水系电解质离子对无定形WO3电致变色性能的影响

WO₃是理想的无机电致变色材料,其电致变色机制是在电压作用下发生可逆的氧化还原反应,并伴随着电解质离子在材料内部的嵌入和脱出。本文研究了含有Li⁺、Zn²⁺、Al³⁺的三种水系电解质对无定形WO₃电致变色性能的影响。结果表明,当以Al³⁺作为嵌入离子时,WO₃获得了最好的电致变色性能,包括快响应速度(着色响应时间2.8 s,褪色响应时间1.1 s)、大光学对比度(700 nm处达83.4%)、优异的循环稳定性(连续循环1 000次仅衰减2.8%)、高着色效率(74.7 cm²·C^-1),其综合性能在已报道的WO₃电致变色器件中处于较高水平。机制研究发现,Al³⁺水系电解质溶液中性能的提升得益于快速的离子传输动力学。这些结果将为高性能电致变色器件构建和电解质优选提供简单有效的指导。     

MeV氢微团簇离子与固体介质的电荷交换

利用静电加速器提供的0.6—1.8MeV的H⁺，H⁺₂，H⁺₃离子，轰击不同厚度的碳膜，分别测量这些离子通过碳膜后各种产物的产额. 得到了不同能量的H⁺通过碳膜后中性原子H和负离子H^-的产额随入射质子速度的变化关系；分别得到能量为1.2MeV,1.8MeV的H⁺₂，H⁺₃团簇离子通过不同厚度碳膜的透射产额及其与团簇离子在碳膜中驻留时间的关系；对结果进行了理论分析与讨论. 关键词： 团簇离子 电荷交换     

4HeH+核间距的实验测定

用MeV量级⁴HeH⁺在超薄无衬碳膜中的库仑爆炸,获得高频离子源产生⁴HeH⁺核间距的实测值为0.094±0.003nm.发现⁴HeH⁺与H⁺₂,H⁺₃不一样,其核间距大小和离子源种类及离子源参数有密切关系,并从⁴HeH⁺的形成机理与形成条件,解 关键词：     

γ-Fe2O3中的氢含量

利用热中子透射法测定γ-Fe₂O₃的氢含量。利用差热分析、磁分析以及穆斯堡尔效应研究γ-Fe₂O₃的相变,实验结果表明在γ-Fe₂O₃结构中确实含有一定量的氢,当γ-Fe₂O₃结构中的阳离子空位被H¹⁺,Co²⁺,Si⁴⁺,P⁵⁺等离子占据时,将 关键词：     

H+2，H+3团簇离子在沟道条件下的背散射 质子产额测量

采用卢瑟福背散射方法，测得了每质子能量为650 keV的H⁺₂，H+₃团簇离子在Si晶体<100>和<110>沟道条件下的质子背散射能谱.结果发现，由于H⁺₂，H⁺₃团簇在晶体中的库仑爆炸和团簇效应，H⁺₂的背散射质子产额大于H ⁺的背散射产额，而H^{+< 关键词： 团簇 沟道效应 库仑爆炸 背散射}     

Ni2+:BeAl2O4晶体发光性质的研究

用时间分辨的激光诱导荧光光谱方法测量了10—300K温度范围内Ni²⁺:BeAl₂O₄晶体的红外荧光光谱和荧光寿命。通过荧光寿命的温度变化特性分析,得出³T_2g态的内禀辐射衰减寿命为123±7.2μs。无辐射弛豫的Mott激活能为1147cm^-1,并导出了此晶体发光量子效率随温度的变化关系式。Ni²⁺:BeAl₂O_{4关键词：}     

掺杂晶体材料Al2O3∶Ni2+中顺磁离子N2+局域结构及其电子顺磁共振参量的研究

按照叠加模型和微扰理论,建立了电子顺磁共振（EPR）参量（D, g_∥, g_⊥）与Al_2O3∶Ni²⁺晶体局域结构之间的定量关系. 利用EPR参量决定了Al₂O₃∶N i²⁺晶体的局域结构. 通过考虑适当的晶格畸变,成功地解释了Al₂O₃∶Ni²⁺晶体基态很大的零场分裂和各向异性的g因子. 获得了Ni²⁺ 离子上方最近邻的三个O^2-离子偏向111〕晶轴0.603°, 而Ni²⁺离子下方的三个O^2-离子偏向〔111〕晶轴0.598°.     

WO3表面的氧缺陷

用不同能量的Ar⁺和H⁺轰击WO₃表面,观察到W_4f峰的位移和加宽。通过谱分解处理得到相应于W_4f电子的W⁶⁺,W⁴⁺和W⁰3个不同的双峰。用表面产生氧缺陷的机理解释了还原过程。UPS谱显示出氧缺陷的存在增加了靠近费密能级处的态密度。H₂O的吸附结果说明WO₃表面的活性与W^{5+< 关键词：}     

氯化氢共振多光子电离光谱：F1Δ2态的光谱微扰分析

通过共振多光子电离-飞行时间法, 记录了氯化氢分子在84800-85700 cm^-1范围内, F¹Δ₂ (v’=1) 里德堡态以及V¹∑⁺ (v’=13, 14) 离子对态的电离产物H⁺, ³⁵Cl⁺, H³⁵Cl⁺ 及其同位素的光谱数据. 由于受离子对态V¹∑⁺ 的作用, F¹Δ₂ (v’=1)态呈现出明显的近共振相互作用特性. 为了分析F¹Δ₂与V¹∑⁺态之间存在的光谱微扰, 基于光解离电离通道的分析, 并针对F¹Δ₂ (v’=1)态离子信号比的变化, 将离子信号二能级作用模型优化到三能级的作用模型, 计算得到了微扰强度值为0.6 cm^-1, 预解离系数γ为0.025. 此外, 对于F¹Δ₂ (v’=1) 与V¹∑⁺ (v’=13, 14)态的三个振动能级的光谱峰位置, 采用光谱解微扰法拟合, 同样得到了类似的微扰强度和去微扰后的各光谱参数. 研究表明, 激发至F¹Δ₂ (v’=1)态得到的H⁺, Cl⁺ 离子主要是该态通过与离子对态耦合作用而产生, 而F¹Δ₂ (v’=1) 态光谱位置偏移不仅受离子对态而且还受其他里德堡态作用的影响. 同时, 非零γ 值证实了F¹Δ₂态预解离的存在. 关键词： 光解离电离 里德堡态 离子对态 光谱微扰     

30 keV H+在聚碳酸酯微孔膜中动态输运过程的实验和理论研究

测量了30 keV的H⁺入射倾斜角度为-1°和-2°的聚碳酸酯微孔膜后,出射粒子二维分布图、角度分布、相对穿透率以及出射H⁺电荷态纯度随沉积电荷的演化.实验中30 keV的H⁺在微孔膜中输运特性与之前其他能区离子在微孔膜中输运特性有显著不同,实验中直接观测到出射粒子导向部分和散射部分的动态演化过程,出射的H⁺由沿微孔孔轴方向的导向H⁺和沿入射束流方向的散射H⁺两部分组成,随着微孔内电荷斑的沉积,出射的导向H⁺的占比不断减小,出射散射H⁺占比不断增加;出射H⁰占总出射粒子的比例不断减小,其中心方向逐步向入射束流方向偏转.微孔膜处于不同倾斜角度时,微孔内沉积电荷斑的位置和电场强度是不同的.同时模拟计算了入射H⁺在微孔内部的运动轨迹、微孔内部电荷斑电势和场强分布,实验结果和理论结果得到了很好的验证.对出射离子导向部分和散射部分的动态演化过程的观测和理论解释,使得对中能区离子在微孔膜中输运机制有更好的认识.     

Effects of nickel doping on structural and optical properties of spinel lithium manganate thin films

Spinel LiNi_xMn_2−xO₄ (x≤0.9) thin films were synthesized by a sol-gel method employing spin-coating. The Ni-doped films were found to maintain cubic structure at low x but to exhibit a phase transition to tetragonal structure for x≥0.6. Such cubic-tetragonal phase transition can be explained in terms of Ni³⁺(d⁷) ions with low-spin (t_2g⁶,e_g¹) configuration occupying the octahedral sites of the compound, thus being subject to the Jahn-Teller effect. By X-ray photoelectron spectroscopy both Ni³⁺ and Ni²⁺ ions were detected where Ni²⁺ is more populated than Ni³⁺. Optical properties of the LiNi_xMn_2−xO₄ films were investigated by spectroscopic ellipsometry in the visible-ultraviolet range. The measured dielectric function spectra mainly consist of broad absorption structures attributed to charge-transfer transitions, O²⁻(2p)→Mn⁴⁺(3d) for 1.9 (t_2g) and 2.8-3.0 eV (e_g) structures and O²⁻(2p)→Mn³⁺(3d) for 2.3 (t_2g) and 3.4-3.6 eV (e_g) structures. Also, sharp absorption structures were observed at about 1.6, 1.7, and 1.9 eV, interpreted as being due to d-d crystal-field transitions within the octahedral Mn³⁺ ion. In terms of these transitions, the evolution of the optical absorption spectrum of LiMn₂O₄ by Ni doping could be explained and the related electronic structure parameters were obtained.     

About the nature of Ni3+ magnetic centres in the LaSrAl1−xNixO4 ceramics

LaSrAl_1?x Ni _x 0₄ (x≤0.11) ceramics werer studied by EPR. It was established that Ni³⁺ ions in this compound may be in two states: a low spin one with t _2g ⁶ e _g ¹ electron configuration and high spin state with t _2g ⁵ e _g ² electron configuration. It was shown that the random distribution of La³⁺ and Sr²⁺ ions in the heavy metal sublattice leads to two kinds for each type of these centres with different degree of tetragonal distortions. The total concentration of NiO₆ isolated centres in these ceramics does not exceed 5–10 % of a total number of nickel ions at a givenx. A model, explaining these peculiarities observed in an experiment by the enhanced tendency of Ni³⁺ ions to clusterization, was proposed. It appears that even at small concentrations Ni³⁺ ions form clusters and conglomerates, whose structural characteristics of the oxygen octahedra are comparable with those in LaSrNiO₄.     

Influence of Fe ions in characteristics and optical properties of mesoporous titanium oxide thin films

Fe-doped mesoporous titanium dioxide (M-TiO₂-Fe) thin films have been prepared on indium tin oxide (ITO) glass substrates by sol–gel and spin coating methods. All films exhibited mesoporous structure with the pore size around 5–9 nm characterized by small angle X-ray diffraction (SAXRD) and further confirmed by high resolution transmission electron microscopy (HRTEM). Raman spectra illustrated that lower Fe-doping contributed to the formation of nanocrystalline of M-TiO₂-Fe thin films. X-ray photoelectron spectroscopy (XPS) data indicated that the doped Fe ions exist in forms of Fe³⁺, which can play a role as e⁻ or h⁺ traps and reduce e⁻/h⁺ pair recombination rate. Optical properties including refractive indices/n, energy gaps/E_g and Urbach energy width/E₀ of the thin films were estimated and investigated by UV/vis transmittance spectra. The presence of Fe content extended the light absorption band and decreased the values of n, implying enhanced light response and performance on dye-sensitized solar cells (DSSC). The optimum Fe content in M-TiO₂-Fe thin films is determined as 10 mol%, for its compatibility of well crystalline and well potential electron transfer performance.     

Structural and optical properties of Ba(Ti1−x,Nix)O3 thin films prepared by sol–gel process

Ba(Ti_1−x,Ni_x)O₃ thin films were prepared on fused quartz substrates by a sol–gel process. X-ray diffraction and Raman scattering measurements showed that the films are of pseudo-cubic perovskite structure with random orientation and the change of lattice constant caused by Ni-doping with different concentrations is very small. Optical transmittance spectra indicated that Ni-doping has an obvious effect on the energy band structure. The energy gap of Ba(Ti_1−x,Ni_x)O₃ decreased linearly with the increase of Ni concentration. It indicates that the adjusting of band gap can be achieved by controlling the Ni-doping content accurately in Ba(Ti_1−x,Ni_x)O₃ thin films. This has potential application in devices based on ferroelectric thin films.     

Studies of the defect structure from the calculations of optical and electron paramagnetic resonance spectra for Ni<Superscript>2+</Superscript> centre in <Emphasis Type="Italic">α</Emphasis>-LiIO<Subscript>3</Subscript> crystal

By calculating the optical spectrum band positions and EPR parameters (g factors, g‖, g⊥ and zero-field splitting D) by diagonalizing the complete energy matrix of 3d⁸ ions in trigonal symmetry, the defect structure of Ni²⁺ centre in α-LiIO₃ crystal is studied. It is found that to reach the good fits of optical and EPR data between calculation and experiment, the Ni²⁺ ion should shift by Δz ≈ 0.298 Å along C₃-axis and the O^2? ions between the Ni²⁺ ion and Li⁺ vacancy (V _Li) should be displaced away from the V _Li by Δx ≈ 0.097 Å because of the electrostatic interaction. The results are discussed.     

X-ray photoelectron spectroscopy study of magnetic films

Ta/NiO_x/Ni₈₁Fe₁₉/Ta films were prepared by rf reactive and dc magnetron sputtering. The exchange coupling field H_ex and the coercivity H_c of NiO_x/Ni₈₁Fe₁₉ as a function of the ratio of Ar to O₂ during the deposition process were studied. The composition and the chemical states in the interface region of NiO_x/NiFe were also investigated using X-ray photoelectron spectroscopy (XPS) and the peak decomposition technique. The results show that the ratio of Ar to O₂ has a great effect on the chemical states of nickel in NiO_x films. The exchange coupling field H_ex and the coercivity H_c of Ta/NiO_x/Ni₈₁Fe₁₉/Ta are thus seriously affected. XPS is shown to be a powerful tool for characterizing magnetic films. Received: 18 July 2001 / Accepted: 21 December 2001 / Published online: 3 June 2002 RID="*" ID="*"Corresponding author. Fax: +86-010/6232-7283, E-mail: guanghua_yu@263.net     

Stoichiometry of LiNiO2 Studied by Mössbauer Spectroscopy

From the ⁶¹Ni and ⁵⁷Fe Mössbauer spectroscopy data follows the cationic site assignment in Li_1–x Ni_1+x O₂. Our data explain the ferromagnetic properties of this material because of the appearance of Ni²⁺ (S=1) among Ni³⁺ (S=1/2) in Ni³⁺O₂ hexagonal planes. We have no evidence for the ferromagnetic interaction between the NiO₂ layers through the excess Ni²⁺ ions substituting the Li⁺ ions. The presence of Ni²⁺ found in the Ni³⁺O₂ planes explains the absence of the Jahn–Teller distortions probably because of the electronic transfer between the Ni³⁺ and Ni²⁺ ions.     

Studies of the g factors and the local structure of the orthorhombic Ni center in KTaO3 crystal

The local structure and the g factor (g_x, g_y, and g_z) of the Ni⁺ center in KTaO₃ are theoretically studied using the perturbation formulas of the g factors for a 3d⁹ ion in orthorhombically elongated octahedra. The orthorhombic field parameters are determined from the superposition model and the local geometry of the system. In view of the covalency, the contributions from the ligand orbital and spin–orbit coupling interactions are taken into account from the cluster approach. In the calculations, the orthorhombic center is attributed to Ni⁺ occupying the host Ta⁵⁺ site, associated with the nearest-neighboring oxygen vacancy V_O along the c-axis. Furthermore, the planar Ni⁺–O²⁻ bonds are found to experience the relative variation ΔR (≈0.076 Å) along the a- and b-axis, respectively, due to the Jahn–Teller effect and the size mismatching substitution of Ta⁵⁺ by Ni⁺. Meanwhile, the effectively positive V_O can make the central Ni⁺ displace away from V_O along the c-axis by about 0.20 Å. The calculated g factors based on the above local distortions show good agreement with the experimental data.     

Room-temperature ferromagnetism in Sn1−xMnxO2 nanocrystalline thin films prepared by ultrasonic spray pyrolysis

Sn_1−xMn_xO₂ (x=0.01-0.05) thin films were synthesized on quartz substrate using an inexpensive ultrasonic spray pyrolysis technique. The influence of doping concentration and substrate temperature on structural and magnetic properties of Sn_1−xMn_xO₂ thin films was systematically investigated. X-ray diffraction (XRD) studies of these films reflect that the Mn³⁺ ions have substituted Sn⁴⁺ ions without changing the tetragonal rutile structure of pure SnO₂. A linear increase in c-axis lattice constant has been observed with corresponding increase in Mn concentration. No impurity phase was detected in XRD patterns even after doping 5 at% of Mn. A systematic change in magnetic behavior from ferromagnetic to paramagnetic was observed with increase in substrate temperature from 500 to 700 °C for Sn_1−xMn_xO₂ (x=0.01) films. Magnetic studies reveal room-temperature ferromagnetism (RTFM) with 3.61×10⁻⁴ emu saturation magnetization and 92 Oe coercivity in case of Sn_1−xMn_xO₂ (x=0.01) films deposited at 500 °C. However, paramagnetic behavior was observed for the films deposited at a higher substrate temperature of 700 °C. The presence of room-temperature ferromagnetism in these films was observed to have an intrinsic origin and could be obtained by controlling the substrate temperature and Mn doping concentration.     

Theoretical study of EPR spectra and local structure for (NiO6) cluster in LiNbO3:Ni and Al2O3:Ni systems

For a d⁸ configuration ion, the 45×45 complete energy matrix, which contains the electron-electron repulsion interaction, the ligand-field interaction, the spin-orbit coupling interaction as well as the Zeeman interaction, has been established. By diagonalizing the complete energy matrix, the local lattice structure, EPR parameters (D, g_//, g_⊥) and optical absorption spectra for Ni²⁺ ions doped in LiNbO₃ and Al₂O₃ have been investigated. The local structure distortion parameters ΔR, Δθ₁ and Δθ₂ are determined for LiNbO₃:Ni²⁺ and Al₂O₃:Ni²⁺ systems, simultaneously. These results show that local structure of (NiO₆)¹⁰⁻ cluster exhibits an elongation distortion in both LiNbO₃:Ni²⁺ and Al₂O₃:Ni²⁺ systems, in spite of the different reasons of the elongation in both systems. In addition, we have found that the orbit reduction effect is very important to understand the anisotropic g-factors for Ni²⁺ ions doped in LiNbO₃ and Al₂O₃ crystals.