JP2021019198A - トポロジー制御されたアモルファスカーボンポリマー膜の形成方法 - Google Patents

トポロジー制御されたアモルファスカーボンポリマー膜の形成方法 Download PDF

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JP2021019198A
JP2021019198A JP2020120474A JP2020120474A JP2021019198A JP 2021019198 A JP2021019198 A JP 2021019198A JP 2020120474 A JP2020120474 A JP 2020120474A JP 2020120474 A JP2020120474 A JP 2020120474A JP 2021019198 A JP2021019198 A JP 2021019198A
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membrane
trench
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ティモシー・ジュリアン・ヴァンサン・ブランカール
Julien Vincent Blanquart Timothee
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ASM IP Holding BV
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Abstract

【課題】本発明は、概ね基材のパターン形成された凹部上にトポロジー制御されたアモルファスカーボン膜を形成する方法に関する。【解決手段】基材のパターン形成された凹部上にトポロジー制御層を形成する方法であって、方法は、（ｉ）ボトムアップ方式またはボトムレス方式で凹部を充填するために、パルスプラズマアシスト堆積によって基材のパターン形成された凹部上に充填能力を有するＳｉを含まないＣ含有膜を堆積させることと、（ｉｉ）主にもしくは実質的に充填膜の底部のみ、または主にもしくは実質的に充填膜の側壁部のみを残す方法で、充填膜のトップ部を除去するために、凹部に充填されたボトムアップまたはボトムレス膜をプラズマアッシングすることと、を含む。【選択図】図１

Description

本発明は、概ね基材のパターン形成された凹部上にトポロジー制御されたアモルファスカーボン膜を形成する方法に関する。
関連技術の説明
集積回路、例えば、シャロートレンチアイソレーション、金属間誘電体層、パッシベーション層等のための集積回路を製造するプロセスでは、多くの場合トレンチ（典型的には１以上のアスペクト比を有する任意の凹部）を絶縁材料で充填することが必要である。しかし、大規模集積（ＬＳＩ）デバイスの配線ピッチの微細化に伴い、既存の堆積プロセスの制限により、高アスペクト比空間（例えば、ＡＲ≧３）のボイドフリー充填がますます困難になっている。
上記を考慮して、本発明者は流動性膜の堆積のためのギャップ充填技術を開発し、その技術を、２０１８年７月３日に出願された米国特許出願第１６／０２６，７１１号に開示した。それは、窒素、酸素、および水素プラズマが必要とされない条件下で実質的にボイドを形成することなく、炭化水素前駆体を使用してプラズマアシスト堆積により完全なギャップ充填を提供し、その開示はその全体が参照により本明細書に組み込まれる。
しかし、例えば、犠牲エッチングストップ層または保護層が凹部の底部にのみ必要な特定の用途が、基材のトレンチ内に上記のギャップ充填技術を使用して、アモルファスカーボンの底部のみの堆積を必要とする場合、次の問題が生じる可能性がある：ｉ）基材のトップ面上に（少量ではあるが無視できない）一定量の膜が堆積する可能性がある、ｉｉ）各トレンチの底部に堆積する膜の量は、各トレンチの構造容積に応じて不規則になる場合がある（図８の（ａ）を参照）、ｉｉｉ）各トレンチの構造容積が類似している場合でも、ギャップ充填にいくらかのランダム性がある場合がある（図８の（ｂ）を参照）。本発明者は、上記の問題に対する解決策をここに提供する。
他のアプリケーション、例えば３Ｄ ＮＡＮＤフラッシュでは、超ディープホールストレートエッチングが必要とされる。しかし、ホールエッチング中に側壁エッチングが発生するため、直線構造をそのまま維持することは非常に困難であり、その結果、ＣＤの完全性が低下する。本発明者は、上記のギャップ充填技術が上記の問題に対する解決策を提供できることを見出した。
関連技術に関わる問題および解決法のいかなる議論も、単に本発明の背景を提供する目的で本開示に含まれ、本発明がなされた時点で、議論のいずれかまたは全てが知られていたという了解のように解釈されるべきではない。
上記を考慮して、いくつかの実施形態は、基材のパターン形成された凹部上にトポロジー制御層を形成する方法を提供し、方法は、（ｉ）ボトムアップ方式またはボトムレス方式で凹部を充填するために、パルスプラズマアシスト堆積によって基材のパターン形成された凹部上に充填能力を有するＳｉを含まないＣ含有膜を堆積させることと、（ｉｉ）主に充填膜の底部のみ、または主に充填膜の側壁部のみを残す方法で、充填膜のトップ部を除去するために、凹部に充填されたボトムアップまたはボトムレス膜をプラズマアッシングすることと、を含む。上記の実施形態によれば、ギャップ充填技術を使用することにより、膜のトポロジーを操作することができる。トレンチのサイズに対する膜の流動性の程度は、堆積がボトムアップ堆積かボトムレス堆積かを主に決定することができる。
膜の流動性が対象トレンチに対して十分に高い場合、ボトムアップ堆積が起こり、トレンチを完全に充填し、さらにトレンチ上に膜を堆積させた後、膜をプラズマアッシングすることにより、トレンチ上の膜のトップ部およびトレンチ内に充填される膜の上部を、トレンチの均一な深さまで等しく除去して、実質的に均一な深さを有する膜で充填されたトレンチを得ることができる。
膜の流動性が対象トレンチに対して十分に低い場合、ボトムレス堆積が起こるが、膜は流動性なので、膜がトレンチの底部に達せず、トレンチの上部開口部を閉じた場合でも、膜は、トレンチの側壁に沿って堆積して、基材のトップ面からある深さまで側壁を覆うことができる。膜の堆積が完了した後、膜をプラズマアッシングすることにより、トレンチの開口部を閉じる膜の部分が除去されてトエレンチを開け、側壁膜を空間として残すことができる。その後、超ディープホールストレートエッチングを行うことができる。トレンチの底部は実質的に膜で覆われておらず、側壁膜は超ディープホールストレートエッチング中に側壁がエッチングされるのを防ぐことができるため、ＣＤの完全性を損なうことなくエッチングを深さ方向に進行して超深穴ストレートを形成できる。
本発明の態様および関連技術を超えて達成される利点を要約するために、本発明のいくつかの目的および利点を本開示に記載する。当然のことながら、必ずしもこうした目的または利点の全てが本発明の任意の特定の実施形態によって達成されなくてもよいことが理解されるべきである。したがって、例えば、当業者であれば、本明細書で教示または示唆される他の目的または利点を必ずしも達成することなく、本明細書で教示される一つの利点または利点の群を達成または最適化する方法で、本発明が具現化または実行され得ることを認識するであろう。
本発明の更なる態様、特徴、および利点は、以下の詳細な説明から明らかになるであろう。
本発明のこれらおよび他の特徴は、例示を意図し、本発明を限定することを意図しない好ましい実施形態の図面を参照して説明される。図面は、例示目的のために非常に単純化されており、必ずしも縮尺どおりではない。
図１Ａは本発明の一実施形態で使用可能な誘電体膜を堆積させるためのＰＥＡＬＤ（プラズマエンハンスト原子層堆積）装置の概略図であり、図１Ｂは本発明の一実施形態で使用可能なフローパスシステム（ＦＰＳ）を用いる前駆体供給システムの概略図である。 本発明の実施形態によるボトムアップ堆積させた（（ａ）→（ｂ）→（ｃ））およびボトムレス堆積させた（（ａ）→（ｄ）→（ｅ））トレンチの概略断面図を例示する図である。 本発明の実施形態による、（ａ）でボトムアップ堆積させ、続いて（ｂ）でＯ２／Ａｒアッシング、または（ｃ）でＮ２／Ｈ２アッシングさせたトレンチの断面のＳＴＥＭ写真である。 アッシングなしでボトムレス堆積（３００サイクル）させたトレンチの断面のＳＴＥＭ写真の概略図である。 本発明の実施形態による、ボトムレス堆積（３００サイクル）させ、それに続きアッシング（９０秒）させたトレンチの断面のＳＴＥＭ写真の概略図である。 アッシングなしでボトムレス堆積（３５０サイクル）させたトレンチの断面のＳＴＥＭ写真の概略図である。 本発明の実施形態による、ボトムレス堆積（３５０サイクル）させ、それに続きアッシング（９０秒）させたトレンチの断面のＳＴＥＭ写真の概略図である。 ボトムアップ堆積させたトレンチの断面のＳＴＥＭ写真であり、（ａ）は異なる幅を有するトレンチを表し、（ｂ）は不規則な量の膜で満たされたトレンチである。 ボトムアップ堆積させたトレンチの断面のＳＴＥＭ写真であり、（ａ）は堆積の完了時のトレンチを表し、（ｂ）は本発明の実施形態によるアッシング後のトレンチを表す。 本発明の実施形態による、ボトムアップ堆積（全充填）させたトレンチの断面のＳＴＥＭ写真であり、行（ａ）は異なる幅を有する広いトレンチと狭いトレンチの混合を表し（スケールは３００ｎｍを表す）、行（ｂ）は中間のトレンチを表し（スケールは６０ｎｍを表す）、行（ｃ）は幅がわずかに異なる広いトレンチ（スケールは６０ｎｍを表す）を表し、列（１）はアッシング前に全充填堆積（２１０サイクルの堆積）させたトレンチを表し、列（２）は１０５秒間のアッシング後のトレンチを表し、列（３）は１２９秒間のアッシング後のトレンチを表し、列（４）は１６５秒間アッシング後のトレンチを表す。 本発明の一実施形態による、ボトムアップ堆積させたトレンチの断面のＳＴＥＭ写真であり、（ａ）は全充填堆積（２１０サイクルの堆積）の完了時のトレンチを表し、（ｂ）は２４０秒間のアッシング後のトレンチを表し、（ｃ）は３００秒間のアッシング後のトレンチを表す。 本発明の実施形態による膜形成のプロセスのシーケンスを例示する図であり、灰色のセルはオン状態を表し、一方、白色のセルはオフ状態を表し、各列の幅は各プロセスの持続時間を表していない。
本開示では、「ガス」は、気化した固体および／または液体を含むことができ、状況に応じて単一のガスまたはガスの混合物によって構成されることができる。同様に、冠詞「ａ」または「ａｎ」は、文脈によって、複数の種を含む種または属を指す。本開示では、シャワーヘッドを介して反応チャンバーに導入されるプロセスガスは、シリコンを含まない炭化水素前駆体と添加ガスとから構成されるもの、それらから本質的になるもの、またはそれらからなるもの、であってもよい。添加ガスは、ＲＦパワーが添加ガスに印加された場合に、前駆体を励起してアモルファスカーボンポリマーを形成するためのプラズマ発生ガスを含むことができる。添加ガスは、キャリアガスおよび／または希釈ガスとして反応チャンバーに供給されることができる不活性ガスであってもよい。添加ガスは、前駆体を酸化または窒化するための反応ガスを含まなくてもよい。あるいは、添加ガスは、アモルファスカーボン系ポリマーを形成するプラズマ重合を妨害しない範囲で前駆体を酸化または窒化するための反応ガスを含んでもよい。さらに、いくつかの実施形態では、添加ガスはプラズマ発生ガス（例えば、希ガス）のみを含む。前駆体および添加ガスを、混合ガスとしてまたは別々に反応空間に導入することができる。前駆体を、キャリアガス、例えば希ガスと共に導入することができる。プロセスガス以外のガス、即ちシャワーヘッドを通過せずに導入されるガスは、例えば、シールガス、例えば希ガスを含む反応空間をシールするために使用されてもよい。いくつかの実施形態では、用語「前駆体」は一般的に、別の化合物を生成する化学反応に関与する化合物、特に膜マトリックスまたは膜の主骨格を構成する化合物を指し、用語「反応物質」は、前駆体を活性化する、前駆体を修飾する、または前駆体の反応を触媒する、前駆体以外の化合物を指し、励起状態では、反応物質は元素（例えば、Ｏ、Ｃ、Ｎ）を膜マトリックスに供給し、膜マトリックスの一部となることができる。用語「プラズマ発生ガス」は、電磁エネルギーに曝される場合、プラズマを発生させる、前駆体および反応物質以外の化合物を指し、プラズマ発生ガスは、膜マトリックスの一部となる膜マトリックスに元素（例えばＯ、Ｃ、Ｎ）を提供しない場合がある。用語「プラズマアッシングガス」は、直流（直流プラズマ）または遠隔（遠隔プラズマ）のいずれかで励起された状態で膜を灰化するガスを指す。いくつかの実施形態では、「プラズマアッシングガス」は、単一のガスまたは二つ以上のガスの混合ガスである。用語「アッシング」は、プラズマを使用して有機物を除去することを指し、鉱物成分を通常は真空ポンプで除去される残留物（灰）として残す。
いくつかの実施形態では、「膜」は、対象物または関連する表面全体を覆うために実質的にピンホールなしで厚さ方向に垂直な方向に連続的に延在する層、または単に対象物もしくは関連する表面を覆う層を指す。いくつかの実施形態では、「層」は、表面上に形成される特定の厚さを有する構造、または膜の同義語、または膜でない構造を指す。膜または層は、特定の特性を有する個別の単一の膜もしくは層、または複数の膜もしくは層によって構成されてもよく、隣接する膜または層の間の境界は、明確であってもなくてもよく、物理的、化学的、および／もしくは他の任意の特徴、形成プロセスもしくはシーケンス、ならびに／または隣接する膜もしくは層の機能もしくは目的に基づいて示される。更に、本開示では、定常業務に基づいて実行可能な範囲を決定することができるので、任意の二つの変数はその変数の実行可能な範囲を構成することができ、示された任意の範囲は端点を含む、または除外することができる。いくつかの実施形態では、更に、示された変数の任意の値は（それらが「約」で示されているか否かにかかわらず）、正確な値またはおおよその値を指し、等価物を含み、平均値、中央値、代表値、または大多数等を指してもよい。更に、本開示では、用語「によって構成される」および「有する」は、いくつかの実施形態では、「典型的にまたは広く含む」、「含む」、「から本質的になる」、または「からなる」を独立して指す。本開示では、あらゆる定義された意味は、いくつかの実施形態では通常および慣習的な意味を必ずしも排除するものではない。
本開示では、「連続的に」とは、真空を破壊することがない、時系列として中断することない、いかなる物質介在工程もない、次の工程として直後に処理条件を変更することがない、またはいくつかの実施形態において二つの構造間にその二つの構造以外の介在する別個の物理的構造または化学構造がない、ことを指す。
本開示では、用語「充填能力」（「流動性」とも呼ばれる）は、実質的にボイドなしに（例えば、直径約５ｎｍ以上のサイズを有するボイドがない）および継ぎ目なしに（例えば、長さが約５ｎｍ以上の継ぎ目なし）、ギャップを充填する能力を指し、アスペクト比が約１以上の幅の広いトレンチに膜を堆積する場合、シームレス／ボイドのないボトムアップ成長の層が観察される。
流動性は、多くの場合トレンチを埋める前に広いトレンチの底部に膜の凹状面として現れ、完全にトレンチを埋めた後に連続して堆積される場合、膜のほぼ平面状のトップ面としても現れる（平坦化）。このような堆積は、「ボトムアップ堆積」と呼ばれる。
トレンチが狭くて深い場合、たとえ膜が流動性であっても、膜がトレンチの底部に達することができない場合がある。その場合、流動性は、多くの場合、トレンチの底部に膜が実質的になく、典型的にはトレンチのトップ開口部が膜によって閉鎖された、トレンチの側壁に沿った粗いまたは実質的に共形な膜として現れる。膜は流動性であるので、側壁膜は側壁に沿って流れて下向きに延在し、それにより薄膜を形成し、膜の実質的に共形部分の平均厚さ（アッシングによって実質的に除去される、トレンチのトップ開口部を閉じるトップ部を除く）の、トレンチ内の膜の深さ（側壁に沿って底部に向かって延在する長さ）に対する比は、０．１％から１０％（通常、０．５％〜５％）の範囲であることができる。このような堆積は、「ボトムレス堆積」と呼ばれる。
本開示では、隣接する突出構造と他の任意の凹部パターンとの間の凹部は「トレンチ」と呼ばれる。すなわち、トレンチは、穴／ビアを備える任意の凹部パターンである。ボトムアップ堆積の場合、いくつかの実施形態では、トレンチは、約２０ｎｍ〜約１００ｎｍ（通常、約３０ｎｍ〜約５０ｎｍ）の幅（トレンチの長さが幅と実質的に同じである場合、それはホール／ビアと呼ばれる）、約３０ｎｍ〜約１００ｎｍ（通常、約４０ｎｍ〜約６０ｎｍ）の深さ、および約２〜約１０（通常、約２〜約５）のアスペクト比を有する。ボトムレス堆積の場合、いくつかの実施形態では、トレンチは、約５．５ｎｍ〜約２００ｎｍ（通常、約１０ｎｍ〜約１００ｎｍ）の幅（ＣＤ）、約８００ｎｍ〜約１０，０００ｎｍ（通常、約３００ｎｍ〜約８，０００ｎｍ）の深さ、および約１５〜約１５０（通常、約２０〜約１００）アスペクト比を有する。トレンチの適切な寸法は、プロセス条件、膜の流動性、膜組成、所定の用途等に応じて変わることができる。膜の流動性を調整することによって、例えば、ボトムアップ堆積およびボトムレス堆積は、上記のものとは異なるサイズを有するトレンチにおいて実現されることができる。
本開示では、用語「実質的に堆積しない」、「実質的に膜がない」等は、ゼロと機能的に同等な量、重要ではないまたは無視できる量、後続のプロセス（たとえば、アッシング）に実質的に干渉しない量、検出可能な量または観測可能な量より少ない量等を指す。
本開示では、定義された意味は、いくつかの実施形態では通常および慣習的な意味を必ずしも排除しない。また、本開示では、「発明」または「本発明」は、本明細書で明示的、必然的、または本質的に開示される実施形態または態様のうちの少なくとも一つを指す。
実施形態は、好ましい実施形態に関して説明される。しかし、本発明は好ましい実施形態に限定されることを意図しない。
いくつかの実施形態は、基材のパターン形成された凹部にトポロジー制御層を形成する方法を提供し、方法は、（ｉ）ボトムアップ方式またはボトムレス方式で凹部を充填するために、パルスプラズマアシスト堆積によって基材のパターン形成された凹部上に充填能力を有するＳｉを含まないＣ含有膜を堆積させることと、（ｉｉ）主に充填膜の底部のみ、または主に充填膜の側壁部のみを残す方法で、充填膜のトップ部を除去するために、凹部に充填されたボトムアップまたはボトムレス膜をプラズマアッシングすることと、を含む。Ｓｉを含まないＣ含有膜は、通常、流動性膜であるアモルファスカーボンポリマー膜であることができる。プラズマアシスト法を用いてアモルファスカーボンポリマー膜を形成される場合、得られるアモルファスカーボンポリマー膜は水素化アモルファスカーボンポリマーからなる。本開示では、水素化アモルファスカーボンポリマーは、アモルファスカーボンポリマーを単に指す場合があり、略語として「ａＣ：Ｈ」または単に「ａＣ」と呼ばれる場合もある。さらにまた、本明細書において、ＳｉＣ、ＳｉＣＯ、ＳｉＣＮ、ＳｉＣＯＮ等は、特に記載のない限り、（単に主構成元素で示す）膜種を非化学量論的に示す略称である。
いくつかの実施形態では、ステップ（ｉ）において、炭化水素前駆体を使用して、Ｓｉを含まないＣ含有膜が堆積される。いくつかの実施形態では、工程（ｉ）は：（ｉａ）基材が配置される反応空間に前駆体を供給することと、（ｉｂ）パターン形成された凹部にＳｉを含まないＣ含有膜を堆積させるために、基材のパターン形成された凹部をプラズマに曝すことと、を含み、工程（ｉｂ）は、プラズマをパルス化する方法で断続的に行われ、工程（ｉａ）は、工程（ｉｂ）の工程前提条件として工程（ｉｂ）と重複することなく、連続的または断続的に行われる。いくつかの実施形態では、Ｓｉを含まないＣ含有膜は、実質的に炭化水素からなる。
流動性膜の堆積は当該技術分野において公知である。しかし、流動性膜の従来の堆積は、パルスプラズマアシスト堆積、例えばＰＥＡＬＤは、流動性膜の特性と全く反対の特性を有する膜である共形の膜を堆積するために周知であるので、ＲＦパワーを一定に印加しながら化学気相堆積（ＣＶＤ）を使用する。いくつかの実施形態では、流動性膜は、アモルファスカーボンポリマーからなるシリコンを含まない炭素含有膜であり、炭化水素前駆体のうちの任意の好適な一つまたは複数が候補となる可能性があるが、いくつかの実施形態では、前駆体は、２５℃で１，０００Ｐａ以上の蒸気圧を有する不飽和または環状炭化水素を含む。いくつかの実施形態では、前記前駆体は、Ｃ２〜Ｃ８アルキン（ＣｎＨ２ｎ−２）、Ｃ２〜Ｃ８アルケン（ＣｎＨ２ｎ）、Ｃ２〜Ｃ８ジエン（ＣｎＨｎ＋２）、Ｃ３〜Ｃ８シクロアルケン、Ｃ３〜Ｃ８アヌレン（ＣｎＨｎ）、Ｃ３〜Ｃ８シクロアルカン、および上記の置換炭化水素からなる群から選択される少なくとも一つの化合物である。いくつかの実施形態では、前駆体はエチレン、アセチレン、プロペン、ブタジエン、ペンテン、シクロペンテン、ベンゼン、スチレン、トルエン、シクロヘキセン、および／またはシクロヘキサンである。
いくつかの実施形態では、流動性膜の堆積のためのギャップ充填技術として、米国特許出願第１６／０２６，７１１号に開示されている方法を使用することができる。この出願は、窒素、酸素、または水素プラズマが必要とされない条件下で実質的にボイドを形成することなく、炭化水素前駆体を使用するプラズマアシスト堆積による完全なギャップ充填を提供し、その開示はその全体が参照により本明細書に組み込まれる。
堆積条件またはプロセスパラメータを変更することにより、非流動性膜を形成することができる。例えば、このようなパラメータとしては、前駆体の分圧、堆積温度、堆積圧力等が挙げられるが、これらに限定されない。例えば、堆積温度を上げること、堆積圧力を下げること、および／または前駆体比（前駆体流量のキャリアガス／希釈ガス流量に対する比）を下げることにより、膜の流動性が低くなる。いくつかの実施形態では、プロセス（ｉ）（堆積プロセス）は、プラズマエンハンスト原子層堆積（ＰＥＡＬＤ）または他の周期的プラズマアシスト堆積（例えば、周期的ＰＥＣＶＤ）によって行われる。プラズマとしては、容量結合プラズマ、誘導結合プラズマ、遠隔プラズマ、ＲＦパワーにより発生するプラズマ、マイクロ波により発生するプラズマ等を用いることができる。
いくつかの実施形態では、工程（ｉｉ）のプラズマアッシングは、直流または遠隔の酸素もしくは水素プラズマを使用して行われる。いくつかの実施形態では、直流または遠隔の酸素もしくは水素プラズマは、Ｈ２のみ、ＡｒとＨ２との混合物（Ａｒ／Ｈ２流量比０．００５〜０．９９５、通常０．０５〜０．７５）、ＨｅとＨ２との混合物（Ｈｅ／Ｈ２流量比０．００５〜０．９９５、通常０．０５〜０．７５）、Ｎ２とＨ２との混合物（Ｎ２／Ｈ２流量比０．００５〜０．９９５、通常０．０５〜０．７５）、Ｏ２のみ、Ｏ２とＡｒとの混合物（Ｏ２／Ａｒ流量比０．００５〜０．９９５、通常０．０５〜０．７５）、Ｏ２とＨｅとの混合物（Ｏ２／Ｈｅ流量比０．００５〜０．９９５、通常０．０５〜０．７５）、およびＯ２とＮ２との混合物（Ｏ２／Ｎ２流量比０．００５〜０．９９５、通常０．０５〜０．７５）からなる群から選択されるガスの直流または遠隔プラズマである。
いくつかの実施形態では、凹部のアスペクト比は１０〜１５０（通常は１５〜１００）の範囲であり、凹部の深さは２００ｎｍを超え、凹部は工程（ｉ）のボトムレス方式で膜で充填され、および充填された膜のトップ部は凹部のトップ開口部を塞ぐ。いくつかの実施形態では、プラズマアッシングは、工程（ｉｉ）で凹部の塞がれたトップ部を開き、充填された膜の側壁部分のみを主にまたは実質的に残すために行われる。
いくつかの実施形態では、基材は、アスペクト比２〜３０（通常は３〜２０）の複数の凹部を有し、凹部は工程（ｉ）のボトムアップ方式で膜で充填され、ローディング効果により表面トポロジーにばらつきがある。いくつかの実施形態では、工程（ｉ）は、複数の凹部上の膜の平坦化が起こるまで続き、次に工程（ｉｉ）でプラズマアッシングが行われ、複数の凹部に充填された膜の表面トポロジーを均一にして、および主にまたは実質的に充填膜の底部のみを残す。
図面を用いて、実施形態を説明する。ただし、本発明は図面に限定されることを意図しない。
図２は本発明の実施形態によるボトムアップ堆積させた（（ａ）→（ｂ）→（ｃ））およびボトムレス堆積させた（（ａ）→ｄ）→（ｅ））トレンチの概略断面図を例示する図である。最初に、図２の（ａ）では、トレンチを有する基材が提供され、ボトムアップ堆積の場合、基材２１は、流動性膜がトレンチ内に流れ込むことができるように十分に広い幅を有し、および流動性膜がトレンチ２０の底部に到達することを可能にするのに十分に小さい深さを有するトレンチ２０を有し、一方、ボトムレス堆積の場合、基材３１は、流動性膜がトレンチ内に流れ込むことができるように十分に広い幅を有するが、膜がトレンチ３０の底部に到達する前に、トレンチ３０のトップ開口部を膜で塞ぐのに十分なほど狭く、流動性膜がトレンチ３０の底部に到達できないように十分に深い深さを有するトレンチ３０を有する。例えば例として、トレンチの好適なサイズは本開示に記載されており、膜の流動性に従って選択することができる。図２は過度に簡略化されており、一定の割合では縮尺されていないことに留意されたい。
次に、堆積プロセスでは、堆積サイクル数、アッシングの継続時間等を除いて、（ｂ）のボトムアップ堆積と（ｄ）のボトムレス堆積の両方に同じ堆積プロセス条件を用いることができ、堆積プロセス条件は、トレンチのサイズ、膜の目標堆積厚さ、目標アッシング量、膜の目標最終トポロジー等に応じて変更される。（ｂ）では、流動性膜がボトムアップ方式でトレンチ２０を充填し、そしてトレンチ２０を完全に充填した後、膜２２のトップ面が平坦化されるまで、基材２１上に連続的に堆積する。膜の流動性により、平坦化できる。（ｄ）では、流動性膜は、基材３１の上部に堆積し、トレンチ３０内に流れ込み、ボトムレス方式でトレンチ３０の側壁に沿って下向きに移動し、流動性膜３２でトレンチ３０のトップ開口部を塞ぐ。流動性膜は、例えば、アスペクト比が約１０〜１００のトレンチ３０の側壁に沿って下向きに流れるため、側壁上の膜は側壁に沿って実質的に共形になり、スペーサとして機能することができる。堆積毎に膜の流動性を調整することにより、同じサイズのトレンチにボトムアップ堆積およびボトムレス堆積が行なわれることができることに留意されたい。例えば、米国特許出願第１６／０２６，７１１号に開示の流動性を調整する方法を使用することができる。
次に、アッシング工程では、膜を構成するアモルファスカーボンは、プラズマに曝されたトップ面から、底部のみのトポロジーまたは側壁のみのトポロジーに好適な深さまで除去（アッシング）される。（ｃ）では、基材２１のトップ面上に堆積させた膜２２の部分、およびボトムアップ方式でトレンチ２０内に充填された膜２２の上部を除去することにより、底部のみのトポロジーを有する膜２３が得られることができる、それは均質でほぼ均一な深さを有する。（ｅ）では、基材３１のトップ面上に堆積させた膜３２の部分、およびボトムレス方式でトレンチ３０の上部開口部を塞ぐ膜３２の上部を除去することにより、側壁のみのトポロジーを有する膜３３が得られることができ、それは均質でほぼ均一な厚みを有する。
米国特許出願第１６／０２６，７１１号に開示のように、いくつかの実施形態では、好ましくは、堆積プロセスはＡＬＤと同様なレシピ（例えば、供給／パージ／プラズマ衝突／パージ）を使用し、プラズマ衝突中に前駆体の高い分圧を残すために、供給後のパージは自発的に大幅に短縮される。これはＡＬＤの化学的性質やメカニズムとは明らかに区別される。ＡＬＤと同様なレシピは後で説明されるようにより有益であることができるが、上記のプロセスは、得られる膜に良好な充填能力も与えるパルスプラズマＣＶＤに基づくことができる。
いくつかの実施形態では、従来のＡＬＤとは異なり、堆積膜の流動性に関する重要な態様には、以下が含まれる。
１）重合／連鎖成長が進行するために全ＲＦ−ＯＮ期間中の十分に高い分圧；
２）（ＲＦ−ＯＮ期間およびＲＦパワーによって定義される）反応を活性化するのに十分なエネルギー、過度に長くないＲＦ−ＯＮ期間；
３）流動性相の融点を超えるが、堆積させる材料の沸点より低く設定された、重合／連鎖成長のための温度および圧力。
いくつかの実施形態では、プロセスパラメータ範囲は、膜の流動性を調整するために以下のように調整される：
圧力に関しては、重力および表面張力は底部で膜を流動させるための駆動力であるので、流動性のためには高圧が好ましい。温度に関しては、流動性のために低温が好ましい（これは直観的にわかりにくい）が、高温はポリマーの連鎖成長速度に有利に働く。
図１２は、本発明の実施形態による膜形成のプロセスのシーケンスを例示する図であり、灰色のセルはオン状態を表し、一方、白色のセルはオフ状態を表し、各列の幅は各プロセスの持続時間を表していない。この簡略化されたプロセスシーケンスは、ボトムアップ堆積およびボトムレス堆積の両方に適用されることができ、いくつかの実施形態では、堆積サイクル数、アッシングの継続時間等を除いて、ボトムアップ堆積とボトムレス堆積の両方に同じ堆積プロセス条件を用いることができ、堆積プロセス条件は、トレンチのサイズ、膜の目標堆積厚さ、目標アッシング量、膜の目標最終トポロジー等に応じて変更される。
このプロセスシーケンスは、堆積プロセス（「供給」→「パージ」→「ＲＦパルス−１」（プラズマ重合）→「パージ」）、およびプラズマアッシングプロセス（「安定化」→「ＲＦパルス−２」（プラズマアッシング））→「パージ」）を含む。プラズマ重合プロセスは、Ｓｉおよび金属を含有しないＣ含有前駆体と、基材が二つの電極と平行に配置されている二つの電極の間にＲＦパワー（ＲＦ）を印加して、プラズマを発生させるプラズマ発生ガスを使用して、ＰＥＡＬＤと同様な堆積によりトレンチを有する基材上にアモルファスカーボンポリマー膜を堆積させることを含み、ＲＦパワーはＰＥＡＬＤと同様な堆積の各サブレイヤー堆積サイクルで印加され、プラズマ発生ガスおよびキャリアガスは連続的に流れ、ならびに「供給」後の「パージ」中および「ＲＦパルス−１」後の「パージ」中もパージガスとして機能する。
いくつかの実施形態では、３００ｍｍウェーハの場合（異なるサイズのウェーハの場合、下記のワット数は、各ウェーハの単位面積（ｃｍ２）あたりのＷとして適用される）、供給時間は０．３〜１０秒（通常０．６〜２秒）の範囲であり、供給後のパージ時間は０〜０．５秒（通常０〜０．３秒）の範囲であり、ＲＦ時間は０．５〜２秒（通常０．８〜１．５秒）の範囲であり、ＲＦ後のパージ時間は０〜０．５秒（通常０〜０．１秒）の範囲であり、キャリアガス流量は０〜０．８ｓｌｍ（通常０．１〜０．３ｓｌｍ）の範囲であり、プラズマ発生ガス流量は０〜０．５ｓｌｍ（通常０．１〜０．３ｓｌｍ）の範囲であり、およびＲＦパワーは５０〜４００Ｗ（通常７５〜２００Ｗ）の範囲である。
膜の流動性は、例えば揮発性炭化水素前駆体がプラズマによって重合され、基材の表面上に堆積する場合に一時的に得られる。気体モノマー（前駆体）は、プラズマガス放電によって供給されるエネルギーによって活性化または断片化されて重合を開始し、得られたポリマー材料が基材の表面上に堆積すると、その材料は一時的に流動性挙動を示す。堆積工程が完了すると、流動性膜はもはや流動性ではなく固化するので、したがって別の固化プロセスは必要とされない。
堆積プロセスは、ＰＥＡＬＤと同様なプロセスであり、サブレイヤー（通常は単層よりも厚い）を形成するためのそれの１サイクルは、プラズマアッシングプロセスを開始する前に、アモルファスカーボンポリマー膜の所望の厚さが得られるまでｑ回繰り返される。ここで、プラズマアッシングプロセスを開始する前に基材のトップ面上に２．５ｎｍ〜５０ｎｍ（好ましくは７．５ｎｍ〜２５ｎｍ）の厚さを有するアモルファスカーボンポリマー膜を堆積させるために、ｑは、トレンチのサイズ、膜の用途等に応じて、ボトムアップ堆積の場合、５〜１００（好ましくは２５〜５０）の整数であり、およびここで、プラズマアッシングプロセスを開始する前に、基材のトップ面上に５ｎｍ〜１００ｎｍ（好ましくは２０ｎｍ〜５０ｎｍ）の厚さを有するアモルファスカーボンポリマー膜を堆積させるために、ｑは、トレンチのサイズ、膜の用途等に応じて、ボトムレス堆積の場合、１０〜２００（好ましくは４０から１００）の整数である。
次に、プラズマアッシングプロセスが始まる。これは、ＲＦパワー（ＲＦ）によって励起されプラズマを発生させてアモルファスカーボンポリマー膜をアッシングする（「ＲＦパルス２」）アッシングガス（Ｈ２もしくはＯ２、または前述のガスとＮ２、Ａｒ、および／もしくはＨｅとの混合物）を、反応空間（「安定化」）に供給することと、その後パージ（「パージ」）することとを含み、アッシングガスは、プラズマアッシングプロセス全体を通して反応空間に連続的に供給される。いくつかの実施形態では、プラズマアッシングのためのＲＦパワーは、１００Ｐａ〜１０００Ｐａ（通常、２００〜６００Ｐａ）の圧力下で５〜２００秒（通常、１０〜１００秒）の継続時間、５０〜５００Ｗ（通常、５０〜２００Ｗ）の範囲であり、安定化時間は５〜６０秒（通常１０〜３０秒）の範囲、ＲＦ後のパージ時間は５〜６０秒（通常１０〜３０秒）の範囲、およびアッシングガス流量は０．１〜１０ｓｌｍ（通常０．５〜２ｓｌｍ）の範囲である。
一部の実施形態では、プロセス全体を通して、キャリアガスは、例えば０ｓｃｃｍ〜２０００ｓｃｃｍ（好ましくは１００ｓｃｃｍ〜５００ｓｃｃｍ）の範囲で反応空間に連続的に供給される。また、プロセスの温度は、−５０℃〜１７５℃（好ましくは３５℃〜１５０℃）の範囲とすることができる。
堆積プロセスにおけるプラズマ発生ガスおよびプラズマアッシングプロセスにおけるアッシングガスは、同じであっても異なっていてもよく、例えば、両方ともＡｒおよび／またはＨｅであってもよい。
キャリアガスの連続流は、フローパスシステム（ＦＰＳ）を使用して達成することができ、キャリアガスラインに前駆体貯留部（ボトル）を有する迂回ラインを設け、主ラインと迂回ラインとを切り替える。キャリアガスのみが反応チャンバーに供給されることが意図される場合、迂回ラインは閉じられ、一方、キャリアガスと前駆体ガスの両方が反応チャンバーに供給されることを意図される場合、主ラインは閉じられ、キャリアガスは迂回ラインを通って流れ、前駆体ガスと共にボトルから流出する。このように、キャリアガスは連続的に反応チャンバー内に流入することができ、主ラインと迂回ラインとを切り替えることによって前駆体ガスをパルス状に運ぶことができる。図１Ｂは、本発明の実施形態によるフローパスシステム（ＦＰＳ）を用いる前駆体供給システムを例示する（黒いバルブはバルブが閉じていることを示す）。図１Ｂの（ａ）に示すように、前駆体を反応チャンバー（図示せず）に供給する場合、まず、キャリアガス、例えばＡｒ（またはＨｅ）がバルブｂおよびｃを有するガスラインを通って流れ、そしてボトル（貯留部）２６に入る。キャリアガスは、ボトル２６内の蒸気圧に応じた量の前駆体ガスを運びながらボトル２６から流出し、バルブｆおよびｅを有するガスラインを通って流れ、そして前駆体と共に反応チャンバーに供給される。上記において、バルブａおよびｄは閉じられている。キャリアガス（希ガス）のみを反応チャンバーに供給する場合、図１Ｂの（ｂ）に示すように、キャリアガスはボトル２６を迂回しながらバルブａを有するガスラインを通って流れる。上記において、バルブｂ、ｃ、ｄ、ｅ、およびｆは閉じられている。
例えば図１Ａに示す装置を含む任意の好適な装置を用いてプロセスサイクルを行うことができる。図１Ａは、本発明のいくつかの実施形態で使用可能な、以下に記載のシーケンスを実行するようにプログラムされた制御装置と望ましくは一体化したＰＥＡＬＤ装置の概略図である。この図において、反応チャンバー３の内部１１（反応領域）に一対の導電性平板電極４、２を互いに平行に対向させて設け、一方の側にＨＲＦパワー（１３．５６ＭＨｚ、または２７ＭＨｚ）２５を印加し、他方の側１２を電気的に接地することにより、プラズマが電極間で励起される。下部ステージ２（下部電極）には温度調節器が設けられており、その上に配置された基材１の温度は所定の温度で一定に保持される。上部電極４はシャワープレートとしても機能し、反応物質ガスおよび／または希釈ガスがあればそれら、ならびに前駆体ガスは、それぞれガスライン２７およびガスライン２８を通り、そしてシャワープレート４を通って反応チャンバー３内に導入される。更に、反応チャンバー３内には、排気ライン７を有する円形ダクト１３が設けられており、これを通って反応チャンバー３の内部１１内のガスが排気される。更に、反応チャンバー３の下方に配置された搬送チャンバー５には、搬送チャンバー５の内部１６（搬送区域）を介して反応チャンバー３の内部１１内にシールガスを導入するためのシールガスライン２４が設けられている。反応区域と搬送区域とを分離するための分離プレート１４が設けられている（ウェーハを搬送チャンバー５内に搬入及び搬送チャンバー５から搬出するのに通過するゲートバルブはこの図から省略されている）。搬送チャンバーには排気ライン６も設けられている。いくつかの実施形態では、多元素膜の堆積及び表面処理は同じ反応空間内で行われるため、基材を空気又は他の酸素含有雰囲気に曝すことなく全ての工程を連続的に実施することができる。
いくつかの実施形態では、図１Ａに示す装置において、（前述の）図１Ｂに例示する不活性ガスの流れと前駆体ガスの流れとを切り替えるシステムを用いて、反応チャンバーの圧力を実質的に変動させることなく前駆体ガスをパルス状に導入することができる。
当業者は、本装置が、本明細書の他の箇所に記載された堆積プロセス及び反応器洗浄プロセスを実行させるようにプログラムされた又はそうでなければ構成された一つもしくは複数の制御装置（図示せず）を備えることを理解するであろう。当業者には理解されるように、制御装置は、様々な電源、加熱システム、ポンプ、ロボット、およびガスフローコントローラ又は反応器のバルブと通信している。
いくつかの実施形態では、デュアルチャンバー反応器（互いに近接して配置されたウェーハを処理するための二つの区域又は区画）を使用することができ、反応物質ガス及び希ガスを共有ラインを介して供給することができるのに対して、前駆体ガスは非共有ラインを介して供給される。
充填能力を有する膜は、３Ｄクロスポイントメモリデバイスにおけるセル分離、自己整合ビア、ダミーゲート（現在のポリＳｉの置き換え）、リバーストーンパターニング、ＰＣ ＲＡＭアイソレーション、カットハードマスク、およびＤＲＡＭストレージノードコンタクト（ＳＮＣ）アイソレーションを含むがこれらに限定されない様々な半導体デバイスに適用することができる。
実施例
条件および／または構造が特定されていない以下の実施例では、当業者は、定常的な実験として、本開示を考慮して、このような条件および／または構造を容易に提供することができる。当業者は、実施例で用いられる装置が、本明細書の他の箇所に記載された堆積プロセスおよび反応器洗浄プロセスを実行させるようにプログラムされたまたはそうでなければ構成された一つまたは複数の制御装置（図示せず）を備えることを理解するであろう。当業者には理解されるように、制御装置は、様々な電源、加熱システム、ポンプ、ロボット、およびガスフローコントローラ又は反応器のバルブと通信している。
参考例１（図３）
アモルファスカーボンポリマー膜を、下の表２に示す条件下で、図１２に示すプロセスシーケンスに従ってボトムアップ方式で、図１Ａに例示の装置および図１Ｂに例示のガス供給システム（ＦＰＳ）を使用するＰＥＡＬＤと同様なプロセスにより、開口部が約２５〜３５ｎｍ、深さが約８５ｎｍ（アスペクト比は約２．４〜３．４である）のトレンチを有するＳｉ基材（直径３００ｍｍ、厚さ０．７ｍｍ）上に堆積させた。膜を堆積し、トレンチを完全に充填し、更にその上堆積して平坦なトップ面を形成した。ＰＥＡＬＤと同様なサイクルを２４２回繰り返した（ｐ＝２４２）。その後、図１２に示すプロセスシーケンスに従って、以下の表２に示す条件で、Ｏ２とＡｒとの混合物またはＮ２とＨ２との混合物を用いて、連続的にアッシングを行った。
図３は、（ａ）でボトムアップ堆積させ、続いて（ｂ）でＯ２／Ａｒアッシング、または（ｃ）でＮ２／Ｈ２アッシングさせたトレンチの断面のＳＴＥＭ写真を示す。図３に示すように、アモルファスカーボンポリマー膜は効果的に流動性があり、全てのトレンチを（サイズの違いに関係なく）完全に満たし、さらにその上に堆積されて平坦なトップ面を形成し、アッシングプロセスによりアモルファスカーボンポリマー膜は、ＣＤの完全性を損なうことなく完全に除去またはアッシングされることができる。すなわち、アッシング時間を操作することにより、ＣＤの完全性を損なうことなく所望の量のアモルファスカーボンポリマー膜は除去されることができる。
実施例１
アモルファスカーボンポリマー膜を、ボトムアップ方式で、ＰＥＡＬＤと同様なプロセスにより、堆積サイクルが２１０回（ｐ＝２１０）繰り返されたこと以外は参考例１と同じ条件下で、開口部が約２０ｎｍ、深さが約２００ｎｍ（アスペクト比は約１０であった）のトレンチを有するＳｉ基材（直径３００ｍｍ、厚さ０．７ｍｍ）上に堆積させ、膜は基材のトップ面上に１００ｎｍの厚さに堆積した。その後、底部のみのトポロジーを有する膜構造を形成するように、ＲＦ時間を９０秒に短縮した以外は参考例１と同様にＯ２とＡｒとの混合物を用いてアッシングを連続的に行い、膜は基材のトップ面から１８１ｎｍの深さまでアッシングされた。
図９はボトムアップ堆積させたトレンチの断面のＳＴＥＭ写真であり、（ａ）は堆積の完了時のトレンチを表し、（ｂ）はアッシング後のトレンチを表す。図９に示すように、アモルファスカーボンポリマー膜は効果的に流動性があり、全てのトレンチを完全に満たし、さらにその上に堆積されて平坦なトップ面を形成し、アッシングプロセスによりアモルファスカーボンポリマー膜は、ＣＤの完全性を損なうことなく全てのトレンチで均一に除去またはアッシングされ、均一な底部だけのトポロジーを有する均質な膜構造を形成することができることが確認された。
実施例２
アッシング時間を変えたこと以外は実施例１と同様にして、トレンチを有するＳｉ基材上にアモルファスカーボンポリマー膜を堆積させた。
図１０はボトムアップ堆積（全充填）させたトレンチの断面図のＳＴＥＭ写真であり、行（ａ）は異なる幅を有する広いトレンチと狭いトレンチの混合を表し（スケールは３００ｎｍを表す）、行（ｂ）は中間のトレンチを表し（スケールは６０ｎｍを表す）、行（ｃ）は幅がわずかに異なる広いトレンチ（スケールは６０ｎｍを表す）を表し、列（１）はアッシング前に全充填堆積（２１０サイクルの堆積）させたトレンチを表し、列（２）は１０５秒間のアッシング後のトレンチを表し、列（３）は１２９秒間のアッシング後のトレンチを表し、列（４）は１６５秒間アッシング後のトレンチを表す。
図１１は、ボトムアップ堆積させたトレンチの断面のＳＴＥＭ写真であり、（ａ）は全充填堆積（２１０サイクルの堆積）の完了時のトレンチを表し、（ｂ）は２４０秒間のアッシング後のトレンチを表し、（ｃ）は３００秒間のアッシング後のトレンチを表す。
図１０および１１に示すように、アモルファスカーボンポリマー膜は効果的に流動性があり、全てのトレンチを完全に満たし、さらにその上に堆積されて平坦なトップ面を形成し、アッシングプロセスにより、アモルファスカーボンポリマー膜は、ＣＤの完全性を損なうことなく全てのトレンチで均一に除去またはアッシングされ、均一な底部だけのトポロジーを有する均質な膜構造を形成することができることが確認された。また、驚くべきことに、全充填堆積とアッシングとの組み合わせは、実質的にローディング効果なしに、底部のみの堆積を均一に達成できることが確認された。
参考例２
アモルファスカーボンポリマー膜を、ボトムレス方式で、ＰＥＡＬＤと同様なプロセスにより、堆積サイクルが３５０回（ｐ＝３５０）繰り返されたこと以外は参考例１と同じ条件下で、開口部が約１５０ｎｍ、深さが約２５００ｎｍ（アスペクト比は約１７であった）のトレンチを有するＳｉ基材（直径３００ｍｍ、厚さ０．７ｍｍ）上に堆積させ、膜は基材のトップ面上に１６０ｎｍの厚さに堆積した。
ボトムレス堆積は、ボトムレス堆積されたトレンチの断面図のＳＴＥＭ写真によって確認される。写真は（ａ）一連の膜が堆積されたトレンチの図、（ｂ）トレンチの一つのトップ部の拡大図、（ｃ）トレンチの底部の拡大図、および（ｄ）トレンチの側壁の拡大図を含む。（ａ）で観察されるようにトレンチが膜で完全に満たされているわけではないが、アモルファスカーボンポリマー膜は効果的に流動性があり、（ｂ）で観察されるようにトレンチのトップ部は膜で塞がれるが（上部は過充填される）、（ｄ）で観察されるように膜は下向きに流れてトレンチの側壁に沿ってトレンチの底に向かって延在し、（ｃ）で観察されるようにトレンチの底に到達せずに、側壁に沿って実質的に共形な（側壁に沿って実質的に均一な厚さ）および均質な膜構造を形成することが確認された。
参考例３
アモルファスカーボンポリマー膜を、ボトムレス方式で、ＰＥＡＬＤと同様なプロセスにより、堆積サイクルが３００回（ｐ＝３００）繰り返されたこと以外は参考例１と同じ条件下で、開口部が約１４０〜１６０ｎｍ、深さが約２５００ｎｍ（アスペクト比は約１６〜１８であった）のトレンチを有するＳｉ基材（直径３００ｍｍ、厚さ０．７ｍｍ）上に堆積させ、膜は基材のトップ面上に１１６ｎｍの厚さに堆積した。
図４はアッシングなしでボトムレス堆積（３００サイクル）させたトレンチの断面のＳＴＥＭ写真の概略図を示す。図４に示すように、トレンチが膜で完全には充填されていないが、アモルファスカーボンポリマー膜は効果的に流動性があり、トレンチのトップ部は膜でちょうどまたはかろうじて塞がれて（上部は過充填され）膜は基材のトップ面上に堆積したが、膜は下向きに流れてトレンチの側壁に沿ってトレンチの底部に向かって延在し、トレンチの底部にわずかに達し、側壁に沿って実質的に共形な（側壁に沿って実質的に均一な厚さ）および均質な膜構造を形成することが確認された。ドライエッチング条件が下層と比較して炭素膜の選択性が高い（例えば、＞１００）ように設定される場合、底部の膜のわずかな堆積は、超ディープホールを形成するためのさらなるエッチングを妨げず、したがって、この堆積は依然としてボトムレス堆積と呼ばれる。さらに、膜の流動性を調整する（流動性をわずかに低下させる）ことにより、側壁に沿った膜の流れを、底部に到達する前に停止させることができる。
実施例３
参考例３と同じ条件下で、アモルファスカーボンポリマー膜をボトムレス方式でＳｉ基材上に堆積させた。その後、ＲＦ時間を９０秒に短縮したこと以外は参考例１と同様に、Ｏ２とＡｒとの混合物を用いて連続的にアッシングを行った。基材のトップ面上に堆積された膜の一部を薄くし、トレンチ内の膜のトップ閉鎖部分（過充填部）を除去してトレンチを開き、それにより、トレンチ内に空間のような構造を形成する。
図５はボトムレス堆積（３００サイクル）させ、続いてアッシング（９０秒）したトレンチの断面のＳＴＥＭ写真の概略図を示す。図５に示すように、ＣＤの完全性を損なうことなくトレンチのトップを開口するために、アッシングにより、過充填されたトレンチのトップ部が効果的に除去され、側壁に沿って実質的に共形な（側壁に沿って実質的に均一な厚さ）および均質な膜構造を形成することが確認された。
参考例４
アモルファスカーボンポリマー膜を、堆積サイクルが３５０回（ｐ＝３５０）繰り返されたこと以外は参考例３と同じ条件下で、ボトムレス方式でＳｉ基材上に堆積させた。その結果、膜は基材のトップ面上に１６０ｎｍの厚さに堆積し、トレンチのトップ開口部を完全に塞いだ（トレンチ上の過充填された部分の厚さは１４５ｎｍであった）。
図６はアッシングなしでボトムレス堆積（３５０サイクル）させたトレンチの断面のＳＴＥＭ写真の概略図を示す。図６に示すように、トレンチが膜で完全には充填されないが、アモルファスカーボンポリマー膜は効果的に流動性があり、トレンチのトップ部は膜で塞がれ、膜は基材のトップ面上に堆積したが、参考例３と同様に膜は下向きに流れてトレンチの側壁に沿ってトレンチの底部に向かって延在することが確認された。
実施例４
参考例４と同じ条件下で、アモルファスカーボンポリマー膜をボトムレス方式でＳｉ基材上に堆積させた。その後、ＲＦ時間を９０秒に短縮したこと以外は参考例１と同様に、Ｏ２とＡｒとの混合物を用いて連続的にアッシングを行った。基材のトップ面上に堆積された膜の一部を薄くし、トレンチ内の膜のトップ閉鎖部分（過充填部）を除去してトレンチを開き、それにより、トレンチ内に空間のような構造を形成する（トレンチ上の過充填部の厚さは９５ｎｍであった）。
図７はボトムレス堆積（３５０サイクル）させ、続いてアッシング（９０秒）したトレンチの断面のＳＴＥＭ写真の概略図を示す。図７に示すように、ＣＤの完全性を損なうことなく各トレンチのトップを開口するために、アッシングにより、過充填されたトレンチのトップ部が効果的に除去され、側壁に沿って実質的に共形な（側壁に沿って実質的に均一な厚さ）および均質な膜構造を形成することが確認された。
本発明の趣旨を逸脱することなく、多数の様々な修正を行うことができることが当業者には理解されよう。したがって、本発明の形態は例示にすぎず、本発明の範囲を限定することを意図するものではないことを明確に理解されるべきである。
２、４ 導電性平板電極
３ 反応チャンバー
５ 搬送チャンバー
６、７ 排気ライン
１１ 反応チャンバーの内部
１３ 円形ダクト
１４ 分離プレート
１６ 搬送チャンバーの内部
２０、３０ トレンチ
２１、３１ 基材
２２、２３、３２、３３ 膜
２４ シールガスライン
２５ ＨＲＦパワー
２７、２８ ガスライン

Claims (10)

  1. 基材のパターン形成された凹部にトポロジー制御層を形成する方法であって、
    （ｉ）ボトムアップ方式またはボトムレス方式で前記凹部を充填するために、パルスプラズマアシスト堆積によって前記基材の前記パターン形成された凹部上に充填能力を有するＳｉを含まないＣ含有膜を堆積させることと、
    （ｉｉ）主にもしくは実質的に前記充填膜の底部のみ、または主にもしくは実質的に前記充填膜の側壁部のみを残す方法で、前記充填膜のトップ部を除去するために、前記凹部内に充填された前記ボトムアップまたはボトムレス膜をプラズマアッシングすることと、を含む、方法。
  2. 工程（ｉｉ）の前記プラズマアッシングは、直流または遠隔の酸素もしくは水素プラズマを使用して行われる、請求項１に記載の方法。
  3. 前記直流または遠隔の酸素もしくは水素プラズマは、Ｈ２のみ、ＡｒとＨ２との混合物、Ｎ２とＨ２との混合物、ＨｅとＨ２との混合物、Ｏ２のみ、Ｏ２とＡｒとの混合物、Ｏ２とＨｅとの混合物、およびＯ２とＮ２との混合物からなる群から選択されるガスの直流または遠隔プラズマである、請求項２に記載の方法。
  4. 工程（ｉ）において、炭化水素前駆体を使用して、前記Ｓｉを含まないＣ含有膜が堆積される、請求項１に記載の方法。
  5. 工程（ｉ）は、（ｉａ）前記基材が配置される反応空間に前駆体を供給することと、（ｉｂ）前記パターン形成された凹部に前記Ｓｉを含まないＣ含有膜を堆積させるために、前記基材の前記パターン形成された凹部をプラズマに曝すことと、を含み、工程（ｉｂ）は、前記プラズマをパルス化する方法で断続的に行われ、工程（ｉａ）は、工程（ｉｂ）の工程前提条件として工程（ｉｂ）と重複することなく、連続的または断続的に行われる、請求項１に記載の方法。
  6. 前記Ｓｉを含まないＣ含有膜は実質的に炭化水素からなる、請求項１に記載の方法。
  7. 前記凹部のアスペクト比は１０〜１００の範囲であり、前記凹部の深さは２００ｎｍを超え、前記凹部は工程（ｉ）のボトムレス方式で前記膜で充填され、および前記充填された膜のトップ部は前記凹部のトップ開口部を塞ぐ、請求項１に記載の方法。
  8. プラズマアッシングは、工程（ｉｉ）で、前記凹部の前記塞がれたトップ部を開くために、および前記充填された膜の前記側壁部のみを主にまたは実質的に残すために行われる、請求項６に記載の方法。
  9. 前記基材は、アスペクト比２〜３０の複数の凹部を有し、前記凹部は工程（ｉ）のボトムアップ方式で前記膜で充填され、ローディング効果により表面トポロジーにばらつきがある、請求項１に記載の方法。
  10. 工程（ｉ）は、前記複数の凹部上の前記膜の平坦化が起こるまで続き、次に工程（ｉｉ）でプラズマアッシングが行われ、前記複数の凹部に充填された前記膜の前記表面トポロジーを均一にして、および主にまたは実質的に前記充填膜の前記底部のみを残す、請求項８に記載の方法。
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