WO2011116223A1 - Silicon-containing block co-polymers, methods for synthesis and use - Google Patents
Silicon-containing block co-polymers, methods for synthesis and use Download PDFInfo
- Publication number
- WO2011116223A1 WO2011116223A1 PCT/US2011/028867 US2011028867W WO2011116223A1 WO 2011116223 A1 WO2011116223 A1 WO 2011116223A1 US 2011028867 W US2011028867 W US 2011028867W WO 2011116223 A1 WO2011116223 A1 WO 2011116223A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- monomer
- silicon
- block copolymer
- polystyrene
- copolymer
- Prior art date
Links
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 72
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000010703 silicon Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims description 68
- 229920001400 block copolymer Polymers 0.000 title claims description 39
- 230000015572 biosynthetic process Effects 0.000 title abstract description 18
- 238000003786 synthesis reaction Methods 0.000 title abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 103
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229920001577 copolymer Polymers 0.000 claims abstract description 25
- JGVXFONXFYPFAK-UHFFFAOYSA-N trimethyl(2-methylidenebut-3-enyl)silane Chemical compound C[Si](C)(C)CC(=C)C=C JGVXFONXFYPFAK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004793 Polystyrene Substances 0.000 claims description 37
- 239000002086 nanomaterial Substances 0.000 claims description 35
- 229920002223 polystyrene Polymers 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 12
- 229920006037 cross link polymer Polymers 0.000 claims description 12
- 229920013730 reactive polymer Polymers 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 150000003440 styrenes Chemical class 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims description 9
- VGOXVARSERTCRY-UHFFFAOYSA-N trimethylsilylmethyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OC[Si](C)(C)C VGOXVARSERTCRY-UHFFFAOYSA-N 0.000 claims description 9
- 238000005530 etching Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 238000004528 spin coating Methods 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 238000005577 Kumada cross-coupling reaction Methods 0.000 claims description 5
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 4
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical group ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 claims description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical group CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- BXBLTKZWYAHPKM-UHFFFAOYSA-M magnesium;methanidyl(trimethyl)silane;chloride Chemical compound [Mg+2].[Cl-].C[Si](C)(C)[CH2-] BXBLTKZWYAHPKM-UHFFFAOYSA-M 0.000 claims description 3
- 229920000428 triblock copolymer Polymers 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 abstract description 10
- 229920000359 diblock copolymer Polymers 0.000 abstract description 8
- 238000001459 lithography Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 238000000746 purification Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 229920001195 polyisoprene Polymers 0.000 description 11
- 150000001450 anions Chemical class 0.000 description 10
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000137 annealing Methods 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000000235 small-angle X-ray scattering Methods 0.000 description 5
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 3
- 238000001127 nanoimprint lithography Methods 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- OXHSYXPNALRSME-UHFFFAOYSA-N (4-ethenylphenyl)-trimethylsilane Chemical group C[Si](C)(C)C1=CC=C(C=C)C=C1 OXHSYXPNALRSME-UHFFFAOYSA-N 0.000 description 2
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- LXHGYJCHFQDQSI-UHFFFAOYSA-N 2-methylbuta-1,3-diene trimethyl(2-methylidenebut-3-enyl)silane Chemical compound CC(=C)C=C.C[Si](C)(C)CC(=C)C=C LXHGYJCHFQDQSI-UHFFFAOYSA-N 0.000 description 2
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- OOCUOKHIVGWCTJ-UHFFFAOYSA-N chloromethyl(trimethyl)silane Chemical compound C[Si](C)(C)CCl OOCUOKHIVGWCTJ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920000140 heteropolymer Polymers 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 150000002924 oxiranes Chemical group 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical compound C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000004639 Schlenk technique Methods 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000609 electron-beam lithography Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001464 small-angle X-ray scattering data Methods 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- ZXCGKLJWOOTGQG-UHFFFAOYSA-N styrene trimethyl(2-methylidenebut-3-enyl)silane Chemical compound C[Si](CC(C=C)=C)(C)C.C=CC1=CC=CC=C1 ZXCGKLJWOOTGQG-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- QVPBMCKCBQURHP-UHFFFAOYSA-N tert-butyl-(4-ethenylphenoxy)-dimethylsilane Chemical compound CC(C)(C)[Si](C)(C)OC1=CC=C(C=C)C=C1 QVPBMCKCBQURHP-UHFFFAOYSA-N 0.000 description 1
- YANSSVVGZPNSKD-UHFFFAOYSA-N tert-butyl-dimethyl-(oxiran-2-ylmethoxy)silane Chemical compound CC(C)(C)[Si](C)(C)OCC1CO1 YANSSVVGZPNSKD-UHFFFAOYSA-N 0.000 description 1
- FIONWRDVKJFHRC-UHFFFAOYSA-N trimethyl(2-phenylethenyl)silane Chemical compound C[Si](C)(C)C=CC1=CC=CC=C1 FIONWRDVKJFHRC-UHFFFAOYSA-N 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
- 238000007514 turning Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- 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
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
- B05D3/107—Post-treatment of applied coatings
-
- 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
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
- G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains
-
- 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
- G03F7/165—Monolayers, e.g. Langmuir-Blodgett
-
- 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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
-
- 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
-
- 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
- B05D2203/00—Other substrates
- B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
-
- 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
- B05D2518/00—Other type of polymers
- B05D2518/10—Silicon-containing polymers
Definitions
- the present invention relates to a heteropolymer or copolymer derived from two (or more) monomelic species, at least one of which incorporates a silicon atom.
- Such compounds have many uses including multiple applications in the semiconductor industry including patterning of templates for use in nanoimprint lithography.
- bitpatterned media can circumvent this limitation by creating isolated magnetic islands separated by a nonmagnetic material.
- Nanoimprint lithography is an attractive solution for producing bit patterned media if a template can be created with sub-25 nm features [2].
- Resolution limits in optical lithography and the prohibitive cost of electron beam lithography due to slow throughput [3] necessitate a new template patterning process.
- the self-assembly of diblock copolymers into well-defined structures [4] on the order of 5-100 nm produces produces features on the length scale required for production of bit patterened media.
- the present invention contemplates silicon-containing compositions, methods of synthesis, and methods of use. More specifically, the present invention relates to a heteropolymer or copolymer derived from two (or more) monomeric species, at least one of which comprising silicon. Such compounds have many uses including multiple applications in the semiconductor industry including making templates for nanoimprint lithography.
- the invention relates to a method of synthesizing a silicon-containing block copolymer, comprising: a) providing first and second monomers (and, in some embodiments, additional monomers), said first monomer comprising a silicon atom and said second monomer being a hydrocarbon monomer (lacking silicon) that can be polymerized; b) treating said second monomer under conditions such that reactive polymer of said second monomer is formed; and c) reacting said first monomer with said reactive polymer of said second monomer under conditions such that said silicon-containing block copolymer is synthesized (e.g. a diblock, triblock etc.).
- said second monomer is styrene and said reactive polymer is reactive polystyrene.
- said reactive polystyrene is anionic polystyrene.
- said first monomer is trimethyl-(2-methylene-but-3-enyl)silane.
- said first monomer was synthesized in a Kumada coupling reaction (see reference 10) of chloroprene and (trimethylsilyl)-niethylmagnesium chloride.
- the conditions of step b) comprise polymerization in cyclohexane.
- the method further comprises d) precipitating said silicon-containing block copolymer in methanol.
- said silicon-containing block copolymer is PS-b-PTMSI.
- said first monomer is a silicon- containing methacrylate. In one embodiment, said first monomer is methacryloxymethyltrimethylsilane (MTMSMA). In one embodiment, said silicon-containing block copolymer is Polystyrene-block-polymethacryloxymethyltrimethylsilane or, more simply, PS-b-P(MTMSMA). In one embodiment, said second monomer is a methacrylate. In one embodiment, said second monomer is an epoxide. In one embodiment, said second monomer is a styrene derivative. In one embodiment, said styrene derivative is p-methylstyrene. In one embodiment, said styrene derivative is p-chlorostyrene.
- the silicon-containing block copolymer is applied to a surface, for example, by spin coating, preferably under conditions such that physical features, such as nanostructures that are less than 100 nm in size (and preferably 50 nm or less in size), are formed on the surface.
- the method further comprises the step d) coating a surface with said block copolymer so as to create a block copolymer film, hi one embodiment, the method further comprises the step e) treating said film under conditions such that nanostructures form.
- said nanostructures comprise cylindrical structures, said cylindrical structures being substantially vertically aligned with respect to the plane of the surface.
- said treating comprises exposing said coated surface to a saturated atmosphere of a solvent (a process also known as "annealing"), such as acetone or THE
- a solvent such as acetone or THE
- said surface is on a silicon wafer.
- said treating comprises exposing said coated surface to heat.
- the film can have different thicknesses.
- said surface is not pre-treated with a cross-linked polymer prior to step d).
- said surface is pre-treated with a cross-linked polymer prior to step d).
- a third monomer is provided and reacted, and the resulting block copolymer is a triblock copolymer.
- the invention contemplates a film made according to the process above.
- the method further comprises the step f) etching said nanostructure-containing coated surface.
- the invention relates to a method of synthesizing a silicon-containing block copolymer, comprising: a) providing first and second monomers, said first monomer comprising a hydrocarbon monomer that does not incorporate silicon (i.e. lacking a silicon atom), said second monomer being a monomer that can be polymerized and comprising a silicon atom; b) treating said second monomer under conditions such that reactive polymer of said second monomer is formed; and c) reacting said first monomer with said reactive polymer of said second monomer under conditions such that said silicon-containing block copolymer is synthesized.
- said second monomer is a silicon-containing styrene derivative.
- said styrene derivative is p-trimethylsilyl styrene.
- said second monomer is a silicon-containing methacrylate.
- the method further comprises the step d) coating a surface with said block copolymer so as to create a block copolymer film.
- the silicon-containing block copolymer is applied to a surface, for example, by spin coating, preferably under conditions such that physical features, such as nano structures that are less than 100 nm in size (and preferably 50 nm or less in size), are formed on the surface.
- the method further comprises the step e) treating said film under conditions such that nanostructures form.
- said nanostructures comprises cylindrical structures, said cylindrical structures being substantially vertically aligned with respect to the plane of the surface.
- said treating comprises exposing said coated surface to a saturated atmosphere of a solvent (a process also known as "annealing") such as acetone or THE
- said treating comprises exposing said coated surface to heat.
- the film can have different thicknesses.
- said surface is on a silicon wafer.
- said surface is not pre-treated with a cross-linked polymer prior to step d).
- said surface is pre-treated with a cross-linked polymer prior to step d).
- the invention relates to a method wherein a third monomer is provided and said block copolymer is a triblock copolymer. In one embodiment, the invention relates to a film made according to the process above. In one embodiment, the method further comprises the step f) etching said nanostructure-containing coated surface.
- the invention relates to a method forming nanostructures on a surface, comprising: a) providing a silicon-containing block copolymer such as PS-b-P(MTMSMA) and a surface; b) spin coating said block copolymer on said surface to create a coated surface; and c) treating said coated surface under conditions such that nanostructures are formed on said surface.
- said nanostructures comprises cylindrical structures, said cylindrical structures being substantially vertically aligned with respect to the plane of the surface.
- said treating comprises exposing said coated surface to a saturated atmosphere of a solvent (a process also known as "annealing") such as acetone or THF.
- said treating comprises exposing said coated surface to heat.
- the film can have different thicknesses.
- said surface is on a silicon wafer.
- said surface is not pre-treated with a cross-linked polymer prior to step b).
- said surface is pre-treated with a cross-linked polymer prior to step b).
- the invention relates to a film made according to the process above.
- the method further comprises the step e) etching said nanostructure-containing coated surface.
- a method of synthesis is contemplated for synthesizing a silicon-containing monomer, comprising reacting 2-chlorobuta-l,3-diene represented by the structure shown as (A) with ((trimethylsilyl)metliyl)magnesium chloride (a Grignard reagent) represented by the structure shown as (B) so as to generate trimethyl-(2 -methyl enebut-3-enyl)silane represented by the structure (C) (see Figure 1).
- the anionic polystyrene represented by the structure (E) can be further reacted with a silicon-containing monomer such as by the addition of trimethyl-(2-methylenebut-3-enyl)silane under such conditions as to generate a poly (styrene- trimethyl-(2-methylenebut-3-enyl)silane) dibolock copolymer represented by the structure (F) (see Figure 2).
- a silicon-containing monomer such as by the addition of trimethyl-(2-methylenebut-3-enyl)silane under such conditions as to generate a poly (styrene- trimethyl-(2-methylenebut-3-enyl)silane) dibolock copolymer represented by the structure (F) (see Figure 2).
- a method of synthesis comprising reacting a monomer such as styrene represented by the structure shown as (D) with sec-butyl lithium and subsequently with ethene-l,l-diyldibenzene (G) so as to generate a diphenyl ethylene end-capped polystyrene anion represented by the structure (H) (see Figure 6).
- a monomer such as styrene represented by the structure shown as (D) with sec-butyl lithium and subsequently with ethene-l,l-diyldibenzene (G) so as to generate a diphenyl ethylene end-capped polystyrene anion represented by the structure (H) (see Figure 6).
- the diphenyl ethylene end-capped polystyrene anion represented by the structure (H) can be further reacted with addition of a silicon-containing monomer such as methacryloxymethyltrimethylsilane (MTMSMA) under such conditions as to generate a diblock copolymer, PS-b-P(MTMSMA) represented by the structure (I) (see Figure 6).
- MTMSMA methacryloxymethyltrimethylsilane
- the invention relates to a method of synthesizing a silicon-containing copolymer, comprising: a) providing first and second monomers, said first monomer being a silicon-functionalized isoprene monomer and said second monomer being a monomer that does not incorporate silicon but can be polymerized such as styrene (e.g. in the case of styrene, it can polymerize because of the vinyl group); b) treating said second monomer under conditions such that a reactive polymer (such anionic as polystyrene) is formed; and c) reacting said first monomer with said reactive polymer (such as anionic polystyrene) under conditions such that said silicon-containing copolymer is synthesized.
- a reactive polymer such anionic as polystyrene
- said first monomer is trimethyl-(2-methylene-but-3-enyl)silane. In one embodiment, said first monomer was synthesized in a Kumada coupling reaction of chloroprene and (trimethylsilyl)-methylmagnesium chloride. In one embodiment, the conditions of step b) comprise polymerization in cyclohexane. In one embodiment, the conditions of step c) comprise anionic polymerization. In one embodiment the present invention contemplates, a further step comprising d) precipitating said silicon-containing copolymer in methanol. In one embodiment, said silicon-containing copolymer is PS-b-PTMSI, polystyrene-block-polytrimethylsilyl isoprene.
- the silicon-containing block copolymer is applied to a surface, for example, by spin coating, preferably under conditions such that physical features, such as nanostructures that are less than 100 nm in size (and preferably 50 nm or less in size), are spontaneously formed on the surface.
- the features have very different etch rates such that one block can be etched without substantial etching of the other.
- such nanostructures have a cylindrical morphology with the domain spacing of approximately 50 nm or less.
- the nanostructures are hexagonally packed. Such conditions for forming nanostructures can involve annealing with heat or solvents.
- the surface can first be treated with a substance that imparts a desired surface energy such that the nature of the surface treatment controls or enables nanostructure development.
- the conditions can involve varying the thickness of the applied silicon-containing copolymer.
- the nanostructures are made, in one embodiment, the method further comprises etching said nanostructures.
- the invention relates to a method of synthesizing a silicon-containing copolymer, comprising: a) providing first and second monomers, said first monomer being a silicon-containing methacrylate and said second monomer being a monomer that does not incorporate the element silicon and can polymerize such as styrene; b) treating said second monomer under conditions such that a reactive polymer such as polystyrene anion is formed; and c) reacting said first monomer with said reactive polymer (e.g. polystyrene anion) under conditions such that said silicon-containing copolymer is synthesized thus producing a block copolymer.
- said reactive polymer e.g. polystyrene anion
- said first monomer is methacryloxymethyltrimethylsilane (MTMSMA).
- the conditions of step c) comprise anionic polymerization.
- said silicon-containing copolymer is PS-b-P(MTMSMA).
- the invention relates to a method of forming nanostructures on a surface, comprising: a) providing a silicon-containing copolymer such as the PS-b-P(MTMSMA) copolymer and a surface; b) spin coating said copolymer on said surface to create a coated surface; and c) treating said coated surface under conditions such that nanostructures are formed on said surface.
- said nanostructures comprise cylindrical structures, said cylindrical structures being substantially vertically aligned with respect to the plane of the surface.
- said treating comprises exposing said coated surface to a saturated atmosphere of solvents such as acetone or THF (or other solvent that can dissolve at least one of the blocks in the copolymer and has a high vapor pressure at room temperature, including but not limited to toluene, benzene, etc.)
- solvents such as acetone or THF (or other solvent that can dissolve at least one of the blocks in the copolymer and has a high vapor pressure at room temperature, including but not limited to toluene, benzene, etc.
- said surface is on a silicon wafer.
- said surface is not pre-treated with a cross-linked polymer prior to step b).
- said surface is pre-treated with a cross-linked polymer prior to step b).
- nanostructures less than lOOnm in size are made with the copolymer by annealing using heat or solvents (as described herein).
- such nanostructures are hexagonally packed cylindrical morphology with the domain spacing of approximately 50 nm or less.
- the method further comprises etching said nanostructures.
- the present invention contemplates compositions comprising thin films (e.g. spin-coated films) of silicon-containing copolymers comprising such nanostructures, e.g. films deposited on a surface.
- diblock (or triblock or more) copolymers can be made.
- the illustrative silicon-containing monomers ( Figure 12) can be combined with any one or more of the hydrocarbon monomers ( Figure 13) lacking silicon.
- a block copolymer may contain over 12 wt% silicon in one block. This provides the etch selectivity to yield a 3-D pattern of self-assembled nanofeatures.
- Polymerization of these monomers can be done using a variety of methods.
- epoxide polymers can be made using the methods of Hillmyer and Bates, Macromolecules 29:6994 (1996). Polymers of trimethylsilyl styrene are described by Harada et al., J. Polymer Sci.
- FIG. 1 shows the synthesis of TMSI monomer.
- TMSI isoprene product monomer
- Figure 2 shows the synthesis of PS-b-PTMSI.
- FIG. 3 shows a Gel Permeation Chromatography (GPC) Chromatogram of the PS aliquot (red) and PS-b-PTMSI (green).
- GPC Gel Permeation Chromatography
- Figure 4 shows a 1H NMR spectrum of PS-b-PTMSI. The integral values were enlarged for clarity; numerical figures are shown in Table 2.
- FIG. 5 shows a Differential Scanning Calorimeter (DSC) trace of PS-b-PTMSI.
- Figure 6 shows the anionic synthesis of PS-b-P(MTMSMA).
- Figure 7 shows the 1H-NMR of PS-b-P(MTMSMA).
- Figure 8 shows a Gel Permeation Chromatography (GPC) chromato grams of PS aliquot (red) and PS-b-P(MTMSMA) (green).
- GPC Gel Permeation Chromatography
- Figure 9 shows the Small Angle X-ray Scattering (SAXS) analysis of a sample ofPS-b-P(MTMSMA).
- Figure 10 shows a THF annealed film with parallel orientation.
- Figure 11 show an acetone annealed film with perpendicular orientation.
- Figure 12 shows the structures of illustrative silicon-containing monomers.
- Figure 13 shows the structures of illustrative hydrocarbon monomers (lacking silicon).
- Table 1 shows a Gel Permeation Chromatography (GPC) characterization of PS-b-PTMSI.
- Table 2 shows 1H NMR data for PS-b-PTMSI.
- atoms making up the compounds of the present invention are intended to include all isotopic forms of such atoms.
- Isotopes include those atoms having the same atomic number but different mass numbers.
- isotopes of hydrogen include tritium and deuterium
- isotopes of carbon include 13 C and 14 C.
- one or more carbon atom(s) of a compound of the present invention may be replaced by a silicon atom(s).
- one or more oxygen atom(s) of a compound of the present invention may be replaced by a sulfur or selenium atom(s).
- Trimeth l-(2-methylene-but-3-enyl)silane is represented by the following abbreviated (TMSI) and whose polymeric version is
- Polystyrene anion is represented by the following structure: ,
- Polystyrene-block-polytrimethylsilyl isoprene is represented by the following
- Styrene (which is indicated by “S” or “St”) is represented by the following structure
- the present invention also contemplates styrene "derivatives" where the basic styrene structure is modified, e.g. by adding substituents to the ring (but preferably maintaining the vinyl group for polymerization).
- Derivatives of any of the compounds shown in Figures 12 and 13 can also be used. Derivatives can be, for example, hydroxy-derivatives, oxo-derivatives or halo-derivatives.
- P-methylstyrene is an example of a styrene derivative and is represented by the follo
- P-chlorostyrene is another example of a styrene haloderivative and is represented
- Trimethyl(4-vinylphenyl)silane is another example of a styrene derivative and is
- polymeric version is and is abbreviated P(TMS-St).
- Tert-butyldimethyl(4-vinylphenoxy)silane is another example of a styrene
- Tert-butyldimethyl(oxiran-2-ylmethoxy)silane is an example of a silicon
- TBDMSO-EO TBDMSO-EO
- P(TBDMSO-EO) TBDMSO-EO
- 1,1-diphenylethene is represented by the following structure:
- Methacryloxymethyltrimethylsilane is represented by the following structures: and abbreviated (MTMSMA) and whose
- polymeric version is S and is abbreviated P(MTMSMA).
- Di henyl ethylene end-capped polystyrene anion is represented by the following
- room temperature (rt) is taken to be 21 to 25 degrees Celsius, or 293 to 298 kelvins (K), or 65 to 72 degrees Fahrenheit. It is desired that the silicon-containing copolymer be used to create
- nano structures “nanofeatures” or “physical features on a nanometer scale” on a surface with controlled orientation. These physical features have shapes and thicknesses.
- various nanostructures can be formed by components of a block copolymer, such as vertical lamellae, in-plane cylinders, and vertical cylinders, and may depend on film thickness, surface treatment, and the chemical properties of the blocks.
- said cylindrical structures being substantially vertically aligned with respect to the plane of the first film.
- Orientation of structures in regions or domains at the nanometer level i.e. "microdomains" or “nanodomains”
- domain spacing of the nanostructures is approximately 50 nm or less.
- the methods described herein can generate structures with the desired size, shape, orientation, and periodicity. Thereafter, in one embodiment, these structures may be etched or otherwise further treated.
- silicon-containing monomers Due to the need for nanofeatures that can be etched, silicon-containing monomers were pursued. It is not intended that the present invention be limited by the nature of the silicon-containing monomer or that the present invention be limited to specific block polymers. However, to illustrate the invention, examples of various silicon-containing monomers and copolymers are provided.
- a monomer trimethyl(2-methylenebut-3-enyl)silane was synthesized. After purification over nBuLi, isoprene trimethyl(2-methylenebut-3-enyl)silane was successfully added on to a living polystyrene (PS) anion (E) in cyclohexane ( Figure 2).
- PS polystyrene
- TMSI was successfully synthesized in good yield by a Kumada coupling reaction [10, 13] of chloroprene with (trimethylsilyl)methylmagnesium chloride ( Figure 1).
- Anionic polymerization was selected for the diblock copolymer synthesis because of its capability to provide narrow polydispersity and its scalability.
- the diblock copolymer synthesis was successfully conducted in cyclohexane ( Figure 2) with good control of molecular weight and polydispersity (Table 1).
- the gel permeation chromatogram shown in Figure 3 demonstrates the successful growth of PS-b-PTMSI.
- the ⁇ NMR spectrum ( Figure 4) shows a molar ratio of 0.84:0.16 PS:P(TMSI) when integrating the five aromatic styrene protons against both the single olefin proton in the backbone of the P(TMSI) block and the 9 TMS protons (Table 2).
- the volume fractions ( ) of each block were calculated. Fortunately, small changes in the density of P(TMSI) produce relatively small changes in the volume f action of P(TMSI).
- TMSI Monomer
- a 250 mL RBF with condenser was charged with freshly ground Mg turnings (2.2 g, 92.2 mmol), a catalytic amount of dibromoethane, diethyl ether (100 mL), and a stir bar. After stirring for 15 min at rt, the reaction mixture was brought to reflux, and chloromethyltrimethylsilane (10.6 mL, 76.8 mmol) was added drop-wise over 30 min.
- TMSI Trimethyl-(2-methylenebut-3-enyl)silane
- the styrene polymerization was initiated with secbutyllithium at 40 °C in cyclohexane. After 12 h, a 5 mL aliquot of polystyrene (PS) was extracted from the reactor and terminated with degassed methanol. Purified TMSI monomer was then added to the reactor drop-wise and reacted for 12 h, followed by addition of degassed methanol to quench the living anions. The block copolymer was precipitated in methanol, filtered and freeze dried in a 10 wt% benzene solution with 0.25 wt% butylated hydroxytoluene inhibitor to prevent oxidative degradation of the P(TMSI) backbone.
- PS polystyrene
- DPE ⁇ , -Diphenylethylene
- ⁇ , -Diphenylethylene (DPE) (97 %, Aldrich) was freeze-dried and vacuumdistilled twice over ⁇ -butyllithium and stored under argon atmosphere inside a dry-box.
- DPE which is a high boiling liquid (bp 270-272 °C) was distilled at 140-160 °C under continuous vacuum.
- High-purity Argon used for maintain inert conditions, was passed through an OMI-2 organometallic Nanochem®resin indicator/purification column (Air Products).
- Methanol (reagent grade, Aldrich) used as termination reagent, was degassed by sparging with argon for 45 min for removing air (particularly oxygen), which can potentially couple "living" polymer chains leading to undesired products.
- Styrene 99 %, 10-15 ppm > ⁇ te7 -butylcatechol inhibitor, Aldrich
- Styrene was freezedried and then purified by two successive distillations over solvent-dried dibutylmagnesium (0.1 mmol/g styrene) at 40 °C for 2 h.
- the styrene burette was covered with aluminum foil to prevent photopolymerization and stored in a freezer. When ready for a reaction, the monomer was freeze-dried twice.
- Trimethyl-(2-methylene-but-3-enyl)silane was freeze-dried, and then dried over n-BuLi twice for at least 1 h at rt.
- the monomer After distilling a burrette, the monomer was freeze dried and used immediately. Methacryloxymethyltrimethylsilane (Gelest, SIM6485.5) was filtered through basic alumina on a bench top open ot the air, and then freeze-dried in a solvent flask. After drying over calcium hydride two times for at least 1 h at rt, the monomer was distilled into a burrette. The monomer was covered in foil and stored in the freezer for up to two days.
- Methacryloxymethyltrimethylsilane (Gelest, SIM6485.5) was filtered through basic alumina on a bench top open ot the air, and then freeze-dried in a solvent flask. After drying over calcium hydride two times for at least 1 h at rt, the monomer was distilled into a burrette. The monomer was covered in foil and stored in the freezer for up to two days.
- Trimethyl-(2-methylene-but-3-enyl)silane was freeze-dried, and then dried over n-BuLi twice for at least 1 h at rt. After distilling a burrette, the monomer was freeze dried and used immediately.
- MTMSMA methacryloxymethyltrimethylsilane
- Gelest, Inc Due to its higher MW and boiling point compared to MMA, the purification proved to be difficult.
- tnoctylaluminum initiated MTMSMA polymerization.
- Attempts to remove alcohols by sodium hydride also led to polymerization. It was determined that alcohols could be removed by passing the monomer through an alumina plug, and then subjected to freeze, pump, thaw cycles and distillation over calcium hydride. This monomer was successfully incorporated PS-b-P (MTMSMA) ( Figure 6).
- Methacryloxymethyltrimethylsilane (MTMSMA) (Gelest, SIM6485.5) was filtered through basic alumina on a bench top open ot the air, and then freeze-dried in a solvent flask. After drying over calcium hydride two times for at least 1 h at rt, the monomer was distilled into a burrette. The monomer was covered in foil and stored in the freezer for up to two days.
- MTMSMA Methacryloxymethyltrimethylsilane
- a 500 mL reactor was loaded with a stir bar and 5 molar equivalents of Li CI to initiator. LiCl suppresses side reactions during methacryloxymethyltrimethylsilane (MTMSMA) propagation [17].
- Purified THF was added into the reactor via a solvent flask, and the reactor was cooled to -72 °C in a dry ice/IPA bath. The total volume of THF used was set to so that the final concentration was 5 wt% monomer. After the solution temperature was stabilized at -72 °C, secBuLi was added and stirred for 5 min. Approximately 20 drops of purified styrene was then added to the reaction via an airlock and a burrette.
- Thin films were spin coated on freshly oxidized wafers with a 1 wt% solution of PS-b-P(MTMSMA) in toluene. The wafers were then annealed under a saturated atmosphere of acetone or THF overnight in a covered glass petti dish. The resulting films were analyzed via AFM, and the images show both parallel ( Figure 10) and perpendicularly (Figure 11) oriented cylinders depending on the solvent and film thickness. The size of the cylinders in these images is approximately 50 nm, which is consistent with the SAXS data.
Abstract
Description
Claims
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Also Published As
Publication number | Publication date |
---|---|
US20130196019A1 (en) | 2013-08-01 |
KR20130039727A (en) | 2013-04-22 |
SG184020A1 (en) | 2012-10-30 |
JP2013528664A (en) | 2013-07-11 |
CN102870247A (en) | 2013-01-09 |
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