CN103975052B - 具有铜/唑类聚合物抑制作用的微电子衬底清洁组合物 - Google Patents
具有铜/唑类聚合物抑制作用的微电子衬底清洁组合物 Download PDFInfo
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- CN103975052B CN103975052B CN201280059946.4A CN201280059946A CN103975052B CN 103975052 B CN103975052 B CN 103975052B CN 201280059946 A CN201280059946 A CN 201280059946A CN 103975052 B CN103975052 B CN 103975052B
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- 239000000203 mixture Substances 0.000 title claims abstract description 161
- 238000004377 microelectronic Methods 0.000 title claims abstract description 29
- 239000000758 substrate Substances 0.000 title claims description 37
- 229920000642 polymer Polymers 0.000 title claims description 21
- 239000010949 copper Substances 0.000 title description 41
- 229910052802 copper Inorganic materials 0.000 title description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title description 16
- 230000002401 inhibitory effect Effects 0.000 title description 3
- 238000005260 corrosion Methods 0.000 claims abstract description 56
- 230000007797 corrosion Effects 0.000 claims abstract description 55
- 239000003112 inhibitor Substances 0.000 claims abstract description 47
- -1 cyclic amide compound Chemical class 0.000 claims abstract description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000008442 polyphenolic compounds Polymers 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 238000004140 cleaning Methods 0.000 claims abstract description 17
- 150000001412 amines Chemical class 0.000 claims abstract description 15
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- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 7
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- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 23
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- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 16
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- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
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- 229940093476 ethylene glycol Drugs 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
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- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 claims description 7
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
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- 125000003831 tetrazolyl group Chemical group 0.000 claims description 7
- 239000006184 cosolvent Substances 0.000 claims description 6
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 6
- 229940043276 diisopropanolamine Drugs 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
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- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 5
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 5
- UGAQMGXCNYQXHP-UHFFFAOYSA-N 1-ethoxypyrrolidin-2-one Chemical compound CCON1CCCC1=O UGAQMGXCNYQXHP-UHFFFAOYSA-N 0.000 claims description 5
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 5
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 claims description 5
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 claims description 5
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 5
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- 238000005530 etching Methods 0.000 claims description 5
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- 150000002596 lactones Chemical class 0.000 claims description 5
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 5
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 5
- RJLKIAGOYBARJG-UHFFFAOYSA-N 1,3-dimethylpiperidin-2-one Chemical class CC1CCCN(C)C1=O RJLKIAGOYBARJG-UHFFFAOYSA-N 0.000 claims description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 4
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 238000001020 plasma etching Methods 0.000 claims description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 3
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 3
- FPEANFVVZUKNFU-UHFFFAOYSA-N 2-sulfanylbenzotriazole Chemical compound C1=CC=CC2=NN(S)N=C21 FPEANFVVZUKNFU-UHFFFAOYSA-N 0.000 claims description 3
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 3
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- 239000011521 glass Substances 0.000 claims description 3
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 3
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 claims description 2
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- QIVFLUKTWJNKHQ-UHFFFAOYSA-N 2-methyl-1H-benzimidazole-4-thiol Chemical compound C1=CC(S)=C2NC(C)=NC2=C1 QIVFLUKTWJNKHQ-UHFFFAOYSA-N 0.000 claims description 2
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims description 2
- CUZKCNWZBXLAJX-UHFFFAOYSA-N 2-phenylmethoxyethanol Chemical compound OCCOCC1=CC=CC=C1 CUZKCNWZBXLAJX-UHFFFAOYSA-N 0.000 claims description 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 claims description 2
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- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 claims description 2
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- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 claims 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
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- WYMDDFRYORANCC-UHFFFAOYSA-N 2-[[3-[bis(carboxymethyl)amino]-2-hydroxypropyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)CN(CC(O)=O)CC(O)=O WYMDDFRYORANCC-UHFFFAOYSA-N 0.000 description 1
- XWSGEVNYFYKXCP-UHFFFAOYSA-N 2-[carboxymethyl(methyl)amino]acetic acid Chemical compound OC(=O)CN(C)CC(O)=O XWSGEVNYFYKXCP-UHFFFAOYSA-N 0.000 description 1
- MBIQENSCDNJOIY-UHFFFAOYSA-N 2-hydroxy-2-methylbutyric acid Chemical class CCC(C)(O)C(O)=O MBIQENSCDNJOIY-UHFFFAOYSA-N 0.000 description 1
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
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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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
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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
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- C11D7/22—Organic compounds
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- C11D7/261—Alcohols; Phenols
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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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or 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
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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
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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
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
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- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
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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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- C11D7/22—Organic compounds
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Abstract
本发明涉及pH>8的半水性、碱性的微电子清洁组合物,包含:(A)至少一种与水接触时会产生氢氧化物的仲链烷醇胺;(B)以乙酸正丁酯的蒸发速率为基准速率1.0计,蒸发速率为0.3或更低的至少一种有机醇醚溶剂;(C)至少一种抑制腐蚀的环状酰胺化合物;(D)占组合物重量的0.08%或更低的至少一种平衡pH的唑类金属腐蚀抑制剂;和(E)水;以及任选的(F)至少一种多羟基酚类类化合物腐蚀抑制剂;和(G)包含邻位羟基或邻位巯基以与多羟基酚类类化合物腐蚀抑制剂进行配对的至少一种多元醇或多元硫醇表面改性剂。
Description
技术领域
本发明涉及一种用于通过去除光刻胶、UV/等离子硬化的光刻胶以及等离子蚀刻后(post plasma etch)或蚀刻/灰化后(post etch/ash)残留物而清洁微电子衬底的组合物,并且能在这样做的同时与铝、铜和低κ电介质(low-kdielectrics)以及特别是多孔的低κ电介质相容。特别地,本发明实质上提供了半水基的清洁剂组合物并且还提供了用于清洁微电子衬底的方法和使用这种组合物的装置。
背景技术
制造半导体装置通过以下步骤:用光刻胶涂覆无机衬底;通过曝光来图案化光刻胶膜以及在这之后显影;利用图案化的光刻胶膜作为掩模来蚀刻无机衬底所曝光的区域以形成精密电路;以及从无机衬底上去除图案化的光刻胶膜。可选地,在按如上述相同的方式形成精密电路后,灰化所述图案化的光刻胶膜,然后从无机衬底上去除余留的光刻胶残余物。
为剥离光刻胶(PR)、UV/等离子硬化的PR以及等离子蚀刻/灰化残留物,单独使用普通的有机溶剂一般不能有效提供所需的清洁能力。特定的活性剂例如氟化物和碱(alkaline base)常用于微电子制剂。然而,许多碱例如胺和氢氧化铵会导致严重的金属腐蚀。腐蚀抑制剂的使用可以减轻/减少这种金属腐蚀,但通常不能针对严重的腐蚀情况/制剂提供足够的保护。因此,工作组合物在无腐蚀抑制剂的情况下必须是与金属完全或“合理相容”的。为了满足现代微电子性能的要求,将“合理相容”定义为“具有或更小的金属蚀刻速率”。将“完全相容”定义为“具有或更小的金属蚀刻速率”。
在碱性的pH条件下,微电子组合物在湿PR剥离以及随后的水冲洗过程中经常会遇到较差的金属堆栈(metal stack)兼容性。金属堆栈的电偶腐蚀带来了更大的挑战。腐蚀抑制剂的使用往往会造成表面改性或在表面上留下残余物,从而导致不期望的电性能变化。
建议在这样的微电子清洁组合物中使用的众多类型的腐蚀抑制剂中包括唑类(azole),尤其是四唑和三唑类,特别是苯并三唑,并且以0.2~2%或更高的水平来使用它们。具有这样的所提及的唑类,尤其是苯并三唑用作腐蚀抑制剂的清洁剂的实例包括,但不限于EP1178359、EP1,752,829、WO2007/111694、US2009/0170037和WO2007/044446。使用苯并三唑作为腐蚀抑制剂的这些清洁组合物通常是基于非水性的有机溶剂的清洁组合物。但是在US2003/144162中的第[0042]段指出苯并三唑并不防止铜的腐蚀。然而,虽然在一些情况下,通常在基于非水性溶剂的清洁组合物中,这些三唑类看起来会为铜提供相当不错的防腐蚀保护,但是我们发现三唑类,例如苯并三唑强烈倾向于在铜表面形成紧密结合的聚合物络合物,其被认为是Cu离子/唑类络合物,例如Cu离子/苯并三唑络合物,下文分别称为Cu(l)/唑类聚合物和Cu(I)/BZT聚合物。若是这样的聚合物的沉积过厚或不受控制,则该Cu(I)/唑类聚合物的形成会导致不利影响。当苯并三唑被用作腐蚀抑制剂时,在铜的表面上形成这种不受期望的Cu(I)/BZT聚合物的现象是特别普遍的,并且尤其是当在具有苯并三唑的清洁组合物中应用二甲基亚砜(DMSO)作为主要的溶剂组分之一时,会造成厚的Cu(l)/BZT聚合物。已发现这些Cu(I)/BZT聚合物会紧密结合到铜的表面并且在于剥离/清洗过程后使用的一般的水清洗过程之后残留在铜的表面。这样的问题已被发现普遍存在于适用平板显示器的衬底中。
对于另一类金属,特别是铜和铝来说,建议使用在这样的清洁组合物中的腐蚀抑制剂为包含邻位羟基的多羟基酚类化合物,例如邻苯二酚、连苯三酚和没食子酸(gallic acid)。使用这样的多羟基酚类化合物作为腐蚀抑制剂的一个缺点是,它们倾向于在被清洗的硅晶片上紧密结合至硅烷醇。即使少量的这种结合也修饰硅表面,且导致性能下降。
因此,丞需一种微电子清洁组合物,其可采用不会形成Cu(I)/唑类聚合物或具有最小化的Cu(I)/唑类聚合物的形成或具有抑制的Cu(I)/唑类聚合物的形成的唑类腐蚀抑制剂。特别需要这样的清洁组合物,其可以是半水性的并且即使在使用该清洁组合物清洗衬底后的水性清洗阶段也不会产生明显的金属腐蚀。额外需要这样的清洁组合物,其对于清洗铝和铜金属化的微电子器件来说表现优异。进一步需要提供这样的清洁组合物,其抑制被用作腐蚀抑制剂的多羟基酚类化合物结合至被清洗的硅晶片上的硅烷醇,并由此抑制了由多羟基酚类腐蚀抑制剂造成的微电子衬底的表面改性。
发明内容
本发明的清洁组合物是半水性的、pH≥8的碱性微电子清洁组合物,其包含以下成分、基本由以下成分组成为或由以下成分组成:
(A)与水接触时生成氢氧化物的至少一种仲链烷醇胺;
(B)以乙酸正丁酯的蒸发速率(evaporation rate)为基准速率1.0计,蒸发速率为0.3或更低的至少一种有机醇醚溶剂;
(C)至少一种抑制腐蚀的环状酰胺化合物;
(D)占该组合物重量的0.08%或更少的至少一种平衡pH的唑类金属腐蚀抑制剂;和
(E)水
以及任选的
(F)至少一种多羟基酚类化合物腐蚀抑制剂;和
(G)至少一种包含邻位羟基或邻位巯基以与所述多羟基酚类化合物腐蚀抑制剂配对的多元醇或多元硫醇表面改性剂。
如果在本发明的组合物中存在组分(F),那么也存在组分(G)。然而,该组合物可以包含组分(G)而不含组分(F)。
本发明的清洁组合物还可任选地包含其他非必要的但有时会需要的组分,例如,
(H)至少一种选自亚砜、砜、酰胺、内酯、醚、醇、叔链烷醇胺和除了那些用作组分(B)的醇醚以外的醇醚的极性有机溶剂/共溶剂;和
(I)至少一种表面活性剂;和
(J)至少一种金属螯合剂或络合剂。
本发明的组合物可用于通过去除光刻胶、UV/等离子硬化的光刻胶以及等离子蚀刻后或蚀刻/灰化后的残留物来清洗微电子衬底,并且能在这样做的同时与铝、铜和低κ电介质以及特别是多孔的低κ电介质相容。为了完成微电子衬底或器件的清洗,使微电子衬底或器件与本发明的组合物在一个足以实现这样的清洗过程的温度接触一段时间。
发明详述
本发明的清洁组合物是微电子清洁组合物,其可采用不会形成Cu(I)/BZT聚合物或具有最小化的Cu(I)/BZT聚合物的形成或具有抑制的Cu(I)/BZT聚合物的形成的唑类腐蚀抑制剂。这样的微电子清洁组合物是半水性的、pH≥8的碱性微电子清洁组合物,其包含以下成分、基本由以下成分组成为或由以下成分组成:
(A)与水接触时生成氢氧化物的至少一种仲链烷醇胺;
(B)以乙酸正丁酯的蒸发速率为基准速率1.0计,蒸发速率为0.3或更低的至少一种有机醇醚溶剂;
(C)至少一种抑制腐蚀的环状酰胺化合物;
(D)占该组合物重量的0.08%或更少的至少一种平衡pH的唑类金属腐蚀抑制剂;和
(E)水。
这样的组合物能够清洗铝和铜金属化的微电子衬底和也具有低κ电介质的衬底。所述衬底可以是任何在微电子器件制造中采用的衬底,特别是硅晶片和玻璃衬底。
在本发明的清洁组合物的另一实施方式中提供了这样的清洁组合物,其还包含用作腐蚀抑制剂的多羟基酚类化合物,该清洁组合物能抑制那些多羟基酚类化合物结合至被清洗的硅晶片上的硅烷醇,并由此抑制了由多羟基酚类腐蚀抑制剂造成的微电子衬底的表面改性。在本发明的清洁组合物的这样的另一实施方式中,该清洁组合物可额外包含:
(F)至少一种多羟基酚类化合物腐蚀抑制剂;和
(G)至少一种包含邻位羟基或邻位巯基以与所述多羟基酚类化合物腐蚀抑制剂配对的多元醇或多元硫醇表面改性剂。如果在本发明的组合物中存在组分(F),那么也存在组分(G)。然而,该组合物可以包含组分(G)而不含组分(F)。
这样的组合物还能够清洗铝和铜金属化的微电子衬底。
本发明的清洁组合物还可任选地包含其他非必要的但有时会需要的组分,例如,
(H)至少一种选自亚砜、砜、酰胺、内酯、醚、醇、叔链烷醇胺和除了那些用作组分(B)的醇醚以外的醇醚的极性有机溶剂/共溶剂;和
(I)至少一种表面活性剂;和
(J)至少一种金属螯合剂或络合剂。
本发明的半水性的碱性微电子清洁组合物具有的pH≥8,优选pH≥9.5,这两者均在未稀释的情况下(“表观pH”),并作为10%的水溶液。
存在于该清洁组合物中的与水接触时生成氢氧化物的至少一种仲链烷醇胺通常占该清洁组合物的重量的约0.1%~约50%,优选约0.5%~约25%,更优选约3%~约15%,以及进一步优选约6%。任何适合的与水接触时生成氢氧化物的仲链烷醇胺可用于本发明的组合物。这样适合的仲链烷醇胺的实例包括,但不限于:二乙醇胺、二异丙醇胺、N-乙基乙醇胺和N-甲基乙醇胺以及它们的混合物。
任何适合的以乙酸正丁酯的蒸发速率为基准速率1.0计,蒸发速率为0.3或更低的有机醇醚溶剂可用于本发明的清洁组合物。优选二醇醚。存在于该清洁组合物中的该有机醇醚溶剂通常占该组合物的重量的约5%~约95%,优选约20%~约80%,更优选约45%~约70%。这样适合的有机醇醚溶剂的实例包括,但不限于:乙二醇丁醚(EGBE)、二乙二醇单甲醚(DEGME)、二乙二醇单乙醚(DEGEE,卡必醇)、丁基乙二醇(butyl glycol)、四乙二醇、二丙二醇甲基醚、乙二醇单甲醚(EGME)、乙二醇单乙醚(EGEE)、乙二醇单丙醚(EGPE)、二甘醇(DEG)、二乙二醇单乙醚(DEGEE)、二乙二醇单丁醚(DEGBE)、丙二醇单甲醚(PGME)、二丙二醇(DPG)、二丙二醇单甲醚(DPGME)、乙二醇单异丙醚、乙二醇单苯醚、乙二醇单苄醚、三乙二醇甲基醚、三乙二醇乙基醚、三乙二醇丁基醚和它们的混合物。优选的有机醇醚溶剂选自乙二醇丁醚、二乙二醇单甲醚、二乙二醇单乙基醚、丁基乙二醇、四乙二醇、二丙二醇甲基醚和它们的混合物。进一步优选为乙二醇丁醚。
存在于该组合物中的至少一种抑制腐蚀的环状酰胺化合物通常占该组合物的重量的约5%~约70%,优选约5%~约50%,更优选约10%~约30%,进一步优选约10%~约20%。任何适合的抑制腐蚀的环状酰胺化合物可用于本发明的组合物。这样适合的抑制腐蚀的环状酰胺化合物的实例包括,但不限于:N-甲基吡咯烷酮、N-乙基吡咯烷酮、N-丙基吡咯烷酮、二甲基-2-哌啶酮、1-(2-羟乙基)-2-吡咯烷酮、β-内酰胺、γ-内酰胺、δ-内酰胺、ε-内酰胺、4-氨基戊酸内酰胺(γ-戊内酰胺)和它们的混合物。抑制腐蚀的环状酰胺化合物优选为N-甲基吡咯烷酮、N-乙基吡咯烷酮、N-丙基吡咯烷酮、二甲基-2-哌啶酮、1-(2-羟乙基)-2-吡咯烷酮和它们的混合物。该环状酰胺化合物进一步优选为N-甲基吡咯烷酮。
存在于该组合物中的至少一种平衡pH的唑类金属腐蚀抑制剂组分的量必须不超过该组合物的重量的约0.08%,优选不超过约0.07%,更优选不超过约0.05%,并且在一个优选的实施方式中不超过该组合物的重量的约0.01%。任何适合的平衡pH的唑类金属腐蚀抑制剂,特别是三唑类和四唑类可用于本发明的组合物。这样适合的平衡pH的唑类腐蚀抑制剂的实例包括,但不限于:苯并三唑、烷基苯并三唑例如甲基苯并三唑(例如4-或5-甲基苯并三唑)、羧基苯并三唑、苯并咪唑、四唑、羟基苯并三唑、2-巯基苯并三唑、2-巯基苯并咪唑、甲苯基三唑、巯基甲基苯并咪唑、1,2,4-三唑、3-氨基-1,2,4-三唑、1-苯基-1H-四唑-5-硫醇和它们的混合物。唑类金属腐蚀抑制剂优选为苯并三唑、羧基苯并三唑、苯并咪唑、四唑、羟基苯并三唑、2-巯基苯并三唑、2-巯基苯并咪唑和它们的混合物。唑类金属腐蚀抑制剂进一步优选为苯并三唑和甲基苯并三唑。
本发明的清洁组合物是半水性的。存在于该组合物中的水通常占该组合物的重量的约5%~约70%,优选约5%~约40%,更优选约10%~约30%,并且在一个优选的实施方式中占该组合物的重量的约20%。
在本发明的清洁组合物的另一个实施方式中,该组合物包含任何适合的多羟基酚类腐蚀抑制剂化合物,当存在于组合物中时,其量通常为该组合物的重量的大于0%~约10%,优选约0.1%~约5%,更优选约0.1%~约1%以及进一步优选约0.1%~约0.5%。可使用任何适合的多羟基酚类腐蚀抑制剂化合物且包括,但不限于:邻苯二酚(儿茶酚)、连苯三酚、没食子酸、没食子酸烷基酯(例如没食子酸甲酯、没食子酸丙酯)、烷基邻苯二酚(例如甲基邻苯二酚、乙基邻苯二酚和叔丁基邻苯二酚)和它们的混合物。该多羟基酚类腐蚀抑制剂化合物优选为邻苯二酚(儿茶酚)、连苯三酚、没食子酸和它们的混合物。该多羟基酚类腐蚀抑制剂化合物进一步优选为邻苯二酚。
当本发明的组合物包含上述多羟基酚类腐蚀抑制剂化合物时,该组合物还包含至少一种多元醇或多元硫醇表面改性抑制剂,其含有邻位羟基或邻位巯基以与所述多羟基酚类化合物腐蚀抑制剂配对,从而起到表面改性防止剂的作用以防止或抑制多羟基酚类化合物结合至被清洗的硅晶片上的硅烷醇。然而,即使不存在多羟基酚类化合物腐蚀抑制剂组分时,所述包含邻位羟基或邻位巯基的至少一种多元醇或多元硫醇表面改性抑制剂也可任选地存在于本发明的组合物中。任何适合的多元醇或多元硫醇表面改性抑制剂可用于本发明的组合物。这样的适合的多元醇或多元硫醇表面改性抑制剂的实例包括,但不限于:链烷二醇、链烷三醇、链烷二硫醇、苯基取代的链烷二醇、苯基取代的链烷三醇、苯基取代的链烷二硫醇和它们的混合物。多元醇或多元硫醇表面改性抑制剂的具体实例包括,但不限于:乙二醇、丙二醇、甘油、丁二醇、戊二醇、己二醇、环己二醇、1,2-乙二硫醇和它们的混合物。该多元醇或多元硫醇表面改性抑制剂优选包括乙二醇、丙二醇、甘油、丁二醇、1,2-乙二硫醇和它们的混合物。若是这样的多元醇或多元硫醇表面改性抑制剂化合物存在于该组合物中,则其在该组合物中的量通常为该组合物的重量的大于0%~约20%,优选约1%~约10%,更优选约3%~约10%以及进一步优选约5%~约10%。
本发明的清洁组合物也可任选地具有存在于该组合物中的至少一种或多种以下组分:
(H)至少一种选自亚砜、砜、酰胺、内酯、醚、醇、叔链烷醇胺和除了那些用作组分(B)的醇醚以外的醇醚的极性有机溶剂/共溶剂;和
(I)至少一种表面活性剂;和
(J)至少一种金属螯合剂或络合剂。
选自亚砜、砜、酰胺、内酯、醚、醇、叔链烷醇胺和那些用作组分(B)的醇醚以外的醇醚的任何适合的其他极性有机溶剂/共溶剂可被任选地用于本发明的组合物,并且当使用时其在该组合物中的量通常为该组合物的重量的大于0%~约50%,优选约5%~约50%,更优选约5%~约25%。这样的适合的其他极性有机溶剂/共溶剂包括,但不限于:二甲亚砜、环丁砜、二甲基砜、二乙基砜、二甲基乙酰胺、甲酰胺、丁内酯、乙二醇二甲醚、乙二醇二乙醚、乙二醇二丁醚、三乙醇胺、N-甲基甲酰胺、N,N-二甲基甲酰胺、苯甲醇、丙醇、丁醇、三乙醇胺、乙二醇和它们的混合物。极性有机溶剂/共溶剂优选为二甲亚砜、环丁砜、二甲基砜、二乙基砜、二甲基乙酰胺、甲酰胺、三乙醇胺和N-甲基甲酰胺。
任何适合的表面活性剂可被任选地用于本发明的组合物。该表面活性剂可以是任何适合的两性、阳离子、阴离子或非离子表面活性剂。用于本发明的组合物的两性表面活性剂包括,但不限于:甜菜碱类和磺基甜菜碱类(sulfobetaines),例如烷基甜菜碱、酰胺基烷基甜菜碱(amidoalkyl betaines)、烷基磺基甜菜碱和酰胺基烷基磺基甜菜碱(amidoalkyl sulfobetaines);氨基羧酸衍生物,例如两性甘氨酸盐、两性丙酸盐、两性二甘氨酸盐和两性二丙酸盐;亚氨基二酸,例如烷氧基烷基亚氨基二酸或烷氧基烷基亚氨基二酸;氧化胺,例如烷基胺氧化物和烷基酰胺基烷基胺氧化物;氟代烷基磺酸盐和氟代烷基两性表面活性剂;和它们的混合物。所述两性表面活性剂优选为椰油酰胺基丙基甜菜碱、椰油酰胺基丙基二甲基甜菜碱、椰油酰胺基丙基羟基磺基甜菜碱、辛酰两性二丙酸盐、椰油酰胺基二丙酸盐、椰油两性丙酸盐、椰油两性羟乙基丙酸盐、异癸氧基丙基亚氨基二丙酸、月桂基亚氨基二丙酸盐、椰油酰胺基丙胺氧化物和椰油胺氧化物以及氟代烷基两性表面活性剂。用于本发明组合物的非离子表面活性剂包括,但不限于:炔二醇、乙氧基化炔二醇、氟代烷基烷氧基化物、氟代烷基酯、氟代聚氧化乙烯链烷醇、多元醇的脂肪酸酯、聚氧化乙烯一烷基醚、聚氧化乙烯二醇、硅氧烷型表面活性剂和亚烷基二醇一烷基醚。所述非离子表面活性剂优选为炔二醇或乙氧基化炔二醇。用于本发明的组合物的阴离子表面活性剂包括,但不限于:羧酸盐、N-酰基肌氨酸盐、磺酸盐、硫酸盐、正磷酸的一酯和二酯,例如磷酸癸酯。所述阴离子表面活性剂优选为不含金属的表面活性剂。用于本发明的组合物的阳离子表面活性剂包括,但不限于:胺乙氧基化物(amine ethoxylates)、二烷基二甲基铵盐、二烷基吗啉盐、烷基苯甲基二甲基铵盐、烷基三甲基铵盐和烷基吡啶盐。所述阳离子表面活性剂优选为不含卤素的表面活性剂。如果使用表面活性剂组分,则其优选为炔二醇表面活性剂。特别适合的表面活性剂的实例包括,但不限于:3,5-二甲基-1-己炔-3-醇(Surfynol-61)、乙氧基化2,4,7,9-四甲基-5-癸炔-4,7-二醇(Surfynol-465)、聚四氟乙烯鲸蜡氧基丙基甜菜碱(polytetrafluoroethylene cetoxypropyl-betaine)(Zonyl FSK)、ZonylFSH、Triton X-100,即辛基苯氧基聚乙氧基乙醇等。在存在这样的表面活性剂组分的情况下,其量通常为该组合物的重量的大于0%~约5%,优选约0.01%~约1%,更优选约0.01%~约0.2%。
在本发明的组合物中可任选地包含任何适合的金属螯合剂或络合剂,并且在存在金属螯合剂或络合剂的情况下,其量通常为该组合物的重量的大于0%~约5%,优选约0.01%~约5%,更优选约0.1%~约1%。这样的适合的金属螯合剂或络合剂包括,但不限于下列的有机酸和它们的异构体及盐:(乙二胺)四乙酸(EDTA)、丁二胺四乙酸、环己-1,2-二胺四乙酸(CyDTA)、二亚乙基三胺五乙酸(DETPA)、乙二胺四丙酸、(羟乙基)乙二胺三乙酸(HEDTA)、N,N,N',N'-乙二胺四(亚甲基膦酸)(EDTMP)、三亚乙基四胺六乙酸(TTHA)、1,3-二氨基-2-羟基丙烷-N,N,N',N'-四乙酸(DHPTA)、甲基亚氨基二乙酸、丙二胺四乙酸、次氮基三乙酸(NTA)、氨基三亚甲基膦酸、柠檬酸、酒石酸、葡萄糖酸、葡糖二酸、甘油酸、草酸、邻苯二甲酸、马来酸、扁桃酸、丙二酸、乳酸、水杨酸、8-羟基喹啉和半胱氨酸。所述金属螯合剂优选为氨基羧酸例如环己-1,2-二胺四乙酸和1,3-二氨基-2-羟基丙烷-N,N,N',N'-四乙酸。
本发明的清洁组合物不仅在以未稀释的(纯的)形式使用时,而且在清洗之后的水冲洗阶段将其用大量的水稀释时均与铜和铝的金属化层(metallizations)相容。例如,在使用95:5的水:清洁混合物的情况下,本发明的组合物具有低的Al和Cu腐蚀速率。此外,本发明的组合物即使是在非常苛刻的高氧/空气暴露的条件下也能表现出良好的铝和铜的相容性。即使使空气鼓泡穿过该清洁组合物也能获得低的腐蚀速率。
可使用本发明的组合物来清洗具有铝或铜的金属化层的微电子衬底,尤其是具有低κ电介质的那些衬底。在足以清洗具有光刻胶、UV/等离子硬化的光刻胶和等离子蚀刻后或蚀刻/灰化后的残留物中的一个或多个的衬底的温度下,使所述清洁组合物与微电子衬底接触一段时间。之后可以用大量的水稀释该组合物以提供在清洗步骤之后的要在衬底上使用的冲洗液。衬底与清洁组合物的接触时间可以为约1分钟~约30分钟,以及可以在约25℃~约85℃的温度进行。
本发明的组合物的优选实施方式的实例包括,但不限于下列组合物。表1中使用了下列缩写:
EGBE=乙二醇丁醚
NMP=N-甲基吡咯烷酮
EG=乙二醇
PG=丙二醇
PEG200=聚乙二醇200
H2O=水
DEA=二乙醇胺
CAR=卡必醇
BZT=苯并三唑
MBZT=甲基苯并三唑
CAT=邻苯二酚
表1:
表中的量均以重量份表示。与具有大于0.08%的唑类组分的类似组合物相比,并且与不含蒸发速率为0.3或更低的至少一种有机醇醚溶剂的类似组合物相比,或与不含与水接触时生成氢氧化物的至少一种仲链烷醇胺的类似组合物相比,或与不含至少一种抑制腐蚀的环状酰胺化合物的类似组合物比较,这些组合物1~6抑制Cu离子/唑类复合物的形成。
实施例1
表2中的数据显示出本发明的组合物的有利的衬底相容性/腐蚀速率。
表2
接下来的实施例显示仲醇与环状酰胺腐蚀抑制剂组分的组合降低Cu(l)/唑类聚合物或使其最小化的属性。
实施例2
60℃时,于100rpm的搅拌速率搅拌的情况下,通过将硅衬底晶片浸渍在由40重量份的二甲亚砜、6重量份的二乙醇胺、60份重量的水和0.5重量份的苯并三唑组成的清洁组合物中20分钟来产生Cu/BZT聚合物,以制造载有不受期望的Cu/BZT聚合物的衬底。将所得到的不受期望的Cu/BZT聚合物衬底切割成大小相等的片。然后,于60℃时在300rpm的搅拌速率的情况下将每一片载有Cu/BZT聚合物的衬底浸渍在不同的溶液中一段指定的时间。对这些经溶液处理的衬底片进行检查和评估以得到Cu/BZT聚合物的去除效率,其中Cu/BZT聚合物负载的标度为0=(表示没有可检测到的Cu/BZT聚合物负载)到10(表示非常严重的Cu/BZT聚合物负载量)。结果参见表3,其中DEA=二乙醇胺,NMP=N-甲基吡咯烷酮以及DMSO=二甲基亚砜。
表3:
尽管参考特定的实施方式本法发明已被揭露如上,但可理解的是,只要不脱离本发明的精神和范围均可作出改变、修改和变化。因此,所作的改变、修改和变化应当落入所附的权利要求的范围内。
Claims (18)
1.一种半水性的、pH≥8的碱性微电子清洁组合物,其包含:
(A)与水接触时生成氢氧化物的至少一种仲链烷醇胺;
(B)当以乙酸正丁酯的蒸发速率为基准速率1.0计,蒸发速率为0.3或更低的至少一种有机醇醚溶剂;
(C)至少一种抑制腐蚀的环状酰胺化合物;
(D)占该组合物重量的0.08%或更少的至少一种平衡pH的唑类金属腐蚀抑制剂;和
(E)水;
以及任选的
(F)至少一种多羟基酚类化合物腐蚀抑制剂;和
(G)至少一种包含邻位羟基或邻位巯基与所述至少一种多羟基酚类化合物腐蚀抑制剂配对的多元醇或多元硫醇表面改性剂,其条件为,如果在所述组合物中存在组分(F),那么也存在组分(G),但是所述组合物可以包含组分(G)而不含组分(F)。
2.根据权利要求1所述的半水性的碱性微电子清洁组合物,其中在所述组合物中同时存在任选组分(F)和(G)。
3.根据权利要求1所述的组合物,其中所述组合物的pH≥9.5。
4.根据权利要求1所述的组合物,其中所述仲链烷醇胺组分(A)在所述组合物中存在的量为0.1重量%~50重量%,所述有机醇醚溶剂(B)在所述组合物中存在的量为5重量%~95重量%,所述环状酰胺腐蚀抑制剂组分(C)在所述组合物中存在的量为5重量%~70重量%,所述唑类金属腐蚀抑制剂组分(D)在所述组合物中存在的量为不超过0.07重量%,以及所述水组分(E)在所述组合物中存在的量为5重量%~75重量%,其中所述重量百分比基于所述组合物的重量。
5.根据权利要求1所述的组合物,其中所述仲链烷醇胺组分(A)选自二乙醇胺、二异丙醇胺、N-乙基乙醇胺、N-甲基乙醇胺及它们的混合物。
6.根据权利要求1所述的组合物,其中所述有机醇醚溶剂组分(B)选自乙二醇丁醚、二乙二醇单甲醚、卡必醇、丁基乙二醇、四乙二醇、二丙二醇甲基醚、乙二醇单甲醚、乙二醇单乙醚、乙二醇单丙醚、二甘醇、二乙二醇单乙醚、二乙二醇单丁醚、丙二醇单甲醚、二丙二醇、二丙二醇单甲醚、乙二醇单异丙醚、乙二醇单苯醚、乙二醇单苄醚、三乙二醇甲基醚、三乙二醇乙基醚、三乙二醇丁基醚和它们的混合物。
7.根据权利要求6所述的组合物,其中所述有机醇醚溶剂组分(B)选自乙二醇丁醚、二乙二醇单甲醚、卡必醇、丁基乙二醇、四乙二醇、二丙二醇甲基醚和它们的混合物。
8.根据权利要求1所述的组合物,其中所述环状酰胺组分(C)选自N-甲基吡咯烷酮、N-乙基吡咯烷酮、二甲基-2-哌啶酮、1-(2-羟乙基)-2-吡咯烷酮、β-内酰胺、γ-内酰胺、δ-内酰胺、ε-内酰胺、4-氨基戊酸内酰胺(γ-戊内酰胺)和它们的混合物。
9.根据权利要求8所述的组合物,其中所述环状酰胺组分(C)选自N-甲基吡咯烷酮、N-乙基吡咯烷酮、二甲基-2-哌啶酮、1-(2-羟乙基)-2-吡咯烷酮和它们的混合物。
10.根据权利要求1所述的组合物,其中所述唑类组分(D)选自苯并三唑、烷基苯并三唑、苯并咪唑、四唑、羟基苯并三唑、羧基苯并三唑、2-巯基苯并三唑、2-巯基苯并咪唑、甲苯基三唑、巯基甲基苯并咪唑、1,2,4-三唑、3-氨基-1,2,4-三唑、1-苯基-1H-四唑-5-硫醇和它们的混合物。
11.根据权利要求10所述的组合物,其中所述唑类组分(D)选自苯并三唑、甲基苯并三唑、苯并咪唑、四唑、羟基苯并三唑、羧基苯并三唑、2-巯基苯并三唑、2-巯基苯并咪唑和它们的混合物。
12.根据权利要求1所述的组合物,其中所述多羟基酚类组分(F)选自邻苯二酚、连苯三酚、没食子酸、没食子酸烷基酯、烷基儿茶酚和它们的混合物,以及所述多元醇或多元硫醇组分(G)选自链烷二醇、链烷三醇、链烷二硫醇、苯基取代的链烷二醇、苯基取代的链烷三醇、苯基取代的链烷二硫醇和它们的混合物。
13.根据权利要求12所述的组合物,其中所述多羟基酚类组分(F)选自邻苯二酚、连苯三酚、没食子酸和它们的混合物,以及所述多元醇或多元硫醇组分(G)选自乙二醇、丙二醇、甘油、丁二醇、环己二醇,1,2-亚乙基二硫醇和它们的混合物。
14.根据权利要求1所述的组合物,其中所述仲链烷醇胺组分(A)选自二乙醇胺、二异丙醇胺、N-乙基乙醇胺、N-甲基乙醇胺及它们的混合物,所述有机醇醚溶剂组分(B)选自乙二醇丁醚、二乙二醇单甲醚、卡必醇、丁基乙二醇、四乙二醇、二丙二醇甲基醚和它们的混合物,所述环状酰胺组分(C)选自N-甲基吡咯烷酮、N-乙基吡咯烷酮、二甲基-2-哌啶酮、1-(2-羟乙基)-2-吡咯烷酮和它们的混合物,所述唑类组分(D)选自苯并三唑、甲基苯并三唑、羧基苯并三唑、苯并咪唑、四唑、羟基苯并三唑、2-巯基苯并三唑、2-巯基苯并咪唑和它们的混合物,以及所述多羟基酚类组分(F)选自邻苯二酚、连苯三酚、没食子酸和它们的混合物,以及所述多元醇或多元硫醇组分(G)选自乙二醇、丙二醇、甘油、丁二醇、1,2-亚乙基二硫醇和它们的混合物。
15.根据权利要求14所述的组合物,其中所述仲链烷醇胺组分(A)为二乙醇胺,所述有机醇醚溶剂组分(B)选自乙二醇丁醚、二乙二醇单甲醚、卡必醇、丁基乙二醇、四乙二醇、二丙二醇甲基醚,所述环状酰胺组分(C)为N-甲基吡咯烷酮,所述唑类组分(D)选自苯并三唑和甲基苯并三唑,以及所述多羟基酚类组分(F)为邻苯二酚,以及所述多元醇或多元硫醇组分(G)选自乙二醇和丙二醇。
16.根据权利要求1~15任一项所述的组合物,其额外包含下列额外的组分中的至少一种:
(H)至少一种选自亚砜、砜、酰胺、内酯、醚、醇、叔链烷醇胺和除了那些用作组分(B)的醇醚以外的醇醚的极性有机溶剂/共溶剂;和
(I)至少一种表面活性剂;和
(J)至少一种金属螯合剂或络合剂。
17.通过从衬底去除光刻胶、UV/等离子硬化的光刻胶、等离子蚀刻后或蚀刻/灰化后残留物中的一种或多种而清洁微电子衬底的方法,其包括使所述微电子衬底与权利要求1~16任一项所述的清洁组合物接触,接触的时间和温度能有效使得该去除发生。
18.根据权利要求17所述的方法,其中所述微电子衬底是硅晶片或玻璃衬底并且所述清洁组合物抑制在清洁过程中的Cu(I)/唑类聚合物的形成或使其最小化。
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CN108235741B (zh) * | 2016-12-28 | 2019-05-28 | 松下知识产权经营株式会社 | 抗蚀剂剥离液 |
WO2020257103A1 (en) * | 2019-06-19 | 2020-12-24 | Versum Materials Us, Llc | Cleaning composition for semiconductor substrates |
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KR20140082713A (ko) | 2014-07-02 |
EP2764079A1 (en) | 2014-08-13 |
US20140249065A1 (en) | 2014-09-04 |
US10133180B2 (en) | 2018-11-20 |
JP2014534627A (ja) | 2014-12-18 |
CN103975052A (zh) | 2014-08-06 |
IL231874A0 (en) | 2014-05-28 |
JP6033314B2 (ja) | 2016-11-30 |
SG11201400840UA (en) | 2014-04-28 |
MY172099A (en) | 2019-11-13 |
WO2013052809A1 (en) | 2013-04-11 |
KR101999641B1 (ko) | 2019-07-12 |
EP2764079A4 (en) | 2015-06-03 |
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