JPH06174615A - Sample plate for analysis - Google Patents
Sample plate for analysisInfo
- Publication number
- JPH06174615A JPH06174615A JP4349880A JP34988092A JPH06174615A JP H06174615 A JPH06174615 A JP H06174615A JP 4349880 A JP4349880 A JP 4349880A JP 34988092 A JP34988092 A JP 34988092A JP H06174615 A JPH06174615 A JP H06174615A
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- Prior art keywords
- analysis
- sample
- analyzed
- sample plate
- plate
- Prior art date
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- Analysing Materials By The Use Of Radiation (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、表面に置かれた液滴状
の液体分析試料を加熱による濃縮するために使用される
分析用試料板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sample plate for analysis used for concentrating a liquid analysis sample in the form of droplets on a surface by heating.
【０００２】[0002]
【従来の技術】半導体用のＳｉウェーハ表面にある酸化
膜に囲まれた金属不純物を、気相のフッ酸で分解し、こ
の表面を希フッ酸の液滴で走査し、該液滴中に金属不純
物を回収し、これをＳｉウェーハ上で濃縮、蒸発乾固
し、その乾固部を全反射蛍光Ｘ線分析装置により分析す
る方法が開発されており、分析面積／液滴の乾固面積の
比を大きくすることで分析感度を大きく向上させ得るこ
とが知られている。この場合、フッ酸で処理されたＳｉ
表面は、著しく疎水性化されるため、該表面において
は、水を主成分とする分析試料液は液滴状となる。従っ
て、この場合には、Ｓｉウェーハがそのまま蒸発乾固を
行なう分析用試料板となる。2. Description of the Related Art Metallic impurities surrounded by an oxide film on the surface of a Si wafer for semiconductors are decomposed by vapor phase hydrofluoric acid, and the surface is scanned with a droplet of dilute hydrofluoric acid. A method has been developed in which metal impurities are recovered, concentrated on a Si wafer, evaporated to dryness, and the dry solid portion is analyzed by a total reflection X-ray fluorescence analyzer. It is known that the sensitivity of analysis can be greatly improved by increasing the ratio of. In this case, Si treated with hydrofluoric acid
Since the surface is remarkably hydrophobicized, the analysis sample liquid containing water as a main component is in the form of droplets on the surface. Therefore, in this case, the Si wafer becomes a sample plate for analysis that evaporates to dryness.
【０００３】[0003]
【発明が解決しようとする課題】上記の分析方法におい
て、分析試料液の乾固部（ほぼ円形となる）の直径は、
Ｓｉウェーハ表面上を走査する希フッ酸の液滴の径とほ
ぼ同じになる。即ち、希フッ酸の走査により、希フッ酸
とＳｉ表面とが、下記式： ＳｉＯ2 ＋４ＨＦ → ＳｉＦ4 ＋２Ｈ2 Ｏ に従って反応し、生成したＳｉＦ4 は、さらに加水分解
してＳｉ（ＯＨ）4 となるが、この反応は、まず蒸発乾
固が行なわれるＳｉウェーハ表面上における液−空気−
Ｓｉの界面である液滴周辺から始まり、この部分にＳｉ
（ＯＨ）4 が析出して所謂ウオーターマークを作るから
である。In the above-mentioned analysis method, the diameter of the dry solid portion (which becomes substantially circular) of the analysis sample liquid is
The diameter is almost the same as the diameter of the droplet of dilute hydrofluoric acid scanning on the surface of the Si wafer. That is, by scanning with dilute hydrofluoric acid, the dilute hydrofluoric acid and the Si surface react according to the following formula: SiO 2 + 4HF → SiF 4 + 2H 2 O, and the produced SiF 4 is further hydrolyzed to Si (OH) 4 However, this reaction is carried out by liquid-air-on the surface of the Si wafer where evaporation to dryness is first performed.
Starting from the periphery of the droplet, which is the interface of Si,
This is because (OH) 4 is deposited to form a so-called water mark.
【０００４】然るに、放射性同位元素で標識した分析対
象金属不純物の微量を、試料液滴に溶解し、これを蒸発
乾固して金属不純物の乾固状態を調べた結果、金属不純
物が59Ｆｅ，22Ｎａ，51Ｃｒ及び64Ｃｕの何れの場合に
も、円形の乾固部の円周部に著しく偏析することが認め
られた。このような偏析は、全反射蛍光Ｘ線分析のみな
らず、どのような局部的表面の分析でも好ましくない。However, as a result of dissolving a trace amount of the metal impurity to be analyzed labeled with a radioisotope in a sample droplet and evaporating it to dryness to examine the dry state of the metal impurity, it was found that the metal impurity was 59 Fe, It was confirmed that, in any of 22 Na, 51 Cr and 64 Cu, significant segregation was observed in the circumferential portion of the circular dry solid portion. Such segregation is not preferable not only for total reflection X-ray fluorescence analysis but also for any local surface analysis.
【０００５】上記のような偏析は、薬液として硝酸を主
とする液を使用することによりかなり改善されるが、こ
の場合には、分析対象の金属不純物以外に周辺部に析出
するＳｉ化合物が増加するために好ましくない。The above-mentioned segregation is considerably improved by using a liquid mainly containing nitric acid as a chemical liquid, but in this case, in addition to the metal impurities to be analyzed, the amount of Si compounds precipitated in the peripheral portion is increased. It is not preferable to do.
【０００６】また、乾固すべき分析試料液を適当な細管
を用いて吸引し、これを吐出して、液滴を小さくして蒸
発乾固を行ない、乾固部の面積を小さくすることによ
り、偏析傾向を抑制することが考えられる。この方法
は、乾固部の面積が小さくなるので、分析面積／液滴の
乾固面積の比が大きくなり、分析感度の点でも好まし
い。しかし、蒸発乾固を行なうための試料板としてＳｉ
ウェーハー等を用いると、乾固部の面積が小さくなるも
のの、この試料板においても偏析傾向が生じるため、未
だ、十分満足のいく方法ではない。Further, the analytical sample liquid to be dried is sucked by using a suitable thin tube, and this is discharged to reduce the liquid droplets to evaporate and dry, thereby reducing the area of the dried portion. It is considered that the segregation tendency is suppressed. This method is preferable in terms of analysis sensitivity because the area of the dry and solid portion becomes small and the ratio of the analysis area / the dry and solid area of the droplet becomes large. However, Si is used as a sample plate for evaporation to dryness.
If a wafer or the like is used, the area of the dry-solidified portion becomes smaller, but segregation tends to occur also in this sample plate, so it is not yet a sufficiently satisfactory method.
【０００７】さらに、前述した気相のフッ酸を用いての
処理により、酸化膜や窒化膜を有しているＳｉウェーハ
の膜中の不純物の分析を行なうと、走査液滴中のＳｉＦ
--の濃度が著しく高くなるため、分析用試料板であるＳ
ｉウェーハの蒸発乾固周辺においてＳｉ化合物の析出量
が増大し、このＳｉの妨害により、分析感度が極端に低
下するという問題もある。Furthermore, when the impurities in the film of the Si wafer having the oxide film or the nitride film are analyzed by the above-mentioned treatment using the vapor phase hydrofluoric acid, the SiF in the scanning droplets is analyzed.
Since the concentration of --becomes extremely high, S which is a sample plate for analysis
There is also a problem that the amount of Si compound deposited increases around the evaporative dryness of the i-wafer, and the interference of this Si significantly reduces the analytical sensitivity.
【０００８】従って本発明の目的は、前述した分析試料
液滴の蒸発乾固に際して、析出成分の偏析傾向が有効に
防止され、しかも分析対象の成分の検出感度を妨害する
Ｓｉの析出が有効に抑制された分析用試料板を提供する
ことにある。Therefore, the object of the present invention is to effectively prevent the segregation tendency of the deposited components during the evaporation and drying of the above-mentioned analytical sample droplets, and to effectively deposit Si which interferes with the detection sensitivity of the components to be analyzed. An object is to provide a suppressed sample plate for analysis.
【０００９】[0009]
【発明が解決しようとする課題】本発明によれば、表面
に置かれた液滴状の液体分析試料を加熱によって濃縮す
るための分析用試料板において、平滑表面を有する板状
支持体の表面にフッ素樹脂薄膜層を設けたことを特徴と
する分析用試料板が提供される。According to the present invention, the surface of a plate-shaped support having a smooth surface in an analytical sample plate for concentrating a liquid analytical sample in the form of droplets placed on the surface by heating. There is provided a sample plate for analysis characterized in that a fluororesin thin film layer is provided on the.
【００１０】[0010]
【作用】即ち本発明においては、蒸発乾固が行なわれる
試料板の表面がフッ素樹脂薄膜層で保護されているた
め、表面のＳｉとフッ酸等の試料液との反応が有効に回
避され、前述した分析対象となる金属の偏析を有効に防
止することができる。しかも、Ｓｉが分析面からフッ酸
の試料液滴中に入った場合にも、それが多量であったと
しても、この試料板上での加熱により、下記式： Ｈ2 ＳｉＦ6 → ＳｉＦ4 ↑ ＋ ２ＨＦ↑ で示される分解反応が生じ、Ｓｉは蒸発飛散し、フッ素
樹脂表面には分析対象である不純物元素のみが残り、分
析のための濃縮が有効に行なわれるのである。That is, in the present invention, since the surface of the sample plate on which evaporation and drying are performed is protected by the fluororesin thin film layer, the reaction between the surface Si and the sample solution such as hydrofluoric acid is effectively avoided, It is possible to effectively prevent the segregation of the metal to be analyzed as described above. Moreover, when Si enters the sample droplet of hydrofluoric acid from the analysis surface, even if a large amount of Si enters, the following formula: H 2 SiF 6 → SiF 4 ↑ The decomposition reaction represented by + 2HF ↑ occurs, Si is evaporated and scattered, and only the impurity element to be analyzed remains on the surface of the fluororesin, and the concentration for analysis is effectively performed.
【００１１】本発明において、フッ素樹脂薄膜層を形成
すべき板状支持体としては、試料液滴を安定に保持する
ために平滑表面を有するものが使用される。かかる支持
体は、試料液滴の加熱濃縮を有効に行なうために、熱伝
導性が良好であり且つ試料液滴の濃縮のための加熱によ
って分析に有害な不純物を発生しないものであることが
望ましく、例えば半導体用シリコンウェハーが好適に使
用されるが、これ以外にも、高純度のゲルマニウム、Ｓ
ｉＣ等の材料から形成されていてもよく、さらには石英
板も使用することができる。この板状支持体の厚みは、
一般に、５００μm 〜２mm程度が好適である。In the present invention, the plate-like support on which the fluororesin thin film layer is to be formed is one having a smooth surface for stably holding the sample droplets. It is desirable that such a support has good thermal conductivity in order to effectively condense the sample droplets by heating and does not generate impurities harmful to the analysis by the heating for concentrating the sample droplets. For example, silicon wafers for semiconductors are preferably used, but in addition to this, high purity germanium, S
It may be formed of a material such as iC, and a quartz plate can also be used. The thickness of this plate-shaped support is
Generally, about 500 μm to 2 mm is suitable.
【００１２】またフッ素樹脂としては、それ自体の種々
のフッ素樹脂、例えばポリテトラフルオロエチレン（Ｐ
ＴＦＥ）、四フッ化エチレンパーフルオロアルコキシエ
チレン（ＰＦＡ）等を使用することができるが、特に全
反射蛍光Ｘ線分析を行なうための試料板としては、アモ
ルファスのフッ素樹脂が好適に使用される。即ち、通常
のＰＦＡ等のフッ素樹脂は結晶性のため、全反射蛍光Ｘ
線分析用に用いた場合には、Ｘ線の散乱を誘発して分析
を有効に行なうことが困難となるからである。勿論、オ
ージェやＥＳＣＡ等の局部表面分析の場合には、このよ
うな制限はなく、結晶質あるいはアモルファスの何れの
フッ素樹脂を使用することもできる。尚、アモルファス
のフッ素樹脂の代表的なものは、テフロンＡＦの商品名
で市販されている。As the fluororesin, various fluororesins per se, such as polytetrafluoroethylene (P
TFE), tetrafluoroethylene perfluoroalkoxyethylene (PFA), or the like can be used, but an amorphous fluororesin is preferably used as a sample plate for performing total reflection X-ray fluorescence analysis. That is, since the fluororesin such as ordinary PFA is crystalline, the total reflection fluorescence X
This is because when it is used for line analysis, it becomes difficult to induce X-ray scattering and effectively perform analysis. Of course, in the case of local surface analysis such as Auger or ESCA, there is no such limitation, and either crystalline or amorphous fluororesin can be used. A typical amorphous fluororesin is commercially available under the trade name of Teflon AF.
【００１３】このフッ素樹脂層の厚みは、厚すぎると、
熱伝導性が悪くなり、細管から吐出させた試料液滴を蒸
発させる場合の液滴の量のコントロールが困難となり、
またバイメタル効果により加熱時に試料板の変形を生じ
ることがある。このため、この厚みは適当な範囲に調整
されていることが好ましく、厳密ではないが、通常、0.
５〜２μm の範囲が適当である。If the thickness of this fluororesin layer is too thick,
The thermal conductivity deteriorates, making it difficult to control the droplet volume when evaporating the sample droplets discharged from the thin tube.
In addition, the sample plate may be deformed during heating due to the bimetal effect. For this reason, this thickness is preferably adjusted to an appropriate range, although not strictly, usually 0.
A range of 5 to 2 μm is suitable.
【００１４】[0014]
実施例１ 高純度の直径 125mm、厚さ１mmの鏡面Ｓｉウェーハにお
いて、その鏡面内を平坦度２μm 以内に仕上げた。商品
名テフロンＡＦのアモルファスフッ素樹脂粉を、蒸留精
製した専用の溶剤に溶解し、スピンナを用いて約5000Å
の厚さに、前記鏡面上にコーティングして分析用試料板
を作成した。次いで、59Ｆｅ標識鉄 4.1×1011atoms を
含む１５０μｌのＨＦ液を、本願出願人の出願である特
願平１−８８１４４号の実施例１で使用されている前処
理用の細管に吸引し、上記分析用試料板の所定位置で、
１５分かけて吐出蒸発せしめた。吐出蒸発した乾固部
（径：約2.５mm) における59Ｆｅ分布を、ラジオルミノ
グラフィにより測定した。結果を図１に示す。Example 1 In a high-purity mirror surface Si wafer having a diameter of 125 mm and a thickness of 1 mm, the inside of the mirror surface was finished to have a flatness of 2 μm or less. Dissolve Teflon AF amorphous fluororesin powder in a special solvent that has been distilled and purified, and use a spinner for approximately 5000 Å
Was coated on the mirror surface to prepare a sample plate for analysis. Then, 150 μl of HF solution containing 4.1 × 10 11 atoms of 59 Fe-labeled iron was sucked into the pretreatment thin tube used in Example 1 of Japanese Patent Application No. 1-88144 filed by the present applicant. , At a predetermined position on the sample plate for analysis,
It was discharged and evaporated over 15 minutes. The 59 Fe distribution in the dry solid portion (diameter: about 2.5 mm) discharged and evaporated was measured by radioluminography. The results are shown in Fig. 1.
【００１５】比較例１ 前記分析用試料板として、アモルファスフッ素樹脂がコ
ーティングされていないものを使用した以外は、実施例
１と同様にして試料板上の乾固部（径：約３mm) におけ
る59Ｆｅ分布を測定した。結果を図２に示す。上記の図
１及び図２を比較することにより、本発明の分析用試料
板を用いて試料液滴の濃縮（蒸発乾固）を行なった場合
には、乾固部周辺の偏析が回避され、かつ乾固面積が小
さくなり中央部に効果的に濃縮されることが了解され
る。Comparative Example 1 59 in a dry solid portion (diameter: about 3 mm) on the sample plate was used in the same manner as in Example 1 except that the sample plate for analysis which was not coated with amorphous fluororesin was used. The Fe distribution was measured. The results are shown in Figure 2. By comparing FIG. 1 and FIG. 2 described above, when the sample droplets are concentrated (evaporated to dryness) using the sample plate for analysis of the present invention, segregation around the dry solid part is avoided, It is also understood that the dry solidification area becomes smaller and it is effectively concentrated in the central part.
【００１６】[0016]
【発明の効果】本発明の分析用試料板によれば、分析す
べき成分元素を含む試料液滴の濃縮を行なう場合、分析
対象となる成分元素の偏析を有効に防止することがで
き、また分析対象となる成分元素が選択的に有効に濃縮
されるため、精度、感度ともによい分析を行なうことが
できる。また蒸発の際の液滴の広がりが防止され、乾固
面積が小さくなる利点がある。かかる分析用試料板にお
いて、特にアモルファスフッ素樹脂を用いて表面層が形
成されているものは、特に全反射蛍光Ｘ線分析等の局部
的分析に極めて有用である。According to the sample plate for analysis of the present invention, when the sample droplet containing the component element to be analyzed is concentrated, segregation of the component element to be analyzed can be effectively prevented, and Since the component element to be analyzed is selectively and effectively concentrated, it is possible to perform analysis with good accuracy and sensitivity. Further, there is an advantage that the spread of droplets at the time of evaporation is prevented and the dry-solid area is reduced. Of such analytical sample plates, those whose surface layer is formed of an amorphous fluororesin are particularly useful for local analysis such as total reflection X-ray fluorescence analysis.
【図１】本発明の分析用試料板を用いて試料液滴の蒸発
乾固を行なった場合において、蒸発乾固部に析出した59
Ｆｅ分布を示す図。FIG. 1 is a graph showing that when a sample droplet is evaporated to dryness using the sample plate for analysis of the present invention, it is deposited in an evaporated dry solid part 59.
The figure which shows Fe distribution.
【図２】フッ素樹脂層が形成されていないＳｉ分析用試
料板を用いて試料液滴の蒸発乾固を行なった場合におい
て、蒸発乾固部に析出した59Ｆｅ分布を示す図。FIG. 2 is a diagram showing a distribution of 59 Fe deposited in a dry evaporation portion in the case where a sample droplet for evaporation is dried to dryness using a Si analysis sample plate on which a fluororesin layer is not formed.
Claims (2)
加熱によって濃縮するための分析用試料板において、 平滑表面を有する板状支持体の表面にフッ素樹脂薄膜層
を設けたことを特徴とする分析用試料板。1. A sample plate for analysis for concentrating a droplet-shaped liquid analysis sample placed on a surface by heating, wherein a fluororesin thin film layer is provided on the surface of a plate-shaped support having a smooth surface. Characteristic sample plate for analysis.
素樹脂である請求項１に記載の分析用試料板。2. The sample plate for analysis according to claim 1, wherein the fluororesin is an amorphous fluororesin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4349880A JPH06174615A (en) | 1992-12-01 | 1992-12-01 | Sample plate for analysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4349880A JPH06174615A (en) | 1992-12-01 | 1992-12-01 | Sample plate for analysis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06174615A true JPH06174615A (en) | 1994-06-24 |
Family
ID=18406742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4349880A Pending JPH06174615A (en) | 1992-12-01 | 1992-12-01 | Sample plate for analysis |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06174615A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0915174A (en) * | 1995-06-30 | 1997-01-17 | Nec Corp | Method for chemical analysis and equipment for pretreatment therefor |
| JP2008020339A (en) * | 2006-07-13 | 2008-01-31 | Sumco Corp | Analyzing method for polishing slurry of silicone wafer |
| JP2008122144A (en) * | 2006-11-09 | 2008-05-29 | Rigaku Industrial Co | Specimen drip substrate for total-reflection fluorescence x-ray analysis, total reflection fluorescent x-ray analyzer, and total reflection fluorescent x-ray analysis method |
| CN102809497A (en) * | 2011-06-03 | 2012-12-05 | 通用电气公司 | Manufacture of engineering components with designed defects for analysis of production components |
| JP5870439B1 (en) * | 2015-04-02 | 2016-03-01 | 株式会社東レリサーチセンター | Method for preparing sample stage for micro-spectral analysis |
-
1992
- 1992-12-01 JP JP4349880A patent/JPH06174615A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0915174A (en) * | 1995-06-30 | 1997-01-17 | Nec Corp | Method for chemical analysis and equipment for pretreatment therefor |
| JP2008020339A (en) * | 2006-07-13 | 2008-01-31 | Sumco Corp | Analyzing method for polishing slurry of silicone wafer |
| JP2008122144A (en) * | 2006-11-09 | 2008-05-29 | Rigaku Industrial Co | Specimen drip substrate for total-reflection fluorescence x-ray analysis, total reflection fluorescent x-ray analyzer, and total reflection fluorescent x-ray analysis method |
| JP4537367B2 (en) * | 2006-11-09 | 2010-09-01 | 株式会社リガク | Sample reflection substrate for total reflection X-ray fluorescence analysis, total reflection X-ray fluorescence analyzer, and total reflection X-ray fluorescence analysis method |
| CN102809497A (en) * | 2011-06-03 | 2012-12-05 | 通用电气公司 | Manufacture of engineering components with designed defects for analysis of production components |
| JP5870439B1 (en) * | 2015-04-02 | 2016-03-01 | 株式会社東レリサーチセンター | Method for preparing sample stage for micro-spectral analysis |
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