TWI805062B - 用於溶解拋光粒子的組合物及使用其的清潔方法 - Google Patents
用於溶解拋光粒子的組合物及使用其的清潔方法 Download PDFInfo
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- TWI805062B TWI805062B TW110141267A TW110141267A TWI805062B TW I805062 B TWI805062 B TW I805062B TW 110141267 A TW110141267 A TW 110141267A TW 110141267 A TW110141267 A TW 110141267A TW I805062 B TWI805062 B TW I805062B
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- TW
- Taiwan
- Prior art keywords
- acid
- composition
- polishing particles
- dissolving
- ammonium
- Prior art date
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- 239000002245 particle Substances 0.000 title claims abstract description 96
- 239000000203 mixture Substances 0.000 title claims abstract description 73
- 238000004140 cleaning Methods 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000005498 polishing Methods 0.000 claims abstract description 116
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 30
- 239000011593 sulfur Substances 0.000 claims abstract description 30
- 150000007524 organic acids Chemical class 0.000 claims abstract description 19
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 15
- 239000011737 fluorine Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 15
- 230000008859 change Effects 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 230000009467 reduction Effects 0.000 claims abstract description 3
- 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 37
- -1 ion compound Chemical class 0.000 claims description 31
- 239000004065 semiconductor Substances 0.000 claims description 25
- 235000012431 wafers Nutrition 0.000 claims description 22
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 14
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 13
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 6
- 229920005591 polysilicon Polymers 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 5
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 5
- 125000005228 aryl sulfonate group Chemical group 0.000 claims description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- RVEZZJVBDQCTEF-UHFFFAOYSA-N sulfenic acid Chemical compound SO RVEZZJVBDQCTEF-UHFFFAOYSA-N 0.000 claims description 5
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 claims description 5
- VBLXCTYLWZJBKA-UHFFFAOYSA-N 2-(trifluoromethyl)aniline Chemical compound NC1=CC=CC=C1C(F)(F)F VBLXCTYLWZJBKA-UHFFFAOYSA-N 0.000 claims description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 4
- 150000003566 thiocarboxylic acids Chemical class 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 4
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 3
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 claims description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 3
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 claims description 2
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 claims description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims 1
- JMQUJWZJDHIEPX-UHFFFAOYSA-M [F-].[NH4+].C(C1=CC=CC=C1)[N+](C)(C)C.[F-] Chemical compound [F-].[NH4+].C(C1=CC=CC=C1)[N+](C)(C)C.[F-] JMQUJWZJDHIEPX-UHFFFAOYSA-M 0.000 claims 1
- QRKHABCNUJTEFW-UHFFFAOYSA-M [F-].[NH4+].[F-].C(C)[N+](CC)(CC)CC Chemical compound [F-].[NH4+].[F-].C(C)[N+](CC)(CC)CC QRKHABCNUJTEFW-UHFFFAOYSA-M 0.000 claims 1
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims 1
- XOGKVJRJHTYDBZ-UHFFFAOYSA-M azanium tetrabutylazanium difluoride Chemical compound [NH4+].[F-].[F-].CCCC[N+](CCCC)(CCCC)CCCC XOGKVJRJHTYDBZ-UHFFFAOYSA-M 0.000 claims 1
- LPLMZAJYUPAYQZ-UHFFFAOYSA-N diazanium;difluoride Chemical compound [NH4+].[NH4+].[F-].[F-] LPLMZAJYUPAYQZ-UHFFFAOYSA-N 0.000 claims 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 235000005985 organic acids Nutrition 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- VYECFMCAAHMRNW-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O.NS(O)(=O)=O VYECFMCAAHMRNW-UHFFFAOYSA-N 0.000 description 14
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000006227 byproduct Substances 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- GXHMMDRXHUIUMN-UHFFFAOYSA-N methanesulfonic acid Chemical compound CS(O)(=O)=O.CS(O)(=O)=O GXHMMDRXHUIUMN-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 230000007547 defect Effects 0.000 description 8
- 239000000356 contaminant Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229940098779 methanesulfonic acid Drugs 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- KFSZGBHNIHLIAA-UHFFFAOYSA-M benzyl(trimethyl)azanium;fluoride Chemical compound [F-].C[N+](C)(C)CC1=CC=CC=C1 KFSZGBHNIHLIAA-UHFFFAOYSA-M 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- GJXIMMNLGULQBX-UHFFFAOYSA-N S(=O)(=O)(O)OC=1C(C(=O)O)=CC=CC1.OC(=O)C=1C(O)=CC=C(S(=O)(=O)O)C1 Chemical compound S(=O)(=O)(O)OC=1C(C(=O)O)=CC=CC1.OC(=O)C=1C(O)=CC=C(S(=O)(=O)O)C1 GJXIMMNLGULQBX-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 3
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 3
- CBXWGGFGZDVPNV-UHFFFAOYSA-N so4-so4 Chemical compound OS(O)(=O)=O.OS(O)(=O)=O CBXWGGFGZDVPNV-UHFFFAOYSA-N 0.000 description 3
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 229940070337 ammonium silicofluoride Drugs 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 229940077388 benzenesulfonate Drugs 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 229960002796 polystyrene sulfonate Drugs 0.000 description 2
- 239000011970 polystyrene sulfonate Substances 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- KDKIWFRRJZZYRP-UHFFFAOYSA-N 1-hydroxypropane-2-sulfonic acid Chemical compound OCC(C)S(O)(=O)=O KDKIWFRRJZZYRP-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- NSRGOAGKXKNHQX-UHFFFAOYSA-N 2-hydroxybutane-1-sulfonic acid Chemical compound CCC(O)CS(O)(=O)=O NSRGOAGKXKNHQX-UHFFFAOYSA-N 0.000 description 1
- QKRMFCXDTFLKKT-UHFFFAOYSA-N 2-hydroxyethanesulfonic acid Chemical compound OCCS(O)(=O)=O.OCCS(O)(=O)=O QKRMFCXDTFLKKT-UHFFFAOYSA-N 0.000 description 1
- CZFRHHAIWDBFCI-UHFFFAOYSA-N 2-hydroxyhexane-1-sulfonic acid Chemical compound CCCCC(O)CS(O)(=O)=O CZFRHHAIWDBFCI-UHFFFAOYSA-N 0.000 description 1
- RIYJUQDMHMUBMK-UHFFFAOYSA-N 2-hydroxypentane-1-sulfonic acid Chemical compound CCCC(O)CS(O)(=O)=O RIYJUQDMHMUBMK-UHFFFAOYSA-N 0.000 description 1
- HSXUNHYXJWDLDK-UHFFFAOYSA-N 2-hydroxypropane-1-sulfonic acid Chemical compound CC(O)CS(O)(=O)=O HSXUNHYXJWDLDK-UHFFFAOYSA-N 0.000 description 1
- ZMPRRFPMMJQXPP-UHFFFAOYSA-N 2-sulfobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1S(O)(=O)=O ZMPRRFPMMJQXPP-UHFFFAOYSA-N 0.000 description 1
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 1
- BZOVBIIWPDQIHF-UHFFFAOYSA-N 3-hydroxy-2-methylbenzenesulfonic acid Chemical compound CC1=C(O)C=CC=C1S(O)(=O)=O BZOVBIIWPDQIHF-UHFFFAOYSA-N 0.000 description 1
- WQPMYSHJKXVTME-UHFFFAOYSA-N 3-hydroxypropane-1-sulfonic acid Chemical compound OCCCS(O)(=O)=O WQPMYSHJKXVTME-UHFFFAOYSA-N 0.000 description 1
- HYKDWGUFDOYDGV-UHFFFAOYSA-N 4-anilinobenzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1NC1=CC=CC=C1 HYKDWGUFDOYDGV-UHFFFAOYSA-N 0.000 description 1
- YEGPVWSPNYPPIK-UHFFFAOYSA-N 4-hydroxybutane-1-sulfonic acid Chemical compound OCCCCS(O)(=O)=O YEGPVWSPNYPPIK-UHFFFAOYSA-N 0.000 description 1
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 description 1
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical compound OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 description 1
- UCVLHOKPJHCDAH-UHFFFAOYSA-N C(CCCCCCCCCCC)C1=C(C=CC=C1)S(=O)(=O)O.C1(=CC=CC=C1)S(=O)(=O)OCCCCCCCCCCCC Chemical compound C(CCCCCCCCCCC)C1=C(C=CC=C1)S(=O)(=O)O.C1(=CC=CC=C1)S(=O)(=O)OCCCCCCCCCCCC UCVLHOKPJHCDAH-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- GCBPWKJIYOCTQC-UHFFFAOYSA-N NS(O)(=O)=O.NS(O)(=O)=O.NS(O)(=O)=O Chemical compound NS(O)(=O)=O.NS(O)(=O)=O.NS(O)(=O)=O GCBPWKJIYOCTQC-UHFFFAOYSA-N 0.000 description 1
- XXBYVLZQVLPBRN-UHFFFAOYSA-N OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O.OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O.OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O XXBYVLZQVLPBRN-UHFFFAOYSA-N 0.000 description 1
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- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- WWIWLTSSHDKOKO-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1.OS(=O)(=O)C1=CC=CC=C1 WWIWLTSSHDKOKO-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- MVIOINXPSFUJEN-UHFFFAOYSA-N benzenesulfonic acid;hydrate Chemical compound O.OS(=O)(=O)C1=CC=CC=C1 MVIOINXPSFUJEN-UHFFFAOYSA-N 0.000 description 1
- GCSVCUMDOQKEMT-UHFFFAOYSA-N butan-1-amine;hydrofluoride Chemical compound [H+].[F-].CCCCN GCSVCUMDOQKEMT-UHFFFAOYSA-N 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- BRXCDHOLJPJLLT-UHFFFAOYSA-N butane-2-sulfonic acid Chemical compound CCC(C)S(O)(=O)=O BRXCDHOLJPJLLT-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 230000009920 chelation Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- URTXPBSKBBUFNK-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O.CCS(O)(=O)=O URTXPBSKBBUFNK-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
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Abstract
本發明係關於一種用於溶解拋光粒子的組合物及使用其的清潔方法,更具體而言,關於一種用於溶解拋光粒子的組合物及使用其的清潔方法,上述用於溶解拋光粒子的組合物包括:含硫有機酸;含氟離子化合物;及溶劑,其中,於60℃溫度下測量15分鐘之濁度變化降低率(%)為-80至-99。
Description
本發明係關於一種用於溶解拋光粒子的組合物及使用其的清潔方法,更具體而言,關於一種用於溶解拋光粒子的組合物及使用其的清潔方法,其中上述用於溶解拋光粒子的組合物可作為用於在化學機械拋光(CMP)後清潔基板之清潔液。
化學機械拋光(CMP,Chemical Mechanical Polishing)是一種自半導體器件表面去除任意材料之過程,其中該表面藉由物理過程(如,拋光)與化學過程(如,氧化或螯合)進行拋光。於其最基本之形式中,CMP涉及將CMP漿料(例如,活性化合物與拋光粒子之溶液)施加至拋光墊上,該拋光墊拋光半導體晶圓之表面以實現去除、平坦化與拋光過程。於CMP步驟中拋光晶圓期間,CMP漿料溶液中所包括之拋光粒子趨向於彼此聚集。由於拋光粒子之此種聚集,即使CMP步驟已完成,仍可能有大量尺寸為幾μm以上之粒子殘留於晶圓上,並且晶圓表面上之劃痕(scratch)等缺陷可能於後續加工過程中由上述粒子引起。因此,於執行CMP步驟之後,需要一種清潔步驟以自晶圓表面去除諸如聚集粒子之類的污染物。
於使用二氧化矽漿料或二氧化鈰漿料等拋光粒子執行拋光步驟後,需要清潔步驟以去除殘留於基板表面上之拋光碎屑、拋光粒子、有機殘留物或副產物,並且,為了應對下一代半導體步驟技術,對研發新的清潔步驟及設備之要求亦越來越高。
用於清潔於其上執行CMP步驟之半導體晶圓之清潔步驟可以包括使用刷子(brush)擦洗(scrubbing)之清潔方法與使用清潔液之化學清潔方法。使用刷子進行擦洗之方法時用於去除吸附於晶圓上之污染物,例如CMP漿料及CMP殘留物,其於晶圓上噴灑去離子水(DI water)時使用刷子,藉此以機械方式去除吸附之污染物。然而,如果僅使用刷子之機械方法,污染物(如CMP漿料與CMP殘留物)可能無法完全去除,並且可能經常殘留,因此,難以執行後續步驟。於CMP步驟之後,有必要使用包含化學材料之清潔液藉由額外之清潔步驟完全去除殘留於晶圓上之污染物,然後執行後續步驟。
於使用清潔液之清潔步驟中,液相清潔於去除金屬污染方面有效,並且,通常使用HPM、SPM、臭氧水、DHF等進行處理。使用HPM與SPM難以完全去除金屬污染物,而DHF正被廣泛使用。
於使用二氧化鈰CMP漿料執行CMP步驟後,通常使用氫氟酸進行清潔,以去除殘留於基板表面上之二氧化鈰粒子作為拋光粒子。由於在使用氫氟酸進行清潔時對熱氧化膜之溶解度極高,因此可能會出現劃痕或表面缺陷,這可能會影響清潔後之步驟,並可能導致半導體器件之成品率與質量降低。
本發明之目的在於解決上述問題,即提供一種用於溶解拋光粒子的組合物,上述組合物包括含硫有機酸,以溶解及去除拋光步驟後殘留之拋光漿料、拋光粒子、源自拋光粒子之碎屑、拋光副產品等,並最小化缺陷。
本發明之另一目的在於在拋光步驟後提供一種使用根據本發明之用於溶解拋光粒子的組合物之清潔方法。
然而,本發明要解決之問題並非受限於以上言及之問題,未言及之其他問題能夠藉由以下記載由本領域普通技術人員所明確理解。
根據本發明一實施例之用於溶解拋光粒子的組合物,包括:含硫有機酸;含氟離子化合物;以及溶劑,其中,於60℃溫度下測量15分鐘之濁度變化降低率(%)為-80至-99。
根據本發明之一實施例,上述含硫有機酸可以占上述用於溶解拋光粒子的組合物之1重量%至10重量%。
根據本發明之一實施例,上述含硫有機酸可以包括選自由次磺酸(Sulfenic acid,RSOH)、亞磺酸(Sulfinic acid,RSO(OH))、有機磺酸(Sulfonic acid,RS(=0)2-OH)、硫代磺酸(Thiosulfonic acid,(RSO2SH))及硫代羧酸(Thiocarboxylic acid,RC(S)OH)所組成之群中之至少一種以上。
根據本發明之一實施例,上述有機磺酸可以包括選自由烷烴磺酸、烷醇磺酸、磺基琥珀酸及芳香族磺酸所組成之群中之至少一種以上。
根據本發明之一實施例,上述含氟離子化合物可以占上述
用於溶解拋光粒子的組合物之2重量%至10重量%。
根據本發明之一實施例,上述含氟離子化合物可以為離子氟化物化合物。
根據本發明之一實施例,上述含氟離子化合物可以包括選自由氟化銨(Ammonium fluoride)、二氟化銨(Ammonium bifluoride)、硼氟酸銨(Ammonium Fluoborate)、氟矽酸銨(Ammonium Silico Fluoride)、胺基三氟甲苯(Aminobenzotrifluoride)、四甲基氟化銨(Tetramethylammonium fluoride)、四乙基氟化銨(Tetraethylammonium fluoride)、四丁基二氟三苯矽酸銨(Tetrabutylammonium difluorotriphenylsilicate)、四丁基氟化銨(Tetrabutylammonium fluoride)及苄基三甲基氟化銨(Benzyltrimethylammonium fluoride)所組成之群中之至少一種以上。
根據本發明之一實施例,進而包括選自由硫代硫酸(Thiosulfuric acid,H2S2O3)、硫酸(Sulfuric acid)、硫化物(Sulfide)、二硫化物(Bisulfide,R-S-S-R')、硫化氫(Hydrogen sulfide,H2S)、三氧化硫(sulfur trioxide,SO3)、胺基磺酸(Sulfamic acid)、硫醇(Mercaptan,R-SH)及磺酸鹽所組成之群中之至少一種以上之含硫化合物,並且,上述含硫化合物可以占上述用於溶解拋光粒子的組合物之5重量%至15重量%。
根據本發明之一實施例,上述含硫化合物與含硫有機酸之質量比可以為2:1至5:1。
根據本發明之一實施例,上述磺酸鹽可以包含選自由烷基磺酸鹽(Alkyl sulfonate)、芳基磺酸鹽(Aryl sulfonate)、烷基芳基磺酸鹽
(Alkyl aryl sulfonate)、烷基醚磺酸鹽(Alkyl ether sulfonate)、聚苯乙烯磺酸鹽(Poly styrene sulfonate)、烷烴磺酸鹽(Alkane sulfonate)、α-烯烴磺酸鹽(α-olefin sulfonate)、十二烷基苯磺酸鹽(Dodecyl benzene sulfonate)及烷基苯磺酸鹽(Alkyl benzene sulfonate)所組成之群中之至少一種以上。
上述用於溶解拋光粒子的組合物可以用於拋光半導體器件晶圓後之清潔,其中,上述半導體器件包括選自由氮化矽膜、氧化矽膜、多晶矽膜及矽膜所組成之群中之至少一種膜。
根據本發明之一實施例,上述用於溶解拋光粒子的組合物可以於使用含有拋光粒子之化學機械拋光(CMP)用漿料來進行拋光後,溶解殘留之拋光粒子。
根據本發明之一實施例,上述拋光粒子可以包括二氧化鈰。
根據本發明一實施例之清潔方法,包括以下步驟:於半導體器件晶圓之化學機械拋光之後,使用根據本發明之用於溶解拋光粒子的組合物來清潔半導體器件晶圓。
根據本發明之一實施例,上述半導體器件晶圓可以包括選自由氮化矽膜、氧化矽膜、多晶矽膜及矽膜所組成之群中之至少一種膜。
本發明可以提供一種用於溶解拋光粒子的組合物,上述組合物包括含硫有機酸,以溶解及去除拋光步驟後殘留之拋光漿料、拋光粒子、源自拋光粒子之碎屑、拋光副產品等,並最小化缺陷。另外,根據本發明之用於溶解拋光粒子的組合物可以用作去除及清潔拋光污染物之清潔
液,尤其,可以用作可替代硫酸過氧化氫混合物(SPM,Sulfuric acid peroxide mixture)之清潔液。
以下,對本發明之實施例進行詳細說明。於說明本發明之過程中,當判斷對於相關公知功能或者構成之具體說明不必要地混淆本發明之要旨時,省略對其進行詳細說明。並且,本說明書中使用之術語用於準確地表達本發明之較佳之實施例,能夠根據使用者、利用者之意圖或者本發明所述技術領域之慣例有所不同。因此,對於本術語之定義應根據本說明書之整體內容進行定義。
於整體說明書中,當記載某個部件位於其他部件“上”時,不僅表示某一部件接觸其他部件之情況,亦包括兩個部件之間存在其他部件之情況。
於整體說明書中,當說明某一部分“包括”某一構成要素時,不表示排除其他構成要素,亦能夠包括其他構成要素。
以下,參照實施例對本發明之用於溶解拋光粒子的組合物及使用其的清潔方法進行具體說明。然而,本發明並非限定於上述實施例。
本發明涉及一種用於溶解拋光粒子的組合物,根據本發明之一實施例,上述用於溶解拋光粒子的組合物可以包括:含硫有機酸;含氟離子化合物;以及溶劑。
根據本發明之一實施例,上述含硫有機酸可以是於分子中具有硫及/或含硫官能團之有機酸,並且,其可以用作溶解活化劑來溶解拋光副產物,例如殘留拋光液、拋光碎片或粒子等。上述含硫有機酸可以
占上述用於溶解拋光粒子的組合物之1重量%至10重量%,當其含量小於上述範圍時,可能不進行溶解;當其超過上述範圍時,可能沈澱化學材料,或可能會降低溶解度。
作為本發明之一示例,上述含硫有機酸可以包括選自由次磺酸(Sulfenic acid,RSOH)、亞磺酸(Sulfinic acid,RSO(OH))、有機磺酸(Sulfonic acid,RS(=0)2-OH)、硫代磺酸(Thiosulfonic acid,(RSO2SH))及硫代羧酸(Thiocarboxylic acid,RC(S)OH)所組成之群中之至少一種以上。此處,R可選自氫、經取代或未經取代之烴(例如,具有1至20個碳數之烷基、具有6至30個碳數之經取代或未經取代之芳基以及經取代或未經取代之芳烷基)(例如,苄基、苯基、甲苯基、萘基等)及酯等,但並不限於此,將於下文中詳細描述。上述取代可以自羥基(-OH)、鹵素、羧基(-COOH)、具有1至10個碳數之烷基及具有6至10個碳數之芳基中之至少一個以上中被取代。上述鹽可以是無機鹽或有機鹽,例如,可以是鈉鹽、鉀鹽、鎂鹽或銨鹽等。
作為本發明之一示例,上述有機磺酸可以包括選自由烷烴磺酸(Alkane sulfonic acid)、烷醇磺酸、磺基琥珀酸及芳香族磺酸所組成之群中之至少一種以上。作為本發明之一示例,上述烷烴磺酸可以由CnH2n+1SO3H(例如,n=1至20)表示,並且例如,可以是甲磺酸、乙磺酸、1-丙磺酸、2-丙磺酸、1-丁磺酸、2-丁磺酸及戊磺酸等。
作為本發明之一示例,上述烷醇磺酸可以由CmH2m+1-CH(OH)-CpH2p-SO3H(例如,m=0至10,p=1至10)表示,並且例如,可以是2-羥基乙烷-1-磺酸(羥乙磺酸)、2-羥基丙烷-1-磺酸(2-丙醇磺酸)、3-羥基丙烷-1-磺酸、2-羥基丁烷-1-磺酸、2-羥基戊烷-1-磺酸、1-羥基丙烷-
2-磺酸、4-羥基丁烷-1-磺酸及2-羥基己烷-1-磺酸等。
作為本發明之一示例,上述芳香族磺酸可以是苯磺酸、烷基苯磺酸、胺基苯磺酸、硝基苯磺酸、磺基苯甲酸、羥基苯磺酸、甲苯磺酸、酚磺酸、萘磺酸、烷基萘磺酸、萘酚磺酸、二甲苯磺酸、甲苯酚磺酸、磺基水楊酸(5-磺基水楊酸)、聚苯乙烯磺酸、二苯胺-4-磺酸等。此處,可以自1至20個碳數中選擇烷基。
作為本發明之一示例,上述含硫有機酸可以是兩種或三種以上類型。第1化合物與第2化合物之比率可以為1至10:1至10;或1至5:1至5(w/w),或者,第1化合物、第2化合物與第3化合物之比率可以為1至10:1至10:1至10;或1至5:1至5:1至5(w/w)。
作為本發明之一示例,上述用於溶解拋光粒子的組合物可以進而包括含硫化合物以進一步激活拋光粒子之溶解。
作為本發明之一示例,上述含硫化合物可以占上述用於溶解拋光粒子的組合物之5重量%至15重量%。當其含量小於5重量%時,可能不會增加拋光粒子之溶解活性;當其超過15重量%時,半導體基板可能受到影響以引起缺陷,並且溶液可能會沈澱,或者可能發生加成反應。
作為本發明之一示例,上述含硫化合物可以包括選自由硫代硫酸(Thiosulfuric acid,H2S2O3)、硫酸(Sulfuric acid)、硫化物(Sulfide)、二硫化物(Bisulfide,R-S-S-R')、硫化氫(Hydrogen sulfide,H2S)、三氧化硫(sulfur trioxide,SO3)、胺基磺酸(Sulfamic acid)、硫醇(Mercaptan,R-SH)、硫酸鹽(Sulfate)、磺酸鹽(Sulfonate,R-SO3 -,R-SO3-R')及其鹽及其酸酐所組成之群中之至少一種以上。此處,R與R'可選自氫、經取代或未經取代之烴(例如,具有1至20個碳數之烷基、具有6至
30個碳數之經取代或未經取代之芳基以及經取代或未經取代之芳烷基)(例如,苄基、苯基、甲苯基、萘基等)及酯等,但並不限於此,將於下文中詳細描述。上述取代可以自羥基(-OH)、羧基(-COOH)、具有1至10個碳數之烷基及具有6至10個碳數之芳基中之至少一個以上中被取代。上述鹽可以是無機鹽或有機鹽,例如,可以是鈉鹽、鉀鹽、鎂鹽或銨鹽等。
作為本發明之一示例,上述磺酸鹽(Sulfonate)可以是上述磺酸之鹽或酯,例如,可以是烷基磺酸鹽(Alkyl sulfonate)、芳基磺酸鹽(Aryl sulfonate)、烷基芳基磺酸鹽(Alkyl aryl sulfonate)、烷基醚磺酸鹽(Alkyl ether sulfonate)、聚苯乙烯磺酸鹽(Poly styrene sulfonate)、烷烴磺酸鹽(Alkane sulfonate)、α-烯烴磺酸鹽(α-olefin sulfonate)、十二烷基苯磺酸鹽(Dodecyl benzene sulfonate)及烷基苯磺酸鹽(Alkyl benzene sulfonate)等。此處,可以自1至20個碳數中選擇烷基及烷烴,可以自6至30個碳數中選擇上述芳基。
作為本發明之一示例,上述含硫化合物可以是兩種或三種以上類型。第1化合物與第2化合物之比率可以為1至10:1至10;或1至5:1至5(w/w),或者,第1化合物、第2化合物與第3化合物之比率可以為1至10:1至10:1至10;或1至5:1至5:1至5(w/w)。
作為本發明之一示例,上述含氟離子化合物可以作為蝕刻劑與還原觸媒,以協助拋光步驟後殘留之拋光粒子、拋光粒子衍生之副產物等以水合物之形式溶解於水中。
作為本發明之一示例,上述含氟離子化合物可以占上述用於溶解拋光粒子的組合物之2重量%至10重量%,並且,當其含量小於2重量%時,可能不會生成水合物;當其超過10重量%時,可能會影響半導體
基板以導致缺陷。
作為本發明之一示例,上述含氟離子化合物可以是離子氟化物化合物。上述含氟離子化合物可以包括選自由氟化銨(Ammonium fluoride)、二氟化銨(Ammonium bifluoride)、硼氟酸銨(Ammonium Fluoborate)、氟矽酸銨(Ammonium Silico Fluoride)、胺基三氟甲苯(Aminobenzotrifluoride)、四甲基氟化銨(Tetramethylammonium fluoride)、四乙基氟化銨(Tetraethylammonium fluoride)、四丁基二氟三苯矽酸銨(Tetrabutylammonium difluorotriphenylsilicate)、四丁基氟化銨(Tetrabutylammonium fluoride)及苄基三甲基氟化銨(Benzyltrimethylammonium fluoride)所組成之群中之至少一種以上。
作為本發明之一示例,上述含硫化合物與含硫有機酸之質量比可以為2:1至5:1。作為本發明之一示例,上述含硫有機酸與上述含氟離子化合物之質量比(w/w)可以為1:1至1:15。即,當含硫有機酸與含氟離子化合物包括於上述質量比範圍內時,可以獲得拋光粒子及其副產物之優異溶解性,並且可以最小化對半導體基板之損傷。
根據本發明之一實施例,上述溶劑可以包括水及/或有機溶劑。上述組合物中之溶劑可用於溶解及/或分散組合物中之其他組分。溶劑較佳為儘可能不包括抑制其他組分作用之雜質。具體而言,上述溶劑可以包括離子交換水、或純水、超純水、去離子水或蒸餾水,其中,上述離子交換水使用離子交換樹脂來去除雜質離子後,藉由過濾器從中去除異物。
作為本發明之一示例,上述組合物之pH值可以在2至7之範圍內。當pH值於上述pH值範圍內時,並且當於其上執行CMP之基板(例
如,使用上述組合物處理半導體器件之晶圓)時,可以充分去除清潔步驟中殘留之拋光粒子、有機材料、雜質等污染物,從而最小化缺陷。
作為本發明之一示例,可以基於濁度之變化來確認上述組合物相對於拋光粒子、源自拋光粒子之碎屑及拋光副產物之溶解及去除性能。例如,於室溫(rt)至80℃;50℃至70℃或約60℃之溫度下,在包括上述組合物及拋光粒子、源自拋光粒子之碎屑及拋光副產物中之任一種之混合溶液中測量15分鐘的濁度變化降低率(%)可以為-80至-99。
根據本發明之一實施例,上述組合物可以用於清潔CMP步驟後之基板表面上之拋光粒子或黏附及/或殘留有源自拋光粒子之異物之基板。例如,上述基板可以是半導體器件用基板,例如矽基板、藍寶石基板、石英基板、玻璃基板、陶瓷基板等。
作為本發明之一示例,上述半導體器件晶圓可以包括選自由氮化矽膜、氧化矽膜、多晶矽膜及矽膜所組成之群中之至少一種膜,並且,上述膜可以於拋光步驟中用作拋光對象膜或拋光停止膜。
作為本發明之一示例,上述組合物可以用於去除已被拋光之半導體器件之晶圓表面上之缺陷、殘留物及污染物,並且可以用於在CMP步驟之後溶解及/或去除拋光步驟殘留物(例如,拋光粒子、源自拋光粒子之異物)。
作為本發明之一示例,上述殘留物可以是CMP拋光漿料之拋光粒子、源自拋光粒子之材料、CMP漿料中存在之化學材料、CMP拋光漿料之副產物、富碳粒子、拋光墊粒子、刷卸粒子、設備材料、金屬及金屬氧化物等。例如,可以用於溶解及/或去除包括拋光粒子之CMP漿料之拋光粒子及/或自拋光粒子衍生之碎屑及粒子。
作為本發明之一示例,上述化學機械拋光漿料之拋光粒子可以包括選自由金屬氧化物、塗覆有有機物或無機物之金屬氧化物及處於膠體狀態之金屬氧化物所組成之群中之至少一種以上,並且,上述金屬氧化物可以包括選自由二氧化矽、二氧化鈰、氧化鋯、氧化鋁、二氧化鈦、鈦酸鋇、氧化鍺、氧化錳及氧化鎂所組成之群中之至少一種以上,較佳可為二氧化鈰。
作為本發明之一示例,上述拋光粒子可以包括10nm至200nm之單一尺寸粒子或具有10nm至200nm之兩種以上不同尺寸之混合粒子。
本發明係關於一種用於溶解拋光粒子的組合物及使用其的清潔方法,根據本發明之一實施例,上述清潔方法可以包括以下步驟:於半導體器件晶圓之化學機械拋光之後,使用本發明之用於溶解拋光粒子的組合物來清潔半導體器件晶圓。
下面,將參考以下實施例及比較例詳細描述本發明。然而,本發明之技術思想並不限於此。
實施例1
製備了包括1重量%至10重量%之甲磺酸(Methane sulfonic acid)及2重量%至10重量%之氟化銨(Ammonium fluoride)之組合物。
實施例2
製備了包括1重量%至10重量%之甲磺酸(Methane sulfonic acid)(含實施例1之10倍含量)及2重量%至10重量%之氟化銨(Ammonium fluoride)之組合物。
實施例3
製備了包括1重量%至10重量%之對甲苯磺酸(p-Toluene sulfonic acid)及2重量%至10重量%之氟化銨(Ammonium fluoride)之組合物。
實施例4
製備了包括1重量%至10重量%之對甲苯磺酸(p-Toluene sulfonic acid)(實施例3之10倍含量)及2重量%至10重量%之氟化銨(Ammonium fluoride)之組合物。
實施例5
製備了包括1重量%至10重量%之甲磺酸(Methane sulfonic acid)、5重量%至15重量%之胺基磺酸(Sulfamic acid)及2重量%至10重量%之氟化銨(Ammonium fluoride)之組合物。
實施例6
製備了包括1重量%至10重量%之甲磺酸(Methane sulfonic acid)及5-磺基水楊酸(Sulfosalicylic acid)、5重量%至15重量%之胺基磺酸(Sulfamic acid)(甲磺酸:5-磺基水楊酸:胺基磺酸=1:1:3(w/w))及2重量%至10重量%之氟化銨(Ammonium fluoride)之組合物。
實施例7
製備了包括1重量%至10重量%之甲磺酸(Methane sulfonic acid)、5重量%至15重量%之胺基磺酸(Sulfamic acid)(甲磺酸:胺基磺酸=1:2(w/w))及2重量%至10重量%之氟化銨(Ammonium fluoride)之組合物。
實施例8
製備了包括1重量%至10重量%之聚苯乙烯磺酸
(Polystyrene sulfonic acid)、5重量%至15重量%之胺基磺酸(Sulfamic acid)及2重量%至10重量%之氟化銨(Ammonium fluoride)之組合物。
實施例9
製備了包括1重量%至10重量%之甲磺酸(Methane sulfonic acid)、5重量%至15重量%之硫酸及2重量%至10重量%之氟化銨(Ammonium fluoride)之組合物。
實施例10
製備了包括1重量%至10重量%之甲磺酸(Methane sulfonic acid)(實施例7之6倍)、5重量%至15重量%之胺基磺酸(Sulfamic acid)及2重量%至10重量%之氟化銨(Ammonium fluoride)之組合物。
實施例11
製備了包括1重量%至10重量%之甲磺酸(Methane sulfonic acid)、5重量%至15重量%之胺基磺酸(Sulfamic acid)及2重量%至10重量%之氟化銨(Ammonium fluoride)(實施例7之1.1至1.5倍)之組合物。
實施例12
製備了包括1重量%至10重量%之乙磺酸(Ethane sulfonic acid)、5重量%至15重量%之胺基磺酸(Sulfamic acid)及2重量%至10重量%氟化銨(Ammonium fluoride)之組合物。
實施例13
製備了包括1重量%至10重量%之苯磺酸(Benzene sulfonic acid)、5重量%至15重量%之胺基磺酸(Sulfamic acid)及2重量%至10重量%之氟化銨(Ammonium fluoride)之組合物。
實施例14
製備了包括1重量%至10重量%之甲磺酸(Methane sulfonic acid)及5-磺基水楊酸(Sulfosalicylic acid)(MSA:SSA=1:1(w/w)及2重量%至10重量%之氟化銨(Ammonium fluoride)之組合物。
實施例15
製備了包括1重量%至10重量%之甲磺酸(Methane sulfonic acid)、5重量%至15重量%之胺基磺酸(Sulfamic acid)及1重量%至10重量%之氟化銨(Ammonium fluoride)之組合物。
實施例16
製備了包括1重量%至10重量%之甲磺酸(Methane sulfonic acid)、5重量%至15重量%之胺基磺酸(Sulfamic acid)及2重量%至10重量%之氟化銨(Ammonium fluoride)(實施例15之5倍)之組合物。
實施例17
製備了包括1重量%至10重量%之甲磺酸(Methane sulfonic acid)、5重量%至15重量%之胺基磺酸(Sulfamic acid)及2重量%至10重量%之氟化銨(Ammonium fluoride)(實施例15之7倍)之組合物。
實施例18
製備了包括1重量%至10重量%之5-磺基水楊酸(Sulfosalicylic acid)、5重量%至15重量%之胺基磺酸(Sulfamic acid)及2重量%至10重量%之氟化銨(Ammonium fluoride)之組合物。
比較例1
市售之硫酸過氧化氫混合物(SPM,Sulfuric Peroxide Mixture)清潔液。
比較例2
包括磷酸及過氧化氫(3:1(w/w),基於重量%)之清潔液。
比較例3
製備了包括0.1重量%至10重量%之甲磺酸(Methane sulfonic acid)及5重量%至20重量%之硫酸之組合物。
*於實施例及比較例中,溶劑為殘留量或適當量之去離子水。
觀察濁度之變化(NTU_%)
為了驗證於實施例及比較例中製備之清潔液之二氧化鈰粒子之溶解性能,將每種清潔液添加至含有0.01重量%之二氧化鈰漿料之溶液中,並分別於室溫60℃及80℃下分別攪拌1分鐘至15分鐘,之後使用濁度變化評估設備(HACH 2100Q)來觀察濁度變化。其結果如表2所示。上述濁度變化之基準是含有0.01重量%之二氧化鈰漿料之溶液(濁度:169)。
參考表2可以看出,根據本發明之組合物於溶解二氧化鈰粒子之過程中根據濁度之變化對二氧化鈰粒子之溶解性變得優異。此外,可以確認,於半導體器件基板之CMP步驟之後之清潔步驟中,二氧化鈰粒子之溶解性能優於SPM之溶解性能,因此,其可適用於在CMP步驟後之清潔步驟之SPM清潔步驟,或可用於可替代SPM之清潔液。此外,考慮到表2中所示之二氧化鈰粒子之溶解及去除性能,於CMP步驟後之清潔步驟中使用刷子(brush)模塊之清潔方法中,預期根據本發明之組合物可以用於去除拋光粒子及自其衍生之副產品、CMP步驟之殘留物等。
綜上,藉由有限之實施例對實施例進行了說明,於本技術領域內具有常識者能夠對上述記載進行多種修改與變化。例如,所說明之技術以與所說明之方法不同之順序執行,及/或所說明之構成要素以與所說明之方法不同之形態結合或組合,或者,由其他構成要素或等同物進行替換或置換也能夠獲得相同之效果。因此,其他體現、其他實施例及權利要求範圍之均等物全部屬於專利權利要求之範圍。
Claims (13)
- 一種用於溶解拋光粒子的組合物,其包括:含硫有機酸;含氟離子化合物;及溶劑;於60℃溫度下測量15分鐘之濁度變化降低率(%)為-80至-99;其中該含硫有機酸占該用於溶解拋光粒子的組合物之1重量%至10重量%;及其中該含氟離子化合物占該用於溶解拋光粒子的組合物之2重量%至10重量%。
- 如請求項1之用於溶解拋光粒子的組合物,其中該含硫有機酸包括選自由次磺酸、亞磺酸、有機磺酸、硫代磺酸及硫代羧酸所組成之群中之至少一種以上。
- 如請求項2之用於溶解拋光粒子的組合物,其中該有機磺酸包括選自由烷烴磺酸、烷醇磺酸、磺基琥珀酸及芳香族磺酸所組成之群中之至少一種以上。
- 如請求項1之用於溶解拋光粒子的組合物,其中該含氟離子化合物為離子氟化物化合物。
- 如請求項1之用於溶解拋光粒子的組合物,其中該含氟離子化合物包括選自由氟化銨、二氟化銨、硼氟酸銨、氟矽酸銨、胺基三氟甲苯、四甲基氟化銨、四乙基氟化銨、四丁基二氟三苯矽酸銨、四丁基氟化銨及苄基三甲基氟化銨所組成之群中之至少一種以上。
- 如請求項1之用於溶解拋光粒子的組合物,其進而包括:選自由硫代硫酸、硫酸、硫化物、二硫化物、硫化氫、三氧化硫、胺基磺酸、硫醇及磺酸鹽所組成之群中之至少一種以上之含硫化合物,該含硫化合物占該用於溶解拋光粒子的組合物之5重量%至15重量%。
- 如請求項6之用於溶解拋光粒子的組合物,其中該含硫化合物與含硫有機酸之質量比為2:1至5:1。
- 如請求項6之用於溶解拋光粒子的組合物,其中該磺酸鹽包含選自由烷基磺酸鹽、芳基磺酸鹽、烷基芳基磺酸鹽、烷基醚磺酸鹽、聚苯乙烯磺酸鹽、烷烴磺酸鹽、α-烯烴磺酸鹽、十二烷基苯磺酸鹽及烷基苯磺酸鹽所組成之群中之至少一種以上。
- 如請求項1之用於溶解拋光粒子的組合物,其中該用於溶解拋光粒子的組合物用於拋光半導體器件晶圓後之清潔,其中,該半導體器件包括選自由氮化矽膜、氧化矽膜、多晶矽膜及矽膜所組成之群中之至少一種膜。
- 如請求項1之用於溶解拋光粒子的組合物,其中該用於溶解拋光粒子的組合物於使用含有拋光粒子之化學機械拋光用漿料來進行拋光後,溶解殘留之拋光粒子。
- 如請求項10之用於溶解拋光粒子的組合物,其中該拋光粒子包括二氧化鈰。
- 一種清潔方法,其包括以下步驟:於半導體器件晶圓之化學機械拋光之後,使用如請求項1至11中任一項之用於溶解拋光粒子的組合物來清潔該半導體器件晶圓。
- 如請求項12之清潔方法,其中該半導體器件晶圓包括選自由氮化矽膜、氧化矽膜、多晶矽膜及矽膜所組成之群中之至少一種膜。
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