CN112041970A - 水性组合物和使用其的清洗方法 - Google Patents
水性组合物和使用其的清洗方法 Download PDFInfo
- Publication number
- CN112041970A CN112041970A CN201980027525.5A CN201980027525A CN112041970A CN 112041970 A CN112041970 A CN 112041970A CN 201980027525 A CN201980027525 A CN 201980027525A CN 112041970 A CN112041970 A CN 112041970A
- Authority
- CN
- China
- Prior art keywords
- fluoride
- alkyl
- compound
- acid
- phosphoric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 109
- 238000004140 cleaning Methods 0.000 title claims description 36
- 238000000034 method Methods 0.000 title claims description 24
- -1 fluoride ions Chemical class 0.000 claims abstract description 68
- 235000011007 phosphoric acid Nutrition 0.000 claims abstract description 31
- 150000003839 salts Chemical class 0.000 claims abstract description 29
- 150000001768 cations Chemical class 0.000 claims abstract description 26
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 20
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 37
- 239000002253 acid Substances 0.000 claims description 27
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 25
- 238000005530 etching Methods 0.000 claims description 21
- 150000002148 esters Chemical class 0.000 claims description 20
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 16
- 125000005600 alkyl phosphonate group Chemical group 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 9
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 239000011698 potassium fluoride Substances 0.000 claims description 8
- 235000003270 potassium fluoride Nutrition 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- AHLATJUETSFVIM-UHFFFAOYSA-M rubidium fluoride Chemical compound [F-].[Rb+] AHLATJUETSFVIM-UHFFFAOYSA-M 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 6
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 5
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 claims description 4
- OZFLRNPZLCUVFP-UHFFFAOYSA-N 8-methylnonyl dihydrogen phosphate Chemical compound CC(C)CCCCCCCOP(O)(O)=O OZFLRNPZLCUVFP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003868 ammonium compounds Chemical class 0.000 claims description 4
- 150000001553 barium compounds Chemical class 0.000 claims description 4
- 150000001573 beryllium compounds Chemical class 0.000 claims description 4
- SCIGVHCNNXTQDB-UHFFFAOYSA-N decyl dihydrogen phosphate Chemical compound CCCCCCCCCCOP(O)(O)=O SCIGVHCNNXTQDB-UHFFFAOYSA-N 0.000 claims description 4
- DZQISOJKASMITI-UHFFFAOYSA-N decyl-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound CCCCCCCCCCP(O)(O)=O DZQISOJKASMITI-UHFFFAOYSA-N 0.000 claims description 4
- SVMUEEINWGBIPD-UHFFFAOYSA-N dodecylphosphonic acid Chemical compound CCCCCCCCCCCCP(O)(O)=O SVMUEEINWGBIPD-UHFFFAOYSA-N 0.000 claims description 4
- GGKJPMAIXBETTD-UHFFFAOYSA-N heptyl dihydrogen phosphate Chemical compound CCCCCCCOP(O)(O)=O GGKJPMAIXBETTD-UHFFFAOYSA-N 0.000 claims description 4
- VAJFLSRDMGNZJY-UHFFFAOYSA-N heptylphosphonic acid Chemical compound CCCCCCCP(O)(O)=O VAJFLSRDMGNZJY-UHFFFAOYSA-N 0.000 claims description 4
- PHNWGDTYCJFUGZ-UHFFFAOYSA-N hexyl dihydrogen phosphate Chemical compound CCCCCCOP(O)(O)=O PHNWGDTYCJFUGZ-UHFFFAOYSA-N 0.000 claims description 4
- GJWAEWLHSDGBGG-UHFFFAOYSA-N hexylphosphonic acid Chemical compound CCCCCCP(O)(O)=O GJWAEWLHSDGBGG-UHFFFAOYSA-N 0.000 claims description 4
- 150000002642 lithium compounds Chemical class 0.000 claims description 4
- 150000002681 magnesium compounds Chemical class 0.000 claims description 4
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 claims description 4
- WYAKJXQRALMWPB-UHFFFAOYSA-N nonyl dihydrogen phosphate Chemical compound CCCCCCCCCOP(O)(O)=O WYAKJXQRALMWPB-UHFFFAOYSA-N 0.000 claims description 4
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 claims description 4
- NJGCRMAPOWGWMW-UHFFFAOYSA-N octylphosphonic acid Chemical compound CCCCCCCCP(O)(O)=O NJGCRMAPOWGWMW-UHFFFAOYSA-N 0.000 claims description 4
- NVTPMUHPCAUGCB-UHFFFAOYSA-N pentyl dihydrogen phosphate Chemical compound CCCCCOP(O)(O)=O NVTPMUHPCAUGCB-UHFFFAOYSA-N 0.000 claims description 4
- CKVICYBZYGZLLP-UHFFFAOYSA-N pentylphosphonic acid Chemical compound CCCCCP(O)(O)=O CKVICYBZYGZLLP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003112 potassium compounds Chemical class 0.000 claims description 4
- 150000003298 rubidium compounds Chemical class 0.000 claims description 4
- 150000003388 sodium compounds Chemical class 0.000 claims description 4
- 150000003438 strontium compounds Chemical class 0.000 claims description 4
- VAIOGRPEROWKJX-UHFFFAOYSA-N undecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCOP(O)(O)=O VAIOGRPEROWKJX-UHFFFAOYSA-N 0.000 claims description 4
- GKIQHTGBORJXKZ-UHFFFAOYSA-N undecylphosphonic acid Chemical compound CCCCCCCCCCCP(O)(O)=O GKIQHTGBORJXKZ-UHFFFAOYSA-N 0.000 claims description 4
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 3
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 3
- JZKFIPKXQBZXMW-UHFFFAOYSA-L beryllium difluoride Chemical compound F[Be]F JZKFIPKXQBZXMW-UHFFFAOYSA-L 0.000 claims description 3
- 229910001633 beryllium fluoride Inorganic materials 0.000 claims description 3
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 claims description 3
- UOKRBSXOBUKDGE-UHFFFAOYSA-N butylphosphonic acid Chemical compound CCCCP(O)(O)=O UOKRBSXOBUKDGE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 claims description 3
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 3
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 3
- OLGGYSFJQGDOFX-UHFFFAOYSA-N nonylphosphonic acid Chemical compound CCCCCCCCCP(O)(O)=O OLGGYSFJQGDOFX-UHFFFAOYSA-N 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 claims description 3
- 229910001637 strontium fluoride Inorganic materials 0.000 claims description 3
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 claims description 3
- POSYVRHKTFDJTR-UHFFFAOYSA-M tetrapropylazanium;fluoride Chemical compound [F-].CCC[N+](CCC)(CCC)CCC POSYVRHKTFDJTR-UHFFFAOYSA-M 0.000 claims description 3
- GAJQCIFYLSXSEZ-UHFFFAOYSA-N tridecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCOP(O)(O)=O GAJQCIFYLSXSEZ-UHFFFAOYSA-N 0.000 claims description 3
- KREGXBHGJXTOKZ-UHFFFAOYSA-N tridecylphosphonic acid Chemical compound CCCCCCCCCCCCCP(O)(O)=O KREGXBHGJXTOKZ-UHFFFAOYSA-N 0.000 claims description 3
- FRCRFINDRJFEFN-UHFFFAOYSA-N CCCCCCCCCCCCCOP(O)=O Chemical compound CCCCCCCCCCCCCOP(O)=O FRCRFINDRJFEFN-UHFFFAOYSA-N 0.000 claims description 2
- MGJJRXIEFROZLZ-UHFFFAOYSA-N CCCCCCCCCCCCOP(O)=O Chemical compound CCCCCCCCCCCCOP(O)=O MGJJRXIEFROZLZ-UHFFFAOYSA-N 0.000 claims description 2
- DEKOLWKUSOWLMN-UHFFFAOYSA-N CCCCCCCCCCCOP(O)=O Chemical compound CCCCCCCCCCCOP(O)=O DEKOLWKUSOWLMN-UHFFFAOYSA-N 0.000 claims description 2
- ZBEKPPVMYNVMQO-UHFFFAOYSA-N CCCCCCCCCCOP(O)=O Chemical compound CCCCCCCCCCOP(O)=O ZBEKPPVMYNVMQO-UHFFFAOYSA-N 0.000 claims description 2
- OCLUUUROQDRUIU-UHFFFAOYSA-N CCCCCCCCCOP(O)=O Chemical compound CCCCCCCCCOP(O)=O OCLUUUROQDRUIU-UHFFFAOYSA-N 0.000 claims description 2
- XJKCIKMIYBWISX-UHFFFAOYSA-N CCCCCCCCOP(O)=O Chemical compound CCCCCCCCOP(O)=O XJKCIKMIYBWISX-UHFFFAOYSA-N 0.000 claims description 2
- DEVJMJPPUVBPOV-UHFFFAOYSA-N CCCCCCCOP(O)=O Chemical compound CCCCCCCOP(O)=O DEVJMJPPUVBPOV-UHFFFAOYSA-N 0.000 claims description 2
- OEODWKRQWJHQSK-UHFFFAOYSA-N CCCCCCOP(O)=O Chemical compound CCCCCCOP(O)=O OEODWKRQWJHQSK-UHFFFAOYSA-N 0.000 claims description 2
- WMFDLEFIURCJJE-UHFFFAOYSA-N CCCCCOP(O)=O Chemical compound CCCCCOP(O)=O WMFDLEFIURCJJE-UHFFFAOYSA-N 0.000 claims description 2
- WCJLOEFXANROAO-UHFFFAOYSA-N CCCCOP(O)=O Chemical compound CCCCOP(O)=O WCJLOEFXANROAO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 description 38
- 238000001312 dry etching Methods 0.000 description 31
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 30
- 239000010408 film Substances 0.000 description 29
- 235000002639 sodium chloride Nutrition 0.000 description 27
- 229910052581 Si3N4 Inorganic materials 0.000 description 23
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 23
- 229910017052 cobalt Inorganic materials 0.000 description 20
- 239000010941 cobalt Substances 0.000 description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 20
- 239000004065 semiconductor Substances 0.000 description 17
- 235000012431 wafers Nutrition 0.000 description 14
- 238000011282 treatment Methods 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 239000011229 interlayer Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 229910000531 Co alloy Inorganic materials 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 239000007769 metal material Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000003405 preventing effect Effects 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- 150000003009 phosphonic acids Chemical class 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000873 masking effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 3
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical class CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 3
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical class CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 3
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- KUCWUAFNGCMZDB-UHFFFAOYSA-N 2-amino-3-nitrophenol Chemical compound NC1=C(O)C=CC=C1[N+]([O-])=O KUCWUAFNGCMZDB-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 159000000009 barium salts Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- LWBPNIJBHRISSS-UHFFFAOYSA-L beryllium dichloride Chemical compound Cl[Be]Cl LWBPNIJBHRISSS-UHFFFAOYSA-L 0.000 description 2
- RFVVBBUVWAIIBT-UHFFFAOYSA-N beryllium nitrate Chemical compound [Be+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O RFVVBBUVWAIIBT-UHFFFAOYSA-N 0.000 description 2
- KQHXBDOEECKORE-UHFFFAOYSA-L beryllium sulfate Chemical compound [Be+2].[O-]S([O-])(=O)=O KQHXBDOEECKORE-UHFFFAOYSA-L 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 229910000344 rubidium sulfate Inorganic materials 0.000 description 2
- GANPIEKBSASAOC-UHFFFAOYSA-L rubidium(1+);sulfate Chemical compound [Rb+].[Rb+].[O-]S([O-])(=O)=O GANPIEKBSASAOC-UHFFFAOYSA-L 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 159000000008 strontium salts Chemical class 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical class C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
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- 238000004364 calculation method Methods 0.000 description 1
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- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
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- ARRNBPCNZJXHRJ-UHFFFAOYSA-M hydron;tetrabutylazanium;phosphate Chemical compound OP(O)([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC ARRNBPCNZJXHRJ-UHFFFAOYSA-M 0.000 description 1
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- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
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- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
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- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
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- IDNLEIKAOODITA-UHFFFAOYSA-N octaazanium fluoro-dioxido-oxo-lambda5-phosphane Chemical compound P(=O)([O-])([O-])F.P(=O)([O-])([O-])F.P(=O)([O-])([O-])F.P(=O)([O-])([O-])F.[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+] IDNLEIKAOODITA-UHFFFAOYSA-N 0.000 description 1
- KBYKOQOSGXIFTR-UHFFFAOYSA-F octapotassium fluoro-dioxido-oxo-lambda5-phosphane Chemical compound P(=O)([O-])([O-])F.P(=O)([O-])([O-])F.P(=O)([O-])([O-])F.P(=O)([O-])([O-])F.[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+] KBYKOQOSGXIFTR-UHFFFAOYSA-F 0.000 description 1
- UKIAUDLPOGWHHI-UHFFFAOYSA-F octasodium fluoro-dioxido-oxo-lambda5-phosphane Chemical compound P(=O)([O-])([O-])F.P(=O)([O-])([O-])F.P(=O)([O-])([O-])F.P(=O)([O-])([O-])F.[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+] UKIAUDLPOGWHHI-UHFFFAOYSA-F 0.000 description 1
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- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
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- 159000000001 potassium salts Chemical class 0.000 description 1
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- 159000000005 rubidium salts Chemical class 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
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- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- MCZDHTKJGDCTAE-UHFFFAOYSA-M tetrabutylazanium;acetate Chemical compound CC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC MCZDHTKJGDCTAE-UHFFFAOYSA-M 0.000 description 1
- ZXUCBXRTRRIBSO-UHFFFAOYSA-L tetrabutylazanium;sulfate Chemical compound [O-]S([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC ZXUCBXRTRRIBSO-UHFFFAOYSA-L 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
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- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- AJPPAKACCOFNEN-UHFFFAOYSA-K tetraethylazanium;phosphate Chemical compound [O-]P([O-])([O-])=O.CC[N+](CC)(CC)CC.CC[N+](CC)(CC)CC.CC[N+](CC)(CC)CC AJPPAKACCOFNEN-UHFFFAOYSA-K 0.000 description 1
- TXBULBYASDPNNC-UHFFFAOYSA-L tetraethylazanium;sulfate Chemical compound [O-]S([O-])(=O)=O.CC[N+](CC)(CC)CC.CC[N+](CC)(CC)CC TXBULBYASDPNNC-UHFFFAOYSA-L 0.000 description 1
- MRYQZMHVZZSQRT-UHFFFAOYSA-M tetramethylazanium;acetate Chemical compound CC([O-])=O.C[N+](C)(C)C MRYQZMHVZZSQRT-UHFFFAOYSA-M 0.000 description 1
- IWISVGQUKNSOCC-UHFFFAOYSA-K tetramethylazanium;phosphate Chemical compound C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.[O-]P([O-])([O-])=O IWISVGQUKNSOCC-UHFFFAOYSA-K 0.000 description 1
- KJFVITRRNTVAPC-UHFFFAOYSA-L tetramethylazanium;sulfate Chemical compound C[N+](C)(C)C.C[N+](C)(C)C.[O-]S([O-])(=O)=O KJFVITRRNTVAPC-UHFFFAOYSA-L 0.000 description 1
- PXJUBOLFJDSAQQ-UHFFFAOYSA-M tetrapropylazanium;acetate Chemical compound CC([O-])=O.CCC[N+](CCC)(CCC)CCC PXJUBOLFJDSAQQ-UHFFFAOYSA-M 0.000 description 1
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-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
- HZPNJVXVIFRTRF-UHFFFAOYSA-N tetrapropylazanium;nitrate Chemical compound [O-][N+]([O-])=O.CCC[N+](CCC)(CCC)CCC HZPNJVXVIFRTRF-UHFFFAOYSA-N 0.000 description 1
- IGZKEGRSNICPPP-UHFFFAOYSA-K tetrapropylazanium;phosphate Chemical compound [O-]P([O-])([O-])=O.CCC[N+](CCC)(CCC)CCC.CCC[N+](CCC)(CCC)CCC.CCC[N+](CCC)(CCC)CCC IGZKEGRSNICPPP-UHFFFAOYSA-K 0.000 description 1
- JYFAUFFZEHJXIM-UHFFFAOYSA-L tetrapropylazanium;sulfate Chemical compound [O-]S([O-])(=O)=O.CCC[N+](CCC)(CCC)CCC.CCC[N+](CCC)(CCC)CCC JYFAUFFZEHJXIM-UHFFFAOYSA-L 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- CPWJKGIJFGMVPL-UHFFFAOYSA-K tricesium;phosphate Chemical compound [Cs+].[Cs+].[Cs+].[O-]P([O-])([O-])=O CPWJKGIJFGMVPL-UHFFFAOYSA-K 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- JOPDZQBPOWAEHC-UHFFFAOYSA-H tristrontium;diphosphate Chemical compound [Sr+2].[Sr+2].[Sr+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JOPDZQBPOWAEHC-UHFFFAOYSA-H 0.000 description 1
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 1
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Abstract
根据本发明,可以提供一种水性组合物,其包含:(A)组合物中的氟化物离子浓度达到0.05~30mmol/L的量的氟化物离子供给源;(B)组合物中的阳离子相对于氟化物离子的摩尔比达到0.3~20的量的阳离子供给源;和,以组合物总量基准计为0.0001~10质量%的(C)选自C4‑13烷基膦酸、C4‑13烷基膦酸酯、C4‑13烷基磷酸和它们的盐中的1种以上的化合物,所述水性组合物的pH处于2~6的范围。
Description
技术领域
本发明涉及水性组合物和使用其的清洗方法,例如涉及:电子器件(例如半导体元件)的制造工序中使用的清洗用组合物、和使用其的清洗方法。
背景技术
制造半导体元件等电子器件的过程中,形成半导体集成电路时,通常采用干蚀刻工序。该干蚀刻工序中,产生干蚀刻残渣(锆系残渣、钛系残渣、聚合物残渣等),需要将其去除。用于去除该干蚀刻残渣的清洗剂优选对成为清洗对象的半导体集成电路中使用的布线用金属材料(例如铜、钛、钴、钨等)不造成不良影响(例如侵蚀)者。
从这样的观点出发,开发了各种清洗剂。例如,专利文献1、专利文献2、专利文献3等公开了用于去除干蚀刻后产生的干蚀刻残渣的清洗用组合物、使用其的清洗方法等。
另外,形成半导体集成电路的过程中有时使用硬掩模。作为硬掩模的材料,一直以来使用硅系、钛系,但近年来还提出了氧化锆系的硬掩模(非专利文献1)。
现有技术文献
专利文献
专利文献1:日本特表2013-533631号公报
专利文献2:日本特开2016-171294号公报
专利文献3:日本特开2006-83376号公报
非专利文献
非专利文献1:M Padmanaban et al,J.Photopolym.Sci.Technol.,27(2014),503
发明内容
发明要解决的问题
电子器件中使用的布线用的金属材料、干蚀刻时使用的掩蔽材料中包括多种,其组合也有多种。因此,从干蚀刻残渣的去除效率、对布线用的金属材料的防腐蚀效果等的观点出发,要求开发出新的清洗用组合物。
用于解决问题的方案
本发明提供:以下的水性组合物、使用其的清洗方法等。
[1]一种水性组合物,其包含:
(A)组合物中的氟化物离子(例如F-等)浓度达到0.05~30mmol/L的量的氟化物离子供给源;
(B)组合物中的阳离子相对于氟化物离子的摩尔比达到0.3~20的量的阳离子供给源;和
以组合物总量基准计为0.0001~10质量%的(C)选自C4-13烷基膦酸、C4-13烷基膦酸酯、C4-13烷基磷酸和它们的盐中的1种以上的化合物,所述水性组合物的pH处于2~6(例如:2~5、2~4或2~3)的范围。
[2]根据上述[1]所述的水性组合物,其中,前述(A)成分的氟化物离子供给源为:氟化氢、氟化铵、酸性氟化铵、四甲基氟化铵、四乙基氟化铵、四丙基氟化铵、四丁基氟化铵、氟化锂、氟化钠、氟化钾、酸性氟化钾、氟化铷、氟化铯、氟化铍、氟化镁、氟化锶、氟化钡或它们的混合物。
[3]根据上述[1]或[2]所述的水性组合物,其中,前述(B)成分的阳离子供给源为:锂化合物、钠化合物、钾化合物、铷化合物、铯化合物、铍化合物、镁化合物、锶化合物、钡化合物、铵化合物、四甲基铵化合物、四乙基铵化合物、四丙基铵化合物、四丁基铵化合物、或它们的混合物(其中,排除含氟化合物)。
[4]根据上述[1]~[3]中任一项所述的水性组合物,其中,前述水性组合物选自如下物质中的至少任意者:
作为前述烷基膦酸的、正丁基膦酸、正戊基膦酸、正己基膦酸、正庚基膦酸、正辛基膦酸、正壬基膦酸、正癸基膦酸、正十一烷基膦酸、正十二烷基膦酸、正十三烷基膦酸、或它们的混合物;
作为前述烷基膦酸酯的、正丁基膦酸酯、正戊基膦酸酯、正己基膦酸酯、正庚基膦酸酯、正辛基膦酸酯、正壬基膦酸酯、正癸基膦酸酯、正十一烷基膦酸酯、正十二烷基膦酸酯、正十三烷基膦酸酯、或它们的混合物、和
前述烷基膦酸和前述烷基膦酸酯的盐。
[4a]根据上述[1]~[4]中任一项所述的水性组合物,其中,前述烷基膦酸为C5-12烷基膦酸(优选C5-11烷基膦酸、更优选C5-9烷基膦酸、进一步优选C6-8烷基膦酸),
前述烷基膦酸酯为这些烷基膦酸的酯。
[5]根据上述[1]~[3]中任一项所述的水性组合物,其中,前述水性组合物包含选自如下物质中的至少任意者:
作为前述烷基磷酸的、正丁基磷酸、正戊基磷酸、正己基磷酸、正庚基磷酸、正辛基磷酸、正壬基磷酸、正癸基磷酸、正十一烷基磷酸、正十二烷基磷酸、正十三烷基磷酸、磷酸-2-乙基己酯、磷酸异癸酯、或它们的混合物;以及,
前述烷基磷酸的盐。
[5a]根据上述[1]~[5]中任一项所述的水性组合物,其中,前述烷基磷酸为C4-13烷基磷酸(优选C5-11烷基磷酸、更优选C5-9烷基磷酸、进一步优选C6-8烷基磷酸)。
[5b]根据上述[1]~[5a]中任一项所述的水性组合物,其为用于去除干蚀刻后的残渣(例如,氧化锆系干蚀刻残渣)的干蚀刻残渣去除用组合物。
[5c]根据上述[1]~[5b]中任一项所述的水性组合物,其为用于对成为清洗对象的电子器件的布线材料(例如,钴或钴合金等)进行防腐蚀的组合物。
[5d]根据上述[1]~[5c]中任一项所述的水性组合物,其中,从前述烷基膦酸中排除十二烷基膦酸。
[5e]根据上述[1]~[5d]中任一项所述的组合物,其中,从氟化物离子供给源供给的氟化物离子的浓度在组合物中为0.05~30mmol/L(优选0.25~20mmol/L、更优选0.5~5mmol/L),以阳离子相对于氟化物离子的摩尔比计达到0.3~20的量包含从阳离子供给源供给的阳离子。
[6]一种电子器件的清洗方法,其包括如下工序:使上述[1]~[5e]中任一项所述的水性组合物与电子器件接触。
[7]一种电子器件的制造方法,其包括如下工序:使上述[1]~[5e]中任一项所述的组合物与电子器件接触。
[8]一种蚀刻液,其包含上述[1]~[5e]中任一项所述的组合物。
[9]一种清洗液,其包含上述[1]~[5e]中任一项所述的组合物。
发明的效果
本发明的优选方案中所述的水性组合物可以对氮化硅等蚀刻阻挡膜、层间绝缘膜、钴或钴合金等布线金属材料等进行防腐蚀,并效率良好地去除干蚀刻残渣(例如,锆系蚀刻残渣、钛系蚀刻残渣、聚合物系蚀刻残渣等)。
根据本发明的优选方案中所述的清洗方法,对氮化硅等蚀刻阻挡膜、层间绝缘膜、钴或钴合金等布线金属材料等的防腐蚀效果、蚀刻残渣去除性良好,因此,半导体元件等电子器件的制造工序中,可以成品率良好地制造高精度、高品质的电子器件。
附图说明
图1为具有去除干蚀刻残渣1前的半导体元件中的氧化锆系硬掩模2、钴或钴合金3、低介电常数层间绝缘膜5、氮化硅6的结构的半导体元件的一方式中的截面图的示意图。
具体实施方式
本发明中的水性组合物包含:(A)组合物中的氟化物离子浓度达到0.05~30mmol/L的量的氟化物离子供给源;(B)组合物中的阳离子相对于氟化物离子的摩尔比达到0.3~20的量的阳离子供给源;和,以组合物总量基准计为0.0001~10质量%的(C)选自C4-13烷基膦酸、C4-13烷基膦酸酯、C4-13烷基磷酸和它们的盐中的1种以上的化合物,所述水性组合物的pH处于2~6的范围。
以下,对本发明中所述的水性组合物详细地进行说明。
[(A)成分:氟化物离子供给源]
本发明中使用的氟化物离子供给源只要可以供给氟化物离子就没有特别限定。作为此处使用的氟化物离子供给源,例如,可以举出:氟化氢、氟化铵、酸性氟化铵、四甲基氟化铵、四乙基氟化铵、四丙基氟化铵、四丁基氟化铵、氟化锂、氟化钠、氟化钾、酸性氟化钾、氟化铷、氟化铯、氟化铍、氟化镁、氟化锶、氟化钡、或它们的混合物。这些之中,特别优选氟化氢、氟化铵、酸性氟化铵、四甲基氟化铵、氟化钾、酸性氟化钾。
氟化物离子供给源作为清洗液等使用时,以水性组合物中的氟化物离子浓度达到0.05~30mmol/L的方式进行配混。组合物中的优选的氟化物离子浓度为0.25~20mmol/L、更优选0.5~5mmol/L、进一步优选1.0~2.5mmol/L。例如,对于氟化物离子供给源的配混量,在组合物中通常以氟化氢换算计,为0.001~0.6质量%、优选0.005~0.5质量%、更优选0.02~0.4质量%。
[(B)成分:阳离子供给源]
本发明中使用的阳离子供给源没有特别限定,例如,可以举出:锂化合物、钠化合物、钾化合物、铷化合物、铯化合物、铍化合物、镁化合物、锶化合物、钡化合物、铵化合物、四甲基铵化合物、四乙基铵化合物、四丙基铵化合物、四丁基铵化合物、或它们的混合物。
作为优选的锂化合物,例如,可以举出:氢氧化锂、硝酸锂、硫酸锂、氯化锂、四氟磷酸锂、磷酸锂、乙酸锂等。
作为优选的钠化合物,例如,可以举出:氢氧化钠、硝酸钠、硫酸钠、氯化钠、四氟磷酸钠、磷酸钠、乙酸钠等。
作为优选的钾化合物,例如,可以举出:氢氧化钾、硝酸钾、硫酸钾、氯化钾、四氟磷酸钾、六氟磷酸钾、磷酸钾、乙酸钾等。
作为优选的铷化合物,例如,可以举出:氢氧化铷、硝酸铷、硫酸铷、氯化铷、四氟磷酸铷、磷酸铷、乙酸铷等。
作为优选的铯化合物,例如,可以举出:氢氧化铯、硝酸铯、硫酸铯、氯化铯、四氟磷酸铯、磷酸铯、乙酸铯等。
作为优选的铍化合物,例如,可以举出:氢氧化铍、硝酸铍、硫酸铍、氯化铍、四氟磷酸铍、磷酸铍、乙酸铍等。
作为优选的镁化合物,例如,可以举出:氢氧化镁、硝酸镁、硫酸镁、氯化镁、四氟磷酸镁、磷酸镁、乙酸镁等。
作为优选的锶化合物,例如,可以举出:氢氧化锶、硝酸锶、硫酸锶、氯化锶、四氟磷酸锶、磷酸锶、乙酸锶等。
作为优选的钡化合物,例如,可以举出:氢氧化钡、硝酸钡、硫酸钡、氯化钡、四氟磷酸钡、磷酸钡、乙酸钡等。
作为优选的铵化合物,例如,可以举出:氨、硝酸铵、硫酸铵、氯化铵、四氟磷酸铵、磷酸铵、乙酸铵等。
作为优选的四甲基铵化合物,例如,可以举出:氢氧化四甲基铵、硝酸四甲基铵、硫酸四甲基铵、氯化四甲基铵、四氟磷酸四甲基铵、磷酸四甲基铵、乙酸四甲基铵等。
作为优选的四乙基铵化合物,例如,可以举出:氢氧化四乙基铵、硝酸四乙基铵、硫酸四乙基铵、氯化四乙基铵、四氟磷酸四乙基铵、磷酸四乙基铵、乙酸四乙基铵等。
作为优选的四丙基铵化合物,例如,可以举出:四丙基氢氧化铵、硝酸四丙基铵、硫酸四丙基铵、氯化四丙基铵、四氟磷酸四丙基铵、磷酸四丙基铵、乙酸四丙基铵等。
作为优选的四丁基铵化合物,例如,可以举出:四丁基氢氧化铵、硝酸四丁基铵、硫酸四丁基铵、氯化四丁基铵、四氟磷酸四丁基铵、磷酸四丁基铵、乙酸四丁基铵等。
这些之中,特别优选硝酸铵、硝酸钾、硫酸钾、六氟磷酸钾、硝酸四甲基铵、硫酸锂、硫酸铷、氢氧化钾。
阳离子供给源作为清洗液等使用时,以水性组合物中的阳离子相对于氟化物离子的摩尔比(阳离子的摩尔浓度/氟化物离子的摩尔浓度)达到0.3~20、优选达到0.4~20、更优选达到0.5~10、进一步优选达到0.6~8的方式进行配混。本发明的另一实施方式中,上述摩尔比的下限值为0.1或0.2。例如,阳离子供给源的配混量通常以组合物总量基准计为0.020~2.00质量%的范围内,优选0.025~1.50质量%、更优选0.05~1.0质量%。
此处,在上述的阳离子相对于氟化物离子的摩尔比(阳离子的摩尔浓度/氟化物离子的摩尔浓度)的计算中,“阳离子的摩尔浓度”中不含源自(A)成分的质子。另一方面,使用除氟化氢(HF)以外的化合物作为(A)成分的情况下,将源自(A)成分的阳离子的摩尔浓度与源自(B)成分的阳离子的摩尔浓度的合计作为上述“阳离子的摩尔浓度”来计算。
[(C)成分:烷基膦酸、烷基膦酸酯、烷基磷酸或它们的盐]
(C1)烷基膦酸、烷基膦酸酯、或其盐
本发明中使用的烷基膦酸为具有4~13个碳原子的C4-13烷基膦酸(具有4~13个碳原子的烷基膦酸)。这样的烷基膦酸为公知的,另外能在商业上获得(例如,能自东京化成工业株式会社获得)。烷基膦酸优选C5-11烷基膦酸、更优选C5-9烷基膦酸、进一步优选C6-8烷基膦酸。烷基膦酸的烷基部分可以为直链也可以为支链,优选直链。烷基膦酸的烷基部分在分支的情况下,支链的数量优选5以下、更优选3以下、特别优选1。
本发明的水性组合物中,也可以使用上述烷基膦酸的酯。即,也可以使用上述C4-13烷基膦酸(具有4~13个碳原子的烷基膦酸)的烷基酯。
烷基膦酸通常用通式R1P(=O)(OH)2(R1为烷基)表示,通式R1P(=O)(OR2)2(R1为烷基、R2为烷基或氢原子:其中,2个R2中的至少一者为烷基)所示的烷基膦酸酯也能用于水性组合物。
另外,本说明书中记载的烷基膦酸酯也包含膦酸的烷基酯(膦酸酯)。即,通式R1P(=O)(OR2)2(R1为氢、R2为烷基或氢原子:其中,2个R2中的至少一者为烷基)所示的膦酸酯在本说明书中也作为烷基膦酸酯能用于水性组合物。
由以上表明,水性组合物中,作为烷基膦酸或烷基膦酸酯,可以使用以下的通式(A)所示的化合物。
R1P(=O)(OR2)2···(A)
(通式(A)中,R1和R2各自独立地为烷基或氢原子:其中,R1和2个R2中的至少一者为烷基。)
本发明中使用的烷基膦酸酯为合计具有4~13个碳原子的C4-13烷基膦酸酯(合计具有4~13个碳原子的烷基膦酸酯)。烷基膦酸酯优选C5-11烷基膦酸酯、更优选C5-9烷基膦酸酯、进一步优选C6-8烷基膦酸酯。另外,上述通式(A)中的R1和R2的烷基链各自独立地优选具有4~12个碳原子、更优选具有6~11个碳原子、进一步优选具有8~10个碳原子。
烷基膦酸酯的烷基、即、上述通式(A)的R1和R2可以为直链也可以为支链,优选包含直链状的烷基。
另外,上述通式(A)中的烷基链的数量、即、R1和R2的烷基链的合计数优选2以下。即,作为烷基膦酸酯,也可以使用上述通式(A)的R1P(=O)(OR2)2中的R1和R2均为烷基者,也可以使用R1为烷基、R2的一个以下为烷基者,或者R1为氢、R2的二个以下为烷基者等。进一步优选的是,优选使用仅具有单一的烷基链的烷基膦酸、即、上述通式(A)的R1P(=O)(OR2)2的R1和2个R2中、仅任一者为烷基者。特别优选的是,优选使用上述通式(A)的仅R1为烷基者。
本发明中使用的烷基膦酸的盐为上述烷基膦酸的盐,例如可以举出铵盐、四甲基铵盐、四乙基铵盐、四丙基铵盐、四丁基铵盐、锂盐、钠盐、钾盐、铷盐、铯盐、铍盐、镁盐、钙盐、锶盐、钡盐等。
作为本发明中使用的烷基膦酸或其盐,优选可以举出正丁基膦酸、正戊基膦酸、正己基膦酸、正庚基膦酸、正辛基膦酸、正壬基膦酸、正癸基膦酸、正十一烷基膦酸、正十二烷基膦酸、正十三烷基膦酸、它们的盐或它们的混合物。更优选使用的烷基膦酸或其盐为:正戊基膦酸、正己基膦酸、正庚基膦酸、正辛基膦酸、正壬基膦酸、正癸基膦酸、正十一烷基膦酸、它们的盐或它们的混合物。另外,本发明的水性组合物中,也可以使用上述烷基膦酸酯的盐。例如,作为烷基膦酸酯的盐,可以举出与上述烷基膦酸的盐对应者。
对于烷基膦酸、烷基膦酸酯、或其盐的水性组合物中的浓度,可以考虑成为蚀刻或清洗对象的电子器件的布线材料的种类、蚀刻工序中使用的掩蔽材料的种类等而适宜变更。优选的烷基膦酸、烷基膦酸酯、或其盐的浓度以组合物总量基准计为0.0003~5质量%、更优选0.0004~1质量%、进一步优选0.0005~0.1质量%、特别优选0.001~0.1质量%。
(C2)烷基磷酸或其盐
本发明中使用的烷基磷酸为具有4~13个碳原子的C4-13烷基磷酸(具有4~13个碳原子的烷基磷酸)。这样的烷基磷酸为公知的,另外能在商业上获得(例如,能自东京化成工业株式会社获得)。烷基磷酸优选C5-11烷基磷酸、更优选C5-9烷基磷酸、进一步优选C6-8烷基磷酸。烷基磷酸的烷基部分可以为直链也可以为支链,优选直链。烷基磷酸的烷基部分在分支的情况下,支链的数量优选5以下、更优选3以下、特别优选1。
本发明的水性组合物中,作为烷基磷酸,除磷酸的单烷基酯之外,也可以使用二烷基酯、和三烷基酯。即,不仅通式P(=O)(OR3)3(R3均为氢原子)所示的磷酸的R3中的仅1个被烷基所取代的磷酸的单烷基酯、而且R3中的2个被烷基所取代的二烷基酯、以及R3均被烷基所取代的三烷基酯都能用于本发明的水性组合物。其中,作为烷基磷酸,优选烷基链的数量为2以下的二烷基酯(上述通式P(=O)(OR3)3的R3中的2个为烷基者)和单烷基酯(上述通式P(=O)(OR3)3的R3中的仅1个为烷基者),更优选烷基链的数量为1的单烷基酯。即,烷基磷酸优选具有单一的烷基链(作为上述R3表示的烷基)。
烷基磷酸无论酯键的数量均具有合计4~13个碳原子。烷基磷酸无论酯键的数量均优选使用C5-11烷基磷酸、更优选使用C5-9烷基磷酸、进一步优选使用C6-8烷基磷酸。
另外,上述通式P(=O)(OR3)3的R3的烷基链优选具有4~12个碳原子,更优选具有6~11个碳原子,进一步优选具有8~10个碳原子。烷基磷酸的烷基、即、上述通式P(=O)(OR3)3的R3可以为直链也可以为支链,优选包含直链状的烷基。
本发明中使用的烷基磷酸的盐为上述磷酸的单烷基酯或者二烷基酯的盐,例如可以举出铵盐、四甲基铵盐、四乙基铵盐、四丙基铵盐、四丁基铵盐、锂盐、钠盐、钾盐、铷盐、铯盐、铍盐、镁盐、钙盐、锶盐、钡盐等。
作为本发明中使用的烷基磷酸或其盐,优选可以举出正丁基磷酸、正戊基磷酸、正己基磷酸、正庚基磷酸、正辛基磷酸、正壬基磷酸、正癸基磷酸、正十一烷基磷酸、正十二烷基磷酸、正十三烷基磷酸、磷酸-2-乙基己酯、磷酸异癸酯、它们的盐或它们的混合物。
作为更优选使用的烷基磷酸或其盐,为正戊基磷酸、正己基磷酸、正庚基磷酸、正辛基磷酸、正壬基磷酸、正癸基磷酸、正十一烷基磷酸、磷酸-2-乙基己酯、磷酸异癸酯、它们的盐或它们的混合物。
对于烷基磷酸或其盐的水性组合物中的浓度,可以考虑成为蚀刻或清洗对象的电子器件的布线材料的种类、蚀刻工序中使用的掩蔽材料的种类等而适宜变更。优选的烷基磷酸或其盐的浓度以组合物总量基准计为0.0003~5质量%、更优选0.0004~1质量%、进一步优选0.0005~0.1质量%、特别优选0.001~0.1质量%。
[(D)成分:水]
本发明的组合物为水性,包含水作为稀释剂。本发明中使用的水没有特别限定,优选通过蒸馏、离子交换处理、过滤器处理、各种吸附处理等而去除了金属离子、有机杂质、颗粒粒子等而成者,特别优选纯水或超纯水。
本组合物中的水的含量通常为40~99.9998质量%、优选89.5~99.998质量%。
[其他成分]
本发明的水性组合物中,根据期望可以在不有损本发明的目的的范围内配混一直以来用于半导体用水性组合物的添加剂。
例如,作为添加剂,可以添加酸、碱、螯合剂、表面活性剂、消泡剂、氧化剂、还原剂、金属防腐蚀剂、水溶性有机溶剂等。这些添加剂为公知的,例如记载于日本特表2013-533631号公报。
[水性组合物(液态组合物)的制备方法]
本发明的水性组合物(液态组合物)可以通过如下来制备:加入上述(A)成分、上述(B)成分、上述(C)成分、水、所需的其他成分,进行搅拌直至成为均匀。
水性组合物的pH的范围为2~6、优选2~5、更优选2~4、进一步优选2~3。
根据优选方案中所述的本发明的水性组合物,可以对氮化硅等蚀刻阻挡层、层间绝缘膜、钴或钴合金等布线金属材料等进行防腐蚀,并效率良好地去除干蚀刻残渣(例如,锆系蚀刻残渣、钛系蚀刻残渣、聚合物系蚀刻残渣等)。
[水性组合物的使用方法:电子器件的清洗/制造方法]
本发明中所述的水性组合物作为清洗用水性组合物(以下,也称为“清洗液”),在湿蚀刻工序(或其前后的工序)中,与电子器件(例如半导体元件)接触,从而可以将干蚀刻残渣去除。作为接触的方法,例如将清洗液收纳于清洗用容器,使成为清洗对象的电子器件浸渍于清洗液,从而可以将干蚀刻残渣去除,对电子器件进行清洗。或,以单张清洗方式对电子器件进行处理,从而可以将干蚀刻残渣去除,对电子器件进行清洗。清洗用水性组合物除适合用于干蚀刻残渣去除液(清洗液)之外还可以适合作为蚀刻液使用。另外,作为在化学机械研磨(CMP)的工序后对电子器件进行清洗的清洗液,也可以使用水性组合物。
如此,本发明的所述水性组合物能适合用于具备对电子器件进行清洗的工序的清洗方法、和包括这样的工序的电子器件的制造方法中。
使用本发明的清洗液的温度通常为10~80℃、优选15~70℃、进一步优选20℃~65℃、特别优选20℃~60℃。温度可以根据蚀刻的条件、使用的电子器件(例如半导体元件)而适宜选择。
使用本发明的清洗液的时间通常为0.2~60分钟。时间可以根据清洗的条件、使用的电子器件(例如半导体元件)而适宜选择。作为使用本发明的清洗液后的冲洗液,可以使用有机溶剂、水、碳酸水、氨水。
[成为清洗/制造对象的电子器件]
本发明可以适合使用的清洗对象、和作为制造对象的电子器件例如为半导体元件和显示元件,通常,干蚀刻工序后的中间制品成为清洗的对象。半导体元件和显示元件为硅、非晶质硅、多晶硅、玻璃等基板材料、氧化硅、氮化硅、碳化硅和它们的衍生物等绝缘材料、钴、钴合金、钨、钛-钨等材料、镓-砷、镓-磷、铟-磷、铟-镓-砷、铟-铝-砷等化合物半导体和铬氧化物等氧化物半导体。作为成为本发明的清洗对象的电子器件,特别优选可以举出使用钴或钴合金布线材料、氧化锆系硬掩模、低介电常数层间绝缘膜的元件。
对于本发明中成为对象的干蚀刻残渣,例如是将氧化锆系的硬掩模作为掩模,通过干蚀刻在低介电常数层间绝缘膜中形成导通孔、沟槽时产生的。干蚀刻残渣的一部分通过蚀刻气体与氧化锆系硬掩模接触而产生。因此,这种情况下,对象的干蚀刻残渣包含锆。
实施例
以下,根据实施例对本发明具体地进行说明,但只要发挥本发明的效果就可以适宜变更实施方式。
需要说明的是,只要没有特别指定,%就是指质量%。
[评价用晶圆]
<评价晶圆A>:用于干蚀刻残渣的去除状态的评价
从下层起将氮化硅、层间绝缘膜、氮化硅、氧化锆(硬掩模)、而且光致抗蚀剂制膜,接着,对光致抗蚀剂进行图案化。
将光致抗蚀剂作为掩模,以干蚀刻去除硬掩模的规定部位,利用基于氧等离子体的灰化去除光致抗蚀剂。进一步将硬掩模作为掩模,通过干蚀刻在氮化硅、层间绝缘膜中形成导通孔。
<带膜的晶圆>:用于使用氧化锆的残渣去除性评价、和用于氮化硅、钴的损伤评价
分别在以下的制膜条件制作氧化锆、氮化硅和钴各材料经制膜而成的带膜的晶圆。
[评价方法]
<膜厚>
带膜的晶圆的膜厚使用SII NanoTechnology Inc制荧光X射线装置SEA1200VX(膜厚测定装置A)、或者n&k technology company制光学式膜厚计n&k1280(膜厚测定装置B)而测定。带氧化锆膜的晶圆、带钴膜的晶圆使用膜厚测定装置A测定膜厚,带氮化硅膜的晶圆使用膜厚测定装置B测定膜厚。
<残渣的去除评价>
利用比表1的处理温度高20℃的温度下的氧化锆的E.R.进行判定。
判定方法:
将A、B判定作为合格。
<防腐蚀材料的防腐蚀评价>
利用在比表1的处理温度高20℃的温度下的氧化锆的E.R.进行判定。
判定方法:
SiN:利用在比表1的处理温度高20℃的温度下的氧化锆的E.R.除以表1的处理温度下的SiN的E.R.而得到的值进行判定。
判定方法:
A:2以上
B:1以上且低于2
B’:0.8以上且低于1
C:低于0.8
将A、B、B’判定作为合格。
Co:利用在比表1的处理温度高20℃的温度下的氧化锆的E.R.除以表1的处理温度下的钴的E.R.而得到的值进行判定。
判定方法:
A:1以上
B:0.1以上且低于1
C:低于0.1
将A、B判定作为合格。
<pH值的测定>
对于各实施例和比较例的水性组合物的pH值,在25℃下、使用pH计(株式会社堀场制作所制pH计F-52)测定。
[实施例1~21和比较例1~7]
试验中使用带氧化锆膜的晶圆、带氮化硅膜的晶圆、带钴膜的晶圆。在表1中记载的处理温度或比其高20℃的温度下,使其浸渍于表1中记载的水性组合物中,之后,进行利用超纯水的冲洗、利用干燥氮气气体喷射的干燥。
带氧化锆膜的晶圆、带氮化硅膜的晶圆、带钴膜的晶圆进行30分钟浸渍处理,由处理前后的膜厚算出E.R.。
可知,在实施例1~21中,可以边防止氮化硅和钴的损伤边去除干蚀刻残渣。
另一方面,可知,在表2的比较例1~7中,存在无法抑制钴的损伤的情况、存在无法边充分防止氮化硅的损伤边去除干蚀刻残渣的情况。
[表1]
[表2]
产业上的可利用性
本发明的优选方案中所述的水性组合物可以对氮化硅等蚀刻阻挡层、层间绝缘膜、钴或钴合金等布线金属材料等进行防腐蚀,并效率良好地去除干蚀刻残渣。
根据本发明的优选方案中所述的蚀刻液、清洗液和清洗方法,对氮化硅等蚀刻阻挡层、层间绝缘膜、钴或钴合金等布线金属材料等的防腐蚀效果、干蚀刻残渣去除性良好,因此,半导体元件等电子器件的制造工序中,可以成品率良好地制造高精度、高品质的电子器件。
附图标记说明
1.氧化锆系干蚀刻残渣
2.氧化锆系硬掩模
3.钴或钴合金
5.低介电常数层间绝缘膜
6.氮化硅(SiN)
Claims (9)
1.一种水性组合物,其包含:
(A)组合物中的氟化物离子浓度达到0.05~30mmol/L的量的氟化物离子供给源;
(B)组合物中的阳离子相对于氟化物离子的摩尔比达到0.3~20的量的阳离子供给源;和
以组合物总量基准计为0.0001~10质量%的(C)选自C4-13烷基膦酸、C4-13烷基膦酸酯、C4-13烷基磷酸、和它们的盐中的1种以上的化合物,
所述水性组合物的pH处于2~6的范围。
2.根据权利要求1所述的水性组合物,其中,所述(A)成分的氟化物离子供给源为:氟化氢、氟化铵、酸性氟化铵、四甲基氟化铵、四乙基氟化铵、四丙基氟化铵、四丁基氟化铵、氟化锂、氟化钠、氟化钾、酸性氟化钾、氟化铷、氟化铯、氟化铍、氟化镁、氟化锶、氟化钡、或它们的混合物。
3.根据权利要求1或2所述的水性组合物,其中,所述(B)成分的阳离子供给源为:锂化合物、钠化合物、钾化合物、铷化合物、铯化合物、铍化合物、镁化合物、锶化合物、钡化合物、铵化合物、四甲基铵化合物、四乙基铵化合物、四丙基铵化合物、四丁基铵化合物、或它们的混合物。
4.根据权利要求1~3中任一项所述的水性组合物,其中,
所述水性组合物包含选自如下物质中的至少任意者:
作为所述烷基膦酸的、正丁基膦酸、正戊基膦酸、正己基膦酸、正庚基膦酸、正辛基膦酸、正壬基膦酸、正癸基膦酸、正十一烷基膦酸、正十二烷基膦酸、正十三烷基膦酸、或它们的混合物;
作为所述烷基膦酸酯的、正丁基膦酸酯、正戊基膦酸酯、正己基膦酸酯、正庚基膦酸酯、正辛基膦酸酯、正壬基膦酸酯、正癸基膦酸酯、正十一烷基膦酸酯、正十二烷基膦酸酯、正十三烷基膦酸酯、或它们的混合物;以及,
所述烷基膦酸和所述烷基膦酸酯的盐。
5.根据权利要求1~3中任一项所述的水性组合物,其中,
所述水性组合物包含选自如下物质中的至少任意者:
作为所述烷基磷酸的、正丁基磷酸、正戊基磷酸、正己基磷酸、正庚基磷酸、正辛基磷酸、正壬基磷酸、正癸基磷酸、正十一烷基磷酸、正十二烷基磷酸、正十三烷基磷酸、磷酸-2-乙基己酯、磷酸异癸酯、或它们的混合物;以及,
所述烷基磷酸的盐。
6.一种电子器件的清洗方法,其包括如下工序:使权利要求1~5中任一项所述的水性组合物与电子器件接触。
7.一种电子器件的制造方法,其包括如下工序:使权利要求1~5中任一项所述的组合物与电子器件接触。
8.一种蚀刻液,其包含权利要求1~5中任一项所述的组合物。
9.一种清洗液,其包含权利要求1~5中任一项所述的组合物。
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CN115074743B (zh) * | 2022-06-30 | 2024-01-23 | 福建省佑达环保材料有限公司 | 一种用于OLED掩膜版表面阴极材料LiF清洗的组合物 |
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