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.     

Fine structure of neutral-acceptor bound excitons in direct gap semiconductors with zinc blende structure

We study the influence of the short-range electron-hole exchange interaction (EHEI) on the (A°, X)-bound exciton ground state, for direct gap semiconductors with positive spin-orbit coupling at $\text{k}\text{= 0}$. The envelope contribution to the EHEI is computed using our previously obtained 35-term Page and Fraser-type wave function, showing that the EHEI are comparable in the cases of excitons and bound excitons. The crystalline part of the EHEI lifts the degeneracy between the states $\text{J =}\text{5}\text{2}$, (Γ₇ + Γ₈) and $\text{J =}\text{3}\text{2}\text{(Γ}{}_8\text{)}$, the former being lower in energy. In the case of GaAs, the EHEI is smaller than the j?j coupling of the two holes, so that the states $\text{J =}\text{1}\text{2}\text{(Γ}{}_6\text{)}$ are the highest in energy in agreement with the experimental data, relative to shallow impurities.     

Oscillator strengths for excitons bound to impurities and quantum wells

It is argued that electron-hole correlation can have a large effect on the oscillator strengths of bound excitons, and may help to explain the observations of shallow excited states for donor bound excitons in direct gap semiconductors. For quantum wells it is found that compression of the exciton wave function yields a $\text{1}\text{L}$ dependence of oscillator strength on well width L for narrow wells.     

Excited states of Ag and Cu acceptors in CdTe

We report on resonantly excited luminescence (REL) at 1.8 K and infrared absorption (IRA) between 6–12 K of CdTe doped with Ag and Cu impurities. The luminescence was excited with a tunable dye laser. Two hole transitions up to $\text{6}\text{S}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ state have been observed, the bound exciton lines have been identified. $\text{2}\text{P}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$ states have been observed in IRA measurements. The binding energies as deduced from REL experiments are 107.5 meV for Ag and 146 meV for Cu. The fitted values of the valence band parameters are Ro = 27 ± 3 meV μ = 0.73 ± 0.03 and δ = 0.12 ± 0.01.     

Synthesis, structural and optical properties of a novel bilayered organic-inorganic perovskite C5Pb2I5

Single crystals of [C₅H₁₁NH₃]Pb₂I₅, abbreviated C₅Pb₂I₅, have been prepared. This compound is a new member of the family of the bilayered organic-inorganic lead-iodide based perovskites. Its crystal structure has been determined by X-ray diffraction. The inorganic sub-lattice consists of periodic bilayers of iodoplumbate octahedra. Each PbI₆ octahedra exhibits both edge- and corner-sharing with adjacent octahedra. The vibrational properties of this compound have been studied by Raman scattering spectroscopy. Optical absorption, photoluminescence and diffuse reflectance measurements have been performed. The room-temperature bandgap and free exciton absorption bands are observed at 2.46 and 2.23 eV, respectively. The exciton binding energy is 230 meV which is the largest value ever reported till date for the bilayered PbI based perovskites. Calculations assuming Wannier-type quasi-two-dimensional excitons and taking into account the image potential of the exciton charges showed that nearly 64% of the exciton binding energy is due to the dielectric confinement effect.     

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.     

Magnetoreflectance of the Γ6 — Γ8 exciton in ZnTe

Magnetoreflectance measurements on the Γ₆ – Γ₈ free exciton state in magnetic fields up to 11.5 Tesla are reported. Five of the theoretically expected eight subcomponents of the 1s state are clearly observed. The transverse eigenenergies corresponding to the measured reflectance structures are derived by a lineshape analysis. From the splitting of the |;1,+1> and |;1,-1> states and that of the |;2,0> and |;1,0> states we derive the conduction electron g-value g_c = - 0.57 and the effective hole g-value $\text{g}\text{?}\text{k = - 0.06}$, corresponding to κ_Lutt = + 0.13. A nonzero short-range electron hole spin exchange Δ could not be observed and an upper limit Δ ? 0.1 meV is derived. The observed diamagnetic shifts are slightly smaller (15–20% at 10T) than predicted by existing low field theories, even if corrections as calculated for the case of a hydrogenic atom in a magnetic field are applied taking into account that the low field limit (γ ? 0.4) is already reached at ～7T     

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.     

Direct observation of localized exciton states in CdS<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Se<Subscript>x</Subscript> solid solutions

A system of isolated localized exciton states corresponding to particular energies from the tail of the density of states is observed in CdS_1?xSe_x crystals. From an analysis of the obtained photoluminescence excitation spectra, the boundary between the free and localized excitons and the length of the tail region of the density of localized states that make an essential contribution to radiative recombination are determined. It is shown that the localized and free excitons prove to be separated and represent two exciton subsystems. The energies of actual optical photons are accurately determined to be 23.6±0.2 and 35.6±0.3 meV for CdS_0.70Se_0.30 and 20.7±0.2 and 31.4±0.3 meV for CdS_0.50Se_0.50.     

Bound exciton luminescence of Ar- and Al-implanted ZnO

Argon- and aluminum-implanted ZnO single crystals (N_impl=10¹⁶?10¹⁹cm^?3) were investigated at liquid helium temperature by photoluminescence. We obtained highly resolved emission spectra of implanted and thermally annealed samples. Maximum luminescence yield was achieved after annealing with an oxygen ambient at 800°C and an anneal time of 30 min. In Al-implanted ZnO crystals, we observed a strong emission line $\text{I}{}_{\mathrm{<mtext>5</mtext><mtext>6</mtext>}}\text{at λ = 3688}\text{A}\text{?}$. The intensity of this line is correlated with the implanted Al concentration. The I_{$\text{5}\text{6}$} line is interpreted as the recombination of a bound exciton at a polycentric Al complex.     

Temperature dependent photoluminescence processes in ZnO thin films grown on sapphire by pulsed laser deposition

Temperature dependence of the photoluminescence (PL) transitions in the range of 10–300 K was studied for ZnO thin films grown on sapphire by pulsed laser deposition. The low temperature PL spectra were dominated by recombination of donor bound excitons (B_X) and their phonon replicas. With increasing temperature, free exciton (F_X) PL and the associated LO phonon replicas increased in intensity at the expense of their bound counterparts. The B_X peak with line width of ∼6 meV at 10 K exhibited thermal activation energy of ∼17 meV, consistent with the exciton-defect binding energy. The separation between the F_X and B_X peak positions was found to reduce with increasing temperature, which was attributed to the transformation of B_X into the shallower donor bound exciton complexes at consecutive lower energy states with increasing temperature, which are possible in ZnO. The energy separation between F_X peak and its corresponding 1-LO phonon replica showed stronger dependence on temperature than that of 2-LO phonon replica. However, their bound counterparts did not exhibit this behavior. The observed temperature dependence of the energy separation between the free exciton and it is LO phonon replicas are explained by considering the kinetic energy of free exciton. The observed PL transitions and their temperature dependence are consistent with observations made with bulk ZnO crystals implying high crystalline and optical quality of the grown films.     

The gallium-site donors germanium and silicon in gallium phosphide

The node in the Bloch part of the electron wave function expected for a Ga-site donor in GaP removes the usual valley-orbit splitting and associated chemical shift. However, the T₂ ground state can still show a small spin-valley splitting into Γ₈ and Γ₇ states, as previously verified for the Sn donor. We find that the optical properties of the Ge and Si donors deviate appreciably from this “normal” behaviour. The Ge donor is anomalously deep, E_D ～ 202 meV, yet binds an exciton by ～63 meV consistent with the Haynes rule for neutral donors in GaP. We find that this exciton possesses the large oscillator strength, f～3.5 × 10^-3, Zeeman and piezo-optical splittings characteristic of a Γ₆, 1s(A₁) ground state, like a P rather than Ga-site donor. However, f and the exciton localization energy are consistent with expectation for E_D ～ 200 meV, as measured from the lowest set of X conduction band minima, if we assume a symmetric A₁-like wave function. A possible explanation for this unexpected result is advanced. The much shallower Si donor, E_D～82 meV, binds an exciton by only ～ 14 meV, also consistent with the Haynes rule. By contrast, we find this Ga-site donor to be normal except that our Zeeman and piezo-optical results indicate an inverted spin-valley splitting, about 25% of that for the still shallower Sn donor. We also discuss the numerous low-lying excited states, some anomalous phonon replicas in the Ge and Si donor bound exciton spectra and the magneto-optical properties of a sharp line near 2.24 eV, attributed to the decay of excitons bound to (S)_p-(Ge)_p donor-acceptor associates.     

GaAs中N等电子陷阱的研究

对离子注N的GaAs样品作了77K的静压光致荧光研究。观察到了N陷阱中心元胞势束缚激子N_x的发光光谱及畸变势束缚激子N_T的发光峰。测量N_X能级的压力系数为2.8meV/kbar,常压下N的共振态高于导带边179meV。讨论了N等电子陷阱的电声子耦合强度及有效束缚激子半径随压力的变化关系。 关键词：     

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.     

Optical detection of triplet excitons in GaS

Optically detected magnetic resonance has been used to investigate exciton recombination in the layered semiconductor GaS. Five triplet exciton resonances have been observed all with the same g-value of g_ex6 = 2.006 ± 0.002 but with different zero field splittings:

$\text{D}{}^{\mathrm{I}}\text{= + 0.013 cm}{}^{\mathrm{?1}}\text{, D}{}^{\mathrm{II}}\text{= + 0.024 cm}{}^{\mathrm{?1}}\text{, D}{}^{\mathrm{III}}\text{= + 0.025 cm}{}^{\mathrm{?1}}$

,

$\text{D}{}^{\mathrm{IV}}\text{= + 0.075 cm}{}^{\mathrm{?1}}\text{, D}{}^{\mathrm{V}}\text{= + 0.010 cm}{}^{\mathrm{?1}}$

. The resonances from the high energy wing are remarkably narrow and we believe that this may be the first observation of resonance from free indirect excitons.     

Electroabsorption in TlInS2

Electroabsorption spectra of single crystals have been studied near the fundamental absorption edge at 77 and 300 K. At 300 K two positive peaks (2.34 and 2.42 eV) and a negative peak (2.38 eV) are observed in the electroabsorption spectrum. At liquid-nitrogen temperature a fine structure corresponding to the formation of a parabolic exciton (2.503 eV) is observed.Values of the width of the forbidden gap E_g, the n = 1 exciton positions, the exciton activation energy ΔE_b, the effective Bohr radius a_exc, the reduced effective mass of an electron-hole pair μ, and the exciton ionization field F(E_g = 2.535 eV, E_exc = 2.503 eV, E_b = 32 meV, $\text{a}{}_{\mathrm{<mtext>exc</mtext>}}\text{=}\text{28}\text{A}\text{A;}\text{;}$;, μ = 0.15 m₀, and F = 1.2 × 10⁵ V cm^-1) have been determined from the electroabsorption spectrum.     

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.     

Limit cycle in a bound exciton recombination model in non-equilibrium semiconductors

A non-equilibrium semiconductor model involving the processes of photogeneration of electron-hole pairs (e-h) (rate G), stimulated creation of excitons from e-h (rate constant C) and decay of excitons on recombination centres (rate constant k) is analyzed in this paper for steady states and limit cycle behaviour. Considering the exciton decay to be similar to enzymatic processes in chemical reactions obeying a Michaelis-Menten law, and choosing units such that k = 1 = N, where N is the concentration of recombination centres, the model represents a 2-parameter (C and G) 2-dimensional (exciton and electron-hole concentrations x, n) dynamical system with a unique steady state (x₀,n₀) which is unstable in the region (l ? G)³?4C, the equality sign corresponding to the bifurcation curve in parameter space. In the region (l ? G)³ > 4C the system displays a unique stable limit cycle which is obtained in analytical form by employing a two-time-scales method for parameters in the neighbourhood of the bifurcation curve. The limit cycles are tilted ellipses with angular frequency $\text{}\text{?}$gw of the order of 10⁶ s^?1. In a realistic semiconductor situation G$\text{\$}\text{?}$10^?3.     

Valence band parameters of cubic zinc selenide derived from magnetoreflectance of the Γ6 − Γ8 exciton

Magnetoreflectance measurements on the Γ₆ ? Γ₈ free exciton ground state in cubic ZnSe in magnetic fields up to 18 Tesla are reported. The diamagnetic shift rate of the ground state components: $\text{|}\text{3}\text{2}\text{>β}$, $\text{|?}\text{3}\text{2}\text{>α}$, $\text{|}\text{1}\text{2}\text{>β}$ and $\text{|?}\text{1}\text{2}\text{>α}$ yield γ₂ = 0.53 ± 0.07 and an exciton reduced mass μ₀ = 0.117 ± 0.003, corresponding to γ₁ = 2.30 ± 0.45 for m_e¹ = 0.16 m₀. γ₁, γ₂ and an effective hole g-value $\text{κ}\text{tilde}\text{= -0.21}$ yield γ₃ = 0.82 ± 0.16 in the parabolic approximation and in agreement with the observed splitting of the $\text{|?}\text{3}\text{2}\text{>α}$, $\text{|?}\text{1}\text{2}\text{>β}$ states for B ∥ [110]. Taking into account polaron effects we derive bare valence band parameters γ₁^L = 2.71 ± 0.60, γ₂^L = 0.63 ± 0.09 and γ₃^L = 0.97 ± 0.21 from the renormalized parameters γ_i. The present results are considerably smaller than earlier theoretical calculations suggest, however they are in good agreement with a recent detailed analysis of two-photon absorption data for 2P exciton states.     

Resonant exciton trapping at impurity states in silver bromide

Excitation spectra near the indirect exciton edge of AgBr at 1.8K are reported for several luminescence lines from weakly localized excitons. Excitation below the exciton absorption threshold reveals several excited bound exciton states the energetic positions of which are determined. For excitation above the threshold, strong energy dependent structure is observed. It is interpreted in terms of resonant trapping of free excitons in both ground and excited bound exciton states associated with emission of LO(Γ), long wavelength acoustic and intervalley TA(X) and LA(X) phonons as well as combinations and overtones of these. From measurements in doped crystals two bound exciton systems are found to be correlated with Cd²⁺ and Ca²⁺, respectively.