201142275 六、發明說明： 【發明所屬之技術領域】 本發明係關於由根據光學顯微鏡的座標計測來決定位 置’即使搭載著試樣而基板（基材）所包含的元素與試樣 所含的元素爲相同，也可以進行安定的微小部分的計測之 微小部X線計測裝置。 【先前技術】 關於大塊試樣的微小部分或被搭載於各種基板的微小 試樣的測定方法，例如已有顯微紅外線分光法、顯微拉曼 分光法、電子束激發螢光X線分析法等種種方法被開發出 來。其中，以紅外線分光法與拉曼分光法，特別適用於有 機材料的計測。此外，電子束分析法一般應用於無機材料 或金屬的計測，特別是藉由在真空中之計測，即使鋁（A1 )這種輕元素也可以計測，所以被廣泛使用。然而，在電 子束分析法，有必要將試樣插入真空中，所以不容易提高 計測的處理能力，同時特別是要適用於大型的試樣或者大 型基板上的試樣之計測是很困難的。 對此，從前例如以下的專利文獻1也記載著，爲了半 導體製造步驟之成膜控制，開發出以微小部的計測爲目的 之企圖達成高感度/高計測處理速度之X線計測裝置。在 此專利文獻1的裝置，爲了在高精度下控制膜厚’在進行 計測的一點（微小部）之計測時間需要5秒〜20秒程度， 必須要花比較長的時間。另一方面，如以下之專利文獻2 -5- 201142275 、專利文獻3或專利文獻4所知的，已開發出倂用光學計測 與X線計測的裝置，但在重視根據光學顯微鏡的計測的裝 置，於X線計測部分不使用光學元件’不考慮螢光X線的 發生效率或是來自基板的背景雜訊’所以特別是對微小金 屬之計測能力，只有微克到毫克程度而已’毫微克（ nano gram )程度的微小量之金屬計測是不可能的。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2006- 1 53 767號公報 [專利文獻2]國際公開公報W02 009 / 09334 1號小 冊 [專利文獻3 ]日本專利特開2 0 0 9 - 1 9 8 4 8 5號公報 [專利文獻4 ]日本專利特開2 0 0 9 - 2 5 8 1 1 4號公報 【發明內容】 [發明所欲解決之課題] 然而’大型的試樣，或者被搭載於大型基板的試樣的 螢光X線計測，有必要在大氣中進行，然而這樣的場合， 會有X線在大氣中衰減的問題。 此外’爲了進行微小部分的X線測定，必須要將X線 光束聚焦於微小的剖面積之X線光學元件，同時必須要有 光學顯微鏡，進而’對此，還必須要針對包含螢光X線計 測用的X線檢測器的配置去下工夫。 201142275 爲此，在本發明，係有鑑於前述先前技術之問題點而 達成之發明，其目的在於提供即使被搭載著試樣的基板（ 基材）所包含的元素，與該試樣所含的元素爲相同，也可 以進行安定的微小部分的成分計測之微小部X線計測裝置 [供解決課題之手段] 本發明，如前所述，係有鑑於對大型的試樣，或者被 搭載於大型的基板（基材）的試樣的螢光X線計測，有在 大氣中進行的必要而達成的發明，特別是藉由以下所述之 根據發明人的知識與見解而達成者。亦即，在大氣中進行 螢光X線計測的場合，例如由輕元素之鋁（A1 )所放出的 營光X線（特性X線能量爲1.5keV)，於大氣中每前進1mm 就會衰減約20°/。。另一方面，由鐵（Fe)或銅（Cu)等過 渡金屬元素所放出的螢光X線（特性X線能量分別爲 6.8keV、8.0keV )，在大氣中前進數個mm程度的距離也 幾乎不會衰減。亦即，如果把由試樣到檢測器的檢測元件 爲止的距離（螢光X線在大氣中的路徑（光徑））儘可能 地縮短’例如設定爲5 m m以下的話，可以使1 . 5 k e V程度的 螢光X線在大氣中的透過率達到30%程度，藉此，可以檢 測出比鋁（A1 )原子序更大的元素的螢光X線。 爲此’在本發明’根據前述之發明人的知識見解，爲 了達成前述目的’首先提供微小部X線計測裝置，其係具 備：X線發生裝置、使由該X線發生裝置放出的X線在測定 201142275 試樣上聚焦照射於50μηι直徑以下的剖面積之X線光學元件 、檢測由前述測定試樣所放出的螢光X線之X線檢測器、 可攝影X線照射位置的光學影像的光學顯微鏡，以及可以 使前述試樣二次元地掃描、定位，且以於高度方向上可以 使空氣路徑成爲5mm以下的方式調整其位置的試樣相對移 動機構；可藉由根據前述光學顯微鏡之影像辨識機能，而 進行前述試樣的特定位置之螢光X線計測，而且也可以計 測來自被置於基材上的測定試樣的螢光X線的微小部X線 計測裝置；使藉由前述X線光學元件聚焦照射於50μιη直徑 以下的剖面積之X線照射位置與前述X線檢測器之間的螢 光X線的光徑，爲抑制該螢光X線的衰減之構造，同時， 進而具備備有即使被置於前述基材上的前述測定試樣包含 與該基材相同的金屬元素，也可以判定出前述測定試樣含 有該相同的金屬元素的資料處理機能之資料處理部。 此外，在本發明，於前述記載之微小部X線計測裝置 ，最好是使被聚焦照射於前述50μηι直徑以下的剖面積之X 線照射位置與前述X線檢測器之間的螢光X線的光徑成爲 真空，或者是使被聚焦照射於前述5 0 μηι直徑以下的剖面 積之X線照射位置與前述X線檢測器之間的螢光X線的光徑 ，藉由氦氣（He )來置換。或者是，於前述X線發生裝置 發生X線的金屬，最好是原子序24之鉻（Cr)、原子序42 之鉬（Mo)至原子序47之銀（Ag)、或者原子序74之鎢 (W)至原子序79之金（Au)爲止之各元素的單體或者包 含複數元素之合金或者層.積膜，將前述X線光學元件的內 -8- 201142275 部空間予以真空排氣或氨氣（He )置換爲較佳。 此外，在本發明，於前述記載之微小部x線計測裝置 ，最好是藉由具有1個或複數個X線光子的能量辨別機能 的半導體X線檢測元件來構成前述X線檢測器，進而，前 述光學顯微鏡，最好是於該光學顯微鏡之中心軸，具備可 插入前述X線檢測元件的孔，而且使該光學顯微鏡之光軸 與照射X線束的中心軸爲同軸。而且，最好是於前述光學 顯微鏡使用卡塞格倫（Cassegrain )型之反射光學顯微鏡 ，於對向於前述試樣的副鏡面背面之照射X線光束與前述 光學顯微鏡的光軸的同軸中心軸的周圍，具備單數或複數 之X線檢測元件，進而，最好是具備抑制由前述試樣所發 散/放出的營光X線的發散角的手段。 [發明之效果] 根據前述之本發明，可提供可以辨識大型試樣或者被 搭載於大型基板的試樣的顯微鏡影像而螢光X線計測特定 微小部分的兀素’同時即使被搭載著試樣的基板（基材） 所包含的元素，與該試樣所含的元素爲相同，也可以進行 安定的微小部分的成分計測之微小部X線計測裝置，於實 用上發揮優異的效果。 【實施方式】 以下，參照附圖詳細說明本發明之實施型態。 201142275[Technical Field] The present invention relates to determining the position by the coordinate measurement by the optical microscope. The elements contained in the substrate (substrate) and the elements contained in the sample even if the sample is mounted thereon In the same manner, it is also possible to perform a small-part X-ray measuring device for measuring a small portion of stability. [Prior Art] A method for measuring a minute portion of a bulk sample or a small sample mounted on various substrates, for example, microscopic infrared spectroscopy, micro Raman spectroscopy, and electron beam excitation fluorimetry Various methods such as law were developed. Among them, infrared spectroscopy and Raman spectroscopy are particularly suitable for the measurement of organic materials. Further, the electron beam analysis method is generally applied to measurement of inorganic materials or metals, and in particular, it can be measured by measurement in a vacuum, and even a light element such as aluminum (A1) can be measured, so it is widely used. However, in the electron beam analysis method, it is necessary to insert the sample into a vacuum, so that it is not easy to improve the processing ability of the measurement, and it is particularly difficult to measure the sample on a large sample or a large substrate. In the past, for example, Patent Document 1 below discloses that an X-ray measuring device that attempts to achieve high sensitivity/high measurement processing speed for the purpose of measurement of a minute portion has been developed for the film formation control of the semiconductor manufacturing step. In the apparatus of Patent Document 1, in order to control the film thickness with high precision, it takes 5 seconds to 20 seconds to measure the point (micro portion) of the measurement, and it takes a long time. On the other hand, as disclosed in the following Patent Documents 2-5-201142275, Patent Document 3, or Patent Document 4, devices for measuring optical and X-rays have been developed, but devices that are based on measurement by optical microscopes are emphasized. In the X-ray measurement section, the optical component is not used 'regardless of the efficiency of the fluorescent X-ray or the background noise from the substrate', so especially for the measurement of tiny metals, only micrograms to milligrams have been 'nanograms (nano Gram) A small amount of metal measurement is impossible. [Prior Art Document] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2006- 1 53 767 [Patent Document 2] International Publication No. WO 02 009 / 09334 Book No. 1 [Patent Document 3] Japanese Patent Laid-Open 2 0 0 9 - 1 9 8 4 8 5 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2000-254-119 The sample or the X-ray measurement of the sample mounted on the large substrate needs to be performed in the atmosphere. However, in this case, there is a problem that the X-ray is attenuated in the atmosphere. In addition, in order to carry out the X-ray measurement of a small part, it is necessary to focus the X-ray beam on the X-ray optics of a small cross-sectional area, and at the same time, an optical microscope must be provided, and in addition, it must be directed to the inclusion of fluorescent X-rays. The configuration of the X-ray detector for measurement is taken down. Therefore, the present invention has been made in view of the problems of the prior art described above, and an object thereof is to provide an element contained in a substrate (substrate) on which a sample is mounted, and a sample contained in the sample. A micro-X-ray measuring device that can measure a component of a stable minute portion, which is the same element. [Means for Solving the Problem] As described above, the present invention is applied to a large sample or a large-sized sample. The X-ray measurement of the sample of the substrate (substrate) is carried out in the atmosphere, and is achieved by the knowledge and insights of the inventors described below. In other words, in the case of performing fluorescent X-ray measurement in the atmosphere, for example, the camping X-ray (characteristic X-ray energy is 1.5 keV) emitted by aluminum (A1) of light element is attenuated every 1 mm in the atmosphere. About 20°/. . On the other hand, the fluorescent X-rays emitted from transition metal elements such as iron (Fe) or copper (Cu) (the characteristic X-ray energies are 6.8 keV and 8.0 keV, respectively), and the distance in the atmosphere is several mm. Almost no attenuation. In other words, if the distance from the sample to the detecting element of the detector (the path (light path) of the fluorescent X-ray in the atmosphere) is shortened as much as possible, for example, if it is set to 5 mm or less, 1.5. The transmittance of the fluorescent X-ray at a level of ke V is 30% in the atmosphere, whereby the fluorescent X-ray of an element larger than the atomic order of aluminum (A1) can be detected. To this end, in the present invention, in order to achieve the above object, in order to achieve the above object, a micro X-ray measuring device is provided, which is provided with an X-ray generating device and an X-ray emitted by the X-ray generating device. An X-ray optical element that focuses on a cross-sectional area of a diameter of 50 μm or less on a sample of 201142275, an X-ray detector that detects a fluorescent X-ray emitted from the measurement sample, and an optical image of a photographable X-ray irradiation position are measured. An optical microscope, and a relative movement mechanism of the sample which can scan and position the sample in a secondary direction and adjust the position of the air path so as to be 5 mm or less in the height direction; By identifying the function, the X-ray measurement of the specific position of the sample is performed, and the X-ray measuring device of the fluorescent X-ray from the measurement sample placed on the substrate can be measured; The X-ray optical element focuses the optical path of the fluorescent X-ray between the X-ray irradiation position of the cross-sectional area irradiated to a diameter of 50 μm or less and the X-ray detector, in order to suppress the It is also possible to determine that the measurement sample contains the same metal even if the measurement sample placed on the substrate contains the same metal element as the substrate. The data processing unit of the data processing function of the element. Further, in the present invention, it is preferable that the micro X-ray measuring device described above is a fluorescent X-ray between the X-ray irradiation position of the cross-sectional area that is focused and irradiated to the diameter of 50 μm or less and the X-ray detector. The optical path is a vacuum or an optical path of a fluorescent X-ray between the X-ray irradiation position of the cross-sectional area that is focused and irradiated to the diameter of 50 μm or less and the X-ray detector, by Helium (He ) to replace. Alternatively, the X-ray metal in the X-ray generating device is preferably chromium (Cr) of atomic order 24, molybdenum (Mo) of atomic order 42, silver (Ag) of atomic order 47, or atomic order 74. A monomer of each element up to the gold (Au) of atomic order 79 or an alloy or layer containing a plurality of elements. The film is formed, and the inner-8-201142275 space of the aforementioned X-ray optical element is vacuum-exhausted. Or ammonia (He) replacement is preferred. Further, in the above-described micro-part x-ray measuring device, it is preferable that the X-ray detector is configured by a semiconductor X-ray detecting element having an energy discrimination function of one or a plurality of X-ray photons, and further Preferably, the optical microscope has a hole into which the X-ray detecting element can be inserted, and the optical axis of the optical microscope is coaxial with a central axis of the X-ray beam. Further, it is preferable that the above-mentioned optical microscope uses a Cassegrain-type reflective optical microscope to align the X-ray beam of the sub-mirror surface of the sample to the coaxial central axis of the optical axis of the optical microscope. The periphery is provided with a single or plural X-ray detecting element, and further preferably, means for suppressing the divergence angle of the camping X-rays emitted/released by the sample. [Effects of the Invention] According to the present invention described above, it is possible to provide a microscope image in which a large sample or a sample mounted on a large substrate can be recognized, and a specific minute portion of the halogen is measured by the fluorescent X-ray, and the sample is mounted thereon. In the substrate (substrate), the element included in the sample is the same as the element contained in the sample, and the micro-section X-ray measuring device that measures the component of the stable minute portion exhibits an excellent effect in practical use. [Embodiment] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. 201142275
構 澧 全 的 置 裝 測 計 線 X 的 11 例 施 實 之 明 發 本1]示 例顯 施係 [«BI 成之立體圖。於此處未圖示的箇體的內部，搭載著χ線發 生裝置1、X線檢測器3、以及光學顯微鏡4。於使在X線發 生裝置1發生的X線聚焦於微小面積之用的X線光學元件2 ，使用聚合毛細管（Polycapillary)型之元件，而且將該 聚合毛細管型之X線光學元件2直接安裝於X線發生裝置1 。藉此，在X線發生裝置1發生的X線，藉由前述聚合毛細 管型之X線光學元件2的作用，例如，被聚焦至50μηι以下 的微小剖面積，接著照射於被載置在試樣相對移動機構（ 移動台）6上的試樣5。又，對於前述X線發生裝置1及根 據聚合毛細管型之X線光學元件2的X線的照射位置之前述 試樣5的位置控制，係藉由試樣移動控制部6 1來進行的。 又，本實施例之聚合毛細管型之X線光學元件2，係 具有於X線發生裝置1把鉬（Mo )金屬作爲X線靶材產生X 線而把對能量1 7.5 keV的X線聚焦至1 5 μηι之直徑，把對能 量8.0keV的X線聚焦至25μιη之直徑的作用。此外，於X線 發生裝置1作爲發生X線的金屬靶材，亦可把由原子序42 之前述的鉬（Mo)至原子序47之銀（Ag)、或者，原子 序74之鎢（W)至原子序79之金（Au)爲止之各元素，作 爲單體，或複數之合金或者層積膜來使用。 此外，前述X線發生裝置1的加速電壓/電流，進而X 線快門等之控制’係以X線發生控制部1 1來進行。此外， 藉由前述聚合毛細管（Polycapillary)型之X線光學元件2 -10- 201142275 而聚焦的X線的照射位置的確認，係藉由光學顯微鏡4來 進行。亦即’由顯微鏡光源4 3射出的光，通過前述光學顯 微鏡4被照射於試樣5，接著由該試樣5反射/散射的光， 於被安裝在上述光學顯微鏡4的CCD單元42上成像爲試樣 影像，因而作爲電氣訊號往顯微鏡控制部41傳送。 接著’未圖示的筐體，藉由終究未被圖示的位置控制 機構，自由地選擇在三次元座標（參照圖之X-Y-Z )上的 位置而設定爲計測位置。其中，X-Y係基板之試樣5上的 二次元座標’ Z爲筐體的高度，這是藉由該基板與光學顯 微鏡4的焦點位置來進行調整。 接著’使用附屬之圖2，說明成爲實施例1的X線計測 裝置之更爲詳細的構造。於試樣5，藉由前述X線發生裝 置1及X線光學元件2，照射X線。此時，在X線發生裝置1 發生的X線，如前所述，藉由通過X線光學元件2，而被聚 焦於小的照射面積。又，此X線光學元件2的內部，被排 氣爲真空’或者藉由氦氣置換，藉此，成爲防止通過其內 部的X線哀減的構造。 另一方面，由被照射X線的試樣（基板）5上的微小 部位5 1所放出的螢光X線32，由X線檢測器3所捕獲，藉由 檢測器控制部3 1，被變換爲X線光子數對螢光X線能量之 柱狀圖而被送至資料處理裝置7。藉此，以光學顯微鏡4所 捕捉到的試樣5，藉由根據試樣相對位置移動機構6之移動 ’而使在X線發生裝置1發生的X線移動至藉由X線光學元 件2而被聚焦/照射的位置，使此時發生的螢光X線藉由χ -11 - 201142275 線檢測器3來捕獲，於資料處理裝置7，進行捕獲的螢光X 線的光子能量分布（光譜）的解析，從而進行被照射X線 的部位的元素分析。又，此時，如果使試樣的微小部位5 1 起至X線檢測器3爲止的距離成爲在5 mm以下，則即使由試 樣的微小部位5 1發生而能量爲1 .OkeV的特性X線，也可以 抑制其在空氣中的衰減，而可以將此檢測出。 特別是，在本實施例，作爲X線發生裝置1的X線靶材 ，使用鉬（Mo)的場合，在施加電壓50kV，電流0.5mA的 動作條件下，3 00Mcps之X線被照射於試樣5的微小部位51 。此時，以原子序42的鉬（Mo )起至原子序47之銀（Ag )爲止的金屬爲X線靶材的話，於照射的X線之中，會混 入L α之特性X線。又，此L α之特性X線，在MoL α ’ X線 能量爲2.29keV，在AgL α ，X線能量爲2.98keV ’亦即， 接近於鋁金屬（A1)的螢光X線激發能量之l_56keV附近， 可以由鋁金屬（A1 )以很高的效率放出A1K α之螢光X線 。另一方面，ΜοΚ α及AgK α之特性X線，對過渡金屬之 激發是有效的，與一般使用的金屬元素之Α1同樣’對於Cr 、Fe、Co、Ni、Cu等過渡金屬的微小部螢光X線分析是有 效的，可以進行高感度的計測。 其次，於附圖3，顯示於本發明之X線計測裝置供進 行X線計測之用的座標測定之流程。 由圖可知，開始XRF (螢光X線）測定位置檢測時’ 首先把測定位置之編號（m)設定爲m=0(步驟S31) ’ 接著，使其値m僅增加1 ( m= m+ 1 )(步驟S32) °接著 -12- 201142275 ，進行座標移動直到測定位置之編號（m )的座標（例如 ，（mx，my ))(步驟S 3 3 )，接著進行Z位置的調整（ 步驟S34)。首先，進行光學測定（步驟S35)，判定有無 微粒子的存在（步驟S 3 6 )。其結果，在判定爲有微粒子 的存在的場合（圖之「Yes」），記錄其座標（步驟S3 7 ) ，其後，藉由前述之m之値，判定所有的測定是否結束（ 步驟S38)。另一方面，在判定沒有微粒子存在的場合（ 圖之「No」），立刻移至前述步驟S37。 接著，前述步驟S 3 7之判定結果，爲測定尙未結束（ 圖之「No」）的場合，處理，會再度回到前述步驟S32， 另一方面，在判定所有的測定都結束（圖之「Yes」）的 場合’將微粒子存在的座標，配置於記錄的座標的前頭（ 步驟S39)，進而作爲M0=m+1 (步驟S40)，結束處理 〇 又，前述之流程，係顯示供決定進行螢光X線測定的 位置的座標之用的，使用可見光來進行之一例。又，爲了 要決定座標，除了前述的可見光以外，例如也可以使用紅 外線或紫外線的方式。又，以可見光決定X線計測座標之 後可以立刻進行X線計測。 進而’於附圖之圖4〜圖6，顯示使用前述圖1及圖2所 示的構成之X線計測裝置來測定的螢光X線的光子能量分 布之一例。又，此測定例的場合，在X線發生裝置發生的 X線的光子能量爲5.4keV。 圖4係顯示試樣所含的元素的特性X線之能量，及藉 201142275 由一定時間的測定而檢測出的光子之計測資料，藉由此圖 4之資料，可以測定在計測區域所含的元素的種類與數量 。接著，在本發明之計測裝置，特別試藉由把大氣中的X 線路徑設定爲5mm以下，可以抑制在大氣中的螢光X線的 衰減，結果，如圖4所示，也可以檢測出鈉（Na )。又， 鈣（Ca)或鋇（Ba)之螢光X線，在大氣中幾乎不會衰減 ，所以可在高感度下進行測定。 其次，使用圖5與圖6，說明於基板包含著與試樣微粒 子相同的原子種的場合之檢測方法。 於大多數領域作爲基板使用的材料，有玻璃。在相關 的玻璃，作爲一般使用的，有氧化鋁矽酸鹽，其組成爲鹼 金屬/驗土類金屬，及氧化銘/氧化砂之混合物。此處使 用的玻璃基板之螢光X線光譜之例顯示於圖5。 於此圖5所示之光譜，被測量到鋁（A1 )、矽（Si ) 、磷（P)、少量的硫（S)、氯（C1)，進而還有大氣中 的氬氣（Ar )。此外，由此測定結果，作爲玻璃中所含有 的元素，檢測出A1與Si。又，P、S、C1係藉由玻璃表面的 處理而附著之物所被測量到的。 此處，在前述之玻璃基板的表面上分散A1金屬粉，藉 由移動基板位置’而將該A1金屬粉導入前述X線照射區域 內，使螢光X線以與前述相同的條件來測定，藉此所得到 的結果顯示於圖6。 在此，取這些被測定的光譜之差的話，得到於附圖之 圖7中標示著「差分光譜」之差分光譜。又，在此例，出 -14- 201142275 現的峰，係由A1的微小金屬粉所造成的峰，亦即，可以檢 測出微小異物。又，根據此方法，藉由本實施例之裝置測 定的結果，可以檢測出1 n g程度的A 1微小金屬粉。 此處’針對在本發明使用的微小金屬粉的檢測，說明 其確定性（確實性）。X線的檢測，係藉由檢測器，藉由 計測入射至該檢測器的X線的光子而進行的，其數目（N )的測量精度，作爲計測統計誤差（1 σ )，係以Ν的平 方根來表示。此外，在X線的計測，必然會觀測到由檢測 器自身，或者是由電子電路所產生的背景雜訊。接著，來 自微小異物的螢光X線的計測強度，係以包含金屬微粒子 的計測値（Ν 1 )，與不含該金屬微粒子的計測値（Ν0 ) 之差（N1-N0 )來表示，分別的計測値，包含，Nl、，NO 之計測統計誤差（1 σ )。亦即，爲了判斷來自微小金屬 粒子的螢光X線強度係以η σ的水準來測定的，而使用以 下之式（1 )。 η = ( Ν 1 -NO ) / ( Ν 1 + Λ NO ) . · . ( 1 ) 在η = 1，常態分佈函數有68%的機率可以判定「有微 小金屬異物」，其機率在η=2的場合成爲95°/。，進而在η =3的場合成爲99.7 %。作爲一例，在Ν1與NO分別爲1000 與900的場合，n = 1.6，接著，N1與NO分別爲500與400的 場合，成爲η = 2.4，即使來自微小金屬粒子的計測強度（ Ν 1-Ν0 )爲相同，也因爲後者的背景螢光X線雜訊強度很 -15- 201142275 低，所以成爲確實性很高的檢測。此外，計測強度（N 1 -NO )係來自微小金屬粒子的螢光X線強度，爲大致比例於 金屬粒子重量之値。 此處，檢測出複數種過度金屬粒子的場合，藉由進行 以下的處理，可謀求資料精度的提高。又，作爲常用的過 渡金屬元素，可以舉出原子序24之鉻（Cr)〜原子序29之 銅（Cu )，但對於各元素被激發的2種螢光X線之中，被 稱爲ΚΘ之高能量側的X線，與原子序大1號之被稱爲Κα 的低能量側的光譜重疊。其模樣顯示於附圖8。亦即，被 檢測出各元素的螢光X線的場合，因爲Κ α以外必定有Κ冷 存在，而在測量到的光譜資料上進行處理。同樣的，對於 進而原子序更大的元素，則作爲有複數之La與者來 進行處理。藉此，可以謀求計測資料的精度提高。 其次，說明使用複數點之資料，來抑制基板所含有的 元素的影響之方法。此處使用的螢光X線檢測器，使用所 謂的能量分散型（ED )檢測器，對於多通道分析器之光 譜，係以數位的方式被蓄積於資料處理裝置7的記憶體。 亦即，此處所述之演算，係以非常高的速度來執行的。 於基板上有複數點之計測資料的場合，不一定對各測 定點都進行沒有金屬微粒子之計測，可以推定來自基板的 螢光X線光譜。基板的種類係屬已知。例如，在玻璃的場 合，其組成爲鹼金屬（Na、K等）、鹼土類金屬（Ca、Ba 等）與鋁（A1 )及矽（S i )與氧（Ο )。亦即，在進行微 粒子的螢光X線測定時，微粒子不是這些元素而是過渡金 -16- 201142275 屬（例如Cr、Fe、Co、Ni、Cu等）的場合，構成微粒子 的元;素以外’都可以判定是來自源於基板的元素的螢光χ 線。亦即’包含微粒子的測定之中，檢測出原本基板不含 有的元素的場合’基板所包含的元素的螢光X線光譜，可 以判斷是來自基板者。 例如’複數之計測金屬微粒子與來自基板的元素爲相 同的場合’比較複數之光譜，例如比較對應於鋁（A1 )的 光譜的螢光X線強度，把最小的數値假定爲源自基板的螢 光X線強度，而藉由前述式（1 )來計算η値。同樣地，最 大的Α1螢光X線的η値，在閾値nt (例如，nt = 2.0 )以上 的場合，把最低的A1螢光X線強度當作爲來自基板的螢光 X線強度。結果，在所有的計測之η値都在閾値nt以下的場 合，把金屬微粒子不存在的場所之螢光X線強度作爲來自 基板的螢光X線強度。如此進行，藉由求出來自基板的螢 光X線強度，總是比較存在金屬微粒子（有）之點，與不 存在（無）之點的計測的場合，可以高速地進行計測。又 ，此時之測定之一例，顯示於附圖9。 如此圖9之流程所示，開始微小部XRF (螢光X線）計 測時，首先，把測定位置的編號（m )設定爲m = 0 (步驟 S91 )，接著，使該値m僅增加l(m=m+i)(步驟S92 )。其次，直到測定位置的編號（m )的座標（例如，（ mx，my ))爲止進行座標移動（步驟S93 )，接著，進行 Z位置的調整（步驟S94 )。其後，進行XRF (螢光X線） 計測（步驟S 9 5 )，藉由其結果所得到的資料，找出m資 -17- 201142275 料的最小値（步驟S96 )。其後，使k = 〇、Ml = m (步驟 S97)，其次，使k逐次增加l(k=k+l)(步驟S98)， 同時算出全測定η値（步驟S 9 9 )，製作圖之左側所示之表 。其後，確認所有的資料處理之結束（步驟S100、S101) ，其後，結束處理。 [實施例2] 於附圖之圖10〜圖13，顯示本發明的實施例2之微小 部X線計測裝置’此處，於以下，以與前述之實施例1的 微小部X線計測裝置之差異點爲主進行說明。亦即，在此 實施例2之微小部X線計測裝置，與前述實施例1之微小部 X線計測裝置不同，其係使光學顯微鏡的光軸，與被照射 於試樣的X線的光學軸一致。根據採用相關的構成，可以 使在前述之實施例1的個別的單元進行一體化。 亦即，圖1 〇係顯示成爲實施例2的微小部X線計測裝 置的正面圖，圖1 1爲其側面圖。此外，圖1 2及圖1 3分別爲 顯示其內部構成之用的縱方向及橫方向之剖面圖。 由這些圖亦可知，在實施例2之微小部X線計測裝置 ，作爲光學顯微鏡使用卡塞格倫（Cassegrain )反射鏡。 於此卡塞格倫（Cassegrain )型光學顯微鏡8的鏡筒44，被 安裝著供觀察試樣或試樣基板的光學影像之用的CCD單元 42、顯微鏡光源43，及X線發生裝置1。 在相關的構成之微小部X線計測裝置，以X線管1 3產 生的X線，由X線焦點1 6放出，通過被設置於X線快門室1 5 18 - 201142275 內部的X線快門1 4，接著，通過聚合毛細管X線光學元件 2 1而照射於X線計測點24。此時，通過聚合毛細管X線光 學元件2 1的X線，藉由光學元件的作用，聚焦於X線計測 點24。此外，佔有X線所通過的路徑的大部分之X線快門 室15、被設置於X線光學元件保持內筒22的內部的聚合毛 細管X線光學元件2 1，及X線檢測器真空室35，係藉由從 真空排氣管2 5排氣而被保持於真空。藉此，抑制空氣所造 成的X線之吸收。 在X線計測點產生的螢光X線，通過X線透過窗2 3，入 射至被設置於X線檢測器真空室3 5的內部的X線檢測元件 33，被變換爲電氣訊號，透過圖12所未圖示的訊號線輸入 至檢測器控制部3 1，接著，於資料處理裝置7獲得螢光X 線光譜。 另一方面，由顯微鏡光源43發出的可見光，藉由稜鏡 45反射，同時藉由卡塞格倫（Cassegrain)型光學顯微鏡8 ，藉由被設置在副鏡保持桿8 3的卡塞格倫副鏡8 2及卡塞格 倫主鏡8 1來反射聚焦，與X線同樣，被聚焦/照射於X線 計測點24。計測點24的光學影像，通過卡塞格倫副鏡82、 卡塞格倫主鏡81及稜鏡47，於CCD單元42上投射試樣影像 〇 以下，參照圖1 3同時詳細說明X線棒測器真空室3 5的 內部之X線檢測元件34之配置。 於X線檢測器真空室35的中央部，被配置聚合毛細管 X線光學元件2 1，於其周圍’被安裝著X線檢測元件3 4。 -19- 201142275 在本實施例’顯示被安裝著4個X線檢測元件之例。此χ線 檢測元件之數目’係以預先設想的螢光X線強度來決定的 ，接著，使用鈹（Be，beryllium)箔之X線透過窗23與X 線檢測器真空室3 5，例如係藉由熔接或黏接而密封，聚合 毛細管X線光學元件21及X線檢測器真空室35被真空排氣 ，而保持於真空。藉此’抑制了由試樣所發生的螢光X線 的路徑之中’在X線透過窗2 3與X線檢測元件3 4的部分之 空氣所導致的X線的吸收。 此外，於X線檢測器真空室3 5_的··.外周部，設有可見光 透過窗26，在構成通往供進行試樣影像的照明及觀察之用 的成像光學系統的光徑之該實施例2，特徵爲被照射X線 之軸與觀察用顯微鏡的光軸一致這一點，據此，可在裝置 製造時藉由調整而固定可見光焦點與X線焦點的位置，所 以可以得到具有可提供容易安裝或調整的微小部X線計測 裝置的優點。 [實施例3] 於附圖之圖1 4，顯示本發明的實施例3之微小部X線 計測裝置，此處’也於以下，以與前述之實施例2的微小 部X線計測裝置之差異點爲主來進行說明。亦即，在此圖 14所示之微小部X線計測裝置，與前述實施例2之微小部X 線計測裝置所採用的卡塞格倫型光學顯微鏡不同，藉由在 折射透鏡的中央光軸部分開設孔，於該處安裝聚合毛細管 X線光學元件2 1，而使試樣觀察用光學系統與試樣照射χ -20- 201142275 線光學系統之軸成爲一致。進而，藉由前述之構成，螢光 X線的檢測，與前述實施例2不同，係作爲另外的單元而 被配置於物鏡4 8的周圍。亦即，在此實施例3，藉由在螢 光X線檢測器36的螢光X線入射側，安裝聚合毛細管螢光X 線光學元件3 7，而使入射至檢測器的X線的取入立體角增 加’因而，實現可以進行高感度的計測的裝置。 即使在本實施例，X線光學元件保持內筒22及螢光X 線光學元件保持內筒38的內部，被真空排氣或被氦氣置換 ’藉此，防止通過被設置於這些的內部之聚合毛細管X線 光學元件21及聚合毛細管螢光X線光學元件37內部的X線 的衰減。 【圖式簡單說明】 圖1係顯示相關於本發明之實施例1的微小部X線計測 裝置的槪略構成之全體立體圖。 圖2係說明前述實施例1之微小部X線計測裝置之來自 試樣的螢光X線的計測之圖。 圖3係於前述實施例1之微小部X線計測裝置，顯示決 定進行螢光X線計測的試樣位置的座標之流程之圖。 圖4係於前述實施例1之微小部X線計測裝置，使用鉻 (Cr )靶之X線產生裝置（X線管）來計測的玻璃基板上 試樣之測定例（測定例1 )之包含X線頻譜之圖。 圖5係於前述實施例1之微小部X線計測裝置，使用鉻 (C r )靶之X線產生裝置（X線管）來計測的玻璃基板上 -21 - 201142275 試樣之其他測定例（測定例3)之包含x線頻譜之圖。 圖6係於前述實施例1之微小部X線計測裝置’使用鉻 (Cr )靶之X線產生裝置（X線管）來計測之於表面存在 鋁質微小金屬粉的玻璃基板上試樣之測定例（測定例3 ) 之包含X線頻譜之圖。 圖7係於前述實施例1之微小部X線計測裝置’使用鉻 (Cr )靶之X線產生裝置（X線管）來計測的前述測定例2 與測定例3，以及顯示其差分的包含X線頻譜之圖。 圖8係由原子序24之鉻（Cr )至原子序29之銅（Cu ) 爲止的過渡金屬元素之Κα及ΚΘ頻譜之例之圖。 圖9係於前述實施例1之微小部X線計測裝置’顯示測 定座標存在複數點的場合之微小部XRF (螢光X線）計測 的流程之圖。 圖1 〇係顯示成爲本發明之實施例2的微小部X線計測 裝置的正面圖。 圖1 1係顯示成爲本發明之實施例2的微小部X線計測 裝置的側面圖。 圖12係說明前述實施例2之微小部X線計測裝置之X線 及可見光光學系統的構成之縱方向剖面圖。 圖13係說明前述實施例2之微小部X線計測裝置之X線 及可見光光學系統的構成之橫方向剖面圖。 圖1 4係顯示相關於本發明之實施例3的微小部X線計 測裝置的內部構成之縱方向剖面圖。 -22- 201142275 【主要元件符號說明】 1 : X線發生裝置 2 : X線光學元件 3 : X線檢測器 4 =光學顯微鏡 5 :試樣，試樣機板 6 =試樣相對移動機構 7 :資料處理裝置 8:卡塞格倫（Cassegrain)型光學顯微鏡 1 1 : X線發生控制部 12 : X線管遮蔽物 1 3 : X線管 14 : X線快門 15 : X線快門室 16 : X線焦點 17 :試樣照射X線 21 :聚合毛細管（Polycapillary ) X線光學元件 22 : X線光學元件保持鏡筒 2 3 : X線透過窗 3 1 ’·檢測器控制部 3 2 :螢光X線 34 : X線檢測元件 35 : X線檢測真空室 36 :螢光X線檢測器 -23- 201142275 37:聚合毛細管（Polycapillary)螢光X線光學元件 38 :螢光X線光學元件保持鏡筒 4 1 :顯微鏡控制部 42 ： CCD單元 43 :顯微鏡光源 44 :鏡筒 4 5 :稜鏡 4 8 :物鏡 5 1 :試樣 6 1 :試樣移動控制部 81 :卡塞格倫（Cassegrain)主鏡 82 :卡塞格倫（Cassegrain)副鏡 8 3 :副鏡保持桿 -24-The eleventh example of the construction of the test line X is given. 1] The example shows the system [«BI into a perspective view. Inside the cartridge body (not shown), a twist line generating device 1, an X-ray detector 3, and an optical microscope 4 are mounted. The X-ray optical element 2 for focusing the X-ray generated by the X-ray generator 1 on a small area is a polycapillary type element, and the X-ray optical element 2 of the polymerization capillary type is directly mounted on the X-ray optical element 2 X-ray generating device 1 . As a result, the X-ray generated by the X-ray generator 1 is focused on a small cross-sectional area of 50 μm or less by the action of the polymeric capillary X-ray optical element 2, and then irradiated onto the sample. The sample 5 on the relative moving mechanism (mobile station) 6. Further, the position control of the sample 5 of the X-ray generating device 1 and the X-ray irradiation position of the X-ray optical element 2 of the polymeric capillary type is performed by the sample movement control unit 61. Further, the X-ray optical element 2 of the polymerized capillary type of the present embodiment has the X-ray generating device 1 that emits X-rays using molybdenum (Mo) metal as an X-ray target and focuses X-rays with an energy of 1 7.5 keV to The diameter of 1 5 μηι, the effect of focusing the X-ray of energy 8.0 keV to the diameter of 25 μm. Further, in the X-ray generating device 1 as the metal target in which the X-ray is generated, the aforementioned molybdenum (Mo) of the atomic order 42 may be added to the silver (Ag) of the atomic order 47 or the tungsten of the atomic order 74 (W). Each element up to the gold (Au) of the atomic sequence 79 is used as a monomer or a complex alloy or a laminated film. Further, the acceleration voltage/current of the X-ray generator 1 and the control of the X-ray shutter or the like are performed by the X-ray generation control unit 11. Further, the confirmation of the irradiation position of the X-ray focused by the above-described polycapillary type X-ray optical element 2 - -10-201142275 is performed by the optical microscope 4. That is, the light emitted from the microscope light source 43 is irradiated to the sample 5 by the optical microscope 4, and then the light reflected/scattered by the sample 5 is imaged on the CCD unit 42 mounted on the optical microscope 4 described above. The sample image is transmitted to the microscope control unit 41 as an electrical signal. Then, the casing (not shown) is set to the measurement position by freely selecting the position on the ternary coordinate (see X-Y-Z in the drawing) by the position control mechanism not shown. Here, the quadratic coordinate 'Z' on the sample 5 of the X-Y substrate is the height of the casing, which is adjusted by the focus position of the substrate and the optical microscope 4. Next, a more detailed structure of the X-ray measuring apparatus of the first embodiment will be described using the attached Fig. 2 . In the sample 5, the X-ray generating device 1 and the X-ray optical element 2 were irradiated with X-rays. At this time, the X-ray generated by the X-ray generating device 1 is focused on a small irradiation area by passing through the X-ray optical element 2 as described above. Further, the inside of the X-ray optical element 2 is evacuated or replaced by helium gas, whereby the X-ray passing through the inner portion thereof is prevented from being reduced. On the other hand, the fluorescent X-rays 32 emitted from the minute portion 51 on the sample (substrate) 5 irradiated with the X-rays are captured by the X-ray detector 3, and are detected by the detector control unit 31. The data is converted to a histogram of X-ray photons to fluorescent X-ray energy and sent to the data processing device 7. Thereby, the X-ray generated in the X-ray generating device 1 is moved to the X-ray optical element 2 by the movement of the sample relative position moving mechanism 6 by the sample 5 captured by the optical microscope 4. The position to be focused/illuminated causes the fluorescent X-rays occurring at this time to be captured by the χ-11 - 201142275 line detector 3, and the photon energy distribution (spectrum) of the captured fluorescent X-rays is performed in the data processing device 7. The analysis is performed to perform elemental analysis of the portion irradiated with the X-ray. In addition, at this time, if the distance from the minute portion 51 of the sample to the X-ray detector 3 is 5 mm or less, the energy is 1. OkeV characteristic X even if the minute portion 51 of the sample is generated. The line can also suppress its attenuation in the air, which can be detected. In particular, in the present embodiment, when molybdenum (Mo) is used as the X-ray target of the X-ray generator 1, the X-ray of 300 cps is irradiated under the operating conditions of a voltage of 50 kV and a current of 0.5 mA. The tiny part 51 of the sample 5. In this case, when the metal from the molybdenum (Mo) of the atomic order 42 to the silver (Ag) of the atomic order 47 is an X-ray target, the characteristic X-ray of L α is mixed into the X-rays to be irradiated. Moreover, the characteristic X line of this L α is 2.29 keV in the MoL α 'X line energy, and the X-ray energy is 2.98 keV in AgL α ', that is, close to the fluorescent X-ray excitation energy of the aluminum metal (A1). Near l_56keV, the fluorescent X-ray of A1K α can be released by aluminum metal (A1) with high efficiency. On the other hand, the characteristic X-rays of ΜοΚ α and AgK α are effective for the excitation of transition metals, and are the same as those of the commonly used metal elements '1 for the micro-parts of transition metals such as Cr, Fe, Co, Ni, and Cu. Optical X-ray analysis is effective and can be used for high sensitivity measurements. Next, Fig. 3 shows the flow of coordinate measurement for X-ray measurement in the X-ray measuring device of the present invention. As can be seen from the figure, when XRF (fluorescence X-ray) measurement position detection is started, 'first set the measurement position number (m) to m = 0 (step S31)'. Next, increase 値m by only 1 ( m = m + 1) (Step S32) ° Next -12- 201142275, coordinate is moved until the coordinate of the number (m) of the position (for example, (mx, my)) is measured (step S3 3), and then the Z position is adjusted (step S34). ). First, optical measurement is performed (step S35), and it is determined whether or not there is the presence of microparticles (step S36). As a result, when it is determined that there is the presence of fine particles ("Yes" in the figure), the coordinates are recorded (step S37), and thereafter, it is determined whether or not all the measurements are completed by the above m (step S38). . On the other hand, when it is determined that no fine particles are present ("No" in the figure), the process proceeds to the above-described step S37. Next, if the result of the determination in the above step S37 is that the measurement is not completed ("No" in the figure), the process returns to the above-described step S32, and on the other hand, it is determined that all the measurements are completed (Fig. In the case of "Yes", the coordinates of the microparticles are placed at the head of the recorded coordinates (step S39), and further, M0 = m+1 (step S40), and the processing is terminated. The above-described flow is displayed for decision. For the coordinates of the position where the fluorescent X-ray measurement is performed, one example of using visible light is used. Further, in order to determine the coordinates, in addition to the visible light described above, for example, an infrared ray or an ultraviolet ray may be used. Further, X-ray measurement can be performed immediately after the X-ray measurement coordinates are determined by visible light. Further, an example of the photon energy distribution of the fluorescent X-rays measured by the X-ray measuring device having the configuration shown in Figs. 1 and 2 is shown in Fig. 4 to Fig. 6 of the drawings. Moreover, in the case of this measurement example, the photon energy of the X-ray generated by the X-ray generator was 5.4 keV. Fig. 4 is a graph showing the energy of the characteristic X-ray of the element contained in the sample, and the measurement data of the photon detected by the measurement of a certain time in 201142275, by which the data contained in the measurement area can be measured. The type and quantity of elements. In the measurement device of the present invention, it is possible to suppress the attenuation of the fluorescent X-rays in the atmosphere by setting the X-ray path in the atmosphere to 5 mm or less. As a result, as shown in FIG. 4, it is also possible to detect Sodium (Na). Further, the fluorescent X-ray of calcium (Ca) or strontium (Ba) is hardly attenuated in the atmosphere, so that it can be measured under high sensitivity. Next, a detection method in the case where the substrate contains the same atomic species as the sample particles will be described with reference to Figs. 5 and 6 . A material used as a substrate in most fields is glass. In the relevant glass, as a general use, there is an alumina silicate which is composed of an alkali metal/earth metal, and a mixture of oxidized/oxidized sand. An example of the fluorescent X-ray spectrum of the glass substrate used herein is shown in Fig. 5. The spectrum shown in Figure 5 is measured for aluminum (A1), bismuth (Si), phosphorus (P), a small amount of sulfur (S), chlorine (C1), and further argon (Ar) in the atmosphere. . Further, as a result of the measurement, A1 and Si were detected as elements contained in the glass. Further, P, S, and C1 were measured by adhering to the surface of the glass. Here, the A1 metal powder is dispersed on the surface of the glass substrate, and the A1 metal powder is introduced into the X-ray irradiation region by moving the substrate position ', and the fluorescent X-ray is measured under the same conditions as described above. The results obtained thereby are shown in Fig. 6. Here, when the difference between the measured spectra is taken, a difference spectrum indicating "differential spectrum" is shown in Fig. 7 of the drawing. Further, in this case, the peak of -14-201142275 is a peak caused by the fine metal powder of A1, that is, a minute foreign matter can be detected. Further, according to this method, the A 1 minute metal powder of a degree of 1 n g can be detected by the result of the apparatus of the present embodiment. Here, the certainty (confirmability) of the detection of the minute metal powder used in the present invention is explained. The detection of the X-ray is performed by measuring the photon of the X-ray incident on the detector by the detector, and the measurement accuracy of the number (N) is measured as a statistical error (1 σ ). The square root is used to indicate. In addition, in the measurement of the X-ray, background noise generated by the detector itself or by the electronic circuit is inevitably observed. Next, the measurement intensity of the fluorescent X-ray from the minute foreign matter is represented by a difference (N1 - N0 ) between the measurement 値 (Ν 1 ) including the metal fine particles and the measurement 値 (Ν 0 ) containing no such metal fine particles, respectively The measurement 値 contains the statistical error (1 σ ) of Nl, NO. That is, in order to judge that the intensity of the fluorescent X-rays from the fine metal particles is measured at the level of η σ, the following formula (1) is used. η = ( Ν 1 -NO ) / ( Ν 1 + Λ NO ) . ( 1 ) At η = 1, the normal distribution function has a 68% chance to determine "there is a tiny metal foreign matter", and its probability is η = 2 The occasion becomes 95°/. Further, when η = 3, it is 99.7 %. As an example, when Ν1 and NO are 1000 and 900, respectively, n = 1.6, and when N1 and NO are 500 and 400, respectively, η = 2.4, even if the measurement intensity from the minute metal particles (Ν 1-Ν0) ) is the same, and because the latter's background fluorescent X-ray noise intensity is very low -15-201142275, it becomes a highly reliable test. Further, the measured intensity (N 1 -NO ) is the intensity of the fluorescent X-ray derived from the fine metal particles, and is approximately equal to the weight of the metal particles. Here, when a plurality of types of excessive metal particles are detected, the following processing can be performed to improve the data accuracy. Further, examples of the commonly used transition metal element include chromium (Cr) to atomic order 29 (Cu) of atomic order 24, but among the two kinds of fluorescent X-rays excited by each element, it is called ΚΘ The X-ray on the high energy side overlaps with the spectrum on the low energy side of the atomic order No. 1 called Κα. Its appearance is shown in Figure 8. In other words, when the fluorescent X-ray of each element is detected, it is necessary to treat the measured spectral data because there is a certain amount of enthalpy. Similarly, for elements with a larger atomic order, they are treated as a complex La. Thereby, the accuracy of the measurement data can be improved. Next, a method of suppressing the influence of elements contained in the substrate by using the data of the complex point will be described. The fluorescent X-ray detector used herein is stored in the memory of the data processing device 7 in a digital manner using a so-called energy dispersive type (ED) detector for the spectrum of the multichannel analyzer. That is, the calculations described here are performed at a very high speed. When there is a measurement data of a plurality of points on the substrate, it is not always necessary to measure the metal microparticles for each measurement point, and the fluorescence X-ray spectrum from the substrate can be estimated. The type of substrate is known. For example, in the case of glass, the composition is an alkali metal (Na, K, etc.), an alkaline earth metal (Ca, Ba, etc.), and aluminum (A1) and bismuth (S i ) and oxygen (Ο). That is, in the case of performing fluorescence X-ray measurement of fine particles, when the fine particles are not these elements but are transitional gold-16-201142275 (for example, Cr, Fe, Co, Ni, Cu, etc.), the particles constituting the fine particles; 'It can be judged to be a fluorescent ray from an element derived from a substrate. In the case where the element containing the original substrate is not detected, the fluorescent X-ray spectrum of the element contained in the substrate can be judged to be from the substrate. For example, 'the measurement of the metal microparticles is the same as the element from the substrate.' Compare the complex spectrum, for example, compare the fluorescence X-ray intensity of the spectrum corresponding to aluminum (A1), and assume the smallest number 値 from the substrate. Fluorescence X-ray intensity, and η値 is calculated by the above formula (1). Similarly, the maximum 値1 of the Α1 fluorescent X-ray, when the threshold 値nt (for example, nt = 2.0) or more, uses the lowest A1 fluorescent X-ray intensity as the intensity of the fluorescent X-ray from the substrate. As a result, in all the cases where the measured η 在 is below the threshold 値 nt, the intensity of the fluorescent X-ray at the place where the metal fine particles are not present is taken as the intensity of the fluorescent X-ray from the substrate. In this way, by determining the intensity of the fluorescent X-ray from the substrate, it is always possible to compare the point where the metal fine particles are present, and the measurement of the point where there is no (none), and the measurement can be performed at a high speed. Further, an example of the measurement at this time is shown in Fig. 9. As shown in the flow of Fig. 9, when the micro-section XRF (fluorescence X-ray) measurement is started, first, the number (m) of the measurement position is set to m = 0 (step S91), and then the 値m is increased by only l. (m=m+i) (step S92). Next, the coordinate movement is performed until the coordinate of the number (m) of the measurement position (for example, (mx, my)) (step S93), and then the Z position is adjusted (step S94). Thereafter, XRF (fluorescence X-ray) measurement is performed (step S 9 5 ), and the data obtained by the result is used to find the minimum m of the m -17-201142275 material (step S96). Thereafter, k = 〇, Ml = m (step S97), and secondly, k is sequentially incremented by l (k = k + 1) (step S98), and the total measurement η 算出 is calculated (step S 9 9 ), and a map is created. The table shown on the left. Thereafter, it is confirmed that all the data processing is completed (steps S100 and S101), and thereafter, the processing is ended. [Embodiment 2] FIG. 10 to FIG. 13 of the drawings show a micro-part X-ray measuring device according to a second embodiment of the present invention. Here, the micro-X-ray measuring device according to the first embodiment described above is used. The difference is mainly explained. That is, the micro X-ray measuring device of the second embodiment differs from the micro X-ray measuring device of the first embodiment in that the optical axis of the optical microscope and the X-ray of the sample are irradiated. The axes are consistent. According to the configuration, the individual units of the first embodiment described above can be integrated. That is, Fig. 1 is a front view showing the micro-part X-ray measuring apparatus of the second embodiment, and Fig. 11 is a side view thereof. Further, Fig. 12 and Fig. 13 are cross-sectional views in the longitudinal direction and the lateral direction for showing the internal structure thereof. As can be seen from these figures, the micro-section X-ray measuring apparatus of the second embodiment uses a Cassegrain mirror as an optical microscope. The lens barrel 44 of the Cassegrain type optical microscope 8 is mounted with a CCD unit 42, an optical source 43, and an X-ray generating device 1 for observing an optical image of a sample or a sample substrate. In the micro-section measuring device of the related configuration, the X-ray generated by the X-ray tube 13 is emitted from the X-ray focal point 16 and passes through the X-ray shutter 1 provided inside the X-ray shutter room 1 5 18 - 201142275. 4. Next, the X-ray measuring point 24 is irradiated by polymerizing the capillary X-ray optical element 21. At this time, the X-ray measurement point 24 is focused by the action of the optical element by polymerizing the X-ray of the capillary X-ray optical element 21. Further, an X-ray shutter room 15 occupying most of the path through which the X-ray passes, a polymeric capillary X-ray optical element 2 1 disposed inside the X-ray optical element holding inner tube 22, and an X-ray detector vacuum chamber 35 It is held in a vacuum by exhausting from the vacuum exhaust pipe 25. Thereby, the absorption of the X-ray caused by the air is suppressed. The X-rays generated at the X-ray measurement points are incident on the X-ray detecting elements 33 provided inside the X-ray detector vacuum chamber 35 through the X-ray transmission window 23, and are converted into electrical signals. The signal lines (not shown) are input to the detector control unit 3 1, and then the fluorescence X-ray spectrum is obtained by the data processing device 7. On the other hand, the visible light emitted by the microscope light source 43 is reflected by the crucible 45 while being passed by the Cassegrain type optical microscope 8 by the Cassegrain disposed on the sub mirror holding rod 8 3 The sub-mirror 8 2 and the Cassegrain main mirror 8 1 reflect the focus, and are focused/illuminated to the X-ray measurement point 24 like the X-ray. The optical image of the measuring point 24 is projected onto the CCD unit 42 by the Cassegrain sub-mirror 82, the Cassegrain main mirror 81 and the 稜鏡47, and the X-ray bar is described in detail with reference to FIG. The arrangement of the X-ray detecting elements 34 inside the detector vacuum chamber 35. In the central portion of the X-ray detector vacuum chamber 35, a polymeric capillary X-ray optical element 2 is disposed around the X-ray detecting element 34. -19- 201142275 In the present embodiment, an example in which four X-ray detecting elements are mounted is shown. The number of the twist line detecting elements is determined by the intensity of the fluorescent X-rays assumed in advance, and then the X-ray transmission window 23 of the beryllium (Be, beryllium) foil and the X-ray detector vacuum chamber 35 are used, for example, The polymerized capillary X-ray optical element 21 and the X-ray detector vacuum chamber 35 are evacuated by vacuum welding while being sealed by welding or bonding, and are kept under vacuum. Thereby, the absorption of the X-ray caused by the air passing through the portion of the X-ray transmission window 23 and the X-ray detecting element 34 among the paths of the fluorescent X-rays generated by the sample is suppressed. Further, a visible light transmission window 26 is provided in the outer peripheral portion of the X-ray detector vacuum chamber 35_, which constitutes the optical path of the imaging optical system for illumination and observation of the sample image. In the second embodiment, the axis of the X-ray to be irradiated coincides with the optical axis of the observation microscope, whereby the position of the visible light focus and the X-ray focus can be fixed by adjustment during the manufacture of the device, so that it is possible to obtain Provides the advantages of a small part X-ray measuring device that is easy to install or adjust. [Embodiment 3] A micro-X-ray measuring device according to Embodiment 3 of the present invention is shown in Fig. 14 of the accompanying drawings, and here, in the following, the micro-X-ray measuring device of the second embodiment described above is used. The difference point is mainly for explanation. That is, the micro-X-ray measuring device shown in FIG. 14 is different from the Cassegrain-type optical microscope used in the micro-X-ray measuring device of the second embodiment, by the central optical axis of the refractive lens. A hole is partially opened, and the polymeric capillary X-ray optical element 2 1 is installed there, and the optical system for sample observation is made to conform to the axis of the sample irradiation χ-20- 201142275 line optical system. Further, according to the configuration described above, the detection of the fluorescent X-rays is different from the above-described second embodiment, and is disposed as a separate unit around the objective lens 48. That is, in this embodiment 3, the X-rays incident on the detector are taken by mounting the polymeric capillary fluorescent X-ray optical element 3 7 on the incident side of the fluorescent X-ray detector of the fluorescent X-ray detector 36. The solid angle is increased. Thus, a device capable of performing high-sensitivity measurement is realized. Even in the present embodiment, the X-ray optical element holds the inner tube 22 and the fluorescent X-ray optical element in the inside of the inner tube 38, and is evacuated or replaced by helium gas, thereby preventing passage through the inside of these. The X-ray attenuation inside the polymeric capillary X-ray optical element 21 and the polymeric capillary fluorescent X-ray optical element 37. [Brief Description of the Drawings] Fig. 1 is a perspective view showing a schematic configuration of a micro-section X-ray measuring apparatus according to a first embodiment of the present invention. Fig. 2 is a view for explaining measurement of fluorescent X-rays from a sample of the micro-part X-ray measuring apparatus of the first embodiment. Fig. 3 is a view showing the flow of the coordinates of the sample position for determining the X-ray measurement by the micro-section X-ray measuring device of the first embodiment. Fig. 4 is a view showing the measurement example (measurement example 1) of the sample on the glass substrate measured by the X-ray generation device (X-ray tube) of the chromium (Cr) target in the micro-section X-ray measuring device of the first embodiment; A diagram of the X-ray spectrum. Fig. 5 is a view showing another measurement example of the sample on the glass substrate 21 - 201142275 measured by the X-ray measuring device (X-ray tube) of the chromium (C r ) target in the micro-section X-ray measuring device of the first embodiment ( A graph containing the x-ray spectrum of the measurement example 3). Fig. 6 is a view showing a sample on a glass substrate on which a surface of aluminum micro-metal powder is present on a surface of a micro-section X-ray measuring device of the first embodiment using an X-ray generating device (X-ray tube) of a chromium (Cr) target; The measurement example (measurement example 3) contains the X-ray spectrum. Fig. 7 is a view showing the measurement example 2 and the measurement example 3 measured by the X-ray measuring device (X-ray tube) using a chromium (Cr) target in the micro-section X-ray measuring device of the first embodiment, and the inclusion of the difference therebetween. A diagram of the X-ray spectrum. Fig. 8 is a view showing an example of the Κα and ΚΘ spectrum of a transition metal element from the chromium (Cr) of atomic order 24 to copper (Cu) of atomic order 29. Fig. 9 is a view showing a flow of micro-section XRF (fluorescence X-ray) measurement in the case where the micro-section X-ray measuring device ’ of the first embodiment shows that the measurement coordinates have a plurality of points. Fig. 1 is a front view showing a micro-part X-ray measuring apparatus according to a second embodiment of the present invention. Fig. 1 is a side view showing a micro-part X-ray measuring apparatus according to a second embodiment of the present invention. Fig. 12 is a longitudinal cross-sectional view showing the configuration of the X-ray and visible light optical system of the micro-part X-ray measuring device of the second embodiment. Fig. 13 is a transverse cross-sectional view showing the configuration of the X-ray and visible light optical system of the micro-part X-ray measuring device of the second embodiment. Fig. 14 is a longitudinal cross-sectional view showing the internal structure of a micro-section X-ray measuring apparatus according to a third embodiment of the present invention. -22- 201142275 [Description of main component symbols] 1 : X-ray generator 2 : X-ray optical component 3 : X-ray detector 4 = Optical microscope 5 : Sample, sample plate 6 = Sample relative movement mechanism 7 : Data processing device 8: Cassegrain type optical microscope 1 1 : X-ray generation control unit 12: X-ray tube shield 1 3 : X-ray tube 14 : X-ray shutter 15 : X-ray shutter room 16: X Line focus 17: Sample irradiation X-ray 21: Polycapillary X-ray optical element 22: X-ray optical element holding lens barrel 2 3 : X-ray transmission window 3 1 '·Detector control unit 3 2 : Fluorescence X Line 34: X-ray detecting element 35: X-ray detecting vacuum chamber 36: Fluorescent X-ray detector-23- 201142275 37: Polycapillary fluorescent X-ray optical element 38: Fluorescent X-ray optical element holding lens barrel 4 1 : Microscope control unit 42 : CCD unit 43 : Microscope light source 44 : Lens barrel 4 5 : 稜鏡 4 8 : Objective lens 5 1 : Sample 6 1 : Sample movement control unit 81 : Cassegrain main Mirror 82: Cassegrain secondary mirror 8 3 : secondary mirror holding rod-24-