Exciton-dissociation and charge-recombination processes in pentacene/C60 solar cells: theoretical insight into the impact of interface geometry.

Science.gov (United States)

Yi, Yuanping; Coropceanu, Veaceslav; Brédas, Jean-Luc

2009-11-04

The exciton-dissociation and charge-recombination processes in organic solar cells based on pentacene/C(60) heterojunctions are investigated by means of quantum-mechanical calculations. The electronic couplings and the rates of exciton dissociation and charge recombination have been evaluated for several geometrical configurations of the pentacene/C(60) complex, which are relevant to bilayer and bulk heterojunctions. The results suggest that, irrespective of the actual pentacene-fullerene orientation, both pentacene-based and C(60)-based excitons are able to dissociate efficiently. Also, in the case of parallel configurations of the molecules at the pentacene/C(60) interface, the decay of the lowest charge-transfer state to the ground state is calculated to be very fast; as a result, it can compete with the dissociation process into mobile charge carriers. Since parallel configurations are expected to be found more frequently in bulk heterojunctions than in bilayer heterojunctions, the performance of pentacene/C(60) bulk-heterojunction solar cells is likely to be more affected by charge recombination than that of bilayer devices.

Exciton-Dissociation and Charge-Recombination Processes in Pentacene/C 60 Solar Cells: Theoretical Insight into the Impact of Interface Geometry

KAUST Repository

Yi, Yuanping

2009-11-04

The exciton-dissociation and charge-recombination processes in organic solar cells based on pentacene/C60 heterojunctions are investigated by means of quantum-mechanical calculations. The electronic couplings and the rates of exciton dissociation and charge recombination have been evaluated for several geometrical configurations of the pentacene/C60 complex, which are relevant to bilayer and bulk heterojunctions. The results suggest that, irrespective of the actual pentacene-fullerene orientation, both pentacene-based and C60-based excitons are able to dissociate efficiently. Also, in the case of parallel configurations of the molecules at the pentacene/C60 interface, the decay of the lowest charge-transfer state to the ground state is calculated to be very fast; as a result, it can compete with the dissociation process into mobile charge carriers. Since parallel configurations are expected to be found more frequently in bulk heterojunctions than in bilayer heterojunctions, the performance of pentacene/C60 bulk-heterojunction solar cells is likely to be more affected by charge recombination than that of bilayer devices. © 2009 American Chemical Society.

Energy transfer of excitons between quantum wells separated by a wide barrier

International Nuclear Information System (INIS)

Lyo, S. K.

2000-01-01

We present a microscopic theory of the excitonic Stokes and anti-Stokes energy-transfer mechanisms between two widely separated unequal quantum wells with a large energy mismatch (Δ) at low temperatures (T). Several important intrinsic energy-transfer mechanisms have been examined, including dipolar coupling, real and virtual photon-exchange coupling, and over-barrier ionization of the excitons via exciton-exciton Auger processes. The transfer rate is calculated as a function of T and the center-to-center distance d between the wells. The rates depend sensitively on T for plane-wave excitons. For localized excitons, the rates depend on T only through the T dependence of the exciton localization radius. For Stokes energy transfer, the dominant energy transfer occurs through a photon-exchange interaction, which enables the excitons from the higher-energy wells to decay into free electrons and holes in the lower-energy wells. The rate has a slow dependence on d, yielding reasonable agreement with recent data from GaAs/Al x Ga 1-x As quantum wells. The dipolar rate is about an order of magnitude smaller for large d (e.g., d=175Aa) with a stronger range dependence proportional to d -4 . However, the latter can be comparable to the radiative rate for small d (e.g., d≤80Aa). For anti-Stokes transfer through exchange-type (e.g., dipolar and photon-exchange) interactions, we show that thermal activation proportional to exp(-Δ/k B T) is essential for the transfer, contradicting a recent nonactivated result based on the Fo''rster-Dexter's spectral-overlap theory. Phonon-assisted transfer yields a negligibly small rate. On the other hand, energy transfer through over-barrier ionization of excitons via Auger processes yields a significantly larger nonactivated rate which is independent of d. The result is compared with recent data

Energy and Information Transfer Via Coherent Exciton Wave Packets

Science.gov (United States)

Zang, Xiaoning

Electronic excitons are bound electron-hole states that are generated when light interacts with matter. Such excitations typically entangle with phonons and rapidly decohere; the resulting electronic state dynamics become diffusive as a result. However, if the exciton-phonon coupling can be reduced, it may be possible to construct excitonic wave packets that offer a means of efficiently transmitting information and energy. This thesis is a combined theory/computation investigation to design condensed matter systems which support the requisite coherent transport. Under the idealizing assumption that exciton-phonon entanglement could be completely suppressed, the majority of this thesis focuses on the creation and manipulation of exciton wave packets in quasi-one-dimensional systems. While each site could be a silicon quantum dot, the actual implementation focused on organic molecular assemblies for the sake of computational simplicity, ease of experimental implementation, potential for coherent transport, and promise because of reduced structural uncertainty. A laser design was derived to create exciton wave packets with tunable shape and speed. Quantum interference was then exploited to manipulate these packets to block, pass, and even dissociate excitons based on their energies. These developments allow exciton packets to be considered within the arena of quantum information science. The concept of controllable excitonic wave packets was subsequently extended to consider molecular designs that allow photons with orbital angular momentum to be absorbed to create excitons with a quasi-angular momentum of their own. It was shown that a well-defined measure of topological charge is conserved in such light-matter interactions. Significantly, it was also discovered that such molecules allow photon angular momenta to be combined and later emitted. This amounts to a new way of up/down converting photonic angular momentum without relying on nonlinear optical materials. The

Exciton generation/dissociation/charge-transfer enhancement in inorganic/organic hybrid solar cells by robust single nanocrystalline LnPxOy (Ln = Eu, Y) doping.

Science.gov (United States)

Jin, Xiao; Sun, Weifu; Chen, Zihan; Wei, Taihuei; Chen, Chuyang; He, Xingdao; Yuan, Yongbiao; Li, Yue; Li, Qinghua

2014-06-11

Low-temperature solution-processed photovoltaics suffer from low efficiencies because of poor exciton or electron-hole transfer. Inorganic/organic hybrid solar cell, although still in its infancy, has attracted great interest thus far. One of the promising ways to enhance exciton dissociation or electron-hole transport is the doping of lanthanide phosphate ions. However, the underlying photophysical mechanism remains poorly understood. Herein, by applying femtosecond transient absorption spectroscopy, we successfully distinguished hot electron, less energetic electron, hole transport from electron-hole recombination. Concrete evidence has been provided that lanthanide phosphate doping improves the efficiency of both hot electron and "less energetic" electron transfers from donor to acceptor, but the hole transport almost remains unchanged. In particular, the hot electron transfer lifetime was shortened from 30.2 to 12.7 ps, that is, more than 60% faster than pure TiO2 acceptor. Such improvement was ascribed to the facts that the conduction band (CB) edge energy level of TiO2 has been elevated by 0.2 eV, while the valence band level almost remains unchanged, thus not only narrowing the energy offset between CB levels of TiO2 and P3HT, but also meanwhile enlarging the band gap of TiO2 itself that permits one to inhibit electron-hole recombination within TiO2. Consequently, lanthanide phosphate doped TiO2/P3HT bulk-heterojunction solar cell has been demonstrated to be a promising hybrid solar cell, and a notable power conversion efficiency of 2.91% is therefore attained. This work indicates that lanthanide compound ions can efficiently facilitate exciton generation, dissociation, and charge transport, thus enhancing photovoltaic performance.

Charge transfer state in DBP:C70 organic solar cells

DEFF Research Database (Denmark)

Sherafatipour, Golenaz; Benduhn, Johannes; Spoltore, Donato

-acceptor interface via delocalized charge-transfer (CT) states, which represents an intermediate state between the exciton dissociation and recombination back to the ground state. In this work we perform the electroluminescence (EL) created by bimolecular free career recombination and sensitive external quantum...

Single-crystal charge transfer interfaces for efficient photonic devices (Conference Presentation)

Science.gov (United States)

Alves, Helena; Pinto, Rui M.; Maçôas, Ermelinda M. S.; Baleizão, Carlos; Santos, Isabel C.

2016-09-01

Organic semiconductors have unique optical, mechanical and electronic properties that can be combined with customized chemical functionality. In the crystalline form, determinant features for electronic applications such as molecular purity, the charge mobility or the exciton diffusion length, reveal a superior performance when compared with materials in a more disordered form. Combining crystals of two different conjugated materials as even enable a new 2D electronic system. However, the use of organic single crystals in devices is still limited to a few applications, such as field-effect transistors. In 2013, we presented the first system composed of single-crystal charge transfer interfaces presenting photoconductivity behaviour. The system composed of rubrene and TCNQ has a responsivity reaching 1 A/W, corresponding to an external quantum efficiency of nearly 100%. A similar approach, with a hybrid structure of a PCBM film and rubrene single crystal also presents high responsivity and the possibility to extract excitons generated in acceptor materials. This strategy led to an extended action towards the near IR. By adequate material design and structural organisation of perylediimides, we demonstrate that is possible to improve exciton diffusion efficiency. More recently, we have successfully used the concept of charge transfer interfaces in phototransistors. These results open the possibility of using organic single-crystal interfaces in photonic applications.

Photoinduced partial charge transfer between conjugated polymer and fullerene in solutions

International Nuclear Information System (INIS)

Lin Hongzhen; Weng Yufeng; Huang Hongmin; He Qingguo; Zheng Min; Bai Fenglian

2004-01-01

Photoinduced charge transfer between a conjugated polymer and C 60 and the related processes were investigated in dilute solutions. The substantial fluorescence quenching is correlated with the efficient exciton diffusion within the polymer chains, according to which a sphere-of-action mechanism is proposed. An emissive exciplex was found formed between the conjugated polymer and fullerene in a nonpolar solvent, indicating the occurrence of a photoinduced partial charge transfer process. The low-energy sites in the polymer are believed to play a crucial role in the partial charge transfer. The asymmetry of the exciplex provides a method for evaluating the tendency of photoinduced charge separation between the donor and the acceptor. This method allows screening candidates for photovoltaic applications

Exciton shelves for charge and energy transport in third-generation quantum-dot devices

Science.gov (United States)

Goodman, Samuel; Singh, Vivek; Noh, Hyunwoo; Casamada, Josep; Chatterjee, Anushree; Cha, Jennifer; Nagpal, Prashant

2014-03-01

Quantum dots are semiconductor nanocrystallites with size-dependent quantum-confined energy levels. While they have been intensively investigated to utilize hot-carriers for photovoltaic applications, to bridge the mismatch between incident solar photons and finite bandgap of semiconductor photocells, efficient charge or exciton transport in quantum-dot films has proven challenging. Here we show development of new coupled conjugated molecular wires with ``exciton shelves'', or different energy levels, matched with the multiple energy levels of quantum dots. Using single nanoparticle and ensemble device measurements we show successful extraction and transport of both bandedge and high-energy charge carriers, and energy transport of excitons. We demonstrate using measurements of electronic density of states, that careful matching of energy states of quantum-dot with molecular wires is important, and any mismatch can generate midgap states leading to charge recombination and reduced efficiency. Therefore, these exciton-shelves and quantum dots can lead to development of next-generation photovoltaic and photodetection devices using simultaneous transport of bandedge and hot-carriers or energy transport of excitons in these nanostructured solution-processed films.

Energy and charge transfer in ionized argon coated water clusters

International Nuclear Information System (INIS)

Kočišek, J.; Lengyel, J.; Fárník, M.; Slavíček, P.

2013-01-01

We investigate the electron ionization of clusters generated in mixed Ar-water expansions. The electron energy dependent ion yields reveal the neutral cluster composition and structure: water clusters fully covered with the Ar solvation shell are formed under certain expansion conditions. The argon atoms shield the embedded (H 2 O) n clusters resulting in the ionization threshold above ≈15 eV for all fragments. The argon atoms also mediate more complex reactions in the clusters: e.g., the charge transfer between Ar + and water occurs above the threshold; at higher electron energies above ∼28 eV, an excitonic transfer process between Ar + * and water opens leading to new products Ar n H + and (H 2 O) n H + . On the other hand, the excitonic transfer from the neutral Ar* state at lower energies is not observed although this resonant process was demonstrated previously in a photoionization experiment. Doubly charged fragments (H 2 O) n H 2 2+ and (H 2 O) n 2+ ions are observed and Intermolecular Coulomb decay (ICD) processes are invoked to explain their thresholds. The Coulomb explosion of the doubly charged cluster formed within the ICD process is prevented by the stabilization effect of the argon solvent

Triplet exciton formation in organic photovoltaics

Energy Technology Data Exchange (ETDEWEB)

Yang, Xudong; Westenhoff, Sebastian; Howard, Ian; Ford, Thomas; Friend, Richard; Hodgkiss, Justin; Greenham, Neil [Cavendish Laboratory, University of Cambridge (United Kingdom)

2009-07-01

We have recently found that the formation of triplet excitons can be an important loss mechanism in organic photovoltaics, particularly in donor-acceptor blends designed to have high open-circuit voltages. This can occur when the intrachain triplet state lies lower in energy than the charge-transfer state formed at the heterojunction. We find that in a blend based on the polyfluorene derivatives F8BT and PFB, triplet excitons are formed after photoexcitation with much higher efficiency than in the component polymers. We use transient absorption spectroscopy to study the dynamics of charges and triplet excitons on timescales from picoseconds to microseconds. This allows us to determine a characteristic time of {proportional_to} 40 ns for intersystem crossing in the charge-separated state, and to estimate that as many as 75% of photoexcitations lead to the formation of triplet states. To avoid losses to triplet excitons in photovoltaic devices, it is necessary to separate charge pairs before intersystem crossing can occur. We also present photophysical measurements of saturation and relaxation of the triplet excited state absorption used to quantify triplet populations.

Electrical control of charged carriers and excitons in atomically thin materials

Science.gov (United States)

Wang, Ke; De Greve, Kristiaan; Jauregui, Luis A.; Sushko, Andrey; High, Alexander; Zhou, You; Scuri, Giovanni; Taniguchi, Takashi; Watanabe, Kenji; Lukin, Mikhail D.; Park, Hongkun; Kim, Philip

2018-02-01

Electrical confinement and manipulation of charge carriers in semiconducting nanostructures are essential for realizing functional quantum electronic devices1-3. The unique band structure4-7 of atomically thin transition metal dichalcogenides (TMDs) offers a new route towards realizing novel 2D quantum electronic devices, such as valleytronic devices and valley-spin qubits8. 2D TMDs also provide a platform for novel quantum optoelectronic devices9-11 due to their large exciton binding energy12,13. However, controlled confinement and manipulation of electronic and excitonic excitations in TMD nanostructures have been technically challenging due to the prevailing disorder in the material, preventing accurate experimental control of local confinement and tunnel couplings14-16. Here we demonstrate a novel method for creating high-quality heterostructures composed of atomically thin materials that allows for efficient electrical control of excitations. Specifically, we demonstrate quantum transport in the gate-defined, quantum-confined region, observing spin-valley locked quantized conductance in quantum point contacts. We also realize gate-controlled Coulomb blockade associated with confinement of electrons and demonstrate electrical control over charged excitons with tunable local confinement potentials and tunnel couplings. Our work provides a basis for novel quantum opto-electronic devices based on manipulation of charged carriers and excitons.

Spectroscopy and dynamics of charge transfer excitons in type-II band aligned quantum confined heterostructures

Energy Technology Data Exchange (ETDEWEB)

Kushavah, Dushyant [Centre for Research in Nanotechnology and Science, IIT Bombay-400076, Mumbai (India); Mohapatra, P. K.; Vasa, P.; Singh, B. P., E-mail: bhanups@iitb.ac.in [Department of physics, IIT Bombay, Mumbai-400076 (India); Rustagi, K. C. [Indian Institute of Science Education and Research Bhopal-462066, Bhopal (India); Bahadur, D. [Department of Metallurgical Engineering and Materials Science, IIT Bombay, Mumbai-400076 (India)

2015-05-15

We illustrate effect of charge transfer (CT) in type-II quantum confined heterostructure by comparing CdSe quantum dots (QDs), CdSe/CdTe heterostructure quantum dots (HQDs) and CdSe/CdTe/CdSe quantum well-quantum dots (QWQDs) heterostructures. CdSe core QDs were synthesized using a kinetic growth method where QD size depends on reaction time. For shell coating we used modified version of successive ionic layer adsorption and reaction (SILAR). Size of different QDs ∼5 to 7 nm were measured by transmission electron microscopy (TEM). Strong red shift from ∼597 to ∼746 nm in photoluminescence (PL) spectra from QDs to QWQDs shows high tunability which is not possible with single constituent semiconductor QDs. PL spectra have been recorded at different temperatures (10K-300K). Room temperature time correlated single photon counting (TCSPC) measurements for QDs to QWQDs show three exponential radiative decay. The slowest component decay constant in QWQDs comes around eight fold to ∼51 ns as compared to ∼6.5 ns in HQD suggesting new opportunities to tailor the radiative carrier recombination rate of CT excitons.

Charge separation in excitonic and bipolar solar cells - A detailed balance approach

International Nuclear Information System (INIS)

Kirchartz, Thomas; Rau, Uwe

2008-01-01

A generalized solar cell model for excitonic and classical, bipolar solar cells is developed that describes the combined transport and interaction of electrons, holes and excitons. Both, conventional inorganic solar cells as well as organic solar cells, where excitons play a dominant role for energy transport, turn out to be special cases of this model. Due to the inclusion of photon recycling effects, the approach is compatible with the principle of detailed balance and the Shockley-Queisser limit. We show how varying the interaction between excitons and charge carriers as well as varying the respective mobilities of the different species changes the operation mode of the solar cell path between excitonic and bipolar

Pentacene Excitons in Strong Electric Fields.

Science.gov (United States)

Kuhnke, Klaus; Turkowski, Volodymyr; Kabakchiev, Alexander; Lutz, Theresa; Rahman, Talat S; Kern, Klaus

2018-02-05

Electroluminescence spectroscopy of organic semiconductors in the junction of a scanning tunneling microscope (STM) provides access to the polarizability of neutral excited states in a well-characterized molecular geometry. We study the Stark shift of the self-trapped lowest singlet exciton at 1.6 eV in a pentacene nanocrystal. Combination of density functional theory (DFT) and time-dependent DFT (TDDFT) with experiment allows for assignment of the observation to a charge-transfer (CT) exciton. Its charge separation is perpendicular to the applied field, as the measured polarizability is moderate and the electric field in the STM junction is strong enough to dissociate a CT exciton polarized parallel to the applied field. The calculated electric-field-induced anisotropy of the exciton potential energy surface will also be of relevance to photovoltaic applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Energy and charge transfer cascade in methylammonium lead bromide perovskite nanoparticle aggregates.

Science.gov (United States)

Bouduban, Marine E F; Burgos-Caminal, Andrés; Ossola, Rachele; Teuscher, Joël; Moser, Jacques-E

2017-06-01

Highly photoluminescent hybrid lead halide perovskite nanoparticles have recently attracted wide interest in the context of high-stake applications, such as light emitting diodes (LEDs), light emitting transistors and lasers. In addition, they constitute ideal model systems to explore energy and charge transport phenomena occurring at the boundaries of nanocrystalline grains forming thin films in high-efficiency perovskite solar cells (PSCs). Here we report a complete photophysical study of CH 3 NH 3 PbBr 3 perovskite nanoparticles suspended in chlorobenzene and highlight some important interaction properties. Colloidal suspensions under study were constituted of dispersed aggregates of quasi-2D platelets of a range of thicknesses, decorated with 3D-like spherical nanoparticles. These types of nanostructures possess different optical properties that afford a handle for probing them individually. The photophysics of the colloidal particles was studied by femtosecond pump-probe spectroscopy and time-correlated single-photon counting. We show here that a cascade of energy and exciton-mediated charge transfer occurs between nanostructures: upon photoexcitation, localized excitons within one nanostructure can either recombine on a ps timescale, yielding a short-lived emission, or form charge-transfer states (CTSs) across adjacent domains, resulting in longer-lived photoluminescence in the millisecond timescale. Furthermore, CTSs exhibit a clear signature in the form of a strong photoinduced electroabsorption evidenced in femtosecond transient absorption measurements. Charge transfer dynamics at the surface of the nanoparticles have been studied with various quenchers in solution. Efficient hole transfer to N , N , N ', N '-tetrakis(4-methoxyphenyl)benzidine (MeO-TPD) and 1,4-bis(diphenyl-amino)benzene (BDB) donors was attested by the quenching of the nanoparticles emission. The charge transfer rate was limited by the organic layer used to stabilize the nanoparticles

Triplet exciton diffusion in organic semiconductors

Energy Technology Data Exchange (ETDEWEB)

Koehler, Anna [Department of Physics, University of Bayreuth (Germany)

2010-07-01

Efficient triplet exciton emission has allowed improved operation of organic light-emitting diodes (LEDs). To enhance the device performance, it is necessary to understand what governs the motion of triplet excitons through the organic semiconductor. We use a series of poly(p-phenylene)-type conjugated polymers and oligomers of variable degree of molecular distortion (i.e. polaron formation) and energetic disorder as model systems to study the Dexter-type triplet exciton diffusion in thin films. We show that triplet diffusion can be quantitatively described in the framework of a Holstein small polaron model (Marcus theory) that is extended to include contributions from energetic disorder. The model predicts a tunnelling process at low temperatures followed by a thermally activated hopping process above a transition temperature. In contrast to charge transfer, the activation energy required for triplet exciton transfer can be deduced from the optical spectra. We discuss the implications for device architecture.

Field-induced exciton dissociation in PTB7-based organic solar cells

Science.gov (United States)

Gerhard, Marina; Arndt, Andreas P.; Bilal, Mühenad; Lemmer, Uli; Koch, Martin; Howard, Ian A.

2017-05-01

The physics of charge separation in organic semiconductors is a topic of ongoing research of relevance to material and device engineering. Herein, we present experimental observations of the field and temperature dependence of charge separation from singlet excitons in PTB7 and PC71BM , and from charge-transfer states created across interfaces in PTB 7 /PC71BM bulk heterojunction solar cells. We obtain this experimental data by time-resolving the near infrared emission of the states from 10 K to room temperature and electric fields from 0 to 2.5 MVcm -1 . Examining how the luminescence is quenched by field and temperature gives direct insight into the underlying physics. We observe that singlet excitons can be split by high fields, and that disorder broadens the high threshold fields needed to split the excitons. Charge-transfer (CT) states, on the other hand, can be separated by both field and temperature. Also, the data imply a strong reduction of the activation barrier for charge splitting from the CT state relative to the exciton state. The observations provided herein of the field-dependent separation of CT states as a function of temperature offer a rich data set against which theoretical models of charge separation can be rigorously tested; it should be useful for developing the more advanced theoretical models of charge separation.

ARCHITECTURE OF A CHARGE-TRANSFER STATE REGULATING LIGHT HARVESTING IN A PLANT ANTENNA PROTEIN

Energy Technology Data Exchange (ETDEWEB)

Fleming, Graham; Ahn, Tae Kyu; Avenson, Thomas J.; Ballottari, Matteo; Cheng, Yuan-Chung; Niyogi, Krishna K.; Bassi, Roberto; Fleming, Graham R.

2008-04-02

Energy-dependent quenching of excess absorbed light energy (qE) is a vital mechanism for regulating photosynthetic light harvesting in higher plants. All of the physiological characteristics of qE have been positively correlated with charge-transfer between coupled chlorophyll and zeaxanthin molecules in the light-harvesting antenna of photosystem II (PSII). In this work, we present evidence for charge-transfer quenching in all three of the individual minor antenna complexes of PSII (CP29, CP26, and CP24), and we conclude that charge-transfer quenching in CP29 involves a de-localized state of an excitonically coupled chlorophyll dimer. We propose that reversible conformational changes in CP29 can `tune? the electronic coupling between the chlorophylls in this dimer, thereby modulating the energy of the chlorophylls-zeaxanthin charge-transfer state and switching on and off the charge-transfer quenching during qE.

Influence of Frenkel Excitons and Charge Transfer States on the Spectroscopic Properties of Organic Molecular Crystals

OpenAIRE

Gisslén, Linus Mathias

2010-01-01

Perylene derivatives are robust organic dyes absorbing and emitting light in the visible range and in the near infrared. They display a strong tendency to self-assemble into molecular aggregates, liquid crystals, or even crystals. In this thesis, we have demonstrated a successful realization of a theoretical approach describing the fundamental interactions influencing on exciton transfer in crystalline perylenes pigments. Furthermore, the microscopic parameter set obtained has allowed to calc...

Optical absorption of charged excitons in semiconducting carbon nanotubes

DEFF Research Database (Denmark)

Rønnow, Troels Frimodt; Pedersen, Thomas Garm; Cornean, Horia

2012-01-01

In this article we examine the absorption coefficient of charged excitons in carbon nanotubes. We investigate the temperature and damping dependence of the absorption spectra. We show that the trion peak in the spectrum is asymmetric for temperatures greater than approximately 1 K whereas...

Hopping approach towards exciton dissociation in conjugated polymers

International Nuclear Information System (INIS)

Emelianova, E. V.; Auweraer, M. van der; Baessler, H.

2008-01-01

By employing random walk an analytic theory for the dissociation of singlet excitons in a random organic solid, for instance, a conjugated polymer, has been developed. At variance of conventional three-dimensional Onsager theory, it is assumed that an exciton with finite lifetime can first transfer endothermically an electron to an adjacent site, thereby generating a charge transfer state whose energy is above the energy of that of the initial exciton. In a second step the latter can fully dissociate in accordance with Onsager's concept Brownian motion. The results indicate that, depending of the energy required for the first jump, the first jump contributes significantly to the field dependence of the dissociation yield. Disorder weakens the temperature dependence of the yield dramatically and precludes extracting information on the exciton binding energy from it

Energy relaxation and transfer in excitonic trimer

International Nuclear Information System (INIS)

Herman, Pavel; Barvik, Ivan; Urbanec, Martin

2004-01-01

Two models describing exciton relaxation and transfer (the Redfield model in the secular approximation and Capek's model) are compared for a simple example - a symmetric trimer coupled to a phonon bath. Energy transfer within the trimer occurs via resonance interactions and coupling between the trimer and the bath occurs via modulation of the monomer energies by phonons. Two initial conditions are adopted: (1) one of higher eigenstates of the trimer is initially occupied and (2) one local site of the trimer is initially occupied. The diagonal exciton density matrix elements in the representation of eigenstates are found to be the same for both models, but this is not so for the off-diagonal density matrix elements. Only if the off-diagonal density matrix elements vanish initially (initial condition (1)), they then vanish at arbitrary times in both models. If the initial excitation is local, the off-diagonal matrix elements essentially differ

Dynamics of Charged Excitons and Biexcitons in CsPbBr3 Perovskite Nanocrystals Revealed by Femtosecond Transient-Absorption and Single-Dot Luminescence Spectroscopy.

Science.gov (United States)

Yarita, Naoki; Tahara, Hirokazu; Ihara, Toshiyuki; Kawawaki, Tokuhisa; Sato, Ryota; Saruyama, Masaki; Teranishi, Toshiharu; Kanemitsu, Yoshihiko

2017-04-06

Metal-halide perovskite nanocrystals (NCs) are promising photonic materials for use in solar cells, light-emitting diodes, and lasers. The optoelectronic properties of these devices are determined by the excitons and exciton complexes confined in their NCs. In this study, we determined the relaxation dynamics of charged excitons and biexcitons in CsPbBr 3 NCs using femtosecond transient-absorption (TA), time-resolved photoluminescence (PL), and single-dot second-order photon correlation spectroscopy. Decay times of ∼40 and ∼200 ps were obtained from the TA and PL decay curves for biexcitons and charged excitons, respectively, in NCs with an average edge length of 7.7 nm. The existence of charged excitons even under weak photoexcitation was confirmed by the second-order photon correlation measurements. We found that charged excitons play a dominant role in luminescence processes of CsPbBr 3 NCs. Combining different spectroscopic techniques enabled us to clarify the dynamical behaviors of excitons, charged excitons, and biexcitons.

Charge transport through exciton shelves in cadmium chalcogenide quantum dot-DNA nano-bioelectronic thin films

Science.gov (United States)

Goodman, Samuel M.; Noh, Hyunwoo; Singh, Vivek; Cha, Jennifer N.; Nagpal, Prashant

2015-02-01

Quantum dot (QD), or semiconductor nanocrystal, thin films are being explored for making solution-processable devices due to their size- and shape-tunable bandgap and discrete higher energy electronic states. While DNA has been extensively used for the self-assembly of nanocrystals, it has not been investigated for the simultaneous conduction of multiple energy charges or excitons via exciton shelves (ES) formed in QD-DNA nano-bioelectronic thin films. Here, we present studies on charge conduction through exciton shelves, which are formed via chemically coupled QDs and DNA, between electronic states of the QDs and the HOMO-LUMO levels in the complementary DNA nucleobases. While several challenges need to be addressed in optimizing the formation of devices using QD-DNA thin films, a higher charge collection efficiency for hot-carriers and our detailed investigations of charge transport mechanism in these thin films highlight their potential for applications in nano-bioelectronic devices and biological transducers.

Charge transport through exciton shelves in cadmium chalcogenide quantum dot-DNA nano-bioelectronic thin films

Energy Technology Data Exchange (ETDEWEB)

Goodman, Samuel M.; Singh, Vivek [Department of Chemical and Biological Engineering, University of Colorado Boulder, 3415 Colorado Avenue, Boulder, Colorado 80303 (United States); Noh, Hyunwoo [Department of Chemical and Biological Engineering, University of Colorado Boulder, 3415 Colorado Avenue, Boulder, Colorado 80303 (United States); Materials Science and Engineering Program and Department of Nanoengineering, University of California, 9500 Gilman Drive, La Jolla, San Diego, California 92093 (United States); Cha, Jennifer N. [Department of Chemical and Biological Engineering, University of Colorado Boulder, 3415 Colorado Avenue, Boulder, Colorado 80303 (United States); Materials Science and Engineering Program and Department of Nanoengineering, University of California, 9500 Gilman Drive, La Jolla, San Diego, California 92093 (United States); Materials Science and Engineering, University of Colorado Boulder, 3415 Colorado Avenue, Boulder, Colorado 80303 (United States); Nagpal, Prashant, E-mail: pnagpal@colorado.edu [Department of Chemical and Biological Engineering, University of Colorado Boulder, 3415 Colorado Avenue, Boulder, Colorado 80303 (United States); Materials Science and Engineering, University of Colorado Boulder, 3415 Colorado Avenue, Boulder, Colorado 80303 (United States); BioFrontiers Institute, University of Colorado Boulder, 3415 Colorado Avenue, Boulder, Colorado 80303 (United States); Renewable and Sustainable Energy Institute, University of Colorado Boulder, 2445 Kittredge Loop, Boulder, Colorado 80309 (United States)

2015-02-23

Quantum dot (QD), or semiconductor nanocrystal, thin films are being explored for making solution-processable devices due to their size- and shape-tunable bandgap and discrete higher energy electronic states. While DNA has been extensively used for the self-assembly of nanocrystals, it has not been investigated for the simultaneous conduction of multiple energy charges or excitons via exciton shelves (ES) formed in QD-DNA nano-bioelectronic thin films. Here, we present studies on charge conduction through exciton shelves, which are formed via chemically coupled QDs and DNA, between electronic states of the QDs and the HOMO-LUMO levels in the complementary DNA nucleobases. While several challenges need to be addressed in optimizing the formation of devices using QD-DNA thin films, a higher charge collection efficiency for hot-carriers and our detailed investigations of charge transport mechanism in these thin films highlight their potential for applications in nano-bioelectronic devices and biological transducers.

Charge transport through exciton shelves in cadmium chalcogenide quantum dot-DNA nano-bioelectronic thin films

International Nuclear Information System (INIS)

Goodman, Samuel M.; Singh, Vivek; Noh, Hyunwoo; Cha, Jennifer N.; Nagpal, Prashant

2015-01-01

Quantum dot (QD), or semiconductor nanocrystal, thin films are being explored for making solution-processable devices due to their size- and shape-tunable bandgap and discrete higher energy electronic states. While DNA has been extensively used for the self-assembly of nanocrystals, it has not been investigated for the simultaneous conduction of multiple energy charges or excitons via exciton shelves (ES) formed in QD-DNA nano-bioelectronic thin films. Here, we present studies on charge conduction through exciton shelves, which are formed via chemically coupled QDs and DNA, between electronic states of the QDs and the HOMO-LUMO levels in the complementary DNA nucleobases. While several challenges need to be addressed in optimizing the formation of devices using QD-DNA thin films, a higher charge collection efficiency for hot-carriers and our detailed investigations of charge transport mechanism in these thin films highlight their potential for applications in nano-bioelectronic devices and biological transducers

Excitonic energy transfer in light-harvesting complexes in purple bacteria

International Nuclear Information System (INIS)

Ye Jun; Sun Kewei; Zhao Yang; Lee, Chee Kong; Yu Yunjin; Cao Jianshu

2012-01-01

Two distinct approaches, the Frenkel-Dirac time-dependent variation and the Haken-Strobl model, are adopted to study energy transfer dynamics in single-ring and double-ring light-harvesting (LH) systems in purple bacteria. It is found that the inclusion of long-range dipolar interactions in the two methods results in significant increase in intra- or inter-ring exciton transfer efficiency. The dependence of exciton transfer efficiency on trapping positions on single rings of LH2 (B850) and LH1 is similar to that in toy models with nearest-neighbor coupling only. However, owing to the symmetry breaking caused by the dimerization of BChls and dipolar couplings, such dependence has been largely suppressed. In the studies of coupled-ring systems, both methods reveal an interesting role of dipolar interactions in increasing energy transfer efficiency by introducing multiple intra/inter-ring transfer paths. Importantly, the time scale (4 ps) of inter-ring exciton transfer obtained from polaron dynamics is in good agreement with previous studies. In a double-ring LH2 system, non-nearest neighbor interactions can induce symmetry breaking, which leads to global and local minima of the average trapping time in the presence of a non-zero dephasing rate, suggesting that environment dephasing helps preserve quantum coherent energy transfer when the perfect circular symmetry in the hypothetic system is broken. This study reveals that dipolar coupling between chromophores may play an important role in the high energy transfer efficiency in the LH systems of purple bacteria and many other natural photosynthetic systems.

Excitonic energy transfer in light-harvesting complexes in purple bacteria

Energy Technology Data Exchange (ETDEWEB)

Ye Jun; Sun Kewei; Zhao Yang; Lee, Chee Kong [School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Yu Yunjin [School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798 (Singapore); College of Physics Science and Technology, Shenzhen University, Guangdong 518060 (China); Cao Jianshu [Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States)

2012-06-28

Two distinct approaches, the Frenkel-Dirac time-dependent variation and the Haken-Strobl model, are adopted to study energy transfer dynamics in single-ring and double-ring light-harvesting (LH) systems in purple bacteria. It is found that the inclusion of long-range dipolar interactions in the two methods results in significant increase in intra- or inter-ring exciton transfer efficiency. The dependence of exciton transfer efficiency on trapping positions on single rings of LH2 (B850) and LH1 is similar to that in toy models with nearest-neighbor coupling only. However, owing to the symmetry breaking caused by the dimerization of BChls and dipolar couplings, such dependence has been largely suppressed. In the studies of coupled-ring systems, both methods reveal an interesting role of dipolar interactions in increasing energy transfer efficiency by introducing multiple intra/inter-ring transfer paths. Importantly, the time scale (4 ps) of inter-ring exciton transfer obtained from polaron dynamics is in good agreement with previous studies. In a double-ring LH2 system, non-nearest neighbor interactions can induce symmetry breaking, which leads to global and local minima of the average trapping time in the presence of a non-zero dephasing rate, suggesting that environment dephasing helps preserve quantum coherent energy transfer when the perfect circular symmetry in the hypothetic system is broken. This study reveals that dipolar coupling between chromophores may play an important role in the high energy transfer efficiency in the LH systems of purple bacteria and many other natural photosynthetic systems.

Density functional theory for the description of charge-transfer processes at TTF/TCNQ interfaces

KAUST Repository

Van Regemorter, Tanguy; Guillaume, Maxime; Sini, Gjergji; Sears, John S.; Geskin, Victor; Bré das, Jean-Luc; Beljonne, David; Cornil, Jé rô me

2012-01-01

In the field of organic electronics, a central issue is to assess how the frontier electronic levels of two adjacent organic layers align with respect to one another at the interface. This alignment can be driven by the presence of a partial charge transfer and the formation of an interface dipole; it plays a key role for instance in determining the rates of exciton dissociation or exciton formation in organic solar cells or light-emitting diodes, respectively. Reliably modeling the processes taking place at these interfaces remains a challenge for the computational chemistry community. Here, we review our recent theoretical work on the influence of the choice of density functional theory (DFT) methodology on the description of the charge-transfer character in the ground state of TTF/ TCNQ model complexes and interfaces. Starting with the electronic properties of the isolated TTF and TCNQ molecules and then considering the charge transfer and resulting interface dipole in TTF/TCNQ donor-acceptor stacks and bilayers, we examine the impact of the choice of DFT functional in describing the interfacial electronic structure. Finally, we employ computations based on periodic boundary conditions to highlight the impact of depolarization effects on the interfacial dipole moment. © Springer-Verlag 2012.

Density functional theory for the description of charge-transfer processes at TTF/TCNQ interfaces

KAUST Repository

Van Regemorter, Tanguy

2012-09-15

In the field of organic electronics, a central issue is to assess how the frontier electronic levels of two adjacent organic layers align with respect to one another at the interface. This alignment can be driven by the presence of a partial charge transfer and the formation of an interface dipole; it plays a key role for instance in determining the rates of exciton dissociation or exciton formation in organic solar cells or light-emitting diodes, respectively. Reliably modeling the processes taking place at these interfaces remains a challenge for the computational chemistry community. Here, we review our recent theoretical work on the influence of the choice of density functional theory (DFT) methodology on the description of the charge-transfer character in the ground state of TTF/ TCNQ model complexes and interfaces. Starting with the electronic properties of the isolated TTF and TCNQ molecules and then considering the charge transfer and resulting interface dipole in TTF/TCNQ donor-acceptor stacks and bilayers, we examine the impact of the choice of DFT functional in describing the interfacial electronic structure. Finally, we employ computations based on periodic boundary conditions to highlight the impact of depolarization effects on the interfacial dipole moment. © Springer-Verlag 2012.

Pressure-Dependent Light Emission of Charged and Neutral Excitons in Monolayer MoSe ₂

Energy Technology Data Exchange (ETDEWEB)

Fu, Xinpeng [State; Li, Fangfei [State; Lin, Jung-Fu [Department; Gong, Yuanbo [State; Huang, Xiaoli [State; Huang, Yanping [State; Han, Bo [State; Zhou, Qiang [State; Cui, Tian [State

2017-07-19

Tailoring the excitonic properties in two-dimensional monolayer transition metal dichalcogenides (TMDs) through strain engineering is an effective means to explore their potential applications in optoelectronics and nanoelectronics. Here we report pressure-tuned photon emission of trions and excitons in monolayer MoSe2 via a diamond anvil cell (DAC) through photoluminescence measurements and theoretical calculations. Under quasi-hydrostatic compressive strain, our results show neutral (X0) and charged (X–) exciton emission of monolayer MoSe2 can be effectively tuned by alcohol mixture vs inert argon pressure transmitting media (PTM). During this process, X– emission undergoes a continuous blue shift until reaching saturation, while X0 emission turns up splitting. The pressure-dependent charging effect observed in alcohol mixture PTM results in the increase of the X– exciton component and facilitates the pressure-tuned emission of X– excitons. This substantial tunability of X– and X0 excitons in MoSe2 can be extended to other 2D TMDs, which holds potential for developing strained and optical sensing devices.

Phosphorescence as a probe of exciton formation and energy transfer in organic light emitting diodes

International Nuclear Information System (INIS)

Baldo, M.; Segal, M.

2004-01-01

The development of highly efficient phosphorescent molecules has approximately quadrupled the quantum efficiency of organic light emitting devices (OLEDs). By harnessing triplet as well as singlet excitons, efficient molecular phosphorescence has also enabled novel studies of exciton physics in organic semiconductors. In this review, we will summarize recent progress in understanding exciton formation and energy transfer using phosphorescent molecular probes. Particular emphasis is given to two topics of current interest: energy transfer in blue phosphorescent OLEDs, and quantifying the formation ratio of singlet to triplet excitons in small-molecular weight materials and polymers. (orig.)

Symposium GC: Nanoscale Charge Transport in Excitonic Solar Cells

Energy Technology Data Exchange (ETDEWEB)

Bommisetty, Venkat [Univ. of South Dakota, Vermillion, SD (United States)

2011-06-23

This paper provides a summary only and table of contents of the sessions. Excitonic solar cells, including all-organic, hybrid organic-inorganic and dye-sensitized solar cells (DSSCs), offer strong potential for inexpensive and large-area solar energy conversion. Unlike traditional inorganic semiconductor solar cells, where all the charge generation and collection processes are well understood, these excitonic solar cells contain extremely disordered structures with complex interfaces which results in large variations in nanoscale electronic properties and has a strong influence on carrier generation, transport, dissociation and collection. Detailed understanding of these processes is important for fabrication of highly efficient solar cells. Efforts to improve efficiency are underway at a large number of research groups throughout the world focused on inorganic and organic semiconductors, photonics, photophysics, charge transport, nanoscience, ultrafast spectroscopy, photonics, semiconductor processing, device physics, device structures, interface structure etc. Rapid progress in this multidisciplinary area requires strong synergetic efforts among researchers from diverse backgrounds. Such effort can lead to novel methods for development of new materials with improved photon harvesting and interfacial treatments for improved carrier transport, process optimization to yield ordered nanoscale morphologies with well defined electronic structures.

Organic solar cells: understanding the role of Förster resonance energy transfer.

Science.gov (United States)

Feron, Krishna; Belcher, Warwick J; Fell, Christopher J; Dastoor, Paul C

2012-12-12

Organic solar cells have the potential to become a low-cost sustainable energy source. Understanding the photoconversion mechanism is key to the design of efficient organic solar cells. In this review, we discuss the processes involved in the photo-electron conversion mechanism, which may be subdivided into exciton harvesting, exciton transport, exciton dissociation, charge transport and extraction stages. In particular, we focus on the role of energy transfer as described by F¨orster resonance energy transfer (FRET) theory in the photoconversion mechanism. FRET plays a major role in exciton transport, harvesting and dissociation. The spectral absorption range of organic solar cells may be extended using sensitizers that efficiently transfer absorbed energy to the photoactive materials. The limitations of F¨orster theory to accurately calculate energy transfer rates are discussed. Energy transfer is the first step of an efficient two-step exciton dissociation process and may also be used to preferentially transport excitons to the heterointerface, where efficient exciton dissociation may occur. However, FRET also competes with charge transfer at the heterointerface turning it in a potential loss mechanism. An energy cascade comprising both energy transfer and charge transfer may aid in separating charges and is briefly discussed. Considering the extent to which the photo-electron conversion efficiency is governed by energy transfer, optimisation of this process offers the prospect of improved organic photovoltaic performance and thus aids in realising the potential of organic solar cells.

Organic Solar Cells: Understanding the Role of Förster Resonance Energy Transfer

Directory of Open Access Journals (Sweden)

Paul C. Dastoor

2012-12-01

Full Text Available Organic solar cells have the potential to become a low-cost sustainable energy source. Understanding the photoconversion mechanism is key to the design of efficient organic solar cells. In this review, we discuss the processes involved in the photo-electron conversion mechanism, which may be subdivided into exciton harvesting, exciton transport, exciton dissociation, charge transport and extraction stages. In particular, we focus on the role of energy transfer as described by F¨orster resonance energy transfer (FRET theory in the photoconversion mechanism. FRET plays a major role in exciton transport, harvesting and dissociation. The spectral absorption range of organic solar cells may be extended using sensitizers that efficiently transfer absorbed energy to the photoactive materials. The limitations of F¨orster theory to accurately calculate energy transfer rates are discussed. Energy transfer is the first step of an efficient two-step exciton dissociation process and may also be used to preferentially transport excitons to the heterointerface, where efficient exciton dissociation may occur. However, FRET also competes with charge transfer at the heterointerface turning it in a potential loss mechanism. An energy cascade comprising both energy transfer and charge transfer may aid in separating charges and is briefly discussed. Considering the extent to which the photo-electron conversion efficiency is governed by energy transfer, optimisation of this process offers the prospect of improved organic photovoltaic performance and thus aids in realising the potential of organic solar cells.

Charge-Transfer States in Organic Solar Cells: Understanding the Impact of Polarization, Delocalization, and Disorder

KAUST Repository

Zheng, Zilong

2017-05-08

We investigate the impact of electronic polarization, charge delocalization, and energetic disorder on the charge-transfer (CT) states formed at a planar C60/pentacene interface. The ability to examine large complexes containing up to seven pentacene molecules and three C60 molecules allows us to take explicitly into account the electronic polarization effects. These complexes are extracted from a bilayer architecture modeled by molecular dynamics simulations and evaluated by means of electronic-structure calculations based on long-range-separated functionals (ωB97XD and BNL) with optimized range-separation parameters. The energies of the lowest charge-transfer states derived for the large complexes are in very good agreement with the experimentally reported values. The average singlet-triplet energy splittings of the lowest CT states are calculated not to exceed 10 meV. The rates of geminate recombination as well as of dissociation of the triplet excitons are also evaluated. In line with experiment, our results indicate that the pentacene triplet excitons generated through singlet fission can dissociate into separated charges on a picosecond time scale, despite the fact that their energy in C60/pentacene heterojunctions is slightly lower than the energies of the lowest CT triplet states.

Modelling excitonic energy transfer in the photosynthetic unit of purple bacteria

International Nuclear Information System (INIS)

Linnanto, J.M.; Korppi-Tommola, J.E.I.

2009-01-01

Molecular mechanics and quantum chemical configuration interaction calculations in combination with exciton theory were used to predict vibronic energies and eigenstates of light harvesting antennae and the reaction centre and to evaluate excitation energy transfer rates in the photosynthetic unit of purple bacteria. Excitation energy transfer rates were calculated by using the transition matrix formalism and exciton basis sets of the interacting antenna systems. Energy transfer rates of 600-800 fs from B800 ring to B850 ring in the LH2 antenna, 3-10 ps from LH2 to LH2 antenna, 2-8 ps from LH2 to LH1 antenna and finally 30-70 ps from LH1 to the reaction centre were obtained. Dependencies of energy transfer rates on lateral and vertical inter-complex distances were determined. The results indicate that a fair amount of spatial heterogeneity of antenna complexes in the photosynthetic membrane is tolerated without much loss in excitation energy transfer efficiency

Modelling excitonic energy transfer in the photosynthetic unit of purple bacteria

Energy Technology Data Exchange (ETDEWEB)

Linnanto, J.M. [Department of Chemistry, P.O. Box 35, FIN-40014 University of Jyvaeskylae, Jyvaeskylae (Finland)], E-mail: juha.m.linnanto@jyu.fi; Korppi-Tommola, J.E.I. [Department of Chemistry, P.O. Box 35, FIN-40014 University of Jyvaeskylae, Jyvaeskylae (Finland)

2009-02-23

Molecular mechanics and quantum chemical configuration interaction calculations in combination with exciton theory were used to predict vibronic energies and eigenstates of light harvesting antennae and the reaction centre and to evaluate excitation energy transfer rates in the photosynthetic unit of purple bacteria. Excitation energy transfer rates were calculated by using the transition matrix formalism and exciton basis sets of the interacting antenna systems. Energy transfer rates of 600-800 fs from B800 ring to B850 ring in the LH2 antenna, 3-10 ps from LH2 to LH2 antenna, 2-8 ps from LH2 to LH1 antenna and finally 30-70 ps from LH1 to the reaction centre were obtained. Dependencies of energy transfer rates on lateral and vertical inter-complex distances were determined. The results indicate that a fair amount of spatial heterogeneity of antenna complexes in the photosynthetic membrane is tolerated without much loss in excitation energy transfer efficiency.

Theory of interfacial charge-transfer complex photophysics in π-conjugated polymer-fullerene blends

Science.gov (United States)

Aryanpour, K.; Psiachos, D.; Mazumdar, S.

2010-03-01

We present a theory of the electronic structure and photophysics of 1:1 blends of derivatives of polyparaphenylenevinylene and fullerenes [1]. Within the same Coulomb-correlated Hamiltonian applied previously to interacting chains of single-component π-conjugated polymers [2], we find an exciplex state that occurs below the polymer's optical exciton. Weak absorption from the ground state occurs to the exciplex. We explain transient photoinduced absorptions in the blend [3], observed for both above-gap and below-gap photoexcitations, within our theory. Photoinduced absorptions for above-gap photoexcitation are from the optical exciton as well as the exciplex, while for below-gap photoexcitation induced absorptions are from the exciplex alone. In neither case are free polarons generated in the time scale of the experiment. Importantly, the photophysics of films of single-component π-conjugated polymers and blends can both be understood by extending Mulliken's theory of ground state charge-transfer to the case of excited state charge-transfer. [1] K. Aryanpour, D. Psiachos, and S. Mazumdar, arXiv:0908.0366 [2] D. Psiachos and S. Mazumdar, Phys. Rev. B. 79 155106 (2009) [3] T. Drori et al., Phys. Rev. Lett. 101, 037402 (2008)

Finite life time effects in the coherent exciton transfer

International Nuclear Information System (INIS)

Barvik, I.; Herman, P.

1992-04-01

The paper addresses a specific problem in the exciton transfer in molecular aggregates, namely the influence of the finite life time effects, on the memory functions entering the Generalized Master Equation (GME) which connect different sites of the system. 7 refs, 2 figs

Exciton broadening in WS2 /graphene heterostructures

International Nuclear Information System (INIS)

Hill, Heather M.; Rigosi, Albert F.; Raja, Archana

2017-01-01

Here, we have used optical spectroscopy to observe spectral broadening of WS 2 exciton reflectance peaks in heterostructures of monolayer WS 2 capped with mono- to few-layer graphene. The broadening is found to be similar for the A and B excitons and on the order of 5–10 meV. No strong dependence on the number of graphene layers was observed within experimental uncertainty. The broadening can be attributed to charge- and energy-transfer processes between the two materials, providing an observed lower bound for the corresponding time scales of 65 fs.

Electrical control of truly two-dimensional neutral and charged excitons in monolayer MoSe2

Science.gov (United States)

Ross, Jason; Wu, Sanfeng; Yu, Hongyi; Ghimire, Nirmal; Jones, Aaron; Aivazian, Grant; Yan, Jiaqiang; Mandrus, David; Xiao, Di; Xiao, Di; Xu, Xiaodong

2013-03-01

Monolayer transition metal dichalcogenides (TMDs) have emerged as ideal 2D semiconductors with valley and spin polarized excitations expected to enable true valley-tronics. Here we investigate MoSe2, a TMD which has yet to be characterized in the monolayer limit. Specifically, we examine excitons and trions (their singly charged counterparts) in the ultimate 2D limit. Utilizing high quality exfoliated MoSe2 monolayers, we report the observation and electrostatic tunability of positively charged (X +) , neutral (Xo), and negatively charged (X-) excitons via photoluminescence in FETs. The trion charging energy is large (30 meV), enhanced by strong confinement and heavy effective masses, while the linewidth is narrow (5 meV) at temperatures below 55 K. This is greater spectral contrast than in any known quasi-2D system. Further, the charging energies for X + and X- to are nearly identical implying the same effective mass for electrons and holes, which supports their recent description as massive Dirac fermions. This work demonstrates that monolayer MoSe2 is an ultimate 2D semiconductor opening the door for the investigation of truly 2D exciton physics while laying the ground work necessary to begin valley-spin polarization studies. Support: US DoE, BES, Division of MSE. HY and WY supported by Research Grant Council of Hong Kong

Ultrafast Exciton Dissociation and Long-Lived Charge Separation in a Photovoltaic Pentacene-MoS2 van der Waals Heterojunction.

Science.gov (United States)

Bettis Homan, Stephanie; Sangwan, Vinod K; Balla, Itamar; Bergeron, Hadallia; Weiss, Emily A; Hersam, Mark C

2017-01-11

van der Waals heterojunctions between two-dimensional (2D) layered materials and nanomaterials of different dimensions present unique opportunities for gate-tunable optoelectronic devices. Mixed-dimensional p-n heterojunction diodes, such as p-type pentacene (0D) and n-type monolayer MoS 2 (2D), are especially interesting for photovoltaic applications where the absorption cross-section and charge transfer processes can be tailored by rational selection from the vast library of organic molecules and 2D materials. Here, we study the kinetics of excited carriers in pentacene-MoS 2 p-n type-II heterojunctions by transient absorption spectroscopy. These measurements show that the dissociation of MoS 2 excitons occurs by hole transfer to pentacene on the time scale of 6.7 ps. In addition, the charge-separated state lives for 5.1 ns, up to an order of magnitude longer than the recombination lifetimes from previously reported 2D material heterojunctions. By studying the fractional amplitudes of the MoS 2 decay processes, the hole transfer yield from MoS 2 to pentacene is found to be ∼50%, with the remaining holes undergoing trapping due to surface defects. Overall, the ultrafast charge transfer and long-lived charge-separated state in pentacene-MoS 2 p-n heterojunctions suggest significant promise for mixed-dimensional van der Waals heterostructures in photovoltaics, photodetectors, and related optoelectronic technologies.

The relationship between the electric field induced dissociation of charge transfer (CT) excitons and the photocurrent in novel hybrid small molecular/polymeric solar cells

Energy Technology Data Exchange (ETDEWEB)

Inal, Sahika; Neher, Dieter [Universitaet Potsdam (Germany). Institut fuer Physik und Astronomie; Sellinger, Alan [Institute of Materials Research and Engineering, Singapore (China)

2010-07-01

Complete dissociation of coulombically bound interfacial states is an ultimate step accounting for photovoltaic performance. Recent work has proposed that the emission of CT-exciton, i.e. an exciplex, is a competing process to the generation of free charges. Here, we investigated the photophysical processes in a bulk heterojunction system using a soluble poly(p-phenylenevinylene) donor and a novel small molecular electron acceptor based on Vinazene (2-vinyl-4,5-dicyanoimidazole). Recent work has shown that this blend exhibits a featureless emission, prominent at long wavelengths of the spectrum, which was attributed to a CT-exciton. We monitored the field induced dissociation of these CT-excitons by means of steady state and time resolved PL spectroscopy. Shortened decay times and reduced PL emission in blend film evidence the dissociation of the emissive intermolecular pair by the external electric field. Analyzing the dependence of the photocurrent and external quantum efficiency on the external field, the fate of the separated exciplex pairs is tackled. It is suggested that the formation of free carriers involves channels other than CT-excitons in such blends.

Perovskite Excitonics : Primary Exciton Creation and Crossover from Free Carriers to a Secondary Exciton Phase

NARCIS (Netherlands)

Sarritzu, Valerio; Sestu, Nicola; Marongiu, Daniela; Chang, Xueqing; Wang, Qingqian; Loi, Maria Antonietta; Quochi, Francesco; Saba, Michele; Mura, Andrea; Bongiovanni, Giovanni

2018-01-01

Understanding exciton formation is of fundamental importance for emerging optoelectronic materials, like hybrid organic-inorganic perovskites, as excitons are the lowest-energy photoexcitations in semiconductors, are electrically neutral, and do not directly contribute to charge transport, but can

Decay dynamics of neutral and charged excitonic complexes in single InAs/GaAs QDs

International Nuclear Information System (INIS)

Feucker, Max; Seguin, Robert; Rodt, Sven; Poetschke, Konstantin; Bimberg, Dieter

2008-01-01

Across the inhomogeneously broadened lineshape of a quantum dot (QD) ensemble the decay times are expected to vary since the wavefunctions and the oscillator strengths are sensitive to the actual geometry of the QD. We performed time-resolved cathodoluminescence spectroscopy of 26 different single InAs/GaAs QDs to investigate the decay dynamics of neutral and charged excitonic complexes. The largest decay rate was found for the XX + , followed by XX, X + and finally the X. We will show that the ratios of lifetimes of the different excitonic complexes are mainly governed by the number of involved recombination channels. There is excellent agreement between the measured and predicted values for the lifetime ratios of the neutral (X/XX) and the positively charged (X + /XX + ) complexes. Surprisingly the lifetime of the exciton (X) shows a much larger yet unexplained scatter than that of all the other complexes

Electrical control of optical orientation of neutral and negatively charged excitons in an n -type semiconductor quantum well

Science.gov (United States)

Dzhioev, R. I.; Korenev, V. L.; Lazarev, M. V.; Sapega, V. F.; Gammon, D.; Bracker, A. S.

2007-01-01

We report electric field induced increase of spin orientation of negatively charged excitons (trions) localized in n -type GaAs/AlGaAs quantum well. Under resonant excitation of free neutral heavy-hole excitons, the polarization of trions increases dramatically with electrical injection of electrons. The polarization enhancement correlates strongly with trion/exciton luminescence intensity ratio. This effect results from a very efficient trapping of free neutral excitons by the quantum well interfacial fluctuations (“natural” quantum dots) containing resident electrons.

Dissociative electron attachment and charge transfer in condensed matter

International Nuclear Information System (INIS)

Bass, A.D.; Sanche, L.

2003-01-01

Experiments using energy-selected beams of electrons incident from vacuum upon thin vapour deposited solids show that, as in the gas-phase, scattering cross sections at low energies are dominated by the formation of temporary negative ions (or resonances) and that molecular damage may be effected via dissociative electron attachment (DEA). Recent results also show that charge transfer between anionic states of target molecules and their environment is often crucial in determining cross sections for electron driven processes. Here, we review recent work from our laboratory, in which charge transfer is observed. For rare gas solids, electron exchange between the electron-exciton complex and either a metal substrate or co-adsorbed molecule enhances the desorption of metastable atoms and/or molecular dissociation. We discuss how transient electron capture by surface electron states of a substrate and subsequent electron transfer to a molecular adsorbate enhances the effective cross sections for DEA. We also consider the case of DEA to CF 2 Cl 2 condensed on water and ammonia ices, where electron exchange between pre-solvated electron states of ice and transient molecular anions can also increase DEA cross sections. Electron transfer from molecular resonances into pre-solvated electron states of ice is also discussed

Energy Migration in Organic Thin Films--From Excitons to Polarons

Science.gov (United States)

Mullenbach, Tyler K.

The rise of organic photovoltaic devices (OPVs) and organic light-emitting devices has generated interest in the physics governing exciton and polaron dynamics in thin films. Energy transfer has been well studied in dilute solutions, but there are emergent properties in thin films and greater complications due to complex morphologies which must be better understood. Despite the intense interest in energy transport in thin films, experimental limitations have slowed discoveries. Here, a new perspective of OPV operation is presented where photovoltage, instead of photocurrent, plays the fundamental role. By exploiting this new vantage point the first method of measuring the diffusion length (LD) of dark (non-luminescent) excitons is developed, a novel photodetector is invented, and the ability to watch exciton arrival, in real-time, at the donor-acceptor heterojunction is presented. Using an enhanced understanding of exciton migration in thin films, paradigms for enhancing LD by molecular modifications are discovered, and the first exciton gate is experimentally and theoretically demonstrated. Generation of polarons from exciton dissociation represents a second phase of energy migration in OPVs that remains understudied. Current approaches are capable of measuring the rate of charge carrier recombination only at open-circuit. To enable a better understanding of polaron dynamics in thin films, two new approaches are presented which are capable of measuring both the charge carrier recombination and transit rates at any OPV operating voltage. These techniques pave the way for a more complete understanding of charge carrier kinetics in molecular thin films.

Efficient Exciton Diffusion and Resonance-Energy Transfer in Multi-Layered Organic Epitaxial Nanofibers

DEFF Research Database (Denmark)

Tavares, Luciana; Cadelano, Michele; Quochi, Francesco

2015-01-01

Multi-layered epitaxial nanofibers are exemplary model systems for the study of exciton dynamics and lasing in organic materials due to their well-defined morphology, high luminescence efficiencies, and color tunability. We resort to temperature-dependent cw and picosecond photoluminescence (PL......) spectroscopy to quantify exciton diffusion and resonance-energy transfer (RET) processes in multi-layered nanofibers consisting of alternating layers of para-hexaphenyl (p6P) and α-sexithiophene (6T), serving as exciton donor and acceptor material, respectively. The high probability for RET processes...... is confirmed by Quantum Chemical calculations. The activation energy for exciton diffusion in p6P is determined to be as low as 19 meV, proving p6P epitaxial layers also as a very suitable donor material system. The small activation energy for exciton diffusion of the p6P donor material, the inferred high p6P...

Influence of image charge effect on exciton fine structure in an organic-inorganic quantum well material

Energy Technology Data Exchange (ETDEWEB)

Takagi, Hidetsugu; Kunugita, Hideyuki; Ema, Kazuhiro [Department of Physics, Sophia University, 7-1 Kioi-cho, Chiyoda-ku, Tokyo 102-8554 (Japan); Sato, Mikio; Takeoka, Yuko [Department of Materials and Life Sciences, Sophia University, 7-1 Kioi-cho, Chiyoda-ku, Tokyo 102-8554 (Japan)

2013-12-04

We have investigated experimentally excitonic properties in organic-inorganic hybrid multi quantum well crystals, (C{sub 4}H{sub 9}NH{sub 3}){sub 2}PbBr{sub 4} and (C{sub 6}H{sub 5}−C{sub 2}H{sub 4}NH{sub 3}){sub 2}PbBr{sub 4}, by measuring photoluminescence, reflectance, photoluminescence excitation spectra. In these materials, the excitonic binding energies are enhanced not only by quantum confinement effect (QCE) but also by image charge effect (ICE), since the dielectric constant of the barrier layers is much smaller than that of the well layers. By comparing the 1s-exciton and 2s-exciton energies, we have investigated the influence of ICE with regard to the difference of the Bohr radius.

Exciton-Dissociation and Charge-Recombination Processes in Pentacene/C 60 Solar Cells: Theoretical Insight into the Impact of Interface Geometry

KAUST Repository

Yi, Yuanping; Coropceanu, Veaceslav; Brédas, Jean-Luc

2009-01-01

The exciton-dissociation and charge-recombination processes in organic solar cells based on pentacene/C60 heterojunctions are investigated by means of quantum-mechanical calculations. The electronic couplings and the rates of exciton dissociation

Exciton and Hole-Transfer Dynamics in Polymer: Fullerene Blends

Directory of Open Access Journals (Sweden)

van Loosdrecht P. H. M.

2013-03-01

Full Text Available Ultrafast hole transfer dynamics from fullerene derivative to polymer in bulk heterojunction blends are studied with visible-pump - IR-probe spectroscopy. The hole transfer process is found to occur in 50/300 fs next to the interface, while a longer 15-ps time is attributed to exciton diffusion towards interface in PC71BM domains. High polaron generation efficiency in P3HT blends indicates excellent intercalation between the polymer and the fullerene even at highest PC71BM concentration thereby yielding a valuable information on the blend morphology.

Field-modulation spectroscopy of pentacene thin films using field-effect devices: Reconsideration of the excitonic structure

Science.gov (United States)

Haas, Simon; Matsui, Hiroyuki; Hasegawa, Tatsuo

2010-10-01

We report pure electric-field effects on the excitonic absorbance of pentacene thin films as measured by unipolar field-effect devices that allowed us to separate the charge accumulation effects. The field-modulated spectra between 1.8 and 2.6 eV can be well fitted with the first derivative curve of Frenkel exciton absorption and its vibronic progression, and at higher energy a field-induced feature appears at around 2.95 eV. The results are in sharp contrast to the electroabsorption spectra reported by Sebastian in previous studies [Chem. Phys. 61, 125 (1981)10.1016/0301-0104(81)85055-0], and leads us to reconsider the excitonic structure including the location of charge-transfer excitons. Nonlinear π -electronic response is discussed based on second-order electro-optic (Kerr) spectra.

Triplet energy transfer and triplet exciton recycling in singlet fission sensitized organic heterojunctions

Science.gov (United States)

Hamid, Tasnuva; Yambem, Soniya D.; Crawford, Ross; Roberts, Jonathan; Pandey, Ajay K.

2017-08-01

Singlet exciton fission is a process where an excited singlet state splits into two triplets, thus leading to generation of multiple excitons per absorbed photon in organic semiconductors. Herein, we report a detailed exciton management approach for multiexciton harvesting over a broadband region of the solar spectrum in singlet fission sensitized organic photodiodes. Through systematic studies on the model cascade of pentacene/rubrene/C60, we found that efficient photocurrent generation from pentacene can still occur despite the presence of a >10nm thick interlayer of rubrene in between the pentacene/C60 heterojunction. Our results show that thin rubrene interlayers of thickness pentacene despite having a reasonably thick rubrene interlayer, that too with higher triplet energy (T1=1.12 eV) than pentacene (T1= 0.86 eV), makes its operation a rather interesting result. We discuss the role of rubrene interlayer film discontinuity, triplet exciton reflection from rubrene interlayer and triplet energy transfer from rubrene to pentacene layer followed by diffusion of triplet excitons through rubrene as plausible mechanisms that would enable triplet excitons from pentacene to generate significant photocurrent in a multilayer organic heterojunction.

Interconversion between Free Charges and Bound Excitons in 2D Hybrid Lead Halide Perovskites.

Science.gov (United States)

Gélvez-Rueda, María C; Hutter, Eline M; Cao, Duyen H; Renaud, Nicolas; Stoumpos, Constantinos C; Hupp, Joseph T; Savenije, Tom J; Kanatzidis, Mercouri G; Grozema, Ferdinand C

2017-11-30

The optoelectronic properties of hybrid perovskites can be easily tailored by varying their components. Specifically, mixing the common short organic cation (methylammonium (MA)) with a larger one (e.g., butyl ammonium (BA)) results in 2-dimensional perovskites with varying thicknesses of inorganic layers separated by the large organic cation. In both of these applications, a detailed understanding of the dissociation and recombination of electron-hole pairs is of prime importance. In this work, we give a clear experimental demonstration of the interconversion between bound excitons and free charges as a function of temperature by combining microwave conductivity techniques with photoluminescence measurements. We demonstrate that the exciton binding energy varies strongly (between 80 and 370 meV) with the thickness of the inorganic layers. Additionally, we show that the mobility of charges increases with the layer thickness, in agreement with calculated effective masses from electronic structure calculations.

Interconversion between Free Charges and Bound Excitons in 2D Hybrid Lead Halide Perovskites

International Nuclear Information System (INIS)

Gélvez-Rueda, María C.; Hutter, Eline M.; Cao, Duyen H.; Renaud, Nicolas; Stoumpos, Constantinos C.

2017-01-01

The optoelectronic properties of hybrid perovskites can be easily tailored by varying their components. Specifically, mixing the common short organic cation (methylammonium (MA)) with a larger one (e.g., butyl ammonium (BA)) results in 2-dimensional perovskites with varying thicknesses of inorganic layers separated by the large organic cation. In both of these applications, a detailed understanding of the dissociation and recombination of electron–hole pairs is of prime importance. Here in this work, we give a clear experimental demonstration of the interconversion between bound excitons and free charges as a function of temperature by combining microwave conductivity techniques with photoluminescence measurements. We demonstrate that the exciton binding energy varies strongly (between 80 and 370 meV) with the thickness of the inorganic layers. Additionally, we show that the mobility of charges increases with the layer thickness, in agreement with calculated effective masses from electronic structure calculations.

Spin-dependent exciton-exciton interaction potential in two- and three-dimensional structure semiconductors under excitation

International Nuclear Information System (INIS)

Nguyen Ba An; Hoang Ngoc Cam; Nguyen Trung Dan

1990-08-01

Analytical expressions of the exciton-exciton interaction potentials have been approximately derived in both 2D and 3D structure materials exhibiting explicit dependences on exciton momentum difference, momentum transfer, electron-hole effective mass ratio and two-exciton state spin symmetry. Numerical calculations show that the character of the exciton-exciton interaction is determined by all of the above-mentioned dependences. (author). 32 refs, 7 figs

Probing Exciton Diffusion and Dissociation in Single-Walled Carbon Nanotube-C60 Heterojunctions

Energy Technology Data Exchange (ETDEWEB)

Dowgiallo, Anne-Marie; Mistry, Kevin S.; Johnson, Justin C.; Reid, Obadiah G.; Blackburn, Jeffrey L.

2016-05-19

The efficiency of thin-film organic photovoltaic (OPV) devices relies heavily upon the transport of excitons to type-II heterojunction interfaces, where there is sufficient driving force for exciton dissociation and ultimately the formation of charge carriers. Semiconducting single-walled carbon nanotubes (SWCNTs) are strong near-infrared absorbers that form type-II heterojunctions with fullerenes such as C60. Although the efficiencies of SWCNT-fullerene OPV devices have climbed over the past few years, questions remain regarding the fundamental factors that currently limit their performance. In this study, we determine the exciton diffusion length in the C60 layer of SWCNT-C60 bilayer active layers using femtosecond transient absorption measurements. We demonstrate that hole transfer from photoexcited C60 molecules to SWCNTs can be tracked by the growth of narrow spectroscopic signatures of holes in the SWCNT 'reporter layer'. In bilayers with thick C60 layers, the SWCNT charge-related signatures display a slow rise over hundreds of picoseconds, reflecting exciton diffusion through the C60 layer to the interface. A model based on exciton diffusion with a Beer-Lambert excitation profile, as well as Monte Carlo simulations, gives the best fit to the data as a function of C60 layer thickness using an exciton diffusion length of approximately 5 nm.

Defects activated photoluminescence in two-dimensional semiconductors: interplay between bound, charged, and free excitons

Science.gov (United States)

Tongay, Sefaattin; Suh, Joonki; Ataca, Can; Fan, Wen; Luce, Alexander; Kang, Jeong Seuk; Liu, Jonathan; Ko, Changhyun; Raghunathanan, Rajamani; Zhou, Jian; Ogletree, Frank; Li, Jingbo; Grossman, Jeffrey C.; Wu, Junqiao

2013-01-01

Point defects in semiconductors can trap free charge carriers and localize excitons. The interaction between these defects and charge carriers becomes stronger at reduced dimensionalities, and is expected to greatly influence physical properties of the hosting material. We investigated effects of anion vacancies in monolayer transition metal dichalcogenides as two-dimensional (2D) semiconductors where the vacancies density is controlled by α-particle irradiation or thermal-annealing. We found a new, sub-bandgap emission peak as well as increase in overall photoluminescence intensity as a result of the vacancy generation. Interestingly, these effects are absent when measured in vacuum. We conclude that in opposite to conventional wisdom, optical quality at room temperature cannot be used as criteria to assess crystal quality of the 2D semiconductors. Our results not only shed light on defect and exciton physics of 2D semiconductors, but also offer a new route toward tailoring optical properties of 2D semiconductors by defect engineering. PMID:24029823

Ultrafast interfacial energy transfer and interlayer excitons in the monolayer WS2/CsPbBr3 quantum dot heterostructure.

Science.gov (United States)

Li, Han; Zheng, Xin; Liu, Yu; Zhang, Zhepeng; Jiang, Tian

2018-01-25

The idea of fabricating artificial solids with band structures tailored to particular applications has long fascinated condensed matter physicists. Heterostructure (HS) construction is viewed as an effective and appealing approach to engineer novel electronic properties in two dimensional (2D) materials. Different from common 2D/2D heterojunctions where energy transfer is rarely observed, CsPbBr 3 quantum dots (0D-QDs) interfaced with 2D materials have become attractive HSs for exploring the physics of charge transfer and energy transfer, due to their superior optical properties. In this paper, a new 0D/2D HS is proposed and experimentally studied, making it possible to investigate both light utilization and energy transfer. Specifically, this HS is constructed between monolayer WS 2 and CsPbBr 3 QDs, and exhibits a hybrid band alignment. The dynamics of energy transfer within the investigated 0D/2D HS is characterized by femtosecond transient absorption spectrum (TAS) measurements. The TAS results reveal that ultrafast energy transfer caused by optical excitation is observed from CsPbBr 3 QDs to the WS 2 layer, which can increase the exciton fluence within the WS 2 layer up to 69% when compared with pristine ML WS 2 under the same excitation fluence. Moreover, the formation and dynamics of interlayer excitons have also been investigated and confirmed in the HS, with a calculated recombination time of 36.6 ps. Finally, the overall phenomenological dynamical scenario for the 0D/2D HS is established within the 100 ps time region after excitation. The techniques introduced in this work can also be applied to versatile optoelectronic devices based on low dimensional materials.

Migration of CT triplet excitons in TCNB-biphenyl and TCNB-HMB crystals

Science.gov (United States)

Kozankiewicz, BolesAw

1994-01-01

Delayed fluorescence decay curves of charge transfer (CT) crystals of tetracyanobenzene with biphenyl (TCNB-B) and with hexamethylbenzene (TCNB-HMB) have been studied over a wide temperature range (5-200 K). The decay curves have been adequately described by decay expressions derived for different mechanisms of triplet-triplet annihilation. This analysis points to one-dimensional, thermally activated motion of CT triplet excitons. The estimated activation energies for the exciton hopping are 360±60 and 650±100 cm -1 (or 550±150 cm -1 depending on the applied model) for the TCNB-B and TCNB-HMB crystals, respectively. The results seem to confirm the self-trapping of triplet CT excitons.

Conformation-related exciton localization and charge-pair formation in polythiophenes: ensemble and single-molecule study.

Science.gov (United States)

Sugimoto, Toshikazu; Habuchi, Satoshi; Ogino, Kenji; Vacha, Martin

2009-09-10

We study conformation-dependent photophysical properties of polythiophene (PT) by molecular dynamics simulations and by ensemble and single-molecule optical experiments. We use a graft copolymer consisting of a polythiophene backbone and long polystyrene branches and compare its properties with those obtained on the same polythiophene derivative without the side chains. Coarse-grain molecular dynamics simulations show that in a poor solvent, the PT without the side chains (PT-R) forms a globulelike conformation in which distances between any two conjugated segments on the chain are within the Forster radius for efficient energy transfer. In the PT with the polystyrene branches (PT-PS), the polymer main PT chain retains an extended coillike conformation, even in a poor solvent, and the calculated distances between conjugated segments favor energy transfer only between a few neighboring chromophores. The theoretical predictions are confirmed by measurements of fluorescence anisotropy and fluorescence blinking of the polymers' single chains. High anisotropy ratios and two-state blinking in PT-R are due to localization of the exciton on a single conjugated segment. These signatures of exciton localization are absent in single chains of PT-PS. Electric-field-induced quenching measured as a function of concentration of PT dispersed in an inert matrix showed that in well-isolated chains of PT-PS, the exciton dissociation is an intrachain process and that aggregation of the PT-R chains causes an increase in quenching due to the onset of interchain interactions. Measurements of the field-induced quenching on single chains indicate that in PT-R, the exciton dissociation is a slower process that takes place only after the exciton is localized on one conjugated segment.

Exciton Seebeck effect in molecular systems

Energy Technology Data Exchange (ETDEWEB)

Yan, Yun-An, E-mail: yunan@nano.gznc.edu.cn [Guizhou Provincial Key Laboratory of Computational Nanomaterial Science, Guizhou Normal College, Guiyang, Guizhou 550018 (China); Cai, Shaohong [Guizhou Key Laboratory of Economic System Simulation, Guizhou University of Finance and Economics, Guiyang 550004 (China)

2014-08-07

We investigate the exciton dynamics under temperature difference with the hierarchical equations of motion. Through a nonperturbative simulation of the transient absorption of a heterogeneous trimer model, we show that the temperature difference causes exciton population redistribution and affects the exciton transfer time. It is found that one can reproduce not only the exciton population redistribution but also the change of the exciton transfer time induced by the temperature difference with a proper tuning of the site energies of the aggregate. In this sense, there exists a site energy shift equivalence for any temperature difference in a broad range. This phenomenon is similar to the Seebeck effect as well as spin Seebeck effect and can be named as exciton Seebeck effect.

PbSe Nanocrystal Excitonic Solar Cells

KAUST Repository

Choi, Joshua J.

2009-11-11

We report the design, fabrication, and characterization of colloidal PbSe nanocrystal (NC)-based photovoltaic test structures that exhibit an excitonic solar cell mechanism. Charge extraction from the NC active layer is driven by a photoinduced chemical potential energy gradient at the nanostructured heterojunction. By minimizing perturbation to PbSe NC energy levels and thereby gaining insight into the "intrinsic" photovoltaic properties and charge transfer mechanism of PbSe NC, we show a direct correlation between interfacial energy level offsets and photovoltaic device performance. Size dependent PbSe NC energy levels were determined by cyclic voltammetry and optical spectroscopy and correlated to photovoltaic measurements. Photovoltaic test structures were fabricated from PbSe NC films sandwiched between layers of ZnO nanoparticles and PEDOT:PSS as electron and hole transporting elements, respectively. The device current-voltage characteristics suggest a charge separation mechanism that Is distinct from previously reported Schottky devices and consistent with signatures of excitonic solar cells. Remarkably, despite the limitation of planar junction structure, and without film thickness optimization, the best performing device shows a 1-sun power conversion efficiency of 3.4%, ranking among the highest performing NC-based solar cells reported to date. © 2009 American Chemical Society.

Ligand-dependent exciton dynamics and photovoltaic properties of PbS quantum dot heterojunction solar cells.

Science.gov (United States)

Chang, Jin; Ogomi, Yuhei; Ding, Chao; Zhang, Yao Hong; Toyoda, Taro; Hayase, Shuzi; Katayama, Kenji; Shen, Qing

2017-03-01

The surface chemistry of colloidal quantum dots (QDs) plays an important role in determining the photoelectric properties of QD films and the corresponding quantum dot heterojunction solar cells (QDHSCs). To investigate the effects of the ligand structure on the photovoltaic performance and exciton dynamics of QDHSCs, PbS QDHSCs were fabricated by the solid state ligand exchange method with mercaptoalkanoic acid as the cross-linking ligand. Temperature-dependent photoluminescence and ultrafast transient absorption spectra show that the electronic coupling and charge transfer rate within QD ensembles were monotonically enhanced as the ligand length decreased. However, in practical QDHSCs, the second shortest ligand 3-mercaptopropionic acid (MPA) showed higher power conversion efficiency than the shortest ligand thioglycolic acid (TGA). This could be attributed to the difference in their surface trap states, supported by thermally stimulated current measurements. Moreover, compared with the non-conjugated ligand MPA, the conjugated ligand 4-mercaptobenzoic acid (MBA) introduces less trap states and has a similar charge transfer rate in QD ensembles, but has poor photovoltaic properties. This unexpected result could be contributed by the QD-ligand orbital mixing, leading to the charge transfer from QDs to ligands instead of charge transfer between adjacent QDs. This work highlights the significant effects of ligand structures on the photovoltaic properties and exciton dynamics of QDHSCs, which would shed light on the further development of QD-based photoelectric devices.

Charge transfer in astrophysical nebulae

International Nuclear Information System (INIS)

Shields, G.A.

1990-01-01

Charge transfer has become a standard ingredient in models of ionized nebulae, supernovae remnants and active galactic nuclei. Charge transfer rate coefficients and the physics of ionized nebulae are considered. Charge transfer is applied to the ionization structure and line emission of ionized nebulae. Photoionized nebulae observations are used to test theoretical predictions of charge transfer rates. (author)

Exciton transfer under dichotomic noise: GME treatment

International Nuclear Information System (INIS)

Barvik, I.; Warns, C.; Reineker, P.

1995-08-01

The exciton energy transfer between molecules in a dimer is investigated using a model, in which the influence of the phonons is described by a dichotomic stochastic process with colored noise giving rise to modulations of the molecular excitation energies. The solution of equations of motion for the density matrix of the system (obtained algebraically on a computer) is used to determine (also algebraically) the form of the memory functions which enter the Generalized Master Equation. The behaviour of the roots and their weights in the memory function is discussed thoroughly. Connection of the so called coherence time to stochastic parameters is treated analytically. Different limiting cases are investigated. (author). 14 refs, 9 figs

Charge migration and charge transfer in molecular systems

Directory of Open Access Journals (Sweden)

Hans Jakob Wörner

2017-11-01

Full Text Available The transfer of charge at the molecular level plays a fundamental role in many areas of chemistry, physics, biology and materials science. Today, more than 60 years after the seminal work of R. A. Marcus, charge transfer is still a very active field of research. An important recent impetus comes from the ability to resolve ever faster temporal events, down to the attosecond time scale. Such a high temporal resolution now offers the possibility to unravel the most elementary quantum dynamics of both electrons and nuclei that participate in the complex process of charge transfer. This review covers recent research that addresses the following questions. Can we reconstruct the migration of charge across a molecule on the atomic length and electronic time scales? Can we use strong laser fields to control charge migration? Can we temporally resolve and understand intramolecular charge transfer in dissociative ionization of small molecules, in transition-metal complexes and in conjugated polymers? Can we tailor molecular systems towards specific charge-transfer processes? What are the time scales of the elementary steps of charge transfer in liquids and nanoparticles? Important new insights into each of these topics, obtained from state-of-the-art ultrafast spectroscopy and/or theoretical methods, are summarized in this review.

Dexter energy transfer pathways.

Science.gov (United States)

Skourtis, Spiros S; Liu, Chaoren; Antoniou, Panayiotis; Virshup, Aaron M; Beratan, David N

2016-07-19

Energy transfer with an associated spin change of the donor and acceptor, Dexter energy transfer, is critically important in solar energy harvesting assemblies, damage protection schemes of photobiology, and organometallic opto-electronic materials. Dexter transfer between chemically linked donors and acceptors is bridge mediated, presenting an enticing analogy with bridge-mediated electron and hole transfer. However, Dexter coupling pathways must convey both an electron and a hole from donor to acceptor, and this adds considerable richness to the mediation process. We dissect the bridge-mediated Dexter coupling mechanisms and formulate a theory for triplet energy transfer coupling pathways. Virtual donor-acceptor charge-transfer exciton intermediates dominate at shorter distances or higher tunneling energy gaps, whereas virtual intermediates with an electron and a hole both on the bridge (virtual bridge excitons) dominate for longer distances or lower energy gaps. The effects of virtual bridge excitons were neglected in earlier treatments. The two-particle pathway framework developed here shows how Dexter energy-transfer rates depend on donor, bridge, and acceptor energetics, as well as on orbital symmetry and quantum interference among pathways.

The role of exciton ionization processes in bulk heterojunction organic photovoltaic cells

Science.gov (United States)

Zou, Yunlong; Holmes, Russell

2015-03-01

Dissociating photogenerated excitons into their constituent charges is essential for efficient photoconversion in organic semiconductors. Organic photovoltaics cells (OPV) widely adopt a heterojunction architecture where dissociation is facilitated by charge transfer at a donor-acceptor (D-A) interface. Interestingly, recent work on MoOx/C60 Schottky OPVs has demonstrated that excitons in C60 may also undergo bulk-ionization to generate photocurrent, driven by the built-in field at the MoOx/C60 interface. Here, we show that bulk-ionization processes also contribute to the photocurrent in bulk heterojunction (BHJ) OPVs with fullerene-rich compositions. The short-circuit current density (JSC) in a MoOx/C60 Schottky OPVs shows almost no dependence on temperature down to 80 K. This characteristic of bulk-ionization allows the use of temperature-dependent measurements of JSC to distinguish dissociation by bulk-ionization from charge transfer at a D-A interface. For BHJ OPVs constructed using the D-A pairing of boron subphthalocyanine chloride (SubPc)-C60, bulk-ionization is found to contribute >10% of the total photocurrent and >30% of the photocurrent from C60. We further find that fullerene-rich SubPc-C60 BHJ OPVs show a larger open-circuit voltage (VOC) than evenly mixed BHJs due to the presence of bulk-ionization. This talk will examine the dependence of JSC and VOC on the relative fraction of dissociation by charge transfer and bulk-ionization processes.

Through space and through bridge channels of charge transfer at p-n nano-junctions: A DFT study

Energy Technology Data Exchange (ETDEWEB)

Dandu, Naveen [Department of Chemistry and Biochemistry, NDSU, Fargo, ND 58108 (United States); Tretiak, Sergei [Theoretical Division, Center for Nonlinear Studies (CNLS) and Center for Integrated Nanotechnologies (CINT), Los Alamos National Laboratory, Los Alamos, 57069, NM 87454 (United States); Kilina, Svetlana [Department of Chemistry and Biochemistry, NDSU, Fargo, ND 58108 (United States); Kilin, Dmitri, E-mail: Dmitri.Kilin@ndsu.edu [Department of Chemistry and Biochemistry, NDSU, Fargo, ND 58108 (United States)

2016-12-20

Highlights: • Properties of interacting QDs depend on the fashion of interaction: through-bond or through-space. • The disconnected and undoped dimer models shows FÓ§rster band formation. • Dimer models with some doping exhibit degenerate charge-transfer excitons. • p- and n-doped qds shows polarization at the interface. • A photoexcitation polarizes p-n interface, in relation to phototovoltaic effect. - Abstract: Details of charge density distribution at p-n nano interface are analyzed with density functional theory techniques using model system of dimers of doped silicon quantum dots interacting through bond and through space. Spatial distributions of transition densities between the ground and excited states suggest the character of essential electronic excitations, which have a FÓ§rster, bound, unbound, or charge transfer character. A redistribution of electronic density from n-impurities to p-impurities results in a ground state polarization and creates an offset of energies of the bands localized on p-doped quantum dot and the bands localized on n-doped quantum dot. Although impurities contribute very few orbitals to the total density, a ground state charge redistribution and polarization are both responsible for the presence of a large number of charge transfer excitations involving solely silicon orbitals.

Exciton management in organic photovoltaic multidonor energy cascades.

Science.gov (United States)

Griffith, Olga L; Forrest, Stephen R

2014-05-14

Multilayer donor regions in organic photovoltaics show improved power conversion efficiency when arranged in decreasing exciton energy order from the anode to the acceptor interface. These so-called "energy cascades" drive exciton transfer from the anode to the dissociating interface while reducing exciton quenching and allowing improved overlap with the solar spectrum. Here we investigate the relative importance of exciton transfer and blocking in a donor cascade employing diphenyltetracene (D1), rubrene (D2), and tetraphenyldibenzoperiflanthene (D3) whose optical gaps monotonically decrease from D1 to D3. In this structure, D1 blocks excitons from quenching at the anode, D2 accepts transfer of excitons from D1 and blocks excitons at the interface between D2 and D3, and D3 contributes the most to the photocurrent due to its strong absorption at visible wavelengths, while also determining the open circuit voltage. We observe singlet exciton Förster transfer from D1 to D2 to D3 consistent with cascade operation. The power conversion efficiency of the optimized cascade OPV with a C60 acceptor layer is 7.1 ± 0.4%, which is significantly higher than bilayer devices made with only the individual donors. We develop a quantitative model to identify the dominant exciton processes that govern the photocurrent generation in multilayer organic structures.

Impact of undamped and damped intramolecular vibrations on the efficiency of photosynthetic exciton energy transfer

Science.gov (United States)

Juhász, Imre Benedek; Csurgay, Árpád I.

2018-04-01

In recent years, the role of molecular vibrations in exciton energy transfer taking place during the first stage of photosynthesis attracted increasing interest. Here, we present a model formulated as a Lindblad-type master equation that enables us to investigate the impact of undamped and especially damped intramolecular vibrational modes on the exciton energy transfer, particularly its efficiency. Our simulations confirm the already reported effects that the presence of an intramolecular vibrational mode can compensate the energy detuning of electronic states, thus promoting the energy transfer; and, moreover, that the damping of such a vibrational mode (in other words, vibrational relaxation) can further enhance the efficiency of the process by generating directionality in the energy flow. As a novel result, we show that this enhancement surpasses the one caused by pure dephasing, and we present its dependence on various system parameters (time constants of the environment-induced relaxation and excitation processes, detuning of the electronic energy levels, frequency of the intramolecular vibrational modes, Huang-Rhys factors, temperature) in dimer model systems. We demonstrate that vibrational-relaxation-enhanced exciton energy transfer (VREEET) is robust against the change of these characteristics of the system and occurs in wide ranges of the investigated parameters. With simulations performed on a heptamer model inspired by the Fenna-Matthews-Olson (FMO) complex, we show that this mechanism can be even more significant in larger systems at T = 300 K. Our results suggests that VREEET might be prevalent in light-harvesting complexes.

Efficient charge-carrier extraction from Ag₂S quantum dots prepared by the SILAR method for utilization of multiple exciton generation.

Science.gov (United States)

Zhang, Xiaoliang; Liu, Jianhua; Johansson, Erik M J

2015-01-28

The utilization of electron-hole pairs (EHPs) generated from multiple excitons in quantum dots (QDs) is of great interest toward efficient photovoltaic devices and other optoelectronic devices; however, extraction of charge carriers remains difficult. Herein, we extract photocharges from Ag2S QDs and investigate the dependence of the electric field on the extraction of charges from multiple exciton generation (MEG). Low toxic Ag2S QDs are directly grown on TiO2 mesoporous substrates by employing the successive ionic layer adsorption and reaction (SILAR) method. The contact between QDs is important for the initial charge separation after MEG and for the carrier transport, and the space between neighbor QDs decreases with more SILAR cycles, resulting in better charge extraction. At the optimal electric field for extraction of photocharges, the results suggest that the threshold energy (hνth) for MEG is 2.41Eg. The results reveal that Ag2S QD is a promising material for efficient extraction of charges from MEG and that QDs prepared by SILAR have an advantageous electrical contact facilitating charge separation and extraction.

Dissipative exciton transfer in donor-bridge-acceptor systems: numerical renormalization group calculation of equilibrium properties

Energy Technology Data Exchange (ETDEWEB)

Tornow, Sabine [Theoretische Physik III, Elektronische Korrelationen und Magnetismus, Universitaet Augsburg, 86135 Augsburg (Germany); Tong, Ning-Hua [Institut fuer Theorie der Kondensierten Materie, Universitaet Karlsruhe, 76128 Karlsruhe (Germany); Bulla, Ralf [Theoretische Physik III, Elektronische Korrelationen und Magnetismus, Universitaet Augsburg, 86135 Augsburg (Germany)

2006-07-05

We present a detailed model study of exciton transfer processes in donor-bridge-acceptor (DBA) systems. Using a model which includes the intermolecular Coulomb interaction and the coupling to a dissipative environment we calculate the phase diagram, the absorption spectrum as well as dynamic equilibrium properties with the numerical renormalization group. This method is non-perturbative and therefore allows one to cover the full parameter space, especially the case when the intermolecular Coulomb interaction is of the same order as the coupling to the environment and perturbation theory cannot be applied. For DBA systems with up to six sites we found a transition to the localized phase (self-trapping) depending on the coupling to the dissipative environment. We discuss various criteria which favour delocalized exciton transfer.

Dissipative exciton transfer in donor-bridge-acceptor systems: numerical renormalization group calculation of equilibrium properties.

Science.gov (United States)

Tornow, Sabine; Tong, Ning-Hua; Bulla, Ralf

2006-07-05

We present a detailed model study of exciton transfer processes in donor-bridge-acceptor (DBA) systems. Using a model which includes the intermolecular Coulomb interaction and the coupling to a dissipative environment we calculate the phase diagram, the absorption spectrum as well as dynamic equilibrium properties with the numerical renormalization group. This method is non-perturbative and therefore allows one to cover the full parameter space, especially the case when the intermolecular Coulomb interaction is of the same order as the coupling to the environment and perturbation theory cannot be applied. For DBA systems with up to six sites we found a transition to the localized phase (self-trapping) depending on the coupling to the dissipative environment. We discuss various criteria which favour delocalized exciton transfer.

Charge-Transfer Dynamics in the Lowest Excited State of a Pentacene–Fullerene Complex: Implications for Organic Solar Cells

KAUST Repository

Joseph, Saju

2017-10-02

We characterize the dynamic nature of the lowest excited state in a pentacene/C60 complex on the femtosecond time scale, via a combination of ab initio molecular dynamics and time-dependent density functional theory. We analyze the correlations between the molecular vibrations of the complex and the oscillations in the electron-transfer character of its lowest excited state, which point to vibration-induced coherences between the (pentacene-based) local-excitation (LE) state and the complex charge-transfer (CT) state. We discuss the implications of our results on this model system for the exciton-dissociation process in organic solar cells.

Coupled quantum-classical method for long range charge transfer: relevance of the nuclear motion to the quantum electron dynamics

International Nuclear Information System (INIS)

Da Silva, Robson; Hoff, Diego A; Rego, Luis G C

2015-01-01

Charge and excitonic-energy transfer phenomena are fundamental for energy conversion in solar cells as well as artificial photosynthesis. Currently, much interest is being paid to light-harvesting and energy transduction processes in supramolecular structures, where nuclear dynamics has a major influence on electronic quantum dynamics. For this reason, the simulation of long range electron transfer in supramolecular structures, under environmental conditions described within an atomistic framework, has been a difficult problem to study. This work describes a coupled quantum mechanics/molecular mechanics method that aims at describing long range charge transfer processes in supramolecular systems, taking into account the atomistic details of large molecular structures, the underlying nuclear motion, and environmental effects. The method is applied to investigate the relevance of electron–nuclei interaction on the mechanisms for photo-induced electron–hole pair separation in dye-sensitized interfaces as well as electronic dynamics in molecular structures. (paper)

Microscopic theory of singlet exciton fission. III. Crystalline pentacene

International Nuclear Information System (INIS)

Berkelbach, Timothy C.; Reichman, David R.; Hybertsen, Mark S.

2014-01-01

We extend our previous work on singlet exciton fission in isolated dimers to the case of crystalline materials, focusing on pentacene as a canonical and concrete example. We discuss the proper interpretation of the character of low-lying excited states of relevance to singlet fission. In particular, we consider a variety of metrics for measuring charge-transfer character, conclusively demonstrating significant charge-transfer character in the low-lying excited states. The impact of this electronic structure on the subsequent singlet fission dynamics is assessed by performing real-time master-equation calculations involving hundreds of quantum states. We make direct comparisons with experimental absorption spectra and singlet fission rates, finding good quantitative agreement in both cases, and we discuss the mechanistic distinctions that exist between small isolated aggregates and bulk systems

Microscopic theory of singlet exciton fission. III. Crystalline pentacene

Energy Technology Data Exchange (ETDEWEB)

Berkelbach, Timothy C., E-mail: tcb2112@columbia.edu; Reichman, David R., E-mail: drr2103@columbia.edu [Department of Chemistry, Columbia University, 3000 Broadway, New York, New York 10027 (United States); Hybertsen, Mark S., E-mail: mhyberts@bnl.gov [Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973-5000 (United States)

2014-08-21

We extend our previous work on singlet exciton fission in isolated dimers to the case of crystalline materials, focusing on pentacene as a canonical and concrete example. We discuss the proper interpretation of the character of low-lying excited states of relevance to singlet fission. In particular, we consider a variety of metrics for measuring charge-transfer character, conclusively demonstrating significant charge-transfer character in the low-lying excited states. The impact of this electronic structure on the subsequent singlet fission dynamics is assessed by performing real-time master-equation calculations involving hundreds of quantum states. We make direct comparisons with experimental absorption spectra and singlet fission rates, finding good quantitative agreement in both cases, and we discuss the mechanistic distinctions that exist between small isolated aggregates and bulk systems.

From Recombination Dynamics to Device Performance: Quantifying the Efficiency of Exciton Dissociation, Charge Separation, and Extraction in Bulk Heterojunction Solar Cells with Fluorine-Substituted Polymer Donors

KAUST Repository

Gorenflot, Julien

2017-09-28

An original set of experimental and modeling tools is used to quantify the yield of each of the physical processes leading to photocurrent generation in organic bulk heterojunction solar cells, enabling evaluation of materials and processing condition beyond the trivial comparison of device performances. Transient absorption spectroscopy, “the” technique to monitor all intermediate states over the entire relevant timescale, is combined with time-delayed collection field experiments, transfer matrix simulations, spectral deconvolution, and parametrization of the charge carrier recombination by a two-pool model, allowing quantification of densities of excitons and charges and extrapolation of their kinetics to device-relevant conditions. Photon absorption, charge transfer, charge separation, and charge extraction are all quantified for two recently developed wide-bandgap donor polymers: poly(4,8-bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b′]dithiophene-3,4-difluorothiophene) (PBDT[2F]T) and its nonfluorinated counterpart poly(4,8-bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b′]dithiophene-3,4-thiophene) (PBDT[2H]T) combined with PC71BM in bulk heterojunctions. The product of these yields is shown to agree well with the devices\\' external quantum efficiency. This methodology elucidates in the specific case studied here the origin of improved photocurrents obtained when using PBDT[2F]T instead of PBDT[2H]T as well as upon using solvent additives. Furthermore, a higher charge transfer (CT)-state energy is shown to lead to significantly lower energy losses (resulting in higher VOC) during charge generation compared to P3HT:PCBM.

From Recombination Dynamics to Device Performance: Quantifying the Efficiency of Exciton Dissociation, Charge Separation, and Extraction in Bulk Heterojunction Solar Cells with Fluorine-Substituted Polymer Donors

KAUST Repository

Gorenflot, Julien; Paulke, Andreas; Piersimoni, Fortunato; Wolf, Jannic Sebastian; Kan, Zhipeng; Cruciani, Federico; El Labban, Abdulrahman; Neher, Dieter; Beaujuge, Pierre; Laquai, Fré dé ric

2017-01-01

An original set of experimental and modeling tools is used to quantify the yield of each of the physical processes leading to photocurrent generation in organic bulk heterojunction solar cells, enabling evaluation of materials and processing condition beyond the trivial comparison of device performances. Transient absorption spectroscopy, “the” technique to monitor all intermediate states over the entire relevant timescale, is combined with time-delayed collection field experiments, transfer matrix simulations, spectral deconvolution, and parametrization of the charge carrier recombination by a two-pool model, allowing quantification of densities of excitons and charges and extrapolation of their kinetics to device-relevant conditions. Photon absorption, charge transfer, charge separation, and charge extraction are all quantified for two recently developed wide-bandgap donor polymers: poly(4,8-bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b′]dithiophene-3,4-difluorothiophene) (PBDT[2F]T) and its nonfluorinated counterpart poly(4,8-bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b′]dithiophene-3,4-thiophene) (PBDT[2H]T) combined with PC71BM in bulk heterojunctions. The product of these yields is shown to agree well with the devices' external quantum efficiency. This methodology elucidates in the specific case studied here the origin of improved photocurrents obtained when using PBDT[2F]T instead of PBDT[2H]T as well as upon using solvent additives. Furthermore, a higher charge transfer (CT)-state energy is shown to lead to significantly lower energy losses (resulting in higher VOC) during charge generation compared to P3HT:PCBM.

Ultrafast Charge Photogeneration in MEH-PPV Charge-Transfer Complexes

NARCIS (Netherlands)

Bakulin, Artem A.; Paraschuk, Dmitry Yu; Pshenichnikov, Maxim S.; van Loosdrecht, Paul H. M.; Corkum, P; DeSilvestri, S; Nelson, KA; Riedle, E; Schoenlein, RW

2009-01-01

Visible-pump - IR-probe spectroscopy is used to study the ultrafast charge dynamics in MEH-PPV based charge-transfer complexes and donor-acceptor blends. Transient anisotropy of the polymer polaron band provides invaluable insights into excitation localisation and charge-transfer pathways.

Photoinduced Charge Transfer from Titania to Surface Doping Site.

Science.gov (United States)

Inerbaev, Talgat; Hoefelmeyer, James D; Kilin, Dmitri S

2013-05-16

We evaluate a theoretical model in which Ru is substituting for Ti at the (100) surface of anatase TiO 2 . Charge transfer from the photo-excited TiO 2 substrate to the catalytic site triggers the photo-catalytic event (such as water oxidation or reduction half-reaction). We perform ab-initio computational modeling of the charge transfer dynamics on the interface of TiO 2 nanorod and catalytic site. A slab of TiO 2 represents a fragment of TiO 2 nanorod in the anatase phase. Titanium to ruthenium replacement is performed in a way to match the symmetry of TiO 2 substrate. One molecular layer of adsorbed water is taken into consideration to mimic the experimental conditions. It is found that these adsorbed water molecules saturate dangling surface bonds and drastically affect the electronic properties of systems investigated. The modeling is performed by reduced density matrix method in the basis of Kohn-Sham orbitals. A nano-catalyst modeled through replacement defect contributes energy levels near the bottom of the conduction band of TiO 2 nano-structure. An exciton in the nano-rod is dissipating due to interaction with lattice vibrations, treated through non-adiabatic coupling. The electron relaxes to conduction band edge and then to the Ru cite with faster rate than hole relaxes to the Ru cite. These results are of the importance for an optimal design of nano-materials for photo-catalytic water splitting and solar energy harvesting.

Employing exciton transfer molecules to increase the lifetime of phosphorescent red organic light emitting diodes

Science.gov (United States)

Lindla, Florian; Boesing, Manuel; van Gemmern, Philipp; Bertram, Dietrich; Keiper, Dietmar; Heuken, Michael; Kalisch, Holger; Jansen, Rolf H.

2011-04-01

The lifetime of phosphorescent red organic light emitting diodes (OLEDs) is investigated employing either N,N'-diphenyl-N,N'-bis(1-naphthylphenyl)-1,1'-biphenyl-4,4'-diamine (NPB), TMM117, or 4,4',4″-tris(N-carbazolyl)-triphenylamine (TCTA) as hole-conducting host material (mixed with an electron conductor). All OLED (organic vapor phase deposition-processed) show similar efficiencies around 30 lm/W but strongly different lifetimes. Quickly degrading OLED based on TCTA can be stabilized by doping exciton transfer molecules [tris-(phenyl-pyridyl)-Ir (Ir(ppy)3)] to the emission layer. At a current density of 50 mA/cm2 (12 800 cd/m2), a lifetime of 387 h can be achieved. Employing exciton transfer molecules is suggested to prevent the degradation of the red emission layer in phosphorescent white OLED.

Exploring ultrafast dynamics of excitons and multiexcitons in "giant" nanocrystal quantum dots

Science.gov (United States)

Sampat, Siddharth

In this work, we have performed extensive time resolved photoluminescence (PL) studies to further the understanding of charge dynamics in semiconductor nanocrystal quantum dots (QDs). Recent developments in QD synthesis have introduced a new set of QD known as "giant" quantum dots (gQDs) that consist of a CdSe core coated with up to 19 monolayers of a CdS shell. The thick shell layer is grown using a SILAR method resulting in a defect free, alloyed CdSe/CdS interface. This has been attributed to gQDs exhibiting excellent optical properties such as high excitonic quantum yield (QY), prolonged photostability and inhibition of flourescence intermittency ("blinking"), which is regularly observed in conventional QDs. In gQDs, however, owing to unique fabrication methods and material selection, the Auger process is strongly suppressed resulting in efficient radiative recombination of photogenerated excitons as well as high PL QY of charged excitonic and multiexcitonic species. We perform extensive single gQDs studies that establish the role played by gQD shell thickness and core size in governing their optical properties. It is found that both the core and shell dimensions can be tuned in order to achieve the smallest gQDs with the highest vii Auger suppression resulting in photostable dots with high QYs. Next, we perform a study of multiexcitonic species in gQDs that are encapsulated in an insulating SiO2shell. These silica-coated gQDs exhibit strong PL from charged excitons, biexcitons as well as triexcitons. This observation has led to an accurate description of excitonic and multiexcitonic behavior which is modeled using a statistical scaling approach. As a demonstration of the practical applicability of gQDs, energy transfer of excitons as well as multiexcitons to different substrates is studied. Finally, a back gated silicon nanomembrane FET device is discussed that exhibits a large photocurrent increase when sensitized with QDs.

Synthesis and Exciton Dynamics of Triplet Sensitized Conjugated Polymers

KAUST Repository

Andernach, Rolf

2015-07-22

We report the synthesis of a novel polythiophene-based host-guest copolymer incorporating a Pt-porphyrin complex (TTP-Pt) into the backbone for efficient singlet to triplet polymer exciton sensitization. We elucidated the exciton dynamics in thin films of the material by means of Transient Absorption Spectrosopcy (TAS) on multiple timescales and investigated the mechanism of triplet exciton formation. During sensitization, single exciton diffusion is followed by exciton transfer from the polymer backbone to the complex where it undergoes intersystem crossing to the triplet state of the complex. We directly monitored the triplet exciton back transfer from the Pt-porphyrin to the polymer and find that 60% of the complex triplet excitons are transferred with a time constant of 1087 ps. We propose an equilibrium between polymer and porphyrin triplet states as a result of the low triplet diffusion length in the polymer backbone and hence an increased local triplet population resulting in increased triplet-triplet annihilation. This novel system has significant implications for the design of novel materials for triplet sensitized solar cells and up-conversion layers.

The excitonic insulator route through a dynamical phase transition induced by an optical pulse

Energy Technology Data Exchange (ETDEWEB)

Brazovskii, S., E-mail: brazov@lptms.u-psud.fr [Université Paris-Saclay, LPTMS, CNRS, Univ. Paris-sud (France); Kirova, N. [Université Paris-Saclay, LPS, CNRS, Univ. Paris-sud (France)

2016-03-15

We consider a dynamical phase transition induced by a short optical pulse in a system prone to thermodynamical instability. We address the case of pumping to excitons whose density contributes directly to the order parameter. To describe both thermodynamic and dynamic effects on equal footing, we adopt a view of the excitonic insulator for the phase transition and suggest a formation of the Bose condensate for the pumped excitons. The work is motivated by experiments in donor–acceptor organic compounds with a neutral- ionic phase transition coupled to the spontaneous lattice dimerization and to charge transfer excitons. The double nature of the ensemble of excitons leads to an intricate time evolution, in particular, to macroscopic quantum oscillations from the interference between the Bose condensate of excitons and the ground state of the excitonic insulator. The coupling of excitons and the order parameter also leads to self-trapping of their wave function, akin to self-focusing in optics. The locally enhanced density of excitons can surpass a critical value to trigger the phase transformation, even if the mean density is below the required threshold. The system is stratified in domains that evolve through dynamical phase transitions and sequences of merging. The new circumstances in experiments and theory bring to life, once again, some remarkable inventions made by L.V. Keldysh.

The nature of singlet excitons in oligoacene molecular crystals

KAUST Repository

Yamagata, H.; Norton, J.; Hontz, E.; Olivier, Y.; Beljonne, D.; Brédas, J. L.; Silbey, R. J.; Spano, F. C.

2011-01-01

A theory for polarized absorption in crystalline oligoacenes is presented, which includes Frenkel exciton coupling, the coupling between Frenkel and charge-transfer (CT) excitons, and the coupling of all neutral and ionic excited states to the dominant ring-breathing vibrational mode. For tetracene, spectra calculated using all Frenkel couplings among the five lowest energy molecular singlet states predict a Davydov splitting (DS) of the lowest energy (0-0) vibronic band of only -32cm-1, far smaller than the measured value of 631cm-1 and of the wrong sign-a negative sign indicating that the polarizations of the lower and upper Davydov components are reversed from experiment. Inclusion of Frenkel-CT coupling dramatically improves the agreement with experiment, yielding a 0-0 DS of 601cm-1 and a nearly quantitative reproduction of the relative spectral intensities of the 0-n vibronic components. Our analysis also shows that CT mixing increases with the size of the oligoacenes. We discuss the implications of these results on exciton dissociation and transport. © 2011 American Institute of Physics.

Single photon emission up to liquid nitrogen temperature from charged excitons confined in GaAs-based epitaxial nanostructures

NARCIS (Netherlands)

Dusanowski, L.; Syperek, M.; Marynski, A.; Li, L.H.; Misiewicz, J.; Höfling, S.; Kamp, M.; Fiore, A.; Sek, G.

2015-01-01

We demonstrate a non-classical photon emitter at near infrared wavelength based on a single (In,Ga)As/GaAs epitaxially grown columnar quantum dot. Charged exciton complexes have been identified in magneto-photoluminescence. Photon auto-correlation histograms from the recombination of a trion

Exciton dynamics at the heteromolecular interface between N,N′-dioctyl-3,4,9,10-perylenedicarboximide and quaterrylene, studied using time-resolved photoluminescence

Directory of Open Access Journals (Sweden)

Nobuya Hiroshiba

2014-06-01

Full Text Available To elucidate the exciton dynamics at the heteromolecular interface, the temperature dependence of time-resolved photoluminescence (TRPL spectra of neat-N,N′-dioctyl-3,4,9,10-perylenedicarboximide (PTCDI-C8 and PTCDI-C8/Quaterrylene (QT heteromolecular thin films was investigated. The lifetimes of excitons were evaluated to identify the Frenkel (FE, high energy charge-transfer (CTEhigh, low energy charge-transfer (CTElow, and excimer exciton states. The thermal activation energy (Δact of CTElow in PTCDI-C8 thin film was evaluated as 25 meV, which is 1/5 of that of FE, indicating that CTElow is more thermally sensitive than FE in PTCDI-C8 thin film. We investigated the exciton transport length (l along the vertical direction against the substrate surface in PTCDI-C8/QT thin film at 30 K, and demonstrated that lFE = 9.9 nm, lCTElow = 4.2 nm, lCTEhigh = 4.3 nm, and lexcimer = 11.9 nm. To elucidate the difference in l among these excitons, the activation energies (Ea for quenching at the heteromolecular interface were investigated. Ea values were estimated to be 13.1 meV for CTElow and 18.6 meV for CTEhigh. These values agree with the thermal sensitivity of CTEs as reported in a previous static PL study. This latter situation is different from the case of FE and excimer excitons, which are transported via a resonant process and have no temperature dependence. The small Ea values of CTEs suggest that exciton transport takes place via a thermal hopping process in CTEs. The present experimental study provides information on nano-scaled exciton dynamics in a well-defined PTCDI-C8 (2 ML/QT (2 ML system.

Interlayer excitons in a bulk van der Waals semiconductor

DEFF Research Database (Denmark)

Arora, Ashish; Drueppel, Matthias; Schmidt, Robert

2017-01-01

Bound electron-hole pairs called excitons govern the electronic and optical response of many organic and inorganic semiconductors. Excitons with spatially displaced wave functions of electrons and holes (interlayer excitons) are important for Bose-Einstein condensation, superfluidity......, dissipationless current flow, and the light-induced exciton spin Hall effect. Here we report on the discovery of interlayer excitons in a bulk van der Waals semiconductor. They form due to strong localization and spin-valley coupling of charge carriers. By combining high-field magneto-reflectance experiments...

Interlayer excitons in a bulk van der Waals semiconductor.

Science.gov (United States)

Arora, Ashish; Drüppel, Matthias; Schmidt, Robert; Deilmann, Thorsten; Schneider, Robert; Molas, Maciej R; Marauhn, Philipp; Michaelis de Vasconcellos, Steffen; Potemski, Marek; Rohlfing, Michael; Bratschitsch, Rudolf

2017-09-21

Bound electron-hole pairs called excitons govern the electronic and optical response of many organic and inorganic semiconductors. Excitons with spatially displaced wave functions of electrons and holes (interlayer excitons) are important for Bose-Einstein condensation, superfluidity, dissipationless current flow, and the light-induced exciton spin Hall effect. Here we report on the discovery of interlayer excitons in a bulk van der Waals semiconductor. They form due to strong localization and spin-valley coupling of charge carriers. By combining high-field magneto-reflectance experiments and ab initio calculations for 2H-MoTe 2 , we explain their salient features: the positive sign of the g-factor and the large diamagnetic shift. Our investigations solve the long-standing puzzle of positive g-factors in transition metal dichalcogenides, and pave the way for studying collective phenomena in these materials at elevated temperatures.Excitons, quasi-particles of bound electron-hole pairs, are at the core of the optoelectronic properties of layered transition metal dichalcogenides. Here, the authors unveil the presence of interlayer excitons in bulk van der Waals semiconductors, arising from strong localization and spin-valley coupling of charge carriers.

Charge Carrier Dynamics at Silver Nanocluster-Molecular Acceptor Interfaces

KAUST Repository

Almansaf, Abdulkhaleq

2017-07-01

A fundamental understanding of interfacial charge transfer at donor-acceptor interfaces is very crucial as it is considered among the most important dynamical processes for optimizing performance in many light harvesting systems, including photovoltaics and photo-catalysis. In general, the photo-generated singlet excitons in photoactive materials exhibit very short lifetimes because of their dipole-allowed spin radiative decay and short diffusion lengths. In contrast, the radiative decay of triplet excitons is dipole forbidden; therefore, their lifetimes are considerably longer. The discussion in this thesis primarily focuses on the relevant parameters that are involved in charge separation (CS), charge transfer (CT), intersystem crossing (ISC) rate, triplet state lifetime, and carrier recombination (CR) at silver nanocluster (NCs) molecular-acceptors interfaces. A combination of steady-state and femto- and nanosecond broadband transient absorption spectroscopies were used to investigate the charge carrier dynamics in various donor-acceptor systems. Additionally, this thesis was prolonged to investigate some important factors that influence the charge carrier dynamics in Ag29 silver NCs donor-acceptor systems, such as the metal doping and chemical structure of the nanocluster and molecular acceptors. Interestingly, clear correlations between the steady-state measurements and timeresolved spectroscopy results are found. In the first study, we have investigated the interfacial charge transfer dynamics in positively charged meso units of 5, 10, 15, 20-tetra (1- methyl-4-pyridino)-porphyrin tetra (p-toluene sulfonate) (TMPyP) and neutral charged 5, 10, 15, 20-tetra (4-pyridyl)-porphyrin (TPyP), with negatively charged undoped and gold (Au)- doped silver Ag29 NCs. Moreover, this study showed the impact of Au doping on the charge carrier dynamics of the system. In the second study, we have investigated the interfacial charge transfer dynamics in [Pt2 Ag23 Cl7 (PPh3

Exciton center-of-mass localization and dielectric environment effect in monolayer WS2

Science.gov (United States)

Hichri, Aïda; Ben Amara, Imen; Ayari, Sabrine; Jaziri, Sihem

2017-06-01

The ultrathin transition metal dichalcogenides (TMDs) have emerged as promising materials for various applications using two dimensional semiconductors. They have attracted increasing attention due to their unique optical properties originate from neutral and charged excitons. In this paper, we study the strong localization of exciton center-of-mass motion within random potential fluctuations caused by the monolayer defects. Here, we report negatively charged exciton formation in monolayer TMDs, notably tungsten disulfide WS2. Our theory is based on an effective mass model of neutral and charged excitons, parameterized by ab-initio calculations. Taking into the account the strong correlation between the monolayer WS2 and the surrounding dielectric environment, our theoretical results are in good agreement with one-photon photoluminescence (PL) and reflectivity measurements. We also show that the exciton state with p-symmetry, experimentally observed by two-photon PL emission, is energetically below the 2s-state. We use the equilibrium mass action law, to quantify the relative weight of exciton and trion PL. We show that exciton and trion emission can be tuned and controlled by external parameters like temperature, pumping, and injection electrons. Finally, in comparison with experimental measurements, we show that exciton emission in monolayer tungsten dichalcogenides is substantially reduced. This feature suggests that free exciton can be trapped in disordered potential wells to form a localized exciton and therefore offers a route toward novel optical properties.

Optical Studies of Excitonic Effects at Two-Dimensional Nanostructure Interfaces

Science.gov (United States)

Ajayi, Obafunso Ademilolu

Atomically thin two-dimensional nanomaterials such as graphene and transition metal dichalcogenides (TMDCs) have seen a rapid growth of exploration since the isolation of monolayer graphene. These materials provide a rich field of study for physics and optoelectronics applications. Many applications seek to combine a two dimensional (2D) material with another nanomaterial, either another two dimensional material or a zero (0D) or one dimensional (1D) material. The work in this thesis explores the consequences of these interactions from 0D to 2D. We begin in Chapter 2 with a study of energy transfer at 0D-2D interfaces with quantum dots and graphene. In our work we seek to maximize the rate of energy transfer by reducing the distance between the materials. We observe an interplay with the distance-dependence and surface effects from our halogen terminated quantum dots that affect our observed energy transfer. In Chapter 3 we study supercapacitance in composite graphene oxide-carbon nanotube electrodes. At this 2D-1D interface we observe a compounding effect between graphene oxide and carbon nanotubes. Carbon nanotubes increase the accessible surface area of the supercapacitors and improve conductivity by forming a conductive pathway through electrodes. In Chapter 4 we investigate effective means of improving sample quality in TMDCs and discover the importance of the monolayer interface. We observe a drastic improvement in photoluminescence when encapsulating our TMDCs with Boron Nitride. We measure spectral linewidths approaching the intrinsic limit due to this 2D-2D interface. We also effectively reduce excess charge and thus the trion-exciton ratio in our samples through substrate surface passivation. In Chapter 5 we briefly discuss our investigations on chemical doping, heterostructures and interlayer decoupling in ReS2. We observe an increase in intensity for p-doped MoS2 samples. We investigated the charge transfer exciton previously identified in

Influence of intra-pigment vibrations on dynamics of photosynthetic exciton.

Science.gov (United States)

Sato, Yoshihiro; Doolittle, Brian

2014-11-14

We have numerically investigated the effect of an underdamped intra-pigment vibrational mode on an exciton's quantum coherence and energy transfer efficiency. Our model describes a bacteriochlorophyll a pigment-protein dimer under the conditions at which photosynthetic energy transfer occurs. The dimer is modeled using a theoretical treatment of a vibronic exciton, and its dynamics are numerically analyzed using a non-Markovian and non-perturbative method. We examined the system's response to various values of the Huang-Rhys factor, site energy difference, reorganization energy, and reorganization energy difference. We found that the inclusion of the intra-pigment vibronic mode allows for long-lived oscillatory quantum coherences to occur. This excitonic coherence is robust against static site-energy disorder. The vibrational mode also promotes exciton transfer along the site-energy landscape thus improving the overall energy transfer efficiency.

Influence of intra-pigment vibrations on dynamics of photosynthetic exciton

International Nuclear Information System (INIS)

Sato, Yoshihiro; Doolittle, Brian

2014-01-01

We have numerically investigated the effect of an underdamped intra-pigment vibrational mode on an exciton's quantum coherence and energy transfer efficiency. Our model describes a bacteriochlorophyll a pigment-protein dimer under the conditions at which photosynthetic energy transfer occurs. The dimer is modeled using a theoretical treatment of a vibronic exciton, and its dynamics are numerically analyzed using a non-Markovian and non-perturbative method. We examined the system's response to various values of the Huang-Rhys factor, site energy difference, reorganization energy, and reorganization energy difference. We found that the inclusion of the intra-pigment vibronic mode allows for long-lived oscillatory quantum coherences to occur. This excitonic coherence is robust against static site-energy disorder. The vibrational mode also promotes exciton transfer along the site-energy landscape thus improving the overall energy transfer efficiency

Influence of intra-pigment vibrations on dynamics of photosynthetic exciton

Energy Technology Data Exchange (ETDEWEB)

Sato, Yoshihiro, E-mail: sato.yoshihiro77@nihon-u.ac.jp, E-mail: ysato.colby@gmail.com; Doolittle, Brian [Department of Physics and Astronomy, Colby College, Waterville, Maine 04901 (United States)

2014-11-14

We have numerically investigated the effect of an underdamped intra-pigment vibrational mode on an exciton's quantum coherence and energy transfer efficiency. Our model describes a bacteriochlorophyll a pigment-protein dimer under the conditions at which photosynthetic energy transfer occurs. The dimer is modeled using a theoretical treatment of a vibronic exciton, and its dynamics are numerically analyzed using a non-Markovian and non-perturbative method. We examined the system's response to various values of the Huang-Rhys factor, site energy difference, reorganization energy, and reorganization energy difference. We found that the inclusion of the intra-pigment vibronic mode allows for long-lived oscillatory quantum coherences to occur. This excitonic coherence is robust against static site-energy disorder. The vibrational mode also promotes exciton transfer along the site-energy landscape thus improving the overall energy transfer efficiency.

Ultrafast exciton decay in PbS quantum dots through simultaneous electron and hole recombination with a surface-localized ion pair

Energy Technology Data Exchange (ETDEWEB)

Edme, Kedy; Bettis Homan, Stephanie; Nepomnyashchii, Alexander B.; Weiss, Emily A., E-mail: e-weiss@northwestern.edu

2016-06-01

Highlights: • We synthesize complexes of PbS quantum dots (QDs) and tetracyanoquinodimethane (TCNQ). Each PbS QD spontaneously reduces up to 17 TCNQ molecules. • The photoluminescence of the PbS QDs is quenched in the presence of the reduced TCNQ species through ultrafast non-radiative, simultaneous decay of the electron and hole. • We assign this decay to a four-carrier, concerted charge recombination mechanism with the surface localized sulfur–TCNQ{sup x−} ion pair. - Abstract: This paper describes the ultrafast decay of the band-edge exciton in PbS quantum dots (QDs) through simultaneous recombination of the excitonic hole and electron with the surface localized ion pair formed upon adsorption of tetracyanoquinodimethane (TCNQ). Each PbS QD (R = 1.8 nm) spontaneously reduces up to 17 TCNQ molecules upon adsorption of the TCNQ molecule to a sulfur on the QD surface. The photoluminescence of the PbS QDs is quenched in the presence of the reduced TCNQ species through ultrafast (⩽15-ps) non-radiative decay of the exciton; the rate constant for the decay process increases approximately linearly with the number of adsorbed, reduced TCNQ molecules. Near-infrared and mid-infrared transient absorption show that this decay occurs through simultaneous transfer of the excitonic electron and hole, and is assigned to a four-carrier, concerted charge recombination mechanism based on the observations that (i) the PL of the QDs recovers when spontaneously reduced TCNQ{sup 1−} desorbs from the QD surface upon addition of salt, and (ii) the PL of the QDs is preserved when another spontaneous oxidant, ferrocinium, which cannot participate in charge transfer in its reduced state, is substituted for TCNQ.

Charge separation at nanoscale interfaces: energy-level alignment including two-quasiparticle interactions.

Science.gov (United States)

Li, Huashan; Lin, Zhibin; Lusk, Mark T; Wu, Zhigang

2014-10-21

The universal and fundamental criteria for charge separation at interfaces involving nanoscale materials are investigated. In addition to the single-quasiparticle excitation, all the two-quasiparticle effects including exciton binding, Coulomb stabilization, and exciton transfer are considered, which play critical roles on nanoscale interfaces for optoelectronic applications. We propose a scheme allowing adding these two-quasiparticle interactions on top of the single-quasiparticle energy level alignment for determining and illuminating charge separation at nanoscale interfaces. Employing the many-body perturbation theory based on Green's functions, we quantitatively demonstrate that neglecting or simplifying these crucial two-quasiparticle interactions using less accurate methods is likely to predict qualitatively incorrect charge separation behaviors at nanoscale interfaces where quantum confinement dominates.

Long-Lived Charge Separation at Heterojunctions between Semiconducting Single-Walled Carbon Nanotubes and Perylene Diimide Electron Acceptors

Energy Technology Data Exchange (ETDEWEB)

Kang, Hyun Suk [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Arias, Dylan H [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Blackburn, Jeffrey L [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Sisto, Thomas J. [Columbia University; Peurifoy, Samuel [Columbia University; Zhang, Boyuan [Columbia University; Nuckolls, Colin [Columbia University

2018-04-13

Nonfullerene electron acceptors have facilitated a recent surge in the efficiencies of organic solar cells, although fundamental studies of the nature of exciton dissociation at interfaces with nonfullerene electron acceptors are still relatively sparse. Semiconducting single-walled carbon nanotubes (s-SWCNTs), unique one-dimensional electron donors with molecule-like absorption and highly mobile charges, provide a model system for studying interfacial exciton dissociation. Here, we investigate excited-state photodynamics at the heterojunction between (6,5) s-SWCNTs and two perylene diimide (PDI)-based electron acceptors. Each of the PDI-based acceptors, hPDI2-pyr-hPDI2 and Trip-hPDI2, is deposited onto (6,5) s-SWCNT films to form a heterojunction bilayer. Transient absorption measurements demonstrate that photoinduced hole/electron transfer occurs at the photoexcited bilayer interfaces, producing long-lived separated charges with lifetimes exceeding 1.0 us. Both exciton dissociation and charge recombination occur more slowly for the hPDI2-pyr-hPDI2 bilayer than for the Trip-hPDI2 bilayer. To explain such differences, we discuss the potential roles of the thermodynamic charge transfer driving force available at each interface and the different molecular structure and intermolecular interactions of PDI-based acceptors. Detailed photophysical analysis of these model systems can develop the fundamental understanding of exciton dissociation between organic electron donors and nonfullerene acceptors, which has not been systematically studied.

Theoretical study of excitonic complexes in semiconductors quantum wells

International Nuclear Information System (INIS)

Dacal, Luis Carlos Ogando

2001-08-01

A physical system where indistinguishable particles interact with each other creates the possibility of studying correlation and exchange effect. The simplest system is that one with only two indistinguishable particles. In condensed matter physics, these complexes are represented by charged excitons, donors and acceptors. In quantum wells, the valence band is not parabolic, therefore, the negatively charged excitons and donors are theoretically described in a simpler way. Despite the fact that the stability of charged excitons (trions) is known since the late 50s, the first experimental observation occurred only at the early 90s in quantum well samples, where their binding energies are one order of magnitude larger due to the one dimensional carriers confinement. After this, these complexes became the subject of an intense research because the intrinsic screening of electrical interactions in semiconductor materials allows that magnetic fields that are usual in laboratories have strong effects on the trion binding energy. Another rich possibility is the study of trions as an intermediate state between the neutral exciton and the Fermi edge singularity when the excess of doping carriers is increased. In this thesis, we present a theoretical study of charged excitons and negatively charged donors in GaAs/Al 0.3 Ga 0.7 As quantum wells considering the effects of external electric and magnetic fields. We use a simple, accurate and physically clear method to describe these systems in contrast with the few and complex treatments s available in the literature. Our results show that the QW interface defects have an important role in the trion dynamics. This is in agreement with some experimental works, but it disagrees with other ones. (author)

One dimensional models of excitons in carbon nanotubes

DEFF Research Database (Denmark)

Cornean, Horia Decebal; Duclos, P.; Pedersen, Thomas Garm

Excitons in carbon nanotubes may be modeled by two oppositely charged particles living on the surface of a cylinder. We derive three one dimensional effective Hamiltonians which become exact as the radius of the cylinder vanishes. Two of them are solvable.......Excitons in carbon nanotubes may be modeled by two oppositely charged particles living on the surface of a cylinder. We derive three one dimensional effective Hamiltonians which become exact as the radius of the cylinder vanishes. Two of them are solvable....

One-dimensional models of excitons in carbon nanotubes

DEFF Research Database (Denmark)

Cornean, Horia Decebal; Duclos, Pierre; Pedersen, Thomas Garm

2004-01-01

Excitons in carbon nanotubes may be modeled by two oppositely charged particles living on the surface of a cylinder. We derive three one-dimensional effective Hamiltonians which become exact as the radius of the cylinder vanishes. Two of them are solvable.......Excitons in carbon nanotubes may be modeled by two oppositely charged particles living on the surface of a cylinder. We derive three one-dimensional effective Hamiltonians which become exact as the radius of the cylinder vanishes. Two of them are solvable....

Charged excitonic complexes in GaAs/Al0.35Ga0.65As p-i-n double quantum wells

DEFF Research Database (Denmark)

Timofeev, V. B.; Larionov, A. V.; Alessi, M. Grassi

1999-01-01

Photoluminescence (PL) and PL excitation measurements (PLE) have been performed in GaAs/AlxGa1-xAs double quantum well (QW) structures under different applied electric fields. An emission due to charged excitons (trions) has been identified in the PL spectra similar to 3 meV below the heavy...

Symmetric charge transfer cross section of uranium

International Nuclear Information System (INIS)

Shibata, Takemasa; Ogura, Koichi

1995-03-01

Symmetric charge transfer cross section of uranium was calculated under consideration of reaction paths. In the charge transfer reaction a d 3/2 electron in the U atom transfers into the d-electron site of U + ( 4 I 9/2 ) ion. The J value of the U atom produced after the reaction is 6, 5, 4 or 3, at impact energy below several tens eV, only resonant charge transfer in which the product atom is ground state (J=6) takes place. Therefore, the cross section is very small (4-5 x 10 -15 cm 2 ) compared with that considered so far. In the energy range of 100-1000eV the cross section increases with the impact energy because near resonant charge transfer in which an s-electron in the U atom transfers into the d-electron site of U + ion. Charge transfer cross section between U + in the first excited state (289 cm -1 ) and U in the ground state was also obtained. (author)

Influence of excitonic effects on luminescence quantum yield in silicon

Energy Technology Data Exchange (ETDEWEB)

Sachenko, A.V.; Kostylyov, V.P.; Vlasiuk, V.M. [V. Lashkaryov Institute of Semiconductor Physics, NAS of Ukraine, 41 prospect Nauky, 03028 Kyiv (Ukraine); Sokolovskyi, I.O., E-mail: isokolovskyi@mun.ca [V. Lashkaryov Institute of Semiconductor Physics, NAS of Ukraine, 41 prospect Nauky, 03028 Kyiv (Ukraine); Department of Physics and Physical Oceanography, Memorial University of Newfoundland, St. John' s, NL, A1B 3X7 Canada (Canada); Evstigneev, M. [Department of Physics and Physical Oceanography, Memorial University of Newfoundland, St. John' s, NL, A1B 3X7 Canada (Canada)

2017-03-15

Nonradiative exciton lifetime in silicon is determined by comparison of the experimental and theoretical curves of bulk minority charge carriers lifetime on doping and excitation levels. This value is used to analyze the influence of excitonic effects on internal luminescence quantum yield at room temperature, taking into account both nonradiative and radiative exciton lifetimes. A range of Shockley-Hall-Reed lifetimes is found, where excitonic effects lead to an increase of internal luminescence quantum yield.

How to Draw Energy Level Diagrams in Excitonic Solar Cells.

Science.gov (United States)

Zhu, X-Y

2014-07-03

Emerging photovoltaic devices based on molecular and nanomaterials are mostly excitonic in nature. The initial absorption of a photon in these materials creates an exciton that can subsequently dissociate in each material or at their interfaces to give charge carriers. Any attempt at mechanistic understanding of excitonic solar cells must start with drawing energy level diagrams. This seemingly elementary exercise, which is described in textbooks for inorganic solar cells, has turned out to be a difficult subject in the literature. The problem stems from conceptual confusion of single-particle energy with quasi-particle energy and the misleading practice of mixing the two on the same energy level diagram. Here, I discuss how to draw physically accurate energy diagrams in excitonic solar cells using only single-particle energies (ionization potentials and electron affinities) of both ground and optically excited states. I will briefly discuss current understanding on the electronic energy landscape responsible for efficient charge separation in excitonic solar cells.

Pathways and timescales of primary charge separation in the photosystem II reaction center as revealed by a simultaneous fit of time-resolved fluorescence and transient absorption

NARCIS (Netherlands)

Novoderezhkin, V.I.; Andrizhiyevskaya, E.G.; Dekker, J.P.; van Grondelle, R.

2005-01-01

We model the dynamics of energy transfer and primary charge separation in isolated photosystem II (PSII) reaction centers. Different exciton models with specific site energies of the six core pigments and two peripheral chlorophylls (Chls) in combination with different charge transfer schemes have

Nearly Perfect Triplet-Triplet Energy Transfer from Wannier Excitons to Naphthalene in Organic-Inorganic Hybrid Quantum-Well Materials

Science.gov (United States)

Ema, K.; Inomata, M.; Kato, Y.; Kunugita, H.; Era, M.

2008-06-01

We report the observation of extremely efficient energy transfer (greater than 99%) in an organic-inorganic hybrid quantum-well structure consisting of perovskite-type lead bromide well layers and naphthalene-linked ammonium barrier layers. Time-resolved photoluminescence measurements confirm that the transfer is triplet-triplet Dexter-type energy transfer from Wannier excitons in the inorganic well to the triplet state of naphthalene molecules in the organic barrier. Using measurements in the 10 300 K temperature range, we also investigated the temperature dependence of the energy transfer.

Exciton fission in monolayer transition metal dichalcogenide semiconductors.

Science.gov (United States)

Steinhoff, A; Florian, M; Rösner, M; Schönhoff, G; Wehling, T O; Jahnke, F

2017-10-27

When electron-hole pairs are excited in a semiconductor, it is a priori not clear if they form a plasma of unbound fermionic particles or a gas of composite bosons called excitons. Usually, the exciton phase is associated with low temperatures. In atomically thin transition metal dichalcogenide semiconductors, excitons are particularly important even at room temperature due to strong Coulomb interaction and a large exciton density of states. Using state-of-the-art many-body theory, we show that the thermodynamic fission-fusion balance of excitons and electron-hole plasma can be efficiently tuned via the dielectric environment as well as charge carrier doping. We propose the observation of these effects by studying exciton satellites in photoemission and tunneling spectroscopy, which present direct solid-state counterparts of high-energy collider experiments on the induced fission of composite particles.

Efficient Long - Range Electron Transfer Processes in Polyfluorene – Perylene Diimide Blends

KAUST Repository

Isakova, Anna

2018-05-17

In bulk heterojunction donor-acceptor (D-A) blends, high photovoltaic yields require charge carrier separation to outcompete geminate recombination. Recently, evidence for long-range electron transfer mechanisms has been presented, avoiding strongly-bound interfacial charge transfer (CT) states. However, due to the lack of specific optical probes at the D-A interface, a detailed quantification of the long-range processes has not been feasible, until now. Here, we present a transient absorption study of long-range processes in a unique phase consisting of perylene diimide (PDI) crystals intercalated with polyfluorene (PFO), as widely used non-fullerene electron acceptor and donor, respectively. The intercalated PDI:PFO phase possesses specific well-separated spectral features for the excited states at the D-A interface. By use of femtosecond spectroscopy we reveal the excitation dynamics in this blend. PDI excitons undergo a clear symmetry-breaking charge separation in the PDI bulk, which occurs within several hundred femtoseconds, thus outcompeting excimer formation, known to limit charge separation yields when PDI is used as an acceptor. In contrast, PFO excitons are dissociated with very high yields in a one-step long-range process, enabled by large delocalization of the PFO exciton wavefunction. Moreover, both scenarios circumvent the formation of strongly-bound interfacial CT states and enable a targeted interfacial design for bulk heterojunction blends with near unity charge separation yields.

Efficient Long - Range Electron Transfer Processes in Polyfluorene – Perylene Diimide Blends

KAUST Repository

Isakova, Anna; Karuthedath, Safakath; Arnold, Thomas; Howse, Jonathan; Topham, Paul D.; Toolan, Daniel Thomas William; Laquai, Fré dé ric; Lü er, Larry

2018-01-01

In bulk heterojunction donor-acceptor (D-A) blends, high photovoltaic yields require charge carrier separation to outcompete geminate recombination. Recently, evidence for long-range electron transfer mechanisms has been presented, avoiding strongly-bound interfacial charge transfer (CT) states. However, due to the lack of specific optical probes at the D-A interface, a detailed quantification of the long-range processes has not been feasible, until now. Here, we present a transient absorption study of long-range processes in a unique phase consisting of perylene diimide (PDI) crystals intercalated with polyfluorene (PFO), as widely used non-fullerene electron acceptor and donor, respectively. The intercalated PDI:PFO phase possesses specific well-separated spectral features for the excited states at the D-A interface. By use of femtosecond spectroscopy we reveal the excitation dynamics in this blend. PDI excitons undergo a clear symmetry-breaking charge separation in the PDI bulk, which occurs within several hundred femtoseconds, thus outcompeting excimer formation, known to limit charge separation yields when PDI is used as an acceptor. In contrast, PFO excitons are dissociated with very high yields in a one-step long-range process, enabled by large delocalization of the PFO exciton wavefunction. Moreover, both scenarios circumvent the formation of strongly-bound interfacial CT states and enable a targeted interfacial design for bulk heterojunction blends with near unity charge separation yields.

Spontaneous charged lipid transfer between lipid vesicles.

Science.gov (United States)

Richens, Joanna L; Tyler, Arwen I I; Barriga, Hanna M G; Bramble, Jonathan P; Law, Robert V; Brooks, Nicholas J; Seddon, John M; Ces, Oscar; O'Shea, Paul

2017-10-03

An assay to study the spontaneous charged lipid transfer between lipid vesicles is described. A donor/acceptor vesicle system is employed, where neutrally charged acceptor vesicles are fluorescently labelled with the electrostatic membrane probe Fluoresceinphosphatidylethanolamine (FPE). Upon addition of charged donor vesicles, transfer of negatively charged lipid occurs, resulting in a fluorescently detectable change in the membrane potential of the acceptor vesicles. Using this approach we have studied the transfer properties of a range of lipids, varying both the headgroup and the chain length. At the low vesicle concentrations chosen, the transfer follows a first-order process where lipid monomers are transferred presumably through the aqueous solution phase from donor to acceptor vesicle. The rate of transfer decreases with increasing chain length which is consistent with energy models previously reported for lipid monomer vesicle interactions. Our assay improves on existing methods allowing the study of a range of unmodified lipids, continuous monitoring of transfer and simplified experimental procedures.

Exciton Transport Simulations in Phenyl Cored Thiophene Dendrimers

Science.gov (United States)

Kim, Kwiseon; Erkan Kose, Muhammet; Graf, Peter; Kopidakis, Nikos; Rumbles, Garry; Shaheen, Sean E.

2009-03-01

Phenyl cored 3-arm and 4-arm thiophene dendrimers are promising materials for use in photovoltaic devices. It is important to understand the energy transfer mechanisms in these molecules to guide the synthesis of novel dendrimers with improved efficiency. A method is developed to estimate the exciton diffusion lengths for the dendrimers and similar chromophores in amorphous films. The approach exploits Fermi's Golden Rule to estimate the energy transfer rates for an ensemble of bimolecular complexes in random orientations. Using Poisson's equation to evaluate Coulomb integrals led to efficient calculation of excitonic couplings between the transition densities. Monte-Carlo simulations revealed the dynamics of energy transport in the dendrimers. Experimental exciton diffusion lengths of the dendrimers range 10 ˜ 20 nm, increasing with the size of the dendrimer. Simulated diffusion lengths correlate well with experiments. The chemical structure of the chromophore, the shape of the transition densities and the exciton lifetime are found to be the most important factors that determine the exciton diffusion length in amorphous films.

Excitons in the Fractional Quantum Hall Effect

Science.gov (United States)

Laughlin, R. B.

1984-09-01

Quasiparticles of charge 1/m in the Fractional Quantum Hall Effect form excitons, which are collective excitations physically similar to the transverse magnetoplasma oscillations of a Wigner crystal. A variational exciton wavefunction which shows explicitly that the magnetic length is effectively longer for quasiparticles than for electrons is proposed. This wavefunction is used to estimate the dispersion relation of these excitons and the matrix elements to generate them optically out of the ground state. These quantities are then used to describe a type of nonlinear conductivity which may occur in these systems when they are relatively clean.

Final Technical Report for the Energy Frontier Research Center Understanding Charge Separation and Transfer at Interfaces in Energy Materials (EFRC:CST)

Energy Technology Data Exchange (ETDEWEB)

Vanden Bout, David A. [Univ. of Texas, Austin, TX (United States)

2015-09-14

Our EFRC was founded with the vision of creating a broadly collaborative and synergistic program that would lead to major breakthroughs in the molecular-level understanding of the critical interfacial charge separation and charge transfer (CST) processes that underpin the function of candidate materials for organic photovoltaic (OPV) and electrical-energy-storage (EES) applications. Research in these energy contexts shares an imposing challenge: How can we understand charge separation and transfer mechanisms in the presence of immense materials complexity that spans multiple length scales? To address this challenge, our 50-member Center undertook a total of 28 coordinated research projects aimed at unraveling the CST mechanisms that occur at interfaces in these nanostructured materials. This rigorous multi-year study of CST interfaces has greatly illuminated our understanding of early-timescale processes (e.g., exciton generation and dissociation dynamics at OPV heterojunctions; control of Li+-ion charging kinetics by surface chemistry) occurring in the immediate vicinity of interfaces. Program outcomes included: training of 72 graduate student and postdoctoral energy researchers at 5 institutions and spanning 7 academic disciplines in science and engineering; publication of 94 peer-reviewed journal articles; and dissemination of research outcomes via 340 conference, poster and other presentations. Major scientific outcomes included: implementation of a hierarchical strategy for understanding the electronic communication mechanisms and ultimate fate of charge carriers in bulk heterojunction OPV materials; systematic investigation of ion-coupled electron transfer processes in model Li-ion battery electrode/electrolyte systems; and the development and implementation of 14 unique technologies and instrumentation capabilities to aid in probing sub-ensemble charge separation and transfer mechanisms.

Exciton in type-II quantum dot

Energy Technology Data Exchange (ETDEWEB)

Sierra-Ortega, J; Escorcia, R A [Universidad del Magdalena, A. A. 731, Santa Marta (Colombia); Mikhailov, I D, E-mail: jsierraortega@gmail.co [Universidad Industrial de Santander, A. A. 678, Bucaramanga (Colombia)

2009-05-01

We study the quantum-size effect and the influence of the external magnetic field on the exciton ground state energy in the type-II InP quantum disk, lens and pyramid deposited on a wetting layer and embedded in a GaInP matrix. We show that the charge distribution over and below quantum dot and wetting layer induced by trapped exciton strongly depends on the quantum dot morphology and the strength of the magnetic field.

Ultrafast endothermic transfer of non-radiative exciplex state to radiative excitons in polyfluorene random copolymer for blue electroluminescence

Science.gov (United States)

Moghe, Dhanashree A.; Dey, Amrita; Johnson, Kerr; Lu, L.-P.; Friend, Richard H.; Kabra, Dinesh

2018-04-01

We report a blue-emitting random copolymer (termed modified Aryl-F8) consisting of three repeat units of polydioctylfluorene (F8), Aryl-polydioctylfluorene (Aryl-F8), and an aromatic amine comonomer unit, poly(bis-N,Ν'-(4-butylphenyl)-bis-N,N'-phenyl-1,4 phenylenediamine) chemically linked to get an improved charge carrier balance without compromising on the photoluminescence (PL) quantum yield with respect to the Aryl-F8 homo-polymer. The measured photoluminescence quantum efficiency (˜70%) of the blue-emitting polymer is comparable to or greater than the individual monomer units. The time resolved PL spectra from the modified Aryl-F8 are similar to those of Arylated-poly(9,9'-dioctylfluorene-co-bis-N,N'-(4-butylphenyl)-bis-N,N'-phenyl-1,4 phenylenediamine) (PFB) even at a time scale of 100-250 ps, indicating an ultrafast energy transfer from the (Aryl-F8 or F8):Arylated-PFB interface to Arylated-PFB, i.e., endothermic transfer of non-radiative exciplex to a radiative molecular exciton. Furthermore, the presence of non-radiative exciplex is confirmed by the photoluminescence decay profile and temperature dependent PL spectra. The luminance efficiency achieved for the modified Aryl-F8 polymer light-emitting diodes is ˜11 cd A-1 with an external quantum efficiency (EQE) of ˜4.5%, whereas it is 0.05 cd/A with an EQE of ˜0.025% for Aryl-F8. Almost two orders of higher efficiency is achieved due to the improved charge carrier balance from the random copolymer without compromising on the photoluminescence yield.

Well separated trion and neutral excitons on superacid treated MoS{sub 2} monolayers

Energy Technology Data Exchange (ETDEWEB)

Cadiz, Fabian, E-mail: cadiz@insa-toulouse.fr; Tricard, Simon; Gay, Maxime; Lagarde, Delphine; Wang, Gang; Robert, Cedric; Renucci, Pierre; Urbaszek, Bernhard; Marie, Xavier [Université de Toulouse, INSA-CNRS-UPS, LPCNO, 135 Av. Rangueil, 31077 Toulouse (France)

2016-06-20

Developments in optoelectronics and spin-optronics based on transition metal dichalcogenide monolayers (MLs) need materials with efficient optical emission and well-defined transition energies. In as-exfoliated MoS{sub 2} MLs, the photoluminescence (PL) spectra even at low temperature consist typically of broad, overlapping contributions from neutral, charged excitons (trions) and localized states. Here, we show that in superacid treated MoS{sub 2} MLs, the PL intensity increases by up to 60 times at room temperature. The neutral and charged exciton transitions are spectrally well separated in PL and reflectivity at T = 4 K, with linewidth for the neutral exciton of 15 meV, but both transitions have similar intensities compared to the ones in as-exfoliated MLs at the same temperature. Time resolved experiments uncover picoseconds recombination dynamics analyzed separately for charged and neutral exciton emissions. Using the chiral interband selection rules, we demonstrate optically induced valley polarization for both complexes and valley coherence for only the neutral exciton.

Fabrication and charge/energy-transfer study of 4,7-bis(4-triphenylamino)benzo- 2,1,3-thiadiazole/CuPc composite films

International Nuclear Information System (INIS)

Zhu Yuanyuan; Wei Xiao; Xue Minzhao; Zhang Qing; Sheng Qiaorong; Liu Yangang; Gu Shuangxi

2010-01-01

Composite films of 4,7-bis(4-triphenylamino)benzo-2,1,3-thiadiazole (TBT) and copper phthalocyanine (CuPc) are fabricated via protonation-coelectrophoretic deposition from nitromethane solutions of TBT/CuPc mixture in the presence of trifluoroacetic acid as a protonation reagent. A nanospheres-nanowires interpenetrating network structure is obtained when the molar percentage of TBT is 70%. Furthermore, the existence of TBT makes α-phased CuPc be partly transformed into the β-phase, and simultaneously, CuPc disorganizes the TBT unit cells. The blue shift on the absorption edge of TBT and the significant fluorescence quenching in the composite films indicate energy/charge transfer and donor-acceptor (D-A) heterojunction formation. Then these results are proved from another point of view: the mutual overlap of absorption and emission spectra of TBT and CuPc lead to a bidirectional Foerster resonance energy transfer at the interface; the molecular energy levels calculated from the results of cyclic voltammetry theoretically determine that there exist a D-A heterojunction and charge transfer from TBT to CuPc. Finally, from the investigation of the field-induced surface photovoltage spectra, it can be concluded that this charge transfer results in efficient dissociation of the photoinduced excitons in the composite films, followed by the generation of a strong photovoltage response.

Fabrication and charge/energy-transfer study of 4,7-bis(4-triphenylamino)benzo- 2,1,3-thiadiazole/CuPc composite films

Energy Technology Data Exchange (ETDEWEB)

Zhu Yuanyuan; Wei Xiao; Xue Minzhao; Zhang Qing; Sheng Qiaorong; Liu Yangang [School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China); Gu Shuangxi, E-mail: mzxue@sjtu.edu.c [Department of Chemistry, Fudan University, Shanghai 200433 (China)

2010-12-15

Composite films of 4,7-bis(4-triphenylamino)benzo-2,1,3-thiadiazole (TBT) and copper phthalocyanine (CuPc) are fabricated via protonation-coelectrophoretic deposition from nitromethane solutions of TBT/CuPc mixture in the presence of trifluoroacetic acid as a protonation reagent. A nanospheres-nanowires interpenetrating network structure is obtained when the molar percentage of TBT is 70%. Furthermore, the existence of TBT makes {alpha}-phased CuPc be partly transformed into the {beta}-phase, and simultaneously, CuPc disorganizes the TBT unit cells. The blue shift on the absorption edge of TBT and the significant fluorescence quenching in the composite films indicate energy/charge transfer and donor-acceptor (D-A) heterojunction formation. Then these results are proved from another point of view: the mutual overlap of absorption and emission spectra of TBT and CuPc lead to a bidirectional Foerster resonance energy transfer at the interface; the molecular energy levels calculated from the results of cyclic voltammetry theoretically determine that there exist a D-A heterojunction and charge transfer from TBT to CuPc. Finally, from the investigation of the field-induced surface photovoltage spectra, it can be concluded that this charge transfer results in efficient dissociation of the photoinduced excitons in the composite films, followed by the generation of a strong photovoltage response.

Dark excitons in transition metal dichalcogenides

Science.gov (United States)

Malic, Ermin; Selig, Malte; Feierabend, Maja; Brem, Samuel; Christiansen, Dominik; Wendler, Florian; Knorr, Andreas; Berghäuser, Gunnar

2018-01-01

Monolayer transition metal dichalcogenides (TMDs) exhibit a remarkably strong Coulomb interaction that manifests in tightly bound excitons. Due to the complex electronic band structure exhibiting several spin-split valleys in the conduction and valence band, dark excitonic states can be formed. They are inaccessibly by light due to the required spin-flip and/or momentum transfer. The relative position of these dark states with respect to the optically accessible bright excitons has a crucial impact on the emission efficiency of these materials and thus on their technological potential. Based on the solution of the Wannier equation, we present the excitonic landscape of the most studied TMD materials including the spectral position of momentum- and spin-forbidden excitonic states. We show that the knowledge of the electronic dispersion does not allow to conclude about the nature of the material's band gap since excitonic effects can give rise to significant changes. Furthermore, we reveal that an exponentially reduced photoluminescence yield does not necessarily reflect a transition from a direct to a nondirect gap material, but can be ascribed in most cases to a change of the relative spectral distance between bright and dark excitonic states.

Charge transfer processes in hybrid solar cells composed of amorphous silicon and organic materials

Energy Technology Data Exchange (ETDEWEB)

Schaefer, Sebastian; Neher, Dieter [Universitaet Potsdam, Inst. Physik u. Astronomie, Karl-Liebknecht-Strasse 24/25, 14467 Potsdam-Golm (Germany); Schulze, Tim; Korte, Lars [Helmholtz Zentrum Berlin, Inst. fuer Silizium Photovoltaik, Kekulestrasse 5, 12489 Berlin (Germany)

2011-07-01

The efficiency of hybrid solar cells composed of organic materials and amorphous hydrogenated silicon (a-Si:H) strongly depends upon the efficiency of charge transfer processes at the inorganic-organic interface. We investigated the performance of devices comprising an ITO/a-Si:H(n-type)/a-Si:H(intrinsic)/organic/metal multilayer structure and using two different organic components: zinc phthalocyanine (ZnPc) and poly(3-hexylthiophene) (P3HT). The results show higher power conversion- and quantum efficiencies for the P3HT based cells, compared to ZnPc. This can be explained by larger energy-level offset at the interface between the organic layer and a-Si:H, which facilitates hole transfer from occupied states in the valence band tail to the HOMO of the organic material and additionally promotes exciton splitting. The performance of the a-Si:H/P3HT cells can be further improved by treatment of the amorphous silicon surface with hydrofluoric acid (HF) and p-type doping of P3HT with F4TCNQ. The improved cells reached maximum power conversion efficiencies of 1%.

Robust singlet fission in pentacene thin films with tuned charge transfer interactions.

Science.gov (United States)

Broch, K; Dieterle, J; Branchi, F; Hestand, N J; Olivier, Y; Tamura, H; Cruz, C; Nichols, V M; Hinderhofer, A; Beljonne, D; Spano, F C; Cerullo, G; Bardeen, C J; Schreiber, F

2018-03-05

Singlet fission, the spin-allowed photophysical process converting an excited singlet state into two triplet states, has attracted significant attention for device applications. Research so far has focused mainly on the understanding of singlet fission in pure materials, yet blends offer the promise of a controlled tuning of intermolecular interactions, impacting singlet fission efficiencies. Here we report a study of singlet fission in mixtures of pentacene with weakly interacting spacer molecules. Comparison of experimentally determined stationary optical properties and theoretical calculations indicates a reduction of charge-transfer interactions between pentacene molecules with increasing spacer molecule fraction. Theory predicts that the reduced interactions slow down singlet fission in these blends, but surprisingly we find that singlet fission occurs on a timescale comparable to that in pure crystalline pentacene. We explain the observed robustness of singlet fission in such mixed films by a mechanism of exciton diffusion to hot spots with closer intermolecular spacings.

Near-infrared exciton-polaritons in strongly coupled single-walled carbon nanotube microcavities

Science.gov (United States)

Graf, Arko; Tropf, Laura; Zakharko, Yuriy; Zaumseil, Jana; Gather, Malte C.

2016-10-01

Exciton-polaritons form upon strong coupling between electronic excitations of a material and photonic states of a surrounding microcavity. In organic semiconductors the special nature of excited states leads to particularly strong coupling and facilitates condensation of exciton-polaritons at room temperature, which may lead to electrically pumped organic polariton lasers. However, charge carrier mobility and photo-stability in currently used materials is limited and exciton-polariton emission so far has been restricted to visible wavelengths. Here, we demonstrate strong light-matter coupling in the near infrared using single-walled carbon nanotubes (SWCNTs) in a polymer matrix and a planar metal-clad cavity. By exploiting the exceptional oscillator strength and sharp excitonic transition of (6,5) SWCNTs, we achieve large Rabi splitting (>110 meV), efficient polariton relaxation and narrow band emission (<15 meV). Given their high charge carrier mobility and excellent photostability, SWCNTs represent a promising new avenue towards practical exciton-polariton devices operating at telecommunication wavelengths.

Excitons in single-walled carbon nanotubes: environmental effect

International Nuclear Information System (INIS)

Smyrnov, O.A.

2010-01-01

The properties of excitons in semiconducting single-walled carbon nanotubes (SWCNTs) isolated in vacuum or a medium and their contributions to the optical spectra of nanotubes are studied within the elementary potential model, in which an exciton is represented as a bound state of two oppositely charged quasiparticles confined to the nanotube surface. The emphasis is given on the influence of the dielectric environment surrounding a nanotube on the exciton spectra. For nanotubes in the environment with a permittivity less than ∼ 1:8; the ground-state exciton binding energies exceed the respective energy gaps, whereas the obtained binding energies of excitons in nanotubes in a medium with permittivity greater than ∼ 4 are in good accordance with the corresponding experimental data and consistent with the known scaling relation for the environmental effect. The stabilization of a single-electron spectrum in SWCNTs in media with rather low permittivities is discussed.

Crystalline Nanoporous Frameworks: a Nanolaboratory for Probing Excitonic Device Concepts.

Energy Technology Data Exchange (ETDEWEB)

Allendorf, Mark D.; Azoulay, Jason; Ford, Alexandra Caroline; Foster, Michael E.; El Gabaly Marquez, Farid; Leonard, Francois Leonard; Leong-Hau, Kirsty; Stavila, Vitalie; Talin, Albert Alec; Wong, Brian M.; Brumbach, Michael T.; Van Gough, D.; Lambert, Timothy N.; Rodriguez, Mark A.; Spoerke, Erik David; Wheeler, David Roger; Deaton, Joseph C.; Centrone, Andrea; Haney, Paul; Kinney, R.; Szalai, Veronika; Yoon, Heayoung P.

2014-09-01

in disordered systems. Implementing this concept also creates entirely new dimensions for device fabrication that could both improve performance, increase durability, and reduce costs with unprecedented control of over properties. This report summarizes the key results of this project and is divided into sections based on publications that resulted from the work. We begin in Section 2 with an investigation of light harvesting and energy transfer in a MOF infiltrated with donor and acceptor molecules of the type typically used in OPV devices (thiophenes and fullerenes, respectively). The results show that MOFs can provide multiple functions: as a light harvester, as a stabilizer and organizer or the infiltrated molecules, and as a facilitator of energy transfer. Section 3 describes computational design of MOF linker groups to accomplish light harvesting in the visible and facilitate charge separation and transport. The predictions were validated by UV-visible absorption spectroscopy, demonstrating that rational design of MOFs for light-harvesting purposes is feasible. Section 4 extends the infiltration concept discussed in Section to, which we now designate as "Molecule@MOF" to create an electrically conducting framework. The tailorability and high conductivity of this material are unprecedented, meriting publication in the journal Science and spawning several Technical Advances. Section 5 discusses processes we developed for depositing MOFs as thin films on substrates, a critical enabling technology for fabricating MOF-based electronic devices. Finally, in Section 6 we summarize results showing that a MOF thin film can be used as a sensitizer in a DSSC, demonstrating that MOFs can serve as active layers in excitonic devices. Overall, this project provides several crucial proofs-of- concept that the potential of MOFs for use in optoelectronic devices that we predicted several years ago [ 3 ] can be realized in practice.

Steric control of the donor/acceptor interface: Implications in organic photovoltaic charge generation

KAUST Repository

Holcombe, Thomas W.; Norton, Joseph E.; Rivnay, Jonathan; Woo, Claire; Goris, Ludwig J.; Piliego, Claudia; Griffini, Gianmarco; Sellinger, Alan; Bré das, Jean Luc; Salleo, Alberto; Frechet, Jean

2011-01-01

The performance of organic photovoltaic (OPV) devices is currently limited by modest short-circuit current densities. Approaches toward improving this output parameter may provide new avenues to advance OPV technologies and the basic science of charge transfer in organic semiconductors. This work highlights how steric control of the charge separation interface can be effectively tuned in OPV devices. By introducing an octylphenyl substituent onto the investigated polymer backbones, the thermally relaxed charge-transfer state, and potentially excited charge-transfer states, can be raised in energy. This decreases the barrier to charge separation and results in increased photocurrent generation. This finding is of particular significance for nonfullerene OPVs, which have many potential advantages such as tunable energy levels and spectral breadth, but are prone to poor exciton separation efficiencies. Computational, spectroscopic, and synthetic methods were combined to develop a structure-property relationship that correlates polymer substituents with charge-transfer state energies and, ultimately, device efficiencies. © 2011 American Chemical Society.

Steric control of the donor/acceptor interface: Implications in organic photovoltaic charge generation

KAUST Repository

Holcombe, Thomas W.

2011-08-10

The performance of organic photovoltaic (OPV) devices is currently limited by modest short-circuit current densities. Approaches toward improving this output parameter may provide new avenues to advance OPV technologies and the basic science of charge transfer in organic semiconductors. This work highlights how steric control of the charge separation interface can be effectively tuned in OPV devices. By introducing an octylphenyl substituent onto the investigated polymer backbones, the thermally relaxed charge-transfer state, and potentially excited charge-transfer states, can be raised in energy. This decreases the barrier to charge separation and results in increased photocurrent generation. This finding is of particular significance for nonfullerene OPVs, which have many potential advantages such as tunable energy levels and spectral breadth, but are prone to poor exciton separation efficiencies. Computational, spectroscopic, and synthetic methods were combined to develop a structure-property relationship that correlates polymer substituents with charge-transfer state energies and, ultimately, device efficiencies. © 2011 American Chemical Society.

Programmed coherent coupling in a synthetic DNA-based excitonic circuit

Science.gov (United States)

Boulais, Étienne; Sawaya, Nicolas P. D.; Veneziano, Rémi; Andreoni, Alessio; Banal, James L.; Kondo, Toru; Mandal, Sarthak; Lin, Su; Schlau-Cohen, Gabriela S.; Woodbury, Neal W.; Yan, Hao; Aspuru-Guzik, Alán; Bathe, Mark

2018-02-01

Natural light-harvesting systems spatially organize densely packed chromophore aggregates using rigid protein scaffolds to achieve highly efficient, directed energy transfer. Here, we report a synthetic strategy using rigid DNA scaffolds to similarly program the spatial organization of densely packed, discrete clusters of cyanine dye aggregates with tunable absorption spectra and strongly coupled exciton dynamics present in natural light-harvesting systems. We first characterize the range of dye-aggregate sizes that can be templated spatially by A-tracts of B-form DNA while retaining coherent energy transfer. We then use structure-based modelling and quantum dynamics to guide the rational design of higher-order synthetic circuits consisting of multiple discrete dye aggregates within a DX-tile. These programmed circuits exhibit excitonic transport properties with prominent circular dichroism, superradiance, and fast delocalized exciton transfer, consistent with our quantum dynamics predictions. This bottom-up strategy offers a versatile approach to the rational design of strongly coupled excitonic circuits using spatially organized dye aggregates for use in coherent nanoscale energy transport, artificial light-harvesting, and nanophotonics.

Charge Transfer into Aqueous Droplets via Kilovolt Potentials

Science.gov (United States)

Hamlin, B. S.; Rosenberg, E. R.; Ristenpart, W. D.

2012-11-01

When an aqueous droplet immersed in an insulating oil contacts an electrified surface, the droplet acquires net charge. For sufficiently large field strengths, the charged droplet is driven back and forth electrophoretically between the electrodes, in essence ``bouncing'' between them. Although it is clear that the droplet acquires charge, the underlying mechanism controlling the charge transfer process has been unclear. Here we demonstrate that the chemical species present in the droplet strongly affect the charge transfer process into the drop. Using two independent charge measurement techniques, high speed video velocimetry and direct current measurement, we show that the charge acquired during contact is strongly influenced by the droplet pH. We also provide physical evidence that the electrodes undergo electroplating or corrosion for droplets with appropriate chemical species present. Together, the observations strongly suggest that electrochemical reactions govern the charge transfer process into the droplet.

Directing energy transport in organic photovoltaic cells using interfacial exciton gates.

Science.gov (United States)

Menke, S Matthew; Mullenbach, Tyler K; Holmes, Russell J

2015-04-28

Exciton transport in organic semiconductors is a critical, mediating process in many optoelectronic devices. Often, the diffusive and subdiffusive nature of excitons in these systems can limit device performance, motivating the development of strategies to direct exciton transport. In this work, directed exciton transport is achieved with the incorporation of exciton permeable interfaces. These interfaces introduce a symmetry-breaking imbalance in exciton energy transfer, leading to directed motion. Despite their obvious utility for enhanced exciton harvesting in organic photovoltaic cells (OPVs), the emergent properties of these interfaces are as yet uncharacterized. Here, directed exciton transport is conclusively demonstrated in both dilute donor and energy-cascade OPVs where judicious optimization of the interface allows exciton transport to the donor-acceptor heterojunction to occur considerably faster than when relying on simple diffusion. Generalized systems incorporating multiple exciton permeable interfaces are also explored, demonstrating the ability to further harness this phenomenon and expeditiously direct exciton motion, overcoming the diffusive limit.

Probing long-lived dark excitons in self-assembled quantum dots

DEFF Research Database (Denmark)

Johansen, Jeppe; Julsgaard, Brian; Stobbe, Søren

2010-01-01

Long-lived dark exciton states are formed in self-assembled quantum dots due to the combination of the angular momentum of electrons and holes. The lifetime of dark excitons are determined by spin-flip processes that transfer dark excitons into radiative bright excitons. We employ time......-resolved spontaneous emission measurements in a modified local density of optical states to unambiguously record the spin-flip rate. Pronounced variations in the spin-flip rate with the quantum dot emission energy are observed demonstrating that the exciton storage time can be extended by controlling the quantum dot......, which illustrates the important role of interfaces for quantum dot based nanophotonic structures....

Exciton delocalization incorporated drift-diffusion model for bulk-heterojunction organic solar cells

Science.gov (United States)

Wang, Zi Shuai; Sha, Wei E. I.; Choy, Wallace C. H.

2016-12-01

Modeling the charge-generation process is highly important to understand device physics and optimize power conversion efficiency of bulk-heterojunction organic solar cells (OSCs). Free carriers are generated by both ultrafast exciton delocalization and slow exciton diffusion and dissociation at the heterojunction interface. In this work, we developed a systematic numerical simulation to describe the charge-generation process by a modified drift-diffusion model. The transport, recombination, and collection of free carriers are incorporated to fully capture the device response. The theoretical results match well with the state-of-the-art high-performance organic solar cells. It is demonstrated that the increase of exciton delocalization ratio reduces the energy loss in the exciton diffusion-dissociation process, and thus, significantly improves the device efficiency, especially for the short-circuit current. By changing the exciton delocalization ratio, OSC performances are comprehensively investigated under the conditions of short-circuit and open-circuit. Particularly, bulk recombination dependent fill factor saturation is unveiled and understood. As a fundamental electrical analysis of the delocalization mechanism, our work is important to understand and optimize the high-performance OSCs.

Modeling temperature dependent singlet exciton dynamics in multilayered organic nanofibers

Science.gov (United States)

de Sousa, Leonardo Evaristo; de Oliveira Neto, Pedro Henrique; Kjelstrup-Hansen, Jakob; da Silva Filho, Demétrio Antônio

2018-05-01

Organic nanofibers have shown potential for application in optoelectronic devices because of the tunability of their optical properties. These properties are influenced by the electronic structure of the molecules that compose the nanofibers and also by the behavior of the excitons generated in the material. Exciton diffusion by means of Förster resonance energy transfer is responsible, for instance, for the change with temperature of colors in the light emitted by systems composed of different types of nanofibers. To study in detail this mechanism, we model temperature dependent singlet exciton dynamics in multilayered organic nanofibers. By simulating absorption and emission spectra, the possible Förster transitions are identified. Then, a kinetic Monte Carlo model is employed in combination with a genetic algorithm to theoretically reproduce time-resolved photoluminescence measurements for several temperatures. This procedure allows for the obtainment of different information regarding exciton diffusion in such a system, including temperature effects on the Förster transfer efficiency and the activation energy of the Förster mechanism. The method is general and may be employed for different systems where exciton diffusion plays a role.

Intramolecular Energy Transfer, Charge Transfer & Hydrogen Bond

Indian Academy of Sciences (India)

Ultrafast Dynamics of Chemical Reactions in Condensed Phase: Intramolecular Energy Transfer, Charge Transfer & Hydrogen Bond · PowerPoint Presentation · Slide 3 · Slide 4 · Slide 5 · Slide 6 · Slide 7 · Slide 8 · Slide 9 · Slide 10 · Slide 11 · Slide 12 · Slide 13 · Slide 14 · Slide 15 · Slide 16 · Slide 17 · Slide 18 · Slide 19.

Photophysics of charge transfer in a polyfluorene/violanthrone blend

Science.gov (United States)

Cabanillas-Gonzalez, J.; Virgili, T.; Lanzani, G.; Yeates, S.; Ariu, M.; Nelson, J.; Bradley, D. D. C.

2005-01-01

We present a study of the photophysical and photovoltaic properties of blends of violanthrone in poly[9, 9-bis (2-ethylhexyl)-fluorene-2, 7-diyl ] (PF2/6) . Photoluminescence quenching and photocurrent measurements show moderate efficiencies for charge generation, characteristic of such polymer/dye blends. Pump-probe measurements on blend films suggest that while ˜47% of the total exciton population dissociates within 4ps of photoexcitation, only ˜32% subsequently results in the formation of dye anions. We attribute the discrepancy to the likely formation of complex species with long lifetimes, such as stabilized interface charge pairs or exciplexes. This conclusion is supported by the appearance of a long lifetime component of 2.4ns in the dynamics of the photoinduced absorption signal associated to polarons in photoinduced absorption bands centered at 560nm .

Organic-Inorganic Composites of Semiconductor Nanocrystals for Efficient Excitonics.

Science.gov (United States)

Guzelturk, Burak; Demir, Hilmi Volkan

2015-06-18

Nanocomposites of colloidal semiconductor nanocrystals integrated into conjugated polymers are the key to soft-material hybrid optoelectronics, combining advantages of both plastics and particles. Synergic combination of the favorable properties in the hybrids of colloidal nanocrystals and conjugated polymers offers enhanced performance and new functionalities in light-generation and light-harvesting applications, where controlling and mastering the excitonic interactions at the nanoscale are essential. In this Perspective, we highlight and critically consider the excitonic interactions in the organic-inorganic nanocomposites to achieve highly efficient exciton transfer through rational design of the nanocomposites. The use of strong excitonic interactions in optoelectronic devices can trigger efficiency breakthroughs in hybrid optoelectronics.

Charge orders in organic charge-transfer salts

International Nuclear Information System (INIS)

Kaneko, Ryui; Valentí, Roser; Tocchio, Luca F; Becca, Federico

2017-01-01

Motivated by recent experimental suggestions of charge-order-driven ferroelectricity in organic charge-transfer salts, such as κ -(BEDT-TTF) 2 Cu[N(CN) 2 ]Cl, we investigate magnetic and charge-ordered phases that emerge in an extended two-orbital Hubbard model on the anisotropic triangular lattice at 3/4 filling. This model takes into account the presence of two organic BEDT-TTF molecules, which form a dimer on each site of the lattice, and includes short-range intramolecular and intermolecular interactions and hoppings. By using variational wave functions and quantum Monte Carlo techniques, we find two polar states with charge disproportionation inside the dimer, hinting to ferroelectricity. These charge-ordered insulating phases are stabilized in the strongly correlated limit and their actual charge pattern is determined by the relative strength of intradimer to interdimer couplings. Our results suggest that ferroelectricity is not driven by magnetism, since these polar phases can be stabilized also without antiferromagnetic order and provide a possible microscopic explanation of the experimental observations. In addition, a conventional dimer-Mott state (with uniform density and antiferromagnetic order) and a nonpolar charge-ordered state (with charge-rich and charge-poor dimers forming a checkerboard pattern) can be stabilized in the strong-coupling regime. Finally, when electron–electron interactions are weak, metallic states appear, with either uniform charge distribution or a peculiar 12-site periodicity that generates honeycomb-like charge order. (paper)

The influence of microstructure on charge separation dynamics in organic bulk heterojunction materials for solar cell applications

KAUST Repository

Scarongella, Mariateresa; Paraecattil, Arun Aby; Buchaca-Domingo, Ester; Douglas, Jessica D.; Beaupré , Serge; McCarthy-Ward, Thomas; Heeney, Martin J.; Moser, Jacques Edouard; Leclerc, Mario; Frechet, Jean; Stingelin, Natalie; Banerji, Natalie

2014-01-01

Light-induced charge formation is essential for the generation of photocurrent in organic solar cells. In order to gain a better understanding of this complex process, we have investigated the femtosecond dynamics of charge separation upon selective excitation of either the fullerene or the polymer in different bulk heterojunction blends with well-characterized microstructure. Blends of the pBTTT and PBDTTPD polymers with PCBM gave us access to three different scenarios: either a single intermixed phase, an intermixed phase with additional pure PCBM clusters, or a three-phase microstructure of pure polymer aggregates, pure fullerene clusters and intermixed regions. We found that ultrafast charge separation (by electron or hole transfer) occurs predominantly in intermixed regions, while charges are generated more slowly from excitons in pure domains that require diffusion to a charge generation site. The pure domains are helpful to prevent geminate charge recombination, but they must be sufficiently small not to become exciton traps. By varying the polymer packing, backbone planarity and chain length, we have shown that exciton diffusion out of small polymer aggregates in the highly efficient PBDTTPD:PCBM blend occurs within the same chain and is helped by delocalization. This journal is © the Partner Organisations 2014.

Exciton diffusion in WSe2 monolayers embedded in a van der Waals heterostructure

Science.gov (United States)

Cadiz, F.; Robert, C.; Courtade, E.; Manca, M.; Martinelli, L.; Taniguchi, T.; Watanabe, K.; Amand, T.; Rowe, A. C. H.; Paget, D.; Urbaszek, B.; Marie, X.

2018-04-01

We have combined spatially resolved steady-state micro-photoluminescence with time-resolved photoluminescence to investigate the exciton diffusion in a WSe2 monolayer encapsulated with hexagonal boron nitride. At 300 K, we extract an exciton diffusion length of LX = 0.36 ± 0.02 μm and an exciton diffusion coefficient of DX = 14.5 ± 2 cm2/s. This represents a nearly 10-fold increase in the effective mobility of excitons with respect to several previously reported values on nonencapsulated samples. At cryogenic temperatures, the high optical quality of these samples has allowed us to discriminate the diffusion of the different exciton species: bright and dark neutral excitons, as well as charged excitons. The longer lifetime of dark neutral excitons yields a larger diffusion length of LXD=1.5 ±0.02 μ m.

Magneto-optical quantum interferences in a system of spinor excitons

Science.gov (United States)

Kuan, Wen-Hsuan; Gudmundsson, Vidar

2018-04-01

In this work we investigate magneto-optical properties of two-dimensional semiconductor quantum-ring excitons with Rashba and Dresselhaus spin-orbit interactions threaded by a magnetic flux perpendicular to the plane of the ring. By calculating the excitonic Aharonov-Bohm spectrum, we study the Coulomb and spin-orbit effects on the Aharonov-Bohm features. From the light-matter interactions of the excitons, we find that for scalar excitons, there are open channels for spontaneous recombination resulting in a bright photoluminescence spectrum, whereas the forbidden recombination of dipolar excitons results in a dark photoluminescence spectrum. We investigate the generation of persistent charge and spin currents. The exploration of spin orientations manifests that by adjusting the strength of the spin-orbit interactions, the exciton can be constructed as a squeezed complex with specific spin polarization. Moreover, a coherently moving dipolar exciton acquires a nontrivial dual Aharonov-Casher phase, creating the possibility to generate persistent dipole currents and spin dipole currents. Our study reveals that in the presence of certain spin-orbit generated fields, the manipulation of the magnetic field provides a potential application for quantum-ring spinor excitons to be utilized in nano-scaled magneto-optical switches.

Bond charges and electronic charge transfer in ternary semiconductors

International Nuclear Information System (INIS)

Pietsch, U.

1986-01-01

By means of a simple molecule-theoretic model of 'linear superposition of two-electron molecules' the bond charges between nearest neighbours and the effective charges of ions are calculated for ternary zinc-blende structure alloys as well as chalcopyrite semiconductors. Taking into account both, the charge transfer among the ions caused by the differences of electronegativities of atoms used and between the bonds created by the internal stress of the lattice a nearly unvaried averaged bond charge amount of the alloy is found, but rather dramatically changed local bond charge parameters in comparison with the respective values of binary compounds used. This fact should influence the noncentral force interaction in such semiconductors. (author)

Efficient charge generation by relaxed charge-transfer states at organic interfaces

KAUST Repository

Vandewal, Koen

2013-11-17

Interfaces between organic electron-donating (D) and electron-accepting (A) materials have the ability to generate charge carriers on illumination. Efficient organic solar cells require a high yield for this process, combined with a minimum of energy losses. Here, we investigate the role of the lowest energy emissive interfacial charge-transfer state (CT1) in the charge generation process. We measure the quantum yield and the electric field dependence of charge generation on excitation of the charge-transfer (CT) state manifold via weakly allowed, low-energy optical transitions. For a wide range of photovoltaic devices based on polymer:fullerene, small-molecule:C60 and polymer:polymer blends, our study reveals that the internal quantum efficiency (IQE) is essentially independent of whether or not D, A or CT states with an energy higher than that of CT1 are excited. The best materials systems show an IQE higher than 90% without the need for excess electronic or vibrational energy. © 2014 Macmillan Publishers Limited.

Efficient charge generation by relaxed charge-transfer states at organic interfaces

KAUST Repository

Vandewal, Koen; Albrecht, Steve N.; Hoke, Eric T.; Graham, Kenneth; Widmer, Johannes; Douglas, Jessica D.; Schubert, Marcel; Mateker, William R.; Bloking, Jason T.; Burkhard, George F.; Sellinger, Alan; Frechet, Jean; Amassian, Aram; Riede, Moritz Kilian; McGehee, Michael D.; Neher, Dieter; Salleo, Alberto

2013-01-01

Interfaces between organic electron-donating (D) and electron-accepting (A) materials have the ability to generate charge carriers on illumination. Efficient organic solar cells require a high yield for this process, combined with a minimum of energy losses. Here, we investigate the role of the lowest energy emissive interfacial charge-transfer state (CT1) in the charge generation process. We measure the quantum yield and the electric field dependence of charge generation on excitation of the charge-transfer (CT) state manifold via weakly allowed, low-energy optical transitions. For a wide range of photovoltaic devices based on polymer:fullerene, small-molecule:C60 and polymer:polymer blends, our study reveals that the internal quantum efficiency (IQE) is essentially independent of whether or not D, A or CT states with an energy higher than that of CT1 are excited. The best materials systems show an IQE higher than 90% without the need for excess electronic or vibrational energy. © 2014 Macmillan Publishers Limited.

The charge transfer structure and effective energy transfer in multiplayer assembly film

International Nuclear Information System (INIS)

Li Mingqiang; Jian Xigao

2005-01-01

Charge transfer multiplayer films have been prepared by layer-by-layer self-assembly technique. The films incorporate the rare-earth-containing polyoxometalate K 11 [Eu{PW 11 O 39 } 2 ].nH 2 O and the rich electron polyelectrolyte poly(3-viny-1-methyl-pyridine) quaternary ammonium and display a linear increase in the absorption and film thickness with the number of deposition cycles. Ultraviolet and visible absorption spectra, atomic force micrographs, small-angle X-ray reflectivity measurements, and photoluminescence spectra were used to determine the structure of films. Linear and regular multilayer growth was observed. We can observe the formation of charge transfer complex compound in multiplayer by layer-by-layer assembly method. Most importantly, the luminescence spectra show the charge transfer band in assembly films, which suggest that energy could be effectively transferred to rare earth ions in assembly multiplayer films

Energy Transfer Kinetics in Photosynthesis as an Inspiration for Improving Organic Solar Cells.

Science.gov (United States)

Nganou, Collins; Lackner, Gerhard; Teschome, Bezu; Deen, M Jamal; Adir, Noam; Pouhe, David; Lupascu, Doru C; Mkandawire, Martin

2017-06-07

Clues to designing highly efficient organic solar cells may lie in understanding the architecture of light-harvesting systems and exciton energy transfer (EET) processes in very efficient photosynthetic organisms. Here, we compare the kinetics of excitation energy tunnelling from the intact phycobilisome (PBS) light-harvesting antenna system to the reaction center in photosystem II in intact cells of the cyanobacterium Acaryochloris marina with the charge transfer after conversion of photons into photocurrent in vertically aligned carbon nanotube (va-CNT) organic solar cells with poly(3-hexyl)thiophene (P3HT) as the pigment. We find that the kinetics in electron hole creation following excitation at 600 nm in both PBS and va-CNT solar cells to be 450 and 500 fs, respectively. The EET process has a 3 and 14 ps pathway in the PBS, while in va-CNT solar cell devices, the charge trapping in the CNT takes 11 and 258 ps. We show that the main hindrance to efficiency of va-CNT organic solar cells is the slow migration of the charges after exciton formation.

Fractional Solitons in Excitonic Josephson Junctions

Science.gov (United States)

Su, Jung-Jung; Hsu, Ya-Fen

The Josephson effect is especially appealing because it reveals macroscopically the quantum order and phase. Here we study this effect in an excitonic Josephson junction: a conjunct of two exciton condensates with a relative phase ϕ0 applied. Such a junction is proposed to take place in the quantum Hall bilayer (QHB) that makes it subtler than in superconductor because of the counterflow of excitonic supercurrent and the interlayer tunneling in QHB. We treat the system theoretically by first mapping it into a pseudospin ferromagnet then describing it by the Landau-Lifshitz-Gilbert equation. In the presence of interlayer tunneling, the excitonic Josephson junction can possess a family of fractional sine-Gordon solitons that resemble the static fractional Josephson vortices in the extended superconducting Josephson junctions. Interestingly, each fractional soliton carries a topological charge Q which is not necessarily a half/full integer but can vary continuously. The resultant current-phase relation (CPR) shows that solitons with Q =ϕ0 / 2 π are the lowest energy states for small ϕ0. When ϕ0 > π , solitons with Q =ϕ0 / 2 π - 1 take place - the polarity of CPR is then switched.

The Role of FRET in Non-Fullerene Organic Solar Cells: Implications for Molecular Design.

Science.gov (United States)

Gautam, Bhoj R; Younts, Robert; Carpenter, Joshua; Ade, Harald; Gundogdu, Kenan

2018-04-19

Non-fullerene acceptors (NFAs) have been demonstrated to be promising candidates for highly efficient organic photovoltaic (OPV) devices. The tunability of absorption characteristics of NFAs can be used to make OPVs with complementary donor-acceptor absorption to cover a broad range of the solar spectrum. However, both charge transfer from donor to acceptor moieties and energy (energy) transfer from high-bandgap to low-bandgap materials are possible in such structures. Here, we show that when charge transfer and exciton transfer processes are both present, the coexistence of excitons in both domains can cause a loss mechanism. Charge separation of excitons in a low-bandgap material is hindered due to exciton population in the larger bandgap acceptor domains. Our results further show that excitons in low-bandgap material should have a relatively long lifetime compared to the transfer time of excitons from higher bandgap material in order to contribute to the charge separation. These observations provide significant guidance for design and development of new materials in OPV applications.

Photosynthesis Revisited: Optimization of Charge and Energy Transfer in Quantum Materials

Science.gov (United States)

Gabor, Nathaniel

2014-03-01

The integration of new nano- and molecular-scale quantum materials into ultra-efficient energy harvesting devices presents significant scientific challenges. Of the many challenges, the most difficult is achieving high photon-to-electron conversion efficiency while maintaining broadband absorption. Due to exciton effects, devices composed of quantum materials may allow near-unity optical absorption efficiency yet require the choice of precisely one fundamental energy (HOMO-LUMO gap). To maximize absorption, the simplest device would absorb at the peak of the solar spectrum, which spans the visible wavelengths. If the peak of the solar spectrum spans the visible wavelengths, then why are terrestrial plants green? Here, I discuss a physical model of photosynthetic absorption and photoprotection in which the cell utilizes active feedback to optimize charge and energy transfer, thus maximizing stored energy rather than absorption. This model, which addresses the question of terrestrial greenness, is supported by several recent results that have begun to unravel the details of photoprotection in higher plants. More importantly, this model indicates a novel route for the design of next-generation energy harvesting systems based on nano- and molecular-scale quantum materials.

Two-Centre Close-Coupling method in charge transfer

Directory of Open Access Journals (Sweden)

Reza Bagheri

2017-09-01

Full Text Available In the present work, the transition matrix elements as well as differential and total scattering cross-sections for positronium formation in Positron-Hydrogen atom collision and hydrogen formation in Positronium-Hydrogen ion collision, through the charge transfer channel by Two-Centre Close-Coupling method up to a first order approximation have been calculated. The charge transfer collision is assumed to be a three-body reaction, while the projectile is a plane wave. Additionally, the hydrogen and positronium atoms are assumed, initially, to be in their ground states. For the case of charge transfer in the scattering of positron by hydrogen atoms, the differential cross sections are plotted for the energy range of 50eV to 10keV, where the Thomas peak is clearly observable. Finally, the total scattering cross-section for the charge transfer in the collision of Positron-Hydrogen and Positronium-Hydrogen ion are plotted as a function of projectile energies and compared with other methods in the literature.

Effects of surface and interface traps on exciton and multi-exciton dynamics in core/shell quantum dots

Science.gov (United States)

Bozio, Renato; Righetto, Marcello; Minotto, Alessandro

2017-08-01

Exciton interactions and dynamics are the most important factors determining the exceptional photophysical properties of semiconductor quantum dots (QDs). In particular, best performances have been obtained for ingeniously engineered core/shell QDs. We have studied two factors entering in the exciton decay dynamics with adverse effects for the luminescence efficiency: exciton trapping at surface and interface traps, and non-radiative Auger recombination in QDs carrying either net charges or multiple excitons. In this work, we present a detailed study into the optical absorption, fluorescence dynamics and quantum yield, as well as ultrafast transient absorption properties of CdSe/CdS, CdSe/Cd0.5Zn0.5S, and CdSe/ZnS QDs as a function of shell thickness. It turns out that de-trapping processes play a pivotal role in determining steady state emission properties. By studying the excitation dependent photoluminescence quantum yields (PLQY) in different CdSe/CdxZn1-xS (x = 0, 0.5, 1) QDs, we demonstrate the different role played by hot and cold carrier trapping rates in determining fluorescence quantum yields. Finally, the use of global analysis allows us untangling the complex ultrafast transient absorption signals. Smoothing of interface potential, together with effective surface passivation, appear to be crucial factors in slowing down both Auger-based and exciton trapping recombination processes.

Metal nanoparticle mediated space charge and its optical control in an organic hole-only device

OpenAIRE

Ligorio, G.; Nardi, M. V.; Steyrleuthner, Robert; Ihiawakrim, D.; Crespo-Monteiro, N.; Brinkmann, M.; Neher, D.; Koch, N.

2017-01-01

We reveal the role of localized space charges in hole-only devices based on an organic semiconductor with embedded metal nanoparticles (MNPs). MNPs act as deep traps for holes and reduce the current density compared to a device without MNPs by a factor of 104 due to the build-up of localized space charge. Dynamic MNPs charged neutrality can be realized during operation by electron transfer from excitons created in the organic matrix, enabling light sensing independent of device bias. In contr...

Energy level alignment and sub-bandgap charge generation in polymer:fullerene bulk heterojunction solar cells.

Science.gov (United States)

Tsang, Sai-Wing; Chen, Song; So, Franky

2013-05-07

Using charge modulated electroabsorption spectroscopy (CMEAS), for the first time, the energy level alignment of a polymer:fullerene bulk heterojunction photovoltaic cell is directly measured. The charge-transfer excitons generated by the sub-bandgap optical pumping are coupled with the modulating electric field and introduce subtle changes in optical absorption in the sub-bandgap region. This minimum required energy for sub-bandgap charge genreation is defined as the effective bandgap. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Impacts of side chain and excess energy on the charge photogeneration dynamics of low-bandgap copolymer-fullerene blends

International Nuclear Information System (INIS)

Huo, Ming-Ming; Zhang, Jian-Ping; Hu, Rong; Xing, Ya-Dong; Liu, Yu-Chen; Ai, Xi-Cheng; Hou, Jian-Hui

2014-01-01

Primary charge photogeneration dynamics in neat and fullerene-blended films of a pair of alternating benzo[1,2-b:4,5-b ′ ]dithiophene (BDT) and thieno[3,4-b]thiophene (TT) copolymers are comparatively studied by using near-infrared, time-resolved absorption (TA) spectroscopy under low excitation photon fluence. PBDTTT-E and PBDTTT-C, differed merely in the respective TT-substituents of ester (-E) and carbonyl (-C), show distinctly different charge photogeneration dynamics. The pair of neat PBDTTT films show exciton lifetimes of ∼0.1 ns and fluorescence quantum yields below 0.2%, as well as prominent excess-energy enhanced exciton dissociation. In addition, PBDTTT-C gives rise to >50% higher P •+ yield than PBDTTT-E does irrespective to the excitation photon energy. Both PBDTTT-E:PC 61 BM and PBDTTT-C:PC 61 BM blends show subpicosecond exciton lifetimes and nearly unitary fluorescence quenching efficiency and, with respect to the former blend, the latter one shows substantially higher branching ratio of charge separated (CS) state over interfacial charge transfer (ICT) state, and hence more efficient exciton-to-CS conversion. For PBDTTT-C:PC 61 BM, the ultrafast charge dynamics clearly show the processes of ICT-CS interconversion and P •+ migration, which are possibly influenced by the ICT excess energy. However, such processes are relatively indistinctive in the case of PBDTTT-E:PC 61 BM. The results strongly prove the importance of ICT dissociation in yielding free charges, and are discussed in terms of the film morphology and the precursory solution-phase macromolecular conformation

Measurement of Exciton Binding Energy of Monolayer WS2

Science.gov (United States)

Chen, Xi; Zhu, Bairen; Cui, Xiaodong

Excitonic effects are prominent in monolayer crystal of transition metal dichalcogenides (TMDCs) because of spatial confinement and reduced Coulomb screening. Here we use linear differential transmission spectroscopy and two-photon photoluminescence excitation spectroscopy (TP-PLE) to measure the exciton binding energy of monolayer WS2. Peaks for excitonic absorptions of the direct gap located at K valley of the Brillouin zone and transitions from multiple points near Γ point of the Brillouin zone, as well as trion side band are shown in the linear absorption spectra of WS2. But there is no gap between distinct excitons and the continuum of the interband transitions. Strong electron-phonon scattering, overlap of excitons around Γ point and the transfer of the oscillator strength from interband continuum to exciton states make it difficult to resolve the electronic interband transition edge even down to 10K. The gap between excited states of the band-edge exciton and the single-particle band is probed by TP-PLE measurements. And the energy difference between 1s exciton and the single-particle gap gives the exciton binding energy of monolayer WS2 to be about 0.71eV. The work is supported by Area of excellency (AoE/P-04/08), CRF of Hong Kong Research Grant Council (HKU9/CRF/13G) and SRT on New Materials of The University of Hong Kong.

Communication: Broad manifold of excitonic states in light-harvesting complex 1 promotes efficient unidirectional energy transfer in vivo

Science.gov (United States)

Sohail, Sara H.; Dahlberg, Peter D.; Allodi, Marco A.; Massey, Sara C.; Ting, Po-Chieh; Martin, Elizabeth C.; Hunter, C. Neil; Engel, Gregory S.

2017-10-01

In photosynthetic organisms, the pigment-protein complexes that comprise the light-harvesting antenna exhibit complex electronic structures and ultrafast dynamics due to the coupling among the chromophores. Here, we present absorptive two-dimensional (2D) electronic spectra from living cultures of the purple bacterium, Rhodobacter sphaeroides, acquired using gradient assisted photon echo spectroscopy. Diagonal slices through the 2D lineshape of the LH1 stimulated emission/ground state bleach feature reveal a resolvable higher energy population within the B875 manifold. The waiting time evolution of diagonal, horizontal, and vertical slices through the 2D lineshape shows a sub-100 fs intra-complex relaxation as this higher energy population red shifts. The absorption (855 nm) of this higher lying sub-population of B875 before it has red shifted optimizes spectral overlap between the LH1 B875 band and the B850 band of LH2. Access to an energetically broad distribution of excitonic states within B875 offers a mechanism for efficient energy transfer from LH2 to LH1 during photosynthesis while limiting back transfer. Two-dimensional lineshapes reveal a rapid decay in the ground-state bleach/stimulated emission of B875. This signal, identified as a decrease in the dipole strength of a strong transition in LH1 on the red side of the B875 band, is assigned to the rapid localization of an initially delocalized exciton state, a dephasing process that frustrates back transfer from LH1 to LH2.

Angular momentum transport with twisted exciton wave packets

Science.gov (United States)

Zang, Xiaoning; Lusk, Mark T.

2017-10-01

A chain of cofacial molecules with CN or CN h symmetry supports excitonic states with a screwlike structure. These can be quantified with the combination of an axial wave number and an azimuthal winding number. Combinations of these states can be used to construct excitonic wave packets that spiral down the chain with well-determined linear and angular momenta. These twisted exciton wave packets can be created and annihilated using laser pulses, and their angular momentum can be optically modified during transit. This allows for the creation of optoexcitonic circuits in which information, encoded in the angular momentum of light, is converted into excitonic wave packets that can be manipulated, transported, and then reemitted. A tight-binding paradigm is used to demonstrate the key ideas. The approach is then extended to quantify the evolution of twisted exciton wave packets in a many-body, multilevel time-domain density functional theory setting. In both settings, numerical methods are developed that allow the site-to-site transfer of angular momentum to be quantified.

Collisional charging of individual submillimeter particles: Using ultrasonic levitation to initiate and track charge transfer

Science.gov (United States)

Lee, Victor; James, Nicole M.; Waitukaitis, Scott R.; Jaeger, Heinrich M.

2018-03-01

Electrostatic charging of insulating fine particles can be responsible for numerous phenomena ranging from lightning in volcanic plumes to dust explosions. However, even basic aspects of how fine particles become charged are still unclear. Studying particle charging is challenging because it usually involves the complexities associated with many-particle collisions. To address these issues, we introduce a method based on acoustic levitation, which makes it possible to initiate sequences of repeated collisions of a single submillimeter particle with a flat plate, and to precisely measure the particle charge in situ after each collision. We show that collisional charge transfer between insulators is dependent on the hydrophobicity of the contacting surfaces. We use glass, which we modify by attaching nonpolar molecules to the particle, the plate, or both. We find that hydrophilic surfaces develop significant positive charges after contacting hydrophobic surfaces. Moreover, we demonstrate that charging between a hydrophilic and a hydrophobic surface is suppressed in an acidic environment and enhanced in a basic one. Application of an electric field during each collision is found to modify the charge transfer, again depending on surface hydrophobicity. We discuss these results within the context of contact charging due to ion transfer, and we show that they lend strong support to O H- ions as the charge carriers.

Charge-transfer channel in quantum dot-graphene hybrid materials

Science.gov (United States)

Cao, Shuo; Wang, Jingang; Ma, Fengcai; Sun, Mengtao

2018-04-01

The energy band theory of a classical semiconductor can qualitatively explain the charge-transfer process in low-dimensional hybrid colloidal quantum dot (QD)-graphene (GR) materials; however, the definite charge-transfer channels are not clear. Using density functional theory (DFT) and time-dependent DFT, we simulate the hybrid QD-GR nanostructure, and by constructing its orbital interaction diagram, we show the quantitative coupling characteristics of the molecular orbitals (MOs) of the hybrid structure. The main MOs are derived from the fragment MOs (FOs) of GR, and the Cd13Se13 QD FOs merge with the GR FOs in a certain proportion to afford the hybrid system. Upon photoexcitation, electrons in the GR FOs jump to the QD FOs, leaving holes in the GR FOs, and the definite charge-transfer channels can be found by analyzing the complex MOs coupling. The excited electrons and remaining holes can also be localized in the GR or the QD or transfer between the QD and GR with different absorption energies. The charge-transfer process for the selected excited states of the hybrid QD-GR structure are testified by the charge difference density isosurface. The natural transition orbitals, charge-transfer length analysis and 2D site representation of the transition density matrix also verify the electron-hole delocalization, localization, or coherence chacracteristics of the selected excited states. Therefore, our research enhances understanding of the coupling mechanism of low-dimensional hybrid materials and will aid in the design and manipulation of hybrid photoelectric devices for practical application in many fields.

Charge separation and transfer in hybrid type II tunneling structures of CdTe and CdSe nanocrystals

Energy Technology Data Exchange (ETDEWEB)

Gross, Dieter Konrad Michael

2013-11-08

-quenching vanishes when this offset approaches 0.0 eV. The fact that PL-quenching and its correlation with the energetic offset was observed for both clustered and layered assembly provides a strong indirect indication of charge separation via electron transfer from CdTe to CdSe nanocrystals. The main result of this thesis is the direct proof of the charge separation on the type II interface of CdTe and CdSe nanocrystal layers. SPV-measurements as a direct measurement methode showed clearly the directionality of charge separation since the SPV measures the electric field of the separated charges. Electrons are collected on CdSe nanocrystal layers, holes on CdTe nanocrystal layers. A change in the order between CdSe and CdTe therefore leads to a change in the sign of the SPV-signal. Both SPVspectra and time-resolved SPV-measurements support this finding and showed that the charge selectivity of the CdTe-CdSe interface is unidirectional for the whole excitation spectrum and the entire investigated time range. This indicates that the directionality of the CdTe-CdSe interface is the only dominant charge separation mechanism that was observed. Hence, the type II alignment of the self-assembled nanocrystals used was clearly proven. Introducing an additional barrier between the nanocrystal layers doubled the barrier width so that the SPV-signal is quenched. This is consistent with tunneling transfer which is exponentially dependent on barrier width. Moreover, we learned that both absorption in CdTe and CdSe nanocrystals and the sample thickness contribute to the SPV-signal. Thus, we could observe electron diffusion in CdSe multilayers which was faster than the charge carrier diffusion dynamics in CdTe nanocrystal multilayers. Future research may address the combination of energy transfer dynamics with the charge separation processes presented in this thesis. On the one hand, this may provide a better understanding of their fundamental processes and differentiate between excitonic FRET and

Effective models for excitons in carbon nanotubes

DEFF Research Database (Denmark)

Cornean, Horia; Duclos, Pierre; Ricaud, Benjamin

2007-01-01

We analyse the low lying spectrum of a model of excitons in carbon nanotubes. Consider two particles with opposite charges and a Coulomb self-interaction, placed on an infinitely long cylinder. If the cylinder radius becomes small, the low lying spectrum of their relative motion is well described...

Excitons in insulators

International Nuclear Information System (INIS)

Grasser, R.; Scharmann, A.

1983-01-01

This chapter investigates absorption, reflectivity, and intrinsic luminescence spectra of free and/or self-trapped (localized) excitons in alkali halides and rare gas solids. Introduces the concepts underlying the Wannier-Mott and Frenkel exciton models, two extreme pictures of an exciton in crystalline materials. Discusses the theoretical and experimental background; excitons in alkali halides; and excitons in rare gas solids. Shows that the intrinsic optical behavior of wide gap insulators in the range of the fundamental absorption edge is controlled by modified Wannier-Mott excitons. Finds that while that alkali halides only show free and relaxed molecular-like exciton emission, in rare gas crystals luminescence due to free, single and double centered localized excitons is observed. Indicates that the simultaneous existence of free and self-trapped excitons in these solid requires an energy barrier for self-trapping

Understanding the free energy barrier and multiple timescale dynamics of charge separation in organic photovoltaic cells.

Science.gov (United States)

Yan, Yaming; Song, Linze; Shi, Qiang

2018-02-28

By employing several lattice model systems, we investigate the free energy barrier and real-time dynamics of charge separation in organic photovoltaic (OPV) cells. It is found that the combined effects of the external electric field, entropy, and charge delocalization reduce the free energy barrier significantly. The dynamic disorder reduces charge carrier delocalization and results in the increased charge separation barrier, while the effect of static disorder is more complicated. Simulation of the real-time dynamics indicates that the free charge generation process involves multiple time scales, including an ultrafast component within hundreds of femtoseconds, an intermediate component related to the relaxation of the hot charge transfer (CT) state, and a slow component on the time scale of tens of picoseconds from the thermally equilibrated CT state. Effects of hot exciton dissociation as well as its dependence on the energy offset between the Frenkel exciton and the CT state are also analyzed. The current results indicate that only a small energy offset between the band gap and the lowest energy CT state is needed to achieve efficient free charge generation in OPV devices, which agrees with recent experimental findings.

Understanding the free energy barrier and multiple timescale dynamics of charge separation in organic photovoltaic cells

Science.gov (United States)

Yan, Yaming; Song, Linze; Shi, Qiang

2018-02-01

By employing several lattice model systems, we investigate the free energy barrier and real-time dynamics of charge separation in organic photovoltaic (OPV) cells. It is found that the combined effects of the external electric field, entropy, and charge delocalization reduce the free energy barrier significantly. The dynamic disorder reduces charge carrier delocalization and results in the increased charge separation barrier, while the effect of static disorder is more complicated. Simulation of the real-time dynamics indicates that the free charge generation process involves multiple time scales, including an ultrafast component within hundreds of femtoseconds, an intermediate component related to the relaxation of the hot charge transfer (CT) state, and a slow component on the time scale of tens of picoseconds from the thermally equilibrated CT state. Effects of hot exciton dissociation as well as its dependence on the energy offset between the Frenkel exciton and the CT state are also analyzed. The current results indicate that only a small energy offset between the band gap and the lowest energy CT state is needed to achieve efficient free charge generation in OPV devices, which agrees with recent experimental findings.

Metal nanoparticle mediated space charge and its optical control in an organic hole-only device

International Nuclear Information System (INIS)

Ligorio, G.; Nardi, M. V.; Steyrleuthner, R.; Neher, D.; Ihiawakrim, D.; Crespo-Monteiro, N.; Brinkmann, M.; Koch, N.

2016-01-01

We reveal the role of localized space charges in hole-only devices based on an organic semiconductor with embedded metal nanoparticles (MNPs). MNPs act as deep traps for holes and reduce the current density compared to a device without MNPs by a factor of 10 4 due to the build-up of localized space charge. Dynamic MNPs charged neutrality can be realized during operation by electron transfer from excitons created in the organic matrix, enabling light sensing independent of device bias. In contrast to the previous speculations, electrical bistability in such devices was not observed.

Luminescence and optical spectroscopy of charge transfer processes in solid solutions NiCMg1−CO and NixZn1−xO

International Nuclear Information System (INIS)

Sokolov, V.I.; Pustovarov, V.A.; Churmanov, V.N.; Gruzdev, N.B.; Uimin, M.A.; Byzov, I.V.; Druzhinin, A.V.; Mironova-Ulmane, N.A.

2016-01-01

In this work photoluminescence spectra for Ni c Mg 1−c O and Ni x Zn 1−x O solid solutions with the rock-salt crystal structure were obtained under synchrotron radiation excitation. Periodical peaks in the photoluminescence excitation spectrum of Ni c Mg 1−c O (c=0.008) have been discovered for a wide-gap oxide doped with 3d impurities for the first time. They can be considered as LO phonon repetitions of the narrow zero phonon line resulted from the optical transitions into the p–d charge transfer exciton [d 9 h] state. A close coincidence in energy of different peculiarities in the optical absorption and photoluminescence excitation spectra for the Ni c Mg 1−c O and Ni x Zn 1−x O solid solutions is due to the practically equal interatomic distances Ni–O in the investigated materials. The bulk of new experimental results is the trustworthy evidence that only the p–d charge transfer transitions manifest themselves in the spectral region of 3.5–6.5 eV. - Highlights: • Emission of Ni c Mg 1−c O nanocystals excited by synchrotron radiation is obtained. • LO phonon repetitions have been observed in PLE spectra of Ni c Mg 1−c O firstly for wide gap oxide materials doped with 3d impurities. • The [d 9 h] acceptor exciton state in Ni c Mg 1−c O (c=0.008) are indirectly revealed. • The begin of PLE spectra of Ni x Zn 1−x O are not virtually shifted with a change of composition x. • The near energy coincidence of absorption peaks for nanocrystals NiO and single crystal Ni c Mg 1−c O (c=0.0006) manifests itself.

Charge transfer reactions in Xe plasma expansion

International Nuclear Information System (INIS)

Jiao, C. Q.; Garscadden, A.; Ganguly, B. N.

2007-01-01

Charge transfer reactions of fast Xe ions with hydrocarbons including methane (CH 4 ), ethene (C 2 H 4 ), and propane (C 3 H 8 ) are studied by adding these hydrocarbon gases into a cross flowing Xe plasma expansion. Branching ratios and relative reaction rates for the charge transfers of fast Xe + with each of the three hydrocarbon gases are measured under different rf powers of the inductively coupled Xe discharge. For CH 4 /Xe system, we find that fast Xe + reacts readily with CH 4 generating CH 4 + and CH 3 + in a ratio of 1:0.56, with an estimated rate coefficient of (2.3±0.3)x10 -10 cm 3 /s at 75 W rf power which slowly increases to (2.9±0.3)x10 -10 cm 3 /s at 250 W (error bars reflect only the uncertainties due to the unknown extent of the ion recombination that follows the charge transfer reaction). These observed charge transfer reactions are made possible by the kinetically excited Xe ions produced by free expansion of the plasma. For the C 2 H 4 /Xe system product ions C 2 H 4 + and C 2 H 2 + are observed, and for C 3 H 8 /Xe, C 2 H 4 + and C 2 H 5 + and minor product ions including C 2 H 2 + and C 3 H 7 + are observed

Charge-transfer cross sections in collisions of ground-state Ca and H+

Science.gov (United States)

Dutta, C. M.; Oubre, C.; Nordlander, P.; Kimura, M.; Dalgarno, A.

2006-03-01

We have investigated collisions of Ca(4s2) with H+ in the energy range of 200eV/u-10keV/u using the semiclassical molecular-orbital close-coupling (MOCC) method with 18 coupled molecular states ( 11Σ+1 and seven Π+1 states) to determine charge-transfer cross sections. Except for the incoming channel 6Σ+1 , the molecular states all correspond to charge-transfer channels. Inclusion of Ca2+-H- is crucial in the configuration-interaction calculation for generating the molecular wave functions and potentials. Because of the Coulomb attraction, the state separating to Ca2+-H- creates many avoided crossings, even though at infinite separation it lies energetically above all other states that we included. Because of the avoided crossings between the incoming channel 6Σ+1 and the energetically close charge-transfer channel 7Σ+1 the charge-transfer interaction occurs at long range. This makes calculations of charge-transfer cross sections by the MOCC method very challenging. The total charge-transfer cross sections increase monotonically from 3.4×10-15cm2 at 200eV/u to 4.5×10-15cm2 at 10keV/u . Charge transfer occurs mostly to the excited Ca+(5p) state in the entire energy range, which is the sum of the charge transfer to 7Σ+1 and 4Π+1 . It accounts for ˜47% of the total charge transfer cross sections at 200eV/u . However, as the energy increases, transfer to Ca+(4d) increases, and at 10keV/u the charge-transfer cross sections for Ca+(5p) and Ca+(4d) become comparable, each giving ˜38% of the total cross section.

Charge-transfer cross sections in collisions of ground-state Ca and H+

International Nuclear Information System (INIS)

Dutta, C. M.; Oubre, C.; Nordlander, P.; Kimura, M.; Dalgarno, A.

2006-01-01

We have investigated collisions of Ca(4s 2 ) with H + in the energy range of 200 eV/u-10 keV/u using the semiclassical molecular-orbital close-coupling (MOCC) method with 18 coupled molecular states (11 1 Σ + and seven 1 Π + states) to determine charge-transfer cross sections. Except for the incoming channel 6 1 Σ + , the molecular states all correspond to charge-transfer channels. Inclusion of Ca 2+ -H - is crucial in the configuration-interaction calculation for generating the molecular wave functions and potentials. Because of the Coulomb attraction, the state separating to Ca 2+ -H - creates many avoided crossings, even though at infinite separation it lies energetically above all other states that we included. Because of the avoided crossings between the incoming channel 6 1 Σ + and the energetically close charge-transfer channel 7 1 Σ + the charge-transfer interaction occurs at long range. This makes calculations of charge-transfer cross sections by the MOCC method very challenging. The total charge-transfer cross sections increase monotonically from 3.4x10 -15 cm 2 at 200 eV/u to 4.5x10 -15 cm 2 at 10 keV/u. Charge transfer occurs mostly to the excited Ca + (5p) state in the entire energy range, which is the sum of the charge transfer to 7 1 Σ + and 4 1 Π + . It accounts for ∼47% of the total charge transfer cross sections at 200 eV/u. However, as the energy increases, transfer to Ca + (4d) increases, and at 10 keV/u the charge-transfer cross sections for Ca + (5p) and Ca + (4d) become comparable, each giving ∼38% of the total cross section

Quasi-resonant K-K charge transfer

International Nuclear Information System (INIS)

Hagmann, S.; Cocke, C.L.; Richard, P.; Skutlartz, A.; Kelbch, S.; Schmidt-Boecking, H.; Schuch, R.

1983-01-01

The impact parameter dependence, P(b), of single and double K to K charge transfer have been deduced from the coincidences between K-Auger electrons and scattered particles for F 9+ + Ne and F 9+ + Ne collisions at 10 MeV and 4.4 MeV. The 4.4 MeV single K-K transfer probability exhibits oscillations with b. The P(b) for delta-electron emission is also reported. To obtain more details on the mechanism, K-Auger electron-Ne recoil ion coincidences are measured for both F 8+ and F 9+ projectiles. The relative amounts of recoil ions and of satellite and hypersatellite Auger transitions vary substantially with projectile charge state. 11 references, 11 figures

Mass and charge transfer within a floating water bridge

Science.gov (United States)

Fuchs, Elmar C.; Agostinho, Luewton L. F.; Eisenhut, Mathias; Woisetschläger, Jakob

2010-11-01

When high voltage is applied to pure water filled into two beakers close to each other, a connection forms spontaneously, giving the impression of a floating water bridge 1-8. This phenomenon is of special interest, since it comprises a number of phenomena currently tackled in modern water science. In this work, the charge and mass transfer through the water bridge are investigated with schlieren visualization and laser interferometry. It can be shown that the addition of a pH dye increases the H+ and OH- production with subsequent electrolysis, whereas schlieren and interferometric methods reveal another mechanism where charge and mass transfer appear to be coupled. Whereas this mechanism seems to be responsible for the electrolysis-less charge and mass transfer in the water bridge, it is increasingly superseded by the electrochemical mechanism with rising conductivity. Thus it can be shown that a pH dye does only indirectly visualize the charge transfer in the water bridge since it is dragged along with the water flow like any other dye, and additionally promotes conventional electrochemical conduction mechanisms, thereby enhancing electrolysis and reducing the masscoupled charge transport and thus destabilizing the bridge.

The Roles of Structural Order and Intermolecular Interactions in Determining Ionization Energies and Charge-Transfer State Energies in Organic Semiconductors

KAUST Repository

Graham, Kenneth; Ngongang Ndjawa, Guy Olivier; Conron, Sarah M.; Munir, Rahim; Vandewal, Koen; Chen, John J.; Sweetnam, Sean; Thompson, Mark E.; Salleo, Alberto; Mcgehee, Michael D.; Amassian, Aram

2016-01-01

The energy landscape in organic semiconducting materials greatly influences charge and exciton behavior, which are both critical to the operation of organic electronic devices. These energy landscapes can change dramatically depending on the phases

Excitons in conjugated polymers: Do we need a paradigma change?

Energy Technology Data Exchange (ETDEWEB)

Beenken, Wichard J.D. [Department of Theoretical Physics I, Ilmenau University of Thechnology (Germany)

2009-12-15

We have previously shown that both, polymer conformation and dynamics are crucial for the exciton transport in conjugated polymers. Thereby we found that the usual Foerster-type hopping transfer model - even if one applies the line-dipole approximation - falls short in one crucial aspect: the nature of the sites the excitons are transferred between is still unclear. We found that the simple model of spectroscopic units defined as segments of the polymer chains separated by structural defects breaking the {pi}-conjugation is only justified for chemical defects like hydrogenated double bonds, or extreme gauche (90 ) torsions between the monomers. Both defects are far too rare in a well-prepared conjugated polymer to explain the mean spectroscopic-unit length of typically 6-7 monomers. Meanwhile, also the concept of dynamical formation of the spectroscopic units, we had previously suggested, has also failed. Thus the question of a paradigma change concerning the exciton transport in conjugated polymers appears on the agenda. (Abstract Copyright [2009], Wiley Periodicals, Inc.)

Effect of localized surface-plasmon mode on exciton transport and radiation emission in carbon nanotubes.

Science.gov (United States)

Roslyak, Oleksiy; Cherqui, Charles; Dunlap, David H; Piryatinski, Andrei

2014-07-17

We report on a general theoretical approach to study exciton transport and emission in a single-walled carbon nanotube (SWNT) in the presence of a localized surface-plasmon (SP) mode within a metal nanoparticle interacting via near-field coupling. We derive a set of quantum mechanical equations of motion and approximate rate equations that account for the exciton, SP, and the environmental degrees of freedom. The material equations are complemented by an expression for the radiated power that depends on the exciton and SP populations and coherences, allowing for an examination of the angular distribution of the emitted radiation that would be measured in experiment. Numerical simulations for a (6,5) SWNT and cone-shaped Ag metal tip (MT) have been performed using this methodology. Comparison with physical parameters shows that the near-field interaction between the exciton-SP occurs in a weak coupling regime, with the diffusion processes being much faster than the exciton-SP population exchange. In such a case, the effect of the exciton population transfer to the MT with its subsequent dissipation (i.e., the Förster energy transfer) is to modify the exciton steady state distribution while reducing the equilibration time for excitons to reach a steady sate distribution. We find that the radiation distribution is dominated by SP emission for a SWNT-MT separation of a few tens of nanometers due to the fast SP emission rate, whereas the exciton-SP coherences can cause its rotation.

Transient and modulated charge separation at CuInSe{sub 2}/C{sub 60} and CuInSe{sub 2}/ZnPc hybrid interfaces

Energy Technology Data Exchange (ETDEWEB)

Morzé, Natascha von, E-mail: natascha.von_morze@helmholtz-berlin.de; Dittrich, Thomas, E-mail: dittrich@helmholtz-berlin.de; Calvet, Wolfram, E-mail: wolfram.calvet@helmholtz-berlin.de; Lauermann, Iver, E-mail: iver.lauermann@helmholtz-berlin.de; Rusu, Marin, E-mail: rusu@helmholtz-berlin.de

2017-02-28

Highlights: • Surface physical properties of non- and Na-treated CuInSe{sub 2} layers studied. • Evidence of exciton dissociation and charge separation at CuInSe{sub 2}/ZnPc interface. • Strong band bending at the CuInSe{sub 2} surface in contact with C{sub 60} observed. • No evidence for exciton dissociation at the CuInSe{sub 2}/C{sub 60} interface found. • Cu-poor phase at CuInSe{sub 2}/organic interface crucial for charge separation. - Abstract: Spectral dependent charge transfer and exciton dissociation have been investigated at hybrid interfaces between inorganic polycrystalline CuInSe{sub 2} (untreated and Na-conditioned) thin films and organic C{sub 60} as well as zinc phthalocyanine (ZnPc) layers by transient and modulated surface photovoltage measurements. The stoichiometry and electronic properties of the bare CuInSe{sub 2} surface were characterized by photoelectron spectroscopy which revealed a Cu-poor phase with n-type features. After the deposition of the C{sub 60} layer, a strong band bending at the CuInSe{sub 2} surface was observed. Evidence for dissociation of excitons followed by charge separation was found at the CuInSe{sub 2}/ZnPc interface. The Cu-poor layer at the CuInSe{sub 2} surface was found to be crucial for transient and modulated charge separation at CuInSe{sub 2}/organic hybrid interfaces.

Impact of the glass transition on exciton dynamics in polymer thin films

Science.gov (United States)

Ehrenreich, Philipp; Proepper, Daniel; Graf, Alexander; Jores, Stefan; Boris, Alexander V.; Schmidt-Mende, Lukas

2017-11-01

In the development of organic electronics, unlimited design possibilities of conjugated polymers offer a wide variety of mechanical and electronic properties. Thereby, it is crucially important to reveal universal physical characteristics that allow efficient and forward developments of new chemical compounds. In particular for organic solar cells, a deeper understanding of exciton dynamics in polymer films can help to improve the charge generation process further. For this purpose, poly(3-hexylthiophene) (P3HT) is commonly used as a model system, although exciton decay kinetics have found different interpretations. Using temperature-dependent time-resolved photoluminescence spectroscopy in combination with low-temperature spectroscopic ellipsometry, we can show that P3HT is indeed a model system in which excitons follow a simple diffusion/hopping model. Based on our results we can exclude the relevance of hot-exciton emission as well as a dynamic torsional relaxation upon photoexcitation on a ps time scale. Instead, we depict the glass transition temperature of polymers to strongly affect exciton dynamics.

Charge transfer cross sections for dysprosium and cerium

Energy Technology Data Exchange (ETDEWEB)

Adachi, Hajime; Tamura, Koji; Okazaki, Tetsuji; Shibata, Takemasa [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

1998-06-01

Symmetric resonant charge transfer cross sections between singly ionized ions and the parent atoms were measured for dysprosium and cerium in the impact energy of 200-2000eV. The cross sections were determined from the ratio between the number of ions produced by charge transfer and those in primary ion beam. The primary ion beam was produced by a laser ion source in which their atoms were ionized by laser resonant photo-ionization. The slow ions produced by charge transfer and fast primary ions were detected with Faraday cups. The obtained cross sections were (1.82{+-}0.14) x 10{sup -14} cm{sup 2} for dysprosium and (0.88{+-}0.12) x 10{sup -14} cm{sup 2} for cerium in the above energy range. The difference of these values can mostly be explained by considering the electron configurations of these atoms and ions. (author)

Charge transfer cross sections for dysprosium and cerium

International Nuclear Information System (INIS)

Adachi, Hajime; Tamura, Koji; Okazaki, Tetsuji; Shibata, Takemasa

1998-06-01

Symmetric resonant charge transfer cross sections between singly ionized ions and the parent atoms were measured for dysprosium and cerium in the impact energy of 200-2000eV. The cross sections were determined from the ratio between the number of ions produced by charge transfer and those in primary ion beam. The primary ion beam was produced by a laser ion source in which their atoms were ionized by laser resonant photo-ionization. The slow ions produced by charge transfer and fast primary ions were detected with Faraday cups. The obtained cross sections were (1.82±0.14) x 10 -14 cm 2 for dysprosium and (0.88±0.12) x 10 -14 cm 2 for cerium in the above energy range. The difference of these values can mostly be explained by considering the electron configurations of these atoms and ions. (author)

Charge Transfer and Catalysis at the Metal Support Interface

Energy Technology Data Exchange (ETDEWEB)

Baker, Lawrence Robert [Univ. of California, Berkeley, CA (United States)

2012-07-31

Kinetic, electronic, and spectroscopic characterization of model Pt–support systems are used to demonstrate the relationship between charge transfer and catalytic activity and selectivity. The results show that charge flow controls the activity and selectivity of supported metal catalysts. This dissertation builds on extensive existing knowledge of metal–support interactions in heterogeneous catalysis. The results show the prominent role of charge transfer at catalytic interfaces to determine catalytic activity and selectivity. Further, this research demonstrates the possibility of selectively driving catalytic chemistry by controlling charge flow and presents solid-state devices and doped supports as novel methods for obtaining electronic control over catalytic reaction kinetics.

Exciton correlations and input–output relations in non-equilibrium exciton superfluids

International Nuclear Information System (INIS)

Ye, Jinwu; Sun, Fadi; Yu, Yi-Xiang; Liu, Wuming

2013-01-01

The photoluminescence (PL) measurements on photons and the transport measurements on excitons are the two types of independent and complementary detection tools to search for possible exciton superfluids in electron–hole semi-conductor bilayer systems. In fact, it was believed that the transport measurements can provide more direct evidences on superfluids than the spectroscopic measurements. It is important to establish the relations between the two kinds of measurements. In this paper, using quantum Heisenberg–Langevin equations, we establish such a connection by calculating various exciton correlation functions in the putative exciton superfluids. These correlation functions include both normal and anomalous greater, lesser, advanced, retarded, and time-ordered exciton Green functions and also various two exciton correlation functions. We also evaluate the corresponding normal and anomalous spectral weights and the Keldysh distribution functions. We stress the violations of the fluctuation and dissipation theorem among these various exciton correlation functions in the non-equilibrium exciton superfluids. We also explore the input–output relations between various exciton correlation functions and those of emitted photons such as the angle resolved photon power spectrum, phase sensitive two mode squeezing spectrum and two photon correlations. Applications to possible superfluids in the exciton–polariton systems are also mentioned. For a comparison, using conventional imaginary time formalism, we also calculate all the exciton correlation functions in an equilibrium dissipative exciton superfluid in the electron–electron coupled semi-conductor bilayers at the quantum Hall regime at the total filling factor ν T =1. We stress the analogies and also important differences between the correlations functions in the two exciton superfluid systems. - Highlights: ► Establish the relations between photoluminescence and transport measurements. ► Stress the

Charge-transfer modified embedded atom method dynamic charge potential for Li-Co-O system.

Science.gov (United States)

Kong, Fantai; Longo, Roberto C; Liang, Chaoping; Nie, Yifan; Zheng, Yongping; Zhang, Chenxi; Cho, Kyeongjae

2017-11-29

To overcome the limitation of conventional fixed charge potential methods for the study of Li-ion battery cathode materials, a dynamic charge potential method, charge-transfer modified embedded atom method (CT-MEAM), has been developed and applied to the Li-Co-O ternary system. The accuracy of the potential has been tested and validated by reproducing a variety of structural and electrochemical properties of LiCoO 2 . A detailed analysis on the local charge distribution confirmed the capability of this potential for dynamic charge modeling. The transferability of the potential is also demonstrated by its reliability in describing Li-rich Li 2 CoO 2 and Li-deficient LiCo 2 O 4 compounds, including their phase stability, equilibrium volume, charge states and cathode voltages. These results demonstrate that the CT-MEAM dynamic charge potential could help to overcome the challenge of modeling complex ternary transition metal oxides. This work can promote molecular dynamics studies of Li ion cathode materials and other important transition metal oxides systems that involve complex electrochemical and catalytic reactions.

Charge separation and transfer in hybrid type II tunneling structures of CdTe and CdSe nanocrystals

Energy Technology Data Exchange (ETDEWEB)

Gross, Dieter Konrad Michael

2013-11-08

-quenching vanishes when this offset approaches 0.0 eV. The fact that PL-quenching and its correlation with the energetic offset was observed for both clustered and layered assembly provides a strong indirect indication of charge separation via electron transfer from CdTe to CdSe nanocrystals. The main result of this thesis is the direct proof of the charge separation on the type II interface of CdTe and CdSe nanocrystal layers. SPV-measurements as a direct measurement methode showed clearly the directionality of charge separation since the SPV measures the electric field of the separated charges. Electrons are collected on CdSe nanocrystal layers, holes on CdTe nanocrystal layers. A change in the order between CdSe and CdTe therefore leads to a change in the sign of the SPV-signal. Both SPVspectra and time-resolved SPV-measurements support this finding and showed that the charge selectivity of the CdTe-CdSe interface is unidirectional for the whole excitation spectrum and the entire investigated time range. This indicates that the directionality of the CdTe-CdSe interface is the only dominant charge separation mechanism that was observed. Hence, the type II alignment of the self-assembled nanocrystals used was clearly proven. Introducing an additional barrier between the nanocrystal layers doubled the barrier width so that the SPV-signal is quenched. This is consistent with tunneling transfer which is exponentially dependent on barrier width. Moreover, we learned that both absorption in CdTe and CdSe nanocrystals and the sample thickness contribute to the SPV-signal. Thus, we could observe electron diffusion in CdSe multilayers which was faster than the charge carrier diffusion dynamics in CdTe nanocrystal multilayers. Future research may address the combination of energy transfer dynamics with the charge separation processes presented in this thesis. On the one hand, this may provide a better understanding of their fundamental processes and differentiate between excitonic FRET and

Charge separation and transfer in hybrid type II tunneling structures of CdTe and CdSe nanocrystals

International Nuclear Information System (INIS)

Gross, Dieter Konrad Michael

2013-01-01

-quenching vanishes when this offset approaches 0.0 eV. The fact that PL-quenching and its correlation with the energetic offset was observed for both clustered and layered assembly provides a strong indirect indication of charge separation via electron transfer from CdTe to CdSe nanocrystals. The main result of this thesis is the direct proof of the charge separation on the type II interface of CdTe and CdSe nanocrystal layers. SPV-measurements as a direct measurement methode showed clearly the directionality of charge separation since the SPV measures the electric field of the separated charges. Electrons are collected on CdSe nanocrystal layers, holes on CdTe nanocrystal layers. A change in the order between CdSe and CdTe therefore leads to a change in the sign of the SPV-signal. Both SPVspectra and time-resolved SPV-measurements support this finding and showed that the charge selectivity of the CdTe-CdSe interface is unidirectional for the whole excitation spectrum and the entire investigated time range. This indicates that the directionality of the CdTe-CdSe interface is the only dominant charge separation mechanism that was observed. Hence, the type II alignment of the self-assembled nanocrystals used was clearly proven. Introducing an additional barrier between the nanocrystal layers doubled the barrier width so that the SPV-signal is quenched. This is consistent with tunneling transfer which is exponentially dependent on barrier width. Moreover, we learned that both absorption in CdTe and CdSe nanocrystals and the sample thickness contribute to the SPV-signal. Thus, we could observe electron diffusion in CdSe multilayers which was faster than the charge carrier diffusion dynamics in CdTe nanocrystal multilayers. Future research may address the combination of energy transfer dynamics with the charge separation processes presented in this thesis. On the one hand, this may provide a better understanding of their fundamental processes and differentiate between excitonic FRET and

Voltammetry for the charge transfer at two immiscible electrolyte solutions interface

International Nuclear Information System (INIS)

Kihara, S.; Suzuki, M.; Maeda, K.; Ogura, K.; Matsui, M.; Yoshida, Z.

1989-01-01

The voltammetry for the charge transfer (VCT) at the interface of immicible solutions is a very powerful method for understanding the dynamic features of the charge transfer because of its unmatched advantage that the transfer energy and the number of charges transferred can be measured simultaneously and in situ. In the present paper, several novel systems for electron transfer are outlined, and the following topics are discussed based on results obtained by the current scan polarography at the solution dropping electrode developed as a technique for VCT: the relation between the half-wave potential in VCT for ion transfer and the characteristics of the ion transferred; the relation between the half-wave potential in VCT for electron transfer and the electrochemical nature of a redox couple added in water and that added in organic solution; and the ion transfer through a liquid membrane promoted by electron transfer. Observations are presented and discussion is made on the characteristics of ion transfer polarograms, those of electron transfer polarograms, and ion transfer promoted by electron transfer at a liquid/membrane interface. (N.K.)

Charge-transfer spectra of tetravalent lanthanide ions in oxides

NARCIS (Netherlands)

Hoefdraad, H.E.

The charge-transfer spectra of Ce4+, Pr4+ and Tb4+ in a number of oxides are reported. It is noted that the position of the first charge-transfer band is fixed for the metal ion in an oxygen coordination of VI, but varies in VIII coordination as a function of the host lattice. It is argued that this

Metal nanoparticle mediated space charge and its optical control in an organic hole-only device

Energy Technology Data Exchange (ETDEWEB)

Ligorio, G.; Nardi, M. V. [Institut für Physik & IRIS Adlershof, Humboldt-Universität zu Berlin, Brook-Taylor Str. 6, 12489 Berlin (Germany); Steyrleuthner, R.; Neher, D. [Institute of Physics and Astronomy, Universität Potsdam, Karl-Liebknecht Str. 24, 14476 Potsdam (Germany); Ihiawakrim, D. [Institut de Physique et de Chimie des Matériaux de Strasbourg, Université de Strasbourg, CNRS UMR 7504, 23 rue du Loess, BP 43, 67034 Strasbourg, Cedex2 (France); Crespo-Monteiro, N.; Brinkmann, M. [Institut Charles Sadron CNRS, 23 rue du Loess, 67034 Strasbourg (France); Koch, N., E-mail: norbert.koch@physik.hu-berlin.de [Institut für Physik & IRIS Adlershof, Humboldt-Universität zu Berlin, Brook-Taylor Str. 6, 12489 Berlin (Germany); Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Erneuerbare Energien, Albert-Einstein Str. 15, 12489 Berlin (Germany)

2016-04-11

We reveal the role of localized space charges in hole-only devices based on an organic semiconductor with embedded metal nanoparticles (MNPs). MNPs act as deep traps for holes and reduce the current density compared to a device without MNPs by a factor of 10{sup 4} due to the build-up of localized space charge. Dynamic MNPs charged neutrality can be realized during operation by electron transfer from excitons created in the organic matrix, enabling light sensing independent of device bias. In contrast to the previous speculations, electrical bistability in such devices was not observed.

Theoretical rationalization of the singlet-triplet gap in OLEDs materials: impact of charge-transfer character.

Science.gov (United States)

Moral, M; Muccioli, L; Son, W-J; Olivier, Y; Sancho-García, J C

2015-01-13

New materials for OLED applications with low singlet-triplet energy splitting have been recently synthesized in order to allow for the conversion of triplet into singlet excitons (emitting light) via a Thermally Activated Delayed Fluorescence (TADF) process, which involves excited-states with a non-negligible amount of Charge-Transfer (CT). The accurate modeling of these states with Time-Dependent Density Functional Theory (TD-DFT), the most used method so far because of the favorable trade-off between accuracy and computational cost, is however particularly challenging. We carefully address this issue here by considering materials with small (high) singlet-triplet gap acting as emitter (host) in OLEDs and by comparing the accuracy of TD-DFT and the corresponding Tamm-Dancoff Approximation (TDA), which is found to greatly reduce error bars with respect to experiments thanks to better estimates for the lowest singlet-triplet transition. Finally, we quantitatively correlate the singlet-triplet splitting values with the extent of CT, using for it a simple metric extracted from calculations with double-hybrid functionals, that might be applied in further molecular engineering studies.

Absence of Intramolecular Singlet Fission in Pentacene-Perylenediimide Heterodimers: The Role of Charge Transfer State.

Science.gov (United States)

Wang, Long; Wu, Yishi; Chen, Jianwei; Wang, Lanfen; Liu, Yanping; Yu, Zhenyi; Yao, Jiannian; Fu, Hongbing

2017-11-16

A new class of donor-acceptor heterodimers based on two singlet fission (SF)-active chromophores, i.e., pentacene (Pc) and perylenediimide (PDI), was developed to investigate the role of charge transfer (CT) state on the excitonic dynamics. The CT state is efficiently generated upon photoexcitation. However, the resulting CT state decays to different energy states depending on the energy levels of the CT state. It undergoes extremely rapid deactivation to the ground state in polar CH 2 Cl 2 , whereas it undergoes transformation to a Pc triplet in nonpolar toluene. The efficient triplet generation in toluene is not due to SF but CT-mediated intersystem crossing. In light of the energy landscape, it is suggested that the deep energy level of the CT state relative to that of the triplet pair state makes the CT state actually serve as a trap state that cannot undergoes an intramolecular singlet fission process. These results provide guidance for the design of SF materials and highlight the requisite for more widely applicable design principles.

The Roles of Structural Order and Intermolecular Interactions in Determining Ionization Energies and Charge-Transfer State Energies in Organic Semiconductors

KAUST Repository

Graham, Kenneth

2016-08-17

The energy landscape in organic semiconducting materials greatly influences charge and exciton behavior, which are both critical to the operation of organic electronic devices. These energy landscapes can change dramatically depending on the phases of material present, including pure phases of one molecule or polymer and mixed phases exhibiting different degrees of order and composition. In this work, ultraviolet photoelectron spectroscopy measurements of ionization energies (IEs) and external quantum efficiency measurements of charge-transfer (CT) state energies (ECT) are applied to molecular photovoltaic material systems to characterize energy landscapes. The results show that IEs and ECT values are highly dependent on structural order and phase composition. In the sexithiophene:C60 system both the IEs of sexithiophene and C60 shift by over 0.4 eV while ECT shifts by 0.5 eV depending on molecular composition. By contrast, in the rubrene:C60 system the IE of rubrene and C60 vary by ≤0.11 eV and ECT varies by ≤0.04 eV as the material composition varies. These results suggest that energy landscapes can exist whereby the binding energies of the CT states are overcome by energy offsets between charges in CT states in mixed regions and free charges in pure phases. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Superposition Principle in Auger Recombination of Charged and Neutral Multicarrier States in Semiconductor Quantum Dots.

Science.gov (United States)

Wu, Kaifeng; Lim, Jaehoon; Klimov, Victor I

2017-08-22

Application of colloidal semiconductor quantum dots (QDs) in optical and optoelectronic devices is often complicated by unintentional generation of extra charges, which opens fast nonradiative Auger recombination pathways whereby the recombination energy of an exciton is quickly transferred to the extra carrier(s) and ultimately dissipated as heat. Previous studies of Auger recombination have primarily focused on neutral and, more recently, negatively charged multicarrier states. Auger dynamics of positively charged species remains more poorly explored due to difficulties in creating, stabilizing, and detecting excess holes in the QDs. Here we apply photochemical doping to prepare both negatively and positively charged CdSe/CdS QDs with two distinct core/shell interfacial profiles ("sharp" versus "smooth"). Using neutral and charged QD samples we evaluate Auger lifetimes of biexcitons, negative and positive trions (an exciton with an extra electron or a hole, respectively), and multiply negatively charged excitons. Using these measurements, we demonstrate that Auger decay of both neutral and charged multicarrier states can be presented as a superposition of independent elementary three-particle Auger events. As one of the manifestations of the superposition principle, we observe that the biexciton Auger decay rate can be presented as a sum of the Auger rates for independent negative and positive trion pathways. By comparing the measurements on the QDs with the "sharp" versus "smooth" interfaces, we also find that while affecting the absolute values of Auger lifetimes, manipulation of the shape of the confinement potential does not lead to violation of the superposition principle, which still allows us to accurately predict the biexciton Auger lifetimes based on the measured negative and positive trion dynamics. These findings indicate considerable robustness of the superposition principle as applied to Auger decay of charged and neutral multicarrier states

Selectively Modulating Triplet Exciton Formation in Host Materials for Highly Efficient Blue Electrophosphorescence.

Science.gov (United States)

Li, Huanhuan; Bi, Ran; Chen, Ting; Yuan, Kai; Chen, Runfeng; Tao, Ye; Zhang, Hongmei; Zheng, Chao; Huang, Wei

2016-03-23

The concept of limiting the triplet exciton formation to fundamentally alleviate triplet-involved quenching effects is introduced to construct host materials for highly efficient and stable blue phosphorescent organic light-emitting diodes (PhOLEDs). The low triplet exciton formation is realized by small triplet exciton formation fraction and rate with high binding energy and high reorganization energy of triplet exciton. Demonstrated in two analogue molecules in conventional donor-acceptor molecule structure for bipolar charge injection and transport with nearly the same frontier orbital energy levels and triplet excited energies, the new concept host material shows significantly suppressed triplet exciton formation in the host to avoid quenching effects, leading to much improved device efficiencies and stabilities. The low-voltage-driving blue PhOLED devices exhibit maximum efficiencies of 43.7 cd A(-1) for current efficiency, 32.7 lm W(-1) for power efficiency, and 20.7% for external quantum efficiency with low roll-off and remarkable relative quenching effect reduction ratio up to 41%. Our fundamental solution for preventing quenching effects of long-lived triplet excitons provides exciting opportunities for fabricating high-performance devices using the advanced host materials with intrinsically small triplet exciton formation cross section.

Charge transfer induced activity of graphene for oxygen reduction

International Nuclear Information System (INIS)

Shen, Anli; Xia, Weijun; Dou, Shuo; Wang, Shuangyin; Zhang, Lipeng; Xia, Zhenhai

2016-01-01

Tetracyanoethylene (TCNE), with its strong electron-accepting ability, was used to dope graphene as a metal-free electrocatalyst for the oxygen reduction reaction (ORR). The charge transfer process was observed from graphene to TCNE by x-ray photoelectron spectroscopy and Raman characterizations. Our density functional theory calculations found that the charge transfer behavior led to an enhancement of the electrocatalytic activity for the ORR. (paper)

Two exciton states in discrete and continuum alpha-helical proteins

International Nuclear Information System (INIS)

Latha, M.M.; Merlin, G.

2012-01-01

The dynamics of alpha-helical proteins is described by proposing a model Hamiltonian representing two exciton bound states. The dynamics is studied by constructing the equations of motion using a two exciton eigen-function in the discrete level. A numerical analysis shows the existence of two excitons in alpha-helical proteins and its propagation as solitons along the hydrogen bonding spines. The lattice model is also treated in the continuum limit which is a valid approximation in the low temperature, long wavelength limit. The resulting equation is studied using the multiple scale perturbation analysis which also shows the transfer of two exciton energy through alpha-helical proteins in the form of solitons with no change in velocity and amplitude. -- Highlights: ► The dynamics of alpha-helical proteins with two exciton states is studied. ► The dynamics is studied both in the discrete and continuum levels. ► The resulting equations are solved numerically and analytically. ► The solution supports the propagation of the energy in the form of solitons.

Plasmonic Structure Enhanced Exciton Generation at the Interface between the Perovskite Absorber and Copper Nanoparticles

Science.gov (United States)

Lin, Kuen-Feng; Chiang, Chien-Hung; Wu, Chun-Guey

2014-01-01

The refractive index and extinction coefficient of a triiodide perovskite absorber (TPA) were obtained by fitting the transmittance spectra of TPA/PEDOT:PSS/ITO/glass using the transfer matrix method. Cu nanoplasmonic structures were designed to enhance the exciton generation in the TPA and to simultaneously reduce the film thickness of the TPA. Excitons were effectively generated at the interface between TPA and Cu nanoparticles, as observed through the 3D finite-difference time-domain method. The exciton distribution is advantageous for the exciton dissociation and carrier transport. PMID:25295290

Does charge transfer correlate with ignition probability?

International Nuclear Information System (INIS)

Holdstock, Paul

2008-01-01

Flammable or explosive atmospheres exist in many industrial environments. The risk of ignition caused by electrostatic discharges is very real and there has been extensive study of the incendiary nature of sparks and brush discharges. It is clear that in order to ignite a gas, an amount of energy needs to be delivered to a certain volume of gas within a comparatively short time. It is difficult to measure the energy released in an electrostatic discharge directly, but it is possible to approximate the energy in a spark generated from a well defined electrical circuit. The spark energy required to ignite a gas, vapour or dust cloud can be determined by passing such sparks through them. There is a relationship between energy and charge in a capacitive circuit and so it is possible to predict whether or not a spark discharge will cause an ignition by measuring the charge transferred in the spark. Brush discharges are in many ways less well defined than sparks. Nevertheless, some work has been done that has established a relationship between charge transferred in brush discharges and the probability of igniting a flammable atmosphere. The question posed by this paper concerns whether such a relationship holds true in all circumstances and if there is a universal correlation between charge transfer and ignition probability. Data is presented on discharges from textile materials that go some way to answering this question.

Enhancing SERS by Means of Supramolecular Charge Transfer

Science.gov (United States)

Wong, Eric; Flood, Amar; Morales, Alfredo

2009-01-01

In a proposed method of sensing small quantities of molecules of interest, surface enhanced Raman scattering (SERS) spectroscopy would be further enhanced by means of intermolecular or supramolecular charge transfer. There is a very large potential market for sensors based on this method for rapid detection of chemical and biological hazards. In SERS, the Raman signals (vibrational spectra) of target molecules become enhanced by factors of the order of 108 when those molecules are in the vicinities of nanostructured substrate surfaces that have been engineered to have plasmon resonances that enhance local electric fields. SERS, as reported in several prior NASA Tech Briefs articles and elsewhere, has remained a research tool and has not yet been developed into a practical technique for sensing of target molecules: this is because the short range (5 to 20 nm) of the field enhancement necessitates engineering of receptor molecules to attract target molecules to the nanostructured substrate surfaces and to enable reliable identification of the target molecules in the presence of interferants. Intermolecular charge-transfer complexes have been used in fluorescence-, photoluminescence-, and electrochemistry-based techniques for sensing target molecules, but, until now, have not been considered for use in SERS-based sensing. The basic idea of the proposed method is to engineer receptor molecules that would be attached to nanostructured SERS substrates and that would interact with the target molecules to form receptor-target supramolecular charge-transfer complexes wherein the charge transfer could be photoexcited.

Integer Charge Transfer and Hybridization at an Organic Semiconductor/Conductive Oxide Interface

KAUST Repository

Gruenewald, Marco; Schirra, Laura K.; Winget, Paul; Kozlik, Michael; Ndione, Paul F.; Sigdel, Ajaya K.; Berry, Joseph J.; Forker, Roman; Bredas, Jean-Luc; Fritz, Torsten; Monti, Oliver L. A.

2015-01-01

with localized states (the shallow donors) in the substrate and charge back-donation, resulting in an effectively integer charge transfer across the interface. Charge transfer is thus not merely a question of locating the Fermi level above the PTCDA electron

Charge transfer devices and their application in physics

Energy Technology Data Exchange (ETDEWEB)

Soroko, L M [Joint Inst. for Nuclear Research, Dubna (USSR)

1979-01-01

Physical properties and technical specifications of charge transfer devices (CTD) are reviewed. The CTD are semiconductor devices based on silicon single crystals. The limiting charge density of the CTD, their efficiency of charge transfer, the background noise and radiation effects are considered. Fast response and low energy consumption are characteristic features of the devices. The application of the CTD in storage devices, real time spectral data processing systems and in streamer chambers is described. The algorithms of topological transformations in the stage of scanning particle track images, which can be realized with the help of the CTD are shortly considered. It is pointed out that applications of the CTD in different fields of science and technology are numerous and expanding.

Exciton localization-delocalization transition in an extended dendrimer

Energy Technology Data Exchange (ETDEWEB)

Pouthier, Vincent, E-mail: vincent.pouthier@univ-fcomte.fr [Institut UTINAM, Université de Franche-Comté, CNRS UMR 6213, 25030 Besançon Cedex (France)

2013-12-21

Exciton-mediated quantum state transfer between the periphery and the core of an extended dendrimer is investigated numerically. By mapping the dynamics onto that of a linear chain, it is shown that a localization-delocalization transition arises for a critical value of the generation number G{sub c} ≈ 5. This transition originates in the quantum interferences experienced by the excitonic wave due to the multiple scatterings that arise each time the wave tunnels from one generation to another. These results suggest that only small-size dendrimers could be used for designing an efficient quantum communication protocol.

Exciton localization-delocalization transition in an extended dendrimer

International Nuclear Information System (INIS)

Pouthier, Vincent

2013-01-01

Exciton-mediated quantum state transfer between the periphery and the core of an extended dendrimer is investigated numerically. By mapping the dynamics onto that of a linear chain, it is shown that a localization-delocalization transition arises for a critical value of the generation number G c ≈ 5. This transition originates in the quantum interferences experienced by the excitonic wave due to the multiple scatterings that arise each time the wave tunnels from one generation to another. These results suggest that only small-size dendrimers could be used for designing an efficient quantum communication protocol

Theoretical study of excitonic complexes in semiconductors quantum wells; Estudo teorico de complexos excitonicos em pocos quanticos de semicondutores

Energy Technology Data Exchange (ETDEWEB)

Dacal, Luis Carlos Ogando

2001-08-01

A physical system where indistinguishable particles interact with each other creates the possibility of studying correlation and exchange effect. The simplest system is that one with only two indistinguishable particles. In condensed matter physics, these complexes are represented by charged excitons, donors and acceptors. In quantum wells, the valence band is not parabolic, therefore, the negatively charged excitons and donors are theoretically described in a simpler way. Despite the fact that the stability of charged excitons (trions) is known since the late 50s, the first experimental observation occurred only at the early 90s in quantum well samples, where their binding energies are one order of magnitude larger due to the one dimensional carriers confinement. After this, these complexes became the subject of an intense research because the intrinsic screening of electrical interactions in semiconductor materials allows that magnetic fields that are usual in laboratories have strong effects on the trion binding energy. Another rich possibility is the study of trions as an intermediate state between the neutral exciton and the Fermi edge singularity when the excess of doping carriers is increased. In this thesis, we present a theoretical study of charged excitons and negatively charged donors in GaAs/Al{sub 0.3}Ga{sub 0.7}As quantum wells considering the effects of external electric and magnetic fields. We use a simple, accurate and physically clear method to describe these systems in contrast with the few and complex treatments s available in the literature. Our results show that the QW interface defects have an important role in the trion dynamics. This is in agreement with some experimental works, but it disagrees with other ones. (author)

Identification of excitons, trions and biexcitons in single-layer WS{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Plechinger, Gerd; Nagler, Philipp; Kraus, Julia; Paradiso, Nicola; Strunk, Christoph; Schueller, Christian; Korn, Tobias [Institut fuer Experimentelle und Angewandte Physik, Universitaet Regensburg, 93040, Regensburg (Germany)

2015-08-15

Single-layer WS{sub 2} is a direct-gap semiconductor showing strong excitonic photoluminescence features in the visible spectral range. Here, we present temperature-dependent photoluminescence measurements on mechanically exfoliated single-layer WS{sub 2}, revealing the existence of neutral and charged excitons at low temperatures as well as at room temperature. By applying a gate voltage, we can electrically control the ratio of excitons and trions and assert a residual n-type doping of our samples. At high excitation densities and low temperatures, an additional peak at energies below the trion dominates the photoluminescence, which we identify as biexciton emission. (copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Proton transfer to charged platinum electrodes. A molecular dynamics trajectory study.

Science.gov (United States)

Wilhelm, Florian; Schmickler, Wolfgang; Spohr, Eckhard

2010-05-05

A recently developed empirical valence bond (EVB) model for proton transfer on Pt(111) electrodes (Wilhelm et al 2008 J. Phys. Chem. C 112 10814) has been applied in molecular dynamics (MD) simulations of a water film in contact with a charged Pt surface. A total of seven negative surface charge densities σ between -7.5 and -18.9 µC cm(-2) were investigated. For each value of σ, between 30 and 84 initial conditions of a solvated proton within a water slab were sampled, and the trajectories were integrated until discharge of a proton occurred on the charged surfaces. We have calculated the mean rates for discharge and for adsorption of solvated protons within the adsorbed water layer in contact with the metal electrode as a function of surface charge density. For the less negative values of σ we observe a Tafel-like exponential increase of discharge rate with decreasing σ. At the more negative values this exponential increase levels off and the discharge process is apparently transport limited. Mechanistically, the Tafel regime corresponds to a stepwise proton transfer: first, a proton is transferred from the bulk into the contact water layer, which is followed by transfer of a proton to the charged surface and concomitant discharge. At the more negative surface charge densities the proton transfer into the contact water layer and the transfer of another proton to the surface and its discharge occur almost simultaneously.

Protein-induced geometric constraints and charge transfer in bacteriochlorophyll-histidine complexes in LH2.

Science.gov (United States)

Wawrzyniak, Piotr K; Alia, A; Schaap, Roland G; Heemskerk, Mattijs M; de Groot, Huub J M; Buda, Francesco

2008-12-14

Bacteriochlorophyll-histidine complexes are ubiquitous in nature and are essential structural motifs supporting the conversion of solar energy into chemically useful compounds in a wide range of photosynthesis processes. A systematic density functional theory study of the NMR chemical shifts for histidine and for bacteriochlorophyll-a-histidine complexes in the light-harvesting complex II (LH2) is performed using the BLYP functional in combination with the 6-311++G(d,p) basis set. The computed chemical shift patterns are consistent with available experimental data for positive and neutral(tau) (N(tau) protonated) crystalline histidines. The results for the bacteriochlorophyll-a-histidine complexes in LH2 provide evidence that the protein environment is stabilizing the histidine close to the Mg ion, thereby inducing a large charge transfer of approximately 0.5 electronic equivalent. Due to this protein-induced geometric constraint, the Mg-coordinated histidine in LH2 appears to be in a frustrated state very different from the formal neutral(pi) (N(pi) protonated) form. This finding could be important for the understanding of basic functional mechanisms involved in tuning the electronic properties and exciton coupling in LH2.

Complexes with charge transfer and ion-radical salts in catalysis

Energy Technology Data Exchange (ETDEWEB)

Krylov, O V [AN SSSR, Moscow. Inst. Khimicheskoj Fiziki

1978-01-01

Considered are the data experimentally proving formation of complexes with charge transfer as intermediate complexes in homogeneous and heterogeneous catalysis. Catalytic activity correlations with charge transfer energy (and in heterogeneous catalysis with width of semiconductor forbidden band can be useful while selection of catalysts (MoO/sub 3//MgO; V/sub 2/O/sub 5//MgO; MoO/sub 3//Al/sub 2/O/sub 3/; V/sub 2/O/sub 5//Al/sub 2/O/sub 3/). A review of papers on catalytic activity of the previously prepared complexes with charge transfer and ion-radical salts is given. The use of alkali metal complexes with aromatic compounds showed their high activity in hydrogenation reactions and proved principle possibility of activation of hydrogen and hydrocarbons by the systems which do not contain transfer metals.

Characterisation of a CMOS charge transfer device for TDI imaging

International Nuclear Information System (INIS)

Rushton, J.; Holland, A.; Stefanov, K.; Mayer, F.

2015-01-01

The performance of a prototype true charge transfer imaging sensor in CMOS is investigated. The finished device is destined for use in TDI applications, especially Earth-observation, and to this end radiation tolerance must be investigated. Before this, complete characterisation is required. This work starts by looking at charge transfer inefficiency and then investigates responsivity using mean-variance techniques

Vacuum ultraviolet synchrotron measurements of excitons in NaMgF{sub 3}:Yb{sup 2+}

Energy Technology Data Exchange (ETDEWEB)

Hughes-Currie, Rosa B. [Department of Physics and Astronomy, University of Canterbury, PB 4800, Christchurch 8140 (New Zealand); Ivanovskikh, Konstantin V. [ANK Service Ltd., PB 58, Novouralsk 624131, Sverdlovsk Region (Russian Federation); Ural Federal University, 19 Mira st., Ekaterinburg 620002 (Russian Federation); Reid, Michael F., E-mail: mike.reid@canterbury.ac.nz [Department of Physics and Astronomy, University of Canterbury, PB 4800, Christchurch 8140 (New Zealand); MacDiarmid Institute for Advanced Materials and Nanotechnology (New Zealand); Wells, Jon-Paul R. [Department of Physics and Astronomy, University of Canterbury, PB 4800, Christchurch 8140 (New Zealand); Dodd-Walls Centre for Quantum and Photonic Technologies (New Zealand); Reeves, Roger J. [Department of Physics and Astronomy, University of Canterbury, PB 4800, Christchurch 8140 (New Zealand); MacDiarmid Institute for Advanced Materials and Nanotechnology (New Zealand); Meijerink, Andries [Debye Institute, Utrecht University, P.O. Box 80 000, 3508 TA Utrecht (Netherlands)

2016-01-15

Results of a vacuum ultraviolet spectroscopic characterization of NaMgF{sub 3}:Yb{sup 2+} are presented. The material demonstrates emission features associated with self-trapped excitons and impurity-trapped excitons. The emission features noticeably overlap giving rise to a broad emission band from 17 000 to 35 000 cm{sup −1} at a sample temperature of 8 K. To identify the true profiles of the emission features we have used a deconvolution procedure. The deconvolution was possible due to the thermal quenching of self-trapped excitons at room temperature that allowed for direct observations of the impurity trapped exciton emission band. Energy transfer between host electronic excitations (excitons and e–h pairs) and Yb{sup 2+} ions leading to the formation of impurity-trapped excitons is evident from excitation spectra. - Highlights: • We present VUV emission and excitation spectra of NaMgF{sub 3}:Yb{sup 2+}. • Formation of free excitons leads to emission from intrinsic and extrinsic excitons. • We deconvolute the emission to separate the two overlapping exciton bands. • The excitation spectra show two mechanisms for forming impurity-trapped excitons.

Tailoring Quantum Dot Assemblies to Extend Exciton Coherence Times and Improve Exciton Transport

Science.gov (United States)

Seward, Kenton; Lin, Zhibin; Lusk, Mark

2012-02-01

The motion of excitons through nanostructured assemblies plays a central role in a wide range of physical phenomena including quantum computing, molecular electronics, photosynthetic processes, excitonic transistors and light emitting diodes. All of these technologies are severely handicapped, though, by quasi-particle lifetimes on the order of a nanosecond. The movement of excitons must therefore be as efficient as possible in order to move excitons meaningful distances. This is problematic for assemblies of small Si quantum dots (QDs), where excitons quickly localize and entangle with dot phonon modes. Ensuing exciton transport is then characterized by a classical random walk reduced to very short distances because of efficient recombination. We use a combination of master equation (Haken-Strobl) formalism and density functional theory to estimate the rate of decoherence in Si QD assemblies and its impact on exciton mobility. Exciton-phonon coupling and Coulomb interactions are calculated as a function of dot size, spacing and termination to minimize the rate of intra-dot phonon entanglement. This extends the time over which more efficient exciton transport, characterized by partial coherence, can be maintained.

The interplay between excitons and trions in a monolayer of MoSe2

Science.gov (United States)

Lundt, N.; Cherotchenko, E.; Iff, O.; Fan, X.; Shen, Y.; Bigenwald, P.; Kavokin, A. V.; Höfling, S.; Schneider, C.

2018-01-01

The luminescence and absorption properties of transition metal dichalcogenide monolayers are widely determined by neutral and charged excitonic complexes. Here, we focus on the impact of a free carrier reservoir on the optical properties of excitonic and trionic complexes in a MoSe2 monolayer at cryogenic temperatures. By applying photodoping via a non-resonant pump laser, the electron density can be controlled in our sample, which is directly reflected in the contribution of excitons and trions to the luminescence signal. We find significant shifts of both the exciton and trion energies in the presence of an induced electron gas both in power- and in time evolution (on the second to minute scale) in our photoluminescence spectra. In particular, in the presence of the photo-doped carrier reservoir, we observe that the splitting between excitons and trions can be enhanced by up to 4 meV. This behaviour is phenomenologically explained by an interplay between an increased screening of excitons via electrons in our system and a modification of the Fermi level. We introduce a simple but still quantitative treatment of these effects within a variational approach that takes into account both screening and phase space filling effects.

Plasmonic, excitonic and exciton-plasmonic photoinduced nanocomposites

Science.gov (United States)

Bityurin, N.; Ermolaev, N.; Smirnov, A. A.; Afanasiev, A.; Agareva, N.; Koryukina, T.; Bredikhin, V.; Kamensky, V.; Pikulin, A.; Sapogova, N.

2016-03-01

UV irradiation of materials consisting of a polymer matrix that possesses precursors of different kinds can result in creation of nanoparticles within the irradiated domains. Such photoinduced nanocomposites are promising for photonic applications due to the strong alteration of their optical properties compared to initial non-irradiated materials. We report our results on the synthesis and investigation of plasmonic, excitonic and exciton-plasmonic photoinduced nanocomposites. Plasmonic nanocomposites contain metal nanoparticles of noble metals with a pronounced plasmon resonance. Excitonic nanocomposites possess semiconductor nanoclusters (quantum dots). We consider the CdS-Au pair because the luminescent band of CdS nanoparticles enters the plasmon resonance band of gold nanoparticles. The obtaining of such particles within the same composite materials is promising for the creation of media with exciton-plasmon resonance. We demonstrate that it is possible to choose appropriate precursor species to obtain the initially transparent poly(methyl methacrylate) (PMMA) films containing both types of these molecules either separately or together. Proper irradiation of these materials by a light-emitting diode operating at the wavelength of 365 nm provides material alteration demonstrating light-induced optical absorption and photoluminescent properties typical for the corresponding nanoparticles. Thus, an exciton-plasmonic photoinduced nanocomposite is obtained. It is important that here we use the precursors that are different from those usually employed.

A new technique for the study of charge transfer in multiply charged ion-ion collisions

International Nuclear Information System (INIS)

Shinpaugh, J.L.; Meyer, F.W.; Datz, S.

1994-01-01

While large cross sections (>10 -16 cm 2 ) have been predicted for resonant charge transfer in ion-ion collisions, no experimental data exist for multiply charged systems. A novel technique is being developed at the ORNL ECR facility to allow study of symmetric charge exchange in multiply charged ion-ion collisions using a single ion source. Specific intra-beam charge transfer collisions occurring in a well-defined interaction region labeled by negative high voltage are identified and analyzed by electrostatic analysis in combination with ion time-of-flight coincidence detection of the collision products. Center-of-mass collision energies from 400 to 1000 eV are obtained by varying source and labeling-cell voltages. In addition, by the introduction of a target gas into the high-voltage cell, this labeling-voltage method allows measurement of electron-capture and -loss cross sections for ion-atom collisions. Consequently, higher collision energies can be investigated without the requirement of placing the ECR source on a high-voltage platform

Charge generation in organic solar cell materials studied by terahertz spectroscopy

KAUST Repository

Scarongella, M.

2015-09-09

We have investigated the photophysics in neat films of conjugated polymer PBDTTPD and its blend with PCBM using terahertz time-domain spectroscopy. This material has very high efficiency when used in organic solar cells. We were able to identify a THz signature for bound excitons in neat PBDTTPD films, pointing to important delocalization in those excitons. Then, we investigated the nature and local mobility (orders of magnitude higher than bulk mobility) of charges in the PBDTTPPD:PCBM blend as a function of excitation wavelength, fluence and pump-probe time delay. At low pump fluence (no bimolecular recombination phenomena), we were able to observe prompt and delayed charge generation components, the latter originating from excitons created in neat polymer domains which, thanks to delocalization, could reach the PCBM interface and dissociate to charges on a time scale of 1 ps. The nature of the photogenerated charges did not change between 0.5 ps and 800 ps after photo-excitation, which indicated that the excitons split directly into relatively free charges on an ultrafast time scale. © (2015) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE). Downloading of the abstract is permitted for personal use only.

Theoretical treatment of charge transfer processes of relevance to astrophysics

Energy Technology Data Exchange (ETDEWEB)

Krstic, P.S.; Stancil, P.C.; Schultz, D.R.

1997-12-01

Charge transfer is an important process in many astrophysical and atmospheric environments. While numerous experimental and theoretical studies exist for H and He targets, data on other targets, particularly metals and molecules, are sparse. Using a variety of theoretical methods and computational techniques the authors are developing methods to estimate the cross sections for electron capture (charge transfer) in slow collisions of low charge state ions with heavy (Mg, Ca, Fe, Co, Ni and Zn) neutrals. In this ongoing work particular attention is paid to ascertaining the importance of double electron capture.

Theoretical treatment of charge transfer processes of relevance to astrophysics

International Nuclear Information System (INIS)

Krstic, P.S.; Stancil, P.C.; Schultz, D.R.

1997-12-01

Charge transfer is an important process in many astrophysical and atmospheric environments. While numerous experimental and theoretical studies exist for H and He targets, data on other targets, particularly metals and molecules, are sparse. Using a variety of theoretical methods and computational techniques the authors are developing methods to estimate the cross sections for electron capture (charge transfer) in slow collisions of low charge state ions with heavy (Mg, Ca, Fe, Co, Ni and Zn) neutrals. In this ongoing work particular attention is paid to ascertaining the importance of double electron capture

A study of polaritonic transparency in couplers made from excitonic materials

Energy Technology Data Exchange (ETDEWEB)

Singh, Mahi R.; Racknor, Chris [Department of Physics and Astronomy, Western University, London, Ontario N6A 3K7 (Canada)

2015-03-14

We have studied light matter interaction in quantum dot and exciton-polaritonic coupler hybrid systems. The coupler is made by embedding two slabs of an excitonic material (CdS) into a host excitonic material (ZnO). An ensemble of non-interacting quantum dots is doped in the coupler. The bound exciton polariton states are calculated in the coupler using the transfer matrix method in the presence of the coupling between the external light (photons) and excitons. These bound exciton-polaritons interact with the excitons present in the quantum dots and the coupler is acting as a reservoir. The Schrödinger equation method has been used to calculate the absorption coefficient in quantum dots. It is found that when the distance between two slabs (CdS) is greater than decay length of evanescent waves the absorption spectrum has two peaks and one minimum. The minimum corresponds to a transparent state in the system. However, when the distance between the slabs is smaller than the decay length of evanescent waves, the absorption spectra has three peaks and two transparent states. In other words, one transparent state can be switched to two transparent states when the distance between the two layers is modified. This could be achieved by applying stress and strain fields. It is also found that transparent states can be switched on and off by applying an external control laser field.

Features of exciton dynamics in molecular nanoclusters (J-aggregates): Exciton self-trapping (Review Article)

Science.gov (United States)

Malyukin, Yu. V.; Sorokin, A. V.; Semynozhenko, V. P.

2016-06-01

We present thoroughly analyzed experimental results that demonstrate the anomalous manifestation of the exciton self-trapping effect, which is already well-known in bulk crystals, in ordered molecular nanoclusters called J-aggregates. Weakly-coupled one-dimensional (1D) molecular chains are the main structural feature of J-aggregates, wherein the electron excitations are manifested as 1D Frenkel excitons. According to the continuum theory of Rashba-Toyozawa, J-aggregates can have only self-trapped excitons, because 1D excitons must adhere to barrier-free self-trapping at any exciton-phonon coupling constant g = ɛLR/2β, wherein ɛLR is the lattice relaxation energy, and 2β is the half-width of the exciton band. In contrast, very often only the luminescence of free, mobile excitons would manifest in experiments involving J-aggregates. Using the Urbach rule in order to analyze the low-frequency region of the low-temperature exciton absorption spectra has shown that J-aggregates can have both a weak (g 1) exciton-phonon coupling. Moreover, it is experimentally demonstrated that under certain conditions, the J-aggregate excited state can have both free and self-trapped excitons, i.e., we establish the existence of a self-trapping barrier for 1D Frenkel excitons. We demonstrate and analyze the reasons behind the anomalous existence of both free and self-trapped excitons in J-aggregates, and demonstrate how exciton-self trapping efficiency can be managed in J-aggregates by varying the values of g, which is fundamentally impossible in bulk crystals. We discuss how the exciton-self trapping phenomenon can be used as an alternate interpretation of the wide band emission of some J-aggregates, which has thus far been explained by the strongly localized exciton model.

Charge-transfer collisions for polarized ion sources

International Nuclear Information System (INIS)

Schlachter, A.S.

1983-06-01

Charge-transfer processes relevant to polarized ion sources are discussed and results are summarized. The primary atom discussed is hydrogen, with particulr emphasis on H - formation. Heavier negative ions are briefly discussed

Analysis of Triplet Exciton Loss Pathways in PTB7:PC71BM Bulk Heterojunction Solar Cells

Science.gov (United States)

Kraus, Hannes; Heiber, Michael C.; Väth, Stefan; Kern, Julia; Deibel, Carsten; Sperlich, Andreas; Dyakonov, Vladimir

2016-07-01

A strategy for increasing the conversion efficiency of organic photovoltaics has been to increase the VOC by tuning the energy levels of donor and acceptor components. However, this opens up a new loss pathway from an interfacial charge transfer state to a triplet exciton (TE) state called electron back transfer (EBT), which is detrimental to device performance. To test this hypothesis, we study triplet formation in the high performing PTB7:PC71BM blend system and determine the impact of the morphology-optimizing additive 1,8-diiodoctane (DIO). Using photoluminescence and spin-sensitive optically detected magnetic resonance (ODMR) measurements at low temperature, we find that TEs form on PC71BM via intersystem crossing from singlet excitons and on PTB7 via EBT mechanism. For DIO blends with smaller fullerene domains, an increased density of PTB7 TEs is observed. The EBT process is found to be significant only at very low temperature. At 300 K, no triplets are detected via ODMR, and electrically detected magnetic resonance on optimized solar cells indicates that TEs are only present on the fullerenes. We conclude that in PTB7:PC71BM devices, TE formation via EBT is impacted by fullerene domain size at low temperature, but at room temperature, EBT does not represent a dominant loss pathway.

Phonon effects on the radiative recombination of excitons in double quantum dots

Science.gov (United States)

Karwat, Paweł; Sitek, Anna; Machnikowski, Paweł

2011-11-01

We study theoretically the radiative recombination of excitons in double quantum dots in the presence of carrier-phonon coupling. We show that the phonon-induced pure dephasing effects and transitions between the exciton states strongly modify the spontaneous emission process and make it sensitive to temperature, which may lead to nonmonotonic temperature dependence of the time-resolved luminescence. We show also that, under specific resonance conditions, the biexcitonic interband polarization can be coherently transferred to the excitonic one, leading to an extended lifetime of the total coherent polarization, which is reflected in the nonlinear optical spectrum of the system. We study the stability of this effect against phonon-induced decoherence.

A multi-timescale map of radiative and nonradiative decay pathways for excitons in CdSe quantum dots.

Science.gov (United States)

Knowles, Kathryn E; McArthur, Eric A; Weiss, Emily A

2011-03-22

A combination of transient absorption (TA) and time-resolved photoluminescence (TRPL) spectroscopies performed on solution-phase samples of colloidal CdSe quantum dots (QDs) allows the construction of a time-resolved, charge carrier-resolved map of decay from the first excitonic state of the QD. Data from TA and TRPL yield the same six exponential components, with time constants ranging from ∼1 ps to 50 ns, for excitonic decay. Comparison of TA signals in the visible and near-infrared (NIR) spectral regions enables determination of the relative contributions of electron and hole dynamics to each decay component, and comparison of TA and TRPL reveals that each component represents a competition between radiative and nonradiative decay pathways. In total, these data suggest that the QD sample comprises at least three distinct populations that differ in both the radiative and nonradiative decay pathways available to the excitonic charge carriers, and provide evidence for multiple emissive excitonic states in which the hole is not in the valence band, but rather a relaxed or trapped state.

Molecular orbital (SCF-Xα-SW) theory of metal-metal charge transfer processes in minerals - II. Application to Fe2+ --> Ti4+ charge transfer transitions in oxides and silicates

Science.gov (United States)

Sherman, David M.

1987-01-01

A molecular orbital description, based on Xα-Scattered wave calculations on a (FeTiO10)14− cluster, is given for Fe2+ → Ti4+ charge transfer transitions in minerals. The calculated energy for the lowest Fe2+ → Ti4+ metal-metal charge transfer transition is 18040 cm−1 in reasonable agreement with energies observed in the optical spectra of Fe-Ti oxides and silicates. As in the case of Fe2+ → Fe3+ charge transfer in mixed-valence iron oxides and silicates, Fe2+ → Ti4+ charge transfer is associated with Fe-Ti bonding across shared polyhedral edges. Such bonding results from the overlap of the Fe(t 2g ) and Ti(t 2g ) 3d orbitals.

Low-Energy Charge Transfer in Multiply-Charged Ion-Atom Collisions Studied with the Combined SCVB-MOCC Approach

Directory of Open Access Journals (Sweden)

B. Zygelman

2002-03-01

Full Text Available A survey of theoretical studies of charge transfer involving collisions of multiply-charged ions with atomic neutrals (H and He is presented. The calculations utilized the quantum-mechanical molecular-orbital close-coupling (MOCC approach where the requisite potential curves and coupling matrix elements have been obtained with the spin-coupled valence bond (SCVB method. Comparison is made among various collision partners, for equicharged systems, where it is illustrated that even for total charge transfer cross sections, scaling-laws do not exist for low-energy collisions (i.e. < 1 keV/amu. While various empirical scaling-laws are well known in the intermediateand high-energy regimes, the multi-electron configurations of the projectile ions results in a rich and varied low-energy dependence, requiring an explicit calculation for each collision-partner pair. Future charge transfer problems to be addressed with the combined SCVB-MOCC approach are briefly discussed.

Exciton-polariton dynamics in a GaAs bulk microcavity

Science.gov (United States)

Ceccherini, S.; Gurioli, M.; Bogani, F.; Colocci, M.; Tredicucci, A.; Bassani, F.; Beltram, F.; Sorba, L.

1998-01-01

We present a full analysis of exciton dynamics in a GaAs λ/2 bulk microcavity following excitation by ultrafast laser pulses. Coherent dynamics was probed by means of an interferometric technique; beating and dephasing times were studied for various excitation intensities. At high incident power, population effects begin to show up reducing exciton oscillator strength and suppressing Rabi splitting. This feature produces marked non-linearities in the input-output characteristic of the optical functions, which were studied in view of reaching bistable operation. Theoretical calculations performed within the transfer-matrix framework show good agreement with experimental results.

Charge transfer and ionization occurring in proton- and helium ion-atom collisions

International Nuclear Information System (INIS)

DuBois, R.D.

1985-12-01

Two examples are presented where specific channels have been identified that are responsible for single and double target ionization via direct coulomb ionization or charge transfer processes. Using ratios of absolute cross sections that have been measured for these processes it was shown that an independent electron model should be appropriate for calculating direct double target ionization but generally appears to be inadequate in calculating charge transfer plus ionization and double charge transfer cross sections. At present such detailed information can be obtained only in limited cases. However cross sections with detailed final charge state information should provide stringent tests for present and future theoretical work. 22 refs., 2 figs

Directional Charge Separation in Isolated Organic Semiconductor Crystalline Nanowires

Energy Technology Data Exchange (ETDEWEB)

Barnes, Michael; Labastide, Joelle; Bond-Thompson, Hilary; Briseno, Alejandro; Collela, Nicolas

2017-03-01

In the conventional view of organic photovoltaics (OPV), localized electronic excitations (excitons) formed in the active layer are transported by random 3D diffusion to an interface where charge separation and extraction take place. Because radiative de-excitation is usually strongly allowed in organic semiconductors, efficient charge separation requires high exciton mobility, with much of the diffusive motion ‘wasted’ in directions that don’t result in an interface encounter. Our research efforts are focused on ways to enforce a preferred directionality in energy and/or charge transport using ordered crystalline nanowires in which the intermolecular interactions that facilitate transport along, for example, the pi-stacking axis, can be made several orders of magnitude stronger than those in a transverse direction. The results presented in our recent work (Nature Communications) is a first step towards realizing the goal of directional control of both energy transport and charge separation, where excitons shared between adjacent molecules dissociate exclusively along the pi-stacking direction.

Computational Approach to Electron Charge Transfer Reactions

DEFF Research Database (Denmark)

Jónsson, Elvar Örn

-molecular mechanics scheme, and tools to analyse statistical data and generate relative free energies and free energy surfaces. The methodology is applied to several charge transfer species and reactions in chemical environments - chemical in the sense that solvent, counter ions and substrate surfaces are taken...... in to account - which directly influence the reactants and resulting reaction through both physical and chemical interactions. All methods are though general and can be applied to different types of chemistry. First, the basis of the various theoretical tools is presented and applied to several test systems...... and asymmetric charge transfer reactions between several first-row transition metals in water. The results are compared to experiments and rationalised with classical analytic expressions. Shortcomings of the methods are accounted for with clear steps towards improved accuracy. Later the analysis is extended...

Excitons in tunnel coupled CdTe and (Cd,Mn)Te quantum wells

Energy Technology Data Exchange (ETDEWEB)

Terletskii, Oleg; Ryabchenko, Sergiy; Tereshchenko, Oleksandr [Institute of Physics NASU, pr. Nauki 46, 03680 Kyiv (Ukraine); Sugakov, Volodymyr; Vertsimakha, Ganna [Institute for Nuclear Research NASU, pr. Nauki 47, 03680 Kyiv (Ukraine); Karczewski, Grzegorz [Institute of Physics PAS, Al. Lotnikow 32/46, PL-02-668 Warsaw (Poland)

2017-05-15

The photoluminescence (PL) from structures containing Cd{sub 0.95}Mn{sub 0.05}Te and CdTe quantum wells (QWs) separated by a narrow (1.94 nm) barrier was studied. The PL lines of comparable intensities from several possible exciton states were observed simultaneously at energy distances substantially exceeding kT. This means that the energy transfer in the studied systems is slower than the radiative recombination of the confined excitons. For the CdTe QW width of about 8.7-9 nm, indirect excitons with the electron and heavy hole chiefly localized in the CdTe and Cd{sub 1-x}Mn{sub x}Te QWs, respectively, were detected in the magnetic field. These indirect excitons have PL energy of about 10-20 meV above the PL line of the direct excitons in the CdTe QW. The observation of the PL from the indirect excitons which are not the lowest excitations in the structure is a distinctive feature of the system. Photoluminescence intensity dependence on the energy and the magnetic field. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Charge transfer properties of pentacene adsorbed on silver: DFT study

Energy Technology Data Exchange (ETDEWEB)

N, Rekha T.; Rajkumar, Beulah J. M., E-mail: beulah-rajkumar@yahoo.co.in [PG & Research Department of Physics, Lady Doak College, Madurai 625002 (India)

2015-06-24

Charge transfer properties of pentacene adsorbed on silver is investigated using DFT methods. Optimized geometry of pentacene after adsorption on silver indicates distortion in hexagonal structure of the ring close to the silver cluster and deviations in co-planarity of carbon atoms due to the variations in bond angles and dihedral angles. Theoretically simulated absorption spectrum has a symmetric surface plasmon resonance peak around 486nm corresponding to the transfer of charge from HOMO-2 to LUMO. Theoretical SERS confirms the process of adsorption, tilted orientation of pentacene on silver surface and the charge transfers reported. Localization of electron density arising from redistribution of electrostatic potential together with a reduced bandgap of pentacene after adsorption on silver suggests its utility in the design of electro active organic semiconducting devices.

Simultaneous monitoring of singlet and triplet exciton variations in solid organic semiconductors driven by an external static magnetic field

Energy Technology Data Exchange (ETDEWEB)

Ding, Baofu, E-mail: b.ding@ecu.edu.au; Alameh, Kamal, E-mail: k.alameh@ecu.edu.au [Electron Science Research Institute, Edith Cowan University, 270 Joondalup Drive, Joondalup, WA 6027 (Australia)

2014-07-07

The research field of organic spintronics has remarkably and rapidly become a promising research area for delivering a range of high-performance devices, such as magnetic-field sensors, spin valves, and magnetically modulated organic light emitting devices (OLEDs). Plenty of microscopic physical and chemical models based on exciton or charge interactions have been proposed to explain organic magneto-optoelectronic phenomena. However, the simultaneous observation of singlet- and triplet-exciton variations in an external magnetic field is still unfeasible, preventing a thorough theoretical description of the spin dynamics in organic semiconductors. Here, we show that we can simultaneously observe variations of singlet excitons and triplet excitons in an external magnetic field, by designing an OLED structure employing a singlet-exciton filtering and detection layer in conjunction with a separate triplet-exciton detection layer. This OLED structure enables the observation of a Lorentzian and a non-Lorentzian line-shape magnetoresponse for singlet excitons and triplet excitons, respectively.

Simultaneous monitoring of singlet and triplet exciton variations in solid organic semiconductors driven by an external static magnetic field

International Nuclear Information System (INIS)

Ding, Baofu; Alameh, Kamal

2014-01-01

The research field of organic spintronics has remarkably and rapidly become a promising research area for delivering a range of high-performance devices, such as magnetic-field sensors, spin valves, and magnetically modulated organic light emitting devices (OLEDs). Plenty of microscopic physical and chemical models based on exciton or charge interactions have been proposed to explain organic magneto-optoelectronic phenomena. However, the simultaneous observation of singlet- and triplet-exciton variations in an external magnetic field is still unfeasible, preventing a thorough theoretical description of the spin dynamics in organic semiconductors. Here, we show that we can simultaneously observe variations of singlet excitons and triplet excitons in an external magnetic field, by designing an OLED structure employing a singlet-exciton filtering and detection layer in conjunction with a separate triplet-exciton detection layer. This OLED structure enables the observation of a Lorentzian and a non-Lorentzian line-shape magnetoresponse for singlet excitons and triplet excitons, respectively.

Hole transfer from CdSe nanoparticles to TQ1 polymer in hybrid solar cell device

Science.gov (United States)

Sohail, Muhammad; Shah, Zawar Hussain; Saeed, Shomaila; Bibi, Nasreen; Shahbaz, Sadia; Ahmed, Safeer; Shabbir, Saima; Siddiq, Muhammad; Iqbal, Azhar

2018-05-01

In view of realizing the economic viability, we fabricate a solar cell device containing low band gap and easily processable polymer 5-yl-8-(thiophene-2,5-diyl)-2,3-bis(3-(octyloxy)phenyl) quinoxaline (TQ1) and CdSe nanoparticles (NPs) and investigate its charge transport properties. When the TQ1 is combined with the CdSe NPs a strong photoluminescence quenching and shortening of photoluminescence lifetime of the TQ1 is observed indicating exciton transfer from TQ1 to the CdSe NPs. The time-resolved photoluminescence further reveals that the exciton transfer from the polymer to CdSe NPs is very efficient (68%) and it occurs in solar cell as compared to polymer only device. These observations suggest the importance of other II-VI semiconductor NPs to achieve higher efficiency for photovoltaic devices containing TQ1 polymer.

Dynamical interaction of He atoms with metal surfaces: Charge transfer processes

International Nuclear Information System (INIS)

Flores, F.; Garcia Vidal, F.J.; Monreal, R.

1993-01-01

A self-consistent Kohn-Sham LCAO method is presented to calculate the charge transfer processes between a He * -atom and metal surfaces. Intra-atomic correlation effects are taken into account by considering independently each single He-orbital and by combining the different charge transfer processes into a set of dynamical rate equations for the different ion charge fractions. Our discussion reproduces qualitatively the experimental evidence and gives strong support to the method presented here. (author). 24 refs, 4 figs

Crystal growth of new charge-transfer salts based on π-conjugated donor molecules

Energy Technology Data Exchange (ETDEWEB)

Morherr, Antonia, E-mail: morherr@stud.uni-frankfurt.de [Physikalisches Institut, Goethe-Universität Frankfurt am Main, 60438 Frankfurt am Main (Germany); Witt, Sebastian [Physikalisches Institut, Goethe-Universität Frankfurt am Main, 60438 Frankfurt am Main (Germany); Chernenkaya, Alisa [Graduate School Materials Science in Mainz, 55128 Mainz (Germany); Institut für Physik, Johannes Gutenberg-Universität, 55099 Mainz (Germany); Bäcker, Jan-Peter [Physikalisches Institut, Goethe-Universität Frankfurt am Main, 60438 Frankfurt am Main (Germany); Schönhense, Gerd [Institut für Physik, Johannes Gutenberg-Universität, 55099 Mainz (Germany); Bolte, Michael [Institut für anorganische Chemie, Goethe-Universität Frankfurt am Main, 60438 Frankfurt am Main (Germany); Krellner, Cornelius [Physikalisches Institut, Goethe-Universität Frankfurt am Main, 60438 Frankfurt am Main (Germany)

2016-09-01

New charge transfer crystals of π-conjugated, aromatic molecules (phenanthrene and picene) as donors were obtained by physical vapor transport. The melting behavior, optimization of crystal growth and the crystal structure are reported for charge transfer salts with (fluorinated) tetracyanoquinodimethane (TCNQ-F{sub x}, x=0, 2, 4), which was used as acceptor material. The crystal structures were determined by single-crystal X-ray diffraction. Growth conditions for different vapor pressures in closed ampules were applied and the effect of these starting conditions for crystal size and quality is reported. The process of charge transfer was investigated by geometrical analysis of the crystal structure and by infrared spectroscopy on single crystals. With these three different acceptor strengths and the two sets of donor materials, it is possible to investigate the distribution of the charge transfer systematically. This helps to understand the charge transfer process in this class of materials with π-conjugated donor molecules.

High Pressure Optical Studies of the Thallous Halides and of Charge-Transfer Complexes

Science.gov (United States)

Jurgensen, Charles Willard

High pressure was used to study the insulator -to-metal transition in sulfur and the thallous halides and to study the intermolecular interactions in charge -transfer complexes. The approach to the band overlap insulator -to-metal transition was studied in three thallous halides and sulfur by optical absorption measurements of the band gap as a function of pressure. The band gap of sulfur continuously decreases with pressure up to the insulator -to-metal transition which occurs between 450 and 485 kbars. The results on the thallous halides indicate that the indirect gap decreases more rapidly than the direct gap; the closing of the indirect gap is responsible for the observed insulator -to-metal transitions. High pressure electronic and vibrational spectroscopic measurements on the solid-state complexes of HMB-TCNE were used to study the intermolecular interactions of charge -transfer complexes. The vibrational frequency shifts indicate that the degree of charge transfer increases with pressure which is independently confirmed by an increase in the molar absorptivity of the electronic charge-transfer peak. Induction and dispersion forces contribute towards a red shift of the charge-transfer peak; however, charge-transfer resonance contributes toward a blue shift and this effect is dominant for the HMB-TCNE complexes. High pressure electronic spectra were used to study the effect of intermolecular interactions on the electronic states of TCNQ and its complexes. The red shifts with pressure of the electronic spectra of TCNQ and (TCNQ)(' -) in polymer media and of crystalline TCNQ can be understood in terms of Van der Waals interactions. None of the calculations which considered intradimer distance obtained the proper behavior for either the charge-transfer of the locally excited states of the complexes. The qualitative behavior of both states can be interpreted as the effect of increased mixing of the locally excited and charge transfer states.

Spin properties of charged Mn-doped quantum dota)

Science.gov (United States)

Besombes, L.; Léger, Y.; Maingault, L.; Mariette, H.

2007-04-01

The optical properties of individual quantum dots doped with a single Mn atom and charged with a single carrier are analyzed. The emission of the neutral, negatively and positively charged excitons coupled with a single magnetic atom (Mn) are observed in the same individual quantum dot. The spectrum of the charged excitons in interaction with the Mn atom shows a rich pattern attributed to a strong anisotropy of the hole-Mn exchange interaction slightly perturbed by a small valence-band mixing. The anisotropy in the exchange interaction between a single magnetic atom and a single hole is revealed by comparing the emission of a charged Mn-doped quantum dot in longitudinal and transverse magnetic field.

Experimental evidence of state-selective charge transfer in inductively coupled plasma-atomic emission spectrometry

International Nuclear Information System (INIS)

Chan, George C.-Y.; Hieftje, Gary M.

2004-01-01

State-selective charge-transfer behavior was observed for Fe, Cr, Mn and Cu in inductively coupled plasma (ICP)-atomic emission spectrometry. Charge transfer from Ar + to Fe, Cr and Mn is state-selective because of inefficient collisional mixing of the quasiresonant charge-transfer energy levels with nearby levels. This low efficiency is the consequence of differences in electronic configuration of the core electrons. The reason for state-selective charge-transfer behavior to Cu is not clear, although a tentative explanation based on efficiency of intramultiplet and intermultiplet mixing for this special case is offered

Surface Plasmon Polariton-Assisted Long-Range Exciton Transport in Monolayer Semiconductor Lateral Heterostructure

Science.gov (United States)

Shi, Jinwei; Lin, Meng-Hsien; Chen, Yi-Tong; Estakhri, Nasim Mohammadi; Tseng, Guo-Wei; Wang, Yanrong; Chen, Hung-Ying; Chen, Chun-An; Shih, Chih-Kang; Alã¹, Andrea; Li, Xiaoqin; Lee, Yi-Hsien; Gwo, Shangjr

Recently, two-dimensional (2D) semiconductor heterostructures, i.e., atomically thin lateral heterostructures (LHSs) based on transition metal dichalcogenides (TMDs) have been demonstrated. In an optically excited LHS, exciton transport is typically limited to a rather short spatial range ( 1 micron). Furthermore, additional losses may occur at the lateral interfacial regions. Here, to overcome these challenges, we experimentally implement a planar metal-oxide-semiconductor (MOS) structure by placing a monolayer of WS2/MoS2 LHS on top of an Al2O3 capped Ag single-crystalline plate. We found that the exciton transport range can be extended to tens of microns. The process of long-range exciton transport in the MOS structure is confirmed to be mediated by an exciton-surface plasmon polariton-exciton conversion mechanism, which allows a cascaded energy transfer process. Thus, the planar MOS structure provides a platform seamlessly combining 2D light-emitting materials with plasmonic planar waveguides, offering great potential for developing integrated photonic/plasmonic functionalities.

Robust Stacking-Independent Ultrafast Charge Transfer in MoS2/WS2 Bilayers.

Science.gov (United States)

Ji, Ziheng; Hong, Hao; Zhang, Jin; Zhang, Qi; Huang, Wei; Cao, Ting; Qiao, Ruixi; Liu, Can; Liang, Jing; Jin, Chuanhong; Jiao, Liying; Shi, Kebin; Meng, Sheng; Liu, Kaihui

2017-12-26

Van der Waals-coupled two-dimensional (2D) heterostructures have attracted great attention recently due to their high potential in the next-generation photodetectors and solar cells. The understanding of charge-transfer process between adjacent atomic layers is the key to design optimal devices as it directly determines the fundamental response speed and photon-electron conversion efficiency. However, general belief and theoretical studies have shown that the charge transfer behavior depends sensitively on interlayer configurations, which is difficult to control accurately, bringing great uncertainties in device designing. Here we investigate the ultrafast dynamics of interlayer charge transfer in a prototype heterostructure, the MoS 2 /WS 2 bilayer with various stacking configurations, by optical two-color ultrafast pump-probe spectroscopy. Surprisingly, we found that the charge transfer is robust against varying interlayer twist angles and interlayer coupling strength, in time scale of ∼90 fs. Our observation, together with atomic-resolved transmission electron characterization and time-dependent density functional theory simulations, reveals that the robust ultrafast charge transfer is attributed to the heterogeneous interlayer stretching/sliding, which provides additional channels for efficient charge transfer previously unknown. Our results elucidate the origin of transfer rate robustness against interlayer stacking configurations in optical devices based on 2D heterostructures, facilitating their applications in ultrafast and high-efficient optoelectronic and photovoltaic devices in the near future.

Confined exciton spectroscopy

International Nuclear Information System (INIS)

Torres, Clivia M.S.

1998-01-01

Full text: In this work, the exciton is considered as a sensor of the electronic and optical properties of materials such as semiconductors, which have size compared to the exciton De Broglie wavelength, approximately 20 nm, depending on the semiconductor. Examples of electron-phonon, electron-electron, photon-electron, exciton-polariton, phonon-plasmon, are presented, under different confinement conditions such as quantum wells, superlattices

Charge transfers in complex transition metal alloys (Ti2Fe)

International Nuclear Information System (INIS)

Abramovici, G.

1998-01-01

We introduce a new non-orthogonal tight-binding model, for complex alloys, in which electronic structure is characterized by charge transfers. We give the analytic calculation of a charge transfer, in which overlapping two-center terms are rigorously taken into account. Then, we apply numerically this result to an approximant phase of a quasicrystal of Ti 2 Fe alloy. This model is more particularly adapted to transition metals, and gives realistic densities of states. (orig.)

Polyoxometalate active charge-transfer material for mediated redox flow battery

Energy Technology Data Exchange (ETDEWEB)

Anderson, Travis Mark; Hudak, Nicholas; Staiger, Chad; Pratt, Harry

2017-01-17

Redox flow batteries including a half-cell electrode chamber coupled to a current collecting electrode are disclosed herein. In a general embodiment, a separator is coupled to the half-cell electrode chamber. The half-cell electrode chamber comprises a first redox-active mediator and a second redox-active mediator. The first redox-active mediator and the second redox-active mediator are circulated through the half-cell electrode chamber into an external container. The container includes an active charge-transfer material. The active charge-transfer material has a redox potential between a redox potential of the first redox-active mediator and a redox potential of the second redox-active mediator. The active charge-transfer material is a polyoxometalate or derivative thereof. The redox flow battery may be particularly useful in energy storage solutions for renewable energy sources and for providing sustained power to an electrical grid.

Charge transfer in chromium-transition metal alloys

International Nuclear Information System (INIS)

Kulakowski, K.; Maksymowicz, A.

1984-07-01

The average T-matrix approximation is applied for calculations of charge transfer of 3d-electrons in transition metal alloys. The role of concentration, long-range and short-range atomic order is investigated. The results are in reasonable agreement with experimental data. (author)

The creation of defects in ammonium halides by excitons

International Nuclear Information System (INIS)

Kim, L.M.

2002-01-01

The ammonium halides crystals and alkali halides crystals are analogous by kind chemical bonds and crystalline lattices. The anionic sublattice is identical in this crystals. It is known the main mechanism of defect creation by irradiation is radiationless decay of excitons in alkali halides crystals. The F-, H-centers are formation in this processes. However, F, H-centres are not detected in ammonium halides. The goal of this work is investigation the creation of defects in ammonium halides by excitons. We established that excitons in ammonium chlorides and bromides are similar to excitons in alkali halides. It is known excitons are self-trapped and have identical parameters of the exciton-phonon interaction in both kind crystals. It is supposed, that processes of radiationless disintegration of excitons are identical in ammonium and alkali halides. It is necessary to understand why F-, H-centers are absent in ammonium halides. V k -centres are created by the excitation of the ammonium halides crystals in the absorption band of excitons. It was established by thermoluminescence and spectrums of absorption. The V k -centers begin to migrate at 110-120 K in ammonium chlorides and bromides. The curve of thermoluminescence have peak with maximum at this temperatures. It is known V k -centers in ammonium chlorides have the absorption band at 380 nm. We discovered this absorption band after irradiation of crystals by ultra-violet. In alkali halides F-center is anionic vacancy with electron. The wave function of electron are spread ed at the cations around anionic vacancy. We established the cation NH 4 + in ammonium halides can to capture electron. The ion NH 4 2+ is unsteady. It is disintegrated to NH 3 + and H + . We suppose that excitons in ammonium and alkali halides are disintegrated identically. When cation NH 4 + capture electron, in the anionic sublattice the configuration are created in a direction (100) The indicated configuration is unsteady in relation to a

Charge-carrier dynamics and Coulomb effects in semiconductor tetrapods

International Nuclear Information System (INIS)

Mauser, Christian

2011-01-01

charge carriers were additionally studied at high excitation energies. An efficient multi-exciton emission of the CdSe/CdS tetrapods could be observed, which is to be lead back to the exciton phase-space filling and a reduced Auger effect. The larger volume of the longer tetrapods allows a dual emission from the CdSe and the CdS with comparable intensities. The occuring Coulomb effects between a spatially separated electron-hole pair were studied in CdSe/CdTe tetrapods, which exhibit a type-II transition. A correlation between the tetrapod leg length and the binding energy of the charge-transfer exciton could be established, which is also reproduced in the theoretical simulations.

How exciton-vibrational coherences control charge separation in the photosystem II reaction center

NARCIS (Netherlands)

Novoderezhkin, V.I.; Romero Mesa, E.; van Grondelle, R.

2015-01-01

In photosynthesis absorbed sun light produces collective excitations (excitons) that form a coherent superposition of electronic and vibrational states of the individual pigments. Two-dimensional (2D) electronic spectroscopy allows a visualization of how these coherences are involved in the primary

Disturbing the coherent dynamics of an excitonic polarization with strong terahertz fields

Science.gov (United States)

Drexler, M. J.; Woscholski, R.; Lippert, S.; Stolz, W.; Rahimi-Iman, A.; Koch, M.

2014-11-01

We present a paper based on combining four-wave mixing and strong fields in the terahertz frequency range to monitor the time evolution of a disturbed excitonic polarization in a multiple quantum well system. Our findings not only confirm a lower field-dependent ionization threshold for higher excitonic states, but furthermore provide experimental evidence for intraexcitonic Rabi flopping in the time domain. These measurements correspond to the picture of a reversible and irreversible transfer as previously predicted by a microscopic theory.

Proton-coupled electron transfer versus hydrogen atom transfer: generation of charge-localized diabatic states.

Science.gov (United States)

Sirjoosingh, Andrew; Hammes-Schiffer, Sharon

2011-03-24

The distinction between proton-coupled electron transfer (PCET) and hydrogen atom transfer (HAT) mechanisms is important for the characterization of many chemical and biological processes. PCET and HAT mechanisms can be differentiated in terms of electronically nonadiabatic and adiabatic proton transfer, respectively. In this paper, quantitative diagnostics to evaluate the degree of electron-proton nonadiabaticity are presented. Moreover, the connection between the degree of electron-proton nonadiabaticity and the physical characteristics distinguishing PCET from HAT, namely, the extent of electronic charge redistribution, is clarified. In addition, a rigorous diabatization scheme for transforming the adiabatic electronic states into charge-localized diabatic states for PCET reactions is presented. These diabatic states are constructed to ensure that the first-order nonadiabatic couplings with respect to the one-dimensional transferring hydrogen coordinate vanish exactly. Application of these approaches to the phenoxyl-phenol and benzyl-toluene systems characterizes the former as PCET and the latter as HAT. The diabatic states generated for the phenoxyl-phenol system possess physically meaningful, localized electronic charge distributions that are relatively invariant along the hydrogen coordinate. These diabatic electronic states can be combined with the associated proton vibrational states to generate the reactant and product electron-proton vibronic states that form the basis of nonadiabatic PCET theories. Furthermore, these vibronic states and the corresponding vibronic couplings may be used to calculate rate constants and kinetic isotope effects of PCET reactions.

Using metal complex-labeled peptides for charge transfer-based biosensing with semiconductor quantum dots

Science.gov (United States)

Medintz, Igor L.; Pons, Thomas; Trammell, Scott A.; Blanco-Canosa, Juan B.; Dawson, Philip E.; Mattoussi, Hedi

2009-02-01

Luminescent colloidal semiconductor quantum dots (QDs) have unique optical and photonic properties and are highly sensitive to charge transfer in their surrounding environment. In this study we used synthetic peptides as physical bridges between CdSe-ZnS core-shell QDs and some of the most common redox-active metal complexes to understand the charge transfer interactions between the metal complexes and QDs. We found that QD emission underwent quenching that was highly dependent on the choice of metal complex used. We also found that quenching traces the valence or number of metal complexes brought into close proximity of the nanocrystal surface. Monitoring of the QD absorption bleaching in the presence of the metal complex provided insight into the charge transfer mechanism. The data suggest that two distinct charge transfer mechanisms can take place. One directly to the QD core states for neutral capping ligands and a second to surface states for negatively charged capping ligands. A basic understanding of the proximity driven charge-transfer and quenching interactions allowed us to construct proteolytic enzyme sensing assemblies with the QD-peptide-metal complex conjugates.

Dependence of Exciton Diffusion Length and Diffusion Coefficient on Photophysical Parameters in Bulk Heterojunction Organic Solar Cells

Science.gov (United States)

Yeboah, Douglas; Singh, Jai

2017-11-01

Recently, the dependence of exciton diffusion length (LD ) on some photophysical parameters of organic solids has been experimentally demonstrated, however no systematic theoretical analysis of this phenomenon has been carried out. We have conducted a theoretical study by using the Förster resonance energy transfer and Dexter carrier transfer mechanisms together with the Einstein-Smoluchowski diffusion equation to derive analytical models for the diffusion lengths (LD ) and diffusion coefficients (D) of singlet (S) and triplet (T) excitons in organic solids as functions of spectral overlap integral (J) , photoluminescence (PL) quantum yield (φD ) , dipole moment (μT ) and refractive index (n) of the photoactive material. The exciton diffusion lengths and diffusion coefficients in some selected organic solids were calculated, and we found that the singlet exciton diffusion length (LDS ) increases with φD and J, and decreases with n. Also, the triplet exciton diffusion length (LDT ) increases with φD and decreases with μT . These may be achieved through doping the organic solids into broad optical energy gap host materials as observed in previous experiments. The calculated exciton diffusion lengths are compared with experimental values and a reasonably good agreement is found between them. The results presented are expected to provide insight relevant to the synthesis of new organic solids for fabrication of bulk heterojunction organic solar cells characterized by better power conversion efficiency.

Active pixel sensor with intra-pixel charge transfer

Science.gov (United States)

Fossum, Eric R. (Inventor); Mendis, Sunetra (Inventor); Kemeny, Sabrina E. (Inventor)

2004-01-01

An imaging device formed as a monolithic complementary metal oxide semiconductor integrated circuit in an industry standard complementary metal oxide semiconductor process, the integrated circuit including a focal plane array of pixel cells, each one of the cells including a photogate overlying the substrate for accumulating photo-generated charge in an underlying portion of the substrate, a readout circuit including at least an output field effect transistor formed in the substrate, and a charge coupled device section formed on the substrate adjacent the photogate having a sensing node connected to the output transistor and at least one charge coupled device stage for transferring charge from the underlying portion of the substrate to the sensing node.

Sensitive triplet exciton detection in polyfluorene using Pd-coordinated porphyrin

NARCIS (Netherlands)

Mikhnenko, O.V.; Blom, P.W.M.; Loi, M.A.

2011-01-01

We developed a sensitive spectroscopic method to probe triplet concentration in thin films of polyfluorene (PF) at room temperature. The energy of photoexcited triplet excitons is transferred to the guest metal-organic complex, meso-tetratolylporphyrin-Pd (PdTPP), and detected as phosphorescent

Interfacial charge separation and recombination in InP and quasi-type II InP/CdS core/shell quantum dot-molecular acceptor complexes.

Science.gov (United States)

Wu, Kaifeng; Song, Nianhui; Liu, Zheng; Zhu, Haiming; Rodríguez-Córdoba, William; Lian, Tianquan

2013-08-15

Recent studies of group II-VI colloidal semiconductor heterostuctures, such as CdSe/CdS core/shell quantum dots (QDs) or dot-in-rod nanorods, show that type II and quasi-type II band alignment can facilitate electron transfer and slow down charge recombination in QD-molecular electron acceptor complexes. To explore the general applicability of this wave function engineering approach for controlling charge transfer properties, we investigate exciton relaxation and dissociation dynamics in InP (a group III-V semiconductor) and InP/CdS core/shell (a heterostructure beween group III-V and II-VI semiconductors) QDs by transient absorption spectroscopy. We show that InP/CdS QDs exhibit a quasi-type II band alignment with the 1S electron delocalized throughout the core and shell and the 1S hole confined in the InP core. In InP-methylviologen (MV(2+)) complexes, excitons in the QD can be dissociated by ultrafast electron transfer to MV(2+) from the 1S electron level (with an average time constant of 11.4 ps) as well as 1P and higher electron levels (with a time constant of 0.39 ps), which is followed by charge recombination to regenerate the complex in its ground state (with an average time constant of 47.1 ns). In comparison, InP/CdS-MV(2+) complexes show similar ultrafast charge separation and 5-fold slower charge recombination rates, consistent with the quasi-type II band alignment in these heterostructures. This result demonstrates that wave function engineering in nanoheterostructures of group III-V and II-VI semiconductors provides a promising approach for optimizing their light harvesting and charge separation for solar energy conversion applications.

Exciton Scattering approach for conjugated macromolecules: from electronic spectra to electron-phonon coupling

Science.gov (United States)

Tretiak, Sergei

2014-03-01

The exciton scattering (ES) technique is a multiscale approach developed for efficient calculations of excited-state electronic structure and optical spectra in low-dimensional conjugated macromolecules. Within the ES method, the electronic excitations in the molecular structure are attributed to standing waves representing quantum quasi-particles (excitons), which reside on the graph. The exciton propagation on the linear segments is characterized by the exciton dispersion, whereas the exciton scattering on the branching centers is determined by the energy-dependent scattering matrices. Using these ES energetic parameters, the excitation energies are then found by solving a set of generalized ``particle in a box'' problems on the graph that represents the molecule. All parameters can be extracted from quantum-chemical computations of small molecular fragments and tabulated in the ES library for further applications. Subsequently, spectroscopic modeling for any macrostructure within considered molecular family could be performed with negligible numerical effort. The exciton scattering properties of molecular vertices can be further described by tight-binding or equivalently lattice models. The on-site energies and hopping constants are obtained from the exciton dispersion and scattering matrices. Such tight-binding model approach is particularly useful to describe the exciton-phonon coupling, energetic disorder and incoherent energy transfer in large branched conjugated molecules. Overall the ES applications accurately reproduce the optical spectra compared to the reference quantum chemistry results, and make possible to predict spectra of complex macromolecules, where conventional electronic structure calculations are unfeasible.

Doping Phosphorene with Holes and Electrons through Molecular Charge Transfer.

Science.gov (United States)

Vishnoi, Pratap; Rajesh, S; Manjunatha, S; Bandyopadhyay, Arkamita; Barua, Manaswee; Pati, Swapan K; Rao, C N R

2017-11-03

An important aspect of phosphorene, the novel two-dimensional semiconductor, is whether holes and electrons can both be doped in this material. Some reports found that only electrons can be preferentially doped into phosphorene. There are some theoretical calculations showing charge-transfer interaction with both tetrathiafulvalene (TTF) and tetracyanoethylene (TCNE). We have carried out an investigation of chemical doping of phosphorene by a variety of electron donor and acceptor molecules, employing both experiment and theory, Raman scattering being a crucial aspect of the study. We find that both electron acceptors and donors interact with phosphorene by charge-transfer, with the acceptors having more marked effects. All the three Raman bands of phosphorene soften and exhibit band broadening on interaction with both donor and acceptor molecules. First-principles calculations establish the occurrence of charge-transfer between phosphorene with donors as well as acceptors. The absence of electron-hole asymmetry is noteworthy. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Charge carrier dynamics and surface plasmon interaction in gold nanorod-blended organic solar cell

International Nuclear Information System (INIS)

Rana, Aniket; Lochan, Abhiram; Chand, Suresh; Kumar, Mahesh; Singh, Rajiv K.; Gupta, Neeraj; Sharma, G. D.

2016-01-01

The inclusion of plasmonic nanoparticles into organic solar cell enhances the light harvesting properties that lead to higher power conversion efficiency without altering the device configuration. This work defines the consequences of the nanoparticle overloading amount and energy transfer process between gold nanorod and polymer (active matrix) in organic solar cells. We have studied the hole population decay dynamics coupled with gold nanorods loading amount which provides better understanding about device performance limiting factors. The exciton and plasmon together act as an interacting dipole; however, the energy exchange between these two has been elucidated via plasmon resonance energy transfer (PRET) mechanism. Further, the charge species have been identified specifically with respect to their energy levels appearing in ultrafast time domain. The specific interaction of these charge species with respective surface plasmon resonance mode, i.e., exciton to transverse mode of oscillation and polaron pair to longitudinal mode of oscillations, has been explained. Thus, our analysis reveals that PRET enhances the carrier population density in polymer via non-radiative process beyond the concurrence of a particular plasmon resonance oscillation mode and polymer absorption range. These findings give new insight and reveal specifically the factors that enhance and control the performance of gold nanorods blended organic solar cells. This work would lead in the emergence of future plasmon based efficient organic electronic devices.

Charge carrier dynamics and surface plasmon interaction in gold nanorod-blended organic solar cell

Science.gov (United States)

Rana, Aniket; Gupta, Neeraj; Lochan, Abhiram; Sharma, G. D.; Chand, Suresh; Kumar, Mahesh; Singh, Rajiv K.

2016-08-01

The inclusion of plasmonic nanoparticles into organic solar cell enhances the light harvesting properties that lead to higher power conversion efficiency without altering the device configuration. This work defines the consequences of the nanoparticle overloading amount and energy transfer process between gold nanorod and polymer (active matrix) in organic solar cells. We have studied the hole population decay dynamics coupled with gold nanorods loading amount which provides better understanding about device performance limiting factors. The exciton and plasmon together act as an interacting dipole; however, the energy exchange between these two has been elucidated via plasmon resonance energy transfer (PRET) mechanism. Further, the charge species have been identified specifically with respect to their energy levels appearing in ultrafast time domain. The specific interaction of these charge species with respective surface plasmon resonance mode, i.e., exciton to transverse mode of oscillation and polaron pair to longitudinal mode of oscillations, has been explained. Thus, our analysis reveals that PRET enhances the carrier population density in polymer via non-radiative process beyond the concurrence of a particular plasmon resonance oscillation mode and polymer absorption range. These findings give new insight and reveal specifically the factors that enhance and control the performance of gold nanorods blended organic solar cells. This work would lead in the emergence of future plasmon based efficient organic electronic devices.

Temperature-dependent kinetics of charge transfer, hydrogen-atom transfer, and hydrogen-atom expulsion in the reaction of CO+ with CH4 and CD4.

Science.gov (United States)

Melko, Joshua J; Ard, Shaun G; Johnson, Ryan S; Shuman, Nicholas S; Guo, Hua; Viggiano, Albert A

2014-09-18

We have determined the rate constants and branching ratios for the reactions of CO(+) with CH4 and CD4 in a variable-temperature selected ion flow tube. We find that the rate constants are collisional for all temperatures measured (193-700 K for CH4 and 193-500 K for CD4). For the CH4 reaction, three product channels are identified, which include charge transfer (CH4(+) + CO), H-atom transfer (HCO(+) + CH3), and H-atom expulsion (CH3CO(+) + H). H-atom transfer is slightly preferred to charge transfer at low temperature, with the charge-transfer product increasing in contribution as the temperature is increased (H-atom expulsion is a minor product for all temperatures). Analogous products are identified for the CD4 reaction. Density functional calculations on the CO(+) + CH4 reaction were also conducted, revealing that the relative temperature dependences of the charge-transfer and H-atom transfer pathways are consistent with an initial charge transfer followed by proton transfer.

Charge-transfer properties in the gas electron multiplier

International Nuclear Information System (INIS)

Han, Sanghyo; Kim, Yongkyun; Cho, Hyosung

2004-01-01

The charge transfer properties of a gas electron multiplier (GEM) were systematically investigated over a broad range of electric field configurations. The electron collection efficiency and the charge sharing were found to depend on the external fields, as well as on the GEM voltage. The electron collection efficiency increased with the collection field up to 90%, but was essentially independent of the drift field strength. A double conical GEM has a 10% gain increase with time due to surface charging by avalanche ions whereas this effect was eliminated with the cylindrical GEM. The positive-ion feedback is also estimated. (author)

Process techniques of charge transfer time reduction for high speed CMOS image sensors

International Nuclear Information System (INIS)

Cao Zhongxiang; Li Quanliang; Han Ye; Qin Qi; Feng Peng; Liu Liyuan; Wu Nanjian

2014-01-01

This paper proposes pixel process techniques to reduce the charge transfer time in high speed CMOS image sensors. These techniques increase the lateral conductivity of the photo-generated carriers in a pinned photodiode (PPD) and the voltage difference between the PPD and the floating diffusion (FD) node by controlling and optimizing the N doping concentration in the PPD and the threshold voltage of the reset transistor, respectively. The techniques shorten the charge transfer time from the PPD diode to the FD node effectively. The proposed process techniques do not need extra masks and do not cause harm to the fill factor. A sub array of 32 × 64 pixels was designed and implemented in the 0.18 μm CIS process with five implantation conditions splitting the N region in the PPD. The simulation and measured results demonstrate that the charge transfer time can be decreased by using the proposed techniques. Comparing the charge transfer time of the pixel with the different implantation conditions of the N region, the charge transfer time of 0.32 μs is achieved and 31% of image lag was reduced by using the proposed process techniques. (semiconductor devices)

Influence of dehydrated nanotubed titanic acid on charge transport and luminescent properties of polymer light-emitting diodes with fluorescent dye

Science.gov (United States)

Qian, Lei; Bera, Debasis; Jin, Zhen-Sheng; Du, Zu-Liang; Xu, Zheng; Teng, Feng; Liu, Wei

2007-09-01

In this paper, we discuss the influence of dehydrated nanotubed titanic acid (DNTA) on charge transport and luminescent properties of polymer light-emitting diodes (PLEDs) doped with fluorescent dye. Photoluminescence results confirm the efficient energy transfer from PVK to 4-(dicyanom-ethylene)-2- t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) and tris-(8-hydroxtquinoline) aluminum (Alq 3) in a DNTA-doped device. The device showed lower turn-on voltages and higher charge current by doping with DNTA, which also caused a shift in the exciton's recombination region.

Bane of Hydrogen-Bond Formation on the Photoinduced Charge-Transfer Process in Donor–Acceptor Systems

KAUST Repository

Alsam, Amani Abdu

2017-03-14

Controlling the ultrafast dynamical process of photoinduced charge transfer at donor acceptor interfaces remains a major challenge for physical chemistry and solar cell communities. The process is complicated by the involvement of other complex dynamical processes, including hydrogen bond formation, energy transfer, and solvation dynamics occurring on similar time scales. In this study, we explore the remarkable impact of hydrogen-bond formation on the interfacial charge transfer between a negatively charged electron donating anionic porphyrin and a positively charged electron accepting pi-conjugated polymer, as a model system in solvents with different polarities and capabilities for hydiogen bonding using femtosecond transient absorption spectroscopy. Unlike the conventional understanding of the key role of hydrogen bonding in promoting the charge-transfer process, our steadystate and time-resolved results reveal that the intervening hydrogen-bonding environment and, consequently, the probable longer spacing between the donor and acceptor molecules significantly hinders the charge-transfer process between them. These results show that site-specific hydrogen bonding and geometric considerations between donor and acceptor can be exploited to control both the charge-transfer dynamics and its efficiency not only at donor acceptor interfaces but also in complex biological systems.

Theory and simulation of charge transfer through DNA - nanotube contacts

International Nuclear Information System (INIS)

Rink, Gunda; Kong Yong; Koslowski, Thorsten

2006-01-01

We address the problem of charge transfer between a single-stranded adenine oligomer and semiconducting boron nitride nanotubes from a theoretical and numerical perspective. The model structures have been motivated by computer simulations; sample geometries are used as the input of an electronic structure theory that is based upon an extended Su-Schrieffer-Heeger Hamiltonian. By analyzing the emerging potential energy surfaces, we obtain hole transfer rates via Marcus' theory of charge transfer. In the presence of nanotubes, these rates exceed those of isolated DNA single strands by a factor of up to 10 4 . This enhancement can be rationalized and quantified as a combination of a template effect and the participation of the tube within a superexchange mechanism

Positron Annihilation in Solid Charge-Transfer Complexes

DEFF Research Database (Denmark)

Lévay, B.; Jansen, P.

1979-01-01

Positron lifetime and angular correlation measurements have been carried out on 1:1 charge-transfer complexes, on their pure donor and acceptor components and on the 1:1 M mechanical mixtures of these components. Complex formation reduced the intensity of the long-lifetime component of the donor...

Charge generation in organic solar cell materials studied by terahertz spectroscopy

KAUST Repository

Scarongella, M.; Brauer, J. C.; Douglas, J. D.; Frechet, Jean; Banerji, N.

2015-01-01

THz signature for bound excitons in neat PBDTTPD films, pointing to important delocalization in those excitons. Then, we investigated the nature and local mobility (orders of magnitude higher than bulk mobility) of charges in the PBDTTPPD:PCBM blend

Effects of acid concentration on intramolecular charge transfer ...

Indian Academy of Sciences (India)

rate. Time-dependent density functional theory calculations have been performed to understand the observed spectroscopic results. Keywords. Intramolecular charge transfer; absorption and fluorescence; time resolved fluorescence measurements; acid concentration dependence; time-dependent density functional theory.

Ultrafast Interfacial Electron and Hole Transfer from CsPbBr3 Perovskite Quantum Dots.

Science.gov (United States)

Wu, Kaifeng; Liang, Guijie; Shang, Qiongyi; Ren, Yueping; Kong, Degui; Lian, Tianquan

2015-10-14

Recently reported colloidal lead halide perovskite quantum dots (QDs) with tunable photoluminescence (PL) wavelengths covering the whole visible spectrum and exceptionally high PL quantum yields (QYs, 50-90%) constitute a new family of functional materials with potential applications in light-harvesting and -emitting devices. By transient absorption spectroscopy, we show that the high PL QYs (∼79%) can be attributed to negligible electron or hole trapping pathways in CsPbBr3 QDs: ∼94% of lowest excitonic states decayed with a single-exponential time constant of 4.5 ± 0.2 ns. Furthermore, excitons in CsPbBr3 QDs can be efficiently dissociated in the presence of electron or hole acceptors. The half-lives of electron transfer (ET) to benzoquinone and subsequent charge recombination are 65 ± 5 ps and 2.6 ± 0.4 ns, respectively. The half-lives for hole transfer (HT) to phenothiazine and the subsequent charge recombination are 49 ± 6 ps and 1.0 ± 0.2 ns, respectively. The lack of electron and hole traps and fast interfacial ET and HT rates are key properties that may enable the development of efficient lead halide perovskite QDs-based light-harvesting and -emitting devices.

Multi-Excitonic Quantum Dot Molecules

Science.gov (United States)

Scheibner, M.; Stinaff, E. A.; Doty, M. F.; Ware, M. E.; Bracker, A. S.; Gammon, D.; Ponomarev, I. V.; Reinecke, T. L.; Korenev, V. L.

2006-03-01

With the ability to create coupled pairs of quantum dots, the next step towards the realization of semiconductor based quantum information processing devices can be taken. However, so far little knowledge has been gained on these artificial molecules. Our photoluminescence experiments on single InAs/GaAs quantum dot molecules provide the systematics of coupled quantum dots by delineating the spectroscopic features of several key charge configurations in such quantum systems, including X, X^+,X^2+, XX, XX^+ (with X being the neutral exciton). We extract general rules which determine the formation of molecular states of coupled quantum dots. These include the fact that quantum dot molecules provide the possibility to realize various spin configurations and to switch the electron hole exchange interaction on and off by shifting charges inside the molecule. This knowledge will be valuable in developing implementations for quantum information processing.

Exciton absorption spectrum of thin Ag sub 2 ZnI sub 4

CERN Document Server

Yunakova, O N; Kovalenko, E N

2002-01-01

In Ag sub 2 ZnI sub 4 compound thin films one investigated into the electron spectrum of absorption within 3-6 eV photon energy range. The boundary of interband absorption is determined to correspond to the direct permitted transitions with E sub g = 3.7 eV forbidden gap width. A strong exciton band at E = 3.625 eV (80 K) GAMMA half width temperature run of which within 80-390 K range is governed by exciton-phonon interaction typical for quasi-single-dimensional excitons, is adjacent to the absorption boundary. At T <= 390 K one observes a bend in E(T) and GAMMA(T) dependences associated with generation of the Frenkel defects and followed by transfer of Ag ions to the interstices and vacancies of the compound crystalline lattice

High-energy behavior of the charge-transfer cross section in the eikonal approximation

International Nuclear Information System (INIS)

Dewangan, D.P.

1982-01-01

In the now popular version of the eikonal theory of charge transfer, the eikonal wave function does not satisfy the proper boundary conditions and the charge-transfer amplitude is uncertain by an undefined phase factor. The inclusion of the internuclear potential in a consistent way, in the eikonal theory overcomes theses difficulties. However, it also changes the high-energy asymptotic form of proton-hydrogen charge-transfer cross section from sigma/sub eik/ approx.(23/48) sigma/sub BK/ by a small amount to sigma/sub G/approx.(20.109/48)sigma/sub BK/ where sigma/sub BK/ is the Brinkman-Kramers cross section

Ultrafast Mid-Infrared Intra-Excitonic Response of Individualized Single-Walled Carbon Nanotubes

International Nuclear Information System (INIS)

Wang, Jigang; Graham, Matt W.; Ma, Yingzhong; Fleming, Graham R.; Kaindl, Robert A.

2009-01-01

The quasi-1D confinement and reduced screening of photoexcited charges in single-walled carbon nanotubes (SWNTs) entails strongly-enhanced Coulomb interactions and exciton binding energies. Such amplified electron-hole (e-h) correlations have important implications for both fundamental physics and optoelectronic applications of nanotubes. The availability of 'individualized' SWNT ensembles with bright and structured luminescence has rendered specific tube chiralities experimentally accessible. In these samples, evidence for excitonic behavior was found in absorption-luminescence maps, two-photon excited luminescence, or ultrafast carrier dynamics. Here, we report ultrafast mid-infrared (mid-IR) studies of individualized SWNTs, evidencing strong photoinduced absorption around 200 meV in semiconducting tubes of (6,5) and (7,5) chiralities. This manifests the observation of quasi-1D intra-excitonic transitions between different relative-momentum states, in agreement with the binding energy and calculated oscillator strength. Our measurements further reveal a saturation of the photoinduced absorption with increasing phase-space filling of the correlated e-h pairs. The transient mid-IR response represents a new tool, unhindered by restrictions of momentum or interband dipole moment, to investigate the density and dynamics of SWNT excitons.

Charge Carrier Dynamics and pH Effect on Optical Properties of Anionic and Cationic Porphyrin-Graphene Oxide Composites

Science.gov (United States)

Bajjou, O.; Bakour, A.; Khenfouch, M.; Baitoul, M.; Mothudi, B.; Maaza, M.; Faulques, E.

2018-02-01

Composites of graphene oxide (GO) functionalized with Sn(V) tetrakis (4-pyridyl)porphyrin (SnTPyP2+) and meso-tetrakis(4-phenylsulfonic acid)porphyrin (H4TPPS4 2- ) were prepared at different pH values.Successful synthesis of water-soluble stable suspension of GO-SnTPyP2+ and GO-H4TPPS4 2-was confirmed using various spectroscopic techniques, including scanning electronic microscopy (SEM), Raman spectroscopy, and ultraviolet-visible (UV-Vis) absorption. Variation of the pH was found to strongly influence the optical properties of the GO-SnTPyP2+ and GO-H4TPPS4 2-composites, as demonstrated by the UV-Vis absorption results. Steady-state photoluminescence (PL) and time-resolved PL (TRPL) results for both composites showed PL quenching and decrease in the exciton mean lifetime, suggesting strong excited-state interactions between the different components. Moreover, charge carrier dynamics study revealed that insertion of GO into both porphyrin derivatives led to faster mean lifetime for excitons with a slight advantage in the case of the cationic porphyrin-GO composite, making it a better choice for charge separation applications thanks to the higher efficiency of charge/energy transfer interactions.

Final Report, DOE grant DE-FG02-99ER45780, "Indirect Excitons in Coupled Quantum Wells"

Energy Technology Data Exchange (ETDEWEB)

Snoke, david W. [University of Pittsburgh

2014-07-21

The is the final technical report for this project, which was funded by the DOE from 1999 to 2012. The project focused on experimental studies of spatially indirect excitons in coupled quantum wells, with the aim of understanding the quantum physics of these particles, including such effects as pattern formation due to electron-hole charge separation, the Mott plasma-insulator transition, luminescence up-conversion through field-assisted tunneling, luminescence line shifts due to many-body renormalization and magnetic field effects on tunneling, and proposed effects such as Bose-Einstein condensation of indirect excitons and phase separation of bright and dark indirect excitons. Significant results are summarized here and the relation to other work is discussed.

Photoinduced charge and energy transfer in dye-doped conjugated polymers

International Nuclear Information System (INIS)

Veldman, Dirk; Bastiaansen, Jolanda J.A.M.; Langeveld-Voss, Bea M.W.; Sweelssen, Joergen; Koetse, Marc M.; Meskers, Stefan C.J.; Janssen, Rene A.J.

2006-01-01

Conjugated polymer-molecular dye blends of MDMO-PPV (poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene]) and PF1CVTP (poly[9,9-dioctylfluorene-2,7-diyl-alt-2,5-bis(2-thienyl-1-cyanovinyl) -1-(3',7= '-dimethyloctyloxy)-4-methoxybenzene-5'',5''-diyl]) with three dipyrrometheneboron difluoride (bodipy) dyes were studied by (time-resolved) fluorescence and photoinduced absorption spectroscopy to determine quantitatively the relation between the electronic HOMO and LUMO levels and the occurrence of energy or charge transfer after optical excitation. We find that for MDMO-PPV photoinduced charge transfer to the dyes occurs, while photoexcitation of PF1CVTP exclusively results in energy transfer. The differences can be rationalized by assuming that the energy of the charge separated state is 0.33-0.45 eV higher than the energy determined from oxidation and reduction potentials of donor and acceptor, respectively. This provides an important design rule to identify appropriate materials for polymer solar cells that can have a high open-circuit voltage

Surface Charge Transfer Doping of Monolayer Phosphorene via Molecular Adsorption.

Science.gov (United States)

He, Yuanyuan; Xia, Feifei; Shao, Zhibin; Zhao, Jianwei; Jie, Jiansheng

2015-12-03

Monolayer phosphorene has attracted much attention owing to its extraordinary electronic, optical, and structural properties. Rationally tuning the electrical transport characteristics of monolayer phosphorene is essential to its applications in electronic and optoelectronic devices. Herein, we study the electronic transport behaviors of monolayer phosphorene with surface charge transfer doping of electrophilic molecules, including 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), NO2, and MoO3, using density functional theory combined with the nonequilibrium Green's function formalism. F4TCNQ shows optimal performance in enhancing the p-type conductance of monolayer phosphorene. Static electronic properties indicate that the enhancement is originated from the charge transfer between adsorbed molecule and phosphorene layer. Dynamic transport behaviors demonstrate that additional channels for hole transport in host monolayer phosphorene were generated upon the adsorption of molecule. Our work unveils the great potential of surface charge transfer doping in tuning the electronic properties of monolayer phosphorene and is of significance to its application in high-performance devices.

An abnormally slow proton transfer reaction in a simple HBO derivative due to ultrafast intramolecular-charge transfer events.

Science.gov (United States)

Alarcos, Noemí; Gutierrez, Mario; Liras, Marta; Sánchez, Félix; Douhal, Abderrazzak

2015-07-07

We report on the steady-state, picosecond and femtosecond time-resolved studies of a charge and proton transfer dye 6-amino-2-(2'-hydroxyphenyl)benzoxazole (6A-HBO) and its methylated derivative 6-amino-2-(2'-methoxyphenyl)benzoxazole (6A-MBO), in different solvents. With femtosecond resolution and comparison with the photobehaviour of 6A-MBO, we demonstrate for 6A-HBO in solution, the photoproduction of an intramolecular charge-transfer (ICT) process at S1 taking place in ∼140 fs or shorter, followed by solvent relaxation in the charge transferred species. The generated structure (syn-enol charge transfer conformer) experiences an excited-state intramolecular proton-transfer (ESIPT) reaction to produce a keto-type tautomer. This subsequent proton motion occurs in 1.2 ps (n-heptane), 14 ps (DCM) and 35 ps (MeOH). In MeOH, it is assisted by the solvent molecules and occurs through tunneling for which we got a large kinetic isotope effect (KIE) of about 13. For the 6A-DBO (deuterated sample in CD3OD) the global proton-transfer reaction takes place in 200 ps, showing a remarkable slow KIE regime. The slow ESIPT reaction in DCM (14 ps), not through tunnelling as it is not sensitive to OH/OD exchange, has however to overcome an energy barrier using intramolecular as well as solvent coordinates. The rich ESIPT dynamics of 6A-HBO in the used solutions is governed by an ICT reaction, triggered by the amino group, and it is solvent dependent. Thus, the charge injection to a 6A-HBO molecular frame makes the ICT species more stable, and the phenol group less acidic, slowing down the subsequent ESIPT reaction. Our findings bring new insights into the coupling between ICT and ESIPT reactions on the potential-energy surfaces of several barriers.

Photo-induced charge transfer at heterogeneous interfaces: Dye-sensitized tin disulfide, the theory and the experiment

International Nuclear Information System (INIS)

Lanzafame, J.M.

1993-01-01

The study of photo-induced charge transfer is an endeavor that spans the entire industrial period of man's history. Its great importance demands an ever greater understanding of its underlying principles. The work discussed here attempts to probe elementary aspects of the charge transfer process. Investigations into the theory of charge transfer reactions are made in an attempt to isolate the relevant parameters. An analytical discussion is made of a simple Golden Rule type rate equation to describe the transfer kinetics. Then a quantum simulation is carried out to follow the wavefunction propagation as a test of the applicability of the assumptions made in deriving the simpler rate equation. Investigation of charge transfer at surfaces is bet served by the application of ultrafast optical spectroscopies to probe carrier dynamics. A discussion of the properties of the short pulse laser systems employed is included along with a discussion of the different optical spectroscopies available. These tools are then brought to bear upon dye-sensitized SnS 2 , a model system for the study of charge injection processes. The unique properties of the semiconductor are discussed with respect to the charge transfer process. The unique properties of the semiconductor are discussed with respect to the charge transfer process. The optical experiments performed on the dye/SnS 2 systems elucidate the fundamental carrier dynamics and these dynamics are discussed within the theoretical framework to provide a complete picture of the charge transfer kinetics

Charge percolation pathways in polymer blend photovoltaic diodes with sub-mesoscopic two-phase microstructures

Science.gov (United States)

Dou, Fei; Silva, Carlos; Zhang, Xinping

2013-05-01

We find that the external quantum efficiency of photovoltaic diodes based on finely mixed blends of poly-9,9’-dioctylfluorene-co-bis-N,N’-(4-butylphenyl)-bis-N,N’-phenyl-l,4-phenylenediamine (PFB) and poly-9,9’- dioctylfluorene-co-benzothiadiazole (F8BT) depends strongly on the blend ratio. The peak external quantum efficiency is optimum for a PFB:F8BT ratio of 3:1. The difference of peak efficiency for this composition and a 1:1 ratio is significantly higher than the reported yield of charge-transfer excitons. From a surface topography analysis, we believe that charge percolation plays a crucial role in photocurrent efficiency in PFB:F8BT diodes. Furthermore, we present a qualitative model for different charge percolation pathways in diodes of different blend ratios.

Super-iron Nanoparticles with Facile Cathodic Charge Transfer

Energy Technology Data Exchange (ETDEWEB)

M Farmand; D Jiang; B Wang; S Ghosh; D Ramaker; S Licht

2011-12-31

Super-irons contain the + 6 valence state of iron. One advantage of this is that it provides a multiple electron opportunity to store additional battery charge. A decrease of particle size from the micrometer to the nanometer domain provides a higher surface area to volume ratio, and opportunity to facilitate charge transfer, and improve the power, voltage and depth of discharge of cathodes made from such salts. However, super-iron salts are fragile, readily reduced to the ferric state, with both heat and contact with water, and little is known of the resultant passivating and non-passivating ferric oxide products. A pathway to decrease the super-iron particle size to the nano-domain is introduced, which overcomes this fragility, and retains the battery capacity advantage of their Fe(VI) valence state. Time and power controlled mechanosynthesis, through less aggressive, dry ball milling, leads to facile charge transfer of super-iron nanoparticles. Ex-situ X-ray Absorption Spectroscopy is used to explore the oxidation state and structure of these iron oxides during discharge and shows the significant change in stability of the ferrate structure to lower oxidation state when the particle size is in the nano-domain.

Charge transfer between O6+ and atomic hydrogen

Science.gov (United States)

Wu, Y.; Stancil, P. C.; Liebermann, H. P.; Buenker, R. J.; Schultz, D. R.; Hui, Y.

2011-05-01

The charge exchange process has been found to play a dominant role in the production of X-rays and/or EUV photons observed in cometary and planetary atmospheres and from the heliosphere. Charge transfer cross sections, especially state-selective cross sections, are necessary parameters in simulations of X-ray emission. In the present work, charge transfer due to collisions of ground state O6+(1s2 1 S) with atomic hydrogen has been investigated theoretically using the quantum-mechanical molecular-orbital close-coupling method (QMOCC). The multi-reference single- and double-excitation configuration interaction approach (MRDCI) has been applied to compute the adiabatic potential and nonadiabatic couplings, and the atomic basis sets used have been optimized with the method proposed previously to obtain precise potential data. Total and state-selective cross sections are calculated for energies between 10 meV/u and 10 keV/u. The QMOCC results are compared to available experimental and theoretical data as well as to new atomic-orbital close-coupling (AOCC) and classical trajectory Monte Carlo (CTMC) calculations. A recommended set of cross sections, based on the MOCC, AOCC, and CTMC calculations, is deduced which should aid in X-ray modeling studies.

Exchange correlation effects on plasmons and on charge-density wave instability in narrow-band quasi-one-dimensional metals

International Nuclear Information System (INIS)

Nobile, A.; Tosatti, E.

1979-05-01

The coexistence of tight-binding and exchange-correlation effects inside each chain of a model quasi-one-dimensional metal, on both plasmon and charge density wave properties have been studied. The results, while in qualitative agreement with other treatments of the problem at long wavelengths, indicate a strong tendency for plasmons to turn into excitons at larger momenta, and to exhibit an ''excitonic'' charge-density wave instability at k approximately 2ksub(F). The nature of the plasmon branches and of the excitonic charge distortion is examined. Relevance to existing quasi-one-dimensional materials is also discussed. (author)

Integer Charge Transfer and Hybridization at an Organic Semiconductor/Conductive Oxide Interface

KAUST Repository

Gruenewald, Marco

2015-02-11

We investigate the prototypical hybrid interface formed between PTCDA and conductive n-doped ZnO films by means of complementary optical and electronic spectroscopic techniques. We demonstrate that shallow donors in the vicinity of the ZnO surface cause an integer charge transfer to PTCDA, which is clearly restricted to the first monolayer. By means of DFT calculations, we show that the experimental signatures of the anionic PTCDA species can be understood in terms of strong hybridization with localized states (the shallow donors) in the substrate and charge back-donation, resulting in an effectively integer charge transfer across the interface. Charge transfer is thus not merely a question of locating the Fermi level above the PTCDA electron-transport level but requires rather an atomistic understanding of the interfacial interactions. The study reveals that defect sites and dopants can have a significant influence on the specifics of interfacial coupling and thus on carrier injection or extraction.

Optical Spectroscopy Of Charged Quantum Dot Molecules

Science.gov (United States)

Scheibner, M.; Bracker, A. S.; Stinaff, E. A.; Doty, M. F.; Gammon, D.; Ponomarev, I. V.; Reinecke, T. L.; Korenev, V. L.

2007-04-01

Coupling between two closely spaced quantum dots is observed by means of photoluminescence spectroscopy. Hole coupling is realized by rational crystal growth and heterostructure design. We identify molecular resonances of different excitonic charge states, including the important case of a doubly charged quantum dot molecule.

Time-dependent screening of a positive charge distribution in metals: Excitons on an ultra-short time scale

OpenAIRE

Schöne, Wolf-Dieter; Ekardt, Walter

2000-01-01

Experiments determining the lifetime of excited electrons in crystalline copper reveal states which cannot be interpreted as Bloch states [S. Ogawa {\\it et al.}, Phys. Rev. B {\\bf 55}, 10869 (1997)]. In this article we propose a model which explains these states as transient excitonic states in metals. The physical background of transient excitons is the finite time a system needs to react to an external perturbation, in other words, the time which is needed to build up a polarization cloud. ...

Charge Transfer Channels in Formation of Exciplex in Polymer Blends

Science.gov (United States)

Dou, Fei; Zhang, Xin-Ping

2011-09-01

The strong dependence of photoluminescence of charge transfer excited states or exciplex in a blend film of poly(9,9'-dioctylfluorene-co-benzothiadiazole) (F8BT) and poly(9,9'-dioctylfluorene-co-bis-N,N'-(4-butylphenyl)-bis-N,N'-phenyl-1,4- phenylenediamine) (PFB) on the excitation wavelengths and morphology is investigated. The experimental results reveal that electron transfer in the LUMOs from PFB to F8BT is more efficient than hole transfer in the HOMOs from PFB to F8BT for the formation of exciplex at the interfacial junctions between these two types of molecules in the blend film. Furthermore, energy transfer from the blue-emitting PFB to the green-emitting F8BT at the interfaces introduces an additional two-step channel and thus enhances the formation of an exciplex. This is important for understanding of charge generation and separation in organic bulk heterojunctions and for design of optoelectronic devices.

Charge Transfer Channels in Formation of Exciplex in Polymer Blends

International Nuclear Information System (INIS)

Dou Fei; Zhang Xin-Ping

2011-01-01

The strong dependence of photoluminescence of charge transfer excited states or exciplex in a blend film of poly(9,9'-dioctylfluorene-co-benzothiadiazole) (F8BT) and poly(9,9'-dioctylfluorene-co-bis-N,N'-(4-butylphenyl)-bis-N,N'-phenyl-1,4- phenylenediamine) (PFB) on the excitation wavelengths and morphology is investigated. The experimental results reveal that electron transfer in the LUMOs from PFB to F8BT is more efficient than hole transfer in the HOMOs from PFB to F8BT for the formation of exciplex at the interfacial junctions between these two types of molecules in the blend film. Furthermore, energy transfer from the blue-emitting PFB to the green-emitting F8BT at the interfaces introduces an additional two-step channel and thus enhances the formation of an exciplex. This is important for understanding of charge generation and separation in organic bulk heterojunctions and for design of optoelectronic devices. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

Charge transfer in gold--alkali-metal systems

International Nuclear Information System (INIS)

Watson, R.E.; Weinert, M.

1994-01-01

Based on conventional electronegativity arguments, gold--alkali-metal compounds are expected to be among the most ''ionic'' of metallic compounds. The concepts of ionicity and charge transfer are difficult to quantify. However, the changes in bonding in the 50/50 Au--alkali-metal systems between the elemental metals and the compounds are so severe that observations can readily be made concerning their character. The results, as obtained from self-consistent electronic-structure calculations, lead to the apparently odd observation that the electron density at the alkali-metal sites in the compound increases significantly and this involves high l componennts in the charge density. This increase, however, can be attributed to Au-like orbitals spatially overlapping the alkali-metal sites. In a chemical sense, it is reasonable to consider the alkali-metal transferring charge to these Au orbitals. While normally the difference in heats of formation between muffin-tin and full-potential calculations for transition-metal--transition-metal and transition-metal--main-group (e.g., Al) compounds having high site symmetry are small, for the gold--alkali-metal systems, the changes in bonding in the compounds cause differences of ∼0.5 eV/atom between the two classes of potential. Any serious estimate of the electronic structure in these systems must account for these aspherical bonding charges. The origin of the semiconducting behavior of the heavy-alkali-metal Au compounds is shown to arise from a combination of the Au-Au separations and the ionic character of the compounds; the light-alkali-metal Au compounds, with their smaller Au-Au separations, do not have a semiconducting gap. Core-level shifts and isomer shifts are also briefly discussed

Ultrafast Microscopy of Energy and Charge Transport

Science.gov (United States)

Huang, Libai

The frontier in solar energy research now lies in learning how to integrate functional entities across multiple length scales to create optimal devices. Advancing the field requires transformative experimental tools that probe energy transfer processes from the nano to the meso lengthscales. To address this challenge, we aim to understand multi-scale energy transport across both multiple length and time scales, coupling simultaneous high spatial, structural, and temporal resolution. In my talk, I will focus on our recent progress on visualization of exciton and charge transport in solar energy harvesting materials from the nano to mesoscale employing ultrafast optical nanoscopy. With approaches that combine spatial and temporal resolutions, we have recently revealed a new singlet-mediated triplet transport mechanism in certain singlet fission materials. This work demonstrates a new triplet exciton transport mechanism leading to favorable long-range triplet exciton diffusion on the picosecond and nanosecond timescales for solar cell applications. We have also performed a direct measurement of carrier transport in space and in time by mapping carrier density with simultaneous ultrafast time resolution and 50 nm spatial precision in perovskite thin films using transient absorption microscopy. These results directly visualize long-range carrier transport of 220nm in 2 ns for solution-processed polycrystalline CH3NH3PbI3 thin films. The spatially and temporally resolved measurements reported here underscore the importance of the local morphology and establish an important first step towards discerning the underlying transport properties of perovskite materials.

Interfacial Charge Transfer States in Condensed Phase Systems

Science.gov (United States)

Vandewal, Koen

2016-05-01

Intermolecular charge transfer (CT) states at the interface between electron-donating (D) and electron-accepting (A) materials in organic thin films are characterized by absorption and emission bands within the optical gap of the interfacing materials. CT states efficiently generate charge carriers for some D-A combinations, and others show high fluorescence quantum efficiencies. These properties are exploited in organic solar cells, photodetectors, and light-emitting diodes. This review summarizes experimental and theoretical work on the electronic structure and interfacial energy landscape at condensed matter D-A interfaces. Recent findings on photogeneration and recombination of free charge carriers via CT states are discussed, and relations between CT state properties and optoelectronic device parameters are clarified.

Effect of exciton pairing on the stationary Josephson current in superconductor-semimetal-superconductor junctions

International Nuclear Information System (INIS)

Itskovich, I.F.; Shekhter, R.I.

1983-01-01

The effect of exciton pairing of charge carriers in a semimetal on the stationary Josephson current in superconductor-semimetal-superconductor junctions is considered. It is shown that the phase transition of the semimetal interlayer into an exciton dielectric state for T/sub γ/< T/sub c/ (T/sub γ/, T/sub c/ are the superconducting and exciton transition temperatures, respectively) is accompanied by a kink on the critical current j/sub c/ versus temperature curve at the point T = T/sub γ/. A sharp nonmonotonic temperature dependence of the reduced current j/sub c//j/sub c/0 (j/sub c/0 is the critical current at T/sub γ/ = 0) is also possible in the range T< T/sub γ/. At low temperatures T<< v/sub 1,2//d<< T/sub γ/ (v/sub 1,2/ are the Fermi velocities of the carriers in the semimetal, d is the thickness of the interlayer) the critical current of the superconductor-semimetal-superconductor junction is exponentially smaller than the current in the absence of exciton pairing

Charge transfer through DNA/DNA duplexes and DNA/RNA hybrids: complex theoretical and experimental studies.

Science.gov (United States)

Kratochvílová, Irena; Vala, Martin; Weiter, Martin; Špérová, Miroslava; Schneider, Bohdan; Páv, Ondřej; Šebera, Jakub; Rosenberg, Ivan; Sychrovský, Vladimír

2013-01-01

Oligonucleotides conduct electric charge via various mechanisms and their characterization and understanding is a very important and complicated task. In this work, experimental (temperature dependent steady state fluorescence spectroscopy, time-resolved fluorescence spectroscopy) and theoretical (Density Functional Theory) approaches were combined to study charge transfer processes in short DNA/DNA and RNA/DNA duplexes with virtually equivalent sequences. The experimental results were consistent with the theoretical model - the delocalized nature of HOMO orbitals and holes, base stacking, electronic coupling and conformational flexibility formed the conditions for more effective short distance charge transfer processes in RNA/DNA hybrids. RNA/DNA and DNA/DNA charge transfer properties were strongly connected with temperature affected structural changes of molecular systems - charge transfer could be used as a probe of even tiny changes of molecular structures and settings. © 2013. Published by Elsevier B.V. All rights reserved.

Towards a coherent picture of excitonic coherence in the Fenna–Matthews–Olson complex

International Nuclear Information System (INIS)

Fidler, Andrew F; Caram, Justin R; Hayes, Dugan; Engel, Gregory S

2012-01-01

Observations of long-lived coherence between excited states in several photosynthetic antenna complexes has motivated interest in developing a more detailed understanding of the role of the protein matrix in guiding the underlying dynamics of the system. These experiments suggest that classical rate laws may not provide an adequate description of the energy transfer process and that quantum effects must be taken into account to describe the near unity transfer efficiency in these systems. Recently, it has been shown that coherences between different pairs of excitons dephase at different rates. These details should provide some insight about the underlying electronic structure of the complex and its coupling to the protein bath. Here we show that a simple model can account for the different dephasing rates as well as the most current available experimental evidence of excitonic coherences in the Fenna–Matthews–Olson complex. The differences in dephasing rates can be understood as arising largely from differences in the delocalization and shared character between the underlying electronic states. We also suggest that the anomalously low dephasing rate of the exciton 1–2 coherence is enhanced by non-secular effects. (paper)

Composition-Dependent Energy Splitting between Bright and Dark Excitons in Lead Halide Perovskite Nanocrystals.

Science.gov (United States)

Chen, Lan; Li, Bin; Zhang, Chunfeng; Huang, Xinyu; Wang, Xiaoyong; Xiao, Min

2018-03-14

Perovskite semiconductor nanocrystals with different compositions have shown promise for applications in light-emitting devices. Dark excitonic states may suppress light emission from such nanocrystals by providing an additional nonradiative recombination channel. Here, we study the composition dependence of dark exciton dynamics in nanocrystals of lead halides by time-resolved photoluminescence spectroscopy at cryogenic temperatures. The presence of a spin-related dark state is revealed by magneto-optical spectroscopy. The energy splitting between bright and dark states is found to be highly sensitive to both halide elements and organic cations, which is explained by considering the effects of size confinement and charge screening, respectively, on the exchange interaction. These findings suggest the possibility of manipulating dark exciton dynamics in perovskite semiconductor nanocrystals by composition engineering, which will be instrumental in the design of highly efficient light-emitting devices.

Optical nutation in the exciton range of spectrum

International Nuclear Information System (INIS)

Khadzhi, P. I.; Vasiliev, V. V.

2013-01-01

Optical nutation in the exciton range of spectrum is studied in the mean field approximation taking into account exciton-photon and elastic exciton-exciton interactions. It is shown that the features of nutation development are determined by the initial exciton and photon densities, the resonance detuning, the nonlinearity parameter, and the initial phase difference. For nonzero initial exciton and photon concentrations, three regimes of temporal evolution of excitons and photons exist: periodic conversion of excitons to photons and vice versa, aperiodic conversion of photons to excitons, and the rest regime. In the rest regime, the initial exciton and photon densities are nonzero and do not change with time. The oscillation amplitudes and periods of particle densities determined by the system parameters are found. The exciton self-trapping and photon trapping appearing in the system at threshold values of the nonlinearity parameter were predicted. As this parameter increases, the oscillation amplitudes of the exciton and photon densities sharply change at the critical value of the nonlinearity parameter. These two phenomena are shown to be caused by the elastic exciton-exciton interaction, resulting in the dynamic concentration shift of the exciton level

Chromophore-Dependent Intramolecular Exciton-Vibrational Coupling in the FMO Complex: Quantification and Importance for Exciton Dynamics.

Science.gov (United States)

Padula, Daniele; Lee, Myeong H; Claridge, Kirsten; Troisi, Alessandro

2017-11-02

In this paper, we adopt an approach suitable for monitoring the time evolution of the intramolecular contribution to the spectral density of a set of identical chromophores embedded in their respective environments. We apply the proposed method to the Fenna-Matthews-Olson (FMO) complex, with the objective to quantify the differences among site-dependent spectral densities and the impact of such differences on the exciton dynamics of the system. Our approach takes advantage of the vertical gradient approximation to reduce the computational demands of the normal modes analysis. We show that the region of the spectral density that is believed to strongly influence the exciton dynamics changes significantly in the timescale of tens of nanoseconds. We then studied the impact of the intramolecular vibrations on the exciton dynamics by considering a model of FMO in a vibronic basis and neglecting the interaction with the environment to isolate the role of the intramolecular exciton-vibration coupling. In agreement with the assumptions in the literature, we demonstrate that high frequency modes at energy much larger than the excitonic energy splitting have negligible influence on exciton dynamics despite the large exciton-vibration coupling. We also find that the impact of including the site-dependent spectral densities on exciton dynamics is not very significant, indicating that it may be acceptable to apply the same spectral density on all sites. However, care needs to be taken for the description of the exciton-vibrational coupling in the low frequency part of intramolecular modes because exciton dynamics is more susceptible to low frequency modes despite their small Huang-Rhys factors.

Charge Carrier Generation Followed by Triplet State Formation, Annihilation, and Carrier Recreation in PBDTTT-C:PC 60 BM Photovoltaic Blends

KAUST Repository

Gehrig, Dominik W.

2015-05-22

Triplet state formation after photoexcitation of low-bandgap polymer:fullerene blends has recently been demonstrated, however, the precise mechanism and its impact on solar cell performance is still under debate. Here, we study exciton dissociation, charge carrier generation and triplet state formation in low-bandgap polymer PBDTTT-C:PC60BM bulk heterojunction photovoltaic blends by a combination of fs-µs broadband Vis-NIR transient absorption (TA) pump-probe spectroscopy and multivariate curve resolution (MCR) data analysis. We found sub-ps exciton dissociation and charge generation followed by sub-ns triplet state creation. The carrier dynamics and triplet state dynamics exhibited a very pronounced intensity dependence indicating non-geminate recombination of free carriers is the origin of triplet formation in these blends. Triplets were found to be the dominant state present on the nanosecond timescale. Surprisingly, the carrier population increased again on the ns-µs timescale. We attribute this to triplet-triplet annihilation and the formation of higher energy excited states that subsequently underwent charge transfer. This unique dip and recovery of the charge population is a clear indication that triplets are formed by non-geminate recombination, as such a kinetic is incompatible with a monomolecular triplet state formation process.

Charge Carrier Generation Followed by Triplet State Formation, Annihilation, and Carrier Recreation in PBDTTT-C:PC 60 BM Photovoltaic Blends

KAUST Repository

Gehrig, Dominik W.; Howard, Ian A.; Laquai, Fré dé ric

2015-01-01

Triplet state formation after photoexcitation of low-bandgap polymer:fullerene blends has recently been demonstrated, however, the precise mechanism and its impact on solar cell performance is still under debate. Here, we study exciton dissociation, charge carrier generation and triplet state formation in low-bandgap polymer PBDTTT-C:PC60BM bulk heterojunction photovoltaic blends by a combination of fs-µs broadband Vis-NIR transient absorption (TA) pump-probe spectroscopy and multivariate curve resolution (MCR) data analysis. We found sub-ps exciton dissociation and charge generation followed by sub-ns triplet state creation. The carrier dynamics and triplet state dynamics exhibited a very pronounced intensity dependence indicating non-geminate recombination of free carriers is the origin of triplet formation in these blends. Triplets were found to be the dominant state present on the nanosecond timescale. Surprisingly, the carrier population increased again on the ns-µs timescale. We attribute this to triplet-triplet annihilation and the formation of higher energy excited states that subsequently underwent charge transfer. This unique dip and recovery of the charge population is a clear indication that triplets are formed by non-geminate recombination, as such a kinetic is incompatible with a monomolecular triplet state formation process.

Spatially indirect excitons in coupled quantum wells

Energy Technology Data Exchange (ETDEWEB)

Lai, Chih-Wei Eddy [Univ. of California, Berkeley, CA (United States)

2004-03-01

Microscopic quantum phenomena such as interference or phase coherence between different quantum states are rarely manifest in macroscopic systems due to a lack of significant correlation between different states. An exciton system is one candidate for observation of possible quantum collective effects. In the dilute limit, excitons in semiconductors behave as bosons and are expected to undergo Bose-Einstein condensation (BEC) at a temperature several orders of magnitude higher than for atomic BEC because of their light mass. Furthermore, well-developed modern semiconductor technologies offer flexible manipulations of an exciton system. Realization of BEC in solid-state systems can thus provide new opportunities for macroscopic quantum coherence research. In semiconductor coupled quantum wells (CQW) under across-well static electric field, excitons exist as separately confined electron-hole pairs. These spatially indirect excitons exhibit a radiative recombination time much longer than their thermal relaxation time a unique feature in direct band gap semiconductor based structures. Their mutual repulsive dipole interaction further stabilizes the exciton system at low temperature and screens in-plane disorder more effectively. All these features make indirect excitons in CQW a promising system to search for quantum collective effects. Properties of indirect excitons in CQW have been analyzed and investigated extensively. The experimental results based on time-integrated or time-resolved spatially-resolved photoluminescence (PL) spectroscopy and imaging are reported in two categories. (i) Generic indirect exciton systems: general properties of indirect excitons such as the dependence of exciton energy and lifetime on electric fields and densities were examined. (ii) Quasi-two-dimensional confined exciton systems: highly statistically degenerate exciton systems containing more than tens of thousands of excitons within areas as small as (10 micrometer)² were

Multiple exciton generation in quantum dot-based solar cells

Science.gov (United States)

Goodwin, Heather; Jellicoe, Tom C.; Davis, Nathaniel J. L. K.; Böhm, Marcus L.

2018-01-01

Multiple exciton generation (MEG) in quantum-confined semiconductors is the process by which multiple bound charge-carrier pairs are generated after absorption of a single high-energy photon. Such charge-carrier multiplication effects have been highlighted as particularly beneficial for solar cells where they have the potential to increase the photocurrent significantly. Indeed, recent research efforts have proved that more than one charge-carrier pair per incident solar photon can be extracted in photovoltaic devices incorporating quantum-confined semiconductors. While these proof-of-concept applications underline the potential of MEG in solar cells, the impact of the carrier multiplication effect on the device performance remains rather low. This review covers recent advancements in the understanding and application of MEG as a photocurrent-enhancing mechanism in quantum dot-based photovoltaics.

Charge transfer and excitation in high-energy ion-atom collisions

International Nuclear Information System (INIS)

Schlachter, A.S.; Berkner, K.H.; McDonald, R.J.

1986-11-01

Coincidence measurements of charge transfer and simultaneous projectile electron excitation provide insight into correlated two-electron processes in energetic ion-atom collisions. Projectile excitation and electron capture can occur simultaneously in a collision of a highly charged ion with a target atom; this process is called resonant transfer and excitation (RTE). The intermediate excited state which is thus formed can subsequently decay by photon emission or by Auger-electron emission. Results are shown for RTE in both the K shell of Ca ions and the L shell of Nb ions, for simultaneous projectile electron loss and excitation, and for the effect of RTE on electron capture

Excitonic pathway to photoinduced magnetism in colloidal nanocrystals with nonmagnetic dopants.

Science.gov (United States)

Pinchetti, Valerio; Di, Qiumei; Lorenzon, Monica; Camellini, Andrea; Fasoli, Mauro; Zavelani-Rossi, Margherita; Meinardi, Francesco; Zhang, Jiatao; Crooker, Scott A; Brovelli, Sergio

2018-02-01

Electronic doping of colloidal semiconductor nanostructures holds promise for future device concepts in optoelectronic and spin-based technologies. Ag + is an emerging electronic dopant in III-V and II-VI nanostructures, introducing intragap electronic states optically coupled to the host conduction band. With its full 4d shell Ag + is nonmagnetic, and the dopant-related luminescence is ascribed to decay of the conduction-band electron following transfer of the photoexcited hole to Ag + . This optical activation process and the associated modification of the electronic configuration of Ag + remain unclear. Here, we trace a comprehensive picture of the excitonic process in Ag-doped CdSe nanocrystals and demonstrate that, in contrast to expectations, capture of the photohole leads to conversion of Ag + to paramagnetic Ag 2+ . The process of exciton recombination is thus inextricably tied to photoinduced magnetism. Accordingly, we observe strong optically activated magnetism and diluted magnetic semiconductor behaviour, demonstrating that optically switchable magnetic nanomaterials can be obtained by exploiting excitonic processes involving nonmagnetic impurities.

Radiative charge-transfer lifetime of the excited state of (NaCa)+

International Nuclear Information System (INIS)

Makarov, Oleg P.; Cote, R.; Michels, H.; Smith, W.W.

2003-01-01

New experiments were proposed recently to investigate the regime of cold atomic and molecular ion-atom collision processes in a special hybrid neutral-atom-ion trap under high-vacuum conditions. We study the collisional cooling of laser precooled Ca + ions by ultracold Na atoms. Modeling this process requires knowledge of the radiative lifetime of the excited singlet A 1 Σ + state of the (NaCa) + molecular system. We calculate the rate coefficient for radiative charge transfer using a semiclassical approach. The dipole radial matrix elements between the ground and the excited states, and the potential curves were calculated using complete active space self-consistent field and Moeller-Plesset second-order perturbation theory with an extended Gaussian basis, 6-311+G (3df). The semiclassical charge-transfer rate coefficient was averaged over a thermal Maxwellian distribution. In addition, we also present elastic collision cross sections and the spin-exchange cross section. The rate coefficient for charge transfer was found to be 2.3x10 -16 cm 3 /sec, while those for the elastic and spin-exchange cross sections were found to be several orders of magnitude higher (1.1x10 -8 cm 3 /sec and 2.3x10 -9 cm 3 /sec, respectively). This confirms our assumption that the milli-Kelvin regime of collisional cooling of calcium ions by sodium atoms is favorable with the respect to low loss of calcium ions due to the charge transfer

Charge transfer excitations from excited state Hartree-Fock subsequent minimization scheme

International Nuclear Information System (INIS)

Theophilou, Iris; Tassi, M.; Thanos, S.

2014-01-01

Photoinduced charge-transfer processes play a key role for novel photovoltaic phenomena and devices. Thus, the development of ab initio methods that allow for an accurate and computationally inexpensive treatment of charge-transfer excitations is a topic that nowadays attracts a lot of scientific attention. In this paper we extend an approach recently introduced for the description of single and double excitations [M. Tassi, I. Theophilou, and S. Thanos, Int. J. Quantum Chem. 113, 690 (2013); M. Tassi, I. Theophilou, and S. Thanos, J. Chem. Phys. 138, 124107 (2013)] to allow for the description of intermolecular charge-transfer excitations. We describe an excitation where an electron is transferred from a donor system to an acceptor one, keeping the excited state orthogonal to the ground state and avoiding variational collapse. These conditions are achieved by decomposing the space spanned by the Hartree-Fock (HF) ground state orbitals into four subspaces: The subspace spanned by the occupied orbitals that are localized in the region of the donor molecule, the corresponding for the acceptor ones and two more subspaces containing the virtual orbitals that are localized in the neighborhood of the donor and the acceptor, respectively. Next, we create a Slater determinant with a hole in the subspace of occupied orbitals of the donor and a particle in the virtual subspace of the acceptor. Subsequently we optimize both the hole and the particle by minimizing the HF energy functional in the corresponding subspaces. Finally, we test our approach by calculating the lowest charge-transfer excitation energies for a set of tetracyanoethylene-hydrocarbon complexes that have been used earlier as a test set for such kind of excitations

Phase Diagram of the Bose Condensation of Interwell Excitons in GaAs/AlGaAs Double Quantum Wells

DEFF Research Database (Denmark)

Dremin, A. A.; Timofeev, V. B.; Larionov, A. V.

2002-01-01

The luminescence of interwell excitons in GaAs/AlGaAs double quantum wells (n–i–n heterostructures) with large-scale fluctuations of random potential in the heteroboundary planes was studied at low temperatures down to 0.5 K. The properties of excitons whose photoexcited electron and hole...... was coated with a metal mask containing special openings (windows) of a micron size or smaller. Both photoexcitation and observation of luminescence were performed through these windows by the fiber optic technique. At low pumping powers, the interwell excitons were strongly localized because of the residual...... charged impurities, and the corresponding photoluminescence line was nonuniformly broadened. As the laser excitation power increased, a narrow line due to delocalized excitons arose in a threshold-like manner, after which its intensity rapidly increased with growing pumping and the line itself narrowed...

Incorporation of charge transfer into the explicit polarization fragment method by grand canonical density functional theory.

Science.gov (United States)

Isegawa, Miho; Gao, Jiali; Truhlar, Donald G

2011-08-28

Molecular fragmentation algorithms provide a powerful approach to extending electronic structure methods to very large systems. Here we present a method for including charge transfer between molecular fragments in the explicit polarization (X-Pol) fragment method for calculating potential energy surfaces. In the conventional X-Pol method, the total charge of each fragment is preserved, and charge transfer between fragments is not allowed. The description of charge transfer is made possible by treating each fragment as an open system with respect to the number of electrons. To achieve this, we applied Mermin's finite temperature method to the X-Pol wave function. In the application of this method to X-Pol, the fragments are open systems that partially equilibrate their number of electrons through a quasithermodynamics electron reservoir. The number of electrons in a given fragment can take a fractional value, and the electrons of each fragment obey the Fermi-Dirac distribution. The equilibrium state for the electrons is determined by electronegativity equalization with conservation of the total number of electrons. The amount of charge transfer is controlled by re-interpreting the temperature parameter in the Fermi-Dirac distribution function as a coupling strength parameter. We determined this coupling parameter so as to reproduce the charge transfer energy obtained by block localized energy decomposition analysis. We apply the new method to ten systems, and we show that it can yield reasonable approximations to potential energy profiles, to charge transfer stabilization energies, and to the direction and amount of charge transferred. © 2011 American Institute of Physics

Positronium Inhibition and Quenching by Organic Electron Acceptors and Charge Transfer Complexes

DEFF Research Database (Denmark)

Jansen, P.; Eldrup, Morten Mostgaard; Jensen, Bror Skytte

1975-01-01

Positron lifetime measurements were performed on a series of organic electron acceptors and charge-transfer complexes in solution. The acceptors cause both positronium (Ps) inhibition (with maybe one exception) and quenching, but when an acceptor takes part in a charge-transfer complex...... in terms of the spur reaction model of Ps formation. Correlation was also made to gas phase reaction between electron acceptors and free electron, as well as to pulse radiolysis data....

Barrier discharge. The transferred charge and ozone synthesis

International Nuclear Information System (INIS)

Gibalov, V.I.; Samoilovich, V.G.

1991-01-01

We have undertaken an experimental investigation of the influence of the conditions of barrier discharge implementation such as: the discharge gap value, the type of gas, and the polarity and dielectric permittivity of the dielectric electrode on the value of charge transferred in a micro-discharge. It is shown that the increase in the specific capacitance of the electrodes leads to proportional increase in the transferred charge value, reaching 100-200 nC in a discharge gap 1 mm, in air. In this case the amplitude and duration of a current pulse in the microdischarge reach, respectively, 10 to 15 A and 40 ns. It is also demonstrated that in air with increase in the discharge gap value one can observe a decrease in the efficiency of the ozone synthesis whereas in oxygen there exists a more complicated dependence: the maximum of efficiency is observed at a discharge gap value of 0.7 to 1.0 mm. (orig.)

Long-range energy transfer in self-assembled quantum dot-DNA cascades

Science.gov (United States)

Goodman, Samuel M.; Siu, Albert; Singh, Vivek; Nagpal, Prashant

2015-11-01

The size-dependent energy bandgaps of semiconductor nanocrystals or quantum dots (QDs) can be utilized in converting broadband incident radiation efficiently into electric current by cascade energy transfer (ET) between layers of different sized quantum dots, followed by charge dissociation and transport in the bottom layer. Self-assembling such cascade structures with angstrom-scale spatial precision is important for building realistic devices, and DNA-based QD self-assembly can provide an important alternative. Here we show long-range Dexter energy transfer in QD-DNA self-assembled single constructs and ensemble devices. Using photoluminescence, scanning tunneling spectroscopy, current-sensing AFM measurements in single QD-DNA cascade constructs, and temperature-dependent ensemble devices using TiO2 nanotubes, we show that Dexter energy transfer, likely mediated by the exciton-shelves formed in these QD-DNA self-assembled structures, can be used for efficient transport of energy across QD-DNA thin films.The size-dependent energy bandgaps of semiconductor nanocrystals or quantum dots (QDs) can be utilized in converting broadband incident radiation efficiently into electric current by cascade energy transfer (ET) between layers of different sized quantum dots, followed by charge dissociation and transport in the bottom layer. Self-assembling such cascade structures with angstrom-scale spatial precision is important for building realistic devices, and DNA-based QD self-assembly can provide an important alternative. Here we show long-range Dexter energy transfer in QD-DNA self-assembled single constructs and ensemble devices. Using photoluminescence, scanning tunneling spectroscopy, current-sensing AFM measurements in single QD-DNA cascade constructs, and temperature-dependent ensemble devices using TiO2 nanotubes, we show that Dexter energy transfer, likely mediated by the exciton-shelves formed in these QD-DNA self-assembled structures, can be used for efficient

Photo-reactive charge trapping memory based on lanthanide complex

Science.gov (United States)

Zhuang, Jiaqing; Lo, Wai-Sum; Zhou, Li; Sun, Qi-Jun; Chan, Chi-Fai; Zhou, Ye; Han, Su-Ting; Yan, Yan; Wong, Wing-Tak; Wong, Ka-Leung; Roy, V. A. L.

2015-10-01

Traditional utilization of photo-induced excitons is popularly but restricted in the fields of photovoltaic devices as well as photodetectors, and efforts on broadening its function have always been attempted. However, rare reports are available on organic field effect transistor (OFET) memory employing photo-induced charges. Here, we demonstrate an OFET memory containing a novel organic lanthanide complex Eu(tta)3ppta (Eu(tta)3 = Europium(III) thenoyltrifluoroacetonate, ppta = 2-phenyl-4,6-bis(pyrazol-1-yl)-1,3,5-triazine), in which the photo-induced charges can be successfully trapped and detrapped. The luminescent complex emits intense red emission upon ultraviolet (UV) light excitation and serves as a trapping element of holes injected from the pentacene semiconductor layer. Memory window can be significantly enlarged by light-assisted programming and erasing procedures, during which the photo-induced excitons in the semiconductor layer are separated by voltage bias. The enhancement of memory window is attributed to the increasing number of photo-induced excitons by the UV light. The charges are stored in this luminescent complex for at least 104 s after withdrawing voltage bias. The present study on photo-assisted novel memory may motivate the research on a new type of light tunable charge trapping photo-reactive memory devices.

Changes in wetting and contact charge transfer by femtosecond laser-ablation of polyimide

Energy Technology Data Exchange (ETDEWEB)

Guo, X.D., E-mail: xiaodong.guo@uib.no [Department of Physics and Technology, Allegaten 55, 5020 Bergen, University of Bergen (Norway); Dai, Y.; Gong, M. [Department of Physics, Shanghai 200444, Shanghai University (China); Qu, Y.G. [Center for Geobiology, Allegaten 41, 5020 Bergen, University of Bergen (Norway); Helseth, L.E. [Department of Physics and Technology, Allegaten 55, 5020 Bergen, University of Bergen (Norway)

2015-09-15

Highlights: • Laser ablation significantly reduced the triboelectric charging of polyimide films. • Hierarchical micro/nanostructures formed on the surface of the sample. • Structural anisotropy leads to spatially varying contact angles of water droplets. • Raman spectroscopy revealed a carbonization of the polyimide sample. • The corresponding loss of insulation may explain the reduction of charge transfer. - Abstract: In this study it is demonstrated that the triboelectric charging of polyimide thin films is significantly reduced by using a femtosecond laser to nanostructure its. It is found that the contact charge transfer between laser-ablated Kapton and aluminum is almost negligible, and even much lower than the significant current occurring when non-treated Kapton touches the metal. Scanning electron microscopy demonstrates that laser ablation produces a hierarchical micro and nanostructure, and it is found that the structural anisotropy leads to spatially varying contact angles of water droplets residing on the surface. Raman spectra suggest that the centers of the laser-ablated tracks are carbonized; therefore, the loss of insulation can be responsible for the reduction of charge transfer.

Polarized electrons, trions, and nuclei in charged quantum dots

Science.gov (United States)

Bracker, A. S.; Tischler, J. G.; Korenev, V. L.; Gammon, D.

2003-07-01

We have investigated spin polarization in GaAs quantum dots. Excitons and trions are polarized directly by optical excitation and studied through polarization of photoluminescence. Electrons and nuclei are polarized indirectly through subsequent relaxation processes. Polarized electrons are identified by the Hanle effect for exciton and trion photoluminescence, while polarized nuclei are identified through the Overhauser effect in individual charged quantum dots.

A comparative theoretical study of exciton-dissociation and charge-recombination processes in oligothiophene/fullerene and oligothiophene/perylenediimide complexes for organic solar cells

KAUST Repository

Yi, Yuanping; Coropceanu, Veaceslav; Bré das, Jean-Luc

2011-01-01

) is faster than that in the fullerene-based devices and (ii) in most cases, can compete with the dissociation of the charge-transfer state into mobile charge carriers. This faster charge-recombination process is consistent with the lower performance observed

Roles of binding energy and diffusion length of singlet and triplet excitons in organic heterojunction solar cells

International Nuclear Information System (INIS)

Narayan, Monishka Rita; Singh, Jai

2012-01-01

The influence of binding energy and diffusion length on the dissociation of excitons in organic solids is studied. The binding energy and excitonic Bohr radius of singlet and triplet excitons are calculated and compared using the dissociation energy of 0.3 eV, which is provided by the lowest unoccupied molecular orbital offset in heterojunction organic solar cells. A relation between the diffusion coefficient and diffusion length of singlet and triplet excitons is derived using the Foerster and Dexter transfer processes and are plotted as a function of the donor-acceptor separation. The diffusion length reduces nearly to a zero if the distance between donor and acceptor is increased to more than 1.5 nm. It is found that the donor-acceptor separation needs to be ≤ 1.5 nm for easy dissociation on singlet excitons leading to better conversion efficiency in heterojunction organic solar cells. (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Roles of binding energy and diffusion length of singlet and triplet excitons in organic heterojunction solar cells

Energy Technology Data Exchange (ETDEWEB)

Narayan, Monishka Rita [Centre for Renewable Energy and Low Emission Technology, Charles Darwin University, Darwin, NT 0909 (Australia); Singh, Jai [School of Engineering and IT, Charles Darwin University, Darwin, NT 0909 (Australia)

2012-12-15

The influence of binding energy and diffusion length on the dissociation of excitons in organic solids is studied. The binding energy and excitonic Bohr radius of singlet and triplet excitons are calculated and compared using the dissociation energy of 0.3 eV, which is provided by the lowest unoccupied molecular orbital offset in heterojunction organic solar cells. A relation between the diffusion coefficient and diffusion length of singlet and triplet excitons is derived using the Foerster and Dexter transfer processes and are plotted as a function of the donor-acceptor separation. The diffusion length reduces nearly to a zero if the distance between donor and acceptor is increased to more than 1.5 nm. It is found that the donor-acceptor separation needs to be {<=} 1.5 nm for easy dissociation on singlet excitons leading to better conversion efficiency in heterojunction organic solar cells. (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Competition between electronic energy transfer and relaxation in Xe doped Ar and Ne matrices studied by photoelectron spectroscopy

International Nuclear Information System (INIS)

Schwentner, N.; Koch, E.E.

1976-01-01

Thin films of solid Ar and Ne doped with 1% Xe were excited with photons in the energy range from 10 eV to 20 eV in order to measure the energy distribution of the emitted electrons. Binding energies of th host and guest levels are deduced. When host excitons are excited, strong emission of electrons is observed indicating an efficient transfer of the host exciton energy to the Xe guest atoms. The energy of the free excitons is transferred, as can be deduced from the kinetic energy of the photoemitted electrons, rather than the energy of the bound (self-trapped) excitons which are observed in luminescence experiments. Furthermore, there is a striking difference between the Ar and the Ne matrix: In the Ne matrix a fast relaxation from the n = 2 to the n = 1 state was observed and only the energy of the n = 1 exciton is transferred even when higher excitons are excited, in contrast to Ar, where the transferred energy is higher for excitation of the n = 2 excitons than for n = 1. From these observations, time hierarchies for the competition between electronic energy transfer and relaxation are deduced. (orig.) [de

Visualization of Excitonic Structure in the Fenna-Matthews-Olson Photosynthetic Complex by Polarization-Dependent Two-Dimensional Electronic Spectroscopy

International Nuclear Information System (INIS)

Fleming, Graham; Read, Elizabeth L.; Schlau-Cohen, Gabriela S.; Engel, Gregory S.; Wen, Jianzhong; Blankenship, Robert E.; Fleming, Graham R.

2008-01-01

Photosynthetic light-harvesting proceeds by the collection and highly efficient transfer of energy through a network of pigment-protein complexes. Inter-chromophore electronic couplings and interactions between pigments and the surrounding protein determine energy levels of excitonic states and dictate the mechanism of energy flow. The excitonic structure (orientation of excitonic transition dipoles) of pigment-protein complexes is generally deduced indirectly from x-ray crystallography in combination with predictions of transition energies and couplings in the chromophore site basis. Here, we demonstrate that coarse-grained excitonic structural information in the form of projection angles between transition dipole moments can be obtained from polarization-dependent two-dimensional electronic spectroscopy of an isotropic sample, particularly when the nonrephasing or free polarization decay signal rather than the photon echo signal is considered. The method provides an experimental link between atomic and electronic structure and accesses dynamical information with femtosecond time resolution. In an investigation of the Fenna-Matthews-Olson complex from green sulfur bacteria, energy transfer connecting two particular exciton states in the protein is isolated as being the primary contributor to a cross peak in the nonrephasing 2D spectrum at 400 fs under a specific sequence of polarized excitation pulses. The results suggest the possibility of designing experiments using combinations of tailored polarization sequences to separate and monitor individual relaxation pathways

Biexciton formation and exciton coherent coupling in layered GaSe

Science.gov (United States)

Dey, P.; Paul, J.; Moody, G.; Stevens, C. E.; Glikin, N.; Kovalyuk, Z. D.; Kudrynskyi, Z. R.; Romero, A. H.; Cantarero, A.; Hilton, D. J.; Karaiskaj, D.

2015-06-01

Nonlinear two-dimensional Fourier transform (2DFT) and linear absorption spectroscopy are used to study the electronic structure and optical properties of excitons in the layered semiconductor GaSe. At the 1s exciton resonance, two peaks are identified in the absorption spectra, which are assigned to splitting of the exciton ground state into the triplet and singlet states. 2DFT spectra acquired for co-linear polarization of the excitation pulses feature an additional peak originating from coherent energy transfer between the singlet and triplet. At cross-linear polarization of the excitation pulses, the 2DFT spectra expose a new peak likely originating from bound biexcitons. The polarization dependent 2DFT spectra are well reproduced by simulations using the optical Bloch equations for a four level system, where many-body effects are included phenomenologically. Although biexciton effects are thought to be strong in this material, only moderate contributions from bound biexciton creation can be observed. The biexciton binding energy of ˜2 meV was estimated from the separation of the peaks in the 2DFT spectra. Temperature dependent absorption and 2DFT measurements, combined with "ab initio" theoretical calculations of the phonon spectra, indicate strong interaction with the A1 ' phonon mode. Excitation density dependent 2DFT measurements reveal excitation induced dephasing and provide a lower limit for the homogeneous linewidth of the excitons in the present GaSe crystal.

Lithium-modulated conduction band edge shifts and charge-transfer dynamics in dye-sensitized solar cells based on a dicyanamide ionic liquid.

Science.gov (United States)

Bai, Yu; Zhang, Jing; Wang, Yinghui; Zhang, Min; Wang, Peng

2011-04-19

Lithium ions are known for their potent function in modulating the energy alignment at the oxide semiconductor/dye/electrolyte interface in dye-sensitized solar cells (DSCs), offering the opportunity to control the associated multichannel charge-transfer dynamics. Herein, by optimizing the lithium iodide content in 1-ethyl-3-methylimidazolium dicyanamide-based ionic liquid electrolytes, we present a solvent-free DSC displaying an impressive 8.4% efficiency at 100 mW cm(-2) AM1.5G conditions. We further scrutinize the origins of evident impacts of lithium ions upon current density-voltage characteristics as well as photocurrent action spectra of DSCs based thereon. It is found that, along with a gradual increase of the lithium content in ionic liquid electrolytes, a consecutive diminishment of the open-circuit photovoltage arises, primarily owing to a noticeable downward movement of the titania conduction band edge. The conduction band edge displacement away from vacuum also assists the formation of a more favorable energy offset at the titania/dye interface, and thereby leads to a faster electron injection rate and a higher exciton dissociation yield as implied by transient emission measurements. We also notice that the adverse influence of the titania conduction band edge downward shift arising from lithium addition upon photovoltage is partly compensated by a concomitant suppression of the triiodide involving interfacial charge recombination. © 2011 American Chemical Society

Ultrafast Photoinduced Electron Transfer in Bimolecular Donor-Acceptor Systems

KAUST Repository

Alsulami, Qana A.

2016-11-30

The efficiency of photoconversion systems, such as organic photovoltaic (OPV) cells, is largely controlled by a series of fundamental photophysical processes occurring at the interface before carrier collection. A profound understanding of ultrafast interfacial charge transfer (CT), charge separation (CS), and charge recombination (CR) is the key determinant to improving the overall performances of photovoltaic devices. The discussion in this dissertation primarily focuses on the relevant parameters that are involved in photon absorption, exciton separation, carrier transport, carrier recombination and carrier collection in organic photovoltaic devices. A combination of steady-state and femtosecond broadband transient spectroscopies was used to investigate the photoinduced charge carrier dynamics in various donor-acceptor systems. Furthermore, this study was extended to investigate some important factors that influence charge transfer in donor-acceptor systems, such as the morphology, energy band alignment, electronic properties and chemical structure. Interestingly, clear correlations among the steady-state measurements, time-resolved spectroscopy results, grain alignment of the electron transporting layer (ETL), carrier mobility, and device performance are found. In this thesis, we explored the significant impacts of ultrafast charge separation and charge recombination at donor/acceptor (D/A) interfaces on the performance of a conjugated polymer PTB7-Th device with three fullerene acceptors: PC71BM, PC61BM and IC60BA. Time-resolved laser spectroscopy and high-resolution electron microscopy can illustrate the basis for fabricating solar cell devices with improved performances. In addition, we studied the effects of the incorporation of heavy metals into π-conjugated chromophores on electron transfer by monitoring the triplet state lifetime of the oligomer using transient absorption spectroscopy, as understanding the mechanisms controlling intersystem crossing and

Luminescence and optical spectroscopy of charge transfer processes in solid solutions Ni{sub C}Mg{sub 1−C}O and Ni{sub x}Zn{sub 1−x}O

Energy Technology Data Exchange (ETDEWEB)

Sokolov, V.I., E-mail: visokolov@imp.uran.ru [Institute of Metal Physics, Russian Academy of Science, Ural Branch, S. Kovalevskaya Street 18, 620990 Yekaterinburg (Russian Federation); Pustovarov, V.A.; Churmanov, V.N. [Ural Federal University, Mira Street 19, 620002 Yekaterinburg (Russian Federation); Gruzdev, N.B.; Uimin, M.A.; Byzov, I.V.; Druzhinin, A.V. [Institute of Metal Physics, Russian Academy of Science, Ural Branch, S. Kovalevskaya Street 18, 620990 Yekaterinburg (Russian Federation); Mironova-Ulmane, N.A. [Institute of Solid State Physics, University of Latvia, Kengaraga Street 8, LV-1063 Riga (Latvia)

2016-01-15

In this work photoluminescence spectra for Ni{sub c}Mg{sub 1−c}O and Ni{sub x}Zn{sub 1−x}O solid solutions with the rock-salt crystal structure were obtained under synchrotron radiation excitation. Periodical peaks in the photoluminescence excitation spectrum of Ni{sub c}Mg{sub 1−c}O (c=0.008) have been discovered for a wide-gap oxide doped with 3d impurities for the first time. They can be considered as LO phonon repetitions of the narrow zero phonon line resulted from the optical transitions into the p–d charge transfer exciton [d{sup 9}h] state. A close coincidence in energy of different peculiarities in the optical absorption and photoluminescence excitation spectra for the Ni{sub c}Mg{sub 1−c}O and Ni{sub x}Zn{sub 1−x}O solid solutions is due to the practically equal interatomic distances Ni–O in the investigated materials. The bulk of new experimental results is the trustworthy evidence that only the p–d charge transfer transitions manifest themselves in the spectral region of 3.5–6.5 eV. - Highlights: • Emission of Ni{sub c}Mg{sub 1−c}O nanocystals excited by synchrotron radiation is obtained. • LO phonon repetitions have been observed in PLE spectra of Ni{sub c}Mg{sub 1−c}O firstly for wide gap oxide materials doped with 3d impurities. • The [d{sup 9}h] acceptor exciton state in Ni{sub c}Mg{sub 1−c}O (c=0.008) are indirectly revealed. • The begin of PLE spectra of Ni{sub x}Zn{sub 1−x}O are not virtually shifted with a change of composition x. • The near energy coincidence of absorption peaks for nanocrystals NiO and single crystal Ni{sub c}Mg{sub 1−c}O (c=0.0006) manifests itself.

Optical pumping and negative luminescence polarization in charged GaAs quantum dots

Science.gov (United States)

Shabaev, Andrew; Stinaff, Eric A.; Bracker, Allan S.; Gammon, Daniel; Efros, Alexander L.; Korenev, Vladimir L.; Merkulov, Igor

2009-01-01

Optical pumping of electron spins and negative photoluminescence polarization are observed when interface quantum dots in a GaAs quantum well are excited nonresonantly by circularly polarized light. Both observations can be explained by the formation of long-lived dark excitons through hole spin relaxation in the GaAs quantum well prior to exciton capture. In this model, optical pumping of resident electron spins is caused by capture of dark excitons and recombination in charged quantum dots. Negative polarization results from accumulation of dark excitons in the quantum well and is enhanced by optical pumping. The dark exciton model describes the experimental results very well, including intensity and bias dependence of the photoluminescence polarization and the Hanle effect.

Charge-Transfer Complexes Studied by Dynamic Force Spectroscopy

Directory of Open Access Journals (Sweden)

Jurriaan Huskens

2013-03-01

Full Text Available In this paper, the strength and kinetics of two charge-transfer complexes, naphthol-methylviologen and pyrene-methylviologen, are studied using dynamic force spectroscopy. The dissociation rates indicate an enhanced stability of the pyrene-methylviologen complex, which agrees with its higher thermodynamic stability compared to naphthol-methylviologen complex.

Energy transfer mechanisms in layered 2D perovskites.

Science.gov (United States)

Williams, Olivia F; Guo, Zhenkun; Hu, Jun; Yan, Liang; You, Wei; Moran, Andrew M

2018-04-07

Two-dimensional (2D) perovskite quantum wells are generating broad scientific interest because of their potential for use in optoelectronic devices. Recently, it has been shown that layers of 2D perovskites can be grown in which the average thicknesses of the quantum wells increase from the back to the front of the film. This geometry carries implications for light harvesting applications because the bandgap of a quantum well decreases as its thickness increases. The general structural formula for the 2D perovskite systems under investigation in this work is (PEA) 2 (MA) n-1 [Pb n I 3n+1 ] (PEA = phenethyl ammonium, MA = methyl ammonium). Here, we examine two layered 2D perovskites with different distributions of quantum well thicknesses. Spectroscopic measurements and model calculations suggest that both systems funnel electronic excitations from the back to the front of the film through energy transfer mechanisms on the time scales of 100's of ps (i.e., energy transfer from thinner to thicker quantum wells). In addition, the model calculations demonstrate that the transient absorption spectra are composed of a progression of single exciton and biexciton resonances associated with the individual quantum wells. We find that exciton dissociation and/or charge transport dynamics make only minor contributions to the transient absorption spectra within the first 1 ns after photo-excitation. An analysis of the energy transfer kinetics indicates that the transitions occur primarily between quantum wells with values of n that differ by 1 because of the spectral overlap factor that governs the energy transfer rate. Two-dimensional transient absorption spectra reveal a pattern of resonances consistent with the dominance of sequential energy transfer dynamics.

Energy transfer mechanisms in layered 2D perovskites

Science.gov (United States)

Williams, Olivia F.; Guo, Zhenkun; Hu, Jun; Yan, Liang; You, Wei; Moran, Andrew M.

2018-04-01

Two-dimensional (2D) perovskite quantum wells are generating broad scientific interest because of their potential for use in optoelectronic devices. Recently, it has been shown that layers of 2D perovskites can be grown in which the average thicknesses of the quantum wells increase from the back to the front of the film. This geometry carries implications for light harvesting applications because the bandgap of a quantum well decreases as its thickness increases. The general structural formula for the 2D perovskite systems under investigation in this work is (PEA)2(MA)n-1[PbnI3n+1] (PEA = phenethyl ammonium, MA = methyl ammonium). Here, we examine two layered 2D perovskites with different distributions of quantum well thicknesses. Spectroscopic measurements and model calculations suggest that both systems funnel electronic excitations from the back to the front of the film through energy transfer mechanisms on the time scales of 100's of ps (i.e., energy transfer from thinner to thicker quantum wells). In addition, the model calculations demonstrate that the transient absorption spectra are composed of a progression of single exciton and biexciton resonances associated with the individual quantum wells. We find that exciton dissociation and/or charge transport dynamics make only minor contributions to the transient absorption spectra within the first 1 ns after photo-excitation. An analysis of the energy transfer kinetics indicates that the transitions occur primarily between quantum wells with values of n that differ by 1 because of the spectral overlap factor that governs the energy transfer rate. Two-dimensional transient absorption spectra reveal a pattern of resonances consistent with the dominance of sequential energy transfer dynamics.

Charge transfer in conjugated oligomers encapsulated into carbon nanotubes

Energy Technology Data Exchange (ETDEWEB)

Almadori, Y.; Alvarez, L.; Michel, T.; Le Parc, R.; Bantignies, J.L.; Hermet, P.; Sauvajol, J.L. [Laboratoire Charles Coulomb UMR 5521, Universite Montpellier 2, 34095 Montpellier (France); Laboratoire Charles Coulomb UMR 5521, CNRS, 34095 Montpellier (France); Arenal, R. [Laboratoire d' Etude des Microstructures, CNRS-ONERA, 92322 Chatillon (France); Laboratorio de Microscopias Avanzadas, Instituto de Nanociencia de Aragon, U. Zaragoza, 50018 Zaragoza (Spain); Babaa, R. [Laboratoire de Chimie des Surfaces et Interfaces, CEA, IRAMIS, SPCSI, 91191 Gif-sur-Yvette Cedex (France); Chemical Engineering Department, University of Technology PETRONAS, UTP, Ipoh-Perak (Malaysia); Jouselme, B.; Palacin, S. [Laboratoire de Chimie des Surfaces et Interfaces, CEA, IRAMIS, SPCSI, 91191 Gif-sur-Yvette Cedex (France)

2011-11-15

This study deals with a hybrid system consisting in quaterthiophene derivative encapsulated inside single-walled and multi-walled carbon nanotubes. Investigations of the encapsulation step are performed by transmission electron microscopy. Raman spectroscopy data point out different behaviors depending on the laser excitation energy with respect to the optical absorption of quaterthiophene. At low excitation energy (far from the oligomer resonance window) there is no significant modification of the Raman spectra before and after encapsulation. By contrast, at high excitation energy (close to the oligomer resonance window), Raman spectra exhibit a G-band shift together with an important RBM intensity loss, suggesting a significant charge transfer between the inserted molecule and the host nanotubes. Those results suggest a photo induced process leading to a significant charge transfer. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Symmetric resonance double charge transfer in Kr++ + Kr and Xe++ + Xe systems

International Nuclear Information System (INIS)

Okuno, K.; Koizumi, T.; Kaneko, Y.

1978-01-01

Cross sections of processes Kr ++ + Kr → Ke + Kr ++ and Xe ++ + Xe → Xe + Xe ++ were measured by the injected-ion-drift-tube technique from 0.04 to 20 eV. For both cases, the cross section below 1 eV coincides with the orbiting cross sections with a charge-transfer probability 1/2. Above 1 eV, the energy dependence of the cross sectcion is like that for single charge transfer. Mobilities of Kr ++ and Xe ++ in He are presented also

Bose-Einstein condensation and indirect excitons: a review.

Science.gov (United States)

Combescot, Monique; Combescot, Roland; Dubin, François

2017-06-01

We review recent progress on Bose-Einstein condensation (BEC) of semiconductor excitons. The first part deals with theory, the second part with experiments. This Review is written at a time where the problem of exciton Bose-Einstein condensation has just been revived by the understanding that the exciton condensate must be dark because the exciton ground state is not coupled to light. Here, we theoretically discuss this missed understanding before providing its experimental support through experiments that scrutinize indirect excitons made of spatially separated electrons and holes. The theoretical part first discusses condensation of elementary bosons. In particular, the necessary inhibition of condensate fragmentation by exchange interaction is stressed, before extending the discussion to interacting bosons with spin degrees of freedom. The theoretical part then considers composite bosons made of two fermions like semiconductor excitons. The spin structure of the excitons is detailed, with emphasis on the crucial fact that ground-state excitons are dark: indeed, this imposes the exciton Bose-Einstein condensate to be not coupled to light in the dilute regime. Condensate fragmentations are then reconsidered. In particular, it is shown that while at low density, the exciton condensate is fully dark, it acquires a bright component, coherent with the dark one, beyond a density threshold: in this regime, the exciton condensate is 'gray'. The experimental part first discusses optical creation of indirect excitons in quantum wells, and the detection of their photoluminescence. Exciton thermalisation is also addressed, as well as available approaches to estimate the exciton density. We then switch to specific experiments where indirect excitons form a macroscopic fragmented ring. We show that such ring provides efficient electrostatic trapping in the region of the fragments where an essentially-dark exciton Bose-Einstein condensate is formed at sub-Kelvin bath

A two-dimensional position sensitive gas chamber with scanned charge transfer readout

Energy Technology Data Exchange (ETDEWEB)

Gomez, F. E-mail: faustgr@usc.es; Iglesias, A.; Lobato, R.; Mosquera, J.; Pardo, J.; Pena, J.; Pazos, A.; Pombar, M.; Rodriguez, A

2003-10-21

We have constructed and tested a two-dimensional position sensitive parallel-plate gas ionization chamber with scanned charge transfer readout. The scan readout method described here is based on the development of a new position-dependent charge transfer technique. It has been implemented by using gate strips perpendicularly oriented to the collector strips. This solution reduces considerably the number of electronic readout channels needed to cover large detector areas. The use of a 25 {mu}m thick kapton etched circuit allows high charge transfer efficiency with a low gating voltage, consequently needing a very simple commutating circuit. The present prototype covers 8x8 cm{sup 2} with a pixel size of 1.27x1.27 mm{sup 2}. Depending on the intended use and beam characteristics a smaller effective pixel is feasible and larger active areas are possible. This detector can be used for X-ray or other continuous beam intensity profile monitoring.

A two-dimensional position sensitive gas chamber with scanned charge transfer readout

International Nuclear Information System (INIS)

Gomez, F.; Iglesias, A.; Lobato, R.; Mosquera, J.; Pardo, J.; Pena, J.; Pazos, A.; Pombar, M.; Rodriguez, A.

2003-01-01

We have constructed and tested a two-dimensional position sensitive parallel-plate gas ionization chamber with scanned charge transfer readout. The scan readout method described here is based on the development of a new position-dependent charge transfer technique. It has been implemented by using gate strips perpendicularly oriented to the collector strips. This solution reduces considerably the number of electronic readout channels needed to cover large detector areas. The use of a 25 μm thick kapton etched circuit allows high charge transfer efficiency with a low gating voltage, consequently needing a very simple commutating circuit. The present prototype covers 8x8 cm 2 with a pixel size of 1.27x1.27 mm 2 . Depending on the intended use and beam characteristics a smaller effective pixel is feasible and larger active areas are possible. This detector can be used for X-ray or other continuous beam intensity profile monitoring

Charge transfer in pi-stacked systems including DNA

International Nuclear Information System (INIS)

Siebbeles, L.D.A.

2003-01-01

Charge migration in DNA is a subject of intense current study motivated by long-range detection of DNA damage and the potential application of DNA as a molecular wire in nanoscale electronic devices. A key structural element, which makes DNA a medium for long-range charge transfer, is the array of stacked base pairs in the interior of the double helix. The overlapping pi-orbitals of the nucleobases provide a pathway for motion of charge carriers generated on the stack. This 'pi-pathway' resembles the columnarly stacked macrocyclic cores in discotic materials such as triphenylenes. The structure of these pi-stacked systems is highly disordered with dynamic fluctuations occurring on picosecond to nanosecond time scales. Theoretical calculations, concerning the effects of structural disorder and nucleobase sequence in DNA, on the dynamics of charge carriers are presented. Electronic couplings and localization energies of charge carriers were calculated using density functional theory (DFT). Results for columnarly stacked triphenylenes and DNA nucleobases are compared. The results are used to provide insight into the factors that control the mobility of charge carriers. Further, experimental results on the site-selective oxidation of guanine nucleobases in DNA (hot spots for DNA damage) are analyzed on basis of the theoretical results

Triplet exciton dynamics

International Nuclear Information System (INIS)

Strien, A.J. van.

1981-01-01

Results are presented of electron spin echo experiments combined with laser flash excitation on triplet states of aromatic molecules. Some of the theoretical and experimental aspects of the photoexcited triplet state are discussed in detail and the electron spin echo spectrometers and laser systems are described. All the experiments described in this thesis were performed at liquid helium temperatures. An account is given of the ESE experiments performed on the photoexcited, non-radiative, triplet state of pentacene in napthalene. This is an example of the ESE technique being used to ascertain the zero-field splitting parameters, the populating and depopulating rates, and the orientation of the pentacene molecules in the naphthalene host. A combination of high resolution laser flash excitation and electron-spin echoes in zero-magnetic field allowed the author to observe directly k(vector)→k(vector)' exciton scattering processes in the one-dimensional triplet excitons in tetrachlorobenzene for the first time. Additional experimental data about exciton scattering is provided and a study of the orientational dependence of the spin-lattice relaxation of the triplet excitons in an external magnetic field is described. (Auth.)

Plasmon-exciton-polariton lasing

NARCIS (Netherlands)

Ramezani, M.; Halpin, A.; Fernández-Dominguez, A.I.; Feist, J.; Rodriguez, S.R.K.; Gómez-Rivas, J.; Garcia-Vidal, F.J.

2016-01-01

Strong coupling of Frenkel excitons with surface plasmons leads to the formation of bosonic quasi-particles known as plasmon-exciton-polaritons (PEPs).Localized surface plasmons in nanoparticles are lossy due to radiative and nonradiative decays, which has hampered the realization of polariton

Ion-atom charge-transfer system for a heavy-ion-beam pumped laser

International Nuclear Information System (INIS)

Ulrich, A.; Gernhaeuser, R.; Kroetz, W.; Wieser, J.; Murnick, D.E.

1994-01-01

An Ar target to which Cs vapor could be added, excited by a pulsed beam of 100-MeV 32 S ions, was studied as a prototype ion-atom charge-transfer system for pumping short-wavelength lasers. Low-velocity Ar 2+ ions were efficiently produced; a huge increase in the intensity of the Ar II 4d-4p spectral lines was observed when Cs vapor was added to the argon. This observation is explained by a selective charge transfer of the Cs 6s electron into the upper levels of the observed transitions. A rate constant of (1.4±0.2)x10 -9 cm 3 /s for the transfer process was determined

The influence of electric charge transferred during electro-mechanical reshaping on mechanical behavior of cartilage

Science.gov (United States)

Protsenko, Dimitry E.; Lim, Amanda; Wu, Edward C.; Manuel, Cyrus; Wong, Brian J. F.

2011-03-01

Electromechanical reshaping (EMR) of cartilage has been suggested as an alternative to the classical surgical techniques of modifying the shape of facial cartilages. The method is based on exposure of mechanically deformed cartilaginous tissue to a low level electric field. Electro-chemical reactions within the tissue lead to reduction of internal stress, and establishment of a new equilibrium shape. The same reactions offset the electric charge balance between collagen and proteoglycan matrix and interstitial fluid responsible for maintenance of cartilage mechanical properties. The objective of this study was to investigate correlation between the electric charge transferred during EMR and equilibrium elastic modulus. We used a finite element model based on the triphasic theory of cartilage mechanical properties to study how electric charges transferred in the electro-chemical reactions in cartilage can change its mechanical responses to step displacements in unconfined compression. The concentrations of the ions, the strain field and the fluid and ion velocities within the specimen subject to an applied mechanical deformation were estimated and apparent elastic modulus (the ratio of the equilibrium axial stress to the axial strain) was calculated as a function of transferred charge. The results from numerical calculations showed that the apparent elastic modulus decreases with increase in electric charge transfer. To compare numerical model with experimental observation we measured elastic modulus of cartilage as a function of electric charge transferred in electric circuit during EMR. Good correlation between experimental and theoretical data suggests that electric charge disbalance is responsible for alteration of cartilage mechanical properties.

Theoretical studies of charge transfer and proton transfer complex formation between 3,5-dinitrobenzic acid and 1,2-dimethylimidazole

Science.gov (United States)

Afroz, Ziya; Faizan, Mohd.; Alam, Mohammad Jane; Ahmad, Shabbir; Ahmad, Afaq

2018-05-01

Natural atomic charge analysis and molecular electrostatic potential (MEP) surface analysis of hydrogen bonded charge transfer (HBCT) and proton transfer (PT) complex of 3,5-dinitrobenzoic acid (DNBA) and 1,2-dimethylimidazole (DMI) have been investigated by theoretical modelling using widely employed DFT/B3LYP/6-311G(d,p) level of theory. Along with this analysis, Hirshfeld surface study of the intermolecular interactions and associated 2D finger plot for reported PT complex between DNBA and DMI have been explored.

Charge transfer in gas electron multipliers

Energy Technology Data Exchange (ETDEWEB)

Ottnad, Jonathan; Ball, Markus; Ketzer, Bernhard; Ratza, Viktor; Razzaghi, Cina [HISKP, Bonn University, Nussallee 14-16, D-53115 Bonn (Germany)

2015-07-01

In order to efficiently employ a Time Projection Chamber (TPC) at interaction rates higher than ∝1 kHz, as foreseen e.g. in the ALICE experiment (CERN) and at CB-ELSA (Bonn), a continuous operation and readout mode is required. A necessary prerequisite is to minimize the space charge coming from the amplification system and to maintain an excellent spatial and energy resolution. Unfortunately these two goals can be in conflict to each other. Gas Electron Multipliers (GEM) are one candidate to fulfill these requirements. It is necessary to understand the processes within the amplification structure to find optimal operation conditions. To do so, we measure the charge transfer processes in and between GEM foils with different geometries and field configurations, and use an analytical model to describe the results. This model can then be used to predict and optimize the performance. The talk gives the present status of the measurements and describes the model.

The charge transfer characteristic of tetraphenylporphyrin iron chloride Langmuir–Blodgett films

International Nuclear Information System (INIS)

Du, Y.; Li, Z.H.; Qi, P.; Wang, F.; Liu, D.

2013-01-01

The charge transfer characteristic of tetraphenylporphyrin iron (III) chloride (FeP) Langmuir–Blodgett (LB) films on the surface of the ITO glass electrode was reported. When the cyclic voltammetry (CV) scanning was running, the charge transfer characteristic was controlled by the oxidation–reduction process of Fe(III)/Fe(II). The charge transfer characteristic was related to the following factors: the cross-sectional area, relative to the electrode, of FeP as the electron donor (or acceptor). The greater the cross-sectional area of the aggregation of FeP as the electron donor (or acceptor) was, the larger the number of the donated (or accepted) electrons was. The projected area of the cross-section on the ITO electrode. The greater the projected area was, the larger the number of the donated (or accepted) electrons was. The distance between the center of the electron donor (or acceptor) of FeP and the surface of ITO electrode. The smaller the distance was, the greater the rate of donating (or accepting) electrons was. The monolayer coverage, which formed because of the FeP lying on the ITO surface in the form of the monomer and aggregate, was more sensitive to detect oxygen

Failures of TDDFT in describing the lowest intramolecular charge-transfer excitation in para-nitroanilin

DEFF Research Database (Denmark)

Eriksen, J.J.; Sauer, S.P.A.; Mikkelsen, K.V.

2013-01-01

We investigate the failure of Time{Dependent Density Functional Theory (TDDFT) with the CAM{B3LYP exchange{correlation (xc) functional coupled to the Polarizable Embedding (PE) scheme (PE-CAM-B3LYP) in reproducing the solvatochromic shift of the lowest intense charge{transfer excitation in para...... the electric dipole moments in the gas phase and for 100 solvent congurations. We find that CAM-B3LYP overestimates the amount of charge separation inherent in the ground state and TDDFT/CAM-B3LYP drastically underestimates this amount in the excited charge-transfer state. As the errors in the solvatochromatic...... to benchmark results of TDDFT calculations with CAM-B3LYP for intramolecular charge{transfer excitations in molecular systems similar to pNA against higher{level ab initio wave function methods, like, e.g., CCSD, prior to their use. Using the calculated change in dipole moment upon excitation as a measure...

A low-spin Fe(III) complex with 100-ps ligand-to-metal charge transfer photoluminescence

DEFF Research Database (Denmark)

Chabera, Pavel; Liu, Yizhu; Prakash, Om

2017-01-01

Transition-metal complexes are used as photosensitizers(1), in light-emitting diodes, for biosensing and in photocatalysis(2). A key feature in these applications is excitation from the ground state to a charge-transfer state(3,4); the long charge-transfer-state lifetimes typical for complexes...

Photoinduced charge transfer within polyaniline-encapsulated quantum dots decorated on graphene.

Science.gov (United States)

Nguyen, Kim Truc; Li, Dehui; Borah, Parijat; Ma, Xing; Liu, Zhaona; Zhu, Liangliang; Grüner, George; Xiong, Qihua; Zhao, Yanli

2013-08-28

A new method to enhance the stability of quantum dots (QDs) in aqueous solution by encapsulating them with conducting polymer polyaniline was reported. The polyaniline-encapsulated QDs were then decorated onto graphene through π-π interactions between graphene and conjugated polymer shell of QDs, forming stable polyaniline/QD/graphene hybrid. A testing electronic device was fabricated using the hybrid in order to investigate the photoinduced charge transfer between graphene and encapsulated QDs within the hybrid. The charge transfer mechanism was explored through cyclic voltammetry and spectroscopic studies. The hybrid shows a clear response to the laser irradiation, presenting a great advantage for further applications in optoelectronic devices.

Cost-Effectiveness Comparison of Coupler Designs of Wireless Power Transfer for Electric Vehicle Dynamic Charging

Directory of Open Access Journals (Sweden)

Weitong Chen

2016-11-01

Full Text Available This paper presents a cost-effectiveness comparison of coupler designs for wireless power transfer (WPT, meant for electric vehicle (EV dynamic charging. The design comparison of three common types of couplers is first based on the raw material cost, output power, transfer efficiency, tolerance of horizontal offset, and flux density. Then, the optimal cost-effectiveness combination is selected for EV dynamic charging. The corresponding performances of the proposed charging system are compared and analyzed by both simulation and experimentation. The results verify the validity of the proposed dynamic charging system for EVs.

Plasma effect on tunnelling, charge transfer and transient quasimolecular states

International Nuclear Information System (INIS)

Fisher, D V

2003-01-01

The influence of a dense plasma environment on electron tunnelling between two ion potential wells in collectivized states and in charge-transfer collisions is studied. We show that the tunnelling probabilities in dilute plasma (in a close ion-ion collision) and in dense plasma differ strongly. The difference is due to the mixing between Stark components of donor-ion energy levels, caused by the field of spectator ions in a dense plasma. The mixing is determined by an angle α between the nearest-neighbour ion field and the total electric field acting on the donor ion. In close ion-ion binary collisions the mixing may be considered weak. However, for most plasma ions charge transfer, electron state collectivization and transient quasimolecule formation are strongly affected by the field of spectator ions. We derive approximate analytical expressions for the distribution function of α in an ideal plasma and perform molecular dynamics simulations to find the distribution function of α in both ideal and nonideal plasmas. Both α-dependent and average mixing coefficients are determined. We have found that the mixing is strong, even in ideal plasmas, and increases further with an increase in plasma nonideality. It is shown that there is no resonant charge transfer in dense plasmas. The applicability of a transient 'dicenter' quasimolecule model for dense plasmas is discussed

Biexciton formation and exciton coherent coupling in layered GaSe

Energy Technology Data Exchange (ETDEWEB)

Dey, P.; Paul, J.; Stevens, C. E.; Glikin, N.; Karaiskaj, D., E-mail: karaiskaj@usf.edu [Department of Physics, University of South Florida, 4202 East Fowler Ave., Tampa, Florida 33620 (United States); Moody, G. [National Institute of Standards and Technology, 325 Broadway, Boulder, Colarado 80305 (United States); Kovalyuk, Z. D.; Kudrynskyi, Z. R. [Chernivtsi Department, Frantsevich Institute of Material Sciences Problems, The National Academy of Sciences of Ukraine, 5, Iryna Vilde St., 58001 Chernivtsi (Ukraine); Romero, A. H. [Physics Department, West Virginia University, Morgantown, West Virginia 26506-6315 (United States); Cantarero, A. [Materials Science Institute, University of Valencia, P.O. Box 2205, 46071 Valencia (Spain); Hilton, D. J. [Department of Physics, University of Alabama at Birmingham, Birmingham, Alabama 35294 (United States)

2015-06-07

Nonlinear two-dimensional Fourier transform (2DFT) and linear absorption spectroscopy are used to study the electronic structure and optical properties of excitons in the layered semiconductor GaSe. At the 1s exciton resonance, two peaks are identified in the absorption spectra, which are assigned to splitting of the exciton ground state into the triplet and singlet states. 2DFT spectra acquired for co-linear polarization of the excitation pulses feature an additional peak originating from coherent energy transfer between the singlet and triplet. At cross-linear polarization of the excitation pulses, the 2DFT spectra expose a new peak likely originating from bound biexcitons. The polarization dependent 2DFT spectra are well reproduced by simulations using the optical Bloch equations for a four level system, where many-body effects are included phenomenologically. Although biexciton effects are thought to be strong in this material, only moderate contributions from bound biexciton creation can be observed. The biexciton binding energy of ∼2 meV was estimated from the separation of the peaks in the 2DFT spectra. Temperature dependent absorption and 2DFT measurements, combined with “ab initio” theoretical calculations of the phonon spectra, indicate strong interaction with the A{sub 1}{sup ′} phonon mode. Excitation density dependent 2DFT measurements reveal excitation induced dephasing and provide a lower limit for the homogeneous linewidth of the excitons in the present GaSe crystal.

Biexciton formation and exciton coherent coupling in layered GaSe

International Nuclear Information System (INIS)

Dey, P.; Paul, J.; Stevens, C. E.; Glikin, N.; Karaiskaj, D.; Moody, G.; Kovalyuk, Z. D.; Kudrynskyi, Z. R.; Romero, A. H.; Cantarero, A.; Hilton, D. J.

2015-01-01

Nonlinear two-dimensional Fourier transform (2DFT) and linear absorption spectroscopy are used to study the electronic structure and optical properties of excitons in the layered semiconductor GaSe. At the 1s exciton resonance, two peaks are identified in the absorption spectra, which are assigned to splitting of the exciton ground state into the triplet and singlet states. 2DFT spectra acquired for co-linear polarization of the excitation pulses feature an additional peak originating from coherent energy transfer between the singlet and triplet. At cross-linear polarization of the excitation pulses, the 2DFT spectra expose a new peak likely originating from bound biexcitons. The polarization dependent 2DFT spectra are well reproduced by simulations using the optical Bloch equations for a four level system, where many-body effects are included phenomenologically. Although biexciton effects are thought to be strong in this material, only moderate contributions from bound biexciton creation can be observed. The biexciton binding energy of ∼2 meV was estimated from the separation of the peaks in the 2DFT spectra. Temperature dependent absorption and 2DFT measurements, combined with “ab initio” theoretical calculations of the phonon spectra, indicate strong interaction with the A 1 ′ phonon mode. Excitation density dependent 2DFT measurements reveal excitation induced dephasing and provide a lower limit for the homogeneous linewidth of the excitons in the present GaSe crystal

Exciton-polaron quenching in organic thin-film transistors studied by fluorescence lifetime imaging microscopy

DEFF Research Database (Denmark)

Jensen, Per Baunegaard With; Leißner, Till; Osadnik, Andreas

Organic semiconductors show great potential in electronic and optical applications. However, a major challenge is the degradation of the semiconductor materials that cause a reduction in device performance. Here, we present our investigations of Organic Thin Film Transistors (OTFT) based...... that correlates with the local charge density indicates a pronounced exciton quenching by the injected charges. Subsequent FLIM measurements on previously biased OTFT devices show a general decrease in fluorescence lifetime suggesting degradation of the organic semiconductor. This is correlated with the results...

Exciton Emission from Bare and Alq3/Gold Coated GaN Nanorods

Science.gov (United States)

Mohammadi, Fatemesadat; Kuhnert, Gerd; Hommel, Detlef; Schmitzer, Heidrun; Wagner, Hans-Peter

We study the excitonic and impurity related emission in bare and aluminum quinoline (Alq3)/gold coated wurtzite GaN nanorods by temperature-dependent time-integrated (TI) and time-resolved (TR) photoluminescence (PL). The GaN nanorods were grown by molecular beam epitaxy. Alq3 as well as Alq3/gold covered nanorods were synthesized by organic molecular beam deposition. In the near-band edge region a donor-bound-exciton (D0X) emission is observed at 3.473 eV. Another emission band at 3.275 eV reveals LO-phonon replica and is attributed to a donor-acceptor-pair (DAP) luminescence. TR PL traces at 20 K show a nearly biexponential decay for the D0X with lifetimes of approximately 180 and 800 ps for both bare and Alq3 coated nanorods. In GaN nanorods which were coated with an Alq3 film and subsequently with a 10 nm thick gold layer we observe a PL quenching of D0X and DAP band and the lifetimes of the D0X transition shorten. The quenching behaviour is partially attributed to the energy-transfer from free excitons and donor-bound-excitons to plasmon oscillations in the gold layer.

Quenching of exciton luminescence due to impact ionization and mechanisms of electron relaxation in cadmium sulphide

International Nuclear Information System (INIS)

Kagan, V.D.; Karpenko, S.L.; Katilyus, R.

1989-01-01

Quenching of exciton luminescence in the constant electric field in cadmium sulfide at 1.8K, caused by impact ionization of free and delocalization of bound excitons by hot electrons is observed. When the field is increase up to 1 kW/cm continuous transfer from the Taundsen-Shockley law to the Davydov-Wolf one takes place. Among the samples studied pure samples are distinguished by the exciton spectrum, where, as it is shown in the work, the high-energy electrons lose quasipulse, radiating spontaneously piezophonons; in other samples scattering on impurities prevails. Theoretical processing of data on the bound exciton radiation line quenching in the moderate field region presents about 10 -4 values in pure and about 5x10 -6 cm ones in other samples for the 4 MeV energy electron free flight length. So, the optical methods used allowed one to determine high-energy electron relaxation mechanisms, prevailing in CdS at low temperature

Excitons in the rare gas solids

International Nuclear Information System (INIS)

1988-01-01

Excitons play a prominent role in the chemistry and physics of condensed matter. Excitons in the rare gas solids, the prototypical van der Waals insulators, will be the focus of the remainder of this report. The goal here is to investigate the controversies surrounding the description of excitons in insulators and, therefore the simplest class of these solids, namely the rare gas solids, is chosen as the exemplary system. Specific problems associated with molecular crystals are, therefore, avoided and only the salient features of excitons are thus considered. 47 refs., 9 figs., 4 tabs

Excitonic Effects in Methylammonium Lead Halide Perovskites

Energy Technology Data Exchange (ETDEWEB)

Beard, Matthew C [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Chen, Xihan [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Lu, Haipeng [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Yang, Ye [National Renewable Energy Laboratory (NREL), Golden, CO (United States)

2018-05-01

The exciton binding energy in methylammonium lead iodide (MAPbI3) is about 10 meV, around 1/3 of the available thermal energy (kBT ~ 26 meV) at room temperature. Thus, exciton populations are not stable at room temperature at moderate photoexcited carrier densities. However, excitonic resonances dominate the absorption onset. Furthermore, these resonances determine the transient absorbance and transient reflectance spectra. The exciton binding energy is a reflection of the Coulomb interaction energy between photoexcited electrons and holes. As such, it serves as a marker for the strength of electron/hole interactions and impacts a variety of phenomena, such as, absorption, radiative recombination, and Auger recombination. In this Perspective, we discuss the role of excitons and excitonic resonances in the optical properties of lead-halide perovskite semiconductors. Finally, we discuss how the strong light-matter interactions induce an optical stark effect splitting the doubly spin degenerate ground exciton states and are easily observed at room temperature.

Signatures of correlated excitonic dynamics in two-dimensional spectroscopy of the Fenna-Matthew-Olson photosynthetic complex

International Nuclear Information System (INIS)

Caram, Justin R.; Lewis, Nicholas H. C.; Fidler, Andrew F.; Engel, Gregory S.

2012-01-01

Long-lived excitonic coherence in photosynthetic proteins has become an exciting area of research because it may provide design principles for enhancing the efficiency of energy transfer in a broad range of materials. In this publication, we provide new evidence that long-lived excitonic coherence in the Fenna-Mathew-Olson pigment-protein (FMO) complex is consistent with the assumption of cross correlation in the site basis, indicating that each site shares bath fluctuations. We analyze the structure and character of the beating crosspeak between the two lowest energy excitons in two-dimensional (2D) electronic spectra of the FMO Complex. To isolate this dynamic signature, we use the two-dimensional linear prediction Z-transform as a platform for filtering coherent beating signatures within 2D spectra. By separating signals into components in frequency and decay rate representations, we are able to improve resolution and isolate specific coherences. This strategy permits analysis of the shape, position, character, and phase of these features. Simulations of the crosspeak between excitons 1 and 2 in FMO under different regimes of cross correlation verify that statistically independent site fluctuations do not account for the elongation and persistence of the dynamic crosspeak. To reproduce the experimental results, we invoke near complete correlation in the fluctuations experienced by the sites associated with excitons 1 and 2. This model contradicts ab initio quantum mechanic/molecular mechanics simulations that observe no correlation between the energies of individual sites. This contradiction suggests that a new physical model for long-lived coherence may be necessary. The data presented here details experimental results that must be reproduced for a physical model of quantum coherence in photosynthetic energy transfer.

Bands dispersion and charge transfer in β-BeH2

Science.gov (United States)

Trivedi, D. K.; Galav, K. L.; Joshi, K. B.

2018-04-01

Predictive capabilities of ab-initio method are utilised to explore bands dispersion and charge transfer in β-BeH2. Investigations are carried out using the linear combination of atomic orbitals method at the level of density functional theory. The crystal structure and related parameters are settled by coupling total energy calculations with the Murnaghan equation of state. Electronic bands dispersion from PBE-GGA is reported. The PBE-GGA, and PBE0 hybrid functional, show that β-BeH2 is a direct gap semiconductor with 1.18 and 2.40 eV band gap. The band gap slowly decreases with pressure and beyond l00 GPa overlap of conduction and valence bands at the r point is observed. Charge transfer is studied by means of Mullikan population analysis.

Transfer of energy or charge between quasi-zero-dimensional nanostructures

Czech Academy of Sciences Publication Activity Database

Král, Karel; Menšík, Miroslav

2016-01-01

Roč. 45, č. 4 (2016), s. 243-255 ISSN 2332-4309 R&D Projects: GA ČR(CZ) GA14-05053S; GA MŠk(CZ) LD14011; GA MŠk LH12236 Institutional support: RVO:68378271 ; RVO:61389013 Keywords : charge transfer * electron-phonon interaction * energy transfer * nanostructures * quantum dots Subject RIV: BM - Solid Matter Physics ; Magnetism; CD - Macromolecular Chemistry (UMCH-V) Impact factor: 0.171, year: 2016

Modeling charge transfer at organic donor-acceptor semiconductor interfaces

NARCIS (Netherlands)

Cakir, Deniz; Bokdam, Menno; de Jong, Machiel Pieter; Fahlman, M.; Brocks, G.

2012-01-01

We develop an integer charge transfer model for the potential steps observed at interfaces between donor and acceptor molecular semiconductors. The potential step can be expressed as the difference between the Fermi energy pinning levels of electrons on the acceptor material and holes on the donor

On the Molecular Origin of Charge Separation at the Donor-Acceptor Interface

KAUST Repository

Sini, Gjergji; Schubert, Marcel; Risko, Chad; Roland, Steffen; Lee, Olivia P.; Chen, Zhihua; Richter, Thomas V.; Dolfen, Daniel; Coropceanu, Veaceslav; Ludwigs, Sabine; Scherf, Ullrich; Facchetti, Antonio; Frechet, Jean; Neher, Dieter

2018-01-01

and theoretical approach is used to understand the intimate mechanisms by which molecular structure contributes to exciton dissociation, charge separation, and charge recombination at the donor–acceptor (D–A) interface. Model systems comprised of polythiophene

Charge transfer in photorechargeable composite films of TiO2 and polyaniline

Science.gov (United States)

Nomiyama, Teruaki; Sasabe, Kenichi; Sakamoto, Kenta; Horie, Yuji

2015-07-01

A photorechargeable battery (PRB) is a photovoltaic device having an energy storage function in a single cell. The photoactive electrode of PRB is a bilayer film consisting of bare porous TiO2 and a TiO2-polyaniline (PANi) mixture that work as a photovoltaic current generator and an electrochemical energy storage by ion dedoping, respectively. To study the charge transfer between TiO2 and PANi, the photorechargeable quantum efficiency QE ([electron count on discharge]/[incident photon count on photocharge]) was measured by varying the thickness LS of the TiO2-PANi mixture. The quantum efficiency QEuv for UV photons had a maximum of ˜7% at LS ˜ 7 µm. The time constant τTP for the charge transfer was about 10-1 s, which was longer ten times or more than the lifetime of excited electrons within TiO2. These facts reveal that the main rate-limiting factor in the photocharging process is the charge transfer between TiO2 and PANi.

Exciton Migration and Amplified Quenching on Two-Dimensional Metal–Organic Layers

Energy Technology Data Exchange (ETDEWEB)

Cao, Lingyun; Lin, Zekai; Shi, Wenjie; Wang, Zi; Zhang, Cankun; Hu, Xuefu; Wang, Cheng; Lin, Wenbin (UC); (Xiamen)

2017-05-10

The dimensionality dependency of resonance energy transfer is of great interest due to its importance in understanding energy transfer on cell membranes and in low-dimension nanostructures. Light harvesting two-dimensional metal–organic layers (2D-MOLs) and three-dimensional metal–organic frameworks (3D-MOFs) provide comparative models to study such dimensionality dependence with molecular accuracy. Here we report the construction of 2D-MOLs and 3D-MOFs from a donor ligand 4,4',4''-(benzene-1,3,5-triyl-tris(ethyne-2,1-diyl))tribenzoate (BTE) and a doped acceptor ligand 3,3',3''-nitro-4,4',4''-(benzene-1,3,5-triyl-tris(ethyne-2,1-diyl))tribenzoate (BTE-NO2). These 2D-MOLs and 3D-MOFs are connected by similar hafnium clusters, with key differences in the topology and dimensionality of the metal–ligand connection. Energy transfer from donors to acceptors through the 2D-MOL or 3D-MOF skeletons is revealed by measuring and modeling the fluorescence quenching of the donors. We found that energy transfer in 3D-MOFs is more efficient than that in 2D-MOLs, but excitons on 2D-MOLs are more accessible to external quenchers as compared with those in 3D-MOFs. These results not only provide support to theoretical analysis of energy transfer in low dimensions, but also present opportunities to use efficient exciton migration in 2D materials for light-harvesting and fluorescence sensing.

Excitons

Energy Technology Data Exchange (ETDEWEB)

Kozhushner, M

1975-06-01

The theory of quasi particles is explained to layman readers and the significance of the discovery of excitons is pointed out. New possibilities of the study of electron-hole interactions and of superconductivity are indicated.

Probing exciton density of states through phonon-assisted emission in GaN epilayers: A and B exciton contributions

Science.gov (United States)

Cavigli, Lucia; Gabrieli, Riccardo; Gurioli, Massimo; Bogani, Franco; Feltin, Eric; Carlin, Jean-François; Butté, Raphaël; Grandjean, Nicolas; Vinattieri, Anna

2010-09-01

A detailed experimental investigation of the phonon-assisted emission in a high-quality c -plane GaN epilayer is presented up to 200 K. By performing photoluminescence and reflectivity measurements, we find important etaloning effects in the phonon-replica spectra, which have to be corrected before addressing the lineshape analysis. Direct experimental evidence for free exciton thermalization is found for the whole temperature range investigated. A close comparison with existing models for phonon replicas originating from a thermalized free exciton distribution shows that the simplified and commonly adopted description of the exciton-phonon interaction with a single excitonic band leads to a large discrepancy with experimental data. Only the consideration of the complex nature of the excitonic band in GaN, including A and B exciton contributions, allows accounting for the temperature dependence of the peak energy, intensity, and lineshape of the phonon replicas.

Scaling laws of Rydberg excitons

Science.gov (United States)

Heckötter, J.; Freitag, M.; Fröhlich, D.; Aßmann, M.; Bayer, M.; Semina, M. A.; Glazov, M. M.

2017-09-01

Rydberg atoms have attracted considerable interest due to their huge interaction among each other and with external fields. They demonstrate characteristic scaling laws in dependence on the principal quantum number n for features such as the magnetic field for level crossing or the electric field of dissociation. Recently, the observation of excitons in highly excited states has allowed studying Rydberg physics in cuprous oxide crystals. Fundamentally different insights may be expected for Rydberg excitons, as the crystal environment and associated symmetry reduction compared to vacuum give not only optical access to many more states within an exciton multiplet but also extend the Hamiltonian for describing the exciton beyond the hydrogen model. Here we study experimentally and theoretically the scaling of several parameters of Rydberg excitons with n , for some of which we indeed find laws different from those of atoms. For others we find identical scaling laws with n , even though their origin may be distinctly different from the atomic case. At zero field the energy splitting of a particular multiplet n scales as n-3 due to crystal-specific terms in the Hamiltonian, e.g., from the valence band structure. From absorption spectra in magnetic field we find for the first crossing of levels with adjacent principal quantum numbers a Br∝n-4 dependence of the resonance field strength, Br, due to the dominant paramagnetic term unlike for atoms for which the diamagnetic contribution is decisive, resulting in a Br∝n-6 dependence. By contrast, the resonance electric field strength shows a scaling as Er∝n-5 as for Rydberg atoms. Also similar to atoms with the exception of hydrogen we observe anticrossings between states belonging to multiplets with different principal quantum numbers at these resonances. The energy splittings at the avoided crossings scale roughly as n-4, again due to crystal specific features in the exciton Hamiltonian. The data also allow us to

The impact of long-range electron-hole interaction on the charge separation yield of molecular photocells

Science.gov (United States)

Nemati Aram, Tahereh; Ernzerhof, Matthias; Asgari, Asghar; Mayou, Didier

2017-01-01

We discuss the effects of charge carrier interaction and recombination on the operation of molecular photocells. Molecular photocells are devices where the energy conversion process takes place in a single molecular donor-acceptor complex attached to electrodes. Our investigation is based on the quantum scattering theory, in particular on the Lippmann-Schwinger equation; this minimizes the complexity of the problem while providing useful and non-trivial insight into the mechanism governing photocell operation. In this study, both exciton pair creation and dissociation are treated in the energy domain, and therefore there is access to detailed spectral information, which can be used as a framework to interpret the charge separation yield. We demonstrate that the charge carrier separation is a complex process that is affected by different parameters, such as the strength of the electron-hole interaction and the non-radiative recombination rate. Our analysis helps to optimize the charge separation process and the energy transfer in organic solar cells and in molecular photocells.

Controlling the exciton emission of gold coated GaAs-AlGaAs core-shell nanowires with an organic spacer layer

Science.gov (United States)

Kaveh, M.; Gao, Q.; Jagadish, C.; Ge, J.; Duscher, G.; Wagner, H. P.

2016-12-01

Excitons are the most prominent optical excitations and controlling their emission is an important step towards new optical devices. We have investigated the exciton emission from uncoated and gold/aluminum quinoline (Alq3) coated GaAs-AlGaAs-GaAs core-shell nanowires (NWs) using temperature-, intensity- and polarization dependent photoluminescence (PL). Plasmonic GaAs-AlGaAs-GaAs NWs with a ˜10 nm thick Au coating but without an Alq3 spacer layer reveal a significant reduction of the PL intensity of the exciton emission compared with the uncoated NW sample. Plasmonic NW samples with the same nominal Au coverage and an additional Alq3 interlayer of 3 or 6 nm thickness show a clearly stronger PL intensity which increases with rising Alq3 spacer thickness. Time-resolved (TR) PL measurements reveal an increase of the exciton decay rate by a factor of up to two with decreasing Alq3 spacer thickness suggesting the presence of Förster energy transfer from NW excitons to plasmon oscillations in the gold film. The weak change of the decay time, however, indicates that Förster energy-transfer is only partially responsible for the PL quenching in the gold coated NWs. The main reason for the reduction of the PL emission is attributed to a gold induced band-bending in the GaAs NW core which causes exciton dissociation. With increasing Alq3 spacer thickness the band-bending decreases leading to a reduction of the exciton dissociation and PL quenching. Our interpretation is supported by electron energy loss spectroscopy measurements which show a signal reduction and blue shift of defect (possibly EL2) transitions when gold particles are deposited on NWs compared with bare or Alq3 coated NWs.

Heat transfer from the evaporator outlet to the charge of thermostatic expansion valves

DEFF Research Database (Denmark)

Langmaack, Lasse Nicolai; Knudsen, Hans-Jørgen Høgaard

2006-01-01

outlet with a special mounting strap. The heat transfer is quite complex because it takes place both directly through the contact points between bulb and pipe and indirectly through the mounting strap The TXV has to react to temperature changes at the evaporator outlet. Therefore, the dynamic behavior...... of the valve (and thereby the whole refrigeration system) depends greatly on the heat transfer between the evaporator outlet tube and the charge in the bulb. In this paper a model for the overall heat transfer between the pipe and the charge is presented. Geometrical data and material properties have been kept...... been found to predict the time constant for the temperature development in the bulb within 1-10 %. Furthermore it has been found that app. 20% of the heat transfer takes place trough the mounting strap....

Chiral Modes at Exceptional Points in Exciton-Polariton Quantum Fluids

Science.gov (United States)

Gao, T.; Li, G.; Estrecho, E.; Liew, T. C. H.; Comber-Todd, D.; Nalitov, A.; Steger, M.; West, K.; Pfeiffer, L.; Snoke, D. W.; Kavokin, A. V.; Truscott, A. G.; Ostrovskaya, E. A.

2018-02-01

We demonstrate the generation of chiral modes-vortex flows with fixed handedness in exciton-polariton quantum fluids. The chiral modes arise in the vicinity of exceptional points (non-Hermitian spectral degeneracies) in an optically induced resonator for exciton polaritons. In particular, a vortex is generated by driving two dipole modes of the non-Hermitian ring resonator into degeneracy. Transition through the exceptional point in the space of the system's parameters is enabled by precise manipulation of real and imaginary parts of the closed-wall potential forming the resonator. As the system is driven to the vicinity of the exceptional point, we observe the formation of a vortex state with a fixed orbital angular momentum (topological charge). This method can be extended to generate higher-order orbital angular momentum states through coalescence of multiple non-Hermitian spectral degeneracies. Our Letter demonstrates the possibility of exploiting nontrivial and counterintuitive properties of waves near exceptional points in macroscopic quantum systems.

Chiral Modes at Exceptional Points in Exciton-Polariton Quantum Fluids.

Science.gov (United States)

Gao, T; Li, G; Estrecho, E; Liew, T C H; Comber-Todd, D; Nalitov, A; Steger, M; West, K; Pfeiffer, L; Snoke, D W; Kavokin, A V; Truscott, A G; Ostrovskaya, E A

2018-02-09

We demonstrate the generation of chiral modes-vortex flows with fixed handedness in exciton-polariton quantum fluids. The chiral modes arise in the vicinity of exceptional points (non-Hermitian spectral degeneracies) in an optically induced resonator for exciton polaritons. In particular, a vortex is generated by driving two dipole modes of the non-Hermitian ring resonator into degeneracy. Transition through the exceptional point in the space of the system's parameters is enabled by precise manipulation of real and imaginary parts of the closed-wall potential forming the resonator. As the system is driven to the vicinity of the exceptional point, we observe the formation of a vortex state with a fixed orbital angular momentum (topological charge). This method can be extended to generate higher-order orbital angular momentum states through coalescence of multiple non-Hermitian spectral degeneracies. Our Letter demonstrates the possibility of exploiting nontrivial and counterintuitive properties of waves near exceptional points in macroscopic quantum systems.

Complexes of dipolar excitons in layered quasi-two-dimensional nanostructures

Science.gov (United States)

Bondarev, Igor V.; Vladimirova, Maria R.

2018-04-01

We discuss neutral and charged complexes (biexcitons and trions) formed by indirect excitons in layered quasi-two-dimensional semiconductor heterostructures. Indirect excitons—long-lived neutral Coulomb-bound pairs of electrons and holes of different layers—have been known for semiconductor coupled quantum wells and have recently been reported for van der Waals heterostructures such as double bilayer graphene and transition-metal dichalcogenides. Using the configuration space approach, we derive the analytical expressions for the trion and biexciton binding energies as a function of interlayer distance. The method captures essential kinematics of complex formation to reveal significant binding energies, up to a few tens of meV for typical interlayer distances ˜3 -5 Å , with the trion binding energy always being greater than that of the biexciton. Our results can contribute to the understanding of more complex many-body phenomena such as exciton Bose-Einstein condensation and Wigner-like electron-hole crystallization in layered semiconductor heterostructures.

Optical and Excitonic Properties of Atomically Thin Transition-Metal Dichalcogenides

Science.gov (United States)

Berkelbach, Timothy C.; Reichman, David R.

2018-03-01

Starting with the isolation of a single sheet of graphene, the study of layered materials has been one of the most active areas of condensed matter physics, chemistry, and materials science. Single-layer transition-metal dichalcogenides are direct-gap semiconducting analogs of graphene that exhibit novel electronic and optical properties. These features provide exciting opportunities for the discovery of both new fundamental physical phenomena as well as innovative device platforms. Here, we review the progress associated with the creation and use of a simple microscopic framework for describing the optical and excitonic behavior of few-layer transition-metal dichalcogenides, which is based on symmetry, band structure, and the effective interactions between charge carriers in these materials. This approach provides an often quantitative account of experiments that probe the physics associated with strong electron–hole interactions in these quasi two-dimensional systems and has been successfully employed by many groups to both describe and predict emergent excitonic behavior in these layered semiconducting systems.

Direct measurement of exciton valley coherence in monolayer WSe2

KAUST Repository

Hao, Kai

2016-02-29

In crystals, energy band extrema in momentum space can be identified by a valley index. The internal quantum degree of freedom associated with valley pseudospin indices can act as a useful information carrier, analogous to electronic charge or spin. Interest in valleytronics has been revived in recent years following the discovery of atomically thin materials such as graphene and transition metal dichalcogenides. However, the valley coherence time—a crucial quantity for valley pseudospin manipulation—is difficult to directly probe. In this work, we use two-dimensional coherent spectroscopy to resonantly generate and detect valley coherence of excitons (Coulomb-bound electron–hole pairs) in monolayer WSe₂ (refs ,). The imposed valley coherence persists for approximately one hundred femtoseconds. We propose that the electron–hole exchange interaction provides an important decoherence mechanism in addition to exciton population recombination. This work provides critical insight into the requirements and strategies for optical manipulation of the valley pseudospin for future valleytronics applications.

Excitons

International Nuclear Information System (INIS)

Kozhushner, M.

1975-01-01

The theory of quasi particles is explained to layman readers and the significance of the discovery of excitons is pointed out. New possibilities of the study of electron-hole interactions and of superconductivity are indicated. (L.O.)

Evidence for charge transfer in Bi-based superconductors studied by positron annihilation

International Nuclear Information System (INIS)

Tang, Z.; Wang, S.J.; Gao, X.H.; Ce, G.C.; Zhao, Z.X.

1993-01-01

We have measured Doppler-broadening annihilation radiation (DBAR) spectra and positron lifetimes in normal and superconducting states for three kinds of Bi-based superconductors: Bi2212, Pb-doped Bi2223, Pb- and F-doped Bi2223. The difference spectra after deconvolution between two states show a sharpening effect with increasing temperature; the F-doped sample has the greatest amplitude in difference spectra but nearly the same positron lifetimes as the Pb-doped sample. The results are interpreted in terms of charge transfer between the Cu-O and Bi-O planes. The role of oxygen defects in charge transfer is discussed. (orig.)

Charge-exchange breakup of the deuteron with the production of two protons and spin structure of the amplitude of the nucleon charge transfer reaction

International Nuclear Information System (INIS)

Glagolev, V.V.; Lyuboshits, V.L.; Lyuboshits, V.V.; Piskunov, N.M.

1999-01-01

In the framework of the impulse approximation, the relation between the effective cross section of the charge-exchange breakup of a fast deuteron d + a → (pp) + b and the effective cross section of the charge transfer process n + a → p + b is discussed. In doing so, the effects of the proton identity (Fermi-statistics) and of the Coulomb and strong interactions of protons in the final state are taken into account. The distribution over relative momenta of the protons, produced in the charge-exchange process d + p → (pp) + n in the forward direction, is investigated. At the transfer momenta being close to zero the effective cross section of the charge-exchange breakup of a fast deuteron, colliding with the proton target, is determined only by the spin-flip part of the amplitude of the charge transfer reaction n + p → p + n at the zero angle. It is shown that the study of the process d + p → (pp) + n in a beam of the polarized (aligned) deuterons allows one, in principle, to separate two spin-dependent terms in the amplitude of the charge transfer reaction n + p → p + n, one of which does not conserve and the other one conserves the projection of the nucleon spin onto the direction of momentum at the transition of the neutron into the proton

Low-Energy Charge Transfer in Multiply-Charged Ion-Atom Collisions Studied with the Combined SCVB-MOCC Approach

OpenAIRE

Cooper, D. L.; Stancil, P. C.; Turner, A. R.; Wang, J. G.; Clarke, N. J.; Zygelman, B.

2002-01-01

A survey of theoretical studies of charge transfer involving collisions of multiply-charged ions with atomic neutrals (H and He) is presented. The calculations utilized the quantum-mechanical molecular-orbital close-coupling (MOCC) approach where the requisite potential curves and coupling matrix elements have been obtained with the spin-coupled valence bond (SCVB) method. Comparison is made among various collision partners, for equicharged systems, where it is illustrated that even for total...

Possible charge analogues of spin transfer torques in bulk superconductors

Science.gov (United States)

Garate, Ion

2014-03-01

Spin transfer torques (STT) occur when electric currents travel through inhomogeneously magnetized systems and are important for the motion of magnetic textures such as domain walls. Since superconductors are easy-plane ferromagnets in particle-hole (charge) space, it is natural to ask whether any charge duals of STT phenomena exist therein. We find that the superconducting analogue of the adiabatic STT vanishes in a bulk superconductor with a momentum-independent order parameter, while the superconducting counterpart of the nonadiabatic STT does not vanish. This nonvanishing superconducting torque is induced by heat (rather than charge) currents and acts on the charge (rather than spin) degree of freedom. It can become significant in the vicinity of the superconducting transition temperature, where it generates a net quasiparticle charge and alters the dispersion and linewidth of low-frequency collective modes. This work has been financially supported by Canada's NSERC.

Charge-transfer complexes and their role in exciplex emission and near-infrared photovoltaics.

Science.gov (United States)

Ng, Tsz-Wai; Lo, Ming-Fai; Fung, Man-Keung; Zhang, Wen-Jun; Lee, Chun-Sing

2014-08-20

Charge transfer and interactions at organic heterojunctions (OHJs) are known to have critical influences on various properties of organic electronic devices. In this Research News article, a short review is given from the electronic viewpoint on how the local molecular interactions and interfacial energetics at P/N OHJs contribute to the recombination/dissociation of electron-hole pairs. Very often, the P-type materials donate electrons to the N-type materials, giving rise to charge-transfer complexes (CTCs) with a P(δ+) -N(δ-) configuration. A recently observed opposite charge-transfer direction in OHJs is also discussed (i.e., N-type material donates electrons to P-type material to form P(δ-) -N(δ+) ). Recent studies on the electronic structures of CTC-forming material pairs are also summarized. The formation of P(δ-) -N(δ+) -type CTCs and their correlations with exciplex emission are examined. Furthermore, the potential applications of CTCs in NIR photovoltaic devices are reviewed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Deflection effects and charge transfer in inner-shell vacancy production

International Nuclear Information System (INIS)

Swafford, G.L.

1978-01-01

A method used in the calculation of inner shell ionization in asymmetric ion-atom collisions is extended to include projectile deflection effects and charge transfer to the projectile. Work is done in an independent electron model (Hartree-Fock) for the target, and the interaction is treated with the projectile as a time-dependent perturbation of the system. It is shown tht the time-dependent problem can be solved for the projectile moving along the classical hyperbolic trajectory that results from the nuclear repulsion. The method is very efficient due to the utilization the target-centered expansion of the system wave function. This means that all the required matrix elements can be pretabulated and are then available for use at all impact parameters. The method is first applied to the impact-parameter dependence of K-shell ionization by protons incident upon copper in the energy range 0.5 to 2 MeV. Excellent agreement with the experiments of Andersen et al., is found at the lower energy. Less satisfactory agreement is obtained in the higher energy region. Next the projectile is considered to move in a straight line path with constant velocity, and extend the method to include charge transfer between the target inner shells and the K-shell of the projectile. A critical feature of the results is the recognition of the importance of target continuum states of energy approximately equal to the kinetic energy (in the target frame) of the electron on the projectile. An approach is developed to properly include such resonance states in our pseudostate calculation. Selected numerical results are presented to illustrate the method and to demonstrate the projectile energy and nuclear charge dependence of the charge transfer cross sections

Excitons in Single-Walled Carbon Nanotubes and Their Dynamics

Science.gov (United States)

Amori, Amanda R.; Hou, Zhentao; Krauss, Todd D.

2018-04-01

Understanding exciton dynamics in single-walled carbon nanotubes (SWCNTs) is essential to unlocking the many potential applications of these materials. This review summarizes recent progress in understanding exciton photophysics and, in particular, exciton dynamics in SWCNTs. We outline the basic physical and electronic properties of SWCNTs, as well as bright and dark transitions within the framework of a strongly bound one-dimensional excitonic model. We discuss the many facets of ultrafast carrier dynamics in SWCNTs, including both single-exciton states (bright and dark) and multiple-exciton states. Photophysical properties that directly relate to excitons and their dynamics, including exciton diffusion lengths, chemical and structural defects, environmental effects, and photoluminescence photon statistics as observed through photon antibunching measurements, are also discussed. Finally, we identify a few key areas for advancing further research in the field of SWCNT excitons and photonics.

Origin of DNA-Induced Circular Dichroism in a Minor-Groove Binder.

Science.gov (United States)

Holmgaard List, Nanna; Knoops, Jérémie; Rubio-Magnieto, Jenifer; Idé, Julien; Beljonne, David; Norman, Patrick; Surin, Mathieu; Linares, Mathieu

2017-10-25

Induced circular dichroism (ICD) of DNA-binding ligands is well known to be strongly influenced by the specific mode of binding, but the relative importance of the possible mechanisms has remained undetermined. With a combination of molecular dynamics simulations, CD response calculations, and experiments on an AT-sequence, we show that the ICD of minor-groove-bound 4',6-diamidino-2-phenylindole (DAPI) originates from an intricate interplay between the chiral imprint of DNA, off-resonant excitonic coupling to nucleobases, charge-transfer, and resonant excitonic coupling between DAPIs. The significant contributions from charge-transfer and the chiral imprint to the ICD demonstrate the inadequacy of a standard Frenkel exciton theory of the DAPI-DNA interactions.

Effect of Molecular Packing and Charge Delocalization on the Nonradiative Recombination of Charge-Transfer States in Organic Solar Cells

KAUST Repository

Chen, Xiankai

2016-09-05

In organic solar cells, a major source of energy loss is attributed to nonradiative recombination from the interfacial charge transfer states to the ground state. By taking pentacene–C60 complexes as model donor–acceptor systems, a comprehensive theoretical understanding of how molecular packing and charge delocalization impact these nonradiative recombination rates at donor–acceptor interfaces is provided.

Models of coherent exciton condensation

International Nuclear Information System (INIS)

Littlewood, P B; Eastham, P R; Keeling, J M J; Marchetti, F M; Simons, B D; Szymanska, M H

2004-01-01

That excitons in solids might condense into a phase-coherent ground state was proposed about 40 years ago, and has been attracting experimental and theoretical attention ever since. Although experimental confirmation has been hard to come by, the concepts released by this phenomenon have been widely influential. This tutorial review discusses general aspects of the theory of exciton and polariton condensates, focusing on the reasons for coherence in the ground state wavefunction, the BCS to Bose crossover(s) for excitons and for polaritons, and the relationship of the coherent condensates to standard lasers

Models of coherent exciton condensation

Energy Technology Data Exchange (ETDEWEB)

Littlewood, P B [Theory of Condensed Matter, Cavendish Laboratory, Cambridge CB3 0HE (United Kingdom); Eastham, P R [Theory of Condensed Matter, Cavendish Laboratory, Cambridge CB3 0HE (United Kingdom); Keeling, J M J [Theory of Condensed Matter, Cavendish Laboratory, Cambridge CB3 0HE (United Kingdom); Marchetti, F M [Theory of Condensed Matter, Cavendish Laboratory, Cambridge CB3 0HE (United Kingdom); Simons, B D [Theory of Condensed Matter, Cavendish Laboratory, Cambridge CB3 0HE (United Kingdom); Szymanska, M H [Theory of Condensed Matter, Cavendish Laboratory, Cambridge CB3 0HE (United Kingdom)

2004-09-08

That excitons in solids might condense into a phase-coherent ground state was proposed about 40 years ago, and has been attracting experimental and theoretical attention ever since. Although experimental confirmation has been hard to come by, the concepts released by this phenomenon have been widely influential. This tutorial review discusses general aspects of the theory of exciton and polariton condensates, focusing on the reasons for coherence in the ground state wavefunction, the BCS to Bose crossover(s) for excitons and for polaritons, and the relationship of the coherent condensates to standard lasers.

Improving radiation hardness in space-based Charge-Coupled Devices through the narrowing of the charge transfer channel

Science.gov (United States)

Hall, D. J.; Skottfelt, J.; Soman, M. R.; Bush, N.; Holland, A.

2017-12-01

Charge-Coupled Devices (CCDs) have been the detector of choice for imaging and spectroscopy in space missions for several decades, such as those being used for the Euclid VIS instrument and baselined for the SMILE SXI. Despite the many positive properties of CCDs, such as the high quantum efficiency and low noise, when used in a space environment the detectors suffer damage from the often-harsh radiation environment. High energy particles can create defects in the silicon lattice which act to trap the signal electrons being transferred through the device, reducing the signal measured and effectively increasing the noise. We can reduce the impact of radiation on the devices through four key methods: increased radiation shielding, device design considerations, optimisation of operating conditions, and image correction. Here, we concentrate on device design operations, investigating the impact of narrowing the charge-transfer channel in the device with the aim of minimising the impact of traps during readout. Previous studies for the Euclid VIS instrument considered two devices, the e2v CCD204 and CCD273, the serial register of the former having a 50 μm channel and the latter having a 20 μm channel. The reduction in channel width was previously modelled to give an approximate 1.6× reduction in charge storage volume, verified experimentally to have a reduction in charge transfer inefficiency of 1.7×. The methods used to simulate the reduction approximated the charge cloud to a sharp-edged volume within which the probability of capture by traps was 100%. For high signals and slow readout speeds, this is a reasonable approximation. However, for low signals and higher readout speeds, the approximation falls short. Here we discuss a new method of simulating and calculating charge storage variations with device design changes, considering the absolute probability of capture across the pixel, bringing validity to all signal sizes and readout speeds. Using this method, we

Density-dependent squeezing of excitons in highly excited semiconductors

International Nuclear Information System (INIS)

Nguyen Hong Quang.

1995-07-01

The time evolution from coherent states to squeezed states of high density excitons is studied theoretically based on the boson formalism and within the Random Phase Approximation. Both the mutual interaction between excitons and the anharmonic exciton-photon interaction due to phase-space filling of excitons are taken into account. It is shown that the exciton squeezing depends strongly on the exciton density in semiconductors and becomes smaller with increasing the latter. (author). 16 refs, 2 figs

Integer charge transfer at the tetrakis(dimethylamino)ethylene/Au interface

DEFF Research Database (Denmark)

Lindell, L.; Unge, Mikael; Osikowicz, W.

2008-01-01

In organic-based electronics, interfacial properties have a profound impact on device performance. The lineup of energy levels is usually dependent on interface dipoles, which may arise from charge transfer reactions. In many applications, metal-organic junctions are prepared under ambient...

Charge transfer and partial pinning at the contacts as the origin of a double dip in the transfer characteristics of graphene-based field-effect transistors

International Nuclear Information System (INIS)

Di Bartolomeo, Antonio; Giubileo, Filippo; Santandrea, Salvatore; Romeo, Francesco; Citro, Roberta; Schroeder, Thomas; Lupina, Grzegorz

2011-01-01

We discuss the origin of an additional dip other than the charge neutrality point observed in the transfer characteristics of graphene-based field-effect transistors with a Si/SiO 2 substrate used as the back-gate. The double dip is proved to arise from charge transfer between the graphene and the metal electrodes, while charge storage at the graphene/SiO 2 interface can make it more evident. Considering a different Fermi energy from the neutrality point along the channel and partial charge pinning at the contacts, we propose a model which explains all the features observed in the gate voltage loops. We finally show that the double dip enhanced hysteresis in the transfer characteristics can be exploited to realize graphene-based memory devices.

Coupled quantum treatment of vibrationally inelastic and vibronic charge transfer in proton-O2 collisions

International Nuclear Information System (INIS)

Gianturco, F.A.; Palma, A.; Semprini, E.; Stefani, F.; Baer, M.

1990-01-01

A three-dimensional quantum-mechanical study of vibrational, state-resolved differential cross sections (DCS) for the direct inelastic and for the charge-transfer scattering channels has been carried out for the H + +O 2 system. The collision energy considered was E c.m. =23.0 eV, which is the same as that examined by Noll and Toennies in their experiments [J. Chem. Phys. 85, 3313 (1986)]. The scattering treatment employed was the charge-transfer infinite-order sudden approximation (CT IOSA) with the vibrational states correctly expanded over the relevant adiabatic basis for each of the two electronic channels. The state-to-state DCS are found to follow closely the behavior of the experimental quantities, both in the inelastic and the charge-transfer channels. Moreover, a careful comparison between the measured relative probabilities and computed values allows us to test in minute detail the efficiency of the scattering model and the reliability of the potential-energy surfaces employed. It is found that vibrational energy transfer is overestimated in the vibrational inelastic channels while in the charge-transfer inelastic channels the same energy transfer is slightly underestimated by the calculations. The total flux distribution, however, is found to be in very good accord with experiments. Angular distributions are also well reproduced both by the DCS and by the average energy-transfer values. The study of some of the CT IOSA quantities also allows us to establish clearly the importance of nonadiabatic transitions in enhancing vibrational inelasticity in the present system

Reconstructing Space- and Energy-Dependent Exciton Generation in Solution-Processed Inverted Organic Solar Cells.

Science.gov (United States)

Wang, Yuheng; Zhang, Yajie; Lu, Guanghao; Feng, Xiaoshan; Xiao, Tong; Xie, Jing; Liu, Xiaoyan; Ji, Jiahui; Wei, Zhixiang; Bu, Laju

2018-04-25

Photon absorption-induced exciton generation plays an important role in determining the photovoltaic properties of donor/acceptor organic solar cells with an inverted architecture. However, the reconstruction of light harvesting and thus exciton generation at different locations within organic inverted device are still not well resolved. Here, we investigate the film depth-dependent light absorption spectra in a small molecule donor/acceptor film. Including depth-dependent spectra into an optical transfer matrix method allows us to reconstruct both film depth- and energy-dependent exciton generation profiles, using which short-circuit current and external quantum efficiency of the inverted device are simulated and compared with the experimental measurements. The film depth-dependent spectroscopy, from which we are able to simultaneously reconstruct light harvesting profile, depth-dependent composition distribution, and vertical energy level variations, provides insights into photovoltaic process. In combination with appropriate material processing methods and device architecture, the method proposed in this work will help optimizing film depth-dependent optical/electronic properties for high-performance solar cells.

Classical/quantum correspondence in state selective charge transfer and excitation reactions involving highly charged ions and hydrogen

International Nuclear Information System (INIS)

Purkait, M

2009-01-01

State selective charge transfer and excitation cross sections for collisions of Ne q+ (q = 1-10) with atomic hydrogen are calculated within the framework of Classical Trajectory Monte Carlo (CTMC) method and Boundary Corrected Continuum Intermediate State (BCCIS) approximation.

Exciton Formation in Disordered Semiconductors

DEFF Research Database (Denmark)

Klochikhin, A.; Reznitsky, A.; Permogorov, S.

1999-01-01

Stationary luminescence spectra of disordered solid solutions can be accounted by the model of localized excitons. Detailed analysis of the long time decay kinetics of luminescence shows that exciton formation in these systems is in great extent due to the bimolecular reaction of separated carrie...

A schematic model for energy and charge transfer in the chlorophyll complex

DEFF Research Database (Denmark)

Bohr, Henrik; Malik, F.B.

2011-01-01

A theory for simultaneous charge and energy transfer in the carotenoid-chlorophyll-a complex is presented here and discussed. The observed charge transfer process in these chloroplast complexes is reasonably explained in terms of this theory. In addition, the process leads to a mechanism to drive...... an electron in a lower to a higher-energy state, thus providing a mechanism for the ejection of the electron to a nearby molecule (chlorophyll) or into the environment. The observed lifetimes of the electronically excited states are in accord/agreement with the investigations of Sundström et al....... and are in the range of pico-seconds and less. The change in electronic charge distribution in internuclear space as the system undergoes an electronic transition to a higher-energy state could, under appropriate physical conditions, lead to oscillating dipoles capable of transmitting energy from the carotenoid-chlorophylls...

Temperature dependence of positronium reactivities with charge transfer molecules in bilayer membranes

International Nuclear Information System (INIS)

Jean, Y.C.; Yu, C.; Wang, Y.Y.; Yeh, Y.Y.

1984-01-01

Rate constants for positronium atoms reacting chemically with charge-transfer molecules such as p-benzoquinone, nitrobenzene, and coenzyme Q-10 in a model bilayer membrane, dipalmitoylphosphatidylcholine (DPPC), have been measured at temperatures between 23 and 65 0 C. A strong variation of the positronium chemical reactivities, k/sub Ps/ was observed in these systems: k/sub Ps/ increases with increasing temperature until the pretransition temperature of the membrane reaches a maximum value near the main transition temperature and decreases at temperatures higher than the main transition temperature. This variation is interpreted in terms of fluidity and permeability changes associated with the phase transitions of membranes and in terms of charge-transfer-complex formation between the solubilized molecules and the polar head of the membrane. These results demonstrate that positronium and its annihilation characteristics can be employed to investigate charge transport phenomena and microstructural changes of real biological membranes

Numerical study on electronic and optical properties of organic light emitting diodes.

Science.gov (United States)

Kim, Kwangsik; Hwang, Youngwook; Won, Taeyoung

2013-08-01

In this paper, we present a finite element method (FEM) study of space charge effects in organic light emitting diodes. Our model includes a Gaussian density of states to account for the energetic disorder in organic semiconductors and the Fermi-Dirac statistics to account for the charge hopping process between uncorrelated sites. The physical model cover all the key physical processes in OLEDs, namely charge injection, transport and recombination, exciton diffusion, transfer and decay as well as light coupling, and thin-film-optics. The exciton model includes generation, diffusion, and energy transfer as well as annihilation. We assumed that the light emission originates from oscillating and thus embodied as excitons and embedded in a stack of multilayer. The out-coupled emission spectrum has been numerically calculated as a function of viewing angle, polarization, and dipole orientation. We discuss the accumulation of charges at internal interfaces and their signature in the transient response as well as the electric field distribution.

Fractional Solitons in Excitonic Josephson Junctions

OpenAIRE

Hsu, Ya-Fen; Su, Jung-Jung

2015-01-01

The Josephson effect is especially appealing to physicists because it reveals macroscopically the quantum order and phase. In excitonic bilayers the effect is even subtler due to the counterflow of supercurrent as well as the tunneling between layers (interlayer tunneling). Here we study, in a quantum Hall bilayer, the excitonic Josephson junction: a conjunct of two exciton condensates with a relative phase ? 0 applied. The system is mapped into a pseudospin ferromagnet then described numeric...

Evaluation of intramolecular charge transfer state of 4-N, N ...

Indian Academy of Sciences (India)

Abstract. Intramolecular charge transfer of 4-N,N-dimethylamino cinnamaldehyde (DMACA) in vacuum and in five different aprotic solvents has been studied by using time-dependent density functional theory. (TDDFT). Polarizable continuum model (PCM) was employed to consider solvent–solute interactions. The potential ...

Low energy cross section data for ion-molecule reactions in hydrogen systems and for charge transfer of multiply charged ions with atoms and molecules

International Nuclear Information System (INIS)

Okuno, Kazuhiko

2007-04-01

Systematic cross section measurements for ion-molecule reactions in hydrogen systems and for charge transfer of multiply charged ions in low energy collisions with atoms and molecules have been performed continuously by the identical apparatus installed with an octo-pole ion beam guide (OPIG) since 1980 till 2004. Recently, all of accumulated cross section data for a hundred collision systems has been entered into CMOL and CHART of the NIFS atomic and molecular numerical database together with some related cross section data. In this present paper, complicated ion-molecule reactions in hydrogen systems are revealed and the brief outlines of specific properties in low energy charge transfer collisions of multiply charged ions with atoms and molecules are introduced. (author)

Tuning electronic properties of graphene nanoflake polyaromatic hydrocarbon through molecular charge-transfer interactions

Science.gov (United States)

Sharma, Vaishali; Dabhi, Shweta D.; Shinde, Satyam; Jha, Prafulla K.

2018-05-01

By means of first principles calculation we have tuned the electronic properties of graphene nanoflake polyaromatic hydrocarbon via molecular charge transfer. Acceptor/donor Tetracyanoquinodimethane (TCNQ) and Tetrathiafulvalene (TTF) organic molecules are adsorbed on polyaromatic hydrocarbons (PAH) in order to introduce the charge transfer. The substrate's n- or p- type nature depends on the accepting/donating behavior of dopant molecules. Two different classes of PAH (extended form of triangulene) namely Bow-tie graphene nanoflake (BTGNF) and triangular zigzag graphene nanoflake (TZGNF). It is revealed that all the TCNQ and TTF modified graphene nanoflakes exhibit significant changes in HOMO-LUMO gap in range from 0.58 eV to 0.64 eV and 0.01 eV to 0.05 eV respectively. The adsorption energies are in the range of -0.05 kcal/mol to -2.6 kcal/mol. The change in work function is also calculated and discussed, the maximum charge transfer is for TCNQ adsorbed BTGNF. These alluring findings in the tuning of electronic properties will be advantageous for promoting graphene nanoflake polyaromatic hydrocarbon for their applications in electronic devices.

Chiral topological excitons in a Chern band insulator

Science.gov (United States)

Chen, Ke; Shindou, Ryuichi

2017-10-01

A family of semiconductors called Chern band insulators are shown to host exciton bands with nonzero topological Chern integers and chiral exciton edge modes. Using a prototypical two-band Chern insulator model, we calculate a cross-correlation function to obtain the exciton bands and their Chern integers. The lowest exciton band acquires Chern integers such as ±1 and ±2 in the electronic Chern insulator phase. The nontrivial topology can be experimentally observed both by a nonlocal optoelectronic response of exciton edge modes and by a phase shift in the cross-correlation response due to the bulk mode. Our result suggests that magnetically doped HgTe, InAs/GaSb quantum wells, and (Bi,Sb)2Te3 thin films are promising candidates for a platform of topological excitonics.

Turn-on fluorescence probes based on pyranine/viologen charge-transfer complexes for the determination of nucleotides

Energy Technology Data Exchange (ETDEWEB)

Schäferling, Michael, E-mail: Michael.schaeferling@utu.fi; Lang, Thomas; Schnettelker, Annette

2014-10-15

The formation of ground state charge-transfer complexes between pyranine (8-hydroxypyrene-1,3,6-trisulfonic acid) and viologen (paraquat) derivatives is utilized for the design of novel fluoroionophores for the determination of phosphate species, particularly of nucleotides. The strong quenching of the pyranine fluorescence by viologen-type charge transfer acceptors can be countermanded if these are functionalized with triethylammonium groups that serve as recognition elements for phosphate anions. We report on the fluorogenic responses of these water-soluble molecular probes in presence of different phosphates. Absorbance measurements give additional information on the charge transfer complex formation and the interaction with nucleotides. The experimental data show that these aggregates form attractive, simple and versatile fluorescence turn-on probes for nucleoside triphosphates. The reversibility of the fluorescence response is demonstrated by means of an enzymatic model assay using ATPase for the decomposition of adenosine triphosphate. - Highlights: • Pyranine/viologen charge-transfer complexes as molecular probe for ATP recognition. • Fluorescence turn on mechanism. • Selective compared to other nucleotides and phosphate anions. • Fast and reversible response applicable to monitor enzymatic reactions.