Oxygen transfer processes in (La,Sr)MnO3/Y2O3-stabilized ZrO2 cathodes: an impedance spectroscopy study

Impedance spectroscopy was used to study the oxygen reaction kinetics of La_0.8Sr_0.2MnO₃ (LSM)-based electrodes on Y₂O₃-stabilized ZrO₂ (YSZ) electrolytes. Three types of electrodes were studied: pure LSM, LSM–YSZ composites, and LSM/LSM–YSZ bilayers. The electrodes were formed by spin coating and sintering on single-crystal YSZ substrates. Measurements were taken at temperatures ranging from 550 to 850°C and oxygen partial pressures from 1×10⁻³ to 1 atm. An arc whose resistance R_el had a high activation energy, E_a=1.61±0.05 eV, and a weak oxygen partial pressure dependence, (P_O2)^−1/6, was observed for the LSM electrodes. A similar arc was observed for LSM–YSZ electrodes, where R_el(P_O2)^−0.29 and the activation energy was 1.49±0.02 eV. The combination of a high activation energy and a weak P_O2 dependence was attributed to oxygen dissociation and adsorption rate-limiting steps for both types of electrodes. LSM–YSZ composite cathodes showed substantially lower overall interfacial resistance values than LSM, but exhibited an additional arc attributed to the resistance of YSZ grain boundaries within the LSM–YSZ. At 850°C and low P_O2, an additional arc was observed with size varying as (P_O2)^−0.80 for LSM and (P_O2)^−0.57 for LSM–YSZ, suggesting that diffusion had become an additional rate limiting step. Bilayer LSM/LSM–YSZ electrodes yielded results intermediate between LSM and LSM–YSZ. The results showed that most of the improvement in electrode performance was achieved for a LSM–YSZ layer only ≈2 μm thick. However, a decrease in the grain-boundary resistance would produce much better performance in thicker LSM–YSZ electrodes.     

Mixed conductivity in SrCe0.95Yb0.05O3 protonic conductors

The results of electrical conductivity measurements on SrCe_0.95Yb_0.05O₃ under controlled oxygen partial pressure and temperature are presented. A defect model consistent with experimental results is proposed which provides for P_O2^−1/4 dependent n-type, P_o2-independent oxygen ion and P_O2^+1/4 dependent p-type conductivity components. The band gap, reduction, oxidation and ion-migration energies are determined from an analysis of the data in terms of the proposed defect model. These results suggest that some earlier data interpreted in terms of protonic conduction may require re-evaluation.     

Ionic and electronic conductivity in lead–zirconate–titanate (PZT)

Accurate impedance measurements on differently sized samples of lead–zirconate–titanate (PbZr_0.53Ti_0.47O₃, PZT) have been analyzed with a CNLS procedure, resulting in the separation of the ionic and electronic conductivities over a temperature range from 150 to 630 °C. At 603 °C the electronic conductivity shows approximately a (P_O2)^1/4 dependence, while the ionic conductivity remains constant. Below the Curie transition temperature the oxygen non-stoichiometry becomes frozen-in and the conductivities are strongly dependent on the sample history with respect to temperature sequence and ambient P_O2. A tentative interpretation assumes defect association, i.e. formation of neutral [V_Pb–V_O^··]^× complexes, and electron-hole transfer between lead sites and lead vacancies to control the oxygen ion conductivity in the tetragonal phase.

Annealing PZT-based devices at about 600 °C under low oxygen pressure (1 Pa oxygen) effectively decreases the low temperature electronic conductivity by a factor of 100 and the ionic conductivity by a factor of 10–15 with respect to normal air processing.     

氧气后处理对氧化锌薄膜紫外发射性质的影响

为了提高ZnO光发射效率和制备p型ZnO,对热处理的氧分压对薄膜的结构、形貌、光致光发射和ZnO/Si异质结的Ⅰ-Ⅴ特性的影响进行了研究.用直流反应溅射法在p型硅衬底上生长ZnO薄膜形成n-ZnO/P-Si异质结.在1000℃下用不同比例的氧和氨热处理,我们发现,在纯氮气中得到的样品有强的紫外发射(390nm),随氧气比例增大,紫外增强,同时绿光也产生并随之增强.但过大的氧分压反而产生多的受主缺陷,使越来越多的激发能量转移到发射能量低的绿光中心,从而使紫外减弱.在纯氧和无氧条件下热处理的俄歇谱表明纯氧下氧过量,而无氧下锌大大过量.ZnO/p-Si异质结的Ⅰ-Ⅴ特性表明,无氧热处理表现为典型的n-ZnO/p-Si异质结;而在纯氧气氛中处理后所得Ⅰ-Ⅴ曲线反向,这表明在高氧压下受主缺陷的产生,表明ZnO薄膜有可能由于高氧压热处理由n型转为p型.     

On the Hebb–Wagner polarisation of SrTiO3 doped with redox-active ions

Hebb–Wagner polarisation is analysed for the case that internal redox-reactions complicate the situation. In the general case current–voltage characteristics deviate significantly from the Hebb–Wagner equation. Analytical results are derived and relevant approximations given. Theoretical and experimental current–voltage relations obtained for a 2.15×10¹⁸ cm⁻³ Fe-doped SrTiO₃ single crystal at P_O2=10⁵ Pa, agree reasonably well, and the results of the partial conductivities match findings obtained from other experiments. In addition, the fact is emphasised that a Hebb–Wagner-type current–voltage relation only requires the fulfilment of a power law for the non-blocked carrier concentrations with respect to the component partial pressure and not a field-free situation. In this case the Faraday constant appearing in the Hebb–Wagner equation has to be replaced by F, where is the product of the number of electrons necessary to ionise the gaseous component (n) times the absolute characteristic exponent (|N|). The condition of zero field, i.e. negligible chemical potential gradient with respect to the non-blocked species is identical to |N|=1/n. If |N|=const≠1/n, the internal field is non-zero but is still proportional to the gradient of the component potential.     

Computer-assisted analysis and calculation of phase diagrams of the Fe---Cr---O, Fe---Ni---O and Cr---Ni---O systems

Available thermodynamic and phase equilibrium data for the Fe---Cr---O, Fe---Ni---O and Cr---Ni---O systems are assessed and equations for the free energies of the phases as functions of composition and temperature are derived. With these mathematical expressions and with a computer program written for the purpose, phase diagram sections at constant temperature, or at constant log p_O2, or at constant P_co/P_co2 or p_H2/P_H2O ratios can be calculated at all compositions and over a wide range of temperature and oxygen potential. The representation and analysis of the phase equilibria are greatly facilitated through the use of isothermal log P_O2-composition phase diagrams which are discussed in some detail. Structural models for the spinel phases are examined.     

A study on the nonstoichiometry of tin oxides by coulometric titration

In this investigation, nonstoichiometries and defect structures of tin oxides were studied between 694 and 990 K by coulometric titration using solid state electrolyte (YSZ) cells. The relationship between nonstoichiometry of the oxide (x) and equilibrium oxygen partial pressure (P_o2) was expressed by the proportionality: xP_O2^−1/6. An intermediate oxide phase, Sn₃O₄ between Sn and SnO₂ was observed in the temperature range of 696–732 K. The standard Gibbs energy of formation of Sn₃O₄ via the reaction; was found to be ΔG^o_Sn3O4 = −1163960+417.36 T (J/mol). The standard Gibbs energy change for the defect formation reaction in SnO_2−x was calculated to be ΔG^o_SnO2−x = 3.05×10⁵−38.97 T (J/mol)).     

铥原子收敛于4f13(2F7/2o)6s(7/2,1/2)4o和4f13(2F7/2o)6s(7/2,1/2)3o偶宇称里德伯系列能级的电子关联效应

本文在多通道量子亏损理论框架下,利用相对论多通道理论,计算了铥原子收敛于4f¹³（²F_7/2^o）6s（7/2,1/2）₄^o和4f¹³（²F_7/2^o）6s（7/2,1/2）₃^o的三个偶宇称里德伯系列.通过将计算结果与美国国家标准与技术研究院数据进行比较,展示了两种类型的电子关联效应：1）里德伯系列之间的相互作用,导致里德伯系列的能级出现整体偏移;2）一个孤立的干扰态镶嵌在一个里德伯系列中,破坏了该里德伯系列能级的规则性.     

Reversible H2 passivation of Si ≡ Si3 interface defects in (1 1 1)Si/SiO2

K-band electron spin resonance (ESR) at 4.3 K has revealed the dipole-dipole (DD) interaction effects between [1 1 1]P_b centers (^*Si ≡ Si₃ defects with unpaired sp³ hybrid [1 1 1]) at the 2 dimensional (1 1 1)Si/SiO₂ interface. This has been enabled by the perfectly reversible H₂ passivation of P_b, which affects the defect's spin state. Sequential hydrogenation at 253–353°C and degassing treatments in high vacuum at 743–835°C allowed to vary the P_b density in the range 5 × 10¹⁰ < [P_b] (1.14 ± 0.06) × 10¹³ cm^-2. With increasing [P_b] fine structure doublets are clearly resolved. It is found that (1 1 1)Si/SiO₂ interfaces, dry thermally grown at ≈920°C, naturally comprise a ^*Si ≡ Si₃ defect density — passivated or not — of 1.14 × 10¹³ cm^-2.     

用同步辐射研究掺Tb3+氟化物K2GdF5的光谱和Gd3+-Tb3+能量传递

对比了不同激发波长下水热法合成的K2GdF5:Tb3+(摩尔分数0.5％)单晶材料的光致发光谱线;监测了5 D3→7F6和5 D4→7 F5的激发谱,给出了几组窄带吸收和3个宽带吸收;分析表明窄带发射为Gd3+的8 S7/2→6FJ、8S7/2→6GJ、8S7/2→6DJ、8S7/2→6IJ的跃迁,宽带发射为Gd3+的...     

Thermal-expansion anomalies and spontaneous magnetostriction of Lu2Fe17−xSix intermetallic compounds

The thermal expansion of Lu₂Fe_17−xSi_x solid solutions has been measured by X-ray powder diffraction. The magnetic ordering in all compounds within the homogeneity range (x3.4) is accompanied by a large spontaneous volume magnetostriction, distributed anisotropically over the principal axes of the hexagonal crystal structure. The volume effect ω_s in the ground state reaches 14.7×10⁻³ in Lu₂Fe₁₇ and decreases monotonously to 8.9×10⁻³ for x=3.4, following the reduction of magnetic moment. Despite a still large ω_s, the Invar behavior observed in Lu₂Fe₁₇ changes to a positive thermal expansion for x>1 due to an increasing Curie temperature.     

共掺杂Ce~(3+)调控β-NaLuF_4:Yb~(3+)/Ho~(3+)纳米晶体的上转换荧光发射

在980 nm近红外光激发下,通过共掺杂Ce~(3+)离子调控六方相NaLuF_4:Yb~(3+)/Ho~(3+)纳米晶体的上转换荧光发射.实验结果表明,当掺杂Ce~(3+)离子浓度从0增加到12.0%时,Ho~(3+)离子的上转换荧光发射实现了由绿光向红光的转变,其红绿比提高了近24倍.根据Ho~(3+)离子的能级结构发现,Ho~(3+)离子的红光发射源自~5F_5能级到5I8能级的辐射跃迁,因此要增强红光发射,必须提高该能级粒子数布居.Ho~(3+)与Ce~(3+)离子之间相近的能级差促使它们之间产生了共振交叉弛豫,从而有效地提高了Ho~(3+)离子~5F_5能级的粒子数布居,增强了红光发射.同时对Ho~(3+)离子的上转换调控机理进行讨论,并借助不同的激发策略,进一步证实了Ho~(3+)与Ce~(3+)离子之间相互作用的发生.     

High temperature transport processes in lithium niobate

The electrical conductivity of single crystal lithium niobate (LiNbO₃) was determined as a function of temperature for various oxygen partial pressures. The electrical conductivity is proportional to P_o2^−1/4 which can be explained by a defect equilibrium involving singly ionized oxygen vacancies and electrons.

Measurements of electrical transport numbers at 1000°K show the electrical conductivity of LiNbO₃ to be ionic at one atmosphere of oxygen and electronic at low oxygen partial pressures.

Thermoelectric measurements indicate that LiNbO₃ at low oxygen partial pressures is n-type and that the concentration of electrons at 1000°K and in an atmosphere of 50% C0/50% CO₂a is 4 × 10¹⁷cm³ with a mobility of 1.7 cm²V sec.

The diffusion of oxygen in LiNbO₃ was determined as a function of temperature at an oxygen partial pressure of 70 Torr. by measuring O¹⁸/O¹⁶ isotope exchange with the gas phase as a function of time. The diffusion data may be represented by D = 3.03 × 10⁻⁶ exp (−29.4 kcal mole⁻¹/RT)cm²sec. Consideration of the Nernst-Einstein relation for oxygen and the variation in conductivity with Li₂O activity indicate that the ionic conduction is caused by transport of lithium ions.     

Chemical diffusivity of BaTiO3−δ: I. Experimental determination

The chemical diffusivity of ‘undoped' polycrystalline BaTiO_3−δ was determined via a conductivity relaxation technique, at elevated temperatures (800≤T/°C≤1100) as a function of the ambient oxygen partial pressure in the range of 10⁻¹⁶≤P_O2/atm≤1 including an n- to p-type transition regime. Mathematical formulation was developed to convert conductivity relaxation to the corresponding nonstoichiometry (δ) relaxation in the transition regime. It has been found that the chemical diffusivity appears to exhibit a maximum at the n-to-p transition point where the electronic minimum conductivity falls, and that surface reaction becomes more rate-determining than diffusion as the transition point is approached from both n-type and p-type branches. Experimental details are given and the results are exhaustively compared with those reported up to date on the ‘undoped' BaTiO₃.     

Duree de vie et depolarisation par collisions avec l''helium des niveaux 5P3/2 Et 5P1/2 de l''ion Cd

The lifetimes of the Cd⁺ 5²P_3/2 and 5²P_1/2 states have been measured by the Hanle effect. The Cd⁺ ions are produced in a d.c. discharge in cadmium vapor, with helium as buffer gas. The results are: τ(5²P_3/2) = (2.60±0.20) ×10⁻⁹sec, and τ(5²P_1/2) = (3.05 ± 0.13) × 10⁻⁹sec.

We measured also the cross sections for the destruction of the orientation in the 5²P_1/2Cd⁺ state (<5Ų), of the orientation (18±10Ų) and of the alignment (46±10Ų) in the 5²P_3/2 state due to collisions with the helium atoms.     

Hydrogen depth profile measurement in a-Si1-xCx:H films by elastic recoil detection

The hydrogen content and depth profile in a-Si_1-xC_x:H films were measured by the elastic recoil detection (ERD) technique. It is shown that the hydrogen content changes from 15 to 50 at% with increasing carbon content x. For x<0.4 the hydrogen content increases mainly due to the increase of the Si-CH₃ contribution and for x > 0.4 due to C-H bonds. By combining the ERD and IR results, the proportionality between the number of Si-CH₃ bonds and the intensity of IR absorption due to the Si-CH₃ rocking mode vibration is ascertained. The proportionality constant is found to be A^roc_Si-CH3 = 5 × 10¹⁹ cm^-2.     

Structure determination, magnetic and optical properties of a new chromium(II) thioantimonate, [Cr((NH2CH2CH2)3N)]Sb4S7

The chromium(II) antimony(III) sulphide, [Cr((NH₂CH₂CH₂)₃N)]Sb₄S₇, was synthesised under solvothermal conditions from the reaction of Sb₂S₃, Cr and S dissolved in tris(2-aminoethyl)amine (tren) at 438 K. The products were characterised by single-crystal X-ray diffraction, elemental analysis, SQUID magnetometry and diffuse reflectance spectroscopy. The compound crystallises in the monoclinic space group P2₁/n with a=7.9756(7), b=10.5191(9), c=25.880(2) Å and β=90.864(5)°. Alternating SbS₃³⁻ trigonal pyramids and Sb₃S₆³⁻ semi-cubes generate Sb₄S₇²⁻ chains which are directly bonded to Cr(tren)²⁺ pendant units. The effective magnetic moment of 4.94(6)μ_B shows a negligible orbital contribution, in agreement with expectations for Cr(II):d⁴ in a ⁵A ground state. The measured band gap of 2.14(3) eV is consistent with a correlation between optical band gap and framework density that is established from analysis of a wide range of antimony sulphides.     

Features of the electrochemical lithium insertion into monophosphate tungsten bronzes (PO2)4(WO3)2m (m=9 and 10)

Electrochemical lithium insertion into (PO₂)₄(WO₃)_2m, where m=9 and 10, has allowed the determination of several phases Li_x(PO₂)₄(WO₃)_2m between 3.4 and 0.01 V vs Li⁺/Li⁰. After the first cycle the electrochemical system was unable to maintain the high specific capacity of the cells (540 Ah/kg) due to irreversible processes. Nevertheless at high voltage values, above 1.4 V vs Li⁺/Li⁰, the lithium insertion proceeded through a reversible mechanism. By means of X-ray diffraction experiments we have detected the nature of different phases Li_x(PO₂)₄(WO₃)_2m formed and we have established a correlation with the reversible/irreversible processes detected during the electrochemical insertion.     

Er3+/Yb3+共掺NaYF4/LiYF4微米晶体的上转换荧光特性

采用水热法成功制备了Er³⁺/Yb³⁺共掺杂的NaYF₄和LiYF₄微米晶体. 通过X射线衍射仪和环境扫描电子显微镜对样品的晶体结构及形貌进行表征. 实验结果表明: 六方相NaYF₄微米晶体为棒状结构, 而四方相LiYF₄微米晶体则为八面体结构. 在近红外光980 nm激发下, NaYF₄:Yb³⁺/Er³⁺和LiYF₄:Yb³⁺/Er³⁺ 微米晶体均展现出很强上转换荧光发射. 且NaYF₄:Yb³⁺/Er³⁺微米晶体的荧光发射强度大约是LiYF₄:Yb³⁺/Er³⁺微米晶体的2倍, 但红绿比明显较低. 根据荧光光谱, 并借助激光光谱学及发光动力学深入探讨基质变化及表面修饰剂乙二胺四乙二酸(EDTA)对荧光特性的影响. 实验结果发现: 影响荧光强度的主要因素是基质环境的局域对称性, 而导致不同红绿比则是由于样品表面较多的EDTA分子所引起. Er³⁺掺杂的NaYF₄和LiYF₄ 微米晶体呈现出很强的绿光发射可被应用于全色显示, 荧光粉和微光电子器件中.     

Electrical properties of ZrO2-In2O3-Y2O3 and its application to a membrane for gas separation

Electrical properties of In₂O₃-doped yttria-stabilized zirconia (In-YSZ) were investigated. The solubility limit of In₂O₃ in YSZ (10 mol% Y₂O₃) is 17.5 mol%. The total conductivity depended on the concentration of In₂O₃. The activation energy of In-YSZ was higher than that of YSZ. From the oxygen partial pressure (P_o2) dependence of the total conductivity of In-YSZ, the electronic conductivity increased with increasing In₂O₃ concentration at low oxygen partial pressures and at high temperature. From the results, we discussed the applicability of In-YSZ to a membrane for hydrogen production from direct water splitting at high temperature.