TWI794326B - 研磨劑與研磨方法、及研磨用添加液 - Google Patents
研磨劑與研磨方法、及研磨用添加液 Download PDFInfo
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- TWI794326B TWI794326B TW107139137A TW107139137A TWI794326B TW I794326 B TWI794326 B TW I794326B TW 107139137 A TW107139137 A TW 107139137A TW 107139137 A TW107139137 A TW 107139137A TW I794326 B TWI794326 B TW I794326B
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- Taiwan
- Prior art keywords
- monomer
- abrasive
- acid
- grinding
- water
- Prior art date
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- -1 grinding method Substances 0.000 title claims abstract description 25
- 238000000227 grinding Methods 0.000 title claims description 63
- 239000007788 liquid Substances 0.000 title claims description 40
- 238000000034 method Methods 0.000 title claims description 29
- 239000003795 chemical substances by application Substances 0.000 title claims description 26
- 239000000654 additive Substances 0.000 title claims description 22
- 230000000996 additive effect Effects 0.000 title claims description 21
- 239000000178 monomer Substances 0.000 claims abstract description 139
- 239000002245 particle Substances 0.000 claims abstract description 58
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 57
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 55
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 55
- 150000003839 salts Chemical class 0.000 claims abstract description 48
- 229920001577 copolymer Polymers 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 150000001991 dicarboxylic acids Chemical class 0.000 claims abstract description 16
- 230000002378 acidificating effect Effects 0.000 claims abstract description 11
- 238000005498 polishing Methods 0.000 claims description 112
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 86
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 28
- 239000006185 dispersion Substances 0.000 claims description 28
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 25
- 239000000758 substrate Substances 0.000 claims description 24
- 239000004065 semiconductor Substances 0.000 claims description 23
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 21
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 20
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 18
- 239000003082 abrasive agent Substances 0.000 claims description 17
- 239000011976 maleic acid Substances 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 13
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 150000001923 cyclic compounds Chemical class 0.000 claims description 7
- 239000003002 pH adjusting agent Substances 0.000 claims description 7
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 5
- 230000033001 locomotion Effects 0.000 claims description 5
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 4
- 239000001530 fumaric acid Substances 0.000 claims description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002274 desiccant Substances 0.000 abstract 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 37
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 37
- 239000000377 silicon dioxide Substances 0.000 description 31
- 235000012239 silicon dioxide Nutrition 0.000 description 31
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 30
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 239000011163 secondary particle Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 235000012431 wafers Nutrition 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 150000001735 carboxylic acids Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- CKKXWJDFFQPBQL-UAIGNFCESA-N diazanium;(z)-but-2-enedioate Chemical compound [NH4+].[NH4+].[O-]C(=O)\C=C/C([O-])=O CKKXWJDFFQPBQL-UAIGNFCESA-N 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- SIOXPEMLGUPBBT-UHFFFAOYSA-N Picolinic acid Natural products OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical group [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000000231 atomic layer deposition Methods 0.000 description 3
- 150000007514 bases Chemical class 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
- 150000001993 dienes Chemical class 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 2
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 2
- IHCCAYCGZOLTEU-UHFFFAOYSA-N 3-furoic acid Chemical compound OC(=O)C=1C=COC=1 IHCCAYCGZOLTEU-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VZFUCHSFHOYXIS-UHFFFAOYSA-N Cycloheptanecarboxylic acid Chemical compound OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-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
- WJJMNDUMQPNECX-UHFFFAOYSA-N Dipicolinic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- OKJIRPAQVSHGFK-UHFFFAOYSA-N N-acetylglycine Chemical compound CC(=O)NCC(O)=O OKJIRPAQVSHGFK-UHFFFAOYSA-N 0.000 description 2
- SEQKRHFRPICQDD-UHFFFAOYSA-N N-tris(hydroxymethyl)methylglycine Chemical compound OCC(CO)(CO)[NH2+]CC([O-])=O SEQKRHFRPICQDD-UHFFFAOYSA-N 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006061 abrasive grain Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- CVSVTCORWBXHQV-UHFFFAOYSA-N creatine Chemical compound NC(=[NH2+])N(C)CC([O-])=O CVSVTCORWBXHQV-UHFFFAOYSA-N 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- JBDSSBMEKXHSJF-UHFFFAOYSA-N cyclopentanecarboxylic acid Chemical compound OC(=O)C1CCCC1 JBDSSBMEKXHSJF-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- YMAWOPBAYDPSLA-UHFFFAOYSA-N glycylglycine Chemical compound [NH3+]CC(=O)NCC([O-])=O YMAWOPBAYDPSLA-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 150000002688 maleic acid derivatives Chemical class 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
- 229920000058 polyacrylate Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 125000004354 sulfur functional group Chemical group 0.000 description 2
- 125000005209 triethanolammonium group Chemical class 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- IUSXXDHQFMPZQX-UHFFFAOYSA-N (2-hydroxyphenyl) prop-2-enoate Chemical compound OC1=CC=CC=C1OC(=O)C=C IUSXXDHQFMPZQX-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- AYAUWVRAUCDBFR-ARJAWSKDSA-N (z)-4-oxo-4-propoxybut-2-enoic acid Chemical compound CCCOC(=O)\C=C/C(O)=O AYAUWVRAUCDBFR-ARJAWSKDSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- GWYPDXLJACEENP-UHFFFAOYSA-N 1,3-cycloheptadiene Chemical compound C1CC=CC=CC1 GWYPDXLJACEENP-UHFFFAOYSA-N 0.000 description 1
- IFXGRVXPSNHLNW-UHFFFAOYSA-N 1-ethenylcyclobutene Chemical compound C=CC1=CCC1 IFXGRVXPSNHLNW-UHFFFAOYSA-N 0.000 description 1
- IGCQXPZQGHULRC-UHFFFAOYSA-N 1-ethenylcycloheptene Chemical compound C=CC1=CCCCCC1 IGCQXPZQGHULRC-UHFFFAOYSA-N 0.000 description 1
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 1
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- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- BZFGKBQHQJVAHS-UHFFFAOYSA-N 2-(trifluoromethyl)pyridine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC(C(F)(F)F)=C1 BZFGKBQHQJVAHS-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- VRPJIFMKZZEXLR-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxycarbonylamino]acetic acid Chemical compound CC(C)(C)OC(=O)NCC(O)=O VRPJIFMKZZEXLR-UHFFFAOYSA-N 0.000 description 1
- CABMTIJINOIHOD-UHFFFAOYSA-N 2-[4-methyl-5-oxo-4-(propan-2-yl)-4,5-dihydro-1H-imidazol-2-yl]quinoline-3-carboxylic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC2=CC=CC=C2C=C1C(O)=O CABMTIJINOIHOD-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
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- C09K13/00—Etching, surface-brightening or pickling compositions
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Abstract
本發明係關於一種研磨劑,其特徵在於含有:包含單體(A)與單體(B)之共聚物之水溶性聚合物、氧化鈰粒子及水,且pH值為4以上且9以下;上述單體(A)包含選自不飽和二羧酸、其衍生物及其等之鹽中之至少1種,上述單體(B)為包含乙烯性雙鍵且不含酸性基之除單體(A)以外者。
Description
本發明係關於一種研磨劑與研磨方法、及研磨用添加液,尤其是關於半導體積體電路之製造中之用以化學機械研磨之研磨劑、使用該研磨劑之研磨方法、及用以製備研磨劑之研磨用添加液。
近年來,隨著半導體積體電路之高積體化或高功能化,用以半導體元件之微細化及高密度化之微細加工技術之開發取得較大之發展。自先前以來,於半導體積體電路裝置(以下,亦稱作半導體裝置)之製造中,為了防止層表面之凹凸(階差)超過微影之焦點深度而無法獲得充分之解像度等問題,採取使用化學機械研磨法(Chemical Mechanical Polishing:以下稱作CMP),使層間絕緣膜或嵌入配線等平坦化之措施。隨著元件之高精細化或微細化之要求變得嚴格,利用CMP之高平坦化之重要性亦逐漸增大。
又,近年來,於半導體裝置之製造中,為了推進半導體元件之更高度之微細化,引入元件分離寬度較小之利用淺溝槽之分離法(Shallow Trench Isolation:以下稱作STI)。
STI係藉由於矽基板上形成溝槽(trench),於溝槽內嵌入絕緣膜,而形成電氣絕緣之元件區域之手法。於STI中,首先,如圖1(a)所示,藉由氮化矽膜2等對矽基板1之元件區域進行遮蔽後,於矽基板1形成溝槽3,以填埋溝槽3之方式堆積二氧化矽膜4等絕緣膜。其次,利用CMP,一面保留作為凹部之溝槽3內之二氧化矽膜4,一面研磨去除作為凸部之氮化矽膜2上之二氧化矽膜4,藉此,如圖1(b)所示,獲得於溝槽3內嵌入有二氧化矽膜4之元件分離構造。
STI之CMP中,藉由提高二氧化矽膜與氮化矽膜之選擇比,可於氮化矽膜露出之時間點使研磨停止進行。如此,將氮化矽膜用作終止膜之研磨方法中,與通常之研磨方法相比,可獲得更平滑之面。並且,近年來之CMP技術中,上述選擇比之大小變得重要。
對應於此種要求特性,提議有改善研磨劑之研磨特性之方法。專利文獻1中揭示有含矽介電基材用研磨劑,其含有氧化鈰粒子等作為研磨粒,且含有聚丙烯酸或聚丙烯酸銨。
然而,專利文獻1中所示之研磨劑由於即便二氧化矽膜之研磨速度被確保有某程度上較高之值,氮化矽膜之研磨速度之抑制亦不充分,故二氧化矽膜與氮化矽膜之選擇比稱不上充分高。因此,獲得之基材之平坦性不充分。 [先前技術文獻] [專利文獻]
[專利文獻1]國際公開第2004/010487號
[發明所欲解決之問題]
本發明係為了解決上述問題而完成者,其目的在於提供一種研磨劑、及研磨方法,上述研磨劑例如於CMP、尤其STI中之包含氧化矽面之被研磨面之CMP中,可維持對如二氧化矽膜之氧化矽膜之充分高之研磨速度,並且將對氮化矽膜之研磨速度抑制得較低,提高二氧化矽膜與氮化矽膜之選擇比(意指二氧化矽膜之研磨速度與氮化矽膜之研磨速度之比。以下,亦僅稱作「選擇比」),並且達成良好之平坦性。 [解決問題之技術手段]
本發明之研磨劑之特徵在於含有:包含單體(A)與單體(B)之共聚物之水溶性聚合物、氧化鈰粒子及水,且pH值為4以上且9以下;上述單體(A)包含選自不飽和二羧酸、其衍生物及其等之鹽中之至少1種,上述單體(B)為包含乙烯性雙鍵且不含酸性基之除單體(A)以外者。
本發明之研磨方法係一面供給研磨劑一面使被研磨面與研磨墊接觸,藉由兩者之相對運動進行研磨者,其特徵在於使用本發明之研磨劑作為上述研磨劑,且對半導體基板之包含含有氧化矽之面之被研磨面進行研磨。
本發明之研磨用添加液之特徵在於:其係用以添加至氧化鈰粒子之分散液而製備研磨劑者,其含有包含單體(A)及單體(B)之共聚物之水溶性聚合物及水,且pH值為4以上且9以下;上述單體(A)包含選自不飽和二羧酸、其衍生物及其等之鹽中之至少1種,上述單體(B)為包含乙烯性雙鍵且不含酸性基之除單體(A)以外者。
再者,於本發明中,「被研磨面」係研磨對象物之被研磨之面,例如指表面。於本說明書中,於製造半導體裝置之過程中出現於半導體基板之中間階段之表面亦包含於「被研磨面」。於本發明中,「氧化矽」具體而言為二氧化矽,但並不限定於此,亦包含二氧化矽以外之矽氧化物。 [發明之效果]
根據本發明之研磨劑及研磨方法,例如於CMP、尤其STI中之包含氧化矽面之被研磨面之CMP中,可維持對氧化矽膜之充分高之研磨速度,並且將對氮化矽膜之研磨速度抑制得較低,達成氧化矽與氮化矽之高選擇比以及良好之平坦性。
以下,對本發明之實施形態進行說明。本發明並不限定於以下之實施形態,只要符合本發明之主旨,則其他實施形態亦能夠屬於本發明之範疇。
<研磨劑> 本發明之研磨劑之特徵在於含有:包含單體(A)及單體(B)之共聚物之水溶性聚合物、氧化鈰粒子及水,且pH值為4以上且9以下;上述單體(A)包含選自不飽和二羧酸、其衍生物及其等之鹽中之至少1種,單體(B)為包含乙烯性雙鍵且不包含酸性基之除單體(A)以外者。
於本說明書中,水溶性係指「於25℃下對於水100 g溶解10 mg以上」。於單體(A)及單體(B)之共聚物中,將基於單體(A)之單元稱作單元(A),將基於單體(B)之單元稱作單元(B)。將包含單體(A)與單體(B)之共聚物之水溶性聚合物僅稱作「水溶性聚合物」。於本說明書中,表示數值範圍之「~」包含上下限。於本說明書中,「(甲基)丙烯酸」為「甲基丙烯酸」與「丙烯酸」之總稱。
於將本發明之研磨劑用於例如STI中之包含氧化矽膜(例如二氧化矽膜)之被研磨面之CMP之情形時,具有對氧化矽膜之較高之研磨速度,並且對氮化矽膜之研磨速度充分低,可達成氧化矽膜與氮化矽膜之高選擇比。並且,可實現平坦性較高之研磨。
於本發明之研磨劑中,氧化鈰粒子作為研磨粒發揮功能。於本發明之研磨劑中,認為包含單體(A)與單體(B)之共聚物之水溶性聚合物溶解於水後pH值為4以上且9以下之範圍,如下所說明般以輔助研磨粒之作用之方式發揮功能,藉此本發明之研磨劑可發揮上述顯著之效果。
關於本發明之研磨劑發揮上述優異之研磨特性之機制雖不明確,但認為水溶性聚合物所具有之羧基藉由吸附於氧化鈰粒子之表面及包含氮化矽膜之被研磨面,而抑制對氮化矽膜之研磨速度。再者,認為即便羧基為鹽亦可與上述同樣地發揮功能。但,若羧基被衍生物化,則該功能將降低。因此,單體(A)較佳為至少包含羧基或羧基之鹽。
進而,構成水溶性聚合物之共聚物之單元(A)為親水性,單元(B)為疏水性。認為藉由共聚物具有疏水性部分與親水性部分,可維持對氧化矽膜之較快之研磨速度並且抑制對氮化矽膜之研磨速度,結果獲得較高之選擇比。
本發明之研磨劑除水溶性聚合物、氧化鈰粒子、水以外,於不損害本發明之效果之範圍內,亦可含有其他成分。以下,對本發明之研磨劑所含有之氧化鈰粒子、水溶性聚合物、水、其他成分等各成分及液體之pH值進行說明。
(氧化鈰粒子) 於本發明之研磨劑中,含有之氧化鈰粒子並無特別限定。例如可使用利用日本專利特開平11-12561號公報或日本專利特開2001-35818號公報中所記載之方法而製造之氧化鈰粒子。即,可使用以如下方法獲得之氧化鈰粒子:向硝酸鈰(IV)銨水溶液中加入鹼,製作氫氧化鈰凝膠,將其過濾、洗淨、焙燒而獲得;或將高純度之碳酸鈰粉碎後焙燒,進一步進行粉碎、分級而獲得。又,如日本專利特表2010-505735號中所記載,亦可使用於液體中使鈰(III)鹽進行化學氧化所獲得之氧化鈰粒子。
氧化鈰粒子之平均粒徑較佳為0.01 μm以上且0.5 μm以下,更佳為0.03 μm以上且0.3 μm以下。若氧化鈰粒子之平均粒徑超過0.5 μm,則有於被研磨面產生刮痕等研磨損傷之虞。又,若氧化鈰粒子之平均粒徑未達0.01 μm,則不僅有研磨速度降低之虞,而且由於每單位體積之表面積之比率較大,故易受到表面狀態之影響,根據pH值或添加劑之濃度等條件而容易產生凝集。
由於氧化鈰粒子於液體中以一次粒子凝集之凝集粒子(二次粒子)之形式存在,故將氧化鈰粒子之較佳粒徑設為以平均二次粒徑所表示者。即,顯示上述數值範圍之平均粒徑通常為平均二次粒徑。平均二次粒徑係使用分散於去離子水等分散介質中之分散液,利用雷射繞射-散射式等之粒度分佈計進行測定。
氧化鈰粒子之含有比率(濃度)相對於研磨劑之總質量較佳為0.05質量%以上且2.0質量%以下。特佳之範圍為0.15質量%以上且1.0質量%以下。於氧化鈰粒子之含有比率為0.05質量%以上且2.0質量%以下之情形時,可獲得對氧化矽膜充分高之研磨速度。又,研磨劑之黏度亦不會過高,操作性亦良好。
氧化鈰粒子亦可使用預先分散於介質中之狀態者(以下稱作氧化鈰粒子分散液)。又,為了獲得最佳之分散效果,亦可含有分散劑。作為介質,並無特別限定,可較佳地使用水。
(水) 本發明之研磨劑中,含有水作為使氧化鈰粒子分散且使下述水溶性聚合物等溶解之介質。水之種類並無特別限定,考慮到對水溶性聚合物等之影響、防止雜質之混入、對pH值等之影響,較佳為使用去離子水、超純水、離子交換水等。
(水溶性聚合物) 本發明之研磨劑中所含有之水溶性聚合物係為了提高對氧化矽膜之研磨速度、以及提高氧化矽膜與氮化矽膜之選擇比而含有。
水溶性聚合物包含以下之單體(A)及單體(B)之共聚物。單體(A)包含選自不飽和二羧酸、其衍生物及其等之鹽中之至少1種。單體(B)含有包含乙烯性雙鍵且不含酸性基之除單體(A)以外之化合物。
共聚物包含基於單體(A)之單元(A)與基於單體(B)之單元(B)各1種或2種以上,各單元可彼此無規鍵結,亦可嵌段鍵結。
單體(A)之不飽和二羧酸只要為一分子內具有2個羧基且具有乙烯性雙鍵之化合物,則可無特別限制地使用。不飽和二羧酸可為鏈式化合物,亦可為環式化合物,較佳為鏈式化合物。不飽和二羧酸中之乙烯性雙鍵之個數並無限制,較佳為1~2,更佳為1。不飽和二羧酸之除羧基外之碳數較佳為2~5,更佳為2~3,特佳為2。
作為不飽和二羧酸,具體而言,可列舉:順丁烯二酸、反丁烯二酸、伊康酸、檸康酸、中康酸、2-烯丙基丙二酸、亞異丙基琥珀酸等。該等之中,較佳為選自順丁烯二酸、反丁烯二酸及伊康酸中之至少1種,就聚合性之觀點而言,特佳為順丁烯二酸。
單體(A)亦可為不飽和二羧酸之衍生物、不飽和二羧酸之鹽、及不飽和二羧酸之衍生物之鹽。不飽和二羧酸之衍生物之鹽係指將不飽和二羧酸之羧基之一者設為衍生物且另一者成為鹽之化合物。
作為不飽和二羧酸之鹽,可列舉鹼金屬鹽、胺鹽。作為具體之鹽,可列舉鈉鹽、鉀鹽、銨鹽、單乙醇銨鹽、二乙醇銨鹽、三乙醇銨鹽,就可不考慮金屬雜質之混入之方面而言,更佳為銨鹽。
作為不飽和二羧酸之衍生物,可列舉酸酐、酯衍生物、醯胺衍生物,作為衍生物,較佳為酯衍生物。不飽和二羧酸之酯或醯胺亦可為不飽和二羧酸之羧基之兩者或一者被酯化或醯胺化者。
作為不飽和二羧酸之酯衍生物,例如為不飽和二羧酸之羧基(-C(=O)-OH)之至少一者成為-C(=O)-O-R1
(R1
為一價取代基)之化合物。R1
較佳為於碳數1~50之碳-碳原子間可具有氧原子之飽和烴基。R1
更佳為於碳數2~30之碳-碳原子間、進而更佳為於碳數5~20之碳-碳原子間可具有氧原子之飽和烴基。飽和烴基可為直鏈、支鏈或環狀,亦可為包含環狀結構之直鏈或支鏈。
作為不飽和二羧酸之醯胺衍生物,例如為不飽和二羧酸之羧基(-C(=O)-OH)之至少一者成為-C(=O)-NR2
R3
(R2
、R3
獨立為氫原子或一價取代基)之化合物。於R2
、R3
為一價取代基之情形時,具體而言,可列舉與上述R1
相同之基。關於較佳之態樣亦與R1
相同。
單體(A)包含選自不飽和二羧酸、其衍生物及其等之鹽中之至少1種。於單體(A)包含該等2種以上之情形時,可為不飽和二羧酸之種類不同之組合,亦可為不飽和二羧酸相同之不飽和二羧酸與其衍生物及/或其等之鹽之組合。
單體(A)較佳為包含不飽和二羧酸之鹽。即,共聚物較佳為基於單體(A)之單元(A)具有羧基之鹽。若單體(A)包含不飽和二羧酸之鹽,則可提高共聚物之水溶性。
單體(A)較佳為包含選自不飽和二羧酸之至少一部分被酯化之酯衍生物及該鹽中之至少1種。再者,該情形時之鹽為不飽和二羧酸之一部分被酯化之酯衍生物之鹽。藉由單體(A)包含不飽和二羧酸之酯衍生物,本發明之研磨劑可進一步提高選擇比,因此,單體(A)特佳為不飽和二羧酸之一部分被酯化之酯衍生物之鹽。
於上述較佳之態樣中,作為單體(A),可列舉包含不飽和二羧酸之羧基之一者或兩者被酯化之酯衍生物、不飽和二羧酸之一者被酯化且另一者成為鹽之化合物及該等之混合物之態樣。又,上述中,於單體(A)為鹽之情形時,單體(A)亦可為包含不飽和二羧酸之至少一部分被酯化之酯衍生物與不飽和二羧酸之鹽之組合之態樣。
再者,於本發明中,單體(A)包含不飽和二羧酸之鹽係指於單體(A)與單體(B)之共聚物中,單元(A)包含羧基之鹽。即,單體(A)包含不飽和二羧酸之鹽包括於製造上述共聚物時單體(A)為鹽之情形,以及獲得共聚物後,將單元(A)之羧基設為鹽之情形之兩者。
於單體(A)中,若例示適宜之順丁烯二酸作為不飽和二羧酸,則單體(A)較佳為包含選自順丁烯二酸單酯、順丁烯二酸二酯及順丁烯二酸單酯之鹽中之至少1種。於該情形時,單體(A)可包含順丁烯二酸,亦可包含順丁烯二酸鹽。單體(A)更佳為包含順丁烯二酸單酯之鹽或將順丁烯二酸酯與順丁烯二酸鹽進行組合而包含,特佳為包含順丁烯二酸單酯之鹽。
於將單體(A)作為整體之情形時,即,於共聚物中之單元(A)中,經酯化之羧基與羧基之鹽之比率較佳為1:9~9:1,特佳為5:5。再者,於單體(A)中,於羧基形成鹽之情形時,製造上,單體(A)中不存在羧基(-COOH)。
單體(B)為包含乙烯性雙鍵且不含酸性基之除單體(A)以外之化合物。單體(B)可為鏈式化合物,亦可為包含環結構之環式化合物,較佳為包含環結構之環式化合物。若單體(B)包含環結構,則可提高獲得之研磨劑之保存穩定性。
於單體(B)包含環結構之情形時,於共聚物中,單元(B)較佳為於側鏈具有環結構。於該情形時,環為脂肪族環或芳香族環,較佳為五員環或六員環。乙烯性雙鍵之個數並無特別限制,可列舉1~5,較佳為1~2,特佳為1。又,於單體(B)包含環結構之情形時,環亦可為於骨架上包含碳原子以外之元素、例如氧原子、氮原子之雜環,鍵結於環上之氫原子亦可被取代為酸性基以外之取代基。作為取代基,可列舉碳數1~30之烴基、氧基(-O-R)、側氧基(=O)、羰基(-CO-R)、胺基(-NH-R)、亞胺基(=N-R)、偶氮基(-N=N-R)、重氮基(-N≡N-R)、鹵基、硫基(-S-R)、膦基等。此處,R為一價有機基。
於單體(B)為鏈式化合物之情形時,乙烯性雙鍵之個數無特別限制,可列舉1~5,較佳為1~2,特佳為1。鏈式化合物為直鏈或支鏈,碳數無特別限制,可列舉2~30,較佳為2~10。
作為包含環結構之單體(B),具體而言可列舉:環丁烯、環戊烯、環己烯、環庚烯、環辛烯等單環環狀烯烴或該等之衍生物,環戊二烯、環己二烯、環庚二烯、環辛二烯等環狀共軛二烯或該等之衍生物,降𦯉烯、二環戊二烯、三環癸烯、四環十二烯、六環十七烯等多環狀烯烴或該等之衍生物,乙烯基環丁烷、乙烯基環丁烯、乙烯基環戊烷、乙烯基環戊烯、乙烯基環己烷、乙烯基環己烯、乙烯基環庚烷、乙烯基環庚烯、乙烯基環辛烷、乙烯基環辛烯、N-乙烯基吡咯啶酮、N-乙烯基咔唑、4-乙烯基吡啶等乙烯基脂環式烴或該等之衍生物,苯乙烯、甲基苯乙烯、乙烯基甲苯、對第三丁基苯乙烯、氯甲基苯乙烯、鄰(或對、間)羥基苯乙烯、丙烯酸鄰(或對、間)羥基苯酯等乙烯基芳香族系單體或該等之衍生物。
作為鏈式化合物之單體(B),具體而言,可列舉:乙烯、丙烯、丁烯、戊烯、己烯、庚烯、辛烯、壬烯、癸烯、異丙烯、異丁烯、異戊烯、異己烯、異庚烯、異辛烯、異壬烯、異癸烯等烯烴或該等之衍生物,丁二烯、1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯、1,3-戊二烯等脂肪族共軛二烯或該等之衍生物,(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸羥基丙酯等(甲基)丙烯酸酯或該等之衍生物,丙烯酸β-羥基乙酯、丙烯酸β-羥基丙酯及甲基丙烯酸β-羥基乙酯等乙烯性不飽和羧酸羥基烷基酯或其衍生物,丙烯酸縮水甘油酯及甲基丙烯酸縮水甘油酯等不飽和羧酸縮水甘油酯或其衍生物,丙烯醛及烯丙醇等乙烯系化合物或其衍生物,丙烯腈、甲基丙烯腈等乙烯性不飽和腈或其衍生物,丙烯醯胺、甲基丙烯醯胺、N-羥甲基丙烯醯胺及二丙酮丙烯醯胺等乙烯性不飽和羧醯胺及其衍生物。
該等之中,作為單體(B),較佳為苯乙烯、N-乙烯基吡咯啶酮、4-乙烯基吡啶、庚烯、辛烯、壬烯、異丁烯,更佳為苯乙烯、N-乙烯基吡咯啶酮、4-乙烯基吡啶,特佳為苯乙烯。
再者,單體(B)可為1種,亦可為2種以上。例如,於單體(B)包含苯乙烯之情形時,亦可包含N-乙烯基吡咯啶酮、庚烯、辛烯、壬烯、異丁烯等除苯乙烯以外之單體。於該情形時,苯乙烯之含有比率相對於單體(B)整體較佳為50~100莫耳%,更佳為70~100莫耳%,特佳為100莫耳%。
對共聚物中之單體(A)與單體(B)分別進行說明。單體(A)與單體(B)可自上述分別適當地選擇1種或2種以上進行組合。較佳之組合為上述中分別較佳之單體(A)與單體(B)之組合。於用於本發明之研磨劑之共聚物中,特佳為單體(A)中之不飽和二羧酸包含順丁烯二酸,且單體(B)包含苯乙烯之組合。
於共聚物中,單體(A)與單體(B)之比率、即單元(A)與單元(B)之比率無特別限制。若考慮到單元(A)之親水性與單元(B)之疏水性之平衡,則作為單元(A)與單元(B)之莫耳比,可列舉10:90~90:10,該莫耳比較佳為20:80~80:20,進而較佳為40:60~60:40。
共聚物之重量平均分子量較佳為500以上且100萬以下,更佳為1000以上且2萬以下,進而較佳為2000以上且1萬以下。若共聚物之重量平均分子量為500以上,則可穩定地確保共聚物吸附於氧化鈰粒子之表面及包含氮化矽膜之被研磨面之狀態。若共聚物之重量平均分子量為100萬以下,則操作性等良好。再者,本說明書中之重量平均分子量(以下亦有時以「Mw」表示)只要無特別說明,則係藉由凝膠滲透層析法(GPC)所測得之重量平均分子量。
水溶性聚合物包含單體(A)與單體(B)之共聚物之1種或2種以上。水溶性聚合物中之酸值及重量平均分子量較佳為與上述共聚物之酸值及重量平均分子量為相同之範圍。
就獲得對氧化矽膜之較高之研磨速度並且獲得較高之選擇比之觀點而言,水溶性聚合物之含有比率(濃度)相對於研磨劑之總質量較佳為0.001質量%以上且10.0質量%以下,更佳為0.01質量%以上且5.0質量%以下。又,於水溶性聚合物之含有比率(濃度)相對於研磨劑之總質量為0.05質量%以上且2.0質量%以下之情形時,能夠獲得對氧化矽膜充分高之研磨速度,並且能夠獲得更高之選擇比,故進而較佳。
(pH值) 本發明之研磨劑之pH值為4以上且9以下。於研磨劑之pH值為9以下之情形時,能夠充分地獲得氮化矽膜之研磨速度之抑制、及選擇比提高之效果。又,於研磨劑之pH值為4以上之情形時,能夠獲得氧化矽膜之研磨速度之提高。研磨劑之pH值更佳為5以上且9以下,特佳為6以上且8以下。
為了將pH值設為特定之值,本發明之研磨劑亦可含有pH值調整劑。作為pH值調整劑,較佳為酸,能夠使用各種無機酸或有機酸、或其等之鹽。作為無機酸,並無特別限定,例如可列舉硝酸、硫酸、鹽酸、磷酸。作為有機酸,並無特別限定,例如可列舉羧酸、磺酸、磷酸等。其中較佳為羧酸。羧酸可為任意之合適之羧酸,將更佳之羧酸例示於以下。
具有含氮雜環基之羧酸(單羧酸、多羧酸):2-吡啶羧酸、3-吡啶羧酸、4-吡啶羧酸、2,3-吡啶二羧酸、2,4-吡啶二羧酸、2,5-吡啶二羧酸、2,6-吡啶二羧酸、3,4-吡啶二羧酸、3,5-吡啶二羧酸、吡𠯤羧酸、2,3-吡𠯤二羧酸、2-喹啉羧酸、焦麩胺酸、吡啶甲酸、DL-哌啶甲酸。
具有氮以外之環狀化合物之羧酸:2-糠酸、3-糠酸、四氫呋喃-2-羧酸、四氫呋喃-2,3,4,5-四羧酸。
具有胺基之羧酸(胺基酸等):丙胺酸、甘胺酸、甘胺醯甘胺酸、胺基丁酸、N-乙醯基甘胺酸、N,N-二(2-羥基乙基)甘胺酸、N-(第三丁氧基羰基)甘胺酸、脯胺酸、反式4-羥基-L-脯胺酸、苯丙胺酸、肌胺酸、脲乙酸、肌酸、N-[三(羥基甲基)甲基]甘胺酸、麩胺酸、天冬胺酸。
具有羥基之羧酸(羥基羧酸等):乳酸、蘋果酸、檸檬酸、酒石酸、乙醇酸、葡萄糖酸、水楊酸、2-羥基異丁酸、甘油酸、2,2-雙(羥基甲基)丙酸、2,2-雙(羥基甲基)丁酸。
具有酮基之羧酸(酮酸):丙酮酸、乙醯乙酸、乙醯丙酸。
環狀羧酸:環戊烷羧酸、環己烷羧酸、環庚烷羧酸、環己基羧酸。
上述以外之多羧酸:草酸、丙二酸、琥珀酸、反丁烯二酸、順丁烯二酸、戊二酸、己二酸、鄰苯二甲酸。
又,上述無機酸或有機酸亦可以鹽之形式使用。作為該等之鹽,可使用鹼金屬鹽或胺鹽等。具體而言可列舉鈉鹽、鉀鹽、銨鹽、單乙醇銨鹽、二乙醇銨鹽、三乙醇銨鹽。
又,於本發明之研磨劑中亦可添加各種鹼性化合物作為pH值調整劑。鹼性化合物較佳為水溶性,但並無特別限定。作為鹼性化合物,例如可使用氨、氫氧化鉀、氫氧化四甲基銨(以下稱作TMAH)或氫氧化四乙基銨等氫氧化四級銨,單乙醇胺(以下稱作MEA)、乙二胺等有機胺等。
本發明之研磨劑除上述成分以外,還可含有防凝集劑或分散劑。
分散劑係為了使氧化鈰粒子穩定地分散於去離子水等分散介質中而含有者。作為分散劑,可列舉陰離子性、陽離子性、非離子性、兩性之界面活性劑,或陰離子性、陽離子性、非離子性、兩性之高分子化合物,可含有該等之1種或2種以上。
又,於本發明之研磨劑中可視需要適當含有潤滑劑、黏性賦予劑或黏度調節劑、防腐劑等。
為了保管或運輸之便利性,本發明之研磨劑可分別準備氧化鈰粒子之分散液(以下稱作分散液)與水中溶解有水溶性聚合物之水溶液(研磨用添加液)之二液,於使用時進行混合。
<研磨用添加液> 本發明之研磨用添加液之特徵在於:其係用以添加至氧化鈰粒子之分散液而製備研磨劑者,其含有包含單體(A)及單體(B)之共聚物之水溶性聚合物及水,且pH值為4以上且9以下;上述單體(A)包含選自不飽和二羧酸、其衍生物及其等之鹽中之至少1種,上述單體(B)為包含乙烯性雙鍵且不含酸性基之除單體(A)以外者。於研磨劑之製備中,藉由採取使用該研磨用添加液並添加至氧化鈰粒子之分散液之方法,可提高研磨劑之保管或運輸之便利性。
於本發明之研磨用添加液中,含有之水溶性聚合物、水之各成分及液體之pH值與關於上述研磨劑中含有之各成分及液體之pH值之記載相同。
於本發明之研磨用添加液中,水溶性聚合物之含有比率(濃度)較佳為添加液整體之0.001質量%以上且30質量%以下,更佳為0.01質量%以上且20質量%以下,進而較佳為0.1質量%以上且10質量%以下。
於添加有此種添加液之氧化鈰粒子之分散液中,液中之氧化鈰粒子之含有比率較佳為0.2質量%以上且40質量%以下,更佳為1質量%以上且20質量%以下,進而較佳為5質量%以上且10質量%以下。
藉由將本發明之研磨用添加液添加至氧化鈰粒子之分散液中,可獲得能夠維持氧化矽膜之較高之研磨速度並且將氮化矽膜之研磨速度抑制得較低,達成高選擇比與平坦性之研磨劑。
再者,於分成氧化鈰粒子之分散液與本發明之研磨用添加液之二液,將該等進行混合以製備研磨劑之情形時,可預先將分散液中之氧化鈰粒子之濃度及研磨用添加液中之水溶性聚合物之濃度濃縮成研磨劑使用時之2倍~100倍,於使用時進行稀釋以製成特定之濃度。更具體而言,例如,於將分散液中之氧化鈰粒子之濃度與添加液中之水溶性聚合物之濃度均濃縮成10倍之情形時,以分散液10質量份、研磨用添加液10質量份、水80質量份之比率進行混合並攪拌,作為研磨劑使用。
<研磨劑之製備方法> 為了製備本發明之研磨劑,可使用如下方法:向使上述氧化鈰粒子分散於去離子水或離子交換水等水而得之分散液中加入水溶性聚合物並進行混合。混合後,使用攪拌機等攪拌特定時間,藉此可獲得均一之研磨劑。又,混合後,亦可使用超音波分散機,獲得更良好之分散狀態。
本發明之研磨劑無需作為預先將構成之研磨成分全部混合者供給至研磨場所。於供給至研磨場所時,亦可將研磨成分混合後成為研磨劑之組成。
為了保管或運輸之便利性,本發明之研磨劑亦可如上所述分別準備氧化鈰粒子之分散液與研磨用添加液之二液,於使用時進行混合。分成該分散液與研磨用添加液之二液,將該等進行混合以製備研磨劑之方法如上所述。
<研磨方法> 本發明之實施形態之研磨方法係一面供給上述研磨劑一面使研磨對象物之被研磨面與研磨墊接觸,藉由兩者之相對運動進行研磨之方法。此處,待研磨之被研磨面例如為半導體基板之包含含有二氧化矽之面之表面。作為半導體基板,可列舉上述STI用基板作為較佳例。於半導體裝置之製造中,本發明之研磨劑對用以使多層配線間之層間絕緣膜平坦化之研磨亦有效。
作為STI用基板中之二氧化矽膜,可列舉以四乙氧基矽烷(TEOS)為原料並利用電漿CVD(Chemical Vapor Deposition,化學氣相沈積)法成膜之所謂PE-TEOS(Plasma Enhanced Tetraethoxysilane,電漿加強四乙氧基矽烷)膜。又,作為二氧化矽膜,可列舉利用高密度電漿CVD法成膜之所謂HDP(High Density Plasma,高密度電漿)膜。又,亦可使用利用其他CVD法成膜之HARP(High-gain Avalanche Rushing Amorphous Photoconductor,高倍增崩潰式放大非晶質光電導元件)膜或FCVD(Flowable Chemical Vapor Deposition,流動性化學氣相沈積)膜、利用旋轉塗佈製膜之SOD(Spin on Dielectric,旋塗式介電質)膜。作為氮化矽膜,可列舉以矽烷或二氯矽烷及氨為原料,利用低壓CVD法或電漿CVD法而成膜者,或藉由ALD(Atomic Layer Deposition,原子層沈積)法而成膜者。
本發明之實施形態之研磨方法可使用公知之研磨裝置。圖2係表示於本發明之研磨方法中能夠使用之研磨裝置之一例之圖。
該研磨裝置20具備保持如STI基板之半導體基板21之研磨頭22、研磨壓盤23、貼附於研磨壓盤23之表面之研磨墊24、以及向研磨墊24供給研磨劑25之研磨劑供給配管26。該研磨裝置以如下方式構成:一面自研磨劑供給配管26供給研磨劑25,一面使保持於研磨頭22之半導體基板21之被研磨面與研磨墊24接觸,使研磨頭22與研磨壓盤23相對地進行旋轉運動以進行研磨。再者,用於本發明之實施形態之研磨裝置不限定於此種構造者。
研磨頭22不僅作旋轉運動,亦可作直線運動。又,研磨壓盤23及研磨墊24亦可為與半導體基板21相同程度或其以下之大小。於該情形時,較佳為藉由使研磨頭22與研磨壓盤23相對地進行移動,可對半導體基板21之被研磨面之整個面進行研磨。進而,研磨壓盤23及研磨墊24亦可不作旋轉運動,例如亦可以皮帶式於一方向上移動。
此種研磨裝置20之研磨條件無特別限制,可藉由對研磨頭22施加負載而壓抵至研磨墊24以進一步提高研磨壓力,提高研磨速度。研磨壓力較佳為0.5~50 kPa左右,就研磨速度下之半導體基板21之被研磨面內之均一性、平坦性、防止刮痕等研磨缺陷之觀點而言,更佳為3~40 kPa左右。研磨壓盤23及研磨頭22之轉數較佳為50~500 rpm左右,但不限定於此。又,關於研磨劑25之供給量,根據研磨劑之組成或上述各研磨條件等進行適當調整。
作為研磨墊24,可使用包含不織布、發泡聚胺基甲酸酯、多孔質樹脂、非多孔質樹脂等者。為了促進研磨劑25對研磨墊24之供給、或使研磨劑25於研磨墊24上積存一定量,亦可對研磨墊24之表面實施格子狀、同心圓狀、螺旋狀等之溝槽加工。又,視需要,亦可使墊調整器與研磨墊24之表面接觸,一面調整研磨墊24之表面一面進行研磨。
根據本發明之研磨方法,於半導體裝置之製造中之層間絕緣膜之平坦化或STI用絕緣膜之平坦化等CMP處理中,可以較高之研磨速度對包含氧化矽(例如二氧化矽)之被研磨面進行研磨,並且可實現氧化矽膜與氮化矽膜之高選擇比,達成高平坦性。 [實施例]
以下,藉由實施例及比較例更具體地說明本發明,但本發明並不限定於該等實施例。於以下之例中,只要未特別說明,則「%」指質量%。又,特性值藉由下述方法測定並進行評價。例1~14為實施例,例15~18為比較例。
[pH值] pH值係使用東亞DKK公司製造之pH計HM-30R而測得。
[平均二次粒徑] 平均二次粒徑係使用雷射散射-繞射式粒度分佈測定裝置(堀場製作所製造,裝置名:LA-920)而測得。
[研磨特性] 研磨特性係使用全自動CMP裝置FREX300(荏原製作所製造)進行評價。研磨墊使用2層墊(Rodel公司製造,IC-1570),研磨墊之調整使用金剛石墊調整器(Diamond Pad Conditioner)(3M公司製造,商品名:A165)。研磨條件係將研磨壓力設為21 kPa,將研磨壓盤之轉數設為100 rpm,將研磨頭之轉數設為102 rpm。又,只要未特別說明,則研磨劑之供給速度設為250毫升/分鐘。
作為用以評價研磨速度及選擇比之研磨對象物(被研磨物),使用於12英吋矽基盤上以四乙氧基矽烷或甲矽烷為原料藉由電漿CVD成膜有二氧化矽膜之附二氧化矽膜之晶圓。又,使用同樣地藉由CVD成膜有氮化矽膜之附氮化矽膜之晶圓(以下將該等稱作「毯覆式晶圓」)。
再者,成膜於毯覆式晶圓上之二氧化矽膜與氮化矽膜之膜厚之測定係使用SCREEN公司之膜厚計VM-3210。藉由求出毯覆式晶圓於研磨前之膜厚與研磨1分鐘後之膜厚之差,分別算出二氧化矽膜及氮化矽膜之研磨速度。將自基板面內49處之研磨速度獲得之研磨速度之平均值(nm/min)作為研磨速度之評價指標。又,算出二氧化矽膜之研磨速度與氮化矽膜之研磨速度之比率(二氧化矽膜之研磨速度/氮化矽膜之研磨速度)作為選擇比。
關於表1中歸納之結果,使用作為實施例之例1~14及作為比較例之例15~18證實:藉由使用本發明之研磨劑對毯覆式晶圓進行研磨,可獲得對二氧化矽之較高之研磨速度,且具有二氧化矽相對於氮化矽之極高之選擇比。
(水溶性聚合物及比較例之水溶性聚合物) 將用於以下各例之包含單體(A)與單體(B)之共聚物之水溶性聚合物(實施例用水溶性聚合物)及比較例用水溶性聚合物之分子構成示於以下。
(實施例用水溶性聚合物) 水溶性聚合物A;作為單體(A)之順丁烯二酸烷基(其中,烷基為碳數19-20之直鏈烷基)酯銨鹽與作為單體(B)之苯乙烯之50:50(莫耳比)共聚物。Mw為3000。 水溶性聚合物B;作為單體(A)之順丁烯二酸2-丁氧基乙酯銨鹽與作為單體(B)之苯乙烯之50:50(莫耳比)共聚物。Mw為7000。
水溶性聚合物C;作為單體(A)之順丁烯二酸銨鹽與作為單體(B)之辛烯(C8
H16
)之共聚物。 水溶性聚合物D;作為單體(A)之順丁烯二酸銨鹽與作為單體(B)之異丁烯之共聚物。Mw為55000-65000。 水溶性聚合物E;作為單體(A)之順丁烯二酸銨鹽與作為單體(B)之苯乙烯之共聚物。Mw為600,000。 水溶性聚合物F;作為單體(A)之順丁烯二酸1-丙酯(假定加成物)銨鹽與作為單體(B)之苯乙烯之33:66(莫耳比)共聚物。Mw為9000。 上述中,順丁烯二酸酯銨鹽中之酯與銨鹽之比率於任一單體(A)中均為1:1。
(比較例用水溶性聚合物) 水溶性聚合物G;丙烯酸銨鹽之均聚物。Mw為5000。 水溶性聚合物H;順丁烯二酸之均聚物。
[例1] 將平均粒徑不同之2種氧化鈰粒子與作為分散劑之分子量5000之聚丙烯酸銨以100:0.7之質量比加入至去離子水中,一面攪拌一面進行混合,實施超音波分散、過濾,製備氧化鈰粒子之濃度為10%、分散劑之濃度為0.07%之氧化鈰粒子分散液。再者,氧化鈰粒子之平均二次粒徑為0.11 μm者(以下表示為氧化鈰分散液A)與0.18 μm者(以下表示為氧化鈰分散液B)。
其次,向去離子水中以相對於研磨劑之總量,濃度成為0.005%之方式加入水溶性聚合物A,並以相對於研磨劑之總量,氧化鈰粒子之濃度成為0.25%之方式加入上述氧化鈰分散液A,進而加入硝酸將pH值調整為7.0,獲得研磨劑(1)。
[例2~8、10、12~14] 將與例1相同之氧化鈰分散液A與水溶性聚合物以分別成為表1所示之濃度之方式添加至去離子水,並進行攪拌,進而加入pH值調整劑,調整為表1所示之pH值,獲得研磨劑(2)~(8)、(10)、(12)~(14)。
[例9、例11] 將氧化鈰粒子分散液B與水溶性聚合物以分別成為表1所示之濃度之方式添加至去離子水,並進行攪拌,進而加入pH值調整劑,調整為表1所示之pH值,獲得研磨劑(9)、(11)。
[例15] 將與例1相同之氧化鈰分散液A以成為表1所示之濃度之方式添加至去離子水,並進行攪拌,不加入水溶性聚合物而獲得研磨劑(15)。
[例16~18] 將與例1相同之氧化鈰分散液A與水溶性聚合物以分別成為表1所示之濃度之方式添加至去離子水,並進行攪拌,進而加入pH值調整劑,調整為表1所示之pH值,獲得研磨劑(16)~(18)。
分別利用上述方法對例1~18所得之研磨劑(1)~(18)之研磨特性(二氧化矽膜之研磨速度、氮化矽膜之研磨速度及選擇比)進行測定。再者,研磨特性之測定中,使用毯覆式晶圓作為研磨對象物(被研磨物)。
[保存穩定性] 向去離子水中以相對於研磨劑之總量,濃度成為0.2%之方式加入下述表2所示之水溶性聚合物,並以相對於研磨劑之總量,氧化鈰粒子之濃度成為1.0%之方式加入上述氧化鈰分散液A,進而添加硝酸將pH值調整為指定之pH值而獲得研磨劑,將所獲得之研磨劑於25℃左右之室溫下保存,確認pH值之經時變化,設為保存穩定性之試驗。將結果示於表2。與製作當天相比,將研磨劑之pH值至7天後仍無變化者評價為“○”,將pH值變化0.5以上者評價為“△”。
自表1及表2,可知以下內容。即,可知藉由使用例1~14之研磨劑(1)~(14)進行研磨,可獲得對二氧化矽膜之較高之研磨速度,且二氧化矽膜與氮化矽膜之選擇比變高,上述例1~14之研磨劑(1)~(14)含有氧化鈰粒子、包含單體(A)及單體(B)之共聚物之水溶性聚合物及水,且pH值為4以上且9以下;上述單體(A)包含選自不飽和二羧酸、其衍生物及其等之鹽中之至少1種,上述單體(B)為包含乙烯性雙鍵且不含酸性基之除單體(A)以外者。於單體(A)為酯衍生物之情形時,可提高選擇比。於單體(B)為環狀結構之情形時,可提高保存穩定性。
相對於此,可知關於不含作為單體(A)與單體(B)之共聚物之水溶性聚合物的研磨劑(15),二氧化矽膜與氮化矽膜之選擇比與使用作為實施例之例1~14之研磨劑(1)~(14)之情形相比降低。
又,可知關於使用結構相近但並非單體(A)與單體(B)之共聚物之水溶性聚合物的研磨劑(16)以及研磨劑(17),二氧化矽膜與氮化矽膜之選擇比與使用例1~14之研磨劑(1)~(14)之情形相比亦降低。進而,可知於使用包含作為單體(A)與單體(B)之共聚物之水溶性聚合物,但pH值為10以上的研磨劑(18)之情形時,二氧化矽膜與氮化矽膜之選擇比與使用例1~14之研磨劑(1)~(14)之情形相比亦降低。
本申請案係基於2017年11月8日提出申請之日本專利申請案2017-215520者,將其內容作為參照引用於本說明中。 [產業上之可利用性]
根據本發明,例如於包含含有氧化矽之面之被研磨面之CMP中,可維持對氧化矽膜之充分高之研磨速度,並且將氮化矽膜之研磨速度抑制得較低,達成氧化矽膜與氮化矽膜之高選擇比。因此,本發明之研磨劑及研磨方法適用於半導體裝置製造中之STI用絕緣膜之平坦化。
1‧‧‧矽基板2‧‧‧氮化矽膜3‧‧‧溝槽4‧‧‧二氧化矽膜20‧‧‧研磨裝置21‧‧‧半導體基板22‧‧‧研磨頭23‧‧‧研磨壓盤24‧‧‧研磨墊25‧‧‧研磨劑26‧‧‧研磨劑供給配管
圖1(a)及1(b)係表示於STI中,藉由CMP進行研磨之方法之半導體基板之剖視圖。 圖2係表示於本發明之研磨方法中能夠使用之研磨裝置之一例之圖。
1‧‧‧矽基板
2‧‧‧氮化矽膜
3‧‧‧溝槽
4‧‧‧二氧化矽膜
Claims (12)
- 一種研磨劑,其特徵在於含有:包含單體(A)與單體(B)之共聚物之水溶性聚合物、氧化鈰粒子及水,上述單體(B)為除單體(A)以外者;上述單體(A)包含選自不飽和二羧酸之至少一部分被酯化之酯衍生物及其鹽中之至少1種,上述單體(B)為碳數2~30之鏈式化合物、或包含環結構之環式化合物,上述單體(B)包含乙烯性雙鍵且不含酸性基,上述研磨劑中之上述水溶性聚合物之含量為0.001質量%以上且10.0質量%以下,上述研磨劑中之上述氧化鈰粒子之含量為0.05質量%以上且2.0質量%以下,且上述研磨劑之pH值為4以上且9以下。
- 如請求項1之研磨劑,其中上述不飽和二羧酸包含選自順丁烯二酸、伊康酸及反丁烯二酸中之至少1種。
- 如請求項1或2之研磨劑,其中上述單體(B)包含含有五員環或六員環之環式化合物。
- 如請求項1或2之研磨劑,其中上述研磨劑進而包含pH值調整劑。
- 如請求項4之研磨劑,其中上述pH值調整劑為酸。
- 如請求項1或2之研磨劑,其中上述共聚物之基於上述單體(A)之單元係具有羧基之鹽。
- 如請求項1或2之研磨劑,其中上述單體(B)包含選自苯乙烯、N-乙烯基吡咯啶酮及4-乙烯基吡啶中之至少1種。
- 如請求項7之研磨劑,其中上述不飽和二羧酸包含順丁烯二酸,且上述單體(B)包含苯乙烯。
- 如請求項7之研磨劑,其中上述單體(A)包含選自順丁烯二酸之至少一部分被酯化之酯衍生物及其鹽中之至少1種。
- 如請求項1或2之研磨劑,其中上述研磨劑中之上述水溶性聚合物之含量為0.01質量%以上且5.0質量%以下。
- 一種研磨方法,其係一面供給研磨劑一面使被研磨面與研磨墊接觸,藉由兩者之相對運動進行研磨者,其特徵在於:使用如請求項1至10中任一項之研磨劑作為上述研磨劑,對半導體基板之包含含有氧化矽之面之被研磨面進行研磨。
- 一種研磨用添加液,其特徵在於:其係用以添加至氧化鈰粒子之分 散液而製備研磨劑者,其含有包含單體(A)及單體(B)之共聚物之水溶性聚合物及水,上述單體(B)為除單體(A)以外者;上述單體(A)包含選自不飽和二羧酸之至少一部分被酯化之酯衍生物及其鹽中之至少1種,上述單體(B)為碳數2~30之鏈式化合物、或包含環結構之環式化合物,上述單體(B)包含乙烯性雙鍵且不含酸性基,上述添加液中之上述水溶性聚合物之含量為0.001質量%以上且10.0質量%以下,且上述研磨用添加液之pH值為4以上且9以下。
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