JPWO2008114309A1 - シリコン系絶縁膜のエッチング後処理剤、半導体装置の製造方法および半導体装置 - Google Patents
シリコン系絶縁膜のエッチング後処理剤、半導体装置の製造方法および半導体装置 Download PDFInfo
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- JPWO2008114309A1 JPWO2008114309A1 JP2009504902A JP2009504902A JPWO2008114309A1 JP WO2008114309 A1 JPWO2008114309 A1 JP WO2008114309A1 JP 2009504902 A JP2009504902 A JP 2009504902A JP 2009504902 A JP2009504902 A JP 2009504902A JP WO2008114309 A1 JPWO2008114309 A1 JP WO2008114309A1
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- silicon
- post
- etching
- treatment agent
- insulating film
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 75
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- LASIJVXABDMKBX-UHFFFAOYSA-N trihydroxy(2-pyridin-4-ylethyl)silane Chemical compound O[Si](O)(O)CCC1=CC=NC=C1 LASIJVXABDMKBX-UHFFFAOYSA-N 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
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- YJDOIAGBSYPPCK-UHFFFAOYSA-N trimethoxy(3-morpholin-4-ylpropyl)silane Chemical compound CO[Si](OC)(OC)CCCN1CCOCC1 YJDOIAGBSYPPCK-UHFFFAOYSA-N 0.000 description 1
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- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 1
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 description 1
- HLSUJEMQFFRRGO-UHFFFAOYSA-N tripropoxy(2-pyridin-2-ylethyl)silane Chemical compound CCCO[Si](OCCC)(OCCC)CCC1=CC=CC=N1 HLSUJEMQFFRRGO-UHFFFAOYSA-N 0.000 description 1
- NQNRFXUFLXAZTC-UHFFFAOYSA-N tripropoxy(2-pyridin-4-ylethyl)silane Chemical compound CCCO[Si](OCCC)(OCCC)CCC1=CC=NC=C1 NQNRFXUFLXAZTC-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
- FBGNFSBDYRZOSE-UHFFFAOYSA-N tris(ethenyl)-ethoxysilane Chemical compound CCO[Si](C=C)(C=C)C=C FBGNFSBDYRZOSE-UHFFFAOYSA-N 0.000 description 1
- JYTZMGROHNUACI-UHFFFAOYSA-N tris(ethenyl)-methoxysilane Chemical compound CO[Si](C=C)(C=C)C=C JYTZMGROHNUACI-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D9/00—Compositions of detergents based essentially on soap
- C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
- C11D9/22—Organic compounds, e.g. vitamins
- C11D9/36—Organic compounds, e.g. vitamins containing silicon
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/042—Acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D9/00—Chemical paint or ink removers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/044—Hydroxides or bases
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/162—Organic compounds containing Si
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
- C11D3/3742—Nitrogen containing silicones
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
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Abstract
Description
式(4)において、ε(誘電率)とCの関係を式(5)に示す。
{(5)式中、Sは電極面積、ε0は真空の誘電率、εrは絶縁膜の誘電率、dは配線間隔である)。
酸、
少なくとも一種のケイ素と炭素と水素とを含んでなるケイ素含有化合物、および、
任意的に界面活性剤
を含有する、シリコン系絶縁膜のエッチング後処理剤
が提供される。
前記ケイ素含有化合物が、上記式(1)〜(3)からなる群から選ばれた化合物のX1,X2および、Yの内のクロロ基、水酸基または炭素数1〜3のアルコキシ基の少なくともいずれか一つを取り去り、窒素を介して互いに結合させて得られる化合物であること、前記窒素含有物質を、0.01〜10重量%の範囲で含むこと、前記酸を、0.01〜10重量%の範囲で含むこと、前記窒素含有物質の合計量対酸の合計量の当量比が、1:0.001〜1000の範囲にあること、前記ケイ素含有化合物を、20〜60重量%の範囲で含むこと、前記界面活性剤がノニオン界面活性剤であること、前記界面活性剤が、アルコール−エチレンオキシド型界面活性剤、アルキルフェノール−エチレンオキシド型界面活性剤およびプロピレン−エチレンオキシドブロックコポリマー型界面活性剤からなる群から選ばれた少なくとも一種の界面活性剤であること、および、前記界面活性剤を、1〜10000重量ppmの範囲で含むこと、が好ましい。
2 素子間分離膜
3 サイドウォールシリコン系絶縁膜
4 ゲート電極
5a ソース拡散層
5b ドレイン拡散層
6 層間シリコン系絶縁膜
7 ストッパ膜
8 TiO
9 導体プラグ(W)
10 SiC膜
11 多孔質絶縁膜
12 SiC膜
13 TaN
14 Cu
15 SiN膜
16 多孔質絶縁膜
17 SiC膜
18 多孔質絶縁膜
19 SiC膜
20 TaN
21 Cu
22 SiN膜
31 絶縁膜
32 TiNバリアメタル層
33 コンタクトホール
34 パッシベーション膜
35 電極パッド
本発明に係るシリコン系絶縁膜のエッチング後処理剤は、(1)アンモニア系塩基およびアミン化合物からなる群から選ばれた、少なくとも一種の窒素含有物質、(2)酸、(3)少なくとも一種のケイ素と炭素と水素とを含んでなるケイ素含有化合物、および、(4)任意的に界面活性剤、を含有する。
ラン、プロピルフェニルジメトキシシラン、プロピルビニルジメトキシシラン、プロピルジメチルメトキシシラン、プロピルジエチルメトキシシラン、プロピルジフェニルメトキシシラン、プロピルジビニルメトキシシラン、ジプロピルメチルメトキシシラン、ジプロピルエチルメトキシシラン、ジプロピルフェニルメトキシシラン、ジプロピルビニルメトキシシラン、プロピルメチルエチルメトキシシラン、プロピルエチルフェニルメトキシシラン、プロピルメチルフェニルメトキシシラン、プロピルメチルビニルメトキシシラン、プロピルエチルビニルメトキシシラン、プロピルフェニルビニルメトキシシラン、ブチルメトキシシラン、ジブチルメトキシシラン、ジブチルジメトキシシラン、トリブチルメトキシシラン、ブチルトリメトキシシラン、ブチルメチルメトキシシラン、ブチルエチルメトキシシラン、ブチルフェニルメトキシシラン、ブチルビニルメトキシシラン、ブチルプロピルメトキシシラン、ブチルメチルジメトキシシラン、ブチルエチルジメトキシシラン、ブチルフェニルジメトキシシラン、ブチルビニルジメトキシシラン、ブチルプロピルジメトキシシラン、ブチルジメチルメトキシシラン、ブチルジエチルメトキシシラン、ブチルジフェニルメトキシシラン、ブチルジビニルメトキシシラン、ブチルジプロピルメトキシシラン、ジブチルメチルメトキシシラン、ジブチルエチルメトキシシラン、ジブチルフェニルメトキシシラン、ジブチルビニルメトキシシラン、ジブチルプロピルメトキシシラン、ブチルメチルエチルメトキシシラン、ブチルメチルフェニルメトキシシラン、ブチルエチルフェニルメトキシシラン、ブチルメチルビニルメトキシシラン、ブチルエチルビニルメトキシシラン、ブチルフェニルビニルメトキシシラン、ブチルメチルプロピルメトキシシラン、ブチルエチルプロピルメトキシシラン、プチルフェニルプロピルメトキシシラン、ブチルビニルプロピルメトキシシラン、p-トリルメトキシシラン、p-トリルジメトキシシラン、p-トリルトリメトキシシラン、p-トリルジメチルメトキシシラン、p-トリルメチルジメトキシシラン、p-トリルフェニルメトキシシラン、p-トリルジフェニルメトキシシラン、p-トリルフェニルジメトキシシラン、1-エチル-4-メトキシシリルベンゼン、1-エチル-4-ジメチルメトキシシリルベンゼン、1-エチル-4-メチルジメトキシシリルベンゼン、1-エチル-4-トリメトキシシリルベンゼン、1-エチル-4-フェニルメトキシシリルベンゼン、1-エチル-4-ジフェニルメトキシシリルベンゼン、1-エチル-4-フェニルジメトキシシリルベンゼン、2,6-ジメチル-4-メトキシシリルベンゼン、2,6-ジメチル-4-ジメトキシシリルベンゼン、2,6-ジメチル-4-トリメトキシシリルベンゼン、2,6-ジメチル-4-メチルメトキシシリルベンゼン、2,6-ジメチル-4-メチルジメトキシシリルベンゼン、2,6-ジメチル-4-ジメチルメトキシシリルベンゼン、2,6-ジメチル-4-フェニルメトキシシリルベンゼン、2,6-ジメチル-4-フェニルジメトキシシリルベンゼン、2,6-ジメチル-4-ジフェニルメトキシシリルベンゼン、トリベンジルメトキシシラン、ジベンジルメトキシシラン、ジベンジルジメトキシシラン、ベンジルトリメトキシシラン、ペンタフルオロフェニルジメチルメトキシシラン、ペンタフルオロフェニルメチルジメトキシシラン、3-モルフォリノプロピルトリメトキシシラン、3-モルフォノプロピルジメチルメトキシシラン、p-メトキリフェニルトリメトキシシラン、p-メトキシフェニルジメチルメトキシシラン、イソプロピルジメチルメトキシシラン、イソプロピルメチルジメトキシシラン、イソブチルトリメトキシシラン、イソブチルジメチルメトキシシラン、イソブチルメチルジメトキシシラン、トリメトキシシリルアナニド、4-[2-(トリメトキシシリル)エチル]ピリジン、2-[2-(トリメトキシシリル)エチル]ピリジン、N-(3-トリメトキシシリルプロピル)-4,5-ジヒドロイミダゾール、3-(トリメトキシシリル)シクロペンテン、エトキシシラン、ジエトキシシラン、トリエトキシシラン、トリメチルエトキシシラン、ジメチルエトキシシラン、ジメチルジエトキシシラン、メチルエトキシシラン、メチルトリエトキシシラン、トリエチルエトキシシラン、ジエチルエトキシシラン、ジエチルジエトキシシラン、エチルエトキシシラン、エチルトリエトキシシラン、エチルメチルエトキシシラン、エチルメチルジエトキシシラン、エチルジメチルエトキシシラン、メチルジエチルエトキシシラン、フェニルエトキシシラン、ジフェニルエトキシシラン、トリフェニルエトキシシラン、フェニルジエトキシシラン、フェニルトリエトキシシラン、ジフェニルジエトキシシラン、フェニルメチルエトキシシラン、フェニルメチルジエトキシシラン、フェニルジメチルエトキシシラン、フェニルジエチルエトキシシラン、ジフェニルメチルエトキシシラン、ジフェニルエチルエトキシシラン、フェニルエチルメチルエトキシシラン、ビニルエトキシシラン、ビニルジエトキシシラン、ビニルトリエトキシシラン、ジビニルエトキシシラン、ジビニルジエトキシシラン、トリビニルエトキシシラン、ビニルメチルエトキシシラン、ビニルエチルエトキシシラン、ビニルメチルジエトキシシラン、ビニルエチルジエトキシシラン、プロピルエトキシシラン、プロピルジエトキシシラン、プロピルトリエトキシシラン、ジプロピルエトキシシラン、ジプロピルエトキシシラン、ジプロピルジエトキシシラン、トリプロピルエトキシシラン、プロピルメチルエトキシシラン、プロピルエチルエトキシシラン、プロピルフェニルエトキシシラン、プロピルビニルエトキシシラン、プロピルメチルジエトキシシラン、プロピルエチルジエトキシシラン、プロピルフェニルジエトキシシラン、プロピルビニルジエトキシシラン、プロピルジメチルエトキシシラン、プロピルジエチルエトキシシラン、プロピルジフェニルエトキシシラン、プロピルジビニルエトキシシラン、ジプロピルメチルエトキシシラン、ジプロピルエチルエトキシシラン、ジプロピルフェニルエトキシシラン、ジプロピルビニルエトキシシラン、プロピルメチルエチルエトキシシラン、プロピルエチルフェニルエトキシシラン、プロピルメチルフェニルエトキシシラン、プロピルメチルビニルエトキシシラン、プロピルエチルビニルエトキシシラン、プロピルフェニルビニルエトキシシラン、ブチルエトキシシラン、ジブチルエトキシシラン、ジブチルジエトキシシラン、トリブチルエトキシシラン、ブチルトリエトキシシラン、ブチルメチルエトキシシラン、ブチルエチルエトキシシラン、ブチルフェニルエトキシシラン、ブチルビニルエトキシシラン、ブチルプロピルエトキシシラン、ブチルメチルジエトキシシラン、ブチルエチルジエトキシシラン、ブチルフェニルジエトキシシラン、ブチルビニルジエトキシシラン、ブチルプロピルジエトキシシラン、ブチルジメチルエトキシシラン、ブチルジエチルエトキシシラン、ブチルジフェニルエトキシシラン、ブチルジビニルエトキシシラン、ブチルジプロピルエトキシシラン、ジブチルメチルエトキシシラン、ジブチルエチルエトキシシラン、ジブチルフェニルエトキシシラン、ジブチルビニルエトキシシラン、ジブチルプロピルエトキシシラン、ブチルメチルエチルエトキシシラン、ブチルメチルフェニルエトキシシラン、ブチルエチルフェニルエトキシシラン、ブチルメチルビニルエトキシシラン、ブチルエチルビニルエトキシシラン、ブチルフェニルビニルエトキシシラン、ブチルメチルプロピルエトキシシラン、ブチルエチルプロピルエトキシシラン、プチルフェニルプロピルエトキシシラン、ブチルビニルプロピルエトキシシラン、p-トリルエトキシシラン、p-トリルジエトキシシラン、p-トリルトリエトキシシラン、p-トリルジメチルエトキシシラン、p-トリルメチルジエトキシシラン、p-トリルフェニルエトキシシラン、p-トリルジフェニルエトキシシラン、p-トリルフェニルジエトキシシラン、1-エチル-4-エトキシシリルベンゼン、1-エチル-4-ジメチルエトキシシリルベンゼン、1-エチル-4-メチルジエトキシシリルベンゼン、1-エチル-4-トリエトキシシリルベンゼン、1-エチル-4-フェニルエトキシシリルベンゼン、1-エチル-4-ジフェニルエトキシシリルベンゼン、1-エチル-4-フェニルジエトキシシリルベンゼン、2,6-ジメチル-4-エトキシシリルベンゼン、2,6-ジメチル-4-ジエトキシシリルベンゼン、2,6-ジメチル-4-トリエトキシシリルベンゼン、2,6-ジメチル-4-メチルエトキシシリルベンゼン、2,6-ジメチル-4-メチルジエトキシシリルベンゼン、2,6-ジメチル-4-ジメチルエトキシシリルベンゼン、2,6-ジメチル-4-フェニルエトキシシリルベンゼン、2,6-ジメチル-4-フェニルジエトキシシリルベンゼン、2,6-ジメチル-4-ジフェニルエトキシシリルベンゼン、トリベンジルエトキシシラン、ジベンジルエトキシシラン、ジベンジルジエトキシシラン、ベンジルトリエトキシシラン、ペンタフルオロフェニルジメチルエトキシシラン、ペンタフルオロフェニルメチルジエトキシシラン、3-モルフォリノプロピルトリエトキシシラン、3-モルフォノプロピルジメチルエトキシ、p-メトキリフェニルトリエトキシシラン、p-メトキシフェニルジメチルエトキシシラン、イソプロピルジメチルエトキシシラン、イソプロピルメチルジエトキシシラン、イソブチルトリエトキシシラン、イソブチルジメチルエトキシシラン、イソブチルメチルジエトキシシラン、トリクロロシエトキシナニド、4-[2-(トリクロロシリル)エチル]ピリジン、2-[2-(トリエトキシシリル)エチル]ピリジン、N-(3-トリエトキシシリルプロピル)-4,5-ジヒドロイミダゾール、3-(トリクロロシリル)シエトキシペンテン、プロポキシシラン、ジプロポキシシラン、トリプロポキシシラン、トリメチルプロポキシシラン、ジメチルプロポキシシラン、ジメチルジプロポキシシラン、メチルプロポキシシラン、メチルトリプロポキシシラン、トリエチルプロポキシシラン、ジエチルプロポキシシラン、ジエチルジプロポキシシラン、エチルプロポキシシラン、エチルトリプロポキシシラン、エチルメチルプロポキシシラン、エチルメチルジプロポキシシラン、エチルジメチルプロポキシシラン、メチルジエチルプロポキシシラン、フェニルプロポキシシラン、ジフェニルプロポキシシラン、トリフェニルプロポキシシラン、フェニルジプロポキシシラン、フェニルトリプロポキシシラン、ジフェニルジプロポキシシラン、フェニルメチルプロポキシシラン、フェニルメチルジプロポキシシラン、フェニルジメチルプロポキシシラン、フェニルジエチルプロポキシシラン、ジフェニルメチルプロポキシシラン、ジフェニルエチルプロポキシシラン、フェニルエチルメチルプロポキシシラン、ビニルプロポキシシラン、ビニルジプロポキシシラン、ビニルトリプロポキシシラン、ジビニルプロポキシシラン、ジビニルジプロポキシシラン、トリビニルプロポキシシラン、ビニルメチルプロポキシシラン、ビニルエチルプロポキシシラン、ビニルメチルジプロポキシシラン、ビニルエチルジプロポキシシラン、プロピルプロポキシシラン、プロピルジプロポキシシラン、プロピルトリプロポキシシラン、ジプロピルプロポキシシラン、ジプロピルプロポキシシラン、ジプロピルジプロポキシシラン、トリプロピルプロポキシシラン、プロピルメチルプロポキシシラン、プロピルエチルプロポキシシラン、プロピルフェニルプロポキシシラン、プロピルビニルプロポキシシラン、プロピルメチルジプロポキシシラン、プロピルエチルジプロポキシシラン、プロピルフェニルジプロポキシシラン、プロピルビニルジプロポキシシラン、プロピルジメチルプロポキシシラン、プロピルジエチルプロポキシシラン、プロピルジフェニルプロポキシシラン、プロピルジビニルプロポキシシラン、ジプロピルメチルプロポキシシラン、ジプロピルエチルプロポキシシラン、ジプロピルフェニルプロポキシシラン、ジプロピルビニルプロポキシシラン、プロピルメチルエチルプロポキシシラン、プロピルエチルフェニルプロポキシシラン、プロピルメチルフェニルプロポキシシラン、プロピルメチルビニルプロポキシシラン、プロピルエチルビニルプロポキシシラン、プロピルフェニルビニルプロポキシシラン、ブチルプロ
ポキシシラン、ジブチルプロポキシシラン、ジブチルジプロポキシシラン、トリブチルプロポキシシラン、ブチルトリプロポキシシラン、ブチルメチルプロポキシシラン、ブチルエチルプロポキシシラン、ブチルフェニルプロポキシシラン、ブチルビニルプロポキシシラン、ブチルプロピルプロポキシシラン、ブチルメチルジプロポキシシラン、ブチルエチルジプロポキシシラン、ブチルフェニルジプロポキシシラン、ブチルビニルジプロポキシシラン、ブチルプロピルジプロポキシシラン、ブチルジメチルプロポキシシラン、ブチルジエチルプロポキシシラン、ブチルジフェニルプロポキシシラン、ブチルジビニルプロポキシシラン、ブチルジプロピルプロポキシシラン、ジブチルメチルプロポキシシラン、ジブチルエチルプロポキシシラン、ジブチルフェニルプロポキシシラン、ジブチルビニルプロポキシシラン、ジブチルプロピルプロポキシシラン、ブチルメチルエチルプロポキシシラン、ブチルメチルフェニルプロポキシシラン、ブチルエチルフェニルプロポキシシラン、ブチルメチルビニルプロポキシシラン、ブチルエチルビニルプロポキシシラン、ブチルフェニルビニルプロポキシシラン、ブチルメチルプロピルプロポキシシラン、ブチルエチルプロピルプロポキシシラン、プチルフェニルプロピルプロポキシシラン、ブチルビニルプロピルプロポキシシラン、p-トリルプロポキシシラン、p-トリルジプロポキシシラン、p-トリルトリプロポキシシラン、p-トリルジメチルプロポキシシラン、p-トリルメチルジプロポキシシラン、p-トリルフェニルプロポキシシラン、p-トリルジフェニルプロポキシシラン、p-トリルフェニルジプロポキシシラン、1-エチル-4-プロポキシシリルベンゼン、1-エチル-4-ジメチルプロポキシシリルベンゼン、1-エチル-4-メチルジプロポキシシリルベンゼン、1-エチル-4-トリプロポキシシリルベンゼン、1-エチル-4-フェニルプロポキシシリルベンゼン、1-エチル-4-ジフェニルプロポキシシリルベンゼン、1-エチル-4-フェニルジプロポキシシリルベンゼン、2,6-ジメチル-4-プロポキシシリルベンゼン、2,6-ジメチル-4-ジプロポキシシリルベンゼン、2,6-ジメチル-4-トリプロポキシシリルベンゼン、2,6-ジメチル-4-メチルプロポキシシリルベンゼン、2,6-ジメチル-4-メチルジプロポキシシリルベンゼン、2,6-ジメチル-4-ジメチルプロポキシシリルベンゼン、2,6-ジメチル-4-フェニルプロポキシシリルベンゼン、2,6-ジメチル-4-フェニルジプロポキシシリルベンゼン、2,6-ジメチル-4-ジフェニルプロポキシシリルベンゼン、トリベンジルプロポキシシラン、ジベンジルプロポキシシラン、ジベンジルジプロポキシシラン、ベンジルトリプロポキシシラン、ペンタフルオロフェニルジメチルプロポキシシラン、ペンタフルオロフェニルメチルジプロポキシシラン、3-モルフォリノプロピルトリプロポキシシラン、3-モルフォノプロピルジメチルプロポキシシラン、p-メトキリフェニルトリプロポキシシラン、p-メトキシフェニルジメチルプロポキシシラン、イソプロピルジメチルプロポキシシラン、イソプロピルメチルジプロポキシシラン、イソブチルトリプロポキシシラン、イソブチルジメチルプロポキシシラン、イソブチルメチルジプロポキシシラン、トリプロポキシシリルアナニド、4-[2-(トリプロポキシシリル)エチル]ピリジン、2-[2-(トリプロポキシシリル)エチル]ピリジン、N-(3-トリプロポキシシリルプロピル)-4,5-ジヒドロイミダゾール、3-(トリプロポキシシリル)シクロペンテンを挙げることができる。
半導体装置のシリコン系絶縁膜上にエッチングを施し、その後、本発明に係るエッチング後処理剤でエッチング面を処理すること、あるいは、その後、50°C〜400°Cの範囲の温度で熱処理を施すことを含む製造方法を採用して半導体装置を製造することにより、エッチングに起因するシリコン系絶縁膜の誘電率の増加を抑制することができ、また、エッチング後の表面に成膜した場合における膜剥がれや不均一な成膜を抑制できるようになる。このため、半導体装置の品質を向上させ、高速で信頼性の高い半導体装置を実現でき、その製造歩留まりを向上させることができる。このため、使用されるシリコン系絶縁膜としては、その比誘電率が2.7以下のときに特に効果が大きく好ましい。
トリメチルエトキシシラン118g(1.0mol)、イソプロパノール100g(1.66mol)を反応容器に仕込み、10°C恒温下で表1のように1.0重量%のアンモニア水17g(0.01mol)と1.0重量%のフッ化アンモニウム水溶液37g(0.01mol)の混合溶液を滴下ロートにて2mL/分の条件で滴下し、滴下終了後2時間撹拌を行った。得られた溶液(エッチング後処理剤)をpHメータにてpH測定したところ、溶液のpHは9.45であった。
トリメチルクロロシラン108g(1.0mol)、イソプロパノール100g(1.66mol)を反応容器に仕込み、10°C恒温下で表1のように1.0重量%のアンモニア水17g(0.01mol)と1.0重量%のフッ化アンモニウム水溶液37g(0.01mol)の混合溶液を滴下ロートにて2mL/分の条件で滴下し、滴下終了後2時間撹拌を行った。得られた溶液をpHメータにてpH測定したところ、溶液(エッチング後処理剤)のpHは9.50であった。
トリエチルシラノール132g(1.0mol)、イソプロパノール150g(2.50mol)を反応容器に仕込み、10°C恒温下で表1のように1.0重量%のアンモニア水17g(0.01mol)と1.0重量%のフッ化アンモニウム水溶液37g(0.01mol)の混合溶液を滴下ロートにて2mL/分の条件で滴下し、滴下終了後2時間撹拌を行った。得られた溶液をpHメータにてpH測定したところ、溶液(エッチング後処理剤)のpHは9.45であった。
ジメチルジメトキシシラン120g(1.0mol)、イソプロパノール150g(2.50mol)を反応容器に仕込み、10°C恒温下で表1のように1.0重量%のアンモニア水17g(0.01mol)と1.0重量%のフッ化アンモニウム水溶液37g(0.01mol)の混合溶液を滴下ロートにて2mL/分の条件で滴下し、滴下終了後2時間撹拌を行った。得られた溶液をpHメータにてpH測定したところ、溶液(エッチング後処理剤)のpHは9.23であった。
フェニルトリエトキシシラン240g(1.0mol)、イソプロパノール200g(3.33mol)およびTN−80(旭電化,アルコール−エチレンオキシド型非イオン界面活性剤;第一級アルコールエトキシレート)0.05g(完成溶液に対して100重量ppm)を反応容器に仕込み、10°C恒温下で表1のように1.0重量%のアンモニア水17g(0.01mol)と1.0重量%のフッ化アンモニウム水溶液37g(0.01mol)の混合溶液を滴下ロートにて2mL/分の条件で滴下し、滴下終了後2時間撹拌を行った。得られた溶液をpHメータにてpH測定したところ、溶液(エッチング後処理剤)のpHは9.13であった。
ヘキサメチルジシラザン161g(1.0mol)、イソプロパノール150g(2.50mol)を反応容器に仕込み、10°C恒温下で表1のように1.0重量%のアンモニア水17g(0.01mol)と1.0重量%のフッ化アンモニウム水溶液37g(0.01mol)の混合溶液を滴下ロートにて2mL/分の条件で滴下し、滴下終了後2時間撹拌を行った。得られた溶液をpHメータにてpH測定したところ、溶液(エッチング後処理剤)のpHは9.55であった。
実施例1において、混合するアンモニア系塩基とフッ化アンモニウムの当量比を1:0.002〜600まで表1のように変更して、エッチング後処理剤を作製した。
実施例5での溶液作製において使用したTN−80の添加量を3〜8000重量ppmまで表1のように変えて溶液(エッチング後処理剤)を作製した。
トリメチルエトキシシラン118g(1.0mol)、ジオキサン100g(1.13mol)を反応容器に仕込み、10°C恒温下で表1のように1.0重量%の水酸化テトラ−n−ブチルアンモニウム水溶液258g(0.01mol)と1.0重量%のリン酸水素二アンモニウム水溶液66g(0.005mol)の混合溶液を滴下ロートにて2mL/分の条件で滴下し、滴下終了後2時間撹拌を行った。得られた溶液をpHメータにてpH測定したところ、溶液(エッチング後処理剤)のpHは9.67であった。
トリメチルエトキシシラン118g(1.0mol)、メチルイソブチルケトン100g(1.00mol)を反応容器に仕込み、10°C恒温下で表1のように1.0重量%の水酸化テトラメチルアンモニウム水溶液91g(0.01mol)と1.0重量%のギ酸アンモニウム水溶液63g(0.01mol)の混合溶液を滴下ロートにて2mL/分の条件で滴下し、滴下終了後2時間撹拌を行った。得られた溶液をpHメータにてpH測定したところ、溶液(エッチング後処理剤)のpHは9.52であった。
トリメチルエトキシシラン118g(1.0mol)、プロピレングリコールモノメチルエーテル100g(0.85mol)を反応容器に仕込み、10°C恒温下で表1のように1.0重量%の水酸化テトラプロピルアンモニウム水溶液203g(0.01mol)と1.0重量%の酢酸アンモニウム水溶液77g(0.01mol)の混合溶液を滴下ロートにて2mL/分の条件で滴下し、滴下終了後2時間撹拌を行った。得られた溶液をpHメータにてpH測定したところ、溶液(エッチング後処理剤)のpHは9.60であった。
トリメチルエトキシシラン118g(1.0mol)、プロピレングリコールモノプロピルエーテル100g(0.85mol)を反応容器に仕込み、10°C恒温下で表1のように1.0重量%のエチレンジアミン水溶液120g(0.02mol)と1.0重量%のシュウ酸水溶液90g(0.01mol)の混合溶液を滴下ロートにて2mL/分の条件で滴下し、滴下終了後2時間撹拌を行った。得られた溶液をpHメータにてpH測定したところ、溶液(エッチング後処理剤)のpHは9.31であった。
従来のエッチング後洗浄剤として用いられる、フッ化アンモニウム水溶液を1.0重量%に調整した。得られた溶液をpH試験紙にてpH測定したところ、液のpHは7.7であった。
従来、エッチング後のシリコン系絶縁膜回復処理剤として用いられる、ヘキサメチルジシラザン161g(1.0mol)を、イソプロパノール161g(2.7mol)と混合し、溶液を調整した。
(処理方法)
Siウエハ上に形成したSiOCH含有材料からなる多孔質絶縁膜(「セラメート NCS」;触媒化成工業製)160nm(以降、これを単に多孔質絶縁膜と呼ぶことがある)をCF4/CHF3を原料としたFプラズマにより20nmエッチングし、その上から実施例処理剤および比較例処理剤を、回転数500rpm、60秒でスピン塗布処理を行い、後に200℃に設定したホットプレートに載せて60秒間の条件で乾燥を施した。
評価対象の膜上に直径1mm金電極を作製し、1MHz、1Vの交流電源を接続したプローバを用いて容量を測定し、該容量と分光エリプソメトリーにより測定した膜厚とから比誘電率を算出した。さらに、該比誘電率とエッチング後の多孔質絶縁膜の比誘電率の差から回復量を算出した。ただし、エッチング前の多孔質絶縁膜の比誘電率は2.25であり、エッチング後の多孔質絶縁膜の比誘電率は3.23であった。
50,000倍の表面SEM写真に於いて、加速電圧5kVで評価対象の膜表面の粗れによりエッチング残渣の有無を目視確認した。
X線光電子分光により表面分析を行い、F 1sピークの積分値から膜表面におけるCFxの割合を算出した。
Cu膜の膜厚の減少率は段差計を用いて測定した。表中のCuの膜厚減少率は、元の厚さに対する腐食後の厚さの割合を表す。
光学顕微鏡にて100倍の倍率で塗布ムラを目視確認した。
図1〜5を参照して、素子間分離膜(2)で分離され、ソース拡散層(5a)とドレイン拡散層(5b)、サイドウォールシリコン系絶縁膜(3)を有するゲート電極を形成したトランンジスタ層が形成されたSiウエハ(1)(ステップ1)に層間シリコン系絶縁膜(6)、ストッパ膜(7)を形成し、電極取り出し用のコンタクトホールを形成した(ステップ2)。
Claims (17)
- アンモニア系塩基およびアミン化合物からなる群から選ばれた、少なくとも一種の窒素含有物質、
酸、および、
少なくとも一種のケイ素と炭素と水素とを含んでなるケイ素含有化合物
を含有する、シリコン系絶縁膜のエッチング後処理剤。 - pHが7を超え10以下の範囲にある、請求項1に記載のエッチング後処理剤。
- 前記ケイ素含有化合物が、式(1)〜(3)からなる群から選ばれた化合物を含む、請求項1または2に記載のエッチング後処理剤、
- 前記ケイ素含有化合物が、式(1)〜(3)からなる群から選ばれた化合物のX1,X2および、Yの内のクロロ基、水酸基または炭素数1〜3のアルコキシ基の少なくともいずれか一つを取り去り、窒素を介して互いに結合させて得られる化合物である、請求項1〜3のいずれかに記載のエッチング後処理剤、
- 前記窒素含有物質を0.01〜10重量%の範囲で含む、請求項1〜4のいずれかに記載のエッチング後処理剤。
- 前記酸を0.01〜10重量%の範囲で含む、請求項1〜5のいずれかに記載のエッチング後処理剤。
- 前記窒素含有物質の合計量対酸の合計量の当量比が、1:0.001〜1000の範囲にある、請求項6に記載のエッチング後処理剤。
- 前記ケイ素含有化合物を20〜60重量%の範囲で含む、請求項1〜7のいずれかに記載のエッチング後処理剤。
- 前記界面活性剤がノニオン界面活性剤である、請求項1〜8のいずれかに記載のエッチング後処理剤。
- 前記界面活性剤が、アルコール−エチレンオキシド型界面活性剤、アルキルフェノール−エチレンオキシド型界面活性剤およびプロピレン−エチレンオキシドブロックコポリマー型界面活性剤からなる群から選ばれた少なくとも一種の界面活性剤である、請求項9に記載のエッチング後処理剤。
- 前記界面活性剤を、1〜10000重量ppmの範囲で含む、請求項1〜10のいずれかに記載のエッチング後処理剤。
- 半導体装置のシリコン系絶縁膜上にエッチングを施し、
その後、請求項1〜11のいずれかに記載のエッチング後処理剤で当該エッチング面を処理し、
その後、50°C〜400°Cの範囲の温度で熱処理を施すことを含む、半導体装置の製造方法。 - 前記シリコン系絶縁膜が、半導体装置の配線層とビアとの少なくともいずれか一方を絶縁するための絶縁膜である、請求項12に記載の半導体装置の製造方法。
- 前記シリコン系絶縁膜の比誘電率が2.7以下である、請求項12または13に記載の製造方法。
- 前記処理が、エッチングによる損傷を回復するためのものである、請求項12〜14のいずれかに記載の半導体装置の製造方法。
- 前記処理が、エッチング残渣を洗浄するためのものである、請求項12〜15のいずれかに記載の半導体装置の製造方法。
- 請求項12〜16のいずれかに記載の半導体装置の製造方法により製造された、半導体装置。
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US10678602B2 (en) * | 2011-02-09 | 2020-06-09 | Cisco Technology, Inc. | Apparatus, systems and methods for dynamic adaptive metrics based application deployment on distributed infrastructures |
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US20150380296A1 (en) * | 2014-06-25 | 2015-12-31 | Lam Research Corporation | Cleaning of carbon-based contaminants in metal interconnects for interconnect capping applications |
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US10167425B2 (en) | 2016-05-04 | 2019-01-01 | Oci Company Ltd. | Etching solution capable of suppressing particle appearance |
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US20190103282A1 (en) * | 2017-09-29 | 2019-04-04 | Versum Materials Us, Llc | Etching Solution for Simultaneously Removing Silicon and Silicon-Germanium Alloy From a Silicon-Germanium/Silicon Stack During Manufacture of a Semiconductor Device |
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