Optical band gap and Raman spectra in some (Bi2O3)x(WO3)y(TeO2)100−x−y and (PbO)x(WO3)y(TeO2)100−x−y glasses

The glasses representing (Bi₂O₃)_x(WO₃)_y(TeO₂)_100?x?y and (PbO)_x(WO₃)_y(TeO₂)_100?x?y systems were prepared. The dilatometric glass-transition temperatures of examined glass samples were found in the region 383–434 °C, the coefficient of thermal expansion varied from 12 to 16 ppm/°C and the density ranged from 6.30₂ to 6.80₈ g/cm³. From the optical transmission measurements of thin glassy bulk samples prepared by a glass blowing, the optical gap values were found in the narrow region 3.21–3.36 eV. For the temperature interval 300–480 K, the values of the temperature coefficient of the optical band gap varied from 3.7 × 10^?4 to 5.24 × 10^?4 eV/K. It is suggested that Raman feature observed at around 350 cm^?1 can be assigned to an overlap of Raman bands attributed to WO₆ corner shared octahedra and to the following three atomic linkages: Bi–O–Te, Pb–O–Te and W–O–Te.     

Structure and properties of ceramic solid solutions Li x Na1 − x Ta y Nb 1 − y O3 (x = 0–0.05, y = 0–0.04)

The structure of Li_0.03Na_0.97Ta _y Nb_{1 ? y} O₃ ceramic solid solutions and the processes of its disordering with a change in composition and temperature have been studied by full-profile X-ray diffraction analysis and Raman spectroscopy. It was established that at room temperature the structure of Li_0.03Na_0.97Ta_0.05Nb_0.95O₃ solid solutions is close to the NaNbO₃ structure and has a space group P21ma with four formula units per unit cell. It was shown that the oxygen octahedra in the Li _x Na_1?x Ta_0.1Nb_0.9O₃ solid solutions (0, 0.15, 0.03, 0.04, 0.05) are slightly distorted and their geometry is identical to that of octahedra in the NaNbO₃ structure. The temperature dependence of the intensities of lines in the Raman spectrum of Li_0.03Na_0.97Ta_0.4Nb_0.6O₃ solid solutions corresponding to vibrations of Li⁺ and Na⁺ cations in the cuboctahedral structural voids revealed a strong disordering in the alkali metal sublattice at a temperature above 322°C. This may indicate the essential stepwise increase in the Li⁺ cation mobility and may result in a change in the kinetic and energetic characteristics of ion charge transport.     

Growth and characterization of lead-free Ba(1−x)CaxTi(1−y)ZryO3 single crystal

A lead-free Ba_(1?x)Ca_xTi_(1?y)Zr_yO₃ (BCZT) single crystal (x=0.08, y=0.26) was grown by the Czochralski (CZ) method in a mixed flux of TiO₂ and ZrO₂. The composition of as-grown BCZT was analyzed by electron probe micro-analysis. The structure, dielectric properties and phase transition were investigated at different temperatures. The X-ray diffraction results confirmed that the structure of the as-grown BCZT crystal was cubic both at 25 °C and 500 °C. The temperature dependence of the dielectric constant and Raman spectra characterization revealed that there was a phase transition from cubic to tetragonal, which happened between 200 K and 250 K. With increasing frequency, the Curie temperature shifted towards high temperature.     

Electromechanical and electro-optic properties of xBiScO3–yBiGaO3–(1−x−y)PbTiO3 single crystals

Single crystals in the xBiScO₃–yBiGaO₃–(1−x−y)PbTiO₃ (BS–BG–PT) system were grown by the high temperature solution method using Pb₃O₄ and Bi₂O₃ as the flux. The dielectric permittivity (ε_r) at room temperature for unpoled tetragonal crystals was determined to be 500–600 with dielectric loss tangents less than 0.3%. The Curie temperature was found to be around ∼420–450°C, with a dielectric maximum, exhibiting relaxor behavior. The longitudinal piezoelectric coefficient (d₃₃) was found to be ∼300 pC/N for 〈0 0 1〉 oriented tetragonal crystals with electromechanical coupling factor (k₃₃) of 75%, with a shear mode, d₁₅∼290 pC/N and k₁₅∼45%, lateral mode, d₃₁∼−55 pC/N and k₃₁∼−37%. The remnant polarization (P_r) was 46 μC/cm² with a coercive field (E_c) of 43 kV/cm at 1 Hz and DC field of 60 kV/cm. The linear electro-optic (E-O) coefficients of poled crystals determined using an automated scanning Mach–Zehnder interferometer method at room temperature and wavelength of 632.8 nm were r₃₃=36 and r₁₃=4 pm/V, respectively.     

Crystal structure of α‴-(Zn1−x Cd x )3As2 (x = 0.26)

Single crystals of the α?-phase of (Zn_{1 ? x} Cd _x )₃As₂ solid solution (x = 0.26) have been prepared and investigated by X-ray diffraction analysis. The tetragonal unit-cell parameters are found to be a = b = 8.5377(2) Å, c = 24.0666(9) Å, sp. gr. I4₁/amd, Z = 16. Zn and Cd atoms in the crystal statistically occupy three symmetrically independent positions in the mirror planes and are tetrahedrally coordinated by arsenic atoms. (Zn,Cd) tetrahedra share edges to form a three-dimensional structure framework. The α?-phase is geometrically related to the fluorite structure. The character of arrangement of tetrahedral vacancies in fluorite-like unit cells is revealed. Chains of tetrahedral vacancies form microchannels oriented parallel the a and b axes, which pierce the three-dimensional structure framework at different levels along the c axis. The structure of α″-Cd₃As₂ crystals is found to be similar to that of α?-(Zn_0.74Cd_0.26)₃As₂.     

Magnetic behavior and microstructure of x%V2O5·(100−x)%As2O3 glasses

The magnetic properties and microstructure of x%V₂O₅·(100−x)%As₂O₃ glasses with x varying in the range 40 to 90 mol% were investigated in order to elucidate their magnetic ordering. Weak antiferromagnetic interactions between V⁴⁺ ions were observed. Glasses with x ⩾ 60 separated into two glassy phases. The effect of microstructure on magnetic properties of these glasses was investigated. Phase separation increases with increasing V₂O₅ content and produces a broadening of the EPR line width of glasses with high vanadium content (x > 70). The c = V⁴⁺/V_total ratio of x%V₂O₅·(100−x)%As₂O₃ glasses, determined from EPR and chemical analysis, are considerably greater than those usually reported for x%V₂O₅·(100−x)%P₂O₅ glasses.     

Thermal and electric transport properties of (60−x)V2O5–xAs2O3–20Fe2O3–10CaO–10Li2O unconventional glassy system

This paper presents the results of kinematical studies of glass transition and crystallization in the unconventional glassy system (60?x)V₂O₅–xAs₂O₃–20Fe₂O₃–10CaO–10Li₂O (x = 0, 10, 20, 30, 40 mol%) using differential scanning calorimetry (DSC). The glass transition temperatures (T_g), the onset crystallization temperatures (T_c), and the peak temperatures of crystallization (T_p) were found to be dependent on the compositions and the heating rates. From the dependence on heating rates of (T_g) and (T_p) the activation energy for glass transition (E_g) and the activation energy for crystallization (E_c) are calculated. The thermal stability of (60?x)V₂O₅–xAs₂O₃–20Fe₂O₃–10CaO–10Li₂O was evaluated in term of, criteria ΔT = T_c ? T_g. All the results confirm that the thermal stability increase with increasing As₂O₃ contents. From the electric–dielectric measurements it was found that, σ_dc, σ_ac(ω) and θ_D/2 decrease with increasing As₂O₃ contents. It is also observed that the dielectric constant (ε₁(ω)) and the loss factor (tan δ) decrease with increasing As₂O₃ contents in this glass system.     

Electrical properties of glass and liquid semiconductor system (As2Te3)x(Tl2Se)1−x

We have measured the electrical conductivity and thermoelectric power of the pseudobinary system (As₂Te₃)_x(Tl₂Se)_1−x both in the glass and liquid states. The effect of the addition of excess Tl has also been examined. It has been found that the activation energy of electronic conduction is closely related to the average atomization energy of these materials.     

Crystal structure of new synthetic Ca,Na carbonate-borate Ca2Na(Na x Ca0.5 ? x )[B 3 t B 2 δ O8(OH)(O1 ? x OH x )](CO3)

New Ca,Na carbonate-borate Ca₂Na(Na _x Ca_{0.5 ? x} ) [B ₃ ^t B ₂ ^?? O₈(OH)(O_{1 ? x} OH _x )](CO₃) crystals (x ?? 0.4) have been synthesized by the hydrothermal method in the Ca(OH)₂-H₃BO₃-Na₂CO₃-NaCl-system at t = 250°C and P = 70?C80 atm; the structure parameters are found to be a = 11.1848(3) ?, b = 6.4727(2) ?, c = 25.8181(7) ?, ?? = 96.364(3)°, V = 1857.60(9) ?³, sp. gr. C2/c, Z = 8, and ??_calcd = 2.801 g/cm³ (Xcalibur S autodiffractometer (CCD), 2663 reflections with I > 2?? (I), direct solution, refinement by the least-squares method in the anisotropic approximation of thermal atomic vibrations, hydrogen localization, R ₁ = 0.0387). The structure is based on boron-oxygen layers of pentaborate radicals 5(2?? + 3T). Ca and Na polyhedra and CO₃ triangles are located between the layers. A crystallochemical analysis of the new Ca,Na carbonate-borate has established its similarity to natural Na,Ca pentaborates (heidornite and tuzlaite) and synthetic Na,Ba-decaborate.     

Growth and properties of mixed K2Ni x Co1−x (SO4)2 · 6H2O crystals

Optically homogeneous mixed K₂Ni _x Co_{(1 ? x)}(SO₄)₂ · 6H₂O crystals are grown from solutions of different compositions by the temperature-reduction technique in static and dynamic regimes. The optical characteristics of the grown crystals are measured: transmittance reaches 80% in the wavelength range of 240–290 nm and no more than 9% in the visible spectral range. The thermal stability of the crystals is studied. It is established that the thermal stability of mixed K₂Ni _x Co_{1 ? x} (SO₄)₂ · 6H₂O crystals is higher than that of K₂Co(SO₄)₂ · 6H₂O crystal. The defects of the mixed crystals grown in static and dynamic regimes are investigated by X-ray topography.     

Raman spectroscopy studies of xNa2S+(1−x)B2S3 glasses and polycrystals

The Raman spectra of binary xNa₂S+(1−x)B₂S₃ glasses and polycrystals have been measured for the first time and are used to develop a structural model of the sodium thioborate glasses. The Raman spectra confirm our previous infrared (IR) experimental conclusions that the structure of vitreous (ν-B₂S₃) is comprised of B3(0) groups and six-membered rings. It was also found that as sodium sulfide is added to the glass in the low alkali (x<0.35) glass forming region, the B4 groups are formed at the expense of the B3(0) groups first and then from the six-membered ring groups. The Raman spectra are also consistent with the presence of a pyramidal structural arrangement of B4 groups with trigonally coordinated sulfur atoms. This structure could explain the existence of the super-stoichiometric amounts of B4 groups found using nuclear magnetic resonance (NMR). Glasses in the high alkali region (0.50<x<0.80) progressively change from being comprised of metathioborate rings to being comprised of B3(3) groups. The Raman spectra also confirms the IR spectra which saw no evidence of B3(2) groups in these sodium thioborate glasses.     

Production and properties of high purity TeO2− WO3−(La2O3, Bi2O3) and TeO2− ZnO−Na2O−Bi2O3 glasses

TeO₂–WO₃ (TW), TeO₂–WO₃–La₂O₃ (TWL), TeO₂–WO₃–La₂O₃–Bi₂O₃ (TWLB) and TeO₂–ZnO–Na₂O–Bi₂O₃ (TZNB) glasses were produced by high-purity oxide mixtures melting in platinum or gold crucible at 800 °C in the atmosphere of purified oxygen. The total content of Cu, Mn, Fe, Co and Ni impurities was not more than 0.1–0.5 ppm wt in the initial oxides and glasses. The stability of TZNB glasses to crystallization, characterized by (T_x ? T_g) value more than 150 °C, was demonstrated by DSC measurements at heating rate 10 K/min. In the case of La₂O₃-containing glasses the thermal effects of both crystallization and fusion of the crystallized phases were not observed. The hydroxyl groups absorption coefficients of pure tellurite glasses at the maximum of the absorption band (λ ~ 3 μm) were in the region of 0.012–0.001 cm^?1. The optical absorption losses, measured by the laser calorimetry method at λ = 1.56 and 1.97 μm, did not exceed 100 dB/km.     

Investigation of the structure and properties of (K x (NH4)1 − x )3H(SO4)2 single crystals

The influence of isomorphous replacement in the cation sublattice on the kinetics of the phase transition in single crystals of the solid solutions (K _x (NH₄)_{1 ? x} ) _m H _n (SO₄)_{(m + n)/2} · yH₂O belonging to the K₃H(SO₄)₂-(NH₄)₃H(SO₄)₂-H₂O salt system was studied. Superproton phase transitions for the end compositions of this system have been found earlier. The optical and thermal properties of crystals with the composition (K,NH₄)₃H(SO₄)₂ in the temperature range from 295 to 500 K were investigated, and the crystal structure was determined at 295 K. The results of the study and the comparison with the literature data show that the replacement of potassium atoms with ammonia leads to a fundamental change in the kinetics of the phase transition, the phase-transition temperature remaining virtually unchanged.     

Growth, structure, and properties of ferroelectric—ferroelastic— superionic K3Nb3B2O12 and K3−x NaxNb3B2O12 crystals

The potassium niobate-borate K₃Nb₃B₂O₁₂ (KNB) crystals and their solid solutions with partial substitution of potassium by sodium (KNB: Na) are grown from flux and their physical properties are studied. The specific feature of the crystals grown is a complicated polymorphism and the unique combination of ferroelectric and ferroelastic properties with superionic conductivity with respect to potassium ions.     

Stoichiometry–structure correlation of epitaxial Ce1−xPrxO2−δ (x=0−1) thin films on Si(111)

Epitaxial oxide thin film layers are of interest for model catalytic studies. We report the growth of Ce_1?xPr_xO_2?δ mixed oxide layers of different stoichiometries (x=0–1) and oxygen deficiency (δ>0) on Si(111) by co-evaporating molecular beam epitaxy. The main objective is to identify the crystal phases and to investigate the correlation between compositions and crystal structures. X-ray photoemission spectroscopy was performed to quantify the stoichiometries. An extensive laboratory and synchrotron based X-ray diffraction analysis was carried out to determine the vertical and lateral lattice orientations and the strain status of the layers. The study revealed that single crystalline Ce_1?xPr_xO_2?δ/Si(111) heterostructures can be epitaxially grown on Si(111) for model catalytic studies. In addition to the structure–stoichiometry relationship typical to mixed oxide bulk powders, we identified a hexagonal mixed Ce–Pr oxide thin film phase not yet reported in bulk studies.