CN1693367A - Forward solution of polyimide/silicon oxide composite its preparation process and manufactured composite from same - Google Patents
Forward solution of polyimide/silicon oxide composite its preparation process and manufactured composite from same Download PDFInfo
- Publication number
- CN1693367A CN1693367A CN 200410034736 CN200410034736A CN1693367A CN 1693367 A CN1693367 A CN 1693367A CN 200410034736 CN200410034736 CN 200410034736 CN 200410034736 A CN200410034736 A CN 200410034736A CN 1693367 A CN1693367 A CN 1693367A
- Authority
- CN
- China
- Prior art keywords
- group
- metacryloxy
- silane
- propyl
- ethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004642 Polyimide Substances 0.000 title claims abstract description 66
- 229920001721 polyimide Polymers 0.000 title claims abstract description 66
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 106
- 239000002131 composite material Substances 0.000 title claims description 56
- 238000002360 preparation method Methods 0.000 title claims description 13
- 229910052814 silicon oxide Inorganic materials 0.000 title abstract description 15
- -1 silicon oxide compound Chemical class 0.000 claims abstract description 94
- 238000000034 method Methods 0.000 claims abstract description 57
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 239000002243 precursor Substances 0.000 claims abstract description 28
- 229910000077 silane Inorganic materials 0.000 claims abstract description 16
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 76
- 239000000243 solution Substances 0.000 claims description 76
- 239000000377 silicon dioxide Substances 0.000 claims description 46
- 206010070834 Sensitisation Diseases 0.000 claims description 43
- 230000008313 sensitization Effects 0.000 claims description 43
- 229920005575 poly(amic acid) Polymers 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 34
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 33
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 239000001301 oxygen Substances 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical group [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 24
- 150000001412 amines Chemical class 0.000 claims description 23
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 claims description 21
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 18
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 claims description 18
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 claims description 18
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 claims description 18
- 229910052736 halogen Inorganic materials 0.000 claims description 16
- 150000002367 halogens Chemical class 0.000 claims description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims description 16
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 15
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 15
- 125000004104 aryloxy group Chemical group 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 claims description 12
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 claims description 12
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical compound CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 claims description 12
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- 125000003368 amide group Chemical group 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 claims description 9
- MMFBQHXDINNBMW-UHFFFAOYSA-N n,n-dipropylaniline Chemical compound CCCN(CCC)C1=CC=CC=C1 MMFBQHXDINNBMW-UHFFFAOYSA-N 0.000 claims description 9
- JLTDJTHDQAWBAV-UHFFFAOYSA-N phenyldimethylamine Natural products CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 9
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000004494 ethyl ester group Chemical group 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- NFIQONWVAQATRV-UHFFFAOYSA-N (3-ethenylphenyl)-triethoxysilane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC(C=C)=C1 NFIQONWVAQATRV-UHFFFAOYSA-N 0.000 claims description 3
- WXUIXCLQMXECCL-UHFFFAOYSA-N (3-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=CC(C=C)=C1 WXUIXCLQMXECCL-UHFFFAOYSA-N 0.000 claims description 3
- ORFPMGWJDWEAAQ-UHFFFAOYSA-N (4-ethenylphenyl)-triethoxysilane Chemical compound CCO[Si](OCC)(OCC)C1=CC=C(C=C)C=C1 ORFPMGWJDWEAAQ-UHFFFAOYSA-N 0.000 claims description 3
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 claims description 3
- CSXPRVTYIFRYPR-UHFFFAOYSA-N bis(ethenyl)-diethoxysilane Chemical compound CCO[Si](C=C)(C=C)OCC CSXPRVTYIFRYPR-UHFFFAOYSA-N 0.000 claims description 3
- ZPECUSGQPIKHLT-UHFFFAOYSA-N bis(ethenyl)-dimethoxysilane Chemical compound CO[Si](OC)(C=C)C=C ZPECUSGQPIKHLT-UHFFFAOYSA-N 0.000 claims description 3
- ZZHNUBIHHLQNHX-UHFFFAOYSA-N butoxysilane Chemical class CCCCO[SiH3] ZZHNUBIHHLQNHX-UHFFFAOYSA-N 0.000 claims description 3
- NWQIWFOQNHTTIA-UHFFFAOYSA-N diethoxy-bis(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(CC=C)OCC NWQIWFOQNHTTIA-UHFFFAOYSA-N 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- WERMRYHPOOABQT-UHFFFAOYSA-N dimethoxy-bis(prop-2-enyl)silane Chemical compound C=CC[Si](OC)(CC=C)OC WERMRYHPOOABQT-UHFFFAOYSA-N 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- PITANJVKTXCWKI-UHFFFAOYSA-N ethoxy-tris(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(CC=C)CC=C PITANJVKTXCWKI-UHFFFAOYSA-N 0.000 claims description 3
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 3
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 claims description 3
- FBGNFSBDYRZOSE-UHFFFAOYSA-N tris(ethenyl)-ethoxysilane Chemical compound CCO[Si](C=C)(C=C)C=C FBGNFSBDYRZOSE-UHFFFAOYSA-N 0.000 claims description 3
- JYTZMGROHNUACI-UHFFFAOYSA-N tris(ethenyl)-methoxysilane Chemical compound CO[Si](C=C)(C=C)C=C JYTZMGROHNUACI-UHFFFAOYSA-N 0.000 claims description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 10
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000004377 microelectronic Methods 0.000 abstract description 2
- 229920001296 polysiloxane Polymers 0.000 abstract 1
- 239000010408 film Substances 0.000 description 42
- 239000002585 base Substances 0.000 description 34
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 22
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 18
- 238000000576 coating method Methods 0.000 description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 16
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 13
- 230000003287 optical effect Effects 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000011159 matrix material Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 11
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 8
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 150000008064 anhydrides Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- 150000004985 diamines Chemical class 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 6
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 5
- 229940043232 butyl acetate Drugs 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 5
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000003384 imaging method Methods 0.000 description 4
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 3
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 235000019439 ethyl acetate Nutrition 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- GIMBWMBFSHKEQU-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O.CCCCCC(C)=O GIMBWMBFSHKEQU-UHFFFAOYSA-N 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 3
- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical compound O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 description 3
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 230000004304 visual acuity Effects 0.000 description 3
- FVFYRXJKYAVFSB-UHFFFAOYSA-N 2,3,5,6-tetrafluorobenzene-1,4-diamine Chemical compound NC1=C(F)C(F)=C(N)C(F)=C1F FVFYRXJKYAVFSB-UHFFFAOYSA-N 0.000 description 2
- PGCBRGRKKOCPAN-UHFFFAOYSA-N 4-triethoxysilylbutanamide Chemical compound CCO[Si](OCC)(OCC)CCCC(N)=O PGCBRGRKKOCPAN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- ULHFFAFDSSHFDA-UHFFFAOYSA-N 1-amino-2-ethoxybenzene Chemical compound CCOC1=CC=CC=C1N ULHFFAFDSSHFDA-UHFFFAOYSA-N 0.000 description 1
- DCTFCVYVHBHICU-UHFFFAOYSA-N 1-n,1-n,2-n,2-n-tetrafluorobenzene-1,2-diamine Chemical compound FN(F)C1=CC=CC=C1N(F)F DCTFCVYVHBHICU-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- VIUDTWATMPPKEL-UHFFFAOYSA-N 3-(trifluoromethyl)aniline Chemical compound NC1=CC=CC(C(F)(F)F)=C1 VIUDTWATMPPKEL-UHFFFAOYSA-N 0.000 description 1
- LKHVCEWNPKEPBT-UHFFFAOYSA-N 4-[(4-amino-3-methoxyphenyl)methyl]-2-methoxyaniline Chemical compound C1=C(N)C(OC)=CC(CC=2C=C(OC)C(N)=CC=2)=C1 LKHVCEWNPKEPBT-UHFFFAOYSA-N 0.000 description 1
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical class NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 1
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 1
- MPUIUFJXCAFVGK-UHFFFAOYSA-N 5-[(3-amino-4-methylphenyl)methyl]-2-methylaniline Chemical compound C1=C(N)C(C)=CC=C1CC1=CC=C(C)C(N)=C1 MPUIUFJXCAFVGK-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- NWAOHOCBUSGNMQ-UHFFFAOYSA-N C(CCC)OC(C(C)(C)C)OOCCCCC Chemical compound C(CCC)OC(C(C)(C)C)OOCCCCC NWAOHOCBUSGNMQ-UHFFFAOYSA-N 0.000 description 1
- GFXHFYHUJAATBP-UHFFFAOYSA-N CO[Si](OC)(OC)CCCC(N)=O Chemical compound CO[Si](OC)(OC)CCCC(N)=O GFXHFYHUJAATBP-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CJQVURJLLPOIIJ-UHFFFAOYSA-N FN(C1=C(C=CC=C1)N(F)F)F.C1(=C(C=CC=C1)N)N Chemical compound FN(C1=C(C=CC=C1)N(F)F)F.C1(=C(C=CC=C1)N)N CJQVURJLLPOIIJ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CHISTDPSKQQHCD-UHFFFAOYSA-N NC(=O)C1=CC=C(C=C1)P(CC)=O Chemical compound NC(=O)C1=CC=C(C=C1)P(CC)=O CHISTDPSKQQHCD-UHFFFAOYSA-N 0.000 description 1
- WQSQCMCLIATTKL-UHFFFAOYSA-N NC(=O)C1=CC=C(C=C1)[SiH](C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound NC(=O)C1=CC=C(C=C1)[SiH](C1=CC=CC=C1)C1=CC=CC=C1 WQSQCMCLIATTKL-UHFFFAOYSA-N 0.000 description 1
- RVOLIYOJRZKPHS-UHFFFAOYSA-N NC(=O)C1=CC=C(C=C1)[SiH](CC)CC Chemical compound NC(=O)C1=CC=C(C=C1)[SiH](CC)CC RVOLIYOJRZKPHS-UHFFFAOYSA-N 0.000 description 1
- LDKULBOPHABTAT-UHFFFAOYSA-N NC(=O)C=1C=C(C=CC1)[Si](OC)(OC)OC Chemical compound NC(=O)C=1C=C(C=CC1)[Si](OC)(OC)OC LDKULBOPHABTAT-UHFFFAOYSA-N 0.000 description 1
- SYGUXQAYOVEDPL-UHFFFAOYSA-N NC(=O)C=1C=C(C=CC1)[Si](OCC)(OCC)OCC Chemical compound NC(=O)C=1C=C(C=CC1)[Si](OCC)(OCC)OCC SYGUXQAYOVEDPL-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- JJDQZIJKWRZLSJ-UHFFFAOYSA-N [O].C=CCCCC Chemical compound [O].C=CCCCC JJDQZIJKWRZLSJ-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- AGSPXMVUFBBBMO-UHFFFAOYSA-N beta-aminopropionitrile Chemical compound NCCC#N AGSPXMVUFBBBMO-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical compound C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 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
- 239000010977 jade Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GBCKRQRXNXQQPW-UHFFFAOYSA-N n,n-dimethylprop-2-en-1-amine Chemical compound CN(C)CC=C GBCKRQRXNXQQPW-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005186 naphthyloxy group Chemical group C1(=CC=CC2=CC=CC=C12)O* 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005096 rolling process Methods 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
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 125000002769 thiazolinyl group Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Abstract
A precursor solution of polyimide/silicone oxide compound used for microelectronic, semiconductor and photoelectric device, the polyimide/silicon oxide compound, the process for preparing said solution and the process for preparing the film of polyimide/silicon oxide compound on a substrate are disclosed. Said process features that the silane compound and another two monomers are sequentially added.
Description
Technical field
The present invention forms the method for polyimide/silica composite material film about the preparation method of the precursor aqueous solution (precursor solution) of polyimide/silica composite material on base material, and the purposes of prepared precursor aqueous solution and matrix material.
Background technology
Metal, pottery, polymer and electronic material are four main fields of Materials science now.Every kind of material has its special property and relative merits.For example polymer has easy processing, tough, tool elasticity, anticorrosive, insulation and advantage such as cheap, but its heat-resisting character and physical strength are relatively poor; That stupalith then has is hard, low activity, excellent thermotolerance and physical strength advantage, but weight is heavier and frangible.Just can access the virgin material that has outstanding character if can remedy its shortcoming in conjunction with the advantage of various materials.This notion has attracted organic and inorganic to blend together material (hybrid material), i.e. matrix material, broad research.
Its size of traditional matrix material (composite) (domain) is generally hundreds of micron orders to centimetre-sized, organic or inorganic composition in this type of material is mainly played the part of the role who changes structure or function, the mode of mainly utilizing physical property to mix (blend) prepares, and blend together the preparation method of material, be mainly sol-gel method (sol-gel) or self-assembly method chemical modes such as (self-assembly), by organic and the shortcoming of improving matrix material inorganic composition mixing under microcosmic.For example, organic materials is imported in the inorganic materials main body, can improve the frangible character of inorganic materials and various color is provided.Perhaps, when importing inorganic materials in the organic materials main body, then can increase its physical strength, thermotolerance, improve hygroscopic nature etc., and more can develop brand-new character by molecular designing.
General organic-inorganic blendes together material need be heated to higher temperature usually with the solvent in the system of removing, and makes inorganic composition finish crosslinking reaction to remove aqueous vapor.Wherein polyimide is because general polymer commonly used has more excellent machinery and heat-resisting character is used in industries such as semi-conductor, printed circuit board (PCB) widely.Therefore polyimide/silicon oxide (polyimide/silica) matrix material causes extensive attention and numerous researchs is arranged, in the hope of obtaining more excellent character and improving its shortcoming.
At present, how polyimide/silica composite material prepares in the following manner:
(1) dicarboxylic anhydride and diamines are added in solvent commonly used such as N,N-DIMETHYLACETAMIDE (DMAc) or the N-Methyl pyrrolidone (NMP) reaction become polyamic acid (poly (amic acid), PAA); Make tetraethoxysilane (TEOS) or tetramethoxy-silicane (TMOS) in ethanol or tetrahydrofuran (THF) (THF); add entry and catalyzer (can be acid catalyst or alkaline catalysts); TEOS or TMOS are hydrolyzed and polycondensation reaction forms oligomerization silicon oxide particle or molecular grouping, again will this PAA solution evenly obtain the precursor aqueous solution of polyimide/silica composite material after the stirring with silica solution.
(2) dicarboxylic anhydride and diamines are added reaction becomes PAA among solvent commonly used such as DMAc or the NMP, directly TEOS or TMOS monomer are added in the PAA solution then, utilize polyamic acid directly to carry out the hydrolysis and the polycondensation reaction of silicon oxide, obtain the precursor aqueous solution of polyimide/silica composite material at last as catalyzer.
(3) dicarboxylic anhydride and diamine reactant are become PAA, add 3-aminocarbonyl propyl triethoxyl silane amido couplers such as (APrTEOS) in the acid anhydrides of PAA end, add capable hydrolysis of TEOS or TMOS and polycondensation reaction again, make the polyimide of organic phase by producing the covalency bond between coupler and the inorganic silicon oxide mutually, improve organic phase and inorganic alternate compatibility, to dwindle the big or small of silicon oxide particle and to improve its distributing homogeneity and obtain preferable character.
(4) dicarboxylic anhydride and diamine reactant are become PAA, directly TEOS or TMOS are added in the PAA solution then, utilize polyamic acid directly to carry out the hydrolysis and the polycondensation reaction of silicon oxide as catalyzer, in addition and add γ-glycidoxypropyltrimewasxysilane couplers such as (GTMOS), improve organic phase and inorganic alternate compatibility by reactive force between the hydrogen bond equimolecular, to dwindle the big or small of silicon oxide particle and to improve its distributing homogeneity, obtain preferable character.
(5) dicarboxylic anhydride and diamine reactant are become PAA, add 3-aminocarbonyl propyl triethoxyl silane amido couplers such as (APrTEOS) in the acid anhydrides of PAA end, add capable hydrolysis of TEOS or TMOS and polycondensation reaction again, in addition and add γ-glycidoxypropyltrimewasxysilane couplers such as (GTMOS), while, dwindles the size of silicon oxide particle and improves its distributing homogeneity to improve organic phase and inorganic alternate compatibility by reactive force (being provided by the GTMOS coupler) between intramolecularly covalent linkage (being provided by the APrTEOS coupler) and hydrogen bond equimolecular.
Aforementioned conventional prepares the method for polyimide/silica composite material, though available matter polyimide originally is good high performance composite, but when desiring on wafer or glass substrate, to make the specific pattern of microstructure or tool function with this material, because material is not had a sensing optical activity, after film hardening, must utilize traditional lithography process to make pattern, comprise: the coating of photoresistance; The exposure imaging of photoresistance; Carry out the etching of composite material film in modes such as active-ion-etch; Reach the steps such as clean of peeling off of carrying out remaining photoresistance with ozone and particular chemicals, the processing step complexity is comparatively consuming time.Moreover the etching resistence of polyimide/silica composite material is good, and the parameter designing when carrying out etching is difficult for.Simultaneously the pattern after the etching easily has side ancient piece of jade, round, flat and with a hole in its centre roughness big and etching is incomplete, and photoresistance easily residues in the first-class shortcoming of pattern.
Summary of the invention
The objective of the invention is to improve the shortcoming of above-mentioned general non-sensing optical activity polyimide/silica composite material film, the invention provides the preparation method of a kind of light-sensitive polyimide/silica composite material film.Method of the present invention can be improved above-mentioned (1) precursor aqueous solution to (5) prepared polyimide/silica composite material, makes it can be used for preparing the low volumetric shrinkage of tool, sensing optical activity polyimide/silica composite material film.Simultaneously, because low volumetric shrinkage of the present invention, sensing optical activity polyimide/silica composite material itself promptly can be considered a kind of photoresistance, its step that can directly carry out exposure imaging significantly reduces fabrication steps to make required pattern, improves turnout and product yield.
" polyamic acid " speech herein, mean the product with carboxylic acid functional by the containing of diamines and dicarboxylic anhydride reaction gained-NH-CO-, " polyimide " speech then makes on the polyamic acid-product of NH-CO-functional group and carboxylic acid functional cyclisation generation heating up to solidify for this polyamic acid.
" halogen " speech means fluorine, chlorine, bromine or iodine herein.
" C herein
1-6Alkoxyl group "; mean-the O-alkyl group; this alkyl is to contain the straight chain of 1 to 6 carbon atom or branch's alkyl and via the Sauerstoffatom bond, the example comprises for example methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, second butoxy, the 3rd butoxy, n-pentyloxy, neopentyl oxygen and hexyloxy etc.
" C herein
2-6Alkene oxygen base " speech, mean-the O-alkenyl group, this thiazolinyl is to contain the straight chain of 2 to 6 carbon atoms or divide branched alkenyl and via the Sauerstoffatom bond, the example comprises for example vinyloxy group, propenyloxy group, butenyloxy, amylene oxygen base and hexene oxygen base etc.
" aryloxy " speech means-the O-aromatic yl group herein, and this aryl is for example phenyl or naphthyl etc.; The example of aryloxy comprises for example phenoxy group and naphthyloxy etc.
" C herein
1-6Stretch alkyl " speech, the alkanes that means self-contained 1 to 6 carbon atom removes two hydrogen atoms and forms divalence C
1-6Stretch alkyl, the example comprise for example stretch methyl, stretch ethyl, stretch propyl group, the 1-methyl is stretched propyl group, the 2-methyl is stretched propyl group, stretch butyl, the 1-methyl is stretched butyl, the 2-methyl is stretched butyl, stretch amyl group and stretch hexyl etc.
The speech of " stretching aryl " herein means from C
6-10Aromatic hydrocarbon removes two formed divalent aryls of hydrogen atom, and example comprises for example to be stretched phenyl and stretch naphthyl etc.
" C herein
1-6Alkyl " speech; mean the alkyl that contains 1 to 6 carbon atom, the example comprises for example methyl, ethyl, n-propyl, sec.-propyl, 1-methyl-propyl, 2-methyl-propyl, normal-butyl, isobutyl-, new butyl, 1-methyl butyl, 2-methyl butyl, amyl group and hexyl etc.
Herein " end has epoxy group(ing) " mean for example glycidoxypropyl methyl, glycidoxypropyl ethyl and glycidoxypropyl etc.
" but end has sensitization polymeric unsaturated group " speech herein, mean end and have ethene and belong to unsaturated group, the example comprises vinyl, allyl group, ethenylphenyl, allyl phenyl, propenyloxy group methyl, propenyloxy group ethyl, propenyloxy group propyl group, propenyloxy group butyl, propenyloxy group amyl group, propenyloxy group hexyl, metacryloxy methyl, metacryloxy ethyl, metacryloxy propyl group, metacryloxy butyl, metacryloxy amyl group and metacryloxy hexyl etc.
The invention relates to a kind of preparation method of precursor aqueous solution of polyimide/silica composite material, this method comprises:
(A) provide a kind of polyamic acid solution;
(B) with a kind of general formula H
2N-R
1-Si (R
2)
3(R wherein
1Be C
1-6Stretch alkyl or stretch aryl, and R
2Can be identical or differently, each represents C
1-6Alkoxyl group) amido coupler adds in the solution of step (A);
(C) a kind of silane compound (silane compound) monomer is added step
(B) in the gained solution, make polyamic acid have the silicon oxide group;
(D) with a kind of general formula (R
6)
xSi (R
7)
(4-x)(R wherein
6For but end has sensitization polymeric unsaturated group, R
7Be halogen, C
1-6Alkoxyl group, C
2-6Alkene oxygen base or aryloxy, and x is 1 to 3 integer) monomer add in step (C) the gained solution, but make the silicon oxide group have sensitization polymeric unsaturated group; And
(E) with a kind of general formula R
8N (R
9)
2(R wherein
8For but end has sensitization polymeric unsaturated group, and R
9Be C
1-6Alkyl) monomer adds in step (D) the gained solution, but makes polyamic acid have sensitization polymeric unsaturated group, but obtains a kind of precursor aqueous solution of sensitization polymeric polyimide/silica composite material.
The preparation method of above-mentioned precursor aqueous solution can further be contained between step (C) and the step (D), with general formula R
4Si (R
5)
3(R wherein
4For end has cycloalkyl groups, and R
5Be halogen, C
1-6Alkyl, C
2-6Alkene oxygen base or aryloxy) coupler add in step (C) the gained solution.
The invention still further relates to the preparation method of the precursor aqueous solution of another kind of polyimide/silica composite material, this method comprises:
(A1) provide a kind of polyamic acid solution;
(B1) form the molecular grouping or the particulate solution of tool silicon oxide group from silane compound (silane compound) monomer;
(C1) with a kind of general formula (R
6)
xSi (R
7)
(4-x)(R wherein
6For but end has sensitization polymeric unsaturated group, R
7Be halogen, C
1-6Alkoxyl group,
C
2-6Alkene oxygen base or aryloxy, and x is 1 to 3 integer) monomer add in step (B1) the gained solution, but make this silicon oxide group have sensitization polymeric unsaturated group;
(D1) mixing step (A1) gained solution and step (C1) gained solution, but the solution that the silicon oxide group has the polyimide/silica composite material of sensitization polymeric unsaturated group formed; And
(E1) with a kind of general formula R
8N (R
9)
2(R wherein
8For but end has sensitization polymeric unsaturated group, and R
9Be C
1-6Alkyl) monomer adds in step (D1) the gained solution, but makes polyamic acid have sensitization polymeric unsaturated group, but forms a kind of precursor aqueous solution of sensitization polymeric polyimide/silica composite material.
The preparation method of above-mentioned precursor aqueous solution can further comprise general formula H
2N-R
1-Si (R
2)
3(R wherein
1Be C
1-6Stretch alkyl or stretch aryl, and R
2Can be identical or differently, each represents C
1-6Alkoxyl group) amido coupler adds in step (A1) the gained solution, remix step (D1) gained solution.
The invention still further relates to a kind of method that forms polyimide/silica composite material film on base material, it comprises that the gained solution coat is on base material with above-mentioned steps (E) and (E1), and after steaming desolventized, irradiation energy ray (energy ray) exposed; Toast again, form polyimide/silica composite material film.
In the present invention, used polyamic acid solution can and get by the preparation of dicarboxylic anhydride and diamine reactant.The dicarboxylic anhydride that can be used among the present invention is an aromatic dianhydride; can be selected from compound well known to those skilled in the art; example is including (but not limited to) pyromellitic dianhydride (PMDA); 4,4-two phthalandione dianhydrides (BPDA); 4,4-hexafluoroisopropyli,ene two phthalandione dianhydrides (6FDA); 1-(trifluoromethyl)-2; 3; 5,6-benzene tertacarbonic acid dianhydride (P3FDA); 1, two (trifluoromethyl)-2 of 4-; 3; 5,6-benzene tertacarbonic acid dianhydride (P6FDA); 1-(3 ', 4 '-the dicarboxyl phenyl)-1; 3; 3-trimethylammonium indane-5, the 6-dicarboxylic acid dianhydride; 1-(3 ', 4 '-the dicarboxyl phenyl)-1; 3; 3-trimethylammonium indane-6, the 7-dicarboxylic acid dianhydride; 1-(3 ', 4 '-the dicarboxyl phenyl)-3-methyl indan-5; the 6-dicarboxylic acid dianhydride; 1-(3 '; 4 '-the dicarboxyl phenyl)-3-methyl indan-6, the 7-dicarboxylic acid dianhydride; 2,3; 9; 10-perylene tetracarboxylic dianhydride; 1,4,5; 8-naphthalene tetracarboxylic acid dianhydride; 2; 6-dichloronaphtalene-1,4,5; the 8-tetracarboxylic dianhydride; 2; 7-dichloronaphtalene-1,4,5; the 8-tetracarboxylic dianhydride; 2; 3,6,7-Tetrachloronaphthalene-2; 4; 5, the 8-tetracarboxylic dianhydride; luxuriant and rich with fragrance-1,8; 9; the 10-tetracarboxylic dianhydride; 3,3 ', 4; 4 '-benzophenone tetracarboxylic dianhydride; 1; 2 ', 3,3 '-benzophenone tetracarboxylic dianhydride; 3; 3 '; 4,4 '-biphenyl tetracarboxylic dianhydride; 3,3 '; 4; 4 '-benzophenone tetracarboxylic dianhydride; 2,2 ', 3; 3 '-biphenyl tetracarboxylic dianhydride; 4; 4 '-isopropylidene two acid dianhydrides; 3,3 '-isopropylidene two phthalandione dianhydrides; 4,4 '-oxygen base two phthalandione dianhydrides; 4; 4 '-alkylsulfonyl two phthalandione dianhydrides; 3; 3 '-oxygen base two phthalandione dianhydrides; 4,4 '-methylene radical two phthalandione dianhydrides; 4,4 '-sulfenyl two phthalandione dianhydrides; 4; 4 '-ethylene phthalandione dianhydride; 2; 3,6, the 7-tetracarboxylic dianhydride; 1; 2; 4, the 5-tetracarboxylic dianhydride; 1,2; 5; 6-naphthalene tetracarboxylic acid dianhydride; benzene-1,2,3; 4-tetracarboxylic dianhydride and pyridine-2; 3,5,6-tetracarboxylic dianhydride and composition thereof.Be preferably pyromellitic dianhydride (PMDA), 4,4-two phthalandione dianhydrides (BPDA), 4,4-hexafluoroisopropyli,ene two phthalandione dianhydrides (6FDA), 1-(trifluoromethyl)-2,3,5,6-benzene tertacarbonic acid dianhydride (P3FDA) or 1, two (trifluoromethyl)-2 of 4-, 3,5,6-benzene tertacarbonic acid dianhydride (P6FDA) or its mixture.
The diamines that can be used among the present invention is an aromatic diamine; optional field is since then known; example is including (but not limited to) 4; 4 '-octafluoro p-diaminodiphenyl (OFB); tetrafluoro-p-phenylenediamine (TFPD); 2; 2 '-5; 5 '-tetrachloro benzidine (TCB); 3; 3 '-dichlorobenzidine (DCB); 3; 3 '-dimethyl-4; 4 '-benzidine; 2; 2 '-dimethyl-4; 4 '-benzidine; 2; 2 '-two (trifluoromethyl)-4; 4 '-benzidine (TF DB); 2; 2 '-two (3-aminocarbonyl phenyl) HFC-236fa; 2; 2 '-two (4-aminocarbonyl phenyl) HFC-236fa; 4; 4 '-oxygen base-two [3-(trifluoromethyl) aniline; 3; 5-two amido phenylfluoroforms (3; 5-diaminobenzotrifluoride); tetrafluoro-1; 4-stretches phenylenediamine (tetrafluorophenylene diamine); tetrafluoro--phenylenediamine stretched; 4; 4 '-oxygen base pentanoic (ODA); 1; two (4-amido the phenoxy group)-2-tributyl benzene (BATB) of 4-; 2; 2 '-dimethyl-4; 4 '-two (4-amido phenoxy group) biphenyl (DB APB); 2; two [4-(the 4-amido phenoxy group) phenyl] HFC-236fa (BAPPH) of 2-; 2; 2 '-two [4-(4-amido phenoxy group) phenyl] norborneol alkane (BAPN); 5-amido-1-(4 '-aminocarbonyl phenyl)-1; 3; 3-trimethylammonium indane; 6-amido-1-(4 '-aminocarbonyl phenyl)-1; 3; 3-trimethylammonium indane; 4; 4 '-methylene-bis (neighbour-chloroaniline); 3; 3 '-dichloro diphenylamine; 3; 3 '-the alkylsulfonyl pentanoic; 4; 4 '-two amido benzophenone; 1; 5-two amido naphthalenes; two (4-aminocarbonyl phenyl) diethylsilane; two (4-aminocarbonyl phenyl) diphenyl silane; two (4-aminocarbonyl phenyl) ethyl phosphine oxide; N-(two (4-aminocarbonyl phenyl))-N-methylamine; N-(two (4-aminocarbonyl phenyl))-N-phenyl amine; 4,4 '-methylene-bis (2-aminotoluene); 4,4 '-methylene-bis(2methoxyaniline); 5; 5 '-methylene-bis (2-amino-phenol); 4; 4 '-methylene-bis (2-aminotoluene); 4,4 '-oxygen base two (2-anisidine); 4,4 '-oxygen base two (2-chloroaniline); 2; 2 '-two (4-amino-phenols); 5; 5 '-oxygen base two (2-amino-phenol); 4,4 '-sulfenyl two (2-aminotoluene); 4,4 '-sulfenyl two (2-anisidine); 4; 4 '-sulfenyl two (2-chloroaniline); 4; 4 '-alkylsulfonyl two (2-aminotoluene); 4,4 '-alkylsulfonyl two (2-phenetidine); 4,4 '-alkylsulfonyl two (2-chloroaniline); 5; 5 '-alkylsulfonyl two (2-amino-phenol); 3; 3 '-dimethyl-4,4 '-two amido benzophenone; 3,3 '-dimethoxy-4 '; 4 '-two amido benzophenone; 3; 3 '-two chloro-4,4 '-two amido benzophenone; 4,4 '-benzidine; between-phenylenediamine; p-phenylenediamine; 4; 4 '-methylene dianiline (MDA); 4; 4 '-the sulfenyl pentanoic; 4,4 '-the alkylsulfonyl pentanoic; 4,4 '-the isopropylidene pentanoic; 3; 3 '-tolidine; 3; 3 '-dimethoxy benzidine; 3,3 '-dicarboxylate biphenyl amine; 2,4-tolyl diamines; 2; 5-tolyl diamines; 2; 6-tolyl diamines; between-the xylyl diamines; 2,4-two amidos-5-toluene(mono)chloride and 2,4-two amidos-6-toluene(mono)chloride and composition thereof.Be preferably 4,4 '-oxygen base pentanoic (ODA) or 4,4 '-octafluoro p-diaminodiphenyl (OFB) or its mixture.
According to the present invention, the optional field since then of silane compound (silane compound) is known, and it generally has formula Si (R
3)
4, R wherein
3Can be identical or differently, each represents halogen, C
1-6Alkoxyl group, C
2-6Alkene oxygen base or aryloxy, restricted condition are 4 R
3Non-is halogen simultaneously.The example of silane compound is including (but not limited to) tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane and four butoxy silanes and composition thereof.Be preferably tetramethoxy-silicane.
The amido coupler that is used for the present invention can be selected from known in the art, and it generally has formula H
2N-R
1-Si (R
2)
3, R wherein
1Represent C
1-6Stretch alkyl or stretch aryl, R
2Can be identical or different, each represents C
1-6Alkoxyl group.The example of this amido coupler is including (but not limited to) 3-aminocarbonyl propyl Trimethoxy silane (APrTMOS), 3-three amido propyl-triethoxysilicanes (APrTEOS), 3-aminocarbonyl phenyl Trimethoxy silane (APTMOS), and 3-aminocarbonyl phenyl triethoxyl silane (APTEOS) and composition thereof.Be preferably 3-three amido propyl-triethoxysilicanes (APrTEOS).
The used general formula R of the present invention
4Si (R
5)
3Coupler (R wherein
4Represent terminal base and the R that has epoxy group(ing)
5Represent halogen, C
1-6Alkoxyl group, C
2-6Alkene oxygen base or aryloxy) example including (but not limited to) γ-glycidoxypropyl trimethoxy silane (GTMOS) and γ-glycidoxypropyl triethoxyl silane (GTEOS).
In the methods of the invention, the preparation of the precursor aqueous solution of polyimide/silicon oxide composite film material should be carried out in solvent.Solvent for use is also without particular limitation, as long as can dissolve the used material of the present invention.The example of this solvent is including (but not limited to) dimethyl sulfoxide (DMSO) (DMSO), N, N-N,N-DIMETHYLACETAMIDE (DMAc), 1-methyl-2-pyrrolidone (NMP), N, dinethylformamide (DMF), tetrahydrofuran (THF) (THF), dioxan, methyl ethyl ketone (MEK), chloroform (CHCl
3), methylene dichloride, gamma-butyrolactone, butylacetate, cyclopentanone, propylene glycol monomethyl ether (PGMEA), furfuryl alcohol (THFA), Methyl amyl ketone (2-heptanone), Diethylene Glycol list hexyl ether (DGME), propylene glycol monomethyl ether (PGME), n-butyl acetate (nBA), dihydroxypropane single-ether, propylene glycol list-just-propyl ether or Diethylene Glycol single-butyl ether acetic ester or its mixture.Be preferably N,N-dimethylacetamide (DMAc) or 1-methyl-2-pyrrolidone (NMP).
According to the inventive method, the mixed ratio of above-mentioned each composition can be any ratio, is preferably behind stirring reaction, does not have the ratio that precipitates or make the situation generation of solution muddiness.Generally speaking, carry out under the temperature that the stirring reaction of each step is in 20 to 40 ℃, be preferably under room temperature and carry out.Simultaneously, the reaction times of each step is at least 1 hour, is generally 1 to 24 hour.
The present invention can import general formula (R
6)
xSi (R
7)
(4-x)Monomer, with solution in the condensation reaction that is hydrolyzed of silicon oxide group, but make the silicon oxide group have sensitization polymeric unsaturated terminal chain base.This monomer example is including (but not limited to) 3-metacryloxy propyl trimethoxy silicane, 3-metacryloxy propyl-triethoxysilicane, 2-metacryloxy ethyl trimethoxy silane, 2-metacryloxy ethyl triethoxysilane, 3-metacryloxy butyl trimethoxy silane, 3-metacryloxy butyl triethoxyl silane, 3-propenyloxy group propyl trimethoxy silicane, 3-propenyloxy group propyl-triethoxysilicane, 2-propenyloxy group ethyl trimethoxy silane, 2-propenyloxy group ethyl triethoxysilane, 3-propenyloxy group butyl trimethoxy silane, 3-propenyloxy group butyl triethoxyl silane, 3-methyl propenyloxy group propyl trimethoxy silicane, 3-methyl propenyloxy group propyl-triethoxysilicane, 3-methyl propenyloxy group ethyl trimethoxy silane, 3-methyl propenyloxy group ethyl triethoxysilane, 3-methyl propenyloxy group butyl trimethoxy silane, 3-methyl propenyloxy group butyl triethoxyl silane, 3-metacryloxy propyl trimethoxy silicane, 3-metacryloxy propyl-triethoxysilicane, 3-metacryloxy ethyl trimethoxy silane, 3-metacryloxy ethyl triethoxysilane, 3-metacryloxy butyl trimethoxy silane, 3-metacryloxy butyl triethoxyl silane, vinyltrimethoxy silane, vinyltriethoxysilane, 3-ethenylphenyl Trimethoxy silane, 3-ethenylphenyl triethoxyl silane, 4-ethenylphenyl Trimethoxy silane, 4-ethenylphenyl triethoxyl silane, allyltrimethoxysilanis, allyltriethoxysilane, 4-allyl phenyl Trimethoxy silane, 4-allyl phenyl triethoxyl silane, two (3-metacryloxy propyl group) dimethoxy silane, two (3-metacryloxy propyl group) diethoxy silane, two (2-metacryloxy ethyl) dimethoxy silane, two (2-metacryloxy ethyl) diethoxy silane, two (3-metacryloxy butyl) dimethoxy silane, two (3-metacryloxy butyl) diethoxy silane, two (3-propenyloxy group propyl group) dimethoxy silane, two (3-propenyloxy group propyl group) diethoxy silane, two (2-propenyloxy group ethyl) dimethoxy silane, two (2-propenyloxy group ethyl) diethoxy silane, two (3-propenyloxy group butyl) dimethoxy silane, two (3-propenyloxy group butyl) diethoxy silane, divinyl dimethoxy silane, the divinyl diethoxy silane, diallyl dimethoxy silane, the diallyl diethoxy silane, three (3-metacryloxy propyl group) methoxy silane, three (3-metacryloxy propyl group) Ethoxysilane, three (2-metacryloxy ethyl) methoxy silane, three (2-metacryloxy ethyl) Ethoxysilane, three (3-metacryloxy butyl) methoxy silane, three (3-metacryloxy butyl) Ethoxysilane, three (3-propenyloxy group propyl group) methoxy silane, three (3-propenyloxy group propyl group) Ethoxysilane, three (2-propenyloxy group ethyl) methoxy silane, three (2-propenyloxy group ethyl) Ethoxysilane, three (3-propenyloxy group butyl) methoxy silane, three (3-propenyloxy group butyl) Ethoxysilane, the trivinyl methoxy silane, the trivinyl Ethoxysilane, triallyl methoxy silane and triallyl Ethoxysilane and composition thereof.Be preferably 3-metacryloxy propyl trimethoxy silicane, 3-metacryloxy propyl-triethoxysilicane, 2-metacryloxy ethyl trimethoxy silane, 2-metacryloxy ethyl triethoxysilane or its mixture.
The present invention can import general formula R
8N (R
9)
2Monomer, so that but polyamic acid has sensitization polymeric unsaturated terminal chain base, this monomer example is including (but not limited to) methacrylic acid 2-dimethylin ethyl ester, methacrylic acid 2-diethylin ethyl ester, methacrylic acid 2-dipropyl amido ethyl ester, 3-metacryloxy propyl-dimethyl amine, 3-metacryloxy propyl group diethylamine, 3-metacryloxy propyl group dipropylamine, 3-propenyloxy group propyl-dimethyl amine, 3-propenyloxy group propyl group diethylamide, 3-propenyloxy group propyl group dipropylamine, 3-methyl propenyloxy group propyl-dimethyl amine, 3-methyl propenyloxy group propyl group diethylamide, 3-methyl propenyloxy group propyl group dipropylamine, 4-(metacryloxy propyl group) phenyl dimethyl amine, 4-(metacryloxy propyl group) diethylamino phenyl base amine, 4-(metacryloxy propyl group) phenyl dipropylamine, 4-(metacryloxy ethyl) phenyl dimethyl amine, 4-(metacryloxy ethyl) diethylamino phenyl base amine, 4-(metacryloxy ethyl) phenyl dipropylamine, 4-(metacryloxy methyl) phenyl dimethyl amine, 4-(metacryloxy methyl) diethylamino phenyl base amine, 4-(metacryloxy methyl) phenyl dipropylamine, allyl dimethyl base amine, the allyl group diethylamide, the allyl group dipropylamine, 4-allyl dimethyl base amine, 4-allyl group diethylamide, 4-allyl group dipropylamine, 4-vinyl-dimethyl base amine, 4-vinyl diethylamide and 4-vinyl dipropylamine and composition thereof.Be preferably methacrylic acid 2-dimethylin ethyl ester, methacrylic acid 2-diethylin ethyl ester, methacrylic acid 2-dipropyl amido ethyl ester, allyl dimethyl base amine or its mixture.
In the present invention, general formula (R
6)
xSi (R
7)
(4-x)Monomer and general formula R
8N (R
9)
2Monomeric usage quantity generally is respectively 2 to 15 not ear equivalents and 25 to 75 equivalents, and after adding reactive system, under 20 to 40 ℃, is preferably under the room temperature, and stirring reaction at least 1 hour was generally 1 to 24 hour.
According to the inventive method, step (E) can further be included under the existence of light initiator carries out.The light initiator that is used for the inventive method is the widely known person in field for this reason; the example is including (but not limited to) 1; 1-dimethyl-1-phenyl benzophenone (as the Irgacure-651 of CIBA Geigy company sale), 1-hydroxyl-cyclohexyl-phenyl ketone and two (2; 4, the 6-trimethylbenzoyl) phenylphosphine oxide (as the Irgacure-819 of CIBA Geigy company sale).
Involved in the present invention with step (E) but the precursor aqueous solution of gained sensitization polymeric polyimide/silica composite material is coated the technology on the base material, can utilize the known coating method in any this field, for example roller coat (rolling coating), flow coat (flow coating), impregnation coating method (dipcoating), spraying coating method (spray coating), method of spin coating (spincoating) or curtain are coated with method (curtain coating).Wherein, to obtain the viewpoint of uniform thin film, preferable use method of spin coating.
Moreover, according to the inventive method,, can the known mode in this field carry out the film forming processing procedure of gained solution coat after on the base material.Say it for example, after above-mentioned application step, carry out soft roasting matrix material about 1 to about 60 minutes with about 40 to about 200 ℃ temperature in hot-plate or baking oven, steaming desolventizes.Carry out exposure program again, utilize one have on it design pattern in advance light shield (mask) with contact or non-contacting mode, with light source (for example ultraviolet ray or the visible light source of wavelength 100 to 500nm, its can be the wideband mercury lamp of continuous wavelength or through the single wavelength light source of filter disc) see through this light shield irradiation or be projected to soft composite material film after roasting; Perhaps utilize the composite material film after focused light sources such as electron beam or laser expose to soft baking, make it carry out the photosensitive cross-linking polyreaction, obtain the sensing optical activity composite material film; Be preferably and use ultraviolet ray to expose.Thereafter, again in hot-plate or baking oven with about 40 to about 200 ℃ temperature roasting about 1 to about 120 minutes of back of exposing to the sun, after removing the interference situations and most solvent of vertical direction in the film, utilization is the photographic developer of matrix with the organic solvent, the film of exposure back gained is soaked wherein or with photographic developer in a suitable manner spray coating on film, make on the film and remove without the exposed areas dissolving.Clean (rinse), solvent blowed or makes modes such as substrate fast rotational drying remove with nitrogen with organic solvent again, and obtain required pattern.At last, film after the patternization is lasted about 30 to about 200 minutes multi-stage type thermofixation baking under about 120 ℃ to about 300 ℃, make partly endless loop formation polyimide of polyamic acid, silicon oxide partly condensation is finished, and can obtain on substrate by low volumetric shrinkage, the formed specific pattern of sensing optical activity composite material film.
Employed photographic developer is used organic solvent with cleaning in above-mentioned film-forming process, to those skilled in the art, is conspicuous.Photographic developer is for example including (but not limited to) dimethyl sulfoxide (DMSO) (DMSO), N, N-N,N-DIMETHYLACETAMIDE (DMAc), 1-methyl-2-pyrrolidone (NMP), N, dinethylformamide (DMF), tetrahydrofuran (THF) (THF), dioxan, methyl ethyl ketone (MEK), chloroform (CHCl
3), methylene dichloride, methyl alcohol, ethanol, Virahol, propyl carbinol, polyoxyethylene glycol two propylene esters (PEGDA), gamma-butyrolactone, butylacetate, cyclopentanone, propylene glycol monomethyl ether (PGMEA), tetrahydrofurfuryl alcohol (THFA), Methyl amyl ketone (2-heptanone), Diethylene Glycol list hexyl ether (DGME), propylene glycol monomethyl ether (PGME), ro-butyl acetate (nBA), propylene glycol list ethyl ether, propylene glycol list-just-propyl ether, Diethylene Glycol single-butyl ether acetic ester and water (H
2O) (its condition is dimethyl Asia (DMSO), N,N-dimethylacetamide (DMAc), 1-methyl pyrrolidone (NMP) or N for a composition wherein, dinethylformamide (DMF) for two compositions, three compositions or four composition mixtures.Wherein, clean with organic solvent including (but not limited to) tetrahydrofuran (THF) (THF), dioxan, methyl ethyl ketone (MEK), chloroform (CHCl
3), methylene dichloride, methyl alcohol, ethanol, Virahol, propyl carbinol, polyoxyethylene glycol two propylene esters (PEGDA), gamma-butyrolactone, butylacetate, cyclopentanone, propylene glycol monomethyl ether (PGMEA), tetrahydrofurfuryl alcohol (THFA), Methyl amyl ketone (2-heptanone), Diethylene Glycol list hexyl ether (DGME), propylene glycol monomethyl ether (PGME), ro-butyl acetate (nBA), propylene glycol list ethyl ether, the propylene glycol list-just-propyl ether or Diethylene Glycol single-butyl ether acetic ester or its mixture.
The base material that uses in the inventive method is including (but not limited to) the not flexual Silicon Wafer of tool, germanium wafer, glass or quartz, and the flexual polyethylene of tool (PE), polyester (PET) or polyimide (PI) base material etc.
Also about a kind of precursor aqueous solution of polyimide/silica composite material, it is to be got by aforesaid the inventive method preparation in the present invention.Precursor aqueous solution of the present invention comprises the polyamic acid with silicon oxide group, but wherein the carboxylic acid group of this silicon oxide group or this silicon oxide group and polyamic acid has sensitization polymeric unsaturated group.But sensitization polymeric unsaturated group is an ethene belongs to unsaturated group, is selected from the group that is made up of vinyl, allyl group, ethenylphenyl, allyl phenyl, propenyloxy group methyl, propenyloxy group ethyl, propenyloxy group propyl group, propenyloxy group butyl, propenyloxy group amyl group, propenyloxy group hexyl, metacryloxy methyl, metacryloxy ethyl, metacryloxy propyl group, metacryloxy butyl, metacryloxy amyl group and metacryloxy hexyl.
Precursor aqueous solution of the present invention can be coated and directly carry out exposure imaging on the base material, and film forming makes polyimide/silica composite material film.
Therefore, the present invention also blendes together material about a kind of polyimide/silicon oxide, and its tool hangs down volumetric shrinkage, and represents excellent heat resistance and optical property, low thermal coefficient of expansion, low-k, and good little shadow resolving power and dimensional stability.Person more so, matrix material of the present invention is through (generally being after about 300 ℃ of bakings) behind the baking-curing, the shrinking percentage of thickness of composite material is lower than 10%.These improvement can obtain further checking by the embodiment that is hereinafter provided.In view of the character of aforementioned excellence, matrix material of the present invention is applicable to many micromodules and semiconductor subassembly, comprises printed circuit board (PCB), flexible circuit board or semiconductor dielectric layer material; And photoelectric subassembly, comprise LCD screen separator, optical waveguide or optical waveguide connector.
Description of drawings
Fig. 1 is this case example 1 and comparative example 1 prepared solution (A) with (A1) after coating, soft roasting, exposure, the change in film thickness situation in stage intensification solidification process.
Fig. 2 is the solution (A) in this case test two and (A1) the TGA figure of the film in coating, soft roasting, exposure, after solidifying.
Fig. 3 is the solution (A) in this case test two and (A1) the DCS figure of the film in coating, soft roasting, exposure, after solidifying.
Fig. 4 is the solution (A) in this case test two and (A1) the TMA figure of the film in coating, soft roasting, exposure, after solidifying.
Fig. 5 for solution (A) in this case test three in coating, soft roasting, exposure, develop, solidify the SEM figure of pattern.
Fig. 6 is this case example 1 and comparative example 1 prepared solution (A) and (A1) infrared spectrogram of the film in coating, soft roasting, exposure, after solidifying.
Fig. 7 is this case example 1 and comparative example 1 prepared solution (A) and (A1) the near infrared light spectrogram of the film in coating, soft roasting, exposure, after solidifying.
Fig. 8 is this case embodiment 1 and comparative example 1 prepared solution (A) and (A1) the XPS spectrum figure of the film in coating, soft roasting, exposure, after solidifying.
Embodiment
The present invention will further be illustrated below with reference to embodiment and accompanying drawing, and embodiment does not only limit the scope of the invention in order to explanation.
Get 8 the milli not ear 4,4 '-oxygen base pentanoic (ODA) is dissolved in the N,N-DIMETHYLACETAMIDE (DMAc), and the dissolving back slowly adds the not pyromellitic dianhydride of ear (PMDA) of 10 millis, feeds nitrogen and also gives high degree of agitation, reaction is 24 hours under room temperature, obtains clarifying viscid polyamic acid (PAA) solution.Add the not 3-aminocarbonyl propyl triethoxyl silane (APrTEOS) of ear of 4 millis, stirring reaction is 4 hours under room temperature, make it connect the polyimide end, add the not tetramethoxy-silicane of ear (TMOS) of 8.21 millis subsequently, stir after 30 minutes add 1.67 millis not the deionized water of ear make it in reaction under the room temperature after 24 hours, the 2-metacryloxy ethyl triethoxysilane (MPTES) that adds 5.61 milli Mo Erke stirring reaction 4 hours under room temperature.Add the not allyl dimethyl base amine (Dimethylallylamine of ear of 20 millis again; DMAA) stirring reaction 4 hours under the room temperature; add at last 0.24 milli not ear two (2; 4; the 6-trimethylbenzoyl) phenylphosphine oxide is as the light initiator; stir made its dissolving in 30 minutes and be uniformly dispersed after, can obtain the precursor aqueous solution of sensing optical activity polyimide/silica composite material, be called solution (A).
Comparative example 1
Get 8 the milli not ear 4,4 '-oxygen base pentanoic ODA is dissolved in the N,N-DIMETHYLACETAMIDE (DMAc), and the dissolving back slowly adds the not pyromellitic dianhydride of ear (PMDA) of 10 millis, feeds nitrogen and also gives high degree of agitation, reaction is 24 hours under room temperature, obtains clarifying viscid polyamic acid (PAA) solution.Add the not 3-aminocarbonyl propyl triethoxyl silane (APrTEOS) of ear of 4 millis; stirring reaction is 4 hours under room temperature; make it connect the polyimide end; add not stirring reaction 4 hours under the allyl dimethyl base amine room temperature of ear of 20 millis again, add at last 0.24 milli not ear two (2,4; the 6-trimethylbenzoyl) phenylphosphine oxide is as the light initiator; stir made its dissolving in 30 minutes and be uniformly dispersed after, can obtain the precursor aqueous solution of sensing optical activity polyimide, be called solution (A1).
Test one:
Borrow method of spin coating with the coating 30 seconds on 4 o'clock Silicon Wafers of 1500rpm rotating speed gained solution (A), then on hot-plate with 120 ℃ soft roasting 4 minutes, the ultraviolet source with blank light shield and wavelength 365nm exposes then, exposure energy is 1800mJ/cm
2, baked 10 minutes with 120 ℃ of backs of exposing to the sun at hot-plate the back of exposing, and carries out the roasting firmly curing of multi-stage type with hot-plate then.Solidification value and time are respectively: 150 ℃ were toasted 30 minutes; 200 ℃ were toasted 30 minutes; 250 ℃ were toasted 30 minutes; 300 ℃ were toasted 30 minutes.Can obtain polyimide/silica composite material film.
Borrow method of spin coating with the coating 30 seconds on 4 o'clock Silicon Wafers of 1500rpm rotating speed gained solution (A1), then on hot-plate with 120 ℃ soft roasting 4 minutes, the ultraviolet source with blank light shield and wavelength 365nm exposes then, exposure energy is 1800mJ/cm
2, baked 10 minutes with 120 ℃ of backs of exposing to the sun at hot-plate the back of exposing, and carries out the roasting firmly curing of multi-stage type with hot-plate then.Solidification value and time are respectively: 150 ℃ were toasted 30 minutes; 200 ℃ were toasted 30 minutes; 250 ℃ were toasted 30 minutes; 300 ℃ were toasted 30 minutes.Can obtain Kapton.
With the solution (A) of embodiment 1, comparative example 1 gained with (A1) via rotary coating and the made film of baking-curing, measure its thickness as shown in Figure 1 with the variation situation in differing temps baking stage.After through 300 ℃ of baking-curings, its film thickness shrinks 9.1% (A) and 21.3% (A1) respectively as shown in Figure 1, and it is low volumetric shrinkage that polyimide of the present invention as can be known/silica composite material film obviously has general Kapton.This be since general Kapton after curing, the endless loop of acid amides acidic group forms imide, makes that tertiary amine on the DMAA can't continue to stay in the film with the form that forms the acid ion alkali ion salt with the acid amides acidic group, and causes tangible volumetric shrinkage.And prepared polyimide/silica composite material film among the present invention, because DMAA forms crosslinking polymerization with the MPTES of silicon oxide group after exposure, therefore after curing, the endless loop of acid amides acidic group forms imide, though the tertiary amine on the DMAA can't continue to exist with the form with acid amides acidic group formation acid ion alkali ion salt, but the covalent linkage that itself and MPTES form makes it still can continue to stay in the film, and reduces the formed volumetric shrinkage because of loss DMAA.
Test two:
With the solution (A) of embodiment 1 and comparative example 1 gained and (A1) in soft roasting, exposure on the Teflon dish, make the thick film of 200 microns of thickness after solidifying, carry out the thermal properties test of TGA, DSC, TMA, TGA, DSC, TMA, result are found in Fig. 2 to Fig. 4.The resulting thermo-cracking temperature of TGA (Td) is respectively 525 ℃ (A), 517 ℃ (A1); Glass tansition temperature (Tg) is respectively 272 ℃ (A), 264 ℃ (A1); Thermal expansivity is respectively 576ppm/ ℃ (A), 737ppm/ ℃ (B).Show that the made polyimide/silica composite material of getting everything ready low volumetric shrinkage of the present invention has simple polyimide material better thermostability and lower thermal expansivity.
Test three:
Borrow method of spin coating to be coated with 30 seconds on the Silicon Wafer at 4 o'clock embodiment 1 gained solution (A) with the 1500rpm rotating speed, then soft roasting 4 minutes with 120 ℃ on hot-plate, expose with light shield with pattern and the ultraviolet source of wavelength 365nm then, exposure energy is 1800mJ/cm
2, baked 10 minutes with 120 ℃ of backs of exposing to the sun at hot-plate the exposure back.Then with DMSO/ gamma-butyrolactone/H
2O=70/20/10 is a photographic developer by the synthetic mixing solutions of part by weight.Wafer is soaked in taking-up after 3 minutes in this developing solution, is that washing fluid is removed the developing solution flushing with methyl alcohol, after with nitrogen methyl alcohol being dried up, carries out the roasting firmly curing of multi-stage type with hot-plate at last again.Solidification value and time are respectively: 150 ℃ were toasted 30 minutes; 200 ℃ were toasted 30 minutes; 250 ℃ were toasted 30 minutes; 300 ℃ were toasted 30 minutes.Can obtain low-shrinkage, the sensing optical activity polyimide/formed pattern of silica composite material film.Little shadow pattern SEM figure of gained is found in Fig. 5, and live width is 3 microns, shows that this material possesses good little shadow pattern resolving power.
Test four:
Property analysis so that the film of embodiment 1 and comparative example 1 gained carries out comprises that infrared spectra, near infrared spectrum, XPS result are found in Fig. 6 to Fig. 8.
Show by the infrared spectra of Fig. 6 that polyimide/silicon oxide (A) has reacted and finish, and collection of illustrative plates (A) can obviously not observed in 1000-1200cm
-1The Si-O-Si absorption of vibrations.
Show that by the near infrared spectrum of Fig. 7 the main absorption loss in 1310nm wavelength place combine absorption from absorbing near c h bond second frequency multiplication to rotate with vibrations, thus the light of matrix material biography lose can be lower and reduce by c h bond density.
Fig. 8 is respectively solution (A) and reaches (A1) photoelectron of made film (XPS) N1s collection of illustrative plates, (A) collection of illustrative plates is Duoed a bond energy (binding energy) than the collection of illustrative plates of (A1) and is the characteristic peak of 398.3eV, caused by the nitrogen on the DMAA, 400.6 common characteristic peaks of two collection of illustrative plates are then caused by the nitrogen on the polyimide, the provable DMAA of XPS collection of illustrative plates is kept somewhere in film, and therefore reduces the volumetric shrinkage of the prepared composite material film of solution (A).
In sum, the prepared low volumetric shrinkage polyimide of the inventive method/silica composite material film has the obtained person of more traditional polyimide material and is low volumetric shrinkage, and has outstanding little shadow pattern resolving power and dimensional stability.In detail, the matrix material that the present invention is prepared has good heat-resisting character, optical property, low thermal coefficient of expansion, the loss of low light biography etc. after solidifying, can be used as the dielectric layer material in the manufacturing of waveguide of resistant to elevated temperatures high-performance optics or microelectronics and semi-conductor.Simultaneously, itself promptly can be used as the photoresistance composition, can directly carry out the step of exposure imaging and make required figure, can significantly reduce and make the complicated etching program of step release tradition, improves turnout and product fine rate.
Claims (29)
1. the preparation method of the precursor aqueous solution of a polyimide/silica composite material, this method comprises:
(A) provide a kind of polyamic acid solution;
(B) with a kind of general formula H
2N-R
1-Si (R
2)
3The amido coupler add in the solution of step (A) R in the general formula
1Be C
1-6Stretch alkyl or stretch aryl, and R
2Can be identical or differently, each represents C
1-6Alkoxyl group;
(C) a kind of silane compound monomer is added in step (B) the gained solution, make polyamic acid have the silicon oxide group;
(D) with a kind of general formula (R
6)
xSi (R
7)
(4-x)Monomer add in step (C) the gained solution, but make the silicon oxide group have sensitization polymeric unsaturated group; R in the general formula
6For but end has sensitization polymeric unsaturated group, R
7Be halogen, C
1-6Alkoxyl group, C
2-6Alkene oxygen base or aryloxy, and x be 1 to 3 integer and
(E) with a kind of general formula R
8N (R
9)
2Monomer add in step (D) the gained solution R in the general formula
8For but end has sensitization polymeric unsaturated group, and R
9Be C
1-6Alkyl, but make polyamic acid have sensitization polymeric unsaturated group, but obtain a kind of precursor aqueous solution of sensitization polymeric polyimide/silica composite material.
2. method that on base material, forms polyimide/silica composite material film, this method comprises:
(A) provide a kind of polyamic acid solution;
(B) with a kind of general formula H
2N-R
1-Si (R
2)
3The amido coupler add in the solution of step (A) R in the general formula
1Be C
1-6Stretch alkyl or stretch aryl, and R
2Can be identical or differently, each represents C
1-6Alkoxyl group;
(C) a kind of silane compound monomer is added in step (B) the gained solution, make polyamic acid have the silicon oxide group;
(D) with a kind of general formula (R
6)
xSi (R
7)
(4-x)Monomer add in step (C) the gained solution, but make the silicon oxide group have sensitization polymeric unsaturated group, R in the general formula
6For but end has sensitization polymeric unsaturated group, R
7Be halogen, C
1-6Alkoxyl group, C
2-6Alkene oxygen base or aryloxy, and x is 1 to 3 integer;
(E) with a kind of general formula R
8N (R
9)
2Monomer add R in step (D) the gained solution formula of
8For but end has sensitization polymeric unsaturated group, and R
9Be C
1-6Alkyl, but make polyamic acid have sensitization polymeric unsaturated group, but obtain a kind of precursor aqueous solution of sensitization polymeric polyimide/silica composite material;
(F) with step (E) gained solution coat on base material, steam desolventize after, the irradiation energy x ray exposure x; And
(G) toast in 120 ℃ to 300 ℃ temperature range, form polyimide/silica composite material film.
3. method according to claim 2, wherein energy-ray is ultraviolet ray.
4. method according to claim 1 and 2, wherein step (E) further is included under the existence of light initiator and carries out.
5. method according to claim 1 and 2, it further is contained in step
(C) and step (D) between with general formula R
4Si (R
5)
3(R wherein
4For end has the base of epoxy group(ing) and R
5Be halogen, C
1-6Alkoxyl group, C
2-6Alkene oxygen base or aryloxy) coupler add in step (C) the gained solution.
6. method according to claim 1 and 2, wherein this silane compound monomer has formula Si (R
3)
4, reach wherein each R
3For can identical or different representative halogen, C
1-6Alkoxyl group, C
2-6Alkene oxygen base or aryloxy, restricted condition are 4 R
3Non-is halogen simultaneously.
7. method according to claim 4, wherein this silane compound monomer comprises tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane or four butoxy silanes or its mixture.
8. method according to claim 1 and 2, but should sensitization polymeric unsaturated group be that ethene belongs to unsaturated group wherein, be selected from the group that is formed by vinyl, allyl group, ethenylphenyl, allyl phenyl, propenyloxy group methyl, propenyloxy group ethyl, propenyloxy group propyl group, propenyloxy group butyl, propenyloxy group amyl group, propenyloxy group hexyl, metacryloxy methyl, metacryloxy ethyl, metacryloxy propyl group, metacryloxy butyl, metacryloxy amyl group and metacryloxy hexyl.
9. method according to claim 1 and 2, wherein this general formula (R
6)
xSi (R
7)
(4-x)Monomer comprise 3-metacryloxy propyl trimethoxy silicane, 3-metacryloxy propyl-triethoxysilicane, 2-metacryloxy ethyl trimethoxy silane, 2-metacryloxy ethyl triethoxysilane, 3-metacryloxy butyl trimethoxy silane, 3-metacryloxy butyl triethoxyl silane, 3-propenyloxy group propyl trimethoxy silicane, 3-propenyloxy group propyl-triethoxysilicane, 2-propenyloxy group ethyl trimethoxy silane, 2-propenyloxy group ethyl triethoxysilane, 3-propenyloxy group butyl trimethoxy silane, 3-propenyloxy group butyl triethoxyl silane, 3-methyl propenyloxy group propyl trimethoxy silicane, 3-methyl propenyloxy group propyl-triethoxysilicane, 3-methyl propenyloxy group ethyl trimethoxy silane, 3-methyl propenyloxy group ethyl triethoxysilane, 3-methyl propenyloxy group butyl trimethoxy silane, 3-methyl propenyloxy group butyl triethoxyl silane, 3-metacryloxy propyl trimethoxy silicane, 3-metacryloxy propyl-triethoxysilicane, 3-metacryloxy ethyl trimethoxy silane, 3-metacryloxy ethyl triethoxysilane, 3-metacryloxy butyl trimethoxy silane, 3-metacryloxy butyl triethoxyl silane, vinyltrimethoxy silane, vinyltriethoxysilane, 3-ethenylphenyl Trimethoxy silane, 3-ethenylphenyl triethoxyl silane, 4-ethenylphenyl Trimethoxy silane, 4-ethenylphenyl triethoxyl silane, allyltrimethoxysilanis, allyltriethoxysilane, 4-allyl phenyl Trimethoxy silane, 4-allyl phenyl triethoxyl silane, two (3-metacryloxy propyl group) dimethoxy silane, two (3-metacryloxy propyl group) diethoxy silane, two (2-metacryloxy ethyl) dimethoxy silane, two (2-metacryloxy ethyl) diethoxy silane, two (3-metacryloxy butyl) dimethoxy silane, two (3-metacryloxy butyl) diethoxy silane, two (3-propenyloxy group propyl group) dimethoxy silane, two (3-propenyloxy group propyl group) diethoxy silane, two (2-propenyloxy group ethyl) dimethoxy silane, two (2-propenyloxy group ethyl) diethoxy silane, two (3-propenyloxy group butyl) dimethoxy silane, two (3-propenyloxy group butyl) diethoxy silane, divinyl dimethoxy silane, the divinyl diethoxy silane, diallyl dimethoxy silane, the diallyl diethoxy silane, three (3-metacryloxy propyl group) methoxy silane, three (3-metacryloxy propyl group) Ethoxysilane, three (2-metacryloxy ethyl) methoxy silane, three (2-metacryloxy ethyl) Ethoxysilane, three (3-metacryloxy butyl) methoxy silane, three (3-metacryloxy butyl) Ethoxysilane, three (3-propenyloxy group propyl group) methoxy silane, three (3-propenyloxy group propyl group) Ethoxysilane, three (2-propenyloxy group ethyl) methoxy silane, three (2-propenyloxy group ethyl) Ethoxysilane, three (3-propenyloxy group butyl) methoxy silane, three (3-propenyloxy group butyl) Ethoxysilane, the trivinyl methoxy silane, the trivinyl Ethoxysilane, triallyl methoxy silane or triallyl Ethoxysilane or its mixture.
10. method according to claim 9, wherein this general formula (R
6)
xSi (R
7)
(4-x)Monomer comprise 3-metacryloxy propyl trimethoxy silicane, 3-metacryloxy propyl-triethoxysilicane, 2-metacryloxy ethyl trimethoxy silane or 2-metacryloxy ethyl triethoxysilane or its mixture.。
11. method according to claim 1 and 2, wherein this general formula R
8N (R
9)
2Monomer comprise methacrylic acid 2-dimethylin ethyl ester, methacrylic acid 2-diethylin ethyl ester, methacrylic acid 2-dipropyl amido ethyl ester, 3-metacryloxy propyl-dimethyl amine, 3-metacryloxy propyl group diethylamine, 3-metacryloxy propyl group dipropylamine, 3-propenyloxy group propyl-dimethyl amine, 3-propenyloxy group propyl group diethylamide, 3-propenyloxy group propyl group dipropylamine, 3-methyl propenyloxy group propyl-dimethyl amine, 3-methyl propenyloxy group propyl group diethylamide, 3-methyl propenyloxy group propyl group dipropylamine, 4-(metacryloxy propyl group) phenyl dimethyl amine, 4-(metacryloxy propyl group) diethylamino phenyl base amine, 4-(metacryloxy propyl group) phenyl dipropylamine, 4-(metacryloxy ethyl) phenyl dimethyl amine, 4-(metacryloxy ethyl) diethylamino phenyl base amine, 4-(metacryloxy ethyl) phenyl dipropylamine, 4-(metacryloxy methyl) phenyl dimethyl amine, 4-(metacryloxy methyl) diethylamino phenyl base amine, 4-(metacryloxy methyl) phenyl dipropylamine, allyl dimethyl base amine, the allyl group diethylamide, the allyl group dipropylamine, 4-allyl dimethyl base amine, 4-allyl group diethylamide, 4-allyl group dipropylamine, 4-vinyl-dimethyl base amine, 4-vinyl diethylamide or 4-vinyl dipropylamine or its mixture.
12. method according to claim 11, this general formula R of tool
8N (R
9)
2Monomer comprise methacrylic acid 2-dimethylin ethyl ester, methacrylic acid 2-diethylin ethyl ester, methacrylic acid 2-dipropyl amido ethyl ester or allyl dimethyl base amine or its mixture.。
13. the preparation method of the precursor aqueous solution of a polyimide/silica composite material, this method comprises:
(A1) provide a kind of polyamic acid solution;
(B1) form the molecular grouping or the particulate solution of tool silicon oxide group from the silane compound monomer;
(C1) with a kind of general formula (R
6)
xSi (R
7)
(4-x)Monomer add in step (B1) the gained solution, but make this silicon oxide group have sensitization polymeric unsaturated group, R in the general formula
6For but end has sensitization polymeric unsaturated group, R
7Be halogen, C
1-6Alkoxyl group, C
2-6Alkene oxygen base or aryloxy, and x is 1 to 3 integer;
(D1) mixing step (A1) gained solution and step (C1) gained solution, but the solution that the silicon oxide group has the polyimide/silica composite material of sensitization polymeric unsaturated group formed; And
(E1) with a kind of general formula R
8N (R
9)
2Monomer add in step (D1) the gained solution R in the general formula
8For but end has sensitization polymeric unsaturated group, and R
9Be C
1-6Alkyl, but make polyamic acid have sensitization polymeric unsaturated group, but form a kind of precursor aqueous solution of sensitization polymeric polyimide/silica composite material.
14. a method that forms polyimide/silica composite material film on base material, this method comprises:
(A1) provide a kind of polyamic acid solution;
(B1) form the molecular grouping or the particulate solution of tool silicon oxide group from the silane compound monomer;
(C1) with a kind of general formula (R
6)
xSi (R
7)
(4-x)Monomer add in step (B1) the gained solution, but make this silicon oxide group have sensitization polymeric unsaturated group, R in the general formula
6For but end has sensitization polymeric unsaturated group, R
7Be halogen, C
1-6Alkoxyl group, C
2-6Alkene oxygen base or aryloxy, and x is 1 to 3 integer;
(D1) mixing step (A1) gained solution and step (C1) gained solution, but the solution that the silicon oxide group has the polyimide/silica composite material of sensitization polymeric unsaturated group formed;
(E1) with a kind of general formula R
8N (R
9)
2Monomer add in step (D1) the gained solution R in the general formula
8For but end has sensitization polymeric unsaturated group, and R
9Be C
1-6Alkyl, but make polyamic acid have sensitization polymeric unsaturated group, but form a kind of precursor aqueous solution of sensitization polymeric polyimide/silica composite material;
(F1) with step (E1) gained solution coat on base material, steam desolventize after, the irradiation energy x ray exposure x; And
(G1) toast in 120 ℃ to 300 ℃ temperature range, form polyimide/silica composite material film.
15. method according to claim 14, wherein energy-ray is ultraviolet ray.
16. according to claim 13 or 14 described methods, wherein step (E1) further is included under the existence of light initiator and carries out.
17. according to claim 13 or 14 described methods, it further comprises general formula H
2N-R
1-Si (R
2)
3The amido coupler add in step (A1) the gained solution R in the general formula
1Be C
1-6Stretch alkyl or stretch aryl, and R
2Can be the identical or different C of representative
1-6Alkoxyl group, remix step (D1) gained solution.
18. according to claim 13 or 14 described methods, wherein this silane compound monomer has formula Si (R
3)
4, reach wherein each R
3For can identical or different representative halogen, C
1-6Alkoxyl group, C
2-6Alkene oxygen base or aryloxy, restricted condition are 4 R
3Non-is halogen simultaneously.
19. method according to claim 18, wherein this silane compound monomer comprises tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane or four butoxy silanes or its mixture.
20. according to claim 13 or 14 described methods, but should sensitization polymeric unsaturated group be that ethene belongs to unsaturated group wherein, be selected from the group that is formed by vinyl, allyl group, ethenylphenyl, allyl phenyl, propenyloxy group methyl, propenyloxy group ethyl, propenyloxy group propyl group, propenyloxy group butyl, propenyloxy group amyl group, propenyloxy group hexyl, metacryloxy methyl, metacryloxy ethyl, metacryloxy propyl group, metacryloxy butyl, metacryloxy amyl group and metacryloxy hexyl.
21. according to claim 13 or 14 described methods, wherein this general formula (R
6)
xSi (R
7)
(4-x)Monomer comprise 3-metacryloxy propyl trimethoxy silicane, 3-metacryloxy propyl-triethoxysilicane, 2-metacryloxy ethyl trimethoxy silane, 2-metacryloxy ethyl triethoxysilane, 3-metacryloxy butyl trimethoxy silane, 3-metacryloxy butyl triethoxyl silane, 3-propenyloxy group propyl trimethoxy silicane, 3-propenyloxy group propyl-triethoxysilicane, 2-propenyloxy group ethyl trimethoxy silane, 2-propenyloxy group ethyl triethoxysilane, 3-propenyloxy group butyl trimethoxy silane, 3-propenyloxy group butyl triethoxyl silane, 3-methyl propenyloxy group propyl trimethoxy silicane, 3-methyl propenyloxy group propyl-triethoxysilicane, 3-methyl propenyloxy group ethyl trimethoxy silane, 3-methyl propenyloxy group ethyl triethoxysilane, 3-methyl propenyloxy group butyl trimethoxy silane, 3-methyl propenyloxy group butyl triethoxyl silane, 3-metacryloxy propyl trimethoxy silicane, 3-metacryloxy propyl-triethoxysilicane, 3-metacryloxy ethyl trimethoxy silane, 3-metacryloxy ethyl triethoxysilane, 3-metacryloxy butyl trimethoxy silane, 3-metacryloxy butyl triethoxyl silane, vinyltrimethoxy silane, vinyltriethoxysilane, 3-ethenylphenyl Trimethoxy silane, 3-ethenylphenyl triethoxyl silane, 4-ethenylphenyl Trimethoxy silane, 4-ethenylphenyl triethoxyl silane, allyltrimethoxysilanis, allyltriethoxysilane, 4-allyl phenyl Trimethoxy silane, 4-allyl phenyl triethoxyl silane, two (3-metacryloxy propyl group) dimethoxy silane, two (3-metacryloxy propyl group) diethoxy silane, two (2-metacryloxy ethyl) dimethoxy silane, two (2-metacryloxy ethyl) diethoxy silane, two (3-metacryloxy butyl) dimethoxy silane, two (3-metacryloxy butyl) diethoxy silane, two (3-propenyloxy group propyl group) dimethoxy silane, two (3-propenyloxy group propyl group) diethoxy silane, two (2-propenyloxy group ethyl) dimethoxy silane, two (2-propenyloxy group ethyl) diethoxy silane, two (3-propenyloxy group butyl) dimethoxy silane, two (3-propenyloxy group butyl) diethoxy silane, divinyl dimethoxy silane, the divinyl diethoxy silane, diallyl dimethoxy silane, the diallyl diethoxy silane, three (3-metacryloxy propyl group) methoxy silane, three (3-metacryloxy propyl group) Ethoxysilane, three (2-metacryloxy ethyl) methoxy silane, three (2-metacryloxy ethyl) Ethoxysilane, three (3-metacryloxy butyl) methoxy silane, three (3-metacryloxy butyl) Ethoxysilane, three (3-propenyloxy group propyl group) methoxy silane, three (3-propenyloxy group propyl group) Ethoxysilane, three (2-propenyloxy group ethyl) methoxy silane, three (2-propenyloxy group ethyl) Ethoxysilane, three (3-propenyloxy group butyl) methoxy silane, three (3-propenyloxy group butyl) Ethoxysilane, the trivinyl methoxy silane, the trivinyl Ethoxysilane, triallyl methoxy silane or triallyl Ethoxysilane or its mixture.
22. method according to claim 21, wherein this general formula (R
6)
xSi (R
7)
(4-x)Monomer comprise 3-metacryloxy propyl trimethoxy silicane, 3-metacryloxy propyl-triethoxysilicane, 2-metacryloxy ethyl trimethoxy silane or 2-metacryloxy ethyl triethoxysilane or its mixture.
23. according to claim 13 or 14 described methods, wherein this general formula R
8N (R
9)
2Monomer comprise methacrylic acid 2-dimethylin ethyl ester, methacrylic acid 2-diethylin ethyl ester, methacrylic acid 2-dipropyl amido ethyl ester, 3-metacryloxy propyl-dimethyl amine, 3-metacryloxy propyl group diethylamine, 3-metacryloxy propyl group dipropylamine, 3-propenyloxy group propyl-dimethyl amine, 3-propenyloxy group propyl group diethylamide, 3-propenyloxy group propyl group dipropylamine, 3-methyl propenyloxy group propyl-dimethyl amine, 3-methyl propenyloxy group propyl group diethylamide, 3-methyl propenyloxy group propyl group dipropylamine, 4-(metacryloxy propyl group) phenyl dimethyl amine, 4-(metacryloxy propyl group) diethylamino phenyl base amine, 4-(metacryloxy propyl group) phenyl dipropylamine, 4-(metacryloxy ethyl) phenyl dimethyl amine, 4-(metacryloxy ethyl) diethylamino phenyl base amine, 4-(metacryloxy ethyl) phenyl dipropylamine, 4-(metacryloxy methyl) phenyl dimethyl amine, 4-(metacryloxy methyl) diethylamino phenyl base amine, 4-(metacryloxy methyl) phenyl dipropylamine, allyl dimethyl base amine, the allyl group diethylamide, the allyl group dipropylamine, 4-allyl dimethyl base amine, 4-allyl group diethylamide, 4-allyl group dipropylamine, 4-vinyl-dimethyl base amine, 4-vinyl diethylamide or 4-vinyl dipropylamine or its mixture.
24. method according to claim 23,, this general formula R wherein
8N (R
9)
2Monomer comprise methacrylic acid 2-dimethylin ethyl ester, methacrylic acid 2-diethylin ethyl ester, methacrylic acid 2-dipropyl amido ethyl ester or allyl dimethyl base amine or its mixture.
25. the precursor aqueous solution of a polyimide/silica composite material, it comprises the polyamic acid with silicon oxide group, has sensitization polymeric unsaturated group but it is characterized by this silicon oxide group.
26. method according to claim 25, wherein but the unsaturated group of photopolymer is that ethene belongs to unsaturated group, is selected from the group that is made up of vinyl, allyl group, ethenylphenyl, allyl phenyl, propenyloxy group methyl, propenyloxy group ethyl, propenyloxy group propyl group, propenyloxy group butyl, propenyloxy group amyl group, propenyloxy group hexyl, metacryloxy methyl, metacryloxy ethyl, metacryloxy propyl group, metacryloxy butyl, metacryloxy amyl group and metacryloxy hexyl.
27. method according to claim 25, but wherein the carboxylic acid group of this silicon oxide group and polyamic acid has sensitization polymeric unsaturated group.
28. a polyimide/silica composite material is characterized by the low volumetric shrinkage of this material tool; And this material is after solidifying, and the shrinking percentage of its thickness is lower than 10%.
29. method according to claim 28, it is by obtained as each method in the claim 1 to 24.
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| WO2020186585A1 (en) * | 2019-03-21 | 2020-09-24 | 深圳先进技术研究院 | Developer and patterning method for photosensitive polyimide precursor |
| CN112375222A (en) * | 2020-11-30 | 2021-02-19 | 拓米(成都)应用技术研究院有限公司 | Intramolecular hybrid semi-inorganic-semi-organic transparent film and preparation method thereof |
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| WO2020186585A1 (en) * | 2019-03-21 | 2020-09-24 | 深圳先进技术研究院 | Developer and patterning method for photosensitive polyimide precursor |
| CN112375222A (en) * | 2020-11-30 | 2021-02-19 | 拓米(成都)应用技术研究院有限公司 | Intramolecular hybrid semi-inorganic-semi-organic transparent film and preparation method thereof |
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