CN113881510A - 一种化学机械抛光清洗液及使用方法 - Google Patents
一种化学机械抛光清洗液及使用方法 Download PDFInfo
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- CN113881510A CN113881510A CN202010634290.0A CN202010634290A CN113881510A CN 113881510 A CN113881510 A CN 113881510A CN 202010634290 A CN202010634290 A CN 202010634290A CN 113881510 A CN113881510 A CN 113881510A
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- cleaning solution
- chemical mechanical
- acid
- mechanical polishing
- surfactant
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- 238000004140 cleaning Methods 0.000 title claims abstract description 114
- 238000005498 polishing Methods 0.000 title claims abstract description 106
- 239000000126 substance Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 84
- 238000010790 dilution Methods 0.000 claims abstract description 8
- 239000012895 dilution Substances 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims description 29
- 239000008139 complexing agent Substances 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000080 wetting agent Substances 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 8
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002736 nonionic surfactant Substances 0.000 claims description 6
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 229940120146 EDTMP Drugs 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 3
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 3
- -1 alkyl sulfuric acid Chemical compound 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 3
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 235000012431 wafers Nutrition 0.000 description 44
- 239000010949 copper Substances 0.000 description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 26
- 229910052802 copper Inorganic materials 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 15
- 239000007788 liquid Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 150000007522 mineralic acids Chemical group 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012487 rinsing solution Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/78—Neutral esters of acids of phosphorus
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
-
- 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
- C11D3/2003—Alcohols; Phenols
- C11D3/2041—Dihydric alcohols
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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
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2041—Dihydric alcohols
- C11D3/2044—Dihydric alcohols linear
-
- 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
- C11D3/2003—Alcohols; Phenols
- C11D3/2065—Polyhydric alcohols
-
- 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
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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
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy 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
- C11D3/33—Amino carboxylic acids
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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
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/364—Organic compounds containing phosphorus 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
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/365—Organic compounds containing phosphorus containing carboxyl groups
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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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- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3707—Polyethers, e.g. polyalkyleneoxides
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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
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- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3753—Polyvinylalcohol; Ethers or esters thereof
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
本发明公开了一种化学机械抛光清洗液及其使用方法,该清洗液包含络合剂、表面活性剂、润湿剂、pH调节剂、余量为水。本发明的化学机械抛光清洗液是一种高度浓缩的清洗液,能够通过调节稀释倍数同时满足对化学机械抛光后的晶圆片和抛光垫的清洗。
Description
技术领域
本发明涉及一种清洗液,尤其涉及一种用于半导体制造化学机械抛光后晶圆片和抛光垫的清洗液。
背景技术
目前超大规模集成电路芯片集成度已达几十亿个元器件,特征尺寸已经进入纳米级别,这就要求微电子工艺中的几百道工序,尤其是多层布线、衬底、介质等必须要经过化学机械平坦化。超大规模集成电路布线正由传统的铝布线工艺向铜布线工艺转化。与Al相比,Cu布线具有电阻率低、抗电迁移率高,RC延迟时间短等优势,这使得Cu布线能够代替Al成为半导体制作中的互联金属。但是目前尚没有对铜材进行有效等离子蚀刻或湿法蚀刻来达到平坦化的技术,化学机械抛光仍然是铜布线平坦化的最有效工艺方法。
化学机械抛光(CMP)工艺就是使用一种含磨料的混合物以及抛光垫,通过化学作用及机械作用,来抛光集成电路的表面。在典型的CMP中,将硅片衬底直接与旋转抛光垫接触,同时用一载重物在衬底背面施加压力。在抛光期间,将磨料和化学活性溶液(通常称为抛光液或抛光浆料)涂于抛光垫上,该抛光液与正在抛光的硅片薄膜发生化学反应,抛光垫和操作台旋转,产生相对运动,同时在衬底背面保持向下的力,进行抛光过程。然而,CMP工艺也带来了一系列的问题。在研磨浆料抛光晶圆片之后,晶圆表面通常会存在各种缺陷,如纳米氧化物颗粒残留、各种有机物残留以及抛光反应生成物质的残留等。在铜抛光过程中,大量的铜会被去除,在抛光垫上的抛光残留物较多,如果每次抛光后不能将这些残留物清除干净,那么随着抛光时间的增加,残留物聚集在抛光垫上,会影响铜去除速率的稳定性,抛光后的铜表面更容易产生划伤、腐蚀等缺陷,缩短了抛光垫的使用寿命。
对于CMP工艺带来的以上问题,通常都是采用清洗液来清洗抛光后的晶圆片和抛光垫,而一般来说,晶圆片清洗液和抛光垫清洗液配方有所差异。晶圆片清洗液大多包括络合剂(螯合剂)、润湿剂、表面活性剂等成分,其中络合剂能够有效的络合溶解铜及其他金属以及氧化物的残留,表面活性剂能够有效的清洗晶圆表面的残留物或颗粒。如专利TW494020B、CN101255386A分别揭示了用于化学机械抛光后晶圆片的清洗液,即使用表面活性剂和螯合剂等物质来清洗晶圆片表面。专利TWI362415B报道了一种含有表面活性剂、络合剂、润湿剂的基板清洗液,能够用于清洗抛光后晶圆表面。专利CN1500857A报道了一种含有表面活性剂的高浓缩晶圆清洗液。而抛光垫清洗液通常是含有络合剂不含表面活性剂,这是因为当清洗液中含有大量表面活性剂时,表面活性剂往往会吸附在抛光垫的表面,从而对抛光速率造成影响,如专利CN102453637A报道了一种含有氨羧络合物的抛光垫清洗液。基于此,目前的清洗液只能用于清洗晶圆片或者抛光垫中的一种,无法同时满足对晶圆片和抛光垫的清洗,使得晶圆片和抛光垫的清洗得在两种不同的清洗液工序进行,增加了清洗工序的复杂性,降低了清洗工作的效率,不利于生产效率的提升。
此外,随着铜布线层数的增加,抛光清洗液的用量也随之增加,如何使得清洗液的使用及存储、运输更为方便、更加经济有效,也是本行业亟待解决解决的问题。
发明内容
本发明的目的是克服上述现有技术的不足,通过清洗液配方的优化设计,制得高度浓缩、且能够调节稀释倍数同时满足对化学机械抛光后晶圆片和抛光垫的清洗液,从而降低清洗液的使用成本,提高生产效率。
为实现以上的技术效果,本发明采用如下的技术方案:
一种化学机械抛光清洗液,包括质量百分数为1%~35%的络合剂、0.05%~2%的表面活性剂、0.1~10%的润湿剂、pH调节剂、余量为水。
在一个优选的实施方案中,所述的化学机械抛光清洗液,包括质量百分数为2%~30%的络合剂、0.1%~1%的表面活性剂、0.5~5%的润湿剂、pH调节剂、余量为水。
在一个具体的实施方案中,所述的络合剂选自乙酸、丙酸、草酸、丙二酸、丁二酸、柠檬酸、磷酸、乙二胺四乙酸、2-膦酸丁烷-1,2,4-三羧酸、氨基三甲叉膦酸、羟基乙叉二膦酸、乙二胺四甲叉膦酸中的一种或多种;优选地,所述的络合剂为磷酸和/或柠檬酸。
在一个具体的实施方案中,所述表面活性剂选自阴离子表面活性剂和/或非离子表面活性剂。
在一个优选的实施方案中,所述阴离子表面活性剂选自烷基苯磺酸、烷基芳烃磺酸、烷基硫酸、烷基芳烃硫酸、磷酸乙酯、磷酸丁酯、磷酸辛酯中的一种或多种;所述非离子表面活性剂选自烷基聚氧乙烯醚、脂肪醇聚氧乙烯醚、聚氧丙烯共聚物中的一种或多种。
在一个具体的实施方案中,所述的润湿剂选自乙二醇、聚乙二醇、乙二醇单乙醚、聚乙烯醇、丙二醇、甘油中的一种或多种。
在一个具体的实施方案中,所述pH调节剂选自HNO3、无机氨或有机胺,所述调节后清洗液的pH范围为1~5,优选地,所述清洗液的pH范围为1~3。
本发明的另一方面,前述化学机械抛光清洗液的使用方法,所述的清洗液可以通过调节稀释比例,同时满足对化学机械抛光后晶圆片和抛光垫的清洗。
在一个具体的实施方案中,所述的清洗液,使用去离子水稀释10~30倍,可满足对化学机械抛光后晶圆片的清洗。
在一个具体的实施方案中,所述的清洗液,使用去离子水稀释50~80倍,可满足对化学机械抛光后抛光垫的清洗。
本发明通过采用上述技术方案,获得了如下的有益效果:
(1)本发明通过优化清洗液配方设计,实现了清洗液的高度浓缩,且能够同时满足对化学机械抛光后晶圆片和抛光垫的清洗。
(2)采用本发明的高度浓缩的化学机械抛光清洗液,通过调节稀释倍数,既能清洗化学机械抛光后的晶圆片,又能清洗抛光垫,这使得清洗工作更加简便、提升了工作效率。
(3)采用本发明的高度浓缩的化学机械抛光清洗液,无需像现有技术一样需要使用晶圆片清洗液和抛光垫清洗液进行不同的清洗步骤,无需采购、存储两种数量庞大的清洗液,本发明通过高度浓缩的清洗液使用时稀释至一定倍数,可以大幅降低产品原材料、包装、运输、仓储、管理、人力等成本。
具体实施方式
为了更好的理解本发明的技术方案,下面的实施例将对本发明所提供的方法予以进一步的说明,但本发明不限于所列出的实施例,还应包括在本发明的权利要求范围内其他任何公知的改变。
一种化学机械抛光清洗液,包含络合剂、表面活性剂、润湿剂、pH调节剂、余量为水。
具体地,其中络合剂为无机酸、有机酸、有机膦酸、氨基酸和/或有机胺,选自如下中的一种或多种:乙酸、丙酸、草酸、丙二酸、丁二酸、柠檬酸、磷酸、乙二胺四乙酸、2-膦酸丁烷-1,2,4-三羧酸、氨基三甲叉膦酸、羟基乙叉二膦酸、乙二胺四甲叉膦酸。其中较佳为磷酸和/或柠檬酸,所述的络合剂的质量百分比的浓度为1~35%,优选为2~30%。
其中表面活性剂为阴离子表面活性剂和/或非离子表面活性剂。其中阴离子表面活性剂,选自如下中的一种或多种:烷基苯磺酸、烷基芳烃磺酸、烷基硫酸、烷基芳烃硫酸、磷酸乙酯、磷酸丁酯或磷酸辛酯。其中非离子表面活性剂选自如下中的一种或多种:烷基聚氧乙烯醚、脂肪醇聚氧乙烯醚或聚氧丙烯共聚物。所述的表面活性剂的质量百分比浓度为0.05~1%,优选为0.1~1%。
其中润湿剂,选自如下中的一种或多种:乙二醇、聚乙二醇、乙二醇单乙醚、聚乙烯醇、丙二醇、甘油。所述的润湿剂的质量百分比浓度为0.1~10%,优选为0.5~5%。
此外,本清洗液还包含pH调节剂,pH调节剂选自HNO3、无机氨或有机胺。通过pH调节剂调节所述清洗液的pH值到1~5,优选地,所述清洗液的pH范围为1~3。
可以发现,本发明的高浓缩的清洗液,包括质量百分数为1%~35%的络合剂、0.05%~2%的表面活性剂、0.1~10%的润湿剂、pH调节剂,余量为水。一个优选的方案,所述的化学机械抛光清洗液,包括质量百分数为2%~30%的络合剂、0.1%~1%的表面活性剂、0.5~5%的润湿剂、pH调节剂,余量为水。
本发明打破现有技术抛光垫清洗液通常含有络合剂不含表面活性剂的常规思路,采用全新的配方设计,使用一种同时含有络合剂和表面活性剂、并加入润湿剂加以调节的高度浓缩的清洗液,采用调节稀释倍数的方法,能够同时满足对化学机械抛光后晶圆片和抛光垫的清洗。当本清洗液低倍稀释时(10~30倍),表面活性剂的含量能够满足对晶圆片清洗的需求;而当本清洗液高倍稀释时(50~80倍),表面活性剂的含量变低,难以在抛光垫上吸附,不会对抛光速率造成影响。在稀释不同倍数时,本发明加入的润湿剂用于平衡表面活性剂的含量,使得本发明的清洗液能够通过调节稀释倍数同时满足对化学机械抛光后晶圆片和抛光垫的清洗。
下面通过更具体的实施例进一步阐述本发明的优点,但本发明的保护范围不仅仅局限于下述实施例。
表1给出了本发明清洗液的成分,按表中所给的配方,余量为水,将各种组分混合均匀,用HNO3、无机氨或有机胺调节到所需要的pH值,即可。
表1实施例1~12的清洗液成分表
为验证本发明清洗液对抛光垫的清洗效果,本发明实施例中所使用的铜抛光液pH=6,抛光条件如下:抛光机台为Logitech,抛光垫IC1010,抛光压力2.5psi,抛光头及抛光盘转速75/65rpm,抛光液流速150mL/min,铜晶圆片。抛光前后分别用四探针电导率仪测试铜晶圆片的电导率,从而计算铜晶圆片的厚度,抛光前后铜晶圆片的厚度差即为铜的去除速率。抛光前用清洗液和/或去离子水清洗抛光垫。
表2给出了本发明的清洗液实施例1~12及对比例1~3对抛光垫的清洗效果。采用对比例1~3以及本发明的清洗液实施例1~12清洗抛光垫,然后再用铜抛光垫对空片铜进行抛光,铜的去除速率见表2。抛光垫的清洗条件为:铜抛光结束后,先用清洗液清洗10秒,流量为500mL/min,然后用去离子水清洗10秒;流量为1200mL/min。对比例1~2的成分为去离子水,对比例3为只含有0.1%脂肪醇聚氧乙烯醚的清洗液。
表2对比例1~2和实施例1~12的清洗液对抛光垫的清洗效果
由表2对比例2的结果可见,当抛光垫上有铜的残留时,继续使用抛光垫进行铜抛光,铜的去除速率明显降低;而由对比例3可知,当使用含有一定量表面活性剂的清洗液清洗抛光垫之后,表面活性剂会吸附在抛光垫上,从而大幅降低铜的抛光速率。而使用本发明的清洗液配方,即使存在表面活性剂,由于加入了润湿剂加以调节,稀释一定的倍数后(50-80倍)对抛光垫进行清洗,铜的去除速率能够明显改善,使得铜的去除基本保持正常速率。
表3给出了本发明的清洗液实施例1~12及对比例1~4对抛光后铜晶圆片的清洗效果。采用对比例1~4以及本发明的清洗液实施例1~12清洗晶圆片,利用接触角测量仪测量清洗后晶圆片表面的接触角,具体数值见表3。晶圆片的清洗条件为:抛光结束后,使用PVA多孔清洗刷(brush)清洗晶圆片,先用清洗液清洗60秒,流量为150mL/min;然后用去离子水清洗90秒,流量为150mL/min。对比例1~2的成分为去离子水,对比例3为只含有0.1%脂肪醇聚氧乙烯醚的清洗液,对比例4为只含有1%甘氨酸的清洗液。
表3对比例1~2和实施例1~12的清洗液对晶圆片的清洗效果
由表3对比例2和4实验结果可见,当晶圆片上有较多的残留物时,晶圆表面的接触角较大,使用只含有络合剂的清洗液清洗晶圆片时,晶圆表面难以清洗干净,仍然有大量的残留且接触角较大。对比例3实验结果可知,使用只含有表面活性剂的清洗液清洗晶圆片时,接触角虽然能够得到改善,但表面残留物却难以清洗干净。而使用本发明的清洗液因为独特的配方设计,既包括表面活性剂和络合剂,又加入了润湿剂加以调节,稀释一定的倍数(10-30倍)后对晶圆片进行清洗,晶圆片表面的残留物含量及接触角都能够明显改善,使得晶圆片表面洁净度得到极大提高。
综上所述,本发明通过优化清洗液配方,实现了清洗液的高度浓缩,且能够通过调节稀释倍数同时满足对化学机械抛光后晶圆片和抛光垫的清洗。本发明清洗液的使用,可简化化学机械抛光后晶圆片和抛光垫的清洗工序,方便清洗液的存储、运输和使用流程,从而降低清洗液的使用成本,提高生产效率。
尽管本发明的内容已经通过上述优选实施例作了详细介绍,但应当认识到上述的描述不应被认为是对本发明的限制。本领域技术人员可以理解,在本说明书的教导之下,可对本发明做出一些修改或调整。这些修改或调整也应当在本发明权利要求所限定的范围之内。
Claims (10)
1.一种化学机械抛光清洗液,包括质量百分数为1%~35%的络合剂、0.05%~2%的表面活性剂、0.1~10%的润湿剂、pH调节剂、余量为水。
2.根据权利要求1所述的化学机械抛光清洗液,其特征在于,包括质量百分数为2%~30%的络合剂、0.1%~1%的表面活性剂、0.5~5%的润湿剂、pH调节剂、余量为水。
3.根据权利要求1或2所述的化学机械抛光清洗液,其特征在于,所述的络合剂选自乙酸、丙酸、草酸、丙二酸、丁二酸、柠檬酸、磷酸、乙二胺四乙酸、2-膦酸丁烷-1,2,4-三羧酸、氨基三甲叉膦酸、羟基乙叉二膦酸、乙二胺四甲叉膦酸中的一种或多种;优选地,所述的络合剂为磷酸和/或柠檬酸。
4.根据权利要求1或2所述的化学机械抛光清洗液,其特征在于,所述表面活性剂选自阴离子表面活性剂和/或非离子表面活性剂。
5.根据权利要求4所述的化学机械抛光清洗液,其特征在于,所述阴离子表面活性剂选自烷基苯磺酸、烷基芳烃磺酸、烷基硫酸、烷基芳烃硫酸、磷酸乙酯、磷酸丁酯、磷酸辛酯中的一种或多种;所述非离子表面活性剂选自烷基聚氧乙烯醚、脂肪醇聚氧乙烯醚、聚氧丙烯共聚物中的一种或多种。
6.根据权利要求1或2所述的化学机械抛光清洗液,其特征在于,所述的润湿剂选自乙二醇、聚乙二醇、乙二醇单乙醚、聚乙烯醇、丙二醇、甘油中的一种或多种。
7.根据权利要求1或2所述的化学机械抛光清洗液,其特征在于,所述pH调节剂选自HNO3、无机氨或有机胺,所述调节后清洗液的pH范围为1~5,优选地,所述清洗液的pH范围为1~3。
8.权利要求1-7任一项所述的化学机械抛光清洗液的使用方法,所述的清洗液可以通过调节稀释比例,同时满足对化学机械抛光后晶圆片和抛光垫的清洗。
9.根据权利要求8所述的化学机械抛光清洗液的使用方法,其特征在于,所述的清洗液,使用去离子水稀释10~30倍,可满足对化学机械抛光后晶圆片的清洗。
10.根据权利要求8所述的化学机械抛光清洗液的使用方法,其特征在于,所述的清洗液,使用去离子水稀释50~80倍,可满足对化学机械抛光后抛光垫的清洗。
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