JP7231353B2 - 改善されたゲルマニウムエッチングのシステム及び方法 - Google Patents

改善されたゲルマニウムエッチングのシステム及び方法 Download PDF

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JP7231353B2
JP7231353B2 JP2018147319A JP2018147319A JP7231353B2 JP 7231353 B2 JP7231353 B2 JP 7231353B2 JP 2018147319 A JP2018147319 A JP 2018147319A JP 2018147319 A JP2018147319 A JP 2018147319A JP 7231353 B2 JP7231353 B2 JP 7231353B2
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ミハイール コロリク,
ニティン イングル,
ディミトリ キオウシス,
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Description

[0001]本技術は、半導体処理及び装置に関する。より具体的には、本技術は、触媒変換を用いて、半導体処理中にSiGeをエッチングすることに関する。
[0002]集積回路は、基板表面上に複雑なパターンの材料層を形成する処理によって可能になる。基板上にパターン形成された材料を作るには、露出した材料を取り除くための制御された方法が必要である。化学エッチングは、様々な目的に使用されており、それには、フォトレジストの中のパターンを下層の中へ転写すること、層を薄くすること、又は表面上にすでに存在する特徴の横寸法を細くすることが含まれる。多くの場合、ある物質を他の材料よりも早くエッチングして、例えば、パターン転写プロセスを促進するエッチング処理を行うことが望ましい。上記エッチング処理は、第1の材料に対して選択的であると言われる。材料、回路、及び処理に多様性があるために、様々な材料に対して選択性を有するエッチング処理が開発されてきた。
エッチング処理は、処理で使用される材料に応じて、湿式又は乾式と呼ばれてよい。湿式HFエッチングは、他の誘電体及び材料よりもシリコン酸化物を優先的に除去する。しかしながら、湿式処理では、一部の制約されたトレンチに浸透することができず、残りの材料が変形してしまうことがある。乾式エッチングは、基板の処理領域内に形成された局所プラズマにおいて行われるが、より制約のあるトレンチに浸透することができ、壊れやすい残りの構造の変形を抑える。しかしながら、局所プラズマは、局所プラズマが放電する際に生じる電気アークによって基板に損傷を与える恐れがある。
したがって、高品質デバイス及び構造体の製造に使用することができる、改善されたシステム及び方法が必要とされている。これらの必要及びその他の必要は、本技術によって対処される。
[0005]ゲルマニウム含有材料をエッチングする例示的な方法は、半導体処理チャンバの遠隔プラズマ領域内でフッ素含有前駆体のプラズマを形成することを含み得る。当該方法は、チャンバ構成要素において画定された開孔を通してフッ素含有前駆体のプラズマ流出物を流動させることを含み得る。開孔は、触媒材料でコーティングされ得る。当該方法は、触媒材料を用いて、プラズマ流出物内のフッ素ラジカルの濃度を減少させることを含み得る。当該方法は、半導体処理チャンバの処理領域にプラズマ流出物を供給することをさらに含み得る。露出したゲルマニウム含有材料を有する基板が、処理領域内に収容され得る。当該方法は、ゲルマニウム含有材料をエッチングすることをさらに含み得る。
[0006]幾つかの実施形態では、触媒材料は、ニッケル、コバルト、バナジウム、ニオブ、タンタル、クロム、マンガン、レニウム、鉄、ルテニウム、オスミウム、パラジウム、プラチナ、ロジウム、及びイリジウムからなる群から選択された元素を含む1つ又は複数の材料を含む。これは、言及された物質のうちのいずれかの酸化物を含み得る。チャンバ構成要素は、約70℃を越える温度で維持され得る。基板は、約30℃未満の温度で維持され得る。ゲルマニウム含有材料は、SiGeであるか、又はSiGeを含み得る。ゲルマニウム含有材料は、第1のゲルマニウム含有材料であり得、第1のゲルマニウム含有材料は、シリコン又は第2のゲルマニウム含有材料に対してエッチングされ得る。第2のゲルマニウム含有材料は、第1のゲルマニウム含有材料より低いゲルマニウム濃度によって特徴付けられ得る。エッチングは、シリコン又は第2のゲルマニウム含有材料に対する第1のゲルマニウム含有材料に対して、約300:1以上の選択性を有し得る。処理チャンバ内の圧力は、約2Torrを越える圧力に維持され得る。チャンバ構成要素は、シャワーヘッド又はイオンサプレッサであってもよい。
[0007]本技術は、ゲルマニウム含有材料をエッチングする追加の方法をさらに包含する。当該方法は、半導体処理チャンバの遠隔プラズマ領域内でフッ素含有前駆体のプラズマを形成することを含み得る。当該方法は、触媒材料を含むチャンバ構成要素を通してフッ素含有前駆体のプラズマ流出物を流動させることを含み得る。当該方法は、触媒材料によって、プラズマ流出物内のフッ素ラジカルの少なくとも一部を触媒反応で変換させることを含み得る。当該方法は、半導体処理チャンバの処理領域にプラズマ流出物を供給することを含み得る。ゲルマニウム含有材料の露出領域を有する基板は、処理領域内に収容され得る。当該方法は、ゲルマニウム含有材料をエッチングすることをさらに含み得る。
[0008]幾つかの実施形態では、変換することは、触媒材料上のフッ素ラジカルから少なくとも2つのフッ素原子を含む材料を形成することを含み得る。チャンバ構成要素は、遠隔プラズマユニット供給チューブ、ブロッカプレート、フェースプレート、イオンサプレッサ、又はシャワーヘッドのうちの1つ又は複数を含み得る。触媒材料は、ニッケル、コバルト、バナジウム、ニオブ、タンタル、クロム、マンガン、レニウム、鉄、ルテニウム、オスミウム、パラジウム、プラチナ、ロジウム、及びイリジウムからなる群から選択された元素、並びにこれらの物質のうちのいずれかの酸化物であってもよく、又はこれらを含んでもよい。チャンバ構成要素は、約70℃を越える温度で維持され得る。基板は、約30℃未満の温度で維持され得る。処理チャンバ内の圧力は、約1Torrと約30Torrとの間で維持され得る。
[0009]本技術は、ゲルマニウム含有材料をエッチングする他の方法をさらに含み得る。当該方法は、半導体処理チャンバの遠隔プラズマ領域内でフッ素含有前駆体のプラズマを形成することを含み得る。当該方法は、チャンバ構成要素において画定された開孔を通してフッ素含有前駆体のプラズマ流出物を流動させることを含み得る。開孔は、触媒材料でコーティングされ得、チャンバ構成要素は、約70℃から約150℃の温度で維持され得る。当該方法は、触媒材料を用いて、プラズマ流出物内のフッ素ラジカルの濃度を減少させることを含み得る。当該方法は、半導体処理チャンバの処理領域にプラズマ流出物を供給することを含み得る。露出したゲルマニウム含有材料を有する基板は、処理領域内に収容され得る。基板は、約30℃未満の温度で維持され得る。当該方法は、ゲルマニウム含有材料をエッチングすることをさらに含み得る。
[0010]幾つかの実施形態では、触媒材料は、ニッケル、コバルト、バナジウム、ニオブ、タンタル、クロム、マンガン、レニウム、鉄、ルテニウム、オスミウム、パラジウム、プラチナ、ロジウム、及びイリジウムからなる群から選択された元素、並びにこれらの物質の酸化物を含む1つ又は複数の材料を含み得る。処理チャンバ内の圧力は、約1Torrと約30Torrとの間で維持され得る。チャンバ構成要素は、シャワーヘッド又はイオンサプレッサであってもよく、又はそれらを含んでもよい。
[0011]上記技術は、従来のシステム及び技法よりも多数の利点を提供することができる。例えば、これらの処理により、基板上の他の露出した材料に対するゲルマニウム含有材料に対して、高い選択性が可能となり得る。さらに、プラズマ工程によって、熱ベースのエッチング工程よりも調整能力が向上し得る。これら実施形態及びその他の実施形態は、その多くの利点や特徴と共に、後述の記載及び添付の図面により詳細に説明されている。
[0012]開示された技術の性質及び利点は、本明細書の残りの部分と図面を参照することによってさらに理解を深めることができる。
本技術の実施形態に係る、例示的な処理システムの一実施形態の上面図を示す。 本技術の実施形態に係る、例示的な処理チャンバの概略断面図を示す。 本技術の実施形態に係る、図2Aに示す処理チャンバの一部の詳細図を示す。 本技術の実施形態に係る、例示的なシャワーヘッドの底面図を示す。 本技術の実施形態に係る方法の例示的な工程を示す。
[0018]幾つかの図面は、概略図として含まれている。図面は例示を目的としており、縮尺どおりであると明記されていない限り、縮尺どおりであるとみなしてはならないと理解するべきである。さらに、概略図として、図面は、理解を助けるために提供されており、現実的な描写に比べてすべての態様又は情報を含まない場合があり、例示を目的として強調された素材を含むことがある。
[0019]添付の図面では、類似の構成要素及び/又は特徴は、同じ参照符号を有し得る。さらに、同じ種類の様々な構成要素は、類似の構成要素間を区別する文字により、参照符号に従って区別することができる。本明細書において第1の参照符号のみが使用される場合、その記載は、文字に関わりなく、同じ第1の参照符号を有する類似の構成要素のうちのいずれにも適用可能である。
[0020]多くの新しい半導体構造は代替材料を利用するので、ゲルマニウム及びシリコンゲルマニウム(又はSiGe)などのゲルマニウム含有材料が益々普及し得る。一部の技術では、ゲルマニウム含有材料をエッチングするためにフッ素含有前駆体を使用してもよいが、基板上の他の多くの露出した材料もエッチングの対象となり得る。例えば、プラズマ流出物内のフッ素材料(例えば、フッ素ラジカル)は、プロセス条件及び処理で利用される追加の前駆体に応じて、シリコン、窒化シリコン、又はシリコン酸化物をエッチングし得る。従来の処理は、この欠陥を受け止め、この限界に対処するために特定のプロセス条件、構造的特徴、及びエッチャント化学物質を調整してきたかもしれない。本技術では、シリコン、窒化物、及びその他の半導体材料との反応性を低下させるために特に調整されたインシトゥ(in-situ)エッチャントの生成により、これらの課題を克服することができる。これにより、従来技術よりエッチング速度が著しく向上することが可能となり得る。
[0021]残りの開示内容は、開示した技術を利用する特定のエッチング処理を通常通りに特定するものであるが、システム及び方法は、記載されたチャンバで起こり得る堆積及び洗浄処理に対しても等しく適用可能であることは、容易に理解されよう。したがって、この技術は、エッチング処理又はチャンバのみに使用されるよう限定されるとみなすべきではない。さらに、本技術の基礎を提供するために例示的なチャンバが説明されているが、本技術は、記載された単一チャンバ操作を可能にし得るいかなる半導体処理チャンバにも適用できることを理解されたい。
[0022]図1は、実施形態に係る、堆積チャンバ、エッチングチャンバ、ベーキングチャンバ、及び硬化チャンバの処理システム100の一実施形態の上面図を示す。図面では、一対の前面開口型統一ポッド(front opening unified pods:FOUP)102により、様々なサイズの基板が供給される。基板は、ロボットアーム104が受け入れ、低圧保持領域106内に置かれ、その後、タンデムセクション109a~cに位置付けされた基板処理チャンバ108a~fのうちの1つの中に配置される。基板ウエハを、保持領域106から基板処理チャンバ108a~fに搬送し、且つその逆方向の搬送を行うために、第2のロボットアーム110が使用され得る。各基板処理チャンバ108a~fは、周期的層堆積(CLD)、原子層堆積(ALD)、化学気相堆積(CVD)、物理的気相堆積(PVD)、エッチング、予洗浄、ガス抜き、配向、及び他の基板処理に加えて、本明細書に記載された乾式エッチング処理を含む数々の基板処理工程を実施するために装備され得る。
[0023]基板処理チャンバ108a~fは、基板ウエハ上で誘電膜又は金属膜を堆積、アニール、硬化、且つ/又はエッチングするために、1つ又は複数のシステム構成要素を含み得る。一構成では、2対の処理チャンバ(例えば、108c~d及び108e~f)が、基板上に材料を堆積するために使用されてもよく、第3の対の処理チャンバ(例えば、108a~b)が、堆積された材料をエッチングするために使用されてもよい。別の構成において、3対全てのチャンバ(例えば、108a~f)が、基板上の誘電体膜又は金属膜をエッチングするように構成されてもよい。記載された処理の1つ又は複数のうちのいずれかを、種々の実施形態に示した製造システムから分離された1つ又は複数のチャンバ内で実行することができる。システム100において、誘電膜のための堆積チャンバ、エッチングチャンバ、アニールチャンバ、及び硬化チャンバのさらなる構成が検討されていることを理解されよう。
[0024]図2Aは、処理チャンバ内部で区切られたプラズマ生成領域を有する例示的な処理チャンバシステム200の断面図を示す。膜(例えば、窒化チタン、窒化タンタル、タングステン、銅、コバルト、シリコン、ポリシリコン、酸化シリコン、窒化シリコン、オキシ窒化シリコン、オキシ炭化シリコン等)のエッチングをする間、処理ガスがガス注入口アセンブリ205を通って第1のプラズマ領域215内に流れることができる。遠隔プラズマシステム(RPS)201が任意選択的にシステム内に含まれ、第1のガスを処理することある。その後、ガスは、ガス注入口アセンブリ205を通って移動する。流入口アセンブリ205は、2つ以上の異なるガス供給チャネルを含むことができ、第2のチャネル(図示せず)は、含まれる場合、RPS201を迂回し得る。
[0025]ブロッカプレート203、フェースプレート217、イオンサプレッサ223、シャワーヘッド225、及び基板255が上部に配置された基板支持ペデスタル265が図示されており、各々は実施形態に従って含まれ得る。ペデスタル265は、基板の温度を制御するために熱交換流体が貫流する熱交換チャネルを有し得る。熱交換チャネルは、処理工程中に基板又はウエハを加熱且つ/又は冷却するように作動し得る。ペデスタル265のウエハ支持プラッタは、アルミニウム、セラミック、又はこれらの組み合わせを含み得、さらに、組込型抵抗加熱要素を用いて、比較的高温(例えば、約100℃以下から約600℃以上)に達するために抵抗加熱され得る。
[0026]フェースプレート217は、最上部が狭く、底部に向けて拡張して広くなっているピラミッド形、円錐形、又は同様の別の構造であってよい。さらに、フェースプレート217は、図示したように平坦で、処理ガスを分配するために使用される複数の貫通チャネルを含んでいてよい。プラズマ生成ガス及び/又はプラズマ励起種は、RPS201の使用に応じて、図2Bに示すフェースプレート217の複数の孔を通過し、第1のプラズマ領域215の中へより均一に供給され得る。
[0027]例示的な構成では、ガス注入口アセンブリ205が、フェースプレート217によって第1のプラズマ領域215から区切られたガス供給領域258に通じることにより、ガス/種がフェースプレート217の孔を介して、第1のプラズマ領域215へ流れ込むことが含まれ得る。第1のプラズマ領域215から、供給領域258、ガス注入口アセンブリ205、及び流体供給システム210へのプラズマの大量逆流を防止するために、構造的及び動作的特徴が選択され得る。フェースプレート217(又はチャンバの導電性上部)及びシャワーヘッド225は、それらの特徴の間に絶縁リング220が配置されているように示されており、それにより、シャワーヘッド225及び/又はイオンサプレッサ223に対するフェースプレート217にAC電位が印加されることが可能となる。絶縁リング220をフェースプレート217とシャワーヘッド225及び/又はイオンサプレッサ223との間に位置付けすることができ、それにより、第1のプラズマ領域内で容量結合プラズマ(CCP)の形成が可能となる。さらに、バッフル(図示せず)を第1のプラズマ領域215内に配置するか、又はさもなければガス注入口アセンブリ205と結合することができ、ガス注入口アセンブリ205を通って領域に流れ込む流体の流れに影響を与える。
[0028]イオンサプレッサ223は、構造体にわたって複数の開孔を画定するプレート又はその他の形状を含み得る。これは、非荷電中性種又はラジカル種がイオンサプレッサ223を通過し、サプレッサとシャワーヘッドとの間の活性化されたガス供給領域内に入ることを可能にしながら、第1のプラズマ領域215から出るイオン帯電種の移動を抑圧するように構成されている。実施形態では、イオンサプレッサ223は、様々な開口構成を有する穴あきプレートを備え得る。これらの非荷電種には、開孔を介して反応性がより低いキャリアガスと共に搬送される非常に反応性の高い種が含まれ得る。上述したように、孔を介したイオン種の移動を減らすことができ、ある場合には、完全に抑えることができる。イオンサプレッサ223を通過するイオン種の量を制御することにより、有利には、下位のウエハ基板と接触させられるガス混合物に対する制御を向上させることができ、それにより、ガス混合物の堆積特性及び/又はエッチング特性に対する制御を向上させることができる。例えば、混合ガスのイオン濃度の調節によって、エッチング選択性、例えば、SiNx:SiOxエッチング比、Si:SiOxエッチング比等を著しく変えることができる。堆積が実行される代替的な実施形態では、誘電材料に対する共形型から流動可能型の堆積のバランスをシフトさせることもできる。
[0029]イオンサプレッサ223の複数の開孔は、イオンサプレッサ223を通る活性ガス(すなわち、イオン種、ラジカル種、及び/又は中性種)の通過を制御するように構成され得る。例えば、イオンサプレッサ223を通過する活性ガスの中のイオン帯電種の流量を減少させるように、孔のアスペクト比(すなわち、孔の長さに対する直径)及び/又は孔の形状寸法を制御することができる。イオンサプレッサ223の孔は、プラズマ励起領域215に対向するテーパ部と、シャワーヘッド225に対向する円筒部とを含み得る。円筒部は、シャワーヘッド225へと通過するイオン種の流量を制御するように成形及び寸法形成され得る。イオンサプレッサ223を通るイオン種の流量を制御する追加手段として、調節可能な電気的バイアスをイオンサプレッサ223に印加してもよい。
[0030]イオンサプレッサ223は、プラズマ生成領域から基板まで移動する帯電種の量を減らすか、又はなくすように機能することができる。非荷電中性種及びラジカル種は、基板と反応するように、さらにイオンサプレッサの開口を通過することができる。基板周囲の反応領域の帯電種の完全な除去は、実施形態によっては実施されない場合があることに留意されたい。特定の場合では、帯電種は、エッチング及び/又は堆積処理を行うために基板に到達することが意図されている。このような場合、イオンサプレッサは、処理を支援する程度に、反応領域内の帯電種の濃度の制御を助けることができる。
[0031]シャワーヘッド225は、イオンサプレッサ223との組み合わせにより、第1のプラズマ領域215内に存在するプラズマが、基板処理領域233内のガスの直接励起を避けることを可能にし得るが、さらに励起種がチャンバプラズマ領域215から基板処理領域233内へ移動することを可能する。このようにして、チャンバは、エッチングされている基板255にプラズマが接触することを防止するように構成され得る。これにより、有利には、基板上にパターン形成された様々な複雑な構造及び膜が保護される。これらの複雑な構造及び膜は、生成されたプラズマが直接接触すると、損傷、位置ずれ、又は歪みが生じ得る。さらに、プラズマが基板に接触するか、又は基板レベルに接近することが許容された場合、酸化物種がエッチングを行う速度が上昇し得る。したがって、材料の露出領域が酸化物である場合、プラズマを基板から遠隔位置に留めることにより、この材料をさらに保護することができる。
[0032]処理システムは、処理チャンバに電気的に接続された電源240をさらに含み得る。電源240は、第1のプラズマ領域215又は処理領域233でプラズマを生成するために、フェースプレート217、イオンサプレッサ223、シャワーヘッド225、及び/又はペデスタル265に電力を供給する。電源は、実行される処理に応じて、チャンバに調節可能な量の電力を送るように構成され得る。このような構成により、実行されている処理において調節可能なプラズマが使用されることが可能となり得る。オン又はオフ機能が提示されることが多い遠隔プラズマユニットとは異なり、調節可能なプラズマは、特定の量の電力をプラズマ領域215に供給するように構成され得る。この結果、特定のプラズマ特性の開発を可能にすることができ、それにより、特定の方法で前駆体を分離し、これらの前駆体によって生成されたエッチングプロファイルを強化することができる。
[0033]プラズマは、シャワーヘッド225の上方のチャンバプラズマ領域215、又は、シャワーヘッド225の下方の基板処理領域233のいずれかにおいて点火することができる。例えば、フッ素含有前駆体又はその他の前駆体の流入からラジカル前駆体を生成するために、プラズマがチャンバプラズマ領域215の中に存在し得る。通常は高周波(RF)範囲内の交流電圧が、フェースプレート217などの処理チャンバの導電性上部とシャワーヘッド225及び/又はイオンサプレッサ223との間に印加されて、堆積中にチャンバプラズマ領域215内でプラズマが点火される。RF電源は、13.56MHzの高RF周波数を発生させ得るが、単独で又は13.56MHzの周波数との組み合わせで他の周波数を発生させることもできる。
[0034]図2Bは、フェースプレート217を介した処理ガスの分配に影響を与える特徴の詳細図253である。図2A及び図2Bに示すように、フェースプレート217、ブロッカプレート203、及びガス注入口アセンブリ205が交差することにより、ガス供給領域258が画定される。ガス供給領域258には、ガス注入口アセンブリ205から処理ガスが供給され得る。ガスは、ガス供給領域258に充満して、フェースプレート217の開孔259を通って、第1のプラズマ領域215まで流れることができる。開孔259は、流れを実質的に一方向へ導くように構成され得る。それにより、処理ガスは、処理領域233内に流れ得るが、フェースプレート217を横断した後、ガス供給領域258内に逆流することが部分的又は完全に防止され得る。
[0035]処理チャンバシステム200で使用されるシャワーヘッド225などのガス分配アセンブリは、デュアルチャネルシャワーヘッド(DCSH)と呼ばれてもよく、図3に記載された実施形態でさらに詳しく示される。デュアルシャワーヘッドは、処理領域233の外のエッチング液の分離を可能にし、処理領域内に送る前に、チャンバ構成要素及び相互との限られた相互作用をもたらすエッチング処理を提供することができる。
[0036]シャワーヘッド225は、上方プレート214と下方プレート216とを含み得る。プレートを互いに連結させて、プレート間の容積218を画定することができる。プレートを連結することにより、上方プレートと下方プレートを通る第1の流体チャネル219と、下方プレート216を通る第2の流体チャネル221とを設けることができる。形成されたチャネルは、第2の流体チャネル221のみを介して、下方プレート216を通して容積218からの流体アクセスをもたらすように構成されてもよく、第1の流体チャネル219は、プレートと第2の流体チャネル221との間の容積218から流体的に分離され得る。容積218は、ガス分配アセンブリ又はシャワーヘッド225の側部を通して流体的にアクセス可能であり得る。
[0037]図3は、実施形態に係る、処理チャンバで使用するためのシャワーヘッド325の底面図である。シャワーヘッド325は、図2Aに示されたシャワーヘッドに対応し得る。第1の流体チャネル219の図を示す貫通孔365は、シャワーヘッド225を通る前駆体の流れを制御して影響を与えるための複数の形状及び構成を有し得る。第2の流体チャネル221の図を示す小さな孔375は、シャワーヘッドの表面上に、貫通孔365の間でさえもほぼ均等に配分される。他の構成に比べて、これらの小さな孔375は、前駆体がシャワーヘッドから流出する際に、より均一な混合をもたらす助けとなり得る。
[0038]上述のチャンバは、エッチング方法を含む例示的な方法の実行に使用され得る。図4を見ると、本技術の実施形態に係る方法400の例示的な工程を示す。方法の第1の工程の前に、基板は、方法400が実行され得るチャンバの処理領域内に配置される前に1つ又は複数の方法で処理され得る。例えば、特徴が生成され得、ゲルマニウム含有材料が基板上に形成され得る。幾つかの実施形態では、第1のゲルマニウム濃度によって特徴付けられた第1のゲルマニウム含有材料が形成され得、第2のゲルマニウム濃度によって特徴付けられた第2のゲルマニウム含有材料が形成され得る。基板上で形成され得る且つ/又は露出され得る追加の材料には、シリコン、窒化物、又は酸化物材料が含まれ得る。
[0039]方法400は、工程405では、半導体処理チャンバの遠隔プラズマ領域内でフッ素含有前駆体のプラズマを形成することを含み得る。遠隔プラズマ領域は、基板が収容され得る処理領域に隣接する領域(例えば、上述の領域215)であり得る。遠隔プラズマ領域は、処理チャンバに流体接続された別個の遠隔プラズマユニット(例えば、上述のRPS201)であってもよい。プラズマは、ウエハ又は基板レベルで形成され得ないという意味で遠隔プラズマであってもよく、幾つかの実施形態では、基板が収容されている処理領域は、エッチング方法400の工程の間、プラズマがない状態に維持され得る。プラズマがない状態(plasma free)とは、遠隔プラズマ領域からの幾らかの移動性要素が処理領域の中へと延在し得るが、ウエハレベルのプラズマは、諸工程の間に形成され得ないことを意味する。
[0040]フッ素含有前駆体は、実施形態では三フッ化窒素であり得る。その他のフッ素供給源を使用して、三フッ化窒素を補強又は置換することができる。概して、フッ素含有前駆体をプラズマ領域の中に流すことができる。当該フッ素含有前駆体には、フッ化炭素、原子状フッ素、二原子フッ素、ハロゲン間フッ化物(三フッ化臭素又は三フッ化塩素)、三フッ化窒素、六フッ化硫黄、或いは二フッ化キセノンなどのような1つ又は複数のフッ素含有材料が含まれ得る。幾つかの実施形態では、フッ素含有前駆体は、プラズマ流出物内で、より寿命の長い励起中性フッ素種を生成し得る三フッ化窒素であってもよい。1つ又は複数の追加の前駆体は、フッ素含有前駆体と共に流されてもよく、キャリアガスとして使用されるか、又は処理チャンバに別個に供給されてもよい。追加の前駆体には、アルゴン、ヘリウム、ネオン、キセノン、又はフッ素含有材料の分離、エッチング液形成、又は流量特徴を補助するように構成されたその他の何らかの材料が含まれ得る。追加の前駆体の流量は、実施形態では、三フッ化窒素の流量よりも2倍、3倍、4倍、又は5倍である場合があり、これにより、シリコンゲルマニウムのエッチング選択性が広がり得る。
[0041]プラズマから形成されたプラズマ流出物は、チャンバ内に流れるか、又は、チャンバを通して流れる場合があり、工程410では、触媒材料に接触するか、又は触媒材料を通過するように仕向けられる。触媒材料は、実施形態では、1つ又は複数のチャンバ構成要素上に含まれ得、プラズマ形成に対して位置付けされ得る。例えば、触媒材料は、イオンサプレッサ又はシャワーヘッド(イオンサプレッサ223及びシャワーヘッド225など)に関連付けられ得る。触媒材料が、構成要素上にコーティングされるか、インサートとして組み込まれてもよく、或いは、構成要素が少なくとも部分的に触媒材料から形成されてもよい。非限定的な実施例として、幾つかの実施形態では、触媒材料は、構成要素の1つ又は複数の表面上にコーティングされてもよい。シャワーヘッド又はイオンサプレッサについては、触媒材料は、構成要素の上流側又は構成要素全体にコーティングされてもよい。
[0042]触媒材料は、特に構成要素の開孔を通して形成され得る。これらの開孔は、高表面積をもたらすことができ、粒子は、構成要素を通って前進する前に、何度か開孔の側壁と衝突又は相互作用し得る。これは、触媒変換が生じる十分な機会をもたらし得る。さらに、処理チャンバの他の構成要素は、触媒材料でコーティングされてもよく、又は触媒材料を含んでもよい。例えば、プラズマ流出物がRPSユニット内で形成される際に、触媒材料がチャンバの1つ又は複数の構成要素に含まれ得る。例えば、注入口アセンブリ205の供給チューブは、触媒材料で覆われてもよい。さらに、ブロッカプレート203、フェースプレート217、イオンサプレッサ223、又はシャワーヘッド225の開口側壁を含む任意の表面は、触媒材料でコーティングされるか、又は触媒材料と結合されてもよい。
[0043]工程415では、プラズマ流出物内のフッ素ラジカルの数量又は濃度を減少させるために触媒変換が起こり得る。触媒材料は、フッ素原子を、分子毎に少なくとも2つのフッ素原子を含む追加の材料に変換することを促進することができる。例えば、三フッ化窒素が例示的なフッ素含有前駆体として使用される場合、プラズマ流出物は、NF、NF 、及びFを含む材料の組み合わせを含み得る。フッ素ラジカルは、基板上で露出したシリコン及び窒化ケイ素材料をエッチングすることができ、これにより、ゲルマニウム又はSiGeのエッチングの選択性が減少し得る。絶えず縮小していくデバイス上の限界寸法が益々減少していく中で、ゲルマニウムをエッチングする間、他の材料を維持するために、10、50、又はさらに100の選択性でも十分ではない場合がある。
[0044]触媒材料は、フッ素ラジカルを代替的なエッチャント材料へ変換することを促進することができる。この代替的なエッチャント材料は、例えば、F、N、或いは複数の結合フッ素原子を有するか、又はラジカル成分が減少した若しくは消滅したその他の組み合わせである。これらのFなどのエッチング液は、シリコン、窒化物、酸化物、及び例えばゲルマニウム濃度が低下したその他のシリコンゲルマニウムに対して、好ましくは、ゲルマニウム又はシリコンゲルマニウムをエッチングし得る。一旦、触媒変換又はフッ素ラジカルの減少が起きると、工程420では、修正されたプラズマ流出物は、基板が収容され得る処理領域に供給され得る。その後、工程425でゲルマニウム含有材料がエッチングされ得る。フッ素ラジカル種の濃度を実質的に減らすことにより、本技術は、従来の技術に対して向上したエッチング選択性をもたらすことができる。例えば、本技術では、実施形態において、約100:1以上、約200:1以上、約300:1以上、約400:1以上、約500:1以上、約600:1以上、約700:1以上、約800:1以上、約900:1以上、又は最大1000:1以上の選択性で、シリコン、窒化ケイ素、又はゲルマニウム濃度がより低いシリコンゲルマニウムに対して、シリコンゲルマニウム又はゲルマニウムがエッチングされ得る。
[0045]本技術では、ゲルマニウム濃度がより低い第2のシリコンゲルマニウムに対して、第1のシリコンゲルマニウムがエッチングされ得る。概して、Si(1-X)Geは、Si(1-Y)Geより迅速にエッチングされ得るが、それは、X>Yのすべての場合において、膜がシリコンを含む、Yがゼロである場合から、膜がゲルマニウムを含む、Xが1である場合までに当てはまる。Si(1-X)Geは、第1のエッチング速度でエッチングを行うことができ、Si(1-Y)Geは、第2のエッチング速度でエッチングを行うことができる。実施形態に応じて、第1のエッチング速度は、第2のエッチング速度より大きい場合がある。2つの材料間のゲルマニウム濃度の違いに応じて、実施形態では、第1のエッチング速度は、第2のエッチング速度を10倍、20倍、50倍、100倍、300倍、500倍又はそれ以上越え得る。
[0046]触媒材料は、触媒面を設けることで知られている任意の数の材料であり得るか、又はそれらを含み得る。例えば、触媒材料は、様々な濃度のニッケル、コバルト、バナジウム、ニオブ、タンタル、クロム、マンガン、レニウム、鉄、ルテニウム、オスミウム、パラジウム、プラチナ、ロジウム、イリジウム、並びにこれらの任意の物質の酸化物、或いは、その他の周知の触媒物質であるか、又はこれらを含み得る。
[0047]温度及び圧力は、本技術の触媒活性及び選択性の両方に影響を与え得る。例えば、十分な触媒活性を確保するために、触媒材料が配置されたデバイスの温度は、実施形態では、約50℃以上であり得る。約50℃以上未満の温度では、フッ素ラジカルが十分に変換され得ず、エッチング処理の選択性が減少又は実質的に減少し得る。さらに、温度は、約60℃以上、約65℃以上、約70℃以上、約75℃以上、約80℃以上、約85℃以上、約90℃以上、約95℃以上、約100℃以上、約105℃以上、約110℃以上、約115℃以上、約120℃以上、約125℃以上、約130℃以上、約135℃以上、約140℃以上、約145℃以上、約150℃以上、又はさらにそれよりも高くてもよい。
[0048]本プラズマ技術によって生成された二原子フッ素は、有益には、ゲルマニウム含有材料をエッチングすることができる。しかしながら、二原子フッ素は、チャンバ環境内で分離しやすい場合があり、処理の選択性を減少させる恐れがある。したがって、幾つかの実施形態では、フッ素の分離を制限し、エッチング選択性を十分に維持するために、温度は、約200℃以下、約180℃以下、約170℃以下、約160℃以下、約150℃以下、約140℃以下、約130℃以下、約120℃以下、又はそれより低くてもよい。
[0049]基板の温度もエッチングの選択性に影響を与える場合がある。触媒温度の上昇はエッチング液の生成にとって有益であり得るが、このような温度は、エッチング液が基板に供給される際に処理の選択性を減少させる場合がある。したがって、方法400の間、基板は、実施形態では、約50℃以下に維持されてもよく、約45℃以下、約40℃以下、約35℃以下、約30℃以下、約25℃以下、約20℃以下、約15℃以下、約10℃以下、約5℃以下、約0℃以下、約-5℃以下、又はそれより低く維持されてもよい。
[0050]処理チャンバ内の圧力は、エッチング液形成及び工程の選択性にも影響を与え得る。幾つかの実施形態では、圧力は、約1Torr以上であってもよく、約2Torr以上、約3Torr以上、約5Torr以上、約10Torr以上、約15Torr以上、約20Torr以上、約25Torr以上、約30Torr以上、約35Torr以上、約40Torr以上、約45Torr以上、約50Torr以上、又はそれより高くてもよい。より高い圧力は、プラズマ流出物種の衝突又は相互作用を促進することができ、実施形態では、チャンバ内の圧力は、約2Torr又は約3Torrを越える圧力に維持され得る。しかしながら、圧力は、分圧が上昇する際にさらに二原子フッ素の分離に影響を与える場合があり、さらに衝突が増えて、形成されたエッチャント種に損傷が生じる場合がある。エッチャント分子が分離する際に、フッ素ラジカル流出物の再生成に起因して、選択性が減少し得る。したがって、上述の選択性を維持するために、圧力は、約50Torr以下、約40Torr以下、約30Torr以下、又は約20Torr以下に維持され得る。
[0051]上述の圧力及び温度状況で工程を実行することにより、本技術は、好ましくはゲルマニウム含有材料を除去するエッチャント種を生成することができる。これらの工程は、従来技術を越えるようなゲルマニウム含有材料の除去率及び選択性をもたらすことができる。
[0052]上記の記載では、説明を目的として、本技術の様々な実施形態の理解を促すために、数々の詳細が提示されている。しかしながら、当業者には、これらの詳細のうちの一部がなくても、或いは、追加の詳細があれば、特定の実施形態を実施することができることは明らかであろう。
[0053]幾つかの実施形態を開示したが、当業者は、実施形態の精神から逸脱することなく、様々な修正例、代替構造物、及び均等物を使用できることを認識されよう。さらに、幾つかの周知の処理及び要素は、本技術を不必要に不明瞭にすることを避けるために説明されていない。したがって、上記の説明は、本技術の範囲を限定するものと見なすべきではない。さらに、方法又は処理は、連続的又は段階的に説明され得るが、工程は、同時に行われてもよく、又は、記載よりも異なる順序で行われてもよいことを理解するべきである。
[0054]値の範囲が提供されている場合、文脈上そうでないと明示されていない限り、当然ながら、その範囲の上限値と下限値との間の各介在値は、下限値の最も小さい単位まで具体的に開示されている。記載された範囲の任意の記載値又は記載されていない介在値の間の任意の小さい範囲、そしてその記載範囲のその他の任意の記載された値又は介在する値も含まれる。これら小さい範囲の上限値及び下限値は、その範囲に個々に含まれ、又はその範囲から除外される場合があり、小さい範囲に限界値のいずれかが含まれる、どちらも含まれない、又は両方が含まれる各範囲もこの技術に含まれ、記載された範囲において任意に具体的に除外された限界値に依存する。記載された範囲に限界値の片方又は両方が含まれる場合、これらの含有限界値のいずれか又は両方を除外する範囲も含まれる。
[0055]本明細書及び特許請求の範囲で使用される単数形「a」、「an」、及び「the」は、文脈が他のことを明らかに示していない限り、複数の参照対象を含む。したがって、例えば、「ある前駆体(a precursor)」への言及は、複数のこのような前駆体を含み、「その層(the layer)」への言及は、当業者に知られている1つ又は複数の層及びその均等物への言及を含み、その他の形にも同様のことが当てはまる。
[0056]さらに、「備える(comprise(s))」、「備えている(comprising)」、「含有する(contain(s))」、「含有している(containing)」、「含む(include(s))」、及び「含んでいる(including)」という用語は、本明細書及び特許請求の範囲で使用された場合、記載された特徴、整数、構成要素、又はステップの存在を特定することを意図しているが、1つ又は複数のその他の特徴、整数、構成要素、工程、動作、又はグループの存在又は追加を除外するものではない。

Claims (13)

  1. ゲルマニウム含有材料をエッチングする方法であって、
    半導体処理チャンバの遠隔プラズマ領域内でフッ素含有前駆体のプラズマを形成することと、
    チャンバ構成要素において画定され、触媒材料でコーティングされた開孔を通して前記フッ素含有前駆体のプラズマ流出物を流動させることと
    前記触媒材料を用いて、前記プラズマ流出物内のフッ素ラジカルの濃度を減少させることと、
    前記半導体処理チャンバの処理領域に前記プラズマ流出物を供給することであって、ゲルマニウム含有材料を含む基板が、前記処理領域内に収容される、前記プラズマ流出物を供給することと、
    前記ゲルマニウム含有材料をエッチングすることと
    を含み、前記チャンバ構成要素が、70℃以上の温度で維持される、方法。
  2. 前記触媒材料が、ニッケル、コバルト、バナジウム、ニオブ、タンタル、クロム、マンガン、レニウム、鉄、ルテニウム、オスミウム、パラジウム、プラチナ、ロジウム、及びイリジウムからなる群から選択された元素を含む1つ又は複数の材料を含む、請求項1に記載のゲルマニウム含有材料をエッチングする方法。
  3. 前記基板が、30℃以下の温度で維持される、請求項1に記載のゲルマニウム含有材料をエッチングする方法。
  4. 前記ゲルマニウム含有材料が、SiGeを含む、請求項1に記載のゲルマニウム含有材料をエッチングする方法。
  5. 前記ゲルマニウム含有材料が、第1のゲルマニウム含有材料であり、前記第1のゲルマニウム含有材料が、シリコン又は第2のゲルマニウム含有材料に対してエッチングされ、前記第2のゲルマニウム含有材料が、前記第1のゲルマニウム含有材料より低いゲルマニウム濃度によって特徴付けられる、請求項1に記載のゲルマニウム含有材料をエッチングする方法。
  6. ゲルマニウム含有材料をエッチングする方法であって、
    半導体処理チャンバの遠隔プラズマ領域内でフッ素含有前駆体のプラズマを形成することと、
    チャンバ構成要素において画定され、触媒材料でコーティングされた開孔を通して前記フッ素含有前駆体のプラズマ流出物を流動させることと、
    前記触媒材料を用いて、前記プラズマ流出物内のフッ素ラジカルの濃度を減少させることと、
    前記半導体処理チャンバの処理領域に前記プラズマ流出物を供給することであって、ゲルマニウム含有材料を含む基板が、前記処理領域内に収容される、前記プラズマ流出物を供給することと、
    前記ゲルマニウム含有材料をエッチングすることと
    を含み、前記半導体処理チャンバ内の圧力が、2Torr以上の圧力で維持される、方法。
  7. ゲルマニウム含有材料をエッチングする方法であって、
    半導体処理チャンバの遠隔プラズマ領域内でフッ素含有前駆体のプラズマを形成することと、
    触媒材料を含むチャンバ構成要素を通して前記フッ素含有前駆体のプラズマ流出物を流動させることと、
    前記触媒材料によって、前記プラズマ流出物内のフッ素ラジカルの少なくとも一部を触媒反応で変換させることと、
    前記半導体処理チャンバの処理領域に前記プラズマ流出物を供給することであって、ゲルマニウム含有材料を含む基板が、前記処理領域内に収容される、前記プラズマ流出物を供給することと、
    前記ゲルマニウム含有材料をエッチングすることと
    を含み、前記チャンバ構成要素が、70℃以上の温度で維持される、方法。
  8. 前記変換させることが、前記触媒材料上のフッ素ラジカルから少なくとも2つのフッ素原子を含む材料を形成することを含む、請求項に記載のゲルマニウム含有材料をエッチングする方法。
  9. 前記チャンバ構成要素が、遠隔プラズマユニット供給チューブ、ブロッカプレート、フェースプレート、イオンサプレッサ、又はシャワーヘッドのうちの1つ又は複数を含む、請求項に記載のゲルマニウム含有材料をエッチングする方法。
  10. 前記触媒材料が、ニッケル、コバルト、バナジウム、ニオブ、タンタル、クロム、マンガン、レニウム、鉄、ルテニウム、オスミウム、パラジウム、プラチナ、ロジウム、及びイリジウムからなる群から選択された元素を含む1つ又は複数の材料を含む、請求項に記載のゲルマニウム含有材料をエッチングする方法。
  11. 前記基板が、30℃以下の温度で維持される、請求項に記載のゲルマニウム含有材料をエッチングする方法。
  12. ゲルマニウム含有材料をエッチングする方法であって、
    半導体処理チャンバの遠隔プラズマ領域内でフッ素含有前駆体のプラズマを形成することと、
    チャンバ構成要素において画定され、触媒材料でコーティングされた開孔を通して前記フッ素含有前駆体のプラズマ流出物を流動させることであって、前記チャンバ構成要素が、70℃と150℃との間の温度で維持される、前記フッ素含有前駆体のプラズマ流出物を流動させることと、
    前記触媒材料を用いて、前記プラズマ流出物内のフッ素ラジカルの濃度を減少させることと、
    前記半導体処理チャンバの処理領域に前記プラズマ流出物を供給することであって、ゲルマニウム含有材料を含む基板が、前記処理領域内に収容され、前記基板が、30℃以下の温度で維持される、前記プラズマ流出物を供給することと、
    前記ゲルマニウム含有材料をエッチングすることと
    を含む方法。
  13. 前記触媒材料が、ニッケル、コバルト、バナジウム、ニオブ、タンタル、クロム、マンガン、レニウム、鉄、ルテニウム、オスミウム、パラジウム、プラチナ、ロジウム、及びイリジウムからなる群から選択された元素を含む1つ又は複数の材料を含む、請求項12に記載のゲルマニウム含有材料をエッチングする方法。
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