Abstract Knowledge of the location and concentration of impurity atoms doped into a synthesized material is of great interest to investigate the effect of doping. This would usually be investigated using X-ray or neutron diffraction methods in combination with Rietveld analysis. However, this technique requires a large-scale facility such as a synchrotron radiation source and nuclear reactor, and can sometimes fail to produce the desired results, depending on the constituent elements and the crystallographic conditions that are being analysed. Thus, it would be preferable to use an element-selective spectroscopy technique that is applicable to any combination of elements. We have established a quantitative method to deduce the occupation sites and their occupancies, as well as the site-dependent chemical states of the doped elements, using a combination of transmission electron microscopy (TEM), energy-dispersive X-ray (EDX) spectroscopy, and electron energy-loss spectroscopy (EELS). The method is based on electron channelling phenomena where the symmetries of the Bloch waves excited in a crystal are dependent on the diffraction condition or incident beam direction with respect to the crystal axes. By rocking the incident electron beam with a fixed pivot point on the sample surface, a set of EDX/EELS spectra are obtained as a function of the beam direction. This is followed by a statistical treatment to extract the atom-site-dependent spectra, thereby quantitatively enabling the estimation of the site occupancies and chemical states of the dopants. This is an extension of the ‘ALCHEMI’ (Atom Location by Channelling Enhanced Microanalysis) method or ‘HARECXS/HARECES’ (High Angular Resolution Channelled X-ray/Electron Spectroscopy), and we further extended the method to be applicable to cases where the crystal of interest contains multiple inequivalent atomic sites for a particular element, applying the precise spectral predictions based on electron elastic/inelastic dynamical scattering theory. After introduction of conceptual aspects of the method, we describe the extension of the method together with the development of the theoretical calculation method. We then demonstrate several useful applications of the method, including luminescent, ferrite, and battery materials. We discuss the advantages and drawbacks of the present method, compared with those of the recently developed atomic column-by-column analysis using aberration-corrected scanning TEM and high-efficiency X-ray detectors.

中文翻译：

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通过电子通道增强微分析对晶体材料中的功能掺杂剂进行高精度定量原子位点分析

摘要 了解掺杂到合成材料中的杂质原子的位置和浓度对于研究掺杂的影响非常重要。这通常会使用 X 射线或中子衍射方法结合 Rietveld 分析进行研究。然而，这种技术需要大型设施，如同步辐射源和核反应堆，有时可能无法产生预期的结果，这取决于所分析的组成元素和晶体学条件。因此，最好使用适用于任何元素组合的元素选择性光谱技术。我们已经建立了一种定量方法来推导占据位点及其占据率，以及掺杂元素的位点相关化学状态，使用透射电子显微镜 (TEM)、能量色散 X 射线 (EDX) 光谱和电子能量损失光谱 (EELS) 的组合。该方法基于电子通道现象，其中晶体中激发的布洛赫波的对称性取决于衍射条件或相对于晶轴的入射光束方向。通过在样品表面上以固定的枢轴点摆动入射电子束，可以获得一组 EDX/EELS 光谱作为束方向的函数。然后进行统计处理以提取原子位点相关光谱，从而定量地估计掺杂剂的位点占有率和化学状态。这是“ALCHEMI”（通过通道增强微分析进行原子定位）方法或“HARECXS/HARECES”（高角分辨率通道 X 射线/电子光谱）方法的扩展，我们进一步扩展了该方法以适用于以下情况感兴趣的晶体包含特定元素的多个不等价原子位点，应用基于电子弹性/非弹性动态散射理论的精确光谱预测。在介绍了该方法的概念方面之后，我们描述了该方法的扩展以及理论计算方法的发展。然后，我们展示了该方法的几种有用应用，包括发光、铁氧体和电池材料。我们讨论了本方法的优缺点，