JP4613587B2 - 酸化膜形成方法とその装置 - Google Patents
酸化膜形成方法とその装置 Download PDFInfo
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- JP4613587B2 JP4613587B2 JP2004326760A JP2004326760A JP4613587B2 JP 4613587 B2 JP4613587 B2 JP 4613587B2 JP 2004326760 A JP2004326760 A JP 2004326760A JP 2004326760 A JP2004326760 A JP 2004326760A JP 4613587 B2 JP4613587 B2 JP 4613587B2
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- C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
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- 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
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- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
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Description
J.Vac.Sci.Technol.A21,728(2003)
図1は本実施形態例の酸化膜形成装置の概略図である。また、図2には本実施形態例に係るプロセスフローを示した。
Si(OC2H5)4 + 8O3 → SiO2 + 8CO2 + 10H2O
TMSの場合
3Si(CH3)4 + 16O3 → 3SiO2 + 12CO2 + 18H2O
但し、基板温度が室温以上の場合、例えば300℃の場合、基板から感じる熱輻射によりオゾンが基板表面に到達する以前に熱分解するため、結果基板表面でのCVD反応ではなく気相でのCVD反応になってしまうため(表面反応の促進により、下地材料の材質や表面状態によって成長膜の表面形状において凹凸が現れることや成長速度が変わるという下地依存性が解消できる、特開平8−31814参照)、上記以上の量のオゾンガスを導入する必要がある。オゾンガスの気相での寿命をオゾンの熱分解の反応速度定数を利用して計算した。
図8は本実施形態例の酸化膜形成装置の概略図である。
図9は本実施形態例に係るプロセスフローを示したものである。
また、シリコン酸化膜の作成ばかりでなく、金属酸化膜作成の際にも、有機金属を含有する原料ガスとオゾン含有ガスとを減圧状態で交互に基板に供給するとよい。このとき、本実施形態例に係る酸化膜形成装置も実施形態例1〜3に示した酸化膜形成装置と同様の構成を採用すればよい。
10…処理炉
11,12,13…配管、V1…原料ガス導入バルブ、V2…オゾン含有ガス導入バルブ、V3…排気バルブ
14…ヒーターユニット
15…紫外光光源
16…紫外光導入窓
Claims (21)
- Si(シリコン)−O(酸素)結合若しくはSi(シリコン)−C(炭素)結合を有する有機シリコンまたは金属元素−酸素結合若しくは金属元素−炭素結合を有する有機金属を含有する原料ガスとオゾン含有ガスとを交互に基板に供給して、この基板の表面に酸化膜を形成する酸化膜形成方法であって、
前記基板の温度を室温から400℃の範囲で調整する共に、前記基板が格納された反応炉内に前記原料ガスを満たし、この原料ガスが満たされた反応炉内に、オゾン濃度が0.1〜100vol%の範囲で調整された前記オゾン含有ガスを供給すること
を特徴とする酸化膜形成方法。 - 前記原料ガスとオゾン含有ガスを交互に供給するサイクルでの原料ガスの導入圧力は、
原料ガス中にシリコン原子を1個含むものである場合、0.1〜100Paの範囲とすること
原料ガス中にシリコン原子をn個含むものである場合、前記圧力範囲の1/nを上限にすること
を特徴とする請求項1記載の酸化膜形成方法。 - 前記原料ガスに対するオゾン含有ガスは、少なくとも原料ガスに含まれる有機シリコンまたは有機金属を全て酸化シリコンまたは金属酸化物に酸化する化学当量分供給すること
を特徴とする請求項1または2項記載の酸化膜形成方法。 - オゾン含有ガスの供給量は、オゾン含有ガスを供給した後の閉じた前記基板と原料ガスとオゾン含有ガスとの反応系において残留するオゾンの熱分解による圧力上昇が確認できる程度に設定すること
を特徴とする請求項3記載の酸化膜形成方法。 - 前記前記原料ガスとオゾン含有ガスの交互供給の各サイクルにおいて、1サイクル当りの成膜速度は基板温度が低いほど小さくすること
を特徴とする請求項1から4のいずれか1項に記載の酸化膜形成方法。 - 前記成膜速度は基板温度200℃で0.2〜1.0nm/サイクルとすること
を特徴とする請求項5記載の酸化膜形成方法。 - 前記成膜速度は基板温度300℃で0.2〜5.0nm/サイクルとすること
を特徴とする請求項5記載の酸化膜形成方法。 - 前記原料ガスとオゾン含有ガスを交互に供給するにあたり、前記基板に紫外光を照射すること
を特徴とする請求項1から7のいずれか1項に記載の酸化膜形成方法。 - 前記反応炉は、前記基板に、前記反応炉に形成された紫外光照射窓を介して、紫外光を照射しながら前記原料ガスとオゾン含有ガスを交互に供給して前記基板の表面に酸化膜を形成する反応炉であって、
この反応炉に設けられた紫外光照射窓から前記基板までの距離は、オゾン分圧で吸収される導入紫外光の吸収深さに比べ短くなるように調整すること
を特徴とする請求項8記載の酸化膜形成方法。 - 前記反応炉は減圧コールドウォール方式またはホットウォール方式のものであることを特徴とする請求項1から9のいずれか1項に記載の酸化膜形成方法。
- 請求項1から10のいずれか1項に記載の酸化膜形成方法において、
前記基板がポリシリコン系の材料からなる場合、前記原料ガスとオゾン含有ガスとを前記基板に交互供給する前に、前記基板に一定温度の基板温度のもとオゾン含有ガスを一定の流量及び時間供給して、この基板に熱酸化膜を形成すること
を特徴とする酸化膜形成方法。 - 前記熱酸化膜を形成する際に、前記基板に紫外光を照射すること
を特徴とする請求項11記載の酸化膜形成方法。 - Si(シリコン)−O(酸素)結合若しくはSi(シリコン)−C(炭素)結合を有する有機シリコンまたは金属元素−酸素結合若しくは金属元素−炭素結合を有する有機金属を含有する原料ガスとオゾン含有ガスとを交互に基板に供給して、この基板の表面にシリコン酸化膜を形成する酸化膜形成装置であって、
前記基板を保持するヒーターユニットを格納した反応炉と、前記原料ガスを前記反応炉内に導入する原料ガス導入バルブを備えた配管と、オゾン含有ガスを前記反応炉内に導入するオゾン含有ガス導入バルブを備えた配管と、前記反応炉内のガスを排出する排気バルブを備えた配管とを備え、
前記原料ガスとオゾン含有ガスを交互に前記反応炉内に供給するように前記原料ガス導入バルブとオゾン含有ガス導入バルブと排気バルブが開閉動作する際、
前記ヒーターユニットは前記基板の温度を室温から400℃までの範囲で調整し、前記原料ガス導入バルブは前記反応炉内に前記原料ガスを満たし、オゾン含有ガス導入バルブはこの原料ガスが満たされた反応炉内にオゾン濃度が0.1〜100vol%の範囲で調整された前記オゾン含有ガスを供給すること
を特徴とする酸化膜形成装置。 - 前記原料ガスとオゾン含有ガスを交互に供給するサイクルでの原料ガスの導入圧力が、
原料ガス中にシリコン原子を1個含むものである場合、0.1〜100Paの範囲とすること、
原料ガス中にシリコン原子をn個含むものである場合、前記圧力範囲の1/nが上限とすることとなるように原料ガス導入バルブと排気バルブが開閉動作すること
を特徴とする請求項13記載の酸化膜形成装置。 - オゾン含有ガス導入バルブは、少なくとも原料ガスに含まれる有機シリコンまたは有機金属を全て酸化シリコンまたは金属酸化物に酸化する化学当量分のオゾン含有ガスを供給するように、開閉動作すること
を特徴とする請求項13または14項記載の酸化膜形成装置。 - オゾン含有ガス導入バルブは、オゾン含有ガスの供給量が、オゾン含有ガスを供給した後の閉じた前記基板と原料ガスとオゾン含有ガスとの反応系において残留するオゾンの熱分解による圧力上昇が確認できる程度に設定されるように、開閉動作すること
を特徴とする請求項15記載の酸化膜形成装置。 - 原料ガス導入バルブとオゾン含有ガス導入バルブと排気バルブは、
前記原料ガスとオゾン含有ガスの交互供給の各サイクルにおいて、基板温度が低いほど1サイクル当りの成膜速度が小さくなるように、開閉動作すること
を特徴とする請求項13から16のいずれか1項に記載の酸化膜形成装置。 - 前記成膜速度は基板温度200℃で0.2〜1.0nm/サイクルとすること
を特徴とする請求項17記載の酸化膜形成装置。 - 前記成膜速度は基板温度300℃で0.2〜5.0nm/サイクルとすること
を特徴とする請求項17記載の酸化膜形成装置。 - 前記反応炉は、前記基板に紫外光を照射するための光源と、前記照射された紫外光を透過する紫外光照射窓とを備えたこと
を特徴とする請求項13から19のいずれか1項に記載の酸化膜形成装置。 - 前記ヒーターユニットは、前記紫外光照射窓から前記基板までの距離がオゾン分圧で吸収される導入紫外光の吸収深さに比べ短くなるように、前記基板の位置を調整すること
を特徴とする請求項20記載の酸化膜形成装置。
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JP2004326760A JP4613587B2 (ja) | 2004-08-11 | 2004-11-10 | 酸化膜形成方法とその装置 |
US11/659,728 US7772133B2 (en) | 2004-08-11 | 2005-08-01 | Method and equipment for forming oxide film |
PCT/JP2005/014054 WO2006016496A1 (ja) | 2004-08-11 | 2005-08-01 | 酸化膜形成方法とその装置 |
KR1020077003069A KR100859115B1 (ko) | 2004-08-11 | 2005-08-01 | 산화막 형성방법 및 장치 |
TW094126930A TWI295079B (en) | 2004-08-11 | 2005-08-09 | Method and device for forming oxide film |
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JP4258536B2 (ja) * | 2006-08-11 | 2009-04-30 | 独立行政法人産業技術総合研究所 | 結晶化金属酸化物薄膜の製造方法 |
US20080044590A1 (en) * | 2006-08-21 | 2008-02-21 | National Institute Of Advanced Industrial Science And Technology | Manufacturing Method of Phosphor Film |
JP5052071B2 (ja) * | 2006-08-25 | 2012-10-17 | 株式会社明電舎 | 酸化膜形成方法とその装置 |
JP4524300B2 (ja) * | 2007-08-10 | 2010-08-11 | 東京エレクトロン株式会社 | 成膜方法 |
US20090081356A1 (en) * | 2007-09-26 | 2009-03-26 | Fedorovskaya Elena A | Process for forming thin film encapsulation layers |
JP2010103495A (ja) * | 2008-09-29 | 2010-05-06 | Adeka Corp | 半導体デバイス、その製造装置及び製造方法 |
JP2011054894A (ja) * | 2009-09-04 | 2011-03-17 | Meidensha Corp | 酸化膜形成方法 |
JP5653018B2 (ja) * | 2009-09-24 | 2015-01-14 | 東京エレクトロン株式会社 | 酸化マンガン膜の成膜方法 |
JP2011176177A (ja) * | 2010-02-25 | 2011-09-08 | Hitachi Kokusai Electric Inc | 半導体デバイスの製造方法、半導体デバイスおよび基板処理装置 |
WO2012008954A1 (en) | 2010-07-14 | 2012-01-19 | Primaxx, Inc. | Process chamber pressure control system and method |
JP5792972B2 (ja) * | 2011-03-22 | 2015-10-14 | 株式会社日立国際電気 | 半導体装置の製造方法及び基板処理装置 |
TWI502645B (zh) | 2012-03-09 | 2015-10-01 | Air Prod & Chem | 低溫含矽膜 |
JP6061240B2 (ja) * | 2012-06-12 | 2017-01-18 | 国立研究開発法人物質・材料研究機構 | オゾンビーム発生装置 |
JP2015012179A (ja) | 2013-06-28 | 2015-01-19 | 住友電気工業株式会社 | 気相成長方法 |
JP2015149461A (ja) | 2014-02-10 | 2015-08-20 | 東京エレクトロン株式会社 | 金属酸化物膜の成膜方法および成膜装置 |
JP6225837B2 (ja) * | 2014-06-04 | 2017-11-08 | 東京エレクトロン株式会社 | 成膜装置、成膜方法、記憶媒体 |
JP6225842B2 (ja) * | 2014-06-16 | 2017-11-08 | 東京エレクトロン株式会社 | 成膜装置、成膜方法、記憶媒体 |
JP6415918B2 (ja) * | 2014-09-29 | 2018-10-31 | 国立研究開発法人物質・材料研究機構 | シリコン表面パッシベーション方法、表面パッシベーション処理されたシリコンの製造方法、及び、太陽電池の製造方法 |
KR102153780B1 (ko) * | 2015-03-09 | 2020-09-08 | 도시바 미쓰비시덴키 산교시스템 가부시키가이샤 | 태양 전지의 제조 방법 |
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