高能分辨率欧杰电子能谱仪的定量分析;关于直接光谱参考目标卷积技术的建议

Katsumi Watanabe, Daisuke Watanabe, Kazutoshi Mamiya, Seiji Koizumi, Noriaki Sanada, Mineharu Suzuki
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摘要

目前,高能分辨率奥杰电子能谱(AES)被用于化学状态定性分析,如 X 射线光电子能谱。利用用于定性分析的高能分辨率直接光谱进行定量分析是非常理想的。然而,高能分辨直接光谱不能采用从传统能分辨分光光谱得出的 AES 分析参数,如相对灵敏度系数 (RSF)。此外,对于高能量分辨率直接光谱的量化,目前还没有确定峰值强度的成熟方法,表面分析界也没有 RSFs 数据库。因此,我们的任务是研究如何将使用圆柱镜分析仪(CMA)型 AES 仪器获得的传统能量分辨率分辨光谱中获得的分析参数用于使用球形电容器分析仪(SCA)型 AES 仪器测量的高能量分辨率直接光谱。本文提出的卷积技术是以 CMA-AES 获得的常规能量分辨率光谱数据集为目标实现的。通过应用高斯函数和矩形函数卷积函数的窗口函数进行卷积,含有精细结构固有性质的高能分辨率直接光谱在经过雪莉型背景减除后被转换成与常规能分辨率直接光谱相似的形状[Watanabe 等人,J. Vac. Sci. Technol. A 41, 043209 (2023)]。结果表明,对于用 CMA-AES 扫描的所有常规能量分辨率光谱,以及用 SCA-AES 扫描的各种能量分辨率的高能量分辨率光谱,背景减去的直接峰面积与区分的峰对峰强度之比均沿着与动能(KE)函数相同的抛物线很好地对齐。实验结果还表明,广义转换函数 f(KE;ΔE)=IareacmaIareaconv.sca(KE;ΔE) 是常规能量分辨率光谱区域(Iareacma)与卷积高能分辨率光谱区域(Iareaconv.sca)的比值,它可以转换卷积高能分辨率光谱的分辨强度,使其与使用 CMA-AES 仪器获得的常规能分辨率光谱的分辨强度相似,是 KE 和能量分辨率 ΔE 的函数。通过应用转换函数,历史上积累的用于常规能量分辨率分辨光谱的 AES 分析参数可用于高能分辨率分辨光谱。最后,研究结果表明,通过对四个参考试样的实际测量获得的转换函数足以用于高能分辨率 AES 直接光谱的实际量化。
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Quantification in high-energy resolution Auger electron spectroscopy; Proposal of a reference target convolution technique for direct spectra
Currently, high-energy resolution Auger electron spectroscopy (AES) is utilized for chemical-state qualitative analysis, such as x-ray photoelectron spectroscopy. It is highly desirable to perform quantitative analysis using the high-energy resolution direct spectra used for qualitative analysis. However, AES analysis parameters, such as relative sensitivity factors (RSFs), derived from conventional-energy resolution differentiated spectra cannot be adopted for high-energy resolution direct spectra. Furthermore, for quantification by high-energy resolution direct spectra, there is no established method for determining peak intensity, and no database of RSFs is available in surface analysis communities. Therefore, we tasked ourselves with investigating the use of the analysis parameters obtained from conventional-energy resolution-differentiated spectra obtained with a cylindrical mirror analyzer (CMA)-type AES instrument for high-energy resolution direct spectra measured with a spherical capacitor analyzer (SCA)-type AES instrument. The convolution technique proposed here is achieved by using a conventional-energy resolution spectral dataset obtained with CMA-AES as a target. By applying the convolution with the window function of the convoluted function of the Gaussian function and rectangular function, high-energy resolution direct spectra containing the inherent nature of fine structures are converted to the similar shapes of conventional-energy resolution direct spectra after the Shirley type background subtraction [Watanabe et al., J. Vac. Sci. Technol. A 41, 043209 (2023)]. Results revealed that for all spectra of conventional-energy resolution spectra taken with CMA-AES, as well as high-energy resolution spectra taken with SCA-AES with various energy resolutions, the ratios of the background-subtracted direct peak areas and the differentiated peak-to-peak intensities were well-aligned along the identical parabolic curve as a function of the kinetic energy (KE). Experimental results also revealed that the generalized conversion function f(KE;ΔE)=IareacmaIareaconv.sca(KE;ΔE), which is the ratio of the conventional-energy resolution spectral area (Iareacma) and the convoluted high-energy resolution spectral area (Iareaconv.sca), which can transform differentiated intensities of convoluted high-energy resolution spectra, such that they are similar to those of conventional-energy resolution spectra obtained using the CMA-AES instrument, being a function of KE and the energy resolution ΔE. By applying the conversion function, the historically accumulated AES analysis parameters for conventional-energy resolution differentiated spectra can be adopted to differentiated high-energy resolution spectra. Finally, the results revealed the sufficiency of the conversion function obtained by the actual measurements of the four reference specimens for the practical quantification of high-energy resolution AES direct spectra.
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