JP4680246B2 - Abnormal product removal method for vapor phase growth apparatus - Google Patents

Abnormal product removal method for vapor phase growth apparatus Download PDF

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JP4680246B2
JP4680246B2 JP2007259420A JP2007259420A JP4680246B2 JP 4680246 B2 JP4680246 B2 JP 4680246B2 JP 2007259420 A JP2007259420 A JP 2007259420A JP 2007259420 A JP2007259420 A JP 2007259420A JP 4680246 B2 JP4680246 B2 JP 4680246B2
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憲二 沼尻
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Canon Anelva Corp
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Description

この発明は、常温常圧で液体または固体である原料を用いて基板に対し膜形成を行う気相成長装置の異常生成物除去方法に関する。   The present invention relates to a method for removing abnormal products of a vapor phase growth apparatus that forms a film on a substrate using a raw material that is liquid or solid at normal temperature and pressure.

半導体デバイスや各種電子部品等を製作する際に行われる、配線膜や絶縁膜等の薄膜の形成に様々な方法が採用されているなか、今後のデバイスの微細化に対応可能な方法として、ＣＶＤ法（Chemical Vapor Deposition ：化学気相成長法）の研究が進んでいる。   As a method that can cope with future miniaturization of devices, various methods are used to form thin films such as wiring films and insulating films, which are performed when manufacturing semiconductor devices and various electronic components. Research on chemical vapor deposition (chemical vapor deposition) is in progress.

このうち、窒化チタン（ＴｉＮ）膜や銅（Ｃｕ）膜のような薄膜を比較的良好な被覆性で作製する方法として、有機金属化合物や有機金属錯体を原料として用いたＣＶＤ技術が注目されている。この方法では、例えばテトラキスジメチルアミノチタン（以下、ＴＤＭＡＴ）のような有機金属化合物や、ヘキサフルオロアセチルアセトナート・トリメチルビニルシラン・銅（以下、Ｃｕ（ｈｆａｃ）（ｔｍｖｓ）とも記載する。）のような有機金属錯体を原料とし、この原料を反応室内に送り込んで所定の温度に加熱し、所定の熱化学反応を生じさせることにより、基板（成膜対象物）に所定の薄膜を形成する。   Among these, as a method for producing a thin film such as a titanium nitride (TiN) film or a copper (Cu) film with relatively good coverage, a CVD technique using an organometallic compound or an organometallic complex as a raw material has attracted attention. Yes. In this method, for example, an organometallic compound such as tetrakisdimethylaminotitanium (hereinafter referred to as TDMAT), hexafluoroacetylacetonate, trimethylvinylsilane, and copper (hereinafter also referred to as Cu (hfac) (tmvs)) are used. An organometallic complex is used as a raw material, and the raw material is sent into a reaction chamber and heated to a predetermined temperature to cause a predetermined thermochemical reaction, thereby forming a predetermined thin film on a substrate (film formation target).

従来の成膜装置としては、例えば以下の特許文献１〜１０に開示されたものが知られている。
特開平３−２５９２３号公報 特開平６−２９２２６号公報 特開平７−２０６５８６号公報 特開平８−２６４５１７号公報 特開平７−３２１０３９号公報 特開平３−１３４１７６号公報 特開平２−２７０９６４号公報 特開平７−２６８６３４号公報 特開平８−１７７４９号公報 特開平８−１８６１０３号公報 As conventional film forming apparatuses, for example, those disclosed in the following Patent Documents 1 to 10 are known.
Japanese Patent Laid-Open No. 3-25923 JP-A-6-29226 JP-A-7-206586 JP-A-8-264517 JP 7-321039 A JP-A-3-134176 JP-A-2-270964 JP-A-7-268634 JP-A-8-17749 JP-A-8-186103

上述したような有機金属化合物または有機金属錯体は、常温常圧で液体または固体である場合が多い。このため、原料を溜めたボンベ内で原料を加熱したり、バブリング法を用いたりすることにより気化させて反応室に供給する（導入する）のが普通であった。しかし、これらの方法では、ボンベ内に残留する原料の量によって熱容量が異なるために、反応室に所定の気化原料を安定して供給することが難しかった。   The organometallic compound or organometallic complex as described above is often liquid or solid at normal temperature and pressure. For this reason, it is common to heat the raw material in a cylinder in which the raw material is stored or to supply (introduce) it to the reaction chamber by vaporizing it by using a bubbling method. However, in these methods, since the heat capacity varies depending on the amount of raw material remaining in the cylinder, it has been difficult to stably supply a predetermined vaporized raw material to the reaction chamber.

このため、上述したようなボンベを用いる方法ではなく、近年では、液相（液体状態）の原料を溜めておく原料液収納部と、原料液収納部から供給された液相の原料を気化する原料ガス供給装置とで少なくとも構成される気相成長装置が開発されてきている（特願平７−９６１６８参照）。原料ガス供給装置は、原料液収納部から供給されたある程度の量の原料液を一旦溜めておく原料容器と、原料容器から配管を介して少しずつ供給される原料液を気化する気化器とを具えている。このような構成の気相成長装置（以下、単に装置ともいう。）とすれば、原料液を少しずつ気化させることができ、前述の熱容量に伴う問題が解消して、所定量の気化原料を安定して供給することが可能である。   For this reason, instead of using the cylinder as described above, in recent years, the raw material liquid storage part for storing the raw material in the liquid phase (liquid state) and the liquid phase raw material supplied from the raw material liquid storage part are vaporized. A vapor phase growth apparatus composed of at least a source gas supply apparatus has been developed (see Japanese Patent Application No. 7-96168). The raw material gas supply device includes a raw material container for temporarily storing a certain amount of raw material liquid supplied from the raw material liquid storage section, and a vaporizer for vaporizing the raw material liquid supplied little by little through the pipe from the raw material container. It has. With a vapor phase growth apparatus having such a configuration (hereinafter also simply referred to as an apparatus), the raw material liquid can be vaporized little by little, and the problems associated with the above-described heat capacity are solved, and a predetermined amount of vaporized raw material is removed. It is possible to supply stably.

このような装置を立ち上げるときには、原料ガス供給装置（以下、単に供給装置ともいう。）内の大気を取り除くために、供給装置に対して不活性ガスによるパージと排気とを繰り返した後に、原料を供給装置の原料容器内に導入し、成膜を開始していた。   When starting up such an apparatus, in order to remove the atmosphere in the raw material gas supply device (hereinafter also simply referred to as a supply device), the supply device is repeatedly purged and exhausted with an inert gas, and then the raw material is supplied. Was introduced into the raw material container of the supply device, and film formation was started.

しかし、このような前処理を施しても供給装置内部の大気を充分に取り除くことは難しく、用いる原料によっては大気中の水分と反応して生成物を形成する場合がある。このため、装置を使用していくうちに、この生成物に起因して成膜速度や成膜特性の低下等の経時変化が見られたり、供給装置内部で詰まり等のトラブルが発生したりするおそれがある。詰まりが発生すると原料の反応室への供給が停止するため、成膜も中断されてしまう。この場合、気相成長装置から供給装置を取り外してメンテナンスを行うことになるが、生成物の完全な除去は難しく、生成物が供給装置に残存してしまうと再利用できる可能性が少ない。   However, even if such pretreatment is performed, it is difficult to sufficiently remove the air inside the supply apparatus, and depending on the raw material used, there is a case where a product is formed by reacting with moisture in the air. For this reason, while using the apparatus, due to this product, changes over time such as a decrease in film formation speed and film formation characteristics are observed, and troubles such as clogging occur inside the supply apparatus. There is a fear. When clogging occurs, the supply of the raw material to the reaction chamber is stopped, so that the film formation is also interrupted. In this case, the supply apparatus is removed from the vapor phase growth apparatus and maintenance is performed. However, it is difficult to completely remove the product, and if the product remains in the supply apparatus, the possibility of being reused is low.

したがって、原料を大気に触れさせることなく安定に反応室に供給することができ、成膜速度や成膜特性の低下等の経時変化のおそれが少なく、長期間安定にガス原料供給装置を使用できる気相成長装置の異常生成物除去方法が望まれていた。   Therefore, the raw material can be stably supplied to the reaction chamber without being exposed to the atmosphere, and there is little risk of change over time such as a decrease in film formation speed and film formation characteristics, and the gas raw material supply apparatus can be used stably for a long period of time. There has been a demand for a method for removing abnormal products from a vapor phase growth apparatus.

この発明は、基板上に膜を形成する反応室と、該反応室に原料ガスと洗浄液と不活性ガスとを供給する原料ガス供給装置と、該原料ガス供給装置に原料ガスを供給する原料ガス供給系と、原料ガス供給装置に洗浄液を供給する洗浄系と、反応室を排気する排気系とを有する気相成長装置の異常生成物除去方法に関する。   The present invention includes a reaction chamber that forms a film on a substrate, a source gas supply device that supplies a source gas, a cleaning liquid, and an inert gas to the reaction chamber, and a source gas that supplies the source gas to the source gas supply device The present invention relates to a method for removing abnormal products of a vapor phase growth apparatus having a supply system, a cleaning system for supplying a cleaning liquid to a source gas supply apparatus, and an exhaust system for exhausting a reaction chamber.

そして、原料ガス供給装置から反応室内に原料ガスを供給することにより基板上に膜を形成する成膜工程と、該成膜工程中に原料ガス供給装置内で異常生成物が発生した時に、該原料ガス供給装置への原料ガスの供給を停止し、該原料ガス供給装置への不活性ガスの供給を開始し、さらに、該不活性ガスの供給圧力を上昇させたときの反応室内の気圧をモニターする不活性ガス送出工程と、該不活性ガス送出工程で不活性ガスの供給圧力を上昇させても反応室内の気圧が上昇しなかった場合に、洗浄液を用いて原料ガス供給装置内および反応室内を洗浄する洗浄工程とを含む。   Then, a film forming step for forming a film on the substrate by supplying a source gas into the reaction chamber from the source gas supply device, and when an abnormal product is generated in the source gas supply device during the film formation step, The supply of the source gas to the source gas supply device is stopped, the supply of the inert gas to the source gas supply device is started, and the pressure in the reaction chamber when the supply pressure of the inert gas is increased is Inert gas delivery process to be monitored, and when the inert gas delivery pressure in the inert gas delivery process does not increase the pressure in the reaction chamber, the cleaning gas is used in the source gas supply apparatus and in the reaction. And a cleaning process for cleaning the room.

この発明では、成膜工程中の異常が発生した場合に、原料ガス供給装置から反応室への原料ガスの供給を停止するとともに、反応室への不活性ガスの供給を開始し、さらに、不活性ガスの供給圧力を上昇させる。これにより、異常の原因となった生成物を除去できる場合がある。生成物が除去された場合、不活性ガスが反応室に供給されるために、反応室内の気圧が上昇する。したがって、生成物が除去されたか否かを、反応室内の気圧が上昇したか否かによって検出することができる。気圧が上昇しなかった場合は、洗浄液を用いて、反応室内を洗浄する。   According to the present invention, when an abnormality occurs during the film forming process, the supply of the source gas from the source gas supply device to the reaction chamber is stopped, the supply of the inert gas to the reaction chamber is started, and Increase the supply pressure of the active gas. Thereby, the product causing the abnormality may be removed. When the product is removed, the inert gas is supplied to the reaction chamber, so that the atmospheric pressure in the reaction chamber increases. Therefore, whether or not the product has been removed can be detected based on whether or not the atmospheric pressure in the reaction chamber has increased. If the atmospheric pressure has not increased, the reaction chamber is cleaned with a cleaning solution.

このように、この発明では、洗浄処理の前に、不活性ガスの供給という簡単な除去処理を試みるので、異常生成物発生による成膜処理中断の時間を全体として低減することができる。   As described above, in the present invention, since a simple removal process of supplying an inert gas is attempted before the cleaning process, it is possible to reduce the entire film formation process interruption time due to the generation of an abnormal product.

以下、図を参照してこの出願の発明の実施の形態について説明する。以下の説明中で挙げる使用材料や数値的な使用条件は、これら発明の範囲内の好適例にすぎない。従って、これらの発明は、これら条件にのみ限定されるものではない。   Hereinafter, embodiments of the invention of this application will be described with reference to the drawings. The materials used and the numerical conditions for use listed in the following description are merely preferred examples within the scope of these inventions. Therefore, these inventions are not limited only to these conditions.

図１は、この発明の実施の形態の気相成長装置１０の説明に供する概略的な装置構成図である。   FIG. 1 is a schematic configuration diagram for explaining a vapor phase growth apparatus 10 according to an embodiment of the present invention.

この発明の気相成長装置によれば、内部を真空に保持した状態で基板に対して膜の形成を行う反応室と、反応室に、膜の原料であるガスを供給する原料ガス供給系と、原料ガス供給系を構成する原料ガス供給装置を洗浄するための洗浄系とを具えている。また、原料ガス供給系は、液相の原料を溜めておく原料液収納部と、この原料液収納部から供給された液相の原料を気化する原料ガス供給装置とを具えている。   According to the vapor phase growth apparatus of the present invention, a reaction chamber that forms a film on a substrate while keeping the inside in a vacuum, and a source gas supply system that supplies a gas that is a raw material of the film to the reaction chamber, And a cleaning system for cleaning the source gas supply device constituting the source gas supply system. The raw material gas supply system includes a raw material liquid storage section that stores liquid phase raw materials, and a raw material gas supply device that vaporizes the liquid phase raw material supplied from the raw material liquid storage section.

ここでは、気相成長装置１０は、上述の反応室１１、図中、破線で囲んで示した原料ガス供給系１３、図中、一点破線で囲んで示した洗浄系１５から主として構成される。   Here, the vapor phase growth apparatus 10 is mainly composed of the reaction chamber 11 described above, a source gas supply system 13 surrounded by a broken line in the drawing, and a cleaning system 15 surrounded by a one-dot broken line in the drawing.

反応室１１は第１排気系１１ａを具えており、内部を真空に保持できるようになっている。第１排気系１１ａは、例えば油回転ポンプやターボ分子ポンプ等を組み合わせた構成となっており、内部を１０-4Ｐａ（パスカル）程度まで排気することが可能である。また、反応室１１は、図示しないヒータや温度制御機構等で構成される温度調節機構を有しており、所定の温度に加熱保持することが可能である。この反応室１１内には、膜形成対象である基板を固定する基板ホルダ（図示せず）が具えられている。 The reaction chamber 11 includes a first exhaust system 11a so that the inside can be maintained in a vacuum. The first exhaust system 11a has a configuration in which, for example, an oil rotary pump, a turbo molecular pump, or the like is combined, and the inside can be exhausted to about 10 −4 Pa (Pascal). Moreover, the reaction chamber 11 has a temperature adjusting mechanism including a heater, a temperature control mechanism, and the like (not shown), and can be heated and held at a predetermined temperature. In the reaction chamber 11, a substrate holder (not shown) for fixing a substrate on which a film is to be formed is provided.

また、原料ガス供給系１３は、次のような構成となっている。反応室１１に、第１配管１７ａを介して原料ガス供給装置（供給装置）１３ａが接続されていて、この第１配管１７ａの中途に第１バルブ１９ａが配設されている。原料ガス供給装置１３ａは、図示しないが、後述する原料液収納部１３ｂから、後述する配管を介して供給された液相の原料をいったん溜めておく原料容器と、この原料容器から配管を介して少しずつ供給された原料液を気化する気化器とで構成されている。気化器としては、市販の液体流量制御器等を用いることができる。   The source gas supply system 13 has the following configuration. A raw material gas supply device (supply device) 13a is connected to the reaction chamber 11 via a first pipe 17a, and a first valve 19a is disposed in the middle of the first pipe 17a. Although not shown, the raw material gas supply device 13a has a raw material container for temporarily storing a liquid phase raw material supplied from a raw material liquid storage unit 13b described later via a pipe described later, and a pipe from the raw material container via the pipe. It consists of a vaporizer that vaporizes the raw material liquid supplied little by little. A commercially available liquid flow rate controller or the like can be used as the vaporizer.

また、供給装置１３ａには、第３配管１７ｃを介して不活性ガス導入部２９が接続してあり、そして、この第３配管１７ｃには、供給装置１３ａに近い方から順に、第３バルブ１９ｃ、第４バルブ１９ｄ、第５バルブ１９ｅが配設されている。   In addition, an inert gas introduction part 29 is connected to the supply device 13a via a third pipe 17c, and the third valve 19c is connected to the third pipe 17c in order from the side closer to the supply device 13a. A fourth valve 19d and a fifth valve 19e are provided.

また、第５バルブ１９ｅを挟む両側の第３配管１７ｃの部分に、第７バルブ１９ｇが配設された第５配管１７ｅと、第８バルブ１９ｈが配設された第６配管１７ｆとが接続してある。この第５配管１７ｅおよび第６配管１７ｆは、液相の原料を収納してある原料液収納部１３ｂ内に向かって伸びている配管である。ここでは、用いる原料をヘキサフルオロアセチルアセトナート・トリメチルビニルシラン・銅（Ｃｕ（ｈｆａｃ）（ｔｍｖｓ））とする。第５配管１７ｅは、原料液吸い上げ用の配管であるため、原料液押し出し用の第６配管１７ｆに比べて長く、第５配管１７ｅの先端は原料液収納部１３ｂの原料液中に浸されているが、第６配管１７ｆの先端は原料液中に浸されていない。また、第３配管１７ｃの、供給装置１３ａに接続してある側とは反対側の先端に、不活性ガス導入部２９が配設してある。この不活性ガス導入部２９より第６配管１７ｆに不活性ガスが導入されると、第５配管１７ｅが原料液を吸い上げる仕組みとなっている。   Further, the fifth pipe 17e provided with the seventh valve 19g and the sixth pipe 17f provided with the eighth valve 19h are connected to the portions of the third pipe 17c on both sides of the fifth valve 19e. It is. The fifth pipe 17e and the sixth pipe 17f are pipes extending toward the inside of the raw material liquid storage portion 13b in which the liquid phase raw material is stored. Here, the raw material used is hexafluoroacetylacetonate / trimethylvinylsilane / copper (Cu (hfac) (tmvs)). Since the fifth pipe 17e is a pipe for sucking up the raw material liquid, it is longer than the sixth pipe 17f for extruding the raw material liquid, and the tip of the fifth pipe 17e is immersed in the raw material liquid in the raw material liquid storage part 13b. However, the tip of the sixth pipe 17f is not immersed in the raw material liquid. In addition, an inert gas introduction portion 29 is disposed at the tip of the third pipe 17c on the side opposite to the side connected to the supply device 13a. When the inert gas is introduced from the inert gas introduction portion 29 into the sixth pipe 17f, the fifth pipe 17e sucks up the raw material liquid.

以上の、第１、第３、第５および第６配管１７ａ、１７ｃ、１７ｅおよび１７ｆと、第１、第３、第４、第５、第７および第８バルブ１９ａ、１９ｃ、１９ｄ、１９ｅ、１９ｇおよび１９ｈと、原料ガス供給装置１３ａと、原料液収納部１３ｂと、不活性ガス導入部２９とで、原料ガス供給系１３を主として構成している。   The first, third, fifth and sixth pipes 17a, 17c, 17e and 17f, and the first, third, fourth, fifth, seventh and eighth valves 19a, 19c, 19d, 19e, 19 g and 19 h, the source gas supply device 13 a, the source liquid storage unit 13 b, and the inert gas introduction unit 29 mainly constitute the source gas supply system 13.

一方、洗浄系１５は、洗浄液収納部１５ａと、高圧不活性ガス導入部１５ｂと、これら洗浄液収納部１５ａ及び高圧不活性ガス導入部１５ｂから供給装置１３ａに至る配管と、この配管に設けられたバルブと、第１および第２排気系２３および２７と、これら排気系と供給装置１３ａに至る配管と、これら配管に設けられたバルブ等で構成されている。上述の第３バルブ１９ｃおよび第４バルブ１９ｄの間の第３配管１７ｃ部分と高圧不活性ガス導入部１５ｂとの間に、第７配管１７ｇが接続してある。この第７配管１７ｇの中途には、第３バルブ１９ｃ側から第９バルブ１９ｉおよび第１０バルブ１９ｊが順次に配設されており、第１０バルブ１９ｊをはさむ両側の第７配管１７ｇの部分に、第１１バルブ１９ｋが配設してある第８配管１７ｈと、第１２バルブ１９ｌが配設してある第９配管１７ｉとが接続してある。この第８配管１７ｈおよび第９配管１７ｉは、それらの先端部分が洗浄液を収納してある洗浄液収納部１５ａ内に向かって伸びている配管である。ここでは、用いる洗浄液をトリメチルビニルシラン（ＴＭＶＳ）とする。洗浄液吸い上げ用の第８配管１７ｈは、洗浄液押し出し用の第９配管１７ｉに比べて長く、第８配管１７ｈの先端は洗浄液収納部１５ａの洗浄液中に浸されているが、第９配管１７ｉの先端は浸されていない。また、第７配管１７ｇの第９バルブ１９ｉとは反対側の先端に、高圧不活性ガスを供給する高圧不活性ガス導入部１５ｂが接続してある。この高圧不活性ガス導入部１５ｂより、高圧に保持された不活性ガスが第９配管１７ｉに導入されると、第８配管１７ｈが洗浄液を吸い上げる仕組みとなっている。高圧不活性ガスは洗浄液と反応しないものが良く、ここではＮ2 （窒素）を用いる。 On the other hand, the cleaning system 15 is provided with a cleaning liquid storage part 15a, a high-pressure inert gas introduction part 15b, a pipe from the cleaning liquid storage part 15a and the high-pressure inert gas introduction part 15b to the supply device 13a, and the pipe. It comprises a valve, first and second exhaust systems 23 and 27, pipes extending to the exhaust system and the supply device 13a, valves provided in these pipes, and the like. A seventh pipe 17g is connected between the third pipe 17c portion between the third valve 19c and the fourth valve 19d and the high-pressure inert gas introduction part 15b. In the middle of the seventh pipe 17g, a ninth valve 19i and a tenth valve 19j are sequentially arranged from the third valve 19c side, and in the seventh pipe 17g on both sides sandwiching the tenth valve 19j, The eighth pipe 17h in which the eleventh valve 19k is arranged is connected to the ninth pipe 17i in which the twelfth valve 19l is arranged. The eighth pipe 17h and the ninth pipe 17i are pipes whose tip portions extend toward the inside of the cleaning liquid storage portion 15a in which the cleaning liquid is stored. Here, the cleaning solution used is trimethylvinylsilane (TMVS). The eighth pipe 17h for cleaning liquid suction is longer than the ninth pipe 17i for pushing out the cleaning liquid, and the tip of the eighth pipe 17h is immersed in the cleaning liquid in the cleaning liquid storage portion 15a, but the tip of the ninth pipe 17i. Is not soaked. A high-pressure inert gas introduction part 15b for supplying high-pressure inert gas is connected to the tip of the seventh pipe 17g opposite to the ninth valve 19i. When the inert gas maintained at a high pressure is introduced into the ninth pipe 17i from the high-pressure inert gas introduction portion 15b, the eighth pipe 17h sucks up the cleaning liquid. The high-pressure inert gas preferably does not react with the cleaning liquid, and N 2 (nitrogen) is used here.

また、第１バルブ１９ａと供給装置１３ａとの間の第１配管１７ａ部分に第２配管１７ｂが接続してあり、第２配管１７ｂは第２バルブ１９ｂを介して第１ベント２１に接続してある。この第１ベント２１の先端に第２排気系２３が配設されている。また、第３バルブ１９ｃと第４バルブ１９ｄとの間の第３配管１７ｃ部分に第４配管１７ｄが接続してあり、第４配管１７ｄは第６バルブ１９ｆを介して第２ベント２５に接続してある。この第２ベント２５の先端に第３排気系２７が配設されている。   The second pipe 17b is connected to the first pipe 17a between the first valve 19a and the supply device 13a, and the second pipe 17b is connected to the first vent 21 via the second valve 19b. is there. A second exhaust system 23 is disposed at the tip of the first vent 21. The fourth pipe 17d is connected to the third pipe 17c portion between the third valve 19c and the fourth valve 19d, and the fourth pipe 17d is connected to the second vent 25 via the sixth valve 19f. It is. A third exhaust system 27 is disposed at the tip of the second vent 25.

以上、第１バルブ１９ａと供給装置１３ａとの間の第１配管１７ａと、第４バルブ１９ｄよりも供給装置１３ａ寄りの第３配管部分と、第２、第４、第７、第８および第９配管１７ｂ、１７ｄ、１７ｇ、１７ｈおよび１７ｉと、第２、第６、第９、第１０、第１１および第１２バルブ１９ｂ、１９ｆ、１９ｉ、１９ｊ、１９ｋおよび１９ｌと、洗浄液収納部１５ａと、高圧不活性ガス導入部１５ｂと、第１ベント２１および第２排気系２３、第２ベント２５および第３排気系２５とで、洗浄系１５を主として構成している。   As described above, the first piping 17a between the first valve 19a and the supply device 13a, the third piping portion closer to the supply device 13a than the fourth valve 19d, the second, fourth, seventh, eighth and eighth 9 piping 17b, 17d, 17g, 17h and 17i, second, sixth, ninth, tenth, eleventh and twelfth valves 19b, 19f, 19i, 19j, 19k and 19l, a cleaning liquid storage portion 15a, The cleaning system 15 is mainly composed of the high-pressure inert gas introduction portion 15b, the first vent 21 and the second exhaust system 23, the second vent 25 and the third exhaust system 25.

次に、この気相成長装置１０の動作について説明する。   Next, the operation of the vapor phase growth apparatus 10 will be described.

まず、原料ガス供給装置１３ａを立ち上げる。最初に、第１バルブ１９ａ、第４バルブ１９ｄ、第９バルブ１９ｉが閉まっていることを確認する。次に、第３バルブ１９ｃおよび第６バルブ１９ｆを開き、第６バルブ１９ｆに接続されている第２ベント２５側の第３排気系２７を用いて、配管を含む供給装置１３ａ内部（原料容器、気化器）の排気を行う。場合によっては、供給装置１３ａ内部がある程度減圧された状態になれば、途中から第１バルブ１９ａを開いて、第１排気系１１ａと第３排気系２７とを同時に用いて、供給装置１３ａの排気を効率よく行っても良い。   First, the source gas supply device 13a is started up. First, it is confirmed that the first valve 19a, the fourth valve 19d, and the ninth valve 19i are closed. Next, the third valve 19c and the sixth valve 19f are opened, and the third exhaust system 27 on the second vent 25 side connected to the sixth valve 19f is used to supply the inside of the supply device 13a including the pipe (raw material container, Exhaust the carburetor. In some cases, when the inside of the supply device 13a is decompressed to some extent, the first valve 19a is opened halfway, and the exhaust of the supply device 13a is simultaneously performed using the first exhaust system 11a and the third exhaust system 27. May be performed efficiently.

次に、第６バルブ１９ｆ、第１１および第１２バルブ１９ｋおよび１９ｌを閉め、第９バルブ１９ｉおよび第１０バルブ１９ｊを開いて、高圧不活性ガス導入部１５ｂよりＮ2 を導入し、供給装置１３ａに対してパージを行う。以上の操作（排気、パージ）を数回繰り返す。 Next, the sixth valve 19f, the eleventh and twelfth valves 19k and 19l are closed, the ninth valve 19i and the tenth valve 19j are opened, N 2 is introduced from the high-pressure inert gas introduction part 15b, and the supply device 13a Purge. The above operations (exhaust and purge) are repeated several times.

次に、第１０バルブ１９ｊを閉めて第１１バルブ１９ｋおよび第１２バルブ１９ｌを開き、洗浄液収納部１５ａに、高圧不活性ガス導入部１５ｂより、第９配管１７ｉを介してＮ2 を導入する。こうして、第８配管１７ｈ→第７配管１７ｇ→第３配管１７ｃの、第４バルブ１９ｄよりも供給装置１３ａ寄りの部分→供給装置１３ａ→供給装置１３ａと第１バルブ１９ａとの間の第１配管１７ａ、の順に、これらを洗浄液で満たす。次に、第１１バルブ１９ｋおよび第１２バルブ１９ｌを閉め、第６バルブ１９ｆを開いて、第３排気系２７より洗浄液を排出する。このとき、第１０バルブ１９ｊを開いて、高圧不活性ガス導入部１５ｂより、同時にＮ2 を導入すると、洗浄液の排出を効率よく行うことができる。ここで用いた洗浄液は蒸気圧が高いため、気体となって排出（排気）される。こうして供給装置１３ａ内部に残存していた大気（大気中の水分）の除去を行う。この洗浄液を用いた立ち上げ時の処理により、供給装置１３ａ内の大気の除去を、より高い効果をもって行うことができる。このため、成膜速度や成膜特性等の低下等の経時変化が起こるおそれが少ない。 Next, the tenth valve 19j is closed and the eleventh valve 19k and the twelfth valve 19l are opened, and N 2 is introduced into the cleaning liquid storage portion 15a from the high-pressure inert gas introduction portion 15b through the ninth pipe 17i. Thus, the portion of the eighth pipe 17h → the seventh pipe 17g → the third pipe 17c closer to the supply device 13a than the fourth valve 19d → the supply device 13a → the first pipe between the supply device 13a and the first valve 19a. These are filled with the cleaning liquid in the order of 17a. Next, the eleventh valve 19k and the twelfth valve 19l are closed, the sixth valve 19f is opened, and the cleaning liquid is discharged from the third exhaust system 27. At this time, if the tenth valve 19j is opened and N 2 is introduced simultaneously from the high-pressure inert gas introduction part 15b, the cleaning liquid can be discharged efficiently. Since the cleaning liquid used here has a high vapor pressure, it is discharged (exhausted) as a gas. In this way, the atmosphere (water in the atmosphere) remaining inside the supply device 13a is removed. By the processing at the time of start-up using this cleaning liquid, the atmosphere in the supply device 13a can be removed with a higher effect. For this reason, there is little possibility that a change with time such as a decrease in film forming speed and film forming characteristics will occur.

次に、第５バルブ１９ｅ、第９バルブ１９ｉおよび第６バルブ１９ｆを閉め、第４バルブ１９ｄ、第７バルブ１９ｇ、第８バルブ１９ｈを開いて、不活性ガス導入部２９より、Ｈｅ等の不活性ガスを、第６配管１７ｆを介して供給装置１３ａ側に送り込む。このため、原料液（Ｃｕ（ｈｆａｃ）（ｔｍｖｓ））は、第５配管１７ｅ、第３配管１７ｃを介して、原料ガス供給装置１３ａ内の図示しない原料容器に送り込まれる。   Next, the fifth valve 19e, the ninth valve 19i and the sixth valve 19f are closed, and the fourth valve 19d, the seventh valve 19g and the eighth valve 19h are opened. The active gas is sent to the supply device 13a side through the sixth pipe 17f. For this reason, the raw material liquid (Cu (hfac) (tmvs)) is sent to a raw material container (not shown) in the raw material gas supply device 13a through the fifth pipe 17e and the third pipe 17c.

次に、原料容器から原料を図示しない気化器に送り込んで気化する。その後、真空排気が済んだ反応室１１に、供給装置１３ａから、第１バルブ１９ａを介して原料ガスを送り込み、熱化学反応を生じさせることにより、基板ホルダに設置した基板に対して成膜を行う。   Next, the raw material is sent from a raw material container to a vaporizer (not shown) and vaporized. Thereafter, a raw material gas is sent from the supply device 13a to the reaction chamber 11 that has been evacuated through the first valve 19a to cause a thermochemical reaction, thereby forming a film on the substrate placed on the substrate holder. Do.

ここで、供給装置１３ａ内部において、何らかの原因で生成物が発生し、詰まり等のトラブルが生じた場合は、次のような処理を行う。   Here, when a product is generated for some reason in the supply device 13a and a trouble such as clogging occurs, the following processing is performed.

１）第１バルブ１９ａ、第３バルブ１９ｃ、第９バルブ１９ｉ、第１０バルブ１９ｊを開き、他のバルブを閉じた後、高圧不活性ガス導入部１５ｂより、第７配管１７ｇ→第３配管１７ｃの、第４バルブ１９ｄよりも供給装置１３ａ寄りの部分→供給装置１３ａ→第１配管１７ａ→反応室の順にＮ2 ガスを送り込む。このとき、反応室１１に具えられている図示しない圧力計をモニターし、反応室１１の圧力上昇を確認する。Ｎ2 の供給圧力を上げることで徐々に反応室１１内の圧力が上昇すれば、高圧不活性ガス（Ｎ2 ）のパージによって供給装置１３ａ内の生成物が除去されて、Ｎ2 が反応室に導入されたことになり、この処理が有効であることを示す。 1) After opening the first valve 19a, the third valve 19c, the ninth valve 19i, and the tenth valve 19j and closing the other valves, the seventh pipe 17g → the third pipe 17c from the high-pressure inert gas introduction part 15b. N 2 gas is fed in the order of the portion closer to the supply device 13a than the fourth valve 19d → the supply device 13a → the first pipe 17a → the reaction chamber. At this time, a pressure gauge (not shown) provided in the reaction chamber 11 is monitored to confirm an increase in pressure in the reaction chamber 11. If gradually increase the pressure inside the reaction chamber 11 by raising the supply pressure of the N 2, it is the product of the supply device 13a by purging pressure inert gas (N 2) is removed, N 2 reaction chamber This indicates that this processing is effective.

２）上記１）の処理を行っても改善が見られない場合は、第１０バルブ１９ｊを閉めて第１１バルブ１９ｋおよび第１２バルブ１９ｌを開き、Ｎ2 ガスを洗浄液収納部１５ａに導入しながら、洗浄液を第８配管１７ｈ→第７配管１７ｇの、第１０バルブ１９ｊが設けられている側の部分→第３配管１７ｃの、第４バルブ１９ｄよりも供給装置１３ａ寄りの部分→供給装置１３ａ→第１配管１７ａ→反応室１１の順に送り込む。Ｎ2 の供給圧力を上げていきながら上述の圧力計をモニターしていると、反応室の圧力の急激な上昇が見られる。これは、洗浄液による洗浄効果と高圧不活性ガス（Ｎ2 ）のパージとによって供給装置１３ａ内部の生成物が除去されて、洗浄液とガスとの混合物が反応室に流れ込むためである。反応室１１に流れ込んだ洗浄液およびガスは、第１排気系１１ａより排気する。 2) If no improvement is observed even after the processing of 1) above, the tenth valve 19j is closed, the eleventh valve 19k and the twelfth valve 19l are opened, and N 2 gas is introduced into the cleaning liquid storage portion 15a. , The portion of the eighth pipe 17h → the seventh pipe 17g on the side where the tenth valve 19j is provided → the part of the third pipe 17c closer to the supply device 13a than the fourth valve 19d → the supply device 13a → The first pipe 17a is sent in the order of the reaction chamber 11. When the above-mentioned pressure gauge is monitored while increasing the supply pressure of N 2 , a rapid increase in the pressure in the reaction chamber is observed. This is because the product inside the supply device 13a is removed by the cleaning effect of the cleaning liquid and the purge of the high-pressure inert gas (N 2 ), and the mixture of the cleaning liquid and the gas flows into the reaction chamber. The cleaning liquid and gas flowing into the reaction chamber 11 are exhausted from the first exhaust system 11a.

このように、洗浄系１５を動作させることにより、供給装置１３ａを取り外すことなく、この供給装置１３ａ内部の詰まりを除去することができ、継続して使用することができる。   Thus, by operating the cleaning system 15, the clogging inside the supply device 13a can be removed without removing the supply device 13a, and it can be used continuously.

なお、ここでは、上記の生成物除去において、洗浄液およびガスを反応室１１の排気系１１ａから排気する例を示したが、反応室１１をクリーンに保つ上からは、第１バルブ１９ａを閉め、第２バルブ１９ｂを開いて第２排気系２３から排気する方が望ましい。   Here, an example in which the cleaning liquid and gas are exhausted from the exhaust system 11a of the reaction chamber 11 in the above product removal is shown, but in order to keep the reaction chamber 11 clean, the first valve 19a is closed, It is desirable to open the second valve 19b and exhaust from the second exhaust system 23.

この発明は、例示の形態に限定されるものではないことは明らかである。例えば、上述の形態では、原料としてＣｕ（ｈｆａｃ）（ｔｍｖｓ）を用い、洗浄液としてＴＭＶＳを用いた例を示したが、その他の適切な組み合わせでも良い。例えば、原料として、テトラキスジメチルアミノチタンやテトラキスジエチルアミノチタン等のテトラキスジアルキルアミノチタンを用いた場合には、洗浄液としてノルマルヘキサンを用いることができる。   Obviously, the present invention is not limited to the illustrated embodiments. For example, in the above-described embodiment, Cu (hfac) (tmvs) is used as the raw material and TMVS is used as the cleaning liquid. However, other appropriate combinations may be used. For example, when tetrakisdialkylaminotitanium such as tetrakisdimethylaminotitanium or tetrakisdiethylaminotitanium is used as a raw material, normal hexane can be used as a cleaning liquid.

この発明の実施の形態の気相成長装置の説明に供する概略的な装置構成図である。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic apparatus configuration diagram for explaining a vapor phase growth apparatus according to an embodiment of the present invention.

符号の説明Explanation of symbols

１０：気相成長装置
１１：反応室
１１ａ：第１排気系
１３：原料ガス供給系
１３ａ：原料ガス供給装置
１３ｂ：原料液収納部
１５：洗浄系
１５ａ：洗浄液収納部
１５ｂ：高圧不活性ガス導入部
１７ａ〜１７ｉ：第１〜第９配管
１９ａ〜１９ｌ：第１〜第１２バルブ
２１：第１ベント
２３：第２排気系
２５：第２ベント
２７：第３排気系
２９：不活性ガス導入部 DESCRIPTION OF SYMBOLS 10: Vapor growth apparatus 11: Reaction chamber 11a: 1st exhaust system 13: Raw material gas supply system 13a: Raw material gas supply apparatus 13b: Raw material liquid storage part 15: Cleaning system 15a: Cleaning liquid storage part 15b: Introducing high-pressure inert gas Parts 17a to 17i: first to ninth pipes 19a to 19l: first to twelfth valves 21: first vent 23: second exhaust system 25: second vent 27: third exhaust system 29: inert gas introduction part

Claims (7)

基板上に膜を形成する反応室と、該反応室に原料ガスと洗浄液と不活性ガスとを供給する原料ガス供給装置と、該原料ガス供給装置に前記原料ガスを供給する原料ガス供給系と、前記原料ガス供給装置に洗浄液を供給する洗浄系と、前記反応室を排気する排気系とを有する気相成長装置の異常生成物除去方法であって、
前記原料ガス供給装置から前記反応室内に前記原料ガスを供給することにより前記基板上に前記膜を形成する成膜工程と、
該成膜工程中に前記原料ガス供給装置内で異常生成物が発生した時に、該原料ガス供給装置への前記原料ガスの供給を停止し、該原料ガス供給装置への前記不活性ガスの供給を開始し、さらに、該不活性ガスの供給圧力を上昇させたときの前記反応室内の気圧をモニターする不活性ガス送出工程と、
該不活性ガス送出工程で前記不活性ガスの供給圧力を上昇させても前記反応室内の気圧が上昇しなかった場合に、前記洗浄液を用いて前記原料ガス供給装置内および前記反応室内を洗浄する洗浄工程と、
を含むことを特徴とする気相成長装置の異常生成物除去方法。 A reaction chamber for forming a film on the substrate, a source gas supply device for supplying source gas, a cleaning liquid and an inert gas to the reaction chamber, and a source gas supply system for supplying the source gas to the source gas supply device; A method for removing abnormal products of a vapor phase growth apparatus having a cleaning system for supplying a cleaning liquid to the source gas supply device and an exhaust system for exhausting the reaction chamber,
A film forming step of forming the film on the substrate by supplying the source gas into the reaction chamber from the source gas supply device;
When an abnormal product is generated in the source gas supply device during the film forming step, the supply of the source gas to the source gas supply device is stopped and the inert gas is supplied to the source gas supply device. And an inert gas delivery step for monitoring the atmospheric pressure in the reaction chamber when the supply pressure of the inert gas is increased, and
If the pressure inside the reaction chamber does not increase even if the supply pressure of the inert gas is increased in the inert gas delivery step, the inside of the source gas supply device and the reaction chamber are cleaned using the cleaning liquid. A cleaning process;
A method for removing abnormal products from a vapor phase growth apparatus. 請求項１に記載の気相成長装置の異常生成物除去方法において、
前記気相成長装置を立ち上げる際に、前記原料ガス供給装置内の大気を取り除くために、不活性ガスのパージおよび排気を繰り返す前処理を行い、
その後で、前記原料ガス供給装置に前記洗浄系の洗浄液を送り込んで洗浄する洗浄処理を行う、
ことを特徴とする気相成長装置の異常生成物除去方法。 In the abnormal product removal method of the vapor phase growth apparatus according to claim 1,
When starting up the vapor phase growth apparatus, in order to remove the atmosphere in the source gas supply apparatus, perform a pretreatment that repeats purging and exhausting inert gas,
Thereafter, a cleaning process is performed in which the cleaning liquid of the cleaning system is sent to the source gas supply device for cleaning.
An abnormal product removing method for a vapor phase growth apparatus. 請求項１に記載の気相成長装置の異常生成物除去方法において、
前記洗浄液は、前記反応室で形成を行う膜の原料と反応することなく前記原料を溶融することが可能な物質からなること特徴とする気相成長装置の異常生成物除去方法。 In the abnormal product removal method of the vapor phase growth apparatus according to claim 1,
The method for removing an abnormal product of a vapor phase growth apparatus, wherein the cleaning liquid is made of a substance capable of melting the raw material without reacting with the raw material of the film to be formed in the reaction chamber. 請求項３に記載の気相成長装置の異常生成物除去方法において、
前記原料としてヘキサフルオロアセチルアセトナート・トリメチルビニルシラン・銅を用い、且つ、前記洗浄液としてトリメチルビニルシランを用いることを特徴とする気相成長装置の異常生成物除去方法。 In the method for removing abnormal products of the vapor phase growth apparatus according to claim 3,
A method for removing an abnormal product of a vapor phase growth apparatus, wherein hexafluoroacetylacetonate / trimethylvinylsilane / copper is used as the raw material, and trimethylvinylsilane is used as the cleaning liquid. 請求項３に記載の気相成長装置の異常生成物除去方法において、
前記原料としてテトラキスジメチルアミノチタンまたはテトラキスジエチルアミノチタンを用い、且つ、前記洗浄液としてノルマルヘキサンを用いることを特徴とする気相成長装置の異常生成物除去方法。 In the method for removing abnormal products of the vapor phase growth apparatus according to claim 3,
An abnormal product removal method for a vapor phase growth apparatus, wherein tetrakisdimethylaminotitanium or tetrakisdiethylaminotitanium is used as the raw material, and normal hexane is used as the cleaning liquid. 請求項２に記載の気相成長装置の異常生成物除去方法において、
前記不活性ガスとして、前記洗浄液と反応しないものを用いることを特徴とする気相成長装置の異常生成物除去方法。 In the abnormal product removal method of the vapor phase growth apparatus according to claim 2,
A method for removing abnormal products of a vapor phase growth apparatus, wherein the inert gas does not react with the cleaning liquid. 請求項６に記載の気相成長装置の異常生成物除去方法において、
前記不活性ガスとして、窒素、アルゴン又はヘリウムを用いることを特徴とする気相成長装置の異常生成物除去方法。 In the abnormal product removal method of the vapor phase growth apparatus according to claim 6,
An abnormal product removing method for a vapor phase growth apparatus, wherein nitrogen, argon or helium is used as the inert gas.
JP2007259420A 2007-10-03 2007-10-03 Abnormal product removal method for vapor phase growth apparatus Expired - Lifetime JP4680246B2 (en)

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