JP4372918B2 - Plasma processing apparatus and plasma processing method - Google Patents

Description

【００５１】
そして、反応容器１を挿着孔１７に差し込むことによって、電極２と電極３を反応容器１の外周に取り付けると共に電極２と電極３の内周面を反応容器１の外周面（側壁１ａと側壁１ｂの外面）に接触させるように配置し、交流電界を発生させる電源１８を電極２に接続すると共に電極３を接地することによって、図１（ａ）に示すようなプラズマ処理装置を形成することができる。ここで、接地される電極３は高電圧が印加される電極２よりも下側に、すなわち、電極３は電極２よりも吹き出し口４の近くに配置されている。このように電極３を電極２よりも吹き出し口４の近くに配置することによって、電極２よりも電極３の方が吹き出し口４の下側に配置される被処理物に近くに位置することになり、すなわち、高電圧となる電極２が電極３よりも被処理物から遠くに位置することになり、電極２から被処理物にアーク放電が飛びにくくなって、アーク放電による被処理物の破損を防止することができる。
【００５２】
電極２と電極３の間隔（電極２の下端と電極３の上端の間隔）は３〜２０ｍｍに設定するのが好ましい。電極２と電極３の間隔が３ｍｍ未満であれば、反応容器１の外部で電極２と電極３の間で短絡が起こって放電空間１５で放電が起こらなくなる恐れがあり、しかも、放電空間１５が狭くなって、効率よくプラズマを生成することが難しくなる恐れがある。また、電極２と電極３の間隔が２０ｍｍを超えると、放電空間１５で放電が起こりにくくなって、効率よくプラズマを生成することが難しくなる恐れがある。
【００５３】
上記のように形成されるプラズマ処理装置では、プラズマ生成用ガスとして不活性ガス（希ガス）あるいは不活性ガスと反応ガスの混合気体を用いる。不活性ガスとしては、ヘリウム、アルゴン、ネオン、クリプトンなどを使用することができるが、放電の安定性や経済性を考慮すると、アルゴンやヘリウムを用いるのが好ましい。また反応ガスの種類は処理の内容によって任意に選択することができる。例えば、被処理物の表面に存在する有機物のクリーニング、レジストの剥離、有機フィルムのエッチングなどを行う場合は、酸素、空気、ＣＯ₂、Ｎ₂Ｏなどの酸化性ガスを用いるのが好ましい。また反応ガスとしてＣＦ₄などのフッ素系ガスも適宜用いることができ、シリコンなどのエッチングを行う場合にはこのフッ素系ガスを用いるのが効果的である。また金属酸化物の還元を行う場合は、水素、アンモニアなどの還元性ガスを用いることができる。反応ガスの添加量は不活性ガスの全量に対して１０重量％以下、好ましくは０．１〜５重量％の範囲である。反応ガスの添加量が０．１重量％未満であれば、処理効果が低くなる恐れがあり、反応ガスの添加量が１０重量％を超えると、放電が不安定になる恐れがある。
【００５４】
上記のように形成されるプラズマ処理装置を用いてプラズマ処理を行うにあたっては、まず、矢印（１）で示すようにガス導入口１６から反応容器１の内部にプラズマ生成用ガスを上から下に向かって流して導入すると共に電極２に電源１８から高周波電圧を印加して、電極２と電極３の間の放電空間１５に高周波の交流電界を印加する。この交流電界の印加により大気圧下で放電空間１５にグロー状の放電を発生させ、グロー状の放電でプラズマ生成用ガスをプラズマ化してプラズマ活性種を含むプラズマを生成した後、矢印（２）で示すように、吹き出し口４から下方にカーテンのような幅を持ったジェット状のプラズマを連続的に流出させ、吹き出し口４の下側に配置された被処理物の表面にプラズマを吹き付けるようにする。このようにして被処理物のプラズマ処理を行うことができる。また、平板状の基板が被処理物であって、その基板の表面全面をプラズマ処理するには、プラズマを吹き出しながら基板あるいはプラズマ処理装置を吹き出し口４の長手方向と直交する方向に移動させ、基板の表面全面にプラズマを走査して吹き付けるようにして行う。さらに、プラズマ処理装置又は被処理物を被処理物の移動方向と直交する方向に振動させることにより、繰り返しプラズマが被処理物に吹き付けられることになってプラズマ処理の均一化を高めることも可能である。
【００５５】
本発明において、印加される交流電界の周波数は１ｋＨｚ〜２００ＭＨｚに設定するのが好ましい。交流の周波数が１ｋＨｚ未満であれば、放電空間１５での放電を安定化させることができなくなり、プラズマ処理を効率よく行うことができなくなる恐れがある。また、交流の周波数が２００ＭＨｚを超えると、放電空間１５でのプラズマの温度上昇が著しくなり、反応容器１や電極２や電極３の寿命が短くなる恐れがあり、しかも、プラズマ処理装置が複雑化及び大型化する恐れがある。また本発明において、放電空間１５に印加される印加電力は２０〜３５００Ｗ／ｃｍ³に設定するのが好ましい。放電空間１５に印加される印加電力が２０Ｗ／ｃｍ³未満であれば、プラズマを充分に発生させることができなくなり、逆に、放電空間１５に印加される印加電力が３５００Ｗ／ｃｍ³を超えると、安定した放電を得ることができなくなる恐れがある。尚、印加電力の密度（Ｗ／ｃｍ³）は、（印加電力／放電空間体積）で定義される。
【００５６】
そしてこの実施の形態では、反応容器１の側壁１ａと側壁１ｂの内面に沿った電気力線ａが形成されるように、反応容器１を挟んで対向させないで電極２と電極３を配置するので、反応容器１の内面の垂直方向に電気力線が生じにくくなって電気力線ａによる反応容器１の劣化を少なくすることができ、反応容器１の側壁１ａと側壁１ｂの内面からその構成物質が飛び出しにくくなって被処理物が不純物により汚染されるのを少なくすることができるものである。すなわち、本発明では図２（ａ）に示すように、電極２と電極３が反応容器１の側壁１ａと側壁１ｂの外面側に設けられてそれぞれの側壁１ａ、１ｂに沿った方向に互いに対向するように配置されるので、電極２と電極３の間に反応容器１の側壁１ａと側壁１ｂの内面に沿った電気力線ａが形成されるが、図２（ｂ）に示すように、電極２と電極３を反応容器１の側壁１ａと側壁１ｂの外面側へ設けて側壁１ａ、１ｂに対する直交方向へ互いに対向するように配置すると、電極２と電極３の間に反応容器１の側壁１ａと側壁１ｂの内面の直交方向に電気力線ａが形成されることになる。そして、本発明では図２（ａ）のように、電極２と電極３が対向する方向（電極２と電極３が並ぶ方向）において、少なくとも一部の電気力線ａが反応容器１の内面に沿って形成されるので、図２（ｂ）のように全ての電気力線ａが反応容器１の側壁１ａと側壁１ｂの内面の垂直方向に形成された場合に比べて反応容器１の劣化が小さくなり、反応容器１の側壁１ａと側壁１ｂの内面からその構成物質が飛び出しにくくなって被処理物が不純物により汚染されるのを少なくすることができるのである。
【００５７】
また、上記の実施の形態では、幅を持ったジェット状のプラズマを吹き出すための吹き出し口４を反応容器１の下面に形成するので、カーテンのような幅を持ったプラズマを吹き出し口４から吹き出しながら基板あるいはプラズマ処理装置を吹き出し口４の長手方向と直交する方向に移動させて基板の表面全面にプラズマを走査して吹き付けることによって、スポット的なプラズマを吹き出すものに比べて被処理物の広い面積を一度にプラズマ処理することができ、ＢＧＡ基板などの基板の全面を処理する場合に処理時間を短くすることができるものである。
【００５８】
さらに、上記の実施の形態では、放電空間１５に交流電界を印加するための電極２と電極３の両方を反応容器１の外側に設けるので、電極２と電極３の両方がプラズマに直接曝されることが無くなってプラズマによりスパッタリングを受けないようにすることができると共に、電極２と電極３の両方が反応ガスにより腐食されないようにすることができ、電極２と電極３がプラズマでダメージを受けなくなって寿命を長くすることができるものである。しかも、スパッタリングや腐食により不純物が生じないので、長期間の使用であっても被処理物が不純物より汚染されないようにすることができるものである。
【００５９】
また、上記の実施の形態では、電極２と電極３をプラズマ生成用ガスの導入方向へ沿って対向するように、すなわち、電極２と電極３を上下に並べて対向させて配置するので、放電空間１５に生成される交流電界の方向（電気力線ａの方向）とプラズマ生成用ガス及びプラズマの流れ方向とをほぼ一致させることができ、プラズマの活性種を効率よく生成することができるものであり、しかも、電極２と電極３の間隔を変えることによって、放電空間１５の大きさを簡単に変えることができ、プラズマの生成量を容易に調整することができるものである。
【００６０】
図３（ａ）（ｂ）に他の実施の形態を示す。このプラズマ処理装置では、電気力線ａが沿って形成される反応容器１の片側の側壁１ａの内面に沿うようにして吹き出し口４を反応容器１の下面に形成したものであり、その他の構成は図１のものと同様に形成されている。すなわち、図１のプラズマ処理装置では、反応容器１の厚み方向において反応容器１の下面を略二等分する中心線Ｄにほぼ沿って吹き出し口４が長く形成されているが、図３（ａ）（ｂ）のプラズマ処理装置では上記の中心線Ｄの位置よりも側壁１ａに近づいた位置で且つ側壁１ａの近傍において、反応容器１の下面の端部に吹き出し口４を側壁１ａの内面に沿って長く形成したものである。また、このプラズマ処理装置では中心線Ｄを挟んで対向する一対の側壁１ａ、１ａのうちの片側の側壁１ａの近傍にのみに吹き出し口４が形成されている。
【００６１】
上記のように図１のプラズマ処理装置では、電極２と電極３が反応容器１の側壁１ａと側壁１ｂの外面に接触することにより、反応容器１の側壁１ａと側壁１ｂの内面に沿った電気力線ａが多く形成されるが、このことで、図３（ｂ）（ｃ）に示すようにプラズマＰは、反応容器１の中央部よりも反応容器１の側壁１ａと側壁１ｂの内面の近傍において集中して生成されて濃度が高くなる傾向にある。従って、図１及び図３（ｃ）に示すように、反応容器１の下面において反応容器１の厚み方向の略中央部に吹き出し口４を形成するよりも、図３（ａ）（ｂ）に示すように、反応容器１の下面において反応容器１の側壁１ａの近傍で側壁１ａに沿って吹き出し口４を形成する方が効率よくプラズマＰを吹き出すことができ、プラズマ処理の能力を向上させることができるものである。
【００６２】
図４に他の実施の形態を示す。このプラズマ処理装置では、電気力線ａが沿って形成される反応容器１の両側の側壁１ａの内面に沿うようにして吹き出し口４を反応容器１の下面に形成したものであり、その他の構成は図１のものと同様に形成されている。すなわち、図１のプラズマ処理装置では、反応容器１の下面を反応容器１の厚み方向に略二等分する中心線Ｄにほぼ沿って吹き出し口４が長く形成されているが、図４（ａ）（ｂ）のプラズマ処理装置では上記の中心線Ｄの位置よりも側壁１ａに近づいた位置で且つ側壁１ａの近傍において、反応容器１の下面の端部に吹き出し口４を側壁１ａの内面に沿って長く形成したものである。また、このプラズマ処理装置では中心線Ｄを挟んで対向する一対の側壁１ａ、１ａの両側の側壁１ａの近傍に吹き出し口４が形成されている。
【００６３】
上記のように図１のプラズマ処理装置では反応容器１の側壁１ａと側壁１ｂの内面に沿った電気力線ａが多く形成されるが、このことで、図４（ａ）に示すようにプラズマＰは、反応容器１の中央部よりも反応容器１の側壁１ａと側壁１ｂの内面の近傍において集中して生成されて濃度が高くなる傾向にある。従って、図１及び図３（ｃ）に示すように、反応容器１の下面において反応容器１の厚み方向の略中央部に吹き出し口４を形成するよりも、図４（ａ）（ｂ）に示すように、反応容器１の下面において反応容器１の側壁１ａの近傍で側壁１ａに沿って吹き出し口４を形成する方が、効率よくプラズマＰを吹き出すことができ、プラズマ処理の能力を向上させることができるものである。しかも、吹き出し口４の下側において、被処理物６０を吹き出し口４の長手方向と直交する方向に搬送してプラズマ処理を行うことによって、プラズマＰを被処理物６０に二重（二回）に吹き付けることができ、図３（ａ）（ｂ）のものに比べて、被処理物６０の一回の搬送におけるプラズマＰの照射時間が二倍になって、プラズマ処理の能力を向上させることができるものである。尚、この実施の形態においては、図１や図３（ａ）（ｂ）のものに比べて吹き出し口４の開口面積が増えるために、プラズマ生成用ガスの流量を増やしてプラズマＰの吹き出しの流速が低下しないようにするのが好ましい。
【００６４】
図５、６に他の実施の形態を示す。この実施の形態は図１のプラズマ処理装置において、電極２と電極３を冷却するものである。つまり、電極２と電極３の内部は冷媒が流通可能な流通部２６として形成されていると共に、電極２と電極３の外周面には流通部２６と連通する供給管２１と排出管２２が突設されており、矢印（３）で示すように供給管２１を通じて電極２と電極３の内部の流通部２６に冷媒を供給することによって、プラズマを発生させている間、電極２と電極３を冷却するのである。流通部２６に供給された冷媒は矢印（４）で示すように排出管２２を通じて電極２と電極３から排出される。
【００６５】
冷媒としてはイオン交換水や純水を使用することができる。イオン交換水や純水を用いることによって、冷媒中に不純物が含まれることがなく、電極２と電極３が冷媒で腐食されにくくなるものである。また、冷媒としては０℃で不凍性を有し、且つ電気絶縁性及び不燃性や化学安定性を有する液体であることが好ましく、例えば、電気絶縁性能は０．１ｍｍ間隔での耐電圧が１０ｋＶ以上であることが好ましい。この範囲の絶縁性を有する冷媒を用いる理由は、高電圧が印加される高圧電極からの漏電を防止するためである。このような性質を有する冷媒としては、パーフルオロカーボン、ハイドロフルオロエーテル等を例示することができ、また純水にエチレングリコールを５〜６０重量％添加した混合液であってもよい。
【００６６】
そして、この実施の形態では、電極２と電極３を冷媒により冷却するので、大気圧下で周波数の高い交流でプラズマを生成しても、電極２と電極３の温度上昇を抑えることができ、よってプラズマの温度（ガス温度）が高くならないようにすることができて被処理物の熱的損傷を少なくすることができるものである。また、電極２と電極３を冷却することによって、放電空間１５の局所的な加熱を防ぐことができ、均質なグロー状の放電を生成してストリーマー放電の生成を抑えることができて被処理物のストリーマー放電による損傷をより少なくすることができるものである。これは、電極２と電極３を冷却することによって、電極２と電極３からの部分的な電子の放出が抑えられるためであると考えられる。尚、この実施の形態では、電極２と電極３の両方を冷却するようにしたが、電極２と電極３のいずれか一方のみを冷却するようにしてもよい。
【００６７】
尚、この実施の形態においても、図３（ａ）（ｂ）に示すように、電気力線ａが沿って形成される反応容器１の片側の側壁１ａの内面に沿うようにして吹き出し口４を反応容器１の下面に形成したり、図４（ａ）（ｂ）に示すように、電気力線ａが沿って形成される反応容器１の両側の側壁１ａの内面に沿うようにして吹き出し口４を反応容器１の下面に形成したりすることができる。
【００６８】
図７に他の実施の形態を示す。この実施の形態は図５、６のプラズマ処理装置において、放電空間１５の体積を減少させるための体積減少具１１を設けたものである。体積減少具１１は図８（ａ）（ｂ）に示すように、反応容器１よりも小さく反応容器１の内部形状と略等しい箱状に形成されるものであって、体積減少具１１の内部には流通管２３が上下方向に蛇行するように配設されている。また、流通管２３の一端は導入部２４として、他端は導出部２５としてそれぞれ形成されており、導入部２４と導出部２５は体積減少具１１の上面から突出して配置されている。そして、体積減少具１１は流通管２３に上記と同様の冷媒を流通させることによって、冷却されるものである。すなわち、矢印（５）で示すように導入部２４を通じて流通管２３の内部に冷媒を供給して流通させることによって、体積減少具１１を冷却するのである。流通管２３に供給された冷媒は矢印（６）で示すように導出部２５を通じて排出される。
【００６９】
この体積減少具１１はその下部が放電空間１５内に位置するように、ガス導入口１６から反応容器１の内部に挿入されて配置されている。従って、この実施の形態における放電空間１５の体積は、図１乃至６のプラズマ処理装置の放電空間１５よりも減少している。そして、このように放電空間１５にその体積を減少させるための体積減少具１１を設けることによって、放電空間１５における単位体積あたりの投入電力（交流電界）を増加させることができ、プラズマの生成の効率を向上させることができるものである。また、プラズマを生成している間、体積減少具１１を冷媒により冷却することによって、体積減少具１１の熱による劣化を低減することができ、体積減少具１１の長寿命化を図ることができるものであり、しかも、体積減少具１１の周囲の放電空間１５で生成されるプラズマの温度を低下させることができ、被処理物の熱によるダメージを少なくすることができるものである。
【００７０】
さらに、体積減少具１１は反応容器１の中心を上下に貫くように配置されている。つまり、反応容器１の長手方向（上下方向）に長い中心線と体積減少具１１の長手方向（上下方向）に長い中心線とがほぼ合致するように、反応容器１と体積減少具１１はほぼ同軸（同心円状）に配置されている。このように反応容器１と体積減少具１１をほぼ同軸に配置することによって、反応容器１の内周面と体積減少具１１の外周面の間に形成される放電空間１５の体積を均一化することができ、放電空間１５における交流電界の密度が均一化されて、プラズマを効率よく生成することができるものであり、しかも、生成されるプラズマが均質化されて高品質のプラズマ処理を行うことができるものである。
【００７１】
体積減少具１１は反応容器１と同様の高融点の絶縁材料で形成するのが好ましく、このことで体積減少具１１からスパッタリングや腐食により不純物が生じないようにすることができ、長期間の使用であっても被処理物が不純物より汚染されないようにすることができるものである。また、体積減少具１１はステンレス鋼等の金属材料で形成することもできるが、この場合、体積減少具１１の表面は、絶縁材料で保護膜でコーティングするのが好ましい。この保護膜に使用する絶縁材料としては、石英、アルミナ、イットリア部分安定化ジルコニウムなどのガラス質材料やセラミック材料などを例示することができる。さらに、アルミナ（Ａｌ₂Ｏ₃）、酸化チタン（チタニアでＴｉＯ₂）、ＳｉＯ₂、ＡｌＮ、Ｓｉ₃Ｎ、ＳｉＣ、ＤＬＣ（ダイヤモンド様炭素被膜）、チタン酸バリウム、ＰＺＴ（チタン酸鉛ジルコネート）などの誘電体材質のものを例示することができる。またマグネシア（ＭｇＯ）単体あるいはマグネシアを含む絶縁材料を用いることもできる。
【００７２】
また、保護膜を形成するにあたっては、絶縁材料で角形筒体（セラミック管やガラス管）を形成し、これの内側に体積減少具１１を挿着して密着させる方法、及びアルミナ、チタン酸バリウム、酸化チタン、ＰＺＴなどの粉末をプラズマ中で分散させ、体積減少具１１の表面に吹き付けるようにするプラズマ溶射法、及びシリカ、酸化スズ、チタニア、ジルコニア、アルミナなどの無機質粉末を溶剤などにより分散し、体積減少具１１の表面にスプレーなどで吹き付けて被覆した後、６００℃以上の温度で溶融させるいわゆる琺瑯被覆方法、及びゾルゲル法によるガラス質膜の形成方法などを採用することができる。さらに気相蒸着法（ＣＶＤ）もしくは物理蒸着法（ＰＶＤ）により体積減少具１１の表面を保護膜でコーティングすることもでき、これらの方法を採用することによって、極めて緻密で平滑な吸着性の乏しい保護膜で体積減少具１１の表面をコーティングすることができ、放電の安定化をより促進することができる。現実的な処理時間及びコストを考慮すると、上記の溶射法を用いるのが好ましい。
【００７３】
また、保護膜の厚みは１０〜５００μｍに設定するのが好ましい。保護膜の厚みが１０μｍ未満であれば、体積減少具１１の劣化防止の効果が小さく、体積減少具１１の長寿命化を図りにくくなる恐れがあり、保護膜の厚みが５００μｍを超えても体積減少具１１の劣化防止の効果は大きく向上せず、保護膜に使用する絶縁材料の消費量が無駄に多くなって経済的に不利になる恐れがある。
【００７４】
また、体積減少具１１の表面と保護膜の間には、ニッケル、クロム、アルミニウム、イットリウムを含む合金膜で形成されるアンダーコートを介在させるのが好ましい。アンダーコートは合金の溶射により形成することができ、具体的な合金としては、Ｎｉ−Ｃｒ、Ｎｉ−Ａｌ、Ｎｉ−Ｃｒ−Ａｌ−Ｙなどを例示することができる。体積減少具１１は室温と高温のプラズマ下の繰り返しによる熱応力負荷環境に置かれることになり、この熱応力で保護膜が剥離してしまう恐れがある。そこで、保護膜にかかる熱応力負荷の衝撃を緩和させるためにアンダーコートを設けるようにする。金属である体積減少具１１と合金であるアンダーコートと絶縁材料である保護膜の熱膨張率の関係は、金属の膨張率＞合金の膨張率＞絶縁材料の膨張率となり、体積減少具１１の熱による伸縮がアンダーコートの介在によって保護膜に伝わりにくくなり、このことで、保護膜が剥離しにくくなって体積減少具１１の長寿命化を図ることができるものである。
【００７５】
また、保護膜には封孔処理を施すのが好ましい。封孔処理は保護膜の欠陥部分を埋める処理であって、ＳｉＯ₂、ＴｉＯ₂、Ａｌ₂Ｏ₃などの誘電体を含む溶液に浸漬して行う。この封孔処理を行うことによって、電極２と金属製の体積減少具１１の間でアーク放電を起こりにくくすることができ、プラズマの加熱による体積減少具１１の劣化を防止して体積減少具１１の長寿命化を図ることができるものである。
【００７６】
体積減少具１１はプラズマ処理を行う被処理物の種類によって使い分けが可能である。例えば、被処理物が金属材料のような高温に曝されても構わない（劣化等が起きない）場合は、冷却機構である流通管２３や冷媒を有さないで絶縁材料で形成される体積減少具１１を用いるようにする。この場合、体積減少具１１は冷却されないので、図９の曲線イで示すようにプラズマのガス温度が高くなり、図９の曲線ロで示すクリーニング性能ように、プラズマの処理速度を高めることができ、プラズマ処理（クリーニング）を短時間で行うことができるものである。一方、回路基板のように、比較的耐熱温度の低い被処理物をプラズマ処理する場合は、冷却機構である流通管２３や冷媒を有し、且つ熱伝導率が絶縁材料よりも高い金属材料で形成される体積減少具１１を用いるようにする。この場合、体積減少具１１は冷却されるので、図９の曲線イで示すようにプラズマのガス温度が低くなり、図９の曲線ロで示すクリーニング性能ように、プラズマの処理速度が多少低下するが、被処理物に熱ダメージを与えないでプラズマ処理（クリーニング）を行うことができるものである。
【００７７】
尚、この実施の形態においても、図３（ａ）（ｂ）に示すように、電気力線ａが沿って形成される反応容器１の片側の側壁１ａの内面に沿うようにして吹き出し口４を反応容器１の下面に形成したり、図４に示すように、電気力線ａが沿って形成される反応容器１の両側の側壁１ａの内面に沿うようにして吹き出し口４を反応容器１の下面に形成したりすることができる。
【００７８】
図１０に参考形態を示す。この参考形態では図２のプラズマ処理装置において、反応容器１の上部にガス均一化室５が一体に形成されている。ガス均一化室５は反応容器１よりも厚い箱状に形成されるものであって、ガス均一化室５の上面はガス供給口３０として全面に亘って開口されていると共にガス均一化室５の下面には反応容器１のガス導入口１６が開口されている。このガス均一化室５内にはシリカボール等で形成される球体６が多数個充填されている。
【００７９】
この参考形態では、ガス均一化室５を介してプラズマ生成用ガスを反応容器１に供給するのである。すなわち、ガス供給口３０からガス均一化室５内にプラズマ生成用ガスを導入し、球体６の間の隙間を通過させるようにしてプラズマ生成用ガスをガス導入口１６まで下流させ、この後、ガス導入口１６から反応容器１内にプラズマ生成用ガスを導入するのである。そして、このようにガス均一化室５を通過させてプラズマ生成用ガスを反応容器１に供給するので、プラズマ生成用ガスが反応容器１内の一部分に偏らないように、反応容器１内の全体に均一な濃度で供給することができ、均質なプラズマを効率よく生成することができるものであり、また、処理むらを少なくすることができるものである。
【００８０】
上記の球体６の直径は３〜７ｍｍに設定するのが好ましく、また、球体６の充填量は球体６の占める割合がガス均一化室５の容積の５０〜８０％になるように設定するのが好ましい。球体６の直径が３ｍｍ未満であったり、球体６の充填量が８０％を超えると、球体６の間の隙間が小さくなり過ぎてプラズマ生成用ガスを反応容器１に導入することができなくなる恐れがある。また、球体６の直径が７ｍｍを超えたり、球体６の充填量が５０％未満であると、球体６の間の隙間が大きくなり過ぎてプラズマ生成用ガスを反応容器１に均一に導入することができなくなる恐れがある。
【００８１】
尚、この参考形態においても、図３（ａ）（ｂ）に示すように、電気力線ａが沿って形成される反応容器１の片側の側壁１ａの内面に沿うようにして吹き出し口４を反応容器１の下面に形成したり、図４に示すように、電気力線ａが沿って形成される反応容器１の両側の側壁１ａの内面に沿うようにして吹き出し口４を反応容器１の下面に形成したりすることができる。また、上記のようなプラズマ生成用ガスを反応容器１に均一に導入するためのガス均一化室５は、本発明のいずれの実施の形態にも形成することができる。
【００８２】
図１１に他の参考形態を示す。この参考形態では図１のプラズマ処理装置において、反応容器１の上部にガス均一化室５が一体に形成されている。その他の構成は図１のものと同様である。図１２（ａ）（ｂ）（ｃ）に示すように、ガス均一化室５は反応容器１よりも厚い箱状に形成されるものであって、ガス均一化室５の上面にはガス供給口３０を設けたガス管部６１が突設されていると共にガス均一化室５の下部は下側ほど厚みが小さくなる絞り部６２として形成されており、ガス均一化室５の下端である絞り部６２の下端が反応容器１の側壁１ａ、１ｂの外面に接合されている。また図１３に示すように、反応容器１と絞り部６２の接合部分にはガス均一化室５内に突出する筒状の鍔部５０が反応容器１に一体に形成されており、鍔部５０の上面が反応容器１のガス導入口１６として開口されている。
【００８３】
この参考形態では、ガス均一化室５を介してプラズマ生成用ガスを反応容器１に供給するのである。すなわち、ガス供給口３０からガス均一化室５内にプラズマ生成用ガスを導入し、プラズマ生成用ガスをガス導入口１６まで下流させ、この後、ガス導入口１６から反応容器１内にプラズマ生成用ガスを導入するのである。そして、このようにガス均一化室５を通過させてプラズマ生成用ガスを反応容器１に供給することで、プラズマ生成用ガスが鍔部５０により撹拌されて反応容器１内の一部分に偏らないように拡散しやすくなり、反応容器１内の全体に均一な濃度で供給することができ、均質なプラズマを効率よく生成することができるものであり、また、処理むらを少なくすることができるものである。尚、このガス均一化室５内には上記と同様の球体６を充填してもよいが、充填しなくても良い。
【００８４】
図１４に他の実施の形態を示す。このプラズマ処理装置は反応容器１がその厚み方向（反応容器１及びプラズマ処理装置の厚み方向を矢印Ｂで示す）に並んで対向する一対の側壁１ａと、反応容器１の幅方向（反応容器１及びプラズマ処理装置の幅方向を矢印Ａで示す）に並んで対向する一対の側壁１ｂと、反応容器１の下面を構成する矩形状（底面視で長方形）の底部１ｃと上面１ｄで角形筒状に形成されている。また、反応容器１の上面１ｄの略中央部にはガス導入口（図示省略）が形成されていると共に反応容器１の矩形状（底面視で長方形）の下面はほぼ平坦な面で形成されている。そして、図１４（ｂ）に示すように、反応容器１の下面の厚み方向の略中央部にはその長手方向（幅方向）と平行な方向に長くて幅広の吹き出し口４が形成されている。吹き出し口４はスリット状であって、反応容器１の底部１ｃを貫通して反応容器１の内部の放電空間１５と連通している。
【００８５】
この反応容器１の外面には電極２と電極３が設けられている。すなわち、反応容器１の上面と反応容器１の幅方向に並んで対向する一対の側面１ｂの外面に電極２と電極３を接触させて設けると共に電極２と電極３を反応容器１の厚み方向に対向させて配置することによって形成されており、反応容器１の内部において電極２と電極３の間に放電空間１５が形成されている。反応容器１は上記と同様の材料で形成されている。
【００８６】
電極２と電極３は同形であって、側面視で下面が開口するコ字状に形成されている。すなわち、電極２と電極３は上片３１と上片３１の端部に下方に突出して延設される一対の側片３２とで構成されており、上片３１と側片３２で囲まれる空間を挿着凹部３３として形成するものである。この挿着凹部３３の幅方向の寸法は反応容器１の幅方向の外形法とほぼ同一に、また、挿着凹部３３の高さ方向の寸法は反応容器１の高さ方向の外寸法とほぼ同一にそれぞれ形成されている（反応容器１及びプラズマ処理装置の高さ方向を矢印Ｃで示す）。さらに、電極２と電極３は上記と同様の材料で形成されている。加えて、電極２と電極３の内面（挿着凹部３３を構成する面）は反応容器１の外周と接触する面であって、その内面の算術平均粗さで表した表面粗度は１０〜１０００μｍに設定されている。
【００８７】
そして、反応容器１を挿着凹部３３に下側から差し込むことによって、電極２と電極３を反応容器１の外面に取り付け、上片３１を反応容器１の上面に接触させると共に、吹き出し口４の長手方向において対向する反応容器１の側面に側片３２を接触させ、交流電界を発生させる電源１８を電極２に接続すると共に電極３を接地することによって、図１４（ａ）に示すようなプラズマ処理装置を形成することができる。電極２と電極３の間隔（反応容器１の厚み方向における電極２と電極３の間隔）は３〜２０ｍｍに設定するのが好ましい。このように形成されるプラズマ処理装置は、上記の図１に示す実施の形態と同様にしてプラズマ処理を行うことができ、また、図１に示す実施の形態と同様の効果を奏するものである。
【００８８】
さらに、この実施の形態では、電極２と電極３がその厚み方向の寸法よりも幅方向の寸法の方が長く形成されている。つまり、平面視において、電極２と電極３は吹き出し口４の長手方向と平行な方向に長く形成されており、しかも、吹き出し口４の幅方向の寸法よりも電極２と電極３の幅寸法の方が長く形成されている。また、電極２と電極３は吹き出し口４の長手方向と直交する方向（厚み方向）に並べて配置されており、しかも、電極２と電極３は、ガス導入口及び吹き出し口４を厚み方向の両側から挟むように並べて配置されている。つまり、平面視において、ガス導入口と吹き出し口４は電極２と電極３の間に形成されている。よって、電極２と電極３の間の放電空間１５は、反応容器１内の吹き出し口４の上側において、吹き出し口４の長手方向と平行に形成され、しかも、吹き出し口４の幅方向の寸法よりも長く形成されることになる。従って、吹き出し口４の上側（上流側）に広域の放電空間１５が形成されることになって、プラズマ生成用ガスのプラズマ化を効率よく行うことができ、密度の高いプラズマを形成することができるものであり、また、吹き出し口４の全長に亘って均質なプラズマを吹き出すことができるものである。よって、高い密度で均質なプラズマが被処理物に吹き付けられることになって、プラズマ処理の性能を向上させることができ、プラズマ処理を短時間で行うことができるものである。
【００８９】
また、この実施の形態では、反応容器１の下面及び電極２と電極３の側片３２の先端面（下面）を平坦な面に形成し、電極２と電極３の側片３２の先端が反応容器１の下面から突出しないように、反応容器１の下面及び電極２と電極３の側片３２の先端面を面一に形成したので、被処理物を吹き出し口４の近傍にまで近づけることが可能となり、吹き出し口４から大気中に吹き出されたプラズマに含まれている活性の高い生きたプラズマ活性種を消滅させる前に被処理物に吹き付けることができ、プラズマ中の活性種を効率よく利用して被処理物のプラズマ処理を高めることができるものである。尚、吹き出し口４と被処理物の間の距離は、印加条件や被処理物の種類などによって異なるが、２〜１０ｍｍに設定することができる。
【００９０】
図１５（ａ）に他の実施の形態を示す。このプラズマ処理装置では、電気力線ａが沿って形成される反応容器１の片側の側壁１ｂの内面に沿うようにして吹き出し口４を反応容器１の下面に形成したものであり、その他の構成は図１１のものと同様に形成されている。すなわち、図１４及び図１５（ｂ）（ｃ）のプラズマ処理装置では、反応容器１の厚み方向において反応容器１の下面を略二等分する中心線Ｄにほぼ沿って吹き出し口４が長く形成されているが、図１５（ａ）のプラズマ処理装置では電極２と電極３が外面に接触する側壁１ｂの近傍において、反応容器１の下面の端部に吹き出し口４を側壁１ｂの内面に沿って反応容器１の幅方向とほぼ平行な方向に長く形成したものである。また、このプラズマ処理装置では反応容器１の幅方向において反応容器１の下面を略二等分する中心線Ｅを挟んで対向する一対の側壁１ｂ、１ｂのうちの片側の側壁１ｂの近傍にのみに吹き出し口４が形成されている。
【００９１】
上記のように図１４のプラズマ処理装置では、電極２と電極３が反応容器１の側壁１ｂの外面に接触することにより、反応容器１の側壁１ｂの内面に沿った電気力線ａが多く形成されるが、このことで、図１５（ｂ）（ｃ）に示すようにプラズマＰは、反応容器１の中央部よりも反応容器１の側壁１ｂの内面の近傍において集中して生成されて濃度が高くなる傾向にある。従って、図１４及び図１５（ｂ）（ｃ）に示すように、反応容器１の下面において反応容器１の厚み方向の略中央部に吹き出し口４を形成するよりも、図１５（ａ）に示すように、反応容器１の下面において反応容器１の側壁１ｂの近傍で側壁１ｂに沿って吹き出し口４を形成する方が効率よくプラズマＰを吹き出すことができ、プラズマ処理の能力を向上させることができるものである。
【００９２】
図１６に他の実施の形態を示す。このプラズマ処理装置では、電気力線ａが沿って形成される反応容器１の両側の側壁１ｂの内面に沿うようにして吹き出し口４を反応容器１の下面に形成したものであり、その他の構成は図１４のものと同様に形成されている。すなわち、図１４のプラズマ処理装置では、反応容器１の厚み方向において反応容器１の下面を略二等分する中心線Ｄにほぼ沿って吹き出し口４が長く形成されているが、図１６のプラズマ処理装置では電極２と電極３が外面に接触する側壁１ｂの近傍において、反応容器１の下面の端部に吹き出し口４を側壁１ｂの内面に沿って反応容器１の幅方向とほぼ平行な方向に長く形成したものである。また、このプラズマ処理装置では反応容器１の幅方向において反応容器１の下面を略二等分する中心線Ｅを挟んで対向する一対の側壁１ｂ、１ｂの両側の側壁１ｂの近傍に吹き出し口４が形成されている。
【００９３】
上記のように図１４のプラズマ処理装置では反応容器１の側壁１ｂの内面に沿った電気力線ａが多く形成されるが、このことで、図１５（ｂ）（ｃ）に示すようにプラズマＰは、反応容器１の中央部よりも反応容器１の側壁１ｂの内面の近傍において集中して生成されて濃度が高くなる傾向にある。
【００９４】
従って、図１４及び図１５（ｂ）（ｃ）に示すように、反応容器１の下面において反応容器１の厚み方向の略中央部に吹き出し口４を形成するよりも、図１６に示すように、反応容器１の下面において反応容器１の側壁１ｂの近傍で側壁１ｂに沿って吹き出し口４を形成する方が、効率よくプラズマＰを吹き出すことができ、プラズマ処理の能力を向上させることができるものである。しかも、図４（ａ）と同様に、吹き出し口４の下側において、被処理物を吹き出し口４の長手方向と直交する方向に搬送してプラズマ処理を行うことによって、プラズマＰを被処理物に二重（二回）に吹き付けることができ、図１５（ａ）のものに比べて、被処理物の一回の搬送におけるプラズマＰの照射時間が二倍になって、プラズマ処理の能力を向上させることができるものである。尚、この実施の形態においては、図１４や図１５（ａ）のものに比べて吹き出し口４の開口面積が増えるために、プラズマ生成用ガスの流量を増やしてプラズマＰの吹き出しの流速が低下しないようにするのが好ましい。
【００９５】
図１７、１８に他の実施の形態を示す。この実施の形態は図１４のプラズマ処理装置において、電極２と電極３を冷却するものである。つまり、電極２と電極３の内部は冷媒が流通可能な流通部２６として形成されていると共に、電極２と電極３のそれぞれにおいて、一方の側片３２の外面に流通部２６と連通する供給管２１が、他方の側片３２の外面に流通部２６と連通する排出管２２がそれぞれ突設されている。そして、矢印（３）で示すように供給管２１を通じて電極２と電極３の内部の流通部２６に冷媒を供給することによって、プラズマを発生させている間、電極２と電極３を冷却するのである。流通部２６に供給された冷媒は矢印（４）で示すように排出管２２を通じて電極２と電極３から排出される。冷媒としては上記と同様のものを使用することができる。そして、この実施の形態は、電極２と電極３を冷却するので、上記の図５、６に示す実施の形態と同様の効果を奏するものである。
【００９６】
尚、この実施の形態においても、図１５（ａ）に示すように、電気力線ａが沿って形成される反応容器１の片側の側壁１ｂの内面に沿うようにして吹き出し口４を反応容器１の下面に形成したり、図１６に示すように、電気力線ａが沿って形成される反応容器１の両側の側壁１ｂの内面に沿うようにして吹き出し口４を反応容器１の下面に形成したりすることができる。
【００９７】
図１９に他の実施の形態を示す。このプラズマ処理装置は、平坦な平面部７と上側に凸曲する断面が略半円弧状の曲面部８とを備えて半円管状の反応容器１を形成し、平面部７の外面である反応容器１の下面に吹き出し口４を形成し、曲面部８の外面に電極２と電極３を接触させて設けると共に反応容器１の幅方向において電極２と電極３を対向させて配置することによって形成されており、反応容器１の内部において電極２と電極３の間に放電空間１５が形成されている。反応容器１は上記と同様の材料で形成されている。また、反応容器１の幅方向の両端面がガス導入口１６として開口されている。そして、図１９（ｂ）に示すように、反応容器１の下面にはその長手方向（反応容器１の幅方向であって、反応容器１及びプラズマ処理装置の幅方向を矢印Ａで示す）と平行な方向に長くて幅広の吹き出し口４が形成されている。吹き出し口４はスリット状であって、平面部７を貫通して反応容器１の内部の放電空間１５と連通している。
【００９８】
電極２と電極３は同形であって、側面視で下面が開口するＣ字状に形成されている。すなわち、電極２と電極３には下面に開口する挿着凹部３３が形成されている。この挿着凹部３３の内面の寸法は反応容器１の曲面部８の周方向の外形寸法とほぼ同一に形成されている。さらに、電極２と電極３は上記と同様の材料で形成されている。加えて、電極２と電極３の内面（挿着凹部３３を構成する面）は反応容器１の曲面部８の外面と接触する面であって、その内面の算術平均粗さで表した表面粗度は１０〜１０００μｍに設定されている。
【００９９】
そして、反応容器１を挿着凹部３３に下側から差し込むことによって、電極２と電極３を反応容器１の外面の曲面部８に取り付けて接触させ、交流電界を発生させる電源１８を電極２に接続すると共に電極３を接地することによって、図１９（ａ）に示すようなプラズマ処理装置を形成することができる。電極２と電極３の間隔（反応容器１の幅方向における電極２と電極３の間隔）は３〜２０ｍｍに設定するのが好ましい。このように形成されるプラズマ処理装置は、上記の図１に示す実施の形態と同様にしてプラズマ処理を行うことができ、また、図１に示す実施の形態と同様の効果を奏するものである。
【０１００】
さらに、この実施の形態では、反応容器１の下面（平面部７）及び電極２と電極３の先端面（下面）を平坦な面に形成し、電極２と電極３の先端が反応容器１の下面から突出しないように、反応容器１の下面及び電極２と電極３の先端面を面一に形成したので、被処理物を吹き出し口４の近傍にまで近づけることが可能となり、吹き出し口４から大気中に吹き出されたプラズマに含まれている活性の高い生きたプラズマ活性種を消滅させる前に被処理物に吹き付けることができ、プラズマ中の活性種を効率よく利用して被処理物のプラズマ処理を高めることができるものである。尚、吹き出し口４と被処理物の間の距離は、印加条件や被処理物の種類などによって異なるが、２〜１０ｍｍに設定することができる。
【０１０１】
また、この実施の形態では、反応容器１の長手方向の両方の端部にガス導入口１６を形成し、ガス導入口１６を通じて横（反応容器１の長手方向と平行な方向）から反応容器１内にプラズマ生成用ガスを導入するので、反応容器１の長手方向と平行に形成される吹き出し口４の全長に亘って均一にプラズマ生成用ガスを供給することができ、均質なプラズマを効率よく生成することができるものである。よって、高い密度で均質なプラズマが被処理物に吹き付けられることになって、プラズマ処理の性能を向上させることができ、プラズマ処理を短時間で行うことができるものである。
【０１０２】
図２０に他の実施の形態を示す。このプラズマ処理装置では、電気力線ａが沿って形成される反応容器１の曲面部８の内面に沿うようにして吹き出し口４を反応容器１の下面に形成したものであり、その他の構成は図１９のものと同様に形成されている。すなわち、図１９のプラズマ処理装置では、反応容器１の厚み方向において反応容器１の下面を略二等分する中心線Ｄにほぼ沿って吹き出し口４が長く形成されているが、図２０（ａ）のプラズマ処理装置では上記の中心線Ｄの位置よりも曲面部８に近づいた位置で且つ曲面部８の近傍において、反応容器１の下面の端部に吹き出し口４を曲面部８の内面に沿って反応容器１の幅方向に長く形成したものである。また、このプラズマ処理装置では反応容器１の下面において、反応容器１の厚み方向の片側の端部のみに吹き出し口４が形成されている。
【０１０３】
上記のように図１９のプラズマ処理装置では、電極２と電極３が反応容器１の曲面部８の外面に接触することにより、反応容器１の曲面部８の内面に沿った電気力線ａが多く形成されるが、このことで、図２０（ｂ）（ｃ）に示すようにプラズマＰは、反応容器１の厚み方向の中央部よりも反応容器１の曲面部８の内面の近傍において集中して生成されて濃度が高くなる傾向にある。従って、図１９及び図２０（ｃ）に示すように、反応容器１の下面において反応容器１の厚み方向の略中央部に吹き出し口４を形成するよりも、図２０（ａ）に示すように、反応容器１の下面において反応容器１の曲面部８の近傍で曲面部８に沿って吹き出し口４を形成する方が効率よくプラズマＰを吹き出すことができ、プラズマ処理の能力を向上させることができるものである。
【０１０４】
図２１に他の実施の形態を示す。このプラズマ処理装置では、電気力線ａが沿って形成される反応容器１の下面の両側の端部において、曲面部８の内面に沿うようにして吹き出し口４を形成したものであり、その他の構成は図１のものと同様に形成されている。すなわち、図１９のプラズマ処理装置では、反応容器１の下面を反応容器１の厚み方向に略二等分する中心線Ｄにほぼ沿って吹き出し口４が長く形成されているが、図２１のプラズマ処理装置では上記の中心線Ｄの位置よりも曲面部８に近づいた位置で且つ曲面部８の近傍において、反応容器１の下面の端部に吹き出し口４を曲面部８の内面に沿って長く形成したものである。また、このプラズマ処理装置では反応容器１の下面において、反応容器１の厚み方向の両側の端部に吹き出し口４が形成されている。
【０１０５】
上記のように図１９のプラズマ処理装置では電極２と電極３が反応容器１の曲面部８の外面に接触することにより、反応容器１の曲面部８の内面に沿った電気力線ａが多く形成されるが、このことで、図２０（ｃ）に示すようにプラズマＰは、反応容器１の厚み方向の中央部よりも反応容器１の曲面部８の内面の近傍において集中して生成されて濃度が高くなる傾向にある。従って、図１９及び図２０（ｃ）に示すように、反応容器１の下面において反応容器１の厚み方向の略中央部に吹き出し口４を形成するよりも、図２１に示すように、反応容器１の下面において反応容器１の曲面部８の近傍で曲面部８に沿って吹き出し口４を形成する方が、効率よくプラズマＰを吹き出すことができ、プラズマ処理の能力を向上させることができるものである。しかも、図４のものと同様に、吹き出し口４の下側において、被処理物６０を吹き出し口４の長手方向と直交する方向に搬送してプラズマ処理を行うことによって、プラズマＰを被処理物６０に二重（二回）に吹き付けることができ、図２０（ａ）のものに比べて、被処理物６０の一回の搬送におけるプラズマＰの照射時間が二倍になって、プラズマ処理の能力を向上させることができるものである。尚、この実施の形態においては、図１９や図２０（ａ）のものに比べて吹き出し口４の開口面積が増えるために、プラズマ生成用ガスの流量を増やしてプラズマＰの吹き出しの流速が低下しないようにするのが好ましい。
【０１０６】
図２２に他の実施の形態を示す。この実施の形態は図１９のプラズマ処理装置において、電極２と電極３を冷却するものである。つまり、電極２と電極３の内部は冷媒が流通可能な流通部２６として形成されていると共に、電極２と電極３のそれぞれにおいて、一側端の外面に流通部２６と連通する供給管２１が、他側端の外面に流通部２６と連通する排出管２２がそれぞれ突設されている。そして、矢印（３）で示すように供給管２１を通じて電極２と電極３の内部の流通部２６に冷媒を供給することによって、プラズマを発生させている間、電極２と電極３を冷却するのである。流通部２６に供給された冷媒は矢印（４）で示すように排出管２２を通じて電極２と電極３から排出される。冷媒としては上記と同様のものを使用することができる。そして、この実施の形態は、電極２と電極３を冷却するので、上記の図３、４に示す実施の形態と同様の効果を奏するものである。
【０１０７】
尚、この実施の形態においても、図２０（ａ）に示すように、電気力線ａが沿って形成される反応容器１の曲面部８の内面に沿うようにして吹き出し口４を反応容器１の下面の片側の端部に形成したり、図２１に示すように、電気力線ａが沿って形成される反応容器１の曲面部８の内面に沿うようにして吹き出し口４を反応容器１の下面の両側の端部に形成したりすることができる。
【０１０８】
図２３に他の実施の形態を示す。この実施の形態は図２２のプラズマ処理装置において、放電空間１５の体積を減少させるための体積減少具１１を設けたものである。体積減少具１１は両端部が開口する円管で形成されるものであって、一端が反応容器１の一方のガス導入口１６から突出し、他端が反応容器１の他方のガス導入口１６から突出するようにして反応容器１を貫通して配置されている。そして、体積減少具１１は冷媒を流通させることによって、冷却されるものである。すなわち、矢印（５）で示すように体積減少具１１の一方の開口を通じて体積減少具１１の内部に冷媒を供給して流通させることによって、体積減少具１１を冷却するのである。体積減少具１１の内部に供給された冷媒は矢印（６）で示すように他方の開口を通じて排出される。また、体積減少具１１は上記と同様の材料で形成されるものである。
【０１０９】
この体積減少具１１は放電空間１５内に位置するように、ガス導入口１６から反応容器１の内部に挿入されて配置されている。従って、この実施の形態における放電空間１５の体積は、図２２のプラズマ処理装置の放電空間１５よりも減少しており、上記の図７に示す実施の形態と同様の効果を奏するものである。
【０１１０】
尚、この実施の形態においても、図２０（ａ）に示すように、電気力線ａが沿って形成される反応容器１の曲面部８の内面に沿うようにして吹き出し口４を反応容器１の下面の片側の端部に形成したり、図２１に示すように、電気力線ａが沿って形成される反応容器１の曲面部８の内面に沿うようにして吹き出し口４を反応容器１の下面の両側の端部に形成したりすることができる。
【０１１１】
図２４に他の参考形態を示す。このプラズマ処理装置は、反応容器１の外周面の全周に亘って電極２と電極３を接触させて設けると共に電極２と電極３を上下に対向させて配置することによって形成されており、反応容器１の内部において電極２と電極３の間に放電空間１５が形成されている。反応容器１は上記と同様の材料で有底の円筒で形成されている。また、反応容器１の上面はガス導入口１６として略全面に亘って開放されていると共に反応容器１の円形の下面はほぼ平坦な面で形成されている。そして、図２４（ｂ）に示すように、反応容器１の下面には多数個の微小孔９を底面視で円形に並べることによって、微小孔９の集合体で円形の幅広の吹き出し口４が形成されている。各微小孔９は反応容器１の内部の放電空間１５と連通している。この微小孔９の直径は、印加条件や被処理物の種類などによって異なるが、０．５〜２ｍｍに設定することができる。
【０１１２】
電極２と電極３は同形であって、平面視でＯ字状（円形環状）に形成されている。すなわち、電極２と電極３の略中央部には上下に貫通する挿着孔１７が形成されている。この挿着孔１７の大きさは反応容器１の外周寸法とほぼ同一に、また、挿着孔１７の平面視の形状は反応容器１の外周形状とほぼ同一にそれぞれ形成されている。電極２と電極３は上記と同様の材料で形成されている。そして、電極２と電極３を平面視でＯ字状の円形環状に形成することによって、反応容器１の全周に亘って電極２と電極３を配置することができ、電極２及び電極３と反応容器１との接触面積を大きくして接触性を向上させることができ、プラズマの生成が容易になるものである。加えて、電極２と電極３の内面（挿着孔１７を構成する面）は反応容器１の外周と接触する面であって、その内面の算術平均粗さで表した表面粗度は１０〜１０００μｍに設定されている。
【０１１３】
そして、反応容器１を挿着孔１７に差し込むことによって、電極２と電極３を反応容器１の外周に取り付けると共に電極２と電極３の内周面を反応容器１の外周面に接触させるように配置し、交流電界を発生させる電源１８を電極２に接続すると共に電極３を接地することによって、図２４（ａ）に示すようなプラズマ処理装置を形成することができる。ここで、接地される電極３は高電圧が印加される電極２よりも下側に、すなわち、電極３は電極２よりも吹き出し口４の近くに配置されている。また、電極２と電極３の間隔は３〜２０ｍｍに設定するのが好ましい。このように形成されるプラズマ処理装置は、上記の図１に示す実施の形態と同様にしてプラズマ処理を行うことができ、また、図１に示す実施の形態と同様の効果を奏するものである。
【０１１４】
さらに、この参考形態では、微小孔９の集合体で吹き出し口４を形成したので、反応容器１の下面の全周に亘ってスリット状の吹き出し口を形成する場合に比べて、放電空間１５の体積を小さくすることなく吹き出し口４から吹き出されるプラズマの流速を加速することができ、短寿命のラジカルなどの反応性ガス活性粒子が消滅する前に被処理物にプラズマジェットを到達させることができて被処理物のプラズマ処理を効率よく行うことができる。
【０１１５】
図２５に他の参考形態を示す。このプラズマ処理装置では、電気力線ａが沿って形成される反応容器１の内周面に沿うようにして吹き出し口４を反応容器１の下面の略半部の周端部に偏らせて形成したものであり、その他の構成は図２１のものと同様に形成されている。すなわち、図２４のプラズマ処理装置では、反応容器１の内周面の全周に沿って吹き出し口４が形成されているが、図２５のプラズマ処理装置では反応容器１の下面の中心線Ｆを挟んで片側の内周面の近傍にのみに吹き出し口４が形成されている。
【０１１６】
上記のように図２４のプラズマ処理装置では、電極２と電極３が反応容器１の外周面に接触することにより、反応容器１の内周面に沿った電気力線ａが多く形成されるが、このことでプラズマＰは、図３（ｂ）（ｃ）に示すように反応容器１の中央部よりも反応容器１の内周面の近傍において集中して生成されて濃度が高くなる傾向にある。従って、反応容器１の下面において反応容器１の厚み方向の略中央部に吹き出し口４を形成するよりも、図２５に示すように、反応容器１の下面において反応容器１の内周面の近傍で内周面に沿って吹き出し口４を形成する方が効率よくプラズマＰを吹き出すことができ、プラズマ処理の能力を向上させることができるものである。
【０１１７】
図２６に他の参考形態を示す。このプラズマ処理装置では、電気力線ａが沿って形成される反応容器１の内周面に沿うようにして吹き出し口４を反応容器１の下面の略半分の両側の周端部に偏らせて形成したものであり、その他の構成は図２４のものと同様に形成されている。すなわち、図２４のプラズマ処理装置では、反応容器１の内周面の全周に沿って吹き出し口４が形成されているが、図２６のプラズマ処理装置では反応容器１の下面の中心線Ｆを挟んで両側の内周面の近傍に吹き出し口４が形成されている。
【０１１８】
上記のように図２４のプラズマ処理装置では、電極２と電極３が反応容器１の外周面に接触することにより、反応容器１の内周面に沿った電気力線ａが多く形成されるが、このことでプラズマＰは、図３（ｂ）（ｃ）に示すように反応容器１の中央部よりも反応容器１の内周面の近傍において集中して生成されて濃度が高くなる傾向にある。従って、反応容器１の下面において反応容器１の厚み方向の略中央部に吹き出し口４を形成するよりも、図２６に示すように、反応容器１の下面において反応容器１の内周面の近傍で内周面に沿って吹き出し口４を形成する方が効率よくプラズマＰを吹き出すことができ、プラズマ処理の能力を向上させることができるものである。しかも、図４と同様に、吹き出し口４の下側において、被処理物６０を吹き出し口４の長手方向とほぼ直交する方向に搬送してプラズマ処理を行うことによって、プラズマＰを被処理物６０に二重（二回）に吹き付けることができ、図２５のものに比べて、被処理物６０の一回の搬送におけるプラズマＰの照射時間が二倍になって、プラズマ処理の能力を向上させることができるものである。尚、この参考形態においては、図２５のものに比べて吹き出し口４の開口面積が増えるために、プラズマ生成用ガスの流量を増やしてプラズマＰの吹き出しの流速が低下しないようにするのが好ましい。
【０１１９】
図２７、２８に他の参考形態を示す。この参考形態は図２４のプラズマ処理装置において、電極２と電極３を冷却するものである。つまり、電極２と電極３の内部は冷媒が流通可能な流通部２６として形成されていると共に、電極２と電極３の外周面には流通部２６と連通する供給管２１と排出管２２が突設されている。そして、矢印（３）で示すように供給管２１を通じて電極２と電極３の内部の流通部２６に冷媒を供給することによって、プラズマを発生させている間、電極２と電極３を冷却するのである。流通部２６に供給された冷媒は矢印（４）で示すように排出管２２を通じて電極２と電極３から排出される。冷媒としては上記と同様のものを使用することができる。そして、この参考形態は、電極２と電極３を冷却するので、上記の図５、６に示す実施の形態と同様の効果を奏するものである。
【０１２０】
尚、この参考形態においても、図２５に示すように、電気力線ａが沿って形成される反応容器１の内周面に沿うようにして吹き出し口４を反応容器１の下面の片側の周端部に形成したり、図２６に示すように、電気力線ａが沿って形成される反応容器１の内周面に沿うようにして吹き出し口４を反応容器１の下面の両側の周端部に形成したりすることができる。
【０１２１】
図２９に他の参考形態を示す。この参考形態は図２７、２８のプラズマ処理装置において、放電空間１５の体積を減少させるための体積減少具１１を設けたものである。体積減少具１１は図３０に示すように、反応容器１よりも小さく反応容器１の内部形状と略等しい円筒状に形成されるものであって、体積減少具１１の内部には導入管４０が上下方向に長く配設されている。また、導入管４０の上端は導入部２４として体積減少具１１の上面に突出されている。さらに、体積減少具１１の上面には導入部２４の両側において、一対の略Ｌ字状の導出管４１が突設されている。そして、体積減少具１１は上記と同様の冷媒を流通させることによって、冷却されるものである。すなわち、矢印（５）で示すように導入部２４を通じて導入管４０及び体積減少具１１の内部に冷媒を供給して流通させることによって、体積減少具１１を冷却するのである。体積減少具１１に供給された冷媒は矢印（６）で示すように導出管４１を通じて排出される。また、体積減少具１１は上記と同様の材料で形成されるものである。
【０１２２】
この体積減少具１１はその下部が放電空間１５内に位置するように、ガス導入口１６から反応容器１の内部に挿入されて配置されている。従って、この実施の形態における放電空間１５の体積は、図２７、２８のプラズマ処理装置の放電空間１５よりも減少しており、上記の図７に示す実施の形態と同様の効果を奏するものである。
【０１２３】
尚、この参考形態においても、図２５に示すように、電気力線ａが沿って形成される反応容器１の内周面に沿うようにして吹き出し口４を反応容器１の下面の片側の周端部に形成したり、図２６に示すように、電気力線ａが沿って形成される反応容器１の内周面に沿うようにして吹き出し口４を反応容器１の下面の両側の周端部に形成したりすることができる。
【０１２４】
図３１に他の参考形態を示す。このプラズマ処理装置は、反応容器１の外周の全周に亘って電極２と電極３を接触させて設けると共に電極２と電極３を上下に対向させて配置することによって形成されており、反応容器１の内部において電極２と電極３の間に放電空間１５が形成されている。反応容器１は上記と同様の材料で円筒で形成されている。また、反応容器１の上面はガス導入口１６として略全面に亘って開放されていると共に反応容器１の下部は下側ほど厚み方向の寸法が小さくなるように絞り込まれた集束部４５として形成されている。そして、図３１（ｂ）に示すように、反応容器１の集束部４５の下面には反応容器１の幅方向に長い直線状の吹き出し口４が形成されている。吹き出し口４はスリット状に形成されており、反応容器１の内部の放電空間１５と連通している。また、電極２と電極３は図２４に示す参考形態と同様に形成されている。
【０１２５】
そして、反応容器１を電極２と電極３の挿着孔１７に差し込むことによって、電極２と電極３を反応容器１の外周に取り付けると共に電極２と電極３の内周面を反応容器１の外周面に接触させるように配置し、交流電界を発生させる電源１８を電極２に接続すると共に電極３を接地することによって、図３１（ａ）に示すようなプラズマ処理装置を形成することができる。ここで、接地される電極３は電極２よりも下側に、すなわち、電極３は電極２よりも吹き出し口４の近くに配置されている。また、電極２と電極３の間隔は３〜２０ｍｍに設定するのが好ましい。このように形成されるプラズマ処理装置は、上記の図１に示す実施の形態と同様にしてプラズマ処理を行うことができ、また、図１に示す実施の形態と同様の効果を奏するものである。
【０１２６】
さらに、この参考形態では、吹き出し口４が直線状となるように絞り込まれた集束部４５を設けることによって、集束部４５を設けないで反応容器１を真っ直ぐに形成した場合に比べて、放電空間１５の体積を小さくすることなく吹き出し口４から吹き出されるプラズマの流速を集束部４５で加速することができ、短寿命のラジカルなどの反応性ガス活性粒子が消滅する前に被処理物にジェット状のプラズマを到達させることができて被処理物のプラズマ処理を効率よく行うことができる。被処理物の表面のクリーニングに適したプラズマの流速を得るためには、集束部４５の外周面と集束部４５以外の反応容器１の外面との間に形成されるテーパー角が１０〜３０°であることが好ましい。
【０１２７】
図３２、３３に他の参考形態を示す。この実施の形態は図３１のプラズマ処理装置において、電極２と電極３を冷却するものである。つまり、電極２と電極３の内部は冷媒が流通可能な流通部２６として形成されていると共に、電極２と電極３の外周面には流通部２６と連通する供給管２１と排出管２２が突設されている。そして、矢印（３）で示すように供給管２１を通じて電極２と電極３の内部の流通部２６に冷媒を供給することによって、プラズマを発生させている間、電極２と電極３を冷却するのである。流通部２６に供給された冷媒は矢印（４）で示すように排出管２２を通じて電極２と電極３から排出される。冷媒としては上記と同様のものを使用することができる。そして、この参考形態は、電極２と電極３を冷却するので、上記の図５、６に示す実施の形態と同様の効果を奏するものである。
【０１２８】
尚、図３１乃至３３の参考形態においても、図３０の体積減少具１１を用いても良い。
【０１２９】
【実施例】
以下本発明を実施例によって具体的に説明する。
【０１３０】
（実施例１）
図５に示す構造のプラズマ処理装置を形成した。反応容器１としては石英ガラスを用い、幅寸法を６０ｍｍ、厚さ寸法を７ｍｍに形成した。また、吹き出し口４は０．２×５５ｍｍに形成した。上側の電極２と下側の電極３は銅製であって、その内周面の算術平均粗さは１００μｍに形成した。また、電極２と電極３を冷却する冷媒としては純水を用いた。被処理物としては、ネガ型レジストを１μｍ塗布したシリコン基板を使用した。
【０１３１】
プラズマ生成用ガスはヘリウムを１リットル／ｍｉｎ、アルゴンを４リットル／ｍｉｎ、酸素を０．０６リットル／ｍｉｎの割合で混合したものを流して反応容器１に供給した。そして放電空間１５に４００Ｗで１３．５６ＭＨｚの高周波電界を印加してプラズマを発生させ、これを吹き出し口４から幅広にジェット状に吹き出して被処理物の表面に供給してプラズマ処理（レジストのエッチング）を行った。
【０１３２】
この結果、５０ｍｍの幅で約７μｍ／分のエッチング速度が得られ、極めて均一な形状にレジストをエッチングすることができた。また、ＸＰＳ分析の結果、レジスト成分以外の不純物は検出されなかった。
【０１３３】
（実施例２）
図１７に示す構造のプラズマ処理装置を形成した。反応容器１としては石英ガラスを用い、幅寸法を６０ｍｍ、厚さ寸法を５０ｍｍに形成した。また、吹き出し口４は０．２×５５ｍｍに形成した。右側の電極２と左側の電極３は銅製であって、その内周面の算術平均粗さは１００μｍに形成した。また、電極２と電極３を冷却する冷媒としては純水を用いた。被処理物としては、ネガ型レジストを１μｍ塗布したシリコン基板を使用した。
【０１３４】
プラズマ生成用ガスはヘリウムを１リットル／ｍｉｎ、アルゴンを４リットル／ｍｉｎ、酸素を０．０６リットル／ｍｉｎの割合で混合したものを流して反応容器１に供給した。そして放電空間１５に４００Ｗで１３．５６ＭＨｚの高周波電界を印加してプラズマを発生させ、これを吹き出し口４から幅広にジェット状に吹き出して被処理物の表面に供給してプラズマ処理（レジストのエッチング）を行った。
【０１３５】
この結果、５０ｍｍの幅で約５μｍ／分のエッチング速度が得られ、極めて均一な形状にレジストをエッチングすることができた。また、ＸＰＳ分析の結果、レジスト成分以外の不純物は検出されなかった。
【０１３６】
（実施例３）
図２３に示す構造のプラズマ処理装置を形成した。反応容器１としては断面半円弧状の石英ガラス管を用い、外径寸法を２０ｍｍに形成した。また、吹き出し口４は０．２×５５ｍｍに形成した。さらに、反応容器１には外径８ｍｍの石英管を体積減少具１１として挿入した。右側の電極２と左側の電極３は銅製であって、その内周面の算術平均粗さは１００μｍに形成した。また、電極２と電極３と体積減少具１１を冷却する冷媒としては純水を用いた。
【０１３７】
被処理物としては、ＯＭＰＡＣ(Over Molded Pad Array Carrier)型ＢＧＡ(Ball Grid Array)基板を使用した。これは、０．５ｍｍ厚のＢＴ（ビスマレイミドトリアジン）基板（サイズは５０×２００ｍｍ）に、太陽インキ社製のレジスト（ＰＳＲ−４０００ＡＵＳ５）を４０μｍ厚に塗布して形成したものである。また、この被処理物の一部には、ボンディングパッドを含む金メッキ回路が形成されていると共にＩＣチップが搭載されている。このＩＣチップは、プラズマ処理によるチャージアップダメージ（給電時における損傷）を評価するために、シリコン基板の上に厚み１０ｎｍのＳｉＯ₂層と厚み３００ｎｍのポリシリコンを形成したものである。
【０１３８】
プラズマ生成用ガスはヘリウムを２リットル／ｍｉｎ、アルゴンを８リットル／ｍｉｎ、酸素を０．２リットル／ｍｉｎの割合で混合したものを流して反応容器１に供給した。そして放電空間１５に５００Ｗで１３．５６ＭＨｚの高周波電界を印加してプラズマを発生させ、これを吹き出し口４から幅広にジェット状に吹き出して被処理物の表面に供給してプラズマ処理（被処理物６の表面の改質処理及びクリーニング処理）を行った。
【０１３９】
この結果、処理の前後でレジスト部分の水の接触角が８０度から８度に低下し、表面の親水性が改善された。また、金メッキ回路のボンディングパッドとＩＣチップとをワイヤボンディングした結果、ワイヤボンディングの強度が処理前では５．１ｇであったのに対して、処理後では８．９ｇに向上し、著しい性能（ワイヤボンディングの強度）の向上が見られた。また、ボンディングパッド部をＸＰＳ分析した結果、表面における炭素原子と金原子の組成比率（Ｃ／Ａｕ）は、処理の前後で約３から約０．５にまで減少しており、ボンディングパッド部の炭素除去が行われていた。このように炭素除去が行われたために、ワイヤボンディングの強度が向上したと考えられる。また、炭素原子と金原子以外の他の不純物は検出されなかった。
【０１４０】
さらに、プラスコン社製の封止樹脂（ＳＭＴ−Ｂ−１）を用いて被処理物の表面に底面積１ｃｍ²のプリン状の封止樹脂を形成し、封止樹脂と被処理物の剪断剥離強度を測定した結果、処理前では２ＭＰａであったのに対して、処理後では１０ＭＰａと大きく強度が向上していた。また、被処理物に搭載したＩＣチップのチャージアップダメージも無かった。
【０１４１】
（参考例１）
図２９に示す構造のプラズマ処理装置Ａを形成した。反応容器１としては石英ガラス管を用い、外径を５８ｍｍ、内寸を５５ｍｍに形成した。上側の電極２と下側の電極３は銅製であって、その内周面の算術平均粗さは１００μｍに形成した。また、反応容器１の内部には体積減少具１１として外径が５０ｍｍのステンレス二重管を挿入して設けた。さらに、電極２と電極３と体積減少具１１を冷却する冷媒としては純水を用いた。
【０１４２】
被処理物としては、アルミナ基板に銀パラジウムペーストをスクリーン印刷し、これを焼き付けしてボンディングパッド部を含む回路を形成したものを使用した。その他の構成は実施例３と同様である。
【０１４３】
プラズマ生成用ガスはヘリウムを２リットル／ｍｉｎ、アルゴンを８リットル／ｍｉｎ、水素を０．１リットル／ｍｉｎの割合で混合したものを流して反応容器１に供給した。そして放電空間１５に５００Ｗで１３．５６ＭＨｚの高周波電界を印加してプラズマを発生させ、これを吹き出し口４から幅広にジェット状に吹き出して被処理物の表面に供給してプラズマ処理（被処理物６の表面の改質処理及びクリーニング処理）を行った。
【０１４４】
ボンディングパッド部をＸＰＳ分析した結果、処理前では酸化銀のピークが確認されたが、処理後にはこのピークは金属銀に変化しており、ボンディングパッド部の酸化銀が減少していた。また、プラズマ処理中に吹き出し口４より５ｍｍ離れた位置でのプラズマの温度を測定した結果、体積減少具８を冷媒で冷却した場合は冷媒で冷却しない場合に比べて、約２００℃低下していた。
【０１４５】
（参考例２）
実施例１において、スリット状の吹き出し口４の代わりに、直径１ｍｍの孔を２ｍｍの間隔で２８個並べ、この孔の集合体を吹き出し口４として形成した。これ以外は実施例１と同様にしてプラズマ処理を行った。
【０１４６】
この結果、５０ｍｍの幅で約７μｍ／分のエッチング速度が得られ、極めて均一な形状にレジストをエッチングすることができた。また、ＸＰＳ分析の結果、レジスト成分以外の不純物は検出されなかった。
【０１４７】
（参考例３）
図１１に示す構造のプラズマ処理装置を形成した。反応容器１としては石英ガラスを用い、幅外寸法を５６ｍｍ、幅内寸法を５４ｍｍ、厚さ外寸法を３ｍｍ、厚さ内寸法を１ｍｍに形成した。また、上側の電極２と下側の電極３は銅製であって、その内周面の算術平均粗さは１００μｍに形成した。また、電極２と電極３を冷却する冷媒としては純水を用いた。被処理物としては、ネガ型レジストを１μｍ塗布したシリコン基板を使用した。
【０１４８】
プラズマ生成用ガスはヘリウムを２リットル／ｍｉｎ、アルゴンを１０リットル／ｍｉｎ、酸素を０．４リットル／ｍｉｎの割合で混合したものを流して反応容器１に供給した。そして放電空間１５に７００Ｗで１３．５６ＭＨｚの高周波電界を印加してプラズマを発生させ、これを吹き出し口４から幅広にジェット状に吹き出して被処理物の表面に供給してプラズマ処理（レジストのエッチング）を行った。
【０１４９】
この結果、５５ｍｍの幅で約１５μｍ／分のエッチング速度が得られ、極めて均一な形状にレジストをエッチングすることができた。また、ＸＰＳ分析の結果、レジスト成分以外の不純物は検出されなかった。
【０１５０】
【発明の効果】
上記のように本発明の請求項１の発明は、絶縁材料で形成される反応容器と、反応容器の外面に接する少なくとも一対の対向する電極とを具備して構成され、反応容器にプラズマ生成用ガスを供給すると共に電極の間に交流電界を印加することにより大気圧下で反応容器内にグロー状の放電を生じさせ、グロー状の放電により反応容器内にプラズマを生成するようにしたプラズマ処理装置において、反応容器の内面に沿った電気力線が形成されるように一対の電極を配置し、幅を持ったジェット状のプラズマを吹き出すための吹き出し口を反応容器に形成するので、反応容器の内面の垂直方向に電気力線が生じにくくなって電気力線による反応容器の劣化を少なくすることができ、反応容器の内面からその構成物質が飛び出しにくくなって被処理物が不純物により汚染されるのを少なくすることができるものであり、しかも、カーテンのような幅を持ったプラズマを吹き出し口から吹き出しながら基板あるいはプラズマ処理装置を吹き出し口の幅方向と直交する方向に移動させて基板の表面全面にプラズマを走査して吹き付けることによって、スポット的なプラズマを吹き出すものに比べて被処理物の広い面積を一度にプラズマ処理することができ、ＢＧＡ基板などの基板の全面を処理する場合に処理時間を短くすることができるものである。
また、吹き出し口をスリット状に形成するので、カーテンのような幅を持ったプラズマを吹き出し口から吹き出しながら基板あるいはプラズマ処理装置を吹き出し口の幅方向と直交する方向に移動させて基板の表面全面にプラズマを走査して吹き付けることによって、スポット的なプラズマを吹き出すものに比べて被処理物の広い面積を一度にプラズマ処理することができ、ＢＧＡ基板などの基板の全面を処理する場合に処理時間を短くすることができるものである。
また、吹き出し口を反応容器の平面部分に形成し、このスリット状の吹き出し口の開口面積を反応容器内部の断面積よりも小さく形成するので、被処理物を吹き出し口の近傍にまで近づけることが可能となり、また、吹き出し口と被処理物の距離を略一定に保つことが容易となり、吹き出し口から大気中に吹き出されたプラズマに含まれている活性の高い生きたプラズマ活性種を消滅させる前に被処理物に吹き付けることができ、プラズマ中の活性種を効率よく利用して被処理物のプラズマ処理を高めることができるものである。
【０１５１】
また本発明の請求項２の発明は、箱状の反応容器の下面に吹き出し口を形成するので、カーテンのような幅を持ったプラズマを反応容器の下面の吹き出し口から下側に吹き出しながら基板あるいはプラズマ処理装置を吹き出し口の幅方向と直交する方向に移動させて基板の表面全面にプラズマを走査して吹き付けることによって、スポット的なプラズマを吹き出すものに比べて被処理物の広い面積を一度にプラズマ処理することができ、ＢＧＡ基板などの基板の全面を処理する場合に処理時間を短くすることができるものである。
【０１５２】
また本発明の請求項３の発明は、一対の電極を上下に対向させて配置するので、一対の電極の間に生成される交流電界の方向（電気力線の方向）とプラズマ生成用ガス及びプラズマの流れ方向とをほぼ一致させることができ、プラズマの活性種を効率よく生成することができるものであり、しかも、一対の電極の間隔を変えることによって、放電空間の大きさを簡単に変えることができ、プラズマの生成量を容易に調整することができるものである。
【０１５３】
また本発明の請求項４の発明は、反応容器を扁平筒状に形成し、反応容器の側壁の対向間隔を幅狭方向へ０．１〜５ｍｍに形成するので、一対の電極の間に形成される放電空間の体積が小さくなって放電空間の単位体積あたりの電力が向上してプラズマ処理の生成効率を向上させることができ、低電力化及び小ガス流量化を図ることができるものである。
【０１５４】
また本発明の請求項５の発明は、電極を平面視でロ字状に形成するので、反応容器の全周に亘って電極を配置することができ、電極と反応容器との接触面積を大きくして接触性を向上させることができ、プラズマの生成が容易になるものである。
【０１５５】
また本発明の請求項６の発明は、接地される一方の電極を高電圧が印加される他方の電極よりも吹き出し口に近づけて配置するので、高電圧が印加される電極が接地される電極よりも被処理物から遠くに位置することになり、高圧となる電極から被処理物にアーク放電が飛びにくくなって、アーク放電による被処理物の破損を防止することができるものである。
【０１５６】
また本発明の請求項７の発明は、吹き出し口の長手方向と平行な方向に長く電極を形成するので、吹き出し口の上側（上流側）に広域の放電空間が形成されることになって、プラズマ生成用ガスのプラズマ化を効率よく行うことができ、密度の高いプラズマを形成することができるものであり、また、吹き出し口の全長に亘って均質なプラズマを吹き出すことができるものである。よって、高い密度で均質なプラズマが被処理物に吹き付けられることになって、プラズマ処理の性能を向上させることができ、プラズマ処理を短時間で行うことができるものである。
【０１５７】
また本発明の請求項８の発明は、電極を側面視で下面が開口するコ字状に形成するので、電極の先端が反応容器の下面から突出しないように、反応容器の下面及び電極の先端面を面一に形成して被処理物を吹き出し口の近傍にまで近づけることが可能となり、吹き出し口から大気中に吹き出されたプラズマに含まれている活性の高い生きたプラズマ活性種を消滅させる前に被処理物に吹き付けることができてプラズマ中の活性種を効率よく利用して被処理物のプラズマ処理を高めることができるものである。
【０１５８】
また本発明の請求項９の発明は、反応容器内でのプラズマ生成用ガスの流れを均一化するためのガス均一化室を設け、前記ガス均一化室は、このガス均一化室に供給されたプラズマ生成用ガスがこのガス均一化室を通過して反応容器内に導入されるように形成されたものであるので、ガス均一化室を通して反応容器にプラズマ生成用ガスを供給することによって、プラズマ生成用ガスが反応容器内の一部分に偏らないように、反応容器内の全体に均一な濃度で供給することができ、均質なプラズマを効率よく生成することができるものである。
【０１５９】
また本発明の請求項１０の発明は、ガス均一化室内に突出する鍔部を反応容器に形成するので、鍔部でプラズマ生成用ガスの撹拌性を高めることができ、より均質なプラズマを効率よく生成することができるものである。
【０１６０】
また本発明の請求項１１の発明は、ガス均一化室に球体を充填するので、ガス均一化室に充填された球体の間の隙間を通して反応容器にプラズマ生成用ガスを供給することによって、プラズマ生成用ガスが反応容器内の一部分に偏らないように、反応容器内の全体により均一な濃度で供給することができ、より均質なプラズマを効率よく生成することができるものである。
【０１６１】
また本発明の請求項１２の発明は、平坦な平面部と断面が半円弧状の曲面部とを備えて反応容器を形成し、平面部に吹き出し口を形成するので、被処理物を吹き出し口の近傍にまで近づけることが可能となり、また、吹き出し口と被処理物の距離を略一定に保つことが容易となり、吹き出し口から大気中に吹き出されたプラズマに含まれている活性の高い生きたプラズマ活性種を消滅させる前に被処理物に吹き付けることができ、プラズマ中の活性種を効率よく利用して被処理物のプラズマ処理を高めることができるものである。
【０１６２】
また本発明の請求項１３の発明は、曲面部に電極を配置するので、反応容器の曲面部の内面の垂直方向に電気力線が生じにくくなって電気力線による反応容器の劣化を少なくすることができ、反応容器の内面からその構成物質が飛び出しにくくなって被処理物が不純物により汚染されるのを少なくすることができるものである。
【０１６３】
また本発明の請求項１４の発明は、電極を半円弧状に形成するので、反応容器の曲面部の全周に亘って電極を配置することができ、電極と反応容器との接触面積を大きくして接触性を向上させることができ、プラズマの生成が容易になるものであり、しかも、反応容器の下面及び電極の先端面を面一に形成して被処理物を吹き出し口の近傍にまで近づけることが可能となり、また、吹き出し口と被処理物の距離を略一定に保つことが容易となり、吹き出し口から大気中に吹き出されたプラズマに含まれている活性の高い生きたプラズマ活性種を消滅させる前に被処理物に吹き付けることができ、プラズマ中の活性種を効率よく利用して被処理物のプラズマ処理を高めることができるものである。
【０１６４】
また本発明の請求項１５の発明は、反応容器の下面を平面部として形成し、プラズマ生成用ガスを反応容器に横から供給するので、吹き出し口の全長に亘って均一にプラズマ生成用ガスを供給することができ、均質なプラズマを効率よく生成することができるものである。よって、高い密度で均質なプラズマが被処理物に吹き付けられることになって、プラズマ処理の性能を向上させることができ、プラズマ処理を短時間で行うことができるものである。
【０１６５】
また本発明の請求項１６の発明は、反応容器を円筒状に形成し、一対の電極を上下に対向させて配置するので、反応容器の内面の垂直方向に電気力線が生じにくくなって電気力線による反応容器の劣化を少なくすることができ、反応容器の内面からその構成物質が飛び出しにくくなって被処理物が不純物により汚染されるのを少なくすることができるものである。
【０１６６】
また本発明の請求項１７の発明は、電極を平面視で環状に形成するので、反応容器の全周に亘って電極を配置することができ、電極と反応容器との接触面積を大きくして接触性を向上させることができ、プラズマの生成が容易になるものである。
【０１６７】
また本発明の請求項１８の発明は、接地される一方の電極を高電圧が印加される他方の電極よりも吹き出し口に近づけて配置するので、高電圧が印加される電極が接地される電極よりも被処理物から遠くに位置することになり、高圧となる電極から被処理物にアーク放電が飛びにくくなって、アーク放電による被処理物の破損を防止することができるものである。
【０１７２】
また本発明の請求項１９の発明は、電気力線が沿って形成される反応容器の内面に沿わせて吹き出し口を形成するので、プラズマが集中して生成されて濃度が高くなる傾向にある反応容器の内面に沿わせて吹き出し口を形成することによって、プラズマを吹き出し口から効率よく吹き出すことができ、プラズマ処理の能力を向上させることができるものである。
【０１７３】
また本発明の請求項２０の発明は、電気力線が沿って形成される反応容器の複数個の内面のそれぞれに沿わせて吹き出し口を形成するので、プラズマが集中して生成されて濃度が高くなる傾向にある反応容器の内面に沿わせて吹き出し口を形成することによって、プラズマを吹き出し口から効率よく吹き出すことができ、プラズマ処理の能力を向上させることができるものであり、しかも、被処理物の複数箇所に一度にプラズマ処理を施すことができ、プラズマ処理の効率を向上させることができるものである。
【０１７４】
また本発明の請求項２１の発明は、少なくとも一方の電極を冷媒で冷却するので、大気圧下で周波数の高い交流でプラズマを生成しても、電極の温度上昇を抑えることができ、よってプラズマの温度（ガス温度）が高くならないようにすることができて被処理物の熱的損傷を少なくすることができるものである。また、電極を冷却することによって、放電空間の局所的な加熱を防ぐことができ、均質なグロー状の放電を生成してストリーマー放電の生成を抑えることができて被処理物のストリーマー放電による損傷をより少なくすることができるものである。
【０１７５】
また本発明の請求項２２の発明は、反応容器内において一対の電極の間に形成される放電空間の体積を減少させるための体積減少具を反応容器内に設けるので、放電空間における単位体積あたりの投入電力（交流電界）を増加させることができ、プラズマの生成の効率を向上させることができるものである。
【０１７６】
また本発明の請求項２３の発明は、体積減少具を絶縁材料で形成するので、体積減少具からスパッタリングや腐食により不純物が生じないようにすることができ、長期間の使用であっても被処理物が不純物より汚染されないようにすることができるものである。
【０１７７】
また本発明の請求項２４の発明は、体積減少具を冷媒で冷却するので、体積減少具の熱による劣化を低減することができ、体積減少具の長寿命化を図ることができるものであり、しかも、体積減少具の周囲の放電空間で生成されるプラズマの温度を低下させることができ、被処理物の熱によるダメージを少なくすることができるものである。
【０１７８】
また本発明の請求項２５の発明は、体積減少具を金属材料で形成すると共に体積減少具を冷媒で冷却するので、体積減少具を絶縁材料で形成する場合に比べて、体積減少具の周囲の放電空間で生成されるプラズマの温度をさらに低下させることができ、被処理物の熱によるダメージをさらに少なくすることができるものである。
【０１７９】
また本発明の請求項２６の発明は、冷媒がイオン交換水であるので、冷媒中に不純物が含まれることがなく、電極と体積減少具が冷媒で腐食されにくくなり、長寿命化を図ることができるものである。
【０１８０】
また本発明の請求項２７の発明は、冷媒が不凍性及び絶縁性を有するので、高電圧が印加される電極からの漏電を防止することができ、プラズマの生成を安定して行うことができるものである。
【０１８１】
また本発明の請求項２８の発明は、一対の電極の間に印加する交流電界の周波数を１ｋＨｚ〜２００ＭＨｚに設定するので、放電空間での放電を安定化させることができ、プラズマ処理を効率よく行うことができるものであり、また、放電空間でのプラズマの温度上昇を抑えて、反応容器や電極や体積減少具の寿命を長くすることができるものであり、しかも、プラズマ処理装置が複雑化及び大型化するのを少なくすることができるものである。
【０１８２】
また本発明の請求項２９の発明は、電極の反応容器と接触する側の表面粗度を１０〜１０００μｍに形成するので、非常に微細なマイクロディスチャージの集合体が形成され、アークへの移行を阻害することができ、放電空間における放電の均一化を図ることができるものである。
【０１８３】
本発明の請求項３０の発明は、請求項１乃至２９のいずれかに記載のプラズマ処理装置の吹き出し口の下方に被処理物を配置し、吹き出し口からプラズマを吹き出して被処理物に供給するので、反応容器の内面の垂直方向に電気力線が生じにくくなって電気力線による反応容器の劣化を少なくすることができ、反応容器の内面からその構成物質が飛び出しにくくなって被処理物が不純物により汚染されるのを少なくすることができるものであり、しかも、カーテンのような幅を持ったプラズマを吹き出し口から吹き出しながら基板あるいはプラズマ処理装置を吹き出し口の幅方向と直交する方向に移動させて基板の表面全面にプラズマを走査して吹き付けることによって、スポット的なプラズマを吹き出すものに比べて被処理物の広い面積を一度にプラズマ処理することができ、ＢＧＡ基板などの基板の全面を処理する場合に処理時間を短くすることができるものである。
【図面の簡単な説明】
【図１】 本発明の実施の形態の一例を示し、（ａ）は斜視図、（ｂ）は底面図である。
【図２】 （ａ）は同上の一部の断面図、（ｂ）は従来例の一部の断面図である。
【図３】 （ａ）は同上の他の実施の形態を示す底面図、（ｂ）は一部の断面図、（ｃ）は図１に示す実施の形態の一部の断面図である。
【図４】 （ａ）は同上の他の実施の形態を示す底面図、（ｂ）は一部の断面図である。
【図５】 同上の他の実施の形態の一例を示す斜視図である。
【図６】 同上の底面図である。
【図７】 同上の他の実施の形態の一例を示す斜視図である。
【図８】 同上の体積減少具の一例を示し、（ａ）は斜視図、（ｂ）は正面図である。
【図９】 同上の体積減少具の種類とクリーニング性能及びプラズマのガス温度の関係を示すグラフである。
【図１０】 同上の参考形態の一例を示し、（ａ）は一部が破断した正面図、（ｂ）は一部が破断した側面図である。
【図１１】 同上の参考形態の一例を示す斜視図である。
【図１２】 同上の反応容器の一例を示し、（ａ）は正面図、（ｂ）は側面図、（ｃ）は底面図である。
【図１３】 図１２（ｂ）におけるア部分を示す断面図である。
【図１４】 同上の他の実施の形態の一例を示し、（ａ）は斜視図、（ｂ）は底面図である。
【図１５】 （ａ）は同上の他の実施の形態を示す底面図、（ｂ）は側面図、（ｃ）は図１４に示す実施の形態の底面図である。
【図１６】 同上の他の実施の形態を示す底面図である。
【図１７】 同上の他の実施の形態の一例を示す斜視図である。
【図１８】 同上の底面図である。
【図１９】 同上の他の実施の形態の一例を示し、（ａ）は斜視図、（ｂ）は底面図である。
【図２０】 （ａ）は同上の他の実施の形態を示す底面図、（ｂ）は図１４に示す実施の形態の斜視図、（ｃ）は図１４に示す実施の形態の底面図である。
【図２１】 同上の他の実施の形態を示す底面図である。
【図２２】 同上の他の実施の形態の一例を示し、（ａ）は正面図、（ｂ）は底面図、（ｃ）は側面図である。
【図２３】 同上の他の実施の形態の一例を示し、（ａ）は正面図、（ｂ）は底面図、（ｃ）は側面図である。
【図２４】 同上の他の参考形態の一例を示し、（ａ）は斜視図、（ｂ）は底面図である。
【図２５】 同上の他の参考形態を示す底面図である。
【図２６】 同上の他の参考形態を示す底面図である。
【図２７】 同上の他の参考形態の一例を示す正面図である。
【図２８】 同上の底面図である。
【図２９】 同上の他の参考形態の一例を示す正面図である。
【図３０】 同上の体積減少具の一例を示す正面図である。
【図３１】 同上の他の参考形態の一例を示し、（ａ）は斜視図、（ｂ）は底面図である。
【図３２】 同上の他の参考形態の一例を示し、（ａ）は正面図、（ｂ）は側面図である。
【図３３】 同上の底面図である。
【符号の説明】
１ 反応容器
２ 電極
３ 電極
４ 吹き出し口
５ ガス均一化室
６ 球体
７ 平面部
８ 曲面部
９ 微小孔
１１ 体積減少具
１５ 放電空間
５０ 鍔部
ａ 電気力線[0001]
BACKGROUND OF THE INVENTION
The present invention is used for plasma treatments such as cleaning of foreign substances such as organic substances existing on the surface of an object to be processed, resist peeling, improvement of adhesion of an organic film, reduction of metal oxide, film formation, surface modification, and the like. In particular, the present invention relates to a plasma processing apparatus for generating a plasma and a plasma processing method using the same, and is particularly suitable for cleaning the surface of an electronic component that requires precise bonding.
[0002]
[Prior art]
Conventionally, an attempt has been made to perform plasma treatment under atmospheric pressure. For example, in JP-A-2-15171, JP-A-3-241539, and JP-A-1-306569, a pair of electrodes are arranged in a discharge space in a reaction vessel and a dielectric is provided between the electrodes. The discharge space is filled with a plasma generating gas mainly composed of a rare gas such as He (helium) or Ar (argon), and an object to be processed is placed in the reaction vessel and an alternating electric field is applied between the electrodes. A plasma processing method is disclosed, and a glow discharge is stably generated by applying an alternating electric field between electrodes on which a dielectric is disposed, and the plasma generating gas is excited by the glow discharge. Thus, plasma is generated in the reaction vessel, and the object to be processed is processed by this plasma.
[0003]
JP-A-4-334543 and JP-A-5-202481 also describe performing plasma treatment under atmospheric pressure. These publications describe a plurality of electrodes on the outer periphery of a cylindrical reaction tube. And an AC voltage is applied between the electrodes to generate plasma in the reaction tube, and the object to be processed is introduced into the reaction tube in which the plasma has been generated to process the object to be processed.
[0004]
However, the method described in the above publication has a problem that it is difficult to perform plasma treatment locally only on a specific portion of the object to be processed, and it takes a long processing time. Therefore, for example, Japanese Patent Application Laid-Open Nos. Hei 3-219082 and Japanese Patent Application Laid-Open No. Hei 3 (1990) disclose that plasma generated by glow discharge under atmospheric pressure (particularly, active species of plasma) is jetted onto the object to be processed. Japanese Patent Laid-Open No. 4-212253, Japanese Patent Laid-Open No. 6-108257, and the like. In the methods described in these publications, jet plasma is blown out in a spot manner and sprayed onto the object to be processed, thereby locally processing the object to be processed.
[0005]
JP-A-4-358076 discloses that plasma treatment is performed by supplying plasma to a workpiece with a certain width. In this method, a pair of dielectric coated electrodes having a solid dielectric disposed on the surface are arranged opposite to each other, a plasma generating gas is introduced between the dielectric coated electrodes from above, and a high voltage is applied to the dielectric coated electrodes. Is applied to generate plasma from the plasma generating gas, and supply this plasma downstream from between the dielectric-coated electrodes to the workpiece.
[0006]
[Problems to be solved by the invention]
However, in this method of blowing out plasma in a spot manner, since the area of the plasma supplied to the object to be processed is small, when processing the entire surface of a substrate such as a BGA (Ball Grid Array) substrate, the plasma is spread over the entire surface of the substrate. There is a problem that the processing time becomes long. Moreover, in the thing of Unexamined-Japanese-Patent No. 4-358076, since plasma is supplied to a board | substrate with a certain amount of width | variety, although processing time can be shortened compared with the method of blowing off plasma in jet shape, Since a pair of dielectric coated electrodes with a solid dielectric is placed facing each other and a high voltage is applied to the dielectric coated electrodes, plasma is generated, so that electricity is generated in the direction perpendicular to the surface of the solid dielectric. As a result of the solid dielectric deterioration caused by the electric lines of force, the constituent material is likely to jump out of the surface of the solid dielectric, and the constituent material of the solid dielectric that sticks out adheres to the workpiece as impurities. There was a problem that the workpiece was contaminated.
[0007]
The present invention has been made in view of the above points, and in the case of processing the entire surface of a substrate such as a BGA substrate, the processing time can be shortened, and the plasma that can reduce contamination of an object to be processed. An object of the present invention is to provide a processing apparatus and a plasma processing method.
[0008]
[Means for Solving the Problems]
A plasma processing apparatus according to a first aspect of the present invention includes a reaction vessel 1 formed of an insulating material and at least a pair of opposed electrodes 2 and 3 that are in contact with the outer surface of the reaction vessel 1. A plasma generating gas is supplied to 1 and an alternating electric field is applied between the electrodes 2 and 3 to cause a glow discharge in the reaction vessel 1 under atmospheric pressure. In the plasma processing apparatus adapted to generate plasma, a pair of electrodes 2 and 3 are arranged so that electric lines of force a along the inner surface of the reaction vessel 1 are formed, and jet plasma having a width is generated. A blowout port 4 for blowing out is formed in a slit shape in the flat plane portion of the reaction vessel 1. The opening area of the slit-like outlet 4 is formed smaller than the cross-sectional area inside the reaction vessel 1. It is characterized by comprising.
[0009]
The plasma processing apparatus according to claim 2 of the present invention is characterized in that, in addition to the structure of claim 1, a blow-out port 4 is formed on the lower surface of the box-shaped reaction vessel 1.
[0010]
A plasma processing apparatus according to a third aspect of the present invention is characterized in that, in addition to the configuration of the first or second aspect, a pair of electrodes 2 and 3 are arranged so as to face each other vertically.
[0011]
A plasma processing apparatus according to a fourth aspect of the present invention includes a reaction vessel 1 in addition to any one of the first to third aspects. To It is formed in a flat cylinder shape, and the opposing interval of the side wall 1a of the reaction vessel 1 is 0.1 to 5 mm in the narrow direction.
[0012]
The plasma processing apparatus according to claim 5 of the present invention is characterized in that, in addition to the structure of any of claims 1 to 4, the electrodes 2 and 3 are formed in a square shape in plan view. It is.
[0013]
According to a sixth aspect of the present invention, in addition to the structure of any one of the first to fifth aspects, the grounded electrode 3 is connected to the blowout port of the other electrode 2 to which a high voltage is applied. It is characterized by being arranged close to 4.
[0014]
The plasma processing apparatus according to claim 7 of the present invention is characterized in that, in addition to the configuration of claim 1 or 2, electrodes 2 and 3 are formed long in a direction parallel to the longitudinal direction of the blowout port 4. To do.
[0015]
The plasma processing apparatus according to claim 8 of the present invention is characterized in that, in addition to the configuration of claim 1 or 2, the electrodes 2 and 3 are formed in a U shape whose bottom surface is opened in a side view. Is.
[0016]
According to a ninth aspect of the present invention, in addition to the structure of any one of the first to eighth aspects, a gas homogenizing chamber for homogenizing the flow of the plasma generating gas in the reaction vessel 1. 5 Set up Katesei The gas homogenization chamber 5 is formed such that the plasma generating gas supplied to the gas homogenization chamber 5 passes through the gas homogenization chamber 5 and is introduced into the reaction vessel 1. Ah It is characterized by that.
[0017]
The plasma processing apparatus according to claim 10 of the present invention is characterized in that, in addition to the structure of claim 9, a flange 50 protruding into the gas homogenization chamber 5 is formed in the reaction vessel 1. It is.
[0018]
The plasma processing apparatus according to claim 11 of the present invention is characterized in that, in addition to the structure of claim 9 or 10, the gas homogenization chamber 5 is filled with spheres 6.
[0019]
A plasma processing apparatus according to a twelfth aspect of the present invention includes a flat plane portion 7 and a cross-section Half The reaction vessel 1 is formed with an arcuate curved surface portion 8, and the blowout port 4 is formed in the flat surface portion 7.
[0020]
According to a thirteenth aspect of the present invention, in addition to the structure of the twelfth aspect, electrodes 2 and 3 are arranged on the curved surface portion 8.
[0021]
A plasma processing apparatus according to a fourteenth aspect of the present invention includes the electrodes 2, 3 in addition to the structure of the twelfth or thirteenth aspect. Half It is characterized by being formed in an arc shape.
[0022]
According to a fifteenth aspect of the present invention, in addition to the structure of any one of the twelfth to fourteenth aspects, the lower surface of the reaction vessel 1 is formed as a flat portion 7 and the plasma generating gas is supplied to the reaction vessel 1 It is characterized by being supplied from the side.
[0023]
The plasma processing apparatus according to claim 16 of the present invention comprises, in addition to the structure of claim 1, a reaction vessel 1 formed in a cylindrical shape and a pair of electrodes 2 and 3 arranged vertically opposite to each other. It is characterized by.
[0024]
A plasma processing apparatus according to claim 17 of the present invention is characterized in that, in addition to the structure of claim 16, electrodes 2 and 3 are formed in an annular shape in plan view.
[0025]
In addition to the configuration of claim 16 or 17, the plasma processing apparatus according to claim 18 of the present invention brings one electrode 3 to be grounded closer to the blowing port 4 than the other electrode 2 to which a high voltage is applied. It is characterized by being arranged.
[0030]
Claims of the invention 19 The plasma processing apparatus according to claim Any one of 1 to 18 In addition to the above structure, the blowout port 4 is formed along the inner surface of the reaction vessel 1 formed along the electric lines of force a.
[0031]
Claims of the invention 20 The plasma processing apparatus according to claim Any one of 1 to 18 In addition to the above structure, the outlet 4 is formed along each of the plurality of inner surfaces of the reaction vessel 1 formed along the electric lines of force a.
[0032]
Claim 2 of the present invention 1 The plasma processing apparatus according to claim 1 to claim 1. 20 In addition to any one of the structures, at least one of the electrodes 2 and 3 is cooled with a refrigerant.
[0033]
Claim 2 of the present invention 2 The plasma processing apparatus according to claim 1 or 2. 1 In addition to any of the above structures, a volume reducing tool 11 for reducing the volume of the discharge space 15 formed between the pair of electrodes 2 and 3 in the reaction vessel 1 is provided in the reaction vessel 1. It is characterized by.
[0034]
Claim 2 of the present invention 3 The plasma processing apparatus according to claim 2 2 In addition to the above structure, the volume reducing tool 11 is formed of an insulating material.
[0035]
Claim 2 of the present invention 4 The plasma processing apparatus according to claim 2 2 Or 2 3 In addition to the above structure, the volume reducing tool 11 is cooled with a refrigerant.
[0036]
Claim 2 of the present invention 5 The plasma processing apparatus according to claim 2 2 In addition to the above structure, the volume reducing tool 11 is formed of a metal material, and the volume reducing tool 11 is cooled with a refrigerant.
[0037]
Claims of the invention 26 The plasma processing apparatus according to claim 21 Thru 25 In addition to any one of the structures, the refrigerant is ion-exchanged water.
[0038]
A plasma processing apparatus according to claim 27 of the present invention comprises: 25 In addition to any of the above-described structures, the refrigerant is characterized by having antifreeze and insulating properties.
[0039]
Claims of the invention 28 The plasma processing apparatus according to claim 1 to claim 1. 27 In addition to any of the configurations, the frequency of the alternating electric field applied between the pair of electrodes 2 and 3 is set to 1 kHz to 200 MHz.
[0040]
Claims of the invention 29 The plasma processing apparatus according to claim 1 to claim 1. 28 In addition to any of the above structures, the surface roughness of the electrodes 2 and 3 on the side in contact with the reaction vessel 1 is formed to be 10 to 1000 μm.
[0041]
Claims of the invention 30 The plasma processing method according to claim 1 to claim 1. 29 The plasma processing apparatus according to any one of the above is characterized in that an object to be processed is arranged below the outlet 4 and plasma is blown out from the outlet 4 to be supplied to the object to be processed.
[0042]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described below.
[0043]
FIG. 1 shows an example of the plasma processing apparatus of the present invention. This plasma processing apparatus is formed by arranging a pair of electrodes 2 and 3 in contact with each other over the entire circumference of the reaction vessel 1 and arranging the electrodes 2 and 3 so as to face each other vertically. Inside the vessel 1, a discharge space 15 is formed between the electrode 2 and the electrode 3. Of the pair of electrodes 2, 3, one electrode 2 is connected to a power source 18 that generates a high frequency and is formed as a high voltage electrode to which a high voltage is applied, and the other electrode 3 is formed as a ground electrode that is grounded. Has been.
[0044]
The reaction vessel 1 is formed of an insulating material (dielectric material) having a high melting point. The dielectric constant of the insulating material constituting the reaction vessel 1 is an important factor for lowering the plasma temperature in the discharge space 15. Specifically, as the insulating material, a vitreous material such as quartz, alumina, or yttria partially stabilized zirconium is used. And ceramic materials.
[0045]
The reaction vessel 1 has a pair of side walls 1a facing each other in the thickness direction (the thickness direction of the reaction vessel 1 and the plasma processing apparatus is indicated by an arrow B), and the width direction of the reaction vessel 1 (of the reaction vessel 1 and the plasma processing apparatus). A pair of side walls 1b facing each other side by side in the width direction (indicated by an arrow A) and a rectangular bottom portion 1c constituting the lower surface of the reaction vessel 1 (rectangular in bottom view) are formed into a bottomed rectangular tube shape. Yes. The upper surface of the reaction vessel 1 is opened as a gas inlet 16 over substantially the entire surface, and the lower surface of the reaction vessel 1 which is the outer surface of the bottom portion 1c is formed as a substantially flat surface. As shown in FIG. 1 (b), a long and wide outlet 4 is formed in a direction parallel to the longitudinal direction (width direction) of the reaction vessel 1 at a substantially central portion in the thickness direction of the lower surface of the reaction vessel 1. Has been. The outlet 4 is slit-shaped and penetrates the bottom 1 c of the reaction vessel 1 and communicates with the discharge space 15 inside the reaction vessel 1.
[0046]
The reaction vessel 1 has a flat shape whose width is much larger than the thickness, and has an inner dimension W in the thickness direction (narrow direction) of the reaction vessel 1, that is, the thickness direction (narrow width) of the reaction vessel 1. The facing interval W between the inner surfaces of the pair of side walls 1a facing each other in the direction is preferably 0.1 to 5 mm. Thus, by setting the inner dimension W in the thickness direction of the reaction vessel 1 to 0.1 to 5 mm, the volume of the discharge space 15 becomes relatively small, and the power per unit space in the discharge space 15 can be increased. In other words, the discharge space density in the discharge space 15 can be increased, the power can be reduced and the gas flow rate can be reduced, and the plasma generation efficiency is increased to improve the plasma processing capability. It can be made to.
[0047]
If the inner dimension W of the reaction vessel 1 is less than 0.1 mm, the blowout port 4 becomes too small, the plasma blowout range becomes narrow, and there is a possibility that the range where plasma treatment can be performed becomes small. There exists a possibility that the intensity | strength of the container 1 may fall. On the other hand, when the inner dimension W of the reaction vessel 1 is larger than 5 mm, the blowout port 4 becomes too large, the flow rate of the jet-like plasma blown out from the blowout port 4 becomes small, and the plasma processing speed may be slowed down. In addition, the volume of the discharge space 15 becomes too large, and the input power (AC electric field) per unit volume in the discharge space 7 is reduced, so that the efficiency of plasma generation may be reduced, and the plasma processing speed may be reduced. . In order to solve these problems, the gas flow rate and electric power must be increased, but as a result, a large amount of gas and electric power may be consumed, and the cost performance may be reduced. Therefore, it is preferable to form the inner dimension W of the reaction vessel 1 to 0.1 to 5 mm.
[0048]
The electrode 2 and the electrode 3 have the same shape and are formed in a square shape (rectangular ring) in plan view. That is, the insertion hole 17 penetrating vertically is formed in the approximate center of the electrodes 2 and 3. The size of the insertion hole 17 is substantially the same as the outer peripheral dimension of the reaction vessel 1, and the shape of the insertion hole 17 in plan view is substantially the same as the outer peripheral shape of the reaction vessel 1. Further, the electrodes 2 and 3 are made of a metal material having high thermal conductivity, for example, copper, aluminum, brass, stainless steel having high corrosion resistance (SUS304, etc.), etc. in order to increase the cooling efficiency. It is also effective to plate the surfaces of the electrodes 2 and 3 with gold or the like having higher corrosion resistance and good high frequency propagation. Then, by forming the electrode 2 and the electrode 3 in a square shape in plan view, the electrode 2 and the electrode 3 can be arranged over the entire circumference of the reaction vessel 1, and the electrode 2, the electrode 3, and the reaction vessel 1 can be arranged. The contact area can be increased to improve the contact property, and plasma generation is facilitated.
[0049]
The inner peripheral surfaces of the electrodes 2 and 3 (surfaces constituting the insertion holes 17) are in contact with the outer periphery of the reaction vessel 1, and the surface roughness expressed by the arithmetic average roughness of the inner peripheral surfaces is 10 It is set to ˜1000 μm. Thus, by setting the surface roughness of the inner peripheral surfaces of the electrodes 2 and 3 to 10 to 1000 μm, the discharge in the discharge space 15 can be made uniform. The glow discharge is considered to be because, when viewed microscopically, a very fine aggregate of microdischarges is formed, and the transition to the arc is hindered. If the surface roughness of the inner peripheral surfaces of the electrodes 2 and 3 is less than 10 μm, it may be difficult to discharge, and if the surface roughness of the inner peripheral surfaces of the electrodes 2 and 3 exceeds 1000 μm, discharge may not occur. Uniformity may occur. As a process for roughening the inner peripheral surfaces of the electrode 2 and the electrode 3 in this way, physical means such as sandblasting can be employed. In addition, arithmetic mean roughness Ra (micrometer) at the time of expressing surface roughness in the form of y = f (x) is defined by the following formula | equation (1) by JISB0601.
[0050]
[Expression 1]

[0051]
Then, by inserting the reaction vessel 1 into the insertion hole 17, the electrode 2 and the electrode 3 are attached to the outer periphery of the reaction vessel 1, and the inner peripheral surface of the electrode 2 and the electrode 3 is set to the outer peripheral surface of the reaction vessel 1 (side wall 1a and side wall). The plasma processing apparatus as shown in FIG. 1 (a) is formed by connecting the power source 18 for generating an alternating electric field to the electrode 2 and grounding the electrode 3 while being in contact with the outer surface of 1b. Can do. Here, the grounded electrode 3 is disposed below the electrode 2 to which a high voltage is applied, that is, the electrode 3 is disposed closer to the outlet 4 than the electrode 2. By disposing the electrode 3 closer to the blowing port 4 than the electrode 2 in this way, the electrode 3 is positioned closer to the workpiece to be disposed below the blowing port 4 than the electrode 2. That is, the electrode 2 having a high voltage is positioned farther from the workpiece than the electrode 3, and it becomes difficult for the arc discharge to fly from the electrode 2 to the workpiece, and the workpiece is damaged by the arc discharge. Can be prevented.
[0052]
The distance between the electrode 2 and the electrode 3 (the distance between the lower end of the electrode 2 and the upper end of the electrode 3) is preferably set to 3 to 20 mm. If the distance between the electrode 2 and the electrode 3 is less than 3 mm, there is a possibility that a short circuit occurs between the electrode 2 and the electrode 3 outside the reaction vessel 1 and no discharge occurs in the discharge space 15. Narrowing may make it difficult to efficiently generate plasma. In addition, if the distance between the electrode 2 and the electrode 3 exceeds 20 mm, it is difficult for discharge to occur in the discharge space 15 and it may be difficult to efficiently generate plasma.
[0053]
In the plasma processing apparatus formed as described above, an inert gas (rare gas) or a mixed gas of an inert gas and a reactive gas is used as a plasma generating gas. As the inert gas, helium, argon, neon, krypton, or the like can be used, but it is preferable to use argon or helium in consideration of discharge stability and economy. Moreover, the kind of reaction gas can be arbitrarily selected according to the content of processing. For example, when cleaning organic substances existing on the surface of the object to be processed, stripping resist, etching organic films, etc., oxygen, air, CO ₂ , N ₂ It is preferable to use an oxidizing gas such as O. CF as a reaction gas _Four A fluorine-based gas such as can also be used as appropriate. When etching silicon or the like, it is effective to use this fluorine-based gas. Moreover, when reducing a metal oxide, reducing gas, such as hydrogen and ammonia, can be used. The amount of reaction gas added is 10% by weight or less, preferably 0.1 to 5% by weight, based on the total amount of the inert gas. If the addition amount of the reaction gas is less than 0.1% by weight, the treatment effect may be lowered, and if the addition amount of the reaction gas exceeds 10% by weight, the discharge may become unstable.
[0054]
When performing plasma processing using the plasma processing apparatus formed as described above, first, the arrow (1) As shown in FIG. 5, a plasma generating gas is introduced from the gas introduction port 16 into the reaction vessel 1 from the top to the bottom, and a high frequency voltage is applied to the electrode 2 from the power source 18 so that the electrodes 2 and 3 are connected. A high-frequency AC electric field is applied to the discharge space 15 therebetween. By applying this AC electric field, a glow-like discharge is generated in the discharge space 15 under atmospheric pressure, and the plasma-generating gas is turned into plasma by the glow-like discharge to generate plasma containing plasma active species, and then the arrow (2) As shown in the figure, a jet-like plasma having a curtain-like width is continuously flowed downward from the blowout port 4 so that the plasma is blown onto the surface of the workpiece disposed below the blowout port 4. To. In this way, the plasma treatment of the workpiece can be performed. Further, a flat substrate is an object to be processed, and in order to perform plasma processing on the entire surface of the substrate, the substrate or the plasma processing apparatus is moved in a direction perpendicular to the longitudinal direction of the blowing port 4 while blowing out plasma, The plasma is scanned and sprayed over the entire surface of the substrate. Further, by oscillating the plasma processing apparatus or the object to be processed in a direction perpendicular to the moving direction of the object to be processed, it is possible to repeatedly spray the plasma on the object to be processed, thereby improving the uniformity of the plasma processing. is there.
[0055]
In the present invention, the frequency of the applied AC electric field is preferably set to 1 kHz to 200 MHz. If the AC frequency is less than 1 kHz, the discharge in the discharge space 15 cannot be stabilized and the plasma treatment may not be performed efficiently. If the AC frequency exceeds 200 MHz, the temperature of the plasma in the discharge space 15 will increase significantly, and the life of the reaction vessel 1, electrode 2 and electrode 3 may be shortened, and the plasma processing apparatus becomes complicated. There is a risk of increasing the size. In the present invention, the applied power applied to the discharge space 15 is 20 to 3500 W / cm. ^Three It is preferable to set to. The applied power applied to the discharge space 15 is 20 W / cm. ^Three If it is less, plasma cannot be generated sufficiently, and conversely, the applied power applied to the discharge space 15 is 3500 W / cm. ^Three If it exceeds, stable discharge may not be obtained. The applied power density (W / cm ^Three ) Is defined by (applied power / discharge space volume).
[0056]
In this embodiment, the electrodes 2 and 3 are disposed without facing the reaction vessel 1 so that the electric lines of force a along the inner surfaces of the side walls 1a and 1b of the reaction vessel 1 are formed. The electric lines of force are less likely to occur in the vertical direction of the inner surface of the reaction vessel 1, and the deterioration of the reaction vessel 1 due to the electric lines of force a can be reduced, and the constituent materials from the inner surfaces of the side walls 1a and 1b of the reaction vessel 1 can be reduced. Is less likely to pop out and the object to be treated is less contaminated with impurities. That is, in the present invention, as shown in FIG. 2A, the electrode 2 and the electrode 3 are provided on the outer surface side of the side wall 1a and the side wall 1b of the reaction vessel 1 and face each other in the direction along the side walls 1a and 1b. The electric lines of force a along the inner surfaces of the side wall 1a and the side wall 1b of the reaction vessel 1 are formed between the electrode 2 and the electrode 3 as shown in FIG. When the electrode 2 and the electrode 3 are provided on the outer surface side of the side wall 1a and the side wall 1b of the reaction vessel 1 and arranged so as to face each other in the direction orthogonal to the side walls 1a and 1b, the side wall of the reaction vessel 1 is interposed between the electrode 2 and the electrode 3 Electric lines of force a are formed in the orthogonal direction between 1a and the inner surface of the side wall 1b. In the present invention, as shown in FIG. 2A, at least a part of the electric lines of force a are formed on the inner surface of the reaction vessel 1 in the direction in which the electrodes 2 and 3 face each other (the direction in which the electrodes 2 and 3 are arranged). As shown in FIG. 2 (b), the reaction vessel 1 is deteriorated as compared with the case where all the lines of electric force a are formed in the vertical direction between the side walls 1a and 1b of the reaction vessel 1 as shown in FIG. As a result, the constituent material is less likely to jump out from the inner surfaces of the side wall 1a and the side wall 1b of the reaction vessel 1, and the object to be processed can be reduced from being contaminated by impurities.
[0057]
Further, in the above embodiment, since the blowout port 4 for blowing out the jet-shaped plasma having a width is formed on the lower surface of the reaction vessel 1, the plasma having a width like a curtain is blown out from the blowout port 4. However, by moving the substrate or the plasma processing apparatus in the direction orthogonal to the longitudinal direction of the blowout port 4 and scanning and spraying the plasma over the entire surface of the substrate, the object to be processed is wider than that for blowing out spot plasma. The area can be plasma processed at a time, and the processing time can be shortened when the entire surface of a substrate such as a BGA substrate is processed.
[0058]
Furthermore, in the above embodiment, since both the electrode 2 and the electrode 3 for applying an alternating electric field to the discharge space 15 are provided outside the reaction vessel 1, both the electrode 2 and the electrode 3 are directly exposed to the plasma. Therefore, both the electrode 2 and the electrode 3 can be prevented from being corroded by the reaction gas, and the electrode 2 and the electrode 3 are damaged by the plasma. It can be used for longer life. In addition, since impurities are not generated by sputtering or corrosion, the object to be processed can be prevented from being contaminated by impurities even after long-term use.
[0059]
In the above embodiment, the electrodes 2 and 3 are arranged so as to face each other in the direction of introducing the plasma generating gas, that is, the electrodes 2 and 3 are arranged side by side so as to face each other. The direction of the alternating electric field generated in the direction 15 (the direction of the electric force line a) and the flow direction of the plasma generating gas and plasma can be substantially matched, and the active species of plasma can be generated efficiently. In addition, by changing the distance between the electrode 2 and the electrode 3, the size of the discharge space 15 can be easily changed, and the amount of plasma generated can be easily adjusted.
[0060]
3A and 3B show another embodiment. In this plasma processing apparatus, the outlet 4 is formed on the lower surface of the reaction vessel 1 along the inner surface of the side wall 1a on one side of the reaction vessel 1 formed along the electric lines of force a. Is formed in the same manner as in FIG. That is, in the plasma processing apparatus of FIG. 1, the outlet 4 is formed long along the center line D that bisects the lower surface of the reaction vessel 1 in the thickness direction of the reaction vessel 1. (B) In the plasma processing apparatus of (b), the outlet 4 is provided at the end of the lower surface of the reaction vessel 1 at the position closer to the side wall 1a than the position of the center line D and in the vicinity of the side wall 1a. It is formed long along. Further, in this plasma processing apparatus, the blowout port 4 is formed only in the vicinity of the side wall 1a on one side of the pair of side walls 1a, 1a facing each other across the center line D.
[0061]
As described above, in the plasma processing apparatus of FIG. 1, the electrodes 2 and 3 come into contact with the outer surfaces of the side walls 1 a and 1 b of the reaction vessel 1, so that electricity along the inner surfaces of the side walls 1 a and 1 b of the reaction vessel 1 is obtained. Although a lot of force lines a are formed, the plasma P is more on the inner surfaces of the side walls 1a and 1b of the reaction vessel 1 than the central portion of the reaction vessel 1 as shown in FIGS. 3 (b) and 3 (c). The concentration tends to increase in the vicinity and increase in concentration. Therefore, as shown in FIG. 1 and FIG. 3 (c), rather than forming the outlet 4 at the substantially central portion in the thickness direction of the reaction vessel 1 on the lower surface of the reaction vessel 1, FIG. As shown, plasma P can be blown out more efficiently by forming the blowout port 4 along the side wall 1a in the vicinity of the side wall 1a of the reaction vessel 1 on the lower surface of the reaction vessel 1, thereby improving the plasma processing capability. It is something that can be done.
[0062]
FIG. 4 shows another embodiment. In this plasma processing apparatus, the outlet 4 is formed on the lower surface of the reaction vessel 1 along the inner surfaces of the side walls 1a on both sides of the reaction vessel 1 formed along the electric lines of force a. Is formed in the same manner as in FIG. That is, in the plasma processing apparatus of FIG. 1, the blowout port 4 is formed long along the center line D that bisects the lower surface of the reaction vessel 1 in the thickness direction of the reaction vessel 1. (B) In the plasma processing apparatus of (b), the outlet 4 is provided at the end of the lower surface of the reaction vessel 1 at the position closer to the side wall 1a than the position of the center line D and in the vicinity of the side wall 1a. It is formed long along. Further, in this plasma processing apparatus, blowout ports 4 are formed in the vicinity of the side walls 1a on both sides of the pair of side walls 1a and 1a facing each other across the center line D.
[0063]
As described above, in the plasma processing apparatus of FIG. 1, many electric lines of force a are formed along the inner surfaces of the side wall 1a and the side wall 1b of the reaction vessel 1, and as a result, as shown in FIG. P is more concentrated in the vicinity of the inner surfaces of the side wall 1a and the side wall 1b of the reaction vessel 1 than in the central portion of the reaction vessel 1, and the concentration tends to increase. Therefore, as shown in FIG. 1 and FIG. 3 (c), rather than forming the outlet 4 at the substantially central portion in the thickness direction of the reaction vessel 1 on the lower surface of the reaction vessel 1, FIG. As shown, plasma P can be blown out more efficiently by forming the blowout port 4 along the side wall 1a in the vicinity of the side wall 1a of the reaction vessel 1 on the lower surface of the reaction vessel 1, thereby improving the plasma processing capability. It is something that can be done. Moreover, the plasma P is doubled (twice) on the workpiece 60 by carrying the plasma treatment by conveying the workpiece 60 in the direction perpendicular to the longitudinal direction of the blowout port 4 below the blowout port 4. The irradiation time of the plasma P in one transfer of the workpiece 60 is doubled as compared with those in FIGS. 3 (a) and 3 (b), and the plasma processing capability is improved. It is something that can be done. In this embodiment, since the opening area of the blowing port 4 is increased as compared with those of FIGS. 1 and 3A and 3B, the flow rate of the plasma P is increased by increasing the flow rate of the plasma generating gas. It is preferable not to reduce the flow rate.
[0064]
5 and 6 show another embodiment. In this embodiment, the electrodes 2 and 3 are cooled in the plasma processing apparatus of FIG. That is, the inside of the electrode 2 and the electrode 3 is formed as a circulation part 26 through which a refrigerant can flow, and the supply pipe 21 and the discharge pipe 22 communicating with the circulation part 26 protrude from the outer peripheral surface of the electrode 2 and the electrode 3. The arrow is set (3) As shown in FIG. 2, the coolant is supplied to the flow passage 26 inside the electrode 2 and the electrode 3 through the supply pipe 21 to cool the electrode 2 and the electrode 3 while generating plasma. The refrigerant supplied to the circulation unit 26 is an arrow. (4) As shown by, the gas is discharged from the electrode 2 and the electrode 3 through the discharge pipe 22.
[0065]
As the refrigerant, ion exchange water or pure water can be used. By using ion exchange water or pure water, impurities are not contained in the refrigerant, and the electrodes 2 and 3 are less likely to be corroded by the refrigerant. The refrigerant is preferably a liquid having antifreezing properties at 0 ° C. and having electrical insulation properties, nonflammability, and chemical stability. For example, the electrical insulation performance has a withstand voltage at intervals of 0.1 mm. It is preferable that it is 10 kV or more. The reason why the refrigerant having the insulating property in this range is used is to prevent leakage from the high voltage electrode to which a high voltage is applied. Examples of the refrigerant having such properties include perfluorocarbon, hydrofluoroether, and the like, and may be a mixed liquid obtained by adding 5 to 60% by weight of ethylene glycol to pure water.
[0066]
And in this embodiment, since the electrode 2 and the electrode 3 are cooled by the refrigerant, even if plasma is generated with an alternating current having a high frequency under atmospheric pressure, the temperature rise of the electrode 2 and the electrode 3 can be suppressed, Therefore, the temperature of the plasma (gas temperature) can be prevented from becoming high, and thermal damage to the object to be processed can be reduced. Further, by cooling the electrode 2 and the electrode 3, local heating of the discharge space 15 can be prevented, generation of a homogeneous glow discharge can be suppressed, and generation of streamer discharge can be suppressed. Damage due to streamer discharge can be reduced. This is considered to be because partial emission of electrons from the electrodes 2 and 3 can be suppressed by cooling the electrodes 2 and 3. In this embodiment, both the electrode 2 and the electrode 3 are cooled, but only one of the electrode 2 and the electrode 3 may be cooled.
[0067]
Also in this embodiment, as shown in FIGS. 3 (a) and 3 (b), the blowout port 4 extends along the inner surface of one side wall 1a of the reaction vessel 1 formed along the electric lines of force a. Is formed on the lower surface of the reaction vessel 1 or is blown out along the inner surfaces of the side walls 1a on both sides of the reaction vessel 1 formed along the lines of electric force a as shown in FIGS. 4 (a) and 4 (b). The mouth 4 can be formed on the lower surface of the reaction vessel 1.
[0068]
FIG. 7 shows another embodiment. In this embodiment, the volume reducing tool 11 for reducing the volume of the discharge space 15 is provided in the plasma processing apparatus of FIGS. As shown in FIGS. 8 (a) and 8 (b), the volume reducing tool 11 is formed in a box shape that is smaller than the reaction vessel 1 and substantially equal to the internal shape of the reaction vessel 1. The flow pipe 23 is arranged so as to meander in the vertical direction. In addition, one end of the flow pipe 23 is formed as an introduction part 24 and the other end is formed as a lead-out part 25, and the lead-in part 24 and the lead-out part 25 are arranged so as to protrude from the upper surface of the volume reducing tool 11. The volume reducing tool 11 is cooled by circulating the same refrigerant as above through the flow pipe 23. That is, the arrow (5) As shown, the volume reducing device 11 is cooled by supplying and circulating a refrigerant through the introduction part 24 into the flow pipe 23. The refrigerant supplied to the flow pipe 23 is an arrow. (6) As shown in FIG.
[0069]
The volume reducing tool 11 is inserted and arranged from the gas inlet 16 into the reaction vessel 1 so that the lower part thereof is located in the discharge space 15. Therefore, the volume of the discharge space 15 in this embodiment is smaller than that of the discharge space 15 of the plasma processing apparatus of FIGS. And by providing the volume reducing tool 11 for reducing the volume in the discharge space 15 in this way, the input power (alternating electric field) per unit volume in the discharge space 15 can be increased, and the generation of plasma can be increased. Efficiency can be improved. Further, by cooling the volume reducing tool 11 with the refrigerant while the plasma is generated, deterioration of the volume reducing tool 11 due to heat can be reduced, and the life of the volume reducing tool 11 can be extended. In addition, the temperature of the plasma generated in the discharge space 15 around the volume reducing tool 11 can be lowered, and damage to the object to be processed due to heat can be reduced.
[0070]
Furthermore, the volume reducing tool 11 is arranged so as to penetrate the center of the reaction vessel 1 up and down. That is, the reaction vessel 1 and the volume reducing tool 11 are substantially aligned so that the long center line in the longitudinal direction (vertical direction) of the reaction container 1 and the long center line of the volume reducing tool 11 substantially coincide with each other. It is arranged coaxially (concentrically). Thus, by arranging the reaction vessel 1 and the volume reducing tool 11 almost coaxially, the volume of the discharge space 15 formed between the inner peripheral surface of the reaction vessel 1 and the outer peripheral surface of the volume reducing tool 11 is made uniform. The density of the alternating electric field in the discharge space 15 can be made uniform, and plasma can be generated efficiently, and the generated plasma is homogenized to perform high-quality plasma processing. It is something that can be done.
[0071]
The volume reducing tool 11 is preferably formed of an insulating material having a high melting point similar to that of the reaction vessel 1, which can prevent impurities from being generated from the volume reducing tool 11 by sputtering or corrosion, and can be used for a long time. Even so, the object to be processed can be prevented from being contaminated by impurities. Moreover, although the volume reducing tool 11 can also be formed with metal materials, such as stainless steel, in this case, it is preferable to coat the surface of the volume reducing tool 11 with an insulating material with a protective film. Examples of the insulating material used for the protective film include glassy materials such as quartz, alumina, and yttria partially stabilized zirconium, and ceramic materials. Furthermore, alumina (Al ₂ O _Three ), Titanium oxide (TiO2 in titania) ₂ ), SiO ₂ , AlN, Si _Three Examples of the dielectric material include N, SiC, DLC (diamond-like carbon coating), barium titanate, and PZT (lead zirconate titanate). An insulating material containing magnesia (MgO) alone or magnesia can also be used.
[0072]
In forming the protective film, a method of forming a rectangular tube (ceramic tube or glass tube) with an insulating material and inserting and attaching the volume reducing tool 11 inside thereof, and alumina and barium titanate. In addition, a powder such as titanium oxide or PZT is dispersed in a plasma and sprayed onto the surface of the volume reducing tool 11 and an inorganic powder such as silica, tin oxide, titania, zirconia, or alumina is dispersed in a solvent. In addition, a so-called soot coating method in which the surface of the volume reducing tool 11 is sprayed onto the surface of the volume reducing tool 11 and then melted at a temperature of 600 ° C. or more, and a glassy film forming method by a sol-gel method can be employed. Further, the surface of the volume reducing device 11 can be coated with a protective film by vapor deposition (CVD) or physical vapor deposition (PVD), and by adopting these methods, extremely dense and smooth adsorption is poor. The surface of the volume reducing tool 11 can be coated with a protective film, and stabilization of discharge can be further promoted. In consideration of realistic processing time and cost, it is preferable to use the above thermal spraying method.
[0073]
The thickness of the protective film is preferably set to 10 to 500 μm. If the thickness of the protective film is less than 10 μm, the effect of preventing the deterioration of the volume reducing tool 11 is small, and it may be difficult to extend the life of the volume reducing tool 11, and even if the thickness of the protective film exceeds 500 μm, the volume is reduced. The effect of preventing the reduction of the reducing tool 11 is not greatly improved, and the consumption of the insulating material used for the protective film is unnecessarily increased, which may be economically disadvantageous.
[0074]
Moreover, it is preferable to interpose an undercoat formed of an alloy film containing nickel, chromium, aluminum, and yttrium between the surface of the volume reducing tool 11 and the protective film. The undercoat can be formed by thermal spraying of an alloy. Specific examples of the alloy include Ni—Cr, Ni—Al, and Ni—Cr—Al—Y. The volume reducing tool 11 is placed in a thermal stress load environment caused by repetition of plasma at room temperature and high temperature, and the protective film may be peeled off by this thermal stress. Therefore, an undercoat is provided to alleviate the impact of thermal stress load on the protective film. The relationship between the thermal expansion coefficient of the metal volume reducing tool 11, the alloy undercoat and the insulating material protective film is metal expansion coefficient> alloy expansion coefficient> insulating material expansion coefficient. The expansion and contraction due to heat becomes difficult to be transmitted to the protective film due to the interposition of the undercoat, which makes it difficult for the protective film to be peeled off and to extend the life of the volume reducing tool 11.
[0075]
The protective film is preferably subjected to a sealing treatment. The sealing process is a process for filling the defective part of the protective film, ₂ TiO ₂ , Al ₂ O _Three It is immersed in a solution containing a dielectric such as By performing this sealing treatment, it is possible to make it difficult for arc discharge to occur between the electrode 2 and the metal volume reducing tool 11, and to prevent the volume reducing tool 11 from being deteriorated by heating of the plasma, thereby reducing the volume reducing tool 11. It is possible to prolong the service life.
[0076]
The volume reduction tool 11 can be selectively used depending on the type of the object to be processed. For example, when the object to be processed may be exposed to a high temperature such as a metal material (deterioration or the like does not occur), the volume formed of the insulating material without the circulation pipe 23 that is a cooling mechanism or the refrigerant. The reduction tool 11 is used. In this case, since the volume reducing tool 11 is not cooled, the plasma gas temperature becomes high as shown by the curve a in FIG. 9, and the plasma processing speed can be increased as in the cleaning performance shown by the curve b in FIG. The plasma treatment (cleaning) can be performed in a short time. On the other hand, when a plasma processing is performed on an object having a relatively low heat-resistant temperature, such as a circuit board, a metal material having a circulation pipe 23 or a refrigerant that is a cooling mechanism and having a higher thermal conductivity than an insulating material. The volume reducing tool 11 to be formed is used. In this case, since the volume reducing tool 11 is cooled, the plasma gas temperature is lowered as shown by the curve (a) in FIG. 9, and the plasma processing speed is somewhat reduced as in the cleaning performance shown by the curve (b) in FIG. However, plasma processing (cleaning) can be performed without causing thermal damage to the object to be processed.
[0077]
Also in this embodiment, as shown in FIGS. 3 (a) and 3 (b), the blowout port 4 extends along the inner surface of one side wall 1a of the reaction vessel 1 formed along the electric lines of force a. Is formed on the lower surface of the reaction vessel 1, or as shown in FIG. 4, the outlet 4 is formed along the inner surfaces of the side walls 1 a on both sides of the reaction vessel 1 formed along the electric lines of force a. Or can be formed on the lower surface of the substrate.
[0078]
In FIG. Reference form Indicates. this Reference form In the plasma processing apparatus of FIG. 2, a gas homogenization chamber 5 is integrally formed on the upper part of the reaction vessel 1. The Yes. The gas homogenization chamber 5 is formed in a box shape thicker than the reaction vessel 1, and the upper surface of the gas homogenization chamber 5 is opened over the entire surface as a gas supply port 30 and the gas homogenization chamber 5. A gas inlet 16 of the reaction vessel 1 is opened on the lower surface of the reactor. The gas homogenization chamber 5 is filled with a large number of spheres 6 formed of silica balls or the like.
[0079]
this Reference form Then, the plasma generation gas is supplied to the reaction vessel 1 through the gas homogenization chamber 5. That is, the gas for generating plasma is introduced into the gas homogenization chamber 5 from the gas supply port 30, and the gas for generating plasma is moved downstream to the gas inlet 16 so as to pass through the gaps between the spheres 6. A plasma generating gas is introduced into the reaction vessel 1 from the gas inlet 16. Since the plasma generating gas is supplied to the reaction vessel 1 through the gas homogenizing chamber 5 in this way, the entire inside of the reaction vessel 1 is prevented so that the plasma generating gas is not biased to a part of the reaction vessel 1. Can be supplied at a uniform concentration, can generate homogeneous plasma efficiently, and can reduce processing unevenness.
[0080]
The diameter of the sphere 6 is preferably set to 3 to 7 mm, and the filling amount of the sphere 6 is set so that the proportion of the sphere 6 is 50 to 80% of the volume of the gas homogenization chamber 5. Is preferred. If the diameter of the sphere 6 is less than 3 mm or the filling amount of the sphere 6 exceeds 80%, the gap between the spheres 6 may become too small to introduce the plasma generating gas into the reaction vessel 1. There is. If the diameter of the sphere 6 exceeds 7 mm or the filling amount of the sphere 6 is less than 50%, the gap between the spheres 6 becomes too large, and the plasma generating gas is uniformly introduced into the reaction vessel 1. There is a risk that it will not be possible.
[0081]
In addition, this Reference form 3 (a) and 3 (b), the outlet 4 is formed along the inner surface of the side wall 1a on one side of the reaction vessel 1 formed along the electric lines of force a. As shown in FIG. 4, the outlet 4 is formed on the lower surface of the reaction vessel 1 along the inner surfaces of the side walls 1a on both sides of the reaction vessel 1 formed along the electric lines of force a. can do. Moreover, the gas homogenization chamber 5 for uniformly introducing the plasma generating gas as described above into the reaction vessel 1 can be formed in any embodiment of the present invention.
[0082]
The other in FIG. Reference form Indicates. this Reference form In the plasma processing apparatus of FIG. 1, the gas homogenization chamber 5 is integrally formed on the upper portion of the reaction vessel 1. Other configurations are the same as those in FIG. As shown in FIGS. 12A, 12B, and 12C, the gas homogenization chamber 5 is formed in a box shape thicker than the reaction vessel 1, and gas is supplied to the upper surface of the gas homogenization chamber 5. A gas pipe portion 61 provided with a port 30 is protruded, and a lower portion of the gas homogenization chamber 5 is formed as a throttle portion 62 whose thickness decreases toward the lower side. The lower end of the part 62 is joined to the outer surfaces of the side walls 1 a and 1 b of the reaction vessel 1. As shown in FIG. 13, a cylindrical flange 50 protruding into the gas homogenization chamber 5 is formed integrally with the reaction container 1 at the junction between the reaction vessel 1 and the throttle portion 62. Is opened as a gas inlet 16 of the reaction vessel 1.
[0083]
this Reference form Then, the plasma generation gas is supplied to the reaction vessel 1 through the gas homogenization chamber 5. That is, a plasma generating gas is introduced from the gas supply port 30 into the gas homogenization chamber 5, the plasma generating gas is brought downstream to the gas introducing port 16, and then the plasma is generated from the gas introducing port 16 into the reaction vessel 1. Gas for use is introduced. Then, the plasma generation gas is supplied to the reaction vessel 1 through the gas homogenization chamber 5 in this way, so that the plasma generation gas is not stirred in the reaction vessel 1 and is not biased to a part in the reaction vessel 1. It is easy to diffuse into the reaction vessel 1 and can be supplied at a uniform concentration throughout the reaction vessel 1, can generate homogeneous plasma efficiently, and can reduce processing unevenness. is there. The gas homogenization chamber 5 may be filled with the same sphere 6 as described above, but may not be filled.
[0084]
FIG. 14 shows another embodiment. In this plasma processing apparatus, the reaction container 1 is arranged in the thickness direction (the thickness direction of the reaction container 1 and the plasma processing apparatus is indicated by an arrow B), and a pair of side walls 1a facing each other, and the width direction of the reaction container 1 (reaction container 1 And a pair of side walls 1b facing each other side by side in the width direction of the plasma processing apparatus (indicated by an arrow A), a rectangular shape (rectangular in bottom view) constituting the lower surface of the reaction vessel 1, and a rectangular tube shape with an upper surface 1d Is formed. In addition, a gas inlet (not shown) is formed in a substantially central portion of the upper surface 1d of the reaction vessel 1, and a rectangular lower surface (rectangular in bottom view) of the reaction vessel 1 is formed as a substantially flat surface. Yes. And as shown in FIG.14 (b), the long and wide blower outlet 4 is formed in the direction parallel to the longitudinal direction (width direction) in the approximate center part of the thickness direction of the lower surface of the reaction container 1. As shown in FIG. . The outlet 4 is slit-shaped and penetrates the bottom 1 c of the reaction vessel 1 and communicates with the discharge space 15 inside the reaction vessel 1.
[0085]
An electrode 2 and an electrode 3 are provided on the outer surface of the reaction vessel 1. That is, the electrode 2 and the electrode 3 are provided in contact with the outer surface of a pair of side surfaces 1 b facing the upper surface of the reaction vessel 1 side by side in the width direction of the reaction vessel 1 and the electrode 2 and the electrode 3 are arranged in the thickness direction of the reaction vessel 1. The discharge space 15 is formed between the electrode 2 and the electrode 3 inside the reaction vessel 1. The reaction vessel 1 is formed of the same material as described above.
[0086]
The electrode 2 and the electrode 3 have the same shape, and are formed in a U shape whose bottom surface is opened in a side view. That is, the electrode 2 and the electrode 3 are composed of an upper piece 31 and a pair of side pieces 32 that protrude downward from the end of the upper piece 31 and are surrounded by the upper piece 31 and the side piece 32. Is formed as the insertion recess 33. The dimension in the width direction of the insertion recess 33 is substantially the same as the outer dimension in the width direction of the reaction vessel 1, and the dimension in the height direction of the insertion recess 33 is substantially the same as the outer dimension in the height direction of the reaction vessel 1. They are formed identically (the height direction of the reaction vessel 1 and the plasma processing apparatus is indicated by an arrow C). Furthermore, the electrode 2 and the electrode 3 are formed of the same material as described above. In addition, the inner surfaces of the electrodes 2 and 3 (surfaces constituting the insertion recesses 33) are in contact with the outer periphery of the reaction vessel 1, and the surface roughness expressed by the arithmetic average roughness of the inner surfaces is 10 to 10. It is set to 1000 μm.
[0087]
Then, by inserting the reaction container 1 into the insertion recess 33 from below, the electrodes 2 and 3 are attached to the outer surface of the reaction container 1, the upper piece 31 is brought into contact with the upper surface of the reaction container 1, and the outlet 4 A plasma as shown in FIG. 14A is obtained by bringing the side piece 32 into contact with the side surface of the reaction vessel 1 facing in the longitudinal direction, and connecting the power source 18 for generating an alternating electric field to the electrode 2 and grounding the electrode 3. A processing device can be formed. The distance between the electrode 2 and the electrode 3 (the distance between the electrode 2 and the electrode 3 in the thickness direction of the reaction vessel 1) is preferably set to 3 to 20 mm. The plasma processing apparatus thus formed can perform plasma processing in the same manner as the embodiment shown in FIG. 1 and has the same effect as the embodiment shown in FIG. .
[0088]
Furthermore, in this embodiment, the electrode 2 and the electrode 3 are formed so that the dimension in the width direction is longer than the dimension in the thickness direction. That is, in plan view, the electrode 2 and the electrode 3 are formed longer in the direction parallel to the longitudinal direction of the outlet 4, and the width dimension of the electrode 2 and the electrode 3 is larger than the dimension in the width direction of the outlet 4. Is formed longer. The electrode 2 and the electrode 3 are arranged side by side in a direction (thickness direction) orthogonal to the longitudinal direction of the blowout port 4, and the electrode 2 and the electrode 3 are arranged on both sides of the gas introduction port and the blowout port 4 in the thickness direction. It is arranged side by side so as to be sandwiched between. That is, the gas inlet and the outlet 4 are formed between the electrode 2 and the electrode 3 in plan view. Therefore, the discharge space 15 between the electrode 2 and the electrode 3 is formed on the upper side of the outlet 4 in the reaction vessel 1 in parallel with the longitudinal direction of the outlet 4, and moreover, from the dimension in the width direction of the outlet 4. Will also be formed longer. Accordingly, a wide discharge space 15 is formed on the upper side (upstream side) of the blowout port 4, and the plasma generating gas can be efficiently converted into a plasma, and a high-density plasma can be formed. In addition, a uniform plasma can be blown out over the entire length of the blowout port 4. Therefore, high density and homogeneous plasma is sprayed on the object to be processed, so that the performance of the plasma processing can be improved and the plasma processing can be performed in a short time.
[0089]
In this embodiment, the lower surface of the reaction vessel 1 and the tip surfaces (lower surfaces) of the side pieces 32 of the electrodes 2 and 3 are formed into flat surfaces, and the tips of the side pieces 32 of the electrodes 2 and 3 are reacted. Since the lower surface of the reaction vessel 1 and the tip surfaces of the side pieces 32 of the electrodes 2 and 3 are formed so as not to protrude from the lower surface of the vessel 1, the object to be processed can be brought close to the vicinity of the outlet 4. It becomes possible, and it can be sprayed on the object to be processed before the active plasma active species contained in the plasma blown out into the atmosphere from the outlet 4 is extinguished, and the active species in the plasma are efficiently used. Thus, the plasma treatment of the workpiece can be enhanced. In addition, although the distance between the blower outlet 4 and a to-be-processed object changes with application conditions, the kind of to-be-processed object, etc., it can set to 2-10 mm.
[0090]
FIG. 15A shows another embodiment. In this plasma processing apparatus, the outlet 4 is formed on the lower surface of the reaction vessel 1 along the inner surface of the side wall 1b on one side of the reaction vessel 1 formed along the electric lines of force a. Is formed in the same manner as in FIG. That is, in the plasma processing apparatus of FIGS. 14 and 15B and 15C, the outlet 4 is formed long along the center line D that substantially bisects the lower surface of the reaction vessel 1 in the thickness direction of the reaction vessel 1. However, in the plasma processing apparatus of FIG. 15A, in the vicinity of the side wall 1b where the electrode 2 and the electrode 3 are in contact with the outer surface, the outlet 4 is provided at the end of the lower surface of the reaction vessel 1 along the inner surface of the side wall 1b. Thus, it is formed long in a direction substantially parallel to the width direction of the reaction vessel 1. Further, in this plasma processing apparatus, only in the vicinity of one side wall 1b of the pair of side walls 1b, 1b facing each other across the center line E that bisects the lower surface of the reaction container 1 in the width direction of the reaction container 1. A blow-out port 4 is formed on the surface.
[0091]
As described above, in the plasma processing apparatus of FIG. 14, when the electrode 2 and the electrode 3 are in contact with the outer surface of the side wall 1 b of the reaction vessel 1, many electric lines of force a are formed along the inner surface of the side wall 1 b of the reaction vessel 1. However, as a result, as shown in FIGS. 15B and 15C, the plasma P is generated more concentrated in the vicinity of the inner surface of the side wall 1b of the reaction vessel 1 than in the central portion of the reaction vessel 1. Tend to be higher. Accordingly, as shown in FIG. 14 and FIGS. 15B and 15C, rather than forming the outlet 4 at the substantially central portion in the thickness direction of the reaction vessel 1 on the lower surface of the reaction vessel 1, FIG. As shown, the plasma P can be blown out more efficiently by forming the blowing port 4 along the side wall 1b in the vicinity of the side wall 1b of the reaction vessel 1 on the lower surface of the reaction vessel 1, thereby improving the plasma processing capability. It is something that can be done.
[0092]
FIG. 16 shows another embodiment. In this plasma processing apparatus, the outlet 4 is formed on the lower surface of the reaction vessel 1 along the inner surfaces of the side walls 1b on both sides of the reaction vessel 1 formed along the electric lines of force a. Is formed in the same manner as in FIG. That is, in the plasma processing apparatus of FIG. 14, the outlet 4 is formed long along the center line D that bisects the lower surface of the reaction container 1 in the thickness direction of the reaction container 1, but the plasma of FIG. In the processing apparatus, in the vicinity of the side wall 1b where the electrode 2 and the electrode 3 are in contact with the outer surface, a blowing port 4 is provided at the end of the lower surface of the reaction vessel 1 along the inner surface of the side wall 1b and in a direction substantially parallel to the width direction of the reaction vessel 1. It was formed long. Further, in this plasma processing apparatus, the outlet 4 is provided in the vicinity of the side walls 1b on both sides of the pair of side walls 1b and 1b facing each other across the center line E that bisects the lower surface of the reaction container 1 in the width direction of the reaction container 1. Is formed.
[0093]
As described above, in the plasma processing apparatus of FIG. 14, many electric lines of force a are formed along the inner surface of the side wall 1b of the reaction vessel 1, and as a result, as shown in FIGS. P is more concentrated in the vicinity of the inner surface of the side wall 1b of the reaction vessel 1 than in the central portion of the reaction vessel 1, and the concentration tends to increase.
[0094]
Accordingly, as shown in FIG. 16 and FIG. 15B and FIG. 15C, as shown in FIG. 16, rather than forming the outlet 4 at the substantially central portion in the thickness direction of the reaction vessel 1 on the lower surface of the reaction vessel 1. In the lower surface of the reaction vessel 1, the plasma P can be blown out more efficiently by forming the blowing port 4 along the side wall 1 b in the vicinity of the side wall 1 b of the reaction vessel 1, and the plasma processing capability can be improved. Is. In addition, similarly to FIG. 4A, the plasma P is processed by conveying the object to be processed in a direction perpendicular to the longitudinal direction of the outlet 4 below the outlet 4 to perform the plasma processing. Can be sprayed twice (twice), and the irradiation time of plasma P in one transfer of the object to be processed is doubled as compared with that in FIG. It can be improved. In this embodiment, since the opening area of the blowing port 4 is increased as compared with those in FIGS. 14 and 15A, the flow rate of the plasma P blowing is decreased by increasing the flow rate of the plasma generating gas. It is preferable not to do so.
[0095]
17 and 18 show another embodiment. In this embodiment, the electrodes 2 and 3 are cooled in the plasma processing apparatus of FIG. That is, the inside of the electrode 2 and the electrode 3 is formed as a flow part 26 through which a refrigerant can flow, and in each of the electrode 2 and the electrode 3, a supply pipe that communicates with the flow part 26 on the outer surface of one side piece 32. 21 and the discharge pipe 22 which each communicates with the circulation part 26 project from the outer surface of the other side piece 32. And arrow (3) As shown in FIG. 2, the coolant is supplied to the flow passage 26 inside the electrode 2 and the electrode 3 through the supply pipe 21 to cool the electrode 2 and the electrode 3 while generating plasma. The refrigerant supplied to the circulation unit 26 is an arrow. (4) As shown by, the gas is discharged from the electrode 2 and the electrode 3 through the discharge pipe 22. The same refrigerant as described above can be used. Since this embodiment cools the electrode 2 and the electrode 3, the same effect as the embodiment shown in FIGS.
[0096]
Also in this embodiment, as shown in FIG. 15 (a), the outlet 4 is set along the inner surface of the side wall 1b on one side of the reaction vessel 1 formed along the electric lines of force a. 16 or on the lower surface of the reaction vessel 1 along the inner surfaces of the side walls 1b on both sides of the reaction vessel 1 formed along the electric lines of force a as shown in FIG. Or can be formed.
[0097]
FIG. 19 shows another embodiment. This plasma processing apparatus includes a flat flat surface portion 7 and a curved surface portion 8 having a substantially semicircular arc-shaped cross section that protrudes upward to form a semicircular reaction vessel 1, and a reaction that is the outer surface of the flat surface portion 7. Formed by forming the outlet 4 on the lower surface of the container 1 and providing the electrode 2 and the electrode 3 in contact with the outer surface of the curved surface portion 8 and arranging the electrode 2 and the electrode 3 so as to face each other in the width direction of the reaction container 1. A discharge space 15 is formed between the electrode 2 and the electrode 3 in the reaction vessel 1. The reaction vessel 1 is formed of the same material as described above. Further, both end faces in the width direction of the reaction vessel 1 are opened as gas inlets 16. And as shown in FIG.19 (b), the longitudinal direction (the width direction of the reaction container 1, Comprising: The width direction of the reaction container 1 and a plasma processing apparatus is shown with the arrow A) on the lower surface of the reaction container 1. A long and wide outlet 4 is formed in the parallel direction. The outlet 4 is slit-shaped and communicates with the discharge space 15 inside the reaction vessel 1 through the flat portion 7.
[0098]
The electrode 2 and the electrode 3 have the same shape, and are formed in a C shape with the lower surface opened in a side view. That is, the electrode 2 and the electrode 3 are formed with an insertion recess 33 that opens on the lower surface. The dimension of the inner surface of the insertion recess 33 is formed substantially the same as the outer dimension in the circumferential direction of the curved surface portion 8 of the reaction vessel 1. Furthermore, the electrode 2 and the electrode 3 are formed of the same material as described above. In addition, the inner surfaces of the electrodes 2 and 3 (surfaces constituting the insertion recesses 33) are surfaces that come into contact with the outer surface of the curved surface portion 8 of the reaction vessel 1, and the surface roughness expressed by the arithmetic average roughness of the inner surfaces. The degree is set to 10 to 1000 μm.
[0099]
Then, by inserting the reaction vessel 1 into the insertion recess 33 from below, the electrode 2 and the electrode 3 are attached to and contacted with the curved surface portion 8 on the outer surface of the reaction vessel 1, and a power source 18 that generates an alternating electric field is applied to the electrode 2. By connecting and grounding the electrode 3, a plasma processing apparatus as shown in FIG. 19A can be formed. The distance between the electrode 2 and the electrode 3 (the distance between the electrode 2 and the electrode 3 in the width direction of the reaction vessel 1) is preferably set to 3 to 20 mm. The plasma processing apparatus thus formed can perform plasma processing in the same manner as the embodiment shown in FIG. 1 and has the same effect as the embodiment shown in FIG. .
[0100]
Furthermore, in this embodiment, the lower surface (planar portion 7) of the reaction vessel 1 and the tip surfaces (lower surfaces) of the electrodes 2 and 3 are formed as flat surfaces, and the tips of the electrodes 2 and 3 are the same as those of the reaction vessel 1. Since the bottom surface of the reaction vessel 1 and the tip surfaces of the electrodes 2 and 3 are formed so as not to protrude from the bottom surface, the object to be processed can be brought close to the vicinity of the blowout port 4. The active plasma in the atmosphere blown out into the atmosphere can be sprayed on the workpiece before the active plasma active species disappear, and the plasma of the workpiece can be efficiently utilized by using the active species in the plasma. The processing can be enhanced. In addition, although the distance between the blower outlet 4 and a to-be-processed object changes with application conditions, the kind of to-be-processed object, etc., it can set to 2-10 mm.
[0101]
In this embodiment, the gas inlet 16 is formed at both ends in the longitudinal direction of the reaction vessel 1, and the reaction vessel 1 is viewed from the side (a direction parallel to the longitudinal direction of the reaction vessel 1) through the gas inlet 16. Since the plasma generating gas is introduced into the inside, the plasma generating gas can be supplied uniformly over the entire length of the blow-out port 4 formed in parallel with the longitudinal direction of the reaction vessel 1, and the homogeneous plasma can be efficiently produced. It can be generated. Therefore, high density and homogeneous plasma is sprayed on the object to be processed, so that the performance of the plasma processing can be improved and the plasma processing can be performed in a short time.
[0102]
FIG. 20 shows another embodiment. In this plasma processing apparatus, the outlet 4 is formed on the lower surface of the reaction vessel 1 along the inner surface of the curved surface portion 8 of the reaction vessel 1 formed along the electric lines of force a. It is formed similarly to that of FIG. That is, in the plasma processing apparatus of FIG. 19, the outlet 4 is formed long along the center line D that substantially bisects the lower surface of the reaction vessel 1 in the thickness direction of the reaction vessel 1. In the plasma processing apparatus (1), the outlet 4 is formed on the inner surface of the curved surface portion 8 at the end of the lower surface of the reaction vessel 1 at a position closer to the curved surface portion 8 than the position of the center line D and in the vicinity of the curved surface portion 8. Along this, the reaction vessel 1 is formed long in the width direction. Further, in this plasma processing apparatus, on the lower surface of the reaction vessel 1, the blowout port 4 is formed only at one end in the thickness direction of the reaction vessel 1.
[0103]
As described above, in the plasma processing apparatus of FIG. 19, when the electrode 2 and the electrode 3 are in contact with the outer surface of the curved surface portion 8 of the reaction vessel 1, the electric lines of force a along the inner surface of the curved surface portion 8 of the reaction vessel 1 are generated. Although many are formed, the plasma P is concentrated in the vicinity of the inner surface of the curved surface portion 8 of the reaction vessel 1 rather than the central portion in the thickness direction of the reaction vessel 1 as shown in FIGS. The concentration tends to increase. Therefore, as shown in FIG. 19 and FIG. 20 (c), as shown in FIG. 20 (a), rather than forming the outlet 4 at the substantially central portion in the thickness direction of the reaction vessel 1 on the lower surface of the reaction vessel 1. In the lower surface of the reaction vessel 1, the plasma P can be blown out more efficiently by forming the blowing port 4 along the curved surface portion 8 near the curved surface portion 8 of the reaction vessel 1, thereby improving the plasma processing capability. It can be done.
[0104]
FIG. 21 shows another embodiment. In this plasma processing apparatus, the outlet 4 is formed along the inner surface of the curved surface portion 8 at both ends of the lower surface of the reaction vessel 1 formed along the electric lines of force a. The configuration is the same as that of FIG. That is, in the plasma processing apparatus of FIG. 19, the blowout port 4 is formed long along the center line D that bisects the lower surface of the reaction vessel 1 in the thickness direction of the reaction vessel 1, but the plasma of FIG. In the processing apparatus, the outlet 4 is made longer along the inner surface of the curved surface portion 8 at the end of the lower surface of the reaction vessel 1 at a position closer to the curved surface portion 8 than the position of the center line D and in the vicinity of the curved surface portion 8. Formed. Further, in this plasma processing apparatus, blowout ports 4 are formed at both ends in the thickness direction of the reaction vessel 1 on the lower surface of the reaction vessel 1.
[0105]
As described above, in the plasma processing apparatus of FIG. 19, when the electrode 2 and the electrode 3 are in contact with the outer surface of the curved surface portion 8 of the reaction vessel 1, there are many electric lines of force a along the inner surface of the curved surface portion 8 of the reaction vessel 1. As a result, as shown in FIG. 20C, the plasma P is generated more concentrated in the vicinity of the inner surface of the curved surface portion 8 of the reaction vessel 1 than in the central portion in the thickness direction of the reaction vessel 1. The concentration tends to increase. Accordingly, as shown in FIG. 21 and FIG. 20 (c), rather than forming the outlet 4 at the substantially central portion in the thickness direction of the reaction vessel 1 on the lower surface of the reaction vessel 1, as shown in FIG. In the lower surface of 1, it is possible to blow out the plasma P more efficiently and improve the performance of the plasma processing by forming the blowout port 4 along the curved surface portion 8 in the vicinity of the curved surface portion 8 of the reaction vessel 1. It is. Moreover, as in the case of FIG. 4, the plasma processing is performed by conveying the workpiece 60 in the direction perpendicular to the longitudinal direction of the blowout port 4 below the blowout port 4 to perform the plasma treatment. 60 can be sprayed twice (twice), and the irradiation time of the plasma P in one transfer of the workpiece 60 is doubled as compared with that in FIG. Capability can be improved. In this embodiment, since the opening area of the blowing port 4 is increased as compared with those of FIGS. 19 and 20A, the flow rate of the plasma P blowing is decreased by increasing the flow rate of the plasma generating gas. It is preferable not to do so.
[0106]
FIG. 22 shows another embodiment. In this embodiment, the electrodes 2 and 3 are cooled in the plasma processing apparatus of FIG. That is, the inside of the electrode 2 and the electrode 3 is formed as a flow part 26 through which a refrigerant can flow, and in each of the electrode 2 and the electrode 3, a supply pipe 21 that communicates with the flow part 26 on the outer surface of one side end. A discharge pipe 22 communicating with the flow part 26 is provided on the outer surface of the other end. And arrow (3) As shown in FIG. 2, the coolant is supplied to the flow passage 26 inside the electrode 2 and the electrode 3 through the supply pipe 21 to cool the electrode 2 and the electrode 3 while generating plasma. The refrigerant supplied to the circulation unit 26 is an arrow. (4) As shown by, the gas is discharged from the electrode 2 and the electrode 3 through the discharge pipe 22. The same refrigerant as described above can be used. Since this embodiment cools the electrode 2 and the electrode 3, the same effects as those of the embodiment shown in FIGS.
[0107]
Also in this embodiment, as shown in FIG. 20 (a), the outlet 4 is set along the inner surface of the curved surface portion 8 of the reaction vessel 1 formed along the electric lines of force a. As shown in FIG. 21, the outlet 4 is formed along the inner surface of the curved surface portion 8 of the reaction vessel 1 formed along the electric lines of force a as shown in FIG. Or may be formed at both ends of the lower surface of the substrate.
[0108]
FIG. 23 shows another embodiment. In this embodiment, the volume reducing tool 11 for reducing the volume of the discharge space 15 is provided in the plasma processing apparatus of FIG. The volume reducing tool 11 is formed by a circular tube having both ends open, and one end projects from one gas inlet 16 of the reaction vessel 1 and the other end from the other gas inlet 16 of the reaction vessel 1. The reaction vessel 1 is disposed so as to protrude. And the volume reduction tool 11 is cooled by distribute | circulating a refrigerant | coolant. That is, the arrow (5) As shown, the coolant is supplied to the interior of the volume reducing tool 11 through one opening of the volume reducing tool 11 to circulate the volume reducing tool 11. The refrigerant supplied to the inside of the volume reducing tool 11 is an arrow. (6) As shown by the figure, it is discharged through the other opening. Further, the volume reducing tool 11 is formed of the same material as described above.
[0109]
The volume reducing tool 11 is inserted into the reaction vessel 1 from the gas inlet 16 so as to be positioned in the discharge space 15. Therefore, the volume of the discharge space 15 in this embodiment is smaller than that of the discharge space 15 of the plasma processing apparatus of FIG. 22, and the same effect as that of the embodiment shown in FIG. 7 is achieved.
[0110]
Also in this embodiment, as shown in FIG. 20 (a), the outlet 4 is set along the inner surface of the curved surface portion 8 of the reaction vessel 1 formed along the electric lines of force a. As shown in FIG. 21, the outlet 4 is formed along the inner surface of the curved surface portion 8 of the reaction vessel 1 formed along the electric lines of force a as shown in FIG. Or may be formed at both ends of the lower surface of the substrate.
[0111]
In FIG. Reference form Indicates. This plasma processing apparatus is formed by placing the electrode 2 and the electrode 3 in contact with each other over the entire outer peripheral surface of the reaction vessel 1 and arranging the electrode 2 and the electrode 3 so as to face each other vertically. Inside the vessel 1, a discharge space 15 is formed between the electrode 2 and the electrode 3. The reaction vessel 1 is formed of a cylinder with a bottom made of the same material as described above. Further, the upper surface of the reaction vessel 1 is opened over almost the entire surface as the gas inlet 16 and the circular lower surface of the reaction vessel 1 is formed as a substantially flat surface. Then, as shown in FIG. 24 (b), a large number of micro holes 9 are arranged in a circle in the bottom view of the reaction vessel 1, so that a circular wide outlet 4 is formed by an aggregate of the micro holes 9. Is formed. Each microhole 9 communicates with the discharge space 15 inside the reaction vessel 1. The diameter of the microhole 9 can be set to 0.5 to 2 mm, although it varies depending on the application condition and the type of the object to be processed.
[0112]
The electrode 2 and the electrode 3 have the same shape and are formed in an O shape (circular ring) in plan view. That is, the insertion hole 17 penetrating vertically is formed in the approximate center of the electrodes 2 and 3. The size of the insertion hole 17 is substantially the same as the outer peripheral dimension of the reaction vessel 1, and the shape of the insertion hole 17 in plan view is substantially the same as the outer peripheral shape of the reaction vessel 1. The electrodes 2 and 3 are made of the same material as described above. Then, by forming the electrode 2 and the electrode 3 in an O-shaped circular ring shape in plan view, the electrode 2 and the electrode 3 can be arranged over the entire circumference of the reaction vessel 1. The contact area with the reaction vessel 1 can be increased to improve the contact property, and plasma generation is facilitated. In addition, the inner surfaces of the electrodes 2 and 3 (surfaces constituting the insertion holes 17) are in contact with the outer periphery of the reaction vessel 1, and the surface roughness expressed by the arithmetic average roughness of the inner surfaces is 10 to 10. It is set to 1000 μm.
[0113]
Then, by inserting the reaction vessel 1 into the insertion hole 17, the electrodes 2 and 3 are attached to the outer periphery of the reaction vessel 1 and the inner peripheral surfaces of the electrodes 2 and 3 are brought into contact with the outer peripheral surface of the reaction vessel 1. A plasma processing apparatus as shown in FIG. 24A can be formed by arranging and connecting a power source 18 for generating an alternating electric field to the electrode 2 and grounding the electrode 3. Here, the grounded electrode 3 is disposed below the electrode 2 to which a high voltage is applied, that is, the electrode 3 is disposed closer to the outlet 4 than the electrode 2. Moreover, it is preferable to set the space | interval of the electrode 2 and the electrode 3 to 3-20 mm. The plasma processing apparatus thus formed can perform plasma processing in the same manner as the embodiment shown in FIG. 1 and has the same effect as the embodiment shown in FIG. .
[0114]
In addition, this Reference form Then, since the outlet 4 is formed by the aggregate of the microholes 9, the volume of the discharge space 15 can be reduced as compared with the case where the slit-like outlet is formed over the entire circumference of the lower surface of the reaction vessel 1. It is possible to accelerate the flow velocity of the plasma blown out from the blow-out port 4 without losing reactive gas active particles such as short-lived radicals before the plasma jet reaches the object to be processed. Can be efficiently performed.
[0115]
In FIG. Reference form Indicates. In this plasma processing apparatus, the blow-out port 4 is formed so as to be biased toward the substantially end portion of the lower surface of the reaction vessel 1 along the inner peripheral surface of the reaction vessel 1 formed along the electric lines of force a. Other configurations are the same as those in FIG. That is, in the plasma processing apparatus of FIG. 24, the blowout ports 4 are formed along the entire circumference of the inner peripheral surface of the reaction vessel 1, but in the plasma processing apparatus of FIG. The blowout port 4 is formed only in the vicinity of the inner peripheral surface on one side.
[0116]
As described above, in the plasma processing apparatus of FIG. 24, the electrode 2 and the electrode 3 are in contact with the outer peripheral surface of the reaction vessel 1, so that many electric lines of force a are formed along the inner peripheral surface of the reaction vessel 1. As a result, as shown in FIGS. 3B and 3C, the plasma P is generated more concentrated in the vicinity of the inner peripheral surface of the reaction vessel 1 than the central portion of the reaction vessel 1, and the concentration tends to increase. is there. Therefore, rather than forming the outlet 4 at the substantially central portion in the thickness direction of the reaction vessel 1 on the lower surface of the reaction vessel 1, as shown in FIG. 25, near the inner peripheral surface of the reaction vessel 1 on the lower surface of the reaction vessel 1. Thus, the formation of the blowout port 4 along the inner peripheral surface can blow out the plasma P more efficiently, and the performance of the plasma processing can be improved.
[0117]
In FIG. Reference form Indicates. In this plasma processing apparatus, the outlet 4 is biased toward the peripheral end portions on both sides of substantially the lower surface of the reaction vessel 1 along the inner peripheral surface of the reaction vessel 1 formed along the electric lines of force a. The other configuration is the same as that of FIG. That is, in the plasma processing apparatus of FIG. 24, the blowout ports 4 are formed along the entire circumference of the inner peripheral surface of the reaction vessel 1, but in the plasma processing apparatus of FIG. Blowing ports 4 are formed in the vicinity of the inner peripheral surfaces on both sides.
[0118]
As described above, in the plasma processing apparatus of FIG. 24, the electrode 2 and the electrode 3 are in contact with the outer peripheral surface of the reaction vessel 1, so that many electric lines of force a are formed along the inner peripheral surface of the reaction vessel 1. As a result, as shown in FIGS. 3B and 3C, the plasma P is generated more concentrated in the vicinity of the inner peripheral surface of the reaction vessel 1 than the central portion of the reaction vessel 1, and the concentration tends to increase. is there. Therefore, rather than forming the outlet 4 at the substantially central portion in the thickness direction of the reaction vessel 1 on the lower surface of the reaction vessel 1, as shown in FIG. Thus, the formation of the blowout port 4 along the inner peripheral surface can blow out the plasma P more efficiently, and the performance of the plasma processing can be improved. In addition, similarly to FIG. 4, the plasma processing is performed by conveying the workpiece 60 in the direction substantially perpendicular to the longitudinal direction of the blowout port 4 below the blowout port 4, thereby performing the plasma treatment on the workpiece 60. Can be sprayed twice (twice), and the plasma P irradiation time in one transfer of the workpiece 60 is doubled as compared with that in FIG. It is something that can be done. In addition, this Reference form In FIG. 25, since the opening area of the blowout port 4 is increased as compared with that in FIG. 25, it is preferable that the flow rate of the plasma P blowout is not lowered by increasing the flow rate of the plasma generating gas.
[0119]
27 and 28 Reference form Indicates. this Reference form Is for cooling the electrode 2 and the electrode 3 in the plasma processing apparatus of FIG. That is, the inside of the electrode 2 and the electrode 3 is formed as a circulation part 26 through which a refrigerant can flow, and the supply pipe 21 and the discharge pipe 22 communicating with the circulation part 26 protrude from the outer peripheral surfaces of the electrodes 2 and 3. It is installed. And arrow (3) As shown in FIG. 2, the coolant is supplied to the flow passage 26 inside the electrode 2 and the electrode 3 through the supply pipe 21 to cool the electrode 2 and the electrode 3 while generating plasma. The refrigerant supplied to the circulation unit 26 is an arrow. (4) As shown by, the gas is discharged from the electrode 2 and the electrode 3 through the discharge pipe 22. The same refrigerant as described above can be used. And this Reference form Since the electrode 2 and the electrode 3 are cooled, the same effects as those of the embodiment shown in FIGS.
[0120]
In addition, this Reference form In FIG. 25, as shown in FIG. 25, the outlet 4 is formed at the peripheral end of one side of the lower surface of the reaction vessel 1 along the inner peripheral surface of the reaction vessel 1 formed along the electric lines of force a. 26, as shown in FIG. 26, the outlet 4 is formed at the peripheral end portions on both sides of the lower surface of the reaction vessel 1 along the inner peripheral surface of the reaction vessel 1 formed along the electric lines of force a. can do.
[0121]
The other in FIG. Reference form Indicates. this Reference form 27 and 28 are provided with a volume reducing tool 11 for reducing the volume of the discharge space 15 in the plasma processing apparatus of FIGS. As shown in FIG. 30, the volume reducing tool 11 is formed in a cylindrical shape that is smaller than the reaction container 1 and substantially equal to the internal shape of the reaction container 1, and an introduction tube 40 is provided inside the volume reducing tool 11. Longer in the vertical direction. Further, the upper end of the introduction tube 40 is projected from the upper surface of the volume reducing tool 11 as the introduction portion 24. Further, a pair of substantially L-shaped outlet pipes 41 project from the upper surface of the volume reducing tool 11 on both sides of the introduction portion 24. And the volume reduction tool 11 is cooled by distribute | circulating the same refrigerant | coolant as the above. That is, the arrow (5) As shown in FIG. 5, the volume reducing tool 11 is cooled by supplying and circulating the refrigerant through the introducing portion 24 into the introduction pipe 40 and the volume reducing tool 11. The refrigerant supplied to the volume reducing tool 11 is an arrow. (6) As shown in FIG. Further, the volume reducing tool 11 is formed of the same material as described above.
[0122]
The volume reducing tool 11 is inserted and arranged from the gas inlet 16 into the reaction vessel 1 so that the lower part thereof is located in the discharge space 15. Accordingly, the volume of the discharge space 15 in this embodiment is smaller than that of the discharge space 15 of the plasma processing apparatus of FIGS. 27 and 28, and the same effect as that of the embodiment shown in FIG. is there.
[0123]
In addition, this Reference form In FIG. 25, as shown in FIG. 25, the outlet 4 is formed at the peripheral end of one side of the lower surface of the reaction vessel 1 along the inner peripheral surface of the reaction vessel 1 formed along the electric lines of force a. 26, as shown in FIG. 26, the outlet 4 is formed at the peripheral end portions on both sides of the lower surface of the reaction vessel 1 along the inner peripheral surface of the reaction vessel 1 formed along the electric lines of force a. can do.
[0124]
Figure 31 shows another Reference form Indicates. This plasma processing apparatus is formed by providing the electrode 2 and the electrode 3 in contact with each other over the entire outer periphery of the reaction vessel 1 and arranging the electrode 2 and the electrode 3 so as to face each other vertically. 1, a discharge space 15 is formed between the electrode 2 and the electrode 3. The reaction vessel 1 is formed in a cylinder with the same material as described above. Further, the upper surface of the reaction vessel 1 is opened as a gas inlet 16 over substantially the entire surface, and the lower portion of the reaction vessel 1 is formed as a converging portion 45 that is narrowed down so that the dimension in the thickness direction becomes smaller toward the lower side. ing. As shown in FIG. 31 (b), a straight outlet 4 that is long in the width direction of the reaction vessel 1 is formed on the lower surface of the converging portion 45 of the reaction vessel 1. The outlet 4 is formed in a slit shape and communicates with the discharge space 15 inside the reaction vessel 1. Electrode 2 and electrode 3 are shown in FIG. Reference form It is formed in the same way.
[0125]
Then, by inserting the reaction vessel 1 into the insertion holes 17 of the electrode 2 and the electrode 3, the electrode 2 and the electrode 3 are attached to the outer periphery of the reaction vessel 1 and the inner peripheral surfaces of the electrode 2 and the electrode 3 are connected to the outer periphery of the reaction vessel 1. A plasma processing apparatus as shown in FIG. 31A can be formed by placing the power supply 18 in contact with the surface and connecting the power source 18 for generating an alternating electric field to the electrode 2 and grounding the electrode 3. Here, the electrode 3 to be grounded is disposed below the electrode 2, that is, the electrode 3 is disposed closer to the blowing port 4 than the electrode 2. Moreover, it is preferable to set the space | interval of the electrode 2 and the electrode 3 to 3-20 mm. The plasma processing apparatus thus formed can perform plasma processing in the same manner as the embodiment shown in FIG. 1 and has the same effect as the embodiment shown in FIG. .
[0126]
In addition, this Reference form Then, by providing the converging part 45 that is narrowed down so that the outlet 4 is linear, the volume of the discharge space 15 is reduced compared to the case where the reaction vessel 1 is formed straight without providing the converging part 45. The flow velocity of the plasma blown out from the blow-out port 4 can be accelerated by the converging unit 45 without reaching the jet-like plasma before the reactive gas active particles such as short-lived radicals disappear. Therefore, the plasma treatment of the workpiece can be performed efficiently. In order to obtain a plasma flow rate suitable for cleaning the surface of the workpiece, the taper angle formed between the outer peripheral surface of the focusing portion 45 and the outer surface of the reaction vessel 1 other than the focusing portion 45 is 10 to 30 °. It is preferable that
[0127]
32 and 33 Reference form Indicates. In this embodiment, the electrodes 2 and 3 are cooled in the plasma processing apparatus of FIG. That is, the inside of the electrode 2 and the electrode 3 is formed as a circulation part 26 through which a refrigerant can flow, and the supply pipe 21 and the discharge pipe 22 communicating with the circulation part 26 protrude from the outer peripheral surfaces of the electrodes 2 and 3. It is installed. And arrow (3) As shown in FIG. 2, the coolant is supplied to the flow passage 26 inside the electrode 2 and the electrode 3 through the supply pipe 21 to cool the electrode 2 and the electrode 3 while generating plasma. The refrigerant supplied to the circulation unit 26 is an arrow. (4) As shown by, the gas is discharged from the electrode 2 and the electrode 3 through the discharge pipe 22. The same refrigerant as described above can be used. And this Reference form Since the electrode 2 and the electrode 3 are cooled, the same effects as those of the embodiment shown in FIGS.
[0128]
In addition, in FIG. 31 thru | or 33 Reference form In this case, the volume reducing tool 11 of FIG.
[0129]
【Example】
Hereinafter, the present invention will be described specifically by way of examples.
[0130]
Example 1
A plasma processing apparatus having the structure shown in FIG. 5 was formed. Quartz glass was used as the reaction vessel 1, and the width dimension was 60 mm and the thickness dimension was 7 mm. Moreover, the blowout port 4 was formed in 0.2 * 55 mm. The upper electrode 2 and the lower electrode 3 were made of copper, and the arithmetic average roughness of the inner peripheral surface was formed to 100 μm. Further, pure water was used as a coolant for cooling the electrodes 2 and 3. As the object to be processed, a silicon substrate coated with 1 μm of a negative resist was used.
[0131]
The plasma generating gas was supplied to the reaction vessel 1 by flowing a mixture of helium at 1 liter / min, argon at 4 liter / min, and oxygen at 0.06 liter / min. Then, a plasma is generated by applying a high frequency electric field of 13.56 MHz at 400 W to the discharge space 15, and this is blown out in a jet shape from the blowing port 4 and supplied to the surface of the object to be processed by plasma processing (resist etching). )
[0132]
As a result, an etching rate of about 7 μm / min was obtained with a width of 50 mm, and the resist could be etched into a very uniform shape. As a result of XPS analysis, no impurities other than the resist component were detected.
[0133]
(Example 2)
A plasma processing apparatus having the structure shown in FIG. 17 was formed. Quartz glass was used as the reaction vessel 1, and the width dimension was 60 mm and the thickness dimension was 50 mm. Moreover, the blowout port 4 was formed in 0.2 * 55 mm. The right electrode 2 and the left electrode 3 were made of copper, and the arithmetic average roughness of the inner peripheral surface was formed to 100 μm. Further, pure water was used as a coolant for cooling the electrodes 2 and 3. As the object to be processed, a silicon substrate coated with 1 μm of a negative resist was used.
[0134]
The plasma generating gas was supplied to the reaction vessel 1 by flowing a mixture of helium at 1 liter / min, argon at 4 liter / min, and oxygen at 0.06 liter / min. Then, a plasma is generated by applying a high frequency electric field of 13.56 MHz at 400 W to the discharge space 15, and this is blown out in a jet shape from the blowing port 4 and supplied to the surface of the object to be processed by plasma processing (resist etching). )
[0135]
As a result, an etching rate of about 5 μm / min was obtained with a width of 50 mm, and the resist could be etched into a very uniform shape. As a result of XPS analysis, no impurities other than the resist component were detected.
[0136]
(Example 3)
A plasma processing apparatus having the structure shown in FIG. 23 was formed. A quartz glass tube having a semicircular cross section was used as the reaction vessel 1 and the outer diameter was formed to 20 mm. Moreover, the blowout port 4 was formed in 0.2 * 55 mm. Further, a quartz tube having an outer diameter of 8 mm was inserted into the reaction vessel 1 as a volume reducing tool 11. The right electrode 2 and the left electrode 3 were made of copper, and the arithmetic average roughness of the inner peripheral surface was formed to 100 μm. Further, pure water was used as a coolant for cooling the electrode 2, the electrode 3, and the volume reducing tool 11.
[0137]
As an object to be processed, an OMPAC (Over Molded Pad Array Carrier) type BGA (Ball Grid Array) substrate was used. This is formed by applying a resist (PSR-4000AUS5) made by Taiyo Ink Co., Ltd. to a thickness of 40 μm on a 0.5 mm-thick BT (bismaleimide triazine) substrate (size: 50 × 200 mm). Further, a gold plating circuit including a bonding pad is formed on a part of the object to be processed, and an IC chip is mounted. This IC chip has a thickness of 10 nm on a silicon substrate in order to evaluate charge-up damage (damage during power feeding) due to plasma processing. ₂ A layer and 300 nm thick polysilicon are formed.
[0138]
The plasma generation gas was supplied to the reaction vessel 1 by flowing a mixture of helium at 2 liter / min, argon at 8 liter / min, and oxygen at 0.2 liter / min. Then, a plasma is generated by applying a high frequency electric field of 13.56 MHz at 500 W to the discharge space 15, and this is blown out in a jet shape from the blowing port 4 and supplied to the surface of the workpiece to be plasma treated (the workpiece to be treated). 6 surface modification treatment and cleaning treatment).
[0139]
As a result, the water contact angle of the resist portion was lowered from 80 degrees to 8 degrees before and after the treatment, and the hydrophilicity of the surface was improved. In addition, as a result of wire bonding the bonding pad of the gold plating circuit and the IC chip, the strength of wire bonding was 5.1 g before processing, but improved to 8.9 g after processing, and remarkable performance (wire The bonding strength was improved. Further, as a result of XPS analysis of the bonding pad part, the composition ratio (C / Au) of carbon atoms and gold atoms on the surface decreased from about 3 to about 0.5 before and after the treatment. Carbon removal was taking place. It is considered that the strength of wire bonding was improved because of the carbon removal. Further, impurities other than carbon atoms and gold atoms were not detected.
[0140]
Furthermore, a bottom area of 1 cm is formed on the surface of the object to be processed using a sealing resin (SMT-B-1) manufactured by Pluscon. ² As a result of forming a pudding-like sealing resin and measuring the shear peel strength between the sealing resin and the object to be processed, it was 2 MPa before the treatment, but the strength was greatly improved to 10 MPa after the treatment. It was. In addition, there was no charge-up damage to the IC chip mounted on the workpiece.
[0141]
( Reference example 1 )
A plasma processing apparatus A having the structure shown in FIG. 29 was formed. A quartz glass tube was used as the reaction vessel 1, and the outer diameter was 58 mm and the inner dimension was 55 mm. The upper electrode 2 and the lower electrode 3 were made of copper, and the arithmetic average roughness of the inner peripheral surface was formed to 100 μm. In addition, a stainless double tube having an outer diameter of 50 mm was inserted inside the reaction vessel 1 as the volume reducing tool 11. Further, pure water was used as a coolant for cooling the electrode 2, the electrode 3, and the volume reducing device 11.
[0142]
As an object to be processed, a substrate in which a silver palladium paste was screen printed on an alumina substrate and baked to form a circuit including a bonding pad portion was used. Other configurations are the same as those of the third embodiment.
[0143]
The plasma generating gas was supplied to the reaction vessel 1 by flowing a mixture of helium at 2 liter / min, argon at 8 liter / min, and hydrogen at 0.1 liter / min. Then, a plasma is generated by applying a high frequency electric field of 13.56 MHz at 500 W to the discharge space 15, and this is blown out in a jet shape from the blowing port 4 and supplied to the surface of the workpiece to be plasma treated (the workpiece to be treated). 6 surface modification treatment and cleaning treatment).
[0144]
As a result of XPS analysis of the bonding pad portion, a peak of silver oxide was confirmed before the treatment, but this peak changed to metallic silver after the treatment, and the silver oxide in the bonding pad portion was reduced. Further, as a result of measuring the temperature of the plasma at a position 5 mm away from the outlet 4 during the plasma treatment, the volume reduction tool 8 is cooled by about 200 ° C. compared to the case where it is not cooled by the refrigerant when cooled by the refrigerant. It was.
[0145]
( Reference example 2 )
In Example 1, instead of the slit-shaped outlet 4, 28 holes with a diameter of 1 mm were arranged at intervals of 2 mm, and an aggregate of the holes was formed as the outlet 4. The plasma treatment was performed in the same manner as in Example 1 except for this.
[0146]
As a result, an etching rate of about 7 μm / min was obtained with a width of 50 mm, and the resist could be etched into a very uniform shape. As a result of XPS analysis, no impurities other than the resist component were detected.
[0147]
( Reference example 3 )
A plasma processing apparatus having the structure shown in FIG. 11 was formed. Quartz glass was used as the reaction vessel 1, and the outer width dimension was 56 mm, the inner width dimension was 54 mm, the outer thickness dimension was 3 mm, and the inner thickness dimension was 1 mm. Moreover, the upper electrode 2 and the lower electrode 3 were made of copper, and the arithmetic average roughness of the inner peripheral surface was formed to 100 μm. Further, pure water was used as a coolant for cooling the electrodes 2 and 3. As the object to be processed, a silicon substrate coated with 1 μm of a negative resist was used.
[0148]
The plasma generation gas was supplied to the reaction vessel 1 by flowing a mixture of helium at 2 liter / min, argon at 10 liter / min, and oxygen at 0.4 liter / min. Then, a plasma is generated by applying a high frequency electric field of 13.56 MHz at 700 W to the discharge space 15, and this is blown out in a jet shape from the blowout port 4 and supplied to the surface of the object to be treated for plasma treatment (resist etching). )
[0149]
As a result, an etching rate of about 15 μm / min was obtained with a width of 55 mm, and the resist could be etched into a very uniform shape. As a result of XPS analysis, no impurities other than the resist component were detected.
[0150]
【The invention's effect】
As described above, the invention of claim 1 of the present invention comprises a reaction vessel formed of an insulating material and at least a pair of opposed electrodes in contact with the outer surface of the reaction vessel, and the reaction vessel is for plasma generation. Plasma treatment that generates a glow-like discharge in the reaction vessel under atmospheric pressure by supplying gas and applying an alternating electric field between the electrodes, and generates plasma in the reaction vessel by glow-like discharge In the apparatus, a pair of electrodes are arranged so that electric lines of force along the inner surface of the reaction vessel are formed, and a blow-out port for blowing out jet plasma having a width is formed in the reaction vessel. This makes it difficult for electric lines of force to be generated in the vertical direction of the inner surface of the reactor, thereby reducing the deterioration of the reaction vessel due to the lines of electric force, making it difficult for the constituent materials to jump out of the inner surface of the reaction vessel. It is possible to reduce the contamination of the physical object by impurities, and the substrate or the plasma processing apparatus is orthogonal to the width direction of the blowout port while blowing out the plasma having a width like a curtain from the blowout port. By moving plasma in a direction and scanning and spraying the entire surface of the substrate, it is possible to perform plasma processing over a large area of the object to be processed at a time as compared with the case of blowing out spot-like plasma, and a substrate such as a BGA substrate. The processing time can be shortened when the entire surface is processed.
In addition, since the blowout port is formed in a slit shape, the substrate or the plasma processing apparatus is moved in a direction perpendicular to the width direction of the blowout port while blowing out plasma having a curtain-like width from the blowout port, so that the entire surface of the substrate is By scanning and spraying plasma, it is possible to perform plasma processing on a large area of an object to be processed at a time as compared with the case of blowing spot plasma, and processing time when processing the entire surface of a substrate such as a BGA substrate. Can be shortened.
In addition, the outlet is formed in the flat part of the reaction vessel. The opening area of this slit-shaped outlet is smaller than the cross-sectional area inside the reaction vessel Therefore, it becomes possible to bring the object to be processed close to the vicinity of the outlet, and it becomes easy to keep the distance between the outlet and the object to be processed substantially constant, and the plasma blown into the atmosphere from the outlet It can be sprayed on the workpiece before extinguishing the active plasma active species contained in it, and the plasma treatment of the workpiece can be enhanced by efficiently using the active species in the plasma. is there.
[0151]
In the invention according to claim 2 of the present invention, since the blowout port is formed on the lower surface of the box-shaped reaction vessel, the substrate having a width like a curtain is blown downward from the blowout port on the lower surface of the reaction vessel. Alternatively, by moving the plasma processing apparatus in a direction perpendicular to the width direction of the blowout port and scanning and spraying the plasma over the entire surface of the substrate, a large area of the object to be processed is once compared with that which blows out spot-like plasma. Plasma processing can be performed, and the processing time can be shortened when the entire surface of a substrate such as a BGA substrate is processed.
[0152]
In the invention of claim 3 of the present invention, the pair of electrodes are arranged so as to be opposed to each other, so that the direction of the alternating electric field generated between the pair of electrodes (direction of electric lines of force), the plasma generating gas, The plasma flow direction can be made substantially coincident, and plasma active species can be generated efficiently, and the size of the discharge space can be easily changed by changing the distance between the pair of electrodes. And the amount of plasma generated can be easily adjusted.
[0153]
The invention of claim 4 of the present invention is a reaction vessel. To Since it is formed in a flat cylinder shape and the opposing spacing of the side walls of the reaction vessel is formed in the narrow direction in the range of 0.1 to 5 mm, the volume of the discharge space formed between the pair of electrodes is reduced, and the unit of the discharge space The power per volume can be improved to improve the generation efficiency of the plasma treatment, and the power can be reduced and the gas flow rate can be reduced.
[0154]
In the invention according to claim 5 of the present invention, since the electrodes are formed in a square shape in plan view, the electrodes can be arranged over the entire circumference of the reaction vessel, and the contact area between the electrode and the reaction vessel is increased. Thus, the contact property can be improved, and the plasma can be easily generated.
[0155]
In the invention according to claim 6 of the present invention, one electrode to be grounded is disposed closer to the outlet than the other electrode to which a high voltage is applied, so that the electrode to which the high voltage is applied is grounded. Therefore, the arc discharge is difficult to fly from the high-pressure electrode to the object to be processed, and the object to be processed can be prevented from being damaged by the arc discharge.
[0156]
In the invention of claim 7 of the present invention, since the electrode is formed long in the direction parallel to the longitudinal direction of the outlet, a wide discharge space is formed on the upper side (upstream side) of the outlet. The plasma generating gas can be efficiently converted into plasma, high density plasma can be formed, and homogeneous plasma can be blown out over the entire length of the blowout port. Therefore, high density and homogeneous plasma is sprayed on the object to be processed, so that the performance of the plasma processing can be improved and the plasma processing can be performed in a short time.
[0157]
In the invention according to claim 8 of the present invention, since the electrode is formed in a U-shape with the lower surface opened in a side view, the lower surface of the reaction vessel and the tip of the electrode are prevented so that the tip of the electrode does not protrude from the lower surface of the reaction vessel. It becomes possible to bring the workpiece close to the vicinity of the blowout port by forming a flat surface, and extinguish the active plasma active species contained in the plasma blown into the atmosphere from the blowout port. It can be previously sprayed on the object to be processed, and the active species in the plasma can be efficiently used to enhance the plasma treatment of the object to be processed.
[0158]
The invention of claim 9 of the present invention provides a gas homogenizing chamber for homogenizing the flow of plasma generating gas in the reaction vessel. Set up The The gas homogenization chamber is formed so that the plasma generating gas supplied to the gas homogenization chamber passes through the gas homogenization chamber and is introduced into the reaction vessel. Therefore, by supplying the plasma generation gas to the reaction vessel through the gas homogenization chamber, the plasma generation gas is supplied at a uniform concentration throughout the reaction vessel so that the plasma generation gas is not biased to a part of the reaction vessel. It is possible to generate homogeneous plasma efficiently.
[0159]
In the invention according to claim 10 of the present invention, since the eaves part protruding into the gas homogenization chamber is formed in the reaction vessel, the agitation of the plasma generating gas can be improved in the eaves part, and more homogeneous plasma can be efficiently produced. It can be generated well.
[0160]
According to the eleventh aspect of the present invention, since the gas homogenization chamber is filled with spheres, the plasma generation gas is supplied to the reaction vessel through the gap between the spheres filled in the gas homogenization chamber, thereby generating plasma. The generation gas can be supplied at a more uniform concentration throughout the reaction vessel so as not to be biased to a part of the reaction vessel, and more uniform plasma can be efficiently generated.
[0161]
The invention of claim 12 of the present invention is a flat plane portion and a cross section. Half Since the reaction vessel is formed with an arcuate curved surface portion and the blowout port is formed in the flat portion, the workpiece can be brought close to the vicinity of the blowout port. It becomes easy to keep the distance substantially constant, and it can be sprayed on the object to be processed before extinguishing the active plasma active species contained in the plasma blown out from the air outlet into the atmosphere. Thus, the active species can be efficiently used to enhance the plasma treatment of the workpiece.
[0162]
In the thirteenth aspect of the present invention, since the electrode is arranged on the curved surface portion, electric lines of force are hardly generated in the vertical direction of the inner surface of the curved surface portion of the reaction vessel, and the deterioration of the reaction vessel due to the electric force lines is reduced. It is possible to reduce the contamination of the object to be processed by impurities because the constituent materials are less likely to jump out from the inner surface of the reaction vessel.
[0163]
The invention of claim 14 of the present invention is an electrode. Half Since it is formed in an arc shape, the electrode can be arranged over the entire circumference of the curved surface portion of the reaction vessel, the contact area between the electrode and the reaction vessel can be increased to improve the contact property, and plasma generation In addition, it is possible to make the lower surface of the reaction vessel and the tip surface of the electrode flush with each other so that the object to be processed can be brought close to the vicinity of the air outlet. It is easy to keep the distance of the plasma constant, and it can be sprayed on the workpiece before the active plasma species with high activity contained in the plasma blown into the atmosphere from the blowout port is extinguished. It is possible to enhance the plasma treatment of the workpiece by efficiently using the active species therein.
[0164]
In the fifteenth aspect of the present invention, the lower surface of the reaction vessel is formed as a flat portion, and the plasma generating gas is supplied to the reaction vessel from the side, so that the plasma generating gas is uniformly distributed over the entire length of the outlet. It can supply and can generate a homogeneous plasma efficiently. Therefore, high density and homogeneous plasma is sprayed on the object to be processed, so that the performance of the plasma processing can be improved and the plasma processing can be performed in a short time.
[0165]
According to the sixteenth aspect of the present invention, since the reaction vessel is formed in a cylindrical shape and the pair of electrodes are arranged so as to face each other vertically, electric lines of force are hardly generated in the vertical direction on the inner surface of the reaction vessel. Deterioration of the reaction vessel due to the lines of force can be reduced, and the constituent material is less likely to jump out from the inner surface of the reaction vessel, so that the object to be treated can be less contaminated with impurities.
[0166]
In the invention of claim 17 of the present invention, since the electrode is formed in an annular shape in plan view, the electrode can be arranged over the entire circumference of the reaction vessel, and the contact area between the electrode and the reaction vessel is increased. Contactability can be improved, and plasma generation is facilitated.
[0167]
In the invention of claim 18 of the present invention, one electrode to be grounded is disposed closer to the blowout port than the other electrode to which a high voltage is applied, so that the electrode to which the high voltage is applied is grounded. Therefore, the arc discharge is difficult to fly from the high-pressure electrode to the object to be processed, and the object to be processed can be prevented from being damaged by the arc discharge.
[0172]
Claims of the invention 19 According to the invention, since the blowout port is formed along the inner surface of the reaction vessel formed along the lines of electric force, the plasma is concentrated and generated along the inner surface of the reaction vessel which tends to increase in concentration. By forming the blowout port, the plasma can be efficiently blown out from the blowout port, and the plasma processing capability can be improved.
[0173]
Claim 2 of the present invention 0 According to the invention, since the blow-out ports are formed along each of the plurality of inner surfaces of the reaction vessel formed along the lines of electric force, the reaction vessel tends to have a high concentration due to plasma concentration. By forming a blowout port along the inner surface of the plasma, the plasma can be efficiently blown out from the blowout port, the plasma processing ability can be improved, and once in a plurality of places on the workpiece. Can be subjected to plasma treatment, and the efficiency of the plasma treatment can be improved.
[0174]
Claim 2 of the present invention 1 In the invention, at least one of the electrodes is cooled by the refrigerant, so that even if plasma is generated with an alternating current having a high frequency under atmospheric pressure, an increase in the temperature of the electrode can be suppressed, so that the plasma temperature (gas temperature) is reduced. It can be prevented from becoming high, and thermal damage to the object to be processed can be reduced. In addition, by cooling the electrodes, local heating of the discharge space can be prevented, and a homogeneous glow discharge can be generated to suppress the generation of streamer discharge. Can be reduced.
[0175]
Claim 2 of the present invention 2 In the invention, a volume reducing tool for reducing the volume of the discharge space formed between the pair of electrodes in the reaction vessel is provided in the reaction vessel, so that the input power per unit volume (AC electric field) in the discharge space is provided. Can be increased, and the efficiency of plasma generation can be improved.
[0176]
Claim 2 of the present invention 3 According to the invention, since the volume reducing tool is formed of an insulating material, impurities can be prevented from being generated by sputtering or corrosion from the volume reducing tool, and the object to be processed is not contaminated by impurities even when used for a long time. It is something that can be done.
[0177]
Claim 2 of the present invention 4 According to the invention, since the volume reducing tool is cooled by the refrigerant, the deterioration of the volume reducing tool due to heat can be reduced, and the life of the volume reducing tool can be extended. The temperature of plasma generated in the surrounding discharge space can be reduced, and damage to the object to be processed due to heat can be reduced.
[0178]
Claim 2 of the present invention 5 In the present invention, since the volume reducing device is formed of a metal material and the volume reducing device is cooled with a refrigerant, the volume reducing device is generated in the discharge space around the volume reducing device as compared with the case where the volume reducing device is formed of an insulating material. The temperature of the plasma can be further lowered, and damage to the object to be processed due to heat can be further reduced.
[0179]
Claims of the invention 26 In this invention, since the refrigerant is ion-exchanged water, impurities are not included in the refrigerant, and the electrode and the volume reducing device are not easily corroded by the refrigerant, thereby extending the life.
[0180]
Claims of the invention 27 In the invention, since the refrigerant has antifreeze and insulating properties, it is possible to prevent leakage from the electrode to which a high voltage is applied, and to stably generate plasma.
[0181]
Claims of the invention 28 In the invention, since the frequency of the alternating electric field applied between the pair of electrodes is set to 1 kHz to 200 MHz, the discharge in the discharge space can be stabilized and the plasma treatment can be performed efficiently. In addition, the temperature rise of the plasma in the discharge space can be suppressed, and the life of the reaction vessel, the electrode, and the volume reducing tool can be extended, and the plasma processing apparatus is less complicated and enlarged. Is something that can be done.
[0182]
Claims of the invention 29 Since the surface roughness of the electrode in contact with the reaction vessel of the electrode is 10 to 1000 μm, a very fine aggregate of microdischarges is formed, which can inhibit the transition to the arc and discharge The discharge in the space can be made uniform.
[0183]
Claim 3 of the present invention 0 According to the present invention, since the object to be processed is disposed below the outlet of the plasma processing apparatus according to any one of claims 1 to 29 and plasma is blown out from the outlet and supplied to the object to be processed, the inner surface of the reaction vessel This makes it difficult to generate electric lines of force in the vertical direction of the reaction vessel, thereby reducing the deterioration of the reaction vessel due to the lines of electric force, making it difficult for the constituent materials to jump out of the inner surface of the reaction vessel and contaminating the object to be treated with impurities. In addition, while the plasma having a curtain-like width is blown out from the blowout port, the substrate or the plasma processing apparatus is moved in a direction orthogonal to the width direction of the blowout port, so that the entire surface of the substrate is Plasma treatment on a large area of the object to be processed at a time compared to those that blow out spot-like plasma Rukoto can, in which it is possible to shorten the processing time when processing the entire surface of the substrate, such as a BGA substrate.
[Brief description of the drawings]
FIG. 1 shows an example of an embodiment of the present invention, where (a) is a perspective view and (b) is a bottom view.
2A is a partial cross-sectional view of the above, and FIG. 2B is a partial cross-sectional view of a conventional example.
3A is a bottom view showing another embodiment of the above, FIG. 3B is a partial cross-sectional view, and FIG. 3C is a partial cross-sectional view of the embodiment shown in FIG. 1;
4A is a bottom view showing another embodiment of the above, and FIG. 4B is a partial cross-sectional view.
FIG. 5 is a perspective view showing an example of another embodiment.
FIG. 6 is a bottom view of the above.
FIG. 7 is a perspective view showing an example of another embodiment.
FIGS. 8A and 8B show an example of the volume reducing device, wherein FIG. 8A is a perspective view and FIG. 8B is a front view.
FIG. 9 is a graph showing the relationship between the type of volume reducing tool, the cleaning performance, and the plasma gas temperature.
[Figure 10] Same as above reference An example of a form is shown, (a) is a front view with a part broken, (b) is a side view with a part broken.
FIG. 11 Same as above reference It is a perspective view which shows an example of a form.
FIG. 12 shows an example of the same reaction vessel, in which (a) is a front view, (b) is a side view, and (c) is a bottom view.
FIG. 13 is a cross-sectional view showing a portion in FIG.
14A and 14B show an example of another embodiment, in which FIG. 14A is a perspective view and FIG. 14B is a bottom view.
15A is a bottom view showing another embodiment of the embodiment, FIG. 15B is a side view, and FIG. 15C is a bottom view of the embodiment shown in FIG. 14;
FIG. 16 is a bottom view showing another embodiment of the above.
FIG. 17 is a perspective view showing an example of another embodiment described above.
FIG. 18 is a bottom view of the above.
FIGS. 19A and 19B show an example of another embodiment, where FIG. 19A is a perspective view and FIG. 19B is a bottom view.
20A is a bottom view showing another embodiment of the embodiment, FIG. 20B is a perspective view of the embodiment shown in FIG. 14, and FIG. 20C is a bottom view of the embodiment shown in FIG. 14; is there.
FIG. 21 is a bottom view showing another embodiment of the above.
FIG. 22 shows an example of another embodiment of the above, (a) is a front view, (b) is a bottom view, and (c) is a side view.
FIG. 23 shows an example of another embodiment described above, (a) is a front view, (b) is a bottom view, and (c) is a side view.
FIG. 24 Other than above reference An example of a form is shown, (a) is a perspective view, (b) is a bottom view.
FIG. 25 Other than above reference It is a bottom view which shows a form.
Fig. 26 Other of the above reference It is a bottom view which shows a form.
[Figure 27] Other above reference It is a front view which shows an example of a form.
FIG. 28 is a bottom view of the above.
[Fig. 29] Other above reference It is a front view which shows an example of a form.
FIG. 30 is a front view showing an example of the volume reducing device according to the embodiment.
FIG. 31 Other than above reference An example of a form is shown, (a) is a perspective view, (b) is a bottom view.
Fig. 32 Other of the above reference An example of a form is shown, (a) is a front view, (b) is a side view.
FIG. 33 is a bottom view of the above.
[Explanation of symbols]
1 reaction vessel
2 electrodes
3 electrodes
4 Outlet
5 Gas homogenization chamber
6 Sphere
7 Flat part
8 Curved surface
9 Micropores
11 Volume reduction tool
15 Discharge space
50 buttocks
a Electric field lines

Claims (30)

A reaction vessel formed of an insulating material and at least a pair of opposing electrodes in contact with the outer surface of the reaction vessel are configured to supply a plasma generating gas to the reaction vessel and apply an alternating electric field between the electrodes. In the plasma processing apparatus in which a glow discharge is generated in the reaction vessel under atmospheric pressure and plasma is generated in the reaction vessel by the glow discharge, the electric lines of force along the inner surface of the reaction vessel are A pair of electrodes are arranged so as to be formed, and a blowout port for blowing out a jet-like plasma having a width is formed in a slit shape in a flat plane portion of the reaction vessel, and the opening area of this slit-like blowout port Is formed smaller than the cross-sectional area inside the reaction vessel .   The plasma processing apparatus according to claim 1, wherein a blow-out port is formed on a lower surface of the box-shaped reaction vessel.   The plasma processing apparatus according to claim 1, wherein the pair of electrodes are arranged so as to face each other vertically. The reaction vessel was formed Bian flat tubular plasma according to any of claims 1 to 3, characterized by comprising forming a 0.1~5mm the opposing distance of the side wall of the reaction vessel to the narrow direction Processing equipment.   5. The plasma processing apparatus according to claim 1, wherein the electrode is formed in a square shape in a plan view.   6. The plasma processing apparatus according to claim 1, wherein one electrode to be grounded is arranged closer to the blowing port than the other electrode to which a high voltage is applied.   3. The plasma processing apparatus according to claim 1, wherein an electrode is formed long in a direction parallel to the longitudinal direction of the blowout port.   The plasma processing apparatus according to claim 1, wherein the electrode is formed in a U shape having a lower surface opened in a side view.   A gas homogenizing chamber is provided for homogenizing the flow of the plasma generating gas in the reaction vessel, and the gas homogenizing chamber is configured such that the plasma generating gas supplied to the gas homogenizing chamber is the gas uniformed. The plasma processing apparatus according to any one of claims 1 to 8, wherein the plasma processing apparatus is formed so as to pass through the chemical conversion chamber and be introduced into the reaction vessel.   The plasma processing apparatus according to claim 9, wherein a flange that protrudes into the gas homogenization chamber is formed in the reaction vessel.   The plasma processing apparatus according to claim 9 or 10, wherein a gas homogenizing chamber is filled with a sphere. The plasma processing apparatus according to claim 1, flat, planar portion and the cross section of the reaction vessel is formed by a semi-circular arc-shaped curved surface portion, characterized by comprising forming a port blowout in the plane portion.   The plasma processing apparatus according to claim 12, wherein an electrode is disposed on the curved surface portion. The plasma processing apparatus according to claim 12 or 13, characterized in that formed by forming electrodes on semicircular shape.   The plasma processing apparatus according to any one of claims 12 to 14, wherein a lower surface of the reaction vessel is formed as a flat portion, and a gas for generating plasma is supplied to the reaction vessel from the side.   2. The plasma processing apparatus according to claim 1, wherein the reaction vessel is formed in a cylindrical shape, and a pair of electrodes are arranged so as to face each other vertically.   The plasma processing apparatus according to claim 16, wherein the electrode is formed in an annular shape in plan view.   18. The plasma processing apparatus according to claim 16, wherein one electrode to be grounded is disposed closer to the blowout port than the other electrode to which a high voltage is applied.   The plasma processing apparatus according to any one of claims 1 to 18, wherein a blowing port is formed along an inner surface of the reaction vessel formed along the lines of electric force.   The plasma processing apparatus according to any one of claims 1 to 18, wherein a blowing port is formed along each of a plurality of inner surfaces of the reaction vessel formed along the lines of electric force.   The plasma processing apparatus according to any one of claims 1 to 20, wherein at least one of the electrodes is cooled with a refrigerant.   The plasma according to any one of claims 1 to 21, wherein a volume reducing tool for reducing the volume of a discharge space formed between the pair of electrodes in the reaction vessel is provided in the reaction vessel. Processing equipment.   The plasma processing apparatus according to claim 22, wherein the volume reducing tool is formed of an insulating material.   24. The plasma processing apparatus according to claim 22, wherein the volume reducing device is cooled with a refrigerant.   The plasma processing apparatus according to claim 22, wherein the volume reducing tool is formed of a metal material and the volume reducing tool is cooled with a coolant.   The plasma processing apparatus according to any one of claims 21 to 25, wherein the refrigerant is ion-exchanged water. The plasma processing apparatus according to any one of claims 21 to 25 , wherein the refrigerant has antifreeze and insulating properties.   The plasma processing apparatus according to any one of claims 1 to 27, wherein a frequency of an alternating electric field applied between the pair of electrodes is set to 1 kHz to 200 MHz.   29. The plasma processing apparatus according to claim 1, wherein the surface roughness of the electrode in contact with the reaction vessel is 10 to 1000 [mu] m.   30. A plasma processing method, comprising: disposing an object to be processed below a blowout port of the plasma processing apparatus according to any one of claims 1 to 29;

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