Photogeneration of electrons and holes in amorphous molecular semiconductors

This paper reports on the results of investigations into the photoconducting properties of amorphous molecular semiconductors based on films of two types: (i) poly(styrene) films doped with epoxypropylcarbazole (EPC) and a cationic polymethine dye (PD1) and (ii) poly(styrene) films doped with tetranitrofluorenone (TNF) and an anionic polymethine dye (PD2). Films of the first type possess p-type conductivity, whereas films of the second type exhibit n-type conductivity. It is found that, for films with n-type conductivity, unlike films with p-type conductivity, the activation energy of photogeneration of mobile charge carriers decreases with a decrease in the optical wavelength in the absorption range of the dyes. The possible mechanisms of the influence of the photoexcitation energy on the initial distance between charge carriers in electron-hole pairs are analyzed. The inference is made that, when the excess thermal energy of excited dye molecules dissipates at a low rate, the distance between the photogenerated electrons and photogeneration centers increases as compared to the distance between the photogenerated holes and photogeneration centers due to the electron-nucleus interaction.     

Electrical and optical properties of pulse plated CdS<Subscript><Emphasis Type="BoldItalic">x</Emphasis></Subscript>Te<Subscript>1-<Emphasis Type="BoldItalic">x</Emphasis></Subscript> films

Thin films of CdS_xTe_1-x were deposited by the pulse electrodeposition technique using cadmium sulfate, sodium thiosulfate, and tellurium dioxide on titanium and conducting glass substrates. Structural studies indicated the formation of polycrystalline films possessing hexagonal structure. The resistivity varies from 53 Ω cm to 8 Ω cm as the stochiometric coefficient “x” value decreases from 1 to 0. The carrier concentration increases with CdTe concentration. It is observed that as the post-heat treatment temperature increases, the photosensitivity also increases. It is observed that a post-heat treatment temperature of 550 °C results in high photosensitivity as well as low light resistance. The optical constants, refractive index (n) and extinction coefficient (k) were evaluated from the transmission spectra of the films of different composition.     

Frequency and density dependent radiative recombination processes in III–V semiconductor quantum wells and superlattices

In this paper we review the radiative recombination processes occurring in semiconductor quantum wells and superlattices under different excitation conditions. We consider processes whose radiative efficiency depends on the photogenerated density of elementary excitations and on the frequency of the exciting field, including luminescence induced by multiphoton absorption, exciton and biexciton radiative decay, luminescence arising from inelastic excitonic scattering, and electron-hole plasma recombination.

Semiconductor quantum wells are ideal systems for the investigation of radiative recombination processes at different carrier densities owing to the peculiar wavefunction confinement which enhances the optical non-linearities and the bistable behaviour of the crystal. Radiative recombination processes induced by multi-photon absorption processes can be studied by exciting the crystal in the transparency region under an intense photon flux. The application of this non-linear spectroscopy gives direct access to the excited excitonic states in the quantum wells owing to the symmetry properties and the selection rules for artificially layered semiconductor heterostructures.

Different radiative recombination processes can be selectively tuned at exciting photon energies resonant with real states or in the continuum of the conduction band depending on the actual density of photogenerated carriers. We define three density regimes in which different quasi-particles are responsible for the dominant radiative recombination mechanisms of the crystal: (i) The dilute boson gas regime, in which exciton density is lower than 10¹⁰ cm^-2. Under this condition the decay of free and bound excitons is the main radiative recombination channel in the crystal. (ii) The intermediate density range (n < 10¹¹ cm^-2) at which excitonic molecules (biexcitons) and inelastic excitonic scattering processes contribute with additional decay mechanisms to the characteristic luminescence spectra. (iii) The high density range (n ?10¹² cm^-2) where screening of the Coulomb interaction leads to exciton ionization. The optical transitions hence originate from the radiative decay of free-carriers in a dense electron-hole plasma.

The fundamental theoretical and experimental aspects of the radiative recombination processes are discussed with special attention to the GaAs/Al _x Ga_1-x As and Ga _x In_1-x As/Al _y In_1-y As materials systems. The experimental investigations of these effects are performed in the limit of intense exciting fields by tuning the density of photogenerated quasi-particles and the frequency of the exciting photons. Under these conditions the optical response of the quantum well strongly deviates from the well-known linear excitonic behaviour. The optical properties of the crystal are then no longer controlled by the transverse dielectric constant or by the first-order dielectric susceptibility. They are strongly affected by many-body interactions between the different species of photogenerated quasi-particles, resulting in dramatic changes of the emission properties of the semiconductor.

The systematic investigation of these radiative recombination processes allows us to selectively monitor the many-body induced changes in the linear and non-linear optical transitions involving quantized states of the quantum wells. The importance of these effects, belonging to the physics of highly excited semiconductors, lies in the possibility of achieving population inversion of states associated with different radiative recombination channels and strong optical non-linearities causing laser action and bistable behaviour of two-dimensional heterostructures, respectively.     

Population inversion in narrow-gap heterostructures due to the interband tunneling

The process of interband tunneling in a heterostructure with a wide-gap barrier between two layers of narrow-gap doped semiconductors is investigated. The tunneling probability, intraband and interband current components, and non-equilibrium carrier concentration are calculated using the transfer matrix method and a Dirac-like model for lead chalcogenide-type heterostructures. It is shown that the generation of electron-hole pairs due to interband tunneling may produce a population inversion and laser generation in the near-barrier region.     

Features of charge-carrier recombination in amorphous molecular semiconductors doped with polymethine dyes

The photogeneration and recombination of charge carriers in poly-N-epoxypropylcarbazole films with additions of a polymethine dye are investigated irradiation of films with blocking contacts by light both within and outside the absorption range of the dye. The kinetics of the accumulation and relaxation of electron-hole pairs, whose lifetimes exceed tens and hundreds of seconds, are studied. It is postulated that an increase in the recombination luminescence intensity occurs in an electric field as a result of an increase in the efficiency of the bimolecular radiative recombination stimulated by trapped electrons from photogenerated excitons. Fiz. Tverd. Tela (St. Petersburg) 40, 629–635 (April 1998)     

N,Co共掺杂锐钛矿相YiO2光催化剂的第一性原理研究

采用第一性原理平面波超软赝势方法研究了N,Co共掺杂锐钛矿相TiO2的微观结构和光学性质.结果表明:N,Co共掺杂后TiO2晶格中产生的偶极矩使光生电子-空穴对更有效地分离;在TiO2导带和价带之间形成了新的杂质能级,一方面使吸收带边红移到可见光区,光吸收性能明显增强,另一方面有利于光生电子-空穴对的分离,提高TiO2的光量子效率;与纯TiO2相比,N,Co共掺杂锐钛矿相TiO2带边的氧化还原势只有微小的变化,共掺杂后TiO2的强氧化还原能力得以保持.     

Dynamics of the electric field-assisted charge carrier photogeneration in ladder-type poly(para-phenylene) at a low excitation intensity

Electric field-assisted charge carrier photogeneration in a ladder-type methyl-substituted poly(paraphenylene) was investigated by ultrafast absorption spectroscopy at low excitation intensity. The dissociation of excitons into electron-hole pairs occurs from the vibrationally relaxed excited state throughout its lifetime and is caused by the applied electric field, rather than by existence of special "dissociation sites." These findings are of importance for material choice in device applications.     

Effect of an electric field on the dissociation of electron-hole pairs interacting with triplet excitons in amorphous molecular semiconductors

The photoconductivity of amorphous molecular semiconductor films increases with the simultaneous photogeneration of singlet electron-hole pairs (EHPs) and triplet excitons but decreases when singlet EHPs are replaced by triplet EHPs. As the electric field increases, the influence of the triplet excitons on the photoconductivity of the films due to the dissociation of EHPs becomes less. It is concluded that as the electric field increases, the current-carrier mobility increases and the dissociation rate of EHPs becomes comparable to the spinconversion rate of EHPs interacting with triplet excitons. Fiz. Tverd. Tela (St. Petersburg) 39, 1020–1023 (June 1997)     

Effect of electric field on the optical absorption of amorphous molecular semiconductors doped with polymethine dyes

The effect of a dc electric field on the evolution of the electronic absorption spectra of poly(N-epoxypropylcarbazole) (PEPC), poly(styrene) (PS), and poly(vinyl butyral) (PVB) films doped with methine dyes is investigated. It is revealed that these spectra in the absorption range of the dye undergo transformations depending on the dipole moment and the symmetry of the π-electron structure of dye molecules. The inference is made that the electron density in the dye molecule is redistributed in an external electric field. This redistribution gives rise to the electric field-induced anisotropy in the spatial distribution function of photogenerated electron-hole pairs in amorphous molecular semiconductors.     

Two-dimensional electron-hole pair diffusivities in thin GaAs/AlGaAs Quantum Wells

Diffusivities of two-dimensional electron-hole pairs in thin GaAs/AlGaAs Quantum Wells (QWs) are studied experimentally and theoretically as functions of temperature and well-width. With growing well-widths, increasing diffusivities are observed for fixed Al-contents. Experimental diffusivities for the lateral carrier motion in continuously as well as in interrupted-grown thin QWs of different barrier Al-content are presented for T>150 K. Increasing diffusivities are observed for rising temperatures in the range T190 K. A comparison of the experimental data and results of theoretical model calculations indicates that the increase is partly related to thermal dissociation of excitons into free carrier pairs. The effective diffusivity of this two-component system is calculated using a system of rate equations and considering acoustic-deformation-potential scattering, polar-optical scattering and barrier-alloy-disorder scattering.The experimental data were obtained at: 4. Physikalisches Institut, Universität Stuttgart, Pfaffenwaldring 57, W-7000 Stuttgart 80, Germany     

Spectroscopic studies of real space indirect symmetric GaAs/AlAs short period superlattices

The band structure and the optical transitions of symmetric ultra-short period (GaAs) _m /(AlAs) _n superlattices (n=m is the number of monolayers) have been studied using different spectroscopic techniques, namely photoacoustic spectroscopy, reflectivity and luminescence, photoluminescence excitation and high excitation intensity time-resolved luminescence. Direct observation of the transition from type I to type II energy band alignment is reported for superlattices whose configuration consists of more than 12 monolayers (i.e. m=n>12). The radiative recombination processes associated with the real space indirect transitions have been investigated as a function of the density of photogenerated electron-hole pairs, revealing an unusual density-dependent behaviour. A tentative interpretation in terms of a condensed electron-hole state at the indirect gap is given, which accounts for the long decay time of the type II luminescence at high excitation rate.     

Electron-hole liquid in strained SiGe layers of silicon heterostructures

The electron-hole liquid has been found in strained SiGe thin films of Si/Si_1?x Ge_x/Si heterostructures. The density and binding energy of the electron-hole liquid have been determined. Owing to the presence of internal strains in the SiGe layer, the density and binding energy are significantly smaller than the respective quantities for the electron-hole liquid in a bulk single crystal of the solid solution of the same composition. The critical temperature of the transition from the exciton gas to the electron-hole liquid is estimated using the experimental data. The Mott transition (from the exciton gas to electron-hole plasma) occurs above the critical temperatures for high excitation intensities.     

Interwell radiative recombination in the presence of random potential fluctuations in GaAs/AlGaAs biased double quantum wells

The interwell radiative recombination from biased double quantum wells (DQW) in pin GaAs/AlGaAs heterostructures is investigated at different temperatures and external electrical fields. The luminescence line of interwell recombination of spatially separated electron-hole pairs exhibits systematic narrowing with temperature increase from 4.5 to 30 K. A theoretical model is presented which explains the observed narrowing in terms of lateral thermally activated tunneling of spatially separated e-h pairs localized by random potential fluctuations in the quantum wells. Pis’ma Zh. éksp. Teor. Fiz. 67, No. 8, 580–585 (25 April 1998) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Photoelectric properties and electroluminescence of <Emphasis Type="Italic">p-i-n</Emphasis> diodes based on GeSi/Si heterostructures with self-assembled nanoclusters

This paper reports on the results of investigations into the photoelectric properties and electroluminescence of p-i-n diodes based on GeSi/Si heterostructures with GeSi self-assembled nanoclusters embedded in the i region. The p-i-n diodes are grown through sublimation molecular-beam epitaxy using a vapor-phase source of germanium. The photovoltage spectra of the p-i-n diodes measured at a temperature of 300 K exhibit a photosensitivity band attributed to interband optical transitions in the GeSi nanoclusters. A new approach to analyzing the photosensitivity spectra of the heterostructures containing GeSi thin layers is proposed, and the energy at the edge of the photosensitivity bands assigned to these layers is determined. The electroluminescence observed in the p-i-n diodes at 77 K is associated with the radiative interband optical transitions in GeSi nanoclusters.     

铁电材料光催化活性的研究进展

光催化技术被认为是最有前景的环境污染处理技术,这就使得光催化剂材料备受瞩目.近年来,铁电材料作为新型光催化剂材料受到人们越来越多的关注,其原因在于铁电材料特有的自发极化有望解决催化反应过程中的电子-空穴对复合问题,进而提高光催化活性.本文从两个方面对铁电极化如何影响光催化进行综述:一方面,从铁电极化入手归纳总结其对电子-空穴对分离的影响,进而更深入地从极化引发的退极化场和能带弯曲两个部分来阐述具体的影响机理;另一方面,为了消除静电屏蔽,分别从温度、应力(应变)、电场三个外场因素调控极化入手,归纳总结外场调控极化对电子-空穴对分离的影响,进而影响光催化活性.最后对该领域今后的发展前景进行了展望.     

Electronic and optical properties of van der Waals vertical heterostructures based on two-dimensional transition metal dichalcogenides: First-principles calculations

Four vertical heterostructures based on two-dimensional transition-metal dichalcogenides (TMDs) – MoS₂/GeC, MoSe₂/GeC, WS₂/GeC, and WSe₂/GeC, were studied by density functional theory calculations to investigate their structure, electronic characteristics, principle of photogenerated electron–hole separation, and optical-absorption capability. The optimized heterostructures were formed by van der Waals (vdW) forces and without covalent bonding. Their most stable geometric configurations and band structures display type-II band alignment, which allows them to spontaneously separate photogenerated electrons and holes. The charge difference and built-in electric field across the interface of these vdW heterostructures also contribute to preventing the photogenerated electron–hole recombination. Finally, the high optical absorption of the four TMD-based vdW heterostructures in the visible and near-infrared regions indicates their suitability for photocatalytic, photovoltaic, and optical devices.     

Blue shift in the luminescence spectra of MEH-PPV films containing ZnO nanoparticles

Luminescence properties of nanocomposites consisting of ZnO nanoparticles in a conjugated polymer, poly [2-methoxy-5-(2′-ethyl hexyloxy)-phenylene vinylene] (MEH-PPV), were investigated. Photoluminescence measurements reveal a blue shift in the emission spectrum of MEH-PPV upon incorporation of ZnO nanoparticles into the polymer film while the emission is increasingly quenched with increasing ZnO concentration. In contrast, the structure of the polymer and its conjugation length are not affected by the presence of ZnO nanoparticles (up to 16 wt% ZnO) as revealed by Raman spectroscopy. The blue shift and photoluminescence quenching are explained by the separation of photogenerated electron-hole pairs at the MEH-PPV/ZnO interface and the charging of the nanoparticles.     

First-principles study of the electronic and optical properties of the (Y, N)-codoped anatase TiO2 photocatalyst

First-principles plane-wave pseudopotential calculations are performed to study the geometrical structures, formation energies, and electronic and optical properties of Y-doped, N-doped, and (Y, N)-codoped TiO₂. The calculated results show that Y and N codoping leads to lattice distortion, easier separation of photogenerated electron-hole pairs and band gap narrowing. The optical absorption spectra indicate that an obvious red-shift occurs upon Y and N codoping, which enhances visible-light photocatalytic activity.     

Formation and properties of high density Si nanodots

Laser induced crystallization of ultrathin hydrogenated amorphous Si films or amorphous Si-based multilayered structures were used to get high density Si nanodots. The present technique can get size controllable Si nanodots embedded in various dielectric materials with uniform distribution which was revealed by cross-section transmission electron microscopy. Room temperature photoluminescence and electroluminescence were achieved with the emission wavelength in a visible light region both from a-SiN/Si nanodots/a-SiN sandwiched and Si nanodots/SiO₂ multilayered structures. The luminescence was associated with the radiative recombination of generated electron-hole pairs in Si nanodots or the luminescent surface states. The electroluminescence intensity is increased with increasing the injection current implying the bipolar carrier injection plays an important role in enhancing the luminescence efficiency. The formed Si nanodots by the present approach can be applied for many kinds of devices such as high efficient light emitting diodes and solar cells.     

Charge separation in semicrystalline polymeric semiconductors by photoexcitation: is the mechanism intrinsic or extrinsic?

We probe charge photogeneration and subsequent recombination dynamics in neat regioregular poly(3-hexylthiophene) films over six decades in time by means of time-resolved photoluminescence spectroscopy. Exciton dissociation at 10 K occurs extrinsically at interfaces between molecularly ordered and disordered domains. Polaron pairs thus produced recombine by tunneling with distributed rates governed by the distribution of electron-hole radii. Quantum-chemical calculations suggest that hot-exciton dissociation at such interfaces results from a high charge-transfer character.