JP6977474B2 - 半導体装置の製造方法 - Google Patents
半導体装置の製造方法 Download PDFInfo
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- JP6977474B2 JP6977474B2 JP2017204747A JP2017204747A JP6977474B2 JP 6977474 B2 JP6977474 B2 JP 6977474B2 JP 2017204747 A JP2017204747 A JP 2017204747A JP 2017204747 A JP2017204747 A JP 2017204747A JP 6977474 B2 JP6977474 B2 JP 6977474B2
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- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
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Description
一方で、犠牲膜を使用した後の製造途中の半導体装置(以下、「構造体」ともいう)の表面には、既述のトレンチホールやビアホールなどの開口が形成されている場合もある。この開口を介して構造体内にエッチングガスやエッチング液(これらをまとめて「エッチャント」ともいう)が進入すると、エッチャントと接触した構造体内部の部材が劣化するなどのダメージを受けてしまうおそれもある。
しかしながら、最終的には保護部自体も製品である半導体装置からは除去されるものであるところ、当該保護部を除去する処理において構造体の内部にダメージを与えてしまうおそれもある。
表面が犠牲膜によって覆われ、パターニングされた前記犠牲膜の開口に対応する凹部が形成された基板に対し、前記犠牲膜の上面側から重合用の原料を供給して、尿素結合を有する重合体からなる重合体膜を形成し、前記凹部内に前記重合体を埋め込む工程と、
前記凹部内に埋め込まれた重合体を残して、前記犠牲膜の上面側の重合体膜を除去する工程と、
前記凹部内に重合体が埋め込まれた状態で前記犠牲膜を除去する工程と、
次いで、前記凹部内の重合体を除去する工程と、を含むことを特徴とする。
<第1の実施形態>
はじめに、本発明の半導体装置の製造方法を半導体装置の配線を形成する工程に適用した実施形態について説明する。詳細には、犠牲膜であるハードマスク22を用いて凹部(トレンチ291)を形成する際に、ポリ尿素の重合体膜(ポリ尿素膜6)を利用する技術について図1〜5を参照しながら説明する。図1〜5は半導体装置の製造途中の構造体の例を示している。当該構造体は基板である半導体ウエハ(以下、「ウエハ」という)Wに形成される。
先ず図1(b)に示すように低誘電率膜20の表面に、トレンチに対応する部位が開口する例えばTiN(チタンナイトライド)膜からなるエッチング用のパターンマスクであるハードマスク22が公知の手法により形成される。
埋め込み部6aの形成にあたっては、上述のビアホール29の形成を行った後、SOC膜23の上面側からポリ尿素膜6を形成することにより、ビアホール29内にポリ尿素を埋め込む(図4(i))。
ポリ尿素は、例えば図6に示すようにイソシアネートとアミンとを用いて共重合により生成することができる。R(置換基)は例えばアルキル基(直鎖状アルキル基または環状アルキル基)またはアリール基であり、nは2以上の整数である。
アミンとしては、例えば脂環式化合物または脂肪族化合物を用いることができ、脂環式化合物としては、例えば1,3−ビス(アミノメチル)シクロヘキサン(H6XDA)が、脂肪族化合物としては、例えば1,12−ジアミノドデカン(DAD)が夫々挙げられる。
このとき、イソシアネートの蒸気の供給を停止し、真空容器70内を真空排気してからアミンの蒸気を供給し、次いでアミンの蒸気の供給を停止し、真空容器70内を真空排気してからイソシアネートの蒸気を供給するという手法を用いてもよい。あるいは一方の蒸気の供給を停止した後、続いて他方の蒸気を供給し、他方の蒸気の供給を停止した後、続いて一方の蒸気を供給する手法を採用してもよい。または、イソシアネートの蒸気とアミンの蒸気とを同時に真空容器70内に供給する手法を用いてもよい。
図中、符号81は、ウエハWを吸着保持して回転機構80により回転する載置台であるバキュームチャック、82は、カップモジュール、83は、下方に伸びる外周壁及び内周壁が筒状に形成されたガイド部材である。84は、全周に亘って排気、排液を行うことができるように外カップ85と前記外周壁との間に形成された排出空間であり、排出空間84の下方側は気液分離できる構造になっている。図中88は、例えば下方側からウエハWに光を照射することにより加熱するLED(発光ダイオード)であり、後述のようにウエハWに薬液が供給されるときに、重合が行われるように、当該ウエハWを加熱する。
更にまた図10(a)、(b)に示すように、イソシアネートと二級アミンとを用いてもよく、この場合に生成される重合体に含まれる結合も尿素結合である。
ポリ尿素においては、重合と解重合との可逆的平衡反応が成り立っており、温度が上昇すると解重合が支配的になる。例えば300℃以上では、平衡が解重合側に偏っており、この温度環境下では解重合により生成されたモノマーが気化し、時間の経過とともにポリ尿素膜6の膜厚が薄くなって、やがて全部が消失する。解重合によりポリ尿素膜6が消失に至るまでの時間は、環境温度が高いほど短い。
ポリ尿素はアミンに解重合して蒸発するが、ウエハW上に既に形成されている素子部分、特に配線材料12を構成する例えば銅配線に悪影響を与えないようにするためには、400℃以下、例えば390℃以下で加熱することが好ましく、例えば300℃〜350℃で加熱することがより好ましい。
また加熱機構としては赤外線ランプ54に限らず、載置台52に設けたヒータであってもよい。
ビアホール29に埋め込み部6aが埋め込まれていることにより、比較的厚いSOC膜23のエッチングを行っている期間中、プラズマがビアホール29内に進入することを防ぎ、低誘電率膜20のダメージの発生を抑制することができる。
加熱のみによる埋め込み部6aの除去は、エッチャントを用いる場合と比較して低誘電率膜20や銅配線12に与える影響が小さい。この観点において、埋め込み部6aの除去時においても低誘電率膜20や銅配線12などに与えるダメージを抑制することができる。
さらに他の手法として、例えば低誘電率膜20や銅配線12へのダメージが小さい場合には、酸素を含むエッチングガスをプラズマ化して活性化したガスにより埋め込み部6a内のポリ尿素をアッシングして除去する手法も採用することができる。
なお、これらバリア層の成膜、銅配線の形成については図示を省略する。
次いで、DRAM(Dynamic Random Access Memory)の製造工程において、キャパシタとなる構造体を構成するSiO2(酸化シリコン)膜に比較的深い凹部を形成する際にポリ尿素のポリ尿素膜6を利用する技術について図15〜17を参照しながら説明する。
凹部301は、ホール径あるいは溝幅が例えば直径80nm×深さ2μmである。
ポリ尿素膜6の成膜手法や構成については、第1の実施形態にて説明した例と同様なので、再度の説明を省略する。
この場合には、凹部301内にシームと呼ばれる空隙302が形成されてしまう。また凹部301に対応する位置においてポリ尿素膜6の表面に窪みが発生してしまう。
なおこのとき、解重合によりポリ尿素膜6の膜厚も小さくなる。加熱温度を高くすることにより埋め込みに要する時間が短くなるが、解重合に伴うポリ尿素膜6の表面からの膜減りの速度も大きくなってしまう。この結果、膜厚の微調整が難しくなることから、ポリ尿素膜6の成膜時の膜厚、及び膜厚の調整量などに応じて加熱温度、加熱時間が設定される。
その後、再度、ウエハWの加熱処理を行うことにより、埋め込み部6aを構成するポリ尿素を解重合させ、凹部301内から埋め込み部6aを除去する(図16(h))。
こうした問題に対して、ポリ尿素の埋め込み部6aは、加熱処理などにより比較的容易に除去可能なので、凹部301に向けて露出する構造体(半導体装置)へのダメージの発生を抑えつつ除去を行うことができる。
図18〜21は、イオン注入処理時のマスクを除去する際にポリ尿素の埋め込み部6aを利用する例を示している。
図18において、符号9aは基板91上に形成されたフィン型FETの製造途中段階の構造体であり、9bはフィン型の半導体デバイスの製造途中段階の構造体である。
溝部94aは、溝幅が例えば10〜100nmであり、アスペクト比が例えば2以上である。
図19(a)は犠牲膜であるマスク901の成膜処理を行う前の基板91の表面部分の状態を示している。先ず基板91に対して、例えばSiOC(炭素及び酸素含有シリコン酸化物)膜、SiN(窒化シリコン)膜、SiO2(酸化シリコン)膜などからなるマスク901を成膜する(図19(b))。
そして、前記レジスト膜902の開口を介してマスク901を除去し、凹部である開口921を形成する。この開口921を介してイオン注入が行われる領域を露出させてからレジスト膜902を除去する(図20(d))。
ポリ尿素膜6の成膜手法や構成については、第1の実施形態にて説明した例と同様なので、再度の説明を省略する。
しかる後、再度、基板91の加熱処理を行うことにより、埋め込み部6aを構成するポリ尿素を解重合させ、不純物領域922の上面から埋め込み部6aを除去する(図21(i))。
ポリ尿素膜6に対し種々の薬液を供給して、ポリ尿素膜6の除去の状況を調べた。
A.実験条件
図12(a)に示す骨格構造を有し、シリコン製の試料基板の表面に、膜厚150nmのポリ尿素膜6を成膜し、各種薬液中に試料基板を浸漬してポリ尿素膜6の膜厚の減少割合を調べた。各参考例の説明中に特記した場合を除いて、薬液の温度は室温(23℃)、試料の浸漬時間は300秒とした。
(参考例2)塩酸水溶液(HCl:35wt%)と、過酸化水素水(H2O2:30wt%)と、水(H2O)とを混合したSC2に試料を浸漬して試験を行った。各原料液の混合比はHCl:H2O2:H2O=1:1:7である。試料の浸漬時間は600秒とした。
(参考例3)硫酸(H2SO4:98wt%)と過酸化水素水(H2O2:30wt%)とを混合したSPMに試料を浸漬して試験を行った。各原料液の混合比はH2SO4:H2O2=1:4である。
(参考例4)レジスト現像液であるNMD−3(東京応化工業株式会社製、TMAH(テトラメチルアンモニウムヒドロキシド)濃度0.25〜5wt%)に試料を浸漬して試験を行った。
(参考例5)溶剤であるIPA(Isopropyl Alcohol)に試料を浸漬して試験を行った。試料の浸漬時間は600秒とした。
(参考例6)溶剤であるアセトンに試料を浸漬して試験を行った。試料の浸漬時間は600秒とした。
(参考例8)硫酸銅溶液(CuSO4:125g、H2SO4(98wt%):25cc、H2O:500cc)に試料を浸漬して試験を行った。試料の浸漬時間は600秒とした。
(参考例9)クエン酸水溶液(50g/Lのクエン酸水溶液をH2Oで希釈、H2O:クエン酸水溶液=1:20)に試料を浸漬して試験を行った。
(参考例10)希フッ酸水溶液(HF:1wt%)に試料を浸漬して試験を行った。
(参考例11)フッ酸水溶液(HF:50wt%)とアンモニア水(NH3:70wt%)との混合液に試料を浸漬して試験を行った。各原料液の混合比はHF:NH3=9:75である。
(参考例12)TMAH水溶液(TMAH:25%)に試料を浸漬して試験を行った。TMAH水溶液の温度は40℃とした。
参考例1〜12の結果を図22に示す。図22の横軸には各試験に用いた薬液を参考例番号と共に示し、縦軸にはポリ尿素膜6の膜厚の減少割合({(試験後の膜厚−試験前の膜厚)/試験前の膜厚}×100(Δ%))を示している。
例えば第2の実施形態に記載のa−Si膜33は、アルカリ系のエッチング液により除去することができる。そこで、アルカリ性の薬液であるSC1やTMAHをエッチング液として用いることにより、ポリ尿素の埋め込み部6aを残したままa−Si膜33を除去することが可能であることを確認できる。
20 低誘電率膜
23 SOC膜
29 ビアホール
291 トレンチ
301 凹部
302 空隙
31 タングステン層
32 SiO2膜
33 a−Si膜
6 ポリ尿素膜
6a 埋め込み部
Claims (9)
- 基板に対して処理を行い、半導体装置を製造する方法において、
表面が犠牲膜によって覆われ、パターニングされた前記犠牲膜の開口を含む凹部が形成された基板に対し、前記犠牲膜の上面側から重合用の原料を供給して、尿素結合を有する重合体からなる重合体膜を形成し、前記凹部内に前記重合体を埋め込む工程と、
前記凹部内に埋め込まれた重合体を残して、前記犠牲膜の上面側の重合体膜を除去する工程と、
前記凹部内に重合体が埋め込まれた状態で前記犠牲膜を除去する工程と、
次いで、前記凹部内の重合体を除去する工程と、を含むことを特徴とする半導体装置の製造方法。 - 前記犠牲膜を除去する工程では、前記犠牲膜と反応して当該犠牲膜を除去することが可能である一方、前記重合体に対する反応性は前記犠牲膜よりも小さいエッチャントを用いて犠牲膜を除去することを特徴とする請求項1に記載の半導体装置の製造方法。
- 前記凹部内の重合体を除去する工程は、前記重合体を加熱することにより、当該重合体を解重合させる工程であることを特徴とする請求項1または2に記載の半導体装置の製造方法。
- 前記犠牲膜の上面側の重合体膜を除去する工程は、前記重合体膜を加熱することにより、当該重合体膜を構成する重合体を解重合させる工程であることを特徴とする請求項1ないし3のいずれか一つに記載の半導体装置の製造方法。
- 前記凹部内に前記重合体を埋め込む工程を行う前に、前記犠牲膜をマスクとして用い基板をエッチングして前記凹部を形成する工程を含むことを特徴とする請求項1ないし4のいずれか一つに記載の半導体装置の製造方法。
- 前記凹部内に前記重合体を埋め込む工程を行う前に、前記基板にイオンを照射して、前記凹部内にイオン注入を行う工程を含むことを特徴とする請求項1ないし5のいずれか一つに記載の半導体装置の製造方法。
- 前記凹部内に前記重合体を埋め込む工程は、前記犠牲膜の上面側に形成された重合体膜を加熱し、一部を解重合させることにより流動性を持たせた重合体膜を前記凹部内に進入させる工程を含むことを特徴とする請求項1ないし6のいずれか一つに記載の半導体装置の製造方法。
- 前記凹部内に前記重合体を埋め込む工程は、イソシアネートの蒸気とアミンの蒸気とを基板に供給すると共に基板を加熱してイソシアネートとアミンとを重合反応させて前記重合体膜を形成する工程であることを特徴とする請求項1ないし7のいずれか一つに記載の半導体装置の製造方法。
- 前記凹部内に前記重合体を埋め込む工程は、イソシアネートを含む溶液とアミンを含む溶液とを基板に供給すると共に前記基板を加熱してイソシアネートとアミンとを重合反応させて前記重合体膜を形成する工程であることを特徴とする請求項1ないし7のいずれか一つに記載の半導体装置の製造方法。
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