About the existence of a Lifshitz point on the phase diagram of Sn2P2(Se x S1– x )6 solid solutions: acoustic and optical studies

On the basis of combined studies of the acoustic and optical properties of Sn₂P₂(Se _x S_{1– x} )₆ solid solutions with x?=?0 and 0.28 it is shown that two special points exist on the x,T-phase diagram of these ferroelectric crystals, a tricritical point and a triple one. With increasing Se concentration, the phase transition changes its character at x?≈?0.28 from second-order to first-order. The phase transition becomes split at x?≈?0.4, with the appearance of an intermediate incommensurate phase.     

Special points on the phase diagrams of langbeinites. The case of (x,T)-phase diagram of mixed K2xRb2(1−x)Cd2(SO4)3 crystals

We have studied special points that appear on the (x, T)-phase diagram of mixed K_2xRb_2(1?x)Cd₂(SO₄)₃ crystals. This phase diagram has been constructed issuing from the changes in domain structure occurring in the course of phase transitions. We have found that two triple points on the (x, T)-phase diagram of the above solid solutions are very close to each other in the phase space and can change their places or transform into a quadruple point. These special points are associated with disappearance of ferroelectric phases with the symmetries P1 and P2₁ taking place when Rb₂⁺ are substituted with K₂⁺ ions.     

Dynamic shift of the phase-transition temperature in (Sn1−x In(2/3)x)2P2S6 crystals with incommensurate phase

The dielectric properties of ferroelectric (Sn_1?x In_(2/3)x )₂P₂S₆ crystals were studied in the region of incommensurate phase transitions occurring upon fast cooling and heating (0.2–11 K/min). The dynamic phase-transition shift observed in these materials was examined.     

Phase transitions in the ferroelectrics (Sn1−x In(2/3)x )2P2S6 at high pressures

New ferroelectric solid solutions (Sn_1−x In_(2/3)x )₂P₂S₆ were investigated at high hydrostatic pressures. The range in which the incommensurate structure exists was determined. A dynamic shift of the incommensurate-ferroelectric phase transition temperature with increasing rate of change of temperature and the appearance of “reverse hysteresis” were observed. The characteristic features in the appearance of the latter effect in these crystals are investigated. Fiz. Tverd. Telsa (St. Petersburg) 41, 1276–1278 (July 1999)     

Influence of Covalence on the Metal-Insulator Temperature in the CuIr 2 (S 1− x Se x ) 4 Spinels

Influence of the covalence on the metal-insulator (M-I) temperature in the CuIr 2 (S 1 m x Se x ) 4 spinel series is considered. For this purpose a vacancy model and the effective number of valence electrons per molecule are used. Calculations of the vacancy model parameters, i.e., the ion packing coefficients, the filling coefficient of the unit cell, the difference of the Pauling electronegativities and the vacancy parameter suggest that the covalence increases with increasing selenium concentration x , leading to a decrease of the metal-insulator temperature. It was observed that the metal-insulator temperature is related to the effective number of valence electrons per molecule, suggesting that with increasing covalence, less and less valence electrons take part in the metal-insulator transition. These effects are explained within the framework of the mixed valence of the iridium ions including structural defects.     

Vortex structure in BaFe2(As1 − x P x )2 single crystals

Single crystals of iron-containing Ba(FeAs)₂ superconductors doped with phosphorus have been studied. The vortex structure has been studied by means of the decoration method. Large domains of the triangular vortex structures have been observed in the phosphorus-doped single crystals of iron-containing superconductors. The effect of doping on pinning in iron-containing superconductors has been discussed.     

Birefringence of CuGa(S1−x Sex)2 single crystals

The magnitude and dispersion of birefringence of single crystals of CuGa(S_1?x Se_x)₂ solid solutions is studied in the spectral region of 0.5–2.5 μ at T=300 K. The effect of the substitution of selenium for sulfur on special features of birefringence dispersion is analyzed within the framework of the single-oscillator model.     

A magnetic study of HoMn6Sn6−xGax single crystals (0.14⩽x⩽1.89)

Single crystals of hexagonal HfFe₆Ge₆-type HoMn₆Sn_6−xGa_x compounds (0.14⩽x⩽1.89) have been obtained by a flux method and studied by magnetisation measurements. All the compounds order ferrimagnetically (308⩽T_c⩽386 K) with moments lying in the (0 0 1) plane and undergo a moment reorientation transition at lower temperatures (156⩽T_SR⩽195 K). At 5 K, the moments are aligned along an intermediate direction (44⩽φ_c⩽50°). These results are discussed and compared with the neutron diffraction results related to the isotypic TmMn₆Sn_6−xGa_x and TbMn₆Sn_6−xGa_x series where a change of the easy direction is observed with increasing gallium contents.     

Elastic properties of (Pb y Sn1−y )2P2S6 solid solutions

Elastic properties of (Pb _y Sn_1?y )₂P₂S₆ solid solutions were studied using Brillouin scattering technique. Different scattering geometries were used for sound velocities determination that make it possible to find all components of the stiffness tensor. The concentration dependencies of volume compressibility, the Grüneisen parameter and Debye temperature were investigated. The results obtained were used to analyze chemical bonding with substitution of tin by lead at room temperature in the crystals under consideration.     

Photovoltaic structures using AgSb(S x Se1−x )2 thin films as absorber

Photovoltaic structures were prepared using AgSb(S _x Se_1?x )₂ as absorber and CdS as window layer at various conditions via a hybrid technique of chemical bath deposition and thermal evaporation followed by heat treatments. Silver antimony sulfo selenide thin films [AgSb(S _x Se_1?x )₂] were prepared by heating multilayers of sequentially deposited Sb₂S₃/Ag dipped in Na₂SeSO₃ solution, glass/Sb₂S₃/Ag/Se. For this, Sb₂S₃ thin films were deposited from a chemical bath containing SbCl₃ and Na₂S₂O₃. Then, Ag thin films were thermally evaporated on glass/Sb₂S₃, followed by selenization by dipping in an acidic solution of Na₂SeSO₃. The duration of dipping was varied as 3, 4 and 5 h. Two different heat treatments, one at 350 °C for 20 min in vacuum followed by a post-heat treatment at 325 °C for 2 h in Ar, and the other at 350 °C for 1 h in Ar, were applied to the multilayers of different configurations. X-ray diffraction results showed the formation of AgSb(S _x Se_1?x )₂ thin films as the primary phase and AgSb(S,Se)₂ and Sb₂S₃ as secondary phases. Morphology and elemental detection were done by scanning electron microscopy and energy dispersive X-ray analysis. X-ray photoelectron spectroscopic studies showed the depthwise composition of the films. Optical properties were determined by UV–vis–IR transmittance and reflection spectral analysis. AgSb(S _x Se_1?x )₂ formed at different conditions was incorporated in PV structures glass/FTO/CdS/AgSb(S _x Se_1?x )₂/C/Ag. Chemically deposited post-annealed CdS thin films of various thicknesses were used as window layer. J–V characteristics of the cells were measured under dark and AM1.5 illumination. Analysis of the J–V characteristics resulted in the best solar cell parameters of V _oc = 520 mV, J _sc = 9.70 mA cm^?2, FF = 0.50 and η = 2.7 %.     

Influence of the composition of TlGa1 − x Er x Se2 crystals on their dielectric characteristics and parameters of localized states

Frequency dependences of the real (?′) and imaginary (?″) parts of the complex permittivity, the dielectric loss tangent (tanδ), and the ac conductivity (σ_ac) in frequency range f = 5 × 10⁴?3.5 × 10⁷ Hz have been investigated for TlGa_{1 ? x} Er _x Se₂ crystals of various compositions. It has been established that the relaxation dispersion of ?′ and ?″ takes place for the studied crystals. The influence of the erbium content in the crystals on their dielectric coefficients has been studied. The ac conductivity of the TlGa_{1 ? x} Er _x Se₂ single crystals in the high-frequency range obeys the law σ_ac ～ f ^0.8, which is characteristic of the hopping mechanism of charge transfer over the states localized in the vicinity of the Fermi level. Parameters of the states localized in the band gap of TlGa_{1 ? x} Er _x Se₂ and the influence of the composition of the crystals on these parameters have been evaluated.     

Tunneling measurements on (La1−x Ce x )Al2 single crystals with wax barriers

In the investigation of the Kondo superconductor (La_1–x Ce _x )Al₂ a new technique is developed to fabricate tunnel junctions of the type: bulk sample — wax barrier — evaporated counterelectrode. Pb, Al, Ag, Au and Mg are used as counterelectrodes. Measurements employing Pb and Al yield the order parameter of nominally pure LaAl₂: ₀=(0.47±0.03) meV=1.63kT _c. The large influence of localized states within the gap is confirmed.     

Thermal diffusivity and 3D-XY critical behavior of ferroelectric semiconductors (PbxSn1−x)2P2Se6

An ac photopyroelectric calorimeter has been used to study the thermal diffusivity of the ferroelectric semiconductors family (Pb_xSn_1−x)₂P₂Se₆ (x=0–1) from 30 K to room temperature. Phase transitions have been found for x=0, 0.05, 0.2, 0.47 but not for x=1 in the full temperature range. A continuous phase transition has been found for x=0, 0.05, 0.2 and 0.47 which corresponds to the paraelectric commensurate to incommensurate phase. It has been possible to study the critical behavior of this transition for x=0, 0.05 and the critical parameters obtained have been α=−0.019, A⁺/A⁻=1.00 and α=−0.026, A⁺/A⁻=1.03, respectively, having fitted at the same time both the low and high temperature branches of the transition as rigorous critical theory indicates; these results agree with the theoretical prediction from renormalization group theory that this kind of transition complies with the 3D-XY universality class (α_theor=−0.014, A⁺/A⁻=1.06), which has been experimentally confirmed only in a few materials. A first order incommensurate to ferroelectric phase transition has been characterized in x=0, 0.05 at lower temperature.     

Phase diagram and domain structure of the Rb2 x Tl2(1− x )Cd2(SO4)3 solid solutions

From measurements of temperature dependences of the birefringence and from observations of the domain structure the x, T–phase diagram for the Rb_{2 x} Tl_{2(1? x )}Cd₂(SO₄)₃ solid solutions have been obtained. Ferroelastic domain structure and movement of phase boundaries have been studied in the course of phase transitions in Rb_{2 x} Tl_{2(1? x )}Cd₂(SO₄)₃ crystals. Possible reasons for the appearance of mechanically non-compatible (‘forbidden’) ferroelastic domain walls are given.     

Neutron diffraction study of the oxide conducting δ1-phase of (Bi2O3)1−x(Y2O3)x (x=0.25)

The atomic parameters of the average cell of δ¹-Bi(Y)O_1.5 were determined by powder neutron diffraction. The evidence indicates that the disorder in the structure has many features in common with the structure of the oxygen deficient zirconia. Most oxygens (78%) are in sites displaced 0.335 Å along 〈100〉 directions from the normal fluorite positions, while a smaller proportion (22%) are displaced 0.80 Å along 〈111〉 directions and no oxygen remains in normal positions. In addition to the anion displacements a smaller displacement (0.25 Å) along the 〈111〉 direction was found for the cations. Comparison with the structure of β-Bi₂O₃ suggests that the displacements may be precursors to a δ→β phase transition.     

Magnetotransmission of unpolarized infrared radiation in Hg1 − x Cd x Cr2Se4 (0 ≤ x ≤ 1) single crystals studied using the voigt geometry

The features characterizing the behavior of magnetotransmission in Hg_{1 ? x} Cd _x Cr₂Se₄ single crystals are studied using natural light in the infrared spectral range. The relation between the changes in the magneto-optical properties and in the electron band structure is found. It is shown that the most significant changes in the magnetotransmission spectrum and the band structure occur within the 0.1 < x < 0.25 range.     

Structural features of the system of cubic crystals Zn0.999Fe0.001S1 ? x Se x (x = 0, 0.2)

The structural state of cubic single crystals Zn_0.999Fe_0.001S_{1 ? x} Se _x (x = 0, 0.2) obtained by the chemical transport method has been investigated using thermal neutron diffraction for the first time. It has been found that the diffraction patterns of these crystals contain the previously unknown effects of diffuse scattering caused by local statistic atomic displacements in the metastable fcc lattice.     

Depth profile of the lattice constant of the Cu-poor surface layer in (Cu2Se)1−x(In2Se3)x evidenced by grazing incidence X-ray diffraction

The surface of CuInSe₂ or related compounds is an essential part of heterojunctions for photovoltaic applications. It is generally accepted that the reconstruction of the surface of slightly Cu-deficient film results in a Cu-depleted defect layer. Since this surface layer generally exhibits a CuIn₃Se₅ stoichiometry the existence of a defect chalcopyrite phase CuIn₃Se₅ has also been proposed. Although efforts have been made to identify this phase structurally by means of grazing incidence X-ray-diffraction (GIXRD), it has not been detected so far. However, the existence of a Cu-depleted surface layer fits well in the existing theory, which models the functioning of photovoltaic devices. In this contribution we present for the first time evidence for a Cu-depleted surface layer measured by X-ray diffraction. A careful analysis of GIXRD-data at incident angles from 0.3 to 10° by comparing the measured shape and width with simulated spectra confirms structural changes in the surface layer. The thickness of this layer varies from 5 to 60 nm with the integral Cu-content of the film. Hence GIXRD provides a unique means for non-destructive depth profiling.     

STM studies on the reconstruction of the Ni2P (101̅0) surface

The surface structure of Ni₂P (101?0), a model for highly active hydrodesulfurization catalysts, was studied using scanning tunneling microscopy (STM) and low energy electron diffraction (LEED) in order to understand the reconstruction of the surface layers. Annealing at 573 K revealed a (1 × 1) LEED pattern which changed to a c(2 × 4) arrangement by further heating to 723 K. Atomic scale STM images were obtained for both the (1 × 1) and c(2 × 4) structures. Bright spots observed in the STM images were interpreted to be due to surface phosphorus atoms and this was supported by a density functional theory (DFT) simulation. Several possible models for the c(2 × 4) reconstructed structures were proposed including a P-dimer defect model, a missing-row model and a missing-row + added-row model. The last model gave the best explanation for the c(2 × 4)structure. The mechanism for the c(2 × 4) reconstruction on the Ni₂P (101?0) surface is discussed.