JP2004190033A - 低誘電率材料及びcvdによる処理方法 - Google Patents
低誘電率材料及びcvdによる処理方法 Download PDFInfo
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- JP2004190033A JP2004190033A JP2003415152A JP2003415152A JP2004190033A JP 2004190033 A JP2004190033 A JP 2004190033A JP 2003415152 A JP2003415152 A JP 2003415152A JP 2003415152 A JP2003415152 A JP 2003415152A JP 2004190033 A JP2004190033 A JP 2004190033A
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- JGWFUSVYECJQDT-UHFFFAOYSA-N trimethyl(2-trimethylsilyloxyethoxy)silane Chemical compound C[Si](C)(C)OCCO[Si](C)(C)C JGWFUSVYECJQDT-UHFFFAOYSA-N 0.000 description 1
- OJAJJFGMKAZGRZ-UHFFFAOYSA-N trimethyl(phenoxy)silane Chemical group C[Si](C)(C)OC1=CC=CC=C1 OJAJJFGMKAZGRZ-UHFFFAOYSA-N 0.000 description 1
- WOBRFSDEZREQAB-UHFFFAOYSA-N trimethyl-(2-trimethylsilyloxycyclobuten-1-yl)oxysilane Chemical compound C[Si](C)(C)OC1=C(O[Si](C)(C)C)CC1 WOBRFSDEZREQAB-UHFFFAOYSA-N 0.000 description 1
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
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Abstract
【解決手段】 好ましい膜は化学式SivOwCxHyFzによって表され、式中、v+w+x+y+z=100%、vが10〜35原子%、wが10〜65原子%、yが10〜50原子%、xが1〜30原子%、及びzが0.1〜15原子%であり、実質的にフッ素が炭素に結合されていない。提供されるCVD法は、真空チャンバーの内部に基材を提供すること、フッ素提供ガスと、酸素提供ガスと、オルガノシラン及びオルガノシロキサンから選択された少なくとも1つの前駆体ガスとを含むガス状試薬を真空チャンバーに導入すること、並びに該チャンバー中のガス状試薬にエネルギーを加えて、ガス状試薬の反応を引き起こし、基材上に膜を形成させることを含む。
【選択図】 なし
Description
オルガノシラン前駆体として1,3,5,7−テトラメチルシクロテトラシロキサン(TMCTS)を使用することに基づいた本発明の有望な例が、200mmシリコンウエハー基材について下表4に示される。
本発明のOFSG膜は、圧力1〜16torr、プラズマ電力100〜1000W、電極間隔200〜400ミリインチ(5.08〜10.16mm)及び温度200〜425℃で、トリメチルシラン(流量1〜1000sccm)、SiF4(流量1〜1000sccm)及びO2(流量1〜200sccm)を組み合せることによって堆積させた。
例22に従って調製した膜の熱的安定性を検討し、その結果を下表8にまとめた。空気雰囲気下425℃で4時間アニーリングした前後のOFSG膜とOSG膜の間の比較は、それらの熱的安定性において相当な相違を示す。OFSG膜の誘電率が2.89〜2.96に増加しているのに対し、OSG膜の誘電率は2.96〜3.50に達している。アニーリング後のOSG膜の硬さの増加と屈折率の減少は、誘電率を増加させる場合があるSi−OHのような不要な化学結合の形成と同時に起こる、多孔度/自由体積を増加させる有機基の損失を示している。
例22に従って調製したOSG及びOFSG膜の組成の安定性は、ダイナミック二次イオン質量分析(ダイナミックSIMS)測定を用いて評価した。2つの試料をシリコン基材上に堆積させた。即ち、第1の試料は0.5ミクロンのOSGキャッピング層を有する1.0ミクロンのOFSG膜から成り、第2の試料は0.5ミクロンのOFSGキャッピング層を有する0.5ミクロンのOSG膜である。プロファイルスペクトルの深さ方向のダイナミックSIMSを熱アニーリング(4時間、425℃、空気雰囲気)の前後で実施した。
例22に従って調製したOSG及びOFSG膜の熱的安定性は、窒素及び空気雰囲気下425℃で時間の関数として減量を測定することによって評価した。OFSG及びOSG膜についての結果を図6の(a)及び(b)に示す。OFSGについての結果は、窒素中で0.05%/h及び空気中で0.10%/hの減量を示している。OSGの分析は、窒素中で0.05%の減量であるが、空気に425℃でさらすと瞬時に2%の減量を受けるということを示している。
例22に従って調製したOSG及びOFSG膜の組成の安定性は、赤外(IR)分光を用いて評価した。OFSG膜の堆積条件は以下の通り、即ち、プラズマ電力400W、間隔200ミル、圧力6torr、温度350℃、トリメチルシラン540sccm、酸素90sccm、四フッ化ケイ素250sccm及び時間200秒であった。OSG膜の堆積条件は以下の通り、即ち、プラズマ電力600W、間隔260ミル、圧力4torr、温度350℃、トリメチルシラン540sccm、酸素90sccm及び時間72秒であった。熱アニーリング(4時間、425℃、空気雰囲気)前後のOFSG及びOSG膜のIRスペクトルを表9に与える。
Claims (31)
- 化学式SivOwCxHyFzによって表され、式中、v+w+x+y+z=100%、vが10〜35原子%、wが10〜65原子%、yが10〜50原子%、xが2〜30原子%、及びzが0.1〜15原子%であり、実質的にフッ素が炭素に結合されていない膜。
- ほとんどの水素が炭素に結合されている、請求項1に記載の膜。
- 3.5未満の誘電率を有する、請求項1に記載の膜。
- 3.0未満の誘電率を有する、請求項1に記載の膜。
- 標準OSG膜に比べて優れた機械的性質を有する、請求項1に記載の膜。
- 2.0g/cc未満のかさ密度を有する、請求項1に記載の膜。
- 1.5g/cc未満のかさ密度を有する、請求項1に記載の膜。
- 小角中性子散乱又は陽電子消滅寿命分光法によって測定された、相当球径5nm未満の細孔サイズを有する、請求項1に記載の膜。
- 小角中性子散乱又は陽電子消滅寿命分光法によって測定された、相当球径2.5nm未満の細孔サイズを有する、請求項1に記載の膜。
- 半導体基材上に堆積された、請求項1に記載の膜。
- 集積回路における絶縁層、層間絶縁層、金属間絶縁層、キャッピング層、化学機械平坦化層若しくはエッチストップ層、バリヤー層又は接着層から成る群のうちの少なくとも1つである、請求項1に記載の膜。
- N2下425℃等温で1.0wt%/h未満の平均減量を有する、請求項1に記載の膜。
- 空気下425℃等温で1.0wt%/h未満の平均減量を有する、請求項1に記載の膜。
- 1.5g/cc未満のかさ密度、小角中性子散乱又は陽電子消滅寿命分光法によって測定された相当球径2.5nm未満の細孔サイズを有し、ほとんどの水素が炭素に結合され、集積回路における絶縁層、層間絶縁層、金属間絶縁層、キャッピング層、化学機械平坦化若しくはエッチストップ層、バリヤー層又は接着層から成る群のうちの少なくとも1つとして基材上に堆積された、請求項1に記載の膜。
- x/z>0.25である、請求項1に記載の膜。
- 化学式SivOwCxHyFzによって表され、式中、v+w+x+y+z=100%、vが10〜35原子%、wが10〜65原子%、yが10〜50原子%、xが1〜30原子%、及びzが0.1〜15原子%であり、x/z>0.25という条件で、実質的にフッ素が炭素に結合されていない膜。
- 1.5g/cc未満のかさ密度、小角中性子散乱又は陽電子消滅寿命分光法によって測定された相当球径2.5nm未満の細孔サイズを有し、ほとんどの水素が炭素に結合され、集積回路における絶縁層、層間絶縁層、金属間絶縁層、キャッピング層、化学機械平坦化若しくはエッチストップ層、バリヤー層又は接着層から成る群のうちの少なくとも1つとして基材上に堆積された、請求項16に記載の膜。
- 化学式SivOwCxHyFzによって表され、式中、v+w+x+y+z=100%、vが10〜35原子%、wが10〜65原子%、yが10〜50原子%、xが2〜30原子%、及びzが0.1〜15原子%であり、0.5原子%以下のフッ素が炭素に結合されており、環境条件による膜特性の変化に抵抗するよう適合された膜。
- 前記環境条件がマイクロエレクトロニクス処理工程である、請求項18に記載の膜。
- 前記マイクロエレクトロニクス処理工程が化学酸化的及び/又は熱酸化的である、請求項19に記載の膜。
- 前記膜特性が誘電率であり、前記環境条件が熱アニーリング工程、誘電エッチング工程及びエッチ後の灰化工程から成る群より選択された、少なくとも1つのマイクロエレクトロニクス処理工程である、請求項18に記載の膜。
- 前記環境条件が前記誘電率を10%以下だけ増加させる、請求項21に記載の膜。
- 前記環境条件が前記誘電率を0.1以下だけ増加させる、請求項21に記載の膜。
- 前記環境条件が前記誘電率を該環境条件が標準OSG膜の標準誘電率を増加させる量よりも小さい分だけ増加させる、請求項21に記載の膜。
- 前記環境条件が前記誘電率を該環境条件が標準OSG膜の標準誘電率を増加させる量の50%以下だけ増加させる、請求項24に記載の膜。
- 前記環境条件が前記誘電率を該環境条件が標準OSG膜の標準誘電率を増加させる量の20%以下だけ増加させる、請求項25に記載の膜。
- 前記膜特性が前記膜全体のフッ素分布である、請求項18に記載の膜。
- 前記膜特性が前記膜中の炭素濃度である、請求項18に記載の膜。
- 前記環境条件が前記膜中の炭素濃度を該環境条件が標準OSG膜の標準誘電率を減少させる量の50%以下だけ減少させる、請求項28に記載の膜。
- 前記環境条件が前記膜中の炭素濃度を減少させ、該環境条件が該膜中の炭素濃度を該環境条件が標準OSG膜の標準誘電率を減少させる量の20%以下だけ減少させる、請求項29に記載の膜。
- 化学式SivOwCxHyFzによって表され、式中、v+w+x+y+z=100%、vが10〜35原子%、wが10〜65原子%、yが10〜50原子%、xが1〜30原子%、及びzが0.1〜15原子%であり、x/z>0.25という条件で、0.5原子%以下のフッ素が炭素に結合されており、マイクロエレクトロニクス処理工程による膜特性の変化に抵抗するよう適合された膜。
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JP2021025124A (ja) * | 2019-08-06 | 2021-02-22 | バーサム マテリアルズ ユーエス,リミティド ライアビリティ カンパニー | ケイ素化合物及びケイ素化合物を使用してフィルムを堆積する方法 |
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JP2008530821A (ja) * | 2005-02-16 | 2008-08-07 | インターナショナル・ビジネス・マシーンズ・コーポレーション | 高度な低誘電率の有機シリコン・プラズマ化学気相堆積膜 |
JP2008063629A (ja) * | 2006-09-08 | 2008-03-21 | Asahi Glass Co Ltd | 低屈折率膜の製膜方法および低屈折率膜を有する物品 |
JP2021025124A (ja) * | 2019-08-06 | 2021-02-22 | バーサム マテリアルズ ユーエス,リミティド ライアビリティ カンパニー | ケイ素化合物及びケイ素化合物を使用してフィルムを堆積する方法 |
JP6993394B2 (ja) | 2019-08-06 | 2022-02-21 | バーサム マテリアルズ ユーエス,リミティド ライアビリティ カンパニー | ケイ素化合物及びケイ素化合物を使用してフィルムを堆積する方法 |
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TWI222961B (en) | 2004-11-01 |
US20030162034A1 (en) | 2003-08-28 |
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EP1918415A1 (en) | 2008-05-07 |
KR20040051537A (ko) | 2004-06-18 |
KR100577059B1 (ko) | 2006-05-10 |
CN1507015A (zh) | 2004-06-23 |
EP1428906A1 (en) | 2004-06-16 |
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