JP4794741B2 - Deposited film forming method and deposited film forming apparatus - Google Patents

Description

上記（１）式を（２）式に代入し、これを満たす点Ａ_j（ｖｔ_j1，ｙ_j），点Ｂ_j（ｖｔ_j2，ｙ_j）を求め、
それぞれ３点以上の点Ａ_j及びＢ_jからそれぞれの近似曲線として下記（３）及び（４）式を得、
ｘ＝Ｆ₁（ｙ） …（３）
ｘ＝Ｆ₂（ｙ） …（４）
（３）式を満たす曲線および（４）式を満たす曲線が、それぞれ放電容器の開口部のＸ方向の両端部（基板搬送方向の両端部にあたる曲線）となるように設定し、放電容器の開口部を開口調整して帯状基板の堆積領域を制限する。
【００１７】
また、放電空間のＸ方向の中心位置から前記点Ａ_j（ｖｔ_j1，ｙ_j）と前記点Ｂ_j（ｖｔ_j2，ｙ_j）までの距離が等しくなるように、点Ａ_j（ｖｔ_j1，ｙ_j）及び点Ｂ_j（ｖｔ_j2，ｙ_j）を求めることが好ましい。
また、上記開口調整板の形状は、帯状基板の幅方向堆積速度分布から求められる前記点Ａ_j（ｖｔ_j1，ｙ_j）を通る弧および前記点Ｂ_j（ｖｔ_j2，ｙ_j）を通る弧が、放電容器の開口部のＸ方向の両端部の形状となるように設定し、放電容器の開口部を開口調整して帯状基板の堆積領域を制限することが好ましい。
【００１８】
さらに、上記開口調整板の形状が、帯状基板の幅方向堆積速度分布から求められる開口形状の±１０％以内になるように設定されることが好ましい。
【００１９】
そして、開口調整板の形状が、堆積膜の帯状基板の幅方向における膜厚分布のむらが１０％以内になるように設定されることが好ましい。
【００２０】
また、上記堆積膜が、マイクロ波プラズマＣＶＤ法により形成されることが好ましい。
【００２１】
さらに、複数の放電容器内をロール状に巻かれた状態から引き出された帯状基板が連続的に移動して再びロール状に巻かれるロール・ツー・ロール方式を採用することが好ましい。
【００２２】
一方、本発明の堆積膜形成装置は、複数の連続した真空容器内にプラズマを生起させ、帯状基板を長手方向に連続的に移動させながら、該基板上に連続的に堆積膜を形成する堆積膜形成装置において、放電容器の開口部に、堆積速度分布の測定に基づいて、基板幅方向における堆積膜厚のむらが減少するように形状を設定した開口調整板を設けるものである。
【００２３】
上記堆積膜形成装置において、
放電空間の前記帯状基板の搬送方向をＸ方向、
放電空間の前記帯状基板の面内で且つ搬送方向に垂直な方向をＹ方向、
放電空間内の帯状基板膜堆積面が通過する任意の点（ｘ_i，ｙ_j）において測定された前記帯状基板への膜の堆積速度をｄ（ｘ_i，ｙ_j）、
（但し、ｉ＝１，２，…，ｍ、ｊ＝１，２，…，ｎ、ここでｍ，ｎは共に３以上）
基板搬送速度をｖ、
理想的な堆積膜厚をδとした上で、
放電空間上のｙ＝ｙ_jにおけるＸ方向での堆積速度分布を前記ｄ（ｘ_i，ｙ_j）から二次曲線で近似し、下記（１）式を得、
ｄ_j（ｘ，ｙ_j）＝ｄ_j（ｖｔ，ｙ_j）＝ａ_jｔ²＋ｂ_jｔ＋ｃ_j （∵ｘ＝ｖｔ、ｔは時間） …（１）
さらに、放電空間上のｙ＝ｙ_jにおける堆積膜厚δ_j（ｘ，ｙ_j）が前記δとなるように下記（２）式を得、
【００２４】
【数６】

上記（１）式を（２）式に代入し、これを満たす点Ａ_j（ｖｔ_j1，ｙ_j），点Ｂ_j（ｖｔ_j2，ｙ_j）を求め、
それぞれ３点以上の点Ａ_j及びＢ_jからそれぞれの近似曲線として下記（３）及び（４）式を得、
ｘ＝Ｆ₁（ｙ） …（３）
ｘ＝Ｆ₂（ｙ） …（４）
（３）式を満たす曲線および（４）式を満たす曲線が、それぞれ放電容器の開口部のＸ方向の両端部となるように設定し、放電容器の開口部に帯状基板の堆積領域を制限するための開口調整板を設置する。
【００２５】
また、放電空間のＸ方向の中心位置から前記点Ａ_j（ｖｔ_j1，ｙ_j）と前記点Ｂ_j（ｖｔ_j2，ｙ_j）までの距離が等しくなるように、点Ａ_j（ｖｔ_j1，ｙ_j）及び点Ｂ_j（ｖｔ_j2，ｙ_j）を求めることが好ましい。
また、上記開口調整板の形状は、帯状基板の幅方向堆積速度分布から求められる前記点Ａ_j（ｖｔ_j1，ｙ_j）を通る弧および前記点Ｂ_j（ｖｔ_j2，ｙ_j）を通る弧が、放電容器の開口部のＸ方向の両端部の形状となるように設定し、放電容器の開口部に帯状基板の堆積領域を制限するための開口調整板を設置することが好ましい。
【００２６】
さらに、上記開口調整板の形状を、帯状基板の幅方向堆積速度分布から求められる開口調整板の形状の±１０％以内になるような形状を有する開口調整板を設置することが好ましい。
【００２７】
そして、上記堆積膜の帯状基板の幅方向における膜厚分布のむらを１０％以内になるような形状を有する開口調整板を設置することが好ましい。
【００２８】
また、上記堆積膜は、マイクロ波プラズマＣＶＤ装置により形成されることが好ましい。
【００２９】
さらに、複数の放電容器内をロール状に巻かれた状態から引き出された帯状基板が連続的に移動して再びロール状に巻かれるロール・ツー・ロール方式の装置として形成することが好ましい。
【００３０】
プラズマＣＶＤ法を用いた堆積膜形成方法では、成膜領域を拡大するために放電空間を広げた場合、堆積膜の膜厚に分布が生じる。また、マイクロ波電力の導入方法や堆積膜の成膜条件により、その分布は大きく変化する。例えば、マイクロ波電力を１方向から導入した場合と２方向から導入した場合とでは、堆積速度分布は大きく異なる。
【００３１】
本発明では、堆積速度分布を測定し、基板幅方向における堆積膜厚が均一になるように、開口調整板の形状を定める。開口調整板を放電容器の開口部に設けることにより、基板と放電領域を遮断し、帯状基板上に堆積する領域を制限することができる。この方法により、大面積にわたって均一な膜厚を有する堆積膜を形成することができる。
【００３２】
さらに、堆積膜の成膜条件を最適化するために、成膜条件を変更した場合においても、その都度開口調整板の形状を再決定することにより、均一な膜厚を有する堆積膜を形成することができる。
【００３３】
具体的に、開口調整板の形状を、帯状基板の幅方向堆積速度分布から求められる開口形状の±１０％以内に設定する方法としては、開口部の両端部の曲線が、前述したｘ＝Ｆ₁（ｙ）及びｘ＝Ｆ₂（ｙ）から±１０％以内ずれるように設定することが考えられる。
【００３４】
具体的には、開口部の一端の曲線が、
【００３５】
【数７】

で表される領域内に存在するようにし、
開口部の他端の曲線が
【００３６】
【数８】

で表される領域内に存在するようにする。
【００３７】
そこで本発明は、複数の連続した真空容器内にプラズマを生起させ、帯状基板をその長手方向に連続的に移動させながら、該基板上に連続的に堆積膜を形成する堆積膜形成方法において、
放電空間の前記帯状基板の搬送方向をＸ方向、
放電空間の前記帯状基板の面内で且つ搬送方向に垂直な方向をＹ方向、
放電空間内の帯状基板膜堆積面が通過する任意の点（ｘ_i，ｙ_j）において測定された前記帯状基板への膜の堆積速度をｄ（ｘ_i，ｙ_j）、
（但し、ｉ＝１，２，…，ｍ、ｊ＝１，２，…，ｎ、ここでｍ，ｎは共に３以上）
基板搬送速度をｖ、
理想的な堆積膜厚をδとした上で、
放電空間上のｙ＝ｙ_jにおけるＸ方向での堆積速度分布を前記ｄ（ｘ_i，ｙ_j）から二次曲線で近似し、下記（１）式を得、
ｄ_j（ｘ，ｙ_j）＝ｄ_j（ｖｔ，ｙ_j）＝ａ_jｔ²＋ｂ_jｔ＋ｃ_j （∵ｘ＝ｖｔ、ｔは時間） …（１）
さらに、放電空間上のｙ＝ｙ_jにおける堆積膜厚δ_j（ｘ，ｙ_j）が前記δとなるように下記（２）式を得、
【００３８】
【数９】

上記（１）式を（２）式に代入し、これを満たす点Ａ_j（ｖｔ_j1，ｙ_j），点Ｂ_j（ｖｔ_j2，ｙ_j）を求め、
それぞれ３点以上の点Ａ_j及びＢ_jからそれぞれの近似曲線として下記（３）及び（４）式を得、
ｘ＝Ｆ₁（ｙ） …（３）
ｘ＝Ｆ₂（ｙ） …（４）
さらに上記（３）式及び（４）式に基づいて定められる下記不等式（５）及び（６）を得、
１．１Ｆ₁（ｙ）−０．１Ｆ₂（ｙ）≦Ｘ≦０．９Ｆ₁（ｙ）＋０．１Ｆ₂（ｙ） …（５）
０．９Ｆ₂（ｙ）＋０．１Ｆ₁（ｙ）≦Ｘ≦１．１Ｆ₂（ｙ）−０．１Ｆ₁（ｙ） …（６）
（５）式を満たす曲線および（６）式を満たす曲線が、それぞれ放電容器の開口部のＸ方向の両端部となるように設定し、放電容器の開口部を開口調整して帯状基板の堆積領域を制限することを特徴とする堆積膜形成方法を提供する。
【００３９】
また、本発明は、複数の連続した真空容器内にプラズマを生起させ、帯状基板をその長手方向に連続的に移動させながら、該基板上に連続的に堆積膜を形成する堆積膜形成装置において、
放電空間の前記帯状基板の搬送方向をＸ方向、
放電空間の前記帯状基板の面内で且つ搬送方向に垂直な方向をＹ方向、
放電空間内の帯状基板膜堆積面が通過する任意の点（ｘ_i，ｙ_j）において測定された前記帯状基板への膜の堆積速度をｄ（ｘ_i，ｙ_j）、
（但し、ｉ＝１，２，…，ｍ、ｊ＝１，２，…，ｎ、ここでｍ，ｎは共に３以上）
基板搬送速度をｖ、
理想的な堆積膜厚をδとした上で、
放電空間上のｙ＝ｙ_jにおけるＸ方向での堆積速度分布を前記ｄ（ｘ_i，ｙ_j）から二次曲線で近似し、下記（１）式を得、
ｄ_j（ｘ，ｙ_j）＝ｄ_j（ｖｔ，ｙ_j）＝ａ_jｔ²＋ｂ_jｔ＋ｃ_j （∵ｘ＝ｖｔ、ｔは時間） …（１）
さらに、放電空間上のｙ＝ｙ_jにおける堆積膜厚δ_j（ｘ，ｙ_j）が前記δとなるように下記（２）式を得、
【００４０】
【数１０】

上記（１）式を（２）式に代入し、これを満たす点Ａ_j（ｖｔ_j1，ｙ_j），点Ｂ_j（ｖｔ_j2，ｙ_j）を求め、
それぞれ３点以上の点Ａ_j及びＢ_jからそれぞれの近似曲線として下記（３）及び（４）式を得、
ｘ＝Ｆ₁（ｙ） …（３）
ｘ＝Ｆ₂（ｙ） …（４）
さらに上記（３）式及び（４）式に基づいて定められる下記不等式（５）及び（６）を得、
１．１Ｆ₁（ｙ）−０．１Ｆ₂（ｙ）≦Ｘ≦０．９Ｆ₁（ｙ）＋０．１Ｆ₂（ｙ） …（５）
０．９Ｆ₂（ｙ）＋０．１Ｆ₁（ｙ）≦Ｘ≦１．１Ｆ₂（ｙ）−０．１Ｆ₁（ｙ） …（６）
（５）式を満たす曲線および（６）式を満たす曲線が、それぞれ放電容器の開口部のＸ方向の両端部となるように設定し、放電容器の開口部を開口調整して帯状基板の堆積領域を制限することを特徴とする堆積膜形成装置を提供する。
【００４１】
【発明の実施の形態】
以下、本発明の好適な実施の形態を添付図面に基づいて詳細に説明するが、本発明はこれらの実施の形態に限られない。
【００４２】
本発明は、上述のように、帯状基板をその長手方向に連続的に搬送して基板表面に機能性堆積膜を形成する装置において、放電容器の開口部に設けた開口調整板より、帯状基板と放電領域を遮断し、帯状基板上に堆積する領域を制御することを可能にしたものである。
【００４３】
これにより、従来のプラズマＣＶＤ法による堆積膜形成方法の大きな課題である放電空間の拡大による堆積膜の大面積化と同時に、帯状基板上に堆積する膜の膜厚および膜質分布を均一化が可能になる。
【００４４】
本発明で使用した堆積膜形成装置について、図面を参照して説明する。本発明で使用した装置は、図２に示す従来のロール・ツー・ロール方式の連続プラズマＣＶＤ装置である。
【００４５】
図２において、堆積膜形成装置は、基本的には帯状基板の巻き出し室２０１、高周波プラズマＣＶＤ法によるｎ型半導体層真空容器２０２、ｉ型半導体層真空容器２０３、ｉ型半導体層真空容器２０４、ｐ型半導体層真空容器２０５、内部に２個の放電容器２０７ａ、２０７ｂを有するマイクロ波プラズマＣＶＤ法によるｉ型半導体層真空容器２０６、および帯状基板の巻き取り室２０８から構成されており、各真空容器２０２〜２０６の間はそれぞれガスゲート２０９によって接続されている。
【００４６】
本発明の装置において、帯状基板２１０は巻き出し室２０１内のボビン２１１から巻き出され、巻き取り室２０８内のボビン２１２に巻き取られるまでにガスゲート２０９で接続された５基の真空容器２０２〜２０６を通過しながら移動させられ、その間に基板表面にｎｉｐ構造の半導体の堆積膜が形成される。
【００４７】
各真空容器２０２〜２０６には、基板を加熱する加熱ヒータ２１３、不図示のガス供給手段から供給される成膜ガスを放電容器内へ導入するガス導入管２１４、導入ガスを加熱するガス加熱ヒータ２１５、不図示の排気手段により放電容器を排気する排気管２１６および排気調整バルブ２１７が設けられている。なお、巻き出し室２０１および巻き取り室２０８にも、排気管２１６および排気調整バルブ２１７が設けられている。
【００４８】
マイクロ波ＣＶＤ法を用いる真空容器２０６内の放電領域２１８には、放電容器２０７ａ、２０７ｂの開口部に帯状基板の堆積膜厚分布を制御するために開口調整板２１９を設置し、マイクロ波発振器２２０から導波管２２１を通して、放電容器内の成膜ガスにエネルギーを与えて放電を生起するためのマイクロ波電力を供給するアプリケータ２２２と、プラズマにＲＦ発振器２２７からＲＦ電力を印加するバイアス棒２２３とが設けられ、供給された原料ガスを分解して堆積膜の形成が行われる。
【００４９】
ＲＦプラズマＣＶＤ法を用いる真空容器２０２〜２０５内の放電領域２２４には、原料ガスにＲＦ電力を印加するカソード２２５が設けられ、ＲＦプラズマＣＶＤ法による堆積膜の形成が行われる。
【００５０】
ガスゲート２０９は、各真空容器を分離独立させ、帯状基板２１０を各放電領域の中を貫通させ、連続的に搬送する目的で設けたものである。ゲートガス導入管２２６からゲートガスを導入し、隣り合う真空容器の原料ガスが混合すること防ぐことにより、異なる組成の良質な堆積膜を多層形成することができる。
【００５１】
このような堆積膜形成装置を用いて、本発明の堆積膜形成方法は実施される。すなわち、本発明の堆積膜形成方法は、複数の連続した真空容器内にプラズマを生起させ、帯状基板をその長手方向に連続的に移動させながら、該基板上に連続的に堆積膜を形成する堆積膜形成方法であり、放電容器の開口部を、堆積速度分布の測定に基づいて、基板幅方向における堆積膜厚のむらが減少するように形状を設定した開口調整板で開口調整して成膜を行う。
【００５２】
具体的には、放電空間の前記帯状基板の搬送方向をＸ方向、
放電空間の前記帯状基板の面内で且つ搬送方向に垂直な方向をＹ方向、
放電空間内の帯状基板膜堆積面が通過する任意の点（ｘ_i，ｙ_j）において測定された前記帯状基板への膜の堆積速度をｄ（ｘ_i，ｙ_j）、
（但し、ｉ＝１，２，…，ｍ、ｊ＝１，２，…，ｎ、ここでｍ，ｎは共に３以上）
基板搬送速度をｖ、
理想的な堆積膜厚をδとする。
ここで放電空間上のｙ＝ｙ_jにおけるＸ方向での堆積速度分布を前記ｄ（ｘ_i，ｙ_j）から二次曲線で近似して、
ｄ_j（ｘ，ｙ_j）＝ｄ_j（ｖｔ，ｙ_j）＝ａ_jｔ²＋ｂ_jｔ＋ｃ_j （∵ｘ＝ｖｔ、ｔは時間） …（１）
とする。一方、放電空間上のｙ＝ｙ_jにおける堆積膜厚δ_j（ｘ，ｙ_j）が前記δとなるようにするためには、
【００５３】
【数１１】

を満たすｔ_j1からｔ_j2までの間、膜堆積を行うこととなる。
そこで、上記（１）式を（２）式に代入し、これを満たす点Ａ_j（ｖｔ_j1，ｙ_j），点Ｂ_j（ｖｔ_j2，ｙ_j）を得ることができる。つまり、点Ａ_jから点Ｂ_jまでの間堆積を行うことにより堆積膜厚をおおむねとすることができる。
そして、それぞれのｊについて点Ａ_jから点Ｂ_jを求め、これらの点のＹ方向における分布をそれぞれ例えば二次曲線で近似すると、
点Ａ_j（３点以上）から近似により導かれる二次曲線は、
ｘ＝Ｆ₁（ｙ） …（３）
点Ｂ_j（３点以上）から近似により導かれる二次曲線は、
ｘ＝Ｆ₂（ｙ） …（４）
となる。
次に、（３）式を満たす曲線および（４）式を満たす曲線が、それぞれ放電容器の開口部の両端部となるように設定し、放電容器の開口部を開口調整して帯状基板の堆積領域を制限することにより、基板の搬送方向と垂直な方向の全ての部分で、膜厚がおおむねδとなるような膜形成条件（開口調整条件）が得られる。
【００５４】
本発明において、（３）式を満たす曲線および（４）式を満たす曲線が、それぞれ放電容器の開口部の両端部となるように設定するとは、帯状基板上に存在するこれらの曲線を、基板面と垂直な方向に所定の距離（公知の距離を採用することが可能）だけ離れた位置に、例えば開口調整板の端部が存在するように設定することを意味する。
【００５５】
尚、上記（１）及び（２）式から点Ａ_j（ｖｔ_j1，ｙ_j）及び点Ｂ_j（ｖｔ_j2，ｙ_j）を求めるに際しては、前提条件として例えば、放電空間のＸ方向の中心位置から点Ａ_j（ｖｔ_j1，ｙ_j）と点Ｂ_j（ｖｔ_j2，ｙ_j）までの距離が等しくなるように設定したり、点Ａ_j（ｖｔ_j1，ｙ_j）もしくは点Ｂ_j（ｖｔ_j2，ｙ_j）の一方のＸ方向の位置（即ちｖｔ_j1もしくはｖｔ_j2）を固定して他方のＸ方向の位置を求めることで行うことができる。この場合、上記の前提条件は、予め測定された堆積速度およびその分布等を考慮して適宜選択することができ、以下で説明する各実施例においては、堆積速度が大きく且つそのばらつきが小さい領域で膜堆積を行うべく、放電空間のＸ方向の中心位置から点Ａ_j（ｖｔ_j1，ｙ_j）と点Ｂ_j（ｖｔ_j2，ｙ_j）までの距離が等しくなるように設定している。
また、開口調整板の形状は、帯状基板の幅方向堆積速度分布から求められる前記点Ａ_j（ｖｔ_j1，ｙ_j）を通る弧および前記点Ｂ_j（ｖｔ_j2，ｙ_j）を通る弧が、放電容器の開口部の両端部の形状となるように設定し、放電容器の開口部を開口調整して帯状基板の堆積領域を制限する。
【００５６】
さらに、開口調整板の形状が、帯状基板の幅方向堆積速度分布から求められる開口形状の±１０％以内になるように設定されることが好ましい。この場合の具体的な設定方法は前述した（５）式（６）式で表すことができる。
【００５７】
この堆積膜はプラズマＣＶＤ法により形成され、特にマイクロ波プラズマＣＶＤ法により形成されることが好ましい。
【００５８】
また、開口調整板の形状が、堆積膜の帯状基板の幅方向における膜厚分布のむらが１０％以内になるように設定されることが好ましい。
【００５９】
堆積膜の形成を連続的に行うには、複数の放電容器内をロール状基板が連続的に移動するロール・ツー・ロール方式を採用することが好ましい。
【００６０】
すなわち、本発明では、堆積速度分布を測定し、基板幅方向における堆積膜厚が均一になるように、開口調整板の形状を定める。開口調整板を放電容器の開口部に設けることにより、基板と放電領域を遮断し、帯状基板上に堆積する領域を制限することができる。この方法により、大面積にわたって均一な膜厚を有する堆積膜を形成することができる。
【００６１】
さらに、堆積膜の成膜条件を最適化するために、成膜条件を変更した場合においても、その都度開口調整板の形状を再決定することにより、均一な膜厚を有する堆積膜を形成することができる。
【００６２】
放電容器の開口部に堆積膜厚分布を制御するための開口調整板を設けず、堆積する領域の制限を行わないで、放電容器の開口部全域にわたって堆積膜を形成すると、その堆積膜厚速度は大きな分布をもつ。なぜなら、マイクロ波電力導入部からの距離が離れるにつれて堆積速度分布は小さくなる傾向があり、堆積速度分布はその堆積膜形成装置のマイクロ波電力の導入方法によって、特徴的な分布が現れる。
【００６３】
例えば、図１に示すような方法でマイクロ波電力を４個のアプリケータ１０１を用いてマイクロ波電力の導入を行った場合、両端部と比較して中心部の堆積速度が小さい分布となる。このような堆積速度分布にあわせて、図１に示すような形状の開口調整板１０２を放電容器の開口部に設けることにより、放電容器開口部に膜厚分布に応じた開口部１０３を形成し、帯状基板１０４上に均一な膜厚および膜質を有する堆積膜を得ることが可能になる。
【００６４】
また、特性を向上させるために、成膜条件を変更させた場合においても、開口調整板の形状を変更することで均一な膜厚を有する堆積膜を形成することが可能となる。
【００６５】
【実施例】
以下、本発明の堆積膜形成方法および堆積膜形成装置について具体的実施例を示すが、本発明はこれらの実施例によって何ら限定されるものではない。
【００６６】
（実施例１）
図２に示した堆積膜形成装置を用いて、本発明の堆積膜形成方法について、手順にしたがって説明する。まず、本実験では、マイクロ波ＣＶＤ法を用いて作製するｉ層の堆積膜の堆積速度分布を調べた。図２の堆積膜形成装置では、４個のアプリケータ２２２を用いてマイクロ波電力の導入を行っている。作製条件を表１に示す。
【００６７】
【表１】

【００６８】
基板送り出し機構を有する真空容器２０１に、十分脱脂、洗浄を行ったステンレス帯状基板（ＳＵＳ４３０、幅３５０ｍｍ×長さ３００ｍ×厚さ０．２ｍｍ）２１０の巻き付けられたボビン２１１をセットし、帯状基板をガスゲート２０９、ｎ型半導体層真空容器２０２、ｉ型半導体層真空容器２０３、ｉ型半導体層真空容器２０６、ｉ型半導体層真空容器２０４、ｐ型半導体層真空容器２０５を順次介して、帯状基板の巻き取り室２０８まで通し、弛みの無い程度に張力調整を行った。各真空容器内は、不図示の排気装置で１．３×１０^-4Ｐａ（１×１０^-6Ｔｏｒｒ）まで減圧した。
【００６９】
まず、放電容器２０７ａ、２０７ｂには、それぞれの放電容器の開口部に堆積膜厚分布を制御するための開口調整板２１９は設けずに、放電容器２０７ａ、２０７ｂの開口部全域にわたって堆積膜を形成し、堆積速度分布を測定した。
【００７０】
成膜時の加熱処理として、ガスゲート２０９にゲートガス導入管２２６から、ゲートガスとしてＨ₂をそれぞれ１０００ｓｃｃｍを導入し、基板加熱用ヒータ２１３により、帯状基板２１０を３００℃に加熱した。
【００７１】
原料ガスをガス導入管２１４から各放電容器に導入し、帯状基板を１２７０ｍｍ／ｍｉｎの速度で搬送させ、マイクロ波発振器２２０およびＲＦ発振器２２７から放電容器内にマイク口波電力およびＲＦ電力を印加して、成膜領域にプラズマ放電を生起し、帯状基板上にｉ型のアモルファスシリコン膜を形成した。
【００７２】
放電状態の安定を確認した後、搬送を止めて静止サンプルを作製した。分光器により得られた堆積膜の堆積速度を測定した。また、幅方向の分布を評価するため、堆積速度は図３に示すように帯状基板の中央部（Ｃ）および両端部（Ｆ、ＦＣ、ＲＣ、Ｒ）の５点、基板搬送方向に１０点の合計５０点を測定した。その結果を、表２および図４に示す。なお、表２中Ｐｏｓｉｔｉｏｎが３０〜１１０ｍｍの点は放電容器２０７ａ中にあり、Ｐｏｓｉｔｉｏｎが２５０〜３３０ｍｍの点は放電容器２０７ｂ中にある。
【００７３】
【表２】

【００７４】
表２および図４から分かるように、得られた堆積膜の堆積速度は帯状基板幅方向および搬送方向に一定ではなく、帯状基板２１０を搬送させながら堆積させた場合、総堆積膜厚は幅方向に大きな分布を生じた。
【００７５】
堆積速度分布の結果をもとに、左右２つの放電容器ごとに開口調整板の形状を決定した。
【００７６】
まず初めに、放電空間Ａについて求めた。
放電空間の帯状基板の搬送方向をＸ方向、
放電空間の帯状基板の面内で且つ搬送方向に垂直な方向をＹ方向、
放電空間内の帯状基板膜堆積面が通過する任意の点（ｘ_i，ｙ_j）において測定された前記帯状基板への膜の堆積速度をｄ（ｘ_i，ｙ_j）、
基板搬送速度をｖ＝１２７０（ｍｍ／ｍｉｎ）
理想的な堆積膜厚δ＝３００（Å）
とする。
【００７７】
先ず、放電空間上のｙ₁＝１７５（ｍｍ），ｘ_P1≦ｘ₁≦ｘ_Q1における堆積膜厚をδ₁（ｘ，ｙ₁）
開口調整板を設けなかった時の放電空間の搬送方向の幅Ｌ＝１４０
ｘ_P1＋ｘ_Q1＝１４０ （この式は放電空間の中心線からみてｘ_P1，ｘ_Q1を対称とするために設定したものであり、必須ではない）
として、
ｄ₁（ｘ，ｙ₁）＝ｄ₁（ｖｔ，ｙ₁）＝−４．２ｔ²＋２７ｔ＋２４ （∵ｘ＝ｖｔ）
【００７８】
【数１２】

（１）式を満たす（ｔ，ｙ₁）＝Ａ₁（０．２８，１７５），Ｂ₁（６．３２，１７５）
∴（ｘ，ｙ）＝Ａ₁（６．０，１７５），Ｂ₁（１３４，１７５）
【００７９】
次に、放電空間上のｙ₂＝３５（ｍｍ），ｘ_P2≦ｘ₂≦ｘ_Q2における堆積膜厚をδ（ｘ，ｙ₂）
開口調整板を設けなかった時の放電空間の搬送方向の幅Ｌ＝１４０
ｘ_P2＋ｘ_Q2＝１４０ （この式は放電空間の中心線からみてｘ_P2，ｘ_Q2を対称とするために設定したものであり、必須ではない）
として、
ｄ₂（ｘ，ｙ₂）＝ｄ₂（ｖｔ，ｙ₂）＝−５．０ｔ²＋３２ｔ＋３７ （∵ｘ＝ｖｔ）
【００８０】
【数１３】

（１）’式を満たす（ｔ，ｙ₂）＝Ａ₂（０．８５，３５），Ｂ₂（５．７５，３５）
∴（ｘ，ｙ）＝Ａ₂（１８，３５），Ｂ₂（１２２，３５）
【００８１】
次に、放電空間上のｙ₃＝３１５（ｍｍ），ｘ_P3≦ｘ₃≦ｘ_Q3における堆積膜厚をδ（ｘ，ｙ₃）
開口調整板を設けなかった時の放電空間の搬送方向の幅Ｌ＝１４０
ｘ_P3＋ｘ_Q3＝１４０ （この式は放電空間の中心線からみてｘ_P3，ｘ_Q3を対称とするために設定したものであり、必須ではない）
として、
ｄ₃（ｘ，ｙ₃）＝ｄ₃（ｖｔ，ｙ₃）＝−５．２ｔ²＋３３ｔ＋３５ （∵ｘ＝ｖｔ）
【００８２】
【数１４】

（１）”式を満たす（ｔ，ｙ₃）＝Ａ₃（０．７８，３１５），Ｂ₃（５．８２，３１５）
∴（ｘ，ｙ）＝Ａ₃（１７，３１５），Ｂ₃（１２３，３１５）
【００８３】
点Ａ₁，Ａ₂，Ａ₃を通る二次曲線 ｘ＝Ｆ₁（ｙ）＝５．９×１０^-4ｙ²−０．２１ｙ＋２４…（２）
点Ｂ₁，Ｂ₂，Ｂ₃を通る二次曲線 ｘ＝Ｆ₂（ｙ）＝−５．９×１０^-4ｙ²＋０．２１＋１１６…（３）
【００８４】
同様に、放電空間Ｂについて求める。
基板搬送速度をｖ＝１２７０（ｍｍ／ｍｉｎ）
理想的な堆積膜厚δ＝３００（Å）
とする。
【００８５】
先ず、放電空間上のｙ₁＝１７５（ｍｍ），ｘ_P1≦ｘ₁≦ｘ_Q1における堆積膜厚をδ₁（ｘ，ｙ₁）
開口調整板を設けなかった時の放電空間の搬送方向の幅Ｌ＝１４０
ｘ_P1＋ｘ_Q1＝１４０ （この式は放電空間の中心線からみてｘ_P1，ｘ_Q1を対称とするために設定したものであり、必須ではない）
として、
ｄ₁（ｘ，ｙ₁）＝ｄ₁（ｖｔ，ｙ₁）＝−４．７ｔ²＋３１ｔ＋１９ （∵ｘ＝ｖｔ）
【００８６】
【数１５】

（１）式を満たす（ｔ，ｙ₁）＝Ａ₁（０．２９，１７５），Ｂ₁（６．３１，１７５）
∴（ｘ，ｙ）＝Ａ₁（６．１，１７５），Ｂ₁（１３３．９，１７５）
【００８７】
次に、放電空間上のｙ₂＝３５（ｍｍ），ｘ_P2≦ｘ₂≦ｘ_Q2における堆積膜厚をδ（ｘ，ｙ₂）
開口調整板を設けなかった時の放電空間の搬送方向の幅Ｌ＝１４０
ｘ_P2＋ｘ_Q2＝１４０ （この式は放電空間の中心線からみてｘ_P2，ｘ_Q2を対称とするために設定したものであり、必須ではない）
として、
ｄ₂（ｘ，ｙ₂）＝ｄ₂（ｖｔ，ｙ₂）＝−５．０ｔ²＋３４ｔ＋３１ （∵ｘ＝ｖｔ）
【００８８】
【数１６】

（１）’式を満たす（ｔ，ｙ₂）＝Ａ₂（０．８３，３５），Ｂ₂（５．７７，３５）
∴（ｘ，ｙ）＝Ａ₂（１７．６，３５），Ｂ₂（１２２．４，３５）
【００８９】
次に、放電空間上のｙ₃＝３１５（ｍｍ），ｘ_P3≦ｘ₃≦ｘ_Q3における堆積膜厚をδ（ｘ，ｙ₃）
開口調整板を設けなかった時の放電空間の搬送方向の幅Ｌ＝１４０
ｘ_P3＋ｘ_Q3＝１４０ （この式は放電空間の中心線からみてｘ_P3，ｘ_Q3を対称とするために設定したものであり、必須ではない）
として、
ｄ₃（ｘ，ｙ₃）＝ｄ₃（ｖｔ，ｙ₃）＝−５．６ｔ²＋３８ｔ＋２５ （∵ｘ＝ｖｔ）
【００９０】
【数１７】

（１）”式を満たす（ｔ，ｙ₃）＝Ａ₃（０．７７，３１５），Ｂ₃（５．８３，３１５）
∴（ｘ，ｙ）＝Ａ₃（１６．３，３１５），Ｂ₃（１２３．７，３１５）
【００９１】
点Ａ₁，Ａ₂，Ａ₃を通る二次曲線 ｘ＝Ｆ₁（ｙ）＝５．９×１０^-4ｙ²−０．２１ｙ＋２４…（２）
点Ｂ₁，Ｂ₂，Ｂ₃を通る二次曲線 ｘ＝Ｆ₂（ｙ）＝−５．９×１０^-4ｙ²＋０．２１＋１１６…（３）
【００９２】
得られた曲線から、図１に示すような堆積領域１０３の幅方向の分布をもたせた開口調整板１０２を使用して、帯状基板１０４の堆積膜厚分布の制御を行い、ｎｉｐ型のシングルセルを作製した。
【００９３】
ガス導入までの工程は実験１と同様に行い、帯状基板を１２７０ｍｍ／ｍｉｎの速度で搬送させ、マイクロ波発振器２２０およびＲＦ発振器２２７から放電容器内にマイクロ波電力およびＲＦ電力を印可して、成膜領域にプラズマ放電を生起し、帯状基板上にｎｉｐ型のアモルファスシリコン膜を形成した。
【００９４】
形成されたｎｉｐ型のアモルファスシリコン膜上に、透明電極としてＩＴＯ（Ｉｎ₂Ｏ₃＋ＳｎＯ₂）を真空蒸着により７０ｎｍ蒸着し、さらに集電電極として、Ａｌを真空蒸着にて２μｍ蒸着し、光起電力素子を作製した。得られた光起電力素子のＣ−Ｖ特性からｉ層の膜厚分布を評価した。得られた堆積膜の膜厚分布を、表３に示す。
【００９５】
【表３】

【００９６】
得られた堆積膜厚は幅方向に均一であり、その堆積膜厚のむらが、０から１０％以内に押さえられることが分かった。
【００９７】
次に、図５に示すようなｎｉｐｎｉｐｎｉｐ型のトリプルセルを形成することが可能なロール・ツー・ロールプラズマＣＶＤ装置を用いて、トリプルセルを作製した。成膜条件を表４に示す。
【００９８】
【表４】

【００９９】
基板送り出し機構を有する真空容器５０１に、上記のステンレス帯状基板（ＳＵＳ４３０）の代わりに、下部電極として、スパッタリング法によりアルミニウム薄膜（０．２μｍ）およびＺｎＯ薄膜（１．２μｍ）を蒸着したステンレス帯状基板（ＳＵＳ４３０）５０２の巻き付けられたボビン５０３をセットし、上記実験と同様に帯状基板をガスゲート５０４、ｎ型半導体層真空容器５０５、５０６、５０７、ｉ型半導体層真空容器５０８、５０９、マイクロ波プラズマ法による第２のｉ型半導体層真空容器５１０、５１１、ＲＦプラズマＣＶＤ法によるｉ型半導体層真空容器５１２、５１３、５１４、ｉ型半導体層真空容器５１５、５１６、ｐ型半導体層真空容器５１７、５１８、５１９を介して、帯状基板の巻き取り室５２０まで通し、弛みの無い程度に張力調整を行った。各真空容器５０５〜５１９を不図示の排気装置で、１．３×１０^-4Ｐａ（１×１０^-6Ｔｏｒｒ）まで減圧した。
【０１００】
マイクロ波プラズマ法によるｉ型半導体層放電容器５２１、５２２には、それぞれの開口部に帯状基板５０２の堆積膜厚分布を制御するために、図１に示すような開口調整板１０２が設けられている。これにより堆積領域１０３は限定される。
【０１０１】
成膜時の加熱処理として、ガスゲートにゲートガス導入管から、ゲートガスとしてＨ₂をそれぞれ１０００ｓｃｃｍ導入し、基板加熱用ヒータにより、帯状基板を３００℃に加熱した。
【０１０２】
原料ガスをガス導入管から各放電容器に導入し、帯状基板を１２７０ｍｍ／ｍｉｎの速度で搬送させ、マイクロ波発振器、高周波発振器から各放電容器内に電力を印加して、成膜領域にプラズマ放電を生起し、帯状基板上にｎｉｐｎｉｐｎｉｐ型のアモルファスシリコン膜を形成した。
【０１０３】
帯状基板の１ロール分を搬送させた後、すべてのプラズマ、すべてのガスの供給、すべてのランプヒータの通電、搬送を停止した。次に放電容器リーク用の窒素（Ｎ₂）ガスを放電容器に導入し、大気圧に戻して巻き取り用ボビンに巻き取られた帯状基板を取り出した。
【０１０４】
形成されたｎｉｐｎｉｐｎｉｐ型のアモルファスシリコン膜上に、透明電極としてＩＴＯ（Ｉｎ₂Ｏ₃＋ＳｎＯ₂）を真空蒸着により７０ｎｍ蒸着し、さらに集電電極として、Ａｌを真空蒸着にて２μｍ蒸着し、光起電力素子を作製した。
【０１０５】
形成された太陽電池の評価はスペクトル感度特性およびＡＭ値１．５、エネルギー密度１００ｍＷ／ｃｍ²の擬似太陽光を照射したときの光電変換効率ηを測定することにより評価した。また、幅方向の分布を評価するため、スペクトル感度特性および光電変換効率は帯状基板の幅方向の中央部（Ｃ）および両端部（Ｆ、ＦＣ、ＲＣ、Ｒ）の５点を測定した。その結果を表５に示す。
【０１０６】
【表５】

【０１０７】
また、３５０ｍｍ×２４０ｍｍの大きさの太陽電池を作製し、基板全体の効率を評価した。その結果を表６に示す。
【０１０８】
【表６】

【０１０９】
表５および表６から明らかなように、開口調整板により、総堆積膜厚のむらが１０％以内に押さえられることにより、その相対感度および光電変換効率のむらが押さえられることが判った。また、光電変換効率のむらが押さえられることにより、光起電力素子の基板幅方向全体の光電変換効率が向上させることが可能であること判った。
【０１１０】
（比較例１）
本比較例では、実施例１が図１に示したような開口調整板１０２を用いて成膜したのに対して、幅方向に開口長が均一な図６に示す開口調整板６０１を用いた。その他の成膜条件は、実施例１と同様とした。本比較例では、マイクロ波電力を初め、その他の成膜条件は表１に示すように設定し作製した。
【０１１１】
得られた堆積膜の幅方向膜厚分布は、表３に示すような結果になった。得られた堆積膜の膜厚分布のむらは、１０％より大きいことが判った。
【０１１２】
実施例１と同様に、帯状基板上にｎｉｐｎｉｐｎｉｐ型のアモルファスシリコン膜を形成した。ｎ型層上に、透明電極としてＩＴＯ（Ｉｎ₂Ｏ₃＋ＳｎＯ₂）を真空蒸着により７０ｎｍ蒸着し、さらに集電電極として、Ａｌを真空蒸着にて２μｍ蒸着し、光起電力素子を作製した。
【０１１３】
形成された光起電力素子の評価はスペクトル感度特性およびＡＭ値１．５、エネルギー密度１００ｍＷ／ｃｍ²の擬似太陽光を照射したときの光電変換効率ηを測定することにより評価した。
【０１１４】
その結果を表５に示す。また、３５０ｍｍ×２４０ｍｍの大きさの光起電力素子を作製し、基板幅方向全体の効率を評価した。その結果を表６に示す。
【０１１５】
開口調整板６０１を用いた場合、堆積膜厚のむらが１０％より大きかった。堆積膜厚のむらにより、光電変換効率のむらが生じ、その結果、光起電力素子の基板幅方向全体の光電変換効率を向上させるには至らなかった。
【０１１６】
（実施例２）
本実施例では、実施例１が図２に示したような４個のアプリケータ２２２用いて、マイクロ波電力を導入してｉ層を成膜したのに対し、図７に示すように、１個のアプリケータ７０１用いて、マイクロ波電力を導入してｉ層を成膜した場合の実施例を述べる。成膜条件は、表１に示すように設定して作製した。なお、図７において、７０２は開口部調整板、７０３は堆積領域、７０４は帯状基板である。
【０１１７】
実施例１に示した手順にしたがって、各真空容器に帯状基板（ＳＵＳ４３０）を通し、不図示の排気装置により１．３×１０^-4Ｐａ（１×１０^-6Ｔｏｒｒ）まで減圧した後、放電を生起し、帯状基板上にｉ型のアモルファスシリコン膜を形成する。放電容器２０７ａ、２０７ｂには、それぞれの放電容器の開口部に堆積膜厚分布を制御するための開口調整板２１９は設けず、放電容器２０７ａ、２０７ｂの開口部全域にわたって堆積膜を形成させる。放電状態の安定を確認した後、搬送を止めて静止サンプルを作製した。
【０１１８】
また、幅方向の分布を評価するため、堆積速度は図３に示すように帯状基板の中央部（Ｃ）および両端部（Ｆ、Ｒ）の３点、基板搬送方向に７点の合計２１点を分光器により、堆積速度を測定した。得られた堆積膜の堆積速度分布の結果を表７および図８に示す。
【０１１９】
【表７】

【０１２０】
表７および図８から分かるように、得られた堆積膜の堆積速度は基板幅方向および搬送方向に一定ではなく、帯状基板２１０を搬送させて堆積させた場合、その総堆積膜厚は、幅方向に大きな分布を生じた。
【０１２１】
その堆積速度分布の測定を基づいて、開口調整板の形状を決定した。
放電空間の帯状基板の搬送方向をＸ方向、
放電空間の帯状基板の面内で且つ搬送方向に垂直な方向をＹ方向、
放電空間内の帯状基板膜堆積面が通過する任意の点（ｘ_i，ｙ_j）において測定された前記帯状基板への膜の堆積速度をｄ（ｘ_i，ｙ_j）、
基板搬送速度をｖ＝１２７０（ｍｍ／ｍｉｎ）
理想的な堆積膜厚δ＝７００（Å）
とする。
【０１２２】
先ず、放電空間上のｙ₁＝６０（ｍｍ），ｘ_P1≦ｘ₁≦ｘ_Q1における堆積膜厚をδ₁（ｘ，ｙ₁）
開口調整板を設けなかった時の放電空間の搬送方向の幅Ｌ＝２５０
ｘ_P1＋ｘ_Q1＝２５０ （この式は放電空間の中心線からみてｘ_P1，ｘ_Q1を対称とするために設定したものであり、必須ではない）
として、
ｄ₁（ｘ，ｙ₁）＝ｄ₁（ｖｔ，ｙ₁）＝−１．２ｔ²＋１６ｔ＋３５ （∵ｘ＝ｖｔ）
【０１２３】
【数１８】

（１）式を満たす（ｔ，ｙ₁）＝Ａ₁（２．８，６０），Ｂ₁（９．０，６０）
∴（ｘ，ｙ）＝Ａ₁（５９，６０），Ｂ₁（１９１，６０）
【０１２４】
次に、放電空間上のｙ₂＝２０（ｍｍ），ｘ_P2≦ｘ₂≦ｘ_Q2における堆積膜厚をδ（ｘ，ｙ₂）
開口調整板を設けなかった時の放電空間の搬送方向の幅Ｌ＝２５０
ｘ_P2＋ｘ_Q2＝２５０ （この式は放電空間の中心線からみてｘ_P2，ｘ_Q2を対称とするために設定したものであり、必須ではない）
として、
ｄ₂（ｘ，ｙ₂）＝ｄ₂（ｖｔ，ｙ₂）＝−１．３ｔ²＋１９ｔ＋２９ （∵ｘ＝ｖｔ）
【０１２５】
【数１９】

（１）’式を満たす（ｔ，ｙ₂）＝Ａ₂（０．９１，３５），Ｂ₂（１０．８９，３５）
∴（ｘ，ｙ）＝Ａ₂（１９，２０），Ｂ₂（２３１，２０）
【０１２６】
次に、放電空間上のｙ₃＝１００（ｍｍ），ｘ_P3≦ｘ₃≦ｘ_Q3における堆積膜厚をδ（ｘ，ｙ₃）
開口調整板を設けなかった時の放電空間の搬送方向の幅Ｌ＝２５０
ｘ_P3＋ｘ_Q3＝２５０ （この式は放電空間の中心線からみてｘ_P3，ｘ_Q3を対称とするために設定したものであり、必須ではない）
として、
ｄ₃（ｘ，ｙ₃）＝ｄ₃（ｖｔ，ｙ₃）＝−５．２ｔ²＋３３ｔ＋３５ （∵ｘ＝ｖｔ）
【０１２７】
【数２０】

（１）”式を満たす（ｔ，ｙ₃）＝Ａ₃（０．３５，１００），Ｂ₃（１１．４５，１００）
∴（ｘ，ｙ）＝Ａ₃（１７，１００），Ｂ₃（１２３，１００）
【０１２８】
点Ａ₁，Ａ₂，Ａ₃を通る二次曲線 ｘ＝Ｆ₁（ｙ）＝２．６×１０^-2ｙ²−５．２ｙ−９４…（２）
点Ｂ₁，Ｂ₂，Ｂ₃を通る二次曲線 ｘ＝Ｆ₂（ｙ）＝−５．９×１０^-4ｙ²＋６．０ｙ＋１０７…（３）
【０１２９】
得られた曲線から、開口調整板の形状を決定し、図７に示すような堆積領域７０３の幅方向の分布をもたせた開口調整板７０２を使用して、帯状基板７０４の堆積膜厚分布を制御を行い、ｎｉｐ型のシングルセルを作製した。ガス導入までの行程は実験１と同様に行い、帯状基板７０４を１２７０ｍｍ／ｍｉｎの速度で搬送させ、マイクロ波発振器２２０およびＲＦ発振器２２７から放電容器内にマイクロ波電力およびＲＦ電力を印可して、成膜領域にプラズマ放電を生起し、帯状基板上にｎｉｐ型のアモルファスシリコン膜を形成した。
【０１３０】
形成されたｎｉｐ型のアモルファスシリコン膜上に、透明電極としてＩＴＯ（Ｉｎ₂Ｏ₃＋ＳｎＯ₂）を真空蒸着により７０ｎｍ蒸着し、さらに集電電極として、Ａｌを真空蒸着にて２μｍ蒸着し、光起電力素子を作製した。得られた光起電力素子のＣ−Ｖ特性からｉ層の膜厚分布を評価した。得られた堆積膜の膜厚分布を、表８に示す。
【０１３１】
【表８】

【０１３２】
得られた堆積膜厚は幅方向に均一であり、その堆積膜厚のむらが、１０％以内に押さえられることが判った。
【０１３３】
次に、図５に示すようなｎｉｐｎｉｐｎｉｐ型のトリプルセルを形成することが可能なロール・ツー・ロールプラズマＣＶＤ装置を用いて、トリプルセルを作製した。成膜条件を表４に示す。
【０１３４】
基板送り出し機構を有する真空容器５０１に、ステンレス帯状基板（ＳＵＳ４３０）の代わりに、下部電極として、スパッタリング法によりアルミニウム薄膜（０．２μｍ）およびＺｎＯ薄膜（１．２μｍ）を蒸着したステンレス帯状基板（ＳＵＳ４３０）５０２の巻き付けられたボビン５０３をセットし、上記実験と同様に帯状基板をガスゲート５０４、ｎ型半導体層真空容器５０５、５０６、５０７、ｉ型半導体層真空容器５０８、５０９、マイクロ波プラズマ法によるｉ型半導体層真空容器５１０、５１１、ＲＦプラズマＣＶＤ法によるｉ型半導体層真空容器５１２、５１３、５１４、ｉ型半導体層真空容器５１５、５１６、ｐ型半導体層真空容器５１７、５１８、５１９、を介して、帯状基板の巻き取り室５２０まで通し、弛みの無い程度に張力調整を行った。各真空容器５０５〜５１９を不図示の排気装置で、１．３×１０^-4Ｐａ（１×１０^-6Ｔｏｒｒ）まで減圧した。
【０１３５】
マイクロ波プラズマ法によるｉ型半導体層放電容器５２１、５２２には、それぞれの開口部に帯状基板５０２の堆積膜厚分布を制御するために、図１に示すような開口調整板１０２が設けられている。これにより堆積領域１０３は限定される。
【０１３６】
成膜時の加熱処理として、ガスゲートにゲートガス導入管から、ゲートガスとしてＨ₂をそれぞれ１０００ｓｃｃｍを導入し、基板加熱用ヒータにより、帯状基板を３００℃に加熱した。
【０１３７】
原料ガスをガス導入管から各放電容器に導入し、帯状基板を１２７０ｍｍ／ｍｉｎの速度で搬送させ、マイクロ波発振器、高周波発振器から各放電容器内に電力を印加して、成膜領域にプラズマ放電を生起し、帯状基板上にｎｉｐｎｉｐｎｉｐ型のアモルファスシリコン膜を形成した。
【０１３８】
帯状基板の１ロール分を搬送させた後、すべてのプラズマ、すべてのガスの供給、すべてのランプヒータの通電、搬送を停止した。次に放電容器リーク用の窒素（Ｎ₂）ガスを放電容器に導入し、大気圧に戻して巻き取り用ボビンに巻き取られた帯状基板を取り出した。
【０１３９】
形成されたｎｉｐｎｉｐｎｉｐ型のアモルファスシリコン膜上に、透明電極としてＩＴＯ（Ｉｎ₂Ｏ₃＋ＳｎＯ₂）を真空蒸着により７０ｎｍ蒸着し、さらに集電電極として、Ａｌを真空蒸着にて２μｍ蒸着し、光起電力素子を作製した。
【０１４０】
形成された光起電力素子の評価はスペクトル感度特性およびＡＭ値１．５、エネルギー密度１００Ｗ／ｃｍ²の擬似太陽光を照射したときの光電変換効率ηを測定することにより評価した。
【０１４１】
また、幅方向の分布を評価するため、スペクトル感度特性および光電変換効率は帯状基板の幅方向の中央部（Ｃ）および両端部（Ｆ、Ｒ）の３点を測定した。その結果を表９に示す。
【０１４２】
【表９】

【０１４３】
また、３５０ｍｍ×２４０ｍｍの大きさの光起電力素子を作製し、基板幅方向全体の効率を評価した。その結果を表１０に示す。
【０１４４】
【表１０】

【０１４５】
表９および表１０から明らかなように、開口調整板により、総堆積膜厚のむらが５％以内に押さえられることにより、その相対感度および光電変換効率のむらが押さえられることが判った。また、光電変換効率のむらが押さえられることにより、光起電力素子の基板幅方向全体の光電変換効率が向上させることが可能であること判った。
【０１４６】
（比較例２）
本比較例では、実施例２が図７に示した開口調整板７０２を用いて成膜したのに対して、幅方向に開口長が均一な図９に示す開口調整板９０１を用いた。その他の成膜条件は、実施例２と同様とした。本比較例では、マイクロ波電力をはじめ、その他の成膜条件は表１に示すように設定し作製した。なお、図９において、９０２はアプリケータ、９０３は堆積領域、９０４は帯状基板である。
【０１４７】
得られた堆積膜の幅方向膜厚分布は、表８に示す結果になった。得られた堆積膜の膜厚分布のむらは、１０％より大きいことが判った。
【０１４８】
実施例２と同様に、帯状基板上にｎｉｐｎｉｐｎｉｐ型のアモルファスシリコン膜を形成した。ｎ型層上に、透明電極としてＩＴＯ（Ｉｎ₂Ｏ₃＋ＳｎＯ₂）を真空蒸着により７０ｎｍ蒸着し、さらに集電電極として、Ａｌを真空蒸着にて２μｍ蒸着し、光起電力素子を作製した。
【０１４９】
形成された光起電力素子の評価はスペクトル感度特性およびＡＭ値１．５、エネルギー密度１００ｍＷ／ｃｍ²の擬似太陽光を照射したときの光電変換効率ηを測定することにより評価した。
【０１５０】
その結果を表９に示す。また、３５０ｍｍ×２４０ｍｍの大きさの光起電力素子を作製し、基板幅方向全体の効率を評価した。その結果を表１０に示す。
【０１５１】
開口調整板９０１を用いた場合、堆積膜厚のむらが１０％より大きかった。堆積膜厚のむらにより、光電変換効率のむらが生じ、その結果、光起電力素子の基板幅方向全体の光電変換効率を向上させるには至らなかった。
【０１５２】
（実施例３）
本実施例では、実施例１が図２に示したような４個のアプリケータ２２２用いて、マイクロ波電力を導入してｉ層を成膜したのに対し、図１０に示すように、２個のアプリケータ１００１用いて、マイクロ波電力を導入してｉ層を成膜した場合の実施例を述べる。成膜条件は、表１に示すように設定し作製した。なお、図１０において、１００２は開口部調整板、１００３は堆積領域、１００４は帯状基板である。
【０１５３】
実施例１に示した手順にしたがって、各真空容器にステンレス帯状基板（ＳＵＳ４３０）を通し、不図示の排気装置により１．３×１０^-4Ｐａ（１×１０^-6Ｔｏｒｒ）まで減圧した後、放電を生起し、帯状基板上にｉ型のアモルファスシリコン膜を形成した。放電容器２０７ａ、２０７ｂには、それぞれの放電容器の開口部に堆積膜厚分布を制御するための開口調整板２１９は設けず、放電容器２０７ａ、２０７ｂの開口部全域にわたって堆積膜を形成される。放電状態の安定を確認したのち、搬送を止めて静止サンプルを作製した。
【０１５４】
また、幅方向の分布を評価するため、堆積速度は図３に示すように帯状基板の中央部（Ｃ）および両端部（Ｆ、Ｒ）の３点、基板搬送方向に５点の合計１５点を分光器により、堆積速度を測定した。得られた堆積膜の堆積速度分布の結果を表１１および図１１に示す。
【０１５５】
【表１１】

【０１５６】
表１１および図１１から分かるように得られた堆積膜の堆積速度は基板幅方向および搬送方向に一定ではなく、帯状基板２１０を搬送させて堆積させた場合、その総堆積膜厚は、幅方向に大きな分布を生じる。
【０１５７】
その堆積速度分布の測定に基づいて、開口調整板の形状を決定した。
放電空間の帯状基板の搬送方向をＸ方向、
放電空間の帯状基板の面内で且つ搬送方向に垂直な方向をＹ方向、
放電空間内の帯状基板膜堆積面が通過する任意の点（ｘ_i，ｙ_j）において測定された前記帯状基板への膜の堆積速度をｄ（ｘ_i，ｙ_j）、
基板搬送速度をｖ＝１２７０（ｍｍ／ｍｉｎ）
理想的な堆積膜厚δ＝６００（Å）
とする。
【０１５８】
先ず、放電空間上のｙ₁＝１７５（ｍｍ），ｘ_P1≦ｘ₁≦ｘ_Q1における堆積膜厚をδ₁（ｘ，ｙ₁）
開口調整板を設けなかった時の放電空間の搬送方向の幅Ｌ＝２４０
ｘ_P1＋ｘ_Q1＝２４０ （この式は放電空間の中心線からみてｘ_P1，ｘ_Q1を対称とするために設定したものであり、必須ではない）
として、
ｄ₁（ｘ，ｙ₁）＝ｄ₁（ｖｔ，ｙ₁）＝−０．９３ｔ²＋１０．５ｔ＋３８．９ （∵ｘ＝ｖｔ）
【０１５９】
【数２１】

（１）式を満たす（ｔ，ｙ₁）＝Ａ₁（０．４３，１７５），Ｂ₁（１０．８７，１７５）
∴（ｘ，ｙ）＝Ａ₁（９，１７５），Ｂ₁（２３１，１７５）
【０１６０】
次に、放電空間上のｙ₂＝３５（ｍｍ），ｘ_P2≦ｘ₂≦ｘ_Q2における堆積膜厚をδ（ｘ，ｙ₂）
開口調整板を設けなかった時の放電空間の搬送方向の幅Ｌ＝２４０
ｘ_P2＋ｘ_Q2＝２４０ （この式は放電空間の中心線からみてｘ_P2，ｘ_Q2を対称とするために設定したものであり、必須ではない）
として、
ｄ₂（ｘ，ｙ₂）＝ｄ₂（ｖｔ，ｙ₂）＝−１．４５ｔ²＋１６．９ｔ＋３２．１ （∵ｘ＝ｖｔ）
【０１６１】
【数２２】

（１）’式を満たす（ｔ，ｙ₂）＝Ａ₂（０．８０，３５），Ｂ₂（１０．５，３５）
∴（ｘ，ｙ）＝Ａ₂（１７，３５），Ｂ₂（２２３，３５）
【０１６２】
次に、放電空間上のｙ₃＝３１５（ｍｍ），ｘ_P3≦ｘ₃≦ｘ_Q3における堆積膜厚をδ（ｘ，ｙ₃）
開口調整板を設けなかった時の放電空間の搬送方向の幅Ｌ＝２４０
ｘ_P3＋ｘ_Q3＝２４０ （この式は放電空間の中心線からみてｘ_P3，ｘ_Q3を対称とするために設定したものであり、必須ではない）
として、
ｄ₃（ｘ，ｙ₃）＝ｄ₃（ｖｔ，ｙ₃）＝−５．２ｔ²＋３３ｔ＋３５ （∵ｘ＝ｖｔ）
【０１６３】
【数２３】

（１）”式を満たす（ｔ，ｙ₃）＝Ａ₃（１．０５，３１５），Ｂ₃（１０．２５，３１５）
∴（ｘ，ｙ）＝Ａ₃（２３，３１５），Ｂ₃（２１７，３１５）
【０１６４】
点Ａ₁，Ａ₂，Ａ₃を通る二次曲線 ｘ＝Ｆ₁（ｙ）＝５．６×１０^-4ｙ²−０．１７ｙ＋２２…（２）
点Ｂ₁，Ｂ₂，Ｂ₃を通る二次曲線 ｘ＝Ｆ₂（ｙ）＝−５．６×１０^-4ｙ²＋０．１７ｙ＋２１８…（３）
【０１６５】
得られた曲線から、開口調整板の形状を決定し、図１０に示すような堆積領域１００３の幅方向の分布をもたせた開口調整板１００２を使用して、帯状基板１００４の堆積膜厚分布を制御を行い、ｎｉｐ型のシングルセルを作製した。ガス導入までの工程は実験１と同様に行い、帯状基板１００４を１２７０ｍｍ／ｍｉｎの速度で搬送させ、マイクロ波発振器２２０およびＲＦ発振器２２７から放電容器内にマイクロ波電力およびＲＦ電力を印可して、成膜領域にプラズマ放電を生起し、帯状基板上にｎｉｐ型のアモルファスシリコン膜を形成した。
【０１６６】
形成されたｎｉｐ型のアモルファスシリコン膜上に、透明電極としてＩＴＯ（Ｉｎ₂Ｏ₃＋ＳｎＯ₂）を真空蒸着により７０ｎｍ蒸着し、さらに集電電極として、Ａｌを真空蒸着にて２μｍ蒸着し、光起電力素子を作製した。得られた光起電力素子のＣ−Ｖ特性からｉ層の膜厚分布を評価した。得られた堆積膜の膜厚分布を、表１２に示す。
【０１６７】
【表１２】

【０１６８】
得られた堆積膜厚は幅方向に均一であり、その堆積膜厚のむらが、１０％以内に押さえられることが分かった。
【０１６９】
次に、図５に示すようなｎｉｐｎｉｐｎｉｐ型のトリプルセルを形成することが可能なロール・ツー・ロールプラズマＣＶＤ装置を用いて、トリプルセルを作製した。成膜条件を表４に示す。
【０１７０】
基板送り出し機構を有する真空容器５０１に、ステンレス帯状基板（ＳＵＳ４３０）の代わりに、下部電極として、スパッタリング法によりアルミニウム薄膜（０．２μｍ）およびＺｎＯ薄膜（１．２μｍ）を蒸着したステンレス帯状基板（ＳＵＳ４３０）５０２の巻き付けられたボビン５０３をセットし、上記実験と同様に帯状基板をガスゲート５０４、ｎ型半導体層真空容器５０５、５０６、５０７、ｉ型半導体層真空容器５０８、５０９、マイクロ波プラズマ法によるｉ型半導体層真空容器５１０、５１１、ＲＦプラズマＣＶＤ法によるｉ型半導体層真空容器５１２、５１３、５１４、ｉ型半導体層真空容器５１５、５１６、ｐ型半導体層真空容器５１７、５１８、５１９、を介して、帯状基板の巻き取り室５２０まで通し、弛みの無い程度に張力調整を行った。各真空容器５０５〜５１９を不図示の排気装置で、１．３×１０^-4Ｐａ（１×１０^-6Ｔｏｒｒ）まで減圧した。
【０１７１】
マイクロ波プラズマ法によるｉ型半導体層放電容器５２１、５２２には、それぞれの開口部に帯状基板５０２の堆積膜厚分布を制御するために、図１に示すような開口調整板１０２が設けられている。これにより堆積領域１０３は限定される。
【０１７２】
成膜時の加熱処理として、ガスゲートにゲートガス導入管から、ゲートガスとしてＨ₂をそれぞれ１０００ｓｃｃｍ導入し、基板加熱用ヒータにより、帯状基板を３００℃に加熱した。
【０１７３】
原料ガスをガス導入管から各放電容器に導入し、帯状基板を１２７０ｍｍ／ｍｉｎの速度で搬送させ、マイクロ波発振器、高周波発振器から各放電容器内に電力を印加して、成膜領域にプラズマ放電を生起し、帯状基板上にｎｉｐｎｉｐｎｉｐ型のアモルファスシリコン膜を形成した。
【０１７４】
帯状基板の１コール分を搬送させた後、すべてのプラズマ、すべてのガスの供給、すべてのランプヒータの通電、搬送を停止した。次に、放電容器リーク用の窒素（Ｎ₂）ガスを放電容器に導入し、大気圧に戻して巻き取り用ボビンに巻き取られた帯状基板を取り出した。
【０１７５】
形成されたｎｉｐｎｉｐｎｉｐ型のアモルファスシリコン膜上に、透明電極としてＩＴＯ（Ｉｎ₂Ｏ₃＋ＳｎＯ₂）を真空蒸着により７０ｎｍ蒸着し、さらに集電電極として、Ａｌを真空蒸着にて２μｍ蒸着し、光起電力素子を作製した。
【０１７６】
形成された光起電力素子の評価はスペクトル感度特性およびＡＭ値１．５、エネルギー密度１００ｍＷ／ｃｍ²の擬似太陽光を照射したときの光電変換効率ηを測定することにより評価した。また、幅方向の分布を評価するため、スペクトル感度特性および光電変換効率は帯状基板の幅方向の中央部（Ｃ）および両端部（Ｆ、Ｒ）の３を測定した。その結果を表１３に示す。
【０１７７】
【表１３】

【０１７８】
また、３５０ｍｍ×２４０ｍｍの大きさの光起電力素子を作製し、光起電力素子の基板幅方向全体の効率を評価した。その結果を表１４に示す。
【０１７９】
【表１４】

【０１８０】
表１３および表１４から明らかなように、開口調整板により、総堆積膜厚のむらが１０％以内に押さえられることにより、その相対感度および光電変換効率のむらが押さえられることが判った。また、光電変換効率のむらが押さえられることにより、光起電力素子の基板幅方向全体の光電変換効率が向上させることが可能であること判った。
【０１８１】
（比較例３）
本比較例では、実施例３が図１０に示した開口調整板１００２を用いて成膜したのに対して、幅方向に開口長が均一な図１２に示す開口調整板１２０１を用いた。その他の成膜条件は、実施例３と同様とした。本比較例では、マイクロ波電力をはじめ、その他の成膜条件は表１に示すように設定し作製した。なお、図１２において、１２０２はアプリケータ、１２０３は堆積領域、１２０４は帯状基板である。
【０１８２】
得られた堆積膜の幅方向膜厚分布は、表１２に示す結果になった。得られた堆積膜の膜厚分布のむらは、１０％より大きいことが判った。
【０１８３】
実施例３と同様に、帯状基板上にｎｉｐｎｉｐｎｉｐ型のアモルファスシリコン膜を形成した。ｎ型層上に、透明電極としてＩＴＯ（Ｉｎ₂Ｏ₃＋ＳｎＯ₂）を真空蒸着により７０ｎｍ蒸着し、さらに集電電極として、Ａｌを真空蒸着にて２μｍ蒸着し、光起電力素子を作製した。
【０１８４】
形成された光起電力素子の評価はスペクトル感度特性およびＡＭ値１．５、エネルギー密度１００ｍＷ／ｃｍ²の擬似太陽光を照射したときの光電変換効率ηを測定することにより評価した。その結果を表１３に示す。
【０１８５】
また、３５０ｍｍ×２４０ｍｍの大きさの光起電力素子を作製し、基板幅方向全体の効率を評価した。その結果を表１４に示す。
【０１８６】
上記開口調整板１２０１を用いた場合、堆積膜厚のむらが１０％より大きかった。堆積膜厚のむらにより、光電変換効率のむらが生じ、その結果、光起電力素子の基板幅方向全体の光電変換効率を低下させる結果となった。
【０１８７】
【発明の効果】
以上説明したように、本発明の堆積膜形成方法および堆積膜形成装置によれば、帯状基板と放電領域を一部遮るように、放電容器開口部に開口調整板を設置することで、堆積膜の幅方向膜厚分布を改善し、堆積膜の諸特性の均一化が可能となる。この結果、均一性が高く、特性の良好な大面積の光起電力素子およびそのデバイスを提供することが可能となる。
【図面の簡単な説明】
【図１】本発明の帯状基板幅方向の膜厚分布を均一化するように、放電容器の開口部に開口調整板を設けた実施例１の概念図である。
【図２】本発明の実施例において、シングルセル作製のために用いたロール・ツー・ロール型プラズマＣＶＤ装置の模式的概略図である。
【図３】本発明の実施例において、幅方向むらの評価を行った場所を示す図である。
【図４】本発明の実施例における静止サンプルの堆積速度分布を示す図である。
【図５】本発明の実施例において、トリプルセル作製のために用いたロール・ツー・ロール型プラズマＣＶＤ装置の模式的概略図である。
【図６】比較例１における開口調整板の模式的概念図である。
【図７】本発明の帯状基板幅方向の膜厚分布を均一化するように、放電容器の開口部に開口調整板を設けた実施例２の概念図である。
【図８】実施例２における静止サンプルの堆積速度分布を示す図である。
【図９】比較例２における開口調整板の模式的概念図である。
【図１０】本発明の帯状基板幅方向の膜厚分布を均一化するように、放電容器の開口部に開口調整板を設けた実施例３の概念図である。
【図１１】実施例３における静止サンプルの堆積速度分布を示す図である。
【図１２】比較例３における開口調整板の模式的概念図である。
【符号の説明】
１０１ アプリケータ
１０２ 開口調整板
１０３ 堆積領域
１０４ 帯状基板
２０１ 基板送出し容器
２０２ ｎ型半導体層真空容器
２０３ ｉ型半導体層真空容器
２０４ ｉ型半導体層真空容器
２０５ ｐ型半導体層真空容器
２０６ ｉ型半導体層真空容器
２０７ａ ｉ型半導体層放電容器
２０７ｂ ｉ型半導体層放電容器
２０８ 基板巻き取り容器
２０９ ガスゲート
２１０ 帯状基板
２１１ 送出しボビン
２１２ 基板巻き取りボビン
２１３ 加熱ヒータ
２１４ ガス導入管
２１５ ガス加熱ヒータ
２１６ ガス排気管
２１７ 排気調整バルブ
２１８ マイクロ波放電領域
２１９ 開口調整板
２２０ マイクロ波発振器
２２１ 導波管
２２２ アプリケータ
２２３ ＲＦバイアス棒
２２４ ＲＦ放電領域
２２５ カソード
２２６ ゲートガス導入管
２２７ ＲＦ発振器
５０１ 基板送出し容器
５０２ 帯状基板
５０３ 送出しボビン
５０４ ガスゲート
５０５ ｎ型半導体層真空容器
５０６ ｎ型半導体層真空容器
５０７ ｎ型半導体層真空容器
５０８ ｉ型半導体層真空容器
５０９ ｉ型半導体層真空容器
５１０ マイクロ波プラズマ法によるｉ型半導体層真空容器
５１１ マイクロ波プラズマ法によるｉ型半導体層真空容器
５１２ ＲＦプラズマＣＶＤ法によるｉ型半導体層真空容器
５１３ ＲＦプラズマＣＶＤ法によるｉ型半導体層真空容器
５１４ ＲＦプラズマＣＶＤ法によるｉ型半導体層真空容器
５１５ ｉ型半導体層真空容器
５１６ ｉ型半導体層真空容器
５１７ ｐ型半導体層真空容器
５１８ ｐ型半導体層真空容器
５１９ ｐ型半導体層真空容器
５２０ 基板巻き取り容器
５２１ マイクロ波プラズマＣＶＤ法によるｉ型半導体層放電容器
５２２ マイクロ波プラズマＣＶＤ法によるｉ型半導体層放電容器
６０１ 開口調整板
６０２ アプリケータ
６０３ 堆積領域
６０４ 帯状基板
７０１ アプリケータ
７０２ 開口調整板
７０３ 堆積領域
７０４ 帯状基板
９０１ 開口調整板
９０２ アプリケータ
９０３ 堆積領域
９０４ 帯状基板
１００１ アプリケータ
１００２ 開口調整板
１００３ 堆積領域
１００４ 帯状基板
１２０１ 開口調整板
１２０２ アプリケータ
１２０３ 堆積領域
１２０４ 帯状基板[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a deposited film forming method and a deposited film forming apparatus for continuously forming a deposited film on a long substrate by plasma CVD.
[0002]
[Prior art]
Conventionally, as a deposition film forming apparatus for continuously forming a thin film on the surface of a belt-shaped substrate, for example, a deposition film forming apparatus using a continuous plasma CVD method employing a roll-to-roll method is known. U.S. Pat. No. 4,400,409.
[0003]
According to this apparatus, a plurality of glow discharge regions are provided, and each glow discharge region is disposed along a path through which a sufficiently long strip-shaped substrate having a desired width is sequentially penetrated, and a conductivity type required in each glow discharge region. It is said that a large-area element having a semiconductor junction can be continuously formed by continuously transporting the substrate in the longitudinal direction while depositing the semiconductor layer. Therefore, it can be said that this roll-to-roll method is suitable for mass production of large-area semiconductor elements.
[0004]
In the conventional CVD method, high frequency (specifically, RF) discharge has been widely used as glow discharge plasma excitation means for decomposing a source gas and forming a deposited film. On the other hand, in recent years, a plasma process using a microwave attracts attention.
[0005]
Since the microwave has a higher frequency than when using conventional RF, it is possible to increase the energy density, and it is suitable for generating and sustaining plasma efficiently.
[0006]
For example, US Pat. Nos. 4,517,223 and 4,504,518 describe a method of depositing a thin film on a small area substrate in a microwave glow discharge plasma under low pressure. However, according to the microwave, discharge under a low pressure is possible as compared with RF, and polymization of active species causing deterioration of film characteristics is prevented, and a high-quality deposited film is formed. In addition to being obtained, it is said that the generation of powder such as polysilane in the plasma can be suppressed and the deposition rate can be dramatically improved.
[0007]
For mass production of semiconductor junction elements such as solar cells, it is indispensable to increase the area of the deposited region of the deposited film forming apparatus by the continuous plasma CVD method employing the roll-to-roll method.
[0008]
[Problems to be solved by the invention]
A deposited film produced by an apparatus using a conventional microwave CVD method and RF plasma CVD method has a large variation in the width direction as the deposition rate increases and the discharge region expands.
[0009]
The deposition rate varies greatly depending on the type of discharge energy for generating plasma, discharge conditions (for example, discharge power, discharge frequency), the flow rate, flow rate, pressure, etc. of the source gas in the vacuum vessel. Changes in gas concentration distribution and plasma density distribution are not taken into consideration, and there is a problem that a deposited film having a uniform film thickness and film quality cannot be formed in a large-area deposition region.
[0010]
For example, in the microwave plasma CVD method, when pursuing characteristics as a solar battery cell, it is necessary to reduce the microwave power and increase the RF bias introduction power. However, the deposited film thickness distribution of the deposited film obtained under these conditions is distributed with respect to the distance from the microwave introduction part, and the deposited film thickness becomes thinner as the distance of the microwave introduction part becomes larger.
[0011]
When such a plasma CVD method is applied to a deposited film having a large area, it is difficult to obtain a deposited film having a uniform film thickness and film quality having a large area over arbitrary film forming conditions.
[0012]
As described above, the conventional roll-to-roll semiconductor laminated film continuous forming apparatus has the characteristics of the photovoltaic element in the substrate width direction when formed by the microwave plasma CVD method capable of high-speed film formation. There is a problem that unevenness is likely to occur.
[0013]
In view of the above problems, an object of the present invention is to provide a deposited film forming method and a deposited film forming apparatus capable of obtaining a photovoltaic element free from characteristic unevenness by depositing a semiconductor layer free from unevenness in film thickness and film quality. It is to provide.
[0014]
[Means for Solving the Problems]
In order to achieve the above object, the deposited film forming method of the present invention continuously generates a plasma in a plurality of continuous vacuum vessels and continuously moves the belt-like substrate in the longitudinal direction on the substrate. In the deposited film forming method for forming a deposited film, the opening of the discharge vessel is adjusted with an aperture adjusting plate whose shape is set to reduce the unevenness of the deposited film thickness in the substrate width direction based on the measurement of the deposition rate distribution. Thus, film formation is performed.
[0015]
In the deposited film forming method,
The transport direction of the strip substrate in the discharge space is the X direction,
A direction perpendicular to the transport direction in the plane of the strip-shaped substrate in the discharge space is the Y direction,
Arbitrary point (x where the belt-like substrate film deposition surface passes in the discharge space)_i, Y_j) Is the deposition rate of the film on the strip substrate measured in d)_i, Y_j),
(However, i = 1, 2,..., M, j = 1, 2,..., N, where m and n are both 3 or more)
Substrate transport speed is v,
With the ideal deposited film thickness as δ,
Y = y on the discharge space_jThe deposition rate distribution in the X direction at d (x_i, Y_j) To approximate a quadratic curve to obtain the following equation (1):
d_j(X, y_j) = D_j(Vt, y_j) = A_jt²+ B_jt + c_j  (∵x = vt, t is time) (1)
Furthermore, y = y on the discharge space_jDeposited film thickness δ_j(X, y_j) To obtain the above δ, the following equation (2) is obtained:
[0016]
[Equation 5]

  Substituting equation (1) into equation (2) and satisfying this point A_j(Vt_j1, Y_j), Point B_j(Vt_j2, Y_j)
  3 or more points A each_jAnd B_jTo obtain the following equations (3) and (4) as approximate curves,
    x = F₁(Y) ... (3)
    x = F₂(Y) ... (4)
  A curve satisfying the equation (3) and a curve satisfying the equation (4) are respectively provided at the opening of the discharge vessel.X directionSet to be both ends (curves corresponding to both ends in the substrate transfer direction) and adjust the opening of the discharge vessel to limit the deposition area of the strip substrateTo do.
[0017]
  Further, the point A from the center position in the X direction of the discharge space._j(Vt_j1, Y_j) And point B_j(Vt_j2, Y_j) So that the distance to_j(Vt_j1, Y_j) And point B_j(Vt_j2, Y_j) Is preferred.
  Further, the shape of the opening adjusting plate is the point A obtained from the widthwise deposition rate distribution of the belt-like substrate._j(Vt_j1, Y_j) And the point B_j(Vt_j2, Y_j) Through the discharge vessel openingX directionIt is preferable to set the shape of both ends, and limit the deposition region of the belt-shaped substrate by adjusting the opening of the discharge vessel.
[0018]
Furthermore, it is preferable that the shape of the opening adjusting plate is set to be within ± 10% of the opening shape obtained from the widthwise deposition rate distribution of the belt-like substrate.
[0019]
The shape of the opening adjusting plate is preferably set so that the unevenness of the film thickness distribution in the width direction of the belt-like substrate of the deposited film is within 10%.
[0020]
The deposited film is preferably formed by a microwave plasma CVD method.
[0021]
Furthermore, it is preferable to adopt a roll-to-roll method in which the belt-like substrate drawn out from the state wound in the roll shape in the plurality of discharge vessels is continuously moved and wound again in the roll shape.
[0022]
On the other hand, the deposited film forming apparatus of the present invention generates plasma in a plurality of continuous vacuum vessels and continuously forms a deposited film on the substrate while moving the strip-shaped substrate continuously in the longitudinal direction. In the film forming apparatus, an opening adjusting plate having a shape set so as to reduce unevenness of the deposited film thickness in the substrate width direction based on the measurement of the deposition rate distribution is provided at the opening of the discharge vessel.
[0023]
In the deposited film forming apparatus,
The transport direction of the strip substrate in the discharge space is the X direction,
A direction perpendicular to the transport direction in the plane of the strip-shaped substrate in the discharge space is the Y direction,
An arbitrary point (x_i, Y_j) Is the deposition rate of the film on the strip substrate measured in d)_i, Y_j),
(However, i = 1, 2,..., M, j = 1, 2,..., N, where m and n are both 3 or more)
Substrate transport speed is v,
With the ideal deposited film thickness as δ,
Y = y on the discharge space_jThe deposition rate distribution in the X direction at d (x_i, Y_j) To approximate a quadratic curve to obtain the following equation (1):
d_j(X, y_j) = D_j(Vt, y_j) = A_jt²+ B_jt + c_j  (∵x = vt, t is time) (1)
Furthermore, y = y on the discharge space_jDeposited film thickness δ_j(X, y_j) To obtain the above δ, the following equation (2) is obtained:
[0024]
[Formula 6]

  Substituting equation (1) into equation (2) and satisfying this point A_j(Vt_j1, Y_j), Point B_j(Vt_j2, Y_j)
  3 or more points A each_jAnd B_jTo obtain the following equations (3) and (4) as approximate curves,
    x = F₁(Y) ... (3)
    x = F₂(Y) ... (4)
  A curve satisfying the equation (3) and a curve satisfying the equation (4) are respectively provided at the opening of the discharge vessel.X directionSet to be at both ends, and install an opening adjustment plate to limit the deposition area of the belt-shaped substrate at the opening of the discharge vesselTo do.
[0025]
  Further, the point A from the center position in the X direction of the discharge space._j(Vt_j1, Y_j) And point B_j(Vt_j2, Y_j) So that the distance to_j(Vt_j1, Y_j) And point B_j(Vt_j2, Y_j) Is preferred.
  Further, the shape of the opening adjusting plate is the point A obtained from the widthwise deposition rate distribution of the belt-like substrate._j(Vt_j1, Y_j) And the point B_j(Vt_j2, Y_j) Through the discharge vessel openingX directionIt is preferable to set an opening adjusting plate for limiting the deposition region of the band-shaped substrate at the opening of the discharge vessel, so that the shape of both ends is set.
[0026]
Furthermore, it is preferable to install an opening adjusting plate having a shape such that the shape of the opening adjusting plate is within ± 10% of the shape of the opening adjusting plate obtained from the widthwise deposition rate distribution of the belt-like substrate.
[0027]
Then, it is preferable to install an opening adjusting plate having a shape such that the unevenness of the film thickness distribution in the width direction of the belt-like substrate of the deposited film is within 10%.
[0028]
The deposited film is preferably formed by a microwave plasma CVD apparatus.
[0029]
Furthermore, it is preferable to form as a roll-to-roll apparatus in which a strip-like substrate drawn out from a state wound in a roll shape in a plurality of discharge vessels is continuously moved and wound again in a roll shape.
[0030]
In the deposited film forming method using the plasma CVD method, when the discharge space is expanded in order to expand the film formation region, the film thickness of the deposited film is distributed. The distribution varies greatly depending on the method of introducing the microwave power and the deposition conditions of the deposited film. For example, the deposition rate distribution differs greatly between when microwave power is introduced from one direction and when introduced from two directions.
[0031]
In the present invention, the deposition rate distribution is measured, and the shape of the aperture adjusting plate is determined so that the deposited film thickness in the substrate width direction is uniform. By providing the opening adjusting plate at the opening of the discharge vessel, the substrate and the discharge region can be blocked and the region deposited on the belt-like substrate can be limited. By this method, a deposited film having a uniform thickness over a large area can be formed.
[0032]
Furthermore, even when the film forming conditions are changed in order to optimize the film forming conditions of the deposited film, the deposited film having a uniform film thickness is formed by re-determining the shape of the aperture adjustment plate each time. be able to.
[0033]
Specifically, as a method of setting the shape of the opening adjusting plate within ± 10% of the opening shape obtained from the widthwise deposition rate distribution of the belt-like substrate, the curve at both ends of the opening is the above-described x = F.₁(Y) and x = F₂It is conceivable to set so as to deviate within ± 10% from (y).
[0034]
Specifically, the curve at one end of the opening is
[0035]
[Expression 7]

In the area represented by
The curve at the other end of the opening is
[0036]
[Equation 8]

It exists in the area represented by.
[0037]
Accordingly, the present invention provides a deposition film forming method in which plasma is generated in a plurality of continuous vacuum vessels, and a deposition film is continuously formed on the substrate while continuously moving the strip substrate in the longitudinal direction thereof.
The transport direction of the strip substrate in the discharge space is the X direction,
A direction perpendicular to the transport direction in the plane of the strip-shaped substrate in the discharge space is the Y direction,
Arbitrary point (x where the belt-like substrate film deposition surface passes in the discharge space)_i, Y_j) Is the deposition rate of the film on the strip substrate measured in d)_i, Y_j),
(However, i = 1, 2,..., M, j = 1, 2,..., N, where m and n are both 3 or more)
Substrate transport speed is v,
With the ideal deposited film thickness as δ,
Y = y on the discharge space_jThe deposition rate distribution in the X direction at d (x_i, Y_j) To approximate a quadratic curve to obtain the following equation (1):
d_j(X, y_j) = D_j(Vt, y_j) = A_jt²+ B_jt + c_j  (∵x = vt, t is time) (1)
Furthermore, y = y on the discharge space_jDeposited film thickness δ_j(X, y_j) To obtain the above δ, the following equation (2) is obtained:
[0038]
[Equation 9]

  Substituting equation (1) into equation (2) and satisfying this point A_j(Vt_j1, Y_j), Point B_j(Vt_j2, Y_j)
  3 or more points A each_jAnd B_jTo obtain the following equations (3) and (4) as approximate curves,
    x = F₁(Y) ... (3)
    x = F₂(Y) ... (4)
  Furthermore, the following inequalities (5) and (6) defined based on the above equations (3) and (4) are obtained,
1.1F₁(Y) -0.1F₂(Y) ≦ X ≦ 0.9F₁(Y) + 0.1F₂(Y) (5)
0.9F₂(Y) + 0.1F₁(Y) ≦ X ≦ 1.1F₂(Y) -0.1F₁(Y) ... (6)
  A curve satisfying the equation (5) and a curve satisfying the equation (6) are respectively present at the opening of the discharge vessel.X directionThere is provided a deposited film forming method characterized in that it is set to be at both ends, and the opening of the discharge vessel is adjusted to limit the deposition region of the belt-like substrate.
[0039]
The present invention also relates to a deposition film forming apparatus that continuously forms a deposition film on a substrate while generating plasma in a plurality of continuous vacuum vessels and continuously moving the belt-like substrate in the longitudinal direction thereof. ,
The transport direction of the strip substrate in the discharge space is the X direction,
A direction perpendicular to the transport direction in the plane of the strip-shaped substrate in the discharge space is the Y direction,
Arbitrary point (x where the belt-like substrate film deposition surface passes in the discharge space)_i, Y_j) Is the deposition rate of the film on the strip substrate measured in d)_i, Y_j),
(However, i = 1, 2,..., M, j = 1, 2,..., N, where m and n are both 3 or more)
Substrate transport speed is v,
With the ideal deposited film thickness as δ,
Y = y on the discharge space_jThe deposition rate distribution in the X direction at d (x_i, Y_j) To approximate a quadratic curve to obtain the following equation (1):
d_j(X, y_j) = D_j(Vt, y_j) = A_jt²+ B_jt + c_j  (∵x = vt, t is time) (1)
Furthermore, y = y on the discharge space_jDeposited film thickness δ_j(X, y_j) To obtain the above δ, the following equation (2) is obtained:
[0040]
[Expression 10]

  Substituting equation (1) into equation (2) and satisfying this point A_j(Vt_j1, Y_j), Point B_j(Vt_j2, Y_j)
  3 or more points A each_jAnd B_jTo obtain the following equations (3) and (4) as approximate curves,
    x = F₁(Y) ... (3)
    x = F₂(Y) ... (4)
  Furthermore, the following inequalities (5) and (6) defined based on the above equations (3) and (4) are obtained,
1.1F₁(Y) -0.1F₂(Y) ≦ X ≦ 0.9F₁(Y) + 0.1F₂(Y) (5)
0.9F₂(Y) + 0.1F₁(Y) ≦ X ≦ 1.1F₂(Y) -0.1F₁(Y) ... (6)
  A curve satisfying the equation (5) and a curve satisfying the equation (6)X directionThere is provided a deposited film forming apparatus characterized in that it is set to be at both ends, and the opening of the discharge vessel is adjusted to limit the deposition region of the belt-like substrate.
[0041]
DETAILED DESCRIPTION OF THE INVENTION
Preferred embodiments of the present invention will be described below in detail with reference to the accompanying drawings, but the present invention is not limited to these embodiments.
[0042]
As described above, the present invention provides an apparatus for forming a functional deposition film on the surface of a substrate by continuously transporting the belt-like substrate in the longitudinal direction thereof, from the opening adjusting plate provided at the opening of the discharge vessel. The discharge region is cut off, and the region deposited on the belt-like substrate can be controlled.
[0043]
This makes it possible to increase the area of the deposited film by enlarging the discharge space, which is a major problem of the conventional deposited film formation method by plasma CVD, and to make the film thickness and film quality distribution of the deposited film uniform. become.
[0044]
The deposited film forming apparatus used in the present invention will be described with reference to the drawings. The apparatus used in the present invention is a conventional roll-to-roll type continuous plasma CVD apparatus shown in FIG.
[0045]
In FIG. 2, the deposited film forming apparatus basically includes an unwinding chamber 201 for a strip-shaped substrate, an n-type semiconductor layer vacuum vessel 202, an i-type semiconductor layer vacuum vessel 203, and an i-type semiconductor layer vacuum vessel 204 by high-frequency plasma CVD. , A p-type semiconductor layer vacuum vessel 205, an i-type semiconductor layer vacuum vessel 206 formed by microwave plasma CVD having two discharge vessels 207a and 207b inside, and a belt-like substrate take-up chamber 208, The vacuum vessels 202 to 206 are connected to each other by a gas gate 209.
[0046]
In the apparatus of the present invention, the belt-like substrate 210 is unwound from the bobbin 211 in the unwinding chamber 201 and is connected to the five vacuum vessels 202-connected by the gas gate 209 until being wound on the bobbin 212 in the winding chamber 208. A semiconductor deposited film having a nip structure is formed on the surface of the substrate during the movement while passing through 206.
[0047]
Each of the vacuum vessels 202 to 206 includes a heater 213 for heating the substrate, a gas introduction pipe 214 for introducing a film forming gas supplied from a gas supply unit (not shown) into the discharge vessel, and a gas heater for heating the introduced gas. 215, an exhaust pipe 216 and an exhaust adjustment valve 217 for exhausting the discharge vessel by exhaust means (not shown) are provided. The unwind chamber 201 and the take-up chamber 208 are also provided with an exhaust pipe 216 and an exhaust adjustment valve 217.
[0048]
In the discharge region 218 in the vacuum vessel 206 using the microwave CVD method, an opening adjusting plate 219 is installed in the opening of the discharge vessels 207a and 207b in order to control the deposited film thickness distribution of the strip substrate, and the microwave oscillator 220 is provided. Through the waveguide 221, an applicator 222 for supplying microwave power for energizing the film forming gas in the discharge vessel to cause discharge, and a bias rod 223 for applying RF power to the plasma from the RF oscillator 227. And the deposited raw material gas is decomposed to form a deposited film.
[0049]
In the discharge region 224 in the vacuum vessels 202 to 205 using the RF plasma CVD method, a cathode 225 for applying RF power to the source gas is provided, and a deposited film is formed by the RF plasma CVD method.
[0050]
The gas gate 209 is provided for the purpose of separating and independently separating each vacuum vessel and continuously transporting the belt-like substrate 210 through each discharge region. By introducing the gate gas from the gate gas introduction pipe 226 and preventing the source gases in the adjacent vacuum containers from being mixed, a high-quality deposited film having different compositions can be formed in multiple layers.
[0051]
The deposited film forming method of the present invention is carried out using such a deposited film forming apparatus. That is, in the deposited film forming method of the present invention, plasma is generated in a plurality of continuous vacuum vessels, and the deposited film is continuously formed on the substrate while continuously moving the strip substrate in the longitudinal direction thereof. A method for forming a deposited film, in which an opening of a discharge vessel is formed by adjusting the opening with an opening adjusting plate whose shape is set so as to reduce the unevenness of the deposited film thickness in the substrate width direction based on the measurement of the deposition rate distribution. I do.
[0052]
Specifically, the transport direction of the strip substrate in the discharge space is the X direction,
A direction perpendicular to the transport direction in the plane of the strip-shaped substrate in the discharge space is the Y direction,
Arbitrary point (x where the belt-like substrate film deposition surface passes in the discharge space)_i, Y_j) Is the deposition rate of the film on the strip substrate measured in d)_i, Y_j),
(However, i = 1, 2,..., M, j = 1, 2,..., N, where m and n are both 3 or more)
Substrate transport speed is v,
Let δ be the ideal deposited film thickness.
Where y = y on the discharge space_jThe deposition rate distribution in the X direction at d (x_i, Y_j) To approximate a quadratic curve
d_j(X, y_j) = D_j(Vt, y_j) = A_jt²+ B_jt + c_j  (∵x = vt, t is time) (1)
And On the other hand, y = y on the discharge space_jDeposited film thickness δ_j(X, y_j) To be the above δ,
[0053]
[Expression 11]

Satisfy t_j1To t_j2In the meantime, film deposition is performed.
Therefore, the above formula (1) is substituted into the formula (2), and the point A satisfying this is substituted._j(Vt_j1, Y_j), Point B_j(Vt_j2, Y_j) Can be obtained. That is, point A_jTo point B_jBy performing the deposition up to this time, the deposited film thickness can be roughly set.
And point A for each j_jTo point B_j, And approximating the distribution of these points in the Y direction with a quadratic curve, for example,
Point A_jA quadratic curve derived by approximation from (3 or more points) is
x = F₁(Y) ... (3)
Point B_jA quadratic curve derived by approximation from (3 or more points) is
x = F₂(Y) ... (4)
It becomes.
Next, the curve satisfying the equation (3) and the curve satisfying the equation (4) are set to be both ends of the opening of the discharge vessel, respectively, and the opening of the discharge vessel is adjusted to deposit the band-shaped substrate. By limiting the region, film formation conditions (opening adjustment conditions) can be obtained such that the film thickness is approximately δ in all portions in the direction perpendicular to the substrate transport direction.
[0054]
In the present invention, setting the curve satisfying the expression (3) and the curve satisfying the expression (4) to be both ends of the opening of the discharge vessel respectively means that these curves existing on the belt-like substrate are For example, it means that the end of the aperture adjustment plate is set at a position separated by a predetermined distance (a known distance can be adopted) in a direction perpendicular to the surface.
[0055]
It should be noted that point A from the above equations (1) and (2)._j(Vt_j1, Y_j) And point B_j(Vt_j2, Y_j) Is obtained as a precondition, for example, the point A from the center position in the X direction of the discharge space._j(Vt_j1, Y_j) And point B_j(Vt_j2, Y_j) To be equal or point A_j(Vt_j1, Y_jOr point B_j(Vt_j2, Y_j) Position in one X direction (ie, vt_j1Or vt_j2) Is fixed and the other position in the X direction is obtained. In this case, the above-mentioned preconditions can be appropriately selected in consideration of the deposition rate measured in advance and the distribution thereof. In each embodiment described below, the deposition rate is large and the variation is small. In order to perform film deposition at a point A from the center position in the X direction of the discharge space._j(Vt_j1, Y_j) And point B_j(Vt_j2, Y_j) To be equal.
Further, the shape of the aperture adjusting plate is the point A obtained from the widthwise deposition rate distribution of the belt-like substrate._j(Vt_j1, Y_j) And the point B_j(Vt_j2, Y_j) Is set to be the shape of both ends of the opening of the discharge vessel, and the opening of the discharge vessel is adjusted to limit the deposition region of the belt-like substrate.
[0056]
Furthermore, it is preferable that the shape of the opening adjusting plate is set to be within ± 10% of the opening shape obtained from the widthwise deposition rate distribution of the belt-like substrate. A specific setting method in this case can be expressed by the above-described equations (5) and (6).
[0057]
This deposited film is formed by a plasma CVD method, and is particularly preferably formed by a microwave plasma CVD method.
[0058]
Further, it is preferable that the shape of the opening adjusting plate is set so that the unevenness of the film thickness distribution in the width direction of the belt-like substrate of the deposited film is within 10%.
[0059]
In order to continuously form the deposited film, it is preferable to adopt a roll-to-roll method in which a roll-shaped substrate continuously moves in a plurality of discharge vessels.
[0060]
That is, in the present invention, the shape of the aperture adjusting plate is determined so that the deposition rate distribution is measured and the deposited film thickness in the substrate width direction is uniform. By providing the opening adjusting plate at the opening of the discharge vessel, the substrate and the discharge region can be blocked and the region deposited on the belt-like substrate can be limited. By this method, a deposited film having a uniform thickness over a large area can be formed.
[0061]
Furthermore, even when the film forming conditions are changed in order to optimize the film forming conditions of the deposited film, the deposited film having a uniform film thickness is formed by re-determining the shape of the aperture adjustment plate each time. be able to.
[0062]
If a deposition film is formed over the entire opening of the discharge vessel without providing an opening adjusting plate for controlling the deposition thickness distribution at the opening of the discharge vessel, and without limiting the deposition region, the deposition thickness rate is increased. Has a large distribution. This is because the deposition rate distribution tends to decrease as the distance from the microwave power introduction unit increases, and a characteristic distribution appears in the deposition rate distribution depending on the method of introducing the microwave power of the deposition film forming apparatus.
[0063]
For example, when the microwave power is introduced by using the four applicators 101 by the method shown in FIG. 1, the distribution of the deposition rate at the center portion is smaller than that at the both end portions. In accordance with such a deposition rate distribution, an opening adjustment plate 102 having a shape as shown in FIG. 1 is provided in the opening of the discharge vessel, so that an opening 103 corresponding to the film thickness distribution is formed in the discharge vessel opening. A deposited film having a uniform film thickness and film quality can be obtained on the belt-like substrate 104.
[0064]
In addition, even when the film formation conditions are changed to improve the characteristics, it is possible to form a deposited film having a uniform film thickness by changing the shape of the aperture adjustment plate.
[0065]
【Example】
Specific examples of the deposited film forming method and the deposited film forming apparatus of the present invention will be described below, but the present invention is not limited to these examples.
[0066]
(Example 1)
The deposited film forming method of the present invention will be described according to the procedure using the deposited film forming apparatus shown in FIG. First, in this experiment, the deposition rate distribution of the deposited film of the i layer manufactured using the microwave CVD method was examined. In the deposited film forming apparatus of FIG. 2, microwave power is introduced using four applicators 222. The production conditions are shown in Table 1.
[0067]
[Table 1]

[0068]
A bobbin 211 wound with a stainless steel strip-shaped substrate (SUS430, width 350 mm × length 300 m × thickness 0.2 mm) 210 that has been sufficiently degreased and cleaned is set in a vacuum container 201 having a substrate feed mechanism, and the strip-shaped substrate is mounted. The band-shaped substrate is sequentially passed through the gas gate 209, the n-type semiconductor layer vacuum vessel 202, the i-type semiconductor layer vacuum vessel 203, the i-type semiconductor layer vacuum vessel 206, the i-type semiconductor layer vacuum vessel 204, and the p-type semiconductor layer vacuum vessel 205. The tension was adjusted to the extent that there was no slack through the winding chamber 208. Each vacuum vessel has an exhaust device (not shown) of 1.3 × 10^-FourPa (1 × 10^-6The pressure was reduced to Torr).
[0069]
First, in the discharge vessels 207a and 207b, a deposited film is formed over the entire opening of the discharge vessels 207a and 207b without providing an opening adjusting plate 219 for controlling the deposited film thickness distribution at the opening of each discharge vessel. The deposition rate distribution was measured.
[0070]
As a heat treatment at the time of film formation, the gas gas is supplied from the gate gas introduction pipe 226 to the gas gate 209 as the gate gas.₂1000 sccm of each was introduced, and the belt-like substrate 210 was heated to 300 ° C. by the substrate heating heater 213.
[0071]
The source gas is introduced into each discharge vessel from the gas introduction tube 214, the belt-like substrate is conveyed at a speed of 1270 mm / min, and the microphone mouth wave power and the RF power are applied from the microwave oscillator 220 and the RF oscillator 227 into the discharge vessel. Then, plasma discharge was generated in the film formation region, and an i-type amorphous silicon film was formed on the belt-like substrate.
[0072]
After confirming the stability of the discharge state, the conveyance was stopped and a stationary sample was produced. The deposition rate of the deposited film obtained by the spectroscope was measured. In order to evaluate the distribution in the width direction, the deposition rate is 5 points at the center (C) and both ends (F, FC, RC, R) of the belt-like substrate as shown in FIG. 3, and 10 points in the substrate transport direction. A total of 50 points were measured. The results are shown in Table 2 and FIG. In Table 2, points with a Position of 30 to 110 mm are in the discharge vessel 207a, and points with a Position of 250 to 330 mm are in the discharge vessel 207b.
[0073]
[Table 2]

[0074]
As can be seen from Table 2 and FIG. 4, the deposition rate of the obtained deposited film is not constant in the width direction of the belt-like substrate and the transport direction, and when the belt-like substrate 210 is deposited while being transported, the total deposited film thickness is the width direction. Produced a large distribution.
[0075]
Based on the results of the deposition rate distribution, the shape of the opening adjusting plate was determined for each of the two right and left discharge vessels.
[0076]
First, the discharge space A was obtained.
The transport direction of the strip-shaped substrate in the discharge space is the X direction,
The direction perpendicular to the transport direction within the plane of the strip-shaped substrate in the discharge space is the Y direction,
Arbitrary point (x where the belt-like substrate film deposition surface passes in the discharge space)_i, Y_j) Is the deposition rate of the film on the strip substrate measured in d)_i, Y_j),
Substrate transport speed is v = 1270 (mm / min)
Ideal deposited film thickness δ = 300 (Å)
And
[0077]
First, y on the discharge space₁= 175 (mm), x_P1≦ x₁≦ x_Q1The deposited film thickness at₁(X, y₁)
The width L in the transport direction of the discharge space when no opening adjusting plate is provided L = 140
x_P1+ X_Q1= 140 (This expression is x as seen from the center line of the discharge space._P1, X_Q1Is set to be symmetric, not required)
As
d₁(X, y₁) = D₁(Vt, y₁) = − 4.2t²+ 27t + 24 (∵x = vt)
[0078]
[Expression 12]

Satisfying equation (1) (t, y₁) = A₁(0.28, 175), B₁(6.32, 175)
∴ (x, y) = A₁(6.0, 175), B₁(134,175)
[0079]
Next, y on the discharge space₂= 35 (mm), x_P2≦ x₂≦ x_Q2The deposited film thickness at δ (x, y₂)
The width L in the transport direction of the discharge space when no opening adjusting plate is provided L = 140
x_P2+ X_Q2= 140 (This expression is x as seen from the center line of the discharge space._P2, X_Q2Is set to be symmetric, not required)
As
d₂(X, y₂) = D₂(Vt, y₂) = − 5.0t²+ 32t + 37 (∵x = vt)
[0080]
[Formula 13]

(1) satisfies the expression (t, y₂) = A₂(0.85, 35), B₂(5.75, 35)
∴ (x, y) = A₂(18, 35), B₂(122, 35)
[0081]
Next, y on the discharge space_Three= 315 (mm), x_P3≦ x_Three≦ x_Q3The deposited film thickness at δ (x, y_Three)
The width L in the transport direction of the discharge space when no opening adjusting plate is provided L = 140
x_P3+ X_Q3= 140 (This expression is x as seen from the center line of the discharge space._P3, X_Q3Is set to be symmetric, not required)
As
d_Three(X, y_Three) = D_Three(Vt, y_Three) =-5.2t²+ 33t + 35 (∵x = vt)
[0082]
[Expression 14]

(1) ”is satisfied (t, y_Three) = A_Three(0.78, 315), B_Three(5.82, 315)
∴ (x, y) = A_Three(17,315), B_Three(123,315)
[0083]
Point A₁, A₂, A_ThreeA quadratic curve passing through x = F₁(Y) = 5.9 × 10^-Foury²-0.21y + 24 (2)
Point B₁, B₂, B_ThreeA quadratic curve passing through x = F₂(Y) = − 5.9 × 10^-Foury²+ 0.21 + 116 (3)
[0084]
Similarly, the discharge space B is obtained.
Substrate transport speed is v = 1270 (mm / min)
Ideal deposited film thickness δ = 300 (Å)
And
[0085]
First, y on the discharge space₁= 175 (mm), x_P1≦ x₁≦ x_Q1The deposited film thickness at₁(X, y₁)
The width L in the transport direction of the discharge space when no opening adjusting plate is provided L = 140
x_P1+ X_Q1= 140 (This expression is x as seen from the center line of the discharge space._P1, X_Q1Is set to be symmetric, not required)
As
d₁(X, y₁) = D₁(Vt, y₁) = − 4.7 t²+ 31t + 19 (∵x = vt)
[0086]
[Expression 15]

Satisfying equation (1) (t, y₁) = A₁(0.29, 175), B₁(6.31, 175)
∴ (x, y) = A₁(6.1, 175), B₁(133.9, 175)
[0087]
Next, y on the discharge space₂= 35 (mm), x_P2≦ x₂≦ x_Q2The deposited film thickness at δ (x, y₂)
The width L in the transport direction of the discharge space when no opening adjusting plate is provided L = 140
x_P2+ X_Q2= 140 (This expression is x as seen from the center line of the discharge space._P2, X_Q2Is set to be symmetric, not required)
As
d₂(X, y₂) = D₂(Vt, y₂) = − 5.0t²+ 34t + 31 (∵x = vt)
[0088]
[Expression 16]

(1) satisfies the expression (t, y₂) = A₂(0.83, 35), B₂(5.77, 35)
∴ (x, y) = A₂(17.6, 35), B₂(122.4, 35)
[0089]
Next, y on the discharge space_Three= 315 (mm), x_P3≦ x_Three≦ x_Q3The deposited film thickness at δ (x, y_Three)
The width L in the transport direction of the discharge space when no opening adjusting plate is provided L = 140
x_P3+ X_Q3= 140 (This expression is x as seen from the center line of the discharge space._P3, X_Q3Is set to be symmetric, not required)
As
d_Three(X, y_Three) = D_Three(Vt, y_Three) = − 5.6 t²+ 38t + 25 (∵x = vt)
[0090]
[Expression 17]

(1) ”is satisfied (t, y_Three) = A_Three(0.77, 315), B_Three(5.83, 315)
∴ (x, y) = A_Three(16.3, 315), B_Three(123.7, 315)
[0091]
Point A₁, A₂, A_ThreeA quadratic curve passing through x = F₁(Y) = 5.9 × 10^-Foury²-0.21y + 24 (2)
Point B₁, B₂, B_ThreeA quadratic curve passing through x = F₂(Y) = − 5.9 × 10^-Foury²+ 0.21 + 116 (3)
[0092]
From the obtained curve, the distribution adjustment of the deposited film thickness of the belt-like substrate 104 is controlled using the aperture adjusting plate 102 having the distribution in the width direction of the deposition region 103 as shown in FIG. Was made.
[0093]
The process up to gas introduction is performed in the same manner as in Experiment 1. The belt-like substrate is transported at a speed of 1270 mm / min, and microwave power and RF power are applied from the microwave oscillator 220 and the RF oscillator 227 into the discharge vessel. Plasma discharge was generated in the film region, and a nip type amorphous silicon film was formed on the strip substrate.
[0094]
On the formed nip type amorphous silicon film, ITO (In₂O_Three+ SnO₂) Was deposited by vacuum deposition to 70 nm, and as a collecting electrode, Al was deposited by 2 μm by vacuum deposition to produce a photovoltaic device. The film thickness distribution of the i layer was evaluated from the CV characteristics of the obtained photovoltaic element. Table 3 shows the film thickness distribution of the obtained deposited film.
[0095]
[Table 3]

[0096]
It was found that the obtained deposited film thickness was uniform in the width direction, and the unevenness of the deposited film thickness was suppressed within 0 to 10%.
[0097]
Next, a triple cell was manufactured using a roll-to-roll plasma CVD apparatus capable of forming a nipnipnip type triple cell as shown in FIG. Table 4 shows the film forming conditions.
[0098]
[Table 4]

[0099]
A stainless steel strip substrate in which an aluminum thin film (0.2 μm) and a ZnO thin film (1.2 μm) are vapor-deposited by sputtering as a lower electrode instead of the stainless steel strip substrate (SUS430) in a vacuum vessel 501 having a substrate delivery mechanism. (SUS430) A bobbin 503 wound with 502 is set, and in the same manner as in the above experiment, the belt-like substrate is a gas gate 504, n-type semiconductor layer vacuum vessels 505, 506, 507, i-type semiconductor layer vacuum vessels 508, 509, microwave plasma. Second i-type semiconductor layer vacuum vessels 510, 511 by the method, i-type semiconductor layer vacuum vessels 512, 513, 514 by the RF plasma CVD method, i-type semiconductor layer vacuum vessels 515, 516, p-type semiconductor layer vacuum vessel 517, Through 518 and 519 to the winding chamber 520 of the belt-like substrate, The tension was adjusted so that there was no slack. Each vacuum vessel 505-519 is 1.3 × 10^-FourPa (1 × 10^-6The pressure was reduced to Torr).
[0100]
The i-type semiconductor layer discharge vessels 521 and 522 by the microwave plasma method are provided with an opening adjusting plate 102 as shown in FIG. Yes. Thereby, the deposition region 103 is limited.
[0101]
As a heat treatment during film formation, H is used as the gate gas from the gate gas introduction pipe to the gas gate.₂Was introduced at 1000 sccm, and the belt-like substrate was heated to 300 ° C. by a substrate heating heater.
[0102]
The source gas is introduced into each discharge vessel from the gas introduction tube, the belt-like substrate is conveyed at a speed of 1270 mm / min, electric power is applied from the microwave oscillator and the high frequency oscillator to each discharge vessel, and plasma discharge is performed in the film formation region. Then, a nipnipnip type amorphous silicon film was formed on the belt-like substrate.
[0103]
After transporting one roll of the belt-like substrate, all plasma, all gas supply, all lamp heater energization, and transportation were stopped. Next, nitrogen (N₂) Gas was introduced into the discharge vessel, the pressure was returned to atmospheric pressure, and the belt-like substrate wound around the winding bobbin was taken out.
[0104]
On the formed nipnipnip type amorphous silicon film, ITO (In₂O_Three+ SnO₂) Was deposited by vacuum deposition to 70 nm, and as a collecting electrode, Al was deposited by 2 μm by vacuum deposition to produce a photovoltaic device.
[0105]
The evaluation of the formed solar cell is based on spectral sensitivity characteristics and AM value of 1.5, energy density of 100 mW / cm.²This was evaluated by measuring the photoelectric conversion efficiency η when irradiated with simulated sunlight. Further, in order to evaluate the distribution in the width direction, the spectral sensitivity characteristic and the photoelectric conversion efficiency were measured at five points at the center (C) and both ends (F, FC, RC, R) in the width direction of the belt-like substrate. The results are shown in Table 5.
[0106]
[Table 5]

[0107]
In addition, a solar cell having a size of 350 mm × 240 mm was produced, and the efficiency of the entire substrate was evaluated. The results are shown in Table 6.
[0108]
[Table 6]

[0109]
As is clear from Tables 5 and 6, it was found that the unevenness of the total deposited film thickness was suppressed to within 10% by the aperture adjusting plate, thereby suppressing the unevenness of the relative sensitivity and photoelectric conversion efficiency. Moreover, it was found that the photoelectric conversion efficiency of the entire photovoltaic device in the substrate width direction can be improved by suppressing the unevenness of the photoelectric conversion efficiency.
[0110]
(Comparative Example 1)
In this comparative example, the film was formed using the opening adjusting plate 102 as shown in FIG. 1 in Example 1, but the opening adjusting plate 601 shown in FIG. 6 having a uniform opening length in the width direction was used. . Other film forming conditions were the same as in Example 1. In this comparative example, the microwave power and other film forming conditions were set as shown in Table 1 and manufactured.
[0111]
The thickness distribution in the width direction of the obtained deposited film was as shown in Table 3. It was found that the uneven thickness distribution of the obtained deposited film was larger than 10%.
[0112]
In the same manner as in Example 1, a nipnipnip type amorphous silicon film was formed on a strip substrate. On the n-type layer, ITO (In₂O_Three+ SnO₂) Was deposited by vacuum deposition to 70 nm, and as a collecting electrode, Al was deposited by 2 μm by vacuum deposition to produce a photovoltaic device.
[0113]
Evaluation of the formed photovoltaic device was performed using spectral sensitivity characteristics and AM value of 1.5, energy density of 100 mW / cm.²This was evaluated by measuring the photoelectric conversion efficiency η when irradiated with simulated sunlight.
[0114]
The results are shown in Table 5. In addition, a photovoltaic device having a size of 350 mm × 240 mm was produced, and the overall efficiency in the substrate width direction was evaluated. The results are shown in Table 6.
[0115]
When the opening adjusting plate 601 was used, the unevenness of the deposited film thickness was larger than 10%. Unevenness of the photoelectric conversion efficiency is caused by the unevenness of the deposited film thickness, and as a result, the photoelectric conversion efficiency in the entire substrate width direction of the photovoltaic element has not been improved.
[0116]
(Example 2)
In this example, the i-layer was formed by introducing microwave power using four applicators 222 as shown in FIG. 2 in Example 1, but as shown in FIG. An example in which microwave power is introduced to form an i layer using a single applicator 701 will be described. The film forming conditions were set as shown in Table 1 and manufactured. In FIG. 7, reference numeral 702 denotes an opening adjustment plate, 703 denotes a deposition region, and 704 denotes a belt-like substrate.
[0117]
In accordance with the procedure shown in the first embodiment, a belt-like substrate (SUS430) is passed through each vacuum vessel, and 1.3 × 10 6 by an exhaust device (not shown).^-FourPa (1 × 10^-6After reducing the pressure to Torr), a discharge is generated to form an i-type amorphous silicon film on the belt-like substrate. The discharge vessels 207a and 207b are not provided with the opening adjusting plate 219 for controlling the deposited film thickness distribution at the openings of the respective discharge vessels, and a deposited film is formed over the entire openings of the discharge vessels 207a and 207b. After confirming the stability of the discharge state, the conveyance was stopped and a stationary sample was produced.
[0118]
Further, in order to evaluate the distribution in the width direction, the deposition rate is 21 points in total, 3 points at the center (C) and both ends (F, R) of the belt-like substrate and 7 points in the substrate transport direction as shown in FIG. The deposition rate was measured with a spectroscope. The results of the deposition rate distribution of the obtained deposited film are shown in Table 7 and FIG.
[0119]
[Table 7]

[0120]
As can be seen from Table 7 and FIG. 8, the deposition rate of the obtained deposited film is not constant in the substrate width direction and the transport direction, and when the belt-like substrate 210 is transported and deposited, the total deposited film thickness is the width. A large distribution was produced in the direction.
[0121]
Based on the measurement of the deposition rate distribution, the shape of the aperture adjusting plate was determined.
The transport direction of the strip-shaped substrate in the discharge space is the X direction,
The direction perpendicular to the transport direction within the plane of the strip-shaped substrate in the discharge space is the Y direction,
Arbitrary point (x where the belt-like substrate film deposition surface passes in the discharge space)_i, Y_j) Is the deposition rate of the film on the strip substrate measured in d)_i, Y_j),
Substrate transport speed is v = 1270 (mm / min)
Ideal deposited film thickness δ = 700 (Å)
And
[0122]
First, y on the discharge space₁= 60 (mm), x_P1≦ x₁≦ x_Q1The deposited film thickness at₁(X, y₁)
The width L in the transport direction of the discharge space when no opening adjusting plate is provided L = 250
x_P1+ X_Q1= 250 (This formula is x as seen from the center line of the discharge space._P1, X_Q1Is set to be symmetric, not required)
As
d₁(X, y₁) = D₁(Vt, y₁) =-1.2t²+ 16t + 35 (∵x = vt)
[0123]
[Formula 18]

Satisfying equation (1) (t, y₁) = A₁(2.8, 60), B₁(9.0, 60)
∴ (x, y) = A₁(59, 60), B₁(191, 60)
[0124]
Next, y on the discharge space₂= 20 (mm), x_P2≦ x₂≦ x_Q2The deposited film thickness at δ (x, y₂)
The width L in the transport direction of the discharge space when no opening adjusting plate is provided L = 250
x_P2+ X_Q2= 250 (This formula is x as seen from the center line of the discharge space._P2, X_Q2Is set to be symmetric, not required)
As
d₂(X, y₂) = D₂(Vt, y₂) =-1.3t²+ 19t + 29 (∵x = vt)
[0125]
[Equation 19]

(1) satisfies the expression (t, y₂) = A₂(0.91,35), B₂(10.89, 35)
∴ (x, y) = A₂(19, 20), B₂(231, 20)
[0126]
Next, y on the discharge space_Three= 100 (mm), x_P3≦ x_Three≦ x_Q3The deposited film thickness at δ (x, y_Three)
The width L in the transport direction of the discharge space when no opening adjusting plate is provided L = 250
x_P3+ X_Q3= 250 (This formula is x as seen from the center line of the discharge space._P3, X_Q3Is set to be symmetric, not required)
As
d_Three(X, y_Three) = D_Three(Vt, y_Three) =-5.2t²+ 33t + 35 (∵x = vt)
[0127]
[Expression 20]

(1) ”is satisfied (t, y_Three) = A_Three(0.35,100), B_Three(11.45, 100)
∴ (x, y) = A_Three(17,100), B_Three(123,100)
[0128]
Point A₁, A₂, A_ThreeA quadratic curve passing through x = F₁(Y) = 2.6 × 10^-2y²-5.2y-94 (2)
Point B₁, B₂, B_ThreeA quadratic curve passing through x = F₂(Y) = − 5.9 × 10^-Foury²+ 6.0y + 107 (3)
[0129]
The shape of the aperture adjusting plate is determined from the obtained curve, and the deposited film thickness distribution of the belt-like substrate 704 is determined using the aperture adjusting plate 702 having a distribution in the width direction of the deposition region 703 as shown in FIG. Control was performed to produce a nip type single cell. The process until gas introduction is performed in the same manner as in Experiment 1. The belt-like substrate 704 is conveyed at a speed of 1270 mm / min, and microwave power and RF power are applied from the microwave oscillator 220 and the RF oscillator 227 into the discharge vessel. Plasma discharge was generated in the film formation region, and a nip type amorphous silicon film was formed on the belt-like substrate.
[0130]
On the formed nip type amorphous silicon film, ITO (In₂O_Three+ SnO₂) Was deposited by vacuum deposition to 70 nm, and as a collecting electrode, Al was deposited by 2 μm by vacuum deposition to produce a photovoltaic device. The film thickness distribution of the i layer was evaluated from the CV characteristics of the obtained photovoltaic element. Table 8 shows the film thickness distribution of the obtained deposited film.
[0131]
[Table 8]

[0132]
It was found that the obtained deposited film thickness was uniform in the width direction, and the unevenness of the deposited film thickness was suppressed within 10%.
[0133]
Next, a triple cell was manufactured using a roll-to-roll plasma CVD apparatus capable of forming a nipnipnip type triple cell as shown in FIG. Table 4 shows the film forming conditions.
[0134]
A stainless steel strip substrate (SUS430) in which an aluminum thin film (0.2 μm) and a ZnO thin film (1.2 μm) are vapor-deposited by sputtering as a lower electrode instead of the stainless steel strip substrate (SUS430) in a vacuum container 501 having a substrate delivery mechanism. ) A bobbin 503 wound with 502 is set, and the belt-like substrate is formed by a gas gate 504, n-type semiconductor layer vacuum vessels 505, 506, 507, i-type semiconductor layer vacuum vessels 508, 509, and a microwave plasma method as in the above experiment. i-type semiconductor layer vacuum vessels 510, 511, i-type semiconductor layer vacuum vessels 512, 513, 514, i-type semiconductor layer vacuum vessels 515, 516, and p-type semiconductor layer vacuum vessels 517, 518, 519 by RF plasma CVD. Through the strip-shaped substrate take-up chamber 520 and no slack. The tension was adjusted to the extent. Each vacuum vessel 505-519 is 1.3 × 10^-FourPa (1 × 10^-6The pressure was reduced to Torr).
[0135]
The i-type semiconductor layer discharge vessels 521 and 522 by the microwave plasma method are provided with an opening adjusting plate 102 as shown in FIG. Yes. Thereby, the deposition region 103 is limited.
[0136]
As a heat treatment during film formation, H is used as the gate gas from the gate gas introduction pipe to the gas gate.₂Each was introduced at 1000 sccm, and the belt-like substrate was heated to 300 ° C. by a substrate heating heater.
[0137]
The source gas is introduced into each discharge vessel from the gas introduction tube, the belt-like substrate is conveyed at a speed of 1270 mm / min, electric power is applied from the microwave oscillator and the high frequency oscillator to each discharge vessel, and plasma discharge is performed in the film formation region. Then, a nipnipnip type amorphous silicon film was formed on the belt-like substrate.
[0138]
After transporting one roll of the belt-like substrate, all plasma, all gas supply, all lamp heater energization, and transportation were stopped. Next, nitrogen (N₂) Gas was introduced into the discharge vessel, the pressure was returned to atmospheric pressure, and the belt-like substrate wound around the winding bobbin was taken out.
[0139]
On the formed nipnipnip type amorphous silicon film, ITO (In₂O_Three+ SnO₂) Was deposited by vacuum deposition to 70 nm, and as a collecting electrode, Al was deposited by 2 μm by vacuum deposition to produce a photovoltaic device.
[0140]
Evaluation of the formed photovoltaic device was performed by spectral sensitivity characteristics and AM value of 1.5, energy density of 100 W / cm.²This was evaluated by measuring the photoelectric conversion efficiency η when irradiated with simulated sunlight.
[0141]
Further, in order to evaluate the distribution in the width direction, spectral sensitivity characteristics and photoelectric conversion efficiency were measured at three points of the central portion (C) and both end portions (F, R) in the width direction of the strip substrate. The results are shown in Table 9.
[0142]
[Table 9]

[0143]
In addition, a photovoltaic device having a size of 350 mm × 240 mm was produced, and the overall efficiency in the substrate width direction was evaluated. The results are shown in Table 10.
[0144]
[Table 10]

[0145]
As is clear from Tables 9 and 10, it was found that the unevenness of the total deposited film thickness was suppressed to within 5% by the aperture adjustment plate, thereby suppressing the unevenness of the relative sensitivity and photoelectric conversion efficiency. Moreover, it was found that the photoelectric conversion efficiency of the entire photovoltaic device in the substrate width direction can be improved by suppressing the unevenness of the photoelectric conversion efficiency.
[0146]
(Comparative Example 2)
In this comparative example, the film was formed using the opening adjusting plate 702 shown in FIG. 7 in Example 2, but the opening adjusting plate 901 shown in FIG. 9 having a uniform opening length in the width direction was used. Other film forming conditions were the same as in Example 2. In this comparative example, the microwave power and other film forming conditions were set as shown in Table 1 and manufactured. In FIG. 9, 902 is an applicator, 903 is a deposition region, and 904 is a belt-like substrate.
[0147]
The thickness direction thickness distribution of the obtained deposited film was as shown in Table 8. It was found that the uneven thickness distribution of the obtained deposited film was larger than 10%.
[0148]
As in Example 2, a nipnipnip type amorphous silicon film was formed on the strip substrate. On the n-type layer, ITO (In₂O_Three+ SnO₂) Was deposited by vacuum deposition to 70 nm, and as a collecting electrode, Al was deposited by 2 μm by vacuum deposition to produce a photovoltaic device.
[0149]
Evaluation of the formed photovoltaic device was performed using spectral sensitivity characteristics and AM value of 1.5, energy density of 100 mW / cm.²This was evaluated by measuring the photoelectric conversion efficiency η when irradiated with simulated sunlight.
[0150]
The results are shown in Table 9. In addition, a photovoltaic device having a size of 350 mm × 240 mm was produced, and the overall efficiency in the substrate width direction was evaluated. The results are shown in Table 10.
[0151]
When the opening adjusting plate 901 was used, the unevenness of the deposited film thickness was larger than 10%. Unevenness of the photoelectric conversion efficiency is caused by the unevenness of the deposited film thickness, and as a result, the photoelectric conversion efficiency in the entire substrate width direction of the photovoltaic element has not been improved.
[0152]
Example 3
In this example, the i-layer was formed by introducing microwave power using four applicators 222 as shown in FIG. 2 in Example 1, but as shown in FIG. An example in which microwave power is introduced to form an i layer using a single applicator 1001 will be described. The film forming conditions were set as shown in Table 1 and manufactured. In FIG. 10, reference numeral 1002 denotes an opening adjusting plate, 1003 denotes a deposition region, and 1004 denotes a belt-like substrate.
[0153]
In accordance with the procedure shown in Example 1, a stainless steel strip substrate (SUS430) is passed through each vacuum vessel, and 1.3 × 10 6 by an exhaust device (not shown).^-FourPa (1 × 10^-6After reducing the pressure to Torr), a discharge was generated, and an i-type amorphous silicon film was formed on the strip substrate. The discharge vessels 207a and 207b are not provided with an opening adjusting plate 219 for controlling the deposited film thickness distribution at the openings of the respective discharge vessels, and a deposited film is formed over the entire openings of the discharge vessels 207a and 207b. After confirming the stability of the discharge state, transportation was stopped and a stationary sample was produced.
[0154]
In addition, in order to evaluate the distribution in the width direction, the deposition rate is 15 points in total, 3 points at the center (C) and both ends (F, R) of the belt-like substrate and 5 points in the substrate transport direction as shown in FIG. The deposition rate was measured with a spectroscope. The result of the deposition rate distribution of the obtained deposited film is shown in Table 11 and FIG.
[0155]
[Table 11]

[0156]
As can be seen from Table 11 and FIG. 11, the deposition rate of the deposited film is not constant in the substrate width direction and the transport direction, and when the belt-like substrate 210 is transported and deposited, the total deposited film thickness is the width direction. Produces a large distribution.
[0157]
Based on the measurement of the deposition rate distribution, the shape of the aperture adjusting plate was determined.
The transport direction of the strip-shaped substrate in the discharge space is the X direction,
The direction perpendicular to the transport direction within the plane of the strip-shaped substrate in the discharge space is the Y direction,
Arbitrary point (x where the belt-like substrate film deposition surface passes in the discharge space)_i, Y_j) Is the deposition rate of the film on the strip substrate measured in d)_i, Y_j),
Substrate transport speed is v = 1270 (mm / min)
Ideal deposited film thickness δ = 600 (Å)
And
[0158]
First, y on the discharge space₁= 175 (mm), x_P1≦ x₁≦ x_Q1The deposited film thickness at₁(X, y₁)
The width L in the transport direction of the discharge space when no opening adjusting plate is provided L = 240
x_P1+ X_Q1= 240 (This expression is x as seen from the center line of the discharge space._P1, X_Q1Is set to be symmetric, not required)
As
d₁(X, y₁) = D₁(Vt, y₁) = − 0.93t²+ 10.5t + 38.9 (∵x = vt)
[0159]
[Expression 21]

Satisfying equation (1) (t, y₁) = A₁(0.43,175), B₁(10.87, 175)
∴ (x, y) = A₁(9,175), B₁(231,175)
[0160]
Next, y on the discharge space₂= 35 (mm), x_P2≦ x₂≦ x_Q2The deposited film thickness at δ (x, y₂)
The width L in the transport direction of the discharge space when no opening adjusting plate is provided L = 240
x_P2+ X_Q2= 240 (This expression is x as seen from the center line of the discharge space._P2, X_Q2Is set to be symmetric, not required)
As
d₂(X, y₂) = D₂(Vt, y₂) = − 1.45t²+ 16.9t + 32.1 (∵x = vt)
[0161]
[Expression 22]

(1) satisfies the expression (t, y₂) = A₂(0.80, 35), B₂(10.5, 35)
∴ (x, y) = A₂(17, 35), B₂(223, 35)
[0162]
Next, y on the discharge space_Three= 315 (mm), x_P3≦ x_Three≦ x_Q3The deposited film thickness at δ (x, y_Three)
The width L in the transport direction of the discharge space when no opening adjusting plate is provided L = 240
x_P3+ X_Q3= 240 (This expression is x as seen from the center line of the discharge space._P3, X_Q3Is set to be symmetric, not required)
As
d_Three(X, y_Three) = D_Three(Vt, y_Three) =-5.2t²+ 33t + 35 (∵x = vt)
[0163]
[Expression 23]

(1) ”is satisfied (t, y_Three) = A_Three(1.05, 315), B_Three(10.25, 315)
∴ (x, y) = A_Three(23,315), B_Three(217,315)
[0164]
Point A₁, A₂, A_ThreeA quadratic curve passing through x = F₁(Y) = 5.6 × 10^-Foury²-0.17y + 22 (2)
Point B₁, B₂, B_ThreeA quadratic curve passing through x = F₂(Y) = − 5.6 × 10^-Foury²+ 0.17y + 218 (3)
[0165]
The shape of the aperture adjusting plate is determined from the obtained curve, and the deposited film thickness distribution of the belt-like substrate 1004 is determined using the aperture adjusting plate 1002 having the distribution in the width direction of the deposition region 1003 as shown in FIG. Control was performed to produce a nip type single cell. The process up to gas introduction is performed in the same manner as in Experiment 1. The belt-like substrate 1004 is transported at a speed of 1270 mm / min, and microwave power and RF power are applied from the microwave oscillator 220 and the RF oscillator 227 into the discharge vessel. Plasma discharge was generated in the film formation region, and a nip type amorphous silicon film was formed on the belt-like substrate.
[0166]
On the formed nip type amorphous silicon film, ITO (In₂O_Three+ SnO₂) Was deposited by vacuum deposition to 70 nm, and as a collecting electrode, Al was deposited by 2 μm by vacuum deposition to produce a photovoltaic device. The film thickness distribution of the i layer was evaluated from the CV characteristics of the obtained photovoltaic element. Table 12 shows the film thickness distribution of the obtained deposited film.
[0167]
[Table 12]

[0168]
It was found that the obtained deposited film thickness was uniform in the width direction, and the unevenness of the deposited film thickness was suppressed within 10%.
[0169]
Next, a triple cell was manufactured using a roll-to-roll plasma CVD apparatus capable of forming a nipnipnip type triple cell as shown in FIG. Table 4 shows the film forming conditions.
[0170]
A stainless steel strip substrate (SUS430) in which an aluminum thin film (0.2 μm) and a ZnO thin film (1.2 μm) are vapor-deposited by sputtering as a lower electrode instead of the stainless steel strip substrate (SUS430) in a vacuum container 501 having a substrate delivery mechanism. ) A bobbin 503 wound with 502 is set, and the belt-like substrate is formed by a gas gate 504, n-type semiconductor layer vacuum vessels 505, 506, 507, i-type semiconductor layer vacuum vessels 508, 509, and a microwave plasma method as in the above experiment. i-type semiconductor layer vacuum vessels 510, 511, i-type semiconductor layer vacuum vessels 512, 513, 514, i-type semiconductor layer vacuum vessels 515, 516, and p-type semiconductor layer vacuum vessels 517, 518, 519 by RF plasma CVD. Through the strip-shaped substrate take-up chamber 520 and no slack. The tension was adjusted to the extent. Each vacuum vessel 505-519 is 1.3 × 10^-FourPa (1 × 10^-6The pressure was reduced to Torr).
[0171]
The i-type semiconductor layer discharge vessels 521 and 522 by the microwave plasma method are provided with an opening adjusting plate 102 as shown in FIG. Yes. Thereby, the deposition region 103 is limited.
[0172]
As a heat treatment during film formation, H is used as the gate gas from the gate gas introduction pipe to the gas gate.₂Was introduced at 1000 sccm, and the belt-like substrate was heated to 300 ° C. by a substrate heating heater.
[0173]
The source gas is introduced into each discharge vessel from the gas introduction tube, the belt-like substrate is conveyed at a speed of 1270 mm / min, electric power is applied from the microwave oscillator and the high frequency oscillator to each discharge vessel, and plasma discharge is performed in the film formation region. Then, a nipnipnip type amorphous silicon film was formed on the belt-like substrate.
[0174]
After one band of the belt-shaped substrate was transported, all plasma, all gas supply, all lamp heater energization, and transport were stopped. Next, nitrogen (N₂) Gas was introduced into the discharge vessel, the pressure was returned to atmospheric pressure, and the belt-like substrate wound around the winding bobbin was taken out.
[0175]
On the formed nipnipnip type amorphous silicon film, ITO (In₂O_Three+ SnO₂) Was deposited by vacuum deposition to 70 nm, and as a collecting electrode, Al was deposited by 2 μm by vacuum deposition to produce a photovoltaic device.
[0176]
Evaluation of the formed photovoltaic device was performed using spectral sensitivity characteristics and AM value of 1.5, energy density of 100 mW / cm.²This was evaluated by measuring the photoelectric conversion efficiency η when irradiated with simulated sunlight. Further, in order to evaluate the distribution in the width direction, spectral sensitivity characteristics and photoelectric conversion efficiency were measured at the central part (C) and both end parts (F, R) in the width direction of the belt-like substrate. The results are shown in Table 13.
[0177]
[Table 13]

[0178]
Moreover, a photovoltaic element having a size of 350 mm × 240 mm was produced, and the efficiency of the entire photovoltaic element in the substrate width direction was evaluated. The results are shown in Table 14.
[0179]
[Table 14]

[0180]
As is apparent from Tables 13 and 14, it was found that the unevenness of the total deposited film thickness was suppressed within 10% by the aperture adjusting plate, thereby suppressing the unevenness of the relative sensitivity and photoelectric conversion efficiency. Moreover, it was found that the photoelectric conversion efficiency of the entire photovoltaic device in the substrate width direction can be improved by suppressing the unevenness of the photoelectric conversion efficiency.
[0181]
(Comparative Example 3)
In this comparative example, while the film was formed using the opening adjustment plate 1002 shown in FIG. 10 in Example 3, the opening adjustment plate 1201 shown in FIG. 12 having a uniform opening length in the width direction was used. Other film forming conditions were the same as in Example 3. In this comparative example, the microwave power and other film forming conditions were set as shown in Table 1 and manufactured. In FIG. 12, reference numeral 1202 denotes an applicator, 1203 denotes a deposition region, and 1204 denotes a belt-like substrate.
[0182]
The thickness direction film thickness distribution of the obtained deposited film was as shown in Table 12. It was found that the uneven thickness distribution of the obtained deposited film was larger than 10%.
[0183]
In the same manner as in Example 3, a nipnipnip type amorphous silicon film was formed on the strip substrate. On the n-type layer, ITO (In₂O_Three+ SnO₂) Was deposited by vacuum deposition to 70 nm, and as a collecting electrode, Al was deposited by 2 μm by vacuum deposition to produce a photovoltaic device.
[0184]
Evaluation of the formed photovoltaic device was performed using spectral sensitivity characteristics and AM value of 1.5, energy density of 100 mW / cm.²This was evaluated by measuring the photoelectric conversion efficiency η when irradiated with simulated sunlight. The results are shown in Table 13.
[0185]
In addition, a photovoltaic device having a size of 350 mm × 240 mm was produced, and the overall efficiency in the substrate width direction was evaluated. The results are shown in Table 14.
[0186]
When the opening adjusting plate 1201 was used, the unevenness of the deposited film thickness was larger than 10%. Unevenness of the photoelectric conversion efficiency is caused by the unevenness of the deposited film thickness, and as a result, the photoelectric conversion efficiency of the entire photovoltaic device in the substrate width direction is lowered.
[0187]
【The invention's effect】
As described above, according to the deposited film forming method and the deposited film forming apparatus of the present invention, the deposited film is formed by installing the opening adjusting plate at the opening of the discharge vessel so as to partially block the strip-shaped substrate and the discharge region. The film thickness distribution in the width direction can be improved and the characteristics of the deposited film can be made uniform. As a result, it is possible to provide a large-area photovoltaic element having high uniformity and good characteristics and a device thereof.
[Brief description of the drawings]
FIG. 1 is a conceptual diagram of Example 1 in which an opening adjusting plate is provided at the opening of a discharge vessel so as to make the film thickness distribution in the width direction of the belt-like substrate of the present invention uniform.
FIG. 2 is a schematic diagram of a roll-to-roll type plasma CVD apparatus used for manufacturing a single cell in an example of the present invention.
FIG. 3 is a diagram illustrating a place where unevenness in the width direction is evaluated in the example of the present invention.
FIG. 4 is a diagram showing a deposition rate distribution of a stationary sample in an example of the present invention.
FIG. 5 is a schematic schematic view of a roll-to-roll type plasma CVD apparatus used for producing a triple cell in an example of the present invention.
6 is a schematic conceptual diagram of an aperture adjustment plate in Comparative Example 1. FIG.
FIG. 7 is a conceptual diagram of Example 2 in which an opening adjusting plate is provided at the opening of the discharge vessel so as to make the film thickness distribution in the width direction of the belt-like substrate of the present invention uniform.
8 is a graph showing a deposition rate distribution of a stationary sample in Example 2. FIG.
9 is a schematic conceptual diagram of an aperture adjustment plate in Comparative Example 2. FIG.
FIG. 10 is a conceptual diagram of Example 3 in which an opening adjusting plate is provided at the opening of the discharge vessel so as to make the film thickness distribution in the width direction of the belt-like substrate of the present invention uniform.
11 is a graph showing a deposition rate distribution of a stationary sample in Example 3. FIG.
12 is a schematic conceptual diagram of an aperture adjustment plate in Comparative Example 3. FIG.
[Explanation of symbols]
101 Applicator
102 Opening adjustment plate
103 deposition area
104 Banded substrate
201 Substrate delivery container
202 n-type semiconductor layer vacuum vessel
203 i-type semiconductor layer vacuum container
204 i-type semiconductor layer vacuum container
205 p-type semiconductor layer vacuum vessel
206 i-type semiconductor layer vacuum vessel
207a i-type semiconductor layer discharge vessel
207b i-type semiconductor layer discharge vessel
208 Substrate winding container
209 Gas gate
210 Banded substrate
211 Delivery bobbin
212 Board winding bobbin
213 Heating heater
214 Gas introduction pipe
215 Gas heater
216 Gas exhaust pipe
217 Exhaust adjustment valve
218 Microwave discharge region
219 Opening adjustment plate
220 microwave oscillator
221 Waveguide
222 Applicator
223 RF bias bar
224 RF discharge region
225 cathode
226 Gate gas introduction pipe
227 RF oscillator
501 Substrate delivery container
502 Strip substrate
503 Delivery bobbin
504 gas gate
505 n-type semiconductor layer vacuum vessel
506 n-type semiconductor layer vacuum vessel
507 n-type semiconductor layer vacuum vessel
508 i-type semiconductor layer vacuum vessel
509 i-type semiconductor layer vacuum vessel
510 i-type semiconductor layer vacuum vessel by microwave plasma method
511 i-type semiconductor layer vacuum vessel by microwave plasma method
512 i-type semiconductor layer vacuum vessel by RF plasma CVD method
513 i-type semiconductor layer vacuum container by RF plasma CVD method
514 i-type semiconductor layer vacuum container by RF plasma CVD method
515 i-type semiconductor layer vacuum vessel
516 i-type semiconductor layer vacuum container
517 p-type semiconductor layer vacuum vessel
518 p-type semiconductor layer vacuum vessel
519 p-type semiconductor layer vacuum vessel
520 Substrate winding container
521 i-type semiconductor layer discharge vessel by microwave plasma CVD method
522 i-type semiconductor layer discharge vessel by microwave plasma CVD method
601 Aperture adjustment plate
602 Applicator
603 Deposition area
604 strip substrate
701 Applicator
702 Opening adjustment plate
703 Deposition area
704 Strip substrate
901 Opening adjustment plate
902 Applicator
903 Deposition area
904 Strip substrate
1001 Applicator
1002 Aperture adjustment plate
1003 Deposition region
1004 Strip substrate
1201 Aperture adjustment plate
1202 Applicator
1203 Deposition region
1204 strip substrate

Claims (18)

In a deposition film forming method for continuously forming a deposition film on a substrate while generating plasma in a plurality of continuous vacuum vessels and continuously moving the strip substrate in the longitudinal direction thereof,
The opening of the discharge vessel, based on the measurement of deposition rate distribution, and opens adjusted by opening adjusting plate set a shape such unevenness of the deposited film thickness in the substrate width direction is reduced, the deposited film forming intends rows deposition A method,
The transport direction of the strip substrate in the discharge space is the X direction,
A direction perpendicular to the transport direction in the plane of the strip-shaped substrate in the discharge space is the Y direction,
D (x _i , y _j ) represents the deposition rate of the film on the band substrate measured at an arbitrary point (x _i , y _j ) through which the band-shaped substrate film deposition surface in the discharge space passes .
(However, i = 1, 2,..., M, j = 1, 2,..., N, where m and n are both 3 or more)
Substrate transport speed is v,
With the ideal deposited film thickness as δ,
The deposition rate distribution in the X direction at y = y _j on the discharge space is approximated by a quadratic curve from the d (x _i , y _j ), and the following equation (1) is obtained:
d _j (x, y _j ) = d _j (vt, y _j ) = a _j t ² + b _j t + c _j (∵x = vt, t is time) (1)
Further, the following equation (2) is obtained so that the deposited film thickness δ _j (x, y _j ) at y = y _j on the discharge space becomes δ,

Substituting the above equation (1) into equation (2 ) to obtain a point A _j (vt _j1 , y _j ) and a point B _j (vt _j2 , y _j ) that satisfy this ,
The following equations (3) and (4) are obtained as approximate curves from three or more points A _j and B _j , respectively.
x = F ₁ (y) (3)
x = F ₂ (y) (4)
The curve satisfying the equation (3) and the curve satisfying the equation (4) are set so as to be at both ends in the X direction of the opening of the discharge vessel, and the opening of the discharge vessel is adjusted to deposit the belt-shaped substrate. A method for forming a deposited film, wherein the region is limited. Wherein the X direction of the center position of the discharge space point _{A j (vt j1, y j} ) and the point _{B j (vt j2, y j} ) as the distance to become equal, the point A _j (vt _j1, y _j ) and point B _j (vt _j2, the deposited film forming method according to claim 1, characterized in that determining the y _j). The shape of the aperture adjusting plate is such that an arc passing through the point A _j (vt _j1 , y _j ) and an arc passing through the point B _j (vt _j2 , y _j ) determined from the widthwise deposition rate distribution of the band-shaped substrate 3. The deposition region of the strip-shaped substrate is limited by setting the shape of both ends in the X direction of the opening of the discharge vessel and adjusting the opening of the discharge vessel. A method for forming a deposited film. The shape of the aperture adjusting plate, according to any one of claims 1 to 3, characterized in that is set to be within ± 10% of the opening shape required from the widthwise deposition rate distribution of the belt-like substrate A method for forming a deposited film. The shape of the aperture adjusting plate, unevenness of the film thickness distribution in the width direction of the belt-like substrate of deposited film according to any one of claims 1-4, characterized in that it is set to be within 10% Deposited film forming method. The deposited film, the deposited film forming method according to any one of claims 1 to 5, characterized in that is formed by the microwave plasma CVD method. A roll-to-roll method is adopted, in which a strip-shaped substrate drawn out from a state wound in a roll shape in a plurality of discharge vessels is continuously moved and wound again in a roll shape. deposited film formation method according to any one of 6. In a deposition film forming apparatus for continuously forming a deposition film on a substrate while generating plasma in a plurality of continuous vacuum vessels and continuously moving the belt-like substrate in the longitudinal direction,
The opening of the discharge vessel, based on the measurement of deposition rate distribution, a deposited film forming apparatus Ru an opening adjusting plate set a shape such unevenness of the deposited film thickness in the substrate width direction is reduced,
The transport direction of the strip substrate in the discharge space is the X direction,
A direction perpendicular to the transport direction in the plane of the strip-shaped substrate in the discharge space is the Y direction,
D (x _i , y _j ) represents the deposition rate of the film on the band substrate measured at an arbitrary point (x _i , y _j ) through which the band-shaped substrate film deposition surface in the discharge space passes .
(However, i = 1, 2,..., M, j = 1, 2,..., N, where m and n are both 3 or more)
Substrate transport speed is v,
With the ideal deposited film thickness as δ,
The deposition rate distribution in the X direction at y = y _j on the discharge space is approximated by a quadratic curve from the d (x _i , y _j ), and the following equation (1) is obtained:
d _j (x, y _j ) = d _j (vt, y _j ) = a _j t ² + b _j t + c _j (∵x = vt, t is time) (1)
Further, the following equation (2) is obtained so that the deposited film thickness δ _j (x, y _j ) at y = y _j on the discharge space becomes δ,

Substituting the above equation (1) into equation (2 ) to obtain a point A _j (vt _j1 , y _j ) and a point B _j (vt _j2 , y _j ) that satisfy this ,
The following equations (3) and (4) are obtained as approximate curves from three or more points A _j and B _j , respectively.
x = F ₁ (y) (3)
x = F ₂ (y) (4)
The curve satisfying the expression (3) and the curve satisfying the expression (4) are set to be both ends in the X direction of the opening of the discharge vessel, respectively, and the deposition region of the belt-like substrate is limited to the opening of the discharge vessel. A deposition film forming apparatus characterized in that an opening adjusting plate is provided. Wherein the X direction of the center position of the discharge space point _{A j (vt j1, y j} ) and the point _{B j (vt j2, y j} ) as the distance to become equal, the point A _j (vt _j1, y _j ) and the deposited film forming apparatus according to claim 8, wherein the determination of the point _{B j (vt j2, y j} ). The shape of the aperture adjusting plate is such that an arc passing through the point A _j (vt _j1 , y _j ) and an arc passing through the point B _j (vt _j2 , y _j ) determined from the widthwise deposition rate distribution of the band-shaped substrate claim 8 set so that the shape of both ends of the X direction of the opening of the discharge vessel, characterized by installing the aperture adjusting plate for restricting the deposition region of the strip substrate in the opening of the discharge vessel Or the deposited film forming apparatus according to 9 . Claim 8, wherein placing the opening adjusting plate having the shape of the aperture adjusting plate, shaped such that within ± 10% of the shape of the opening adjusting plate obtained from the width direction deposition rate distribution of the belt-like substrate 10. The deposited film forming apparatus according to any one of 10 to 10 . The deposition according to any one of claims 8 to 11 , wherein an opening adjusting plate having a shape such that the unevenness of the film thickness distribution in the width direction of the belt-like substrate of the deposited film is within 10% is installed. Film forming device. The deposited film, the deposited film forming apparatus according to any one of claims 8 to 12, characterized in that it is formed by the microwave plasma CVD apparatus. 2. A roll-to-roll system device in which a strip-shaped substrate drawn out from a state wound in a roll shape in a plurality of discharge vessels is continuously moved and wound again in a roll shape. The deposited film forming apparatus according to any one of 8 to 13 . In a deposition film forming method for continuously forming a deposition film on a substrate while generating plasma in a plurality of continuous vacuum vessels and continuously moving the strip substrate in the longitudinal direction thereof,
The transport direction of the strip substrate in the discharge space is the X direction,
A direction perpendicular to the transport direction in the plane of the strip-shaped substrate in the discharge space is the Y direction,
D (x _i , y _j ) represents the deposition rate of the film on the band substrate measured at an arbitrary point (x _i , y _j ) through which the band-shaped substrate film deposition surface in the discharge space passes.
(However, i = 1, 2,..., M, j = 1, 2,..., N, where m and n are both 3 or more)
Substrate transport speed is v,
With the ideal deposited film thickness as δ,
The deposition rate distribution in the X direction at y = y _j on the discharge space is approximated by a quadratic curve from the d (x _i , y _j ), and the following equation (1) is obtained:
d _j (x, y _j ) = d _j (vt, y _j ) = a _j t ² + b _j t + c _j (∵x = vt, t is time) (1)
Further, the following equation (2) is obtained so that the deposited film thickness δ _j (x, y _j ) at y = y _j on the discharge space becomes δ,

Substituting the above equation (1) into equation (2) to obtain a point A _j (vt _j1 , y _j ) and a point B _j (vt _j2 , y _j ) that satisfy this,
The following equations (3) and (4) are obtained as approximate curves from three or more points A _j and B _j , respectively.
x = F ₁ (y) (3)
x = F ₂ (y) (4)
Furthermore, the following inequalities (5) and (6) defined based on the above equations (3) and (4) are obtained,
1.1F ₁ (y) −0.1F ₂ (y) ≦ X ≦ 0.9 F ₁ (y) + 0.1F ₂ (y) (5)
0.9F ₂ (y) + 0.1F ₁ (y) ≦ X ≦ 1.1F ₂ (y) −0.1F ₁ (y) (6)
The curve satisfying the equation (5) and the curve satisfying the equation (6) are set so as to be both ends in the X direction of the opening of the discharge vessel, and the opening of the discharge vessel is adjusted to deposit the belt-shaped substrate. A method for forming a deposited film, wherein the region is limited. Wherein the X direction of the center position of the discharge space point _{A j (vt j1, y j} ) and the point _{B j (vt j2, y j} ) as the distance to become equal, the point A _j (vt _j1, y _j ) and point B _j (vt _j2, the deposited film forming method according to claim 15, wherein the determination of the y _j). In a deposition film forming apparatus for continuously forming a deposition film on a substrate while generating plasma in a plurality of continuous vacuum vessels and continuously moving the strip substrate in the longitudinal direction thereof,
The transport direction of the strip substrate in the discharge space is the X direction,
A direction perpendicular to the transport direction in the plane of the strip-shaped substrate in the discharge space is the Y direction,
D (x _i , y _j ) represents the deposition rate of the film on the band substrate measured at an arbitrary point (x _i , y _j ) through which the band-shaped substrate film deposition surface in the discharge space passes.
(However, i = 1, 2,..., M, j = 1, 2,..., N, where m and n are both 3 or more)
Substrate transport speed is v,
With the ideal deposited film thickness as δ,
The deposition rate distribution in the X direction at y = y _j on the discharge space is approximated by a quadratic curve from the d (x _i , y _j ), and the following equation (1) is obtained:
d _j (x, y _j ) = d _j (vt, y _j ) = a _j t ² + b _j t + c _j (∵x = vt, t is time) (1)
Further, the following equation (2) is obtained so that the deposited film thickness δ _j (x, y _j ) at y = y _j on the discharge space becomes δ,

Substituting the above equation (1) into equation (2) to obtain a point A _j (vt _j1 , y _j ) and a point B _j (vt _j2 , y _j ) that satisfy this,
The following equations (3) and (4) are obtained as approximate curves from three or more points A _j and B _j , respectively.
x = F ₁ (y) (3)
x = F ₂ (y) (4)
Furthermore, the following inequalities (5) and (6) defined based on the above equations (3) and (4) are obtained,
1.1F ₁ (y) −0.1F ₂ (y) ≦ X ≦ 0.9 F ₁ (y) + 0.1F ₂ (y) (5)
0.9F ₂ (y) + 0.1F ₁ (y) ≦ X ≦ 1.1F ₂ (y) −0.1F ₁ (y) (6)
The curve satisfying the equation (5) and the curve satisfying the equation (6) are set so as to be both ends in the X direction of the opening of the discharge vessel, and the opening of the discharge vessel is adjusted to deposit the belt-shaped substrate. An apparatus for forming a deposited film, wherein the region is limited. Wherein the X direction of the center position of the discharge space point _{A j (vt j1, y j} ) and the point _{B j (vt j2, y j} ) as the distance to become equal, the point A _j (vt _j1, y _j ) and the deposited film forming apparatus according to claim 17, wherein the determination of the point _{B j (vt j2, y j} ).

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