US20030013386A1 - Chemical mechanical polishing compositions and methods relating thereto - Google Patents
Chemical mechanical polishing compositions and methods relating thereto Download PDFInfo
- Publication number
- US20030013386A1 US20030013386A1 US10/150,211 US15021102A US2003013386A1 US 20030013386 A1 US20030013386 A1 US 20030013386A1 US 15021102 A US15021102 A US 15021102A US 2003013386 A1 US2003013386 A1 US 2003013386A1
- Authority
- US
- United States
- Prior art keywords
- polishing composition
- weight
- copolymer
- composition
- accordance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 114
- 238000005498 polishing Methods 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims description 17
- 239000000126 substance Substances 0.000 title description 2
- 229920001577 copolymer Polymers 0.000 claims abstract description 90
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- 125000000524 functional group Chemical group 0.000 claims abstract description 30
- 239000003112 inhibitor Substances 0.000 claims abstract description 20
- 239000008139 complexing agent Substances 0.000 claims abstract description 12
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims description 81
- -1 aromatic triazole Chemical class 0.000 claims description 32
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 21
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 239000004065 semiconductor Substances 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical group OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- 229920005603 alternating copolymer Polymers 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 4
- 229920005605 branched copolymer Polymers 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- 229920005604 random copolymer Polymers 0.000 claims description 4
- 238000005389 semiconductor device fabrication Methods 0.000 claims 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 15
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 15
- 239000004094 surface-active agent Substances 0.000 description 8
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 7
- 239000012964 benzotriazole Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 206010042618 Surgical procedure repeated Diseases 0.000 description 4
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 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
- 239000000839 emulsion Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 3
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- ATZHWSYYKQKSSY-UHFFFAOYSA-N tetradecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C(C)=C ATZHWSYYKQKSSY-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 101100107923 Vitis labrusca AMAT gene Proteins 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical class [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])* 0.000 description 2
- 235000010350 erythorbic acid Nutrition 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- JEBMFONDEFPKAD-UHFFFAOYSA-N heptacosan-13-yl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCC(OC(=O)C(C)=C)CCCCCCCCCCCC JEBMFONDEFPKAD-UHFFFAOYSA-N 0.000 description 2
- HJSMBDKULYJQKM-UHFFFAOYSA-N hexacosan-13-yl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCC(OC(=O)C(C)=C)CCCCCCCCCCCC HJSMBDKULYJQKM-UHFFFAOYSA-N 0.000 description 2
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 description 2
- CFBXDFZIDLWOSO-UHFFFAOYSA-N icosyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCCCOC(=O)C(C)=C CFBXDFZIDLWOSO-UHFFFAOYSA-N 0.000 description 2
- 229940026239 isoascorbic acid Drugs 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 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 2
- YOTGRUGZMVCBLS-UHFFFAOYSA-N pentadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCOC(=O)C(C)=C YOTGRUGZMVCBLS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- 229940001584 sodium metabisulfite Drugs 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 1
- HLOUDBQOEJSUPI-UHFFFAOYSA-N 1-ethenyl-2,3-dimethylbenzene Chemical class CC1=CC=CC(C=C)=C1C HLOUDBQOEJSUPI-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- BDHGFCVQWMDIQX-UHFFFAOYSA-N 1-ethenyl-2-methylimidazole Chemical compound CC1=NC=CN1C=C BDHGFCVQWMDIQX-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- UXYMHGCNVRUGNO-UHFFFAOYSA-N 1-hydroxypropan-2-yl prop-2-enoate Chemical compound OCC(C)OC(=O)C=C UXYMHGCNVRUGNO-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 1
- SXZSFWHOSHAKMN-UHFFFAOYSA-N 2,3,4,4',5-Pentachlorobiphenyl Chemical compound C1=CC(Cl)=CC=C1C1=CC(Cl)=C(Cl)C(Cl)=C1Cl SXZSFWHOSHAKMN-UHFFFAOYSA-N 0.000 description 1
- PQDKOKTULASSPO-UHFFFAOYSA-N 2-(1,3-oxazolidin-2-yl)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1NCCO1 PQDKOKTULASSPO-UHFFFAOYSA-N 0.000 description 1
- WMEHNYPPAXVRAU-UHFFFAOYSA-N 2-(1,3-oxazolidin-2-yl)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCC1NCCO1 WMEHNYPPAXVRAU-UHFFFAOYSA-N 0.000 description 1
- XEXAZMUXZYILPC-UHFFFAOYSA-N 2-(2-aminoethoxy)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCN XEXAZMUXZYILPC-UHFFFAOYSA-N 0.000 description 1
- XJEJWEGBNZTQCR-UHFFFAOYSA-N 2-(2-methyl-2-propyl-1,3-oxazolidin-3-yl)ethyl 2-methylprop-2-enoate Chemical compound CCCC1(C)OCCN1CCOC(=O)C(C)=C XJEJWEGBNZTQCR-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- JFYPYUCFINOOIR-UHFFFAOYSA-N 2-[2-(1,3-oxazolidin-3-yl)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCN1CCOC1 JFYPYUCFINOOIR-UHFFFAOYSA-N 0.000 description 1
- HGSFRDZJSRAGOF-UHFFFAOYSA-N 2-[2-(1,3-oxazolidin-3-yl)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCN1CCOC1 HGSFRDZJSRAGOF-UHFFFAOYSA-N 0.000 description 1
- OSJKZFBLZVKMPX-UHFFFAOYSA-N 2-[2-(2,2-dimethyl-1,3-oxazolidin-3-yl)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCN1CCOC1(C)C OSJKZFBLZVKMPX-UHFFFAOYSA-N 0.000 description 1
- JZZMADAWOOJCMS-UHFFFAOYSA-N 2-[2-(2-phenyl-1,3-oxazolidin-3-yl)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCN1CCOC1C1=CC=CC=C1 JZZMADAWOOJCMS-UHFFFAOYSA-N 0.000 description 1
- ZECBHOZDFMSBFY-UHFFFAOYSA-N 2-[2-(5-methyl-1,3-oxazolidin-3-yl)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC1CN(CCOCCOC(=O)C(C)=C)CO1 ZECBHOZDFMSBFY-UHFFFAOYSA-N 0.000 description 1
- YESFFMFOQBIWMM-UHFFFAOYSA-N 2-[2-(5-methyl-1,3-oxazolidin-3-yl)ethoxy]ethyl prop-2-enoate Chemical compound CC1CN(CCOCCOC(=O)C=C)CO1 YESFFMFOQBIWMM-UHFFFAOYSA-N 0.000 description 1
- UGIJCMNGQCUTPI-UHFFFAOYSA-N 2-aminoethyl prop-2-enoate Chemical compound NCCOC(=O)C=C UGIJCMNGQCUTPI-UHFFFAOYSA-N 0.000 description 1
- HDEFKPTUGHCBCD-UHFFFAOYSA-N 2-ethenoxy-n-methylethanamine Chemical compound CNCCOC=C HDEFKPTUGHCBCD-UHFFFAOYSA-N 0.000 description 1
- CEYHHQSTMVVZQP-UHFFFAOYSA-N 2-ethenoxyethanamine Chemical compound NCCOC=C CEYHHQSTMVVZQP-UHFFFAOYSA-N 0.000 description 1
- JEIWZOOQUZYRFS-UHFFFAOYSA-N 2-ethenylsulfanylethanamine Chemical compound NCCSC=C JEIWZOOQUZYRFS-UHFFFAOYSA-N 0.000 description 1
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- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 125000004079 stearyl 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])C([H])([H])C([H])([H])[H] 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
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- OIUCPPFBFOLPIO-UHFFFAOYSA-N tetratriacontyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCOC(=O)C(C)=C OIUCPPFBFOLPIO-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical class [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
- KRLHYNPADOCLAJ-UHFFFAOYSA-N undecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCOC(=O)C(C)=C KRLHYNPADOCLAJ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000000080 wetting agent Substances 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
-
- 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
-
- 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
-
- 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
- B24B37/11—Lapping tools
- B24B37/20—Lapping pads for working plane surfaces
- B24B37/24—Lapping pads for working plane surfaces characterised by the composition or properties of the pad materials
-
- 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]
Definitions
- the invention relates to chemical mechanical polishing (CMP) of a semiconductor substrate.
- CMP refers to removal and planarization of thin films or layers on a semiconductor substrate, which form integrated circuits, multi-chip modules, capacitors and the like.
- the films or layers are classified according to three different materials: (i) a conductive metal layer; (ii) a barrier film or liner film between the conductive metal layer and an underlying dielectric layer; and (iii) an underlying dielectric layer having recessed metal lines that form metal circuit interconnects.
- a polishing pad in combination with a fluid polishing composition removes a layer of metal, and polishes the semiconductor substrate with a smooth planar polished surface on which are manufactured successive layers. The successive layers themselves are polished by CMP.
- the polishing composition comprises, a slurry having abrasive particles or a slurry, referred to as a reactive liquid, that comprises a substantially particle-free polishing composition.
- a reactive liquid that comprises a substantially particle-free polishing composition.
- the polishing pad undergoes motion relative to the semiconductor substrate, and applies friction to the substrate. The friction is combined with chemical reaction of the polishing composition with the surface of the substrate to remove material from the semiconductor substrate.
- Dishing refers to unwanted cavities that are caused by removal of metal from the circuit interconnects, during a CMP process.
- Erosion refers to excessive removal of dielectric material surrounding the circuit interconnects, during a CMP process.
- U.S. Pat. No. 6,117,775 discloses an inhibitor and a surfactant that suppress removal by etching and oxidation of circuit interconnects during CMP, while the inhibitor and surfactant adheres to a metal that is being removed by CMP.
- the inhibitor and surfactant are removed by friction applied by a polishing pad.
- the inhibitor comprises BTA
- the surfactant comprises, one of; polyacrylic acid, polyammoniumacrylate, polymethacrylic acid and polyammoniumacrylate.
- the invention is directed to an engineered copolymer for suppressing dishing during CMP of a semiconductor substrate, wherein the engineered copolymer comprises, molecules of a first moiety having one or more hydrophilic functional groups forming bonds with the metal on the substrate surface, and molecules of a second moiety having one or more hydrophobic functional groups that engage the polishing pad during CMP for the pad to remove the engineered copolymer from the surface of the metal being polished, which enables removal of the metal by CMP, while minimizing removal of the engineering copolymer from the recessed circuit interconnects to minimize dishing.
- the engineered copolymer is derived from one or more monomers forming molecules of a first moiety having one or more hydrophilic functional groups forming bonds with the metal on the substrate surface, and forming molecules of a second moiety having one or more hydrophobic functional groups that engage the polishing pad during CMP for the pad to remove the engineered copolymer from the surface of the metal being polished, which enables removal of the metal by CMP, while minimizing removal of the engineering copolymer from the recessed circuit interconnects to minimize dishing.
- Hydrophilic functional groups are ionizable functional groups.
- Hydrophobic functional groups are non-ionizable functional groups.
- the engineered copolymer enhances removal of metal from a substrate, while minimizing dishing of recessed metal circuit interconnects through controlled contact-mediated reactions with the substrate surface and the polishing pad surface.
- the engineered copolymer is derived from one or more monomers to provide hydrophilic functional groups that readily form strong bonds, e.g. coordinate covalent bonds, with the substrate surface during CMP. Further, the engineered copolymer is derived from one or more monomers to provide hydrophobic functional groups that provide structural rigidity to the copolymer molecules by van der Waals forces or other interactions. The rigidity of the engineered copolymer is adjusted by varying the mole ratios of the monomers forming the functional groups. When two monomers are utilized to derive or synthesize the engineering copolymer, the mole ratio of each monomer can be varied from about 1:20 to about 20:1.
- the total of all mole ratios is 1.
- one monomer is polyethylenically unsaturated and serves as the extending agent or crosslinking agent in the copolymer.
- the molecules of the first moiety comprises, hydrophilic functional groups of one or more of; carboxyl, hydroxyl, halogen, phosphonate, phosphate, sulfonate, sulfate, nitro and the like, to form bonds with the metal being removed by CMP.
- At least one or more engineered copolymers are present up to about 1% by weight in a reactive liquid.
- the reactive liquid is a particle-free polishing composition that comprises, (i) up to about 15% by weight of an oxidizing agent; (ii) up to about 2% by weight of a corrosion inhibitor; and (iii) up to about 3% by weight of a complexing agent forming complex metal ions in the reactive liquid.
- the reactive liquid comprises, a pH under about 5.0, alternatively, a pH in a range of about 2.8 to about 4.2, and alternatively, a pH in a range of about 2.8 to about 3.8.
- At least one or more engineered copolymers are present up to about 1% by weight in a polishing composition having abrasive particles.
- the composition comprises, (i) up to about 15% by weight of an oxidizing agent; (ii) up to about 2% by weight of a corrosion inhibitor; (iii) up to about 3% by weight of a complexing agent, and (iv) up to about 3% by weight of abrasive particles.
- the composition comprises, a pH under about 5.0, alternatively, a pH in a range of about 2.8 to about 4.2, and alternatively, a pH in a range of about 2.8 to about 3.8.
- the engineered copolymer is derived from a mixture of monomers, for example, an acrylic acid monomer and methacrylic acid monomer, combined at a mole ratio in a range of about 1:20 to about 20:1, and alternatively in a range of about 1:1.
- the engineered copolymer is derived from a mixture of monomers, for example, a mixture of, two or more, ethylenically unsaturated monomers, said mixture containing at least about 50% by weight of an unsaturated carboxylic acid monomer to form branched and/or unbranched copolymer molecules.
- the unsaturated carboxylic acid monomer comprises, either an unsaturated monocarboxylic acid monomer or an unsaturated dicarboxylic acid monomer.
- An unsaturated monocarboxylic acid monomer refers to one of unsaturated carboxylic acid monomers containing 3 to 6 carbon atoms per molecule with a single carboxylic acid group and water-soluble salts thereof.
- Suitable ethylenically unsaturated monocarboxylic acid monomers are, for example, acrylic acid, oligomeric acrylic acid, methacrylic acid, crotonic acid, vinylacetic acid and derivatives thereof such as corresponding anhydrides, amides, esters and water-soluble salts thereof.
- An unsaturated dicarboxylic acid monomer refers to one of unsaturated dicarboxylic acid monomers containing 4 to 8 carbon atoms per molecule, anhydrides of the cis-and trans-dicarboxylic acids, and water-soluble salts thereof.
- Suitable unsaturated dicarboxylic acid monomers comprrse, for example, maleic acid, fumaric acid, alpha-methylene glutaric acid, itaconic acid, citraconic acid, mesaconic acid, cyclohexenedicarboxylic acid, and derivatives such as corresponding anhydrides, amides, esters and water-soluble salts thereof.
- the engineered copolymer is derived from one or more of monoethylenically unsaturated monomers, such as, vinylaromatic monomers comprising, for example, styrene, ⁇ -methylstyrene, vinyltoluene, ortho-, meta- and para-methylstyrene, ethylvinylbenzene, vinylnaphthalene and vinylxylenes.
- monoethylenically unsaturated monomers such as, vinylaromatic monomers comprising, for example, styrene, ⁇ -methylstyrene, vinyltoluene, ortho-, meta- and para-methylstyrene, ethylvinylbenzene, vinylnaphthalene and vinylxylenes.
- the vinylaromatic monomer includes a corresponding substituted counterpart, for example, one of halogenated derivatives, containing one or more halogen groups, such as fluorine, chlorine or bromine; and nitro, or, for example, derivatives of, cyano, alkoxy, haloalkyl, carbalkoxy, carboxy, amino and alkylamino.
- halogenated derivatives such as fluorine, chlorine or bromine
- nitro or, for example, derivatives of, cyano, alkoxy, haloalkyl, carbalkoxy, carboxy, amino and alkylamino.
- the engineered copolymer is derived from one or more of monoethylenically unsaturated monomers comprising, for example, nitrogen-containing ring compounds, for example, vinylpyridine, 2-methyl-5-vinylpyridine, 2-ethyl-5-vinylpyridine, 3-methyl-5-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, 2-methyl-3-ethyl-5-vinylpyridine, methyl-substituted quinolines and isoquinolines, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylcaprolactam, N-vinylbutyrolactam and N-vinylpyrrolidone.
- nitrogen-containing ring compounds for example, vinylpyridine, 2-methyl-5-vinylpyridine, 2-ethyl-5-vinylpyridine, 3-methyl-5-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, 2-methyl-3-ethyl-5-viny
- Monoethylenically unsaturated monomers also comprise ethylene and substituted ethylene monomers, for example: ⁇ -olefins such as propylene, isobutylene and long chain alkyl ⁇ -olefins (such as (C 10 -C 20 )alkyl ⁇ -olefins); vinyl alcohol esters such as vinyl acetate and vinyl stearate; vinyl halides such as vinyl chloride, vinyl fluoride, vinyl bromide, vinylidene chloride, vinylidene fluoride and vinylidene bromide; vinyl nitriles such as acrylonitrile and methacrylonitrile.
- ⁇ -olefins such as propylene, isobutylene and long chain alkyl ⁇ -olefins (such as (C 10 -C 20 )alkyl ⁇ -olefins)
- vinyl alcohol esters such as vinyl acetate and vinyl stearate
- vinyl halides such as vinyl chloride,
- the engineered copolymer is derived from the polymerization of one of acrylic monomers and one of alkyl methacrylate monomers.
- alkyl methacrylate monomer wherein the alkyl group contains from 1 to 6 carbon atoms also called the “low-cut” alkyl methacrylates
- MMA methyl methacrylate
- BMA butyl methacrylate
- BA butyl acrylate
- IBMA isobutyl methacrylate
- hexyl and cyclohexyl methacrylate cyclohexyl acrylate and combinations thereof.
- alkyl methacrylate monomer wherein the alkyl group contains from 7 to 15 carbon atoms are 2-ethylhexyl acrylate (EHA), 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, isodecyl methacrylate (IDMA, based on branched (C 10 )alkyl isomer mixture), undecyl methacrylate, dodecyl methacrylate (also known as lauryl methacrylate), tridecyl methacrylate, tetradecyl methacrylate (also known as myristyl methacrylate), pentadecyl methacrylate and combinations thereof.
- EHA 2-ethylhexyl acrylate
- IDMA isodecyl methacrylate
- IDMA isodecyl methacrylate
- undecyl methacrylate dodecyl methacrylate
- dodecyl-pentadecyl methacrylate DPMA
- DPMA dodecyl-pentadecyl methacrylate
- LMA lauryl-myristyl methacrylate
- alkyl methacrylate monomers wherein the alkyl group contains from 16 to 24 carbon atoms are hexadecyl methacrylate (also known as cetyl methacrylate), heptadecyl methacrylate, octadecyl methacrylate (also known as stearyl methacrylate), nonadecyl methacrylate, eicosyl methacrylate, behenyl methacrylate and combinations thereof.
- cetyl-eicosyl methacrylate (CEMA), a mixture of hexadecyl, octadecyl, and eicosyl methacrylate
- cetyl-stearyl methacrylate (SMA), a mixture of hexadecyl and octadecyl methacrylate.
- the engineered copolymer is derived from one or more of, alkyl methacrylate monomers and acrylate monomers with a dialkylamino group in the alkyl radical, such as dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate; dialkylaminoalkyl methacrylamide and acrylamide monomers, such as N,N-dimethylaminoethyl methacrylamide, N,N-dimethylaminopropyl methacrylamide, N,N-dimethylaminobutyl methacryl-amide, N,N-diethylaminoethyl methacrylamide, N,N-diethylaminopropyl methacrylamide and N,N-diethylaminobutyl methacrylamide.
- alkyl methacrylate monomers and acrylate monomers with a dialkylamino group in the alkyl radical such as dimethylaminoethyl methacryl
- Hydroxyalkyl methacrylate and acrylate monomers have a substituted alkyl group (C 2 -C 6 )alkyl, branched or unbranched Hydroxy-alkyl methacrylate and acrylate monomers comprise, 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 1-methyl-2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 1-methyl-2-hydroxyethyl acrylate, 2-hydroxybutyl methacrylate and 2-hydroxybutyl acrylate.
- HEMA 2-hydroxyethyl methacrylate
- a mixture of 1-methyl-2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate is known as “
- the engineered copolymer is derived from one or more of, amine-containing monomers comprising, for example, amide monomers, such as, dialkylaminoalkyl acrylamides or methacrylamides (for example, dimethylaminopropyl methacrylamide), N,N-bis-(dimethylaminoalkyl) acrylamides or methacrylamides, N- ⁇ -aminoethyl acrylamide or methacrylamide, N-(methylamino-ethyl)acrylamide or methacrylamide, aminoalkylpyrazine acrylamides or methacrylamides; acrylic ester monomers such as dialkylaminoalkyl acrylates or methacrylates (for example, dimethylaminoethyl acrylate or methacrylate), ⁇ -aminoethyl acrylate or methacrylate, N-(n-butyl)-4-aminobutyl acrylate or methacrylate;
- the engineered copolymer is derived from one or more of, monomers with an unsaturated sulfonic acid monomer selected from one or more of 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-pro-panesulfonic acid, 3-methacrylamido-2-hydroxy-1-propanesulfonic acid, allylsulfonic acid, allyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate and water-soluble salts thereof.
- an engineered copolymer is derived from acrylic acid monomer and methacrylic acid monomer combined at a mole ratio in a range of
- an engineered copolymer is derived from polymerization of one or more of, monomers selected from the aforementioned classes of monomers, including, random copolymers, branched copolymers, block copolymers and alternating copolymers.
- the engineered copolymer is used in a polishing composition for CMP together with a commercially available polishing pad, for example, a polishing pad described in U.S. Pat. No. 5,489,233 and U.S. Pat. No. 5,932,486 and U.S. Pat. No. 5,932,486.
- Removal of material, e.g., copper, from a substrate surface during CMP utilizes a polishing composition containing, a metal oxidizing agent, a corrosion inhibitor, e.g., benzotriazole, BTA, and molecules of an engineered copolymer derived from monomers having hydrophilic functional groups and hydrophobic functional groups.
- a corrosion inhibitor e.g., benzotriazole, BTA
- the metal surface comprises hydrated metal atoms and hydrated metal atom-corrosion inhibitor molecular complexes.
- a surface of an exemplary copper layer on a substrate has hydrated copper atoms and hydrated copper atom-BTA complexes.
- the hydrophilic functional groups form strong bonds, e.g., coordinate covalent bonds.
- the hydrophobic functional groups form strong van der Waals bonds with known nanoasperities on the polishing pad surface.
- An oxidizing agent used in a polishing composition for CMP includes, but is not limited to, peroxides such as hydrogen peroxide, iodates such as potassium iodate, nitrates such as cesium nitrate, barium nitrate, ammonium nitrate, and/or mixtures of ammonium nitrate and cesium nitrate, carbonates such as ammonium carbonate, and persulfates such as ammonium persulfate and/or sodium persulfate and perchlorates.
- peroxides such as hydrogen peroxide
- iodates such as potassium iodate
- nitrates such as cesium nitrate, barium nitrate, ammonium nitrate, and/or mixtures of ammonium nitrate and cesium nitrate
- carbonates such as ammonium carbonate
- persulfates such as ammonium persulfate and/or sodium persulfate and per
- a complexing agent includes a carboxylic acid containing two or more carboxylate groups with hydroxy groups.
- a complexing agent includes, but is not limited to, straight chain mono-and dicarboxylic acids and their corresponding salts such as malic acid and malates; tartaric acid and tartarates; gluconic acid and gluconates; citric acid and citrates; malonic acid and malonates; formic acid and formates; lactic acid and lactates; phthalic acid and phthalates; and polyhydroxybenzoic acid and its salts. can also be used in the polishing composition.
- Corrosion inhibitors used in polishing compositions for CMP include BTA (benzotriazole) and TTA (tolyltriazole) or mixtures thereof.
- Other inhibitors that are suitable for use include: 1-hydroxybenzotriazole,N-(1H-benzotriazole-1-ylmethyl)formamide; 3,5-dimethylpyrazole; indazole; 4-bromopyrazole; 3-amino-5-phenylpyrazole; 3-amino-4-pyrazolecarbonitrile; 1-methyimidazole; Indolin QTS and the like.
- a polishing composition for CMP is substantially particle-free or, alternatively, contains abrasive particles of a material that includes, but is not limited to, alumina, silica, ceria, germania, diamond, silicon carbide, titania, zirconia and various mixtures thereof.
- the polishing composition of the invention does not contain any abrasive particles.
- the polishing composition contains low levels of abrasives in a range from about 0 to about 3%, with an average particle diameter less than 50 nm.
- the weight % of abrasive can be up to about 50%.
- a polishing composition for CMP may contain pH buffers such as amines, and may contain surfactants, deflocculants, viscosity modifiers, wetting agents, cleaning agents and the like.
- Engineered copolymers I and II were derived or synthesized as described below. All molecular weights were determined utilizing GPC analysis according to the following procedure. Molecular weight Determination: Samples were dissolved in 0.02M sodium dihydrogen phosphate at pH 7 at a concentration of approximately 0.1% w/v and shaken for 10 minutes, followed by filtration through a 0.45 micron PTFE polytetrafluoroethylene membrane filter.
- the analysis was performed by injecting 100 microliters of this solution into a 2-column set consisting of a TosoHaas TSKgel GMPWx1 and a TosoHaas TSKgel G2500PWx1 and a TosoHaas TSKgel G2500 Wx1 30 cm ⁇ 8 mm column, held at 40 C.
- the mobile phase used was this solution at a flow rate of 1 ml/min. Detection was via a differential refractive index measurement. The system was calibrated with narrow poly(acrylic) acid standards.
- the aqueous copolymer solution at pH 3.8 had a solids content of 24.3%, 548 ppm, parts per million, of acrylic acid, no detectable methacrylic acid and a molecular weight (MW) of 178,700 with a corresponding mole ratio.
- the aqueous copolymer solution at pH 3.6 had a solids content of 24.3%, 426 ppm of acrylic acid, no detectable methacrylic acid and a MW of 28,800 with a corresponding mole ratio.
- aqueous copolymer solution at pH 3.6 had a solids content of 26.8%, no detectable methacrylic acid or acrylic acid and a molecular weight (Mw) of 29,600 with a corresponding mole ratio.
- glacial acrylic acid were added separately and linearly over 120 min. After addition, the solution was held at temperature for 30 min., and then cooled to 70° C. Next, 20.20 g. of 50% sodium hydroxide was added, dropwise.
- the aqueous copolymer solution at pH 3.8 had a solids content of 29.8%, no detectable methacrylic acid or acrylic acid and a molecular weight (Mw) of 19,500 with a corresponding mole ratio.
- Each of the engineered copolymers I, II, IIA and IIB was combined with a polishing composition, which was used in CMP to polish respective copper patterned wafers on an AMAT Mirra polishing machine. Polishing by CMP was performed under the following conditions: First step at 5 psi down force, 93 rpm platen speed and 87 rpm carrier speed for 60 seconds; Second step at 3 psi down force, 93 rpm platen speed, 87 rpm carrier speed for 60 seconds. The first step of polishing was performed until endpoint was achieved on the AMAT Mirra as determined by the Mirra endpoint detection system. The second polishing step was terminated when the endpoint curve slope was zero.
- All polishing compositions contained 9% hydrogen peroxide, 0.3% BTA and 0.22% malic acid.
- Control contained 0.18% of a 1:1 mixture of polyacrylic acids with number average molecular weights of 250,000 and 30,000, respectively.
- Polishing compositions A1 and A2 contained 0.36% of active engineered copolymer I.
- Polishing compositions B1 and B2 contained 0.36% of active engineered copolymer II.
- Polishing composition C1 contained 0.18% of active engineered copolymer IIB and Polishing composition D1 contained 0.18% of active engineered copolymer IIA.
- the remaining weight percentage of each polishing composition comprised water.
- Engineered copolymers III, IV and V were synthesized as described below.
- the aqueous copolymer solution at pH 6.2 had a solids content of 25.9%, 1450 ppm methacrylic acid and a MW of 20,100 with a corresponding mole ratio.
- the aqueous copolymer solution at pH 5.9 had a solids content of 34.0%, 397 ppm methacrylic acid and a MW of 14,100 with a corresponding mole ratio.
- the emulsion polymer at pH 2.8 had a solids content of 31.4%, 331 ppm of methacrylic acid, 171 ppm of methyl methacrylate, a MW of 56,400 with a corresponding mole ratio, and a particle size of 105 nm.
- Table 2 summarizes removal rate data obtained, according to the method of the invention, utilizing polishing compositions containing engineered copolymers III, IV and V. All polishing compositions contained 0.36% of the respective engineered copolymer, 9% hydrogen peroxide, 0.3% BTA, and 0.22% malic acid. The remaining weight percentage of each polishing composition comprised water. TABLE 2 Engineered Molecular Removal Rate Copolymer Weight (MW) (Angstroms/minute) III 20,100 1,500 IV 14,100 3,000 V 56,400 ⁇ 1,000
- the data in Table 2 illustrate that removal rates in excess of 1,000 Angstroms per minute are obtained utilizing the invention.
- the exemplified polishing compositions respectively comprised engineered copolymers made from a mixture of monomers, wherein the mixture has greater than 50 mole % of acid-containing monomers.
- a polishing composition for CMP is provided with an engineered copolymer comprising, molecules of a first moiety having one or more hydrophilic functional groups forming bonds with the metal on the substrate surface, and further comprising, molecules of a second moiety having one or more hydrophobic functional groups that engage the polishing pad during CMP for the pad to remove the engineered copolymer from the surface of the metal being polished, which enables removal of the metal by CMP, while minimizing removal of the engineering copolymer from the recessed circuit interconnects to minimize dishing.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
A polishing composition for removing metal by CMP comprises, a metal oxidizer, an oxide inhibitor, a complexing agent, and an engineered copolymer comprising, molecules of a first moiety having hydrophilic functional groups forming bonds with the metal, and molecules of a second moiety having hydrophobic functional groups.
Description
- This application is a continuation in part of application Ser. No. 09/860,933, filed May 18, 2001.
- The invention relates to chemical mechanical polishing (CMP) of a semiconductor substrate.
- CMP refers to removal and planarization of thin films or layers on a semiconductor substrate, which form integrated circuits, multi-chip modules, capacitors and the like. The films or layers are classified according to three different materials: (i) a conductive metal layer; (ii) a barrier film or liner film between the conductive metal layer and an underlying dielectric layer; and (iii) an underlying dielectric layer having recessed metal lines that form metal circuit interconnects. During a CMP process, a polishing pad in combination with a fluid polishing composition removes a layer of metal, and polishes the semiconductor substrate with a smooth planar polished surface on which are manufactured successive layers. The successive layers themselves are polished by CMP.
- The polishing composition comprises, a slurry having abrasive particles or a slurry, referred to as a reactive liquid, that comprises a substantially particle-free polishing composition. During CMP, the polishing pad undergoes motion relative to the semiconductor substrate, and applies friction to the substrate. The friction is combined with chemical reaction of the polishing composition with the surface of the substrate to remove material from the semiconductor substrate. Dishing refers to unwanted cavities that are caused by removal of metal from the circuit interconnects, during a CMP process. Erosion refers to excessive removal of dielectric material surrounding the circuit interconnects, during a CMP process.
- U.S. Pat. No. 6,117,775 discloses an inhibitor and a surfactant that suppress removal by etching and oxidation of circuit interconnects during CMP, while the inhibitor and surfactant adheres to a metal that is being removed by CMP. The inhibitor and surfactant are removed by friction applied by a polishing pad. The inhibitor comprises BTA, and the surfactant comprises, one of; polyacrylic acid, polyammoniumacrylate, polymethacrylic acid and polyammoniumacrylate.
- The invention is directed to an engineered copolymer for suppressing dishing during CMP of a semiconductor substrate, wherein the engineered copolymer comprises, molecules of a first moiety having one or more hydrophilic functional groups forming bonds with the metal on the substrate surface, and molecules of a second moiety having one or more hydrophobic functional groups that engage the polishing pad during CMP for the pad to remove the engineered copolymer from the surface of the metal being polished, which enables removal of the metal by CMP, while minimizing removal of the engineering copolymer from the recessed circuit interconnects to minimize dishing.
- Embodiments of the invention will now be described by way of example with reference to the accompanying detailed description.
- The engineered copolymer is derived from one or more monomers forming molecules of a first moiety having one or more hydrophilic functional groups forming bonds with the metal on the substrate surface, and forming molecules of a second moiety having one or more hydrophobic functional groups that engage the polishing pad during CMP for the pad to remove the engineered copolymer from the surface of the metal being polished, which enables removal of the metal by CMP, while minimizing removal of the engineering copolymer from the recessed circuit interconnects to minimize dishing. Hydrophilic functional groups are ionizable functional groups. Hydrophobic functional groups are non-ionizable functional groups. The engineered copolymer enhances removal of metal from a substrate, while minimizing dishing of recessed metal circuit interconnects through controlled contact-mediated reactions with the substrate surface and the polishing pad surface.
- In an embodiment, the engineered copolymer is derived from one or more monomers to provide hydrophilic functional groups that readily form strong bonds, e.g. coordinate covalent bonds, with the substrate surface during CMP. Further, the engineered copolymer is derived from one or more monomers to provide hydrophobic functional groups that provide structural rigidity to the copolymer molecules by van der Waals forces or other interactions. The rigidity of the engineered copolymer is adjusted by varying the mole ratios of the monomers forming the functional groups. When two monomers are utilized to derive or synthesize the engineering copolymer, the mole ratio of each monomer can be varied from about 1:20 to about 20:1. When more than two monomers are used to generate the copolymer, the total of all mole ratios is 1. In an embodiment, wherein the engineered copolymer of the invention is derived from at least two monomers, one monomer is polyethylenically unsaturated and serves as the extending agent or crosslinking agent in the copolymer.
- According to an embodiment, the molecules of the first moiety comprises, hydrophilic functional groups of one or more of; carboxyl, hydroxyl, halogen, phosphonate, phosphate, sulfonate, sulfate, nitro and the like, to form bonds with the metal being removed by CMP.
- According to an embodiment, at least one or more engineered copolymers are present up to about 1% by weight in a reactive liquid. The reactive liquid is a particle-free polishing composition that comprises, (i) up to about 15% by weight of an oxidizing agent; (ii) up to about 2% by weight of a corrosion inhibitor; and (iii) up to about 3% by weight of a complexing agent forming complex metal ions in the reactive liquid. Further, the reactive liquid comprises, a pH under about 5.0, alternatively, a pH in a range of about 2.8 to about 4.2, and alternatively, a pH in a range of about 2.8 to about 3.8.
- According to another embodiment, at least one or more engineered copolymers are present up to about 1% by weight in a polishing composition having abrasive particles. The composition comprises, (i) up to about 15% by weight of an oxidizing agent; (ii) up to about 2% by weight of a corrosion inhibitor; (iii) up to about 3% by weight of a complexing agent, and (iv) up to about 3% by weight of abrasive particles. Further, the composition comprises, a pH under about 5.0, alternatively, a pH in a range of about 2.8 to about 4.2, and alternatively, a pH in a range of about 2.8 to about 3.8.
- In an embodiment, the engineered copolymer is derived from a mixture of monomers, for example, an acrylic acid monomer and methacrylic acid monomer, combined at a mole ratio in a range of about 1:20 to about 20:1, and alternatively in a range of about 1:1.
- In another embodiment, the engineered copolymer is derived from a mixture of monomers, for example, a mixture of, two or more, ethylenically unsaturated monomers, said mixture containing at least about 50% by weight of an unsaturated carboxylic acid monomer to form branched and/or unbranched copolymer molecules.
- The unsaturated carboxylic acid monomer comprises, either an unsaturated monocarboxylic acid monomer or an unsaturated dicarboxylic acid monomer. An unsaturated monocarboxylic acid monomer refers to one of unsaturated carboxylic acid monomers containing 3 to 6 carbon atoms per molecule with a single carboxylic acid group and water-soluble salts thereof. Suitable ethylenically unsaturated monocarboxylic acid monomers are, for example, acrylic acid, oligomeric acrylic acid, methacrylic acid, crotonic acid, vinylacetic acid and derivatives thereof such as corresponding anhydrides, amides, esters and water-soluble salts thereof.
- An unsaturated dicarboxylic acid monomer refers to one of unsaturated dicarboxylic acid monomers containing 4 to 8 carbon atoms per molecule, anhydrides of the cis-and trans-dicarboxylic acids, and water-soluble salts thereof. Suitable unsaturated dicarboxylic acid monomers comprrse, for example, maleic acid, fumaric acid, alpha-methylene glutaric acid, itaconic acid, citraconic acid, mesaconic acid, cyclohexenedicarboxylic acid, and derivatives such as corresponding anhydrides, amides, esters and water-soluble salts thereof.
- In another embodiment, the engineered copolymer is derived from one or more of monoethylenically unsaturated monomers, such as, vinylaromatic monomers comprising, for example, styrene, α-methylstyrene, vinyltoluene, ortho-, meta- and para-methylstyrene, ethylvinylbenzene, vinylnaphthalene and vinylxylenes. The vinylaromatic monomer includes a corresponding substituted counterpart, for example, one of halogenated derivatives, containing one or more halogen groups, such as fluorine, chlorine or bromine; and nitro, or, for example, derivatives of, cyano, alkoxy, haloalkyl, carbalkoxy, carboxy, amino and alkylamino.
- In another embodiment, the engineered copolymer is derived from one or more of monoethylenically unsaturated monomers comprising, for example, nitrogen-containing ring compounds, for example, vinylpyridine, 2-methyl-5-vinylpyridine, 2-ethyl-5-vinylpyridine, 3-methyl-5-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, 2-methyl-3-ethyl-5-vinylpyridine, methyl-substituted quinolines and isoquinolines, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylcaprolactam, N-vinylbutyrolactam and N-vinylpyrrolidone. Monoethylenically unsaturated monomers also comprise ethylene and substituted ethylene monomers, for example: α-olefins such as propylene, isobutylene and long chain alkyl α-olefins (such as (C10-C20)alkyl α-olefins); vinyl alcohol esters such as vinyl acetate and vinyl stearate; vinyl halides such as vinyl chloride, vinyl fluoride, vinyl bromide, vinylidene chloride, vinylidene fluoride and vinylidene bromide; vinyl nitriles such as acrylonitrile and methacrylonitrile.
- In another embodiment, the engineered copolymer is derived from the polymerization of one of acrylic monomers and one of alkyl methacrylate monomers. Examples of the alkyl methacrylate monomer wherein the alkyl group contains from 1 to 6 carbon atoms (also called the “low-cut” alkyl methacrylates), are methyl methacrylate (MMA), methyl and ethyl acrylate, propyl methacrylate, butyl methacrylate (BMA) and butyl acrylate (BA), isobutyl methacrylate (IBMA), hexyl and cyclohexyl methacrylate, cyclohexyl acrylate and combinations thereof. Examples of the alkyl methacrylate monomer wherein the alkyl group contains from 7 to 15 carbon atoms (also called the “mid-cut” alkyl methacrylates), are 2-ethylhexyl acrylate (EHA), 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, isodecyl methacrylate (IDMA, based on branched (C10)alkyl isomer mixture), undecyl methacrylate, dodecyl methacrylate (also known as lauryl methacrylate), tridecyl methacrylate, tetradecyl methacrylate (also known as myristyl methacrylate), pentadecyl methacrylate and combinations thereof. Also included in an embodiment are: dodecyl-pentadecyl methacrylate (DPMA), a mixture of linear and branched isomers of dodecyl, tridecyl, tetradecyl and pentadecyl methacrylates; and lauryl-myristyl methacrylate (LMA), a mixture of dodecyl and tetradecyl methacrylates. Examples of alkyl methacrylate monomers wherein the alkyl group contains from 16 to 24 carbon atoms (also called the “high-cut” alkyl methacrylates), are hexadecyl methacrylate (also known as cetyl methacrylate), heptadecyl methacrylate, octadecyl methacrylate (also known as stearyl methacrylate), nonadecyl methacrylate, eicosyl methacrylate, behenyl methacrylate and combinations thereof. Also useful are: cetyl-eicosyl methacrylate (CEMA), a mixture of hexadecyl, octadecyl, and eicosyl methacrylate; and cetyl-stearyl methacrylate (SMA), a mixture of hexadecyl and octadecyl methacrylate.
- In another embodiment, the engineered copolymer is derived from one or more of, alkyl methacrylate monomers and acrylate monomers with a dialkylamino group in the alkyl radical, such as dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate; dialkylaminoalkyl methacrylamide and acrylamide monomers, such as N,N-dimethylaminoethyl methacrylamide, N,N-dimethylaminopropyl methacrylamide, N,N-dimethylaminobutyl methacryl-amide, N,N-diethylaminoethyl methacrylamide, N,N-diethylaminopropyl methacrylamide and N,N-diethylaminobutyl methacrylamide. Alkyl methacrylate and acrylate monomers with one or more hydroxyl groups in the alkyl radical, especially those wherein the hydroxyl group is found at the β-position (2-position) in the alkyl radical. Hydroxyalkyl methacrylate and acrylate monomers have a substituted alkyl group (C2-C6)alkyl, branched or unbranched Hydroxy-alkyl methacrylate and acrylate monomers comprise, 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 1-methyl-2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 1-methyl-2-hydroxyethyl acrylate, 2-hydroxybutyl methacrylate and 2-hydroxybutyl acrylate. A mixture of 1-methyl-2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate, is known as “hydroxypropyl methacrylate” or HPMA.
- In another embodiment, the engineered copolymer is derived from one or more of, amine-containing monomers comprising, for example, amide monomers, such as, dialkylaminoalkyl acrylamides or methacrylamides (for example, dimethylaminopropyl methacrylamide), N,N-bis-(dimethylaminoalkyl) acrylamides or methacrylamides, N-β-aminoethyl acrylamide or methacrylamide, N-(methylamino-ethyl)acrylamide or methacrylamide, aminoalkylpyrazine acrylamides or methacrylamides; acrylic ester monomers such as dialkylaminoalkyl acrylates or methacrylates (for example, dimethylaminoethyl acrylate or methacrylate), β-aminoethyl acrylate or methacrylate, N-(n-butyl)-4-aminobutyl acrylate or methacrylate, methacryloxyethoxyethylamine, and acryloxypropoxypropoxypropylamine; vinyl monomers such as vinyl pyridines; aminoalkyl vinyl ethers or sulfides such as β-aminoethyl vinyl ether, β-aminoethyl vinyl sulfide, N-methyl-β-aminoethyl vinyl ether or sulfide, N-ethyl-p-aminoethyl vinyl ether or sulfide, N-butyl-β-aminoethyl vinyl ether or sulfide, and N-methyl-3-aminopropyl vinyl ether or sulfide; N-acryloxyalkyloxazolidines and N-acryloxyalkyltetrahydro-1,3-oxazines such as oxazolidinylethyl methacrylate, oxazolidinylethyl acrylate, 3-(γ-methacryloxypropyl)tetrahydro-1,3-oxazine, 3-(β-methacryloxyethyl)-2,2pentamethylene-oxazolidine, 3-(β-methacryloxyethyl)-2-methyl-2-propyl-oxazolidine, N-2-(2-acryloxyethoxy)ethyl-oxazolidine, N-2-(2-meth-acryloxyethoxy)-ethyl-5-methyl-oxazolidine, 3-[2-(2-methacryloxyethoxy)ethyl]-2,2-dimethyloxazolidine, N-2-(2-acryloxyethoxy)ethyl-5-methyl-oxazolidine, 3-[2-(meth-acryloxyethoxy)-ethyl]-2-phenyl-oxazolidine, N-2-(2-methacryloxyethoxy)ethyl-oxa-zolidine, and 3-[2-(2-methacryloxyethoxy)ethyl]-2,2-pentamethylene-oxazolidine.
- In another embodiment, the engineered copolymer is derived from one or more of, monomers with an unsaturated sulfonic acid monomer selected from one or more of 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-pro-panesulfonic acid, 3-methacrylamido-2-hydroxy-1-propanesulfonic acid, allylsulfonic acid, allyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate and water-soluble salts thereof. According to an embodiment, an engineered copolymer is derived from acrylic acid monomer and methacrylic acid monomer combined at a mole ratio in a range of about 1:20 to about 20:1, and alternatively, about 1:1 (±25%).
- Accordingly, an engineered copolymer is derived from polymerization of one or more of, monomers selected from the aforementioned classes of monomers, including, random copolymers, branched copolymers, block copolymers and alternating copolymers.
- The engineered copolymer is used in a polishing composition for CMP together with a commercially available polishing pad, for example, a polishing pad described in U.S. Pat. No. 5,489,233 and U.S. Pat. No. 5,932,486 and U.S. Pat. No. 5,932,486.
- Removal of material, e.g., copper, from a substrate surface during CMP utilizes a polishing composition containing, a metal oxidizing agent, a corrosion inhibitor, e.g., benzotriazole, BTA, and molecules of an engineered copolymer derived from monomers having hydrophilic functional groups and hydrophobic functional groups. During CMP, the corrosion inhibitor molecules and the engineered copolymer molecules undergo redistribution and compete to form bonds with the metal surface on the substrate. The metal surface comprises hydrated metal atoms and hydrated metal atom-corrosion inhibitor molecular complexes. For example, a surface of an exemplary copper layer on a substrate has hydrated copper atoms and hydrated copper atom-BTA complexes. The hydrophilic functional groups form strong bonds, e.g., coordinate covalent bonds. The hydrophobic functional groups form strong van der Waals bonds with known nanoasperities on the polishing pad surface.
- The engineered copolymer is added to conventional polishing compositions, in a manner now described. An oxidizing agent used in a polishing composition for CMP includes, but is not limited to, peroxides such as hydrogen peroxide, iodates such as potassium iodate, nitrates such as cesium nitrate, barium nitrate, ammonium nitrate, and/or mixtures of ammonium nitrate and cesium nitrate, carbonates such as ammonium carbonate, and persulfates such as ammonium persulfate and/or sodium persulfate and perchlorates.
- A complexing agent, disclosed by U.S. Pat. No. 5,391,258, includes a carboxylic acid containing two or more carboxylate groups with hydroxy groups. Further, a complexing agent includes, but is not limited to, straight chain mono-and dicarboxylic acids and their corresponding salts such as malic acid and malates; tartaric acid and tartarates; gluconic acid and gluconates; citric acid and citrates; malonic acid and malonates; formic acid and formates; lactic acid and lactates; phthalic acid and phthalates; and polyhydroxybenzoic acid and its salts. can also be used in the polishing composition.
- Corrosion inhibitors used in polishing compositions for CMP include BTA (benzotriazole) and TTA (tolyltriazole) or mixtures thereof. Other inhibitors that are suitable for use include: 1-hydroxybenzotriazole,N-(1H-benzotriazole-1-ylmethyl)formamide; 3,5-dimethylpyrazole; indazole; 4-bromopyrazole; 3-amino-5-phenylpyrazole; 3-amino-4-pyrazolecarbonitrile; 1-methyimidazole; Indolin QTS and the like.
- A polishing composition for CMP is substantially particle-free or, alternatively, contains abrasive particles of a material that includes, but is not limited to, alumina, silica, ceria, germania, diamond, silicon carbide, titania, zirconia and various mixtures thereof. In an embodiment, the polishing composition of the invention does not contain any abrasive particles. In another embodiment, the polishing composition contains low levels of abrasives in a range from about 0 to about 3%, with an average particle diameter less than 50 nm. In other embodiments, the weight % of abrasive can be up to about 50%.
- Optionally, a polishing composition for CMP may contain pH buffers such as amines, and may contain surfactants, deflocculants, viscosity modifiers, wetting agents, cleaning agents and the like.
- The following examples illustrate various aspects of the invention. All parts and percentages are on a weight basis (i.e., by weight of the polishing composition) and all molecular weights are determined by gel permeation chromatography (GPC) and are weight-average molecular weights unless otherwise indicated.
- Engineered copolymers I and II were derived or synthesized as described below. All molecular weights were determined utilizing GPC analysis according to the following procedure. Molecular weight Determination: Samples were dissolved in 0.02M sodium dihydrogen phosphate at pH 7 at a concentration of approximately 0.1% w/v and shaken for 10 minutes, followed by filtration through a 0.45 micron PTFE polytetrafluoroethylene membrane filter. The analysis was performed by injecting 100 microliters of this solution into a 2-column set consisting of a TosoHaas TSKgel GMPWx1 and a TosoHaas TSKgel G2500PWx1 and a TosoHaas TSKgel G2500 Wx1 30 cm×8 mm column, held at 40 C. The mobile phase used was this solution at a flow rate of 1 ml/min. Detection was via a differential refractive index measurement. The system was calibrated with narrow poly(acrylic) acid standards.
- Engineered Copolymer I:
- To a 1 liter, 4-neck flask equipped with a mechanical stirrer, a reflux condenser, a thermocouple, and septum inlets was added 575.00 g (grams) deionized (D.I.) water and 5.00 g of 0.15 weight % FeSO4.7H2O. To this stirred solution at 60° C., 20.00 g of a monomer mixture containing 109.00 g of glacial methacrylic acid and 91.00 g of glacial acrylic acid was added. At 65° C., 0.50 g of sodium persulfate in 10.00 g D.I. water and 4.00 g sodium metabisulfite in 30.00 g D.I. water were added linearly and separately over 130 min. Ten minutes later, the remaining monomer mixture was added linearly over 120 min., at 72° C. After addition, the solution was held at temperature for 10 min., then cooled to 62° C. Next, 0.12 g of sodium persulfate in 5.00 g D.I. water was added. The solution was held for 10 min. and the procedure repeated. The stirred solution was adjusted with 20.20 g of 50% sodium hydroxide and 2.70 g of 30% hydrogen peroxide. Next, 0.25 g of isoascorbic acid in 5.00 g D.I. water was added. The solution was held for 5 min. and the procedure repeated. The aqueous copolymer solution at pH 3.8 had a solids content of 24.3%, 548 ppm, parts per million, of acrylic acid, no detectable methacrylic acid and a molecular weight (MW) of 178,700 with a corresponding mole ratio.
- Engineered Copolymer II:
- To a 1 liter, 4-neck flask equipped with a mechanical stirrer, reflux condenser, thermocouple, and septum inlets, was added, 575.00 g of D.I. water and 5.00 g of 0.15 weight % FeSO4.7H2O. To this stirred solution at 72° C., 1.00 g of sodium persulfate in 10.00 g D.I. water, 12.00 g sodium metabisulfite in 60.00 g D.I. water and a mixture containing 109.00 g of glacial methacrylic acid and 91.00 g of glacial acrylic acid were added linearly and separately over 120 min. After addition, the solution was held at temperature for 10 min., cooled to 62° C. and followed by the addition of 0.12 g sodium persulfate in 5.00 g D.I. water. The solution was held at temperature for 10 min. and another 0.12 g of sodium persulfate in 5.00 g D.I. water was added. The stirred solution was adjusted with 20.20 g of 50% sodium hydroxide and 6.00 g of 30% hydrogen peroxide. Next, 0.25 g of isoascorbic acid in 5.00 g D.I. water was added. The solution was held for 5 min. and the procedure repeated. The aqueous copolymer solution at pH 3.6 had a solids content of 24.3%, 426 ppm of acrylic acid, no detectable methacrylic acid and a MW of 28,800 with a corresponding mole ratio.
- Engineered Copolymer IIA.
- To a 1 liter, 4-neck flask equipped with a mechanical stirrer, reflux condenser, thermocouple, and septum inlets was added 500.00 grams (g.) deionized (DI) water and 5.00 g. of 0.15 weight % FeSO4.7H2O. To this stirred solution at 90° C., 0.80 g. of sodium persulfate in 10.00 g. of DI water was added. After holding five minutes at 90° C., 12.00 g. of a monomer mixture containing 67.70 g. of glacial methacrylic acid and 132.30 g. of glacial acrylic acid was added. Five minutes later, at 92° C., 7.20 g. of sodium persulfate in 40.00 g. DI water, 2.00 g. sodium hypophosphite in 20.00 g. DI water and the remaining monomer mixture were added separately and linearly over 120 min. After addition, the solution was held at temperature for 30 min., then cooled to 70° C. Next, 20.20 g. of 50% sodium hydroxide was added, dropwise. The aqueous copolymer solution at pH 3.6 had a solids content of 26.8%, no detectable methacrylic acid or acrylic acid and a molecular weight (Mw) of 29,600 with a corresponding mole ratio.
- Engineered Copolymer IIB.
- To a 1 liter, 4-neck flask equipped with a mechanical stirrer, reflux condenser, thermocouple, and septum inlets was added 410.00 grams (g.) deionized (DI) water and 5.00 g. of 0.15 weight % FeSO4.7H2O. To this stirred solution at 92° C., 10.00 g. sodium persulfate in 60.00 g. DI water was added linearly over 122 minutes. Two minutes later, at 92° C., 1.50 g. sodium hypophosphite in 20.00 g. DI water and a monomer mixture containing 147.20 g. glacial methacrylic acid and 52.80 g. glacial acrylic acid were added separately and linearly over 120 min. After addition, the solution was held at temperature for 30 min., and then cooled to 70° C. Next, 20.20 g. of 50% sodium hydroxide was added, dropwise. The aqueous copolymer solution at pH 3.8 had a solids content of 29.8%, no detectable methacrylic acid or acrylic acid and a molecular weight (Mw) of 19,500 with a corresponding mole ratio.
- Each of the engineered copolymers I, II, IIA and IIB was combined with a polishing composition, which was used in CMP to polish respective copper patterned wafers on an AMAT Mirra polishing machine. Polishing by CMP was performed under the following conditions: First step at 5 psi down force, 93 rpm platen speed and 87 rpm carrier speed for 60 seconds; Second step at 3 psi down force, 93 rpm platen speed, 87 rpm carrier speed for 60 seconds. The first step of polishing was performed until endpoint was achieved on the AMAT Mirra as determined by the Mirra endpoint detection system. The second polishing step was terminated when the endpoint curve slope was zero. An IC1000 (X-Y grooved) polishing pad available from Rodel, Inc., Newark, Del. was used for each polishing test. The slurry flow rate was held constant at 250 ml/min during each polishing test. A Tencor P1 profilometer was used to measure dishing of 100 μm lines in the center, middle and edge of each test wafer. The data obtained during the various polishing tests are summarized in Table 1 below.
TABLE 1 Average Removal Rate Dishing Sample pH (Angstroms/min) (Angstroms) Residuals Control 3.1 3,435 1,300 Significant residuals A1 3.0 5,394 1,920 Clear/no residuals A2 3.5 3,285 1,580 Clear/no residuals B1 3.0 4,611 1,350 Clear/no residuals B2 3.5 3,200 990 Clear/no residuals C1 3.0 2014 Clear/no residuals D1 3.0 831 Significant residuals - All polishing compositions contained 9% hydrogen peroxide, 0.3% BTA and 0.22% malic acid.
- The Control contained 0.18% of a 1:1 mixture of polyacrylic acids with number average molecular weights of 250,000 and 30,000, respectively.
- Polishing compositions A1 and A2 contained 0.36% of active engineered copolymer I.
- Polishing compositions B1 and B2 contained 0.36% of active engineered copolymer II.
- Polishing composition C1 contained 0.18% of active engineered copolymer IIB and Polishing composition D1 contained 0.18% of active engineered copolymer IIA.
- The remaining weight percentage of each polishing composition comprised water.
- The data in Table I indicates that a copolymer containing a 7:3 molar composition of polymethacrylic acid to polyacrylic acid clears the wafer of all copper residue whereas a copolymer containing a 3:7 molar composition of polymethacrylic acid to polyacrylic acid does not clear all the cooper residue. Accordingly, clearing of copper residuals requires at least an equimolar ratio 1:1 or greater ratio, of the polymethylacrylic acid in the copolymer.
- Engineered copolymers III, IV and V were synthesized as described below.
- Engineered Copolymer III:
- To a 2 liter, 4-neck round bottom flask equipped with a mechanical stirrer, reflux condenser, thermocouple, and septum inlets was added 700.00 g (grams) of D.I. water and 6.00 g of 0.15 weight % FeSO4.7H2O. To this stirred solution at 80° C., 13.50 g of sodium persulfate in 100.00 g D.I. water; 75.00 g of 50% sodium hydroxide and a mixture containing 106.00 g of glacial methacrylic acid and 160.00 g hydroxyethyl methacrylate were added linearly and separately over 125 min. as the kettle temperature was allowed to rise to 92° C. After addition, the solution was held for 30 min. and 0.20 g sodium persulfate in 1.00 g D.I. water was then added. The solution was held at temperature for 10 min. and the procedure repeated with 0.50 g sodium persulfate in 4.00 g D.I. water. The aqueous copolymer solution at pH 6.2 had a solids content of 25.9%, 1450 ppm methacrylic acid and a MW of 20,100 with a corresponding mole ratio.
- Engineered Copolymer IV:
- To a 2 liter, 4-neck round bottom flask equipped with a mechanical stirrer, reflux condenser, thermocouple, and septum inlets was added 577.00 g of D.I. water and 3.00 g of 0.15 weight % FeSO4.7H2O. To this stirred solution at 88° C., 10.20 g of sodium persulfate in 50.00 g D.I. water, 99.00 g of 50% sodium hydroxide and a mixture containing 206.50 g of glacial methacrylic acid and 132.60 g hydroxyethyl methacrylate were added linearly and separately over 125 min. After addition, the solution was held at 88 to 90° C. for 55 min. and 1.10 g sodium persulfate in 7.20 g D.I. water was then added and the solution held at temperature for 60 min., cooled to 65° C. and diluted with 40.00 g D.I. water. The aqueous copolymer solution at pH 5.9 had a solids content of 34.0%, 397 ppm methacrylic acid and a MW of 14,100 with a corresponding mole ratio.
- Engineered Copolymer V:
- To a 2 liter, 4-neck round bottom flask equipped with a mechanical stirrer, reflux condenser, thermocouple, septum inlets and containing 800.00 g D.I. water at 86° C. was added; 0.25 g of inhibitor, 70.80 g of a 1.75 wt % surfactant solution, 68.30 g of a monomer emulsion, containing 300.00 g D.I. water, 2.20 g of a 30% surfactant solution, 325.00 g of methyl methacrylate, and 4.20 g of glacial methacrylic acid followed by 2.30 g of sodium persulfate in 16.7 g D.I. water. After addition, the kettle material was held at 86° C. for 15 minutes. To the remaining monomer emulsion 23.00 g of a 30% surfactant solution, 248.50 g of glacial methacrylic acid, and 5.70 g of n-dodecyl mercaptan was added followed by 30.00 g of rinse water. This monomer emulsion was added linearly over 120 min. to the kettle at 85° C. After addition, the reaction was held at temperature for 15 min., cooled, then filtered through 100/325 mesh screens. The emulsion polymer at pH 2.8 had a solids content of 31.4%, 331 ppm of methacrylic acid, 171 ppm of methyl methacrylate, a MW of 56,400 with a corresponding mole ratio, and a particle size of 105 nm.
- Table 2 summarizes removal rate data obtained, according to the method of the invention, utilizing polishing compositions containing engineered copolymers III, IV and V. All polishing compositions contained 0.36% of the respective engineered copolymer, 9% hydrogen peroxide, 0.3% BTA, and 0.22% malic acid. The remaining weight percentage of each polishing composition comprised water.
TABLE 2 Engineered Molecular Removal Rate Copolymer Weight (MW) (Angstroms/minute) III 20,100 1,500 IV 14,100 3,000 V 56,400 <1,000 - The data in Table 2 illustrate that removal rates in excess of 1,000 Angstroms per minute are obtained utilizing the invention. The exemplified polishing compositions respectively comprised engineered copolymers made from a mixture of monomers, wherein the mixture has greater than 50 mole % of acid-containing monomers.
- A polishing composition for CMP is provided with an engineered copolymer comprising, molecules of a first moiety having one or more hydrophilic functional groups forming bonds with the metal on the substrate surface, and further comprising, molecules of a second moiety having one or more hydrophobic functional groups that engage the polishing pad during CMP for the pad to remove the engineered copolymer from the surface of the metal being polished, which enables removal of the metal by CMP, while minimizing removal of the engineering copolymer from the recessed circuit interconnects to minimize dishing.
Claims (35)
1. A polishing composition for removing metal by CMP comprises, a metal oxidizer, an oxide inhibitor and a complexing agent, further characterised by;
an engineered copolymer comprising, molecules of a first moiety having hydrophilic functional groups forming bonds with the metal, and further comprising, molecules of a second moiety having hydrophobic functional groups that engage a polishing pad during CMP for the pad to remove the engineered copolymer from a surface of the metal, which enables removal of the metal by CMP, while minimizing removal of the engineering copolymer from recessed circuit interconnects to minimize dishing.
2. The polishing composition as in claim 1 , wherein said engineered copolymer is selected from a group consisting of; random copolymers, block copolymers, branched copolymers and alternating copolymers.
3. The polishing composition as in claim 1 wherein the engineered copolymer is present at a concentration up to about 1% by weight.
4. The polishing composition as in claim 1 , further characterised by; abrasive particles up to about 3% by weight.
5. A polishing composition as in claim 1 wherein the engineered copolymer is derived from an acrylic acid monomer and a methacrylic acid monomer at a mole ratio of acrylic acid monomer to methacrylic acid monomer in a range of, about 1:20 to about 20:1.
6. A polishing composition as in claim 1 wherein the engineered copolymer is derived from a mixture of ethylenically unsaturated monomers.
7. A polishing composition as in claim 1 wherein the engineered copolymer has a concentration up to about 1% by weight, the oxidizing agent has a concentration up to about 15% by weight, the complexing agent has a concentration up to about 3% by weight, and the inhibitor has a concentration up to about 2% by weight.
8. A method for removing metal by CMP, comprising: polishing the metal with a polishing pad and a polishing composition, the polishing composition having, a metal oxidizer, an oxide inhibitor, a complexing agent, and an engineered copolymer comprising, molecules of a first moiety having hydrophilic functional groups forming bonds with the metal, and further comprising, molecules of a second moiety having hydrophobic functional groups that engage the polishing pad during CMP for the pad to remove the engineered copolymer from a surface of the metal, which enables removal of the metal by CMP while minimizing removal of the engineering copolymer from recessed circuit interconnects to minimize dishing.
9. The method as in claim 8 wherein the polishing composition further comprises abrasive particles of a concentration up to about 3% by weight.
10. An aqueous polishing composition for selectively removing a portion of a metal layer from a semiconductor substrate during semiconductor device fabrication, comprising: at least one engineered copolymer, wherein said engineered copolymer comprises a first moiety and a second moiety, said first moiety comprising a hydrophilic functional group and said second moiety being relatively less hydrophilic than the first moiety.
11. polishing composition in accordance with claim 11 wherein the first moiety comprises a hydrophilic functional group with an affinity for the semiconductor substrate surface.
12. A polishing composition in accordance with claim 11 wherein the second moiety comprises a hydrophobic functional group which interacts with the polishing pad surface.
13. A polishing composition in accordance with claim 11 wherein said engineered copolymer is selected from a group consisting of random, block, branched and alternating copolymers.
14. A polishing composition in accordance with claim 13 wherein at least one engineered copolymer component is present at a concentration up to about 1% by weight of said composition.
15. A polishing composition in accordance with claim 14 further comprising abrasive particles up to about 3% by weight of said composition.
16. A polishing composition in accordance with claim 15 further comprising an oxidizing agent up to about 15% by weight of said composition.
17. A polishing composition in accordance with claim 16 further comprising a complexing agent up to about 3% by weight of said composition.
18. A polishing composition in accordance with claim 17 further comprising an inhibitor up to about 2% by weight of said composition.
19. A polishing composition in accordance with claim 18 wherein said copolymer is derived from a mixture comprising acrylic acid monomer and methacrylic acid monomer at a mole ratio of acrylic acid monomer to methacrylic acid monomer of about 1:20 to about 20:1.
20. A polishing composition in accordance with claim 19 wherein the copolymer has a weight average molecular weight in a range of about 20,000 to about 30,000.
21. A polishing composition in accordance with claim 20 further having a pH less than 5.
22. A polishing composition in accordance with claim 16 wherein the oxidizing agent is hydrogen peroxide.
23. A polishing composition in accordance with claim 17 wherein the complexing agent is malic acid.
24. A polishing composition in accordance with claim 18 wherein the inhibitor is an aromatic triazole.
25. A polishing composition of claim 13 wherein said engineered copolymer comprises the reaction product derived from a mixture of two or more ethylenically unsaturated monomers.
26. A polishing composition in accordance with claim 25 wherein at least 50% by weight of said mixture is an unsaturated carboxylic acid monomer.
27. A method for selectively removing a portion of a metal layer from a semiconductor substrate, during semiconductor device fabrication, comprising:
providing a substrate having a metal layer requiring removal;
providing a polishing pad;
biasing said substrate and said polishing pad under a pressure; and
dispensing a polishing composition comprising at least one engineered copolymer, wherein said engineered copolymer comprises a first moiety and a second moiety, said first moiety comprising a hydrophilic functional group and said second moiety being relatively less hydrophilic than the first moiety.
28. A method in accordance with claim 18 performed utilizing a polishing composition wherein the first moiety comprises a hydrophilic functional group with an affinity for the semiconductor substrate surface.
29. A method in accordance with claim 27 performed utilizing a polishing composition wherein the second moiety comprises a hydrophobic functional group which interacts with the polishing pad surface.
30. A method in accordance with claim 27 wherein said engineered copolymer is selected from a group consisting of random, block, branched and alternating copolymers.
31. A method in accordance with claim 27 performed on a semiconductor substrate containing a copper layer requiring removal and copper interconnects utilizing an aqueous polishing composition comprising:
at least one engineered copolymer up to about 1% by weight of said composition;
an oxidizing agent up to about 15% by weight of said composition;
a complexing agent up to about 3% by weight of said composition; and
an inhibitor up to about 2% by weight of said composition.
32. A method in accordance with claim 31 performed utilizing a polishing composition further comprising abrasive particles up to about 3% by weight of said composition.
33. A method in accordance with claim 27 performed utilizing a polishing composition containing a copolymer derived from a mixture comprising acrylic acid monomer and methacrylic acid monomer at a mole ratio of acrylic acid monomer to methacrylic acid monomer of about 1:20 to about 20:1.
34. A method in accordance with claim 33 performed utilizing a polishing composition containing a copolymer derived from a mixture comprising acrylic acid monomer and methacrylic acid monomer at a mole ratio of acrylic acid monomer to methacrylic acid monomer of about 1:20 to about 20:1, said copolymer further having a molecular weight in a range of about 20,000 to about 30,000.
35. A method in accordance with claim 31performed utilizing a polishing composition comprising: at least one engineered copolymer up to about 1% by weight of said composition; an oxidizing agent up to about 15% by weight of said composition; a complexing agent up to about 3% by weight of said composition; an inhibitor up to about 2% by weight of said composition; and a pH less than 5.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US10/150,211 US20030013386A1 (en) | 2001-05-18 | 2002-05-17 | Chemical mechanical polishing compositions and methods relating thereto |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/860,933 US6632259B2 (en) | 2001-05-18 | 2001-05-18 | Chemical mechanical polishing compositions and methods relating thereto |
US10/150,211 US20030013386A1 (en) | 2001-05-18 | 2002-05-17 | Chemical mechanical polishing compositions and methods relating thereto |
Related Parent Applications (1)
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US09/860,933 Continuation-In-Part US6632259B2 (en) | 2001-05-18 | 2001-05-18 | Chemical mechanical polishing compositions and methods relating thereto |
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US20030013386A1 true US20030013386A1 (en) | 2003-01-16 |
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US10/150,211 Abandoned US20030013386A1 (en) | 2001-05-18 | 2002-05-17 | Chemical mechanical polishing compositions and methods relating thereto |
US10/664,723 Expired - Lifetime US6902590B2 (en) | 2001-05-18 | 2003-09-17 | Chemical mechanical polishing compositions and methods relating thereto |
US11/077,671 Expired - Lifetime US7300874B2 (en) | 2001-05-18 | 2005-03-10 | Chemical mechanical polishing compositions and methods relating thereto |
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US09/860,933 Expired - Lifetime US6632259B2 (en) | 2001-05-18 | 2001-05-18 | Chemical mechanical polishing compositions and methods relating thereto |
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US10/664,723 Expired - Lifetime US6902590B2 (en) | 2001-05-18 | 2003-09-17 | Chemical mechanical polishing compositions and methods relating thereto |
US11/077,671 Expired - Lifetime US7300874B2 (en) | 2001-05-18 | 2005-03-10 | Chemical mechanical polishing compositions and methods relating thereto |
Country Status (7)
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US (4) | US6632259B2 (en) |
EP (1) | EP1399517A2 (en) |
JP (1) | JP2005502188A (en) |
KR (1) | KR20040002972A (en) |
CN (1) | CN1261511C (en) |
TW (1) | TWI241328B (en) |
WO (1) | WO2002094957A2 (en) |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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US20050136590A1 (en) * | 2003-12-19 | 2005-06-23 | Hynix Semiconductor Inc. | Method for forming capacitor of semiconductor device |
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US20080042099A1 (en) * | 2006-08-17 | 2008-02-21 | Comeau Joseph K V | Solution for forming polishing slurry, polishing slurry and related methods |
US20080081539A1 (en) * | 2006-09-29 | 2008-04-03 | Depuy Products, Inc. | Orthopaedic component manufacturing method and equipment |
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Families Citing this family (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6632259B2 (en) * | 2001-05-18 | 2003-10-14 | Rodel Holdings, Inc. | Chemical mechanical polishing compositions and methods relating thereto |
US6783432B2 (en) * | 2001-06-04 | 2004-08-31 | Applied Materials Inc. | Additives for pressure sensitive polishing compositions |
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Family Cites Families (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4017662A (en) * | 1967-11-29 | 1977-04-12 | Rohm And Haas Company | Polishing method |
US4299749A (en) * | 1980-06-30 | 1981-11-10 | Sterling Drug Inc. | Floor coating composition |
US4752628A (en) | 1987-05-15 | 1988-06-21 | Nalco Chemical Company | Concentrated lapping slurries |
US4869934A (en) * | 1988-09-16 | 1989-09-26 | Sterling Drug Inc. | Floor polishing and coating composition |
US5073285A (en) * | 1989-06-12 | 1991-12-17 | Lever Brothers Company, Division Of Conopco, Inc. | Stably suspended organic peroxy bleach in a structured aqueous liquid |
US5391258A (en) | 1993-05-26 | 1995-02-21 | Rodel, Inc. | Compositions and methods for polishing |
US5489233A (en) | 1994-04-08 | 1996-02-06 | Rodel, Inc. | Polishing pads and methods for their use |
US5614444A (en) | 1995-06-06 | 1997-03-25 | Sematech, Inc. | Method of using additives with silica-based slurries to enhance selectivity in metal CMP |
US5932486A (en) | 1996-08-16 | 1999-08-03 | Rodel, Inc. | Apparatus and methods for recirculating chemical-mechanical polishing of semiconductor wafers |
JP3371775B2 (en) | 1997-10-31 | 2003-01-27 | 株式会社日立製作所 | Polishing method |
JPH11162910A (en) | 1997-11-25 | 1999-06-18 | Sumitomo Chem Co Ltd | Abrasive for manufacturing semiconductor device and polishing method |
US6432828B2 (en) | 1998-03-18 | 2002-08-13 | Cabot Microelectronics Corporation | Chemical mechanical polishing slurry useful for copper substrates |
JP2002517593A (en) | 1998-06-10 | 2002-06-18 | ロデール ホールディングス インコーポレイテッド | Polishing composition and polishing method in metal CMP |
AU5445899A (en) | 1998-08-31 | 2000-03-21 | Hitachi Chemical Company, Ltd. | Abrasive liquid for metal and method for polishing |
JP4095731B2 (en) | 1998-11-09 | 2008-06-04 | 株式会社ルネサステクノロジ | Semiconductor device manufacturing method and semiconductor device |
KR100472882B1 (en) | 1999-01-18 | 2005-03-07 | 가부시끼가이샤 도시바 | Aqueous Dispersion, Chemical Mechanical Polishing Aqueous Dispersion Composition, Wafer Surface Polishing Process and Manufacturing Process of a Semiconductor Apparatus |
JP3941284B2 (en) | 1999-04-13 | 2007-07-04 | 株式会社日立製作所 | Polishing method |
TWI254070B (en) | 1999-08-18 | 2006-05-01 | Jsr Corp | Aqueous dispersion for chemical mechanical polishing |
EP1210395B1 (en) | 1999-08-24 | 2003-10-22 | Rodel Holdings, Inc. | Compositions for insulator and metal cmp and methods relating thereto |
US6443812B1 (en) | 1999-08-24 | 2002-09-03 | Rodel Holdings Inc. | Compositions for insulator and metal CMP and methods relating thereto |
JP2002050595A (en) | 2000-08-04 | 2002-02-15 | Hitachi Ltd | Polishing method, wiring forming method, and semiconductor device manufacturing method |
US6605537B2 (en) | 2000-10-27 | 2003-08-12 | Rodel Holdings, Inc. | Polishing of metal substrates |
JP3768402B2 (en) | 2000-11-24 | 2006-04-19 | Necエレクトロニクス株式会社 | Chemical mechanical polishing slurry |
US6632259B2 (en) * | 2001-05-18 | 2003-10-14 | Rodel Holdings, Inc. | Chemical mechanical polishing compositions and methods relating thereto |
-
2001
- 2001-05-18 US US09/860,933 patent/US6632259B2/en not_active Expired - Lifetime
-
2002
- 2002-05-17 TW TW091110370A patent/TWI241328B/en not_active IP Right Cessation
- 2002-05-17 EP EP02736981A patent/EP1399517A2/en not_active Withdrawn
- 2002-05-17 US US10/150,211 patent/US20030013386A1/en not_active Abandoned
- 2002-05-17 WO PCT/US2002/015825 patent/WO2002094957A2/en not_active Application Discontinuation
- 2002-05-17 JP JP2002592420A patent/JP2005502188A/en not_active Withdrawn
- 2002-05-17 CN CNB028100328A patent/CN1261511C/en not_active Expired - Lifetime
- 2002-05-17 KR KR20037014999A patent/KR20040002972A/en not_active Withdrawn
-
2003
- 2003-09-17 US US10/664,723 patent/US6902590B2/en not_active Expired - Lifetime
-
2005
- 2005-03-10 US US11/077,671 patent/US7300874B2/en not_active Expired - Lifetime
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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US20110104992A1 (en) * | 2008-04-15 | 2011-05-05 | Kouji Haga | Polishing solution for metal films and polishing method using the same |
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US9120199B2 (en) * | 2010-12-09 | 2015-09-01 | Kao Corporation | Polishing liquid composition |
Also Published As
Publication number | Publication date |
---|---|
CN1509322A (en) | 2004-06-30 |
US6902590B2 (en) | 2005-06-07 |
US6632259B2 (en) | 2003-10-14 |
WO2002094957A2 (en) | 2002-11-28 |
US7300874B2 (en) | 2007-11-27 |
US20040065020A1 (en) | 2004-04-08 |
US20030032371A1 (en) | 2003-02-13 |
TWI241328B (en) | 2005-10-11 |
WO2002094957A3 (en) | 2003-10-23 |
US20050159003A1 (en) | 2005-07-21 |
EP1399517A2 (en) | 2004-03-24 |
JP2005502188A (en) | 2005-01-20 |
CN1261511C (en) | 2006-06-28 |
KR20040002972A (en) | 2004-01-07 |
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