TWI592471B - Polishing composition - Google Patents
Polishing composition Download PDFInfo
- Publication number
- TWI592471B TWI592471B TW102140486A TW102140486A TWI592471B TW I592471 B TWI592471 B TW I592471B TW 102140486 A TW102140486 A TW 102140486A TW 102140486 A TW102140486 A TW 102140486A TW I592471 B TWI592471 B TW I592471B
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- polishing
- acid
- polishing composition
- metal substrate
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims description 148
- 239000000203 mixture Substances 0.000 title claims description 87
- -1 ethyl fluorenyl group Chemical group 0.000 claims description 97
- 229910052751 metal Inorganic materials 0.000 claims description 86
- 239000002184 metal Substances 0.000 claims description 85
- 239000000758 substrate Substances 0.000 claims description 65
- 239000002245 particle Substances 0.000 claims description 49
- 239000006061 abrasive grain Substances 0.000 claims description 38
- 229910044991 metal oxide Inorganic materials 0.000 claims description 25
- 150000004706 metal oxides Chemical class 0.000 claims description 25
- 125000000524 functional group Chemical group 0.000 claims description 21
- 230000004048 modification Effects 0.000 claims description 18
- 238000012986 modification Methods 0.000 claims description 18
- 239000007800 oxidant agent Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 238000005260 corrosion Methods 0.000 claims description 9
- 230000007797 corrosion Effects 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 125000003172 aldehyde group Chemical group 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 claims description 4
- 125000002098 pyridazinyl group Chemical group 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 125000003831 tetrazolyl group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 125000005956 isoquinolyl group Chemical group 0.000 claims description 2
- 125000001786 isothiazolyl group Chemical group 0.000 claims description 2
- 125000000842 isoxazolyl group Chemical group 0.000 claims description 2
- 125000002971 oxazolyl group Chemical group 0.000 claims description 2
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 2
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 2
- 125000005493 quinolyl group Chemical group 0.000 claims description 2
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 claims description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 2
- 125000000335 thiazolyl group Chemical group 0.000 claims description 2
- 125000001425 triazolyl group Chemical group 0.000 claims description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 claims 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 claims 1
- 125000001624 naphthyl group Chemical group 0.000 claims 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 56
- 239000007822 coupling agent Substances 0.000 description 22
- 229910000420 cerium oxide Inorganic materials 0.000 description 19
- 239000010410 layer Substances 0.000 description 19
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 19
- 125000001931 aliphatic group Chemical group 0.000 description 18
- 125000005647 linker group Chemical group 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 13
- 125000001424 substituent group Chemical group 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 10
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 10
- 239000012964 benzotriazole Substances 0.000 description 10
- 239000004020 conductor Substances 0.000 description 10
- 150000002430 hydrocarbons Chemical group 0.000 description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 9
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 150000005215 alkyl ethers Chemical class 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 125000004093 cyano group Chemical group *C#N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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
- 150000001875 compounds Chemical class 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 150000002391 heterocyclic compounds Chemical group 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 229910002808 Si–O–Si Inorganic materials 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 239000003945 anionic surfactant Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 150000007522 mineralic acids Chemical class 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000003002 pH adjusting agent Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 229960002449 glycine Drugs 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000006748 scratching Methods 0.000 description 4
- 230000002393 scratching effect Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- DFYGYTNMHPUJBY-UHFFFAOYSA-N 4-(trimethoxymethyl)dodecane-1-thiol Chemical compound SCCCC(C(OC)(OC)OC)CCCCCCCC DFYGYTNMHPUJBY-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
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000004438 BET method Methods 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000004471 Glycine Substances 0.000 description 3
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-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
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 3
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 125000005047 dihydroimidazolyl group Chemical group N1(CNC=C1)* 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 229960004295 valine Drugs 0.000 description 3
- 239000004474 valine Substances 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 2
- LJVQHXICFCZRJN-UHFFFAOYSA-N 1h-1,2,4-triazole-5-carboxylic acid Chemical compound OC(=O)C1=NC=NN1 LJVQHXICFCZRJN-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
- SGVYKUFIHHTIFL-UHFFFAOYSA-N 2-methylnonane Chemical compound CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-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
- ONYNOPPOVKYGRS-UHFFFAOYSA-N 6-methylindole Natural products CC1=CC=C2C=CNC2=C1 ONYNOPPOVKYGRS-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- KMNUEKYYJJXDHF-UHFFFAOYSA-N C(#N)CCC(C(OCC)(OCC)OCC)CCCCCCCC Chemical compound C(#N)CCC(C(OCC)(OCC)OCC)CCCCCCCC KMNUEKYYJJXDHF-UHFFFAOYSA-N 0.000 description 2
- KFHNUDMOWFYDHZ-UHFFFAOYSA-N C(#N)CCCC(C(OC)(OC)OC)CCCCCCCC Chemical compound C(#N)CCCC(C(OC)(OC)OC)CCCCCCCC KFHNUDMOWFYDHZ-UHFFFAOYSA-N 0.000 description 2
- HMWGIKRPUHMXKA-UHFFFAOYSA-N C(C)OC(CCCCCCCCCCCCN1C=NCC1)(OCC)OCC Chemical compound C(C)OC(CCCCCCCCCCCCN1C=NCC1)(OCC)OCC HMWGIKRPUHMXKA-UHFFFAOYSA-N 0.000 description 2
- JSGRIFNBTXDZQU-UHFFFAOYSA-N C1(=CC=CC=C1)C(C(OC)(OC)OC)CCCCCCCC Chemical compound C1(=CC=CC=C1)C(C(OC)(OC)OC)CCCCCCCC JSGRIFNBTXDZQU-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-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
- 239000004593 Epoxy Substances 0.000 description 2
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- IVYPNXXAYMYVSP-UHFFFAOYSA-N Indole-3-carbinol Natural products C1=CC=C2C(CO)=CNC2=C1 IVYPNXXAYMYVSP-UHFFFAOYSA-N 0.000 description 2
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- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-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
- SEQKRHFRPICQDD-UHFFFAOYSA-N N-tris(hydroxymethyl)methylglycine Chemical compound OCC(CO)(CO)[NH2+]CC([O-])=O SEQKRHFRPICQDD-UHFFFAOYSA-N 0.000 description 2
- XJDCHDFUMGSEHD-UHFFFAOYSA-N NCCCC(C(OC)(OC)OC)CCCCCCCC Chemical compound NCCCC(C(OC)(OC)OC)CCCCCCCC XJDCHDFUMGSEHD-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- 229910019142 PO4 Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical class NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- 150000001298 alcohols Chemical class 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- QWCKQJZIFLGMSD-UHFFFAOYSA-N alpha-aminobutyric acid Chemical compound CCC(N)C(O)=O QWCKQJZIFLGMSD-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229940024606 amino acid Drugs 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 229960005261 aspartic acid Drugs 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N benzopyrazine Natural products N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
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Classifications
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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
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Description
本發明係關於研磨用組成物。
近年來,伴隨LSI之高積體化.高速化,正開發嶄新的微細加工技術。化學機械性研磨(以下亦單稱為「CMP」)法亦為其中之一,LSI製造步驟尤其是頻繁被利用在多層配線形成步驟之層間絕緣膜的平坦化、金屬插頭形成、嵌入配線(鑲嵌配線)形成之技術。
形成半導體裝置之配線時,一般首先係於具有凹槽之絕緣膜之上依阻隔層及導電性物質層順序形成。然後,由化學機械研磨(CMP)至少去除位於凹槽外之導電性物質層部分(導電性物質層的外側部分)及位於凹槽外之阻隔層部分(阻隔層的外側部分)。此至少用以去除導電性物質層的外側部分及阻隔層的外側部分之研磨,通常係分成第1研磨步驟與第2研磨步驟進行。於第1研磨步驟,為了使阻隔層之上面露出,而去除導電性物質層的外側部分之一部分。接著於第2研磨步驟,使絕緣膜露出的同時,為了得到平坦之表面,至少去除導電性物質層的外側部分之殘部
及阻隔層的外側部分。
於用以形成如此半導體裝置之配線之CMP,一般係使用含有酸等之研磨促進劑及氧化劑,進而如有必要使用亦含有研磨粒之研磨用組成物。又,改善研磨後之研磨對象物的平坦性,亦即配線部為了抑制被過度研磨之碟形凹陷,亦提案使用進一步添加金屬防腐蝕劑之研磨用組成物。例如於日本特開平8-83780號公報,已揭示含有胺基乙酸及/或醯胺硫酸、氧化劑、苯并三唑及水之研磨用組成物。
由CMP之半導體裝置,尤其是導電性物質層為形成由銅或銅合金所構成之半導體裝置之配線時,配線部被過度研磨碟形凹陷或刮傷成為課題。又裝置越成為最先端,越被要求碟形凹陷之值或刮傷數目減少。即使使用如上述日本特開平8-83780號公報所揭示之研磨用組成物,達到此等最先端裝置所要求之性能實為困難。
因此本發明之目的為提供一種可一邊抑制研磨對象物之金屬基板的碟形凹陷,一邊抑制金屬基板表面的刮傷之研磨用組成物。
為了解決上述課題,本發明者們經重複累積銳意研究。其結果由包含新穎研磨粒之研磨用組成物,該研磨用組成物為包含:單末端為具有以對於金屬基板為進行吸附而抑制前述金屬基板溶解之官能基的表面修飾基、與前述表
面修飾基所固定化的金屬氧化物粒子,發現可以解決上述課題。而且根據上述卓見,終至完成本發明。
亦即,本發明係一種研磨用組成物,其係包含功能性研磨粒與水,前述功能性研磨粒為包含:單末端為具有以對於金屬基板為進行吸附而抑制前述金屬基板溶解之官能基的表面修飾基、與前述表面修飾基所固定化的金屬氧化物粒子。
本發明係一種研磨用組成物,其係包含功能性研磨粒與水,前述功能性研磨粒為包含:單末端為具有以對於金屬基板為進行吸附而抑制前述金屬基板溶解之官能基的表面修飾基、與前述表面修飾基所固定化的金屬氧化物粒子。藉由成為如此之構成,成為可一邊抑制研磨對象物之金屬基板的碟形凹陷,一邊抑制金屬基板表面的刮傷之研磨用組成物。
藉由使用本發明之研磨用組成物而得到如上述效果之詳細理由雖尚不明瞭,但被認為係藉由使用上述之功能性研磨粒,表面修飾基中之官能基對於金屬基板進行吸附,抑制從金屬基板之金屬的溶解,作為其結果,被認為可抑制金屬基板的碟形凹陷。又,關於刮傷,被認為應該是有藉由金屬氧化物粒子被表面修飾而提昇功能性研磨粒之分散性,而抑制起於凝集之研磨粒所造成的金屬基板表面之刮傷之效果。尚且,上述機制係藉由推測者,本發明並非
被限定於上述機制。
以下,對於本發明之研磨用組成物之構成進行詳細說明。
成為本發明研磨對象物之金屬基板,較佳為具有導電性物質層,如有必要具有阻隔層及絕緣膜。
導電性物質層所包含之材料並未特別限制,例如可列舉銅、鋁、鉿、鈷、鎳、鈦、鎢等之金屬。上述之金屬以合金或金屬化合物之形態可包含於導電性物質層。較佳為銅、或銅合金。此等之材料可單獨或組合2種以上使用。
作為阻隔層所包含之材料,雖並未特別限制,但例如可列舉鉭、鈦、鎢、鈷、金、銀、白金、鈀、銠、釕、銥、鋨等之貴金屬等。此等金屬係可以合金或金屬化合物之形態包含於阻隔層。此等金屬可單獨或組合2種以上使用。
作為絕緣膜所包含之材料,可列舉含有TEOS(四乙氧基甲矽烷)等Si之材料。
本發明之研磨用組成物中所包含之功能性研磨粒係具有機械性研磨金屬基板之作用,又,抑制金屬基板之碟形凹陷。
進而,該功能性研磨粒因為金屬氧化物粒子為以經表
面修飾之形態,具有良好之分散性。據此,亦具有抑制起於凝集之研磨粒所造成的金屬基板表面之刮傷的效果。
該功能性研磨粒係包含:單末端為具有以對於金屬基板為進行吸附而抑制前述金屬基板溶解之官能基的表面修飾基、與前述表面修飾基所固定化的金屬氧化物粒子。作為固定化之形態雖並未特別限制,但以前述表面修飾基化學鍵結於前述金屬氧化物粒子形態為佳。
作為金屬氧化物粒子之具體例,例如可列舉二氧化矽、氧化鋁、氧化鈰、二氧化鈦等。該金屬氧化物粒子可單獨或混合2種以上使用。又,該研磨粒可使用市售品亦可使用合成品。
此等金屬氧化物當中,以二氧化矽為佳,特佳為膠態二氧化矽。
關於本發明之表面修飾基,藉由對於金屬基板進行吸附抑制,於單末端具有前述金屬基板溶解之官能基(以下亦單稱為官能基)。進而以具有連結前述官能基與上述金屬氧化物粒子之2價連結基(以下亦單稱為連結基)為佳。
作為官能基之例,例如可列舉醯基、乙醯基、醛基、環氧基、羧基、磺基、巰基、硝基、磷酸基、醯胺基、胺基、氰基、羰基、亞胺基、偶氮基、疊氮基、苯基、吡咯
基、吡唑基、咪唑基、二氫咪唑基、三唑基、苯并三唑基、四唑基、吡啶基、吡嗪基、噠嗪基、氮茚基(Pyrindinyl)、茚基(Indolizinyl)、吲哚基、異吲哚基、吲唑基、嘌呤基、喹嗪基、喹啉基、異喹啉基、萘錠基(Naphthyridinyl)、酞嗪基(Phthalazinyl)、喹喔啉基、喹唑啉基、噌啉基(Cinnolinyl)、喋啶基(Pteridinyl)、噻唑基、異噻唑基、噁唑基、異噁唑基、呋呫基(Furazanyl)等。關於本發明之功能性研磨粒,可僅具有1種此等之官能基,亦可具有複數種。又,此等之官能基可具有取代基,亦可不具有。作為取代基之例,例如可列舉烷基、環烷基、芳烷基、烷氧基、芳基、芳氧基、鹵素原子(Cl、Br、F)、烷氧基羰基、烷硫基、芳硫基、胺基、取代胺基、醯胺基、磺胺基、脲、取代脲基、胺甲醯基、取代胺甲醯基、胺磺醯基、取代胺磺醯基、烷磺醯基、芳基磺醯基、羥基、氰基、硝基、磺基、羧基等。
此等官能基當中,從碟形凹陷抑制之觀點,較佳為選自由巰基、氰基、苯基、二氫咪唑基、苯并三唑基、及四唑基所構成之群中至少1種。
又,作為連結基之例,可列舉可具有取代基之2價烴基、包含雜原子之2價連結基、伸烷基矽烷氧基等作為合適者。該烴基所謂「具有取代基」,係意味著在該烴基之氫原子的一部分或全部被氫原子以外之基或原子所取代。該烴基以脂肪族烴基為佳。脂肪族烴基意味著不具有芳香族性之烴基。該脂肪族烴基可為飽和,可為不飽和,通常
以飽和為佳。
在2價之烴基,作為前述脂肪族烴基,更具體而言,可列舉直鏈狀或分支鏈狀之脂肪族烴基、於構造中包含環之脂肪族烴基等。
直鏈狀或分支鏈狀之脂肪族烴基以碳數1~10為佳,以1~8較佳,以1~5更佳。
作為直鏈狀之脂肪族烴基,以直鏈狀之伸烷基為佳,具體而言可列舉伸甲基(-CH2-)、伸乙基(-(CH2)2-)、三伸甲基(伸丙基)(-(CH2)3-)、四伸甲基(伸丁基)(-(CH2)4-)、五伸甲基(伸戊基)(-(CH2)5-)等。
作為分支鏈狀之脂肪族烴基,以分支鏈狀之伸烷基為佳,具體而言可列舉-CH(CH3)-、-CH(CH2CH3)-、-C(CH3)2-、-C(CH3)(CH2CH3)-、-C(CH3)(CH2CH2CH3)-、-C(CH2CH3)2-等之烷基伸甲基;-CH(CH3)CH2-、-CH(CH3)CH(CH3)-、-C(CH3)2CH2-、-CH(CH2CH3)CH2-、-C(CH2CH3)2-CH2-等之烷基伸乙基;-CH(CH3)CH2CH2-、-CH2CH(CH3)CH2-等之烷基三伸甲基;-CH(CH3)CH2CH2CH2-、-CH2CH(CH3)CH2CH2-等之烷基四伸甲基等之烷基伸烷基等。作為烷基伸烷基之烷基,以碳數1~5之直鏈狀烷基為佳。
鏈狀之脂肪族烴基可具有取代基,亦可不具有。作為該取代基,可列舉氧原子(=O)等。
作為於構造中包含環之脂肪族烴基,可列舉環狀之脂肪族烴基(從脂肪族烴環除掉2個氫原子之基)、該環狀之脂肪族烴基為鍵結於前述鏈狀之脂肪族烴基之末端或介在
於鏈狀之脂肪族烴基途中之基等。
環狀之脂肪族烴基以碳數3~20為佳,以3~12更佳。
環狀之脂肪族烴基可為多環式基,可為單環式基。作為單環式基,以從碳數3~6之單環烷烴移除2個氫原子之基為佳,作為該單環烷烴可例示環戊烷、環己烷等。作為多環式基,以從碳數7~12之聚環烷烴移除2個氫原子之基為佳,作為該聚環烷烴,具體而言可列舉金剛烷、降莰烷、異降莰烷、三環癸烷、四環十二烷等。
環狀之脂肪族烴基可具有取代基,亦可不具有。作為取代基,可列舉碳數1~5之烷基、氧原子(=O)等。
連結基為包含雜原子之2價連結基時,作為包含雜原子之2價連結基,可列舉-O-、-C(=O)-O-、-C(=O)-、-O-C(=O)-O-、-C(=O)-NH-、-NH-(H可被烷基、醯基等取代基所取代)、-S-、-S(=O)2-、-S(=O)2-O-、「-A-O(氧原子)-B-(惟,A及B分別獨立為可具有取代基之2價烴基)」、或可具有取代基之2價烴基與包含雜原子之2價連結基的組合等。作為可具有取代基之2價烴基,可列舉與可具有上述取代基之烴基相同者,以直鏈狀、分支鏈狀、或於構造中包含環之脂肪族烴基為佳。
作為連結基為伸烷基矽烷氧基時之例,例如可列舉伸乙基二甲氧基矽烷氧基(-(CH2)2-Si(OCH3)2-O-)、伸丙基二甲氧基矽烷氧基(-(CH2)3-Si(OCH3)2-O-)、伸丁基二甲氧基矽烷氧基(-(CH2)4-Si(OCH3)2-O-)、伸乙基二甲氧基
矽烷氧基(-(CH2)2-Si(OC2H5)2-O-)、伸丙基二乙氧基矽烷氧基(-(CH2)3-Si(OC2H5)2-O-)、伸丁基二乙氧基矽烷氧基(-(CH2)4-Si(OC2H5)2-O-)等。
此等連結基當中,以伸乙基二甲氧基矽烷氧基(-(CH2)2-Si(OCH3)2-O-)、伸丙基二甲氧基矽烷氧基(-(CH2)3-Si(OCH3)2-O-)、或伸丁基二甲氧基矽烷氧基(-(CH2)4-Si(OCH3)2-O-)為佳。
作為更佳之表面修飾基,可列舉具有伸丙基二甲氧基矽烷氧基之表面修飾基作為連結基。
關於本發明之功能性研磨粒之製造方法雖並未特別限制,但例如可藉由對於上述金屬氧化物粒子添加矽烷偶合劑,使其反應並使其結合來製造。
作為所使用矽烷偶合劑之例,例如可列舉苯基三甲氧基矽烷、苯基三乙氧基矽烷等之芳香族矽烷;3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、2-(3,4環氧基環己基)乙基三甲氧基矽烷等之環氧系矽烷;3-胺基丙基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基二甲基乙氧基矽烷、3-胺基丙基甲基二乙氧基矽烷、4-胺基丁基三乙氧基矽烷、3-胺基丙基二異丙基乙氧基矽烷、1-胺基-2-(二甲基乙氧基矽烷基)丙烷、(胺基乙基胺基)-3-異丁基二甲基甲氧基矽烷、N-(2-胺基乙基)-3-胺基異丁基甲基二
甲氧基矽烷、(胺基乙基胺甲基)苯乙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三乙氧基矽烷、N-(6-胺基己基)胺甲基三甲氧基矽烷、N-(6-胺基己基)胺甲基三乙氧基矽烷、N-(6-胺基己基)胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-11-胺基十一烷基三甲氧基矽烷、11-胺基十一烷基三乙氧基矽烷、3-(m-胺基苯氧基)丙基三甲氧基矽烷、m-胺基苯基三甲氧基矽烷、p-胺基苯基三甲氧基矽烷、(3-三甲氧基矽烷基丙基)二伸乙基三胺、N-甲基胺基丙基甲基二甲氧基矽烷、N-甲基胺基丙基三甲氧基矽烷、二甲基胺甲基乙氧基矽烷、(N,N-二甲基胺基丙基)三甲氧基矽烷、(N-乙醯基縮水甘油基)-3-胺基丙基三甲氧基矽烷等之胺基矽烷;3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷等之巰基系矽烷;N-(3-三乙氧基矽烷基丙基)-4,5-二氫咪唑、N-[3-(三乙氧基矽烷基丙基)]苯并三唑、2-(三甲氧基矽烷基乙基)吡啶、N-(3-三甲氧基矽烷基丙基)吡咯、N-[3-(三乙氧基矽烷基)丙基]-2-甲氧甲醯基氮丙啶等具有含氮雜環之有機烷氧基矽烷;3-(2,4-二硝基苯基胺基)丙基三乙氧基矽烷、3-(三乙氧基矽烷基丙基)-p-硝基苯并(Benz)醯胺等具有硝基之有機烷氧基矽烷;2-(甲氧甲醯基)乙基三甲氧基矽烷等之具有烷氧羰基之有機烷氧基矽烷;作為具有醛基之有機烷氧基矽烷之具有三乙氧基矽烷基丁基醛等醛基之有機烷氧基矽烷;2-羥基-4-(3-
甲基二乙氧基矽烷基丙氧基)二苯基酮等具有酮基之有機烷氧基矽烷;2-氰乙基三乙氧基矽烷、3-氰丙基苯基二甲氧基矽烷、11-氰癸基三甲氧基矽烷、3-氰丙基三甲氧基矽烷、3-氰丙基三乙氧基矽烷等具有氰基之有機烷氧基矽烷等。
此等矽烷偶合劑可單獨或併用2種以上。
此等矽烷偶合劑當中,以苯基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、N-(3-三乙氧基矽烷基丙基)-4,5-二氫咪唑、N-[3-(三乙氧基矽烷基丙基)]苯并三唑、3-氰丙基三甲氧基矽烷為佳。
該矽烷偶合劑可使用市售品,可使用合成品。合成矽烷偶合劑之方法雖並未特別限制,但例如可列舉將3-溴丙基三甲氧基矽烷等之鹵素含有矽烷化合物、與具有上述官能基之化合物,於硫酸等之酸觸媒存在下,於甲苯、二甲苯等之溶劑中使其反應之公知之方法。
作為金屬氧化物粒子與矽烷偶合劑的合成反應所使用之溶劑,雖並未特別限制,但例如可列舉水、或其他亦有作為有機溶劑之甲醇、乙醇、n-丙醇、異丙醇等之低級醇類、丙酮、甲基乙基酮等之酮類、二乙基醚、二噁烷、四氫呋喃等之醚類、N,N-二甲基甲醯胺等之醯胺類、二甲基亞碸等之亞碸類等。其中較佳為有機溶劑。此等溶劑可單獨或混合2種以上使用。
例如,於水分散之膠態二氧化矽添加矽烷偶合劑時,以矽烷偶合劑為溶解程度時加入親水性溶劑為佳。作為親
水性有機溶劑,例如可列舉甲醇、乙醇、異丙醇等之醇。此等之中,以由所使用矽烷偶合劑之水解使用與生成之醇同種之醇為佳。此係因為由矽烷偶合劑之水解藉由使用與生成之醇同種之醇,可更容易進行溶劑之回收、再利用。
合成反應之際,矽烷偶合劑之使用量的下限係將金屬氧化物粒子之莫耳數作為100莫耳%,以0.1莫耳%以上為佳,以1莫耳%以上較佳,以10莫耳%以上更佳。合成反應之際,矽烷偶合劑之使用量的上限係將金屬氧化物粒子之莫耳數作為100莫耳%,以90莫耳%以下為佳,以85莫耳%以下較佳,以80莫耳%以下更佳。若為於此範圍,在酸性之仄他電位(Zeta potential)十分穩定,又,可防止隨著時間而使金屬氧化物粒子凝膠化。
尚且,使用膠態二氧化矽等之膠態狀金屬氧化物粒子時,遵循下述數式1,可從以BET法測定之金屬氧化物粒子之比表面積決定矽烷偶合劑之使用量。
[數1]於金屬氧化物粒子1g所必需之矽烷偶合劑的莫耳數=金屬氧化物粒子之BET比表面積/(矽烷偶合劑1分子之占有面積)/(6.02×1023(個/mol).......數式1
合成反應之際之氛圍雖並未特別限定,但可於空氣氛圍下、氮、氬等之惰性氣體氛圍下、或真空下等進行。
合成反應時之pH亦雖並未特別限制,但以7以上且
11以下為佳。若為於此範圍,矽烷偶合劑係有效率與金屬氧化物粒子反應,可減低矽烷偶合劑之間進行自縮合之虞。
反應溫度之下限雖並未特別限制,但以5℃以上為佳,以7℃以上較佳,以10℃以上更佳。又,反應溫度之上限雖並未特別限制,但以100℃以下為佳,以95℃以下較佳,以90℃以下更佳。
反應時間之下限雖並未特別限制,但以1小時以上為佳,以2小時以上較佳,以3小時以上更佳。
尚且,該合成反應可以1階段進行,又,改變溫度可以2階段進行。
反應終了後,藉由使用旋轉蒸發器等減壓餾除反應溶劑,可得到目的之經表面修飾之金屬氧化物粒子。
功能性研磨粒之平均一次粒徑的下限,以5nm以上為佳,以7nm以上較佳,以10nm以上更佳。又,功能性研磨粒之平均一次粒徑的上限,以500nm以下為佳,以250nm以下較佳,以100nm以下更佳。若為於如此之範圍,可更加抑制於使用研磨用組成物之經研磨後之金屬基板的表面產生碟形凹陷。尚且,研磨粒之平均一次粒徑,例如根據以BET法測定之研磨粒之比表面積而算出。
研磨用組成物中功能性研磨粒之含量的下限,以0.01g/L以上為佳,以0.1g/L以上較佳,以1g/L以上更佳。又,研磨用組成物中功能性研磨粒之含量的上限,以200g/L以下為佳,以150g/L以下較佳,以100g/L以下更
佳。若為於如此之範圍,可抑制研磨用組成物的成本,可更加抑制於使用研磨用組成物之經研磨後之金屬基板的表面所產生之碟形凹陷。
本發明之研磨用組成物,除了上述之功能性研磨粒之外,亦可包含其他研磨粒。這樣的其他研磨粒,可為無機粒子、有機粒子、及有機無機複合粒子之任一者。作為無機粒子之具體例,例如可列舉二氧化矽、氧化鋁、氧化鈰、二氧化鈦等之未經表面修飾之由金屬氧化物所構成之粒子、氮化矽粒子、碳化矽粒子、氮化硼粒子。作為有機粒子之具體例,例如可列舉聚甲基丙烯酸甲酯(PMMA)粒子。該其他研磨粒可單獨或混合2種以上使用。又,該其他研磨粒可使用市售品亦可使用合成品。
本發明之研磨用組成物,含有水作為用以分散或溶解研磨粒之分散媒或溶劑。從抑制阻礙其他成分之作用的觀點來看,以盡可能不含有雜質之水為佳,具體而言,以在離子交換樹脂去除雜質離子之後,通過過濾器去除異物之純水或超純水、或蒸餾水為佳。
本發明之研磨用組成物係如有必要可進一步包含氧化劑、金屬防腐蝕劑、研磨促進劑、界面活性劑、防腐劑、防黴劑、還原劑、水溶性高分子、用以溶解難溶性之有機
物之有機溶劑等之其他成分。此等其他成分之中,以選自由氧化劑、金屬防腐蝕劑、研磨促進劑、及界面活性劑所構成之群中至少1種為佳。以下,對於係較佳之其他成分之氧化劑、金屬防腐蝕劑、研磨促進劑、界面活性劑進行說明。
關於本發明之研磨用組成物可包含氧化劑。研磨用組成物中所包含之氧化劑,具有氧化金屬基板之表面之作用,由研磨用組成物提昇金屬基板之研磨速度。
可使用之氧化劑,例如過氧化物。作為過氧化物之具體例,可列舉過氧化氫、過乙酸、過碳酸鹽、過氧化脲及過氯酸、以及過硫酸鈉、過硫酸鉀、過硫酸銨等之過硫酸鹽。此等氧化劑可單獨或混合2種以上使用。其中以過硫酸鹽及過氧化氫為佳,特佳為過氧化氫。
研磨用組成物中氧化劑的含量以0.1g/L以上為佳,較佳為1g/L以上,更佳為3g/L以上。隨著氧化劑的含量變多,來提昇藉由研磨用組成物之金屬基板的研磨速度。
研磨用組成物中氧化劑的含量,又,以200g/L以下為佳,較佳為100g/L以下,更佳為50g/L以下。隨著氧化劑的含量變少,除了可抑制研磨用組成物之材料成本,可減輕研磨使用後研磨用組成物之處理、亦即廢液處理之負荷。又,亦可減少由於氧化劑造成有引起金屬基板表面過度氧化之虞。
關於本發明之研磨用組成物,可包含金屬防腐蝕劑。藉由於研磨用組成物中加入金屬防腐蝕劑,可更加抑制經研磨後之金屬基板的碟形凹陷。
可使用之金屬防腐蝕劑雖並未特別限制,但較佳為雜環式化合物。雜環式化合物中雜環之員數並未特別限定。又,雜環式化合物可為單環化合物,可為具有縮合環之多環化合物。該金屬防腐蝕劑可單獨或混合2種以上使用。又,該金屬防腐蝕劑可使用市售品亦可使用合成品。
作為金屬防腐蝕劑之可使用之雜環化合物之具體例,例如可列舉吡咯化合物、吡唑化合物、咪唑化合物、三唑化合物、四唑化合物、吡啶化合物、吡化合物、噠嗪化合物、氮茚(Pyrindine)化合物、茚(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(quinolizine)化合物、喹啉化合物、異喹啉化合物、萘錠(Naphthyridine)化合物、酞嗪(Phthalazine)化合物、喹喔啉化合物、喹唑啉化合物、噌啉(Cinnoline)化合物、喋啶(Pteridine)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、呋呫(Furazan)化合物等之含氮雜環化合物。
進而列舉具體之例時,作為吡唑化合物之例,例如可列舉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、異嘌呤醇(Allopurinol)、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-胺等。
作為咪唑化合物之例,例如可列舉咪唑、1-甲基咪唑、2-甲基咪唑、4-甲基咪唑、1,2-二甲基吡唑、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(Benz)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、5-硝基苯并咪唑、1H-嘌呤等。
作為三唑化合物之例,例如可列舉1,2,3-三唑(1H-BTA)、1,2,4-三唑、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)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-3,5-二庚基-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)胺甲基]苯并三唑、1-[N,N-雙(羥基乙基)胺甲基]-5-甲基苯并三唑、1-[N,N-雙(羥基乙基)胺甲基]-4-甲基苯并三唑等。
作為四唑化合物之例,例如可列舉1H-四唑、5-甲基四唑、5-胺基四唑、及5-苯基四唑等。
作為吲唑化合物之例,例如可列舉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。
作為吲哚化合物之例,例如可列舉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。
此等之中較佳之雜環化合物為三唑化合物,尤其是以1H-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)胺甲基]-5-甲基苯并三唑、1-[N,N-雙(羥基乙基)胺甲基]-4-甲基苯并三唑、1,2,3-三唑、及1,2,4-三唑為佳。此等之雜環化合物因為對金屬基板表面之化學性或物理性吸附力高,可於金屬基板表面形成更強固之保護膜。因此,使用本發明之研磨用組成物進行研磨之後,於提昇金屬基板表面之平坦性係為有利。
此等之中較佳之金屬防腐蝕劑為含氮五員環化合物,以選自由1H-吡唑、1,2,4-三唑、及1H-四唑所構成之群中至少1種更佳。藉由使用此等之化合物,可抑制金屬基板之過度蝕刻。
研磨用組成物中金屬防腐蝕劑之含量的下限,以0.001g/L以上為佳,較佳為0.005g/L以上,更佳為0.01g/L以上。又,研磨用組成物中金屬防腐蝕劑之含量的上限,以20g/L以下為佳,較佳為15g/L以下,更佳為10g/L以下。若為於如此之範圍,提昇使用研磨用組成物進行研磨後之金屬基板表面的平坦性,又,提昇藉由研磨用組成物之金屬基板的研磨速度。
關於本發明之研磨用組成物包含研磨促進劑。研磨促進劑係錯合化而結合於金屬基板表面,藉由將不溶性之脆性膜形成於金屬基板表面,進行由研磨用組成物提昇金屬基板的研磨速度的功能。又,藉由研磨促進劑具有蝕刻作用,於藉由研磨用組成物提昇金屬基板的研磨速度具有有利的效果。
作為研磨促進劑,例如可使用無機酸、有機酸、胺基酸、腈化合物及螯合劑等。作為無機酸之具體例,可列舉硫酸、硝酸、硼酸、碳酸、次亞磷酸、亞磷酸、磷酸等。作為有機酸之具體例,可列舉甲酸、乙酸、丙酸、丁酸、戊酸、2-甲基丁酸、n-己酸、3,3-二甲基丁酸、2-乙基丁酸、4-甲基戊酸、n-庚酸、2-甲基己酸、n-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、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之有機硫酸。取代無機酸或有機酸,與或無機酸或有機酸組合,可使用無機酸或有機酸之鹼金屬鹽等之鹽。
作為胺基酸之具體例,可列舉甘胺酸、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、纈氨酸、白胺酸、正白胺酸、異白胺酸、苯基丙胺酸、脯胺酸、肌胺酸、鳥胺酸、蓖麻毒素、牛磺酸、絲胺酸、息寧胺酸、類絲胺酸、酪胺酸、二羥乙甘胺酸(Bicine)、三(羥甲基)甲基甘胺酸(Tricine)、3,5-二碘-
酪胺酸、β-(3,4-二羥基苯基)-丙胺酸、甲狀腺素、4-羥基-脯胺酸、半胱胺酸、甲硫胺酸、乙硫胺酸、羊毛硫胺酸、胱硫醚(Cystathionine)、胱胺酸、氧化半胱胺酸、天冬胺酸、麩胺酸、S-(羧基甲基)-半胱胺酸、4-胺基丁酸、天冬醯胺酸、麩胺醯胺酸、氮絲胺酸、L-精胺酸、刀豆胺酸(Canavanine)、瓜胺酸、δ-羥基-蓖麻毒素、肌酸、組胺酸、1-甲基-組胺酸、3-甲基-組胺酸及色胺酸。其中較佳為甘胺酸、丙胺酸、蘋果酸、酒石酸、檸檬酸、乙醇酸、羥乙磺酸或該等之鹽。
作為腈化合物之具體例,例如可列舉乙睛、胺基乙睛、丙睛、丁睛、異丁睛、苯并腈、戊二腈、甲氧基乙睛等。
作為螯合劑之具體例,可列舉氮基三乙酸、二乙烯三胺五乙酸、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、甘醇醚二胺四乙酸、乙二胺鄰羥基苯基乙酸、乙二胺二琥珀酸(SS體)、N-(2-羧酸乙酯)-L-天冬胺酸、β-丙胺酸二乙酸、2-膦醯基丁烷-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。
研磨用組成物中研磨促進劑之含量的下限,以0.01g/L以上為佳,較佳為0.1g/L以上,更佳為1g/L以上。隨著研磨促進劑之含量增多,藉由研磨用組成物提昇金屬基板的研磨速度。另外,研磨用組成物中研磨促進劑之含量的上限,以50g/L以下為佳,較佳為30g/L以下,更
佳為15g/L以下。隨著研磨促進劑之含量變少,可抑制研磨用組成物之材料成本。
關於本發明之研磨用組成物可包含界面活性劑。藉由於研磨用組成物中加入界面活性劑,可更加抑制經研磨後之金屬基板的碟形凹陷。
被使用之界面活性劑雖可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性界面活性劑之任一者,但其中以陰離子性界面活性劑及非離子性界面活性劑為佳。可組合複數種類之界面活性劑使用,尤其是以組合陰離子性界面活性劑與非離子性界面活性劑使用為佳。
作為陰離子性界面活性劑之具體例,例如可列舉聚氧乙烯烷基醚乙酸、聚氧乙烯烷基醚硫酸、烷基醚硫酸、聚氧乙烯烷基硫酸酯、烷基硫酸酯、聚氧乙烯烷基硫酸、烷基硫酸、烷基苯磺酸、烷基磷酸酯、聚氧乙烯烷基磷酸酯、聚氧乙烯磺基琥珀酸、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。其中以聚氧乙烯烷基醚乙酸、聚氧乙烯烷基醚硫酸鹽、烷基醚硫酸鹽及烷基苯磺酸鹽為佳。此等中較佳之陰離子性界面活性劑因為對金屬基板表面之化學性或物理性吸附力高,於金屬基板表面形成更強固之保護膜。因此,使用研磨用組成物進行研磨之後,於提昇金屬基板表面之平坦性係為有利。
作為陽離子性界面活性劑之具體例,例如可列舉烷基三甲基銨鹽、烷基二甲基銨鹽、烷基苄基二甲基銨鹽、及烷基胺鹽。
作為兩性界面活性劑之具體例,例如可列舉烷基甜菜鹼及烷基氧化胺。
作為非離子性界面活性劑之具體例,例如可列舉聚氧乙烯烷基醚等之聚氧化烯烷基醚、山梨醇酐脂肪酸酯、甘油脂肪酸酯、聚氧乙烯脂肪酸酯、聚氧乙烯烷基胺、及烷基烷醇醯胺。其中以聚氧化烯烷基醚為佳。聚氧化烯烷基醚因為對金屬基板表面之化學性或物理性吸附力高,於金屬基板表面形成更強固之保護膜。因此,使用研磨用組成物進行研磨之後,於提昇金屬基板表面之平坦性係為有利。
研磨用組成物中界面活性劑的含量,以0.001g/L以上為佳,較佳為0.005g/L以上,更佳為0.01g/L以上。隨著界面活性劑的含量增多,使用研磨用組成物進行研磨之後提昇金屬基板表面之平坦性係有利點。研磨用組成物中界面活性劑的含量,又以20g/L以下為佳,較佳為15g/L以下,更佳為10g/L以下。隨著界面活性劑的含量變少,藉由研磨用組成物提昇研磨速度係有利點。
本發明之研磨用組成物之pH的下限以1.5以上為佳。隨著研磨用組成物之pH增大,可減少藉由研磨用組成
物引起金屬基板表面過度蝕刻之虞。
又,研磨用組成物之pH的上限以12以下為佳。隨著研磨用組成物之pH變小,可更加抑制由於使用研磨用組成物之研磨而於所形成配線之側面產生凹陷,可進一步防止研磨粒之溶解。
為了將研磨用組成物之pH調整為所期望之值,可使用pH調整劑。使用之pH調整劑可為酸及鹼之任一者,又可為無機及有機之化合物之任一者。尚且,pH調節劑可單獨或混合2種以上使用。又,作為上述之各種添加劑,使用具有pH調整機能者(例如各種酸等)時,可將該添加劑作為pH調整劑的至少一部分利用。
本發明之研磨用組成物之製造方法雖並未特別限制,但例如將功能性研磨粒、及如有必要之其他成分可藉由於水中進行攪拌混合得到。
混合各成分之際的溫度雖並未特別限制,但以10~40℃為佳,為了提昇溶解速度可加熱。又,混合時間亦未特別限制。
如上述,本發明之研磨用組成物適合使用於經以上述說明之金屬基板的研磨。因此,本發明係提供一種將金屬基板使用本發明之研磨用組成物進行研磨之研磨方法。又
,本發明係提供一種包含將金屬基板以前述研磨方法進行研磨之步驟之金屬基板之製造方法。
作為研磨裝置,可使用具有安裝保持金屬基板等之支持器與可變更旋轉數之馬達等、可貼附研磨墊(研磨布)之研磨定盤之一般性研磨裝置。
作為上述研磨墊,並未特別限制可使用一般之不織布、聚胺基甲酸乙酯、及多孔質氟樹脂等。於研磨墊以實施如滯留研磨液方式之溝加工為佳。
研磨條件亦並未特別限制,例如研磨定盤之旋轉速度以10~500rpm為佳,加在金屬基板之壓力(研磨壓力)以0.5~10psi為佳。供給研磨用組成物於研磨墊之方法雖亦並未特別限制,但例如、採用連續性供給泵等之方法。此供給量雖並未限制,但以研磨墊之表面經常被覆本發明之研磨用組成物為佳。
研磨終了後,於流水中洗淨基板,藉由脫水機等甩落附著於基板上之水滴並藉由使其乾燥,而得到金屬基板。
本發明之研磨用組成物可為一液型,可為一開始為二液型之多液型。又,本發明之研磨用組成物係將研磨用組成物之原液使用水等之稀釋液,例如可藉由稀釋成10倍以上來調製。
於具備溫度計、攪拌翼之10L反應器,加入3-溴丙基三甲氧基矽烷2432g(10mol)、及甲苯:二甲苯=1:1(體積比)之混合溶劑5L,攪拌1小時而得到溶液。於此溶液,添加1,2,3-苯并三唑1191g(10mol)並進而攪拌1小時。然後,添加10μmol係酸觸媒之硫酸後,攪拌10分鐘。然後於50℃之空氣浴靜置4小時,使其進行反應。反應終了後,以旋轉式蒸發器取出甲苯與硫酸,而得到係目的物之N-[3-(三乙氧基矽烷基丙基)]苯并三唑。
準備膠態二氧化矽水溶液1000g(濃度19.5重量%)。秤量7.5g以其他途徑之上述合成例所得到之係矽烷偶合劑之N-[3-(三乙氧基矽烷基丙基)]苯并三唑,並使其溶解於甲醇50g。此矽烷偶合劑的量從以BET法測定之前述膠態二氧化矽的比表面積,遵循上述數式1,將矽烷偶合劑1分子之占有面積定為(5×10-10)2(m2)=25×10-20(m2),算出膠態二氧化矽之表觀莫耳數,係相當於其所算出莫耳數之50莫耳%的量。
將膠態二氧化矽溶液於空氣氛圍下、40℃下,一邊以攪拌翼之旋轉數600rpm攪拌,一邊將上述矽烷偶合劑之甲醇溶液以1ml/min之速度滴下。滴下後,以溶液之pH成為8.0-9.0之方式,使用pH調整劑(KOH)來調整pH。
pH調整後,將溶液於40℃之空氣浴靜置8小時,然
後於60℃之空氣浴靜置12小時。然後在旋轉式蒸發器,取出甲醇,得到功能性研磨粒1。
對於所得到功能性研磨粒1,可藉由進行XPS(X線光電子分光)分析,確認已形成Si-O-Si之化學鍵結。進而,對於所得到之功能性研磨粒1,藉由進行FT-IR(傅立葉轉換紅外光譜)分析,可確認具有係官能基之苯并三唑基。據此,由這2個分析方法,可確認已形成包含作為目的,於單末端具有苯并三唑基、且具有伸丙基二甲氧基矽烷氧基之表面修飾基作為連結基、與前述表面修飾基經固定化之二氧化矽之功能性研磨粒。
除了取代N-[3-(三乙氧基矽烷基丙基)]苯并三唑,改使用IM-2000(JX日礦日石金屬股份有限公司製)8.2g(相對於膠態二氧化矽之表觀莫耳數為50莫耳%)之外,其他與實施例1相同方式進行,得到功能性研磨粒2。
對於所得到之功能性研磨粒2,藉由進行XPS(X線光電子分光)分析,可確認已形成Si-O-Si之化學鍵結。進而,對於所得到之功能性研磨粒2,藉由進行FT-IR(傅立葉轉換紅外光譜)分析,可確認具有係官能基之巰基。據此,由這2個分析方法,可確認已形成包含作為目的,於單末端具有二氫咪唑基、且具有伸丙基二甲氧基矽烷氧基之表面修飾基作為連結基、與前述表面修飾基經固定化之二氧化矽之功能性研磨粒。
除了取代N-[3-(三乙氧基矽烷基丙基)]苯并三唑,改使用KBM-803(信越化學工業股份有限公司製、3-巰基丙基三甲氧基矽烷)3.9g(相對於膠態二氧化矽之表觀莫耳數為50莫耳%)之外,其他與實施例1相同方式進行,得到功能性研磨粒3。
對於所得到之功能性研磨粒3,由進行XPS(X線光電子分光)分析,可確認已形成Si-O-Si之化學鍵結。進而,對於所得到之功能性研磨粒3,由進行FT-IR(傅立葉轉換紅外光譜)分析,可確認具有係官能基之苯基。據此,由這2個分析方法,可確認已形成包含作為目的,於單末端具有巰基、且具有伸丙基二甲氧基矽烷氧基之表面修飾基作為連結基、與前述表面修飾基經固定化之二氧化矽之功能性研磨粒。
除了取代N-[3-(三乙氧基矽烷基丙基)]苯并三唑,改使用三甲氧基苯基矽烷(東京化成工業股份有限公司製)4.1g(相同於膠態二氧化矽之表觀莫耳數為50莫耳%)之外,其他與實施例1相同方式進行,得到功能性研磨粒4。
對於所得到之功能性研磨粒4,由進行XPS(X線光電子分光)分析,可確認已形成Si-O-Si之化學鍵結。進而,對於所得到之功能性研磨粒4,由進行FT-IR(傅立葉轉換紅外光譜)分析,可確認具有係官能基之氰基。據此,據
此,由這2個分析方法,可確認已形成包含作為目的,於單末端具有苯基、且具有伸丙基二甲氧基矽烷氧基之表面修飾基作為連結基、與前述表面修飾基經固定化之二氧化矽之功能性研磨粒。
除了取代N-[3-(三乙氧基矽烷基丙基)]苯并三唑,改使用2-氰乙基三乙氧基矽烷(東京化成工業股份有限公司製)3.2g(相對於膠態二氧化矽之表觀莫耳數為50莫耳%)之外,其他與實施例1相同方式進行,得到功能性研磨粒5。
對於所得到之功能性研磨粒5,由進行XPS(X線光電子分光)分析,可確認已形成Si-O-Si之化學鍵結。進而,對於所得到之功能性研磨粒5,由進行FT-IR(傅立葉轉換紅外光譜)分析,可確認具有係官能基之氰基。據此,由這2個分析方法,可確認已形成包含作為目的,於單末端具有氰基、且具有伸丙基二甲氧基矽烷氧基之表面修飾基作為連結基、與前述表面修飾基經固定化之二氧化矽之功能性研磨粒。
使用所得到之功能性研磨粒1~5來調製研磨用組成物。具體而言,分別以功能性研磨粒成為6g/L、作為研磨促進劑之甘胺酸成為10g/L、作為氧化劑之過氧化氫成為35g/L、及作為金屬防腐蝕劑之1H-苯并三唑成為0.2g/L
之濃度的方式,於水中進行攪拌混合(混合溫度:約25℃、混合時間:約10分鐘),來調製研磨用組成物1~5。尚且,研磨用組成物之pH加入氫氧化鉀調整為pH7.0。
使用所得到之研磨用組成物1~5,評估對於Cu之研磨速度及蝕刻速度。尚且,研磨條件係如下述表1所示。
研磨速度係將研磨前後200mm之Cu晶圓的厚度從藉由直流4探針法之片電阻的測定求得,藉由其差除以研磨時間來評估。
蝕刻速度於25℃下浸漬1分鐘Cu晶圓,從其重量變化來評估。
尚且,作為比較例,除了取代功能性研磨粒1~5,改使用未經表面修飾之膠態二氧化矽(平均一次粒徑:35nm、平均二次粒徑:68nm)之研磨用組成物以與上述相同之方式進行調製,相同方式進行評估。
將評估結果示於下述表2。
從上述表2清楚明白,包含功能性研磨粒之實施例之研磨用組成物(本發明之研磨用組成物)係蝕刻速度低,可抑制金屬表面的碟形凹陷。
又,使用實施例1與比較例之研磨用組成物,進行研磨後200mm之Cu晶圓的刮傷評估。刮傷以光干涉式晶圓表面檢査裝置,以可檢查0.16um以上尺寸者之條件進行評估。
其結果,刮傷之個數於使用比較例之研磨用組成物時為65個,於使用實施例1之研磨用組成物時變成20個。據此,於使用實施例1之研磨用組成物時,判斷減低刮傷。
尚且,本申請係根據2012年12月28日所申請之日本專利申請第2012-288415號,其揭示內容由參照被作為整體引用。
Claims (5)
- 一種研磨用組成物,其係包含功能性研磨粒與水,前述功能性研磨粒為包含:單末端為具有以對於金屬基板為進行吸附而抑制前述金屬基板溶解之官能基的表面修飾基、與前述表面修飾基所固定化的金屬氧化物粒子,前述官能基為選自由乙醯基、醛基、羧基、磺基、硝基、磷酸基、胺基、羰基、亞胺基、偶氮基、疊氮基、吡咯基、吡唑基、咪唑基、三唑基、苯并三唑基、四唑基、吡啶基、吡嗪基、噠嗪基、氮茚基、茚基、吲哚基、異吲哚基、吲唑基、嘌呤基、喹嗪基、喹啉基、異喹啉基、萘錠基、酞嗪基、喹喔啉基、喹唑啉基、噌啉基、喋啶基、噻唑基、異噻唑基、噁唑基、異噁唑基、及呋呫基所構成之群中之至少1種。
- 如請求項1之研磨用組成物,其中,前述官能基為苯并三唑基。
- 如請求項1或2之研磨用組成物,其係進一步包含選自由氧化劑、金屬防腐蝕劑、研磨促進劑、及界面活性劑所構成之群中之至少1種。
- 一種研磨方法,其係將金屬基板使用請求項1~3中任一項記載之研磨用組成物進行研磨。
- 一種金屬基板之製造方法,其係包含將金屬基板以請求項4記載之研磨方法進行研磨之步驟。
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WO2016102279A1 (en) * | 2014-12-22 | 2016-06-30 | Basf Se | Use of a chemical mechanical polishing (cmp) composition for polishing of cobalt and / or co-balt alloy comprising substrates |
US9528030B1 (en) * | 2015-10-21 | 2016-12-27 | Cabot Microelectronics Corporation | Cobalt inhibitor combination for improved dishing |
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US10647887B2 (en) | 2018-01-08 | 2020-05-12 | Cabot Microelectronics Corporation | Tungsten buff polishing compositions with improved topography |
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