JP2008122144A - Specimen drip substrate for total-reflection fluorescence x-ray analysis, total reflection fluorescent x-ray analyzer, and total reflection fluorescent x-ray analysis method - Google Patents

Specimen drip substrate for total-reflection fluorescence x-ray analysis, total reflection fluorescent x-ray analyzer, and total reflection fluorescent x-ray analysis method Download PDF

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JP2008122144A
JP2008122144A JP2006304082A JP2006304082A JP2008122144A JP 2008122144 A JP2008122144 A JP 2008122144A JP 2006304082 A JP2006304082 A JP 2006304082A JP 2006304082 A JP2006304082 A JP 2006304082A JP 2008122144 A JP2008122144 A JP 2008122144A
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drip
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substrate
total reflection
drying
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JP4537367B2 (en
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Yuichiro Shimizu
雄一郎 清水
Naoki Kawahara
直樹 河原
Takashi Yamada
隆 山田
Koichi Aoyanagi
光一 青柳
Tsuneo Kandori
恒夫 神鳥
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Rigaku Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a specimen drip substrate for total reflection fluorescent X-ray analysis, a total reflection fluorescent X-ray analyzer, and a total reflection fluorescent X-ray analysis method, wherein a trace amount liquid sample is accurately made to dripped, in order to be dried onto a prescribed part of a sample drip substrate, and to improve the sensitivity and accuracy of total reflection fluorescent X-ray analysis on the liquid sample. <P>SOLUTION: This specimen drip substrate 15 for total reflection fluorescent X-ray analysis is a sample drip substrate for thereonto dripping and drying the liquid specimen, comprising a planar substrate 15K with its surface being hydrophobic and having planarity of mirror polishing level, and a synthetic resin drip dried trace 41, made by dripping a prescribed amount of synthetic resin solution 40 onto a prescribed part of a surface of the planar substrate 15K and drying it; the resin solution 40, obtained by dissolving a synthetic resin into a prescribed concentration by using a solvent. By using this total reflection fluorescent X-ray analyzer and its method, a sample solution 70 is dripped onto and dried on the dried trace 41 on the drip substrate 15, to perform total reflection fluorescent X-ray analysis. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、蛍光X線分析用試料点滴基板に関する。さらに詳しくは、液体試料を試料基板に点滴乾燥して、その試料基板上に形成された点滴乾燥痕にX線源から1次X線を照射して、点滴乾燥痕から発生する蛍光X線を測定するための試料点滴基板およびその基板を有する全反射蛍光X線分析装置ならびにその基板を用いる全反射蛍光X線分析方法に関する。   The present invention relates to a sample drip substrate for fluorescent X-ray analysis. More specifically, a liquid sample is drip-dried onto a sample substrate, and a primary X-ray is irradiated from an X-ray source onto a drip-drying mark formed on the sample substrate, and fluorescent X-rays generated from the drip-drying mark are emitted. The present invention relates to a sample drip substrate for measurement, a total reflection X-ray fluorescence analyzer having the substrate, and a total reflection X-ray fluorescence analysis method using the substrate.

従来、液体試料を基板やフィルム上に濃縮する技術として、疎水性の厚さ30〜40μmテフロン(登録商標)膜が形成された基板上にフォトリソグラフィックマスクを用いて30nmの金を蒸着した基板を作成し、その基板の金蒸着部位に液体試料を滴下する方法が知られている。この方法では、テフロン(登録商標)とこのテフロン(登録商標)上に蒸着されている金との疎水性と親水性の違いにより、滴下された液体試料の液滴は蒸着された金を中心にして集結し、液滴を乾燥させると蒸着された金を中心に濃縮される。   Conventionally, as a technique for concentrating a liquid sample on a substrate or a film, a substrate obtained by depositing 30 nm of gold using a photolithographic mask on a substrate on which a hydrophobic 30 to 40 μm Teflon (registered trademark) film is formed is used. A method of creating and dropping a liquid sample on a gold vapor deposition site of the substrate is known. In this method, due to the difference in hydrophobicity and hydrophilicity between Teflon (registered trademark) and gold deposited on the Teflon (registered trademark), the droplet of the dropped liquid sample is centered on the deposited gold. When the droplets are collected and dried, they are concentrated mainly on the deposited gold.

従来から蛍光X線分析においても前記と同様な方法として、金属板や金属箔上に液体試料を点滴し、点滴した液滴を乾燥させた金属基板や金属箔を蛍光X線分析装置で測定する技術がある。この方法では、液体試料の成分に液体試料を点滴乾燥させる金属基板や金属箔と同じ成分が含まれていると分析ができない場合や正確な分析を行うことができない場合などの問題が生じる。また、例えば厚さが0.5μmの薄膜フィルム上に液体試料を点滴乾燥させて、この点滴乾燥痕に1次X線を照射して点滴乾燥痕から発生する蛍光X線を測定する蛍光X線分析方法がある。この方法では、測定成分と金属基板成分の問題は生じないが、点滴した液滴が薄膜フィルム上で広がったり、所望の部位に留まらず所望の極小な領域に点滴することが困難である。   Conventionally, also in fluorescent X-ray analysis, as a method similar to the above, a liquid sample is instilled onto a metal plate or metal foil, and a metal substrate or metal foil on which the instilled liquid droplet has been dried is measured with an X-ray fluorescence analyzer. There is technology. In this method, if the components of the liquid sample include the same components as those of the metal substrate or the metal foil that drip-drys the liquid sample, problems such as when analysis cannot be performed or when accurate analysis cannot be performed occur. Further, for example, a liquid sample is drip-dried on a thin film having a thickness of 0.5 μm, and the X-rays emitted from the drip-dried trace are measured by irradiating the drip-dried trace with primary X-rays. There is an analysis method. In this method, the problem of the measurement component and the metal substrate component does not occur, but it is difficult for the instilled droplet to spread on the thin film or to be instilled into a desired minimal region without staying at a desired site.

そこで、これらの問題を解決するために、厚さが0.5〜0.6μmのポリマーフィルム上の領域に、カーボン蒸着膜を形成し、カーボン蒸着膜が形成された点滴フィルム上のカーボン蒸着膜部位に液体試料を点滴した後、乾燥させてから蛍光X線分析する蛍光X線分析方法がある(特許文献1)。この点滴フィルム91は実際の蛍光X線分析に適用されるためには、図9に示すように環状の支持枠94に張架され、点滴フィルム体91Sとして完成され、この点滴フィルム体91Sのカーボン蒸着膜部位93に液体試料を点滴乾燥して測定される。   Therefore, in order to solve these problems, a carbon vapor deposition film is formed in a region on a polymer film having a thickness of 0.5 to 0.6 μm, and the carbon vapor deposition film on the drip film in which the carbon vapor deposition film is formed. There is a fluorescent X-ray analysis method in which a liquid sample is instilled into a region and then dried and then subjected to fluorescent X-ray analysis (Patent Document 1). In order to be applied to actual fluorescent X-ray analysis, this drip film 91 is stretched over an annular support frame 94 as shown in FIG. 9 to complete a drip film body 91S. The liquid sample is drip-dried on the deposited film portion 93 and measured.

しかし、試料によって支持枠94に張架され点滴フィルム91が均一な平面状態でなく、凹凸や面だれが生じていると、試料間で蛍光X線強度が変動し精度のよい分析をすることができない。特に、全反射蛍光X線分析においては、試料の高さが変動すると全反射条件を満たすことができなくなり測定ができなくなったり、バックグラウンドが異常に高くなり測定が困難になったりする。このため、この点滴フィルム91を全反射蛍光X線分析に使用することはできい。
特開2003−90810号公報
However, if the drip film 91 is stretched around the support frame 94 by a sample and is not in a uniform flat state, and unevenness and surface sag are generated, the fluorescent X-ray intensity varies between samples, and an accurate analysis can be performed. Can not. In particular, in total reflection X-ray fluorescence analysis, if the height of the sample fluctuates, the total reflection condition cannot be satisfied and measurement cannot be performed, or the background becomes abnormally high and measurement becomes difficult. For this reason, this drip film 91 cannot be used for total reflection fluorescent X-ray analysis.
JP 2003-90810 A

本発明は前記従来の問題に鑑みてなされたもので、微量の液体試料を所定の部位に精度よく試料点滴基板上に点滴乾燥させている全反射蛍光X線分析用試料点滴基板および全反射蛍光X線分析装置ならびに全反射蛍光X線分析方法を提供し、液体試料の全反射蛍光X線分析の感度と精度を向上させることを目的とする。   The present invention has been made in view of the above-described conventional problems. A sample drip substrate for total reflection fluorescent X-ray analysis and a total reflection fluorescence in which a small amount of liquid sample is accurately drip-dried on a sample drip substrate at a predetermined site. An object of the present invention is to provide an X-ray analyzer and a total reflection X-ray fluorescence analysis method, and to improve the sensitivity and accuracy of total reflection X-ray fluorescence analysis of a liquid sample.

前記目的を達成するために、本発明の第1構成にかかる全反射蛍光X線分析用試料点滴基板は液体試料を点滴乾燥させるための試料点滴基板であって、表面が疎水性であり、鏡面研磨の平面度を有する平面基板と、前記平面基板の表面の所定の部位に、合成樹脂を溶剤にて所定の濃度に溶解された合成樹脂溶液の所定量を点滴乾燥された合成樹脂点滴乾燥痕とを有する。   In order to achieve the above object, a sample drip substrate for total reflection X-ray fluorescence analysis according to the first configuration of the present invention is a sample drip substrate for drip-drying a liquid sample, and has a hydrophobic surface and a mirror surface. A flat substrate having polishing flatness, and a synthetic resin drip-dried trace obtained by drip-drying a predetermined amount of a synthetic resin solution in which a synthetic resin is dissolved in a predetermined concentration with a solvent at a predetermined portion of the surface of the flat substrate And have.

本発明の第1構成においては、平面基板は、例えば幅10〜30mm、長さ40〜80mm、厚み0.5〜5mmの矩形状のものや直径20〜50mmの円板状などのガラス板、シリコンウエハ、石英板の表面が鏡面研磨され、その上に厚さ5nmのシリコンコートやテフロン(登録商標)コートを施し、ガラス板や石英板の表面を疎水性にされている。   In the first configuration of the present invention, the planar substrate is, for example, a glass plate such as a rectangular shape having a width of 10 to 30 mm, a length of 40 to 80 mm, and a thickness of 0.5 to 5 mm, or a disk shape having a diameter of 20 to 50 mm, The surfaces of the silicon wafer and the quartz plate are mirror-polished, and a 5 nm thick silicon coat or Teflon (registered trademark) coat is applied thereon to make the surface of the glass plate or quartz plate hydrophobic.

合成樹脂点滴乾燥痕は、合成樹脂を有機溶剤にて溶解して、例えば所定の濃度である0.01〜5%重量の合成樹脂溶液を作成し、この合成樹脂溶液をマイクロピペットで所定量である1〜3μl採取して、前記平面基板の所定の部位に点滴し、乾燥させて形成される。合成樹脂溶液の濃度は0.02〜1.0%重量が好ましい。平面基板に点滴される合成樹脂溶液量は0.5〜3μlが好ましく、形成される合成樹脂点滴痕の大きさは1φ以下の大きさが好ましい。合成樹脂溶液の濃度も高くなると形成される合成樹脂点滴乾燥痕からのバックグラウンドが高くなる。また、平面基板に点滴される合成樹脂溶液量が多くなると形成される合成樹脂点滴乾燥痕の厚さが厚くなり、全反射蛍光X線分析を行った場合、バックグラウンドが高くなり、分析の正確さや精度が低下する。合成樹脂溶液を点滴する平面基板の所定の部位は基板の表面の中心位置が好ましい。   Synthetic resin drip marks are prepared by dissolving a synthetic resin in an organic solvent to prepare a synthetic resin solution having a predetermined concentration of 0.01 to 5% by weight, for example. It is formed by taking 1 to 3 μl and instilling it on a predetermined part of the flat substrate and drying it. The concentration of the synthetic resin solution is preferably 0.02 to 1.0% by weight. The amount of the synthetic resin solution to be instilled on the flat substrate is preferably 0.5 to 3 μl, and the size of the formed synthetic resin infusion mark is preferably 1φ or less. As the concentration of the synthetic resin solution increases, the background from the synthetic resin drip drying marks formed increases. In addition, when the amount of synthetic resin solution that is instilled onto a flat substrate increases, the thickness of the synthetic resin drip drying trace formed increases, and when total reflection X-ray fluorescence analysis is performed, the background increases and the analysis accuracy is increased. The sheath accuracy decreases. The predetermined position of the flat substrate on which the synthetic resin solution is dropped is preferably the center position of the surface of the substrate.

合成樹脂点滴乾燥痕の形成には、全反射蛍光X線分析に影響を及ぼす不純物を含有していない合成樹脂や溶剤が使用され、また形成された合成樹脂点滴乾燥痕が親水性を有する合成樹脂や溶剤が使用される。例えば、合成樹脂としてはアクリル樹脂が好ましく、有機溶剤としては、1−メトキシ−2−プロパノール(プロピレングリコールモノメチルエーテルやエーテル)とトルエンの混合溶剤が好ましい。   For the formation of synthetic resin drip drying marks, synthetic resins and solvents that do not contain impurities affecting total reflection X-ray fluorescence analysis are used, and the synthetic resin drip drying marks formed are hydrophilic. And solvents are used. For example, an acrylic resin is preferable as the synthetic resin, and a mixed solvent of 1-methoxy-2-propanol (propylene glycol monomethyl ether or ether) and toluene is preferable as the organic solvent.

本発明の第1構成の全反射蛍光X線分析用試料点滴基板によれば、全反射蛍光X線分析に影響を及ぼす不純物を含有していない合成樹脂や溶剤が使用され、また形成された合成樹脂点滴乾燥痕が親水性を有する合成樹脂や溶剤が使用されているので、微量の液体試料を形成された合成樹脂点滴乾燥痕の上に微量の液体試料を点滴すると合成樹脂点滴乾燥痕の親水性により、液体試料が合成樹脂点滴乾燥痕を中心とする位置に集結させることができ、試料位置の変動が少なく検出する蛍光X線強度の変動が少なくなる。また、不純物を含有しておらず、合成樹脂点滴乾燥痕の厚みが例えば1μmと極薄く全反射蛍光X線分析のバックグラウンドの発生がほとんどなく、前記の蛍光X線強度の変動が少なくなることと相まって、正確な精度のよい全反射蛍光X線分析を行うことができる。また、液体試料が集結するので、絞り込んだ1次X線を照射することによって励起効率を上げることができ、分析感度を向上させることができる。   According to the sample drip substrate for total reflection X-ray fluorescence analysis of the first configuration of the present invention, a synthetic resin or solvent that does not contain impurities that affect total reflection X-ray fluorescence analysis is used and formed. Since synthetic resins and solvents that have hydrophilic resin drip marks are used, if a small amount of liquid sample is instilled on a synthetic resin drip mark formed on a small amount of liquid sample, the hydrophilicity of the synthetic resin drip mark Therefore, the liquid sample can be concentrated at a position centered on the synthetic resin drip drying mark, and the variation in the fluorescent X-ray intensity to be detected is small with little variation in the sample position. In addition, it does not contain impurities, the thickness of the synthetic resin drip dry trace is as thin as 1 μm, for example, and there is almost no background of total reflection X-ray fluorescence analysis, and the fluctuation of the X-ray fluorescence intensity is reduced. In combination with this, accurate and accurate total reflection X-ray fluorescence analysis can be performed. Further, since the liquid sample is concentrated, the excitation efficiency can be increased by irradiating the narrowed primary X-ray, and the analysis sensitivity can be improved.

本発明の第2構成にかかる全反射蛍光X線分析装置は、第1構成に係る全反射蛍光X線分析用試料点滴基板と、前記全反射蛍光X線分析用試料点滴基板の合成樹脂点滴乾燥痕上に点滴された液体試料を乾燥させる乾燥手段と、前記乾燥手段によって乾燥された試料乾燥痕に1次X線を照射するX線源と、前記1次X線が照射される前記試料乾燥痕から発生する蛍光X線を検出する検出器とを有する。   The total reflection X-ray fluorescence analyzer according to the second configuration of the present invention is a synthetic resin drip drying of the total reflection X-ray fluorescence analysis sample drip substrate according to the first configuration and the total reflection X-ray fluorescence analysis sample drip substrate. Drying means for drying the liquid sample dripped on the trace, an X-ray source for irradiating the sample drying trace dried by the drying means with primary X-rays, and the sample drying for irradiating the primary X-ray And a detector for detecting fluorescent X-rays generated from the mark.

本発明の第2構成においては、全反射蛍光X線分析用試料点滴基板は第1構成にかかる試料点滴基板と同一である。全反射蛍光X線分析用試料点滴基板の合成樹脂点滴乾燥痕上に点滴された液体試料を乾燥させる乾燥手段は、全反射蛍光X線分析用試料点滴基板の合成樹脂点滴乾燥痕上に所定量の液体試料を点滴し、点滴された液体試料をマイルドに乾燥させる機構であり、全反射蛍光X線分析用試料点滴基板を所定の位置に載置する基板載置台、液体試料を点滴するためのマイクロピペット、マイクロピペット保持部、全反射蛍光X線分析用試料点滴基板上に点滴された液体試料を乾燥させる乾燥部、乾燥部の乾燥温度を制御する乾燥制御部およびこれらを収納するケースとで構成されている。マイクロピペットはマイクロシリンジなどの他の微量液体試料採取器具でもよい。乾燥部は、例えば電球やニクロム線などのヒータおよびこれらと電動ファンや空気吸引ポンプなどと組み合わせてもよい。   In the second configuration of the present invention, the sample drip substrate for total reflection X-ray fluorescence analysis is the same as the sample drip substrate according to the first configuration. The drying means for drying the liquid sample drip on the synthetic resin drip drying trace on the sample drip substrate for total reflection fluorescent X-ray analysis has a predetermined amount on the synthetic resin drip drying trace on the sample drip substrate for total reflection fluorescent X-ray analysis. This is a mechanism to drip a liquid sample and dry the drip liquid sample mildly, a substrate mounting table for placing a sample drip substrate for total reflection X-ray fluorescence analysis at a predetermined position, and a drip for liquid sample A micropipette, a micropipette holder, a drying unit for drying a liquid sample dripped on a sample drip substrate for total reflection X-ray fluorescence analysis, a drying control unit for controlling the drying temperature of the drying unit, and a case for housing these It is configured. The micropipette may be another trace liquid sampling device such as a microsyringe. The drying unit may be combined with a heater such as a light bulb or nichrome wire, and an electric fan or an air suction pump, for example.

前記乾燥手段によって乾燥された試料乾燥痕に1次X線を照射するX線源は、蛍光X線分析で一般的に使用されるW、Cu、CrなどのX線管である。前記1次X線が照射される前記試料乾燥痕から発生する蛍光X線を検出する検出器は、全反射X線分析で使用されるSSDやSDDなどの半導体検出器である。   An X-ray source for irradiating the sample drying traces dried by the drying means with primary X-rays is an X-ray tube of W, Cu, Cr or the like generally used in fluorescent X-ray analysis. The detector for detecting the fluorescent X-rays generated from the sample drying trace irradiated with the primary X-ray is a semiconductor detector such as SSD or SDD used in total reflection X-ray analysis.

本発明の第2構成によれば、前記の第1構成にかかる全反射蛍光X線分析用試料点滴基板と、前記全反射蛍光X線分析用試料点滴基板の合成樹脂点滴乾燥痕上に点滴された液体試料を乾燥させる乾燥手段とを有する全反射蛍光X線分析装置であるので、形成された合成樹脂点滴乾燥痕の上に微量の液体試料を点滴すると合成樹脂点滴乾燥痕の親水性により、合成樹脂点滴乾燥痕を中心とする位置に集結させることができる。この点滴液体試料を乾燥手段によってマイルドに乾燥することにより、合成樹脂点滴乾燥痕の位置を中心に集結して試料乾燥痕を形成することができ、測定試料位置の変動が少なく検出する蛍光X線強度の変動が少なくなる。また、合成樹脂点滴乾燥痕は不純物を含有しておらず、厚みが1μmと極薄く全反射蛍光X線分析のバックグラウンドの発生がほとんどなく、蛍光X線強度の変動が少なくなることと相まって、正確な精度のよい全反射蛍光X線分析を行うことができる。   According to the second configuration of the present invention, the sample is drip on the synthetic resin drip drying traces of the total reflection X-ray fluorescence analysis sample drip substrate according to the first configuration and the total reflection X-ray fluorescence analysis sample drip substrate. A total reflection X-ray fluorescence analyzer having a drying means for drying the liquid sample, so when a small amount of liquid sample is instilled on the formed synthetic resin drip drying trace, due to the hydrophilicity of the synthetic resin drip drying trace, It can be concentrated at a position centering on the synthetic resin drip drying trace. By drying this drip liquid sample mildly by a drying means, it is possible to form a sample dry mark by focusing on the position of the synthetic resin drip dry mark, and to detect the measurement sample position with little fluctuation. Variation in intensity is reduced. In addition, the synthetic resin drip trace does not contain impurities, is very thin with a thickness of 1 μm, and there is almost no background of total reflection X-ray fluorescence analysis, coupled with the fact that fluctuation in fluorescence X-ray intensity is reduced, Accurate and accurate total reflection X-ray fluorescence analysis can be performed.

本発明の第3構成にかかる全反射蛍光X線分析方法は、第1構成にかかる全反射蛍光X線分析用試料点滴基板の合成樹脂点滴乾燥痕上に液体試料の所定量を点滴し、点滴された前記液体試料を乾燥させ試料乾燥痕を生成し、前記試料乾燥痕が生成された前記蛍光X線分析用試料点滴基板を全反射蛍光X線分析装置の基板載置台にセットし、測定を開始して前記試料乾燥痕から発生する蛍光X線の強度を測定し、前記液体試料中に含有される成分を分析する。     The total reflection X-ray fluorescence analysis method according to the third configuration of the present invention is a method in which a predetermined amount of a liquid sample is instilled on a synthetic resin drip drying mark on a sample drip substrate for total reflection X-ray fluorescence analysis according to the first configuration. The dried liquid sample is dried to generate a sample drying mark, and the sample drip substrate for X-ray fluorescence analysis on which the sample drying mark is generated is set on the substrate mounting table of the total reflection X-ray fluorescence analyzer, and measurement is performed. The intensity | strength of the fluorescent X-ray | X_line generate | occur | produced from the sample dry trace is started, and the component contained in the said liquid sample is analyzed.

本発明の第3構成によれば、前記の第1構成にかかる全反射蛍光X線分析用試料点滴基板を用いて全反射蛍光X線分析を行う方法であるので、本発明の第1構成と同様の作用、効果を得ることができる。   According to the third configuration of the present invention, since it is a method for performing total reflection X-ray fluorescence analysis using the sample drip substrate for total reflection X-ray fluorescence analysis according to the first configuration, Similar actions and effects can be obtained.

以下、本発明の第1実施形態である全反射蛍光X線分析用試料点滴基板について説明する。図1に示す平面基板15Kは、厚みが1.3mm、26×76mmの矩形の表面が鏡面研磨された透明なガラス板であり、その表面に厚さ5nmのシリコンコートが施されている。このシリコンコートにより平面基板15Kは疎水性を有している。この平面基板15Kの表面の所定の部位に、図3に示す合成樹脂点滴乾燥痕形成具50のマイクロピペット61を用いて、図1に示すように合成樹脂溶液40を点滴し、図2に示すように乾燥させて合成樹脂点滴乾燥痕41を形成する。   Hereinafter, a sample drip substrate for total reflection X-ray fluorescence analysis which is a first embodiment of the present invention will be described. A flat substrate 15K shown in FIG. 1 is a transparent glass plate having a rectangular surface with a thickness of 1.3 mm and a size of 26 × 76 mm, and a silicon coat with a thickness of 5 nm is applied to the surface. By this silicon coating, the planar substrate 15K has hydrophobicity. Using a micropipette 61 of the synthetic resin drip drying trace forming tool 50 shown in FIG. 3, a synthetic resin solution 40 is dropped on a predetermined portion of the surface of the flat substrate 15K as shown in FIG. The synthetic resin drip drying trace 41 is formed by drying as described above.

図3に示すように、合成樹脂点滴乾燥痕形成具50は平面基板台51、マイクロピペット保持具60およびマイクロピペット61で構成されている。平面基板台51は、平面基板15Kの所定の部位に合成樹脂溶液40を点滴するためのセット溝である平面基板セット溝52、平面基板セット溝52内で平面基板15Kの位置決めをするための位置合わせエッジ55、平面基板15Kの所定の部位に合成樹脂溶液40を点滴するための点滴位置マーク53、マイクロピペット保持具60の支持柱66、67、68の脚と嵌合する嵌合孔57、58、59を4組有している。点滴位置マーク53は、例えば、0.5mmドリル刃でマーキングされている。   As shown in FIG. 3, the synthetic resin drip drying trace forming tool 50 includes a flat substrate base 51, a micropipette holder 60, and a micropipette 61. The flat substrate base 51 is a flat substrate set groove 52 which is a set groove for instilling the synthetic resin solution 40 onto a predetermined portion of the flat substrate 15K, and a position for positioning the flat substrate 15K in the flat substrate set groove 52. A mating edge 55, an infusion position mark 53 for instilling the synthetic resin solution 40 onto a predetermined portion of the flat substrate 15K, a fitting hole 57 for fitting with the legs of the support columns 66, 67, 68 of the micropipette holder 60, There are 4 sets of 58 and 59. The drip position mark 53 is marked with, for example, a 0.5 mm drill blade.

マイクロピペット保持具60は、上部保持板62、下部保持板64および支持柱66、67、68で構成され、上部保持板62および下部保持板64は、それぞれマイクロピペット61を保持するための上部保持孔63および下部保持孔65を有している。マイクロピペット61は市販されている0.5〜10μlに容量が可変できるピペットである。1、2、3μlと採取容量が固定型のピペットでもよい。合成樹脂点滴乾燥痕形成具50の材料はマイクロピペット61を除き、ステンレスである。   The micropipette holder 60 includes an upper holding plate 62, a lower holding plate 64, and support pillars 66, 67, 68. The upper holding plate 62 and the lower holding plate 64 are each an upper holding for holding the micropipette 61. A hole 63 and a lower holding hole 65 are provided. The micropipette 61 is a commercially available pipette whose volume can be changed to 0.5 to 10 μl. A pipette with a fixed collection volume of 1, 2, 3 μl may be used. The material of the synthetic resin drip drying mark forming tool 50 is stainless steel except for the micropipette 61.

平面基板15Kと合成樹脂点滴乾燥痕形成具50を用いて、全反射蛍光X線分析用試料点滴基板15を形成する行程について説明する。合成樹脂であるアクリル樹脂の粉末100mg(ミリグラム)をスパチュラで採取し、電子天秤で秤量後、ガラスビーカに採取し、溶剤であるトルエン5mlをホールピペットで秤量して、このガラスビーカに加え、アクリル樹脂粉末を溶解する。アクリル樹脂が溶解しているこの溶液に1−メトキシ−2−プロパノール(プロピレングリコールモノメチルエーテル、PGMME)を20ml(ミリリットル)を加え、全量25mlの溶液とする。この溶液をビーカに1ml秤量し、1−メトキシ−2−プロパノールを9ml加えて10倍に希釈して、0.04%重量の合成樹脂溶液であるアクリル樹脂溶液40を作成する。合成樹脂点滴乾燥痕形成具50の4つの平面基板セット溝52に4枚の平面基板15Kをそれぞれセットして、80℃に加熱されたホットプレート(図示なし)に載せる。上方にマイクロピペット保持具60がセットされている平面基板セット溝52の位置合わせエッジ55と、近接している平面基板15Kの1つの角とを、平面基板15Kを平面基板セット溝52の底に沿ってスライドさせて合わせる。   The process of forming the sample drip substrate 15 for total reflection X-ray fluorescence analysis using the flat substrate 15K and the synthetic resin drip drying trace forming tool 50 will be described. 100 mg (milligram) of acrylic resin powder is collected with a spatula, weighed with an electronic balance, then collected in a glass beaker, 5 ml of solvent toluene is weighed with a whole pipette, added to this glass beaker, and acrylic Dissolve the resin powder. To this solution in which the acrylic resin is dissolved, 20 ml (milliliter) of 1-methoxy-2-propanol (propylene glycol monomethyl ether, PGMME) is added to make a total solution of 25 ml. 1 ml of this solution is weighed in a beaker, 9 ml of 1-methoxy-2-propanol is added and diluted 10 times to prepare an acrylic resin solution 40 which is a 0.04% weight synthetic resin solution. Four planar substrates 15K are set in the four planar substrate setting grooves 52 of the synthetic resin drip drying mark forming tool 50, and placed on a hot plate (not shown) heated to 80 ° C. The alignment edge 55 of the flat substrate setting groove 52 on which the micropipette holder 60 is set above and one corner of the adjacent flat substrate 15K are connected to the bottom of the flat substrate setting groove 52 with the flat substrate 15K. Slide along to match.

前工程で作成した0.04%重量のアクリル樹脂溶液40をマイクロピペット61で、例えば2μl採取し、図3に示すように、マイクロピペット61の下部を下部保持孔65に合わせ、次にマイクロピペット61の上部を上部保持孔63に合わせ、マイクロピペット61の当接部611と上部保持板62の上面とを当接させ、マイクロピペット61のチップの先端と点滴位置マーク53とがXY平面で合致する位置に合わせ、マイクロピペット61の押出ボタン612を押して、アクリル樹脂溶液40を平面基板15K上に点滴する。平面基板台51がホットプレートによって80℃に加熱されているので、点滴されたアクリル樹脂溶液は直ぐに乾燥し、合成樹脂点滴乾燥痕となり、全反射蛍光X線分析用試料点滴基板15が形成される。   For example, 2 μl of the 0.04% weight acrylic resin solution 40 prepared in the previous step is collected with a micropipette 61, and the lower part of the micropipette 61 is aligned with the lower holding hole 65 as shown in FIG. The upper part of 61 is aligned with the upper holding hole 63, the contact part 611 of the micropipette 61 and the upper surface of the upper holding plate 62 are brought into contact with each other, and the tip of the tip of the micropipette 61 and the drip position mark 53 match on the XY plane. The push button 612 of the micropipette 61 is pushed in accordance with the position to be moved, and the acrylic resin solution 40 is instilled onto the flat substrate 15K. Since the flat substrate stand 51 is heated to 80 ° C. by the hot plate, the drip acrylic resin solution is immediately dried to form a synthetic resin drip dry trace, and the sample drip substrate 15 for total reflection X-ray fluorescence analysis is formed. .

残りの3箇所の平面基板セット溝52にセットされている3枚の平面基板15Kも前記と同様の行程により全反射蛍光X線分析用試料点滴基板15に形成される。このように点滴位置マーク53に合わせてアクリル樹脂溶液40が点滴されるので、平面基板15Kの所定の位置である中心位置に合成樹脂点滴乾燥痕41が形成される。本実施形態では、平面基板15Kの中心位置に合成樹脂点滴乾燥痕41を形成したが、合成樹脂点滴乾燥痕形成具50を変形することによりその他の所定の部位に形成することができる。また、本実施形態では、平面基板セット溝52が4個であったが、1個でも10個、30個などであってもよい。   The three planar substrates 15K set in the remaining three planar substrate setting grooves 52 are also formed on the total reflection fluorescent X-ray analysis sample drip substrate 15 by the same process as described above. Thus, since the acrylic resin solution 40 is instilled in accordance with the drip position mark 53, the synthetic resin drip drying trace 41 is formed at the center position which is a predetermined position of the flat substrate 15K. In this embodiment, the synthetic resin drip drying trace 41 is formed at the center position of the flat substrate 15K. However, the synthetic resin drip drying trace forming tool 50 can be deformed and formed at other predetermined sites. In the present embodiment, the number of planar substrate set grooves 52 is four, but may be one, ten, thirty, or the like.

本実施形態では、合成樹脂としてアクリル樹脂、溶剤としてトルエンおよび1−メトキシ−2−プロパノールを用いたが、全反射蛍光X線分析用試料点滴基板に生成される合成樹脂点滴乾燥痕が親水性を示し、液体試料が合成樹脂点滴乾燥痕を中心とする位置に集結させることができる合成樹脂と溶剤の組み合わせであれば、アクリル樹脂やトルエンおよび1−メトキシ−2−プロパノールでなくてもよい。   In this embodiment, an acrylic resin is used as the synthetic resin, and toluene and 1-methoxy-2-propanol are used as the solvent. However, the synthetic resin drip dried trace generated on the sample drip substrate for total reflection X-ray fluorescence analysis is hydrophilic. As long as the liquid sample is a combination of a synthetic resin and a solvent that can be collected at a position centered on a synthetic resin drip drying mark, the resin may not be acrylic resin, toluene, and 1-methoxy-2-propanol.

以下、本発明の第2実施形態の全反射蛍光X線分析装置について図4にしたがって説明する。この全反射蛍光X線分析装置は特願2006−207420号に記載されている全反射蛍光X線分析装置に、本発明の第1実施形態にかかる全反射蛍光X線分析用試料点滴基板15、および前記全反射蛍光X線分析用試料点滴基板の合成樹脂点滴乾燥痕41上に点滴された液体試料を乾燥させる乾燥手段8を備えた装置である。本明細書では、特願2006−207420号に記載されている全反射蛍光X線分析装置部分を分析部1という。また、特願2006−207420号の明細書に記載されている全事項は本明細書に引用されたものとして取り扱う。   The total reflection X-ray fluorescence spectrometer according to the second embodiment of the present invention will be described below with reference to FIG. This total reflection X-ray fluorescence analyzer is the same as the total reflection X-ray fluorescence analyzer described in Japanese Patent Application No. 2006-207420, but the sample reflection substrate 15 for total reflection X-ray fluorescence analysis according to the first embodiment of the present invention, And a drying means 8 for drying the liquid sample dripped onto the synthetic resin drip drying trace 41 of the sample drip substrate for total reflection X-ray fluorescence analysis. In this specification, the total reflection fluorescent X-ray analyzer part described in Japanese Patent Application No. 2006-207420 is referred to as an analysis unit 1. In addition, all matters described in the specification of Japanese Patent Application No. 2006-207420 are treated as cited in this specification.

乾燥手段8は、全反射蛍光X線分析用試料点滴基板15を載置する基板乾燥載置台84、液体試料を点滴するためのマイクロピペット81、マイクロピペット81を所定の位置に保持するマイクロピペット保持上部86、マイクロピペット保持下部87、全反射蛍光X線分析用試料点滴基板15上に点滴された液体試料を乾燥させる乾燥部82、乾燥部82の乾燥温度を制御する乾燥制御部83、これらを収納するケース80および乾燥部82の放射熱の発散を防ぐためのカバー88で構成されている。マイクロピペット81は10〜100μlに容量が可変できる。乾燥部82は、例えば100W(ワット)電球82である。乾燥制御部83は、液体試料の乾燥温度を制御するために電球82に流す電力と通電時間を制御する。   The drying means 8 includes a substrate drying stage 84 on which the total reflection fluorescent X-ray analysis sample drip substrate 15 is placed, a micropipette 81 for dipping a liquid sample, and a micropipette holder for holding the micropipette 81 in a predetermined position. The upper part 86, the micropipette holding lower part 87, the drying part 82 for drying the liquid sample dripped onto the sample drip substrate 15 for total reflection X-ray fluorescence analysis, the drying control part 83 for controlling the drying temperature of the drying part 82, The cover 80 is configured to prevent the radiation of the radiant heat from the case 80 to be stored and the drying unit 82. The volume of the micropipette 81 can be varied from 10 to 100 μl. The drying unit 82 is, for example, a 100 W (watt) bulb 82. The drying control unit 83 controls the power to be supplied to the light bulb 82 and the energization time in order to control the drying temperature of the liquid sample.

分析部1は、X線源2であるX線管11と、例えば累積多層膜で構成される分光素子13と、測定部3とで構成されており、X線管11からのX線12を、分光素子13で単色化し、一次X線14として、液体試料が乾燥手段8によって全反射蛍光X線分析用試料点滴基板15の合成樹脂点滴乾燥痕41上に点滴され、乾燥された試料乾燥痕72に照射し、試料乾燥痕72から発生する蛍光X線16を、例えば半導体検出器(SSDまたはSDD)である検出器17で検出し、液体試料である試料乾燥痕72に含有されている成分を定量・定性分析する。このとき、基板載置台30に載せられた全反射蛍光X線分析用試料点滴基板15の分析面15aの裏面15bが押圧手段20によって押圧され、分析面15aが、当接手段25の保持部26に保持されている当接部であるアルミナ製のセラミックスボール27に当接し、全反射蛍光X線分析用試料点滴基板15が所定の位置に設定される。   The analysis unit 1 includes an X-ray tube 11 that is an X-ray source 2, a spectroscopic element 13 formed of, for example, a cumulative multilayer film, and a measurement unit 3, and the X-ray 12 from the X-ray tube 11 is obtained. The liquid sample was instilled onto the synthetic resin drip drying mark 41 of the sample drip substrate 15 for total reflection fluorescent X-ray analysis as the primary X-ray 14 by the monochromator 13, and dried as the primary X-ray 14. 72, and the fluorescent X-rays 16 generated from the sample dry trace 72 are detected by the detector 17 which is a semiconductor detector (SSD or SDD), for example, and are contained in the sample dry trace 72 which is a liquid sample Quantitative and qualitative analysis. At this time, the back surface 15b of the analysis surface 15a of the total reflection X-ray fluorescence analysis sample drip substrate 15 placed on the substrate mounting table 30 is pressed by the pressing means 20, and the analysis surface 15a is held by the holding portion 26 of the contact means 25. The sample reflection substrate 15 for total reflection X-ray fluorescence analysis is set at a predetermined position by contacting with the ceramic ball 27 made of alumina which is a contact portion held by the substrate.

次に、本実施形態の装置の動作について説明する。図5に示すように、全反射蛍光X線分析用試料点滴基板15を乾燥手段8の基板乾燥載置台84に載置する。液体試料を、例えば20μl採取したマイクロピペット81がマイクロピペット保持下部87とマイクロピペット保持上部86の所定の位置に合わせてセットされ、全反射蛍光X線分析用試料点滴基板15の合成樹脂乾燥痕41上に液体試料70が点滴される。次に、乾燥制御部83でケース内に収納されている電球82に通電する電力と通電時間が
60W・4分間に設定され、電球82の放射熱により液体試料が加熱される。液体試料70は加熱乾燥されると、試料乾燥痕の形成の第1行程を示す図6、第2行程を示す図7および第3行程を示す図8に示すように液滴70が徐々に小さくなり凝縮され液滴71となり、乾燥が終了すると約2φの試料乾燥痕72が形成される。電球82に通電する電力と通電時間を30W・4分間以上に設定して加熱乾燥する場合もある。
Next, the operation of the apparatus of this embodiment will be described. As shown in FIG. 5, the sample drip substrate 15 for total reflection X-ray fluorescence analysis is placed on the substrate drying stage 84 of the drying means 8. For example, a micropipette 81 in which 20 μl of a liquid sample is collected is set in accordance with predetermined positions of the micropipette holding lower portion 87 and the micropipette holding upper portion 86, and the synthetic resin dry trace 41 of the sample drip substrate 15 for total reflection X-ray fluorescence analysis 15 is set. The liquid sample 70 is instilled on the top. Next, the electric power to be applied to the light bulb 82 accommodated in the case and the energization time are set to 60 W · 4 minutes by the drying control unit 83, and the liquid sample is heated by the radiant heat of the light bulb 82. When the liquid sample 70 is heated and dried, the droplet 70 gradually becomes smaller as shown in FIG. 6 showing the first process of forming the sample drying trace, FIG. 7 showing the second process, and FIG. 8 showing the third process. As a result, it is condensed into droplets 71. When drying is completed, a sample drying trace 72 of about 2φ is formed. In some cases, the electric power to be applied to the light bulb 82 and the energization time are set to 30 W · 4 minutes or more and heat drying.

液体試料70が点滴された全反射蛍光X線分析用試料点滴基板15を乾燥する加熱温度や加熱時間は、採取する液体試料量や液性などの条件により適宜設定すればよい。なお、図2、6、7および8に示した合成樹脂乾燥痕、液体試料の液滴および試料乾燥痕の大きさは図面上で明確に示すために、実際の大きさより大きく表されている。   What is necessary is just to set suitably the heating temperature and heating time which dry the sample drip board | substrate 15 for the total reflection fluorescent X-ray analysis in which the liquid sample 70 was instilled according to conditions, such as the amount of liquid samples extract | collected, and a liquid property. The sizes of the synthetic resin dry marks, the liquid sample droplets and the sample dry marks shown in FIGS. 2, 6, 7 and 8 are shown larger than the actual sizes in order to clearly show them on the drawings.

図4に示すように、試料乾燥痕72が形成された全反射蛍光X線分析用試料点滴基板15を、基板載置台30の基板載置溝31にセットして、その後、測定を開始すると、駆動制御部によって駆動された押圧手段20が基板載置台30の押圧手段通過孔32を通過し、基板載置溝31にセットされた全反射蛍光X線分析用試料点滴基板15の裏面15bを押圧しながらガラス基板の分析面15aをセラミックスボール27に当接させると押圧手段20を駆動しているステッピングモータが停止し、全反射蛍光X線分析用試料点滴基板15が所定の位置に設定され、その位置で保持される。   As shown in FIG. 4, the sample drip substrate 15 for total reflection X-ray fluorescence analysis on which the sample drying trace 72 is formed is set in the substrate placement groove 31 of the substrate placement table 30, and then the measurement is started. The pressing unit 20 driven by the drive control unit passes through the pressing unit passage hole 32 of the substrate mounting table 30 and presses the back surface 15b of the sample drip substrate 15 for total reflection X-ray fluorescence analysis set in the substrate mounting groove 31. However, when the analysis surface 15a of the glass substrate is brought into contact with the ceramic ball 27, the stepping motor driving the pressing means 20 is stopped, and the total reflection fluorescent X-ray analysis sample drip substrate 15 is set at a predetermined position. Held in that position.

全反射蛍光X線分析用試料点滴基板15が所定の位置に保持されると、全反射蛍光X線分析用試料点滴基板15にX線管11からのX線12を分光素子13で単色化した1次X線14が照射され、全反射蛍光X線分析用試料点滴基板15の試料点滴乾燥痕72から発生した蛍光X線を検出器17で検出し、試料中に含有する成分を分析する。測定が終了すると押圧手段20を駆動しているステッピングモータが回転を始め、押圧手段20が下降し、全反射蛍光X線分析用試料点滴基板15が基板載置溝31に収容される。順次、同様の操作で分析目的個数の試料の分析を行う。   When the total reflection fluorescent X-ray analysis sample drip substrate 15 is held at a predetermined position, X-rays 12 from the X-ray tube 11 are monochromatized by the spectroscopic element 13 on the total reflection fluorescent X-ray analysis sample drip substrate 15. The primary X-ray 14 is irradiated, and the fluorescent X-ray generated from the sample drip drying trace 72 of the sample drip substrate 15 for total reflection X-ray fluorescence analysis is detected by the detector 17, and the components contained in the sample are analyzed. When the measurement is completed, the stepping motor that drives the pressing unit 20 starts rotating, the pressing unit 20 descends, and the total reflection fluorescent X-ray analysis sample drip substrate 15 is accommodated in the substrate mounting groove 31. Sequentially, the same number of samples are analyzed by the same operation.

本実施形態の全反射蛍光X線分析装置で分析すると、合成樹脂点滴乾燥痕の親水性により、液体試料が試料乾燥痕72として合成樹脂点滴乾燥痕を中心とする位置に集結しているので、測定試料位置の変動が少なく検出する蛍光X線強度の変動が少なくなる。また、合成樹脂点滴乾燥痕は不純物を含有しておらず、厚みが1μmと極薄く全反射蛍光X線分析のバックグラウンドの発生がほとんどなくなる。従来の全反射蛍光X線分析装置を用いて、合成樹脂点滴乾燥痕が形成されていないシリコンコートガラス基板に液体試料を点滴して測定した場合の10回の繰り返し変動係数は15%であったが、本実施形態の全反射蛍光X線分析装置を用いて、全反射蛍光X線分析用試料点滴基板に液体試料を点滴して測定した場合の10回の繰り返し変動係数は8%であり、分析精度が大きく向上した。   When analyzed with the total reflection X-ray fluorescence spectrometer of the present embodiment, the liquid sample is concentrated as a sample dry mark 72 at a position centered on the synthetic resin drip dry mark due to the hydrophilicity of the synthetic resin drip dry mark. There is little variation in the position of the measurement sample, and the variation in the detected fluorescent X-ray intensity is small. Further, the synthetic resin drip drying trace does not contain impurities, and the thickness is as extremely thin as 1 μm, and almost no background of total reflection X-ray fluorescence analysis occurs. Using a conventional total reflection X-ray fluorescence analyzer, the coefficient of variation of 10 repetitions when a liquid sample was measured by dipping on a silicon-coated glass substrate on which no synthetic resin drip drying marks were formed was 15%. However, using the total reflection X-ray fluorescence analyzer of the present embodiment, the variation coefficient of 10 repetitions when the liquid sample is measured on the total reflection X-ray fluorescence analysis sample drip substrate is 8%, Analysis accuracy has been greatly improved.

次に、本発明の第3実施形態の全反射蛍光X線分析方法について説明する。マイクロピペットで液体試料を、例えば20μl採取し、本発明の第1実施形態の全反射蛍光X線分析用試料点滴基板15の合成樹脂点滴乾燥痕41上に点滴する。点滴された液体試料70は図6に示すように、合成樹脂点滴乾燥痕41の上に盛り上がった形状になる。次に、この全反射蛍光X線分析用試料点滴基板15を乾燥させる。乾燥はこの全反射蛍光X線分析用試料点滴基板15を取り囲んだヒータなどで加熱して乾燥させると、前記した図6、7および8に示すように、盛り上がった液体試料の液滴70が徐々に小さく凝縮し液滴71となり、乾燥が終了すると約2φの試料乾燥痕72が生成される。   Next, a total reflection X-ray fluorescence analysis method according to the third embodiment of the present invention will be described. For example, 20 μl of a liquid sample is collected with a micropipette and dropped on the synthetic resin drip drying trace 41 of the sample drip substrate 15 for total reflection X-ray fluorescence analysis of the first embodiment of the present invention. As shown in FIG. 6, the drip liquid sample 70 has a shape raised on the synthetic resin drip drying trace 41. Next, the sample drip substrate 15 for total reflection fluorescent X-ray analysis is dried. When drying is performed by heating with a heater or the like surrounding the sample drip substrate 15 for total reflection X-ray fluorescence analysis, as shown in FIGS. When the drying is completed, a sample drying mark 72 of about 2φ is generated.

試料乾燥痕72が生成された全反射蛍光X線分析用試料点滴基板15を全反射蛍光X線分析装置の基板載置台にセットし、測定を開始して試料乾燥痕72から発生する蛍光X線の強度を測定し、試料乾燥痕72中に含有される成分を分析する。   The sample drip substrate 15 for total reflection X-ray fluorescence analysis on which the sample drying trace 72 is generated is set on the substrate mounting table of the total reflection X-ray fluorescence analyzer, and the measurement is started and the fluorescent X-ray generated from the sample drying trace 72 The component contained in the sample drying mark 72 is analyzed.

本発明の第1実施形態である全反射蛍光X線分析用試料点滴基板を形成する説明図である。It is explanatory drawing which forms the sample drip board | substrate for total reflection X-ray fluorescence analysis which is 1st Embodiment of this invention. 同形成された全反射蛍光X線分析用試料点滴基板の斜視図である。It is a perspective view of the sample drip board for total reflection fluorescence X-ray analysis formed similarly. 同全反射蛍光X線分析用試料点滴基板を形成するための合成樹脂点滴乾燥痕形成具の概略斜視図である。It is a schematic perspective view of the synthetic resin drip drying trace formation tool for forming the sample drip board for the total reflection X-ray fluorescence analysis. 本発明の第2実施形態である全反射蛍光X線分析装置の概略図である。It is the schematic of the total reflection X-ray fluorescence spectrometer which is 2nd Embodiment of this invention. 同全反射蛍光X線分析装置の乾燥手段の概略斜視図である。It is a schematic perspective view of the drying means of the same total reflection fluorescent X-ray analyzer. 同全反射蛍光X線分析装置での試料乾燥痕の形成の第1行程を示す図である。It is a figure which shows the 1st process of formation of the sample dry trace in the same total reflection fluorescent-X-ray-analysis apparatus. 同第2行程を示す図である。It is a figure which shows the 2nd process. 同第3行程を示す図である。It is a figure which shows the 3rd process. 従来技術の点滴フイルム体の断面図である。It is sectional drawing of the drip film body of a prior art.

符号の説明Explanation of symbols

2 X線源
8 乾燥手段
14 1次X線
15 全反射蛍光X線分析用試料点滴基板
15K 平面基板
16 蛍光X線
17 検出器
30 基板載置台
41 合成樹脂点滴乾燥痕
70 液体試料
72 試料乾燥痕
2 X-ray source 8 Drying means 14 Primary X-ray 15 Sample reflection substrate 15K for total reflection X-ray fluorescence analysis Flat substrate 16 Fluorescence X-ray 17 Detector 30 Substrate mounting table 41 Synthetic resin drip drying mark 70 Liquid sample 72 Sample drying mark

Claims (4)

液体試料を点滴乾燥させるための試料点滴基板であって、
表面が疎水性であり、鏡面研磨の平面度を有する平面基板と、
前記平面基板の表面の所定の部位に、合成樹脂を溶剤にて所定の濃度に溶解された合成樹脂溶液の所定量を点滴乾燥された合成樹脂点滴乾燥痕と、
を有する全反射蛍光X線分析用試料点滴基板。
A sample drip substrate for drip-drying a liquid sample,
A planar substrate having a hydrophobic surface and having a mirror polished flatness;
Synthetic resin drip-dried traces obtained by drip-drying a predetermined amount of a synthetic resin solution in which a synthetic resin is dissolved in a predetermined concentration with a solvent at a predetermined site on the surface of the flat substrate,
A sample drip substrate for total reflection X-ray fluorescence analysis.
請求項1において、
前記合成樹脂がアクリル樹脂である全反射蛍光X線分析用試料点滴基板。
In claim 1,
A sample drip substrate for total reflection X-ray fluorescence analysis, wherein the synthetic resin is an acrylic resin.
請求項1または2に記載の全反射蛍光X線分析用試料点滴基板と、
前記全反射蛍光X線分析用試料点滴基板の合成樹脂点滴乾燥痕上に点滴された液体試料を乾燥させる乾燥手段と、
前記乾燥手段によって乾燥された試料乾燥痕に1次X線を照射するX線源と、
前記1次X線が照射される前記試料乾燥痕から発生する蛍光X線を検出する検出器と、
を有する全反射蛍光X線分析装置。
A sample drip substrate for total reflection X-ray fluorescence analysis according to claim 1 or 2,
A drying means for drying the liquid sample drip on the synthetic resin drip drying trace of the sample drip substrate for total reflection X-ray fluorescence analysis;
An X-ray source that emits primary X-rays to a sample drying mark dried by the drying means;
A detector for detecting fluorescent X-rays generated from the sample drying trace irradiated with the primary X-ray;
A total reflection fluorescent X-ray analyzer.
請求項1または2に記載の全反射蛍光X線分析用試料点滴基板の合成樹脂点滴乾燥痕上に液体試料の所定量を点滴し、
点滴された前記液体試料を乾燥させ試料乾燥痕を生成し、
前記試料乾燥痕が生成された前記蛍光X線分析用試料点滴基板を全反射蛍光X線分析装置の基板載置台にセットし、
測定を開始して前記試料乾燥痕から発生する蛍光X線の強度を測定し、
前記液体試料中に含有される成分を分析する全反射蛍光X線分析方法。
Injecting a predetermined amount of a liquid sample onto the synthetic resin drip drying trace of the sample drip substrate for total reflection fluorescent X-ray analysis according to claim 1 or 2,
Drying the drip liquid sample to produce a sample dry mark,
Set the sample drip substrate for X-ray fluorescence analysis in which the sample dry trace is generated on a substrate mounting table of a total reflection X-ray fluorescence analyzer,
Start measurement and measure the intensity of fluorescent X-rays generated from the sample dry trace,
A total reflection X-ray fluorescence analysis method for analyzing a component contained in the liquid sample.
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