Structural and optical properties of (100 − x)(Li2B4O7) − x(SrO–Bi2O3–0.7Nb2O5–0.3V2O5) glasses and glass nanocrystal composites

Glasses of various compositions in the system (100 − x)(Li₂B₄O₇) − x(SrO–Bi₂O₃–0.7Nb₂O₅–0.3V₂O₅) (10  x  60, in molar ratio) were prepared by splat quenching technique. The glassy nature of the as-quenched samples was established by differential thermal analyses (DTA). The amorphous nature of the as-quenched glasses and crystallinity of glass nanocrystal composites were confirmed by X-ray powder diffraction studies. Glass composites comprising strontium bismuth niobate doped with vanadium (SrBi₂(Nb_0.7V_0.3)₂O_9−δ (SBVN)) nanocrystallites were obtained by controlled heat-treatment of the as-quenched glasses at 783 K for 6 h. High resolution transmission electron microscopy (HRTEM) of the glass nanocrystal composites (heat-treated at 783 K/6 h) confirm the presence of rod shaped crystallites of SBVN embedded in Li₂B₄O₇ glass matrix. The optical transmission spectra of these glasses and glass nanocrystal composites of various compositions were recorded in the wavelength range 190–900 nm. Various optical parameters such as optical band gap (E_opt), Urbach energy (ΔE), refractive index (n), optical dielectric constant and ratio of carrier concentration to the effective mass (N/m^*) were determined. The effects of composition of the glasses and glass nanocrystal composites on these parameters were studied.     

Nanocrystallization of SrBi2Nb2O9 from glasses in the system Li2B4O7---SrO---Bi2O3---Nb2O5

Transparent glasses in the system (100−x)Li₂B₄O₇–x(SrO---Bi₂O₃---Nb₂O₅) (10≤x≤60) (in molar ratio) were fabricated by a conventional melt-quenching technique. Amorphous and glassy characteristics of the as-quenched samples were established via X-ray powder diffraction (XRD) and differential thermal analyses (DTA) respectively. Glass–ceramics embedded with strontium bismuth niobate, SrBi₂Nb₂O₉ (SBN) nanocrystals were produced by heat-treating the as-quenched glasses at temperatures higher than 500 °C. Perovskite SBN phase formation through an intermediate fluorite phase in the glass matrix was confirmed by XRD and transmission electron microscopy (TEM). Infrared and Raman spectroscopic studies corroborate the observation of fluorite phase formation. The dielectric constant (_r) and the loss factor (D) for the lithium borate, Li₂B₄O₇ (LBO) glass comprising randomly oriented SBN nanocrystals were determined and compared with those predicted based on the various dielectric mixture rule formalism. The dielectric constant was found to increase with increasing SBN content in LBO glass matrix.     

Influence of rare-earth oxides on structure and crystallization properties of Bi2O3–B2O3 glass

Bi₂O₃·B₂O₃ glasses doped with rare-earth oxides (RE₂O₃) (RE³⁺ = La³⁺, Pr³⁺, Sm³⁺, Gd³⁺, Er³⁺ and Yb³⁺) were prepared by the melting–quenching method. The relationships between composition and properties were demonstrated by IR, DSC, XRD and SEM analysis. The results show that the network structure resembles that of undoped Bi₂O₃·B₂O₃ glass, composing of [BO₃], [BO₄] and [BiO₆] units. RE₂O₃ stabilizes the glass structure as a modifier. Transition temperature (T_g) increases linearly with cationic field strength (CFS) of RE³⁺. La₂O₃, Pr₂O₃, Sm₂O₃ and Gd₂O₃ are benefit to promote the formation of BiBO₃ crystal. When Er₂O₃ and Yb₂O₃ are introduced, respectively, the main crystal phase changes to Bi₆B₁₀O₂₄. Transparent surface crystallized samples are obtained by reheating at 460–540 °C for 5 h. In this case, needle like BiBO₃ crystal or rare-earth-doped BiBO₃ crystal (Pr_xBi_1−xBO₃ and Gd_xBi_1−xBO₃) are observed, which is promising for non-linear optical application.     

Fabrication and characterization of (1−x)SrBi2Ta2O9–xBi3TaTiO9 layered structure solid solution thin films for ferroelectric random access memory (FRAM) applications

We report on the properties of (1−x)SrBi₂Ta₂O₉–xBi₃TaTiO₉ solid solution thin films for ferroelectric non-volatile memory applications. The solid solution thin films fabricated by modified metalorganic solution deposition technique showed much improved properties compared to SrBi₂Ta₂O₉. A pyrochlore free crystalline phase was obtained at a low annealing temperature of 600°C and grain size was found to be considerably increased for the solid solution compositions. The film properties were found to be strongly dependent on the composition and annealing temperatures. The measured dielectric constant of the solid solution thin films was in the range 180–225 for films with 10–50% of Bi₃TaTiO₉ content in the solid solution. Ferroelectric properties of (1−x)SrBi₂Ta₂O₉–xBi₃TaTiO₉ thin films were significantly improved compared to SrBi₂Ta₂O₉. For example, the observed remanent polarization (2P_r) and coercive field (E_c) values for films with 0.7SrBi₂Ta₂O₉–0.3Bi₃TaTiO₉ composition, annealed at 650°C, were 12.4 μC/cm² and 80 kV/cm, respectively. The solid solution thin films showed less than 5% decay of the polarization charge after 10¹⁰ switching cycles and good memory retention characteristics after about 10⁶ s of memory retention. The improved microstructural and ferroelectric properties of (1−x)SrBi₂Ta₂O₉–xBi₃TaTiO₉ thin films compared to SrBi₂Ta₂O₉, especially at lower annealing temperatures, suggest their suitability for high density FRAM applications.     

Bi2O3助熔剂对CaO-B2O3-SiO2/Al2O3玻璃陶瓷复合材料性能的影响

以CaO-B₂O₃-SiO₂(CBS)玻璃粉体和Al₂O₃陶瓷粉体为原料,通过在CBS与Al₂O₃的质量比固定为50:50的玻璃-陶瓷复合材料中添加适量的Bi₂O₃作为烧结助熔剂,探讨了Bi₂O₃助熔剂对CBS/Al₂O₃复合材料的烧结性能、介电性能、抗弯强度和热膨胀系数的影响规律.研究表明:Bi₂O₃助熔剂能通过降低CBS玻璃的转变温度和黏度促进CBS/Al₂O₃复合材料的致密化进程,于880 ℃下烧结即能获得结构较致密、气孔较少的CBS/Al₂O₃复合材料.然而,过量添加Bi₂O₃将使玻璃的黏度过低,从而恶化CBS/Al₂O₃复合材料的烧结性能、介电性能及抗弯强度.当Bi₂O₃的添加量为CBS/Al₂O₃复合材料的1.5wt%时,于880 ℃下烧结即能获得最为致密的CBS/Al₂O₃复合材料,密度为2.82 g·cm^-3,这一材料具有良好的介电性能(介电常数为7.21,介电损耗为1.06×10^-3),抗弯强度为190.34 MPa,0~300 ℃的热膨胀系数为3.52×10^-6 K^-1.     

Infrared optical properties of Bi2Ti2O7 thin films by spectroscopic ellipsometry

Bi₂Ti₂O₇ thin films have been grown directly on n-type GaAs (1 0 0) by the chemical solution decomposition technique. X-ray diffraction analysis shows that the Bi₂Ti₂O₇ thin films are polycrystalline. The optical properties of the thin films are investigated using infrared spectroscopic ellipsometry (3.0–12.5 μm). By fitting the measured ellipsometric parameter (Ψ and Δ) data with a three-phase model (air/Bi₂Ti₂O₇/GaAs), and Lorentz–Drude dispersion relation, the optical constants and thickness of the thin films have been obtained simultaneously. The refractive index and extinction coefficient increase with increasing wavelength. The fitted plasma frequency ω_p is 1.64×10¹⁴ Hz, and the electron collision frequency γ is 1.05×10¹⁴ Hz, and it states that the electron average scattering time is 0.95×10⁻¹⁴ s. The absorption coefficient variation with respect to increasing wavelength has been obtained.     

Influence of Mn doping on microstructure and DC-accelerated aging behaviors of ZnO–V2O5-based varistors

The microstructure, electrical properties, dielectric characteristics, and DC-accelerated aging behavior of the ZnO–V₂O₅–MnO₂ system sintered were investigated for MnO₂ content of 0.0–2.0 mol% by sintering at 900 °C. For all samples, the microstructure of the ZnO–V₂O₅–MnO₂ system consisted of mainly ZnO grain and secondary phase Zn₃(VO₄)₂. The incorporation of MnO₂ to the ZnO–V₂O₅ system was found to restrict the abnormal grain growth of ZnO. The nonlinear properties and stability against DC-accelerated aging stress improved with the increase of MnO₂ content. The ZnO–V₂O₅–MnO₂ system added with MnO₂ content of 2.0 mol% exhibited not only a high nonlinearity, in which the nonlinear coefficient is 27.2 and the leakage current density is 0.17 mA/cm², but also a good stability, in which %ΔE_1 mA = −0.6%, %Δ = −26.1%, and %Δtan δ = +22% for DC-accelerated aging stress of 0.85E_1 mA/85 °C/24 h.     

Determining crystallization kinetic parameters of Li2O–Al2O3–SiO2 glass from derivative differential thermal analysis curves

The kinetic parameters such as crystallization activation energy, E, and the frequency factor, ν, of Li₂O–Al₂O₃–SiO₂ glass were determined by a new non-isothermal method. The method is described by the equation

Full-size image

, where β is the heating rate and T_f is the inflection-point temperature of differential thermal analysis (DTA). The value of T_f is determined as the maximum peak temperature on derivative differential thermal analysis (DDTA) curves. Values of E and ν of Li₂O–Al₂O₃–SiO₂ glass were also determined by two existing non-isothermal methods, namely the Kissinger plot and the Ozawa plot, and compared with those determined by isothermal method. Values of E and ν determined by the proposed equation were 332 kJ/mol and 1.4×10¹³ s⁻¹, respectively. They are excellent agreement with the isothermal analysis results, 336 kJ/mol and 1.8×10¹³ s⁻¹, respectively. In contrast, both the Kissinger equation and the Ozawa equation give much higher values of E and ν.     

Effect of radiation trapping on the emission properties of Er: I13/2 → I15/2 transition in oxide glasses

The effect of radiation trapping on the emission properties of Er³⁺-doped tellurite and phosphate glasses has been investigated as the function of sample thickness and doping concentration. It was found that radiation trapping exists generally in two glass matrices, even at low doping concentration (0.1 mol% Er₂O₃). The larger effect of radiation trapping in tellurite glasses compared with phosphate glasses is due to its larger emission cross-section at 1.5 μm band and the spectral overlap between the emission and absorption spectra of Er³⁺: ⁴I_13/2 ↔ ⁴I_15/2transition. Due to radiation trapping, the measured lifetime of the Er³⁺: ⁴I_13/2 level in tellurite glasses increases by about 11–37% with increasing the sample thickness at the different erbium doping concentration, while 6–17% for phosphate glasses. And the full-width at half maximum of fluorescence (FWHM) of Er³⁺: ⁴I_13/2 → ⁴I_15/2 transition in tellurite glasses increased by about 15–64% with increasing the sample thickness, while 11–55% for phosphate glasses. It caused a high overestimation on the figure of merits (FOM) for amplifier bandwidth (σ_e × FWHM).     

Low-temperature ionic conductivity of the solid solution in the system ZrO2–Y2O3–Yb2O3

Compositional dependence of ionic conductivity in the system ZrO₂–Y₂O₃–Yb₂O₃ was investigated in the temperature range 573–873 K using the complex impedance technique. It was shown that the conductivity decreases with increasing concentration of Yb₂O₃ in the system ZrO₂–Y₂O₃–Yb₂O₃. Analyzing the experimental data according to the classic Arrhenius equation showed that such an experimental phenomenon can be attributed to the tighter association between Yb³⁺ and oxygen vacancy, compared with that between Y³⁺ and oxygen vacancy, which hinders the migration of oxygen vacancy in the materials.     

Synthesis, phase transformation and dielectric properties of sol–gel derived Bi2Ti2O7 ceramics

Sol–gel derived Bi₂Ti₂O₇ ceramic powders have been prepared from methoxyethoxides of bismuth and titanium (molar ratio of Ti/Bi = 1.23 and water/alkoxides = 1.31). The Bi₂Ti₂O₇ phase was stable at a low temperature (700 °C), but it then transformed into mixed phases of Bi₄Ti₃O₁₂ and Bi₂Ti₄O₁₁ at 850–1150 °C. The single phase of Bi₂Ti₂O₇ reoccurred at 1200 °C. Dielectric properties and ferroelectric behavior of samples sintered at 1150 and 1200 °C were examined. Under frequency of 1 MHz, samples sintered at 1150 and 1200 °C had a dielectric constant of 101.3 and 104.2, and a loss tangent of 0.0193 and 0.0145, respectively. Only the sample sintered at 1150 °C showed ferroelectric behavior, where remanent polarization is 3.77 μC cm⁻² and coercive field is 24 kV cm⁻¹. Thus, the Bi₂Ti₂O₇ did not exhibit ferroelectricity, but the mixed phase of Bi₄Ti₃O₁₂ and Bi₂Ti₄O₁₁ did.     

Photoinduced nonlinear optics in Sb2Se3–BaCl2–PbCl2 glasses

Photoinduced structural transformations in amorphous Sb₂Se₃–BaCl₂–PbCl₂ glasses were studied using a differential IR spectroscopy Fourier technique in the spectral region between 100 and 300 cm⁻¹. A stage of the reversible photodarkening is realized in the Sb₂Se₃ fragments after the first cycle of photoexposure and thermoannealing. The whole scheme of the photo- and thermoinduced transformations in the amorphous system may be explained as a coordination of formation and annihilation of defects. The vibrational density of states calculated using quantum chemical solid state methods confirms our experimental results and their interpretation. Photoinduced photodarkening changes using a CO₂ pulse laser (λ=10.6 μm) in new synthesized Sb₂Se₃–BaCl₂–PbCl₂ glasses were investigated. At the same time we have studied photoinduced second harmonic generation (SHG) and two-photon absorption (TPA). The possibility of using this glass as perspective materials for IR optoelectronics and nonlinear optics was shown.     

Highly stable persistent spectral hole burning in Eu ions doped oxy-fluoride glasses of 30CaF2–10Al2O3–60B2O3

High temperature persistent spectral hole burning up to room temperature has been observed in Eu³⁺ ions doped oxy-fluoride glasses with a composition of 30CaF₂–10Al₂O₃–60B₂O₃ (mol%) melted in a reducing atmosphere. The hole stability was studied through light-induced hole refilling and temperature cycling experiments. The burned holes survive thermal cycling to 300 K due to a high barrier height of 0.69 eV in the sample.     

Microwave dielectric characteristics of Ba(Mg1/3Ta2/3)O3 ceramics sintered at low-temperatures

The microwave dielectric properties and microstructures of Ba(Mg_1/3Ta_2/3)O₃ (BMT) ceramics sintered at low temperatures with 2–3 wt.% NaF additives were investigated. BMT ceramics sintered at 1340 °C for 3–12 h showed dielectric constants (_r) of 25.5–25.7, Qf values of 41 500–50 400 GHz and temperature coefficients of the resonator frequency (τ_f) of 10.9–21.4 ppm °C⁻¹. The variation of sintering time almost had no effect on the dielectric constant. The Qf value increased and the τ_f decreased with increasing sintering time. The ordering degree of Mg²⁺ and Ta⁵⁺ at B-sites increased with increasing sintering time.     

Optical band gap studies on xPb3O4–(1−x)P2O5 lead[(II, IV)] phosphate glasses

A series of glasses in the xPb₃O₄–(1−x)P₂O₅ (red lead phosphate) (RLP) system with ‘x' varying from 0.075 to 0.4 were prepared by the single-step melt quenching process from Pb₃O₄ and NH₄H₂PO₄. The optical absorption spectra of these glasses have been recorded in the ultraviolet region from 200 to 400 nm and the fundamental absorption edges have been identified. The optical band gap E_opt values have been determined for all the glasses using the known theories. The (E_opt) values vary from 4.90 to 3.21 eV the highest being 4.57 eV, corresponding to the most stable glass of x=0.225. The absorption edge is attributed to the indirect transitions and the origin of the Urbach energy ΔE is suggested to be thermal vibrations. These glasses promise as potential candidates for application in optical technology compared to simple xPbO–(1−x)P₂O₅ (lead phosphate) (LP) glasses.     

Sintering behavior and microwave dielectric properties of Bi3(Nb1−xTax)O7 solid solutions

Solid solutions of Bi₃(Nb_1−xTa_x)O₇ (x = 0.0, 0.3, 0.7, 1) were synthesized using solid state reaction method and their microwave dielectric properties were first reported. Pure phase of fluorite-type could be obtained after calcined at 700 °C (2 h)⁻¹ between 0 ≤ x ≤ 1 and Bi₃(Nb_1−xTa_x)O₇ ceramics could be well densified below 990 °C. As x increased from 0.0 to 1.0, saturated density of Bi₃(Nb_1−xTa_x)O₇ ceramics increased from 8.2 to 9.1 g cm⁻³, microwave permittivity decreased from 95 to 65 while Q_f values increasing from 230 to 560 GHz. Substitution of Ta for Nb modified temperature coefficient of resonant frequency τ_f from −113 ppm °C⁻¹ of Bi₃NbO₇ to −70 ppm °C⁻¹ of Bi₃TaO₇. Microwave permittivity, Q_f values and τ_f values were found to correlate strongly with the structure parameters of fluorite solid solutions and the correlation between them was discussed in detail. Considering the low densified temperature and good microwave dielectric proprieties, solid solutions of Bi₃(Nb_1−xTa_x)O₇ ceramics could be a good candidate for low temperature co-fired ceramics application.     

New transparent conducting MgIn2O4---Zn2In2O5 thin films prepared by magnetron sputtering

New materials for a transparent conducting oxide film are demonstrated. Highly transparent Zn₂In₂O₅ films with a resistivity of 3.9 × 10⁻⁴ Ω cm were prepared on substrates at room temperature using a pseudobinary compound powder target composed of ZnO (50 mol.%) and In₂O₃ (50 mol.%) by r.f. magnetron sputtering. MgIn₂O₄---Zn₂In₂O₅ films were prepared using MgIn₂O₄ targets with a ZnO content of 0–100 wt.%. The resistivity of the deposited films gradually decreased from 2 × 10⁻³ to 3.9 × 10⁻⁴ Ω cm as the Zn/(Mg + Zn) atomic ratio introduced into the films was increased. The greatest transparency was obtained in a MgIn₂O₄ film. The optical absorption edge of the films decreased as the Zn/(Mg + Zn) atomic ratio was increased, corresponding to the bandgap energy of their materials. It was found that the resistance of the undoped Zn₂In₂O₅ films was more stable than either the undoped MgIn₂O₄, ZnO or In₂O₃ films in oxidizing environments at high temperatures.     

Microstructure and piezoelectric properties of (Na0.5K0.5)NbO3 lead-free piezoelectric ceramics with V2O5 addition

Various amounts of Nb₂O₅ in the (Na_0.5K_0.5) NbO₃ (NKN) ceramic were replaced by V₂O₅ to decrease its sintering temperature to below 950°C. A small V₂O₅ content resulted in a dense microstructure with an increased grain size for the specimen sintered at 900°C due to the presence of a liquid phase. When V₂O₅ was added to the NKN ceramics, their orthorhombic-to-tetragonal transition temperature increased from 178°C to around 200°C. However, their Curie temperature decreased from 402°C to around 330°C. The k_p, _ε3 ^T/_ε0, and Q_m values increased with V₂O₅ addition, probably due to the increased density and poling state, which was identified by the phase angle. The specimen with x = 0.05, sintered at 900°C for 8 h, exhibited the following piezoelectric properties: k_p = 0.32, _ε3 ^T/_ε0 = 245, d₃₃ = 120 (pC/N), and Q_m = 232.     

Microstructures, densification and mechanical properties of TiC–Al2O3–Al composite by field-activated combustion synthesis

Dense TiC–Al₂O₃–Al composite was prepared with Al, C and TiO₂ powders by means of electric field-activated combustion synthesis and infiltration of the molten metal (here Al) into the synthesized TiC–Al₂O₃ ceramic. An external electric field can effectively improve the adiabatic combustion temperature of the reactive system and overcome the thermodynamic limitation of reaction with x < 10 mol. Thereby, it can induce a self-sustaining combustion synthesis process. During the formation of Al₂O₃–TiC–Al composite, Al is molten first, and reacted with TiO₂ to form Al₂O₃, followed by the formation of TiC through the reaction between the displaced Ti and C. Highly dense TiC–Al₂O₃–Al with relative density of up to 92.5% was directly fabricated with the application of a 14 mol excess Al content and a 25 V cm⁻¹ field strength, in which TiC and Al₂O₃ particles possess fine-structured sizes of 0.2–1.0 μm, with uniform distribution in metal Al. The hardness, bending strength and fracture toughness of the synthesized TiC–Al₂O₃–Al composite are 56.5 GPa, 531 MPa and 10.96 MPa m^1/2, respectively.     

Effect of Al2O3 particles on mechanical properties of directionally solidified intermetallic Ti–46Al–2W–0.5Si alloy

The effect of Al₂O₃ particles on microhardness and room-temperature compression properties of directionally solidified (DS) intermetallic Ti–46Al–2W–0.5Si (at.%) alloy was studied. The ingots with various volume fractions of Al₂O₃ particles and mean ₂–₂ interlamellar spacings were prepared by directional solidification at constant growth rates ranging from 2.78×10⁻⁶ to 1.18×10⁻⁴ ms⁻¹ in alumina moulds. The ingots with constant volume fraction of Al₂O₃ particles and various mean interlamellar spacings were prepared by directional solidification at a growth rate of 1.18×10⁻⁴ ms⁻¹ and subsequent solution annealing followed by cooling at constant rates varying between 0.078 and 1.889 K s⁻¹. The mean ₂–₂ interlamellar spacing λ for both DS and heat-treated (HT) ingots decreased with increasing cooling rate according to the relationship λ∝ ^−0.46. In DS ingots, microhardness, ultimate compression strength, yield strength and plastic deformation to fracture increased with increasing cooling rate. In HT ingots, microhardness and yield strength increased and ultimate compression strength and plastic deformation to fracture decreased with increasing cooling rate. The yield stress increased with decreasing interlamellar spacing and increasing volume fraction of Al₂O₃ particles. A linear relationship between the Vickers microhardness and yield stress was found for both DS and HT ingots. A simple model including the effect of interlamellar spacing and increasing volume fraction of Al₂O₃ particles was proposed for the prediction of the yield stress.