US20010004651A1 - Epoxy resin compositions and premolded semiconductor packages - Google Patents
Epoxy resin compositions and premolded semiconductor packages Download PDFInfo
- Publication number
- US20010004651A1 US20010004651A1 US09/726,575 US72657500A US2001004651A1 US 20010004651 A1 US20010004651 A1 US 20010004651A1 US 72657500 A US72657500 A US 72657500A US 2001004651 A1 US2001004651 A1 US 2001004651A1
- Authority
- US
- United States
- Prior art keywords
- epoxy resin
- porous silica
- resin composition
- silica
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 89
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 84
- 239000000203 mixture Substances 0.000 title claims abstract description 60
- 239000004065 semiconductor Substances 0.000 title claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 161
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 76
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 239000011256 inorganic filler Substances 0.000 claims abstract description 18
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 18
- 230000005484 gravity Effects 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 16
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 8
- 229910002027 silica gel Inorganic materials 0.000 claims description 8
- 239000000741 silica gel Substances 0.000 claims description 8
- 238000003980 solgel method Methods 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 230000035699 permeability Effects 0.000 abstract description 8
- 239000000945 filler Substances 0.000 abstract description 2
- 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 25
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000002274 desiccant Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229920001568 phenolic resin Polymers 0.000 description 9
- 239000005011 phenolic resin Substances 0.000 description 9
- 229920003986 novolac Polymers 0.000 description 8
- 239000012798 spherical particle Substances 0.000 description 8
- 239000012634 fragment Substances 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 239000007822 coupling agent Substances 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- -1 laminates Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 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 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 230000009969 flowable effect Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 229910002026 crystalline silica Inorganic materials 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 0 *OC.*OC.*OC.*OC.*OC.*OC.*OC.*OC.*Oc1c(C)cc(-c2cc(C)c(O*)c(C)c2)cc1C.CCCC.CCCC.CCc1ccc(-c2ccc(CC)cc2)cc1.CCc1ccc(-c2ccc(CC)cc2)cc1.CCc1ccc(-c2ccccc2)cc1.CCc1ccc(-c2ccccc2)cc1.CCc1ccc(CC)cc1.[H]C.c1ccc2ccccc2c1.c1ccc2ccccc2c1.c1ccc2ccccc2c1.c1ccc2ccccc2c1.c1ccc2ccccc2c1.c1ccccc1.c1ccccc1.c1ccccc1 Chemical compound *OC.*OC.*OC.*OC.*OC.*OC.*OC.*OC.*Oc1c(C)cc(-c2cc(C)c(O*)c(C)c2)cc1C.CCCC.CCCC.CCc1ccc(-c2ccc(CC)cc2)cc1.CCc1ccc(-c2ccc(CC)cc2)cc1.CCc1ccc(-c2ccccc2)cc1.CCc1ccc(-c2ccccc2)cc1.CCc1ccc(CC)cc1.[H]C.c1ccc2ccccc2c1.c1ccc2ccccc2c1.c1ccc2ccccc2c1.c1ccc2ccccc2c1.c1ccc2ccccc2c1.c1ccccc1.c1ccccc1.c1ccccc1 0.000 description 1
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- SMQYUKULHKFWAU-UHFFFAOYSA-N C1=CC2=C(C=C1)C=CC=C2.C1=CC2=C(C=C1)C=CC=C2.C1=CC=C2C=CC=CC2=C1.C1=CC=C2C=CC=CC2=C1.C1=CC=C2C=CC=CC2=C1.C1=CC=CC=C1.C1=CC=CC=C1.C1=CC=CC=C1.CCC.CCC1=CC=C(C2=CC=C(CC)C=C2)C=C1.CCC1=CC=C(C2=CC=C(CC)C=C2)C=C1.CCC1=CC=C(C2=CC=CC=C2)C=C1.CCC1=CC=C(C2=CC=CC=C2)C=C1.CCC1=CC=C(CC)C=C1.CCC1=CC=C(CC)C=C1.CCCC.CCCC.CO.CO.CO.CO.CO.CO.CO.CO.OC1=CC=CC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1.[H]C Chemical compound C1=CC2=C(C=C1)C=CC=C2.C1=CC2=C(C=C1)C=CC=C2.C1=CC=C2C=CC=CC2=C1.C1=CC=C2C=CC=CC2=C1.C1=CC=C2C=CC=CC2=C1.C1=CC=CC=C1.C1=CC=CC=C1.C1=CC=CC=C1.CCC.CCC1=CC=C(C2=CC=C(CC)C=C2)C=C1.CCC1=CC=C(C2=CC=C(CC)C=C2)C=C1.CCC1=CC=C(C2=CC=CC=C2)C=C1.CCC1=CC=C(C2=CC=CC=C2)C=C1.CCC1=CC=C(CC)C=C1.CCC1=CC=C(CC)C=C1.CCCC.CCCC.CO.CO.CO.CO.CO.CO.CO.CO.OC1=CC=CC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1.[H]C SMQYUKULHKFWAU-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 238000000563 Verneuil process Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- BVURNMLGDQYNAF-UHFFFAOYSA-N dimethyl(1-phenylethyl)amine Chemical compound CN(C)C(C)C1=CC=CC=C1 BVURNMLGDQYNAF-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical class S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-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
- AUOZNINQGUNWOV-UHFFFAOYSA-N triphenyl borate;triphenylphosphane Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 AUOZNINQGUNWOV-UHFFFAOYSA-N 0.000 description 1
- IUURMAINMLIZMX-UHFFFAOYSA-N tris(2-nonylphenyl)phosphane Chemical compound CCCCCCCCCC1=CC=CC=C1P(C=1C(=CC=CC=1)CCCCCCCCC)C1=CC=CC=C1CCCCCCCCC IUURMAINMLIZMX-UHFFFAOYSA-N 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/06—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising selenium or tellurium in uncombined form other than as impurities in semiconductor bodies of other materials
- H01L21/10—Preliminary treatment of the selenium or tellurium, its application to the foundation plate, or the subsequent treatment of the combination
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/295—Organic, e.g. plastic containing a filler
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/02—Containers; Seals
- H01L23/06—Containers; Seals characterised by the material of the container or its electrical properties
- H01L23/08—Containers; Seals characterised by the material of the container or its electrical properties the material being an electrical insulator, e.g. glass
-
- 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
- H01L2224/02—Bonding areas; Manufacturing methods related thereto
- H01L2224/04—Structure, shape, material or disposition of the bonding areas prior to the connecting process
- H01L2224/05—Structure, shape, material or disposition of the bonding areas prior to the connecting process of an individual bonding area
- H01L2224/0554—External layer
- H01L2224/05599—Material
-
- 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
-
- 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
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/85—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a wire connector
- H01L2224/8538—Bonding interfaces outside the semiconductor or solid-state body
- H01L2224/85399—Material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—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
- H01L24/42—Wire connectors; Manufacturing methods related thereto
- H01L24/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L24/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
-
- 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
- H01L2924/00014—Technical content checked by a classifier the subject-matter covered by the group, the symbol of which is combined with the symbol of this group, being disclosed without further technical details
-
- 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
- H01L2924/01—Chemical elements
- H01L2924/01012—Magnesium [Mg]
-
- 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
- H01L2924/01—Chemical elements
- H01L2924/01019—Potassium [K]
-
- 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
- H01L2924/01—Chemical elements
- H01L2924/0102—Calcium [Ca]
-
- 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
- H01L2924/01—Chemical elements
- H01L2924/01067—Holmium [Ho]
-
- 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
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/11—Device type
- H01L2924/12—Passive devices, e.g. 2 terminal devices
- H01L2924/1204—Optical Diode
- H01L2924/12042—LASER
-
- 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
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/151—Die mounting substrate
- H01L2924/1515—Shape
- H01L2924/15153—Shape the die mounting substrate comprising a recess for hosting the device
-
- 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
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/151—Die mounting substrate
- H01L2924/15165—Monolayer substrate
-
- 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
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/161—Cap
- H01L2924/1615—Shape
- H01L2924/16195—Flat cap [not enclosing an internal cavity]
-
- 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
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/181—Encapsulation
-
- 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
- H01L2924/30—Technical effects
- H01L2924/301—Electrical effects
- H01L2924/3025—Electromagnetic shielding
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/259—Silicic material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
Definitions
- This invention relates to epoxy resin compositions which are easily moldable, have a low moisture permeability and reliability in the cured state, and are suitable for encapsulating semiconductor chips and especially as premolded hollow semiconductor packages. It also relates to premolded hollow semiconductor packages encapsulated with the epoxy resin compositions in the cured state.
- epoxy resins featuring mechanical strength, moisture resistance and moldability find a variety of applications as insulating materials, laminates, adhesives and semiconductor encapsulants.
- thermosetting resins As opposed to essentially moisture impermeable metals and ceramics, epoxy resins classified as thermosetting resins have a coefficient of moisture diffusion. Upon exposure to humid conditions, epoxy resins absorb moisture and allow moisture to permeate therethrough. The moisture permeability of thermosetting resins often becomes a problem when they are used in the application requiring hermetic and water-proof seals, for example, in precision machines such as watches and electronic calculators, and electronic parts such as semiconductor packages, especially solid state imaging device (generally known as CCD) hollow packages and quartz oscillator hollow packages.
- CCD solid state imaging device
- quartz oscillator hollow packages for example, resin packages of CCD slowly absorb moisture when exposed to a hot humid environment for an extended period of time, though not in direct contact with water. If moisture is introduced into the hermetic space in excess of the saturated steam amount determined from the saturated water vapor pressure, moisture condenses. The device becomes inoperable by dew condensation.
- An improvement in moisture permeability has long been desired for prior art epoxy resin compositions comprising an epoxy resin, a curing agent and an inorganic filler for use in hollow packages.
- One known means is to add an inorganic desiccant to the epoxy resin composition so that the desiccant adsorbs moisture permeating through the cured item, preventing moisture from entering the hollow interior.
- JP-A 8-157694 of the same assignee as the present invention discloses an epoxy resin composition comprising at least 10 parts by weight of an inorganic desiccant per 100 parts by weight of an epoxy resin and a curing agent combined. Specifically, using AMT silica by Mizusawa Chemical K. K. as the inorganic desiccant, the composition is rendered low moisture permeable.
- AMT silica however, has a low true specific gravity and contains a relatively large amount of ionic impurities since it is porous silica obtained by sintering zeolite.
- the low true specific gravity means that a certain weight of silica added accounts for a larger volume so that an increased amount of silica can obstruct flow.
- the large amount of ionic impurities interfere with the curing function of the curing catalyst so that cure may become short, resulting in drops of hot strength and bond strength.
- JP 2,750,254 discloses a semiconductor package comprising an insulating substrate containing 0.1 to 50% by weight of a desiccant.
- the amount of desiccant added to an epoxy resin composition should preferably be increased since a small amount of desiccant does not fully adsorb moisture penetrating through the cured item.
- a package sample containing a small amount of desiccant allows moisture to reach the cavity so that moisture may condense on the glass lid. This drawback can be eliminated by increasing the amount of desiccant.
- conventional desiccants are poorly compatible with epoxy resins and curing agents, they exacerbate the flow particularly when added in large amounts.
- the epoxy resin composition with retarded flow can cause such defects as short shots and voids when molded by a transfer molding machine, and is thus unsuitable for semiconductor encapsulating purposes.
- An object of the invention is to provide an epoxy resin composition which is flowable and easily moldable and cures into a product having a low moisture permeability, and a premolded hollow semiconductor package encapsulated with the epoxy resin composition in the cured state.
- an epoxy resin composition comprising an epoxy resin, a curing agent, and an inorganic filler flows smoothly and is easily moldable when the filler is porous silica having a specific surface area of 6 to 200 m 2 /g, a true specific gravity of 2.0 to 2.2, and a mean particle size of 2 to 50 ⁇ m.
- the composition cures into a product of quality having a low moisture permeability.
- the composition is smoothly flowable and readily bondable and curable into a product having minimized moisture permeation.
- the composition is thus suited for forming premolded hollow semiconductor packages.
- the invention provides an epoxy resin composition
- an epoxy resin composition comprising an epoxy resin, a curing agent, and an inorganic filler in the form of porous silica having a specific surface area of 6 to 200 m 2 /g, a true specific gravity of 2.0 to 2.2, and a mean particle size of 2 to 50 ⁇ m.
- the porous silica has been prepared by forming a silica gel having a weight average particle size of up to 50 ⁇ m by a sol-gel process, and firing the silica gel at a temperature of 700 to 1,200° C.; the porous silica has a moisture pickup of at least 0.3% by weight when kept at 25° C.
- the porous silica contains up to 1 ppm of each of alkali and alkaline earth metals.
- the porous silica preferably accounts for 40 to 90% by weight, more preferably at least 55% by weight of the entire epoxy resin composition.
- the invention also provides a premolded hollow semiconductor package encapsulated with a cured product of an epoxy resin composition comprising an epoxy resin, a curing agent, and an inorganic filler including a porous silica having a specific surface area of 6 to 200 m 2 /g, a true specific gravity of 2.0 to 2.2, and a mean particle size of 2 to 50 ⁇ m.
- FIG. 1 is a schematic cross-sectional view of a premolded hollow semiconductor package molded in Examples.
- the epoxy resin composition according to the invention contains an epoxy resin, a curing agent, and an inorganic filler.
- the epoxy resin used herein is not limited in molecular structure and molecular weight as long as it has at least two epoxy groups in a molecule and can be cured with curing agents to be described later. A proper choice may be made among conventional well-known epoxy resins.
- useful epoxy resins include bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins, novolak type epoxy resins such as phenol novolak type epoxy resins and cresol novolak type epoxy resins, triphenolalkane type epoxy resins such as triphenolmethane type epoxy resins and triphenolpropane type epoxy resins and polymers thereof, epoxy resins having a biphenyl skeleton, epoxy resins having a naphthalene skeleton, dicyclopentadiene-phenol novolak resins, phenolaralkyl type epoxy resins, glycidyl ester type epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, and halogenated epoxy resins.
- bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins
- novolak type epoxy resins such as phenol novolak type epoxy resins and cresol novolak type epoxy resins
- triphenolalkane type epoxy resins such as
- G is glycidyl
- Me is methyl
- n is an integer of 0 to 10, and preferably 0 to 5.
- the curing agent is not critical and may be any of phenolic compounds, amine compounds and acid anhydrides commonly used for the curing of conventional epoxy resins. Of these, phenolic resins having at least two phenolic hydroxyl groups per molecule are preferred.
- Exemplary curing agents include bisphenol type resins such as bisphenol A type resins and bisphenol F type resins; novolak-type phenolic resins such as phenolic novolak resins and cresol novolak resins; triphenolalkane resins such as triphenolmethane resins and triphenolpropane resins; resole type phenolic resins, phenol aralkyl resins, biphenyl type phenolic resins, naphthalene type phenolic resins, and cyclopentadiene type phenolic resins. These curing agents may be used alone or in admixture of two or more. Several preferred, non-limiting examples of the curing agent are given below.
- m is an integer of 0 to 10 and preferably 0 to 5.
- the curing agent is blended in an effective amount to cause the epoxy resin to cure.
- a phenolic resin is used as the curing agent, it is preferably blended in an epoxy resin in such amounts that 0.5 to 1.6 mol, more preferably 0.6 to 1.4 mol of phenolic hydroxyl groups are available per mol of epoxy groups. Less than 0.5 mol of hydroxyl groups have a possibility that more epoxy groups polymerize alone (homo-polymerization), resulting in a lower glass transition temperature. More than 1.6 mol means an excess of phenolic hydroxyl groups which may lower reactivity, resulting in a lower crosslinking density and insufficient strength.
- the porous silica used herein as the inorganic filler should have a specific surface area of 6 to 200 m 2 /g as expressed in BET specific surface by the nitrogen adsorption method, a true specific gravity of 2.0 to 2.2, and a mean particle size of 2 to 50 ⁇ m. It is noted that the mean particle size as used herein can be determined, for example, as the weight average (or median diameter) in the particle size distribution as measured by the laser light diffraction method.
- the porous silica has a specific surface area of 6 to 200 m 2 /g and preferably 20 to 150 m 2 /g. Silica with a specific surface of less than 6 m 2 /g has a poor water absorbing capacity whereas a specific surface of more than 200 m 2 /g adversely affects the flow.
- the porous silica has a true specific gravity of 2.0 to 2.2. Silica with a true specific gravity of less than 2.0 has an insufficient degree of sintering and is less wettable to the epoxy resin. A true specific gravity of more than 2.2 indicates mixing of crystalline silica, which is outside the scope of porous silica which is amorphous. Additionally the porous silica has a mean particle size of 2 to 50 ⁇ m and preferably 4 to 20 ⁇ m. Outside this range, there can arise some problems including retarded flow and burr formation.
- the content of each of alkali metals such as Na and K and alkaline earth metals such as Mg and Ca should preferably be 1 ppm or lower. Most preferably the total content of alkali and alkaline earth metals is 1 ppm or lower.
- a higher content of such ionic impurities can reduce the activity of the curing catalyst, resulting in undercure. In a composition having a large amount of porous silica added, this tendency becomes outstanding if the content of ionic impurities is high.
- the porous silica itself has a water absorbing capacity corresponding to a moisture pickup of at least 0.3%, more preferably at least 0.4%, and most preferably at least 1.0% by weight when kept at 25° C. and RH 70% for 24 hours. If the moisture pickup of porous silica is less than 0.3% by weight, the composition filled therewith may have an insufficient water absorbing capacity.
- the porous silica has a pore volume of 0.05 to 10 ml/g, more preferably of 0.1 to 1.0 ml/g and a pore diameter of 3 to 100 ⁇ .
- the porous silica is prepared by forming a silica gel having a weight average particle size of up to 50 ⁇ m by a sol-gel process, and firing the silica gel at a temperature of 700 to 1,200° C.
- the sol-gel process used herein may be any of the methods described in JP-B 7-98659, JP-A 62-283809 and JP-A 62-3011 both corresponding to U.S. Pat. No. 4,683,128, for example.
- the porous silica takes the form of spherical particles or fragments.
- spherical porous silica is obtained by forcedly agitating an aqueous alkali metal silicate emulsion in the presence of a surfactant, followed by water washing, drying, and sintering.
- Fragment porous silica is obtained by extruding an aqueous alkali metal silicate emulsion into a water-miscible organic solvent or acid solution through orifices, treating the resulting fibrous coagulums with an acidic solution, washing them with water to extract impurities away, followed by pulverization and sintering.
- the preferred conditions under which the porous silica obtained by the sol-gel process is fired include a temperature of about 700 to 1,200° C., more preferably about 800 to 1,100° C. and a time of about 2 to 16 hours, more preferably about 4 to 12 hours. If the firing temperature is below 700° C. or the firing time is too short, silica is sintered to an insufficient extent to be wettable to the epoxy resin and curing agent, failing to provide smooth flow. If the firing temperature is above 1,200° C. or the firing time is too long, the number of pores on the silica surface is reduced due to over-sintering so that the silica may have a low water absorbing capacity.
- the porous silica used herein is in the form of spherical particles or fragments.
- Spherical particles are preferred when the composition flow is taken into account.
- Silica fragments are preferred for the mechanical strength of the composition in the cured state. Since spherical particles are superior to fragments with respect to the water absorbing capacity of porous silica, it is preferred for increasing the water absorbing capacity to add spherical particles more. It is noted that the magnitude of water absorbing capacity depends on the size of pores.
- the proportion of spherical particles and fragments is not critical although a weight ratio of fragments/spherical particles in the range from 0/10 to 3/7 is preferred for a good balance of flow and strength. Particularly when a large amount of porous silica is added, it is recommended to increase the proportion of spherical particles.
- the amount of porous silica added is preferably 40 to 90%, more preferably 50 to 90%, most preferably 55 to 80% by weight of the entire epoxy resin composition. If the amount of porous silica added is less than 40% by weight, the composition may sometimes have a poor capacity to trap externally penetrating water, failing to achieve the desired low moisture permeability. If the amount of porous silica added is greater than 90% by weight, the composition may become less flowable and difficult to mold.
- porous silica While it is essential that the porous silica be used as the inorganic filler, other inorganic fillers may be additionally blended in the epoxy resin composition of the invention.
- Such other inorganic fillers include fused silica as milled in a ball mill, spherical silica obtained by flame fusion, crystalline silica, fumed silica, precipitated silica, alumina, boron nitride, aluminum nitride, silicon nitride, magnesia, and magnesium silicate.
- the other inorganic filler if any, is used in such amounts that the total of inorganic fillers (inclusive of the inventive porous silica) may be 100 to 1,000 parts by weight per 100 parts by weight of the epoxy resin and curing agent combined. If the total amount is less than 100 parts, the composition may have a higher coefficient of expansion. If the total amount is more than 1,000 parts, the composition may become too viscous to mold. More preferably the total amount is 200 to 900 parts by weight.
- the inorganic filler is preferably surface treated beforehand with coupling agents such as silane and titanate coupling agents.
- Preferred coupling agents are silane coupling agents in the form of alkoxysilanes having alkyl groups substituted with such functional groups as epoxy, amino and mercapto groups, including epoxy silanes such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, and ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane; aminosilanes such as N- ⁇ -(aminoethyl)- ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, and N-phenyl- ⁇ -amino-propyltrimethoxysilane; and mercaptosilanes such as
- inventive composition conventional well-known silicone rubber and gel in powder form, silicone-modified epoxy resins, silicone-modified phenolic resins, and thermoplastic resins such as methyl methacrylate-butadiene-styrene copolymers may be added as stress-relieving agents and adhesives.
- a curing accelerator is preferably used for promoting the curing reaction between the epoxy resin and the curing agent.
- the curing accelerator may be any suitable substance that promotes the curing reaction.
- Illustrative, non-limiting examples of curing accelerators that may be used include organic phosphorus compounds such as triphenylphosphine, tributylphosphine, tri(p-methylphenyl)phosphine, tri(nonylphenyl)phosphine, triphenylphosphine triphenyl-borate, and tetraphenylphosphine tetraphenylborate; tertiary amine compounds such as triethylamine, benzyldimethylamine, ⁇ -methylbenzyldimethylamine, and 1,8-diazabicyclo[5.4.0]-undecene-7; and imidazole compounds such as 2-methyl-imidazole, 2-phenylimidazole, and 2-pheny
- the epoxy resin composition may further include various additives, if necessary.
- Illustrative examples include coupling agents such as silane, titanium and aluminum coupling agents; colorants such as carbon black; parting agents such as natural wax; wetting modifiers such as fluorochemical surfactants and silicone oil; and halogen trapping agents.
- the epoxy resin composition may be prepared by uniformly mixing the essential and optional ingredients in a high-speed mixer or other appropriate apparatus, and fully milling the mixture in a roll mill or continuous kneader.
- the desired milling temperature is about 50 to 120° C. After milling, the compound is sheeted, cooled and ground.
- the resulting epoxy resin composition is useful as a general molding material and especially a semiconductor encapsulant.
- the epoxy resin composition of the invention can be effectively used for encapsulating various types of semiconductor devices, and especially for forming premolded hollow packages.
- the method of encapsulation most commonly used is low-pressure transfer molding.
- the epoxy resin composition is preferably molded at a temperature of about 150 to 180° C. for a period of about 30 to 180 seconds, followed by postcuring at about 150 to 180° C. for about 2 to 16 hours.
- the package is encapsulated with a cured product of an epoxy resin composition comprising an epoxy resin, a curing agent, and an inorganic filler.
- the inorganic filler includes a porous silica having a specific surface area of 6 to 200 m 2 /g, a true specific gravity of 2.0 to 2.2, and a mean particle size of 2 to 50 ⁇ m, as described above.
- the amount of the porous silica in the cured product or the entire epoxy resin composition is described above and preferably at least 55% by weight.
- Semiconductor-encapsulating epoxy resin compositions were prepared by mixing the porous silica shown in Table 1 with the ingredients shown in Tables 2 and 3, and uniformly melt milling the mixture in a hot two-roll mill, followed by cooling and grinding.
- the spiral flow was measured by molding the composition at 175° C. and 6.9 N/mm 2 for 120 seconds in a mold in accordance with EMMI standards.
- the gel time was measured as the time until the epoxy resin composition gelled on a hot plate at 175° C.
- melt viscosity was measured at 175° C. under a load of 10 kg with a constant-load orifice-type flow testing apparatus of the kind known in Japan as a Koka-type flow tester (Shimadzu Mfg. K. K.).
- a shear bond strength test piece was prepared by molding the composition over a frame of Alloy 42 at 175° C. and 6.9 N/mm 2 for 120 seconds and curing at 180° C. for 4 hours. A bonding force was measured. The bond area between the frame and the resin was 10 mm 2 .
- a disc having a diameter of 50 mm and a thickness of 3 mm was molded at 175° C. and 6.9 N/mm 2 for 120 seconds and cured at 180° C. for 4 hours. The disc was held at 85° C. and RH 85% for 48 hours before the amount of water absorbed was measured.
- a disc having a diameter of 50 mm and a thickness of 3 mm was molded at 175° C. and 6.9 N/mm 2 for 120 seconds and cured at 180° C. for 4 hours.
- Thermal conductivity was measured in accordance with ASTM E 1530 using ANTAR 2021.
- a premolded package 1 of hollow box shape as shown in FIG. 1 was prepared by molding the epoxy resin composition over a lead frame 2 (including inner and outer leads 2 a and 2 b ) at 175° C. and 6.9 N/mm 2 for 120 seconds and postcuring at 180° C. for 4 hours.
- a transparent glass shield 4 was joined to the top of the package 1 with an epoxy resin adhesive 3 , completing the hollow package. Note that a semiconductor chip 5 and metal bonding wires 6 are on the lead frame 2 .
- This package was subjected to a thermal cycling test.
- the test procedure included four steps of (1) holding in an atmosphere of 121° C./RH 100%/2 atm. for 4 hours, (2) holding at room temperature (25° C.) for 30 minutes, (3) placing the glass shield in contact with a hot plate at 100° C. for 10 seconds, and (4) placing the glass shield in contact with an iron plate at room temperature for 7 seconds. This was repeated four cycles. It was observed whether or not the glass shield was clouded by dew condensation. The sample was rated “NG? when dew condensation occurred in the first cycle, and “1,” 2,” “3” and “4” when it cleared the first, second, third and fourth cycle, respectively.
- porous silica Nos. 1 to 5 were respectively prepared by forming a silica gel having a weight average particle size of 9.2 ⁇ m, 10 ⁇ m, 17 ⁇ m, 32 ⁇ m and 13 ⁇ m by the sol-gel process, and firing the silica gel at the indicated temperature for 8 hours.
- the contents of Al, Fe, Na, Ca, Mg and K were measured by ICP, and the content of U was measured by fluorescent x-ray analysis.
- Porous silica Nos. 1 to 4 were used in Examples and porous silica No. 5 and AMT #2000 (zeolite by Mizusawa Chemical K. K.) were used in Comparative Examples.
- the epoxy resin compositions within the scope of the invention and the semiconductor packages encapsulated therewith exhibit excellent properties as demonstrated by the above Examples. It is seen from Table 2 that when silica having a smaller specific surface area and a smaller moisture pickup is used, the hollow package does not provide a satisfactory hermetic seal in the hermetic test. When conventional porous silica (zeolite) is used, flow, cure, adhesion and hermetic seal are unsatisfactory under the influence of impurities. It is seen from Table 3 that when porous silica within the scope of the invention is used, but in a smaller amount, the results of the hermetic test are unsatisfactory. The hermetic level rises as the amount of porous silica added increases.
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
- This invention relates to epoxy resin compositions which are easily moldable, have a low moisture permeability and reliability in the cured state, and are suitable for encapsulating semiconductor chips and especially as premolded hollow semiconductor packages. It also relates to premolded hollow semiconductor packages encapsulated with the epoxy resin compositions in the cured state.
- In the electrical and electronic fields, epoxy resins featuring mechanical strength, moisture resistance and moldability find a variety of applications as insulating materials, laminates, adhesives and semiconductor encapsulants.
- As opposed to essentially moisture impermeable metals and ceramics, epoxy resins classified as thermosetting resins have a coefficient of moisture diffusion. Upon exposure to humid conditions, epoxy resins absorb moisture and allow moisture to permeate therethrough. The moisture permeability of thermosetting resins often becomes a problem when they are used in the application requiring hermetic and water-proof seals, for example, in precision machines such as watches and electronic calculators, and electronic parts such as semiconductor packages, especially solid state imaging device (generally known as CCD) hollow packages and quartz oscillator hollow packages. For example, resin packages of CCD slowly absorb moisture when exposed to a hot humid environment for an extended period of time, though not in direct contact with water. If moisture is introduced into the hermetic space in excess of the saturated steam amount determined from the saturated water vapor pressure, moisture condenses. The device becomes inoperable by dew condensation.
- An improvement in moisture permeability has long been desired for prior art epoxy resin compositions comprising an epoxy resin, a curing agent and an inorganic filler for use in hollow packages. One known means is to add an inorganic desiccant to the epoxy resin composition so that the desiccant adsorbs moisture permeating through the cured item, preventing moisture from entering the hollow interior.
- JP-A 8-157694 of the same assignee as the present invention discloses an epoxy resin composition comprising at least 10 parts by weight of an inorganic desiccant per 100 parts by weight of an epoxy resin and a curing agent combined. Specifically, using AMT silica by Mizusawa Chemical K. K. as the inorganic desiccant, the composition is rendered low moisture permeable.
- AMT silica, however, has a low true specific gravity and contains a relatively large amount of ionic impurities since it is porous silica obtained by sintering zeolite. The low true specific gravity means that a certain weight of silica added accounts for a larger volume so that an increased amount of silica can obstruct flow. The large amount of ionic impurities interfere with the curing function of the curing catalyst so that cure may become short, resulting in drops of hot strength and bond strength.
- JP 2,750,254 (JPA 6-232292) discloses a semiconductor package comprising an insulating substrate containing 0.1 to 50% by weight of a desiccant. The amount of desiccant added to an epoxy resin composition should preferably be increased since a small amount of desiccant does not fully adsorb moisture penetrating through the cured item. Illustratively, in a moisture permeation reliability test, a package sample containing a small amount of desiccant allows moisture to reach the cavity so that moisture may condense on the glass lid. This drawback can be eliminated by increasing the amount of desiccant. However, since conventional desiccants are poorly compatible with epoxy resins and curing agents, they exacerbate the flow particularly when added in large amounts. The epoxy resin composition with retarded flow can cause such defects as short shots and voids when molded by a transfer molding machine, and is thus unsuitable for semiconductor encapsulating purposes.
- An object of the invention is to provide an epoxy resin composition which is flowable and easily moldable and cures into a product having a low moisture permeability, and a premolded hollow semiconductor package encapsulated with the epoxy resin composition in the cured state.
- We have found that an epoxy resin composition comprising an epoxy resin, a curing agent, and an inorganic filler flows smoothly and is easily moldable when the filler is porous silica having a specific surface area of 6 to 200 m2/g, a true specific gravity of 2.0 to 2.2, and a mean particle size of 2 to 50 μm. The composition cures into a product of quality having a low moisture permeability. In summary, the composition is smoothly flowable and readily bondable and curable into a product having minimized moisture permeation. The composition is thus suited for forming premolded hollow semiconductor packages.
- Accordingly the invention provides an epoxy resin composition comprising an epoxy resin, a curing agent, and an inorganic filler in the form of porous silica having a specific surface area of 6 to 200 m2/g, a true specific gravity of 2.0 to 2.2, and a mean particle size of 2 to 50 μm. In some preferred embodiments, the porous silica has been prepared by forming a silica gel having a weight average particle size of up to 50 μm by a sol-gel process, and firing the silica gel at a temperature of 700 to 1,200° C.; the porous silica has a moisture pickup of at least 0.3% by weight when kept at 25° C. and RH 70% for 24 hours; the porous silica contains up to 1 ppm of each of alkali and alkaline earth metals. The porous silica preferably accounts for 40 to 90% by weight, more preferably at least 55% by weight of the entire epoxy resin composition.
- The invention also provides a premolded hollow semiconductor package encapsulated with a cured product of an epoxy resin composition comprising an epoxy resin, a curing agent, and an inorganic filler including a porous silica having a specific surface area of 6 to 200 m2/g, a true specific gravity of 2.0 to 2.2, and a mean particle size of 2 to 50 μm.
- The only figure, FIG. 1 is a schematic cross-sectional view of a premolded hollow semiconductor package molded in Examples.
- The epoxy resin composition according to the invention contains an epoxy resin, a curing agent, and an inorganic filler. The epoxy resin used herein is not limited in molecular structure and molecular weight as long as it has at least two epoxy groups in a molecule and can be cured with curing agents to be described later. A proper choice may be made among conventional well-known epoxy resins. Examples of useful epoxy resins include bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins, novolak type epoxy resins such as phenol novolak type epoxy resins and cresol novolak type epoxy resins, triphenolalkane type epoxy resins such as triphenolmethane type epoxy resins and triphenolpropane type epoxy resins and polymers thereof, epoxy resins having a biphenyl skeleton, epoxy resins having a naphthalene skeleton, dicyclopentadiene-phenol novolak resins, phenolaralkyl type epoxy resins, glycidyl ester type epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, and halogenated epoxy resins. Several preferred epoxy resins are illustrated by the following formulas although the epoxy resin is not limited thereto.
- Herein, G is glycidyl, Me is methyl, and n is an integer of 0 to 10, and preferably 0 to 5.
- The curing agent is not critical and may be any of phenolic compounds, amine compounds and acid anhydrides commonly used for the curing of conventional epoxy resins. Of these, phenolic resins having at least two phenolic hydroxyl groups per molecule are preferred. Exemplary curing agents include bisphenol type resins such as bisphenol A type resins and bisphenol F type resins; novolak-type phenolic resins such as phenolic novolak resins and cresol novolak resins; triphenolalkane resins such as triphenolmethane resins and triphenolpropane resins; resole type phenolic resins, phenol aralkyl resins, biphenyl type phenolic resins, naphthalene type phenolic resins, and cyclopentadiene type phenolic resins. These curing agents may be used alone or in admixture of two or more. Several preferred, non-limiting examples of the curing agent are given below.
- Herein, m is an integer of 0 to 10 and preferably 0 to 5.
- The curing agent is blended in an effective amount to cause the epoxy resin to cure. When a phenolic resin is used as the curing agent, it is preferably blended in an epoxy resin in such amounts that 0.5 to 1.6 mol, more preferably 0.6 to 1.4 mol of phenolic hydroxyl groups are available per mol of epoxy groups. Less than 0.5 mol of hydroxyl groups have a possibility that more epoxy groups polymerize alone (homo-polymerization), resulting in a lower glass transition temperature. More than 1.6 mol means an excess of phenolic hydroxyl groups which may lower reactivity, resulting in a lower crosslinking density and insufficient strength.
- The porous silica used herein as the inorganic filler should have a specific surface area of 6 to 200 m2/g as expressed in BET specific surface by the nitrogen adsorption method, a true specific gravity of 2.0 to 2.2, and a mean particle size of 2 to 50 μm. It is noted that the mean particle size as used herein can be determined, for example, as the weight average (or median diameter) in the particle size distribution as measured by the laser light diffraction method.
- More illustratively, the porous silica has a specific surface area of 6 to 200 m2/g and preferably 20 to 150 m2/g. Silica with a specific surface of less than 6 m2/g has a poor water absorbing capacity whereas a specific surface of more than 200 m2/g adversely affects the flow. The porous silica has a true specific gravity of 2.0 to 2.2. Silica with a true specific gravity of less than 2.0 has an insufficient degree of sintering and is less wettable to the epoxy resin. A true specific gravity of more than 2.2 indicates mixing of crystalline silica, which is outside the scope of porous silica which is amorphous. Additionally the porous silica has a mean particle size of 2 to 50 μm and preferably 4 to 20 μm. Outside this range, there can arise some problems including retarded flow and burr formation.
- In the porous silica, the content of each of alkali metals such as Na and K and alkaline earth metals such as Mg and Ca should preferably be 1 ppm or lower. Most preferably the total content of alkali and alkaline earth metals is 1 ppm or lower. A higher content of such ionic impurities can reduce the activity of the curing catalyst, resulting in undercure. In a composition having a large amount of porous silica added, this tendency becomes outstanding if the content of ionic impurities is high.
- Also preferably, the porous silica itself has a water absorbing capacity corresponding to a moisture pickup of at least 0.3%, more preferably at least 0.4%, and most preferably at least 1.0% by weight when kept at 25° C. and RH 70% for 24 hours. If the moisture pickup of porous silica is less than 0.3% by weight, the composition filled therewith may have an insufficient water absorbing capacity.
- Further preferably the porous silica has a pore volume of 0.05 to 10 ml/g, more preferably of 0.1 to 1.0 ml/g and a pore diameter of 3 to 100 Å.
- In one preferred embodiment, the porous silica is prepared by forming a silica gel having a weight average particle size of up to 50 μm by a sol-gel process, and firing the silica gel at a temperature of 700 to 1,200° C. The sol-gel process used herein may be any of the methods described in JP-B 7-98659, JP-A 62-283809 and JP-A 62-3011 both corresponding to U.S. Pat. No. 4,683,128, for example. Depending on its preparation method, the porous silica takes the form of spherical particles or fragments. For example, spherical porous silica is obtained by forcedly agitating an aqueous alkali metal silicate emulsion in the presence of a surfactant, followed by water washing, drying, and sintering. Fragment porous silica is obtained by extruding an aqueous alkali metal silicate emulsion into a water-miscible organic solvent or acid solution through orifices, treating the resulting fibrous coagulums with an acidic solution, washing them with water to extract impurities away, followed by pulverization and sintering.
- The preferred conditions under which the porous silica obtained by the sol-gel process is fired include a temperature of about 700 to 1,200° C., more preferably about 800 to 1,100° C. and a time of about 2 to 16 hours, more preferably about 4 to 12 hours. If the firing temperature is below 700° C. or the firing time is too short, silica is sintered to an insufficient extent to be wettable to the epoxy resin and curing agent, failing to provide smooth flow. If the firing temperature is above 1,200° C. or the firing time is too long, the number of pores on the silica surface is reduced due to over-sintering so that the silica may have a low water absorbing capacity.
- As mentioned above, the porous silica used herein is in the form of spherical particles or fragments. Spherical particles are preferred when the composition flow is taken into account. Silica fragments are preferred for the mechanical strength of the composition in the cured state. Since spherical particles are superior to fragments with respect to the water absorbing capacity of porous silica, it is preferred for increasing the water absorbing capacity to add spherical particles more. It is noted that the magnitude of water absorbing capacity depends on the size of pores. The proportion of spherical particles and fragments is not critical although a weight ratio of fragments/spherical particles in the range from 0/10 to 3/7 is preferred for a good balance of flow and strength. Particularly when a large amount of porous silica is added, it is recommended to increase the proportion of spherical particles.
- The amount of porous silica added is preferably 40 to 90%, more preferably 50 to 90%, most preferably 55 to 80% by weight of the entire epoxy resin composition. If the amount of porous silica added is less than 40% by weight, the composition may sometimes have a poor capacity to trap externally penetrating water, failing to achieve the desired low moisture permeability. If the amount of porous silica added is greater than 90% by weight, the composition may become less flowable and difficult to mold.
- While it is essential that the porous silica be used as the inorganic filler, other inorganic fillers may be additionally blended in the epoxy resin composition of the invention. Such other inorganic fillers include fused silica as milled in a ball mill, spherical silica obtained by flame fusion, crystalline silica, fumed silica, precipitated silica, alumina, boron nitride, aluminum nitride, silicon nitride, magnesia, and magnesium silicate. Preferably, the other inorganic filler, if any, is used in such amounts that the total of inorganic fillers (inclusive of the inventive porous silica) may be 100 to 1,000 parts by weight per 100 parts by weight of the epoxy resin and curing agent combined. If the total amount is less than 100 parts, the composition may have a higher coefficient of expansion. If the total amount is more than 1,000 parts, the composition may become too viscous to mold. More preferably the total amount is 200 to 900 parts by weight.
- For enhancing the bond strength of the inorganic filler to the resin, the inorganic filler is preferably surface treated beforehand with coupling agents such as silane and titanate coupling agents. Preferred coupling agents are silane coupling agents in the form of alkoxysilanes having alkyl groups substituted with such functional groups as epoxy, amino and mercapto groups, including epoxy silanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; aminosilanes such as N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N-phenyl-γ-amino-propyltrimethoxysilane; and mercaptosilanes such as γ-mercaptosilanes. No particular limitation is imposed on the amount of coupling agent used for surface treatment or the method of surface treatment.
- In the inventive composition, conventional well-known silicone rubber and gel in powder form, silicone-modified epoxy resins, silicone-modified phenolic resins, and thermoplastic resins such as methyl methacrylate-butadiene-styrene copolymers may be added as stress-relieving agents and adhesives.
- In the practice of this invention, a curing accelerator is preferably used for promoting the curing reaction between the epoxy resin and the curing agent. The curing accelerator may be any suitable substance that promotes the curing reaction. Illustrative, non-limiting examples of curing accelerators that may be used include organic phosphorus compounds such as triphenylphosphine, tributylphosphine, tri(p-methylphenyl)phosphine, tri(nonylphenyl)phosphine, triphenylphosphine triphenyl-borate, and tetraphenylphosphine tetraphenylborate; tertiary amine compounds such as triethylamine, benzyldimethylamine, α-methylbenzyldimethylamine, and 1,8-diazabicyclo[5.4.0]-undecene-7; and imidazole compounds such as 2-methyl-imidazole, 2-phenylimidazole, and 2-phenyl-4-methyl-imidazole. An appropriate amount of the curing accelerator is about 0.01 to 10 parts by weight per 100 parts by weight of the epoxy resin and curing agent (e.g., phenolic resin) combined.
- The epoxy resin composition may further include various additives, if necessary. Illustrative examples include coupling agents such as silane, titanium and aluminum coupling agents; colorants such as carbon black; parting agents such as natural wax; wetting modifiers such as fluorochemical surfactants and silicone oil; and halogen trapping agents.
- The epoxy resin composition may be prepared by uniformly mixing the essential and optional ingredients in a high-speed mixer or other appropriate apparatus, and fully milling the mixture in a roll mill or continuous kneader. The desired milling temperature is about 50 to 120° C. After milling, the compound is sheeted, cooled and ground. The resulting epoxy resin composition is useful as a general molding material and especially a semiconductor encapsulant.
- The epoxy resin composition of the invention can be effectively used for encapsulating various types of semiconductor devices, and especially for forming premolded hollow packages. The method of encapsulation most commonly used is low-pressure transfer molding. The epoxy resin composition is preferably molded at a temperature of about 150 to 180° C. for a period of about 30 to 180 seconds, followed by postcuring at about 150 to 180° C. for about 2 to 16 hours.
- In the premolded hollow semiconductor package of the present invention, the package is encapsulated with a cured product of an epoxy resin composition comprising an epoxy resin, a curing agent, and an inorganic filler. The inorganic filler includes a porous silica having a specific surface area of 6 to 200 m2/g, a true specific gravity of 2.0 to 2.2, and a mean particle size of 2 to 50 μm, as described above. The amount of the porous silica in the cured product or the entire epoxy resin composition is described above and preferably at least 55% by weight.
- Examples of the invention are given below by way of illustration and not by way of limitation. All parts are by weight.
- Semiconductor-encapsulating epoxy resin compositions were prepared by mixing the porous silica shown in Table 1 with the ingredients shown in Tables 2 and 3, and uniformly melt milling the mixture in a hot two-roll mill, followed by cooling and grinding.
- These epoxy resin compositions were examined for various properties by the following tests (1) to (9). The results are also shown in Tables 2 and 3.
- (1) Spiral Flow:
- The spiral flow was measured by molding the composition at 175° C. and 6.9 N/mm2 for 120 seconds in a mold in accordance with EMMI standards.
- (2) Gel time
- The gel time was measured as the time until the epoxy resin composition gelled on a hot plate at 175° C.
- (3) Melt viscosity
- The melt viscosity was measured at 175° C. under a load of 10 kg with a constant-load orifice-type flow testing apparatus of the kind known in Japan as a Koka-type flow tester (Shimadzu Mfg. K. K.).
- (4) Hardness as molded
- According to JIS K6911, a rod measuring 100×10×4 mm was molded at 175° C. and 6.9 N/mm2 for 120 seconds. The hardness when hot was measured with a Barcol Impressor.
- (5) Flexural strength
- According to JIS K6911, a rod measuring 100×10×4 mm was molded at 175° C. and 6.9 N/mm2 for 120 seconds and cured at 180° C. for 4 hours before it was measured for flexural strength.
- (6) Adhesion
- A shear bond strength test piece was prepared by molding the composition over a frame of Alloy 42 at 175° C. and 6.9 N/mm2 for 120 seconds and curing at 180° C. for 4 hours. A bonding force was measured. The bond area between the frame and the resin was 10 mm2.
- (7) Moisture pickup
- A disc having a diameter of 50 mm and a thickness of 3 mm was molded at 175° C. and 6.9 N/mm2 for 120 seconds and cured at 180° C. for 4 hours. The disc was held at 85° C. and RH 85% for 48 hours before the amount of water absorbed was measured.
- (8) Thermal conductivity
- A disc having a diameter of 50 mm and a thickness of 3 mm was molded at 175° C. and 6.9 N/mm2 for 120 seconds and cured at 180° C. for 4 hours. Thermal conductivity was measured in accordance with ASTM E 1530 using ANTAR 2021.
- (9) Hermetic test
- A
premolded package 1 of hollow box shape as shown in FIG. 1 was prepared by molding the epoxy resin composition over a lead frame 2 (including inner andouter leads transparent glass shield 4 was joined to the top of thepackage 1 with anepoxy resin adhesive 3, completing the hollow package. Note that a semiconductor chip 5 andmetal bonding wires 6 are on thelead frame 2. - This package was subjected to a thermal cycling test. The test procedure included four steps of (1) holding in an atmosphere of 121° C./RH 100%/2 atm. for 4 hours, (2) holding at room temperature (25° C.) for 30 minutes, (3) placing the glass shield in contact with a hot plate at 100° C. for 10 seconds, and (4) placing the glass shield in contact with an iron plate at room temperature for 7 seconds. This was repeated four cycles. It was observed whether or not the glass shield was clouded by dew condensation. The sample was rated “NG? when dew condensation occurred in the first cycle, and “1,” 2,” “3” and “4” when it cleared the first, second, third and fourth cycle, respectively.
TABLE 1 Used in Used in Example Comparative Example Porous silica 1 2 3 4 5 AMT#2000 Shape spherical spherical spherical fragment spherical — Sintering temp. (° C.) 800 900 980 1,100 1,250 — Mean particle size 8.7 9.6 16 31 15 2 (μm) Specific surface(m2/g) 144 75 21 35 4 125 Moisture pickup @ 15 7.4 3.4 0.48 0.2 17 25° C./RH70%/24 hr (wt %) Extracted water pH 4.4 4.4 4.5 4.4 4.5 5.8 True specific gravity 2.1 2.2 2.2 2.2 2.2 1.9 (g/cm3) Specific gravity 0.95 1.00 1.00 1.00 1.00 0.86 ratio to specific gravity 2.20 fused silica Al content (ppm) 1.0 1.2 1.0 0.9 0.9 1,100 Fe content (ppm) 2.1 2.0 2.3 2.0 2.3 25 Total content of <1 <1 <1 <1 <1 243 alkali metal (Na and K) (ppm) Total content of <1 <1 <1 <1 <1 364 alkali earth metal (Mg and Ca) (ppm) U content (ppb) 0.1 0.1 0.1 0.1 0.1 1.4 - Note that porous silica Nos. 1 to 5 were respectively prepared by forming a silica gel having a weight average particle size of 9.2 μm, 10 μm, 17 μm, 32 μm and 13 μm by the sol-gel process, and firing the silica gel at the indicated temperature for 8 hours. The contents of Al, Fe, Na, Ca, Mg and K were measured by ICP, and the content of U was measured by fluorescent x-ray analysis. Porous silica Nos. 1 to 4 were used in Examples and porous silica No. 5 and AMT #2000 (zeolite by Mizusawa Chemical K. K.) were used in Comparative Examples.
TABLE 2 Example Comparative Example Formulation (pbw) 1 2 3 4 5 1 2 Novolak type epoxy resin1) 59.1 59.1 59.1 59.1 59.1 59.1 59.1 Curing agent3) 35.4 35.4 35.4 35.4 35.4 35.4 35.4 Brominated epoxy resin5) 5 5 5 5 5 5 5 Silane coupling agent6) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Hoechst Wax E 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Triphenyiphosphine 1.3 1.3 1.3 1.3 1.3 1.3 1.3 Sb2O3 5 5 5 5 5 5 5 Porous silica No. 1 346 — — 277 277 — — Porous silica No. 2 — 346 — — — — — Porous silica No. 3 — — 346 — — — — Porous silica No. 4 — — — 69 — — — Porous silica No. 5 — — — — — 346 — AMT #2000 — — — — — — 346 Spherical silica7) 18 18 18 18 18 18 18 Micro-spherical silica8) 104 104 104 104 104 104 104 Micro-spherical silica9) 52 52 52 52 52 52 52 Spherical alumina10) — — — — 69 — — Porous silica content (wt %) 55 55 55 55 44 55 — Spiral flow (cm) 95 105 110 95 96 106 32 Gel time (sec) 16 16 15 16 15 16 20 Melt viscosity (Pa · s) 20 18 18 20 16 18 500 Molded hardness 85 87 85 85 86 87 75 Flexural strength (N/mm2) 142 142 132 142 142 142 108 Bonding force (kg) 4.2 4.1 3.9 4.3 4.0 3.8 0.2 Moisture pickup (wt %) 3.0 2.3 2.1 1.8 1.8 1.0 3.0 Thermal conductivity (W/mK) 0.9 0.9 0.9 0.9 1.4 0.9 0.9 Hermetic test 4 4 4 4 3 NG 1 -
TABLE 3 Example Comparative Example Formulation (pbw) 6 7 8 9 10 3 Novolac type epoxy resin1) 59.1 59.1 59.1 59.1 — 59.1 Biphenyl type epoxy resin2) — — — — 45.6 — Curing agent3) 35.4 35.4 35.4 35.4 — 35.4 Curing agent4) — — — — 47.0 — Brominated epoxy resin5) 5 5 5 5 5 5 Silane coupling agent6) 1.5 1.5 1.5 1.5 1.5 1.5 Hoechst Wax E 1.5 1.5 1.5 1.5 1.5 1.5 Triphenyiphosphine 1.3 1.3 1.3 1.3 1.3 1.3 Sb2O3 5 5 5 5 5 5 Porous silica No. 1 63 315 378 362 472.5 — Spherical silica7) 301 49 — 56 73.5 364 Micro-spherical silica8) 104 104 90 120 156 104 Micro-spherical silica9) 52 52 52 60 78 52 Porous silica content (wt %) 10 50 60 51 53 — Spiral flow (cm) 115 112 90 95 100 120 Gel time (sec) 16 16 16 16 16 16 Melt viscosity (Pa.s) 19 18 21 16 18 14 Molded hardness 85 86 87 86 85 86 Flexural strength (N/nm2) 142 137 147 147 147 137 Bonding force (kg) 4.1 3.9 3.9 4.2 4.0 2.8 Moisture pickup (wt %) 0.7 3.1 3.3 2.6 2.2 0.4 Hermetic test 1 3 4 3 3 NC - The epoxy resin compositions within the scope of the invention and the semiconductor packages encapsulated therewith exhibit excellent properties as demonstrated by the above Examples. It is seen from Table 2 that when silica having a smaller specific surface area and a smaller moisture pickup is used, the hollow package does not provide a satisfactory hermetic seal in the hermetic test. When conventional porous silica (zeolite) is used, flow, cure, adhesion and hermetic seal are unsatisfactory under the influence of impurities. It is seen from Table 3 that when porous silica within the scope of the invention is used, but in a smaller amount, the results of the hermetic test are unsatisfactory. The hermetic level rises as the amount of porous silica added increases.
- There has been described a porous silica-loaded epoxy resin composition which is easy to mold and cures into a part having low moisture permeability and high reliability.
- Japanese Patent Application No. 11-342946 is incorporated herein by reference.
- Although some preferred embodiments have been described, many modifications and variations may be made thereto in light of the above teachings. It is therefore to be understood that the invention may be practiced otherwise than as specifically described without departing from the scope of the appended claims.
Claims (8)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/988,752 US6569532B2 (en) | 1999-12-02 | 2001-11-20 | Epoxy resin compositions and premolded semiconductor packages |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP34294699 | 1999-12-02 | ||
JP11-342946 | 1999-12-02 | ||
JP2000-360597 | 2000-11-28 | ||
JP2000360597A JP4614214B2 (en) | 1999-12-02 | 2000-11-28 | Hollow package for semiconductor device elements |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/988,752 Division US6569532B2 (en) | 1999-12-02 | 2001-11-20 | Epoxy resin compositions and premolded semiconductor packages |
Publications (2)
Publication Number | Publication Date |
---|---|
US20010004651A1 true US20010004651A1 (en) | 2001-06-21 |
US6399677B2 US6399677B2 (en) | 2002-06-04 |
Family
ID=26577387
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/726,575 Expired - Lifetime US6399677B2 (en) | 1999-12-02 | 2000-12-01 | Epoxy resin compositions and premolded semiconductor packages |
US09/988,752 Expired - Lifetime US6569532B2 (en) | 1999-12-02 | 2001-11-20 | Epoxy resin compositions and premolded semiconductor packages |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/988,752 Expired - Lifetime US6569532B2 (en) | 1999-12-02 | 2001-11-20 | Epoxy resin compositions and premolded semiconductor packages |
Country Status (4)
Country | Link |
---|---|
US (2) | US6399677B2 (en) |
JP (1) | JP4614214B2 (en) |
KR (1) | KR100678345B1 (en) |
TW (1) | TW561177B (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030168731A1 (en) * | 2002-03-11 | 2003-09-11 | Matayabas James Christopher | Thermal interface material and method of fabricating the same |
US20090084602A1 (en) * | 2007-09-28 | 2009-04-02 | Shin-Etsu Chemical Co., Ltd. | Automotive electric/electronic package |
US20120153513A1 (en) * | 2007-05-17 | 2012-06-21 | Nitto Denko Corporation | Thermosetting encapsulation adhesive sheet |
US20130202816A1 (en) * | 2007-06-25 | 2013-08-08 | Empire Technology Development Llc | Bonded structure, sealed structure, electronic component including the same, bonding method, and sealing method |
US20160276317A1 (en) * | 2010-08-26 | 2016-09-22 | Intel Corporation | Bumpless build-up layer package with pre-stacked microelectronic devices |
CN108473777A (en) * | 2015-12-25 | 2018-08-31 | 住友电木株式会社 | Resin composition for encapsulating and semiconductor device |
US10472496B2 (en) * | 2013-09-20 | 2019-11-12 | Toagosei Co., Ltd. | Flame-retardant adhesive composition, coverlay film using same, and flexible copper-clad laminate |
CN111095440A (en) * | 2017-09-07 | 2020-05-01 | 日产化学株式会社 | Insulating composition containing silica |
US11092632B2 (en) | 2016-10-05 | 2021-08-17 | Hydro-Quebec | Resistance-measuring device and method |
Families Citing this family (37)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6670430B1 (en) * | 1999-12-17 | 2003-12-30 | Henkel Loctite Corporation | Thermosetting resin compositions comprising epoxy resins, adhesion promoters, and curatives based on the combination of nitrogen compounds and transition metal complexes |
JP3489025B2 (en) * | 2000-01-14 | 2004-01-19 | 大塚化学ホールディングス株式会社 | Epoxy resin composition and electronic component using the same |
JP2002322345A (en) * | 2001-04-24 | 2002-11-08 | Matsushita Electric Works Ltd | Resin composition for photosemiconductor device and photosemiconductor device |
US6951907B1 (en) | 2001-11-19 | 2005-10-04 | Henkel Corporation | Composition of epoxy resin, secondary amine-functional adhesion promotor and curative of nitrogen-compound and transition metal complex |
EP1668078A1 (en) * | 2003-09-30 | 2006-06-14 | Siemens Aktiengesellschaft | Potting compound, use thereof and components encapsulated in said potting compound |
JP2005146157A (en) * | 2003-11-18 | 2005-06-09 | Mitsui Chemicals Inc | Epoxy resin composition and hollow package for housing semiconductor element |
JP4720095B2 (en) * | 2004-03-31 | 2011-07-13 | Tdk株式会社 | Resin composition, electronic component, coil body and inductor |
JP2006057015A (en) * | 2004-08-20 | 2006-03-02 | Kyocera Chemical Corp | Sealing resin composition and resin-sealed type semiconductor device |
JP4148932B2 (en) * | 2004-08-31 | 2008-09-10 | シャープ株式会社 | Semiconductor device, semiconductor module, and semiconductor device manufacturing method |
US9339789B2 (en) | 2004-10-12 | 2016-05-17 | Multisorb Technologies, Inc. | Thermoset desiccant product and method for making same |
US7501011B2 (en) * | 2004-11-09 | 2009-03-10 | Multisorb Technologies, Inc. | Humidity control device |
US8853124B2 (en) | 2005-01-21 | 2014-10-07 | Multisorb Technologies, Inc. | Resin bonded sorbent |
US7595278B2 (en) * | 2005-01-21 | 2009-09-29 | Multisorb Technologies, Inc. | Resin bonded sorbent |
US7989388B2 (en) | 2005-01-21 | 2011-08-02 | Multisorb Technologies, Inc. | Resin bonded sorbent |
US20060166818A1 (en) * | 2005-01-21 | 2006-07-27 | Thomas Powers | Resin bonded sorbent |
US8097221B2 (en) * | 2005-01-21 | 2012-01-17 | Multisorb Technologies, Inc. | Lamp assembly |
EP1861880B1 (en) * | 2005-03-25 | 2012-06-20 | FUJIFILM Corporation | Method of manufacturing solid state imaging device |
US20060223978A1 (en) * | 2005-04-04 | 2006-10-05 | Shengqian Kong | Radiation- or thermally-curable oxetane barrier sealants |
US20060223937A1 (en) * | 2005-04-04 | 2006-10-05 | Herr Donald E | Radiation curable cycloaliphatic barrier sealants |
US7687119B2 (en) * | 2005-04-04 | 2010-03-30 | Henkel Ag & Co. Kgaa | Radiation-curable desiccant-filled adhesive/sealant |
TWI261350B (en) * | 2005-09-02 | 2006-09-01 | Wintek Corp | Electronic member with conductive connection structure |
US20070131348A1 (en) * | 2005-10-19 | 2007-06-14 | Katsuhiko Nakajima | Process for laser welding |
JP4866056B2 (en) * | 2005-10-26 | 2012-02-01 | 吉川工業株式会社 | Epoxy resin composition |
DE102005051289B3 (en) * | 2005-10-26 | 2007-05-16 | Siemens Ag | Piezoelectric actuator and method for producing the same |
KR101090562B1 (en) * | 2006-02-27 | 2011-12-08 | 스미토모 베이클리트 컴퍼니 리미티드 | Adhesive film |
KR20090077957A (en) * | 2006-11-15 | 2009-07-16 | 히다치 가세고교 가부시끼가이샤 | Heat curable resin composition for light reflection, process for producing the resin composition, and optical semiconductor element mounting substrate and optical semiconductor device using the resin composition |
JP5270833B2 (en) * | 2006-12-20 | 2013-08-21 | パナソニック株式会社 | Liquid resin composition, semiconductor device and manufacturing method thereof |
JP5125450B2 (en) * | 2007-03-13 | 2013-01-23 | 日立化成工業株式会社 | Thermosetting light reflecting resin composition, substrate for mounting optical semiconductor element, manufacturing method thereof, and optical semiconductor device |
US8057586B2 (en) | 2008-07-28 | 2011-11-15 | Multisorb Technologies, Inc. | Humidity control for product in a refrigerator |
JP5358355B2 (en) * | 2009-08-28 | 2013-12-04 | 豊田通商株式会社 | Resin composition and method for producing metal resin laminate |
CN102237319A (en) * | 2010-04-23 | 2011-11-09 | 三星半导体(中国)研究开发有限公司 | Package |
JP2013525593A (en) | 2010-05-05 | 2013-06-20 | タイコ エレクトロニクス サービシズ ゲゼルシャフト ミット ベシュレンクテル ハフツンク | Potting for electronic parts |
GB2524235A (en) * | 2014-03-07 | 2015-09-23 | Melexis Technologies Nv | Semiconductor device having a transparent window for passing radiation |
CN106475556B (en) * | 2016-11-06 | 2018-07-17 | 合肥圣达电子科技实业有限公司 | A method of using graphite jig sintered microwave metal-packaged shell |
JP7275100B2 (en) * | 2018-03-01 | 2023-05-17 | 株式会社トクヤマ | Fused spherical silica powder and method for producing the same |
TWI727769B (en) * | 2020-04-24 | 2021-05-11 | 長春人造樹脂廠股份有限公司 | Resin composition and uses of the same |
US11699647B2 (en) | 2021-04-15 | 2023-07-11 | Infineon Technologies Ag | Pre-molded lead frames for semiconductor packages |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1271307A (en) | 1985-06-27 | 1990-07-10 | Iwao Ohshima | Process for manufacturing high purity silica |
JPH07107091B2 (en) * | 1988-03-23 | 1995-11-15 | 住友ベークライト株式会社 | Epoxy resin composition for semiconductor encapsulation |
JPH062799B2 (en) * | 1988-04-20 | 1994-01-12 | 住友ベークライト株式会社 | Epoxy resin composition for semiconductor encapsulation |
JPH062801B2 (en) * | 1988-04-28 | 1994-01-12 | 住友ベークライト株式会社 | Epoxy resin composition for semiconductor encapsulation |
JPH0232115A (en) * | 1988-07-22 | 1990-02-01 | Sumitomo Bakelite Co Ltd | Epoxy resin composition for sealing semiconductor |
JPH02219814A (en) * | 1989-02-21 | 1990-09-03 | Sumitomo Bakelite Co Ltd | Epoxy resin composition |
JPH02173033A (en) * | 1988-12-27 | 1990-07-04 | Sumitomo Bakelite Co Ltd | Epoxy resin composition for semiconductor sealing |
MY104894A (en) * | 1988-12-08 | 1994-06-30 | Sumitomo Bakelite Co | Epoxy resin composition for semiconductor sealing. |
JPH04253760A (en) * | 1991-02-04 | 1992-09-09 | Matsushita Electric Works Ltd | Epoxy resin molding material for sealing |
JP2750254B2 (en) | 1993-02-08 | 1998-05-13 | 京セラ株式会社 | Package for storing semiconductor elements |
JP3296520B2 (en) | 1993-09-29 | 2002-07-02 | 東芝テック株式会社 | Download bootstrap method |
US5827908A (en) * | 1994-01-26 | 1998-10-27 | Shin-Etsu Chemical Co., Ltd. | Naphthalene and or biphenyl skeleton containing epoxy resin composition |
JP3119104B2 (en) * | 1994-12-09 | 2000-12-18 | 信越化学工業株式会社 | Epoxy resin composition |
JP3471514B2 (en) * | 1996-02-01 | 2003-12-02 | 水澤化学工業株式会社 | Resin composition for semiconductor encapsulation and hygroscopic filler used therein |
JP3375835B2 (en) * | 1996-10-28 | 2003-02-10 | 住友ベークライト株式会社 | Liquid sealing resin composition and semiconductor product using the liquid sealing resin composition |
KR100240121B1 (en) * | 1997-08-30 | 2000-01-15 | 성재갑 | Epoxy molding compound for package of plastic charge coupled device |
JP2000191890A (en) * | 1998-10-20 | 2000-07-11 | Nitto Denko Corp | Resin composition for sealing semiconductor and semiconductor device made by using it |
-
2000
- 2000-11-28 JP JP2000360597A patent/JP4614214B2/en not_active Expired - Lifetime
- 2000-12-01 TW TW89125643A patent/TW561177B/en not_active IP Right Cessation
- 2000-12-01 US US09/726,575 patent/US6399677B2/en not_active Expired - Lifetime
- 2000-12-02 KR KR1020000072696A patent/KR100678345B1/en active IP Right Grant
-
2001
- 2001-11-20 US US09/988,752 patent/US6569532B2/en not_active Expired - Lifetime
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030168731A1 (en) * | 2002-03-11 | 2003-09-11 | Matayabas James Christopher | Thermal interface material and method of fabricating the same |
US20120153513A1 (en) * | 2007-05-17 | 2012-06-21 | Nitto Denko Corporation | Thermosetting encapsulation adhesive sheet |
US8922031B2 (en) * | 2007-05-17 | 2014-12-30 | Nitto Denko Corporation | Thermosetting encapsulation adhesive sheet |
US20130202816A1 (en) * | 2007-06-25 | 2013-08-08 | Empire Technology Development Llc | Bonded structure, sealed structure, electronic component including the same, bonding method, and sealing method |
US20090084602A1 (en) * | 2007-09-28 | 2009-04-02 | Shin-Etsu Chemical Co., Ltd. | Automotive electric/electronic package |
US9831213B2 (en) * | 2010-08-26 | 2017-11-28 | Intel Corporation | Bumpless build-up layer package with pre-stacked microelectronic devices |
US20160276317A1 (en) * | 2010-08-26 | 2016-09-22 | Intel Corporation | Bumpless build-up layer package with pre-stacked microelectronic devices |
US10472496B2 (en) * | 2013-09-20 | 2019-11-12 | Toagosei Co., Ltd. | Flame-retardant adhesive composition, coverlay film using same, and flexible copper-clad laminate |
CN108473777A (en) * | 2015-12-25 | 2018-08-31 | 住友电木株式会社 | Resin composition for encapsulating and semiconductor device |
US10262914B2 (en) | 2015-12-25 | 2019-04-16 | Sumitomo Bakelite Co., Ltd. | Resin composition for encapsulation, and semiconductor device |
US11092632B2 (en) | 2016-10-05 | 2021-08-17 | Hydro-Quebec | Resistance-measuring device and method |
CN111095440A (en) * | 2017-09-07 | 2020-05-01 | 日产化学株式会社 | Insulating composition containing silica |
EP3680918A4 (en) * | 2017-09-07 | 2021-06-30 | Nissan Chemical Corporation | Silica-containing insulating composition |
US11961636B2 (en) | 2017-09-07 | 2024-04-16 | Nissan Chemical Corporation | Silica-containing insulating composition |
Also Published As
Publication number | Publication date |
---|---|
US6399677B2 (en) | 2002-06-04 |
JP2001220496A (en) | 2001-08-14 |
US6569532B2 (en) | 2003-05-27 |
TW561177B (en) | 2003-11-11 |
KR20010062093A (en) | 2001-07-07 |
US20020076558A1 (en) | 2002-06-20 |
JP4614214B2 (en) | 2011-01-19 |
KR100678345B1 (en) | 2007-02-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6399677B2 (en) | Epoxy resin compositions and premolded semiconductor packages | |
JP2874089B2 (en) | Resin composition for semiconductor encapsulation and semiconductor device | |
JPS63245426A (en) | Epoxy resin composition and resin-sealed semiconductor device | |
KR101585271B1 (en) | Epoxy resin composition for semiconductor encapsulation and semiconductor device using the same | |
JP2701695B2 (en) | Epoxy resin composition and semiconductor device | |
JP3022135B2 (en) | Epoxy resin composition | |
JP2006265370A (en) | Epoxy resin composition for sealing optical semiconductor and optical semiconductor device | |
JP4496740B2 (en) | Epoxy resin composition and semiconductor device | |
JPH10173103A (en) | Epoxy resin compsn. for sealing semiconductor | |
JP2005089710A (en) | Epoxy resin composition for sealing semiconductor and semiconductor device | |
JPH05299537A (en) | Epoxy resin composition | |
JP2006257309A (en) | Epoxy resin composition for sealing semiconductor and semiconductor device | |
JP2002179773A (en) | Epoxy resin composition and semiconductor device | |
JPH10182944A (en) | Resin composition for sealing electronic parts | |
JP2005225971A (en) | Epoxy resin composition and semiconductor device | |
JP2816290B2 (en) | Resin-sealed semiconductor device | |
JP2006206748A (en) | Epoxy resin composition and semiconductor device | |
JPH03115455A (en) | Sealing resin composition and resin-sealed semiconductor device | |
JP2954413B2 (en) | Epoxy resin composition | |
JPH11335527A (en) | Epoxy resin composition for semiconductor sealing | |
JP2006143784A (en) | Epoxy resin composition and semiconductor device | |
JP2005053978A (en) | Epoxy resin composition for semiconductor sealing, and semiconductor device | |
JP3093051B2 (en) | Epoxy resin composition | |
JPH09165498A (en) | Resin composition for sealing of electronic component part | |
JPH0794641A (en) | Semiconductor device |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: SHIN-ETSU CHEMICAL CO., LTD., JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:TOMIYOSHI, KAZUTOSHI;ARAI, KAZUHIRO;SHIOBARA, TOSHIO;AND OTHERS;REEL/FRAME:011563/0478;SIGNING DATES FROM 20010104 TO 20010216 Owner name: SONY CORPORATION, JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:TOMIYOSHI, KAZUTOSHI;ARAI, KAZUHIRO;SHIOBARA, TOSHIO;AND OTHERS;REEL/FRAME:011563/0478;SIGNING DATES FROM 20010104 TO 20010216 |
|
AS | Assignment |
Owner name: SHIN-ETSU CHEMICAL CO., LTD., JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:SONY CORPORATION;REEL/FRAME:012313/0811 Effective date: 20011105 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
FPAY | Fee payment |
Year of fee payment: 8 |
|
FPAY | Fee payment |
Year of fee payment: 12 |