WO2023013683A1 - Cmp用研磨液、cmp用研磨液セット及び研磨方法 - Google Patents
Cmp用研磨液、cmp用研磨液セット及び研磨方法 Download PDFInfo
- Publication number
- WO2023013683A1 WO2023013683A1 PCT/JP2022/029820 JP2022029820W WO2023013683A1 WO 2023013683 A1 WO2023013683 A1 WO 2023013683A1 JP 2022029820 W JP2022029820 W JP 2022029820W WO 2023013683 A1 WO2023013683 A1 WO 2023013683A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mass
- polishing
- less
- liquid
- polishing liquid
- Prior art date
Links
- 238000005498 polishing Methods 0.000 title claims abstract description 358
- 239000007788 liquid Substances 0.000 title claims abstract description 228
- 238000000034 method Methods 0.000 title claims description 82
- 239000006061 abrasive grain Substances 0.000 claims abstract description 95
- 239000000654 additive Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 239000002245 particle Substances 0.000 claims abstract description 34
- 230000000996 additive effect Effects 0.000 claims abstract description 31
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 24
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims abstract description 24
- -1 4-pyrone compound Chemical class 0.000 claims abstract description 21
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 21
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 21
- 229940081066 picolinic acid Drugs 0.000 claims abstract description 12
- 125000001424 substituent group Chemical group 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 91
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 83
- BYACHAOCSIPLCM-UHFFFAOYSA-N 2-[2-[bis(2-hydroxyethyl)amino]ethyl-(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(CCO)CCN(CCO)CCO BYACHAOCSIPLCM-UHFFFAOYSA-N 0.000 claims description 20
- 229920006395 saturated elastomer Polymers 0.000 claims description 17
- ORAJHYSVXOYBCP-UHFFFAOYSA-N 3-[2-[bis(3-hydroxypropyl)amino]ethyl-(3-hydroxypropyl)amino]propan-1-ol Chemical compound OCCCN(CCCO)CCN(CCCO)CCCO ORAJHYSVXOYBCP-UHFFFAOYSA-N 0.000 claims description 16
- XPCTZQVDEJYUGT-UHFFFAOYSA-N 3-hydroxy-2-methyl-4-pyrone Chemical compound CC=1OC=CC(=O)C=1O XPCTZQVDEJYUGT-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 7
- YIKYNHJUKRTCJL-UHFFFAOYSA-N Ethyl maltol Chemical compound CCC=1OC=CC(=O)C=1O YIKYNHJUKRTCJL-UHFFFAOYSA-N 0.000 claims description 5
- BEJNERDRQOWKJM-UHFFFAOYSA-N kojic acid Chemical compound OCC1=CC(=O)C(O)=CO1 BEJNERDRQOWKJM-UHFFFAOYSA-N 0.000 claims description 5
- OXXDGKNPRNPMLS-UHFFFAOYSA-N 2-Hydroxy-3-methyl-4H-pyran-4-one Natural products CC1=C(O)OC=CC1=O OXXDGKNPRNPMLS-UHFFFAOYSA-N 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 3
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 3
- 235000012431 wafers Nutrition 0.000 description 64
- 239000010408 film Substances 0.000 description 60
- 239000000758 substrate Substances 0.000 description 56
- 239000004065 semiconductor Substances 0.000 description 26
- 238000004519 manufacturing process Methods 0.000 description 23
- 229910000420 cerium oxide Inorganic materials 0.000 description 22
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 22
- 230000008569 process Effects 0.000 description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- 235000013339 cereals Nutrition 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- CVQUWLDCFXOXEN-UHFFFAOYSA-N Pyran-4-one Chemical compound O=C1C=COC=C1 CVQUWLDCFXOXEN-UHFFFAOYSA-N 0.000 description 7
- 229910052581 Si3N4 Inorganic materials 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OXQGTIUCKGYOAA-UHFFFAOYSA-N 2-Ethylbutanoic acid Chemical compound CCC(CC)C(O)=O OXQGTIUCKGYOAA-UHFFFAOYSA-N 0.000 description 2
- OVBFMEVBMNZIBR-UHFFFAOYSA-N 2-methylvaleric acid Chemical compound CCCC(C)C(O)=O OVBFMEVBMNZIBR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-N isocaproic acid Chemical compound CC(C)CCC(O)=O FGKJLKRYENPLQH-UHFFFAOYSA-N 0.000 description 2
- WZNJWVWKTVETCG-UHFFFAOYSA-N kojic acid Natural products OC(=O)C(N)CN1C=CC(=O)C(O)=C1 WZNJWVWKTVETCG-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- LWMWZNOCSCPBCH-UHFFFAOYSA-N 1-[bis[2-[bis(2-hydroxypropyl)amino]ethyl]amino]propan-2-ol Chemical compound CC(O)CN(CC(C)O)CCN(CC(O)C)CCN(CC(C)O)CC(C)O LWMWZNOCSCPBCH-UHFFFAOYSA-N 0.000 description 1
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- VUAXHMVRKOTJKP-UHFFFAOYSA-N 2,2-dimethylbutyric acid Chemical compound CCC(C)(C)C(O)=O VUAXHMVRKOTJKP-UHFFFAOYSA-N 0.000 description 1
- XFOASZQZPWEJAA-UHFFFAOYSA-N 2,3-dimethylbutyric acid Chemical compound CC(C)C(C)C(O)=O XFOASZQZPWEJAA-UHFFFAOYSA-N 0.000 description 1
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- MLMQPDHYNJCQAO-UHFFFAOYSA-N 3,3-dimethylbutyric acid Chemical compound CC(C)(C)CC(O)=O MLMQPDHYNJCQAO-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- HYMLWHLQFGRFIY-UHFFFAOYSA-N Maltol Natural products CC1OC=CC(=O)C1=O HYMLWHLQFGRFIY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910004166 TaN Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000005380 borophosphosilicate glass Substances 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 1
- 229960001759 cerium oxalate Drugs 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- XHKOOTFZHJHDTI-UHFFFAOYSA-K cerium(3+);tribromate Chemical compound [Ce+3].[O-]Br(=O)=O.[O-]Br(=O)=O.[O-]Br(=O)=O XHKOOTFZHJHDTI-UHFFFAOYSA-K 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- KHSBAWXKALEJFR-UHFFFAOYSA-H cerium(3+);tricarbonate;hydrate Chemical compound O.[Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O KHSBAWXKALEJFR-UHFFFAOYSA-H 0.000 description 1
- KKVSNHQGJGJMHA-UHFFFAOYSA-H cerium(3+);trisulfate;hydrate Chemical compound O.[Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KKVSNHQGJGJMHA-UHFFFAOYSA-H 0.000 description 1
- MOOUSOJAOQPDEH-UHFFFAOYSA-K cerium(iii) bromide Chemical compound [Br-].[Br-].[Br-].[Ce+3] MOOUSOJAOQPDEH-UHFFFAOYSA-K 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229960004705 kojic acid Drugs 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 229940043353 maltol Drugs 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000012134 supernatant fraction Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000000733 zeta-potential measurement Methods 0.000 description 1
Images
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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
Definitions
- the present disclosure relates to a polishing liquid for CMP (Chemical Mechanical Polishing), a polishing liquid set for CMP, a polishing method, and the like.
- CMP Chemical Mechanical Polishing
- CMP technology is one of the most important technologies in the process of manufacturing a device with multi-layered wiring.
- CMP technology is a technology for flattening the surface of a substrate obtained by forming a thin film on a substrate by chemical vapor deposition (CVD) or the like.
- CVD chemical vapor deposition
- planarization by CMP is essential to ensure the depth of focus of lithography. If the surface of the substrate has irregularities, problems such as the impossibility of focusing in the exposure process and the inability to sufficiently form a fine wiring structure occur.
- CMP technology forms element isolation (isolation between elements; STI: Shallow Trench Isolation) regions by polishing plasma oxide films (BPSG, HDP-SiO 2 , p-TEOS, etc.) in the device manufacturing process.
- step of forming an ILD film interlayer insulating film; an insulating film that electrically insulates metal members (such as wiring) in the same layer); , Al/Cu plugs).
- the CMP is usually performed using a device capable of supplying a polishing liquid onto the polishing pad. Then, the surface of the substrate is polished by pressing the substrate against the polishing pad while supplying a polishing liquid between the surface of the substrate and the polishing pad.
- the polishing liquid is one of the elemental technologies, and in order to obtain a high-performance polishing liquid, various polishing liquids have been developed (for example, Patent Document 1 below). reference).
- a silica-based polishing liquid (polishing liquid using abrasive grains containing silica-based particles) having a high polishing rate is mainly used (for example, see Patent Document 2 below).
- a silica-based polishing liquid it tends to be difficult to control polishing scratches that cause defects.
- JP 2008-288537 A JP-A-9-316431 JP-A-10-102038
- the cerium-based polishing liquid has a fine concave-convex pattern composed of convex portions (e.g., Line portions) and concave portions (e.g., Space portions).
- convex portions e.g., Line portions
- concave portions e.g., Space portions
- the present disclosure relates to the following [1] to [17] and the like.
- a polishing liquid for CMP comprising a compound and (B) a compound having two or more nitrogen atoms to which hydroxyalkyl groups are bonded.
- X 11 , X 12 and X 13 are each independently a hydrogen atom or a monovalent substituent.
- Component (A1) is 3-hydroxy-2-methyl-4-pyrone, 5-hydroxy-2-(hydroxymethyl)-4-pyrone, and 2-ethyl-3-hydroxy-4-pyrone
- the components of the polishing liquid for CMP according to any one of [1] to [14] are stored separately as a first liquid and a second liquid, and the first liquid is the A polishing liquid set for CMP, containing abrasive grains and water, wherein the second liquid contains at least one of the additives and water.
- the polishing liquid for CMP according to any one of [1] to [14], or the first liquid and the second liquid in the polishing liquid set for CMP according to [15] A polishing method comprising a step of polishing a surface to be polished using a CMP polishing liquid obtained by mixing.
- the polishing method according to [16] wherein the surface to be polished contains silicon oxide.
- a polishing liquid for CMP that can achieve a high polishing rate for silicon oxide on convex portions in polishing a patterned wafer having a fine concave-convex pattern.
- a CMP polishing liquid set for obtaining the CMP polishing liquid.
- FIG. 4 is a schematic cross-sectional view showing the process of polishing an ILD film
- a numerical range indicated using “-” indicates a range that includes the numerical values before and after "-" as the minimum and maximum values, respectively.
- “A or more” in a numerical range means A and a range exceeding A.
- “A or less” in a numerical range means A and a range less than A.
- the upper limit value or lower limit value of the numerical range in one step can be arbitrarily combined with the upper limit value or lower limit of the numerical range in another step.
- the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
- “A or B” may include either A or B, or may include both.
- each component in the composition means the total amount of the plurality of substances present in the composition unless otherwise specified when there are multiple substances corresponding to each component in the composition.
- layer or film includes not only a shape structure formed over the entire surface but also a shape structure formed partially when viewed as a plan view.
- process is included in the term not only as an independent process, but also as long as the intended action of the process is achieved even if it is not clearly distinguishable from other processes.
- a "hydroxy group” does not include an OH structure contained in a carboxy group.
- the CMP polishing liquid according to the present embodiment contains abrasive grains, an additive, and water. (referred to as "polishing liquid").
- the abrasive grains contain cerium-based particles (particles containing a cerium-based compound).
- the additives of the polishing liquid according to the first embodiment include (A1) a 4-pyrone compound represented by the following general formula (1) (component (A1)) and (B) two or more hydroxyalkyl groups bonded together.
- the additives of the polishing liquid according to the second embodiment are (A2) picolinic acid (component (A2)) and (B) a compound having two or more nitrogen atoms bonded to hydroxyalkyl groups (component (B)). ,including.
- the additive of the polishing liquid according to the present embodiment may contain component (A1), component (A2) and component (B).
- X 11 , X 12 and X 13 are each independently a hydrogen atom or a monovalent substituent. ]
- the silicon oxide of the convex portions can be polished at a high rate.
- L/S Line/Space
- high-speed polishing of silicon oxide for example, a polishing rate of 100 nm/min or more (preferably 250 nm/min or more), etc.) on a blanket wafer having no uneven pattern is achieved.
- a polishing rate for silicon oxide on the convex portions in the polishing of the region of L/S 30 ⁇ m/570 ⁇ m on the patterned wafer.
- the polishing liquid according to this embodiment can be used for CMP of semiconductor wafer materials, and can be used, for example, for polishing a silicon oxide film provided on the surface of a semiconductor wafer.
- the polishing liquid according to this embodiment can be used in the CMP process of the ILD film.
- the abrasive grains contain cerium-based particles. By using the cerium-based particles as the abrasive grains, it is easy to obtain a high polishing rate of silicon oxide on the convex portions of the pattern wafer while reducing polishing scratches on the surface to be polished.
- Cerium-based compounds of cerium-based particles include cerium oxide, cerium hydroxide, cerium ammonium nitrate, cerium acetate, cerium sulfate hydrate, cerium bromate, cerium bromide, cerium chloride, cerium oxalate, cerium nitrate, cerium carbonate, etc. is mentioned.
- cerium-based particles containing cerium oxide (cerium oxide particles)
- the cerium oxide particles may contain polycrystalline cerium oxide having grain boundaries. Such polycrystalline cerium oxide particles have the property that active surfaces appear one after another as they become finer during polishing, and can maintain a high polishing rate of silicon oxide on convex portions of a pattern wafer.
- Examples of methods for producing cerium oxide particles include a calcination method and an oxidation method using hydrogen peroxide.
- the firing temperature may be 350 to 900°C. If the cerium oxide particles produced are agglomerated, the particles may be mechanically crushed.
- the pulverization method may be, for example, dry pulverization using a jet mill or the like, or wet pulverization using a planetary bead mill or the like.
- As the jet mill for example, one described in Kagaku Kogaku Ronbunshu, Vol. 6, No. 5, (1980), pp. 527-532 can be used.
- the zeta potential (surface potential) of the abrasive grains in the polishing liquid may be positive (the zeta potential may exceed 0 mV) from the viewpoint of easily obtaining a high polishing rate of silicon oxide on the convex portions of the pattern wafer.
- the zeta potential of abrasive grains can be measured, for example, using a dynamic light scattering zeta potential measuring device (eg, trade name: DelsaNano C manufactured by Beckman Coulter, Inc.).
- the zeta potential of abrasive grains can be adjusted using additives.
- abrasive grains having a positive zeta potential can be obtained by contacting the abrasive grains with an acid component (eg, acetic acid).
- the average grain size of the abrasive grains is 50 nm or more, 70 nm or more, 100 nm or more, 100 nm or more, 105 nm or more, 110 nm or more, 115 nm or more, 120 nm or more from the viewpoint of easily obtaining a high polishing rate of silicon oxide on the convex portions of the pattern wafer. , 125 nm or greater, 130 nm or greater, 135 nm or greater, or 140 nm or greater.
- the average grain size of the abrasive grains may be 500 nm or less, 300 nm or less, 200 nm or less, 180 nm or less, 150 nm or less, or 140 nm or less from the viewpoint of easily suppressing the occurrence of polishing scratches. From these viewpoints, the average grain size of the abrasive grains is 50 to 500 nm, 50 to 200 nm, 50 to 150 nm, 70 to 500 nm, 70 to 200 nm, 70 to 150 nm, 100 to 500 nm, 100 to 200 nm, or 100 to 150 nm. can be By adjusting the average grain size of the abrasive grains, it is possible to efficiently obtain a high-speed polishing rate and low scratch properties for silicon oxide in accordance with the average grain size of the abrasive grains.
- Average particle diameter of abrasive grains means the median value of the volume distribution of a sample of slurry in which abrasive grains are dispersed, measured with a laser diffraction/scattering particle size distribution measuring device, MicrotracBEL Corp. product name: Microtrac MT3300EXII or the like.
- a sample is prepared by adjusting the content of abrasive grains by dispersing abrasive grains in water so that the content of abrasive grains is 0.25% by mass based on the total mass of the sample, and this sample is measured. Set in the device and measure the median volume distribution.
- the content of abrasive grains may be within the following ranges based on the total mass of the polishing liquid, from the viewpoint of achieving an excellent balance between the polishing rate of silicon oxide on the convex portions of the pattern wafer and the dispersion stability of the abrasive grains.
- the content of abrasive grains is 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 0.15% by mass or more, 0.2% by mass or more, 0.25% by mass or more, 0 .3% by mass or more, 0.5% by mass or more, 0.8% by mass or more, or 1% by mass or more.
- the content of abrasive grains is 10% by mass or less, 5% by mass or less, 3% by mass or less, 1% by mass or less, 0.8% by mass or less, 0.5% by mass or less, 0.3% by mass or less, or It may be 0.25% by mass or less. From these viewpoints, the content of abrasive grains is 0.01 to 10% by mass, 0.01 to 2% by mass, 0.01 to 1% by mass, 0.01 to 0.5% by mass, 0.1 to 10% by mass, 0.1 to 2% by mass, 0.1 to 1% by mass, 0.1 to 0.5% by mass, 0.5 to 10% by mass, 0.5 to 2% by mass, or 0. It may be 5 to 1% by mass.
- the additive of the polishing liquid according to the first embodiment includes, as the (A1) component, a 4-pyrone compound represented by the general formula (1) (hereinafter sometimes simply referred to as "4-pyrone compound").
- a 4-pyrone compound represented by the general formula (1)
- the 4-pyrone compound is an additive that can increase the interaction between the polishing liquid and silicon oxide, it does not have the effect of weakening the repulsive force such as the electrostatic repulsive force between abrasive grains. , it is thought that the agglomeration of abrasive grains can be suppressed.
- a 4-pyrone-based compound is a compound represented by the following general formula (1), and is a compound having a structure in which a hydroxy group is bonded to a carbon atom adjacent to a carbon atom of a carbonyl group.
- a "4-pyrone compound” is a heterocyclic compound having an oxy group and a carbonyl group, and a ⁇ -pyrone ring (6-membered ring) in which the carbonyl group is located at the 4-position relative to the oxy group. .
- a hydroxy group is bonded to the carbon atom adjacent to the carboxy group in the ⁇ -pyrone ring, and other carbon atoms are substituted with substituents other than hydrogen atoms. good too.
- X 11 , X 12 and X 13 each independently represent a hydrogen atom or a monovalent substituent.
- monovalent substituents include aldehyde group, hydroxy group, carboxyl group, carboxylic acid group, sulfonic acid group, phosphoric acid group, bromine atom, chlorine atom, iodine atom, fluorine atom, nitro group, hydrazine group, alkyl group ( Examples thereof include an alkyl group having 1 to 8 carbon atoms), an aryl group (eg an aryl group having 6 to 12 carbon atoms), an alkenyl group (eg an alkenyl group having 1 to 8 carbon atoms).
- Alkyl groups, aryl groups and alkenyl groups may be substituted with OH, COOH, Br, Cl, I, NO2 and the like.
- the substituents may be attached to the carbon atoms adjacent to the oxy group, i.e. X 11 and X 12 may be substituents .
- At least two of X 11 , X 12 and X 13 may be hydrogen atoms.
- the 4-pyrone compound is 3-hydroxy-2-methyl-4-pyrone ( Alias: 3-hydroxy-2-methyl-4H-pyran-4-one, maltol), 5-hydroxy-2-(hydroxymethyl)-4-pyrone (alias: 5-hydroxy-2-(hydroxymethyl)-4H -pyran-4-one, kojic acid), and at least selected from the group consisting of 2-ethyl-3-hydroxy-4-pyrone (alias: 2-ethyl-3-hydroxy-4H-pyran-4-one) may include one, and may include 3-hydroxy-2-methyl-4-pyrone.
- the 4-pyrone compounds can be used singly or in combination of two or more.
- the 4-pyrone compound may be water-soluble.
- a compound with high solubility in water By using a compound with high solubility in water, the desired amount of additive can be dissolved in the polishing liquid, and the effect of improving the polishing speed and suppressing the aggregation of abrasive grains can be improved to a higher level. can be achieved.
- the solubility of the 4-pyrone compound in 100 g of water at normal temperature (25° C.) may be 0.001 g or more, 0.005 g or more, 0.01 g or more, or 0.05 g or more.
- the upper limit of solubility is not particularly limited.
- the content of the 4-pyrone-based compound is the total mass of the polishing liquid, from the viewpoint of easily obtaining a high polishing rate of silicon oxide on the convex portions of the pattern wafer, and from the viewpoint of easily achieving high-speed polishing of silicon oxide on the blanket wafer.
- the content of the 4-pyrone compound is 0.001 mass% or more, 0.005 mass% or more, 0.01 mass% or more, 0.015 mass% or more, 0.02 mass% or more, 0.025 mass% 0.03% by mass or more, 0.032% by mass or more, 0.034% by mass or more, 0.035% by mass or more, 0.04% by mass or more, 0.05% by mass or more, 0.08% by mass or more , 0.1% by mass or more, 0.13% by mass or more, 0.15% by mass or more, 0.18% by mass or more, or 0.2% by mass or more.
- the content of the 4-pyrone compound is 5% by mass or less, 3% by mass or less, 1% by mass or less, 0.8% by mass or less, 0.5% by mass or less, 0.3% by mass or less, and 0.2% by mass. % or less, 0.18 mass % or less, 0.15 mass % or less, 0.13 mass % or less, 0.1 mass % or less, 0.08 mass % or less, 0.05 mass % or less, 0.04 mass % Below, it may be 0.035% by mass or less, or 0.034% by mass or less. From these viewpoints, the content of the 4-pyrone compound is 0.001 to 5% by mass, 0.001 to 1% by mass, 0.001 to 0.3% by mass, and 0.001 to 0.1% by mass.
- 0.001 to 0.05% by mass 0.01 to 5% by mass, 0.01 to 1% by mass, 0.01 to 0.3% by mass, 0.01 to 0.1% by mass, 0.01 ⁇ 0.05% by mass, 0.02-5% by mass, 0.02-1% by mass, 0.02-0.3% by mass, 0.02-0.1% by mass, or 0.02-0 0.05% by weight.
- the mass ratio A1 of the content of the 4-pyrone compound to the content of the abrasive grains (4-pyrone compound/abrasive grains) is as follows from the viewpoint of easily obtaining a high polishing rate of silicon oxide on the convex portions of the pattern wafer. may be in the range of The mass ratio A1 is 0.01 or more, 0.03 or more, 0.5 or more, 0.08 or more, 0.1 or more, 0.12 or more, 0.13 or more, 0.15 or more, 0.18 or more, Alternatively, it may be 0.2 or more.
- Mass ratio A1 is 1 or less, less than 1, 0.8 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.3 or less, 0.2 or less, 0.18 or less, 0.15 or less , 0.13 or less, 0.12 or less, or 0.1 or less. From these viewpoints, the mass ratio A1 is 0.01 to 1, 0.01 to 0.3, 0.01 to 0.15, 0.1 to 1, 0.1 to 0.3, 0.1 to It may be 0.15, 0.12-1, 0.12-0.3, or 0.12-0.15.
- the additive of the polishing liquid according to the second embodiment contains picolinic acid as the (A2) component. It is presumed that the use of the component (A2) increases the interaction between the polishing liquid and the silicon oxide, thereby increasing the polishing rate.
- the content of picolinic acid may be within the following range based on the total mass of the polishing liquid, from the viewpoint of easily obtaining a high polishing rate of silicon oxide on the convex portions of the pattern wafer.
- the content of picolinic acid is 0.001% by mass or more, 0.005% by mass or more, 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, 0.08% by mass or more, 0 0.1% by mass or more, 0.12% by mass or more, 0.15% by mass or more, 0.18% by mass or more, or 0.2% by mass or more.
- the content of picolinic acid is 5% by mass or less, 3% by mass or less, 1% by mass or less, 0.8% by mass or less, 0.5% by mass or less, 0.4% by mass or less, 0.3% by mass or less, Alternatively, it may be 0.2% by mass or less. From these viewpoints, the content of picolinic acid is 0.001 to 5% by mass, 0.001 to 1% by mass, 0.001 to 0.5% by mass, 0.001 to 0.3% by mass, 01 to 5% by mass, 0.01 to 1% by mass, 0.01 to 0.5% by mass, 0.01 to 0.3% by mass, 0.1 to 5% by mass, 0.1 to 1% by mass, It may be from 0.1 to 0.5 mass %, or from 0.1 to 0.3 mass %.
- the mass ratio A2 of the content of picolinic acid to the content of abrasive grains may be in the following range from the viewpoint of easily obtaining a high polishing rate of silicon oxide on the convex portions of the pattern wafer. .
- Mass ratio A2 is 0.01 or more, 0.03 or more, 0.05 or more, 0.08 or more, 0.1 or more, 0.12 or more, 0.15 or more, 0.18 or more, or 0.2 or more.
- the mass ratio A2 is 1 or less, less than 1, 0.8 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.3 or less, 0.25 or less, or 0.2 or less good.
- the mass ratio A2 is 0.01 to 1, 0.01 to 0.5, 0.01 to 0.3, 0.01 to 0.2, 0.05 to 1, 0.05 to 0.5, 0.05-0.3, 0.05-0.2, 0.1-1, 0.1-0.5, 0.1-0.3, or 0.1-0. can be two.
- the additive of the polishing liquid according to the present embodiment contains a compound (nitrogen-containing hydroxyalkyl compound) having two or more nitrogen atoms bonded to hydroxyalkyl groups as the component (B).
- the hydroxyalkyl group is directly bonded to the nitrogen atom, and the hydroxy group is directly bonded to the alkyl group directly bonded to the nitrogen atom.
- Component (B) can use an alkyl group having no substituent other than a hydroxy group as the hydroxyalkyl group bonded to the nitrogen atom.
- the component (B) may contain a compound having a nitrogen atom to which two hydroxyalkyl groups are bonded, from the viewpoint of easily obtaining a high polishing rate of silicon oxide on the convex portions of the pattern wafer.
- the number of nitrogen atoms in one molecule in the component (B) is 2 to 5, 2 to 4, or 2 to 3 from the viewpoint of easily obtaining a high polishing rate of silicon oxide on the protrusions of the pattern wafer. good.
- the number of hydroxy groups in one molecule in the component (B) is 2 to 6, 2 to 5, 2 to 4, 3 to 6, from the viewpoint of easily obtaining a high polishing rate of silicon oxide on the protrusions of the pattern wafer. It may be 3-5, 3-4, 4-6, or 4-5.
- Component (B) has 1 to 4, 2 to 4, 3 to 4 carbon atoms as a hydroxyalkyl group bonded to a nitrogen atom, from the viewpoint of easily obtaining a high polishing rate of silicon oxide on convex portions of a pattern wafer. It may have hydroxyalkyl groups that are 1-3, 2-3 or 1-2. Component (B) is a hydroxyalkyl group having 1 to 3 or 1 to 2 hydroxy groups as a hydroxyalkyl group bonded to a nitrogen atom, from the viewpoint of easily obtaining a high polishing rate of silicon oxide on convex portions of a pattern wafer. It may have an alkyl group.
- the component (B) may have an alkylene group between the two nitrogen atoms to which the hydroxyalkyl groups are bonded, from the viewpoint of easily obtaining a high polishing rate of silicon oxide on the protrusions of the pattern wafer.
- the number may be 1-4, 2-4, 1-3, 2-3, or 1-2.
- the (B) component may contain a compound represented by the following general formula (I) from the viewpoint of easily obtaining a high polishing rate of silicon oxide on the convex portions of the pattern wafer.
- n is an integer of 1 or more
- R 11 , R 12 , R 13 and R 14 each independently represent a hydrogen atom or an organic group, and one or both of R 11 and R 12 are hydroxy an alkyl group and one or both of R 13 and R 14 is a hydroxyalkyl group.
- n may be in the range described above as the number of carbon atoms in the alkylene group between the two nitrogen atoms to which the hydroxyalkyl group is attached.
- the organic group may be a substituted or unsubstituted alkyl group, a hydroxyalkyl group, or a group having a nitrogen atom to which a hydroxyalkyl group is attached.
- Substituents for the alkyl group include a hydroxy group, a carboxy group, an amino group, a sulfo group, a nitro group and the like.
- R 11 , R 12 , R 13 or R 14 is a hydroxyalkyl group
- the number of carbon atoms in the hydroxyalkyl group may be within the range described above as the number of carbon atoms in the hydroxyalkyl group bonded to the nitrogen atom.
- ethylenedinitrilotetraethanol TBEED: 2,2′,2′′,2′′′-ethylenedinitrilotetraethanol (alias: N,N,N′,N′-Tetrakis (2 -hydroxyethyl) ethylenediamine), etc.
- ethylenedinitrilotetrapropanol EDTP: 1,1',1'',1'''-ethylenedinitrilotetra-2-propanol (alias: N,N,N',N' -Tetrakis(2-hydroxypropyl)ethylenediamine), N,N,N',N'',N'-pentakis(2-hydroxypropyl)diethylenetriamine, and the like.
- the component (B) contains ethylene dinitrilotetraethanol and ethylene from the viewpoints of easily obtaining a high polishing rate of silicon oxide on the convex portions of the pattern wafer and from the viewpoint of easily achieving high-speed polishing of the silicon oxide on the blanket wafer. It may contain at least one selected from the group consisting of dinitrilotetrapropanol, may contain ethylene dinitrilotetraethanol, and may contain ethylene dinitrilotetrapropanol.
- the component (B) may contain a compound having no carboxyl group from the viewpoint of easily obtaining a high polishing rate of silicon oxide on the protrusions of the pattern wafer.
- the molecular weight of the component (B) may be within the following range from the viewpoint of easily obtaining a high polishing rate of silicon oxide on the protrusions of the pattern wafer.
- Component (B) has a molecular weight of 50 or more, 60 or more, 70 or more, 80 or more, 85 or more, 90 or more, 100 or more, 110 or more, 120 or more, 123 or more, 125 or more, 130 or more, 140 or more, 148 or more, It may be 150 or more, 160 or more, 170 or more, 180 or more, 200 or more, 210 or more, 230 or more, 250 or more, more than 250, or 280 or more.
- the molecular weight of component (B) is 1000 or less, less than 1000, 900 or less, 800 or less, 700 or less, 600 or less, 500 or less, 400 or less, 350 or less, 300 or less, 280 or less, 250 or less, less than 250, or 240. may be: From these viewpoints, the molecular weight of component (B) is 50 to 1000, 50 to 500, 50 to 300, 50 to 250, 200 to 1000, 200 to 500, 200 to 300, 200 to 250, 250 to 1000, 250 ⁇ 500, or 250-300.
- the content B1 is From the viewpoint of easily obtaining a high polishing rate for silicon oxide, the amount may be within the following range based on the total mass of the polishing liquid.
- Content B1 is 0.001% by mass or more, 0.005% by mass or more, 0.01% by mass or more, 0.015% by mass or more, 0.02% by mass or more, 0.025% by mass or more, 0.03 % by mass or more, 0.035% by mass or more, 0.04% by mass or more, 0.045% by mass or more, or 0.05% by mass or more.
- the content B1 is 5% by mass or less, 3% by mass or less, 1% by mass or less, 0.5% by mass or less, 0.4% by mass or less, 0.3% by mass or less, 0.2% by mass or less, and 0.5% by mass or less. 15% by mass or less, 0.1% by mass or less, 0.08% by mass or less, 0.06% by mass or less, 0.05% by mass or less, 0.045% by mass or less, 0.04% by mass or less, 0.035 % by mass or less, 0.03% by mass or less, 0.025% by mass or less, or 0.02% by mass or less.
- the content B1 is 0.001 to 5% by mass, 0.001 to 1% by mass, 0.001 to 0.1% by mass, 0.001 to 0.05% by mass, 0.01 to 5% by mass, 0.01 to 1% by mass, 0.01 to 0.1% by mass, 0.01 to 0.05% by mass, 0.02 to 5% by mass, 0.02 to 1% by mass, 0. 02 to 0.1 mass %, or 0.02 to 0.05 mass %.
- the content of the component (B) is from the viewpoint of easily obtaining a high polishing rate for silicon oxide and from the viewpoint of easily achieving high-speed polishing of silicon oxide on a blanket wafer, the total mass of the polishing liquid may be in the following range.
- Content B2 is 0.001% by mass or more, 0.005% by mass or more, 0.01% by mass or more, 0.015% by mass or more, 0.02% by mass or more, 0.025% by mass or more, 0.03 % by mass or more, 0.035% by mass or more, 0.04% by mass or more, 0.045% by mass or more, 0.05% by mass or more, 0.06% by mass or more, 0.08% by mass or more, 0.1% by mass % or more, 0.12 mass % or more, 0.13 mass % or more, 0.15 mass % or more, 0.2 mass % or more, or 0.22 mass % or more.
- the content B2 is 5% by mass or less, 3% by mass or less, 1% by mass or less, 0.5% by mass or less, 0.4% by mass or less, 0.3% by mass or less, 0.22% by mass or less, and 0.5% by mass or less.
- 2% by mass or less 0.15% by mass or less, 0.13% by mass or less, 0.12% by mass or less, 0.1% by mass or less, 0.08% by mass or less, 0.06% by mass or less, 0.05 % by mass or less, 0.045% by mass or less, 0.04% by mass or less, 0.035% by mass or less, 0.03% by mass or less, 0.025% by mass or less, 0.02% by mass or less, 0.015% by mass % or less, or 0.01% by mass or less.
- the content B2 is 0.001 to 5% by mass, 0.001 to 1% by mass, 0.001 to 0.3% by mass, 0.001 to 0.05% by mass, 0.01 to 5% by mass, 0.01 to 1% by mass, 0.01 to 0.3% by mass, 0.01 to 0.05% by mass, 0.02 to 5% by mass, 0.02 to 1% by mass, 0. 02 to 0.3 mass %, or 0.02 to 0.05 mass %.
- the mass ratio B11 is 0.001 or more, 0.005 or more, 0.01 or more, 0.02 or more, 0.03 or more, 0.05 or more, 0.08 or more, 0.1 or more, 0.12 or more, It may be 0.15 or more, 0.18 or more, or 0.2 or more.
- the mass ratio B11 is 10 or less, 5 or less, 2 or less, 1 or less, less than 1, 0.5 or less, 0.3 or less, 0.2 or less, 0.18 or less, 0.15 or less, 0.12 or less, It may be 0.1 or less, 0.08 or less, 0.05 or less, 0.03 or less, or 0.02 or less.
- the mass ratio B11 is 0.001 to 10, 0.001 to 1, 0.001 to 0.3, 0.001 to 0.1, 0.01 to 10, 0.01 to 1, It may be 0.01-0.3, 0.01-0.1, 0.02-10, 0.02-1, 0.02-0.3, or 0.02-0.1.
- the mass ratio B21 is 0.001 or more, 0.005 or more, 0.01 or more, 0.02 or more, 0.03 or more, 0.04 or more, 0.05 or more, 0.06 or more, 0.08 or more, It may be 0.1 or more, 0.13 or more, 0.15 or more, 0.2 or more, or 0.22 or more.
- the mass ratio B21 is 10 or less, 5 or less, 2 or less, 1 or less, less than 1, 0.5 or less, 0.3 or less, 0.25 or less, 0.22 or less, 0.2 or less, 0.15 or less, may be 0.13 or less, 0.1 or less, 0.08 or less, 0.06 or less, 0.05 or less, 0.04 or less, 0.03 or less, 0.02 or less, or 0.01 or less .
- the mass ratio B21 is 0.001 to 10, 0.001 to 1, 0.001 to 0.3, 0.001 to 0.2, 0.01 to 10, 0.01 to 1, It may be 0.01-0.3, 0.01-0.2, 0.03-10, 0.03-1, 0.03-0.3, or 0.03-0.2.
- the mass ratio of the content of component (B) to the content of component (A1) ((B) component/(A1) component),
- the mass ratio of the content of nitrilotetraethanol (ethylenedinitrilotetraethanol/component (A1)), or the mass ratio of the content of ethylenedinitrilotetrapropanol to the content of component (A1) (ethylenedinitrilotetrapropanol/ As the (A1) component) may be within the following range from the viewpoint of easily obtaining a high polishing rate of silicon oxide on the convex portions of the pattern wafer.
- Mass ratio B12 is 0.01 or more, 0.05 or more, 0.1 or more, 0.15 or more, 0.2 or more, 0.3 or more, 0.5 or more, 0.6 or more, 0.8 or more, It may be 0.85 or greater, 0.9 or greater, 1 or greater, greater than 1, 1.1 or greater, 1.2 or greater, or 1.4 or greater.
- the mass ratio B12 is 10 or less, 8 or less, 5 or less, 2 or less, 1.5 or less, 1.4 or less, 1.2 or less, 1.1 or less, 1 or less, less than 1, 0.9 or less, 0.9 or less. It may be 85 or less, 0.8 or less, 0.6 or less, 0.5 or less, 0.3 or less, 0.2 or less, 0.15 or less, or 0.1 or less.
- the mass ratio B12 is 0.01-10, 0.01-2, 0.01-1, 0.01-0.5, 0.05-10, 0.05-2, 0.01-10.
- the mass ratio of the content of component (B) to the content of component (A2) ((B) component/(A2) component),
- the mass ratio of the content of nitrilotetraethanol (ethylenedinitrilotetraethanol/component (A2)), or the mass ratio of the content of ethylenedinitrilotetrapropanol to the content of component (A2) (ethylenedinitrilotetrapropanol/ As the (A2) component) may be within the following range from the viewpoint of easily obtaining a high polishing rate of silicon oxide on the convex portions of the pattern wafer.
- the mass ratio B22 is 0.01 or more, 0.05 or more, 0.1 or more, 0.15 or more, 0.2 or more, 0.25 or more, 0.3 or more, 0.5 or more, 0.6 or more, It may be 0.65 or greater, 0.7 or greater, 0.8 or greater, 1 or greater, greater than 1, or 1.1 or greater.
- the mass ratio B22 is 10 or less, 8 or less, 5 or less, 2 or less, 1.5 or less, 1.2 or less, 1.1 or less, 1 or less, less than 1, 0.8 or less, 0.7 or less, 0.1 or less. It may be 65 or less, 0.6 or less, 0.5 or less, 0.3 or less, 0.25 or less, 0.2 or less, 0.15 or less, 0.1 or less, or 0.05 or less.
- the mass ratio B22 is 0.01-10, 0.01-2, 0.01-1, 0.01-0.8, 0.1-10, 0.1-2, 0.01-10. It may be 1 to 1, 0.1 to 0.8, 0.2 to 10, 0.2 to 2, 0.2 to 1, or 0.2 to 0.8.
- the additive of the polishing liquid according to this embodiment may contain a saturated monocarboxylic acid.
- a saturated monocarboxylic acid By using a saturated monocarboxylic acid, it is easy to obtain a sufficiently low polishing rate of silicon nitride that can be used as a stopper material, and not only the dispersibility of cerium-based particles is improved, but also patterned wafers (e.g., semiconductors with uneven patterns) In-plane uniformity, which is an index of variations in polishing rate within the surface to be polished, can be improved without lowering the polishing rate of the substrate.
- Saturated monocarboxylic acids include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, hydroangelic acid, caproic acid, 2-methylpentanoic acid, 4-methylpentanoic acid, 2,3- dimethylbutanoic acid, 2-ethylbutanoic acid, 2,2-dimethylbutanoic acid, 3,3-dimethylbutanoic acid and the like.
- the saturated monocarboxylic acid may contain an aliphatic carboxylic acid from the viewpoint of easily obtaining the above-mentioned effect of addition of the saturated monocarboxylic acid.
- the saturated monocarboxylic acid is a saturated monocarboxylic acid having 2 to 6 carbon atoms from the viewpoint of effectively obtaining the effect of suppressing the polishing rate of silicon nitride and further obtaining the effect of improving the in-plane uniformity more favorably. and may contain at least one selected from the group consisting of acetic acid and propionic acid.
- the content of a saturated monocarboxylic acid (for example, a saturated monocarboxylic acid having 2 to 6 carbon atoms) has an effect of improving in-plane uniformity, an effect of improving the polishing rate of patterned wafers, and an effect of suppressing the polishing rate of silicon nitride. From the viewpoint of effectively obtaining the above, it may be in the following ranges based on the total mass of the polishing liquid.
- the content of saturated monocarboxylic acid is 0.0001% by mass or more, 0.0005% by mass or more, 0.001% by mass or more, 0.002% by mass or more, 0.005% by mass or more, 0.01% by mass or more , 0.02% by mass or more, 0.03% by mass or more, 0.04% by mass or more, or 0.045% by mass or more.
- the content of saturated monocarboxylic acid is 5% by mass or less, 3% by mass or less, 1% by mass or less, 0.5% by mass or less, 0.4% by mass or less, 0.3% by mass or less, and 0.2% by mass. Below, it may be 0.1% by mass or less, 0.05% by mass or less, or 0.045% by mass or less.
- the content of the saturated monocarboxylic acid is 0.0001 to 5% by mass, 0.0001 to 1% by mass, 0.0001 to 0.1% by mass, 0.0001 to 0.05% by mass, 0.01 to 5% by mass, 0.01 to 1% by mass, 0.01 to 0.1% by mass, 0.01 to 0.05% by mass, 0.03 to 5% by mass, 0.03 to 1% by mass %, 0.03-0.1% by weight, or 0.03-0.05% by weight.
- the content of saturated monocarboxylic acid is 0.04% by mass or less, 0.03% by mass or less, 0.02% by mass or less, 0.01% by mass or less, 0.005% by mass or less, 0.002% by mass or less , 0.001 mass % or less, 0.0005 mass % or less, or substantially 0 mass %.
- the additive of the polishing liquid according to the present embodiment may further contain other components (components not corresponding to the above components) in accordance with desired properties.
- components include nonionic polymers; cationic compounds; pH adjusters described later; polar solvents such as ethanol and acetone; and cyclic monocarboxylic acids.
- the polishing liquid according to the present embodiment may contain a compound a having a molecular weight of 100000 or less and having 4 or more hydroxy groups, or may contain no compound a.
- the polishing liquid according to this embodiment may contain the compound b having four or more amino groups, or may not contain the compound b.
- the content of compound b is 0.001% by mass or less, less than 0.001% by mass, 0.0001% by mass or less, 0.00001% by mass or less, or substantially 0, based on the total mass of the polishing liquid. % by mass.
- the mass ratio of the content of compound a to the content of compound b (compound a/compound b) may be 0.10 or less, or less than 0.10.
- Water is not particularly limited, but may contain at least one selected from the group consisting of deionized water, ion-exchanged water and ultrapure water.
- the pH of the polishing liquid according to this embodiment may be within the following range.
- the pH has the viewpoint of easily suppressing the aggregation of abrasive grains, the viewpoint of easily obtaining a high polishing rate of silicon oxide on the convex portions of the pattern wafer, the viewpoint of easily suppressing the polishing rate of silicon nitride that can be used as a stopper material, and , 12.0 or less, 11.0 or less, 10.5 or less, 10.5 or less, 10.0 or less, 10.0 or less, 9.5 or less, from the viewpoint of easily obtaining the effect of adding the above additives, 9.0 or less, less than 9.0, 8.5 or less, 8.0 or less, less than 8.0, 7.5 or less, 7.3 or less, 7.0 or less, less than 7.0, 6.5 or less, 6.0 or less, less than 6.0, 5.6 or less, 5.5 or less, less than 5.5, 5.1 or less, 5.0 or less, 4.8 or less, 4.7 or less, 4.6 or less, It may
- the pH tends to suppress the silicon oxide to be polished from having a zeta potential with a large absolute value on the same positive side as the cerium-based particles (e.g., cerium oxide particles), and the polishing rate of the silicon oxide on the convex portions of the pattern wafer is high.
- cerium-based particles e.g., cerium oxide particles
- the pH is 3.0 to 12.0, 3.0 to less than 9.0, 3.0 to 8.0, 3.0 to 5.5, 3.0 to 5.0, 3 .5 to 12.0, 3.5 to less than 9.0, 3.5 to 8.0, 3.5 to 5.5, 3.5 to 5.0, 4.0 to 12.0, 4. It may be 0 or more and less than 9.0, 4.0 to 8.0, 4.0 to 5.5, or 4.0 to 5.0.
- the pH can be measured by the method described in Examples.
- a pH adjuster may be used to adjust the pH to the above range.
- the pH adjuster is not particularly limited, but examples include acids such as nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, and boric acid; bases such as sodium hydroxide, ammonia (eg, aqueous ammonia), potassium hydroxide, and calcium hydroxide; etc.
- Additives mentioned above, such as saturated monocarboxylic acids, may be used for pH adjustment. From the viewpoint of improving productivity, a polishing liquid may be prepared without using a pH adjuster, and this polishing liquid may be applied to CMP as it is.
- the polishing liquid according to the present embodiment can be classified into (a) a normal type, (b) a concentrated type, and (c) a multiple-liquid type (for example, a two-liquid type, polishing liquid set for CMP). Law is different.
- the normal type is a polishing liquid that can be used as it is without pretreatment such as dilution at the time of polishing.
- the (b) concentrated type is a polishing liquid in which the components are concentrated compared to the (a) normal type in consideration of the convenience of storage or transportation.
- Multiple-liquid type is a state in which the components are divided into multiple liquids (for example, a first liquid containing a certain component and a second liquid containing other components) during storage or transportation. It is a polishing liquid that is mixed with these liquids before use.
- the normal type can be obtained by dissolving or dispersing abrasive grains and additives in water, which is the main dispersion medium.
- the blending amount may be adjusted so that 5 g and 1 g of the additive are obtained.
- the polishing liquid can be prepared using, for example, a stirrer, homogenizer, ultrasonic disperser, wet ball mill, or the like. It should be noted that, in the process of preparing the polishing liquid, a process of making the abrasive grains into fine particles may be performed so that the average grain size of the abrasive grains is within the desired range.
- Abrasive grain micronization can be performed by a sedimentation classification method or a method using a high-pressure homogenizer.
- the sedimentation classification method is a method comprising a step of forcibly sedimenting slurry containing abrasive grains with a centrifuge and a step of taking out only the supernatant liquid.
- the method using a high-pressure homogenizer is a method in which abrasive grains in a dispersion medium collide with each other at high pressure.
- (b) Concentrated type is diluted with water so that the content of the ingredients is the desired content immediately before use. After dilution, (a) liquid characteristics (pH, grain size of abrasive grains, etc.) and polishing characteristics (silicon oxide polishing rate, polishing selectivity between silicon oxide and silicon nitride, etc.) comparable to those of the normal type can be obtained. Stirring may be performed for any length of time up to . In such a (b) concentration type, the volume becomes smaller according to the degree of concentration, so the cost for storage and transportation can be reduced.
- liquid characteristics pH, grain size of abrasive grains, etc.
- polishing characteristics silicon oxide polishing rate, polishing selectivity between silicon oxide and silicon nitride, etc.
- the concentration ratio may be 1.5 times or more, 2 times or more, 3 times or more, or 5 times or more. When the concentration ratio is 1.5 times or more, there is a tendency to obtain advantages in terms of storage and transportation as compared with cases where the concentration ratio is less than 1.5 times.
- the concentration factor may be 40 times or less, 20 times or less, or 15 times or less. When the concentration ratio is 40 times or less, the agglomeration of abrasive grains tends to be suppressed more easily than when the concentration ratio exceeds 40 times.
- the (c) multi-liquid type has the advantage of being able to avoid agglomeration of abrasive grains compared to the (b) concentrated type by appropriately separating each liquid (first liquid, second liquid, etc.). .
- the components contained in each liquid are optional.
- Multi-liquid type (polishing liquid set for CMP) is a polishing liquid set for obtaining a polishing liquid by mixing a first liquid (slurry) and a second liquid (additive liquid).
- the constituent components of the polishing liquid for CMP are stored separately into a first liquid and a second liquid, the first liquid containing abrasive grains and water, and the second liquid containing abrasive grains and water. contains at least one additive and water.
- the first liquid contains abrasive grains and water
- the second liquid is selected from the group consisting of components (A1) and (A2). It contains at least one kind, component (B), and water.
- the first liquid contains abrasive grains, at least one selected from the group consisting of components (A1) and (A2), and water, and the second contains the component (B) and water.
- the first liquid contains abrasive grains, one of the components (A1) and (A2), the component (B), and water
- the second liquid contains the other of the components (A1) and (A2) and water.
- the first liquid contains abrasive grains, the component (B), and water
- the second liquid contains the components (A1) and (A2). At least one selected from the group consisting of and water.
- the first liquid and the second liquid may contain other components blended as necessary.
- any acid or alkali may be added to the first liquid to adjust the pH.
- a multi-liquid type polishing liquid is useful in the case of a combination of components whose polishing properties tend to deteriorate in a relatively short period of time due to aggregation of abrasive grains when mixed.
- the liquids may be of the concentrated type from the viewpoint of cost reduction for storage and transportation.
- each liquid and water may be mixed when using the polishing liquid.
- concentration ratio and pH of each solution are arbitrary, and it is sufficient that the final mixture has the same level of liquid characteristics and polishing characteristics as (a) ordinary type polishing solutions.
- the polishing method according to this embodiment includes a polishing step of polishing a surface to be polished using the polishing liquid according to this embodiment.
- the polishing liquid used in the polishing step may be a polishing liquid obtained by mixing the first liquid and the second liquid in the polishing liquid set described above. That is, the polishing method according to the present embodiment may include a polishing step of polishing the surface to be polished using the polishing liquid obtained by mixing the first liquid and the second liquid in the polishing liquid set described above. .
- the polishing method according to the present embodiment uses a polishing liquid in which the content of each component, pH, etc. are adjusted, and can planarize a substrate having a silicon oxide film on its surface by CMP technology.
- the polishing method according to the present embodiment is suitable for polishing that requires high speed, high flatness, and low polishing scratches, such as the polishing of ILD films, and is suitable for polishing many ILD films in a short time. .
- the polishing step may be a step of supplying the polishing liquid according to the present embodiment between the substrate and a polishing member (polishing member, polishing pad, etc.) and polishing the substrate with the polishing member.
- the polishing method according to this embodiment is suitable for polishing a substrate having a silicon oxide film on its surface. Therefore, the surface to be polished may contain silicon oxide, and in the polishing step, the polishing liquid according to the present embodiment is supplied between the silicon oxide film on the substrate having the silicon oxide film on the surface thereof and the polishing member, and polishing is performed. It may be a step of polishing the silicon oxide film with a member.
- the polishing method according to this embodiment is suitable for polishing a substrate having a silicon oxide film on its surface in the device manufacturing process.
- Devices include discrete semiconductors such as diodes, transistors, compound semiconductors, thermistors, varistors, and thyristors; DRAM (dynamic random access memory), SRAM (static random access memory), EPROM (erasable programmable read) memory), mask ROM (mask read only memory), EEPROM (electrically erasable programmable read only memory), flash memory, etc.; logic circuits such as microprocessors, DSPs, ASICs, etc. Devices; integrated circuit devices such as compound semiconductors represented by MMICs (monolithic microwave integrated circuits); hybrid integrated circuits (hybrid ICs); light emitting diodes;
- a high polishing rate can be achieved without greatly depending on the uneven shape of the surface to be polished. Therefore, the polishing method using the polishing liquid can be applied to a substrate for which it is difficult to achieve a high polishing rate with the conventional method using the polishing liquid.
- the polishing method according to the present embodiment is suitable for flattening a surface to be polished having steps (unevennesses) on the surface.
- Substrates having such a polished surface include, for example, logic semiconductor devices.
- the polishing method according to the present embodiment is suitable for polishing a surface including a portion in which concave portions or convex portions are T-shaped or lattice-shaped when viewed from above.
- the polishing method according to the present embodiment can polish a silicon oxide film provided on the surface of a semiconductor device (DRAM, flash memory, etc.) having memory cells at a high speed. For these reasons, it has been difficult to achieve a high polishing rate with a conventional method using a polishing liquid for CMP. It shows that a high polishing rate can be achieved without depending on
- the substrate is not limited to a substrate having only a silicon oxide film on the surface, and may be a substrate having a silicon nitride film, a polycrystalline silicon film, etc. on the surface in addition to the silicon oxide film.
- the substrate is an inorganic insulating film such as silicon oxide, glass, silicon nitride, etc.; a film mainly containing polysilicon, Al, Cu, Ti, TiN, W, Ta, TaN, etc., on a wiring board having predetermined wiring. It may be a substrate having
- FIG. 1 is a schematic cross-sectional view showing the process of polishing an ILD film, showing the process of forming an ILD film between wirings.
- FIG. 1(a) is a schematic cross-sectional view showing a substrate before polishing.
- FIG. 1(b) is a schematic cross-sectional view showing the substrate after polishing.
- a wiring 20 is formed through an ILD film 10 on a lower substrate (not shown) having predetermined lower wiring (not shown).
- a silicon oxide film 30 is formed to cover the wiring 20 . Since the silicon oxide film 30 is formed on the ILD film 10 on which the wirings 20 are formed, the portion above the wirings 20 is higher than the other portion, thereby forming a step on the surface of the silicon oxide film 30 . D is occurring.
- the wiring 20 is connected to lower wiring and the like by a contact plug 40 formed to penetrate the ILD film 10 .
- the partially protruding unnecessary portions on the surface of the silicon oxide film 30 are preferentially removed by CMP.
- the substrate 100 is placed on the polishing member so that the surface of the silicon oxide film 30 and the polishing member are in contact with each other, and the surface of the silicon oxide film 30 is polished by the polishing member. More specifically, the surface to be polished (surface) side of the silicon oxide film 30 is pressed against the polishing member of the polishing platen, and the polishing liquid is supplied between the surface to be polished and the polishing member while the two are placed relatively to each other.
- the silicon oxide film 30 is polished by moving the .
- step D is eliminated, and finally, as shown in FIG. 1(b), the height of the portion of the wiring 20 on the surface of the silicon oxide film 30 and the height of the other portions become substantially the same, and the surface is flat.
- a substrate 100a having a silicon oxide film 30 (ILD film) with a smooth surface is obtained.
- polishing apparatus used for polishing for example, an apparatus comprising a holder for holding a substrate, a polishing platen to which a polishing pad is attached, and means for supplying polishing liquid onto the polishing pad can be used.
- the polishing device include polishing devices manufactured by Ebara Corporation (model numbers: EPO-111, EPO-222, F-REX200 and F-REX300), and polishing devices manufactured by Applied Materials (trade names: Mirra3400 and Reflexion). be done.
- the constituent material of the polishing pad is not particularly limited, and for example, general non-woven fabric, foamed polyurethane, porous fluororesin, etc. can be used. Further, the polishing pad may be grooved so that the polishing liquid is accumulated.
- the polishing conditions are not particularly limited, but from the viewpoint of preventing the substrate from popping out, the rotational speed of the polishing platen may be 200 min ⁇ 1 or less.
- the pressure (processing load) applied to the substrate may be 100 kPa or less from the viewpoint of easily suppressing scratches on the surface to be polished.
- the polishing liquid may be continuously supplied to the polishing pad by a pump or the like. There is no limit to the amount of supply, but the surface of the polishing pad may always be covered with the polishing liquid. After the polishing is finished, the substrate may be thoroughly washed in running water, and dried after removing water droplets adhering to the substrate using a spin dryer or the like.
- a structure having a desired number of layers can be manufactured by repeating the steps of forming a film and polishing the film a predetermined number of times.
- the substrate (structure) thus obtained can be used as various electronic components.
- electronic components include semiconductor elements; optical glasses such as photomasks, lenses, and prisms; inorganic conductive films such as ITO; optical integrated circuits, optical switching elements, and optical waveguides composed of glass and crystalline materials; optical single crystals such as scintillators; solid laser single crystals; sapphire substrates for blue laser LEDs; semiconductor single crystals such as SiC, GaP and GaAs; magnetic disk glass substrates;
- a method for manufacturing a component according to this embodiment includes a component manufacturing step of obtaining a component using a substrate (member to be polished) that has been polished by a polishing method according to this embodiment.
- a component according to this embodiment is a component obtained by a method for manufacturing a component according to this embodiment.
- the component according to the present embodiment is not particularly limited, but may be an electronic component (for example, a semiconductor component such as a semiconductor package), a wafer (for example, a semiconductor wafer), or a chip (for example, a semiconductor chip). good.
- an electronic component is obtained using a substrate polished by the polishing method according to the present embodiment.
- a semiconductor component for example, a semiconductor package
- the component manufacturing method according to the present embodiment may include a polishing step of polishing the substrate by the polishing method according to the present embodiment before the component manufacturing step.
- the method for manufacturing a component according to the present embodiment may include, as one aspect of the component manufacturing process, a singulation step for singulating the substrate (member to be polished) that has been polished by the polishing method according to the present embodiment.
- the singulation step may be, for example, a step of obtaining chips (eg, semiconductor chips) by dicing a wafer (eg, semiconductor wafer) polished by the polishing method according to the present embodiment.
- the method for manufacturing an electronic component according to the present embodiment comprises dividing the substrate polished by the polishing method according to the present embodiment into individual electronic components (for example, semiconductor parts).
- the method for manufacturing a semiconductor component according to the present embodiment includes dividing a substrate polished by the polishing method according to the present embodiment into individual semiconductor components (for example, semiconductor package).
- the method for manufacturing a component according to the present embodiment connects (for example, electrically connection).
- the object to be connected to be connected to the substrate polished by the polishing method according to the present embodiment is not particularly limited, and may be the substrate polished by the polishing method according to the present embodiment. It may be an object to be connected that is different from the substrate polished by.
- the substrate and the object to be connected may be directly connected (connected while the substrate and the object to be connected are in contact), or the substrate and the object to be connected may be connected via another member (such as a conductive member). You can
- the connection step can be performed before the singulation step, after the singulation step, or before and after the singulation step.
- the connecting step may be a step of connecting the surface to be polished of the substrate polished by the polishing method according to the present embodiment and the object to be connected, and connecting the substrates polished by the polishing method according to the present embodiment. It may be a step of connecting the surface and the connection surface of the object to be connected.
- the connecting surface of the substrate may be a surface to be polished that has been polished by the polishing method according to this embodiment. Through the connecting step, it is possible to obtain a connecting body comprising a base body and a connected body.
- the connecting step when the connecting surface of the substrate has a metal portion, the object to be connected may be brought into contact with the metal portion.
- the connection surface of the substrate has a metal portion and the connection surface of the object to be connected has a metal portion
- the metal portions may be brought into contact with each other.
- the metal portion may contain copper.
- a device according to the present embodiment includes at least one selected from the group consisting of a substrate polished by the polishing method according to the present embodiment and the component according to the present embodiment.
- each of the cerium oxide mixed liquid sent through ultrasonic irradiation was put into four 1000mL polyethylene containers.
- the cerium oxide mixture in each container was centrifuged for 20 minutes under the condition that the centrifugal force applied to the outer periphery was 500G. After centrifugation, the supernatant fraction of the vessel was collected to obtain a slurry.
- the slurry contained about 10.0% by weight of cerium oxide particles (abrasive grains) on a total weight basis.
- a sample for particle size measurement was obtained by diluting the slurry with pure water so that the abrasive grain content was 0.25% by mass based on the total mass.
- the average particle size of the abrasive grains was measured using a laser diffraction/scattering particle size distribution analyzer (manufactured by Microtrac BEL Corp., trade name: Microtrac MT3300EXII), resulting in an average particle size of 140 nm.
- polishing liquid for CMP> By mixing the slurry, each additive and deionized water according to the following procedure, a polishing liquid having the composition (remainder: deionized water) shown in each table below was obtained.
- TBEED means 2,2',2'',2''-ethylenedinitrilotetraethanol
- EDTP means 1,1',1'',1'''-ethylenedi means nitrilotetra-2-propanol.
- Each polishing liquid contains acetic acid in a content corresponding to the content of each abrasive grain as the acetic acid mixed during preparation of the slurry.
- an additive solution was obtained by dissolving each additive in deionized water. Next, equal amounts of the slurry and the additive solution were mixed and stirred for 10 minutes to obtain a concentrated polishing liquid storage liquid containing 5.0% by mass of abrasive grains based on the total mass. rice field.
- the polishing liquid storage liquid contains 20 times the amount of abrasive grains and additives as compared to the final abrasive grain content of 0.25% by mass in the polishing liquid. It contains 5 times the amount of abrasive grains and additives to 1.00% by mass.
- polishing liquids of Examples A1, A4, and Comparative Example A1 were obtained by diluting the polishing liquid storage liquid 20 times with deionized water. Further, the polishing liquids of Examples A2 to A3 and B1 to B6 and Comparative Examples A2 to A3 and B1 were obtained by diluting the polishing liquid storage liquid 5 times with deionized water.
- the abrasive grain content is 0.25 mass % based on the total mass (for the polishing liquid with the abrasive grain content of 1.00 mass %, the abrasive grain content is adjusted to 0.25 mass %)
- the average grain size of the abrasive grains in the case where the slurry was used was the same as the average grain size of the abrasive grains in the above-described slurry.
- ⁇ Zeta potential measurement> An appropriate amount of the polishing liquid was put into "DelsaNano C" (trade name) manufactured by Beckman Coulter, Inc., and the measurement was performed twice at 25°C. The mean value of the indicated zeta potentials was taken as the zeta potential. In each of the examples and comparative examples, the zeta potential of the abrasive grains was positive.
- a silicon oxide film (initial film thickness: 7200 nm) with a test pattern (manufactured by our company, ⁇ 200 mm) having an uneven pattern on the surface was prepared.
- the convex portion (line portion) has an initial level difference higher than the concave portion (space portion) by 6000 nm, and the convex portion assumes polishing evaluation of a high-level, low-density protrusion portion due to etchback.
- the pattern wafer has a plurality of die units of 26 mm ⁇ 26 mm, each die unit has a plurality (four) of 13 mm ⁇ 13 mm unit areas, and one of the unit areas is Line/Space ( Evaluation was performed in a region of parallel line patterns with L/S) of 30 ⁇ m/570 ⁇ m (convex density: 5%).
- a polishing apparatus (trade name: Mirra 3400, manufactured by Applied Materials) was used to polish the evaluation wafers described above.
- the evaluation wafer described above was set on a holder having a suction pad for attaching a substrate.
- a porous urethane resin polishing pad (K-groove groove, manufactured by DuPont (Dow), model number: IC-1010) was attached to a polishing platen having a diameter of 500 mm.
- the holder was placed on the polishing pad with the surface to be polished of the evaluation wafer facing downward.
- the inner tube pressure, retainer ring pressure and membrane pressure were set to 14 kPa, 21 kPa and 14 kPa, respectively.
- the polishing surface plate and the evaluation wafer were rotated at 93 min ⁇ 1 and 87 min ⁇ 1 respectively. to polish the surface to be polished. Blanket wafers were polished for 30 seconds. For the pattern wafer, polishing was performed for 60 seconds so that convex portions remained after polishing. Subsequently, the polished wafer for evaluation was thoroughly washed with pure water using a PVA brush (polyvinyl alcohol brush), and then dried.
- PVA brush polyvinyl alcohol brush
- the film thickness variation was measured at a total of 41 measurement points (20 points on both sides of the center point) including the center point of the wafer and points spaced 5 mm apart from the center point in the diameter direction (20 points on both sides of the center point). The measurement point next to the measurement point 95 mm from the center was 97 mm from the center). At these 41 points, the amount of change in film thickness was measured for a polishing time of 30 seconds, and the average value was obtained as the polishing rate of the blanket wafer.
- one point of L/S 30 ⁇ m/570 ⁇ m pattern central convex part (30 ⁇ m width line) of one unit area (13 mm ⁇ 13 mm) was measured to obtain the polishing rate of the patterned wafer.
- Reference numerals 10 ILD film, 20: Wiring, 30: Silicon oxide film, 40: Contact plug, 100, 100a: Substrate, D: Step.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
Description
[1]砥粒と、添加剤と、水と、を含有し、前記砥粒がセリウム系粒子を含み、前記添加剤が、(A1)下記一般式(1)で表される4-ピロン系化合物と、(B)ヒドロキシアルキル基が結合した2以上の窒素原子を有する化合物と、を含む、CMP用研磨液。
[2]前記(A1)成分が、3-ヒドロキシ-2-メチル-4-ピロン、5-ヒドロキシ-2-(ヒドロキシメチル)-4-ピロン、及び、2-エチル-3-ヒドロキシ-4-ピロンからなる群より選ばれる少なくとも一種を含む、[1]に記載のCMP用研磨液。
[3]前記(A1)成分の含有量が0.01~5質量%である、[1]又は[2]に記載のCMP用研磨液。
[4]前記(B)成分がエチレンジニトリロテトラエタノールを含む、[1]~[3]のいずれか一つに記載のCMP用研磨液。
[5]前記(B)成分がエチレンジニトリロテトラプロパノールを含む、[1]~[4]のいずれか一つに記載のCMP用研磨液。
[6]前記(B)成分の含有量が0.001~5質量%である、[1]~[5]のいずれか一つに記載のCMP用研磨液。
[7]前記添加剤が飽和モノカルボン酸を更に含む、[1]~[6]のいずれか一つに記載のCMP用研磨液。
[8]pHが8.0以下である、[1]~[7]のいずれか一つに記載のCMP用研磨液。
[9]砥粒と、添加剤と、水と、を含有し、前記砥粒がセリウム系粒子を含み、前記添加剤が、(A2)ピコリン酸と、(B)ヒドロキシアルキル基が結合した2以上の窒素原子を有する化合物と、を含む、CMP用研磨液。
[10]前記(A2)成分の含有量が0.001~5質量%である、[9]に記載のCMP用研磨液。
[11]前記(B)成分がエチレンジニトリロテトラエタノールを含む、[9]又は[10]に記載のCMP用研磨液。
[12]前記(B)成分がエチレンジニトリロテトラプロパノールを含む、[9]~[11]のいずれか一つに記載のCMP用研磨液。
[13]前記(B)成分の含有量が0.001~5質量%である、[9]~[12]のいずれか一つに記載のCMP用研磨液。
[14]pHが8.0以下である、[9]~[13]のいずれか一つに記載のCMP用研磨液。
[15][1]~[14]のいずれか一つに記載のCMP用研磨液の構成成分が第1の液と第2の液とに分けて保存され、前記第1の液が、前記砥粒と、水と、を含み、前記第2の液が、前記添加剤の少なくとも一種と、水と、を含む、CMP用研磨液セット。
[16][1]~[14]のいずれか一つに記載のCMP用研磨液、又は、[15]に記載のCMP用研磨液セットにおける前記第1の液と前記第2の液とを混合して得られるCMP用研磨液を用いて被研磨面を研磨する工程を備える、研磨方法。
[17]前記被研磨面が酸化ケイ素を含む、[16]に記載の研磨方法。
本実施形態(第1実施形態及び第2実施形態。以下同様)に係るCMP用研磨液は、砥粒と、添加剤と、水と、を含有するCMP用研磨液(以下、場合により、単に「研磨液」という)である。砥粒は、セリウム系粒子(セリウム系化合物を含む粒子)を含む。第1実施形態に係る研磨液の添加剤は、(A1)下記一般式(1)で表される4-ピロン系化合物((A1)成分)と、(B)ヒドロキシアルキル基が結合した2以上の窒素原子を有する化合物((B)成分)と、を含む。第2実施形態に係る研磨液の添加剤は、(A2)ピコリン酸((A2)成分)と、(B)ヒドロキシアルキル基が結合した2以上の窒素原子を有する化合物((B)成分)と、を含む。本実施形態に係る研磨液の添加剤は、(A1)成分、(A2)成分及び(B)成分を含んでよい。
砥粒は、セリウム系粒子を含む。セリウム系粒子を砥粒として用いることにより、被研磨面に生じる研磨傷を低減しつつパターンウエハの凸部における酸化ケイ素の高い研磨速度を得やすい。
[(A1)成分:4-ピロン系化合物]
第1実施形態に係る研磨液の添加剤は、(A1)成分として、一般式(1)で表される4-ピロン系化合物(以下、場合により、単に「4-ピロン系化合物」という)を含む。4-ピロン系化合物を用いることで、研磨液と酸化ケイ素との相互作用が大きくなることにより研磨速度が高くなりやすいと推測される。また、4-ピロン系化合物は、研磨液と酸化ケイ素との相互作用を大きくし得る添加剤であるにもかかわらず、砥粒同士の静電的反発力等の反発力を弱める効果がないため、砥粒の凝集を抑制することができると考えられる。
第2実施形態に係る研磨液の添加剤は、(A2)成分として、ピコリン酸を含む。(A2)成分を用いることで、研磨液と酸化ケイ素との相互作用が大きくなることにより研磨速度が高くなりやすいと推測される。
本実施形態に係る研磨液の添加剤は、(B)成分として、ヒドロキシアルキル基が結合した2以上の窒素原子を有する化合物(窒素含有ヒドロキシアルキル化合物)を含む。(B)成分では、窒素原子にヒドロキシアルキル基が直接結合しており、窒素原子に直接結合したアルキル基にヒドロキシ基が直接結合している。(B)成分は、窒素原子に結合したヒドロキシアルキル基として、ヒドロキシ基以外の置換基を有しないアルキル基を用いることができる。
本実施形態に係る研磨液の添加剤は、飽和モノカルボン酸を含んでよい。飽和モノカルボン酸を用いることにより、ストッパ材料として使用可能な窒化ケイ素の充分小さい研磨速度を得やすいと共に、セリウム系粒子の分散性を向上させるだけでなく、パターンウエハ(例えば、凹凸パターンを有する半導体基板)の研磨速度を低下させることなく、研磨速度の被研磨面内のばらつきの指標である面内均一性を向上させたりできるという利点が得られる。
本実施形態に係る研磨液の添加剤は、所望とする特性に合わせて他の成分(上述の各成分に該当しない成分)を更に含んでよい。このような成分としては、非イオン性ポリマ;カチオン性化合物;後述するpH調整剤;エタノール、アセトン等の極性溶媒;環状モノカルボン酸などが挙げられる。
水は、特に制限されるものではないが、脱イオン水、イオン交換水及び超純水からなる群より選ばれる少なくとも一種を含んでよい。
本実施形態に係る研磨液のpHは、下記の範囲であってよい。pHは、砥粒の凝集等を抑制しやすい観点、パターンウエハの凸部における酸化ケイ素の高い研磨速度が得られやすい観点、ストッパ材料として使用可能な窒化ケイ素の研磨速度を抑制しやすい観点、及び、上記添加剤を添加した効果が得られやすい観点から、12.0以下、11.0以下、10.5以下、10.5未満、10.0以下、10.0未満、9.5以下、9.0以下、9.0未満、8.5以下、8.0以下、8.0未満、7.5以下、7.3以下、7.0以下、7.0未満、6.5以下、6.0以下、6.0未満、5.6以下、5.5以下、5.5未満、5.1以下、5.0以下、4.8以下、4.7以下、4.6以下、4.5以下、4.4以下、4.3以下、4.2以下、4.1以下、又は、4.0以下であってよい。pHは、研磨対象の酸化ケイ素が、セリウム系粒子(例えば酸化セリウム粒子)と同じプラス側において絶対値の大きいゼータ電位を有することを抑制しやすく、パターンウエハの凸部における酸化ケイ素の高い研磨速度が得られやすい観点から、3.0以上、3.5以上、3.7以上、3.8以上、4.0以上、4.0超、4.1以上、4.2以上、4.3以上、4.4以上、4.5以上、4.6以上、4.7以上、4.8以上、5.0以上、5.1以上、5.5以上、5.5超、5.6以上、6.0以上、6.0超、6.5以上、7.0以上、7.0超、又は、7.3以上であってよい。これらの観点から、pHは、3.0~12.0、3.0以上9.0未満、3.0~8.0、3.0~5.5、3.0~5.0、3.5~12.0、3.5以上9.0未満、3.5~8.0、3.5~5.5、3.5~5.0、4.0~12.0、4.0以上9.0未満、4.0~8.0、4.0~5.5、又は、4.0~5.0であってよい。pHは、実施例に記載の方法により測定できる。
本実施形態に係る研磨液は、(a)通常タイプ、(b)濃縮タイプ及び(c)複数液タイプ(例えば2液タイプ。CMP用研磨液セット)に分類でき、タイプによってそれぞれ調製法及び使用法が相違する。(a)通常タイプは、研磨時に希釈等の前処理をせずにそのまま使用できる研磨液である。(b)濃縮タイプは、保管又は輸送の利便性を考慮し、(a)通常タイプと比較して含有成分を濃縮した研磨液である。(c)複数液タイプは、保管時又は輸送時には、含有成分を複数の液に分けた状態(例えば、一定の成分を含む第1の液と、他の成分を含む第2の液とに分けた状態)としておき、使用に際してこれらの液を混合して使用する研磨液である。
本実施形態に係る研磨方法は、本実施形態に係る研磨液を用いて被研磨面を研磨する研磨工程を含む。研磨工程で用いられる研磨液は、上述の研磨液セットにおける第1の液と第2の液とを混合して得られる研磨液であってもよい。すなわち、本実施形態に係る研磨方法は、上述の研磨液セットにおける第1の液と第2の液とを混合して得られる研磨液を用いて被研磨面を研磨する研磨工程を含んでよい。
本実施形態に係る部品の製造方法は、本実施形態に係る研磨方法により研磨された基体(被研磨部材)を用いて部品を得る部品作製工程を備える。本実施形態に係る部品は、本実施形態に係る部品の製造方法により得られる部品である。本実施形態に係る部品は、特に限定されないが、電子部品(例えば、半導体パッケージ等の半導体部品)であってよく、ウエハ(例えば半導体ウエハ)であってよく、チップ(例えば半導体チップ)であってよい。本実施形態に係る部品の製造方法の一態様として、本実施形態に係る電子部品の製造方法では、本実施形態に係る研磨方法により研磨された基体を用いて電子部品を得る。本実施形態に係る部品の製造方法の一態様として、本実施形態に係る半導体部品の製造方法では、本実施形態に係る研磨方法により研磨された基体を用いて半導体部品(例えば半導体パッケージ)を得る。本実施形態に係る部品の製造方法は、部品作製工程の前に、本実施形態に係る研磨方法により基体を研磨する研磨工程を備えてよい。
炭酸セリウム水和物40kgをアルミナ製容器10個に分けて入れ、それぞれ830℃で2時間、空気中で焼成して黄白色の粉末を計20kg得た。この粉末についてX線回折法で相同定を行い、当該粉末が多結晶体の酸化セリウムを含むことを確認した。焼成によって得られた粉末の粒径をSEMで観察したところ、20~100μmの範囲であった。次いで、ジェットミルを用いて酸化セリウム粉末20kgの乾式粉砕を行うことにより酸化セリウム粉末A(後述の砥粒Aを与える粉末)を得た。粉砕後の酸化セリウム粉末Aの比表面積は9.4m2/gであった。比表面積の測定はBET法によって実施した。
上記で得られた酸化セリウム粉末15.0kg及び脱イオン水84.5kgを容器内に入れて混合した。次に、1M(mol/L、約6質量%)の酢酸を0.5kg添加した後、10分間撹拌することにより酸化セリウム混合液を得た。この酸化セリウム混合液を別の容器に30分かけて送液した。その間、送液する配管内で、酸化セリウム混合液に対して超音波周波数400kHzにて超音波照射を行った。
上述のスラリ、各添加剤及び脱イオン水を下記の手順で混合することにより、下記各表の組成(残部:脱イオン水)を有する研磨液を得た。表中、「THEED」は2,2’,2’’,2’’’-エチレンジニトリロテトラエタノールを意味し、「EDTP」は1,1’,1’’,1’’’-エチレンジニトリロテトラ-2-プロパノールを意味する。各研磨液は、上述のスラリの調製時に混合した酢酸として、それぞれの砥粒含有量に応じた含有量の酢酸を含有している。
ベックマン・コールター株式会社製の商品名「DelsaNano C」内に適量の研磨液を投入し、25℃において測定を2回行った。表示されたゼータ電位の平均値をゼータ電位として得た。実施例及び比較例のそれぞれにおいて、砥粒のゼータ電位は正であった。
(研磨液のpH)
下記の条件で研磨液のpHを測定した。結果を各表に示す。
測定温度:25℃
測定装置:株式会社堀場製作所の商品名:Model(D-71)
測定方法:フタル酸塩pH標準液(pH:4.01)と、中性リン酸塩pH標準液(pH:6.86)と、ホウ酸塩pH標準液(pH:9.18)とをpH標準液として用いてpHメーターを3点校正した後、pHメーターの電極を研磨液に入れて、2min以上経過して安定した後のpHを前記測定装置により測定した。
(評価用ウエハの準備)
ブランケットウエハ(BKW)として、表面に酸化ケイ素膜(SiO2、初期膜厚:1000nm)を有するφ200mmのパターン無しのウエハを準備した。
研磨装置(アプライドマテリアル製、商品名:Mirra3400)を用いて上述の評価用ウエハを研磨した。基体取り付け用の吸着パッドを有するホルダーに上述の評価用ウエハをセットした。直径500mmの研磨定盤に多孔質ウレタン樹脂製の研磨パッド(K-groove溝、DuPont(Dow)社製、型番:IC-1010)を貼り付けた。
光干渉式膜厚測定装置(ナノメトリクス・ジャパン株式会社製、商品名:AFT-5100)を用いて下記のとおり研磨前後の被研磨膜の膜厚変化量を測定し、研磨速度を得た。結果を各表に示す。
Claims (19)
- 前記(A1)成分が、3-ヒドロキシ-2-メチル-4-ピロン、5-ヒドロキシ-2-(ヒドロキシメチル)-4-ピロン、及び、2-エチル-3-ヒドロキシ-4-ピロンからなる群より選ばれる少なくとも一種を含む、請求項1に記載のCMP用研磨液。
- 前記(A1)成分の含有量が0.001~5質量%である、請求項1に記載のCMP用研磨液。
- 前記(B)成分がエチレンジニトリロテトラエタノールを含む、請求項1に記載のCMP用研磨液。
- 前記(B)成分がエチレンジニトリロテトラプロパノールを含む、請求項1に記載のCMP用研磨液。
- 前記(B)成分の含有量が0.001~5質量%である、請求項1に記載のCMP用研磨液。
- 前記添加剤が飽和モノカルボン酸を更に含む、請求項1に記載のCMP用研磨液。
- pHが8.0以下である、請求項1に記載のCMP用研磨液。
- 砥粒と、添加剤と、水と、を含有し、
前記砥粒がセリウム系粒子を含み、
前記添加剤が、(A2)ピコリン酸と、(B)ヒドロキシアルキル基が結合した2以上の窒素原子を有する化合物と、を含む、CMP用研磨液。 - 前記(A2)成分の含有量が0.001~5質量%である、請求項9に記載のCMP用研磨液。
- 前記(B)成分がエチレンジニトリロテトラエタノールを含む、請求項9に記載のCMP用研磨液。
- 前記(B)成分がエチレンジニトリロテトラプロパノールを含む、請求項9に記載のCMP用研磨液。
- 前記(B)成分の含有量が0.001~5質量%である、請求項9に記載のCMP用研磨液。
- pHが8.0以下である、請求項9に記載のCMP用研磨液。
- 請求項1~14のいずれか一項に記載のCMP用研磨液の構成成分が第1の液と第2の液とに分けて保存され、前記第1の液が、前記砥粒と、水と、を含み、前記第2の液が、前記添加剤の少なくとも一種と、水と、を含む、CMP用研磨液セット。
- 請求項1~14のいずれか一項に記載のCMP用研磨液を用いて被研磨面を研磨する工程を備える、研磨方法。
- 前記被研磨面が酸化ケイ素を含む、請求項16に記載の研磨方法。
- 請求項15に記載のCMP用研磨液セットにおける前記第1の液と前記第2の液とを混合して得られるCMP用研磨液を用いて被研磨面を研磨する工程を備える、研磨方法。
- 前記被研磨面が酸化ケイ素を含む、請求項18に記載の研磨方法。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202280053924.0A CN117751430A (zh) | 2021-08-06 | 2022-08-03 | Cmp用研磨液、cmp用研磨液套组及研磨方法 |
JP2023540385A JPWO2023013683A1 (ja) | 2021-08-06 | 2022-08-03 | |
KR1020247003998A KR20240027830A (ko) | 2021-08-06 | 2022-08-03 | Cmp용 연마액, cmp용 연마액 세트 및 연마 방법 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JPPCT/JP2021/029409 | 2021-08-06 | ||
PCT/JP2021/029409 WO2023013059A1 (ja) | 2021-08-06 | 2021-08-06 | Cmp用研磨液、cmp用研磨液セット及び研磨方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2023013683A1 true WO2023013683A1 (ja) | 2023-02-09 |
Family
ID=85155470
Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2021/029409 WO2023013059A1 (ja) | 2021-08-06 | 2021-08-06 | Cmp用研磨液、cmp用研磨液セット及び研磨方法 |
PCT/JP2022/029837 WO2023013692A1 (ja) | 2021-08-06 | 2022-08-03 | Cmp用研磨液、cmp用研磨液セット及び研磨方法 |
PCT/JP2022/029843 WO2023013695A1 (ja) | 2021-08-06 | 2022-08-03 | Cmp用研磨液、cmp用研磨液セット及び研磨方法 |
PCT/JP2022/029820 WO2023013683A1 (ja) | 2021-08-06 | 2022-08-03 | Cmp用研磨液、cmp用研磨液セット及び研磨方法 |
Family Applications Before (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2021/029409 WO2023013059A1 (ja) | 2021-08-06 | 2021-08-06 | Cmp用研磨液、cmp用研磨液セット及び研磨方法 |
PCT/JP2022/029837 WO2023013692A1 (ja) | 2021-08-06 | 2022-08-03 | Cmp用研磨液、cmp用研磨液セット及び研磨方法 |
PCT/JP2022/029843 WO2023013695A1 (ja) | 2021-08-06 | 2022-08-03 | Cmp用研磨液、cmp用研磨液セット及び研磨方法 |
Country Status (5)
Country | Link |
---|---|
JP (3) | JPWO2023013695A1 (ja) |
KR (3) | KR20240027830A (ja) |
CN (3) | CN117751431A (ja) |
TW (3) | TW202313923A (ja) |
WO (4) | WO2023013059A1 (ja) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10102038A (ja) | 1996-09-30 | 1998-04-21 | Hitachi Chem Co Ltd | 酸化セリウム研磨剤及び基板の研磨法 |
JP2008288537A (ja) | 2007-05-21 | 2008-11-27 | Fujifilm Corp | 金属用研磨液及び化学的機械的研磨方法 |
WO2012161202A1 (ja) * | 2011-05-24 | 2012-11-29 | 株式会社クラレ | 化学機械研磨用エロージョン防止剤、化学機械研磨用スラリーおよび化学機械研磨方法 |
WO2016006553A1 (ja) * | 2014-07-09 | 2016-01-14 | 日立化成株式会社 | Cmp用研磨液及び研磨方法 |
US20200071566A1 (en) * | 2018-08-30 | 2020-03-05 | Kctech Co., Ltd. | Slurry composition for chemical mechanical polishing |
JP2020517117A (ja) * | 2017-04-17 | 2020-06-11 | キャボット マイクロエレクトロニクス コーポレイション | バルク酸化物の平坦化のための自己停止研磨組成物および方法 |
JP2020105345A (ja) * | 2018-12-27 | 2020-07-09 | 花王株式会社 | 研磨液組成物 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09316431A (ja) | 1996-05-27 | 1997-12-09 | Showa Kiyabotsuto Super Metal Kk | 研磨用スラリー |
US7071105B2 (en) * | 2003-02-03 | 2006-07-04 | Cabot Microelectronics Corporation | Method of polishing a silicon-containing dielectric |
JP5441362B2 (ja) * | 2008-05-30 | 2014-03-12 | 富士フイルム株式会社 | 研磨液及び研磨方法 |
WO2019069370A1 (ja) * | 2017-10-03 | 2019-04-11 | 日立化成株式会社 | 研磨液、研磨液セット、研磨方法及び欠陥抑制方法 |
-
2021
- 2021-08-06 WO PCT/JP2021/029409 patent/WO2023013059A1/ja unknown
-
2022
- 2022-08-03 CN CN202280053925.5A patent/CN117751431A/zh active Pending
- 2022-08-03 KR KR1020247003998A patent/KR20240027830A/ko unknown
- 2022-08-03 WO PCT/JP2022/029837 patent/WO2023013692A1/ja active Application Filing
- 2022-08-03 CN CN202280053929.3A patent/CN117751432A/zh active Pending
- 2022-08-03 KR KR1020247003963A patent/KR20240027827A/ko unknown
- 2022-08-03 JP JP2023540392A patent/JPWO2023013695A1/ja active Pending
- 2022-08-03 CN CN202280053924.0A patent/CN117751430A/zh active Pending
- 2022-08-03 JP JP2023540385A patent/JPWO2023013683A1/ja active Pending
- 2022-08-03 JP JP2023540390A patent/JPWO2023013692A1/ja active Pending
- 2022-08-03 KR KR1020247002674A patent/KR20240024993A/ko unknown
- 2022-08-03 WO PCT/JP2022/029843 patent/WO2023013695A1/ja active Application Filing
- 2022-08-03 WO PCT/JP2022/029820 patent/WO2023013683A1/ja active Application Filing
- 2022-08-04 TW TW111129315A patent/TW202313923A/zh unknown
- 2022-08-04 TW TW111129312A patent/TW202321390A/zh unknown
- 2022-08-04 TW TW111129319A patent/TW202313924A/zh unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10102038A (ja) | 1996-09-30 | 1998-04-21 | Hitachi Chem Co Ltd | 酸化セリウム研磨剤及び基板の研磨法 |
JP2008288537A (ja) | 2007-05-21 | 2008-11-27 | Fujifilm Corp | 金属用研磨液及び化学的機械的研磨方法 |
WO2012161202A1 (ja) * | 2011-05-24 | 2012-11-29 | 株式会社クラレ | 化学機械研磨用エロージョン防止剤、化学機械研磨用スラリーおよび化学機械研磨方法 |
WO2016006553A1 (ja) * | 2014-07-09 | 2016-01-14 | 日立化成株式会社 | Cmp用研磨液及び研磨方法 |
JP2020517117A (ja) * | 2017-04-17 | 2020-06-11 | キャボット マイクロエレクトロニクス コーポレイション | バルク酸化物の平坦化のための自己停止研磨組成物および方法 |
US20200071566A1 (en) * | 2018-08-30 | 2020-03-05 | Kctech Co., Ltd. | Slurry composition for chemical mechanical polishing |
JP2020105345A (ja) * | 2018-12-27 | 2020-07-09 | 花王株式会社 | 研磨液組成物 |
Non-Patent Citations (1)
Title |
---|
KAGAKU KOUGAKU RONBUNSHU (COLLECTION OF CHEMICAL ENGINEERING PAPERS, vol. 6, no. 5, 1980, pages 527 - 532 |
Also Published As
Publication number | Publication date |
---|---|
CN117751430A (zh) | 2024-03-22 |
CN117751431A (zh) | 2024-03-22 |
JPWO2023013692A1 (ja) | 2023-02-09 |
WO2023013692A1 (ja) | 2023-02-09 |
KR20240027827A (ko) | 2024-03-04 |
KR20240024993A (ko) | 2024-02-26 |
CN117751432A (zh) | 2024-03-22 |
WO2023013695A1 (ja) | 2023-02-09 |
WO2023013059A1 (ja) | 2023-02-09 |
TW202321390A (zh) | 2023-06-01 |
TW202313923A (zh) | 2023-04-01 |
TW202313924A (zh) | 2023-04-01 |
JPWO2023013695A1 (ja) | 2023-02-09 |
JPWO2023013683A1 (ja) | 2023-02-09 |
KR20240027830A (ko) | 2024-03-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101268615B1 (ko) | Cmp용 연마액 및 이것을 이용한 연마 방법 | |
TWI542676B (zh) | CMP polishing solution and grinding method using the same | |
KR101389151B1 (ko) | Cmp용 연마액 및 이를 이용한 연마 방법 | |
JP7180756B2 (ja) | 研磨液、研磨液セット、研磨方法及び欠陥抑制方法 | |
JP5375025B2 (ja) | 研磨液 | |
JP2013038211A (ja) | Cmp用研磨液及びこれを用いた研磨方法 | |
WO2023013683A1 (ja) | Cmp用研磨液、cmp用研磨液セット及び研磨方法 | |
JP6601209B2 (ja) | Cmp用研磨液及びこれを用いた研磨方法 | |
WO2016021325A1 (ja) | Cmp用研磨液及びこれを用いた研磨方法 | |
WO2024111032A1 (ja) | Cmp用研磨液、cmp用研磨液セット及び研磨方法 | |
WO2024111174A1 (ja) | Cmp用研磨液、cmp用研磨液セット及び研磨方法 | |
JP6551053B2 (ja) | Cmp用研磨液及びこれを用いた研磨方法 | |
JP6938855B2 (ja) | Cmp用研磨液及びこれを用いた研磨方法 | |
JP2011243789A (ja) | Cmp用研磨液及びこれを用いた研磨方法 | |
JP6657935B2 (ja) | 研磨液 | |
JP2017206647A (ja) | 研磨パッド用洗浄液及び研磨パッドの洗浄方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22853102 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2023540385 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202280053924.0 Country of ref document: CN |
|
ENP | Entry into the national phase |
Ref document number: 20247003998 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020247003998 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2022853102 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2022853102 Country of ref document: EP Effective date: 20240228 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |