Transport properties of CdIn2S4 single crystals

Several transport properties have been studied on CdIn₂S₄ singlê crystals with different degrees of deviation from stoichiometry. The energy gap at 0 K was determined from the electrical measurements to be 2.2 eV. The anisotropy of the magnetoresistance effect was found and it was suggested that the minima of the conduction band were located at points along the [100] directions in k space. From an analysis of the mobility data it was found that the high resistivity of the samples is due to compensation of donors by acceptors introduced by excess sulphur. Several band parameters, the carrier scattering mechanisms and the impurity levels were determined. The thermal conductivity was measured from 4 K to 300 K and analysed by Callaway's formalism.     

Phonon spectra of stoichiometric rare-earth compound of EuGa2S4

Investigations of EuGa₂S₄ have been done on the photoluminescence (PL) related to the transition between 4f⁶5d and 4f⁷ configuration of the Eu²⁺ ion and its excitation (PLE) spectra, Raman scattering and infrared absorption. The energies of phonons coupled to the ground and the excited states of the transition are analyzed to be 34 and 19 meV from the shapes of the PL and PLE bands, respectively. The former corresponds to the energy of the Raman line showing the highest intensity. The latter is close to the value obtained from analysis of the temperature dependence of the half width of the PL band. These correspondences indicate that the relevant emission of EuGa₂S₄ surely has phonon-terminated character.     

Vibrational modes in ZnAl2S4 and CdIn2S4 crystals

Infrared reflectivity spectra and Raman scattering of the ZnAl₂S₄ and CdIn₂S₄ crystals have been investigated. Reflectivity spectra contours were calculated and phonon parameters and dielectric constants were determined. Effective charges for the Zn, Cd, In and S ions of these materials were determined.     

Magnetic anisotropy in colossal magnetoresistive FeCr2S4 single crystals

The magnetic properties of spinel FeCr₂S₄ single crystals were investigated by ferromagnetic resonance (FMR). The FMR spectrum displays a single absorption line in the whole temperature range measured for both H∥(111) and H⊥(111). With decreasing temperature, the line with H∥(111) shifts to lower fields, while that with H⊥(111) shifts to higher fields. By superposing all the FMR spectra measured in different directions at 110 K, a double-peak is obtained, which clarifies the origin of the FMR double-peak in polycrystalline sample. By taking account of magnetic anisotropy and demagnetizing effect, the orientation dependence of resonance field is well fitted. It is found that the magnetic anisotropy strengthens with decreasing temperature; however, it has no evident influence on transport and colossal magnetoresistance behavior.     

Birefringence of CuGa2S4 crystals

The interference of optical transmission spectra of thin CuGaS₂ single crystals is measured in E||c and E⊥c polarizations. The spectral dependencies of the refractive indexes n_o, n_e and Δn = n_o − n_e near the absorption edge have been determined from interference spectra. The intersection of refractive indexes at two wavelengths has been revealed at 300 K and 10 K. The characteristics of Band-Pass-Mode Filter and Band-Elimination-Mode Filter have been measured, which possess 7 narrow absorption (transmission) bands and represent a comb filter. The characteristics of these filters have been studied.     

Photoluminescence spectra of rare earth doped CaGa2S4 single crystals

Six kind CaGa₂S₄ single crystals doped with different rare earth (RE) elements are grown by the horizontal Bridgman method, and their photoluminescence (PL) spectra are measured in the temperature range from 10 to 300 K. The PL spectra of Ce or Eu doped crystals have broad line shapes due to the phonon assisted 4f-5d transitions. On the other hand, those of Pr³⁺, Tb³⁺, Er³⁺ or Tm³⁺ doped samples show narrow ones owing to the 4f-4f transitions. The assignments of the electronic levels are made in reference to the reported data of RE 4f multiplets observed in same materials.     

Electrical properties of FeCr2S4 and CoCr2S4

Resistivity and magnetoresistance are measured as functions of temperature (77–450 K) on several FeCr₂S₄ and CoCr₂S₄ single crystals (as-grown, annealed in vacuum, annealed in S-atmosphere, and doped) and found to be very sensitive to these treatments. These results are discussed on the basis of the model consisting of donor level due to S-deficiencies in addition to Fe²⁺ and Cr²⁺ levels.     

Magnetic properties of V5S8 single crystals

The magnetic properties of V₅S₈ single crystals have been investigated by susceptibility and torque measurements. The susceptibilities parallel and perpendicular to the magnetic easy axis show a remarkable anisotropy below the Neel temperature of 32 K and are nearly Isotropie above that temperature. The easy axis is found to be nearly along the c-axis of the monoclinic lattice, being inclined at an angle of 9.6 ± 1.0° from the c-axis toward the a-axis. The torque curves, measured up to 24.4 kOe at liquid helium temperature, deviate from the usual form of a sine function with increasing magnetic field. The analysis of these torque curves suggests that spin flopping may occur at 43 kOe, a comparatively low critical field. Using these experimental results, a localized d-electron model for a particular site of the vanadium-ion, proposed by previous investigators, is examined.     

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.     

Structural determination of CoIn2S4 single crystal spinel

Single crystals of the spinel CoIn₂S₄ were grown by iodine vapor transport. The structural determination leads to Fd3m space group with Co²⁺ ions distribution between O_h (63%) and T_d (37%) sites of the spinel structure.     

Raman and infrared spectra of CdIn2S4 and ZnIn2S4

Four one-phonon Raman lines have been found in CdIn₂S₄ (ZnIn₂S₄) spinels at 92 (72) cm^-1, 186 (184) cm^-1, 246 (253) cm^-1, and 367 (372) cm^-1 for incident photon energies well below the energy gap E_G ～ 2.4 (2.2) eV at 300 K. For photon energies close to E_G, the 367 cm^-1 mode underwent a resonant enhancement in CdIn₂S₄ and four infrared active but Raman forbidden F_1u modes appeared in the CdIn₂S₄ and ZnIn₂S₄ Raman spectra: TO modes at 226 (221) cm^-1 and 309 (312) cm^-1, and LO modes at 274 (272) cm^-1 and 340 (342) cm^-1.     

Neodymium luminescence in chalcogenides of europium-gallium: EuGaS4 and EuGa2Se4

Photoluminescence of chalcogenides of europium-gallium, EuGa₂S₄ and EuGa₂Se₄, doped with neodymium is investigated. The positions of Stark levels are determined from the spectra. The symmetry of luminescence centres is shown to be lower than cubic and the existence of nonequivalent centers is established. At 77 K the decay time of luminescence from the excited levels of Nd³⁺ depends on the spin of the states. That indicates a slow relaxation rate in the crystals under investigation. It is probable that these crystals can be used as effective luminophores.     

Low frequency dielectric relaxation in lightly doped VO2 single crystals

The relative effects of intrinsic and extrinsic defects on the dielectric relaxation of VO₂ crystals have been investigated by measurement of the dielectric parameters of undoped crystals and crystals doped with Ti, Cr and Al. Measurements have been made in the temperature range 77–250 K and the frequency range 50–100 kHz. The dielectric data is described by a Cole-Cole distribution function with a distribution parameter α ? 0.45 which decreases with increasing temperature. However, the distribution of activation energies g(E) derived from α is almost independent of temperature. The overall dielectric relaxation behaviour is determined primarily by the intrinsic defect structure of VO₂, and the effect of impurities is observed only in changes in the low frequency limiting (static) value of the dielectric constant. The same transport mechanism is found to determine the dc conductivity and the dielectric relaxation and evidence is presented that the dielectric relaxation is of dipolar origin.     

Band structure calculations on the layered compounds FeGa2S4 and NiGa2S4

For the compounds FeGa₂S₄ and NiGa₂S₄ band structure calculations have been performed by the ab initio plane wave pseudo-potential method. The valence charge density distribution points to an ionic type of chemical bonding between the transition metal atoms and the ligand atoms. Two models for the pseudo-potentials are used to calculate the band structures: (a) only s and p electrons and (b) also the d-shells of the transition metal atoms are included in the pseudo-potentials. The differences between these two cases of band structures are discussed. Energy gap formation peculiarities are analysed for both crystals. Zak's elementary energy band concept is demonstrated for the energy spectra of the considered crystals.     

Geometric frustration in CuV2S4

A cubic spinel conductor CuV₂S₄, containing the corner-sharing tetrahedral lattice of V, was investigated. Above a structural transition at 90 K, the ⁵¹V nuclear spin-relaxation rate 1/T₁ is comparatively large in magnitude and tends to saturate at higher temperatures, indicating that the V lattice behaves as a nearly antiferromagnetic metal. By substituting nonmagnetic Sn for V, the susceptibility turns to be of Curie-Weiss type and temperature-independent, suggesting recovery of hidden spins as a result of a partial release of the frustration. These results lead to the conclusion that CuV₂S₄ is an itinerant-electron frustrated system as YMn₂. The CDW transition of CuV₂S₄ accompanied by a tetragonal distortion which may be understood as a result of lowering of interaction dimensionality inherent to the corner-sharing tetrahedral lattice.     

On photoluminescence in HgGa2S4

In this paper, we investigate the kinetics of photoluminescence in excited crystals of HgGa₂S₄ which have recently been proposed for implementing tunable luminescent devices. From photoluminescence experiments, performed at various temperatures and excitation powers, it appears that two kinds of radiative recombination processes take place during crystal excitation. These originate two bands in emission spectra which were resolved by means of a fitting procedure. The dependencies of these bands on temperature and excitation power density are explained by means of a specific kinetic model. A broad band, peaking at about 1.8 eV, is ascribed to electron-hole tunnel recombinations occurring in associated donor-acceptor pairs, according to a Prener-Williams scheme. The second narrow band, peaking at about 2.3 eV, is ascribed to electron-hole recombinations occurring in centres presenting short () and long-life () excited states. At room temperature, owing to thermally activated relaxation from short- to long-life states, these centres saturate under relatively low excitation powers. The tunability of photoluminescence is a consequence of competition between monomolecular and bimolecular recombination processes.     

Magnetic properties of CuCr2Se4 single crystals

The magnetic properties of CuCr₂Se₄ single crystals, which were grown by chemical transport reactions using iodine as a carrier, have been investigated. The magnetic moment at 0 K is found to be 5.07 μ_B per mole. The susceptibility at high temperatures follows a Curie-Weiss law with an asymptotic Curie temperature 430 K and a Curie constant 2.55 emu · $\text{deg}\text{mol}$. The magnetocrystalline anisotropy constants K₁ and K₂ are ? 6.9x 10⁵ and ? 0.9x 10⁵$\text{erg}\text{cm}{}^3$, respectively, at 5.1 K.In order to examine the effects of annealing on the magnetocrystalline anisotropy, the ferromagnetic resonance at room temperature was measured after annealing in vacuum and subsequently in an atmosphere of Se. It is found that the absolute values of K₁ and K₂ decrease after annealing in vacuum and increase to the initial values after annealing in an atmosphere of Se.     

Cation ordering and crystal structures in AGa2X4 compounds (CoGa2S4, CdGa2S4, CdGa2Se4, HgGa2Se4, HgGa2Te4)

Single crystals of some AGa₂X₄ compounds (CoGa₂S₄, CdGa₂S₄, CdGa₂Se₄, HgGa₂Se₄, HgGa₂Te₄) were prepared by chemical vapour deposition and flux method.The X-ray structural investigations indicated blende or defect chalcopyrite structures.A simple relationship is suggested between the c/a ratio and the cationic sublattice ordering.     

非线性光学晶体HgGa2S4 和 Hg0.5Cd0.5Ga2S4的能带结构、化学键及光学性质研究

用密度泛函理论和非谐振子模型计算了晶体HgGa₂S₄和Hg_0.5Cd_0.5Ga₂S₄的能带结构、态密度、化学成键及线性、非线性光学性质。结果表明：HgGa₂S₄的价带顶部主要是Ga-S成键态的贡献，导带底部主要是Ga-S反键态的贡献; Hg_0.5Cd_0.5Ga₂S₄的价带顶部主要由S-3p轨道组成，导带底部主要是Ga-S反键态的贡献。布居分析表明Ga-S键主要是共价成分，而Hg-S和Cd-S键主要是离子成分。HgGa₂S₄的折射率计算值与实验值在低能量区很好吻合。另外，HgGa₂S₄的能隙计算值比Hg_0.5Cd_0.5Ga₂S₄小，而二阶非线性极化率比Hg_0.5Cd_0.5Ga₂S₄大。