JPH08321535A - Recovery method of impurities - Google Patents
Recovery method of impuritiesInfo
- Publication number
- JPH08321535A JPH08321535A JP17468796A JP17468796A JPH08321535A JP H08321535 A JPH08321535 A JP H08321535A JP 17468796 A JP17468796 A JP 17468796A JP 17468796 A JP17468796 A JP 17468796A JP H08321535 A JPH08321535 A JP H08321535A
- Authority
- JP
- Japan
- Prior art keywords
- semiconductor substrate
- impurities
- gas
- decomposition
- hydrofluoric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Sampling And Sample Adjustment (AREA)
- Testing Or Measuring Of Semiconductors Or The Like (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、半導体基板の表面
の不純物の超微量不純物分析用の試料を調整するための
半導体基板の表面の不純物回収方法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for recovering impurities from the surface of a semiconductor substrate for preparing a sample for analysis of ultratrace impurities of impurities on the surface of a semiconductor substrate.
【０００２】[0002]
【従来の技術】従来の半導体基板の表面の不純物回収装
置としては、例えば特開昭６０−６９５３１号公報に示
されている。図２はこの従来の半導体基板の表面の不純
物回収装置の概略縦断面図であり、図において、３１は
密閉容器、３２はその密閉容器３１内に配設されたフッ
化水素ガス発生用フッ化水素酸貯蔵容器、３３はウエハ
キャリアであり、半導体基板を保持するためにある。３
４は分解液受容器であり、貯蔵容器３２を加熱すること
によりフッ化水素ガスを発生させて半導体薄膜を分解
し、分解された分解液を受容するためにある。2. Description of the Related Art A conventional device for recovering impurities from the surface of a semiconductor substrate is disclosed in, for example, Japanese Patent Laid-Open No. 60-69531. FIG. 2 is a schematic vertical cross-sectional view of the conventional impurity recovery device for the surface of a semiconductor substrate. In the figure, 31 is a closed container, and 32 is a fluoride for generating hydrogen fluoride gas arranged in the closed container 31. The hydrogen acid storage container 33 is a wafer carrier for holding a semiconductor substrate. Three
Reference numeral 4 denotes a decomposed liquid receiver, which is used to generate hydrogen fluoride gas by heating the storage container 32 to decompose the semiconductor thin film, and to receive the decomposed decomposed liquid.
【０００３】[0003]
【発明が解決しようとする課題】このような従来の半導
体基板の表面の不純物回収装置では、フッ化水素ガスの
発生量を制御することができない。また、貯蔵容器３２
を密閉容器３１内に設置するため、密閉容器３１の容積
を大きくする必要がある。またフッ化水素ガスを半導体
基板の表面で結露させ分解液を回収するために、多量の
フッ化水素ガスが必要である。さらに半導体基板の表面
から内部の深さ方向に分布する不純物を回収することが
できないという課題を有していた。In such a conventional apparatus for collecting impurities on the surface of a semiconductor substrate, the amount of hydrogen fluoride gas generated cannot be controlled. In addition, the storage container 32
Since it is installed in the closed container 31, it is necessary to increase the volume of the closed container 31. Further, a large amount of hydrogen fluoride gas is necessary to collect the decomposed liquid by causing the hydrogen fluoride gas to condense on the surface of the semiconductor substrate. Further, there is a problem that impurities distributed in the depth direction inside the semiconductor substrate cannot be recovered.
【０００４】本発明は上記課題を解決するもので、環境
からの汚染なしに容易に半導体基板の表面から内部の深
さ方向に分布する不純物の回収ができる半導体基板の表
面の不純物回収方法および不純物回収装置を提供するこ
とを目的とする。An object of the present invention is to solve the above-mentioned problems, and a method and a method for collecting impurities distributed on the surface of a semiconductor substrate from the surface of the semiconductor substrate easily without contaminating the environment. An object is to provide a recovery device.
【０００５】[0005]
【課題を解決するための手段】本発明は上記目的を達成
するために、半導体基板を酸化雰囲気に曝して酸化する
酸化工程と、上記半導体基板表面に形成された酸化膜を
酸化膜分解雰囲気に曝して分解する分解工程と、分解液
を回収する回収工程と、上記酸化雰囲気を上記分解雰囲
気に置換する置換工程とを有し、上記４工程を含む回収
サイクルを繰り返す半導体基板表面の不純物回収方法と
する。In order to achieve the above object, the present invention provides an oxidizing step of oxidizing a semiconductor substrate by exposing it to an oxidizing atmosphere, and an oxide film formed on the surface of the semiconductor substrate into an oxide film decomposing atmosphere. A method for recovering impurities on the surface of a semiconductor substrate, which has a decomposition step of exposing and decomposing, a recovery step of recovering a decomposition solution, and a replacement step of replacing the oxidizing atmosphere with the decomposition atmosphere, and repeating a recovery cycle including the four steps. And
【０００６】本発明は上記した構成により、不純物を含
まない高純度の過酸化水素ガスが半導体基板の表面を酸
化し、引き続き酸化膜を分解する高純度のフッ化水素ガ
スを供給し半導体基板の表面の不純物を溶かした分解液
が得られることになる。According to the present invention, the high purity hydrogen peroxide gas containing no impurities oxidizes the surface of the semiconductor substrate, and subsequently the high purity hydrogen fluoride gas which decomposes the oxide film is supplied to supply the high purity hydrogen fluoride gas to the semiconductor substrate. A decomposition liquid in which impurities on the surface are dissolved can be obtained.
【０００７】[0007]
【発明の実施の形態】図１は本発明の一実施例における
半導体基板の表面の不純物回収装置の概略構成図であ
る。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 is a schematic configuration diagram of an impurity recovery device for a surface of a semiconductor substrate according to an embodiment of the present invention.
【０００８】図において、１は密閉容器、２，３は薬品
を貯蔵する貯蔵容器であり、貯蔵容器２，３と密閉容器
１はガス供給管４，５により接続されている。また貯蔵
容器２，３は不活性ガス配管６，７を備えている。半導
体基板８を半導体基板支持部９にのせ半導体基板押さえ
１０で固定する。１１は不活性ガス供給配管で、１２は
排出配管である。１３は純水を半導体基板の表面に定量
的に供給するための定量ポンプで、配管１４から純水を
供給して配管１５により密閉容器１内の半導体基板８上
に滴下する。１６は分解液１６ａを採取する治具であ
る。なお図において、１７，１８は貯蔵容器２，３の加
熱手段、１９，２０はガス供給管４，５のバルブ、２１
は不活性ガス供給配管１１のバルブ、２２は半導体基板
支持部９の回転手段である。In the figure, 1 is a closed container, 2 and 3 are storage containers for storing chemicals, and the storage containers 2 and 3 and the closed container 1 are connected by gas supply pipes 4 and 5. The storage containers 2 and 3 are provided with inert gas pipes 6 and 7. The semiconductor substrate 8 is placed on the semiconductor substrate supporting portion 9 and fixed by the semiconductor substrate retainer 10. Reference numeral 11 is an inert gas supply pipe, and 12 is a discharge pipe. Reference numeral 13 denotes a metering pump for quantitatively supplying pure water to the surface of the semiconductor substrate. Pure water is supplied from a pipe 14 and dropped on the semiconductor substrate 8 in the closed container 1 through the pipe 15. Reference numeral 16 is a jig for collecting the decomposition liquid 16a. In the figure, 17 and 18 are heating means of the storage containers 2 and 3, 19 and 20 are valves of the gas supply pipes 4 and 5, and 21.
Is a valve of the inert gas supply pipe 11, and 22 is a rotating means of the semiconductor substrate supporting portion 9.
【０００９】以上のように構成されたこの実施例の半導
体基板の表面の不純物回収装置において、以下にその動
作を説明する。The operation of the apparatus for recovering impurities on the surface of a semiconductor substrate according to this embodiment constructed as described above will be described below.
【００１０】例えば、薬品を貯蔵する貯蔵容器２にフッ
化水素酸を満たしておき、貯蔵容器３に過酸化水素水を
満たしておく。加熱手段１７，１８によって加熱する。
加熱温度は３０℃程度が好ましい。温度を上げ過ぎると
ガスの発生量は増加するが、ミストも発生しやすくな
り、不純物がそのミストと共に密閉容器１へ導入されて
しまうからである。まずバルブ１９は閉めておき、不活
性ガスＮ2の供給も行なわない。バルブ２０を開き配管
７よりＮ2を流し密閉容器１内に過酸化水素ガスを供給
する。過酸化水素ガスにより半導体基板８は酸化され
る。このとき半導体基板８の酸化速度は約０．５Ａ／時
間である。ある時間過酸化水素ガスを供給した後、バル
ブ２０を閉じる。次にバルブ２１を開けＮ2ガスを密閉
容器１内に供給して密閉容器内の過酸化水素ガスをＮ2
で置換する。過酸化水素ガスとフッ酸ガスが共存される
と半導体基板の表面の過酸化水素ガスの濃度とフッ酸ガ
スの濃度の違いにより半導体基板８の位置によるエッチ
ング速度が異なり深さ方向の不純物測定が困難となる。
過酸化水素ガスを完全に置換した後バルブ２１を閉じ、
バルブ１９を開き分解ガスであるフッ酸ガスを密閉容器
１内へ供給する。フッ酸ガスにより酸化膜分解完了後、
バルブ１９を閉じ、バルブ２１を開き密閉容器１内のフ
ッ酸ガスをＮ2で置換する。次に回転手段２２により半
導体基板支持部９を回転させる。続いて、配管１５より
半導体基板８上に純水を滴下させる。従来フッ酸ガスを
半導体基板８の表面で結露させるために多量のフッ酸ガ
スを供給する必要があったが、純水によってフッ酸ガス
で分解された不純物を溶解させることによりフッ酸ガス
の供給を減少させることができる。滴下させた後回転を
止め遠心力により半導体基板８の外周に集まった分解液
１６ａを治具１６により採取する。その後、例えばフレ
ームレス原子吸光でこの分解液１６ａの不純物を測定す
ることにより半導体基板８の表面の不純物濃度の測定を
行なうことができる。For example, the storage container 2 for storing chemicals is filled with hydrofluoric acid, and the storage container 3 is filled with hydrogen peroxide solution. It is heated by the heating means 17 and 18.
The heating temperature is preferably about 30 ° C. This is because if the temperature is raised too high, the amount of gas generated increases, but mist also tends to be generated, and impurities are introduced into the closed container 1 together with the mist. First, the valve 19 is closed and the inert gas N 2 is not supplied. The valve 20 is opened and N 2 is flown from the pipe 7 to supply hydrogen peroxide gas into the closed container 1. The semiconductor substrate 8 is oxidized by the hydrogen peroxide gas. At this time, the oxidation rate of the semiconductor substrate 8 is about 0.5 A / hour. After supplying hydrogen peroxide gas for a certain period of time, the valve 20 is closed. Next, the valve 21 is opened and N 2 gas is supplied into the closed container 1 to remove the hydrogen peroxide gas in the closed container from N 2.
Replace with. When the hydrogen peroxide gas and the hydrofluoric acid gas coexist, the etching rate varies depending on the position of the semiconductor substrate 8 due to the difference between the concentration of the hydrogen peroxide gas and the concentration of the hydrofluoric acid gas on the surface of the semiconductor substrate. It will be difficult.
After completely replacing the hydrogen peroxide gas, close the valve 21,
The valve 19 is opened, and hydrofluoric acid gas which is a decomposition gas is supplied into the closed container 1. After completion of oxide film decomposition with hydrofluoric acid gas,
The valve 19 is closed and the valve 21 is opened to replace the hydrofluoric acid gas in the closed container 1 with N 2 . Next, the semiconductor substrate supporting portion 9 is rotated by the rotating means 22. Then, pure water is dropped on the semiconductor substrate 8 from the pipe 15. Conventionally, a large amount of hydrofluoric acid gas had to be supplied in order to cause the hydrofluoric acid gas to condense on the surface of the semiconductor substrate 8, but the supply of hydrofluoric acid gas was accomplished by dissolving impurities decomposed by hydrofluoric acid gas with pure water. Can be reduced. After the dropping, the rotation is stopped and the decomposition liquid 16a collected on the outer periphery of the semiconductor substrate 8 is collected by the jig 16 by the centrifugal force. After that, the impurity concentration of the surface of the semiconductor substrate 8 can be measured by measuring the impurities in the decomposition liquid 16a by, for example, flameless atomic absorption.
【００１１】以上のような構成および操作により密閉容
器１内で反応させるため、環境からの不純物による汚染
を低減することができ、微量の不純物量を測定が可能と
なる。また上記の過酸化水素ガスによる酸化工程、フッ
酸ガスによる分解工程、純水による分解液回収工程を繰
り返し行なうことにより、半導体基板８の表面から内部
の深さ方向の不純物濃度を知ることができる。Since the reaction is carried out in the closed container 1 by the configuration and operation as described above, contamination by impurities from the environment can be reduced and a trace amount of impurities can be measured. Further, by repeating the above-mentioned oxidation step with hydrogen peroxide gas, decomposition step with hydrofluoric acid gas, and decomposition solution recovery step with pure water, it is possible to know the impurity concentration in the depth direction from the surface of the semiconductor substrate 8 to the inside. .
【００１２】なお、本発明の不純物回収装置を構成する
材料は、半導体基板８の表面の不純物を測定する場合に
妨害となる不純物を含まないものであればいかなるもの
でもよいが、特に酸性やアルカリ性のガスを用いること
から、フッ素系樹脂やその他高分子樹脂、例えばポリエ
チレンやポリプロピレン、またセラミックスや不動態化
処理を行なったステンレスで構成するのがよい。Any material may be used as the material for the impurity recovery device of the present invention, as long as it does not contain impurities that interfere with the measurement of impurities on the surface of the semiconductor substrate 8, but is particularly acidic or alkaline. Since this gas is used, it is preferable to use a fluororesin or other polymer resin such as polyethylene or polypropylene, ceramics, or passivated stainless steel.
【００１３】また過酸化水素ガスによる酸化工程を省い
て、フッ酸ガスのみを供給することにより、半導体基板
８の表面に付着した不純物のみを回収することができ
る。なお本実施例では酸化性ガスの原料として過酸化水
素を用いているが、酸化速度を変えるためにアンモニア
水、硝酸等を用いてもよいことは言うまでもない。Further, by omitting the step of oxidizing with hydrogen peroxide gas and supplying only hydrofluoric acid gas, only impurities attached to the surface of the semiconductor substrate 8 can be recovered. Although hydrogen peroxide is used as a raw material for the oxidizing gas in this embodiment, it goes without saying that ammonia water, nitric acid, or the like may be used to change the oxidation rate.
【００１４】[0014]
【発明の効果】以上の実施例から明らかなように本発明
によれば、密閉容器外に設置された貯蔵容器から純度の
高い過酸化水素ガスとフッ素酸ガスを密閉容器内に供給
し、過酸化水素ガスによる酸化工程、フッ酸ガスによる
分解工程、分解液回収工程を繰り返し行なうことによ
り、半導体基板の表面から内部の深さ方向の微量な不純
物の分析が可能となる半導体基板の表面不純物回収方法
を提供できる。As is apparent from the above embodiments, according to the present invention, hydrogen peroxide gas and fluoric acid gas of high purity are supplied from the storage container installed outside the closed container into the closed container, and By repeating the oxidation process with hydrogen oxide gas, the decomposition process with hydrofluoric acid gas, and the decomposition liquid recovery process, it is possible to analyze a minute amount of impurities from the surface of the semiconductor substrate to the inside depth direction. A method can be provided.
【図１】本発明の一実施例における半導体基板の表面の
不純物回収装置の概略構成図FIG. 1 is a schematic configuration diagram of an impurity recovery device for a surface of a semiconductor substrate according to an embodiment of the present invention.
【図２】従来の半導体基板の表面の不純物回収装置の概
略構成図FIG. 2 is a schematic configuration diagram of a conventional impurity recovery device for the surface of a semiconductor substrate.
１ 密閉容器 ２，３ 貯蔵容器 ４，５ ガス供給管 ６，７ 不活性ガスを供給する配管 ８ 半導体基板 ９ 半導体基板支持部 １０ 半導体基板押さえ １１ 密閉容器内に不活性ガスを供給する配管 １２ 排出配管 １３ 定量ポンプ １７，１８ 加熱手段 ２２ 回転手段 1 Airtight container 2,3 Storage container 4,5 Gas supply pipe 6,7 Pipe for supplying inert gas 8 Semiconductor substrate 9 Semiconductor substrate support 10 Semiconductor substrate retainer 11 Pipe for supplying inert gas in airtight container 12 Emission Piping 13 Metering pump 17,18 Heating means 22 Rotating means
Claims (1)
酸化工程と、上記半導体基板表面に形成された酸化膜を
酸化膜分解雰囲気に曝して分解する分解工程と、分解液
を回収する回収工程と、上記酸化雰囲気を上記分解雰囲
気に置換する置換工程とを有し、上記４工程を含む回収
サイクルを繰り返すことを特徴とする半導体基板表面の
不純物回収方法。1. An oxidation step of exposing a semiconductor substrate to an oxidizing atmosphere to oxidize it, a decomposition step of exposing an oxide film formed on the surface of the semiconductor substrate to an atmosphere for decomposition of an oxide film to decompose it, and a recovery step of recovering a decomposition solution. And a replacement step of replacing the oxidizing atmosphere with the decomposition atmosphere, and a collection cycle including the above-mentioned four steps is repeated to collect impurities on the surface of the semiconductor substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17468796A JPH08321535A (en) | 1996-07-04 | 1996-07-04 | Recovery method of impurities |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17468796A JPH08321535A (en) | 1996-07-04 | 1996-07-04 | Recovery method of impurities |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2408117A Division JP2568756B2 (en) | 1990-12-27 | 1990-12-27 | Semiconductor substrate surface impurity recovery system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08321535A true JPH08321535A (en) | 1996-12-03 |
Family
ID=15982935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17468796A Pending JPH08321535A (en) | 1996-07-04 | 1996-07-04 | Recovery method of impurities |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08321535A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2933811A1 (en) * | 2008-07-09 | 2010-01-15 | Soitec Silicon On Insulator | Silicon material etching method for use during fabrication of e.g. opto-electronic component, involves utilizing solutions of each of mixture constituents, mixing solutions in vapor phase, and etching material using acid base mixture |
| KR101523943B1 (en) * | 2013-12-24 | 2015-06-01 | 주식회사 엘지실트론 | Method for analyzing pollution induced by manufacture of wafer |
| JP2021063588A (en) * | 2019-10-16 | 2021-04-22 | ダリオン インコーポレイテッド | Balanced exhaust valve for corrosive gas and acidic and alkaline gas |
-
1996
- 1996-07-04 JP JP17468796A patent/JPH08321535A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2933811A1 (en) * | 2008-07-09 | 2010-01-15 | Soitec Silicon On Insulator | Silicon material etching method for use during fabrication of e.g. opto-electronic component, involves utilizing solutions of each of mixture constituents, mixing solutions in vapor phase, and etching material using acid base mixture |
| KR101523943B1 (en) * | 2013-12-24 | 2015-06-01 | 주식회사 엘지실트론 | Method for analyzing pollution induced by manufacture of wafer |
| JP2021063588A (en) * | 2019-10-16 | 2021-04-22 | ダリオン インコーポレイテッド | Balanced exhaust valve for corrosive gas and acidic and alkaline gas |
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