JP2005260119A - Method for eliminating residue in mocvd - Google Patents
Method for eliminating residue in mocvd Download PDFInfo
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- JP2005260119A JP2005260119A JP2004072248A JP2004072248A JP2005260119A JP 2005260119 A JP2005260119 A JP 2005260119A JP 2004072248 A JP2004072248 A JP 2004072248A JP 2004072248 A JP2004072248 A JP 2004072248A JP 2005260119 A JP2005260119 A JP 2005260119A
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Abstract
Description
本発明はＭＯＣＶＤ残渣の除去方法に関し、詳しくはＭＯＣＶＤ装置の内部に堆積したＭＯＣＶＤ残渣を除去する方法に関する。 The present invention relates to a method for removing MOCVD residues, and more particularly to a method for removing MOCVD residues deposited inside an MOCVD apparatus.
揮発性の有機金属化合物（Ｍｅｔａｌｏｒｇａｎｉｃ、ＭＯ）を気相中で化学反応させ、生成物を基体上に堆積させる化学気相堆積法（Ｍｅｔａｌｏｒｇａｎｉｃ ＣｈｅｍｉｃａｌＶａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ法、ＭＯＣＶＤ法）は、例えば化合物半導体の薄膜を基体上に形成するための方法として用いられている〔特許文献１（特開２００３−１７９０８１号公報）など〕。ＭＯＣＶＤ法による薄膜の形成には、図２に示すようなＭＯＣＶＤ装置(1)が広く用いられている。 A chemical vapor deposition method (Metalorganic Chemical Vapor Deposition method, MOCVD method) in which a volatile organometallic compound (Metalorganic, MO) is chemically reacted in a gas phase and a product is deposited on a substrate is, for example, a thin film of a compound semiconductor. It is used as a method for forming on a substrate [Patent Document 1 (Japanese Patent Laid-Open No. 2003-179081), etc.]. For forming a thin film by the MOCVD method, an MOCVD apparatus (1) as shown in FIG. 2 is widely used.
ＭＯＣＶＤ装置(1)とは、チャンバー(2)内で減圧下に有機金属化合物(A)を揮発させ、反応させて基体(B)上に薄膜を形成するための装置である。チャンバー(2)内は真空ポンプ(3)によって減圧される。ＭＯＣＶＤ装置(1)には、チャンバー(2)と真空ポンプ(3)とを接続するための真空配管(4)が設けられている。また、チャンバー(2)には、反応中間体、生成物などの固形物などが真空配管(4)を通じて真空ポンプ(3)へ飛散することを防止するために、真空配管(4)との接続部分にフィルター材(5)が設けられていて、このフィルター材によって固形物を捕集している。 The MOCVD apparatus (1) is an apparatus for forming a thin film on the substrate (B) by volatilizing and reacting the organometallic compound (A) in the chamber (2) under reduced pressure. The inside of the chamber (2) is depressurized by a vacuum pump (3). The MOCVD apparatus (1) is provided with a vacuum pipe (4) for connecting the chamber (2) and the vacuum pump (3). The chamber (2) is connected to the vacuum pipe (4) to prevent solids such as reaction intermediates and products from scattering to the vacuum pump (3) through the vacuum pipe (4). A filter material (5) is provided in the part, and solids are collected by this filter material.
ＭＯＣＶＤ装置による薄膜の形成には、反応中間体や生成物などの一部がＭＯＣＶＤ残渣となってフィルター材(5)、チャンバー(2)の内壁などに付着する。これら装置内部に付着した残渣は、薄膜の形成後、装置内に空気を導入し、装置を大気に開放してから除去される。 When a thin film is formed by the MOCVD apparatus, a part of the reaction intermediate or product becomes a MOCVD residue and adheres to the filter material (5), the inner wall of the chamber (2), and the like. Residues adhering to the inside of the apparatus are removed after air is introduced into the apparatus after the thin film is formed and the apparatus is opened to the atmosphere.
しかし、ＭＯＣＶＤ残渣の多くは粉末状で付着するので、飛散し易く、これを除去することは困難であった。特にフィルター材(5)には、多くの残渣が付着し易く、このフィルター材(5)に捕集された残渣の容易に除去できる方法が求められていた。 However, since most of the MOCVD residue adheres in powder form, it easily scatters and it is difficult to remove it. In particular, the filter material (5) is liable to have many residues adhering thereto, and there has been a demand for a method that can easily remove the residue collected on the filter material (5).
そこで本発明者は、ＭＯＣＶＤ装置内の残渣を飛散させることなく、簡便に除去できる方法を開発するべく鋭意検討した結果、ＭＯＣＶＤ残渣に水を加えると、残渣の飛散を防止でき、しかも除去も容易となることを見出し、本発明に至った。 Therefore, the present inventor has intensively studied to develop a method that can be easily removed without scattering the residue in the MOCVD apparatus. As a result, when water is added to the MOCVD residue, the residue can be prevented from being scattered and easily removed. As a result, the present invention has been achieved.
すなわち本発明は、ＭＯＣＶＤ装置の内部に堆積したＭＯＣＶＤ残渣を除去する方法であり、ＭＯＣＶＤ残渣に水を加えて含水率１５質量％以上としてから除去することを特徴とするＭＯＣＶＤ残渣の除去方法を提供するものである。 That is, the present invention provides a method for removing MOCVD residue deposited inside an MOCVD apparatus, and removing the MOCVD residue after adding water to the MOCVD residue so that the water content is 15% by mass or more. To do.
本発明の方法によれば、ＭＯＣＶＤ残渣に水を加えるので、残渣の飛散を防止しながら、簡便に除去できる。 According to the method of the present invention, since water is added to the MOCVD residue, it can be easily removed while preventing the residue from scattering.
本発明の除去方法で除去されるＭＯＣＶＤ残渣は、有機金属化合物を用いてＭＯＣＶＤ装置内で、ＭＯＣＶＤ法により、薄膜を形成する際に装置内に堆積するものであって、例えば有機金属化合物から化学反応により化合物半導体を形成する際に発生する反応中間体や、基体に堆積することなく装置の内壁などに堆積した反応生成物などが挙げられる。 The MOCVD residue removed by the removing method of the present invention is deposited in the MOCVD apparatus using the organometallic compound and is formed in the apparatus when the thin film is formed by the MOCVD method. Examples include reaction intermediates that are generated when a compound semiconductor is formed by reaction, and reaction products that are deposited on the inner wall of the apparatus without being deposited on the substrate.
本発明の除去方法は、有機金属化合物として、例えばトリメチルアルミニウム、トリエチルアルミニウムなどの有機アルミニウム化合物、
トリメチルガリウム、トリエチルガリウムなどの有機ガリウム化合物、
トリメチルインジウムなどの有機インジウム化合物、
トリメチルアルシン、ｔ−ブチルアルシンなどの有機ヒ素化合物、
トリメチルホスフィン、ｔ−ブチルホスフィンなどの有機リン化合物などを用いたときに堆積した残渣に適用することができ。これらの有機金属化合物はそれぞれ１種、または２種以上を組み合わせて用いられる。また、これらの有機金属化合物と共に、ホスフィン、アルシンなどの水素化物を用いたときに堆積した残渣に適用することもできる。
The removal method of the present invention includes, as an organometallic compound, for example, an organoaluminum compound such as trimethylaluminum and triethylaluminum,
Organic gallium compounds such as trimethylgallium and triethylgallium,
Organic indium compounds such as trimethylindium,
Organic arsenic compounds such as trimethylarsine and t-butylarsine,
It can be applied to residues deposited when using organophosphorus compounds such as trimethylphosphine and t-butylphosphine . These organometallic compounds are each used alone or in combination of two or more. In addition, these organic metal compounds can be applied to residues deposited when hydrides such as phosphine and arsine are used.
本発明の方法では、装置を大気に開放する前に、このＭＯＣＶＤ残渣に水を加えて含水率を１５質量％以上、好ましくは２０質量％以上、通常は３０質量％以下、好ましくは２５質量％としてから除去する。１５質量％未満では、十分な効果を発揮できないことがあり、また３０質量％を超えるほど大量の水を用いたのでは、大量の水を含んだ残渣が流動して装置内に拡がってしまう虞れがあり、好ましくない。水の使用量は、例えば同様の操作で薄膜を形成した過去の実績から予測されるＭＯＣＶＤ残渣の量から、上記含水率になる量として求めることができる。水は、通常の水道水、工業用水などを用いてもよいが、ＭＯＣＶＤ装置の内部の無用な汚染を防止しうる点で、蒸留水、イオン交換水などのような精製水を用いることが好ましい。 In the method of the present invention, before the apparatus is opened to the atmosphere, water is added to the MOCVD residue so that the water content is 15% by mass or more, preferably 20% by mass or more, usually 30% by mass or less, preferably 25% by mass. Remove as from. If it is less than 15% by mass, a sufficient effect may not be exhibited. If a large amount of water is used exceeding 30% by mass, a residue containing a large amount of water may flow and spread in the apparatus. This is undesirable. The amount of water used can be determined, for example, from the amount of MOCVD residue predicted from the past performance of forming a thin film by the same operation as the amount of water content. As the water, normal tap water, industrial water, or the like may be used, but it is preferable to use purified water such as distilled water or ion-exchanged water from the viewpoint that unnecessary contamination inside the MOCVD apparatus can be prevented. .
ＭＯＣＶＤ装置を大気に開放する前に残渣に水を加えるには、例えば図１に示すように装置(1)内にスプレーなどの噴霧器(6)を設けておき、この噴霧器(6)から水(C)を噴霧すればよい。噴霧器は、装置内部の全てに水を噴霧できるように設けてもよいが、残渣が付着し易い部分、例えば真空ポンプへの真空配管(4)との接続部とその周辺や、この接続部に設けられたフィルター材(5)、チャンバー(2)内壁、特に有機金属化合物の導入部付近などが挙げられる。図１に示す装置(1)では、接続部とその周辺やフィルター材に水(C)を噴霧するためのスプレー(6)を設けている。 In order to add water to the residue before opening the MOCVD apparatus to the atmosphere, for example, as shown in FIG. 1, a sprayer (6) such as a spray is provided in the apparatus (1), and water ( C) may be sprayed. The sprayer may be provided so that water can be sprayed to the entire interior of the device, but the part where residues are likely to adhere, for example, the connection with the vacuum pipe (4) to the vacuum pump (4) and its surroundings, and the connection Examples thereof include the provided filter material (5), the inner wall of the chamber (2), particularly the vicinity of the introduction portion of the organometallic compound. In the apparatus (1) shown in FIG. 1, a spray (6) for spraying water (C) onto the connecting portion, its periphery, and the filter material is provided.
また、加熱された飽和水蒸気を装置内に導入して、ＭＯＣＶＤ装置の内部で凝縮させてもよい。加熱飽和水蒸気は、例えばＭＯＣＶＤ装置の温度よりも高い温度、通常は５℃〜２０℃程度高い温度で、減圧下に水を揮発させて飽和させて得ることができ、得られた飽和水蒸気をＭＯＣＶＤ装置に導入すればよい。 Alternatively, heated saturated water vapor may be introduced into the apparatus and condensed inside the MOCVD apparatus. The heated saturated water vapor can be obtained by evaporating water under reduced pressure and saturating it at a temperature higher than the temperature of the MOCVD apparatus, usually about 5 ° C. to 20 ° C., and the obtained saturated water vapor can be obtained by MOCVD. What is necessary is just to introduce into an apparatus.
水は、装置の内部が薄膜を形成している間と同様の減圧状態のままで供給してもよいが、特に水を噴霧して加える場合に、減圧状態で水を加えると、この水が急激に揮発して、風圧により残渣が飛散する畏れがあるため、例えばＭＯＣＶＤ装置の内部にガスを充填し、大気圧と等しいか、これを超える圧力としてから水を加えることが好ましい。内部に充填されるガスとしては、窒素ガス、アルゴンガスなどの不活性ガスを用いてもよいが、装置内部に僅かに残留することがある未反応の有機金属化合物を酸化して不活性化できる点で、空気などの酸素含有ガスを充填することが、好ましい。 Water may be supplied in the same reduced pressure state as the inside of the apparatus is forming a thin film, but when water is added by spraying water, this water is Since there is a possibility that the residue volatilizes rapidly and the residue is scattered by wind pressure, for example, it is preferable to add water after filling the inside of the MOCVD apparatus with a pressure equal to or exceeding the atmospheric pressure. As the gas filled inside, an inert gas such as nitrogen gas or argon gas may be used, but it is possible to inactivate an unreacted organometallic compound that may remain slightly in the apparatus. In this respect, it is preferable to fill an oxygen-containing gas such as air.
本発明の除去方法では、このようにして残渣に水を加えるので、この後に装置内部を大気に開放したとしても、この残渣が飛散したりすることがなく、容易に残渣を除去することができる。 In the removal method of the present invention, since water is added to the residue in this way, even if the inside of the apparatus is subsequently opened to the atmosphere, the residue does not scatter and can be easily removed. .
本発明の除去方法によれば、Ａｌ、Ｇａ、Ｉｎ、Ｐ、Ａｓなどを含む有機金属化合物を原料として、ＭＯＣＶＤ法により、薄膜を形成するためのＭＯＣＶＤ装置の内部に付着したＭＯＣＶＤ残渣を簡便に除去することができる。 According to the removal method of the present invention, an MOCVD residue adhered to the inside of an MOCVD apparatus for forming a thin film can be easily formed by MOCVD using an organometallic compound containing Al, Ga, In, P, As, etc. as a raw material. Can be removed.
以下、実施例によって本発明をより詳細に説明するが、本発明は、かかる実施例により限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by this Example.
実施例１
有機金属化合物(A)として、トリメチルアルミニウム、トリメチルガリウムおよびトリメチルインジウムを用い、これらと共にホスフィンおよびアルシンを用いてＭＯＣＶＤ法により減圧下に基板(B)上に薄膜を形成した後のＭＯＣＶＤ装置(1)に、空気を導入し、装置(1)内の圧力を大気圧と等しくする。次いで、このＭＯＣＶＤ装置(1)内に水(C)を導入して、ＭＯＣＶＤ残渣に水を加える。水(C)は、ＭＯＣＶＤ装置(1)内に設けられたスプレー(6)により、フィルター材(5)の近傍に噴霧して加える。ＭＯＣＶＤ装置(1)を開放し、フィルター材(5)を取り出す。このときにフィルター材(5)に補修されたＭＯＣＶＤ残渣が飛散することはない。このフィルター材(5)に捕集される残渣の主な金属成分は、Ａｌ、Ｇａ、Ｉｎ、Ｐ、Ａｓである。
Example 1
MOCVD apparatus (1) after forming a thin film on substrate (B) under reduced pressure by MOCVD using trimethylaluminum, trimethylgallium and trimethylindium as organometallic compound (A) and phosphine and arsine together with them Then, air is introduced to make the pressure in the device (1) equal to the atmospheric pressure. Next, water (C) is introduced into the MOCVD apparatus (1), and water is added to the MOCVD residue. Water (C) is sprayed and added to the vicinity of the filter material (5) by the spray (6) provided in the MOCVD apparatus (1). Open the MOCVD apparatus (1) and take out the filter material (5). At this time, the MOCVD residue repaired on the filter material (5) is not scattered. The main metal components of the residue collected in the filter material (5) are Al, Ga, In, P, and As.
１：ＭＯＣＶＤ装置
２：チャンバー ３：真空ポンプ ４：真空配管
５：フィルター材 ６：噴霧器（スプレー）
Ａ：有機金属化合物 Ｂ：基体 Ｃ：水
1: MOCVD apparatus 2: Chamber 3: Vacuum pump 4: Vacuum piping 5: Filter material 6: Nebulizer (spray)
A: Organometallic compound B: Substrate C: Water
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| JP2007088295A (en) * | 2005-09-22 | 2007-04-05 | Toshiba Corp | Method and device for manufacturing semiconductor |
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