Valence band contributions to photoluminescence excitation spectra of tightly bound holes in zincblende semiconductors

Photoluminescence excitation (PLE) spectra of deep acceptor states in ZnSe, for example the Cu-related luminescence band at ≈1.95 eV, contain a prominent excitation band at ≈3.25 eV. This band lies above the structure marking the lowest direct E_O band gap E_g by the spin-orbit splitting energy Δ of the valence bands at Γ. The higher energy feature is either absent or greatly de-emphasised in the PLE spectra of shallow acceptor states in ZnSe and of the oxygen iso-electronic trap in ZnTe, where the electron rather than the hole is tightly bound. However, a significant PLE component at E_g + Δ is observed for deep acceptor-like states in ZnTe, where Δ is ≈0.95 eV. Efficient PLE at E + Δ for luminescence from deep acceptor-like states is shown to be consistent with the extended wave-vector contributions to the bound state wave-functions of holes of binding energies ≈Δ.     

Shallow acceptor bound exciton and free exciton states in high-purity zinc telluride

We investigated excitons bound to shallow acceptors in high-purity ZnTe and measured excitation spectra of two-hole luminescence lines at 1.6 K using a tunable dye-laser. The electron-hole coupling in the bound exciton (BE) states appears to be very different for the various acceptors even for almost identical exciton localisation energies. Three different types of BE are reported. For the Li-acceptor BE we observe three sub-components separated by 0.22 and 0.17 meV and interpreted as J = $\text{1}\text{2}$, $\text{3}\text{2}$, $\text{5}\text{2}$ states. The Ag-acceptor BE exhibits a strong ground state and a weak excited state at 1.3 meV higher energy. For the as yet unidentified k-acceptor we observe a single BE level, degenerate with the Ag-acceptor BE ground state. Dips in the excitation spectra due to absorption into free exciton 1S, 2S, and 3S states yield an exciton Rydberg R₀ = 12.8±0.3 meV and a free exciton binding energy FE(1S) = 13.2±0.3 meV.     

Optically detected electron resonance in phosphorus-doped ZnTe

Samples of ZnTe showing near gap edge luminescence predominantly due to exciton recombination at shallow neutral acceptors and donor- acceptor pair recombination have been investigated using optically detected magnetic resonance (ODMR). Emission polarization changes at 2.318 eV were observed due to magnetic resonance of electrons at g_e = + 0.401 ± 0.004. The observations are consistent with the donor trapped electron resonance resulting from microwave induced changes in donor-acceptor pair photoluminescence.     

Strong excitonic effect in organic–inorganic hybrid crystals

We investigate the optical properties of the hybrid crystal ZnTe(C₂H₈N₂)_0.5 from first principles. The excitonic effect is included by solving the Bethe–Salpeter equation for the two-particle Green's function. The inorganic ZnTe acts as optical active layer and the excitonic wave function is confined within it by C₂H₈N₂ layers. Due to the confinement of electronic states, electron–hole interaction within ZnTe layers is enhanced and the absorption spectra are thus changed drastically. The exciton binding energies are 0.54 and 0.42 eV for α and β structures, respectively. The calculated quasiparticle gap of the β structure is 3.68 eV.     

Zeeman splitting of ground and excited acceptor states in ZnTe

Zeeman splittings of Li-acceptor states in ZnTe are investigated by Selective Pair Luminescence. From a detailed study of the polarization dependent absorption and emission of photons by donor-acceptor pairs, the g-values of both ground and excited Li-acceptor states are determined. The method presented here is appropriate to the study of donors as well as acceptors in semiconductors.     

Copper,the dominant acceptor in refined,undoped zinc telluride

Comparative measurements have been made of optical absorption and photoluminescence of refined undoped and Cu in-diffused ZnTe single crystals. Strong increases in a bound exciton BE line near 2.375 eV previously identified with the electrically dominant point defect acceptor ‘a’, with binding energy E_A ? 149 meV, suggests that this acceptor is substitutional Cu_Zn. Similarly strong increases in a relatively broad band at slightly higher energy suggests the simultaneous incorporation of shallow donors, possibly interstital Cu_I. These findings indicate that intrinsic defects such as V_Zn neither control the Fermi level in refined ZnTe nor produce shallow acceptors with E_A ? 250 meV, contrary to much previous speculation.     

The nature of the predominant acceptors in high quality zinc telluride

We report very sharp bound exciton luminescence spectra in high quality melt-grown very lightly compensated ZnTe, p-type with N_A-N_D in the low 10⁺¹⁵ cm^-3. Bound exciton localisation energies at seven shallow neutral acceptors with E_A between ~55 and ~150 meV are very insensitive to E_A. Optical absorption and dye laser luminescence excitation spectroscopy were necessary to obtain a full separation of the transitions due to different acceptors, together with a study of certain ‘two-hole’ luminescence satellites in which the acceptor is left in a series of orbital states after bound exciton decay. Two shallow acceptors are P_Te and As_Te, a third possibly Li_Zn while a fourth, relatively prominent in our best undoped crystals, may be a complex. A deeper, 150 meV acceptor, frequently reported in the ZnTe literature and electrically dominant in most of our undoped crystals has the Zeeman character of a point defect. We present clear evidence from our spectra that this energy does not represent the binding of a single hole at a doubly ionized cation vacancy, a popular attribution since 1963. This acceptor may be covered by another impurity, possibly Cu_Zn. We also report bound phonon effects, lifetime broadening of excited bound exciton states and observe a single unidentified donor with E_D ~18.5 meV. This energy is determined using selective dye laser excitation at the weak neutral donor bound exciton line and from the onset of valence band to ionized donor photo-absorption.     

Optical response of saddle point excitons

The linear optical response of interband transitions near saddle points is studied within the framework of the effective mass approximation. The method is based on Stahl's configuration space theory. Unlike previous works the present treatment allows an unrestricted range of effective mass ratios, and it generates both real and imaginary part of the dielectric function. Spectra are calculated by numerical integration of a two dimensional second order partial differential equation. The results obtained for M₁ saddle points agree well with the observed lineshape of the E₁ peak in ZnTe.     

Selective pair luminescence in semiconductors

A novel, highly sensitive spectroscopic technique for the investigation of excited impurity states in semiconductors is demonstrated for Li- compensated n-type ZnSe and for p-type ZnTe:P. Donor/acceptor pairs with one partner in an excited state are pumped selectively to assure optimal radiative re-emission after fast de-excitation of the electron or hole, respectively. Luminescence is confined to a sharp line riding on the high energy shoulder of the pair band.     

Magnetic studies on ZnTe:Cr film grown on glass substrate by thermal evaporation method

ZnTe and ZnTe:Cr films were prepared on glass substrate by using thermal evaporation method. X-ray diffraction analysis revealed the presence of ZnCrTe phase. X-ray photoelectron spectroscopy was used to estimate the composition of as-prepared films. The valence state of Cr in ZnTe:Cr film is determined to be +2 by using electron spin resonance spectroscopy. Magnetic moment data as a function of magnetic field was recorded by using superconducting quantum interference device magnetometry at 300 K. The result showed a clear hysteresis loop with coercive field of 48 Oe. Magnetic domains were observed by using magnetic force microscopy and the average value of domain size was 3.7 nm.     

Oxygen incorporation in ZnTe thin films grown by plasma-assisted pulsed laser deposition

We studied oxygen incorporation into ZnTe thin films with nitrogen and oxygen plasma during a plasma-assisted pulsed laser deposition (PA-PLD). It was shown that ZnTe:O layer formed with oxygen plasma exhibits an enhancement of optical transparency in visible spectral region due to the formation of amorphous TeO_x. Especially, the ZnTe:NO deposited by PA-PLD under nitrogen and oxygen partial pressures with N₂:O₂ of 10:3 sccm showed p-type semiconducting characteristics and the formation of intermediate band at about 0.5–0.8 eV below the ZnTe band edge. These results for oxygen incorporation in ZnTe thin film such as the enhancement of optical transparency in visible spectral region and the intermediate band formation will be useful for optoelectronic devices or intermediate band solar cells.     

Magnetoreflectance of the Γ6 – Γ8 exciton ground state in cubic ZnSe

Magnetoreflectance measurements on the ground state of the Γ₆ – Γ₈ free exciton in cubic ZnSe in magnetic fields up to 18 T are reported. The splitting between the |1, ±1〉 states was derived from the measured difference spectrum between σ⁺ and σ^--polarized reflectance in Faraday configuration. The splitting between the two states corresponding to |2, 0〉 and |1, 0〉 at B = 0 was determined by means of a lineshape analysis. We derive an electron g-factor g = 1.48 ± 0.25, in reasonable agreement with existing k · p calculations, and obtain an effective hole g-value $\text{K}\text{?}\text{= -0.26±0.06}$. In addition, we find an upper limit for the short range electron-hole spin exchange energy Δ ? 0.1 meV, which is considerably smaller than values, which is considerably smaller than values reported in the literature, but agrees with recent results on ZnTe obtained by uniaxial stress and also magnetoreflectance measurements.     

Influence of the thickness of CdTe and ZnTe layers on cathodoluminescence spectra of strained CdTe/ZnTe superlattices with quantum-dot layers

The influence of the thickness of ZnTe barrier layers on the cathodoluminescence spectra of strained CdTe/ZnTe superlattices containing layers of quantum dots with an average lateral size of approximately 3 nm has been investigated. In samples with thick barrier layers (30, 15 nm), the cathodoluminescence spectra of quantum dots exhibit one band with a maximum at E = 2.03 eV. It has been revealed that, at a barrier layer thickness of ∼3 nm, the luminescence band is split. However, at a ZnTe layer thickness of 1.5 nm, the luminescence spectrum also contains one band. The experimental results have been interpreted with allowance made for the influence of elastic biaxial strains on the energy states of light and heavy holes in the CdTe and ZnTe layers. For the CdTe/ZnTe heterostructure with quantum dots in which the thickness of the deposited CdTe layer is 1.5 monolayers and the thickness of the barrier layer is 100 monolayers, the cathodoluminescence spectrum contains 2LO-phonon replicas. This effect has been explained by the resonance between two-phonon LO states and the difference between the energy states in the electronic spectrum of wetting layer fragments.     

Energy barrier between states of a bistable center in photochromic crystals CdF2:Ga and CdF2:In

The establishment of thermal equilibrium between photoinduced (shallow) and ground (deep) states of bistable DX centers in photochromic crystals CdF₂:In and CdF₂:Ga, which are used as real-time holographic media, is studied based on the notions of chemical kinetics. Two mechanisms of mutual transformation of shallow and deep centers—the tunnel mechanism and the mechanism with the participation of free charge carriers—are considered. Equations describing the decay of a photoinduced shallow state are obtained. These equations take into account the distribution of electrons between the photoinduced and ground states and the conduction band. Analysis of the experimental kinetic curves of the decay of photoexcited shallow centers makes it possible to determine the activation energies and barrier height for thermally activated processes of mutual transformation of shallow and deep centers. In CdF₂:In and CdF₂:Ga, this barrier, which determines the decay kinetics of holograms, lies above the bottom of the conduction band by ～10 and ～500 meV, respectively.     

Low-temperature photoluminescence of II–VI films obtained by close-spaced vacuum sublimation

Low-temperature photoluminescence (PL) spectra of CdTe and ZnTe films obtained by a close-spaced volume sublimation technique under different technological conditions (substrate temperatures) were investigated. Analysis of the experimental results made it possible to conclude that the nature of the structure of the PL spectra observed experimentally is caused by the recombination of the excitons bound to shallow neutral acceptors, donor–acceptor pairs with the participation of the complex acceptors, and the presence of the extended defects like dislocations. The presence of neutral acceptors is related to the Li, Na, P or Cu residual impurities. As a result of the study of the PL spectra of CdTe and ZnTe films the optimal temperature conditions of their growth were determined as the substrate temperature T_s=623 K and 673 K, respectively.     

Impact of ZnTe buffer on the electrical properties of n-type GaSb:Te films

We have investigated on the molecular beam epitaxy (MBE) of Te-doped GaSb films on ZnTe buffer. Te-doped GaSb (GaSb:Te) films with and without ZnTe buffer were grown on (0 0 1) GaAs substrates. GaSb:Te/ZnTe/GaAs film revealed higher mobility (=631 cm²/V s) in comparison to GaSb:Te/GaAs film (=249 cm²/V s). To explain the higher mobility of GaSb:Te on ZnTe buffer, dislocation density and temperature dependence of Hall measurement results were analyzed. Temperature dependence of Hall measurement shows strong influence of the dislocation scattering, which indicates that dislocation reduction by the ZnTe buffer enhances the carrier mobility of GaSb films.     

Far-infrared quasi-local modes of ZnTe in CdTe

We report the very far-infrared absorption spectra of the mixed-crystals Cd_1-xZn_xTe for small x in the temperature range of 4.2K–150K and the wavenumber region of 20cm⁻¹–100cm⁻¹. The quasi-local mode induced by ZnTe in CdTe and CdTe-like 2TA two-phonon creations are observed, to be best of our knowledge, for the first time. The frequencies of the modes are estimated by using the mass-defect model combined with Green's functions calculations. Besides, the temperature dependence of the absorption peak is well explained in the light of the characteristics of the modes.     

Photodielectric effect and “Configuration” modes of bistable centers in the CdF<Subscript>2</Subscript>: Ga crystal

A photoinduced increase in the real (?′) and imaginary (?″) parts of the permittivity (Δ?′ ≈ 0.23 and Δ?″ ≈ 0.10 at a frequency of 15 cm^?1) is revealed experimentally. This photodielectric effect is adequately described by the predicted configuration modes at the frequencies gv ₁ = 354 cm^?1 and gv ₂ = 123 cm^?1, which correspond to the potential-energy curves previously calculated for deep and shallow impurity states in CdF₂: Ga crystals. The dielectric contributions of these modes are determined, and the corresponding concentrations of Ga ions in deep (N ₁) and shallow (N ₂) impurity states are calculated. It is found that, unlike the CdF₂: In crystals, the changes in the quantities ?′ and ?″ before and after illumination of the CdF₂: Ga crystals are predominantly determined by the change in the contribution from the configuration mode of the shallow state, because the contribution from the configuration mode of the deep state is very small. A photoinduced decrease in the lattice reflection in the CdF₂: Ga crystals due to the change in the dielectric contribution from the impurity mode of the lattice is predicted.     

Direct emission and Auger decay from multiplet final states in Zr observed by ultraviolet photoemission CFS techniques

Photoemission techniques have been used to investigate the structures accompanying excitation of shallow p-core states in crystalline Zr. The continuum nature of synchrotron radiation has been exploited between hv = 20 and 45 eV to determine the Constant Final-state-energy Spectra (CFS) over a range of kinetic energies of the emitted electrons. The results reveal strong direct emission from the multiplet final states and indicate that the final states are broadened by configuration interaction. Auger processes appear to be a probable mode of decay of the p-hole. Secondaries resulting from the Auger processes give rise to structures in the CFS's which compare well to structures in the optical absorption coefficient.