CN107396639B - 研磨用组合物 - Google Patents
研磨用组合物 Download PDFInfo
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- CN107396639B CN107396639B CN201680009819.1A CN201680009819A CN107396639B CN 107396639 B CN107396639 B CN 107396639B CN 201680009819 A CN201680009819 A CN 201680009819A CN 107396639 B CN107396639 B CN 107396639B
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- China
- Prior art keywords
- polishing
- acid
- polishing composition
- silicon
- abrasive grains
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000005498 polishing Methods 0.000 title claims abstract description 155
- 239000000203 mixture Substances 0.000 title claims abstract description 82
- 239000006061 abrasive grain Substances 0.000 claims abstract description 53
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 42
- 239000010703 silicon Substances 0.000 claims abstract description 42
- 125000005372 silanol group Chemical group 0.000 claims abstract description 31
- 239000002210 silicon-based material Substances 0.000 claims abstract description 14
- 239000002612 dispersion medium Substances 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- 239000008119 colloidal silica Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000003980 solgel method Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000007800 oxidant agent Substances 0.000 description 11
- -1 polysilicon Chemical compound 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229910052581 Si3N4 Inorganic materials 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 8
- 150000007524 organic acids Chemical class 0.000 description 7
- 239000003002 pH adjusting agent Substances 0.000 description 7
- 239000011163 secondary particle Substances 0.000 description 7
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 6
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000003755 preservative agent Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 150000002391 heterocyclic compounds Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920005591 polysilicon Polymers 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 241000218033 Hibiscus Species 0.000 description 2
- 235000005206 Hibiscus Nutrition 0.000 description 2
- 235000007185 Hibiscus lunariifolius Nutrition 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003429 antifungal agent Substances 0.000 description 2
- 229940121375 antifungal agent Drugs 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000005661 hydrophobic surface Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-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
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- RLCKHJSFHOZMDR-UHFFFAOYSA-N (3R, 7R, 11R)-1-Phytanoid acid Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)CC(O)=O RLCKHJSFHOZMDR-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- FGFBEHFJSQBISW-UHFFFAOYSA-N 1h-cyclopenta[b]pyridine Chemical class C1=CNC2=CC=CC2=C1 FGFBEHFJSQBISW-UHFFFAOYSA-N 0.000 description 1
- OXQGTIUCKGYOAA-UHFFFAOYSA-N 2-Ethylbutanoic acid Chemical compound CCC(CC)C(O)=O OXQGTIUCKGYOAA-UHFFFAOYSA-N 0.000 description 1
- GLVYLTSKTCWWJR-UHFFFAOYSA-N 2-carbonoperoxoylbenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1C(O)=O GLVYLTSKTCWWJR-UHFFFAOYSA-N 0.000 description 1
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- CVKMFSAVYPAZTQ-UHFFFAOYSA-N 2-methylhexanoic acid Chemical compound CCCCC(C)C(O)=O CVKMFSAVYPAZTQ-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- RLCKHJSFHOZMDR-PWCSWUJKSA-N 3,7R,11R,15-tetramethyl-hexadecanoic acid Chemical compound CC(C)CCC[C@@H](C)CCC[C@@H](C)CCCC(C)CC(O)=O RLCKHJSFHOZMDR-PWCSWUJKSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- GUUULVAMQJLDSY-UHFFFAOYSA-N 4,5-dihydro-1,2-thiazole Chemical compound C1CC=NS1 GUUULVAMQJLDSY-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 125000002471 4H-quinolizinyl group Chemical class C=1(C=CCN2C=CC=CC12)* 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
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- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
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- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- RKKOMEIYHHASIN-UHFFFAOYSA-N hydroperoxyboronic acid Chemical compound OOB(O)O RKKOMEIYHHASIN-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 1
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- HOBCFUWDNJPFHB-UHFFFAOYSA-N indolizine Chemical compound C1=CC=CN2C=CC=C21 HOBCFUWDNJPFHB-UHFFFAOYSA-N 0.000 description 1
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- 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
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Abstract
本发明提供可以以更高的研磨速度对单质硅进行研磨的研磨用组合物。本发明的研磨用组合物用于对包含单质硅和除单质硅以外的含硅化合物的研磨对象物进行研磨的用途,该研磨用组合物包含磨粒和分散介质,前述磨粒的单位表面积的硅烷醇基数超过0个/nm2且为2.0个/nm2以下。
Description
技术领域
本发明涉及研磨用组合物。
背景技术
近年来,随着LSI(大规模集成电路(Large Scale Integration))的高集成化、高性能化而开发了新的微细加工技术。化学机械研磨(chemical mechanical polishing;CMP)法也为其一,其是在LSI制造工序、特别是多层布线形成工序中的层间绝缘膜的平坦化、金属塞形成、嵌入布线(镶嵌布线)形成中被频繁利用的技术。
该CMP已应用于半导体制造中的各工序,作为其一个实施方式,例如可举出:对晶体管制作中的栅形成工序的应用。晶体管制作时,有时对硅、多晶硅(polysilicon)、硅氮化物(氮化硅)这样的含Si材料进行研磨,根据晶体管的结构,要求控制各含Si材料的研磨速率。
例如,在日本特开2013-41992号公报、国际公开第2008/105223号(相当于美国专利申请公开第2010/0001229号说明书)、和日本特开2006-344786号公报中公开了以包含磨粒、表面活性剂等的研磨剂对多晶硅进行研磨的技术。
发明内容
然而,上述专利文献中记载的研磨用组合物对多晶硅等单质硅的研磨速度的提高并不充分,要求进一步改善。
因此,本发明的目的在于,提供可以以更高的研磨速度对单质硅进行研磨的研磨用组合物。
为了解决上述问题,本发明人反复进行了深入研究。其结果发现,通过研磨用组合物中所含的磨粒的单位表面积的硅烷醇基数处于特定范围的研磨用组合物,能够解决上述问题。因此,基于上述见解,从而完成了本发明。
即,本发明为一种研磨用组合物,其用于对包含单质硅和除单质硅以外的含硅化合物的研磨对象物进行研磨的用途,该研磨用组合物包含磨粒和分散介质,前述磨粒的单位表面积的硅烷醇基数超过0个/nm2且为2.0个/nm2以下。
具体实施方式
本发明为一种研磨用组合物,其用于对包含单质硅和除单质硅以外的含硅化合物的研磨对象物进行研磨的用途,该研磨用组合物包含磨粒和分散介质,前述磨粒的单位表面积的硅烷醇基数超过0个/nm2且为2.0个/nm2以下。具有这种构成的本发明的研磨用组合物可以以更高的研磨速度对单质硅进行研磨。
在使用本发明的研磨用组合物时,对于单质硅的研磨速度提高的详细理由虽然不明,但可认为是如下理由。需要说明的是,本发明并不限定于下述内容。
即,通过使磨粒的单位表面积的硅烷醇基数(以下,也简称为硅烷醇基数)超过0个/nm2且为2.0个/nm2以下,从而磨粒表面的疏水性变高,且与同样具有疏水性表面的单质硅的相互作用变强。其结果,认为可以提高单质硅的研磨速度。
以往,磨粒表面的硅烷醇基数减少时,磨粒彼此和/或磨粒的表面结合变得更牢固,其结果磨粒的硬度变高,因此,无论研磨对象物的材料种类如何,均会观察到研磨速度提高。
然而,本发明中发现:通过使磨粒的单位表面积的硅烷醇基数为特定的范围,磨粒表面的疏水性变高,同样具有疏水性表面的单质硅与磨粒的相互作用变强,从而单质硅的研磨速度提高这样的至今未知的作用机理,并发现可以解决上述课题。此外,通过使用本发明的研磨用组合物,也可以获得提高单质硅的研磨速度并维持或抑制除单质硅以外的含硅化合物的研磨速度的效果,即提高单质硅的研磨速度相对于除单质硅以外的含硅化合物的研磨速度之比(选择比)的效果。
以下,对本发明进行详细说明。
[研磨对象物]
本发明的研磨对象物包含单质硅和除单质硅以外的含硅化合物。作为单质硅的例子,可举出:多晶硅(Poly Si、polysilicon)、单晶硅、非晶硅等。
作为除单质硅以外的含硅化合物的例子,例如可举出:氧化硅(SiO2)、氮化硅(SiN)、原硅酸四乙酯(TEOS)等。这些含硅化合物可以单独使用或组合2种以上使用。
接着,针对本发明的研磨用组合物的构成进行详细说明。
[磨粒]
研磨用组合物中所含的磨粒具有对研磨对象物进行机械研磨的作用,使研磨用组合物对研磨对象物的研磨速度提高。
本发明中使用的磨粒只要具有硅烷醇基就没有特别的限制。作为其具体例,例如可举出:由二氧化硅、氧化铝、氧化锆、二氧化钛等金属氧化物形成的颗粒。该磨粒可以单独使用或混合2种以上使用。另外,该磨粒可以使用市售品,也可以使用合成品。
这些磨粒之中,优选二氧化硅,更优选气相二氧化硅、胶体二氧化硅,特别优选胶体二氧化硅。作为胶体二氧化硅的制造方法,可举出:硅酸钠法、溶胶凝胶法,以任一制造方法制造的胶体二氧化硅均可以适宜地用作本发明的磨粒。然而,从减少金属杂质的观点出发,优选通过可以以高纯度制造的溶胶凝胶法制造的胶体二氧化硅。
进而,磨粒只要单位表面积的硅烷醇基数满足上述范围,就也可以经表面修饰。其中,特别优选的是固定化有有机酸的胶体二氧化硅。有机酸在研磨用组合物中所含的胶体二氧化硅的表面上的固定化例如可以通过使有机酸的官能团化学键合于胶体二氧化硅的表面而进行。仅通过使胶体二氧化硅与有机酸简单地共存不会实现有机酸在胶体二氧化硅上的固定化。如果将作为有机酸的一种的磺酸固定化在胶体二氧化硅上,则例如可以通过“Sulfonic acid-functionalized silica through quantitative oxidation of thiolgroups”,Chem.Commun.246-247(2003)中记载的方法来进行。具体而言,使3-巯基丙基三甲氧基硅烷等具有巯基的硅烷偶联剂与胶体二氧化硅偶联后,用过氧化氢将巯基氧化,由此可以得到表面固定化有磺酸的胶体二氧化硅。或者,如果将羧酸固定化在胶体二氧化硅上,例如可以通过“Novel Silane Coupling Agents Containing a Photolabile 2-Nitrobenzyl Ester for Introduction of a Carboxy Group on the Surface ofSilica Gel”,Chemistry Letters,3,228-229(2000)中记载的方法来进行。具体而言,使含有光反应性2-硝基苄酯的硅烷偶联剂与胶体二氧化硅偶联后,进行光照射,由此可以获得在表面固定化有羧酸的胶体二氧化硅。
本发明的研磨用组合物中所含的磨粒中,磨粒的单位表面积的硅烷醇基数为超过0个/nm2且2.0个/nm2以下的范围。磨粒表面不具有硅烷醇基时,即上述硅烷醇基数的单位表面积为0个/nm2时,磨粒彼此聚集,单质硅的研磨速度降低。另一方面,超过2.0个/nm2时,磨粒表面的亲水基的数量变多,从而与研磨对象物的疏水性相互作用降低,因此,单质硅的研磨速度降低。磨粒的单位表面积的硅烷醇基数优选为0.5个/nm2以上且2.0个/nm2以下。
磨粒的单位表面积的硅烷醇基数可以通过基于G.W.Sears的AnalyticalChemistry,vol.28,No.12,1956,1982~1983中记载的使用中和滴定的Sears法来算出。对于硅烷醇基数的计算式,通过以下的式子来计算。
ρ:硅烷醇基数[个/nm2]
c:滴定中使用的氢氧化钠溶液的浓度[mol/L]
a:pH4-9的氢氧化钠溶液的滴加量[ml]
NA:阿伏伽德罗数[6.022×1023个/mol]
C:二氧化硅质量[g]
S:BET比表面积[nm2/g]
磨粒的单位表面积的硅烷醇基数可以通过磨粒的制造方法的选择等来控制。
磨粒的平均二次粒径的下限优选为5nm以上,更优选为7nm以上,进一步优选为10nm以上。另外,磨粒的平均二次粒径的上限优选为500nm以下,更优选为300nm以下,进一步优选为200nm以下。若在这样的范围内,则可以提高研磨用组合物对单质硅的研磨速度。
另外,可以进一步抑制在使用研磨用组合物进行了研磨后的研磨对象物的表面产生凹陷(dishing)。需要说明的是,磨粒的平均二次粒径可以通过例如动态光散射法来算出。
研磨用组合物中的磨粒的含量的下限优选为0.002质量%以上,更优选为0.02质量%以上,进一步优选为0.1质量%以上。另外,研磨用组合物中的磨粒的含量的上限优选为10质量%以下,更优选为8质量%以下,进一步优选为5质量%以下。若在这样的范围内,则可以抑制成本,且获得高研磨速度,可以有效地进行加工。
[水]
本发明的研磨用组合物包含用于将各成分分散的分散介质。作为分散介质,优选水。从抑制对其它成分的作用造成阻碍的观点出发,优选尽可能不含杂质的水,具体而言,优选利用离子交换树脂去除了杂质离子后通过过滤器去除了异物的纯水、超纯水或蒸馏水。
[研磨用组合物的pH]
对于本发明的研磨用组合物的pH没有特别的限制,在较宽的pH范围内发挥提高单质硅的研磨速度这样的效果。其中,从磨粒的分散稳定性的观点出发,pH的下限优选为pH1.0以上,更优选为pH2.0以上。另外,pH的上限优选为pH12以下,更优选为pH10.5以下。
该pH可以通过适量添加pH调节剂来调整。为了将研磨用组合物的pH调整至期望的值,根据需要使用的pH调节剂可以为酸和碱中的任意者,另外,可以为无机化合物和有机化合物中的任意者。作为酸的具体例,例如可举出:硫酸、硝酸、硼酸、碳酸、次磷酸、亚磷酸和磷酸等无机酸;甲酸、乙酸、丙酸、丁酸、戊酸、2-甲基丁酸、正己酸、3,3-二甲基丁酸、2-乙基丁酸、4-甲基戊酸、正庚酸、2-甲基己酸、正辛酸、2-乙基己酸、苯甲酸、乙醇酸、水杨酸、甘油酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、马来酸、邻苯二甲酸、苹果酸、酒石酸、柠檬酸和乳酸等羧酸、以及甲磺酸、乙磺酸和羟乙基磺酸等有机硫酸、肌醇六磷酸、羟基乙叉二膦酸等有机磷系的酸等有机酸等。作为碱的具体例,可举出:氢氧化钾等碱金属的氢氧化物、氨、乙二胺和哌嗪等胺、以及四甲基铵和四乙基铵等季铵盐。这些pH调节剂可以单独使用或混合2种以上使用。
[其它成分]
本发明的研磨用组合物根据需要还可以含有氧化剂、金属防腐蚀剂、防腐剂、防霉剂、水溶性高分子、用于溶解难溶性有机物的有机溶剂等其它成分。以下,是优选的其它成分,针对氧化剂、金属防腐蚀剂、防腐剂和防霉剂进行说明。
〔氧化剂〕
可以添加至研磨用组合物中的氧化剂具有将研磨对象物的表面氧化的作用,使研磨用组合物对研磨对象物的研磨速度提高。
能使用的氧化剂可举出:过氧化氢、过氧化钠、过氧化钡、臭氧水、银(II)盐、铁(III)盐、高锰酸、铬酸、重铬酸、过氧二硫酸、过氧磷酸、过氧硫酸、过氧硼酸、过甲酸、过乙酸、过苯甲酸、过邻苯二甲酸、次氯酸、次溴酸、次碘酸、氯酸、亚氯酸、高氯酸、溴酸、碘酸、高碘酸、过硫酸、二氯异氰脲酸及它们的盐等。这些氧化剂可以单独使用或混合2种以上使用。
研磨用组合物中的氧化剂的含量优选为0.1g/L以上,更优选为1g/L以上,进一步优选为3g/L以上。随着氧化剂的含量变多,研磨用组合物对研磨对象物的研磨速度进一步提高。
另外,研磨用组合物中的氧化剂的含量优选为200g/L以下,更优选为100g/L以下,进一步优选为40g/L以下。随着氧化剂的含量变少,不仅能够抑制研磨用组合物的材料成本,而且能够减少研磨使用后的研磨用组合物的处理、即减少废液处理的负担。另外,也能够减少由氧化剂导致的研磨对象物表面发生过度氧化的担心。
〔金属防腐蚀剂〕
通过在研磨用组合物中加入金属防腐蚀剂,可以进一步抑制因使用研磨用组合物的研磨而在布线的旁边产生凹陷。另外,可以进一步抑制在使用研磨用组合物进行了研磨后的研磨对象物的表面产生凹陷。
对于能使用的金属防腐蚀剂没有特别的限制,优选为杂环化合物或表面活性剂。对于杂环化合物中的杂环的元数没有特别的限制。另外,杂环化合物可以为单环化合物,也可以为具有稠环的多环化合物。该金属防腐蚀剂可以单独使用或混合2种以上使用。另外,该金属防腐蚀剂可以使用市售品,也可以使用合成品。
对于能够作为金属防腐蚀剂使用的杂环化合物的具体例,例如可举出:吡咯化合物、吡唑化合物、咪唑化合物、三唑化合物、四唑化合物、吡啶化合物、吡嗪化合物、哒嗪化合物、氮茚(pyrindine)化合物、中氮茚化合物、吲哚化合物、异吲哚化合物、吲唑化合物、嘌呤化合物、喹嗪化合物、喹啉化合物、异喹啉化合物、萘啶化合物、酞嗪化合物、喹喔啉化合物、喹唑啉化合物、噌啉化合物、布替利嗪(Buterizine)化合物、噻唑化合物、异噻唑化合物、噁唑化合物、异噁唑化合物、呋咱化合物等含氮杂环化合物。
〔防腐剂和防霉剂〕
作为本发明中使用的防腐剂和防霉剂,例如可举出:2-甲基-4-异噻唑啉-3-酮、5-氯-2-甲基-4-异噻唑啉-3-酮等异噻唑啉系防腐剂、对羟基苯甲酸酯类、及苯氧基乙醇等。这些防腐剂和防霉剂可以单独使用或混合2种以上使用。
[研磨用组合物的制造方法]
对于本发明的研磨用组合物的制造方法没有特别的限制,例如可以通过将磨粒、以及根据需要的其它成分在水中搅拌混合来获得。
对于混合各成分时的温度没有特别的限制,优选为10~40℃,为了提高溶解速度也可以进行加热。另外,对于混合时间也没有特别的限制。
[研磨方法和基板的制造方法]
如上所述,本发明的研磨用组合物特别适用于包含单质硅和除单质硅以外的含硅化合物的研磨对象物的研磨。因此,本发明提供用本发明的研磨用组合物对包含单质硅和除单质硅以外的含硅化合物的研磨对象物进行研磨的研磨方法。另外,本发明提供一种基板的制造方法,其包括用前述研磨方法对包含单质硅和除单质硅以外的含硅化合物的研磨对象物进行研磨的工序。
作为研磨装置,可以使用如下的通常的研磨装置:其安装有用于保持具有研磨对象物的基板等的保持件和可改变转速的电动机等,且具有可贴附研磨垫(研磨布)的研磨平板。
作为前述研磨垫,可以没有特别限制地使用通常的无纺布、聚氨酯及多孔质氟树脂等。优选对研磨垫实施使研磨液积存那样的槽加工。
对于研磨条件也没有特别的限制,例如,研磨平板的转速优选10~500rpm,对具有研磨对象物的基板施加的压力(研磨压力)优选0.5~10psi。对于向研磨垫供给研磨用组合物的方法也没有特别的限制,例如,可以采用通过泵等连续地供给的方法。对该供给量没有限制,优选研磨垫的表面一直被本发明的研磨用组合物覆盖。
研磨结束后,在流水中清洗基板,利用旋转式干燥机等甩掉附着在基板上的水滴,使其干燥,由此得到具有含有金属或含硅材料的层的基板。
实施例
用以下的实施例和比较例进一步对本发明进行详细说明。但是,本发明的保护范围并不仅限于以下的实施例。
需要说明的是,磨粒的单位表面积的硅烷醇基数(单位:个/nm2)是通过以下的测定方法或计算方法测定或算出各参数后,通过下述方法算出的。另外,磨粒的平均二次粒径利用动态光散射式的粒径测定装置进行测定。
<硅烷醇基数的算出方法>
磨粒的单位表面积的硅烷醇基数可以通过基于G.W.Sears的AnalyticalChemistry,vol.28,No.12,1956,1982~1983中记载的使用中和滴定的Sears法来算出。对于硅烷醇基数的计算式,通过以下的式子来计算。
ρ:硅烷醇基数[个/nm2]
c:滴定中使用的氢氧化钠溶液的浓度[mol/L]
a:pH4-9的氢氧化钠溶液的滴加量[ml]
NA:阿伏伽德罗数[6.022×1023个/mol]
C:二氧化硅质量[g]
S:BET比表面积[nm2/g]
[在pH4下的研磨]
(实施例1-1)
将作为磨粒的硅烷醇基数为1.5个/nm2的胶体二氧化硅(平均二次粒径:67nm,通过溶胶凝胶法合成)以成为0.1质量%的浓度的方式与水混合(混合温度:25℃,混合时间:10分钟),进而添加作为pH调节剂的硝酸调整pH,制备研磨用组合物。研磨用组合物的pH通过pH计确认为4。
(实施例1-2)
将研磨用组合物中的磨粒的浓度变更为4质量%,除此以外,与实施例1-1进行同样地操作,制备研磨用组合物。
(实施例1-3)
将作为磨粒的硅烷醇基数为1.6个/nm2的胶体二氧化硅(用硅酸钠法合成的)以成为4质量%的浓度的方式与水混合(混合温度:25℃,混合时间:10分钟),进而添加作为pH调节剂的硝酸调整pH,制备研磨用组合物。研磨用组合物的pH通过pH计确认为4。
(实施例1-4)
将作为磨粒的硅烷醇基数为1.9个/nm2的气相二氧化硅以成为1质量%的浓度的方式与水混合(混合温度:25℃,混合时间:10分钟),进而添加作为pH调节剂的硝酸调整pH,制备研磨用组合物。研磨用组合物的pH通过pH计确认为4。
(比较例1-1)
使用硅烷醇基数为5.7个/nm2的胶体二氧化硅(商品名:SS-3P,扶桑化学工业株式会社制,平均二次粒径:70nm,用溶胶凝胶法合成的)作为磨粒,除此以外,与实施例1-1进行同样地操作,制备研磨用组合物。
(比较例1-2)
使用硅烷醇基数为5.7个/nm2的胶体二氧化硅(商品名:SS-3P,扶桑化学工业株式会社制,平均二次粒径:70nm,用溶胶凝胶法合成的)作为磨粒,除此以外,与实施例1-2进行同样的操作,制备研磨用组合物。
(比较例1-3)
使用不具有硅烷醇基的α-氧化铝作为磨粒,除此以外,与实施例1-1进行同样的操作,制备研磨用组合物。
(比较例1-4)
使用不具有硅烷醇基的γ-氧化铝作为磨粒,除此以外,与实施例1-1进行同样的操作,制备研磨用组合物。
(评价)
<磨粒的真密度>
磨粒的真密度通过下述式示出的比重瓶法来计算。
Sg:磨粒的真密度
Wa:比重瓶的质量
Wb:试样与比重瓶的质量
Wc:试样与乙醇、比重瓶的质量
Wd:乙醇与比重瓶的质量
Ld:乙醇的质量
<研磨速度>
研磨速度通过以下的式子来计算。
针对Poly Si、SiN和TEOS,利用光干涉式膜厚测定装置求出膜厚,通过将其差除以研磨时间来进行评价。
将实施例1-1~1-4和比较例1-1~1-4的研磨用组合物的评价结果示于下述表1。需要说明的是,在表1~3中的选择比的栏中,分别在“Poly Si/TEOS”的栏中示出Poly Si的研磨速度除以TEOS的研磨速度而得到的值,在“Poly Si/SiN”的栏中示出Poly Si的研磨速度除以SiN的研磨速度而得到的值。
[表1]
如上述表1所示,可知:实施例1-1~1-4的研磨用组合物与比较例1-1~1-4的研磨用组合物相比,进一步提高多晶硅(Poly Si)的研磨速度。另外,实施例1-1和实施例1-2中,多晶硅(Poly Si)的研磨速度相对于TEOS的研磨速度之比(选择比)与比较例1-1~1-4相比有提高。
[在pH7下的研磨]
(实施例2-1)
使用硝酸和氢氧化钾作为pH调节剂,将研磨用组合物的pH调整至7,除此以外,与实施例1-2进行同样的操作,制备研磨用组合物。
(比较例2-1)
使用硝酸和氢氧化钾作为pH调节剂,将研磨用组合物的pH调整至7,除此以外,与比较例1-2进行同样的操作,制备研磨用组合物。
将实施例2-1和比较例2-1的研磨用组合物的评价结果示于下述表2。
[表2]
如上述表2所示,可知:实施例2-1的研磨用组合物与比较例2-1的研磨用组合物相比,进一步提高多晶硅(Poly Si)的研磨速度。另外,实施例2-1中,多晶硅(Poly Si)的研磨速度相对于TEOS的研磨速度之比(选择比)、以及多晶硅(Poly Si)的研磨速度相对于SiN的研磨速度之比(选择比)与比较例2-1相比有提高。
[在pH10下的研磨]
(实施例3-1)
使用氢氧化钾作为pH调节剂,将研磨用组合物的pH调整至10,除此以外,与实施例1-2进行同样的操作,制备研磨用组合物。
(比较例3-1)
使用氢氧化钾作为pH调节剂,将研磨用组合物的pH调整至10,除此以外,与比较例1-2进行同样的操作,制备研磨用组合物。
将实施例3-1和比较例3-1的研磨用组合物的评价结果示于下述表3。
[表3]
如上述表3所示,实施例3-1的研磨用组合物中,多晶硅(Poly Si)的研磨速度相对于TEOS的研磨速度之比(选择比)、以及多晶硅(Poly Si)的研磨速度相对于SiN的研磨速度之比(选择比)与比较例3-1相比有提高。
需要说明的是,本申请基于2015年2月10日申请的日本专利申请第2015-024377号,其公开内容通过参照整体被引用。
Claims (3)
1.一种研磨用组合物,其用于对包含单质硅和除单质硅以外的含硅化合物的研磨对象物进行研磨的用途,
该研磨用组合物包含作为磨粒的用溶胶凝胶法制造的胶体二氧化硅和分散介质,
所述用溶胶凝胶法制造的胶体二氧化硅的单位表面积的硅烷醇基数为1.5个/nm2以上且为1.9个/nm2以下,
所述用溶胶凝胶法制造的胶体二氧化硅的含量为0.002质量%以上10质量%以下。
2.一种研磨方法,其利用权利要求1所述的研磨用组合物对包含单质硅和除单质硅以外的含硅化合物的研磨对象物进行研磨。
3.一种基板的制造方法,其包括通过权利要求2所述的研磨方法对包含单质硅和除单质硅以外的含硅化合物的研磨对象物进行研磨的工序。
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JP7493367B2 (ja) | 2020-03-27 | 2024-05-31 | 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 |
JP2022052548A (ja) * | 2020-09-23 | 2022-04-04 | 株式会社フジミインコーポレーテッド | 研磨用組成物 |
JP2023146034A (ja) * | 2022-03-29 | 2023-10-12 | 株式会社フジミインコーポレーテッド | 研磨用組成物およびこれを用いた研磨方法 |
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JP4635217B2 (ja) * | 2003-09-17 | 2011-02-23 | 学校法人慶應義塾 | 表面処理剤及び材料及び表面処理方法 |
GB2415199B (en) * | 2004-06-14 | 2009-06-17 | Kao Corp | Polishing composition |
JP2006231436A (ja) * | 2005-02-23 | 2006-09-07 | Tokyo Seimitsu Co Ltd | 研磨用スラリーおよび研磨方法 |
WO2006098141A1 (ja) * | 2005-03-16 | 2006-09-21 | Asahi Glass Company, Limited | 半導体集積回路装置用研磨剤、研磨方法および半導体集積回路装置の製造方法 |
US7902072B2 (en) * | 2006-02-28 | 2011-03-08 | Fujifilm Corporation | Metal-polishing composition and chemical-mechanical polishing method |
JP2008135452A (ja) * | 2006-11-27 | 2008-06-12 | Fujimi Inc | 研磨用組成物及び研磨方法 |
TWI436947B (zh) * | 2007-03-27 | 2014-05-11 | Fuso Chemical Co Ltd | 膠體矽石及其製法 |
EP2188344B1 (en) * | 2007-09-21 | 2016-04-27 | Cabot Microelectronics Corporation | Polishing composition and method utilizing abrasive particles treated with an aminosilane |
WO2009104465A1 (ja) * | 2008-02-18 | 2009-08-27 | Jsr株式会社 | 化学機械研磨用水系分散体および化学機械研磨方法 |
JP2010034497A (ja) * | 2008-02-18 | 2010-02-12 | Jsr Corp | 化学機械研磨用水系分散体およびその製造方法、ならびに化学機械研磨方法 |
JP2009289885A (ja) * | 2008-05-28 | 2009-12-10 | Fujifilm Corp | 研磨液及び研磨方法 |
JP2010067914A (ja) * | 2008-09-12 | 2010-03-25 | Fujifilm Corp | 化学的機械的研磨液、及び化学的機械的研磨方法 |
US8883031B2 (en) * | 2009-08-19 | 2014-11-11 | Hitachi Chemical Company, Ltd. | CMP polishing liquid and polishing method |
JP5744597B2 (ja) * | 2011-03-31 | 2015-07-08 | Hoya株式会社 | マスクブランクス用ガラス基板の製造方法、マスクブランクスの製造方法、転写マスクの製造方法、及び半導体装置の製造方法 |
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SG11201706046PA (en) | 2017-08-30 |
EP3258484A1 (en) | 2017-12-20 |
SG10201907376RA (en) | 2019-09-27 |
US20180022959A1 (en) | 2018-01-25 |
CN107396639A (zh) | 2017-11-24 |
KR20170115058A (ko) | 2017-10-16 |
TW202340406A (zh) | 2023-10-16 |
TWI814030B (zh) | 2023-09-01 |
TWI746433B (zh) | 2021-11-21 |
TWI755727B (zh) | 2022-02-21 |
TW202033312A (zh) | 2020-09-16 |
TW202140706A (zh) | 2021-11-01 |
WO2016129508A1 (ja) | 2016-08-18 |
JP2016149402A (ja) | 2016-08-18 |
KR102649656B1 (ko) | 2024-03-21 |
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