JP6355210B2 - Curable silicone composition for semiconductor device and semiconductor element sealing - Google Patents
Curable silicone composition for semiconductor device and semiconductor element sealing Download PDFInfo
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- JP6355210B2 JP6355210B2 JP2015519987A JP2015519987A JP6355210B2 JP 6355210 B2 JP6355210 B2 JP 6355210B2 JP 2015519987 A JP2015519987 A JP 2015519987A JP 2015519987 A JP2015519987 A JP 2015519987A JP 6355210 B2 JP6355210 B2 JP 6355210B2
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- 229920001296 polysiloxane Polymers 0.000 title claims description 66
- 239000004065 semiconductor Substances 0.000 title claims description 62
- 239000000203 mixture Substances 0.000 title claims description 60
- 238000007789 sealing Methods 0.000 title claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 29
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 29
- 229910052710 silicon Inorganic materials 0.000 claims description 27
- 125000003342 alkenyl group Chemical group 0.000 claims description 25
- 239000010703 silicon Substances 0.000 claims description 22
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 18
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 9
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 125000004434 sulfur atom Chemical group 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 4
- -1 heptenyl group Chemical group 0.000 description 31
- 239000000047 product Substances 0.000 description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 15
- 239000004954 Polyphthalamide Substances 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 12
- 229920006375 polyphtalamide Polymers 0.000 description 12
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003566 sealing material Substances 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 7
- 229910052737 gold Inorganic materials 0.000 description 7
- 239000010931 gold Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000002318 adhesion promoter Substances 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052693 Europium Inorganic materials 0.000 description 4
- 229910004283 SiO 4 Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 125000005388 dimethylhydrogensiloxy group Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 2
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000002223 garnet Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000004344 phenylpropyl group Chemical group 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002683 reaction inhibitor Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- HMVBQEAJQVQOTI-SOFGYWHQSA-N (e)-3,5-dimethylhex-3-en-1-yne Chemical compound CC(C)\C=C(/C)C#C HMVBQEAJQVQOTI-SOFGYWHQSA-N 0.000 description 1
- GRGVQLWQXHFRHO-AATRIKPKSA-N (e)-3-methylpent-3-en-1-yne Chemical compound C\C=C(/C)C#C GRGVQLWQXHFRHO-AATRIKPKSA-N 0.000 description 1
- VEJOYRPGKZZTJW-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;platinum Chemical compound [Pt].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VEJOYRPGKZZTJW-FDGPNNRMSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical class C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 1
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 1
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 1
- MBNRBJNIYVXSQV-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propane-1-thiol Chemical compound CCO[Si](C)(OCC)CCCS MBNRBJNIYVXSQV-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JSAYQGVHWNBMNG-UHFFFAOYSA-N bis(2-methylbut-3-yn-2-yloxy)-prop-1-enylsilane Chemical compound CC=C[SiH](OC(C#C)(C)C)OC(C#C)(C)C JSAYQGVHWNBMNG-UHFFFAOYSA-N 0.000 description 1
- GKPOMITUDGXOSB-UHFFFAOYSA-N but-3-yn-2-ol Chemical compound CC(O)C#C GKPOMITUDGXOSB-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
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- 238000009833 condensation Methods 0.000 description 1
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- 238000006482 condensation reaction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- RQCQBDUYEHRNPP-UHFFFAOYSA-N dimethyl-bis(2-methylbut-3-yn-2-yloxy)silane Chemical compound C#CC(C)(C)O[Si](C)(C)OC(C)(C)C#C RQCQBDUYEHRNPP-UHFFFAOYSA-N 0.000 description 1
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- KPWVUBSQUODFPP-UHFFFAOYSA-N ethenyl-(ethenyl-methyl-phenylsilyl)oxy-methyl-phenylsilane Chemical compound C=1C=CC=CC=1[Si](C)(C=C)O[Si](C)(C=C)C1=CC=CC=C1 KPWVUBSQUODFPP-UHFFFAOYSA-N 0.000 description 1
- HOMYFVKFSFMSFF-UHFFFAOYSA-N ethenyl-[ethenyl(diphenyl)silyl]oxy-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C=C)O[Si](C=C)(C=1C=CC=CC=1)C1=CC=CC=C1 HOMYFVKFSFMSFF-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 125000005417 glycidoxyalkyl group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- NYMPGSQKHIOWIO-UHFFFAOYSA-N hydroxy(diphenyl)silicon Chemical class C=1C=CC=CC=1[Si](O)C1=CC=CC=C1 NYMPGSQKHIOWIO-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- PIZSEPSUZMIOQF-UHFFFAOYSA-N platinum;2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical class [Pt].C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 PIZSEPSUZMIOQF-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- NQRACKNXKKOCJY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSCCC[Si](OC)(OC)OC NQRACKNXKKOCJY-UHFFFAOYSA-N 0.000 description 1
- JTTSZDBCLAKKAY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSSSCCC[Si](OC)(OC)OC JTTSZDBCLAKKAY-UHFFFAOYSA-N 0.000 description 1
- KOFGNZOFJYBHIN-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyltrisulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSSCCC[Si](OC)(OC)OC KOFGNZOFJYBHIN-UHFFFAOYSA-N 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical class C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、半導体装置および該半導体装置中の半導体素子を封止するための硬化性シリコーン組成物に関する。 The present invention relates to a semiconductor device and a curable silicone composition for sealing a semiconductor element in the semiconductor device.
ＬＥＤ等の光半導体装置では、リードや基板の腐食を防止し、発光ダイオード（ＬＥＤ）素子からの光を効率良く反射するため、銀メッキしたリードや基板が使用されている。銀は硫化水素等の硫黄含有ガスにより黒色化する問題がある。このため、銀より反射率が劣るものの、硫黄含有ガスによる黒色化の問題がない、金メッキされたリードや基板の使用が検討されている。
一方、ヒドロシリル化反応硬化性シリコーン組成物は、加熱により速やかに硬化し、硬化の際に副生成物を生じないことから半導体素子の封止剤や接着剤として利用されている。ヒドロシリル化反応硬化性シリコーン組成物は、接着性が乏しいため、例えば、特開２００７−１３４３７２号公報では、金メッキされた基板上に搭載した半導体素子をヒドロシリル化反応硬化性シリコーン組成物で封止する際には、前記基板を予め酸無水物基含有アルコキシシランもしくはその部分加水分解縮合物で処理することが提案されている。
しかし、特開２００７−１３４３７２号公報により提案される方法では、金メッキされた基板を予め酸無水物基含有アルコキシシランもしくはその部分加水分解縮合物で処理しなければならないという不都合がある。
ところで、特開２０１１−０６３６６３号公報には、ケイ素原子結合水酸基を有する分岐状オルガノポリシロキサン、無機充填剤、縮合触媒、直鎖状ジオルガノポリシロキサン残基を有するオルガノポリシロキサン、および３−メルカプトプロピルトリメトキシシラン等のシランカップリング剤からなるアンダーフィル材組成物が提案され、リフロー時の反りの挙動への影響が無く、耐熱性、耐光性、金バンプへの接着性に優れることが提案されている。しかし、この組成物は、アンダーフィル材用途であり、また、縮合反応により硬化するため、反応により、副生成物が発生するという課題がある。一方で、ヒドロシリル化反応硬化性シリコーン組成物において、３−メルカプトプロピルトリメトキシシラン等の硫黄原子を結合し、ケイ素原子結合加水分解性基を有する有機ケイ素化合物は、硬化阻害を生じやすいことから、前記有機ケイ素化合物を接着促進剤として使用することは検討されていなかった。In an optical semiconductor device such as an LED, a silver-plated lead or substrate is used in order to prevent corrosion of the lead and the substrate and efficiently reflect light from a light emitting diode (LED) element. Silver has a problem of being blackened by a sulfur-containing gas such as hydrogen sulfide. For this reason, the use of gold-plated leads and substrates, which are less reflective than silver but have no problem of blackening due to sulfur-containing gas, has been studied.
On the other hand, the hydrosilylation reaction curable silicone composition is rapidly cured by heating and does not produce a by-product during curing, and thus is used as a sealant or adhesive for semiconductor elements. Since the hydrosilylation reaction-curable silicone composition has poor adhesiveness, for example, in Japanese Patent Application Laid-Open No. 2007-134372, a semiconductor element mounted on a gold-plated substrate is sealed with the hydrosilylation reaction-curable silicone composition. In this case, it has been proposed to treat the substrate in advance with an acid anhydride group-containing alkoxysilane or a partial hydrolysis condensate thereof.
However, the method proposed in Japanese Patent Application Laid-Open No. 2007-134372 has the disadvantage that the gold-plated substrate must be previously treated with an acid anhydride group-containing alkoxysilane or a partially hydrolyzed condensate thereof.
JP 2011-063663 A discloses branched organopolysiloxane having a silicon atom-bonded hydroxyl group, inorganic filler, condensation catalyst, organopolysiloxane having a linear diorganopolysiloxane residue, and 3-mercapto. An underfill material composition consisting of a silane coupling agent such as propyltrimethoxysilane has been proposed, and there is no effect on the warping behavior during reflow, and it has excellent heat resistance, light resistance, and adhesion to gold bumps. Has been. However, since this composition is used for an underfill material and is cured by a condensation reaction, there is a problem that a by-product is generated by the reaction. On the other hand, in the hydrosilylation reaction curable silicone composition, an organosilicon compound having a silicon atom-bonded hydrolyzable group and a sulfur atom such as 3-mercaptopropyltrimethoxysilane is likely to cause inhibition of curing. The use of the organosilicon compound as an adhesion promoter has not been studied.
本発明の目的は、金メッキされたリードまたは基板と半導体素子をシリコーン硬化物で封止してなる、吸湿リフロー試験後の信頼性が優れる半導体装置を提供することにある。また、本発明の他の目的は、金メッキされたリードまたは基板に対する接着性が良好な、前記リードまたは基板と半導体素子を封止するための硬化性シリコーン組成物を提供することにある。 An object of the present invention is to provide a semiconductor device having excellent reliability after a moisture absorption reflow test, in which a gold-plated lead or substrate and a semiconductor element are sealed with a cured silicone. Another object of the present invention is to provide a curable silicone composition for sealing the lead or substrate and the semiconductor element, which has good adhesion to the gold-plated lead or substrate.
本発明の半導体装置は、金メッキされたリードまたは基板と半導体素子をシリコーン硬化物で封止した半導体装置であって、前記シリコーン硬化物が、（Ａ）一分子中に少なくとも２個のアルケニル基を有するオルガノポリシロキサン、（Ｂ）一分子中に少なくとも２個のケイ素原子結合水素原子を有するオルガノハイドロジェンポリシロキサン｛（Ａ）成分中のアルケニル基１モルに対して、本成分中のケイ素原子結合水素原子が０．１〜１０モルとなる量｝、（Ｃ）硫黄原子を結合し、ケイ素原子結合加水分解性基を有する有機ケイ素化合物（本組成物に対して０．０００１〜２質量％）、および（Ｄ）ヒドロシリル化反応用白金系触媒（本組成物に対して、白金原子が０．０１〜５００質量ｐｐｍとなる量）から少なくともなるヒドロシリル化反応硬化性シリコーン組成物の硬化物であることを特徴とする。
上記半導体装置において、シリコーン硬化物のＪＩＳ Ｋ ６２５３に規定のタイプＡデュロメータ硬さは１０〜９９であることが好ましい。
また、上記半導体装置において、半導体素子は発光ダイオード（ＬＥＤ）素子であることが好ましい。
また、本発明の半導体素子封止用硬化性シリコーン組成物は、半導体装置中の金メッキされたリードまたは基板と半導体素子を封止するためのヒドロシリル化反応硬化性シリコーン組成物であって、（Ａ）一分子中に少なくとも２個のアルケニル基を有するオルガノポリシロキサン、（Ｂ）一分子中に少なくとも２個のケイ素原子結合水素原子を有するオルガノハイドロジェンポリシロキサン｛（Ａ）成分中のアルケニル基１モルに対して、本成分中のケイ素原子結合水素原子が０．１〜１０モルとなる量｝、（Ｃ）硫黄原子を結合し、ケイ素原子結合加水分解性基を有する有機ケイ素化合物（本組成物に対して０．０００１〜２質量％）、および（Ｄ）ヒドロシリル化反応用白金系触媒（本組成物に対して、白金原子が０．０１〜５００質量ｐｐｍとなる量）から少なくともなることを特徴とする。The semiconductor device of the present invention is a semiconductor device in which a gold-plated lead or substrate and a semiconductor element are sealed with a silicone cured product, wherein the silicone cured product has (A) at least two alkenyl groups in one molecule. Organopolysiloxane having (B) organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule {bonding silicon atoms in this component to 1 mol of alkenyl groups in component (A) Amount in which hydrogen atom is 0.1 to 10 mol}, (C) an organosilicon compound having a sulfur atom bonded and a silicon atom-bonded hydrolyzable group (0.0001 to 2% by mass based on the present composition) And (D) a hydrosilation reaction platinum-based catalyst (the amount of platinum atoms in the composition is 0.01 to 500 ppm by mass). Characterized in that it is a cured product of Lil reaction curable silicone composition.
In the above semiconductor device, the type A durometer hardness defined in JIS K 6253 of the cured silicone is preferably 10-99.
In the semiconductor device, the semiconductor element is preferably a light emitting diode (LED) element.
The curable silicone composition for encapsulating a semiconductor element of the present invention is a hydrosilylation reaction curable silicone composition for encapsulating a gold-plated lead or substrate in a semiconductor device and the semiconductor element. ) Organopolysiloxane having at least two alkenyl groups in one molecule, (B) Organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule {alkenyl group 1 in component (A) Amount in which silicon-bonded hydrogen atoms in this component are 0.1 to 10 moles per mole}, (C) an organosilicon compound having a sulfur atom-bonded and silicon-bonded hydrolyzable group (this composition 0.0001-2 mass% with respect to the product), and (D) platinum catalyst for hydrosilylation reaction (0.01-500 platinum atoms with respect to the present composition) And at least consisting of a ppm amount).
本発明の半導体装置は、吸湿リフロー試験後の信頼性が優れるという特徴がある。また、本発明の半導体素子封止用硬化性シリコーン組成物は、金メッキされたリードまたは基板に対する接着性が良好であるという特徴がある。 The semiconductor device of the present invention is characterized by excellent reliability after the moisture absorption reflow test. In addition, the curable silicone composition for sealing a semiconductor element of the present invention is characterized by good adhesion to a gold-plated lead or substrate.
図１は、本発明の半導体装置の一例である光半導体装置（ＬＥＤ）の断面図である。 FIG. 1 is a cross-sectional view of an optical semiconductor device (LED) which is an example of a semiconductor device of the present invention.
はじめに、本発明の半導体装置について詳細に説明する。
本発明の半導体装置は、金メッキされたリードまたは基板と半導体素子をシリコーン硬化物で封止した半導体装置である。この半導体素子としては、発光ダイオード（ＬＥＤ）素子、半導体レーザ素子、フォトダイオード素子、フォトトランジスタ素子、固体撮像素子、フォトカプラー用の発光素子または受光素子が例示され、特に、発光ダイオード（ＬＥＤ）素子であることが好ましい。
本発明の半導体装置を図１により詳細に説明する。
図１は半導体装置の一例である光半導体装置（ＬＥＤ）の断面図である。この光半導体装置（ＬＥＤ）では、ポリフタルアミド（ＰＰＡ）樹脂製筐体１内のダイパッド３上に発光ダイオード（ＬＥＤ）素子５が接着材４によりダイボンディングされ、発光ダイオード（ＬＥＤ）素子５と金メッキされたリード２とが金製ボンディングワイヤ６によりワイヤボンディングされ、発光ダイオード（ＬＥＤ）素子５と金メッキされたリード２と金製ボンディングワイヤ６とが、シリコーン硬化物からなる封止材７により封止されている。
本発明の半導体装置では、金メッキされたリードまたは基板と半導体素子を封止したシリコーン硬化物が、（Ａ）一分子中に少なくとも２個のアルケニル基を有するオルガノポリシロキサン、（Ｂ）一分子中に少なくとも２個のケイ素原子結合水素原子を有するオルガノハイドロジェンポリシロキサン｛（Ａ）成分中のアルケニル基１モルに対して、本成分中のケイ素原子結合水素原子が０．１〜１０モルとなる量｝、（Ｃ）硫黄原子を結合し、ケイ素原子結合加水分解性基を有する有機ケイ素化合物（本組成物に対して０．０００１〜２質量％）、および（Ｄ）ヒドロシリル化反応用白金系触媒（本組成物に対して、白金原子が０．０１〜５００質量ｐｐｍとなる量）から少なくともなるヒドロシリル化反応硬化性シリコーン組成物の硬化物であることを特徴とする。
（Ａ）成分は上記組成物の主剤であり、一分子中に少なくとも２個のアルケニル基を有するオルガノポリシロキサンである。（Ａ）成分中のアルケニル基としては、ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基、ウンデセニル基、ドデセニル基等の炭素数が２〜１２個のアルケニル基が例示され、好ましくは、ビニル基である。また、（Ａ）成分中のアルケニル基以外のケイ素原子に結合する基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、シクロヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基等の炭素数が１〜１２個のアルキル基；フェニル基、トリル基、キシリル基、ナフチル基等の炭素数が６〜２０個のアリール基；ベンジル基、フェネチル基、フェニルプロピル基等の炭素数が７〜２０個のアラルキル基；これらの基の水素原子の一部または全部をフッ素原子、塩素原子、臭素原子等のハロゲン原子で置換した基が例示される。なお、（Ａ）成分中のケイ素原子には、本発明の目的を損なわない範囲で、少量の水酸基やメトキシ基、エトキシ基等のアルコキシ基を有していてもよい。
（Ａ）成分の分子構造は特に限定されないが、例えば、直鎖状、一部分岐を有する直鎖状、分岐鎖状、環状、および三次元網状構造が挙げられる。（Ａ）成分は、これらの分子構造を有する単独のオルガノポリシロキサン、あるいはこれらの分子構造を有する二種以上のオルガノポリシロキサンの混合物であってもよい。
このような（Ａ）成分は、ケイ素原子結合全有機基に対して、アルケニル基が０．０１〜５０モル％、０．０５〜４０モル％、あるいは、０．０９〜３２モル％であることが好ましい。これは、（Ａ）成分中のアルケニル基が少なすぎると硬化物が得られないおそれがあり、また、（Ａ）成分中のアルケニル基が多すぎると得られる硬化物の機械的特性が悪くなるおそれがあるからである。また、（Ａ）成分中のアルケニル基は、オルガノポリシロキサンの分子鎖両末端にあることが好ましい。なお、（Ａ）成分中のアルケニル基のモル％は、例えば、フーリエ変換赤外分光光度計（ＦＴ−ＩＲ）、核磁気共鳴（ＮＭＲ）、ゲル浸透クロマトグラフィー（ＧＰＣ）等の分析によって求めることができる。
（Ａ）成分は、２５℃で液状又は固体状のオルガノポリシロキサンである。（Ａ）成分が２５℃で液状である場合、その２５℃での粘度は、１〜１，０００，０００ｍＰａ・ｓの範囲内、または１０〜１，０００，０００ｍＰａ・ｓの範囲内であることが好ましい。なお、オルガノポリシロキサンの２５℃での粘度は、例えば、ＪＩＳ Ｋ７１１７−１に準拠してＢ型粘度計を用いた測定により求めることができる。
（Ｂ）成分は上記組成物の架橋剤であり、一分子中に少なくとも２個のケイ素原子結合水素原子を有するオルガノハイドロジェンポリシロキサンである。（Ｂ）成分中の水素原子以外のケイ素原子に結合する基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、シクロヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基等の炭素数が１〜１２個のアルキル基；フェニル基、トリル基、キシリル基、ナフチル基等の炭素数が６〜２０個のアリール基；ベンジル基、フェネチル基、フェニルプロピル基等の炭素数が７〜２０個のアラルキル基；これらの基の水素原子の一部または全部をフッ素原子、塩素原子、臭素原子等のハロゲン原子で置換した基が例示される。なお、（Ｂ）成分中のケイ素原子には、本発明の目的を損なわない範囲で、少量の水酸基やメトキシ基、エトキシ基等のアルコキシ基を有していてもよい。
（Ｂ）成分の分子構造は特に限定されないが、例えば、直鎖状、一部分岐を有する直鎖状、分岐鎖状、環状、および三次元網状構造が挙げられ、好ましくは、一部分岐を有する直鎖状、分岐鎖状、および三次元網状構造が挙げられる。
（Ｂ）成分は、２５℃で固体状又は液状である。（Ｂ）成分が２５℃で液状である場合は、その２５℃での粘度は、１０，０００ｍＰａ・ｓ以下、０．１〜５，０００ｍＰａ・ｓの範囲内、あるいは、０．５〜１，０００ｍＰａ・ｓの範囲内であることが好ましい。なお、オルガノポリシロキサンの２５℃での粘度は、例えば、ＪＩＳ Ｋ７１１７−１に準拠してＢ型粘度計を用いた測定により求めることができる。
（Ｂ）成分は、本発明の目的を達成できる限り、特に特定のオルガノポリシロキサンに限定されないが、例えば、１，１，３，３−テトラメチルジシロキサン、１，３，５，７−テトラメチルシクロテトラシロキサン、トリス（ジメチルハイドロジェンシロキシ）メチルシラン、トリス（ジメチルハイドロジェンシロキシ）フェニルシラン、１−グリシドキシプロピル−１，３，５，７−テトラメチルシクロテトラシロキサン、１，５−ジグリシドキシプロピル−１，３，５，７−テトラメチルシクロテトラシロキサン、１−グリシドキシプロピル−５−トリメトキシシリルエチル−１，３，５，７−テトラメチルシクロテトラシロキサン、分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンポリシロキサン、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルポリシロキサン、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンシロキサン・ジフェニルシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンシロキサン・ジフェニルシロキサン・ジメチルシロキサン共重合体、（ＣＨ３）２ＨＳｉＯ１／２単位とＳｉＯ４／２単位とからなる共重合体、および（ＣＨ３）２ＨＳｉＯ１／２単位とＳｉＯ４／２単位と（Ｃ６Ｈ５）ＳｉＯ３／２単位とからなる共重合体等からなる群から選ばれる１種又は２種以上が挙げられる。
（Ｂ）成分の含有量は、（Ａ）成分中のアルケニル基１モルに対して、本成分中のケイ素原子結合水素原子が０．１〜１０モルとなる量であり、好ましくは、０．５〜５モルとなる量である。これは、（Ｂ）成分の含有量が上記範囲の上限以下であると、得られる硬化物の機械的特性の低下を抑えることができるからであり、一方、上記範囲の下限以上であると、得られる組成物が十分に硬化するからである。なお、（Ｂ）成分中のケイ素原子結合水素原子の含有量は、例えば、フーリエ変換赤外分光光度計（ＦＴ−ＩＲ）、核磁気共鳴（ＮＭＲ）、ゲル浸透クロマトグラフィー（ＧＰＣ）等の分析によって求めることができる。
（Ｃ）成分の有機ケイ素化合物は、硫黄原子を結合し、ケイ素原子結合加水分解性基を有するものであり、上記組成物に金メッキされたリードフレームへの良好な接着性を付与する成分である。このような（Ｃ）成分としては、３−メルカプトプロピルトリメトキシシラン、３−メルカプトプロピルトリエトキシシラン、３−メルカプトプロピルメチルジメトキシシラン、３−メルカプトプロピルメチルジエトキシシラン等のメルカプトアルキルアルコキシシラン；ビス（トリメトキシシリルプロピル）ジスルフィド、ビス（トリメトキシシリルプロピル）トリスルフィド、ビス（トリメトキシシリルプロピル）テトラスルフィド等のビス（アルコキシシリルアルキル）スルフィドが例示される。
（Ｃ）成分の含有量は、上記組成物に対して、０．０００１〜２質量％であり、好ましくは、０．００１〜１質量％、あるいは、０．０１〜０．２質量％となる量である。これは上記範囲の下限以上であると、金メッキされたリードや基板に対する接着性が向上し、一方、上記範囲の上限以下であると、上記組成物の硬化阻害を生じにくいからである。
（Ｄ）成分は、上記組成物のヒドロシリル化反応を促進するためのヒドロシリル化反応用白金系触媒である。このような（Ｄ）成分としては、白金微粉末、白金黒、塩化白金酸、塩化白金酸のアルコール変性物、塩化白金酸とジオレフィンの錯体、白金−オレフィン錯体、白金ビス（アセトアセテート）、白金ビス（アセチルアセトネート）等の白金−カルボニル錯体、塩化白金酸−ジビニルテトラメチルジシロキサン錯体、塩化白金酸−テトラビニルテトラメチルシクロテトラシロキサン錯体等の塩化白金酸−アルケニルシロキサン錯体、白金−ジビニルテトラメチルジシロキサン錯体、白金−テトラビニルテトラメチルシクロテトラシロキサン錯体等の白金−アルケニルシロキサン錯体、および塩化白金酸とアセチレンアルコール類との錯体が例示され、特に、ヒドロシリル化反応の促進効果が高いことから、白金−アルケニルシロキサン錯体であることが好ましい。これらのヒドロシリル化反応用白金系触媒は、一種単独で用いてもよいし、二種以上を併用してもよい。
白金−アルケニルシロキサン錯体に用いられるアルケニルシロキサンは、特に限定されないが、例えば、１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン、１，３，５，７−テトラメチル−１，３，５，７−テトラビニルシクロテトラシロキサン、これらのアルケニルシロキサンのメチル基の一部をエチル基、フェニル基等で置換したアルケニルシロキサンオリゴマー、およびこれらのアルケニルシロキサンのビニル基をアリル基、ヘキセニル基等で置換したアルケニルシロキサンオリゴマー等が挙げられる。特に、生成する白金−アルケニルシロキサン錯体の安定性が良好であることから、１，３−ジビニル−１，１，３，３−テトラメチルジシロキサンが好ましい。
また、白金−アルケニルシロキサン錯体の安定性を向上させるため、これらの白金−アルケニルシロキサン錯体を、１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン、１，３−ジアリル−１，１，３，３−テトラメチルジシロキサン、１，３−ジビニル−１，３−ジメチル−１，３−ジフェニルジシロキサン、１，３−ジビニル−１，１，３，３−テトラフェニルジシロキサン、および１，３，５，７−テトラメチル−１，３，５，７−テトラビニルシクロテトラシロキサン等のアルケニルシロキサンオリゴマーやジメチルシロキサンオリゴマー等のオルガノシロキサンオリゴマーに溶解していることが好ましく、特にアルケニルシロキサンオリゴマーに溶解していることが好ましい。
（Ｄ）成分の含有量は、上記組成物に対して、（Ｄ）成分中の白金原子が０．０１〜５００質量ｐｐｍとなる量であり、好ましくは、０．０１〜１００質量ｐｐｍの範囲内、あるいは、０．１〜５０質量ｐｐｍの範囲内となる量である。これは、（Ｄ）成分の含有量が上記範囲の下限以上であると、得られる組成物が十分に硬化するからであり、一方、上記範囲の上限以下であると、得られる硬化物の着色が抑えられるからである。
上記組成物には、常温での可使時間を延長し、保存安定性を向上させるための任意の成分として、（Ｅ）ヒドロシリル化反応抑制剤を含有してもよい。このような（Ｅ）成分としては、１−エチニルシクロヘキサン−１−オール、２−メチル−３−ブチン−２−オール、３，５−ジメチル−１−ヘキシン−３−オール、および２−フェニル−３−ブチン−２−オール等のアルキンアルコール；３−メチル−３−ペンテン−１−イン、および３，５−ジメチル−３−ヘキセン−１−イン等のエンイン化合物；１，３，５，７−テトラメチル−１，３，５，７−テトラビニルシクロテトラシロキサン、および１，３，５，７−テトラメチル−１，３，５，７−テトラヘキセニルシクロテトラシロキサン等のメチルアルケニルシロキサンオリゴマー；ジメチルビス（３−メチル−１−ブチン−３−オキシ）シラン、およびメチルビニルビス（３−メチル−１−ブチン−３−オキシ）シラン等のアルキンオキシシラン、並びにトリアリルイソシアヌレート系化合物が例示される。
（Ｅ）成分の含有量は特に限定されないが、上記、（Ａ）成分〜（Ｄ）成分の混合時にゲル化を抑制し、または硬化を抑制するのに十分な量であり、さらには長期間保存可能とするために十分な量である。（Ｅ）成分の含有量としては、具体的には、上記（Ａ）成分〜（Ｄ）成分の合計１００質量部に対して０．０００１〜５質量部の範囲内、あるいは、０．０１〜３質量部の範囲内であることが好ましい。
また、上記組成物には、硬化中に接触している基材への接着性を更に向上させるために、接着促進剤を含有してもよい。この接着促進剤としては、ケイ素原子に結合したアルコキシ基を一分子中に１個または２個以上有する有機ケイ素化合物が好ましい。このアルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、およびメトキシエトキシ基が例示され、特に、メトキシ基またはエトキシ基が好ましい。また、この有機ケイ素化合物のケイ素原子に結合するアルコキシ基以外の基としては、アルキル基、アルケニル基、アリール基、アラルキル基、およびハロゲン化アルキル基等の置換もしくは非置換の一価炭化水素基；３−グリシドキシプロピル基、および４−グリシドキシブチル基等のグリシドキシアルキル基；２−（３，４−エポキシシクロヘキシル）エチル基、および３−（３，４−エポキシシクロヘキシル）プロピル基等のエポキシシクロヘキシルアルキル基；４−オキシラニルブチル基、および８−オキシラニルオクチル基等のオキシラニルアルキル基；３−メタクリロキシプロピル基等のアクリル基含有一価有機基；イソシアネート基；イソシアヌレート基；並びに水素原子が例示される。この有機ケイ素化合物は本組成物中のアルケニル基またはケイ素原子結合水素原子と反応し得る基を有することが好ましく、具体的には、ケイ素原子結合水素原子またはアルケニル基を有することが好ましい。
接着促進剤の含有量は限定されないが、上記（Ａ）成分〜（Ｄ）成分の合計１００質量部に対して０．０１〜１０質量部の範囲内、あるいは、０．１〜３質量部の範囲内であることが好ましい。
また、上記組成物には、その他任意の成分として、蛍光体を含有することができる。この蛍光体としては、例えば、発光ダイオード（ＬＥＤ）に広く利用されている、酸化物系蛍光体、酸窒化物系蛍光体、窒化物系蛍光体、硫化物系蛍光体、酸硫化物系蛍光体等からなる黄色、赤色、緑色、青色発光蛍光体が挙げられる。酸化物系蛍光体としては、セリウムイオンを包含するイットリウム、アルミニウム、ガーネット系のＹＡＧ系緑色〜黄色発光蛍光体；セリウムイオンを包含するテルビウム、アルミニウム、ガーネット系のＴＡＧ系黄色発光蛍光体；および、セリウムやユーロピウムイオンを包含するシリケート系緑色〜黄色発光蛍光体が例示される。酸窒化物系蛍光体としては、ユーロピウムイオンを包含するケイ素、アルミニウム、酸素、窒素系のサイアロン系赤色〜緑色発光蛍光体が例示される。窒化物系蛍光体としては、ユーロピウムイオンを包含するカルシウム、ストロンチウム、アルミニウム、ケイ素、窒素系のカズン系赤色発光蛍光体が例示される。硫化物系蛍光体としては、銅イオンやアルミニウムイオンを包含するＺｎＳ系緑色発色蛍光体が例示される。酸硫化物系蛍光体としては、ユーロピウムイオンを包含するＹ２Ｏ２Ｓ系赤色発光蛍光体が例示される。これらの蛍光体は、１種もしくは２種以上の混合物を用いてもよい。
この蛍光体の含有量は特に限定されないが、上記組成物中、０．１〜７０質量％の範囲内、あるいは、１〜２０質量％の範囲内であることが好ましい。
また、上記組成物には、本発明の目的を損なわない限り、その他の任意の成分として、シリカ、ガラス、およびアルミナ等から選択される１種又は２種以上の無機質充填剤；シリコーンゴム粉末；シリコーン樹脂、およびポリメタクリレート樹脂等の樹脂粉末；耐熱剤、染料、顔料、難燃性付与剤、界面活性剤、溶剤等から選択される１種又は２種以上の成分を含有してもよい。
本発明の半導体装置の製造方法は特に限定されず、例えば、図１で示される光半導体装置（ＬＥＤ）は次のようにして製造することができる。
ポリフタルアミド（ＰＰＡ）樹脂製筐体１内のダイパッド３上に発光ダイオード（ＬＥＤ）素子５を接着材４によりダイボンディングする。次に、発光ダイオード（ＬＥＤ）素子５と金メッキされたリード２とを金製ボンディングワイヤ６によりワイヤボンディングする。次いで、ポリフタルアミド（ＰＰＡ）樹脂製筐体１内に上記組成物を注入し、硬化させることにより、発光ダイオード（ＬＥＤ）素子５と金メッキされたリード２と金製ボンディングワイヤ６とをシリコーン硬化物からなる封止材で封止する。この製造方法において、上記組成物を硬化する方法としては、室温放置、あるいは加熱により硬化することができ、迅速に硬化させるためには加熱することが好ましい。加熱温度としては、５０〜２００℃の範囲内であることが好ましい。
このようにして得られる半導体装置において、シリコーン硬化物のＪＩＳ Ｋ６２５３に規定されるタイプＡデュロメータ硬さは１０〜９９であることが好ましく、特に、１５〜９５であることが好ましい。これは、シリコーン硬化物の硬さが上記範囲の下限以上であると、硬化物の強度が大きくなり、外部からの応力に対して半導体素子を十分に保護することができるからであり、一方、上記範囲の上限以下であると、硬化物が柔軟となり、熱衝撃に対して半導体素子を十分に保護することができるからである。
次に、本発明の半導体素子封止用硬化性シリコーン組成物を詳細に説明する。
本発明の半導体素子封止用硬化性シリコーン組成物は、半導体装置中の金メッキされたリードまたは基板と半導体素子を封止するためのヒドロシリル化反応硬化性シリコーン組成物であって、（Ａ）一分子中に少なくとも２個のアルケニル基を有するオルガノポリシロキサン、（Ｂ）一分子中に少なくとも２個のケイ素原子結合水素原子を有するオルガノハイドロジェンポリシロキサン｛（Ａ）成分中のアルケニル基１モルに対して、本成分中のケイ素原子結合水素原子が０．１〜１０モルとなる量｝、（Ｃ）硫黄原子を結合し、ケイ素原子結合加水分解性基を有する有機ケイ素化合物（本組成物に対して０．０００１〜２質量％）、および（Ｄ）ヒドロシリル化反応用白金系触媒（本組成物に対して、白金原子が０．０１〜５００質量ｐｐｍとなる量）から少なくともなることを特徴とする。
上記（Ａ）成分〜（Ｄ）成分については、前述のとおりである。また、本組成物には、常温での可使時間を延長し、保存安定性を向上させるための（Ｅ）ヒドロシリル化反応抑制剤の他；接着促進剤；蛍光体；シリカ、ガラス、およびアルミナ等から選択される１種又は２種以上の無機質充填剤；シリコーンゴム粉末；シリコーン樹脂、およびポリメタクリレート樹脂等の樹脂粉末；耐熱剤、染料、顔料、難燃性付与剤、界面活性剤、溶剤等から選択される１種又は２種以上の成分を含有してもよい。これらの成分およびその含有量については前述のとおりである。
このような本発明の硬化性シリコーン組成物は、上記（Ａ）成分〜（Ｄ）成分、さらには、上記の任意成分からなるものであり、一液型、あるいは任意の成分に分けられた二液型とすることができる。First, the semiconductor device of the present invention will be described in detail.
The semiconductor device of the present invention is a semiconductor device in which a gold-plated lead or substrate and a semiconductor element are sealed with a silicone cured product. Examples of the semiconductor element include a light emitting diode (LED) element, a semiconductor laser element, a photodiode element, a phototransistor element, a solid-state imaging element, a light emitting element or a light receiving element for a photocoupler, and in particular, a light emitting diode (LED) element. It is preferable that
The semiconductor device of the present invention will be described in detail with reference to FIG.
FIG. 1 is a cross-sectional view of an optical semiconductor device (LED) which is an example of a semiconductor device. In this optical semiconductor device (LED), a light emitting diode (LED)
In the semiconductor device of the present invention, the cured silicon product in which the gold-plated lead or substrate and the semiconductor element are sealed is (A) an organopolysiloxane having at least two alkenyl groups in one molecule, and (B) in one molecule. Organohydrogenpolysiloxane having at least two silicon atom-bonded hydrogen atoms in {1 mol of alkenyl groups in component (A) is 0.1 to 10 mol of silicon atom-bonded hydrogen atoms in this component Amount}, (C) an organic silicon compound having a silicon atom-bonded hydrolyzable group bonded to a sulfur atom (0.0001 to 2% by mass with respect to the present composition), and (D) a platinum system for hydrosilylation reaction Curing of a hydrosilylation reaction-curable silicone composition comprising at least a catalyst (amount in which platinum atoms are 0.01 to 500 ppm by mass with respect to the present composition) And characterized in that.
Component (A) is the main component of the above composition and is an organopolysiloxane having at least two alkenyl groups in one molecule. As the alkenyl group in the component (A), the vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, etc. Twelve alkenyl groups are exemplified, and a vinyl group is preferable. In addition, as the group bonded to the silicon atom other than the alkenyl group in the component (A), a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, Alkyl groups having 1 to 12 carbon atoms such as hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group; carbon such as phenyl group, tolyl group, xylyl group, naphthyl group An aryl group having 6 to 20 carbon atoms; an aralkyl group having 7 to 20 carbon atoms such as a benzyl group, a phenethyl group, and a phenylpropyl group; a part or all of hydrogen atoms of these groups may be a fluorine atom, a chlorine atom, Examples thereof include a group substituted with a halogen atom such as a bromine atom. In addition, the silicon atom in the component (A) may have a small amount of a hydroxyl group, an alkoxy group such as a methoxy group, an ethoxy group or the like as long as the object of the present invention is not impaired.
The molecular structure of the component (A) is not particularly limited, and examples thereof include linear, partially branched linear, branched, cyclic, and three-dimensional network structures. The component (A) may be a single organopolysiloxane having these molecular structures or a mixture of two or more organopolysiloxanes having these molecular structures.
In such component (A), the alkenyl group is 0.01 to 50 mol%, 0.05 to 40 mol%, or 0.09 to 32 mol% with respect to the silicon-bonded total organic group. Is preferred. This is because if there are too few alkenyl groups in the component (A), a cured product may not be obtained, and if there are too many alkenyl groups in the component (A), the mechanical properties of the resulting cured product will deteriorate. Because there is a fear. Moreover, it is preferable that the alkenyl group in (A) component exists in the both ends of the molecular chain of organopolysiloxane. In addition, the mol% of the alkenyl group in the component (A) is determined by analysis such as Fourier transform infrared spectrophotometer (FT-IR), nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), etc. Can do.
Component (A) is an organopolysiloxane that is liquid or solid at 25 ° C. When the component (A) is liquid at 25 ° C., the viscosity at 25 ° C. is in the range of 1 to 1,000,000 mPa · s, or in the range of 10 to 1,000,000 mPa · s. Is preferred. The viscosity of the organopolysiloxane at 25 ° C. can be determined, for example, by measurement using a B-type viscometer according to JIS K7117-1.
Component (B) is a crosslinking agent of the above composition, and is an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule. (B) As a group couple | bonded with silicon atoms other than a hydrogen atom in a component, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group Alkyl groups having 1 to 12 carbon atoms such as cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc .; carbon numbers such as phenyl group, tolyl group, xylyl group, naphthyl group, etc. 6 to 20 aryl groups; aralkyl groups having 7 to 20 carbon atoms such as benzyl group, phenethyl group and phenylpropyl group; some or all of hydrogen atoms of these groups are fluorine atom, chlorine atom, bromine atom And a group substituted with a halogen atom such as In addition, the silicon atom in the component (B) may have a small amount of a hydroxyl group, an alkoxy group such as a methoxy group, an ethoxy group or the like as long as the object of the present invention is not impaired.
The molecular structure of the component (B) is not particularly limited, and examples thereof include linear, linear, partially branched, branched, cyclic, and three-dimensional network structures. Examples include chain, branched chain, and three-dimensional network structures.
The component (B) is solid or liquid at 25 ° C. When the component (B) is liquid at 25 ° C., the viscosity at 25 ° C. is 10,000 mPa · s or less, within the range of 0.1 to 5,000 mPa · s, or 0.5 to 1, It is preferably within the range of 000 mPa · s. The viscosity of the organopolysiloxane at 25 ° C. can be determined, for example, by measurement using a B-type viscometer according to JIS K7117-1.
The component (B) is not particularly limited to a specific organopolysiloxane as long as the object of the present invention can be achieved. For example, 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetra Methylcyclotetrasiloxane, tris (dimethylhydrogensiloxy) methylsilane, tris (dimethylhydrogensiloxy) phenylsilane, 1-glycidoxypropyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-digly Sidoxypropyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-glycidoxypropyl-5-trimethoxysilylethyl-1,3,5,7-tetramethylcyclotetrasiloxane, both ends of molecular chain Trimethylsiloxy group-blocked methylhydrogenpolysiloxane, trimer at both ends of molecular chain Lucyloxy-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, dimethylhydrogensiloxy-blocked dimethylpolysiloxane with molecular chain at both ends, dimethylhydrogensiloxy-blocked dimethylsiloxane / methylhydrogensiloxane copolymer with molecular chain at both ends Trimethylsiloxy group-capped methylhydrogensiloxane / diphenylsiloxane copolymer at both ends of the chain, trimethylsiloxy group-capped methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer at both ends of the molecular chain, (CH 3 ) 2 HSiO 1/2 unit and a copolymer consisting of SiO 4/2 units, and (CH 3) 2 HSiO 1/2 units and the SiO 4/2 units (C 6 H 5) consisting of SiO 3/2 units, and copolymers and the like Group 1 type (s) or 2 or more types selected from are mentioned.
The content of the component (B) is an amount such that the silicon-bonded hydrogen atom in the component is 0.1 to 10 mol, preferably 0.1%, with respect to 1 mol of the alkenyl group in the component (A). The amount is 5 to 5 mol. This is because when the content of the component (B) is not more than the upper limit of the above range, it is possible to suppress a decrease in the mechanical properties of the obtained cured product, and on the other hand, if it is not less than the lower limit of the above range, This is because the resulting composition is sufficiently cured. In addition, content of the silicon atom bond hydrogen atom in (B) component is analysis, such as a Fourier-transform infrared spectrophotometer (FT-IR), nuclear magnetic resonance (NMR), gel permeation chromatography (GPC) etc., for example. Can be obtained.
The organosilicon compound (C) is a component that binds sulfur atoms and has a silicon atom-bonded hydrolyzable group, and imparts good adhesion to a lead frame that is gold-plated to the above composition. . Examples of such a component (C) include mercaptoalkylalkoxysilanes such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxysilane; Examples thereof include bis (alkoxysilylalkyl) sulfides such as (trimethoxysilylpropyl) disulfide, bis (trimethoxysilylpropyl) trisulfide, and bis (trimethoxysilylpropyl) tetrasulfide.
(C) Content of component is 0.0001-2 mass% with respect to the said composition, Preferably, it will be 0.001-1 mass% or 0.01-0.2 mass%. Amount. This is because if it is at least the lower limit of the above range, the adhesion to a gold-plated lead or substrate is improved, while if it is below the upper limit of the above range, the composition is less likely to be inhibited from curing.
Component (D) is a platinum catalyst for hydrosilylation reaction for promoting the hydrosilylation reaction of the composition. As such component (D), platinum fine powder, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid and diolefin complex, platinum-olefin complex, platinum bis (acetoacetate), Platinum-carbonyl complex such as platinum bis (acetylacetonate), chloroplatinic acid-divinyltetramethyldisiloxane complex, chloroplatinic acid-alkenylsiloxane complex such as chloroplatinic acid-tetravinyltetramethylcyclotetrasiloxane complex, platinum-divinyl Examples include platinum-alkenylsiloxane complexes such as tetramethyldisiloxane complexes, platinum-tetravinyltetramethylcyclotetrasiloxane complexes, and complexes of chloroplatinic acid and acetylene alcohols, and particularly high hydrosilylation reaction promoting effects. From the platinum-alkenylsiloxane complex Rukoto is preferable. These platinum catalysts for hydrosilylation reaction may be used individually by 1 type, and may use 2 or more types together.
The alkenyl siloxane used in the platinum-alkenyl siloxane complex is not particularly limited. For example, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1 , 3,5,7-tetravinylcyclotetrasiloxane, alkenylsiloxane oligomers in which part of the methyl groups of these alkenylsiloxanes are substituted with ethyl groups, phenyl groups, etc., and the vinyl groups of these alkenylsiloxanes are allyl groups, hexenyls And alkenylsiloxane oligomers substituted with a group. In particular, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferred because the resulting platinum-alkenylsiloxane complex has good stability.
In order to improve the stability of the platinum-alkenylsiloxane complex, these platinum-alkenylsiloxane complexes may be converted to 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-diallyl-1 1,3,3-tetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane, 1,3-divinyl-1,1,3,3-tetraphenyldisiloxane , And 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane and other alkenylsiloxane oligomers and dimethylsiloxane oligomers and other organosiloxane oligomers, It is preferably dissolved in the alkenylsiloxane oligomer.
The content of the component (D) is such that the platinum atom in the component (D) is 0.01 to 500 ppm by mass, preferably in the range of 0.01 to 100 ppm by mass with respect to the composition. The amount is within the range of 0.1 to 50 ppm by mass. This is because when the content of the component (D) is not less than the lower limit of the above range, the resulting composition is sufficiently cured, whereas when it is not more than the upper limit of the above range, the resulting cured product is colored. It is because it is suppressed.
The composition may contain (E) a hydrosilylation reaction inhibitor as an optional component for extending the pot life at room temperature and improving storage stability. Examples of such component (E) include 1-ethynylcyclohexane-1-ol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, and 2-phenyl- Alkyne alcohols such as 3-butyn-2-ol; Enyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; 1,3,5,7 Methyl alkenylsiloxane oligomers such as tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane and 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane; Alkyl such as dimethylbis (3-methyl-1-butyne-3-oxy) silane and methylvinylbis (3-methyl-1-butyne-3-oxy) silane Oxysilane, and triallyl isocyanurate compounds.
Although the content of the component (E) is not particularly limited, it is an amount sufficient to suppress gelation or suppress curing when the above components (A) to (D) are mixed, and for a long period of time. Sufficient to allow storage. Specifically, the content of the component (E) is in the range of 0.0001 to 5 parts by mass with respect to the total of 100 parts by mass of the components (A) to (D), or 0.01 to It is preferably within the range of 3 parts by mass.
Moreover, in order to further improve the adhesiveness to the base material which is contacting during hardening, you may contain an adhesion promoter in the said composition. As this adhesion promoter, an organosilicon compound having one or more alkoxy groups bonded to silicon atoms in one molecule is preferable. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a methoxyethoxy group, and a methoxy group or an ethoxy group is particularly preferable. In addition, as a group other than the alkoxy group bonded to the silicon atom of the organosilicon compound, a substituted or unsubstituted monovalent hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group, an aralkyl group, and a halogenated alkyl group; Glycidoxyalkyl groups such as 3-glycidoxypropyl group and 4-glycidoxybutyl group; 2- (3,4-epoxycyclohexyl) ethyl group and 3- (3,4-epoxycyclohexyl) propyl group Epoxy cyclohexyl alkyl groups such as 4-oxiranyl butyl group and oxiranyl alkyl groups such as 8-oxiranyl octyl group; acrylic group-containing monovalent organic groups such as 3-methacryloxypropyl group; isocyanate groups; Examples include isocyanurate groups; as well as hydrogen atoms. This organosilicon compound preferably has an alkenyl group or a group capable of reacting with a silicon atom-bonded hydrogen atom in the composition, and specifically, preferably has a silicon atom-bonded hydrogen atom or an alkenyl group.
The content of the adhesion promoter is not limited, but is within the range of 0.01 to 10 parts by mass, or 0.1 to 3 parts by mass with respect to 100 parts by mass in total of the above components (A) to (D). It is preferable to be within the range.
Moreover, the said composition can contain fluorescent substance as another arbitrary component. Examples of the phosphor include oxide phosphors, oxynitride phosphors, nitride phosphors, sulfide phosphors, and oxysulfide phosphors that are widely used in light emitting diodes (LEDs). Examples thereof include yellow, red, green, and blue light emitting phosphors. Examples of oxide phosphors include yttrium, aluminum, and garnet-based YAG green to yellow light-emitting phosphors containing cerium ions; terbium, aluminum, and garnet-based TAG yellow light-emitting phosphors containing cerium ions; and Examples include silicate green to yellow light emitting phosphors containing cerium and europium ions. Examples of the oxynitride phosphor include silicon, aluminum, oxygen, and nitrogen-based sialon-based red to green light-emitting phosphors containing europium ions. Examples of nitride-based phosphors include calcium, strontium, aluminum, silicon, and nitrogen-based casoon-based red light-emitting phosphors containing europium ions. Examples of sulfide-based phosphors include ZnS-based green color phosphors including copper ions and aluminum ions. Examples of oxysulfide phosphors include Y 2 O 2 S red light-emitting phosphors containing europium ions. These phosphors may use one kind or a mixture of two or more kinds.
Although content of this fluorescent substance is not specifically limited, It is preferable that it exists in the range of 0.1-70 mass% in the said composition, or the range of 1-20 mass%.
Further, in the above composition, as long as the object of the present invention is not impaired, one or more inorganic fillers selected from silica, glass, alumina and the like as other optional components; silicone rubber powder; Resin powders such as silicone resins and polymethacrylate resins; one or more components selected from heat-resistant agents, dyes, pigments, flame retardants, surfactants, solvents and the like may be contained.
The manufacturing method of the semiconductor device of the present invention is not particularly limited. For example, the optical semiconductor device (LED) shown in FIG. 1 can be manufactured as follows.
A light emitting diode (LED)
In the semiconductor device thus obtained, the type A durometer hardness defined in JIS K6253 of the silicone cured product is preferably 10 to 99, and particularly preferably 15 to 95. This is because when the hardness of the silicone cured product is equal to or higher than the lower limit of the above range, the strength of the cured product is increased, and the semiconductor element can be sufficiently protected against external stress, It is because hardened | cured material will become flexible and it can fully protect a semiconductor element with respect to a thermal shock as it is below the upper limit of the said range.
Next, the curable silicone composition for sealing a semiconductor element of the present invention will be described in detail.
The curable silicone composition for encapsulating a semiconductor element of the present invention is a hydrosilylation reaction curable silicone composition for encapsulating a gold-plated lead or substrate in a semiconductor device and the semiconductor element. Organopolysiloxane having at least two alkenyl groups in the molecule, (B) Organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule {in 1 mol of alkenyl groups in component (A) In contrast, the amount of silicon atom-bonded hydrogen atoms in this component is 0.1 to 10 moles}, (C) an organosilicon compound having a silicon atom-bonded hydrolyzable group bonded to a sulfur atom (in this composition) 0.0001-2 mass%) and (D) a platinum catalyst for hydrosilylation reaction (the platinum atom is 0.01-500 mass pp with respect to the present composition). Characterized by at least comprising that from the amount) to be.
The components (A) to (D) are as described above. In addition to the (E) hydrosilylation reaction inhibitor for extending the pot life at room temperature and improving the storage stability, the present composition includes: an adhesion promoter; a phosphor; silica, glass, and alumina. 1 type or 2 or more types of inorganic fillers selected from, etc .; silicone rubber powder; resin powder such as silicone resin and polymethacrylate resin; heat-resistant agent, dye, pigment, flame retardant, surfactant, solvent You may contain 1 type, or 2 or more types of components selected from etc. These components and their contents are as described above.
Such a curable silicone composition of the present invention is composed of the above components (A) to (D) and the above optional components, and is divided into one component type or optional components. It can be a liquid type.
本発明の半導体装置および半導体素子封止用硬化性シリコーン組成物を実施例および比較例を用いて詳細に説明する。なお、化学式中、Ｍｅ、Ｖｉ、およびＰｈは、それぞれ、メチル基、ビニル基、およびフェニル基を示す。
［実施例１〜５、比較例１〜７］
次の成分を表１に示す組成（質量部）で均一に混合して実施例１〜５及び比較例１〜７の硬化性シリコーン組成物を調製した。また、表１中、ＳｉＨ／Ｖｉは、硬化性シリコーン組成物において、（Ａ）成分中のビニル基の合計１モルに対する、（Ｂ）成分中のケイ素原子結合水素原子の合計モル数を示す。
（Ａ）成分として、次の成分を用いた。なお、オルガノポリシロキサンは、公知の製法によって得ることができる。また、粘度は２５℃における値であり、ＪＩＳ Ｋ７１１７−１に準拠してＢ型粘度計を用いて測定した。また、ビニル基の含有量は、ＦＴ−ＩＲ、ＮＭＲ、ＧＰＣ等の分析によって測定した。
（ａ−１）成分：粘度３００ｍＰａ・ｓであり、平均式：
Ｍｅ２ＶｉＳｉＯ（Ｍｅ２ＳｉＯ）１５０ＳｉＭｅ２Ｖｉ
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン（ビニル基の含有量＝０．４８質量％）
（ａ−２）成分：粘度１０，０００ｍＰａ・ｓであり、平均式：
Ｍｅ２ＶｉＳｉＯ（Ｍｅ２ＳｉＯ）５００ＳｉＭｅ２Ｖｉ
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン（ビニル基の含有量＝０．１５質量％）
（ａ−３）成分：粘度１，０００ｍＰａ・ｓであり、平均式：
Ｍｅ２ＶｉＳｉＯ（ＭｅＰｈＳｉＯ）３０ＳｉＭｅ２Ｖｉ
で表されるメチルフェニルポリシロキサン（ビニル基の含有量＝１．２７質量％）
（ａ−４）成分：２５℃において白色固体状で、トルエン可溶性である、平均単位式：
（Ｍｅ２ＶｉＳｉＯ１／２）０．１３（Ｍｅ３ＳｉＯ１／２）０．４５（ＳｉＯ４／２）０．４２（ＨＯ１／２）０．０１
で表される一分子中に２個以上のビニル基を有するオルガノポリシロキサンレジン（ビニル基の含有量＝３．４質量％）
（ａ−５）成分：２５℃において白色固体状で、トルエン可溶性である、平均単位式：
（Ｍｅ２ＶｉＳｉＯ１／２）０．１５（Ｍｅ３ＳｉＯ１／２）０．３８（ＳｉＯ４／２）０．４７（ＨＯ１／２）０．０１
で表される一分子中に２個以上のビニル基を有するオルガノポリシロキサン（ビニル基の含有量＝４．２質量％）
（ａ−６）成分：２５℃において白色固体状で、トルエン可溶性である、平均単位式：
（ＰｈＳｉＯ３／２）０．７５（Ｍｅ２ＶｉＳｉＯ１／２）０．２５
で表される一分子中に２個以上のビニル基を有するオルガノポリシロキサン（ビニル基の含有量＝５．６質量％）
（Ｂ）成分として、次の成分を用いた。なお、オルガノハイドロジェンポリシロキサンは、公知の製法によって得ることができる。また、粘度は、２５℃における値であり、ＪＩＳ Ｋ７１１７−１に準拠してＢ型粘度計を用いて測定した。また、ケイ素原子結合水素原子の含有量と一分子当たりのケイ素原子結合水素原子の個数は、ＦＴ−ＩＲ、ＮＭＲ、ＧＰＣ等の分析によって測定した。
（ｂ−１）成分：平均式：
Ｍｅ３ＳｉＯ（ＭｅＨＳｉＯ）１５ＳｉＭｅ３
で表される、粘度５ｍＰａ・ｓの分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンポリシロキサン（ケイ素原子結合水素原子の含有量＝１．４２質量％）
（ｂ−２）成分：平均式：
Ｍｅ３ＳｉＯ（ＭｅＨＳｉＯ）５５ＳｉＭｅ３
で表される、粘度２０ｍＰａ・ｓの分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンポリシロキサン（ケイ素原子結合水素原子の含有量＝１．６質量％）
（ｂ−３）成分：平均式：
ＨＭｅ２ＳｉＯ（Ｐｈ２ＳｉＯ）ＳｉＭｅ２Ｈ
で表される、粘度５ｍＰａ・ｓの分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジフェニルポリシロキサン（ケイ素原子結合水素原子の含有量＝０．６質量％）
（ｂ−４）成分：平均単位式：
（ＰｈＳｉＯ３／２）０．４（ＨＭｅ２ＳｉＯ１／２）０．６
で表される、粘度２５ｍＰａ・ｓの一分子中に２個以上のケイ素原子結合水素原子を有する分岐鎖状オルガノポリシロキサン（ケイ素原子結合水素原子の含有量＝０．６５質量％）
（Ｃ）成分として、次の成分を用いた。
（ｃ−１）成分：３−メルカプトプロピルトリメトキシシラン
（ｃ−２）成分：ビス（３−トリエトキシシリルプロピル）テトラスルフィド
（ｃ−３）成分：１，３，５−トリグリシジルイソシアヌル酸
（ｃ−４）成分：３−メタクリロキシプロピルトリメトキシシラン
（ｃ−５）成分：３−アクリロキシプロピルトリメトキシシラン
（ｃ−６）成分：３−グリシドキシプロピルトリメトキシシラン
（ｃ−７）成分：２−メルカプトベンゾチアゾール
（Ｄ）成分として、白金の１，３−ジビニルテトラメチルジシロキサン錯体の１，３−ジビニルテトラメチルジシロキサン溶液（白金金属の含有量＝約５０００質量ｐｐｍ）を用いた。
（Ｅ）成分として、１−エチニルシクロヘキサン−１−オールを用いた。
［評価と結果］
実施例１〜５および比較例１〜７で得られた硬化性シリコーン組成物について、「１５０℃のゲル化時間」、「シリコーン硬化物の硬さ」、「封止材の初期剥離率」、および「封止材の吸湿リフロー後の剥離率」を次のようにして測定し、その結果を表１に示した。
［１５０℃のゲル化時間］
１５０℃のゲル化時間（秒）は、Ａｌｐｈａ Ｔｅｃｈｎｏｌｏｇｉｅｓ Ｒｈｅｏｍｅｔｅｒ ＭＤＲ ２０００Ｐを用いて測定した。
［シリコーン硬化物の硬さ］
シリコーン硬化物の硬さは、実施例１〜５及び比較例１〜７で得られた硬化性シリコーン組成物を１５０℃で１時間、５ＭＰａの圧力でプレス成形することによりシート状のシリコーン硬化物を作製し、この硬さをＪＩＳ Ｋ ６２５３に規定されるタイプＡデュロメータにより測定した。
［光半導体装置（ＬＥＤ）の作製］
底部が塞がった円筒状のポリフタルアミド（ＰＰＡ）樹脂ケース（内径２．０ｍｍ、深さ１．０ｍｍ）の内底部の中心部に向かって、金メッキされたリードが側壁から延出しており、金メッキされたリードの中央部上にＬＥＤチップが載置されており、ＬＥＤチップと金メッキされたリードは金製ボンディングワイヤにより電気的に接続している前駆体の、ポリフタルアミド（ＰＰＡ）樹脂ケース内に、各実施例または各比較例の硬化性シリコーン組成物を脱泡してディスペンサーを用いて注入し、加熱オーブン中、１００℃で３０分、続いて１５０℃で１時間加熱して、硬化させることにより、各々２０個の図１に示す光半導体装置（ＬＥＤ）を作製した。
［封止材の初期剥離率］
上記光半導体装置（ＬＥＤ）２０個について、金メッキされたリード２と封止材７間の剥離状態を光学顕微鏡で観察し、剥離した個数／２０個を剥離率とした。
［吸湿リフロー後の剥離率］
上記光半導体装置（ＬＥＤ）２０個を、８５℃／８５％ＲＨの高温高湿条件下で１６８時間保持した後、２８０℃のオーブン内に３０秒間静置した。その後、室温（２５℃）にして、金メッキされたリード２と封止材７間の剥離状態を光学顕微鏡で観察し、剥離した個数／２０個を剥離率とした。
[Examples 1 to 5, Comparative Examples 1 to 7]
The following components were uniformly mixed in the composition (parts by mass) shown in Table 1 to prepare curable silicone compositions of Examples 1 to 5 and Comparative Examples 1 to 7. In Table 1, SiH / Vi represents the total number of moles of silicon-bonded hydrogen atoms in the component (B) relative to a total of 1 mole of vinyl groups in the component (A) in the curable silicone composition.
The following components were used as the component (A). The organopolysiloxane can be obtained by a known production method. The viscosity is a value at 25 ° C., and was measured using a B-type viscometer in accordance with JIS K7117-1. The vinyl group content was measured by analysis such as FT-IR, NMR, GPC and the like.
(A-1) Component: Viscosity of 300 mPa · s, average formula:
Me 2 ViSiO (Me 2 SiO) 150 SiMe 2 Vi
Dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by formula (Vinyl group content = 0.48 mass%)
(A-2) component: viscosity is 10,000 mPa · s, average formula:
Me 2 ViSiO (Me 2 SiO) 500 SiMe 2 Vi
Dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by formula (Vinyl group content = 0.15 mass%)
(A-3) Component: Viscosity of 1,000 mPa · s, average formula:
Me 2 ViSiO (MePhSiO) 30 SiMe 2 Vi
Methylphenyl polysiloxane represented by the formula (vinyl group content = 1.27% by mass)
(A-4) Component: A white solid at 25 ° C. and soluble in toluene. Average unit formula:
(Me 2 ViSiO 1/2 ) 0.13 (Me 3 SiO 1/2 ) 0.45 (SiO 4/2 ) 0.42 (HO 1/2 ) 0.01
An organopolysiloxane resin having two or more vinyl groups in one molecule represented by (content of vinyl group = 3.4% by mass)
(A-5) Component: Average unit formula that is white solid at 25 ° C. and soluble in toluene:
(Me 2 ViSiO 1/2 ) 0.15 (Me 3 SiO 1/2 ) 0.38 (SiO 4/2 ) 0.47 (HO 1/2 ) 0.01
An organopolysiloxane having two or more vinyl groups in one molecule represented by the formula (vinyl group content = 4.2 mass%)
(A-6) Component: Average unit formula that is white solid at 25 ° C. and soluble in toluene:
(PhSiO 3/2 ) 0.75 (Me 2 ViSiO 1/2 ) 0.25
An organopolysiloxane having two or more vinyl groups in one molecule represented by the formula (vinyl group content = 5.6% by mass)
As the component (B), the following components were used. The organohydrogenpolysiloxane can be obtained by a known production method. Moreover, a viscosity is a value in 25 degreeC and measured using the B-type viscosity meter based on JISK7117-1. The content of silicon-bonded hydrogen atoms and the number of silicon-bonded hydrogen atoms per molecule were measured by analysis such as FT-IR, NMR, GPC and the like.
(B-1) Component: Average formula:
Me 3 SiO (MeHSiO) 15 SiMe 3
The molecular chain both ends trimethylsiloxy group-capped methylhydrogenpolysiloxane with a viscosity of 5 mPa · s (content of silicon-bonded hydrogen atoms = 1.42 mass%)
(B-2) Component: Average formula:
Me 3 SiO (MeHSiO) 55 SiMe 3
The molecular chain both ends trimethylsiloxy group-blocked methyl hydrogen polysiloxane with a viscosity of 20 mPa · s (content of silicon-bonded hydrogen atoms = 1.6 mass%)
(B-3) Component: Average formula:
HMe 2 SiO (Ph 2 SiO) SiMe 2 H
Dimethylhydrogensiloxy group-blocked diphenylpolysiloxane having a viscosity of 5 mPa · s and having a viscosity of 5 mPa · s (content of silicon-bonded hydrogen atoms = 0.6 mass%)
(B-4) Component: Average unit formula:
(PhSiO 3/2 ) 0.4 (HMe 2 SiO 1/2 ) 0.6
A branched organopolysiloxane having two or more silicon atom-bonded hydrogen atoms in one molecule with a viscosity of 25 mPa · s (content of silicon atom-bonded hydrogen atoms = 0.65 mass%)
As the component (C), the following components were used.
(C-1) component: 3-mercaptopropyltrimethoxysilane (c-2) component: bis (3-triethoxysilylpropyl) tetrasulfide (c-3) component: 1,3,5-triglycidyl isocyanuric acid ( c-4) component: 3-methacryloxypropyltrimethoxysilane (c-5) component: 3-acryloxypropyltrimethoxysilane (c-6) component: 3-glycidoxypropyltrimethoxysilane (c-7) Component: 2-mercaptobenzothiazole As component (D), a 1,3-divinyltetramethyldisiloxane solution of platinum with a 1,3-divinyltetramethyldisiloxane complex (platinum metal content = about 5000 mass ppm) is used. It was.
As component (E), 1-ethynylcyclohexane-1-ol was used.
[Evaluation and results]
For the curable silicone compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 7, “150 ° C. gelation time”, “hardness of silicone cured product”, “initial release rate of sealing material”, And “the peeling rate after moisture absorption reflow of the sealing material” was measured as follows, and the results are shown in Table 1.
[Gelation time at 150 ° C.]
The gelation time (seconds) at 150 ° C. was measured using Alpha Technologies Rheometer MDR 2000P.
[Hardness of cured silicone]
The hardness of the silicone cured product is a sheet-shaped silicone cured product obtained by press molding the curable silicone compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 7 at 150 ° C. for 1 hour at a pressure of 5 MPa. The hardness was measured with a type A durometer as defined in JIS K 6253.
[Production of optical semiconductor device (LED)]
A gold-plated lead extends from the side wall toward the center of the inner bottom of a cylindrical polyphthalamide (PPA) resin case (inner diameter 2.0 mm, depth 1.0 mm) whose bottom is closed. The LED chip is placed on the center of the lead, and the LED chip and the gold-plated lead are electrically connected by a gold bonding wire in the precursor of the polyphthalamide (PPA) resin case The curable silicone composition of each Example or each Comparative Example was defoamed and poured using a dispenser, and cured by heating in a heating oven at 100 ° C. for 30 minutes and then at 150 ° C. for 1 hour. As a result, 20 optical semiconductor devices (LEDs) shown in FIG. 1 were produced.
[Initial peeling rate of sealing material]
For the 20 optical semiconductor devices (LEDs), the peeled state between the gold-plated lead 2 and the sealing material 7 was observed with an optical microscope, and the peeled number / 20 was defined as the peel rate.
[Peeling rate after moisture absorption reflow]
Twenty optical semiconductor devices (LEDs) were held under high temperature and high humidity conditions of 85 ° C./85% RH for 168 hours, and then left in an oven at 280 ° C. for 30 seconds. Thereafter, the peeled state between the gold-plated lead 2 and the sealing material 7 was observed with an optical microscope at room temperature (25 ° C.), and the peeled number / 20 was defined as the peel rate.
本発明の半導体装置は、吸湿リフロー試験後、金メッキされたリードとシリコーン硬化物からなる封止材との剥離を生じ難いので、信頼性の要求が厳しい光半導体装置（ＬＥＤ）として好適である。 The semiconductor device of the present invention is suitable as an optical semiconductor device (LED) having a strict requirement for reliability because it is difficult to cause peeling between the gold-plated lead and the sealing material made of the cured silicone after the moisture absorption reflow test.
１ ポリフタルアミド（ＰＰＡ）樹脂製筐体
２ 金メッキされたリード
３ ダイパッド
４ 接着材
５ 発光ダイオード（ＬＥＤ）素子
６ 金製ボンディングワイヤ
７ シリコーン硬化物からなる封止材DESCRIPTION OF SYMBOLS 1 Polyphthalamide (PPA) resin housing 2 Gold-plated lead 3 Die pad 4
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| ATE555178T1 (en) * | 2009-12-18 | 2012-05-15 | Sika Technology Ag | HOT MEL ADHESIVE COMPOSITIONS WITH GOOD ADHESION TO BOTH POLAR AND APOLAR SUBSTRATES |
| JP5682257B2 (en) * | 2010-07-30 | 2015-03-11 | 三菱化学株式会社 | Resin composition for semiconductor light emitting device |
| KR101305438B1 (en) * | 2011-05-13 | 2013-09-06 | 현대자동차주식회사 | Adhesives for Bonding Polyurethane and Aluminium |
| JP2013043901A (en) * | 2011-08-22 | 2013-03-04 | Sumitomo Rubber Ind Ltd | Rubber composition for tire and pneumatic tire |
| JP5545601B2 (en) * | 2011-11-07 | 2014-07-09 | 信越化学工業株式会社 | Phosphor highly-filled wavelength conversion sheet, method for manufacturing light-emitting semiconductor device using the same, and light-emitting semiconductor device |
| JP6087127B2 (en) * | 2012-12-14 | 2017-03-01 | 株式会社カネカ | Thermosetting resin composition with improved fluidity and semiconductor package using the same |
-
2014
- 2014-05-28 KR KR1020157033397A patent/KR20160013872A/en not_active Application Discontinuation
- 2014-05-28 CN CN201480029204.6A patent/CN105229783B/en active Active
- 2014-05-28 JP JP2015519987A patent/JP6355210B2/en active Active
- 2014-05-28 WO PCT/JP2014/064798 patent/WO2014192969A1/en active Application Filing
- 2014-05-29 TW TW103118858A patent/TWI621664B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105229783A (en) | 2016-01-06 |
| CN105229783B (en) | 2018-06-22 |
| WO2014192969A1 (en) | 2014-12-04 |
| TW201502208A (en) | 2015-01-16 |
| KR20160013872A (en) | 2016-02-05 |
| TWI621664B (en) | 2018-04-21 |
| JPWO2014192969A1 (en) | 2017-02-23 |
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