JP3814644B2 - X-ray fluorescence analysis method and apparatus - Google Patents

X-ray fluorescence analysis method and apparatus Download PDF

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JP3814644B2
JP3814644B2 JP2004223426A JP2004223426A JP3814644B2 JP 3814644 B2 JP3814644 B2 JP 3814644B2 JP 2004223426 A JP2004223426 A JP 2004223426A JP 2004223426 A JP2004223426 A JP 2004223426A JP 3814644 B2 JP3814644 B2 JP 3814644B2
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基行 山上
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理学電機工業株式会社
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Description

本発明は、シリコン基板のような試料の試料表面部に存在する被測定物を蛍光Ｘ線分析する蛍光Ｘ線分析方法および装置に関するものである。   The present invention relates to a fluorescent X-ray analysis method and apparatus for fluorescent X-ray analysis of a measurement object existing on a sample surface portion of a sample such as a silicon substrate.

従来から、例えばシリコン基板表面に付着した被測定物である汚染物質の種類、存在量を決定するために、全反射蛍光Ｘ線分析を行うことが知られている。被測定物としてシリコン基板表面近傍に存在する汚染物質、主に鉄、ニッケル、銅、亜鉛といった遷移金属の分析を行うためには、例えば、１次Ｘ線源としてＷ−Ｌβ線等を用い、１次Ｘ線をシリコン基板表面に微小な所定の入射角度で照射し、被測定物からの蛍光Ｘ線のエネルギーから種類を、蛍光Ｘ線の強度から存在量を決定している。   Conventionally, it is known to perform total reflection X-ray fluorescence analysis in order to determine, for example, the type and abundance of a contaminant that is an object to be measured attached to the surface of a silicon substrate. In order to analyze contaminants present near the silicon substrate surface as the object to be measured, mainly transition metals such as iron, nickel, copper, and zinc, for example, using W-Lβ ray as a primary X-ray source, The primary X-ray is irradiated onto the silicon substrate surface at a minute predetermined incident angle, the type is determined from the energy of the fluorescent X-ray from the object to be measured, and the abundance is determined from the intensity of the fluorescent X-ray.

しかし、図３に示すように、酸化膜を有するシリコン基板表面に付着した被測定物が、（Ａ）のように酸化膜ＳｉＯ2 上にフィルム状に分散して存在する場合、（Ｂ）のように粒状に存在する場合、または（Ｃ）のように酸化膜ＳｉＯ2 中や酸化膜ＳｉＯ2 とシリコンＳｉとの界面に存在する場合がある。これらの場合、被測定物の存在量が同一でも、被測定物の形態によって、所定の１次Ｘ線を照射した場合の蛍光Ｘ線強度の測定値がそれぞれ異なる。このため、この測定した蛍光Ｘ線強度に基づいて算出された被測定物の存在量も被測定物の形態によって異なる結果となることから、全反射蛍光Ｘ線分析において被測定物の存在量を正確に得ることができない場合があった。 However, as shown in FIG. 3, when the object to be measured attached to the surface of the silicon substrate having the oxide film is dispersed in the form of a film on the oxide film SiO2 as shown in (A), as shown in (B). Or in the oxide film SiO2 or at the interface between the oxide film SiO2 and silicon Si as shown in FIG. In these cases, even if the amount of the object to be measured is the same, the measured value of the fluorescent X-ray intensity when the predetermined primary X-ray is irradiated differs depending on the form of the object to be measured. For this reason, since the abundance of the measured object calculated based on the measured fluorescent X-ray intensity varies depending on the form of the measured object, the abundance of the measured object is determined in the total reflection X-ray fluorescence analysis. In some cases, it could not be obtained accurately.

本発明は、前記の問題点を解決して、被測定物の存在量を正確に得ることができる蛍光Ｘ線分析方法および装置を提供することを目的としている。   An object of the present invention is to provide a fluorescent X-ray analysis method and apparatus capable of solving the above-described problems and accurately obtaining the abundance of an object to be measured.

前記目的を達成するために、本発明に係る蛍光Ｘ線分析方法は、試料表面に１次Ｘ線を照射し、試料表面部に存在する被測定物から発生した蛍光Ｘ線を測定する蛍光Ｘ線分析方法であって、被測定物の存在量は等しいが、被測定物の付着形態がフィルム状である標準試料１および粒状である標準試料２について、前記１次Ｘ線をそれぞれ相異なる複数の照射角度φ１〜φｎで照射して蛍光Ｘ線の強度を測定する。
複数の照射角度φ１〜φｎのうち任意の２つの照射角度φa ，φb （φa ＜φb ）の複数の組について、それぞれ標準試料１の蛍光Ｘ線強度Ｉa1，Ｉb1の比を標準試料１の粒度係数ＰＦ１として求め、標準試料２の蛍光Ｘ線強度Ｉa2，Ｉb2の比を標準試料２の粒度係数ＰＦ２として求める。本発明では２つの照射角度での蛍光Ｘ線強度比を粒度係数ＰＦと定義する。
そして、これら得られた各組についての蛍光Ｘ線強度Ｉa1，Ｉa2および粒度係数ＰＦ１、ＰＦ２から、Ｉa2・ＰＦ１／ＰＦ２の値がＩa1の値に最も近づくように、照射角度φａ，φｂの組を選択し、前記選択した照射角度φａ，φｂにおける測定対象試料についての蛍光Ｘ線の強度Ｉa3，Ｉb3から、被測定物の存在量を決定するものである。 In order to achieve the above object, a fluorescent X-ray analysis method according to the present invention irradiates primary X-rays on a sample surface, and measures fluorescent X-rays generated from an object existing on the sample surface. In the line analysis method, the abundance of the object to be measured is the same, but for the standard sample 1 in which the object is attached in a film form and the standard sample 2 in a granular form, the primary X-rays are different from each other. The intensity of fluorescent X-rays is measured by irradiation at irradiation angles φ1 to φn.
The ratio of the fluorescent X-ray intensities Ia1 and Ib1 of the standard sample 1 with respect to a plurality of sets of arbitrary two irradiation angles φa and φb (φa <φb) among the plurality of irradiation angles φ1 to φn, respectively. Obtained as PF1, and the ratio of the fluorescent X-ray intensities Ia2 and Ib2 of the standard sample 2 is obtained as the particle size coefficient PF2 of the standard sample 2. In the present invention, the fluorescent X-ray intensity ratio at two irradiation angles is defined as a particle size coefficient PF.
Then, from the X-ray fluorescence intensities Ia1 and Ia2 and the particle size coefficients PF1 and PF2 for each of these obtained sets, the set of irradiation angles φa and φb is set so that the value of Ia2 · PF1 / PF2 is closest to the value of Ia1. Then, the abundance of the object to be measured is determined from the intensities Ia3 and Ib3 of the fluorescent X-rays for the sample to be measured at the selected irradiation angles φa and φb.

前記した蛍光Ｘ線分析方法に対応する蛍光Ｘ線分析装置は、試料表面に１次Ｘ線を照射し、試料表面部に存在する被測定物から発生した蛍光Ｘ線を測定するものであって、被測定物の存在量は等しいが、被測定物の付着形態がフィルム状である標準試料１および粒状である標準試料２について、前記１次Ｘ線をそれぞれ相異なる複数の照射角度φ１〜φｎで照射して蛍光Ｘ線の強度を測定する測定手段と、前記測定された複数の照射角度のうち任意の２つの照射角度φa ，φb （φa ＜φb ）の複数の組について、それぞれ標準試料１の蛍光Ｘ線強度Ｉa1，Ｉb1の比を標準試料１の粒度係数ＰＦ１として求め、標準試料２の蛍光Ｘ線強度Ｉa2，Ｉb2の比を標準試料２の粒度係数ＰＦ２として求めて、これら得られた各組についての蛍光Ｘ線強度Ｉa1，Ｉa2および粒度係数ＰＦ１、ＰＦ２から、Ｉa2・ＰＦ１／ＰＦ２の値がＩa1の値に最も近づくように、照射角度φａ，φｂの組を選択する演算手段と、前記選択した照射角度φａ，φｂにおける測定対象試料についての蛍光Ｘ線の強度Ｉa3，Ｉb3から、被測定物の存在量を決定する存在量決定手段とを備えている。 An X-ray fluorescence analyzer corresponding to the above-described X-ray fluorescence analysis method irradiates primary X-rays on a sample surface and measures fluorescent X-rays generated from an object existing on the sample surface. In the standard sample 1 in which the abundance of the object to be measured is the same, but the adhesion form of the object to be measured is a film-like standard sample 2 and a granular standard sample 2 , the primary X-rays are respectively irradiated with a plurality of different irradiation angles φ1 to φn. Measuring means for measuring the intensity of fluorescent X-rays by irradiation with a standard sample 1 for each of a plurality of sets of arbitrary two irradiation angles φa and φb (φa <φb) among the plurality of measured irradiation angles. The ratio of the fluorescent X-ray intensities Ia1 and Ib1 is obtained as the particle size factor PF1 of the standard sample 1, and the ratio of the fluorescent X-ray intensities Ia2 and Ib2 of the standard sample 2 is obtained as the particle size factor PF2 of the standard sample 2. X-ray fluorescence intensity Ia1, Ia for each set 2 and the particle size coefficients PF1 and PF2, the calculation means for selecting a set of irradiation angles φa and φb so that the value of Ia2 · PF1 / PF2 is closest to the value of Ia1, and measurement at the selected irradiation angles φa and φb Abundance determining means for determining the abundance of the object to be measured based on the fluorescent X-ray intensities Ia3 and Ib3 of the target sample.

この構成によれば、標準試料２の蛍光Ｘ線強度Ｉa2に標準試料１と標準試料２の粒度係数の比ＰＦ１／ＰＦ２を乗じた値が、標準試料１の蛍光Ｘ線強度Ｉa1の値に近づくように、照射角度φａ，φｂを選択し、その選択した照射角度φａ，φｂにおける測定対象試料についての蛍光Ｘ線の強度Ｉa3，Ｉb3から、被測定物の存在量を決定するので、正確に測定対象試料の被測定物の存在量を決定できる。 According to this configuration , the value obtained by multiplying the fluorescent X-ray intensity Ia2 of the standard sample 2 by the ratio PF1 / PF2 of the particle size coefficients of the standard sample 1 and the standard sample 2 approaches the value of the fluorescent X-ray intensity Ia1 of the standard sample 1. As described above, the irradiation angles φa and φb are selected , and the abundance of the object to be measured is determined from the fluorescent X-ray intensities Ia3 and Ib3 of the measurement target sample at the selected irradiation angles φa and φb. The abundance of the object to be measured in the target sample can be determined.

本発明において、Ｉa2・ＰＦ１／ＰＦ２の値がＩa1の値に近づく場合とは、（Ｉa2／Ｉa1）・（ＰＦ１／ＰＦ２）＝Ａとしたときに係数Ａが１に近づくことをいう。係数Ａが１に近づくにしたがって、高精度に被測定物の存在量を決定できる。係数Ａの範囲は０．３〜３が好ましく、０．４〜２．５がより好ましく、０．５〜２がさらに好ましく、０．７〜１．５が特に好ましく、０．８〜１．２が最も好ましい。   In the present invention, the case where the value of Ia2 · PF1 / PF2 approaches the value of Ia1 means that the coefficient A approaches 1 when (Ia2 / Ia1) · (PF1 / PF2) = A. As the coefficient A approaches 1, the abundance of the object to be measured can be determined with high accuracy. The range of the coefficient A is preferably 0.3 to 3, more preferably 0.4 to 2.5, still more preferably 0.5 to 2, particularly preferably 0.7 to 1.5, and 0.8 to 1. 2 is most preferred.

以下、本発明の実施形態を図面に基づいて説明する。
図１は、本発明の一実施形態に係る全反射蛍光Ｘ線分析装置の概略側面図を示す。本装置は、Ｘ線を発生させるＸ線源２と、Ｘ線源２からのＸ線を回折させて単色化させ、その１次Ｘ線Ｂ１を試料台７０上のシリコン基板のような試料５０の表面に向かって微小な所定の入射角度（例えば、０．０５°〜０．２°）で入射させる分光結晶３と、試料５０表面に対向して、１次Ｘ線Ｂ１を受けた試料５０からの蛍光Ｘ線Ｂ３を検出する検出器４とを備えており、試料５０の試料表面部に存在する被測定物から発生した蛍光Ｘ線Ｂ３を分析する。試料５０をのせた試料台７０が図示しない駆動手段によって駆動されて、試料５０に対して任意の照射（入射）角度および位置で１次Ｘ線Ｂ１が照射される。 Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 1 shows a schematic side view of a total reflection X-ray fluorescence spectrometer according to an embodiment of the present invention. In this apparatus, an X-ray source 2 for generating X-rays, and X-rays from the X-ray source 2 are diffracted and monochromatic, and the primary X-ray B1 is converted into a sample 50 such as a silicon substrate on a sample stage 70. The spectroscopic crystal 3 incident at a minute predetermined incident angle (for example, 0.05 ° to 0.2 °) toward the surface of the sample 50 and the sample 50 that has received the primary X-ray B1 facing the surface of the sample 50 And a detector 4 for detecting the fluorescent X-ray B3 from the sample 50, and the fluorescent X-ray B3 generated from the measurement object existing on the sample surface of the sample 50 is analyzed. The sample stage 70 on which the sample 50 is placed is driven by a driving means (not shown), and the sample 50 is irradiated with the primary X-ray B1 at an arbitrary irradiation (incident) angle and position.

前記Ｘ線源２、分光結晶３、検出器４、試料台７０および駆動手段により測定手段５が構成され、この測定手段５は、前記１次Ｘ線Ｂ１を標準試料と測定対象試料について、それぞれ相異なる複数の照射角度φ１〜φｎで照射して蛍光Ｘ線Ｂ３の強度を測定する。   The X-ray source 2, the spectral crystal 3, the detector 4, the sample stage 70 and the driving means constitute a measuring means 5, which measures the primary X-ray B 1 for the standard sample and the measurement target sample, respectively. Irradiation is performed at a plurality of different irradiation angles φ1 to φn, and the intensity of the fluorescent X-ray B3 is measured.

本装置の演算手段６は、前記測定された複数の照射角度のうち任意の２つの照射角度φa ，φb （φa ＜φb ）について、標準試料１の蛍光Ｘ線強度Ｉa1，Ｉb1の比を標準試料１の粒度係数ＰＦ１として求め、標準試料２の蛍光Ｘ線強度Ｉa2，Ｉb2の比を標準試料２の粒度係数ＰＦ２として求めて、Ｉa2・ＰＦ１／ＰＦ２の値がＩa1の値に近づくように、照射角度φａ，φｂを決定する。また、存在量決定手段８は、前記決定した照射角度φａ，φｂにおける測定対象試料についての蛍光Ｘ線の強度Ｉa3，Ｉb3の比ＰＦ３から、被測定物の存在量を決定する。   The calculation means 6 of this apparatus calculates the ratio of the fluorescent X-ray intensities Ia1 and Ib1 of the standard sample 1 for any two of the measured irradiation angles φa and φb (φa <φb). The particle size factor PF1 of 1 is obtained, and the ratio of the fluorescent X-ray intensities Ia2 and Ib2 of the standard sample 2 is obtained as the particle size factor PF2 of the standard sample 2. The angles φa and φb are determined. Further, the abundance determining means 8 determines the abundance of the object to be measured from the ratio PF3 of the fluorescent X-ray intensities Ia3 and Ib3 with respect to the sample to be measured at the determined irradiation angles φa and φb.

以下、本装置の動作を説明する。
例えば、シリコン基板上の被測定物である汚染物質のニッケルの定量分析を行う場合、汚染量が既知の標準試料に対して、予め全反射蛍光Ｘ線分析（照射角度φｃ（例えば、０．０９°）における測定）を行い、汚染量と蛍光Ｘ線強度との関係を明らかにしておく。つまり、汚染量と蛍光Ｘ線強度との関係を示す検量線を作成しておく。つぎに、汚染量が未知の測定対象試料に対して全反射蛍光Ｘ線測定を行い、測定対象試料の蛍光Ｘ線強度を測定する。その強度を前記検量線を用いて汚染量に換算する。本実施形態では、標準試料１における被測定物の付着形態をフィルム状とし、標準試料２における被測定物の付着形態を粒状とする。 The operation of this apparatus will be described below.
For example, when a quantitative analysis of nickel, which is a contaminant on the silicon substrate, is performed, a total reflection fluorescent X-ray analysis ( irradiation angle φc (for example, 0.09 ) is performed on a standard sample with a known contamination amount. ))) To clarify the relationship between the amount of contamination and the fluorescent X-ray intensity. That is, a calibration curve indicating the relationship between the contamination amount and the fluorescent X-ray intensity is created. Next, total reflection fluorescent X-ray measurement is performed on the measurement target sample whose amount of contamination is unknown, and the fluorescent X-ray intensity of the measurement target sample is measured. The intensity is converted into the amount of contamination using the calibration curve. In the present embodiment, the adhesion form of the measurement object in the standard sample 1 is a film, and the adhesion form of the measurement object in the standard sample 2 is granular.

本実施形態では、フィルム状の標準試料１をフッ化水素雰囲気中に３０分間放置することにより、試料表面のシリコン酸化膜をフッ化水素に溶解させ、その後、試料を大気中に放置して、シリコン基板上で溶解液を乾燥させ、シリコン基板上の被測定物の付着形態をフィルム状から粒状に変化させて、粒状の標準試料２とした。この場合、被測定物の存在量は変化していない。   In this embodiment, the film-like standard sample 1 is left in a hydrogen fluoride atmosphere for 30 minutes to dissolve the silicon oxide film on the sample surface in hydrogen fluoride, and then the sample is left in the atmosphere. The dissolved liquid was dried on the silicon substrate, and the adhesion form of the object to be measured on the silicon substrate was changed from a film shape to a granular shape to obtain a granular standard sample 2. In this case, the abundance of the object to be measured has not changed.

図２は、シリコン基板表面の被測定物から発生した蛍光Ｘ線Ｂ３の強度と１次Ｘ線Ｂ１の照射角度との関係を示す。（Ａ）は被測定物が基板上にフィルム状に存在する場合、（Ｂ）は粒状に存在する場合である。図２（Ａ）と（Ｂ）を比較すると、被測定物の存在量が等しくても、フィルム状の標準試料１と粒状の標準試料２とでは、蛍光Ｘ線Ｂ３の強度と１次Ｘ線Ｂ１の照射角度との関係は大きく異なる。   FIG. 2 shows the relationship between the intensity of the fluorescent X-ray B3 generated from the object to be measured on the surface of the silicon substrate and the irradiation angle of the primary X-ray B1. (A) is the case where the object to be measured is present in the form of a film on the substrate, and (B) is the case where it is present in a granular form. Comparing FIGS. 2A and 2B, the intensity of the fluorescent X-ray B3 and the primary X-ray are obtained for the film-like standard sample 1 and the granular standard sample 2 even if the abundance of the object to be measured is equal. The relationship with the irradiation angle of B1 is greatly different.

本装置では、まず、測定手段５により、１次Ｘ線Ｂ１を標準試料１と標準試料２について、それぞれ相異なる複数の照射角度φ１〜φｎで照射して蛍光Ｘ線Ｂ３の強度を測定する。   In this apparatus, first, the measurement means 5 irradiates the primary X-ray B1 with respect to the standard sample 1 and the standard sample 2 at a plurality of different irradiation angles φ1 to φn, and measures the intensity of the fluorescent X-ray B3.

つぎに、演算手段６の動作を、測定された複数の照射角度のデータのうち、それぞれ異なる２つの照射角度φａ、φｂを選択した種々のケース（複数組）のうち例えば２つのケースについて説明する。 Next, the operation of the calculation means 6 will be described in, for example, two cases among various cases (plural sets) in which two different irradiation angles φa and φb are selected from the measured data of the plurality of irradiation angles. .

ケース１：照射角度φａ＝０．０５°、φｂ＝０．１５°を選択したとき
この場合、フィルム状の標準試料１についてのＮｉ−Ｋα線の強度は０．０５°のとき２０．６５ｃｐｓ、０．１５°のとき３３５．６５ｃｐｓである。したがって、標準試料１についての蛍光Ｘ線強度Ｉa1，Ｉb1の比である標準試料１の粒度係数ＰＦ１を求めると、ＰＦ１＝２０．６５／３３５．６５＝０．０６である。
粒状の標準試料２についてのＮｉ−Ｋα線の強度は０．０５°のとき１５８．７９ｃｐｓ、０．１５°のとき４４４．０５ｃｐｓである。したがって、標準試料２についての蛍光Ｘ線強度Ｉa2，Ｉb2の比である標準試料２の粒度係数ＰＦ２を求めると、ＰＦ２＝１５８．７９／４４４．０５＝０．３６である。これにより、ＰＦ１／ＰＦ２＝０．０６／０．３６＝１／６となる。 Case 1: When the irradiation angle φa = 0.05 ° and φb = 0.15 ° are selected In this case, the intensity of the Ni-Kα ray for the film-like standard sample 1 is 20.65 cps when 0.05 °, It is 335.65 cps at 0.15 °. Therefore, when the particle size coefficient PF1 of the standard sample 1 which is the ratio of the fluorescent X-ray intensities Ia1 and Ib1 for the standard sample 1 is obtained, PF1 = 20.65 / 335.65 = 0.06.
The intensity of the Ni-Kα ray for the granular standard sample 2 is 158.79 cps at 0.05 ° and 444.05 cps at 0.15 °. Therefore, when the particle size coefficient PF2 of the standard sample 2 which is the ratio of the fluorescent X-ray intensities Ia2 and Ib2 for the standard sample 2 is obtained, PF2 = 158.79 / 444.05 = 0.36. As a result, PF1 / PF2 = 0.06 / 0.36 = 1/6.

このとき、係数Ａは、Ａ＝（Ｉa2／Ｉa1）・（ＰＦ１／ＰＦ２）＝（１５８．７９／２０．６５）・（０．０６／０．３６）≒１．３である。   At this time, the coefficient A is A = (Ia2 / Ia1) · (PF1 / PF2) = (158.79 / 20.65) · (0.06 / 0.36) ≈1.3.

ケース２：照射角度φａ＝０．０９°、φｂ＝０．１７°を選択したとき
この場合、フィルム状の標準試料１について全反射蛍光Ｘ線測定した結果、Ｎｉ−Ｋα線の強度は０．０９°のとき１０３．６０ｃｐｓ、０．１７°のとき４１９．５８ｃｐｓである。したがって、標準試料１についての蛍光Ｘ線強度Ｉa1，Ｉb1の比である標準試料１の粒度係数ＰＦ１は、ＰＦ１＝１０３．６０／４１９．５８＝０．２５である。前記定量分析用の照射角度φｃ＝０．０９°での検量線を用いて、Ｎｉ−Ｋα線の強度を標準試料１のニッケルの汚染量に換算すると、約１．５×１０12atoms/cm2 となる。
粒状の標準試料２については、Ｎｉ−Ｋα線の強度は０．０９°のとき４０４．９１ｃｐｓ、０．１７°のとき４１５．３０ｃｐｓである。したがって、標準試料２についての蛍光Ｘ線強度Ｉa2，Ｉb2の比である標準試料２の粒度係数ＰＦ２は、ＰＦ２＝４０４．９１／４１５．３０＝０．９７である。これにより、前記粒度係数ＰＦ１とＰＦ２の比は、ＰＦ１／ＰＦ２＝０．２５／０．９７≒１／４となる。 Case 2: When irradiation angle φa = 0.09 ° and φb = 0.17 ° are selected
In this case, as a result of the total reflection fluorescent X-ray measurement for the film-like standard sample 1, the intensity of the Ni-Kα ray is 103.60 cps at 0.09 ° and 419.58 cps at 0.17 °. Therefore, the particle size factor PF1 of the standard sample 1, which is the ratio of the fluorescent X-ray intensities Ia1 and Ib1 for the standard sample 1, is PF1 = 103.60 / 419.58 = 0.25. Using the calibration curve at the irradiation angle φc = 0.09 ° for quantitative analysis, the intensity of the Ni-Kα ray is converted into the nickel contamination amount of the standard sample 1, and about 1.5 × 10 12 atoms / cm 3. 2
Regarding the granular standard sample 2, the intensity of the Ni-Kα ray is 404.91 cps at 0.09 ° and 415.30 cps at 0.17 °. Therefore, the particle size factor PF2 of the standard sample 2, which is the ratio of the fluorescent X-ray intensities Ia2 and Ib2 for the standard sample 2, is PF2 = 404.91 / 415.30 = 0.97. As a result, the ratio between the particle size coefficients PF1 and PF2 is PF1 / PF2 = 0.25 / 0.97≈1 / 4.

このとき、係数Ａは、Ａ＝（Ｉa2／Ｉa1）・（ＰＦ１／ＰＦ２）＝（４０４．９１／１０３．６０）・（０．２５／０．９７）≒１である。したがって、ケース１を含む種々のケースのうち、ケース２の係数Ａが１に近いので、ケース２の照射角度φａ＝０．０９°，φｂ＝０．１７°に決定する。 At this time, the coefficient A is A = (Ia2 / Ia1) · (PF1 / PF2) = (404.91 / 103.60) · (0.25 / 0.97) ≈1. Accordingly, among the various cases including the case 1, since the coefficient A of the case 2 is close to 1, the irradiation angles φa = 0.09 ° and φb = 0.17 ° of the case 2 are determined.

つぎに、被測定物の付着形態が未知の測定対象試料について、前記決定した照射角度φａ＝０．０９°，φｂ＝０．１７°で全反射蛍光Ｘ線測定する。粒状の測定対象試料の場合、前記標準試料２の場合と同様に、Ｎｉ−Ｋα線の強度Ｉa3，Ｉb3は、０．０９°のとき４０４．９１ｃｐｓ、０．１７°のとき４１５．３０ｃｐｓである。したがって、測定対象試料についての蛍光Ｘ線強度Ｉa3，Ｉb3の比である測定対象試料の粒度係数ＰＦ３は、ＰＦ３＝４０４．９１／４１５．３０＝０．９７である。この場合、前記した照射角度φｃ＝０．０９°での検量線を用いて、Ｎｉ−Ｋα線の強度を測定対象試料のニッケルの汚染量Ｃ１に換算すると、約５．８×１０12atoms/cm2 となる。 Next, a total reflection fluorescent X-ray measurement is performed with respect to the measurement target sample whose attachment form of the object to be measured is unknown at the determined irradiation angles φa = 0.09 ° and φb = 0.17 °. In the case of a granular sample to be measured, as in the case of the standard sample 2, the intensities Ia3 and Ib3 of the Ni-Kα line are 404.91 cps at 0.09 ° and 415.30 cps at 0.17 °. . Therefore, the particle size factor PF3 of the measurement target sample, which is the ratio of the fluorescent X-ray intensities Ia3 and Ib3 for the measurement target sample, is PF3 = 404.91 / 415.30 = 0.97. In this case, using the calibration curve at the irradiation angle φc = 0.09 °, when the intensity of the Ni-Kα ray is converted into the nickel contamination amount C1 of the sample to be measured, about 5.8 × 10 12 atoms / cm 2

存在量決定手段８は、例えば標準試料１の粒度係数ＰＦ１＝０．２５と測定対象試料の粒度係数ＰＦ３＝０．９７に基づき、粒度係数ＰＦ１とＰＦ３の比（すなわち蛍光Ｘ線の強度比）ＰＦ１／ＰＦ３を用いて、測定対象試料のニッケルの汚染量Ｃ１について、次式により補正を行う。補正後のニッケルの汚染量をＣ２とする。
Ｃ２＝Ｃ１・（ＰＦ１／ＰＦ３）
＝５．８×１０12・（０．２５／０．９７）
＝１．５×１０12
このように、補正後のニッケルの汚染量Ｃ２は約１．５×１０12atoms/cm2 であり、前記した標準試料１のニッケルの汚染量に等しく、被測定物の存在量を正確に決定できる。 The abundance determination means 8 is based on, for example, the particle size factor PF1 = 0.25 of the standard sample 1 and the particle size factor PF3 = 0.97 of the sample to be measured, that is, the ratio of the particle size factors PF1 and PF3 (that is, the fluorescent X-ray intensity ratio). Using PF1 / PF3, the nickel contamination amount C1 of the sample to be measured is corrected by the following equation. Let the amount of nickel contamination after correction be C2.
C2 = C1 · (PF1 / PF3)
= 5.8 × 10 12 · (0.25 / 0.97)
= 1.5 × 10 12
Thus, the corrected nickel contamination amount C2 is about 1.5 × 10 12 atoms / cm 2, which is equal to the nickel contamination amount of the standard sample 1 described above, and accurately determines the abundance of the object to be measured. it can.

したがって、本発明は、Ｉa2・ＰＦ１／ＰＦ２の値がＩa1の値に近づくように、つまり、係数Ａが１に近づくように、照射角度φａ、φｂを決定し、この決定した照射角度φａ、φｂにおける測定対象試料についての蛍光Ｘ線の強度Ｉa3，Ｉb3の比ＰＦ３を用いて、被測定物の存在量を正確に決定することができる。   Therefore, in the present invention, the irradiation angles φa and φb are determined so that the value of Ia2 · PF1 / PF2 approaches the value of Ia1, that is, the coefficient A approaches 1, and the determined irradiation angles φa and φb are determined. The abundance of the object to be measured can be accurately determined using the ratio PF3 of the fluorescent X-ray intensities Ia3 and Ib3 for the measurement target sample in FIG.

なお、本実施形態では、存在量決定手段８は、ケース２のＰＦ１／ＰＦ３の値１／４に基づいて被測定物の存在量を決定しているが、ケース１の場合の係数Ａは１．３であり、ケース２の場合の係数Ａが１であるのに比較して、精度は劣るが、ケース２の精度で十分な場合には、ケース１のＰＦ１／ＰＦ３の値１／６に基づいて被測定物の存在量を決定するようにしてもよい。 In the present embodiment, the abundance determination means 8 determines the abundance of the DUT based on the value ¼ of PF1 / PF3 in case 2, but the coefficient A in case 1 is 1. .3, and the accuracy is inferior to the coefficient A in case 2 being 1. However, if the accuracy in case 2 is sufficient, the value of PF1 / PF3 in case 1 is reduced to 1/6. The abundance of the object to be measured may be determined based on this.

なお、本実施形態では、測定対象試料についての蛍光Ｘ線の強度比から、被測定物の存在量を決定しているが、蛍光Ｘ線の強度差によって、強度比と同じようにして、被測定物の存在量を決定するようにしてもよい。   In this embodiment, the abundance of the object to be measured is determined from the intensity ratio of the fluorescent X-rays for the sample to be measured. The abundance of the measurement object may be determined.

本発明の一実施形態に係る蛍光Ｘ線分析装置を示す側面図である。1 is a side view showing a fluorescent X-ray analyzer according to an embodiment of the present invention. （Ａ）、（Ｂ）は蛍光Ｘ線強度と１次Ｘ線の照射角度との関係を示す特性図である。(A) and (B) are characteristic diagrams showing the relationship between the fluorescent X-ray intensity and the primary X-ray irradiation angle. （Ａ）〜（Ｃ）は被測定物の形態を示す側面図である。(A)-(C) are side views which show the form of a to-be-measured object.

符号の説明Explanation of symbols

５…測定手段、６…演算手段、８…存在量決定手段、５０…試料、Ｂ１…１次Ｘ線、Ｂ３…蛍光Ｘ線。   5 ... Measurement means, 6 ... Calculation means, 8 ... Abundance determination means, 50 ... Sample, B1 ... Primary X-ray, B3 ... Fluorescent X-ray.

Claims (2)

試料表面に１次Ｘ線を照射し、試料表面部に存在する被測定物から発生した蛍光Ｘ線を測定する蛍光Ｘ線分析方法であって、
被測定物の存在量は等しいが、被測定物の付着形態がフィルム状である標準試料１および粒状である標準試料２について、前記１次Ｘ線をそれぞれ相異なる複数の照射角度φ１〜φｎで照射して蛍光Ｘ線の強度を測定し、そのうち任意の２つの照射角度φa ，φb （φa ＜φb ）の複数の組について、それぞれ標準試料１の蛍光Ｘ線強度Ｉa1，Ｉb1の比を標準試料１の粒度係数ＰＦ１として求め、標準試料２の蛍光Ｘ線強度Ｉa2，Ｉb2の比を標準試料２の粒度係数ＰＦ２として求めて、これら得られた各組についての蛍光Ｘ線強度Ｉa1，Ｉa2および粒度係数ＰＦ１、ＰＦ２から、Ｉa2・ＰＦ１／ＰＦ２の値がＩa1の値に最も近づくように、照射角度φａ，φｂの組を選択し、
前記選択した照射角度φａ，φｂにおける測定対象試料についての蛍光Ｘ線の強度Ｉa3，Ｉb3から、付着形態がフィルム状または粒状である被測定物の存在量を決定する蛍光Ｘ線分析方法。 A fluorescent X-ray analysis method for irradiating a sample surface with primary X-rays and measuring fluorescent X-rays generated from an object existing on the sample surface,
Although the abundance of the object to be measured is the same, the primary X-ray is irradiated at a plurality of different irradiation angles φ1 to φn with respect to the standard sample 1 and the standard sample 2 having a granular form in which the object to be measured is attached. The intensity of fluorescent X-rays is measured by irradiation, and the ratio of the fluorescent X-ray intensities Ia1 and Ib1 of the standard sample 1 is determined for each of a plurality of pairs of arbitrary two irradiation angles φa and φb (φa <φb). 1 as the particle size factor PF1, and the ratio of the fluorescent X-ray intensities Ia2 and Ib2 of the standard sample 2 is obtained as the particle size factor PF2 of the standard sample 2, and the fluorescent X-ray intensities Ia1, Ia2 and the particle size of each of these obtained sets From the coefficients PF1 and PF2, a set of irradiation angles φa and φb is selected so that the value of Ia2 · PF1 / PF2 is closest to the value of Ia1.
A fluorescent X-ray analysis method for determining an abundance of an object to be measured having a film form or a granular form from the intensities Ia3 and Ib3 of the fluorescent X-rays with respect to the sample to be measured at the selected irradiation angles φa and φb. 試料表面に１次Ｘ線を照射し、試料表面部に存在する被測定物から発生した蛍光Ｘ線を測定する蛍光Ｘ線分析装置であって、
被測定物の存在量は等しいが、被測定物の付着形態がフィルム状である標準試料１および粒状である標準試料２について、前記１次Ｘ線をそれぞれ相異なる複数の照射角度φ１〜φｎで照射して蛍光Ｘ線の強度を測定する測定手段と、
前記複数の照射角度のうち任意の２つの照射角度φa ，φb （φa ＜φb ）の複数の組について、それぞれ標準試料１の蛍光Ｘ線強度Ｉa1，Ｉb1の比を標準試料１の粒度係数ＰＦ１として求め、標準試料２の蛍光Ｘ線強度Ｉa2，Ｉb2の比を標準試料２の粒度係数ＰＦ２として求めて、これら得られた各組についての蛍光Ｘ線強度Ｉa1，Ｉa2および粒度係数ＰＦ１、ＰＦ２から、Ｉa2・ＰＦ１／ＰＦ２の値がＩa1の値に最も近づくように、照射角度φａ，φｂの組を選択する演算手段と、
前記選択した照射角度φａ，φｂにおける測定対象試料についての蛍光Ｘ線の強度Ｉa3，Ｉb3から、付着形態がフィルム状または粒状である被測定物の存在量を決定する存在量決定手段とを備えた蛍光Ｘ線分析装置。 A fluorescent X-ray analyzer that irradiates a sample surface with primary X-rays and measures fluorescent X-rays generated from an object existing on the sample surface,
Although the abundance of the object to be measured is the same, the primary X-ray is irradiated at a plurality of different irradiation angles φ1 to φn with respect to the standard sample 1 and the standard sample 2 having a granular form in which the object to be measured is attached. Measuring means for irradiating and measuring the intensity of fluorescent X-rays;
The ratio of the fluorescent X-ray intensities Ia1 and Ib1 of the standard sample 1 is set as the particle size factor PF1 of the standard sample 1 for a plurality of sets of any two irradiation angles φa and φb (φa <φb) among the plurality of irradiation angles. The ratio of the fluorescent X-ray intensities Ia2 and Ib2 of the standard sample 2 is obtained as the particle size coefficient PF2 of the standard sample 2, and from the fluorescent X-ray intensities Ia1 and Ia2 and the particle size coefficients PF1 and PF2 for each of these obtained sets, Arithmetic means for selecting a set of irradiation angles φa and φb so that the value of Ia2 · PF1 / PF2 is closest to the value of Ia1;
Abundance determining means for determining the abundance of the object to be measured having a film form or a granular form based on the fluorescent X-ray intensities Ia3 and Ib3 of the sample to be measured at the selected irradiation angles φa and φb; X-ray fluorescence analyzer.
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