Urbach rule and disordering processes in Cu6P(S1−xSex)5Br1−yIy superionic conductors

Compositional behavior of Urbach absorption edge is studied as well as the effect of compositional disordering on the parameters of exciton-phonon interaction, phase transition temperatures and electric conductivity in Cu₆P(S_1−xSe_x)₅Br_1−yI_y superionic solid solutions. The effect of different types of disordering on the optical absorption processes and specific features of compositional changes in the absorption edge spectra under S→Se and Br→I anion substitution in the mixed crystals are investigated. (x, T) phase diagrams for Cu₆P(S_1−xSe_x)₅X (X=I, Br) solid solutions are studied.     

On the Urbach rule in sulphur-implanted Cu6PS5I superionic conductors

Cu₆PS₅I superionic crystals, grown using chemical vapour transport, were implanted by sulphur ions. The ion implantation effect on the phase transitions is studied by temperature isoabsorption investigation of the optical absorption edge. For the implanted crystals the optical absorption edge shape is studied in the temperature range 77-320 K, the parameters of exciton-phonon interaction, resulting in the Urbach behaviour of the optical absorption edge, are determined, the temperature dependences of the optical pseudogap and Urbach energy are obtained. The implantation effect on the ordering-disordering processes in Cu₆PS₅I superionic conductors is studied.     

Isoabsorption and spectrometric studies of optical absorption edge in Cu6AsS5I superionic crystal

Cu₆AsS₅I single crystals were grown using chemical vapour transport method. Two low-temperature phase transitions (PT) are observed from isoabsorption studies: a first-order PT at Т_?=153±1 K and a second-order PT in the temperature interval T_?I=260–280 K. At low temperatures and high absorption levels an excitonic absorption band was revealed in the range of direct optical transitions. At Т>Т_?, the absorption edge has an exponential shape and a characteristic Urbach bundle is observed. The influence of the cationic P→As substitution on the parameters of the Urbach absorption edge, parameters of exciton–phonon interaction, and phase transitions temperatures are studied.     

Electrical and optical absorption studies of Cu7GeS5I fast-ion conductor

Electrical conductivity and fundamental absorption spectra of monocrystalline Cu₇GeS₅I were measured in the temperature ranges 95-370 and 77-373 K, respectively. A rather high electrical conductivity (σ_t=6.98×10⁻³Ω⁻¹ cm⁻¹ at 300 K) and low activation energy (ΔE_a=0.183 eV) was found. The influence of different types of disordering on the Urbach absorption edge and electron-phonon interaction parameters were calculated, discussed and compared with the same parameters in Cu₇GeS₅I, Cu₆PX₅I (X=S,Se) and Ag₇GeX₅I (X=S,Se) compounds. We have concluded that the P→Ge and Cu→Ag cation substitution results in an increase of the electrical conductivity and a decrease of the activation energy. Besides, P→Ge substitution, results in complete smearing and disappearance of the exciton absorption bands and in blue shift of the Urbach absorption edge, an increase of the edge energy width and an electron-phonon-interaction enhancement.     

Effect of composition and thermal annealing on the absorption and electrical conduction of Se85−xTe15Sbx glasses

The optical absorption of the as-prepared and thermally annealed Se_85−xTe₁₅Sb_x (0≤x≤9) thin films was measured. The mechanism of the optical absorption follows the rule of non-direct transition. The optical energy gap (E₀) decreased from 1.12 to 0.84 eV with increasing Sb content of the as-prepared films from 0 to 9 at.%. The as-prepared Se₇₆Te₁₅Sb₉ films showed an increase in (E₀) with increasing the temperature of annealing in the range above T_g (363 K). The electrical conductivity of the as-prepared and annealed films was found to be of Arrhenius type with temperature in the range 300-360 K. The activation energy for conduction was found to decrease with increasing both the Sb content and temperature of annealing. The results were discussed on the basis of the lone-pair electron effect and of amorphous crystalline transformation.     

The influence of microscopic parameters on the ionic conductivity of SrBi2(Nb1−xVx)2O9−δ(0≤x≤0.3) ceramics

Layered SrBi₂(Nb_1−xV_x)₂O_9−δ (SBVN) ceramics with x lying in the range 0-0.3 (30 mol%) were fabricated by the conventional sintering technique. The microstructural studies confirmed the truncating effect of V₂O₅ on the abnormal platy growth of SBN grains. The electrical conductivity studies were centred in the 573-823 K as the Curie temperature lies in this range. The concentration of mobile charge carriers (n), the diffusion constant (D₀) and the mean free path (a) were calculated by using Rice and Roth formalism. The conductivity parameters such as ion-hopping rate (ω_p) and the charge carrier concentration (K′) term have been calculated using Almond and West formalism. The aforementioned microscopic parameters were found to be V₂O₅ content dependent on SrBi₂(Nb_1−xV_x)₂O_9−δ ceramics.     

Metal-insulator transition in the spinel-type Cu(Ir1−xCrx)2S4 system

A normal thiospinel CuIr₂S₄ exhibits a temperature-induced metal-insulator (M-I) transition around 230 K with structural transformation, showing hysteresis on heating and cooling. On the other hand, CuCr₂S₄ has the same normal spinel structure without the structural transformation. CuCr₂S₄ has been found to be metallic and ferromagnetic with the Curie temperature T_c~377 K. In order to see the effect of substituting Cr for Ir on the M-I transition, we have carried out a systematic experimental study of electrical and magnetic properties of Cu(Ir_1−xCr_x)₂S₄. The M-I transition temperature shifts to lower temperature with increasing Cr-concentration x and this transition is not detected above x~0.05. The ferromagnetic transition temperature decreases as x is decreased and the transition does not occur below x~0.20.     

Temperature variation of electrical conductivity and absorption edge in Cu7GeSe5I advanced superionic conductor

Single crystals of Cu₇GeSe₅I superionic conductor were grown by chemical transport. Their electrical conductivity in the frequency range 1.0×10⁶–1.2×10⁹ Hz and in the temperature range 196–295 K was measured. Cu₇GeSe₅I crystal is shown to exhibit a rather high electrical conductivity (σ₂₉₅=64.0 S/m at 295 K) and a low activation energy (ΔE_a=0.125 eV). Optical absorption edge of Cu₇GeSe₅I crystals in the temperature range 77–300 K was studied, the temperature dependences of the optical pseudogap and Urbach energy being obtained. The effect of different types of disordering on the Urbach absorption edge and electron–phonon interaction parameters was investigated.     

Electrical and optical properties of GexFexSe100−2x chalcogenide thin films

Optical absorption at room temperature and electrical conductivity at temperatures between 283 and 333 K of vacuum evaporated Ge_xFe_xSe_100−2x (0≤x≤15) amorphous thin films have been studied as a function of composition and film thickness. It was found that the optical absorption is due to indirect transition and the energy gap increases with increasing both Ge and Fe content; on the other hand, the width of the band tail exhibits the opposite behavior. The optical band gap E_opt was found to be almost thickness independent. The electrical conductivity show two types of conduction, at higher temperature the conduction is due to extended states, while the conduction at low temperature is due to variable range hopping in the localized states near Fermi level. Increasing Ge and Fe contents were found to decrease the localized state density N(E_F), electrical conductivity and increase the activation energy for conduction, which is nearly thickness independent. Variation of the atomic densities ρ, molar volume V, glass transition temperature T_g cohesive energy C.E and number of constraints N_Co with average coordination number Z was investigated. The relationship between the optical gap and chemical composition is discussed in terms of the cohesive energy C.E, average heat of atomization and coordination numbers.     

Preparation of REFeAsO1−xFx (RE=Sm and Gd) superconductors at a relatively low temperature

A series of the SmFeAsO_1−xF_x and GdFeAsO_1−xF_x (x=0.05, 0.1, 0.15, 0.2, 0.25) samples have been prepared using nano-scaled ReF₃ as the fluorine resource at a relatively low temperature. The samples have been sintered at 1100 and 1120 °C for SmFeAsO_1−xF_x and GdFeAsO_1−xF_x, respectively. These temperatures are at least 50-60° lower than other previous reports. All of the so-prepared samples possess a tetragonal ZrCuSiAs-type structure. Dramatically supression of the lattice parameters and increase in T_c proved that this low temperature process was more effective to introduce fluorine into R_EFeAsO. Superconducting transition appeared at 39.5 K for SmFeAsO_1−xF_x with x=0.05 and at 22 K for GdFeAsO_1−xF_x with x=0.1. The highest T_c was detected to be 54 K in SmFeAsO_0.8F_0.2 and 40.2 K in GdFeAsO_0.75F_0.25. The use of the nano-scaled ReF₃ compounds has improved the efficiency of the present low temperature method in synthesizing the fluorine-doped iron-based superconductors.     

Investigation of the structural distortion in FeSex crystals by X-ray absorption near edge structures (XANES) spectroscopy

Crystals of the new superconductor FeSe were investigated by X-ray absorption near edge structures spectroscopy (XANES) in the temperature range 300-77 K. Crystals with Se content varying from x=1-0.8 were used. The Fe K-edge spectra show a structure distortion and increase in hole content as x decreases. The Fe K-edge spectra also show changes when the crystals are cooled to 100 K which may be related to the orthorhombic distortion reported in these crystals. The data is examined in conjunction with XRD measurements on the crystals to seek a correlation.     

Structural,thermal and electrical properties of the semiconductor system Ag(1−x)CuxInSe2

This paper presents a study of bulk samples synthesized of the Ag_1−xCu_xInSe₂ semiconductor system. Structural, thermal and electrical properties, as a function of the nominal composition (Cu content) x=0.0, 0.2, 0.4, 0.6, 0.8, and 1.0 were studied. The influence of x on parameters such as melting temperature, solid phase transition temperature, lattice parameters, bond lengths, crystallite size t (coherent domain), electrical resistivity, electrical mobility and majority carrier concentration was analyzed. The electrical parameters are analyzed at room temperature. In general, it is observed that the properties of the Ag_1−xCu_xInSe₂ system for x≤0.4 are dominated by n-AgInSe₂, while for x>0.4, these are in the domain of p-CuInSe₂. The crystallite size t in the whole composition range (x) is of the order of the nanoparticles. Secondary phases (CuSe, Ag₂Se and InSe) in small proportion were identified by XRD and DTA.     

Low-temperature thermoelectric properties of Bi85Sb15−xNbx alloys prepared by high-press sintering

The nanocrystalline materials with the general formula Bi₈₅Sb_15−xNb_x (x=0, 0.5, 1, 2, 3) were prepared by mechanical alloying and subsequent high-pressure sintering. Their transport properties involving electrical conductivity, Seebeck coefficient and thermal conductivity have been investigated in the temperature range of 80-300 K. The absolute value of Seebeck coefficient of Bi₈₅Sb₁₃Nb₂ reaches a maximum of 161 μV/K at 105 K, which is 69% larger than that of Bi₈₅Sb₁₅ at the same temperature. The power factor and figure-of-merit are 4.45×10⁻³ WK⁻²m⁻¹ at 220 K and 1.79×10⁻³ K⁻¹ at 196 K, respectively. These results suggest that thermoelectric properties of Bi₈₅Sb₁₅ based material can be improved by Nb doping.     

Role of exciton-phonon interactions and disordering processes in the formation of the absorption edge in Cu<Subscript>6</Subscript>P(S<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Se<Subscript>x</Subscript>)<Subscript>5</Subscript>Br crystals

The absorption edge in Cu₆P(S_1?x Se_x)⁵Br crystals has been studied for strong absorption in the temperature range of 77–330 K. The parameters of the Urbach absorption edge and exciton-phonon interactions in Cu₆P(S_1-x Se_x)₅Br crystals are determined and their effect on the composition disorder is studied.     

Temperature dependence of the indirect band gap, steepness parameter and related optical constants of [Kx(NH4)1−x]2ZnCl4 mixed crystals

Optical transmittance measurements near the absorption edge of [K_x(NH₄)_1−x]₂ZnCl₄ mixed crystals, where x=0.00, 0.232, 0.522, 0.644, 0.859 and 1.00, are reported over 276–350 K range. Analysis reveals that the type of transition is the indirect allowed one. The absorption edge shifted towards lower energy with increasing temperature. It is shown that [K_x(NH₄)_1−x]₂ZnCl₄ mixed crystals with x0.644 reveal a phase transition at 319 K, this phase disappeared at high concentrations of K⁺ ions. The steepness parameter is given, its value is used to estimate the temperature dependence of the indirect energy gap. In the region of the absorption edge, the absorption coefficient obeys Urbach's rule. Urbach parameters are investigated as a function of temperature.     

Chemical pressure effect in CeFeAs1−xPxO0.95F0.05

We investigate the chemical pressure effect due to P doping in the CeFeAs_1−xP_xO_0.95F_0.05(0≤x≤0.4) system. The compound CeFeAsO_0.95F_0.05 without P doping is on the boundary between antiferromagnet (AFM) and superconductor. The AFM order of Ce³⁺ local moments causes a significant reentrance behavior in both resistivity and magnetic susceptibility. Upon P doping, T_c increases and reaches a maximum of 21.3 K at x=0.15, and then it is suppressed to lower temperatures. Meanwhile, the AFM order of Ce³⁺ ions remains nearly the same in the whole doping range (0≤x≤0.4). Our experimental results suggest a competition between superconductivity and Kondo effect in the Ce 1111 system.     

Surface morphology of DyxOy films grown on Si

The crystalline structure and surface morphology of Dy_xO_y dielectric films grown on Si substrates were studied by grazing incidence diffraction and absorption with use of synchrotron radiation and by atomic force microscopy. The crystalline structure and the roughness of Dy_xO_y films were found to be strongly dependent on the deposition rate. The dielectric-silicon interface depends on the type of gas used in the annealing process. Moreover, results from the near edge X-ray absorption studies, have revealed that none of the examined films has a stoichiometry close to the Dy₂O₃. The level of stoichiometry is determined by the technological conditions. Nevertheless, MOS structures with Dy_xO_y films (EOT ∼ 23 Å) have shown a rather good Dy_xO_y-Si interface properties, which can be further improve by thermal annealing, and introducing of several additives, therefore Dy_xO_y films can be considered as suitable candidates for gate dielectric in MOS devices.     

Magnetic and related properties of the solid solution CeCuxGa4−x

Physical properties of polycrystalline samples of CeCu_xGa_4−x (x = 0.2–1.4), crystallizing in the tetragonal BaAl₄-type structure (space group I 4/mmm), were studied by means of X-ray powder diffraction, magnetization, specific heat, electrical resistivity and magnetoresistivity measurements in wide temperature and magnetic fields ranges. The unit-cell volume of the system was found to decrease with increasing x (in total by about 4%) but the magnetic moments of Ce³⁺ ions remain localized in the whole x-range studied. The alloys exhibit ferromagnetic order at low temperatures, which manifests itself as distinct and relatively sharp anomalies in all the temperature characteristics measured. The ordering temperature decreases with increasing the Cu content from 5.5(1) K for x = 0.2 down to 1.35(5) K for x = 1.4, and the electrical transport properties of the system show some features characteristic of Kondo lattices.     

Properties of CuIn(SxSe1−x)2 polycrystalline thin films prepared by chemical spray pyrolysis

CuIn(S_xSe_1−x)₂ thin polycrystalline films were grown by the chemical spray pyrolysis method on the glass substrate at 280-400°C. The alloy composition in the film was studied with relation to that in the splay solution. Films were characterized by X-ray diffraction, optical absorption, Raman spectroscopy, resistivity and surface morphology. The CuInSe₂-rich alloy films grown at high substrate temperature had chalcopyrite structure, while, the CuInS₂-rich films grown at low substrate temperature exhibited sphalerite structure. Optical-gap energies were smaller than that of the bulk crystal by 0.1-0.2 eV for CuInS₂-rich films. Raman spectra exhibited both CuInSe₂-like and CuInS₂-like A₁ modes, and their relative changed systematically with alloy composition.     

Absorption spectra near the absorption edge of the system HgxZn1−xCr2Se4

Optical absorption spectra near the absorption edge of the system Hg_xZn_1?xCr₂Se₄ have been measured for various compositions in the temperature range between room and liquid helium temperatures. A correlation between the optical properties and magnetic structures becomes obvious from the measurements of the energy at the absorption edge and the change in the magnetic property with composition variation, and by measuring the optical absorption spectra under the applied magnetic field.