WO2009151050A1 - 中空パッケージ用感光性樹脂組成物、その硬化物及び該樹脂組成物を用いた積層体並びにマイクロデバイス - Google Patents
中空パッケージ用感光性樹脂組成物、その硬化物及び該樹脂組成物を用いた積層体並びにマイクロデバイス Download PDFInfo
- Publication number
- WO2009151050A1 WO2009151050A1 PCT/JP2009/060525 JP2009060525W WO2009151050A1 WO 2009151050 A1 WO2009151050 A1 WO 2009151050A1 JP 2009060525 W JP2009060525 W JP 2009060525W WO 2009151050 A1 WO2009151050 A1 WO 2009151050A1
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- WO
- WIPO (PCT)
- Prior art keywords
- resin composition
- photosensitive resin
- hollow
- epoxy
- formula
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 112
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 69
- 239000003822 epoxy resin Substances 0.000 claims abstract description 64
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims description 51
- 239000004593 Epoxy Substances 0.000 claims description 32
- 125000003700 epoxy group Chemical group 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 14
- 239000003505 polymerization initiator Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 238000007789 sealing Methods 0.000 claims description 14
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 239000011256 inorganic filler Substances 0.000 claims description 5
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 5
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001721 transfer moulding Methods 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 8
- 238000012663 cationic photopolymerization Methods 0.000 abstract description 3
- 239000003999 initiator Substances 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract 1
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- 238000000034 method Methods 0.000 description 25
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- -1 diphenyliodonium hexafluorophosphate Chemical compound 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 13
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- 239000004020 conductor Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 9
- 239000013039 cover film Substances 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 238000000206 photolithography Methods 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 239000006087 Silane Coupling Agent Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000001723 curing Methods 0.000 description 6
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000000059 patterning Methods 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- SURWYRGVICLUBJ-UHFFFAOYSA-N 2-ethyl-9,10-dimethoxyanthracene Chemical compound C1=CC=CC2=C(OC)C3=CC(CC)=CC=C3C(OC)=C21 SURWYRGVICLUBJ-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 2
- KSMGAOMUPSQGTB-UHFFFAOYSA-N 9,10-dibutoxyanthracene Chemical compound C1=CC=C2C(OCCCC)=C(C=CC=C3)C3=C(OCCCC)C2=C1 KSMGAOMUPSQGTB-UHFFFAOYSA-N 0.000 description 2
- NHRINLYFOKGDFL-UHFFFAOYSA-N CC(COC)OC1=C[I]=CC=C1 Chemical compound CC(COC)OC1=C[I]=CC=C1 NHRINLYFOKGDFL-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- SJWNMXYJLKDWOG-UHFFFAOYSA-N [2-(4-methoxynaphthalen-1-yl)-2-oxoethyl]-dimethylsulfanium Chemical compound C1=CC=C2C(OC)=CC=C(C(=O)C[S+](C)C)C2=C1 SJWNMXYJLKDWOG-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- XALRUHBKYUUYEF-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)methylsulfonyl-trifluoromethane;tris[4-(4-acetylphenyl)sulfanylphenyl]sulfanium Chemical compound FC(F)(F)S(=O)(=O)[C-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F.C1=CC(C(=O)C)=CC=C1SC1=CC=C([S+](C=2C=CC(SC=3C=CC(=CC=3)C(C)=O)=CC=2)C=2C=CC(SC=3C=CC(=CC=3)C(C)=O)=CC=2)C=C1 XALRUHBKYUUYEF-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 229920006336 epoxy molding compound Polymers 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 2
- 239000005001 laminate film Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000005459 micromachining Methods 0.000 description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000010897 surface acoustic wave method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- JFZKOODUSFUFIZ-UHFFFAOYSA-N trifluoro phosphate Chemical compound FOP(=O)(OF)OF JFZKOODUSFUFIZ-UHFFFAOYSA-N 0.000 description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- ZIKLJUUTSQYGQI-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxypropoxy)propane Chemical compound CCOCC(C)OCC(C)OCC ZIKLJUUTSQYGQI-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- BRKORVYTKKLNKX-UHFFFAOYSA-N 2,4-di(propan-2-yl)thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC(C(C)C)=C3SC2=C1 BRKORVYTKKLNKX-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- HSDVRWZKEDRBAG-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COC(CCCCC)OCC1CO1 HSDVRWZKEDRBAG-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 description 1
- PLDLPVSQYMQDBL-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethoxy)-2,2-bis(oxiran-2-ylmethoxymethyl)propoxy]methyl]oxirane Chemical compound C1OC1COCC(COCC1OC1)(COCC1OC1)COCC1CO1 PLDLPVSQYMQDBL-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- SQLIUQWZSOABAR-UHFFFAOYSA-N 2-chloro-9,10-dimethoxyanthracene Chemical compound ClC1=CC=C2C(OC)=C(C=CC=C3)C3=C(OC)C2=C1 SQLIUQWZSOABAR-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- BDPJILVXUVJWBF-UHFFFAOYSA-N 2-ethyl-9,10-dipropoxyanthracene Chemical compound CCC1=CC=C2C(OCCC)=C(C=CC=C3)C3=C(OCCC)C2=C1 BDPJILVXUVJWBF-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 1
- WSMQKESQZFQMFW-UHFFFAOYSA-N 5-methyl-pyrazole-3-carboxylic acid Chemical compound CC1=CC(C(O)=O)=NN1 WSMQKESQZFQMFW-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- FUWFDADDJOUNDL-UHFFFAOYSA-N 9,10-diethoxy-2-ethylanthracene Chemical compound CCC1=CC=C2C(OCC)=C(C=CC=C3)C3=C(OCC)C2=C1 FUWFDADDJOUNDL-UHFFFAOYSA-N 0.000 description 1
- GJNKQJAJXSUJBO-UHFFFAOYSA-N 9,10-diethoxyanthracene Chemical compound C1=CC=C2C(OCC)=C(C=CC=C3)C3=C(OCC)C2=C1 GJNKQJAJXSUJBO-UHFFFAOYSA-N 0.000 description 1
- JWJMBKSFTTXMLL-UHFFFAOYSA-N 9,10-dimethoxyanthracene Chemical compound C1=CC=C2C(OC)=C(C=CC=C3)C3=C(OC)C2=C1 JWJMBKSFTTXMLL-UHFFFAOYSA-N 0.000 description 1
- LBQJFQVDEJMUTF-UHFFFAOYSA-N 9,10-dipropoxyanthracene Chemical compound C1=CC=C2C(OCCC)=C(C=CC=C3)C3=C(OCCC)C2=C1 LBQJFQVDEJMUTF-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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Images
Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
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- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
Definitions
- the present invention relates to a photosensitive resin composition. More specifically, the present invention relates to a photosensitive resin composition for a hollow package suitable for a semiconductor / MEMS photosensitive material, particularly a hollow package of a microdevice having a fine mechanical structure such as MEMS.
- a photosensitive resin composition for a hollow package suitable for a semiconductor / MEMS photosensitive material particularly a hollow package of a microdevice having a fine mechanical structure such as MEMS.
- micro-electro-mechanical systems such as switches and micro-variable capacitors, or by combining with semiconductor chips, It is expected that more precise control will be possible.
- the various MEMS described above require a certain space (cavity) around the structure in order for the mechanical structure itself to operate and function. Many.
- a mechanical structure since such a mechanical structure is very fine, it may be destroyed during a subsequent process such as dicing, and may not fully function. Therefore, it is necessary to protect the mechanical structure from the external environment at the wafer level by a hollow package surrounded by a protective material so as to have a certain cavity.
- a hollow package is used in which a substrate having an uneven structure is bonded to a substrate having a mechanical structure by a technique such as anodic bonding, eutectic bonding, or diffusion bonding.
- these methods generally require work at a very high temperature, so that the processing takes time and the productivity is poor.
- Non-Patent Document 1 proposes a method for obtaining a hollow package by performing photolithography using a certain photosensitive resin composition.
- the method using the photosensitive resin composition does not require a high-temperature process, and a hollow package can be obtained simply and with high throughput, so that the production cost can be kept low and the microfabrication is relatively easy. There is an advantage that it can be downsized and thinned.
- the present inventors have conducted intensive studies. As a result, by selecting a specific epoxy resin, the present inventors show high strength even in a high temperature range where transfer molding is performed, and are sufficient as a material for a MEMS package. A photosensitive resin composition having strength can be obtained, and further by adding a liquid epoxy resin, a photosensitive resin composition that can be easily handled as a laminate (dry film resist) can be obtained without reducing the strength of the cured product. As a result, the present invention has been completed.
- a photosensitive resin composition for a hollow package comprising a trisphenolmethane type epoxy resin (A) represented by the following formula (1) and a photocationic polymerization initiator (B)
- each R independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group or a phenyl group, and m is the number of R and represents an integer of 1 to 3. Is an average value and 0 ⁇ n ⁇ 10).
- the photosensitive resin composition for a hollow package according to the above item (2) which is one type or two or more types selected from the group consisting of epoxy resins (C-3) represented by: (4) The photosensitive resin composition for a hollow package according to any one of (1) to (3), further comprising a reactive epoxy monomer (D), (5) The photosensitive resin composition for a hollow package according to (4), wherein the reactive epoxy monomer (D) is bisphenol A diglycidyl ether, (6) The photosensitive resin composition for a hollow package according to any one of (1) to (5), further including an inorganic filler (F), (7) A cured product obtained by curing the photosensitive resin composition for a hollow package according to any one of (1) to (6), (8) A substrate, a microelectromechanical system formed on the substrate, and the cured product described in (7) above, wherein the microelectronic system is provided so as to secure a space around the microelectromechanical system.
- C-3 epoxy resins
- a micro device comprising a cavity securing portion that covers a mechanical system, and a sealing layer that is formed to include resin and is provided so as to cover the cavity securing portion; (9) A laminate of a photosensitive resin composition for a hollow package in which the photosensitive resin composition for a hollow package according to any one of (1) to (6) is sandwiched between substrates, About.
- the cured product of the photosensitive resin composition for a hollow package of the present invention is characterized by exhibiting high strength even in a high temperature range.
- the hollow package is sealed by a transfer molding method.
- the space (cavity) formed by the hollow package can be sufficiently retained.
- the photosensitive resin composition for a hollow package of the present invention is useful for producing a MEMS device having a cavity.
- each R independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group or a phenyl group.
- M is the number of R and represents an integer of 1 to 3
- n is (Average value, 0 ⁇ n ⁇ 10.)
- the trisphenolmethane type epoxy resin (A) represented by the formula (1) is an epoxy resin known per se. For example, if necessary, a phenol derivative obtained by reacting phenols and hydroxybenzaldehyde in a nitrogen atmosphere is usually used. It is produced by glycidylation with epihalohydrin such as epichlorohydrin by the method.
- the “trisphenolmethane type epoxy resin (A) represented by the formula (1)” means an epoxy resin mainly composed of the epoxy resin represented by the formula (1).
- the technical scope of the present invention also includes subcomponents produced when the epoxy resin is produced, high molecular weight polymers of the epoxy resin represented by the formula (1), and the like.
- Examples of the alkyl group having 1 to 6 carbon atoms in R in the formula (1) include a methyl group, an ethyl group, a propyl group, a butyl group, and a cyclohexyl group.
- R is preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom.
- These trisphenol methane type epoxy resins (A) can also be obtained from the market.
- EPPN-501H (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 162-172 g / eq., Softening point 51-57 ° C.)
- EPPN-501HY (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 163- 175 g / eq., Softening point 57-63 ° C.)
- EPPN-502H (trade name, Nippon Kayaku Co., Ltd., epoxy equivalent 158-178 g / eq., Softening point 60-72 ° C.)
- EPPN-503 (trade name) Available from Nippon Kayaku Co., Ltd., with an epoxy equivalent of 170 to 190 g / eq., Softening point of 80 to 100 ° C.).
- the epoxy equivalent of the trisphenolmethane type epoxy resin (A) used in the present invention is preferably 400 or less.
- a crosslinking density becomes low and the tendency of the strength of a cured film, chemical resistance, heat resistance, and crack resistance to fall is seen.
- the softening point of the epoxy resin is too low, mask sticking is likely to occur during patterning, and further, it tends to be softened at room temperature when used as a laminate (dry film resist).
- the softening point of the epoxy resin is too high, it is difficult to soften the laminate (dry film resist) when it is laminated on the substrate, and there is a tendency that the bonding property to the substrate is deteriorated.
- the preferred softening point of the trisphenolmethane type epoxy resin (A) is 50 to 100 ° C., more preferably 60 to 90 ° C.
- the photocationic polymerization initiator (B) means a chemical species that generates a cationic species by irradiation with active energy rays.
- the cationic photopolymerization initiator used in the present invention is not particularly limited as long as it has sufficient performance to cure the trisphenolmethane type epoxy resin (A).
- Examples of the photocationic polymerization initiator (B) that can be used include aromatic iodonium complex salts and aromatic sulfonium complex salts.
- aromatic iodonium complex salt examples include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, and triluku.
- Miliodonium tetrakis (pentafluorophenyl) borate (trade name: Rhodosyl Photoinitiator 2074, manufactured by Rhodia), di (4-tert-butyl) iodonium tris (trifluoromethanesulfonyl) methanide (trade name: CGI BBIC C1, Ciba Specialty Chemicals Etc.).
- aromatic sulfonium complex salt examples include 4-thiophenyldiphenylsulfonium hexafluoroantimonate (trade name CPI-101A, manufactured by San Apro Corporation), thiophenyldiphenylsulfonium tris (pentafluoroethyl) tri Fluorophosphate (trade name CPI-210S, manufactured by San Apro Corporation), 4- ⁇ 4- (2-chlorobenzoyl) phenylthio ⁇ phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate (trade name SP-172, Asahi Denka Kogyo Co., Ltd.), a mixture of aromatic sulfonium hexafluoroantimonate containing 4-thiophenyldiphenylsulfonium hexafluoroantimonate (trade name UVI-6976, manufactured by Dow Chemical Co., Ltd.) and triphenyl Rus
- aromatic sulfonium complex salts are preferred because they are excellent in thermal stability in the present invention.
- aromatic sulfonium complex salts non-antimony thiophenyldiphenylsulfonium tris (pentafluoroethyl) is preferred.
- Trifluorophosphate triphenylsulfonium tris (trifluoromethanesulfonyl) methanide, (2- (4-methoxynaphthalen-1-yl) -2-oxoethyl) dimethylsulfonium tetrakis (pentafluorophenyl) borate, tris [4- (4- Acetylphenylsulfanyl) phenyl] sulfonium tris [(trifluoromethyl) sulfonyl] methanide and the like are more preferable.
- photocationic polymerization initiators (B) can be used alone or in combination of two or more in the photosensitive resin composition for hollow packages of the present invention. If the content of the photocationic polymerization initiator in the photosensitive resin composition for a hollow package is too small, it becomes difficult to obtain a sufficient curing rate, and conversely if too large, it is not economical. From these points, the content of the photocationic polymerization initiator (B) in the photosensitive resin composition for a hollow package of the present invention is the total amount of epoxy resin (epoxy resin (C) and / or reactive epoxy monomer described later). In the case of containing (D), the content is preferably 0.01 to 15% by mass, more preferably 1 to 10% by mass.
- the photosensitive resin composition for a hollow package in the present invention can further contain an epoxy resin (C) having two or more epoxy groups in one molecule.
- the epoxy resin (C) is not particularly limited as long as it has two or more epoxy groups in one molecule, but an aromatic polyfunctional glycidyl ether in which the cured product exhibits high strength even in a high temperature range is preferable.
- aromatic polyfunctional glycidyl ethers that can be used include bisphenol A novolak type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, phenol aralkyl type epoxy resins, dicyclopentadiene type epoxy resins, and naphthol cresol copolycondensation type epoxies.
- the resin include polyfunctional epoxy resins (C-1) to (C-3) represented by the following formulas (2) to (4).
- epoxy resin (C-1) represented by the formula (2) include jER157 (trade name, manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent of 180 to 250 g / eq., Softening point of 80 to 90 ° C.), EPON SU-8 (trade name, manufactured by Resolution Performance Products, epoxy equivalent of 195 to 230 g / eq., Softening point of 80 to 90 ° C.) and the like can be obtained from the market.
- each R independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group or a phenyl group, m is the number of R, and represents an integer of 1 to 3; Is an average value, and 0 ⁇ p ⁇ 10.
- the alkyl group having 1 to 6 carbon atoms in R in the formula (3) include a methyl group, an ethyl group, a propyl group, a butyl group, and a cyclohexyl group.
- a hydrogen atom or a methyl group is preferable, and a methyl group is more preferable. preferable.
- the most preferred combination in the formula (3) includes an o-cresol novolac type epoxy resin in which R is a methyl group and m is 1, and the substitution position of R is an ortho position relative to the glycidyl group.
- Specific examples of the epoxy resin (C-2) represented by the formula (3) include EOCN-1020 (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of 190 to 210 g / eq., Softening point of 55 to 85 ° C.
- Specific examples of the epoxy resin (C-3) represented by the formula (4) include NC-6000 (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of 205 to 215 g / eq., Softening point of 55 to 65 ° C. NC-6300H (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 230 to 235 g / eq., Softening point: 70 to 72 ° C.), etc. are available from the market.
- one or more of epoxy resins (C) having two or more epoxy groups in one molecule can be arbitrarily selected and used. It is preferable to use one or more of the epoxy resins (C-1) to (C-3) represented by the formulas (2) to (4).
- the blending ratio of the epoxy resin (C) having two or more epoxy groups in one molecule is trisphenolmethane.
- Type epoxy resin (A) (hereinafter sometimes simply referred to as “component A”), usually 0 to 95% by mass, preferably 50 to 95%, based on the total amount of reactive epoxy monomer (D) and component C described later % By mass. When content exceeds 95 mass%, the mixture ratio of A component will decrease too much, and hardened
- the content is less than 50% by mass, the sensitivity of the photosensitive resin composition may be lowered, and in order to obtain a cured product having high strength even in a high temperature range, it is necessary to irradiate with light for a long time. Not right.
- a reactive epoxy monomer (D) (hereinafter simply referred to as “D”) is used in order to further improve the flexibility when a laminate (dry film resist) is used.
- component may be added.
- the reactive epoxy monomer here refers to an epoxy resin that is liquid at normal temperature or has a softening point of 40 ° C. or lower.
- a glycidyl ether compound having miscibility with the A component, the B component, and the C component can be used.
- Specific examples thereof include diethylene glycol diglycidyl ether, hexanediol diglycidyl ether, Methylolpropane diglycidyl ether, polypropylene glycol diglycidyl ether (trade name: ED506, manufactured by ADEKA Corporation), trimethylolpropane triglycidyl ether (trade name: ED505, manufactured by ADEKA Corporation), trimethylolpropane triglycidyl ether (trade name: EX321L, Nagase ChemteX Corporation, low chlorine type), pentaerythritol tetraglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether And the like.
- bisphenol A diglycidyl ether is preferable because a cured product having high strength can be obtained even in a high temperature range.
- These can be used alone or in admixture of two or more.
- the addition amount of the D component is preferably 20% by mass or less, and particularly preferably 5% by mass to 15% by mass with respect to the total of the A component, the C component and the D component.
- the solvent (E) can be used to lower the viscosity of the photosensitive resin composition for a hollow package of the present invention and improve the coating properties.
- organic solvents that are usually used for inks, paints, and the like can be used, and any solvent having a sufficient dissolving power for the above-described components can be used.
- organic solvents include ketones such as acetone, ethyl methyl ketone, cyclohexanone and cyclopentanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether.
- Glycol ethers ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate and esters such as ⁇ -butyrolactone, alcohols such as methanol, ethanol, ceresolve and methyl ceresolve, octane and decane, etc.
- examples thereof include petroleum solvents such as aliphatic hydrocarbons, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.
- solvents can be used alone or in admixture of two or more.
- the solvent component is added for the purpose of adjusting the film thickness and applicability when applied to the base material, in order to appropriately maintain the solubility and volatility of each component, the liquid viscosity of the entire resin composition, and the like.
- the content of the solvent in the photosensitive resin composition for a hollow package is preferably 95% by mass or less, and particularly preferably 10 to 90% by mass.
- a miscible adhesion imparting agent may be used for the purpose of further improving the adhesion of the resin composition to the substrate.
- a coupling agent such as a silane coupling agent and a titanium coupling agent can be used, and a silane coupling agent is preferable.
- silane coupling agents that can be used include 3-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-methacryloxypropyltri Methoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (amino Ethyl) -3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane and the like.
- These adhesiveness imparting agents can be used alone or in combination of two or more.
- the adhesion-imparting agent When the adhesion-imparting agent is used in excess, the physical properties of the cured product can be reduced by reducing the crosslink density of the cured product of the epoxy resin composition for hollow packages of the present invention or remaining in the cured product unreacted. May decrease.
- the adhesion-imparting agent is suitable for use within a range that does not adversely affect the effect of a small amount depending on the substrate, and the use ratio thereof is determined in the epoxy resin composition for a hollow package of the present invention. 15 mass% or less is preferable, Most preferably, it is 5 mass% or less.
- a sensitizer that plays a role of absorbing ultraviolet light and supplying the absorbed light energy to the photocationic polymerization initiator may be used.
- sensitizers that can be used include anthracene compounds having an alkoxy group at the 9th and 10th positions (9,10-dialkoxyanthracene derivatives), thioxanthones, and the like.
- alkoxy group in the 9,10-dialkoxyanthracene derivative include C1-C4 alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
- the 9,10-dialkoxyanthracene derivative may further have a substituent at sites other than the 9th and 10th positions.
- substituents which may be included include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, C1-C4 alkyl groups such as methyl group, ethyl group and propyl group, and sulfonic acid alkyl esters. Groups, carboxylic acid alkyl ester groups and the like. Examples of the alkyl in the sulfonic acid alkyl ester group and the carboxylic acid alkyl ester include C1-C4 alkyl such as methyl, ethyl, and propyl. The substitution position of these substituents is preferably the 2-position.
- 9,10-dialkoxyanthracene derivative examples include, for example, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10- Dimethoxy-2-ethylanthracene, 9,10-diethoxy-2-ethylanthracene, 9,10-dipropoxy-2-ethylanthracene, 9,10-dimethoxy-2-chloroanthracene, 9,10-dimethoxyanthracene-2-sulfone And acid methyl ester, 9,10-diethoxyanthracene-2-sulfonic acid methyl ester, and 9,10-dimethoxyanthracene-2-carboxylic acid methyl ester.
- the use of 9,10-dimethoxy-2-ethylanthracene and 9,10-dibutoxyanthracene is particularly preferred.
- thioxanthones include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, and the like.
- 2,4-diethylthioxanthone (trade name: Kayacure DETX- S, manufactured by Nippon Kayaku Co., Ltd.), 2-isopropylthioxanthone is preferable, and 2,4-diethylthioxanthone is particularly preferable.
- sensitizers can be used alone or in admixture of two or more. However, since the sensitizer component exhibits its effect in a small amount, its use ratio is 100 with respect to the photocationic polymerization initiator (B). It is preferably at most 20 mass%, particularly preferably at most 20 mass%.
- an ion catcher may be added when it is necessary to reduce the adverse effects due to the ions derived from the photocationic polymerization initiator (B).
- the ion catcher include trismethoxyaluminum, trisethoxyaluminum, trisisopropoxyaluminum, isopropoxydiethoxyaluminum, trisbutoxyaluminum and other alkoxyaluminum, trisphenoxyaluminum and trisparamethylphenoxyaluminum such as phenoxyaluminum, tris Acetoxyaluminum, trisstearatoaluminum, trisbutyratealuminum, trispropionatoaluminum, trisacetylacetonatoaluminum, tristrifluoroacetylacetonatoaluminum, trisethylacetoacetatoaluminum, diacetylacetonatodip
- thermoplastic resin examples include polyethersulfone, polystyrene, and polycarbonate.
- colorant examples include phthalocyanine blue, phthalocyanine green, iodin green, crystal violet, titanium oxide, carbon black, and naphthalene black.
- thickener examples include olben, benton and montmorillonite.
- antifoaming agent examples include silicone-based, fluorine-based and polymer-based antifoaming agents.
- the amount of these additives used is, for example, approximately 0.1 to 30% by mass in the photosensitive resin composition for hollow packages of the present invention, but may be increased or decreased as appropriate according to the purpose of use. Can do.
- Examples of the photosensitive resin composition for a hollow package of the present invention include barium sulfate, barium titanate, silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica powder.
- An inorganic filler (F) can be used, and the usage-amount is 60 mass% or less in the photosensitive resin composition for hollow packages of this invention. If the particle size of the inorganic filler is too large, the light transmittance may be reduced and sufficient lithography performance may not be exhibited. Therefore, the average particle diameter of the inorganic filler is preferably 5 ⁇ m or less, and more preferably 1 ⁇ m or less.
- the photosensitive resin composition for a hollow package of the present invention is prepared by adding the above-mentioned optional components to the above-mentioned essential components, mixing and stirring as necessary, but if necessary, a dissolver, a homogenizer, three You may disperse and mix using dispersers, such as a roll mill. Moreover, after mixing, you may further filter using a mesh, a membrane filter, etc.
- the photosensitive resin composition for a hollow package of the present invention is preferably used in a liquid state.
- an outline of a coating method and a curing method will be described below.
- the photosensitive resin composition for a hollow package of the present invention on a metal substrate such as silicon, aluminum or copper, a ceramic substrate such as lithium tantalate, glass, silicon oxide or silicon nitride, a substrate such as polyimide or polyethylene terephthalate. Is applied by using a spin coater or the like at a thickness of 0.1 to 1000 ⁇ m, and the solvent is removed by a heat treatment at 60 to 130 ° C. for about 5 to 60 minutes to form a photosensitive resin composition layer. Next, a mask having a predetermined pattern was placed on the photosensitive resin composition layer provided on the substrate and irradiated with ultraviolet rays, and heat treatment (PEB) was performed at 50 to 130 ° C. for about 1 to 50 minutes.
- PEB heat treatment
- a pattern is formed by developing the unexposed portion at room temperature to 50 ° C. for about 1 to 180 minutes using a developer. Further, by subjecting the obtained pattern to heat treatment at 130 to 200 ° C. for about 10 to 360 minutes, a cured product of the photosensitive resin composition for a hollow package of the present invention that satisfies various characteristics can be obtained.
- the developer for example, an organic solvent such as ⁇ -butyrolactone, triethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, or a mixed solution of the organic solvent and water can be used.
- a paddle type, spray type, shower type, or other developing device may be used, and ultrasonic irradiation may be performed as necessary.
- the photosensitive resin composition for a hollow package of the present invention is applied on a base film using a roll coater, a die coater, a knife coater, a bar coater, a gravure coater, etc., and then used in a drying furnace set at 45 to 100 ° C. Then, a predetermined amount of the solvent is removed, and a cover film or the like is further laminated as necessary to obtain a laminate (dry film resist). At this time, the thickness of the resist on the base film is adjusted to 2 to 100 ⁇ m.
- a film of polyester, polypropylene, polyethylene, TAC, polyimide, or the like is used for example.
- These films may be subjected to a release treatment with a silicone-type release treatment agent, a non-silicone-type release treatment agent, or the like as necessary.
- a laminate obtained by peeling a cover film onto a substrate with a hand roll, a laminator or the like at a temperature of 40 to 100 ° C. and a pressure of 0.05 to 2 MPa is obtained.
- the resin composition layer (resin layer) may be subjected to exposure, post-exposure baking, development, and heat treatment in the same manner as in the case where the above-described photosensitive resin composition for hollow packages of the present invention is used in liquid form.
- the steps of coating on a substrate and drying can be omitted, and the photosensitive resin composition for a hollow package of the present invention can be simplified. Pattern formation using objects can be performed.
- a resin cured product structure having a predetermined space (cavity) is prepared by combining the liquid resin and / or laminate-shaped photosensitive resin composition for a hollow package of the present invention and using a photolithography technique. can do.
- the photosensitive resin composition for a hollow package of the present invention can stably maintain a substrate, wiring, elements, etc. while having a certain space (cavity) around an element having a mechanical structure. It is suitably used for making a hollow package for the purpose of blocking intrusion of gas or liquid.
- the photosensitive resin composition for a hollow package of the present invention is most suitably used for producing a package when the device is a MEMS device.
- FIG. 1 is a cross-sectional view showing an example of a microdevice.
- the microdevice 1 is configured to cover the substrate 2, the MEMS 3 formed on the substrate 2, the cavity securing portion 4 for securing the cavity C (space, hollow) provided around the MEMS 3, and the same.
- the sealing layer 6 and the other provided are provided.
- the substrate 2 placed on the lead frame 5 is made of silicon or the like, and a conductor pattern 7 made of a metal thin film or the like is formed on one surface thereof by etching or the like.
- the MEMS 3 is electrically connected to the conductor pattern 7 and formed on the substrate 2.
- the conductor pattern 7 is connected to the lead frame 5 via a wire 8 so that the microdevice 1 can be incorporated into another device.
- the cavity securing part 4 is a substantially box-shaped structure including a side wall 4A arranged so as to surround the periphery of the MEMS 3 arranged on the substrate 2, and a ceiling 4B provided above the side wall 4A.
- a cavity C that is a space for driving the MEMS 3 is formed around the MEMS 3 by covering the periphery and the upper part of the MEMS 3 in the horizontal direction with the cavity securing portion 4.
- a material for forming the cavity securing portion 4 a cured product of the photosensitive resin composition for a package of the present invention is used.
- the sealing layer 6 is formed by transfer molding so as to cover the outside of the substrate 2, and has a function of protecting the MEMS 3 on the substrate 2 and the connection portion between the conductor pattern 7 and the wire 8 from the external environment.
- the same material as that used for sealing a general semiconductor chip or the like can be used, and examples thereof include various epoxy sealants.
- These epoxy sealants are generally composed of an epoxy resin, a phenol curing agent, a curing accelerator, a filler, and the like, and may contain a flame retardant, a release agent, a colorant, and a coupling agent.
- a high fluidity one using a low viscosity epoxy resin is preferable.
- microdevice 1 configured as described above.
- the following is an example of manufacturing the microdevice 1 by so-called wafer level packaging, in which a plurality of substrates 2 of the microdevice 1 are formed on a single silicon wafer.
- This method has advantages such as no need for assembly process equipment and protection of the MEMS when divided, but the manufacturing method is not limited thereto.
- the step of forming the MEMS 3 on the substrate 2 comprises three steps of the step of sealing (third step).
- a MEMS is formed on the substrate.
- the substrate is formed by providing a plurality of recesses on the surface of the silicon wafer, and then surface micromachining in which a device is formed by combining an integrated circuit fabrication technique and a sacrificial layer etching technique, or mainly SOI (Silicon On Insulator).
- a MEMS and a conductor pattern are formed by bulk micromachining in which a device is formed by processing a wafer or a substrate itself by wet etching or deep dry etching, or a combination of both.
- the conductor pattern may be protected by an inorganic insulating film such as SiO 2 or SiN, polyimide, polybenzoxazole, benzocyclobutene, epoxy resin, or the like, except for the location where the MEMS and the wire are connected.
- the conductor pattern 7 may be mounted from the back surface (surface opposite to the surface on which the MEMS is formed) of the substrate through a through hole created by deep etching or sand blasting.
- a cavity securing portion is formed around the MEMS.
- the thickness (the horizontal dimension of 4A in FIG. 2A) and the height (the vertical dimension of 4A in FIG. 2A) and the height of the side wall 4A are determined according to the dimensions of each part of the MEMS 3 and the driving mode. It may be set as appropriate based on the required cavity size.
- the cover film of the laminate of the photosensitive resin composition for hollow packages is peeled and laminated on the side wall 4A to form a ceiling 4B.
- the cavity securing portion 4 that holds the cavity C is completed as shown in FIG.
- a cavity securing portion 4 is formed by transfer after laminating a structure on a base material by photolithography, or unevenness is preliminarily formed by a technique such as imprinting. It is also possible to form a cavity securing part by photolithography after transferring the photosensitive resin layer on which is formed. Also, after sealing the MEMS in advance with a sacrificial layer material, the liquid photosensitive resin composition for a hollow package is dried after being applied with a spray coater, a bar coater, a spin coater or the like, or the photosensitive resin composition for a hollow package is used.
- the photosensitive resin composition layer for the hollow package is formed so as to cover the sacrificial layer by peeling the cover film of the laminated body in a vacuum after being peeled off, and then sacrificing a part of the cavity securing part 4 by photolithography
- a hole for removing the layer is formed at the same time, the sacrificial layer is removed from the formed hole, and further, a photosensitive resin composition for a hollow package is coated or laminated, and the cavity securing portion can be formed by photolithography.
- 2 (a), 2 (b) and 2 (c) 2 represents a substrate (silicon wafer), 3 represents a MEMS, and 7 represents a conductor pattern. Is performed on a substrate (silicon wafer).
- the substrate on which the cavity securing portion is formed is separated by dicing or the like, the individual substrates are arranged at the center of the lead frame, the conductor pattern and the lead frame are collectively connected via wires, and then transferred. Perform molding. When the unnecessary portion is removed after the curing is completed, a micro device as shown in FIG. 1 is completed.
- the cavity securing portion is formed of the cured product of the photosensitive resin composition for a hollow package of the present invention that exhibits high strength even at high temperatures, a sealing layer is formed by transfer molding.
- the occurrence of defects such as deformation or crushing of the cavity securing portion 4 is suppressed when the conductor pattern and the lead frame are collectively connected, or when the substrate is separated by dicing or the like. Therefore, the cavity inside the cavity securing portion is securely held, and a highly reliable microdevice can be provided.
- the formation of the cavity securing portion is performed by a photolithography process using the photosensitive resin composition for a hollow package. Therefore, it is not necessary to form a cavity securing portion by bonding a material such as silicon or glass at a high temperature in order to secure the cavity, and it is possible to provide a highly reliable microdevice with high productivity and low cost. .
- the configuration of the cavity securing portion is not limited to this.
- a columnar structure that supports the ceiling may be provided at a position that does not hinder the driving of the MEMS in the cavity, and the cavity securing portion may be configured to support the ceiling with the side wall and the columnar structure.
- an oxide film may be provided on the surface of the side wall or the ceiling to increase the rigidity.
- a part of the substrate is dug by etching or the like to form a concave cavity, and after forming a MEMS in the cavity, a laminate-shaped cavity securing part material is disposed above the cavity to form a cavity. May be.
- the cavity securing part is formed by a side wall formed by a part of the substrate and a ceiling made of the cavity securing part material.
- the cavity securing portion may be formed in a substantially cylindrical shape by forming the side wall in a circular shape.
- the pressure resistance may be further increased by forming the cavity securing portion into a dome shape by using transfer or the like. Even with such a configuration, it is possible to satisfactorily secure a cavity for driving the MEMS.
- the photosensitive resin composition for a hollow package of the present invention is extremely excellent in strength (particularly strength at high temperature), it is a case where a transfer mold method is adopted in providing a sealing layer of an element having a hollow structure. However, there is a feature that the space can be sufficiently retained. Therefore, by using the photosensitive resin composition for a hollow package of the present invention, it is possible to obtain an inexpensive, high-yield and highly reliable hollow package in manufacturing a device such as a MEMS device or a semiconductor device having a hollow structure. Can do.
- the present invention will be described in more detail by way of examples. However, these examples are merely examples for suitably explaining the present invention, and do not limit the present invention.
- the photosensitive resin composition for a hollow package of the present invention is simply referred to as a photosensitive resin composition. “Part” means part by mass.
- Examples 1 to 7 and Comparative Example Preparation of photosensitive resin composition and resin composition (for comparison) and creation of laminate using them) According to the blending amount (unit is part) shown in Table 1, trisphenolmethane type epoxy resin (A), photocationic polymerization initiator (B), epoxy resin having two or more epoxy groups in one molecule (C) The reactive epoxy monomer (D) and other components were stirred in a flask equipped with a stirrer at 80 ° C. for 1 hour to obtain a photosensitive resin composition of the present invention and a comparative resin composition, respectively.
- A trisphenolmethane type epoxy resin
- B photocationic polymerization initiator
- epoxy resin having two or more epoxy groups in one molecule C
- the reactive epoxy monomer (D) and other components were stirred in a flask equipped with a stirrer at 80 ° C. for 1 hour to obtain a photosensitive resin composition of the present invention and a comparative resin composition, respectively.
- photosensitive resin compositions and resin compositions were uniformly applied onto a 50 ⁇ m-thick polyethylene terephthalate (PET) film (base film, manufactured by Toray Industries, Inc.), and 95 ° C. by a hot air convection dryer. After drying for 5 minutes at 110 ° C. and 5 minutes at 110 ° C., 38 ⁇ m release-treated PET film (cover film, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) is laminated on the exposed surface, and each is a 50 ⁇ m thick photosensitive resin. A laminate (dry film resist) of the composition and the resin composition (for comparison) was obtained.
- PET polyethylene terephthalate
- KBM-303 trade name, manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent
- Lamination was performed at 5 m / min.
- Pattern exposure soft contact, ultra-high pressure mercury lamp
- a mask aligner MA-20, manufactured by Mikasa Co., Ltd.
- PEB was performed for 1 minute at 65 ° C. for 6 minutes at 95 ° C. using a hot plate, and after heat treatment at 200 ° C. for 30 minutes using an oven, the substrate was cut and the ceiling of the cavity was a photosensitive resin composition or resin.
- a test piece made of a cured product of each laminated film of the composition was obtained. The test piece was fixed to a polyimide film, and transfer mold molding was performed at a molding temperature of 180 ° C.
- ⁇ The ceiling of the cavity with a side of 300 ⁇ m square is not in contact with the substrate, The ceiling of the cavity having a side of 500 ⁇ m square is in contact with the substrate.
- X Although the ceiling part of the cavity whose side is 100 ⁇ m square is not in contact with the substrate, The ceiling of the cavity with a side of 300 ⁇ m square is in contact with the substrate.
- a to G are as follows.
- C-2 Epoxy resin having two or more epoxy groups in one molecule in which p in Formula (3) is about 6 (trade name EOCN-103S, manufactured by Nippon Kayaku Co., Ltd.)
- Example 8 20 parts of a trisphenolmethane type epoxy resin (trade name EPPN-502H, manufactured by Nippon Kayaku Co., Ltd.) in which n in the formula (1) is about 1.3, a photocationic polymerization initiator (trade name: GSID26-1, Ciba) 0.5 parts by Specialty Chemicals), epoxy resin having two or more epoxy groups in one molecule in which k in formula (2) is about 2 (trade name EPON SU-8, Resolution Performance) 65 parts by product), 15 parts of reactive epoxy monomer (trade name jER828, manufactured by Japan Epoxy Resin Co., Ltd.), 40 parts of cyclopentanone as a solvent, fluorine leveling agent (trade name: MegaFuck F-470, manufactured by DIC Corporation) ) According to the compounding amount of 0.05 part, 2 parts of silane coupling agent (trade name S-510, manufactured by Chisso Corporation) In the same manner as in Example 1 described above, a laminate of the photosensitive resin composition was obtained. When the obtained laminate was evaluated
- Example 9 Epoxy resin having two or more epoxy groups in one molecule in which k in Formula (2) is about 2 (trade name EPON SU-8, manufactured by Resolution Performance Products), propylene glycol monomethyl ether 60 parts of nanotech alumina SPC (manufactured by C-I Kasei Co., Ltd .; spherical alumina, average particle size 50 nm) were dispersed for 4 hours using DISPERMAT SL-C-12 (manufactured by Eiko Seiki Co., Ltd.).
- a trisphenolmethane type epoxy resin (trade name: EPPN-502H, manufactured by Nippon Kayaku Co., Ltd.) in which n in the formula (1) is about 1.3, a cationic photopolymerization initiator (trade name: GSID26) -1, 0.5 parts manufactured by Ciba Specialty Chemicals), 15 parts reactive epoxy monomer (trade name jER828, manufactured by Japan Epoxy Resin Co., Ltd.), fluorine leveling agent (trade name: Megafuck F-470, manufactured by DIC Corporation) ) 0.05 part and 2 parts of a silane coupling agent (trade name S-510, manufactured by Chisso Corporation) were added, and the same operation as in Example 1 was performed to obtain a laminate of the photosensitive resin composition.
- the exposure amount was 1000 mJ / cm 2
- the resolution was ⁇
- the storage elastic modulus was 2.8 GPa
- the mold resistance was ⁇ .
- the photosensitive resin composition for a hollow package of the present invention is a photosensitive resin composition for a hollow package that can produce a hollow structure by photolithography and can maintain a sufficient space even in a transfer molding method.
- the photosensitive resin composition for a hollow package of the present invention it is possible to produce a hollow package that is inexpensive, has a good yield, and is highly reliable in manufacturing a device such as a MEMS device and a semiconductor.
- Microdevice 2 Substrate 3 Microelectromechanical system (MEMS) 4 Cavity securing part (4A side wall, 4B ceiling, C cavity) 5 Lead frame 6 Sealing layer 7 Conductor pattern 8 Wire
- MEMS Microelectromechanical system
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Abstract
Description
本願は、2008年6月10日に、日本に出願された特願2008-151273号に基づき優先権を主張し、その内容をここに援用する。
(1)下記式(1)で表されるトリスフェノールメタン型エポキシ樹脂(A)と光カチオン重合開始剤(B)とを含有してなる中空パッケージ用感光性樹脂組成物
(2)1分子中に2個以上のエポキシ基を有するエポキシ樹脂(C)をさらに含有してなる前項(1)に記載の中空パッケージ用感光性樹脂組成物、
(3)1分子中に2個以上のエポキシ基を有するエポキシ樹脂(C)が下記式(2)
で表されるエポキシ樹脂(C-1)、下記式(3)
で表されるエポキシ樹脂(C-2)及び下記式(4)
(4)反応性エポキシモノマー(D)をさらに含有してなる前項(1)乃至(3)のいずれか一項に記載の中空パッケージ用感光性樹脂組成物、
(5)反応性エポキシモノマー(D)がビスフェノールAジグリシジルエーテルである前項(4)に記載の中空パッケージ用感光性樹脂組成物、
(6)無機充填剤(F)をさらに含有してなる前項(1)乃至(5)のいずれか一項に記載の中空パッケージ用感光性樹脂組成物、
(7)前項(1)乃至(6)のいずれか一項に記載の中空パッケージ用感光性樹脂組成物を硬化して得られる硬化物、
(8)基板と、該基板上に形成されたマイクロ電子機械システムと、前項(7)記載の硬化物を含んで形成され、前記マイクロ電子機械システムの周囲に空間を確保するように前記マイクロ電子機械システムを被覆するキャビティ確保部と、樹脂を含んで形成され、前記キャビティ確保部を被覆するように設けられた封止層を備えてなるマイクロデバイス、
(9)前項(1)乃至(6)のいずれか一項に記載の中空パッケージ用感光性樹脂組成物を基材で挟み込んだ中空パッケージ用感光性樹脂組成物の積層体、
に関する。
本発明における式(1)
で表されるトリスフェノールメタン型エポキシ樹脂(A)は、それ自体公知のエポキシ樹脂であり、例えば、必要により窒素雰囲気下でフェノール類とヒドロキシベンズアルデヒド類とを反応させて得られるフェノール誘導体を、常法によりエピクロルヒドリン等のエピハロヒドリンによりグリシジル化することにより製造されるものである。
尚、ここでいう「式(1)で表されるトリスフェノールメタン型エポキシ樹脂(A)」とは、式(1)で表されるエポキシ樹脂を主成分とするエポキシ樹脂を意味するものであり、該エポキシ樹脂を製造する際に生成する副成分や式(1)で表されるエポキシ樹脂の高分子量体等が含有される場合も本発明の技術範囲に含まれる。
これらトリスフェノールメタン型エポキシ樹脂(A)は市場より入手することもできる。例えばEPPN-501H(商品名、日本化薬株式会社製、エポキシ当量162~172g/eq.、軟化点51~57℃)、EPPN-501HY(商品名、日本化薬株式会社製、エポキシ当量163~175g/eq.、軟化点57~63℃)、EPPN-502H(商品名、日本化薬株式会社製、エポキシ当量158~178g/eq.、軟化点60~72℃)、EPPN-503(商品名、日本化薬株式会社製、エポキシ当量170~190g/eq.、軟化点80~100℃)等として入手可能である。
以上の光カチオン重合開始剤のうち、本発明では熱安定性に優れることから芳香族スルホニウム錯塩が好ましく、芳香族スルホニウム錯塩のなかでは非アンチモン系のチオフェニルジフェニルスルフォニウムトリス(ペンタフルオロエチル)トリフルオロホスフェート、トリフェニルスルホニウムトリス(トリフルオロメタンスルホニル)メタニド、(2-(4-メトキシナフタレン-1-イル)-2-オキソエチル)ジメチルスルホニウムテトラキス(ペンタフルオロフェニル)ボレート、トリス[4-(4-アセチルフェニルスルファニル)フェニル]スルホニウムトリス[(トリフルオロメチル)スルホニル]メタニド等がより好ましい。
式(2)で表されるエポキシ樹脂(C-1)の具体例としては、jER157(商品名、ジャパンエポキシレジン株式会社製、エポキシ当量180~250g/eq.、軟化点80~90℃)、EPON SU-8(商品名、レゾリューション・パフォーマンス・プロダクツ社製、エポキシ当量195~230g/eq.、軟化点80~90℃)等が市場から入手できる。
式(3)のRにおける炭素数1~6のアルキル基としては、例えばメチル基、エチル基、プロピル基、ブチル基及びシクロヘキシル基などが挙げられ、水素原子又はメチル基が好ましく、メチル基がより好ましい。式(3)における最も好ましい組み合わせとしては、Rがメチル基でmが1であり、かつRの置換位置がグリシジル基に対するオルト位であるo-クレゾールノボラック型エポキシ樹脂が挙げられる。式(3)で表されるエポキシ樹脂(C-2)の具体例としては、EOCN-1020(商品名、日本化薬株式会社製、エポキシ当量190~210g/eq.、軟化点55~85℃)、EOCN-4400H(商品名、日本化薬株式会社製、エポキシ当量185~200g/eq.、軟化点55~64℃)、EOCN-102S(商品名、日本化薬株式会社製、エポキシ当量205~225g/eq.、軟化点55~80℃)、EOCN-103S(商品名、日本化薬株式会社製、エポキシ当量210~230g/eq.、軟化点80~90℃)、EOCN-104S(商品名、日本化薬株式会社製、エポキシ当量210~230g/eq.、軟化点90~95℃)、EPPN-201(商品名、日本化薬株式会社製、エポキシ当量180~200g/eq.、軟化点65~78℃)等が市場から入手できる。
前述した液状及び/又は積層体状の本発明の中空パッケージ用感光性樹脂組成物を組み合わせて、フォトリソグラフィーの手法を用いることにより、一定の空間(キャビティ)を有する樹脂硬化物の構造体を調製することができる。
図1はマイクロデバイスの一例を示す断面図である。マイクロデバイス1は、基板2と、基板2上に形成されたMEMS3と、MEMS3の周囲に設けられたキャビティC(空間、中空)を確保する為のキャビティ確保部4、並びにそれらを被覆するように設けられた封止層6他とを備えて構成されている。
キャビティ確保部4を形成する材料として、本発明のパッケージ用感光性樹脂組成物の硬化物が用いられる。
以下は単一のシリコンウエハ上にマイクロデバイス1の基板2を複数形成する、いわゆるウエハレベルパッケージングによってマイクロデバイス1を製造する例である。この方法は、組立工程の設備が不要である、MEMSが分割時に保護される等の利点を有するが、製造方法はこれに限定されるものではない。
基板は、シリコンウエハの表面に、複数の凹部を設けることによって形成され、その後、集積回路作成技術及び犠牲層エッチング技術を組み合わせてデバイスを作成するサーフェイスマイクロマシニング、又は主にSOI(Silicon On Insulator)ウエハや基板そのものをウェットエッチングや深堀ドライエッチング等で加工してデバイスを作成するバルクマイクロマシニング、あるいは両者の組み合わせによりMEMS及び導体パターンを形成する。
なお、導体パターンは、MEMS及びワイヤを接続する箇所以外は、SiO2やSiNといった無機絶縁膜や、ポリイミド、ポリベンゾオキサゾール、ベンゾシクロブテン、エポキシ樹脂等によって保護されてもよい。また、導体パターン7は、深堀エッチングやサンドブラストによって作成された貫通孔を介して、基板の裏面(MEMSが形成される面と反対側の面)から実装されてもよい。
まず、MEMS3の周囲に本発明の中空パッケージ用感光性樹脂組成物を塗布したのち、フォトマスクを介し露光、PEB、現像を行い、側壁4Aを形成する。側壁4Aの厚み(図2(a)における4Aの左右方向の寸法)や高さ(図2(a)における4Aの上下方向の寸法)は、MEMS3の各部寸法や駆動態様に応じて決定される必要なキャビティの大きさに基づいて、適宜設定されてよい。
また、MEMSを予め犠牲層材料で封止した後、液状の中空パッケージ用感光性樹脂組成物をスプレーコーター、バーコーター、スピンコーターなどで塗布後に乾燥したり、或いは中空パッケージ用感光性樹脂組成物の積層体のカバーフィルムを剥離後に真空中でラミネートしたりすることで犠牲層を覆うように中空パッケージ用感光性樹脂組成物層を形成し、次いでフォトリソグラフィーでキャビティ確保部4の一部と犠牲層を除去する穴とを同時に作製し、作製した穴より犠牲層を除去し、更に中空パッケージ用感光性樹脂組成物をコートまたはラミネートし、フォトリソグラフィーによりキャビティ確保部を形成することもできる。
なお、第2図(a)、同(b)及び同(c)において、2は基板(シリコンウエハ)を、3はMEMSを、7は導体パターンをそれぞれ表し、第2工程までの各工程は、基板(シリコンウエハ)上で行われる。
一例として、キャビティ内のMEMSの駆動に支障のない位置に、天井を支える柱状構造を設け、側壁及び柱状構造で天井を支えるようにキャビティ確保部を構成してもよい。また、側壁や天井の表面に酸化膜を設けて剛性を高めてもよい。
さらに、基板の一部をエッチング等によって掘り込んで凹状のキャビティを形成し、当該キャビティ内にMEMSを形成した後、キャビティの上方に積層体状のキャビティ確保部材料を配置してキャビティを形成してもよい。この場合、キャビティ確保部は基板の一部で形成された側壁と、キャビティ確保部材料からなる天井とから形成されることとなる。
(感光性樹脂組成物及び樹脂組成物(比較用)の調製並びにそれらを用いた積層体の作成)
表1に記載の配合量(単位は部)に従って、トリスフェノールメタン型エポキシ樹脂(A)、光カチオン重合開始剤(B)、1分子中に2個以上のエポキシ基を有するエポキシ樹脂(C)、反応性エポキシモノマー(D)、及びその他の成分を撹拌機付きフラスコで80℃、1時間撹拌し、それぞれ本発明の感光性樹脂組成物及び比較用の樹脂組成物を得た。これらの感光性樹脂組成物及び樹脂組成物(比較用)を膜厚50μmのポリエチレンテレフタレート(PET)フィルム(ベースフィルム、東レ株式会社製)上に均一に塗布し、温風対流乾燥機により95℃で5分間及び110℃で5分間乾燥した後、露出面上に38μmの離型処理されたPETフィルム(カバーフィルム、三菱化学ポリエステルフィルム株式会社製)をラミネートして、それぞれ50μm厚の感光性樹脂組成物及び樹脂組成物(比較用)の積層体(ドライフィルムレジスト)を得た。
前記で得られた各積層体のカバーフィルムを剥離し、ロール温度70℃、エアー圧0.2MPa、速度0.5m/minでシリコンウエハ上にラミネートし、50μmの感光性樹脂組成物及び樹脂組成物(比較用)の樹脂層を得た。これらの樹脂層に、マスクアライナー(MA-20、ミカサ株式会社製)を用いて250~1000mJ/cm2の露光量でパターン露光(ソフトコンタクト、超高圧水銀灯)を行った。その後ホットプレートにより95℃で6分間露光後ベーク(PEB)を行い、プロピレングリコールモノメチルエーテルアセテート(PGMEA)を用いて浸漬法により23℃で6分間現像処理を行い、基板上に硬化した樹脂パターンを得た。
前記積層体のパターニングにおいて、50μmのラインアンドスペースのフォトマスクを使用して露光を行い、現像処理により残渣無く基板に密着した樹脂パターンが得られ、且つDSCによる分析でエポキシ基の反応に由来する発熱が観測されない最小の露光量を確認した。結果を表1に示す。
前記パターン露光において、50μmのラインアンドスペースのフォトマスクを使用し残渣無く解像され、基板に密着しているかを評価した。結果を表1に示す。
評価基準
○:残渣無く、且つ基板にも密着
×:残渣有り、基板から剥離のいずれか、もしくは両方
前記で得られた各積層体をそれぞれ2枚用意し、それぞれのカバーフィルムを剥離し、ロール温度70℃、エアー圧0.2MPa、速度0.5m/minで貼り合せ100μm厚の積層膜をそれぞれ形成した。各積層膜の積層体の一方のベースフィルムを剥離し超高圧水銀灯露光装置(ウシオ電機社製)を用い2000mJ/cm2の露光量で露光した。露光後ホットプレートを用い95℃で10分間PEBを行い、積層膜を5mm幅に切断後、他方のベースフィルムを剥離し、更にオーブンを用い200℃で30分間熱処理を行った。得られた硬化物のフィルムを用いて動的粘弾性測定装置(DMS6100、セイコーインスツル株式会社製)を用いて180℃における貯蔵弾性率を測定し、熱時強度の指標とした。結果を表1に示す。
EOCN-1020-62(商品名、日本化薬株式会社製、o-クレゾールノボラック型エポキシ樹脂)36.8部、H-1(商品名、明和化成株式会社製、フェノールノボラック樹脂)19.6部、トリフェニルホスフィン0.624部、キクロスMSR-2212(商品名、株式会社龍森製、フィラー)340部、カルナウバワックス1号(商品名、株式会社セラリカ野田製、ワックス)1.2部及びKBM-303(商品名、信越化学工業株式会社製、シランカップリング剤)1.35部を、ニーダーを用いて均一になるまで混合した後、プレス機によってタブレット状に成型した。
前記で得られた各感光性樹脂組成物及び樹脂組成物(比較用)の積層体を各2枚用意し、それぞれのカバーフィルムを剥離し、ロール温度70℃、エアー圧0.2MPa、速度0.5m/minで貼り合せ100μm厚の感光性樹脂組成物又は樹脂組成物(比較用)の積層膜を形成した。これらの積層膜の一方のベースフィルムを剥離し、深さが50μmで一辺が100、300及び500μm角のキャビティを有するシリコンウエハの基板上に、ロール温度45℃、エアー圧0.2MPa、速度0.5m/minでラミネートした。マスクアライナー(MA-20、ミカサ株式会社製)を用いて250~1000mJ/cm2の露光量でパターン露光(ソフトコンタクト、超高圧水銀灯)を行った。その後ホットプレートにより65℃で1分間、95℃で6分間PEBを行い、更にオーブンを用い200℃で30分間熱処理を行った後、基板を切断しキャビティの天井部が感光性樹脂組成物又は樹脂組成物の各積層膜の硬化物からなる試験片を得た。試験片をポリイミドフィルムに固定しトランスファーモールド用金型を用いて、前記エポキシモールディングコンパウンドを用い成型温度180℃、成型圧8MPaでトランスファーモールド成型を行った。ダイシングによりキャビティ部を切断し、天井部の積層膜硬化物がトランスファーモールド時の圧力で変形して基板に接触しているかどうかを顕微鏡で確認し、下記基準で評価した。結果を表1に示す。
○:一辺が500μm角のキャビティの天井部が基板に接触していない。
△:一辺が300μm角のキャビティの天井部は基板に接触していないが、
一辺が500μm角のキャビティの天井部が基板に接触している。
×:一辺が100μm角のキャビティの天井部は基板に接触していないが、
一辺が300μm角のキャビティの天井部が基板に接触している。
A:前記式(1)におけるnが約1.3であるトリスフェノールメタン型エポキシ樹脂(商品名 EPPN-502H、日本化薬株式会社製)
B:光カチオン重合開始剤(商品名 UVI-6976、ダウケミカル社製)
C-1:前記式(2)におけるkが約2である1分子中に2個以上のエポキシ基を有するエポキシ樹脂(商品名 EPON SU-8、レゾリューション・パフォーマンス・プロダクツ製)
C-2:前記式(3)におけるpが約6である1分子中に2個以上のエポキシ基を有するエポキシ樹脂(商品名 EOCN-103S、日本化薬株式会社製)
C-3:前記式(4)で示される1分子中に2個以上のエポキシ基を有するエポキシ樹脂(商品名 NC-6300H、日本化薬株式会社製)
C-4:特許文献1記載のエポキシ樹脂(商品名 NC-3000H、日本化薬株式会社製)
C-5:特許文献1記載のエポキシ樹脂(商品名 NER-7604、日本化薬株式会社製)
D-1:反応性エポキシモノマー(商品名 jER828、ジャパンエポキシレジン株式会社製)
D-2:反応性エポキシモノマー(商品名 EX-321L、ナガセケムテックス株式会社製)
E:溶剤 シクロペンタノン
F:フッ素系レベリング剤(商品名 メガファックF-470、DIC株式会社製)
G:シランカップリング剤(商品名 S-510、チッソ株式会社製)
前記式(1)におけるnが約1.3であるトリスフェノールメタン型エポキシ樹脂(商品名 EPPN-502H、日本化薬株式会社製)20部、光カチオン重合開始剤(商品名 GSID26-1、チバスペシャルティケミカルズ社製)0.5部、前記式(2)におけるkが約2である1分子中に2個以上のエポキシ基を有するエポキシ樹脂(商品名 EPON SU-8、レゾリューション・パフォーマンス・プロダクツ製)65部、反応性エポキシモノマー(商品名 jER828、ジャパンエポキシレジン株式会社製)15部、溶剤としてシクロペンタノン40部、フッ素系レベリング剤(商品名 メガファックF-470、DIC株式会社製)0.05部、シランカップリング剤(商品名 S-510、チッソ株式会社製)2部の配合量に従い、前述した実施例1と同様の操作を行い感光性樹脂組成物の積層体を得た。得られた積層体に実施例1と同様の評価を行ったところ、露光量1000mJ/cm2、解像性 ○、貯蔵弾性率2.3GPa、モールド耐性 ○であった。
前記式(2)におけるkが約2である1分子中に2個以上のエポキシ基を有するエポキシ樹脂(商品名 EPON SU-8、レゾリューション・パフォーマンス・プロダクツ製)65部、プロピレングリコールモノメチルエーテル60部、ナノテックアルミナSPC(シーアイ化成株式会社製;球状アルミナ、平均粒径50nm)30部をDISPERMAT SL-C-12(英弘精機株式会社製)を用いて4時間分散させた。分散液に、前記式(1)におけるnが約1.3であるトリスフェノールメタン型エポキシ樹脂(商品名 EPPN-502H、日本化薬株式会社製)20部、光カチオン重合開始剤(商品名 GSID26-1、チバスペシャルティケミカルズ社製)0.5部、反応性エポキシモノマー(商品名 jER828、ジャパンエポキシレジン株式会社製)15部、フッ素系レベリング剤(商品名 メガファックF-470、DIC株式会社製)0.05部、シランカップリング剤(商品名 S-510、チッソ株式会社製)2部を加え、前述した実施例1と同様の操作を行い感光性樹脂組成物の積層体を得た。得られた積層体に実施例1と同様の評価を行ったところ、露光量1000mJ/cm2、解像性 ○、貯蔵弾性率2.8GPa、モールド耐性 ○であった。
2 基板
3 マイクロ電子機械システム(MEMS)
4 キャビティ確保部(4A 側壁、4B 天井、C キャビティ)
5 リードフレーム
6 封止層
7 導体パターン
8 ワイヤ
Claims (9)
- 1分子中に2個以上のエポキシ基を有するエポキシ樹脂(C)をさらに含有してなる請求項1に記載の中空パッケージ用感光性樹脂組成物。
- 反応性エポキシモノマー(D)をさらに含有してなる請求項1乃至3のいずれか一項に記載の中空パッケージ用感光性樹脂組成物。
- 反応性エポキシモノマー(D)がビスフェノールAジグリシジルエーテルである請求項4に記載の中空パッケージ用感光性樹脂組成物。
- 無機充填剤(F)をさらに含有してなる請求項1乃至5のいずれか一項に記載の中空パッケージ用感光性樹脂組成物。
- 請求項1乃至6のいずれか一項に記載の中空パッケージ用感光性樹脂組成物を硬化して得られる硬化物。
- 基板と、該基板上に形成されたマイクロ電子機械システムと、請求項7記載の硬化物を含んで形成され、前記マイクロ電子機械システムの周囲に空間を確保するように前記マイクロ電子機械システムを被覆するキャビティ確保部と、樹脂を含んで形成され、前記キャビティ確保部を被覆するように設けられた封止層を備えてなるマイクロデバイス。
- 請求項1乃至6のいずれか一項に記載の中空パッケージ用感光性樹脂組成物を基材で挟み込んだ中空パッケージ用感光性樹脂組成物の積層体。
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