WO2015174141A1 - 液状封止材、それを用いた電子部品 - Google Patents
液状封止材、それを用いた電子部品 Download PDFInfo
- Publication number
- WO2015174141A1 WO2015174141A1 PCT/JP2015/058558 JP2015058558W WO2015174141A1 WO 2015174141 A1 WO2015174141 A1 WO 2015174141A1 JP 2015058558 W JP2015058558 W JP 2015058558W WO 2015174141 A1 WO2015174141 A1 WO 2015174141A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- silica filler
- component
- sealing material
- liquid sealing
- liquid
- Prior art date
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- 239000007788 liquid Substances 0.000 title claims abstract description 102
- 239000003566 sealing material Substances 0.000 title claims abstract description 86
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 300
- 239000000945 filler Substances 0.000 claims abstract description 164
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 150
- 239000002245 particle Substances 0.000 claims abstract description 47
- 239000004065 semiconductor Substances 0.000 claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 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 claims abstract description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 27
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002879 Lewis base Substances 0.000 claims description 11
- 150000007527 lewis bases Chemical class 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000000758 substrate Substances 0.000 abstract description 30
- 238000002347 injection Methods 0.000 abstract description 12
- 239000007924 injection Substances 0.000 abstract description 12
- 238000007789 sealing Methods 0.000 abstract description 5
- 239000003822 epoxy resin Substances 0.000 description 32
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- 238000000034 method Methods 0.000 description 21
- 238000001723 curing Methods 0.000 description 20
- 238000003756 stirring Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 125000005372 silanol group Chemical group 0.000 description 10
- -1 3,4-epoxy-6-methylcyclohexylmethyl Chemical group 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- 238000004381 surface treatment Methods 0.000 description 8
- 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 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011256 inorganic filler Substances 0.000 description 6
- 229910003475 inorganic filler Inorganic materials 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000008393 encapsulating agent Substances 0.000 description 5
- 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 description 5
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
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- 239000011342 resin composition Substances 0.000 description 4
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- 239000000126 substance Substances 0.000 description 4
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 3
- CBEVWPCAHIAUOD-UHFFFAOYSA-N 4-[(4-amino-3-ethylphenyl)methyl]-2-ethylaniline Chemical compound C1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=CC=2)=C1 CBEVWPCAHIAUOD-UHFFFAOYSA-N 0.000 description 3
- AOFIWCXMXPVSAZ-UHFFFAOYSA-N 4-methyl-2,6-bis(methylsulfanyl)benzene-1,3-diamine Chemical compound CSC1=CC(C)=C(N)C(SC)=C1N AOFIWCXMXPVSAZ-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
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- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
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- 229910000679 solder Inorganic materials 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-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
- MFIBZDZRPYQXOM-UHFFFAOYSA-N [dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silyl]oxy-dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound C1OC1COCCC[Si](C)(C)O[Si](C)(C)CCCOCC1CO1 MFIBZDZRPYQXOM-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- LJCJRRKKAKAKRV-UHFFFAOYSA-N (2-amino-2-methylpropyl) 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(N)COC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 LJCJRRKKAKAKRV-UHFFFAOYSA-N 0.000 description 1
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- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical class C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- LPVHVQFTYXQKAP-YFKPBYRVSA-N (4r)-3-formyl-2,2-dimethyl-1,3-thiazolidine-4-carboxylic acid Chemical compound CC1(C)SC[C@@H](C(O)=O)N1C=O LPVHVQFTYXQKAP-YFKPBYRVSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-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
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 description 1
- HIGURUTWFKYJCH-UHFFFAOYSA-N 2-[[1-(oxiran-2-ylmethoxymethyl)cyclohexyl]methoxymethyl]oxirane Chemical compound C1OC1COCC1(COCC2OC2)CCCCC1 HIGURUTWFKYJCH-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- OVEUFHOBGCSKSH-UHFFFAOYSA-N 2-methyl-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound CC1=CC=CC=C1N(CC1OC1)CC1OC1 OVEUFHOBGCSKSH-UHFFFAOYSA-N 0.000 description 1
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- QDFXRVAOBHEBGJ-UHFFFAOYSA-N 3-(cyclononen-1-yl)-4,5,6,7,8,9-hexahydro-1h-diazonine Chemical compound C1CCCCCCC=C1C1=NNCCCCCC1 QDFXRVAOBHEBGJ-UHFFFAOYSA-N 0.000 description 1
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 1
- CPXYLMJQRDHHCI-UHFFFAOYSA-N 4-(1,3-dioxan-2-yl)-7-oxabicyclo[4.1.0]heptane Chemical compound O1CCCOC1C1CC2OC2CC1 CPXYLMJQRDHHCI-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- CXXSQMDHHYTRKY-UHFFFAOYSA-N 4-amino-2,3,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1=C(O)C(CC2OC2)=C(CC2OC2)C(N)=C1CC1CO1 CXXSQMDHHYTRKY-UHFFFAOYSA-N 0.000 description 1
- JBBURRWEMSTGIX-UHFFFAOYSA-N 5-ethyl-5-methyl-1,3-bis(oxiran-2-ylmethyl)imidazolidine-2,4-dione Chemical compound O=C1N(CC2OC2)C(=O)C(CC)(C)N1CC1CO1 JBBURRWEMSTGIX-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- IPHKNOWSJUHYSE-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) 3-methylcyclohexane-1,2-dicarboxylate Chemical compound CC1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 IPHKNOWSJUHYSE-UHFFFAOYSA-N 0.000 description 1
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 description 1
- HGXHJQLDZPXEOG-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,4-dicarboxylate Chemical compound C1CC(C(=O)OCC2OC2)CCC1C(=O)OCC1CO1 HGXHJQLDZPXEOG-UHFFFAOYSA-N 0.000 description 1
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- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
- AVKNGPAMCBSNSO-UHFFFAOYSA-N cyclohexylmethanamine Chemical compound NCC1CCCCC1 AVKNGPAMCBSNSO-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
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- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
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- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- KEZAKPHSMMMPQD-UHFFFAOYSA-N methylsulfanyl-(2-methylsulfanylphenyl)methanediamine Chemical compound CSC1=CC=CC=C1C(N)(N)SC KEZAKPHSMMMPQD-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
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- 229920001187 thermosetting polymer Polymers 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—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
- C08G59/20—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 epoxy compounds used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—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
- C08G59/40—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 curing agents used
- C08G59/50—Amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/295—Organic, e.g. plastic containing a filler
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/296—Organo-silicon compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
- H01L21/563—Encapsulation of active face of flip-chip device, e.g. underfilling or underencapsulation of flip-chip, encapsulation preform on chip or mounting substrate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- the present invention relates to a resin composition suitable for a one-component adhesive for applications requiring thermosetting.
- the resin composition of the present invention is used in the manufacture of image sensor modules used as camera modules for mobile phones and smartphones, and electronic components such as semiconductor elements, integrated circuits, large-scale integrated circuits, transistors, thyristors, diodes, and capacitors. It is suitable as a one-component adhesive. Further, the resin composition of the present invention is expected to be used as a liquid sealing material used at the time of manufacturing a semiconductor device.
- a flip chip type semiconductor device has a structure in which an electrode portion on a substrate and a semiconductor element are connected via a bump electrode.
- a stress is applied to the bump electrode due to a difference in coefficient of thermal expansion between the substrate made of an organic material such as an epoxy resin and the semiconductor element. It is a problem that defects such as cracks occur.
- a liquid sealant called underfill is used to seal the gap between the semiconductor element and the substrate and fix them together to improve thermal cycle resistance. Is widely practiced.
- the liquid sealant used as the underfill is required to have excellent injectability, adhesiveness, curability, storage stability and the like, and no voids are generated. Moreover, it is calculated
- a liquid sealing material used as an underfill those mainly composed of an epoxy resin are widely used.
- a filler made of an inorganic substance such as silica filler hereinafter referred to as “filler”. It is effective to control the difference in thermal expansion coefficient between the substrate made of an organic material such as an epoxy resin and the semiconductor element or to reinforce the bump electrode by adding to the liquid sealing material. It is known (see Patent Document 1).
- the liquid sealing material is required to have a further lower thermal expansion (lowering the thermal expansion coefficient of the liquid sealing material).
- the gap between the semiconductor element and the substrate and the distance between the bumps tend to be narrow.
- the underfill material In order to reduce the thermal expansion of the underfill material, it is essential to increase the filling of the filler (increase the filling rate of the filler). However, as the filling rate of the filler increases, the viscosity also increases. The injectability of the underfill material into the gap between the two decreases. In addition, in the case of silica filler, since there are many silanol groups that are hydrophilic groups on the surface, the compatibility with the hydrophobic component of the underfill material (for example, the epoxy resin that forms the main agent) is not good, and the underfill agent There is a tendency that the dispersibility of the filler in is poor.
- the filler When the filler is highly filled, a finer filler is used, but the surface area of the filler increases exponentially as the filler becomes finer. As a result, the dispersibility of the filler is deteriorated for the reasons described above, the viscosity of the underfill material is increased, and the injectability of the underfill material into the gap between the semiconductor element and the substrate is reduced.
- the inorganic filler is surface-treated with a silane coupling agent to increase the blending amount of the inorganic filler, but the average particle is surface-treated with the silane coupling agent.
- the present invention uses a liquid sealing material that achieves both low thermal expansion and injectability into the gap between the semiconductor element and the substrate, and a liquid sealing material.
- An object of the present invention is to provide an electronic component formed by sealing a sealing portion.
- silanol groups which are hydrophilic groups, on the surface of the silica filler, the compatibility with the hydrophobic component of the underfill material (for example, the epoxy resin that forms the main agent) is not good, and the underfill is not good.
- the dispersibility of the filler in the agent tends to be inferior.
- silanol groups also act as Lewis acids and have activity.
- the silica filler having a particle size of the order of nm has a much larger surface area than the silica filler having an average particle size of 5 to 40 ⁇ m.
- a conventional silane coupling agent having high activity such as that described in Patent Document 2 is used for the surface treatment of the silica filler
- silanol groups present on the surface of the silica filler and the silane coupling agent And excessively react, the dispersibility of the filler in the underfill material deteriorates, the viscosity of the underfill material increases, and the injectability into the gap between the semiconductor element and the substrate decreases.
- the present invention has been made on the basis of the above findings, and is surface-treated with (A) a liquid epoxy resin, (B) a curing agent, and (C) 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
- Silica filler (1) having an average particle size of 7 to 50 nm
- (D) silica filler (1) having an average particle size of 0.2 to 5 ⁇ m
- the total content of the silica filler (1) of the component (C) and the silica filler (2) of the component (D) is 45 to 77 masses with respect to a total of 100 parts by mass of all components of the liquid sealing material.
- the mixing ratio (mass ratio) of the silica filler (1) as the component (C) and the silica filler (2) as the component (D) is from 1: 10.2 to 1: 559.
- a liquid encapsulant is provided.
- liquid epoxy resin of the component (A) and the silica filler (1) of the component (C) are mixed in advance.
- the curing agent of the component (B) is preferably an amine curing agent.
- the silica filler (2) as the component (D) may be surface-treated with a silane coupling agent.
- the liquid sealing material of the present invention may further contain (E) a Lewis base or a salt thereof.
- the component (E) is preferably triphenylphosphine.
- the present invention also provides a semiconductor device having a flip chip type semiconductor element sealed using the liquid sealing material of the present invention.
- the liquid sealing material of the present invention has good injectability into the gap between the semiconductor element and the substrate.
- the liquid encapsulant of the present invention has a low thermal expansion, in a semiconductor device encapsulated with the liquid encapsulant of the present invention, destruction of the Low-K layer due to thermal stress, solder bumps, etc. It is possible to suppress the occurrence of cracks in
- the resin composition of the present invention contains the following components (A) to (D) as essential components.
- the liquid epoxy resin of a component is a component which makes the main ingredient of the liquid sealing material of this invention.
- the liquid epoxy resin means an epoxy resin that is liquid at room temperature.
- the liquid epoxy resin in the present invention includes a bisphenol A type epoxy resin having an average molecular weight of about 400 or less; a branched polyfunctional bisphenol A type epoxy resin such as p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether; F type epoxy resin; phenol novolac type epoxy resin having an average molecular weight of about 570 or less; vinyl (3,4-cyclohexene) dioxide, 3,4-epoxycyclohexylcarboxylic acid (3,4-epoxycyclohexyl) methyl, adipic acid Alicyclic epoxy resins such as bis (3,4-epoxy-6-methylcyclohexylmethyl), 2- (3,4-epoxycyclohexyl) 5,1-
- An epoxy resin having a silicone skeleton such as 1,3-bis (3-glycidoxypropyl) -1,1,3,3-tetramethyldisiloxane can also be used.
- diepoxide compounds such as (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane dimethanol diglycidyl ether; trimethylolpropane triglycidyl Examples include ethers and triepoxide compounds such as glycerin triglycidyl ether.
- liquid bisphenol type epoxy resin a liquid aminophenol type epoxy resin, a silicone-modified epoxy resin, and a naphthalene type epoxy resin are preferable. More preferred are liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, p-aminophenol type liquid epoxy resin, and 1,3-bis (3-glycidoxypropyl) tetramethyldisiloxane.
- the liquid epoxy resin as a component may be individual or may be used together 2 or more types. Moreover, even if it is an epoxy resin solid at normal temperature, it can be used when it shows liquid as a mixture by using together with a liquid epoxy resin.
- the curing agent of the component (B) is not particularly limited as long as it is a curing agent for an epoxy resin, and a known one can be used.
- curing agent can be used.
- the acid anhydride-based curing agent examples include methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride such as methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, Examples include methyl hymic acid anhydride, succinic acid anhydride substituted with an alkenyl group, methyl nadic acid anhydride, glutaric acid anhydride and the like.
- amine curing agent examples include aliphatic polyamines such as triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, isophoronediamine, 1,3- Alicyclic polyamines such as bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, N-aminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) )
- Piperazine type polyamines such as piperazine, diethyltoluenediamine, dimethylthiotoluenediamine, 4,4′-diamino-3,3′-diethyldiphenylmethane, bis (methylthio) toluenediamine, diaminodiphenylmethane, - phenyl
- phenolic curing agents include monomers, oligomers, and polymers in general having a phenolic hydroxyl group.
- phenol novolak resins and alkylated products or allylated products thereof cresol novolak resins, phenol aralkyls (including phenylene and biphenylene skeletons) ) Resin, naphthol aralkyl resin, triphenol methane resin, dicyclopentadiene type phenol resin and the like.
- amine-based curing agents are preferable because they are excellent in moisture resistance and thermal cycle resistance, and among them, diethyltoluenediamine, dimethylthiotoluenediamine, 4,4′-diamino-3,3′-diethyldiphenylmethane, It is preferable from the viewpoint of heat resistance, mechanical properties, adhesion, electrical properties, and moisture resistance. Moreover, the point which exhibits liquid at normal temperature is also preferable as a hardening
- Component curing agents may be used alone or in combination of two or more.
- the blending ratio of the curing agent of the component (B) is not particularly limited, but is 0.5 to 1.6 equivalents relative to 1 equivalent of the epoxy group of the liquid epoxy resin of the component (A). It is preferable that the amount is 0.6 to 1.3 equivalents.
- the silica filler (1) as the component (C) and the silica filler (2) as the component (D) are liquid-sealed for the purpose of improving the moisture resistance and thermal cycle resistance of the sealed portion, particularly the thermal cycle resistance. Added to the stop material.
- the reason why the thermal cycle resistance is improved by the addition of the silica filler is that the expansion / contraction of the cured product of the liquid sealing material due to the thermal cycle can be suppressed by lowering the linear expansion coefficient.
- silica filler (1) having an average particle diameter of 7 to 50 nm as component (C) and silica filler (2) having an average particle diameter of 0.2 to 5 ⁇ m as component (D).
- component (C) silica filler (1) having an average particle diameter of 7 to 50 nm as component (C)
- silica filler (2) having an average particle diameter of 0.2 to 5 ⁇ m as component (D).
- Two types of silica fillers having different average particle diameters are used in combination. The reason why two types of silica fillers having different average particle diameters are used in combination is as follows.
- silica filler Focusing only on silica filler and considering that silica filler is close to the closest packed state, only silica filler with an average particle size in the same range, that is, rather than using a silica filler with a single particle diameter, It is preferable to use two types of silica fillers having different average particle sizes in combination, that is, use a silica filler having a multi-component particle size. This is because the silica filler having a smaller particle size enters the gap between the silica fillers having a larger particle size, so that the silica filler can be more densely filled.
- the silica filler (1) as the component (C) has an average particle diameter of 7 to 50 nm, in order to improve the dispersibility in the liquid sealing material, it is necessary to use one that has been surface-treated with a silane coupling agent. is there.
- the silica filler having a particle size of the order of nm is much larger in surface area than the silica filler having an average particle size of 5 to 40 ⁇ m described in Patent Document 2,
- a conventional silane coupling agent having a high activity such as the one described, is used, the silanol group present on the surface of the silica filler and the silane coupling agent react excessively, and in the liquid sealing material The dispersibility of the silica filler is deteriorated, the viscosity of the liquid sealing material is increased, and the injectability into the gap between the semiconductor element and the substrate is lowered.
- the silica filler (1) as the component (C) is one that has been surface-treated with 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane in advance.
- 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane has a structure represented by the following formula and has a cyclo ring at the end. Due to this steric hindrance due to the cyclo ring, the activity is more limited than that of a glycidyl group of a glycidyl ether type silane coupling agent conventionally used such as that described in Patent Document 2.
- the silanol group present on the surface of the silica filler and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane as a silane coupling agent react appropriately, dispersibility in the liquid sealing material is improved. It is good. For this reason, the viscosity of the liquid sealing material does not increase, and the injectability into the gap between the semiconductor element and the substrate is good.
- the method of surface-treating the silica filler using 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane as the silane coupling agent is not particularly limited.
- it is carried out by a stirring method, a wet method, a dry method, or the like. can do.
- the stirring method is a method in which a silane coupling agent and a silica filler are previously charged in a stirring device and stirred under appropriate conditions.
- a mixer capable of stirring and mixing at high speed such as a Henschel mixer is used. Although it can be used, it is not particularly limited.
- a compound that forms a silane coupling agent by dissolving a sufficient amount of a silane coupling agent in water or an organic solvent with respect to the surface area of the silica filler to be surface-treated that is, 2- (3,4) -Epoxycyclohexyl) ethyltrimethoxysilane is hydrolyzed to form a surface treatment solution.
- a silica filler is added to the obtained surface treatment solution and stirred so as to form a slurry.
- the silica filler is separated from the surface treatment solution by a method such as filtration or centrifugation, and then dried by heating.
- the dry method is a method in which a stock solution or a solution of a silane coupling agent is uniformly dispersed in a silica filler that is stirred at high speed by a stirring device.
- a stirring device a mixer capable of stirring and mixing at high speed such as a Henschel mixer can be used, but is not particularly limited.
- an integrator that modifies the surface of the silica filler by directly adding a silane coupling agent to a silica filler dispersion in which the silica filler is dispersed in a solvent.
- the blend method can also be suitably used.
- the average particle diameter of the silica filler (1) of the component (C) is less than 7 nm, the specific surface area of the silica filler increases exponentially, so the silica filler (1) of the component (C) in the liquid sealing material Dispersibility deteriorates and the injection property into the gap between the semiconductor element and the substrate decreases.
- the average particle diameter of the silica filler (1) of the component (C) exceeds 50 nm, the difference in average particle diameter from the silica filler (2) of the component (D) becomes small.
- Component silica filler (1) and (D) component silica filler (2) are both dispersible and the gap between the semiconductor element and the substrate is poorly injected.
- the silica filler (1) as the component (C) more preferably has an average particle size of 7 to 15 nm.
- the shape of the silica filler (1) as the component (C) is not particularly limited, and may be any form such as granular, powder, flakes, and the like.
- the average particle diameter of a silica filler means the average maximum diameter of a silica filler.
- forming a substantially spherical shape with a sphericity of 0.8 or more improves the dispersibility of the silica filler in the liquid encapsulant and the injectability of the liquid encapsulant, and the silica filler It is preferable from the viewpoint of closer to the closest packing state.
- silica filler as component (C) preferably has a sphericity of 0.9 or more.
- the silica filler (2) as the component (D) has an average particle diameter of 0.2 to 5 ⁇ m, the dispersibility in the liquid sealing material does not become a problem even without surface treatment. However, when the surface-treated one with a silane coupling agent is used, the dispersibility in the liquid sealing material is improved, so that it is suitable for increasing the content of the silica filler (2) as the component (D). .
- silane coupling agents such as vinyl, glycidoxy, methacryl, amino, and mercapto can be used.
- silane coupling agent it is the same as having described about the silica filler (1) of (C) component.
- the average particle size of the silica filler (2) of component (D) is less than 0.2 ⁇ m, the specific surface area increases exponentially as described above, so that the viscosity of the liquid sealing material increases, and the semiconductor element and the substrate Injectability into the gap decreases.
- the average particle diameter of the silica filler (2) of the component (D) exceeds 5 ⁇ m, the size of the silica filler is too large with respect to the gap between the semiconductor element and the substrate, and void entrainment becomes a problem at the time of injection.
- the silica filler (2) as the component (D) preferably has an average particle size of 0.25 to 0.6 ⁇ m.
- the shape of the silica filler (2) as the component (D) is the same as that described for the silica filler (1) as the component (C).
- the total content of the silica filler (1) as the component (C) and the silica filler (2) as the component (D) with respect to a total of 100 parts by mass of all the components of the liquid sealing material.
- the amount is 45 to 77 parts by mass.
- the total content of silica fillers (1) and (2) is less than 45 parts by mass, the linear expansion coefficient of the liquid sealing material increases, and the thermal cycle resistance of the site sealed with the liquid sealing material decreases.
- the total content of the silica fillers (1) and (2) exceeds 77 parts by mass, the viscosity of the liquid sealing material increases, and the injectability into the gap between the semiconductor element and the substrate decreases.
- the total content of silica fillers (1) and (2) is more preferably 50 to 70 parts by mass.
- the blending ratio (mass ratio) of the silica filler (1) as the component (C) and the silica filler (2) as the component (D) is 1: 10.2 to 1: 559. It is.
- the blending ratio of the silica filler (1) is more than 1: 10.2, the dispersibility of the silica filler (1) in the liquid sealing material is deteriorated, the viscosity of the liquid sealing material is increased, and the semiconductor element and the substrate Injectability into the gap between the two decreases.
- the blending ratio of the silica filler (1) is less than 1: 559, the dispersibility of the silica filler (1) and (2) in the liquid sealing material is deteriorated, or the dispersibility of the silica filler (2) is decreased. It deteriorates and the injectability into the gap between the semiconductor element and the substrate decreases.
- the blending ratio of the silica fillers (1) and (2) is more preferably 1: 17.7 to 1: 111, and further preferably 1: 17.7 to 1:76.
- the liquid sealing material of the present invention may contain the components described below as needed in addition to the components (A) to (D).
- the liquid sealing material of the present invention may contain a Lewis base or salt thereof as the component (E).
- a Lewis base or salt thereof As described above, a large number of silanol groups, which are hydrophilic groups, are present on the surface of the silica filler (1) as the component (C) and the silica filler (2) as the component (D). These silanol groups also act as Lewis acids and have activity.
- the Lewis acid activity of silanol groups present on the surfaces of the silica fillers (1) and (2) is suppressed. Thereby, the dispersibility of the silica fillers (1) and (2) in the liquid sealing material is further improved.
- the content of the Lewis base in the liquid sealing material of the present invention is the silica filler (1) as the component (C) and the silica filler (2) as the component (D).
- the silica filler (1) is preferably 0.1 to 0.8 parts by mass, more preferably 0.2 to 0.5 parts by mass with respect to 100 parts by mass in total.
- the liquid sealing material of the present invention may further contain components other than the components (A) to (E) as necessary.
- Specific examples of such components include elastomers, curing accelerators, metal complexes, leveling agents, colorants, ion trapping agents, antifoaming agents, flame retardants, and the like.
- the type and amount of each compounding agent are as usual.
- the liquid sealing material of the present invention is prepared by mixing and stirring the components (A) to (D), and, if included, the component (E), and other compounding agents to be blended as necessary. Prepared. Although mixing and stirring can be performed using a roll mill, of course, it is not limited to this.
- mixing and stirring can be performed using a roll mill, of course, it is not limited to this.
- the epoxy resin as the component (A) is solid, it is preferably liquefied or fluidized and mixed by heating. Each component may be mixed at the same time, or a part of the components may be mixed first, and the remaining components may be mixed later.
- the liquid epoxy resin of the component (A) and the silica filler of the component (C) (1) may be mixed first, and the remaining components may be mixed later.
- the liquid epoxy resin of component (A) and the silica filler (1) of component (C) are mixed first, and the remaining components are mixed.
- the ingredients may be mixed later.
- the liquid sealing materials (1) and (2) of the present invention preferably have a viscosity at room temperature (25 ° C.) of 200 Pa ⁇ s or less, and have good injectability when used as an underfill.
- the viscosity in normal temperature (25 degreeC) is 100 Pa.s or less.
- the liquid sealing material of the present invention has good injection properties by capillary flow when used as an underfill material.
- the injection time is preferably 1200 seconds or less when the gap injection property is evaluated by the procedure described in the examples described later.
- the liquid sealing material of this invention is filled into the gap between a board
- the liquid sealing material of the present invention is applied to one end of the semiconductor element while heating the substrate to 70 to 130 ° C., for example, the liquid sealing material of the present invention is formed in the gap between the substrate and the semiconductor element due to capillary action. Filled.
- the substrate may be inclined or a pressure difference may be generated inside and outside the gap.
- the substrate is heated at a predetermined temperature for a predetermined time, specifically at 80 to 200 ° C. for 0.2 to 6 hours to obtain a liquid sealing material.
- the gap is sealed by heat curing.
- the semiconductor device of the present invention uses the liquid sealing material of the present invention as an underfill, and seals the sealing portion, that is, the gap between the substrate and the semiconductor element by the above procedure.
- the semiconductor element to be sealed here is not particularly limited to an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, a diode, a capacitor, and the like.
- Examples 1 to 15, Comparative Examples 1 to 6 The raw material was kneaded using a roll mill so that the blending ratios shown in the following table were obtained, thereby preparing liquid sealing materials of Examples 1 to 15 and Comparative Examples 1 to 6. However, the liquid epoxy resin of the component (A) and the silica filler (1) of the component (C) were mixed first, and the remaining components were mixed later. In addition, the numerical value regarding each composition in a table
- surface represents the mass part.
- Epoxy resin Epoxy resin A-1 Bisphenol F type epoxy resin, product name YDF8170, manufactured by Nippon Steel Chemical Co., Ltd., epoxy equivalent 158
- Epoxy resin A-2 aminophenol type epoxy resin, product name jER630, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 94 g / eq
- Epoxy resin A-3 1,4 hexanedimethanol diglycidyl ether, product name EP-4085S, manufactured by ADEKA Corporation, epoxy equivalent 135 g / eq
- Curing agent curing agent B-1 4,4'-diamino-3,3'-diethyldiphenylmethane, product name Kayahard AA, Nippon Kayaku Co., Ltd.
- curing agent B-2 diethyltrienediamine, product Name Ecure 100, Hardener B-3 manufactured by Albemarle Japan Co., Ltd .: Dimethylthiotoluenediamine, Product name HARTCURE30, manufactured by Johnson Fine Chemical
- Silica filler (1) Silica filler C-1: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane surface-treated silica filler (average particle size: 7 nm), product name YN010A-JGP, silica filler C-2 manufactured by Admatechs Co., Ltd.
- silica filler C-3 manufactured by Admatechs Co., Ltd .: 2- (3,4-epoxy Cyclohexyl) ethyltrimethoxysilane surface-treated silica filler (average particle size: 50 nm), product name YA050A-JGP, silica filler C-4 manufactured by Admatechs Co., Ltd .: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane surface Treated silica filler (average particle size: 10 nm), product name YC100A-JGP, Ltd.
- silica filler C-5 surface untreated silica filler (average particle size 12 nm), product name R200, Evonik Industries AG made Silica filler C-6: Trimethylsilyl surface-treated silica filler (average particle size 12 nm), product name RX200, silica filler C-7 manufactured by Evonik Industries AG: Octylsilyl surface-treated silica filler (average particle size 12 nm), product name R805, Evonik Made by Industries AG
- Thixotropic index (TI) Thixotropic index (TI)
- TI Thixotropic index
- test piece was prepared by providing a 20 ⁇ m or 50 ⁇ m gap on an organic substrate (FR-4 substrate) and fixing a glass plate instead of a semiconductor element. This test piece was placed on a hot plate set at 110 ° C., a liquid sealing material was applied to one end of the glass plate, and the time until the injection distance reached 20 mm was measured. This procedure was performed twice, and the average value of the measured values was taken as the measured value of the injection time.
- the liquid sealing materials of Examples 1 to 15 all had good evaluation results for viscosity, thixotropy index (TI), and 20 mm injectability measured at a liquid temperature of 25 ° C. and 50 rpm.
- Example 7 containing Lewis base (triphenylphosphine) as the component (E), the physical properties (viscosity, TI, 20 mm injection property) of the liquid sealing material were further improved.
- silica filler surface-treated with a silane coupling agent was used as component (D) silica filler 2
- physical properties of the liquid sealing material viscosity, TI, 20 mm injectability
- Comparative Example 1 using an average particle size of more than 50 nm (100 nm) was inferior in 20 mm injectability of the liquid sealing material.
- Comparative Example 2 in which the silica filler 1 of component (C) is untreated Comparative Example 3, 4 in which the surface treatment was performed with a coupling agent other than 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane
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Abstract
Description
フリップチップ型の半導体装置は、バンプ電極を介して基板上の電極部と半導体素子とが接続された構造を持っている。この構造の半導体装置は、温度サイクル等の熱付加が加わった際に、エポキシ樹脂等の有機材料製の基板と、半導体素子と、の熱膨張係数の差によってバンプ電極に応力がかかり、バンプ電極にクラック等の不良が発生することが問題となっている。この不良発生を抑制するためにアンダーフィルと呼ばれる液状封止剤を用いて、半導体素子と基板との間のギャップを封止し、両者を互いに固定することによって、耐サーマルサイクル性を向上させることが広く行われている。
液状封止材によって封止した部位の耐湿性および耐サーマルサイクル性、特に耐サーマルサイクル性を向上させるためには、シリカフィラーのような無機物質からなる充填材(以下、「フィラー」という。)を液状封止材に添加することにより、エポキシ樹脂等の有機材料製の基板と、半導体素子と、の熱膨張係数差のコントロールを行うことや、バンプ電極を補強することが有効であることが知られている(特許文献1参照)。
その一方で半導体素子と基板とのギャップや、バンプ間の距離は狭くなっている傾向がある。
また、シリカフィラーの場合、その表面に親水基であるシラノール基が多数存在するため、アンダーフィル材の疎水性成分(たとえば、主剤をなすエポキシ樹脂)との相溶性が良好ではなく、アンダーフィル剤におけるフィラーの分散性が劣る傾向がある。
フィラーを高充填化する場合、より微細なフィラーを使用することになるが、フィラーの微細化に伴ってフィラーの表面積は指数関数的に増加する。その結果、上述した理由によりフィラーの分散性が悪化し、アンダーフィル材の粘度が増加し、半導体素子と基板との間のギャップへのアンダーフィル材の注入性の低下を招く。
より微細な粒径がnmオーダーの無機充填剤を、特許文献2に記載のシランカップリング剤で表面処理したところ、アンダーフィル材の粘度が増加して、半導体素子と基板との間のギャップへの注入性の低下や、貯蔵安定性およびポットライフの悪化といった問題が生じることが明らかになった。
上述したように、シリカフィラーの表面には親水基であるシラノール基が多数存在するため、アンダーフィル材の疎水性成分(たとえば、主剤をなすエポキシ樹脂)との相溶性が良好ではなく、アンダーフィル剤におけるフィラーの分散性が劣る傾向がある。これらのシラノール基は、ルイス酸としても作用し活性を持つ。フィラーの微細化に伴ってその表面積は指数関数的に増加するため、粒径がnmオーダーのシリカフィラーは、平均粒径5~40μmのシリカフィラーよりもその表面積がはるかに大きくなる。その結果、シリカフィラーの表面処理に、特許文献2に記載されたもののような、活性が高い従来のシランカップリング剤を使用した場合、シリカフィラーの表面に存在するシラノール基と、シランカップリング剤と、が過度に反応して、アンダーフィル材におけるフィラーの分散性が悪化し、アンダーフィル材の粘度が増加し、半導体素子と基板との間のギャップへの注入性が低下する。
液状封止材の全成分の合計100質量部に対し、前記(C)成分のシリカフィラー(1)、および、前記(D)成分のシリカフィラー(2)の合計含有量が、45~77質量部であり、
前記(C)成分のシリカフィラー(1)と、前記(D)成分のシリカフィラー(2)と、の配合割合(質量比)が1:10.2~1:559であることを特徴とする液状封止材を提供する。
前記(E)成分は、トリフェニルホスフィンであることが好ましい。
また、本発明の液状封止材は、低熱膨張化されているため、本発明の液状封止材を用いて封止された半導体装置において、熱応力によるLow-K層の破壊や、半田バンプでのクラックの発生を抑制できる。
本発明の樹脂組成物は、以下に示す(A)~(D)成分を必須成分として含有する。
(A)成分の液状エポキシ樹脂は、本発明の液状封止材の主剤をなす成分である。
本発明において、液状エポキシ樹脂とは常温で液状のエポキシ樹脂を意味する。
本発明における液状エポキシ樹脂としては、ビスフェノールA型エポキシ樹脂の平均分子量が約400以下のもの;p-グリシジルオキシフェニルジメチルトリスビスフェノールAジグリシジルエーテルのような分岐状多官能ビスフェノールA型エポキシ樹脂;ビスフェノールF型エポキシ樹脂;フェノールノボラック型エポキシ樹脂の平均分子量が約570以下のもの;ビニル(3,4-シクロヘキセン)ジオキシド、3,4-エポキシシクロヘキシルカルボン酸(3,4-エポキシシクロヘキシル)メチル、アジピン酸ビス(3,4-エポキシ-6-メチルシクロヘキシルメチル)、2-(3,4-エポキシシクロヘキシル)5,1-スピロ(3,4-エポキシシクロヘキシル)-m-ジオキサンのような脂環式エポキシ樹脂;3,3´,5,5´-テトラメチル-4,4´-ジグリシジルオキシビフェニルのようなビフェニル型エポキシ樹脂;ヘキサヒドロフタル酸ジグリシジル、3-メチルヘキサヒドロフタル酸ジグリシジル、ヘキサヒドロテレフタル酸ジグリシジルのようなグリシジルエステル型エポキシ樹脂;ジグリシジルアニリン、ジグリシジルトルイジン、トリグリシジル-p-アミノフェノール、テトラグリシジル-m-キシリレンジアミン、テトラグリシジルビス(アミノメチル)シクロヘキサンのようなグリシジルアミン型エポキシ樹脂;ならびに1,3-ジグリシジル-5-メチル-5-エチルヒダントインのようなヒダントイン型エポキシ樹脂;ナフタレン環含有エポキシ樹脂が例示される。また、1,3-ビス(3-グリシドキシプロピル)-1,1,3,3-テトラメチルジシロキサンのようなシリコーン骨格をもつエポキシ樹脂も使用することができる。さらに、(ポリ)エチレングリコールジグリシジルエーテル、(ポリ)プロピレングリコールジグルシジルエーテル、ブタンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、シクロヘキサンジメタノールジグリシジルエーテルのようなジエポキシド化合物;トリメチロールプロパントリグリシジルエーテル、グリセリントリグリシジルエーテルのようなトリエポキシド化合物等も例示される。
中でも好ましくは、液状ビスフェノール型エポキシ樹脂、液状アミノフェノール型エポキシ樹脂、シリコーン変性エポキシ樹脂、ナフタレン型エポキシ樹脂である。さらに好ましくは液状ビスフェノールA型エポキシ樹脂、液状ビスフェノールF型エポキシ樹脂、p-アミノフェノール型液状エポキシ樹脂、1,3-ビス(3-グリシドキシプロピル)テトラメチルジシロキサンである。
(A)成分としての液状エポキシ樹脂は、単独でも、2種以上併用してもよい。
また、常温で固体のエポキシ樹脂であっても、液状のエポキシ樹脂と併用することにより、混合物として液状を示す場合は用いることができる。
(B)成分の硬化剤は、エポキシ樹脂の硬化剤であれば、特に限定されず、公知のものを使用することができ、酸無水物系硬化剤、アミン系硬化剤、および、フェノール系硬化剤のいずれも使用できる。
(D):シリカフィラー(2)
(C)成分のシリカフィラー(1)、および、(D)成分のシリカフィラー(2)は、封止した部位の耐湿性および耐サーマルサイクル性、特に耐サーマルサイクル性を向上させる目的で液状封止材に添加される。シリカフィラーの添加により耐サーマルサイクル性が向上するのは、線膨張係数を下げることにより、サーマルサイクルによる、液状封止材の硬化物の膨張・収縮を抑制できるからである。
本発明の液状封止材では、(C)成分として、平均粒径が7~50nmのシリカフィラー(1)と、(D)成分として、平均粒径が0.2~5μmのシリカフィラー(2)という、平均粒径が互いに異なる2種類のシリカフィラーを併用する。平均粒径が互いに異なる2種類のシリカフィラーを併用する理由は以下の通り。
シリカフィラーのみに着目して、シリカフィラーを最密充填状態に近づけることを考えた場合、平均粒径が同一の範囲のシリカフィラーのみ、つまり、単一粒子径のシリカフィラーを使用するよりも、平均粒径が互いに異なる2種類のシリカフィラーを併用する、つまり、多成分粒子径のシリカフィラーを使用するほうが好ましい。それは粒径が大きいシリカフィラー同士の間隙に、粒径がより小さいシリカフィラーが入りこむことで、シリカフィラーをより密に充填できるからである。シリカフィラー単体として、最密充填状態に近づくということは、該シリカフィラーを成分とする液状封止材では、シリカフィラー同士の間隙が広がるために分散性が向上することになる。これは、液状封止材の流動性に寄与する樹脂成分が多くなるためである。結果として液状封止材の粘度が低くなり、半導体素子と基板との間のギャップへの注入性が向上する。上記の理由から、(C)成分のシリカフィラー(1)と、(D)成分のシリカフィラー(2)と、の平均粒径の差が大きいことが望ましい。
これに対し、本発明の液状封止材では、(C)成分のシリカフィラー(1)として、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランで予め表面処理されたものを使用する。
2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランは、下記式に示す構造をなしており、末端にシクロ環が存在する。
このシクロ環による立体障害のため、特許文献2に記載されたもののような、従来使用される、グリシジルエーテル型シランカップリング剤のグリシジル基よりも活性が制限される。そのため、シリカフィラーの表面に存在するシラノール基と、シランカップリング剤としての2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランと、が適度に反応するため、液状封止材における分散性が良好である。このため、液状封止材の粘度が増加することがなく、半導体素子と基板との間のギャップへの注入性が良好である。
撹拌法は、予めシランカップリング剤とシリカフィラーとを撹拌装置に仕込み、適切な条件で撹拌する方法である、上記撹拌装置としては、ヘンシェルミキサー等の高速回転で撹拌・混合が可能なミキサーを用いることができるが、特に限定されるものではない。
湿式法は、表面処理しようとするシリカフィラーの表面積に対して十分な量のシランカップリング剤を水または有機溶剤に溶解して、シランカップリング剤をなす化合物、すなわち、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランを加水分解させることにより、表面処理溶液とする。得られた表面処理溶液に対してシリカフィラーを添加し、スラリー状となるように撹拌する。撹拌によってシランカップリング剤およびシリカフィラーを十分反応させた後、濾過や遠心分離等の方法によりシリカフィラーを表面処理溶液から分離し、加熱乾燥する。
乾式法は、攪拌装置によって高速攪拌しているシリカフィラーに、シランカップリング剤の原液あるいは溶液を均一に分散させて処理する方法である。上記撹拌装置としては、ヘンシェルミキサー等の高速回転で撹拌・混合が可能なミキサーを用いることができるが、特に限定されるものではない。
なお、上記撹拌法、湿式法、乾式法以外にも、例えば、シリカフィラーを溶媒中に分散させてなるシリカフィラー分散液に直接シランカップリング剤を添加し、シリカフィラーの表面を改質するインテグラルブレンド法も好適に用いることができる。
一方、(C)成分のシリカフィラー(1)の平均粒径50nm超だと、(D)成分のシリカフィラー(2)との平均粒径の差が小さくなるため、液状封止材における(C)成分のシリカフィラー(1)、および、(D)成分のシリカフィラー(2)の両方の分散性が低下し、半導体素子と基板との間のギャップへの注入性が低下する。
(C)成分のシリカフィラー(1)は、平均粒径が7~15nmであることがより好ましい。
但し、真球度0.8以上の略真球状の形状をなすことが、液状封止材中でのシリカフィラーの分散性、および、液状封止材の注入性が向上するとともに、シリカフィラーをより最密充填状態に近づけるという観点から好ましい。本明細書における「真球度」は、「粒子の最大径に対する最小径の比」と定義する。例えば、走査型電子顕微鏡(SEM)による観察の結果、観測される最大径に対する最小径の比が0.8以上であればよい。(C)成分のシリカフィラーは、真球度が0.9以上であることが好ましい。
シランカップリング剤によるシリカフィラーの表面処理方法については、(C)成分のシリカフィラー(1)について記載したのと同様である。
一方、(D)成分のシリカフィラー(2)の平均粒径5μm超だと、半導体素子と基板とのギャップに対してシリカフィラーのサイズが大き過ぎ、注入時にボイドの巻き込みが問題となる。
(D)成分のシリカフィラー(2)は、平均粒径が0.25~0.6μmであることがより好ましい。
シリカフィラー(1),(2)の合計含有量が45質量部未満だと、液状封止材の線膨張係数が大きくなり、液状封止材で封止した部位の耐サーマルサイクル性が低下する。
一方、シリカフィラー(1),(2)の合計含有量が77質量部超だと、液状封止材の粘度が増加し、半導体素子と基板とのギャップへの注入性が低下する。
シリカフィラー(1),(2)の合計含有量は、50~70質量部であることがより好ましい。
シリカフィラー(1)の配合割合が1:10.2より多いと、液状封止材におけるシリカフィラー(1)の分散性が悪化し、液状封止材の粘度が増加し、半導体素子と基板との間のギャップへの注入性が低下する。
一方、シリカフィラー(1)の配合割合が1:559より少ないと、液状封止材におけるシリカフィラー(1)、(2)の分散性が悪化し、もしくは、シリカフィラー(2)の分散性が悪化し、半導体素子と基板との間のギャップへの注入性が低下する。
シリカフィラー(1),(2)の配合割合は、1:17.7~1:111であることがより好ましく、1:17.7~1:76が更に好ましい。
本発明の液状封止材は、(E)成分としてルイス塩基もしくはその塩を含有してもよい。
上述したように、(C)成分のシリカフィラー(1)、および、(D)成分のシリカフィラー(2)の表面には親水基であるシラノール基が多数存在する。これらのシラノール基は、ルイス酸としても作用し活性を持つ。
(E)成分として、ルイス塩基もしくはその塩を含有することにより、シリカフィラー(1),(2)の表面に存在するシラノール基のルイス酸活性が抑制される。これにより、液状封止材におけるシリカフィラー(1),(2)の分散性がさらに向上する。これにより、半導体素子と基板との間のギャップへの注入性がさらに向上する。
(E)成分のルイス塩基もしくはその塩としては、イミダゾール類、ジアザビシクロノネン、ジアザビシクロウンデセン等のアミン化合物、もしくはそれらの塩、トリフェニルホスフィン、ジフェニルホスフィン、フェニルホスフィン等のホスフィン化合物、もしくはそれらの塩を用いることができる。
これらの中でも、トリフェニルホスフィンが、シリカフィラー表面のシラノール基に効果的に作用し、かつ液状封止材の貯蔵安定性が良好になるため好ましい。
(E)成分として、ルイス塩基を含有させる場合、本発明の液状封止材におけるルイス塩基の含有量は、(C)成分のシリカフィラー(1)、および、(D)成分のシリカフィラー(2)の合計量100質量部に対して、0.1~0.8質量部であることが好ましく、0.2~0.5質量部であることがより好ましい。
本発明の液状封止材は、上記(A)~(E)成分以外の成分を必要に応じてさらに含有してもよい。このような成分の具体例としてはエラストマー、硬化促進剤、金属錯体、レベリング剤、着色剤、イオントラップ剤、消泡剤、難燃剤などを配合することができる。各配合剤の種類、配合量は常法通りである。
本発明の液状封止材は、上記(A)~(D)成分、および、含有させる場合はさらに(E)成分、ならびに、さらに必要に応じて配合するその他の配合剤を混合し、攪拌して調製される。
混合攪拌は、ロールミルを用いて行うことができるが、勿論、これに限定されない。(A)成分のエポキシ樹脂が固形の場合には、加熱などにより液状化ないし流動化し混合することが好ましい。
各成分を同時に混合しても、一部成分を先に混合し、残りの成分を後から混合するなど、適宜変更しても差支えない。(A)成分の液状エポキシ樹脂に対し、(C)成分のシリカフィラー(1)を均一に分散させることが困難な場合は、(A)成分の液状エポキシ樹脂と、(C)成分のシリカフィラー(1)を先に混合し、残りの成分を後から混合してもよい(A)成分の液状エポキシ樹脂と、(C)成分のシリカフィラー(1)と、を先に混合し、残りの成分を後から混合してもよい。
本発明の液状封止材は、常温(25℃)での粘度が100Pa・s以下であることがより好ましい。
本発明の液状封止材をアンダーフィルとして使用する場合、以下の手順で基板と半導体素子との間のギャップに本発明の液状封止材を充填する。
基板をたとえば70~130℃に加熱しながら、半導体素子の一端に本発明の液状封止材を塗布すると、毛細管現象によって、基板と半導体素子との間のギャップに本発明の液状封止材が充填される。この際、本発明の液状封止材充填に要する時間を短くするため、基板を傾斜させたり、該ギャップ内外に圧力差を生じさせてもよい。
該ギャップに本発明の液状封止材を充填させた後、該基板を所定温度で所定時間、具体的には、80~200℃で0.2~6時間加熱して、液状封止材を加熱硬化させることによって、該ギャップを封止する。
下記表に示す配合割合となるように、ロールミルを用いて原料を混練して実施例1~15、比較例1~6の液状封止材を調製した。但し、(A)成分の液状エポキシ樹脂と、(C)成分のシリカフィラー(1)を先に混合し、残りの成分を後から混合した。なお、表中の各組成に関する数値は質量部を表している。
エポキシ樹脂A-1:ビスフェノールF型エポキシ樹脂、製品名YDF8170、新日鐵化学株式会社製、エポキシ当量158
エポキシ樹脂A-2:アミノフェノール型エポキシ樹脂、製品名jER630、三菱化学株式会社製、エポキシ当量94g/eq
エポキシ樹脂A-3:1,4ヘキサンジメタノールジグリシジルエーテル、製品名EP-4085S、株式会社ADEKA製、エポキシ当量135g/eq
硬化剤B-1:4,4’-ジアミノ-3,3’-ジエチルジフェニルメタン、製品名カヤハードA-A、日本化薬株式会社製
硬化剤B-2:ジエチルトリエンジアミン、製品名エタキュア100、アルベマール日本株式会社製
硬化剤B-3:ジメチルチオトルエンジアミン、製品名HARTCURE30、Jonson Fine Chemical製
シリカフィラーC-1:2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン表面処理シリカフィラー(平均粒径:7nm)、製品名YN010A-JGP、株式会社アドマテックス製
シリカフィラーC-2:2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン表面処理シリカフィラー(平均粒径:10nm)、製品名YA010A-JGP、株式会社アドマテックス製
シリカフィラーC-3:2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン表面処理シリカフィラー(平均粒径:50nm)、製品名YA050A-JGP、株式会社アドマテックス製
シリカフィラーC-4:2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン表面処理シリカフィラー(平均粒径:100nm)、製品名YC100A-JGP、株式会社アドマテックス製
シリカフィラーC-5:表面未処理シリカフィラー(平均粒径12nm)、製品名R200、Evonik Industries AG製
シリカフィラーC-6:トリメチルシリル表面処理シリカフィラー(平均粒径12nm)、製品名RX200、Evonik Industries AG製
シリカフィラーC-7:オクチルシリル表面処理シリカフィラー(平均粒径12nm)、製品名R805、Evonik Industries AG製
シリカフィラーD-1:表面未処理シリカフィラー(平均粒径:0.3μm)、製品名SP-03B、扶桑化学株式会社製
シリカフィラーD-2:シランカップリング剤(3-グリシドキシプロピルトリメトキシシラン)表面処理シリカフィラー(平均粒径:0.25μm)、製品名SE1053-SEO、株式会社アドマテックス製
シリカフィラーD-3:シランカップリング剤(3-グリシドキシプロピルトリメトキシシラン)表面処理シリカフィラー(平均粒径:0.5μm)、製品名SE2200-SEE、株式会社アドマテックス製
シリカフィラーD-4:シランカップリング剤(3-グリシドキシプロピルトリメトキシシラン)表面処理シリカフィラー(平均粒径:1.5μm)、製品名SE5050-SEJ、株式会社アドマテックス製
(E)ルイス塩基
ルイス塩基E-1:トリフェニルホスフィン、製品名TPP、北興化学工業株式会社製
(粘度)
ブルックフィールド粘度計を用いて、液温25℃、50rpmで調製直後の評価用試料の粘度を測定した。
ブルックフィールド社製回転粘度計HBDV-1(スピンドルSC4-14使用)用いて、5rpmで25℃における粘度(Pa・s)、および、50rpmで25℃における粘度(Pa・s)測定し、5rpmで測定した粘度の測定値を、50rpmで測定した粘度の測定値により除した値(50rpmでの粘度に対する5rpmでの粘度の比)を、チクソトロピー指数として示す。
有機基板(FR-4基板)上に、20μmまたは50μmのギャップを設けて、半導体素子の代わりにガラス板を固定した試験片を作製した。この試験片を110℃に設定したホットプレート上に置き、ガラス板の一端側に液状封止材を塗布し、注入距離が20mmに達するまでの時間を測定した。この手順を2回実施し、測定値の平均値を注入時間の測定値とした。
(E)成分として、ルイス塩基(トリフェニルホスフィン)を含有させた実施例7では、液状封止材の物性(粘度、T.I.、20mm注入性)がさらに向上した。
また、(D)成分のシリカフィラー2として、シランカップリング剤で表面処理したシリカフィラーを使用した実施例13~15では、液状封止材の物性(粘度、T.I.、20mm注入性)を損なうことなく、シリカフィラー2の含有量を増加することができた。
一方、(C)成分のシリカフィラー1として、平均粒径が50nm超(100nm)のものを使用した比較例1は、液状封止材の20mm注入性が劣っていた。(C)成分のシリカフィラー1として、表面未処理のものを使用した比較例2、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン以外のカップリング剤で表面処理した比較例3、4、(C)成分のシリカフィラー1の配合割合を(D)成分のシリカフィラー2に対して、1:10.2より多くした比較例5は、液状封止材の物性(粘度、T.I.、20mm注入性)が劣っていた。
Claims (7)
- (A)液状エポキシ樹脂、(B)硬化剤、(C)2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランで表面処理された平均粒径7~50nmのシリカフィラー、および、(D)平均粒径0.2~5μmのシリカフィラーを含み、
液状封止材の全成分の合計100質量部に対し、前記(C)成分のシリカフィラー、および、前記(D)成分のシリカフィラーの合計含有量が、45~77質量部であり、
前記(C)成分のシリカフィラーと、前記(D)成分のシリカフィラーと、の配合割合(質量比)が1:10.2~1:559であることを特徴とする液状封止材。 - 前記(A)成分の液状エポキシ樹脂と、前記(C)成分の2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランで表面処理された平均粒径7~50nmのシリカフィラーと、が予め混合されている、請求項1に記載の液状封止材。
- 前記(B)成分の硬化剤がアミン系硬化剤である、請求項1または2に記載の液状封止材。
- 前記(D)成分のシリカフィラーが、シランカップリング剤で表面処理されている、請求項1~3のいずれかに記載の液状封止材。
- さらに、(E)ルイス塩基もしくはその塩を含有する、請求項1~4のいずれかに記載の液状封止材。
- 前記(E)成分が、トリフェニルホスフィンである、請求項5に記載の液状封止材。
- 請求項1~6のいずれかに記載の液状封止材を用いて封止されたフリップチップ型半導体素子を有する半導体装置。
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- 2015-03-20 US US15/309,972 patent/US9994729B2/en active Active
- 2015-04-29 TW TW104113693A patent/TWI667267B/zh active
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US20190270881A1 (en) * | 2017-03-22 | 2019-09-05 | Lg Chem, Ltd. | Resin composition for semiconductor package, prepreg, and metal clad laminate using the same |
US11091630B2 (en) * | 2017-03-22 | 2021-08-17 | Lg Chem, Ltd | Resin composition for semiconductor package, prepreg, and metal clad laminate using the same |
US11214677B2 (en) * | 2017-03-22 | 2022-01-04 | Lg Chem, Ltd. | Resin composition for semiconductor package, prepreg and metal clad laminate using the same |
Also Published As
Publication number | Publication date |
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JP2015218229A (ja) | 2015-12-07 |
US9994729B2 (en) | 2018-06-12 |
TW201544519A (zh) | 2015-12-01 |
MY184315A (en) | 2021-04-01 |
TWI667267B (zh) | 2019-08-01 |
CN106232763A (zh) | 2016-12-14 |
JP6415104B2 (ja) | 2018-10-31 |
KR20170008210A (ko) | 2017-01-23 |
US20170145251A1 (en) | 2017-05-25 |
KR102337127B1 (ko) | 2021-12-07 |
CN106232763B (zh) | 2018-05-11 |
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