Bi2O3—Sb2O3二元系的研究

本文用 X 射线衍射及差热-热重分析方法研究了 Bi_2O_3-Sb_2O_3二元系在 N_2和空气中的相关系.研究结果表明,在 N_2中发生自氧化-还原化学反应5Bi_2O_3+3Sb_2O_3→4Bi+6BiSbO4在空气中 Bi 和 Sb 分别主要以+3和+5价的形式存在.Sb 在 Bi_2O_3中的溶解度不超过3mol%.形成三种化合物:Bi3SbO_7、Bi_5Sb_2O_(12.5)和 BiSbO_4.前两者为包品反应产物,后者为固液同份化合物.BiSbO_4的熔点为1276℃.BiSbO_4与Sb_2O_4属共晶反应.并讨论了Sb 对 Bi-Sr-Ca-Cu-O 体系形成超导相的影响.     

Eu3+掺杂Bi2O3-TeO2-B2O3-ZnO玻璃光谱性质

测量了Eu3+（1 mol%）掺杂(60-χ)Bi2O3-χ TeO2-30B2O3-10ZnO（χ＝5,10,20,30,摩尔百分比）玻璃的吸收光谱、发射光谱、激发光谱以及声子边带谱.根据稀土离子Eu3+光学跃起矩阵元的特点,从发射光谱获得了Eu3+光学跃起的J-O参数Ω2与Ω4.结果显示,强度参量Ω2随着Bi2O3量的增加与TeO2量的减少而减小,表明材料的对称性提高, Eu-O键强减弱,共价性减弱.随着Bi2O3量的增加,电－声子偶合减弱,材料的热稳定性大幅度提高.     

Study of electrical conductivity and phase transition in Bi2O3–V2O5 system

The solid solutions of bismuth–vanadate were prepared by the conventional solid-state reaction. The sample characterization and the study of phase transition were done by using FT-IR, X-ray diffraction (XRD) and DSC measurements. AC impedance measurements proved that the oxide ion conductivity predominantly arises from the grain and grain boundary contributions as two well-defined semicircles are clearly seen along with an inclined spike. The electrical conductivity of Bi₂O₃–V₂O₅ has been studied at different temperatures for various molar ratios. The isothermal conductivity increases with an increase in the concentration of V₂O₅ due to the vacancy migration phenomenon. It has been found that the conductivity of different compositions of Bi₂O₃–V₂O₅ increases and shows a jump in the temperature range 230–260°C due to the phase transition of BiVO₄ from monoclinic scheelite type to that of tetragonal scheelite type. The endothermic peak in DSC at around 260°C reveals the phase transition, which is also confirmed by the XRD and FT-IR analysis. The XRD patterns confirmed the monoclinic structure of BiVO₄.     

Current-voltage curves from a Bi2O3Y2O3 oxygen ion conductor

The solid ionic conductor cell Bi₂O₃Y₂O₃ was used to the current-voltage behaviour under different temperatures and voltage scan rate, as is usually done in cyclic voltammetry in three-electrode cells using liquid electrolytes. The result shows that the reactions are different at the electrodes and a hysteresis effect is presented at low temperatures and high voltage scanning rates.     

Superconducting energy gap in Bi2Sr2Ca2Cu3O10+δ (Bi2223) single crystals

Current-voltage characteristics of S-I-S tunnel break junctions fabricated from pure undoped Bi2223 single crystals (T _c =110 K) were measured. High quality of the crystals enabled production of good tunnel junctions with a low or almost zero leakage current and well developed gap structure in the tunneling spectra. The peak-to-peak energy gap values 2Δ_p-p in different crystals and the tunnel junctions ranged from 80 to 105 meV. The tunneling conductance in the superconducting state was normalized to that in the normal state and compared to a smeared BCS density of states. A simple fit of the data gave the average value of Δ=38.5 meV and reduced gap 2Δ/kT _c ?8, consistent with a very strong coupling mechanism.     

Electrical transport characteristics of ZnO–Bi2O3–B2O3 glasses

Optically clear glasses in the ZnO–Bi₂O₃–B₂O₃ (ZBBO) system were fabricated via the conventional melt-quenching technique. Dielectric constant and loss measurements carried out on ZBBO glasses unraveled nearly frequency (1 kHz–10 MHz)-independent dielectric characteristics associated with significantly low loss (D?=?0.004). However, weak temperature response was found with temperature coefficient of dielectric constant 18?±?4 ppm °C^?1 in the 35–250 °C temperature range. The conduction and relaxation phenomena were rationalized using universal AC conductivity power law and modulus formalism respectively. The activation energy for relaxation determined using imaginary parts of modulus peaks was 2.54 eV which was close to that of the DC conduction implying the involvement of similar energy barriers in both the processes. Stretched and power exponents were temperature dependent. The relaxation and conduction in these glasses were attributed to the hoping and migration of Bi³⁺ cations in their own and different local environment.     

Thermal dependence of conduction properties in the Bi2O3Pb2OF2 system

Conduction properties of bismuth-lead oxyfluorides (Bi,Pb)₂(O,F)₃ have been investigated by complex impedance analysis. A special attention has been drawn to a hexagonal solid solution Bi_(1−x)Pb_xO_(1.5−x)F_x (0.45⩽x⩽0.741 at 770 K), which is isostructural with ALa₂O₃. Conductivity values range from 3 × 10⁻⁵ to 3 × 10⁻² (ω cm)⁻¹ at 585 K. A minimum associated with a maximum in activation energy is observed for the composition x = 0.5 i.e. BiPbO₂F.     

Ultrasonic and FT-IR studies on Bi2O3–Er2O3–PbO glasses

Glasses in the 90Bi₂O₃–(10?x)Er₂O₃?xPbO (x = 3, 5, 7, 9 and 10 mol%) system have been prepared by the melt-quenching technique. Elastic properties and FT-IR spectroscopic studies have been employed to study the role of PbO in the structure of the investigated system. Elastic properties and Debye temperature were recorded using sound wave velocity measurements at 4 MHz at room temperature. The results showed that density increased and molar volume decreased, while both sound velocities increased with an increase in x. Infrared spectra of the glasses revealed that the bismuthate network is affected by an increase in PbO content. The results are interpreted in terms of the conversion of [BiO₆] into [BiO₃] structural units, indicating that Pb ions have been substituted for erbium ions as tetrahedral network formers. The elastic moduli increased with increasing PbO content due to the increased average bond strength and degree of connectivity, as a direct effect of the increase in [BiO₃] structural units.     

Broadband 1.5-μm emission of high erbium-doped Bi2O3–B2O3–Ga2O3 glasses

High Erbium-doped glass showing the wider 1.5-μm emission band is reported in the Bi₂O₃–B₂O₃–Ga₂O₃ system and its thermal stability and optical properties such as absorption, emission spectra, absorption and stimulated emission cross-sections and fluorescence lifetime are investigated. Compared with other glass hosts, the gain bandwidth properties of high Er³⁺ content in BBG glass are better than those of tellurite, germanate, silicate and phosphate glasses. The broad and flat ⁴I_13/2→⁴I_15/2 emission and the larger stimulated emission cross-section of Er³⁺ ions around 1.5 μm enable it to be used as a host material for potential broadband optical amplifiers at C and L bands in the microchip configuration.     

GeO2对Eu3+掺杂Bi2O3-B2O3-ZnO玻璃光谱性质的影响

用高温融熔法制备了Eu^3＋掺杂摩尔分数为1％的（60-X）Bi2O3-XGeO2-30B2O3-10ZnO（摩尔分数X=5,10,20,30）系统玻璃。测定了玻璃的差热分析曲线、发射光谱与激发光谱。从发射光谱与稀土Eu^3＋离子光学跃起矩阵元的特点,计算了Eu^3＋光学跃迁的参量Ω2与Ω1。结果显示强度参量Ω2与Ω4随着GeO2量的增加而增加,表明材料的对称性降低,Eu-O键强增加,共价性增加。玻璃的软化温度随GeO2组份的增加而提高。在GeO2摩尔分数达10％时．析晶起始温度与玻璃软化温度的差达最大,约146℃,表明该玻璃的热稳定性最好。     

The broadband NIR emission properties of Bi doped La2O3–Al2O3–SiO2 glass

Bi₂O₃ doped 65SiO₂–20Al₂O₃–15La₂O₃ (in mole%) glasses were prepared by the traditional melting–quenching method. The spectroscopic properties and mechanism of NIR broadband emission in these glasses were investigated in this work. Three excitation wavelengths of 500, 700 and 800 nm were used to test emission spectra. The emission band under 500 nm excitation can be regarded as combination of emission bands under 700 and 800 nm excitation. 2.0 mole% is found to be the optimal Bi₂O₃ doping level in this glass. Under 500 nm excitation its emission peak, FWHM and lifetime of emission band are 1160 nm, 300 nm and 569 μs, respectively. The longest fluorescent lifetime reaches 620 μs under 700 nm excitation. The valence state of Bi in these glasses is suggested to be lower than +3 by X-ray photoelectron spectroscopy. With the help of energy matching, we infer that both Bi⁰ and Bi⁺ centers are responsible for the NIR fluorescence of Bi₂O₃ doped 65SiO₂–20Al₂O₃–15La₂O₃ glass.     

Investigation of a high-temperature phase of 3Bi2O3·2TeO2 binary oxide

The high-temperature phase of 3Bi₂O₃·2TeO₂ binary oxide is characterized by thermal analysis, X-ray powder diffraction, and¹²⁵Te Mössbauer spectroscopy. The phase, obtained by rapid quenching from 900 °C, is identified to be cubic Bi₆Te₂O₁₃ with an oxygen-deficient fluorite structure, which is isomorphous with -Bi₂O₃.     

Spectroscopic Properties of Er3+/Yb3+-codoped PbO–Bi2O3–Ga2O3–GeO2 Glasses

We investigate the spectroscopic properties of the 1.5-μm emission from the ⁴I_13/2 → ⁴I_15/2 transition of Er³⁺ ions in PbO–Bi₂O₃–Ga₂O₃–GeO₂ glasses for applications in broadband fiber amplifiers. The measured emission peak locates at 1,532 nm with a full width at half-maximum of ∼45 nm. The glasses exhibit a large stimulated emission cross-section of 0.89 × 10⁻²⁰ cm² and a large product of 40.0. Infrared-to-green upconversion occurs simultaneously upon excitation of the 1.5-μm emission with a commercially available 980 nm laser diode. The green-upconversion intensity has a quadratic dependence on incident pump laser power, indicating a two-photon process. Energy transfer processes and nonradiative phonon-assisted decays could account for the population of the ²H_11/2 of Er³⁺. The results indicate the possibility towards the development of lead–bismuth–gallate–germanate based glasses as photonics devices.     

Luminescence and energy transfer in La2O3–Nb2O5–B2O3:M3+ (M=Bi,Eu, Dy) glasses

The luminescence and energy transfer processes in La₂O₃–Nb₂O₅–B₂O₃:M³⁺ (M=Bi, Eu, Dy) glasses were investigated using luminescence spectroscopy (excitation and emission, down to 4.2 K) and decay time measurements at room temperature. The observation of niobate luminescence implies a considerable degree of short- and intermediate-range order in these glasses. Energy transfer from the niobate groups to the lanthanide ions was observed for Eu³⁺, but not for Dy³⁺, suggesting that the energy transfer process occurs to the charge-transfer state of the Eu³⁺ ion, rather than to its f-levels. Inter-Eu³⁺ energy transfer was negligible in the concentration range investigated (up to 3 mol%). In contrast, cross-relaxation processes between Dy³⁺ ions were active at concentrations as low as 0.5 mol%. In the Bi³⁺ doped glasses the energy transfer was observed from the Bi³⁺ excited levels to the oxygen deficient niobate groups.     

Infrared absorption of O−H in thin films of hydrogenated Bi2Sr2CaCu2O8

Thin films of hydrogenated Bi₂Sr₂CaCu₂O₈ show three O–H vibrational absorption bands that shift upon deuteration with frequency ratiosv _O-H/v _O-D1.3, as expected for local modes. The band positions indicate that hydrogen atoms may be located at two different sites, namely in CuO₂ layers and, for the most part, in BiO double layers. The temperature dependences of these absorption bands give no hint of any direct interactions between the O–H vibrational modes and the superconducting phase transition.     

ВЛИЯНИЕ СТАРЕНИЯ НА Э ЛЕКТРИЧЕСКИЕ СВОЙСТ ВА ПОЛУПРОВОДНИКОВОЙ С ИСТЕМЫ Bi2Te3-Bi2Se3

, Bi₂Te₃-Bi₂Se₃. , , , . .

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Influence of ageing on change in electrical properties of semiconducting systems of Bi₂Te₃-Bi₂Se₃

The paper describes the effect of ageing observed on a semiconducting system Bi₂Te₃ — Bi₂Se₃. It is shown that the change in electrical conductivity and thermoelectric force, which takes place during ageing, is caused by the change in concentration of the free electrons. The influence of this process on the efficiency of equipment employing the Peltier effect is analyzed.

     

Asymmetric local displacements in the Bi2Sr2CaCu2O8+β superconductor

Instantaneous in-plane Cu-O bond distribution in the Bi₂Sr₂CaCu₂O_8+β (Bi2212) superconductor has been investigated by high k-resolution Cu K-edge extended X-ray absorption fine structure (EXAFS) measured with polarized vector parallel to the two orthogonal Cu-O-Cu bonds of the CuO₂ square plane. The results show an anisotropic Cu-O distribution in the two directions and provide further information on the local atomic displacements in the lattice-charge stripes. Received 5 June 2000