TWI591085B - 嵌段共聚物 - Google Patents
嵌段共聚物 Download PDFInfo
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- TWI591085B TWI591085B TW103142790A TW103142790A TWI591085B TW I591085 B TWI591085 B TW I591085B TW 103142790 A TW103142790 A TW 103142790A TW 103142790 A TW103142790 A TW 103142790A TW I591085 B TWI591085 B TW I591085B
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- carbon atoms
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- block
- block copolymer
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- 229920001400 block copolymer Polymers 0.000 title claims description 79
- 125000003118 aryl group Chemical group 0.000 claims description 69
- 125000005843 halogen group Chemical group 0.000 claims description 62
- 125000004432 carbon atom Chemical group C* 0.000 claims description 61
- 125000003342 alkenyl group Chemical group 0.000 claims description 52
- 125000000304 alkynyl group Chemical group 0.000 claims description 51
- 125000001424 substituent group Chemical group 0.000 claims description 51
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 47
- 125000000217 alkyl group Chemical group 0.000 claims description 45
- 125000004429 atom Chemical group 0.000 claims description 43
- 125000002947 alkylene group Chemical group 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 34
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 30
- 229910052717 sulfur Inorganic materials 0.000 claims description 30
- 125000004434 sulfur atom Chemical group 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 26
- 125000003545 alkoxy group Chemical group 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- -1 X 1 is Single bond Chemical group 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 150000001450 anions Chemical class 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 125000001188 haloalkyl group Chemical group 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 150000001721 carbon Chemical group 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000002560 nitrile group Chemical group 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 3
- 150000001345 alkine derivatives Chemical class 0.000 claims 1
- 125000000732 arylene group Chemical group 0.000 claims 1
- 125000003943 azolyl group Chemical group 0.000 claims 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 125000005567 fluorenylene group Chemical group 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 125000000335 thiazolyl group Chemical group 0.000 claims 1
- 125000001544 thienyl group Chemical group 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- 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 26
- 239000010410 layer Substances 0.000 description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 150000002738 metalloids Chemical class 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 238000001338 self-assembly Methods 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 125000004122 cyclic group Chemical group 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000523 sample Substances 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000010526 radical polymerization reaction Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 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 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052752 metalloid Inorganic materials 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 230000002441 reversible effect Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 125000005647 linker group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000002070 nanowire Substances 0.000 description 3
- 239000012985 polymerization agent Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- NCLFXQTYZIBYNO-UHFFFAOYSA-N CCCCCCCCCCCCC(CC(CCC)(CCCCCCCCCC)C#N)OC(=O)O Chemical compound CCCCCCCCCCCCC(CC(CCC)(CCCCCCCCCC)C#N)OC(=O)O NCLFXQTYZIBYNO-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
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 230000032683 aging Effects 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
- 238000004630 atomic force microscopy Methods 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
- 230000000052 comparative effect Effects 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
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 239000003505 polymerization initiator Substances 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
- 150000004060 quinone imines Chemical class 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000003303 reheating Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 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
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- MYMSJFSOOQERIO-UHFFFAOYSA-N 1-bromodecane Chemical compound CCCCCCCCCCBr MYMSJFSOOQERIO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WZKHBEGQWSEAJI-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol;1-methoxy-2-(2-methoxyethoxy)ethane Chemical compound OCCOCCO.COCCOCCOC WZKHBEGQWSEAJI-UHFFFAOYSA-N 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- VXVUDUCBEZFQGY-UHFFFAOYSA-N 4,4-dimethylpentanenitrile Chemical compound CC(C)(C)CCC#N VXVUDUCBEZFQGY-UHFFFAOYSA-N 0.000 description 1
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-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
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-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
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 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
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
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- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000006612 decyloxy group Chemical group 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000001654 grazing-incidence X-ray scattering Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229940030980 inova Drugs 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 1
- 239000011707 mineral 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
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
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- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
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- 239000004626 polylactic acid Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002717 polyvinylpyridine 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011084 recovery Methods 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
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 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
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
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
-
- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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Description
本發明係關於嵌段共聚物。
嵌段共聚物具有化學結構彼此不同的聚合物次單元藉共價鍵彼此連接之分子結構。嵌段共聚物能夠經由相分離而形成週期性排列的結構,如球、圓筒或積層。藉嵌段共聚物之自組裝而形成之結構的區域尺寸可調整於寬範圍內,並可製成各種結構形狀。因此,彼等可用於藉蝕刻而形成圖案的方法、各種磁性記錄介質或新一代奈米裝置(如金屬點、量子點或奈米線)、高密度磁性儲存介質等。
本申請案提供嵌段共聚物和其應用。
除非另外界定,否則文中所用“烷基”是指具1至20,1至16,1至12,1至8,或1至4個碳原子的烷基。烷基可具有直鏈、支鏈或環狀結構,且可任意地經至少一個取代基取代。
除非另外界定,否則文中所用“烷氧基”是指具1至20,1至16,1至12,1至8,或1至4個碳原子的烷氧基。烷氧基可具有直鏈、支鏈或環狀結構,且可任意地經至少一個取代基取代。
除非另外界定,否則文中所用“烯基或炔基”是指具2至20,2至16,2至12,2至8,或2至4個碳原子的烯基或炔基。烯基或炔基可具有直鏈、支鏈或環狀結構,且可任意地經至少一個取代基取代。
除非另外界定,否則文中所用“伸烷基”是指具1至20,1至16,1至12,1至8,或1至4個碳原子的伸烷基。伸烷基可具有直鏈、支鏈或環狀結構,且可任意地經至少一個取代基取代。
除非另外界定,否則文中所用“伸烯基或伸炔基”是指具2至20,2至16,2至12,2至8,或2至4個碳原子的伸烯基或伸炔基。伸烯基或伸炔基可具有直鏈、支鏈或環狀結構,且可任意地經至少一個取代基取代。
除非另外界定,否則文中所用“芳基或伸芳基”是指自包括一個苯環結構的化合物衍生的單價或二價取代基,或至少兩個苯環以共享的一或兩個碳原子或藉任
意的連接劑連接之結構,或此化合物之衍生物。除非另外界定,否則芳基或伸芳基可為具6至30,6至25,6至21,6至18,或6至13個碳原子的芳基。
文中所用“芳族結構”是指芳基或伸芳基。
除非另外界定,否則文中所用“脂環族結構”是指非芳環結構的環狀烴結構。除非另外界定,否則脂環族結構可為具3至30,3至25,3至21,3至18,或3至13個碳原子的結構。
文中所用“單鍵”是指在相關位置沒有原子的情況。例如,“A-B-C”所示結構中的“B”是單鍵的情況,意謂“B”位置沒有原子並因此而使得“A-C”所示結構係藉“A”直接連接至“C”而形成。
可任意地取代烷基、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可為羥基、鹵原子、羧基、環氧丙基、丙烯醯基、甲基丙烯醯基、丙烯醯氧基、甲基丙烯醯氧基、巰基、烷基、烯基、炔基、伸烷基、伸烯基、伸炔基、烷氧基或芳基,但不限於此。
一個具體實施例中,提供具有新穎結構且能夠形成嵌段共聚物之以下的式1所示單體。
式1中,R是氫或烷基,X是單鍵、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可為氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基,而Y可為包括具8或更多個成鏈原子連接之環狀結構的單價取代基。
另一具體實施例中,式1中,X可為單鍵、氧原子、羰基、-C(=O)-O-或-O-C(=O)-;或X可為-C(=O)-O-,但不限於此。
式1中,單價取代基Y包括藉至少8個成鏈原子形成的鏈結構。
文中所用“成鏈原子”是指形成某些鏈的直鏈結構之原子。此鏈可具有直鏈或支鏈結構;但是,成鏈原子的數目僅以形成最長直鏈的原子數計算。因此,其他原子如,在成鏈原子是碳原子的情況中,連接至碳原子之類的氫原子未計入成鏈原子數。此外,在支鏈的情況中,成鏈原子數是形成最長鏈的原子數。例如,鏈為正戊基,所有的成鏈原子是碳原子且其數目為5。若鏈是2-甲基戊基,所有的成鏈原子亦為碳原子且其數目是5。成鏈原子可為碳、氧、硫或氮等且適當的成鏈原子可為碳、氧或氮;或碳或氧。成鏈原子的數目可為8或更高,9或更高,10或更高,11或更高,或12或更高。成鏈原子數可為30或更低,25或更低,20或更低,或16或更低。
當式1化合物形成嵌段共聚物時,因為鏈的存在,嵌段共聚物可展現極佳的自組裝性質。
一個具體實施例中,鏈可為直鏈烴鏈,如直鏈烷基。此情況中,烷基可為具8或更多,8至30,8至25,8至20,或8至16個碳原子的烷基。烷基的至少一個碳原子可任意地經氧原子取代,且烷基的至少一個氫原子可任意地經另一取代基取代。
式1中,Y可包括環狀結構。此鏈可連接至環狀結構。藉化合物形成之嵌段共聚物的自組裝性質可因為環狀結構而獲進一步改良。環狀結構可為芳族結構或脂環族結構。
此鏈可直接連接至環狀結構或可經由連接劑連接至環狀結構。作為連接劑,氧原子、硫原子、-NR1-、-S(=O)2-、羰基、伸烷基、伸烯基、伸炔基、-C(=O)-X1或-X1-C(=O)-可為例示。其中,R1可為氫、烷基、烯基、炔基、烷氧基或芳基且X1可為單鍵、氧原子、硫原子、-NR2-、-S(=O)2-、伸烷基、伸烯基或伸炔基,其中,R2可為氫、烷基、烯基、炔基、烷氧基或芳基。適當的連接劑可為氧原子或氮原子。例如,此鏈可經由氧原子或氮原子連接至芳族結構。此情況中,此連接劑可為氧原子或-NR1-、其中,R1可為氫、烷基、烯基、炔基、烷氧基或芳基。
一個具體實施例中,式1的Y可係由以下的式2表示。
[式2]-P-Q-Z
式2中,P可為伸芳基,Q可為單鍵、氧原子或-NR3-,其中,R3可為氫、烷基、烯基、炔基、烷氧基或芳基,而Z是具至少8個成鏈原子的鏈。在式1的Y是式2的取代基的情況中,式2的P可直接連接至式1的X。
式2中,適當的P可為具6至12個碳原子的伸芳基,如伸苯基,但不限於此。
式2中,適當的Q可為氧原子或-NR1-,其中,R1可為氫、烷基、烯基、炔基、烷氧基或芳基。
作為式1所示之單體之適當的具體實施例,式1單體中的R為氫原子或烷基;或氫原子或具1至4個碳原子的烷基,X為-C(=O)-O-且Y為式2的取代基,其中,P是具6至12個碳原子的伸芳基或伸苯基,Q是氧原子且Z是具8或更多個成鏈原子的鏈。
因此,作為適當的具體實施例,以下的式3之單體可為例示。
式3中,R是氫原子或具1至4個碳原子的
烷基,X是-C(=O)-O-,P是具6至12個碳原子的伸芳基,Q是氧原子,Z是前述具8或更多個成鏈原子的鏈。
本申請案的另一具體實施例係關於製造嵌段共聚物之方法,其包含藉聚合單體而形成嵌段之步驟。
未特別限制製造嵌段共聚物之特定方法,只要其包含藉由使用前述單體形成嵌段共聚物的至少一個嵌段的步驟即可。
例如,可藉存活的自由基聚合反應(LPR)使用單體製造嵌段共聚物。例如,方法如陰離子聚合反應,其中,在無機酸鹽(如鹼金屬或鹼土金屬鹽)存在下,合成嵌段共聚物,此使用有機稀土金屬錯合物或有機鹼金屬化合物作為聚合反應引發劑;陰離子聚合反應,其中,在有機鋁化合物存在下,合成嵌段共聚物,此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(ATRP),此使用原子轉移自由基聚合劑作為聚合反應控制劑;藉電子轉移(ATGET)ATRP產生的活化劑進行聚合反應,此在生成電子的有機或無機還原劑存在下,使用原子轉移自由基聚合反應劑作為聚合反應控制劑;用於連續活化劑再生(ICAR)ATRP之引發劑;可逆加成-開環鏈轉移(RAFT)聚合反應,其使用無機還原劑可逆加成-開環鏈轉移劑;及使用有機鉈化合物作為引發劑之方法,適當的方法可選自以上方法。
一個具體實施例中,製造嵌段共聚物的方法可包括在自由基引發劑和存活的自由基聚合反應劑存在
下,藉存活的自由基聚合反應,將包含能夠形成嵌段的單體之材料加以聚合。
在嵌段共聚物之製造中,未特別限制用於形成嵌段共聚物中所含括之其他嵌段及藉以上單體形成嵌段的方法,此其他嵌段可藉由考慮待形成的嵌段種類,選擇適當的單體而形成。
製造嵌段共聚物之方法可進一步包括令藉前述方法製得的聚合產物沉澱於非溶劑中。
可以考慮聚合效能,無特別限制地適當地選擇自由基引發劑的種類,且可以使用偶氮化合物(如偶氮基雙異丁腈(AIBN)或2,2’-偶氮基雙-(2,4-二甲基戊腈))或過氧化物化合物(如苄醯基過氧化物(BPO)或二-三級丁基過氧化物(DTBP))。
LPR可在溶劑(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、二噁烷、乙二醇二甲醚(monoglyme)、二乙二醇二甲醚(diglyme)、二甲基甲醯胺、二甲亞碸或二甲基乙醯胺)中進行。
作為非溶劑,例如,可以無限制地使用醇(如甲醇、乙醇、正丙醇或異丙醇)、二醇(如乙二醇)、或醚化合物(如正己烷、環己烷、正庚烷或石油醚)。
本申請案的另一具體實施例係關於包括藉由使用單體而形成的嵌段(下文中,可稱為第一嵌段)之嵌
段共聚物。
此嵌段可藉,例如,式4表示。
式4中,R、X和Y可與前述關於式1的R、X和Y所述者相同。
因此,式4中,R可為氫或具1至4個碳原子的烷基,X可為單鍵、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是氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基,而Y是單價取代基,其含有具有8或更多個成鏈原子的鏈連接之環狀結構。至於以上各取代基的特定類型,以上描述可以相同方式施用。
一個具體實施例中,第一嵌段可為式4的嵌段,其中,R是氫或烷基;或氫或具1至4個碳原子的烷基,X是-C(=O)-O-,Y是式2所示的取代基。可將此嵌段稱為1A嵌段,但不限於此。此嵌段可由以下的式5表示。
式5中,R可為氫原子或具1至4個碳原子的烷基,X可為單鍵、氧原子、-C(=O)-O-或-O-C(=O)-,P可為伸芳基,Q可為氧原子或-NR3-,其中,R3可為氫、烷基、烯基、炔基、烷氧基或芳基,Z是具8或更多成鏈原子的鏈。另一具體實施例中,式5的Q可為氧原子。
另一具體實施例中,第一嵌段可為藉式6所示的嵌段。文中可將此第一嵌段稱為1B嵌段。
式6中,R1和R2可以各自獨立地為氫或具1至4個碳原子的烷基,X可為單鍵、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可為單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基,T可為單鍵或伸芳基,Q可為單鍵或羰基且Y可為具有至少8個成鏈原子的鏈。
式6的1B嵌段中,X可為單鍵、氧原子、羰基、-C(=O)-O-或-O-C(=O)-。
作為1B嵌段中之鏈Y的特別具體實施例,以上關於式1之描述可以類似方式施用至彼。
另一具體實施例中,第一嵌段可為藉式4至6中之至少一者所示的嵌段,其中,具8或更多個成鏈原子之至少一個成鏈原子的陰電性是3或更高。另一具體實施例中,成鏈原子的陰電性可為3.7或更低。此處,可將此嵌段稱為1C嵌段。陰電性為3或更高的原子的例子可為氮原子或氧原子,但不限於此。
未特別限制嵌段共聚物中與第一嵌段(如1A、1B或1C)一併含括之另一嵌段(下文中稱為第二嵌段)的類型。
例如,第二嵌段可為聚乙烯基吡咯烷酮嵌段、聚乳酸嵌段、聚乙烯基吡啶嵌段、聚苯乙烯嵌段(如聚苯乙烯嵌段或聚三甲基甲矽基苯乙烯)、聚伸烷化氧嵌段(如聚伸乙化氧嵌段)或聚烯烴嵌段(如聚乙烯嵌段或
聚異戊烯嵌段或聚丁二烯嵌段)。可將此處所用嵌段稱為2A嵌段。
一個具體實施例中,與第一嵌段(如1A、1B或1C嵌段)一起含括於嵌段共聚物中之第二嵌段可為包括含有至少一個鹵原子的芳族結構之嵌段。
此第二嵌段可以,例如,由以下的式7表示且可被稱為2B嵌段。
式7中,B可為具有包括至少一個鹵原子的芳族結構之單價取代基。
此第二嵌段可以有效地與前述第一嵌段作用,使得嵌段共聚物具有極佳的自組裝特性。
式7的芳族結構可為,例如,具6至18或6至12個碳原子的芳族結構。
此外,式7中所包括的鹵原子可為,但不限於,氟原子或氯原子,且適當地為氟原子。
一個具體實施例中,式7的B可為單價取代基,該單價取代基具有具6至12個碳原子之芳族結構,其經1或更多,2或更多,3或更多,4或更多,或5或更多個鹵原子取代。未特別限制鹵原子數的上限,但可為
10或更少,9或更少,8或更少,7或更少,或6或更少個鹵原子。
例如,式7所示的嵌段,其為2B嵌段,可由以下的式8表示。
式8中,X2可為單鍵、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是單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基,而W可為經至少一個鹵原子取代的芳基。以上,W可為芳基,其經至少一個鹵原子取代,例如,具6至12個碳原子且經2或更多,3或更多,4或更多,或5或更多個鹵原子取代的芳基。
2B嵌段可以,例如,由以下的式9表示。
式9中,X2可為單鍵、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是單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基,而R1至R5可以各自獨立地為氫、烷基、鹵烷基或鹵原子。R1至R5中所含括的鹵原子數為1或更多。
式9中,另一具體實施例中,X2可為單鍵、氧原子、伸烷基、-C(=O)-O-或-O-C(=O)-。
式9中,R1至R5可以各自獨立地為氫、烷基、鹵烷基或鹵原子,且R1至R5可包括1或更多,2或更多,3或更多,4或更多,或5或更多,個鹵原子,如氟原子。R1至R5所包括的鹵原子(如氟原子)數可為,例如,10或更少,9或更少,8或更少,7或更少,6或更少。
一個具體實施例中,第二嵌段可為式10所示的嵌段。可將此處所用的此嵌段稱為2C嵌段。
式10中,T和K可以各自獨立地為氧原子或單鍵,U可為伸烷基。
一個具體實施例中,2C嵌段中,式10的U可為具1至20,1至16,1至12,1至8或1至4個碳原子的伸烷基。
另一具體實施例中,2C嵌段可為式10的嵌段,其中,式10的T和K之一為單鍵,式10的T和K之他者是氧原子。以上嵌段中,U可為具1至20,1至16,1至12,1至8或1至4個碳原子的伸烷基。
又另一具體實施例中,2C嵌段可為式10的嵌段,式10中的T和K二者是氧原子。以上嵌段中,U可為具1至20,1至16,1至12,1至8或1至4個碳原子的伸烷基。
又另一具體實施例中,第二嵌段可為包括至少一個金屬原子或類金屬原子的嵌段。可將此嵌段稱為2D嵌段。當以例如,包括自組裝的嵌段共聚物之膜進行蝕刻法時,此嵌段可改良蝕刻選擇性。
2D嵌段中的金屬原子或類金屬原子可為矽原子、鐵原子或硼原子,但無特別限制,只要其可因為與嵌段共聚物中之另一原子的差異而展現適當的蝕刻選擇性即
可。
2D嵌段可包括1或更多,2或更多,3或更多,4或更多,或5或更多個鹵原子,例如,氟原子,及金屬或類金屬原子。2D嵌段可包括10或更少,9或更少,8或更少,7或更少,或6或更少個鹵原子,如氟原子。
2D嵌段可藉式11表示。
式11中,B可為具有芳族結構的單價取代基,該芳族結構包含鹵原子和含有陰電性為3或更高的非鹵系原子之取代基。
式11的芳族結構可為具6至12個碳原子的芳族結構,例如,芳基或伸芳基。
式11的2D嵌段可由以下的式12表示。
式12中,X2可為單鍵、氧原子、硫原子、-NR1-、-S(=O)2-、伸烷基、伸烯基、伸炔基、-C(=O)-X1-或-X1-C(=O)-,其中,R1是氫、烷基、烯基、炔基、烷氧基或芳基,X1是單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基,而W可為包括至少一個鹵原子的芳基和包括金屬原子或類金屬原子的取代基。
其中,W可為具6至12個碳原子並包括至少一個鹵原子和包括金屬原子或類金屬原子之取代基的芳基。
芳基可包括至少一或1至3個包括金屬原子或類金屬原子和1或更多,2或更多,3或更多,4或更多,或5或更多個鹵原子的取代基。
其中可包括10或更少,9或更少,8或更少,7或更少,或6或更少個鹵原子。
式12的2D嵌段可由以下的式13表示。
式13中,X2可為單鍵、氧原子、硫原子、-NR1-、-S(=O)2-、伸烷基、伸烯基、伸炔基、-C(=O)-X1-或-X1-C(=O)-,其中,R1可為氫、烷基、烯基、炔基、烷氧基或芳基,而X1可為單鍵、氧原子、硫原子、-NR2-、-S(=O)2-、伸烷基、伸烯基或伸炔基,R1至R5可以各自獨立地為氫、烷基、鹵烷基、鹵原子和包括金屬或類金屬的取代基,前提為R1至R5中之至少一者包括氫原子,且R1至R5中之至少一者係包括金屬或類金屬原子之取代基。
式13中,R1至R5中之1或更多,1至3或1至2者可為包括金屬或類金屬的取代基。
式13中,R1至R5中,可含括1或更多,2或更多,3或更多,4或更多,或5或更多個鹵原子。R1至R5中所含括的鹵原子數可為10或更少,9或更少,8或更少,7或更少,或6或更少。
前述包括金屬或類金屬的取代基可為碳硼基(carboranyl group)或矽倍半氧烷基(如多面狀寡聚矽倍半氧烷)、二茂鐵基或三烷基矽氧基。但是,無特別限制,只要藉由含括至少一種金屬或類金屬原子,其選擇能夠得到蝕刻選擇性即可。
又另一具體實施例中,第二嵌段可為包括陰電性為3或更高且非鹵素原子之原子(下文中稱為非鹵系原子)的嵌段。可將此嵌段稱為2E嵌段。另一具體實施例中,2E嵌段中之非鹵系原子的陰電性可為3.7或更低。
2E嵌段中之非鹵系原子可為,但不限於,氮原子或氧原子。
除了陰電性為3或更高的非鹵系原子以外,2E嵌段可包括1或更多,2或更多,3或更多,4或更多,或5或更多個鹵原子,例如,氟原子。2E嵌段中的鹵原子(如氟原子)數可包括10或更少,9或更少,8或更少,7或更少,或6或更少。
2E嵌段可以式14所示者表示。
式14中,B可為具有芳族結構的單價取代基,該芳族結構包括含有陰電性為3或更高的非鹵系原子和含有鹵原子之取代基。
式14的芳族結構可為具6至12個碳原子的芳族結構,例如,芳基或伸芳基。
另一具體實施例中,式14的嵌段可由以下的式15表示。
式15中,X2可為單鍵、氧原子、硫原子、-NR1-、-S(=O)2-、伸烷基、伸烯基、伸炔基、-C(=O)-X1-或-X1-C(=O)-,其中R1可為氫、烷基、烯基、炔基、烷氧基或芳基,X1可為單鍵、氧原子、硫原子、-NR2-、-S(=O)2-、伸烷基、伸烯基或伸炔基,而W可為芳基,其具有包括含有陰電性為3或更高的非鹵系原子和至少一個鹵原子之取代基的芳基。
其中,W可為具6至12個碳原子的芳基,其包括含有陰電性為3或更高的非鹵系原子並包括至少一個鹵原子之取代基。
此芳基可包括至少一個或1至3個包括具有3或更高的陰電性之非鹵系原子之取代基。此外,此芳基可包括1或更多,2或更多,3或更多,4或更多,5或更多個鹵原子。其中,芳基可包括10或更少,9或更少,8或更少,7或更少,或6或更少個鹵原子。
另一具體實施例中,式15的嵌段可以式16表示。
式16中,X2可為單鍵、氧原子、硫原子、-NR1-、-S(=O)2-、伸烷基、伸烯基、伸炔基、-C(=O)-X1-或-X1-C(=O)-,其中R1是氫、烷基、烯基、炔基、烷氧基或芳基,X1是單鍵、氧原子、硫原子、-NR2-、-S(=O)2-、伸烷基、伸烯基或伸炔基,R1至R5可以各自獨立地為氫、烷基、鹵烷基、鹵原子和包括陰電性為3或更高的非鹵系原子之取代基。其中,R1至R5中之至少一者是鹵原子,且R1至R5中之至少一者是包括陰電性為3或更高的非鹵系原子之取代基。
式16中,R1至R5中之至少一者,1至3,或1至2者可為前述包括陰電性為3或更高的非鹵系原子之取代基。
式16中,R1至R5可包括1或更多,2或更多,3或更多,4或更多,或5或更多個鹵原子。R1至R5可包括10或更少,9或更少,8或更少,7或更少,或6或更少個鹵原子。
前述包括陰電性為3或更高的非鹵系原子之取代基可為,但不限於,羥基、烷氧基、羧基、醯胺基、伸乙氧基、腈基、吡啶基或胺基。
另一具體實施例中,第二嵌段可包括具有雜環狀取代基的芳族結構。可將此第二嵌段稱為2F嵌段。
2F嵌段可由式17表示。
式17中,B可為具有具6至12個碳原子且經雜環狀取代基取代之具有芳族結構的單價取代基。
必要時,式17的芳族結構可包括至少一個鹵原子。
式17的嵌段可以式18表示。
式18中,X2可為單鍵、氧原子、硫原子、-NR1-、-S(=O)2-、伸烷基、伸烯基、伸炔基、-C(=O)-X1-
或-X1-C(=O)-,其中,R1是氫、烷基、烯基、炔基、烷氧基或芳基,X1是單鍵、氧原子、硫原子、-NR2-、-S(=O)2-、伸烷基、伸烯基或伸炔基,而W可為具有6至12個碳原子並具有雜環狀取代基的芳基。
式18的嵌段可以式19表示。
式19中,X2可為單鍵、氧原子、硫原子、-NR1-、-S(=O)2-、伸烷基、伸烯基、伸炔基、-C(=O)-X1-或-X1-C(=O)-,其中,R1是氫、烷基、烯基、炔基、烷氧基或芳基,X1是單鍵、氧原子、硫原子、-NR2-、-S(=O)2-、伸烷基、伸烯基或伸炔基,而R1至R5可以各自獨立地為氫、烷基、鹵烷基、鹵原子或雜環狀取代基。其中,R1至R5中之至少一者是雜環狀取代基。
式19中,R1至R5中之至少一者,例如,1至3或1至2者可為雜環狀取代基,其他者可為氫原子、烷基或鹵原子;或氫原子或鹵原子;或氫原子。
上述雜環狀取代基可為,但不限於,自酞醯亞胺衍生的取代基、自噻吩衍生的取代基、自噻唑衍生的取代基、自咔唑衍生的取代基或自咪唑衍生的取代基。
本申請案之嵌段共聚物可包括至少一個上述第一嵌段和至少一個上述第二嵌段。此嵌段共聚物可包括2或3個嵌段,或3或更多個嵌段。具體實施例中,嵌段共聚物可為包括第一嵌段之任一者和第二嵌段之任一者的二嵌段共聚物。
嵌段共聚物可具有,例如,約3,000至300,000範圍內的數量平均分子量。文中所用“數量平均分子量”是指藉GPC(凝膠穿透層析法)測定,相對於聚苯乙烯標準品之轉化值。除非另外指出,否則文中所用“分子量”是指數量平均分子量。另一具體實施例中,分子量(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。另一具體實施例中,此分子量(Mn)可為,例如,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。嵌段共聚物可具有在1.01至1.60之範圍內的多分散性(Mw/Mn)。另一具體實施例中,多分散性可為約1.1或更高,約1.2或更高,約1.3或更高,或約1.4或更高。
在以上範圍中,嵌段共聚物展現適當的自組裝性質。可以考慮目標的自組裝結構,控制嵌段共聚物的數量平均分子量等。
若嵌段共聚物至少包括第一和第二嵌段,則第一嵌段(例如,嵌段共聚物中之包括該鏈的嵌段)之比可在10莫耳%至90莫耳%範圍內。
本申請案係關於包括嵌段共聚物之聚合物層。此聚合物層可用於各種應用。例如,其可用於生物感知器、記錄介質(如快閃記憶體)、磁性記憶介質或圖案形成方法或電力裝置或電子裝置等。
一個具體實施例中,聚合物層中之嵌段共聚物可藉自組裝物製成周期性結構,包括球、圓筒、螺旋二十四面體、或層合物。
例如,在嵌段共聚物中經由共價鍵連接至以上嵌段之第一嵌段或第二嵌段或其他嵌段的一個鏈段中,其他鏈段可形成規則結構,如層合形式、圓筒形式等。
本申請案亦係關於使用嵌段共聚物形成聚合物層之方法。此方法包括在基板上形成包括自組裝狀態之嵌段共聚物之聚合物層。例如,此方法包括形成嵌段共聚物層或藉塗覆之類將塗覆液(其中,嵌段共聚物稀釋於適當溶劑上)塗覆於基板上,和必要時,之後老化或熱處理該層。
此老化或熱處理可基於,例如,嵌段共聚物的相過渡溫度或玻璃轉變溫度,進行,且例如,可於高於
玻璃轉變溫度或相轉變溫度的溫度進行。未特別限制熱處理的時間,且熱處理可進行約1分鐘至72小時,但可因需要而改變。此外,聚合物層的熱處理溫度可為,例如,100℃至250℃,但可考慮此處所用嵌段共聚物而改變。
形成的層可在非極性溶劑和/或極性溶劑中於室溫老化約1分鐘至72小時。
本申請案亦係關於形成圖案的方法。該方法包括從包括基板和形成於基板上並含有自組裝的嵌段共聚物之聚合物層之層合物選擇性地移除嵌段共聚物中的第一或第二嵌段。此方法可為在以上基板上形成圖案之方法。例如,此方法可包括在基板上形成聚合物層,選擇性地移除嵌段共聚物(其為聚合物層)中的一個嵌段或二或更多個嵌段;及之後蝕刻此基板。藉以上方法,例如,可形成奈米尺寸的微圖案。此外,根據聚合物層中之嵌段共聚物的形狀,可藉以上方法形成各種形狀的圖案(如奈米棍或奈米孔)。必要時,為形成圖案,嵌段共聚物可與另一共聚物或均聚物混合。可以無特別限制地選擇施用於此方法之基板的種類,且,例如,可施用氧化矽等。
例如,根據此方法,可形成具有高縱橫比之氧化矽的奈米尺寸圖案。例如,藉由在氧化矽上形成聚合物層,在聚合物層中的嵌段共聚物以預定結構形成的狀態下,選擇性地移除嵌段共聚物的任一嵌段,並以各種方法(例如,反應性離子蝕刻)蝕刻氧化矽,可形成各種類型的圖案(如奈米棍或奈米孔圖案)。此外,根據以上方
法,可形成具有高縱橫比的奈米圖案。
例如,形成的圖案尺寸可為數十奈米,且此圖案可用於各種用途,包括下一代資訊電子磁記錄介質。
例如,藉上述方法,可形成以約6至80奈米的間隔放置之具有約3至40的寬度之奈米結構圖案(例如,奈米線)。另一具體實施例中,可得到例如,約3至40奈米直徑以約6至80奈米間隔排列的奈米孔結構。
此外,此結構中,可形成具有高縱橫比的奈米線或奈米孔。
此方法中,未特別限制選擇性地移除嵌段共聚物中之任何嵌段的方法,例如,可以使用藉照射適當的電磁波(例如,超紫外射線)於聚合物層以移除相對軟嵌段之方法。此情況中,用於超紫外射線的條件可以根據嵌段共聚物的嵌段類型而決定,且具有約254nm的波長之超紫外射線可照射1至60分鐘。
此外,超紫外射線照射之後,聚合物層經酸處理以進一步移除被超紫外射線破壞的鏈段。
此外,對使用自彼選擇性地移除嵌段之聚合物層之基板進行蝕刻處理,此可藉由使用CF4/Ar離子藉反應性離子蝕刻進行,且在以上方法之後,可進一步藉氧電漿處理而自基板移除聚合物層。
本申請案提供嵌段共聚物和其應用。該嵌段共聚物具有極佳的自組裝性質和相分離,且必要時,可自由地對其施加各種要求的功能。
圖1至2是聚合物層的SEM或AFM影像並
出示聚合物層上的GISAXS分析結果。
下文中,將參考實例和比較例,詳細描述本申請案,但本申請案之範圍未限於以下實例。
1. NMR分析
藉由使用包括具有三重共振5mm探頭的Varian Unity Inova(500MHz)光譜儀之NMR光譜儀,於室溫進行NMR分析。待分析的樣品稀釋於用於NMR分析的溶劑(CDCl3)中至約10mg/ml的濃度之後,進行分析,化學位移(δ)以ppm表示。
<縮寫>
br=寬訊號,s=單峰,d=二重峰,dd=兩個二重峰,t=三重峰,dt=兩個三重峰,q=四重峰,p=五重峰,m=多重峰
2. GPC(凝膠穿透層析)
藉GPC(凝膠穿透層析)測定數量平均分子量和多分散性。在5mL小瓶中,實例或比較例之待測定的嵌段共聚物或巨引發劑稀釋至約1mg/mL的濃度。之
後,用於校正的標準樣品和待分析的樣品以注射濾器(孔尺寸:0.45微米)過濾並於之後分析。得自Agilent technologies,Co.的ChemStation作為分析程式。藉由比較樣品的沖提時間和校正曲線,得到數量平均分子量(Mn)和重量平均分子量(Mw),之後自其比(Mw/Mn)得到多分散性(PDI)。GPC的測定條件如下。
<GPC測定條件>
裝置:Agilent technologies,Co.的1200系列
管柱:使用Polymer laboratories,Co.,的PLgel mixed B中之二者
溶劑:THF
管柱溫度:35℃
樣品濃度:1mg/mL,注射200L
標準樣品:聚苯乙烯(Mp:3900000,723000,316500,52200,31400,7200,3940,485)
製備例1
藉以下方法合成以下式A化合物(DPM-C12)。在250mL瓶中,添加氫醌(10.0g,94.2mmole)和1-溴癸烷(23.5g,94.2mmole)並溶於100mL乙腈中,過量的碳酸鉀加至其中,此混合物於75℃在氮下反應約48小時。反應之後,移除剩餘的碳酸鉀和反應所用的乙腈。添加二氯甲烷(DCM)和水之混合溶劑進行處理,收集分離的有機層並經由MgSO4脫水。之後,使用DCM,
經由管柱層析術,得到白色固態中間產物,產率約37%。
<中間產物的NMR分析結果>
1H-NMR(CDCl3):δ6.77(dd,4H);δ4.45(s,1H);δ3.89(t,2H);δ1.75(p,2H);δ1.43(p,2H);δ1.33-1.26(m,16H);δ0.88(t,3H)
合成的中間產物(9.8g,35.2mmole)、甲基丙烯酸(6.0g,69.7mmole)、二環己基碳二亞胺(DCC;10.8g,52.3mmole)和對-二甲胺基吡啶(DMPA;1.7g,13.9mmole)置於瓶中,添加120ml二氯甲烷,於室溫在氮下反應24小時。反應完全之後,藉濾器移除反應中製得的脲鹽,亦移除剩餘的二氯甲烷。使用己烷和DCM(二氯甲烷)作為流動相通過管柱層析術移除雜質,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,藉此得到白色固體產物(DPM-C12)(7.7g,22.2mmole),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)
其中,R是具12個碳原子的直鏈烷基。
實例1
單體之合成
根據以下方法合成3-羥基-1,2,4,5-四氟苯乙烯。五氟苯乙烯(25g,129mmole)加至400mL三級丁醇和氫氧化鉀(37.5g,161mmole)的混合溶液中;之後進行2小時的回流反應。反應之後,產物冷卻至室溫,添加1200mL水,反應所用的剩餘丁醇經揮發。加合物以二乙醚(300mL)萃取三次,含水相以10重量%氫氯酸溶液酸化直到其pH變成3,藉此沉澱出標的產物。沉澱的產物以二乙醚(300mL)萃取三次並收集有機相。有機層藉MgSO4脫水並移除溶劑。粗製產物在管柱層析法中藉由使用己烷和DCM(二氯甲烷)作為流動相而純化,並藉此得到無色的液態3-羥基-1,2,4,5-四氟苯乙烯(11.4g)。其NMR分析結果如下。
<NMR分析結果>
1H-NMR(DMSO-d):δ11.7(s,1H);δ6.60(dd,1H);δ5.89(d,1H);δ5.62(d,1H)
嵌段共聚物之合成
在苯中,AIBN(偶氮基雙異丁腈)、RAFT
(可逆加成裂片鏈轉移)試劑(2-氰基-2-丙基十二碳烷基三巰基碳酸酯)和製備例1的化合物(DPM-C12)以50:1:0.2的重量比(DPM-C12:RAFT試劑:AIBN)溶解(濃度:70重量%),之後,藉由使得此混合物於氮下於70℃反應4小時而製得巨引發劑(數量平均分子量:14000,多分散性:1.2)。之後,在苯中,合成的巨引發劑,3-羥基-1,2,4,5-四氟苯乙烯(TFS-OH)和AIBN(偶氮基雙異丁腈)以1:200:0.5的重量比(巨引發劑:TFS-OH:AIBN)溶解(濃度:30重量%),藉由令此混合物在氮下於70℃反應6小時,製得嵌段共聚物(數量平均分子量:35000,多分散性:1.2)。此嵌段共聚物包括自製備例1的化合物衍生的第一嵌段和自3-羥基-1,2,4,5-四氟苯乙烯衍生的第二嵌段。
實例2
單體之合成
根據以下方法合成以下式H化合物。酞醯亞胺(10.0g,54mmole)和氯甲基苯乙烯(8.2g,54mmole)加至50mL DMF(二甲基甲醯胺)中並於之後在氮下於55℃反應18小時。反應之後,100mL乙酸乙酯和100mL蒸餾水加至反應產物中,之後收集有機層並以鹽水溶液清洗。收集的有機層經MgSO4處理並藉此移除水,最後移除溶劑,之後以戊烷再結晶,以得到白色固態標的化合物(11.1g)。其NMR分析結果如下。
<NMR分析結果>
1H-NMR(CDCl3):δ7.84(dd,2H);δ7.70(dd,2H);δ7.40-7.34(m,4H);δ6.67(dd,1H);δ5.71(d,1H);δ5.22(d,1H);δ4.83(s,2H)
嵌段共聚物之合成
在苯中,AIBN(偶氮基雙異丁腈)、RAFT(可逆加成裂片鏈轉移)試劑(2-氰基-2-丙基十二碳烷基三巰基碳酸酯)和製備例1的化合物(DPM-C12)以50:1:0.2的重量比(DPM-C12:RAFT試劑:AIBN)溶解(濃度:70重量%),之後,藉由使得此混合物於氮下於70℃反應4小時而製得巨引發劑(數量平均分子量:14000,多分散性:1.2)。之後,在苯中,合成的巨引發劑、式H的化合物(TFS-PhIM)和AIBN(偶氮基雙異丁腈)以1:200:0.5的重量比(巨引發劑:TFS-PhIM:AIBN)溶解(濃度:30重量%),藉由令此混合物在氮下於70℃反應6小時,製得嵌段共聚物(數量平均分子量:
35000,多分散性:1.2)。此嵌段共聚物包括自製備例1的化合物衍生的第一嵌段和自式H化合物衍生的第二嵌段。
試驗例1
藉使用實例1和2之嵌段共聚物製得自組裝聚合物層並觀察其結果。特定言之,各嵌段共聚物溶於溶劑中至1.0重量%的濃度,之後以3000rpm的速率以60秒鐘旋轉塗覆於矽晶圓上。之後,藉溶劑回溫或熱回溫進行自組裝。之後,藉由使各聚合物層進行AFM(原子力顯微鏡)分析,以評估自組裝性質。圖1和2分別為實例1和2的結果,且自以上者,證實實現適當的自組裝。
特定言之,圖1係藉由將塗覆液(藉由將實例1的嵌段共聚物溶於甲苯中至1.0重量%的濃度)於3000rpm的速率旋轉塗覆於矽晶圓上達60秒,之後使用THF(四氫呋喃)和去離子水的混合溶劑(THF:去離子水=4:6(重量比)),對塗層進行溶劑為時約2小時的溶劑回溫處理而得之自組裝物的結果,而圖2係藉由將塗覆液(藉由將實例2的嵌段共聚物溶於二噁烷中至1.0重量%的濃度)於3000rpm的速率旋轉塗覆於矽晶圓上達60秒,之後使用氯仿,對塗層進行溶劑為時約2小時的溶劑回溫處理而得之自組裝物的結果。
Claims (14)
- 一種嵌段共聚物,其含有以下式5所示的第一嵌段和以下式14所示且包括含有陰電性為3或更高的非鹵系原子之取代基的第二嵌段:
- 如申請專利範圍第1項之嵌段共聚物,其中該成鏈原子係碳或氧。
- 如申請專利範圍第1項之嵌段共聚物,其中該直鏈係烴鏈。
- 如申請專利範圍第1項之嵌段共聚物,其中該陰電性為3或更高的非鹵系原子係氧原子或氮原子。
- 如申請專利範圍第1項之嵌段共聚物,其中該鹵素原子係氟。
- 如申請專利範圍第1項之嵌段共聚物,其中式14的B係具有芳族結構的單價取代基,該芳族結構具6至12個碳原子並包含至少3個鹵原子及含有陰電性為3或更高的非鹵系原子之取代基。
- 如申請專利範圍第1項之嵌段共聚物,其中該第二嵌段藉以下式16表示:
- 如申請專利範圍第1項之嵌段共聚物,其中該含有陰電性為3或更高的非鹵系原子之取代基係羥基、烷氧基、羧基、醯胺基、伸烷氧基、腈基、吡啶基或胺基。
- 如申請專利範圍第1項之嵌段共聚物,其中該含有具有該陰電性之非鹵系原子之取代基係含有雜環狀取代基的芳族結構。
- 如申請專利範圍第1項之嵌段共聚物,其中該第二嵌段藉以下式19表示:
- 如申請專利範圍第1項之嵌段共聚物,其中該雜環狀取代基是酞醯亞胺基、噻吩基、噻唑基、咔唑基或咪 唑基。
- 一種聚合物層,其含有如申請專利範圍第1項之嵌段共聚物的自組裝產物。
- 一種形成聚合物層之方法,其包括形成含有如申請專利範圍第1項之嵌段共聚物的自組裝產物之聚合物層。
- 一種形成圖案之方法,其含有從包括基板和形成於該基板上並含有如申請專利範圍第1項之嵌段共聚物的自組裝產物之聚合物層之層合物選擇性地移除該嵌段共聚物中的第一嵌段或第二嵌段。
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