JP4401912B2 - 半導体多層配線板の形成方法 - Google Patents
半導体多層配線板の形成方法 Download PDFInfo
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- JP4401912B2 JP4401912B2 JP2004265445A JP2004265445A JP4401912B2 JP 4401912 B2 JP4401912 B2 JP 4401912B2 JP 2004265445 A JP2004265445 A JP 2004265445A JP 2004265445 A JP2004265445 A JP 2004265445A JP 4401912 B2 JP4401912 B2 JP 4401912B2
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- film
- forming
- layer
- interlayer insulating
- insulating layer
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- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- GIHPVQDFBJMUAO-UHFFFAOYSA-N tributoxy(ethyl)silane Chemical compound CCCCO[Si](CC)(OCCCC)OCCCC GIHPVQDFBJMUAO-UHFFFAOYSA-N 0.000 description 1
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 1
- WAAWAIHPWOJHJJ-UHFFFAOYSA-N tributoxy(propyl)silane Chemical compound CCCCO[Si](CCC)(OCCCC)OCCCC WAAWAIHPWOJHJJ-UHFFFAOYSA-N 0.000 description 1
- HSDAZXVGQVMFAY-UHFFFAOYSA-N tributyl methyl silicate Chemical compound CCCCO[Si](OC)(OCCCC)OCCCC HSDAZXVGQVMFAY-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- QYBKVVRRGQSGDC-UHFFFAOYSA-N triethyl methyl silicate Chemical compound CCO[Si](OC)(OCC)OCC QYBKVVRRGQSGDC-UHFFFAOYSA-N 0.000 description 1
- CXZMPNCYSOLUEK-UHFFFAOYSA-N triethyl propyl silicate Chemical compound CCCO[Si](OCC)(OCC)OCC CXZMPNCYSOLUEK-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- LTOKKZDSYQQAHL-UHFFFAOYSA-N trimethoxy-[4-(oxiran-2-yl)butyl]silane Chemical compound CO[Si](OC)(OC)CCCCC1CO1 LTOKKZDSYQQAHL-UHFFFAOYSA-N 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- WKEXHTMMGBYMTA-UHFFFAOYSA-N trimethyl propyl silicate Chemical compound CCCO[Si](OC)(OC)OC WKEXHTMMGBYMTA-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- H01L21/76807—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics for dual damascene structures
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- H01L21/76814—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics post-treatment or after-treatment, e.g. cleaning or removal of oxides on underlying conductors
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- H01L21/76822—Modification of the material of dielectric layers, e.g. grading, after-treatment to improve the stability of the layers, to increase their density etc.
- H01L21/76826—Modification of the material of dielectric layers, e.g. grading, after-treatment to improve the stability of the layers, to increase their density etc. by contacting the layer with gases, liquids or plasmas
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- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
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- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
- H01L21/76829—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers
- H01L21/76831—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers in via holes or trenches, e.g. non-conductive sidewall liners
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- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76853—Barrier, adhesion or liner layers characterized by particular after-treatment steps
- H01L21/76855—After-treatment introducing at least one additional element into the layer
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- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
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- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76853—Barrier, adhesion or liner layers characterized by particular after-treatment steps
- H01L21/76861—Post-treatment or after-treatment not introducing additional chemical elements into the layer
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- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
- H01L21/76874—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroless plating
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Description
なお、SOG系材料とは、主にアルコキシシランの加水分解生成物を有機溶剤に溶解して調製された溶液である。
すなわち、まず、シリカ系層間絶縁層の形成については、「CVD用材料、もしくはSOG用材料、好ましくはSOG用原料を用いて基板上に被膜を形成し、次いで所望により特定の温度で熱処理して焼成被膜を形成した後、デュアルダマシン法により配線層形成空間を形成するエッチング工程を行った後、シリカ系層間絶縁層の表面にSi−OH結合を生成させる処理を行う」ことにより、実現できることが確認された。
このようにして表面処理されたシリカ系層間絶縁層にデュアルダマシン法により形成した配線層形成空間への拡散防止膜の形成については、(i)配線層形成空間の内面を有機シラン化合物により処理することにより、有機シラン化合物の単分子層からなる膜を密着させることができる、(ii)前記単分子層膜の表面は良好な平滑性を有しており、しかもパラジウム化合物を含む水溶液により容易に表面を触媒化することができる、(iii)前記触媒化単分子層膜に無電解メッキを施すことで、前記単分子層膜上に銅拡散防止性の高いメッキ膜を形成することができ、これらにより、配線層形成空間内面への密着性が高く、銅拡散防止特性が高い、薄い膜厚の拡散防止膜が形成可能であることを確認できた。
ただし、当該酸素プラズマ処理は非常に強く作用するため、被膜表面のみをSi−OH結合に変化させる目的においては、作業が簡便な紫外線照射による処理を選択する方が好ましい。特にSi−H結合はSi−OH結合に変化し易いため、紫外線照射による処理で十分である。
シリコン基板上に無機SOG材料としてトリアルコキシシランの加水分解生成物を主成分とするスピンオングラス塗布液(東京応化工業株式会社製、商品名:OCD T−12 800)を、スピンナーにより2000rpmで20秒間塗布し、次いでホットプレート上で80℃で1分間、150℃で1分間、200℃で1分間ずつ順次乾燥させ、窒素雰囲気中にて450℃で30分間熱処理し、膜厚400nmの塗膜を得た。得られたシリカ系層間絶縁膜の誘電率は3.0であった。
上記拡散防止膜の形成後、表4に示す組成の電気銅メッキ浴を用いて銅メッキを行ったところ、直接良好なメッキを行うことができ、配線層を直接銅メッキすることによって形成し得ることが認められた。
無機SOG系材料としてスピンオングラス塗布液(東京応化工業株式会社製、商品名:OCD T−12 800)を用いてシリカ系層間絶縁膜を形成し、このシリカ系層間絶縁膜の表面にSi−OH結合を形成するための処理としてヘリウム(He)プラズマ照射処理および紫外線照射処理を用いて、本発明の半導体多層配線板の擬似的モデルを以下の通り形成した。この形成した擬似的モデルを用いて、本発明の半導体多層配線板における拡散防止膜の拡散防止特性を評価した。この擬似的モデルは配線形成空間を備えていないが、この擬似的モデルにおける拡散防止膜は本発明の半導体多層配線板における拡散防止膜と同一であるため、この擬似的モデルを拡散防止特性の評価に用いることができる。
有機SOG系材料としてメチルトリアルコキシシランの加水分解生成物を主成分とするスピンオングラス塗布液(東京応化工業株式会社製、商品名:OCD T−9)を用い、シリカ系層間絶縁膜の表面にSi−OH結合を形成するための処理として、大気中185〜254nmの遠紫外線を含む紫外線を1分間照射する紫外線照射処理を用いたこと以外は、実施例2および3と同様にして、本発明の半導体多層配線板の擬似的モデル3および4を形成した。
図6のグラフで示されるように、本発明の半導体多層配線板の擬似的モデル1〜4を用いた実施例2〜5においては、抵抗値に大きな変化が認められず、拡散が起こっていないことが判明した。この結果は本発明の半導体多層配線板の擬似的モデルにおける拡散防止膜の優れた拡散防止特性を示しており、デュアルダマシン法により形成した配線形成空間がさらに設けられている本発明の半導体多層配線板における拡散防止膜も同様に優れた拡散防止特性を有することを示している。
2 層間絶縁層
3 レジスト膜
4 配線溝(トレンチ)
5 バリアメタル膜(拡散防止膜)
6 下層配線層
7 キャッピング層
8 第1の低誘電体層
9 第1のエッチングストッパ層
10 第2の低誘電体層
11 第2のエッチングストッパ層
12 レジストマスク
13 ビアホール
14 埋込材
15 レジストマスク
16 配線溝(トレンチ)
17 バリアメタル膜(拡散防止膜)
18 ビア配線
19 上層配線層
20 キャッピング層
21 導通層
8a,10a シリカ系層間絶縁層
13 ビア
16 トレンチ
30 配線層形成空間
31 密着層
32 拡散防止膜
33 配線層
40 単分子層膜
41 層間絶縁層(Ni系化合物)
42 銅配線層
43 測定子
Claims (4)
- 半導体基板上に形成された下層配線層と、その上に低誘電率のシリカ系層間絶縁層を介して形成された上層配線層とが、前記層間絶縁層を上下に貫通するビア配線によって接続されている半導体多層配線を有する半導体多層配線板の形成方法であって、
前記基板上に低誘電率のシリカ系層間絶縁層を形成する層間絶縁層形成工程と、
前記低誘電率のシリカ系層間絶縁層にデュアルダマシン法により配線層形成空間を形成するエッチング工程と、
前記低誘電率のシリカ系層間絶縁層表面にSi−OH結合を形成するための処理をする工程と、
前記配線層形成空間の内面を有機シラン化合物により処理してシラン系単分子層膜を密着させる単分子層膜形成工程と、
前記単分子層膜をパラジウム化合物を含む水溶液により表面を触媒化する表面触媒化工程と、
前記触媒化単分子層膜に無電解メッキにより、該単分子層膜上に銅拡散防止性の高いメッキ膜を形成して、銅拡散防止膜を得る銅拡散防止膜形成工程と、
前記銅拡散防止膜上に銅メッキ層を形成することにより配線層を得る配線層形成工程と、を有し、前記単分子層膜形成工程の後、余剰の有機シラン化合物を除去し、前記下層配線層を露出させ、次いで前記表面触媒化工程を行うことを特徴とする半導体多層配線板の形成方法。 - 上記低誘電率のシリカ系層間絶縁層を形成する工程が、スピンオングラス(SOG)材料を用いて行うことを特徴とする請求項1記載の半導体多層配線板の形成方法。
- 上記シリカ系層間絶縁層表面にSi−OH結合を形成するための処理工程が、シリカ系層間絶縁層を酸化性雰囲気下にて紫外線を照射する紫外線照射処理を少なくとも含むことを特徴とする請求項1又は2に記載の半導体多層配線板の形成方法。
- 上記無電解メッキは、Co系もしくはNi系メッキであることを特徴とする請求項1〜3のいずれか1項に記載の半導体多層配線板の形成方法。
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