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.     

Influence of S→Se substitution on chemical and physical properties of Cu7Ge(S1−xSex)5I superionic solid solutions

Phase diagram of Cu₇GeS₅I-Cu₇GeSe₅I superionic system was investigated by the differential thermal analysis (DTA). Chemical interaction in Cu₇GeS₅I-Cu₇GeSe₅I system was studied by X-ray phase analysis (XPA), microstructural analysis, and density determination. Compositional behaviour of diffuse reflection spectra and energy gap due to S→Se anion substitution in Cu₇Ge(S_1−xSe_x)₅I solid solutions are discussed.     

Interrelation between optical, refractometric, and lattice parameters of Cu6P(S1−x Sex)5I crystals

The influence of the compositional disordering on the energy of the fundamental absorption edge and the refractive index dispersion of the crystalline solid solutions Cu₆P(S_1?x Se_x)₅I is studied. It is shown that the concentration dependences of the optical pseudogap width, the refractive index, and the lattice parameter in these crystalline solid solutions are interrelated.     

Activation energies of the acceptor-bound excitons and the donor-acceptor pairs in nitrogen-doped p-type ZnSe, p-type ZnSySe1−y, and p-type Zn1−xMgxSySe1−y epitaxial films grown on GaAs (1 0 0) substrates

Nitrogen-doped p-type ZnSe, p-type ZnS_ySe_1−y, and p-type Zn_1−xMg_xS_ySe_1−y epilayers were grown on n-type GaAs (1 0 0) substrates by molecular beam epitaxy. Photoluminescence (PL) spectra for the p-type ZnSe and the lattice-matched p-type ZnS_0.06Se_0.94, and p-type Zn_0.92Mg_0.08S_0.12Se_0.88 epilayers showed a deep acceptor bound exciton emission and a donor-acceptor pair emission. Temperature-dependent PL measurements were carried out to determine the activation energies of these states. The activation energies of the acceptor-bound excitons and the donor-acceptor pairs were determined to be 40 and 65 meV in the p-type ZnSe epilayer, 20 and 45 meV in the p-type ZnS_0.06Se_0.94, and 45 and 43 meV in the p-type Zn_0.92Mg_0.08S_0.12Se_0.88 epilayers.     

Enhanced ferroelectric, magnetic and magnetoelectric properties of Bi1−xCaxFe1−xTixO3 solid solutions

We report on the enhanced electromechanical, magnetic and magnetoelectric properties of Bi_1−xCa_xFe_1−xTi_xO₃ solid solutions. The crystal structure of the x≈0.25 compounds are close to the rhombohedral-orthorhombic phase boundary, and the solid solutions are characterized by increased electromechanical properties due to the polarization extension near the polar-nonpolar border. The homogenous weakly ferromagnetic state is established at x>0.15 doping. The chemical doping shifts the magnetic transition close to room temperature, thus enlarging the magnetic susceptibility of the compounds. The solid solutions at the morphotropic phase boundary exhibit a nearly twofold increase in piezoelectric response, whereas the magnetoelectric coupling shows five times enhancement in comparison with the parent bismuth ferrite.     

Theoretical investigation of the conduction and valence band offsets of GaAs1−x Nx/GaAs1−yNy heterointerfaces

Theoretical investigations of the conduction band offset (CBO) and valence band offset (VBO) of the relaxed and pseudo-morphically strained GaAs_1−xN_x/GaAs_1−yN_y heterointerfaces at various nitrogen concentrations (x and y) within the range 0-0.05 and along the [0 0 1] direction are performed by means of the model-solid theory combined with the empirical pseudopotential method under the virtual crystal approximation that takes into account the effects of the compositional disorder. It has been found that for y < x, the CBO and VBO have negative and positive signs, respectively, whereas the reverse is seen when y > x. The band gap of the GaAs_1−xN_x over layer falls completely inside the band gap of the substrate GaAs_1−yN_y and thus the alignment is of type I (straddling) for y < x. When y > x, the alignment remains of type I but in this case it is the band gap of the substrate GaAs_1−yN_y which is fully inside the band gap of the GaAs_1−xN_x over layer. Besides the CBO, the VBO and the relaxed/strained band gap of two particular cases: GaAs_1−xN_x/GaAs and GaAs_1−xN_x/GaAs_0.98N_0.02 heterointerfaces have been determined.     

Structure and magnetic properties of Ca1−x−yMgxCu2+yO3 influenced by isoelectronic substitution x

Phases of the composition Ca_1−x−yMg_xCu_2+yO₃ have been prepared for the first time. The compounds are isostructural with the known end-members CaCu₂O₃ and MgCu₂O₃ showing a two-leg spin-ladder-like connection of copper and oxygen atoms within the Cu₂O₃-layer. Opposite the spin ladders this layer is folded, which results in a long-range antiferromagnetic ordering of these phases. The Néel temperature can be adapted by variation of x in Ca_1−x−yMg_xCu_2+yO₃ between 24 and 80 K. Several structural features, which influence the magnetic ordering, are discussed.     

Increase of Tc in the 1:2:3 superconductors YBCO and (CaxLa1−x)(LauBa1−u)2Cu3Oy after slow cooling or low temperature annealing

The well known phenomenon of the increase of T_c of YBCO after slow cooling or low temperature annealing without change of the oxygen content, was found also for the YBCO like tetragonal superconductors of (Ca_xLa_1−x)(La_uBa_1−u)₂Cu₃O_y (this compound has been previously denoted as CLBLCO, CLBCO or CaLaBaCuO). It has been observed at 150 and 100 °C for oxygen underdoped, optimally- and overdoped ceramics. The products retain their tetragonal unit cells. The possible reasons of this phenomenon are discussed.     

Superconductivity and magnetism of La2Cu1−xZnxO4+δ chemically oxidized by NaClO

The structural, superconducting and magnetic properties of La₂Cu_1−xZn_xO_4+δ (0≤x≤0.1) chemically oxidized by NaClO at room temperature were studied. All the samples before and after oxidation are single phase with orthorhombic structure, as indicated by their powder X-ray diffraction analysis. The iodometric titration results indicate that Zn-substituted La₂Cu_1−xZn_xO₄ is more favorable for the insertion of the excess oxygen, as compared to the Zn-free La₂CuO₄. The T_c suppression rate resulting from Zn substitution in La₂Cu_1−xZn_xO_4+δ is −12.4 K/%. The effective magnetic moment induced by the non-magnetic Zn ion is the order of one Bohr magneton, which decreases with increasing the Zn concentrations in the range examined. The latter two results are qualitatively well consistent with those obtained in La_2−xSr_xCu_1−yZn_yO₄ with the Sr optimal doping. This reveals that the non-magnetic Zn ions play the same role in both of the La₂Cu_1−xZn_xO_4+δ with the excess oxygen content of about 0.1 and the La_2−xSr_xCu_1−yZn_yO₄ with the Sr optimal doping.     

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.     

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.     

Electrodeposition of n-type Bi2Te3−ySey thermoelectric thin films on stainless steel and gold substrates

Thermoelectric films of n-Bi₂Te_3−ySe_y were prepared by potentiostatic electrodeposition technique onto stainless steel and gold substrates at room temperature. These films were used for morphological, compositional and structural analysis by environment scanning electron microscope (ESEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). The effect of different substrates on the structure and morphology of Bi₂Te_3−ySe_y films and relation between Se content in the electrodepositing solutions and in the films were also investigated. These studies revealed that Bi, Te and Se could be co-deposited to form Bi₂Te_3−ySe_y semiconductor compound in the solution containing Bi³⁺, HTeO₂⁺ and H₂SeO₃. The morphology and structure of the films are sensitive to the substrate material. The doped content of Se element in the Bi₂Te_3−ySe_y compound can be controlled by adjusting the Se⁴⁺ concentration in the electrodepositing solution. X-ray diffraction analysis indicates that the films prepared at −40 mV versus saturated calomel electrode (SCE) exhibit strong (1 1 0) orientation with rhombohedral structure.     

Structural,thermal and electrical properties of the semiconductor system Ag(1−x)CuxInSe2

This paper presents a study of bulk samples synthesized of the Ag_1−xCu_xInSe₂ semiconductor system. Structural, thermal and electrical properties, as a function of the nominal composition (Cu content) x=0.0, 0.2, 0.4, 0.6, 0.8, and 1.0 were studied. The influence of x on parameters such as melting temperature, solid phase transition temperature, lattice parameters, bond lengths, crystallite size t (coherent domain), electrical resistivity, electrical mobility and majority carrier concentration was analyzed. The electrical parameters are analyzed at room temperature. In general, it is observed that the properties of the Ag_1−xCu_xInSe₂ system for x≤0.4 are dominated by n-AgInSe₂, while for x>0.4, these are in the domain of p-CuInSe₂. The crystallite size t in the whole composition range (x) is of the order of the nanoparticles. Secondary phases (CuSe, Ag₂Se and InSe) in small proportion were identified by XRD and DTA.     

Evolution from relaxor-like dielectric to ferroelectric in Ba[(Fe0.5Nb0.5)1−xTix]O3 solid solutions

Ba[(Fe_0.5Nb_0.5)_1−xTi_x]O₃ (x=0.2,0.4,0.6,0.8,0.85,0.9 and 0.95) solid solutions were synthesized by a standard solid-state reaction technique. X-ray diffraction at room temperature and dielectric characteristics over a broad temperature and frequency range were evaluated systematically. The structure of Ba[(Fe_0.5Nb_0.5)_1−xTi_x]O₃ solid solutions changed from cubic to tetragonal with increasing x. A Debye-like dielectric relaxation following the Arrhenius law similar to that in Ba(Fe_0.5Nb_0.5)O₃ was observed at lower temperature in the composition range 0.2≤x≤0.8, while the relaxor ferroelectric, diffused ferroelectric and normal ferroelectric behavior were observed for x=0.85,0.9 and 0.95, respectively. The process of the evolution of relaxor-like dielectric to ferroelectric suggested the changing from dilute polar micro-domains to polar micro-domains, polar micro/macro-domains and then polar macro-domains in the present ceramics.     

Luminescent properties of HTP AgGd1−xW2O8:Eux and AgGd1−x(W1−yMoy)2O8:Eux phosphor for white LED

Intense red phosphors, AgGd_1−xEu_x(W_1−yMo_y)₂O₈ (x=0.0-1.0, y=0.0-1.0), have been synthesized through traditional solid-state reaction and characterized by X-ray diffraction (XRD) and photoluminescence (PL). XRD results reveal that AgGd_1−xEu_xW₂O₈ synthesized at 1000 °C has a tetragonal crystal structure, which is named as high temperature phase (HTP) AgGdW₂O₈. All phosphors compositions with Eu³⁺ show red and green emission on excitation either in the charge-transfer or Eu³⁺ levels. Analysis of the emission spectra with different Eu³⁺ concentrations reveal that the optimum dopant concentration for Eu³⁺ is x=0.6 in the HTP AgGd_1−xEu_xW₂O₈ (x=0.0-1.0). Studies on the AgGd_0.4Eu_0.6(W_1−yMo_y)₂O₈ (y=0.0-1.0) and AgGd_1−xEu_x(W_0.7Mo_0.3)₂O₈ (x=0.0-1.0) show that the emission intensity is maximum for compositions with y=0.3 and x=0.5, respectively, and a decrease in emission intensity is observed for higher y or x values. The Mo⁶⁺ and Eu³⁺ co-doped AgGd(WO₄)₂ phosphors show higher emission intensity in comparison with the singly Eu³⁺-doped AgGd(WO₄)₂ in UV region. The intense emission of the tungstate/molybdate phosphors under 394 and 465 nm excitations, respectively, suggests that these materials are promising candidates as red-emitting phosphors for near-UV/blue GaN-based white LED for white light generation.     

Electrical and optical absorption studies of Cu7GeS5I fast-ion conductor

Electrical conductivity and fundamental absorption spectra of monocrystalline Cu₇GeS₅I were measured in the temperature ranges 95-370 and 77-373 K, respectively. A rather high electrical conductivity (σ_t=6.98×10⁻³Ω⁻¹ cm⁻¹ at 300 K) and low activation energy (ΔE_a=0.183 eV) was found. The influence of different types of disordering on the Urbach absorption edge and electron-phonon interaction parameters were calculated, discussed and compared with the same parameters in Cu₇GeS₅I, Cu₆PX₅I (X=S,Se) and Ag₇GeX₅I (X=S,Se) compounds. We have concluded that the P→Ge and Cu→Ag cation substitution results in an increase of the electrical conductivity and a decrease of the activation energy. Besides, P→Ge substitution, results in complete smearing and disappearance of the exciton absorption bands and in blue shift of the Urbach absorption edge, an increase of the edge energy width and an electron-phonon-interaction enhancement.     

Structural and magnetic properties of Cr1+x(Se1−yTey)2 compounds

The structural and magnetic properties of Cr_1+x(Se_1−yTe_y)₂ having a NiAs structure has been studied for (1+x)=1.27, 1.32 and 1.36 and y=0.75 by means of the Korringa-Kohn-Rostoker (KKR) band structure method. The sub-stoichiometry and the disorder on the chalcogenide sub-lattice has been treated by means of the coherent potential approximation (CPA) alloy theory. From total energy calculations a preferential site occupation on the Cr sub-lattice was found together with an antiparallel alignment of the magnetic moments on the two inequivalent Cr layers. The magnetic properties at finite temperature has been studied by means of Monte Carlo simulations on the basis of a classical Heisenberg Hamiltonian and the exchange coupling parameters calculated from first principles. This approach allowed to determine the critical temperature in good agreement with experiment.     

Effect of composition and thermal annealing on the absorption and electrical conduction of Se85−xTe15Sbx glasses

The optical absorption of the as-prepared and thermally annealed Se_85−xTe₁₅Sb_x (0≤x≤9) thin films was measured. The mechanism of the optical absorption follows the rule of non-direct transition. The optical energy gap (E₀) decreased from 1.12 to 0.84 eV with increasing Sb content of the as-prepared films from 0 to 9 at.%. The as-prepared Se₇₆Te₁₅Sb₉ films showed an increase in (E₀) with increasing the temperature of annealing in the range above T_g (363 K). The electrical conductivity of the as-prepared and annealed films was found to be of Arrhenius type with temperature in the range 300-360 K. The activation energy for conduction was found to decrease with increasing both the Sb content and temperature of annealing. The results were discussed on the basis of the lone-pair electron effect and of amorphous crystalline transformation.     

Heat capacity and magnetocaloric effect in manganites (La1−yEuy)0.7Pb0.3MnO3 (y:0.2; 0.6)

Heat capacity and intensive magnetocaloric effect (MCE) in manganites (La_1−yEu_y)_0.7Pb_0.3MnO₃ [y=0.2; 0.6] (LEPM) were investigated by means of adiabatic calorimeter. The heat capacity anomaly as well as the values of both the intensive (ΔT_AD) and the extensive (ΔS_MCE) MCE were found to decrease upon increased replacement of La with nonmagnetic Eu. However, because of widening of the MCE peaks, the LEPM compounds show the relative cooling power, RCP/ΔH, comparable to other solid solutions of manganites. Owing to strong effect of Eu→La substitution on the Curie temperature, LEPM might have potential as the solid state refrigerants in multi-element cooling apparatus operating in a wide temperature range.     

Magnetism on Mg1−xZnxCyNi3

The magnetic phase diagram for Mg_1−xZn_xC_yNi₃ has been tentatively constructed based on magnetization and muon spin relaxation (μSR) measurements. The superconducting phase was observed to fade as x (y) increases (decreases). The low y samples show early stages of long-range ferromagnetism, or complete long-range ferromagnetism. In the phase diagram, the ferromagnetic phase exists in addition to the superconducting phase, suggesting that there is some correlation between superconductivity and ferromagnetism, even though the coexistence of ferromagnetism and superconductivity is not observed from the μSR measurements down to 20 mK for the superconducting sample (T_c=2.5 K, (x, y)=(0, 0.9)).