TWI571475B - 嵌段共聚物 - Google Patents
嵌段共聚物 Download PDFInfo
- Publication number
- TWI571475B TWI571475B TW104132189A TW104132189A TWI571475B TW I571475 B TWI571475 B TW I571475B TW 104132189 A TW104132189 A TW 104132189A TW 104132189 A TW104132189 A TW 104132189A TW I571475 B TWI571475 B TW I571475B
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- Prior art keywords
- block copolymer
- group
- block
- atom
- structural formula
- Prior art date
Links
- 229920001400 block copolymer Polymers 0.000 title claims description 146
- 238000000034 method Methods 0.000 claims description 65
- 125000004429 atom Chemical group 0.000 claims description 39
- 125000003342 alkenyl group Chemical group 0.000 claims description 35
- 125000003118 aryl group Chemical group 0.000 claims description 34
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 34
- 125000005843 halogen group Chemical group 0.000 claims description 29
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- 125000000304 alkynyl group Chemical group 0.000 claims description 28
- 229920006254 polymer film Polymers 0.000 claims description 28
- 238000004132 cross linking Methods 0.000 claims description 25
- 125000000524 functional group Chemical group 0.000 claims description 25
- 125000002947 alkylene group Chemical group 0.000 claims description 24
- 229910052717 sulfur Inorganic materials 0.000 claims description 24
- 125000004434 sulfur atom Chemical group 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 19
- -1 -S(=O) 2 - Chemical group 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 125000004419 alkynylene group Chemical group 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 125000001188 haloalkyl group Chemical group 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 150000001540 azides Chemical class 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- 239000013598 vector Substances 0.000 description 18
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 14
- 238000001654 grazing-incidence X-ray scattering Methods 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 238000005530 etching Methods 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- 238000005191 phase separation Methods 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 238000001338 self-assembly Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 230000005660 hydrophilic surface Effects 0.000 description 6
- 230000005661 hydrophobic surface Effects 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000010526 radical polymerization reaction Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 125000005647 linker group Chemical group 0.000 description 5
- LVJZCPNIJXVIAT-UHFFFAOYSA-N 1-ethenyl-2,3,4,5,6-pentafluorobenzene Chemical compound FC1=C(F)C(F)=C(C=C)C(F)=C1F LVJZCPNIJXVIAT-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 241000446313 Lamella Species 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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002070 nanowire Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 238000000059 patterning Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- AISZNMCRXZWVAT-UHFFFAOYSA-N 2-ethylsulfanylcarbothioylsulfanyl-2-methylpropanenitrile Chemical compound CCSC(=S)SC(C)(C)C#N AISZNMCRXZWVAT-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- SZBHRHYLUMGWPX-UHFFFAOYSA-N 5-ethenyl-2,3,5,6-tetrafluorocyclohexa-1,3-dien-1-ol Chemical compound OC=1C(C(C=C)(C=C(C=1F)F)F)F SZBHRHYLUMGWPX-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000012987 RAFT agent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- WYSAWGCLEHCQLX-UHFFFAOYSA-N 2-azidophenol Chemical compound OC1=CC=CC=C1N=[N+]=[N-] WYSAWGCLEHCQLX-UHFFFAOYSA-N 0.000 description 1
- QSVOWVXHKOQYIP-UHFFFAOYSA-N 2-dodecylsulfanylcarbothioylsulfanyl-2-methylpropanenitrile Chemical compound CCCCCCCCCCCCSC(=S)SC(C)(C)C#N QSVOWVXHKOQYIP-UHFFFAOYSA-N 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 241000252506 Characiformes Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 210000003918 fraction a Anatomy 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229940030980 inova Drugs 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000006574 non-aromatic ring group Chemical group 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 239000012985 polymerization agent Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00388—Etch mask forming
- B81C1/00428—Etch mask forming processes not provided for in groups B81C1/00396 - B81C1/0042
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/002—Processes for applying liquids or other fluent materials the substrate being rotated
- B05D1/005—Spin coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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Description
本申請案係關於嵌段共聚物及其用途。
嵌段共聚物之分子結構為各具不同化學結構之聚合物嵌段藉由共價鍵而彼此連接。嵌段共聚物可透過相分離(phase separation)而構成規則排列結構(例如球、圓柱及層狀物(lamella))。由嵌段共聚物之自組裝現象(self-assembly phenomenon)所形成的結構具有其尺寸可作寬範圍調整之區段(domain),且其可構成各種形式而能夠用於製作各種次世代奈米裝置、磁性儲存媒介(magnetic storage media)、及圖案(藉微影術(lithography)等等):具體而言,製造高密度磁性記錄媒介(high-density magnetic recording media)、奈米線(nanowire)、量子點(quantum dot)、金屬點(metal dot)等等。
為了用於上述圖案製作所需之嵌段共聚物材料性質包括蝕刻選擇性(etching selectivity)還有自組裝性(self-assembling property)。即,製造用於圖案製作的遮罩
(mask)會需要從自組裝的嵌段共聚物之嵌段(其彼此具有化學性差異)中選擇性移除任一嵌段的程序;在未確保上述程序期間該嵌段間之蝕刻選擇性的情況下,難以將嵌段共聚物用於圖案製作。
本申請案提供嵌段共聚物及其用途。
除非另有具體指明,本說明書中之用語“烷基”可指具1至20個碳、1至16個碳、1至12個碳、1至8個碳、或1至4個碳的烷基。上述烷基可為直鏈型(linear-type)、支鏈型(branched-type)或環型(ring-type),且其可任意地經一或更多取代基所部份取代。
除非另有具體指明,本說明書中之用語“烷氧基”可指具1至20個碳、1至16個碳、1至12個碳、1至8個碳、或1至4個碳的烷氧基。上述烷氧基可為直鏈型、支鏈型或環型,且其可任意地經一或更多取代基所部份取代。
除非另有具體指明,本說明書中之用語“烯基”或“炔基”可指具2至20個碳、2至16個碳、2至12個碳、2至8個碳、或2至4個碳的烯基或炔基。上述烯基或炔基可為直鏈型、支鏈型或環型,且其可任意地經一或更多取
代基所部份取代。
除非另有具體指明,本說明書中之用語“伸烷基(alkylene group)”可指具1至20個碳、1至16個碳、1至12個碳、1至8個碳、或1至4個碳的伸烷基。上述伸烷基可為直鏈型、支鏈型或環型,且其可任意地經一或更多取代基所部份取代。
除非另有具體指明,本說明書中之用語“伸烯基(alkenylene group)”或“伸炔基(alkynylene group)”可指具2至20個碳、2至16個碳、2至12個碳、2至8個碳、或2至4個碳的伸烯基或伸炔基。上述伸烯基或伸炔基可為直鏈型、支鏈型或環型,且其可任意地經一或更多取代基所部份取代。
除非另有具體指明,本說明書中之用語“芳基”或“伸芳基(arylene group)”可指從具有苯環結構或其中有二或更多苯環彼此相連(藉由共享一或兩個碳原子或藉由任何連接子)之結構的化合物所衍生、或者從上述化合物之衍生物所衍生的單價或二價基團。除非另有具體指明,上述芳基或伸芳基可指例如具6至30個碳、6至25個碳、6至21個碳、6至18個碳、或6至13個碳的芳基。
本申請案中,用語“芳族結構(aromatic structure)”可指上述芳基或伸芳基。
除非另有具體指明,本說明書中之用語“脂環族環結構(alicyclic ring structure)”是指非芳環結構(aromatic ring structure)的環型烴原子結構(ring-type hydrocarbon atom
structure)。除非另有具體指明,上述脂環族環結構可指具有例如3至30個碳、3至25個碳、3至21個碳、3至18個碳、或3至13個碳的脂環族環結構。
本申請案中,用語“單鍵”可指在相應區域沒有個別原子的情況。例如,若B係表示A-B-C所示結構中的單鍵,則可認為標為B的區並沒有個別原子存在,使得A與C間直接連接而形成由A-C所示之結構。
本申請案中,可任意地部份取代烷基、烯基、炔基、伸烷基、伸烯基、伸炔基、烷氧基、芳基、伸芳基、鏈、芳族結構等之取代基的實例可包括,但不限於:羥基、鹵素原子、羧基、環氧丙基(glycidyl group)、丙烯醯基(acryloyl group)、甲基丙烯醯基(methacryloyl group)、丙烯醯氧基(acryloyloxy group)、甲基丙烯醯氧基(methacryloyloxy group)、硫基(thiol group)、烷基、烯基、炔基、伸烷基、伸烯基、伸炔基、烷氧基、芳基等等。
本申請案之嵌段共聚物可包含含有以下結構式1所示之結構單元的嵌段(後文中可稱為嵌段1)。嵌段1可僅由以下結構式1所示之結構單元所組成或者是除了以上結構式1所示之結構單元以外還含另外的結構單元。
結構式1中,R表示氫原子或烷基;X表示單鍵、氧原子、硫原子、-S(=O)2-、羰基、伸烷基、伸烯基、伸炔基、-C(=O)-X1-或-X1-C(=O)-,其中,X1表示氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基;以及Y表示單價取代基,其包含連接了含有8或更多成鏈原子(chain-forming atom)之鏈的環結構。
於另一實例中,結構式1之X可表示單鍵、氧原子、羰基、-C(=O)-O-、-O-C(=O)-或-C(=O)-O-,但其並不限於此。
結構式1中Y表示之單價取代基係包含由至少8個成鏈原子構成之鏈結構。
本申請案中之用語“成鏈原子(chain-forming atom)”係指形成預定鏈之直鏈結構的原子。該鏈可為直鏈型或支鏈型,但是,成鏈原子的數目僅以形成最長直鏈之原子數目計算,而鍵結至上述成鏈原子的其他原子(例如,成鏈原子為碳原子時,鍵結至該碳原子的氫原子等等)並未列入計算。在支鏈的情況中,成鏈原子的數目可以形成最長鏈的成鏈原子數目計算。例如,鏈為正戊基時,所有的成鏈原子是碳且成鏈原子數目為五;而上述鏈為2-甲基戊基
時,所有的成鏈原子是碳且成鏈原子數目為5。成鏈原子(chain-forming atom)的實例可包括碳、氧、硫及氮;合適的成鏈原子可為碳、氧及氮中之任一者,或是碳及氧中之任一者。鏈中的成鏈原子數目可為8或更高、9或更高、10或更高、11或更高、或12或更高。鏈中的成鏈原子數目亦可為30或更低,25或更低,20或更低,或16或更低。
結構式1所示之結構單元可賦予其所屬之上述嵌段共聚物極佳的自組裝性(self-assembling property)。
於一實例中,前述之鏈可為直鏈烴鏈(linear hydrocarbon chain)例如直鏈烷基。此情況中,烷基可為具8或更多個碳、8至30個碳、8至25個碳、8至20個碳、或8至16個碳的烷基。上述烷基中的一或更多碳原子可各自任意地經氧原子取代,且烷基中的至少一個氫原子可各任意地經其他取代基取代。
結構式1中,Y可包含環結構,上述之鏈可連接至該環結構。此環結構可使其所屬之由單體所組成之嵌段共聚物的自組裝性等等獲得進一步的改良。環結構可為芳族結構或脂環族結構。
上述之鏈可直接連接至上述環結構或可經由連接子連接至上述環結構。連接子(linker)的實例可包括氧原子、硫原子、-NR1-、-S(=O)2-、羰基、伸烷基、伸烯基、伸炔基、-C(=O)-X1-及-X1-C(=O)-,其中,R1可表示氫原子、烷基、烯基、炔基、烷氧基或芳基,且X1可表示單鍵、
氧原子、硫原子、-NR2-、-S(=O)2-、伸烷基、伸烯基或伸炔基,其中R2可表示氫原子、烷基、烯基、炔基、烷氧基、或芳基。合適之連接子的實例可包括氧原子及氮原子。上述之鏈可藉由例如氧原子或氮原子連接至芳族結構。此情況中,上述連接子可為氧原子或-NR1-(其中,R1表示氫原子、烷基、烯基、炔基、烷氧基、或芳基)。
於一實例中,結構式1的Y可由以下結構式2表示。
[結構式2]-P-Q-Z
結構式2中,P表示伸芳基;Q表示單鍵、氧原子或-NR3-,其中,R3表示氫原子、烷基、烯基、炔基、烷氧基或芳基;以及,Z表示上述含8或更多成鏈原子的鏈。結構式1的Y是結構式2所示取代基時,結構式2的P可直接連接至結構式1的X。
結構式2之P的合適實例可包括,但不限於:具6至12個碳的伸芳基,例如伸苯基(phenylene group)。
結構式2之Q的合適實例可包括氧原子及-NR1-(其中,R1表示氫原子、烷基、烯基、炔基、烷氧基、或芳基)。
結構式1之結構單元的合適實例可包括:結構式1之結構單元中,R表示氫原子或烷基(例如,具1至4個碳的烷基),X表示-C(=O)-O-,以及Y係由結構式2表示,其中,P表示具6至12個碳的伸苯基(phenylene)或伸芳基,Q表示氧原子,以及Z表示前述之含8或更多成
鏈原子的鏈。
因此,合適的結構式1之結構單元的例子可包括以下結構式3所示之結構單元。
結構式3中,R表示氫原子或具1至4個碳原子的烷基,X表示-C(=O)-O-,P表示具6至12個碳的伸芳基,Q表示氧原子,以及,Z表示前述之含8或更多成鏈原子的鏈。
於另一實例中,嵌段1之結構單元(由結構式1所示)亦可由以下結構式4表示。
結構式4中,R1及R2係各自獨立地表示氫原子或具
1至4個碳的烷基;X表示單鍵、氧原子、硫原子、-S(=O)2-、羰基、伸烷基、伸烯基、伸炔基、-C(=O)-X1-或-X1-C(=O)-,其中,X1表示單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基;T表示單鍵或伸芳基;Q表示單鍵或羰基;以及,Y表示含8或更多成鏈原子的鏈。
結構式4中,X可表示單鍵、氧原子、羰基、-C(=O)-O-、或-O-C(=O)-。
結構式4之Y的鏈之具體實例可與於結構式1所述者相同。
於另一實例中,可在嵌段1之任一結構單元(由結構式1、3及4表示)中所含的鏈(具8或更多成鏈原子)之至少一成鏈原子觀察到陰電性(electronegativity)為3或更高。於另一實例中,上述原子的陰電性可為3.7或更低。其陰電性為3或更高之上述原子的實例可包括,但不限於:氮原子及氧原子。
與嵌段1(其含有上述結構單元)一起包含在嵌段共聚物中的嵌段2,可至少含有由以下結構式5表示之結構單元。
結構式5中,X2表示單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基、伸炔基、-C(=O)-X2-或-X2-C(=O)-,其中,X2表示單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基;以及,R1至R5係各自獨立地表示氫原子、烷基、鹵烷基、鹵素原子或交聯官能基(crosslinking functional group),其中,標為R1至R5的位置所含之交聯官能基的數目為1或更多。
嵌段2可僅由結構式5所示之結構單元所組成或者含有一或更多另外的結構單元(將於本說明書後文中描述)。嵌段2除了結構式5所示之結構單元以外還含有一或更多另外的結構單元時,各結構單元可於嵌段2中形成個別次嵌段(subblock)、或隨機安置。
如上所述,結構式5所示之結構單元含有至少一交聯官能基。嵌段共聚物可在形成自組裝結構(self-assembled structure)之前或之後藉由此交聯官能基而交聯。僅於嵌段2中引發交聯反應時,可改進嵌段1與嵌段2之間的蝕刻
選擇性(etching selectivity)。
對可含於結構式5所示之結構單元中的交聯官能基(crosslinking functional group)之種類並無特別限制;可使用任何種類的交聯官能基,只要其可藉由例如加熱或光照射(photoirradiation)而實現交聯結構(crosslinked structure)即可。交聯官能基的實例可包括,但不限於:含疊氮官能基(azide-containing functional group)(例如,諸如疊氮烷基羰基氧基(azide alkylcarbonyloxy group)、環氧丙基疊氮(glycidyl azide)、及羥苯基疊氮(hydroxyphenyl azide)的含疊氮官能基)、含硫官能基(sulfur-containing functional group)、以及含不飽和雙鍵之官能基。
結構式5所示之結構單元可含有1或更多交聯官能基(crosslinking functional group);例如,至少R3可表示上述交聯官能基。
結構式5所示之結構單元,除了上述交聯官能基以外,可含有1或更多、2或更多、3或更多、4或更多、或5或更多鹵素原子(例如,氟原子)。結構單元中所含之鹵素原子(諸如氟原子)的數目,亦可為10或更少、9或更少、8或更少、7或更少、或6或更少。
結構式5所示之結構單元中,R1至R5中之至少一者、1至3者或1至2者可表示上述交聯官能基。
結構式5所示之結構單元中,標為R1至R5的位置中可含有1或更多、2或更多、3或更多、4或更多、或5或更多鹵素原子。標為R1至R5的位置中所含之鹵素原子
的數目亦可為10或更少、9或更少、8或更少、7或更少、或6或更少。
當嵌段2,除了結構式5所示之結構單元以外,含有另外的結構單元時,可將結構式5所示之結構單元的比例調整至在維持嵌段共聚物之自組裝性同時能發生足夠的交聯反應之範圍。例如,上述結構單元(結構式5所示)於嵌段2中的比例可為約0.1mol%至5mol%、0.5mol%至5mol%、1mol%至5mol%、1.5mol%至5mol%、1.5mol%至4mol%、或1.5mol%至3mol%(以嵌段2中之結構單元的總莫耳數為基準計)。可依據嵌段共聚物中所含之結構單元或嵌段的種類而調整此比例。
嵌段共聚物之嵌段2,除了上述結構式5所示之結構單元以外,可含有另外的結構單元。於此例中,可另外含有之結構單元的種類並無特別限制。
例如,嵌段2可另外含有聚乙烯吡咯啶酮(polyvinylpyrrolidone)結構單元、聚乳酸(polylactic acid)結構單元、聚乙烯吡啶(poly(vinylpyridine))結構單元、聚苯乙烯(polystyrene)結構單元諸如聚苯乙烯及聚(三甲基矽基苯乙烯)(poly(trimethylsilyl styrene))、聚環氧烷(polyalkylene oxide)結構單元諸如聚環氧乙烷(polyethylene oxide)、聚丁二烯(polybutadiene)結構單元、聚異戊二烯(polyisoprene)結構單元、或聚烯烴(polyolefin)結構單元諸如聚乙烯(polyethylene)。
於一實例中,嵌段2可含有,除了結構式5所示之結
構單元以外,具有含一或更多鹵素原子之芳族結構的結構單元。
例如,上述結構單元可為不含交聯官能基的結構單元(與結構式5不同)。
嵌段2之此第二結構單元可為例如由以下結構式6所示之結構單元。
結構式6中,B表示具有含一或更多鹵素原子之芳族結構的單價取代基。
含有如上述者之結構單元的嵌段可透過具有與其他嵌段如嵌段1的極佳交互作用而賦予所屬之嵌段共聚物極佳的自組裝性(self-assembling property)。
結構式6中,芳族結構可為例如具6至18個碳或6至12個碳的芳族結構。
結構式6之鹵素原子的例子可為氟原子或氯原子,且較佳選擇氟原子,但不限於此。
於一實例中,結構式6的B可為具有含6至12個碳且經1或更多、2或更多、3或更多、4或更多、或5或更多鹵素原子部份取代的芳族結構之單價取代基。於以上描述中,對鹵素原子的最大數目並無特別限制,且可存在例如10或更少、9或更少、8或更少、7或更少、或6或更少個鹵素原子。
於此例中,上述結構單元(結構式6所示)亦可由以下結構式7表示。
結構式7中,,X2表示單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基、伸炔基、-C(=O)-X1-或-X1-C(=O)-,其中,X1表示單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基;以及,W表示具至少一鹵素原子的芳基。W可為經至少一鹵素原子部份取代的芳基;例如,其可為具6至12個碳且經2或更多、3或更多、4或更多、或5或更多鹵素原子部份取代的芳基。
於另一實例中,上述結構單元(結構式6所示)亦可由以下結構式8表示。
結構式8中,X3表示單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基、伸炔基、-C(=O)-X1-或-X1-C(=O)-,其中,X1表示單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基;以及,Ra至Re係各自獨立地表示氫原子、烷基、鹵烷基或鹵素原子,其中,標為Ra至Re的位置中所含之鹵素原子的數目為1或更多。
於另一實例中,結構式8的X3可表示單鍵、氧原子、伸烷基、-C(=O)-O-、或-O-C(=O)-。
結構式8中,Ra至Re係各自獨立地表示氫原子、烷基、鹵烷基或鹵素原子,標為Ra至Re的位置中可含有1或更多、2或更多、3或更多、4或更多、或5或更多鹵素原子(例如,氟原子)。標為Ra至Re的位置中所含之鹵素原子(例如,氟原子)的數量亦可為10或更少、9或更少、8或更少、7或更少、或6或更少。
當嵌段2,除了結構式5所示之結構單元以外,含有上述具有含一或更多鹵素原子之芳族結構的結構單元(例如,結構式6至8中任一者所示之結構單元)時,上述結構單元(具有含一或更多鹵素原子之芳族結構)的莫耳數(DH)對結構式5所示之結構單元的莫耳數(D5)之比例(DH/D5)可為約35至65、約40至60、或約40至50。
本申請案之嵌段共聚物為由一或更多的各上述之嵌段1及嵌段2所組成的嵌段共聚物。其可為僅由兩種上述嵌段所組成之二嵌段共聚物(diblock copolymer)、或者其可
為三嵌段(triblock)或多嵌段(multiblock)(具有大於三種嵌段)共聚物(其含有2或更多的嵌段1和嵌段2之一或兩者或者含有嵌段1和嵌段2以外之其他種類的嵌段)。
如上述者之嵌段共聚物本質上可展現極佳的相分離(phase separation)或極佳的自組裝性(self-assembling property)。藉由嵌段之適當的選擇和組合以及符合本說明書下文中所描述的一或多個參數,可進一步改善相分離或自組裝性。
嵌段共聚物含有透過共價鍵彼此連接的2或更多聚合物鏈(polymer chain),因而發生相分離。本申請案之嵌段共聚物展現相分離性(phase separation property),且需要時可藉由微相分離(microphase separation)形成奈米尺寸結構。此奈米結構的形式及尺寸可藉由嵌段共聚物的尺寸(分子量等等)或嵌段間的相對比例而控制。可藉由相分離而形成之結構的實例可包括球、圓柱、螺旋二十四面體(gyroid)、層狀物(lamella)及倒置結構(inverted structure),嵌段共聚物形成此結構的能力可稱為“自組裝(self-assembling)”。本案發明人證實,在本說明書之上述各種嵌段共聚物中,符合說明書下文中所述之各種參數中至少一者的嵌段共聚物可展現出對嵌段共聚物基本上具有之自組裝性(self-assembling property)的顯著改良。本申請案之嵌段共聚物可符合任一參數,或者可同時符合2或更多參數。尤其是,證實可藉由符合一或更多適當參數而使嵌段共聚物展現垂直定向(vertical orientation)。本申請案
中,用語“垂直定向(vertical orientation)”是指嵌段共聚物定位的方向且可以是指嵌段共聚物所形成之奈米結構係以垂直於基板的方向定位。控制嵌段共聚物之自組裝結構為平行或垂直於各種基板的技術係於嵌段共聚物之實際應用中占極大部分。在嵌段共聚物膜中之奈米結構的定向(orientation)通常取決於構成嵌段共聚物的嵌段中之暴於表面或空氣中的嵌段為何。一般而言,多數基板具極性且空氣為非極性;因而構成嵌段共聚物的嵌段中之具有較高極性的嵌段係潤濕(wet)於基板,而具有較低極性的嵌段係潤濕於與空氣之界面(interface)。因此,提出許多技術以使得嵌段共聚物中各具不同性質的不同種類嵌段同時能潤濕基板側,其中最具代表性者為產生中性表面以控制定向。不過,於本申請案之一態樣中,當適當控制以下參數時,嵌段共聚物亦可垂直定向於並未以本領域已知能達成垂直定向的任何方法(例如表面中性化(surface neutralization))事先處理之基板。此外,於本申請案之另一態樣中,藉由熱退火(thermal annealing),亦可在短時間內於大面積獲致如上述之垂直定向。
本申請案一態樣之嵌段共聚物可形成膜,其在掠角入射小角度X射線散射(grazing-incidence small-angle X-ray scattering)(GISAXS)期間於疏水表面產生面內繞射圖案(in-plane diffraction pattern)。上述嵌段共聚物可形成膜,其在GISAXS期間於親水表面產生面內繞射圖案(in-plane diffraction pattern)。
本申請案中,在GISAXS期間產生面內繞射圖案係可指在GISAXS分析期間,在GISAXS繞射圖案中有垂直於x分量(x-component)的峰(peak)。能觀察到此峰係因嵌段共聚物的垂直定向所致。因此,產生面內繞射圖案之嵌段共聚物,表明了垂直定向。於另一實例中,上述於GISAXS繞射圖案的x分量(x-component)觀察到的峰的數量可為至少2,當出現多個峰時,可證實峰之散射向量(scattering vector)(q值)具有整數比,於該情況中,可進一步改良嵌段共聚物之相分離效率(phase separation efficiency)。
本申請案中,“垂直”係考量誤差的用語;例如,此用語之定義可包括±10度、±8度、±6度、±4度、或±2度範圍內的誤差。
能夠形成在親水表面和疏水表面二者上產生面內繞射圖案之膜的嵌段共聚物可在未事先以任何引發垂直定向之特定方法處理的各種表面上展現垂直定向。本申請案中,用語“親水表面(hydrophilic surface)”是指其對純水的潤濕角(wetting angle)為5度至20度的表面。親水表面的實例可包括,但不限於:以氧電漿(oxygen plasma)、硫酸或食人魚洗液(piranha solution)表面處理過的矽(silicon)表面。本申請案中,用語“疏水表面(hydrophobic surface)”是指其對純水的室溫潤濕角為50度至70度的表面。疏水表面的實例可包括,但不限於:以氧電漿(oxygen plasma)表面處理過的聚二甲基矽氧烷(polydimethylsiloxane)(PDMS)表
面、以六甲基二矽氮烷(hexamethyldisilazane)(HMDS)表面處理過的矽(silicon)表面、和以氟化氫(HF)表面處理過的矽(silicon)表面。
除非另有具體指明,本申請案中,會隨溫度而改變之性質(例如,潤濕角)係於室溫測量的數值。用語“室溫”是指未經加熱或冷卻之自然狀態下的溫度,可指為約10℃至30℃、約25℃、或約23℃的溫度。
形成於親水或疏水表面且於GISAXS期間產生面內繞射圖案的膜可為經熱退火(thermal annealing)的膜。用於GISAXS之量測的膜的形成係可藉由例如將溶液(將上述嵌段共聚物以約0.7wt%的濃度溶於溶劑(例如,氟苯(flourobenzene))而製備)施加於對應的親水或疏水表面上,厚度為約25nm且塗覆面積為2.25cm2(寬:1.5cm,長:1.5cm),並對塗層進行熱退火。熱退火係可藉由例如使上述膜於約160℃的溫度維持約1小時而進行。GISAXS之量測係可藉由使X射線以在約0.12至0.23度之範圍的入射角入射於以前述方式所製之膜。藉由本領域熟知的測量裝置(例如,2D marCCD),可得到從膜散射的繞射圖案。利用繞射圖案確認是否有面內繞射圖案(in-plane diffraction pattern)的方法係本領域已知的。
GISAXS期間觀察到具有上述峰的嵌段共聚物可展現極佳的自組裝性(self-assembling property),其亦可根據目的而有效控制。
本申請案之嵌段共聚物可在X射線繞射(XRD)分析
時於預定散射向量q範圍內顯現至少一個峰。
例如,上述嵌段共聚物於XRD分析時可在0.5nm-1至10nm-1的散射向量q範圍具有至少一個峰。於另一實例中,出現上述峰的散射向量q可為0.7nm-1或更高、0.9nm-1或更高、1.1nm-1或更高、1.3nm-1或更高、或1.5nm-1或更高。再者,於另一實例中,出現上述峰的散射向量q可為9nm-1或更低、8nm-1或更低、7nm-1或更低、6nm-1或更低、5nm-1或更低、4nm-1或更低、3.5nm-1或更低、或3nm-1或更低。
在上述散射向量q範圍內所觀察到的峰的半高寬(full width at half maximum)(FWHM)可為於0.2至0.9nm-1的範圍。於另一實例中,上述FWHM可為0.25nm-1或更高、0.3nm-1或更高、或0.4nm-1或更高。再者,於另一實例中,上述FWHM可為0.85nm-1或更低、0.8nm-1或更低、或0.75nm-1或更低。
本申請案中,用語“半高寬(full width at half maximum)”可指最大的峰於最大振輻的一半處之寬度(即,兩散射向量q極值(extreme scattering vector q value)間的差)。
上述於XRD分析中之散射向量q及FWHM係藉由數值分析方法(利用XRD分析結果之最小平方迴歸(least-squares regression))所獲得的數值。上述方法中,對應於XRD繞射圖案中最低強度的部分係設為基線(baseline)且將最低強度設為零,然後使上述XRD圖案之峰輪廓(peak
profile)進行高斯擬合(Gaussian fitting),從擬合結果獲得上述之散射向量q及FWHM。進行上述高斯擬合時,R平方值(R-square value)為至少0.9或更高、0.92或更高、0.94或更高、或0.96或更高。從XRD分析獲得資訊的方法(如上所述)是本領域已知的;例如,可使用數值分析程式,諸如Origin。
於前述散射向量q範圍產生具有前述FWHM值之峰的嵌段共聚物可具有適於自組裝的結晶區(crystalline region)。於前述散射向量q範圍確認的嵌段共聚物可展現極佳的自組裝性(self-assembling property)。
XRD分析可藉由令X射線通過嵌段共聚物樣品之後測量相關於散射向量之散射強度而進行。可對嵌段共聚物進行XRD分析而毋需任何特定前處理;例如,其可藉由使嵌段共聚物在適當條件下乾燥之後令X射線通過彼而進行。可使用垂直尺寸為0.023mm及水平尺寸為0.3mm的X射線。可透過藉由使用測定裝置(例如,2D marCCD)得到從樣品散射的2D繞射圖案之影像以及對所得的繞射圖案之擬合(上述方法中),以獲得散射向量及FWHM。
當構成嵌段共聚物之嵌段中的至少一者含有上述鏈時(如於本說明書下文中所述),該鏈中之成鏈原子的數目n可符合由前述XRD分析所得之散射向量q、以及以下的方程式1。
[方程式1]3nm-1至5nm-1=nq/(2×π)
方程式1中,n表示前述成鏈原子的數目,而q表示上述嵌段共聚物之XRD分析中可偵測到之峰的最小散射向量、或者是觀察到具有峰面積最大之峰的散射向量。此外,方程式1中,π表示圓之圓周對其直徑的比。
方程式1中的q等等係以如前述XRD分析方法中所述之同樣方式所得到的數值。
方程式1的q可為例如於0.5nm-1至10nm-1範圍的散射向量。於另一實例中,方程式1的q可為0.7nm-1或更高、0.9nm-1或更高、1.1nm-1或更高、1.3nm-1或更高、或1.5nm-1或更高。再者,於另一實例中,方程式1的q可為9nm-1或更低、8nm-1或更低、7nm-1或更低、6nm-1或更低、5nm-1或更低、4nm-1或更低、3.5nm-1或更低、或3nm-1或更低。
方程式1描述了嵌段共聚物為自組裝(self-assembled)而形成相分離結構(phase-separated structure)時之嵌段(含有上述鏈)間的距離D與成鏈原子數目之間的關係。含有上述鏈之嵌段共聚物中的成鏈原子數目符合方程式1時,該鏈的結晶性(crystallinity)提高,因而相分離(phase separation)或垂直定向(vertical orientation)性質可獲大幅改良。於另一實例中,方程式1中的nq/(2×π)可為4.5nm-1或更低。以上描述中的含有上述鏈之嵌段間的距離(D,單位是nm)係可藉使用方程式D=2×π/q來計算,其中,D表示上述嵌段間的距離(D,單位是nm),而π和q則如方程式1中所定義。
於本申請案一態樣中,嵌段共聚物中的嵌段1之表面能與嵌段2之表面能之間的差的絕對值可為10mN/m或更低、9mN/m或更低、8mN/m或更低、7.5mN/m或更低、或7mN/m或更低。再者,上述表面能之間的差的絕對值可為1.5mN/m、2mN/m、或2.5mN/m或更高。嵌段1和嵌段2(其具有之表面能間之差的絕對值係於上述範圍)經由共價鍵彼此連接之結構係可獲致因足夠之不混溶性(immiscibility)程度而相分離所致之微相分離(microphase separation)。以上描述中之嵌段1可為例如上述含有前述的鏈之嵌段。
可使用液滴形狀分析儀(Drop Shape Analyzer)DSA100(KRUSS GmbH製造)測定表面能。具言之,係可於如下製備之膜測定表面能:將塗覆溶液(將待測定的標的樣品(即,嵌段共聚物或均聚物(homopolymer))溶於氟苯至固體濃度(solid concentration)為約2wt%而製備)施加於基板上,厚度為約50nm且塗覆面積為4cm2(寬:2cm,長:2cm),於室溫乾燥約1小時,之後於160℃熱退火約1小時。藉由於上述經熱退火的膜上滴加去離子水(其表面張力為本領域已知)以測定接觸角(contact angle)的方法係重覆5次,並計算該5次接觸角測量值的平均。同樣地,於上述經熱退火的膜上滴加二碘甲烷(diiodomethane)(其表面張力為本領域已知)以測定接觸角的方法係重覆5次,並計算該5次接觸角測量值的平均。接著,使用分別利用去離子水和二碘甲烷所測量之
接觸角的平均值,並將對應溶劑之表面張力的數值(Strom值)代入方程式(根據Owens-Wendt-Rabel-Kaelble方法),以獲得表面能。對應於嵌段共聚物中各嵌段之表面能的數值係可藉由對僅由構成上述嵌段之單體所組成的均聚物(homopolymer)使用上述方法而得到。
在嵌段共聚物含有上述鏈的情況中,含有該鏈的嵌段可具有比其他嵌段還高的表面能。例如,若嵌段共聚物之嵌段1含有上述之鏈,則嵌段1的表面能會大於嵌段2的表面能。此情況中,嵌段1的表面能可為於約20mN/m至40mN/m的範圍。上述嵌段1的表面能可為22mN/m或更高、24mN/m或更高、26mN/m或更高、或28mN/m或更高。再者,上述嵌段1的表面能可為38mN/m或更低、36mN/m或更低、34mN/m或更低、或32mN/m或更低。含有上述嵌段1且嵌段1所具有之表面能係如上所述地不同於嵌段2之表面能的嵌段共聚物,可展現極佳的自組裝性(self-assembling property)。
嵌段共聚物中,嵌段1與嵌段2間的密度之差的絕對值可為0.25g/cm3或更高、0.3g/cm3或更高、0.35g/cm3或更高、0.4g/cm3或更高、或0.45g/cm3或更高。上述密度之差的絕對值可為0.9g/cm3或更低、0.8g/cm3或更低、0.7g/cm3或更低、0.65g/cm3或更低、或0.6g/cm3或更低。其中嵌段1與嵌段2係具有於上述範圍內的密度之差的絕對值且係經由共價鍵彼此連接的結構,可獲致有效的微相分離(因足夠之不混溶性(immiscibility)程度而
相分離所致)。
上述嵌段共聚物中各嵌段的密度可利用本領域已知的減浮法(buoyancy method)來量測;例如,可藉由分析嵌段共聚物在溶劑諸如乙醇(其於空氣中的質量和密度係已知)中的質量以測定密度。
嵌段共聚物含有上述鏈時,含有該鏈的嵌段之密度係低於其他嵌段。例如,當嵌段共聚物之嵌段1含有上述鏈時,嵌段1的密度會低於嵌段2的密度。此情況中,嵌段1的密度可於約0.9g/cm3至1.5g/cm3的範圍。上述嵌段1的密度可為0.95g/cm3或更高。上述嵌段1的密度可為1.4g/cm3或更低、1.3g/cm3或更低、1.2g/cm3或更低、1.1g/cm3或更低、或1.05g/cm3或更低。含有上述嵌段1且嵌段1之密度係如上所述地不同於嵌段2之密度的嵌段共聚物,可展現極佳的自組裝性。上述表面能和密度可為於室溫測得之數值。
嵌段共聚物可含有體積分率(volume fraction)係於0.4至0.8之範圍的嵌段以及體積分率係於0.2至0.6之範圍的嵌段。在嵌段共聚物含有上述鏈的情況中,含有該鏈之嵌段的體積分率係可於0.4至0.8之範圍。例如,該鏈係包含於嵌段1中時,嵌段1的體積分率可為於0.4至0.8之範圍,而嵌段2的體積分率可為於0.2至0.6之範圍。嵌段1與嵌段2的體積分率之總和可等於1。以上述體積分率而含有各嵌段的嵌段共聚物可展現極佳的自組裝性。嵌段共聚物中各嵌段的體積分率可根據嵌段的密度以及分
子量(以凝膠滲透層析法(gel permeation chromatography)(GPC)測量)而獲得。
嵌段共聚物之數量平均分子量(Mn)可為例如於3,000至300,000之範圍。本說明書中,用語“數量平均分子量(number average molecular weight)”是指以GPC測定且根據標準品聚苯乙烯校準(calibrate)之數值,並且,除非另有具體指明,本說明書中之用語“分子量”是指數量平均分子量。於另一實例中,Mn可為例如3000或更高、5000或更高、7000或更高、9000或更高、11000或更高、13000或更高、或15000或更高。於又另一實例中,Mn可為約250000或更低、200000或更低、180000或更低、160000或更低、140000或更低、120000或更低、100000或更低、90000或更低、80000或更低、70000或更低、60000或更低、50000或更低、40000或更低、30000或更低、或25000或更低。嵌段共聚物之多分散性(polydispersity)(Mw/Mn)可為於1.01至1.60之範圍。於另一實例中,Mw/Mn可為約1.1或更高、約1.2或更高、約1.3或更高、或約1.4或更高。
於此範圍內,嵌段共聚物可展現足夠的自組裝性。嵌段共聚物的Mn等等係可考量目標之自組裝結構等等而加以調整。
在嵌段共聚物至少含有上述嵌段1及嵌段2的情況中,於上述嵌段共聚物中之嵌段1的比例(例如,含有上述鏈之嵌段的比例)可為於10mol%至90mol%的範圍。
本申請案中,對製備如上述之嵌段共聚物的詳細方法並無特別限制,只要該方法包括使用可形成各上述結構單元的單體以形成嵌段共聚物之至少一嵌段即可。
例如,可藉活性自由基聚合反應(living radical polymerization)(LRP)方法(使用上述單體)以製備嵌段共聚物。該方法之實例包括:利用陰離子聚合反應(anionic polymerization)合成,其中,係在鹼金屬與無機酸鹽諸如鹼土金屬的存在下,使用有機稀土金屬錯合物(organic rare-earth metal complex)或有機鹼金屬化合物作為聚合反應引發劑;利用陰離子聚合反應法合成,其中,係在有機鋁化合物存在下,使用有機鹼金屬化合物作為聚合反應引發劑;原子轉移自由基聚合反應(atom transfer radical polymerization)(ATRP)法,其中係使用ATRP劑作為聚合反應控制劑;電子轉移再生活化劑(activators regenerated by electron transfer)(ARGET)之ATRP法,其中係使用ATRP劑作為聚合反應控制劑,而聚合反應係在產生電子的有機或無機還原劑存在下發生;引發劑持續再生活化劑(initiators for continuous activator regeneration)(ICAR)之ATRP法;利用可逆加成-開環鏈轉移(reversible addition-fragmentation chain transfer)(RAFT)法之聚合反應,其中係使用無機還原劑以及RAFT劑;以及,使用有機碲化合物作為引發劑之方法,可由其中選擇合適的方法來使用。
例如,上述嵌段共聚物之製備係可藉由:在自由基引發劑(radical initiator)及活性自由基聚合反應劑(living
radical polymerization reagent)存在下,利用活性自由基聚合反應(living radical polymerization)法,將反應物(其包含能形成上述嵌段之單體)加以聚合。
在嵌段共聚物之製造中,對欲與上述單體所形成之嵌段一起包含於嵌段共聚物中的另外的嵌段之形成方法並無特別限制;可考量用於形成其他嵌段之目標嵌段種類以適當選擇單體。
製備嵌段共聚物的方法可進一步包括例如令藉由上述方法製得的聚合產物沉澱於非溶劑(nonsolvent)中。
對自由基引發劑(radical initiator)的種類並無特別限制,可考量聚合效能而適當地選擇自由基引發劑;例如,可使用偶氮化合物諸如偶氮雙異丁腈(azobisisobutyronitrile)(AIBN)及2,2’-偶氮雙-(2,4-二甲基戊腈)(2,2’-azobis-(2,4-dimethylvaleronitrile))、或過氧化物類諸如苄醯基過氧化物(benzoyl peroxide)(BPO)及二-三級丁基過氧化物(di-t-butyl peroxide)(DTBP)。
活性自由基聚合反應(living radical polymerization)方法係可在例如溶劑(諸如二氯甲烷、1,2-二氯乙烷、氯苯、二氯苯、苯、甲苯、丙酮、氯仿、四氫呋喃、二烷(dioxane)、單甘醇二甲醚(monoglyme)、二甘醇二甲醚(diglyme)、二甲基甲醯胺、二甲亞碸、及二甲基乙醯胺(dimethylacetamide))中進行。
非溶劑(nonsolvent)的實例包括,但不限於:醇(如甲醇、乙醇、正丙醇及異丙醇)、二醇(如乙二醇)、正
己烷、環己烷、正庚烷,以及醚(如石油醚(petroleum ether))。
本申請案亦關於包含上述之嵌段共聚物的聚合物膜。聚合物膜可於各種應用中使用,例如,各種電子或電性裝置、形成上述圖案之方法、磁性儲存記錄媒介(magnetic storage recording media)諸如快閃記憶體(flash memory)、或者生物感測器(biosensor)。
於一實例中,上述嵌段共聚物可藉由上述聚合物膜中之自組裝(self-assembly)而實現規則結構(regular structure),例如球、圓柱、螺旋二十四面體(gyroid)或層狀物(lamella)。
例如,在嵌段共聚物中,嵌段1、嵌段2或(在共價結合至嵌段1及嵌段2中任一者之其他嵌段的鏈段中)鏈段(segment)可形成規則結構諸如層狀物型或圓柱型。
本申請案中之上述聚合物膜,於GISAXS分析時,可具有面內繞射圖案(in-plane diffraction pattern),其係垂直於GISAXS繞射圖案之x分量(x-component)的峰(peak)。於另一實例中,沿上述GISAXS繞射圖案之x分量所觀察到之峰的數量可為至少2,當出現多個峰時,觀察到之峰的散射向量q值可為整數比(integer ratio)。
上述嵌段2可於如上述之聚合物膜中形成交聯結構。即,可藉由例如於自組裝結構(self-assembled structure)存在下使上述嵌段2中之結構式5之結構單元的交聯官能基進行交聯的方法而形成交聯結構(crosslinked structure)。
於此情況中,形成交聯結構的條件並無特別限制且可考量所使用之交聯官能基的種類及量而加以調整。例如,上述交聯官能基為前述之含疊氮官能基(azide-containing functional group)中之一者時,可藉由使自組裝的嵌段共聚物維持於約200℃至230℃的溫度約30分鐘至1小時以進行交聯。
本申請案亦關於利用上述嵌段共聚物形成聚合物膜之方法。該方法可包括於基板上形成包含上述嵌段共聚物的聚合物膜(於自組裝狀態)。例如,上述方法可包括藉由沉積(deposition)等等在基板上形成上述嵌段共聚物之層或者塗覆溶液(其中,嵌段共聚物係溶於適當溶劑中)之層,且需要時亦可包括退火(annealing)或熱處理上述層的程序。
上述之退火或者熱處理(heat-treating/heat-treatment)係可例如基於嵌段共聚物的相轉變溫度(phase transition temperature)或玻璃轉變溫度(glass transition temperature)而進行;例如,其可在等於或高於上述玻璃轉變溫度或相轉變溫度的溫度進行。未特別限制此熱處理的時間,可為例如於約1分鐘至72小時的範圍(可因需求而改變)。此外,聚合物薄膜的熱處理溫度可為例如約100℃至250℃,其可視所使用之嵌段共聚物而改變。
於另一實例中,如上述所形成的層可於室溫在非極性溶劑及/或極性溶劑中進行溶劑退火(solvent-anneal)約1分鐘至72小時。
可於聚合物膜如上述形成之後另進行交聯上述嵌段2的程序。此交聯之進行係如本說明前文中所描述。
本申請案亦關於形成圖案之方法。上述方法可包括例如從由基板以及聚合物膜(其係形成於該基板上且包含上述自組裝的嵌段共聚物)所組成的層合物(laminate)選擇性地移除嵌段共聚物的嵌段1或嵌段2的程序。上述方法可為於上述基板形成圖案的方法。例如,上述方法可包括於基板上形成含有上述嵌段共聚物的聚合物膜、選擇性地移除存在於上述膜中之嵌段共聚物的任一或更多嵌段、以及接著蝕刻該基板。上述方法使得能形成例如為奈米尺寸(nanoscale)的微圖案(micropattern)。此外,視聚合物膜中之嵌段共聚物的結構而定,可藉上述方法形成各種圖案諸如奈米棍(nanorod)及奈米孔(nanohole)。需要時,上述嵌段共聚物可與其他共聚物或均聚物等等混合,以形成圖案。上述方法中所使用之基板的種類並無特別限制,可配合應用而選擇;例如,可使用氧化矽(silicon oxide)。
在選擇性地移除上述嵌段1及/或嵌段2的程序中所使用之上述聚合物膜中的嵌段2,可含有交聯結構(crosslinked structure),其中,實現交聯結構之方法係如本說明書前文中所述。
例如,上述方法可形成具有高縱橫比(aspect ratio)之氧化矽的奈米尺寸圖案。例如,藉由在氧化矽上形成上述聚合物膜、選擇性地移除上述聚合物膜中之嵌段共聚物的任一嵌段(其中該嵌段共聚物構成預定結構)、以及接著
以各種方法(例如,反應性離子蝕刻(reactive-ion etching))中的任一者蝕刻氧化矽,以完成各種形式如奈米棍(nanorod)及奈米孔(nanohole)。此外,上述方法,可實現具有高縱橫比的奈米圖案。
例如,可實現為數十奈米尺寸的上述圖案,且此圖案可用於各種用途,包括,例如,次世代資訊及電子之磁性記錄媒介(magnetic recording media)。
例如,藉上述方法可形成其中寬度為約3nm至40nm之奈米結構(例如,奈米線)係間隔(例如,以6nm至80nm)設置的圖案。於另一實例中,可實現其中寬度(例如,直徑)為約3nm至40nm之奈米孔係以約6nm至80nm而間隔設置的結構。
此外,上述結構之奈米線或奈米孔可形成為具有高縱橫比。
上述方法中,對選擇性地移除嵌段共聚物之任一嵌段的方法並無特別限制;例如,可使用以適當電磁波(例如,紫外線)照射聚合物膜以移除相對軟嵌段之方法。此情況中,紫外線照射的條件係由嵌段共聚物中的嵌段類型而決定;例如,可包括以波長為約254nm的紫外線照射1分鐘至60分鐘。
此外,紫外線照射之後,可藉由使用酸等等來處理聚合物膜以進行進一步移除之前被紫外線破壞的鏈段的程序。
此外,對於使用聚合物膜(已選擇性地移除某些嵌
段)作為遮罩以蝕刻基板之方法並無特別限制;例如,上述蝕刻可藉由使用CF4/Ar離子等等的反應性離子蝕刻(reactive-ion etching)來進行。在上述蝕刻之後可進行藉由氧電漿處理等等而從基板移除聚合物膜的程序。
本申請案可提供嵌段共聚物及其用途。本申請案之嵌段共聚物具有極佳的自組裝性(self-assembling property)或相分離性(phase separation property),可具備各種需要的功能而無限制,尤其是可確保蝕刻選擇性(etching selectivity),使該嵌段共聚物可有效的應用於例如圖案形成等用途。
圖1及2為說明聚合物膜之SEM結果的影像。
以下透過根據本申請案之實施例更詳細描述本申請案,但本申請案之範疇並未受限於以下所提之實施例。
NMR分析係於室溫、藉由使用包括具5-mm三重共振探針(triple resonance probe)之Varian Unity Inova(500MHz)光譜儀的NMR光譜儀進行。分析標的材料係以溶劑
(CDCl3)稀釋(用於NMR量測)至約10mg/ml的濃度待用,化學位移(chemical shift)係以ppm表示。
br=寬訊號(broad signal),s=單峰(singlet),d=二重峰(doublet),dd=雙二重峰(doublet of doublet),t=三重峰(triplet),dt=雙三重峰(doublet of triplet),q=四重峰(quartet),p=五重峰(quintet),m=多重峰(multiplet)。
藉GPC測定數量平均分子量(Mn)和分子量分佈(molecular weight distribution)。將分析標的材料例如巨分子引發劑(macroinitiator)或實施例的嵌段共聚物置於5-mL小瓶中並以四氫呋喃(THF)稀釋至約1mg/mL的濃度。然後將用於校準的標準品及待分析的樣品以注射過濾器(syringe filter)(孔尺寸:0.45μm)過濾之後進行分析。使用ChemStation(Agilent Technologies Inc.)作為分析程式,藉由將樣品的沖提時間(elution time)與校準曲線(calibration curve)比對,以得到各重量平均分子量(Mw)及Mn,然後分子量分佈(多分散性指數(polydispersity index),PDI)係計算為比例(Mw/Mn)。GPC的測量條件如下:
裝置:Agilent Technologies Inc.的1200系列
管柱:Polymer Laboratories的兩PLgel MIXED-B
溶劑:THF
管柱溫度:35℃
樣品濃度:1mg/mL,注射200L
標準品:聚苯乙烯(Mp:3900000,723000,316500,52200,31400,7200,3940,485)
藉以下方法合成由以下結構式A所示之化合物(DPM-C12):於250-mL瓶中加入氫醌(hydroquinone)(10.0g,94.2mmol)及1-溴十二烷(1-bromododecane)(23.5g,94.2mmol),溶於100mL乙腈中;然後將過量的碳酸鉀添加至上述溶液並使於氮氣氛下在約75℃反應約48小時;反應完成後,反應產物係移除所餘之碳酸鉀和反應所用的乙腈;之後,物質係透過添加二氯甲烷(DCM)和水之混合溶劑進行後處理(work up),分離的有機層係以MgSO4脫水;接著,使用管柱層析術(column chromatography)(CC)以DCM進行物質之純化以獲得白色固體中間物,產率為約37%。
<中間物(intermediate)的NMR分析結果>
1H-NMR(CDCl3):δ6.77(dd,4H);δ4.45(s,1H);δ 3.89(t,2H);δ1.75(p,2H);δ1.43(p,2H);δ1.33-1.26(m,16H);δ0.88(t,3H)。
將合成的中間物(9.8g,35.2mmol)、甲基丙烯酸(6.0g,69.7mmol)、二環己碳二亞胺(dicyclohexylcarbodiimide)(DCC)(10.8g,52.3mmol)及對-二甲胺基吡啶(p-dimethylaminopyridine)(DMAP)(1.7g,13.9mmol)加入瓶中,添加120mL二氯甲烷,然後使於氮氣氛下在室溫反應24小時;反應完成後,過濾反應產物以移除反應期間產生之脲鹽(urea salt)以及所餘之二氯甲烷;然後藉由使用己烷和二氯甲烷(DCM)作為流動相(mobile phase)的管柱層析術(CC)移除物質之雜質,所得產物在甲醇和水的混合溶劑(以1:1重量比混合)中再結晶以獲得白色固體標的物(DPM-C12)(7.7g,22.2mmol),產率為63%。
<DPM-C12的NMR分析結果>
1H-NMR(CDCl3):δ7.02(dd,2H);δ6.89(dd,2H);δ6.32(dt,1H);δ5.73(dt,1H);δ3.94(t,2H);δ2.05(dd,3H);δ1.76(p,2H);δ1.43(p,2H);1.34-1.27(m,16H);δ0.88(t,3H)。
結構式A中,R表示具12個碳的直鏈烷基。
由以下結構式B所示之化合物係藉由以下方式合成:首先,3-羥基-1,2,4,5-四氟苯乙烯(3-hydroxy-1,2,4,5-tetrafluorostyrene)之合成及獲得係藉由:將五氟苯乙烯(pentafluorostyrene)(25g,129mmol)添加至400mL之三級丁醇(tert-butanol)和氫氧化鉀(37.5g,161mmol)的混合溶液中,令其全進行2小時的回流反應(reflux reaction);反應物冷卻至室溫,然後添加1200mL水;加成物(adduct)以二乙醚(diethyl ether)(300mL)萃取三次(透過使任何所餘之用於先前反應的丁醇揮發的程序);水溶液層係以10-wt%鹽酸溶液酸化至pH為約3以沉澱標的物;藉由再以二乙醚(300mL)萃取3次以收集有機層然後以MgSO4脫水並移除溶劑;以及,藉由使用己烷和二氯甲烷(DCM)作為流動相的管柱層析術純化所得之粗產物以得到無色的液態3-羥基-1,2,4,5-四氟苯乙烯(11.4g)。上述物質之NMR分析結果如下。
1H-NMR(DMSO-d):δ11.7(s,1H);δ6.60(dd,1H);δ5.89(d,1H);δ5.62(d,1H)
將所得之3-羥基-1,2,4,5-四氟苯乙烯(3.0g,16mmol)、氯乙醯氯(chloroacetyl chloride)(3.5g,31mmol)及三乙胺(2.5g,25mmol)溶於乙醚(250mL);反應1小時後,反應產物係移除溶劑然後置入通
過管柱層析(與氯甲烷(MC)/己烷溶液)以獲得透明液態標的化合物(由以下結構式B表示)(2g,8mmol,51%)。
上述化合物之NMR分析結果如下。
1H-NMR(CDCl3-d):δ6.66(dd,1H);δ6.12(d,1H);δ5.75(d,1H),δ4.41(s,2H)
為了使用合成單體以聚合嵌段共聚物,使用偶氮雙異丁腈(azobisisobutyronitrile)(AIBN)作為聚合引發劑(polymerization initiator),其係與可逆加成裂片鏈轉移(reversible addition-fragmentation chain transfer)(RAFT)劑(2-氰基-2-丙基十二基三硫碳酸酯(2-cyano-2-propyl dodecyl trithiocarbonate))及製備例1之結構式A所示的化合物(DPM單體)溶於大茴香醚(anisole)中,重量比為
30:2:0.2(DPM:RAFT劑:AIBN),以獲得固體濃度為約30wt%的溶液。令上述溶液在氮氣氛下於70℃反應4小時以合成巨分子引發劑(數量平均分子量:6800,分子量分佈:1.16),其係與AIBN、五氟苯乙烯(PFS)及上述結構式B之化合物(製備例2)溶於大茴香醚(anisole)中,重量比為1:490:10:0.5(巨分子引發劑:PFS:結構式B所示化合物:AIBN)以製備固體濃度為約70wt%的溶液。使所製得的溶液在氮氣氛下於70℃反應2.5小時以製備嵌段共聚物(數量平均分子量:13500,分子量分佈:1.20)。所製得之嵌段共聚物係與NaN3在室溫反應24小時以用疊氮官能基(azide functional group)取代所含的氯離子(Cl)(其係衍生自化合物(由結構式B表示)的結構單元),以獲得嵌段共聚物。
使用實施例1中合成的嵌段共聚物形成自組裝聚合物膜並觀察其結果。所製得之嵌段共聚物係溶於溶劑至濃度為0.5wt%後,以約3000rpm的速度、約60秒鐘旋塗(spin-coat)於矽晶圓(silicon wafer)以形成聚合物薄膜。該膜係於160℃熱退火1小時以引發微相分離(microphase separation),可於下圖1中看到對應之嵌段共聚物的微結構。圖2顯示結果確認交聯(crosslinking)上述嵌段共聚物(於約200℃或更高)之後的選擇性蝕刻,如圖2所示上述嵌段共聚物之選擇性蝕刻(selective etching)成為可能。
Claims (21)
- 一種嵌段共聚物,其包括含有以下結構式1所示之結構單元的第一嵌段、以及含有以下結構式3所示之結構單元的第二嵌段:
- 如申請專利範圍第1項之嵌段共聚物,其中,X表示單鍵、氧原子、羰基、-C(=O)-O-、或-O-C(=O)-。
- 如申請專利範圍第1項之嵌段共聚物,其中,該直鏈含有8至20個成鏈原子。
- 如申請專利範圍第1項之嵌段共聚物,其中,該成鏈原子為碳、氧、氮或硫。
- 如申請專利範圍第1項之嵌段共聚物,其中,該成鏈原子為碳或氧。
- 如申請專利範圍第1項之嵌段共聚物,其中,Y之環結構為芳環結構或脂環族環(alicyclic ring)結構。
- 如申請專利範圍第1項之嵌段共聚物,其中,結構式1之Y係由以下結構式2所示:[結構式2]-P-Q-Z其中,結構式2中,P表示伸芳基;Q表示單鍵、氧原子或-NR3-,其中,R3表示氫原子、烷基、烯基、炔基、烷氧基或芳基;以及 Z表示具8或更多成鏈原子的直鏈。
- 如申請專利範圍第1項之嵌段共聚物,其中,該交聯官能基(crosslinking functional group)為含疊氮官能基(azide-containing functional group)、含硫官能基(sulfur-containing functional group)、或含一或更多不飽和雙鍵之官能基。
- 如申請專利範圍第1項之嵌段共聚物,其中,結構式3中標為R1至R5的位置包含一或更多鹵素原子。
- 如申請專利範圍第1項之嵌段共聚物,包括:該第二嵌段包含比例範圍為0.1mol%至5mol%的結構式3之結構單元。
- 如申請專利範圍第1項之嵌段共聚物,其中,該第二嵌段進一步包含由以下結構式4所示之結構單元:
- 如申請專利範圍第1項之嵌段共聚物,其中,該 第二嵌段進一步包含由以下結構式5所示之結構單元:
- 如申請專利範圍第12項之嵌段共聚物,其中,標為Ra至Re的位置包含3或更多鹵素原子。
- 如申請專利範圍第12項之嵌段共聚物,其中,標為Ra至Re的位置包含5或更多鹵素原子。
- 如申請專利範圍第12項之嵌段共聚物,其中,該鹵素原子為氟原子。
- 一種聚合物膜,其包括如申請專利範圍第1項之嵌段共聚物,其中,該嵌段共聚物為自組裝的(self- assembled)。
- 如申請專利範圍第16項之聚合物膜,其中,該嵌段共聚物之第二嵌段包含交聯結構(crosslinked structure)。
- 一種形成聚合物膜之方法,該方法包括:於基板上形成包含如申請專利範圍第1項之嵌段共聚物的聚合物膜,其中,該嵌段共聚物為自組裝的。
- 如申請專利範圍第18項之方法,進一步包括:交聯(crosslinking)該嵌段共聚物之第二嵌段,其中,該嵌段共聚物為自組裝的。
- 一種形成圖案之方法,該方法包括:從由基板以及聚合物膜所組成的層合物(laminate)選擇性地移除如申請專利範圍第1項之嵌段共聚物的任一嵌段,該聚合物膜係形成於該基板上且包含該嵌段共聚物,其中,該嵌段共聚物為自組裝的。
- 如申請專利範圍第20項之聚合物膜,其中,該嵌段共聚物之第二嵌段包含交聯結構(crosslinked structure)。
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