Zr单晶早期氧化的晶向依赖性：亚氧化物形成及深度分布的XPS研究
Crystallographic-orientation dependence of the early-stage oxidation of Zr single crystals: an XPS study of suboxide formation and in-depth distribution
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中文总结 AI 辅助
本研究通过XPS揭示Zr单晶早期氧化受晶向影响，近棱柱取向比基面氧化更快更深，形成ZrO2外层及两种亚氧化物均匀分布，厚度随压力变化。
中文摘要 AI 辅助
通过X射线光电子能谱（XPS）研究了晶体取向对纯Zr单晶早期氧化阶段的影响。从同一α-Zr单晶切割的两个样品，在室温及O2压力分别为1×10⁻⁸、1×10⁻⁷和1×10⁻⁶托的条件下同时氧化：一个样品的表面法线平行于c轴（Z1，基面（0001）），另一个样品的法线与棱柱面法线偏离12度（Z2，近棱柱取向）。在所有三个压力下，两个样品的氧化动力学均遵循三阶段对数型行为，但在每种情况下，近棱柱样品（Z2）比基面样品（Z1）更快且更深度地吸收氧。对Zr 3d芯能级谱的反卷积，除金属Zr和ZrO2外，还分辨出两种亚化学计量Zr-O化合物，记为(ZrO)a和(ZrO)b，其相对于金属Zr的结合能位移分别为1.3和2.3 eV，与先前报道的多晶Zr的亚氧化物一致。角分辨XPS显示，在两种取向上，ZrO2均为最外层化合物，而两种亚氧化物在薄膜中几乎均匀分布。根据金属Zr 3d信号的衰减计算得到的氧化层厚度，Z1为10至13 Å，Z2为14至19 Å，取决于氧化压力，与先前对冷加工多晶Zr的测量结果密切一致，后者的表面织构以棱柱取向晶粒为主。
英文摘要
The influence of crystallographic orientation on the early stages of the oxidation of pure Zr single crystals was studied by X ray photoelectron spectroscopy (XPS). Two samples, cut from the same a-Zr single crystal, were oxidized simultaneously at room temperature and O2 pressures of 1 X 10-8, 1 X 10-7 and 1 X 10-6 torr: one with its surface normal parallel to the c-axis (Z1, basal (0001) plane) and the other with its normal 12deg from that of a prismatic plane (Z2, near-prismatic orientation). At all three pressures the oxidation kinetics of both samples followed a three stage, logarithmic type behaviour, but the near prismatic sample (Z2) incorporated oxygen faster and to a greater extent than the basal sample (Z1) in every case. Deconvolution of the Zr 3d core level spectra resolved, in addition to metallic Zr and ZrO2, two sub-stoichiometric Zr O compounds, denoted (ZrO)a and (ZrO)b, with binding-energy shifts of 1.3 and 2.3 eV with respect to metallic Zr, consistent with sub oxides previously reported for polycrystalline Zr. Angle resolved XPS showed that ZrO2 is the outermost compound in both orientations, while the two sub-oxides are distributed nearly homogeneously through the film. Oxide thicknesses, calculated from the attenuation of the metallic Zr 3d signal, ranged from 10 to 13 A for Z1 and from 14 to 19 A for Z2 depending on the oxidation pressure, in close agreement with earlier measurements on cold worked polycrystalline Zr, whose surface texture is dominated by prismatic-oriented grains.
发表机构
- Comisión Nacional de Energía Atómica (CNEA)（阿根廷国家原子能委员会）
- Instituto de Nanociencia y Nanotecnología, CNEA-CONICET（纳米科学与技术研究所，CNEA-CONICET）
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