Spectroscopy of resonant excitation of exciton luminescence of GaSe–GaTe solid solutions

The luminescence excitation spectra of localized excitons in GaSe_0.85Te_0.15 solid solutions have been investigated at the temperature T = 2 K. It has been shown that the excitation spectra of excitons with the localization energy ε > 10 mV exhibit an additional maximum M _E located on the low-energy side of the maximum corresponding to the free exciton absorption band with n = 1. It has been found that the shift in the position of the maximum M _E in the excitation spectrum with respect to the energy of detected photons increases as the energy of detected photons decreases, i.e., with an increase in the localization energy of excitons. Under the resonant excitation of localized excitons by a monochromatic light from the region of the exciton emission band, in the exciton luminescence spectrum on the low-energy side from the excitation line, there is also a maximum of the luminescence (M _L ). The energy distance between the position of the excitation line and the position of the maximum in the luminescence spectrum increases with a decrease in the frequency of the excitation light. The possible mechanisms of the formation of the described structure of the luminescence excitation and exciton luminescence spectra of GaSe_0.85Te_0.15 have been considered. It has been concluded that the maximum M _E in the excitation spectrum and the maximum M _L in the luminescence spectrum are attributed to electronic–vibrational transitions with the creation and annihilation of localized excitons, respectively.     

On the physical basis for Urbach's rule

The low-energy tail of the E 6 a exciton in GeS obeys Urbach's rule, with Urbach parameters σ₀ = 1.45 ± 0.05, and $\text{h}\text{?}\text{ω}{}_{\mathrm{p}}\text{= 8.7 ± 0.6 meV}$. The energy ?ω_p corresponds to a previously measured rigid-layer vibrational mode which has no associated electric field. This finding is inconsistent with Dow and Redfield's unified theory of Urbach and exponential absorption edges. Our results are consistent with Sumi and Toyazawa's theory of Urbach edges, and with Fivaz and Mooser's model for electron-phonon interactions in layered compounds.     

Temperature changes in the photoluminescence and the intrinsic absorption edge of the (Ga0.1In0.9)2Se3 crystal

The photoluminescence and the intrinsic absorption edge of the (Ga_0.1In_0.9)₂Se₃ uniaxial crystal are investigated in the temperature range 77–300 K. Exciton and impurity luminescence bands are revealed at low temperatures and the Urbach tail of the absorption edge is found in the temperature range under study. The temperature dependences of the spectral position and the half-width of the luminescence bands, as well as the optical pseudogap and the energy width of the absorption edge, are studied. The mechanisms of radiative recombination and light absorption and the processes of lattice disordering in the (Ga_0.1In_0.9)₂Se₃ crystal are discussed.     

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.     

Electronic excitations and luminescence of SrMgF4 single crystals

The electronic and crystal structures of SrMgF₄ single crystals grown by the Bridgman method have been investigated. The undoped SrMgF₄ single crystals have been studied using low-temperature (T = 10 K) time-resolved fluorescence optical and vacuum ultraviolet spectroscopy under selective excitation by synchrotron radiation (3.7–36.0 eV). Based on the measured reflectivity spectra and calculated spectra of the optical constants, the following parameters of the electronic structure have been determined for the first time: the minimum energy of interband transitions E _g = 12.55 eV, the position of the first exciton peak E _n = 1 = 11.37 eV, the position of the maximum of the “exciton” luminescence excitation band at 10.7 eV, and the position of the fundamental absorption edge at 10.3 eV. It has been found that photoluminescence excitation occurs predominantly in the region of the low-energy fundamental absorption edge of the crystal and that, at energies above E _g , the energy transfer from the matrix to luminescence centers is inefficient. The exciton migration is the main excitation channel of photoluminescence bands at 2.6–3.3 and 3.3–4.2 eV. The direct photoexcitation is characteristic of photoluminescence from defects at 1.8–2.6 and 4.2–5.5 eV.     

Optical and luminescence characteristics of BaF2 and BaF2:Tm in vacuum UV and UV spectral regions

The spectral characteristics of BaF₂ and BaF₂:Tm crystals and ceramics are compared. The vacuum UV (VUV) and UV absorption spectra and excitation spectra of core-valence and exciton luminescence are investigated. The main exciton and electron-hole processes responsible for the structure of recorded spectra are considered.     

Evidence for exciton binding at Ni impurity sites in ZnSe

A broad charge transfer band is observed in the photoluminescence excitation (PLE) spectrum of the 2.5 μ Ni²⁺ luminescence in ZnSe : Ni. This band lies above the highest energy d-d excitation bands and exhibits a ZPL at 1.8163 eV and LO(#38;0lambda;) phonon replicas at higher energy. In contrast, PLE spectra of Co²⁺ luminescence in ZnSe:Co contain only d-d excitation bands. The charge transfer band in ZnSe:Ni is interpreted as evidence for bound exciton formation at the Ni site. The recombination energy of this exciton is transferred efficiently to the excited d-band states of the Ni ion, leading to characteristic Ni²⁺d-d luminescence.     

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.     

Alloying induced shift between excitation and luminescence of the nitrogen bound exciton in GaPxAs1−x alloys

Photoluminescence and luminescence excitation spectra have been performed on epitaxial layers of nitrogen doped GaP_xAs_1?x alloys (x > 0.85). The main luminescence excitation band A appears above the photoluminescence band N_x. The composition dependence of this energy shift suggests an alloying energy shift. The origin of this new effect would be the thermalization of the bound exciton population to the lower energy states of the A absorption band which reflects the density of states broadening due to As-P disorder around N atoms     

The location of the lowest conduction band minima in gallium phosphide from bound exciton luminescence

Two weak satellite series with acceptor-independent displacement energies of 4.2₃ meV and 7.8₃ meV have been observed in the luminescence of excitons bound to neutral acceptors in GaP. These satellites contain broad background luminescence. Rather well defined superimposed peaks show relative strength which increases dramatically with decrease in exciton binding energy. The most plausible mechanism for these satellites involves bound exciton recombination with emission of one phonon to conserve momentum in the indirect transition and one or two further phonons to conserve momentum in g-type inter-valley scattering processes. This model is consistent with all known properties of the satellites and is strongly supported by a quantum-mechanical line width calculation. The narrow components arise from a diffuse tail on the bound exciton wave-function which is enhanced by the electron-hole correlation. The existence of this g-scattering process shows that the conduction band minima in GaP lie at 0.953 K^max_〈100〉, not exactly at K^max_〈100〉 as believed hitherto. This revision has important consequences for several properties of n-type GaP.     

Effects of optical activity on exciton luminescence of CdS

The luminescence spectra have been investigated in the vicinity of the B_n=1 exciton resonance in CdS at T = 2 K. The effect of “weak” optical activity on luminescence has been observed for the first time. The observed spectra are compared with the frequency dependences of the polariton transmission coefficients.     

Energy fluctuations in optical transitions in CuHal crystals

This paper reports on a comprehensive study of fundamental-absorption spectra of CuCl and CuBr nanocrystals measured in the temperature range extending from 80 K up to the melting point. The temperature dependences of the energy E, oscillator strength f, and temperature-broadening coefficient σ of optical-transition spectral to excitonic states were determined. A new approach to the calculation of the shape and temperature-broadening of absorption spectra, based on quantum statistics, was employed. The crystal is treated as a quantum statistical ensemble. The set of atoms involved in the electronic transition initiated by a photon absorption is taken as an element of the ensemble. Energy fluctuations of electronic states occurring in the elements of the ensemble give rise to temperature broadening of the optical-transition spectra. The temperature dependence of the χ coefficient of thermodynamic fluctuations of the Z _{1, 2} and Z ₃ exciton states was found. A theoretical substantiation of the Urbach rule was obtained in terms of the model proposed.     

The optical properties of Be,Mg and Zn-diffused gallium phosphide

Interest in the Ga-site acceptors Be and Mg was stimulated by the possibility that they might produce efficient luminescence on association with O, analogous to the well-known red Zn-O luminescence in GaP but at higher transition energy. Attention was directed to diffusion doping by Be and Mg of GaP O-doped during growth because the reactivity of Be and Mg with O renders double doping during crystal growth very difficult. Structured green donor-acceptor pair spectra were observed at 1.6°K from many Be-diffused crystals, yielding an accurate measure of (E_A)_BE, 50 ± 1 meV. Moderately efficient orange-red luminescence was also observed below ∼ 100 °K from these crystals, but the intensity of this luminescence decreased rapidly to negligible levels by ∼ 200°K. This luminescence also contains sharp structure at 1.6°K, of a form characteristic of the decay of excitons bound to complex centres. Many sharp phonon replicas occur, involving local modes as well as characteristic GaP modes. One set of no-phonon lines, at least, near 2.19 eV, shows zero-field splitting, luminescence decay times and behaviour in magnetic and external strain fields characteristic of exciton decay at a centre with <100>; or <111>-type symmetry axes, containing no extra electronic particles. The exciton state is split by 2.4 meV by J-J coupling, and the axial field of the centre splits the hole states by ∼ 1.0 meV. These bound excitons are specifically characteristics of diffused GaP and appear analogous to bound excitons observed below 2.12 eV in Zn-diffused GaP. It is probable that the relevant centres contain diffusion components such as Be or Zn interstitials and improbable that O_P is involved. By contrast, weak orange bound exciton luminescence observed in Mg-diffused GaP does involve O, presumably as O_P. No analysis of the magneto-optical behaviour of this Mg-related bound exciton was possible in our crystals, so its symmetry axis was not established. It is possible that this is the Mg_Ga-O_P bound exciton. If so, the two-fold reductions in the exciton localisation energy from ∼ 0.32 eV to ∼ 0.15 eV and in the mass of the Ga-site substituent has produced dramatic changes in the form of the phonon cooperation between the Zn-O and “Mg-O” excitons. The “Mg-O” exciton luminescence is not dominant in our crystals, even at low temperature. The exciton state is again split by a local crystal field as well as by J-J coupling, but here the former splitting is predominant; 2_∈0 = 3.9 meV, Δ = 0.60 meV.     

Optical spectra and energy band structure of AgAsS2 crystals

Ground and excited states of three exciton series are observed in the region of fundamental absorption edge of AgAsS₂ crystals. The contours of exciton reflection spectra are calculated and the main parameters of excitons and energy bands are determined in the center of Brillouin zone. The optical reflection spectra are investigated at 30 K in E∥c and E⊥c polarizations in AgAsS₂ crystals in the region of 2-6 eV. The optical functions are calculated from the reflection spectra and a scheme of electronic transitions responsible for peculiarities of reflection spectra deep into the absorption band is proposed.     

Optical absorption in sputtered amorphous phosphorus

Optical absorption measurements are reported on r.f. sputtered films of a-P prepared at variable substrate temperatures. With decreasing substrate temperature the absorption spectra shift to lower frequencies and the energy gap decreases. The form of the spectra are, however, similar both in the band edge and Urbach tail regions. The Urbach slope is found to differ substantially from that of a-As, indicating that factors other than coordination number may influence this parameter. The changes in the absorption spectra are suggestive of a possible role of intermediate range order on the electronic states in a-P.     

Modeling of the luminescence-decay kinetics of self-trapped excitons at a high excitation density under conditions of absorption saturation

An analytical model for determining the spatial distribution of self-trapped excitons upon excitation at the Urbach absorption tail under conditions of absorption saturation is developed, and an expression for exciton luminescence decay kinetics in wide band-gap crystals was derived taking into account concentrational exciton self-quenching under such excitation conditions.     

Influence of exciton decay on the polariton luminescence spectra of CdTe crystal

The polariton luminescence spectra of CdTe crystals have been numerically calculated with allowance for the decay of mechanical excitons and compared with the known experimental low-temperature photoluminescence spectra of these crystals. The mechanism of formation of polariton luminescence in dependence of the optical parameters of crystal for the exciton resonance A _n=1 is discussed.     

Investigation of the optoelectronic properties of columbite ZnNb2O6 crystal

A high-quality ZnNb₂O₆ single-crystal grown by optical floating zone method has been used as a research prototype to analyze the optoelectronic parameters by measuring the absorption coefficient and transmittance spectra along the b-axis from 200 nm to 1000 nm at room temperature. The optical interband transitions of ZnNb₂O₆ have been determined as a direct transition with a band gap of 3.84 eV. The refractive index, extinction coefficient, and real and imaginary parts of the complex dielectric constants as functions of the wavelength for ZnNb₂O₆ crystal are obtained from the measured absorption coefficients and transmittance spectra. In the Urbach tail of 3.16–3.60 eV, the validity of the Cauchy–Sellmeier equation has also been evaluated. Using the single effective oscillator model, the oscillator energy E_o is found to be 4.77 eV. The dispersion energy E_d is 26.88 eV and ZnNb₂O₆ crystal takes an ionic value.     

Photoinduced relaxation processes in self-assembling complexes from CdSe/ZnS water-soluble nanocrystals and cationic porphyrins

Particular features and quenching mechanisms of exciton luminescence of water-soluble nanocomposites that are formed as a result of the interaction of surface charged semiconductor quantum dots (QDs) CdSe/ZnS (d _CdSe = 2.8 nm) and cationic porphyrins (H₂TMPyrP⁴⁺ and ZnTMPyrP⁴⁺) have been studied theoretically and experimentally. It has been found that, in CdSe/ZnS??Porphyrin conjugates, there occurs long-range inductive resonance electronic excitation energy transfer from surface modified (with thioglycolic or mercaptoundecanoic acid) QDs to porphyrins, which is accompanied by quenching of the exciton luminescence of QDs and an increase in the fluorescence intensity of porphyrin. It has been shown that, when mercaptoundecanoic acid is used as a QD shell, the QD luminescence quenching efficiency by porphyrins follows the F?rster-Galanin theory and depends on the overlap integral between the CdSe/ZnS luminescence band and the absorption spectra of free-base porphyrin H₂TMPyrP⁴⁺ and its metal complex ZnTMPyrP⁴⁺. It has been revealed that, as the QDs ? Zn-porphyrin intercenter distance decreases from 39.1 (mercaptoundecanoic acid) to 30.1), a considerable QD luminescence quenching is observed; however, the energy transfer efficiency substantially decreases, from 55% in the former case to 23% in the latter one. Based on the spectral-luminescent data and quantum-chemical calculations, it has been found that the chemical change of H₂TMPyrP⁴⁺ in the structure of the complex with CdSe/ZnS QDs passivated by thioglycolic or mercaptoundecanoic acid is caused by the formation of a metal complex ZnTMPyrP⁴⁺. Based on calculations of the redox-potentials, it has been concluded that the low luminescence quantum yield of CdSe/ZnS QDs passivated by residues of mercaptocarboxylic acids S^?(CH₂) _n COO^? and its dependence on the number of CH₂ groups are related to the possibility of photoinduced electron transfer from the HOMO of passivating molecules to QDs (QD* ? S^?(CH₂)nCOO^? hole transfer). It has been shown that the quenching of the exciton luminescence of QDs in heterogeneous structures CdSe/ZnS(thioglycolic acid)??ZnTMPyrP⁴⁺, which is complementary to the energy transfer, can be caused by the photoinduced electron transfer that involves the participation of the LUMO of the ZnTMPyrP⁴⁺ molecule (QD* ? ZnTMPyrP⁴⁺).