Magneto-optical study of the I2 bound exciton in ZnTe

The 1L0-phonon replica of the I₂ bound exciton in ZnTe at 2.374 eV is fully resolved into a quintet at fields of 130 kG. Analysis of the data shows that the I₂ complex consists of an exciton bound to an $\text{ionized}$ donor or acceptor; the electron and hole gyromagnetic ratios deduced, $\text{g}{}_{\mathrm{h}}\text{= ? 1.2}$ and g_e = ± 1.7, are in excellent agreement with the values determined from recent spin-flip scattering experiments, viz. g_h = 1.07 ± 0.1, g_e = 1.74 ± 0.05.     

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 excitonic complexes in ZnTe

Uniaxial stress experiments were used to investigate the nature of the luminescence lines observed at low temperatures in ZnTe in the vicinity of the absorption edge. The single crystals used in this experiment were grown from solution of ZnTe in tellurium. Both “as-grown” crystals and crystals annealed in Zn vapour were investigated. The most intense line in “as-grown” crystals is attributed to an exciton bound to a neutral acceptor. The binding energy of the exciton in this center is 6 meV. After annealing a new center appears in the same spectral region. Stress experiments as well as the temperature dependence of the intensity of the luminescence indicate that this center is a complex consisting of an exciton and an ionized donor. Splitting of J = 1 (Γ₅) and J = 2 (Γ₃ + Γ₄) levels was found to be 1.2 meV.     

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.     

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.     

Excited states of bound excitons in ZnO

The bound exciton lines I₅, I₆, and I_{$\text{7}\text{8}$} in ZnO at 5 K are studied in the energetic region of the free excitons and below by means of excitation spectroscopy. Apart from the maxima at the free exciton energies, additional resonances are observed and interpreted as the direct creation of bound excitons in excited states which lie 6meV and 4.5 meV above the ground states.     

Donor-like excited states of exciton bound to neutral acceptor in ZnTe

Photoexcitation spectroscopy has been used to study the excited states of the neutral c-acceptor bound exciton complex A^c₁ in ZnTe. We have detected four excited states at ～ 11.2 meV above the bound exciton ground state. Zeeman effects on these excited states have also been studied. The results show that they correspond to excitations of the bound electron to donor-like 2p and 2s orbital states. This represents an unambiguous experimental evidence of the pseudo-donor model previously suggested by Rühle and Bimberg for acceptor bound exciton complexes when m_e ? m_h.     

Features of the absorption spectra of thin films of M 2Ag1 − x CuxI3 solid solutions (M = Rb, Cs)

The absorption spectra of thin films of (MI)_{1 ? y} (Ag_{1 ? x} Cu_xI)_y solid solutions (M = Rb, Cs) with the initial molar concentration y = 0.33 have been investigated. It is established that, at low concentrations x, a local exciton band due to Cu⁺ ions is split off from the main long-wavelength exciton bands. In Rb₂Ag_{1 ? x} Cu_xI₃ solutions, the concentration shift of exciton bands indicates the formation of a persistent-type exciton spectrum. However, in Rb₂Ag_{1 ? x} Cu_xI₃ with x ≥ 0.5 and in Cs₂Ag_{1 ? x} Cu_xI₃ with x > 0.2, exciton spectra of amalgamation type are observed, which are related to the formation of more stable M ₃Ag_{2 ? 2x} Cu_2x I₅ solid solutions. The formation of these solutions leads to broadening of the exciton bands and to the concentration transition from persistent-to amalgamation-type exciton spectra.     

Zeeman spectroscopy of exciton bound to trigonal acceptor center in ZnTe

Zeeman effects have been measured for the A^c₁ line at 2.368 eV in ZnTe. The results are interpreted in terms of exciton recombination at a neutral acceptor center in a strong trigonal crystal field. The relevant g-factors are : g_e = -0.50 ± 0.05 for the electron ; g_h = +0.90 ± 0.05 for the hole.     

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.     

沉积条件对ZnTe/ZnTe:Cu薄膜结构及CdTe电池性能的影响

用共蒸发法沉积了ZnTe/ZnTe:Cu复合多晶薄膜,通过XRD,XPS,C-V,I-V等研究了沉积温度对薄膜结构、Cu浓度分布及电池性能的影响.结果表明,沉积温度对薄膜的结构影响不明显,薄膜呈立方相,经185 ℃退火后出现了六方相.对薄膜的剖析发现,Cu浓度分布呈现先上升到一极大值而后快速下降的趋势, 100 ℃沉积的ZnTe/ZnTe:Cu薄膜,ZnTe层起到了阻止Cu扩散作用,用这种薄膜制作的太阳电池X_D较大 关键词： ZnTe多晶薄膜 沉积温度 薄膜结构 器件性能     

Changes in the photoluminescence spectrum near twin boundaries in ZnTe crystals produced by rapid crystallization

{111} ZnTe crystals with various densities of twin boundaries in the growth direction were produced at ～670°C by the chemical vapor deposition method with the vapor environment offset toward an excess of Zn. Defects are formed in conical crystallites (up to 5 mm in height and with lateral dimensions of 10–500 μm at the bottom and up to 2 mm at the top) due to instabilities in the crystallization front, which arise because of convection-type heat and mass exchange in the oversaturated vapor medium. The influence of twin boundaries on the distribution of chemical impurities and the electronic spectrum of ZnTe was studied using x-ray diffractometry, scanning electron microscopy, and low-temperature photoluminescence (PL). It is found that rapid low-temperature growth of [111] ZnTe polycrystals from the vapor phase with an excessive Zn content favors the intensive formation of rotation and reflection twins. The incoherent [111] boundary of reflection twins is conductive to the separation and accumulation of impurities. In the regions of a crystal with a high density of reflection twins, exciton-impurity complexes (I _C , I _X ) and a Y strip, which is usually related to extended defects (dislocations, twins, crystallite boundaries), are found in the low-temperature PL spectra. Additional studies show that I _X is related to excitons trapped by neutral isoelectronic or charged defects and that I _C is probably due to an impurity of group IV of the Periodic Table.     

Inhomogeneous broadening of the dynamically split Kramers spectral line and up-conversion in the pair and quartet centers in CaF2:Nd

The site-selective and time-resolved fluorescence laser spectroscopy and kinetic measurements with high spectral and nanosecond temporal resolution was applied to analyze the high-energy wing of the M and N absorption bands of the ⁴I_9/2(1)→⁴G_5/2(1) crystal-field (CF) transition in a CaF₂:Nd³⁺ (0.6 wt%) crystal at 4.2 K. It was found that at helium temperatures the dynamically split spectral line assigned as the ⁴I_9/2(1)→⁴G_5/2(1) (CF) transition of coherently coupled Nd³⁺ ions in the pair M- and quartet N-centers of CaF₂:Nd³⁺ (0.6 wt%) is inhomogeneously broadened. It consists of the pair M- and quartet N-centers with at least 0.1 A variation of the positions of the fluorescence-excitation spectral lines registered at the ⁴F_3/2(1)→⁴I_9/2(1) CF transition. Small fluorescence-lifetimes variation of the ⁴F_3/2 and ⁴D_3/2 levels from the small variation of the distances R between Nd³⁺ ions in the pair is found. At least 2.7% variation of the value of the Nd-Nd distance R in the pair M-center was determined from the lifetime variation of the ⁴F_3/2 manifold with the assumption of a dipole-dipole interaction between the ions in the pair.The energy transfer up-conversion process responsible for the UV fluorescence observed when pumping the ⁴I_9/2(1)→⁴G_5/2(1) transition has been determined.     

Magnetopolaritons in ZnTe

From an invariant expansion, we construct the exciton Hamiltonian for the Γ₆×Γ₈ excitons in theT _d -type material ZnTe represented by an 8×8 matrix including the influences of a finite wave vector and an external magnetic field. We diagonalize the Hamiltonian matrix to obtain the exciton states. Then the excitons are coupled to the electromagnetic radiation field thus giving the polariton states. The theoretical dispersion curves are fitted to the results of two-photon Raman scattering and reflection experiments in magnetic fields up to 22 T. From this fit we deduce precise values for the eigenergies, exciton masses,g-factors, and diamagnetic shifts.     

Direct determination of the phase of reflectivity by means of modulation technique

A method is described by which the phase of reflectivity for cubic crystals is measured. It involves modulated piezo-reflectance at the frequency ω₁ and modulation of the polarization of light with a $\text{1}\text{2}$λ-plate rotating with the frequency ω₂. The signal of frequency 2ω₂ yields the phase, and the signals of frequencies (ω₁± 2ω₂) yield the derivative of the phase. We have applied this method to measure the exciton spectra of ZnTe. It turns out that the phase becomes negative in certain spectral regions. This behaviour is interpreted in terms of Hopfield and Thomas' model of exciton free surface layers.     

Temperature dependence of the energy gap of MgxZn1−xTe semiconductors alloys

Wavelength-modulation spectroscopy is used to obtain the temperature dependence of the near band gap reflectivity spectrum E_o of Mg_xZn_1?xTe ternary semiconducting alloys. Results are given in the range 80–100 K for the cubic materials: 0〈x〈0.5. The analysis of the line shapes as a function of x and T confirms the hypothesis of an exciton bound to the complex defect associated with zinc vacancy, as ZnTe. The E_o(x) curve is parabolic. The bowing parameter is C=0.45 ± 0.1 eV at 80 K, C=0.6 ± 0.1 eV at 300 K. Within experimental scattering the temperature coefficient dE₀dT is nearly constant with x:-4.5±0.3 × 10^?4eVK^?1. This data is smaller than the value calculated in the literature for ZnTe from pseudo potential method.     

Investigation of free and bound excitons in strained ZnTe films grown by MBE on GaAs(100) substrates

A study is reported of the reflectance and low-temperature photoluminescence (PL) spectra of ZnTe films grown by molecular-beam epitaxy (MBE) on GaAs substrates [(100) orientation, 3° deflection toward 〈110〉]. It is shown that the strain-induced splitting of the free-exciton energy level (ΔE _ex) does not depend on ZnTe film thickness within the 1–5.7 μm range and is due to biaxial in-plane film tension. The stresses are primarily determined by the difference between the thermal expansion coefficients of the film and the substrate. It is also shown that the residual stresses originating from incomplete relaxation of the film lattice parameter to its equilibrium value at the growth temperature likewise provide a certain contribution. The position of the spectral line of an exciton bound to a neutral acceptor (As) is well approximated in terms of the present models, taking into account the stresses calculated using the value of ΔE _ex.     

Influence of magnetic field on exciton luminescence

The magnetic field dependence of the exciton emission intensity I_ex(H) has been investigated in Ge crystals stressed along the direction near 〈100〉. In the low field limit the magnetic field correction has been evaluated to the wave functions of the ground and some excited states of an isotropic exciton. The calculated dependence I_ex(H) in the case of Ge is in a good agreement with the experimental one at H ? 0.5 T.     

Resonant Brillouin scattering via free and bound excitons in CdSe

We report resonant Brillouin scattering results in CdSe. Enhancements in Brillouin scattering have been observed at both the I₂ bound exciton and the free exciton. As a result of the spatial dispersion of the exciton-polariton, the Brillouin frequencies vary with the polariton energy. From this variation of the Brillouin frequencies, we deduced the following parameters in CdSe: transverse exciton frequency =14713 cm^?1, splitting between longitudinal and transverse exciton frequencies = 4cm^?1 and exciton effective mass (perpendicular to the c-axis) =0.40 times free electron mass. The Brillouin linewidths were found to vary with polariton energies in qualitative agreement with the theory of Brenig, Zeyher and Birman.     

Specific features in the temperature dependence of photoluminescence from CdTe/ZnTe size-quantized islands and ultrathin quantum wells

A study has been carried out of the temperature dependences of luminescence spectra on a large number of CdTe/ZnTe structures differing in average thickness, 〈L _z〉=0.25–4 monolayers (ML), and CdTe layer geometry (continuous, island type). The influence of geometric features in the structure of ultrathin layers on linewidth, the extent of lateral localization of excitons, their binding energy, and exciton-phonon coupling is discussed. It is shown that in island structures there is practically no lateral exciton migration. The exciton-phonon coupling constant in a submonolayer structure has been determined, Γ_ph=53 meV, and it is shown that in structures with larger average thicknesses Γ_ph is considerably smaller. Substantial lateral exciton migration was observed to occur in a quantum well with 〈L _z〉=4 ML, and interaction with acoustic phonons was found to play a noticeable part in transport processes. It has been established that the depth of the exciton level in a quantum well and structural features of an ultrathin layer significantly affect the temperature dependences of integrated photoluminescence intensity. Fiz. Tverd. Tela (St. Petersburg) 41, 717–724 (April 1999)