WO2018008734A1 - 膜形成用組成物、膜形成方法及び自己組織化リソグラフィープロセス - Google Patents
膜形成用組成物、膜形成方法及び自己組織化リソグラフィープロセス Download PDFInfo
- Publication number
- WO2018008734A1 WO2018008734A1 PCT/JP2017/024875 JP2017024875W WO2018008734A1 WO 2018008734 A1 WO2018008734 A1 WO 2018008734A1 JP 2017024875 W JP2017024875 W JP 2017024875W WO 2018008734 A1 WO2018008734 A1 WO 2018008734A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- group
- repeating unit
- forming composition
- substrate
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims description 68
- 230000008569 process Effects 0.000 title claims description 34
- 238000001459 lithography Methods 0.000 title claims description 19
- 238000002408 directed self-assembly Methods 0.000 title abstract description 5
- 230000015572 biosynthetic process Effects 0.000 title description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 55
- 239000000758 substrate Substances 0.000 claims abstract description 54
- 239000002904 solvent Substances 0.000 claims abstract description 42
- 229920001400 block copolymer Polymers 0.000 claims abstract description 30
- 229910008051 Si-OH Inorganic materials 0.000 claims abstract description 18
- 229910006358 Si—OH Inorganic materials 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 229910007991 Si-N Inorganic materials 0.000 claims abstract description 17
- 229910006294 Si—N Inorganic materials 0.000 claims abstract description 17
- 239000002344 surface layer Substances 0.000 claims abstract description 9
- -1 methylol group Chemical group 0.000 claims description 48
- 238000000576 coating method Methods 0.000 claims description 46
- 239000011248 coating agent Substances 0.000 claims description 42
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 22
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 238000005530 etching Methods 0.000 claims description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 14
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 5
- 229910018557 Si O Inorganic materials 0.000 claims description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 238000005191 phase separation Methods 0.000 abstract description 28
- 230000007547 defect Effects 0.000 abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 51
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 17
- 239000007787 solid Substances 0.000 description 16
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 14
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 229910021642 ultra pure water Inorganic materials 0.000 description 13
- 239000012498 ultrapure water Substances 0.000 description 13
- 239000002585 base Substances 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- VMGSQCIDWAUGLQ-UHFFFAOYSA-N n',n'-bis[2-(dimethylamino)ethyl]-n,n-dimethylethane-1,2-diamine Chemical compound CN(C)CCN(CCN(C)C)CCN(C)C VMGSQCIDWAUGLQ-UHFFFAOYSA-N 0.000 description 7
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 7
- 230000005855 radiation Effects 0.000 description 7
- 230000007261 regionalization Effects 0.000 description 7
- 150000003440 styrenes Chemical class 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 238000000137 annealing Methods 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000004699 copper complex Chemical class 0.000 description 6
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 150000005846 sugar alcohols Polymers 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000004210 ether based solvent Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- MHXMVFDLNGKBSR-UHFFFAOYSA-N 2-hydroxyethyl 2-bromo-2-methylpropanoate Chemical compound CC(C)(Br)C(=O)OCCO MHXMVFDLNGKBSR-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000001020 plasma etching Methods 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000001338 self-assembly Methods 0.000 description 4
- 125000002653 sulfanylmethyl group Chemical group [H]SC([H])([H])[*] 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- FXRQXYSJYZPGJZ-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]ethenylbenzene Chemical compound CC(C)(C)OC=CC1=CC=CC=C1 FXRQXYSJYZPGJZ-UHFFFAOYSA-N 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- DTGDMPJDZKDHEP-UHFFFAOYSA-N 4-ethenylbicyclo[4.2.0]octa-1(6),2,4-triene Chemical compound C=CC1=CC=C2CCC2=C1 DTGDMPJDZKDHEP-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229920000359 diblock copolymer Polymers 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003759 ester based solvent Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000005453 ketone based solvent Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000004292 cyclic ethers Chemical group 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229940116333 ethyl lactate Drugs 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N isobutyl acetate Chemical compound CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000004094 surface-active agent Substances 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
- 238000001039 wet etching Methods 0.000 description 2
- CORMBJOFDGICKF-UHFFFAOYSA-N 1,3,5-trimethoxy 2-vinyl benzene Natural products COC1=CC(OC)=C(C=C)C(OC)=C1 CORMBJOFDGICKF-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- VKSWWACDZPRJAP-UHFFFAOYSA-N 1,3-dioxepan-2-one Chemical compound O=C1OCCCCO1 VKSWWACDZPRJAP-UHFFFAOYSA-N 0.000 description 1
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical compound C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 description 1
- HMDQPBSDHHTRNI-UHFFFAOYSA-N 1-(chloromethyl)-3-ethenylbenzene Chemical compound ClCC1=CC=CC(C=C)=C1 HMDQPBSDHHTRNI-UHFFFAOYSA-N 0.000 description 1
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- KWHSBYQFELZKKS-UHFFFAOYSA-N 1-ethenyl-4-iodobenzene Chemical compound IC1=CC=C(C=C)C=C1 KWHSBYQFELZKKS-UHFFFAOYSA-N 0.000 description 1
- YFZHODLXYNDBSM-UHFFFAOYSA-N 1-ethenyl-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(C=C)C=C1 YFZHODLXYNDBSM-UHFFFAOYSA-N 0.000 description 1
- UJEGHEMJVNQWOJ-UHFFFAOYSA-N 1-heptoxyheptane Chemical compound CCCCCCCOCCCCCCC UJEGHEMJVNQWOJ-UHFFFAOYSA-N 0.000 description 1
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 1
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 description 1
- MGMSZKIPUNOMCS-UHFFFAOYSA-N 2-(2-ethenoxyethoxy)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC=C MGMSZKIPUNOMCS-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- XXSPGBOGLXKMDU-UHFFFAOYSA-N 2-bromo-2-methylpropanoic acid Chemical compound CC(C)(Br)C(O)=O XXSPGBOGLXKMDU-UHFFFAOYSA-N 0.000 description 1
- PDELBHCVXBSVPJ-UHFFFAOYSA-N 2-ethenyl-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=C(C=C)C(C)=C1 PDELBHCVXBSVPJ-UHFFFAOYSA-N 0.000 description 1
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 1
- 125000006321 2-propynyl amino group Chemical group [H]C#CC([H])([H])N([H])* 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- PKNKULBDCRZSBT-UHFFFAOYSA-N 3,4,5-trimethylnonan-2-one Chemical compound CCCCC(C)C(C)C(C)C(C)=O PKNKULBDCRZSBT-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- SNTUCKQYWGHZPK-UHFFFAOYSA-N 4-ethenylbenzonitrile Chemical compound C=CC1=CC=C(C#N)C=C1 SNTUCKQYWGHZPK-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 101100215341 Arabidopsis thaliana ACT12 gene Proteins 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- JABXMSSGPHGCII-UHFFFAOYSA-N acetic acid;propane-1,2-diol Chemical compound CC(O)=O.CC(O)CO JABXMSSGPHGCII-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- UOCJDOLVGGIYIQ-PBFPGSCMSA-N cefatrizine Chemical group S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)[C@H](N)C=2C=CC(O)=CC=2)CC=1CSC=1C=NNN=1 UOCJDOLVGGIYIQ-PBFPGSCMSA-N 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000003950 cyclic amides Chemical class 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- IIRFCWANHMSDCG-UHFFFAOYSA-N cyclooctanone Chemical compound O=C1CCCCCCC1 IIRFCWANHMSDCG-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 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
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- XVEOUOTUJBYHNL-UHFFFAOYSA-N heptane-2,4-diol Chemical compound CCCC(O)CC(C)O XVEOUOTUJBYHNL-UHFFFAOYSA-N 0.000 description 1
- OHMBHFSEKCCCBW-UHFFFAOYSA-N hexane-2,5-diol Chemical compound CC(O)CCC(C)O OHMBHFSEKCCCBW-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- QJQAMHYHNCADNR-UHFFFAOYSA-N n-methylpropanamide Chemical compound CCC(=O)NC QJQAMHYHNCADNR-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- GTCCGKPBSJZVRZ-UHFFFAOYSA-N pentane-2,4-diol Chemical compound CC(O)CC(C)O GTCCGKPBSJZVRZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000001955 polymer synthesis method Methods 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 229920003046 tetrablock copolymer Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/026—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising acrylic acid, methacrylic acid or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
- C09D201/08—Carboxyl groups
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
- H01L21/3081—Chemical or electrical treatment, e.g. electrolytic etching using masks characterised by their composition, e.g. multilayer masks, materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
Definitions
- the present invention relates to a film forming composition, a film forming method, and a self-organized lithography process.
- pattern miniaturization is required in the pattern formation process.
- a self-organized lithography process using a so-called self-organized phase separation structure that spontaneously forms an ordered pattern has been proposed.
- a method is known in which a block copolymer composed of blocks having different properties is used to form an ultrafine pattern by self-organization (Japanese Patent Laid-Open No. 2008-149447, Special Table 2002). No. -5,728 and Japanese Patent Application Laid-Open No. 2003-218383).
- a method of forming a fine pattern by self-organizing a composition containing a plurality of polymers having different properties US Patent Application Publication No. 2009/0214823 and JP 2010-58403 A). See the official gazette). According to these methods, by annealing a film containing the polymer, polymer structures having the same properties tend to gather together, so that a pattern can be formed in a self-aligning manner.
- phase separation due to self-organization may occur effectively by forming a film containing a component such as a polymer to be self-assembled on a base. It has been.
- various studies have been made on this underlayer, and it is said that various phase separation structures can be formed by appropriately controlling the surface free energy of the underlayer when the block copolymer is self-assembled ( (See JP2008-36491 and JP2012-174984).
- the invention made in order to solve the above problems includes a first repeating unit containing a crosslinkable group (hereinafter also referred to as “repeating unit (I)”) and a second repeating unit which is a repeating unit different from the repeating unit (I). (Hereinafter also referred to as “repeat unit (II)”), and a third repeat unit (hereinafter also referred to as “repeat unit (III)”) that is different from the repeat unit (I) and has a higher polarity than the repeat unit (II).
- a film comprising a polymer having a unit (X) ”(hereinafter also referred to as“ [A] polymer ”) and a solvent (hereinafter also referred to as“ [B] solvent ”). It is a composition for formation.
- Another invention made in order to solve the above-mentioned problems is a step of applying the film-forming composition to one surface side of the substrate and a step of heating the coating film formed by the coating step. Is a film forming method.
- Still another invention made in order to solve the above-mentioned problems is to heat the coating film formed by the step of coating the film-forming composition on one surface side of the substrate and the coating step.
- a step of phase-separating the polymer film, a step of removing one phase of the phase-separated block copolymer film, and a step of etching directly or indirectly using the resist pattern formed by the removal step A self-organized lithography process.
- self-organization refers to a phenomenon in which an organization or structure is spontaneously constructed without being caused only by control from an external factor.
- the “main chain” in the present invention refers to a polymer chain containing a bond including all the repeating units (I), (II) and (III).
- the film forming composition, the film forming method, and the self-assembled lithography process of the present invention it is possible to form a phase separation structure by self-assembly well and to form a pattern with few residues and defects. Therefore, they can be suitably used in pattern formation processes in the manufacture of various electronic devices such as semiconductor devices and liquid crystal devices that are required to be further miniaturized.
- the film-forming composition is applied to one surface side of a substrate to form a film having excellent heat resistance, substrate adhesion, etc., especially the formation of a base for a self-assembled film in a self-organized lithography process. It is a composition suitably used for.
- the film-forming composition contains a [A] polymer and a [B] solvent.
- the film-forming composition may contain an optional component as long as the effects of the present invention are not impaired. Hereinafter, each component will be described.
- the polymer has a repeating unit (I), a repeating unit (II) and a repeating unit (III), and interacts with Si—OH, Si—H or Si—N at at least one terminal of the main chain.
- the structural unit (X) includes a group (X).
- the polymer may have repeating units (I) to (III) randomly or in blocks. That is, the [A] polymer may be a random copolymer or a block copolymer, but a random copolymer is preferable from the viewpoint of further reducing pattern residues and defects.
- the polymer may have one or more repeating units (I) to (III).
- the film-forming composition contains a repeating unit (I) to (III) and a [A] polymer having a structural unit (X) at least at one end of the main chain, thereby self-organizing.
- a phase separation structure can be formed satisfactorily and a pattern with few residues and defects can be formed.
- the reason why the film-forming composition has the above-described configuration and exhibits the above-mentioned effects is not necessarily clear, but can be inferred as follows, for example. That is, the [A] polymer has a repeating unit (I) containing a crosslinkable group and a structural unit containing a group (X) interacting with Si—OH, Si—H or Si—N at the terminal ( X).
- the coated film-forming composition has the structural unit (X)
- the [A] polymer is formed on the surface of the substrate due to the interaction with Si—OH, Si—H or Si—N of the substrate. It becomes possible to exist at high density.
- membrane density of polymer chains can be formed by presence of a repeating unit (I).
- a repeating unit (I) it is possible to increase the effect of a film that covers or modifies the substrate surface such as a base film on the self-assembled film.
- the repeating units (I) to (III) and the structural unit (X) will be described.
- the repeating unit (I) is a repeating unit containing a crosslinkable group.
- the “crosslinkable group” refers to a group that forms a crosslinked structure by a reaction under heating conditions, irradiation conditions of active energy rays, acidic conditions, and the like.
- crosslinkable group examples include a carbon-carbon double bond-containing group such as vinyl group, vinyloxy group, allyl group, (meth) acryloyl group, styryl group; Carbon-carbon triple bond-containing groups such as ethynyl group, propargyl group, propargyloxy group, propargylamino group; Cyclic ether groups such as oxiranyl group, oxiranyloxy group, oxetanyl group, oxetanyloxy group; An aryl group condensed with a cyclobutane ring such as a phenyl group condensed with a cyclobutane ring, a naphthyl group condensed with a cyclobutane ring; An aryl group to which a phenolic hydroxyl group protected with an acid group or a thermally dissociable group such as an acetoxyphenyl group and a t-butoxyphenyl group; An aryl
- the aryl groups condensed with the cyclobutane ring form a covalent bond under heating conditions.
- “Acid group” refers to a group obtained by removing OH from an acid and protecting it by replacing a hydrogen atom of a phenolic hydroxyl group or a methylol group.
- the “thermally dissociable group” refers to a group that substitutes a hydrogen atom of a phenolic hydroxyl group, a methylol group, or a sulfanylmethyl group, and dissociates when heated.
- Examples of the acid group in the aryl group to which a protected phenolic hydroxyl group, methylol group, or sulfanylmethyl group is bonded include formyl group, acetyl group, propionyl group, butyryl group, and benzoyl group.
- thermally dissociable group in the aryl group to which the protected phenolic hydroxyl group is bonded examples include tertiary alkyl groups such as t-butyl group and t-amyl group.
- thermally dissociable group in the aryl group to which a protected methylol group or sulfanylmethyl group is bonded examples include alkyl groups such as a methyl group, an ethyl group, and a propyl group.
- a crosslinkable group includes a carbon-carbon double bond-containing group, an aryl group condensed with a cyclobutane ring, and a phenolic hydroxyl group or a methylol group protected with an acid group or a heat dissociable group.
- An aryl group is preferable, a carbon-carbon double bond-containing group, an aryl group condensed with a cyclobutane ring, and a phenolic hydroxyl group protected with an acid group or a heat dissociable group are more preferable, and a vinyloxy group, an allyl group, or a cyclobutane ring is more preferable. More preferred are a fused ring phenyl group and a t-butoxyphenyl group.
- repeating unit (I) examples include a repeating unit derived from a vinyl compound having a crosslinkable group and a repeating unit derived from a (meth) acrylic compound having a crosslinkable group.
- the repeating unit (I) includes a repeating unit derived from a (meth) acrylic compound having a carbon-carbon double bond-containing group, a repeating unit derived from a vinyl compound having an aryl group fused with a cyclobutane ring, and an acid group or Preferred is a repeating unit derived from a vinyl compound having a phenolic hydroxyl group protected by a heat dissociable group, and a repeating unit derived from 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, allyl (meth) acrylate More preferred are repeating units derived from 1, repeating units derived from 4-vinylbenzocyclobutene and repeating units derived from t-butoxystyrene.
- the lower limit of the content ratio of the repeating unit (I) is preferably 0.1 mol%, more preferably 1 mol%, still more preferably 3 mol%, based on all repeating units constituting the [A] polymer. 4 mol% is particularly preferred.
- As an upper limit of the said content rate 30 mol% is preferable, 15 mol% is more preferable, 10 mol% is further more preferable, and 8 mol% is especially preferable.
- the repeating unit (II) and the repeating unit (III) are different repeating units from the repeating unit (I).
- the repeating unit (III) is more polar than the repeating unit (II).
- repeating unit (II) and the repeating unit (III) include a repeating unit derived from substituted or unsubstituted styrene, a repeating unit derived from (meth) acrylate ester, and a repeating unit containing a Si—O bond in the main chain. , Repeating units derived from hydroxycarboxylic acid, repeating units derived from alkylene carbonate, repeating units derived from alkylene glycol, and the like.
- the repeating unit derived from hydroxycarboxylic acid is a repeating unit containing —COO— in the main chain.
- the repeating unit derived from the alkylene carbonate is a repeating unit having a —OCOO— group and an alkylene group in the main chain.
- the repeating unit derived from polyalkylene glycol is a repeating unit containing a polyalkylene glycol chain in the main chain.
- styrene As a monomer that gives a repeating unit derived from substituted or unsubstituted styrene, for example, styrene; ⁇ -methylstyrene; o-, m- or p-methylstyrene, pt-butylstyrene, 2,4,6-trimethylstyrene, p-methoxystyrene, pt-butoxystyrene, o-, m- or electron-donating group-substituted styrene such as p-vinylstyrene; Electron withdrawing properties such as o-, m- or p-hydroxystyrene, m- or p-chloromethylstyrene, p-chlorostyrene, p-bromostyrene, p-iodostyrene, p-nitrostyrene, p-cyanostyrene Examples thereof
- Monomers that give repeating units derived from (meth) acrylic acid esters include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, t-butyl (meth) acrylate, (meth) acrylic acid 2- (Meth) acrylic acid alkyl esters such as ethylhexyl; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 1-methylcyclopentyl (meth) acrylate, 2-ethyladamantyl (meth) acrylate, 2- (adamantan-1-yl) propyl (meth) acrylate, etc.
- (Meth) acrylic acid alicyclic hydrocarbon group ester (Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and naphthyl (meth) acrylate; Examples include (meth) acrylic acid-substituted alkyl esters such as 2-hydroxyethyl (meth) acrylate, 3-hydroxyadamantyl (meth) acrylate, and 3-glycidylpropyl (meth) acrylate.
- Examples of the repeating unit containing a Si—O bond in the main chain include a polydimethylsiloxane chain and a polymethylphenylsiloxane chain.
- Examples of the monomer that gives a repeating unit derived from hydroxycarboxylic acid include glycolic acid, lactic acid, 3-hydroxypropanoic acid, 4-hydroxybutanoic acid, esters of these acids, and lactides of these acids and esters. It is done.
- Examples of the monomer that gives a repeating unit derived from alkylene carbonate include ethylene carbonate, trimethylene carbonate, and tetramethylene carbonate.
- Examples of monomers that give repeating units derived from alkylene glycol include ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, and 2-methyl-2,4-pentanediol. 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and the like.
- repeating unit (II) a repeating unit having an aromatic ring is preferable, and a repeating unit derived from substituted or unsubstituted styrene is more preferable.
- repeating unit (III) a repeating unit derived from (meth) acrylic acid ester, a repeating unit containing a Si—O bond in the main chain, a repeating unit derived from hydroxycarboxylic acid, and a repeating unit derived from alkylene carbonate are preferable. .
- the lower limit of the content ratio of the repeating unit (II) is preferably 20 mol%, more preferably 40 mol%, still more preferably 60 mol%, based on all repeating units constituting the [A] polymer.
- As an upper limit of the said content rate 90 mol% is preferable, 80 mol% is more preferable, and 75 mol% is further more preferable.
- the lower limit of the content ratio of the repeating unit (III) is preferably 5 mol%, more preferably 10 mol%, further preferably 20 mol%, based on all repeating units constituting the [A] polymer.
- As an upper limit of the said content rate 70 mol% is preferable, 50 mol% is more preferable, and 30 mol% is further more preferable.
- the structural unit (X) is a structural unit including a group (X) present at at least one end of the main chain.
- the group (X) is a group that interacts with Si—OH, Si—H, or Si—N.
- “Interacting” with Si—OH, Si—H or Si—N means, for example, forming a chemical bond between them.
- “Chemical bond” is a concept including electrostatic attraction and hydrogen bond between molecules in addition to covalent bond, ionic bond, metal bond and coordination bond, preferably covalent bond, ionic bond, metal bond or coordination. It is a bond.
- Examples of the group (X) include a hydroxy group, a carboxy group, an amino group, and a sulfanyl group. Among these, at least one of a hydroxy group and a carboxy group is preferable, and a hydroxy group is more preferable.
- Examples of the structural unit (X) include a structural unit derived from a (meth) acrylic compound having a group (X), a structural unit derived from a vinyl compound having a group (X), and the like.
- a structural unit derived from a (meth) acrylic compound having a hydroxy group and a structural unit derived from a vinyl compound having a hydroxy group are preferable, and a structure derived from a (meth) acrylic compound having a hydroxy group More preferred are units, more preferred are repeating units derived from hydroxyalkyl (meth) acrylate, and particularly preferred are repeating units derived from 2-hydroxyethyl (meth) acrylate.
- the structural unit (X) may be present only at one end of the main chain or at both ends of the main chain. However, from the viewpoint of ease of synthesis of the polymer [A], It is preferable that it exists only at one terminal.
- [A] Polymer Synthesis Method] include, for example, monomers that give repeating units (I) to (III), amine compounds such as copper (II) bromide and tris [(2-dimethylamino) ethyl] amine, anisole, etc. And a halogen compound that gives structural unit (X) such as 2-hydroxyethyl 2-bromoisobutyrate is added to the solvent, and the repeating units (I) to (III) are added by atom transfer radical polymerization. And a polymer having the structural unit (X) at one end of the main chain can be synthesized.
- the upper limit of the Mw is preferably 50,000, more preferably 20,000, and still more preferably 10,000.
- the lower limit of Mn of the polymer is preferably 1,000, more preferably 3,000, and still more preferably 5,000.
- the upper limit of Mw is preferably 40,000, more preferably 15,000, and still more preferably 8,000.
- the upper limit of Mw / Mn of the polymer is preferably 5, more preferably 3, more preferably 2, more preferably 1.5, and still more preferably 1.2. As a minimum of the above-mentioned Mw / Mn, it is usually 1 and 1.1 is more preferred.
- the solvent can be used without any particular limitation as long as it is a solvent capable of dissolving or dispersing at least the [A] polymer and optionally contained optional components.
- Examples of the solvent include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, hydrocarbon solvents, and the like.
- the alcohol solvent examples include aliphatic monoalcohol solvents having 1 to 18 carbon atoms such as 4-methyl-2-pentanol and n-hexanol; An alicyclic monoalcohol solvent having 3 to 18 carbon atoms such as cyclohexanol; A polyhydric alcohol solvent having 2 to 18 carbon atoms such as 1,2-propylene glycol; Examples thereof include polyhydric alcohol partial ether solvents having 3 to 19 carbon atoms such as propylene glycol monomethyl ether.
- ether solvent examples include dialkyl ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, and diheptyl ether; Cyclic ether solvents such as tetrahydrofuran and tetrahydropyran; Aromatic ring-containing ether solvents such as diphenyl ether and anisole (methylphenyl ether) are exemplified.
- dialkyl ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, and diheptyl ether
- Cyclic ether solvents such as tetrahydrofuran and tetrahydropyran
- Aromatic ring-containing ether solvents such as diphenyl ether and anisole (methylphenyl ether)
- ketone solvent examples include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, 2-heptanone (methyl-n-pentyl ketone), ethyl-n- Chain ketone solvents such as butyl ketone, methyl-n-hexyl ketone, di-iso-butyl ketone, trimethylnonanone; Cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone; Examples include 2,4-pentanedione, acetonylacetone, acetophenone, and the like.
- amide solvent examples include cyclic amide solvents such as N, N′-dimethylimidazolidinone and N-methylpyrrolidone; Examples thereof include chain amide solvents such as N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, and N-methylpropionamide.
- cyclic amide solvents such as N, N′-dimethylimidazolidinone and N-methylpyrrolidone
- chain amide solvents such as N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, and N-methylpropionamide.
- ester solvent examples include monocarboxylic acid ester solvents such as n-butyl acetate and ethyl lactate; Polyhydric alcohol carboxylate solvents such as propylene glycol acetate; Polyhydric alcohol partial ether carboxylate solvents such as propylene glycol monomethyl ether acetate; Lactone solvents such as ⁇ -butyrolactone and ⁇ -valerolactone; Polycarboxylic acid diester solvents such as diethyl oxalate; Examples thereof include carbonate solvents such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate.
- monocarboxylic acid ester solvents such as n-butyl acetate and ethyl lactate
- Polyhydric alcohol carboxylate solvents such as propylene glycol acetate
- Polyhydric alcohol partial ether carboxylate solvents such as propylene glycol monomethyl ether acetate
- Lactone solvents such as ⁇ -buty
- hydrocarbon solvent examples include aliphatic hydrocarbon solvents having 5 to 12 carbon atoms such as n-pentane and n-hexane; Examples thereof include aromatic hydrocarbon solvents having 6 to 16 carbon atoms such as toluene and xylene.
- ester solvents are preferable, polyhydric alcohol partial ether carboxylate solvents are more preferable, polyhydric alcohol partial ether acetate solvents are more preferable, and propylene glycol monomethyl ether acetate is particularly preferable.
- the film-forming composition may contain one or more [B] solvents.
- ⁇ Optional component> examples of optional components that may be contained in the film-forming composition include a surfactant.
- the film-forming composition can further improve the applicability to a substrate or the like by containing a surfactant.
- the film-forming composition for example, the [A] polymer, the [B] solvent, and optional components as necessary are mixed at a predetermined ratio.
- the obtained mixture has pores of about 0.45 ⁇ m. It can be prepared by filtering with a high density polyethylene filter or the like.
- the lower limit of the solid content concentration of the film-forming composition is preferably 0.01% by mass, more preferably 0.1% by mass, still more preferably 0.5% by mass, and particularly preferably 1.0% by mass.
- the upper limit of the solid content concentration is preferably 30% by mass, more preferably 10% by mass, further preferably 5% by mass, and particularly preferably 2% by mass.
- the film-forming composition is preferably applied to the upper surface side of a substrate having Si—OH, Si—H and / or Si—N as a surface layer.
- the film-forming composition is preferably used for forming a base of a self-assembled film containing a block copolymer having a block containing the repeating unit (II) and a block containing the repeating unit (III).
- the film forming method includes a step of coating the film forming composition on one surface side of the substrate and a step of heating the coating film formed by the coating step.
- the coating step and the heating step can be performed in the same manner as the coating step (1) and the heating step in the self-organized lithography process described later, respectively.
- the substrate on which the film-forming composition is applied examples include a silicon substrate such as a silicon wafer, a metal substrate on which a siloxane film is formed, and the like. These substrates usually have Si—OH, Si—H or Si—N on their surface layers by the action of oxygen, water, etc. in the air. These substrates can also have Si—OH, Si—H or Si—N on the surface layer by surface treatment with an acid such as sulfuric acid.
- the lower limit of the average thickness of the film obtained by the film forming method is preferably 1 nm, more preferably 2 nm, and further preferably 3 nm.
- the upper limit of the average thickness of the film is preferably 2,000 nm, more preferably 100 nm, and still more preferably 20 nm.
- the self-assembled lithography process includes a step of coating the film-forming composition on one surface side of the substrate (hereinafter also referred to as “coating step (1)”) and the coating step (1).
- a step of heating the coating film formed by the above hereinafter, also referred to as “heating step”
- a step of coating the composition to be coated hereinafter also referred to as “coating step (2)”
- phase phase-separating the block copolymer film formed by the coating step (2)
- phase-separation step a step of removing one phase of the phase-separated block copolymer film (hereinafter also referred to as “removal step”), and a resist pattern formed by the removal step directly or Indirectly used and etching process (hereinafter “ It provided with the also referred to) and the etching process ".
- the self-organized lithography process includes a step of forming a pre-pattern on the surface opposite to the base substrate formed by the heating step (hereinafter referred to as the following step) after the heating step and before the coating step (2). , Also referred to as “pre-pattern forming step”), and in this case, it may further include a step of removing the pre-pattern simultaneously with, before or after the removing step.
- pre-pattern forming step also referred to as “pre-pattern forming step”
- the film-forming composition is applied to one surface side of the substrate.
- Examples of the substrate 101 include a silicon substrate such as a silicon wafer and a metal substrate on which a siloxane film is formed. These substrates usually have Si—OH, Si—H or Si—N on their surface layers by the action of oxygen, water, etc. in the air. These substrates can also have Si—OH, Si—H or Si—N on the surface layer by surface treatment with an acid such as sulfuric acid.
- the coating method of the film forming composition is not particularly limited, and examples thereof include a spin coating method. Thereby, a coating film is formed.
- Examples of the method for heating the coating film include a method using an oven, a hot plate, and the like.
- 100 degreeC is preferable and 150 degreeC is more preferable.
- 400 degreeC is preferable and 300 degreeC is more preferable.
- the lower limit of the heating time is preferably 10 seconds, and more preferably 60 seconds.
- the upper limit of the time is preferably 600 seconds, and more preferably 300 seconds.
- the atmosphere for heating is not particularly limited, and may be an air atmosphere or an inert gas atmosphere such as nitrogen gas. Further, after heating the coating film, it may be washed with a solvent such as propylene glycol monomethyl ether acetate (PGMEA).
- PGMEA propylene glycol monomethyl ether acetate
- the lower limit of the average thickness of the substrate 102 is preferably 1 nm, more preferably 2 nm, and even more preferably 3 nm.
- the upper limit of the average thickness is preferably 2,000 nm, more preferably 100 nm, and even more preferably 20 nm.
- a prepattern 103 is formed on the base 102.
- the phase separation during the formation of the self-assembled film 105 is further controlled, and a phase separation structure by self-assembly can be formed better. That is, among the components that form the self-assembled film 105, components that have high affinity with the side surface of the prepattern 103 form a phase along the prepattern 103, and components that have low affinity from the prepattern 103. Form a phase at a remote location. Thereby, the phase separation structure by self-organization can be formed more satisfactorily.
- phase separation structure to be formed can be finely controlled by the material, length, thickness, shape and the like of the pre-pattern 103.
- the pre-pattern 103 can be partially modified by partial exposure, laser abrasion, or the like.
- the pre-pattern 103 can be appropriately selected according to the pattern to be finally formed. For example, a line and space pattern, a hole pattern, a pillar pattern, or the like can be used.
- a method for forming the prepattern 103 a method similar to a known resist pattern forming method can be used.
- the conventional composition for resist film formation can be used.
- a specific method for forming the pre-pattern 103 for example, a chemically amplified resist composition such as “ARX2928JN” manufactured by JSR Co., Ltd. is used and applied onto the base 102 to form a resist film. Next, exposure is performed by irradiating a desired region of the resist film with radiation through a mask having a specific pattern.
- Examples of radiation include far ultraviolet rays such as ArF excimer laser light and KrF excimer laser light, electromagnetic waves such as ultraviolet rays and X-rays, and charged particle beams such as electron beams. Among these, far ultraviolet rays are preferable, ArF excimer laser light and KrF excimer laser light are more preferable, and ArF excimer laser light is more preferable.
- post-exposure baking PEB is performed, and development is performed using a developer such as an alkali developer or an organic solvent, so that a desired pre-pattern 103 can be formed.
- the surface of the pre-pattern 103 may be subjected to a hydrophilic treatment.
- a hydrogenation treatment by exposing to hydrogen plasma for a certain period of time can be cited.
- the Si—OH on the surface is increased, the interaction with the [A] polymer is strengthened, and the above self-assembly can be promoted.
- the pattern forming composition usually contains a block copolymer and a solvent.
- the block copolymer any polymer having two or more blocks can be used, and it may be a diblock copolymer, a triblock copolymer, or a tetrablock copolymer.
- a diblock copolymer is preferable from the viewpoint that a phase separation structure by self-organization can be formed more satisfactorily.
- the block copolymer is the [A] polymer in the above-mentioned film-forming composition.
- a block copolymer having a block to be contained is more preferable.
- the coating method of the composition is not particularly limited, and examples thereof include a spin coating method.
- Phase separation process In this step, the block copolymer film formed by the coating step is phase separated. As a result, a self-assembled film 105 having a phase separation structure is formed as shown in FIG. Examples of the phase separation method include an annealing method.
- An example of the annealing method is an oven, a hot plate, or the like.
- 80 degreeC is preferable and 150 degreeC is more preferable.
- 400 degreeC is preferable and 300 degreeC is more preferable.
- the lower limit of the annealing time is preferably 10 seconds, and more preferably 30 seconds.
- the upper limit of the time is preferably 120 minutes, and more preferably 10 minutes.
- the lower limit of the average thickness of the self-assembled film 105 is preferably 0.1 nm, and more preferably 0.5 nm.
- the upper limit of the average thickness is preferably 500 nm, and more preferably 100 nm.
- one phase of the phase-separated block copolymer film is removed.
- a part of the block phase 105a in the phase separation structure of the self-assembled film 105 is removed.
- the block phase 105a can be removed by etching using the difference in the etching rate of the phases separated by self-organization.
- FIG. 5 shows a state after the block phase 105a in the phase separation structure and the pre-pattern 103 are removed as will be described later. In addition, you may irradiate a radiation before the said etching process as needed.
- the block phase 105a is a polymethyl methacrylate block phase
- radiation of 254 nm can be used. Since the polymethyl methacrylate block phase is decomposed by the radiation irradiation, etching becomes easier.
- RIE reactive ion etching
- chemical dry etching or chemical wet etching etching or chemical wet etching
- sputter etching or ion beam etching or the like.
- physical etching are mentioned.
- RIE reactive ion etching
- Chemical dry etching using CF 4 , O 2 gas, etc. etching of liquid such as organic solvent, hydrofluoric acid, etc.
- Chemical wet etching (wet development) using a solution is more preferable.
- organic solvent examples include alkanes such as n-pentane, n-hexane, and n-heptane, cycloalkanes such as cyclohexane, cycloheptane, and cyclooctane, ethyl acetate, n-butyl acetate, i-butyl acetate, and methyl propionate.
- alkanes such as n-pentane, n-hexane, and n-heptane
- cycloalkanes such as cyclohexane, cycloheptane, and cyclooctane
- ethyl acetate n-butyl acetate, i-butyl acetate
- methyl propionate examples of the organic solvent
- Saturated carboxylic acid esters acetone, 2-butanone, 4-methyl-2-pentanone, ketones such as 2-heptanone
- Pre-pattern removal process This step is a step of removing the pre-pattern 103 as shown in FIGS. By removing the pre-pattern 103, a finer and more complicated pattern can be formed.
- the method of removing the pre-pattern 103 the above description of the method of removing a part of the block phases 105a in the phase separation structure can be applied. Moreover, this process may be performed simultaneously with the said removal process, and may be performed before or after a removal process.
- the resist pattern formed by the removal step is directly or indirectly used for etching.
- the base and the substrate are etched using a resist pattern composed of the block phase 105b which is a part of the block phase of the remaining phase separation film as a mask.
- the phase used as a mask is removed from the substrate by dissolution treatment or the like, and a finally patterned substrate (pattern) can be obtained.
- the etching method a method similar to that exemplified in the removing step can be used, and the etching gas and the etching solution can be appropriately selected depending on the material of the base and the substrate.
- a mixed gas of chlorofluorocarbon gas and SF 4 can be used.
- the pattern obtained by the pattern forming method is suitably used for semiconductor elements and the like, and the semiconductor elements are widely used for LEDs, solar cells and the like.
- Mw and Mn of the polymer are measured by gel permeation chromatography (GPC) using GPC columns (two "G2000HXL", one "G3000HXL” and one "G4000HXL” from Tosoh Corporation) under the following conditions. did.
- Eluent Tetrahydrofuran (Wako Pure Chemical Industries)
- Flow rate 1.0 mL / min
- Sample concentration 1.0% by mass
- Sample injection volume 100 ⁇ L
- Detector Differential refractometer Standard material: Monodisperse polystyrene
- This polymer (a-1) had Mw of 5,600, Mn of 4,600, and Mw / Mn of 1.22. Further, as a result of 1 H-NMR analysis, the content ratio of the structural unit derived from styrene, the structural unit derived from methyl methacrylate, and the structural unit derived from 2-hydroxyethyl methacrylate was 80 mol%, 15 mol%, and 5 mol%, respectively. there were.
- This polymer (a-2) had Mw of 8,800, Mn of 6,900, and Mw / Mn of 1.23.
- the content ratios of structural units derived from styrene and structural units derived from methyl methacrylate were 70 mol% and 30 mol%, respectively.
- the obtained polymerization solution was filtered through Celite to remove the copper complex, and washing with 500 g of ultrapure water was repeated three times. After collecting the organic layer, it was concentrated, and the resulting concentrate, to which 50 g of THF was added, was added to 1,000 g of a methanol / ultra pure water (mass ratio 5/5) mixture to precipitate the polymer. It was. The obtained solid was recovered with a Buchner funnel and washed with 50 g of methanol. The obtained solid was dried under reduced pressure to obtain 11.5 g of a white polymer (A-1).
- This polymer (A-1) had Mw of 7,300, Mn of 6,400, and Mw / Mn of 1.14. Further, as a result of 1 H-NMR analysis, the content ratio of the structural unit derived from styrene, the structural unit derived from methyl methacrylate, and the structural unit derived from 2- (2-vinyloxyethoxy) ethyl methacrylate was 70 mol%. 25 mol% and 5 mol%.
- the obtained polymerization solution was filtered through Celite to remove the copper complex, and washing with 500 g of ultrapure water was repeated three times. After collecting the organic layer, it was concentrated, and the resulting concentrate, to which 50 g of THF was added, was added to 1,000 g of a methanol / ultra pure water (mass ratio 5/5) mixture to precipitate the polymer. It was. The obtained solid was recovered with a Buchner funnel and washed with 50 g of methanol. The obtained solid was dried under reduced pressure to obtain 11.5 g of a white polymer (A-2).
- This polymer (A-2) had Mw of 7,800, Mn of 6,900, and Mw / Mn of 1.13. Further, as a result of 1 H-NMR analysis, the content ratio of the structural unit derived from styrene, the structural unit derived from methyl methacrylate, and the structural unit derived from 4-vinylbenzocyclobutene was 70 mol%, 25 mol%, and 5 mol%, respectively. Met.
- This resin (A-3) had Mw: 7000, Mn: 6200, and Mw / Mn: 1.13.
- styrene was found to be 70 mol%, methyl methacrylate 25 mol%, and allyl methacrylate 5 mol%.
- This resin (A-4) had Mw: 7000, Mn: 6000, and Mw / Mn: 1.17.
- the content of styrene was 70 mol%, methyl methacrylate 25 mol%, and tert-butoxystyrene 5 mol%.
- reaction was continued for 120 minutes. Thereafter, 1 mL of methanol as a terminal terminator was injected to terminate the polymerization terminal. The reaction solution was warmed to room temperature, and the resulting reaction solution was concentrated and replaced with methyl isobutyl ketone (MIBK). Thereafter, 1,000 g of a 2% by mass aqueous solution of oxalic acid was injected and stirred, and after standing, the lower aqueous layer was removed. This operation was repeated three times to remove the Li salt. Thereafter, 1,000 g of ultrapure water was injected and stirred, and the lower aqueous layer was removed. This operation was repeated three times, and oxalic acid was removed.
- MIBK methyl isobutyl ketone
- This block copolymer (B-1) had Mw of 58,600, Mn of 57,000, and Mw / Mn of 1.03.
- the block copolymer (A-1) had a content ratio of the repeating unit derived from styrene and the repeating unit derived from methyl methacrylate of 50.0% by mass (50. 0 mol%) and 50.0 mass% (50.0 mol%).
- the block copolymer (B-1) is a diblock copolymer.
- Comparative Example 1 was the same as Comparative Example 1 except that instead of the polymer (a-1), any one of the polymers (a-2) and (A-1) to (A-4) was used. Thus, film-forming compositions (CA-2) and (A-1) to (A-4) were prepared.
- Each film-forming composition prepared above was spin-coated at 1,500 rpm on a silicon substrate using a track (“TEL DSA ACT12” manufactured by Tokyo Electron Ltd.), and baked at 250 ° C. for 180 seconds. This substrate was washed with PGMEA to remove the unreacted film forming composition. The average thickness of the coating film formed on the silicon substrate was about 5 nm from the result of measuring the thickness of the ellipsometer.
- the pattern-forming composition (S-1) prepared above was spin-coated at 1,500 rpm on the substrate on which the coating film (underlying) was formed to form a coating film, And phase separation by annealing at 220 ° C. for 60 seconds.
- a substrate having a phase-separated coating film was irradiated with 172 nm radiation at an intensity of 300 mJ / cm 2 and then immersed in a solution of 2-propanol (IPA) to form a phase composed of a poly (methyl methacrylate) block.
- IPA 2-propanol
- a line and space pattern was formed by dissolving and removing.
- Table 1 below shows the contact angle, surface tension (dyn / cm), number of residues / number of defects, and pitch size (nm) when each of the film-forming compositions prepared above is used.
- the film forming composition of the example As is apparent from the results in Table 3, according to the film forming composition of the example, a phase separation structure by self-organization can be satisfactorily formed, and a pattern with few residues and defects can be formed.
- the film-forming compositions of the examples can significantly reduce the number of residues and the number of defects as compared with the film-forming compositions of the comparative examples.
- the film forming composition, the film forming method, and the self-assembled lithography process of the present invention it is possible to form a phase separation structure by self-assembly well and to form a pattern with few residues and defects. Therefore, they can be suitably used in pattern formation processes in the manufacture of various electronic devices such as semiconductor devices and liquid crystal devices that are required to be further miniaturized.
- Substrate 101 Substrate 102 Base 103 Pre-pattern 104 Coating film 105 Self-assembled films 105a and 105b Block phase
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Structural Engineering (AREA)
- Architecture (AREA)
- Inorganic Chemistry (AREA)
- Materials For Photolithography (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Paints Or Removers (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
自己組織化リソグラフィープロセスにおいては、未だ自己組織化による相分離構造を良好に形成させ、また、エッチング不良によって後に残る不溶物や残りかすである残渣、及び相分離不良によって得られる不良パターンである欠陥が少ないパターンを形成させるまでには至っていない。
また基板をカバーしたり修飾したりする材料においても、簡便性、耐熱性などの性能が未だ不十分で検討が進められている。
本発明は、以上のような事情に基づいてなされたものであり、その目的は、微細なパターン形成に好適に用いられる膜形成用組成物を提供することにある。具体的な一例としては、自己組織化による相分離構造を良好に形成させ、かつ残渣及び欠陥の少ないパターンを形成させることができる下地を形成する膜形成用組成物を提供することにある。
なお、本発明における「主鎖」とは、繰り返し単位(I)、(II)及び(III)を全て含む結合手を含有するポリマー鎖を指す。
当該膜形成用組成物は、基板の一方の面側に塗工することで、耐熱性や基板密着性等に優れた膜の形成、とりわけ自己組織化リソグラフィープロセスにおける自己組織化膜の下地の形成に好適に用いられる組成物である。
[A]重合体は、繰り返し単位(I)、繰り返し単位(II)及び繰り返し単位(III)を有し、主鎖の少なくとも一方の末端にSi-OH、Si-H又はSi-Nと相互作用する基(X)を含む構造単位(X)を有する。[A]重合体は、繰り返し単位(I)~(III)をランダム状に有していてもよく、ブロック状に有していてもよい。すなわち、[A]重合体は、ランダム共重合体でもブロック共重合体でもよいが、パターンの残渣及び欠陥をより低減する観点から、ランダム共重合体が好ましい。[A]重合体は、繰り返し単位(I)~(III)を1種又は2種以上有していてもよい。
繰り返し単位(I)は、架橋性基を含む繰り返し単位である。「架橋性基」とは、加熱条件下、活性エネルギー線照射条件下、酸性条件下等における反応により、架橋構造を形成する基をいう。
ビニル基、ビニロキシ基、アリル基、(メタ)アクリロイル基、スチリル基等の炭素-炭素二重結合含有基;
エチニル基、プロパルギル基、プロパルギルオキシ基、プロパルギルアミノ基等の炭素-炭素三重結合含有基;
オキシラニル基、オキシラニルオキシ基、オキセタニル基、オキセタニルオキシ基等の環状エーテル基;
シクロブタン環が縮環したフェニル基、シクロブタン環が縮環したナフチル基等のシクロブタン環が縮環したアリール基;
アセトキシフェニル基、t-ブトキシフェニル基等の酸基又は熱解離性基で保護されたフェノール性水酸基が結合したアリール基;
アセトキシメチルフェニル基、メトキシメチルフェニル基等の酸基又は熱解離性基で保護されたメチロール基(-CH2OH)が結合したアリール基;
スルファニルメチルフェニル基、メチルスルファニルメチルフェニル基等の置換又は非置換のスルファニルメチル基(-CH2SH)が結合したアリール基などが挙げられる。
繰り返し単位(II)及び繰り返し単位(III)は、繰り返し単位(I)と異なる繰り返し単位である。繰り返し単位(III)は繰り返し単位(II)よりも極性が高い。
スチレン;
α-メチルスチレン;o-、m-又はp-メチルスチレン、p-t-ブチルスチレン、2,4,6-トリメチルスチレン、p-メトキシスチレン、p-t-ブトキシスチレン、o-、m-又はp-ビニルスチレン等の電子供与性基置換スチレン;
o-、m-又はp-ヒドロキシスチレン、m-又はp-クロロメチルスチレン、p-クロロスチレン、p-ブロモスチレン、p-ヨードスチレン、p-ニトロスチレン、p-シアノスチレン等の電子求引性基置換スチレンなどの置換スチレンが挙げられる。
(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸t-ブチル、(メタ)アクリル酸2-エチルヘキシル等の(メタ)アクリル酸アルキルエステル;
(メタ)アクリル酸シクロペンチル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸1-メチルシクロペンチル、(メタ)アクリル酸2-エチルアダマンチル、(メタ)アクリル酸2-(アダマンタン-1-イル)プロピル等の(メタ)アクリル酸脂環式炭化水素基エステル;
(メタ)アクリル酸フェニル、(メタ)アクリル酸ナフチル等の(メタ)アクリル酸アリールエステル;
(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸3-ヒドロキシアダマンチル、(メタ)アクリル酸3-グリシジルプロピル等の(メタ)アクリル酸置換アルキルエステルなどが挙げられる。
構造単位(X)は、主鎖の少なくとも一方の末端に存在する基(X)を含む構造単位である。基(X)は、Si-OH、Si-H又はSi-Nと相互作用する基である。
[A]重合体は、例えば繰り返し単位(I)~(III)を与える単量体と、臭化銅(II)及びトリス[(2-ジメチルアミノ)エチル]アミン等のアミン化合物と、アニソール等の溶媒とを仕込み、これに、2-ブロモイソ酪酸2-ヒドロキシエチル等の構造単位(X)を与えるハロゲン化合物を加える方法により、原子移動ラジカル重合によって、繰り返し単位(I)~(III)を有し、かつ主鎖の一方の末端に構造単位(X)を有する重合体を合成することができる。
[B]溶媒は、少なくとも[A]重合体及び所望により含有される任意成分を溶解又は分散可能な溶媒であれば特に限定されず用いることができる。
4-メチル-2-ペンタノール、n-ヘキサノール等の炭素数1~18の脂肪族モノアルコール系溶媒;
シクロヘキサノール等の炭素数3~18の脂環式モノアルコール系溶媒;
1,2-プロピレングリコール等の炭素数2~18の多価アルコール系溶媒;
プロピレングリコールモノメチルエーテル等の炭素数3~19の多価アルコール部分エーテル系溶媒などが挙げられる。
ジエチルエーテル、ジプロピルエーテル、ジブチルエーテル、ジペンチルエーテル、ジイソアミルエーテル、ジヘキシルエーテル、ジヘプチルエーテル等のジアルキルエーテル系溶媒;
テトラヒドロフラン、テトラヒドロピラン等の環状エーテル系溶媒;
ジフェニルエーテル、アニソール(メチルフェニルエーテル)等の芳香環含有エーテル系溶媒などが挙げられる。
アセトン、メチルエチルケトン、メチル-n-プロピルケトン、メチル-n-ブチルケトン、ジエチルケトン、メチル-iso-ブチルケトン、2-ヘプタノン(メチル-n-ペンチルケトン)、エチル-n-ブチルケトン、メチル-n-ヘキシルケトン、ジ-iso-ブチルケトン、トリメチルノナノン等の鎖状ケトン系溶媒;
シクロペンタノン、シクロヘキサノン、シクロヘプタノン、シクロオクタノン、メチルシクロヘキサノン等の環状ケトン系溶媒;
2,4-ペンタンジオン、アセトニルアセトン、アセトフェノン等が挙げられる。
N,N’-ジメチルイミダゾリジノン、N-メチルピロリドン等の環状アミド系溶媒;
N-メチルホルムアミド、N,N-ジメチルホルムアミド、N,N-ジエチルホルムアミド、アセトアミド、N-メチルアセトアミド、N,N-ジメチルアセトアミド、N-メチルプロピオンアミド等の鎖状アミド系溶媒などが挙げられる。
酢酸n-ブチル、乳酸エチル等のモノカルボン酸エステル系溶媒;
プロピレングリコールアセテート等の多価アルコールカルボキシレート系溶媒;
プロピレングリコールモノメチルエーテルアセテート等の多価アルコール部分エーテルカルボキシレート系溶媒;
γ-ブチロラクトン、δ-バレロラクトン等のラクトン系溶媒;
シュウ酸ジエチル等の多価カルボン酸ジエステル系溶媒;
ジメチルカーボネート、ジエチルカーボネート、エチレンカーボネート、プロピレンカーボネート等のカーボネート系溶媒などが挙げられる。
n-ペンタン、n-ヘキサン等の炭素数5~12の脂肪族炭化水素系溶媒;
トルエン、キシレン等の炭素数6~16の芳香族炭化水素系溶媒等が挙げられる。
当該膜形成用組成物が含有していてもよい任意成分としては、例えば界面活性剤等が挙げられる。当該膜形成用組成物は、界面活性剤を含有することで、基板等への塗布性をより向上できる。
当該膜形成用組成物は、例えば[A]重合体、[B]溶媒及び必要に応じて任意成分を所定の割合で混合し、好ましくは、得られた混合物を0.45μm程度の細孔を有する高密度ポリエチレンフィルター等により濾過することにより調製できる。当該膜形成用組成物の固形分濃度の下限としては、0.01質量%が好ましく、0.1質量%がより好ましく、0.5質量%がさらに好ましく、1.0質量%が特に好ましい。上記固形分濃度の上限としては、30質量%が好ましく、10質量%がより好ましく、5質量%がさらに好ましく、2質量%が特に好ましい。
当該膜形成方法は、基板の一方の面側に、当該膜形成用組成物を塗工する工程と、上記塗工工程により形成された塗工膜を加熱する工程とを備える。
当該自己組織化リソグラフィープロセスは、基板の一方の面側に、当該膜形成用組成物を塗工する工程(以下、「塗工工程(1)」ともいう)と、上記塗工工程(1)により形成された塗工膜を加熱する工程(以下、「加熱工程」ともいう)と、上記加熱工程により形成された膜の上記基板とは反対の面側に、ブロック共重合体及び溶媒を含有する組成物を塗工する工程(以下、「塗工工程(2)」ともいう)と、上記塗工工程(2)により形成されたブロック共重合体膜を相分離させる工程(以下、「相分離工程」ともいう)と、上記相分離したブロック共重合体膜の一方の相を除去する工程(以下、「除去工程」ともいう)と、上記除去工程により形成されるレジストパターンを直接的又は間接的に用い、エッチングする工程(以下、「エッチング工程」ともいう)とを備える。
本工程では、基板の一方の面側に、当該膜形成用組成物を塗工する。
本工程では、上記塗工工程(1)により形成された塗工膜を加熱する。これにより、図1に示すように、基板101上に下地102が形成される。
本工程では、下地102上にプレパターン103を形成する。本工程を行うことで、自己組織化膜105形成の際の相分離がより制御され、より良好に自己組織化による相分離構造を形成できる。すなわち、自己組織化膜105を形成する成分等のうち、プレパターン103の側面と親和性が高い成分等はプレパターン103に沿って相を形成し、親和性の低い成分等はプレパターン103から離れた位置に相を形成する。これにより、より良好に自己組織化による相分離構造を形成することができる。また、プレパターン103の材質、長さ、厚さ、形状等により、形成される相分離構造を細かく制御することができる。さらに、プレパターン103は、部分露光、レーザーアブレージョン等により部分改質を行うこともできる。なお、プレパターン103としては、最終的に形成したいパターンに合わせて適宜選択することができ、例えばラインアンドスペースパターン、ホールパターン、ピラーパターン等を用いることができる。
本工程では、上記加熱工程により形成された下地の上記基板とは反対の面側に、ブロック共重合体及び溶媒を含有する組成物を塗工する。プレパターン103を形成した場合には、図3に示すように、プレパターン103によって区切られた下地102上の領域に、ブロック共重合体及び溶媒を含有する組成物(以下、「パターン形成用組成物(I)」ともいう)を塗工する。これによりブロック共重合体膜が形成される。
本工程では、上記塗工工程により形成されたブロック共重合体膜を相分離させる。これにより図4に示すように相分離構造を有する自己組織化膜105が形成される。相分離させる方法としては、例えばアニーリングする方法等が挙げられる。
本工程では、上記相分離したブロック共重合体膜の一方の相を除去する。例えば図4及び図5に示すように、上記自己組織化膜105が有する相分離構造のうちの一部のブロック相105aを除去する。自己組織化により相分離した各相のエッチングレートの差を用いて、ブロック相105aをエッチング処理により除去することができる。相分離構造のうちのブロック相105a及び後述するようにプレパターン103を除去した後の状態を図5に示す。なお、上記エッチング処理の前に、必要に応じて放射線を照射してもよい。上記放射線としては、例えばブロック相105aがポリメタクリル酸メチルブロック相である場合には、254nmの放射線を用いることができる。上記放射線照射により、ポリメタクリル酸メチルブロック相が分解されるため、よりエッチングされ易くなる。
本工程は、図4及び図5に示すように、プレパターン103を除去する工程である。プレパターン103を除去することにより、より微細かつ複雑なパターンを形成することが可能となる。なお、プレパターン103の除去の方法については、相分離構造のうちの一部のブロック相105aの除去の方法の上記説明を適用できる。また、本工程は、上記除去工程と同時に行ってもよいし、除去工程の前又は後に行ってもよい。
本工程では、上記除去工程により形成されるレジストパターンを直接的又は間接的に用い、エッチングする。
重合体のMw及びMnは、ゲルパーミエーションクロマトグラフィー(GPC)によりGPCカラム(東ソー社の「G2000HXL」2本、「G3000HXL」1本及び「G4000HXL」1本)を使用し、以下の条件により測定した。
溶離液:テトラヒドロフラン(和光純薬工業社)
流量:1.0mL/分
試料濃度:1.0質量%
試料注入量:100μL
カラム温度:40℃
検出器:示差屈折計
標準物質:単分散ポリスチレン
1H-NMR分析は、核磁気共鳴装置(日本電子社の「JNM-ECX400」)を使用して行った。各重合体における各構造単位の含有割合は、1H-NMRで得られたスペクトルにおける各構造単位に対応するピークの面積比から算出した。
[合成例1]
冷却管、滴下ロート及び温度計を備えた200mL三口フラスコに、アニソール40g、スチレン16.7g(0.160mol)、メタクリル酸メチル3.00g(0.030mol)、2-ヒドロキシエチルメタクリレート1.30g(0.01mol)、臭化銅(II)0.29g(2.00mmol)及びトリス[(2-ジメチルアミノ)エチル]アミン0.46g(2mmol)を仕込み、100℃に加熱した後、2-ブロモイソ酪酸エチル0.53mL(3.6mmol)を加え、窒素フロー下、8時間加熱撹拌した。得られた重合液は、セライト濾過して銅錯体を除去し、超純水500gにて洗浄を3回繰り返した。有機層を回収した後、濃縮し、得られた濃縮物にテトラヒドロフラン(THF)50gを加えたものをメタノール/超純水(質量比5/5)混合液1,000gへ加えて、重合体を析出させた。得られた固体をブフナーロートにて回収し、メタノール50gを用いて洗浄した。得られた固体を減圧乾燥することで、白色の重合体(a-1)11.2gを得た。
冷却管、滴下ロート及び温度計を備えた200mL三口フラスコに、アニソール40g、スチレン14.6g(0.140mol)、メタクリル酸メチル6.00g(0.060mol)、臭化銅(II)0.29g(2.00mmol)及びトリス[(2-ジメチルアミノ)エチル]アミン0.46g(2.0mmol)を仕込み、100℃に加熱した後、2-ブロモイソ酪酸2-ヒドロキシエチル0.53mL(3.6mmol)をシリンジにて加え、窒素フロー下、8時間加熱撹拌した。得られた重合液は、セライト濾過し銅錯体を除去し、超純水500gにて洗浄を3回繰り返した。有機層を回収した後、濃縮し、得られた濃縮物に、THF50gを加えたものをメタノール/超純水(質量比5/5)の混合液1,000gへ加えて、重合体を析出させた。得られた固体をブフナーロートにて回収し、メタノール50gを用いて洗浄した。得られた固体を減圧乾燥することで、白色の重合体(a-2)11.5gを得た。
冷却管、滴下ロート及び温度計を備えた200mL三口フラスコに、アニソール40g、スチレン14.6g(0.140mol)、メタクリル酸メチル5.61g(0.056mol)、メタクリル酸2-(2-ビニロキシエトキシ)エチル(日本触媒社の「VEEM」)0.80g(0.004mol)、臭化銅(II)0.29g(2.00mmol)及びトリス[(2-ジメチルアミノ)エチル]アミン0.46g(2.0mmol)を仕込み、100℃に加熱し、2-ブロモイソ酪酸2-ヒドロキシエチル0.53mL(3.6mmol)をシリンジにて加え、窒素フロー下、8時間加熱撹拌した。得られた重合液は、セライト濾過し銅錯体を除去し、超純水500gにて洗浄を3回繰り返した。有機層を回収した後、濃縮し、得られた濃縮物に、THF50gを加えたものをメタノール/超純水(質量比5/5)の混合液1,000gへ加えて、重合体を析出させた。得られた固体をブフナーロートにて回収し、メタノール50gを用いて洗浄した。得られた固体を減圧乾燥することで、白色の重合体(A-1)11.5gを得た。
冷却管、滴下ロート及び温度計を備えた200mL三口フラスコに、アニソール40g、スチレン14.6g(0.140mol)、メタクリル酸メチル5.61g(0.056mol)、4-ビニルベンゾシクロブテン(Amadis chemical社の「vBCB」)0.53g(0.004mol)、臭化銅(II)0.29g(2.00mmol)及びトリス[(2-ジメチルアミノ)エチル]アミン0.46g(2.0mmol)を仕込み、100℃に加熱し、2-ブロモイソ酪酸2-ヒドロキシエチル0.53mL(3.6mmol)をシリンジにて加え、窒素フロー下、8時間加熱撹拌した。得られた重合液は、セライト濾過し銅錯体を除去し、超純水500gにて洗浄を3回繰り返した。有機層を回収した後、濃縮し、得られた濃縮物に、THF50gを加えたものをメタノール/超純水(質量比5/5)の混合液1,000gへ加えて、重合体を析出させた。得られた固体をブフナーロートにて回収し、メタノール50gを用いて洗浄した。得られた固体を減圧乾燥することで、白色の重合体(A-2)11.5gを得た。
冷却管と滴下ロート、温度計を備えた200mL三口フラスコにアニソール40g、スチレン14.6g(0.140mol)、メタクリル酸メチル5.61g(0.056mol)、メタクリル酸アリル0.51g(0.004mmol)、臭化銅(II)0.29g(2.00mmol)、トリス[(2-ジメチルアミノ)エチル]アミン0.46g(2.0mmol)を加え、100℃ヘ加熱し、2-ブロモイソ酪酸2-ヒドロキシエチル0.53ml(3.6mmol)をシリンジにて加え、窒素フロー下、8時間加熱撹拌した。得られた重合溶液は、セライト濾過し銅錯体を除去し、超純水500gにて洗浄を3回繰り返した。有機層を回収したのち、濃縮した樹脂溶液にテトラヒドロフラン50gを加えたものをメタノール/超純水=5/5、1000gへ沈殿精製させポリマーを析出させた。この固体をブフナーロートにて回収し、メタノール50gにてすすいだ。白色の固体は、減圧乾燥することで(A-3)11.3gを得た。
冷却管と滴下ロート、温度計を備えた200mL三口フラスコにアニソール40g、スチレン14.6g(0.140mol)、メタクリル酸メチル5.61g(0.056mol)、tert-ブトキシスチレン0.71g(0.004mmol)、臭化銅(II)0.29g(2.00mmol)、トリス[(2-ジメチルアミノ)エチル]アミン0.46g(2.0mmol)を加え、100℃へ加熱し、2-ブロモイソ酪酸2-ヒドロキシエチル0.53ml(3.6mmol)をシリンジにて加え、窒素フロー下、8時間加熱撹拌した。得られた重合溶液は、セライト濾過し銅錯体を除去し、超純水500gにて洗浄を3回繰り返した。有機層を回収したのち、濃縮した樹脂溶液にテトラヒドロフラン50gを加えたものをメタノール/超純水=5/5、1000gへ沈殿精製させポリマーを析出させた。この固体をブフナーロートにて回収し、メタノール50gにてすすいだ。白色の固体は、減圧乾燥することで(A-4)11.7gを得た。
[合成例7]
500mLのフラスコ反応容器を減圧乾燥した後、窒素雰囲気下、蒸留脱水処理を行ったTHF200gを注入し、-78℃まで冷却した。その後、このTHFにsec-ブチルリチウム(sec-BuLi)の1Nシクロヘキサン溶液を0.40mL(0.356mmol)注入し、その後、重合禁止剤除去のためシリカゲルによる吸着濾別と蒸留脱水処理とを行ったスチレン22.1mL(0.192mol)を30分かけて滴下注入し、重合系が橙色であることを確認した。この滴下注入のとき、反応溶液の内温が-60℃以上にならないように注意した。滴下終了後に30分間熟成し、その後、1,1-ジフェニルエチレン0.15mL(0.00107mol)及び塩化リチウムの0.5NTHF溶液1.42mL(0.0007mol)を加え、重合系が暗赤色になったことを確認した。さらに、重合禁止剤除去のためシリカゲルによる吸着濾別と蒸留脱水処理とを行ったメタクリル酸メチル18.0mL(0.180mol)をこの溶液に30分かけて滴下注入して重合系が薄黄色になったことを確認し、その後120分間反応させた。この後、末端停止剤としてのメタノール1mLを注入し重合末端の停止反応を行った。この反応溶液を室温まで昇温し、得られた反応溶液を濃縮してメチルイソブチルケトン(MIBK)で置換した。その後、シュウ酸2質量%水溶液1,000gを注入撹拌し、静置後、下層の水層を取り除いた。この操作を3回繰り返し、Li塩を除去した。その後、超純水1,000gを注入撹拌し、下層の水層を取り除いた。この操作を3回繰り返しシュウ酸を除去した後、溶液を濃縮してメタノール500g中に滴下することで重合体を析出させ、ブフナーロートにて固体を回収した。次にポリスチレンのホモポリマーを除去するためシクロヘキサン500gを注ぎ、ポリスチレンホモポリマーをシクロヘキサンへ溶解させ、ブロック共重合体を洗浄した。なお、この作業は4回繰り返し、再度、ブフナーロートにて固体を回収した。この重合体を60℃で減圧乾燥させることで白色のブロック共重合体(B-1)37.4gを得た。
[比較例1]
上記合成した重合体(a-1)1.2g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98.8gを加え溶解させたのち、0.45μmの細孔を有する高密度ポリエチレンフィルターにて濾過し、膜形成用組成物(CA-1)を調製した。
上記比較例1において、重合体(a-1)の代わりに、重合体(a-2)並びに(A-1)~(A-4)のいずれかを用いた以外は、比較例1と同様にして、膜形成用組成物(CA-2)、(A-1)~(A-4)を調製した。
上記合成したブロック共重合体(B-1)1.5g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69g及び乳酸エチル29.5gを加え、撹拌した後、0.45μmの細孔を有する高密度ポリエチレンフィルターにて濾過し、パターン形成用組成物(S-1)を調製した。
シリコン基板上に、トラック(東京エレクトロン社の「TEL DSA ACT12」)を用いて、上記調製した各膜形成用組成物を、1,500rpmにてスピンコートし、250℃で180秒間焼成した。この基板をPGMEAにて洗浄し、未反応の膜形成用組成物を除去した。シリコン基板上に形成された塗膜の平均厚みは、エリプソメータの膜厚測定結果より、5nm程度であった。次に、この塗膜(下地)が形成された基板に、上記調製したパターン形成用組成物(S-1)を1,500rpmにてスピン塗工し、塗工膜を形成した後、窒素下、220℃で60秒間アニールすることで相分離させた。
[相分離構造の良好性並びに残渣及び欠陥]
ウェット現像後の基板について、基板上に広がるフィンガープリントパターンについて、日立ハイテクノロジーズ社の「CG5000」を用いて、10万倍の倍率にて、相分離構造を観察し、また、ピッチサイズのパターン測長を実施した。実施例1~4の膜形成用組成物を用いた場合は、相分離構造が良好に形成されていた。一方、比較例1及び2の膜形成用組成物を用いた場合は、相分離構造は良好には形成されていなかった。
上記レジストパターンの形成の際に形成した塗膜(未反応の膜形成用組成物の除去後)について、この塗膜の表面における水の接触角を自動接触角計(協和界面科学社の「Drop Master DM-501」)を用いて測定した。なお、ポリスチレンホモポリマーの接触角値は90°、ポリメタクリル酸メチルの接触角値は68°であった。
上記レジストパターンの形成の際に形成した塗膜(未反応の膜形成用組成物の除去後)について、この塗膜の表面における水の接触角の値と、ジヨードメタンの接触角の値とを測定し、これらの測定値から、表面自由エネルギーの値を算出した。
102 下地
103 プレパターン
104 塗工膜
105 自己組織化膜
105a、105b ブロック相
Claims (12)
- 架橋性基を含む第1繰り返し単位、第1繰り返し単位と異なる繰り返し単位である第2繰り返し単位、及び第1繰り返し単位と異なりかつ第2繰り返し単位より極性が高い第3繰り返し単位を有し、主鎖の少なくとも一方の末端にSi-OH、Si-H又はSi-Nと相互作用する第1基を含む構造単位を有する重合体と、
溶媒と
を含有することを特徴とする膜形成用組成物。 - 自己組織化リソグラフィープロセスにおける自己組織化膜の下地用組成物である、請求項1に記載の膜形成用組成物。
- Si-OH、Si-H又はSi-Nを表層に有する基板の上面側に形成され、上記第2繰り返し単位を含むブロック及び上記第3繰り返し単位を含むブロックを有するブロック共重合体を含有する自己組織化膜の下地の形成に用いられる請求項1又は請求項2に記載の膜形成用組成物。
- 上記第1基が、ヒドロキシ基及びカルボキシ基の少なくとも一方である請求項1、請求項2又は請求項3に記載の膜形成用組成物。
- 上記架橋性基が、炭素-炭素二重結合含有基、シクロブタン環が縮環したアリール基、又は酸基若しくは熱解離性基で保護されたフェノール性水酸基若しくはメチロール基が結合したアリール基である請求項1から請求項4のいずれか1項に記載の膜形成用組成物。
- 上記第2繰り返し単位が芳香環を有する、請求項1から請求項5のいずれか1項に記載の膜形成用組成物。
- 上記第2繰り返し単位が、置換又は非置換のスチレンに由来する請求項6に記載の膜形成用組成物。
- 上記第3繰り返し単位が、(メタ)アクリル酸エステルに由来する繰り返し単位、主鎖にSi-O結合を含む繰り返し単位、ヒドロキシカルボン酸に由来する繰り返し単位又はアルキレンカーボネートに由来する繰り返し単位である請求項1から請求項7のいずれか1項に記載の膜形成用組成物。
- 基板の一方の面側に、請求項1から請求項8のいずれか1項に記載の膜形成用組成物を塗工する工程と、
上記塗工工程により形成された塗工膜を加熱する工程と
を備える、膜形成方法。 - 上記基板がSi-OH、Si-H又はSi-Nを表層に有する基板である、請求項9に記載の膜形成方法。
- 基板の一方の面側に、請求項1から請求項8のいずれか1項に記載の膜形成用組成物を塗工する工程と、
上記塗工工程により形成された塗工膜を加熱する工程と、
上記加熱工程により形成された膜の上記基板とは反対の面側に、ブロック共重合体及び溶媒を含有する組成物を塗工する工程と、
上記塗工工程により形成されたブロック共重合体膜を相分離させる工程と、
上記相分離したブロック共重合体膜の一方の相を除去する工程と、
上記除去工程により形成されるレジストパターンを直接的又は間接的に用い、エッチングする工程と
を備える自己組織化リソグラフィープロセス。 - 上記基板がSi-OH、Si-H又はSi-Nを表層に有する基板である、請求項11に記載の自己組織化リソグラフィープロセス。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020197000050A KR102443384B1 (ko) | 2016-07-06 | 2017-07-06 | 막 형성용 조성물, 막 형성 방법 및 자기 조직화 리소그래피 프로세스 |
JP2018526447A JP6955176B2 (ja) | 2016-07-06 | 2017-07-06 | 膜形成用組成物、膜形成方法及び自己組織化リソグラフィープロセス |
US16/239,592 US11460767B2 (en) | 2016-07-06 | 2019-01-04 | Composition for film formation, film-forming method and directed self-assembly lithography process |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016134633 | 2016-07-06 | ||
JP2016-134633 | 2016-07-06 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/239,592 Continuation US11460767B2 (en) | 2016-07-06 | 2019-01-04 | Composition for film formation, film-forming method and directed self-assembly lithography process |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018008734A1 true WO2018008734A1 (ja) | 2018-01-11 |
Family
ID=60912159
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2017/024875 WO2018008734A1 (ja) | 2016-07-06 | 2017-07-06 | 膜形成用組成物、膜形成方法及び自己組織化リソグラフィープロセス |
Country Status (4)
Country | Link |
---|---|
US (1) | US11460767B2 (ja) |
JP (1) | JP6955176B2 (ja) |
KR (1) | KR102443384B1 (ja) |
WO (1) | WO2018008734A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2021046484A (ja) * | 2019-09-18 | 2021-03-25 | 三菱瓦斯化学株式会社 | 極性ビニルポリマーの製造方法 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102549753B1 (ko) * | 2021-11-01 | 2023-06-30 | 한국화학연구원 | 상향식 패턴 제조방법, 이에 의해 제조된 복합구조체 및 복합구조체를 포함하는 반도체 소자 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011059583A (ja) * | 2009-09-14 | 2011-03-24 | Jsr Corp | 微細パターン形成用樹脂組成物および微細パターン形成方法、ならびに重合体 |
JP2013212489A (ja) * | 2012-03-09 | 2013-10-17 | Tokyo Ohka Kogyo Co Ltd | ブロックコポリマーを含む層のパターン形成方法、及び下地剤 |
JP2014078540A (ja) * | 2012-10-09 | 2014-05-01 | Toshiba Corp | 自己組織化パターンの形成方法 |
WO2014184114A1 (en) * | 2013-05-13 | 2014-11-20 | AZ Electronic Materials (Luxembourg) S.à.r.l. | Template for self assembly and method of making a self assembled pattern |
WO2015091047A1 (en) * | 2013-12-16 | 2015-06-25 | AZ Electronic Materials (Luxembourg) S.à.r.l. | Underlayer composition for promoting self assembly and method of making and using |
JP2015168732A (ja) * | 2014-03-05 | 2015-09-28 | Jsr株式会社 | パターン形成用組成物及びパターン形成方法 |
JP2016108436A (ja) * | 2014-12-05 | 2016-06-20 | 東京応化工業株式会社 | 下地剤、及び相分離構造を含む構造体の製造方法 |
US20160186001A1 (en) * | 2014-12-30 | 2016-06-30 | Rohm And Haas Electronic Materials Llc | Copolymer formulation for directed self assembly, methods of manufacture thereof and articles comprising the same |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19829172A1 (de) | 1998-06-30 | 2000-01-05 | Univ Konstanz | Verfahren zur Herstellung von Antireflexschichten |
JP3782357B2 (ja) | 2002-01-18 | 2006-06-07 | 株式会社東芝 | 半導体発光素子の製造方法 |
JP4673266B2 (ja) | 2006-08-03 | 2011-04-20 | 日本電信電話株式会社 | パターン形成方法及びモールド |
US20080038467A1 (en) | 2006-08-11 | 2008-02-14 | Eastman Kodak Company | Nanostructured pattern method of manufacture |
US7906031B2 (en) | 2008-02-22 | 2011-03-15 | International Business Machines Corporation | Aligning polymer films |
JP2010058403A (ja) | 2008-09-04 | 2010-03-18 | Fujifilm Corp | 高分子膜および積層体 |
US8821978B2 (en) * | 2009-12-18 | 2014-09-02 | International Business Machines Corporation | Methods of directed self-assembly and layered structures formed therefrom |
US8828493B2 (en) * | 2009-12-18 | 2014-09-09 | International Business Machines Corporation | Methods of directed self-assembly and layered structures formed therefrom |
TWI556958B (zh) * | 2010-09-14 | 2016-11-11 | 東京應化工業股份有限公司 | 基質劑及含嵌段共聚物之層的圖型形成方法 |
JP5254381B2 (ja) | 2011-02-23 | 2013-08-07 | 株式会社東芝 | パターン形成方法 |
US9134617B2 (en) * | 2011-06-10 | 2015-09-15 | Tokyo Ohka Kogyo Co., Ltd. | Solvent developable negative resist composition, resist pattern formation method, and method for forming pattern of layer including block copolymer |
US8691925B2 (en) * | 2011-09-23 | 2014-04-08 | Az Electronic Materials (Luxembourg) S.A.R.L. | Compositions of neutral layer for directed self assembly block copolymers and processes thereof |
JP6454324B2 (ja) * | 2013-04-03 | 2019-01-16 | ブルーワー サイエンス アイ エヌ シー. | 誘導自己組織化用ブロックコポリマーに用いる高エッチング耐性ポリマーブロック |
JP6558894B2 (ja) * | 2013-12-31 | 2019-08-14 | ローム アンド ハース エレクトロニック マテリアルズ エルエルシーRohm and Haas Electronic Materials LLC | コポリマーの設計、その製造方法およびそれを含む物品 |
JP6623505B2 (ja) * | 2014-05-20 | 2019-12-25 | 東洋インキScホールディングス株式会社 | 無機微粒子分散体の製造方法、無機微粒子分散体、塗膜、および積層体 |
KR102395336B1 (ko) * | 2014-12-05 | 2022-05-06 | 도오꾜오까고오교 가부시끼가이샤 | 하지제, 및 상 분리 구조를 포함하는 구조체의 제조 방법 |
US9574104B1 (en) * | 2015-10-16 | 2017-02-21 | Az Electronic Materials (Luxembourg) S.A.R.L. | Compositions and processes for self-assembly of block copolymers |
KR102508525B1 (ko) * | 2015-10-19 | 2023-03-09 | 삼성전자주식회사 | 블록 코폴리머 및 이를 이용한 집적회로 소자의 제조 방법 |
-
2017
- 2017-07-06 WO PCT/JP2017/024875 patent/WO2018008734A1/ja active Application Filing
- 2017-07-06 KR KR1020197000050A patent/KR102443384B1/ko active IP Right Grant
- 2017-07-06 JP JP2018526447A patent/JP6955176B2/ja active Active
-
2019
- 2019-01-04 US US16/239,592 patent/US11460767B2/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011059583A (ja) * | 2009-09-14 | 2011-03-24 | Jsr Corp | 微細パターン形成用樹脂組成物および微細パターン形成方法、ならびに重合体 |
JP2013212489A (ja) * | 2012-03-09 | 2013-10-17 | Tokyo Ohka Kogyo Co Ltd | ブロックコポリマーを含む層のパターン形成方法、及び下地剤 |
JP2014078540A (ja) * | 2012-10-09 | 2014-05-01 | Toshiba Corp | 自己組織化パターンの形成方法 |
WO2014184114A1 (en) * | 2013-05-13 | 2014-11-20 | AZ Electronic Materials (Luxembourg) S.à.r.l. | Template for self assembly and method of making a self assembled pattern |
WO2015091047A1 (en) * | 2013-12-16 | 2015-06-25 | AZ Electronic Materials (Luxembourg) S.à.r.l. | Underlayer composition for promoting self assembly and method of making and using |
JP2015168732A (ja) * | 2014-03-05 | 2015-09-28 | Jsr株式会社 | パターン形成用組成物及びパターン形成方法 |
JP2016108436A (ja) * | 2014-12-05 | 2016-06-20 | 東京応化工業株式会社 | 下地剤、及び相分離構造を含む構造体の製造方法 |
US20160186001A1 (en) * | 2014-12-30 | 2016-06-30 | Rohm And Haas Electronic Materials Llc | Copolymer formulation for directed self assembly, methods of manufacture thereof and articles comprising the same |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2021046484A (ja) * | 2019-09-18 | 2021-03-25 | 三菱瓦斯化学株式会社 | 極性ビニルポリマーの製造方法 |
Also Published As
Publication number | Publication date |
---|---|
KR20190024952A (ko) | 2019-03-08 |
JP6955176B2 (ja) | 2021-10-27 |
KR102443384B1 (ko) | 2022-09-16 |
JPWO2018008734A1 (ja) | 2019-04-25 |
US11460767B2 (en) | 2022-10-04 |
US20190233561A1 (en) | 2019-08-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI535770B (zh) | 用於導向自組裝嵌段共聚物之中性層組合物及其方法 | |
JP2018503241A (ja) | 誘導自己集合体パターン化のための欠陥低減方法および組成物 | |
EP3500637B1 (en) | Polymer compositions for self-assembly applications | |
JP6394042B2 (ja) | パターン形成用組成物及びパターン形成方法 | |
WO2018008734A1 (ja) | 膜形成用組成物、膜形成方法及び自己組織化リソグラフィープロセス | |
WO2016088785A1 (ja) | 自己組織化膜の形成方法、パターン形成方法及び自己組織化膜形成用組成物 | |
WO2018008481A1 (ja) | パターン形成用組成物及びパターン形成方法 | |
JP2023061994A (ja) | ブロックコポリマーの自己組織化のための新規組成物及び方法 | |
WO2018066716A1 (ja) | パターン形成方法及び組成物 | |
JP2016161886A (ja) | 下層膜形成用組成物、下層膜の形成方法及び自己組織化リソグラフィープロセス | |
JP2024514938A (ja) | 誘導自己集合用途のための増強された速度を有するマルチピッチ許容ブロックコポリマー | |
JPWO2015046510A1 (ja) | ブロック共重合体、パターン形成用自己組織化組成物およびパターン形成方法 | |
WO2022049968A1 (ja) | 自己組織化膜形成用組成物及びパターン形成方法 | |
JP2016134580A (ja) | パターン形成用組成物、パターン形成方法及びブロック共重合体 | |
WO2022039082A1 (ja) | 下層膜形成用組成物、下層膜、及び、リソグラフィープロセス | |
TW202406953A (zh) | 開發含有羥基單體之新型中性墊以改善用於雙嵌段共聚物定向自組裝之SiARC基板的相容性 | |
TW202319412A (zh) | 新型親水性釘壓mat之開發 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2018526447 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17824337 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20197000050 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 17824337 Country of ref document: EP Kind code of ref document: A1 |