TW201610046A - 研磨用組成物 - Google Patents
研磨用組成物 Download PDFInfo
- Publication number
- TW201610046A TW201610046A TW104122154A TW104122154A TW201610046A TW 201610046 A TW201610046 A TW 201610046A TW 104122154 A TW104122154 A TW 104122154A TW 104122154 A TW104122154 A TW 104122154A TW 201610046 A TW201610046 A TW 201610046A
- Authority
- TW
- Taiwan
- Prior art keywords
- acid
- polishing
- cobalt
- compound
- polishing composition
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 198
- 239000000203 mixture Substances 0.000 title claims abstract description 93
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 95
- 239000010941 cobalt Substances 0.000 claims abstract description 95
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000010949 copper Substances 0.000 claims abstract description 66
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052802 copper Inorganic materials 0.000 claims abstract description 63
- 238000004090 dissolution Methods 0.000 claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000003112 inhibitor Substances 0.000 claims abstract description 27
- 239000007800 oxidant agent Substances 0.000 claims abstract description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 10
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 5
- -1 carboxyl group aminocarboxylic acids Chemical class 0.000 claims description 79
- 238000000034 method Methods 0.000 claims description 27
- 239000004094 surface-active agent Substances 0.000 claims description 22
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 13
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 claims description 3
- XNSPQPOQXWCGKC-UHFFFAOYSA-N C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.[N] Chemical compound C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.[N] XNSPQPOQXWCGKC-UHFFFAOYSA-N 0.000 claims description 3
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 claims description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical group C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 3
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 2
- WTBIAPVQQBCLFP-UHFFFAOYSA-N N.N.N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O Chemical compound N.N.N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O WTBIAPVQQBCLFP-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 134
- 229910052751 metal Inorganic materials 0.000 description 44
- 239000002184 metal Substances 0.000 description 44
- 150000003839 salts Chemical class 0.000 description 41
- 239000002253 acid Substances 0.000 description 28
- 230000004888 barrier function Effects 0.000 description 28
- 239000006061 abrasive grain Substances 0.000 description 24
- 125000004432 carbon atom Chemical group C* 0.000 description 18
- 229910000420 cerium oxide Inorganic materials 0.000 description 15
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- 125000003118 aryl group Chemical group 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 239000002585 base Substances 0.000 description 11
- 239000003002 pH adjusting agent Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229920003169 water-soluble polymer Polymers 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 10
- 150000007524 organic acids Chemical class 0.000 description 10
- 125000005013 aryl ether group Chemical group 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000005530 etching Methods 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
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- 235000012431 wafers Nutrition 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 239000011163 secondary particle Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 150000007522 mineralic acids Chemical class 0.000 description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000000908 ammonium hydroxide Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000002612 dispersion medium Substances 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 5
- 239000003755 preservative agent Substances 0.000 description 5
- 239000011164 primary particle Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 239000012212 insulator Substances 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
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- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 4
- 230000001629 suppression Effects 0.000 description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-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
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 3
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- 230000015572 biosynthetic process Effects 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
- 239000002738 chelating agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001869 cobalt compounds Chemical class 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 150000002391 heterocyclic compounds Chemical group 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
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- 238000012876 topography Methods 0.000 description 3
- 229940005605 valeric acid Drugs 0.000 description 3
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 2
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- OXQGTIUCKGYOAA-UHFFFAOYSA-N 2-Ethylbutanoic acid Chemical compound CCC(CC)C(O)=O OXQGTIUCKGYOAA-UHFFFAOYSA-N 0.000 description 2
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- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- NLSIIPKSANRIGS-UHFFFAOYSA-N 4-pyrrol-1-ylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1N1C=CC=C1 NLSIIPKSANRIGS-UHFFFAOYSA-N 0.000 description 2
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- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229960003104 ornithine Drugs 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 229960005190 phenylalanine Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229960005141 piperazine Drugs 0.000 description 1
- 229960003506 piperazine hexahydrate Drugs 0.000 description 1
- AVRVZRUEXIEGMP-UHFFFAOYSA-N piperazine;hexahydrate Chemical compound O.O.O.O.O.O.C1CNCCN1 AVRVZRUEXIEGMP-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 235000019448 polyvinylpyrrolidone-vinyl acetate copolymer Nutrition 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- AVTYONGGKAJVTE-UHFFFAOYSA-L potassium tartrate Chemical compound [K+].[K+].[O-]C(=O)C(O)C(O)C([O-])=O AVTYONGGKAJVTE-UHFFFAOYSA-L 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229940043230 sarcosine Drugs 0.000 description 1
- 229960001153 serine Drugs 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- KNRUQUSSDKZTSQ-UHFFFAOYSA-N tetrazol-1-amine Chemical compound NN1C=NN=N1 KNRUQUSSDKZTSQ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- BMCJATLPEJCACU-UHFFFAOYSA-N tricin Natural products COc1cc(OC)c(O)c(c1)C2=CC(=O)c3c(O)cc(O)cc3O2 BMCJATLPEJCACU-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 229960004295 valine Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
-
- 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
-
- 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
- C09K3/1409—Abrasive particles per se
-
- 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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- 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]
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
本發明提供一種研磨具有含銅之層與含鈷之層之研磨對象物時,可一方面對含銅之層展現高的研磨速度一方面抑制含鈷之層之溶解之研磨用組成物。
本發明係一種研磨用組成物,其為研磨具有含銅之層與含鈷之層之研磨對象物之用途中使用之研磨用組成物,且含有氧化劑、與由具有含氮5員環構造之化合物及具有2個以上羧基之胺基羧酸所組成之群選出之至少一種鈷溶解抑制劑。
Description
本發明係關於研磨用組成物,尤其是關於適於研磨具有含銅之層及含鈷之層之研磨對象物之研磨用組成物。
近年來,隨著LSI(Large Scale Integration,大型積體化)之高積體化、高性能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,係於LSI製造步驟,尤其是多層配線形成步驟中之層間絕緣膜之平坦化、金屬柱塞形成、埋入配線(鑲嵌(damascene)配線)形成中頻繁被利用之技術。鑲嵌配線技術可簡化配線步驟,或提高良率及信賴性,認為在爾後會擴大應用。
CMP之一般方法係將研磨墊貼附於圓形之研磨壓盤(platen)上,以研磨劑浸漬研磨墊表面,且壓抵向基板之形成金屬膜之面,於自其背面施加特定壓力(以下亦簡稱為研磨壓力)之狀態下旋轉研磨壓盤,藉由研磨劑與金屬膜之凸部之機械摩擦,而去除凸部之金屬膜者。
不過,目前鑲嵌配線由於為低阻抗故而主要使用銅作
為配線金屬,銅認為在日後之DRAM(動態隨機存取記憶體)為代表之記憶體裝置中將被擴大使用。而且,於形成鑲嵌配線之導電性物質(銅或銅合金等)之下層形成障蔽層以防止導電性物質擴散至層間絕緣膜中。構成該障蔽層之材料過去係使用鉭、鉭合金、或鉭化合物等(參照例如日本特開2001-85372號公報及日本特開2001-139937號公報)。
近年來,隨著配線微細化之傾向,銅之鍍敷不易上手而引起產生孔洞(局部不存在任何物質之現象)之現象。因此,為解決上述缺點,近年來已檢討在障蔽層與銅之間使用不易與銅親和之鈷或鈷化合物而補足密著性。且,已檢討使用鈷或鈷化合物作為障蔽層。
鑲嵌配線技術一般係在設有溝槽之絕緣體層上形成障蔽層、金屬配線層後,利用CMP去除配線部分以外之多餘配線材(金屬配線層)及障蔽層之操作而進行。
然而,近年來,如上述,已檢討使用含鈷之層的鑲嵌配線技術,以CMP研磨含鈷之層時,發生鈷易溶解之問題。更詳細而言,鑲嵌配線技術中,進行CMP以去除多餘之金屬配線層及障蔽層時,會有含鈷之層溶解,而在表面發生針孔或腐蝕之問題。據此,進行CMP時若於含鈷之層產生針孔或腐蝕,而有損及含鈷之層的功能之虞。
因此,要求在研磨具有含銅之層與含鈷之層之研磨對
象物時,可一方面對含銅之層展現高的研磨速度一方面抑制含鈷元素之層之溶解之研磨用組成物。
據此,本發明之目的係提供一種研磨用組成物,其在研磨具有含銅之層與含鈷之層之研磨對象物時,可一方面對含銅之層展現高的研磨速度一方面抑制含鈷之層之溶解。
為解決上述課題,本發明人等重複積極研究。結果,發現藉由使用含有氧化劑、與由特定之化合物群選出之鈷溶解抑制劑之研磨用組成物,能解決上述課題。更詳言之,基於藉由使用由具有含氮5員環構造之化合物及具有2個以上羧基之化合物所組成之群選出之至少一種有機化合物作為鈷溶解抑制劑,可一方面展現對含銅之層高的研磨速度一方面有效的抑制鈷之溶解之見解,因而完成本發明。
亦即,本發明係一種研磨用組成物,其係研磨具有含銅之層及含鈷之層之研磨對象物之用途中使用之研磨用組成物,且含有氧化劑、與鈷溶解抑制劑,前述鈷溶解抑制劑係由具有含氮5員環構造之化合物及具有2個以上羧基之化合物所組成之群選出之至少一種。
1‧‧‧部分
2‧‧‧含銅之層之部分
圖1為顯示使用實施例10之研磨用組成物,研磨鈷/銅圖型化晶圓後之圖型之剖面之SEM(掃描型電子顯微鏡)照片,1表示障蔽層(Ta層),2表示含銅之層。
圖2為顯示使用比較例12之研磨用組成物,研磨鈷/銅圖型化晶圓後之圖型之剖面之SEM(掃描型電子顯微鏡)照片,1表示障蔽層(Ta層),2表示含銅之層。
本發明係一種研磨用組成物,其係研磨具有含銅之層及含鈷之層之研磨對象物之用途中使用之研磨用組成物,且含有氧化劑、與鈷溶解抑制劑,前述鈷溶解抑制劑為由具有含氮5員環構造之化合物及具有2個以上羧基之化合物所組成之群選出之至少一種。藉由此構成,可一方面對含銅之層展現高的研磨速度一方面有效抑制含鈷之層之溶解。
構成障蔽層之鈷一般由於在障蔽層(及金屬配線層)之研磨條件下會溶解,故本發明人等檢討各種化合物作為鈷溶解抑制劑。結果,出乎意料地發現於研磨用組成物中添加由具有含氮5員環構造之化合物及具有2個以上羧基之化合物所組成之群選出之至少一種時,獲得優異之鈷溶解抑制效果。其機制如以下說明,但以下之機制為推測者,本發明並不受下述機制之任何限制。
構成障蔽層之鈷一般在障蔽層(及金屬配線層)之研磨條件之弱酸性~鹼性(約pH為4以上12以下之區域)時,容易因研磨時使用之水等而氧化。結果,認為表面經氧化之鈷於進行CMP時容易被溶解。
此時,鈷之最表面推測為以羥基(-OH)等被覆之狀
態。本發明之鈷溶解抑制劑認為係成為對該羥基配位或形成錯合物之形成,可謂於鈷之表面形成保護膜。結果,認為可有效抑制含鈷之層之溶解。此外,氧化劑具有對含銅之層展現高的研磨速度之作用。據此,依據本發明之研磨用組成物,可一方面對含銅之層展現高的研磨速度一方面抑制含鈷之層之溶解。
首先,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。
首先,於基板上形成具有溝槽之絕緣體層。接著,於該絕緣體層上依序形成障蔽層、含鈷之層、金屬配線層的含銅之層。又,本說明書中,所謂「含鈷」係顯示層中含鈷元素之樣態者,層中之鈷可為單體,亦可以鈷氧化物、鈷化合物、鈷合金等形態存在。同樣地,本說明書中,所謂「含銅」係顯示層中含銅元素之樣態者,層中之銅可為單體,亦可以銅氧化物、銅化合物、銅合金等形態存在。
障蔽層及含鈷之層係在含銅之層(金屬配線層)形成之前,以被覆絕緣層表面之方式形成於絕緣體層上。該等層之形成方法並無特別限制,可藉由例如濺鍍法、鍍敷法等習知方法形成。障蔽層及含鈷之層之厚度係小於溝槽之深度及寬度。含銅之層(金屬配線層)係接續於障蔽層及含鈷之層形成之後,以至少埋填溝槽之方式形成於障蔽層上。含銅之層(金屬配線層)之形成方法並無特別限制,
可以例如濺鍍法、鍍敷法等習知方法形成。
接著,以CMP去除配線部分以外之多餘之含銅之層(金屬配線層)、含鈷之層及障蔽層。結果,使位在溝槽中之障蔽層之部分(障蔽層之內側部分)之至少一部分、位在溝槽中之含鈷層之部分(含鈷層之內側部分)之至少一部分及位在溝槽中之含銅之層(金屬配線層)之部分(含銅之層之內側部分)之至少一部份殘留在絕緣體層上。亦即,溝槽之內側殘留障蔽層之一部分、含鈷之層之一部分及含銅之層之一部分。因此,殘留在溝槽內側之含銅之層之部分作為配線發揮功能。
障壁層中所含之金屬之例列舉為例如鉭、鈦、鎢;金、銀、鉑、鈀、銠、釕、銦、鋨等貴金屬等。該等其他金屬可單獨使用亦可組合2種以上使用。
含銅之層亦可含有銅以外之金屬。列舉為例如鋁、鉿、鈷、鎳、鈦、鎢等。該等金屬可以合金或金屬化合物之形態含於含銅之層中。該等金屬可單獨使用或組合2種以上使用。
接著,針對本發明之研磨用組成物之構成加以詳細說明。
本發明之研磨用組成物含有氧化劑。氧化劑對含銅之層具有展現高的研磨速度之作用。
可使用之氧化劑為例如過氧化物。過氧化物之具體例列舉為例如過氧化氫、過乙酸、過碳酸鹽、過氧化脲、過氯酸鹽、氯酸鹽、亞氯酸鹽、次氯酸鹽等鹵元素之含氧酸鹽以及過硫酸鈉、過硫酸鉀及過硫酸銨等之過硫酸鹽等。其中過硫酸鹽及過氧化氫基於研磨速度之觀點而言較佳,基於在水溶液中之安定性及對環境負荷之觀點以過氧化氫最好。
研磨用組成物中之氧化劑含量之下限較好為0.01質量%以上,更好為0.05質量%以上,又更好為0.1質量%以上。隨著氧化劑之含量增多,可進一步提高含銅之層之研磨速度。且,研磨用組成物中之氧化劑含量之上限較好為20質量%以下,更好為15質量%以下,又更好為10質量%以下。隨著氧化劑之含量減少,除了可抑制研磨用組成物之材料成本以外,亦具有可減輕研磨使用後之研磨用組成物之處理亦即廢液處理之負荷之優點。另外,亦具有不易因氧化劑而引起研磨對象物表面之過度氧化之優點。
本發明之研磨用組成物含有鈷溶解抑制劑。鈷溶解抑制劑添加之目的係如上述,在進行CMP時抑制鈷之溶解。本發明中,鈷溶解抑制劑係由具有含氮5員環構造之化合物及具有2個以上羧基之化合物所組成之群選出之至少一種。
具有含氮5員環構造之化合物列舉為例如吡咯化合物、吡唑化合物、咪唑化合物、三唑化合物、四唑化合物、吲哚嗪化合物、吲哚化合物、異吲哚化合物、吲唑化合物、嘌呤化合物、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。
若列舉更具體之例,吡咯化合物之例列舉為1H-吡咯、3-甲基吡咯、3-己基吡咯、3-苯基吡咯、N-苯基吡咯、N-乙基磺酸鹽吡咯、3,4-環己基吡咯、N-(4-氟苯基)吡咯、N-(4-氯苯基)吡咯、N-(4-氰基苯基)吡咯、N-(4-硝基苯基)吡咯、N-(4-胺基苯基)吡咯、N-(4-甲氧基苯基)吡咯、N-(4-(1-氧代乙基)苯基)吡咯、N-(4-三氟甲基苯基)吡咯、N-(4-羧基苯基)吡咯、N-(4-羧基苯基)吡咯、N-(1-萘基)吡咯、N-(2-萘基)吡咯等。
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、1,2-二甲基吡唑、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。
咪唑化合物之例列舉為例如1H-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、5-硝基苯并咪唑等。
三唑化合物之例列舉為例如1,2,3-三唑、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)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-甲基苯并三唑等。
四唑化合物之例列舉為例如1H-四唑、5,5’-雙-1H-四唑、5-甲基-1H-四唑、5-苯基-1H-四唑、5-胺基-1H-四
唑、5-巰基-1H-四唑、1-甲基-1H-四唑、1-苯基-1H-四唑、1-胺基-1H-四唑、1-巰基-1H-四唑、1-苯基-5-甲基-1H-四唑、1-苯基-5-胺基-1H-四唑、1-苯基-5-巰基-1H-四唑等。
吲哚嗪化合物之例列舉為例如吲哚嗪等。
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。
異吲哚化合物之例列舉為例如2H-異吲哚等。
吲唑化合物之例列舉為例如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。
嘌昤化合物之例列舉為例如嘌呤等。噻唑化合物之例列舉為例如1,3-噻唑等。異噻唑化合物之例列舉為例如1,2-噻唑等。噁唑化合物之例列舉為例如1,3-噁唑等。異噁唑化合物之例列舉為例如1,2-噁唑等。呋咱化合物之例列舉為例如1,2,5-噁二唑等。
該等中,基於確保對含銅之層之高研磨速度之觀點,較好為由1H-苯并三唑、5-甲基-1H-苯并三唑、1H-咪唑及1H-四唑所組成之群選出之至少一種。
具有2個以上羧基之胺基羧酸之例列舉為例如N,N’-雙(2-羥基苄基)乙二胺-N,N’-二乙酸、二伸乙基三胺五乙酸、三伸乙基四胺-N,N,N”,N”,N’”,N’”-六乙酸、氮基三乙酸、N-(2-羥基乙基)亞胺基二乙酸、N-(2-羥基乙基)乙二胺-N,N’,N’-三乙酸、1,2-二胺基丙烷-N,N,N’,N’-四乙酸、1,3-二胺基丙烷-N,N,N’,N’-四乙酸、反式-環己烷二胺-N,N,N’,N’-四乙酸、亞胺基二乙酸、乙醚二胺四乙酸、二醇醚二胺四乙酸、乙二胺四丙酸、苯二胺四乙酸等。
該等中,基於確保對含銅之層之高的研磨速度之觀點,較好為由二伸乙基三胺五乙酸、三伸乙基四胺-
N,N,N”,N”,N’”,N’”-六乙酸、氮基三乙酸、N-(2-羥基乙基)亞胺基二乙酸及N-(2-羥基乙基)乙二胺-N,N’,N’-三乙酸所組成之群選出之至少一種。
鈷溶解抑制劑在研磨用組成物中之含量之下限較好為0.001mol/L以上,更好為0.005mol/L以上,又更好為0.01mol/L以上。隨著鈷溶解抑制劑之含量增多,可進一步抑制含鈷之層之溶解。
且,鈷溶解抑制劑在研磨用組成物中之含量上限較好為100mol/L以下,更好為50mol/L以下,又更好為10mol/L以下。隨著鈷溶解抑制劑之含量減少,可確保保存安定性。
本發明之研磨用組成物亦可視需要進一步含有研磨粒、分散介質、溶劑、pH調整劑、研磨促進劑、金屬防腐蝕劑、界面活性劑、防腐劑、防黴劑、水溶性高分子等其他成分。以下針對其他成分加以說明。
本發明之研磨用組成物較好含有研磨粒。研磨粒具有對研磨對象物進行機械研磨之作用,且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、氧化鋁較佳,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,即使在酸性條件下具有Zeta電位較大之負值之經表面修飾之研磨粒,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。
本發明之研磨用組成物中所含之研磨粒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,無法發揮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。
且,如日本特開平4-214022號公報所揭示,亦可使用添加鹼性鋁鹽或鹼性鋯鹽製造之陽離子性二氧化矽作為研磨粒。
研磨粒之平均一次粒徑之下限較好為3nm以上,更
好為5nm以上,又更好為7nm以上。且,研磨粒之平均一次粒徑之上限較好為200nm以下,更好為150nm以下,又更好為100nm以下。
若為該範圍,則研磨用組成物對研磨對象物之研磨速度獲得提高,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凹陷。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算出。
研磨粒之平均二次粒徑之下限較好為10nm以上,更好為15nm以上,又更好為20nm以上。且,研磨粒之平均二次粒徑之上限較好為300nm以下,更好為260nm以下,又更好為220nm以下。若為該範圍,則研磨用組成物對研磨對象物之研磨速度獲得提高,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凹陷。又,此處所謂之二次粒徑係指研磨粒在研磨用組成物中締合而形成之粒子。該二次粒子之平均二次粒徑可藉例如動態光散射法測定。
本發明之研磨用組成物中之研磨粒之含量下限基於提高研磨對象物之研磨速度之觀點,較好為0.005質量%以上,更好為0.01質量%以上,又更好為0.1質量%以上。且,研磨用組成物中之研磨粒之含量基於降低研磨用組成
物之成本,抑制研磨後之研磨對象物表面產生之表面缺陷之觀點,上限較好為50重量%以下,更好為30重量%以下,又更好為20重量%以下。
本發明之研磨用組成物通常使用分散介質或溶劑以使各成分分散或溶解。分散介質或溶劑可考慮有機溶劑、水,但其中以含水較佳。就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。
本發明之研磨用組成物之pH可視需要藉由添加適量之pH調整劑而調整。pH調整劑可為酸及鹼之任一種,且亦可為無機化合物及有機化合物之任一種。藉此,可控制研磨對象物之研磨速度或研磨粒之分散性等。pH調整劑可單獨使用或亦可混合2種以上使用。
pH調整劑可使用習知之酸、鹼、或彼等之鹽。酸之具體例列舉為例如硫酸、硝酸、硼酸、碳酸、次磷酸、亞磷酸及磷酸等無機酸;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、鄰苯二酸、蘋果酸、酒石酸、檸檬酸及乳酸等羧酸,以及甲烷磺酸、乙烷磺酸及羥乙烷磺酸等有機硫酸等之有機酸等。
可使用作為pH調整劑之鹼之具體例列舉為鹼金屬之氫氧化物或鹽、第2族元素之氫氧化物或鹽、氫氧化四級銨或其鹽、氨、胺等。鹼金屬之具體例列舉為鉀、鈉等。鹽之具體例列舉為碳酸鹽、碳酸氫鹽、硫酸鹽、乙酸鹽等。四級銨之具體例列舉為四甲基銨、四乙基銨、四丁基銨等。
氫氧化四級銨化合物包含氫氧化四級銨或其鹽,具體例列舉為氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四丁基銨等。
胺之具體例列舉為甲胺、二甲胺、三甲胺、乙胺、二乙胺、三乙胺、乙二胺、單乙醇胺、N-(β-胺基乙基)乙醇胺、六亞甲基二胺、二伸乙基三胺、三伸乙基四胺、無水哌嗪、哌嗪六水合物、1-(2-胺基乙基)哌嗪、N-甲基哌嗪、胍等。該等鹼可單獨使用1種,亦可組合2種以上使用。
該等鹼中,以氨、銨鹽、鹼金屬氫氧化物、鹼金屬鹽、氫氧化四級銨化合物、及胺較佳。更好係使用氨、鉀化合物、氫氧化鈉、氫氧化四級銨化合物、碳酸氫銨、碳酸銨、碳酸氫鈉及碳酸鈉。又,研磨用組成物中,基於防止金屬污染之觀點更好含有鉀化合物作為鹼。鉀化合物列舉為鉀之氫氧化物或鹽,具體列舉為氫氧化鉀、碳酸鉀、
碳酸氫鉀、硫酸鉀、乙酸鉀、氯化鉀等。
pH調整劑之添加量並無特別限制,只要以使研磨用組成物成為期望之pH之方式適當調整即可。
本發明之研磨用組成物之pH之範圍的下限,基於隨著pH變高,研磨對象物之溶解進展而提高研磨用組成物之研磨速度之觀點,較好為3以上,更好為4以上,又更好為5以上。且,pH之範圍的上限,基於隨著pH變低,操作上較容易之觀點,較好未達14。
本發明之研磨用組成物較好含有研磨促進劑。研磨促進劑具有化學蝕刻研磨對象物表面之作用,且提高研磨用組成物對研磨對象物之研磨速度。
研磨促進劑列舉為例如無機酸或其鹽、有機酸或其鹽、腈化合物、胺基酸及螯合劑等。該等研磨促進劑可單獨使用或亦可混合2種以上使用。且,該研磨促進劑可使用市售品亦可使用合成品。
無機酸之具體例列舉為例如、硫酸、硝酸、碳酸、硼酸、四氟硼酸、次磷酸、亞磷酸、磷酸、焦磷酸等。
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、乳酸、乙醇酸、甘油酸、苯甲酸、水楊酸等一元羧酸。另外,亦可使用甲烷磺酸、乙烷磺酸及羥乙磺酸等磺
酸。
亦可使用前述無機酸或前述有機酸之鹽作為研磨促進劑。尤其,使用弱酸與強鹼之鹽、強酸與弱鹼之鹽、或弱酸與弱鹼之鹽時,可期待pH之緩衝作用。此種鹽之例列舉為例如氯化鉀、硫酸鈉、硝酸鉀、碳酸鉀、四氟硼酸鉀、焦磷酸鉀、草酸鉀、草酸三鈉、(+)-酒石酸鉀、六氟磷酸鉀等。
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。
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-甲基組胺酸及色胺酸等。
螯合劑之具體例列舉為N,N,N-三亞甲基膦酸、乙二胺-N,N,N’,N’-四亞甲基磺酸、2-膦醯丁烷-1,2,4-三羧酸、1-羥基亞乙基-1,1-二膦酸、1,2-二羥基苯-4,6-二磺酸等。
該等中,較好為選自由無機酸或其鹽、羧酸或其鹽、及腈化合物所組成群組之至少1種,就與研磨對象物所含之金屬化合物之錯合構造之安定性之觀點而言,更好為無機酸或其鹽。此外,使用具有pH調整劑者(例如各種酸等)作為上述之各種研磨促進劑時,亦可利用該研磨促進劑作為pH調整劑之至少一部份。
研磨用組成物之研磨促進劑含量(濃度)之下限由於即使少量即可發揮效果故未特別限制,但較好為0.001g/L以上,更好為0.01g/L以上,又更好為1g/L以上。隨著含量變多,而進一步提高研磨速度。且,研磨用組成物中之研磨促進劑含量(濃度)之上限較好為200g/L以下,更好為150g/L以下,又更好為100g/L以下。隨著含量變少,而防止鈷之溶解,且提高階差消除性。
本發明之研磨用組成物亦可含金屬防腐蝕劑。藉由於研磨用組成物中添加金屬防腐蝕劑,可抑制金屬之溶解,尤其是藉由防止含銅之層之溶解而抑制研磨表面之表面粗糙等之表面狀態之惡化。
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啶化合物、哌啶化合物、嗒啶化合物、嘧啶化合物、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、呋咱化合物等含氮雜環化合物。
研磨用組成物中之金屬防腐蝕劑含量之下限較好為0.001g/L以上,更好為0.005g/L以上,又更好為0.01g/L以上。隨著金屬防腐蝕劑之含量變多,可防止金屬之溶解,且可提高階差之消除性。此外,研磨用組成物中之金屬防腐蝕劑含量之上限較好為10g/L以下,更好為5g/L以下,又更好為2g/L以下。隨著金屬防腐蝕劑之含量變少,而提高研磨速度。
本發明之研磨用組成物較好含有界面活性劑。界面活性劑可抑制研磨後之研磨表面之凹陷。界面活性劑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種。
陰離子性界面活性劑之具體例包含聚氧伸乙基烷基醚乙酸、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、該等之鹽等。
陽離子性界面活性劑之具體例包含烷基三甲基銨鹽、烷基二甲基銨鹽、烷基苄基二甲基銨鹽、烷基胺鹽等。
兩性界面活性劑之具體例包含烷基甜菜鹼、烷基胺氧化物等。非離子性界面活性劑之具體例包含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、烷基烷醇醯胺等。該等界面活性劑可單獨使用1種,亦可組合2種以上使用。
又上述界面活性劑較好使用以下述式1表示之界面活性劑:
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,惟,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以下式表示之化合物或其鹽:
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。以上述式1表示之界面活性劑包含磷酸骨架,對金屬配線(例如銅、銅合金)具有螯合效果,但若存在聚氧伸烷基芳基醚基,則降低螯合劑能而調整成適度之螯合能。結果,可一方面展現金屬配線之研磨速率,一方面防止金屬配線之凹陷。
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,惟A1~A3中至少一者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,A1~A3中之一者較好為聚氧伸烷基芳基醚基。且,基於界面活性劑在研磨用組成物中之分散性之觀點,A1~A3中之至少一者較好為氫原子。又,基於可一方面維持高研磨速度一方面實現低階差之觀點,A1~A3中,較好一者為具有作為Ar而後述之式3之聚氧伸烷基芳基醚基,其餘為氫原子。又,式1之化合物可為1種,亦可為2種以上。且,亦可併用單酯、二酯、三酯。
上述式1所示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,較好為胺鹽、鉀鹽。此處,胺鹽之具體例列舉為三乙醇胺、三甲醇胺等,基於研磨性能之觀點以三乙醇胺較適當。又,鹽之形態為A1~A3之一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。
上述聚氧伸烷基芳基醚基係以下式表示:
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」中芳基之碳數為碳數6~20,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,可有效發揮本發明期望之效果。此外「Ar」之具體例亦無特別限制,列舉為例如苯基、萘基或蒽基等,尤其若為苯基時,可有效發揮本發明期望之效果。
鑒於上述,前述Ar係以下述式3表示:
式3中,R1~R5各獨立表示氫原子、可經取代或未取代之碳數1~21之烷基、或可經取代或未取代之碳數6~20之芳基。
可經取代或未取代之碳數1~21之烷基中之烷基之碳數基於分散安定性之觀點,較好為1~18,更好為1~10,又更好為1~5,最好為1~3。又,烷基之具體例亦無特別限制,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,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。
又,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,芳基較好為苯基、萘基等,鹵原子以氯、溴、碘等較佳。尤其,若具有芳基作為取代基,則吸附於Cu表面時Cu表面成為撥水性,使研磨粒與錯化劑難以與Cu表面接液,可防止障蔽膜露出後之過度研磨。
又,R1~R5中之經烷基之取代數基於分散安定性之觀點較好為1~3之整數。且R1~R5中之烷基之取代部位亦無特別限制,但基於實現高研磨速度且低階差,且抑制蝕刻之觀點,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。
芳基係由芳香族烴衍生之官能基或取代基。芳基為碳數6~20,但基於分散安定性之觀點,較好為碳數6~14,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之烷基之例同樣適用上述之例。
鑑於上述,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,基於分散安定性之觀點,更好為1~3之整數;且,上述Ar2中,s為1~5之整數,基於分散安定性之觀點,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,基於實現高研磨速度且低階差,且蝕刻抑制效果之觀點,較好為2位、4位、6位。又,s=1時,以2位、3位或4為較佳,基於蝕刻抑制效果之觀點最好為3位。
且,上述式2中「E」中之碳數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期待之效果。又,n為1~100,但基於分散安定性之觀點,較好為4~80之整數,更好為8~50之整數。
鑒於上述,基於有效發揮本發明之期望效果之觀點,較好使用下述式4~6表示之化合物或其鹽之界面活性劑。
尤其,欲提高保存安定性時,若考慮分散安定性,較好使用以式6表示之化合物或其鹽之界面活性劑,且,若考慮兼具研磨性能,則以式4表示之化合物或其鹽之界面活性劑較適當。據此,若於苯基(苯基醚基)上,取代有被苯基取代之乙基或取代有烷基而成時,可有效發揮高的研磨速度與高的蝕刻抑制之效果。
上述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。
上述式1所示之界面活性劑只要是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組合而合成。
研磨用組成物中之界面活性劑之含量下限值較好為0.0001g/L以上,更好為0.001g/L以上。隨著界面活性劑之含量變多,可更減低研磨後之凹陷。且,研磨用組成物中之界面活性劑之含量上限值較好為20g/L以下,更好為10g/L以下。隨著界面活性劑之含量變少,可抑制研磨速度之降低。
可添加於本發明之研磨用組成物中之防腐劑或防黴劑列舉為例如2-甲基-4-異噻唑啉-3-酮或5-氯-2-甲基-4-異噻唑啉-3-酮等異噻唑啉系防腐劑、過氧苯甲酸酯類、及苯氧基乙醇等。該等防腐劑及防黴劑可單獨使用或混合2種以上使用。
本發明之研磨用組成物亦可含有水溶性高分子或其
鹽。藉由水溶性高分子或其鹽可提高研磨用組成物之分散安定性,且因漿液濃度之均勻化而可使研磨用組成物之供給安定化。又,可進一步降低使用研磨用組成物研磨後之研磨對象物表面之粗糙度。
水溶性高分子之具體例列舉為例如聚苯乙烯磺酸鹽、聚異戊二烯磺酸鹽、聚丙烯酸鹽、聚馬來酸、聚衣康酸、聚乙酸乙烯酯、聚乙烯醇、聚丙三醇、聚乙烯基吡咯啶酮、聚異戊二烯磺酸與丙烯酸之共聚物、聚乙烯基吡咯啶酮-聚丙烯酸共聚物、聚乙烯基吡咯啶酮-乙酸乙烯酯共聚物、萘磺酸甲醛縮合物之鹽、二烯丙基胺鹽酸鹽-二氧化硫共聚物、羧基甲基纖維素、羧基甲基纖維素之鹽、羥基乙基纖維素、羥基丙基纖維素、普魯蘭多醣(pullulan)、殼聚糖及殼聚糖鹽類。該等水溶性高分子可單獨使用1種,亦可組合2種以上使用。
研磨用組成物中之水溶性高分子或其鹽之含量下限較好為0.0001g/L以上,更好為0.001g/L以上。隨著水溶性高分子或其鹽之含量變多,可更降低藉研磨用組成物所致之研磨面之表面粗糙度。且,研磨用組成物中之水溶性高分子或其鹽之含量上限較好為10g/L以下,更好為1g/L以下。隨著水溶性高分子或其鹽之含量變少,而降低水溶性高分子或其鹽對研磨面之殘留量,更提高洗淨效率。
本發明之研磨用組成物之製造方法並未特別限制,可藉由例如在水等分散介質或溶劑中攪拌混合氧化劑、鈷溶解抑制劑、及視需要之其他成分而得。
混合各成分時之溫度並無特別限制,較好為10~40℃,亦可加熱以提高溶解速度。又,混合時間亦無特別限制。
如上述,本發明之研磨用組成物較好地使用於具有含銅之層及含鈷之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研磨具有含銅之層與含鈷之層之研磨對象物之研磨方法。為了更有效獲得本發明之效果,較好同時研磨含銅之層與含鈷之層。且,本發明提供包含以上述研磨方法研磨具有含銅之層與含鈷之層之研磨對象物之步驟之基板之製造方法。
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,施加至研磨對象物之壓力(研磨壓力)較好為0.1~10psi。將研磨用組成物供給於研磨墊之方法亦無
特別限制,例如可採用以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,在水流中洗淨研磨對象物,以旋轉乾燥機等甩掉附著於研磨對象物上之水滴予以乾燥,而獲得已研磨之研磨對象物。
使用以下之實施例及比較例更詳細說明本發明。但,本發明之技術範圍並不僅受限於以下之實施例。
以分別成為作為氧化劑之過氧化氫水溶液(濃度:31質量%)30g/L(以過氧化氫計在研磨用組成物中為9.3g/L)、作為鈷溶解抑制劑之下述表1所示之化合物0.1mol/L、及作為研磨促進劑之甘胺酸10g/L之含量在水中攪拌混合(混合溫度:約25℃,混合時間:約10分鐘),調製研磨用組成物。
蝕刻試驗係將加工成30mm四方形尺寸之鈷晶圓於放入500ml燒杯內之研磨用組成物中,邊以300rpm旋轉邊浸漬於液體中3分鐘。將浸漬前後之試片之厚度差除以浸漬時間之值作為對於含鈷之層之蝕刻速率。結果示於下述表1。
如由上述表1可了解,實施例1~9之研磨用組成物對含鈷之層之蝕刻速率相較於比較例1~11之研磨用組成物對含鈷之層之蝕刻速率大幅降低。
以如分別記載之含量之方式在水中攪拌混合(混合溫度:約25℃,混合時間:約10分鐘)作為研磨粒之膠體二氧化矽(平均一次粒徑:10nm,平均二次粒徑:28nm)3g/L、作為氧化劑之過氧化氫10g/L、作為界面活性劑之聚氧伸乙基烷基醚0.5g/L及以上述式4表示之三苯乙烯基苯基醚EO磷酸酯(RHODIA日華股份有限公司製,SOPROPHOR(註冊商標)3D33)0.2g/L、下述表3所示之鈷溶解抑制劑0.1mol/L、作為研磨促進劑之甘胺酸10g/L。進而,使用氫氧化鉀作為pH調整劑,將pH調整成7.0獲得研磨用組成物。所得研磨用組成物之pH係以pH計在25℃下確認。
使用所得研磨用組成物(實施例10~13、比較例12),以下述表2之研磨條件,研磨鈷/銅圖型化晶圓(具有Ta層作為障蔽層)。
研磨速度係使用以直流4碳針法為原理之薄片電阻測定器測定之研磨前後之鈷/銅圖型化晶圓中含銅之層及含
鈷之層之各自厚度之差除以研磨時間而求出。結果示於下述表3。
以上述表2所記載之研磨條件研磨具有各種大小之線與空間(L/S)之基板(具有障蔽層之鈷/銅圖型晶圓)直至障蔽層露出為止,以原子力顯微鏡(AFM)測定含鈷之層之表面之剖面地形。
以掃描型電子顯微鏡觀察使用實施例10~13及比較例12之研磨用組成物研磨鈷/銅圖形化晶圓後之圖型之剖面。
研磨速度、地形及含鈷之層之凹陷之觀察結果示於下述表3。
如由上述表3所了解,可知使用實施例10~13之研磨用組成物時,含銅之層之研磨速度較高,含鈷之層之研磨速度較低。且,可知含鈷之層之階差受抑制。
使用實施例10~13之研磨用組成物時,未觀察到含鈷之層之凹陷,但使用比較例12之研磨用組成物時,觀察到含鈷之層之凹陷。圖1係顯示使用實施例10之研磨用組成物,圖2係顯示使用比較例12之研磨用組成物,研磨鈷/銅圖型化晶圓後之圖型之剖面的SEM(掃描型電子顯微鏡)照片。圖1及圖2中,黑色部分1為障蔽層(Ta層),以虛線包圍之部分2為含銅之層,部分1與部分2之界面有含鈷之層。圖1中,幾乎未見到含銅之層(部分2)及含鈷之層(部分1與部分2之界面)之溶解,但圖2中,由於以存在於部分2與部分1之界面之含鈷之層為中心引起溶解,故可知與部分2及部分1之界面之含鈷之層鄰接之含銅之層(部分2)之溶解進展。
又,本申請案係基於2014年9月8號申請之日本專利申請案第2014-182583號,其揭示內容藉由參考整體加以援用。
Claims (9)
- 一種研磨用組成物,其係研磨具有含銅之層與含鈷之層之研磨對象物之用途中使用之研磨用組成物,且含有氧化劑、與由具有含氮5員環構造之化合物及具有2個以上羧基之胺基羧酸所組成之群選出之至少一種之鈷溶解抑制劑。
- 如請求項1之研磨用組成物,其中前述具有含氮5員環構造之化合物係由1H-苯并三唑、5-甲基-1H-苯并三唑、1H-咪唑及1H-四唑所組成之群選出之至少一種。
- 如請求項1之研磨用組成物,其中前述胺基羧酸係由二伸乙基三胺五乙酸、三伸乙基四胺-N,N,N”,N”,N’”,N’”-六乙酸、氮基三乙酸、N-(2-羥基乙基)亞胺基二乙酸及N-(2-羥基乙基)乙二胺-N,N’,N’-三乙酸所組成之群選出之至少一種。
- 如請求項1~3中任一項之研磨用組成物,其進而含有研磨促進劑。
- 如請求項1~4中任一項之研磨用組成物,其進而含有界面活性劑。
- 一種研磨用組成物之製造方法,其包合使氧化劑、與由具有含氮5員環構造之化合物及具有2個以上羧基之胺基羧酸所組成之群選出之至少一種鈷溶解抑制劑混合。
- 一種研磨方法,其係研磨具有含銅之層與含鈷之層之研磨對象物之方法,且包含使用如請求項1~5中任一項之研磨用組成物,或以如 請求項6之製造方法獲得之研磨用組成物,同時研磨前述含銅之層與前述含鈷之層。
- 一種基板之製造方法,其包含以如請求項7之研磨方法研磨具有含銅之層與含鈷之層之研磨對象物之步驟。
- 一種基板,其係以如請求項8之製造方法獲得。
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JP2006282755A (ja) * | 2005-03-31 | 2006-10-19 | Dainippon Ink & Chem Inc | 有機無機ハイブリッド粒子水性分散体及びそれから得られる研磨スラリー |
JP2007081316A (ja) * | 2005-09-16 | 2007-03-29 | Fujifilm Corp | 金属用研磨液、及び、化学機械的研磨方法 |
JP2009087968A (ja) * | 2007-09-27 | 2009-04-23 | Fujifilm Corp | 金属用研磨液、及び化学的機械的研磨方法 |
JP2011003665A (ja) * | 2009-06-17 | 2011-01-06 | Jsr Corp | 化学機械研磨用水系分散体およびそれを用いた化学機械研磨方法 |
CN102304327A (zh) * | 2011-07-05 | 2012-01-04 | 复旦大学 | 一种基于金属Co的抛光工艺的抛光液 |
US20130018838A1 (en) * | 2011-07-14 | 2013-01-17 | Parnaby Tracey J | System and Method for Social Influence Credentialing within a Sentiment Sharing Community |
JP6051632B2 (ja) * | 2011-07-20 | 2016-12-27 | 日立化成株式会社 | 研磨剤及び基板の研磨方法 |
US20130186850A1 (en) * | 2012-01-24 | 2013-07-25 | Applied Materials, Inc. | Slurry for cobalt applications |
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KR102226501B1 (ko) * | 2013-02-21 | 2021-03-11 | 가부시키가이샤 후지미인코퍼레이티드 | 연마용 조성물 및 연마물 제조 방법 |
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2014
- 2014-09-08 JP JP2014182583A patent/JP2016056254A/ja active Pending
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2015
- 2015-07-02 US US15/505,672 patent/US20180215952A1/en not_active Abandoned
- 2015-07-02 CN CN201580046678.6A patent/CN106661432A/zh active Pending
- 2015-07-02 KR KR1020177004599A patent/KR20170052570A/ko unknown
- 2015-07-02 WO PCT/JP2015/069198 patent/WO2016038995A1/ja active Application Filing
- 2015-07-08 TW TW104122154A patent/TW201610046A/zh unknown
Cited By (2)
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TWI648359B (zh) * | 2016-06-16 | 2019-01-21 | 慧盛材料美國責任有限公司 | 含鈷基材的化學機械研磨 |
US10745589B2 (en) | 2016-06-16 | 2020-08-18 | Versum Materials Us, Llc | Chemical mechanical polishing (CMP) of cobalt-containing substrate |
Also Published As
Publication number | Publication date |
---|---|
JP2016056254A (ja) | 2016-04-21 |
KR20170052570A (ko) | 2017-05-12 |
CN106661432A (zh) | 2017-05-10 |
US20180215952A1 (en) | 2018-08-02 |
WO2016038995A1 (ja) | 2016-03-17 |
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