JP2010280991A - 薄膜形成方法 - Google Patents
薄膜形成方法 Download PDFInfo
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- JP2010280991A JP2010280991A JP2010195006A JP2010195006A JP2010280991A JP 2010280991 A JP2010280991 A JP 2010280991A JP 2010195006 A JP2010195006 A JP 2010195006A JP 2010195006 A JP2010195006 A JP 2010195006A JP 2010280991 A JP2010280991 A JP 2010280991A
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- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
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- 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
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Abstract
【解決手段】 プラズマを用いる原子層蒸着装置の反応器内において基板上に金属酸化物膜を形成する方法であって、反応器内に金属原料化合物を供給する段階と、反応器内に酸素ガスを供給する段階と、反応器内に所定時間中に酸素プラズマを生じさせる段階と、を含む金属酸化物膜の形成方法。
【選択図】図1
Description
[(Ti原料→N原料)→(NまたはHプラズマ)→]
または
[{(Ti原料→N原料)→}n回繰り返し(NまたはHプラズマ)→]
を繰り返して特性が改善されたTiN膜を形成し得る。ここで、各供給原料が予め反応することを防止するために、各原料の供給前後にパージガスを用いて反応器をパージする段階を行う。
[(金属原料)→酸素ガス→(酸素プラズマ)→]
を繰り返して金属酸化物を形成し得、この場合、パージガスを用いた場合より高速で金属酸化物膜を形成し得る。他の例として、金属原料と反応しない窒素ガス(N2)及び水素ガス(H2)を用い、
[(金属原料)→(窒素ガス+水素ガス)→(窒素水素プラズマ)→]
を繰り返してパージガスを用いた場合より高速で金属窒化物膜を形成し得る。金属窒化物膜は、窒素ガス(N2)及び水素ガス(H2)の代わりにアンモニア(NH3)プラズマを反応器内に生じさせる方法によっても蒸着可能であるが、前記窒素ガス及び水素ガスを用いる方法は、パージガスを用いずに工程サイクルを具現し得るという長所がある。また、
[(金属原料)→水素ガス→(水素プラズマ)→]
の工程サイクルを繰り返すことにより、低温でもTi、Al及びWなどの純粋な金属膜を形成し得る。
酸素ガスは、有機金属原料と遅く反応するために、一般に、400℃以下の温度において有機金属原料及び酸素ガスを原料として用いて金属酸化物膜を形成し難いばかりではなく、成膜速度が極めて遅い。これにより、この実施例では、酸素プラズマを用いてアルミニウム酸化膜を形成する方法について説明する。図1は、本発明の実施例1によるALD法を示すフローチャートである。
図3は、本実施例により酸化タンタル(Ta2O5)膜を形成するALD法を示すフローチャートである。図3に示されたように、TAE(dmae)として知られているジメトキシアミドエチル酸テトラエチル酸タンタル(Ta(OC2H5)4(OCH2CH2N(CH3)2)をタンタルの原料として用いて基板温度250℃、反応器圧力4Torrの条件下でTAE(dmae)(0.3秒)→Ar(1.7秒)→O2(1秒)→(O2+プラズマ)(2秒)→Ar(1秒)の段階よりなる工程サイクル(全体周期は6秒、図3における段階303ないし307)を繰り返して酸化タンタル(Ta2O5)膜を形成した。全体周期である6秒のうち2秒間180WのRF電力を加えて酸素プラズマを生じさせた。このようにして形成された膜の厚みは、原料供給周期当たり0.67Åであった。
この実施例では、プラズマを用いたALD法によるストロンチウム−チタン酸化物(SrTiO3;STO)を形成する方法について説明する。STOやバリウム−ストロンチウム−チタン酸化物((Ba,Sr)TiO3;BST)は誘電率が高いために、高集積DRAMの記憶素子において、電荷貯蔵用キャパシタの誘電物質として用いられる。
この実施例では、プラズマを用いるALD法によりBST膜を形成する方法について述べる。まず、Ba(thd)2を反応器に供給し、アルゴンガスにより反応器をパージし、酸素を供給し、反応器にプラズマを生じさせた後にプラズマを切って、アルゴンガスにより反応器をパージする。次に、Ti(O−i−Pr)4(またはTi(O−i−Pr)2(thd)2)及びSr(thd)2を各々用いて同じ工程サイクルを行う。次に、Ti(O−i−Pr)4(またはTi(O−i−Pr)2(thd)2)を反応器に供給し、アルゴンガスにより反応器をパージし、酸素を供給し、反応器にプラズマを生じさせた後にプラズマを切って、アルゴンガスにより反応器をパージする。このようにBa−O−Ti−O−Sr−O−Ti−Oの原料供給サイクルを一回以上繰り返して所望の厚みのBST膜を形成する。金属原料の供給順序を変えてBa→O→Sr→O→Ti→O→Ti→OまたはSr→O→Ba→O→Ti→O→Ti→Oの段階よりなる原料供給サイクルを繰り返して所望の厚みのBST膜を形成しても良い。
ストロンチウム−ビスマス−タンタル酸化物(SrBi2Ta2O9;SBT)や鉛−ジルコニウム−チタン酸化物(Pb(Zr,Ti)O3;PZT)のような強誘電体膜は電源が切れても記憶された情報が消去されない不揮発性記憶素子の製造に用いられる。実施例5A及び実施例5BではSBT膜を形成する方法について説明し、PZT膜を形成する過程は実施例6において説明する。
この実施例では、Sr及びTaが1:2の割合で混合されているエチル酸及びストロンチウムタンタル(Sr{Ta(OEt)6}2)(ここで、原料としてエチル酸及びストロンチウムタンタルdmae((Sr{Ta(OEt)5(dmae)}2) を用いても良い)を用いてSBT膜を形成する方法について説明する。
この実施例では、プラズマを用いるALD法によりPZT膜を形成する方法について説明する。Pb(thd)2を反応器に供給し、アルゴンガスを用いて反応器をパージし、酸素を供給し、反応器にプラズマを生じさせた後にプラズマを切って、アルゴンガスを用いて反応器をパージする。次に、Zr(O−t−Bu)4(またはZr(O−t−Bu)2(thd)2)及びPb(thd)2を各々用いて同じ工程サイクルを行う。最終的に、Ti(O−i−Pr)4(またはTi(O−i−Pr)2(thd)2)を反応器に供給し、アルゴンガスを用いて反応器をパージし、酸素を供給し、反応器にプラズマを生じさせた後にプラズマを切って、アルゴンガスを用いて反応器をパージする。このようにPb→O→Zr→O→Pb→O→Ti→O順序の原料供給サイクルを1回以上繰り返せば、所望の厚みのPZT膜が形成される。Pb:Zr:Tiの割合を調節するためには、前記原料供給サイクルを繰り返す間にある元素の原料供給段階を追加または省略しても良い。例えば、Pb→O→Zr→O→Pb→O→Ti→Oの原料供給サイクルにおいてTi→Oの供給段階を追加または省略しても良く、Zr→Oの供給段階を追加してZr:Tiの割合を変えても良い。
酸化シリコン(SiO2)より誘電率が一層高いジルコニウム−シリコン酸化物(Zr−Si−O)及びハフニウム−シリコン酸化物(Hf−Si−O)はトランジスターのゲート絶縁膜として良い材料になり得る。
この実施例では、プラズマを用いるALD法によりハフニウム−シリコン酸化物膜を形成する方法について述べる。すなわち、t−ブチル酸ハフニウム(Hf(O−t−Bu)4)を反応器に供給してアルゴンガスを用いて反応器をパージし、酸素を供給し、反応器にプラズマを生じさせた後にプラズマを切って、アルゴンガスを用いて反応器をパージする。その後、テトラエチル酸シリコン(TEOS)を反応器に供給し、アルゴンガスを用いて反応器をパージし、酸素を供給し、反応器にプラズマを生じさせた後にプラズマを切って、アルゴンガスを用いて反応器をパージする。前述した過程を1回または1回以上繰り返して所望の厚みのハフニウムシリコン酸化物(Hf−Si−O)膜を得る。
この実施例では、半導体工程において金属配線材料として用いられるアルミニウム膜をトリアルキルアルミニウム(Al(CnH2n+1)3、ここで、n=1〜6)原料及び水素(H2)プラズマを用いたALD法により形成する。トリアルキルアルミニウム(Al(CnH2n+1)3、ここで、n=1〜6)としては、トリメチルアルミニウム(Al(CH3)3)、トリエチルアルミニウム(Al(C2H5)3)またはトリイソブチルアルミニウム(Al(CH2CH(CH3)2)3)などが用いられ得るが、成膜温度が高いほどアルミニウム膜の誘電性が一層良くなる。従って、熱分解温度が最も高いトリメチルアルミニウムを原料として用いた方が、ALDの反応温度が最も高いために好ましい。
または
R3Al→H2→(H2+プラズマ)→H2(1秒未満)
シリコン基板上の半導体素子(トランジスタなど)、キャパシタ、抵抗素子などを接続したり電源を供給したりするために、アルミニウム(Al)のような金属が用いられる。最近は銅も用いられているが、プラズマを用いた原子層CVD法により銅原子の拡散防止膜であるTaN膜またはTa−N−C膜を形成すれば、プラズマを用いない場合に比べて膜の電気伝導度が高まる。例えば、Taのアミド化合物またはアミドイミド化合物及びアンモニア(NH3)ガスを順次に供給するサイクルを繰り返すALD法に比べて、プラズマを生じさせる段階をさらに含む工程サイクルを繰り返すALD法の場合、一層高い電気伝導度を有した膜を形成し得る。そして、アンモニア(NH3)ガスを供給する段階の代わりに、プラズマにより活性化された窒素(N2)ガスを供給する段階を含むサイクルを繰り返すALD法によっても、膜の電気伝導度を高め得る。
この実施例では、テトラキスジメチルアミドチタン(TDMAT)をチタン原料として用いるプラズマALD法による窒化チタン膜の形成方法について説明する。TDMAT→Ar→NH3→Arの原料供給サイクルを繰り返して形成したTiN膜の比抵抗は10000μΩ・cmであった。これに対し、TDMAT→Ar→NH3→Ar→(H2+プラズマ)の工程サイクルを数十回ないし数百回繰り返してALD法により形成したTiN膜は、比抵抗が1800μΩ・cmとはるかに低かった。
この実施例では、反応性がほとんどない窒素ガス(N2)を用いて窒化チタン(TiN)膜または窒化タンタル膜(TaN)を蒸着する方法について説明する。TiCl4(窒化タンタル膜の場合にはTaCl5)をチタン(またはタンタル)の蒸着原料として用いて基板温度300℃、反応器圧力5Torrの条件下でTiCl4(またはTaCl5)(0.2秒)→(N2+H2)(1.2秒)→(プラズマ発生)(2.0秒)の工程サイクルを繰り返す。反応ガス及びパージガスの機能を合わせ持つ(N2+H2)の混合ガスの供給のために、N2及びH2が各々60sccmの流量にて供給され、150ワット(8インチのウェーハ基準)のRF電力を加えてプラズマを生じさせる。このような過程を通じて形成された膜の厚みは、工程サイクル当たり0.5Åであった。この時、N2(またはH2)の流量を調節して窒化チタン(または窒化タンタル膜)の組成を調節することが可能である。すなわち、水素の供給なしにN2だけを供給することも可能であり、H2の割合を調節して窒化チタン(または窒化タンタル)膜内のTi(またはTa)の濃度を調節することも可能である。反応時の基板の温度が低過ぎると、TiCl4(またはTaCl5)ガスの凝縮により粒子が形成され、その一方、高過ぎると、配線材料に悪影響を及ぼすため、反応時の基板の温度は150℃ないし500℃の範囲内に維持することが好ましい。また、反応器内の圧力は、0.5ないし10Torrの範囲内に、プラズマ発生のためのRF電力は、基板の上面の単位面積当たり0.01ないし2.0W/cm2の範囲内に維持することが好ましい。
シリコン基板上の半導体素子やキャパシタ及び抵抗素子などの素子を接続したり電源を供給したりするためには、アルミニウム(Al)のような金属を用いる。最近は銅も用いられているが、銅を蒸着する時に銅原子が絶縁膜に拡散することを防止するために拡散防止膜が必要となる。拡散防止膜としては、TiNやTaNなどが使用でき、これらの材料は銅との接着力が悪いという問題点があるため、この実施例では、このような問題を解決し得る拡散防止膜の蒸着方法について説明する。
この実施例では、プラズマを用いるALD法により銅との接着力に優れており、且つ、銅原子の拡散を防止し得る拡散防止膜を形成する方法について説明する。まず、窒化チタン(TiN)(または窒化タンタル(TaN))膜を形成するための工程サイクルを繰り返して銅原子の拡散を防止し得る厚みのTiN(またはTaN)膜をALD法により形成する。その後、窒化チタン(TiN)(または窒化タンタル(TaN))を形成する工程サイクルの間に銅との接着性に優れた金属膜を形成する工程サイクルの追加を次第に増やす。 例えば、Ti(またはTa)→Ar→N→Arの供給サイクル2回及びCu(またはAl)→Ar→H→Arの供給サイクル1回を含む拡大サイクルを2回繰り返した後、Ti(またはTa)→Ar→N→Arの供給サイクル1回及びCu(またはAl)→Ar→H→Arの供給サイクル1回を含む拡大サイクルを2回繰り返し、Ti(またはTa)→Ar→N→Arの供給サイクル1回及びCu(またはAl)→Ar→H→Arの供給サイクル2回を含む拡大サイクルを2回繰り返した後、Cu(またはAl)→Ar→H→Arの供給サイクルを3回繰り返す。このように窒化チタン(TiN)(または窒化タンタル(TaN))から銅との接着性に優れた金属へと組成が次第に変わる膜を形成することにより、拡散防止膜と銅配線との間の接着力が改善される結果が得られる。
この実施例では、原料供給周期に同期させたプラズマを用いるALD法によりチタン(Ti)膜またはタンタル(Ta)膜を蒸着する方法について説明する。TiCl4(タンタルの場合にはTaCl5)をチタン(またはタンタル)の原料として用いて基板の温度300℃、反応器の圧力5Torrの条件下でTiCl4(またはTaCl5)(0.2秒)→H2(1.9秒)→(プラズマ発生)(2.0秒)の工程サイクルを繰り返す。この時、150ワット(8インチのウェーハ基準)のRF電力を加えてプラズマを生じさせる。この実施例では、反応ガス兼パージガスとしてH2を用いたが、パージの効率性を高めるために、ヘリウムまたはアルゴンなどの不活性ガスを混合して用いても良い。反応時の基板の温度が低過ぎると、TiCl4(またはTaCl5)ガスの凝縮により粒子が形成され、その一方、高過ぎると、配線材料に悪影響を及ぼすため、反応時の基板の温度は、150℃ないし500℃の範囲内に維持することが好ましい。また、反応器内の圧力は、0.5ないし10Torrの範囲内に、プラズマ発生のためのRF電力は、基板の上面の単位面積当たり0.01ないし2.0W/cm2の範囲内に維持することが好ましい。
この実施例では、原料供給周期に同期させたプラズマを用いるALD法によりタングステン(W)膜を蒸着する方法について説明する。WF6をタングステンの原料として用いて基板の温度300℃、反応器の圧力5Torrの条件下でWF6(1.0秒)→(H2+Ar)(6.0秒)→(プラズマ発生)(2.0秒)の工程サイクルを繰り返す。この時、WF6を2sccmの流量にて供給し、反応ガス及びパージガスの機能を合わせ持つN2+Arの混合ガスの供給のために、N2及びArを各々100sccmの流量にて供給する。また、100ワット(8インチのウェーハ基準)のRF電力を加えてプラズマを生じさせる。反応時の基板の温度は、100℃ないし450℃の範囲内に維持することが好ましい。また、反応器内の圧力は、0.5ないし10Torrの範囲内に、プラズマ発生のためのRF電力は、基板の上面の単位面積当たり0.01ないし2.0W/cm2の範囲内に維持することが好ましい。
この実施例では、原料供給周期に同期させたプラズマを用いるALD法により窒化タングステン(WN)膜を蒸着する方法について説明する。WF6をタングステンの原料として用いて基板の温度300℃、反応器の圧力5Torrの条件下でWF6(1.0秒)→(H2+N2)(6.0秒)→(プラズマ発生)(2.0秒)→(H2+N2)(1秒)の工程サイクルを繰り返す。この時、WF6を2sccmの流量にて供給し、反応ガス及びパージガスの機能を合わせ持つ(N2+H2)の混合ガスの供給のために、N2及びArを各々100sccm及び50sccmの流量にて供給する。また、100ワット(8インチのウェーハ基準)のRF電力を加えてプラズマを生じさせる。ここで、N2(またはH2)の流量を調節して窒化タングステン膜の組成を調節することが可能である。すなわち、水素の供給なしにN2のみを供給することも可能であり、H2の割合を調節してWN内のWの濃度を調節することも可能である。反応時の基板の温度は100℃ないし450℃の範囲内に維持することが好ましい。また、反応器内の圧力は0.5ないし10Torrの範囲内に、プラズマ発生のためのRF電力は基板の上面の単位面積当たり0.01ないし2.0W/cm2の範囲内に維持することが好ましい。
Claims (29)
- プラズマを用いる原子層蒸着装置の反応器内において基板上に金属酸化物膜を形成する方法であって、
前記反応器内に金属原料化合物を供給する段階と、
前記反応器内に酸素ガスを供給する段階と、
前記反応器内に所定時間中に酸素プラズマを生じさせる段階と、を含む金属酸化物膜の形成方法。 - 前記金属原料化合物を供給する段階前、段階後または段階前後共に前記反応器の内部を不活性ガスでパージする段階をさらに含むことを特徴とする請求項1に記載の金属酸化物膜の形成方法。
- 前記金属原料化合物がトリメチルアルミニウム(Al(CH3)3)であり、前記金属酸化物が酸化アルミニウム(Al2O3)であることを特徴とする請求項1に記載の金属酸化物膜の形成方法。
- 前記金属原料化合物がジメトキシアミドエチル酸テトラエチル酸タンタル(Ta(OC2H5)4(OC2H4N(CH3)2)またはエチル酸タンタル(Ta(OC2H5)5)であり、
前記金属酸化物が酸化タンタル(Ta2O5)であることを特徴とする請求項1に記載の金属酸化物膜の形成方法。 - プラズマを用いる原子層蒸着装置の反応器内において基板上にストロンチウム−チタン酸化物(STO)膜を形成する方法であって、
(5−1)前記反応器内にストロンチウム有機金属化合物を供給する段階と、
(5−2)前記反応器内に酸素ガスを供給し、所定の第1の時間中に酸素ガスプラズマを生じさせる段階と、
(5−3)前記反応器内にチタン有機金属化合物を供給する段階と、
(5−4)前記反応器内に酸素ガスを供給して所定の第2の時間中に酸素ガスプラズマを生じさせる段階と、を含む工程サイクルを一回以上繰り返すが、
前記(5−1)ないし(5−4)の各段階後に前記反応器内を不活性ガスでパージする段階をさらに含むことを特徴とするSTO膜の形成方法。 - プラズマを用いる原子層蒸着装置の反応器内において基板上にバリウム−ストロンチウム−チタン酸化物(BST)膜を形成する方法であって、
(6−1)前記反応器内にバリウム有機金属化合物を供給する段階と、
(6−2)前記反応器内に酸素ガスを供給して所定の第1の時間中に酸素ガスプラズマを生じさせる段階と、
(6−3)前記反応器内にチタン有機金属化合物を供給する段階と、
(6−4)前記反応器内に酸素ガスを供給して所定の第2の時間中に酸素ガスプラズマを生じさせる段階と、
(6−5)前記反応器内にストロンチウム有機金属化合物を供給する段階と、
(6−6)前記反応器内に酸素ガスを供給して所定の第3の時間中に酸素ガスプラズマを生じさせる段階と、
(6−7)前記反応器内にチタン有機金属化合物を供給する段階と、
(6−8)前記反応器内に酸素ガスを供給して所定の第4の時間中に酸素ガスプラズマを生じさせる段階と、を含む工程サイクルを繰り返すが、
前記(6−1)ないし(6−8)の各段階後に前記反応器内を不活性ガスでパージする段階をさらに含むことを特徴とするBST膜の形成方法。 - プラズマを用いる原子層蒸着装置の反応器内において基板上にストロンチウム−ビスマス−タンタル酸化物(SBT)膜を形成する方法であって、
(7−1)前記反応器内にストロンチウム有機金属化合物を供給する段階と、
(7−2)前記反応器内に酸素ガスを供給して所定の第1の時間中に酸素ガスプラズマを生じさせる段階と、
(7−3)前記反応器内にビスマス有機金属化合物を供給する段階と、
(7−4)前記反応器内に酸素ガスを供給して所定の第2の時間中に酸素ガスプラズマを生じさせる段階と、
(7−5)前記反応器内にタンタル有機金属化合物を供給する段階と、
(7−6)前記反応器内に酸素ガスを供給して所定の第3の時間中に酸素ガスプラズマを生じさせる段階と、
(7−7)前記反応器内にビスマス有機金属化合物を供給する段階と、
(7−8)前記反応器内に酸素ガスを供給して所定の第4の時間中に酸素ガスプラズマを生じさせる段階と、
(7−9)前記反応器内にタンタル有機金属化合物を供給する段階と、
(7−10)前記反応器内に酸素ガスを供給して所定の第5の時間中に酸素ガスプラズマを生じさせる段階と、を含む工程サイクルを繰り返すが、
前記(7−1)ないし(7−10)の各段階後に前記反応器内を不活性ガスでパージする段階をさらに含むことを特徴とするSBT膜の形成方法。 - プラズマを用いる原子層蒸着装置の反応器内において基板上にストロンチウム−ビスマス−タンタル酸化物(SBT)膜を形成する方法であって、
(8−1)前記反応器内にビスマス有機金属化合物を供給する段階と、
(8−2)前記反応器内に酸素ガスを供給して所定の第1の時間中に酸素ガスプラズマを生じさせる段階と、
(8−3)前記反応器内にストロンチウム及びタンタルが1:2の割合で混合された有機金属化合物を供給する段階と、
(8−4)前記反応器内に酸素ガスを供給して所定の第2の時間中に酸素ガスプラズマを生じさせる段階と、を含む工程サイクルを繰り返すが、
前記(8−1)ないし(8−4)の各段階後に前記反応器内を不活性ガスでパージする段階をさらに含むことを特徴とするSBT膜の形成方法。 - プラズマを用いる原子層蒸着装置の反応器内において基板上に鉛−ジルコニウム−チタン酸化物(PZT)膜を形成する方法であって、
(9−1)前記反応器内に鉛有機金属化合物を供給する段階と、
(9−2)前記反応器内に酸素ガスを供給して所定の第1の時間中に酸素ガスプラズマを生じさせる段階と、
(9−3)前記反応器内にジルコニウム有機金属化合物を供給する段階と、
(9−4)前記反応器内に酸素ガスを供給して所定の第2の時間中に酸素ガスプラズマを生じさせる段階と、
(9−5)前記反応器内に鉛有機金属化合物を供給する段階と、
(9−6)前記反応器内に酸素ガスを供給して所定の第3の時間中に酸素ガスプラズマを生じさせる段階と、
(9−7)前記反応器内にチタン有機金属化合物を供給する段階と、
(9−8)前記反応器内に酸素ガスを供給して所定の第4の時間中に酸素ガスプラズマを生じさせる段階と、を含む工程サイクルを繰り返すが、
前記(9−1)ないし(9−8)の各段階後に前記反応器内を不活性ガスでパージする段階をさらに含むことを特徴とするPZT膜の形成方法。 - プラズマを用いる原子層蒸着装置の反応器内において基板上にジルコニウム−シリコン酸化物(Zr−Si−O)膜を形成する方法であって、
(10−1)前記反応器内にジルコニウム有機金属化合物を供給する段階と、
(10−2)前記反応器内に酸素ガスを供給して所定の第1の時間中に酸素ガスプラズマを生じさせる段階と、
(10−3)前記反応器内にシリコン化合物を供給する段階と、
(10−4)前記反応器内に酸素ガスを供給して所定の第2の時間中に酸素ガスプラズマを生じさせる段階と、を含む工程サイクルを繰り返すが、
前記(10−1)ないし(10−4)の各段階後に前記反応器内を不活性ガスでパージする段階をさらに含むことを特徴とするZr−Si−O膜の形成方法。 - プラズマを用いる原子層蒸着装置の反応器内において基板上にハフニウム−シリコン酸化物(Hf−Si−O)膜を形成する方法であって、
(11−1)前記反応器内にハフニウム有機金属化合物を供給する段階と、
(11−2)前記反応器内に酸素ガスを供給して所定の第1の時間中に酸素ガスプラズマを生じさせる段階と、
(11−3)前記反応器内にシリコン化合物を供給する段階と、
(11−4)前記反応器内に酸素ガスを供給して所定の第2の時間中に酸素ガスプラズマを生じさせる段階と、を含む工程サイクルを繰り返すが、
前記(11−1)ないし(11−4)の各段階後に前記反応器内を不活性ガスでパージする段階をさらに含むことを特徴とするHf−Si−O膜の形成方法。 - アルミニウム膜を形成する方法であって、
反応器にトリアルキルアルミニウム(Al(CnH2n+1)3、ここで、n=1〜6)を供給する段階と、
前記反応器に水素ガスを供給して所定の時間中に水素ガスプラズマを生じさせる段階と、を含む工程サイクルを一回以上繰り返すことを特徴とする方法。 - プラズマを用いる原子層蒸着装置の反応器内において基板上に金属窒化物膜を形成する方法であって、
前記反応器内に金属原料化合物を供給する段階と、
前記反応器内に窒素と水素との混合ガスを供給する段階と、
前記反応器内に所定の時間中に窒素と水素との混合ガスのプラズマを生じさせる段階と、を含むことを特徴とする金属窒化物膜の形成方法。 - 前記金属原料化合物が4塩化チタン(TiCl4)であり、前記金属窒化物が窒化チタン(TiN)であることを特徴とする請求項13に記載の方法。
- 窒化チタンの蒸着中に前記反応器内に配された前記基板の温度を150℃ないし500℃の範囲内に維持し、前記反応器内の圧力を0.5Torrないし10Torrの範囲内に維持し、前記プラズマを生じさせるために加えられるRF電力が前記基板の上面の単位面積当たり0.01ないし2.0W/cm2の範囲内であることを特徴とする請求項14に記載の方法。
- 前記金属原料化合物が5塩化タンタル(TaCl5)であり、前記金属窒化物が窒化タンタル(TaN)であることを特徴とする請求項13に記載の方法。
- 誘電性金属窒化物膜を形成する方法であって、
反応器に金属原料を供給する段階と、
前記反応器にアンモニアガスを供給する段階と、
前記反応器に水素ガスを供給して所定の時間中に水素ガスプラズマを生じさせる段階と、を含む工程サイクルを繰り返して誘電性がさらに高い金属窒化物膜を形成することを特徴とする方法。 - タンタルの窒化炭化(Ta−N−C)膜を形成する方法であって、
反応器に窒素を含むタンタルの有機化合物原料を供給する段階と、
前記反応器に水素ガスを供給して所定の時間中に水素ガスプラズマを生じさせる段階と、を含む工程サイクルを一回以上繰り返すことを特徴とするタンタルの窒化炭化膜の形成方法。 - プラズマを用いる原子層蒸着装置の反応器内において基板上に銅配線を形成するために、銅原子の絶縁層への拡散を防止する拡散防止膜及び銅との接着性を高めるための接着膜を形成する方法であって、
窒化チタン膜を形成する第1の工程サイクルと、アルミニウム膜を形成する第2の工程サイクルとを繰り返して行い、窒化チタンからアルミニウムへと組成が変わる層を順次に形成するが、
前記第1の工程サイクルは、
前記反応器内にチタン化合物を供給する段階と、
前記反応器内を不活性ガスでパージする段階と、
前記反応器内にアンモニアまたは窒素ガスを供給して所定の第1の時間中にアンモニアまたは窒素ガスプラズマを生じさせる段階と、
前記反応器内を不活性ガスでパージする段階と、を含み、
前記第2の工程サイクルは、
前記反応器内に銅またはアルミニウム化合物を供給する段階と、
前記反応器内を不活性ガスでパージする段階と、
前記反応器内に水素ガスを供給して所定の第2の時間中に水素ガスプラズマを生じさせる段階と、
前記反応器内を不活性ガスでパージする段階と、を含むことを特徴とする接着膜の形成方法。 - プラズマを用いる原子層蒸着装置の反応器内において基板上に銅配線をするために、銅原子の絶縁層への拡散を防止する拡散防止膜及び銅との接着性を高めるための接着膜を形成する方法であって、
窒化タンタル膜を形成する第1の工程サイクルと、アルミニウム膜を形成する第2の工程サイクルとを繰り返して行い、窒化タンタルからアルミニウムへと組成が変わる層を順次に形成するが、
前記第1の工程サイクルは、
前記反応器内にタンタル化合物を供給する段階と、
前記反応器内を不活性ガスでパージする段階と、
前記反応器内にアンモニアまたは窒素ガスを供給して所定の第1の時間中にアンモニアまたは窒素ガスプラズマを生じさせる段階と、
前記反応器内を不活性ガスでパージする段階と、を含み、
前記第2の工程サイクルは、
前記反応器内に銅またはアルミニウム化合物を供給する段階と、
前記反応器内を不活性ガスでパージする段階と、
前記反応器内に水素ガスを供給して所定の第2の時間中に水素ガスプラズマを生じさせる段階と、
前記反応器内を不活性ガスでパージする段階と、を含むことを特徴とする接着膜の形成方法。 - 前記金属原料化合物が6フッ化タングステン(WF6)であり、金属窒化物が窒化タングステン(WN)であることを特徴とする請求項13に記載の方法。
- 窒化タングステンの蒸着中に前記反応器内に配された前記基板の温度を100℃ないし450℃の範囲内に維持し、前記反応器内の圧力を0.5Torrないし10Torrの範囲内に維持し、前記プラズマを生じさせるために加えられるRF電力が前記基板の上面の単位面積当たり0.01ないし2.0W/cm2の範囲内であることを特徴とする請求項21に記載の方法。
- 窒化タンタルの蒸着中に前記反応器内に配された前記基板の温度を150℃ないし500℃の範囲内に維持し、前記反応器内の圧力を0.5Torrないし10Torrの範囲内に維持し、前記プラズマを生じさせるために加えられるRF電力が前記基板の上面の単位面積当たり0.01ないし2.0W/cm2の範囲内であることを特徴とする請求項16に記載の方法。
- チタン膜を形成する方法であって、
反応器に4塩化チタン(TiCl4)を供給する段階と、
前記反応器に水素ガスまたは水素ガスと不活性ガスとの混合ガスを供給し、所定の時間中に水素ガスまたは前記混合ガスのプラズマを生じさせる段階と、を含む工程サイクルを一回以上繰り返すことを特徴とする方法。 - チタンの蒸着中に前記反応器内に配された前記基板の温度を150℃ないし500℃の範囲内に維持し、前記反応器内の圧力を0.5Torrないし10Torrの範囲内に維持し、前記プラズマを生じさせるために加えられるRF電力が前記基板の上面の単位面積当たり0.01ないし2.0W/cm2の範囲内であることを特徴とする請求項24に記載の方法。
- タングステン膜を形成する方法であって、
反応器に6フッ化タングステン(WF6)を供給する段階と、
前記反応器に水素ガスと不活性ガスとの混合ガスを供給し、所定の時間中に前記混合ガスのプラズマを生じさせる段階と、を含む工程サイクルを一回以上繰り返すことを特徴とする方法。 - タングステンの蒸着中に前記反応器内に配された前記基板の温度を100℃ないし450℃の範囲内に維持し、前記反応器内の圧力を0.5Torrないし10Torrの範囲内に維持し、前記プラズマを生じさせるために加えられるRF電力が前記基板の上面の単位面積当たり0.01ないし2.0W/cm2の範囲内であることを特徴とする請求項26に記載の方法。
- タンタル膜を形成する方法であって、
反応器に5塩化タンタル(TaCl5)を供給する段階と、
前記反応器に水素ガスまたは水素ガスと不活性ガスとの混合ガスを供給し、所定の時間中に水素ガスまたは前記混合ガスのプラズマを生じさせる段階と、を含む工程サイクルを一回以上繰り返すことを特徴とする方法。 - タンタルの蒸着中に前記反応器内に配された前記基板の温度を150℃ないし500℃の範囲内に維持し、前記反応器内の圧力を0.5Torrないし10Torrの範囲内に維持し、前記プラズマを生じさせるために加えられるRF電力が前記基板の上面の単位面積当たり0.01ないし2.0W/cm2の範囲内であることを特徴とする請求項28に記載の方法。
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JP7447432B2 (ja) | 2019-11-05 | 2024-03-12 | 東京エレクトロン株式会社 | 基板を処理する装置、原料カートリッジ、基板を処理する方法、及び原料カートリッジを製造する方法 |
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EP1292970A1 (en) | 2003-03-19 |
JP4684706B2 (ja) | 2011-05-18 |
WO2001099166A1 (en) | 2001-12-27 |
JP2010278473A (ja) | 2010-12-09 |
EP1292970B1 (en) | 2011-09-28 |
EP1292970A4 (en) | 2007-12-19 |
US7141278B2 (en) | 2006-11-28 |
US20070048455A1 (en) | 2007-03-01 |
US20040009307A1 (en) | 2004-01-15 |
JP3687651B2 (ja) | 2005-08-24 |
JP2003536272A (ja) | 2003-12-02 |
JP2005277426A (ja) | 2005-10-06 |
US7485349B2 (en) | 2009-02-03 |
JP2010275641A (ja) | 2010-12-09 |
EP2293322A1 (en) | 2011-03-09 |
JP2005229129A (ja) | 2005-08-25 |
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