CN106281789A - 一种配线基板干刻后残渣清洗剂 - Google Patents
一种配线基板干刻后残渣清洗剂 Download PDFInfo
- Publication number
- CN106281789A CN106281789A CN201610654390.3A CN201610654390A CN106281789A CN 106281789 A CN106281789 A CN 106281789A CN 201610654390 A CN201610654390 A CN 201610654390A CN 106281789 A CN106281789 A CN 106281789A
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- Prior art keywords
- abluent
- residue
- dry etching
- wiring substrate
- metal coating
- Prior art date
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- 239000000758 substrate Substances 0.000 title claims abstract description 32
- 238000001312 dry etching Methods 0.000 title claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 56
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000011248 coating agent Substances 0.000 claims abstract description 43
- -1 phosphine metalloid Chemical class 0.000 claims abstract description 32
- 150000001412 amines Chemical class 0.000 claims abstract description 19
- 239000003223 protective agent Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003381 stabilizer Substances 0.000 claims abstract description 13
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052752 metalloid Inorganic materials 0.000 claims abstract description 10
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 5
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 5
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 5
- 230000003139 buffering effect Effects 0.000 claims description 5
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 5
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical class OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- LEAHFJQFYSDGGP-UHFFFAOYSA-K trisodium;dihydrogen phosphate;hydrogen phosphate Chemical compound [Na+].[Na+].[Na+].OP(O)([O-])=O.OP([O-])([O-])=O LEAHFJQFYSDGGP-UHFFFAOYSA-K 0.000 claims description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 229940050410 gluconate Drugs 0.000 claims description 2
- 229940049920 malate Drugs 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
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- 239000010931 gold Substances 0.000 claims 1
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- LJSOLTRJEQZSHV-UHFFFAOYSA-L potassium;sodium;hydron;hydroxide;phosphate Chemical compound [OH-].[Na+].[K+].OP(O)([O-])=O LJSOLTRJEQZSHV-UHFFFAOYSA-L 0.000 claims 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 16
- 239000012530 fluid Substances 0.000 abstract description 16
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- 230000007797 corrosion Effects 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 8
- 239000010936 titanium Substances 0.000 abstract description 8
- 229910052719 titanium Inorganic materials 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
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- 230000001590 oxidative effect Effects 0.000 abstract description 3
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005530 etching Methods 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
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- 239000003795 chemical substances by application Substances 0.000 description 6
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- YPHMISFOHDHNIV-FSZOTQKASA-N cycloheximide Chemical compound C1[C@@H](C)C[C@H](C)C(=O)[C@@H]1[C@H](O)CC1CC(=O)NC(=O)C1 YPHMISFOHDHNIV-FSZOTQKASA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
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- FTOAOBMCPZCFFF-UHFFFAOYSA-N 5,5-diethylbarbituric acid Chemical compound CCC1(CC)C(=O)NC(=O)NC1=O FTOAOBMCPZCFFF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
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- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- KRZMDEOMIPKDLV-UHFFFAOYSA-N 2-hydroxy-2-phosphanylacetic acid Chemical compound OC(P)C(O)=O KRZMDEOMIPKDLV-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- SLTNJGDECJATET-RIVJSTIKSA-N [(8r,9s,10r,13s,14s,17s)-10,13-dimethyl-3-oxo-1,2,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl] 4-methylpentanoate;[(8r,9s,10r,13s,14s,17s)-10,13-dimethyl-3-oxo-1,2,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](OC(=O)CC)[C@@]1(C)CC2.C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](OC(=O)CCC(C)C)[C@@]1(C)CC2.C([C@]1(C2CC[C@@H]1O)C)CC(C1=CC=3)C2CCC1=CC=3OC(=O)C1=CC=CC=C1.O([C@H]1CCC2C3C(C4=CC=C(O)C=C4CC3)CC[C@@]21C)C(=O)CCC1=CC=CC=C1.O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(CCC(=O)C=C4CC3)C)CC[C@@]21C)C(=O)CCC1=CC=CC=C1 SLTNJGDECJATET-RIVJSTIKSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical compound OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
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- 238000010668 complexation reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
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- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 229950006191 gluconic acid Drugs 0.000 description 1
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical compound OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- ZJAOAACCNHFJAH-UHFFFAOYSA-N phosphonoformic acid Chemical class OC(=O)P(O)(O)=O ZJAOAACCNHFJAH-UHFFFAOYSA-N 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical group [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- OTNVGWMVOULBFZ-UHFFFAOYSA-N sodium;hydrochloride Chemical compound [Na].Cl OTNVGWMVOULBFZ-UHFFFAOYSA-N 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000010792 warming Methods 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3937—Stabilising 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
- 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
- C11D1/721—End blocked ethers
-
- 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3937—Stabilising agents
- C11D3/394—Organic 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
- 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
- C11D7/08—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
- 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
- C11D7/26—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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
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Abstract
本发明公开了一种配线基板干刻后残渣清洗剂，其特征在于，其主要组分为H2O2、金属保护剂、双氧水稳定剂、pH 值调节剂和水，清洗剂的pH 值为5～8，金属保护剂的主要组成为有机胺类金属保护剂和有机膦类金属保护剂。本发明配线基板干刻后残渣清洗剂为弱酸弱碱体系，与现有技术中的氧化性酸和碱性体系相比，对配线的侵蚀作用较弱，尤其是对配线侧面钛层的侵蚀作用；采用有机胺类金属保护剂和有机膦类金属保护剂复配，可在配线表面形成稳定的保护膜，并且上述两种金属保护剂均具有表面活性，可优化清洗液的润湿和渗透能力，加速残渣的剥离。
Description
技术领域
本发明涉及半导体蚀刻后清洗剂技术领域，具体涉及一种配线基板干刻后残渣清洗剂。
背景技术
蚀刻形成铜配线基板的方法包括两种：湿式蚀刻和干式蚀刻。湿式蚀刻选用蚀刻液与表面覆有铜层的基板反应，具体包括化学蚀刻液扩散至待蚀刻材料之表面、蚀刻液与待蚀刻材料发生化学反应、反应后之产物从蚀刻材料之表面扩散至溶液中并随溶液排出三步骤。干式刻蚀以气体作为主要的蚀刻媒介，并藉由电浆能量来驱动反应，将铜层和铜层与基板之间的过渡金属层（例如钛层）自基板表面移除。由于在干刻工序后的侧面和底面附着有蚀刻残渣，上述残渣会直接导致高电阻化或产生电短路。为了除去该蚀刻残渣，通常具有利用洗涤液实施洗涤、并在洗涤后立即用有机溶剂或超纯水冲洗洗涤液的工序。
如中国专利CN101331811A中背景技术部分提及的，常用的清洗剂为双氧水体系，具体包括过氧化氢-季铵盐-缓蚀剂体系、过氧化氢-硫酸铵-氟化物-螯合剂体系、过氧化氢-碱性物质（季铵氢氧化物、氢氧化钾）-缓蚀剂体系和氧化剂-唑系化合物酸性组合物体系，后一体系中的氧化剂为选自过氧化氢、臭氧、高锰酸钾、过碳酸及其盐、过磷酸及其盐、过硫酸及其盐、碘酸及其盐、溴酸及其盐、高氯酸及其盐、氯酸及其盐、次氯酸及其盐中的至少一种。随着现有技术中配线间距的细微化，含氟离子源、碱性物质的清洗剂容易侵蚀铜配线下方的钛层，还会引起铜布线材料表面的氧化或腐蚀之类的铜布线材料表面状态的变化、变质。加入碱性物质如季铵氢氧化物、氢氧化钾等碱性物质可以与水反应电离出氢氧根，同样存在二次腐蚀金属线的风险；就金属保护剂而言，唑系化合物能在铜表面形成一层致密的保护膜，但对配线槽侧面的钛层防护有限。另外，清洗液体系的 pH值对于金属保护剂的缓蚀作用和双氧水的反应活性有明显的影响。
发明内容
本发明的目的在于克服现有技术中存在的缺陷，提供一种配线基板干刻后残渣清洗剂，该清洗液能有效去除干刻产生的蚀刻残渣，体系组分稳定，对配线表面的侵蚀程度小。
为实现上述目的，本发明的技术方案为：一种配线基板干刻后残渣清洗剂，其特征在于，其主要组分为H2O2、金属保护剂、双氧水稳定剂、pH 值调节剂和水，清洗剂的pH 值为5～8，金属保护剂的主要组成为有机胺类金属保护剂和有机膦类金属保护剂。
采用弱酸弱碱性的清洗剂，可以降低氧化性酸和碱对于铜配线的侵蚀作用。有机胺类金属保护剂和有机膦类金属保护剂与金属表面之间均可以形成配位键，在配线正面和侧面的铜、钛表面形成络合物，胺类金属保护剂在弱酸性条件下比较有效，而有机膦金属保护剂的耐酸碱性能良好，适用于弱酸弱碱条件下的金属保护，将两者复配用于弱酸弱碱的清洗液中，金属表面的成膜更趋稳定。
为了优化缓蚀性能和对残渣的剥离性能，优选的技术方案为，配线基板干刻后残渣清洗剂质量按100%计，主要组分的质量百分比分别为：H2O2 0.1～10%、金属保护剂0.05～2%、双氧水稳定剂0.005～3%、pH 值调节剂3～7%和水80～96%。金属保护剂含量大于5%，缓蚀剂的复配性能较差。
优选的技术方案为，有机胺类金属保护剂为选自水溶性的环状亚胺、松香胺和季铵盐中的至少一种，有机膦类金属保护剂为选自烃基膦酸型金属保护剂和磷羧酸型金属保护剂中的至少一种。
为了进一步优化金属保护剂的复配效果，优选的技术方案为，金属保护剂中有机膦类金属保护剂的重量百分比为60～78%。
优选的技术方案为，有机胺类金属保护剂由2-膦酸丁烷 -1, 2, 4-三羧酸和选自咪唑啉季铵盐、喹啉季铵盐和吡啶季铵盐中的至少一种与组合而成。2-膦酸丁烷 -1, 2,4-三羧酸具有良好的耐高低温性能、耐氧化性和化学稳定性，另外，两种金属保护剂局具有一定的表面活性，可以加速残渣自配线表面的剥离。
优选的技术方案为，双氧水稳定剂为选自可溶性苹果酸盐、酒石酸盐、葡萄糖酸盐、羟乙酸盐中的至少一种。加入上述双氧水稳定剂对应的有机酸对清洗液体系的酸碱度影响较大，多羧酸型双氧水稳定剂的酸根离子对铜离子和钛离子具有较强的螯合作用，所得螯合产物在弱酸弱碱或中性的清洗液体系中具有溶解度较高，保证清洗后的配线基板表面无残渣。
优选的技术方案为，配线基板干刻后残渣清洗剂的组成还包括质量百分比为0.005～0.2%的氯盐，氯盐为氯化钠、氯化钾中的至少一种。氯盐电离出的氯离子可在金属表面形成负的吸附电位，加强有机胺和有机膦金属保护剂阳离子的吸附，有助于进一步优化配线保护效果。
为了稳定清洗液的pH值，减少因清洗液体系酸碱度的变化而导致过氧化氢活性降低和金属保护剂的保护效果减弱，优选的技术方案为，pH 值调节剂为选自磷酸二氢钾-氢氧化钠缓冲对或磷酸氢二钠-磷酸二氢钠缓冲对。清洗液中常用的pH值为5～8的缓冲对也可以使用，不限于此。
为了进一步优化清洗液对残渣的包覆润湿及残渣与金属表面之间间隙的渗透效果，优选的技术方案为，配线基板干刻后残渣清洗剂还包括表面活性剂，所述表面活性剂为脂肪醇聚氧乙烯醚。
本发明的优点和有益效果在于：
本发明配线基板干刻后残渣清洗剂为弱酸弱碱体系，与现有技术中的氧化性酸和碱性体系相比，对配线的侵蚀作用较弱，尤其是对配线侧面钛层的侵蚀作用；
采用有机胺类金属保护剂和有机膦类金属保护剂复配，可在配线表面形成稳定的保护膜，并且上述两种金属保护剂均具有表面活性，可优化清洗液的润湿和渗透能力，加速残渣的剥离；
清洗液中不含有强碱性物质，经清洗后的配线基板水洗过程中被二次腐蚀的几率低。
具体实施方式
下面结合实施例，对本发明的具体实施方式作进一步描述。以下实施例仅用于更加清楚地说明本发明的技术方案，而不能以此来限制本发明的保护范围。
烃基膦酸型金属保护剂的具体选择可为：烃基氨基甲撑基膦酸、α-氨基烃基膦酸、多氨基多醚基甲叉膦酸；
磷羧酸型金属保护剂的具体选择不限于2-膦酸丁烷 -1, 2, 4-三羧酸，还可为2-羟基膦基乙酸、膦酰基羧酸；
环状亚胺具有较强的提供π电子的能力，对金属的吸附性能也较强，可选环己亚胺、环庚亚胺、环辛亚胺中的一种。
实施例1-4
按照下表所列内容配置实施例1-5清洗剂：
实施例1-5中，金属保护剂为环己亚胺和烃基氨基甲撑基膦酸等重混合而成，双氧水稳定剂采用锡酸盐，实施例2和实施例3的pH值调节剂为巴比妥钠-盐酸缓冲对，实施例1和实施例4的pH值调节剂为磷酸氢二钠-磷酸二氢钠缓冲对。
实施例6-8以实施例5为基础，各组分的质量百分比同实施例5，pH值调节剂为磷酸二氢钾-氢氧化钠缓冲对，其他区别在于：
实施例6的金属保护剂为松香胺和α-氨基烃基膦酸组合而成，松香胺在水中的溶解度较小，因此金属保护剂中松香胺的重量百分比为10%，双氧水稳定剂为柠檬酸钠。
实施例7的金属保护剂为2-膦酸丁烷 -1, 2, 4-三羧酸和咪唑啉季铵盐组合而成，金属保护剂中2-膦酸丁烷 -1, 2, 4-三羧酸的重量百分比为60%，双氧水稳定剂为酒石酸盐和葡萄糖酸盐以质量比2:1混合而成。
实施例8的金属保护剂为为2-膦酸丁烷 -1, 2, 4-三羧酸、吡啶季铵盐和喹啉季铵盐组合而成，吡啶季铵盐和喹啉季铵盐等重，金属保护剂中2-膦酸丁烷 -1, 2, 4-三羧酸的重量百分比为78%，双氧水稳定剂为羟乙酸钠。
实施例9-11以实施例8为基础，各组分的质量百分比同实施例8，区别在于：
实施例9的清洗剂中加入0.005%的氯化钠，水含量略减少；
实施例10的清洗剂中加入0.2%的氯化铵；上述氯化铵还可以采用氯化钾替代。
实施例11中的清洗剂中加入0.008%的脂肪醇聚氧乙烯醚，水含量略减少；
对比例：对比例均基于实施例5的组成，pH值相同，采用乙酸或氨水作为pH值调节剂。
对比例1的组成同实施例5，区别在于，清洗液的pH值为3，金属保护剂为α-氨基烃基膦酸。
对比例2的组成同实施例5，区别在于，清洗液的pH值为9.5，金属保护剂为环庚亚胺。
对比例3的区别在于加入0.5%氢氧化钾，水含量略减少，pH值与实施例5相同；
对比例4的区别在于加入0.5%季铵氢氧化物，水含量略减少，pH值与实施例5相同；
对比例5的区别在于加入0.5%单乙醇胺，水含量略减少，pH值与实施例5相同；
实施例和对比例性能测试对比：
A:将表面覆有钛层和铜层的基板试片经过相同的干刻梳理，将配线基板干刻后残渣清洗液升温至40℃，将配线基板置于其中浸渍处理3min，用超纯水冲洗，氮气冲干，用扫描电镜观察试片的配线表面是否被腐蚀以及是否存在残渣残留。
对配线层的腐蚀性评价标准如下：
○完全观察不到配线被腐蚀
◎观察到一部分配线被腐蚀
●观察到整体配线层被腐蚀
对残渣残留情况的评价标准如下：
○完全观察不到残渣残留
◎观察到一部分残渣残留
●观察到整体残渣的残留
电镜观察结果见下表：
电镜观察表明，对配线的腐蚀主要表现在钛层，其次为铜层表面；实施例9和实施例10的配线腐蚀情况略优于实施例6-8，原因在于氯离子在金属表面形成负的吸附电位较弱，因此有机胺和有机膦金属保护剂阳离子的吸附增加幅度不大；对实施例11清洗时间缩短为2min，清洗效果同表中实施例11；
B: 对比清洗液中的双氧水的受热稳定性：通过将一定量蚀刻液在85±1℃的烘箱内加热24小时，滴定其在加热前后所含H2O2浓度，计算其活性氧损失（A.O.损失）：
A.O.损失=【(H2O2初始浓度)-(H2O2结束浓度) 】/ H2O2初始浓度。
实施例1-8、对比例1-2蚀刻液的A.O.损失分别为4.1%、5.7%、4.8%、3.7%、3.5%、2.7%、3.6%和4.2%。
从上述双氧水的A.O.损失对比可以看出，pH值和双氧水稳定剂的具体选择对A.O.损失数据均由影响，其中，清洗液中的有机胺金属保护剂和有机膦金属保护剂同样可以作为双氧水保护剂，络合蚀刻产生的铜离子和钛离子，酸性却强，对比例和对比例2比较得出，双氧水的稳定性越强。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (9)
1.一种配线基板干刻后残渣清洗剂，其特征在于，其主要组分为H2O2、金属保护剂、双氧水稳定剂、pH 值调节剂和水，清洗剂的pH 值为5～8，金属保护剂的主要组成为有机胺类金属保护剂和有机膦类金属保护剂。
2.根据权利要求1所述的配线基板干刻后残渣清洗剂，其特征在于，配线基板干刻后残渣清洗剂质量按100%计，主要组分的质量百分比分别为：H2O2 0.1～10%、金属保护剂0.05～2%、双氧水稳定剂0.005～3%、pH 值调节剂3～7%和水80～96%。
3.根据权利要求1或2所述的配线基板干刻后残渣清洗剂，其特征在于，有机胺类金属保护剂为选自水溶性的环状亚胺、松香胺和季铵盐中的至少一种，有机膦类金属保护剂为选自烃基膦酸型金属保护剂和磷羧酸型金属保护剂中的至少一种。
4.根据权利要求3所述的配线基板干刻后残渣清洗剂，其特征在于，金属保护剂中有机膦类金属保护剂的重量百分比为60～78%。
5.根据权利要求4所述的配线基板干刻后残渣清洗剂，其特征在于，有机胺类金属保护剂由2-膦酸丁烷 -1, 2, 4-三羧酸和选自咪唑啉季铵盐、喹啉季铵盐和吡啶季铵盐中的至少一种与组合而成。
6.根据权利要求1或2所述的配线基板干刻后残渣清洗剂，其特征在于，双氧水稳定剂为选自可溶性苹果酸盐、酒石酸盐、葡萄糖酸盐、羟乙酸盐中的至少一种。
7.根据权利要求6所述的配线基板干刻后残渣清洗剂，其特征在于，配线基板干刻后残渣清洗剂的组成还包括质量百分比为0.005～0.2%的氯盐，氯盐为氯化钠、氯化钾中的至少一种。
8.根据权利要求1或2所述的配线基板干刻后残渣清洗剂，其特征在于，pH 值调节剂为选自磷酸二氢钾-氢氧化钠缓冲对或磷酸氢二钠-磷酸二氢钠缓冲对。
9.根据权利要求1或2所述的配线基板干刻后残渣清洗剂，其特征在于，配线基板干刻后残渣清洗剂还包括表面活性剂，所述表面活性剂为脂肪醇聚氧乙烯醚。
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