TWI666260B - Resin composition for encapsulation and semiconductor device - Google Patents
Resin composition for encapsulation and semiconductor device Download PDFInfo
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- TWI666260B TWI666260B TW104115725A TW104115725A TWI666260B TW I666260 B TWI666260 B TW I666260B TW 104115725 A TW104115725 A TW 104115725A TW 104115725 A TW104115725 A TW 104115725A TW I666260 B TWI666260 B TW I666260B
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- resin composition
- sealing
- sealing resin
- mass
- content
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- 239000011342 resin composition Substances 0.000 title claims abstract description 108
- 239000004065 semiconductor Substances 0.000 title claims abstract description 85
- 238000005538 encapsulation Methods 0.000 title description 2
- 238000007789 sealing Methods 0.000 claims abstract description 126
- 239000003822 epoxy resin Substances 0.000 claims abstract description 63
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 63
- 239000004848 polyfunctional curative Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims description 53
- 239000000945 filler Substances 0.000 claims description 39
- 239000007822 coupling agent Substances 0.000 claims description 31
- 238000003860 storage Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000005011 phenolic resin Substances 0.000 claims description 14
- 238000001723 curing Methods 0.000 claims description 11
- 239000007769 metal material Substances 0.000 claims description 11
- 238000010298 pulverizing process Methods 0.000 claims description 11
- 238000003809 water extraction Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000000284 extract Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical group S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910002026 crystalline silica Inorganic materials 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 239000007787 solid Substances 0.000 claims 2
- 238000013007 heat curing Methods 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 235000010215 titanium dioxide Nutrition 0.000 claims 1
- -1 polytetrafluoroethylene Polymers 0.000 description 68
- 150000001875 compounds Chemical class 0.000 description 24
- 239000000203 mixture Substances 0.000 description 20
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 19
- 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 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 16
- 125000003118 aryl group Chemical group 0.000 description 15
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 14
- 229910000077 silane Inorganic materials 0.000 description 13
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- 150000003254 radicals Chemical class 0.000 description 11
- 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 10
- 239000013078 crystal Substances 0.000 description 9
- 125000001624 naphthyl group Chemical group 0.000 description 9
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 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 8
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 125000000962 organic group Chemical group 0.000 description 7
- 125000004437 phosphorous atom Chemical group 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 150000003003 phosphines Chemical class 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 5
- 239000013522 chelant Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 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 4
- 229930185605 Bisphenol Natural products 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 4
- JRNGUTKWMSBIBF-UHFFFAOYSA-N naphthalene-2,3-diol Chemical compound C1=CC=C2C=C(O)C(O)=CC2=C1 JRNGUTKWMSBIBF-UHFFFAOYSA-N 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 229960003237 betaine Drugs 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 150000001343 alkyl silanes Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001409 amidines Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004203 carnauba wax Substances 0.000 description 2
- 235000013869 carnauba wax Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000001139 pH measurement Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 230000000284 resting effect Effects 0.000 description 2
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- SJJCQDRGABAVBB-UHFFFAOYSA-N 1-hydroxy-2-naphthoic acid Chemical compound C1=CC=CC2=C(O)C(C(=O)O)=CC=C21 SJJCQDRGABAVBB-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-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
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-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
- XFZVQMVEKCAHDA-UHFFFAOYSA-N 3-phenylsulfanylbenzene-1,2-diamine Chemical compound NC1=CC=CC(SC=2C=CC=CC=2)=C1N XFZVQMVEKCAHDA-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- MBSPLHJILPYMOT-UHFFFAOYSA-N 4-methoxy-2-methyl-6-trimethoxysilylhex-1-en-3-one Chemical compound C(=O)(C(=C)C)C(CC[Si](OC)(OC)OC)OC MBSPLHJILPYMOT-UHFFFAOYSA-N 0.000 description 1
- VGDAMJGKFYMEDE-UHFFFAOYSA-N 5-(dimethoxymethylsilyl)pentane-1,3-diamine Chemical compound NCCC(CC[SiH2]C(OC)OC)N VGDAMJGKFYMEDE-UHFFFAOYSA-N 0.000 description 1
- ZLPHWFDYGOHXJD-UHFFFAOYSA-N C(=O)(C(=C)C)[SiH2]C1=CC=CC=2C3=CC=CC=C3CC12 Chemical compound C(=O)(C(=C)C)[SiH2]C1=CC=CC=2C3=CC=CC=C3CC12 ZLPHWFDYGOHXJD-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
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- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
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- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
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- 125000004354 sulfur functional group Chemical group 0.000 description 1
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- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
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- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- DMEUUKUNSVFYAA-UHFFFAOYSA-N trinaphthalen-1-ylphosphane Chemical compound C1=CC=C2C(P(C=3C4=CC=CC=C4C=CC=3)C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 DMEUUKUNSVFYAA-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
-
- 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
-
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/32245—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
- H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
- H01L2224/45001—Core members of the connector
- H01L2224/45099—Material
- H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
- H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
- H01L2224/45147—Copper (Cu) as principal constituent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/484—Connecting portions
- H01L2224/48463—Connecting portions the connecting portion on the bonding area of the semiconductor or solid-state body being a ball bond
- H01L2224/48465—Connecting portions the connecting portion on the bonding area of the semiconductor or solid-state body being a ball bond the other connecting portion not on the bonding area being a wedge bond, i.e. ball-to-wedge, regular stitch
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73251—Location after the connecting process on different surfaces
- H01L2224/73265—Layer and wire connectors
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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
- H01L2924/00011—Not relevant to the scope of the group, the symbol of which is combined with the symbol of this group
Abstract
本發明係關於一種密封用樹脂組成物，其係用以密封半導體元件、及連接於上述半導體元件且以Cu為主成分之接合線；且其含有環氧樹脂及硬化劑；於條件1下測定之pH(1)與於條件2下測定之pH(2)之差(pH(1)-pH(2))為1.1以下。 The present invention relates to a resin composition for sealing, which is used to seal a semiconductor element and a bonding wire containing Cu as a main component connected to the semiconductor element; and it contains an epoxy resin and a hardener; measured under condition 1 The difference between the pH (1) and the pH (2) measured under Condition 2 (pH (1) -pH (2) ) is 1.1 or less.
Description
本發明係關於一種密封用樹脂組成物、及半導體裝置。 The present invention relates to a sealing resin composition and a semiconductor device.
為了提昇具備接合線之半導體裝置之可靠性，一直對密封用樹脂組成物進行各種研究。作為此種技術，例如可列舉專利文獻1中記載者。 In order to improve the reliability of a semiconductor device including a bonding wire, various studies have been conducted on a resin composition for sealing. Examples of such a technique include those described in Patent Document 1.
專利文獻1中記載有一種含有水解性氯量為10~20ppm之聯苯型環氧樹脂的半導體密封用環氧樹脂組成物。 Patent Document 1 describes an epoxy resin composition for semiconductor sealing containing a biphenyl epoxy resin having a hydrolyzable chlorine content of 10 to 20 ppm.
[先前技術文獻] [Prior technical literature]
[專利文獻] [Patent Literature]
專利文獻1：日本特開2013-67694號公報 Patent Document 1: Japanese Patent Application Publication No. 2013-67694
本發明謀求提昇藉由密封用樹脂組成物之硬化物將半導體 元件、及連接於半導體元件且以Cu為主成分之接合線密封而成的半導體裝置之可靠性。 The present invention seeks to improve the performance of semiconductors by hardening the sealing resin composition. Reliability of a device and a semiconductor device formed by sealing a bonding wire connected to a semiconductor device with Cu as a main component.
根據本發明可提供一種密封用樹脂組成物，其用以密封半導體元件、及連接於上述半導體元件且以Cu為主成分之接合線；且含有：環氧樹脂、及硬化劑；且於以下之條件1下測定之pH(1)與於以下之條件2下測定之pH(2)之差(pH(1)-pH(2))為1.1以下。 According to the present invention, there can be provided a sealing resin composition for sealing a semiconductor element and a bonding wire containing Cu as a main component connected to the semiconductor element; and containing: an epoxy resin and a hardener; and The difference between the pH (1) measured under Condition 1 and the pH (2) measured under Condition 2 below (pH (1) -pH (2) ) is 1.1 or less.
(條件1：將使上述密封用樹脂組成物於175℃、4小時之條件下熱硬化而獲得之硬化物粉碎，獲得粉碎物。繼而，將剛粉碎後之上述粉碎物5g放入純水50ml中後，於125℃、20小時之條件下對該純水進行熱水萃取處理，測定所獲得之萃取液之pH(pH(1))) (Condition 1: The hardened material obtained by thermally curing the sealing resin composition at 175 ° C. for 4 hours was pulverized to obtain a pulverized material. Then, 5 g of the pulverized material immediately after pulverization was put into 50 ml of pure water. After neutralization, the pure water was subjected to hot water extraction treatment at 125 ° C for 20 hours, and the pH (pH (1) ) of the obtained extract was measured.
(條件2：將使上述密封用樹脂組成物於175℃、4小時之條件下熱硬化而獲得之硬化物粉碎，獲得粉碎物。繼而，將上述粉碎物於175℃保管500小時。繼而，將保管後之上述粉碎物5g放入純水50ml中後，於125℃、20小時之條件下對該純水進行熱水萃取處理，測定所獲得之萃取液之pH(pH(2))) (Condition 2: The hardened material obtained by thermally curing the sealing resin composition at 175 ° C for 4 hours is pulverized to obtain a pulverized material. Then, the pulverized material is stored at 175 ° C for 500 hours. Then, the pulverized material is stored for 500 hours. After storing 5 g of the above-mentioned pulverized material in 50 ml of pure water, the pure water was subjected to hot water extraction treatment at 125 ° C for 20 hours, and the pH (pH (2) ) of the obtained extract was measured.
根據本發明可提供一種半導體裝置，其具備：半導體元件；接合線，其連接於上述半導體元件且以Cu為主成分；及 密封樹脂，其係由上述密封用樹脂組成物之硬化物所構成，且密封上述半導體元件與上述接合線。 According to the present invention, there can be provided a semiconductor device including: a semiconductor element; a bonding wire connected to the semiconductor element and containing Cu as a main component; and The sealing resin is composed of a hardened body of the sealing resin composition, and seals the semiconductor element and the bonding wire.
根據本發明，可提昇半導體裝置之可靠性。 According to the present invention, the reliability of a semiconductor device can be improved.
10‧‧‧晶粒黏著材 10‧‧‧ Grain Adhesive
20‧‧‧半導體元件 20‧‧‧Semiconductor element
22‧‧‧電極墊 22‧‧‧electrode pad
30‧‧‧基材 30‧‧‧ substrate
32‧‧‧晶座 32‧‧‧ Crystal Block
34‧‧‧外引線 34‧‧‧Outer Lead
40‧‧‧接合線 40‧‧‧ bonding wire
50‧‧‧密封樹脂 50‧‧‧sealing resin
100‧‧‧半導體裝置 100‧‧‧ semiconductor device
上述目的、及其他目的、特徵及優點係藉由以下所述之較佳之實施形態、及隨附於此之以下之圖式而更明瞭。 The above object, and other objects, features, and advantages are made clearer by the preferred embodiments described below and the following drawings attached thereto.
圖1係表示本實施形態之半導體裝置之剖視圖。 FIG. 1 is a sectional view showing a semiconductor device according to this embodiment.
以下，使用圖式對實施之形態進行說明。再者，對全部圖式，對相同之構成要素標註相同之符號，並適當省略說明。 Hereinafter, embodiments will be described using drawings. In addition, the same symbols are assigned to the same components in all the drawings, and the description is appropriately omitted.
圖1係表示本實施形態之半導體裝置100之剖視圖。 FIG. 1 is a cross-sectional view showing a semiconductor device 100 according to this embodiment.
本實施形態之密封用樹脂組成物係用以密封半導體元件、及連接於上述半導體元件且以Cu為主成分之接合線；且其含有環氧樹脂及硬化劑。又，密封用樹脂組成物之於以下之條件1下測定之pH(1)與於以下之條件2下測定之pH(2)之差(pH(1)-pH(2))為1.1以下。 The sealing resin composition of this embodiment is used to seal a semiconductor element and a bonding wire containing Cu as a main component connected to the semiconductor element; and it contains an epoxy resin and a hardener. The difference (pH (1) -pH (2) ) between the pH (1) measured under the following Condition 1 and the pH (2) measured under the following Condition 2 of the resin composition for sealing is 1.1 or less.
(條件1：將使上述密封用樹脂組成物於175℃、4小時之條件下熱硬化而獲得之硬化物粉碎，獲得粉碎物。繼而，將剛粉碎後之上述粉碎物5g放入純水50ml中後，於125℃、20小時之條件下對該純水進行熱水萃取處理，測定所獲得之萃取液之pH(pH(1))) (Condition 1: The hardened material obtained by thermally curing the sealing resin composition at 175 ° C. for 4 hours was pulverized to obtain a pulverized material. Then, 5 g of the pulverized material immediately after pulverization was put into 50 ml of pure water. After neutralization, the pure water was subjected to hot water extraction treatment at 125 ° C for 20 hours, and the pH (pH (1) ) of the obtained extract was measured.
(條件2：將使上述密封用樹脂組成物於175℃、4小時之條件下熱硬化而獲得之硬化物粉碎，獲得粉碎物。繼而，將上述粉碎物於175℃保管500小時。繼而，將保管後之上述粉碎物5g放入純水50ml中後，於125℃、20小時之條件下對該純水進行熱水萃取處理，測定所獲得之萃取液之pH(pH(2))) (Condition 2: The hardened material obtained by thermally curing the sealing resin composition at 175 ° C for 4 hours is pulverized to obtain a pulverized material. Then, the pulverized material is stored at 175 ° C for 500 hours. Then, After storing 5 g of the above-mentioned pulverized material in 50 ml of pure water, the pure water was subjected to hot water extraction treatment at 125 ° C for 20 hours, and the pH (pH (2) ) of the obtained extract was measured.
作為表示半導體裝置之可靠性之指標之一，可列舉高溫保管特性。高溫保管特性例如可基於以Cu為主成分之接合線與半導體元件之連接部於高溫環境下保管後之連接性而評價。然而，例如於1000小時之長時間之高溫保管時，有難以維持接合線與半導體元件之良好連接性之擔憂。因此，謀求進一步提昇高溫保管特性以使即便於極長時間之高溫保管時亦可維持良好之連接性。 As one of the indicators showing the reliability of a semiconductor device, high-temperature storage characteristics can be cited. The high-temperature storage characteristics can be evaluated, for example, based on the connectivity of a bonding wire containing Cu as a main component and a connection portion of a semiconductor element after storage in a high-temperature environment. However, there is a concern that it is difficult to maintain a good connection between the bonding wire and the semiconductor element during storage at a high temperature for a long time of 1,000 hours, for example. Therefore, it is sought to further improve the high-temperature storage characteristics so that good connectivity can be maintained even during extremely high-temperature storage.
本發明人對可提昇高溫保管特性之密封用樹脂組成物進行了努力研究。結果有如下新發現：藉由控制於上述條件1下測定之pH(1)與於上述條件2下測定之pH(2)之差(pH(1)-pH(2))而可謀求高溫保管特性之提昇。本實施形態係基於此種見解而實現(pH(1)-pH(2))為1.1以下之密封用樹脂組成物。藉此，可提昇使用密封用樹脂組成物而製造之半導體裝置之高溫保管特性。因此，可提昇半導體裝置之可靠性。 The present inventors have made intensive studies on a sealing resin composition capable of improving high-temperature storage characteristics. As a result, there was a new finding that high-temperature storage can be achieved by controlling the difference (pH (1) -pH (2) ) between the pH (1) measured under the above-mentioned condition 1 and the pH (2) measured under the above-mentioned condition 2. Improvement of features. This embodiment is based on such a knowledge, and achieves the sealing resin composition (pH (1) -pH (2) ) of 1.1 or less. Thereby, the high-temperature storage characteristics of the semiconductor device manufactured using the sealing resin composition can be improved. Therefore, the reliability of the semiconductor device can be improved.
以下，對本實施形態之密封用樹脂組成物、及具備由密封用樹脂組成物之硬化物構成之密封樹脂50之半導體裝置100進行詳細說明。 Hereinafter, the sealing resin composition and the semiconductor device 100 provided with the sealing resin 50 which consists of the hardened | cured material of the sealing resin composition of this embodiment are demonstrated in detail.
首先，對密封用樹脂組成物進行說明。 First, the sealing resin composition will be described.
密封用樹脂組成物係用以密封半導體元件及連接於半導體元件且以Cu為主成分之接合線。於本實施形態中，例示如下情形：利用由密封用樹脂 組成物之硬化物構成之密封樹脂將半導體元件及接合線密封，藉此形成半導體封裝。 The sealing resin composition is used to seal a semiconductor element and a bonding wire connected to the semiconductor element and containing Cu as a main component. In this embodiment, a case where the resin for sealing is used is exemplified. A sealing resin composed of a cured product of the composition seals the semiconductor element and the bonding wire, thereby forming a semiconductor package.
半導體元件例如搭載於構成引線框架之晶座或者有機基板等基材上、或其他半導體元件上。此時，半導體元件經由接合線而與構成引線框架之外引線、有機基板或其他半導體元件電性連接。接合線例如連接於設置於半導體元件之電極墊。半導體元件之電極墊例如藉由至少表面以Al為主成分之金屬材料構成。 The semiconductor element is mounted on a base material such as a crystal base or an organic substrate constituting a lead frame, or other semiconductor elements. At this time, the semiconductor element is electrically connected to a lead other than the lead frame, an organic substrate, or another semiconductor element via a bonding wire. The bonding wire is connected to, for example, an electrode pad provided on a semiconductor element. The electrode pad of the semiconductor element is made of, for example, a metal material whose main component is Al at least on the surface.
接合線係藉由以Cu為主成分之金屬材料構成。作為此種金屬材料，例如可列舉由Cu單質所構成之金屬材料、或以Cu為主成分並含有其他金屬之合金材料。 The bonding wire is made of a metal material containing Cu as a main component. Examples of such a metal material include a metal material composed of a Cu simple substance, or an alloy material containing Cu as a main component and containing other metals.
於本實施形態中，就低成本化等觀點而言，作為較佳態樣之一例可列舉使用由Cu之含量為99.9質量%以上之金屬材料所構成之接合線。通常，於使用此種Cu線之情形時，有難以提昇半導體裝置之高溫保管特性之擔憂。然而，根據本實施形態，藉由如下述般控制(pH(1)-pH(2))，即便於使用如上述之Cu線之情形時，亦可實現優異之高溫保管特性。 In this embodiment, from the viewpoint of cost reduction and the like, as an example of a preferable aspect, a bonding wire composed of a metal material having a Cu content of 99.9% by mass or more is used. Generally, when such a Cu wire is used, there is a concern that it is difficult to improve the high-temperature storage characteristics of a semiconductor device. However, according to this embodiment, by controlling (pH (1) -pH (2) ) as described below, even when a Cu wire as described above is used, excellent high-temperature storage characteristics can be achieved.
密封用樹脂組成物之於以下之條件1下測定之pH(1)與於以下之條件2下測定之pH(2)之差(pH(1)-pH(2))為1.1以下。藉此，如上所述，可提昇半導體裝置之高溫保管特性。 The difference (pH (1) -pH (2) ) between the pH (1) measured under the following Condition 1 and the pH (2) measured under the following Condition 2 of the resin composition for sealing is 1.1 or less. Thereby, as described above, the high-temperature storage characteristics of the semiconductor device can be improved.
(條件1) (Condition 1)
將使上述密封用樹脂組成物於175℃、4小時之條件下熱硬化而獲得之硬化物粉碎，獲得粉碎物。繼而，將剛粉碎後之上述粉碎物5g放入純水50ml中後，於125℃、20小時之條件下對該純水進行熱水萃取處理，測定 所獲得之萃取液之pH(pH(1))。 The hardened | cured material obtained by heat-hardening the said sealing resin composition at 175 degreeC for 4 hours was pulverized, and the pulverized material was obtained. Next, 5 g of the above-mentioned pulverized product was put into 50 ml of pure water immediately after pulverization, and the pure water was subjected to hot water extraction treatment at 125 ° C for 20 hours, and the pH (pH (1 ) ).
(條件2) (Condition 2)
將使上述密封用樹脂組成物於175℃、4小時之條件下熱硬化而獲得之硬化物粉碎，獲得粉碎物。繼而，將上述粉碎物於175℃保管500小時。繼而，將保管後之上述粉碎物5g放入純水50ml中後，於125℃、20小時之條件下對該純水進行熱水萃取處理，測定所獲得之萃取液之pH(pH(2))。 The hardened | cured material obtained by heat-hardening the said sealing resin composition at 175 degreeC for 4 hours was pulverized, and the pulverized material was obtained. Then, the crushed material was stored at 175 ° C for 500 hours. Next, 5 g of the above-mentioned pulverized material after storage was put into 50 ml of pure water, and the pure water was subjected to hot water extraction treatment at 125 ° C for 20 hours, and the pH (pH (2)) of the obtained extract was measured. ).
於上述條件1及上述條件2中，硬化物之粉碎處理例如可藉由使用TI-100(CMT股份有限公司製造)並將硬化物5.2g放入粉碎釜中粉碎2分鐘而進行。又，於上述條件1及上述條件2中，熱水萃取處理例如可使用內容器為聚四氟乙烯製、外容器為金屬製之耐壓容器而進行。又，於上述條件2中，粉碎物之保管並無特別限定，例如可藉由於溫度保持為175℃之無塵烘箱內載置放入有上述密封用樹脂組成物之密閉容器而進行。 In the above Condition 1 and Condition 2, the pulverization treatment of the hardened material can be performed, for example, by using TI-100 (manufactured by CMT Co., Ltd.) and pulverizing 5.2 g of the hardened material in a pulverizer for 2 minutes. In the above Condition 1 and Condition 2, the hot water extraction treatment can be performed using, for example, a pressure-resistant container made of polytetrafluoroethylene in the inner container and a metal container in the outer container. In the above Condition 2, the storage of the pulverized material is not particularly limited, and it can be performed, for example, by placing a closed container containing the sealing resin composition in a dust-free oven maintained at a temperature of 175 ° C.
就可更有效地提昇半導體裝置之高溫保管特性之觀點而言，(pH(1)-pH(2))更佳為0.8以下，尤佳為0.6以下。(pH(1)-pH(2))之下限值並無特別限定，例如可設為0.1。 From the viewpoint that the high-temperature storage characteristics of the semiconductor device can be more effectively improved, (pH (1) -pH (2) ) is more preferably 0.8 or less, and even more preferably 0.6 or less. (pH (1) -pH (2) ) The lower limit value is not particularly limited, and may be, for example, 0.1.
於本實施形態中，密封用樹脂組成物之藉由上述條件1測定之pH(1)較佳為5以上且7以下，更佳為5以上且6.5以下。藉此，可更有效地提昇高溫保管特性或耐回流焊性等密封用樹脂組成物所要求之各特性之平衡。因此，亦可有助於提昇使用密封用樹脂組成物而獲得之半導體裝置之可靠性。 In this embodiment, the pH (1) of the sealing resin composition measured under the above condition 1 is preferably 5 or more and 7 or less, and more preferably 5 or more and 6.5 or less. Thereby, the balance of various characteristics required for the sealing resin composition such as high-temperature storage characteristics and reflow resistance can be more effectively improved. Therefore, it can also contribute to improving the reliability of the semiconductor device obtained by using the resin composition for sealing.
於本實施形態中，密封用樹脂組成物之pH(1)、pH(2)、及(pH(1)-pH(2))例如可藉由適當調整密封用樹脂組成物所含有之各成分之種類或含 量、及密封用樹脂組成物之製備方法等而控制。作為該密封用樹脂組成物之製備方法之一例，可列舉下述對填充材(C)利用偶合劑(D)進行之表面處理。 In this embodiment, the pH (1) , pH (2), and (pH (1) -pH (2) ) of the resin composition for sealing can be adjusted, for example, by each component contained in the resin composition for sealing. The type or content, and the method of preparing the sealing resin composition are controlled. As an example of a method for producing the sealing resin composition, the following surface treatment of the filler (C) with a coupling agent (D) is mentioned.
密封用樹脂組成物含有環氧樹脂(A)及硬化劑(B)。藉此，可使用密封用樹脂組成物形成用以密封接合線及半導體元件之密封樹脂。 The resin composition for sealing contains an epoxy resin (A) and a hardener (B). Thereby, a sealing resin for sealing a bonding wire and a semiconductor element can be formed using the sealing resin composition.
((A)環氧樹脂) ((A) Epoxy)
作為環氧樹脂(A)，可使用於1分子內具有2個以上環氧基之所有單體、低聚物、聚合物，其分子量或分子結構並無特別限定。 The epoxy resin (A) can be used for all monomers, oligomers, and polymers having two or more epoxy groups in one molecule, and its molecular weight or molecular structure is not particularly limited.
於本實施形態中，環氧樹脂(A)例如可含有選自聯苯型環氧樹脂；雙酚A型環氧樹脂、雙酚F型環氧樹脂、四甲基雙酚F型環氧樹脂等雙酚型環氧樹脂；茋型環氧樹脂；苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂等酚醛清漆型環氧樹脂；三苯酚甲烷型環氧樹脂、烷基改質三苯酚甲烷型環氧樹脂等多官能環氧樹脂；具有伸苯基骨架之苯酚芳烷基型環氧樹脂、具有聯伸苯基骨架之苯酚芳烷基型環氧樹脂等芳烷基型環氧樹脂；二羥基萘型環氧樹脂、將二羥基萘之二聚物縮水甘油醚化而獲得之環氧樹脂等萘型環氧樹脂；三縮水甘油基異氰尿酸酯、單烯丙基二縮水甘油基異氰尿酸酯等含三核環氧樹脂；二環戊二烯改質酚型環氧樹脂等橋接環狀烴化合物改質酚型環氧樹脂中之一種或兩種以上。該等中，更佳為含有萘型環氧樹脂、芳烷基型環氧樹脂、及聯苯型環氧樹脂中之一種或兩種以上，尤佳為含有芳烷基型環氧樹脂。再者，芳烷基型環氧樹脂、聯苯型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、及四甲基雙酚F型環氧樹脂等雙酚型環氧樹脂、以及茋型環氧樹脂較佳為具有結晶性者。 In this embodiment, the epoxy resin (A) may contain, for example, a biphenyl epoxy resin; a bisphenol A epoxy resin, a bisphenol F epoxy resin, or a tetramethylbisphenol F epoxy resin. Other bisphenol-type epoxy resins; 茋 -type epoxy resins; novolac-type epoxy resins such as phenol novolac-type epoxy resins, cresol novolac-type epoxy resins; triphenol methane-type epoxy resins, alkyl modification Multifunctional epoxy resins such as triphenol methane epoxy resins; phenol aralkyl epoxy resins having a phenylene skeleton; aralkyl ring epoxy resins having a phenylarene skeleton; Oxygen resins; dihydroxynaphthalene-type epoxy resins, naphthalene-type epoxy resins such as epoxy resins obtained by etherifying the dimer of dihydroxynaphthalene; triglycidyl isocyanurate, monoallyl Diglycidyl isocyanurate Nuclear epoxy resin; dicyclopentadiene-modified phenol-type epoxy resin; bridged cyclic hydrocarbon compounds; phenol-type epoxy resin; Among these, one or two or more of naphthalene-type epoxy resins, aralkyl-type epoxy resins, and biphenyl-type epoxy resins are more preferable, and aralkyl-type epoxy resins are more preferable. Furthermore, bisphenol-type rings such as aralkyl-type epoxy resin, biphenyl-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and tetramethylbisphenol F-type epoxy resin. The oxygen resin and the fluorene type epoxy resin are preferably those having crystallinity.
作為環氧樹脂(A)，更佳為使用含有選自由下述式(1)所表示之環氧樹脂、下述式(2)所表示之環氧樹脂、下述式(3)所表示之環氧樹脂、及下述式(4)所表示之環氧樹脂所組成之群中之至少一種者。該等中，尤佳為使用含有下述式(1)所表示之環氧樹脂、下述式(2)所表示之環氧樹脂、及下述式(4)所表示之環氧樹脂中之至少一種者。 As the epoxy resin (A), it is more preferable to use an epoxy resin containing the epoxy resin represented by the following formula (1), the epoxy resin represented by the following formula (2), and the formula (3). At least one of the group consisting of an epoxy resin and an epoxy resin represented by the following formula (4). Among these, it is particularly preferable to use an epoxy resin containing the epoxy resin represented by the following formula (1), the epoxy resin represented by the following formula (2), and the epoxy resin represented by the following formula (4). At least one of them.
(式(1)中，Ar1表示伸苯基或伸萘基，於Ar1為伸萘基之情形時，縮水甘油醚基可鍵結於α位、β位中之任一處。Ar2表示伸苯基、聯伸苯基或伸萘基中之任一基。Ra及Rb分別獨立表示碳數1~10之烴基。g為0~5之整數，h為0~8之整數。n3表示聚合度，其平均值為1~3) (In the formula (1), Ar 1 represents a phenylene group or a naphthyl group. When Ar 1 is a naphthyl group, a glycidyl ether group may be bonded to any one of the α position and the β position. Ar 2 Represents any of phenylene, biphenylene, or naphthyl. R a and R b each independently represent a hydrocarbon group having 1 to 10 carbon atoms. G is an integer of 0 to 5 and h is an integer of 0 to 8 (N 3 represents the degree of polymerization, and its average value is 1 to 3)
(式(2)中，複數個存在之Rc分別獨立表示氫原子或碳數1~4之烴基。n5表示聚合度，其平均值為0~4) (In the formula (2), a plurality of existing R c each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. N 5 represents a degree of polymerization, and an average value thereof is 0 to 4)
(式(3)中，複數個存在之Rd及Re分別獨立表示氫原子或碳數1~4之烴基。n6表示聚合度，其平均值為0~4) (In formula (3), a plurality of R d and R e each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. N 6 represents a degree of polymerization, and the average value is 0 to 4)
(式(4)中，Rf分別獨立表示氫或碳數1~4之烴基，Rg分別獨立表示碳數1~4之烴基。a及b為0或1之整數，c為0~5之整數) (In formula (4), R f independently represents hydrogen or a hydrocarbon group having 1 to 4 carbon atoms, and R g independently represents a hydrocarbon group having 1 to 4 carbon atoms. A and b are integers of 0 or 1, and c is 0 to 5 Integer)
密封用樹脂組成物中之環氧樹脂(A)之含量例如相對於密封用樹脂組成物整體較佳為1質量%以上，更佳為2質量%以上，尤佳為5質量%以上。藉由將環氧樹脂(A)之含量設為上述下限值以上，可提昇密封用樹脂組成物之流動性。又，亦可更確實地抑制因密封用樹脂組成物之黏度上升而引起之接合線斷裂。另一方面，密封用樹脂組成物中之環氧樹脂(A)之含量例如相對於密封用樹脂組成物整體較佳為50質量%以下，更佳為30質量%以下，尤佳為20質量%以下。藉由將環氧樹脂(A)之含量設為上述上限值以下，而可提昇半導體裝置之耐濕可靠性或耐回流焊性。 The content of the epoxy resin (A) in the sealing resin composition is, for example, preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more with respect to the entire sealing resin composition. When the content of the epoxy resin (A) is at least the above-mentioned lower limit value, the fluidity of the sealing resin composition can be improved. In addition, it is also possible to more surely prevent the bonding wire from being broken due to an increase in the viscosity of the sealing resin composition. On the other hand, the content of the epoxy resin (A) in the sealing resin composition is, for example, preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass relative to the entire sealing resin composition. the following. By setting the content of the epoxy resin (A) to be equal to or less than the above-mentioned upper limit, the moisture resistance reliability and reflow resistance of the semiconductor device can be improved.
((B)硬化劑) ((B) Hardener)
作為密封用樹脂組成物所含有之硬化劑(B)，例如可大致分為加成聚合型硬化劑、觸媒型硬化劑、及縮合型硬化劑3類。 The hardener (B) contained in the sealing resin composition can be roughly classified into, for example, an addition polymerization type hardener, a catalyst type hardener, and a condensation type hardener.
作為硬化劑(B)所使用之加成聚合型硬化劑，例如可列舉：包括二伸乙基三胺(DETA)、三伸乙基四胺(TETA)、間苯二甲胺(MXDA)等脂肪族聚胺、二胺基二苯基甲烷(DDM)、間苯二胺(MPDA)、二胺基二苯基碸(DDS)等芳香族聚胺、以及雙氰胺(DICY)、有機二醯肼等之聚胺化合物；包括六氫鄰苯二甲酸酐(HHPA)、甲基四氫鄰苯二甲酸酐(MTHPA)等脂環族酸酐、偏苯三甲酸酐(TMA)、均苯四甲酸二酐(PMDA)、二苯甲酮四羧酸(BTDA)等芳香族酸酐等之酸酐；酚醛清漆型酚系樹脂、聚乙烯苯酚等酚系樹脂系硬化劑；多硫化物、硫酯、硫醚等聚硫醇化合物；異氰酸酯預聚物、封端化異氰酸酯等異氰酸酯化合物；含羧酸之聚酯樹脂等有機酸類等。 Examples of the addition polymerization type curing agent used as the curing agent (B) include diethylenetriamine (DETA), triethylenetetraamine (TETA), and m-xylylenediamine (MXDA). Aromatic polyamines such as aliphatic polyamines, diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), diaminodiphenylsulfonium (DDS), dicyandiamide (DICY), and organic diamines Polyamine compounds such as hydrazine; including alicyclic anhydrides such as hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA), trimellitic anhydride (TMA), pyromellitic acid Acid anhydrides such as aromatic anhydrides such as dianhydride (PMDA) and benzophenone tetracarboxylic acid (BTDA); novolac phenol resins, polyvinyl phenol resin hardeners such as polyvinyl phenol; polysulfides, thioesters, sulfur Polythiol compounds such as ethers; isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; organic acids such as carboxylic acid-containing polyester resins, etc.
硬化劑(B)所使用之觸媒型硬化劑，例如可列舉：二甲苄胺(BDMA)、2,4,6-三(二甲胺基甲基)苯酚(DMP-30)等三級胺化合物；2-甲咪唑、2-乙基-4-甲咪唑(EMI24)等咪唑化合物；BF3錯合物等路易斯酸等。 Examples of the catalyst-type hardener used in the hardener (B) include tertiary grades such as dimethylbenzylamine (BDMA) and 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30). Amine compounds; imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole (EMI24); Lewis acids such as BF3 complex.
硬化劑(B)所使用之縮合型硬化劑，例如可列舉：可溶酚醛型酚樹脂；如含羥甲基之脲樹脂之脲樹脂；如含羥甲基之三聚氰胺樹脂之三聚氰胺樹脂等。 Examples of the condensation-type curing agent used for the curing agent (B) include soluble phenol-type phenol resins; urea resins such as methylol-containing urea resins; and melamine resins such as methylol-containing melamine resins.
該等中，就提昇耐燃性、耐濕性、電特性、硬化性、及保存穩定性等之平衡之觀點而言，較佳為酚樹脂系硬化劑。作為酚樹脂系硬化 劑，可使用於一分子內具有2個以上酚性羥基之所有單體、低聚物、聚合物，其分子量、分子結構並無特別限定。 Among these, a phenol resin-based hardener is preferred from the viewpoint of improving the balance of flame resistance, moisture resistance, electrical characteristics, hardenability, and storage stability. Hardened as phenol resin The agent can be used for all monomers, oligomers, and polymers having two or more phenolic hydroxyl groups in one molecule, and the molecular weight and molecular structure are not particularly limited.
用作硬化劑(B)之酚樹脂系硬化劑，例如可含有選自苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂、雙酚酚醛清漆樹脂等酚醛清漆型樹脂；聚乙烯苯酚；三苯酚甲烷型酚樹脂等多官能型酚樹脂；萜烯改質酚樹脂、二環戊二烯改質酚樹脂等改質酚樹脂；具有伸苯基骨架及/或聯伸苯基骨架之苯酚芳烷基樹脂、具有伸苯基及/或聯伸苯基骨架之萘酚芳烷基樹脂等芳烷基型樹脂；雙酚A、雙酚F等雙酚化合物等中之一種或兩種以上。該等中，就提昇耐回流焊性或高溫保管特性之平衡之觀點而言，較佳為含有芳烷基型樹脂及多官能型酚樹脂中之至少一者。 The phenol resin-based hardener used as the hardener (B) may contain, for example, novolac resins selected from phenol novolac resins, cresol novolac resins, bisphenol novolac resins, etc .; polyvinyl phenol; triphenol methane-type phenols Polyfunctional phenol resins such as resins; modified phenol resins such as terpene modified phenol resins and dicyclopentadiene modified phenol resins; phenol aralkyl resins with a phenylene skeleton and / or a phenylene skeleton, One or two or more of aralkyl type resins such as naphthol aralkyl resins having a phenylene and / or biphenylene skeleton; bisphenol compounds such as bisphenol A and bisphenol F. Among these, from the viewpoint of improving the balance between reflow resistance and high-temperature storage characteristics, it is preferable to contain at least one of an aralkyl resin and a polyfunctional phenol resin.
作為硬化劑(B)，尤佳為含有選自由下述式(5)所表示之化合物、及下述式(6)所表示之化合物所組成之群中之至少1種硬化劑。 The hardening agent (B) is particularly preferably one containing at least one hardening agent selected from the group consisting of a compound represented by the following formula (5) and a compound represented by the following formula (6).
(式(5)中，Ar3表示伸苯基或伸萘基，於Ar3為伸萘基之情形時，羥基可鍵結於α位、β位中之任一處。Ar4表示伸苯基、聯伸苯基或伸萘基中之任一基。Rn及Rm分別獨立表示碳數1~10之烴基。i為0~5之整數，j為0~8之整數。n4表示聚合度，其平均值為1~3) (In the formula (5), Ar 3 represents a phenylene group or a naphthyl group. When Ar 3 is a naphthyl group, a hydroxyl group may be bonded to any one of an α position and a β position. Ar 4 represents a phenylene Any one of a radical, a biphenylene or a naphthyl. R n and R m each independently represent a hydrocarbon group having 1 to 10 carbon atoms. I is an integer of 0 to 5 and j is an integer of 0 to 8. n 4 (Indicates the degree of polymerization, and its average value is 1 to 3)
(式(6)中，複數個存在之Rh分別獨立表示氫原子或碳數1~4之烴基。n8表示聚合度，其平均值為0~4) (In the formula (6), a plurality of existing R h each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. N 8 represents a degree of polymerization, and an average value thereof is 0 to 4)
密封用樹脂組成物中之硬化劑(B)之含量例如相對於密封用樹脂組成物整體較佳為2質量%以上，更佳為3質量%以上，尤佳為4質量%以上。藉由將硬化劑(B)之含量設為上述下限值以上，而可實現具有充分之流動性之密封用樹脂組成物，可謀求成形性之提昇。另一方面，密封用樹脂組成物中之硬化劑(B)之含量例如相對於密封用樹脂組成物整體較佳為15質量%以下，更佳為13質量%以下，尤佳為11質量%以下。藉由將硬化劑(B)之含量設為上述上限值以下，而可提昇半導體裝置之耐濕可靠性或耐回流焊性。 The content of the hardener (B) in the sealing resin composition is, for example, preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 4% by mass or more with respect to the entire sealing resin composition. When the content of the hardener (B) is equal to or more than the above-mentioned lower limit value, a sealing resin composition having sufficient fluidity can be realized, and moldability can be improved. On the other hand, the content of the hardener (B) in the sealing resin composition is, for example, preferably 15% by mass or less, more preferably 13% by mass or less, and even more preferably 11% by mass or less based on the entire sealing resin composition. . By setting the content of the hardener (B) to be equal to or less than the above-mentioned upper limit, the moisture resistance reliability and reflow resistance of the semiconductor device can be improved.
((C)填充材) ((C) filler)
密封用樹脂組成物例如可進而含有填充材(C)。作為填充材(C)，可使用通常之半導體密封用環氧樹脂組成物所使用者，例如可列舉：熔融球形二氧化矽、熔融粉碎二氧化矽、晶質二氧化矽、滑石、氧化鋁、鈦白、氮化矽等無機填充材；有機聚矽氧粉末、聚乙烯粉末等有機填充材。該等中，尤佳為使用熔融球形二氧化矽。該等填充材可單獨使用1種，亦可將2種以上併用。 The resin composition for sealing may further contain a filler (C), for example. As the filler (C), a user of an ordinary epoxy resin composition for semiconductor encapsulation can be used, and examples thereof include fused spherical silica, melt-pulverized silica, crystalline silica, talc, alumina, Titanium dioxide, silicon nitride and other inorganic fillers; organic polysiloxane powder, polyethylene powder and other organic fillers. Among these, it is particularly preferable to use fused spherical silica. These fillers may be used individually by 1 type, and may use 2 or more types together.
又，作為填充材(C)之形狀，並無特別限定，就抑制密封用樹脂組成物之熔融黏度之上升、並且提高填充材之含量之觀點而言，較佳為儘可能地為正球狀、且粒度分佈較寬者。 The shape of the filler (C) is not particularly limited. From the viewpoint of suppressing an increase in the melt viscosity of the sealing resin composition and increasing the content of the filler, it is preferably as spherical as possible. , And the particle size distribution is wider.
密封用樹脂組成物中之填充材(C)之含量例如相對於密封用樹脂組成物整體較佳為35質量%以上，更佳為50質量%以上，尤佳為65質量%以上。藉由將填充材(C)之含量設為上述下限值以上，而可提昇低吸濕性及低熱膨脹性，可更有效地提昇耐濕可靠性或耐回流焊性。另一方面，密封用樹脂組成物中之填充材(C)之含量較佳為95質量%以下，更佳為93質量%以下，尤佳為90質量%以下。藉由將填充材(C)之含量設為上述上限值以下，而可抑制密封用樹脂組成物之流動性之降低帶來之成形性之降低、或因高黏度化而引起之接合線偏移等。 The content of the filler (C) in the sealing resin composition is, for example, preferably 35% by mass or more, more preferably 50% by mass or more, and even more preferably 65% by mass or more with respect to the entire sealing resin composition. By setting the content of the filler (C) to be more than the above-mentioned lower limit, low moisture absorption and low thermal expansion can be improved, and moisture resistance reliability or reflow resistance can be improved more effectively. On the other hand, the content of the filler (C) in the sealing resin composition is preferably 95% by mass or less, more preferably 93% by mass or less, and even more preferably 90% by mass or less. By setting the content of the filler (C) to be equal to or smaller than the above-mentioned upper limit value, it is possible to suppress a decrease in moldability due to a decrease in the fluidity of the sealing resin composition, or a deviation in the bonding line due to a high viscosity. Shift etc.
((D)偶合劑) ((D) Coupling agent)
對填充材(C)可使用偶合劑(D)實施表面處理。作為偶合劑(D)，例如可使用環氧矽烷、巰基矽烷、胺基矽烷、烷基矽烷、脲基矽烷、乙烯基矽烷、甲基丙烯醯基矽烷等各種矽烷系化合物、鈦系化合物、鋁螯合物類、鋁/鋯系化合物等公知之偶合劑。若例示該等，則可列舉：乙烯基三氯矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三(β-甲氧基乙氧基)矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、β-(3,4-環氧基環己基)乙基三甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基三乙氧基矽烷、γ-縮水甘油氧基丙基甲基二甲氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、γ-甲基丙烯醯氧基丙基三乙氧基矽烷、乙烯基三乙醯氧基矽烷、γ-巰基丙基三甲氧基矽烷、 γ-胺基丙基三乙氧基矽烷、γ-苯胺基丙基三甲氧基矽烷、γ-苯胺基丙基甲基二甲氧基矽烷、γ-[雙(β-羥乙基)]胺基丙基三乙氧基矽烷、N-β-(胺基乙基)-γ-胺基丙基三甲氧基矽烷、N-β-(胺基乙基)-γ-胺基丙基三乙氧基矽烷、N-β-(胺基乙基)-γ-胺基丙基甲基二甲氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷、γ-(β-胺基乙基)胺基丙基二甲氧基甲基矽烷、N-(三甲氧基矽烷基丙基)乙二胺、N-(二甲氧基甲基矽烷基異丙基)乙二胺、甲基三甲氧基矽烷、二甲基二甲氧基矽烷、甲基三乙氧基矽烷、N-β-(N-乙烯基苄基胺基乙基)-γ-胺基丙基三甲氧基矽烷、γ-氯丙基三甲氧基矽烷、六甲基二矽烷、乙烯基三甲氧基矽烷、γ-巰基丙基甲基二甲氧基矽烷、3-異氰酸酯基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、3-三乙氧基矽烷基-N-(1,3-二甲基-亞丁基)丙基胺之水解物等矽烷系偶合劑；三異硬脂醯基鈦酸異丙酯、三(二辛基焦磷醯氧基)鈦酸異丙酯、三(N-胺基乙基-胺基乙基)鈦酸異丙酯、雙(二-十三烷基亞磷醯氧基)鈦酸四辛酯、四(2,2-二烯丙氧基甲基-1-丁基)雙(二-十三烷基)亞磷醯氧基鈦酸酯、雙(二辛基焦磷醯氧基)羥乙酸鈦酸酯、雙(二辛基焦磷醯氧基)鈦酸乙二酯、三辛醯基鈦酸異丙酯、二甲基丙烯醯基異硬脂醯基鈦酸異丙酯、三(十二烷基苯磺醯基)鈦酸異丙酯、異硬脂醯基二丙烯醯基鈦酸異丙酯、三(二辛基亞磷醯氧基)鈦酸異丙酯、三(異丙苯基苯基)鈦酸異丙酯、雙(二辛基亞磷醯氧基)鈦酸四異丙酯等鈦酸酯系偶合劑。該等可單獨使用1種，亦可將2種以上組合使用。該等中，更佳為環氧矽烷、巰基矽烷、胺基矽烷、烷基矽烷、脲基矽烷或乙烯基矽烷等矽烷系化合物。又，就提昇耐回流焊性等半導體裝置之可靠性之觀點而言， 尤佳為使用巰基矽烷。 The filler (C) may be surface-treated with a coupling agent (D). As the coupling agent (D), for example, various silane-based compounds such as epoxy silane, mercapto silane, amine silane, alkyl silane, ureido silane, vinyl silane, methacryl fluorenyl silane, etc. Well-known coupling agents such as chelate compounds and aluminum / zirconium compounds. Examples of these include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (β-methoxyethoxy) silane, and γ-methacryl Methoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl Triethoxysilane, γ-glycidyloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyl Triethoxysilane, vinyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-anilinepropyltrimethoxysilane, γ-anilinepropylmethyldimethoxysilane, γ- [bis (β-hydroxyethyl)] amine Propyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethyl Oxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ- (β- Aminoethyl) aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine , Methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxy Silane, γ-chloropropyltrimethoxysilane, hexamethyldisila, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-isocyanatepropyltriethoxysilane , 3-propenyloxypropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylene) propylamine hydrolysate, and other silane Couplings; isopropyl triisostearate, isopropyl titanate, isopropyl tris (dioctylpyrophosphinoyloxy) titanate, tris (N-aminoethyl-aminoethyl) titanate Propyl ester, bis (di-tridecylphosphophosphinoyloxy) tetraoctyl titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) ) Phosphorous phosphonium oxytitanate, bis (dioctylpyrophosphinooxy) glycolate titanate, bis (dioctylpyrophosphinooxy) ethylene titanate, trioctylphosphonate isopropyl Esters, dimethylpropenyl isostearyl isopropyl titanate isopropyl, tris (dodecylbenzenesulfonyl) isopropyl isopropyl ester, isostearyl dipropenyl isopropyl titanate , Isopropyl tris (dioctylphosphinofluorenyloxy) titanate, isopropyl tris (cumylphenylphenyl) titanate, tetraisopropyl bis (dioctylphosphonoxy) titanate And other titanate-based coupling agents. These may be used individually by 1 type, and may use 2 or more types together. Among these, a silane-based compound such as epoxy silane, mercapto silane, amine silane, alkyl silane, ureido silane, or vinyl silane is more preferable. From the viewpoint of improving the reliability of semiconductor devices such as reflow resistance, Especially preferred is the use of mercaptosilane.
對填充材(C)利用偶合劑(D)進行之表面處理例如可以如下方式進行。首先，將填充材(C)投入攪拌機後，開始攪拌，於其中進而投入偶合劑(D)後攪拌1~5分鐘，獲得填充材(C)及偶合劑(D)之混合物。繼而，將該混合物自攪拌機中取出並靜置。靜置時間可適當選擇，例如可設為3分鐘~1小時。藉此，可獲得藉由偶合劑(D)實施了表面處理之填充材(C)。又，對靜置處理後之填充材(C)亦可進而實施熱處理。熱處理例如可於30~80℃、0.1~10小時之條件下進行。進而，於本實施形態中，亦可藉由一面對攪拌機內之填充材(C)使用噴霧器噴霧偶合劑(D)一面攪拌填充材(C)，而獲得填充材(C)及偶合劑(D)之混合物。作為噴霧器，例如可使用具備二流體噴嘴等之可噴霧微細液滴之裝置。藉由使用此種噴霧器，而可更均勻地利用偶合劑(D)處理填充材(C)表面，較佳。 The surface treatment of the filler (C) with the coupling agent (D) can be performed, for example, as follows. First, the filler (C) is put into a mixer, and stirring is started, and then the coupling agent (D) is further added thereto and stirred for 1 to 5 minutes to obtain a mixture of the filler (C) and the coupling agent (D). Then, the mixture was taken out of the blender and left to stand. The standing time can be appropriately selected, and for example, it can be set to 3 minutes to 1 hour. Thereby, a filler (C) which has been surface-treated with the coupling agent (D) can be obtained. Further, the filler (C) after the standing treatment may be further subjected to a heat treatment. The heat treatment can be performed at, for example, 30 to 80 ° C. for 0.1 to 10 hours. Furthermore, in this embodiment, the filling material (C) and the coupling agent (C) can be obtained by spraying the coupling agent (D) with the sprayer on the filling material (C) inside the mixer. D) mixture. As the sprayer, for example, a device capable of spraying fine droplets having a two-fluid nozzle or the like can be used. By using such a sprayer, the surface of the filler (C) can be more evenly treated with the coupling agent (D), which is preferable.
於本實施形態中，例如藉由調整上述表面處理之條件，而可控制密封用樹脂組成物之pH(1)、pH(2)、及(pH(1)-pH(2))。作為該表面處理之條件，例如可列舉有無使用噴霧器、靜置時間、有無熱處理及熱處理條件等。 In this embodiment, for example, the pH (1) , pH (2) , and (pH (1) -pH (2) ) of the sealing resin composition can be controlled by adjusting the conditions of the surface treatment described above. Examples of the conditions for the surface treatment include the presence or absence of use of a sprayer, standing time, presence or absence of heat treatment, and heat treatment conditions.
再者，偶合劑(D)係藉由對填充材(C)進行上述表面處理而含有於密封用樹脂組成物內，除此情形以外，亦可藉由直接投入攪拌機內與其他成分混合而含有於密封用樹脂組成物內。 In addition, the coupling agent (D) is contained in the sealing resin composition by subjecting the filler (C) to the above-mentioned surface treatment. Alternatively, the coupling agent (D) may be directly mixed into the blender and mixed with other ingredients and contained. In the sealing resin composition.
密封用樹脂組成物中之偶合劑(D)之含量例如相對於密封用樹脂組成物整體較佳為0.05質量%以上，更佳為0.1質量%以上，尤佳為0.15質量%以上。藉由將偶合劑(D)之含量設為上述下限值以上，而可使 密封用樹脂組成物中之填充材(C)之分散性良好。因此，可更有效地提昇耐濕可靠性或耐回流焊性等。另一方面，密封用樹脂組成物中之偶合劑(D)之含量例如較佳為2質量%以下，更佳為1質量%以下，尤佳為0.5質量%以下。藉由將偶合劑(D)之含量設為上述上限值以下，而可使密封用樹脂組成物之流動性良好，可謀求成形性之提昇。 The content of the coupling agent (D) in the sealing resin composition is, for example, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.15% by mass or more with respect to the entire sealing resin composition. By setting the content of the coupling agent (D) to the above lower limit value or more, The filler (C) in the sealing resin composition has good dispersibility. Therefore, it is possible to more effectively improve the humidity resistance reliability and reflow resistance. On the other hand, the content of the coupling agent (D) in the resin composition for sealing is, for example, preferably 2% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less. By setting the content of the coupling agent (D) to be equal to or smaller than the above-mentioned upper limit value, the fluidity of the sealing resin composition can be made good, and the moldability can be improved.
((E)離子捕捉劑) ((E) ion trapping agent)
密封用樹脂組成物例如可進而含有離子捕捉劑(E)。 The sealing resin composition may further contain, for example, an ion trapping agent (E).
作為離子捕捉劑(E)，並無特別限定，例如可列舉水滑石類及多價金屬酸性鹽等無機離子交換體。該等可單獨使用1種，亦可將2種以上組合使用。該等中，就提昇高溫保管特性之觀點而言，尤佳為使用水滑石類。 The ion trapping agent (E) is not particularly limited, and examples thereof include inorganic ion exchangers such as hydrotalcites and polyvalent metal acid salts. These may be used individually by 1 type, and may use 2 or more types together. Among these, the use of hydrotalcites is particularly preferable from the viewpoint of improving high-temperature storage characteristics.
密封用樹脂組成物中之離子捕捉劑(E)之含量例如相對於密封用樹脂組成物整體較佳為0.05質量%以上，更佳為0.1質量%以上，尤佳為0.15質量%以上。藉由將離子捕捉劑(E)之含量設為上述下限值以上，而可更有效地提昇高溫保管特性。又，可確實地抑制接合線與半導體元件間之腐蝕，可良好地保持連接可靠性。另一方面，密封用樹脂組成物中之離子捕捉劑(E)之含量例如較佳為1質量%以下，更佳為0.8質量%以下，尤佳為0.5質量%以下。藉由將離子捕捉劑(E)之含量設為上述上限值以下，而可提昇半導體裝置之耐濕可靠性或耐回流焊性。 The content of the ion trapping agent (E) in the sealing resin composition is, for example, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.15% by mass or more with respect to the entire sealing resin composition. By setting the content of the ion trapping agent (E) to the above lower limit value or more, the high-temperature storage characteristics can be improved more effectively. In addition, corrosion between the bonding wire and the semiconductor element can be reliably suppressed, and connection reliability can be favorably maintained. On the other hand, the content of the ion trapping agent (E) in the sealing resin composition is, for example, preferably 1% by mass or less, more preferably 0.8% by mass or less, and even more preferably 0.5% by mass or less. By setting the content of the ion trapping agent (E) to be equal to or less than the above-mentioned upper limit, the moisture resistance reliability and reflow resistance of the semiconductor device can be improved.
(硬化促進劑(F)) (Hardening accelerator (F))
密封用樹脂組成物例如可含有硬化促進劑(F)。硬化促進劑(F)只要為可促進環氧樹脂(A)之環氧基與硬化劑(B)(例如酚樹脂系硬化劑之酚性羥基)之交聯反應者即可，例如可使用通常之密封用環氧樹脂組成物所 使用者。 The resin composition for sealing may contain a hardening accelerator (F), for example. The hardening accelerator (F) may be any one that can accelerate the cross-linking reaction between the epoxy group of the epoxy resin (A) and the hardener (B) (for example, the phenolic hydroxyl group of a phenol resin-based hardener). Epoxy resin composition for sealing user.
於本實施形態中，硬化促進劑(F)例如可含有選自有機膦、四取代鏻化合物、磷酸酯甜菜鹼化合物、膦化合物與醌化合物之加成物、鏻化合物與矽烷化合物之加成物等含磷原子化合物；1,8-二氮雙環(5,4,0)十一烯-7、二甲苄胺、2-甲咪唑等所例示之脒或三級胺、上述脒或胺之四級鹽等含氮原子化合物中之1種或2種以上。該等中，就提昇硬化性之觀點而言，更佳為含有含磷原子化合物。又，就提昇成形性與硬化性之平衡性之觀點而言，更佳為含有四取代鏻化合物、磷酸酯甜菜鹼化合物、膦化合物與醌化合物之加成物、鏻化合物與矽烷化合物之加成物等具有潛伏性者。 In this embodiment, the hardening accelerator (F) may contain, for example, an organic phosphine, a tetra-substituted phosphonium compound, a phosphate betaine compound, an adduct of a phosphine compound and a quinone compound, and an adduct of a sulfonium compound and a silane compound. And other phosphorus atom-containing compounds; 1,8-diazabicyclo (5,4,0) undecene-7, dimethylbenzylamine, 2-methylimidazole, and other examples of the amidine or tertiary amines, the above amidines or amines One or more nitrogen-containing compounds such as quaternary salts. Among these, from the viewpoint of improving the hardenability, it is more preferable to contain a phosphorus atom-containing compound. From the viewpoint of improving the balance between moldability and hardenability, it is more preferable to contain a tetra-substituted fluorene compound, a phosphate betaine compound, an adduct of a phosphine compound and a quinone compound, and an addition of a sulfonium compound and a silane compound. There are latent people.
作為密封用樹脂組成物可使用之有機膦，例如可列舉：乙基膦、苯基膦等一級膦；二甲基膦、二苯基膦等二級膦；三甲基膦、三乙基膦、三丁基膦、三苯基膦等三級膦。 Examples of organic phosphines that can be used as the sealing resin composition include primary phosphines such as ethylphosphine and phenylphosphine; secondary phosphines such as dimethylphosphine and diphenylphosphine; trimethylphosphine and triethylphosphine. Tertiary phosphines such as, tributylphosphine and triphenylphosphine.
作為密封用樹脂組成物可使用之四取代鏻化合物，例如可列舉下述通式(7)所表示之化合物等。 Examples of the tetra-substituted fluorene compound that can be used as the sealing resin composition include a compound represented by the following general formula (7).
(於上述通式(7)中，P表示磷原子。R4、R5、R6及R7表示芳香族基或烷基。A表示於芳香環具有至少1個選自羥基、羧基、硫醇基中之任一官能基的芳香族有機酸之陰離子。AH表示於芳香環具有至少1個選自羥 基、羧基、硫醇基中之任一官能基之芳香族有機酸。x、y為1~3之數、z為0~3之數，且x=y) (In the general formula (7), P represents a phosphorus atom. R 4 , R 5 , R 6, and R 7 represent an aromatic group or an alkyl group. A represents that the aromatic ring has at least one selected from a hydroxyl group, a carboxyl group, and a sulfur group. An anion of an aromatic organic acid having any functional group in an alcohol group. AH represents an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group in an aromatic ring. X and y are 1 ~ 3, z is 0 ~ 3, and x = y)
通式(7)所表示之化合物例如係以如下方式獲得，但並不限定於此。首先，將四取代鏻鹵化物、芳香族有機酸與鹼混入有機溶劑並均勻地混合，使該溶液系內產生芳香族有機酸陰離子。繼而，若加入水，則可使通式(7)所表示之化合物沈澱。於通式(7)所表示之化合物中，較佳為與磷原子鍵結之R4、R5、R6及R7為苯基，且AH為於芳香環具有羥基之化合物，即酚類，且A為該酚類之陰離子。作為上述酚類，可例示：苯酚、甲酚、間苯二酚、鄰苯二酚等單環式酚類；萘酚、二羥基萘、蒽二酚等縮合多環式酚類；雙酚A、雙酚F、雙酚S等雙酚類；苯基苯酚、聯苯酚等多環式酚類等。 The compound represented by the general formula (7) is obtained, for example, as follows, but is not limited thereto. First, a tetra-substituted phosphonium halide, an aromatic organic acid, and a base are mixed into an organic solvent and uniformly mixed to generate an aromatic organic acid anion in the solution system. When water is added, the compound represented by the general formula (7) can be precipitated. Among the compounds represented by the general formula (7), R 4 , R 5 , R 6, and R 7 bonded to a phosphorus atom are preferably phenyl groups, and AH is a compound having a hydroxyl group in an aromatic ring, that is, phenols And A is the anion of the phenol. Examples of the phenols include monocyclic phenols such as phenol, cresol, resorcinol, and catechol; condensed polycyclic phenols such as naphthol, dihydroxynaphthalene, and anthradiol; bisphenol A , Bisphenols such as bisphenol F, bisphenol S; polycyclic phenols such as phenylphenol and biphenol.
作為密封用樹脂組成物可使用之磷酸酯甜菜鹼化合物，例如可列舉下述通式(8)所表示之化合物等。 Examples of the phosphoric acid betaine compound that can be used as the sealing resin composition include compounds represented by the following general formula (8).
(於上述通式(8)中，R8表示碳數1~3之烷基，R9表示羥基。f為0~5之數，g為0~3之數) (In the general formula (8), R 8 represents an alkyl group having 1 to 3 carbon atoms, and R 9 represents a hydroxyl group. F is a number of 0 to 5 and g is a number of 0 to 3)
通式(8)所表示之化合物例如可以如下方式獲得。經由如下步驟獲得：首先，使作為三級膦之三芳香族取代膦與重氮鎓鹽接觸，使 三芳香族取代膦與重氮鎓鹽所具有之重氮鎓基置換。然而，並不限定於此。 The compound represented by the general formula (8) can be obtained, for example, as follows. Obtained by the following steps: First, a triaromatic substituted phosphine as a tertiary phosphine is contacted with a diazonium salt, so that The triaromatic substituted phosphine is replaced with the diazonium group of the diazonium salt. However, it is not limited to this.
作為密封用樹脂組成物可使用之膦化合物與醌化合物之加成物，例如可列舉下述通式(9)所表示之化合物等。 The adduct of a phosphine compound and a quinone compound that can be used as the sealing resin composition includes, for example, a compound represented by the following general formula (9).
(於上述通式(9)中，P表示磷原子。R10、R11及R12表示碳數1~12之烷基或碳數6~12之芳基，相互可相同亦可不同。R13、R14及R15表示氫原子或碳數1~12之烴基，相互可相同亦可不同，R14與R15亦可鍵結而形成環狀結構) (In the general formula (9), P represents a phosphorus atom. R 10 , R 11, and R 12 represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, which may be the same as or different from each other. R 13 , R 14 and R 15 represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, which may be the same as or different from each other, and R 14 and R 15 may be bonded to form a cyclic structure)
作為膦化合物與醌化合物之加成物所使用之膦化合物，例如較佳為三苯基膦、三(烷基苯基)膦、三(烷氧基苯基)膦、三萘基膦、三(苄基)膦等於芳香環未經取代或存在烷基、烷氧基等取代基者，可列舉烷基、烷氧基等作為取代基具有1~6之碳數者。就獲得容易性之觀點而言，較佳為三苯基膦。 As the phosphine compound used as an adduct of a phosphine compound and a quinone compound, for example, triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, trisine The (benzyl) phosphine is equivalent to those in which an aromatic ring is unsubstituted or a substituent such as an alkyl group or an alkoxy group is present, and examples thereof include an alkyl group and an alkoxy group having a carbon number of 1 to 6 as a substituent. From the viewpoint of availability, triphenylphosphine is preferred.
又，作為膦化合物與醌化合物之加成物所使用之醌化合物，可列舉苯醌、蒽醌類，其中，就保存穩定性方面而言，較佳為對苯醌。 Examples of the quinone compound used as an adduct of a phosphine compound and a quinone compound include benzoquinone and anthraquinones. Among them, p-benzoquinone is preferred in terms of storage stability.
作為膦化合物與醌化合物之加成物之製造方法，可藉由使有機三級膦與苯醌類兩者於可使其等溶解之溶劑中接觸並加以混合而獲得加成物。作為溶劑，為丙酮或甲基乙基酮等酮類且對加成物之溶解性較低者 即可。然而，並不限定於此。 As a method for producing an adduct of a phosphine compound and a quinone compound, an adduct can be obtained by contacting and mixing both an organic tertiary phosphine and a benzoquinone in a solvent capable of dissolving them. As the solvent, ketones such as acetone or methyl ethyl ketone, and those with low solubility in adducts Just fine. However, it is not limited to this.
於通式(9)所表示之化合物中，與磷原子鍵結之R10、R11及R12為苯基、且R13、R14及R15為氫原子之化合物，即，使1,4-苯醌與三苯基膦加成而得之化合物其於降低密封用樹脂組成物之硬化物之熱時彈性模數方面較佳。 In the compound represented by the general formula (9), a compound in which R 10 , R 11, and R 12 bonded to a phosphorus atom are phenyl groups, and R 13 , R 14, and R 15 are hydrogen atoms, that is, 1, The compound obtained by the addition of 4-benzoquinone and triphenylphosphine is preferable in terms of reducing the thermal modulus of elasticity of the hardened product of the sealing resin composition.
作為密封用樹脂組成物可使用之鏻化合物與矽烷化合物之加成物，例如可列舉下述通式(10)所表示之化合物等。 Examples of the adduct of a sulfonium compound and a silane compound that can be used as the sealing resin composition include a compound represented by the following general formula (10).
(於上述通式(10)中，P表示磷原子，Si表示矽原子。R16、R17、R18及R19分別表示具有芳香環或雜環之有機基、或者脂肪族基，相互可相同亦可不同。式中R20為與基Y2及Y3鍵結之有機基。式中R21為與基Y4及Y5鍵結之有機基。Y2及Y3表示供質子性基釋出質子而成之基，同一分子內之基Y2及Y3與矽原子鍵結而形成螯合結構。Y4及Y5表示供質子性基釋出質子而成之基，同一分子內之基Y4及Y5與矽原子鍵結而形成螯合結構。R20及R21相互可相同亦可不同，Y2、Y3、Y4及Y5相互可相同亦可不同。Z1為具有芳香環或雜環之有機基、或者脂肪族基) (In the general formula (10), P represents a phosphorus atom, and Si represents a silicon atom. R 16 , R 17 , R 18, and R 19 each represent an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group, and may be mutually The same or different. In the formula, R 20 is an organic group bonded to the groups Y 2 and Y 3. In the formula, R 21 is an organic group bonded to the groups Y 4 and Y 5. Y 2 and Y 3 represent proton donating properties The radicals from which the radicals are released, the radicals Y 2 and Y 3 in the same molecule are bonded to the silicon atom to form a chelate structure. Y 4 and Y 5 represent the radicals from which the protonic radical is released from the proton. The internal groups Y 4 and Y 5 are bonded to the silicon atom to form a chelate structure. R 20 and R 21 may be the same or different from each other, and Y 2 , Y 3 , Y 4, and Y 5 may be the same or different from each other. Z (1 is an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group)
於通式(10)中，作為R16、R17、R18及R19，例如可列舉：苯基、甲基苯基、甲氧基苯基、羥基苯基、萘基、羥基萘基、苄基、甲基、 乙基、正丁基、正辛基及環己基等，該等中，更佳為苯基、甲基苯基、甲氧基苯基、羥基苯基、羥基萘基等具有烷基、烷氧基、羥基等取代基之芳香族基或者未經取代之芳香族基。 In the general formula (10), examples of R 16 , R 17 , R 18 and R 19 include phenyl, methylphenyl, methoxyphenyl, hydroxyphenyl, naphthyl, hydroxynaphthyl, Benzyl, methyl, ethyl, n-butyl, n-octyl, cyclohexyl, etc., among these, phenyl, methylphenyl, methoxyphenyl, hydroxyphenyl, hydroxynaphthyl, etc. An aromatic group having a substituent such as an alkyl group, an alkoxy group, or a hydroxyl group, or an unsubstituted aromatic group.
又，於通式(10)中，R20為與Y2及Y3鍵結之有機基。同樣地，R21為與基Y4及Y5鍵結之有機基。Y2及Y3為供質子性基釋出質子而成之基，同一分子內之基Y2及Y3與矽原子鍵結而形成螯合結構。同樣地，Y4及Y5為供質子性基釋出質子而成之基，同一分子內之基Y4及Y5與矽原子鍵結而形成螯合結構。基R20及R21相互可相同亦可不同，基Y2、Y3、Y4、及Y5相互可相同亦可不同。此種通式(10)中之-Y2-R20-Y3-、及-Y4-R21-Y5-所表示之基係由質子供與體釋出2個質子而成之基所構成者，作為質子供與體，較佳為於分子內具有至少2個羧基、或羥基之有機酸，進而較佳為於構成芳香環之鄰接之碳具有至少2個羧基或羥基之芳香族化合物，更佳為於構成芳香環之鄰接之碳具有至少2個羥基之芳香族化合物，例如可列舉：鄰苯二酚、鄰苯三酚、1,2-二羥基萘、2,3-二羥基萘、2,2'-聯苯酚、1,1'-聯-2-萘酚、水楊酸、1-羥基-2-萘甲酸、3-羥基-2-萘甲酸、氯冉酸、丹寧酸、2-羥基苄醇、1,2-環己二醇、1,2-丙二醇及甘油等，該等中，更佳為鄰苯二酚、1,2-二羥基萘、2,3-二羥基萘。 In the general formula (10), R 20 is an organic group bonded to Y 2 and Y 3 . Similarly, R 21 is an organic group bonded to the groups Y 4 and Y 5 . Y 2 and Y 3 are proton-derived groups that release protons. The Y 2 and Y 3 groups in the same molecule are bonded to silicon atoms to form a chelate structure. Similarly, Y 4 and Y 5 are radicals formed by proton-donating radicals, and the radicals Y 4 and Y 5 in the same molecule are bonded to silicon atoms to form a chelate structure. The radicals R 20 and R 21 may be the same or different from each other, and the radicals Y 2 , Y 3 , Y 4 , and Y 5 may be the same or different from each other. The base represented by -Y 2 -R 20 -Y 3 -and -Y 4 -R 21 -Y 5 -in the general formula (10) is a base formed by the release of two protons from a proton donor. As a proton donor, an organic acid having at least two carboxyl groups or hydroxyl groups in the molecule is preferable, and an aromatic having at least two carboxyl groups or hydroxyl groups is more preferable in the adjacent carbon constituting the aromatic ring. The compound is more preferably an aromatic compound having at least two hydroxyl groups on adjacent carbons constituting the aromatic ring, and examples thereof include catechol, catechol, 1,2-dihydroxynaphthalene, and 2,3-di Hydroxynaphthalene, 2,2'-biphenol, 1,1'-bi-2-naphthol, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chlororanic acid, dan Succinic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol, glycerol, etc. Among these, catechol, 1,2-dihydroxynaphthalene, 2,3 -Dihydroxynaphthalene.
又，通式(10)中之Z1表示具有芳香環或雜環之有機基或脂肪族基，作為該等之具體例，可列舉：甲基、乙基、丙基、丁基、己基及辛基等脂肪族烴基；或苯基、苄基、萘基及聯苯基等芳香族烴基；縮水甘油氧基丙基、巰基丙基、胺基丙基等具有縮水甘油氧基、巰基、胺基之烷基、及乙烯基等反應性取代基等，該等中，甲基、乙基、苯基、萘基及 聯苯基就熱穩定性方面而言更佳。 Z 1 in the general formula (10) represents an organic group or an aliphatic group having an aromatic ring or a heterocyclic ring. Specific examples of these include methyl, ethyl, propyl, butyl, hexyl, and Aliphatic hydrocarbon groups such as octyl; or aromatic hydrocarbon groups such as phenyl, benzyl, naphthyl, and biphenyl; glycidyloxypropyl, mercaptopropyl, and aminopropyl have glycidyloxy, mercapto, and amine Alkyl groups, reactive substituents such as vinyl groups, etc. Among these, methyl, ethyl, phenyl, naphthyl, and biphenyl groups are more preferred in terms of thermal stability.
作為鏻化合物與矽烷化合物之加成物之製造方法，係於添加有甲醇之燒瓶中加入苯基三甲氧基矽烷等矽烷化合物、2,3-二羥基萘等質子供與體並溶解，繼而於室溫攪拌下滴加甲醇鈉-甲醇溶液。進而，若於室溫攪拌下將預先準備之將四苯基溴化鏻等四取代鏻鹵化物溶解於甲醇中而得之溶液滴加於其中，則析出結晶。若將析出之結晶過濾、水洗、真空乾燥，則可獲得鏻化合物與矽烷化合物之加成物。然而，並不限定於此。 As a method for producing an adduct of a sulfonium compound and a silane compound, a silane compound such as phenyltrimethoxysilane and a proton donor such as 2,3-dihydroxynaphthalene are added to a flask containing methanol and dissolved, and then A sodium methoxide-methanol solution was added dropwise with stirring at room temperature. Furthermore, when a solution prepared by dissolving a tetrasubstituted phosphonium halide such as tetraphenylphosphonium bromide in methanol in advance at room temperature is added dropwise thereto, crystals are precipitated. If the precipitated crystals are filtered, washed with water, and dried under vacuum, an adduct of an amidine compound and a silane compound can be obtained. However, it is not limited to this.
密封用樹脂組成物中之硬化促進劑(F)之含量例如相對於密封用樹脂組成物整體較佳為0.05質量%以上，更佳為0.1質量%以上。藉由將硬化促進劑(F)之含量設為上述下限值以上，而可抑制密封用樹脂組成物之硬化性之降低。另一方面，密封用樹脂組成物中之硬化促進劑(F)之含量例如相對於密封用樹脂組成物整體較佳為1質量%以下，更佳為0.8質量%以下。藉由將硬化促進劑(F)之含量設為上述上限值以下，而可抑制密封用樹脂組成物之流動性之降低。 The content of the hardening accelerator (F) in the sealing resin composition is, for example, preferably 0.05% by mass or more, and more preferably 0.1% by mass or more, based on the entire sealing resin composition. When the content of the hardening accelerator (F) is at least the above-mentioned lower limit value, it is possible to suppress a decrease in the hardenability of the sealing resin composition. On the other hand, the content of the hardening accelerator (F) in the sealing resin composition is, for example, preferably 1% by mass or less, and more preferably 0.8% by mass or less, based on the entire sealing resin composition. When the content of the hardening accelerator (F) is equal to or less than the above-mentioned upper limit value, a decrease in the fluidity of the sealing resin composition can be suppressed.
於密封用樹脂組成物中，視需要進而亦可適當摻合如下各種添加劑：碳黑、鐵丹等著色劑；聚矽氧橡膠等低應力成分；巴西棕櫚蠟等天然蠟、合成蠟、硬脂酸鋅等高級脂肪酸及其金屬鹽類或者石蠟等脫模劑；氫氧化鋁、氫氧化鎂、硼酸鋅、鉬酸鋅、磷腈等難燃劑；抗氧化劑等。 In the resin composition for sealing, if necessary, various additives such as carbon black, iron dan, and other coloring agents; low-stress components such as silicone rubber; natural waxes such as carnauba wax, synthetic waxes, and stearin may also be appropriately blended. Higher fatty acids such as zinc acid and their metal salts or release agents such as paraffin; flame retardants such as aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, phosphazene, and antioxidants.
作為密封用樹脂組成物，例如可使用將上述各成分利用公知之手段加以混合，進而利用輥、捏合機或擠出機等混練機熔融混練，冷卻後粉碎而成者等視需要調整為適當分散指數或流動性等者。 As the sealing resin composition, for example, the above components can be mixed by a known means, and further melt-kneaded with a kneading machine such as a roll, a kneader, or an extruder, and pulverized after cooling, etc., as necessary to adjust the dispersion appropriately. Index or liquidity.
繼而，對本實施形態之半導體裝置100進行說明。 Next, the semiconductor device 100 according to this embodiment will be described.
半導體裝置100具備半導體元件20、接合線40、及密封樹脂50。接合線40連接於半導體元件20且以Cu為主成分。又，密封樹脂50係藉由上述密封用樹脂組成物之硬化物而構成，並密封半導體元件20及接合線40。 The semiconductor device 100 includes a semiconductor element 20, a bonding wire 40, and a sealing resin 50. The bonding wire 40 is connected to the semiconductor element 20 and contains Cu as a main component. The sealing resin 50 is formed of a hardened body of the sealing resin composition, and seals the semiconductor element 20 and the bonding wire 40.
半導體元件20搭載於基材30上。基材30例如為引線框架或有機基板。又，基材30連接於接合線40。圖1中例示有於作為引線框架之基材30中之晶座32上經由晶粒黏著材10搭載半導體元件20之情形。作為引線框架之基材30，例如係由以Cu或42合金為主成分之金屬材料所構成。再者，半導體元件20亦可配置於其他半導體元件上。 The semiconductor element 20 is mounted on a base material 30. The base material 30 is, for example, a lead frame or an organic substrate. The base material 30 is connected to the bonding wire 40. FIG. 1 illustrates a case where a semiconductor element 20 is mounted on a wafer base 32 in a base material 30 as a lead frame via a die bonding material 10. The base material 30 as the lead frame is made of, for example, a metal material mainly composed of Cu or 42 alloy. The semiconductor element 20 may be disposed on another semiconductor element.
於半導體元件20之上表面，例如形成有複數個電極墊22。設置於半導體元件20之電極墊22之至少表面層例如係由以Al為主成分之金屬材料所構成。藉此，可提昇以Cu為主成分之接合線40與電極墊22之連接可靠性。 A plurality of electrode pads 22 are formed on the upper surface of the semiconductor element 20, for example. At least a surface layer of the electrode pad 22 provided in the semiconductor element 20 is made of, for example, a metal material containing Al as a main component. Thereby, the connection reliability of the bonding wire 40 and the electrode pad 22 mainly composed of Cu can be improved.
於圖1中例示有接合線40將半導體元件20之電極墊22、與基材30中之外引線34電性連接之情形。 FIG. 1 illustrates a case where the bonding wire 40 electrically connects the electrode pad 22 of the semiconductor element 20 and the outer lead 34 in the base material 30.
密封樹脂50係由上述密封用樹脂組成物之硬化物所構成。因此，可獲得對基材30或接合線40之密接性良好、耐回流焊性或耐濕可靠性、高溫動作特性優異之半導體裝置100。該效果於接合線40由以Cu為主成分之金屬材料所構成、且基材30由以Cu或42合金為主成分之金屬材料所構成之情形時，可尤其顯著地獲得。又，亦可謀求半導體裝置100之高溫保管特性之提昇。 The sealing resin 50 is composed of a hardened product of the resin composition for sealing. Therefore, a semiconductor device 100 having good adhesion to the base material 30 or the bonding wire 40, reflow resistance, moisture resistance reliability, and high-temperature operation characteristics can be obtained. This effect is particularly remarkable when the bonding wire 40 is composed of a metal material mainly composed of Cu and the base material 30 is composed of a metal material mainly composed of Cu or 42 alloy. In addition, the high-temperature storage characteristics of the semiconductor device 100 can be improved.
半導體裝置100例如係以如下方式製造。 The semiconductor device 100 is manufactured, for example, as follows.
首先，於基材30上搭載半導體元件20。繼而，藉由以Cu為主成分之 接合線40使基材30與半導體元件20相互連接。繼而，藉由上述密封用樹脂組成物將半導體元件20與接合線40密封。作為密封成形之方法並無特別限定，例如可列舉轉移成形法或壓縮成形法。藉此，可製造半導體裝置100。 First, a semiconductor element 20 is mounted on a base material 30. Then, by using Cu as the main component The bonding wire 40 connects the substrate 30 and the semiconductor element 20 to each other. Then, the semiconductor element 20 and the bonding wire 40 are sealed with the sealing resin composition. The method for the sealing molding is not particularly limited, and examples thereof include a transfer molding method and a compression molding method. Thereby, the semiconductor device 100 can be manufactured.
再者，本發明並不限定於上述實施形態，於可達成本發明之目的之範圍內之變化、改良等包含於本發明中。 In addition, the present invention is not limited to the above-mentioned embodiments, and changes, improvements, and the like within a range that can achieve the object of the present invention are included in the present invention.
[實施例] [Example]
繼而，對本發明之實施例進行說明。 Next, an embodiment of the present invention will be described.
(密封用樹脂組成物) (Resin composition for sealing)
對實施例1~14及比較例1~2之各者以如下方式製備密封用樹脂組成物。首先，藉由表1所示之摻合量之偶合劑(D)對填充材(C)實施表面處理。繼而，根據表1所示之組成，使用攪拌機將各成分於15~28℃混合。繼而，對所獲得之混合物於70~100℃進行輥混練。繼而，將混練後之混合物冷卻並粉碎而獲得環氧樹脂組成物。再者，表1中之各成分之詳細情況係如下所述。又，表1中之單位為質量%。 About each of Examples 1-14 and Comparative Examples 1-2, the sealing resin composition was prepared as follows. First, the filler (C) was surface-treated with the coupling agent (D) in the blending amount shown in Table 1. Then, according to the composition shown in Table 1, each component was mixed at 15-28 degreeC using the stirrer. Then, the obtained mixture was roll-kneaded at 70 to 100 ° C. Then, the kneaded mixture was cooled and pulverized to obtain an epoxy resin composition. The details of each component in Table 1 are as follows. The unit in Table 1 is mass%.
(A)環氧樹脂 (A) Epoxy resin
環氧樹脂1：含聯伸苯基骨架之苯酚芳烷基型環氧樹脂(NC-3000P，日本化藥股份有限公司製造) Epoxy resin 1: phenol aralkyl type epoxy resin containing biphenylene skeleton (NC-3000P, manufactured by Nippon Kayaku Co., Ltd.)
環氧樹脂2：聯苯型環氧樹脂(YX4000K，三菱化學股份有限公司製造) Epoxy resin 2: Biphenyl epoxy resin (YX4000K, manufactured by Mitsubishi Chemical Corporation)
環氧樹脂3：萘型環氧樹脂(HP-4770，DIC股份有限公司製造) Epoxy resin 3: Naphthalene type epoxy resin (HP-4770, manufactured by DIC Corporation)
(B)硬化劑 (B) Hardener
硬化劑1：含聯伸苯基骨架之苯酚芳烷基樹脂(MEH-7851SS，明和化成股份有限公司製造) Hardener 1: Phenol aralkyl resin containing biphenylene skeleton (MEH-7851SS, manufactured by Meiwa Chemical Co., Ltd.)
硬化劑2：含伸苯基骨架之苯酚芳烷基樹脂(XLC-4L，三井化學股份有限公司製造) Hardener 2: Phenyl aralkyl resin with phenylene skeleton (XLC-4L, manufactured by Mitsui Chemicals Co., Ltd.)
硬化劑3：三苯酚甲烷型酚樹脂(MEH-7500，明和化成股份有限公司製造) Hardener 3: Triphenol methane type phenol resin (MEH-7500, manufactured by Meiwa Chemical Co., Ltd.)
(C)填充材 (C) Filler
填充材1：二氧化矽(平均粒徑26μm、比表面積2.4mm2/g) Filling material 1: Silicon dioxide (average particle size: 26 μm, specific surface area: 2.4 mm 2 / g)
填充材2：二氧化矽(SO-25R，Admatechs股份有限公司製造，平均粒徑0.5μm、比表面積6.0mm2/g) Filling material 2: Silicon dioxide (SO-25R, manufactured by Admatechs, average particle diameter 0.5 μm, specific surface area 6.0 mm 2 / g)
(D)偶合劑 (D) Coupling agent
γ-巰基丙基三甲氧基矽烷(信越化學工業股份有限公司製造，KBM-803) γ-Mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., KBM-803)
(E)離子捕捉劑 (E) Ion trapping agent
水滑石(DHT-4H，協和化學工業股份有限公司製造) Hydrotalcite (DHT-4H, manufactured by Kyowa Chemical Industry Co., Ltd.)
(F)硬化促進劑 (F) Hardening accelerator
硬化促進劑1：下述式(11)所表示之化合物 Hardening accelerator 1: Compound represented by the following formula (11)
硬化促進劑2：下述式(12)所表示之化合物 Hardening accelerator 2: Compound represented by the following formula (12)
(硬化促進劑1之合成方法) (Synthesis method of hardening accelerator 1)
於附有冷卻管及攪拌裝置之可分離式燒瓶中添加苯醌6.49g(0.060mol)、三苯基膦17.3g(0.066mol)及丙酮40ml，攪拌下於室溫中進行反應。將析出之結晶以丙酮洗淨後過濾、乾燥而獲得深綠色結晶之硬化促進劑1。 In a separable flask equipped with a cooling tube and a stirring device, 6.49 g (0.060 mol) of benzoquinone, 17.3 g (0.066 mol) of triphenylphosphine and 40 ml of acetone were added, and the reaction was carried out at room temperature with stirring. The precipitated crystals were washed with acetone, filtered, and dried to obtain a hardening accelerator 1 for dark green crystals.
(硬化促進劑2之合成方法) (Synthesis method of hardening accelerator 2)
於附有冷卻管及攪拌裝置之可分離式燒瓶中添加2,3-二羥基萘12.81g(0.080mol)、四苯基溴化鏻16.77g(0.040mol)及甲醇100ml，並攪拌使其等均勻地溶解。若將預先將氫氧化鈉1.60g(0.04ml)溶解於10ml之甲醇中而獲得之氫氧化鈉溶液緩慢滴加於燒瓶內，則析出結晶。將析出之結晶過濾、水洗、真空乾燥而獲得硬化促進劑2。 In a separable flask equipped with a cooling tube and a stirring device, 12.81 g (0.080 mol) of 2,3-dihydroxynaphthalene, 16.77 g (0.040 mol) of tetraphenylphosphonium bromide, and 100 ml of methanol were added, and stirred to wait. Dissolve evenly. When a sodium hydroxide solution obtained by dissolving 1.60 g (0.04 ml) of sodium hydroxide in 10 ml of methanol in advance was slowly dropped into the flask, crystals were precipitated. The precipitated crystal was filtered, washed with water, and dried under vacuum to obtain a hardening accelerator 2.
(G)脫模劑 (G) Release agent
巴西棕櫚蠟 Carnauba wax
於實施例1~4、7~14及比較例1~2中，以如下方式對填充材(C)利用偶合劑(D)進行表面處理。首先，將填充材1及填充材2投入攪拌機後，開始攪拌，於其中進而投入偶合劑(D)並將該等攪拌3.0分鐘，獲得填充材1、填充材2及偶合劑(D)之混合物。繼而，將該混合物自攪拌機中取出，靜置表1所示之時間(靜置時間)。藉此，獲得藉由偶合劑(D)進行過表面處理之填充材(C)。 In Examples 1-4, 7-14, and Comparative Examples 1-2, the filler (C) was surface-treated with the coupling agent (D) as follows. First, after the filler 1 and the filler 2 are put into a mixer, stirring is started, a coupling agent (D) is further added thereto, and these are stirred for 3.0 minutes to obtain a mixture of the filler 1, the filler 2 and the coupling agent (D). . Then, the mixture was taken out of the blender, and allowed to stand for the time shown in Table 1 (resting time). Thereby, a filler (C) having been surface-treated with the coupling agent (D) was obtained.
於實施例5中，將上述混合物靜置後，於55℃、3小時之條件下對上述 混合物進行熱處理，除此以外，與實施例1同樣地進行表面處理。 In Example 5, the mixture was allowed to stand, and the mixture was subjected to the above conditions at 55 ° C for 3 hours. The surface treatment was performed in the same manner as in Example 1 except that the mixture was heat-treated.
於實施例6中，以如下方式獲得填充材1、填充材2及偶合劑(D)之混合物，除此以外，與實施例1同樣地進行表面處理。首先，將填充材1及填充材2投入攪拌機，使其等混合。繼而，對攪拌機內之填充材1及填充材2一面使用噴霧器噴霧偶合劑(D)，一面將其等攪拌3.0分鐘，獲得填充材1、填充材2及偶合劑(D)之混合物。繼而，將該混合物自攪拌機中取出，靜置表1所示之時間(靜置時間)。 In Example 6, the same procedure as in Example 1 was carried out except that a mixture of the filler 1, the filler 2 and the coupling agent (D) was obtained as follows. First, the filler 1 and the filler 2 are put into a mixer, and they are mixed. Then, the filler (1) and the filler (2) in the mixer were sprayed with the coupling agent (D) while stirring the mixture for 3.0 minutes to obtain a mixture of the filler (1), the filler (2), and the coupling agent (D). Then, the mixture was taken out of the blender, and allowed to stand for the time shown in Table 1 (resting time).
(pH(1)之測定) (Measurement of pH (1) )
對各實施例及各比較例以如下方式測定所獲得之密封用樹脂組成物之pH(1)。首先，將於175℃、4小時之條件下使密封用樹脂組成物熱硬化而獲得之硬化物粉碎，獲得粉碎物。粉碎處理係藉由利用TI-100(CMT股份有限公司製造)並將硬化物5.2g放入粉碎釜中粉碎2分鐘而進行。繼而，將剛粉碎後之上述粉碎物5g加入純水50ml中。繼而，於125℃、20小時之條件下使用內容器為聚四氟乙烯製、外容器為金屬製之耐壓容器對該純水進行熱水萃取處理。用pH計測定藉此所獲得之萃取液之pH值，將其設為pH(1)。 About each Example and each comparative example, pH (1) of the obtained sealing resin composition was measured as follows. First, a hardened material obtained by thermally curing the sealing resin composition at 175 ° C. for 4 hours is pulverized to obtain a pulverized material. The pulverization treatment was performed by using TI-100 (manufactured by CMT Co., Ltd.) and pulverizing 5.2 g of the cured product in a pulverizer for 2 minutes. Next, 5 g of the above-mentioned pulverized product immediately after pulverization was added to 50 ml of pure water. Then, the pure water was subjected to hot water extraction treatment at 125 ° C. for 20 hours using a pressure-resistant container made of polytetrafluoroethylene as the inner container and a metal container as the outer container. The pH value of the extraction liquid thus obtained was measured with a pH meter, and it was set to pH (1) .
(pH(2)之測定) (Measurement of pH (2) )
對各實施例及各比較例以如下方式測定所獲得之密封用樹脂組成物之pH(2)。首先，將於175℃、4小時之條件使密封用樹脂組成物熱硬化而獲得之硬化物粉碎，獲得粉碎物。粉碎處理係藉由利用TI-100(CMT股份有限公司製造)並將硬化物5.2g放入粉碎釜中粉碎2分鐘而進行。繼而，將所獲得之上述粉碎物於175℃下保管500小時。繼而，將保管後之上述粉碎物 5g加入純水50ml中。繼而，於125℃、20小時之條件下使用內容器為聚四氟乙烯製、外容器為金屬製之耐壓容器對該純水進行熱水萃取處理。用pH計測定藉此所獲得之萃取液之pH值，將其設為pH(2)。 About each Example and each comparative example, the pH (2) of the obtained sealing resin composition was measured as follows. First, a hardened material obtained by thermally curing the sealing resin composition at 175 ° C. for 4 hours is pulverized to obtain a pulverized material. The pulverization treatment was performed by using TI-100 (manufactured by CMT Co., Ltd.) and pulverizing 5.2 g of the cured product in a pulverizer for 2 minutes. Then, the obtained pulverized material was stored at 175 ° C for 500 hours. Then, 5 g of the above-mentioned pulverized material after storage was added to 50 ml of pure water. Then, the pure water was subjected to hot water extraction treatment at 125 ° C. for 20 hours using a pressure-resistant container made of polytetrafluoroethylene as the inner container and a metal container as the outer container. The pH value of the extraction liquid thus obtained was measured with a pH meter, and it was set to pH (2) .
(半導體裝置之製作) (Manufacturing of semiconductor devices)
對實施例1~14、比較例1~2之各者以如下方式製作半導體裝置。 A semiconductor device was produced for each of Examples 1 to 14 and Comparative Examples 1 to 2 as follows.
首先，將具備鋁製電極墊之TEG(Test Element Group，測試元件組)晶片(3.5mm×3.5mm)搭載於表面藉由Ag鍍敷之引線框架(引線框架材質：42合金)之晶座部上。繼而，對TEG晶片之電極墊(以下為電極墊)與引線框架之外引線部使用由Cu 99.9%之金屬材料所構成之接合線，以線距120μm進行打線接合。對藉此獲得之構造體使用低壓轉移成形機於模具溫度175℃、注入壓力10.0MPa、硬化時間2分鐘之條件下使用密封用樹脂組成物進行密封成形，而製作半導體封裝(封裝尺寸：7.2mm×11.5mm×1.95mm)。之後，將所獲得之半導體封裝於175℃、4小時之條件下進行後硬化，獲得半導體裝置。 First, a TEG (Test Element Group) wafer (3.5 mm x 3.5 mm) provided with an aluminum electrode pad was mounted on a crystal base portion of a lead frame (lead frame material: 42 alloy) plated with Ag. on. Next, the electrode pads (hereinafter referred to as electrode pads) of the TEG wafer and the lead portions outside the lead frame were bonded using a bonding wire made of Cu 99.9% metal material at a wire pitch of 120 μm. A semiconductor package (package size: 7.2 mm) was produced by using the low-pressure transfer molding machine under the conditions of a mold temperature of 175 ° C, an injection pressure of 10.0 MPa, and a hardening time of 2 minutes to seal the structure using the resin composition for sealing. X 11.5 mm x 1.95 mm). Thereafter, the obtained semiconductor package was post-cured at 175 ° C for 4 hours to obtain a semiconductor device.
(MSL(耐回流焊性評價)) (MSL (Reflow Resistance Evaluation))
對實施例1~14、比較例1~2之各者，將所獲得之12個半導體裝置於85℃相對濕度60%之環境下靜置168小時後進行IR回流焊處理(260℃)。繼而，利用超音波探傷裝置觀察處理後之半導體裝置內部，算出於密封樹脂與引線框架之界面所產生之剝離之面積。對全部半導體裝置，將剝離面積未達5%之情形記為◎，將5%以上且10%以下之情形記為○，將超過10%之情形記為×。 For each of Examples 1 to 14, and Comparative Examples 1 to 2, the obtained 12 semiconductor devices were left to stand in an environment of 85 ° C and 60% relative humidity for 168 hours and then subjected to IR reflow treatment (260 ° C). Then, the inside of the processed semiconductor device was observed with an ultrasonic flaw detection device, and the area of peeling generated at the interface between the sealing resin and the lead frame was calculated. For all semiconductor devices, a case where the peeling area is less than 5% is denoted as ◎, a case where 5% or more and 10% or less is denoted as ○, and a case where it exceeds 10% is denoted as ×.
(HTSL(高溫保管特性評價)) (HTSL (High Temperature Storage Characteristics Evaluation))
對實施例1~14、比較例1~2之各者，將所獲得之半導體裝置保管於150℃之環境下，每隔24小時測定半導體晶片之電極墊與接合線間之電阻值，將該值相對於初始值增加20%之半導體裝置記為不良。將即便保管2000小時亦不產生不良者記為◎，將於1000~2000小時之間產生不良者記為○，將於1000小時以內產生不良者記為×。 For each of Examples 1 to 14, and Comparative Examples 1 to 2, the obtained semiconductor device was stored in an environment of 150 ° C, and the resistance value between the electrode pad and the bonding wire of the semiconductor wafer was measured every 24 hours, and A semiconductor device whose value is increased by 20% from the initial value is regarded as defective. Those who did not produce defects even after being stored for 2000 hours were recorded as ◎, those who produced defects between 1000 and 2000 hours were recorded as ○, and those who produced defects within 1,000 hours were recorded as ×.
如表1所示，於實施例1~14中，關於耐回流焊性及高溫保管特性獲得良好之結果。實施例1~6、8、10、12~14與實施例7、9、11相比，顯示更優異之高溫保管特性。又，實施例2~14與實施例1相比，顯示更優異之耐回流焊性。 As shown in Table 1, in Examples 1 to 14, good results were obtained regarding reflow resistance and high-temperature storage characteristics. Examples 1 to 6, 8, 10, and 12 to 14 exhibited more excellent high-temperature storage characteristics than Examples 7, 9, and 11. In addition, Examples 2 to 14 showed more excellent reflow resistance than Example 1.
該申請案係主張以2014年5月28日提出申請之日本專利特願2014-109860號為基礎之優先權，其揭示之內容全部併入本文中。 This application claims priority based on Japanese Patent Application No. 2014-109860, filed on May 28, 2014, and the disclosure thereof is incorporated herein in its entirety.
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