Polarized optical absorption of MnGa<Subscript>2</Subscript>S<Subscript>4</Subscript> single crystals

Optical absorption of MnGa₂S₄ single crystals is studied at two light polarizations (E ||C and E⊥ C). The polarization splitting of the absorption edge points to a splitting of the valence band of MnGa₂S₄. A contribution to the crystal-field splitting is made by two factors, namely, by a difference in the pseudopotential of cationic sublattice atoms and by tetragonal compression of the lattice along the C axis. A scheme of optical transitions in MnGa₂S₄ in the Brillouin zone center is suggested, according to which the optical transitions Г₃ + Г₄ → Г₁ occur in the polarization E ⊥ C, and the Г₂ → Г₁ transitions occur in the polarization E || C.     

Magnetic structure of the quasi-one-dimensional frustrated antiferromagnet LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript> with Spin <Emphasis Type="Italic">S</Emphasis> = 1/2

The magnetic properties of LiCu₂O₂ single-crystal samples without twinning are investigated using electron spin resonance and nuclear magnetic resonance spectroscopy. The experimental results obtained are described in terms of the model of a planar spiral antiferromagnet for the orientation of the magnetic field H ‖ b or H ‖ c and the model of a collinear spin-modulated antiferromagnet for the orientation of the static magnetic field H ‖ a.     

Effect of a Rare-Earth Ion on the Structural Instability in RFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> Crystals

The dynamics of the crystal lattice of RFe₃(BO₃)₄ (R = Pr, Nd, Sm, Gd, Tb, Dy, and Ho) compounds in the high-symmetry R32 phase has been calculated. Significant changes in spectra of compounds with various rare-earth ions have been obtained only near the edge Λ point of the Brillouin zone (qΛ = 1/3(?2b₁ + b₂ + b₃, where b₁, b₂, and b₃ are the reciprocal lattice vectors) for acoustic oscillation branches. A decrease in the frequency of an acoustic mode at the point Λ has been revealed in all studied compounds. This frequency depends on the type of rare-earth ion and decreases from a compound with Pr to a compound with Ho down to imaginary values. Such a behavior of the frequency of the unstable acoustic mode is in good agreement with experimental data on the dependence of the temperature of the R32 → P3₁21 structural phase transition on the type of rare-earth ion in ferroborates.     

High-temperature deformation and specific features of dislocation structure of Ti<Subscript>3</Subscript>Al

The transmission electron microscopy was used to examine the dislocation structure of intermetallic Ti₃Al after deformation at temperatures T = 1073–1273 K. It is established that its microstructure contains mobile 2c + a and superdislocations. Possible models describing the destruction of barriers associated with 2c + a superdislocations in pyramidal planes are discussed using the results of computer simulation of the superdislocation core structure in Ti₃Al.     

Anisotropy of magnetic properties of Sm<Subscript>0.55</Subscript>Sr<Subscript>0.45</Subscript>MnO<Subscript>3</Subscript> single crystals

Anisotropy of the magnetic properties of Sm_0.55Sr_0.45MnO₃ single crystals has been studied. A significant increase in the antiferromagnetic component of magnetization in the case of orientation of an external magnetic field H close to the c axis has been found. Magnetization for a field lying in the ab plane seems typical of a ferromagnet. Anisotropy of susceptibility reaches 2.2 in weak fields and nearly vanishes at H > 1 T.     

Ordering of the lowest tungsten carbide W<Subscript>2</Subscript>C

Atomic-vacancy ordering of the lowest tungsten carbide W₂C with the basis hexagonal structure of the L’3 type is analyzed by neutron and x-ray diffraction studies. It is found that the trigonal phase ?-W₂C (space group \(P\bar 3\) 1m) is the only ordered phase in the temperature range from ～2700 to 1370 K. The disorder-order phase transition channel associated with the formation of the trigonal ?-W₂C phase is found to include three superstructure vectors k ₁₅ ⁽¹⁾ , k ₁₅ ⁽²⁾ , and k ₁₇ ⁽¹⁾ of two stars {k ₁₅} and {k ₁₇}. The distribution function of the carbon atoms in the trigonal ?-W₂C superstructure is calculated.     

V<Subscript>52</Subscript>O<Subscript>64</Subscript> tetragonal superstructure of cubic vanadium monoxide with vacancies in the metal sublattice

The atom-vacancy ordering of cubic vanadium monoxide VO_1.29, which has basis cubic structure B1 and structural vacancies in the metal sublattice, has been studied using the x-ray diffraction method. It has been shown that the formation of the tetragonal (space group I4₁/amd) ordered phase V₅₂O₆₄ of cubic vanadium monoxide VO_y proceeds as a first-order phase transition through the disorder-order channel including 22 nonequivalent superstructure vectors of four stars {k ₁₀}, {k ₄}, {k ₃}, and {k ₂}. The distribution function of the vanadium atoms in the V₅₂O₆₄ tetragonal superstructure has been calculated.     

Nucleation of microcracks during dislocation interactions in a Ti<Subscript>3</Subscript>Al single crystal

Reactions between superdislocations involved in deformation in the basal, prismatic, and type-I and II pyramidal planes in single-crystal Ti₃Al are considered. The types of dislocation interactions are established that result in the formation dislocation barriers (microcrack nuclei). The force and energy conditions for microcracks to arise are found. The interaction between a and 2c + a superdislocations results in microcracks with the plane of opening lying in basal and pyramidal planes; the interaction of 2c + a superdislocations in different pyramidal planes results in the formation of microcracks in prismatic and pyramidal planes; and the interaction of a superdislocations in basal and/or pyramidal planes does not cause the formation of dislocation barriers. The types of microcracks are classified in terms of the orientation of deformation axes of single crystals, and the regions of the stereographic triangle are determined characterized by a preferential type of crack opening.     

Formation of the incommensurate ordered phase in TaC<Subscript>y</Subscript> carbide

Structural neutron diffraction studies indicate that only one ordered phase arises after the disorder-order transition in nonstoichiometric cubic tantalum carbide TaC_y. This phase arises in the composition range y = 0.79–0.89 due to long-term annealing with a decrease in temperature from 1600 to 300 K. It is incommensurate in the [1–11]_B1 direction, but it is close to commensurate M₆C₅ structures (C2/m and P3₁ space groups) in mutual arrangement of atoms and vacancies in nonmetallic (1–11)_B1 planes. The disorder-order transition channel that is associated with the formation of the incommensurate superstructure in TaC_y carbide includes two arms k ₅ ⁽⁶⁾ ≈ 0.473b₂ and k ₅ ⁽⁵⁾ = ?k ₅ ⁽⁶⁾ of the {k₅} star and arms of the {k₄} and {k₃} stars. The translation period of the incommensurate phase in the [1–11]_B1 direction is 8.9–9.1 nm, which is larger than that in the commensurate phase M₆C₅ by a factor of about 18.     

Interrelation of anisotropy of magnetic properties and magnetodielectric effect in a Cu<Subscript>3</Subscript>B<Subscript>2</Subscript>O<Subscript>6</Subscript> single crystal

The effect of an external magnetic field on permittivity has been studied in a Cu₃B₂O₆ single crystal with a layered structure in the direction perpendicular to layers (bc-planes). It has been found that the appreciable magnetodielectric effect in the temperature range below the Néel temperature (≈10 K) takes place only at one magnetic field orientation H and one crystallographic direction, i.e., H || b. Such “selectivity” of the magnetodielectric effect correlates with the anisotropic behavior of magnetic properties of the crystal.     

Optical absorption and photoconductivity of MnGaInS<Subscript>4</Subscript> single crystals in polarized light

The results of studying optical-absorption and spectral curves of photoconductivity in MnGaInS₄ single crystals are presented for two light polarizations (E || C and E ⊥ C). The intrinsic absorption edge and the band-gap width of MnGaInS4 single crystals in polarized light are determined. The anisotropy of optical absorption and photoconductivity spectrum of MnGaInS₄ single crystals is observed. It is suggested that the polarization splitting of the absorption edge is related to the splitting of the MnGaInS₄ valence band.     

Influence of the ground state of the Pr<Superscript>3+</Superscript> ion on magnetic and magnetoelectric properties of the PrFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> multiferroic

The magnetic, magnetoelectric, and magnetoelastic properties of a PrFe₃(BO₃)₄ single crystal and the phase transitions induced in this crystal by the magnetic field are studied both experimentally and theoretically. Unlike the previously investigated ferroborates, this material is characterized by a singlet ground state of the rare-earth ion. It is found that, below T _N = 32 K, the magnetic structure of the crystal in the absence of the magnetic field is uniaxial (l ∥ c), while, in a strong magnetic field H ∥ c (H _cr ～ 43 kOe at T = 4.2 K), a Fe³⁺ spin reorientation to the basal plane takes place. The reorientation is accompanied by anomalies in magnetization, magnetostriction, and electric polarization. The threshold field values determined in the temperature interval 2–32 K are used to plot an H-T phase diagram. The contribution of the Pr³⁺ ion ground state to the parameters under study is revealed, and the influence of the praseodymium ion on the magnetic and magnetoelectric properties of praseodymium ferroborate is analyzed.     

Galvanomagnetic properties of atomically disordered Sr<Subscript>2</Subscript>RuO<Subscript>4</Subscript> single crystals

The effect of neutron-bombardment-induced atomic disorder on the galvanomagnetic properties of Sr₂RuO₄ single crystals has been experimentally studied in a broad range of temperatures (1.7–380 K) and magnetic fields (up to 13.6 T). The disorder leads to the appearance of negative temperature coefficients for both the in-plane electric resistivity (ρ_a) and that along the c axis (ρ_c), as well as the negative magnetoresistance Δρ, which is strongly anisotropic to the magnetic field orientation (H ∥ a and H ∥ c), with the easy magnetization direction along the c axis and a weak dependence on the probing current direction in the low-temperature region. The experimental ρ_a(T) and ρ_c(T) curves obtained for the initial and radiation-disordered samples can be described within the framework of a theoretical model with two conductivity channels. The first channel corresponds to the charge carriers with increased effective masses (～10m _e , where m _e is the electron mass) and predominantly electron-electron scattering, which leads to the quadratic temperature dependences of ρ_a and ρ_c. The second channel corresponds to the charge carriers with lower effective masses exhibiting magnetic scattering at low temperatures, which leads to the temperature dependence of the ρ_{a, c}(T) ∝ 1/T type.     

First- and second-order Raman scattering from MoTe<Subscript>2</Subscript> single crystal

We report on Raman experiments performed on a MoTe₂ single crystal. The system belongs to the wide family of transition metal dichalcogenides which includes several of the most interesting two-dimensional materials for both basic and applied physics. Measurements were performed in the standard basal plane configuration, by placing the ab plane of the crystal perpendicular to the wave vector k _i of the incident beam to explore the in-plane vibrational modes, and in the edge plane configuration with k _i perpendicular to the crystal c axis, thus mainly exciting out-of-plane modes. For both configurations we performed a polarization-dependent study of the first-order Raman components and detailed computation of the corresponding selection rules. We were thus able to provide a complete assignment of the observed first-order Raman peaks, in agreement with previous literature results. A thorough analysis of the second-order Raman bands, as observed in both basal and edge plane configurations, provides new information and allows a precise assignment of these spectral structures. In particular, we have observed and assigned Raman active modes of the M point of the Brillouin zone previously predicted by ab initio calculations but never previously measured.     

NMR studies of single crystals of the topological insulator Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> at low temperatures

A powder sample and single-crystal plates of the topological insulator Bi₂Te₃ have been investigated using the ¹²⁵Te NMR method at room temperature and at low temperatures in the range from 12.5 to 16.5 K. The NMR spectra of the single-crystal plates have been studied in the orientation where the crystallographic axis c is directed parallel or perpendicular to the magnetic field. The spectra have been obtained by means of recording spin-echo signals and plotting their envelopes. It has been shown that the NMR spectra for the bismuth telluride powder and plates with the orientation c ⊥ B consist of two lines, which are presumably attributed to tellurium nuclei in two crystallographic positions in the bulk of the sample. The position and shape of the lines are determined by the chemical shift and the Knight shift. For the orientation of the plates c || B, the spectrum contains an additional component in the high-frequency region, which cannot appear due to the angular dependence of the line shifts caused by tellurium nuclei in the bulk of the topological insulator. At a low temperature, the additional line dominates in the spectrum.     

Enhanced photocatalytic activity of ternary CuInS<Subscript>2</Subscript> nanocrystals synthesized from the combination of a binary Cu(I)S precursor and InCl<Subscript>3</Subscript>

Ternary copper indium sulfide (CIS) nanocrystals (NCs) have been synthesized by mixing of binary precursor [Cu^I(bdpa)₂][Cu^ICl₂] (1) and/or [Cu^I(mdpa)₂][Cu^ICl₂] (2) (where, mdpa and bdpa represent methyl and benzyl ester of 3,5-dimethyl pyrazole-1-dithioic acid, respectively) with InCl₃ in a low-temperature solvothermal process. The +1 oxidation state of copper and the atomic ratio Cu to S (1:2) is atomically maintained in the pyrazole-based Cu(I)–S precursor to synthesize phase pure CuInS₂. Coordinating solvents like ethylene diamine (EN) and ethylene glycol (EG) have been used in the synthesis without any surfactants. No use of external surfactants in the synthesis of CIS nanoparticles reveals that precursor acts as stabilizing agent. The synthesized nanocrystals were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and energy dispersive X-ray spectroscopy (EDX) studies. The optical property of the nanocrystals shows a pronounced quantum confinement effect in the particles with band gap energy ca. 1.5 eV. The formation mechanism of ternary CIS has been proposed. The pore size distributions of the particles show the average pore diameters 13.1 nm from 1 and 5.3 nm from 2. The calculated values of the specific surface area are 8.123 and 9.577 m²/g for 1 and 2, respectively. The excellent photocatalytic degradation of rose bengal (RB) and rhodamine B (RhB) was demonstrated by the porous CIS nanocrystals.

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Graphical abstract Enhanced photocatalytic activity of ternary CuInS₂ nanocrystals synthesized from the combination of a binary Cu(I)S precursor and InCl₃. Gopinath Mondal, Ananyakumari Santra, Sumanta Jana, Nimai Chand Pramanik, Anup Mondal and Pulakesh Bera

     

Edge absorption spectra of crystalline and glassy PbGeS<Subscript>3</Subscript>

Edge absorption spectra of crystalline and glassy lead thiogermanate (PbGeS₃) have been measured in the temperature range from 77 to 470 K. It is shown that the dependence of the absorption coefficient on the photon energy for the glassy and crystalline states in the polarization E ∥ c is described by the Urbach rule. For the crystal in the polarization E ∥ b, at T < 300 K, an almost parallel shift of the intrinsic absorption edge to lower energies occurs with an increase in temperature, whereas at T ≥ 300 K, the Urbach absorption edge is observed. The parameter σ₀, related to the electron-phonon coupling constant, and the energy ?ω_ph of the effective phonons involved in the formation of the absorption edge of crystalline PbGeS₃ are determined from the temperature dependence of the parameter of the absorption edge slope. The contributions of the dynamic and static disorders to the diffusion of the absorption edge of crystalline PbGeS₃, as well as the topological disorder of glassy PbGeS₃, have been estimated.     

High-frequency properties of KNiPO<Subscript>4</Subscript> in alternating magnetic and electric fields

The dependences of the antiferromagnetic resonance frequencies on the constant magnetic field H and constant electric field E are calculated for a KNiPO₄ crystal with spontaneous electric polarization and antiferromagnetic order. It is demonstrated that the KNiPO₄ crystal is characterized by an exchange-enhanced effect of the electric field E on the antiferromagnetic resonance frequencies. This effect is not revealed in the magnetoelectric materials studied earlier. It is established that oscillations of both magnetization and electric polarization exhibit resonance response at antiferromagnetic resonance frequencies. The expressions for these responses in alternating magnetic and electric fields are presented.     

Thermal and electrochemical properties of poly(butylene sulfite)-based polymer electrolyte

Poly(butylene sulfite) (poly-1) was synthesized by cationic ring-opening polymerization of butylene sulfite (1), which was prepared by the reaction of 1,4-butanediol and thionyl chloride, with trifluoromethanesulfonic acid (TfOH) in bulk. The polymer electrolytes composed of poly-1 with lithium salts such as bis(trifluoromethanesulfonyl)imide (LiN(SO₂CF₃)₂, LiTFSI) and bis(fluorosulfonyl)imide (LiN(SO₂F)₂, LiFSI) were prepared, and their ionic conductivities, thermal, and electrochemical properties were investigated. Ionic conductivities of the polymer electrolytes for the poly-1/LiTFSI system increased with lithium salt concentrations, reached maximum values at the [LiTFSI]/[repeating unit] ratio of 1/10, and then decreased in further more salt concentrations. The highest ionic conductivity values at the [LiTFSI]/[repeating unit] ratio of 1/10 were 2.36?×?10^?4 S/cm at 80 °C and 1.01?×?10^?5 S/cm at 20 °C. On the other hand, ionic conductivities of the polymer electrolytes for the poly-1/LiFSI system increased with an increase in lithium salt concentrations, and ionic conductivity values at the [LiFSI]/[repeating unit] ratio of 1/1 were 1.25?×?10^?3 S/cm at 80 °C and 5.93?×?10^?5 S/cm at 20 °C. Glass transition temperature (T _g) increased with lithium salt concentrations for the poly-1/LiTFSI system, but T _g for the poly-1/LiFSI system was almost constant regardless of lithium salt concentrations. Both polymer electrolytes showed high transference number of lithium ion: 0.57 for the poly-1/LiTFSI system and 0.56 for the poly-1/LiFSI system, respectively. The polymer electrolytes for the poly-1/LiTFSI system were thermally more stable than those for the poly-1/LiFSI system.     

Topological invariants for phase transition points of one-dimensional Z<Subscript>2</Subscript> topological systems

We study topological properties of phase transition points of two topologicallynon-trivial Z₂ classes (D and DIII) in one dimension byassigning a Berry phase defined on closed circles around the gap closing points in theparameter space of momentum and a transition driving parameter. While the topologicalproperty of the Z₂ system is generally characterized by aZ₂topological invariant, we identify that it has a correspondence to the quantized Berryphase protected by the particle-hole symmetry, and then give a proper definition of Berryphase to the phase transition point. By applying our scheme to some specific models ofclass D and DIII, we demonstrate that the topological phase transition can be wellcharacterized by the Berry phase of the transition point, which reflects the change ofBerry phases of topologically different phases across the phase transition point.