presented for different perturbations to the sillenite structure - partial substitution of the M site by Bi{sup 3+}, random and ordered oxygen-vacancies, and a frozen-phonon model. Although comparison of experimental data to simulations cannot be conclusive, we consider the streaks as evidence of short-range ordered oxygen-vacancies.

Oxygen vacancy defect engineering using atomic layer deposited HfAlOx in multi-layered gate stack

Science.gov (United States)

Bhuyian, M. N.; Sengupta, R.; Vurikiti, P.; Misra, D.

2016-05-01

This work evaluates the defects in high quality atomic layer deposited (ALD) HfAlOx with extremely low Al (estimated by the high temperature current voltage measurement shows that the charged oxygen vacancies, V+/V2+, are the primary source of defects in these dielectrics. When Al is added in HfO2, the V+ type defects with a defect activation energy of Ea ˜ 0.2 eV modify to V2+ type to Ea ˜ 0.1 eV with reference to the Si conduction band. When devices were stressed in the gate injection mode for 1000 s, more V+ type defects are generated and Ea reverts back to ˜0.2 eV. Since Al has a less number of valence electrons than do Hf, the change in the co-ordination number due to Al incorporation seems to contribute to the defect level modifications. Additionally, the stress induced leakage current behavior observed at 20 °C and at 125 °C demonstrates that the addition of Al in HfO2 contributed to suppressed trap generation process. This further supports the defect engineering model as reduced flat-band voltage shifts were observed at 20 °C and at 125 °C.

Oxygen vacancy as fatigue evidence of La0.5Sr0.5CoO3/PbZr0.4Ti0.6O3/La0.5Sr0.5CoO3 capacitors

Science.gov (United States)

Liu, B. T.; Chen, J. E.; Sun, J.; Wei, D. Y.; Chen, J. H.; Li, X. H.; Bian, F.; Zhou, Y.; Guo, J. X.; Zhao, Q. X.; Guan, L.; Wang, Y. L.; Guo, Q. L.; Ma, L. X.

2010-09-01

La0.5Sr0.5CoO3 (LSCO) films grown on SrTiO3 substrates, cooled at reduced oxygen pressures, ranging from 8×104 to 1×10-4 Pa, from the depostion temperature, are used as the bottom electrodes of PbZr0.4Ti0.6O3 (PZT) capacitors to study the impact of oxygen stoichiometry of the LSCO bottom electrodes on the structural and physical properties of LSCO/PZT/LSCO capacitors. It is found that the tetragonality, polarization and fatigue-resistance of PZT films decrease with the decrease of the cooling oxygen pressure. Almost 60% polarization degradation occurs for the PZT capacitor with the LSCO bottom electrode cooled in 1×10-4 Pa oxygen up to 1010 switching cycles, indicating that the oxygen vacancy of the bottom electrode can result in fatigue of the LSCO/PZT/LSCO capacitor.

Band gap effects of hexagonal boron nitride using oxygen plasma

International Nuclear Information System (INIS)

Sevak Singh, Ram; Leong Chow, Wai; Yingjie Tay, Roland; Hon Tsang, Siu; Mallick, Govind; Tong Teo, Edwin Hang

2014-01-01

Tuning of band gap of hexagonal boron nitride (h-BN) has been a challenging problem due to its inherent chemical stability and inertness. In this work, we report the changes in band gaps in a few layers of chemical vapor deposition processed as-grown h-BN using a simple oxygen plasma treatment. Optical absorption spectra show a trend of band gap narrowing monotonically from 6 eV of pristine h-BN to 4.31 eV when exposed to oxygen plasma for 12 s. The narrowing of band gap causes the reduction in electrical resistance by ∼100 fold. The x-ray photoelectron spectroscopy results of plasma treated hexagonal boron nitride surface show the predominant doping of oxygen for the nitrogen vacancy. Energy sub-band formations inside the band gap of h-BN, due to the incorporation of oxygen dopants, cause a red shift in absorption edge corresponding to the band gap narrowing

Band gap effects of hexagonal boron nitride using oxygen plasma

Energy Technology Data Exchange (ETDEWEB)

Sevak Singh, Ram; Leong Chow, Wai [School of Electrical and Electronic Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Yingjie Tay, Roland [School of Electrical and Electronic Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Temasek Laboratories-NTU, 50 Nanyang Avenue, Singapore 639798 (Singapore); Hon Tsang, Siu [Temasek Laboratories-NTU, 50 Nanyang Avenue, Singapore 639798 (Singapore); Mallick, Govind [Temasek Laboratories-NTU, 50 Nanyang Avenue, Singapore 639798 (Singapore); Weapons and Materials Research Directorate, U.S. Army Research Laboratory, Aberdeen Proving Ground, Maryland 21005 (United States); Tong Teo, Edwin Hang, E-mail: htteo@ntu.edu.sg [School of Electrical and Electronic Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore)

2014-04-21

Tuning of band gap of hexagonal boron nitride (h-BN) has been a challenging problem due to its inherent chemical stability and inertness. In this work, we report the changes in band gaps in a few layers of chemical vapor deposition processed as-grown h-BN using a simple oxygen plasma treatment. Optical absorption spectra show a trend of band gap narrowing monotonically from 6 eV of pristine h-BN to 4.31 eV when exposed to oxygen plasma for 12 s. The narrowing of band gap causes the reduction in electrical resistance by ∼100 fold. The x-ray photoelectron spectroscopy results of plasma treated hexagonal boron nitride surface show the predominant doping of oxygen for the nitrogen vacancy. Energy sub-band formations inside the band gap of h-BN, due to the incorporation of oxygen dopants, cause a red shift in absorption edge corresponding to the band gap narrowing.

Zn-vacancy related defects in ZnO grown by pulsed laser deposition

Science.gov (United States)

Ling, F. C. C.; Luo, C. Q.; Wang, Z. L.; Anwand, W.; Wagner, A.

2017-02-01

Undoped and Ga-doped ZnO (002) films were grown c-sapphire using the pulsed laser deposition (PLD) method. Znvacancy related defects in the films were studied by different positron annihilation spectroscopy (PAS). These included Doppler broadening spectroscopy (DBS) employing a continuous monenergetic positron beam, and positron lifetime spectroscopy using a pulsed monoenergetic positron beam attached to an electron linear accelerator. Two kinds of Znvacancy related defects namely a monovacancy and a divacancy were identified in the films. In as-grown undoped samples grown with relatively low oxygen pressure P(O2)≤1.3 Pa, monovacancy is the dominant Zn-vacancy related defect. Annealing these samples at 900 oC induced Zn out-diffusion into the substrate and converted the monovacancy to divacancy. For the undoped samples grown with high P(O2)=5 Pa irrespective of the annealing temperature and the as-grown degenerate Ga-doped sample (n=1020 cm-3), divacancy is the dominant Zn-vacancy related defect. The clustering of vacancy will be discussed.

Thermal conductivity reduction in oxygen-deficient strontium titanates

NARCIS (Netherlands)

Yu, Choongho; Scullin, Matthew L.; Huijben, Mark; Ramesh, Ramamoorthy; Majumdar, Arun

2008-01-01

We report significant thermal conductivity reduction in oxygen-deficient lanthanum-doped strontium titanate (Sr1−xLaxTiO3−δ) films as compared to unreduced strontium titanates. Our experimental results suggest that the oxygen vacancies could have played an important role in the reduction. This could

Positron lifetime in vacancy clusters. Application to the study of vacancy-impurity interactions

International Nuclear Information System (INIS)

Corbel, C.

1986-02-01

Positron lifetime measurements are used to study the vacancy recovery (77-650 K) in 20 K electron irradiated dilute gold or iron alloys in stainless steels. Positron lifetimes in clusters of various shapes and structures are calculated to precise the information obtained by measuring the positron lifetime in a vacancy cluster of unknown size and configuration. From the calculations, we have drawn the following conclusions: - the minimal size of an unknown cluster can be deduced from the measurement of the positron lifetime in the cluster; - a decrease of the positron lifetime when the structure of the cluster evolves, means either a decrease of the size of the cluster, or, the appearance of a relaxed configuration. - The positron lifetime is very useful to discriminate between a spatial planar or relaxed configuration and a tri-dimensional one. In AuGe, AuSb, AuTn alloys, vacancy clusters decorated by solute atoms appear at 250 K. Their configurations are different from those in pure Au. Mobile vacancy-solutes complexes are involved in the clustering process in AuGe, AuSb. The clusters are probably decorated by several solute atoms in AuGe and AuSb where the resistivity evidences a clustering of solute atoms. In AuFe, vacancy-single or multi-complexes stable up to 670 K prevent cluster formation. In FeTi, FeSb, FeAu, vacancy migration is hindered by the formation of vacancy-solute complexes up to 315 K (Ti), up to 670 K (Sb), up to 700 K (Au). In FeSi, FeCu, FeAg, tri-dimensional clusters grow less easily than Fe. This is likely due to the formation of several kinds of small decorated clusters with relaxed or planar configurations. They are peculiarly stable, surviving up to 700 K at least. In Si (resp. Ti) doped 59Fe25Ni16Cr, solute atoms retain the vacancies up to 300 K (resp. 320 K) [fr

Chemistry of SOFC Cathode Surfaces: Fundamental Investigation and Tailoring of Electronic Behavior

Energy Technology Data Exchange (ETDEWEB)

Yildiz, Bilge; Heski, Clemens

2013-08-31

1) Electron tunneling characteristics on La0.7Sr0.3MnO3 (LSM) thin-film surfaces were studied up to 580oC in 10-3mbar oxygen pressure, using scanning tunneling microscopy/ spectroscopy (STM/STS). A threshold-like drop in the tunneling current was observed at positive bias in STS, which is interpreted as a unique indicator for the activation polarization in cation oxygen bonding on LSM cathodes. Sr-enrichment was found on the surface at high temperature using Auger electron spectroscopy, and was accompanied by a decrease in tunneling conductance in STS. This suggests that Sr-terminated surfaces are less active for electron transfer in oxygen reduction compared to Mn-terminated surfaces on LSM. 2) Effects of strain on the surface cation chemistry and the electronic structure are important to understand and control for attaining fast oxygen reduction kinetics on transition metal oxides. Here, we demonstrate and mechanistically interpret the strain coupling to Sr segregation, oxygen vacancy formation, and electronic structure on the surface of La0.7Sr0.3MnO3 (LSM) thin films as a model system. Our experimental results from x-ray photoelectron spectroscopy and scanning tunneling spectroscopy are discussed in light of our first principles-based calculations. A stronger Sr enrichment tendency and a more facile oxygen vacancy formation prevail for the tensile strained LSM surface. The electronic structure of the tensile strained LSM surface exhibits a larger band gap at room temperature, however, a higher tunneling conductance near the Fermi level than the compressively strained LSM at elevated temperatures in oxygen. Our findings suggest lattice strain as a key parameter to tune the reactivity of perovskite transition metal oxides with oxygen in solid oxide fuel cell cathodes. 3) Cation segregation on perovskite oxide surfaces affects vastly the oxygen reduction activity and stability of solid oxide fuel cell (SOFC) cathodes. A unified theory that explains the physical

Phosphorous–vacancy–oxygen defects in silicon

KAUST Repository

Wang, Hao; Chroneos, Alexander; Hall, D.; Schwingenschlö gl, Udo; Sgourou, E. N.

2013-01-01

Electronic structure calculations employing the hybrid functional approach are used to gain fundamental insight in the interaction of phosphorous with oxygen interstitials and vacancies in silicon. It recently has been proposed, based on a binding

Characterisation and modelling of vacancy dynamics in Ni–Mn–Ga ferromagnetic shape memory alloys

Energy Technology Data Exchange (ETDEWEB)

Merida, D., E-mail: david.merida@ehu.es [Fisika Aplikatua II Saila, Euskal Herriko Unibertsitatea UPV/EHU, p.k. 644, 48080 Bilbao (Spain); Elektrizitate eta Elektronika Saila, Euskal Herriko Unibertsitatea UPV/EHU, p.k. 644, 48080 Bilbao (Spain); García, J.A. [Fisika Aplikatua II Saila, Euskal Herriko Unibertsitatea UPV/EHU, p.k. 644, 48080 Bilbao (Spain); BC Materials (Basque Centre for Materials, Application and Nanostructures), 48040 Leioa (Spain); Sánchez-Alarcos, V. [Departamento de Física, Universidad Pública de Navarra, Campus de Arrosadia, 31006 Pamplona (Spain); Pérez-Landazábal, J.I.; Recarte, V. [Departamento de Física, Universidad Pública de Navarra, Campus de Arrosadia, 31006 Pamplona (Spain); Institute for Advanced Materials (INAMAT), Universidad Pública de Navarra, Campus de Arrosadía, 31006 Pamplona (Spain); Plazaola, F. [Elektrizitate eta Elektronika Saila, Euskal Herriko Unibertsitatea UPV/EHU, p.k. 644, 48080 Bilbao (Spain)

2015-08-05

Highlights: • We study the dynamics of vacancies for three different Ni–Mn–Ga alloy samples. • The formation and migration energies have been obtained experimentally. • The entropic factor and the distance a vacancy has to reach a sink are measured. • We present a theoretical model to explain the dynamics of vacancies. • Results are applicable for any thermal treatment and extensible to other alloys. - Abstract: The dynamics of vacancies in Ni–Mn–Ga shape memory alloys has been studied by positron annihilation lifetime spectroscopy. The temperature evolution of the vacancy concentration for three different Ni–Mn–Ga samples, two polycrystalline and one monocrystalline, have been determined. The formation and migration energies and the entropic factors are quite similar in all cases, but vary slightly according to composition. However, the number of jumps a vacancy has to overtake to reach a sink is five times higher in the single crystal. This is an expected result, due to the role that surfaces and grain boundaries should play in balancing the vacancy concentration. In all cases, the initial vacancy concentration for the samples quenched from 1173 K lies between 1000 ppm and 2000 ppm. A phenomenological model able to explain the dynamics of vacancies has been developed in terms of the previous parameters. The model can reproduce the vacancy dynamics for any different kind of thermal history and can be easily extended to other alloys.

First-principles study on migration of vacancy in tungsten

International Nuclear Information System (INIS)

Oda, Yasuhiro; Ito, Atsushi M.; Takayama, Arimichi; Nakamura, Hiroaki

2014-03-01

We calculated di-vacancy binding energies and migration energies of mono-vacancy and di-vacancy in tungsten material using DFT calculation. The mono-vacancy diffuses in [111] direction easily rather than in [001] direction. The migration energies of di-vacancies are almost the same value of the mono-vacancy. The migration of di-vacancy is approximately the same as the migration of mono-vacancy. The di-vacancy binding energies are almost zero or negative. The interactions between two vacancies in tungsten material are repulsive from the second to fifth nearest-neighbor. The vacancies are difficult to aggregate since di-vacancy is less stable than mono-vacancy. (author)

Improved thrombogenicity on oxygen etched Ti6Al4V surfaces

International Nuclear Information System (INIS)

Riedel, Nicholas A.; Smith, Barbara S.; Williams, John D.; Popat, Ketul C.

2012-01-01

Thrombus formation on blood contacting biomaterials continues to be a key factor in initiating a critical mode of failure in implantable devices, requiring immediate attention. In the interest of evaluating a solution for one of the most widely used biomaterials, titanium and its alloys, this study focuses on the use of a novel surface oxidation treatment to improve the blood compatibility. This study examines the possibility of using oblique angle ion etching to produce a high quality oxide layer that enhances blood compatibility on medical grade titanium alloy Ti6Al4V. An X-ray photoelectron spectroscopy (XPS) analysis of these oxygen-rich surfaces confirmed the presence of TiO 2 peaks and also indicated increased surface oxidation as well as a reduction in surface defects. After 2 h of contact with whole human plasma, the oxygen etched substrates demonstrated a reduction in both platelet adhesion and activation as compared to bare titanium substrates. The whole blood clotting behavior was evaluated for up to 45 min, showing a significant decrease in clot formation on oxygen etched substrates. Finally, a bicinchoninic acid (BCA) total protein assay and XPS were used to evaluate the degree of key blood serum protein (fibrinogen, albumin, immunoglobulin G) adsorption on the substrates. The results showed similar protein levels for both the oxygen etched and control substrates. These results indicate that oblique angle oxygen etching may be a promising method to increase the thrombogenicity of Ti6Al4V. - Highlights: ►Oblique angle oxygen ion etching creates a high quality, uniform oxide surface. ►Oxygen etched substrates showed fewer adhered platelets. ►Platelet activation was reduced by the improved oxide surface. ►Oxygen etched substrates exhibited increased whole blood clotting times. ►Although clotting reductions were seen, protein adsorption remained similar.

Indium vacancy induced d0 ferromagnetism in Li-doped In2O3 nanoparticles

Science.gov (United States)

Cao, Haiming; Xing, Pengfei; Zhou, Wei; Yao, Dongsheng; Wu, Ping

2018-04-01

Li-doped In2O3 nanoparticles with room temperature d0 ferromagnetism were prepared by a sol-gel method. X-ray diffraction, X-ray photoelectron spectroscopy and photoluminescence were carried out to investigate the effects of Li incorporation on the lattice defects. As the content of Li increases, non-monotonic changes in shifts of XRD peak (2 2 2) and the intensity ratios of indium vacancies related photoluminescence peak (PII) with respect to oxygen vacancies related peak (PI) are observed. Results show that at low doping level (≤2 at.%) Li prefers to occupy In sites, while with further doping the interstitial sites are more favorable for Li. Combined with the consistent non-monotonic change in saturation magnetization, we think that indium vacancies resulting from Li-doping play an important role in inducing d0 ferromagnetism in our Li-doped In2O3 nanoparticles, and the FM coupling is mainly mediated by the LiIn-ONN-VIn-ONN-LiIn chains.

Surface morphology of laser superheated Pb(100)

Energy Technology Data Exchange (ETDEWEB)

Zhang, Z.H.; Lin, B.; Elsayed-Ali, H.E.

1999-11-01

The change in the surface vacancy density after heating of Pb(100) with {approximately}100 ps laser pulses is investigated using reflection high-energy electron diffraction. The surface vacancy density remains unchanged when the surface is superheated without melting. However, when the laser fluence is high enough to cause surface melting, the surface vacancy density increases. This increase in vacancy density is attributed to fast diffusion of atoms in the liquid film formed on Pb(100) during laser melting.

Surface Wettability of Oxygen Plasma Treated Porous Silicon

Directory of Open Access Journals (Sweden)

Lei Jiang

2014-01-01

Full Text Available Oxygen plasma treatment on porous silicon (p-Si surfaces was studied as a practical and effective means to modify wetting properties of as-fabricated p-Si surfaces, that is, contact angles of the p-Si materials. P-Si samples spanning a wide range of surface nanostructures have been fabricated which were subjected to a series of oxygen plasma treatments. Reduction of the p-Si surface contact angles has been systematically observed, and the surface activation rate constant as a function of different pore geometries has been analyzed to achieve an empirical equation. The underlying diffusion mechanisms have been discussed by taking into account of different pore diameters of p-Si samples. It is envisaged that such an approach as well as the corresponding empirical equation may be used to provide relevant process guidance in order to achieve precise control of p-Si contact angles, which is essential for many p-Si applications especially in biosensor areas.

First principles study of dissolved oxygen water adsorption on Fe (001 surfaces

Directory of Open Access Journals (Sweden)

Dong ZHANG

2018-02-01

Full Text Available In order to study the mechanism of dissolved oxygen content on the surface corrosion behavior of Fe-based heat transfer, the first principle is used to study the adsorption of O2 monomolecular, H2O monolayer and dissolved oxygen system on Fe-based heat transfer surface. The GGA/PBE approximation is used to calculate the adsorption energy, state density and population change during the adsorption process. Calculations prove that when the dissolved oxygen is adsorbed on the Fe-based surface, the water molecule tends to adsorb at the top sites, and the oxygen molecule tends to adsorb at Griffiths. When the H2O molecule adsorbs and interacts on the Fe (001 surface, the charge distribution of the interfacial double electric layer changes to cause the Fe atoms to lose electrons, resulting in the change of the surface potential. When the O2 molecule adsorbs on the Fe (001 crystal surfaces, the electrons on the Fe (001 surface are lost and the surface potential increases. O2 molecule and the surface of the Fe atoms are prone to electron transfer, in which O atom's 2p orbit for the adsorption of O2 molecule on Fe (001 crystal surface play a major role. With the increase of the proportion of O2 molecule in the dissolved oxygen water, the absolute value of the adsorption energy increases, and the interaction of the Fe-based heat transfer surface is stronger. This study explores the influence law of different dissolved oxygen on the Fe base heat exchange surface corrosion, and the base metal corrosion mechanism for experimental study provides a theoretical reference.

Solute-vacancy binding in aluminum

International Nuclear Information System (INIS)

Wolverton, C.

2007-01-01

Previous efforts to understand solute-vacancy binding in aluminum alloys have been hampered by a scarcity of reliable, quantitative experimental measurements. Here, we report a large database of solute-vacancy binding energies determined from first-principles density functional calculations. The calculated binding energies agree well with accurate measurements where available, and provide an accurate predictor of solute-vacancy binding in other systems. We find: (i) some common solutes in commercial Al alloys (e.g., Cu and Mg) possess either very weak (Cu), or even repulsive (Mg), binding energies. Hence, we assert that some previously reported large binding energies for these solutes are erroneous. (ii) Large binding energies are found for Sn, Cd and In, confirming the proposed mechanism for the reduced natural aging in Al-Cu alloys containing microalloying additions of these solutes. (iii) In addition, we predict that similar reduction in natural aging should occur with additions of Si, Ge and Au. (iv) Even larger binding energies are found for other solutes (e.g., Pb, Bi, Sr, Ba), but these solutes possess essentially no solubility in Al. (v) We have explored the physical effects controlling solute-vacancy binding in Al. We find that there is a strong correlation between binding energy and solute size, with larger solute atoms possessing a stronger binding with vacancies. (vi) Most transition-metal 3d solutes do not bind strongly with vacancies, and some are even energetically strongly repelled from vacancies, particularly for the early 3d solutes, Ti and V

Magnetism and metal-insulator transition in oxygen deficient SrTiO3

Science.gov (United States)

Lopez-Bezanilla, Alejandro; Ganesh, P.; Littlewood, Peter

2015-03-01

We report new findings in the electronic structure and magnetism of oxygen vacancies in SrTiO3. By means of first-principles calculations we show that the appearance of magnetism in oxygen-deficient SrTiO3 is not determined solely by the presence of a single oxygen vacancy but by the density of free carriers and the relative proximity of the vacant sites. While an isolated vacancy behaves as a non-magnetic double donor, manipulation of the doping conditions allows the stability of a single donor state with emergent local moments. Strong local lattice distortions enhance the binding of this state. Consequently we find that the free-carrier density and strain are fundamental components to obtaining trapped spin-polarized electrons in oxygen-deficient SrTiO3, which may have important implications in the design of switchable magneto-optic devices. AL-B and PBL were supported by DOE-BES under Contract No. DE-AC02-06CH11357. PG was sponsored by the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory, managed by UT- Battelle, LLC, for the US Department of Energy.

Ab initio study of vacancy formation in cubic LaMnO{sub 3} and SmCoO{sub 3} as cathode materials in solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Olsson, Emilia; Aparicio-Anglès, Xavier [Department of Chemistry, University College London, London WC1H 0AJ (United Kingdom); Leeuw, Nora H. de, E-mail: deleeuwn@cardiff.ac.uk [Department of Chemistry, University College London, London WC1H 0AJ (United Kingdom); School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT (United Kingdom)

2016-07-07

Doped LaMnO{sub 3} and SmCoO{sub 3} are important solid oxide fuel cell cathode materials. The main difference between these two perovskites is that SmCoO{sub 3} has proven to be a more efficient cathode material than LaMnO{sub 3} at lower temperatures. In order to explain the difference in efficiency, we need to gain insight into the materials’ properties at the atomic level. However, while LaMnO{sub 3} has been widely studied, ab initio studies on SmCoO{sub 3} are rare. Hence, in this paper, we perform a comparative DFT + U study of the structural, electronic, and magnetic properties of these two perovskites. To that end, we first determined a suitable Hubbard parameter for the Co d–electrons to obtain a proper description of SmCoO{sub 3} that fully agrees with the available experimental data. We next evaluated the impact of oxygen and cation vacancies on the geometry, electronic, and magnetic properties. Oxygen vacancies strongly alter the electronic and magnetic structures of SmCoO{sub 3}, but barely affect LaMnO{sub 3}. However, due to their high formation energy, their concentrations in the material are very low and need to be induced by doping. Studying the cation vacancy concentration showed that the formation of cation vacancies is less energetically favorable than oxygen vacancies and would thus not markedly influence the performance of the cathode.

Mathematical modeling of oxygen transport in solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Svensson, Ann Mari

1997-12-31

This thesis develops mathematical models to describe the electrochemical performance of a solid oxide fuel cell cathode based on electrochemical kinetics and mass transfer. The individual effects of various coupled processes are investigated. A one-dimensional model is developed based on porous electrode theory. Two different mechanisms are investigated for the charge transfer reaction. One of these assumes that intermediately adsorbed oxygen atoms are reduced at the electrode/electrolyte interface, similar to the models proposed for metal electrodes. Simulated polarization curves exhibit limited currents due to depletion of oxygen adsorbates at high cathodic overvoltages. An empirical correlation is confirmed to exist between the limiting current an the oxygen partial pressure, however, a similar correlation often assumed to exist between the measured polarization resistance and the oxygen partial pressure could not be justified. For the other model, oxygen vacancies are assumed to be exchanged directly at the electrode/electrolyte interface. The electrochemical behaviour is improved by reducing the oxygen partial pressure, due to increased vacancy concentration of the electrode material. Simulated polarization curves exhibit Tafel-like slopes in the cathodic direction, which are due to polarization concentration, and not activation polarization in the conventional sense. Anodic limiting currents are predicted due to lack of available free sites for vacancy exchange at the cathode side. The thesis also presents a theoretical treatment of current and potential distributions in simple two-dimensional cell geometries, and a two-dimensional model for a porous electrode-electrolyte system for investigation of the effect of interfacial diffusion of adsorbates along the electrode/electrolyte interface. 172 refs., 60 figs., 11 tabs.

Positron-annihilation study of oxygen-deficient YBa2Cu3Ox (6.3

International Nuclear Information System (INIS)

Tang, C.Q.; Li, B.R.; Chen, A.

1990-01-01

We have measured the positron-lifetime spectra of oxygen-deficient YBa 2 Cu 3 O x for 6.3 m , τ 1 , τ 2 , and I 2 have a significant oxygen-content dependence. It is suggested that there are many kinds of positron states in polycrystalline YBa 2 Cu 3 O x , the disordering of O(1) vacancies strongly affects positron lifetime, and with gradually decreasing x the average electronic density decreases and the configuration and/or the charge states of the oxygen vacancies change in the region containing Cu(1)-O(1) chains

Probing of O2 vacancy defects and correlated magnetic, electrical and photoresponse properties in indium-tin oxide nanostructures by spectroscopic techniques

Science.gov (United States)

Ghosh, Shyamsundar; Dev, Bhupendra Nath

2018-05-01

Indium-tin oxide (ITO) 1D nanostructures with tunable morphologies i.e. nanorods, nanocombs and nanowires are grown on c-axis (0 0 0 1) sapphire (Al2O3) substrate in oxygen deficient atmosphere through pulsed laser deposition (PLD) technique and the effect of oxygen vacancies on optical, electrical, magnetic and photoresponse properties is investigated using spectroscopic methods. ITO nanostructures are found to be enriched with significant oxygen vacancy defects as evident from X-ray photoelectron and Raman spectroscopic analysis. Photoluminescence spectra exhibited intense mid-band blue emission at wavelength of region of 400-450 nm due to the electronic transition from conduction band maxima (CBM) to the singly ionized oxygen-vacancy (VO+) defect level within the band-gap. Interestingly, ITO nanostructures exhibited significant room-temperature ferromagnetism (RTFM) and the magnetic moment found proportional to concentration of VO+ defects which indicates VO+ defects are mainly responsible for the observed RTFM in nanostructures. ITO nanowires being enriched with more VO+ defects exhibited strongest RTFM as compared to other morphologies. Current voltage (I-V) characteristics of ITO nanostructures showed an enhancement of current under UV light as compared to dark which indicates such 1D nanostructure can be used as photovoltaic material. Hence, the study shows that there is ample opportunity to tailor the properties of ITOs through proper defect engineering's and such photosensitive ferromagnetic semiconductors might be promising for spintronic and photovoltaic applications.

Improved thrombogenicity on oxygen etched Ti6Al4V surfaces

Energy Technology Data Exchange (ETDEWEB)

Riedel, Nicholas A. [Department of Mechanical Engineering, Colorado State University, Fort Collins, CO 80523 (United States); Smith, Barbara S. [School of Biomedical Engineering, Colorado State University, Fort Collins, CO 80523 (United States); Williams, John D. [Department of Mechanical Engineering, Colorado State University, Fort Collins, CO 80523 (United States); Popat, Ketul C., E-mail: ketul.popat@colostate.edu [Department of Mechanical Engineering, Colorado State University, Fort Collins, CO 80523 (United States); School of Biomedical Engineering, Colorado State University, Fort Collins, CO 80523 (United States)

2012-07-01

Thrombus formation on blood contacting biomaterials continues to be a key factor in initiating a critical mode of failure in implantable devices, requiring immediate attention. In the interest of evaluating a solution for one of the most widely used biomaterials, titanium and its alloys, this study focuses on the use of a novel surface oxidation treatment to improve the blood compatibility. This study examines the possibility of using oblique angle ion etching to produce a high quality oxide layer that enhances blood compatibility on medical grade titanium alloy Ti6Al4V. An X-ray photoelectron spectroscopy (XPS) analysis of these oxygen-rich surfaces confirmed the presence of TiO{sub 2} peaks and also indicated increased surface oxidation as well as a reduction in surface defects. After 2 h of contact with whole human plasma, the oxygen etched substrates demonstrated a reduction in both platelet adhesion and activation as compared to bare titanium substrates. The whole blood clotting behavior was evaluated for up to 45 min, showing a significant decrease in clot formation on oxygen etched substrates. Finally, a bicinchoninic acid (BCA) total protein assay and XPS were used to evaluate the degree of key blood serum protein (fibrinogen, albumin, immunoglobulin G) adsorption on the substrates. The results showed similar protein levels for both the oxygen etched and control substrates. These results indicate that oblique angle oxygen etching may be a promising method to increase the thrombogenicity of Ti6Al4V. - Highlights: Black-Right-Pointing-Pointer Oblique angle oxygen ion etching creates a high quality, uniform oxide surface. Black-Right-Pointing-Pointer Oxygen etched substrates showed fewer adhered platelets. Black-Right-Pointing-Pointer Platelet activation was reduced by the improved oxide surface. Black-Right-Pointing-Pointer Oxygen etched substrates exhibited increased whole blood clotting times. Black-Right-Pointing-Pointer Although clotting reductions were

Adsorption and dehydrogenation of ammonia at the V{sub 2}O{sub 5}(010) surface: DFT cluster studies

Energy Technology Data Exchange (ETDEWEB)

Gruber, Mathis; Hermann, Klaus [Fritz-Haber-Institut der MPG, Berlin (Germany)

2008-07-01

Transition metal oxide catalysts are widely used for selective oxidation reactions. However, in many cases details of the catalytic reaction mechanisms are still under discussion. One prominent example is the ammoxidation of propylene to acrylonitrile at transition metal oxide surfaces (SOHIO process). This catalytic reaction includes, amongst other steps, the adsorption and dehydrogenation of NH{sub x}, x<4, at the catalyst surface. We have performed theoretical studies on these reaction steps where the catalyst is simulated by a finite section of the V{sub 2}O{sub 5}(010) surface. The calculations use density-functional theory combined with clusters modeling the surface and adsorbate system. Calculations for the clean V{sub 2}O{sub 5}(010) surface show that binding energies of the H atom are always significantly larger than of the NH{sub x} species. Further, the substrate is found to lower corresponding dehydrogenation energies compared with values for the gas phase reaction. However, the lowering is too small to make dehydrogenation likely to happen under ammoxidation reaction conditions. This suggests that surface defects such as oxygen vacancies become important for the reaction. Therefore, the role of oxygen vacancies for the dehydrogenation of NH{sub x} is discussed in detail.

Enhanced tunability of electrical and magnetic properties in (La,Sr)MnO3 thin films via field-assisted oxygen vacancy modulation

Science.gov (United States)

Wong, Hon Fai; Ng, Sheung Mei; Cheng, Wang Fai; Liu, Yukuai; Chen, Xinxin; von Nordheim, Danny; Mak, Chee Leung; Dai, Jiyan; Ploss, Bernd; Leung, Chi Wah

2017-12-01

We investigated the tunability of the transport and magnetic properties in 7.5 nm La0.7Sr0.3MnO3 (LSMO) epitaxial films in a field effect geometry with the ferroelectric copolymer P(VDF-TrFE) as the gate insulator. Two different switching behaviors were observed upon application of gate voltages with either high or low magnitudes. The application of single voltage pulses of alternating polarity with an amplitude high enough to switch the remanent polarization of the ferroelectric copolymer led to a 15% change of the resistance of the LSMO channel at temperature 300 K (but less than 1% change at 20 K). A minimal shift of the peak in the resistance-temperature plot was observed, implying that the Curie temperature TC of the manganite layer is not changed. Alternatively, the application of a chain of low voltage pulses was found to shift TC by more than 16 K, and a change of the channel resistance by a 45% was obtained. We attribute this effect to the field-assisted injection and removal of oxygen vacancies in the LSMO layer, which can occur across the thickness of the oxide film. By controlling the oxygen migration, the low-field switching route offers a simple method for modulating the electric and magnetic properties of manganite films.

OXYGEN TRANSPORT CERAMIC MEMBRANES

Energy Technology Data Exchange (ETDEWEB)

Dr. Sukumar Bandopadhyay; Dr. Nagendra Nagabhushana

2000-10-01

This is the third quarterly report on oxygen Transport Ceramic Membranes. In the following, the report describes the progress made by our university partners in Tasks 1 through 6, experimental apparatus that was designed and built for various tasks of this project, thermodynamic calculations, where applicable and work planned for the future. (Task 1) Design, fabricate and evaluate ceramic to metal seals based on graded ceramic powder/metal braze joints. (Task 2) Evaluate the effect of defect configuration on ceramic membrane conductivity and long term chemical and structural stability. (Task 3) Determine materials mechanical properties under conditions of high temperatures and reactive atmospheres. (Task 4) Evaluate phase stability and thermal expansion of candidate perovskite membranes and develop techniques to support these materials on porous metal structures. (Task 5) Assess the microstructure of membrane materials to evaluate the effects of vacancy-impurity association, defect clusters, and vacancy-dopant association on the membrane performance and stability. (Task 6) Measure kinetics of oxygen uptake and transport in ceramic membrane materials under commercially relevant conditions using isotope labeling techniques.

The role of oxygen during the catalytic oxidation of ammonia on Co{sub 3}O{sub 4}(1 0 0)

Energy Technology Data Exchange (ETDEWEB)

Shojaee, Kambiz; Haynes, Brian S.; Montoya, Alejandro, E-mail: alejandro.montoya@sydney.edu.au

2014-10-15

Graphical abstract: - Highlights: • Ammonia oxidation on Co{sub 3}O{sub 4}(1 0 0) surface is studied using Density Functional Theory. • The role of lattice O, on-surface O and OH in the dehydrogenation of ammonia is clarified. • NO and H{sub 2}O are the main products of ammonia oxidation on Co{sub 3}O{sub 4}(1 0 0). • The Co{sub 3}O{sub 4} surface is itself capable of oxidising NH{sub 3} to NO using the lattice O, opening the way for a Mars–van Krevelen mechanism of reaction. - Abstract: The adsorption selectivity and dehydrogenation energy barriers of NH{sub 3}, NH{sub 2} and NH on the (1 0 0) surface planes of Co{sub 3}O{sub 4} are determined by means of density functional methods. Stepwise hydrogen abstraction is effected by lattice O{sup 3o} associated with octahedrally coordinated surface Co atoms. The final H-abstraction, from NH, leads directly to the formation of gaseous product NO with the creation of a lattice oxygen vacancy. Reaction of this vacancy with gas-phase O{sub 2} repairs the vacancy and creates surface-adsorbed O{sup *} which is also capable of abstracting H from NH{sub 3}{sup *}, NH{sub 2}{sup *} and NH{sup *}, the final step leading to directly again to NO formation. The mobile surface OH{sup *} formed from the O{sup *}-mediated abstraction steps is also capable of abstracting H from the NH{sub x}{sup *} species, leading ultimately to surface N{sup *} which then easily extracts a lattice O{sup 3o} to form NO and a new vacancy. The overall mechanism to form NO is a complex cycle of lattice- and surface-mediated abstractions. The hydrogen budget in the reaction shows corresponding complexity. Surface H{sup *} (formed when lattice O{sup 3o} abstracts H from NH{sub x}) is stable and immobile but it can be abstracted by surface OH{sup *} to form water. OH{sup *} disproportionation reaction also forms water.

Surface core level shifts of clean and oxygen covered Ir(111)

Energy Technology Data Exchange (ETDEWEB)

Bianchi, M; Cassese, D; Cavallin, A; Comin, R; Orlando, F; Postregna, L [Universita degli Studi di Trieste, Via A Valerio 2, 34127, Trieste (Italy); Golfetto, E; Baraldi, A [Dipartimento di Fisica e CENMAT, Universita degli Studi di Trieste, Via A Valerio 2, 34127, Trieste (Italy); Lizzit, S [Sincrotrone Trieste S.C.p.A., S.S. 14 Km 163.5, 34012 Trieste (Italy)], E-mail: alessandro.baraldi@elettra.trieste.it

2009-06-15

We present the results of high resolution core level photoelectron spectroscopy employed to investigate the electronic structure of clean and oxygen covered Ir(111) surface. Ir 4f{sub 7/2} core level spectra are shown to be very sensitive to the local atomic environment. For the clean surface we detected two distinct components shifted by 550 meV, originated by surface and bulk atoms. The larger Gaussian width of the bulk component is explained as due to experimentally unresolved subsurface components. In order to determine the relevance of the phonon contribution we examined the thermal behaviour of the core level lineshape using the Hedin-Rosengren theory. From the phonon-induced spectral broadening we found the Debye temperature of bulk and surface atoms to be 298 and 181 K, respectively, which confirms the softening of the vibrational modes at the surface. Oxygen adsorption leads to the appearance of new surface core level components at -200 meV and +230 meV, which are interpreted as due to first-layer Ir atoms differently coordinated with oxygen. The coverage dependence of these components demonstrates that the oxygen saturation corresponds to 0.38 ML, in good agreement with recent density functional theory calculations.

Origin of room temperature ferromagnetism in SnO{sub 2} films

Energy Technology Data Exchange (ETDEWEB)

Li, Jing [School of Materials Science and Engineering, State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027 (China); College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018 (China); National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093 (China); Bai, Guohua; Jiang, Yinzhu [School of Materials Science and Engineering, State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027 (China); Du, Youwei [National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093 (China); Wu, Chen, E-mail: chen_wu@zju.edu.cn [School of Materials Science and Engineering, State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027 (China); Yan, Mi, E-mail: mse_yanmi@zju.edu.cn [School of Materials Science and Engineering, State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027 (China)

2017-03-15

SnO{sub 2} films exhibiting room temperature ferromagnetism (RTFM) have been prepared on Si (001) by pulsed laser deposition. The saturation magnetization (M{sub s}) of the films experiences a decreasing trend followed by increasing with the growth temperature increased from RT to 400 ℃. The growth temperature affects both the concentration and the location of the oxygen vacancies as the origin of the RTFM. With lower growth temperatures (<300 ℃), more oxygen vacancies exist in the inner film for the samples with less crystallinity, resulting in enhanced magnetism. Higher deposition temperature leads to less oxygen vacancies in the inner film but more oxygen defects at the film surface, which is also beneficial to achieve greater magnetism. Various oxygen pressures during growth and post-annealing have also been used to confirm the role of oxygen vacancies. The study demonstrates that the surface oxygen defects and the positively charged monovalent O vacancies (V{sub O}{sup +}) in the inner film are the origin of the magnetism in SnO{sub 2} films. - Highlights: • SnO{sub 2} films exhibiting room temperature ferromagnetism (RTFM) have been prepared on Si (001) by pulsed laser deposition. • Growth temperature, oxygen pressure and annealing affect the growth of SnO{sub 2} films. • Both the concentration and location of the oxygen vacancies play critical roles in the magnetization.

Chip-integrated plasmonic cavity-enhanced single nitrogen-vacancy center emission

DEFF Research Database (Denmark)

Siampour, Hamidreza; Kumar, Shailesh; Bozhevolnyi, Sergey I.

2017-01-01

High temporal stability and spin dynamics of individual nitrogen-vacancy (NV) centers in diamond crystals make them one of the most promising quantum emitters operating at room temperature. We demonstrate a chip-integrated cavity-coupled emission into propagating surface plasmon polariton (SPP...

Tungsten oxides. I. Effects of oxygen vacancies and doping on electronic and optical properties of different phases of WO3

Science.gov (United States)

Migas, D. B.; Shaposhnikov, V. L.; Rodin, V. N.; Borisenko, V. E.

2010-11-01

In this part we present results of our ab initio calculations indicating that dispersion of the bands near the gap region for different phases of WO3 (namely, ɛ-WO3, δ-WO3, γ-WO3, β-WO3, orth-WO3, α-WO3, and hex-WO3) is rather close. The rapid increase in the absorption coefficient starts at the lower energy range for α-WO3 and hex-WO3 than for the other phases in accordance with the calculated band gaps. An oxygen vacancy has turned out to decrease the gap by 0.50 eV and to shift the absorption coefficient to the lower energy range in the room temperature γ-WO3 phase. We have also traced changes caused by molybdenum and sulfur doping of γ-WO3. Only sulfur doped γ-WO3 has been revealed to display the formation of the impurity band along with a sizable reduction in the gap and the shift in the absorption coefficient to the lower energy range.

Oxygen and disorder effect in the magnetic properties of manganite films

Energy Technology Data Exchange (ETDEWEB)

Sirena, M. E-mail: sirenam@ib.cnea.gov.ar; Haberkorn, N.; Granada, M.; Steren, L.B.; Guimpel, J

2004-05-01

We have made a systematic study of the magnetic properties of low doped manganite films submitted to different oxygenation treatments. We have found that oxygenation dynamics depends critically of the strain field in the sample. The T{sub C} and the Mr increase as the oxygen content is increased. A decrease of the coercive field of the LSMO-STO films was observed, indicating that annealing treatments increase the oxygen content reducing oxygen vacancies.

Oxygen and disorder effect in the magnetic properties of manganite films

International Nuclear Information System (INIS)

Sirena, M.; Haberkorn, N.; Granada, M.; Steren, L.B.; Guimpel, J.

2004-01-01

We have made a systematic study of the magnetic properties of low doped manganite films submitted to different oxygenation treatments. We have found that oxygenation dynamics depends critically of the strain field in the sample. The T C and the Mr increase as the oxygen content is increased. A decrease of the coercive field of the LSMO-STO films was observed, indicating that annealing treatments increase the oxygen content reducing oxygen vacancies

Surface Charge-Transfer Doping of Graphene Nanoflakes Containing Double-Vacancy (5-8-5) and Stone-Wales (55-77) Defects through Molecular Adsorption.

Science.gov (United States)

Shakourian-Fard, Mehdi; Jamshidi, Zahra; Kamath, Ganesh

2016-10-18

The adsorption of six electron donor-acceptor (D/A) organic molecules on various sizes of graphene nanoflakes (GNFs) containing two common defects, double-vacancy (5-8-5) and Stone-Wales (55-77), are investigated by means of ab initio DFT [M06-2X(-D3)/cc-pVDZ]. Different D/A molecules adsorb on a defect graphene (DG) surface with binding energies (ΔE b ) of about -12 to -28 kcal mol -1 . The ΔE b values for adsorption of molecules on the Stone-Wales GNF surface are higher than those on the double vacancy GNF surface. Moreover, binding energies increase by about 10 % with an increase in surface size. The nature of cooperative weak interactions is analyzed based on quantum theory of atoms in molecules, noncovalent interactions plot, and natural bond order analyses, and the dominant interaction is compared for different molecules. Electron density population analysis is used to explain the n- and p-type character of defect graphene nanoflakes (DGNFs) and also the change in electronic properties and reactivity parameters of DGNFs upon adsorption of different molecules and with increasing DGNF size. Results indicate that the HOMO-LUMO energy gap (E g ) of DGNFs decreases upon adsorption of molecules. However, by increasing the size of DGNFs, the E g and chemical hardness of all complexes decrease and the electrophilicity index increases. Furthermore, the values of the chemical potential of acceptor-DGNF complexes decrease with increasing size, whereas those of donor-DGNF complexes increase. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Vacancy ordered γ-Fe{sub 2}O{sub 3} nanoparticles functionalized with nanohydroxyapatite: XRD, FTIR, TEM, XPS and Mössbauer studies

Energy Technology Data Exchange (ETDEWEB)

Ramos Guivar, Juan A., E-mail: juan.ramos5@unmsm.edu.pe [Faculty of Physical Sciences, National University of San Marcos, P. O. Box 14- 0149, Lima 14 (Peru); Sanches, Edgar A., E-mail: sanches.ufam@gmail.com [Federal University of Amazonas, Department of Physics, Manaus/AM (Brazil); Bruns, Florian, E-mail: f.bruns@tu-braunschweig.de [Institut für Physik der Kondensierten Materie, Technische Universität Braunschweig, 38110 Braunschweig (Germany); Sadrollahi, Elaheh, E-mail: elahe.sadrollahi@gmail.com [Institut für Physik der Kondensierten Materie, Technische Universität Braunschweig, 38110 Braunschweig (Germany); Morales, M.A., E-mail: marco.moralestorres@gmail.com [Department of Theoretical and Experimental Physics, UFRN, Natal, RN 59078- 970 (Brazil); López, Elvis O., E-mail: lopmezel@gmail.com [Brazilian Center for Research in Physics (CBPF), Rio de Janeiro, RJ 22290-180 (Brazil); Litterst, F. Jochen, E-mail: litterst@cbpf.br [Institut für Physik der Kondensierten Materie, Technische Universität Braunschweig, 38110 Braunschweig (Germany); Brazilian Center for Research in Physics (CBPF), Rio de Janeiro, RJ 22290-180 (Brazil)

2016-12-15

Graphical abstract: Possible bonding configuration in the γ-Fe{sub 2}O{sub 3} nanoparticles functionalized with nanoHAp. - Highlights: • Coprecipitation in alkaline medium for the synthesis of vacancy ordered γ-Fe{sub 2}O{sub 3}@HAp nanocomposite. • Samples were characterized by XRD, FTIR, XPS, TEM, VSM and Mössbauer spectroscopy. • The functionalization is explained with the binding of two oxygens of chemisorbed H{sub 2}O molecules at the common interface of HAp/C{sub 6}H{sub 8}O{sub 7}/γ-Fe{sub 2}O{sub 3}. - Abstract: Vacancy ordered maghemite (γ-Fe{sub 2}O{sub 3}) nanoparticles functionalized with nanohydroxyapatite (HAp – Ca{sub 10}(PO{sub 4}) {sub 6}(OH){sub 2}) have been successfully synthesized using an inexpensive co-precipitation chemical route. Evidence for the presence of vacancy order in maghemite was shown by the superstructure lines observed in X-ray diffraction. The adsorption of carboxyl groups of citric acid (C{sub 6}H{sub 8}O{sub 7}) onto γ-Fe{sub 2}O{sub 3} nanoparticles was investigated by FTIR, XPS and Mössbauer spectroscopy. From XPS surface analysis, two binding energies related to oxygen were attributed to bindings between C{sub 6}H{sub 8}O{sub 7}/γ- Fe{sub 2}O{sub 3} and C{sub 6}H{sub 8}O{sub 7}/HAp from an interfacial reaction promoted by strongly adsorbed H{sub 2}O molecules at the surface of these nanomaterials. Le Bail refinement of the XRD patterns showed the formation of well-crystallized pure tetragonal maghemite before and after functionalization with nanoHAp. The temperature dependence of hyperfine parameters of pure and functionalized γ-Fe{sub 2}O{sub 3} nanoparticles was investigated via Mössbauer spectroscopy. TEM revealed the formation of quasi-spherical γ- Fe{sub 2}O{sub 3} nanoparticles with an average diameter of ca. 12 nm and 16 nm before and after functionalization with nanoHAp in agreement with Le Bail refinement. Magnetometry measurements showed a saturation magnetization of 12 emu/g and a blocking

Study on Surface Structure of U1-yGdyO2-x Using Raman Spectroscopy

International Nuclear Information System (INIS)

Lee, Jeong Mook; Kim, Jan Dee; Youn, Young Sang; Kim, Jong Goo; Ha, Yeong Keong; Kim, Jong Yun

2016-01-01

To understand the structural character of the spent nuclear fuel, rare earth element (REE) doped UO 2±x have been studied as simulated spent fuel. The REE doping effect has influence on the phase stability in U-FP-O system, thermal conductivity and the relevant fuel performance. Raman spectroscopy has been used to investigate surface structure of the nuclear fuel materials, because of its sensitivity, convenience and non-destructive sample preparation. The Raman studies on trivalent-doped UO 2 directly show the defect due to oxygen vacancy that could be created by loss of oxygen for charge compensation. This defect has significant effect on the kinetics of fuel oxidation. In this study, we have been investigated the effect on Gd-doping on the UO 2 structure with Raman spectroscopy to characterize the defect structure of nuclear fuel material. The oxygen deficiencies of pellets were estimated by the relation between the doping concentration and a lattice parameter evaluated from XRD spectra. The Raman spectra of U 1-y GdyO 2-x solid solution pellets show the distorted fluorite structure with defect structure due to oxygen vacancies with increasing Gd contents.

Study on Surface Structure of U1-yGdyO2-x Using Raman Spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Lee, Jeong Mook; Kim, Jan Dee; Youn, Young Sang; Kim, Jong Goo; Ha, Yeong Keong; Kim, Jong Yun [KAERI, Daejeon (Korea, Republic of)

2016-05-15

To understand the structural character of the spent nuclear fuel, rare earth element (REE) doped UO{sub 2±x} have been studied as simulated spent fuel. The REE doping effect has influence on the phase stability in U-FP-O system, thermal conductivity and the relevant fuel performance. Raman spectroscopy has been used to investigate surface structure of the nuclear fuel materials, because of its sensitivity, convenience and non-destructive sample preparation. The Raman studies on trivalent-doped UO{sub 2} directly show the defect due to oxygen vacancy that could be created by loss of oxygen for charge compensation. This defect has significant effect on the kinetics of fuel oxidation. In this study, we have been investigated the effect on Gd-doping on the UO{sub 2} structure with Raman spectroscopy to characterize the defect structure of nuclear fuel material. The oxygen deficiencies of pellets were estimated by the relation between the doping concentration and a lattice parameter evaluated from XRD spectra. The Raman spectra of U{sub 1-y}GdyO{sub 2-x} solid solution pellets show the distorted fluorite structure with defect structure due to oxygen vacancies with increasing Gd contents.

Vacancies in thermal equilibrium in Nb

International Nuclear Information System (INIS)

Nielsen, B.; Lynn, K.G.; Hurst, J.; Vehanen, A.; Schultz, P.J.

1985-06-01

We have measured the diffusion of positrons in Nb(110) in the temperature range from 300K to 2450K utilizing a variable energy positron beam. The purpose was to study the vacancy formation. However, no significant sign of vacancy trapping was observed. This could be due to a high detrapping rate caused by a low positron binding energy or due to a high vacancy formation enthalpy H/sub IV//sup F/. The last possibility is consistent with recent studies of the vacancy migration and with calculation of the positron binding energy. In this case we find the H/sub IV//sup F/ > 3 eV

7 CFR 1221.105 - Vacancies.

Science.gov (United States)

2010-01-01

... Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (MARKETING AGREEMENTS... INFORMATION ORDER Sorghum Promotion, Research, and Information Order Sorghum Promotion, Research, and Information Board § 1221.105 Vacancies. To fill any vacancy occasioned by the death, removal, resignation, or...

Suppression of oxygen diffusion by thin Al2O3 films grown on SrTiO3 studied using a monoenergetic positron beam

International Nuclear Information System (INIS)

Uedono, A.; Kiyohara, M.; Yasui, N.; Yamabe, K.

2005-01-01

The annealing behaviors of oxygen vacancies introduced by the epitaxial growth of thin SrTiO 3 and Al 2 O 3 films on SrTiO 3 substrates were studied by using a monoenergetic positron beam. The films were grown by molecular-beam epitaxy without using an oxidant. The Doppler broadening spectra of the annihilation radiation were measured as a function of the incident positron energy for samples fabricated under various growth conditions. The line-shape parameter S, corresponding to the annihilation of positrons in the substrate, was increased by the film growth, suggesting diffusion of oxygen from the substrate into the film and a resultant introduction of vacancies (mainly oxygen vacancies). A clear correlation between the value of S and the substrate conductivity was obtained. From isochronal annealing experiments, the Al 2 O 3 thin film was found to suppress the penetration of oxygen from the atmosphere for annealing temperatures below 600 deg. C. Degradation of the film's oxygen blocking property occurred due to the annealing at 700 deg. C, and this was attributed to the oxidation of the Al 2 O 3 by the atmosphere and the resultant introduction of vacancy-type defects

Identification of different oxygen species in oxide nanostructures with 17O solid-state NMR spectroscopy

Science.gov (United States)

Wang, Meng; Wu, Xin-Ping; Zheng, Sujuan; Zhao, Li; Li, Lei; Shen, Li; Gao, Yuxian; Xue, Nianhua; Guo, Xuefeng; Huang, Weixin; Gan, Zhehong; Blanc, Frédéric; Yu, Zhiwu; Ke, Xiaokang; Ding, Weiping; Gong, Xue-Qing; Grey, Clare P.; Peng, Luming

2015-01-01

Nanostructured oxides find multiple uses in a diverse range of applications including catalysis, energy storage, and environmental management, their higher surface areas, and, in some cases, electronic properties resulting in different physical properties from their bulk counterparts. Developing structure-property relations for these materials requires a determination of surface and subsurface structure. Although microscopy plays a critical role owing to the fact that the volumes sampled by such techniques may not be representative of the whole sample, complementary characterization methods are urgently required. We develop a simple nuclear magnetic resonance (NMR) strategy to detect the first few layers of a nanomaterial, demonstrating the approach with technologically relevant ceria nanoparticles. We show that the 17O resonances arising from the first to third surface layer oxygen ions, hydroxyl sites, and oxygen species near vacancies can be distinguished from the oxygen ions in the bulk, with higher-frequency 17O chemical shifts being observed for the lower coordinated surface sites. H217O can be used to selectively enrich surface sites, allowing only these particular active sites to be monitored in a chemical process. 17O NMR spectra of thermally treated nanosized ceria clearly show how different oxygen species interconvert at elevated temperature. Density functional theory calculations confirm the assignments and reveal a strong dependence of chemical shift on the nature of the surface. These results open up new strategies for characterizing nanostructured oxides and their applications. PMID:26601133

The surface oxide as a source of oxygen on Rh(1 1 1)

Energy Technology Data Exchange (ETDEWEB)

Lundgren, E. [Department of Synchrotron Radiation Research, Institute of Physics, Lund University, Box 118, S-221 00 Lund (Sweden)]. E-mail: edvin.lundgren@sljus.lu.se; Gustafson, J. [Department of Synchrotron Radiation Research, Institute of Physics, Lund University, Box 118, S-221 00 Lund (Sweden); Resta, A. [Department of Synchrotron Radiation Research, Institute of Physics, Lund University, Box 118, S-221 00 Lund (Sweden); Weissenrieder, J. [Department of Synchrotron Radiation Research, Institute of Physics, Lund University, Box 118, S-221 00 Lund (Sweden); Mikkelsen, A. [Department of Synchrotron Radiation Research, Institute of Physics, Lund University, Box 118, S-221 00 Lund (Sweden); Andersen, J.N. [Department of Synchrotron Radiation Research, Institute of Physics, Lund University, Box 118, S-221 00 Lund (Sweden); Koehler, L. [Institut fuer Materialphysik and Centre for Computational Materials Science, Universitaet Wien, A-1090 Vienna (Austria); Kresse, G. [Institut fuer Materialphysik and Centre for Computational Materials Science, Universitaet Wien, A-1090 Vienna (Austria); Klikovits, J. [Institut fuer Allgemeine Physik, Technische Universitaet Wien, A-1040 Vienna (Austria); Biederman, A. [Institut fuer Allgemeine Physik, Technische Universitaet Wien, A-1040 Vienna (Austria); Schmid, M. [Institut fuer Allgemeine Physik, Technische Universitaet Wien, A-1040 Vienna (Austria); Varga, P. [Institut fuer Allgemeine Physik, Technische Universitaet Wien, A-1040 Vienna (Austria)

2005-06-15

The reduction of a thin surface oxide on the Rh(1 1 1) surface by CO is studied in situ by photoemission spectroscopy, scanning tunneling microscopy, and density functional theory. CO molecules are found not to adsorb on the surface oxide at a sample temperature of 100 K, in contrast to on the clean and chemisorbed oxygen covered surface. Despite this behavior, the surface oxide may still be reduced by CO, albeit in a significantly different fashion as compared to the reduction of a phase containing only chemisorbed on surface oxygen. The experimental observations combined with theoretical considerations concerning the stability of the surface oxide, result in a model of the reduction process at these pressures suggesting that the surface oxide behaves as a source of oxygen for the CO-oxidation reaction.

Plasma treatment effect on charge carrier concentrations and surface traps in a-InGaZnO thin-film transistors

Energy Technology Data Exchange (ETDEWEB)

Kim, Jae-Sung; Xing Piao, Ming; Jang, Ho-Kyun; Kim, Gyu-Tae, E-mail: gtkim@korea.ac.kr [School of Electrical Engineering, Korea University, Seoul 136-701 (Korea, Republic of); Joo, Min-Kyu [School of Electrical Engineering, Korea University, Seoul 136-701 (Korea, Republic of); IMEP-LAHC, Grenoble INP, Minatec, CS 50257, 38016 Grenoble (France); Ahn, Seung-Eon [School of Electrical Engineering, Korea University, Seoul 136-701 (Korea, Republic of); Samsung Advanced Institute of Technology, Samsung Electronics Corporations, Yongin, Gyeonggi-Do 446-712 (Korea, Republic of); Choi, Yong-Hee [School of Electrical Engineering, Korea University, Seoul 136-701 (Korea, Republic of); Semiconductor R and D Center, Samsung Electronics, Hwasung, Gyeonggi-do 445-701 (Korea, Republic of)

2014-03-21

Various plasma treatment effects such as oxygen (O{sub 2}), nitrogen (N{sub 2}), and argon (Ar) on amorphous indium gallium zinc oxide thin-film transistors (a-IGZO TFTs) are investigated. To study oxygen stoichiometry in a-IGZO TFTs with respect to various plasma environments, X-ray photoelectron spectroscopy was employed. The results showed that oxygen vacancies were reduced by O{sub 2} and N{sub 2} plasmas while they were increased after Ar plasma treatment. Additionally, the effects of plasma treatment on trap distribution in bulk and surface channels were explored by means of low-frequency noise analysis. Details of the mechanisms used for generating and restoring traps on the surface and bulk channel are presented.

Phosphorous–vacancy–oxygen defects in silicon

KAUST Repository

Wang, Hao

2013-07-30

Electronic structure calculations employing the hybrid functional approach are used to gain fundamental insight in the interaction of phosphorous with oxygen interstitials and vacancies in silicon. It recently has been proposed, based on a binding energy analysis, that phosphorous–vacancy–oxygen defects may form. In the present study we investigate the stability of this defect as a function of the Fermi energy for the possible charge states. Spin polarization is found to be essential for the charge neutral defect.

Changing vacancy balance in ZnO by tuning synthesis between zinc/oxygen lean conditions

Science.gov (United States)

Venkatachalapathy, Vishnukanthan; Galeckas, Augustinas; Zubiaga, Asier; Tuomisto, Filip; Kuznetsov, Andrej Yu.

2010-08-01

The nature of intrinsic defects in ZnO films grown by metal organic vapor phase epitaxy was studied by positron annihilation and photoluminescence spectroscopy techniques. The supply of Zn and O during the film synthesis was varied by applying different growth temperatures (325-485 °C), affecting decomposition of the metal organic precursors. The microscopic identification of vacancy complexes was derived from a systematic variation in the defect balance in accordance with Zn/O supply trends.

Surface modification of polystyrene with atomic oxygen radical anions-dissolved solution

International Nuclear Information System (INIS)

Wang Lian; Yan Lifeng; Zhao Peitao; Torimoto, Yoshifumi; Sadakata, Masayoshi; Li Quanxin

2008-01-01

A novel approach to surface modification of polystyrene (PS) polymer with atomic oxygen radical anions-dissolved solution (named as O - water) has been investigated. The O - water, generated by bubbling of the O - (atomic oxygen radical anion) flux into the deionized water, was characterized by UV-absorption spectroscopy and electron paramagnetic resonance (EPR) spectroscopy. The O - water treatments caused an obvious increase of the surface hydrophilicity, surface energy, surface roughness and also caused an alteration of the surface chemical composition for PS surfaces, which were indicated by the variety of contact angle and material characterization by atomic force microscope (AFM) imaging, field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), and attenuated total-reflection Fourier transform infrared (ATR-FTIR) measurements. Particularly, it was found that some hydrophilic groups such as hydroxyl (OH) and carbonyl (C=O) groups were introduced onto the polystyrene surfaces via the O - water treatment, leading to the increases of surface hydrophilicity and surface energy. The active oxygen species would react with the aromatic ring molecules on the PS surfaces and decompose the aromatic compounds to produce hydrophilic hydroxyl and carbonyl compounds. In addition, the O - water is also considered as a 'clean solution' without adding any toxic chemicals and it is easy to be handled at room temperature. Present method may suit to the surface modification of polymers and other heat-sensitive materials potentially

Diffusion in a pure, high-vacancy-content crystal

International Nuclear Information System (INIS)

McKee, R.A.

1981-01-01

The idea that vacancies can follow a nonrandom walk in a solid has been developed and put into a quantitative form for diffusion in a pure, high-vacancy-content crystal. Intrinsic and tracer diffusion in a metal have been analyzed, and the electrical mobility in an ionic solid has been expressed in terms of the tracer diffusion coefficient and the separate correlation factors for atoms and vacancies. The description uses classical methods of diffusion theory, and generalized results that account for nonrandom vacancy walk have been shown to reduce to those obtained by Howard and Lidiard in a system where the vacancy moves randomly as an isolated point defect. Experimental data for carbon diffusion in fcc iron have been examined to illustrate an interstitial-vacancy analogy that was used in this analysis, and the general result has been applied specifically to discuss vacancy diffusion in Fe/sub 1-x/S

Quantum Control of a Nitrogen-Vacancy Center using Surface Acoustic Waves in the Resolved Sideband Limit

Science.gov (United States)

Golter, David; Oo, Thein; Amezcua, Maira; Wang, Hailin

Micro-electromechanical systems research is producing increasingly sophisticated tools for nanophononic applications. Such technology is well-suited for achieving chip-based, integrated acoustic control of solid-state quantum systems. We demonstrate such acoustic control in an important solid-state qubit, the diamond nitrogen-vacancy (NV) center. Using an interdigitated transducer to generate a surface acoustic wave (SAW) field in a bulk diamond, we observe phonon-assisted sidebands in the optical excitation spectrum of a single NV center. This exploits the strong strain sensitivity of the NV excited states. The mechanical frequencies far exceed the relevant optical linewidths, reaching the resolved-sideband regime. This enables us to use the SAW field for driving Rabi oscillations on the phonon-assisted optical transition. These results stimulate the further integration of SAW-based technologies with the NV center system.

Reconciling in vivo and in vitro kinetics of the polymorphic transformation in zirconia-toughened alumina for hip joints: III. Molecular scale mechanisms

Energy Technology Data Exchange (ETDEWEB)

Pezzotti, Giuseppe, E-mail: pezzotti@kit.ac.jp [Ceramic Physics Laboratory, Kyoto Institute of Technology, Sakyo-ku, Matsugasaki, 606-8126 Kyoto (Japan); Bal, B. Sonny [Department of Orthopaedic Surgery, University of Missouri, Columbia, MO 65212 (United States); Amedica Corporation, 1885 West 2100 South, Salt Lake City, UT 84119 (United States); Zanocco, Matteo; Marin, Elia [Ceramic Physics Laboratory, Kyoto Institute of Technology, Sakyo-ku, Matsugasaki, 606-8126 Kyoto (Japan); Sugano, Nobuhiko [Department of Medical Engineering for Treatment of Bone and Joint Disorders, Osaka University, 2-2 Yamadaoka, Suita, Osaka 565-0854 (Japan); McEntire, Bryan J. [Amedica Corporation, 1885 West 2100 South, Salt Lake City, UT 84119 (United States); Zhu, Wenliang, E-mail: wlzhu2002@hotmail.com [Department of Medical Engineering for Treatment of Bone and Joint Disorders, Osaka University, 2-2 Yamadaoka, Suita, Osaka 565-0854 (Japan)

2017-02-01

Understanding the intrinsic reason(s) for the enhanced tetragonal to monoclinic (t → m) polymorphic phase transformation observed on metal-stained surfaces of zirconia-toughened alumina (ZTA) requires detailed knowledge of off-stoichiometry reactions at the molecular scale. In this context, knowledge of the mechanism(s) for oxygen vacancy creation or annihilation at the material surface is a necessary prerequisite. The crucial aspect of the surface destabilization phenomenon, namely the availability of electrons and holes that allow for vacancy creation/annihilation, is elucidated in this paper. Metal-enhanced alterations of the oxygen sublattice in both Al{sub 2}O{sub 3} and ZrO{sub 2} of the ZTA composite play a decisive role in accelerating the polymorphic transformation. According to spectroscopic evidences obtained through nanometer-scale analyses, enhanced annihilation of oxygen vacancies triggers polymorphic transformation in ZrO{sub 2} near the metal stain, while the overall Al{sub 2}O{sub 3} lattice tends to dehydroxylate by forming oxygen vacancies. A mechanism for chemically driven “reactive metastability” is suggested, which results in accelerating the polymorphic transformation. The Al{sub 2}O{sub 3} matrix is found to play a key-role in the ZrO{sub 2} transformation process, with unambiguous confirmation of oxygen and hydrogen transport at the material surface. It is postulated that this transport is mediated by migration of dissociated O and H elements at the surface of the stained transition metal as they become readily available by the thermally activated surrounding. - Graphical abstract: Metal-enhanced alterations of the oxygen sublattice in both Al{sub 2}O{sub 3} and ZrO{sub 2} of the ZTA composite play a decisive role in the polymorphic transformation. According to spectroscopic evidence obtained through nanometer-scale analyses, enhanced annihilation of oxygen vacancies in Al{sub 2}O{sub 3} and ZrO{sub 2} occurs near the metal stain

HYDROGEN VACANCY INTERACTION IN TUNGSTEN

NARCIS (Netherlands)

FRANSENS, [No Value; ELKERIEM, MSA; PLEITER, F

1991-01-01

Hydrogen-vacancy interaction in tungsten was investigated by means of the perturbed angular correlation technique, using the isotope In-111 as a probe. Hydrogen trapping at an In-111-vacancy cluster manifests itself as a change of the local electric field gradient, which gives rise to an observable

Invariance of the mobility edge in anodic titanium oxides

International Nuclear Information System (INIS)

Tit, N.; Halley, J.W.; Shore, H.B.

1992-05-01

We present a theoretical investigation to explain the electronic and optical properties of anodic rutile TiO 2 thin films of different thicknesses (ranging from 5nm to 20nm). There is experimental evidence that the observed gap state at 0.7eV below the edge of conduction-band is due to an oxygen vacancy. For this reason, oxygen vacancies are used as defects in our model. A comparison of the calculated bulk-photoconductivity to photospectroscopy experiment reveals that the films have bulk-like transport properties with a bandgap E g =3.0eV. On the other hand, a fit of the surface density of states to the scanning tunneling microscopy (STM) experiment on the (001) surfaces has suggested a surface defect density of 5% of oxygen vacancies. To resolve this discrepancy, we calculated the dc-conductivity where localization effects are included. Our results show an impurity band formation at about p c =9% of oxygen vacancies. We concluded that the studied films have defect densities below the threshold of impurity band formation. As a consequence the gap states seen in STM are localized (i.e. the oxygen vacancies are playing the role of trapping centers, deep levels) and the mobility edge is invariant. (author). 11 refs, 3 figs

Dynamics of ordering processes in annealed dilute systems: Island formation, vacancies at domain boundaries, and compactification

DEFF Research Database (Denmark)

Shah, Peter Jivan; Mouritsen, Ole G.

1990-01-01

The dynamics of the ordering processes in two-dimensional lattice models with annealed vacancies and nonconserved order parameter is studied as a function of temperature and vacancy concentration by means of Monte Carlo temperature-quenching simulations. The models are Ising antiferromagnets...... with couplings leading to twofold-degenerate as well as fourfold-degenerate ordering. The models are quenched into a phase-separation region, which makes it possible for both types of ordering to observe the following scenario of ordering processes: (i) early-time nucleation and growth of ordered domains, (ii......) intermediate-time trapping of the mobile vacancies at the domain boundaries, and (iii) late-time diffusion of vacancies along the domain-boundary network towards the surface. In the case of high dilution, the ordering processes correspond to early-time island formation and late-time coarsening...

Effect of polar and non-polar surfaces of ZnO nanostructures on photocatalytic properties

International Nuclear Information System (INIS)

Yang Jinghai; Wang Jian; Li Xiuyan; Lang Jihui; Liu Fuzhu; Yang Lili; Zhai Hongju; Gao Ming; Zhao Xiaoting

2012-01-01

Highlights: ► Large-scale arrayed ZnO nanocrystals including ZnO hexagonal platforms and hamburger-like samples have been successfully fabricated by a simple hydrothermal method. ► ZnO with hexagonal platform-like morphology exhibited higher photocatalytic activity compared with that of the hamburger-like ZnO nanostructures. ► The theories of expose surfaces and oxygen vacancies were utilized to explain the photocatalytic mechanism. - Abstract: Large-scale arrayed ZnO nanocrystals with two different expose surfaces, including ZnO hexagonal nanoplatforms with the major expose plane of (0 0 0 1) and hamburger-like samples with the nonpolar planes of {101 ¯ 0} mainly exposed, were successfully fabricated by a simple hydrothermal method. Mechanisms for compare the photocatalytic activity of two typical ZnO nanostructures were systematic explained as the key point in the paper. Compared with the hamburger-like ZnO nanostructures, the ZnO with hexagonal platform-like morphology exhibited improved ability on the photocatalytic degradation of Rhodamine B (RhB) in aqueous solution under UV radiation. The relative higher photocatalytic activity of the ZnO hexagonal nanoplatforms was attributed to the exposed polar surfaces and the content of oxygen vacancy on the nanostructures surface. The Zn-terminated (0 0 0 1) polar face and the surface defects are facile to adsorb O 2− and OH − ions, resulting in a greater production rate of O 2 · − and OH· − , hence promoting the photocatalysis reaction.

Atomic structure and composition of the yttria-stabilized zirconia (111) surface.

Science.gov (United States)

Vonk, Vedran; Khorshidi, Navid; Stierle, Andreas; Dosch, Helmut

2013-06-01

Anomalous and nonanomalous surface X-ray diffraction is used to investigate the atomic structure and composition of the yttria-stabilized zirconia (YSZ)(111) surface. By simulation it is shown that the method is sensitive to Y surface segregation, but that the data must contain high enough Fourier components in order to distinguish between different models describing Y/Zr disorder. Data were collected at room temperature after two different annealing procedures. First by applying oxidative conditions at 10 - 5  mbar O 2 and 700 K to the as-received samples, where we find that about 30% of the surface is covered by oxide islands, which are depleted in Y as compared with the bulk. After annealing in ultrahigh vacuum at 1270 K the island morphology of the surface remains unchanged but the islands and the first near surface layer get significantly enriched in Y. Furthermore, the observation of Zr and oxygen vacancies implies the formation of a porous surface region. Our findings have important implications for the use of YSZ as solid oxide fuel cell electrode material where yttrium atoms and zirconium vacancies can act as reactive centers, as well as for the use of YSZ as substrate material for thin film and nanoparticle growth where defects control the nucleation process.

A close correlation between induced ferromagnetism and oxygen deficiency in Fe doped In2O3

International Nuclear Information System (INIS)

Singhal, R.K.; Samariya, A.; Kumar, Sudhish; Sharma, S.C.; Xing, Y.T.; Deshpande, U.P.; Shripathi, T.; Saitovitch, E.

2010-01-01

We report on the reversible manipulation of room temperature ferromagnetism in Fe (5%) doped In 2 O 3 polycrystalline magnetic semiconductor. The X-ray diffraction and photoemission measurements confirm that the Fe ions are well incorporated into the lattice, substituting the In 3+ ions. The magnetization measurements show that the host In 2 O 3 has a diamagnetic ground state, while it shows weak ferromagnetism at 300 K upon Fe doping. The as-prepared sample was then sequentially annealed in hydrogen, air, vacuum and finally in air. The ferromagnetic signal shoots up by hydrogenation as well as vacuum annealing and bounces back upon re-annealing the samples in air. The sequence of ferromagnetism shows a close inter-relationship with the behavior of oxygen vacancies (V o ). The Fe ions tend to a transform from 3+ to 2+ state during the giant ferromagnetic induction, as revealed by photoemission spectroscopy. A careful characterization of the structure, purity, magnetic, and transport properties confirms that the ferromagnetism is due to neither impurities nor clusters but directly related to the oxygen vacancies. The ferromagnetism can be reversibly controlled by these vacancies while a parallel variation of carrier concentration, as revealed by resistance measurements, appears to be a side effect of the oxygen vacancy variation.

The influence of positron trapping at vacancies on a pattern of the Fermi surface of #betta#-brass studied by positron annihilation

International Nuclear Information System (INIS)

Rozenfeld, B.; Chabik, S.; Pajak, J.

1982-01-01

Angular correlations of positron annihilation quanta (ACPAQ) have been measured for differently oriented monocrystalline samples of the ordered #betta#-brass under conditions permitting the neglecting of the trapping of positrons at vacancies as well as in the case when almost all the positrons annihilate being trapped at vacancies. It has been shown that trapping of positrons at vacancies can make the observation of the directional anisotropy in electron momentum distribution impossible. (Auth.)

Vacancy complexes induce long-range ferromagnetism in GaN

KAUST Repository

Zhang, Zhenkui

2014-11-14

By means of density functional theory, we argue that ferromagnetism in GaN can be induced by vacancy complexes. Spin polarization originates from the charge compensation between neutral N and Ga vacancies. Defect formation energy calculations predict that a vacancy complex of two positively charged N vacancies and one doubly negative Ga vacancy is likely to form. This defect complex induces a net moment of 1 μB, which is localized around the negative Ga center and exhibits pronounced in-plane ferromagnetic coupling. In contrast to simple Ga vacancy induced ferromagnetism, the proposed picture is in line with the fact that N vacancies have a low formation energy. Formation energies indicate mutual stabilization of the intrinsic defects in GaN.

Vacancy complexes induce long-range ferromagnetism in GaN

Energy Technology Data Exchange (ETDEWEB)

Zhang, Zhenkui; Schwingenschlögl, Udo, E-mail: Udo.Schwingenschlogl@kaust.edu.sa, E-mail: Iman.Roqan@kaust.edu.sa; Roqan, Iman S., E-mail: Udo.Schwingenschlogl@kaust.edu.sa, E-mail: Iman.Roqan@kaust.edu.sa [Physical Sciences and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900 (Saudi Arabia)

2014-11-14

By means of density functional theory, we argue that ferromagnetism in GaN can be induced by vacancy complexes. Spin polarization originates from the charge compensation between neutral N and Ga vacancies. Defect formation energy calculations predict that a vacancy complex of two positively charged N vacancies and one doubly negative Ga vacancy is likely to form. This defect complex induces a net moment of 1 μ{sub B}, which is localized around the negative Ga center and exhibits pronounced in-plane ferromagnetic coupling. In contrast to simple Ga vacancy induced ferromagnetism, the proposed picture is in line with the fact that N vacancies have a low formation energy. Formation energies indicate mutual stabilization of the intrinsic defects in GaN.

Vacancy complexes induce long-range ferromagnetism in GaN

KAUST Repository

Zhang, Zhenkui; Schwingenschlö gl, Udo; Roqan, Iman S.

2014-01-01

By means of density functional theory, we argue that ferromagnetism in GaN can be induced by vacancy complexes. Spin polarization originates from the charge compensation between neutral N and Ga vacancies. Defect formation energy calculations predict that a vacancy complex of two positively charged N vacancies and one doubly negative Ga vacancy is likely to form. This defect complex induces a net moment of 1 μB, which is localized around the negative Ga center and exhibits pronounced in-plane ferromagnetic coupling. In contrast to simple Ga vacancy induced ferromagnetism, the proposed picture is in line with the fact that N vacancies have a low formation energy. Formation energies indicate mutual stabilization of the intrinsic defects in GaN.

Structural/surface characterization and catalytic evaluation of rare-earth (Y, Sm and La) doped ceria composite oxides for CH{sub 3}SH catalytic decomposition

Energy Technology Data Exchange (ETDEWEB)

He, Dedong; Chen, Dingkai; Hao, Husheng; Yu, Jie; Liu, Jiangping; Lu, Jichang; Liu, Feng [Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming, 650500 (China); Wan, Gengping [Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming, 650500 (China); Research Center for Analysis and Measurement, Hainan University, Haikou, 570228 (China); He, Sufang [Research Center for Analysis and Measurement, Kunming University of Science and Technology, Kunming, 650093 (China); Luo, Yongming, E-mail: environcatalysis222@yahoo.com [Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming, 650500 (China)

2016-12-30

Highlights: • Ce{sub 0.75}RE{sub 0.25}O{sub 2-δ} (RE = Y, Sm and La) were synthesized by citrate complexation method. • Ce{sub 0.75}Y{sub 0.25}O{sub 2-δ} exhibited the best stability for the decomposition of CH{sub 3}SH. • Cation radius played a key role in determining structure and surface characteristics. • Catalytic behavior depended on synergistic role of oxygen vacancies and basic sites. • Ce{sub 2}S{sub 3} accumulation on the surface was responsible for the deactivation of catalyst. - Abstract: A series of rare earth (Y, Sm and La) doped ceria composite oxides and pure CeO{sub 2} were synthesized and evaluated by conducting CH{sub 3}SH catalytic decomposition test. Several characterization studies, including XRD, BET, Raman, H{sub 2}-TPR, XPS, FT-IR, CO{sub 2}-TPD and CH{sub 3}SH-TPD, were undertaken to correlate structural and surface properties of the obtained ceria-based catalysts with their catalytic performance for CH{sub 3}SH decomposition. More oxygen vacancies and increased basic sites exhibited in the rare earth doped ceria catalysts. Y doped ceria sample (Ce{sub 0.75}Y{sub 0.25}O{sub 2-δ}), with a moderate increase in basic sites, contained more oxygen vacancies. More structural defects and active sites could be provided, and a relatively small amount of sulfur would accumulate, which resulted in better catalytic performance. The developed catalyst presented good catalytic behavior with stability very similar to that of typical zeolite-based catalysts reported previously. However, La doped ceria catalyst (Ce{sub 0.75}La{sub 0.25}O{sub 2-δ}) with the highest alkalinity was not the most active one. More sulfur species would be adsorbed and a large amount of cerium sulfide species (Ce{sub 2}S{sub 3}) would accumulate, which caused deactivation of the catalysts. The combined effect of increased oxygen vacancies and alkalinity led to the catalytic stability of Ce{sub 0.75}Sm{sub 0.25}O{sub 2-δ} sample was comparable to that of pure Ce

Reactivity of chemisorbed oxygen atoms and their catalytic consequences during CH4-O2 catalysis on supported Pt clusters.

Science.gov (United States)

Chin, Ya-Huei Cathy; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

2011-10-12

Kinetic and isotopic data and density functional theory treatments provide evidence for the elementary steps and the active site requirements involved in the four distinct kinetic regimes observed during CH(4) oxidation reactions using O(2), H(2)O, or CO(2) as oxidants on Pt clusters. These four regimes exhibit distinct rate equations because of the involvement of different kinetically relevant steps, predominant adsorbed species, and rate and equilibrium constants for different elementary steps. Transitions among regimes occur as chemisorbed oxygen (O*) coverages change on Pt clusters. O* coverages are given, in turn, by a virtual O(2) pressure, which represents the pressure that would give the prevalent steady-state O* coverages if their adsorption-desorption equilibrium was maintained. The virtual O(2) pressure acts as a surrogate for oxygen chemical potentials at catalytic surfaces and reflects the kinetic coupling between C-H and O═O activation steps. O* coverages and virtual pressures depend on O(2) pressure when O(2) activation is equilibrated and on O(2)/CH(4) ratios when this step becomes irreversible as a result of fast scavenging of O* by CH(4)-derived intermediates. In three of these kinetic regimes, C-H bond activation is the sole kinetically relevant step, but occurs on different active sites, which evolve from oxygen-oxygen (O*-O*), to oxygen-oxygen vacancy (O*-*), and to vacancy-vacancy (*-*) site pairs as O* coverages decrease. On O*-saturated cluster surfaces, O*-O* site pairs activate C-H bonds in CH(4) via homolytic hydrogen abstraction steps that form CH(3) groups with significant radical character and weak interactions with the surface at the transition state. In this regime, rates depend linearly on CH(4) pressure but are independent of O(2) pressure. The observed normal CH(4)/CD(4) kinetic isotope effects are consistent with the kinetic-relevance of C-H bond activation; identical (16)O(2)-(18)O(2) isotopic exchange rates in the presence or

Vacancy decay in endohedral atoms

International Nuclear Information System (INIS)

Amusia, M. Ya.; Baltenkov, A. S.

2006-01-01

It is demonstrated that the fullerene shell dramatically affects the radiative and Auger vacancy decay of an endohedral atom A-C 60 . The collectivized electrons of the C 60 shell add new possibilities for radiative and nonradiative decays similar to that in ordinary atoms where the vacancies in the initial and final state almost always belong to different subshells. It is shown that the smallness of the atomic shell radii as compared to that of the fullerene shell provides an opportunity to derive the simple formulas for the probabilities of the electron transitions. It is shown that the radiative and Auger (or Koster-Kronig) widths of the vacancy decay due to electron transition in the atom A in A-C 60 acquire an additional factor that can be expressed via the polarizability of the C 60 at transition energy. It is demonstrated that due to an opening of the nonradiative decay channel for vacancies in subvalent subshells the decay probability increases by five to six orders of magnitude

Correlation between stoichiometry and surface structure of the polar MgAl2O4(100) surface as a function of annealing temperature

DEFF Research Database (Denmark)

Jensen, Thomas Nørregaard; Rasmussen, Morten Karstoft; Knudsen, Jan

2015-01-01

is found to significantly increase as the surface is sputtered and annealed in oxygen at intermediate temperatures ranging from 800-1000 [degree]C. The Al excess is explained by the observed surface structure, where the formation of nanometer sized pits and elongated patches with Al terminated step edges....... The excess of Al and high concentration of octahedral vacancies, very interestingly means, that the top few surface layers of the MgAl2O4(100) adopts a surface structure similar to that of a spinel-like transition Al2O3 film. However, after annealing at a high temperature of 1200 [degree]C, the Al/Mg ratio...... are filled by Mg from the bulk, due to the increased mobility at high annealing temperatures....

Analysis of heterogeneous oxygen exchange and fuel oxidation on the catalytic surface of perovskite membranes

KAUST Repository

Hong, Jongsup

2013-10-01

The catalytic kinetics of oxygen surface exchange and fuel oxidation for a perovskite membrane is investigated in terms of the thermodynamic state in the immediate vicinity of or on the membrane surface. Perovskite membranes have been shown to exhibit both oxygen perm-selectivity and catalytic activity for hydrocarbon conversion. A fundamental description of their catalytic surface reactions is needed. In this study, we infer the kinetic parameters for heterogeneous oxygen surface exchange and catalytic fuel conversion reactions, based on permeation rate measurements and a spatially resolved physical model that incorporates detailed chemical kinetics and transport in the gas-phase. The conservation equations for surface and bulk species are coupled with those of the gas-phase species through the species production rates from surface reactions. It is shown that oxygen surface exchange is limited by dissociative/associative adsorption/desorption of oxygen molecules onto/from the membrane surface. On the sweep side, while the catalytic conversion of methane to methyl radical governs the overall surface reactions at high temperature, carbon monoxide oxidation on the membrane surface is dominant at low temperature. Given the sweep side conditions considered in ITM reactor experiments, gas-phase reactions also play an important role, indicating the significance of investigating both homogeneous and heterogeneous chemistry and their coupling when examining the results. We show that the local thermodynamic state at the membrane surface should be considered when constructing and examining models of oxygen permeation and heterogeneous chemistry. © 2013 Elsevier B.V.

Analysis of heterogeneous oxygen exchange and fuel oxidation on the catalytic surface of perovskite membranes

KAUST Repository

Hong, Jongsup; Kirchen, Patrick; Ghoniem, Ahmed F.

2013-01-01

The catalytic kinetics of oxygen surface exchange and fuel oxidation for a perovskite membrane is investigated in terms of the thermodynamic state in the immediate vicinity of or on the membrane surface. Perovskite membranes have been shown to exhibit both oxygen perm-selectivity and catalytic activity for hydrocarbon conversion. A fundamental description of their catalytic surface reactions is needed. In this study, we infer the kinetic parameters for heterogeneous oxygen surface exchange and catalytic fuel conversion reactions, based on permeation rate measurements and a spatially resolved physical model that incorporates detailed chemical kinetics and transport in the gas-phase. The conservation equations for surface and bulk species are coupled with those of the gas-phase species through the species production rates from surface reactions. It is shown that oxygen surface exchange is limited by dissociative/associative adsorption/desorption of oxygen molecules onto/from the membrane surface. On the sweep side, while the catalytic conversion of methane to methyl radical governs the overall surface reactions at high temperature, carbon monoxide oxidation on the membrane surface is dominant at low temperature. Given the sweep side conditions considered in ITM reactor experiments, gas-phase reactions also play an important role, indicating the significance of investigating both homogeneous and heterogeneous chemistry and their coupling when examining the results. We show that the local thermodynamic state at the membrane surface should be considered when constructing and examining models of oxygen permeation and heterogeneous chemistry. © 2013 Elsevier B.V.

Remarkable changes in interface O vacancy and metal-oxide bonds in amorphous indium-gallium-zinc-oxide thin-film transistors by long time annealing at 250 °C

International Nuclear Information System (INIS)

Chowdhury, Md Delwar Hossain; Um, Jae Gwang; Jang, Jin

2014-01-01

We have studied the effect of long time post-fabrication annealing on negative bias illumination stress (NBIS) of amorphous indium-gallium-zinc-oxide (a-IGZO) thin-film-transistors. Annealing for 100 h at 250 °C increased the field effect mobility from 14.7 cm 2 /V s to 17.9 cm 2 /V s and reduced the NBIS instability remarkably. Using X-ray photoelectron spectroscopy, the oxygen vacancy and OH were found to exist at the interfaces of a-IGZO with top and bottom SiO 2 . Long time annealing helps to decrease the vacancy concentration and increase the metal-oxygen bonds at the interfaces; this leads to increase in the free carrier concentrations in a-IGZO and field-effect mobility. X-ray reflectivity measurement indicated the increment of a-IGZO film density of 5.63 g cm −3 to 5.83 g cm −3 (3.4% increase) by 100 h annealing at 250 °C. The increase in film density reveals the decrease of O vacancy concentration and reduction of weak metal-oxygen bonds in a-IGZO, which substantially helps to improve the NBIS stability

Role of vacancy defects in Al doped ZnO thin films for optoelectronic devices

Science.gov (United States)

Rotella, H.; Mazel, Y.; Brochen, S.; Valla, A.; Pautrat, A.; Licitra, C.; Rochat, N.; Sabbione, C.; Rodriguez, G.; Nolot, E.

2017-12-01

We report on the electrical, optical and photoluminescence properties of industry-ready Al doped ZnO thin films grown by physical vapor deposition, and their evolution after annealing under vacuum. Doping ZnO with Al atoms increases the carrier density but also favors the formation of Zn vacancies, thereby inducing a saturation of the conductivity mechanism at high aluminum content. The electrical and optical properties of these thin layered materials are both improved by annealing process which creates oxygen vacancies that releases charge carriers thus improving the conductivity. This study underlines the effect of the formation of extrinsic and intrinsic defects in Al doped ZnO compound during the fabrication process. The quality and the optoelectronic response of the produced films are increased (up to 1.52 mΩ \\cdotcm and 3.73 eV) and consistent with the industrial device requirements.

Excitation of surface plasmon polariton modes with multiple nitrogen vacancy centers in single nanodiamonds

International Nuclear Information System (INIS)

Kumar, Shailesh; Lausen, Jens L; Andersen, Sebastian K H; Roberts, Alexander S; Radko, Ilya P; Bozhevolnyi, Sergey I; Garcia-Ortiz, Cesar E; Smith, Cameron L C; Kristensen, Anders

2016-01-01

Nitrogen-vacancy (NV) centers in diamonds are interesting due to their remarkable characteristics that are well suited to applications in quantum-information processing and magnetic field sensing, as well as representing stable fluorescent sources. Multiple NV centers in nanodiamonds (NDs) are especially useful as biological fluorophores due to their chemical neutrality, brightness and room-temperature photostability. Furthermore, NDs containing multiple NV centers also have potential in high-precision magnetic field and temperature sensing. Coupling NV centers to propagating surface plasmon polariton (SPP) modes gives a base for lab-on-a-chip sensing devices, allows enhanced fluorescence emission and collection which can further enhance the precision of NV-based sensors. Here, we investigate coupling of multiple NV centers in individual NDs to the SPP modes supported by silver surfaces protected by thin dielectric layers and by gold V-grooves (VGs) produced via the self-terminated silicon etching. In the first case, we concentrate on monitoring differences in fluorescence spectra obtained from a source ND, which is illuminated by a pump laser, and from a scattering ND illuminated only by the fluorescence-excited SPP radiation. In the second case, we observe changes in the average NV lifetime when the same ND is characterized outside and inside a VG. Fluorescence emission from the VG terminations is also observed, which confirms the NV coupling to the VG-supported SPP modes. (paper)

Excitation of surface plasmon polariton modes with multiple nitrogen vacancy centers in single nanodiamonds

Science.gov (United States)

Kumar, Shailesh; Lausen, Jens L.; Garcia-Ortiz, Cesar E.; Andersen, Sebastian K. H.; Roberts, Alexander S.; Radko, Ilya P.; Smith, Cameron L. C.; Kristensen, Anders; Bozhevolnyi, Sergey I.

2016-02-01

Nitrogen-vacancy (NV) centers in diamonds are interesting due to their remarkable characteristics that are well suited to applications in quantum-information processing and magnetic field sensing, as well as representing stable fluorescent sources. Multiple NV centers in nanodiamonds (NDs) are especially useful as biological fluorophores due to their chemical neutrality, brightness and room-temperature photostability. Furthermore, NDs containing multiple NV centers also have potential in high-precision magnetic field and temperature sensing. Coupling NV centers to propagating surface plasmon polariton (SPP) modes gives a base for lab-on-a-chip sensing devices, allows enhanced fluorescence emission and collection which can further enhance the precision of NV-based sensors. Here, we investigate coupling of multiple NV centers in individual NDs to the SPP modes supported by silver surfaces protected by thin dielectric layers and by gold V-grooves (VGs) produced via the self-terminated silicon etching. In the first case, we concentrate on monitoring differences in fluorescence spectra obtained from a source ND, which is illuminated by a pump laser, and from a scattering ND illuminated only by the fluorescence-excited SPP radiation. In the second case, we observe changes in the average NV lifetime when the same ND is characterized outside and inside a VG. Fluorescence emission from the VG terminations is also observed, which confirms the NV coupling to the VG-supported SPP modes.

Direct observation of hopping induced spin polarization current in oxygen deficient Co-doped ZnO by Andreev reflection technique

Energy Technology Data Exchange (ETDEWEB)

Yang, Kung-Shang; Huang, Tzu-Yu; Dwivedi, G.D. [Department of Physics, National Sun Yat-sen University, Kaohsiung, Taiwan (China); Lin, Lu-Kuei; Lee, Shang-Fan [Taiwan Institute of Physics, Academia Sinica, Taipei, Taiwan (China); Sun, Shih-Jye [Department of Applied Physics, National Kaohsiung University, Kaohsiung, Taiwan (China); Chou, Hsiung, E-mail: hchou@mail.nsysu.edu.tw [Department of Physics, National Sun Yat-sen University, Kaohsiung, Taiwan (China)

2017-07-01

Highlights: • Co-doped ZnO thin-films were grown with varying V{sub O} concentartion. • PCAR measurements were done to study the SPC. • High spin polarization was observed above a certain V{sub O} concentartion. • High V{sub O} samples provide a high density of completed percolation path. • This complete percolation path gives rise to high SPC. - Abstract: Oxygen vacancy induced ferromagnetic coupling in diluted magnetic oxide (DMO) semiconductors have been reported in several studies, but technologically more crucial spin-polarized current (SPC) is still under-developed in DMOs. Few studies have claimed that VRH mechanism can originate the SPC, but, how VRH mechanism associated with percolation path, is not clearly understood. We used Point-contact Andreev reflection (PCAR) technique to probe the SPC in Co-doped ZnO (CZO) films. Since the high resistance samples cause broadening in conductance(G)-voltage(V) curves, which may result in an unreliable evaluation of spin polarization, we include two extra parameters, (i) effective temperature and (ii) spreading resistance, for the simulation to avoid the uncertainty in extracting spin polarization. The effective G-V curves and higher spin polarization can be obtained above a certain oxygen vacancy concentration. The number of completed and fragmentary percolation paths is proportional to the concentration of oxygen vacancies. For low oxygen vacancy samples, the Pb-tip has a higher probability of covering fragmentary percolation paths than the complete ones, due to its small contact size. The completed paths may remain independent of one another and get polarized in different directions, resulting in lower spin-polarization value. High oxygen vacancy samples provide a high density of completed path, most of them link to one another by crossing over, and gives rise to high spin-polarization value.

Excitation of surface plasmon polariton modes with multiple nitrogen vacancy centers in single nanodiamonds

DEFF Research Database (Denmark)

Kumar, Shailesh; Larsen Lausen, Jens; García Ortíz, César Eduardo

2016-01-01

Nitrogen-vacancy (NV) centers in diamonds are interesting due to their remarkable characteristics that are well suited to applications in quantum-information processing and magnetic field sensing, as well as representing stable fluorescent sources. Multiple NV centers in nanodiamonds (NDs) are es...

Surface defect chemistry and oxygen exchange kinetics in La2-xCaxNiO4+δ

Science.gov (United States)

Tropin, E. S.; Ananyev, M. V.; Farlenkov, A. S.; Khodimchuk, A. V.; Berenov, A. V.; Fetisov, A. V.; Eremin, V. A.; Kolchugin, A. A.

2018-06-01

Surface oxygen exchange kinetics and diffusion in La2-xCaxNiO4+δ (x = 0; 0.1; 0.3) have been studied by the isotope exchange method with gas phase equilibration in the temperature range of 600-800 °C and oxygen pressure range 0.13-2.5 kPa. Despite an enhanced electrical conductivity of La2-xCaxNiO4+δ theirs oxygen surface exchange (k*) and oxygen tracer diffusion (D*) coefficients were significantly lower in comparison with La2NiO4+δ. The rates of the elementary stages of oxygen exchange have been calculated. Upon Ca doping the change of the rate-determining stage was observed. The surface of the oxides was found to be inhomogeneous towards oxygen exchange process according to the recently developed model. The reasons of such inhomogeneity are discussed as well as Ca influence on the surface defect chemistry and oxygen surface exchange and diffusivity.

A high resolution photoemission study of surface core-level shifts in clean and oxygen-covered Ir(2 1 0) surfaces

Energy Technology Data Exchange (ETDEWEB)

Gladys, M.J.; Ermanoski, I.; Jackson, G.; Quinton, J.S.; Rowe, J.E.; Madey, T.E. E-mail: madey@physics.rutgers.edu

2004-04-01

High resolution soft X-ray photoemission electron spectroscopy (SXPS), using synchrotron radiation, is employed to investigate 4f core-level features of four differently-prepared Ir(2 1 0) surfaces: clean planar, oxygen-covered planar, oxygen-induced faceted, and clean faceted surfaces. Surface and bulk peak identifications are supported by measurements at different photon energies (thus probing different electron escape depths) and variable emission angles. Iridium 4f{sub 7/2} photoemission spectra are fitted with Doniach-Sunjic lineshapes. The surface components are identified with core levels positioned at lower binding energies than the bulk components, in contrast to previous reports of binding energy inversion on Ir(1 0 0) (1x1) and (5x1) surfaces. For clean planar Ir(2 1 0) three surface Ir 4f{sub 7/2} features are observed with core-level shifts of -765, -529, and -281 meV, with respect to the bulk; these are associated with the first, second and third layers of atoms, respectively, for atomically rough Ir(2 1 0). Adsorption of oxygen onto the planar Ir(2 1 0) surface is found to cause a suppression and shift of the surface features to higher binding energies. Annealing at T{>=}600 K in oxygen produces a faceted surface as verified by low energy electron diffraction (LEED). A comparison of planar and faceted oxygen-covered surfaces reveals minor differences in the normal emission SXPS spectra, while grazing emission spectra exhibit differences. The SXPS spectrum of the clean, faceted Ir(2 1 0) exhibits small differences in comparison to the clean planar case, with surface features having binding energy shifts of -710, -450, and -230 meV.

Experimental impact-parameter--dependent probabilities for K-shell vacancy production by fast heavy-ion projectiles

International Nuclear Information System (INIS)

Randall, R.R.; Bednar, J.A.; Curnutte, B.; Cocke, C.L.

1976-01-01

The impact-parameter dependence of the probability for production of target K x rays has been measured for oxygen projectiles on copper and for carbon and fluorine projectiles on argon at scaled velocities near 0.5. The O-on-Cu data were taken for 1.56-, 1.88-, and 2.69-MeV/amu O beams incident upon thin Cu foils. A thin Ar-gas target was used for 1.56-MeV/amu C and F beams, permitting measurements to be made for charge-pure C +4 , C +6 , F +9 and F +5 projectiles. Ar and Cu K x rays were observed with a Si(Li) detector and scattered projectiles with a collimated surface-barrier detector. Comparison of the shapes of the measured K-vacancy--production probability curves with predictions of the semiclassical Coulomb approximation (SCA) shows adequate agreement for the O-on-Cu system. For the higher ratio of projectile-to-target nuclear charge (Z 1 /Z 2 ) characterizing the C-on-Ar and F-on-Ar systems, the SCA predictions are entirely inadequate in describing the observed impact-parameter dependence. In particular, they cannot account for large probabilities found at large impact parameters. Furthermore, the dependence of the shapes on the projectile charge state is found to become pronounced at larger Z 1 /Z 2 . Attempts to account for this behavior in terms of alternative vacancy-production processes are discussed

Passivation of CdZnTe surfaces by oxidation in low energy atomic oxygen

International Nuclear Information System (INIS)

Chen, H.; Chattopadhyay, K.; Chen, K.; Burger, A.; George, M.A.; Gregory, J.C.; Nag, P.K.; Weimer, J.J.; James, R.B.

1999-01-01

A method of surface passivation of Cd 1-x Zn x Te (CZT) x-ray and gamma ray detectors has been established by using microwave-assisted atomic oxygen bombardment. Detector performance is significantly enhanced due to the reduction of surface leakage current. CZT samples were exposed to an atomic oxygen environment at the University of Alabama in Huntsville close-quote s Thermal Atomic Oxygen Facility. This system generates neutral atomic oxygen species with kinetic energies of 0.1 - 0.2 eV. The surface chemical composition and its morphology modification due to atomic oxygen exposure were studied by x-ray photoelectron spectroscopy and atomic force microscopy and the results were correlated with current-voltage measurements and with room temperature spectral responses to 133 Ba and 241 Am radiation. A reduction of leakage current by about a factor of 2 is reported, together with significant improvement in the gamma-ray line resolution. copyright 1999 American Vacuum Society

Density Functional Theory plus Hubbard U Study of the Segregation of Pt to the CeO2- x Grain Boundary.

Science.gov (United States)

Zhou, Guoli; Li, Pan; Ma, Qingmin; Tian, Zhixue; Liu, Ying

2018-03-14

Grain boundaries (GBs) can be used as traps for solute atoms and defects, and the interaction between segregants and GBs is crucial for understanding the properties of nanocrystalline materials. In this study, we have systematically investigated the Pt segregation and Pt-oxygen vacancies interaction at the ∑3 (111) GB in ceria (CeO 2 ). The Pt atom has a stronger tendency to segregate to the ∑3 (111) GB than to the (111) and (110) free surfaces, but the tendency is weaker than to (112) and (100). Lattice distortion plays a dominant role in Pt segregation. At the Pt-segregated-GB (Pt@GB), oxygen vacancies prefer to form spontaneously near Pt in the GB region. However, at the pristine GB, oxygen vacancies can only form under O-poor conditions. Thus, Pt segregation to the GB promotes the formation of oxygen vacancies, and their strong interactions enhance the interfacial cohesion. We propose that GBs fabricated close to the surfaces of nanocrystalline ceria can trap Pt from inside the grains or other types of surface, resulting in the suppression of the accumulation of Pt on the surface under redox reactions, especially under O-poor conditions.

Vacancy profile in reverse osmosis membranes studied by positron annihilation lifetime measurements and molecular dynamics simulations

International Nuclear Information System (INIS)

Shimazu, A; Shintani, T; Hirose, M; Goto, H; Suzuki, R; Kobayashi, Y

2013-01-01

The positron annihilation technique using a slow positron beam can be used for the study of the vacancy profiles in typical reverse osmosis (RO) membranes. In this study, the vacancy profile in the polyamide membrane that exhibits a high permselectivity between ions and water was studied using the positron annihilation technique and molecular dynamics simulations. Ortho-positronium (o-Ps) lifetimes in the surface region of the membranes were evaluated by using a slow positron beam. The diffusion behavior of Na + and water in the polyamides was simulated by molecular dynamics (MD) methods using the TSUBAME2 supercomputer at the Tokyo Institute of Technology and discussed with the vacancy profile probed by the o-Ps. The results suggested that the large hydration size of Na + compared to the vacancy size in the polyamides contributes to the increased diffusivity selectivity of water/Na + that is related to the NaCl desalination performance of the membrane. Both the hydration size of the ions and the vacancy size appeared to be significant parameters to discuss the diffusivity selectivity of water/ions in typical polyamide membranes.

Optical absorption and oxygen passivation of surface states in III-nitride photonic devices

Science.gov (United States)

Rousseau, Ian; Callsen, Gordon; Jacopin, Gwénolé; Carlin, Jean-François; Butté, Raphaël; Grandjean, Nicolas

2018-03-01

III-nitride surface states are expected to impact high surface-to-volume ratio devices, such as nano- and micro-wire light-emitting diodes, transistors, and photonic integrated circuits. In this work, reversible photoinduced oxygen desorption from III-nitride microdisk resonator surfaces is shown to increase optical attenuation of whispering gallery modes by 100 cm-1 at λ = 450 nm. Comparison of photoinduced oxygen desorption in unintentionally and n+-doped microdisks suggests that the spectral changes originate from the unpinning of the surface Fermi level, likely taking place at etched nonpolar III-nitride sidewalls. An oxygen-rich surface prepared by thermal annealing results in a broadband Q improvement to state-of-the-art values exceeding 1 × 104 at 2.6 eV. Such findings emphasize the importance of optically active surface states and their passivation for future nanoscale III-nitride optoelectronic and photonic devices.

Effect of vacancy loops on swelling of metals under irradiation

International Nuclear Information System (INIS)

Golubov, S.I.

1981-01-01

Subsequent analysis of vacancy loops formation in metals under irradiation is carried out and effect of vacancy loops on vacancy porosity is studied. Expression for quasistationary function of vacancy loops distribution according to sizes taking into consideration two mechanisms of their initiation-cascade and fluctuational ones - is obtained. It is shown that rate of vacancy absorption and interstitials by vacancy loops in quasiequilibrium state is similar and depends only on summary length of loops, for its calculations the self-coordinated procedure is formulated. For the rate of metal swelling under irradiation obtained is the expression taking into consideration the presence of vacancy loops [ru

First-principles studies of various crystallographic phases and neutral atomic vacancies in KNbO3 and KTaO3

International Nuclear Information System (INIS)

Shigemi, A.; Koyama, T.; Wada, T.

2006-01-01

We evaluated enthalpies of formation and formation energies of neutral vacancies in KNbO 3 and KTaO 3 using a plane-wave pseudopotential method within a density functional formalism. The KNbO 3 (R3mR) phase with the lowest symmetry was found to have the lowest enthalpy of formation. On the other hand, the various virtual KTaO 3 phases (P4mm, Bmm2 and R3mR) with the lower symmetry were found to be approximately equal to the enthalpy of formation of a cubic KTaO 3 phase at 0 K. For both KNbO 3 and KTaO 3 , the formation energy of a K vacancy was found to be the lowest under an oxidizing atmosphere and that of an O vacancy was found to be the lowest under a reducing atmosphere. The formation energy of a Nb/Ta vacancy was the highest under both oxygen-rich and -poor conditions. These results are in good agreement with the empirical rule that B site defects in perovskite-type oxide do not exist. (copyright 2006 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Vacancy ordering and superstructure formation in dry and hydrated strontium tantalate perovskites: A TEM perspective

DEFF Research Database (Denmark)

Ashok, Anuradha M.; Haavik, Camilla; Norby, Poul

2014-01-01

Crystal structures of Sr4(Sr2Ta2)O11 and Sr4(Sr1.92Ta2.08)O11.12, synthesized by solid state reaction technique in dry and hydrated state have been studied mainly using Transmission Electron Microscopy. Due to the lesser ability of X-rays to probe details in oxygen sublattice, the change in crystal...... and corresponding unit cells of all the perovskites based on the ordering of oxygen vacancies is deduced. Crystal unit cells based on the observations are proposed with ideal atomic coordinates. Finally an attempt is made to explain the water uptake behaviour of these perovskites based on the proposed crystal...

The modification of nanocomposite hybrid polymer surfaces by exposure to oxygen containing plasmas

Science.gov (United States)

Figueiredo, Ashley; Zimmermann, Katherine; Augustine, Brian; Hughes, Chris; Chusuei, Charles

2006-11-01

The wetting properties of the surfaces of the nanocomposite hybrid polymer poly[(propylmethacryl-heptaisobutyl- polyhedral oligomeric silsequioxane)-co-(methylmethacrylate)] (POSS-PMMA)has been studied before and after exposure to plasmas containing oxygen. The contact angle of water droplets on the surface showed a substantial decrease after plasma exposure indicating an increase in the hydrophilicity of the surface. A model was developed in which the plasma preferentially removed organic material including both the PMMA backbone and isobutyl groups from the corners of the POSS cages leaving behind a surface characterized by the silicon oxide-like POSS material. Measurements of surface concentrations of oxygen, silicon, and carbon by x-ray photoelectron spectroscopy (XPS) showed an increase in the amount of oxygen and silicon compared to carbon and the appropriate chemical shifts were observed in the XPS data to support the model of Si-O enrichment on the surface. Variable angle spectroscopic ellipsometry (VASE) and atomic force microscopy (AFM) measurements also supported the model and these results will be presented.

Mechanism for wettability alteration of ZnO nanorod arrays via thermal annealing in vacuum and air