A new route for the synthesis of Mg2B2O5 nanorods by mechano-chemical and sintering process

Single crystalline Mg₂B₂O₅ nanorods have been synthesized by a two-step process involving the mechano-chemical technique and sintering method. Using MgCl₂·6H₂O and NaBH₄ powders as the starting materials, the mixture was firstly milled for 120 h, and then sintered at 800 °C for 2 h. The X-ray diffraction indicates the final product is monoclinic Mg₂B₂O₅. SEM and TEM results show that the Mg₂B₂O₅ is nanorod with the diameter about 200-400 nm and the length up to 5 μm. SAED analysis shows that the nanorod is single crystalline and twinned structure. The by-product NaCl is necessary for the formation of the single phase Mg₂B₂O₅.     

Mixed cation effect in xR2O-(40 − x)Na2O-50B2O3-10Bi2O3 (R = Li, K) glasses

Mass density, glass transition temperature and ionic conductivity are measured in xLi₂O-(40 − x)Na₂O-50B₂O₃-10Bi₂O₃ and xK₂O-(40 − x)Na₂O-50B₂O₃-10Bi₂O₃ glass systems with 0 ≤ x ≤ 40 mol%. The strength of the mixed alkali effect in T_g, dc electrical conductivity and activation energy has been determined in each glass system. The magnitudes of the mixed alkali effect in T_g for the mixed Li/Na glass system are much smaller than those in the mixed K/Na glasses. The impact of mixed alkali effect on dc electrical conductivity in mixed Li/Na glass system is more pronounced than in the K/Na glass system. The results are explained based on dynamic structure model.     

Melt growth and characterization of Mg2Si bulk crystals

We have grown Mg₂Si bulk crystals by the vertical Bridgman method using a high-purity Mg (6N-up) source. The grown crystals were single-phase Mg₂Si and had well-developed grains (1-5 mm³). Laue observations and SEM-EDX observations confirmed that crystalline quality in the grains was single crystal with stoichiometric composition. Electron concentration of the single crystalline specimens grown from 6N-up-Mg was 4.0 × 10¹⁵ cm^− 3 at room temperature (RT). This value is more than one order of magnitude lower than that of specimens grown from 4N-Mg [(5-7) × 10¹⁶ cm^− 3]. The Hall mobility of 14,500 cm²/Vs was observed at 45 K in the crystals grown from 6N-up-Mg. We also found that Al impurity plays an important role in the crystals grown from a low-purity Mg source. From the optical absorption measurement, we estimated that the indirect energy gap was about 0.66 eV at 300 K and about 0.74 eV at 4 K.     

Electrical conductivity and Hall mobility in p-type TlGaSe2 crystals

Systematic dark electrical conductivity and Hall mobility measurements have been carried out in the temperature range of 200-350 K on p-type TlGaSe₂ crystals. The analysis of the temperature-dependent electrical conductivity and carrier concentration reveals the extrinsic type of conduction with an acceptor impurity level located at 0.33 eV, and donor and acceptor concentrations of 9.0×10¹⁵ and 1.3×10¹⁶ cm⁻³, respectively. A hole and electron effective masses of 0.520m₀ and 0.325m₀, respectively, with a donor to acceptor compensating ratio of 0.69 are also being identified. The Hall mobility is found to be limited by the hole-phonon short-range interactions scattering with a hole-phonon coupling constant of 0.17.     

Microwave dielectric properties and microstructures of the 11Li2O-3Nb2O5-12TiO2 ceramics with B2O3 addition

The effects of B₂O₃ addition, as a sintering agent, on the sintering behavior, microstructure and microwave dielectric properties of the 11Li₂O-3Nb₂O₅-12TiO₂ (LNT) ceramics have been investigated. With the low-level doping of B₂O₃ (≤2 wt.%), the sintering temperature of the LNT ceramic could be effectively reduced to 900 °C. The B₂O₃-doped LNT ceramics are also composed of Li₂TiO₃ss and “M-phase” phases. No other phase could be observed in the 0.5-2 wt.% B₂O₃-doped ceramics sintered at 840-920 °C. The addition of B₂O₃ induced no obvious degradation in the microwave dielectric properties but increased the τ_f values. Typically, the 0.5 wt.% B₂O₃-doped ceramics sintered at 900 °C have better microwave dielectric properties of ?_r = 49.2, Q × f = 8839 GHz, τ_f = 57.6 ppm/°C, which suggest that the ceramics could be applied in multilayer microwave devices requiring low sintering temperatures.     

Single-step sputtered Cu2SnSe3 films using the targets composed of Cu2Se and SnSe2

Cu₂SnSe₃ thin films were prepared by single-step D.C. sputtering at 100-400 °C for 3 h using targets composed of Cu₂Se and SnSe₂ in three different ratios of 2/1 (target A), 1.8/1 (target B), and 1.6/1 (target C). The advantages of self-synthesized SnSe₂ instead of commercially available SnSe for depositing Cu₂SnSe₃ thin films were demonstrated. Effects of target composition and substrate temperature on the properties of Cu₂SnSe₃ thin films were investigated. Structure, surface morphology, composition, electrical and optical properties at different process conditions were measured. The 400 °C-sputtered films obtained from target B display with direct band gap of 0.76 eV, electrical resistivity of 0.12 Ω cm, absorption coefficient of 10⁴-10⁵ cm^− 1, carrier concentration of ∼ 1.8 × 10¹⁹ cm^− 3, and electrical mobility of 2.9 cm²/V s.     

Synthesis of non-stoichiometric Bi2O4−x by oxidative precipitation

Bi₂O_4−x, a Bi mixed-valence phase was prepared at 95 °C, by a precipitation process, in a basic medium with a highly oxidizing K₂S₂O₈/Na₂S₂O₈. This phase has a low thermal stability as it decomposes below 400 °C in a multiple step process by some O₂ losses prior to finally transforming into γ-Bi₂O₃. The as-prepared powders are 50-60 nm in size with a narrow size distribution. Optical spectra of Bi₂O_4−x exhibit a broad absorption band with a band gap of ∼1.4 eV as compared to 2.61 eV for Bi₂O₃. The composition of this non-stoichiometric phase, which crystallizes in cubic fluorite related structure with a cell parameter of 5.538(3) Å, is Bi₂O_{3.65 ± 0.10}.     

Optical properties of sputter deposited transparent and conducting TiO2:Nb films

Transparent and conducting thin films of TiO₂:Nb were prepared on glass by reactive dc magnetron sputtering in Ar + O₂. Post-deposition annealing in vacuum at 450 °C led to good electrical conductivity and optical transparency. The optical properties in the sub-bandgap region were in good agreement with Drude free electron theory, which accounts for intraband absorption. The band gap of the films was found to be in the range of 3.3 to 3.5 eV and signifies the onset of interband absorption. Electrical conductivities in the 10^− 3 Ω cm range were obtained both from dc electrical measurements and from analysis of the optical measurements.     

Temperature dependence of dielectric function and optical transitions in TlInSe2 and TlGaTe2

The principal components of the dielectric function of TlInSe₂ and TlGaTe₂ crystals with quasi-one-dimensional chain structure have been studied over the photon energies 1.5-5.0eV in the temperature range 140-400 K, with due regard to the reported phase transitions. For TlGaTe₂, the absolute values of the dielectric function experience a sudden temperature-induced change at 290 K in nearly all the accessed photon energy range. The energy and other parameters of the critical points for inter-band optical transitions related to the obtained dielectric function have then been retrieved for both TlInSe₂ and TlGaTe₂. An abrupt change in the energy of the critical point, positioned at 2.93 eV at room temperature and formed by optical transitions induced by the light polarized along the chains, has then been disclosed for TlGaTe₂ at 290 K.     

Green hydrothermal synthesis and optical absorption properties of ZnO2 nanocrystals and ZnO nanorods

A green hydrothermal method was proposed for the controllable synthesis of ZnO₂ nanocrystals and ZnO nanorods, using the common and cost-effective 2ZnCO₃·3Zn(OH)₂ powder and 30 mass% H₂O₂ aqueous solution as the raw materials. The characterization results from X-ray diffraction, high resolution transmission electron microscopy, transmission electron microscopy and energy dispersive X-ray spectroscopy indicated that the products synthesized at 100-120 °C for 6 h or at 170 °C for 0 h were cubic phase ZnO₂ nanocrystals; while those synthesized at 170 °C for 3-6 h were hexagonal phase ZnO nanorods. The UV-vis absorption spectra showed that the as-synthesized ZnO₂ nanocrystals and ZnO nanorods had optical band gaps of about 4.1 and 3.3 eV, respectively.     

Synthesis and Li ion conductivity of Li2O-Nb2O5-P2O5 glasses and glass-ceramics

Glasses with the compositions of xLi₂O-(70 − x)Nb₂O₅-30P₂O₅, x = 30-60, and their glass-ceramics are synthesized using a conventional melt-quenching method and heat treatments in an electric furnace, and Li⁺ ion conductivities of glasses and glass-ceramics are examined to clarify whether the glasses and glass-ceramics prepared have a potential as Li⁺ conductive electrolytes or not. The electrical conductivity (σ) of the glasses increases monotonously with increasing Li₂O content, and the glass of 60Li₂O-10Nb₂O₅-30P₂O₅ shows the value of σ = 2.35 × 10⁻⁶ S/cm at room temperature and the activation energy (E_a) of 0.48 eV for Li⁺ ion mobility in the temperature range of 25-200 °C. It is found that two kinds of the crystalline phases of Li₃PO₄ and NbPO₅ are formed in the crystallization of the glasses and the crystallization results in the decrease in Li⁺ ion conductivity in all samples, indicating that any high Li⁺ ion conducting crystalline phases have not been formed in the present glasses. 60Li₂O-10Nb₂O₅-30P₂O₅ glass shows a bulk nanocrystallization (Li₃PO₄ nanocrystals with a diameter of ∼70 nm) and the glass-ceramic obtained by a heat treatment at 544 °C for 3 h in air exhibits the values of σ = 1.23 × 10⁻⁷ S/cm at room temperature and E_a = 0.49 eV.     

Solution calorimetric study of mixing enthalpy in 0.8[xB2O3-(1 − x)SiO2]-0.2K2O glasses at 298 K

The mixing enthalpies in the 0.8[xB₂O₃-(1 − x)SiO₂]-0.2K₂O glassy system with 0 ≤ x ≤ 1 have been deduced from accurate calorimetric measurements of solution enthalpies in acidic solvent at 298 K. The substitution of SiO₂ by B₂O₃ corresponds to a negative enthalpic effect and suggests the absence of some glassy miscibility gap. The mixing enthalpies are of the same order of magnitude as mixing enthalpies usually found in molten salts.     

Preparation of VO2 nanowires and their electric characterization

Large-scale VO₂ nanowires have been synthesized by two-step method. First, we have been obtained (NH₄)_0.5V₂O₅ nanowire precursors by hydrothermal treatment of ammonium metavanadate solution at 170 °C. Secondly, the precursors have been sealed in quartz tube in vacuum and annealed to form VO₂ nanowires at 570 °C. Scanning electron microscope and transmission electron microscope analysis show that the nanowires have self-assembling nanostructure with the diameter of about 80-200 nm, length up to125 μm. Electrical transport measurements show that it is semiconductor with conduction activate energy of 0.128 eV. A metal-semiconductor transition can be observed around 341 K.     

Electrodeposition of As2Se3 thin films

Semiconducting As₂Se₃ thin films have been prepared from an aqueous bath at room temperature onto stainless steel and fluorine-doped tin oxide (F.T.O.)-coated glass substrates using an electrodeposition technique. It has been found that As₂O₃ and SeO₂ in the volumetric proportion as 4:6 and their equimolar solutions of 0.075 M concentration forms good quality films of As₂Se₃. The films are annealed in a nitrogen atmosphere at temperature of 200 °C for 2 h. The films are characterised by scanning electron microscopy, X-ray diffraction and optical absorption techniques. Studies reveal that asdeposited and annealed thin films are polycrystalline in nature. The optical band gap has been found to be 2.15 eV for the above-mentioned composition and concentration of the film.     

Formation of TiB2 by volume combustion and mechanochemical process

Titanium diboride was produced both by volume combustion synthesis (VCS) and by mechanochemical synthesis (MCP) through the reaction of TiO₂, B₂O₃ and Mg. VCS products, expected to be composed of TiB₂ and MgO, were found to contain also side products such as Mg₂TiO₄, Mg₃B₂O₆, MgB₂ and TiN. HCl leaching was applied to the reaction products with the objective of removing MgO and the side products. Formation of TiN could be prevented by conducting the VCS under an argon atmosphere. Mg₂TiO₄ did not form when 40% excess Mg was used. Wet ball milling of the products before leaching was found to be effective in removal of Mg₃B₂O₆ during leaching in 1 M HCl. When stoichiometric starting mixtures were used, all of the side products could be removed after wet ball milling in ethanol and leaching in 5 M HCl when pure TiB₂ was obtained with a molar yield of 30%. Pure TiB₂ could also be obtained at a molar yield of 45.6% by hot leaching of VCS products at 75 °C in 5 M HCl, omitting the wet ball milling step. By MCP, products containing only TiB₂ and MgO were obtained after 15 h of ball milling. Leaching in 0.5 M HCl for 3 min was found to be sufficient for elimination of MgO. Molar yield of TiB₂ was 89.6%, much higher than that of VCS. According to scanning electron microscope analyses, the TiB₂ produced had average grain size of 0.27 ± 0.08 μm.     

Physical properties of a new cuprate superconductor Pr2Ba4Cu7O15−δ

We present studies of the thermal, magnetic, and electrical transport properties of reduced polycrystalline Pr₂Ba₄Cu₇O_15−δ (Pr247) showing a superconducting transition at T_c=10-16 K, and compare them with those of as-sintered non-superconducting Pr247. The electrical resistivity in the normal state exhibited T² dependence up to approximately 150 K. A clear specific heat anomaly was observed at T_c for Pr247 reduced in a vacuum for 24 h, proving the bulk nature of the superconducting state. By the reduction treatment, the magnetic ordering temperature T_N of Pr moments decreased from 16 to 11 K, and the entropy associated with the ordering increased, while the effective paramagnetic moments obtained from the DC magnetic susceptibility varied from 2.72 to 3.13μ_B. The sign of Hall coefficient changed from positive to negative with decreasing temperature in the normal state of a superconducting Pr247, while that of the as-sintered one was positive down to 5 K. The electrical resistivity under high magnetic fields was found to exhibit T^α dependence (α=0.08-0.4) at low temperatures. A possibility of superconductivity in the so-called CuO double chains is discussed.     

Phase relations of the Li2O-Ta2O5-B2O3 and Li2O-WO3-B2O3 systems and promising nonlinear optical compounds in K2O-Ta2O5-B2O3 system

The subsolidus phase equilibria of the Li₂O-Ta₂O₅-B₂O₃, K₂O-Ta₂O₅-B₂O₃ and Li₂O-WO₃-B₂O₃ systems have been investigated mainly by means of the powder X-ray diffraction method. Two ternary compounds, KTaB₂O₆ and K₃Ta₃B₂O₁₂ were confirmed in the system K₂O-Ta₂O₅-B₂O₃. Crystal structure of compound KTaB₂O₆ has been refined from X-ray powder diffraction data using the Rietveld method. The compound crystallizes in the orthorhombic, space group Pmn2₁ (No. 31), with lattice parameters a = 7.3253(4) Å, b = 3.8402(2) Å, c = 9.3040(5) Å, z = 2 and D_calc = 4.283 g/cm³. The powder second harmonic generation (SHG) coefficients of KTaB₂O₆ and K₃Ta₃B₂O₁₂ were five times and two times as large as that of KH₂PO₄ (KDP), respectively.     

Highly stable nonlinear behavior against impulse current of ZnO-Pr6O11-CoO-Cr2O3-Y2O3 varistors

The nonlinear electrical behavior against the impulse stress (400-1200 A) in the ZnO-Pr₆O₁₁-CoO-Cr₂O₃-Y₂O₃ varistors has been investigated with sintering time. The sintering time did have a significant effect on the clamp ratio, which exhibits a surge protection capability. The varistors sintered for 1 h exhibited the best clamp characteristics, in which the clamp voltage ratio was in the range of K = 1.61-1.92 at a lower impulse current region (5-50 A) and was in the range of K = 2.06-2.55 at a higher single impulse current region (400-1200 A). The best electrical stability against the multi-impulse aging stress of 1200 A was also obtained from the varistors sintered for 2 h, where %ΔE_{1 mA} =−1.6%, %Δα =1.3%, and %ΔJ_L =−4.9%.     

Improved microwave dielectric properties of B2O3-doped Nd(Co1/2Ti1/2)O3 ceramics with near zero temperature coefficient of resonant frequency

The microwave dielectric properties and the microstructures of Nd(Co_1/2Ti_1/2)O₃ ceramics prepared by conventional solid-state route have been studied. The prepared Nd(Co_1/2Ti_1/2)O₃ exhibited a mixture of Co and Ti showing 1:1 order in the B-site. It is found that low-level doping of B₂O₃ (up to 0.75 wt.%) can significantly improve the density and dielectric properties of Nd(Co_1/2Ti_1/2)O₃ ceramics. Nd(Co_1/2Ti_1/2)O₃ ceramics with additives could be sintered to a theoretical density higher than 98.5% at 1320 °C. Second phases were not observed at the level of 0.25-0.75 wt.% B₂O₃ addition. The temperature coefficient of resonant frequency (τ_f) was not significantly affected, while the dielectric constants (?_r) and the unloaded quality factors Q were effectively promoted by B₂O₃ addition. At 1320 °C/4 h, Nd(Co_1/2Ti_1/2)O₃ ceramics with 0.75 wt.% B₂O₃ addition possesses a dielectric constant (?_r) of 27.2, a Q × f value of 153,000 GHz (at 9 GHz) and a temperature coefficient of resonant frequency (τ_f) of 0 ppm/°C. The B₂O₃-doped Nd(Co_1/2Ti_1/2)O₃ ceramics can find applications in microwave devices requiring low sintering temperature.     

Temperature shift of the optical gap in some PbO-ZnO-P2O5 glasses

The optical gap (E_g) between 4.54 eV-4.88 eV at room temperature was determined for PbO-ZnO-P₂O₅ glasses with the formal content of P₂O₅ in the region of 30 to 50 mol% and with the formal content of PbO in the region of 50 to 45 mol%, respectively. The temperature (T) dependence of the optical gap (E_g(T)) in the region 80 < T[K] < 600 was determined, and an electron-phonon interaction is suggested to be a major contribution to the temperature shift of the optical gap. In the temperature region of 300-600 K, the E_g(T) dependence can be approximated by a simple linear relation with the temperature coefficient (γ) of the optical gap in the region 6.04 ≤ γ × 10⁴ [eV/K] ≤ 7.39.