JP2008246876A - Film-depositing composition for nano imprinting, manufacturing method of structure and structure - Google Patents
Film-depositing composition for nano imprinting, manufacturing method of structure and structure Download PDFInfo
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- JP2008246876A JP2008246876A JP2007091695A JP2007091695A JP2008246876A JP 2008246876 A JP2008246876 A JP 2008246876A JP 2007091695 A JP2007091695 A JP 2007091695A JP 2007091695 A JP2007091695 A JP 2007091695A JP 2008246876 A JP2008246876 A JP 2008246876A
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- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000000151 deposition Methods 0.000 title abstract 3
- 229920005989 resin Polymers 0.000 claims abstract description 116
- 239000011347 resin Substances 0.000 claims abstract description 116
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 16
- 238000003825 pressing Methods 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 239000000470 constituent Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 47
- 238000000059 patterning Methods 0.000 description 28
- 239000000126 substance Substances 0.000 description 20
- 238000001127 nanoimprint lithography Methods 0.000 description 12
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PWATWSYOIIXYMA-UHFFFAOYSA-N Pentylbenzene Chemical compound CCCCCC1=CC=CC=C1 PWATWSYOIIXYMA-UHFFFAOYSA-N 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 230000007261 regionalization Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- XXXFZKQPYACQLD-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl acetate Chemical compound CC(=O)OCCOCCO XXXFZKQPYACQLD-UHFFFAOYSA-N 0.000 description 1
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- PPPFYBPQAPISCT-UHFFFAOYSA-N 2-hydroxypropyl acetate Chemical compound CC(O)COC(C)=O PPPFYBPQAPISCT-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- AXPZDYVDTMMLNB-UHFFFAOYSA-N Benzyl ethyl ether Chemical compound CCOCC1=CC=CC=C1 AXPZDYVDTMMLNB-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- XRLHGXGMYJNYCR-UHFFFAOYSA-N acetic acid;2-(2-hydroxypropoxy)propan-1-ol Chemical compound CC(O)=O.CC(O)COC(C)CO XRLHGXGMYJNYCR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000002635 aromatic organic solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YFNONBGXNFCTMM-UHFFFAOYSA-N butoxybenzene Chemical compound CCCCOC1=CC=CC=C1 YFNONBGXNFCTMM-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- -1 cresyl methyl ether Chemical compound 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 229930007927 cymene Natural products 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UHKJHMOIRYZSTH-UHFFFAOYSA-N ethyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OCC UHKJHMOIRYZSTH-UHFFFAOYSA-N 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 229940117360 ethyl pyruvate Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 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
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Shaping Of Tube Ends By Bending Or Straightening (AREA)
- Paints Or Removers (AREA)
- Silicon Polymers (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
本発明は、ナノインプリント用の膜形成組成物、並びに構造体の製造方法及び製造された構造体に関する。 The present invention relates to a film forming composition for nanoimprinting, a method for producing a structure, and a produced structure.
リソグラフィ技術は、半導体デバイスプロセスのコアテクノロジーであり、近年の半導体集積回路（ＩＣ）の高集積化に伴い、さらなる配線の微細化が進行している。微細化手法としては、より短波長の光源、例えばＫｒＦエキシマレーザー、ＡｒＦエキシマレーザー、Ｆ２レーザー、ＥＵＶ（極端紫外光）、ＥＢ（電子線）、Ｘ線等を用いる光源波長の短波長化や、露光装置のレンズの開口数（ＮＡ）の大口径化（高ＮＡ化）等が一般的である。しかしながら、光源波長の短波長化は、高額な新たな露光装置が必要となってしまう。 Lithography technology is a core technology of semiconductor device processes, and further miniaturization of wiring is progressing with the recent high integration of semiconductor integrated circuits (ICs). As a miniaturization method, a light source having a shorter wavelength, for example, a KrF excimer laser, an ArF excimer laser, an F 2 laser, EUV (extreme ultraviolet light), EB (electron beam), X-ray, or the like is used. In general, the numerical aperture (NA) of the lens of the exposure apparatus is increased (higher NA) or the like. However, shortening the wavelength of the light source requires an expensive new exposure apparatus.
このような状況のもと、Ｃｈｏｕらによって、ナノインプリントリソグラフィが提案された（特許文献１参照）。ナノインプリントリソグラフィでは、所定のパターンが形成されたモールドを、表面に樹脂層が形成された基体に対して押し付け、モールドのパターンを樹脂層に転写している。 Under such circumstances, Chou et al. Proposed nanoimprint lithography (see Patent Document 1). In nanoimprint lithography, a mold on which a predetermined pattern is formed is pressed against a substrate on which a resin layer is formed, and the pattern of the mold is transferred to the resin layer.
Ｃｈｏｕらによって最初に提案されたナノインプリントリソグラフィは、樹脂層に熱可塑性樹脂であるポリメタクリル酸メチル（ＰＭＭＡ）が用いられ、樹脂層を変形させる前に加熱により樹脂を軟化させておき、次いで、モールドを押し付けて樹脂層を変形させ、その後、樹脂層を冷却して固化させる工程を経ることから、「熱サイクルナノインプリントリソグラフィ」と呼ばれている。 In the nanoimprint lithography first proposed by Chou et al., Polymethyl methacrylate (PMMA), which is a thermoplastic resin, is used for the resin layer, and the resin is softened by heating before the resin layer is deformed. Since the resin layer is deformed by pressing and the resin layer is then cooled and solidified, it is called “thermal cycle nanoimprint lithography”.
しかしながら、この熱サイクルナノインプリントリソグラフィには、樹脂層の昇温、冷却に時間を要するためスループットが低いという問題や、温度差によりパターン寸法が変化するという問題等があった。 However, this thermal cycle nanoimprint lithography has problems such as low throughput due to the time required for temperature rise and cooling of the resin layer and a problem that pattern dimensions change due to temperature differences.
そこで、熱可塑性樹脂の代わりに、光（紫外線、電子線）で硬化する光硬化性樹脂を用いたナノインプリントリソグラフィが提案された。このプロセスは、光硬化性樹脂を含む樹脂層にモールドを押し付け、次いで、光を照射して樹脂を硬化させ、その後、モールドを剥離することにより転写パターン（構造体）を得る。この手法は、光を利用して樹脂層を硬化させることから、「光ナノインプリントリソグラフィ」と呼ばれている。 Therefore, nanoimprint lithography using a photocurable resin that is cured by light (ultraviolet rays, electron beams) instead of a thermoplastic resin has been proposed. In this process, a mold is pressed against a resin layer containing a photo-curable resin, and then the resin is irradiated with light to cure the resin, and then the mold is peeled to obtain a transfer pattern (structure). This technique is called “optical nanoimprint lithography” because the resin layer is cured using light.
しかしながら、この光ナノインプリントリソグラフィには、モールドを押し付けた状態で紫外線等を照射して樹脂を硬化させるため、大掛かりな装置が必要になるという問題や、光照射による転写パターン形成速度が遅いという問題等があった。
一方、別のナノインプリントリソグラフィ技術において、スピンオングラス（ＳＯＧ）等をレジスト形成材料として使用することが提案されている（特許文献２参照）。このプロセスでは、基板上に形成されたレジスト形成材料からなる樹脂層にモールドを押し付け、次いで、モールドを剥離することにより転写パターン（構造体）を得ている。この手法は、室温にて転写パターンを得ることから、「室温ナノインプリントリソグラフィ」と呼ばれている。この室温ナノインプリントリソグラフィにおいて形成される転写パターン（構造体）は、微小なパターンであるため、リソグラフィ以外にも、ＣＣＤに用いられる微小なレンズ等への応用が期待されている。本明細書では、室温ナノインプリントリソグラフィにおける転写パターン（構造体）を形成することを「室温ナノインプリント」という。 On the other hand, in another nanoimprint lithography technique, it has been proposed to use spin-on-glass (SOG) or the like as a resist forming material (see Patent Document 2). In this process, a mold is pressed against a resin layer made of a resist forming material formed on a substrate, and then the mold is peeled to obtain a transfer pattern (structure). This method is called “room temperature nanoimprint lithography” because a transfer pattern is obtained at room temperature. Since the transfer pattern (structure) formed in this room temperature nanoimprint lithography is a minute pattern, it is expected to be applied to a minute lens used for a CCD other than lithography. In this specification, forming a transfer pattern (structure) in room temperature nanoimprint lithography is referred to as “room temperature nanoimprint”.
この室温ナノインプリントでは、特に微細なパターンが形成されたモールドを樹脂層に押し付けたときに、モールドの凹部の隅にまで樹脂が充填されず、パターン形状が高精度に転写されないという問題や、モールドを剥離したときに、転写パターンが基体から剥がれてしまうという問題等があった。また、形成される構造体自体をそのまま使用するため、形成された構造体の熱等に対する形状安定性が求められていた。 In this room temperature nanoimprint, especially when a mold with a fine pattern formed is pressed against the resin layer, the resin is not filled into the corners of the recesses of the mold, and the pattern shape is not transferred with high accuracy. When peeled off, there was a problem that the transfer pattern was peeled off from the substrate. In addition, since the formed structure itself is used as it is, shape stability of the formed structure against heat or the like has been demanded.
本発明は、このような従来の課題に鑑みてなされたものであり、モールドの形状を高精度に転写することができ、且つ、基体との密着性、モールドの剥離性が良好なナノインプリント用の膜形成組成物、並びに構造体の製造方法及び製造された構造体を提供することを目的とする。 The present invention has been made in view of such a conventional problem, and can be used for nanoimprinting that can transfer the shape of a mold with high accuracy and has good adhesion to a substrate and good mold releasability. An object is to provide a film-forming composition, a method for producing a structure, and a produced structure.
本発明の第一の態様は、下記一般式（ａ−１）で表される構成単位を有するシルセスキオキサン樹脂（Ａ）を含有することを特徴とするナノインプリント用の膜形成組成物である。
本発明の第二の態様は、基体上にシルセスキオキサン樹脂を含む膜形成組成物を塗布して樹脂層を形成する工程と、前記樹脂層にモールドを押し付ける工程と、前記樹脂層から前記モールドを剥離する工程と、を含むことを特徴とする構造体の製造方法である。 The second aspect of the present invention includes a step of applying a film-forming composition containing a silsesquioxane resin on a substrate to form a resin layer, a step of pressing a mold against the resin layer, and And a step of peeling the mold.
本発明の第三の態様は、本発明の構造体の製造方法により得られた構造体である。 The third aspect of the present invention is a structure obtained by the method for producing a structure of the present invention.
本発明の膜形成組成物は、モールドの形状を高精度に転写することができ、且つ、基体との密着性、モールドの剥離性が良好である。したがって、この膜形成組成物からなる樹脂層にモールドを押し付けることにより、モールドの形状を高精度に反映した構造体を製造することができる。さらに、本発明の構造体の製造方法によれば、特に製造された構造体の熱等に対する形状安定性を向上させることができる。 The film forming composition of the present invention can transfer the shape of the mold with high accuracy, and has good adhesion to the substrate and good mold releasability. Therefore, a structure that reflects the shape of the mold with high accuracy can be manufactured by pressing the mold against the resin layer made of the film-forming composition. Furthermore, according to the structure manufacturing method of the present invention, the shape stability of the manufactured structure against heat and the like can be improved.
以下、本発明の実施形態について説明する。 Hereinafter, embodiments of the present invention will be described.
≪膜形成組成物≫
＜シルセスキオキサン樹脂（Ａ）＞
本発明の膜形成組成物は、下記一般式（ａ−１）で表される構成単位を有するシルセスキオキサン樹脂（Ａ）を含有することを特徴とする。この構成単位は、１種を用いてもよく、２種以上組み合わせて用いてもよい。
<< Film-forming composition >>
<Silsesquioxane resin (A)>
The film forming composition of the present invention contains a silsesquioxane resin (A) having a structural unit represented by the following general formula (a-1). As this structural unit, one type may be used, or two or more types may be used in combination.
上記一般式（ａ−１）中、Ｒ１は水素原子又は炭素数１〜５のアルキル基を表す。炭素数１〜５のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基等の直鎖状のアルキル基や、イソプロピル基、ｔｅｒｔ−ブチル基等の分岐鎖状のアルキル基が挙げられる。このＲ１としては、水素原子が特に好ましい。
また、Ｒ２は単結合又は炭素数１〜５のアルキレン基を表す。炭素数１〜５のアルキレン基としては、メチレン基、エチレン基、ｎ−プロピレン基、ｎ−ブチレン基等の直鎖状のアルキレン基や、イソプロピレン基、ｎ−ブチレン基等の分岐鎖状のアルキレン基が挙げられる。このＲ２としては、メチレン基及びエチレン基が特に好ましい。
In the general formula (a-1), R 1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms include linear alkyl groups such as methyl group, ethyl group, n-propyl group, and n-butyl group, and branched chain alkyl groups such as isopropyl group and tert-butyl group. Groups. R 1 is particularly preferably a hydrogen atom.
R 2 represents a single bond or an alkylene group having 1 to 5 carbon atoms. Examples of the alkylene group having 1 to 5 carbon atoms include linear alkylene groups such as methylene group, ethylene group, n-propylene group and n-butylene group, and branched chain groups such as isopropylene group and n-butylene group. An alkylene group is mentioned. As R 2 , a methylene group and an ethylene group are particularly preferable.
本発明の膜形成組成物は、この一般式（ａ−１）で表される構成単位を有するシルセスキオキサン樹脂（Ａ）を含有するため、微小空間への埋め込み性が良好なものとなる。したがって、この膜形成組成物からなる樹脂層にモールドを押し付けた場合、低いプレス圧力且つ短いプレス時間で、モールドの形状を高精度に転写することができる。
また、このようなシルセスキオキサン樹脂（Ａ）を含有する本発明の膜形成組成物は、樹脂層と基体との密着性、樹脂層からのモールドの剥離性も良好なものとなる。
さらに、このようなシルセスキオキサン樹脂（Ａ）を含有する本発明の膜形成組成物は、高い透明性・屈折率を有する。したがって、この膜形成組成物により、レンズ等の高屈折率部材を製造することが可能となる。
Since the film-forming composition of the present invention contains the silsesquioxane resin (A) having the structural unit represented by the general formula (a-1), the embedding property in a minute space is good. . Therefore, when the mold is pressed against the resin layer made of this film-forming composition, the shape of the mold can be transferred with high accuracy with a low pressing pressure and a short pressing time.
In addition, the film-forming composition of the present invention containing such a silsesquioxane resin (A) also has good adhesion between the resin layer and the substrate and mold releasability from the resin layer.
Furthermore, the film-forming composition of the present invention containing such a silsesquioxane resin (A) has high transparency and refractive index. Therefore, a high refractive index member such as a lens can be produced by this film forming composition.
一般式（ａ−１）で表される構成単位の割合は、シルセスキオキサン樹脂（Ａ）の全構成単位に対して１０〜１００モル％であることが好ましく、１５〜１００モル％であることがより好ましい。 The proportion of the structural unit represented by the general formula (a-1) is preferably 10 to 100 mol% with respect to all the structural units of the silsesquioxane resin (A), and is 15 to 100 mol%. It is more preferable.
シルセスキオキサン樹脂（Ａ）は、下記一般式（ａ−２）で表される構成単位をさらに有していてもよい。 The silsesquioxane resin (A) may further have a structural unit represented by the following general formula (a-2).
上記一般式（ａ−２）中、Ｒ３は炭素数１〜１５のアルキル基又は炭素数６〜１５の芳香族炭化水素基を表す。炭素数１〜１５のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基等の直鎖状のアルキル基、イソプロピル基、ｔｅｒｔ−ブチル基等の分岐鎖状のアルキル基、或いはシクロペンタン、シクロヘキサン、アダマンタン、ノルボルナン等から１個の水素原子を除いた環状のアルキル基が挙げられる。また、炭素数６〜１５の芳香族炭化水素基としては、フェニル基、ナフチル基、アントラセニル基等が挙げられる。このＲ３としては、フェニル基、ナフチル基が特に好ましい。 In the general formula (a-2), R 3 represents an alkyl group having 1 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 15 carbon atoms. Examples of the alkyl group having 1 to 15 carbon atoms include linear alkyl groups such as methyl group, ethyl group, n-propyl group and n-butyl group, and branched alkyl groups such as isopropyl group and tert-butyl group. Or a cyclic alkyl group obtained by removing one hydrogen atom from cyclopentane, cyclohexane, adamantane, norbornane and the like. Examples of the aromatic hydrocarbon group having 6 to 15 carbon atoms include a phenyl group, a naphthyl group, and an anthracenyl group. R 3 is particularly preferably a phenyl group or a naphthyl group.
シルセスキオキサン樹脂（Ａ）は、上記一般式（ａ−１）、（ａ−２）で表される構成単位以外の構成単位をさらに有していてもよい。 The silsesquioxane resin (A) may further have structural units other than the structural units represented by the general formulas (a-1) and (a-2).
シルセスキオキサン樹脂（Ａ）の質量平均分子量は、特に限定されないが、２０００〜３００００であることが好ましく、３０００〜１５０００であることがより好ましい。上記範囲とすることで、有機溶剤への溶解性が良好となる。また、本発明の膜形成組成物からなる樹脂層にモールドを押し付けたとき、モールドの形状が高精度に転写されるようになる。 Although the mass average molecular weight of silsesquioxane resin (A) is not specifically limited, It is preferable that it is 2000-30000, and it is more preferable that it is 3000-15000. By setting it as the said range, the solubility to an organic solvent becomes favorable. Further, when the mold is pressed against the resin layer made of the film-forming composition of the present invention, the shape of the mold is transferred with high accuracy.
＜有機溶剤（Ｂ）＞
本発明の膜形成組成物は、前述のシルセスキオキサン樹脂（Ａ）等の全ての成分を適当な有機溶剤に溶解して溶液の形態で用いるのが好ましい。
有機溶剤（Ｂ）としては、具体的には、メタノール、エタノール、プロパノール、ｎ−ブタノール等のアルコール類；エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール等の多価アルコール類；アセトン、メチルエチルケトン、シクロヘキサノン、メチル−ｎ−アミルケトン、メチルイソアミルケトン、２−ヘプタノン等のケトン類；エチレングリコールモノアセテート、ジエチレングリコールモノアセテート、プロピレングリコールモノアセテート、又はジプロピレングリコールモノアセテート等のエステル結合を有する化合物、上記多価アルコール類又は上記エステル結合を有する化合物のモノメチルエーテル、モノエチルエーテル、モノプロピルエーテル、モノブチルエーテル等のモノアルキルエーテル若しくはモノフェニルエーテル等のエーテル結合を有する化合物等の多価アルコール類の誘導体；ジオキサン等の環状エーテル類；乳酸メチル、乳酸エチル、酢酸メチル、酢酸エチル、酢酸ブチル、ピルビン酸メチル、ピルビン酸エチル、メトキシプロピオン酸メチル、エトキシプロピオン酸エチル等のエステル類；アニソール、エチルベンジルエーテル、クレジルメチルエーテル、ジフェニルエーテル、ジベンジルエーテル、フェネトール、ブチルフェニルエーテル、エチルベンゼン、ジエチルベンゼン、アミルベンゼン、イソプロピルベンゼン、トルエン、キシレン、シメン、メシチレン等の芳香族系有機溶剤等が挙げられる。これらの有機溶剤（Ｂ）は、１種を用いてもよく、２種以上組み合わせて用いてもよい。中でも、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）、ｎ−ブタノールを用いることが好ましい。
<Organic solvent (B)>
The film-forming composition of the present invention is preferably used in the form of a solution by dissolving all the components such as the silsesquioxane resin (A) described above in a suitable organic solvent.
Specific examples of the organic solvent (B) include alcohols such as methanol, ethanol, propanol and n-butanol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; acetone, methyl ethyl ketone and cyclohexanone. , Ketones such as methyl-n-amyl ketone, methyl isoamyl ketone, 2-heptanone; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, the above polyvalent Monoalcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether of alcohols or compounds having an ester bond Derivatives of polyhydric alcohols such as compounds having an ether bond such as ruether or monophenyl ether; cyclic ethers such as dioxane; methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate , Esters such as methyl methoxypropionate and ethyl ethoxypropionate; anisole, ethylbenzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butylphenyl ether, ethylbenzene, diethylbenzene, amylbenzene, isopropylbenzene, toluene, Aromatic organic solvents such as xylene, cymene, and mesitylene are listed. These organic solvents (B) may be used alone or in combination of two or more. Among these, it is preferable to use propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), or n-butanol.
有機溶剤（Ｂ）の配合量は、特に限定されないが、シルセスキオキサン樹脂（Ａ）の濃度が０．１〜４０質量％となるように用いることが好ましく、１〜３０質量％となるように用いることがより好ましい。 Although the compounding quantity of an organic solvent (B) is not specifically limited, It is preferable to use it so that the density | concentration of silsesquioxane resin (A) may be 0.1-40 mass%, and it will be 1-30 mass%. It is more preferable to use for.
＜界面活性剤（Ｃ）＞
本発明の膜形成組成物は、必要に応じて界面活性剤（Ｃ）を含有していてもよい。界面活性剤（Ｃ）を含有することにより、モールドの形状の転写性が良好なものとなる。界面活性剤（Ｃ）としては、特に限定されず、公知の成分を用いることができる。
<Surfactant (C)>
The film-forming composition of the present invention may contain a surfactant (C) as necessary. By containing the surfactant (C), the mold shape transferability is improved. It does not specifically limit as surfactant (C), A well-known component can be used.
≪構造体の製造方法≫
本発明の構造体の製造方法は、基体上にシルセスキオキサン樹脂を含む膜形成組成物を塗布して樹脂層を形成する工程と、樹脂層にモールドを押し付ける工程と、樹脂層からモールドを剥離する工程と、を含むことを特徴とする。
≪Structure manufacturing method≫
The structure manufacturing method of the present invention includes a step of applying a film-forming composition containing a silsesquioxane resin on a substrate to form a resin layer, a step of pressing a mold against the resin layer, and a mold from the resin layer. And a step of peeling.
先ず、基体上にシルセスキオキサン樹脂を含む膜形成組成物をスピンコート法等により塗布し、樹脂層を形成する。樹脂層の膜厚は、製造する構造体の種類にもよるが、例えば１０ｎｍ〜５μｍ程度が好ましい。
また、基体としては、特に限定されず、例えば、シリコン、銅、クロム、鉄、アルミニウム等の金属からなる基板やガラス基板、或いはこれらに所定の配線パターンが形成されたものを用いることができる。また、これらの基板に有機層や無機層が形成されたものを用いてもよい。
First, a film-forming composition containing a silsesquioxane resin is applied on a substrate by a spin coating method or the like to form a resin layer. The film thickness of the resin layer depends on the type of structure to be manufactured, but is preferably about 10 nm to 5 μm, for example.
The substrate is not particularly limited, and for example, a substrate or glass substrate made of a metal such as silicon, copper, chromium, iron, or aluminum, or a substrate on which a predetermined wiring pattern is formed can be used. Moreover, you may use what formed the organic layer and the inorganic layer in these board | substrates.
次に、基体上に形成された樹脂層に所定の形状のモールドを押し付け、モールドの形状を樹脂層に転写する。この際、シルセスキオキサン樹脂を含む膜形成組成物として本発明の膜形成組成物を用いた場合には、プレス圧力が比較的低い場合であっても、短時間でモールドの凹部の隅にまで樹脂が充填されるため、モールドの形状を高精度に転写することができるとともに、加熱したり紫外線を照射したりすることなく樹脂層がモールドの形状に硬化するため、好ましい。 Next, a mold having a predetermined shape is pressed against the resin layer formed on the substrate, and the shape of the mold is transferred to the resin layer. At this time, when the film-forming composition of the present invention is used as a film-forming composition containing a silsesquioxane resin, even in a case where the pressing pressure is relatively low, the corners of the concave portions of the mold can be obtained in a short time. Since the resin is filled up to, the shape of the mold can be transferred with high accuracy, and the resin layer is cured to the shape of the mold without being heated or irradiated with ultraviolet rays, which is preferable.
モールドのプレス圧力は、１０〜５０ＭＰａ程度であることが好ましい。また、プレス時間は、樹脂層の厚さにもよるが、１０〜１２０秒程度であることが好ましい。このようにモールドを押し付けた状態で所定時間プレスすることにより、樹脂層の形状がより硬化する。 The pressing pressure of the mold is preferably about 10 to 50 MPa. Moreover, although it depends on the thickness of the resin layer, the pressing time is preferably about 10 to 120 seconds. The shape of the resin layer is further cured by pressing for a predetermined time in a state where the mold is pressed.
その後、樹脂層からモールドを剥離する。この際、シルセスキオキサン樹脂を含む膜形成組成物として本発明の膜形成組成物を用いて樹脂層を形成した場合には、基体との密着性が高く、且つモールドの剥離性が良好であるため、モールドを剥離したときに、樹脂層が基体から剥がれてしまうことがない。 Thereafter, the mold is peeled from the resin layer. At this time, when the resin layer is formed using the film-forming composition of the present invention as a film-forming composition containing a silsesquioxane resin, the adhesion to the substrate is high and the mold releasability is good. Therefore, when the mold is peeled off, the resin layer is not peeled off from the substrate.
このようにして、モールドの形状が高精度に転写された構造体を基体上に形成することができる。なお、モールドの剥離後に構造体を加熱したり紫外線（ＵＶ光）等を照射したりして、構造体をさらに硬化させるようにしても構わない。特にＵＶ光の照射は、構造体を安定化させることができ、形成された構造体の変形（シュリンク、型崩れ等）を防止することができ好ましい。このようにＵＶ光が照射された構造体は、その後に加熱等の工程がある場合にも形状変化することがなく、特にシュリンクすることがないため、そのまま構造体として用いる場合に特に好ましい。 In this way, a structure having the mold shape transferred with high precision can be formed on the substrate. Note that the structure may be further cured by heating the structure or irradiating ultraviolet rays (UV light) or the like after the mold is peeled off. In particular, irradiation with UV light is preferable because it can stabilize the structure and prevent deformation (shrink, loss of shape, etc.) of the formed structure. Thus, the structure irradiated with UV light does not change its shape even when there is a subsequent process such as heating and is not particularly shrunk.
得られる構造体の形状は、モールドの形状に応じて様々に変更することができる。例えば、所定のパターンが形成されたモールドを用いる場合、モールドを変更することにより、例えば１０ｎｍ間隔の極微細パターンが形成された構造体から、２μｍ間隔のラフパターンが形成された構造体まで、様々に製造することができる。また、本発明の膜形成組成物は高い透明性・屈折率を有するため、レンズ形状のモールドを用いることにより、ＣＭＯＳセンサー等に使用可能な極小レンズを製造することができる。 The shape of the resulting structure can be variously changed according to the shape of the mold. For example, when using a mold in which a predetermined pattern is formed, by changing the mold, for example, various structures ranging from a structure in which an extremely fine pattern having an interval of 10 nm is formed to a structure having a rough pattern having an interval of 2 μm are formed. Can be manufactured. In addition, since the film-forming composition of the present invention has high transparency and refractive index, it is possible to produce a microlens that can be used for a CMOS sensor or the like by using a lens-shaped mold.
≪パターン形成方法≫
上述のように、本発明の構造体の製造方法によれば様々な形状の構造体を製造することができるが、以下では、本発明の膜形成組成物により、基体上に所定のパターンの構造体を形成し、この構造体をレジストとして用いる場合について、さらに説明する。但し、このパターン形成方法は、上述した構造体の製造方法と同様であるため、同一の部分については記載を省略又は簡略化する。
≪Pattern formation method≫
As described above, according to the structure manufacturing method of the present invention, structures having various shapes can be manufactured. Hereinafter, a structure having a predetermined pattern on the substrate is formed by the film forming composition of the present invention. A case where a body is formed and this structure is used as a resist will be further described. However, since this pattern forming method is the same as the above-described structure manufacturing method, description of the same portion is omitted or simplified.
先ず、基体上に本発明の膜形成組成物をスピンコート法等により塗布し、樹脂層を形成する。樹脂層の膜厚は、１０〜２００ｎｍが好ましく、３０〜１５０ｎｍがより好ましい。この範囲内の膜厚とすることにより、十分なエッチング耐性が確保できる。 First, the film-forming composition of the present invention is applied on a substrate by a spin coating method or the like to form a resin layer. 10-200 nm is preferable and, as for the film thickness of a resin layer, 30-150 nm is more preferable. By setting the film thickness within this range, sufficient etching resistance can be ensured.
なお、高アスペクト比のパターンを形成する場合、基体としては、基板上に有機層が形成されたものを用いることが好ましい。有機層の形成に用いられる樹脂としては、酸素プラズマによりエッチングしやすいと同時に、シリコン基板等のエッチングに用いられるフッ化炭素系ガスに対する耐性が高いこと等から、ノボラック樹脂、アクリル樹脂、可溶性ポリイミド等が好ましい。
有機層の膜厚は、１００〜１４０００ｎｍが好ましく、３００〜５０００ｎｍがより好ましい。この範囲内の膜厚とすることにより、十分なエッチング耐性が確保できる。
When a high aspect ratio pattern is formed, it is preferable to use a substrate in which an organic layer is formed on a substrate. As the resin used for forming the organic layer, novolak resin, acrylic resin, soluble polyimide, etc. are easily etched by oxygen plasma and at the same time have high resistance to fluorocarbon gases used for etching silicon substrates. Is preferred.
The film thickness of the organic layer is preferably from 100 to 14000 nm, more preferably from 300 to 5000 nm. By setting the film thickness within this range, sufficient etching resistance can be ensured.
次に、基体上に形成された樹脂層に所定のパターンが形成されたモールドを押し付け、モールドのパターンを樹脂層に転写する。この際、本発明の膜形成組成物は、プレス圧力が比較的低い場合であっても、短時間でモールドの凹部の隅にまで樹脂が充填されるため、モールドの形状を高精度に転写することができる。 Next, a mold in which a predetermined pattern is formed is pressed against the resin layer formed on the substrate to transfer the mold pattern to the resin layer. At this time, the film-forming composition of the present invention can transfer the shape of the mold with high accuracy because the resin is filled into the corners of the concave portion of the mold in a short time even when the pressing pressure is relatively low. be able to.
その後、樹脂層からモールドを剥離する。この際、本発明の膜形成組成物からなる樹脂層は、基体との密着性が高く、且つモールドの剥離性が良好であるため、モールドを剥離したときに、樹脂層が基体から剥がれてしまうことがない。 Thereafter, the mold is peeled from the resin layer. At this time, since the resin layer made of the film-forming composition of the present invention has high adhesion to the substrate and good mold releasability, the resin layer is peeled off from the substrate when the mold is peeled off. There is nothing.
モールドのパターンが転写されたレジストが基体上に形成された後は、以下のようにして、エッチングにより基板上にパターンを形成することができる。 After the resist to which the pattern of the mold has been transferred is formed on the substrate, the pattern can be formed on the substrate by etching as follows.
すなわち、モールドのパターンが転写されたレジストをマスクとして、基板をフッ化炭素系ガスによりエッチングし、基板にパターンを形成する。なお、基板上に有機層が形成されている場合には、モールドのパターンが転写されたレジストをマスクとして、有機層を酸素プラズマによりエッチングした後、基板をフッ化炭素系ガスによりエッチングする。その後、基板上のレジスト等を溶解除去する。 That is, using the resist to which the mold pattern is transferred as a mask, the substrate is etched with a fluorocarbon gas to form a pattern on the substrate. In the case where an organic layer is formed on the substrate, the organic layer is etched by oxygen plasma using the resist to which the mold pattern is transferred as a mask, and then the substrate is etched by a fluorocarbon-based gas. Thereafter, the resist on the substrate is dissolved and removed.
次に、本発明を実施例に基づいてさらに詳細に説明するが、本発明はこれに限定されるものではない。 Next, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.
＜実施例１＞
下記化学式（１）及び（２）で表される構成単位を有するシルセスキオキサン樹脂（質量平均分子量：８５００、（１）：（２）＝３０：７０（モル比））を用い、この樹脂の濃度が１５質量％となるようにｎ−ブタノールで調整し、膜形成組成物１を得た。
<Example 1>
Using this silsesquioxane resin (mass average molecular weight: 8500, (1) :( 2) = 30: 70 (molar ratio)) having structural units represented by the following chemical formulas (1) and (2) The film-forming composition 1 was obtained by adjusting with n-butanol so that the concentration of was 15% by mass.
シリコン基板表面上にこの膜形成組成物１をスピンコート法にて塗布し、膜厚６００ｎｍの樹脂層を得た。樹脂層を乾燥や硬化することなく、ナノインプリンター ＮＭ−０４０１（明昌機工社製）を用いて、樹脂層に対してモールド(凹型パターン、ライン／スペース２００ｎｍ)をプレス圧力２０ＭＰａ（５０００Ｎの荷重）にて室温（２５℃）で６０秒間押し付けた。その後、モールドを剥離することにより、基板上にパターン状の構造体を形成した。 This film-forming composition 1 was applied on the surface of a silicon substrate by a spin coating method to obtain a resin layer having a thickness of 600 nm. Without using a nanoimprinter NM-0401 (manufactured by Meisho Kiko Co., Ltd.) without drying or curing the resin layer, a mold (concave pattern, line / space 200 nm) is pressed against the resin layer at a pressure of 20 MPa (load of 5000 N). For 60 seconds at room temperature (25 ° C.). Thereafter, the mold was removed to form a patterned structure on the substrate.
得られた構造体を走査型電子顕微鏡（ＳＥＭ）により観察したところ、高精度のパターンが基板上に再現されていることが分かった。また、プレス圧力２０ＭＰａにて、６０秒間という非常に短いプレス時間で５０％（３００ｎｍ）の深さまでパターニングできていることを確認した。
プレス圧力２０ＭＰａにて４０％（２４０ｎｍ）以上の深さまでパターニングできているものを○、４０％（２４０ｎｍ）未満の深さまでしかパターニングできていないものを×として、パターニング深さを評価した結果を表１に示す。また、ボイド、基板からの剥がれ等が発生していないものを○、発生しているものを×として、パターニング形状を評価した結果を表１に示す。
When the obtained structure was observed with a scanning electron microscope (SEM), it was found that a highly accurate pattern was reproduced on the substrate. It was also confirmed that patterning was possible to a depth of 50% (300 nm) in a very short press time of 60 seconds at a press pressure of 20 MPa.
Table 7 shows the results of evaluating the patterning depth with ○ indicating that the patterning can be performed to a depth of 40% (240 nm) or more at a pressing pressure of 20 MPa and x indicating that the patterning can be performed only to a depth of less than 40% (240 nm). It is shown in 1. In addition, Table 1 shows the results of evaluating the patterning shape, where “V” indicates that no void or peeling from the substrate occurs, and “×” indicates that the void is generated.
＜実施例２＞
上記化学式（１）及び下記化学式（３）で表される構成単位を有するシルセスキオキサン樹脂（質量平均分子量：２８００、（１）：（３）＝２８：７２（モル比））を用い、この樹脂の濃度が２０質量％となるようにプロピレングリコールモノメチルエーテルアセテートで調整し、膜形成組成物２を得た。
<Example 2>
Using a silsesquioxane resin (mass average molecular weight: 2800, (1) :( 3) = 28: 72 (molar ratio)) having structural units represented by the above chemical formula (1) and the following chemical formula (3), A film-forming composition 2 was obtained by adjusting with propylene glycol monomethyl ether acetate so that the concentration of the resin was 20% by mass.
この膜形成組成物２を用いて実施例１と同様に構造体を形成し、パターニング深さ、パターニング形状を評価した。結果を表１に示す。 A structure was formed using this film-forming composition 2 in the same manner as in Example 1, and the patterning depth and patterning shape were evaluated. The results are shown in Table 1.
＜実施例３＞
下記化学式（４）及び上記化学式（２）で表される構成単位を有するシルセスキオキサン樹脂（質量平均分子量：３０００、（４）：（２）＝７０：３０（モル比））を用い、この樹脂の濃度が２０質量％となるようにプロピレングリコールモノメチルエーテルで調整し、膜形成組成物３を得た。
<Example 3>
Using silsesquioxane resin (mass average molecular weight: 3000, (4) :( 2) = 70: 30 (molar ratio)) having structural units represented by the following chemical formula (4) and the above chemical formula (2), It adjusted with propylene glycol monomethyl ether so that the density | concentration of this resin might be 20 mass%, and the film formation composition 3 was obtained.
この膜形成組成物３を用いて実施例１と同様に構造体を形成し、パターニング深さ、パターニング形状を評価した。結果を表１に示す。 A structure was formed using this film-forming composition 3 in the same manner as in Example 1, and the patterning depth and patterning shape were evaluated. The results are shown in Table 1.
＜実施例４＞
下記化学式（５）及び上記化学式（２）で表される構成単位を有するシルセスキオキサン樹脂（質量平均分子量：３６００、（５）：（２）＝７０：３０（モル比））を用い、この樹脂の濃度が２０質量％となるようにプロピレングリコールモノメチルエーテルアセテートで調整し、膜形成組成物４を得た。
<Example 4>
Using a silsesquioxane resin (mass average molecular weight: 3600, (5) :( 2) = 70: 30 (molar ratio)) having structural units represented by the following chemical formula (5) and the above chemical formula (2), A film-forming composition 4 was obtained by adjusting with propylene glycol monomethyl ether acetate so that the concentration of this resin was 20% by mass.
この膜形成組成物４を用いて実施例１と同様に構造体を形成し、パターニング深さ、パターニング形状を評価した。結果を表１に示す。 A structure was formed using this film-forming composition 4 in the same manner as in Example 1, and the patterning depth and patterning shape were evaluated. The results are shown in Table 1.
＜実施例５＞
上記化学式（２）で表される構成単位を有するシルセスキオキサン樹脂（質量平均分子量：７０００）と上記化学式（１）で表される構成単位を有するシルセスキオキサン樹脂（質量平均分子量：６０００）とを７０：３０のモル比で混合し、この混合樹脂の濃度が２０質量％となるようにプロピレングリコールモノメチルエーテルアセテートで調整し、膜形成組成物５を得た。
<Example 5>
Silsesquioxane resin (mass average molecular weight: 7000) having a structural unit represented by the chemical formula (2) and silsesquioxane resin (mass average molecular weight: 6000) having a structural unit represented by the chemical formula (1) ) In a molar ratio of 70:30, and adjusted with propylene glycol monomethyl ether acetate so that the concentration of the mixed resin is 20% by mass to obtain a film-forming composition 5.
この膜形成組成物５を用いて実施例１と同様に構造体を形成し、パターニング深さ、パターニング形状を評価した。結果を表１に示す。 A structure was formed using this film-forming composition 5 in the same manner as in Example 1, and the patterning depth and patterning shape were evaluated. The results are shown in Table 1.
＜実施例６＞
上記化学式（２）で表される構成単位を有するシルセスキオキサン樹脂（質量平均分子量：７０００）と下記化学式（６）で表される構成単位を有するシルセスキオキサン樹脂（製品名：ＯＣＤ Ｔ−２、東京応化工業社製、質量平均分子量：１５００）とを５０：５０のモル比で混合し、この混合樹脂の濃度が２０質量％となるように、プロピレングリコールモノメチルエーテルアセテート：エタノール：酢酸エチル＝５：４：１の混合溶剤で調整し、膜形成組成物６を得た。
<Example 6>
Silsesquioxane resin (mass average molecular weight: 7000) having a structural unit represented by the chemical formula (2) and a silsesquioxane resin (product name: OCD T) having a structural unit represented by the following chemical formula (6) -2, manufactured by Tokyo Ohka Kogyo Co., Ltd., mass average molecular weight: 1500) at a molar ratio of 50:50, and propylene glycol monomethyl ether acetate: ethanol: acetic acid so that the concentration of the mixed resin is 20% by mass. A film forming composition 6 was obtained by adjusting with a mixed solvent of ethyl = 5: 4: 1.
この膜形成組成物６を用いて実施例１と同様に構造体を形成し、パターニング深さ、パターニング形状を評価した。結果を表１に示す。 A structure was formed using this film-forming composition 6 in the same manner as in Example 1, and the patterning depth and patterning shape were evaluated. The results are shown in Table 1.
＜実施例７＞
上記化学式（２）で表される構成単位を有するシルセスキオキサン樹脂（質量平均分子量：７０００）と下記化学式（７）で表される構成単位を有するシルセスキオキサン樹脂（製品名：ＯＣＤ Ｔ−９、東京応化工業社製、質量平均分子量：２２００）とを５０：５０のモル比で混合し、この混合樹脂の濃度が２０質量％となるように、プロピレングリコールモノメチルエーテルアセテート：エタノール：ｎ−ブタノール：メトキシプロピオン酸メチル＝５：２：２：１の混合溶剤で調整し、膜形成組成物７を得た。
<Example 7>
Silsesquioxane resin (mass average molecular weight: 7000) having a structural unit represented by the above chemical formula (2) and silsesquioxane resin (product name: OCD T) having a structural unit represented by the following chemical formula (7) -9, manufactured by Tokyo Ohka Kogyo Co., Ltd., mass average molecular weight: 2200) at a molar ratio of 50:50, and propylene glycol monomethyl ether acetate: ethanol: n so that the concentration of the mixed resin is 20% by mass. -Butanol: methyl methoxypropionate = 5: 2: 2: 1 was used to prepare a film-forming composition 7.
この膜形成組成物７を用いて実施例１と同様に構造体を形成し、パターニング深さ、パターニング形状を評価した。結果を表１に示す。 A structure was formed using this film-forming composition 7 in the same manner as in Example 1, and the patterning depth and patterning shape were evaluated. The results are shown in Table 1.
＜実施例８＞
上記化学式（２）で表される構成単位を有するシルセスキオキサン樹脂（質量平均分子量：７０００）と下記化学式（８）で表される構成単位を有するシルセスキオキサン樹脂（製品名：ＯＣＤ Ｔ−１２、東京応化工業社製、質量平均分子量：１８００）とを５０：５０のモル比で混合し、この混合樹脂の濃度が２０質量％となるように、プロピレングリコールモノメチルエーテルアセテート：プロピレングリコールジメチルエーテル＝５：５の混合溶剤で調整し、膜形成組成物８を得た。
<Example 8>
Silsesquioxane resin (mass average molecular weight: 7000) having a structural unit represented by the chemical formula (2) and a silsesquioxane resin (product name: OCD T) having a structural unit represented by the following chemical formula (8) -12, manufactured by Tokyo Ohka Kogyo Co., Ltd., mass average molecular weight: 1800) in a molar ratio of 50:50, and propylene glycol monomethyl ether acetate: propylene glycol dimethyl ether so that the concentration of the mixed resin is 20% by mass. = 5: 5 A mixed solvent was used to obtain a film-forming composition 8.
この膜形成組成物８を用いて実施例１と同様に構造体を形成し、パターニング深さ、パターニング形状を評価した。結果を表１に示す。 A structure was formed using this film-forming composition 8 in the same manner as in Example 1, and the patterning depth and patterning shape were evaluated. The results are shown in Table 1.
＜実施例９＞
上記化学式（２）で表される構成単位を有するシルセスキオキサン樹脂（質量平均分子量：７０００）と上記化学式（６）及び（７）で表される構成単位を有するシルセスキオキサン樹脂（製品名：ＯＣＤ Ｔ−７、東京応化工業社製、質量平均分子量：２０００、（６）：（７）＝５０：５０（モル比））とを５０：５０のモル比で混合し、この混合樹脂の濃度が２０質量％となるように、プロピレングリコールモノメチルエーテルアセテート：イソプロパノール：アセトン＝５：３：２の混合溶剤で調整し、膜形成組成物９を得た。
<Example 9>
Silsesquioxane resin (mass average molecular weight: 7000) having a structural unit represented by the chemical formula (2) and a silsesquioxane resin having a structural unit represented by the chemical formulas (6) and (7) (product) Name: OCD T-7, manufactured by Tokyo Ohka Kogyo Co., Ltd., mass average molecular weight: 2000, (6): (7) = 50: 50 (molar ratio)) were mixed at a molar ratio of 50:50, and this mixed resin The film-forming composition 9 was obtained by adjusting with a mixed solvent of propylene glycol monomethyl ether acetate: isopropanol: acetone = 5: 3: 2 so that the concentration of was 20% by mass.
この膜形成組成物９を用いて実施例１と同様に構造体を形成し、パターニング深さ、パターニング形状を評価した。結果を表１に示す。 A structure was formed using this film-forming composition 9 in the same manner as in Example 1, and the patterning depth and patterning shape were evaluated. The results are shown in Table 1.
＜比較例１＞
上記化学式（１）で表される構成単位を有するシルセスキオキサン樹脂（質量平均分子量：６０００）を用い、この樹脂の濃度が２０質量％となるようにプロピレングリコールモノメチルエーテルアセテートで調整し、膜形成組成物１０を得た。
<Comparative Example 1>
A silsesquioxane resin (mass average molecular weight: 6000) having a structural unit represented by the above chemical formula (1) was used, and the concentration of this resin was adjusted with propylene glycol monomethyl ether acetate so as to be 20% by mass. A forming composition 10 was obtained.
この膜形成組成物１０を用いて実施例１と同様に構造体を形成し、パターニング深さ、パターニング形状を評価した。結果を表１に示す。 A structure was formed using this film-forming composition 10 in the same manner as in Example 1, and the patterning depth and patterning shape were evaluated. The results are shown in Table 1.
＜比較例２＞
上記化学式（６）で表される構成単位を有するシルセスキオキサン樹脂（製品名：ＯＣＤ Ｔ−２、東京応化工業社製、質量平均分子量：１５００）を用い、この樹脂の濃度が２０質量％となるように、エタノール：酢酸エチル＝８：２の混合溶剤で調整し、膜形成組成物１１を得た。
<Comparative example 2>
Using a silsesquioxane resin (product name: OCD T-2, manufactured by Tokyo Ohka Kogyo Co., Ltd., mass average molecular weight: 1500) having a structural unit represented by the above chemical formula (6), the concentration of this resin is 20% by mass. Thus, a film-forming composition 11 was obtained by adjusting with a mixed solvent of ethanol: ethyl acetate = 8: 2.
この膜形成組成物１１を用いて実施例１と同様に構造体を形成し、パターニング深さ、パターニング形状を評価した。結果を表１に示す。 A structure was formed using this film-forming composition 11 in the same manner as in Example 1, and the patterning depth and patterning shape were evaluated. The results are shown in Table 1.
＜比較例３＞
上記化学式（８）で表される構成単位を有するシルセスキオキサン樹脂（製品名：ＯＣＤ Ｔ−１２、東京応化工業社製、質量平均分子量：１８００）を用い、この樹脂の濃度が２０質量％となるようにプロピレングリコールジメチルエーテルで調整し、膜形成組成物１２を得た。
<Comparative Example 3>
Using a silsesquioxane resin (product name: OCD T-12, manufactured by Tokyo Ohka Kogyo Co., Ltd., mass average molecular weight: 1800) having a structural unit represented by the above chemical formula (8), the concentration of this resin is 20% by mass. The film forming composition 12 was obtained by adjusting with propylene glycol dimethyl ether.
この膜形成組成物１２を用いて実施例１と同様に構造体を形成し、パターニング深さ、パターニング形状を評価した。結果を表１に示す。 A structure was formed using this film-forming composition 12 in the same manner as in Example 1, and the patterning depth and patterning shape were evaluated. The results are shown in Table 1.
表１から分かるように、上記一般式（ａ−１）で表される構成単位を有するシルセスキオキサン樹脂を用いた実施例１〜９では、プレス圧力２０ＭＰａにて、６０秒間という非常に短いプレス時間で４０％（２４０ｎｍ）を超える深さまでモールドを押し込むことができ、しかもモールドの剥離時に樹脂層が基板から剥がれてしまうこと等がなかった。一方、上記一般式（ａ−１）で表される構成単位を有さないシルセスキオキサン樹脂を用いた比較例１〜３では、４０％（２４０ｎｍ）未満の深さまでしかモールドを押し込むことができないか、又はモールドの剥離時に樹脂層が基板から剥がれた。 As can be seen from Table 1, in Examples 1 to 9 using the silsesquioxane resin having the structural unit represented by the general formula (a-1), the press pressure is 20 MPa and the time is very short as 60 seconds. The mold could be pushed to a depth exceeding 40% (240 nm) in the pressing time, and the resin layer was not peeled off from the substrate when the mold was peeled off. On the other hand, in Comparative Examples 1 to 3 using the silsesquioxane resin not having the structural unit represented by the general formula (a-1), the mold can be pushed only to a depth of less than 40% (240 nm). The resin layer was peeled off from the substrate when the mold was peeled off.
＜実施例１０＞
シリコン基板表面上に膜形成組成物１をスピンコート法にて塗布し、膜厚１００ｎｍの樹脂層を得た。樹脂層を乾燥や硬化することなく、ナノインプリンター ＮＭ−０４０１（明昌機工社製）を用いて、樹脂層に対してモールド(凹型パターン、ライン／スペース４０ｎｍ)をプレス圧力２０ＭＰａ（５０００Ｎの荷重）にて室温（２５℃）で６０秒間押し付けた。その後、モールドを剥離することにより、基板上にパターン状の構造体を形成した。
<Example 10>
The film forming composition 1 was applied onto the surface of the silicon substrate by a spin coating method to obtain a resin layer having a thickness of 100 nm. Without drying or curing the resin layer, a nanoimprinter NM-0401 (manufactured by Meisho Kiko Co., Ltd.) was used to press the mold (concave pattern, line / space 40 nm) against the resin layer at a pressure of 20 MPa (load of 5000 N). For 60 seconds at room temperature (25 ° C.). Thereafter, the mold was peeled to form a patterned structure on the substrate.
得られた構造体を走査型電子顕微鏡（ＳＥＭ）により観察したところ、高精度のパターンが基板上に再現されていることが分かった。また、プレス圧力２０ＭＰａにて、６０秒間という非常に短いプレス時間で１００ｎｍの膜厚を貫通する１００％の深さまでパターニングできていることを確認した。 When the obtained structure was observed with a scanning electron microscope (SEM), it was found that a highly accurate pattern was reproduced on the substrate. It was also confirmed that patterning was possible to a depth of 100% penetrating a film thickness of 100 nm with a press pressure of 20 MPa and a very short press time of 60 seconds.
さらに、上記実施例１〜９、比較例１〜３で得られた膜形成組成物を用いて形成された構造体に低圧水銀灯（製品名：ＤｅｅｐＵＶＰｒｏｃｅｓｓｏｒ ランプＬ−８００ＦＳ、日本電池社製、メイン波長２５４，１８５ｎｍ）にて５０℃、９０秒の条件でＵＶ光を照射したもの、および照射していないものについて、４００℃、窒素中での加熱後の形状変化について検討した。結果を表２に示す。なお、形状変化はシュリンク率により評価した。このシュリンク率は、加熱前における構造体の膜厚１００ｎｍに対する加熱後における構造体の膜厚の割合が１０％以上変化していないものを○、１０％以上変化したものを×とした。 Further, a low-pressure mercury lamp (product name: DeepUVProcessor lamp L-800FS, manufactured by Nippon Battery Co., Ltd., main wavelength) was formed on the structures formed using the film-forming compositions obtained in Examples 1-9 and Comparative Examples 1-3. 254, 185 nm), the shape change after heating in nitrogen at 400 ° C. was examined for those irradiated with UV light at 50 ° C. for 90 seconds and those not irradiated. The results are shown in Table 2. The shape change was evaluated by the shrink rate. The shrinkage ratio was evaluated as ◯ when the ratio of the film thickness of the structure after heating to the film thickness of 100 nm before heating did not change by 10% or more, and x when the ratio changed by 10% or more.
表２から分かるように、構造体にＵＶ光を照射することにより、形状変化を抑制できることが確認された。
As can be seen from Table 2, it was confirmed that the shape change can be suppressed by irradiating the structure with UV light.
Claims (10)
前記樹脂層にモールドを押し付ける工程と、
前記樹脂層から前記モールドを剥離する工程と、を含むことを特徴とする構造体の製造方法。 Applying a film-forming composition containing a silsesquioxane resin on a substrate to form a resin layer;
Pressing the mold against the resin layer;
And a step of peeling the mold from the resin layer.
A structure obtained by the method for producing a structure according to claim 5.
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| PCT/JP2008/053988 WO2008126523A1 (en) | 2007-03-30 | 2008-03-05 | Film forming composition for nanoimprinting, process for production of structures, and structures |
| KR1020097019775A KR20090117947A (en) | 2007-03-30 | 2008-03-05 | Film forming compositions for nanoimprints, and methods and structures for producing structures |
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| JP2009007515A (en) * | 2007-06-29 | 2009-01-15 | Showa Denko Kk | Fine pattern transfer material composition and formation method of fine pattern |
| JP2010141064A (en) * | 2008-12-11 | 2010-06-24 | Hitachi High-Technologies Corp | Stamper for minute pattern transfer, and method for manufacturing the same |
| JP2011204309A (en) * | 2010-03-25 | 2011-10-13 | Hitachi High-Technologies Corp | Stamper for micropattern transfer |
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| JP2009007515A (en) * | 2007-06-29 | 2009-01-15 | Showa Denko Kk | Fine pattern transfer material composition and formation method of fine pattern |
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| US9816003B2 (en) | 2013-10-25 | 2017-11-14 | Tokyo Ohka Kogyo Co., Ltd. | Method of producing structure containing phase-separated structure |
| US9442371B2 (en) | 2014-01-23 | 2016-09-13 | Tokyo Ohka Kogyo Co., Ltd. | Method of producing structure containing phase-separated structure, method of forming pattern and method of forming fine pattern |
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