Monovalent copper in the chalcogenide spinel CuCr2Se4

X-ray photoelectron spectra of CuCr₂Se₄ and some other copper and chromium containing compounds were studied to reveal the valence state of the copper atom in CuCr₂Se₄. Binding energies of the core electrons of the constituting atoms were determined. From these data it is concluded that copper in CuCr₂Se₄ is monovalent.     

Magnetic properties of chalcogenide spinel CuCr2Se4 nanocrystals

The magnetic properties of chalcogenide spinel CuCr₂Se₄ nanocrystals have been studied as a function of crystallite size (15-30 nm). A solution-based method is used for the facile synthesis of the nanocrystals with good size control. They have close to cubic morphology with a narrow size distribution and exhibit superparamagnetic behavior at room temperature. The Curie temperature and saturation magnetization of the nanocrystals are lower as compared with the bulk and decrease with decreasing nanocrystal size. A similar trend is observed in the paramagnetic state for the Curie-Weiss temperature and effective magnetic moment. The low temperature magnetization behavior can be qualitatively explained by spin glass dynamics.     

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.     

The ESR study of single crystal spinel ZnCr2Se4 diluted with Sb and V

The single crystal of Sb³⁺ and V³⁺ doped zinc chromium selenide spinel ZnCr₂Se₄ were prepared by a chemical transport method and characterized by ESR spectroscopy in order to examine the effect of nonmagnetic antimony and magnetic vanadium on properties of the system. For antimony admixtures the Neel temperature is very similar to that of the parent spinel ZnCr₂Se₄ (22 K). However, upon incorporating vanadium ions, the T_N temperature decreases down to 17.5 K, determined for the maximum vanadium content (x=0.06). The temperature dependence of the ESR linewidth over paramagnetic region is interpreted by an occurrence of spin-phonon interaction. The strong broadening linewidth together with its strong temperature dependence for vanadium doped ZnCr₂Se₄ is explained by the complex paramagnetic relaxation model.     

Low temperature photoconductivity of ZnIn2Se4 and CdIn2Se4

The photoconductivity of ZnIn₂Se₄ and CdIn₂Se₄ single crystals has been studied at 4.2 K. The spectra are compared to reflectivity spectra and relevant structures are interpreted in terms of interband transitions. The absence of excitonic transitions is discussed in connection with the crystalline perfection.     

Photoconductivity spectra of HgCr2Se4

The photoconductivity spectra of ferromagnetic semiconductor HgCr₂Se₄ single crystals in the intrinsic transition region were measured at a number of fixed temperatures covering T_c = 106 K. The photoconductivity edge, 0.88 eV, at room temperature shifted to 0.35 eV at 52 K.The temperature dependence of the photoconductivity edge is in good correspondence with that of the absorption edge, and is explained qualitatively well with the calculated spin correlation functions in spinels.From the theoretical calculations by Kambara et al., the lowest transition associated with the photoconduction in HgCr₂Se₄ was interpreted to be the electronic transition from the highest d? to the lowest A [dγ-p] states for up-spin at X point. The many doby effects should be taken into account.     

A direct determination of cation disorder in MgAl2O4 spinel by ESR

Satellite ESR lines of Cr³⁺ ions having a disordered nearest cation environment allow a direct determination of cation disorder in natural MgAl₂O₄ spinel. In addition, this disorder has been measured as a function of peak temperature.     

Radiated recombination in CdGa2Se4

The photoluminescence of single crystals of CdGa₂Se₄ is studied as a function of temperature, of the excitation intensity, and of the polarization of the exciting light. A possible level scheme for optical transitions in the perfect crystal is given and evidence is also found for donor-acceptor pair recombination luminescence.     

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.     

The micromagnetic study of the vanadate spinel MnV2O4

MnV₂O₄ exhibits a paramagnetic to ferrimagnetic transition at 57 K and shows significant magnetic hysteresis below 55 K. By performing detailed powder X-ray diffraction at the same temperature during cooling and warming sequences, it is found that the magnetic hysteresis observed here is owing to strains induced by the structural phase separation. The intensity of the electron spin resonance spectra shows unusual temperature dependence, which might be related to the phase separation induced by the structural transition. By performing a mean field analysis, we obtained the exchange energies among the different magnetic moments and qualitatively understood the micromagnetic properties.     

Resonant Raman scattering of CdCr2Se4

The scattering cross section of the Raman-active phonons at 156 cm^?1 (Eg) and 169 cm^?1 (F2g) in the ferromagnetic semiconductor CdCr₂Se₄ (T_c=130 K) has been measured as a function of incident photon energy between 1.55 and 2.81 eV, both in the ferromagnetic and paramagnetic phases. The resonance curve peaks sharply near 2 eV and shows a broadening for temperatures below the Curie point. The relative line intensities change significantly with photon energy. The results show that the concept of spin-dependent Raman scattering in the ferromagnetic spinels has to be revised in terms of exchange-splitting-induced resonant Raman scattering.     

Magnetic and electric properties of antimony selenide (Sb2Se3) crystals

The magnetic susceptibility in the three principal crystallographic directions, and the electrical conductivity and thermoelectric power parallel and perpendicular to the basal plane of Sb₂Se₃ single crystals, have been measured over the temperature range 100–550 K. The different results obtained from the magnetic and electric studies have been accounted for on the basis of non-stoichiometry of the compound and localized lone electrons. A hopping mechanism in the higher temperature region simultaneously with impurity excitation is suggested.     

Enhanced magnetization and ferrimagnetic behavior of normal spinel ZnFe2O4 thin film irradiated with femtosecond laser

We report on spatially selective change of magnetism from paramagnetic to ferrimagnetic-like behaviors in normal spinel ZnFe₂O₄ thin film under irradiation with 780 nm femtosecond laser pulses. The distribution of Zn²⁺ and Fe³⁺ ions in the irradiated region on the film surface becomes disordered because of local heating to high temperatures, and the metastable phase of ZnFe₂O₄ is frozen in by the rapid quenching after irradiation, resulting in the formation of the ferrimagnetic phase. The ferrimagnetic phase reverts to the paramagnetic state by annealing at 800°C. The present technique is useful for two-dimensional patterning of magnetic thin films.     

Effective ionic charges in CdGa2Se4 and CdGa2S4

Available experimental data (Raman and Infrared) on the optic phonon spectra in defect chalcopyrite crystals CdGa₂Se₄ and CdGa₂S₄ are used to determine the dynamical ionic effective charges. The results are compared with those found in other ternary compounds as spinels and chalcopyrites. An emperical correlation between the normalized Szigeti charges and the optical dielectric constant is discussed.     

Photoelectrical memory effect in ZnIn2Se4

The compound ZnIn₂Se₄ with n-type conductivity is shown to exhibit electro-optical memory effect and negative resistance effect similar to those previously reported for ZnIn₂S₄. At low temperature ZnIn₂Se₄ material will present a high conductivity during and after illumination by light of energy greater than the band gap. This high conductivity state can be quenched in three different ways (i) by heating the sample until it reaches room temperature, (ii) by illumination with monochromatic light of appropriate energy, (iii) by an electric field. In the latter case the material exhibits a negative resistance effect in the transition between the low and high conductivity conditions. These charge storage phenomena have been explained by assuming the presence of a level, localized in the forbidden gap, which is twofold negative charged and presents a repulsive barrier to the recombination of electrons.     

High pressure Raman spectroscopic study of spinel MgCr2O4

An in situ Raman spectroscopic study was conducted to investigate the pressure induced phase transformation of MgCr₂O₄ spinel up to pressures of 76.4 GPa. Results indicate that MgCr₂O₄ spinel undergoes a phase transformation to the CaFe₂O₄ (or CaTi₂O₄) structure at 14.2 GPa, and this transition is complete at 30.1 GPa. The coexistence of two phases over a wide range of pressure implies a sluggish transition mechanism. No evidence was observed to support the pressure-induced dissociation of MgCr₂O₄ at 5.7-18.8 GPa, predicted by the theoretical simulation. This high pressure MgCr₂O₄ polymorphism remains stable upon release of pressure, but at ambient conditions, it transforms to the spinel phase.     

Heat capacity and thermal expansion of CdCr2Se4 and CdCr2S4

The thermodynamic properties of the spinel ferromagnetic compounds CdCr₂Se₄ and CdCr₂S₄ have been investigated by making heat capacity and thermal expansion measurements on single crystals. For both compounds, the ferromagnetic transition is marked by λ-type thermal anomalies, and the results provide a pressure dependence of the transition temperatures that is in agreement with direct measurements. Below the transition, CdCr₂S₄ shows an anomalous heat-capacity contribution and negative thermal expansion, which are in contrast to the conventional behavior found in CdCr₂Se₄.     

Lattice vibrations of MgAl2O4 spinel

Raman spectra have been measured on oriented single crystals of MgAl₂O₄ spinel. The fundamental frequencies are A_1g = 772, E_g = 410, and T_2g = 671, 492 and 311 cm^?1. A Kramers-Kronig analysis of the reflectance spectrum of spinel yields the i. r. -active vibrations T_1u = 670, 485, 428 and 305 cm^?1.