JP4546675B2 - Multistage discharge plasma processing method and apparatus - Google Patents

Multistage discharge plasma processing method and apparatus Download PDF

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JP4546675B2
JP4546675B2 JP2001248039A JP2001248039A JP4546675B2 JP 4546675 B2 JP4546675 B2 JP 4546675B2 JP 2001248039 A JP2001248039 A JP 2001248039A JP 2001248039 A JP2001248039 A JP 2001248039A JP 4546675 B2 JP4546675 B2 JP 4546675B2
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plasma generation
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勇司 江口
基和 湯浅
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Sekisui Chemical Co Ltd
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Description

【０００１】
【発明の属する技術分野】
本発明は、放電プラズマ処理方法による酸化金属膜／窒化金属膜の薄膜を形成する多段型の放電プラズマ処理方法及びその装置に関し、特に、金属元素含有ガスを励起プラズマ化した後に酸素含有ガス及び／又は窒素含有ガスを混合して、反応を進行させて薄膜を形成する多段型の放電プラズマ処理方法及びその装置に関する。
【０００２】
【従来の技術】
ＬＳＩの高密度化に伴い、基材上に目的とする材料の薄膜を形成できるＣＶＤ処理方法が利用されてきており、熱プラズマＣＶＤ法や低圧プラズマＣＶＤ法が多用されてきている。熱プラズマＣＶＤ法は高温によるダメージが避けられず、低圧プラズマＣＶＤ法は真空に近い装置が必要であるため低圧設備にコストがかかり、さらに、両者とも製膜速度が不十分であるという問題があった。特に酸素とシラン化合物を用いるような混合ガスから酸化シリコン膜等を成膜する場合は、均一性の高い膜を形成するのが難しく、さらに膜中にＯＨ基が形成されており、膜質が向上しないという問題があった。この問題を解決するため、特開平７−３３５５７６号公報では、酸素含有ガス等を高温非平衡プラズマまたは高温平衡プラズマを使用した酸性活性種発生機構に導入する前処理をすることによりその改善を図っているが、装置全体では、低圧設備が必要であり、未だ反応効率も劣っているという問題があった。
【０００３】
これに対して、大気圧近傍で処理を行うことのできる常圧プラズマ処理方法が開発され、熱プラズマＣＶＤ法のような高温によるダメージを受けず、低圧プラズマＣＶＤ法のような低圧設備を必要としない技術を用い、金属系ガスの薄膜等が簡易な装置で容易に基材上に形成できるようになった。この常圧プラズマ法による薄膜の形成においても、酸化金属膜／窒化金属膜を作成する場合、金属系ガスと酸素系ガス／窒素系ガスを混合した状態でプラズマ励起させると、反応が十分に進まない場合があり、膜質の向上が求められていた。
【０００４】
【発明が解決しようとする課題】
本発明は、上記問題に鑑み、放電プラズマ処理による酸化金属薄膜又は窒化金属薄膜の形成において、膜質に優れ、産業上必要とされる成膜速度で酸化金属薄膜又は窒化金属薄膜を容易に形成できる方法及びその装置を提供することを目的とする。
【０００５】
【課題を解決するための手段】
本発明者らは、上記課題を解決すべく鋭意研究した結果、大気圧条件下で安定した放電状態を実現できるプラズマ発生室で、金属元素含有ガスを予めプラズマ励起させた後に、酸素含有ガス及び／又は窒素含有ガスを導入して反応を進行させることにより、簡便に目的とする薄膜が形成できることを見出し本発明を完成した。
【０００６】
すなわち、本発明の第１は、金属元素含有ガスと酸素含有ガス及び／又は窒素含有ガスを反応させて酸化金属化合物及び／又は窒化金属化合物からなる薄膜を被処理基材の表面に形成する放電プラズマ処理方法において、一つのプラズマ発生室を通過した金属元素含有ガスに、酸素含有ガス及び／又は窒素含有ガスを合流させて、別のプラズマ発生室を通過させてこれらプラズマ発生室の外部に配置した上記被処理基材に吹き付け、上記被処理基材の表面に上記薄膜を形成し、上記各プラズマ発生室が、少なくとも一方の対向面が固体誘電体で被覆された一対の対向電極の間に形成され、かつ上記対向電極間に電界を印加することでプラズマを発生させる空間であることを特徴とする多段型の放電プラズマ処理方法である。
【０００７】
また、本発明の第２の発明は、金属元素含有ガスと酸素含有ガス及び／又は窒素含有ガスを反応させて酸化金属化合物及び／又は窒化金属化合物からなる薄膜を被処理基材の表面に形成する放電プラズマ処理方法において、一つのプラズマ発生室を通過した金属元素含有ガスと、別のプラズマ発生室を通過した酸素含有ガス及び／又は窒素含有ガスとを合流させて、更に他のプラズマ発生室を通過させてこれらプラズマ発生室の外部に配置した上記被処理基材に吹き付け、上記被処理基材の表面に上記薄膜を形成し、上記各プラズマ発生室が、少なくとも一方の対向面が固体誘電体で被覆された一対の対向電極の間に形成され、かつ前記対向電極間に電界を印加することでプラズマを発生させる空間であることを特徴とする多段型の放電プラズマ処理方法である。
【０００９】
また、本発明の第３の発明は、電界が、パルス立ち上がり及び／又は立ち下がり時間が１０μｓ以下であるパルス状電界であることを特徴とする第１又は２の発明に記載の多段型の放電プラズマ処理方法である。
【００１０】
また、本発明の第４の発明は、電界が、電界強度が１０〜１０００ｋＶ／ｃｍであるパルス状電界であることを特徴とする第１〜３のいずれかの発明に記載の多段型の放電プラズマ処理方法である。
【００１１】
また、本発明の第５の発明は、金属元素含有ガスと酸素含有ガス及び／又は窒素含有ガスを反応させて酸化金属化合物及び／又は窒化金属化合物からなる薄膜を被処理基材の表面に形成する放電プラズマ処理装置において、少なくとも一方の対向面が固体誘電体で被覆された一対の対向電極を有し、上記対向電極どうし間の一の端部に１の処理ガス導入口が設けられ、上記対向電極どうし間の別の端部にガス吹出口が設けられ、上記対向電極どうし間の上記１の処理ガス導入口とガス吹出口の中間に別の処理ガス導入口が設けられ、上記対向電極どうし間における上記１の処理ガス導入口と上記別の処理ガス導入口との間の部分が、１のプラズマ発生室を構成し、上記対向電極どうし間における上記別の処理ガス導入口と上記ガス吹出口との間の部分が、別のプラズマ発生室を構成し、上記対向電極間に電界が印加されることにより上記各プラズマ発生室内でプラズマが発生し、上記金属元素含有ガスが、上記１の処理ガス導入口から上記１のプラズマ発生室に導入され、上記酸素含有ガス及び／又は窒素含有ガスと混合されることなく上記１のプラズマ発生室内にてプラズマ励起され、上記酸素含有ガス及び／又は窒素含有ガスが、上記別の処理ガス導入口から上記別のプラズマ発生室に導入されて上記１のプラズマ発生室を通過した上記金属元素含有ガスと合流し、合流したガスが、上記別のプラズマ発生室を通過して上記ガス吹出口から吹き出され、上記対向電極間の外部に配置された上記被処理基材に吹き付けられ、上記被処理基材の表面に上記薄膜が形成されることを特徴とする放電プラズマ処理装置である。
【００１２】
また、本発明の第６の発明は、上記別の処理ガス導入口が、上記一対の対向電極のうちの１つの電極に設けられた穴によって形成されていることを特徴とする第５の発明に記載の放電プラズマ処理装置である。
【００１４】
また、本発明の第７の発明は、一の対向電極によって形成される第１のプラズマ発生室、他の対向電極によって形成される第２のプラズマ発生室を備え、第１のプラズマ発生室と第２のプラズマ発生室から吹き出したガス流が合流して、第３のプラズマ発生室に導入されるようになされ、第１のプラズマ発生室と第３のプラズマ発生室の電界印加側の電極が共通のものであることを特徴とする放電プラズマ処理装置である。
【００１５】
また、本発明の第８の発明は、一の対向電極によって形成される第１のプラズマ発生室、他の対向電極によって形成される第２のプラズマ発生室を備え、第１のプラズマ発生室と第２のプラズマ発生室から吹き出したガス流が合流して、第３のプラズマ発生室に導入されるようになされ、第１のプラズマ発生室と第２のプラズマ発生室の電界印加側の電極が共通のものであることを特徴とする放電プラズマ処理装置である。
【００１６】
また、本発明の特許請求しない第１１の発明は、第１のプラズマ発生室には金属元素含有ガスが導入され、第２のプラズマ発生室には酸素含有ガス及び／又は窒素含有ガスが導入されるものであることを特徴とする第７又は８の発明に記載の放電プラズマ処理装置である。
【００１７】
【発明の実施の形態】
本発明の酸化金属化合物薄膜又は窒化金属化合物薄膜の形成方法は、金属元素含有ガスと酸素含有ガス及び／又は窒素含有ガスを反応させて酸化金属化合物及び／又は窒化金属化合物からなる薄膜を形成する方法において、励起しにくい金属元素含有ガスを予めプラズマ発生室でプラズマ励起させた後に、酸素含有ガス又は窒素含有ガスを導入して、さらに、次のプラズマ発生室でプラズマ処理反応を進行させる多段型の放電プラズマ処理方法である。該処理方法には、次の２種類の方法が含まれる。（１）金属元素含有ガスを一つのプラズマ発生室の前半部でプラズマ励起させた後に酸素含有ガス及び／又は窒素含有ガスを合流させ、合流させた混合ガスをプラズマ発生室の後半部でプラズマ励起させて、基材に吹き付ける方法と（２）金属元素含有ガスと、酸素含有ガス及び／又は窒素含有ガスとをそれぞれ別のプラズマ発生室で励起させた後に合流させて、合流後に、別のプラズマ発生室で混合ガスをプラズマ励起させて、基材に吹き付ける方法である。いずれの方法を用いても、膜質に優れた酸化金属薄膜又は窒化金属薄膜を得ることができる。
【００１８】
ここで、プラズマ発生室とは、少なくとも一対の対向電極を有し、対向電極の少なくとも一方の対向面が固体誘電体で被覆された電極間に電界を印加してプラズマを発生させる電極間の放電空間である。本発明においては、このプラズマ発生室に処理ガスを導入してプラズマ化してから、放電空間の外にプラズマを吹き出させ、プラズマ流を放電空間の外に配置された被処理基材表面に吹き付けて処理を行う。プラズマ発生室は、主に、平行平板型電極や同軸円筒型電極からなり、その出口は長尺型ノズルや円筒型ノズル等を用いてプラズマ流を放電空間の外に配置された被処理基材表面に吹き付けることができるようにするのが好ましい。
【００１９】
本発明の多段型の放電プラズマ処理装置は、一つのプラズマ発生室を通過した第１のガスに第２のガスを合流させて、別のプラズマ発生室を通過させて混合ガスの放電プラズマを被処理基材に吹き付ける処理装置である。本発明においては、第２のガスを予めプラズマ放電させておく場合と、予め放電させておかない場合の２種類の装置がある。
【００２０】
第２のガスを予めプラズマ放電させておかない場合の装置としては、対向電極の一の端部に処理ガス導入口（１）と別の端部にガス吹出口、前記処理ガス導入口（１）とガス吹出口の中間に処理ガス導入口（２）を設けた放電プラズマ処理装置からなるものが挙げられる。この装置における上記薄膜の形成においては、処理ガス導入口（１）から金属元素含有ガスが導入され、処理ガス導入口（２）からは酸素含有ガス及び／又は窒素含有ガスが導入される。処理ガス導入口（２）が設けられる中間の位置とは、導入口（１）と吹出口の間に存在すればよく、厳密に中心に位置しなくてもよい。また、処理ガス導入口（２）は、対向電極の電極に設けられた穴でよく、穴は、一つであっても多数であってもよい。処理ガス導入口（２）の上流側では、金属元素含有ガスが励起され、下流側では混合ガスが励起される。
【００２１】
第２のガスを予めプラズマ放電させて置く場合の装置としては、一の対向電極によって形成される第１のプラズマ発生室、他の対向電極によって形成される第２のプラズマ発生室を備え、第１のプラズマ発生室と第２のプラズマ発生室から吹き出したガス流が合流して、第３のプラズマ発生室に導入されるようになされた放電プラズマ処理装置を挙げることができる。この装置における上記薄膜の形成においては、第１のプラズマ発生室で金属元素含有ガスが励起され、第２のプラズマ発生室で酸素含有ガス及び／又は窒素含有ガスが励起され、第３のプラズマ発生室で混合ガスが励起される。
【００２２】
本発明の方法及び装置の一例を図で説明する。図１は、金属元素含有ガスをプラズマ励起させた後に酸素含有ガス及び／又は窒素含有ガスを合流させ、合流させた混合ガスをプラズマ励起させて、基材に吹き付ける方法及び装置を説明する図である。図１において、一対の対向電極２と３を有し、電極に電源１から電界を印加してプラズマを発生させるプラズマ発生室６のガス導入口５から、矢印方向に金属元素含有ガスが導入され、プラズマ発生室６でプラズマ励起される。一方、酸素含有ガス及び／又は窒素含有ガスは、電極２に設けられた導入口４から、プラズマ発生室に導入され、プラズマ発生室６でプラズマ励起された金属元素含有ガスと合流され、プラズマ発生室６’で、さらにプラズマ励起される。プラズマ発生室６’でプラズマ励起され、酸化反応及び／又は窒化反応が促進された混合ガスのプラズマ流は、プラズマ吹出口７より被処理基材８に吹き付けられ、基材上に金属酸化物膜及び／又は金属窒化物膜の薄膜を形成させる。
【００２３】
図２は、金属元素含有ガスと、酸素含有ガス及び／又は窒素含有ガスとをそれぞれ、第１のプラズマ発生室と第２のプラズマ発生室で励起させた後に合流させて、合流後に、第３のプラズマ発生室で合流した混合ガスをプラズマ励起させて、基材に吹き付ける方法及び装置を説明する図である。図２において、一対の対向電極２と３を有し、電極に電源１から電界を印加してプラズマを発生させるプラズマ発生室６のガス導入口５から、矢印方向に金属元素含有ガスが導入され、プラズマ発生室６でプラズマ励起される。一方、酸素含有ガス及び／又は窒素含有ガスは、一対の対向電極２’と３’’を有し、電極に電源１’から電界を印加してプラズマを発生させるプラズマ発生室６’’のガス導入口から、矢印方向に酸素含有ガス及び／又は窒素含有ガスが導入され、プラズマ発生室６’’でプラズマ励起される。酸素含有ガス及び／又は窒素含有ガスのプラズマ流は、プラズマ発生室６からの金属元素含有ガスのプラズマ流と合流され、一対の対向電極２と３’を有し、電極に電源１から電界を印加してプラズマを発生させるプラズマ発生室６’に導入され、プラズマ発生室６’でさらにプラズマ励起される。プラズマ発生室６’でプラズマ励起され、酸化反応及び／又は窒化反応が促進された合流ガスのプラズマ流は、プラズマ吹出口７より被処理基材８に吹き付けられ、基材上に金属酸化物及び／又は金属窒化物の薄膜を形成させる。この装置においては、第１のプラズマ発生室と第３のプラズマ発生室の電界印加側の電極である印加電極２を接地電極３と３’に対して共有することにより、設備の重複を防ぐことができる。
【００２４】
図３は、金属元素含有ガスと、酸素含有ガス及び／又は窒素含有ガスとをそれぞれ、第１のプラズマ発生室と第２のプラズマ発生室で励起させた後に合流させて、合流後に、第３のプラズマ発生室で合流した混合ガスをプラズマ励起させて、基材に吹き付ける方法及び装置を説明する図である。図３において、印加電極２を共有し、接地電極３及び３’からなるプラズマ発生室６及び６’を有する装置であって、金属元素含有ガスをプラズマ発生室６においてプラズマ励起し、酸素含有ガス及び／又は窒素含有ガスをプラズマ発生室６’’においてプラズマ励起し、プラズマ発生室６’’で合流すると同時に、さらにプラズマ発生室６’でプラズマ励起される。プラズマ発生室６’でプラズマ励起され、酸化反応及び／又は窒化反応が促進された合流ガスのプラズマ流は、プラズマ吹出口７より被処理基材８に吹き付けられ、基材上に金属酸化物膜及び／又は金属窒化物膜の薄膜を形成させる。この装置においては、第１のプラズマ発生室と第２のプラズマ発生室の電界印加側の電極を共有化し、設備の重複を防いだ装置である。
【００２５】
上記のような装置を用いる本発明の薄膜の製造は、大気圧近傍の圧力下で電界を印加することにより発生するプラズマを利用して金属元素含有ガスを励起する常圧プラズマによる方法が好ましい。
【００２６】
上記大気圧近傍の圧力下とは、１．３３３×１０4〜１０．６６４×１０4Ｐａの圧力下を指す。中でも、圧力調整が容易で、装置が簡便になる９．３３１×１０4〜１０．３９７×１０4Ｐａの範囲が好ましい。
【００２７】
上記で用いる電極の材質としては、例えば、銅、アルミニウム等の金属単体、ステンレス、真鍮等の合金、金属間化合物等からなるものが挙げられる。上記対向電極は、電界集中によるアーク放電の発生を避けるために、対向電極間の距離が略一定となる構造であることが好ましい。この条件を満たす電極構造としては、例えば、平行平板型、円筒型構造等が挙げられるが、本発明では、３枚以上の電極を用いる場合は、平行平板型が好ましい。
【００２８】
さらに、プラズマを発生させる電極は、一対のうち少なくとも一方の対向面に固体誘電体が配置されている必要がある。この際、固体誘電体と設置される側の電極が密着し、かつ、接する電極の対向面を完全に覆うようにすることが好ましい。固体誘電体によって覆われずに電極同士が直接対向する部位があると、そこからアーク放電が生じやすいためである。
【００２９】
上記固体誘電体の形状は、シート状でもフィルム状でもよく、厚みが０．０１〜４ｍｍであることが好ましい。厚すぎると放電プラズマを発生するのに高電圧を要することがあり、薄すぎると電圧印加時に絶縁破壊が起こり、アーク放電が発生することがある。
【００３０】
上記固体誘電体の材質としては、例えば、ポリテトラフルオロエチレン、ポリエチレンテレフタレート等のプラスチック、ガラス、二酸化珪素、酸化アルミニウム、二酸化ジルコニウム、二酸化チタン等の金属酸化物、チタン酸バリウム等の複酸化物、及びこれらの複層化したもの等が挙げられる。
【００３１】
また、上記固体誘電体は、比誘電率が２以上（２５℃環境下、以下同じ）であることが好ましい。比誘電率が２以上の誘電体の具体例としては、ポリテトラフルオロエチレン、ガラス、金属酸化膜等を挙げることができる。さらに高密度の放電プラズマを安定して発生させるためには、比誘電率が１０以上の固定誘電体を用いことが好ましい。比誘電率の上限は特に限定されるものではないが、現実の材料では１８，５００程度のものが知られている。比誘電率が１０以上の固体誘電体としては、例えば、酸化チタニウム５〜５０重量％、酸化アルミニウム５０〜９５重量％で混合された金属酸化物皮膜、または、酸化ジルコニウムを含有する金属酸化物皮膜からなるものが好ましい。
【００３２】
上記電極間の距離は、固体誘電体の厚さ、印加電圧の大きさ、プラズマを利用する目的等を考慮して適宜決定されるが、０．１〜５０ｍｍであることが好ましく、より好ましくは５ｍｍ以下である。５０ｍｍを超えると、均一な放電プラズマを発生させにくい。
【００３３】
上記電極間には、電界が印加され、プラズマを発生させるが、パルス電界を印加することが好ましく、特に、電界の立ち上がり及び／又は立ち下がり時間が、１０μｓ以下である電界が好ましい。１０μｓを超えると放電状態がアークに移行しやすく不安定なものとなり、パルス電界による高密度プラズマ状態を保持しにくくなる。また、立ち上がり時間及び立ち下がり時間が短いほどプラズマ発生の際のガスの電離が効率よく行われるが、４０ｎｓ未満の立ち上がり時間のパルス電界を実現することは、実際には困難である。より好ましくは５０ｎｓ〜５μｓである。なお、ここでいう立ち上がり時間とは、電圧（絶対値）が連続して増加する時間、立ち下がり時間とは、電圧（絶対値）が連続して減少する時間を指すものとする。
【００３４】
上記パルス電界の電界強度は、１０〜１０００ｋＶ／ｃｍであり、好ましくは２０〜３００ｋＶ／ｃｍである。電界強度が１０ｋＶ／ｃｍ未満であると処理に時間がかかりすぎ、１０００ｋＶ／ｃｍを超えるとアーク放電が発生しやすくなる。
【００３５】
上記パルス電界の周波数は、０．５ｋＨｚ以上であることが好ましい。０．５ｋＨｚ未満であるとプラズマ密度が低いため処理に時間がかかりすぎる。上限は特に限定されないが、常用されている１３．５６ＭＨｚ、試験的に使用されている５００ＭＨｚといった高周波帯でも構わない。負荷との整合のとり易さや取り扱い性を考慮すると、５００ｋＨｚ以下が好ましい。このようなパルス電界を印加することにより、処理速度を大きく向上させることができる。
【００３６】
また、上記パルス電界におけるひとつのパルス継続時間は、２００μｓ以下であることが好ましく、より好ましくは３〜２００μｓである。２００μｓを超えるとアーク放電に移行しやすくなる。ここで、ひとつのパルス継続時間とは、ＯＮ、ＯＦＦの繰り返しからなるパルス電界における、ひとつのパルスの連続するＯＮ時間を言う。
【００３７】
本発明の薄膜を形成するためにプラズマ発生室に導入するガスとしては、金属酸化膜又は金属窒化膜を形成するガスの組み合わせであって、▲１▼薄膜中に含まれる金属元素を含有する原料ガスである金属元素含有ガスと、▲２▼この金属元素を含有する原料ガスと反応して薄膜形成を促進する酸素含有ガス又は窒素含有ガスの反応ガスと、▲３▼ほとんど反応させずに希釈するのみかもしくは前記ガスの励起を促進するかあるいは励起種を安定させるための希釈ガスとの組み合わせよりなる。具体的には、次のような例が挙げられ、それぞれを適宜組み合わせて用いることができる。
【００３８】
（１）酸化膜
酸化膜の種類としては、絶縁膜、Ｈｉｇｈ−ｋ膜、透明導電膜が挙げられる。
▲１▼原料用ガス
（ｉ）絶縁膜（ＳｉＯ2）用原料ガス
ＳｉＨ4、Ｓｉ2Ｈ6等のシラン系ガス、Ｓｉ（ＣＨ3）4等のアルキルシラン系ガス、Ｓｉ（ＯＣ2Ｈ5）4、Ｓｉ（ＯＣＨ3）4等のアルコキシシラン系ガス、Ｓｉ（ＯＣＯＣＨ3）4等のアセトキシシラン系ガス、Ｓｉ（ＮＣＯ）4ガスが挙げられる。また、これらのガスには、Ｐ（ＣＨ3）3、Ｂ（ＣＨ3）3、ＰＨ3、Ｂ2Ｈ6等を添加して複合酸化物としてもよい。
（ｉｉ）Ｈｉｇｈ−ｋ膜用原料ガス
Ｔａ（ＯＣ2Ｈ5）5からのＴａ2Ｏ5膜、Ｙ（ＯｉＣ3Ｈ7）3からのＹ2Ｏ5膜、Ｈｆ（ＯｉＣ3Ｈ7）4からのＨｆＯ2膜、Ｚｎ（Ｃ2Ｈ5）2、Ｚｎ（ＯＣ2Ｈ5）2からＺｎＯ2膜が挙げられる。
（ｉｉｉ）透明導電膜用原料ガス
Ｉｎ（Ｏｉ−Ｃ3Ｈ7）3、Ｉｎ（ＣＨ3）3、Ｚｎ（Ｃ2Ｈ5）2、Ｚｎ（ＯＣ2Ｈ5）2等が挙げられる。さらにドーピング用として、ＳｎＣｌ2、Ａｌ（ＣＨ3）3、Ａｌ（ＯｉＣ3Ｈ7）3、Ｓｂ（ＯＣ2Ｈ5）3等が挙げられる。
▲２▼反応性ガス
酸素元素含有ガスとしては、Ｏ2、Ｏ3、Ｎ2Ｏ、乾燥空気等の酸素含有ガスが挙げられる。
▲３▼希釈ガス
ネオン、アルゴン、キセノン、Ｎ2、ヘリウム等が挙げられる。
【００３９】
（２）窒化膜
▲１▼原料ガス
ＳｉＨ4、Ｓｉ2Ｈ6等のシラン系ガス、Ｓｉ（ＣＨ3）4等のアルキルシラン系ガス、ＴｉＣｌ2、Ａｌ（ＣＨ3）3等が挙げられる。
▲２▼反応ガス
無水アンモニア、Ｎ2等の窒素含有ガスが挙げられる。
▲３▼希釈ガス
ネオン、アルゴン、キセノン、Ｎ2、ヘリウム等が挙げられる。
【００４０】
本発明では、経済性及び安全性等の観点から、原料ガスを希釈ガスによって希釈し、これを処理ガスとして用いる方法が特に好ましい。希釈ガスは、単独でも２種以上を混合して用いてもよい。
【００４１】
原料ガスの不活性ガスとの混合比は、使用する不活性ガスの種類により適宜決定される。パルス電界を印加する場合は、任意の混合比の雰囲気下で処理が可能であるが、原料ガスの濃度が高すぎると放電プラズマが発生し難くなるため、原料ガスの濃度が、原料ガスと不活性ガスとの混合ガス中の０．００１〜１０体積％であることが好ましく、より好ましくは０．００１〜０．５体積％である。
【００４２】
本発明において、酸化金属薄膜又は窒化金属薄膜を形成する被処理基材としては、プラズマ放電手段がリモート型であるので、特に限定されないが、例えば、シリコンウェーハ、石英ガラス、プラスチックフィルム等が挙げられる。
【００４３】
本発明のパルス電界を用いた大気圧放電では、全くガス種に依存せず、電極間において直接大気圧に放電を生じせしめることが可能であり、より単純化された電極構造、放電手順による大気圧プラズマ装置、及び処理手法でかつ高速処理を実現することができる。また、パルス周波数、電圧、電極間隔等のパラメータにより各薄膜に関する半導体素子処理パラメータも調整できる。
【００４４】
さらに、印加パルス電界の形状及び変調を含む周波数制御により選択励起が可能であり、特定化合物の成膜速度を選択的に向上させたり不純物等の純度制御が可能である。
【００４５】
【実施例】
以下に実施例を挙げて本発明を具体的に説明するが、本発明はこれら実施例のみに限定されるものではない。
【００４６】
実施例１
図１に示す装置において、平行平板型電極として、幅１５０ｍｍ×長さ６０ｍｍ×厚み１５ｍｍのＳＵＳ製の電極に固体誘電体として、厚さ０．５ｍｍにアルミナを溶射したものを用い、２ｍｍの間隔を置いて平行に設置した。また、一方の電極の中間に酸素導入口４として、１ｍｍ幅のスリット状の穴を設けた。処理ガスとして、ＴＥＯＳ／Ｎ2の混合ガスをガス導入口５からプラズマ発生室６に導入し、酸素導入口４からＯ2を導入し、プラズマ発生室６’内においてＴＥＯＳ／Ｎ2／Ｏ2が０．０５（ｇ／ｍｉｎ）／８（Ｌ／ｍｉｎ）／２（Ｌ／ｍｉｎ）になるようにした。電極には、ＶP-P２０ｋＶ、１０ｋＨｚのパルス電界を印加し、１００℃に加熱したＳｉウェーハ基材上にプラズマ流を吹き付け基材上にＳｉＯ2膜を形成した。得られたＳｉＯ2膜をＦＴ−ＩＲで測定し、９４０ｃｍ-1のＳｉＯＨ基と１０７０ｃｍ-1のＳｉＯＳｉ基のピーク強度比を求め、膜質の評価を行ったところ、ＳｉＯＨ／ＳｉＯＳｉが０．０５の酸化膜が形成されていた。
【００４７】
実施例２
図２に示す装置において、プラズマ発生室６及び６’用の印加側平板型電極として、幅１５０ｍｍ×長さ７０ｍｍ×厚み１５ｍｍのＳＵＳ製の電極に固体誘電体として、厚さ０．５ｍｍにアルミナを溶射したものを用い、接地側平板型電極３と３’用電極として、幅１５０ｍｍ×長さ３０ｍｍ×厚み１５ｍｍのＳＵＳ製の電極に固体誘電体として、厚さ０．５ｍｍにアルミナを溶射したものを用い、それぞれ２ｍｍの間隔を置いて平行に設置した。また、プラズマ発生室６’’用として、平行平板型電極として、幅１５０ｍｍ×長さ３０ｍｍ×厚み１５ｍｍのＳＵＳ製の電極に固体誘電体として、厚さ０．５ｍｍにアルミナを溶射したものを用い、２ｍｍの間隔を置いて平行に設置した。処理ガスとしてＴＥＯＳ／Ｎ2／Ｏ2ガスを混合比０．０５（ｇ／ｍｉｎ）／９（Ｌ／ｍｉｎ）／１（Ｌ／ｍｉｎ）でプラズマ発生室６に導入した。一方、プラズマ発生室６’’には、Ｎ2／Ｏ2の混合ガスを４（Ｌ／ｍｉｎ）／１（Ｌ／ｍｉｎ）で導入し、プラズマ発生室６’で両プラズマ発生室からのガスを合流させるようにした。それぞれの電極に、ＶP-P２０ｋＶ、１０ｋＨｚのパルス電界を印加し、１００℃に加熱したＳｉウェーハ基材上にプラズマ流を吹き付け基材上にＳｉＯ2膜を形成した。得られたＳｉＯ2膜をＦＴ−ＩＲで測定し、９４０ｃｍ-1のＳｉＯＨ基と１０７０ｃｍ-1のＳｉＯＳｉ基のピーク強度比を求め、膜質の評価を行ったところ、ＳｉＯＨ／ＳｉＯＳｉが０．０５の酸化膜が形成されていた。
【００４８】
実施例３
図３に示す装置において、プラズマ発生室６及び６’’用の印加側平板型電極として、幅３０ｍｍ×長さ６０ｍｍ×厚み１０ｍｍのＳＵＳ製の電極に固体誘電体として、厚さ０．５ｍｍにアルミナを溶射したものを用い、接地側平板型電極として３と３’のような形状の電極を使用し、放電面に固体誘電体として、厚さ０．５ｍｍにアルミナを溶射したものを用い、２ｍｍの間隔を置いて平行に設置した。処理ガスとしてＴＥＯＳ／Ｎ2／Ｏ2ガスを混合比０．０５（ｇ／ｍｉｎ）／４（Ｌ／ｍｉｎ）／１（Ｌ／ｍｉｎ）でプラズマ発生室６に導入した。一方、プラズマ発生室６’’には、Ｎ2／Ｏ2の混合ガスを４（Ｌ／ｍｉｎ）／１（Ｌ／ｍｉｎ）で導入し、プラズマ発生室６’で両プラズマ発生室からのガスを合流させるようにした。電極に、ＶP-P２０ｋＶ、１０ｋＨｚのパルス電界を印加し、１００℃に加熱したＳｉウェーハ基材上にプラズマ流を吹き付け基材上にＳｉＯ2膜を形成した。得られたＳｉＯ2膜をＦＴ−ＩＲで測定し、９４０ｃｍ-1のＳｉＯＨ基と１０７０ｃｍ-1のＳｉＯＳｉ基のピーク強度比を求め、膜質の評価を行ったところ、ＳｉＯＨ／ＳｉＯＳｉが０．０５の酸化膜が形成されていた。
【００４９】
比較例１
実施例１と同じ装置を使用し、酸素導入口から酸素を導入しない以外は、実施例１と同様にして基材上にプラズマ流を吹き付け基材上にＳｉＯ2膜を形成した。得られたＳｉＯ2膜をＦＴ−ＩＲで測定し、９４０ｃｍ-1のＳｉＯＨ基と１０７０ｃｍ-1のＳｉＯＳｉ基のピーク強度比を求め、膜質の評価を行ったところ、ＳｉＯＨ／ＳｉＯＳｉが０．１５の酸化膜が形成されていた。
【００５０】
【発明の効果】
本発明の多段プラズマ処理方法は、リモート型のプラズマ処理装置において、金属元素含有ガスを予めプラズマ励起した後に酸素含有ガス及び／又は窒素含有ガスを導入して、さらにプラズマ励起させることによる多段型の放電プラズマ処理を行うので、安定して均質な金属酸化膜又は窒化膜を形成することができる。
したがって、半導体素子に必要な絶縁膜、Ｈｉｇｈ−ｋ膜、透明導電膜、窒化膜の形成を容易に形成できる。
【図面の簡単な説明】
【図１】本発明の多段型の放電プラズマ処理方法の一例を説明する図である。
【図２】本発明の多段型の放電プラズマ処理方法の一例を説明する図である。
【図３】本発明の多段型の放電プラズマ処理方法の一例を説明する図である。
【符号の説明】
１、１’ 電源
２、２’ 電極
３、３’、３’’ 電極
４ 酸素導入口
５ 処理ガス導入口
６、６’、６’’ プラズマ発生室
７ プラズマ吹出口
８ 被処理基材[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a multi-stage type discharge plasma processing method and apparatus for forming a metal oxide film / metal nitride film thin film by a discharge plasma processing method, and more particularly to an oxygen-containing gas and / or an apparatus after the metal element-containing gas is converted into an excited plasma. Alternatively, the present invention relates to a multistage discharge plasma processing method and apparatus for forming a thin film by mixing nitrogen-containing gas and advancing the reaction.
[0002]
[Prior art]
With increasing density of LSIs, CVD processing methods capable of forming a thin film of a target material on a substrate have been used, and thermal plasma CVD methods and low-pressure plasma CVD methods have been frequently used. Thermal plasma CVD is unavoidable for damage caused by high temperatures, and low pressure plasma CVD requires a device close to a vacuum, which requires high cost for low-pressure equipment. It was. In particular, when a silicon oxide film or the like is formed from a mixed gas using oxygen and a silane compound, it is difficult to form a highly uniform film, and OH groups are formed in the film, improving the film quality. There was a problem of not doing. In order to solve this problem, Japanese Patent Application Laid-Open No. 7-335576 discloses an improvement by performing a pretreatment by introducing an oxygen-containing gas or the like into an acidic active species generation mechanism using high temperature non-equilibrium plasma or high temperature equilibrium plasma. However, the entire apparatus requires low-pressure equipment, and there is a problem that the reaction efficiency is still inferior.
[0003]
On the other hand, a normal pressure plasma processing method capable of performing processing near atmospheric pressure has been developed, and is not damaged by high temperature as in the thermal plasma CVD method, and requires low pressure equipment as in the low pressure plasma CVD method. With this technology, metal-based gas thin films can be easily formed on a substrate with a simple apparatus. Even in the formation of a thin film by the atmospheric pressure plasma method, when a metal oxide film / metal nitride film is formed, the reaction proceeds sufficiently if plasma excitation is performed in a mixed state of a metal-based gas and an oxygen-based gas / nitrogen-based gas. In some cases, improvement in film quality has been demanded.
[0004]
[Problems to be solved by the invention]
In view of the above problems, the present invention is excellent in film quality in forming a metal oxide thin film or metal nitride thin film by discharge plasma treatment, and can easily form a metal oxide thin film or metal nitride thin film at a deposition rate required in the industry. It is an object to provide a method and apparatus.
[0005]
[Means for Solving the Problems]
As a result of diligent research to solve the above-mentioned problems, the present inventors have conducted plasma excitation of a metal element-containing gas in advance in a plasma generation chamber capable of realizing a stable discharge state under atmospheric pressure conditions, and then oxygen-containing gas and The present invention was completed by finding that the intended thin film can be easily formed by introducing a nitrogen-containing gas and / or allowing the reaction to proceed.
[0006]
That is, the first aspect of the present invention is a thin film made of a metal oxide compound and / or a metal nitride compound by reacting a metal element-containing gas with an oxygen-containing gas and / or a nitrogen-containing gas. On the surface of the substrate to be treated In the discharge plasma processing method to be formed, an oxygen-containing gas and / or a nitrogen-containing gas are merged with a metal element-containing gas that has passed through one plasma generation chamber, and then passed through another plasma generation chamber. Spraying the substrate to be processed placed outside the plasma generation chamber, the surface of the substrate to be processed A thin film was formed, and each of the plasma generation chambers was covered with a solid dielectric on at least one opposing surface. Formed between a pair of counter electrodes and facing the above electrode while Apply electric field to by doing A multistage discharge plasma processing method characterized by being a space for generating plasma.
[0007]
According to a second aspect of the present invention, there is provided a thin film comprising a metal oxide compound and / or a metal nitride compound by reacting a metal element-containing gas with an oxygen-containing gas and / or a nitrogen-containing gas. On the surface of the substrate to be treated In the discharge plasma processing method to be formed, the metal element-containing gas that has passed through one plasma generation chamber and the oxygen-containing gas and / or nitrogen-containing gas that has passed through another plasma generation chamber are merged to generate another plasma. Let the room pass Spraying the substrate to be processed placed outside the plasma generation chamber, the surface of the substrate to be processed A thin film was formed, and each of the plasma generation chambers was covered with a solid dielectric on at least one opposing surface. Formed between a pair of counter electrodes, and the counter electrode while Apply electric field to by doing A multistage discharge plasma processing method characterized by being a space for generating plasma.
[0009]
According to a third aspect of the present invention, the electric field is a pulsed electric field having a pulse rise and / or fall time of 10 μs or less. Or 2 It is the multistage type discharge plasma processing method as described in this invention.
[0010]
In addition, the first of the present invention 4 According to the present invention, the electric field is a pulsed electric field having an electric field strength of 10 to 1000 kV / cm. 3 A multistage discharge plasma processing method according to any one of the inventions.
[0011]
The fifth invention of the present invention is: In a discharge plasma processing apparatus in which a metal element-containing gas and an oxygen-containing gas and / or a nitrogen-containing gas are reacted to form a thin film made of a metal oxide compound and / or a metal nitride compound on the surface of a substrate to be processed, at least one facing Having a pair of opposing electrodes whose surfaces are coated with a solid dielectric, Counter electrode Between At one end of 1's Process gas inlet Is provided , Between the counter electrodes Gas outlet at another end Is provided , (1) between the counter electrodes Between the processing gas inlet and the gas outlet another Process gas inlet The portion between the one processing gas introduction port and the other processing gas introduction port between the counter electrodes constitutes one plasma generation chamber, and the other electrode between the counter electrodes is provided. A portion between the processing gas inlet and the gas outlet forms another plasma generation chamber, and when an electric field is applied between the counter electrodes, plasma is generated in each plasma generation chamber, and the metal The element-containing gas is introduced into the one plasma generation chamber from the one processing gas inlet and is plasma-excited in the first plasma generation chamber without being mixed with the oxygen-containing gas and / or the nitrogen-containing gas. The oxygen-containing gas and / or the nitrogen-containing gas is introduced into the another plasma generation chamber from the other processing gas inlet and passes through the one plasma generation chamber. The merged and merged gas passes through the another plasma generation chamber and is blown out from the gas outlet, and blown onto the substrate to be processed disposed outside the counter electrode, and the substrate to be processed The above thin film is formed on the surface of This is a discharge plasma processing apparatus.
[0012]
The sixth invention of the present invention is Another Process gas inlet One of the pair of counter electrodes The discharge plasma processing apparatus according to the fifth aspect, wherein the discharge plasma processing apparatus is formed by a hole provided in the electrode.
[0014]
In addition, the first of the present invention 7 The invention of A gas flow blown out of the first plasma generation chamber and the second plasma generation chamber, comprising a first plasma generation chamber formed by one counter electrode and a second plasma generation chamber formed by another counter electrode Are merged and introduced into the third plasma generation chamber, The discharge plasma processing apparatus is characterized in that the electrodes on the electric field application side of the first plasma generation chamber and the third plasma generation chamber are common.
[0015]
In addition, the first of the present invention 8 The invention of A gas flow blown out of the first plasma generation chamber and the second plasma generation chamber, comprising a first plasma generation chamber formed by one counter electrode and a second plasma generation chamber formed by another counter electrode Are merged and introduced into the third plasma generation chamber, The discharge plasma processing apparatus is characterized in that the electric field application side electrodes of the first plasma generation chamber and the second plasma generation chamber are common.
[0016]
In addition, the present invention Do not claim The eleventh invention is characterized in that a metal element-containing gas is introduced into the first plasma generation chamber and an oxygen-containing gas and / or a nitrogen-containing gas is introduced into the second plasma generation chamber. First 7 or 8 It is a discharge plasma processing apparatus as described in this invention.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
In the method for forming a metal oxide compound thin film or a metal nitride compound thin film of the present invention, a metal element-containing gas and an oxygen-containing gas and / or a nitrogen-containing gas are reacted to form a thin film made of a metal oxide compound and / or a metal nitride compound. In this method, a metal element-containing gas which is difficult to be excited is pre-excited in a plasma generation chamber, then an oxygen-containing gas or a nitrogen-containing gas is introduced, and further a plasma treatment reaction proceeds in the next plasma generation chamber This is a discharge plasma treatment method. The processing method includes the following two types of methods. (1) After the metal element-containing gas is plasma-excited in the first half of one plasma generation chamber, the oxygen-containing gas and / or nitrogen-containing gas is merged, and the merged mixed gas is plasma-excited in the second half of the plasma generation chamber And (2) the metal element-containing gas and the oxygen-containing gas and / or the nitrogen-containing gas are excited in separate plasma generation chambers and merged, and after merging, another plasma In this method, a mixed gas is plasma-excited in a generation chamber and sprayed onto a substrate. Whichever method is used, a metal oxide thin film or a metal nitride thin film excellent in film quality can be obtained.
[0018]
Here, the plasma generation chamber has at least a pair of counter electrodes, and discharge between the electrodes that generates plasma by applying an electric field between electrodes in which at least one counter surface of the counter electrode is coated with a solid dielectric. It is space. In the present invention, a processing gas is introduced into the plasma generation chamber to form plasma, and then plasma is blown out of the discharge space, and a plasma flow is sprayed onto the surface of the substrate to be processed disposed outside the discharge space. Process. The plasma generation chamber is mainly composed of parallel plate electrodes or coaxial cylindrical electrodes, and the outlet is a substrate to be processed in which a plasma flow is arranged outside the discharge space using a long nozzle or a cylindrical nozzle. It is preferable to be able to spray on the surface.
[0019]
The multistage type discharge plasma processing apparatus of the present invention joins the second gas to the first gas that has passed through one plasma generation chamber, passes through the other plasma generation chamber, and receives the discharge plasma of the mixed gas. It is the processing apparatus sprayed on a processing base material. In the present invention, there are two types of apparatuses: a case where the second gas is previously plasma-discharged and a case where the second gas is not previously discharged.
[0020]
In the case where the second gas is not plasma-discharged in advance, a processing gas inlet (1) is provided at one end of the counter electrode, a gas outlet is provided at the other end, and the processing gas inlet (1 ) And a gas outlet, and a discharge plasma processing apparatus provided with a processing gas inlet (2). In the formation of the thin film in this apparatus, a metal element-containing gas is introduced from the processing gas inlet (1), and an oxygen-containing gas and / or a nitrogen-containing gas is introduced from the processing gas inlet (2). The intermediate position at which the processing gas inlet (2) is provided only needs to be between the inlet (1) and the outlet, and does not have to be strictly located at the center. Further, the processing gas introduction port (2) may be a hole provided in the electrode of the counter electrode, and the number of holes may be one or many. The metal element-containing gas is excited on the upstream side of the processing gas inlet (2), and the mixed gas is excited on the downstream side.
[0021]
The apparatus in the case where the second gas is preliminarily plasma-discharged includes a first plasma generation chamber formed by one counter electrode, a second plasma generation chamber formed by another counter electrode, A discharge plasma processing apparatus in which the gas flow blown out from the first plasma generation chamber and the second plasma generation chamber merges and is introduced into the third plasma generation chamber can be given. In the formation of the thin film in this apparatus, the metal element-containing gas is excited in the first plasma generation chamber, the oxygen-containing gas and / or the nitrogen-containing gas is excited in the second plasma generation chamber, and a third plasma is generated. The mixed gas is excited in the chamber.
[0022]
An example of the method and apparatus of the present invention will be described with reference to the drawings. FIG. 1 is a diagram for explaining a method and an apparatus in which an oxygen-containing gas and / or a nitrogen-containing gas are merged after plasma excitation of a metal element-containing gas, and the mixed gas mixture is plasma-excited and sprayed onto a substrate. is there. In FIG. 1, a metal element-containing gas is introduced in the direction of an arrow from a gas introduction port 5 of a plasma generation chamber 6 which has a pair of counter electrodes 2 and 3 and generates an plasma by applying an electric field from a power source 1 to the electrodes. Plasma excitation is performed in the plasma generation chamber 6. On the other hand, the oxygen-containing gas and / or the nitrogen-containing gas is introduced into the plasma generation chamber from the inlet 4 provided in the electrode 2 and merged with the metal element-containing gas excited in the plasma generation chamber 6 to generate plasma. Plasma is further excited in the chamber 6 '. The plasma flow of the mixed gas, which is plasma-excited in the plasma generation chamber 6 ′ and promoted the oxidation reaction and / or nitridation reaction, is blown from the plasma outlet 7 to the substrate 8 to be processed, and a metal oxide film is formed on the substrate. And / or a metal nitride film is formed.
[0023]
FIG. 2 shows that the metal element-containing gas and the oxygen-containing gas and / or the nitrogen-containing gas are combined after being excited in the first plasma generation chamber and the second plasma generation chamber, respectively, It is a figure explaining the method and apparatus which plasma-excited the mixed gas merged in the plasma generation chamber of this, and sprays it on a base material. In FIG. 2, a metal element-containing gas is introduced in the direction of an arrow from a gas inlet 5 of a plasma generation chamber 6 that has a pair of counter electrodes 2 and 3 and generates an plasma by applying an electric field from a power source 1 to the electrodes. Plasma excitation is performed in the plasma generation chamber 6. On the other hand, the oxygen-containing gas and / or the nitrogen-containing gas has a pair of counter electrodes 2 ′ and 3 ″, and a gas in a plasma generation chamber 6 ″ that generates plasma by applying an electric field from a power source 1 ′ to the electrodes. From the introduction port, an oxygen-containing gas and / or a nitrogen-containing gas is introduced in the direction of the arrow, and plasma excitation is performed in the plasma generation chamber 6 ''. The plasma flow of the oxygen-containing gas and / or the nitrogen-containing gas is merged with the plasma flow of the metal element-containing gas from the plasma generation chamber 6 and has a pair of counter electrodes 2 and 3 ′. It is introduced into a plasma generation chamber 6 ′ that generates a plasma upon application, and is further excited in the plasma generation chamber 6 ′. The plasma flow of the combined gas that has been plasma-excited in the plasma generation chamber 6 ′ and promoted the oxidation reaction and / or nitridation reaction is sprayed from the plasma outlet 7 to the substrate 8 to be treated, and the metal oxide and the A metal nitride thin film is formed. In this apparatus, the application electrode 2 which is the electrode on the electric field application side of the first plasma generation chamber and the third plasma generation chamber is shared with the ground electrodes 3 and 3 ′, thereby preventing duplication of equipment. Can do.
[0024]
FIG. 3 shows a case where a metal element-containing gas and an oxygen-containing gas and / or a nitrogen-containing gas are combined after being excited in the first plasma generation chamber and the second plasma generation chamber, respectively. It is a figure explaining the method and apparatus which plasma-excited the mixed gas merged in the plasma generation chamber of this, and sprays it on a base material. In FIG. 3, an apparatus having plasma generating chambers 6 and 6 ′ that share an applied electrode 2 and are composed of ground electrodes 3 and 3 ′, which excites a metal element-containing gas in the plasma generating chamber 6, thereby generating an oxygen-containing gas. And / or a nitrogen-containing gas is plasma-excited in the plasma generation chamber 6 ″, and merged in the plasma generation chamber 6 ″ and simultaneously plasma-excited in the plasma generation chamber 6 ′. The plasma flow of the combined gas that has been plasma-excited in the plasma generation chamber 6 ′ and promoted the oxidation reaction and / or nitridation reaction is sprayed from the plasma outlet 7 onto the substrate 8 to be processed, and a metal oxide film is formed on the substrate. And / or a metal nitride film is formed. In this apparatus, the electrodes on the electric field application side of the first plasma generation chamber and the second plasma generation chamber are shared to prevent duplication of equipment.
[0025]
The production of the thin film of the present invention using the apparatus as described above is preferably a method using atmospheric pressure plasma that excites a metal element-containing gas using plasma generated by applying an electric field under a pressure close to atmospheric pressure.
[0026]
The pressure near the atmospheric pressure is 1.333 × 10 Four ~ 10.664 × 10 Four It refers to the pressure under Pa. Above all, pressure adjustment is easy and the apparatus is simple 9.331 × 10 Four ~ 10.397 × 10 Four A range of Pa is preferred.
[0027]
Examples of the material of the electrode used above include a metal simple substance such as copper and aluminum, an alloy such as stainless steel and brass, and an intermetallic compound. The counter electrode preferably has a structure in which the distance between the counter electrodes is substantially constant in order to avoid occurrence of arc discharge due to electric field concentration. Examples of the electrode structure that satisfies this condition include a parallel plate type and a cylindrical type structure. In the present invention, a parallel plate type is preferable when three or more electrodes are used.
[0028]
Furthermore, the electrode for generating plasma needs to have a solid dielectric disposed on at least one opposing surface of the pair. At this time, it is preferable that the solid dielectric and the electrode on the side to be installed are in close contact with each other and the opposite surface of the electrode in contact is completely covered. This is because if there is a portion where the electrodes directly face each other without being covered by the solid dielectric, arc discharge is likely to occur therefrom.
[0029]
The solid dielectric may have a sheet shape or a film shape, and preferably has a thickness of 0.01 to 4 mm. If it is too thick, a high voltage may be required to generate discharge plasma, and if it is too thin, dielectric breakdown may occur when a voltage is applied, and arc discharge may occur.
[0030]
Examples of the material of the solid dielectric include, for example, plastics such as polytetrafluoroethylene and polyethylene terephthalate, glass, metal oxides such as silicon dioxide, aluminum oxide, zirconium dioxide, and titanium dioxide, double oxides such as barium titanate, And those having a multi-layered structure.
[0031]
The solid dielectric preferably has a relative dielectric constant of 2 or more (the same applies below at 25 ° C.). Specific examples of the dielectric having a relative dielectric constant of 2 or more include polytetrafluoroethylene, glass, and metal oxide film. In order to stably generate a high-density discharge plasma, it is preferable to use a fixed dielectric having a relative dielectric constant of 10 or more. The upper limit of the relative dielectric constant is not particularly limited, but about 18,500 is known as an actual material. Examples of the solid dielectric having a relative dielectric constant of 10 or more include a metal oxide film mixed with 5 to 50% by weight of titanium oxide and 50 to 95% by weight of aluminum oxide, or a metal oxide film containing zirconium oxide. Those consisting of are preferred.
[0032]
The distance between the electrodes is appropriately determined in consideration of the thickness of the solid dielectric, the magnitude of the applied voltage, the purpose of using plasma, etc., but is preferably 0.1 to 50 mm, more preferably 5 mm or less. If it exceeds 50 mm, it is difficult to generate uniform discharge plasma.
[0033]
An electric field is applied between the electrodes to generate plasma, but a pulsed electric field is preferably applied, and an electric field having a rising time and / or a falling time of 10 μs or less is particularly preferable. If it exceeds 10 μs, the discharge state tends to shift to an arc and becomes unstable, and it becomes difficult to maintain a high-density plasma state by a pulse electric field. Also, the shorter the rise time and fall time, the more efficiently ionization of the gas during plasma generation, but it is actually difficult to realize a pulsed electric field with a rise time of less than 40 ns. More preferably, it is 50 ns to 5 μs. The rise time here refers to the time during which the voltage (absolute value) increases continuously, and the fall time refers to the time during which the voltage (absolute value) decreases continuously.
[0034]
The electric field strength of the pulse electric field is 10 to 1000 kV / cm, preferably 20 to 300 kV / cm. If the electric field strength is less than 10 kV / cm, the process takes too much time, and if it exceeds 1000 kV / cm, arc discharge tends to occur.
[0035]
The frequency of the pulse electric field is preferably 0.5 kHz or more. If it is less than 0.5 kHz, the plasma density is low, and the processing takes too long. The upper limit is not particularly limited, but it may be a high frequency band such as 13.56 MHz that is commonly used and 500 MHz that is used experimentally. In consideration of ease of matching with the load and handleability, 500 kHz or less is preferable. By applying such a pulse electric field, the processing speed can be greatly improved.
[0036]
Moreover, it is preferable that one pulse duration in the said pulse electric field is 200 microseconds or less, More preferably, it is 3-200 microseconds. If it exceeds 200 μs, it tends to shift to arc discharge. Here, one pulse duration refers to the continuous ON time of one pulse in a pulse electric field consisting of repetition of ON and OFF.
[0037]
The gas introduced into the plasma generation chamber for forming the thin film of the present invention is a combination of gases forming a metal oxide film or a metal nitride film, and (1) a raw material containing a metal element contained in the thin film (2) dilution with little reaction with (3) a gas containing a metal element that is a gas and (2) a reaction gas of an oxygen-containing gas or a nitrogen-containing gas that reacts with the source gas containing this metal element to promote thin film formation Or a combination with a diluent gas for promoting the excitation of the gas or stabilizing the excited species. Specific examples include the following, which can be used in appropriate combination.
[0038]
(1) Oxide film
Examples of the oxide film include an insulating film, a high-k film, and a transparent conductive film.
(1) Raw material gas
(I) Insulating film (SiO 2 ) Raw material gas
SiH Four , Si 2 H 6 Silane gases such as Si (CH Three ) Four Alkylsilane gases such as Si (OC 2 H Five ) Four , Si (OCH Three ) Four Alkoxysilane gases such as Si (OCOCH Three ) Four Acetoxysilane-based gas such as Si (NCO) Four Gas. These gases include P (CH Three ) Three , B (CH Three ) Three , PH Three , B 2 H 6 Etc. may be added to form a composite oxide.
(Ii) High-k film source gas
Ta (OC 2 H Five ) Five Ta from 2 O Five Film, Y (OiC Three H 7 ) Three Y from 2 O Five Membrane, Hf (OiC Three H 7 ) Four HfO from 2 Film, Zn (C 2 H Five ) 2 Zn (OC 2 H Five ) 2 To ZnO 2 A membrane is mentioned.
(Iii) Raw material gas for transparent conductive film
In (Oi-C Three H 7 ) Three , In (CH Three ) Three Zn (C 2 H Five ) 2 Zn (OC 2 H Five ) 2 Etc. In addition, SnCl for doping 2 , Al (CH Three ) Three , Al (OiC Three H 7 ) Three , Sb (OC 2 H Five ) Three Etc.
(2) Reactive gas
As the oxygen element-containing gas, O 2 , O Three , N 2 O and oxygen-containing gas such as dry air can be used.
(3) Dilution gas
Neon, argon, xenon, N 2 , Helium and the like.
[0039]
(2) Nitride film
(1) Raw material gas
SiH Four , Si 2 H 6 Silane gases such as Si (CH Three ) Four Alkylsilane gases such as TiCl 2 , Al (CH Three ) Three Etc.
(2) Reaction gas
Anhydrous ammonia, N 2 And nitrogen-containing gases such as
(3) Dilution gas
Neon, argon, xenon, N 2 , Helium and the like.
[0040]
In the present invention, from the viewpoints of economy and safety, a method of diluting the raw material gas with a diluent gas and using this as the processing gas is particularly preferable. The dilution gas may be used alone or in combination of two or more.
[0041]
The mixing ratio of the source gas to the inert gas is appropriately determined depending on the type of the inert gas used. When a pulsed electric field is applied, processing can be performed in an atmosphere having an arbitrary mixing ratio. However, if the concentration of the source gas is too high, it is difficult to generate discharge plasma. It is preferable that it is 0.001-10 volume% in mixed gas with an active gas, More preferably, it is 0.001-0.5 volume%.
[0042]
In the present invention, the substrate to be treated for forming the metal oxide thin film or the metal nitride thin film is not particularly limited because the plasma discharge means is remote type, and examples thereof include silicon wafers, quartz glass, and plastic films. .
[0043]
In the atmospheric pressure discharge using the pulsed electric field of the present invention, it is possible to cause discharge to atmospheric pressure directly between the electrodes without depending on the gas type at all. High-speed processing can be realized with the atmospheric pressure plasma apparatus and the processing technique. In addition, semiconductor element processing parameters for each thin film can be adjusted by parameters such as pulse frequency, voltage, and electrode interval.
[0044]
Furthermore, selective excitation is possible by frequency control including the shape and modulation of the applied pulse electric field, and the film formation rate of a specific compound can be selectively improved and the purity of impurities and the like can be controlled.
[0045]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to only these examples.
[0046]
Example 1
In the apparatus shown in FIG. 1, as a parallel plate type electrode, a SUS electrode having a width of 150 mm × a length of 60 mm × a thickness of 15 mm is used as a solid dielectric, and alumina is sprayed to a thickness of 0.5 mm, with a spacing of 2 mm. Placed in parallel. Further, a slit-like hole having a width of 1 mm was provided as an oxygen inlet 4 in the middle of one of the electrodes. As processing gas, TEOS / N 2 Is introduced into the plasma generation chamber 6 from the gas inlet 5 and O is introduced from the oxygen inlet 4. 2 TEOS / N in the plasma generation chamber 6 ' 2 / O 2 Of 0.05 (g / min) / 8 (L / min) / 2 (L / min). The electrode has V PP A plasma flow was sprayed on a Si wafer substrate heated to 100 ° C. by applying a pulse electric field of 20 kV and 10 kHz, and SiO on the substrate. 2 A film was formed. Obtained SiO 2 Membrane measured by FT-IR, 940cm -1 1070 cm with SiOH group -1 When the peak intensity ratio of the SiOSi group was obtained and the film quality was evaluated, an oxide film having a SiOH / SiOSi ratio of 0.05 was formed.
[0047]
Example 2
In the apparatus shown in FIG. 2, as an application-side flat electrode for the plasma generation chambers 6 and 6 ′, a SUS electrode having a width of 150 mm × a length of 70 mm × a thickness of 15 mm is used as a solid dielectric, and an alumina is formed to a thickness of 0.5 mm. As a ground side flat plate electrode 3 and 3 ′ electrode, a SUS electrode having a width of 150 mm × a length of 30 mm × a thickness of 15 mm was sprayed as a solid dielectric, and alumina was sprayed to a thickness of 0.5 mm. These were installed in parallel at intervals of 2 mm. Also, for the plasma generation chamber 6 ″, a parallel plate type electrode having a width of 150 mm × length of 30 mm × thickness of 15 mm made of SUS as a solid dielectric and a thickness of 0.5 mm of alumina sprayed is used. They were installed in parallel with an interval of 2 mm. TEOS / N as processing gas 2 / O 2 The gas was introduced into the plasma generation chamber 6 at a mixing ratio of 0.05 (g / min) / 9 (L / min) / 1 (L / min). On the other hand, the plasma generation chamber 6 ″ has N 2 / O 2 Was introduced at 4 (L / min) / 1 (L / min), and the gases from both plasma generation chambers were merged in the plasma generation chamber 6 ′. Each electrode has a V PP A plasma flow was sprayed on a Si wafer substrate heated to 100 ° C. by applying a pulse electric field of 20 kV and 10 kHz, and SiO on the substrate. 2 A film was formed. Obtained SiO 2 Membrane measured by FT-IR, 940cm -1 1070 cm with SiOH group -1 When the peak intensity ratio of the SiOSi group was obtained and the film quality was evaluated, an oxide film having a SiOH / SiOSi ratio of 0.05 was formed.
[0048]
Example 3
In the apparatus shown in FIG. 3, as an application-side plate-type electrode for the plasma generation chambers 6 and 6 ″, a SUS electrode having a width of 30 mm × a length of 60 mm × a thickness of 10 mm is used as a solid dielectric, and the thickness is 0.5 mm. Using a thermal sprayed alumina, using electrodes with shapes like 3 and 3 'as the ground side flat plate electrode, using a solid dielectric on the discharge surface, and spraying alumina to a thickness of 0.5 mm, They were installed in parallel with an interval of 2 mm. TEOS / N as processing gas 2 / O 2 The gas was introduced into the plasma generation chamber 6 at a mixing ratio of 0.05 (g / min) / 4 (L / min) / 1 (L / min). On the other hand, the plasma generation chamber 6 '' has N 2 / O 2 Was introduced at 4 (L / min) / 1 (L / min), and the gases from both plasma generation chambers were merged in the plasma generation chamber 6 ′. V on the electrode PP A plasma flow was sprayed on a Si wafer substrate heated to 100 ° C. by applying a pulse electric field of 20 kV and 10 kHz, and SiO on the substrate. 2 A film was formed. Obtained SiO 2 Membrane measured by FT-IR, 940cm -1 1070 cm with SiOH group -1 When the peak intensity ratio of the SiOSi group was obtained and the film quality was evaluated, an oxide film having a SiOH / SiOSi ratio of 0.05 was formed.
[0049]
Comparative Example 1
Using the same apparatus as in Example 1, except that oxygen was not introduced from the oxygen inlet, a plasma flow was sprayed onto the substrate in the same manner as in Example 1, and SiO was formed on the substrate. 2 A film was formed. Obtained SiO 2 Membrane measured by FT-IR, 940cm -1 1070 cm with SiOH group -1 When the peak intensity ratio of the SiOSi group was obtained and the film quality was evaluated, an oxide film having a SiOH / SiOSi of 0.15 was formed.
[0050]
【The invention's effect】
The multi-stage plasma processing method of the present invention is a multi-stage plasma processing apparatus in which a metal element-containing gas is pre-excited in a remote plasma processing apparatus and then an oxygen-containing gas and / or a nitrogen-containing gas is introduced and further plasma excited. Since the discharge plasma treatment is performed, a stable and homogeneous metal oxide film or nitride film can be formed.
Therefore, the insulating film, high-k film, transparent conductive film, and nitride film necessary for the semiconductor element can be easily formed.
[Brief description of the drawings]
FIG. 1 is a diagram illustrating an example of a multistage discharge plasma processing method of the present invention.
FIG. 2 is a diagram illustrating an example of a multistage discharge plasma processing method of the present invention.
FIG. 3 is a diagram illustrating an example of a multistage discharge plasma processing method of the present invention.
[Explanation of symbols]
1, 1 'power supply
2, 2 'electrode
3, 3 ', 3''electrode
4 Oxygen inlet
5 Process gas inlet
6, 6 ', 6 "plasma generation chamber
7 Plasma outlet
8 treated substrate

Claims (8)

金属元素含有ガスと酸素含有ガス及び／又は窒素含有ガスを反応させて酸化金属化合物及び／又は窒化金属化合物からなる薄膜を被処理基材の表面に形成する放電プラズマ処理方法において、一つのプラズマ発生室を通過した金属元素含有ガスに、酸素含有ガス及び／又は窒素含有ガスを合流させて、別のプラズマ発生室を通過させてこれらプラズマ発生室の外部に配置した上記被処理基材に吹き付け、上記被処理基材の表面に上記薄膜を形成し、上記各プラズマ発生室が、少なくとも一方の対向面が固体誘電体で被覆された一対の対向電極の間に形成され、かつ上記対向電極間に電界を印加することでプラズマを発生させる空間であることを特徴とする多段型の放電プラズマ処理方法。One plasma generation in a discharge plasma processing method in which a metal element-containing gas is reacted with an oxygen-containing gas and / or a nitrogen-containing gas to form a thin film made of a metal oxide compound and / or a metal nitride compound on the surface of the substrate to be processed. The metal element-containing gas that has passed through the chamber is joined to the oxygen-containing gas and / or the nitrogen-containing gas, passed through another plasma generation chamber, and sprayed onto the substrate to be processed disposed outside the plasma generation chamber, The thin film is formed on the surface of the substrate to be treated , and each plasma generation chamber is formed between a pair of counter electrodes whose at least one counter surface is coated with a solid dielectric , and between the counter electrodes A multistage type discharge plasma processing method characterized by being a space where plasma is generated by applying an electric field. 金属元素含有ガスと酸素含有ガス及び／又は窒素含有ガスを反応させて酸化金属化合物及び／又は窒化金属化合物からなる薄膜を被処理基材の表面に形成する放電プラズマ処理方法において、一つのプラズマ発生室を通過した金属元素含有ガスと、別のプラズマ発生室を通過した酸素含有ガス及び／又は窒素含有ガスとを合流させて、更に他のプラズマ発生室を通過させてこれらプラズマ発生室の外部に配置した上記被処理基材に吹き付け、上記被処理基材の表面に上記薄膜を形成し、上記各プラズマ発生室が、少なくとも一方の対向面が固体誘電体で被覆された一対の対向電極の間に形成され、かつ前記対向電極間に電界を印加することでプラズマを発生させる空間であることを特徴とする多段型の放電プラズマ処理方法。One plasma generation in a discharge plasma processing method in which a metal element-containing gas and an oxygen-containing gas and / or a nitrogen-containing gas are reacted to form a thin film made of a metal oxide compound and / or a metal nitride compound on the surface of a substrate to be processed The metal element-containing gas that has passed through the chamber and the oxygen-containing gas and / or nitrogen-containing gas that has passed through another plasma generation chamber are merged and further passed through other plasma generation chambers to the outside of these plasma generation chambers. The thin film is formed on the surface of the substrate to be treated, sprayed onto the substrate to be treated , and each plasma generation chamber is between a pair of counter electrodes whose at least one opposed surface is coated with a solid dielectric. And a multistage discharge plasma processing method characterized by being a space in which plasma is generated by applying an electric field between the counter electrodes. 電界が、パルス立ち上がり及び／又は立ち下がり時間が１０μｓ以下であるパルス状電界であることを特徴とする請求項１又は２に記載の多段型の放電プラズマ処理方法。  The multistage discharge plasma processing method according to claim 1 or 2, wherein the electric field is a pulsed electric field having a pulse rise time and / or a fall time of 10 µs or less. 電界が、電界強度が１０〜１０００ｋＶ／ｃｍであるパルス状電界であることを特徴とする請求項１〜３のいずれか１項に記載の多段型の放電プラズマ処理方法。  The multistage discharge plasma processing method according to any one of claims 1 to 3, wherein the electric field is a pulsed electric field having an electric field strength of 10 to 1000 kV / cm. 金属元素含有ガスと酸素含有ガス及び／又は窒素含有ガスを反応させて酸化金属化合物及び／又は窒化金属化合物からなる薄膜を被処理基材の表面に形成する放電プラズマ処理装置において、少なくとも一方の対向面が固体誘電体で被覆された一対の対向電極を有し、上記対向電極どうし間の一の端部に１の処理ガス導入口が設けられ、上記対向電極どうし間の別の端部にガス吹出口が設けられ、上記対向電極どうし間の上記１の処理ガス導入口とガス吹出口の中間に別の処理ガス導入口が設けられ、上記対向電極どうし間における上記１の処理ガス導入口と上記別の処理ガス導入口との間の部分が、１のプラズマ発生室を構成し、上記対向電極どうし間における上記別の処理ガス導入口と上記ガス吹出口との間の部分が、別のプラズマ発生室を構成し、上記対向電極間に電界が印加されることにより上記各プラズマ発生室内でプラズマが発生し、上記金属元素含有ガスが、上記１の処理ガス導入口から上記１のプラズマ発生室に導入され、上記酸素含有ガス及び／又は窒素含有ガスと混合されることなく上記１のプラズマ発生室内にてプラズマ励起され、上記酸素含有ガス及び／又は窒素含有ガスが、上記別の処理ガス導入口から上記別のプラズマ発生室に導入されて上記１のプラズマ発生室を通過した上記金属元素含有ガスと合流し、合流したガスが、上記別のプラズマ発生室を通過して上記ガス吹出口から吹き出され、上記対向電極間の外部に配置された上記被処理基材に吹き付けられ、上記被処理基材の表面に上記薄膜が形成されることを特徴とする放電プラズマ処理装置。 In a discharge plasma processing apparatus in which a metal element-containing gas and an oxygen-containing gas and / or a nitrogen-containing gas are reacted to form a thin film made of a metal oxide compound and / or a metal nitride compound on the surface of a substrate to be processed, at least one facing It has a pair of counter electrodes whose surfaces are coated with a solid dielectric , one processing gas inlet is provided at one end between the counter electrodes, and a gas is provided at another end between the counter electrodes. A blower outlet is provided , another process gas inlet is provided between the one process gas inlet between the counter electrodes and the gas blower outlet, and the first process gas inlet between the counter electrodes is provided. A portion between the other processing gas introduction port constitutes one plasma generation chamber, and a portion between the other processing gas introduction port and the gas blowout port between the counter electrodes is different from each other. Plasma generation When the electric field is applied between the counter electrodes, plasma is generated in each of the plasma generation chambers, and the metal element-containing gas is introduced into the one plasma generation chamber from the one processing gas introduction port. The plasma is excited in the plasma generating chamber of the first without being mixed with the oxygen-containing gas and / or the nitrogen-containing gas, and the oxygen-containing gas and / or the nitrogen-containing gas is supplied from the other processing gas inlet. The metal element-containing gas that has been introduced into the another plasma generation chamber and passed through the one plasma generation chamber merges, and the merged gas passes through the other plasma generation chamber and is blown out from the gas outlet. , blown to the treated substrate disposed outside between the opposed electrodes, a discharge plasma processing device, characterized in that said thin film is formed on the surface of the treated substrate 上記別の処理ガス導入口が、上記一対の対向電極のうちの１つの電極に設けられた穴によって形成されていることを特徴とする請求項５に記載の放電プラズマ処理装置。6. The discharge plasma processing apparatus according to claim 5, wherein the another processing gas introduction port is formed by a hole provided in one of the pair of counter electrodes . 一の対向電極によって形成される第１のプラズマ発生室、他の対向電極によって形成される第２のプラズマ発生室を備え、第１のプラズマ発生室と第２のプラズマ発生室から吹き出したガス流が合流して、第３のプラズマ発生室に導入されるようになされ、第１のプラズマ発生室と第３のプラズマ発生室の電界印加側の電極が共通のものであることを特徴とする放電プラズマ処理装置。  A gas flow blown out of the first plasma generation chamber and the second plasma generation chamber, comprising a first plasma generation chamber formed by one counter electrode and a second plasma generation chamber formed by another counter electrode Are combined and introduced into the third plasma generation chamber, and the electrodes on the electric field application side of the first plasma generation chamber and the third plasma generation chamber are common. Plasma processing equipment. 一の対向電極によって形成される第１のプラズマ発生室、他の対向電極によって形成される第２のプラズマ発生室を備え、第１のプラズマ発生室と第２のプラズマ発生室から吹き出したガス流が合流して、第３のプラズマ発生室に導入されるようになされ、第１のプラズマ発生室と第２のプラズマ発生室の電界印加側の電極が共通のものであることを特徴とする放電プラズマ処理装置。  A gas flow blown out of the first plasma generation chamber and the second plasma generation chamber, comprising a first plasma generation chamber formed by one counter electrode and a second plasma generation chamber formed by another counter electrode Are combined and introduced into the third plasma generation chamber, and the electrodes on the electric field application side of the first plasma generation chamber and the second plasma generation chamber are common. Plasma processing equipment.
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