JP6729335B2 - 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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- JP6729335B2 JP6729335B2 JP2016237922A JP2016237922A JP6729335B2 JP 6729335 B2 JP6729335 B2 JP 6729335B2 JP 2016237922 A JP2016237922 A JP 2016237922A JP 2016237922 A JP2016237922 A JP 2016237922A JP 6729335 B2 JP6729335 B2 JP 6729335B2
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Description
次いで前記低誘電率膜の表面にエッチング用のパターンマスクを形成する工程と、
しかる後、前記低誘電率膜をエッチングする工程と、
その後、前記パターンマスクを除去すると共に前記基板を加熱して前記重合体を解重合する工程と、を含み、
前記埋め込み工程は、イソシアネートの液体またはミストを前記低誘電率膜に染み込ませると共に、前記低誘電率膜に水分を供給してイソシアネートを加水分解してアミンを生成し、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る工程を含むことを特徴とする。
他の発明の半導体装置の製造方法は、半導体装置を製造するための基板上に形成された多孔質の低誘電率膜に対して、重合用の原料を供給して、前記低誘電率膜内の孔部に尿素結合を有する重合体を埋め込む埋め込み工程と、
次いで前記低誘電率膜の表面にエッチング用のパターンマスクを形成する工程と、
しかる後、前記低誘電率膜をエッチングする工程と、
その後、前記パターンマスクを除去すると共に前記基板を加熱して前記重合体を解重合する工程と、を含み、
前記埋め込み工程は、イソシアネートの蒸気とアミンの蒸気との一方及び他方を前記低誘電率膜内に順番に拡散させ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る工程であることを特徴とする。
更に他の発明の半導体装置の製造方法は、半導体装置を製造するための基板上に形成された多孔質の低誘電率膜に対して、重合用の原料を供給して、前記低誘電率膜内の孔部に尿素結合を有する重合体を埋め込む埋め込み工程と、
次いで前記低誘電率膜の表面にエッチング用のパターンマスクを形成する工程と、
しかる後、前記低誘電率膜をエッチングする工程と、
その後、前記パターンマスクを除去すると共に前記基板を加熱して前記重合体を解重合する工程と、を含み、
前記埋め込み工程は、尿素結合を有する化合物の液体、ミストまたは蒸気を前記低誘電率膜に染み込ませると共に、基板に光を照射して当該化合物を重合反応させる工程を含むことを特徴とする。
本実施形態の方法では、基板である半導体ウエハ(以下ウエハという)の表面に、図1(a)に示すように下層側の回路部分が形成され、この回路部分の上に低誘電率膜20が形成されている状態から処理が始まる。
先ず自己重合の原料である、イソシアネート(液体)を低誘電率膜20の中に染み込ませ(図1(b))、次いで低誘電率膜20の中に水分、例えば水蒸気を染み込ませる(図1(c))。イソシアネートと水分とを反応させると、イソシアネートが加水分解して直ちにポリ尿素が生成され、低誘電率膜20の孔部21がポリ尿素で埋められる。図5は、この反応を示しており、イソシアネートの一部が不安定な中間生成物であるアミンとなり、当該中間生成物と加水分解しなかったイソシアネートとが反応してポリ尿素が生成される。図4中、R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。
図6は、H6XDIを原料モノマーとして用いた処理の様子を、ウエハWに対する処理と化学式とを対応付けて模式的に記載した説明図である。図6(a)は、図1(b)に示した、ウエハWに対してイソシアネートを供給する処理に相当し、先ずウエハWに対してH6XDIの液体をスピン塗布することにより、当該液体を低誘電率膜20に染み込ませる。
水蒸気処理を行う装置としては、例えば図9に示す装置を用いることができる。図9中、41は水蒸気雰囲気を形成するための処理容器、42は水蒸気発生部、43は下面に多数の孔部が形成された水蒸気吐出部、44は水蒸気を水蒸気吐出部43内の拡散空間に導く管路、45はヒータ46を内蔵した載置台、47は吸引機構により排気される排気管である。処理容器41の内壁は、図示しない加熱機構により例えば80℃に加熱されている。ウエハWは載置台45の上に載置され、水蒸気吐出部43から吐出された水蒸気の雰囲気に置かれる。
また水蒸気処理を行う装置としては、水蒸気発生部42及び水蒸気吐出部43を設けることに代えて、載置台45の上方に蓋付きの扁平な容器を設け、この容器内に水を収容した状態で当該容器を加熱し、処理容器内を水蒸気雰囲気とする構成を採用してもよい。この場合、ウエハWを搬入出するときには蓋により容器が閉じられる。
次に低誘電率膜20及びハードマスク61の上にビアホールをエッチングするときのマスクとなるマスク用の膜62を形成し、更にマスク用の膜62の上に反射防止膜63及びレジスト膜64をこの順に積層する(図2(e))。マスク用の膜62は、例えば炭素を主成分とする有機膜が用いられ、この有機膜は、反射防止膜63及びレジスト膜64を形成してレジストパターンを形成する装置内にて、薬液をウエハWにスピンコーティングすることにより得られる。
続いてマスク用の膜62をエッチングマスクとして用い、低誘電率膜20をエッチングし、ビアホール201を形成する(図3(i))。低誘電率膜20、この例ではSiOC膜をエッチングする手法としては、C6F6ガスをプラズマ化して得たプラズマにより行うことができ、この場合、更に微量の酸素ガスを添加するようにしてもよい。
次にビアホール201を形成したプロセスと同様にして、ハードマスク61を用いて低誘電率膜20をエッチングし、ビアホール201を囲む領域にトレンチ202を形成する(図4(k))。その後、ハードマスク61を除去する(図4(l))。ハードマスク61がTiN膜であるときには、例えば硫酸、過酸化水素水及び水の混合溶液をエッチング液としてウエットエッチングにより除去することができる。
以上において、この段階までに行われる各プロセスは、ポリ尿素が解重合する温度よりも低い温度で実施されることが必要である。
上述の実施形態では、イソシアネートの自己重合によりポリ尿素膜を生成しているが、図11に一例を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ポリ尿素膜を生成するようにしてもよい。なお、R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。
この場合、例えばイソシアネート及びアミンの一方である液体を既述のようにスピンコーティング法によりウエハに供給して低誘電率膜に浸透させ、次いでイソシアネート及びアミンの他方である液体を同様にスピンコーティング法によりウエハに供給して低誘電率膜に浸透させる手法を採用することができる。またイソシアネート及びアミンを気体(蒸気)の状態でウエハに順番に供給するように、例えば交互に複数回供給するようにしてもよい。この場合には、例えばイソシアネートの蒸気が低誘電率膜の孔部に拡散して吸着し、次いでアミンの蒸気が孔部に拡散して重合反応が起こり、このような作用が繰り返されて孔部がポリ尿素膜により埋め尽くされる。
ポリ尿素自体は、固体であって液体にすることができないため、上述のようにポリ尿素となる原料を別々に膜に供給して膜中にてポリ尿素を生成する手法を採用している。
イソシアネート及びアミンの蒸気圧差が1桁以上である組み合わせとしては、イソシアネートからイソシアネート官能基を除いた骨格分子とアミンからアミン官能基を除いた骨格分子とが同一である例、即ち互いに同一骨格分子を備えたイソシアネート及びアミンを挙げることができる。例えばアミン官能基が結合したH6XDAの蒸気圧は、当該H6XDAの骨格分子と同一の骨格分子であって、イソシアネート官能基が結合したH6XDIの蒸気圧に比べて1桁以上高い。
更にまた図13(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。
そして尿素結合を備えた原料モノマーを重合させてポリ尿素膜を得るようにしてもよい。この場合の原料モノマーは、液体、ミストまたは蒸気の状態で低誘電率膜に供給することができる。図14はこのような例を示し、原料モノマーに対して光、例えば紫外線を照射して光エネルギーを与えることにより重合が起こってポリ尿素膜が生成され、このポリ尿素膜を例えば350℃で加熱すると、イソシアネートとアミンとに解重合する。
膜厚(nm) 193.7 194.3 196.0
屈折率 1.303 1.445 1.286
電気容量(pF) 73 91 68
誘電率 2.2 2.5 2.1
また埋め込み前及び埋め込み後の低誘電率膜について走査顕微鏡で撮像した写真を夫々図17及び図18として載せておく。
特に誘電率に関しては測定誤差などを考慮すれば、全く変わりがないということができる。そして吸収スペクトルの特性図からは、上述の実施形態で述べた手法により低誘電率膜内の孔部にポリ尿素が埋め込まれていること、またポリ尿素の除去処理を行うことで、ポリ尿素が低誘電率膜の中に全く残っていないこと、が裏付けられている。
また図17及び図18の写真を比較すると、埋め込み後の膜には白い粒状のものが散在していることが観察できており、ポリ尿素が膜内に埋め込まれていることが伺える。そして膜厚測定結果からは埋め込み前後で若干膜厚が変動しているが、写真からすると、膜厚の変動はほとんどないということができる。
12 銅配線
13 エッチングストッパー膜
W 半導体ウエハ
31 バキュームチャック
32 カップモジュール
36 ノズル
41 処理容器
43 水蒸気吐出部
51 処理容器
54 加熱ランプ
61 ハードマスク
62 マスク用の膜
63 反射防止膜
64 レジスト膜
201 ビアホール
202 トレンチ
70 配線金属
Claims (8)
- 半導体装置を製造するための基板上に形成された多孔質の低誘電率膜に対して、重合用の原料を供給して、前記低誘電率膜内の孔部に尿素結合を有する重合体を埋め込む埋め込み工程と、
次いで前記低誘電率膜の表面にエッチング用のパターンマスクを形成する工程と、
しかる後、前記低誘電率膜をエッチングする工程と、
その後、前記パターンマスクを除去すると共に前記基板を加熱して前記重合体を解重合する工程と、を含み、
前記埋め込み工程は、イソシアネートの液体またはミストを前記低誘電率膜に染み込ませると共に、前記低誘電率膜に水分を供給してイソシアネートを加水分解してアミンを生成し、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る工程を含むことを特徴とする半導体装置の製造方法。 - 前記アミンを生成する工程は、イソシアネートの液体またはミストを前記低誘電率膜に染み込ませた後、基板が置かれる雰囲気を水蒸気雰囲気とする工程であることを特徴とする請求項1記載の半導体装置の製造方法。
- 前記イソシアネートの液体を前記低誘電率膜に染み込ませる工程は、基板を回転させることにより基板表面の過剰なイソシアネートの液体を振り払う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。
- 半導体装置を製造するための基板上に形成された多孔質の低誘電率膜に対して、重合用の原料を供給して、前記低誘電率膜内の孔部に尿素結合を有する重合体を埋め込む埋め込み工程と、
次いで前記低誘電率膜の表面にエッチング用のパターンマスクを形成する工程と、
しかる後、前記低誘電率膜をエッチングする工程と、
その後、前記パターンマスクを除去すると共に前記基板を加熱して前記重合体を解重合する工程と、を含み、
前記埋め込み工程は、イソシアネートの蒸気とアミンの蒸気との一方及び他方を前記低誘電率膜内に順番に拡散させ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る工程であることを特徴とする半導体装置の製造方法。 - 半導体装置を製造するための基板上に形成された多孔質の低誘電率膜に対して、重合用の原料を供給して、前記低誘電率膜内の孔部に尿素結合を有する重合体を埋め込む埋め込み工程と、
次いで前記低誘電率膜の表面にエッチング用のパターンマスクを形成する工程と、
しかる後、前記低誘電率膜をエッチングする工程と、
その後、前記パターンマスクを除去すると共に前記基板を加熱して前記重合体を解重合する工程と、を含み、
前記埋め込み工程は、尿素結合を有する化合物の液体、ミストまたは蒸気を前記低誘電率膜に染み込ませると共に、基板に光を照射して当該化合物を重合反応させる工程を含むことを特徴とする半導体装置の製造方法。 - 前記パターンマスクを除去すると共に前記基板を加熱して前記重合体を解重合する工程は、前記パターンマスクを除去した後、前記基板を加熱して前記重合体を解重合する工程であることを特徴とする請求項1ないし5のいずれか一項に記載の半導体装置の製造方法。
- 前記低誘電率膜は、シリコン、炭素及び酸素を含む絶縁膜であることを特徴とする請求項1ないし6のいずれか一項に記載の半導体装置の製造方法。
- 前記重合体を解重合する工程は、基板を300℃〜400℃に加熱して行われることを特徴とする請求項1ないし7のいずれか一項に記載の半導体装置の製造方法。
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