JP4168775B2 - Thin film manufacturing method - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、金属元素を含む第１の原料物質と金属元素と反応する元素を含む第２の原料物質とを、基板に対して交互に供給することにより薄膜を形成する薄膜の製造方法、いわゆる原子層成長法に関する。
【０００２】
【従来の技術】
従来より、原子層成長法（Ａｔｏｍｉｃ Ｌａｙｅｒ Ｅｐｉｔａｘｙ：ＡＬＥ法）は、金属酸化物や金属硫化物の薄膜を形成する際に用いられ、結晶性が良く、膜厚制御性に優れた成膜方法として使用されている（例えば、特許文献１参照）。
【０００３】
この方法は、金属元素を含む第１の原料物質（例えば金属塩化物や有機金属化合物等）と、金属元素と反応する元素を含む第２の原料物質（例えば水等の酸化物質や硫化水素等の還元性物質等）とを、基板に対して交互に供給するサイクルを単純に繰り返すことにより、基板表面の反応にて反応化合物を１層ずつ基板表面に配置するものであり、供給する回数により膜厚を容易に制御できるとされている。
【０００４】
このＡＬＥ法を使用して、様々な薄膜を形成することが可能である。例えばエレクトロルミネッセンス素子において、絶縁層として用いられる酸化アルミニウムと酸化チタニウムとの複合膜であるＡＴＯ薄膜や、発光層として用いられる硫化亜鉛、硫化ストロンチウムがある。
【０００５】
【特許文献１】
特開昭５５−１３０８９６号公報
【０００６】
【発明が解決しようとする課題】
しかしながら、ＡＬＥ法は、上記のような利点があるが、一層づつ原子を配置するという形成方法であるため、薄膜を構成する各原料の供給時間を長くすると、所望の膜厚を得るために膨大な時間を要するという問題がある。
【０００７】
一方、本発明者の検討によれば、例えばＡＴＯ薄膜をＡＬＥ法にて形成する際、Ａｌ２Ｏ３薄膜とＴｉＯ２薄膜を交互に積層する場合において、Ａｌ２Ｏ３薄膜上にＴｉＯ２薄膜を形成する際、若しくはＴｉＯ２薄膜上にＡｌ２Ｏ３薄膜を形成する際に、成膜時間を短くしようとすると、単分子層膜厚から算出した原料供給回数で形成した膜厚が、狙い膜厚と異なり薄くなってしまうという問題が生じた。
【０００８】
そこで、本発明は上記問題に鑑み、金属元素を含む第１の原料物質と金属元素と反応する元素を含む第２の原料物質とを、基板に対して交互に供給することにより薄膜を形成する原子層成長法による薄膜の製造方法において、できるだけ短い形成時間で狙いの膜厚を適切に実現できるようにすることを目的とする。
【０００９】
【課題を解決するための手段】
本発明者は、上述したＡＴＯ薄膜の形成において狙い膜厚よりも薄くなってしまうという問題について、さらに検討を進めた。
【００１０】
例えばＴｉＯ２薄膜上にＡｌ２Ｏ３薄膜を形成する際、通常であればＡｌの原料であるＡｌＣｌ３を供給し、Ｈ２Ｏを供給することにより酸化しＡｌ２Ｏ３分子を形成する。
【００１１】
このとき、全体の薄膜形成時間を短縮する目的で、ＡｌＣｌ３原料の供給時間、すなわち１回のＡｌＣｌ３原料の供給量が少ないと、下地である異種の膜（つまりＴｉＯ２薄膜）上には結晶の整合性の悪化により、うまく成長することができない。その結果、１回の原料供給では下地の表面を十分にＡｌＣｌ３で覆うことができない。
【００１２】
そして、このままの状態で、ＡｌＣｌ３とＨ２Ｏの供給サイクルを繰り返し、膜成長を継続させると、部分的に成長の早い部分ができ、クラスター状にＡｌ２Ｏ３が成長する。その結果、できあがったＡｌ２Ｏ３薄膜が不均一な厚さとなり、所望の膜厚を制御良く得ることができないということが実験により判明した。
【００１３】
また、逆に１回のＡｌＣｌ３原料の供給量を十分な量として、供給サイクルを繰り返し継続した場合には、所望の膜厚を得るための成膜時間が膨大なものとなってしまう。
【００１４】
さらに、ＴｉＯ２薄膜上にＡｌ２Ｏ３薄膜を形成するような場合には、最初にＡｌの原料であるＡｌＣｌ３を供給すると、下地であるＴｉＯ２表面の分子とＡｌＣｌ３分子が置換反応し、ＴｉＯ２を侵食することを発見した。このことは、蒸気圧が薄膜原料よりも相対的に下地膜の方が高いような場合に起こりうると考えられる。
【００１５】
したがって、ＡｌＣｌ３原料が不均一に供給されると、ＴｉＯ２との置換反応が不均一に行われ、上記した下地との結晶の整合性不良による成長不良と相俟って、薄膜成長速度が異なる部分が生じ、不均一な膜厚となってしまうということがわかった。
【００１６】
これらの検討結果から、供給サイクルの初期の段階において下地との結晶の整合性不良や下地と薄膜原料物質との不均一な反応を解消してやれば、その後の供給において均一な膜成長ができるのではないかと考えた。本発明は、このような点に着目し、実験検討した結果、得られたものである。
【００１７】
すなわち、請求項１に記載の発明では、金属元素を含む第１の原料物質と金属元素と反応する元素を含む第２の原料物質とを、基板に対して交互に供給することにより薄膜を形成する原子層成長法による薄膜の製造方法において、供給サイクルのうち１回目のサイクルにおける第１の原料物質の供給時間を、２回目以降のサイクルにおける第１の原料物質の供給時間よりも長くすることを特徴とする。
【００１８】
それによれば、供給サイクルのうち１回目のサイクルにおける第１の原料物質の供給時間を十分に長くすることで、金属元素を含む第１の原料物質によって下地を十分に被覆することができる。
【００１９】
そのため、形成される薄膜とその下地との結晶の整合性が悪かったり、下地と薄膜原料物質との反応が起こりやすい場合であっても、供給サイクルの２回目以降においては、下地との結晶の整合性が良くなり、また、下地との反応も起こらないため、均一な層成長が可能となる。
【００２０】
そして、供給サイクルのうち１回目のサイクルにおける第１の原料物質の供給時間は長くなるが、２回目以降はそれよりも短く、ほぼ通常の供給時間とすることができるため、薄膜の形成時間全体ではさほど長時間とはならない。
【００２１】
よって、本発明によれば、できるだけ短い形成時間で狙いの膜厚を適切に実現することができる。
【００２２】
ここで、請求項２に記載の発明のように、第１の原料物質としては金属ハロゲン化物または有機金属化合物を用いることができる。
【００２３】
また、薄膜としてはアルミナ（Ａｌ２Ｏ３）等のようなが絶縁体や、チタニア（ＴｉＯ２）等のような半導体とすることができる。
【００２４】
なお、上記各手段の括弧内の符号は、後述する実施形態に記載の具体的手段との対応関係を示す一例である。
【００２５】
【発明の実施の形態】
以下、本発明を具体的な実施形態に基づいて説明する。本実施形態では、形成する薄膜は、ＥＬ素子の絶縁膜として用いられるＡＴＯ薄膜とした。これは、絶縁体であるＡｌ２Ｏ３（アルミナ）薄膜と半導体であるＴｉＯ２（チタニア）薄膜とをＡＬＥ法によって交互に多数積層してなる膜である。
【００２６】
ＥＬ素子の絶縁膜としてのＡＴＯ薄膜においては、ＡＬＥ法によって、Ａｌ２Ｏ３薄膜から順にＴｉＯ２薄膜、Ａｌ２Ｏ３薄膜の順に交互に積層し、最後に再びＡｌ２Ｏ３薄膜を形成する。
【００２７】
具体的には、Ａｌ２Ｏ３薄膜をＡＬＥ法にて形成する場合は、金属元素を含む第１の原料物質であるＡｌＣｌ３と、金属元素と反応する元素を含む第２の原料物質であるＨ２Ｏとを、基板に対して交互に供給するサイクルを繰り返すことで、Ａｌ２Ｏ３を１原子層ずつ成長させ、所定の膜厚のＡｌ２Ｏ３薄膜を形成する。
【００２８】
また、ＴｉＯ２薄膜をＡＬＥ法にて形成する場合は、金属元素を含む第１の原料物質であるＴｉＣｌ４と金属元素と反応する元素を含む第２の原料物質であるＨ２Ｏとを、基板に対して交互に供給するサイクルを繰り返すことで、ＴｉＯ２を１原子層ずつ成長させ、所定の膜厚のＴｉＯ２薄膜を形成する。
【００２９】
そして、各々所定の膜厚のＡｌ２Ｏ３薄膜とＴｉＯ２薄膜とが交互に積層されて、ＡＴＯ薄膜ができあがるのである。
【００３０】
ここでは、ＡＴＯ薄膜の最上部のＡｌ２Ｏ３薄膜および最下部のＡｌ２Ｏ３薄膜を除くＡｌ２Ｏ３薄膜の膜厚は５ｎｍとし、ＴｉＯ２薄膜の膜厚は１．５から５ｎｍの範囲であれば良く、本例では２ｎｍとした。また、最上部および最下部のＡｌ２Ｏ３薄膜の膜厚は１５から３０ｎｍの範囲であれば良く、本例では２０ｎｍとした。
【００３１】
次に、ＡＴＯ薄膜の具体的な製造方法について述べる。なお、ここでは、ＡＴＯ薄膜のうちＡｌ２Ｏ３薄膜を形成する方法について、供給サイクルのうち１回目のサイクルにおけるＡｌＣｌ３の供給時間を、２回目以降のサイクルにおけるＡｌＣｌ３の供給時間よりも長くするようにし、ＴｉＯ２薄膜については、通常のＡＬＥ法にて成膜する例を述べる。
【００３２】
まず、基板を固定するための基板ホルダーボックス内に基板をセットする。このとき本例では、基板において薄膜が成膜される面を垂直に立ててセットする。そして、基板がセットされた基板ホルダーボックスを真空引き可能なロードロック室に投入する。
【００３３】
次に、ロードロック室内を１０-3Ｔｏｒｒ以下まで真空引きし、原料を輸送するキャリアガスである窒素を導入する。この操作を繰り返し、最終的にロードロック室内が再び１０-3Ｔｏｒｒ以下になるように真空引きを行う。
【００３４】
そして、ロードロック室で十分に窒素置換され、真空引きされた基板ホルダーボックスを、予め窒素で置換および真空引きされた薄膜形成のための成膜室内に移動させる。
【００３５】
そして、基板ホルダーボックスを、成膜室内に設置してある加熱ヒータにて加熱し、基板温度を成膜時の温度である５００℃にする。ただし、この加熱中は、成膜開始時の供給ガスによる温度低下を防止するため、キャリアガスである窒素を成膜時と同量、基板ホルダーボックス内に導入しておく。
【００３６】
基板温度が５００℃に到達し温度が安定したら、その後、次に示すプロセスの内、まず、第１、第２のプロセスを実施し、次に、第３、第４、第５のプロセスを２８回繰り返し、最後に第６のプロセスを実施することによりＡＴＯ薄膜（Ａｌ２Ｏ３薄膜とＴｉＯ２薄膜の積層複合膜）を形成する。なお、各プロセスにおいて（）内は供給時間を示す。
【００３７】
「第１のプロセス」：原料ガスであるＡｌＣｌ３ガス（第１の原料物質）を含んだ窒素ガス供給（９秒）と、配管内に残留したＡｌＣｌ３ガスを押し出すための窒素ガスによる配管パージガス供給（１秒）、原料ガスであるＨ２Ｏ（第２の原料物質）を含んだ窒素ガス供給（２秒）と、配管内に残留したＨ２Ｏを押し出すための窒素ガスによる配管パージガス供給（１．５秒）のサイクルを１回実施する。
【００３８】
「第２のプロセス」：原料ガスであるＡｌＣｌ３ガスを含んだ窒素ガス供給（０．５秒）と、配管内に残留したＡｌＣｌ３ガスを押し出すための窒素ガスによる配管パージガス供給（１秒）、原料ガスであるＨ２Ｏを含んだ窒素ガス供給（０．８秒）と、配管内に残留したＨ２Ｏを押し出すための窒素ガスによる配管パージガス供給（１．５秒）のサイクルを３３３回繰り返す。
【００３９】
「第３のプロセス」：原料ガスであるＡｌＣｌ３ガスを含んだ窒素ガス供給（０．５秒）と、配管内に残留したＡｌＣｌ３ガスを押し出すための窒素ガスによる配管パージガス供給（１秒）、原料ガスであるＨ２Ｏを含んだ窒素ガス供給（０．８秒）と、配管内に残留したＨ２Ｏを押し出すための窒素ガスによる配管パージガス供給（１．５秒）のサイクルを１１１回繰り返す。
【００４０】
「第４のプロセス」：原料ガスであるＴｉＣｌ４ガスを含んだ窒素ガス供給（０．６秒）と、配管内に残留したＴｉＣｌ４ガスを押し出すための窒素ガスによる配管パージガス供給（１秒）、原料ガスであるＨ２Ｏを含んだ窒素ガス供給（０．８秒）と、配管内に残留したＨ２Ｏを押し出すための窒素ガスによる配管パージガス供給（２秒）のサイクルを５１回繰り返す。
【００４１】
「第５のプロセス」：原料ガスであるＡｌＣｌ３ガスを含んだ窒素ガス供給（９秒）と、配管内に残留したＡｌＣｌ３ガスを押し出すための窒素ガスによる配管パージガス供給（１秒）、原料ガスであるＨ２Ｏを含んだ窒素ガス供給（２秒）と、配管内に残留したＨ２Ｏを押し出すための窒素ガスによる配管パージガス供給（１．５秒）のサイクルを１回実施する。
【００４２】
「第６のプロセス」：原料ガスであるＡｌＣｌ３ガスを含んだ窒素ガス供給（０．５秒）と、配管内に残留したＡｌＣｌ３ガスを押し出すための窒素ガスによる配管パージガス供給（１秒）、原料ガスであるＨ２Ｏを含んだ窒素ガス供給（０．８秒）と配管内に残留したＨ２Ｏを押し出すための窒素ガスによる配管パージガス供給（１．５秒）のサイクルを４４４回繰り返す。
【００４３】
ここで、第１、第２、第３のプロセスを１回実施することでＡＴＯ薄膜における最下部のＡｌ２Ｏ３薄膜（厚さ２０ｎｍ）が形成される。次に、第４のプロセスを１回実施することで、その上のＴｉＯ２薄膜（厚さ２ｎｍ）が形成される。
【００４４】
次に、第５のプロセス、第３のプロセスをこの順に１回実施することで、その上のＡｌ２Ｏ３薄膜（厚さ５ｎｍ）が形成される。次に、第４のプロセスを１回実施してその上のＴｉＯ２薄膜（厚さ２ｎｍ）を形成し、次に、第５のプロセス、第３のプロセスをこの順に１回実施してその上のＡｌ２Ｏ３薄膜（厚さ５ｎｍ）を形成する。
【００４５】
本例では、このような第３、第４、第５のプロセスの繰り返しが２８回行われる。そして、最後のＴｉＯ２薄膜の形成すなわち最後の第４のプロセスが終了した後、第５のプロセス、第６のプロセスをこの順に１回実施することにより最上部のＡｌ２Ｏ３薄膜（厚さ２０ｎｍ）が形成され、本例のＡＴＯ薄膜が完成する。
【００４６】
ここで、上記原料ガスおよびパージガスは、基板ホルダーボックスの上部に設置されたガス分配器にて、基板上部からそれぞれ均等に分配されるようになっている。分配された原料ガスおよびパージガスは、成膜面が垂直に配置された基板の上部から下部に向かって流れる。すなわち成膜面に沿ってガスが流れる。
【００４７】
また原料となるＡｌＣｌ３およびＴｉＣｌ４の原料供給量は、それぞれ７．２×１０-6〜９．８×１０-5ｍｏｌ／ｐｕｌｓｅ、６．０×１０-6〜２．４×１０-4ｍｏｌ／ｐｕｌｓｅ（いずれも計算値）の範囲内で、それぞれの原料を基板に供給した。
【００４８】
上記製造方法において、Ａｌ２Ｏ３薄膜の形成について、供給サイクルのうち１回目のサイクルにおけるＡｌＣｌ３の供給時間を、２回目以降のサイクルにおけるＡｌＣｌ３の供給時間よりも長くしたことは、具体的には、次のようなことである。
【００４９】
まず、最下部のＡｌ２Ｏ３薄膜（厚さ２０ｎｍ）は、第１、第２、第３のプロセスを１回実施することで形成されるが、これら第１〜第３のプロセスを１回実施することとは、ＡｌＣｌ３とＨ２Ｏとの交互の供給サイクルを（１＋３３３＋１１１）回すなわち４４５回繰り返すことである。
【００５０】
ここで、この供給サイクルの１回目は、第１のプロセスであって、そのＡｌＣｌ３の供給時間は９秒であり、２回目以降のサイクルにおけるＡｌＣｌ３の供給時間である０．５秒よりも長くしている。
【００５１】
また、１回目のサイクルにおいてＡｌＣｌ３の供給時間を長くしたことに対応して、１回目のサイクルではＨ２Ｏの供給時間（２秒）も２回目以降のサイクルにおけるＨ２Ｏの供給時間（０．８秒）よりも長くしている。
【００５２】
また、中間のＡｌ２Ｏ３薄膜（厚さ５ｎｍ）は、第５のプロセス、第３のプロセスを順に１回実施することで形成されるが、これら第５、第３のプロセスを１回実施することとは、ＡｌＣｌ３とＨ２Ｏとの交互の供給サイクルを（１＋１１１）回すなわち１１２回繰り返すことである。
【００５３】
ここで、この供給サイクルの１回目は、第５のプロセスであって、そのＡｌＣｌ３の供給時間は９秒であり、２回目以降のサイクルにおけるＡｌＣｌ３の供給時間である０．５秒よりも長くしている。Ｈ２Ｏについても、１回目のサイクルの供給時間（２秒）を２回目以降のサイクルにおける供給時間（０．８秒）よりも長くしている。
【００５４】
さらに、最上部のＡｌ２Ｏ３薄膜についても、これら最下部および中間のＡｌ２Ｏ３薄膜と同様である。このように本実施形態では、Ａｌ２Ｏ３薄膜の形成について、供給サイクルのうち１回目のサイクルにおけるＡｌＣｌ３の供給時間を、２回目以降のサイクルにおけるＡｌＣｌ３の供給時間よりも長くしている。
【００５５】
ここで、図１に、上述した本例のＡｌ２Ｏ３薄膜の形成における初期から３回目の供給サイクルまでのＡｌＣｌ３原料、Ｈ２Ｏ原料およびそれぞれのパージガスの供給タイミングチャートを同軸の時間軸にて示しておく。図１では、横軸に時間軸、縦軸に原料供給を示すパルス波形を示している。
【００５６】
また、図２は、上記製造方法によって、中間のＡｌ２Ｏ３薄膜（厚さ５ｎｍ）を形成する場合の膜の成長の様子をＡｌ、Ｏ、Ｃｌの薄膜表面における挙動として模式的に表した図である。この場合、下地はＴｉＯ２薄膜であり、初期、ステップ１、２、３、４の順に膜が成長していく。
【００５７】
さらに、図３は、上記図１に対する比較例として、従来のＡＬＥ法によるＡｌ２Ｏ３薄膜の形成における各原料の供給タイミングチャートを示す図である。この場合、Ａｌ２Ｏ３薄膜は、上記第３のプロセスに示した原料供給時間によってすべての供給サイクルが行われる。
【００５８】
そして、図４は、上記図２に対する比較例として、従来のＡＬＥ法によって、中間のＡｌ２Ｏ３薄膜（厚さ５ｎｍ）を形成する場合の膜の成長の様子を分子レベルにて模式的に表した図である。
【００５９】
図４に示す従来の製造方法では、１回目のサイクルにおけるＡｌＣｌ３の供給時間が短く不十分であるため、ステップ１に示すように、ＴｉＯ２薄膜の表面に乱雑にＡｌＣｌ３分子が部分的に配置（置換）される。そのため、その後の原料供給サイクルにおいて、ステップ２、３、４の順に示すように、島状にＡｌ２Ｏ３薄膜が成長していく。そのため、不均一な膜厚となってしまう。
【００６０】
一方、図２に示す本実施形態では、金属元素を含む原料であるＡｌＣｌ３をＴｉＯ２薄膜上に配置する場合、通常０．５秒間であるＡｌＣｌ３の原料供給時間に対して、１回目のサイクルでは９秒間の長時間の原料供給時間としている。
【００６１】
つまり、従来の製造方法に対して、本実施形態のＡｌ２Ｏ３薄膜の製造方法は、上記第１のプロセス、第５のプロセスを１回目の供給サイクルに入れた独自の方法となっている。
【００６２】
そのため、図２のステップ１に示すように、１回目のＡｌＣｌ３の供給により、ＴｉＯ２薄膜表面に整然とＡｌＣｌ３分子が配列し、その後の通常の原料供給時間（０．５秒）の繰り返しサイクルにおいても、整然とＡｌおよびＯが配置される。こうして、本実施形態によれば、原料の供給サイクル回数に応じた均一な膜厚が得られる。
【００６３】
図５は、上記した本実施形態の製造方法によってＡｌ２Ｏ３薄膜を形成した場合において、原料（ＡｌＣｌ３、Ｈ２Ｏ）の供給回数（供給サイクル回数）とＡｌ２Ｏ３の膜厚との関係を調べた結果を示す図である。なお、図５には、上記した従来法にてＡｌ２Ｏ３薄膜を形成した場合についても調べた結果を併記してある。
【００６４】
図５からわかるように、従来法で形成した場合には、薄膜形成初期の成膜速度が不安定であったために、その後の成膜速度も不安定であり、安定した膜厚が得られなかった。それに対して、本実施形態の製造方法を使用することにより、薄膜形成初期の速度が安定し、その結果、膜厚のばらつきがほとんど無くなり、安定した膜の供給が可能になった。
【００６５】
例えば、膜厚５ｎｍのＡｌ２Ｏ３薄膜を形成する場合、従来の製造方法では、狙いの膜厚５ｎｍに対して１ｎｍ程度の膜厚分布のばらつきが生じたのに対し、本実施形態の製造方法では、狙いの膜厚５ｎｍに対して０．３ｎｍ程度のばらつきに抑えることができた。
【００６６】
すなわち、従来法では、成膜初期段階の成膜状態が不良で、原料が部分的に表面に配置していることから、膜厚分布が悪かった。これに対して、本実施形態の製造方法で形成した場合には、原料供給回数に対して正確に膜厚が制御でき、均一にＡｌＣｌ３が配置されていることから、膜厚分布状態も良好なものにすることができる。
【００６７】
なお、上記例では、ＡＴＯ薄膜のうちＡｌ２Ｏ３薄膜を形成する方法に対して、供給サイクルのうち１回目のサイクルにおける金属元素を含む第１の原料物質の供給時間を２回目以降のサイクルにおける供給時間よりも長くするという製造方法を適用した例を述べたが、ＴｉＯ２薄膜の形成についても同様の方法を適用して良いことは勿論である。
【００６８】
その場合、供給サイクルのうち１回目のサイクルにおけるＴｉＣｌ４の供給時間を、２回目以降のサイクルにおけるＴｉＣｌ４の供給時間よりも長くするようにすればよい。それによって、上述したＡｌ２Ｏ３薄膜の場合と同様の効果が得られた。
【００６９】
以上述べてきたように、本実施形態によれば、金属元素を含む第１の原料物質と金属元素と反応する元素を含む第２の原料物質とを、基板に対して交互に供給することにより薄膜を形成する薄膜の製造方法において、供給サイクルのうち１回目のサイクルにおける第１の原料物質の供給時間を、２回目以降のサイクルにおける第１の原料物質の供給時間よりも長くすることを特徴とする薄膜の製造方法が提供される。
【００７０】
それによれば、供給サイクルのうち１回目のサイクルにおける第１の原料物質の供給時間を十分に長くすることで、金属元素を含む第１の原料物質によって下地を十分に被覆することができる。
【００７１】
そのため、形成される薄膜とその下地との結晶の整合性が悪かったり、下地と薄膜原料物質との反応が起こりやすい場合であっても、供給サイクルの２回目以降においては、下地との結晶の整合性が良くなり、また、下地との反応も起こらないため、均一な層成長が可能となる。
【００７２】
そして、供給サイクルのうち１回目のサイクルにおける第１の原料物質の供給時間は、長くなるが、２回目以降はそれよりも短く、ほぼ通常の供給時間とすることができるため、薄膜の形成時間全体ではさほど長時間とはならない。
【００７３】
よって、本実施形態によれば、薄膜の形成時間を極力短い時間としつつ、狙いの膜厚を適切に実現することができる。
【００７４】
なお、２回目以降の供給において、後のサイクルに行くに連れて第１の原料物質の供給時間を短くするようにしても良い。例えば、２回目のサイクルにおけるＡｌＣｌ３の供給時間を３回目以降のＡｌＣｌ３の供給時間よりも長くしても良い。ただし、１回目のサイクルの供給時間を最も長いものとした上で行う必要がある。
【００７５】
また、本発明の製造方法は、上記したＴｉＯ２薄膜上にＡｌ２Ｏ３薄膜を形成するプロセスのみでなく、Ａｌ２Ｏ３薄膜上にＴｉＯ２薄膜を形成するプロセス、ガラス基板上にＡｌ２Ｏ３薄膜を形成するプロセス、ＺｎＳ等の発光層上にＡｌ２Ｏ３薄膜を形成するプロセス、その他、有機錯体や塩化物等のハロゲン化物を出発原料とする酸化物薄膜をＡＬＥ法で形成するプロセス等において適用可能である。
【図面の簡単な説明】
【図１】本発明の実施形態におけるＡｌ２Ｏ３薄膜の形成における各原料の供給タイミングチャートを示す図である。
【図２】上記実施形態においてＡｌ２Ｏ３薄膜を形成する場合の膜の成長の様子を分子レベルにて模式的に表した図である。
【図３】従来の製造方法によるＡｌ２Ｏ３薄膜の形成における各原料の供給タイミングチャートを示す図である。
【図４】従来の製造方法においてＡｌ２Ｏ３薄膜を形成する場合の膜の成長の様子を分子レベルにて模式的に表した図である。
【図５】実施形態の製造方法によってＡｌ２Ｏ３薄膜を形成した場合において、原料供給回数と膜厚との関係を調べた結果を示す図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a thin film manufacturing method for forming a thin film by alternately supplying a first source material containing a metal element and a second source material containing an element that reacts with the metal element to a substrate, a so-called thin film manufacturing method. It relates to atomic layer growth.
[0002]
[Prior art]
Conventionally, atomic layer epitaxy (ALE method) has been used when forming a thin film of metal oxide or metal sulfide as a film forming method with good crystallinity and excellent film thickness controllability. It is used (for example, refer to Patent Document 1).
[0003]
In this method, a first raw material containing a metal element (for example, a metal chloride or an organometallic compound) and a second raw material containing an element that reacts with the metal element (for example, an oxidizing substance such as water or hydrogen sulfide) By simply repeating the cycle of alternately supplying the reducing substance to the substrate, the reaction compound is arranged on the substrate surface one layer at a time by the reaction on the substrate surface. It is said that the film thickness can be easily controlled.
[0004]
Using this ALE method, various thin films can be formed. For example, in an electroluminescence element, there are an ATO thin film which is a composite film of aluminum oxide and titanium oxide used as an insulating layer, and zinc sulfide and strontium sulfide used as a light emitting layer.
[0005]
[Patent Document 1]
Japanese Patent Laid-Open No. 55-130896
[Problems to be solved by the invention]
However, the ALE method has the advantages as described above. However, since the ALE method is a formation method in which atoms are arranged one by one, if the supply time of each raw material constituting the thin film is lengthened, it is enormous to obtain a desired film thickness There is a problem that it takes a long time.
[0007]
On the other hand, according to the study of the present inventor, for example, when an ATO thin film is formed by the ALE method, when an Al2O3 thin film and a TiO2 thin film are alternately laminated, when forming a TiO2 thin film on the Al2O3 thin film, or a TiO2 thin film If an attempt is made to shorten the film formation time when forming an Al2O3 thin film on the film, the problem arises that the film thickness formed by the number of times of supplying the raw material calculated from the monomolecular layer film thickness becomes different from the target film thickness. It was.
[0008]
In view of the above problems, the present invention forms a thin film by alternately supplying a first source material containing a metal element and a second source material containing an element that reacts with the metal element to the substrate. It is an object of the present invention to achieve a target film thickness appropriately in as short a formation time as possible in a thin film manufacturing method using an atomic layer growth method .
[0009]
[Means for Solving the Problems]
The present inventor further investigated the problem that the film thickness becomes thinner than the target film thickness in the formation of the ATO thin film described above.
[0010]
For example, when an Al2O3 thin film is formed on a TiO2 thin film, AlCl3, which is a raw material for Al, is usually supplied and oxidized by supplying H2O to form Al2O3 molecules.
[0011]
At this time, for the purpose of shortening the entire thin film formation time, if the supply time of the AlCl 3 raw material, that is, the supply amount of the AlCl 3 raw material at one time is small, the alignment of the crystal on the dissimilar film (ie, the TiO 2 thin film) as the base Cannot grow well due to sexual deterioration. As a result, it is not possible to sufficiently cover the underlying surface with AlCl 3 with a single supply of raw material.
[0012]
In this state, when the supply cycle of AlCl3 and H2O is repeated and the film growth is continued, a part with a fast growth is formed, and Al2O3 grows in a cluster shape. As a result, it has been experimentally found that the finished Al2O3 thin film has a non-uniform thickness and a desired film thickness cannot be obtained with good control.
[0013]
On the other hand, if the supply cycle is continued repeatedly with a sufficient supply amount of the AlCl 3 raw material once, the film formation time for obtaining a desired film thickness becomes enormous.
[0014]
Further, in the case of forming an Al2O3 thin film on a TiO2 thin film, when AlCl3 as an Al raw material is first supplied, a molecule on the surface of the TiO2 as a base and an AlCl3 molecule undergo a substitution reaction to erode TiO2. discovered. This is considered to occur when the vapor pressure is relatively higher in the base film than in the thin film material.
[0015]
Therefore, when the AlCl 3 raw material is supplied non-uniformly, the substitution reaction with TiO 2 is performed non-uniformly, and the thin film growth rate differs from the above-described growth failure due to poor crystal alignment with the base. As a result, it was found that the film thickness was uneven.
[0016]
From these examination results, if the poor crystal alignment with the substrate and the non-uniform reaction between the substrate and the thin film raw material are eliminated at the initial stage of the supply cycle, uniform film growth cannot be achieved in the subsequent supply. I thought. The present invention has been obtained as a result of experimental studies focusing on these points.
[0017]
That is, in the first aspect of the invention, the thin film is formed by alternately supplying the first source material containing the metal element and the second source material containing the element that reacts with the metal element to the substrate. In the thin film manufacturing method using the atomic layer growth method, the supply time of the first source material in the first cycle of the supply cycles is made longer than the supply time of the first source material in the second and subsequent cycles. It is characterized by.
[0018]
According to this, by sufficiently increasing the supply time of the first raw material in the first cycle of the supply cycles, the base can be sufficiently covered with the first raw material containing the metal element.
[0019]
Therefore, even if the crystal matching between the thin film to be formed and the base is poor or the reaction between the base and the thin film raw material is likely to occur, the crystal of the base and the base is not used after the second supply cycle. Consistency is improved and no reaction with the base occurs, so that uniform layer growth is possible.
[0020]
The supply time of the first source material in the first cycle of the supply cycle becomes longer, but the second and subsequent times are shorter than that, and can be set to a substantially normal supply time. It won't be that long.
[0021]
Therefore, according to the present invention, a target film thickness can be appropriately realized in as short a formation time as possible.
[0022]
Here, as in the invention described in claim 2, a metal halide or an organometallic compound can be used as the first raw material.
[0023]
The thin film may be an insulator such as alumina (Al2O3) or a semiconductor such as titania (TiO2).
[0024]
In addition, the code | symbol in the bracket | parenthesis of each said means is an example which shows a corresponding relationship with the specific means as described in embodiment mentioned later.
[0025]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described based on specific embodiments. In this embodiment, the thin film to be formed is an ATO thin film used as an insulating film of an EL element. This is a film formed by alternately laminating an Al2O3 (alumina) thin film as an insulator and a TiO2 (titania) thin film as a semiconductor alternately by the ALE method.
[0026]
In the ATO thin film as the insulating film of the EL element, the TiO 2 thin film and the Al 2 O 3 thin film are alternately laminated in this order from the Al 2 O 3 thin film by the ALE method, and finally the Al 2 O 3 thin film is formed again.
[0027]
Specifically, when an Al2O3 thin film is formed by the ALE method, AlCl3 that is a first raw material containing a metal element and H2O that is a second raw material containing an element that reacts with the metal element are used. By repeating the cycle of alternately supplying the substrate, Al2O3 is grown one atomic layer at a time, and an Al2O3 thin film having a predetermined thickness is formed.
[0028]
When the TiO2 thin film is formed by the ALE method, TiCl4, which is a first raw material containing a metal element, and H2O, which is a second raw material containing an element that reacts with the metal element, are formed on the substrate. By repeating the cycle of supplying alternately, TiO2 is grown one atomic layer at a time, and a TiO2 thin film having a predetermined thickness is formed.
[0029]
Then, an Al2O3 thin film and a TiO2 thin film each having a predetermined thickness are alternately laminated to complete an ATO thin film.
[0030]
Here, the film thickness of the Al2O3 thin film excluding the uppermost Al2O3 thin film and the lowermost Al2O3 thin film of the ATO thin film may be 5 nm, and the film thickness of the TiO2 thin film may be in the range of 1.5 to 5 nm. In this example, 2 nm It was. Further, the film thickness of the uppermost and lowermost Al2O3 thin films may be in the range of 15 to 30 nm, and in this example 20 nm.
[0031]
Next, a specific method for manufacturing the ATO thin film will be described. Here, regarding the method of forming the Al2O3 thin film among the ATO thin films, the supply time of AlCl3 in the first cycle of the supply cycles is made longer than the supply time of AlCl3 in the second and subsequent cycles, and TiO2 As for the thin film, an example of forming a film by a normal ALE method will be described.
[0032]
First, a substrate is set in a substrate holder box for fixing the substrate. At this time, in this example, the surface on which the thin film is formed on the substrate is set upright. Then, the substrate holder box on which the substrate is set is put into a load lock chamber that can be evacuated.
[0033]
Next, the load lock chamber is evacuated to 10 −3 Torr or less, and nitrogen, which is a carrier gas for transporting the raw material, is introduced. This operation is repeated, and evacuation is finally performed so that the load lock chamber becomes 10 −3 Torr or less again.
[0034]
Then, the substrate holder box that has been sufficiently purged with nitrogen and evacuated in the load lock chamber is moved into the deposition chamber for forming a thin film that has been previously purged and evacuated with nitrogen.
[0035]
Then, the substrate holder box is heated by a heater installed in the film formation chamber, and the substrate temperature is set to 500 ° C. which is the temperature at the time of film formation. However, during this heating, in order to prevent a temperature drop due to the supply gas at the start of film formation, nitrogen as a carrier gas is introduced into the substrate holder box in the same amount as during film formation.
[0036]
When the substrate temperature reaches 500 ° C. and the temperature becomes stable, first, the first and second processes are performed first, and then the third, fourth, and fifth processes are performed. The ATO thin film (laminated composite film of an Al2O3 thin film and a TiO2 thin film) is formed by repeating the process six times and finally performing the sixth process. In each process, the parentheses indicate the supply time.
[0037]
“First process”: supply of nitrogen gas containing AlCl 3 gas (first source material) as a source gas (9 seconds) and supply of pipe purge gas with nitrogen gas for extruding AlCl 3 gas remaining in the pipe ( 1 second), nitrogen gas supply (2 seconds) containing H2O (second raw material) as a source gas, and pipe purge gas supply (1.5 seconds) using nitrogen gas to push out H2O remaining in the pipe This cycle is performed once.
[0038]
"Second process": supply of nitrogen gas containing AlCl3 gas, which is a raw material gas (0.5 seconds), supply of pipe purge gas with nitrogen gas (1 second) for extruding AlCl3 gas remaining in the pipe, raw material A cycle of supplying nitrogen gas containing gas H2O (0.8 seconds) and supplying pipe purge gas with nitrogen gas (1.5 seconds) for extruding H2O remaining in the pipe is repeated 333 times.
[0039]
“Third process”: supply of nitrogen gas containing AlCl 3 gas, which is a raw material gas (0.5 seconds), supply of pipe purge gas with nitrogen gas (1 second) for extruding AlCl 3 gas remaining in the pipe, raw material A cycle of supplying nitrogen gas containing H 2 O as a gas (0.8 seconds) and supplying pipe purge gas with nitrogen gas (1.5 seconds) for extruding H 2 O remaining in the pipe is repeated 111 times.
[0040]
"Fourth process": Nitrogen gas supply containing TiCl4 gas, which is a raw material gas (0.6 seconds), pipe purge gas supply using nitrogen gas (1 second) for extruding TiCl4 gas remaining in the pipe, raw material The cycle of supplying nitrogen gas containing gas H2O (0.8 seconds) and supplying pipe purge gas with nitrogen gas (2 seconds) for extruding H2O remaining in the pipe is repeated 51 times.
[0041]
"Fifth process": supply of nitrogen gas containing AlCl3 gas, which is a raw material gas (9 seconds), supply of pipe purge gas with nitrogen gas (1 second) to push out AlCl3 gas remaining in the pipe, and supply gas A cycle of supplying nitrogen gas containing H2O (2 seconds) and supplying pipe purge gas with nitrogen gas (1.5 seconds) for extruding H2O remaining in the pipe is performed once.
[0042]
“Sixth process”: supply of nitrogen gas containing AlCl 3 gas, which is a raw material gas (0.5 seconds), supply of pipe purge gas with nitrogen gas (1 second) for extruding AlCl 3 gas remaining in the pipe, raw material A cycle of supplying a nitrogen gas containing H 2 O as a gas (0.8 seconds) and supplying a pipe purge gas with nitrogen gas (1.5 seconds) for extruding H 2 O remaining in the pipe is repeated 444 times.
[0043]
Here, by performing the first, second, and third processes once, the lowermost Al 2 O 3 thin film (thickness 20 nm) in the ATO thin film is formed. Next, by performing the fourth process once, a TiO2 thin film (thickness 2 nm) thereon is formed.
[0044]
Next, by performing the fifth process and the third process once in this order, an Al2O3 thin film (thickness 5 nm) thereon is formed. Next, the fourth process is performed once to form a TiO2 thin film (thickness 2 nm) thereon, then the fifth process and the third process are performed once in this order, and then An Al2O3 thin film (thickness 5 nm) is formed.
[0045]
In this example, the repetition of the third, fourth and fifth processes is performed 28 times. Then, after the final formation of the TiO2 thin film, that is, the final fourth process, the fifth process and the sixth process are performed once in this order to form the uppermost Al2O3 thin film (thickness 20 nm). Thus, the ATO thin film of this example is completed.
[0046]
Here, the source gas and the purge gas are equally distributed from the upper part of the substrate by a gas distributor installed at the upper part of the substrate holder box. The distributed source gas and purge gas flow from the upper part to the lower part of the substrate on which the film formation surfaces are arranged vertically. That is, the gas flows along the film formation surface.
[0047]
The raw material supply amounts of AlCl3 and TiCl4 used as raw materials are 7.2 × 10 −6 to 9.8 × 10 −5 mol / pulse, 6.0 × 10 −6 to 2.4 × 10 −4 mol / pulse, respectively. Each raw material was supplied to the substrate within the range of pulse (both calculated values).
[0048]
In the above manufacturing method, regarding the formation of the Al2O3 thin film, the supply time of AlCl3 in the first cycle of the supply cycles is longer than the supply time of AlCl3 in the second and subsequent cycles. It is like that.
[0049]
First, the lowermost Al2O3 thin film (thickness 20 nm) is formed by performing the first, second, and third processes once, and these first to third processes are performed once. Is to repeat the alternating supply cycle of AlCl 3 and H 2 O (1 + 333 + 111) times, that is, 445 times.
[0050]
Here, the first supply cycle is the first process, and the AlCl3 supply time is 9 seconds, which is longer than the 0.5 second supply time of AlCl3 in the second and subsequent cycles. ing.
[0051]
Corresponding to the increase in the supply time of AlCl3 in the first cycle, the supply time of H2O (2 seconds) in the first cycle is also the supply time of H2O in the second and subsequent cycles (0.8 seconds). Longer than that.
[0052]
The intermediate Al2O3 thin film (thickness 5 nm) is formed by performing the fifth process and the third process once in order. The fifth and third processes are performed once. Is to repeat the alternating supply cycle of AlCl 3 and H 2 O (1 + 111) times, ie 112 times.
[0053]
Here, the first supply cycle is the fifth process, and the supply time of AlCl3 is 9 seconds, which is longer than the 0.5 second supply time of AlCl3 in the second and subsequent cycles. ing. Also for H2O, the supply time (2 seconds) of the first cycle is longer than the supply time (0.8 seconds) of the second and subsequent cycles.
[0054]
Further, the uppermost Al 2 O 3 thin film is the same as the lowermost and intermediate Al 2 O 3 thin films. Thus, in this embodiment, regarding the formation of the Al 2 O 3 thin film, the supply time of AlCl 3 in the first cycle of the supply cycles is set longer than the supply time of AlCl 3 in the second and subsequent cycles.
[0055]
Here, in FIG. 1, the supply timing chart of the AlCl 3 raw material, the H 2 O raw material and the respective purge gases from the initial stage to the third supply cycle in the formation of the Al 2 O 3 thin film of this example described above is shown on a coaxial time axis. In FIG. 1, the horizontal axis represents a time axis, and the vertical axis represents a pulse waveform indicating material supply.
[0056]
FIG. 2 is a diagram schematically showing the state of film growth when an intermediate Al 2 O 3 thin film (thickness 5 nm) is formed by the above manufacturing method as the behavior of the Al, O, Cl thin film surface. . In this case, the base is a TiO 2 thin film, and the film grows in the order of
[0057]
Furthermore, FIG. 3 is a diagram showing a supply timing chart of each raw material in the formation of the Al 2 O 3 thin film by the conventional ALE method as a comparative example with respect to FIG. In this case, all supply cycles of the Al 2 O 3 thin film are performed according to the raw material supply time shown in the third process.
[0058]
FIG. 4 is a diagram schematically showing the state of film growth at the molecular level when an intermediate Al 2 O 3 thin film (thickness 5 nm) is formed by a conventional ALE method as a comparative example with respect to FIG. It is.
[0059]
In the conventional manufacturing method shown in FIG. 4, since the supply time of AlCl3 in the first cycle is short and insufficient, as shown in
[0060]
On the other hand, in this embodiment shown in FIG. 2, when AlCl3, which is a raw material containing a metal element, is arranged on a TiO2 thin film, the AlCl3 raw material supply time, which is normally 0.5 seconds, is 9 in the first cycle. The raw material supply time is a long time for a second.
[0061]
That is, compared with the conventional manufacturing method, the manufacturing method of the Al2O3 thin film of this embodiment is an original method in which the first process and the fifth process are put into the first supply cycle.
[0062]
Therefore, as shown in
[0063]
FIG. 5 is a diagram showing the results of examining the relationship between the number of times of supplying the raw materials (AlCl3, H2O) (the number of supply cycles) and the thickness of the Al2O3 when the Al2O3 thin film is formed by the manufacturing method of the present embodiment described above. It is. Note that FIG. 5 also shows the results obtained by examining the case where the Al 2 O 3 thin film is formed by the above-described conventional method.
[0064]
As can be seen from FIG. 5, when the film was formed by the conventional method, the film formation speed at the initial stage of the thin film formation was unstable, so the subsequent film formation speed was also unstable, and a stable film thickness could not be obtained. It was. On the other hand, by using the manufacturing method of this embodiment, the speed at the initial stage of thin film formation is stabilized, and as a result, there is almost no variation in film thickness, and a stable film supply is possible.
[0065]
For example, when an Al2O3 thin film having a thickness of 5 nm is formed, the conventional manufacturing method has a variation in film thickness distribution of about 1 nm with respect to the target thickness of 5 nm, whereas in the manufacturing method of the present embodiment, The variation was about 0.3 nm with respect to the target film thickness of 5 nm.
[0066]
That is, in the conventional method, since the film formation state at the initial stage of film formation is poor and the raw materials are partially arranged on the surface, the film thickness distribution is poor. On the other hand, when formed by the manufacturing method of the present embodiment, the film thickness can be accurately controlled with respect to the number of times the raw material is supplied, and the AlCl 3 is uniformly arranged, so the film thickness distribution state is also good. Can be a thing.
[0067]
In the above example, compared to the method of forming the Al 2 O 3 thin film among the ATO thin films, the supply time of the first source material containing the metal element in the first cycle in the supply cycle is the supply time in the second and subsequent cycles. Although an example in which the manufacturing method of making it longer is applied has been described, it goes without saying that the same method may be applied to the formation of the TiO 2 thin film.
[0068]
In that case, the supply time of TiCl 4 in the first cycle of the supply cycles may be made longer than the supply time of TiCl 4 in the second and subsequent cycles. Thereby, the same effect as the case of the Al2O3 thin film described above was obtained.
[0069]
As described above, according to the present embodiment, the first source material containing the metal element and the second source material containing the element that reacts with the metal element are alternately supplied to the substrate. In the method of manufacturing a thin film for forming a thin film, the supply time of the first source material in the first cycle of the supply cycles is made longer than the supply time of the first source material in the second and subsequent cycles. A method for producing a thin film is provided.
[0070]
According to this, by sufficiently increasing the supply time of the first raw material in the first cycle of the supply cycles, the base can be sufficiently covered with the first raw material containing the metal element.
[0071]
Therefore, even if the crystal matching between the thin film to be formed and the base is poor or the reaction between the base and the thin film raw material is likely to occur, the crystal of the base and the base is not used after the second supply cycle. Consistency is improved and no reaction with the base occurs, so that uniform layer growth is possible.
[0072]
The supply time of the first source material in the first cycle of the supply cycle becomes longer, but the second and subsequent times are shorter than that, and can be set to a substantially normal supply time. Overall it will not be very long.
[0073]
Therefore, according to the present embodiment, the target film thickness can be appropriately realized while making the thin film formation time as short as possible.
[0074]
In the second and subsequent supply, the supply time of the first source material may be shortened as the cycle proceeds. For example, the supply time of AlCl 3 in the second cycle may be longer than the supply time of AlCl 3 in the third and subsequent cycles. However, it is necessary to carry out after making the supply time of the first cycle the longest.
[0075]
The manufacturing method of the present invention is not limited to the process of forming the Al2O3 thin film on the TiO2 thin film as described above, the process of forming the TiO2 thin film on the Al2O3 thin film, the process of forming the Al2O3 thin film on the glass substrate, ZnS, etc. The present invention can be applied to a process for forming an Al2O3 thin film on a light emitting layer, and a process for forming an oxide thin film using an organic complex, a halide such as chloride as a starting material by the ALE method, and the like.
[Brief description of the drawings]
FIG. 1 is a view showing a supply timing chart of each raw material in forming an Al 2 O 3 thin film in an embodiment of the present invention.
FIG. 2 is a diagram schematically showing a state of film growth at the molecular level when an Al 2 O 3 thin film is formed in the embodiment.
FIG. 3 is a view showing a supply timing chart of each raw material in forming an Al 2 O 3 thin film by a conventional manufacturing method.
FIG. 4 is a diagram schematically showing the state of film growth at the molecular level when an Al 2 O 3 thin film is formed in a conventional manufacturing method.
FIG. 5 is a diagram showing a result of examining a relationship between the number of times of supplying a raw material and a film thickness when an Al 2 O 3 thin film is formed by the manufacturing method of the embodiment.
Claims (6)
供給サイクルのうち１回目のサイクルにおける前記第１の原料物質の供給時間を、２回目以降のサイクルにおける前記第１の原料物質の供給時間よりも長くすることを特徴とする薄膜の製造方法。 A thin film manufacturing method by an atomic layer growth method in which a thin film is formed by alternately supplying a first raw material containing a metal element and a second raw material containing an element that reacts with the metal element to a substrate. In
A method for producing a thin film, characterized in that a supply time of the first source material in a first cycle of the supply cycle is made longer than a supply time of the first source material in a second and subsequent cycles.
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