JP4742665B2 - Method of manufacturing processed substrate processed by etching - Google Patents
Method of manufacturing processed substrate processed by etching Download PDFInfo
- Publication number
- JP4742665B2 JP4742665B2 JP2005131674A JP2005131674A JP4742665B2 JP 4742665 B2 JP4742665 B2 JP 4742665B2 JP 2005131674 A JP2005131674 A JP 2005131674A JP 2005131674 A JP2005131674 A JP 2005131674A JP 4742665 B2 JP4742665 B2 JP 4742665B2
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- mold
- resist
- pattern
- acrylate
- 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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- 239000000758 substrate Substances 0.000 title claims description 76
- 238000005530 etching Methods 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000000178 monomer Substances 0.000 claims description 75
- 239000000203 mixture Substances 0.000 claims description 73
- 229910052731 fluorine Inorganic materials 0.000 claims description 53
- 239000004094 surface-active agent Substances 0.000 claims description 33
- 239000011737 fluorine Substances 0.000 claims description 30
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 28
- 125000001153 fluoro group Chemical group F* 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 239000003505 polymerization initiator Substances 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 37
- -1 perfluoro Chemical group 0.000 description 36
- 150000001875 compounds Chemical class 0.000 description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 18
- 229910052710 silicon Inorganic materials 0.000 description 18
- 239000010703 silicon Substances 0.000 description 17
- 239000002904 solvent Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000001020 plasma etching Methods 0.000 description 5
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- 238000001127 nanoimprint lithography Methods 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920001567 vinyl ester resin Polymers 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000001312 dry etching Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 2
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 2
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 2
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 2
- IBTLFDCPAJLATQ-UHFFFAOYSA-N 1-prop-2-enoxybutane Chemical compound CCCCOCC=C IBTLFDCPAJLATQ-UHFFFAOYSA-N 0.000 description 2
- LWJHSQQHGRQCKO-UHFFFAOYSA-N 1-prop-2-enoxypropane Chemical compound CCCOCC=C LWJHSQQHGRQCKO-UHFFFAOYSA-N 0.000 description 2
- DSSAWHFZNWVJEC-UHFFFAOYSA-N 3-(ethenoxymethyl)heptane Chemical compound CCCCC(CC)COC=C DSSAWHFZNWVJEC-UHFFFAOYSA-N 0.000 description 2
- OJPSFJLSZZTSDF-UHFFFAOYSA-N 3-ethoxyprop-1-ene Chemical compound CCOCC=C OJPSFJLSZZTSDF-UHFFFAOYSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical group C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 238000007607 die coating method Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- BLZSRIYYOIZLJL-UHFFFAOYSA-N ethenyl pentanoate Chemical compound CCCCC(=O)OC=C BLZSRIYYOIZLJL-UHFFFAOYSA-N 0.000 description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 230000015654 memory Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical group C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 2
- 238000004382 potting Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- ZHOFTZAKGRZBSL-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-8-methoxyoctane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZHOFTZAKGRZBSL-UHFFFAOYSA-N 0.000 description 1
- RFPMOTJETISENI-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7-pentadecafluoro-7-methoxyheptane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RFPMOTJETISENI-UHFFFAOYSA-N 0.000 description 1
- HRXXERHTOVVTQF-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoro-2-methoxypropane Chemical compound COC(F)(C(F)(F)F)C(F)(F)F HRXXERHTOVVTQF-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 description 1
- JMGNVALALWCTLC-UHFFFAOYSA-N 1-fluoro-2-(2-fluoroethenoxy)ethene Chemical compound FC=COC=CF JMGNVALALWCTLC-UHFFFAOYSA-N 0.000 description 1
- GKZPEYIPJQHPNC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GKZPEYIPJQHPNC-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- MXXJCTNAJZKLJJ-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxyperoxymethyl)oxirane Chemical compound C1OC1COOOCC1CO1 MXXJCTNAJZKLJJ-UHFFFAOYSA-N 0.000 description 1
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- IXPWKHNDQICVPZ-UHFFFAOYSA-N 2-methylhex-1-en-3-yne Chemical compound CCC#CC(C)=C IXPWKHNDQICVPZ-UHFFFAOYSA-N 0.000 description 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- SKKHNUKNMQLBTJ-UHFFFAOYSA-N 3-bicyclo[2.2.1]heptanyl 2-methylprop-2-enoate Chemical compound C1CC2C(OC(=O)C(=C)C)CC1C2 SKKHNUKNMQLBTJ-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N DEAEMA Natural products CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 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
- 125000003700 epoxy group Chemical group 0.000 description 1
- JZRGFKQYQJKGAK-UHFFFAOYSA-N ethenyl cyclohexanecarboxylate Chemical compound C=COC(=O)C1CCCCC1 JZRGFKQYQJKGAK-UHFFFAOYSA-N 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- GVGCUCJTUSOZKP-UHFFFAOYSA-N nitrogen trifluoride Chemical group FN(F)F GVGCUCJTUSOZKP-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 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
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- FYJQJMIEZVMYSD-UHFFFAOYSA-N perfluoro-2-butyltetrahydrofuran Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)OC(F)(F)C(F)(F)C1(F)F FYJQJMIEZVMYSD-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- CDXZRBLOGJXGTN-UHFFFAOYSA-N prop-2-enoxycyclohexane Chemical compound C=CCOC1CCCCC1 CDXZRBLOGJXGTN-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 238000000992 sputter etching Methods 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
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Description
本発明は、基板と、高精度な所望レジストパターンが形成された、エッチング耐性に優れるレジスト膜とが一体化した加工基板の簡易な製造方法に関する。 The present invention relates to a simple manufacturing method of a processed substrate in which a substrate and a resist film excellent in etching resistance on which a highly accurate desired resist pattern is formed are integrated.
近年、モールドのパターンをレジスト膜に転写することによって所望レジストパターンが形成されたレジスト膜を有する基材を得て、ついで該基材のレジスト膜をマスクとして機能させ、これにエッチング処理を行うことによりエッチング処理された基材を得る方法が注目されている。該方法はナノインプリントリソグラフィーと呼ばれている（特許文献１、特許文献２など参照。）。 In recent years, a substrate having a resist film on which a desired resist pattern is formed is obtained by transferring a mold pattern to a resist film, and then the resist film of the substrate is made to function as a mask, followed by etching treatment. Attention has been focused on a method for obtaining a base material etched by the above-mentioned method. This method is called nanoimprint lithography (see Patent Document 1, Patent Document 2, etc.).
ナノインプリントリソグラフィーにおけるレジスト膜を形成する硬化性のレジスト組成物として、含フッ素界面活性剤を含まない、光重合性モノマーを含む組成物が知られている。しかし、該組成物から形成するレジスト膜はモールドとの離型性が不充分でありモールド表面から剥離しにくい。剥離を円滑に行うためにモールド表面に離型剤が塗布されるが、離型剤層に厚さムラによりレジストパターンの精度が低下しやすい。また、モールドを連続使用する場合には、繰り返し離型剤を塗布する必要があり生産効率が低い。 As a curable resist composition for forming a resist film in nanoimprint lithography, a composition containing a photopolymerizable monomer that does not contain a fluorine-containing surfactant is known. However, the resist film formed from the composition has insufficient releasability from the mold and is difficult to peel off from the mold surface. A release agent is applied to the mold surface in order to perform the peeling smoothly, but the accuracy of the resist pattern tends to decrease due to uneven thickness of the release agent layer. Moreover, when using a mold continuously, it is necessary to apply | coat a mold release agent repeatedly and production efficiency is low.
本発明の目的は、基板と、所望レジストパターンが形成されたレジスト膜とが一体化した加工基板を高精度に生産効率よく製造する方法の提供にある。 An object of the present invention is to provide a method for manufacturing a processed substrate in which a substrate and a resist film on which a desired resist pattern is formed are integrated with high accuracy and high production efficiency.
本発明は、下記の発明を提供する。
［１］：下記工程１、下記工程２、および下記工程３を順に行うことにより、基板と所望レジストパターンが形成されたレジスト膜とが一体化した加工基板を得て、つぎに該加工基板のレジスト膜が形成された面をエッチングして基板をエッチング処理することを特徴とするエッチング処理された処理基板の製造方法。
工程１：基板と、所望レジストパターンの反転パターンを表面に有するモールドとを組み合わせて、ノニオン性含フッ素界面活性剤と、環構造を有する重合性モノマー、または重合により環構造を形成する重合性モノマーとを含むレジスト組成物を、該基板表面と該モールドのパターン面との間に挟持させる工程。
工程２：前記レジスト組成物中の重合性モノマーを重合させて該組成物からレジスト膜を形成させる工程。
工程３：モールドをレジスト膜から剥離して加工基板を得る工程。
The present invention provides the following inventions.
[1]: By performing the following step 1, the following step 2, and the following step 3 in order, a processed substrate in which the substrate and the resist film on which the desired resist pattern is formed is obtained is obtained. A method of manufacturing an etched processed substrate, wherein the substrate is etched by etching the surface on which the resist film is formed.
Step 1: A nonionic fluorine-containing surfactant and a polymerizable monomer having a ring structure, or a polymerizable monomer forming a ring structure by polymerization, by combining a substrate and a mold having a reverse pattern of a desired resist pattern on the surface A step of sandwiching a resist composition comprising: the substrate surface and the pattern surface of the mold.
Step 2: A step of polymerizing a polymerizable monomer in the resist composition to form a resist film from the composition.
Step 3: A step of removing the mold from the resist film to obtain a processed substrate.
［２］：反転パターンを表面に有するモールドの反転パターンが、凸部と凹部を有する微細パターンであり、かつ、該凸部の間隔の平均値が１ｎｍ〜５００μｍである［１］に記載の製造方法。
［３］：レジスト組成物が、重合開始剤を含むレジスト組成物である［１］または［２］に記載の製造方法。
［４］：含フッ素界面活性剤が、フッ素原子含有量が１０〜７０質量％の含フッ素界面活性剤である［１］〜［３］のいずれかに記載の製造方法。
[2]: The production according to [1], wherein the reversal pattern of the mold having the reversal pattern on the surface is a fine pattern having a convex portion and a concave portion, and the average value of the interval between the convex portions is 1 nm to 500 μm. Method.
[3] The production method according to [1] or [2], wherein the resist composition is a resist composition containing a polymerization initiator.
[4]: fluorinated surfactant, produced how according to any one of fluorine atom content of 10 to 70 wt% of the fluorinated surfactant [1] to [3].
本発明においては、含フッ素界面活性剤と、環構造を有する重合性モノマー、または重合により環構造を形成する重合性モノマーとを含むレジスト組成物を用いる。そのためレジスト組成物から形成するレジスト膜は、モールドから円滑に剥離でき、かつエッチング耐性に優れる。したがって本発明により高精度なナノインプリントリソグラフィーを効率よく実施できる。 In the present invention, a resist composition containing a fluorine-containing surfactant and a polymerizable monomer having a ring structure or a polymerizable monomer that forms a ring structure by polymerization is used. Therefore, the resist film formed from the resist composition can be smoothly peeled off from the mold and has excellent etching resistance. Therefore, highly accurate nanoimprint lithography can be efficiently performed by the present invention.
本発明においては、式（１）で表される化合物を化合物１と表す。他の式で表される化合物も同様に表す。 In the present invention, the compound represented by the formula (1) is represented as Compound 1. Compounds represented by other formulas are also represented in the same manner.
本発明の製造方法において、基板と、所望レジストパターンの反転パターンを表面に有するモールドとを組み合わせて、含フッ素界面活性剤と、環構造を有する重合性モノマー、または重合により環構造を形成する重合性モノマーとを含むレジスト組成物を、該基板表面と該モールドのパターン面との間に挟持させる工程（工程１）、前記レジスト組成物中の重合性モノマーを重合させて該組成物からレジスト膜を形成させる工程（工程２）、およびモールドをレジスト膜から剥離して、基板と、所望レジストパターンが形成されたレジスト膜とが一体化した加工基板を得る工程（工程３）を順に行う。工程１、工程２、および工程３における操作条件は後述する。 In the production method of the present invention, a combination of a substrate and a mold having a reverse pattern of a desired resist pattern on the surface, a fluorine-containing surfactant, a polymerizable monomer having a ring structure, or polymerization for forming a ring structure by polymerization A step of sandwiching a resist composition containing a polymerizable monomer between the substrate surface and the pattern surface of the mold (step 1), polymerizing the polymerizable monomer in the resist composition, and then forming a resist film from the composition Step (step 2) of forming the substrate and a step of removing the mold from the resist film to obtain a processed substrate in which the substrate and the resist film on which the desired resist pattern is formed (step 3) are sequentially performed. The operating conditions in step 1, step 2, and step 3 will be described later.
本発明におけるレジスト組成物は、含フッ素界面活性剤を含むため工程２において離型性に優れたレジスト膜を形成する。そのため工程３における剥離が円滑に進行し高精度な所望レジストパターンが形成されたレジスト膜が得られる。 Since the resist composition in the present invention contains a fluorine-containing surfactant, a resist film excellent in releasability is formed in Step 2. Therefore, peeling in step 3 proceeds smoothly, and a resist film on which a desired resist pattern with high accuracy is formed is obtained.
含フッ素界面活性剤は、フッ素原子含有量が１０〜７０質量％の含フッ素界面活性剤が好ましい。
含フッ素界面活性剤は、ＲＦ基とアニオン性基を有するアニオン性含フッ素界面活性剤、ＲＦ基とカチオン性基を有するカチオン性含フッ素界面活性剤、ＲＦ基、カチオン性基、およびアニオン性基を有する両性含フッ素界面活性剤、またはＲＦ基を有するノニオン性含フッ素界面活性剤が好ましい。ただしＲＦは含フッ素有機基であり、炭素数が１〜２０のポリフルオロアルキル基または炭素数が１〜２０のペルフルオロ（ポリオキシアルキレン）基が好ましい（以下同様。）。含フッ素界面活性剤は、レジスト組成物における相溶性とレジスト膜中への分散性が良好であることから、本発明では、ノニオン性含フッ素界面活性剤を選択する。また含フッ素界面活性剤は、水溶性であっても脂溶性であってもよい。
The fluorine-containing surfactant is preferably a fluorine-containing surfactant having a fluorine atom content of 10 to 70% by mass.
Fluorinated surfactants, anionic fluorinated surfactant having a R F group and an anionic group, a cationic fluorine-containing surfactant having a R F group and a cationic group, R F group, a cationic group, and amphoteric fluorinated surfactant having an anionic group, or a nonionic fluorinated surfactant having a R F group is preferred. However, RF is a fluorine-containing organic group and is preferably a polyfluoroalkyl group having 1 to 20 carbon atoms or a perfluoro (polyoxyalkylene) group having 1 to 20 carbon atoms (the same applies hereinafter). Since the fluorine-containing surfactant has good compatibility in the resist composition and dispersibility in the resist film , the nonionic fluorine-containing surfactant is selected in the present invention . The fluorine-containing surfactant may be water-soluble or fat-soluble.
アニオン性含フッ素界面活性剤は、ポリフルオロアルキルカルボン酸塩、ポリフルオロアルキル燐酸エステル、またはポリフルオロアルキルスルホン酸塩が好ましい。これらのカチオン性界面活性剤は、サーフロンＳ−１１１（商品名、セイミケミカル社製）、フロラードＦＣ−１４３（商品名、スリーエム社製）、メガファークＦ−１２０（商品名、大日本インキ工業社製）等として容易に入手できる。 The anionic fluorine-containing surfactant is preferably a polyfluoroalkyl carboxylate, a polyfluoroalkyl phosphate, or a polyfluoroalkyl sulfonate. These cationic surfactants are Surflon S-111 (trade name, manufactured by Seimi Chemical Co., Ltd.), Florard FC-143 (trade name, manufactured by 3M), Megafark F-120 (trade name, manufactured by Dainippon Ink Industries, Ltd.). ) Etc.
カチオン性含フッ素界面活性剤は、ポリフルオロアルキルカルボン酸のトリメチルアンモニウム塩、またはポリフルオロアルキルスルホン酸アミドのトリメチルアンモニウム塩が好ましい。これらのカチオン性界面活性剤は、サーフロンＳ−１２１（商品名、セイミケミカル社製）、フロラードＦＣ−１３４（商品名、スリーエム社製）、メガファークＦ−１５０（商品名、大日本インキ工業社製）等として容易に入手できる。 The cationic fluorine-containing surfactant is preferably a trifluoroammonium salt of polyfluoroalkylcarboxylic acid or a trimethylammonium salt of polyfluoroalkylsulfonic acid amide. These cationic surfactants are Surflon S-121 (trade name, manufactured by Seimi Chemical Co., Ltd.), Florard FC-134 (trade name, manufactured by 3M), Megafark F-150 (trade name, manufactured by Dainippon Ink Industries, Ltd.). ) Etc.
両性含フッ素界面活性剤としては、ポリフルオロアルキルベタインが好ましい。これらの両性界面活性剤は、サーフロンＳ−１３２（商品名、セイミケミカル社製）、フロラードＦＸ−１７２（商品名、スリーエム社製）、メガファークＦ−１２０（商品名、大日本インキ工業社製）等として容易に入手できる。 As the amphoteric fluorine-containing surfactant, polyfluoroalkyl betaine is preferable. These amphoteric surfactants include Surflon S-132 (trade name, manufactured by Seimi Chemical Co., Ltd.), Florard FX-172 (trade name, manufactured by 3M), Megafark F-120 (trade name, manufactured by Dainippon Ink Industries, Ltd.) Etc. are easily available.
ノニオン性含フッ素界面活性剤は、ポリフルオロアルキルアミンオキサイド、ポリフルオロアルキル・アルキレンオキサイド付加物、またはＲＦ基を有するポリマーが好ましく、ポリフルオロアルキル・アルキレンオキサイド付加物、またはＲＦ基を有するポリマーが特に好ましい。 The nonionic fluorine-containing surfactant is preferably a polyfluoroalkylamine oxide, a polyfluoroalkyl / alkylene oxide adduct, or a polymer having an R F group, and a polyfluoroalkyl / alkylene oxide adduct or a polymer having an R F group Is particularly preferred.
ポリフルオロアルキル・アルキレンオキサイド付加物としては、Ｆ（ＣＦ2）6ＣＨ2ＣＨ2Ｏ（ＣＨ2ＣＨ2Ｏ）10Ｈ、Ｆ（ＣＦ2）8ＣＨ2ＣＨ（ＯＨ）ＣＨ2Ｏ（ＣＨ2ＣＨ2Ｏ）10Ｈ、Ｆ（ＣＦ2）8ＣＨ2ＣＨ（ＯＨ）ＣＨ2Ｏ（ＣＨ2ＣＨ2Ｏ）10ＣＨ2ＣＨ（ＯＨ）ＣＨ2（ＣＦ2）8Ｆ等が挙げられる。 Examples of the polyfluoroalkyl / alkylene oxide adduct include F (CF 2 ) 6 CH 2 CH 2 O (CH 2 CH 2 O) 10 H, F (CF 2 ) 8 CH 2 CH (OH) CH 2 O (CH 2 CH 2 O) 10 H, F (CF 2) 8 CH 2 CH (OH) CH 2 O (CH 2 CH 2 O) 10 CH 2 CH (OH) CH 2 (CF 2) 8 F , and the like.
ＲＦ基を有するポリマーは、ＲＦ基を有するモノマーに基づくモノマー単位を含むポリマーが好ましい。該モノマーとしては、ＲＦ基と、エポキシ基、ビニル基、アリル基、アクリロイル基、またはメタクリロイル基とを含むモノマーが好ましく、ＲＦ基と、アクリロイル基、またはメタクリロイル基とを含むモノマーが特に好ましい。 Polymers having a R F group, the polymer comprising monomer units based on a monomer having an R F group is preferred. As the monomer, a monomer containing an R F group and an epoxy group, a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group is preferable, and a monomer containing an R F group and an acryloyl group or a methacryloyl group is particularly preferable. .
ＲＦ基を有するモノマーの具体例としては、フルオロ（メタ）アクリレートが好ましい。ただし（メタ）アクリレートとはアクリレートとメタクリレートの総称である（以下同様。）。フルオロ（メタ）アクリレートとしては、下記の化合物が挙げられる（ただし、ｍ１〜ｍ６はそれぞれ独立に０〜１０の整数を、ｊ５およびｊ６はそれぞれ独立に１〜１０の整数を、ｎ１、ｎ２、ｎ５およびｎ６はそれぞれ独立に１〜２０の整数を、示す。）。
ＣＨ2＝ＣＨＣＯＯ（ＣＨ2）m1（ＣＦ2）n1Ｆ、
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯ（ＣＨ2）m2（ＣＦ2）n2Ｆ、
ＣＨ2＝ＣＨＣＯＯ（ＣＨ2）m3ＣＦ（ＣＦ3）2、
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯ（ＣＨ2）m4ＣＦ（ＣＦ3）2、
ＣＨ2＝ＣＨＣＯＯ（ＣＨ2）m5Ｎ（ＣＨ2）j5ＳＯ2（ＣＦ2）n5Ｆ、
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯ（ＣＨ2）m6Ｎ（ＣＨ2）j6ＳＯ2（ＣＦ2）n6Ｆ。
As a specific example of the monomer having an R F group, fluoro (meth) acrylate is preferable. However, (meth) acrylate is a general term for acrylate and methacrylate (the same applies hereinafter). Examples of the fluoro (meth) acrylate include the following compounds (where m1 to m6 are each independently an integer of 0 to 10, j5 and j6 are each independently an integer of 1 to 10, n1, n2, n5 And n6 each independently represents an integer of 1 to 20.)
CH 2 = CHCOO (CH 2 ) m1 (CF 2 ) n1 F,
CH 2 = C (CH 3) COO (CH 2) m2 (CF 2) n2 F,
CH 2 = CHCOO (CH 2) m3 CF (CF 3) 2,
CH 2 = C (CH 3) COO (CH 2) m4 CF (CF 3) 2,
CH 2 = CHCOO (CH 2) m5 N (CH 2) j5 SO 2 (CF 2) n5 F,
CH 2 = C (CH 3) COO (CH 2) m6 N (CH 2) j6 SO 2 (CF 2) n6 F.
ＲＦ基を有するポリマーは、ＲＦ基を有するモノマー以外のフッ素原子を含まないモノマー（以下、単に他のモノマーという。）に基づくモノマー単位を含んでいてもよい。他のモノマーは、フッ素原子を含まない（メタ）アクリレートが好ましい。（メタ）アクリレートは、芳香族（メタ）アクリレートであっても脂肪族（メタ）アクリレートであってもよい。 Polymers having a R F group is a monomer containing no fluorine atom other than the monomer having a R F group (hereinafter, simply. That other monomer) may contain monomer units based on. The other monomer is preferably a (meth) acrylate containing no fluorine atom. The (meth) acrylate may be an aromatic (meth) acrylate or an aliphatic (meth) acrylate.
芳香族（メタ）アクリレートとしては、フェノキシエチルアクリレート、ベンジルアクリレート、ナフチルアクリレート等が挙げられる。脂肪族（メタ）アクリレートとしては、鎖状脂肪族の単官能（メタ）アクリレート、環状脂肪族の単官能（メタ）アクリレート、多官能（メタ）アクリレートが挙げられる。 Examples of aromatic (meth) acrylates include phenoxyethyl acrylate, benzyl acrylate, and naphthyl acrylate. Examples of aliphatic (meth) acrylates include chain aliphatic monofunctional (meth) acrylates, cycloaliphatic monofunctional (meth) acrylates, and polyfunctional (meth) acrylates.
鎖状脂肪族の単官能（メタ）アクリレートとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ステアリル（メタ）アクリレート、ラウリル（メタ）アクリレート、エトキシエチル（メタ）アクリレート、メトキシエチル（メタ）アクリレート、グリシジル（メタ）アクリレート、テトラヒドロフルフリール（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、ジメチルアミノエチル（メタ）メタクリレート等が挙げられる。 As chain aliphatic monofunctional (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) Acrylate, lauryl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, dimethylaminoethyl Meth) methacrylate.
環状脂肪族の単官能（メタ）アクリレートの具体例としては、アダマンチル（メタ）アクリレート、メチルアダマンチル（メタ）アクリレート、ヒドロキシアダマンチル（メタ）アクリレート、ノルボルニル（メタ）アクリレート等が挙げられる。 Specific examples of the cycloaliphatic monofunctional (meth) acrylate include adamantyl (meth) acrylate, methyladamantyl (meth) acrylate, hydroxyadamantyl (meth) acrylate, norbornyl (meth) acrylate, and the like.
多官能（メタ）アクリレートの具体例としては、１ｃ−ブタンジオールジアクリレート、１，４−ブタンジオールジアクリレート、１，６−ヘキサンジオールジアクリレート、トリメチロールプロパントリアクリレート、ペンタアエリスリトールトリアクリレート、ジペンタエリスリトールヘキサアクリレート、ジエチレングリコールジアクリレート、ネオペンチルグリコールジアクリレート、ポリオキシエチレングリコールジアクリレート、トリプロピレングリコールジアクリレート等が挙げられる。 Specific examples of the polyfunctional (meth) acrylate include 1c-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaaerythritol triacrylate, diester Examples include pentaerythritol hexaacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, polyoxyethylene glycol diacrylate, and tripropylene glycol diacrylate.
また他のモノマーとして、アルキルビニルエーテル（エチルビニルエーテル、プロピルビニルエーテル、イソブチルビニルエーテル、２−エチルヘキシルビニルエーテル、シクロヘキシルビニルエーテル等。）、アルキルビニルエステル（酢酸ビニル、プロピオン酸ビニル、（イソ）酪酸ビニル、吉草酸ビニル、シクロヘキサンカルボン酸ビニル等。）、安息香酸ビニル、アルキルアリルエーテル（エチルアリルエーテル、プロピルアリルエーテル、（イソ）ブチルアリルエーテル、シクロヘキシルアリルエーテル等。）、アルキルアリルエステル（エチルアリルエステル、プロピルアリルエステル、イソブチルアリルエステル等。）等を用いてもよい。 Other monomers include alkyl vinyl ethers (ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, etc.), alkyl vinyl esters (vinyl acetate, vinyl propionate, vinyl (iso) butyrate, vinyl valerate, Vinyl cyclohexanecarboxylate), vinyl benzoate, alkyl allyl ether (ethyl allyl ether, propyl allyl ether, (iso) butyl allyl ether, cyclohexyl allyl ether, etc.), alkyl allyl ester (ethyl allyl ester, propyl allyl ester, Isobutyl allyl ester, etc.) may also be used.
またＲＦ基を有するポリマーの重量平均分子量は、モノマーとの相溶性の観点から、５００〜５０００００が好ましく、１０００〜１００００が特に好ましい。 The weight average molecular weight of the polymer having an R F group, from the viewpoint of compatibility with the monomers, preferably from 500 to 500,000, particularly preferably 1,000 to 10,000.
これらのノニオン性界面活性剤も、サーフロンＳ−１４５（商品名、セイミケミカル社製）、サーフロンＳ−３９３（商品名、セイミケミカル社製）、サーフロンＫＨ−２０（商品名、セイミケミカル社製）、サーフロンＫＨ−４０（商品名、セイミケミカル社製）、フロラードＦＣ−１７０（商品名、スリーエム社製）、フロラードＦＣ−４３０（商品名、スリーエム社製）、メガファークＦ−１４１（商品名、大日本インキ工業社製）等として工業的に容易に入手できる。 These nonionic surfactants are also Surflon S-145 (trade name, manufactured by Seimi Chemical), Surflon S-393 (trade name, manufactured by Seimi Chemical), Surflon KH-20 (trade name, manufactured by Seimi Chemical) , Surflon KH-40 (trade name, manufactured by Seimi Chemical Co., Ltd.), Florard FC-170 (trade name, manufactured by 3M), Fluorard FC-430 (trade name, manufactured by 3M), Megafark F-141 (trade name, large (Manufactured by Nippon Ink Industries Co., Ltd.) etc.
レジスト組成物における含フッ素界面活性剤の含有量は、０．０１〜１０質量％が好ましく、０．１〜５質量％が特に好ましい。この範囲において、レジスト組成物の調整が容易であり離型性に優れたレジスト膜が得られる。 The content of the fluorine-containing surfactant in the resist composition is preferably 0.01 to 10% by mass, particularly preferably 0.1 to 5% by mass. Within this range, it is easy to adjust the resist composition, and a resist film excellent in releasability can be obtained.
本発明におけるレジスト組成物は、環構造を有する重合性モノマー（以下、環状モノマーともいう。）、または重合により環構造を形成する重合性モノマー（以下、環化モノマーともいう。）を含む。環状モノマーと環化モノマーを総称して環形成モノマーともいう。本発明におけるレジスト膜は、環形成モノマーの重合により形成した環構造を有する重合体を含むためエッチング耐性に優れる。その理由は必ずしも明確ではないが、環構造を有する重合体はエッチングにより炭素−炭素結合が切断されても環構造に由来するかさ高い構造が保持されやすいためと考えられる。 The resist composition in the present invention includes a polymerizable monomer having a ring structure (hereinafter also referred to as a cyclic monomer) or a polymerizable monomer that forms a ring structure by polymerization (hereinafter also referred to as a cyclized monomer). The cyclic monomer and the cyclized monomer are collectively referred to as a ring-forming monomer. Since the resist film in the present invention contains a polymer having a ring structure formed by polymerization of a ring-forming monomer, it has excellent etching resistance. The reason is not necessarily clear, but it is considered that a polymer having a ring structure is likely to retain a bulky structure derived from the ring structure even if the carbon-carbon bond is broken by etching.
エッチング耐性の観点からは、環形成モノマーはフッ素原子を含まないのが好ましい。含フッ素界面活性剤との相溶性の観点からは、環形成モノマーはフッ素原子を含むのが好ましい。環形成モノマーがフッ素原子を含む場合、環形成モノマーのフッ素原子含有量は１０〜７０質量％が好ましい。また基材との密着性を向上させる観点からは、環形成モノマーは官能基（水酸基が好ましい。）を含むのが好ましい。 From the viewpoint of etching resistance, the ring-forming monomer preferably does not contain a fluorine atom. From the viewpoint of compatibility with the fluorine-containing surfactant, the ring-forming monomer preferably contains a fluorine atom. When the ring-forming monomer contains a fluorine atom, the fluorine atom content of the ring-forming monomer is preferably 10 to 70% by mass. Further, from the viewpoint of improving the adhesion with the substrate, the ring-forming monomer preferably contains a functional group (preferably a hydroxyl group).
環状モノマーは、重合性基と環構造を有する重合性モノマーが好ましい。
重合性基は、オキシラン基、または重合性炭素−炭素２重結合が好ましく、ビニル基、アリル基、アクリロイル基、またはメタクリロイル基がより好ましく、アクリロイル基、またはメタクリロイル基が特に好ましい。
The cyclic monomer is preferably a polymerizable monomer having a polymerizable group and a ring structure.
The polymerizable group is preferably an oxirane group or a polymerizable carbon-carbon double bond, more preferably a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group, and particularly preferably an acryloyl group or a methacryloyl group.
環構造の環は、炭化水素環であってもヘテロ環であってもよく、炭化水素環が好ましい。また環は飽和環であっても不飽和環であってもよい。不飽和環は共役環であってもよい。 The ring of the ring structure may be a hydrocarbon ring or a heterocycle, and is preferably a hydrocarbon ring. The ring may be a saturated ring or an unsaturated ring. The unsaturated ring may be a conjugated ring.
炭化水素環は、単環炭化水素、縮合多環炭化水素、橋かけ環炭化水素、またはスピロ環炭化水素が好ましく、縮合多環炭化水素、または橋かけ環炭化水素がより好ましく、コレステロール環、アダマンタン環、またはノルボルナン環が特に好ましい。ただし、アダマンタン環とは下記（１）で表される橋かけ環を、ノルボルナン構造とは下記（２）で表される橋かけ環を、意味する。 The hydrocarbon ring is preferably a monocyclic hydrocarbon, a condensed polycyclic hydrocarbon, a bridged ring hydrocarbon, or a spiro ring hydrocarbon, more preferably a condensed polycyclic hydrocarbon or a bridged ring hydrocarbon, a cholesterol ring, an adamantane A ring or a norbornane ring is particularly preferable. However, the adamantane ring means a bridged ring represented by the following (1), and the norbornane structure means a bridged ring represented by the following (2).
また炭化水素環は、環を構成する原子以外の原子として、珪素原子、硫黄原子、酸素原子、窒素原子、ホウ素原子、リン原子、ハロゲン原子（塩素原子、臭素原子、ヨウ素原子等。）等を含んでいてもよい。 The hydrocarbon ring includes a silicon atom, a sulfur atom, an oxygen atom, a nitrogen atom, a boron atom, a phosphorus atom, a halogen atom (a chlorine atom, a bromine atom, an iodine atom, etc.), etc. as atoms other than the atoms constituting the ring. May be included.
環状モノマーの具体例としては、下記の化合物が挙げられる。 Specific examples of the cyclic monomer include the following compounds.
環化モノマーとしては、ＣＦ２＝ＣＦＯＣＦ２ＣＦ２ＣＦ＝ＣＦ２、ＣＦ２＝ＣＦＯＣＦ（ＣＦ３）ＣＦ２ＣＦ＝ＣＦ２、ＣＦ２＝ＣＦＯＣＦ２ＣＦ（ＣＦ３）ＣＦ＝ＣＦ２、ＣＦ２＝ＣＦＣＦ２ＣＦ＝ＣＦ２、ＣＦ２＝ＣＦＣＦ２ＣＨ＝ＣＨ２、ＣＦ２＝ＣＦＣＦ２Ｃ（ＣＦ３）（ＯＨ）ＣＨ２ＣＨ＝ＣＨ２、ＣＦ２＝ＣＦＣＦ２Ｃ（ＣＦ３）（ＯＨ）ＣＨ＝ＣＨ２、ＣＦ２＝ＣＦＣＨ２ＣＨ（ＣＨ２Ｃ（ＣＦ３）２ＯＨ）ＣＨ２ＣＨ＝ＣＨ２、ＣＦ２＝ＣＦＣＨ２ＣＨ（ＣＨ２Ｃ（ＣＦ３）２ＯＨ）ＣＨ＝ＣＨ２、ＣＦ２＝ＣＦＣＨ２ＣＨ（Ｃ（ＣＦ３）２ＯＨ）ＣＨ２ＣＨ＝ＣＨ２、ＣＦ２＝ＣＦＣＨ２ＣＨ（Ｃ（ＣＦ３）２ＯＨ）ＣＨ＝ＣＨ２等のフッ素原子を含む環化モノマー；ビス−(２，３−エポキシプロポキシ)エーテル、ビス［２−(ｔ−ブトキシカルボニル)アリル］エーテル、１ｂ：５，６−ジアンヒドロ−Ｄ−マンニトール、Ｎ−ヘキシル−Ｎ−アリル−２−(エトキシカルボニル)アリルアミン等のフッ素原子を含まない環化モノマーが挙げられる。 As the cyclized monomer, CF 2 = CFOCF 2 CF 2 CF = CF 2 , CF 2 = CFOCF (CF 3 ) CF 2 CF = CF 2 , CF 2 = CFOCF 2 CF (CF 3 ) CF═CF 2 , CF 2 = CFCF 2 CF = CF 2, CF 2 = CFCF 2 CH = CH 2, CF 2 = CFCF 2 C (CF 3) (OH) CH 2 CH = CH 2, CF 2 = CFCF 2 C (CF 3) (OH ) CH = CH 2, CF 2 = CFCH 2 CH (CH 2 C (CF 3) 2 OH) CH 2 CH = CH 2, CF 2 = CFCH 2 CH (CH 2 C (CF 3) 2 OH) CH = CH 2, CF 2 = CFCH 2 CH (C (CF 3) 2 OH) CH 2 CH = CH 2, CF 2 = CFCH 2 CH (C (CF 3) 2 OH) CH = CH 2 and fluorine Hara Bis- (2,3-epoxypropoxy) ether, bis [2- (t-butoxycarbonyl) allyl] ether, 1b: 5,6-dianhydro-D-mannitol, N-hexyl-N- Examples thereof include cyclized monomers containing no fluorine atom, such as allyl-2- (ethoxycarbonyl) allylamine.
レジスト組成物においては、環形成モノマー以外の重合性モノマー（以下、他の重合性モノマーという。）を用いてもよい。他の重合性モノマーは、フッ素原子を含む他の重合性モノマーであってもフッ素原子を含まない他の重合性モノマーであってもよい。 In the resist composition, a polymerizable monomer other than the ring-forming monomer (hereinafter referred to as other polymerizable monomer) may be used. The other polymerizable monomer may be another polymerizable monomer containing a fluorine atom or another polymerizable monomer containing no fluorine atom.
フッ素原子を含む他の重合性モノマーとしては、フルオロビニルエーテル、フルオロアリルエーテル、フルオロジエン、フルオロ（メタ）アクリレート、フルオロオレフィン等が挙げられる。 Examples of the other polymerizable monomer containing a fluorine atom include fluorovinyl ether, fluoroallyl ether, fluorodiene, fluoro (meth) acrylate, and fluoroolefin.
フッ素原子を含む他の重合性モノマーの具体例としては、ＣＦ2＝ＣＦＯ（ＣＦ2）3ＣＯＯＣＨ3、ＣＨ2＝ＣＨＣＯＯ（ＣＨ2）2（ＣＦ2）10Ｆ、ＣＨ2＝ＣＨＣＯＯ（ＣＨ2）2（ＣＦ2）8Ｆ、ＣＨ2＝ＣＨＣＯＯ（ＣＨ2）2（ＣＦ2）6Ｆ、ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯ（ＣＨ2）2（ＣＦ2）10Ｆ、ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯ（ＣＨ2）2（ＣＦ2）8Ｆ、ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯ（ＣＨ2）2（ＣＦ2）6Ｆ、ＣＨ2＝ＣＨＣＯＯＣＨ2（ＣＦ2）7Ｆ、ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2（ＣＦ2）7Ｆ、ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＦ2ＣＦ2Ｈ、ＣＨ2＝ＣＨＣＯＯＣＨ2（ＣＦ2ＣＦ2）2Ｈ、ＣＨ2＝ＣＨＣＯＯＣＨ2（ＣＦ2ＣＦ2）4Ｈ、ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2（ＣＦ2ＣＦ2）Ｈ、ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2（ＣＦ2ＣＦ2）2Ｈ、ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2（ＣＦ2ＣＦ2）4Ｈ、ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＦ2ＯＣＦ2ＣＦ2ＯＣＦ３、ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＦ2Ｏ（ＣＦ2ＣＦ2Ｏ）3ＣＦ3、ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＦ2ＯＣＦ2ＣＦ2ＯＣＦ３、ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＦ2Ｏ（ＣＦ2ＣＦ2Ｏ）3ＣＦ3、ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＦ（ＣＦ3）ＯＣＦ2ＣＦ（ＣＦ3）Ｏ（ＣＦ2）3Ｆ、ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＦ（ＣＦ3）Ｏ（ＣＦ2ＣＦ（ＣＦ3）Ｏ）2（ＣＦ2）3Ｆ、ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＦ（ＣＦ3）ＯＣＦ2ＣＦ（ＣＦ3）Ｏ（ＣＦ2）3Ｆ、ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＦ（ＣＦ3）Ｏ（ＣＦ2ＣＦ（ＣＦ3）Ｏ）2（ＣＦ2）3Ｆ、ＣＨ2＝ＣＦＣＯＯＣＨ2ＣＨ（ＯＨ）ＣＨ2（ＣＦ2）6ＣＦ（ＣＦ3）2、ＣＨ2＝ＣＦＣＯＯＣＨ2ＣＨ（ＣＨ2ＯＨ）ＣＨ2（ＣＦ2）6ＣＦ（ＣＦ3）2、ＣＨ2＝ＣＦＣＯＯＣＨ2ＣＨ（ＯＨ）ＣＨ2（ＣＦ2）10Ｆ、ＣＨ2＝ＣＦＣＯＯＣＨ2ＣＨ（ＣＨ2ＯＨ）ＣＨ2（ＣＦ2）10Ｆ、下記化合物が挙げられる（ただし、ｐ１〜ｐ４はそれぞれ独立に３〜１０の整数を示す。ｑ１およびｑ２はそれぞれ独立に０または１〜６の整数を示す。ＣｙＦはペルフルオロ（１，４−シクロへキシレン）基を示す。）。 Specific examples of other polymerizable monomer containing a fluorine atom include CF 2 ═CFO (CF 2 ) 3 COOCH 3 , CH 2 ═CHCOO (CH 2 ) 2 (CF 2 ) 10 F, CH 2 ═CHCOO (CH 2 ) 2 (CF 2 ) 8 F, CH 2 = CHCOO (CH 2 ) 2 (CF 2 ) 6 F, CH 2 = C (CH 3 ) COO (CH 2 ) 2 (CF 2 ) 10 F, CH 2 = C (CH 3 ) COO (CH 2 ) 2 (CF 2 ) 8 F, CH 2 ═C (CH 3 ) COO (CH 2 ) 2 (CF 2 ) 6 F, CH 2 ═CHCOOCH 2 (CF 2 ) 7 F, CH 2 = C (CH 3 ) COOCH 2 (CF 2 ) 7 F, CH 2 = CHCOOCH 2 CF 2 CF 2 H, CH 2 = CHCOOCH 2 (CF 2 CF 2 ) 2 H, CH 2 = CHCOOCH 2 (CF 2 CF 2) 4 H, CH 2 = C (CH 3) COOCH 2 (CF 2 CF 2) H, H 2 = C (CH 3) COOCH 2 (CF 2 CF 2) 2 H, CH 2 = C (CH 3) COOCH 2 (CF 2 CF 2) 4 H, CH 2 = CHCOOCH 2 CF 2 OCF 2 CF 2 OCF 3, CH 2 = CHCOOCH 2 CF 2 O (CF 2 CF 2 O) 3 CF 3, CH 2 = C (CH 3) COOCH 2 CF 2 OCF 2 CF 2 OCF 3, CH 2 = C (CH 3) COOCH 2 CF 2 O (CF 2 CF 2 O) 3 CF 3, CH 2 = CHCOOCH 2 CF (CF 3) OCF 2 CF (CF 3) O (CF 2) 3 F, CH 2 = CHCOOCH 2 CF (CF 3) O (CF 2 CF (CF 3) O) 2 (CF 2) 3 F, CH 2 = C (CH 3) COOCH 2 CF (CF 3) OCF 2 CF (CF 3) O (CF 2) 3 F, CH 2 = C (CH 3) COOCH 2 CF (CF 3) O (CF 2 CF (C 3) O) 2 (CF 2 ) 3 F, CH 2 = CFCOOCH 2 CH (OH) CH 2 (CF 2) 6 CF (CF 3) 2, CH 2 = CFCOOCH 2 CH (CH 2 OH) CH 2 (CF 2) 6 CF (CF 3) 2, CH 2 = CFCOOCH 2 CH (OH) CH 2 (CF 2) 10 F, CH 2 = CFCOOCH 2 CH (CH 2 OH) CH 2 (CF 2) 10 F, the following compound (However, p1-p4 shows the integer of 3-10 each independently. q1 and q2 each independently represent 0 or an integer of 1 to 6. Cy F represents a perfluoro (1,4-cyclohexylene) group. ).
フッ素原子を含まない他の重合性モノマーとしては、（メタ）アクリレート、（メタ）アクリル酸、ビニルエーテル、ビニルエステル、アリルエーテル、アリルエステル、オレフィン（エチレン、プロピレン、ブテン、ブタジエン等。）、無水マレイン酸、ビニレンカーボネート等が挙げられる。 Other polymerizable monomers that do not contain fluorine atoms include (meth) acrylate, (meth) acrylic acid, vinyl ether, vinyl ester, allyl ether, allyl ester, olefin (ethylene, propylene, butene, butadiene, etc.), and anhydrous maleic acid. An acid, vinylene carbonate, etc. are mentioned.
（メタ）アクリレートの具体例としては、下記の化合物が挙げられる。
メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ステアリルアクリレート、ラウリルアクリレート、エトキシエチルアクリレート、メトキシエチルアクリレート、グリシジルアクリレート、テトラヒドロフルフリールアクリレート、２−ヒドロキシエチルアクリレート、２−ヒドロキシプロピルアクリレート、４−ヒドロキシブチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチルアクリレート、Ｎ，Ｎ−ジメチルアミノエチルアクリレート、Ｎ−ビニルピロリドン、ジメチルアミノエチルメタクリレート等の単官能（メタ）アクリレート。
Specific examples of (meth) acrylates include the following compounds.
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl acrylate, lauryl acrylate, ethoxyethyl acrylate, methoxyethyl acrylate, glycidyl acrylate, tetrahydro Furfuryl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl (meth) acrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, N-vinylpyrrolidone, dimethylamino Monofunctional (meth) acrylates such as ethyl methacrylate.
１ｃ−ブタンジオールジアクリレート、１，４−ブタンジオールジアクリレート、１，６−ヘキサンジオールジアクリレート、トリメチロールプロパントリアクリレート、ペンタアエリスリトールトリアクリレート、ジペンタエリスリトールヘキサアクリレート、ジエチレングリコールジアクリレート、ネオペンチルグリコールジアクリレート、ポリオキシエチレングリコールジアクリレート、トリプロピレングリコールジアクリレート等の単官能（メタ）アクリレート。 1c-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaaerythritol triacrylate, dipentaerythritol hexaacrylate, diethylene glycol diacrylate, neopentyl glycol Monofunctional (meth) acrylates such as diacrylate, polyoxyethylene glycol diacrylate, and tripropylene glycol diacrylate.
ビニルエーテルの具体例としては、下記の化合物が挙げられる。
エチルビニルエーテル、プロピルビニルエーテル、イソブチルビニルエーテル、２−エチルヘキシルビニルエーテル、シクロヘキシルビニルエーテル等のアルキルビニルエーテル；安息香酸ビニル。
ビニルエステルの具体例としては、下記の化合物が挙げられる。
酢酸ビニル、プロピオン酸ビニル、（イソ）酪酸ビニル、吉草酸ビニル等のアルキルビニルエステル。
アリルエーテルの具体例としては、下記の化合物が挙げられる。
エチルアリルエーテル、プロピルアリルエーテル、（イソ）ブチルアリルエーテル等のアルキルアリルエーテル。
アリルエステルの具体例としては、下記の化合物が挙げられる。
エチルアリルエステル、プロピルアリルエステル、イソブチルアリルエステル等のアルキルアリルエステル。
Specific examples of the vinyl ether include the following compounds.
Alkyl vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether; vinyl benzoate.
Specific examples of the vinyl ester include the following compounds.
Alkyl vinyl esters such as vinyl acetate, vinyl propionate, vinyl (iso) butyrate and vinyl valerate.
Specific examples of allyl ether include the following compounds.
Alkyl allyl ethers such as ethyl allyl ether, propyl allyl ether, and (iso) butyl allyl ether;
Specific examples of allyl esters include the following compounds.
Alkyl allyl esters such as ethyl allyl ester, propyl allyl ester and isobutyl allyl ester;
レジスト組成物において環形成モノマーは、１種を用いても２種以上を用いてもよい。また環形成モノマーの１種以上と他の重合性モノマーの１種以上とを併用してもよい。他の重合性モノマーを用いる場合、全モノマーに対する環形成モノマーの割合は、５質量％以上１００質量％未満が好ましい。また併用する場合の組合せは、環状モノマーとフッ素原子を含む他の重合性モノマー、もしくはフッ素原子を含む環化モノマーとフッ素原子を含まない他の重合性モノマーが好ましい。この場合、モノマーと含フッ素界面活性剤が均一に溶解したレジスト組成物を調整しやすく、レジスト組成物を基板表面に配置しやすい。環状モノマーとフッ素原子を含む他の重合性モノマーを用いる場合、全モノマーに対するフッ素原子を含む他の重合性モノマーの割合は、５質量％以上が好ましく、２０質量％以上が特に好ましい。 In the resist composition, one or more ring-forming monomers may be used. One or more ring-forming monomers may be used in combination with one or more other polymerizable monomers. When using other polymerizable monomer, the ratio of the ring-forming monomer to the total monomer is preferably 5% by mass or more and less than 100% by mass. In addition, the combination when used in combination is preferably a cyclic monomer and another polymerizable monomer containing a fluorine atom, or a cyclized monomer containing a fluorine atom and another polymerizable monomer containing no fluorine atom. In this case, it is easy to adjust the resist composition in which the monomer and the fluorine-containing surfactant are uniformly dissolved, and the resist composition is easily arranged on the substrate surface. When using the other polymerizable monomer containing a cyclic monomer and a fluorine atom, 5 mass% or more is preferable and, as for the ratio of the other polymerizable monomer containing a fluorine atom with respect to all the monomers, 20 mass% or more is especially preferable.
本発明における基板としては、シリコン基板、化合物半導体基板、ガラス基板、非磁性セラミックス基板等が挙げられる。基板上には、所望の層が形成されていてもよい。所望の層としては、シリコン酸化物層、配線用金属層、層間絶縁膜、磁性膜、反射防止膜層等が挙げられる。所望の層は、各種配線、回路等として形成されていてもよい。 Examples of the substrate in the present invention include a silicon substrate, a compound semiconductor substrate, a glass substrate, and a nonmagnetic ceramic substrate. A desired layer may be formed on the substrate. Examples of the desired layer include a silicon oxide layer, a wiring metal layer, an interlayer insulating film, a magnetic film, and an antireflection film layer. The desired layer may be formed as various wirings, circuits, and the like.
本発明におけるモールドとしては、シリコンウェハ、ＳｉＣ、マイカ等の非透光材料製モールド；ガラス、ポリジメチルシロキサン、透明フッ素樹脂等の透光材料製モールドが挙げられる。
工程２における重合を光により行う場合には、透光材料製モールドが好ましい。また透光材料製加工基板を用い非透光材料製モールドを用いてもよい。工程２における重合を熱により行う場合は非透光材料製モールドを用いてもよい。
Examples of the mold in the present invention include a mold made of a non-translucent material such as a silicon wafer, SiC, and mica; and a mold made of a translucent material such as glass, polydimethylsiloxane, and transparent fluororesin.
In the case where the polymerization in step 2 is performed by light, a mold made of a translucent material is preferable. Moreover, you may use the mold made from a non-light-transmitting material using the process substrate made from a light-transmitting material. When the polymerization in the step 2 is performed by heat, a mold made of a non-translucent material may be used.
本発明におけるモールドは、所望レジストパターンの反転パターンである微細パターンを表面に有する。該微細パターンは、凸部と凹部を有する微細パターンが好ましい。該微細パターンにおける凸部の間隔（Ｌ１）の平均値は、１ｎｍ〜５００μｍが好ましく、１ｎｍ〜５０μｍが特に好ましい。凸部の幅（Ｌ２）の平均値は、１ｎｍ〜１００μｍが好ましく、１０ｎｍ〜１０μｍが特に好ましい。凸部の高さ（Ｌ３）の平均値は、１ｎｍ〜１００μｍが好ましく、１０ｎｍ〜１０μｍが特に好ましい。 The mold in the present invention has a fine pattern which is a reverse pattern of a desired resist pattern on the surface. The fine pattern is preferably a fine pattern having convex portions and concave portions. The average value of the convex spacing (L 1 ) in the fine pattern is preferably 1 nm to 500 μm, particularly preferably 1 nm to 50 μm. The average value of the width (L 2 ) of the convex portion is preferably 1 nm to 100 μm, and particularly preferably 10 nm to 10 μm. The average value of the height (L 3 ) of the convex portion is preferably 1 nm to 100 μm, and particularly preferably 10 nm to 10 μm.
本発明においては、モールドの微細パターンの最小寸法が５０μｍ以下、より小さくは５００ｎｍ以下、さらに小さくは５０ｎｍ以下であっても、微細パターン（すなわち所望レジストパターン）を高精度にレジスト膜に転写できる。微細パターンの最小寸法とは、モールド凸部高さ、モールド凹凸部間隔、およびモールド凸部長さのうち最小の値を意味する。最小寸法の下限は、特に限定されず、１ｎｍ以上が好ましい。 In the present invention, even when the minimum dimension of the fine pattern of the mold is 50 μm or less, smaller is 500 nm or less, and even smaller is 50 nm or less, the fine pattern (that is, the desired resist pattern) can be transferred to the resist film with high accuracy. The minimum dimension of a fine pattern means the minimum value among mold convex part height, mold uneven | corrugated part space | interval, and mold convex part length. The minimum of the minimum dimension is not specifically limited, 1 nm or more is preferable.
本発明の工程１において、基板表面とモールドパターン面との間はモールドの微細パターンの高さ未満であるのが好ましい。 In step 1 of the present invention, the space between the substrate surface and the mold pattern surface is preferably less than the height of the fine pattern of the mold.
工程１の好ましい態様としては、下記工程１ａ、下記工程１ｂ、下記工程１ｃが挙げられる。
工程１ａ：レジスト組成物を加工基板表面に配置し、次いで該レジスト組成物がモールドのパターン面に接するように、該加工基板と前記モールドとを押し合わせる工程。
工程１ａにおいて、レジスト組成物の配置は、ポッティング法、スピンコート法、ロールコート法、キャスト法、ディップコート法、ダイコート法、ラングミュアープロジェット法、真空蒸着法等の方法を用いレジスト組成物を加工基板表面に被覆して行うのが好ましい。レジスト組成物は、加工基板全面に被覆させるのが好ましい。
As a preferable aspect of the process 1, the following process 1a, the following process 1b, and the following process 1c are mentioned.
Step 1a: A step of placing the resist composition on the surface of the processed substrate and then pressing the processed substrate and the mold so that the resist composition is in contact with the pattern surface of the mold.
In step 1a, the resist composition is arranged using a method such as a potting method, a spin coating method, a roll coating method, a casting method, a dip coating method, a die coating method, a Langmuir projet method, or a vacuum deposition method. It is preferable to coat the processed substrate surface. The resist composition is preferably coated on the entire processed substrate.
また溶剤を加えて粘度調整したレジスト組成物を用い該レジスト組成物の塗膜を加工基板表面に形成し、次いで溶剤を留去させてレジスト組成物を加工基板表面に被覆させてもよい。溶剤は、レジスト組成物を均一に溶解または分散する、沸点が８０〜２００℃の溶剤が好ましい。溶剤としては、キシレン、酢酸ブチル等の非フッ素系有機溶媒；ペルフルオロ（２−ブチルテトラヒドロフラン）、メチル（ペルフルオロイソプロピル）エーテル、メチル（ペルフルオロヘキシルメチル）エーテル、メチル（ペルフルオロオクチル）エーテル等の含フッ素系溶媒；水が挙げられる。
基板とモールドを押し合わせる圧力であるプレス圧力（ゲージ圧）は、０超１０ＭＰａ以下が好ましく、０．１〜５ＭＰａがより好ましい。
Alternatively, a resist composition having a viscosity adjusted by adding a solvent may be used to form a coating film of the resist composition on the processed substrate surface, and then the solvent may be distilled off to coat the resist composition on the processed substrate surface. The solvent is preferably a solvent having a boiling point of 80 to 200 ° C., which uniformly dissolves or disperses the resist composition. Solvents include non-fluorine organic solvents such as xylene and butyl acetate; fluorine-containing systems such as perfluoro (2-butyltetrahydrofuran), methyl (perfluoroisopropyl) ether, methyl (perfluorohexylmethyl) ether, and methyl (perfluorooctyl) ether Solvent; water.
The press pressure (gauge pressure) that is the pressure for pressing the substrate and the mold is preferably more than 0 and 10 MPa or less, and more preferably 0.1 to 5 MPa.
工程１ｂ：レジスト組成物をモールドのパターン面に配置し、次いで加工基板表面がレジスト組成物に接するように、加工基板とモールドとを押し合わせる工程。
工程１ｂにおいて、レジスト組成物の配置は、ポッティング法、スピンコート法、ロールコート法、キャスト法、ディップコート法、ダイコート法、ラングミュアープロジェット法、真空蒸着法等の方法を用いレジスト組成物をモールドのパターン面に被覆して行うのが好ましい。レジスト組成物は、パターン面全面に被覆させてもパターン面一部のみに被覆させてもよい。
Step 1b: a step of placing the resist composition on the pattern surface of the mold and then pressing the processed substrate and the mold so that the surface of the processed substrate is in contact with the resist composition.
In step 1b, the resist composition is arranged using a method such as potting, spin coating, roll coating, casting, dip coating, die coating, Langmuir projet, and vacuum deposition. It is preferable to cover the pattern surface of the mold. The resist composition may be coated on the entire pattern surface or only on a part of the pattern surface.
また溶剤を加えて粘度調整したレジスト組成物を用い該レジスト組成物の塗膜をパターン面に形成し、次いで溶剤を留去させてレジスト組成物をパターン面に被覆させてもよい。溶剤は、工程１ａの溶剤と同じ溶剤を用いられる。
基板とモールドを押し合わせる圧力であるプレス圧力（ゲージ圧）は、０超１０ＭＰａ以下が好ましく、０．１〜５ＭＰａがより好ましい。
Alternatively, a resist composition having a viscosity adjusted by adding a solvent may be used to form a coating film of the resist composition on the pattern surface, and then the solvent may be distilled off to coat the resist composition on the pattern surface. As the solvent, the same solvent as that used in the step 1a is used.
The press pressure (gauge pressure) that is the pressure for pressing the substrate and the mold is preferably more than 0 and 10 MPa or less, and more preferably 0.1 to 5 MPa.
工程１ｃにおいて、空隙にレジスト組成物を充填する方法としては、毛細管現象により空隙にレジスト組成物を吸引する方法が挙げられる。 In step 1c, the method of filling the void with the resist composition includes a method of sucking the resist composition into the void by capillary action.
本発明の工程２において、重合性モノマーの重合方法は環形成モノマーの物性、レジスト組成物が重合開始剤を含む場合にはその種類を考慮して適宜決定できる。重合方法は、熱または光による方法が好ましい。低温（０〜６０℃）重合が可能でありレジスト膜の体積収縮を抑制できる、光重合開始剤を含むレジスト組成物を用いた光照射による重合方法が特に好ましい。 In Step 2 of the present invention, the polymerization method of the polymerizable monomer can be appropriately determined in consideration of the physical properties of the ring-forming monomer and the type of the resist composition containing a polymerization initiator. The polymerization method is preferably a method using heat or light. A polymerization method by light irradiation using a resist composition containing a photopolymerization initiator that can be polymerized at a low temperature (0 to 60 ° C.) and can suppress volume shrinkage of the resist film is particularly preferred.
光照射の方法としては、透光材料製モールド側から光照射する方法、透光材料製基板側から光照射する方法が挙げられる。光照射の光は、低温重合が可能な光重合開始剤が容易に反応する、２００〜４００ｎｍの波長光が好ましい。また光照射時に、系全体を加熱して環形成モノマーの重合を加速させてもよい。加熱の温度範囲は、３００℃以下が好ましく、０〜６０℃がより好ましく、２５〜５０℃が特に好ましい。 Examples of the light irradiation method include a method of irradiating light from the light transmitting material mold side and a method of irradiating light from the light transmitting material substrate side. The light irradiated with light is preferably light having a wavelength of 200 to 400 nm, which is easily reacted with a photopolymerization initiator capable of low-temperature polymerization. Moreover, at the time of light irradiation, the entire system may be heated to accelerate the polymerization of the ring-forming monomer. The heating temperature range is preferably 300 ° C. or less, more preferably 0 to 60 ° C., and particularly preferably 25 to 50 ° C.
本発明の工程３において、モールドをレジスト膜から剥離する際の温度は０〜５０℃が好ましい。 In step 3 of the present invention, the temperature at which the mold is peeled from the resist film is preferably 0 to 50 ° C.
本発明の製造方法の工程１〜３により得た加工基板（以下、単に加工基板ともいう。）は、基板とエッチング耐性に優れたレジスト膜とが一体化されている。該レジスト膜の所望レジストパターンをマスクとして機能させ、基板をエッチングすることによってエッチング処理された処理基板を製造する。本発明においてレジスト膜は、高精度な所望レジストパターンを有し、かつエッチング耐性に優れるため、高精度パターンを有する処理基板を製造できる。該処理基板のレジスト膜は除去する。 In the processed substrate (hereinafter also simply referred to as a processed substrate) obtained by steps 1 to 3 of the manufacturing method of the present invention, the substrate and a resist film having excellent etching resistance are integrated. Made to function desired resist pattern of the resist film as a mask, you produce processed substrate which has been etched by etching a substrate. In the present invention, the resist film has a desired resist pattern with high accuracy and is excellent in etching resistance, so that a processing substrate having a high accuracy pattern can be manufactured. Resist film of the substrate is you removed.
エッチングは、ドライエッチング、またはウェットエッチングが好ましく、ドライエッチングが特に好ましい。ドライエッチングとしては、ガスと高温で反応させる気相エッチング、低温ガスプラズマを用いたプラズマエッチング、反応性イオンエッチング（ＲＩＥ）、イオンのスパッタエッチング、イオン銃を用いたイオンビームエッチング、光エッチング等が挙げられる。レジスト膜の除去は定法にしたがって実施できる。 Etching is preferably dry etching or wet etching, and dry etching is particularly preferable. Examples of dry etching include gas phase etching that reacts with gas at high temperature, plasma etching using low temperature gas plasma, reactive ion etching (RIE), ion sputter etching, ion beam etching using an ion gun, and photo etching. Can be mentioned. The removal of the resist film can be performed according to a conventional method.
以下、実施例により本発明を詳細に説明するが、本発明はこれらに限定されない。フッ素原子含有量をＦ含有量と、重量平均分子量をＭＷと、記す。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. And a fluorine atom content of the F content, and M W a weight average molecular weight referred.
実施例においては、環構造を有するモノマーとして、下記化合物ａ１、下記化合物ａ２、または下記化合物ａ３を、フッ素原子を含む他のモノマーとして、下記化合物ｃ１（Ｆ含有量５７．２％）を、フッ素原子を含まない他のモノマーとして、下記化合物ｄ１、または下記化合物ｄ２を、用いた。 In Examples, the following compound a1, the following compound a2, or the following compound a3 is used as a monomer having a ring structure, and the following compound c1 (F content: 57.2%) is used as another monomer containing a fluorine atom. As another monomer containing no atom, the following compound d1 or the following compound d2 was used.
重合開始剤は、光重合開始剤のイルガキュア６５１（商品名、チバ・スペシャルティ・ケミカルズ株式会社製）を用いた。
含フッ素界面活性剤は、ノニオン性のＲＦ基を有するポリマー（Ｆ含有量約３０％、Ｍｗ約３０００）を用いた。
As the polymerization initiator, Irgacure 651 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), a photopolymerization initiator, was used.
As the fluorine-containing surfactant, a polymer having a nonionic R F group (F content: about 30%, Mw: about 3000) was used.
［レジスト組成物の調製］
紫外線をカットしたクリーンルーム内で、バイヤル容器（内容積６ｍＬ）中に化合物ａ１の０．４５ｇ、化合物ｄ１の０．１０ｇ、化合物ｄ２の０．４０ｇ、および含フッ素界面活性剤の０．０１ｇを混合した。さらに光重合開始剤の０．０４ｇを混合してレジスト組成物（以下、組成物１という。）を調製した。同様にして下記組成物２、下記組成物３、および下記組成物４を調製した。
[Preparation of resist composition]
In a clean room where ultraviolet rays were cut, 0.45 g of compound a1, 0.10 g of compound d1, 0.40 g of compound d2 and 0.01 g of fluorine-containing surfactant were mixed in a vial container (internal volume 6 mL). did. Further, 0.04 g of a photopolymerization initiator was mixed to prepare a resist composition (hereinafter referred to as composition 1). In the same manner, the following composition 2, the following composition 3, and the following composition 4 were prepared.
組成物２：化合物ａ１の０．３０ｇ、化合物ｃ１の０．２５ｇ、化合物ｄ１の０．３０ｇ、含フッ素界面活性剤の０．０１ｇ、および光重合開始剤の０．０４ｇからなるレジスト組成物。
組成物３：化合物ａ２の０．３０ｇ、化合物ｃ１の０．２５ｇ、化合物ｄ１の０．４０ｇ、含フッ素界面活性剤の０．０１ｇ、および光重合開始剤の０．０４ｇからなるレジスト組成物。
組成物４：化合物ａ３の０．３０ｇ、化合物ｃ１の０．２５ｇ、化合物ｄ１の０．４０ｇ、含フッ素界面活性剤の０．０１ｇ、および光重合開始剤の０．０４ｇからなるレジスト組成物。
Composition 2: A resist composition comprising 0.30 g of compound a1, 0.25 g of compound c1, 0.30 g of compound d1, 0.01 g of a fluorine-containing surfactant, and 0.04 g of a photopolymerization initiator.
Composition 3: A resist composition comprising 0.30 g of compound a2, 0.25 g of compound c1, 0.40 g of compound d1, 0.01 g of a fluorine-containing surfactant, and 0.04 g of a photopolymerization initiator.
Composition 4: A resist composition comprising 0.30 g of compound a3, 0.25 g of compound c1, 0.40 g of compound d1, 0.01 g of a fluorinated surfactant, and 0.04 g of a photopolymerization initiator.
［例１］加工基板、および該加工基板を用いた処理基板の製造例（その１）
組成物１の１滴をシリコンウェハ上にスピンコートして、組成物１からなる被膜（膜厚５０ｎｍ）で表面が被覆されたシリコンウェハを得る。幅４００ｎｍ、深さ１００ｎｍの凹構造が２００ｎｍの等間隔で配置された凹凸構造を表面に有する透明モールド（石英製）を組成物１の被膜面に押し付けて、シリコンウェハと透明モールドを２５℃にて０．５ＭＰａ（ゲージ圧）でプレスする。
[Example 1] Processed substrate and process substrate manufacturing example using the processed substrate (part 1)
One drop of the composition 1 is spin-coated on a silicon wafer to obtain a silicon wafer whose surface is coated with a film (film thickness 50 nm) made of the composition 1. A transparent mold (made of quartz) having a concavo-convex structure in which concave structures having a width of 400 nm and a depth of 100 nm are arranged at equal intervals of 200 nm on the surface is pressed against the coating surface of the composition 1 to bring the silicon wafer and the transparent mold to 25 ° C. Press at 0.5 MPa (gauge pressure).
そのままモールド側から高圧水銀灯（周波数：１．５ｋＨｚ〜２．０ｋＨｚ，主波長光：２５５ｎｍ、３１５ｎｍおよび３６５ｎｍ）の光を１５秒間照射して、組成物１においてモノマーの重合反応を行う。モールドをシリコンウェハからゆっくり剥離させると、組成物１より生成したレジスト膜と一体化したシリコンウェハ（加工基板）を得る。該レジスト膜の表面にはモールドの凹凸構造が高精度に転写した凹凸構造が形成している。 The composition 1 is subjected to a monomer polymerization reaction by irradiating light from a high pressure mercury lamp (frequency: 1.5 kHz to 2.0 kHz, dominant wavelength light: 255 nm, 315 nm, and 365 nm) for 15 seconds. When the mold is slowly peeled from the silicon wafer, a silicon wafer (processed substrate) integrated with the resist film formed from the composition 1 is obtained. A concavo-convex structure in which the concavo-convex structure of the mold is transferred with high accuracy is formed on the surface of the resist film.
つぎにＯ２、Ａｒ、およびＣＦ４の混合ガスをエッチングガスに用いたＲＩＥ（リアクティブ・イオン・エッチング）法により、加工基板をドライエッチングする。レジスト膜のエッチング耐性はノボラック樹脂とほぼ同等である。ついでシリコンウェハ上のレジスト膜を灰化除去しシリコンウェハを酸洗浄すると、モールドの凹凸構造に対応したパターンが表面に形成されたシリコンウェハを得る。 Next, the processed substrate is dry-etched by RIE (reactive ion etching) using a mixed gas of O 2 , Ar, and CF 4 as an etching gas. The etching resistance of the resist film is almost equal to that of novolak resin. Next, the resist film on the silicon wafer is removed by ashing and the silicon wafer is acid cleaned to obtain a silicon wafer having a pattern corresponding to the concavo-convex structure of the mold on the surface.
［例２］加工基板、および該加工基板を用いた処理基板の製造例（その２）
組成物１の代わりに組成物２を用いる以外は、例１と同様に組成物２の重合により生成したレジスト膜と一体化したシリコンウェハを得る。該レジスト膜の表面にはモールドの凹凸構造が高精度に転写した凹凸構造が形成している。加工基板を例１と同様にエッチング処理してモールドの凹凸構造に対応したパターンが表面に形成されたシリコンウェハを得る。レジスト膜のエッチング耐性はノボラック樹脂とほぼ同等である。
[Example 2] Processed substrate and manufacturing example of a processed substrate using the processed substrate (part 2)
A silicon wafer integrated with a resist film formed by polymerization of the composition 2 is obtained in the same manner as in Example 1 except that the composition 2 is used instead of the composition 1. A concavo-convex structure in which the concavo-convex structure of the mold is transferred with high accuracy is formed on the surface of the resist film. The processed substrate is etched in the same manner as in Example 1 to obtain a silicon wafer having a pattern corresponding to the concavo-convex structure of the mold formed on the surface. The etching resistance of the resist film is almost equal to that of novolak resin.
［例３］加工基板、および該加工基板を用いた処理基板の製造例（その３）
組成物１の代わりに組成物３を用いる以外は、例１と同様に組成物３の重合により生成したレジスト膜と一体化したシリコンウェハを得る。該レジスト膜の表面にはモールドの凹凸構造が高精度に転写した凹凸構造が形成している。またレジスト膜とシリコンウェハの密着性も特に良好である。加工基板を例１と同様にエッチングしてモールドの凹凸構造に対応したパターンが表面に形成されたシリコンウェハを得る。レジスト膜のエッチング耐性はノボラック樹脂とほぼ同等である。
[Example 3] Processing substrate and processing substrate manufacturing example using the processing substrate (part 3)
A silicon wafer integrated with a resist film formed by polymerization of the composition 3 is obtained in the same manner as in Example 1 except that the composition 3 is used instead of the composition 1. A concavo-convex structure in which the concavo-convex structure of the mold is transferred with high accuracy is formed on the surface of the resist film. Also, the adhesion between the resist film and the silicon wafer is particularly good. The processed substrate is etched in the same manner as in Example 1 to obtain a silicon wafer having a pattern corresponding to the concavo-convex structure of the mold formed on the surface. The etching resistance of the resist film is almost equal to that of novolak resin.
［例４］加工基板、および該加工基板を用いた処理基板の製造例（その４）
組成物１の代わりに組成物４を用いる以外は、例１と同様に組成物４の重合により生成したレジスト膜と一体化したシリコンウェハを得る。該レジスト膜の表面にはモールドの凹凸構造が高精度に転写した凹凸構造が形成している。加工基板を例１と同様にエッチングしてモールドの凹凸構造に対応したパターンが表面に形成されたシリコンウェハを得る。レジスト膜のエッチング耐性はノボラック樹脂に若干劣る。
[Example 4] Processed substrate and manufacturing example of a processed substrate using the processed substrate (part 4)
A silicon wafer integrated with a resist film formed by polymerization of the composition 4 is obtained in the same manner as in Example 1 except that the composition 4 is used instead of the composition 1. A concavo-convex structure in which the concavo-convex structure of the mold is transferred with high accuracy is formed on the surface of the resist film. The processed substrate is etched in the same manner as in Example 1 to obtain a silicon wafer having a pattern corresponding to the concavo-convex structure of the mold formed on the surface. The etching resistance of the resist film is slightly inferior to that of novolak resin.
以上の結果から、含フッ素界面活性剤と環形成モノマーとを含むレジスト組成物を用いる本発明によって、基板と、高精度な所望レジストパターンを有しかつエッチング耐性に優れるレジスト膜とが一体化した加工基板を容易に製造できることがわかる。よって本発明によって高精度なナノインプリントリソグラフィーが実現される。 From the above results, according to the present invention using the resist composition containing the fluorine-containing surfactant and the ring-forming monomer, the substrate and the resist film having a highly accurate desired resist pattern and excellent in etching resistance are integrated. It can be seen that the processed substrate can be easily manufactured. Therefore, highly accurate nanoimprint lithography is realized by the present invention.
本発明の製造方法により得た加工基板をエッチングした処理基板は、半導体装置として有用である。半導体装置の具体例としては、ＤＲＡＭ、フラッシュメモリ等のメモリＩＣ；システムＬＳＩ等のロジックＩＣ；ＬＥＤ（発光ダイオード）、ＬＤ（半導体レーザ）等の光半導体；マイクロコンピュータ、半導体センサー、汎用リニアＩＣ、制御・ドライバーＩＣ等が挙げられる。
A processed substrate obtained by etching a processed substrate obtained by the manufacturing method of the present invention is useful as a semiconductor device. Specific examples of semiconductor devices include memory ICs such as DRAMs and flash memories; logic ICs such as system LSIs; optical semiconductors such as LEDs (light emitting diodes) and LDs (semiconductor lasers); microcomputers, semiconductor sensors, general-purpose linear ICs, Control / driver IC and the like.
Claims (4)
工程１：基板と、所望レジストパターンの反転パターンを表面に有するモールドとを組み合わせて、ノニオン性含フッ素界面活性剤と、環構造を有する重合性モノマー、または重合により環構造を形成する重合性モノマーとを含むレジスト組成物を、該基板表面と該モールドのパターン面との間に挟持させる工程。
工程２：前記レジスト組成物中の重合性モノマーを重合させて該組成物からレジスト膜を形成させる工程。
工程３：モールドをレジスト膜から剥離して加工基板を得る工程。 By performing the following step 1, the following step 2, and the following step 3 in order, a processed substrate in which the substrate and the resist film on which the desired resist pattern is formed is obtained is obtained, and then a resist film of the processed substrate is formed. Etching the processed surface and etching the substrate, A method for producing an etched processed substrate.
Step 1: A nonionic fluorine-containing surfactant and a polymerizable monomer having a ring structure, or a polymerizable monomer forming a ring structure by polymerization, by combining a substrate and a mold having a reverse pattern of a desired resist pattern on the surface A step of sandwiching a resist composition comprising: the substrate surface and the pattern surface of the mold.
Step 2: A step of polymerizing a polymerizable monomer in the resist composition to form a resist film from the composition.
Step 3: A step of removing the mold from the resist film to obtain a processed substrate.
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