TWI632233B - Grinding composition - Google Patents
Grinding composition Download PDFInfo
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- TWI632233B TWI632233B TW103123302A TW103123302A TWI632233B TW I632233 B TWI632233 B TW I632233B TW 103123302 A TW103123302 A TW 103123302A TW 103123302 A TW103123302 A TW 103123302A TW I632233 B TWI632233 B TW I632233B
- Authority
- TW
- Taiwan
- Prior art keywords
- polishing
- polishing composition
- group
- acid
- surfactant
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 140
- 238000000227 grinding Methods 0.000 title claims description 13
- 238000005498 polishing Methods 0.000 claims abstract description 272
- 229910052751 metal Inorganic materials 0.000 claims abstract description 67
- 239000002184 metal Substances 0.000 claims abstract description 67
- 239000004094 surface-active agent Substances 0.000 claims abstract description 63
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 39
- 125000003118 aryl group Chemical group 0.000 claims abstract description 21
- 125000005013 aryl ether group Chemical group 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 15
- 150000008378 aryl ethers Chemical class 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 12
- 125000001424 substituent group Chemical group 0.000 claims abstract description 10
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 8
- 239000006061 abrasive grain Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 33
- 230000004888 barrier function Effects 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 238000005260 corrosion Methods 0.000 claims description 18
- 239000003112 inhibitor Substances 0.000 claims description 17
- 230000007797 corrosion Effects 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 13
- 235000000346 sugar Nutrition 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000011164 primary particle Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 4
- 150000004676 glycans Chemical class 0.000 claims description 4
- 229920001282 polysaccharide Polymers 0.000 claims description 4
- 239000005017 polysaccharide Substances 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 16
- 238000003860 storage Methods 0.000 abstract description 15
- 230000009467 reduction Effects 0.000 abstract description 7
- -1 amine salt Chemical class 0.000 description 76
- 239000010410 layer Substances 0.000 description 47
- 239000010949 copper Substances 0.000 description 35
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 23
- 230000000694 effects Effects 0.000 description 21
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 17
- 239000007800 oxidant agent Substances 0.000 description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 229910019142 PO4 Inorganic materials 0.000 description 14
- 229910000420 cerium oxide Inorganic materials 0.000 description 14
- 229910052802 copper Inorganic materials 0.000 description 14
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 14
- 239000010452 phosphate Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 238000005530 etching Methods 0.000 description 12
- 150000007524 organic acids Chemical class 0.000 description 10
- 150000005215 alkyl ethers Chemical class 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 238000005192 partition Methods 0.000 description 9
- 230000009471 action Effects 0.000 description 8
- 230000007246 mechanism Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000003945 anionic surfactant Substances 0.000 description 7
- 239000002736 nonionic surfactant Substances 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 230000001681 protective effect Effects 0.000 description 7
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229910000881 Cu alloy Inorganic materials 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 230000006870 function Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 5
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 5
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 5
- 150000002391 heterocyclic compounds Chemical group 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 230000001629 suppression Effects 0.000 description 5
- XZHWEHOSQYNGOL-UHFFFAOYSA-N 1-(1h-benzimidazol-2-yl)ethanol Chemical compound C1=CC=C2NC(C(O)C)=NC2=C1 XZHWEHOSQYNGOL-UHFFFAOYSA-N 0.000 description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 4
- JWYUFVNJZUSCSM-UHFFFAOYSA-N 2-aminobenzimidazole Chemical compound C1=CC=C2NC(N)=NC2=C1 JWYUFVNJZUSCSM-UHFFFAOYSA-N 0.000 description 4
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- 229920001353 Dextrin Polymers 0.000 description 4
- 239000004375 Dextrin Substances 0.000 description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 235000019425 dextrin Nutrition 0.000 description 4
- 238000013467 fragmentation Methods 0.000 description 4
- 238000006062 fragmentation reaction Methods 0.000 description 4
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 3
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 3
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 3
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 3
- COYPLDIXZODDDL-UHFFFAOYSA-N 3h-benzimidazole-5-carboxylic acid Chemical compound OC(=O)C1=CC=C2N=CNC2=C1 COYPLDIXZODDDL-UHFFFAOYSA-N 0.000 description 3
- PZOUSPYUWWUPPK-UHFFFAOYSA-N 4-methyl-1h-indole Chemical compound CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 3
- LRSYZHFYNDZXMU-UHFFFAOYSA-N 9h-carbazol-3-amine Chemical compound C1=CC=C2C3=CC(N)=CC=C3NC2=C1 LRSYZHFYNDZXMU-UHFFFAOYSA-N 0.000 description 3
- XHGKPMMTTJRQLM-UHFFFAOYSA-N 9h-carbazol-4-amine Chemical compound N1C2=CC=CC=C2C2=C1C=CC=C2N XHGKPMMTTJRQLM-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000004471 Glycine Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- DBVDJVCGWHBNJB-UHFFFAOYSA-N OC1=CCC2=NC3=CC=CC=C3C2=C1 Chemical compound OC1=CCC2=NC3=CC=CC=C3C2=C1 DBVDJVCGWHBNJB-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 229920001218 Pullulan Polymers 0.000 description 3
- 239000004373 Pullulan Substances 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229940024606 amino acid Drugs 0.000 description 3
- 235000001014 amino acid Nutrition 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 229940063953 ammonium lauryl sulfate Drugs 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- FVEXIHSMWMFMRK-UHFFFAOYSA-N benzotriazol-1-yl(pyridin-4-yl)methanone Chemical compound N1=NC2=CC=CC=C2N1C(=O)C1=CC=NC=C1 FVEXIHSMWMFMRK-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000009920 chelation Effects 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- QMPFMODFBNEYJH-UHFFFAOYSA-N methyl 1h-1,2,4-triazole-5-carboxylate Chemical compound COC(=O)C1=NC=NN1 QMPFMODFBNEYJH-UHFFFAOYSA-N 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 235000019423 pullulan Nutrition 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 229910021653 sulphate ion Inorganic materials 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- OBENDWOJIFFDLZ-UHFFFAOYSA-N (3,5-dimethylpyrazol-1-yl)methanol Chemical compound CC=1C=C(C)N(CO)N=1 OBENDWOJIFFDLZ-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 2
- HXQHRUJXQJEGER-UHFFFAOYSA-N 1-methylbenzotriazole Chemical compound C1=CC=C2N(C)N=NC2=C1 HXQHRUJXQJEGER-UHFFFAOYSA-N 0.000 description 2
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 2
- GRWAIJBHBCCLGS-UHFFFAOYSA-N 2-(tetrazol-1-yl)acetic acid Chemical compound OC(=O)CN1C=NN=N1 GRWAIJBHBCCLGS-UHFFFAOYSA-N 0.000 description 2
- HHYPDQBCLQZKLI-UHFFFAOYSA-N 2-[2-hydroxyethyl-[(5-methylbenzotriazol-1-yl)methyl]amino]ethanol Chemical compound CC1=CC=C2N(CN(CCO)CCO)N=NC2=C1 HHYPDQBCLQZKLI-UHFFFAOYSA-N 0.000 description 2
- BHNHHSOHWZKFOX-UHFFFAOYSA-N 2-methyl-1H-indole Chemical compound C1=CC=C2NC(C)=CC2=C1 BHNHHSOHWZKFOX-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 description 2
- MVPKIPGHRNIOPT-UHFFFAOYSA-N 5,6-dimethyl-2h-benzotriazole Chemical compound C1=C(C)C(C)=CC2=NNN=C21 MVPKIPGHRNIOPT-UHFFFAOYSA-N 0.000 description 2
- HHDRWGJJZGJSGZ-UHFFFAOYSA-N 5-benzyl-2h-tetrazole Chemical compound C=1C=CC=CC=1CC=1N=NNN=1 HHDRWGJJZGJSGZ-UHFFFAOYSA-N 0.000 description 2
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 2
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- ONYNOPPOVKYGRS-UHFFFAOYSA-N 6-methylindole Natural products CC1=CC=C2C=CNC2=C1 ONYNOPPOVKYGRS-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- IVOOEPCXVYAICH-UHFFFAOYSA-N CC(=O)CNC(=O)CCl Chemical compound CC(=O)CNC(=O)CCl IVOOEPCXVYAICH-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 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 description 2
- NTYJJOPFIAHURM-UHFFFAOYSA-N Histamine Chemical compound NCCC1=CN=CN1 NTYJJOPFIAHURM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IVYPNXXAYMYVSP-UHFFFAOYSA-N Indole-3-carbinol Natural products C1=CC=C2C(CO)=CNC2=C1 IVYPNXXAYMYVSP-UHFFFAOYSA-N 0.000 description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- FHQDWPCFSJMNCT-UHFFFAOYSA-N N(tele)-methylhistamine Chemical compound CN1C=NC(CCN)=C1 FHQDWPCFSJMNCT-UHFFFAOYSA-N 0.000 description 2
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 2
- FFDGPVCHZBVARC-UHFFFAOYSA-N N,N-dimethylglycine Chemical compound CN(C)CC(O)=O FFDGPVCHZBVARC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 108010077895 Sarcosine Proteins 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/04—Aqueous dispersions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1436—Composite particles, e.g. coated particles
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Dispersion Chemistry (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
本發明之課題係提供一種於研磨具有金屬配線層之研磨對象物之用途中使用之研磨用組成物,而可以維持高的研磨速度之狀態實現凹陷等之階差缺陷之減低,進而提高保存安定性之手段。
本發明之研磨用組成物,係於具有金屬配線層之研磨對象物之研磨所用之研磨用組成物,其含有界面活性劑與水,前述界面活性劑係以下述式1表示之化合物或其鹽:
式1中,A1~A3各獨立為氫原子、甲基、乙基或聚氧伸烷基芳基醚基,但,A1~A3中至少一個為聚氧伸烷基芳基醚基,且前述聚氧伸烷基芳基醚基係:
式2中,Ar表示可具有取代基之碳數6~20之芳基,E為碳數1~3之伸烷基,n為1~100。
Description
本發明係關於研磨用組成物。且,本發明係關於使用該研磨用組成物之研磨方法及基板之製造方法。
本發明係關於例如半導體積體電路(以下稱為「LSI」)中,含金屬之基板表面(以下稱為「研磨對象物」)之研磨用組成物。
隨著LSI之高積體化、高速化已開發新的微細加工技術。化學機械研磨(Chemical Mechanical Polishing,以下亦簡稱為「CMP」)法亦為其一種,並已應用於LSI製造步驟,尤其是應用於多層配線形成步驟中之層間絕緣膜之平坦化、接觸栓柱之形成、埋入配線之形成。該技術揭示於例如專利文獻1中。
接觸栓柱之形成係使用鎢作為埋入材料及其相互擴散障壁之材料等。前述接觸栓柱之形成係使用藉CMP去除鎢以外之多餘部分之製造方法。且,埋入配線之形成中,最近為了使LSI高性能化,而嘗試利用銅或銅合金作為配線材料之金屬配線。銅或銅合金藉由以往之鋁
合金配線之形成而頻繁使用之乾式蝕刻法難以微細加工,故主要採用於預先形成溝槽之絕緣膜上堆積銅或銅合金之薄膜且埋入,並藉CMP去除溝槽部以外之前述薄膜而形成埋入配線之所謂的鑲嵌(damascene)法。CMP中所用之金屬用研磨用組成物一般含有酸等之研磨促進劑及氧化劑,進而視需要含有研磨粒。
且,欲改善研磨後之研磨對象物之平坦性,亦提案使用進一步添加金屬防腐蝕劑之研磨用組成物。例如,專利文獻2中揭示使用含胺基乙酸及/或醯胺基硫酸、氧化劑、苯并三唑及水之研磨用組成物。然而,使用專利文獻1或專利文獻2所記載之組成物實施CMP法時,雖達成高的研磨速度,但另一方面關於凹陷等之階差惡化方面尚有改良餘地。此外,為了解決該等問題,專利文獻3或專利文獻4中揭示含有研磨粒與特定之添加劑及水,且表面張力規定在一定值以下之研磨用組成物。此外,為了以維持高的研磨速度之狀態減低凹陷等之階差缺陷,亦存在有使用月桂基硫酸銨作為界面活性劑之技術(專利文獻5)。
[專利文獻1]日本特開昭62-102543號公報
[專利文獻2]日本特開平8-83780號公報
[專利文獻3]日本特開2011-171446號公報
[專利文獻4]日本特開2008-277723號公報
[專利文獻5]日本特開2008-041781號公報
專利文獻3或專利文獻4所記載之研磨用組成物雖認為發現到藉由降低研磨用組成物本身之表面張力,而提高研磨用組成物對研磨對象物之潤濕性(親水性)或均一性而能解決,但針對凹陷等階差之問題有進一步改良之餘地。且,專利文獻5所記載之使用月桂基硫酸銨作為界面活性劑之技術存在有保存安定性低之課題。
因此本發明之目的係提供一種在研磨具有金屬配線層之研磨對象物之用途中使用之研磨用組成物,而以維持高的研磨速度之狀態實現凹陷等之階差缺陷減低,進而提高保存安定性之手段。
本發明藉由於研磨用組成物中含有具有聚氧伸烷基芳基醚基之界面活性劑而解決上述課題。
亦即,本發明發現藉由提供一種研磨用組成物,可解決上述課題,因而完成本發明,該研磨用組成物係於具有金屬配線層之研磨對象物的研磨中所用之研磨用組成物,其含有界面活性劑與水,前述界面活性劑係以下述式1表示之化合物或其鹽:
式1中,A1~A3各獨立為氫原子、甲基、乙基或聚氧伸烷基芳基醚基,但,A1~A3中至少一個為聚氧伸烷基芳基醚基,前述聚氧伸烷基芳基醚基係:
式2中,Ar表示可具有取代基之碳數6~20之芳基,E為碳數1~3之伸烷基,n為1~100。
依據本發明,可提供在研磨具有金屬配線層之研磨對象物之用途中使用之研磨用組成物中,以維持高的研磨速度之狀態實現凹陷等之階差缺陷之減低,進而提高保存安定性之方法。
以下,說明本發明之實施形態,又,本發明並不僅限於以下之實施形態。此外,圖式之尺寸比率為說明方便而
言有所誇大,會有與實際比率不同之情況。又,本說明書中,表示範圍之「X~Y」意指「不小於X且不大於Y」,「重量」與「質量」、「重量%」與「質量%」及「重量份」與「質量份」係作為同義詞處理。且,若沒有特別指明,則操作及物性等之測定係在室溫(20~25℃)/相對濕度40~50%之條件測定。
本發明為一種研磨用組成物,其係於具有金屬配線層之研磨對象物的研磨中所用之研磨用組成物,其含有界面活性劑與水,前述界面活性劑係以下述式1表示之化合物或其鹽:
式1中,A1~A3各獨立為氫原子、甲基、乙基或聚氧伸烷基芳基醚基,但,A1~A3中至少一個為聚氧伸烷基芳基醚基,前述聚氧伸烷基芳基醚基係:
式2中,Ar表示可具有取代基之碳數6~20之芳基,E為碳數1~3之伸烷基,n為1~100。又,本
說明書中,研磨物組成物有時簡稱為「組成物」。
藉由使研磨用組成物成為如此構成,可以維持高的研磨速度之狀態減低階差缺陷,且保存安定性亦優異。
不過,界面活性劑中含磷酸骨架時,該磷酸骨架對於作為配線材料之金屬配線(例如,銅、銅合金)具有強的螯合效果。因此通常,具有磷酸骨架之界面活性劑雖具有高防腐蝕功能,但相反地由於其過強的鍵結力故亦會抑制研磨速率。亦即,高研磨速度與凹陷等階差缺陷降低原本具有折衝關係。
相對於此,若為含有本發明特有之界面活性劑之研磨用組成物,則可打破其折衝關係,且一方面展現金屬配線之研磨速率,而且可防止金屬配線之凹陷。本發明中,具有該效果之機制雖未必明確,但認為係界面活性劑中存在該聚氧伸烷基芳基醚基時,能使螯合能降低而調整成適度螯合能,結果,不會發生過度抑制研磨速率。且聚氧伸烷基芳基醚基中之「芳基部位」形成保護膜,且失去蝕刻作用,結果,認為亦可抑制凹陷。
另一方面,認為如專利文獻5所揭示般使用月桂基硫酸銨作為界面活性劑時,因研磨粒表面之羥基與界面活性劑間之相互作用而使保存安定性變低,但若為含本發明特有之界面活性劑之研磨用組成物,則認為由於親水性比以往之界面活性劑高,故與研磨粒表面之羥基之相
互作用變弱可有意義地提高保存安定性。又,該機制不過為本發明人之推測,不能說是以該機制限制本發明之技術範圍。
以下,針對本發明之研磨用組成物加以詳細說明。
上述式1中,A1~A3各獨立為氫原子、甲基、乙基或聚氧伸烷基芳基醚基,但A1~A3中之至少一個為聚氧伸烷基芳基醚基。惟,基於金屬表面之蝕刻抑制效果之觀點而言,A1~A3中之一個較好為聚氧伸烷基芳基醚基。且,基於界面活性劑之研磨用組成物中之分散性之觀點而言,A1~A3中至少一個較好為氫原子。又,就可一面維持高研磨速度一面實現低階差之觀點而言,A1~A3中,較好一個為具有後述之式3之聚氧伸烷基芳基醚基作為Ar,其餘部分為氫原子。又,式1之化合物可為1種,亦可為2種以上。另外,亦可併用單酯、二酯、三酯。
本發明之界面活性劑亦可為鹽之形態。鹽之具體例列舉為一價或二價之金屬鹽,或銨鹽、胺鹽等。一價或二價之金屬鹽列舉為鋰鹽、鈉鹽、鉀鹽、鎂鹽、鈣鹽等。其中,基於半導體用之研磨用組成物之金屬雜質之觀點,以胺鹽、鉀鹽較佳。此處,作為胺鹽具體列舉為三乙醇胺、三甲醇胺等。就研磨性能之觀點而言以三乙醇胺較適當。又,所謂鹽之形態,在A1~A3之一個或複數個為氫原子時,係指其一部分或全部氫原子經取代為上述列舉
之鹽之形態。
本發明之聚氧伸烷基芳基醚基係以下述式(2)表示:
式2中,Ar表示可具有取代基之碳數6~20之芳基,E為碳數1~3之伸烷基,n為1~100。
此處「Ar」中,芳基之碳數雖為碳數6~20,但較好為碳數6~15,更好為碳數6~13,又更好為碳數6~8。藉由使碳數落在該範圍,可有效地發揮本發明期望之效果(高研磨速度、凹陷等階差缺陷之減低及保存安定性提高之效果)。此外「Ar」之具體例並未特別限制,列舉為例如苯基、萘基或蒽基等,尤其為苯基時可有效地發揮本發明之期望效果。
鑒於上述時,前述Ar係以下述式3表示:
式3中,R1~R5各獨立為氫原子、經取代或
未取代之碳數1~21之烷基或經取代或未經取代之碳數6~20之芳基。
經取代或未經取代之碳數1~21之烷基中之烷基的碳數,就分散安定性之觀點而言,較好為1~18,更好為1~10,就立體障礙之觀點而言,更好為1~5,最好為1~3。此外,烷基之具體例並無特別限制,可為直鏈亦可為分支,列舉為甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、異戊基、第三戊基、新戊基、己基、異己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、2-乙基己基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基等。其中,就有效地發揮本發明期望之效果之觀點而言,以甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基較佳,更好為甲基、乙基、丙基、異丙基,最好為甲基、乙基。
且經取代或未取代之碳數1~21之烷基中之取代基較好為芳基或鹵原子,至於芳基較好為苯基、萘基,鹵原子較好為氯、溴、碘等。尤其,具有芳基作為取代基時,吸附於研磨對象物(例如Cu)表面時,研磨對象物(例如Cu)之表面成為撥水性,使研磨粒或錯化劑難以與研磨對象物(例如Cu表面)接液。因此,可防止障蔽膜露出後之過度研磨,可有效發揮本發明期望之效果(高的研磨速度、凹陷等階差缺陷之減低及保存安定性提高之效果)。
導入「經取代或未取代之碳數1~21之烷基」時,認為具有如下之作用效果。亦即,疏水部之佔有面積變大時,每一分子之疏水部之佔有面積變大。
結果,同樣地可作用於研磨對象物(例如Cu)之每單位面積之分子數減少,吸附於研磨對象物(例如Cu)表面上之界面活性劑之官能基數亦減少。
因此,藉由研磨用組成物中所含之研磨粒之作用,於去除研磨用組成物時,去除所需之能量變低。且,疏水部大時,基於立體障礙方面,難以形成緻密之膜,以奈米等級觀看時形成多孔質膜。因此,認為去除較容易。
若為此種較佳形態,認為磷酸系界面活性劑中,可實現高的研磨速度與凹陷等之階差缺陷之減低,可有效地打破本來處於折衝之關係。此對「經取代或未取代之碳數6~20之芳基」亦適用同樣考量。
此外R1~R5中之「經取代或未取代之碳數1~21之烷基」之數或「經取代或未取代之碳數6~20之芳基」之數,就分散安定性之觀點而言,較好為1~3之整數。且R1~R5中之烷基之取代部位亦未特別限制,但就高研磨速度且實現低階差、蝕刻抑制效果之觀點而言,取代數為1時,較好為3位,取代數為3時較好為2位、4位、6位。
又,芳基係由芳香族烴衍生之官能基或取代基。R1~R5中之芳基之碳數較好為6~21,但就分散安定性之觀點而言,更好為碳數6~14,又更好為碳數6~8。
該芳基之具體例亦無特別限制,列舉為苯基、萘基或蒽基等。且經取代或未取代之碳數6~20之芳基中之取代基,較好為碳數1~21之烷基、或鹵原子等。碳數1~21之烷基之例為上述之例亦同樣妥當。
鑒於上述時,前述Ar之具體例較好使用下述所示者:
此處,上述Ar1中,r為1~5之整數,就分散安定性之觀點而言,更好為1~3之整數;且,上述Ar2
中,s為1~5之整數,就分散安定性之觀點而言,更好為1~3之整數,又更好為1~2之整數,最好為1。Ar1中之苯基上所取代之乙基之取代位置亦無特別限制,但r=1時,以3位或4位較佳,r=3時,就高研磨速度且實現低階差、蝕刻抑制效果之觀點而言,較好為2位、4位、6位。又,s=1時,以2位、3位或4位較佳,就蝕刻抑制效果之觀點而言最好為3位。
此外,上述式2中之「E」中,碳數1~3之伸烷基之具體例亦無特別限制,可為直鏈狀、分支狀,列舉為例如亞甲基、伸乙基、三亞甲基、伸丙基等,尤其為伸乙基時,可有效發揮上述本發明之期望效果。且,n為1~100,但就分散安定性之觀點而言,較好為4~80之整數,更好為8~50之整數。
鑒於上述時,就有效發揮本發明之期望效果之觀點而言,可適當地使用以下述式4~6表示之化合物或其鹽之界面活性劑。針對鹽之說明由已於上述說明故此處省略。
式4、式5及式6中之「n」可應用上述說明者。
考慮兼具保存安定性、研磨性能時,以式4表示之化合物或其鹽、或以式6表示之化合物或其鹽較佳。因此,本發明之界面活性劑中,苯基(苯基醚基)上取代有(a)取代有苯基之碳數1~3之烷基、或(b)碳數1~3之烷基時,可有效發揮高的研磨速度與高的蝕刻抑制之本發明期望之效果。
本發明之具有聚氧伸烷基芳基醚基之界面活性劑在研磨用組成物中之含量較好為不小於0.01mM,更好不小於0.05mM,又更好為不小於0.08mM。隨著界面活性劑之含量變多會有成為低凹陷之優點。本發明之具有聚氧伸烷基芳基醚基之界面活性劑在研磨用組成物中之含量
又較好為不大於1M,更好不大於0.5M,又更好不大於0.1M,再更好不大於10mM,最好不大於1mM。隨著界面活性劑之含量減少,有促進研磨速度之優點。
此外,本發明之具有聚氧伸烷基芳基醚基之界面活性劑之數平均分子量(Mn)較好為200~100000之範圍內,更好為300~5000之範圍內。又,本發明中,數平均分子量(Mn)係採用以GPC(凝膠滲透層析)法測定之聚苯乙烯換算之值者。
本發明之研磨用組成物之界面活性劑只要為具有聚氧伸烷基芳基醚基者即可,可購入市售品,亦可視需要參照過去習知之見解,或者組合進行合成。
接著,說明本發明之研磨對象物及半導體配線製程之一例。半導體配線製程通常包含以下步驟,但本發明並不限於使用以下步驟。
在設於基板上之具有溝槽之絕緣體層上依序形成障壁層及金屬配線層。障壁層係在金屬配線層形成之前,以被覆絕緣體層表面之方式形成於絕緣體層上。障壁層之厚度比溝槽之深度及寬度小。金屬配線層係在形成障壁層之後,以至少埋入溝槽之方式形成於障壁層上。
藉由CMP,至少去除金屬配線層之外側部分及障壁層之外側部分時,首先,去除金屬配線層之外側部分之大部分。接著,為了使障壁層之外側部分之上面露
出,而去除金屬配線層之外側部分之多餘部分。隨後,利用CMP去除至少位在溝槽外之金屬配線層之部分及位在溝槽外之障壁層之部分。結果,使位在溝槽中之障壁層之部分之至少一部分及位在溝槽中之金屬配線層之部分之至少一部分殘留在絕緣體層上。亦即,於溝槽之內側殘留障壁層之一部分及金屬配線層之一部分。因此,殘留在溝槽內側之金屬配線層之部分係作為配線發揮功能。
較佳之實施形態中,本發明之研磨用組成物係使用於如上述之具有金屬配線層及障壁層之研磨對象物之研磨者。
金屬配線層中所含之金屬並無特別限制,列舉為例如銅、鋁、鉿、鈷、鎳、鈦、鎢等。該等金屬亦可以合金或金屬化合物之形態包含於金屬配線層中。就導電率之觀點而言,較好為銅、或銅合金。該等金屬可單獨使用或組合2種以上使用。
又,障壁層中所含金屬並無特限制,列舉為例如鈦、組之金屬及釕、銀、金、鈀、鉑、銠、銦及鋨等貴金屬。該等金屬及貴金屬亦可以合金或金屬化合物之形態包含於障壁層中,可單獨或組合2種以上使用。依據本發明之較佳實施形態,就防止銅對絕緣膜擴散之效果之觀點而言,以金屬化合物之形態之氮化鈦(TiN)包含於障蔽層中。
本發明之研磨用組成物較好含有水作為用以使各成分分散或溶解之分散介質或溶劑。就抑制阻礙其他成分之作用之觀點而言,較好為儘可能不含雜質之水,具體而言較好為以離子交換樹脂去除雜質離子後,通過過濾器去除異物之純水或超純水、或蒸餾水。
接著,針對本發明之研磨用組成物中所含各成分加以詳細說明。
藉由於研磨用組成物中添加錯化劑(本說明書中亦稱為「錯體形成劑」),藉由錯化劑所具有之蝕刻作用,而有提高以研磨用組成物進行之研磨對象物之研磨速度的有利效果。
錯化劑係使用例如無機酸、有機酸、胺基酸、腈化合物及螯合劑等。無機酸之具體例列舉為硫酸、硝酸、硼酸、碳酸等。有機酸之具體例列舉為甲酸、乙酸、丙酸、丁酸、戊酸、2-甲基丁酸、正己酸、3,3-二甲基丁酸、2-乙基丁酸、4-甲基戊酸、正庚酸、2-甲基己酸、正辛酸、2-乙基己酸、苯甲酸、乙醇酸、水楊酸、甘油酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、馬來酸、鄰苯二甲酸、蘋果酸、酒石酸、檸檬酸、乳酸等。亦可使用甲烷磺酸、乙烷磺酸及羥乙磺酸等有機硫酸。亦可替代無機酸或有機酸或與無機酸或有機酸組合而使用無機酸或有機酸之鹼金屬鹽等之鹽。
胺基酸之具體例列舉為甘胺酸、α-丙胺酸、β-丙胺酸、N-甲基甘胺酸、N,N-二甲基甘胺酸、2-胺基丁酸、正纈胺酸、纈胺酸、亮胺酸、正亮胺酸、異亮胺酸、苯基丙胺酸、脯胺酸、肌胺酸、鳥胺酸、離胺酸、牛磺酸、絲胺酸、蘇胺酸、高絲胺酸、酪胺酸、N,N-二羥乙基甘胺酸(bicine)、N-參羥甲基甲基甘胺酸(tricin)、3,5-二碘酪胺酸、β-(3,4-二羥基苯基)-丙胺酸、甲狀腺素(thyroxin)、4-羥基-脯胺酸、半胱胺酸、甲硫胺酸、乙硫胺酸、羊毛硫胺酸(lanthionine)、胱硫醚(cystathionine)、胱胺酸、磺基丙胺酸(cysteic acid)、天門冬胺酸、穀胺酸、S-(羧基甲基)-半胱胺酸、4-胺基丁酸、天冬醯胺、穀醯胺、氮雜絲胺酸(azaserine)、精胺酸、刀豆胺酸(canavanine)、瓜胺酸、δ-羥基離胺酸、肌酸、組胺酸、1-甲基組胺酸、3-甲基組胺酸、色胺酸等。其中以甘胺酸、丙胺酸、蘋果酸、酒石酸、檸檬酸、乙醇酸、羥乙磺酸或該等之鹽較佳。
腈化合物之具體例列舉為例如乙腈、胺基乙腈、丙腈、丁腈、異丁腈、苄腈、戊二腈、甲氧基乙腈等。
螯合劑之具體例列舉為氮基三乙酸、二伸乙基三胺五乙酸、乙二胺四乙酸、N,N,N-三亞甲基膦酸、乙二胺-N,N,N’,N’-四亞甲基磺酸、反式環己烷二胺四乙酸、1,2-二胺基丙烷四乙酸、二醇醚二胺四乙酸、乙二胺鄰羥基苯基乙酸、乙二胺二琥珀酸(SS體)、N-(2-羧酸根乙基)-
L-天門冬胺酸、β-丙胺酸二乙酸、2-膦醯丁烷-1,2,4-三羧酸、1-羥基亞乙基-1,1-二膦酸、N,N’-雙(2-羥基苄基)乙二胺-N,N’-二乙酸、1,2-二羥基苯-4,6-二磺酸等。
研磨用組成物之錯化劑之含量下限較好為不小於0.01(g/L),更好為不小於0.1(g/L),又更好為不小於1(g/L),最好為不小於5g/L。隨著錯化劑之含量變多,研磨用組成物對研磨對象物之研磨速度提高。另一方面,基於減低因添加錯化劑而使研磨對象物容易接受過度蝕刻之虞(防止過度蝕刻)之觀點而言,該研磨用組成物中之該錯化劑含量上限相對於組成物較好為不大於50(g/L),更好為不大於30(g/L),又更好為不大於15g/L。
本發明中亦可使用「其他界面活性劑」。其他界面活性劑為上述式1所示之以外之界面活性劑。實施例中係以「界面活性劑2」表示。
藉由於研磨用組成物中添加其他界面活性劑,除了更不易因使用研磨用組成物研磨而於形成之配線側邊產生凹陷以外,亦有更不易於使用研磨用組成物研磨後之研磨對象物表面形成凹陷之優點。此外,亦有提高研磨速度之優點。亦即,藉由併用本發明之磷酸系界面活性劑與其他界面活性劑,而能有效地以維持高研磨速度之狀態實現凹陷等階差缺陷之減低。
使用之其他界面活性劑為陰離子性界面活性
劑、陽離子性界面活性劑、兩性界面活性劑及非離子界面活性劑之任一種均可,但其中以陰離子性界面活性劑及/或非離子性界面活性劑較佳。亦可組合複數種之界面活性劑使用,該情況下,較好組合陰離子性界面活性劑與非離子性界面活性劑使用。尤其,本發明之具有聚氧伸烷基芳基醚基之界面活性劑藉由與非離子性界面活性劑組合使用,而於基板上形成之保護層上形成多層非離子性界面活性劑之保護層、促進了抑制蝕刻作用之作用,且亦使非離子性界面活性劑吸附於研磨粒表面,故而提高研磨粒與前述保護層之親和性,且適度提高研磨粒之機械作用,因此在不降低研磨速率下進一步提高抑制凹陷之效果。
陰離子性界面活性劑之具體例較好具有單氧伸乙基或聚氧伸乙基。此種陰離子性界面活性劑之具體例列舉為例如聚氧伸乙基烷基醚磷酸、聚氧伸乙基烷基醚乙酸、聚氧伸乙基烷基醚硫酸。亦即,可使用進一步具有磷酸基、羧基或磺基之陰離子性界面活性劑,更具體舉例為聚氧伸乙基烷基醚乙酸、聚氧伸乙基烷基醚硫酸、烷基醚硫酸、聚氧伸乙基烷基硫酸酯、烷基硫酸酯、聚氧伸乙基烷基硫酸、烷基硫酸、烷基苯磺酸、烷基磷酸酯、聚氧伸乙基烷基磷酸酯、聚氧伸乙基磺基琥珀酸、烷基磺基琥珀酸、烷基萘磺酸、烷基二苯基醚二磺酸、及該等之鹽。其中以聚氧伸乙基烷基醚乙酸、聚氧伸乙基烷基醚硫酸鹽、烷基醚硫酸鹽及烷基苯磺酸鹽較佳。此外,就提高研磨用組成物與研磨對象物間之撥水作用之觀點而言,研磨用組
成物中所含之陰離子性界面活性劑較好具有烷基,更具體而言更好烷基之重複碳數為8個以上,具體而言更好為辛基硫酸鹽、癸基硫酸鹽、月桂基硫酸鹽、十八烷基硫酸鹽。該等之較佳陰離子性界面活性劑由於提高對研磨對象物表面之化學或物理的吸附力,故更提高研磨對象物之撥水性,且於研磨對象物之表面形成更堅固之保護膜。此對於提高使用研磨用組成物研磨後之研磨對象物的表面之平坦性有利。
陽離子性界面活性劑之具體例列舉為例如烷基三甲基銨鹽、烷基二甲基銨鹽、烷基苄基二甲基銨鹽、及烷基胺鹽。
兩性界面活性劑之具體例列舉為例如烷基甜菜鹼及烷基氧化胺等。
非離子性界面活性劑之具體例列舉為例如聚氧伸乙基烷基醚等聚氧伸烷基烷基醚、山梨糖醇酐脂肪酸酯、甘油脂肪酸酯、聚氧伸乙基脂肪酸酯、聚氧伸乙基烷基胺、及烷基烷醇醯胺。其中以聚氧伸烷基烷基醚較佳。聚氧伸烷基烷基醚由於提高對研磨對象物表面之化學或物理之吸附力,故於研磨對象物表面形成更堅固之保護膜。此對於提高使用研磨用組成物研磨後之研磨對象物表面之平坦性有利。因此,藉由與本發明之具有聚氧伸烷基芳基醚基之界面活性劑組合,不使研磨速率降低,而能增強抑制凹陷之效果。
此處,針對聚氧伸烷基烷基醚進一步說明
時,較佳之實施形態中,聚氧伸烷基烷基醚係示於下:【化13】X-O-(YO)m-H
但,X為氫原子或經取代或未取代之碳數1~21之烷基,Y為與前述E相同之定義,m為1~8。
此處,經取代或未取代之碳數1~21之烷基之具體例同樣適用上述說明。烷基可為直鏈狀亦可為分支狀者,但就不降低研磨速率而可抑制凹陷之觀點而言,以分支狀較佳。又,就蝕刻抑制之觀點而言,X較好為碳數3~18之烷基,更好為碳數8~18之烷基,又更好為碳數10~16之烷基,再更好為碳數12~14之烷基。又,就相溶性之觀點而言,Y較好為伸乙基、伸丙基,更好為伸乙基。此外,就相溶性之觀點而言,m更好為2~8,又更好為4~6。
本發明中,特別就抑制研磨對象物上凹坑之觀點,較好組合本發明之特定磷酸系界面活性劑與聚氧伸烷基烷基醚,進而添加具有後述之特定分配係數之金屬腐蝕劑。且,本發明中,就抑制TiN研磨速率之觀點,以組合本發明之特定磷酸系界面活性劑與聚氧伸烷基烷基醚,進而添加後述之糖較佳。
研磨用組成物中之「其他界面活性劑」之含量較好為不小於0.01(g/L),更好不小於0.05(g/L),又更好不小於0.1(g/L)。隨著界面活性劑之含量變多,有提高使用研磨用組成物研磨後之研磨對象物表面之平坦性之優
點。研磨用組成物中之界面活性劑含量較好不大於50(g/L),更好不大於25(g/L),又更好不大於5(g/L),最好不大於1(g/L)。隨著界面活性劑之含量變少,有提高利用研磨用組成物之研磨速度之優點。
研磨組成物中所含之研磨粒具有對研磨對象物機械研磨之作用,且可提高研磨用組成物對研磨對象物之研磨速度。
使用之研磨粒可為無機粒子、有機粒子及有機無機複合粒子之任一種。無機粒子之具體例列舉為例如由二氧化矽、氧化鋁、氧化鈰、氧化鈦等金屬氧化物所成之粒子,以及氮化矽粒子、碳化矽粒子、氮化硼粒子。有機粒子之具體例列舉為例如聚甲基丙烯酸甲酯(PMMA)粒子。該研磨粒可單獨使用或混合2種以上使用。另外,該研磨粒可使用市售品亦可使用合成品。
該等研磨粒中以二氧化矽較佳,最好為膠體二氧化矽。
研磨粒亦可經表面修飾。通常之膠體二氧化矽由於在酸性條件下之Zeta電位值接近於零,故在酸性條件下二氧化矽粒子彼此間不會靜電排斥而容易引起凝聚。相對於此,經表面修飾為即使在酸性條件下具有Zeta電位較大之負值的研磨粒,在酸性條件下相互間強烈排斥而成良好分散之結果,提高了研磨用組成物之保存安定
性。如此之表面修飾研磨粒可藉由例如使鋁、鈦或鋯等金屬或該等之氧化物與研磨粒混合而摻雜於研磨粒之表面而獲得。其中,最好為固定化有有機酸之膠體二氧化矽。有機酸對研磨用組成物中所含之膠體二氧化矽表面之固定化係藉由例如使有機酸之官能基化學鍵結於膠體二氧化矽表面而進行。僅單使膠體二氧化矽與有機酸共存,無法達到有機酸朝膠體二氧化矽之固定化。若使有機酸之一種的磺酸固定化於膠體二氧化矽上,則可藉例如“Sulfonic acid-functionalized silica through quantitative oxidation of thiol groups”,Chem.Commun.246-247(2003)中所記載之方法進行。具體而言,使3-巰丙基三甲氧基矽烷等之具有硫醇基之矽烷偶合劑偶合於膠體二氧化矽上後,以過氧化氫使硫醇基氧化,藉此可獲得磺酸固定化於表面之膠體二氧化矽。或者,若使羧酸固定化於膠體二氧化矽上,則可藉例如“Novel Silane Coupling Agents Containing a Photolabile 2-Nitrobenzyl Ester for Introduction of a Carboxy Group on the Surface of Silica Gel”,Chemistry Letters,3,228-229(2000)中所記載之方法進行。具體而言,在將含有光反應性2-硝基苄酯之矽烷偶合劑偶合於膠體二氧化矽後,藉由光照射,可獲得使羧酸固定化於表面之膠體二氧化矽。
研磨粒之平均一次粒徑之下限較好為不小於1nm,更好不小於3nm,又更好不小於5nm。且,研磨粒之平均一次粒徑之上限較好不大於500nm,更好不大於
100nm,又更好不大於70nm,最好不大於50nm。若為該範圍,則研磨用組成物對研磨對象物之研磨速度提高,且可進一步抑制使用研磨用組成物研磨後之研磨對象物表面產生傷痕(刮痕)。又,研磨粒之平均一次粒徑係採用基於以BET法測定之研磨粒之比表面積而算出。本案之實施例中亦係如此般算出。
研磨粒之平均二次粒徑較好不大於500nm,更好不大於400nm,又更好不大於300nm。研磨粒之平均二次粒徑之值可利用雷射光散射法測定。
又,依據本發明之較佳實施形態,較好組合兩種粒徑(平均一次粒徑)不同之研磨粒。該形態對於提高研磨時作用於基材上之研磨粒個數有效果。二種類組合時之粒徑比,就兼具高研磨速度與低階差之觀點而言,較好為0.01~0.95,更好為0.1~0.5。
研磨粒之平均二次粒徑之值除以平均一次粒徑之值所得之研磨粒之平均凝聚度較好為不小於1,更好不小於1.2。隨著研磨粒之平均一次粒徑變大,具有提高研磨用組成物對研磨對象物之去除速度之優點。
研磨粒之平均凝聚度較好不大於5,更好不大於4,又更好不大於3。隨著研磨粒之平均凝聚度變小,藉由使用研磨用組成物研磨研磨對象物容易獲得表面缺陷少之研磨面。
研磨用組成物中之研磨粒含量下限較好不小於0.01(g/L),更好不小於0.03(g/L),又更好不小於0.05
(g/L),最好不小於0.1(g/L)。且,研磨用組成物中之研磨粒含量上限較好為不大於100(g/L),更好不大於50(g/L),又更好不大於10(g/L),再更好不大於5(g/L),最好不大於2(g/L)。又,研磨用組成物中混合存在有具有兩種以上之平均一次粒徑之研磨粒時,含量為其合計量。若在該範圍,則可提高研磨對象物之研磨速度,且可抑制研磨用組成物之成本,可更抑制使用研磨用組成物研磨後之研磨對象物表面產生凹陷等之階差缺陷。
本形態之研磨用組成物亦可含氧化劑。本說明書中之所謂氧化劑意指可對研磨對象物中所含之金屬發揮作為氧化劑功能之化合物。因此,氧化劑係依據是否為發揮該功能時具有充分之氧化還原電位者之基準進行選定。因此,氧化劑之延伸並非一定可統一明確定義者,但其一例列舉為例如過氧化氫、硝酸、亞氯酸、次氯酸、過碘酸、過硫酸鹽、氧化氫及其加成物,例如尿素過氧化氫及碳酸酯、有機過氧化物,例如苯甲醯、過乙酸及二第三丁基、硫氧化物(SO5)、硫氧化物(S5O8)、以及過氧化鈉。此外,列舉有過碘酸、亞碘酸、次碘酸、氫碘酸、過溴酸、亞溴酸、次溴酸、氫溴酸、過氯酸、氫氯酸、過氯酸、過硼酸、及該等之鹽等。
本形態之研磨用組成物含氧化劑時,該研磨用組成物中之該氧化劑之含量下限相對於組成物較好不小
於1(g/L),更好不小於5(g/L)。隨著氧化劑之含量變多,有利用研磨用組成物對研磨對象物之研磨速度提高之傾向。另一方面,本形態之研磨用組成物含氧化劑時,該研磨用組成物中之該氧化劑之含量上限相對於組成物1L,較好不大於100(g/L),更好不大於50(g/L)。隨著氧化劑之含量變少,除了可抑制研磨用組成物之材料成本以外,可減輕研磨使用後之研磨用組成物之處理,亦即可減輕廢液處理之負荷。且,亦可獲得可防止因氧化劑所致之研磨對象物過度氧化之有利效果。
本發明之研磨用組成物中,亦可添加金屬防腐蝕劑(本說明書中,有時亦簡稱為「防腐蝕劑」)。藉由於研磨用組成物中添加金屬防腐蝕劑,可進一步抑制使用研磨用組成物之研磨而在配線之側邊產生凹陷。且,可更抑制在使用研磨用組成物研磨後之研磨對象物之表面產生凹陷等之階差缺陷。
可使用之金屬防腐蝕劑並無特別限制,但較好為雜環式化合物。雜環式化合物中之雜環之員數並無特別限制。另外,雜環式化合物可為單環化合物,亦可為具有縮合環之多環化合物。該金屬防腐蝕劑可單獨使用或混合2種以上使用。另外,該金屬防腐蝕劑可使用市售品,亦可使用合成品。
可作為金屬防腐蝕劑使用之雜環化合物之具
體例列舉為例如吡咯化合物、吡唑化合物、咪唑化合物、吡唑酮(pyrazolone)化合物、三唑化合物、四唑化合物、吡啶化合物、哌啶化合物、嗒嗪化合物、吡嗪化合物、吲哚嗪(indolizine)化合物、吲哚化合物、異吲哚化合物、吲唑化合物、嘌呤化合物、喹嗪(quinolizine)化合物、喹啉化合物、異喹啉化合物、萘啶化合物、酞嗪化合物、喹喔啉化合物、喹唑啉化合物、噌啉化合物、喋啶化合物、噻唑化合物、異噻唑化合物、噁唑化合物、異噁唑化合物、呋咱化合物等含氮雜環化合物。
進一步列舉具體例時,吡唑化合物之例列舉為例如1H-吡唑、4-硝基-3-吡唑羧酸、3,5-吡唑羧酸、3-胺基-5-苯基吡唑、5-胺基-3-苯基吡唑、3,4,5-三溴吡唑、3-胺基吡唑、3,5-二甲基吡唑、3,5-二甲基-1-羥基甲基吡唑、3-甲基吡唑、1-甲基吡唑、3-胺基-5-甲基吡唑、4-胺基-吡唑并[3,4-d]嘧啶、4-氯-1H-吡唑并[3,4-D]嘧啶、3,4-二羥基-6-甲基吡唑并(3,4-B)-吡啶、6-甲基-1H-吡唑并[3,4-b]吡啶-3-胺、1,2-二甲基吡唑等。
尤其,基於保存安定性與不因氧化劑而劣化而言,較好為3,5-二甲基吡唑、1H-吡唑、3,5-二甲基-1-羥基甲基吡唑。
咪唑化合物之具體例列舉為例如咪唑、1,2-二甲基咪唑、1H-咪唑(咪唑)、1-甲基咪唑、2-甲基咪唑、4-甲基咪唑、2-乙基-4-甲基咪唑、2-異丙基咪唑、苯并咪唑、5,6-二甲基苯并咪唑、2-胺基苯并咪唑、2-氯苯并咪
唑、2-甲基苯并咪唑、2-(1-羥基乙基)苯并咪唑、2-羥基苯并咪唑、2-苯基苯并咪唑、2,5-二甲基苯并咪唑、5-甲基苯并咪唑、2-乙基咪唑、5-硝基苯并咪唑、N-甲基咪唑等。
尤其,就保存安定性與不因氧化劑而劣化而言,以咪唑、2-異丙基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、2-乙基咪唑、4-甲基咪唑、N-甲基咪唑較佳。
三唑化合物之例列舉為例如1-甲基苯并三唑、1,2,3-三唑、1,2,4-三唑、1-(4-吡啶基羰基)苯并三唑、1-甲基-1,2,4-三唑、甲基-1H-1,2,4-三唑-3-羧酸酯、1,2,4-三唑-3-羧酸、1,2,4-三唑-3-羧酸甲酯、1H-1,2,4-三唑-3-硫醇、3,5-二胺基-1H-1,2,4-三唑、3-胺基-1,2,4-三唑-5-硫醇、3-胺基-1H-1,2,4-三唑、3-胺基-5-苄基-4H-1,2,4-三唑、3-胺基-5-甲基-4H-1,2,4-三唑、3-硝基-1,2,4-三唑、3-溴-5-硝基-1,2,4-三唑、4-(1,2,4-三唑-1-基)苯酚、4-胺基-1,2,4-三唑、4-胺基-3,5-二丙基-4H-1,2,4-三唑、4-胺基-3,5-二甲基-4H-1,2,4-三唑、4-胺基-3,5-二戊基-4H-1,2,4-三唑、5-甲基-1,2,4-三唑-3,4-二胺、1H-苯并三唑、1-羥基苯并三唑、1-胺基苯并三唑、1-羧基苯并三唑、5-氯-1H-苯并三唑、5-硝基-1H-苯并三唑、5-羧基-1H-苯并三唑、5-甲基-1H-苯并三唑、5,6-二甲基-1H-苯并三唑、1-(1’,2’-二羧基乙基)苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]-5-甲基苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]-4-甲基苯并三
唑、1H-苯并咪唑、苯并咪唑-5-羧酸、2-(1-羥基乙基)苯并咪唑、2-胺基苯并咪唑等。
尤其,以1-(4-吡啶基羰基)苯并三唑、5-甲基-1H-苯并三唑、5,6-二甲基-1H-苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]-5-甲基苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]-4-甲基苯并三唑、1,2,3-三唑、1H-苯并咪唑、苯并咪唑-5-羧酸、2-(1-羥基乙基)苯并咪唑、2-胺基苯并咪唑及1,2,4-三唑較佳。該等雜環化合物由於對研磨對象物表面之化學或物理之吸附力高,故使研磨對象物表面之撥水性更高,且可形成牢固的保護膜。此對於提高使用本發明之研磨用組成物研磨後之研磨對象物表面之平坦性有利。
四唑化合物之例列舉為例如四唑、1H-四唑、5-甲基四唑、5-苄基-1H-四唑、5-胺基-1H-四唑、5-胺基四唑、1H-四唑-1-乙酸、5,5’-雙四唑二銨及5-苯基四唑等。
吲唑化合物之例列舉為例如1H-吲唑、5-胺基吲唑、6-胺基吲唑、3-羥基-1H-吲唑、5-胺基-1H-吲唑、5-硝基-1H-吲唑、5-羥基-1H-吲唑、6-胺基-1H-吲唑、6-硝基-1H-吲唑、6-羥基-1H-吲唑、3-羧基-5-甲基-1H-吲唑等。
尤其,就保存安定性及不因氧化劑而劣化而言,以5-胺基吲唑、6-胺基吲唑、3-羥基-1H-吲唑較佳。
吲哚化合物之例列舉為例如1H-吲哚、1-甲基-1H-吲哚、2-甲基-1H-吲哚、3-甲基-1H-吲哚、4-甲基-
1H-吲哚、5-甲基-1H-吲哚、6-甲基-1H-吲哚、7-甲基-1H-吲哚、4-胺基-1H-吲哚、5-胺基-1H-吲哚、6-胺基-1H-吲哚、7-胺基-1H-吲哚、4-羥基-1H-吲哚、5-羥基-1H-吲哚、6-羥基-1H-吲哚、7-羥基-1H-吲哚、4-甲氧基-1H-吲哚、5-甲氧基-1H-吲哚、6-甲氧基-1H-吲哚、7-甲氧基-1H-吲哚、4-氯-1H-吲哚、5-氯-1H-吲哚、6-氯-1H-吲哚、7-氯-1H-吲哚、4-羧基-1H-吲哚、5-羧基-1H-吲哚、6-羧基-1H-吲哚、7-羧基-1H-吲哚、4-硝基-1H-吲哚、5-硝基-1H-吲哚、6-硝基-1H-吲哚、7-硝基-1H-吲哚、4-腈-1H-吲哚、5-腈-1H-吲哚、6-腈-1H-吲哚、7-腈-1H-吲哚、2,5-二甲基-1H-吲哚、1,2-二甲基-1H-吲哚、1,3-二甲基-1H-吲哚、2,3-二甲基-1H-吲哚、5-胺基-2,3-二甲基-1H-吲哚、7-乙基-1H-吲哚、5-(胺基甲基)吲哚、2-甲基-5-胺基-1H-吲哚、3-羥基甲基-1H-吲哚、6-異丙基-1H-吲哚、5-氯-2-甲基-1H-吲哚等。
又,乙醯基丙酮、3-氯乙醯基丙酮等二酮化合物;3-甲基-5-腙等腙化合物;嘌呤、1H-嘌呤;異嘌呤醇(allopurinol)等嘌呤化合物亦適當。
此外,依據本發明之較佳實施形態,金屬防腐蝕劑之辛醇-水分配係數(logP)(本說明書中亦簡稱為「分配係數」)不大於1.8,依據更佳實施形態係不大於1.3。尤其藉由使用不大於1.3之金屬防腐蝕劑,尤其可抑制研磨對象物上之凹坑。藉由使用分配係數不大於1.3之金屬防腐蝕劑,尤其可抑制凹坑之機制雖尚不清楚,但推
測如下。但不用說本發明之技術範圍並不因該機制而受限。
亦即,分配係數雖為疏水性之指標,但有意義降低疏水性時,與研磨對象物(例如氧化銅)之表面或研磨粒之親和性提高。本發明中使用特定之磷酸系界面活性劑,但認為該金屬防腐蝕劑可發揮補強由磷酸系界面活性劑所得之保護膜之效果者。
亦即,本發明之特定磷酸系界面活性劑係在研磨對象物(尤其是銅基鈑)上以銅-磷酸部-EO-疏水部(芳基)(一實施形態中為三苯乙烯基)之形態形成保護膜,但因鄰接之分子使疏水部成為立體障礙而使膜密度下降,會有產生保護膜之間隙之情況。此處之「EO」作為一實施形態係表示環氧乙烷。
本發明之研磨用組成物不僅含有特定之磷酸系界面活性劑且藉由含有分配係數有意義低的金屬防腐蝕劑,而使該金屬防腐蝕劑埋入上述間隙間,而抑制或防止腐蝕或凹坑之產生。且,該金屬防腐蝕劑藉由含氮原子,使該氮原子作為吸附部位而吸附、保護研磨對象物(尤其是氧化銅)表面,可說是發揮凹坑抑制劑之作用。因此,本發明藉由特定磷酸系界面活性劑與特定金屬防腐蝕劑之協同作用,而發揮非常有利之效果。
又,分配係數之下限較好為不小於-1.5,更好不小於-1,又更好不小於-0.5。下限若不小於-1.5,則作為金屬防腐蝕劑之功能優異(通常對於疏水性的研磨對象
物表面之防腐蝕膜形成能較高)。
此處,分配係數(logP)之測定可藉JIS Z-7260-107(2000)中記載之燒杯浸漬法進行。又,分配係數(logP)亦可替代實測而藉由計算化學手法或依經驗法估算者。
計算方法較好使用Crippen's fragmentation法(“J.Chem.Inf.Comput.Sci.”,27卷,p21(1987年))、Viswanadhan’s fragmentation法(“J.Chem.Inf.Comput.Sci.”,29卷,p163(1989年))、Broto’s fragmentation法(“Eur.J.Med.Chem.-Chim.Theor.”,19卷,p71(1984年))、CLogP法(參考文獻Leo,A.,Jow,P.Y.C.,Silipo,C.,Hansch,C.,J.Med.Chem.,18,865 1975年)等。但更好為Crippen's fragmentation法(“J.Chem.Inf.Comput.Sci.”,27卷,p21(1987年))。
後述之實施例中,使用Molinspiration Cheminformatics公司之網站所公開之免費軟體進行計算。
分配係數(logP)不大於1.3之防腐蝕劑之例列舉為例如1-甲基苯并三唑、1-羥基苯并三唑、1-(4-吡啶基羰基)苯并三唑等之苯并三唑化合物;1,2,3-三唑、1,2,4-三唑、1,2,4-三唑-3-羧酸甲酯、3-胺基-1H-1,2,4-三唑等之三唑化合物;四唑、5-甲基四唑、5-胺基-1H-四唑、5-苄基-1H-四唑、5,5’-聯四唑二銨、1H-四唑-1-乙酸等四唑化合物;3-羥基-1H-吲唑、5-胺基吲唑、6-胺基吲唑等吲唑化合物;1H-咪唑、2-甲基咪唑、1,2-二甲基咪唑、2-異丙
基咪唑、2-乙基-4-甲基咪唑、2-乙基咪唑、4-甲基咪唑、N-甲基咪唑等咪唑化合物;1H-苯并咪唑、苯并咪唑-5-羧酸、2-(1-羥基乙基)苯并咪唑、2-胺基苯并咪唑等苯并咪唑化合物;1H-吡唑、3,5-二甲基吡唑、3,5-二甲基-1-羥基甲基吡唑等吡唑化合物;乙醯基丙酮、3-氯乙醯基丙酮等二酮化合物;3-甲基-5-吡唑酮等吡唑酮化合物;嘌呤、1H-嘌呤、異嘌呤醇等嘌呤化合物。
其中,就凹坑抑制、研磨速率(較好為Cu研磨速率)、與凹陷性能之觀點而言,以三唑化合物、吡唑化合物、咪唑化合物、吡唑酮化合物較佳,尤其以3-甲基-5-吡唑酮、1,2,4-三唑、3,5-二甲基吡唑、1H-吡唑、1H-咪唑最佳。此外,要求更強的凹陷性能時,以如3,5-二甲基吡唑、1H-吡唑之吡唑化合物最佳。
研磨用組成物中之金屬防腐蝕劑含量下限較好不小於0.001(g/L),更好不小於0.005(g/L),又更好不小於0.01(g/L)。又,研磨用組成物中之金屬防腐蝕劑含量之上限較好不大於10(g/L),更好不大於5(g/L),又更好不大於1(g/L)。若以莫耳濃度(mM)考量,則下限較好不小於0.01mM,更好不小於0.05mM,又更好不小於0.1mM。此外,上限較好不大於100mM,更好不大於50mM,又更好不大於10mM。若為該範圍,則可減低使用研磨用組成物研磨後之研磨對象物之階差,且,可提高利用研磨用組成物對研磨對象物之研磨速度。
依據本發明之較佳實施形態,研磨用組成物中亦可添加糖作為TiN研磨速率抑制劑。藉由於研磨用組成物中添加糖,在進行障壁製程時,可抑制或防止尖端或腐蝕等之階差形狀之惡化。
如上述之說明,本發明之較佳實施形態中,障壁層中使用氮化鈦等含氮化合物。因此,不抑制該障壁層中之氮化鈦(TiN)之研磨速率時,在進行障壁製程時,會有尖端或腐蝕等之階差形狀惡化之虞。
藉由於本發明之研磨用組成物中進一步添加糖,可抑制氮化鈦(TiN)之研磨速率,可提高研磨對象物(例如銅)之研磨選擇性,進而可抑制或防止尖端或腐蝕等之階差形狀之惡化。
藉由添加糖而抑制氮化鈦(TiN)之研磨速率,因此可抑制尖端或腐蝕等之階差形狀之惡化之機制未必不清楚,但推測如下。亦即,認為藉由糖選擇性的附著於障壁層中所含之TiN上,而緩和因研磨粒所致之機械研削作用者。但,不用說該機制並不限制本發明之技術範圍。
可添加於本發明之研磨用組成物中之糖可使用阿拉伯糖、木糖、核糖、木酮糖、核酮糖等五碳糖類;葡萄糖、甘露糖、半乳糖、果糖、山梨糖、塔格糖(tagatose)等之六碳糖(Hexose);景天庚酮糖(sedoheptulose)等七碳糖類;海藻糖(trehalose)、蔗糖(saccharose)、麥芽糖、纖維二糖、龍膽二糖(gentiobiose)、蔗糖(sucrose)、乳糖等
二糖類;棉仔糖(raffinose)、麥芽三糖(maltotriose)等三糖類;且亦可使用由各單糖類所成之多糖;澱粉、支鏈澱粉(amylopectin)、糖原(glycogen)、纖維素、果膠、半纖維素、普魯蘭多糖(pullulan)、痂囊腔菌聚糖(Elsinan)、糊精等之多糖。
其中,就進一步抑制氮化鈦(TiN)之研磨速率、可進一步抑制或防止尖端或腐蝕等之階差形狀之惡化之觀點而言,糖較佳為多糖,其中就TiN研磨速率抑制效果之觀點而言,以普魯蘭多糖、糊精較佳,就兼具TiN研磨速率抑制與Cu研磨速率之觀點而言最好添加糊精。
研磨用組成物中之糖含量,就TiN研磨速率抑制量之觀點而言,較好不小於0.001g/L,更好不小於0.01g/L,又更好不小於0.05g/L。另一方面,就保存安定性之觀點而言,較好不大於10g/L,更好不大於5g/L,又更好不大於1g/L。
研磨用組成物之pH並無特別限制。但若不大於11.0,進而換言之不大於10.0之pH,則由於防止研磨粒溶解故而提高研磨用組成物之安定性。且,若不小於2.0,進而換言之不小於6.0,則研磨用組成物含研磨粒時可提高該研磨粒之分散性。
研磨用組成物之pH亦可使用pH調整劑調整至期望之值。使用之pH調整劑可為酸及鹼之任一種,且
可為無機及有機化合物之任一種。該等pH調節劑可單獨使用或混合2種以上使用。又,本說明書中之「pH」係指液溫(25℃)下使用堀場製作所製造之型號F-72之pH計測定之值。
本發明之研磨用組成物之製造方法並未特別限制,可藉由例如於水中攪拌混合構成本發明之研磨用組成物之各成分而得。
依據較佳形態,提供一種研磨用組成物之製造方法,其係於具有金屬配線層之研磨對象物的研磨中所用之研磨用組成物之製造方法,該方法係混合界面活性劑與水,前述界面活性劑係以下述式1表示之化合物或其鹽:
式1中,A1~A3各獨立為氫原子、甲基、乙基或聚氧伸烷基芳基醚基,但,A1~A3中至少一個為聚氧伸烷基芳基醚基,前述聚氧伸烷基芳基醚基係:
式2中,Ar表示可具有取代基之碳數6~20之芳
基,E為碳數1~3之伸烷基,n為1~100。
又,混合各成分時之溫度並無特別限制,較好為10~40℃,為了提高溶解速度亦可加熱。且,混合時間亦無特別限制。
如上述,本發明之研磨用組成物適用於具有金屬配線層之研磨對象物之研磨。因此,本發明提供以本發明之研磨用組成物或上述研磨用組成物之製造方法製造之研磨用組成物研磨具有金屬配線層之研磨對象物之研磨方法。另外,本發明提供包含以前述研磨方法研磨具有金屬配線層之研磨對象物之步驟之基板的製造方法。
研磨裝置可使用安裝有保持具有研磨對象物之基板等之載具與可改變轉數之馬達等,且具有可貼附研磨墊(研磨布)之研磨壓盤之一般研磨裝置。前述研磨墊可無特別限制的使用一般之不織布、聚胺基甲酸酯及多孔質氟樹脂等。研磨墊中較好施以可使研磨液積存之溝槽加工。
研磨條件亦無特別限制,例如研磨壓盤之轉數較好為10~500rpm,對具有研磨對象物之基板施加之壓力(研磨壓力)較好為0.5~10psi(3.45~69KPa)。將研磨
用組成物供給於研磨墊之方法亦無特別限制,例如可採用泵等連續供給之方法。其供給量並無限制,但較好隨時以本發明之研磨用組成物覆蓋研磨墊表面。
研磨結束後,在水流中洗淨基板,以旋轉乾燥機等甩掉附著於基板上之水滴予以乾燥,而獲得具有金屬配線層及障壁層之基板。
以下,列舉實施例及比較例更詳細說明前述實施形態。
將表1、表3、表4中所示之各成分攪拌混合於水中(混合溫度:約25℃,混合時間:約10分鐘),調製實施例1~19、比較例1~4之研磨用組成物。又,研磨用組成物中之pH一律調製成7.0。
此外,研磨粒1係使用膠體二氧化矽平均一次粒徑12nm(平均凝聚度:2.6),研磨粒2係使用膠體二氧化矽平均一次粒徑35nm(平均凝聚度:1.9),將該等一起混合調製成研磨用組成物。
此外,「三苯乙烯基苯基醚EO磷酸酯」(Rhodia Nicca製之SOPROPHOR 3D33)係以下式表示:
「POE芳基苯基醚磷酸酯胺鹽」(竹本油脂New Collagen FS-3AQ)係以下式表示:
此時n為20。
此外「芳香族EO磷酸酯」(Rhodia Nicca製造RHOFAFAC H66)係以下式表示:
此外,「月桂基磷酸」、「POE月桂基磷酸」、「月桂基硫酸銨」分別以下述式7~式9表示:
上述式8中,n=10。
又,聚氧伸烷基烷基醚係以下式表示:
【化22】(CH3CH2CH2CH2CH2CH2)2CH-O(CH2CH2O)5-H
Cu之研磨速率(研磨速度)係使用所得研磨用組成物(實施例1~12、比較例1~3),以表2之條件研磨,且使用所得研磨用組成物(實施例13~19、比較例4),以表5之條件研磨而算出。
TiN之研磨速率(研磨速度)係使用所得研磨用組成物(實施例13~19、比較例4),以表5之研磨條件研磨而算出。
更具體而言,研磨速度係將使用以直流4探針法為原理之薄片電阻測定器測定之研磨前後之銅無圖型晶圓(直徑300mm)及TiN無圖型晶圓(直徑300mm)之厚度差除以研磨時間而求出。結果示於表1、表3及表4。
首先,如實施例1~19所示,藉由使用本發明之特定界面活性劑,與如比較例1~2所示之使用以往之界面活性劑進行比較,可知Cu之研磨速率較快速。
此處,過去一般已知研磨速度較快越容易產生凹坑等缺陷。相對於此,依據本發明之防腐蝕劑,與通常之預測相反,難以產生缺陷。此與以往之防腐蝕劑相比較,認為是由於覆蓋研磨對象物Cu表面之佔有面積較廣,故成為該結果。
又,比較實施例5~7之Cu研磨速率與實施例8~12之Cu研磨速率時,後者快2倍以上。此認為係後者之凹
坑抑制劑之分配係數(logP)為不大於1.3,而難以自Cu表面去除。因此,認為疏水性低亦即成為親水性狀態者,研磨用組成物中之研磨粒或甘胺酸等之構成物容易與Cu表面接觸,使反應頻度變高,而進行Cu之去除。
此外,如實施例14~19所示,教示藉由添加TiN研磨速率抑制劑,而抑制TiN之研磨速率,且可選擇性研磨Cu。此外,教示根據TiN研磨速率抑制劑之種類而定,Cu研磨之選擇性亦不同,實施例18、19中使用之糊精、普魯蘭多糖為最適用。其理由為由HSAB定律之酸.鹼之相容性考量(硬路易斯酸(電子對受體)與硬路易斯鹼(電子對給予體)之親和性高,軟的路易斯酸與軟的路易斯鹼之親和性高),由於Ti歸類為硬的酸,故認為是否是與硬的鹼-OH-之相容性良好。但該機制僅為推測,並不限制本發明之技術範圍。
針對階差缺陷的指標之凹陷係使用所得研磨用組成物(實施例1~19、比較例1~4),以表2所示之研磨條件,研磨銅圖型晶圓(直徑300mm,研磨前之銅膜厚7000Å,溝槽深度3000Å)之表面直至銅殘膜成為300nm為止。隨後,使用相同之研磨用組成物,以表2所示之研磨條件對研磨後之銅圖型晶圓表面進行研磨直至障壁膜露出。結果示於表1、表3及表4。又,比較例1及2中之「不清晰」係指配線間連接,電性短路。
又,表中之「@L/S=100 100μm」意指如下。亦即,「L/S」係指Cu之圖型晶圓上之「線與間隔」。此處,Cu之配線部稱為「線」,將無配線之部分稱為「間隔」。因此,「100 100μm」係指「線」具有100μm之寬度,且「間隔」亦具有100μm之寬度。
如由結果所明瞭,與比較例1、2不同,所有實施例之「地形形態」之結果雖然各數值有差,但由於『清晰(亦即無電性短路)』,故教示為相當實用。
保存安定性係將研磨用組成物(實施例1~19、比較例1~4)之溫度(組成物溫度)設為70℃,放置7天(168小時)後,使用其放置後之各研磨用組成物,以表2所示之研磨條件進行研磨而調查「研磨速率之變化」是否侷限在10%以內,且調查各實施例.比較例之研磨用組成物之保存安定性。
結果,如表1及表3所示,除了使用「月桂基硫酸銨」作為界面活性劑1之比較例3以外,可知放置7天後研磨速率之變化亦侷限在10%以內,使用月桂基硫酸銨作為界面活性劑之比較例3於7天後之研磨速率變化超過10%,可知不利長期保存(表1中「×」表示)。
此外,表中雖未顯示,但可知實施例13~19中,放置7天後研磨速率變化亦侷限在10%以內,為保存安定性優異。另一方面,比較例4與比較例3同樣,保存安定性
為「×」。
針對圖型晶圓上之凹坑數,係使用所得研磨用組成物(實施例3、5~12)以表2所示之研磨條件研磨銅圖型晶圓(直徑300mm)表面。
又,關於研磨壓力,係以2.3psi進行至2500Å,隨後以0.8psi進行至障壁膜露出為止。
此外,關於研磨時間,係自無圖型晶圓之研磨速率算出殘膜成為2500Å之時間,隨後僅改變0.8psi之壓力進而研磨至障壁膜自其露出為止。
又,如下述般測定圖型晶圓上之凹坑數。亦即,使用聚乙烯醇製刷,使用水作為洗淨藥劑,對已研磨過之晶圓進行洗淨60秒。洗淨後,利用附有光干涉式圖型之晶圓表面檢查裝置,以檢測出0.16μm以上尺寸之條件進行測定,計算凹坑數。結果示於表3。
結果,實施例8~12之防腐蝕劑(凹坑抑制劑)由於分配係數(logP)為不大於1.3,故藉由與本發明特有之磷酸系界面活性劑併用,不僅可有意義減輕圖型晶圓上之凹坑數,且基於凹陷(地形形態)、或Cu研磨速率、保存安定性之觀點而言,均見到非常優異者。
[表1]
[表3]
又,本申請案係基於2013年7月12日申請之日本國專利申請案第2013-146541號及2014年2月27日申請之日本專利申請案第2014-37409號,其揭示內容藉由參照全文被援用。
Claims (11)
- 一種研磨用組成物,其係於具有金屬配線層之研磨對象物的研磨中所用之研磨用組成物,其含有界面活性劑、水、與平均一次粒徑不同的二種類的研磨粒,前述界面活性劑在研磨用組成物中之含量為0.01mM以上1M以下,前述研磨粒在研磨用組成物中之含量為0.01g/L以上100g/L以下,前述界面活性劑係以下述式1表示之化合物或其鹽:
- 如請求項1之研磨用組成物,其中前述Ar係以下述式3表示:
- 如請求項2之研磨用組成物,其中A1~A3中之一個係Ar為以式3表示之聚氧伸烷基芳基醚基,其餘為氫原子。
- 如請求項1~3中任一項之研磨用組成物,其中進一步含有以前述式1表示以外之界面活性劑。
- 如請求項1~3中任一項之研磨用組成物,其進一步含有金屬防腐蝕劑,且前述金屬防腐蝕劑之分配係數(logP)為不大於1.3。
- 如請求項1~3中任一項之研磨用組成物,其進一步含有糖。
- 如請求項6之研磨用組成物,其中前述糖為多糖。
- 一種研磨用組成物之製造方法,其係於具有金屬配 線層之研磨對象物的研磨中所用之研磨用組成物之製造方法,該方法係混合界面活性劑、水、與平均一次粒徑不同的二種類的研磨粒,前述界面活性劑在研磨用組成物中之含量為0.01mM以上1M以下,前述研磨粒在研磨用組成物中之含量為0.01g/L以上100g/L以下,前述界面活性劑係以下述式1表示之化合物或其鹽:
- 一種研磨方法,其係以如請求項1~7中任一項之研磨用組成物、或以如請求項8之製造方法所製造之研磨用組成物研磨具有金屬配線層之研磨對象物。
- 如請求項9之研磨方法,其中前述研磨對象物進一步具有障壁層。
- 一種基板之製造方法,其包含以如請求項9或10之研磨方法研磨前述研磨對象物之步驟。
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