JP5171625B2 - 半導体デバイスの製造方法及び基板処理装置 - Google Patents
半導体デバイスの製造方法及び基板処理装置 Download PDFInfo
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- JP5171625B2 JP5171625B2 JP2008525899A JP2008525899A JP5171625B2 JP 5171625 B2 JP5171625 B2 JP 5171625B2 JP 2008525899 A JP2008525899 A JP 2008525899A JP 2008525899 A JP2008525899 A JP 2008525899A JP 5171625 B2 JP5171625 B2 JP 5171625B2
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Description
少なくとも1枚の基板を処理室内に搬入する工程と、
第1の原料である金属化合物あるいはケイ素化合物と、第2の原料である酸素原子を含む酸化原料と、第3の原料である水素化原料とを、前記処理室内に所定回数繰り返し供給して前記基板表面に金属酸化膜あるいはケイ素酸化膜を形成する工程と、
前記基板を前記処理室内から搬出する工程と、を有し、
前記金属酸化膜あるいはケイ素酸化膜を形成する工程では、
前記第1の原料、前記第2の原料、前記第3の原料を前記処理室内に供給するごとに、それぞれ前記処理室内を不活性ガスによりパージする半導体デバイスの製造方法が提供される。
少なくとも1枚の基板を処理する処理室と、
第1の原料である金属化合物あるいはケイ素化合物を前記処理室内に供給する第1の供給系と、
第2の原料である酸素原子を含む酸化原料を前記処理室内に供給する第2の供給系と、
第3の原料である水素化原料を前記処理室内に供給する第3の供給系と、
前記処理室内の雰囲気を排気する排気系と、
前記第1の供給系、前記第2の供給系、前記第3の供給系を制御して、前記第1の原料、前記第2の原料、前記第3の原料を前記処理室内に所定回数繰り返し供給させ、前記第1の原料、前記第2の原料、前記第3の原料を前記処理室内に供給するごとに、それぞれ前記処理室内を不活性ガスによりパージさせる制御部と、
を有する基板処理装置が提供される。
M.A.AlamとM.L.GreenはHfCl4とH2Oの反応系においてHfO2の成膜速度を以下の式(1)(2)で表した。 (Journal of Applied Physics, Vol. 94, 2003)
dNHfO / dC = KCOV NOH 式(1)
dNOH / dC = K2 (N0− NSiOH) + (αCOV − 1)KCOVNOH 式(2)
ここで、NHfOはALD反応後に単位面積あたりに堆積したHfO2膜の総量、CはALDのサイクル数、KCOVはHfCl4と反応するヒドロキシル基(-OH)の数、NOHはヒドロキシル基の表面濃度、K2は新しくSiと結合するヒドロキシル基の速度定数を表している。
第1のステップではまず反応室内に金属有機化合物原料であるTDMASを流し、Si基板表面に吸着させる。第2のステップでは不活性ガスでパージを行い反応室内の残留Si原料を反応室外に排出する。第3ステップで第2の原料ガスであるオゾンを流して基板に吸着した第1の原料ガスTDMASのジメチルアミンN(Me)2基を脱離させる。第4ステップでは不活性ガスにより反応室内をパージして、第5ステップで原子状水素(水素プラズマ)を反応室内に供給する。原子状水素(水素プラズマ)により基板表面はSi-OHに置換される。第6ステップで不活性ガスにより反応室内をパージする。これら第1のステップから第6のステップを所定回数繰り返す。その結果、基板表面にケイ素酸化膜(SiO2)が形成される。
1つのサイクルは4工程であり、第1のステップではまず反応室内にケイ素化合物原料であるTDMASを流し、Si基板表面にこの原料を吸着させる。第2のステップでは不活性ガスによりパージを行い反応室内の残留Si原料を反応室外に排出する。第3のステップでは酸化材が流され、Si基板表面に吸着したSi原料とO3の反応によりSiO2を形成する。第4のステップでは不活性ガスにより反応室内がパージされ、反応室内の残留オゾンは反応室外に排出される。それそれのステップ時間は一例としては第1ステップ(Si原料供給工程)は1−30秒、第2ステップ(パージ工程)は5-15秒、第3ステップ(O3供給工程)は5−60秒、第4ステップ(パージ工程)は5-15秒である。
なお、本実施形態の処理炉202では、SiO2のようなケイ素酸化膜やHfO2のような金属酸化膜が成膜される。その材料として、SiO2用としてはTDMAS(トリス(ジメチルアミノ)シラン、SiH(NMe2)3)、HfO2用として、TEMAH(テトラキス(メチルエチルアミノ)ハフニウム、Hf(NEtMe)4)、TDEAH(テトラキス(ジエチルアミノ)ハフニウム、Hf(NEt2)4)などのアミノ系原料などが用いられる。尚、Meはメチル基(CH3)、Etはエチル基(C2H5)をそれぞれ表している。又、金属化合物としてアルミニウム原子、チタン原子、ジルコニウム原子、ハフニウム原子、タンタル原子、ルテニウム原子、イリジウム原子を含む有機化合物や、前記原子の塩化物から選ばれた原料をも用いることができる。
バルブ243を開としてポンプ19により処理室内を真空に引いた後、バルブ31を開として第1のガスを処理室内に供給する。第1のガスであるTDMASは液体材料であるため液体原料供給ユニット15にて気化され流量制御される。一定時間バルブ31を開として原料を処理室内に供給して第1の原料を基板上に吸着させる。このとき処理室201内の圧力は1〜10000Paとし、好ましくは26-266Paの範囲であって、例えば66Paに維持する。この後、バルブ31を閉とする。
その後、処理室内の第1の原料を排出(パージ)するためキャリアガスがキャリアガス供給管51から流れ、マスフローコントローラ41により流量調整される。このとき処理室201内の圧力は1〜10000Paとし、好ましくは26-266Paの範囲であって、例えば66Paに維持する。
バルブ34を開として第2 のガスを処理室内に供給する。第2のガスであるオゾンはオゾン供給ユニット16にて流量制御される。一定時間バルブ34を開として原料を処理室内に供給する。このとき処理室201内の圧力は1〜10000Paとし、好ましくは26-266Paの範囲であって、例えば66Paに維持する。この後、バルブ34を閉とする。
その後、処理室内の第2の原料を排出(パージ)するためキャリアガスをキャリアガス供給管52から流し、マスフローコントローラ42により流量調整する。このとき処理室201内の圧力は1〜10000Paとし、好ましくは26-266Paの範囲であって、例えば66Paに維持する。
バルブ35を開として第3のガスを反応室内に供給する。第3のガスである水素はバッファ室内に設けられた電極により原子状水素(水素プラズマ)を発生する。この時電極に印加される高周波としては一般的には13.56MHzの周波数が用いられる。水素流量はマスフローコントローラ44にて流量制御される。一定時間バルブ35を開として原料を反応室内に供給して第3の原料を供給する。このとき処理室201内の圧力は1〜10000Paとし、好ましくは26-266Paの範囲であって、例えば66Paに維持する。この後、バルブ35を閉とする。
その後、反応室内の第3の原料を排出(パージ)するためキャリアガスがキャリアガス供給管56から流れ、マスフローコントローラ45により流量調整される。このとき処理室201内の圧力は1〜10000Paとし、好ましくは26-266Paの範囲であって、例えば66Paに維持する。
少なくとも1枚の基板を処理室内に搬入する工程と、
第1の原料である金属化合物あるいはケイ素化合物と、第2の原料である酸素原子を含む酸化原料と、第3の原料である水素化原料とを、前記処理室内に所定回数繰り返し供給して前記基板表面に金属酸化膜あるいはケイ素酸化膜を形成する工程と、
前記基板を前記処理室内から搬出する工程と、
を有する半導体デバイスの製造方法が提供される。
前記第2の原料と前記第3の原料とを前記処理室内に供給することで前記基板表面の反応サイトをOH基に置換する。
前記金属酸化膜あるいはケイ素酸化膜を形成する工程では、
前記第1の原料、第2の原料、第3の原料を前記処理室内に供給するごとに、それぞれ前記処理室内を不活性ガスによりパージする。
前記金属酸化膜あるいはケイ素酸化膜を形成する工程では、
前記第1の原料と前記第3の原料とを前記処理室内に供給するごとに、それぞれ前記処理室内をパージガスによりパージし、
前記第2の原料を前記処理室内に供給した後は、前記処理室内をパージガスによりパージしない。
前記金属酸化膜あるいはケイ素酸化膜を形成する工程では、
前記第1〜第3の原料を、前記第1の原料、前記第2の原料、前記第3の原料の順序で、前記処理室内に供給する。
前記金属酸化膜あるいはケイ素酸化膜を形成する工程では、
前記第1〜第3の原料を、前記第1の原料、前記第3の原料、前記第2の原料の順序で、前記処理室内に供給する。
前記金属酸化膜あるいはケイ素酸化膜は、Al2O3, TiO2, ZrO2, HfO2, Ta2O5, RuO2, IrO2, SiO2からなる群から選択される一つからなる膜である。
前記第1の原料は、金属化合物あるいはケイ素化合物としてアルミニウム原子、チタン原子、ジルコニウム原子、ハフニウム原子、タンタル原子、ルテニウム原子、イリジウム原子或いはケイ素原子を含む有機化合物や、前記原子の塩化物からなる群から選ばれた一つの原料である。
前記第1の原料が、M Hn[OCR1R2R3]m−n、 M Hn[N R4R5] m−nである。
但し、Mは上記に記載の金属を示し、mは該金属の安定価数、nは0〜2の整数(Mが珪素以外の原子である場合には0を表す)、R1〜R5は水素または炭素数1から4の中間にエーテル結合を含んでも良いアルキル基である。
前記第2の原料は、オゾン(O3)、過酸化水素(H2O2)、酸素或いは原子状酸素から選ばれた原料である。
前記第3の原料は、脱離水素を含む原料或いは水素プラズマから選ばれた原料である。
前記不活性ガスとしてヘリウム(He)、ネオン(Ne)、アルゴン(Ar)、窒素(N2)を用いる。
前記金属酸化膜あるいはケイ素酸化膜を形成する工程では、
前記処理室内の温度を20℃以上、700℃以下とする。
前記金属酸化膜あるいはケイ素酸化膜を形成する工程では、
前記処理室内の圧力を1Pa以上、10,000Pa以下とする。
少なくとも1枚の基板を処理する処理室と、
第1の原料である金属化合物あるいはケイ素化合物を前記処理室内に供給する第1の供給系と、
第2の原料である酸素原子を含む酸化原料を前記処理室内に供給する第2の供給系と、
第3の原料である水素化原料を前記処理室内に供給する第3の供給系と、
前記処理室内の雰囲気を排気する排気系と、
前記第1の供給系、前記第2の供給系、第3の供給系を制御して、前記第1の原料、前記第2の原料、前記第3の原料を前記処理室内に所定回数繰り返し供給させる制御部と、
を有する基板処理装置が提供される。
その結果、本発明は、半導体集積回路の製造方法において、半導体ウェーハにALD法により酸化膜を形成する技術に特に好適に利用できる。
Claims (14)
- 少なくとも1枚の基板を処理室内に搬入する工程と、
第1の原料である金属化合物あるいはケイ素化合物と、第2の原料である酸素原子を含む酸化原料と、第3の原料である水素化原料とを、前記処理室内に所定回数繰り返し供給して前記基板表面に金属酸化膜あるいはケイ素酸化膜を形成する工程と、
前記基板を前記処理室内から搬出する工程と、を有し、
前記金属酸化膜あるいはケイ素酸化膜を形成する工程では、
前記第1の原料、前記第2の原料、前記第3の原料を前記処理室内に供給するごとに、それぞれ前記処理室内を不活性ガスによりパージする半導体デバイスの製造方法。 - 請求項1に記載の半導体デバイスの製造方法において、
前記第2の原料と前記第3の原料とを前記処理室内に供給することで前記基板表面の反応サイトをOH基に置換する半導体デバイスの製造方法。 - 請求項1に記載の半導体デバイスの製造方法において、
前記金属酸化膜あるいはケイ素酸化膜を形成する工程では、
前記第1の原料と前記第3の原料とを前記処理室内に供給するごとに、それぞれ前記処理室内をパージガスによりパージし、
前記第2の原料を前記処理室内に供給した後は、前記処理室内をパージガスによりパージしない半導体デバイスの製造方法。 - 請求項1に記載の半導体デバイスの製造方法において、
前記金属酸化膜あるいはケイ素酸化膜を形成する工程では、
前記第1〜第3の原料を、前記第1の原料、前記第2の原料、前記第3の原料の順序で、前記処理室内に供給する半導体デバイスの製造方法。 - 請求項1に記載の半導体デバイスの製造方法において、
前記金属酸化膜あるいはケイ素酸化膜を形成する工程では、
前記第1〜第3の原料を、前記第1の原料、前記第3の原料、前記第2の原料の順序で、前記処理室内に供給する半導体デバイスの製造方法。 - 請求項1に記載の半導体デバイスの製造方法において、
前記金属酸化膜あるいはケイ素酸化膜は、Al 2 O 3 ,TiO 2 ,ZrO 2 ,HfO 2 ,Ta 2 O 5 ,RuO 2 ,IrO 2 ,SiO 2 からなる群から選択される一つからなる膜である半導体デバイスの製造方法。 - 請求項1に記載の半導体デバイスの製造方法において、
前記第1の原料は、金属化合物あるいはケイ素化合物としてアルミニウム原子、チタン原子、ジルコニウム原子、ハフニウム原子、タンタル原子、ルテニウム原子、イリジウム原子或いはケイ素原子を含む有機化合物や、前記原子の塩化物からなる群から選ばれた一つの原料である半導体デバイスの製造方法。 - 請求項7に記載の半導体デバイスの製造方法において、
前記第1の原料が、MH n [OCR 1 R 2 R 3 ] m−n 、MH n [NR 4 R 5 ] m−n である半導体デバイスの製造方法。
(但し、Mは請求項8に記載の金属を示し、mは該金属の安定価数、nは0〜2の整数(Mが珪素以外の原子である場合には0を表す)、R 1 〜R 5 は水素または炭素数1から4の中間にエーテル結合を含んでも良いアルキル基である) - 請求項1に記載の半導体デバイスの製造方法において、
前記第2の原料は、オゾン、過酸化水素、酸素或いは原子状酸素から選ばれた原料である半導体デバイスの製造方法。 - 請求項1に記載の半導体デバイスの製造方法において、
前記第3の原料は、脱離水素を含む原料或いは水素プラズマから選ばれた原料である半導体デバイスの製造方法。 - 請求項1に記載の半導体デバイスの製造方法において、
前記不活性ガスとしてヘリウム、ネオン、アルゴン、窒素を用いる半導体デバイスの製造方法。 - 請求項1に記載の半導体デバイスの製造方法において、
前記金属酸化膜あるいはケイ素酸化膜を形成する工程では、
前記処理室内の温度を20℃以上、700℃以下とする半導体デバイスの製造方法。 - 請求項1に記載の半導体デバイスの製造方法において、
前記金属酸化膜あるいはケイ素酸化膜を形成する工程では、
前記処理室内の圧力を1Pa以上、10,000Pa以下とする半導体デバイスの製造方法。 - 少なくとも1枚の基板を処理する処理室と、
第1の原料である金属化合物あるいはケイ素化合物を前記処理室内に供給する第1の供給系と、
第2の原料である酸素原子を含む酸化原料を前記処理室内に供給する第2の供給系と、
第3の原料である水素化原料を前記処理室内に供給する第3の供給系と、
前記処理室内の雰囲気を排気する排気系と、
前記第1の供給系、前記第2の供給系、前記第3の供給系を制御して、前記第1の原料、前記第2の原料、前記第3の原料を前記処理室内に所定回数繰り返し供給させ、前記第1の原料、前記第2の原料、前記第3の原料を前記処理室内に供給するごとに、それぞれ前記処理室内を不活性ガスによりパージさせる制御部と、
を有する基板処理装置。
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