Photoacoustic spectroscopy of thin films of As<Subscript>2</Subscript>S<Subscript>3</Subscript>, As<Subscript>2</Subscript>Se<Subscript>3</Subscript> and GeSe<Subscript>2</Subscript>

Photoacoustic spectroscopy (PAS) is one of the important branches of spectroscopy, which enables one to detect light-induced heat production following the absorption of pulsed radiation by the sample. As₂S₃, As₂Se₃ and GeSe₂ exhibit a wide variety of photo-induced phenomena that enable them to be used as optical imaging or storage medium and various electronic devices, including electro-optic information storage devices and optical mass memories. Therefore, accurate measurement of thermal properties of semiconducting films is necessary to study the memory density. The thermal conductivity of thin films of As₂S₃ (thickness 100 μm and 80 μm), As₂Se₃ (thickness 100 μm and 80 μm) and GeSe₂ (thickness 120 μm and 100 μm) has been measured using PAS technique. Our result shows that the thermal conductivity of thicker films is larger than the thinner films. This can be explained by the thermal resistance effect between the film and the surface of the substrate.      

Optical properties of films of the ternary compound CuIn<Subscript>3</Subscript>Se<Subscript>5</Subscript>

We have used the laser vaporization method to obtain films of the ternary compound CuIn₃Se₅ and have studied the composition and structure of the films obtained. We have determined the energy and nature of the optical transitions for the indicated compound from the transmission spectra in the region of the intrinsic absorption edge. We have calculated the valence-band crystal-field (Δ_CF) and spin-orbit (Δ_SO) splitting energies according to Hopfield’s quasicubic model for the ternary compound CuIn₃Se₅. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 82–85, January–February, 2007.     

Geometries and electronic structures of Ga<Subscript>2</Subscript>Se<Subscript>3</Subscript>, Ga<Subscript>3</Subscript>Se<Subscript>2</Subscript> and their anions. Theoretical insights

We hereby report a theoretical study on the equilibrium geometries, electronic structures and harmonic vibrational frequencies of Ga₂Se₃, Ga₃Se₂ and their anions. The ground and low-lying excited states of Ga₂Se₃⁻, Ga₂Se₃, Ga₃Se₂⁻ and Ga₃Se₂ are studied at the B3LYP and/or MP2 and CCSD(T) levels in conjunction with 6-311+G(d) and 6-311+G(2df) one particle basis sets. Ga₂Se₂⁻ adopts the C_2v kite geometry while Ga₂Se₃ has a ‘V’ geometry. Ga₃Se₂⁻ has a three-dimensional ‘D_3h ’ geometry and Ga₃Se₂ prefers the three-dimensional ‘C_2v ’ structure. Electron detachment energies from the ground electronic states of the anions to several neutral states are reported and discussed. At CCSD(T)//MP2 level, the adiabatic electron affinity (AEA) of Ga₂Se₃ is calculated to be 3.23 eV when using the 6-311+G(2df) basis set and that of Ga₃Se₂ is 2.77 eV with the 6-311+G(d) basis set. The findings of this research are analyzed and compared with gallium oxide and sulfide analogues.     

Photoelectric properties of Al/In<Subscript>2</Subscript>Se<Subscript>3</Subscript> Schottky barriers

We used directional solidification of the melt to grow single crystals of the binary compound In2Se3 and then determined the composition of the crystals obtained and their structure. From Hall effect measurements, we determined the type of conductivity, the concentration, and the Hall mobility of the free electrons in the single crystals obtained, on which we developed photosensitive Al/In₂Se₃ Schottky barriers for the first time and determined their photoelectric properties. We established that the indicated barriers can be used to design broadband optical photoconverters based on In₂Se₃ single crystals. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 3, pp. 425–427, May–June, 2008.     

H<Subscript>2</Subscript>O/CuIn<Subscript>3</Subscript>Se<Subscript>5</Subscript> photoelectrochemical cells: Fabrication and properties

Single-phase coarse-grained CuIn₃Se₅ ingots are grown by horizontal oriented crystallization from the near-stoichiometric melt. Photosensitive structures based on the interface between these crystals and an electrolyte (H₂O) are created. It is shown that the CuIn₃Se₅ ternary compound is a direct-gap semiconductor with an energy gap Eg ≃ 1.1 eV (T = 300 K). H₂O/CuIn₃Se₅ photoelectrochemical cells seem to be promising for efficient wide-band photodetectors of natural light.     

Study on the spin-states of cobalt-based double-layer perovskite Sr<Subscript>2</Subscript>Y<Subscript>0.5</Subscript>Ca<Subscript>0.5</Subscript>Co<Subscript>2</Subscript>O<Subscript>7</Subscript>

The spin-states of cobalt based perovskite compounds depend sensitively on the valence state and local crystal environment of Co ions and the rich physical properties arise from strong coupling among charge, spin, and orbital degrees of freedom. While extensive studies have been carried out in the past, most of them concentrated on the isotropic compound LaCoO₃. In this paper, using the unrestricted Hartree-Fock approximation and the real-space recursion method, we have investigated the competition of various magnetically ordered spin-states of anisotropic double-layered perovskite Sr₂Y_0.5Ca_0.5Co₂O₇. The energy comparison among these states shows that the nearest-neighbor high-spin-intermediate-spin ferromagnetically ordered state is the relevant magnetic ground state of the compound. The magnetic structure and sizes of magnetic moments are consistent with the recent experimental observation.     

The influence of crystalline grain size on the thermal stability of the Er<Subscript>0.45</Subscript>Ho<Subscript>0.55</Subscript>Fe<Subscript>2</Subscript> compound

The phase composition and the temperature dependence of the magnetization of the Er_0.45Ho_0.55Fe₂ compound in coarse-grained, microcrystalline, and submicrocrystalline states are investigated experimentally. It is found that, upon heating under vacuum, the Er_0.45Ho_0.55Fe₂ microcrystalline powder with a crystalline grain size of ∼1 μm undergoes decomposition into pure iron and rare-earth (erbium and holmium) oxides and nitrides at a temperature of 500 K. The changes observed in the phase composition of the microcrystalline powder due to annealing are confirmed by x-ray diffraction analysis. Heating of the Er_0.45Ho_0.55Fe₂ submicrocrystalline sample leads to a partial change in the phase composition. The phase composition of a large crystal (∼1 mm in size) remains unchanged upon heating to 1080 K. It is shown that the thermal stability of the Er_0.45Ho_0.55Fe₂ compound depends on the crystalline grain size. __________ Translated from Fizika Tverdogo Tela, Vol. 44, No. 6, 2002, pp. 1060–1063. Original Russian Text Copyright ? 2002 by Mulyukov, Sharipov, Korznikova.     

Impurity band in SnBi<Subscript>4</Subscript>Se<Subscript>7</Subscript>: thermoelectric power and electrical resistivity measurements

Thermoelectric power and electrical resistivity measurements on polycrystalline samples of Bi₂Se₃ and stoichiometric ternary compound in the quasi-binary system SnSe–Bi₂Se₃ in the temperature range of 90–420 K are presented and explained assuming the existence of an impurity band. The variation of the electron concentration with temperature above 300 K is explained in terms of the thermal activation of a shallow donor, by using a single conduction band model. The density of states effective mass m ^*=0.15m ₀ of the electrons, the activation energy of the donors, their concentration, and the compensation ratio are estimated. The temperature dependence of the electron mobility in conduction band is analyzed by taking into account the scattering of the charge carriers by acoustic phonon, optical phonon, and polar optical phonon as well as by alloy and ionized impurity modes. On the other hand, by considering the two-band model with electrons in both the conduction and impurity bands, the change in the electrical resistivity with temperature between 420 and 90 K is explained.     

Physical properties,crystal and magnetic structure of layered Fe<Subscript>1.11</Subscript>Te<Subscript>1-</Subscript><Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Se<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> superconductors

The physical and structural properties of Fe_1.11Te and Fe_1.11Te_0.5Se_0.5 have been investigated by means of X-ray and neutron diffraction as well as physical property measurements. For the Fe_1.11Te compound, the structure distortion from a tetragonal to monoclinic phase takes place at 64 K accompanied with the onset of antiferromagnetic order upon cooling. The magnetic structure of the monoclinic phase was confirmed to be of antiferromagnetic configuration with a propagation vector k = (1/2, 0, 1/2) based on Rietveld refinement of neutron powder diffraction data. The structural/magnetic transitions are also clearly visible in magnetic, electronic and thermodynamic measurements. For superconducting Fe_1.11Te_0.5Se_0.5 compound, the superconducting transition with T _c = 13.4 K is observed in the resistivity and ac susceptibility measurements. The upper critical field H _c2 is obtained by measuring the resistivity under different magnetic fields. The Kim’s critical state model is adopted to analyze the temperature dependence of the ac susceptibility and the intergranular critical current density is calculated as a function of both field amplitude and temperature. Neutron diffraction results show that Fe_1.11Te_0.5Se_0.5 crystalizes in tetragonal structure at 300 K as in the parent compound Fe_1.11Te and no structural distortion is detected upon cooling to 2 K. However an anisotropic thermal expansion anomaly is observed around 100 K.     

Spectral properties of a Nd<Superscript>3+</Superscript>-doped Li<Subscript>3</Subscript>Ba<Subscript>2</Subscript>Gd<Subscript>3</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>8</Subscript> crystal

The spectral properties of a promising laser material, ternary molybdate Li₃Ba₂Gd₃(MoO₄)₈:Nd³⁺, are studied (i.e., its optical absorption spectra, luminescence spectra, kinetic of luminescence decay, and temperature dependence of luminescence). Luminescence of the crystalline matrix is detected, and the temperature dependence of its intensity and reabsorption by neodymium are investigated.     

Specific features of the electronic,spin, and atomic structures of a topological insulator Bi<Subscript>2</Subscript>Te<Subscript>2.4</Subscript>Se<Subscript>0.6</Subscript>

The specific features of the electronic and spin structures of a triple topological insulator Bi₂Te_2.4Se_0.6, which is characterized by high-efficiency thermoelectric properties, have been studied with the use of angular- and spin-resolved photoelectron spectroscopy and compared with theoretical calculations in the framework of the density functional theory. It has been shown that the Fermi level for Bi₂Te_2.4Se_0.6 falls outside the band gap and traverses the topological surface state (the Dirac cone). Theoretical calculations of the electronic structure of the surface have demonstrated that the character of distribution of Se atoms on the Te–Se sublattice practically does not influence the dispersion of the surface topological electronic state. The spin structure of this state is characterized by helical spin polarization. Analysis of the Bi₂Te_2.4Se_0.6 surface by scanning tunnel microscopy has revealed atomic smoothness of the surface of a sample cleaved in an ultrahigh vacuum, with a lattice constant of ~4.23 Å. Stability of the Dirac cone of the Bi₂Te_2.4Se_0.6 compound to deposition of a Pt monolayer on the surface is shown.     

luminescence of BaGa<Subscript>2</Subscript>Se<Subscript>4</Subscript> crystals activated by Eu<Superscript>2+</Superscript> and Ce<Superscript>3+</Superscript> ions

We have studied the effect of doping with Eu²⁺ and Ce³⁺ ions on the photoluminescence (PL) of BaGa₂Se₄ crystals in the temperature range 77–300 K. We have established that the broad bands with maxima at wavelengths 456 nm and 506 nm observed in the photoluminescence spectra of BaGa₂Se₄:Ce³⁺ crystals are due to intracenter transitions 5d → ²F_7/2 and 5d →²F_5/2 of the Ce³⁺ ions, while the broad photoluminescence band with maximum at 521 nm in the spectrum of BaGa₂Se₄:Eu²⁺ is associated with 4f⁶ 5d → 4f⁷ (⁸S_7/2) transitions of the Eu²⁺ ion. We show that in BaGa₂Se₄:Eu²⁺,Ce³⁺ crystals, excitation energy is transferred from the Ce³⁺ ions to the Eu²⁺ ions.     

High-frequency tunable EPR spectroscopy of non-Kramers ions in AgGaSe<Subscript>2</Subscript>: Cr,AgGaS<Subscript>2</Subscript>: Cr,and CdGa<Subscript>2</Subscript>S<Subscript>4</Subscript>: Cr crystals

Crystals of the chalcopyrite family, AgGaSe₂, AgGaS₂, and CdGa₂S₄, doped with chromium ions have been investigated using high-frequency broad-band EPR spectroscopy in the range 65–530 GHz at T = 4.2 K. It has been revealed that, in the AgGaSe₂ and AgGaS₂ crystals, the Cr²⁺ ions occupy positions with orthorhombic and tetragonal symmetry, whereas the previously investigated CdGaS₄ crystals contain only tetragonal centers. The observed spectra have been described in the framework of the spin-Hamiltonian formalism. Apart from the divalent chromium centers, the EPR lines attributed to non-Kramers ions are observed in the frequency range 300–450 GHz for all the crystals under investigation. The nature of these lines has been discussed.     

Colossal magnetoresistance of the inhomogeneous ferromagnetic semiconductor HgCr<Subscript>2</Subscript>Se<Subscript>4</Subscript>

A new method is described for attaining high magnetoresistance in inhomogeneous magnetic materials, which makes use of the formation of a depleted layer and a contact potential difference at the interface separating two semiconductors with different Fermi levels and the magnetic-field-induced variation in the contact potential difference and thickness of the interface layer. The proposed model of the magnetoresistive structure is realized on the basis of the HgCr₂Se₄ magnetic semiconductor. Layers of n-HgCr₂Se₄ up to a few tens of microns thick were prepared on the surface of p-HgCr₂Se₄ bulk single crystals by the diffusion technique. Application of a magnetic field stimulated in the structures a strong (by a factor of more than 200) increase of the current flowing through the n-layer.     

NMR study and electrical properties investigation of Zn<Subscript>2</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>

The α-Zn₂P₂O₇ compound was obtained by conventional solid-state reaction. The sample was characterized by X-ray powder diffraction, solid state ³¹P NMR MAS, and electrical impedance spectroscopy. The solid state ³¹P MAS NMR, performed at 121.49 MHz, shows three isotropic resonances at −21.1, −18.8, and −15.8 ppm, confirming the non-equivalency of the three PO₄ groups in the α-Zn₂P₂O₇ form. They are characterized by different chemical shift tensor parameters with the local geometrical features of the tetrahedra. Electrical impedance measurements of β-Zn₂P₂O₇, form stable for temperature greater than 403 K, were performed as a function of both temperature and frequency. The electrical conduction and dielectric relaxation have been studied. The AC conductivity obeys the universal power law. The approximation type correlated barrier hopping model explains the universal behavior of the n exponent. The impedance plane plot shows semicircle arcs at different temperatures, and an electrical equivalent circuit has been proposed to explain the impedance results. The circuits consist of the parallel combination of bulk resistance R _p and constant phase elements CPE. The simulated spectra show a good correlation with the experimental data.     

Electronic structure,ferroelectricity and optical properties of CaBi<Subscript>2</Subscript>Ta<Subscript>2</Subscript>O<Subscript>9</Subscript>

Using first-principles calculations based on density-functional theory in its local-density approximation, we investigated the Electronic structure, ferroelectricity and optical properties of CaBi₂Ta₂O₉ (CBT) for the first time. It is found that CBT compound has an indirect band gap of 3.114 eV and the O 2s and 2p states are strongly hybridized with the 6s states of Bi which belong to the (Bi₂O₂)²⁺ planes. The quite strong Ta–O and Bi–O hybridization is the primary source for ferroelectricity. Our results imply that the interaction between Bi and O is highly covalent. The anisotropy occurs mainly above 4 eV in the optical properties. The different optical properties have been discussed.     

Impact of Ultrathin Pb Films on the Topological Surface and Quantum-Well States of Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript> and Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript> Topological Insulators

The effect of an ultrathin Pb film deposited on the surface of Bi₂Se₃ and Sb₂Te₃ compounds on the electronic state structure of topological insulators is studied experimentally by the angle-resolved photoemission spectroscopy (ARPES) technique. The following features are revealed: formation of two-dimensional quantum-well states in the near-surface region, an increase in the binding energy of the Dirac cone and the core levels, and a simultaneous electronic states intensity redistribution in the system in photoemission spectra. The results obtained show that topological states may coexist at the interface between studied materials and a superconductor, which seems to be promising for application in quantum computers.     

<Superscript>77</Superscript>Se Low-Temperature NMR in the Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript> Single Crystalline Topological Insulator

⁷⁷Se nuclear magnetic resonance (NMR) measurements in the Bi₂Se₃ topological insulator single crystal were carried out at temperatures 15.8, 88, and 293 K. Bismuth selenide single crystalline plate was studied in the orientation when the crystallographic c-axis was parallel to the external magnetic field B₀. We observed two component NMR spectra at the three temperatures. It was shown that the NMR spectrum almost did not move with decreasing temperature and the density of charge carriers did not follow the thermal activation law.     

Synthesis,crystal structure,Hirshfeld surface analysis,and vibrational and DFT investigation of [C<Subscript>6</Subscript>H<Subscript>10</Subscript>(NH<Subscript>3</Subscript>)<Subscript>2</Subscript>]<Subscript>3</Subscript>CuBr<Subscript>4</Subscript>.3Br

Single crystal of a new organic–inorganic hybrid material [C₆H₁₀(NH₃)₂]₃CuBr₄.3Br was synthesized by the slow evaporation method at room temperature and characterized by X-ray diffraction, FTIR, Raman spectroscopy, UV–Vis, dielectric measurements, and Hirschfield surface analysis. The title compound crystallizes in trigonal system \( P\overline{3} \).The crystal packing is governed by the N-H…Br and non-classical C-H…Br hydrogen-bonding interactions between the 1, 2-diamoniumcyclohexane cations, the tetrahedral [CuBr₄]^3? anions, and the isolated ion Br^?. Theoretical calculations were performed using density functional theory (DFT) for studying the molecular structure, vibrational spectra, and optical properties of the investigated molecule in the ground state. The optimized geometrical parameters obtained by DFT calculations are in good agreement with single crystal XRD data. The optical properties were investigated by optical absorption and show two bands at 260 and 305 nm.     

Optical properties of ZnCr<Subscript>2</Subscript>Se<Subscript>4</Subscript>

We studied the optical properties of antiferromagnetic ZnCr₂Se₄ by infrared spectroscopy up to 28,000 cm^-1 and for temperatures from 5 to 295 K. At the magnetic phase transition at 21 K, one of the four phonon modes reveals a clear splitting of 3 cm^-1 as a result of spin-phonon coupling, the other three optical eigenmodes only show shifts of the eigenfrequencies. The antiferromagnetic ordering and the concomitant splitting of the phonon mode can be suppressed in a magnetic field of 7 T. At higher energies we observed a broad excitation band which is dominated by a two-peak-structure at about 18,000 cm^-1 and 22,000 cm^-1, respectively. These energies are in good agreement with the expected spin-allowed crystal-field transitions of the Cr³⁺ ions. The unexpected strength of these transitions with d-d character is attributed to a considerable hybridization of the selenium p with the chromium d orbitals.