JP3865113B2 - Cleaning gas and etching gas - Google Patents
Cleaning gas and etching gas Download PDFInfo
- Publication number
- JP3865113B2 JP3865113B2 JP2000207473A JP2000207473A JP3865113B2 JP 3865113 B2 JP3865113 B2 JP 3865113B2 JP 2000207473 A JP2000207473 A JP 2000207473A JP 2000207473 A JP2000207473 A JP 2000207473A JP 3865113 B2 JP3865113 B2 JP 3865113B2
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- gas
- silicon
- coochf
- compound
- etching
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- 238000004140 cleaning Methods 0.000 title claims description 56
- 238000005530 etching Methods 0.000 title claims description 37
- 239000007789 gas Substances 0.000 claims description 86
- 150000001875 compounds Chemical class 0.000 claims description 29
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 21
- 229910052731 fluorine Inorganic materials 0.000 claims description 21
- 239000011737 fluorine Substances 0.000 claims description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- 239000002210 silicon-based material Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 150000003377 silicon compounds Chemical class 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000003870 refractory metal Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000010408 film Substances 0.000 description 38
- 239000004065 semiconductor Substances 0.000 description 12
- 238000010792 warming Methods 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 239000010409 thin film Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000002222 fluorine compounds Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- -1 perfluoro compounds Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
- C23C16/4405—Cleaning of reactor or parts inside the reactor by using reactive gases
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Drying Of Semiconductors (AREA)
- Chemical Vapour Deposition (AREA)
- Detergent Compositions (AREA)
- Physical Vapour Deposition (AREA)
Description
【０００１】
【発明の技術分野】
本発明は、チャンバークリーニング用ガス及びエッチングガスに関する。さらに詳しくは、地球温暖化への寄与の小さいフッ素系化合物からなる半導体基板製造に好適なＣＶＤ装置等のチャンバークリーニング用ガス及びエッチングガスに関する。
【０００２】
【発明の技術的背景】
従来、半導体製造等における薄膜デバイスの製造プロセス等においては、ＣＶＤ法等を用いて、種々の薄膜、厚膜の形成が行われている。このような半導体用の薄膜を形成する際、膜を成膜させるべき目的物以外の反応容器内壁、目的物を担持する冶具、配管等にも薄膜原料と同じものが付着してしまう。このような付着物は、半導体製品への微粒子の混入原因となり、高品質な薄膜製造が困難となるとともに製品の歩留りの低下を招くこともあり、随時除去することが必要であり、従来、人手あるいはクリーニングガスなどにより付着物の除去が行われていた。
【０００３】
また、半導体等においては、半導体回路を構成する各種の薄膜材料に回路パターンを形成するため、薄膜材料を部分的に除去するガスエッチングが用いられていた。
このようなクリーニングガスあるいはエッチングガスに求められる基本的な性能は、クリーニングガスの場合はクリーニング速度が速いこと、エッチングガスの場合は、目的物に対するエッチング速度が速いこと、選択性が高いことなどである。また、両者に共通して、排ガスの処理が容易であること、取り扱いが容易であること、さらに地球環境にやさしいこと等が挙げられる。
【０００４】
従来、このような付着物のクリーニングガスあるいは薄膜のエッチングガスとしては、ＣＦ4、Ｃ2Ｆ6、ＳＦ6、ＮＦ3などのパーフルオロ化合物が半導体の製造工程で大量に用いられていた。
しかしながら、これらのフッ素系ガスは、大気中で寿命の長い安定な化合物であり、また、エッチング後の排ガス処理が困難で、その処理コストが高いという問題点があった。また、地球温暖化係数（積分期間１００年値）が、ＣＦ4は６５００、Ｃ2Ｆ6は９２００、ＳＦ6は２３９００、ＮＦ3は８０００と極めて大きく、環境への悪影響が懸念されるという問題点もあった。このため、地球温暖化係数が小さく、しかも半導体のケイ素系化合物に対するクリーニング性能、あるいはケイ素系化合物膜に対するエッチング性能に優れた代替ガスの開発が求められていた。
【０００５】
そこで本願発明者らは、上記問題を解決すべく鋭意研究し、特定のフッ素系エステル化合物が、大気寿命が短く、地球温暖化に与える影響が小さく、かつ取扱いが容易であり、クリーニング後あるいはエッチング後の排ガス処理がしやすく、ケイ素系化合物膜に対し優れたクリーニング性能及びエッチング性能を有していることを見出し、本願発明を完成するに至った。
【０００６】
【発明の目的】
本発明は、地球温暖化の影響が小さく、しかも取扱いが容易であり、排ガス処理性に優れるとともに、ケイ素系化合物に対するクリーニング性能あるいはケイ素系化合物膜に対するクリーニング性能に優れ、半導体製造に好適なＣＶＤ装置等のチャンバークリーニング用ガス及びエッチングガスを提供することを目的としている。
【０００７】
【発明の概要】
本発明に係るチャンバークリーニング用ガスは、ＣＦ3ＣＯＯＣＨＦ2、Ｃ2Ｆ5ＣＯＯＣＨＦ2、ＣＦ3ＣＯＯＣ2Ｆ5及びＣ2Ｆ5ＣＯＯＣ2Ｆ5からなる群から選ばれる少なくとも１種のフッ素系化合物であることを特徴としている。また、前記フッ素系化合物は、ＣＦ3ＣＯＯＣＨＦ2またはＣ2Ｆ5ＣＯＯＣＨＦ2から選ばれる少なくとも１種であることが好ましい。前記チャンバークリーニング用ガスは、ＣＶＤ装置チャンバーのクリーニングガスであることが好ましい。前記チャンバークリーニング用ガスは、ケイ素系化合物からなる付着物のクリーニング用ガスであることが好ましい。また、前記ケイ素系化合物は、（１）ケイ素からなる化合物、（２）酸素、窒素、フッ素または炭素のうちの少なくとも１種と、ケイ素とからなる化合物、または（３）高融点金属シリサイトからなる化合物のうちの少なくとも１種であることが好ましい。
【０００８】
本発明に係るケイ素系化合物膜用エッチングガスは、ＣＦ3ＣＯＯＣＨＦ2、Ｃ2Ｆ5ＣＯＯＣＨＦ2、ＣＦ3ＣＯＯＣ2Ｆ5及びＣ2Ｆ5ＣＯＯＣ2Ｆ5からなる群から選ばれる少なくとも１種のフッ素系化合物であることを特徴としている。また、前記ケイ素系化合物膜は、（１）ケイ素からなる膜、（２）酸素、窒素、フッ素または炭素のうちの少なくとも１種と、ケイ素とからなる膜、または（３）高融点金属シリサイト膜のうちの少なくとも１種であることが好ましい。
【０００９】
さらに、前記フッ素系化合物は、ＣＦ3ＣＯＯＣＨＦ2またはＣ2Ｆ5ＣＯＯＣＨＦ2から選ばれる少なくとも１種であることが好ましい。
【００１０】
【発明の具体的説明】
本発明に係るケイ素系化合物膜用チャンバークリーニング用ガス及びエッチングガスは、特定のフッ素系エステル化合物である。以下にそれぞれについて詳細に説明する。
［チャンバークリーニング用ガス］
本発明に係る、チャンバークリーニング用ガスは、ＣＦ3ＣＯＯＣＨＦ2、Ｃ2Ｆ5ＣＯＯＣＨＦ2、ＣＦ3ＣＯＯＣ2Ｆ5及びＣ2Ｆ5ＣＯＯＣ2Ｆ5からなる群から選ばれる少なくとも１種のフッ素系化合物である。
【００１１】
このうち、本発明においては、好ましくはＣＦ3ＣＯＯＣＨＦ2及び／またはＣ2Ｆ5ＣＯＯＣＨＦ2をチャンバークリーニング用ガスとして用いることが望ましい。
なお、本明細書においてチャンバークリーニングとは、ＣＶＤ装置等の半導体製造装置内のチャンバー壁あるいは冶具、配管等に付着した付着物の除去を意味している。
【００１２】
これらのフッ素系化合物は１種単独で、または２種以上を混合して、ＣＶＤ装置等のチャンバークリーニング用ガスとして用いることができる。
このような本発明に係るチャンバークリーニング用ガスは、エステル結合を有し、大気中での寿命が極めて短く地球温暖化への寄与度が小さいことから、未反応の前記チャンバークリーニング用ガスの放出による環境影響を小さく抑えることができる。また、既存のパーフルオロ化合物の大気寿命（たとえば、ＣＦ4は５００００年、Ｃ2Ｆ6は１００００年、Ｃ3Ｆ8は７０００年、ＳＦ6は３２００年、ＮＦ3は７４０年である。）に対し、本発明に係るチャンバークリーニング用ガスの大気寿命は、数年以内と推定される。さらに、本発明に係るチャンバークリーニング用ガスは、排ガス処理が容易である。
【００１３】
またさらに、前記フッ素系化合物は、比較的沸点が低く、半導体製造条件下では気体であることから、チャンバークリーニングにおける取扱いが容易である。このようなフッ素系化合物によるチャンバークリーニングの目的化合物としては、ＣＶＤ法等により、ＣＶＤチャンバー壁あるいはＣＶＤ装置の冶具等に付着した、前記ケイ素系化合物からなる付着物が挙げられる。このようなケイ素系化合物の付着物としては、たとえば、
（１）ケイ素からなる化合物、
（２）酸素、窒素、フッ素または炭素のうちの少なくとも１種と、ケイ素とからなる化合物、または
（３）高融点金属シリサイトからなる化合物
などのうちの少なくとも１種が挙げられ、より具体的には、たとえば、Ｓｉ、ＳｉＯ2、Ｓｉ3Ｎ4、ＷＳｉ等の高融点金属シリサイトなどが挙げられる。
【００１４】
また、本発明に係るクリーニングガスは、適宜他のガスを混合して用いることができる。このような他のガスとしては、たとえば、Ｈｅ、Ｎｅ、Ａｒ、Ｏ2などが挙げられる。このような他のガスの配合量は特に限定されず、ＣＶＤ装置等のチャンバーに付着した付着物の量、厚みなどに対応して決定することができる。
【００１５】
これらのフッ素系化合物の製造方法は、特に限定されない。たとえば、ＣＦ3ＣＯＯＣＨＦ2は、次の方法により収率良く製造することができる。
（ＣＨ3ＣＯＯ）2Ｈｇ ＋ ２ＣＦ2ＨＩ → ２ＣＨ3ＣＯＯＣＨＦ2 ＋ ＨｇＩ反応温度は、２０〜８０℃、好ましくは４０〜７０℃程度であり、反応時間は、２〜３０時間、好ましくは１０〜２０時間程度であることが望ましい。前記反応は、無溶媒で行うことができる。
【００１６】
また、たとえばＣＦ3ＣＯＯＣ2Ｆ5は、ＣＨ3ＣＯＯＣ2Ｈ5に、低温（−１９６〜０℃）にて、Ｆ2ガスを直接作用させることにより得ることができる。
本発明に係るチャンバークリーニング用ガスを用いるチャンバーの材料は特に限定されず、公知の材料が挙げられる。このようなチャンバーの材料としては、たとえば、ステンレス、アルミニウム、あるいはこれらの合金などが挙げられる。 本発明に係るチャンバークリーニング用ガスは、このようなチャンバーに対しては腐食等の作用を及ぼすことが少なく、チャンバーに付着した前記付着物を選択的かつ迅速に除去することができる。
【００１７】
このような本発明に係るフッ素系化合物を用いて、チャンバー内のケイ素系化合物等からなる付着物をクリーニングするには、公知の方法が採用でき、たとえば、プラズマクリーニング、リモートプラズマクリーニング、マイクロ波クリーニングなどの各種ドライクリーニング法が適用できる。
このような本発明に係るチャンバークリーニング用ガスによれば、ケイ素系化合物を除去することが可能である。
［ケイ素系化合物膜用エッチングガス］
本発明に係る、ケイ素系化合物膜用エッチングガスは、ＣＦ3ＣＯＯＣＨＦ2、Ｃ2Ｆ5ＣＯＯＣＨＦ2、ＣＦ3ＣＯＯＣ2Ｆ5及びＣ2Ｆ5ＣＯＯＣ2Ｆ5からなる群から選ばれる少なくとも１種のフッ素系化合物である。
【００１８】
このうち、本発明においては、好ましくはＣＦ3ＣＯＯＣＨＦ2及び／またはＣ2Ｆ5ＣＯＯＣＨＦ2をケイ素系化合物膜のエッチングガスとして用いることが望ましい。
これらのフッ素系化合物は１種単独で、または２種以上を混合して、エッチングに用いることができる。
【００１９】
また、本発明に係るエッチングガスは、Ｈｅ、Ｎｅ、Ａｒ、Ｈ2、Ｎ2、Ｏ2などの単体ガス、ＣＨ4、Ｃ2Ｈ6、ＮＨ3などの化合物ガスを適宜混合して用いることができる。このような他のガスの配合量は特に限定されず、エッチングの対象物であるケイ素系化合物膜の厚み、量などに対応して決定することができる。
エッチングの目的化合物としては、ケイ素系化合物からなる薄膜等が挙げられる。このようなケイ素系化合物膜としては、たとえば、
（１）ケイ素からなる膜、
（２）酸素、窒素、フッ素または炭素のうちの少なくとも１種と、ケイ素とからなる膜、または
（３）高融点金属シリサイト膜
などのうちの少なくとも１種が挙げられる。
【００２０】
より具体的には、たとえば、Ｓｉ膜、ＳｉＯ2膜、Ｓｉ3Ｎ4膜、ＷＳｉ膜等の高融点金属シリサイト膜などが挙げられる。
このようなケイ素系化合物膜を、本発明に係るフッ素系化合物によりエッチングする方法は、公知の方法が採用でき、たとえば、プラズマエッチング、反応性イオンエッチング、マイクロ波エッチングなどの各種ドライエッチング法が適用できる。また、ケイ素系化合物膜のエッチング条件は、公知のエッチング条件を採用できる。
【００２１】
このような本発明に係るエッチングガスは、エステル結合を有するため大気中で容易に加水分解し、大気寿命が短いことから地球温暖化への寄与度が小さく、未反応の前記エッチングガスの放出における環境影響を小さく抑えることができ、また、排ガス処理も容易である。
【００２２】
【発明の効果】
本発明に係るチャンバークリーニング用ガスは、地球温暖化への寄与度が小さいことから、未反応の前記チャンバークリーニング用ガスの放出による環境影響を小さく抑えることができるとともに、排ガス処理が容易である。またこのチャンバークリーニング用ガスは、既存ガスに匹敵するクリーニング速度を有している。
【００２３】
本発明に係るケイ素系化合物膜用エッチングガスは、地球温暖化寄与度が小さいことから、未反応のエッチングガスの放出による環境影響を低く抑えることができるとともに、排ガス処理が容易である。また、ケイ素系化合物の除去を効率的に、しかも半導体パターンの寸法精度を高精度に保ちながらエッチングが可能であり、既存ガスに匹敵するエッチング性能を有している。
【００２４】
【実施例】
以下、実施例に基づいて本発明をより詳細に説明するが、これらの実施例により本発明は限定されるものではない。
【００２５】
【調製例１】
［ＣＦ3ＣＯＯＣＨＦ2の合成］
容器内を窒素で置換、乾燥した２５ｍｌのＳＵＳ−３１６製の反応容器に、（ＣＦ3ＣＯＯ）2Ｈｇを２．２ｇ（１０ｍｍｏｌ）を装入し、反応容器内を減圧した後、反応容器を液体窒素で冷却し、ＣＦ2ＨＩを２２０ｍｌ（９．１５ｍｍｏｌ）加えた。次いで、反応容器を５０℃に昇温し、この温度で１５．５時間反応させた。
【００２６】
得られた化合物（沸点１９℃）をガスクロマトグラフィー及びＦＴ−ＩＲで分析し、得られた化合物はＣＦ3ＣＯＯＣＨＦ2であることを確認した。収率は、９９％であった。
【００２７】
【実施例１】
［チャンバークリーニング］
調製例１で合成したＣＦ3ＣＯＯＣＨＦ2を３５％、酸素を６５％含有する混合ガスを用いて、圧力１１０Ｐａ、入力Ｒｆ電力２９０Ｗ、トータルガス流量６０sccmの条件下で、ＳｉＯ2膜を堆積したシリコンウェハーをＣＶＤチャンバー内に置いてＳｉＯ2膜をクリーニングした。
【００２８】
上記条件下で２分間クリーニングしたところ、クリーニング速度は５４０Å／minであった。
【００２９】
【実施例２】
［チャンバークリーニング］
調製例１で合成したＣＦ3ＣＯＯＣＨＦ2を２５％、酸素を７５％含有する混合ガスを用いて、圧力１１０Ｐａ、入力Ｒｆ電力２９０Ｗ、トータルガス流量６０sccmの条件下で、Ｓｉ3Ｎ4膜を堆積したシリコンウェハーをＣＶＤチャンバー内に置いてＳｉ3Ｎ4膜をクリーニングした。
【００３０】
上記条件下で２分間クリーニングしたところ、クリーニング速度は４８５０Å／minであった。
【００３１】
【実施例３】
［エッチング］
調製例１で合成したＣＦ3ＣＯＯＣＨＦ2を４５％、酸素を６０％含有する混合ガスを用いて、圧力１１０Ｐａ、入力Ｒｆ電力３００Ｗ、トータルガス流量６０sccmの条件下で、Ｓｉ3Ｎ4膜、ＳｉＯ2膜をそれぞれ堆積したシリコンウェハーをエッチングして、Ｓｉ3Ｎ4膜とＳｉＯ2膜の選択比（Ｓｉ3Ｎ4膜のエッチング速度／ＳｉＯ2膜のエッチング速度）を求めたところ、選択比は、１７倍であった。
【００３２】
【比較例１】
［チャンバークリーニング］
Ｃ2Ｆ6を３５％、酸素を６５％含有する混合ガスを用いて、圧力１１０Ｐａ、入力Ｒｆ電力２９０Ｗ、トータルガス流量６０sccmの条件下で、ＳｉＯ2膜を堆積したシリコンウェハーをＣＶＤチャンバー内に置いてＳｉＯ2膜をクリーニングした。
【００３３】
上記条件下で２分間クリーニングしたところ、クリーニング速度は６３０Å／minであった。
なお、Ｃ2Ｆ6は地球温暖化作用が大きいため、同作用の小さいクリーニングガスへの代替が求められているガスである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a chamber cleaning gas and an etching gas. More specifically, the present invention relates to a chamber cleaning gas and an etching gas such as a CVD apparatus suitable for manufacturing a semiconductor substrate made of a fluorine-based compound that has a small contribution to global warming.
[0002]
TECHNICAL BACKGROUND OF THE INVENTION
2. Description of the Related Art Conventionally, in a thin film device manufacturing process in semiconductor manufacturing or the like, various thin films and thick films are formed using a CVD method or the like. When such a thin film for a semiconductor is formed, the same material as the thin film raw material adheres to the inner wall of the reaction vessel other than the target object on which the film is to be formed, the jig carrying the target object, the piping, and the like. Such deposits cause contamination of semiconductor products with fine particles, which makes it difficult to produce high-quality thin films and may reduce product yield. Alternatively, deposits have been removed with a cleaning gas or the like.
[0003]
In semiconductors and the like, gas etching for partially removing the thin film material has been used to form circuit patterns on various thin film materials constituting the semiconductor circuit.
The basic performance required for such a cleaning gas or etching gas is that the cleaning speed is high in the case of the cleaning gas, the etching speed with respect to the target is high in the case of the etching gas, and the selectivity is high. is there. Further, in common with both, it is easy to treat exhaust gas, easy to handle, and friendly to the global environment.
[0004]
Conventionally, perfluoro compounds such as CF 4 , C 2 F 6 , SF 6 , and NF 3 have been used in large amounts in the semiconductor manufacturing process as cleaning gases for such deposits or etching gases for thin films.
However, these fluorine-based gases are stable compounds having a long life in the atmosphere, and there are problems in that exhaust gas treatment after etching is difficult and the treatment cost is high. In addition, the global warming potential (integral period 100-year value) is as large as 6500 for CF 4 , 9200 for C 2 F 6 , 23900 for SF 6 and 8000 for NF 3. There was also a point. For this reason, there has been a demand for the development of an alternative gas that has a low global warming potential and that is excellent in cleaning performance of silicon based semiconductor compounds or etching performance of silicon based compound films.
[0005]
Therefore, the inventors of the present application have made extensive studies to solve the above-mentioned problems, and the specific fluorine-based ester compound has a short atmospheric life, has a small effect on global warming, is easy to handle, and after cleaning or etching. The inventors have found that the later exhaust gas treatment is easy and that the silicon compound film has excellent cleaning performance and etching performance, and the present invention has been completed.
[0006]
OBJECT OF THE INVENTION
The present invention is a CVD apparatus that is less affected by global warming, is easy to handle, has excellent exhaust gas treatment properties, has excellent cleaning performance for silicon compounds, or cleaning performance for silicon compound films, and is suitable for semiconductor manufacturing It is an object to provide a chamber cleaning gas and an etching gas.
[0007]
SUMMARY OF THE INVENTION
The chamber cleaning gas according to the present invention includes at least one fluorine-based compound selected from the group consisting of CF 3 COOCHF 2 , C 2 F 5 COOCHF 2 , CF 3 COOC 2 F 5 and C 2 F 5 COOC 2 F 5 . It is characterized by being. Further, the fluorine compound is preferably at least one selected from CF 3 COOCHF 2 or C 2 F 5 COOCHF 2. The chamber cleaning gas is preferably a cleaning gas for a CVD apparatus chamber. The chamber cleaning gas is preferably a cleaning gas for deposits made of a silicon compound. In addition, the silicon-based compound includes (1) a compound composed of silicon, (2) a compound composed of at least one of oxygen, nitrogen, fluorine, and carbon and silicon, or (3) a refractory metal silicite. It is preferable that it is at least 1 type of the compound which becomes.
[0008]
The etching gas for a silicon-based compound film according to the present invention is at least one selected from the group consisting of CF 3 COOCHF 2 , C 2 F 5 COOCHF 2 , CF 3 COOC 2 F 5 and C 2 F 5 COOC 2 F 5 . It is a fluorine compound. The silicon-based compound film may be (1) a film made of silicon, (2) a film made of silicon and at least one of oxygen, nitrogen, fluorine or carbon, or (3) a refractory metal silicite. It is preferably at least one of the membranes.
[0009]
Furthermore, the fluorine-based compound is preferably at least one selected from CF 3 COOCHF 2 or C 2 F 5 COOCHF 2 .
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The silicon-based compound film chamber cleaning gas and the etching gas according to the present invention are specific fluorine-based ester compounds. Each will be described in detail below.
[Gas for chamber cleaning]
The chamber cleaning gas according to the present invention is at least one fluorine-based material selected from the group consisting of CF 3 COOCHF 2 , C 2 F 5 COOCHF 2 , CF 3 COOC 2 F 5 and C 2 F 5 COOC 2 F 5. A compound.
[0011]
Among these, in the present invention, it is preferable to use CF 3 COOCHF 2 and / or C 2 F 5 COOCHF 2 as the chamber cleaning gas.
In this specification, chamber cleaning means removal of deposits attached to a chamber wall, jig, piping, or the like in a semiconductor manufacturing apparatus such as a CVD apparatus.
[0012]
These fluorine compounds can be used alone or in combination of two or more as a chamber cleaning gas for a CVD apparatus or the like.
Such a chamber cleaning gas according to the present invention has an ester bond and has a very short lifetime in the atmosphere and a small contribution to global warming. Environmental impact can be kept small. In addition, the atmospheric lifetime of existing perfluoro compounds (for example, CF 4 is 50,000 years, C 2 F 6 is 10,000 years, C 3 F 8 is 7000 years, SF 6 is 3200 years, and NF 3 is 740 years). On the other hand, the atmospheric lifetime of the chamber cleaning gas according to the present invention is estimated to be within several years. Further, the chamber cleaning gas according to the present invention can be easily treated with an exhaust gas.
[0013]
Furthermore, since the fluorine-based compound has a relatively low boiling point and is a gas under semiconductor manufacturing conditions, it is easy to handle in chamber cleaning. Examples of the target compound for chamber cleaning with such a fluorine-based compound include deposits made of the silicon-based compound attached to a CVD chamber wall or a jig of a CVD apparatus by a CVD method or the like. Examples of such silicon compound deposits include:
(1) a compound comprising silicon,
(2) At least one of oxygen, nitrogen, fluorine, or carbon and a compound composed of silicon, or (3) a compound composed of refractory metal silicite, and the like. Examples thereof include refractory metal silicite such as Si, SiO 2 , Si 3 N 4 , and WSi.
[0014]
In addition, the cleaning gas according to the present invention can be used by appropriately mixing other gases. Examples of such other gas include He, Ne, Ar, O 2 and the like. The blending amount of such other gas is not particularly limited, and can be determined in accordance with the amount, thickness, and the like of deposits attached to a chamber such as a CVD apparatus.
[0015]
The method for producing these fluorine compounds is not particularly limited. For example, CF 3 COOCHF 2 can be produced with good yield by the following method.
(CH 3 COO) 2 Hg + 2CF 2 HI → 2CH 3 COOCHF 2 + HgI The reaction temperature is 20 to 80 ° C., preferably about 40 to 70 ° C., and the reaction time is 2 to 30 hours, preferably 10 to 10 ° C. It is desirable to be about 20 hours. The reaction can be performed without a solvent.
[0016]
For example, CF 3 COOC 2 F 5 can be obtained by direct action of F 2 gas on CH 3 COOC 2 H 5 at a low temperature (−196 to 0 ° C.).
The material of the chamber using the chamber cleaning gas according to the present invention is not particularly limited, and may be a known material. Examples of such a chamber material include stainless steel, aluminum, and alloys thereof. The chamber cleaning gas according to the present invention is less likely to cause corrosion or the like on such a chamber, and can selectively and quickly remove the deposits attached to the chamber.
[0017]
In order to clean the deposits made of the silicon compound in the chamber using such a fluorine compound according to the present invention, a known method can be adopted, for example, plasma cleaning, remote plasma cleaning, microwave cleaning, etc. Various dry cleaning methods can be applied.
With such a chamber cleaning gas according to the present invention, it is possible to remove the silicon-based compound.
[Etching gas for silicon compound film]
The silicon compound film etching gas according to the present invention is at least one selected from the group consisting of CF 3 COOCHF 2 , C 2 F 5 COOCHF 2 , CF 3 COOC 2 F 5 and C 2 F 5 COOC 2 F 5. This is a fluorine-based compound.
[0018]
Among these, in the present invention, it is preferable to use CF 3 COOCHF 2 and / or C 2 F 5 COOCHF 2 as an etching gas for the silicon-based compound film.
These fluorine compounds can be used for etching alone or in combination of two or more.
[0019]
In addition, as an etching gas according to the present invention, a simple gas such as He, Ne, Ar, H 2 , N 2 , or O 2 and a compound gas such as CH 4 , C 2 H 6 , or NH 3 are appropriately mixed and used. Can do. The blending amount of such other gas is not particularly limited, and can be determined according to the thickness, amount, etc., of the silicon-based compound film that is an object to be etched.
Examples of the target compound for etching include a thin film made of a silicon-based compound. As such a silicon-based compound film, for example,
(1) a film made of silicon,
(2) At least one of oxygen, nitrogen, fluorine or carbon and a film made of silicon, or (3) a refractory metal silicite film, and the like.
[0020]
More specifically, for example, refractory metal silicite films such as Si film, SiO 2 film, Si 3 N 4 film, and WSi film can be used.
As a method of etching such a silicon-based compound film with the fluorine-based compound according to the present invention, a known method can be adopted, and various dry etching methods such as plasma etching, reactive ion etching, and microwave etching are applied. it can. Moreover, well-known etching conditions can be employ | adopted for the etching conditions of a silicon-type compound film | membrane.
[0021]
Since the etching gas according to the present invention has an ester bond, it easily hydrolyzes in the atmosphere, and since the atmospheric lifetime is short, the contribution to global warming is small and in the release of the unreacted etching gas. Environmental impact can be kept small, and exhaust gas treatment is easy.
[0022]
【The invention's effect】
Since the chamber cleaning gas according to the present invention has a small contribution to global warming, it is possible to suppress the environmental influence due to the release of the unreacted chamber cleaning gas, and the exhaust gas treatment is easy. The chamber cleaning gas has a cleaning speed comparable to that of the existing gas.
[0023]
Since the etching gas for silicon-based compound film according to the present invention has a small contribution to global warming, it is possible to suppress the environmental impact due to the release of unreacted etching gas and to facilitate the exhaust gas treatment. Moreover, it is possible to perform etching while efficiently removing the silicon-based compound and maintaining the dimensional accuracy of the semiconductor pattern with high accuracy, and the etching performance is comparable to that of the existing gas.
[0024]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited by these Examples.
[0025]
[Preparation Example 1]
[Synthesis of CF 3 COOCHF 2 ]
Into a 25 ml reaction vessel made of SUS-316 that was replaced with nitrogen and dried, the reactor was charged with 2.2 g (10 mmol) of (CF 3 COO) 2 Hg, and the reaction vessel was depressurized. After cooling with liquid nitrogen, 220 ml (9.15 mmol) of CF 2 HI was added. Next, the reaction vessel was heated to 50 ° C. and reacted at this temperature for 15.5 hours.
[0026]
The obtained compound (boiling point 19 ° C.) was analyzed by gas chromatography and FT-IR, and it was confirmed that the obtained compound was CF 3 COOCHF 2 . The yield was 99%.
[0027]
[Example 1]
[Chamber cleaning]
Silicon in which a SiO 2 film is deposited using a mixed gas containing 35% CF 3 COOCHF 2 synthesized in Preparation Example 1 and 65% oxygen under the conditions of a pressure of 110 Pa, an input Rf power of 290 W, and a total gas flow rate of 60 sccm. The wafer was placed in a CVD chamber to clean the SiO 2 film.
[0028]
When cleaned for 2 minutes under the above conditions, the cleaning rate was 540 kg / min.
[0029]
[Example 2]
[Chamber cleaning]
Using a mixed gas containing 25% CF 3 COOCHF 2 synthesized in Preparation Example 1 and 75% oxygen, a Si 3 N 4 film is deposited under conditions of pressure 110 Pa, input Rf power 290 W, and total gas flow rate 60 sccm. The silicon wafer was placed in a CVD chamber to clean the Si 3 N 4 film.
[0030]
When cleaned for 2 minutes under the above-mentioned conditions, the cleaning speed was 4850 kg / min.
[0031]
[Example 3]
[etching]
Using a mixed gas containing 45% CF 3 COOCHF 2 synthesized in Preparation Example 1 and 60% oxygen, under the conditions of pressure 110 Pa, input Rf power 300 W, total gas flow rate 60 sccm, Si 3 N 4 film, SiO 2 The silicon wafer on which the two films were deposited was etched to obtain the selectivity ratio between the Si 3 N 4 film and the SiO 2 film (Si 3 N 4 film etching rate / SiO 2 film etching rate). 17 times.
[0032]
[Comparative Example 1]
[Chamber cleaning]
Using a mixed gas containing 35% C 2 F 6 and 65% oxygen, a silicon wafer having a SiO 2 film deposited in a CVD chamber under the conditions of pressure 110 Pa, input Rf power 290 W, total gas flow 60 sccm The SiO 2 film was placed and cleaned.
[0033]
When cleaned for 2 minutes under the above conditions, the cleaning rate was 630 Å / min.
Since C 2 F 6 has a large global warming effect, it is a gas that is required to be replaced with a cleaning gas having a small effect.
Claims (8)
（１）ケイ素からなる化合物、
（２）酸素、窒素、フッ素または炭素のうちの少なくとも１種と、ケイ素とからなる化合物、または
（３）高融点金属シリサイトからなる化合物
のうちの少なくとも１種であることを特徴とする請求項４に記載のチャンバークリーニング用ガス。The silicon compound is
(1) a compound comprising silicon,
(2) At least one of oxygen, nitrogen, fluorine or carbon and a compound composed of silicon, or (3) at least one compound composed of a refractory metal silicite. Item 5. The chamber cleaning gas according to Item 4.
（１）ケイ素からなる膜、
（２）酸素、窒素、フッ素または炭素のうちの少なくとも１種と、ケイ素とからなる膜、または
（３）高融点金属シリサイト膜
のうちの少なくとも１種であることを特徴とする請求項６に記載のケイ素系化合物膜用エッチングガス。The silicon-based compound film is
(1) a film made of silicon,
7. (2) At least one of oxygen, nitrogen, fluorine or carbon and silicon, or (3) at least one of refractory metal silicite films. Etching gas for silicon-based compound film as described in 1.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000207473A JP3865113B2 (en) | 2000-07-07 | 2000-07-07 | Cleaning gas and etching gas |
| PCT/JP2001/005761 WO2002005338A1 (en) | 2000-07-07 | 2001-07-03 | Cleaning gas and etching gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000207473A JP3865113B2 (en) | 2000-07-07 | 2000-07-07 | Cleaning gas and etching gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002020796A JP2002020796A (en) | 2002-01-23 |
| JP3865113B2 true JP3865113B2 (en) | 2007-01-10 |
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|---|---|---|---|
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| WO (1) | WO2002005338A1 (en) |
Families Citing this family (1)
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06163476A (en) * | 1992-11-18 | 1994-06-10 | Sony Corp | Dry etching method |
| US5626775A (en) * | 1996-05-13 | 1997-05-06 | Air Products And Chemicals, Inc. | Plasma etch with trifluoroacetic acid and derivatives |
| JPH10223614A (en) * | 1997-02-12 | 1998-08-21 | Daikin Ind Ltd | Etching gas and cleaning gas |
| JP2000038675A (en) * | 1998-07-22 | 2000-02-08 | Central Glass Co Ltd | Cleaning gas |
-
2000
- 2000-07-07 JP JP2000207473A patent/JP3865113B2/en not_active Expired - Lifetime
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| WO2002005338A1 (en) | 2002-01-17 |
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