掠射软X射线荧光分析技术研究
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摘要
掠射X射线分析是近年来迅速发展的一门分析技术，在科学研究以及分析检测和质量控制等生产领域都有着广泛的应用。X射线分析技术具有试样无损分析、制样经济方便、操作简单、分析结果重现性好及精度高等优点，使得这项技术在薄膜特性分析、半导体材料及磁铁材料表面检测方面受到特别的青睐。本文在综述了国内外掠射X射线荧光分析技术的研发和应用的基础上，对掠出射X射线荧光技术在薄膜特性分析上的理论、装置和实验三方面进行了研究。
在理论研究方面，首先讨论了软X射线荧光产生的原子物理相关理论；其次根据洛伦兹互换定理，得出了掠出射和掠入射两种荧光分析理论具有互换性的结论。介绍了掠射X射线与薄膜样品作用时产生的干涉现象，给出了X射线双光束干涉和多光束干涉产生极值的条件。最后，利用平稳位相方法建立了掠出射情况下薄层样品产生的荧光强度和掠出射角的对应关系数学模型，推导了薄层样品荧光强度理论计算公式，并以此为依据模拟计算得出了Cr、Fe、Ti和Ni等几种以Si作基底的单层薄膜样品的荧光强度随掠出射角变化的理论曲线。
在装置研究方面，提出了掠出射软X射线荧光分析装置的结构布局要求，并利用实验室现有的一台单色仪，设计并建造了国内首台掠出射软X射线荧光光谱仪。光谱仪包括激发光源、精密样品台、单色仪系统、探测和数据处理系统等几部分，其特点是采用超薄窗流气正比计数管作探测器的波长色散系统，适合探测样品产生的软X射线荧光。
在实验研究方面，首先对掠出射X射线荧光光谱仪的色散单元进行了调整和波长标定。其次利用~(55)Fe作放射源对探测器和MCA多道分析系统进行了标校。最后利用同步辐射光源做激发源，在掠出射方式下研究了Si片上不同厚度单层Cr膜和双层Fe／V膜样品产生的荧光光强和掠出射角的对应关系。实验结果和理论计算符合得很好，这表明掠出射X射线荧光光谱分析技术完全可以用来分析薄膜厚度等特性。
本论文采用理论、装置和实验研究密切结合的方式，开展了掠射X射线荧光分析技术研究工作，在国内建立了首台掠出射X射线荧光光谱分析装置，并对不同厚度单层和双层薄膜样品在掠出射条件下产生的荧光光强与掠射角的对应
博士学位论文:掠射X射线荧光分析技术研究
关系进行了实验测定。本文所进行的工作为进一步开展掠射X射线荧光分析技术
研究奠定了基础。
Grazing X-ray fluorescence analysis is a new development approach of x-ray fluorescence technique in recent years. It will have good prospects and wide application in various fields, such as scientific research, quality monitoring and controlling. Especially, it becomes more and more important in the field of analysis of the thin layer's characteristics, analysis of contaminants on semiconductor wafers and surface test for ferromagnetic substance. Because grazing x-ray fluorescence techniques have the advantages, which are non-destructive nature analysis method, simple and economical for sample preparation, good fidelity and high precision for results. In this dissertation, according to the summarization of R&D and application of this kind of techniques, the theory, setup and experiment of grazing-emission x-ray fluorescence techniques are studied, which is used to characterize thin layer characteristics.
In theory, firstly, the theorectical considerations on soft X-ray are discussed. Secondly, the conclusion is obtained based on the applying the Lorentz reciprocity theorem, which demonstrates that equivalence of brazing exit and grazing incidence methods. The phenomenon of interference is presented when the X-ray beam hits the thin layer sample at glancing angle, the angles corresponding maximal and minimal intensity of x-ray fluorescence are described when the phenomenon of double-beam interference or multiple-beam interference is occurred. In the theoretical description of grazing emission fluorescence, the mode of fluorescence intensity emitted from layered materials dependence of grazing angle is established by applying asymptotic approximations to double Fourier integrals, and the theoretic calculation formula of fluorescence intensity from a thin layer is derived. By the derived expressions, the theoretic simulation curves of several thin layers on Si substrate are calculated.
In the experimental setup, the requirement of construction of the setup and some important parameters are brought forward. By using of an old monochomator, a set of grazing emission X-ray fluorescence spectrometer, which includes exciting source,
fine sample stage, a monochromator, detecting sub-system and data processing sub-system, is designed and built with many limiting conditions exist in our laboratory. The spectrometer is the first one in our domestic area, which allows the use of gas-flow proportional counter and wavelength dispersive method. This type of configuration has the advantages of better energy resolution at longer wavelengths (soft x-ray and light elements) and a much larger dynamic range than the energy dispersive method.
In experiment, the alignment and calibration to the monochromator were described firstly. Then, a gas-flow proportional counter and the Multi-Channel Analyzer (MCA) are calibrated by the radio isotope source 55Fe, and the dead time, counting rate plateau and x-ray linearity have been measured. Finally, the angular dependence of the top layer fluorescence intensity was investigated when varying the thickness of the top layer. The experimental results are good agreement with the theoretical calculations. This demonstrates the feasibility of using grazing emission x-ray fluorescence spectroscopy as a method of studying the thin layer's characteristics, such as composition and thickiness etc.
With the intimately combining of theoretical, set-up and experimental research, the study on the analysis techniques of grazing emission x-ray fluorescence is developed, and the first set of grazing emission x-ray fluorescence setup is established. At the same time, the angular dependence of the fluorescence intensity with different thickness layer is measured. All the work in this thesis provides the basis for the further researches.
在理论研究方面，首先讨论了软X射线荧光产生的原子物理相关理论；其次根据洛伦兹互换定理，得出了掠出射和掠入射两种荧光分析理论具有互换性的结论。介绍了掠射X射线与薄膜样品作用时产生的干涉现象，给出了X射线双光束干涉和多光束干涉产生极值的条件。最后，利用平稳位相方法建立了掠出射情况下薄层样品产生的荧光强度和掠出射角的对应关系数学模型，推导了薄层样品荧光强度理论计算公式，并以此为依据模拟计算得出了Cr、Fe、Ti和Ni等几种以Si作基底的单层薄膜样品的荧光强度随掠出射角变化的理论曲线。
在装置研究方面，提出了掠出射软X射线荧光分析装置的结构布局要求，并利用实验室现有的一台单色仪，设计并建造了国内首台掠出射软X射线荧光光谱仪。光谱仪包括激发光源、精密样品台、单色仪系统、探测和数据处理系统等几部分，其特点是采用超薄窗流气正比计数管作探测器的波长色散系统，适合探测样品产生的软X射线荧光。
在实验研究方面，首先对掠出射X射线荧光光谱仪的色散单元进行了调整和波长标定。其次利用~(55)Fe作放射源对探测器和MCA多道分析系统进行了标校。最后利用同步辐射光源做激发源，在掠出射方式下研究了Si片上不同厚度单层Cr膜和双层Fe／V膜样品产生的荧光光强和掠出射角的对应关系。实验结果和理论计算符合得很好，这表明掠出射X射线荧光光谱分析技术完全可以用来分析薄膜厚度等特性。
本论文采用理论、装置和实验研究密切结合的方式，开展了掠射X射线荧光分析技术研究工作，在国内建立了首台掠出射X射线荧光光谱分析装置，并对不同厚度单层和双层薄膜样品在掠出射条件下产生的荧光光强与掠射角的对应
博士学位论文:掠射X射线荧光分析技术研究
关系进行了实验测定。本文所进行的工作为进一步开展掠射X射线荧光分析技术
研究奠定了基础。
Grazing X-ray fluorescence analysis is a new development approach of x-ray fluorescence technique in recent years. It will have good prospects and wide application in various fields, such as scientific research, quality monitoring and controlling. Especially, it becomes more and more important in the field of analysis of the thin layer's characteristics, analysis of contaminants on semiconductor wafers and surface test for ferromagnetic substance. Because grazing x-ray fluorescence techniques have the advantages, which are non-destructive nature analysis method, simple and economical for sample preparation, good fidelity and high precision for results. In this dissertation, according to the summarization of R&D and application of this kind of techniques, the theory, setup and experiment of grazing-emission x-ray fluorescence techniques are studied, which is used to characterize thin layer characteristics.
In theory, firstly, the theorectical considerations on soft X-ray are discussed. Secondly, the conclusion is obtained based on the applying the Lorentz reciprocity theorem, which demonstrates that equivalence of brazing exit and grazing incidence methods. The phenomenon of interference is presented when the X-ray beam hits the thin layer sample at glancing angle, the angles corresponding maximal and minimal intensity of x-ray fluorescence are described when the phenomenon of double-beam interference or multiple-beam interference is occurred. In the theoretical description of grazing emission fluorescence, the mode of fluorescence intensity emitted from layered materials dependence of grazing angle is established by applying asymptotic approximations to double Fourier integrals, and the theoretic calculation formula of fluorescence intensity from a thin layer is derived. By the derived expressions, the theoretic simulation curves of several thin layers on Si substrate are calculated.
In the experimental setup, the requirement of construction of the setup and some important parameters are brought forward. By using of an old monochomator, a set of grazing emission X-ray fluorescence spectrometer, which includes exciting source,
fine sample stage, a monochromator, detecting sub-system and data processing sub-system, is designed and built with many limiting conditions exist in our laboratory. The spectrometer is the first one in our domestic area, which allows the use of gas-flow proportional counter and wavelength dispersive method. This type of configuration has the advantages of better energy resolution at longer wavelengths (soft x-ray and light elements) and a much larger dynamic range than the energy dispersive method.
In experiment, the alignment and calibration to the monochromator were described firstly. Then, a gas-flow proportional counter and the Multi-Channel Analyzer (MCA) are calibrated by the radio isotope source 55Fe, and the dead time, counting rate plateau and x-ray linearity have been measured. Finally, the angular dependence of the top layer fluorescence intensity was investigated when varying the thickness of the top layer. The experimental results are good agreement with the theoretical calculations. This demonstrates the feasibility of using grazing emission x-ray fluorescence spectroscopy as a method of studying the thin layer's characteristics, such as composition and thickiness etc.
With the intimately combining of theoretical, set-up and experimental research, the study on the analysis techniques of grazing emission x-ray fluorescence is developed, and the first set of grazing emission x-ray fluorescence setup is established. At the same time, the angular dependence of the fluorescence intensity with different thickness layer is measured. All the work in this thesis provides the basis for the further researches.
引文
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