JP7400013B2 - 半導体基板の残渣を除去するための洗浄用調合物 - Google Patents
半導体基板の残渣を除去するための洗浄用調合物 Download PDFInfo
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- JP7400013B2 JP7400013B2 JP2022081185A JP2022081185A JP7400013B2 JP 7400013 B2 JP7400013 B2 JP 7400013B2 JP 2022081185 A JP2022081185 A JP 2022081185A JP 2022081185 A JP2022081185 A JP 2022081185A JP 7400013 B2 JP7400013 B2 JP 7400013B2
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- DCZFGQYXRKMVFG-UHFFFAOYSA-N cyclohexane-1,4-dione Chemical compound O=C1CCC(=O)CC1 DCZFGQYXRKMVFG-UHFFFAOYSA-N 0.000 description 1
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- NUUPJBRGQCEZSI-UHFFFAOYSA-N cyclopentane-1,3-diol Chemical compound OC1CCC(O)C1 NUUPJBRGQCEZSI-UHFFFAOYSA-N 0.000 description 1
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- 229960004132 diethyl ether Drugs 0.000 description 1
- JQDCIBMGKCMHQV-UHFFFAOYSA-M diethyl(dimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)CC JQDCIBMGKCMHQV-UHFFFAOYSA-M 0.000 description 1
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- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 1
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- 235000006666 potassium iodate Nutrition 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
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- 235000002906 tartaric acid Nutrition 0.000 description 1
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- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- LUVHDTDFZLTVFM-UHFFFAOYSA-M tetramethylazanium;chlorate Chemical compound [O-]Cl(=O)=O.C[N+](C)(C)C LUVHDTDFZLTVFM-UHFFFAOYSA-M 0.000 description 1
- FDXKBUSUNHRUIZ-UHFFFAOYSA-M tetramethylazanium;chlorite Chemical compound [O-]Cl=O.C[N+](C)(C)C FDXKBUSUNHRUIZ-UHFFFAOYSA-M 0.000 description 1
- ZRVXFJFFJZFRLQ-UHFFFAOYSA-M tetramethylazanium;iodate Chemical compound [O-]I(=O)=O.C[N+](C)(C)C ZRVXFJFFJZFRLQ-UHFFFAOYSA-M 0.000 description 1
- HLQAWDQQEJSALG-UHFFFAOYSA-M tetramethylazanium;periodate Chemical compound C[N+](C)(C)C.[O-]I(=O)(=O)=O HLQAWDQQEJSALG-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-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
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- C11D7/02—Inorganic compounds
- C11D7/20—Water-insoluble oxides
-
- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0042—Reducing agents
-
- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0047—Other compounding ingredients characterised by their effect pH regulated compositions
-
- 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
- C11D3/2079—Monocarboxylic 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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- 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
- C11D3/34—Organic compounds containing sulfur
- C11D3/3409—Alkyl -, alkenyl -, cycloalkyl - or terpene sulfates or sulfonates
-
- 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
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- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/3427—Organic compounds containing sulfur containing thiol, mercapto or sulfide groups, e.g. thioethers or mercaptales
-
- 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
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/06—Hydroxides
-
- 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
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
-
- 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
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3209—Amines or imines with one to four nitrogen atoms; 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3245—Aminoacids
-
- 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
- C11D7/22—Organic compounds
- C11D7/34—Organic compounds containing sulfur
-
- 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
- C11D7/50—Solvents
-
- 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
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5022—Organic solvents containing oxygen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
- H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
-
- C11D2111/22—
-
- 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
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/261—Alcohols; Phenols
-
- 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
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/263—Ethers
-
- C—CHEMISTRY; METALLURGY
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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Description
本出願は、2016年12月8日に出願された米国仮特許出願第62/431,620号及び2016年10月6日に出願された米国仮特許出願第62/404,852号の優先権を主張するものであり、それらの全体が参照により本明細書に取り込まれる。
本開示は、半導体基板のための新規な洗浄組成物及び半導体基板を洗浄する方法に関する。具体的には、本開示は、半導体基板に配置された金属層又は誘電体材料層がプラズマエッチングされ、プラズマアッシングプロセスによりレジスト全体が除去された後に前記基板上に残る残渣を除去するための洗浄組成物に関する。
集積回路デバイスの製造において、一連のフォトリソグラフィ及びプラズマエッチング工程によりレチクルの原マスクパターンをウェハ基板に転写するための中間マスクとして、フォトレジストが用いられる。集積回路デバイスの製造プロセスにおける必須工程の1つは、パターニングされたフォトレジト膜をウェハ基板から除去することである。この工程は一般に、以下2つの方法のうちの1つによって行われる。
1)少なくとも1種のレドックス剤;
2)水溶性アルコール類、水溶性ケトン類、水溶性エステル類、及び水溶性エーテル類からなる群より選択される少なくとも1種の有機溶媒;
3)少なくとも1種の金属含有添加剤;並びに
4) 水、
を含む、洗浄組成物に関する。
(A)エッチング後の残渣及び/又はアッシング後の残渣を含む半導体基板を提供する工程;
(B)前記半導体基板を、本明細書に記載の洗浄組成物と接触させる工程;
(C)前記半導体基板を、適切なリンス溶媒でリンスする工程;並びに
(D)所望により、前記リンス溶媒を除去し前記半導体基板の品質を損なわない何らかの手段によって、前記半導体基板を乾燥させる工程、
を含んでいてもよい。
1)少なくとも1種のレドックス剤;
2)水溶性アルコール類、水溶性ケトン類、水溶性エステル類、及び水溶性エーテル類からなる群より選択される少なくとも1種の有機溶媒;
3)少なくとも1種の金属含有添加剤;並びに
4) 水、
を含む、非腐食性洗浄組成物に関する。
(NH4)mMXn 式(I)
式(I)中、mは、1、2、3、又は4であり;nは、1、2、3、4、5、又は6であり;Mは、金属イオン(第2A族金属、第3B族金属、第4B族金属、第5B族金属、又はランタニド金属のイオンなど)であり;Xは、ハロゲン化物イオン(例えば、F、Cl、Br、又はI)である。
(A)エッチング後の残渣及び/又はアッシング後の残渣を含む半導体基板を提供する工程;
(B)前記半導体基板を、本明細書に記載の洗浄組成物と接触させる工程;
(C)前記半導体基板を、適切なリンス溶媒でリンスする工程;並びに
(D)所望により、前記リンス溶媒を除去し前記半導体基板の品質を損なわない何らかの手段によって、前記半導体基板を乾燥させる工程、
を含む。ある実施形態では、前記洗浄方法は、上述の方法により得られた前記半導体基板から半導体デバイス(例えば、半導体チップなどの集積回路デバイス)を形成することを更に含む。
調合物ブレンド
本開示の組成物を、有機溶媒及び超純粋脱イオン水(DIW)と撹拌しながら混合することにより調製した。均一な溶液が得られた後、残りの成分を添加した。用いた成分はすべて、市販されている高純度のものであった。
ビーカー試験による洗浄評価
リソグラフィでパターニングされ、プラズマ金属エッチング装置でエッチングし、続いて酸素プラズマアッシングによりフォトレジストのトップ層を完全に除去した、フォトレジスト/TiOx/SiN/Co/ILD(ILD=層間絶縁体)又はフォトレジスト/TiOx/SiN/W/ILDの多層基板を用いて、基板のPER(エッチング後の残渣)を上述の洗浄組成物により洗浄した。
ビーカー試験による材料相溶性評価
シリコン基板上のブランケットCo、シリコン基板上のW、シリコン基板上のSiO2上TiOx、シリコン基板上のSiN、シリコン基板上のILD、シリコン基板上のSiC、及びシリコン基板上のW合金をさいの目に切り、材料相溶性試験用のおよそ1インチ×1インチの正方形試験クーポンにした。まず、試験クーポンについて、金属膜(Co、W)の場合は4点プローブ、CDE Resmap 273により、又は誘電体膜(TiOx、SiN、及びILD)の場合はWoollam M‐2000Xを用いたエリプソメトリにより、厚み又はシート抵抗を測定した。次に、試験クーポンを長さ4インチのプラスチックロッキングピンセットにセットし、クーポンのCo、W、W合金、TiOx、SiN、SiC、又はILD層を有する側が撹拌子側になるようにして、一般手順2の洗浄手順に記載の通りに10分間処理した。
表1に、一般手順1に従って調製した調合物FE-1~FE-7(硫黄含有添加剤を含む)を示す。
露出している金属又は誘電体との洗浄剤の相溶性
調合物FE-4、FE-6、及びFE-7を、一般手順2に従い洗浄力について試験し、一般手順3に従って材料相溶性について65℃で4分間試験した。洗浄組成物によるCo、W、W合金、TiOx、SiN、SiC、及びILDのエッチレート(ER)(オングストローム/分)を表2に示す。
表3に、一般手順1に従って調製した調合物FE-8~FE-26(いかなる硫黄含有添加剤も含まないか、いかなる酸も含まない)を示す。
露出している金属との洗浄剤の相溶性
調合物FE-8~FE-26及びCFE-1を、一般手順3に従い材料相溶性について65℃で4分間試験した。洗浄用調合物によるW合金、TiOx、Co、及びWのエッチレート(ER)(オングストローム/分)を表4に示す。
表5に、一般手順1に従って調製した調合物FE-27~FE-32(アミノ酸グリシンを含む)を示す。
露出している金属との洗浄剤の相溶性
調合物FE-27~FE-32を、一般手順3に従って材料相溶性について65℃で4分間試験した。洗浄用調合物によるW合金、Co、AlOx、及びTiOxのエッチレート(ER)(オングストローム/分)を表6に示す。
表7に、一般手順1に従って調製した調合物FE-33~FE-40(アミノ酸グリシンを含む)を示す。
露出している金属との洗浄剤の相溶性
調合物FE-33~FE-40を、一般手順3に従って材料相溶性について65℃で4分間試験した。洗浄用調合物によるW合金、Co、AlOx、及びTiOxのエッチレート(ER)(オングストローム/分)を表8に示す。
表9に、一般手順1に従って調製した調合物FE-41~FE-52(FE-41以外は導電性向上剤を含む)を示す。
本開示は下記の実施形態<1>~<34>も含む。
<1>
1)少なくとも1種のレドックス剤;
2)水溶性アルコール類、水溶性ケトン類、水溶性エステル類、及び水溶性エーテル類からなる群より選択される少なくとも1種の有機溶媒;
3)少なくとも1種の金属含有添加剤;並びに
4) 水、
を含む、洗浄組成物。
<2>
約7~約11のpHを有する、<1>に記載の組成物。
<3>
前記少なくとも1種のレドックス剤は、ヒドロキシルアミンを含む、<1>に記載の組成物。
<4>
前記少なくとも1種のレドックス剤は、前記組成物の約5重量%~約20重量%である、<1>に記載の組成物。
<5>
前記少なくとも1種の有機溶媒は、2種の有機溶媒を含む、<1>に記載の組成物。
<6>
前記2種の有機溶媒は、それぞれ独立して、アルキレングリコール類及びアルキレングリコールエーテル類からなる群より選択される、<5>に記載の組成物。
<7>
前記少なくとも1種の有機溶媒は、前記組成物の約60重量%~約95重量%である、<1>に記載の組成物。
<8>
前記少なくとも1種の金属含有添加剤は、金属ハロゲン化物、金属水酸化物、金属ホウ化物、金属アルコキシド、金属酸化物、又は金属含有アンモニウム塩を含む、<1>に記載の組成物。
<9>
前記少なくとも1種の金属含有添加剤は、第2A族金属、第3B族金属、第4B族金属、第5B族金属、又はランタニド金属を含む、<1>に記載の組成物。
<10>
前記少なくとも1種の金属含有添加剤は、Ca、Ba、Ti、Hf、Sr、La、Ce、W、V、Nb、又はTaを含む、<9>に記載の組成物。
<11>
前記少なくとも1種の金属含有添加剤は、ホウ化タングステン、Ca(OH) 2 、BaCl 2 、SrCl 2 、LaCl 3 、CeCl 3 、(NH 4 ) 2 TiF 6 、BaTiO 3 、Ti(OEt) 4 、Ti(OCH(CH 3 ) 2 ) 4 、HfO 2 、V 2 O 5 、Nb 2 O 5 、又はTaF 3 を含む、<1>に記載の組成物。
<12>
前記少なくとも1種の金属含有添加剤は、前記組成物の約0.001重量%~約0.5重量%である、<1>に記載の組成物。
<13>
前記水は、前記組成物の約5%~約28%である、<1>に記載の組成物。
<14>
pH調整剤をさらに含む、<1>に記載の組成物。
<15>
前記pH調整剤は、1,8-ジアザビシクロ[5.4.0]-7-ウンデセンである、<14>に記載の組成物。
<16>
少なくとも1種の洗浄添加剤をさらに含む、<1>に記載の組成物。
<17>
前記少なくとも1種の洗浄添加剤は、硫黄含有添加剤である、<16>に記載の組成物。
<18>
前記硫黄含有添加剤は、チオール又はチオエーテルを含む、<17>に記載の組成物。
<19>
前記硫黄含有添加剤は、3-アミノ-5-メルカプト-1H-1,2,4-トリアゾール、β-メルカプトエタノール、3-アミノ-5-メチルチオ-1H-1,2,4-トリアゾール、1-フェニル-1H-テトラゾール-5-チオール、4-メチル-4H-1,2,4-トリアゾール-3-チオール、2-ピリジンチオール、又は3-メルカプトプロピオン酸を含む、<18>に記載の組成物。
<20>
前記硫黄含有添加剤は、前記組成物の約0.01重量%~約0.15重量%である、<17>に記載の組成物。
<21>
前記少なくとも1種の洗浄添加剤は、アミノ酸を含む、<16>に記載の組成物。
<22>
前記アミノ酸は、グリシンである、<21>に記載の組成物。
<23>
前記アミノ酸は、前記組成物の約0.01重量%~約0.15重量%である、<21>に記載の組成物。
<24>
少なくとも1種の有機酸をさらに含む、<1>に記載の組成物。
<25>
前記少なくとも1種の有機酸は、カルボン酸又はスルホン酸を含む、<24>に記載の組成物。
<26>
前記少なくとも1種の有機酸は、前記組成物の約0.1重量%~約0.5重量%である、<24>に記載の組成物。
<27>
水酸化第四級アンモニウム類、第四級アンモニウム塩類、及びイミダゾリウム塩類からなる群より選択される少なくとも1種の導電性向上剤をさらに含む、<1>に記載の組成物。
<28>
前記導電性向上剤は、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラブチルアンモニウム、塩化テトラブチルアンモニウム、水酸化ベンジルトリメチルアンモニウム、又は1-ブチル-3-メチルイミダゾリウムメタンスルホネートである、<27>に記載の組成物。
<29>
前記少なくとも1種の導電性向上剤は、前記組成物の約1重量%~約10重量%である、<27>に記載の組成物。
<30>
エッチング後の残渣又はアッシング後の残渣を含む半導体基板を、<1>~<29>のいずれか1つに記載の洗浄組成物と接触させることを含む、方法。
<31>
前記半導体基板は、Cu、Co、W、AlOx、AlN、AlOxNy、Ti、TiN、Ta、TaN、TiOx、ZrOx、HfOx、及びTaOxからなる群より選択される材料を含む層をさらに有する、<30>に記載の方法。
<32>
前記接触工程の後に、前記半導体基板をリンス溶媒でリンスすることをさらに含む、<30>に記載の方法。
<33>
前記リンス工程の後に、前記半導体基板を乾燥させることをさらに含む、<32>に記載の方法。
<34>
前記半導体基板から半導体デバイスを形成することをさらに含む、<30>に記載の方法。
Claims (34)
- 1)組成物の0.5重量%~20重量%の量である少なくとも1種のレドックス剤;
2)水溶性アルコール類、水溶性ケトン類、水溶性エステル類、及び水溶性エーテル類からなる群より選択される少なくとも1種の有機溶媒であって、組成物の60重量%~90重量%の量である前記少なくとも1種の有機溶媒;
3)組成物の0.001重量%~0.5重量%の量である少なくとも1種の金属含有添加剤;並びに
4) 組成物の5重量%~28重量%の量である水、
を含み、
前記少なくとも1種の金属含有添加剤は、金属ハロゲン化物、金属水酸化物、金属ホウ化物、金属アルコキシド、金属酸化物、又は金属含有アンモニウム塩を含み、
前記金属酸化物は、第2A族金属、第3B族金属、又は第5B族金属を含む、
洗浄組成物。 - 7~11のpHを有する、請求項1に記載の組成物。
- 前記少なくとも1種のレドックス剤は、ヒドロキシルアミンを含む、請求項1又は請求項2に記載の組成物。
- 前記少なくとも1種のレドックス剤は、前記組成物の5重量%~20重量%である、請求項1~請求項3のいずれか1項に記載の組成物。
- 前記少なくとも1種の有機溶媒は、2種の有機溶媒を含む、請求項1~請求項4のいずれか1項に記載の組成物。
- 前記2種の有機溶媒は、それぞれ独立して、アルキレングリコール類及びアルキレングリコールエーテル類からなる群より選択される、請求項5に記載の組成物。
- 前記少なくとも1種の有機溶媒は、前記組成物の65重量%~90重量%である、請求項1~請求項6のいずれか1項に記載の組成物。
- 前記少なくとも1種の金属含有添加剤は、金属ハロゲン化物、金属水酸化物、金属ホウ化物、金属アルコキシド、又は金属含有アンモニウム塩を含む、請求項1~請求項7のいずれか1項に記載の組成物。
- 前記金属ハロゲン化物、金属水酸化物、金属ホウ化物、金属アルコキシド、又は金属含有アンモニウム塩は、第2A族金属、第3B族金属、第4B族金属、第5B族金属、又はランタニド金属を含む、請求項8に記載の組成物。
- 前記少なくとも1種の金属含有添加剤は、Ca、Ba、Ti、Hf、Sr、La、Ce、W、V、Nb、又はTaを含む、請求項9に記載の組成物。
- 前記少なくとも1種の金属含有添加剤は、前記組成物の0.001重量%~0.4重量%である、請求項1~請求項10のいずれか1項に記載の組成物。
- 前記水は、前記組成物の8重量%~28重量%である、請求項1~請求項11のいずれか1項に記載の組成物。
- pH調整剤をさらに含む、請求項1~請求項12のいずれか1項に記載の組成物。
- 前記pH調整剤は、1,8-ジアザビシクロ[5.4.0]-7-ウンデセン又は1,5-ジアザビシクロ[4.3.0]-5-ノネンである、請求項13に記載の組成物。
- 少なくとも1種の洗浄添加剤をさらに含む、請求項1~請求項14のいずれか1項に記載の組成物。
- 前記少なくとも1種の洗浄添加剤は、硫黄含有添加剤を含む、請求項15に記載の組成物。
- 前記硫黄含有添加剤は、チオール又はチオエーテルを含む、請求項16に記載の組成物。
- 前記硫黄含有添加剤は、3-アミノ-5-メルカプト-1H-1,2,4-トリアゾール、β-メルカプトエタノール、3-アミノ-5-メチルチオ-1H-1,2,4-トリアゾール、1-フェニル-1H-テトラゾール-5-チオール、4-メチル-4H-1,2,4-トリアゾール-3-チオール、2-ピリジンチオール、又は3-メルカプトプロピオン酸を含む、請求項17に記載の組成物。
- 前記硫黄含有添加剤は、前記組成物の0.01重量%~0.15重量%である、請求項16~請求項18のいずれか1項に記載の組成物。
- 前記少なくとも1種の洗浄添加剤は、アミノ酸を含む、請求項15~請求項19のいずれか1項に記載の組成物。
- 前記アミノ酸は、グリシンである、請求項20に記載の組成物。
- 前記アミノ酸は、前記組成物の0.01重量%~0.15重量%である、請求項20又は請求項21に記載の組成物。
- 少なくとも1種の有機酸をさらに含む、請求項1~請求項22のいずれか1項に記載の組成物。
- 前記少なくとも1種の有機酸は、カルボン酸又はスルホン酸を含む、請求項23に記載の組成物。
- 前記少なくとも1種の有機酸は、前記組成物の0.1重量%~0.5重量%である、請求項23又は請求項24に記載の組成物。
- 水酸化第四級アンモニウム類、第四級アンモニウム塩類、及びイミダゾリウム塩類からなる群より選択される少なくとも1種の導電性向上剤をさらに含む、請求項1~請求項25のいずれか1項に記載の組成物。
- 前記導電性向上剤は、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラブチルアンモニウム、塩化テトラブチルアンモニウム、水酸化ベンジルトリメチルアンモニウム、又は1-ブチル-3-メチルイミダゾリウムメタンスルホネートである、請求項26に記載の組成物。
- 前記少なくとも1種の導電性向上剤は、前記組成物の1重量%~10重量%である、請求項26又は請求項27に記載の組成物。
- 前記pH調整剤は、前記組成物の0.1重量%~3重量%である、請求項13又は14に記載の組成物。
- エッチング後の残渣又はアッシング後の残渣を含む半導体基板を、請求項1~請求項29のいずれか1項に記載の洗浄組成物と接触させることを含む、方法。
- 前記半導体基板は、Cu、Co、W、AlOx、AlN、AlOxNy、Ti、TiN、Ta、TaN、TiOx、ZrOx、HfOx、及びTaOxからなる群より選択される材料を含む層をさらに有する、請求項30に記載の方法。
- 前記接触工程の後に、前記半導体基板をリンス溶媒でリンスすることをさらに含む、請求項30又は請求項31に記載の方法。
- 前記リンス工程の後に、前記半導体基板を乾燥させることをさらに含む、請求項32に記載の方法。
- 前記半導体基板から半導体デバイスを形成することをさらに含む、請求項30~請求項33のいずれか1項に記載の方法。
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US10752867B2 (en) | 2018-03-28 | 2020-08-25 | Fujifilm Electronic Materials U.S.A., Inc. | Cleaning compositions |
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