First direct observation of EL2-like defect levels in annealed LT-GaAS

Nonstoichiometric arsenic-rich GaAs grown at low temperatures by molecular beam epitaxy (LT-GaAs) has been found to be semi-insulating after high-temperature annealing. The origin of this technologically important conversion is not yet fully understood. In order to study this effect, we performed photocurrent measurements on p-LT GaAs-n diodes in the spectral range between 0.75 and 1.5eV at 8K. The photocurrent spectra revealed the following features which are unique to the EL2 level: photoquenching, characteristic photoionization transitions to conduction band minima and a presence of a broad band due to the effect of auto-ionization from the excited state. Moreover, modeling of the optical excitation process using realistic band structure demonstrates that these features cannot be explained by “internal photoemission” originating from As precipitates, as the “buried Schottky barrier model” predicts. This is the first direct experimental evidence for the existence of EL2-like defect levels and their importance for understanding the optical and electronic properties of annealed LT-GaAs.     

Hopping conduction and its photoquenching in molecular beam epitaxial GaAs grown at low temperatures

As the growth temperature of molecular beam epitaxial GaAs is increased from 250 to 400°C, the dominant conduction changes from hopping conduction to band conduction with a donor activation energy of 0.65 eV. A 300°C grown layer is especially interesting because each conduction mechanism is dominant in a particular temperature range, hopping below 300K and band conduction above. Below 140K, the hopping conduction is greatly diminished (quenched) by irradiation with either infrared (hv≤1.12 eV) or 1.46 eV light, but then recovers above 140K with exactly the same thermal kinetics as are found for the famous EL2. Thus, the 0.65 eV donor, which is responsible for both the hopping and band conduction, is very similar to EL2, but not identical because of the different activation energy (0.65 eV vs 0.75 eV for EL2).     

半绝缘GaAs中EL2能级低温精细结构和光猝灭效应

本研究采用近红外光谱法和低温测量技术,获得了EL2能级的心内跃迁特征光谱和包括6个小峰的精细结构。探讨了心内跃迁与横向声学(TA)声子的耦合机理,系统观察了它的光猝灭效应,提出亚稳态模型,得出了由10K升温过程EL2能级近红外吸收与温度的依赖关系,确定了115K为亚稳态恢复至稳态的最低温度转变点。由实验结果提供的EL2能级内部结构的信息,提出EL2能级的理论模型。     

Kinetics of charge transfer processes in organic solar cells: Implications for the design of acceptor molecules

We report the electronic properties of a new class of non-fullerene electron acceptor molecules with electron affinities tunable over an approximately 1 eV range. This tunability allows us to vary the thermodynamic driving force for electron transfer (ΔG°) such that it is equal-and-opposite-to the reorganization energy for the ionized states (λ). We utilize this design principle, derived from Marcus–Hush theory, to optimize the rate of charge transfer in blends of these acceptors with poly(3-n-hexylthiophene-2,5-diyl) (P3HT) – a standard organic solar cell donor material. We show that computationally inexpensive calculations can be used to parameterize Marcus–Hush theory so as to correctly predict whether quenching will occur. Arguments based solely on energetics are common in the literature and we show that such theories do not predict the trends observed in our photoluminescence quenching experiments. This is the case whether the energies determined from experiments [cyclic voltammetry (CV) and the optical gap] or calculated from density functional theory for the solid state. We predict essentially barrier-less photoelectron transfer (PET) from P3HT to the acceptor 2-[{7-(9,9-di-n-propyl-9H-fluoren-2-yl)benzo[c] ,  and  thiadiazol-4-yl}methylene]malononitrile (or K12), consistent with the experimental photoluminescence quenching efficiencies found for P3HT:K12 blends. Our results clearly show that energetics alone is not sufficient to predict PET between the acceptor–donor pair, and that kinetics are an important determining factor.     

Investigations on the structural and optical properties of Li,N and (Li,N) co-doped ZnO thin films prepared by sol–gel technique

Pure and doped zinc oxide thin films have been deposited on sapphire substrates by using the sol–gel method and spin coating technique. The X-ray diffraction pattern showed that the deposited films exhibit hexagonal zinc oxide structure. Room temperature photoluminescence measurements show the presence of two emission bands. The predominant near band edge ultraviolet emission is at 3.28 eV and a suppressed broad band of deep level emission in the range of 2.1–2.5 eV. The incorporation of nitrogen is indicative of p-type behavior as observed from X-ray photoelectron spectrum of nitrogen in the doped samples. The p-type conduction of Li, N:ZnO may be attributed to the formation of a LiZn–N complex acceptor.     

Photoluminescence Studies of Si-Doped Epitaxial GaAs Films Grown on (100)- and (111)A-Oriented GaAs Substrates at Lowered Temperatures

The electrical properties and photoluminescence features of uniformly Si-doped GaAs layers grown on GaAs substrates with the (100) and (111)A crystallographic orientations of the surface are studied. The samples are grown at the same As₄ pressure in the growth temperature range from 350 to 510°C. The samples grown on GaAs(100) substrates possess n-type conductivity in the entire growth temperature range, and the samples grown on GaAs(111)A substrates possess p-type conductivity in the growth temperature range from 430 to 510°C. The photoluminescence spectra of the samples exhibit an edge band and an impurity band. The edge photoluminescence band corresponds to the photoluminescence of degenerate GaAs with n- and p-type conductivity. The impurity photoluminescence band for samples on GaAs(100) substrates in the range 1.30–1.45 eV is attributed to V_As defects and Si_As–V_As defect complexes, whose concentration varies with sample growth temperature. Transformation of the impurity photoluminescence spectra of the samples on GaAs(111)A substrates is interpreted as being a result of changes in the V_As and V_Ga defect concentrations under variations in the growth temperature of the samples.     

Photoluminescence in silicon implanted with erbium ions at an elevated temperature

Photoluminescence spectra of n-type silicon upon implantation with erbium ions at 600°C and oxygen ions at room temperature and subsequent annealings at 1100°C in a chlorine-containing atmosphere have been studied. Depending on the annealing duration, photoluminescence spectra at 80 K are dominated by lines of the Er³⁺ ion or dislocation-related luminescence. The short-wavelength shift of the dislocation-related luminescence line observed at this temperature is due to implantation of erbium ions at an elevated temperature. At room temperature, lines of erbium and dislocation-related luminescence are observed in the spectra, but lines of near-band-edge luminescence predominate.     

Growth of phosphorus-doped p-type ZnO thin films by MOCVD

Phosphorus-doped p-type ZnO thin films are prepared on glass substrates by metalorganic chemical vapor deposition (MOCVD). DEZn, O2, and P2O5 powders are used as reactant and dopant sources. The p-type ZnO films are grown at a temperature between 673 K and 723 K. The best p-type sample has a low resistivity of A strong emission peak at 3.354 eV corresponding to neutral acceptor bound excitons is observed at 77 K in the photoluminescence spectra, which further verifies the p-type characteristics of the films.     

MIS characterization and modeling of the electrical properties of the epitaxial Caf2/Si(111) interface

CaF₂ layers have grown by molecular beam epitaxy on bothn-type andp- type Si(111). Capacitance-voltage (C-V) and current-voltage (I-V) measurements have been made on metal-insulator-semiconductor (MIS) capacitors to characterize these structures. For devices onp-type Si, C-V characteristics show only the insulator value of the capacitance over a wide range of applied voltages, indicating an accumulated surface. At room temperature, C-V characteristics ofn-type devices show the minimum value of the capacitance (corresponding to inversion) for small voltages, but modulation of the capacitance at larger voltages. At 200 K, this modulation is no longer present in the C-V curves. I-V curves show a rapid increase in the leakage current at relatively low fields at room temperature, and this leakage decreases dramatically with temperature. These results are largely independent of cleaning procedure, growth temperature, and the degree of misalignment of the substrate. The characteristics are modeled by assuming the Fermi level to be pinned at the valence-band edge, and the modulation in the C-V characteristics ofn-type samples to be driven by leakage currents. Work done at GE while a graduate student in the School of Electrical Engineering, Cornell University. Present address: Jet Propulsion Laboratory, 4800 Oak Grove Dr., Pasadena, CA 91109.     

Optical properties and thermal transport of carriers in (Zn,Cd)Se-ZnSe heterostructures

We report a detailed optical study of ZnSe-based graded index separate confinement heterostructures. These structures were grown by metalorganic vapor phase epitaxy and are composed of either one or two Zn_0.79Cd_0.21Se central well(s) embedded between two ZnCdSe barriers which cadmium composition varies linearly from 5% near the wells to 0% at the end of the barriers. 2K photoreflectance and reflectivity experiments allow the observation of excitonic transitions involving the third electron and heavy hole confined states. The temperature dependence of the photoluminescence lines under in-well resonant excitation conditions (E_exc = 2.661 eV) shows that the thermal quenching of the photoluminescence line is ruled by nonradiative recombinations on defects localized at the heterointerfaces at low temperature and by the thermal escape of the minority carriers at higher temperatures. Under above-barrier excitation conditions (E_exc=3.814 eV), the temperature dependence of the photoluminescence line from the well shows a strong influence of the mechanism of diffusion of the carriers from the barriers to the well.     

High-temperature luminescence in an n-GaSb/n-InGaAsSb/p-AlGaAsSb light-emitting heterostructure with a high potential barrier

The electroluminescent properties of an n-GaSb/n-InGaAsSb/p-AlGaAsSb heterostructure with a high potential barrier in the conduction band (large conduction-band offset) at the n-GaSb/n-InGaAsSb type-II heterointerface (ΔE _c = 0.79 eV) are studied. Two bands with peaks at 0.28 and 0.64 eV at 300 K, associated with radiative recombination in n-InGaAsSb and n-GaSb, respectively, are observed in the electroluminescence (EL) spectrum. In the entire temperature range under study, T = 290–480 K, additional electron-hole pairs are formed in the n-InGaAsSb active region by impact ionization with hot electrons heated as a result of the conduction-band offset. These pairs contribute to radiative recombination, which leads to a nonlinear increase in the EL intensity and output optical power with increasing pump current. A superlinear increase in the emission power of the long-wavelength band is observed upon heating in the temperature range T = 290–345 K, and a linear increase is observed at T > 345 K. This work for the first time reports an increase in the emission power of a light-emitting diode structure with increasing temperature. It is shown that this rise is caused by a decrease in the threshold energy of the impact ionization due to narrowing of the band gap of the active region.     

Photoluminescence of anodized layers of CdSiAs2

CdSiAs₂ belongs to the II-IV-V₂ group of chalcopyrite semiconductors with a direct band gap of 1.51 eV at T=300 K. In this paper we investigate the spectral dependence of the steady-state photoluminescence of CdSiAs₂ anodized layers. These layers were fabricated by electrochemical anodization of unoriented p-type CdSiAs₂ wafers in an solution of HF in ethanol. It is found that a broad photoluminescence band with a maximum at the photon energy ℏω=1.82 eV at 300 K arises. This band lies deep in the fundamental absorption region of CdSiAs₂ crystals. The dependence of the parameters of the photoluminescence spectra of anodized Si, GaAs, and CdSiAs₂ layers is discussed. Fiz. Tekh. Poluprovodn. 31, 313–314 (February 1997)     

Inelastic scattering of hot electrons by neutral donors in heavily silicon-doped GaAs/AlAs quantum wells

The energy and momentum relaxation of hot electrons in n-type GaAs/AlAs quantum wells is studied. Hot photoluminescence due to the recombination of hot electrons with holes bound on Si acceptors is observed in structures with a high level of doping with silicon. Using the method of magnetic depolarization of hot photoluminescence, the probability of scattering of hot electrons is found to decrease substantially with increasing temperature in the range 4–80 K. This effect is shown to be due to the ionization of donors. It is established that the probability of inelastic scattering by neutral donors is several times greater than the probability of quasielastic electron-electron scattering. Fiz. Tekh. Poluprovodn. 33, 1235–1239 (October 1999)     

Effect of in situ photoexcitation of n-type Si as a result of ion implantation at low doses on the formation of radiation defects

The effect of in situ photoexcitation of the electronic subsystem of a semiconductor as a result of implantation of low ion doses on the formation of complexes of radiation defects in n-type Si is investigated by the DLTS method. The n-type Si samples were irradiated with 150-keV O ₂ ⁺ and N ₂ ⁺ ions at the same dose 10¹¹ cm⁻² and Ar⁺ ions at doses 7×10¹⁰ and 2×10¹¹ cm⁻². With the exception of the latter case, the ion energy and dose were chosen so as to produce approximately the same number of initially displaced Si atoms and the same depth distribution of such atoms from the target surface. The temperature of the n-type Si samples during irradiation was 300 or 600 K. Photoexcitation of the semiconductor was performed using UV radiation with various power densities. It is shown that radiative heating of the samples during ion implantation suppresses the formation of radiation-defect complexes, while photoexcitation of n-type Si, in contrast, intensifies their formation. It is found that the effect of illumination increases with decreasing ion mass and with increasing target temperature. The effect of UV illumination on defect formation in n-type Si as a function of sample temperature during ion implantation is established. It is found that the density of divacancies in n-type Si saturates with increasing illumination intensity. Fiz. Tekh. Poluprovodn. 33, 537–541 (May 1999)     

Electrical,optical and photoelectrochemical properties of natural enargite,Cu3AsS4

The semiconducting properties of natural samples of enargite, a copper and arsenic suphide (Cu₃AsS₄), have been studied. They have been found to be p-type semiconductors with a resistivity of about 7 Ω cm, a doping level of about 10¹⁷ cm^?3 and a mobility of 9 cm²V^?1 s^?1. The variation of the resistivity as a function of temperature allows to determine an activation energy of 0.11 eV. Two optical transitions have been determined, an indirect one at 1.19 eV and a direct one at 1.44 eV. The samples, mounted as working electrodes in a photoelectrochemical set-up, are photosensitive and behave as p-type photocathodes. The two transitions are found again from the analysis of photocurrent spectra. The direct band gap value is close to the ideal value required for photovoltaic applications. However the quantum efficiencies obtained here are still low.     

Accurate measurement of capture cross sections in deep level transient spectroscopy: Application to EL2 in GaAs

A rigorous formulation of capacitance changes during trap filling processes is presented and used to accurately determine the electron capture cross section of EL2 in GaAs at a particular temperature, 377K, in this case. The value, σ_n (377K) = 2.7 × 10⁻¹⁶ cm², is compared with that predicted from the emission dependence.     

Electrical properties and luminescence of CuInSe2

We have studied the electrical properties and luminescence spectra of melt-grown CuInSe₂ single crystals and the doping of the crystals with intrinsic defects and extrinsic impurities. The preparation and the properties of p-n junctions are also discussed. We find that the low temperature photoluminescence spectra of crystals as-grown or annealed between 400 and 700 C are characteristic of the conductivity type. At 77 K, p-type crystals emit in a band peaked at 1.00 eV (type A spectrum) whereas the emission of n-type crystals peaks at 0.93 eV (type B spectrum). Type A and type B spectra can be interchanged by alternate anneals in minimum or maximum Se pressure. Type B emission dominates the electroluminescence spectrum of p-n junctions. These features are explained by the appearing and disappearing of a donor level as a consequence of annealing in vacuum or in Se atmosphere. We find that Zn and Cd act as donors. Crystals doped with these impurities have electron concentrations above 10¹⁸ cm⁻³. Zn-dopped samples exhibit a very broad recombination band below the bandgap in photoluminescence both at 77 and 300 K.     

Excitation photocapacitance study of EL2 in n-GaAs and its relation to non-stoichiometry

The excitation photocapacitance measurements are performed on n-GaAs to obtain charge transition characteristics of EL2 defects in a full spectral region. It is shown that the threshold photon energy for EL2⁺⁺ to EL2⁺ transition is changed as a function of the primary excitation photon energy. It is also shown that the Frank–Condon shifts (d_FC) changed. It is considered that the lattice relaxation around the EL2 defect is affected by the deviation from the stoichiometric composition.     

Selenium Substitution in Bithiophene Imide Polymer Semiconductors Enables High-Performance n-Type Organic Thermoelectric

Designing n-type polymers with high electrical conductivity remains a major challenge for organic thermoelectrics (OTEs). Herein, by devising a novel selenophene-based electron-deficient building block, the pronounced advantages of selenium substitution in simultaneously enabling advanced n-type polymers is demonstrated with high mobility (≈2 orders of magnitude higher versus their sulfur-based analogues due to both intensified intra- and inter-chain interactions) and much improved n-doping efficiency (enabled by the largely lowered LUMO level with a ≈0.2 eV margin) of the resulting polymers. Via side chain optimization and donor engineering, the selenium-substituted polymer, f-BSeI2TEG-FT, achieves a highest conductivity of 103.5 S cm⁻¹ and power factor of 70.1 µW m⁻¹ K⁻², which are among the highest values reported in literature for n-type polymers, and f-BSeI2TEG-FT greatly outperformed the sulfur-based analogue polymer by 40% conductivity increase. These results demonstrate that selenium substitution is a very effective strategy for improving n-type performance and provide important structure-property correlations for developing high-performing n-type OTE materials.     

Fabrication of Bismuth Telluride-Based Alloy Thin Film Thermoelectric Devices Grown by Metal Organic Chemical Vapor Deposition

Bismuth–antimony–telluride based thin film materials were grown by metal organic vapor phase deposition (MOCVD). A planar-type thermoelectric device was fabricated with p-type Bi_0.4Sb_1.6Te₃ and n-type Bi₂Te₃ thin films. The generator consisted of 20 pairs of p-type and n-type legs. We demonstrated complex structures of different conduction types of thermoelectric elements on the same substrate using two separate deposition runs of p-type and n-type thermoelectric materials. To demonstrate power generation, we heated one side of the sample with a heating block and measured the voltage output. An estimated power of 1.3 μW was obtained for the temperature difference of 45 K. We provide a promising procedure for fabricating thin film thermoelectric generators by using MOCVD grown thermoelectric materials that may have a nanostructure with high thermoelectric properties.