WO2015146468A1 - 研磨用組成物およびそれを用いた研磨方法 - Google Patents
研磨用組成物およびそれを用いた研磨方法 Download PDFInfo
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- WO2015146468A1 WO2015146468A1 PCT/JP2015/055683 JP2015055683W WO2015146468A1 WO 2015146468 A1 WO2015146468 A1 WO 2015146468A1 JP 2015055683 W JP2015055683 W JP 2015055683W WO 2015146468 A1 WO2015146468 A1 WO 2015146468A1
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- polishing
- acid
- polishing composition
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- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 235000020669 docosahexaenoic acid Nutrition 0.000 description 1
- 229940090949 docosahexaenoic acid Drugs 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JAZBEHYOTPTENJ-UHFFFAOYSA-N eicosapentaenoic acid Natural products CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O JAZBEHYOTPTENJ-UHFFFAOYSA-N 0.000 description 1
- 235000020673 eicosapentaenoic acid Nutrition 0.000 description 1
- 229960005135 eicosapentaenoic acid Drugs 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- RKKOMEIYHHASIN-UHFFFAOYSA-N hydroperoxyboronic acid Chemical compound OOB(O)O RKKOMEIYHHASIN-UHFFFAOYSA-N 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- GEOVEUCEIQCBKH-UHFFFAOYSA-N hypoiodous acid Chemical compound IO GEOVEUCEIQCBKH-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229940045996 isethionic acid Drugs 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- NHLDKDYUMJJCHD-UHFFFAOYSA-N methyl 4-ethenylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C=C)C=C1 NHLDKDYUMJJCHD-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- OIGSXRLVIQGTAV-UHFFFAOYSA-N methyl ethenesulfonate Chemical compound COS(=O)(=O)C=C OIGSXRLVIQGTAV-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- NZZGQZMNFCTNAM-UHFFFAOYSA-N naphthalene-2,6-dicarbonyl chloride Chemical compound C1=C(C(Cl)=O)C=CC2=CC(C(=O)Cl)=CC=C21 NZZGQZMNFCTNAM-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- LJDZFAPLPVPTBD-UHFFFAOYSA-N nitroformic acid Chemical compound OC(=O)[N+]([O-])=O LJDZFAPLPVPTBD-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- SFBTTWXNCQVIEC-UHFFFAOYSA-N o-Vinylanisole Chemical compound COC1=CC=CC=C1C=C SFBTTWXNCQVIEC-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical compound OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 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 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 229960004025 sodium salicylate Drugs 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000002130 sulfonic acid ester group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 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
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/14—Carbides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
Definitions
- the present invention relates to a polishing composition used in a semiconductor device manufacturing process and a polishing method using the same.
- CMP Chemical Mechanical Polishing
- the semiconductor circuit becomes finer, the flatness required for the unevenness of the patterned wafer becomes higher, and it is required to realize high flatness on the nano order by CMP.
- the silicon nitride film usually has irregularities, not only the convex parts but also the concave parts are polished when polishing such a material. Are also shaved together, and the unevenness is hard to be solved sufficiently.
- the semiconductor wafer is composed of dissimilar materials such as polycrystalline silicon forming the circuit, silicon oxide as the insulating material, and silicon nitride to protect the silicon dioxide surface that is not part of the trench or via from damage during etching. Is done. For this reason, a phenomenon such as dishing occurs in which a relatively soft material that easily reacts with an abrasive such as polycrystalline silicon or silicon oxide is excessively shaved compared to surrounding silicon nitride or the like, and a step remains.
- dissimilar materials such as polycrystalline silicon forming the circuit, silicon oxide as the insulating material, and silicon nitride to protect the silicon dioxide surface that is not part of the trench or via from damage during etching. Is done. For this reason, a phenomenon such as dishing occurs in which a relatively soft material that easily reacts with an abrasive such as polycrystalline silicon or silicon oxide is excessively shaved compared to surrounding silicon nitride or the like, and a step remains.
- Japanese Translation of PCT International Publication No. 2009-530811 includes both a circuit material containing tungsten and titanium nitride which is a hard coat layer.
- a chemical mechanical polishing composition used for the simultaneous polishing (a) abrasive, (b) malonic acid 0.1 mM to 10 mM, (c) aminocarboxylic acid 0.1 mM to 100 mM, (d) sulfate ion
- a composition comprising 0.1 mM to 100 mM and (e) water and having a pH of 1 to 6 is disclosed.
- JP 2012-040671 A (US Patent Application Publication No. 2013/146804) can polish an object to be polished with poor chemical reactivity such as silicon nitride at a higher speed than polycrystalline silicon or the like.
- a polishing composition comprising a colloidal silica in which an organic acid is immobilized and having a pH of 6 or less is disclosed.
- the conventional polishing composition has a problem that the unevenness of the SiN film or the like cannot be sufficiently eliminated in the semiconductor polishing process.
- an object of the present invention is to provide a polishing composition that can sufficiently eliminate the step of the SiN film.
- the present inventor has conducted earnest research. As a result, when an acidic polishing composition containing a specific anionic copolymer is used together with abrasive grains, the polishing speed of silicon nitride whose surface is positively charged at a pH of less than 6 is significantly higher than the recess. And found that it can be polished. And based on the said knowledge, it came to complete this invention.
- the present invention is used for polishing a polishing object whose surface is positively charged under a pH of less than 6, and is represented by water, abrasive grains, and the following general formula 1 or the following general formula 2.
- An anionic copolymer having a unit structure, having a pH of less than 6, and the anionic copolymer is a polishing composition having two or more acidic groups having different acidities.
- Q 1 is hydrogen; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl
- Q 1 ′ is a single bond, an ether bond, an ester bond, an amide bond, or a carbonyl bond, x is an integer from 0 to 10, y is an integer from 0 to 10, X is an acidic group selected from a
- Ar is a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms
- substituent include a methyl group, an ethyl group, n
- An alkoxy group, Q 2 is any one of a single bond, an ether bond, an ester bond, an amide bond, and a carbonyl bond, x is
- the first aspect of the present invention is used for polishing a polishing object whose surface is positively charged in the pH range of the polishing composition used for polishing, and is represented by abrasive grains, the above general formula 1.
- a polishing composition comprising an anionic copolymer having a unit structure or a unit structure represented by the general formula 2 and having a pH of less than 6.
- the surface of a polishing object such as silicon nitride is positively charged under the condition that the pH is less than 6.
- the hydroxy group on the surface of the abrasive grain such as silica is protonated and the negative charge on the surface is reduced.
- an acidic group having a relatively low acidity and difficult to ionize exhibits affinity with the surface of the abrasive grains such as silica.
- acidic groups that are highly acidic and easily ionized, such as sulfonic acid groups have an affinity for an aqueous phase or an object to be polished having positive charge.
- Such an anionic copolymer is electrostatically adsorbed on a positively charged object to be polished, but the convex portion receives a polishing pressure due to collision with the abrasive grains, and the anionic copolymer and the abrasive grains Are attracted to each other by the polishing pressure, and the anionic copolymer of the convex portion is more easily removed from the surface of the object to be polished than the concave portion. Therefore, polishing proceeds at the convex portion without being affected by the anionic copolymer. On the other hand, it is considered that the polishing rate can be suppressed because the abrasive grains are less likely to collide with each other in a three-dimensional manner and a layer on which the anionic copolymer is adsorbed easily remains.
- the anionic copolymer contained in the polishing composition according to the present invention has two or more types of acidic groups having different acidities, preferably two types of acidic groups having different acidities, and more preferably. Has both an acidic group having a high acid dissociation constant with respect to the pH of the polishing composition and an acidic group having a low acid dissociation constant with respect to the pH of the polishing composition. If the anionic copolymer has two or more types of acidic groups having different acidities, the unit structure may be represented by any one of the general formula 1 and the general formula 2 It may have both a unit structure represented by 1 and a unit structure represented by General Formula 2. X and Y may be acidic groups having the same structure. The anionic copolymer may have three or more types of unit structures.
- the polishing composition according to the present invention includes the anionic copolymer so that the surface of the polishing object having a positive charge on the surface of the silicon nitride or the like having a pH of less than 6 is uneven. Has the effect of scraping with high selectivity.
- the step of polishing a convex portion of the surface of the polishing object whose surface is positively charged under a pH of less than 6 at a polishing rate of 10 times or more that of the concave portion A polishing method or a substrate manufacturing method is provided.
- the anionic copolymer may be a copolymer of two or more types of monomers having an acidic group, and after copolymerizing two or more types of monomers having a functional group that can be converted to an acidic group, The functional group may be converted to an acidic group.
- the copolymer may be any of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer, but preferably a block copolymer in which acidic groups are unevenly distributed for each type. It is.
- the anionic copolymer contained in the polishing composition according to the present invention is particularly limited as long as it has a unit structure represented by the following general formula 1 or a unit structure represented by the following general formula 2. Instead, it may be a vinyl copolymer or a condensation copolymer.
- the anionic copolymer may be a commercially available product or may be obtained by introducing an acidic group into a commercially available resin.
- Q 1 is hydrogen; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl
- Q 1 ′ is a single bond, an ether bond, an ester bond, an amide bond, or a carbonyl bond, x is an integer from 0 to 10, y is an integer from 0 to 10, X is an acidic group selected from a
- Ar is a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms
- substituent include a methyl group, an ethyl group, n
- An alkoxy group, Q 2 is any one of a single bond, an ether bond, an ester bond, an amide bond, and a carbonyl bond, x is
- the anionic copolymer has acidic groups having different acidities or substituents to which acidic groups are bonded may have the same structure or different structures.
- a preferable combination of different acidic groups includes a combination of a sulfonic acid group and a carboxyl group.
- the difference in acidity may be expressed by different main chain structures.
- a copolymer of acrylic acid and fumaric acid it consists of a unit structure represented by —CH (COOH) — and a unit structure represented by —CH 2 CH (COOH) —.
- the molecular weight of the anionic copolymer is preferably 500 or more, more preferably 1000 or more from the viewpoint of protective action. Moreover, it is preferable that it is 100,000 or less from a dispersible viewpoint, and it is more preferable that it is 50000 or less.
- the weight average molecular weight can be measured by GPC (gel permeation chromatography).
- the content of the anionic copolymer in the polishing composition according to the present invention can be appropriately adjusted depending on the content of the abrasive grains and the object to be polished, and is not particularly limited, but may be in the range of 0.1 to 100,000 ppm. Good. Within such a range, a polishing object such as silicon nitride can be planarized at a sufficient polishing rate.
- the acid dissociation constant (pKa) of at least one acidic group of acidic groups having different acidities of the anionic copolymer is preferably small with respect to the pH of the polishing composition.
- the anionic copolymer is ionized and easily adsorbed to the object to be polished. Therefore, it can suppress that a recessed part is scraped off with an abrasive grain.
- the anionic copolymer contained in the polishing composition according to the present invention can be synthesized by a conventionally known method, and can be produced, for example, by the following method.
- a monomer capable of introducing an anionic group such as styrene, vinyl toluene, vinyl naphthalene, or a copolymer of the monomer and a vinyl compound monomer.
- the monomer capable of introducing styrene include diacrylate or dimethacrylate of ethylene glycol or polyethylene glycol, styrene, vinyl toluene, vinyl sulfone, vinyl naphthalene and the like.
- an anionic copolymer used in the present invention can be produced by sulfonating a cross-linked copolymer of styrene and divinylbenzene.
- the vinyl compound monomer that can be used for the preparation of the anionic copolymer by such a method is not particularly limited, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n- Butyl (meth) acrylate, isobutyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl ( (Meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxy
- An ion exchange capacity (cation exchange capacity) can also be prepared by hydrolyzing a carboxylic acid ester group or a sulfonic acid ester group in a polymer.
- the vinyl compound having an anionic group that can be used for the preparation of an anionic copolymer by such a method is not particularly limited, and examples thereof include the following.
- vinyl compound having a carboxyl group examples include acrylic acid monomers such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, 2-ethylacrylic acid, and 3-tert-butylacrylic acid; maleic acid, methylmaleic acid, Examples thereof include maleic monomers such as phenylmaleic acid, chloromaleic acid, fumaric acid, itaconic acid and muconic acid.
- Examples of the vinyl compound having a sulfonic acid group include 2-acrylamidopropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamide-n-hexanesulfonic acid, 2-acrylamido-n-octanesulfonic acid, 2 -Acrylamide-n-dodecanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-phenylpropanesulfonic acid, 2-acrylamide-2,4,4-trimethylpentanesulfonic acid, 2-acrylamide- 2- (4-chlorophenyl) propanesulfonic acid, 2-methacrylamide-n-tetradecanesulfonic acid, sodium 4-methacrylamideamidobenzenesulfonate, 2-sulfoethylmethacrylate, p-vinylbenzenesulfonic acid, styrene Acid, ethylene sulfonic
- Examples of the vinyl compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 3-hydroxy-2-ethylhexyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate , Dipentaerythritol penta (meth) acrylate, glycidyl methacrylate- (meth) acrylic acid adduct, 1,1,1-trimethylolpropane or glycerol (Meth) acrylic acid ester.
- vinyl compounds having a phosphoric acid group examples include vinylphosphonic acid, (methacryloxyethyl) phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxyethyl phosphate, and the like. Is mentioned.
- phenols having an anionic group include phenolsulfonic acid, naphtholsulfonic acid, p-oxybenzenesulfonic acid, sodium salicylate Etc.
- aldehydes formalin, paraformaldehyde, glyoxazal, furfurals and the like are used.
- phenol, cresol, naphthol, resol or the like can be used as a copolymerization component.
- polyesters can be prepared by forming monomers or oligomers followed by polycondensation under vacuum. An acidic group may be introduced later into the polyester thus synthesized, or a substituent that can be converted into an acidic group in advance is introduced into the monomer, and the polyester may be converted into an acidic group after condensation polymerization.
- dicarboxylic acid dihalides that can be used in this method include terephthalic acid chloride, 2-chloroterephthalic acid chloride, 2, 5 -Dichloro terephthalic acid chloride, 2,6-dichloro terephthalic acid chloride, 2,6-naphthalenedicarboxylic acid chloride, and examples of diamines that can be used include p-phenylenediamine, 2-chlorop-phenylenediamine, 2, 5-dichloro p-phenylenediamine, 2,6-dichloro p-phenylenediamine, m-phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4
- the abrasive grains contained in the polishing composition according to the present invention have an action of mechanically polishing the object to be polished, and improve the polishing rate of the object to be polished by the polishing composition.
- the abrasive used may be any of inorganic particles, organic particles, and organic-inorganic composite particles.
- the inorganic particles include particles made of metal oxides such as silica, alumina, ceria, titania, silicon nitride particles, silicon carbide particles, and boron nitride particles.
- Specific examples of the organic particles include polymethyl methacrylate (PMMA) particles.
- PMMA polymethyl methacrylate
- silica is preferable, and colloidal silica is particularly preferable.
- Abrasive grains may be surface-modified. Since normal colloidal silica has a surface charge close to zero under acidic conditions, silica particles are not electrically repelled with each other under acidic conditions and are likely to agglomerate. On the other hand, the abrasive grains surface-modified so that the surface is negatively charged even under acidic conditions below pH 6 are strongly repelled and dispersed well even under acidic conditions, resulting in storage stability of the polishing composition. Will be improved.
- Such surface-modified abrasive grains include, for example, a method in which a metal such as aluminum, titanium or zirconium or an oxide thereof is mixed with the abrasive grains and doped on the surface of the abrasive grains, or an acidic functional group such as sulfonic acid on the silica surface. It can be obtained by a method of introducing a group. Among them, preferred is Al (aluminum) doped silica or colloidal silica in which an organic acid is immobilized.
- a method for obtaining Al-doped silica a method of adding sodium aluminate to a colloidal silica dispersion can be used. This method is described in detail in Japanese Patent No. 3463328 and Japanese Patent Laid-Open No. 63-123807, and this description can be applied to the present invention.
- Colloidal silica in which an organic acid is immobilized is performed, for example, by chemically bonding a functional group of the organic acid to the surface of the colloidal silica. If the colloidal silica and the organic acid are simply allowed to coexist, the organic acid is not fixed to the colloidal silica. If sulfonic acid, which is a kind of organic acid, is immobilized on colloidal silica, for example, the method described in “Sulfonic acid-functionalized silica through quantitative oxidation of thiol groups”, Chem. Commun. 246-247 (2003) It can be carried out.
- a silane coupling agent having a thiol group such as 3-mercaptopropyltrimethoxysilane is coupled to colloidal silica and then oxidized with hydrogen peroxide to fix the sulfonic acid on the surface.
- the colloidal silica thus obtained can be obtained.
- the carboxylic acid is immobilized on colloidal silica, for example, “Novel Silane Coupling Agents Containing a Photolabile 2-Nitrobenzyl Ester for Introduction of a Carboxy Group on the Surface of Silica Gel”, Chemistry Letters, 229 (2000).
- colloidal silica having a carboxylic acid immobilized on the surface can be obtained by irradiating light after coupling a silane coupling agent containing a photoreactive 2-nitrobenzyl ester to colloidal silica. .
- the lower limit of the average primary particle diameter of the abrasive grains is preferably 5 nm or more, more preferably 7 nm or more, and further preferably 10 nm or more.
- the upper limit of the average primary particle diameter of the abrasive grains is preferably 500 nm or less, more preferably 250 nm or less, and further preferably 100 nm or less. Within such a range, the polishing rate of the object to be polished by the polishing composition is improved, and polishing scratches (scratches) are generated on the surface of the object to be polished after polishing with the polishing composition. Can be further suppressed.
- the average primary particle diameter of an abrasive grain is calculated based on the specific surface area of the abrasive grain measured by BET method, for example.
- the upper limit of the average secondary particle diameter of the abrasive grains is preferably 500 nm or less, more preferably 400 nm or less, and further preferably 300 nm or less.
- the value of the average secondary particle diameter of the abrasive grains can be measured by, for example, a laser light scattering method.
- the lower limit of the average secondary particle diameter of the abrasive grains is preferably 5 nm or more, more preferably 7 nm or more, and further preferably 10 nm or more.
- the average degree of association of the abrasive grains obtained by dividing the average secondary particle diameter value of the abrasive grains by the average primary particle diameter value is preferably 1 or more, and more preferably 1.2 or more. As the average degree of association of the abrasive grains increases, there is an advantage that the removal rate of the object to be polished by the polishing composition is improved.
- the average degree of association of the abrasive grains is also preferably 5 or less, more preferably 4 or less, and further preferably 3 or less. As the average degree of association of the abrasive grains decreases, it becomes easier to obtain a polished surface with few surface defects when the polishing object is polished using the polishing composition.
- the lower limit of the content of the abrasive grains in the polishing composition is preferably 0.05% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more. Most preferably, it is 2 mass% or more.
- the upper limit of the content of the abrasive grains in the polishing composition is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less. Within such a range, the polishing rate of the object to be polished can be improved, and the cost of the polishing composition can be reduced.
- the polishing composition of the present invention has a pH value of less than 6.
- the pH value is 6 or more, since the positive charge on the surface of the object to be polished such as silicon nitride is reduced, it is difficult to polish the object to be polished at high speed using abrasive grains whose surface is negatively charged. become.
- the pH value of the polishing composition is preferably 5 or less, more preferably 4 or less, and particularly preferably 3 It is as follows.
- the pH value of the polishing composition is also preferably 1 or more from the viewpoint of safety, and more preferably 1.5 or more.
- the polishing composition of the present invention contains a pH adjuster.
- the following acid or chelating agent can be used as the pH adjuster.
- Examples of the acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, oleic acid , Linoleic acid, linolenic acid, arachidonic acid, docosahexaenoic acid, eicosapentaenoic acid, lactic acid, malic acid, citric acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, melicic acid, cinnamic acid, oxalic acid Carboxylic acids such as acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, aconitic acid, amino acid, nitrocarboxylic acid, me
- sulfonic acid include carbonic acid, hydrochloric acid, nitric acid, phosphoric acid, hypophosphorous acid, phosphorous acid, phosphonic acid, sulfuric acid, boric acid, hydrofluoric acid, orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, metaphosphoric acid, hexametaphosphoric acid Examples include acids.
- chelating agent examples include polyamine, polyphosphonic acid, polyaminocarboxylic acid, polyaminophosphonic acid and the like.
- pH adjusters can be used alone or in combination of two or more.
- inorganic acids and carboxylic acids are preferable.
- the addition amount of the pH adjusting agent is not particularly limited, and may be appropriately selected so that the pH is within the above range.
- the polishing composition of the present invention contains water. From the viewpoint of preventing the influence of impurities on the other components of the polishing composition, it is preferable to use water with a purity as high as possible. Specifically, pure water, ultrapure water, or distilled water from which foreign ions are removed through a filter after removing impurity ions with an ion exchange resin is preferable. Further, as a dispersion medium or a solvent, an organic solvent or the like may further be included for the purpose of controlling the dispersibility of other components of the polishing composition.
- the polishing composition of the present invention further contains other components such as a complexing agent, a metal anticorrosive, an antiseptic, an antifungal agent, an oxidizing agent, a reducing agent, a surfactant, and a water-soluble polymer as necessary. May be included.
- a complexing agent such as a metal anticorrosive, an antiseptic, an antifungal agent, an oxidizing agent, a reducing agent, a surfactant, and a water-soluble polymer as necessary. May be included.
- a complexing agent such as a complexing agent, a metal anticorrosive, an antiseptic, an antifungal agent, an oxidizing agent, a reducing agent, a surfactant, and a water-soluble polymer as necessary. May be included.
- the oxidizing agent, preservative, fungicide, and water-soluble polymer will be described.
- the oxidizing agent that can be added to the polishing composition has an action of oxidizing the surface of the polishing object, and improves the polishing rate of the polishing object by the polishing composition.
- oxidizing agents are hydrogen peroxide, sodium peroxide, barium peroxide, organic oxidizing agent, ozone water, silver (II) salt, iron (III) salt, permanganic acid, chromic acid, dichromic acid, peroxo Disulfuric acid, peroxophosphoric acid, peroxosulfuric acid, peroxoboric acid, performic acid, peracetic acid, perbenzoic acid, perphthalic acid, hypochlorous acid, hypobromite, hypoiodous acid, chloric acid, chlorous acid, Examples include perchloric acid, bromic acid, iodic acid, periodic acid, persulfuric acid, dichloroisocyanuric acid, and salts thereof. These oxidizing agents may be used alone or in combination of two or more. Among these, hydrogen peroxide, ammonium persulfate, periodic acid, hypochlorous acid, and sodium dichloroisocyanurate are preferable.
- the content of the oxidizing agent in the polishing composition is preferably 0.1 g / L or more, more preferably 1 g / L or more, and further preferably 3 g / L or more. As the content of the oxidizing agent increases, the polishing rate of the object to be polished by the polishing composition is further improved.
- the content of the oxidizing agent in the polishing composition is also preferably 200 g / L or less, more preferably 100 g / L or less, and further preferably 40 g / L or less.
- the content of the oxidizing agent decreases, the material cost of the polishing composition can be reduced, and the load on the processing of the polishing composition after polishing, that is, the waste liquid treatment can be reduced.
- the possibility of excessive oxidation of the surface of the object to be polished by the oxidizing agent can be reduced.
- Preservatives and fungicides examples include 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one. And the like, and isothiazoline preservatives such as paraoxybenzoic acid esters and phenoxyethanol. These antiseptics and fungicides may be used alone or in combination of two or more.
- a water-soluble polymer may be added to the polishing composition according to the present invention for the purpose of improving the hydrophilicity of the surface of the polishing object and improving the dispersion stability of the abrasive grains.
- water-soluble polymers include hydroxymethylcellulose, hydroxyethylcellulose (HEC), hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, methylcellulose, ethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, and other cellulose derivatives; poly (N-acylalkyleneimines) ) And the like; polyvinyl alcohol; modified (cation modified or nonionic modified) polyvinyl alcohol; polyvinyl pyrrolidone; polyvinyl caprolactam; polyoxyalkylene such as polyoxyethylene; and copolymers containing these structural units . These water-soluble polymers may be used alone or in combination of two or more.
- the method for producing the polishing composition of the present invention is not particularly limited.
- an anionic copolymer having abrasive grains, a unit structure represented by the above general formula 1 or a unit structure represented by the above general formula 2 is used.
- PH adjuster, water and other components as required can be obtained by stirring and mixing.
- the temperature at the time of mixing each component is not particularly limited, but is preferably 10 to 40 ° C., and may be heated to increase the dissolution rate.
- the material to be polished of the present invention is not particularly limited as long as the surface is positively charged under the condition that the pH is less than 6.
- nitrides such as silicon nitride, aluminum-magnesium, silicon-germanium, etc.
- a material to be polished containing an object to be polished such as an alloy of these or a composite material thereof.
- These polishing objects may be used alone or in combination of two or more.
- the object to be polished may have a single layer structure or two or more types of multilayer structures. In the case of a multilayer structure, each layer may contain the same material or different materials.
- Whether or not the surface of the material to be polished is positively charged under the condition that the pH is less than 6 is determined based on the zeta of the material to be polished in the solution whose pH is adjusted to less than 6 or the same component as the material to be polished. This can be determined by measuring the potential.
- the polishing object whose surface is positively charged under the condition that the pH is less than 6 may be a substance having a pH region that is positively charged under the condition that the pH is less than 6, and in the entire pH region less than 6. It need not be positively charged.
- the material to be polished in the present invention may have the above-described polishing object and a layer containing a material different from the polishing object.
- the material different from the object to be polished examples include, for example, polycrystalline silicon, single crystal silicon, tetraethyl orthosilicate (TEOS), silicon oxide, and the like. These materials may be used alone or in combination of two or more.
- the layer containing a material different from the object to be polished may have a single-layer structure or two or more types of multilayer structures. In the case of a multilayer structure, each layer may contain the same material or different materials.
- the polishing composition of the present invention is suitably used for polishing an object to be polished whose surface is positively charged under conditions where the pH is less than 6, such as silicon nitride. Therefore, the second of the present invention is a polishing method for polishing an object to be polished whose surface is positively charged under a pH of less than 6 using the polishing composition of the present invention.
- a third aspect of the present invention is a method for manufacturing a substrate including a step of polishing, by the polishing method, a polishing object whose surface is positively charged under a pH of less than 6.
- polishing a polishing object whose surface is positively charged under the condition that the pH is less than 6 using the polishing composition of the present invention it may be performed using an apparatus and conditions used for normal metal polishing. it can.
- General polishing apparatuses include a single-side polishing apparatus and a double-side polishing apparatus. In a single-side polishing machine, hold the substrate using a holder called a carrier, and supply the polishing composition from above while pressing the surface plate with the polishing pad affixed to the opposite surface of the substrate to rotate the surface plate To polish one side of the material to be polished.
- polishing is performed by a physical action due to friction between the polishing pad and the polishing composition and the material to be polished, and a chemical action that the polishing composition brings to the material to be polished.
- a porous material such as a nonwoven fabric, polyurethane, or suede can be used without particular limitation.
- the polishing pad is preferably processed so that the polishing liquid is accumulated.
- the polishing conditions in the polishing method according to the present invention include polishing load, platen rotation number, carrier rotation number, flow rate of the polishing composition, and polishing time. These polishing conditions are not particularly limited.
- the polishing load is preferably 0.1 psi or more and 10 psi or less, more preferably 0.5 psi or more and 8.0 psi or less per unit area of the substrate, More preferably, it is 1.0 psi or more and 6.0 psi or less.
- the higher the load the higher the frictional force caused by the abrasive grains, and the higher the mechanical working force, the higher the polishing rate.
- the platen rotation speed and the carrier rotation speed are preferably 10 to 500 rpm.
- the supply amount of the polishing composition may be any supply amount that covers the entire substrate of the material to be polished, and may be adjusted according to conditions such as the size of the substrate.
- the polishing composition of the present invention may be a one-component type or a multi-component type including a two-component type. Further, the polishing composition of the present invention may be prepared by diluting the stock solution of the polishing composition, for example, 10 times or more using a diluent such as water.
- Examples 1 to 10, Comparative Examples 1 to 7 Colloidal silica shown in Table 1 as an abrasive grain and an anionic copolymer were mixed in water in the amounts shown in Table 3, and the pH was adjusted with a pH adjuster to obtain a polishing composition (mixing temperature of about 25). ° C, mixing time: about 10 minutes). The pH of the polishing composition was confirmed with a pH meter.
- polishing rate when the polishing target substrate was polished under the following polishing conditions was measured using the polishing composition according to the present invention.
- the polishing rate was calculated by the following formula.
- Polishing rate [ ⁇ / min] Change in film thickness when polished for 1 minute
- Table 3 below shows the measurement results of the polishing rate.
- the polishing rate ratio in Table 3 is a value calculated by dividing the polishing rate of the convex portion by the polishing rate of the concave portion.
- a polishing composition not containing an organic compound (Comparative Example 1), a polishing composition using a nonionic organic polymer (Comparative Examples 2 and 3), and a homopolymer having a strongly acidic group are used.
- a polishing composition using a nonionic organic polymer (Comparative Examples 2 and 3)
- a homopolymer having a strongly acidic group are used.
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Abstract
Description
Q1’は、単結合、エーテル結合、エステル結合、アミド結合、カルボニル結合のいずれかであり、
xは、0~10の整数であり、
yは、0~10の整数であり、
Xは、スルホン酸基、カルボキシル基、ヒドロキシル基、もしくはリン酸基から選択される酸性基、またはこれらの酸性基を少なくとも1つ有する炭素数1~10の脂肪族炭化水素基、もしくは前記酸性基を少なくとも1つ有する炭素数6~12の芳香族炭化水素基である。)
Q2は、単結合、エーテル結合、エステル結合、アミド結合、カルボニル結合のいずれかであり、
xは、0~10の整数であり、
yは、0~10の整数であり、
Yは、スルホン酸基、カルボキシル基、ヒドロキシル基、もしくはリン酸基から選択される酸性基、またはこれらの酸性基を少なくとも1つ有する炭素数1~10の脂肪族炭化水素基、もしくは前記酸性基を少なくとも1つ有する炭素数6~12の芳香族炭化水素基である。)
本発明の第一は、研磨する際に使用される研磨用組成物のpH領域において表面が正に帯電する研磨対象物を研磨する用途で用いられ、砥粒、上記一般式1で表される単位構造または上記一般式2で表される単位構造を有するアニオン性共重合体を含み、pHが6未満である研磨用組成物である。このような構成とすることにより、凹凸を有するSiN膜を含むパターンウェハの凸部を高選択的に削り取ることができ、よってパターンウェハの段差を十分に解消することができる。
本発明に係る研磨用組成物中に含まれるアニオン性共重合体は、酸性度が異なる2種類以上の酸性基を有し、好ましくは2種類の酸性度が異なる酸性基を有し、より好ましくは研磨用組成物のpHに対して高い酸解離定数の酸性基と、研磨用組成物のpHに対して低い酸解離定数の酸性基とを併有する。酸性度が異なる2種類以上の酸性基を有していれば、該アニオン性共重合体は、単位構造が、すべて一般式1または一般式2のいずれか一方のみで表されても、一般式1で表される単位構造と一般式2で表される単位構造との両方を有していてもよい。XおよびYは、構造が同一の酸性基であってもよい。また、前記アニオン性共重合体は、3種類以上の単位構造を有していてもよい。
Q1’は、単結合、エーテル結合、エステル結合、アミド結合、カルボニル結合のいずれかであり、
xは、0~10の整数であり、
yは、0~10の整数であり、
Xは、スルホン酸基、カルボキシル基、ヒドロキシル基、もしくはリン酸基から選択される酸性基、またはこれらの酸性基を少なくとも1つ有する炭素数1~10の脂肪族炭化水素基、もしくは前記酸性基を少なくとも1つ有する炭素数6~12の芳香族炭化水素基である。)
Q2は、単結合、エーテル結合、エステル結合、アミド結合、カルボニル結合のいずれかであり、
xは、0~10の整数であり、
yは、0~10の整数であり、
Yは、スルホン酸基、カルボキシル基、ヒドロキシル基、もしくはリン酸基から選択される酸性基、またはこれらの酸性基を少なくとも1つ有する炭素数1~10の脂肪族炭化水素基、もしくは前記酸性基を少なくとも1つ有する炭素数6~12の芳香族炭化水素基である。)
また単結合とは、共有電子対1組を共有することによる結合を示すため、Q1’またはQ2が、単結合を表すとき、Q1’またはQ2に炭素原子等の原子は含まれず、Q1’またはQ2の両隣りの原子が互いに単結合で結合していることを意味する。
本発明に係る研磨用組成物が含有するアニオン性共重合体は、従来公知の方法で合成することができ、例えば、以下のような方法によって製造することができる。
上記のアニオン性基を導入し得るモノマーとしては、例えばエチレングリコールまたはポリエチレングリコールのジアクリル酸エステルもしくはジメタクリル酸エステル、スチレン、ビニルトルエン、ビニルスルホン、ビニルナフタレン等が挙げられる。
この方法においては、必要により、イオン性基を有していないモノマーを共重合させたり、あるいは得られた共重合体中のカルボン酸エステル基、スルホン酸エステル基を加水分解させたりしてイオン交換容量(カチオン交換容量)を調製することもできる。
この方法において、アニオン性基を有するフェノール類としては、フェノールスルホン酸、ナフトールスルホン酸、p-オキシベンゼンスルホン酸、サリチル酸ソーダ等を例示することができる。また、アルデヒド類としては、ホルマリン、パラホルムアルデヒド、グリオキサザール、フルフラール類などが使用される。この場合、カチオン交換容量を調整するために、フェノール、クレゾール、ナフト-ル、レゾール等を共重合成分として使用することもできる。
この方法においては、例えば、2,6-ナフタレンジカルボン酸またはそのエステル形成性誘導体、イソフタル酸またはそのエステル形成性誘導体および5-ナトリウムスルホイソフタル酸またはそのエステル形成性誘導体を、テトラメチレングリコール、9,9-ビス[4-(2-ヒドロキシエトキシ)フェニル]フルオレン、ビスフェノールAエチレンオキサイド付加体成分と反応させてモノマーもしくはオリゴマーを形成し、その後真空下で重縮合させることによってポリエステルを調製できる。このようにして合成したポリエステルに後から酸性基を導入してもよく、あらかじめ酸性基に変換しうる置換基をモノマーに導入しておき、縮合重合後に酸性基に変換してもよい。
この方法においては、使用し得る酸性基含有芳香族ジハライドとして、4,4’-ジクロロジフェニルスルホン、4,4’-ジフルオロジフェニルスルホン、4,4’-ジクロロジフェニルケトン、4,4’-ジクロロジフェニルフェニルホスフィンオキシド、4,4’-ジフルオロジフェニルフェニルホスフィンオキシド等を挙げることができる。
この方法において使用し得るジカルボン酸ジハライドとしては、例えば、テレフタル酸クロライド、2-クロルテレフタル酸クロライド、2,5-ジクロルテレフタル酸クロライド、2,6-ジクロルテレフタル酸クロライド、2,6-ナフタレンジカルボン酸クロライドがあげられ、使用し得るジアミンとしてはp-フェニレンジアミン、2-クロルp-フェニレンジアミン、2,5-ジクロルp-フェニレンジアミン、2,6-ジクロルp-フェニレンジアミン、m-フェニレンジアミン、3,4’-ジアミノジフェニルエーテル、4,4’-ジアミノジフェニルエーテル、4,4’-ジアミノジフェニルメタン、4,4’-ジアミノジフェニルスルホン、3,3’-ジアミノジフェニルスルホンなどの芳香族ジアミンなどが挙げられる。
本発明に係る研磨用組成物中に含まれる砥粒は、研磨対象物を機械的に研磨する作用を有し、研磨用組成物による研磨対象物の研磨速度を向上させる。
本発明の研磨用組成物のpHの値は、6未満である。pHの値が6以上であると、窒化ケイ素といった研磨対象物の表面の正の電荷が小さくなるため、表面が負に帯電した砥粒を用いて研磨対象物を高速度で研磨することも困難になる。研磨用組成物により窒化ケイ素などの研磨対象物を十分な研磨速度で研磨する観点から、研磨用組成物のpHの値は、好ましくは5以下、さらに好ましくは4以下であり、特に好ましくは3以下である。
本発明の研磨用組成物は、水を含む。不純物による研磨用組成物の他の成分への影響を防ぐ観点から、できる限り高純度な水を使用することが好ましい。具体的には、イオン交換樹脂にて不純物イオンを除去した後フィルタを通して異物を除去した純水や超純水、または蒸留水が好ましい。また、分散媒または溶媒として、研磨用組成物の他の成分の分散性などを制御する目的で、有機溶媒などをさらに含んでもよい。
本発明の研磨用組成物は、必要に応じて、錯化剤、金属防食剤、防腐剤、防カビ剤、酸化剤、還元剤、界面活性剤、水溶性高分子等の他の成分をさらに含んでもよい。以下、酸化剤、防腐剤、防カビ剤、水溶性高分子について説明する。
研磨用組成物に添加し得る酸化剤は、研磨対象物の表面を酸化する作用を有し、研磨用組成物による研磨対象物の研磨速度を向上させる。
本発明に係る研磨用組成物に添加し得る防腐剤および防カビ剤としては、例えば、2-メチル-4-イソチアゾリン-3-オンや5-クロロ-2-メチル-4-イソチアゾリン-3-オン等のイソチアゾリン系防腐剤、パラオキシ安息香酸エステル類、及びフェノキシエタノール等が挙げられる。これら防腐剤および防カビ剤は、単独でもまたは2種以上混合して用いてもよい。
本発明に係る研磨用組成物には、研磨対象物表面の親水性を向上させることや砥粒の分散安定性を向上させることを目的として水溶性高分子を添加してもよい。水溶性高分子としては、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース(HEC)、ヒドロキシプロピルセルロース、ヒドロキシエチルメチルセルロース、ヒドロキシプロピルメチルセルロース、メチルセルロース、エチルセルロース、エチルヒドロキシエチルセルロース、カルボキシメチルセルロース等のセルロース誘導体;ポリ(N-アシルアルキレンイミン)等のイミン誘導体;ポリビニルアルコール;変性(カチオン変性、またはノニオン変性)ポリビニルアルコール;ポリビニルピロリドン;ポリビニルカプロラクタム;ポリオキシエチレン等のポリオキシアルキレン等;並びにこれらの構成単位を含む共重合体が挙げられる。これら水溶性高分子は、単独で用いても、2種以上を混合して用いてもよい。
本発明の研磨用組成物の製造方法は、特に制限されず、例えば、砥粒、上記一般式1で表される単位構造または上記一般式2で表される単位構造を有するアニオン性共重合体、pH調整剤、水および必要に応じて他の成分を、攪拌混合して得ることができる。
本発明の被研磨材料は、pHが6未満の条件で表面が正に帯電する研磨対象物であれば、特に制限されず、例えば、窒化ケイ素等の窒化物、アルミニウム-マグネシウム、シリコン-ゲルマニウム等の合金、またはこれらの複合材料などの研磨対象物を含む被研磨材料が挙げられる。これら研磨対象物は、単独でもまたは2種以上の組み合わせであってもよい。なお、研磨対象物は、単層構造でもよいし2種以上の多層構造であってもよい。多層構造の場合、各層は同じ材料を含んでもよいし、異なる材料を含んでもよい。
上述のように、本発明の研磨用組成物は、窒化ケイ素などのpHが6未満の条件で表面が正に帯電する研磨対象物の研磨に好適に用いられる。よって、本発明の第二は、pHが6未満の条件で表面が正に帯電する研磨対象物を本発明の研磨用組成物を用いて研磨する研磨方法である。また、本発明の第三は、pHが6未満の条件で表面が正に帯電する研磨対象物を前記研磨方法で研磨する工程を含む基板の製造方法である。
砥粒として表1に示したコロイダルシリカ、およびアニオン性共重合体を表3に示す量、水中で混合し、pH調整剤でpHを調整し、研磨用組成物を得た(混合温度約25℃、混合時間:約10分)。研磨用組成物のpHは、pHメーターにより確認した。
研磨速度の測定結果を下記表3に示す。なお、表3中の研磨速度比は、凸部の研磨速度を凹部の研磨速度で除すことにより算出される値である。
Claims (6)
- pHが6未満の条件で表面が正に帯電する研磨対象物を研磨する用途で用いられ、
水と、
砥粒と、
下記一般式1または下記一般式2で表される単位構造を有するアニオン性共重合体と、
を含み、pHが6未満であり、
前記アニオン性共重合体は、酸性度の異なる2種類以上の酸性基を有する研磨用組成物。
Q1’は、単結合、エーテル結合、エステル結合、アミド結合、カルボニル結合のいずれかであり、
xは、0~10の整数であり、
yは、0~10の整数であり、
Xは、スルホン酸基、カルボキシル基、ヒドロキシル基、もしくはリン酸基から選択される酸性基、またはこれらの酸性基を少なくとも1つ有する炭素数1~10の脂肪族炭化水素基、もしくは前記酸性基を少なくとも1つ有する炭素数6~12の芳香族炭化水素基である。)
Q2は、単結合、エーテル結合、エステル結合、アミド結合、カルボニル結合のいずれかであり、
xは、0~10の整数であり、
yは、0~10の整数であり、
Yは、スルホン酸基、カルボキシル基、ヒドロキシル基、もしくはリン酸基から選択される酸性基、またはこれらの酸性基を少なくとも1つ有する炭素数1~10の脂肪族炭化水素基、もしくは前記酸性基を少なくとも1つ有する炭素数6~12の芳香族炭化水素基である。) - 前記アニオン性共重合体は、前記一般式1で表される単位構造を有するビニル系共重合体である、請求項1に記載の研磨用組成物。
- 前記砥粒は、pH6未満において表面が負に帯電している、請求項1または2に記載の研磨用組成物。
- 前記研磨対象物は、窒化ケイ素を含む基板である、請求項1~3のいずれか1項に記載の研磨用組成物。
- pHが6未満の条件下で表面が正に帯電した研磨対象物表面の凸部を凹部に対して10倍以上の研磨速度で研磨する工程を有する、研磨方法。
- 請求項5に記載の研磨方法で研磨する工程を含む、基板の製造方法。
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2015
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- 2015-02-26 KR KR1020167026180A patent/KR102416182B1/ko active IP Right Grant
- 2015-02-26 JP JP2016510165A patent/JPWO2015146468A1/ja active Pending
- 2015-02-26 SG SG11201607461PA patent/SG11201607461PA/en unknown
- 2015-02-26 WO PCT/JP2015/055683 patent/WO2015146468A1/ja active Application Filing
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- 2015-03-12 TW TW104107910A patent/TWI656205B/zh active
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WO2017163910A1 (ja) * | 2016-03-24 | 2017-09-28 | 株式会社フジミインコーポレーテッド | 研磨用組成物 |
JPWO2017163910A1 (ja) * | 2016-03-24 | 2019-02-14 | 株式会社フジミインコーポレーテッド | 研磨用組成物 |
JPWO2018168206A1 (ja) * | 2017-03-14 | 2020-01-16 | 株式会社フジミインコーポレーテッド | 研磨用組成物、その製造方法ならびにこれを用いた研磨方法および基板の製造方法 |
JP7209620B2 (ja) | 2017-03-14 | 2023-01-20 | 株式会社フジミインコーポレーテッド | 研磨用組成物、その製造方法ならびにこれを用いた研磨方法および基板の製造方法 |
US11643573B2 (en) | 2017-03-14 | 2023-05-09 | Fujimi Incorporated | Polishing composition, production method therefor, and polishing method and production method for substrate, using polishing composition |
JP2019059921A (ja) * | 2017-09-26 | 2019-04-18 | 株式会社フジミインコーポレーテッド | 研磨用組成物、研磨用組成物の製造方法、研磨方法および半導体基板の製造方法 |
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JP7070803B1 (ja) * | 2020-06-09 | 2022-05-18 | Jsr株式会社 | 化学機械研磨用組成物及び研磨方法 |
Also Published As
Publication number | Publication date |
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SG11201607461PA (en) | 2016-10-28 |
JP6768115B2 (ja) | 2020-10-14 |
JP2019194329A (ja) | 2019-11-07 |
TW201538701A (zh) | 2015-10-16 |
US20170136600A1 (en) | 2017-05-18 |
US10406652B2 (en) | 2019-09-10 |
EP3124569A1 (en) | 2017-02-01 |
CN106133105B (zh) | 2018-04-03 |
TWI656205B (zh) | 2019-04-11 |
CN106133105A (zh) | 2016-11-16 |
KR20160138964A (ko) | 2016-12-06 |
KR102416182B1 (ko) | 2022-07-04 |
JPWO2015146468A1 (ja) | 2017-04-13 |
EP3124569A4 (en) | 2017-03-15 |
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