JP3669864B2 - Cleaning method for Si3N4 film forming apparatus - Google Patents
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- JP3669864B2 JP3669864B2 JP10199899A JP10199899A JP3669864B2 JP 3669864 B2 JP3669864 B2 JP 3669864B2 JP 10199899 A JP10199899 A JP 10199899A JP 10199899 A JP10199899 A JP 10199899A JP 3669864 B2 JP3669864 B2 JP 3669864B2
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- 238000004140 cleaning Methods 0.000 title claims description 23
- 238000000034 method Methods 0.000 title claims description 12
- 229910052581 Si3N4 Inorganic materials 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000002210 silicon-based material Substances 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010408 film Substances 0.000 description 18
- 229910021417 amorphous silicon Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910017855 NH 4 F Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Cleaning In General (AREA)
- Chemical Vapour Deposition (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、ＣＶＤ法、スパッタリング法、ゾルゲル法、蒸着法等を用いて薄膜、厚膜、粉体、ウイスカを製造する装置において装置内壁、冶具等に堆積した不要な堆積物を除去するためのクリーニング方法で、特にＳｉ3Ｎ4成膜装置のクリーニング方法に関する。
【０００２】
【従来の技術および発明が解決しようとする課題】
ＳｉＨ2Ｃｌ2やＮＨ3を原料としてＳｉ3Ｎ4を成膜する装置の低温部、特に排気系配管内やトラップ内にはアモルファス状シリコン、アモルファス状窒化珪素、アモルファス状酸化シリコンなどのアモルファス状Ｓｉ系化合物を含有するＮＨ4Ｃｌが多量に堆積する。そのため、これらを除去するため頻繁に清掃しなければならず装置稼働率を著しく低下させている。また、Ｓｉ3Ｎ4膜を製造する工場から排出される廃棄物量も非常に多量になり、製品コストの上昇を招いている。
【０００３】
ＮＨ4ＣｌをＣｌＦ3でクリーニングすることに関しては、特開平１−２３１９３６号公報に具体的な条件は記述されており、具体的な温度条件等に関しては特開平６−３３０５４号公報に記載されている。また、Ｓｉ系化合物がＣｌＦ3でクリーニング可能であることは特開昭６４−１７８５７号公報に述べられている。しかしながら、半導体等の製造プロセスでは、近年、シリコンウエハの大口径化が進んでおり、流通させるガス量も増加している傾向にあり、実際のＳｉ3Ｎ4成膜装置では、配管等の低温部にはＳｉ系化合物を含有したＮＨ4Ｃｌが堆積している。このようなＳｉ系化合物を含有した堆積物の場合には、ＣｌＦ3を流通させるのみではクリーニングができないため、ＣｌＦ3によるクリーニングは、Ｓｉ3Ｎ4成膜装置には用いられていないのが現状である。
【０００４】
Ｓｉ系化合物を含有しているＮＨ4ＣｌをＣｌＦ3でガス化除去できない原因は、Ｓｉ系化合物がフッ素化され生成したＳｉＦ4とＣｌＦ3が共存するとＣｌＦ3とほとんど反応しない（ＮＨ4)2ＳｉＦ6が堆積物表面に皮膜状に生成し、これがクリーニング反応を妨害するためである。反応式を以下に示す。
【０００５】
Ｓｉ＋３ＣｌＦ3＋２ＮＨ4Ｃｌ→（ＮＨ4)2ＳｉＦ6＋３ＣｌＦ＋Ｃｌ2
まず、ＮＨ4ＣｌとＣｌＦ3との反応によりＮＨ4Ｆの生成が起こる。この中でＮＨ4ＣｌとＳｉＦ4が接触しても（ＮＨ4)2ＳｉＦ6は生成しないが、ＮＨ4ＦはＳｉＦ4と接触すると（ＮＨ4)2ＳｉＦ6が生成することが分かっている（MOURI，I．，1998，(ＣＶＤ装置クリーニングへの応用を目的としたフッ化物ガスの反応特性に関する研究) 鳥取大学博士論文）。
【０００６】
以上のことはＳｉ系化合物を含有していないＮＨ4Ｃｌが堆積した排気配管の場合でも、反応器内のＳｉ3Ｎ4膜をクリーニングした際の排ガス中に未反応のＣｌＦ3が残っていると、配管内等のＮＨ4Ｃｌと接触することにより（ＮＨ4)2ＳｉＦ6が生成するためクリーニングできないことを示している。
【０００７】
また、(ＮＨ4)2ＳｉＦ6とＣｌＦ3との反応速度は、温度依存性が非常に高く（活性化エネルギー：０．７４ｅＶ）、かなり高温にしなければ反応除去できないが、アモルファス状のＳｉまたはＳｉ系化合物が含有されている場合、高温で処理したり、高ＣｌＦ3分圧下で処理した場合には、ＮＨ4Ｃｌが揮発し、ガス状態では、ＮＨ4Ｃｌ＝ＮＨ3＋ＨＣｌの平衡状態にあるため発火現象を起こすなどの問題がある。従って、この堆積物をクリーニングする場合にはＮＨ4Ｃｌの昇華温度まで堆積物温度が上がらないようにすることも重要であり、このことは（ＮＨ4)2ＳｉＦ6をガス化除去するために高温が必要であることと矛盾するといった技術的に非常に困難な条件が必要であることがわかる。
【０００８】
以上のように、現状ではＳｉ3Ｎ4成膜装置の有効なガスクリーニング方法は見出されておらず、湿式洗浄が行われているのが現状である。
【０００９】
【課題を解決するための具体的手段】
本発明者等は、鋭意検討の結果、Ｓｉ3Ｎ4膜製造装置のガスクリーニングの問題点を考慮して、Ｓｉ3Ｎ4とＳｉまたはＳｉ系化合物を含有したＮＨ4Ｃｌ（以下、ＮＨ4Ｃｌ堆積物と表記する）をＣｌＦ3でクリーニングする方法を見出し本発明に到達した。
【００１０】
すなわち本発明は、Ｓｉ3Ｎ4膜を製造する装置において、排気系配管内に堆積したＳｉまたはＳｉ系化合物を含有したＮＨ4ＣｌをＣｌＦ3で反応除去するＳｉ3Ｎ4成膜装置のクリーニング方法、さらに、反応器内に堆積したＳｉ3Ｎ4および排気系配管内に堆積したＳｉまたはＳｉ系化合物を含有したＮＨ4Ｃｌをクリーニングする際に、排気系配管内を先にＣｌＦ3で反応除去した後、反応器内をＣｌＦ3で反応除去するＳｉ3Ｎ4成膜装置のクリーニング方法を提供するものである。
【００１１】
本発明の方法を用いる対象物であるＳｉ系化合物とは、具体的には、アモルファス状シリコン、アモルファス状水素化シリコン、アモルファス状窒化珪素、アモルファス状酸化シリコン、アモルファス状ポリクロルシラン、アモルファス状ポリシランなどである。
【００１２】
本発明の方法において、圧力が、０．１〜２００Ｔｏｒｒの範囲で、温度が、７０〜１５０℃の範囲の条件で、ＣｌＦ3の流量を、単位時間当たりＮＨ4Ｃｌ堆積物に含有しているＳｉ量（モル量）に対して０．０１〜２０倍量（モル量）の範囲でクリーニングすることが好ましく、クリーニング残渣を処理前重量の５％以下に低減できるものである。これらの条件、範囲をはずれるとクリーニングが不十分であったり、発火現象を起こすため好ましくない。この場合の発火は、ＮＨ4Ｃｌ堆積物にともなうＮＨ3が、ＣｌＦ3とＳｉの反応により発生するものである。
【００１３】
また、反応器内のＳｉ3Ｎ4膜をＣｌＦ3でクリーニングする場合には、クリーニングの妨害物質である（ＮＨ4)2ＳｉＦ6を生成する原因となるＳｉＦ4が生成し、ＣｌＦ3と共に排気系配管に流入するため、反応器内をクリーニングする前に排気系配管を先に洗浄した後、反応器内をクリーニングすることが好ましい。排気系配管等が洗浄された後は、圧力が、０．１〜２００Ｔｏｒｒの範囲で、温度が、３００〜７００℃の範囲で、下式から得られるエッチング速度がプロセスの操業条件に見合った値である条件を適時選択すればよい。また、ＣｌＦ3流量は、装置の形状、大きさ及びＳｉ3Ｎ4の堆積量を鑑みて適時選択すればよいが、通常は１０ＳＣＣＭから１ＳＬＭの範囲で選択すればよい。
【００１４】
Ｒ（Ｓｉ3Ｎ4）＝１．３１×１０6・Ｐ・Ｔ1/2ｅｘｐ（−０．６４９／ｋＴ）
ここで、
Ｒ（Ｓｉ3Ｎ4）：エッチング速度（Å／ｍｉｎ） Ｐ：圧力（Ｔｏｒｒ）
ｋ：ボルツマン定数（８．６１７３×１０−５ｅＶ／Ｋ）
Ｔ：温度（Ｋ）
を示す。
【００１５】
【実施例】
以下、実施例により本発明を詳細に説明するが、本発明はかかる実施例に限定されるものではない。
【００１６】
実施例１〜１０、比較例１〜５
ＳｉＨ2Ｃｌ2とＮＨ3を原料としてＳｉ3Ｎ4を成膜するための横型熱ＣＶＤ装置の排気配管内には、分厚い膜状の物質が堆積していた。この堆積物を採取し、Ｘ線回折装置で分析を行ったところＮＨ4Ｃｌとアモルファス状の化合物の存在が確認された。また、蛍光Ｘ線分析装置で原子番号９以上の元素について元素分析を行ったところＳｉ、Ｃｌのみ検出された。さらにＩＣＰ分析によって堆積物中のＳｉ含有量を定量した。その結果、Ｓｉ含有量は７．８％であった。
【００１７】
この堆積物を各０．５ｇ採取し、Ｎｉ製のヒータを石英製のチャンバ内に備えた内容積１６Ｌのコールドウオール型反応器を用いて、種々の条件でＣｌＦ3による暴露試験を行い、ガス化除去を試みた。それらの条件、結果を表１に示した。なお、表１中のＣｌＦ3／Ｓｉ比は、ＮＨ4Ｃｌ堆積物中に含有するＳｉのモル量でＣｌＦ3の単位時間流量(モル/ｍｉｎ)を除した値である。
【００１８】
【表１】
実施例１１
ＳｉＨ2Ｃｌ2とＮＨ3を原料としてＳｉ3Ｎ4を成膜するＣＶＤ装置の排気系配管に、白色のＳｉを含有したＮＨ4Ｃｌが厚さ約２ｍｍ（総重量２００ｇ)で堆積していた。この配管にガス導入管を取り付け、配管を１００℃に加温し、ＣｌＦ3を５Ｔｏｒｒ、６３ＳＣＣＭ（堆積物中のＳｉ含有量に対するＣｌＦ3のモル比＝０．０５）の条件で６０分間導入した。配管内面を観察したところ配管は完全にクリーニングされており腐蝕も起きていなかった。
【００２０】
比較例６
実施例１１と同様の成膜反応を行った後、反応器内面には厚さ約２０μｍの厚みでＳｉ3Ｎ4膜が、配管には厚さ約２ｍｍのＳｉ系化合物を含有したＮＨ4Ｃｌが堆積していた。反応器を４３０℃、配管を１００℃に加温し、反応器のガス導入口から実施例１１と同様の条件でＣｌＦ3を導入したところ、Ｓｉ3Ｎ4は完全に除去できていたが、配管内堆積物の表面は白色から黄赤色に変色し、厚みも反応前からほとんど変化していなかった。このＣｌＦ3反応後の堆積物を採取し、Ｘ線回折装置にて分析したところ（ＮＨ4)2ＳｉＦ6とＮＨ4Ｃｌを主成分とする物質であった。
【００２１】
実施例１２
実施例１１と同様の成膜反応を行った後、反応器内面には厚さ約２０μｍの厚みでＳｉ3Ｎ4膜が、配管には厚さ約２ｍｍのＳｉ系化合物を含有したＮＨ4Ｃｌが堆積していた。反応器を４３０℃、配管を１００℃に加温し、配管のガス導入口から実施例１１と同様の条件でＣｌＦ3を６０分導入し、続けて反応器のガス導入口からＣｌＦ3を同様の条件で導入したところＳｉ3Ｎ4も配管内堆積物も除去されていた。
【００２２】
【発明の効果】
本発明のクリーニング方法を用いることにより、Ｓｉ3Ｎ4成膜装置、配管等を損傷することなく容易にクリーニングを行うことができる。[0001]
BACKGROUND OF THE INVENTION
The present invention is for removing unnecessary deposits deposited on an inner wall of a device, a jig, etc. in an apparatus for producing a thin film, thick film, powder, whisker using a CVD method, a sputtering method, a sol-gel method, a vapor deposition method, etc. More particularly, the present invention relates to a cleaning method for a Si 3 N 4 film forming apparatus.
[0002]
[Background Art and Problems to be Solved by the Invention]
Amorphous materials such as amorphous silicon, amorphous silicon nitride, and amorphous silicon oxide are used in the low-temperature part of equipment that deposits Si 3 N 4 using SiH 2 Cl 2 and NH 3 as raw materials, especially in exhaust pipes and traps. A large amount of NH 4 Cl containing Si-based compounds is deposited. Therefore, it is necessary to clean frequently in order to remove these, and the apparatus operation rate is significantly reduced. In addition, the amount of waste discharged from the factory that manufactures the Si 3 N 4 film has become very large, leading to an increase in product cost.
[0003]
Regarding the cleaning of NH 4 Cl with ClF 3 , specific conditions are described in JP-A-1-231936, and specific temperature conditions and the like are described in JP-A-6-33054. Yes. Moreover, it is described in Japanese Patent Application Laid-Open No. 64-17857 that Si-based compounds can be cleaned with ClF 3 . However, in the manufacturing process of semiconductors and the like, the diameter of silicon wafers has been increasing in recent years, and the amount of gas to be circulated has been increasing. In an actual Si 3 N 4 film forming apparatus, the temperature of piping and the like is low. In this part, NH 4 Cl containing a Si compound is deposited. In the case of deposits containing such Si-based compounds, cleaning cannot be performed only by circulating ClF 3, and therefore cleaning with ClF 3 is not used in the Si 3 N 4 film forming apparatus. It is.
[0004]
Cause can not be removed gasifying NH 4 Cl in ClF 3 containing the Si-based compound, hardly reacts with ClF 3 when SiF 4 and ClF 3 of Si compound was formed fluorinated coexist (NH 4) 2 This is because SiF 6 is formed as a film on the surface of the deposit, which interferes with the cleaning reaction. The reaction formula is shown below.
[0005]
Si + 3ClF 3 + 2NH 4 Cl → (NH 4 ) 2 SiF 6 + 3ClF + Cl 2
First, NH 4 F generation of takes place by reaction with NH 4 Cl and ClF 3. It is NH 4 Cl and SiF 4 in the contacts (NH 4) 2 SiF 6 is not generated, NH 4 F is found to be in contact with the SiF 4 to (NH 4) 2 SiF 6 is produced (MOURI, I., 1998, (Research on reaction characteristics of fluoride gas for application to CVD equipment cleaning) Doctoral dissertation in Tottori University).
[0006]
As described above, unreacted ClF 3 remains in the exhaust gas when the Si 3 N 4 film in the reactor is cleaned even in the case of an exhaust pipe in which NH 4 Cl containing no Si-based compound is deposited. This indicates that (NH 4 ) 2 SiF 6 is produced by contact with NH 4 Cl in the pipe or the like, so that it cannot be cleaned.
[0007]
The reaction rate between (NH 4 ) 2 SiF 6 and ClF 3 is very high in temperature dependence (activation energy: 0.74 eV) and cannot be removed unless the temperature is considerably increased. When Si-based compounds are contained, NH 4 Cl is volatilized when treated at a high temperature or under a high ClF 3 partial pressure, and in a gas state, NH 4 Cl = NH 3 + HCl is brought into an equilibrium state. There are problems such as causing an ignition phenomenon. Therefore, when cleaning this deposit, it is also important not to raise the deposit temperature to the sublimation temperature of NH 4 Cl, which is necessary for gasifying and removing (NH 4 ) 2 SiF 6. It can be seen that technically very difficult conditions are necessary that contradict the need for high temperatures.
[0008]
As described above, no effective gas cleaning method for the Si 3 N 4 film forming apparatus has been found at present, and wet cleaning is currently performed.
[0009]
[Specific means for solving the problem]
The present inventors have conducted extensive studies results, Si 3 N 4 in view of the problems of the gas cleaning film production apparatus, Si 3 N 4 NH 4 containing a Si or Si compound Cl (hereinafter, NH 4 The present inventors have found a method of cleaning (denoted as Cl deposits) with ClF 3 and reached the present invention.
[0010]
That is, the present invention, Si 3 N in a device for producing a 4 film, cleaning the Si 3 N 4 film forming apparatus for reacting remove NH 4 Cl containing Si or Si compound deposited in the exhaust system in the pipe with ClF 3 In the method, when cleaning NH 3 Cl containing Si 3 N 4 deposited in the reactor and Si or Si-based compound deposited in the exhaust system pipe, the exhaust system pipe is first reacted with ClF 3 . The present invention provides a cleaning method for a Si 3 N 4 film forming apparatus in which the inside of a reactor is removed by reaction with ClF 3 after the removal.
[0011]
Specifically, the Si-based compound that is an object using the method of the present invention includes amorphous silicon, amorphous hydrogenated silicon, amorphous silicon nitride, amorphous silicon oxide, amorphous polychlorosilane, and amorphous polysilane. Etc.
[0012]
In the method of the present invention, the flow rate of ClF 3 is contained in the NH 4 Cl deposit per unit time under the conditions that the pressure is in the range of 0.1 to 200 Torr and the temperature is in the range of 70 to 150 ° C. It is preferable to perform cleaning in the range of 0.01 to 20 times (molar amount) with respect to the Si amount (molar amount), and the cleaning residue can be reduced to 5% or less of the pre-treatment weight. Any deviation from these conditions and ranges is not preferable because of insufficient cleaning or ignition. The ignition in this case is that NH 3 accompanying NH 4 Cl deposits is generated by the reaction of ClF 3 and Si.
[0013]
Further, when the Si 3 N 4 film in the reactor is cleaned with ClF 3 , SiF 4 causing generation of (NH 4 ) 2 SiF 6 which is a cleaning interfering substance is generated, and exhausted together with ClF 3. In order to flow into the system piping, it is preferable to clean the inside of the reactor after the exhaust system piping is first cleaned before the inside of the reactor is cleaned. After the exhaust system piping is cleaned, the pressure is in the range of 0.1 to 200 Torr, the temperature is in the range of 300 to 700 ° C., and the etching rate obtained from the following equation is a value suitable for the process operating conditions. A condition that is: The ClF 3 flow rate may be selected in a timely manner in consideration of the shape and size of the apparatus and the deposition amount of Si 3 N 4 , but is usually selected in the range of 10 SCCM to 1 SLM.
[0014]
R (Si 3 N 4 ) = 1.31 × 10 6 · P · T 1/2 exp (−0.649 / kT)
here,
R (Si 3 N 4 ): Etching rate (Å / min) P: Pressure (Torr)
k: Boltzmann constant (8.6173 × 10 −5 eV / K)
T: Temperature (K)
Indicates.
[0015]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to this Example.
[0016]
Examples 1-10, Comparative Examples 1-5
A thick film-like substance was deposited in the exhaust pipe of the horizontal thermal CVD apparatus for forming Si 3 N 4 using SiH 2 Cl 2 and NH 3 as raw materials. This deposit was collected and analyzed with an X-ray diffractometer, and the presence of NH 4 Cl and an amorphous compound was confirmed. Further, when elemental analysis was performed on an element having an atomic number of 9 or more using a fluorescent X-ray analyzer, only Si and Cl were detected. Further, the Si content in the deposit was quantified by ICP analysis. As a result, the Si content was 7.8%.
[0017]
0.5 g of each deposit was sampled, and an exposure test using ClF 3 was conducted under various conditions using a cold wall reactor having an internal volume of 16 L equipped with a Ni heater in a quartz chamber. Tried to remove. The conditions and results are shown in Table 1. The ClF 3 / Si ratio in Table 1 is a value obtained by dividing the unit time flow rate (mol / min) of ClF 3 by the molar amount of Si contained in the NH 4 Cl deposit.
[0018]
[Table 1]
Example 11
NH 4 Cl containing white Si was deposited in a thickness of about 2 mm (total weight 200 g) on the exhaust system piping of the CVD apparatus for forming Si 3 N 4 using SiH 2 Cl 2 and NH 3 as raw materials. . A gas introduction pipe was attached to this pipe, the pipe was heated to 100 ° C., and ClF 3 was introduced for 60 minutes under the conditions of 5 Torr and 63 SCCM (molar ratio of ClF 3 to Si content in the deposit = 0.05). . When the inner surface of the pipe was observed, the pipe was completely cleaned and no corrosion occurred.
[0020]
Comparative Example 6
After performing the same film formation reaction as in Example 11, the reactor inner surface had a Si 3 N 4 film with a thickness of about 20 μm, and the pipe had NH 4 Cl containing a Si-based compound with a thickness of about 2 mm. Was deposited. When the reactor was heated to 430 ° C. and the piping was heated to 100 ° C. and ClF 3 was introduced from the gas inlet of the reactor under the same conditions as in Example 11, Si 3 N 4 was completely removed. The surface of the sediment in the pipe changed from white to yellow-red, and the thickness hardly changed from before the reaction. The deposit after the ClF 3 reaction was collected and analyzed by an X-ray diffractometer. As a result, the substance was composed mainly of (NH 4 ) 2 SiF 6 and NH 4 Cl.
[0021]
Example 12
After performing the same film formation reaction as in Example 11, the reactor inner surface had a Si 3 N 4 film with a thickness of about 20 μm, and the pipe had NH 4 Cl containing a Si-based compound with a thickness of about 2 mm. Was deposited. The reactor is heated to 430 ° C. and the pipe is heated to 100 ° C., and ClF 3 is introduced from the gas inlet of the pipe under the same conditions as in Example 11 for 60 minutes, and then ClF 3 is similarly supplied from the gas inlet of the reactor. When introduced under these conditions, Si 3 N 4 and deposits in the piping were removed.
[0022]
【The invention's effect】
By using the cleaning method of the present invention, cleaning can be easily performed without damaging the Si 3 N 4 film forming apparatus, piping, and the like.
Claims (1)
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