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.     

Lifetimes of bound excitons in CdSe

Lifetime measurements have been made on bound excitons in CdSe, by using the time-correlated single photon counting and a cw mode-locked dye laser. The lifetimes of the T₂ (an exciton bound to a neutral donor) and I₁ (an exciton bound to be a neutral acceptor) bound excitons have been determined to be 0.50±0.05 and 0.80±0.05 ns, respectively. These values are in good agreement with those predicted by the model of Rashba and Gurgenishvili.     

On the possibility of determining the diffusion length of excitons in semiconductors from photomagnetic measurement data

The effect of a magnetic field on the photocurrent I_ph in Si and GaAs solar cells is investigated. It is shown that the observed change in the photocurrent I_ph of the solar cells in response to a magnetic field can be caused by a decrease in the diffusion length of excitons L_exc. A simplified model of the photomagnetic experiment is proposed to estimate the diffusion length of excitons L_exc and the contribution made by excitons to the photocurrent of the solar cells.     

Multiplasmon replicas of the emission lines of bound excitons in ZnSe crystals

This paper reports on the results of investigations into the cathodoluminescence spectra of ZnSe crystals grown from a vapor phase and annealed in a bismuth melt [ZnSe(Bi) crystals], as well as in a bismuth melt containing aluminum [ZnSe(Bi,Al) crystals], at a temperature of 1200 K for 120 h. The longitudinal optical (LO) phonon replicas of the emission lines of free excitons are dominant in the cathodoluminescence spectra of the samples subjected to annealing in the bismuth melt with subsequent quenching. The emission spectra of all the samples studied, including the initial crystals, contain series of I ₁ ^s,d -nLO lines of bound excitons. It is revealed that plasmon replicas are characteristic not only of the I ₁ ^s -nLO lines. A weak exciton-plasmon interaction manifests itself in the form of single-plasmon Stokes satellites of the I ₁ ^d -nLO spectral lines. A theory describing the multiphoton optical transitions of bound excitons with the participation of mixed plasmonphonon vibrational modes is proposed. This theory makes it possible to calculate the shape function of an emission spectrum without recourse to model concepts. The results of the theoretical calculations are in agreement with the experimental data.     

Resonant Raman scattering from superconducting single crystals of (BEDT-TTF)2I3

A study of low energetic resonant Raman scattering of (BEDT-TTF)₂I₃ superconducors was performed. The vanishing of phonon bands accompanied by a decrease of the electronic background was observed belowT _c . We propose a theoretical explanation for this novel effect in terms of the Balseiro-Falicov model of phonon-superconducting amplitude mode interaction.     

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.     

Edge emissions of ion-implanted CdS

Edge emissions of CdS crystals implanted with Li⁺, N⁺, Ne⁺ and P⁺ are studied. Li and P are found to form acceptors and give rise to I₁ lines in the blue and donor-acceptor pair recombination emissions in the green. N gives rise to two kinds of I₂ lines (excitons bound to neutral donors) and donor-acceptor pair recombination emissions. An acceptor due to a defect is found in N⁺ and Ne⁺ implanted CdS. The temperature range of thermal treatment where impurity centers are formed is also investigated. The relationship among impurity centers produced by N⁺ implantation is, moreover, discussed based upon the results obtained here and previous works.     

高速沉积微晶硅薄膜光发射谱的研究

采用PR650光谱光度计对高速沉积微晶硅薄膜的生长过程进行了在线监测研究,并对所对应的材料进行了Raman谱和红外吸收谱(FTIR)的测试.结果表明：能反映材料晶化程度的I_［SiH^*］/I_［Hβ^*］比值在沉积时间为100 s之内有下降的趋势,且反应气体总流量T_fl越小下降趋势越明显,这与拉曼散射光谱对材料的结构测试结果一致;沉积5 min时I 关键词： 高速沉积 微晶硅薄膜 电子温度     

Low-temperature photoluminescence of MBE-grown GaAs subject to an electric field

Low-temperature photoluminescence of GaAs has been investigated in MBE-grown Al _x Ga_1–x As-GaAs single heterojunctions subject to an electric field. No peak energy shift is observed in the emission lines due to free excitons and excitons bound to isolated centers when the electric field is applied. In contrast, the excitonic lines arising from the previously described defect-induced bound exciton (DIBX) transitions exhibit a prominent low-energy shift when the electric field is increased. We attribute these lines to excitons bound to acceptor pairs. The excitons bound to distant pairs have smaller binding energies than those bound to closer pairs. They are, therefore, easily dissociated in a weak electric field. The electrons and holes thus dissociated may again be trapped by closer pairs, which results in a low-energy shift of the overall spectrum. The photocurrent measured as a function of the electric field supports Dingle's rule for the valence bandedge discontinuity.     

Platinum and palladium as substrates for surface enhanced Raman spectroscopy

Surface enhanced Raman scattering (SERS) has been observed from the electrogenerated I₂ and I^-₃ coadsorbed on Pt and Pd electrodes. Theoretical models on the SERS process that emphasize the important role of the optical properties of the metal substrate cannot be used to explain this observation. The electronic interaction between the adsorbate and the substrate is believed to be the most important mechanism for the observed SERS.     

Thermal dissociation of excitons in a type-I GaAs/AlAs superlattice studied by time-resolved photoluminescence measurements

In order to investigate thermal properties of excitons, we have performed time-resolved photoluminescence (PL) measurements for a type-I (GaAs)₁₅/(AlAs)₁₅ superlattice. At low temperatures, PL signals show ordinal exponential time decay, whereas at high temperatures, the PL shows power decay. Such change of PL signals is understood by considering thermal dissociation of exciton into account. At low temperatures, recombination of bound excitons generates PL which shows exponential decay. At temperatures higher than the exciton binding energy, correlation between electrons and holes disappears. Recombination of free excitons causes PL which decays by a power function. By means of the least-squares fitting, we evaluate the portion of bound excitons, recombination time of bound and free excitons as functions of temperatures.     

Metastable optical absorption of relaxed electronic excitations in BeO-Zn crystals

Spectra of metastable optical absorption and its relaxation kinetics have been studied in zinc-doped BeO crystals by time-resolved pulsed absorption spectroscopy. A comparison of the observed induced optical absorption of self-trapped excitons and small-radius excitons bound to the zinc impurity suggests that their hole components have similar structures and reveals distinctive features of “forbidden” optical transitions in the electronic components. Metastable optical absorption in Zn⁺ centers has been discovered. It is shown that the small-radius excitons bound to the zinc impurity form in the hole stages of thermally stimulated tunneling recombination processes involving Zn⁺ electronic centers. It has been found that the high recombination probability of the electronic and hole centers created in BeO-Zn crystals by an electron beam may be due to the high degree of their spatial correlation. Fiz. Tverd. Tela (St. Petersburg) 41, 601–605 (April 1999)     

Electromodulation spectroscopy of excitons: High field regime

The effects of electric field on excitons have been investigated experimentally by means of electroabsorption (EA). The behavior of excitons with ionization fields F_I of the same order of magnitude as or smaller than typical applied fields is reported. EA spectra associated with excitons in TlBr, PbI₂, BiI₃, trigonal Se, and α-monoclinic Se will illustrate this case. In this situation the EA signal arises principally from the effect on the exciton ground state, and no finer structure could be detected. The exciton ground state undergoes a shift to higher energies with the applied field. Characteristic dependences with field of the sizes, energy position of the peaks, and zero crossing points of the EA signals have been found. Estimates of exciton parameters can be readily obtained from the EA spectra. Unusual features of the exciton EA spectra PbI₂ are discussed. Qualitatively, at least, theoretical predictions are obeyed.     

Relaxation dynamics of electronic excitations in CaWO4 and CdWO4 crystals studied by femtosecond interferometry technique

The relaxation of electronic excitations in CdWO₄ and CaWO₄ crystals was studied using the method of time-resolved interferometry with 100-fs temporal resolution at temperatures 15–295 K. The electronic system was excited in the one-photon and two-photon regime within the excitonic band in CaWO₄ and in the electron-hole continuum in CdWO₄. Immediate trapping of charge carriers was detected under pumping in the excitonic band of CaWO₄. This result is in agreement with decay kinetics measurements with nanosecond time resolution under direct creation of excitons by 100-fs laser pulses. Fast relaxation of charge carriers followed by formation of excitons was observed in CdWO₄. The comparison with previous work allows suggesting the formation of bulk excitons and surface-perturbed excitons in the multi-photon and one-photon regime. The corresponding models of self-trapped exciton creation in tungstate crystals are discussed.     

Raman scattering of Zn doped CuGaS2 layers grown by vapor phase epitaxy

Raman spectra for non-site-selectively and site-selectively Zn-doped CuGaS₂ layers grown by vapor phase epitaxy (VPE) were investigated. Although an appearance of characteristic Raman line(s) related with the doped Zn atom was not seen, an enhancement of the Raman intensity ratio of the highest LO mode to the A₁ mode (I_LO/I_A1) was observed. The site-selectively Zn-doped layers with p-type conductivity exhibited larger I_LO/I_A1 ratio compared to those with n-type conductivity. The observed correlation between the I_LO/I_A1 ratio and the peak energy of the photoluminescence characteristic for Zn-doped p-type samples (L emission) suggests that the enhancement of I_LO/I_A1 is due to the increase of Zn atom substituting Ga site (Zn_Ga) which is acting as an acceptor.     

Raman analysis of amorphous silicon ruthenium thin films embedded with nanocrystals

We report the Raman analysis of both as‐deposited and annealed amorphous silicon ruthenium thin films embedded with nanocrystals. In the Raman spectra of as‐deposited films, variations of TO peak indicate a short‐range disorder of a‐Si network with an increase of Ru concentration. The substitutional Ru atoms lower the concentration of Si―Si bonds and suppress the intensity of TO peak, but have less effect on TA, LA and LO peaks. In the Raman spectra of annealed films, characteristic parameters confirm the upgrade of a‐Si network at a low annealing temperature and the emergence of both ruthenium silicide and silicon nanocrystals at 700 °C. Although ruthenium silicide nanocrystals present no Raman peaks in the Raman spectra of as‐deposited samples, the non‐linear variations of intensity ratios I_{LA + LO}/I_TO and I_TA/I_TO still suggest their existence, and these nanocrystals are subsequently verified by high‐resolution transmission electron microscopy. Copyright © 2015 John Wiley & Sons, Ltd.     

Two-photon multiterm nonadiabatic transitions

The resonance Raman scattering phenomenon via the predissociated state is described in the four crossing terms A-(1, 2)-B model when terms 1 and 2 strongly interact. The Green's function closed representation for the coupled intermediate electronic terms 1 and 2 is obtained. The transition amplitude I _{A-(1, 2)-B} is found in the WKB approximation. The resonance Raman scattering via the predissociated ³Π_Ou ⁺ state of the interhalogen molecules is treated in detail.     

Exciton fission in excimer-forming crystal dynamics of excimer build-up

The optically induced fission of singlet excitons in both α- and β-perylene crystals is investigated at room temperature. In the monomeric β-perylene the fission thresold coincides with the energy of two triplet excitons whereas it is blueshifted by ～3500 cm^-1 in the excimer forming α-crystal. This indicates that the excimer is formed prior to the fission of the initially excited monomer state and it implies that the rate of excimer formation is exceeding 10¹² s^-1. Theoretical estimates led to k_exc ≈ 10¹²-10¹³ s^-1. Analysis of the experimental data shows also that two adjacent perylene molecules in the α-crystal, each of them in the T₁ electronic state, are bound with the binding energy B_2T1 ≈ 350 cm^-1.     

The location and shape of the conduction band minima in cubic silicon carbide

We have measured the inter-bound state excitation spectrum of the N_C donor in cubic β-SiC through the ‘two-electron’ transition satellites observed in the luminescent recombination of excitons bound to neutral N donors. Transitions are seen to p as well as s-like donor states although the transition oscillator strength is derived from interaction with the impurity core since parity is conserved through inter-valley scattering by p-like X phonons. The Zeeman splitting of a luminescence line involving the 2p± donor state yield the electron mass parameter m_t = 0.24 ± 0.01 m₀. This and the directly measured energy separations of the 2p₀ and 2p± states yields m_t/m₁ = 0.36 ± 0.01 with the static dielectric constant K = 9.92 ± 0.1. Mutually consistent central cell corrections of 1.1 and 8.4 meV are observed for the 2s(A₁) and 1s(A₁) donor states, the latter being in agreement with a recent estimate from electronic Raman scattering by Gaubis and Colwell. The ionization donor energy of the N_C donor, 53.6 ± 0.5 meV is consistent with earlier, less accurate estimates from donor-acceptor pair and free to bound luminescence. There is no evidence for a ‘camel's back’ conduction band structure in cubic SiC, unlike GaP. The two-phonon sidebands of the N_C donor exciton luminescence spectrum in SiC can be constructed by X and Г phonons only.     

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.