Intrinsic luminescence of amorphous and disordered crystalline systems

A unified method is developed for describing the steady-state luminescence of exciton fluctuation states for weak excitation in different disordered systems. The phononless luminescence band is found to be formed by “radiative” states of the fluctuation tail in the density of states, i.e., by states for which nonradiative states are either nonexistent or have a low probability. The shape of the emission spectra calculated including the phonon interaction is in good agreement with experimental luminescence spectra of α Si:H and of solid solutions of ZnSe_(1−c)Te_c and CdS_(1−c)Se_c. Fiz. Tverd. Tela (St. Petersburg) 40, 890–891 (May 1998)     

Fluctuation states and optical spectra of solid solutions with a strong isoelectronic perturbation

We propose an approach to describing the density of fluctuation states in a disordered solid solution with a strong perturbation introduced by isoelectronic substitution in the range of attraction-center concentrations below the threshold of percolation along the sites of a disordered sublattice. To estimate the number of localized states we use the results of lattice percolation theory. We describe a method for distinguishing, within the continuum percolation theory, among the various “radiating” states of the fluctuation-induced tail, states that form the luminescence band at weak excitation. We also establish the position of the band of radiating states in relation to the absorption band of the excitonic ground state and the mobility edge of the system. The approach is used to describe the optical spectra of the solid solution ZnSe_1−c Te_c, which at low Te concentrations can be interpreted as a system with strong scattering. We take into account the exciton-phonon interaction and show that the calculated and observed luminescence spectra of localized excitons are in good agreement with each other. Zh. éksp. Teor. Fiz. 115, 1039–1062 (March 1999)     

Photoelectron spectra of thin films of the high-T c superconductor YBa2Cu3O7−δ

The results of calculations of the energy band structure of thin films are used to obtain theoretical photoelectron spectra of the valence band of the compound YBa₂Cu₃O_7−δ for δ=0 and δ=1 at various photon energies; the spectra are averaged over the photoelectron emission angles. The principal structural features of the spectra are determined by the d states of copper atoms, while the variation of the shape of the spectra with increasing photon energy is attributed to a relative decrease in the contribution from the p states of oxygen atoms. The density of d states around the Fermi level for YBa₂Cu₃O₆ films is observed to increase relative to YBa₂Cu₃O₇ films. Fiz. Tverd. Tela (St. Petersburg) 39, 437–440 (March 1997)     

Optical spectra and a tail in the density of states of the disordered solid solution ZnSe1−c Tec

A calculational scheme is presented to determine the density of states in the fluctuation tail for the disordered solid solution ZnSe_1−c Te_c at concentrations below the threshold for percolation over sublattice sites. Zero-phonon absorption and luminescence bands in the region of the exciton ground state are found using an approach developed earlier. Phonon coupling is taken into account, and vibronic absorption and luminescence bands are obtained. Experimental data are shown to be in a good agreement with the calculations. Fiz. Tverd. Tela (St. Petersburg) 40, 1420–1425 (August 1998)     

X-ray microanalysis of quaternary semiconductor solid solutions and its application to the (SnTe-SnSe):In system

A reliable technique of local chemical characterization of multicomponent semiconductor solid solutions has been developed, and the possibility of its application to the SnTe-SnSe quaternary solid solutions doped with 16 at.% In verified. The behavior of the electrical resistivity of samples of these solid solutions at low temperatures, 0.4–4.2 K, has been studied. The critical temperature T _c and the second critical magnetic field H _c2 of the superconducting transition and their dependences on the solid-solution composition have been determined. The superconducting transition at T _c≈2–3 K is due to hole filling of the In-impurity resonance states, and the observed variation of the superconducting transition parameters with increasing Se content in the solid solution is related to the extrema in the valence band and the In band of resonance states shifting with respect to one another. Fiz. Tverd. Tela (St. Petersburg) 41, 612–617 (April 1999)     

Intraband luminescence spectra of insulators and semiconductors excited by pulsed electron beams or electric fields

The features of the intraband luminescence spectrum of wide-gap insulators (KI, KBr, CsCl, etc.) and semiconductors (GaP, CdS, α-SiC, and ZnS) are studied in the temperature interval 80–760 K. The spectra of the intraband luminescence are compared with the spectra of the pre-breakdown electroluminescence of GaP and α-SiC surface-barrier diode structures and of a ZnS thin-film electroluminescence indicator. In alkali halide crystals the short-wavelength boundary hν _m of the intraband luminescence is less than the band gap E _g and is governed by complex excitonic processes. In semiconductors with indirect transitions hν _m>E _g. The differences in the spectra of the intraband luminescence and the intraband pre-breakdown electroluminescence can be explained by differences in the distributions of the hot charge carriers over levels of the allowed bands and in the maximum energies of the carriers involved in the formation of the spectra. Fiz. Tverd. Tela (St. Petersburg) 39, 613–617 (April 1997)     

Electronic excitations in ZnWO4 and ZnxNi1?xWO4 (x = 0.1 ? 0.9) using VUV synchrotron radiation

The photoluminescence spectra and luminescence excitation spectra of pure microcrystalline and nano-sized ZnWO₄ as well as the Zn _x Ni_1−x WO₄ solid solutions were studied using vacuum ultraviolet (VUV) synchrotron radiation. The samples were also characterized by x-ray powder diffraction. We found that: (i) the shape of the photoluminescence band at 2.5 eV, being due to radiative electron transitions within the [WO₆]⁶⁻ anions, becomes modulated by the optical absorption of Ni²⁺ ions in the Zn _x Ni_1−x WO₄ solid solutions; and (ii) no significant change in the excitation spectra of Zn_0.9Ni_0.1WO₄ is observed compared to pure ZnWO₄. At the same time, a shift of the excitonic bands to smaller energies and a set of peaks, attributed to the one-electron transitions from the top of the valence band to quasi-localized states, were observed in the excitation spectrum of nano-sized ZnWO₄.     

Free and localized excitons in the luminescence spectrum of C60 crystals at high pressure

The luminescence spectra of C₆₀ single crystals are studied at T≅10 K and pressure up to 4.0 GPa. It is observed that as the pressure increases, one fine-structure band in the spectrum intensifies sharply and dominates at pressures P≥1.7 GPa. The pressure shift of this band is much larger than the shift of other bands in the spectrum, and its magnitude correlates with the pressure dependence of the band gap. It is shown that this band could be due to radiative recombination of free Frenkel excitons. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 3, 234–238 (10 August 1998)     

Luminescence spectra and crystal structure of high-temperature superconductors

The luminescence spectra are obtained in the visible region for the high-T _c superconductors La₂CuO₄, YBA₂Cu₃O_7−δ , Bi₂Sr₂CaCu₂O_8±δ , and YBa₂Cu₃O_8±δ and for the secondary phases BaCuO_2±γ and Y₂Cu₂O₅. The presence of a luminescence band with energy E _lum∼2.4 eV in the spectra of all the investigated compounds is established. The nature of the observed luminescence bands is discussed on the basis of a comparative analysis of the crystal structures and luminescence spectra and on the basis of notions as to the presence of bands in the spectra accompanied by photoinduced diffusion of weakly bound oxygen and photoinduced charge transfer in the CuO₂ planes. Fiz. Tverd. Tela (St. Petersburg) 39, 1739–1746 (October 1997)     

Luminescence properties of oxide coatings on aluminum alloys

This is a study of the luminescence properties of coatings formed on aluminum alloys by anodizing in electrolytic solutions based on oxalic, sulfuric, and tartaric-sulfonic acids. At least two emission centers, with band maxima in the ranges of 390–410 and 470–510 nm, can be reliably identified in the photoluminescence spectra. The first type of center is characterized by single-band photoluminescence excitation spectra and the second, by two-band spectra. An analysis of the two-band photoluminescence excitation (PLE) spectra in the range of 470–510 nm shows that the position of the narrow short-wavelength PLE spectrum near 272 nm is independent of the type of acid used in the anodization process. The position and shape of the other PLE spectral bands depend both on the type of acid used and on the processing of the alloy or alumina surfaces. It is assumed that defect-free alumina centers are responsible for the 272 nm PLE band, while the other photoluminescence bands are caused primarily by different divacancies of oxygen (F₂⁺ {F_2^+} , F ₂, and F₂⁺² {F_2^{+2}} centers) whose origin is governed by the type of electrolyte.     

Thermoactivated spectroscopy of heterovalent impurity traps in CdWO4

Abstract

Recombination luminescence emission spectra, TSL and trap spectra estimated by fractional glow technique (FGT), in nominally pure and Li-, Bi- and Ho-doped CdWO₄, crystals are reported. According to the investigations by FGT heterovalent impurities Li, Bi and Ho causes localized electronic states which act as traps for charge carriers. It is shown that TSL results in emission of known blue-green luminescence band by emptying of the Li⁺-related traps in CdWO₄-Li and yellow luminescence band by emptying of the Bi³⁺-related traps in CdWO₄-Bi. It is proposed that blue-green and yellow luminescence occur by recombination correspondingly of free holes and free electrons at different intrinsic tungstate group related luminescence centers.     

Density of states and dispersion of quasiparticles in the Emery model: Nonlocal path-integral Monte Carlo algorithm

The spectral density of states for a 108-site Cu₃₆O₇₂ cluster in the two-dimensional three-band Emery model is reconstructed with the aid of a path integral Monte Carlo algorithm. Dispersion relations are obtained for quasiparticles in the upper Hubbard band and in the correlated-states band; this corresponds to electron and hole doping of high-T _c superconductors. The form of the isoenergy surfaces is close to the experimentally observed form and confirms the existence of singularities in the density of states near the Fermi level. Pis’ma Zh. éksp. Teor. Fiz. 63, No. 11, 860–865 (10 June 1996)     

Burstein–Moss shift and room temperature near-band-edge luminescence in lithium-doped zinc oxide

Nanopowders of pure and lithium-doped semiconducting ZnO (Zn_1−x Li _x O, where x= 0, 0.01, 0.03, 0.06, 0.09 and 0.15 in atomic percent (at.%)) are prepared by PEG-assisted low-temperature hydrothermal method. The average crystallite size is calculated using Debye–Scherrer formula and corrected for strain-induced broadening by Williamson–Hall (W–H) plot. The peak shift in XRD and the lattice constant of ZnO as a function of unit cell composition are predicted by Vegard’s law. The evolution of ZnO nanostructures from rod-shaped to particle nature is observed from TEM images and the influence of dopant on the morphology is investigated. The optical absorption measurement marks an indication that the incorporation of lithium ion into the lattice of ZnO widens the optical band gap energy from ∼2.60 to ∼3.20 eV. The near band edge (NBE) emission peak centered at ∼3.10 eV is considered to be the dominant emission peak in the PL spectra. Blue emission peak is not observed in doped ZnO, thus promoting defect-free nanoparticles. The Burstein–Moss shift serves as a qualitative tool to analyze the widening of the optical band gap and to study the shape of the NBE luminescence in doped ZnO nanopowders. FT-IR spectra are used to identify the strong metal–oxide (Zn–O) interaction.     

Anti-stokes luminescence of solid AgCl<Subscript>0.95</Subscript>I<Subscript>0.05</Subscript> solutions

An anti-Stokes luminescence band with λ_max = 515 nm of microcrystals of solid AgCl_0.95I_0.05 solutions excited by a radiation flux of density 10¹³–10¹⁵ quanta/cm²·sec in the range 600–800 nm at 77 K was detected. It is shown that the intensity of this luminescence and the frequency of its excitation depend on the prior UV-irradiation of samples. Analysis of the stimulated-photoluminescence spectra and the anti-Stokes luminescence excitation spectra of the indicated microcrystals has shown that to the centers of anti-Stokes luminescence excitation correspond local levels in the forbidden band of the crystals. These states are apparently due to the atomic and molecular disperse silver particles that can be inherent in character or formed as a result of a low-temperature photochemical process. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 738–742, November–December, 2005.     

Cathodoluminescence of ZnSe(Bi):Al crystals

The cathodoluminescence (CL) in ZnSe crystals annealed at T=1200 K in a Bi melt containing an aluminum impurity is investigated. The spectra are recorded for different excitation levels, temperatures, and detection delay times t ₀. As t ₀ is increased, the intensity of the orange band at λ _max=630 nm (1.968 eV) in the CL spectrum decreases in comparison to the intensity of the dominant yellow-green band at λ _max=550 nm (2.254 eV), whose half-width increases in the temperature range 6–120 K and then decreases as the temperature increases further. It is shown that such behavior of the yellow-green band is caused by the competition between two processes: recombination of donor-acceptor pairs and of free electrons with holes trapped on acceptors. The former mechanism is dominant at low temperatures, and the latter mechanism is dominant at high temperatures. At T∼120 mK the contributions of the two mechanisms to the luminescence are comparable. The resultant structureless band then achieves its greatest half-width, which is dictated by the interaction of the recombining charge carriers with longitudinal-optical and longitudinal-acoustic phonons and with the free-electron plasma. The mean number of longitudinal-optical phonons emitted per photon is determined mainly by their interaction with holes trapped on deep acceptors in the form of Al atoms replacing Se. The donor in the pair under consideration is an interstitial Al atom. Fiz. Tverd. Tela (St. Petersburg) 39, 1526–1531 (September 1997)     

Muonic study of type II superconductors

A theory of μSR method is developed for uniaxial anisotropic high-T _c superconductors. In two extreme cases ofH _ext‖c andH _ext⊥c analytical formulas are obtained which makes it possible to determine from the position of van Hove singularities in the Fourier-spectrum of muonium polarization, the type and parameters of the vortex lattice, such as λ _ab (λ _c ). In caseH _ext≲H _c2 we obtained the shape of the Fourier-spectrum in analytical form and the simple method of determining the Ginsburg-Landau parameter κ. Convenient expressions for numerical calculations are obtained for the arbitrary orientation of the external field, and an algorithm is provided to compute the mean fieldB, the vortex lattice parameters and the bulk field distribution in anisotropic superconductor. The Fourier spectrum of polarization based on these calculations can be used to independently check the validity of the high-T _c parameters determination for “appropriate” orientations.     

Anisotropy of permittivity of the hexagonal multiferroic HoMnO<Subscript>3</Subscript> in the spectral range 0.6–5.0 eV

The anisotropy of the optical properties of a single crystal of the hexagonal manganite HoMnO₃ has been investigated by spectroscopic ellipsometry in the spectral range 0.6–5.0 eV. It has been demonstrated that the optical absorption edge for the polarization E ⊥ c is determined by the intense narrow transition O(2p) → Mn(3d) centered at 1.5 eV, whereas this transition for the polarization E ‖ c is strongly suppressed and shifted toward higher energies by 0.2 eV. It has been revealed that, at the temperature T = 293 K, the spectra for both polarizations E ‖ c and E ⊥ c exhibit a broad absorption band centered at ∼2.4 eV, which was earlier observed in nonlinear spectra during optical second harmonic generation.     

Two-photon-excited luminescence spectra in diamond nanocrystals

Two-photon-excited luminescence (TEL) spectra have been recorded in the blue (400–500 nm) and near-ultraviolet (300–400 nm) ranges for diamond particles with 4 nm average size, which were obtained by detonation synthesis from explosives. The observed TEL bands are attributed, by comparing the obtained spectra with the impurity luminescence spectra in large diamond crystals, to N2 and N3 defects associated with the presence of nitrogen impurities in diamond. The TEL spectra presented are found to have certain distinguishing features: short-wavelength shift of the maximum and changes in the shape and width of the spectral bands for ultradispersed diamond compared with the spectrum in bulk crystals. Fiz. Tverd. Tela (St. Petersburg) 41, 1110–1112 (June 1999)     

Electronic structure of semiconductor solutions of cadmium chalcogenides

The electronic structure of the semiconductor solid solutions CdS_xSe_1−x x=(0, 0.17, 0.33, 0.5, 0.67, 0.83, 1.0) is investigated. The experimental x-ray and x-ray-induced electronic spectra of sulfur in CdS are compared with computed spectra. The calculations are performed using the FEFF (Version 7) program and a package of programs that implements a cluster version of the local-coherent-potential approximation. The effect of an electron vacancy in the 1s level on the x-ray absorption spectrum is investigated. The band gap as a function of the anion concentration in the solution is estimated. Fiz. Tverd. Tela (St. Petersburg) 41, 41–43 (January 1999)