JP6082237B2 - テクスチャー構造を有するシリコン基板の製法 - Google Patents
テクスチャー構造を有するシリコン基板の製法 Download PDFInfo
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- JP6082237B2 JP6082237B2 JP2012266499A JP2012266499A JP6082237B2 JP 6082237 B2 JP6082237 B2 JP 6082237B2 JP 2012266499 A JP2012266499 A JP 2012266499A JP 2012266499 A JP2012266499 A JP 2012266499A JP 6082237 B2 JP6082237 B2 JP 6082237B2
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- meth
- silicon substrate
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- 239000000758 substrate Substances 0.000 title claims description 211
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- 229910052710 silicon Inorganic materials 0.000 title claims description 207
- 239000010703 silicon Substances 0.000 title claims description 205
- 238000004519 manufacturing process Methods 0.000 title claims description 45
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- 238000005530 etching Methods 0.000 claims description 136
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- 239000011347 resin Substances 0.000 claims description 117
- 238000000034 method Methods 0.000 claims description 98
- 239000000178 monomer Substances 0.000 claims description 85
- 239000007789 gas Substances 0.000 claims description 82
- 125000004432 carbon atom Chemical group C* 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 53
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- 238000000576 coating method Methods 0.000 claims description 35
- 239000011248 coating agent Substances 0.000 claims description 34
- 125000000217 alkyl group Chemical group 0.000 claims description 32
- 229910052731 fluorine Inorganic materials 0.000 claims description 31
- 239000007864 aqueous solution Substances 0.000 claims description 30
- 239000011737 fluorine Substances 0.000 claims description 30
- 150000004703 alkoxides Chemical class 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
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- 125000003118 aryl group Chemical group 0.000 claims description 8
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- 239000010936 titanium Chemical group 0.000 claims description 6
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 9
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- 239000012298 atmosphere Substances 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 125000001033 ether group Chemical group 0.000 description 6
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 6
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- 238000002360 preparation method Methods 0.000 description 6
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- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical class OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 5
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- PUBNJSZGANKUGX-UHFFFAOYSA-N 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=C(C)C=C1 PUBNJSZGANKUGX-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
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- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 description 4
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- ISGXOWLMGOPVPB-UHFFFAOYSA-N n,n-dibenzylaniline Chemical compound C=1C=CC=CC=1CN(C=1C=CC=CC=1)CC1=CC=CC=C1 ISGXOWLMGOPVPB-UHFFFAOYSA-N 0.000 description 1
- FZPXKEPZZOEPGX-UHFFFAOYSA-N n,n-dibutylaniline Chemical compound CCCCN(CCCC)C1=CC=CC=C1 FZPXKEPZZOEPGX-UHFFFAOYSA-N 0.000 description 1
- HKJNHYJTVPWVGV-UHFFFAOYSA-N n,n-diethyl-4-methylaniline Chemical compound CCN(CC)C1=CC=C(C)C=C1 HKJNHYJTVPWVGV-UHFFFAOYSA-N 0.000 description 1
- AJUXDFHPVZQOGF-UHFFFAOYSA-N n,n-dimethyl-1-naphthylamine Chemical compound C1=CC=C2C(N(C)C)=CC=CC2=C1 AJUXDFHPVZQOGF-UHFFFAOYSA-N 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- QMHNQZGXPNCMCO-UHFFFAOYSA-N n,n-dimethylhexan-1-amine Chemical compound CCCCCCN(C)C QMHNQZGXPNCMCO-UHFFFAOYSA-N 0.000 description 1
- IKZPRXHVTFNIEK-UHFFFAOYSA-N n,n-dimethylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C)C)=CC=C21 IKZPRXHVTFNIEK-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- LXTZRIBXKVRLOA-UHFFFAOYSA-N padimate a Chemical compound CCCCCOC(=O)C1=CC=C(N(C)C)C=C1 LXTZRIBXKVRLOA-UHFFFAOYSA-N 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- NQFOGDIWKQWFMN-UHFFFAOYSA-N phenalene Chemical compound C1=CC([CH]C=C2)=C3C2=CC=CC3=C1 NQFOGDIWKQWFMN-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- SFLGSKRGOWRGBR-UHFFFAOYSA-N phthalane Chemical compound C1=CC=C2COCC2=C1 SFLGSKRGOWRGBR-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 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
- 229920000136 polysorbate Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 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
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- XZTJQQLJJCXOLP-UHFFFAOYSA-M sodium;decyl sulfate Chemical compound [Na+].CCCCCCCCCCOS([O-])(=O)=O XZTJQQLJJCXOLP-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 1
- 229960000909 sulfur hexafluoride Drugs 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ZLGWXNBXAXOQBG-UHFFFAOYSA-N triethoxy(3,3,3-trifluoropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)F ZLGWXNBXAXOQBG-UHFFFAOYSA-N 0.000 description 1
- NYIKUOULKCEZDO-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,6-nonafluorohexyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)F NYIKUOULKCEZDO-UHFFFAOYSA-N 0.000 description 1
- AVYKQOAMZCAHRG-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AVYKQOAMZCAHRG-UHFFFAOYSA-N 0.000 description 1
- MLXDKRSDUJLNAB-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F MLXDKRSDUJLNAB-UHFFFAOYSA-N 0.000 description 1
- XQDKPCKQUIWESK-UHFFFAOYSA-N triethoxy-[5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluoro-2-(1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexyl)decyl]silane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(C[Si](OCC)(OCC)OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F XQDKPCKQUIWESK-UHFFFAOYSA-N 0.000 description 1
- IJROHELDTBDTPH-UHFFFAOYSA-N trimethoxy(3,3,4,4,5,5,6,6,6-nonafluorohexyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)F IJROHELDTBDTPH-UHFFFAOYSA-N 0.000 description 1
- BVQYIDJXNYHKRK-UHFFFAOYSA-N trimethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BVQYIDJXNYHKRK-UHFFFAOYSA-N 0.000 description 1
- KGDRVNVVENRUAE-UHFFFAOYSA-N trimethoxy-[3-(1,2,2,3,3,4,4,5,5,6,6-undecafluorocyclohexyl)oxypropyl]silane Chemical compound CO[Si](OC)(OC)CCCOC1(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F KGDRVNVVENRUAE-UHFFFAOYSA-N 0.000 description 1
- RDYMVWVBSWCBKT-UHFFFAOYSA-N trimethoxy-[5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluoro-2-(1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexyl)decyl]silane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(C[Si](OC)(OC)OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RDYMVWVBSWCBKT-UHFFFAOYSA-N 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- 239000012953 triphenylsulfonium Substances 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- JAIHDOVRCZNXDU-UHFFFAOYSA-N violanthrene Chemical compound C12=C3C4=CC=C2C2=CC=CC=C2CC1=CC=C3C1=CC=C2CC3=CC=CC=C3C3=CC=C4C1=C32 JAIHDOVRCZNXDU-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- 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
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
- H01L21/3081—Chemical or electrical treatment, e.g. electrolytic etching using masks characterised by their composition, e.g. multilayer masks, materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
-
- 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
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
- H01L21/3083—Chemical or electrical treatment, e.g. electrolytic etching using masks characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
- H01L21/3085—Chemical or electrical treatment, e.g. electrolytic etching using masks characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by their behaviour during the process, e.g. soluble masks, redeposited masks
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Ceramic Engineering (AREA)
- Electromagnetism (AREA)
- Theoretical Computer Science (AREA)
- Mathematical Physics (AREA)
- Shaping Of Tube Ends By Bending Or Straightening (AREA)
- Weting (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Silicon Polymers (AREA)
- Drying Of Semiconductors (AREA)
- Photovoltaic Devices (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Description
(A)シリコン基板上に樹脂を含有する組成物でパターンを形成する工程、
(B)エッチングガスをパターン部分以外のシリコン基板表面に照射する工程、
(C)エッチングガスを照射したシリコン基板をアルカリエッチング液により処理し、パターン部分の下に凹構造を形成する工程、
を含むことを特徴とするテクスチャー構造を有するシリコン基板の製法に係る。
パターンの形成方法としては、公知のパターンの形成方法を、何ら制限されずに用いることができるが、数μmオーダー以下の微細なパターン形成を勘案すると、好ましくは、インプリント技術でパターンを形成する方法が使用される。
本発明において、(メタ)アクリル基を有する重合性単量体((メタ)アクリル基含有重合性単量体)は、特に制限されるものではなく、光重合に使用される公知の重合性単量体を使用することができる。この(メタ)アクリル基含有重合性単量体は、当然のことながら、(メタ)アクリル基含有アルコキシシランを含まない。そして、好ましい化合物としては、(メタ)アクリル基を有し、分子中にケイ素原子を含まない重合性単量体が挙げられる。これら重合性単量体は、1分子中に1つの(メタ)アクリル基を有する単官能重合性単量体であってもよいし、1分子中に2つ以上の(メタ)アクリル基を有する多官能重合性単量体であってもよい。さらには、これら単官能重合性単量体及び多官能重合性単量体を組み合わせて使用することもできる。(メタ)アクリル基含有重合性単量体において、ビニルエーテル基も有するものは、光重合の他に、熱処理によっても重合反応が進行することから、本発明の効果をより高める点で好ましく用いることができる。
(メタ)アクリル基を有する酸性基含有重合性単量体としては、特に制限されるものではなく、光重合に使用される公知のリン酸基、カルボン酸基、又はスルホ基を有する重合性単量体を使用することができる。さらには、これらリン酸基、カルボン酸基、又はスルホ基を有する重合性単量体は組み合わせても使用される。
アルコキシシラン類の加水分解物は、アルコキシシラン類のアルコキシ基の一部又は全部の加水分解による生成物、アルコキシシランの重縮合体、該重縮合体のアルコキシ基の一部又は全部の加水分解による生成物及びこれらの種々の混合物を意味する。
アルコキシシラン類の内、一般的なアルコキシシランとしては、一般式(2)
(メタ)アクリル基含有アルコキシシランとしては、一般式(3)
上記ハロゲン元素を有するアルコキシシランとしては、一般式(4)
上述の(A)工程において形成されたパターンを有するシリコン基板に対して、エッチングガスをパターン部分以外のシリコン基板表面に照射する。ここで「パターン部分以外のシリコン基板表面」とは、シリコン基板表面のうち、シリコン基板上に工程(A)で積層した樹脂含有組成物からなるパターン部分の直下のシリコン基板表面を除外した部分を指称する。すなわち、エッチングガスが、パターン部分の直下に存在する領域のシリコン基板表面に照射されない限りは、パターン部分に照射されても構わない。
アルカリエッチング液としては、太陽電池用シリコン基板のテクスチャー構造形成等で一般的に使用されているアルカリエッチング液を何ら制限なく用いることができ、例えば、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物の水溶液、水酸化セシウム水溶液、ヒドラジン水溶液、炭酸塩水溶液、珪酸ナトリウム水溶液、水酸化テトラメチルアンモニウム水溶液、水酸化テトラエチルアンモニウム水溶液、水酸化テトラブチルアンモニウム水溶液等が挙げられ、なかでも、シリコンの結晶方位面で100面・110面・111面のエッチング速度が異なることを利用して、異方性エッチングを行うことから、シリコンの結晶格子に応じた溶解性において、溶解速度や均一溶解等の溶解挙動から水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物の水溶液が好ましく用いられる。添加剤として、界面活性剤、塩酸塩、硫酸塩、カルボン酸塩、イソプロピルアルコール、ブチルアルコール、ポリビニルアルコール等を含んでいても良い。
本発明のテクスチャー構造を有するシリコン基板の製法で得られたシリコン基板は、太陽電池用又はLED発光素子用のシリコン基板又はナノインプリント用モールドとして使用することもできる。
反応性イオンエッチング装置を用いて、以下の条件にて、酸素ガス、CHF3ガス、Arガスによるドライエッチングを行った。本条件でのエッチング時間と各種光硬化膜の塗膜減少量との関係から、予め、ドライエッチング速度(nm/min)を算出した。
酸素ガス:ガスフロー50sccm、RFパワー100W、制御圧力5.0Pa
CHF3ガス:ガスフロー50sccm、RFパワー100W、制御圧力2.0Pa
Arガス:ガスフロー50sccm、RFパワー100W、制御圧力2.0Pa
[実施例1]
エタノール13.6g、(メタ)アクリル基含有アルコキシシランとしてトリメトキシシリルプロピルアクリレート3.0g、一般的なアルコキシシランとしてエチルシリケート40(コルコール(株)製、テトラエトキシシランの平均5量体物)6.8g、金属アルコキシドとして、85質量%ジルコニウムブトキシド(テトラブチルジルコニウムアルコキシド)の1−ブタノール溶液1.7gを混合し、得られた混合物に、撹拌混合しながら、エタノール4.25g/水0.85g/2N−HCl 0.16gの2N−HCl/エタノール混合水溶液を、室温において徐々に滴下した。さらに、エタノール1g/水0.46gのエタノール水溶液を徐々に滴下し、室温において1時間撹拌し、一般的なアルコキシシラン、(メタ)アクリル基含有アルコキシシラン及び金属アルコキシドからなる加水分解物(c)を得た。
得られた樹脂含有組成物を、1−メトキシ−2−プロパノールにて20重量%溶液となるよう希釈した。希釈した樹脂含有組成物を、シリコン(100)ウエハー(P型、片鏡面、酸化膜なし)に、1000rpm、30秒間でスピンコートし、110℃で2分間乾燥して、樹脂含有組成物の塗膜がコーティングされたシリコンウエハーを得た。該シリコンウエハーに対して、ライン(凸)幅300nm、ピッチ3μm、高さ380nmの格子パターンを備えた石英製モールドを使用し、光ナノインプリント装置において、圧力1MPaをかけ、LED365nm光源から光を60秒間照射して、光ナノインプリントを行った。シリコンウエハー上に形成されたナノインプリントパターンをSEMにて観察し、そのSEM写真を図4(表面)に示した。
上記のようにして得られたナノインプリントパターンについて、CHF3ガスにてドライエッチングを5分間行い、残膜を除去した。
上記のCHF3ガスのドライエッチング処理にて残膜を除去したサンプルを、水酸化ナトリウム5%/イソプロピルアルコール3%の水溶液からなるアルカリエッチング液中に浸漬し、55℃で20分間アルカリエッチング処理を行った。その後、リンス処理として、該サンプルを水酸化ナトリウム2.5%水溶液中で2分間超音波処理し、さらに、水中にて1分間超音波処理した。リンス処理前のSEM写真を図5(表面)及び図6(断面)に、リンス処理後のSEM写真を図7(表面)及び図8(断面)に示した。
実施例1と同様にして、樹脂含有組成物の調製、パターンの転写・光硬化を行った。
得られたナノインプリントパターンについて、酸素ガスにてドライエッチングを8分間行い、残膜の除去を行った。
エタノール13.6g、(メタ)アクリル基含有アルコキシシランとしてトリメトキシシリルプロピルアクリレート3.0g、一般的なアルコキシシランとしてエチルシリケート40(コルコール(株)製、テトラエトキシシランの平均5量体物)6.8gを混合し、得られた混合物に、撹拌混合しながら、エタノール4.25g/水0.85g/2N−HCl 0.16gの2N−HCl/エタノール混合水溶液を、室温において徐々に滴下した。さらに、エタノール1g/水0.32gのエタノール水溶液を徐々に滴下し、室温において1時間撹拌し、一般的なアルコキシシラン及び(メタ)アクリル基含有アルコキシシランからなる加水分解物(c)を得た。
実施例1と同様にして、樹脂含有組成物の調製、パターンの転写・光硬化、ドライエッチング処理を行った。
(メタ)アクリル基を有する重合性単量体(a)として、ポリエチレングリコールジアクリレート(新中村化学工業(株)製、NKエステル A−200)2.5g、エトキシ化ビスフェノールAジアクリレート(新中村化学工業(株)製、NKエステル A−BPE−10)7.5g、フェノキシポリエチレングリコールアクリレート(新中村化学工業(株)製、NKエステル AMP−10G)5.0g、ヒドロキシエチル化o−フェニルフェノールアクリレート(新中村化学工業(株)製、NKエステル A−LEN−10)5.0g、トリシクロデカンジメタノールジアクリレート(新中村化学工業(株)製、NKエステルA−DCP)5.0gを使用した。
重合性単量体として、ポリエチレングリコールジアクリレート(新中村化学工業(株)製、NKエステル A−200)2.5g、トリシクロデカンジメタノールジアクリレート(新中村化学工業(株)製、NKエステル A−DCP)5.0g、2−ヒドロキ−3−アクリロイロキシプロピルメタクリレート(新中村化学工業(株)製、NKエステル 701A)7.5g((メタ)アクリル基を有する重合性単量体(a)として)及びカルボキシル基を有する重合性単量体であるフタル酸モノ[2−アクリロイルオキシエチル](共栄社化学(株)製、ライトアクリレート HOA―MPL(N))10.0g((メタ)アクリル基を有する酸性基含有重合性単量体(a')として)を使用した。
エタノール4.4g、(メタ)アクリル基含有アルコキシシランとしてトリメトキシシリルプロピルアクリレート3.0gを混合し、ケイ素化合物(c)のエタノール溶液を調製した。
実施例1と同様にして、樹脂含有組成物を調製した。
実施例1と同様にして、樹脂含有組成物の調製を行った。
ハロゲン元素を有するアルコキシシラン類であるフッ素化シラン化合物として(3,3,3−トリフルオロプロピル)トリメトキシシランを、固形分10%となるようエタノールで希釈することによって得られた溶液0.28g、(メタ)アクリル基含有アルコキシシランとしてトリメトキシシリルトリメチレンアクリレート3.0g、エタノール13.6gに、撹拌混合しながら、エタノール1.63g/水0.31g/2N−HCl 0.06gの2N−HCl/エタノール混合水溶液を徐々に滴下し、室温において1時間撹拌し、フッ素化シラン化合物及び(メタ)アクリル基含有アルコキシシランの混合物からなる加水分解物を得た。得られた加水分解物に、一般的なアルコキシシランとして、エチルシリケート40(コルコート(株)製、テトラエトキシシランの平均5量体物)6.8g、金属アルコキシドとして85質量%ジルコニウムブトキシド(テトラブチルジルコニウムアルコキシド)の1−ブタノール溶液1.70gを混合し、この混合物に、撹拌混合しながら、エタノール2.62g/水0.66g/2N−HCl 0.10gの2N−HCl/エタノール混合水溶液を室温において徐々に滴下した。さらに、エタノール1.00g/水0.37gのエタノール水溶液を徐々に滴下し、室温において1時間撹拌し、アルコキシシランの加水分解物及び金属アルコキシドの加水分解物をさらに含んだ加水分解物(c)を得た。
実施例1と同様にして、樹脂を含有する組成物の調製、パターンの転写・光硬化を行った。
実施例1においてドライエッチング処理による残膜の除去を行わなかったこと以外は、実施例1と同様にして、樹脂を含有する組成物の調製、パターンの転写・光硬化、アルカリエッチング処理・リンス処理を行った。リンス処理後のサンプルのSEM観察結果(図20(表面)参照)より、パターン部分の下に凹構造が形成されたテクスチャー構造を有するシリコン基板が作製されていないことが確認された。
実施例1において得られたナノインプリントパターンについて、CHF3ガスによるドライエッチングを1分間しか行なわず、残膜を除去しなかったこと(SEM観察に結果、残膜が残留していることが確認された)以外は、実施例1と同様にして、樹脂を含有する組成物の調製、パターンの転写・光硬化、アルカリエッチング処理・リンス処理を行った。リンス処理後のサンプルのSEM観察結果より、パターン部分の下に凹構造が形成されテクスチャー構造を有するシリコン基板が作製されていないことが確認された。
Claims (12)
- テクスチャー構造を有するシリコン基板を製造する方法であって、該方法は、
(A)シリコン基板上に、樹脂を含有する組成物でパターンを形成する工程、
(B)エッチングガスを、パターン部分以外のシリコン基板表面に照射する工程、
(C)エッチングガスを照射したシリコン基板を、アルカリエッチング液により処理し、パターン部分の下に凹構造を形成する工程
を含んでなり、前記樹脂を含有する組成物が、(a)(メタ)アクリル基を有する重合性単量体、(b)光重合開始剤、及び(c)アルコキシシラン類の加水分解物からなるケイ素化合物を含んでなり、前記アルコキシシラン類の加水分解物が、一般式(2)
- アルコキシシラン類の加水分解物が、さらに、一般式(4)
- 樹脂を含有する組成物が、さらに、(a')(メタ)アクリル基を有する酸性基含有重合性単量体を含むものである請求項1又は2に記載の製法。
- 工程(A)において、シリコン基板上に、樹脂を含有する組成物を塗布して、塗膜を形成させた後、モールドにより塗膜にパターンを転写して、基板上にパターンを形成する請求項1〜3のいずれかに記載の製法。
- 工程(A)において、シリコン基板が、酸化膜を形成させる工程を経ていないシリコン基板である請求項1〜4のいずれかに記載の製法。
- 得られるシリコン基板のテクスチャー構造が、太陽電池ウエハー用又はLED基板用に適するテクスチャー構造である請求項1〜5のいずれかに記載の製法。
- 工程(B)において、エッチングガスが、少なくともフッ素系ガス又は酸素ガスを含むエッチングガスである請求項1〜6のいずれかに記載の製法。
- 工程(C)において、アルカリエッチング液が、アルカリ金属水酸化物/イソプロピルアルコールの水溶液である請求項1〜7のいずれかに記載の製法。
- さらに、工程(C)で得られたテクスチャー構造を有するシリコン基板をアルカリリンスして、パターンの残渣を除去する工程を含んでなる、請求項1〜8のいずれかに記載の製法。
- 請求項1記載の製法において使用される、樹脂を含有する組成物であって、該組成物は、
(a)(メタ)アクリル基を有する重合性単量体、
(b)光重合開始剤、及び
(c)アルコキシシラン類の加水分解物からなるケイ素化合物
を含んでなるものであり、前記アルコキシシラン類の加水分解物が、一般式(2)
- アルコキシシラン類の加水分解物が、さらに、一般式(4)
- さらに、(a')(メタ)アクリル基を有する酸性基含有重合性単量体を含むものである請求項10又は11に記載の組成物。
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KR102098764B1 (ko) * | 2017-03-07 | 2020-04-08 | 주식회사 엘지화학 | 정점 쌍 안정 액정 패널의 액정 배향을 위한 패턴 형성방법, 이에 따라 형성된 패턴을 포함하는 액정 배향기판 및 상기 패턴의 형성에 사용된 마스크 기판 |
JP7001511B2 (ja) * | 2017-03-27 | 2022-01-19 | 三洋化成工業株式会社 | 活性エネルギー線硬化型樹脂組成物 |
CN110271119B (zh) * | 2019-05-23 | 2021-07-20 | 深圳市伊声声学科技有限公司 | 一种利用模具制造防水透气膜的方法 |
KR102565935B1 (ko) * | 2020-11-20 | 2023-08-11 | 재단법인 구미전자정보기술원 | 가스 분위기 조절을 통한 반도체 기판 텍스쳐링 방법 |
CN113136144A (zh) * | 2021-03-18 | 2021-07-20 | 武汉风帆电化科技股份有限公司 | 一种用于晶硅片快速碱抛光的抛光剂及其应用方法 |
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US8158728B2 (en) * | 2004-02-13 | 2012-04-17 | The University Of North Carolina At Chapel Hill | Methods and materials for fabricating microfluidic devices |
US20050221222A1 (en) * | 2004-03-22 | 2005-10-06 | Canon Kabushiki Kaisha | Photosensitive resin composition, resist pattern forming method, substrate processing method, and device manufacturing method |
JP4430488B2 (ja) | 2004-09-02 | 2010-03-10 | シャープ株式会社 | 太陽電池及びその製造方法 |
JP5000112B2 (ja) * | 2005-09-09 | 2012-08-15 | 東京応化工業株式会社 | ナノインプリントリソグラフィによるパターン形成方法 |
JP5309436B2 (ja) * | 2006-10-16 | 2013-10-09 | 日立化成株式会社 | 樹脂製微細構造物、その製造方法及び重合性樹脂組成物 |
JP5611519B2 (ja) * | 2008-10-29 | 2014-10-22 | 富士フイルム株式会社 | ナノインプリント用組成物、パターンおよびその形成方法 |
WO2010090142A1 (ja) | 2009-02-03 | 2010-08-12 | 株式会社カネカ | 透明導電膜付き基板および薄膜光電変換装置 |
CN102362356A (zh) * | 2009-03-25 | 2012-02-22 | 三菱电机株式会社 | 衬底的表面粗化方法以及光伏装置的制造方法 |
JP5445743B2 (ja) * | 2009-04-14 | 2014-03-19 | 日産化学工業株式会社 | 光インプリント用被膜形成用組成物 |
JP5430751B2 (ja) * | 2010-04-21 | 2014-03-05 | 三菱電機株式会社 | 低反射基板の製造方法、および光起電力装置の製造方法 |
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