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.     

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.     

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.     

Compositional behaviour of Urbach absorption edge and exciton-phonon interaction parameters in Cu6PS5I1−xBrx superionic mixed crystals

Temperature behaviour of optical absorption edge in Cu₆PS₅I_1−xBr_x mixed crystals is studied in the interval 77-325 K. It is shown that the absorption edge has Urbach shape in the 215-325 K temperature interval. The influence of temperature and compositional disorder on the Urbach absorption edge parameters is presented. The mechanism of the Urbach bundle formation and the effect of I→Br anionic substitution on the exciton-phonon interaction parameters is elucidated.     

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.     

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.     

Electrical conductivities of the Ag6PS5X and the Cu6PSe5X (X=Br, I) argyrodites

The Ag₆PS₅Br and Ag₆PS₅I argyrodites crystallize in a face-centered-cubic lattice at room temperature. Both compounds exhibit purely Arrhenius behavior throughout the temperature range 150-400 K with similar activation energies of about 0.23 eV. Cu₆PSe₅Br and Cu₆PSe₅I also crystallize in a face-centered-cubic structure at room temperature. Cu₆PSe₅Br exhibits a distinctive anomaly in electrical conductivity near 286 K while Cu₆PSe₅I undergoes a first-order electrical phase transition near 265 K. Their activation energies above room temperature are 0.13 and 0.30 eV, respectively.     

Low-temperature absorption edge and photoluminescence in layered structured Tl2Ga2S3Se single crystals

The absorption edge of undoped Tl₂Ga₂S₃Se crystals have been studied through transmission and reflection measurements in the wavelength range 440–1100 nm and in the temperature range 10–300 K. The absorption edge was observed to shift toward lower energy values with increasing temperature. As a result, the rate of the indirect band gap variation with temperature γ=−2.6×10⁻⁴ eV/K and the absolute zero value of the band gap energy E_gi(0)=2.42 eV were obtained.     

The effect of sulfide substitution in the mixed conductor Cu7PSe6

Cu₇PSe₆ is a mixed conductor exhibiting structural phase transitions above and below room temperature that are accompanied by step-like changes in electrical conductivity. The substitution of S²⁻ for Se²⁻ in Cu₇PSe₆ significantly enhances electrical conductivity at room temperature compared to that observed for the pure compound. In the case of Cu₇P(Se_0.80S_0.20)₆, a nearly temperature-independent electrical conductivity exceeds 1 S/cm with no evidence of any phase transitions throughout the temperature interval 200-400 K. However, the ionic contribution accounts for just 2% of the total electrical conductivity in this solid solution at room temperature.     

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.     

Electrical properties of the Ag6PSe5X (X=Cl, Br, I) argyrodites

The total electrical conductivities at room temperature of Ag₆PSe₅Cl, Ag₆PSe₅Br, and Ag₆PSe₅I were found to be 2.0×10⁻⁴, 5.6×10⁻⁴, and 6.8×10⁻⁴ S/cm, respectively. In the chloride and iodide compounds, the electronic contribution comprises approximately 1% of the total conductivity, although it exceeds 10% of the total conductivity in the bromide compound. Ag₆PSe₅Cl and Ag₆PSe₅Br exhibit purely Arrhenius behavior throughout the temperature range 150-300 K. Ag₆PSe₅I exhibits a second-order anomaly in electrical conductivity at 324 K.     

The effect of temperature and pressure on the optical absorption edge in Cu6PS5X (X=Cl,Br,I) crystals

The absorption edge of monocrystalline Cu₆PS₅X (X=Cl,Br,I) superionic ferroelastics was studied in the 77–303 K temperature range and the mechanisms of exciton–phonon interactions resulting in exponential absorption edges and Urbach tails were analysed. Various types of disordering, affecting the optical absorption tails, were studied. The investigation of the influence of hydrostatic pressure (up to 400 MPa) on optical transitions of Cu₆PS₅X at 295 K revealed that the increase of pressure causes an increase of the optical pseudogap as well as the increase of the slope of the absorption edge indicating pronounced ordering in most disordered crystals. Data obtained from the pressure studies confirmed the predominant contribution of exciton–phonon interaction to the temperature shift of the Urbach absorption edge.     

Temperature induced band gap shrinkage in Cu2GeSe3: Role of electron-phonon interaction

The ternary semiconducting compound Cu₂GeSe₃ has been investigated for optical properties with photoacoustic spectroscopy. Optical absorption spectra of Cu₂GeSe₃ is obtained in the range of 0.76-0.81 eV photon-energy at temperatures between 80 and 300 K. The thermal variation of band gap energy has been examined from the optical absorption spectra at different temperatures. The temperature induced band gap shrinkage has been explained on the basis of electron-phonon interaction. Varshni's empirical relation in conjunction with Vina and Passler model is taken into consideration for data fitting. The Debye temperature was calculated approximately as 240 K. The acoustic phonons with a characteristic temperature as 160 K corresponding to effective mean frequency have been attributed to the thermal variation of the energy gap.     

The effect of Ag substitution in the mixed conductor Cu7PSe6

Cu₇PSe₆ is a mixed conductor that crystallizes in the simple cubic structure at room temperature. Structural transitions above and below room temperature are accompanied by step-like changes in electrical conductivity. The substitution of Ag⁺ for Cu⁺ in Cu₇PSe₆ stabilized the simple cubic structure over a wider range of temperatures than is observed for the pure compound. A disproportionate decrease in electrical conductivity accompanies modest levels of silver substitution. The prominent step in electrical conductivity associated with the low-temperature crystallographic phase transition disappears in (Ag_xCu_1−x)₇PSe₆ solid solutions for a composition parameter x=0.20, replaced by two distinct changes in the slope of conductivity below room temperature.     

Optical absorption and exciton-phonon interaction in solid solutions Cu<Subscript>6</Subscript>PS<Subscript>5</Subscript>I<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Cl<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

We have studied the optical absorption edge of solid solutions Cu₆PS₅I_{1 − x} Cl _x at high absorption levels in the temperature range of 77–320 K. In a superionic state, we have revealed the Urbach behavior of the absorption edge, determined its parameters, and studied their temperature and concentration variations. We consider exciton-phonon interaction as a mechanism by which the Urbach bundle is formed and show that this bundle can be described in terms of the Dow-Redfield model.     

Influence of S→Se substitution on chemical and physical properties of Cu7Ge(S1−xSex)5I superionic solid solutions

Phase diagram of Cu₇GeS₅I-Cu₇GeSe₅I superionic system was investigated by the differential thermal analysis (DTA). Chemical interaction in Cu₇GeS₅I-Cu₇GeSe₅I system was studied by X-ray phase analysis (XPA), microstructural analysis, and density determination. Compositional behaviour of diffuse reflection spectra and energy gap due to S→Se anion substitution in Cu₇Ge(S_1−xSe_x)₅I solid solutions are discussed.     

ESR spectra of Eu centers in defect Ga2S3 single crystals

In this paper, the author presents the results of measurements of the low-temperature and angular dependences of the ESR spectra of Eu²⁺ centers in defect Ga₂S₃ single crystals in the temperature range 8–29 K and for 0–180° orientations of the static magnetic field. The electron structure of impurity ¹⁵¹Eu atoms in Ga₂S₃:Eu single crystals has been studied by using the ESR method at different doping proportions of Eu atoms. Ga₂S₃ single crystals were grown from the melt using the Bridgman method. The Eu concentration was determined by atomic absorption analysis and X–ray fluorescence analysis (XRFA). By investigation on the ESR spectra, the author has first determined the values of charge states for Eu, which have turned out to be a Eu²⁺(4f⁷) ion with spin S=7/2, g=4.18±0.02 and concentration of the states of Eu N=6.3×10¹⁴ cm⁻³.     

Nature of optical properties of GdFe3(BO3)4 and GdFe2.1Ga0.9(BO3)4 crystals and other 3d5 antiferromagnets

Influence of the partial substitution of paramagnetic Fe³⁺ ions by diamagnetic Ga³⁺ ions in the trigonal crystal GdFe₃ (BO₃)₄ on its optical and magnetic properties is studied and discussed in connection with problems common for all antiferromagnets containing 3d ⁵ ions. Polarized optical absorption spectra and linear birefringence of GdFe₃ (BO₃)₄ and GdFe_2.1Ga_0.9 (BO₃)₄ single crystals have been measured in the temperature range 85–293 K. Specific heat temperature dependence (2–300 K) and structure of GdFe_2.1Ga_0.9 (BO₃)₄ crystal have been also studied. As a result of substitution of 30% Fe to Ga the Neel temperature diminishes from 38 till 16 K, the strong absorption band edge shifts on 860 cm^-1 (0.11 eV) to higher energy and the d-d transitions intensity decreases substantially larger than the Fe concentration does. Strong absorption band edge is shown to be due to Mott-Hubbard transitions. Correlation between position of the strong absorption band edge and the Neel temperature of antiferromagnets has been revealed. Properties of the doubly forbidden d-d transitions in the studied crystals and in other antiferromagnets are explained within the framework of the model of the exchange-vibronic pair absorption, which is theoretically analyzed in detail. The model permitted us to determine the connection between parameters of d-d absorption bands (intensity, width and their temperature dependences), on the one hand, and the exchange, spin-orbit and electron-lattice interactions, on the other hand.     

Low temperature electrical conductivity and magnetoconductivity of Fe39Ni39Mo4Si6B12 and Co58Ni10Fe5Si11B16 metallic glass alloys

A detailed study on the weak localization phenomenon vis-a-vis electron-electron interaction effects in magnetic metallic glasses has been carried out. We measured the electrical conductivity and magnetoconductivity within the temperature range 1.8≤T≤300K. A maximum on the conductivity versus temperature curve exists atT=T _m. The conductivity was observed to follow aT ^1/2 law forT<T _m andT ² law forT>T _m. Magnetoconductivity data of these alloys indicate the prominence of electron-electron interaction at low temperatures. The authors have determined the inelastic scattering field and spin-orbit scattering field from the magnetoconductivity data. The inelastic scattering field obeys aT ^p law (p=2) at low temperatures.     

Structure and low-temperature properties of Ba8Ni6Ge40

Structural, magnetic, heat capacity, electrical and thermal transport properties are reported on polycrystalline Ba₈Ni₆Ge₄₀. Ba₈Ni₆Ge₄₀ crystallizes in a cubic type I clathrate structure with unit cell a=10.5179 (4) Å. It is diamagnetic with susceptibility χ_dia=−1.71×10^-6 emu/g Oe. An Einstein temperature 75 K and a Debye temperature 307 K are estimated from heat capacity data. It exhibits n-type conducting behavior below 300 K. It shows high Seebeck coefficients (−111×10^-6 V/K), low thermal conductivity (2.25 W/K m), and low electrical resistivity (8.8 mΩ cm) at 300 K.