CN117756615A - Benzocyclobutene monomer capable of being cured at low temperature and having aggregation-induced emission effect, resin, preparation method and photoresist - Google Patents
Benzocyclobutene monomer capable of being cured at low temperature and having aggregation-induced emission effect, resin, preparation method and photoresist Download PDFInfo
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- CN117756615A CN117756615A CN202311695654.6A CN202311695654A CN117756615A CN 117756615 A CN117756615 A CN 117756615A CN 202311695654 A CN202311695654 A CN 202311695654A CN 117756615 A CN117756615 A CN 117756615A
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- benzocyclobutene
- tetraphenyl ethylene
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- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical compound C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229920005989 resin Polymers 0.000 title claims abstract description 45
- 239000011347 resin Substances 0.000 title claims abstract description 45
- 239000000178 monomer Substances 0.000 title claims abstract description 32
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000000694 effects Effects 0.000 title abstract description 9
- 230000002776 aggregation Effects 0.000 title abstract description 8
- 238000004220 aggregation Methods 0.000 title abstract description 8
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims abstract description 8
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 claims abstract description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 7
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 3
- 150000001875 compounds Chemical class 0.000 claims description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000003504 photosensitizing agent Substances 0.000 claims description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000012442 inert solvent Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 8
- AYNXHFRDABNHRX-UHFFFAOYSA-N 7-bromobicyclo[4.2.0]octa-1,3,5-triene Chemical compound C1=CC=C2C(Br)CC2=C1 AYNXHFRDABNHRX-UHFFFAOYSA-N 0.000 claims description 7
- 238000006266 etherification reaction Methods 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000005859 coupling reaction Methods 0.000 claims description 6
- 229940078552 o-xylene Drugs 0.000 claims description 6
- 125000003944 tolyl group Chemical group 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- WTWLGTHCUYESQD-UHFFFAOYSA-N 7-chlorobicyclo[4.2.0]octa-1,3,5-triene Chemical compound C1=CC=C2C(Cl)CC2=C1 WTWLGTHCUYESQD-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000011229 interlayer Substances 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 150000001540 azides Chemical group 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 238000013035 low temperature curing Methods 0.000 abstract description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 abstract 1
- 125000005605 benzo group Chemical group 0.000 abstract 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000007142 ring opening reaction Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 238000001723 curing Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 230000005587 bubbling Effects 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- -1 polyethylene terephthalate Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 238000001259 photo etching Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012536 packaging technology Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- FGTHNRJXIKCBGC-JIBZRZDWSA-N (2e,6e)-2,6-bis[(4-azidophenyl)methylidene]-4-ethylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(CC)C\C1=C/C1=CC=C(N=[N+]=[N-])C=C1 FGTHNRJXIKCBGC-JIBZRZDWSA-N 0.000 description 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- ICLZNGAELWYHKL-CAPFRKAQSA-N (E)-3-[5-[5-[4-(N-phenylanilino)phenyl]thiophen-2-yl]thiophen-2-yl]prop-2-enoic acid Chemical compound OC(=O)\C=C\c1ccc(s1)-c1ccc(s1)-c1ccc(cc1)N(c1ccccc1)c1ccccc1 ICLZNGAELWYHKL-CAPFRKAQSA-N 0.000 description 1
- IGVLCAYLCAIWHV-UHFFFAOYSA-N 2,6-bis[(4-aminophenyl)methylidene]-4-ethylcyclohexan-1-one Chemical compound O=C1C(=CC=2C=CC(N)=CC=2)CC(CC)CC1=CC1=CC=C(N)C=C1 IGVLCAYLCAIWHV-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002073 fluorescence micrograph Methods 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000004984 smart glass Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- SEDZOYHHAIAQIW-UHFFFAOYSA-N trimethylsilyl azide Chemical compound C[Si](C)(C)N=[N+]=[N-] SEDZOYHHAIAQIW-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a benzocyclobutene monomer and resin which can be cured at low temperature and have aggregation-induced emission effect, a preparation method and photoresist. The tetraphenyl ethylene functionalized benzo ring of the inventionThe structural formula of the butene monomer is shown as formula I, wherein R 1 、R 2 、R 3 、R 4 Each independently selected from hydrogen, C1-C8 alkyl, fluoro, phenyl, vinyl, trifluoropropyl or perfluorooctyl. The four-styrene functional benzocyclobutene monomer is obtained by introducing the four-styrene group on the BCB four-membered ring, and the four-styrene functional benzocyclobutene monomer is heated and cured into the resin, so that the resin has obvious low-temperature curing characteristic, and the material has low dielectric constant and dielectric loss, low moisture absorption rate and good mechanical property; meanwhile, the four-styrene functionalized benzocyclobutene prepolymer can be cured under ultraviolet light to form a target pattern with fluorescent effect.
Description
Technical Field
The invention belongs to the field of high-performance electronic packaging resin, and particularly relates to a benzocyclobutene monomer which can be cured at a low temperature and has an aggregation-induced emission effect, a resin, a preparation method and photoresist.
Background
With the rapid development of the fifth generation mobile communication technology (5G), significant progress has been made in the fields of internet of things and augmented reality technology. Advances in 5G technology have led to the development of a series of flexible wearable electronic products such as smartphones, smartbracelets, smartglasses, etc., which are visible everywhere in daily life. All electronic products are not separated from a small chip, along with the development of microelectronic products towards miniaturization and portability, the integration level of the chip is continuously improved, higher requirements are put on packaging technology and packaging materials, and innovative development of the packaging materials with better performance becomes a current focus. Commonly used encapsulation materials such as epoxy, polyimide, polybenzoxazole, benzocyclobutene (BCB) have become a superior choice for multilayer wiring processes in integrated circuit fabrication. For example, commercial DVSBCB resins are known for their excellent dielectric properties, high thermal stability, low water absorption, and dimensional stability, and are ideal interlayer dielectric materials in multi-chip assemblies. However, there is still considerable room for development of conventional BCB thermosets.
Important imaging electronics in flexible liquid crystal displays organic thin film transistors employing flexible substrate materials such as polyethylene terephthalate often cannot withstand the excessive curing temperatures of the polymer dielectric layers. The research reports that the introduction of substituent groups on the quaternary ring of BCB can greatly reduce the activation energy barrier of the ring-opening reaction, thereby reducing the ring-opening temperature (the ring-opening temperature refers to the ring-opening peak temperature of a differential scanning calorimeter curve in the invention). The reported low temperature cross-linked benzocyclobutene related studies have mainly surrounded complex synthesis of BCB monomers and the crosslinked polymer is unstable or polymerization relies on additional crosslinking agents.
In addition, in the wafer bonding process of the three-dimensional stacked package of the chip, the requirement for improving the positioning precision is increasingly highlighted. Currently, the positioning tools used for multi-layer wafer bonding mainly rely on optical microscopy. In response to this challenge, we explored replacing existing interlayer positioning materials with luminescent materials in the hope of achieving higher positioning accuracy by fluorescence microscopy. Luminescent materials have received considerable attention in the fields of fluorescence sensing, information storage, bioimaging, crack detection, etc. in recent decades. Tetraphenyl ethylene (TPE) is one of the most widely studied aggregation-induced emission (AIE) molecules in the field of luminescent materials because of its easy synthesis, easy modification and stable emission characteristics.
In summary, aiming at the defects of the traditional BCB resin and the current packaging technology requirements, how to introduce proper groups on the BCB four-membered ring to ensure that the cured resin has the characteristics of low-temperature curing and aggregation-induced emission so as to more comprehensively meet the requirements of the market on the BCB resin with different property requirements becomes the technical problem to be solved currently.
Disclosure of Invention
The invention aims to provide a benzocyclobutene monomer which can be cured at low temperature and has aggregation-induced emission effect, a resin, a preparation method and a photoresist, wherein the obtained tetraphenyl ethylene functionalized benzocyclobutene resin has obvious low-temperature curing characteristic and can be formed by heating and curing the tetraphenyl ethylene functionalized benzocyclobutene monomer by introducing tetraphenyl ethylene groups on a BCB four-membered ring; the material has low dielectric constant and dielectric loss, low moisture absorption rate and good mechanical property; meanwhile, the four-styrene functionalized benzocyclobutene polymer can be cured under ultraviolet light to form a target pattern with fluorescent effect. The fully cured BCB resin prepared by the strategy is expected to become a novel packaging material which can be applied to the field of high temperature sensitivity and has higher positioning precision.
In a first aspect, the present invention provides a tetraphenyl ethylene functionalized benzocyclobutene monomer having a structural formula as shown in formula I:
in the formula I, R 1 、R 2 、R 3 、R 4 Each independently selected from hydrogen, C1-C8 alkyl, fluoro, phenyl, vinyl, trifluoropropyl or perfluorooctyl.
In the tetraphenyl ethylene functionalized benzocyclobutene monomer, R 1 、R 2 、R 3 、R 4 May be the same or different, and illustratively R 1 、R 2 、R 3 、R 4 The same is selected from hydrogen, C1-C8 alkyl, fluorine, phenyl, vinyl, trifluoropropyl or perfluorooctyl; alternatively, R 1 And R is 3 Identical, R 2 And R is 4 And are the same and are each independently selected from hydrogen, C1-C8 alkyl, fluoro, phenyl, vinyl, trifluoropropyl or perfluorooctyl.
The term C1-C8 alkyl refers to a linear or branched alkyl group having 1 to 8 carbon atoms, and includes, for example, "C1-4 alkyl group" such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, etc., and further includes n-pentyl, 3-methylbutyl, 2-methylbutyl, 1-ethylpropyl, n-hexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3-ethylbutyl, 2-ethylbutyl, n-octyl, etc. The C1-20 alkyl group also includes a C1-6 alkyl group having 1 to 6 carbon atoms.
By way of example, the structural formula of the tetraphenyl ethylene functionalized benzocyclobutene monomer is shown as formula I-a, I-b or I-c:
in a second aspect, the present invention provides a process for the preparation of the tetraphenyl ethylene functionalized benzocyclobutene monomer comprising the steps of:
(1) In the presence of titanium tetrachloride, performing a MaxMerry coupling reaction between a compound shown in a formula II and a compound shown in a formula III in a dry solvent under the action of a reducing agent to obtain a compound shown in a formula IV;
in the formula II, R 1 、R 2 Is defined as in formula I;
in the formula III, R 3 、R 4 Is defined as in formula I;
in the formula IV, R 1 、R 2 、R 3 、R 4 Is defined as in formula I;
(2) Under the action of inorganic base, the compound shown in the formula IV and 1-bromo-benzocyclobutene or 1-chlorobenzocyclobutene are subjected to Williamson etherification reaction in an inert solvent, so that the tetraphenyl ethylene functionalized benzocyclobutene monomer is obtained.
In the above preparation method, the molar ratio of the compound represented by formula ii to the compound represented by formula iii may be 1: (1-1.5); it will be appreciated that when R 1 And R is 3 Identical, R 2 And R is 4 The compound shown in the formula II is the same as the compound shown in the formula III;
the reducing agent is zinc powder;
the molar ratio of the titanium tetrachloride to the reducing agent may be 1:2;
the drying solvent may be ultra-dry tetrahydrofuran;
the temperature of the Maxmery coupling reaction can be 70-80 ℃, such as reflux temperature, and the time can be 10-12 hours, such as 11 hours;
the Maxwell coupling reaction is carried out in an oxygen-free environment;
in step (1), the product is subjected to the following post-treatments:
(i) Quenching with 10% potassium carbonate solution;
(ii) Filtering the reaction solution, sequentially extracting the reaction solution with saturated sodium bicarbonate, saturated saline and dichloromethane, evaporating the solvent, and purifying by column chromatography to obtain light green compound;
the inorganic base can be potassium carbonate, sodium carbonate, cesium carbonate, potassium hydroxide, sodium hydroxide;
the molar ratio of the compound of formula iv to the 1-bromo-benzocyclobutene or 1-chloro-benzocyclobutene may be 1: (2.2-3), specifically 1:2.5;
the inert solvent can be ultra-dry dimethyl sulfoxide, ultra-dry N, N-dimethylformamide or ultra-dry N, N-dimethylacetamide;
the temperature of the Williamson etherification reaction can be 50-55 ℃, such as 50 ℃, and the time can be 10-12 hours, such as 11 hours;
the Williamson etherification reaction is carried out in an oxygen-free environment;
in step (2), the product is subjected to the following post-treatments:
(i) The reacted mixture (yellow emulsion) was passed through a short silica gel pad and the silica gel pad was repeatedly washed with ethyl acetate, and the filtrate was collected.
(ii) The filtrate was extracted with saturated brine, and the solvent was evaporated after water removal with anhydrous magnesium sulfate to give a yellow solid.
(iii) The yellow solid obtained is purified by column chromatography to obtain yellow compound with higher purity.
In a third aspect, the present invention provides a tetraphenyl ethylene functionalized benzocyclobutene resin having a structural formula as shown in formula v:
in V, R 1 、R 2 、R 3 、R 4 Each independently selected from hydrogen, C1-C8 alkyl, fluoro, phenyl, vinyl, trifluoropropyl or perfluorooctyl; n is any integer from 3 to 100.
As an example, the formula V resin has the structural formula shown in formula V-a:
in a fourth aspect, the present invention provides a tetraphenyl ethylene functionalized benzocyclobutene resin, which is obtained by heating the tetraphenyl ethylene functionalized benzocyclobutene monomer in an inert solvent and performing crosslinking curing.
In the above-mentioned four-styrene functional benzocyclobutene curing resin, the inert solvent is selected from toluene, o-xylene, 1,3, 5-trimethylbenzene, N-dimethylformamide or N, N-dimethylacetamide;
the crosslinking curing is performed in a vacuum environment;
the heating is gradient heating, and the conditions are as follows: 150 ℃/1h,160 ℃/1h,170 ℃/3h.
In a fifth aspect, the present invention provides a tetraphenyl ethylene functionalized benzocyclobutene prepolymer which is prepared by heating the tetraphenyl ethylene functionalized benzocyclobutene monomer in an inert solvent and prepolymerizing.
In the above-mentioned tetraphenyl ethylene functionalized benzocyclobutene prepolymer, the inert solvent is selected from toluene, o-xylene, 1,3, 5-trimethylbenzene, N-dimethylformamide or N, N-dimethylacetamide;
the heating temperature is 120-150 ℃ and the time is 20-36 h, such as prepolymerization for 24h at 130 ℃.
The post-treatment step in the pre-polymerization step is as follows: and (3) spin-drying the solvent of the reacted mixture, dissolving in dichloromethane again, adding absolute ethyl alcohol for precipitation, standing and centrifuging to obtain a light yellow solid.
In a sixth aspect, the present invention provides the use of said tetraphenyl ethylene functionalized benzocyclobutene resin or said tetraphenyl ethylene functionalized benzocyclobutene prepolymer as or in the preparation of an encapsulating material or interlayer positioning material.
In a seventh aspect, the present invention provides a photoresist made from components including the tetraphenyl ethylene functionalized benzocyclobutene prepolymer, a photosensitive agent and an organic solvent.
In the photoresist, the weight parts of the components are as follows:
1 to 1.5 parts of the four-styrene functional benzocyclobutene prepolymer;
0.03-0.3 part of photosensitizer;
5-50 parts of organic solvent.
In an alternative embodiment of the present invention, the photoresist is made of components including, by weight:
1 part of the tetraphenyl ethylene functionalized benzocyclobutene polymer;
0.03-0.3 part of photosensitizer;
5-50 parts of organic solvent.
As an example, the photoresist is made of components including, by weight:
1 part of the tetraphenyl ethylene functionalized benzocyclobutene polymer;
0.1 part of photosensitizer;
10 parts of organic solvent.
In the photoresist, the photosensitizer is an azide organic substance, and the structural formula is shown in a formula VI:
in the formula VI, R is any group;
the organic solvent is toluene, o-xylene, mesitylene, methylene dichloride, chloroform or tetrahydrofuran.
As an example, the photosensitizer is a compound of formula VI-a, but is not limited to the structure of formula VI-a,
the chemical name of the compound shown in the formula VI-a is 2, 6-bis- (4-azidobenzylidene) -4-ethyl-cyclohexanone (2, 6-bis (4-azidobenzofuranidene) -4-ethylcylohexanone, BAC-E).
The invention has the following beneficial effects:
the invention provides a benzocyclobutene monomer and resin which can be cured at low temperature and have aggregation-induced emission effect through Williamson etherification reaction. The resin has remarkable low-temperature curing characteristics and exhibits excellent dielectric properties at both low and high frequencies. The resin has good hydrophobic property, large hydrophobic angle and low water absorption. The resin also has unique fluorescence characteristic and high positioning accuracy, and is expected to be used as a wafer bonding positioning material for chip packaging. The photoresist compounded by the polymer and the photosensitizer has uniform thickness of a film layer and clear pattern edges after being solidified. The body or the modified resin can be applied to the fields of large-scale integrated circuit multi-chip modules, high polymer film waveguides, wafer level chip scale packaging, micro motor systems, liquid crystal display packaging, flexible wearable electronic product packaging and the like.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a monomer of formula I-a in example 2 of the present invention.
FIG. 2 is a Differential Scanning Calorimetry (DSC) curve of the monomer of formula I-a in example 3 of the present invention.
FIG. 3 shows the photo-crosslinking mechanism (a), the photolithographic pattern optical microscope images (b-c) and the fluorescence microscope images (d-e) of the compound photoresist of the formula V-a prepolymer and the photosensitizer in example 6 of the present invention.
FIG. 4 is a scanning electron microscope image of the lithographic pattern of the V-a prepolymer and photosensitizer compounded photoresist of example 6 of the present invention.
FIG. 5 is a graph showing the results of a lithographic pattern profiler test on a photoresist formulated from a V-a prepolymer and a photosensitizer in example 6 of the present invention.
Detailed Description
The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof. The examples provided below are intended as guidelines for further modifications by one of ordinary skill in the art and are not to be construed as limiting the invention in any way.
The methods used in the examples described below, unless otherwise specified, are conventional methods, and are carried out according to techniques or conditions described in the literature in the field or according to the specifications of the product. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified. Percentages and parts are by weight unless otherwise indicated.
EXAMPLE 1 Synthesis of Compounds of formula IV-a (according to the methods described in documents Angewandte Chemie International Edition,2015,54 (50), 15160-15164)
5g (25 mmol) of the compound of formula II-a, 7.25g (110 mmol) of zinc powder and 250mL of ultra-dry tetrahydrofuran are added to a 500mL flame-dried three-necked flask, and deoxygenated by bubbling under an ice bath for 30min. Cooled to-78 ℃, titanium tetrachloride (6.25 ml,55 mmol) was added dropwise to the flask. The mixture was slowly warmed to room temperature, stirred for 0.5h, then refluxed overnight (11 h) at reflux temperature. After the reaction was completed, it was quenched with 10% aqueous potassium carbonate. The reaction solution was filtered, and the reaction solution was extracted with saturated sodium bicarbonate solution, saturated brine and dichloromethane in this order, the solvent was evaporated, and the compound of formula IV-a was purified by column chromatography in a yield of 81%. Eluent: petroleum ether/ethyl acetate (v/v 1:1).
1 H NMR(300MHz,CDCl 3 )δ＝7.06(m,11H),6.88(t,J＝8.8Hz,3H),6.56(t,J＝9.1Hz,4H)
EXAMPLE 2 Synthesis of Compounds of formula I-a
1g (2.746 mmol) of a compound of formula IV-a, 4.47g (13.73 mmol) Cs 2 CO 3 In a 50mL three-necked flask, 20mL of ultra-dry DMSO was added, bubbling was deoxygenated for 30min, and 1.25g (6.87 mmol) of 1-bromo-benzocyclobutene was added to react overnight (11 h) at 50 ℃. After the reaction, the reaction mixture was filtered and saturated common salt was usedAfter extraction with water and ethyl acetate and removal of excess solvent by rotary evaporation, purification by column chromatography gave 1.159g of yellow solid in 74.3% yield. Eluent: petroleum ether/ethyl acetate (v/v 300:1).
The nuclear magnetic hydrogen spectrum is shown in figure 1.
1 H NMR(300MHz,CDCl 3 )δ＝7.32(t,J＝6.0Hz,2H),7.24–7.20(m,3H),7.19-7.14(m,4H),7.13-7.04(m,9H),6.98(t,J＝9.0Hz,4H),6.76(dd,J＝12.0,9.0Hz,4H),5.61(t,J＝6.0Hz,2H),3.66(m,2H),3.27(dd,J＝15.0,3.0Hz,2H).
13 C NMR(75MHz,CDCl 3 )δ＝156.52,156.48,144.78,144.22,144.11,142.63,139.85,136.88,136.79,132.66,131.47,129.87,127.73,127.62,127.38,127.34,126.27,126.24,123.45,123.10,114.31,114.25,74.21,39.49,39.45.
EXAMPLE 3 Synthesis of Compounds of formula IV-b
5.3g (25 mmol) of the compound of formula II-b, 7.25g (110 mmol) of zinc powder and 250mL of ultra-dry tetrahydrofuran are added to a 500mL flame-dried three-necked flask, and deoxygenated by bubbling in an ice bath for 30min. Cooled to-78 ℃, titanium tetrachloride (6.25 ml,55 mmol) was added dropwise to the flask. The mixture was slowly warmed to room temperature, stirred for 0.5h, then refluxed overnight (11 h) at reflux temperature. After the reaction was completed, it was quenched with 10% aqueous potassium carbonate. The reaction solution was filtered, and the reaction solution was extracted with saturated sodium hydrogencarbonate solution, saturated brine and methylene chloride in this order, the solvent was evaporated, and 4.06g of the compound of formula IV-b was purified by column chromatography, with a yield of 83%. Eluent: petroleum ether/ethyl acetate (v/v 1:1).
1 H NMR(300MHz,CDCl 3 )δ＝7.12(m,10H),6.74(t,J＝8.8Hz,2H),6.62(t,J＝9.1Hz,4H),2.40(s,6H).
EXAMPLE 4 Synthesis of Compounds of formula I-b
1.08g (2.75 mmol) of the compound of formula IV-a, 4.47g (13.73 mmol) Cs 2 CO 3 In a 50mL three-necked flask, 20mL of ultra-dry DMSO was added, bubbling was deoxygenated for 30min, and 1.25g (6.87 mmol) of 1-bromo-benzocyclobutene was added to react overnight (11 h) at 50 ℃. After completion of the reaction, the reaction mixture was filtered, extracted with saturated brine and ethyl acetate, and after removing the excess solvent by rotary evaporation, it was purified by column chromatography to obtain 1.15g of a solid with a yield of 70%. Eluent: petroleum ether/ethyl acetate (v/v 300:1).
1 H NMR(300MHz,CDCl 3 )δ＝7.32(t,J＝6.0Hz,2H),7.25–7.20(m,3H),7.18-7.14(m,4H),7.14-7.04(m,7H),6.97(t,J＝9.0Hz,4H),6.76(dd,J＝12.0,9.0Hz,4H),5.60(t,J＝6.0Hz,2H),3.66(m,2H),3.28(dd,J＝15.0,3.0Hz,2H),2.40(s,6H).
EXAMPLE 5 Synthesis of Compounds of formula IV-c
5.4g (25 mmol) of the compound of formula II-c, 7.25g (110 mmol) of zinc powder and 250mL of ultra-dry tetrahydrofuran are added to a 500mL flame-dried three-necked flask, and deoxygenated by bubbling in an ice bath for 30min. Cooled to-78 ℃, titanium tetrachloride (6.25 ml,55 mmol) was added dropwise to the flask. The mixture was slowly warmed to room temperature, stirred for 0.5h, then refluxed overnight (11 h) at reflux temperature. After the reaction was completed, it was quenched with 10% aqueous potassium carbonate. The reaction solution was filtered, and the reaction solution was extracted with saturated sodium bicarbonate solution, saturated brine and dichloromethane in this order, the solvent was evaporated, and 3.85g of the compound of formula IV-c was purified by column chromatography, with a yield of 77%. Eluent: petroleum ether/ethyl acetate (v/v 1:1).
1 H NMR(300MHz,CDCl 3 )δ＝7.09(m,10H),6.70(t,J＝8.8Hz,2H),6.58(t,J＝9.1Hz,4H)
EXAMPLE 6 Synthesis of Compounds of formula I-c
1.1g (2.75 mmol) of the compound of formula IV-c, 4.47g (13.73 mmol) Cs 2 CO 3 In a 50mL three-necked flask, 20mL of ultra-dry DMSO was added, bubbling was deoxygenated for 30min, and 1.25g (6.87 mmol) of 1-bromo-benzocyclobutene was added to react overnight (11 h) at 50 ℃. After the completion of the reaction, the reaction mixture was filtered, extracted with saturated brine and ethyl acetate, and after removing the excess solvent by rotary evaporation, it was purified by column chromatography to obtain 1.25g of a solid of the formula I-c in 75% yield. Eluent: petroleum ether/ethyl acetate (v/v 300:1).
1 H NMR(300MHz,CDCl 3 )δ＝7.32(t,J＝6.0Hz,2H),7.28–7.22(m,3H),7.17-7.14(m,4H),7.15-7.06(m,7H),6.98(t,J＝9.0Hz,4H),6.74(dd,J＝12.0,9.0Hz,4H),5.48(t,J＝6.0Hz,2H),3.64(m,2H),3.26(dd,J＝15.0,3.0Hz,2H).
Example 7 Ring opening temperature characterization of the monomers of formula I-a
3-5 mg of the monomer of formula I-a are weighed and placed in a solid alumina crucible for paving, and the ring opening temperature is measured by a differential scanning calorimeter, and the test result is shown in figure 2. Test atmosphere: nitrogen gas; flow rate: 50mL/min. As can be seen from FIG. 2, the ring opening peak temperature of the polymer monomer is 188 ℃, and the ring opening temperature can be greatly reduced by introducing ether bonds on the four-membered ring of BCB.
Example 8 curing and characterization of the V-a resin
500mg of the monomer of formula I-a are completely dissolved in 2mL of 1,3, 5-trimethylbenzene solution and placed in a mold, and cured in a vacuum atmosphere by gradient heating (150 ℃ C./1 h,160 ℃ C./1 h,170 ℃ C./3 h) to give a yellow sheet (diameter: 3.5cm thickness: 0.4 cm).
The dielectric constants of the formula V-a resin and the DVSBCB resin were measured using a parallel plate capacitor method in the range of 10Hz to 1MHz at room temperature, and the dielectric constants of the formula V-a resin and the DVSBCB resin were measured using a resonator method at 10 GHz. Dielectric constant of 2.62.8. Dielectric loss factor of 1.3X10 -3 ～3.15×10 -3 . As can be seen from the dielectric property test, the dielectric constant of the cured resin of formula V-a is lower than DVSBCB within 10 Hz-1 MHz, and still lower than 2.8 at 10 GHz.
The water absorption and contact angle of the resin after curing at room temperature were measured for 72 hours. The weight change was measured by immersing the two resins in a beaker filled with deionized water at normal temperature, and both V-a resin and DVSBCB resin were as low as 0.23%. By means ofThe DSA 100 instrument characterizes the static contact angle of v-a resin with DVSBCB resin at room temperature. Both resins had nearly the same large hydrophobic angle (TPE-BCB resin contact angle of 109 ° and DVSBCB resin contact angle of 108 °), and their hydrophobic properties were comparable.
Thermal stability of the resin of formula V-a was determined by thermogravimetric analysis (TGA), 5% thermogravimetric loss temperature in nitrogen of 248 ℃, sample size: 3-5 mg, nitrogen flow rate: 50mL/min.
The mechanical properties of V-a resin were measured by nanoindentation, hardness 0.33GPa, young's modulus 0.44GPa, maximum penetration depth: 2000nm, sample piece: diameter 3.5cm x thickness 0.4cm.
EXAMPLE 9 preparation of prepolymer of formula V-a
500mg of the monomer of formula I-a and 4.5g of 1,3, 5-trimethylbenzene solvent were successively charged into a 120mL high-temperature pressure-resistant bottle, and deoxygenated three times by freezing with liquid nitrogen. The reaction system was subjected to prepolymerization at 130℃for 24h. The mixture after the reaction was dried by spin-drying, then dissolved in 5mL of methylene chloride, precipitated with 50mL of absolute ethanol, left to stand, and centrifuged to obtain a pale yellow V-a prepolymer (number average molecular weight: l3163, PDI: 1.56).
Example 10 preparation of Photoresist
(1) Preparation of photosensitizer formula VI-a Compounds
10g (30 mmol) of 2, 6-bis- (4-aminobenzylidene) -4-ethyl-cyclohexanone are added to a beaker, which is placed in an ice-water bath and cooled 150mL of 2.5mol/L (375 mmol) aqueous sodium nitrite are added dropwise. 167mL of a 1mol/L (375 mmol) hydrochloric acid solution were then slowly added dropwise with stirring, the pH was adjusted to 7-8 with sodium bicarbonate, 8.32g (72 mmol) of azido-trimethylsilane were added to the inside, and after stirring at 0℃for 10min, 10.1g of the brick-red product of formula VI-a (2, 6-bis- (4-azidobenzene) -4-ethyl-cyclohexanone) were obtained by recrystallization. The yield was 94%.
1 H NMR(300MHz,CDCl 3 )δ＝7.75(s,2H),7.48(d,J＝8.2Hz,4H),7.08(d,J＝8.1Hz,4H),3.13-3.00(m,2H),2.57-2.44(m,2H),1.43(m,2H),0.90(t,J＝7.4Hz,3H).
(2) Lithographic process and surface topography of lithographic patterns
100mg of prepolymer of the formula V-a and 10mg of photosensitizer 2, 6-bis- (4-azidobenzene) -4-ethyl-cyclohexanone are dissolved in 1mL of toluene solution and stirred uniformly to prepare the photosensitive adhesive. The photosensitive paste was spin coated on a silicon wafer (1000 rpm,10s;2000rpm,60 s), and baked for 2min with a hot plate at 80 ℃. The silicon wafer is placed in a photoetching machine and exposed to ultraviolet light with the wavelength of 365nm for 5s, and developed by a developing solution for 35s. Finally, the photoetching pattern is obtained, the surface morphology of the photoetching pattern is observed, and the optical microscope, the fluorescence microscope and the scanning electron microscope are shown as fig. 3 and 4, so that the photoetching pattern can be clearly seen to have obvious fluorescence effect. The surface profile test curve is shown in FIG. 5, and a resolution of 10 μm can be achieved at a uniform film thickness of 230 nm.
The present invention is described in detail above. It will be apparent to those skilled in the art that the present invention may be practiced in a wide variety of equivalent parameters, concentrations, and conditions without departing from the spirit and scope of the invention. While the invention has been described with respect to specific embodiments, it will be appreciated that the invention may be further modified. In general, this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains.
Claims (13)
1. A structural formula of the tetraphenyl ethylene functionalized benzocyclobutene monomer is shown in a formula I:
in the formula I, R 1 、R 2 、R 3 、R 4 Each independently selected from hydrogen, C1-C8 alkyl, fluoro, phenyl, vinyl, trifluoropropyl or perfluorooctyl.
2. The tetraphenyl ethylene functionalized benzocyclobutene monomer of claim 1, wherein: the structural formula of the tetraphenyl ethylene functionalized benzocyclobutene monomer is shown as the formula I-a, I-b or I-c:
3. a process for the preparation of the tetraphenyl ethylene functionalized benzocyclobutene monomer of any one of claims 1-2 comprising the steps of:
(1) In the presence of titanium tetrachloride, performing a MaxMerry coupling reaction between a compound shown in a formula II and a compound shown in a formula III in a dry solvent under the action of a reducing agent to obtain a compound shown in a formula IV;
in the formula II, R 1 、R 2 Is defined as in formula I;
in the formula III, R 3 、R 4 Is defined as in formula I;
in the formula IV, R 1 、R 2 、R 3 、R 4 Is defined as in formula I;
(2) Under the action of inorganic alkali, the compound shown in the formula IV and 1-bromo-benzocyclobutene or 1-chloro-benzocyclobutene inert solvent are subjected to Williamson etherification reaction to obtain the tetraphenyl ethylene functionalized benzocyclobutene monomer.
4. A method of preparation according to claim 3, characterized in that: the molar ratio of the compound shown in the formula II to the compound shown in the formula III is 1: (1-1.5);
the reducing agent is zinc powder;
the molar ratio of the titanium tetrachloride to the reducing agent is 1:2;
the drying solvent is ultra-dry tetrahydrofuran;
the reaction temperature of the Maxmery coupling reaction is 70-80 ℃ and the time is 10-12 h;
the Maxwell coupling reaction is carried out in an oxygen-free environment;
the inorganic base is potassium carbonate, sodium carbonate, cesium carbonate, potassium hydroxide or sodium hydroxide;
the molar ratio of the compound shown in the formula IV to the 1-bromo-benzocyclobutene or the 1-chloro-benzocyclobutene is 1: (2.2-3);
the inert solvent is ultra-dry dimethyl sulfoxide, ultra-dry N, N-dimethylformamide or ultra-dry N, N-dimethylacetamide;
the temperature of the Williamson etherification reaction is 50-55 ℃ and the time is 10-12 h;
the Williamson etherification reaction is carried out in an oxygen-free environment.
5. A structural formula of the tetraphenyl ethylene functionalized benzocyclobutene resin is shown in a formula V:
in V, R 1 、R 2 、R 3 、R 4 Each independently selected from hydrogen, C1-C8 alkyl, fluoro, phenyl, vinyl, trifluoropropyl or perfluorooctyl; n is any integer from 3 to 100.
6. A tetraphenyl ethylene functionalized benzocyclobutene resin obtained by heating the tetraphenyl ethylene functionalized benzocyclobutene monomer of claim 1 or 2 in an inert solvent and curing by crosslinking.
7. The tetraphenyl ethylene functionalized benzocyclobutene resin of claim 6, characterized in that:
the inert solvent is selected from toluene, o-xylene, 1,3, 5-trimethylbenzene, N-dimethylformamide or N, N-dimethylacetamide;
the crosslinking curing is performed in a vacuum environment;
the heating is gradient heating, and the conditions are as follows: 150 ℃/1h,160 ℃/1h,170 ℃/3h.
8. A tetraphenyl ethylene functionalized benzocyclobutene prepolymer obtained by heating the tetraphenyl ethylene functionalized benzocyclobutene monomer of claim 1 or 2 in an inert solvent and prepolymerizing.
9. The tetraphenyl ethylene functionalized benzocyclobutene prepolymer of claim 8, characterized in that:
the inert solvent is selected from toluene, o-xylene, 1,3, 5-trimethylbenzene, N-dimethylformamide or N, N-dimethylacetamide;
the heating temperature is 120-150 ℃ and the heating time is 20-36 h.
10. Use of the tetraphenyl ethylene functionalized benzocyclobutene resin of any one of claims 5 to 7 or the tetraphenyl ethylene functionalized benzocyclobutene prepolymer of claim 8 or 9 as or in the preparation of an encapsulating material or an interlayer positioning material.
11. A photoresist, characterized by being made of components comprising the tetraphenyl ethylene functionalized benzocyclobutene prepolymer of claim 8 or 9, a photosensitizer and an organic solvent.
12. The photoresist according to claim 11, characterized in that: the weight portions of the components are as follows:
1 to 1.5 parts of the four-styrene functional benzocyclobutene prepolymer;
0.03-0.3 part of photosensitizer;
5-50 parts of organic solvent.
13. The photoresist according to claim 11 or 12, characterized in that: the photosensitizer is an azide organic substance, and the structural formula is shown in a formula VI:
in the formula VI, R is any group;
the organic solvent is toluene, o-xylene, mesitylene, methylene dichloride, chloroform or tetrahydrofuran.
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