JP2010267716A - 低誘電率絶縁膜の作製方法、半導体装置およびその製造方法 - Google Patents
低誘電率絶縁膜の作製方法、半導体装置およびその製造方法 Download PDFInfo
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- JP2010267716A JP2010267716A JP2009116601A JP2009116601A JP2010267716A JP 2010267716 A JP2010267716 A JP 2010267716A JP 2009116601 A JP2009116601 A JP 2009116601A JP 2009116601 A JP2009116601 A JP 2009116601A JP 2010267716 A JP2010267716 A JP 2010267716A
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- insulating film
- dielectric constant
- low dielectric
- constant insulating
- porous silica
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- BCLLLHFGVQKVKL-UHFFFAOYSA-N tetratert-butyl silicate Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C BCLLLHFGVQKVKL-UHFFFAOYSA-N 0.000 description 1
- MQVCTPXBBSKLFS-UHFFFAOYSA-N tri(propan-2-yloxy)-propylsilane Chemical compound CCC[Si](OC(C)C)(OC(C)C)OC(C)C MQVCTPXBBSKLFS-UHFFFAOYSA-N 0.000 description 1
- DEKZKCDJQLBBRA-UHFFFAOYSA-N tributoxy(butyl)silane Chemical compound CCCCO[Si](CCCC)(OCCCC)OCCCC DEKZKCDJQLBBRA-UHFFFAOYSA-N 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
- LEZQEMOONYYJBM-UHFFFAOYSA-N tributoxy(propan-2-yl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C(C)C LEZQEMOONYYJBM-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
- MVXBTESZGSNIIB-UHFFFAOYSA-N tributoxy(tert-butyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C(C)(C)C MVXBTESZGSNIIB-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ZLGWXNBXAXOQBG-UHFFFAOYSA-N triethoxy(3,3,3-trifluoropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)F ZLGWXNBXAXOQBG-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
- XVYIJOWQJOQFBG-UHFFFAOYSA-N triethoxy(fluoro)silane Chemical compound CCO[Si](F)(OCC)OCC XVYIJOWQJOQFBG-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
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-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
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- RTMJRVHEBLESPE-UHFFFAOYSA-N trimethoxy(1,1,2,2,2-pentafluoroethyl)silane Chemical compound CO[Si](OC)(OC)C(F)(F)C(F)(F)F RTMJRVHEBLESPE-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- LGROXJWYRXANBB-UHFFFAOYSA-N trimethoxy(propan-2-yl)silane Chemical compound CO[Si](OC)(OC)C(C)C LGROXJWYRXANBB-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
- ORVBHOQTQDOUIW-UHFFFAOYSA-N trimethoxy(trifluoromethyl)silane Chemical compound CO[Si](OC)(OC)C(F)(F)F ORVBHOQTQDOUIW-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- IXJNGXCZSCHDFE-UHFFFAOYSA-N triphenoxy(phenyl)silane Chemical compound C=1C=CC=CC=1O[Si](C=1C=CC=CC=1)(OC=1C=CC=CC=1)OC1=CC=CC=C1 IXJNGXCZSCHDFE-UHFFFAOYSA-N 0.000 description 1
- FNNJGIKXHZZGCV-UHFFFAOYSA-N triphenoxy(propan-2-yl)silane Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(C(C)C)OC1=CC=CC=C1 FNNJGIKXHZZGCV-UHFFFAOYSA-N 0.000 description 1
- AMUIJRKZTXWCEA-UHFFFAOYSA-N triphenoxy(propyl)silane Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(CCC)OC1=CC=CC=C1 AMUIJRKZTXWCEA-UHFFFAOYSA-N 0.000 description 1
- VUWVDNLZJXLQPT-UHFFFAOYSA-N tripropoxy(propyl)silane Chemical compound CCCO[Si](CCC)(OCCC)OCCC VUWVDNLZJXLQPT-UHFFFAOYSA-N 0.000 description 1
- OZWKZRFXJPGDFM-UHFFFAOYSA-N tripropoxysilane Chemical compound CCCO[SiH](OCCC)OCCC OZWKZRFXJPGDFM-UHFFFAOYSA-N 0.000 description 1
- PJEMIBXFOHYKMS-UHFFFAOYSA-N tris(2-methylpropoxy)-phenylsilane Chemical compound CC(C)CO[Si](OCC(C)C)(OCC(C)C)C1=CC=CC=C1 PJEMIBXFOHYKMS-UHFFFAOYSA-N 0.000 description 1
- MOGQHPIOEFLJQH-UHFFFAOYSA-N tris(2-methylpropoxy)-propan-2-ylsilane Chemical compound CC(C)CO[Si](OCC(C)C)(OCC(C)C)C(C)C MOGQHPIOEFLJQH-UHFFFAOYSA-N 0.000 description 1
- POQYUENPWRRXNK-UHFFFAOYSA-N tris(2-methylpropoxy)-propylsilane Chemical compound CC(C)CO[Si](CCC)(OCC(C)C)OCC(C)C POQYUENPWRRXNK-UHFFFAOYSA-N 0.000 description 1
- KGOOITCIBGXHJO-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]-phenylsilane Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)C1=CC=CC=C1 KGOOITCIBGXHJO-UHFFFAOYSA-N 0.000 description 1
- MJIHPVLPZKWFBL-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]-propan-2-ylsilane Chemical compound CC(C)(C)O[Si](C(C)C)(OC(C)(C)C)OC(C)(C)C MJIHPVLPZKWFBL-UHFFFAOYSA-N 0.000 description 1
- DIZPPYBTFPZSGK-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]-propylsilane Chemical compound CCC[Si](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C DIZPPYBTFPZSGK-UHFFFAOYSA-N 0.000 description 1
- XMUJIPOFTAHSOK-UHFFFAOYSA-N undecan-2-ol Chemical compound CCCCCCCCCC(C)O XMUJIPOFTAHSOK-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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Abstract
【解決手段】基板上に多孔質シリカ膜形成用原料を塗布する工程と、多孔質シリカ膜形成用原料が塗布された基板を水を添加しない有機アミン蒸気雰囲気中に暴露する気相処理工程と、を含む多孔質シリカ膜からなる低誘電率絶縁膜の作製方法。
【選択図】図6
Description
基板上に多孔質シリカ膜形成用原料を塗布し、多孔質シリカ前駆体膜を形成する工程と、
前記多孔質シリカ前駆体膜が形成された前記基板を水を添加しない有機アミン蒸気雰囲気中に暴露する気相処理工程と、
を含むことを特徴とする多孔質シリカ膜からなる低誘電率絶縁膜の作製方法である。
本発明のシリカ前駆体にはポリシロキサンを用いる。ポリシロキサンとしては、一般式(1)で表わされる化合物の加水分解縮合物を用いることができる。
(式中、Rは水素原子または炭素数1〜20の有機基を示し、Xは同一または異なる加水分解性基を示し、nは0〜2の整数である。nが2のときRは同一でもよく異なっていてもよい。)
本発明にかかる多孔質シリカ膜の形成方法は、基板上に上記の多孔質シリカ膜形成用原料を塗布する塗布工程と、塗布された多孔質シリカ膜形成用原料から溶媒を蒸発させるプリベーク工程をさらに有する。これにより、基板上に多孔質シリカ前駆体膜が形成される。
本発明にかかる多孔質シリカ膜の形成方法は、プリベーク処理工程の後、多孔質シリカ前駆体膜中に含まれるシリカ前駆体の重合を促進させると同時に疎水化のための気相処理工程を有する。本発明における気相処理とは、基板上に形成された多孔質シリカ前駆体膜を有機アミン蒸気に暴露する処理を意味する。この気相処理によって、多孔質シリカ前駆体膜中に有機アミンを拡散させ、シリカ前駆体を疎水化すると同時に一部の空孔発生剤を分解、揮発させることができる。本発明においては、気相処理に用いる蒸気には水蒸気を含まない構成とする。すなわち、有機アミン蒸気を発生させる溶液には水を積極的に添加しない構成とする。溶液に水を添加すると、蒸気に水蒸気が多く含まれてしまい、疎水性の発現が不十分となる傾向がある。また、後述するように、空孔径の制御が困難となる。なお、プリベーク処理工程の後、多孔質シリカ前駆体膜中に残存する水や、シリカ前駆体の脱水・縮合過程で生成する水に由来する微量の水蒸気までも否定するものではない。また、有機アミン中に不純物として含まれる水も、その量が微量である限り効果に影響するものではない。
本発明にかかる多孔質シリカ膜の形成方法は、気相処理工程の後、空孔発生剤の分解・揮発を完結させる焼成工程として加熱処理を施すことが好ましい。前工程の気相処理においても、空孔発生剤の分解・揮発は進行するが、より好ましい210℃以上250℃以下の温度範囲では空孔発生剤の分解・揮発が不十分であり、これを完結させるために本焼成工程を実施することが好ましい。加熱温度は、空孔発生剤の種類にもよるが、350℃以上450℃以下が好ましく、390℃以上410℃以下がより好ましい。加熱処理雰囲気は特に制限されず、空気中でも良い。時間は、3〜5時間が好ましく、3.8〜4.2時間がより好ましい。1から20℃/分の昇温速度で所定の温度まで昇温し、所定時間焼成を行う。焼成工程には通常使用されるベーク炉を用いることができる。
図7は、気相処理を用いた多孔質シリカ膜を適用した半導体装置の実施例を示す工程断面図である。ここでは、ダマシン法により銅配線を形成する例を説明する。半導体基板(Siウェハ)100にSi3N4膜等のバリア膜101を形成後、多孔質シリカ膜102を成膜(塗布→気相処理→焼成)する(工程(a))。ハードマスク、レジスト塗布、露光・現像、エッチングを行い、多孔質シリカ膜102に所望の配線パターン103を形成する(工程(b))。全面にCu膜104をメッキ法にて成膜し、その後、必要によりアニールを行う(工程(c))。最後に、化学機械研磨法(Chemical Mechanical Polishing:CMP)で多孔質シリカ膜102上のCuの除去を行うことでCu配線105が形成される(工程(d))。
12 容器
13 オートクレーブ
14 有機アミン(蒸気及び溶液)
100 半導体基板(Siウエハ)
101 バリア膜
102 多孔質シリカ膜
103 配線パターン
104 Cu膜
105 Cu配線
Claims (24)
- 基板上に多孔質シリカ膜形成用原料を塗布し、多孔質シリカ前駆体膜を形成する工程と、
前記多孔質シリカ前駆体膜が形成された前記基板を水を添加しない有機アミン蒸気雰囲気中に暴露する気相処理工程と、
を含むことを特徴とする多孔質シリカ膜からなる低誘電率絶縁膜の作製方法。 - 前記気相処理工程の後、焼成熱処理工程をさらに有することを特徴とする請求項1に記載の低誘電率絶縁膜の作製方法。
- 前記有機アミンは少なくとも1級ジアミンを含有することを特徴とする請求項1または請求項2に記載の低誘電率絶縁膜の作製方法。
- 前記1級ジアミンはエチレンジアミンであることを特徴とする請求項3に記載の低誘電率絶縁膜の作製方法。
- 前記有機アミンは少なくとも3級アミンを含有することを特徴とする請求項1から4のいずれか1項に記載の低誘電率絶縁膜の作製方法。
- 前記3級アミンはトリエチルアミンであることを特徴とする請求項5に記載の低誘電率絶縁膜の作製方法。
- 前記多孔質シリカ膜は、直径の平均値で示される4nmから8nmの空孔径を有する膜であることを特徴とする請求項1乃至6のいずれか1項に記載の低誘電率絶縁膜の作製方法。
- 前記有機アミンはエチレンジアミンとトリエチルアミンとを100:0〜0:100の溶液状態での体積比で使用したものであって、前記空孔径は、前記エチレンジアミンと前記トリエチルアミンとの体積混合比を調整することにより制御することを特徴とする請求項7に記載の低誘電率絶縁膜の作製方法。
- 前記気相処理工程は、前記多孔質シリカ膜を疎水化する工程であり、これにより前記多孔質シリカ膜の吸湿を防止することを特徴とする請求項1に記載の低誘電率絶縁膜の作製方法。
- 前記気相処理工程における前記有機アミンの蒸気は、前記有機アミンを沸点以上250℃以下の温度範囲に加熱することにより発生させることを特徴とする請求項1から6のいずれか1項に記載の低誘電率絶縁膜の作製方法。
- 前記気相処理工程における基板の温度は、100℃から450℃に設定されることを特徴とする請求項1、請求項9または請求項10に記載の低誘電率絶縁膜の作製方法。
- 前記気相処理工程における基板の温度は、210℃から250℃に設定されることを特徴とする請求項11に記載の低誘電率絶縁膜の作製方法。
- 前記気相処理工程は、1時間から6時間の範囲で行うことを特徴とする請求項1および請求項9から12のいずれか1項に記載の低誘電率絶縁膜の作製方法。
- 前記気相処理工程の後、前記焼成熱処理工程の前に、前記基板の表面に付着している有機アミンを除去するリンス工程と、リンス工程に続く乾燥工程をさらに含むことを特徴とする請求項1に記載の低誘電率絶縁膜の作製方法。
- 前記多孔質シリカ膜形成用原料はシリカ前駆体、触媒、水、溶媒、空孔発生剤の攪拌合成によって生成され、前記焼成熱処理工程は、前記気相処理工程で未分解の空孔発生剤を分解揮発させることによって前記多孔質シリカ前駆体膜を多孔質シリカ膜に変換する工程であることを特徴とする請求項1に記載の低誘電率絶縁膜の作製方法。
- 前記焼成熱処理工程は、前記基板を1から20℃/分の速度で室温から400℃まで昇温し、1から6時間の範囲で加熱することを特徴とする請求項1または請求項15に記載の低誘電率絶縁膜の作製方法。
- 半導体基板上に、金属配線と層間絶縁膜とが積層形成され多層配線構造を有する半導体装置の製造方法において、
前記層間絶縁膜は低誘電率絶縁膜を含み、
前記低誘電率絶縁膜は、請求項1乃至16のいずれか1項に記載の方法で作製されることを特徴とする半導体装置の製造方法。 - 前記金属配線は、前記層間絶縁膜に形成される溝を埋め込んで形成されることを特徴とする請求項17に記載の半導体装置の製造方法。
- 前記金属配線は、前記層間絶縁膜に形成される溝と、前記溝の底面の一部に形成されるコンタクトホールを埋め込んで形成されることを特徴とする請求項17または請求項18に記載の半導体装置の製造方法。
- 前記金属配線は、銅配線である請求項17から19のいずれか1項に記載の半導体装置の製造方法。
- 半導体基板上に、金属配線と層間絶縁膜とが積層形成され多層配線構造を有する半導体装置であって、
前記層間絶縁膜は低誘電率絶縁膜を含み、前記低誘電率絶縁膜は、請求項1乃至16のいずれか1項に記載の方法で作製された多孔質シリカ膜であることを特徴とする半導体装置。 - 前記金属配線は、前記層間絶縁膜に形成される溝を埋め込んで形成されたことを特徴とする請求項21に記載の半導体装置。
- 前記金属配線は、前記層間絶縁膜に形成される溝と、前記溝の底面の一部に形成されたコンタクトホールを埋め込んで形成されたことを特徴とする請求項21または請求項22に記載の半導体装置。
- 前記金属配線は、銅配線である請求項21から23のいずれか1項に記載の半導体装置。
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US12/617,040 US8030221B2 (en) | 2009-05-13 | 2009-11-12 | Method for producing low-k l film, semiconductor device, and method for manufacturing the same |
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CN201010003231.XA CN101887853B (zh) | 2009-05-13 | 2010-01-11 | 低k膜的制造方法、半导体装置及其制造方法 |
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US8030221B2 (en) | 2011-10-04 |
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