Brillouin scattering study of phase transitions in LiK0.80(NH4)0.20SO4 mixed crystals

Brillouin spectroscopy was used to study the phase transitions of LiK_0.80(NH₄)_0.20SO₄ mixed crystals in the temperature range 10-300 K. The relevant elastic stiffness coefficients were evaluated at room temperature. The quasi-longitudinal γ₁₆ and the quasi-transverse γ₁₇ mode frequencies were measured in the above temperature range. From their frequency vs. temperature curve, three different phase transitions were determined. Two of the four phases presented by the crystal were found to be ferroelastic. The observed phases are tentatively assigned through a comparison with the phase transitions undergone by LiKSO₄ and LiK_0.96(NH₄)_0.04SO₄ crystals. An anomalous behavior of the Brillouin linewidth near the 260 K phase transition was observed.     

Magnetic, electric, and optical functionalities of (PLZT)x(BiFeO3)1−x ferroelectric-ferromagnetic thin films

We have prepared a series of (PLZT)_x(BiFeO₃)_1−x transparent thin films with thickness of 300 nm by a thermal pyrolysis method. Only films with x≦0.10 formed a single phase of perovskite structure. The film where x=0.10 exhibited both ferromagnetic and ferroelectric properties at room temperature with spontaneous magnetization and coercive magnetic fields of 0.0027μ_B and 5500 G, respectively. The remanent electric polarization and coercive electric field for the film where x=0.10 were 3.0 μC/cm² and 24 kV/cm, respectively. Additionally, films with 0.02≦x≦0.10 showed both magneto-optical effects and the second harmonic generation of transmitted light.     

EPR investigations of oxidation effects in (V1−xMox)2−δO3

Electron paramagnetic resonance (EPR) investigations has been carried out on the new family of molybdenum doped vanadium sesquioxides (V_1−xMo_x)_2−δO₃. The oxidation effects were monitored from the rate of paramagnetic V⁴⁺ created when the sample is exposed to the air. The effects of the oxidation time, sample temperature, and annealing at 1000 °C under a diluted hydrogen atmosphere on the EPR signal features are analyzed. The V⁴⁺ concentration in the oxidized samples is determined and the relaxation effects driven by the conduction electrons are pointed out from the thermal behaviour of the EPR line features. EPR spectra of all the oxidized samples also reveal a small ferromagnetic contribution strongly correlated with the V⁴⁺ content.     

Phase transformation behavior and dielectric characteristics of BaTi1−x(Al1/2Nb1/2)xO3 (0.01≤x≤0.40) ceramics

Microstructure, phase transformation behavior and dielectric properties of BaTi_1−x(Al_1/2Nb_1/2)_xO₃ (0.01≤x≤0.40) ceramics were investigated. A high level of (Al_1/2Nb_1/2)⁴⁺ substitution for Ti⁴⁺ ions was not conducive to the stability of the perovskite structure and resulted in the formation of BaAl₂O₄. As x was increased, lattice constants and unit cell volume decreased, reached a minimum at x=0.10 and then increased. The BaTi_1−x(Al_1/2Nb_1/2)_xO₃ ceramics at room temperature experienced a transformation from ferroelectric to paraelectric phase with increasing (Al_1/2Nb_1/2)⁴⁺ concentration. Meanwhile, permittivity of the BaTi_1−x(Al_1/2Nb_1/2)_xO₃ ceramics was markedly reduced, while Q value was slightly increased. Frequency dispersion of dielectric peak was obviously increased as x was increased from 0.01 to 0.10. It is of great interest that a dielectric abnormity represented by a broad dielectric peak at 200-400 K was observed for the composition with x=0.40.     

Kondo behaviour of the solid solution (Ce1−xLax)PtGa

The solid solution (Ce_1−xLa_x)PtGa has been studied through X-ray diffraction, magnetization (σ(B)), magnetic susceptibility (χ(T)), electrical resistivity (ρ(T)), magnetoresistivity (MR) and heat capacity (C_P(T)) measurements. The Néel temperature (T_N=3.3 K) for CePtGa is lowered upon La substitution as observed from χ(T) and ρ(T) measurements. The Kondo temperature T_K as calculated from MR measurements is comparable to T_N and also decreases with La substitution. The volume dependence of T_K is in accordance with the compressible Kondo lattice model and a Doniach diagram of the results is presented. C_P(T) measurements are presented for CePtGa, Ce_0.2La_0.8PtGa and LaPtGa and the results are discussed in terms of the electronic and magnetic properties. Other features of interest are anomalies in ρ(T) and C_P(T) due to crystalline electric field effects and metamagnetism as observed in σ(B) studies for samples with 0≤x≤ 0.3.     

Preparation of (CdO)1−x(PbO)x and (CdS)1−x(PbS)x thin films by spray pyrolysis technique and their characterization

Mixed thin films of (CdO)_1−x(PbO)_x and (CdS)_1−x(PbS)_x (x=0.25) were prepared on glass substrates by spray pyrolysis technique for various substrate temperatures 300, 320 and 340 °C. Structural and optical properties were studied. XRD studies reveal the formation of mixed films. The substrate temperature of 340 °C seems to be critical for the formation of CdO-PbO mixed films. It is observed that (CdS)_1−x(PbS)_x mixed films were formed at all the three substrate temperatures. The direct band gap value of (CdO)_1−x(PbO)_x and (CdS)_1−x(PbS)_x mixed films is about 2.6 and 2.37 eV, respectively.     

Properties of CuIn(SxSe1−x)2 polycrystalline thin films prepared by chemical spray pyrolysis

CuIn(S_xSe_1−x)₂ thin polycrystalline films were grown by the chemical spray pyrolysis method on the glass substrate at 280-400°C. The alloy composition in the film was studied with relation to that in the splay solution. Films were characterized by X-ray diffraction, optical absorption, Raman spectroscopy, resistivity and surface morphology. The CuInSe₂-rich alloy films grown at high substrate temperature had chalcopyrite structure, while, the CuInS₂-rich films grown at low substrate temperature exhibited sphalerite structure. Optical-gap energies were smaller than that of the bulk crystal by 0.1-0.2 eV for CuInS₂-rich films. Raman spectra exhibited both CuInSe₂-like and CuInS₂-like A₁ modes, and their relative changed systematically with alloy composition.     

The influence of microscopic parameters on the ionic conductivity of SrBi2(Nb1−xVx)2O9−δ(0≤x≤0.3) ceramics

Layered SrBi₂(Nb_1−xV_x)₂O_9−δ (SBVN) ceramics with x lying in the range 0-0.3 (30 mol%) were fabricated by the conventional sintering technique. The microstructural studies confirmed the truncating effect of V₂O₅ on the abnormal platy growth of SBN grains. The electrical conductivity studies were centred in the 573-823 K as the Curie temperature lies in this range. The concentration of mobile charge carriers (n), the diffusion constant (D₀) and the mean free path (a) were calculated by using Rice and Roth formalism. The conductivity parameters such as ion-hopping rate (ω_p) and the charge carrier concentration (K′) term have been calculated using Almond and West formalism. The aforementioned microscopic parameters were found to be V₂O₅ content dependent on SrBi₂(Nb_1−xV_x)₂O_9−δ ceramics.     

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-dependent Fe Mössbauer spectroscopy and local structure of the mullite-type Bi2(FexGa1−x)4O9 (0.1≤x≤1) solid solution

The Bi₂(Fe_xGa_1−x)₄O₉ oxide solid solution possessing a mullite-type structure has been investigated by ⁵⁷Fe Mössbauer spectroscopy in dependence of composition (0.1≤x≤1) and temperature (293≤T/K≤1073). The spectra have been fitted with two doublets for tetrahedrally and octahedrally coordinated high-spin Fe³⁺ ions, respectively. The experimental areas of the subspectra were used to determine the distribution of iron on the two inequivalent structural sites. The fraction of iron cations occupying the octahedral site is found to increase with decreasing Fe content and the cation distribution is almost independent of temperature. The unusual temperature dependence of the quadrupolar splitting, QS, observed for the octahedral site with dQS/dT>0 is discussed in connexion with structural data for Bi₂Fe₄O₉. The temperature dependence of Mössbauer isomer shifts and signal intensities is examined in the context of local vibrational properties of iron on the two inequivalent sites of the mullite-type lattice structure.     

Metal-insulator transition in the spinel-type Cu(Ir1−xCrx)2S4 system

A normal thiospinel CuIr₂S₄ exhibits a temperature-induced metal-insulator (M-I) transition around 230 K with structural transformation, showing hysteresis on heating and cooling. On the other hand, CuCr₂S₄ has the same normal spinel structure without the structural transformation. CuCr₂S₄ has been found to be metallic and ferromagnetic with the Curie temperature T_c~377 K. In order to see the effect of substituting Cr for Ir on the M-I transition, we have carried out a systematic experimental study of electrical and magnetic properties of Cu(Ir_1−xCr_x)₂S₄. The M-I transition temperature shifts to lower temperature with increasing Cr-concentration x and this transition is not detected above x~0.05. The ferromagnetic transition temperature decreases as x is decreased and the transition does not occur below x~0.20.     

Electroresistance effect in La1−xCaxMnO3 (0<x<1) ceramics

Electroresistance (ER) effects were investigated for a full series of manganite ceramics La_1−xCa_xMnO₃ (0<x<1), synthesized by solid state reaction. The results indicate that while the ER effects are large only in the presence of electrically active, high E-field boundaries, the equilibrium or metastable electronic-magnetic states in the adjoining domains are also significant, as a large ER occurs only at x=0.51 and x=0.17; those compositions are both near a two-phase coexistence region, i.e. close to a compositional regime where equilibrium insulating/metallic phase domains and interfaces would occur spontaneously.     

Growth and X-ray studies of (NaCl)x(KCl)y−x(KBr)1−y single crystals

Ternary mixed crystals of NaCl, KCl and KBr were grown by the melt method for the first time. Densities and refractive indices of all the grown crystals were determined and also used for the estimation of the bulk composition in the crystal. Lattice parameters and thermal parameters like Debye-Waller factor, mean square amplitude of vibration, Debye temperature and Debye frequency were determined from the X-ray powder diffraction data. The observed lattice parameters showed the existence of two phases in crystals with NaCl content greater than 0.1 mole fraction. The thermal parameters show a highly non-linear composition dependence. The results are reported.     

Solubility and diffusion of H in ordered (L12) and disordered Pd3Mn

Hydrogen isotherms have been measured from 423 to 573 K for the disordered and L1₂ ordered forms of Pd₃Mn and, from these equilibrium isotherms, Δ_HH$\mathrm{\Delta }{H}_{\mathrm{H}}$ and Δ_SH$\mathrm{\Delta }{S}_{\mathrm{H}}$ have been determined over a range of r values where r  =H-to-metal, atom ratio. Δ_HH$\mathrm{\Delta }{H}_{\mathrm{H}}$ values are significantly more negative for the L1₂ ordered form than for the disordered form. H diffusion constants have been determined for the L1₂ and disordered forms of Pd₃Mn from gas phase H permeation measurements through Pd₃Mn membranes (423–573 K). The activation energy for diffusion of H in the L1₂ form is 35.2 kJ/mol H which is more reasonable than the value of 76.3 kJ/mol H previously reported. The diffusion constant is greater for the disordered than for the L1₂ form.     

Substitutional sites of Co ions in CuGa1−xAlxSe2:Co crystals

The substitutional sites of Co²⁺ ions in Co²⁺-doped CuG_1−xAl_xSe₂ (including CuGaSe₂ where x=0 and CuAlSe₂ where x=1) semiconductors are studied by analyzing the composition x dependence of optical spectral parameters reported in the previous literature for these materials. From the studies, we suggest that Co²⁺ occupy I-group cation site rather than III-group cation site. The suggestion is discussed.     

Pressure dependent elastic properties of diluted magnetic semiconductors: Hg1−xMnxS (x=0.02 and 0.07)

A theoretical study of the elastic properties in diluted magnetic semiconductors Hg_1−xMn_xS (x=0.02 and 0.07) using an effective interionic interaction potential (EIoIP) in which long-range Coulomb interactions, charge transfer mechanism (three body interaction) and the Hafemeister and Flygare type short-range overlap repulsion extending up to the second neighbor ions and the van der Waals (vdW) interaction is considered. Particular attention is devoted to evaluate Poisson's ratio ν, the ratio R_S/B of S (Voigt averaged shear modulus) over B (bulk modulus), elastic anisotropy parameter, elastic wave velocity, average wave velocity and thermodynamic property as Debye temperature is calculated. By analyzing Poisson's ratio ν and the ratio R_S/B we conclude that Hg_1−xMn_xS is brittle in zinc blende (B3). To our knowledge this is the first quantitative theoretical prediction of the pressure dependence of ductile (brittle) nature of Hg_1−xMn_xS compounds and still awaits experimental confirmations.     

On the origin of irreproducible behaviour of Na1−xLixNbO3 solid solutions

The irreproducibility of electrical properties of Na_0.88Li_0.12NbO₃ solid solution on thermal cycling reported by M.A.L. Nobre and S. Lanfredi is explained by gradual decomposition of the supersaturated solid solution below ca. 800 °C.     

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.     

Annealing of thin Zr films on Si1−xGex(0≤x≤1): X-ray diffraction and Raman studies

X-ray diffraction experiments have been combined with Raman scattering and transmission electron microscopy data to analyze the result of rapid thermal annealing (RTA) applied to Zr films, 16 or 80 nm thick, sputtered on Si_1−xGe_x epilayers (0≤x≤1). The C49 Zr(Si_1−xGe_x)₂ is the unique phase obtained after complete reaction. ZrSi_1−xGe_x is formed as an intermediate phase. The C49 formation temperature T_f is lowered by the addition of Ge in the structure. Above a critical Ge composition close to x=0.33, a film microstructure change was observed. Films annealed at temperatures close to T_f are continuous and relaxed. Annealing at T>T_f leads to discontinuous films: surface roughening resulting from SiGe diffusion at film grain boundaries occurred. Grains are ultimately partially embedded in a SiGe matrix. A reduction in the lattice parameters as well as a shift of Raman lines are observed as T exceeds T_f. Both Ge non-stoichiometry and residual stress have been considered as possible origins for these changes. However, as Ge segregation has never been detected, even by using very efficient techniques, it is thought that the changes originate merely from residual stress. The C49 grains are expected to be strained under the SiGe matrix effect and shift of the Raman lines would indicate the stress is compressive. Some simple evaluations of the stress values indicate that it varies between −0.3 and −3.5 GPa for 0≤x≤1 which corresponds to a strain in the range (−0.11, −1.15%). X-ray and Raman determinations are in good agreement.     

On the power-law behavior of the AC conductivity of the mixed crystal (NH4)3H(SO4)1.42(SeO4)0.58

A power law used to describe the AC conductivity from 299 to 393 K of the mixed crystal (NH₄)₃H(SO₄)_1.42(SeO₄)_0.58 led to fractional exponent values ranging from 1.08 to 0.91, depending on structural changes induced on temperature variation [B. Louati, M. Gargouri, K. Guidara and T. Mhiri, J. Phys. Chem. Solids 66 (2005) 762]. In the present note, we suggest that the fractional law exhibits features of lattice relaxation. Despite the structural changes, the parameters of the power law are mutually interconnected to yield a temperature independent phenomenon. Such behavior is probably of general validity and characterizes the universal fractional dispersion of the AC conductivity, as it was also observed in glasses of different composition.