Study of shallow impurity states in compound semiconductors using high resolution photoluminescence spectroscopy

In this paper we review briefly the use of high resolution photoluminescence to study the behavior of shallow impurity states in compound semiconductors. As an illustration we focus our review on GaAs. The binding energies of the ground state and of several low-lying excited states of the impurity centers are determined by studying the radiative transitions associated with excitons bound to neutral donors or acceptors. The difference between the binding energies of different donors in GaAs is rather small. Thus to resolve transitions associated with different chemical donors a magnetic field is used. This has the effect of sharpening the transitions as well as increasing the separation between them. One can identify donors in samples with total impurity concentrations as high as 5X10¹⁵/cm³. The binding energies of different chemical acceptors in GaAs are much higher. Thus the radiative transitions associated with excitons bound to neutral acceptors can be resolved in zero magnetic field. Energy levels of shallow donors and acceptors in GaAs are reviewed.     

Slow relaxation of the spin doublet decamethylferrocenium cation as a probe for spin on organo-polycyanides,new organoferromagnets

The contributions of Mössbauer spectroscopy and susceptibility studies to the discovery of a variety of new and some cases unprecedented magnetic behavior in polymeric charge transfer salts are highlighted. The materials are based on electron transfer from decamethylferrocene to polycyanide electron acceptors.     

Gate-tunable bandgap in bilayer graphene

The tight-binding model of bilayer graphene is used to find the gap between the conduction and valence bands as a function of both the gate voltage and the doping level by donors or acceptors. The total Hartree energy is minimized and an equation for the gap is obtained. This equation for the ratio of the gap to the chemical potential is determined only by the screening constant. Therefore, the gap is strictly proportional to the gate voltage or the carrier concentration in the absence of donors or acceptors. But in the case where the donors or acceptors are present, the gap demonstrates an asymmetric behavior on the electron and hole sides of the gate bias. A comparison with experimental data obtained by Kuzmenko et al. demonstrates a good agreement.     

Assignment of the low frequency vibrations in electron donor-acceptor complexes by ultrafast coherent spectroscopy

Coherent oscillations in a spontaneous fluorescence of electron donor-acceptor (EDA) complexes in solution were observed with three different acceptors: tetracyanoethylene (TCNE), chloranil, and fluoranil with various electron donors. Different oscillatory frequencies were observed for the complexes with different acceptors. The similar frequencies are observed for the complexes with different donors and a common acceptor: 155 cm⁻¹ (period of 215 fs) for the complexes with TCNE, 178 cm⁻¹ (187 fs) for the complexes with chloranil, and 212 cm⁻¹ (157 fs) for the complex with fluoranil. It is concluded, that the out-of-plane vibrational mode of the acceptor, having b_3u symmetry, is responsible for the observed oscillations in all three cases (three acceptors). The time-dependent fluorescence spectrum for the TCNE - HMB complex is reconstructed and the fluorescence peak-shift correlation function is obtained. The ultrafast relaxation of the fluorescence peak position is superimposed with the oscillatory component. The main component of the spectral relaxation of 115 fs is attributed mainly to the intramolecular vibrational energy redistribution process in both donor and acceptor parts of the complex. The oscillatory behavior of the fluorescence peak position demonstrates the modulation of the transition frequency during the vibrations. The modulation of the mean transition moment is observed as well. Thus two mechanisms are observed to be responsible for the oscillations: the modulation of the transition frequency and the modulation of the mean transition moment by the vibrational motion.     

Evidence for a donor-acceptor pair band in CuInSe2

The broad-band emission, observed in p-type crystals, was studied as a function of excitation intensity and temperature. The band peak is usually in the energy range of 0.93–0.95 eV at 4.2°K. The band shifts to higher energy as the excitation intensity of temperature increases. This behavior is consistent with a donor-acceptor pair-band mechanism. The acceptor energy E_A is 85 ± 2 meV. The acceptors and donors involved in the pair band appear to be Cu and Se vacancies.     

Far-infrared photoconductivity spectra of quenched-in acceptors in germanium: Chemical effects on the SA1 acceptors

Far-I.R. photoconductivity reveals the existence of at least four different kinds of SA₁ acceptors in germanium quenched from T > 800 each acceptor producing two or more hydrogenic excitation line series. One acceptor is correlated with the presence of Ni, another one with strong Cu contamination. The two other acceptors, which we call ‘normal’ and ‘shifted’, occur in samples quenched without intentional doping. The experiments indicate that the SA₁ acceptors in germanium are impurity complexes involving fast diffusing elements. We discuss a model according to which the SA₁ acceptors would be interstitial-substitutional pairs of transition metals. In particular, we propose to assign the ‘normal’ SA₁ acceptors to Fe_I-Cu_S pairs.     

Shallow impurity centers in semiconductor quantum well structures

Interest in the study of the behavior of shallow impurity centers in superlattices and quantum well structures is fairly recent. This paper reviews briefly both the theoretical and experimental work done in this field in the last few years. Several recent calculations of the energy levels of hydrogenic impurity states in quantum well structures, such as Ga_1?xAl_xAsGaAsGa_1?xAl_xAs, are reviewed. The behavior of these levels as a function of the quantum well size is discussed. Recent experimental data concerning the variations of the binding energies of shallow donors and acceptors as a function of the GaAs quantum well size are reviewed. A comparison between these experimental measurements and the results of recent calculations is presented.     

Design and characterization of TlInSe2 varactor devices

TlInSe₂ single crystal has been successfully prepared by the Bridgman crystal growth technique. The crystal, which exhibits compositional atomic percentages of 25.4%, 25.2% and 49.4% for Tl, In and Se, respectively, is found to be of tetragonal structure with lattice parameters of a=0.8035 and c=0.6883 nm. The crystals were used to design radio frequency sensitive varactor device. The temperature dependence of the current-voltage characteristics of the device allowed the calculation of the room temperature barrier height and ideality factor as 0.87 eV and as 3.2, respectively. Rising the device temperature increased the barrier height and decreased the ideality factor. This behavior was attributed to the current transport across the metal-semiconductor interface. The capacitance of the device is observed to increase with increasing voltage and increasing temperature as well. The temperature activation of the capacitance starts above 82 °C with a temperature coefficient of capacitance being 1.08×10⁻³ K⁻¹. Furthermore, the capacitance of the device was observed to increase with increasing frequency up to a maximum critical frequency of 4.0 kHz, after which the capacitance decreased with increasing frequency. The behavior reflected the ability of maximum amount of charge holding being at a 4.0 kHz. The analysis of the capacitance-voltage characteristics at fixed frequencies reflected a frequency dependent barrier height and acceptors density. The decrease in the barrier height and acceptors density with increasing frequency is mainly due to the inability of the free charge to follow the ac signal.     

Binding energy of positively charged acceptors in germanium - a Green's function Monte Carlo calculation

Recent spectroscopic measurements in Ge reveal positively charged acceptors consisting of an extra hole bound to a double or triple acceptor. Using the effective-mass approximation and a pseudo-atom model which permits up to four holes in the 1s ground state, we calculate the binding energies of these positively charged acceptors by the Green's function Monte Carlo method. For double acceptors the results of the pseudo-atom model compare favorably with experiments, whereas for triple acceptors the differences are significant.     

Electron paramagnetic resonance of scandium in silicon carbide

The EPR spectra of scandium acceptors and Sc²⁺(3d) ions are observed in 6H-SiC crystals containing a scandium impurity. The EPR spectra of scandium acceptors are characterized by comparatively small hyperfine interaction constants, whose values are consistent with the constants for other group III elements in SiC: boron, aluminum, and gallium acceptors. The EPR spectra of scandium acceptors undergo major changes in the temperature interval 20–30 K. In the low-temperature phase the EPR spectra are characterized by orthorhombic symmetry, whereas the high-temperature phase has higher axial symmetry. The EPR spectra observed at temperatures above 35 K and ascribed by the authors to Sc²⁺(3d) ions, or to the A ²⁻ state of scandium, have significantly larger hyperfine structure constants and narrower lines in comparison with the EPR spectra of scandium acceptors. The parameters of these EPR spectra are close to those of Sc²⁺(3d) in ionic crystals and ZnS, whereas the parameters of the EPR spectra of scandium acceptors correspond more closely to the parameters of holes localized at group III atoms, in particular, at scandium atoms in GeO₂. It is concluded that in all centers the scandium atoms occupy silicon sites. Fiz. Tverd. Tela (St. Petersburg) 39, 52–57 (January 1997)     

“Charge transfer Complexes of Indolyldiene Aniline derivatives with p-benzoquinone derivatives”

Abstract

Charge transfer (CT) complexes of p-benzoquinone derivatives with Indolyldiene aniline derivatives have been prepared and investigated by Elemental analysis, IR, ¹H-NMR and electronic absorption spectroscopy. The spectral changes revealed that acidic acceptors form complexes with π - π? electronic interaction and proton transfer while non-acidic acceptors yield complexes having π - π transition only. The formation of 1:2 (D:A) complexes is also ascertained. The ionization potential and electron affinity are determined from the electronic absorption spectra for both the donors and acceptors respectivily.     

Certain characteristics of the energy spectra of impurity centers and charge-carrier scattering processes in high-resistivity GaAs(O)

The behavior of electron and hole mobilities in illuminated high-resistivity single crystals of oxygen-doped gallium arsenide has been investigated and compared with the behavior of these parameters in the unilluminated specimen. A complete liquidation of charged centers was observed at temperatures below 50°K which shows that these crystals do not contain shallow donors or acceptors. The electron-to-hole mobility ratio in the neutral-center scattering region has also been determined.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No.2, pp.25–34, February, 1976.In conclusion the authors express their appreciation to V. B. Dik for designing and constructing the helium cryostat and to M. S. Al' Kuveiti for performing some of the measurements of dark characteristics of some of the samples.     

Room-temperature ferromagnetism in N+-implanted ZnO:Mn thin films

Mn–N co-doped ZnO films with wurtzite structure were fabricated by RF magnetron sputtering together with the ion-implantation technique. Then a post-annealing at 650 °C for 10 min in a N₂ atmosphere was performed to activate the implanted N⁺ ions and recover the crystal quality, and a p-type ZnO:Mn–N film with a hole concentration of about 2.1×10¹⁶ cm^?3 was obtained. It is found that the Mn mono-doped ZnO film only exhibits paramagnetic behavior, while after N⁺-implantation, it shows ferromagnetism at 300 K, and the magnetization of the ZnO:Mn–N films can be further enhanced by thermal annealing due to the activation of the N acceptors. Our experimental results confirm that the codoping N acceptors are favorable for ferromagnetic ordering of Mn²⁺ ions in ZnO, which is consistent with the recent theoretical calculations.     

Suppression of electron spin relaxation in Mn-doped GaAs

We report a surprisingly long spin relaxation time of electrons in Mn-doped p-GaAs. The spin relaxation time scales with the optical pumping and increases from 12 ns in the dark to 160 ns upon saturation. This behavior is associated with the difference in spin relaxation rates of electrons precessing in the fluctuating fields of ionized or neutral Mn acceptors, respectively. For the latter, the antiferromagnetic exchange interaction between a Mn ion and a bound hole results in a partial compensation of these fluctuating fields, leading to the enhanced spin memory.     

Magneto-piezospectroscopy of acceptors in tetrahedrally coordinated semiconductors

This paper presents a study of the magnetospectroscopy of acceptors in elemental group-IV semiconductors in the presence of uniaxial stress. We use a formulation of the effect of stress on the transition probabilities for optical absorption which represents a considerable simplification over previous treatments. We give an analysis of both the longitudinal and the transverse magneto-spectroscopy of acceptors in semiconductors having the diamond structure under uniaxial stress. The results are used to determine the values of theg-factors for two levels of Ga acceptors in Ge by comparing the present results with the experimental data. Due to the relevance of its scientific content, this paper has been given priority by the Journal Direction.     

掺铍GaAs量子阱的光致荧光

测量了掺铍的,阱宽约为10nm的GaAs量子阱在4.2K的光致荧光。掺杂浓度分别为1×10¹⁷和5×10¹⁸cm^-3。测量结果表明:对于无规掺杂,局域在阱中心的铍的状态密度与导带电子从n=1量子能级到阱中心中性铍的跃迁概率的乘积大于对应于介面铍的乘积。另外,实验结果也表明:当掺杂浓度升高时,由于带隙收缩的影响,阱中心铍的电离能减小。     

Resonance spectroscopy of donor and acceptor centers in compensated cadmium telluride

Methods based on the selective excitation of low-temperature photoluminescence (LTPL) are applied to the analysis of the electron spectrum of defects created in strongly compensated cadmium telluride (CdTe). It is shown that dominant (with the highest concentration) acceptors have activation energies of 48.2 ± 0.4 meV, 97.9 ± 0.6 meV, and 119.7 ± 1.0 meV, which is not characteristic of known substitutional impurities in CdTe. For each of the acceptors listed above, the excitation energies of states are determined and preliminary conclusions are made about the symmetry of the centers. The observed structure of the excited states differs from the spectrum of standard substitutional acceptors and allows one to simulate the electron configuration of defects.     

Photoluminescence studies of the amphoteric behavior of carbon and germanium in GaAs

Recombination radiation due to an exciton bound to neutral donors and neutral acceptors in high purity vapor phase epitaxial GaAs is investigated using high resolution photoluminescence spectroscopy at liquid helium temperatures. It is found that those samples which show the presence of germanium acceptors also exhibit a strong residual donor referred to in the literature as X₃. Samples containing carbon acceptors however, do not show the presence of X₃. In the past X₃ has been identified by some groups as due to carbon on the gallium site. The work presented here sugests that the X₃ donor is associated with germanium. This identification of the X₃ donor is in agreement with a recent assignment based on the far infrared study of neutron transmuted GaAs.     

Photoluminescence of the ZnSe single crystals doped by thermal diffusion of nitrogen

Photoluminescence (PL) spectra of ZnSe single crystals annealed in different ambients containing molecular nitrogen are investigated. The compensating activity of N impurity in n-ZnSe crystals is shown. It is caused by the formation of N_Se acceptor centers, having 101-108 meV activation energy. The intensity of amplification of both long-wave luminescence spectra bands and the edge luminescence spectra bands caused by the presence of nitrogen in annealing medium is investigated. The presented results allow one to assign the long-wave luminescence to deep acceptors caused by uncontrollable impurities, and the relevant bands of the edge luminescence spectra to the excitons bound with the same deep acceptors. The model explaining the transformations of the luminescent properties of ZnSe crystals by means of nitrogen impurity doping is proposed. The model considers the presence of donors having 75 meV activation energy, acceptors having 220-720 meV activation energy and centers having levels localized near the middle of the band gap.     

“Discrete shell model” for analysing time-resolved energy transfer in solids

We present a new mathematical method to describe the time-resolved fluorescence response of donors and acceptors for the case of energy transfer in crystals, taking into account energy diffusion within the donor system, direct donor-acceptor transfer with any arbitrary dependence of the transfer probability on distance, and the discrete crystal structure. For the first time we give the fluorescence responses for elevated temperatures including transfer of optical excitation energy from the acceptors back to the donors. Furthermore, the competition between neighbouring acceptors (excitation sinks), important for most real acceptor concentrations, is taken into account. The fluorescence responses of donors and acceptors to four commonly realized excitation conditions are given explicitly to any desired degree of precision as sums of exponential functions; they are based on the numerical solution of an eigenproblem. The method is designed to be used in computer analysis of time-resolved fluorescence data.