WO2015034073A1 - Method of manufacturing optical semiconductor device and optical semiconductor device - Google Patents
Method of manufacturing optical semiconductor device and optical semiconductor device Download PDFInfo
- Publication number
- WO2015034073A1 WO2015034073A1 PCT/JP2014/073592 JP2014073592W WO2015034073A1 WO 2015034073 A1 WO2015034073 A1 WO 2015034073A1 JP 2014073592 W JP2014073592 W JP 2014073592W WO 2015034073 A1 WO2015034073 A1 WO 2015034073A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- optical semiconductor
- semiconductor device
- curable silicone
- hydrosilylation reaction
- silicone composition
- Prior art date
Links
- 230000003287 optical effect Effects 0.000 title claims abstract description 127
- 239000004065 semiconductor Substances 0.000 title claims abstract description 127
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 85
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 242
- 239000000203 mixture Substances 0.000 claims abstract description 180
- 238000007789 sealing Methods 0.000 claims abstract description 83
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 69
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims description 61
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 60
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 35
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 32
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 22
- 239000011256 inorganic filler Substances 0.000 claims description 19
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 18
- 229910052697 platinum Inorganic materials 0.000 claims description 13
- 125000003342 alkenyl group Chemical group 0.000 claims description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 239000003365 glass fiber Substances 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 9
- 239000012463 white pigment Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000002683 reaction inhibitor Substances 0.000 claims description 7
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 5
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 4
- 229910002113 barium titanate Inorganic materials 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 80
- 238000002845 discoloration Methods 0.000 abstract description 35
- 238000003860 storage Methods 0.000 abstract description 8
- 238000001723 curing Methods 0.000 description 39
- -1 3-chloropropyl group Chemical group 0.000 description 35
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 24
- 125000003700 epoxy group Chemical group 0.000 description 18
- 238000011156 evaluation Methods 0.000 description 16
- 239000002131 composite material Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- BSXVSQHDSNEHCJ-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)oxy-diphenylsilyl]oxy-dimethylsilicon Chemical compound C=1C=CC=CC=1[Si](O[Si](C)C)(O[Si](C)C)C1=CC=CC=C1 BSXVSQHDSNEHCJ-UHFFFAOYSA-N 0.000 description 6
- 239000002318 adhesion promoter Substances 0.000 description 6
- 239000011164 primary particle Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- 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 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000748 compression moulding Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000001721 transfer moulding Methods 0.000 description 4
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000005350 fused silica glass Substances 0.000 description 3
- 239000002184 metal Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000001282 organosilanes Chemical class 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920000193 polymethacrylate Polymers 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 239000002904 solvent Substances 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
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl 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
- 125000003118 aryl group Chemical group 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical group [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-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
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- QWOVEJBDMKHZQK-UHFFFAOYSA-N 1,3,5-tris(3-trimethoxysilylpropyl)-1,3,5-triazinane-2,4,6-trione Chemical compound CO[Si](OC)(OC)CCCN1C(=O)N(CCC[Si](OC)(OC)OC)C(=O)N(CCC[Si](OC)(OC)OC)C1=O QWOVEJBDMKHZQK-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
- KSLSOBUAIFEGLT-UHFFFAOYSA-N 2-phenylbut-3-yn-2-ol Chemical compound C#CC(O)(C)C1=CC=CC=C1 KSLSOBUAIFEGLT-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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
- HMVBQEAJQVQOTI-UHFFFAOYSA-N 3,5-dimethylhex-3-en-1-yne Chemical compound CC(C)C=C(C)C#C HMVBQEAJQVQOTI-UHFFFAOYSA-N 0.000 description 1
- GRGVQLWQXHFRHO-UHFFFAOYSA-N 3-methylpent-3-en-1-yne Chemical compound CC=C(C)C#C GRGVQLWQXHFRHO-UHFFFAOYSA-N 0.000 description 1
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 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
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 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
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 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 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 150000008282 halocarbons Chemical group 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 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 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 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 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-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
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
-
- 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
- H01L2224/48257—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 die pad of the item
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73251—Location after the connecting process on different surfaces
- H01L2224/73265—Layer and wire connectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L2224/85909—Post-treatment of the connector or wire bonding area
- H01L2224/8592—Applying permanent coating, e.g. protective coating
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/181—Encapsulation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0025—Processes relating to coatings
Definitions
- the present invention relates to a method of manufacturing an optical semiconductor device, and particularly relates to a method of manufacturing an optical semiconductor device in which the storage stability of the sealing agent of the optical semiconductor device can be realized, and the sealing agent has good heat resistance and can greatly resist discoloration, and an optical semiconductor device obtained by the manufacturing method.
- Curable silicone compositions that cure due to a hydrosilylation reaction have been used as sealing agents, coating agents, lens-molding materials, light reflection materials, and the like for optical semiconductor elements in optical semiconductor devices such as photocouplers, light-emitting diodes, solid-state image sensors, and the like.
- a curable silicone composition is proposed, the composition being composed of an organopolysiloxane having an average of not less than 0.2 silicon-bonded alkenyl groups per molecule, an organopolysiloxane having a three- dimensional network structure, an organopolysiloxane having not less than two silicon- bonded hydrogen atoms per molecule, and a hydrosilylation reaction catalyst.
- a curable silicone composition is proposed, the composition being composed of an organopolysiloxane having a silicon-bonded phenyl group and a silicon-bonded alkenyl group, an organopolysiloxane having a silicon-bonded hydrogen atom, and a hydrosilylation reaction catalyst.
- hydrosilylation reaction catalyst because the reaction does not proceed to begin with, and it is also considered that a sealing agent or the like composed of a composition that does not contain the hydrosilylation reaction catalyst cannot be provided as a product.
- the conventional cured silicones have the following problems. While high heat resistance is required of sealing agents of optical semiconductor elements, because the sealing agents directly receive heat generated from the elements, the conventional cured silicones yellow when exposed to high temperatures.
- Prior Art Documents
- Patent Document 1 Japanese Unexamined Patent Application Publication No. 2006- 213789
- Patent Document 2 Japanese Unexamined Patent Application Publication No. 2009- 185226
- an object of the present invention is to provide a method of manufacturing an optical semiconductor device in which the storage stability of the sealing agent of the optical semiconductor device can be realized, and the sealing agent has good heat resistance and can greatly resist discoloration even when exposed to high temperatures, and an optical semiconductor device obtained by the manufacturing method.
- the present inventors discovered that discoloration arising due to the fact that the sealing agent contains a hydrosilylation reaction catalyst can be suppressed and good heat resistance can be realized by using a curable silicone composition that cures due to a hydrosilylation reaction and contains very little or no hydrosilylation reaction catalyst as the sealing agent of an optical semiconductor element and by disposing cured silicone containing a hydrosilylation reaction catalyst as a member separate from the sealing agent.
- curable silicone composition that forms the sealing agent does not itself cure, a curable silicone composition, which is conventionally provided in a two- part form, can be provided in a one-part form, and therefore the complexity of the mixing operation of the two parts and the degassing operation after mixing can be avoided, and mistakes in compounding when mixing can be prevented.
- a first embodiment of the present invention is a method of manufacturing an optical semiconductor device comprising a step of sealing an optical semiconductor element using a curable silicone composition, wherein the curable silicone composition, although cured by a hydrosilylation reaction, does not contain a
- the curable silicone composition does contain the hydrosilylation reaction catalyst, a content of the hydrosilylation reaction catalyst is not enough to cure the composition, and the optical semiconductor element is sealed in a state in which the curable silicone composition contacts cured silicone that contains the hydrosilylation reaction catalyst.
- the curable silicone composition comprising: (A) at least one type of organopolysiloxane having not less than two silicon-bonded alkenyl groups per molecule, and (B) at least one type of organopolysiloxane having not less than two silicon- bonded hydrogen atoms per molecule, and does not contain the hydrosilylation reaction catalyst, or, if curable silicone composition does contain the hydrosilylation reaction catalyst, the content of the hydrosilylation reaction catalyst is preferably not enough to cure the composition.
- the hydrosilylation reaction catalyst is preferably a platinum-based catalyst, and the curable silicone composition preferably does not contain a hydrosilylation reaction inhibitor.
- the cured silicone is preferably a light reflection material, substrate, a dam material, or a fluorescent substance-containing sheet.
- the cured silicone preferably contains at least one type of white pigment selected from the group consisting of titanium oxide, zinc oxide, barium titanate, barium sulfate, and zirconium oxide, and preferably contains at least one type of inorganic filler selected from the group consisting of non-spherical silica, spherical silica, and glass fibers.
- Another embodiment of the present invention is an optical semiconductor device manufactured by the above-described method of manufacturing an optical semiconductor device. Effects of Invention
- a method of manufacturing an optical semiconductor device in which the sealing agent of the optical semiconductor device realizes storage stability, has good heat resistance, and can greatly resist discoloration can be provided; and an optical semiconductor device obtained by the manufacturing method can be provided.
- the sealing agent is optically transparent or white even when it has been exposed to high temperature
- the optical semiconductor device obtained by the method of manufacturing the present invention can also be used alone or in combination with various substrates for electrical and electronic parts or optical elements.
- FIG. 1 is a cross-sectional view of an LED that is an example of an optical semiconductor device of the present invention.
- FIG. 2 is a cross- sectional view of an LED that is another example of the optical semiconductor device of the present invention.
- FIG. 3 is a cross-sectional view of an LED that is yet another example of the optical semiconductor device of the present invention.
- FIG. 4 is a cross-sectional view of an LED that is still another example of the optical semiconductor device of the present invention.
- the method of manufacturing an optical semiconductor device according to the present invention includes a step of sealing an optical semiconductor element using a curable silicone composition.
- an optical semiconductor element 1 is sealed by disposing cured silicone (light reflection material 5 in FIG. 1) containing a hydrosilylation reaction catalyst, and then, using a curable silicone composition that cures due to a hydrosilylation reaction and contains no hydrosilylation reaction catalyst, or, if the curable silicone composition does contain one, the content is not enough to cure the composition, putting a sealing agent 6 composed of that curable silicone composition in contact with the cured silicone 5.
- the curable silicone composition contains extremely little or no hydrosilylation reaction catalyst, discoloration at high temperature caused by a
- hydrosilylation reaction catalyst can be suppressed. Furthermore, because the curable silicone composition curing reaction itself is effectively performed by a hydrosilylation reaction catalyst in the cured silicone that contacts the sealing agent, a sealing agent of which the desired heat resistance and storage stability are assured can be formed.
- the composition does not contain the hydrosilylation reaction catalyst from the viewpoint of suppressing discoloration at high temperature. Nevertheless, in cases where the composition unavoidably contains a hydrosilylation reaction catalyst and cases where the composition contains a trace amount for some reason, it is stipulated that not only "the composition does not contain a hydrosilylation reaction catalyst," but also "if the composition does contain one, the content is not enough to cure the composition.”
- cured silicone is disposed at a position so as to contact the sealing agent around the periphery of the semiconductor element.
- the cured silicone means herein a material obtained by curing a prescribed curable silicone composition, and in the optical semiconductor device, the cured silicone is not limited to a specific one provided that the cured silicone is a member disposed so as to contact the sealing agent. Specific examples include a light reflection material, a substrate, a dam material, and a fluorescent substance-containing sheet.
- composition that forms the cured silicone is not limited to a curable system, and may be any system provided that the system contains a hydrosilylation reaction catalyst. It is, however, preferably a curable silicone composition comprising:
- Examples of the silicon-bonded alkenyl group in component (a) are a vinyl group, an aryl group, a butenyl group, a pentenyl group, and a hexenyl group, and a vinyl group is preferred.
- Examples of groups bonded to the silicon atom other than the alkenyl groups in component (a) include monovalent hydrocarbon groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, or a similar chain alkyl group; a cyclopentyl group, a cyclohexyl group, or a similar cycloalkyl group; a phenyl group, a tolyl group, a xylyl group, a naphthyl group, or a similar aryl group; a benzyl group, a phenethyl group, a 3-phenylpropyl group, or a similar aralkyl group; a chloromethyl group, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, a nonafluorobutyleth
- component (a) examples include straight chain, cyclic, partially-branched straight chain, and branched, but at least one type of branched organopolysiloxane is preferably used as component (a) from the viewpoint that it can impart sufficient hardness and strength to the obtained cured silicone.
- the viscosity of component (a) is preferably from 1 to 10,000 mPa s at 25°C.
- Examples of the groups bonded to silicon other than a hydrogen atom in component (b) include the same monovalent hydrocarbon groups as described above.
- component (b) examples include straight chain, cyclic, partially-branched straight chain, and branched.
- Component (b) having a plurality of structures is preferably used in combination from the viewpoint of adjusting the hardness and strength of the obtained cured silicone.
- the viscosity of straight chain, cyclic, and partially-branched straight chain component (b) is preferably from 1 to 10,000 mPa s at 25°C.
- the compounded quantity of component (b) in the composition may be an amount sufficient to cure the curable silicone composition, and the amount of silicon- bonded hydrogen atoms in component (b) is preferably from 0.3 to 10 mol per 1 mol of the alkenyl groups in component (a). If the amount of silicon-bonded hydrogen atoms in component (b) per 1 mol of alkenyl groups in component (a) is below this range, it is undesirable because the composition tends to be insufficiently cured. On the other hand, if it exceeds this range, it is undesirable because the mechanical strength of the obtained cured silicone tends to be reduced.
- the hydrosilylation reaction catalyst of component (c) is a catalyst for accelerating crosslinking of the composition, preferably a platinum-based catalyst.
- platinum-based catalysts include chloroplatinic acid, alcohol solutions of chloroplatinic acid, olefin complexes of platinum, alkenylsiloxane complexes of platinum, platinum black, and platinum-supported silica.
- the compounded quantity thereof is preferably from 1 to 1,000 ppm in mass units as platinum metal in the composition. It is preferably not less than 5 ppm from the viewpoint of accelerating curing of the curing silicone composition as the sealing agent, and not greater than 100 ppm from the viewpoint of increasing heat resistance of the obtained cured silicone.
- compositions may contain include hydrosilylation reaction inhibitors such as 3-methyl-l-butyn-3-ol, 3,5-dimethyl-l- hexyn-3-ol, 3-phenyl-l-butyn-3-ol, or a similar alkyne alcohol; 3-methyl-3-penten-l-yne, and 3,5-dimethyl-3-hexen-l-yne, or a similar ene-yne compound; 1 ,3,5,7-tetramethyl- 1 ,3,5-tetravinylcyclotetrasiloxane, 1 ,3,5,7-tetramethyl-l ,3,5,7- tetrahexenylcyclotetrasiloxane, and benzotriazole.
- the content of the hydrosilylation reaction inhibitor is preferably from 10 to 50,000 ppm of the composition in mass units.
- white pigment is preferably contained in the composition that constitutes the cured silicone for the purpose of increasing whiteness.
- the white pigment include metal oxides such as titanium oxide, alumina, zinc oxide, zirconium oxide and magnesium oxide; and barium sulfate, zinc sulfate, barium titanate, aluminum nitride, boron nitride, antimony oxide, and the like. Titanium oxide is preferred from the viewpoint of high light reflectance and blocking capability, and zinc oxide or barium titanate is preferred from the viewpoint of light reflectance in the UV range.
- the shape and the average particle diameter of the white pigment are not limited, the average particle diameter is preferably from 0.05 to 10.0 ⁇ , and particularly preferably from 0.1 to 5.0 ⁇ .
- the white pigment may be surface-treated using a silane coupling agent, silica, alumina, or the like.
- the added quantity of white pigment is not less than 50 parts by mass, and preferably not less than 60 parts by mass, per 100 parts by mass of the total of components (a) and (b). This is because the light reflectance of the cured silicone is good when the content is not less than this lower limit. [0035] When the cured silicone is used as light reflection material, because
- the inorganic filler includes spherical silica, non-spherical silica, and glass fibers.
- the spherical silica of the inorganic filler include dry-method silica, wet-method silica, fused silica, and deflagration-method silica, but fused silica is preferred due to exhibiting good filling properties in the present composition.
- the non-spherical silica of the inorganic filler include quartz powder and glass beads, but quartz powder is preferred.
- the glass fibers of the inorganic filler include chopped glass fibers and milled glass fibers, but milled glass fibers are preferred.
- the particle diameter of the spherical silica for the inorganic filler is not limited, but the average particle diameter is preferably from 0.1 to 50 ⁇ , and particularly preferably from 0.5 to 30 ⁇ .
- the particle diameter of the non-spherical silica for the inorganic filler is not limited, but the average particle diameter is preferably from 0.1 to 50 ⁇ , and particularly preferably from 0.5 to 30 ⁇ .
- the shape of the glass fibers for the inorganic filler is not limited, but the diameter of the fibers is preferably from 1 to 50 ⁇ , and particularly preferably from 5 to 20 ⁇ , and the length of the fibers is preferably from 5 to 500 ⁇ , and particularly preferably from 10 to 300 ⁇ .
- the content of the inorganic filler is not less than 100 parts by mass, and preferably not less than 120 parts by mass, per 100 parts by mass of components (a) and (b).
- the linear expansion coefficient of the obtained cured product is low and
- dimensional stability is good when the content of inorganic filler is not less than the lower limit of this range.
- the total content of the pigment component and the inorganic filler component is not great than 700 parts by mass, and preferably not greater than 600 parts by mass, per 100 parts by mass of components (a) and (b).
- the viscosity of the obtained composition is good.
- various additives may be compounded as necessary in the composition that constitutes the cured silicone.
- Other optional components that may be contained include inorganic fillers other than the spherical silica, non-spherical silica and glass fibers; fine powders of organic resins such as polymethacrylate resins and silicone resins; mold release agents such as carnauba wax, higher fatty acids, metal salts of higher fatty acids, and methyl silicone oils; heat-resistant agents; flame retardants; solvents; and the like.
- the cured silicone When the cured silicone is used as something other than a light reflection material, for example, a fluorescent body-containing sheet, various additives may be compounded as necessary in the composition that constitutes the cured silicone.
- Other optional components that may be contained include inorganic fillers other than the spherical silica, non-spherical silica and glass fibers; fine powders of organic resins such as polymethacrylate resins and silicone resins; heat-resistant agents; dyes; pigments, fluorescent substances; flame retardants; solvents; and the like.
- a semiconductor element is sealed using a curable silicone composition that cures due to a hydrosilylation reaction and does not contain a hydrosilylation reaction catalyst, or, if the curable silicone composition does contain one, the content is not enough to cure the composition.
- the curable silicone composition used in the present invention comprises:
- the content is preferably not enough to cure the composition.
- the aforementioned composition preferably does not contain a hydrosilylation reaction catalyst, or, if the curable silicone composition does contain one, the hydrosilylation reaction catalyst contains not more than 0.1 ppm metal atoms with respect to the mass of the composition.
- the curable silicone composition that forms the cured silicone or the sealing agent may contain various adhesion promoters to improve adhesion with various materials.
- adhesion promoters include: organosilanes or linear, branched, or cyclic organosiloxane oligomers having approximately 4 to 20 silicon atoms having a trialkoxysiloxy group (e.g., a trimethoxysiloxy group or triethoxysiloxy group) or a trialkoxysilylalkyl group (e.g., a trimethoxysilylethyl group or triethoxysilylethyl group), and a hydrosilyl group or alkenyl group (e.g., a vinyl group or allyl group); organosilanes or linear, branched, or cyclic organosiloxane oligomers having approximately 4 to 20 silicon atoms having a trialkoxysiloxy group or trialkoxysilylalkyl
- methacryloxyalkyl group e.g., a 3-methacryloxypropyl group
- organosilanes or linear, branched, or cyclic organosiloxane oligomers having approximately 4 to 20 silicon atoms having a trialkoxysiloxy group or trialkoxysilylalkyl group, and an epoxy group-bonded alkyl group (e.g., a 3 -glycidoxypropyl group, 4-glycidoxybutyl group, 2-(3,4- epoxycyclohexyl)ethyl group, or 3-(3,4-epoxycyclohexyl)propyl group); and reaction products of aminoalkyl trialkoxysilanes and epoxy group-bonded alkyltrialkoxysilanes, and epoxy group- containing ethyl polysilicates.
- adhesion promoters include: vinyl trimethoxysilane, allyl trimethoxysilane, allyl triethoxysilane, hydrogen triethoxysilane, 3 -glycidoxypropyl trimethoxysilane, 3 -glycidoxypropyl triethoxysilane, 2-(3,4-epoxy cyclohexyl)ethyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, reaction products of 3- glycidoxypropyl triethoxysilane and 3-aminopropyl triethoxysilane, condensation reaction products of silanol group-terminated methylvinylsiloxane oligomers and 3- glycidoxypropyl trimethoxysilane, condensation reaction products of silanol group- terminated methylvinylsiloxane oligomers and 3- gly
- adhesion promoters are preferably low-viscosity liquids, and their viscosity at 25°C is not particularly limited but is preferably from 1 to 500 mPa s.
- the content of the adhesion promoter is not particularly limited, but is preferably from 0.01 to 10 parts by mass with respect to a total of 100 parts by mass of components (A) and (B) in the composition. If the respective aforementioned adhesion promoters are added to the curable silicone composition, it does not matter if they are the same or different.
- the curable silicone composition preferably does not contain a hydrosilylation reaction inhibitor. This is because there is no need to add a
- hydrosilylation reaction inhibitor because the curable silicone composition according to the present invention contains no or substantially no hydrosilylation reaction catalyst to begin with.
- the reason that curing of the curable silicone composition proceeds even without a hydrosilylation reaction catalyst is thought to be that the hydrosilylation reaction catalyst migrates during curing from the cured silicone that contacts it.
- this migration is suppressed and curing ends up being slower.
- various fillers may be compounded as optional components in addition to the above-described mandatory components in order to improve mechanical strength of the silicone layer obtained by curing the composition, provided that the object of the present invention is preserved.
- fillers examples include inorganic reinforcing fillers such as precipitated silica, fumed silica, fused silica, and fumed titanium oxide; inorganic non-reinforcing fillers such as crushed quartz, diatomaceous earth, aluminosilicate, iron oxide, zinc oxide, and calcium carbonate; organic fillers such as polymethcrylate resin; and inorganic or organic fillers obtained by treating the surface with an organosilicon compound such as hexamethylsilazane, trimethylchlorosilane, polydimethylsiloxane, or polymethyl hydrogen siloxane.
- organosilicon compound such as hexamethylsilazane, trimethylchlorosilane, polydimethylsiloxane, or polymethyl hydrogen siloxane.
- the primary particle diameter of these fillers is preferably not greater than 0.5 ⁇ , and more preferably not greater than 0.1 ⁇ .
- the content thereof is controlled such that the light transmittance of the cured silicone of the curable silicone composition is not less than 80%, but it is typically not more than 10 percent by mass of the curable silicone composition, preferably not more than 5 percent by mass, and more preferably not more than 1 percent by mass. If transparency of the sealing agent and lens material is considered important, it is preferable not to compound any inorganic filler.
- the curable silicone composition is used as a sealing agent or lens material of an optical semiconductor device, as components other than the
- additives may be compounded as necessary.
- Other optional components that may be contained include fine powders of organic resins such as polymethacrylate resins and silicone resins, heat-resistant agents, dyes, pigments, fluorescent substances, flame retardants, solvents, and the like.
- a composite material (silicone composite material) of the aforementioned cured silicone and a sealing agent or the like obtained using the aforementioned curable silicone composition will now be described.
- the shape of the cured silicone that constitutes the silicone composite material of the present invention is not particularly limited, but if a shape like that shown in FIG. 1 is used, the minimum distance from any point in the sealing agent 6 to the interface between the sealing agent 6 and the cured silicone 5 is preferably not greater than 5 mm, and more preferably not greater than 3 mm.
- the curing catalyst required for heat curing of the curable silicone composition comes from the adjacently disposed cured silicone; therefore, when it is too far from the interface with the cured silicone, there is the possibility that the curing catalyst will not reach the curable silicone composition and curing will be insufficient.
- a sealing agent composed of the curable silicone composition may be used in coating applications in which it is spread on the cured silicone, or in electronic materials applications in which the silicone compound itself is small, e.g., composite of light reflection material and sealing agent for optical semiconductor devices.
- the curing temperature of the silicone composition that constitutes the cured silicone and the curing temperature of the aforementioned curable silicone composition are not particularly limited, but good curing is generally obtained from room temperature to 220°C. Curing at a temperature from 60°C to 180°C is preferable, and curing at a temperature from 80°C to 150°C is more preferable, because it results in strong adhesion between the silicone layer and substrate. Furthermore, step curing is preferable, wherein the composite is heated at from room temperature to 100°C, preferably from 60°C to 80°C, and is then heated at from 80°C to 180°C, preferably from 100°C to 150°C, because adhesion between the silicone layer and substrate is further improved in some cases.
- the material and shape of the substrate is not particularly limited.
- the substrate may be constructed from organic substances such as heat-curable resin and thermoplastic resin, or various structural bodies such as fabrics, non- woven fabrics or porous bodies, and the substrate may have various shapes such as a sheet, a rod, a hemisphere, a sphere and the like.
- various additional layers such as transparent acrylic resin layers may be provided as necessary on the surface of the silicone composite material of the present invention.
- the silicone composite material of the present invention is not limited to being incorporated into an optical semiconductor device.
- the silicone composite material may itself be used as various electrical and electronic parts or medical products such as bandages, or may be used in combination with various substrates such as metal substrates, metal oxide substrates, glass substrates and plastic films. Additionally, because the silicone composite material of the present invention may have both an optically transparent portion and a reflective portion, the silicone composite material may be used as a portion of or an entire part for optical elements.
- optical semiconductor device of the present invention will now be explained.
- the optical semiconductor device according to the present invention is characterized by being manufacture by the above-described manufacturing method.
- An example of such an optical semiconductor device of the present invention is a light-emitting diode (LED) (see FIGS. 1 to 4).
- a light reflection material 5 composed of cured silicone functions as a frame material (packaging material) of the optical semiconductor device, and a sealing agent 6 functions as a protectant of an optical semiconductor element 1.
- a sealing agent 6 functions as a protectant of an optical semiconductor element 1.
- a substrate 7 which has cured silicone functions as a substrate on which an optical semiconductor element 1 is mounted, and a sealing agent 6 functions as a protectant and a lens material of the optical semiconductor element 1.
- a dam material 8 composed of cured silicone controls outflow of a sealing agent 6 as frame material of the optical semiconductor device, and the sealing agent 6 functions as a protectant of an optical semiconductor element 1.
- a fluorescent body-containing sheet composed of cured silicone converts the wavelength of light from an optical semiconductor element and diffuses light, and a sealing agent 6 functions as a protectant of the optical semiconductor element 1.
- an optical semiconductor element 1 is die bonded to a lead frame 2 by a die bonding material, and this optical semiconductor element 1 is wire bonded to lead frames 2, 3 by bonding wires 4, 4'.
- a light reflection material 5 composed of the cured silicone is present.
- the optical semiconductor element 1 within this light reflection material 5 is sealed by the sealing agent 6.
- the flow of manufacturing a surface mounted LED shown in FIG. 1 is exemplified by a method including the steps of; (1) forming the light reflection material 5 integrated with the lead frames 2, 3 by transfer molding, compression molding or injection molding a hydrosilylation reaction-curable silicone composition, (2) die bonding the optical semiconductor element 1 on the lead frame 2 using the die bonding material, (3) wire bonding the optical semiconductor element 1 and the lead frames 2, 3 using the bonding wires 4, 4', and (4) sealing the optical semiconductor element 1 using the sealing agent 6.
- the molding is preferably performed at a temperature of from 1 10°C to 170°C for from 60 to 300 seconds.
- Post curing may be performed for about 1 to 8 hours at a temperature of from 130°C to 180°C.
- an optical semiconductor element 1 is die bonded to a lead frame 2 by a die bonding material, and this optical semiconductor element 1 is wire bonded to lead frames 2, 3 by bonding wires 4, 4'.
- the aforementioned cured silicone is present, and the optical semiconductor element 1 is sealed by the sealing agent 6.
- the flow of manufacturing the surface mounted LED shown in FIG. 2 is exemplified by a method including the steps of: (1) forming the substrate 7 integrated with the lead frames 2, 3 by transfer molding, compression molding or injection molding the hydrosilylation reaction-curable silicone composition, (2) die bonding the optical semiconductor element 1 on the lead frame 2 using the die bonding material, (3) wire bonding the optical semiconductor element 1 and the lead frames 2, 3 using the bonding wires 4, 4', and (4) sealing the optical semiconductor element 1 using the sealing agent 6 composed of curable silicone composition.
- an optical semiconductor element 1 is die bonded to a lead frame 2 by a die bonding material, and this optical semiconductor element 1 is wire bonded to lead frames 2, 3 by bonding wires 4, 4'.
- a dam material 8 composed of cured silicone is present. The optical semiconductor element 1 within this dam material 8 is sealed by the sealing agent 6.
- the flow of manufacturing the surface mounted LED shown in FIG. 3 is exemplified by a method including the steps of: (1) die bonding the optical semiconductor element 1 on the lead frame 2 using the die bonding material, (2) wire bonding the optical semiconductor element 1 and the lead frames 2, 3 using the bonding wires 4, 4', (3) forming the dam material 8 around the periphery of the optical semiconductor element 1 on the substrate by dispensing a hydrosilylation reaction-curable silicone composition, and (4) sealing the optical semiconductor element 1 using the sealing agent 6 composed of a curable silicone composition.
- an optical semiconductor element 1 is die bonded to a lead frame 2 by a die bonding material, and this optical semiconductor element 1 is wire bonded to lead frames 2, 3 by bonding wires 4, 4'.
- This optical semiconductor element 1 is covered by a fluorescent substance-containing sheet 10 composed of cured silicone, and this fluorescent substance-containing sheet 10 and the optical semiconductor element 1 are sealed by the sealing agent 6.
- the flow of manufacturing the surface mounted LED shown in FIG. 4 is exemplified by a method including the steps of: (1) forming a frame material 9 integrated with the lead frames 2, 3 by transfer molding, compression molding or injection molding a hydrosilylation reaction-curable silicone composition, (2) die bonding the optical semiconductor element 1 on the lead frame 2 using the die bonding material, (3) wire bonding the optical semiconductor element 1 and the lead frames 2, 3 using the bonding wires 4, 4', (4) covering the optical semiconductor element 1 with the fluorescent substance-containing sheet 10, and (5) filling the optical semiconductor element 1 and the fluorescent body-containing sheet 10 with the sealing agent 6 composed of a curable silicone composition.
- the curing temperature of the sealing agent 6 is not particularly limited, but good curing is generally able to be obtained from room temperature to 220°C. Curing at a temperature from 60°C to 180°C is preferable, and curing at a temperature from 80°C to 150°C is more preferable, because it results in strong adhesion between the silicone layer and substrate. Furthermore, step curing is preferable, wherein the composite is heated at from room temperature to 100°C, preferably from 60°C to 80°C, and is then heated at from 80°C to 180°C, preferably from 100°C to 150°C, because adhesion between the silicone layer and substrate is further improved in some cases. Examples
- the light reflection material 5 (cured silicone) illustrated in FIG. 1 was produced by molding a hydrosilylation reaction-curable silicone composition integrated with lead frames 2, 3 at 150°C using a transfer molder. After the light reflection material was post- cured for 3 hours at 130°C, it was filled by dispensing the prescribed curable silicone composition to form the sealing agent 6. With the light reflection material filled with the curable silicone composition, curing of the curable silicone composition was begun at 150°C. The surface tack of the cured sealing agent 6 was checked at 5, 10, 30, 60, and 120 minutes after the start of curing, and the time until there was no tackiness was taken to be the curing time.
- the viscosity of the curable silicone composition immediately after preparation was measured with a shear rate of 20 (1/sec) using a rheometer (AR550, manufactured by TA Instruments Corp.). After the composition was prepared and then left to stand for 24 hours at 25°C, the viscosity was measured by the same method and compared with the initial viscosity.
- the produced optical semiconductor device was left for 20 minutes in a 300°C oven, and the degree of discoloration of the sealing agent was checked visually.
- curable silicone composition 3 (amount resulting in 0.18 mol of silicon-bonded hydrogen atoms in this component relative to 1 mol of total vinyl groups in the aforementioned methylvinylphenylpolysiloxane, 1 ,3,5,7-tetramethyl- 1 ,3,5,7-tetravinylcyclotetrasiloxane, and dimethylvinylsiloxy- terminated methylphenylpolysiloxane); l ,3-divinyl-l ,l ,3,3-tetramethyldisiloxane solution of l,3-divinyl-l ,l ,3,3-tetramethyldisiloxane complex of platinum (amount resulting in 10 ppm by mass of the platinum metal in the present composition); and 1 -ethynyl- 1 - cyclohexanol (amount resulting in 250 ppm by mass in the present composition) were homogeneously blended to prepare curable silicone composition 3.
- methylphenylpolysiloxane l,3-divinyl-l,l,3,3-tetramethyldisiloxane solution of 1 ,3- divinyl-l ,l,3,3-tetramethyldisiloxane complex of platinum (amount resulting in 10 ppm by mass of the platinum metal in the present composition); 1-ethynyl-l-cyclohexanol (amount resulting in 250 ppm by mass in the present composition); 118 parts by mass of titanium oxide having 0.2 ⁇ average primary particle diameter (SX-3103, manufactured by Sakai Chemical Industry Co., Ltd.); and 213 parts by mass of spherical silica having 15 ⁇ average particle diameter (HS-202, manufactured by Nippon Steel & Sumikin Materials Co., Ltd.) were homogeneously blended to prepare curable silicone composition 5.
- curable silicone composition 6 having viscosity of 2,400 mPa s. After the curable silicone composition 6 was left to stand for 24 hours at 25°C, its viscosity was 2,400 mPa s.
- curable silicone composition 7 having viscosity of 4,600 mPa-s. After the curable silicone composition 7 was left to stand for 24 hours at 25°C, its viscosity was 4,600 mPa s.
- curable silicone composition 8 having viscosity of 2,400 mPa s. After the curable silicone composition 8 was left to stand for 24 hours at 25°C, its viscosity was 2,400 mPa-s.
- curable silicone composition 9 having viscosity of 4,600 mPa s. After the curable silicone composition 4 was left to stand for 24 hours at 25°C, its viscosity was 4,600 mPa s.
- the curable silicone composition 1 prepared in Production Example 1 was molded integrated with a lead frame for 2 minutes at 150°C, and then post-cured for 1 hour in a 150°C oven to obtain a light reflection material. This was filled by dispensing the curable silicone composition 6 prepared in Production Example 6 and then curing was performed for a prescribed time in a 150°C oven, and curability was assessed according to surface tack. The obtained optical semiconductor device was put in a 300°C oven, and a heat resistance test was performed for 20 minutes. The degree of discoloration of the sealing agent was checked visually. Results of the evaluation are shown in Table 1.
- the curable silicone composition 1 prepared in Production Example 1 was molded integrated with a lead frame for 2 minutes at 150°C, and then post-cured for 1 hour in a 150°C oven to obtain a light reflection material. This was filled by dispensing the curable silicone composition 7 prepared in Production Example 7 and then curing was performed for a prescribed time in a 150°C oven, and curability was assessed according to surface tack. The obtained optical semiconductor device was put in a 300°C oven, and a heat resistance test was performed for 20 minutes. The degree of discoloration of the sealing agent was checked visually. Results of the evaluation are shown in Table 1.
- the curable silicone composition 2 prepared in Production Example 2 was molded integrated with a lead frame for 2 minutes at 150°C, and then post-cured for 1 hour in a 150°C oven to obtain a light reflection material. This was filled by dispensing the curable silicone composition 6 prepared in Production Example 6 and then curing was performed for a prescribed time in a 150°C oven, and curability was assessed according to surface tack. The obtained optical semiconductor device was put in a 300°C oven, and a heat resistance test was performed for 20 minutes. The degree of discoloration of the sealing agent was checked visually. Results of the evaluation are shown in Table 1.
- the curable silicone composition 2 prepared in Production Example 2 was molded integrated with a lead frame for 2 minutes at 150°C, and then post-cured for 1 hour in a
- the curable silicone composition 3 prepared in Production Example 3 was molded integrated with a lead frame for 2 minutes at 150°C, and then post-cured for 1 hour in a
- the curable silicone composition 4 prepared in Production Example 4 was molded integrated with a lead frame for 2 minutes at 150°C, and then post-cured for 1 hour in a 150°C oven to obtain a light reflection material. This was filled by dispensing the curable silicone composition 7 prepared in Production Example 7 and then curing was performed for a prescribed time in a 150°C oven, and curability was assessed according to surface tack. The obtained optical semiconductor device was put in a 300°C oven, and a heat resistance test was performed for 20 minutes. The degree of discoloration of the sealing agent was checked visually. Results of the evaluation are shown in Table 1.
- the curable silicone composition 5 prepared in Production Example 5 was molded integrated with a lead frame for 2 minutes at 150°C, and then post-cured for 1 hour in a 150°C oven to obtain a light reflection material. This was filled by dispensing the curable silicone composition 6 prepared in Production Example 6 and then curing was performed for a prescribed time in a 150°C oven, and curability was assessed according to surface tack.
- the obtained optical semiconductor device was put in a 300°C oven, and a heat resistance test was performed for 20 minutes. The degree of discoloration of the sealing agent was checked visually. Results of the evaluation are shown in Table 1.
- the curable silicone composition 5 prepared in Production Example 5 was molded integrated with a lead frame for 2 minutes at 150°C, and then post-cured for 1 hour in a 150°C oven to obtain a light reflection material. This was filled by dispensing the curable silicone composition 7 prepared in Production Example 7 and then curing was performed for a prescribed time in a 150°C oven, and curability was assessed according to surface tack. The obtained optical semiconductor device was put in a 300°C oven, and a heat resistance test was performed for 20 minutes. The degree of discoloration of the sealing agent was checked visually. Results of the evaluation are shown in Table 1.
- the curable silicone composition 1 prepared in Production Example 1 was molded integrated with a lead frame for 2 minutes at 150°C, and then post-cured for 1 hour in a 150°C oven to obtain a light reflection material. This was filled by dispensing the curable silicone composition 8 prepared in Production Example 8 and then curing was performed for a prescribed time in a 150°C oven, and curability was assessed according to surface tack. The obtained optical semiconductor device was put in a 300°C oven, and a heat resistance test was performed for 20 minutes. The degree of discoloration of the sealing agent was checked visually. Results of the evaluation are shown in Table 1.
- the curable silicone composition 2 prepared in Production Example 2 was molded integrated with a lead frame for 2 minutes at 150°C, and then post-cured for 1 hour in a 150°C oven to obtain a light reflection material. This was filled by dispensing the curable silicone composition 9 prepared in Production Example 9 and then curing was performed for a prescribed time in a 150°C oven, and curability was assessed according to surface tack. The obtained optical semiconductor device was put in a 300°C oven, and a heat resistance test was performed for 20 minutes. The degree of discoloration of the sealing agent was checked visually. Results of the evaluation are shown in Table 1.
- the curable silicone composition 4 prepared in Production Example 4 was molded integrated with a lead frame for 2 minutes at 150°C, and then post-cured for 1 hour in a 150°C oven to obtain a light reflection material. This was filled by dispensing the curable silicone composition 10 prepared in Production Example 10 and then curing was performed for a prescribed time in a 150°C oven, and curability was assessed according to surface tack. The obtained optical semiconductor device was put in a 300°C oven, and a heat resistance test was performed for 20 minutes. The degree of discoloration of the sealing agent was checked visually. Results of the evaluation are shown in Table 1.
- the curable silicone composition 5 prepared in Production Example 5 was molded integrated with a lead frame for 2 minutes at 150°C, and then post-cured for 1 hour in a 150°C oven to obtain a light reflection material. This was filled by dispensing the curable silicone composition 1 1 prepared in Production Example 11 and then curing was performed, for a prescribed time in a 150°C oven, and curability was assessed according to surface tack.
- the obtained optical semiconductor device was put in a 300°C oven, and a heat resistance test was performed for 20 minutes. The degree of discoloration of the sealing agent was checked visually. Results of the evaluation are shown in Table 1.
- a method of manufacturing an optical semiconductor device of which the sealing agent realizes storage stability, has good heat resistance, and can greatly resist discoloration can be provided; and an optical semiconductor device obtained by the manufacturing method can be provided.
- Fluorescent substance-containing sheet composed of cured silicone
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Abstract
The present invention relates to a method of manufacturing an optical semiconductor device comprising a step of sealing an optical semiconductor element using a curable silicone composition, the curable silicone composition, although cured by a hydrosilylation reaction, being hydro silylation reaction catalyst free, or, if containing a hydrosilylation reaction catalyst, a content of the curable silicone composition being insufficient to cure the composition, and the optical semiconductor element being sealed in a state in which the curable silicone composition contacts a cured silicone that contains a hydrosilylation reaction catalyst. According to the present invention, a method of manufacturing an optical semiconductor device of which the sealing agent realizes storage stability, has good heat resistance, and can greatly resist discoloration can be provided; and an optical semiconductor device obtained by the manufacturing method can be provided.
Description
DESCRIPTION
METHOD OF MANUFACTURING OPTICAL SEMICONDUCTOR DEVICE AND OPTICAL SEMICONDUCTOR DEVICE
Technical Field
[0001] The present invention relates to a method of manufacturing an optical semiconductor device, and particularly relates to a method of manufacturing an optical semiconductor device in which the storage stability of the sealing agent of the optical semiconductor device can be realized, and the sealing agent has good heat resistance and can greatly resist discoloration, and an optical semiconductor device obtained by the manufacturing method.
[0002] Priority is claimed on Japanese Patent Application No. 2013-184438, filed on September 5, 2013, the content of which is incorporated herein by reference.
Background Art
[0003] Curable silicone compositions that cure due to a hydrosilylation reaction have been used as sealing agents, coating agents, lens-molding materials, light reflection materials, and the like for optical semiconductor elements in optical semiconductor devices such as photocouplers, light-emitting diodes, solid-state image sensors, and the like. For example, in Patent Document 1 , a curable silicone composition is proposed, the composition being composed of an organopolysiloxane having an average of not less than 0.2 silicon-bonded alkenyl groups per molecule, an organopolysiloxane having a three- dimensional network structure, an organopolysiloxane having not less than two silicon- bonded hydrogen atoms per molecule, and a hydrosilylation reaction catalyst.
Additionally, in Patent Document 2, a curable silicone composition is proposed, the composition being composed of an organopolysiloxane having a silicon-bonded phenyl group and a silicon-bonded alkenyl group, an organopolysiloxane having a silicon-bonded hydrogen atom, and a hydrosilylation reaction catalyst.
[0004] In such curable silicone compositions, a reaction control agent is added to suppress a hydrosilylation reaction because the hydrosilylation reaction proceeds even at room temperature; however, these compositions have the problem that viscosity increases over time.
[0005] Furthermore, in such curable silicone compositions, a rise in viscosity is suppressed since the hydrosilylation reaction does not proceed unless a hydrosilylation
reaction catalyst is added. It is, however, considered to be necessary to add a
hydrosilylation reaction catalyst because the reaction does not proceed to begin with, and it is also considered that a sealing agent or the like composed of a composition that does not contain the hydrosilylation reaction catalyst cannot be provided as a product.
[0006] Further, in addition to the above problems, the conventional cured silicones have the following problems. While high heat resistance is required of sealing agents of optical semiconductor elements, because the sealing agents directly receive heat generated from the elements, the conventional cured silicones yellow when exposed to high temperatures. Prior Art Documents
Patent Documents
[0007]
Patent Document 1 : Japanese Unexamined Patent Application Publication No. 2006- 213789
Patent Document 2: Japanese Unexamined Patent Application Publication No. 2009- 185226
Summary of Invention
Technical Problem
[0008] In consideration of the above, an object of the present invention is to provide a method of manufacturing an optical semiconductor device in which the storage stability of the sealing agent of the optical semiconductor device can be realized, and the sealing agent has good heat resistance and can greatly resist discoloration even when exposed to high temperatures, and an optical semiconductor device obtained by the manufacturing method.
Solution to Problem
[0009] As a result of diligent research to solve the above problems, the present inventors discovered that discoloration arising due to the fact that the sealing agent contains a hydrosilylation reaction catalyst can be suppressed and good heat resistance can be realized by using a curable silicone composition that cures due to a hydrosilylation reaction and contains very little or no hydrosilylation reaction catalyst as the sealing agent of an optical semiconductor element and by disposing cured silicone containing a hydrosilylation reaction catalyst as a member separate from the sealing agent. They also discovered that, because the curable silicone composition that forms the sealing agent does
not itself cure, a curable silicone composition, which is conventionally provided in a two- part form, can be provided in a one-part form, and therefore the complexity of the mixing operation of the two parts and the degassing operation after mixing can be avoided, and mistakes in compounding when mixing can be prevented.
[0010] That is to say, a first embodiment of the present invention is a method of manufacturing an optical semiconductor device comprising a step of sealing an optical semiconductor element using a curable silicone composition, wherein the curable silicone composition, although cured by a hydrosilylation reaction, does not contain a
hydrosilylation reaction catalyst, or, if the curable silicone composition does contain the hydrosilylation reaction catalyst, a content of the hydrosilylation reaction catalyst is not enough to cure the composition, and the optical semiconductor element is sealed in a state in which the curable silicone composition contacts cured silicone that contains the hydrosilylation reaction catalyst.
[0011] Furthermore, the curable silicone composition comprising: (A) at least one type of organopolysiloxane having not less than two silicon-bonded alkenyl groups per molecule, and (B) at least one type of organopolysiloxane having not less than two silicon- bonded hydrogen atoms per molecule, and does not contain the hydrosilylation reaction catalyst, or, if curable silicone composition does contain the hydrosilylation reaction catalyst, the content of the hydrosilylation reaction catalyst is preferably not enough to cure the composition.
[0012] The hydrosilylation reaction catalyst is preferably a platinum-based catalyst, and the curable silicone composition preferably does not contain a hydrosilylation reaction inhibitor.
[0013] Furthermore, the cured silicone is preferably a light reflection material, substrate, a dam material, or a fluorescent substance-containing sheet.
[0014] Moreover, the cured silicone preferably contains at least one type of white pigment selected from the group consisting of titanium oxide, zinc oxide, barium titanate, barium sulfate, and zirconium oxide, and preferably contains at least one type of inorganic filler selected from the group consisting of non-spherical silica, spherical silica, and glass fibers.
[0015] Another embodiment of the present invention is an optical semiconductor device manufactured by the above-described method of manufacturing an optical semiconductor device.
Effects of Invention
[0016] According to the present invention, a method of manufacturing an optical semiconductor device in which the sealing agent of the optical semiconductor device realizes storage stability, has good heat resistance, and can greatly resist discoloration can be provided; and an optical semiconductor device obtained by the manufacturing method can be provided.
[0017] Because the sealing agent is optically transparent or white even when it has been exposed to high temperature, the optical semiconductor device obtained by the method of manufacturing the present invention can also be used alone or in combination with various substrates for electrical and electronic parts or optical elements.
Brief Description of the Drawings
[0018]
FIG. 1 is a cross-sectional view of an LED that is an example of an optical semiconductor device of the present invention.
FIG. 2 is a cross- sectional view of an LED that is another example of the optical semiconductor device of the present invention.
FIG. 3 is a cross-sectional view of an LED that is yet another example of the optical semiconductor device of the present invention.
FIG. 4 is a cross-sectional view of an LED that is still another example of the optical semiconductor device of the present invention.
Detailed Description of the Invention
[0019] A method of manufacturing an optical semiconductor device and an optical semiconductor device according to the present invention will be specifically described below using the drawings.
[0020]
[Method of manufacturing optical semiconductor device]
The method of manufacturing an optical semiconductor device according to the present invention includes a step of sealing an optical semiconductor element using a curable silicone composition.
[0021] As a first embodiment of the present invention, as shown in FIG. 1 , an optical semiconductor element 1 is sealed by disposing cured silicone (light reflection material 5 in FIG. 1) containing a hydrosilylation reaction catalyst, and then, using a curable silicone
composition that cures due to a hydrosilylation reaction and contains no hydrosilylation reaction catalyst, or, if the curable silicone composition does contain one, the content is not enough to cure the composition, putting a sealing agent 6 composed of that curable silicone composition in contact with the cured silicone 5.
[0022] Because the curable silicone composition contains extremely little or no hydrosilylation reaction catalyst, discoloration at high temperature caused by a
hydrosilylation reaction catalyst can be suppressed. Furthermore, because the curable silicone composition curing reaction itself is effectively performed by a hydrosilylation reaction catalyst in the cured silicone that contacts the sealing agent, a sealing agent of which the desired heat resistance and storage stability are assured can be formed.
[0023] As described above, there is a technical concept that, as a rule, the composition does not contain the hydrosilylation reaction catalyst from the viewpoint of suppressing discoloration at high temperature. Nevertheless, in cases where the composition unavoidably contains a hydrosilylation reaction catalyst and cases where the composition contains a trace amount for some reason, it is stipulated that not only "the composition does not contain a hydrosilylation reaction catalyst," but also "if the composition does contain one, the content is not enough to cure the composition."
[0024]
[Cured silicone]
In the manufacturing method according to the present invention, cured silicone is disposed at a position so as to contact the sealing agent around the periphery of the semiconductor element.
[0025] The cured silicone means herein a material obtained by curing a prescribed curable silicone composition, and in the optical semiconductor device, the cured silicone is not limited to a specific one provided that the cured silicone is a member disposed so as to contact the sealing agent. Specific examples include a light reflection material, a substrate, a dam material, and a fluorescent substance-containing sheet.
[0026] The composition that forms the cured silicone is not limited to a curable system, and may be any system provided that the system contains a hydrosilylation reaction catalyst. It is, however, preferably a curable silicone composition comprising:
(a) an organopolysiloxane having not less than two silicon-bonded alkenyl groups per molecule,
(b) an organopolysiloxane having not less than two silicon-bonded hydrogen atoms per
molecule, and
(c) a hydrosilylation reaction catalyst.
[0027] Examples of the silicon-bonded alkenyl group in component (a) are a vinyl group, an aryl group, a butenyl group, a pentenyl group, and a hexenyl group, and a vinyl group is preferred. Examples of groups bonded to the silicon atom other than the alkenyl groups in component (a) include monovalent hydrocarbon groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, or a similar chain alkyl group; a cyclopentyl group, a cyclohexyl group, or a similar cycloalkyl group; a phenyl group, a tolyl group, a xylyl group, a naphthyl group, or a similar aryl group; a benzyl group, a phenethyl group, a 3-phenylpropyl group, or a similar aralkyl group; a chloromethyl group, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, a nonafluorobutylethyl group, or a similar halogenated hydrocarbon group. Examples of the molecular structure of component (a) include straight chain, cyclic, partially-branched straight chain, and branched, but at least one type of branched organopolysiloxane is preferably used as component (a) from the viewpoint that it can impart sufficient hardness and strength to the obtained cured silicone. The viscosity of component (a) is preferably from 1 to 10,000 mPa s at 25°C.
[0028] Examples of the groups bonded to silicon other than a hydrogen atom in component (b) include the same monovalent hydrocarbon groups as described above.
Examples of the molecular structure of component (b) include straight chain, cyclic, partially-branched straight chain, and branched. Component (b) having a plurality of structures is preferably used in combination from the viewpoint of adjusting the hardness and strength of the obtained cured silicone. The viscosity of straight chain, cyclic, and partially-branched straight chain component (b) is preferably from 1 to 10,000 mPa s at 25°C.
[0029] The compounded quantity of component (b) in the composition may be an amount sufficient to cure the curable silicone composition, and the amount of silicon- bonded hydrogen atoms in component (b) is preferably from 0.3 to 10 mol per 1 mol of the alkenyl groups in component (a). If the amount of silicon-bonded hydrogen atoms in component (b) per 1 mol of alkenyl groups in component (a) is below this range, it is undesirable because the composition tends to be insufficiently cured. On the other hand, if it exceeds this range, it is undesirable because the mechanical strength of the obtained cured silicone tends to be reduced.
[0030] The hydrosilylation reaction catalyst of component (c) is a catalyst for accelerating crosslinking of the composition, preferably a platinum-based catalyst.
Examples of platinum-based catalysts include chloroplatinic acid, alcohol solutions of chloroplatinic acid, olefin complexes of platinum, alkenylsiloxane complexes of platinum, platinum black, and platinum-supported silica. The compounded quantity thereof is preferably from 1 to 1,000 ppm in mass units as platinum metal in the composition. It is preferably not less than 5 ppm from the viewpoint of accelerating curing of the curing silicone composition as the sealing agent, and not greater than 100 ppm from the viewpoint of increasing heat resistance of the obtained cured silicone.
[0031] Examples of other optional components that the composition may contain include hydrosilylation reaction inhibitors such as 3-methyl-l-butyn-3-ol, 3,5-dimethyl-l- hexyn-3-ol, 3-phenyl-l-butyn-3-ol, or a similar alkyne alcohol; 3-methyl-3-penten-l-yne, and 3,5-dimethyl-3-hexen-l-yne, or a similar ene-yne compound; 1 ,3,5,7-tetramethyl- 1 ,3,5-tetravinylcyclotetrasiloxane, 1 ,3,5,7-tetramethyl-l ,3,5,7- tetrahexenylcyclotetrasiloxane, and benzotriazole. The content of the hydrosilylation reaction inhibitor is preferably from 10 to 50,000 ppm of the composition in mass units.
[0032] When the cured silicone is used as a light reflection material for an optical semiconductor device, white pigment is preferably contained in the composition that constitutes the cured silicone for the purpose of increasing whiteness. Examples of the white pigment include metal oxides such as titanium oxide, alumina, zinc oxide, zirconium oxide and magnesium oxide; and barium sulfate, zinc sulfate, barium titanate, aluminum nitride, boron nitride, antimony oxide, and the like. Titanium oxide is preferred from the viewpoint of high light reflectance and blocking capability, and zinc oxide or barium titanate is preferred from the viewpoint of light reflectance in the UV range.
[0033] Although the shape and the average particle diameter of the white pigment are not limited, the average particle diameter is preferably from 0.05 to 10.0 μπι, and particularly preferably from 0.1 to 5.0 μιη. In order to increase the compatibility and dispersion ability of the white pigment with the resin and inorganic filler, the white pigment may be surface-treated using a silane coupling agent, silica, alumina, or the like.
[0034] The added quantity of white pigment is not less than 50 parts by mass, and preferably not less than 60 parts by mass, per 100 parts by mass of the total of components (a) and (b). This is because the light reflectance of the cured silicone is good when the content is not less than this lower limit.
[0035] When the cured silicone is used as light reflection material, because
dimensional stability of the cured silicone is required, it is preferable if certain inorganic filler is contained in the composition that constitutes the cured silicone for the purpose of reducing the linear expansion coefficient of the obtained cured silicone. Examples of the inorganic filler include spherical silica, non-spherical silica, and glass fibers. Examples of the spherical silica of the inorganic filler include dry-method silica, wet-method silica, fused silica, and deflagration-method silica, but fused silica is preferred due to exhibiting good filling properties in the present composition. Examples of the non-spherical silica of the inorganic filler include quartz powder and glass beads, but quartz powder is preferred. Examples of the glass fibers of the inorganic filler include chopped glass fibers and milled glass fibers, but milled glass fibers are preferred.
[0036] The particle diameter of the spherical silica for the inorganic filler is not limited, but the average particle diameter is preferably from 0.1 to 50 μηι, and particularly preferably from 0.5 to 30 μιη. The particle diameter of the non-spherical silica for the inorganic filler is not limited, but the average particle diameter is preferably from 0.1 to 50 μηι, and particularly preferably from 0.5 to 30 μπι. The shape of the glass fibers for the inorganic filler is not limited, but the diameter of the fibers is preferably from 1 to 50 μπι, and particularly preferably from 5 to 20 μηι, and the length of the fibers is preferably from 5 to 500 μηι, and particularly preferably from 10 to 300 μιη.
[0037] The content of the inorganic filler is not less than 100 parts by mass, and preferably not less than 120 parts by mass, per 100 parts by mass of components (a) and (b). The linear expansion coefficient of the obtained cured product is low and
dimensional stability is good when the content of inorganic filler is not less than the lower limit of this range.
[0038] The total content of the pigment component and the inorganic filler component is not great than 700 parts by mass, and preferably not greater than 600 parts by mass, per 100 parts by mass of components (a) and (b). When the total content of the pigment component and the inorganic filler component is not greater than the aforementioned upper limit, the viscosity of the obtained composition is good.
[0039] Additionally, when the cured silicone is used as a light reflection material, various additives may be compounded as necessary in the composition that constitutes the cured silicone. Other optional components that may be contained include inorganic fillers other than the spherical silica, non-spherical silica and glass fibers; fine powders of organic
resins such as polymethacrylate resins and silicone resins; mold release agents such as carnauba wax, higher fatty acids, metal salts of higher fatty acids, and methyl silicone oils; heat-resistant agents; flame retardants; solvents; and the like.
[0040] When the cured silicone is used as something other than a light reflection material, for example, a fluorescent body-containing sheet, various additives may be compounded as necessary in the composition that constitutes the cured silicone. Other optional components that may be contained include inorganic fillers other than the spherical silica, non-spherical silica and glass fibers; fine powders of organic resins such as polymethacrylate resins and silicone resins; heat-resistant agents; dyes; pigments, fluorescent substances; flame retardants; solvents; and the like.
[0041]
[Curable silicone composition]
With the method of manufacturing the present invention, a semiconductor element is sealed using a curable silicone composition that cures due to a hydrosilylation reaction and does not contain a hydrosilylation reaction catalyst, or, if the curable silicone composition does contain one, the content is not enough to cure the composition.
[0042] Similar to the composition that constitutes the cured silicone, the curable silicone composition used in the present invention comprises:
(A) at least one type of organopolysiloxane having not less than two silicon-bonded
alkenyl groups per molecule, and
(B) at least one type of organopolysiloxane having not less than two silicon-bonded
hydrogen atoms per molecule,
and does not contain a hydrosilylation reaction catalyst, or, if the curable silicone composition does contain one, the content is preferably not enough to cure the composition. The aforementioned composition preferably does not contain a hydrosilylation reaction catalyst, or, if the curable silicone composition does contain one, the hydrosilylation reaction catalyst contains not more than 0.1 ppm metal atoms with respect to the mass of the composition.
[0043] Furthermore, the curable silicone composition that forms the cured silicone or the sealing agent may contain various adhesion promoters to improve adhesion with various materials. Examples of such adhesion promoters include: organosilanes or linear, branched, or cyclic organosiloxane oligomers having approximately 4 to 20 silicon atoms having a trialkoxysiloxy group (e.g., a trimethoxysiloxy group or triethoxysiloxy group) or
a trialkoxysilylalkyl group (e.g., a trimethoxysilylethyl group or triethoxysilylethyl group), and a hydrosilyl group or alkenyl group (e.g., a vinyl group or allyl group); organosilanes or linear, branched, or cyclic organosiloxane oligomers having approximately 4 to 20 silicon atoms having a trialkoxysiloxy group or trialkoxysilylalkyl group, and a
methacryloxyalkyl group (e.g., a 3-methacryloxypropyl group); organosilanes or linear, branched, or cyclic organosiloxane oligomers having approximately 4 to 20 silicon atoms having a trialkoxysiloxy group or trialkoxysilylalkyl group, and an epoxy group-bonded alkyl group (e.g., a 3 -glycidoxypropyl group, 4-glycidoxybutyl group, 2-(3,4- epoxycyclohexyl)ethyl group, or 3-(3,4-epoxycyclohexyl)propyl group); and reaction products of aminoalkyl trialkoxysilanes and epoxy group-bonded alkyltrialkoxysilanes, and epoxy group- containing ethyl polysilicates. Specific examples of the adhesion promoters include: vinyl trimethoxysilane, allyl trimethoxysilane, allyl triethoxysilane, hydrogen triethoxysilane, 3 -glycidoxypropyl trimethoxysilane, 3 -glycidoxypropyl triethoxysilane, 2-(3,4-epoxy cyclohexyl)ethyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, reaction products of 3- glycidoxypropyl triethoxysilane and 3-aminopropyl triethoxysilane, condensation reaction products of silanol group-terminated methylvinylsiloxane oligomers and 3- glycidoxypropyl trimethoxysilane, condensation reaction products of silanol group- terminated methylvinylsiloxane oligomers and 3-methacryloxypropyl triethoxysilane, tris(3-trimethoxysilylpropyl) isocyanurate, acid anhydrides, and the like. These adhesion promoters are preferably low-viscosity liquids, and their viscosity at 25°C is not particularly limited but is preferably from 1 to 500 mPa s. The content of the adhesion promoter is not particularly limited, but is preferably from 0.01 to 10 parts by mass with respect to a total of 100 parts by mass of components (A) and (B) in the composition. If the respective aforementioned adhesion promoters are added to the curable silicone composition, it does not matter if they are the same or different.
[0044] Furthermore, the curable silicone composition preferably does not contain a hydrosilylation reaction inhibitor. This is because there is no need to add a
hydrosilylation reaction inhibitor because the curable silicone composition according to the present invention contains no or substantially no hydrosilylation reaction catalyst to begin with. The reason that curing of the curable silicone composition proceeds even without a hydrosilylation reaction catalyst is thought to be that the hydrosilylation reaction catalyst migrates during curing from the cured silicone that contacts it. However, when the
curable silicone composition contains a hydrosilylation reaction inhibitor, this migration is suppressed and curing ends up being slower.
[0045] When the curable silicone composition is used as a sealing agent or lens material for an optical semiconductor device, various fillers may be compounded as optional components in addition to the above-described mandatory components in order to improve mechanical strength of the silicone layer obtained by curing the composition, provided that the object of the present invention is preserved.
[0046] Examples of the fillers include inorganic reinforcing fillers such as precipitated silica, fumed silica, fused silica, and fumed titanium oxide; inorganic non-reinforcing fillers such as crushed quartz, diatomaceous earth, aluminosilicate, iron oxide, zinc oxide, and calcium carbonate; organic fillers such as polymethcrylate resin; and inorganic or organic fillers obtained by treating the surface with an organosilicon compound such as hexamethylsilazane, trimethylchlorosilane, polydimethylsiloxane, or polymethyl hydrogen siloxane.
[0047] The primary particle diameter of these fillers is preferably not greater than 0.5 μηι, and more preferably not greater than 0.1 μηι. The content thereof is controlled such that the light transmittance of the cured silicone of the curable silicone composition is not less than 80%, but it is typically not more than 10 percent by mass of the curable silicone composition, preferably not more than 5 percent by mass, and more preferably not more than 1 percent by mass. If transparency of the sealing agent and lens material is considered important, it is preferable not to compound any inorganic filler.
[0048] Additionally, if the curable silicone composition is used as a sealing agent or lens material of an optical semiconductor device, as components other than the
aforementioned fillers, various additives may be compounded as necessary. Other optional components that may be contained include fine powders of organic resins such as polymethacrylate resins and silicone resins, heat-resistant agents, dyes, pigments, fluorescent substances, flame retardants, solvents, and the like.
[0049]
[Silicone composite material]
A composite material (silicone composite material) of the aforementioned cured silicone and a sealing agent or the like obtained using the aforementioned curable silicone composition will now be described.
[0050] The shape of the cured silicone that constitutes the silicone composite material
of the present invention is not particularly limited, but if a shape like that shown in FIG. 1 is used, the minimum distance from any point in the sealing agent 6 to the interface between the sealing agent 6 and the cured silicone 5 is preferably not greater than 5 mm, and more preferably not greater than 3 mm. According to the present invention, the curing catalyst required for heat curing of the curable silicone composition comes from the adjacently disposed cured silicone; therefore, when it is too far from the interface with the cured silicone, there is the possibility that the curing catalyst will not reach the curable silicone composition and curing will be insufficient. Due to this fact, a sealing agent composed of the curable silicone composition may be used in coating applications in which it is spread on the cured silicone, or in electronic materials applications in which the silicone compound itself is small, e.g., composite of light reflection material and sealing agent for optical semiconductor devices.
[0051] The curing temperature of the silicone composition that constitutes the cured silicone and the curing temperature of the aforementioned curable silicone composition are not particularly limited, but good curing is generally obtained from room temperature to 220°C. Curing at a temperature from 60°C to 180°C is preferable, and curing at a temperature from 80°C to 150°C is more preferable, because it results in strong adhesion between the silicone layer and substrate. Furthermore, step curing is preferable, wherein the composite is heated at from room temperature to 100°C, preferably from 60°C to 80°C, and is then heated at from 80°C to 180°C, preferably from 100°C to 150°C, because adhesion between the silicone layer and substrate is further improved in some cases.
[0052] In cases where the silicone composite material of the present invention is used in combination with another material such as a substrate, the material and shape of the substrate is not particularly limited. The substrate may be constructed from organic substances such as heat-curable resin and thermoplastic resin, or various structural bodies such as fabrics, non- woven fabrics or porous bodies, and the substrate may have various shapes such as a sheet, a rod, a hemisphere, a sphere and the like. Furthermore, various additional layers such as transparent acrylic resin layers may be provided as necessary on the surface of the silicone composite material of the present invention.
[0053] The silicone composite material of the present invention is not limited to being incorporated into an optical semiconductor device. The silicone composite material may itself be used as various electrical and electronic parts or medical products such as bandages, or may be used in combination with various substrates such as metal substrates,
metal oxide substrates, glass substrates and plastic films. Additionally, because the silicone composite material of the present invention may have both an optically transparent portion and a reflective portion, the silicone composite material may be used as a portion of or an entire part for optical elements.
[0054]
[Optical semiconductor device]
The optical semiconductor device of the present invention will now be explained.
[0055] The optical semiconductor device according to the present invention is characterized by being manufacture by the above-described manufacturing method.
[0056] An example of such an optical semiconductor device of the present invention is a light-emitting diode (LED) (see FIGS. 1 to 4). In the optical semiconductor device of FIG. 1, a light reflection material 5 composed of cured silicone functions as a frame material (packaging material) of the optical semiconductor device, and a sealing agent 6 functions as a protectant of an optical semiconductor element 1. In the optical
semiconductor device of FIG. 2, a substrate 7 which has cured silicone functions as a substrate on which an optical semiconductor element 1 is mounted, and a sealing agent 6 functions as a protectant and a lens material of the optical semiconductor element 1. In the optical semiconductor device of FIG. 3, a dam material 8 composed of cured silicone controls outflow of a sealing agent 6 as frame material of the optical semiconductor device, and the sealing agent 6 functions as a protectant of an optical semiconductor element 1. In the optical semiconductor device of FIG. 4, a fluorescent body-containing sheet composed of cured silicone converts the wavelength of light from an optical semiconductor element and diffuses light, and a sealing agent 6 functions as a protectant of the optical semiconductor element 1.
[0057] In the optical semiconductor device of the present invention, as illustrated in FIG. 1 , an optical semiconductor element 1 is die bonded to a lead frame 2 by a die bonding material, and this optical semiconductor element 1 is wire bonded to lead frames 2, 3 by bonding wires 4, 4'. Around the periphery of this optical semiconductor element 1 , with the exception of the upper part thereof, a light reflection material 5 composed of the cured silicone is present. The optical semiconductor element 1 within this light reflection material 5 is sealed by the sealing agent 6.
[0058] The flow of manufacturing a surface mounted LED shown in FIG. 1 is exemplified by a method including the steps of; (1) forming the light reflection material 5
integrated with the lead frames 2, 3 by transfer molding, compression molding or injection molding a hydrosilylation reaction-curable silicone composition, (2) die bonding the optical semiconductor element 1 on the lead frame 2 using the die bonding material, (3) wire bonding the optical semiconductor element 1 and the lead frames 2, 3 using the bonding wires 4, 4', and (4) sealing the optical semiconductor element 1 using the sealing agent 6.
[0059] If the light reflection material is formed by the aforementioned transfer molding, compression molding or injection molding, the molding is preferably performed at a temperature of from 1 10°C to 170°C for from 60 to 300 seconds. Post curing may be performed for about 1 to 8 hours at a temperature of from 130°C to 180°C.
[0060] Furthermore, in another optical semiconductor device of the present invention, as illustrated in FIG. 2, an optical semiconductor element 1 is die bonded to a lead frame 2 by a die bonding material, and this optical semiconductor element 1 is wire bonded to lead frames 2, 3 by bonding wires 4, 4'. On a portion of the substrate 7 on which the optical semiconductor element 1 is mounted that contacts a sealing agent 6, the aforementioned cured silicone is present, and the optical semiconductor element 1 is sealed by the sealing agent 6.
[0061] The flow of manufacturing the surface mounted LED shown in FIG. 2 is exemplified by a method including the steps of: (1) forming the substrate 7 integrated with the lead frames 2, 3 by transfer molding, compression molding or injection molding the hydrosilylation reaction-curable silicone composition, (2) die bonding the optical semiconductor element 1 on the lead frame 2 using the die bonding material, (3) wire bonding the optical semiconductor element 1 and the lead frames 2, 3 using the bonding wires 4, 4', and (4) sealing the optical semiconductor element 1 using the sealing agent 6 composed of curable silicone composition.
[0062] Furthermore, in another optical semiconductor device of the present invention, as illustrated in FIG. 3, an optical semiconductor element 1 is die bonded to a lead frame 2 by a die bonding material, and this optical semiconductor element 1 is wire bonded to lead frames 2, 3 by bonding wires 4, 4'. Around the periphery of this optical semiconductor element 1 , with the exception of the upper part thereof, a dam material 8 composed of cured silicone is present. The optical semiconductor element 1 within this dam material 8 is sealed by the sealing agent 6.
[0063] The flow of manufacturing the surface mounted LED shown in FIG. 3 is
exemplified by a method including the steps of: (1) die bonding the optical semiconductor element 1 on the lead frame 2 using the die bonding material, (2) wire bonding the optical semiconductor element 1 and the lead frames 2, 3 using the bonding wires 4, 4', (3) forming the dam material 8 around the periphery of the optical semiconductor element 1 on the substrate by dispensing a hydrosilylation reaction-curable silicone composition, and (4) sealing the optical semiconductor element 1 using the sealing agent 6 composed of a curable silicone composition.
[0064] Furthermore, in another optical semiconductor device of the present invention, as illustrated in FIG. 4, an optical semiconductor element 1 is die bonded to a lead frame 2 by a die bonding material, and this optical semiconductor element 1 is wire bonded to lead frames 2, 3 by bonding wires 4, 4'. This optical semiconductor element 1 is covered by a fluorescent substance-containing sheet 10 composed of cured silicone, and this fluorescent substance-containing sheet 10 and the optical semiconductor element 1 are sealed by the sealing agent 6.
[0065] The flow of manufacturing the surface mounted LED shown in FIG. 4 is exemplified by a method including the steps of: (1) forming a frame material 9 integrated with the lead frames 2, 3 by transfer molding, compression molding or injection molding a hydrosilylation reaction-curable silicone composition, (2) die bonding the optical semiconductor element 1 on the lead frame 2 using the die bonding material, (3) wire bonding the optical semiconductor element 1 and the lead frames 2, 3 using the bonding wires 4, 4', (4) covering the optical semiconductor element 1 with the fluorescent substance-containing sheet 10, and (5) filling the optical semiconductor element 1 and the fluorescent body-containing sheet 10 with the sealing agent 6 composed of a curable silicone composition.
[0066] The curing temperature of the sealing agent 6 is not particularly limited, but good curing is generally able to be obtained from room temperature to 220°C. Curing at a temperature from 60°C to 180°C is preferable, and curing at a temperature from 80°C to 150°C is more preferable, because it results in strong adhesion between the silicone layer and substrate. Furthermore, step curing is preferable, wherein the composite is heated at from room temperature to 100°C, preferably from 60°C to 80°C, and is then heated at from 80°C to 180°C, preferably from 100°C to 150°C, because adhesion between the silicone layer and substrate is further improved in some cases.
Examples
[0067] The method of manufacturing an optical semiconductor device and the optical semiconductor device of the present invention will now be described in detail using
Examples. Furthermore, the curability and storage stability of the curable silicone composition, and the heat resistance of the cured silicone thereof were evaluated by the following methods.
[0068]
[(1) Evaluation of curability of curable silicone composition]
The light reflection material 5 (cured silicone) illustrated in FIG. 1 was produced by molding a hydrosilylation reaction-curable silicone composition integrated with lead frames 2, 3 at 150°C using a transfer molder. After the light reflection material was post- cured for 3 hours at 130°C, it was filled by dispensing the prescribed curable silicone composition to form the sealing agent 6. With the light reflection material filled with the curable silicone composition, curing of the curable silicone composition was begun at 150°C. The surface tack of the cured sealing agent 6 was checked at 5, 10, 30, 60, and 120 minutes after the start of curing, and the time until there was no tackiness was taken to be the curing time.
[0069]
[(2) Evaluation of long-term storability of curable silicone composition]
The viscosity of the curable silicone composition immediately after preparation was measured with a shear rate of 20 (1/sec) using a rheometer (AR550, manufactured by TA Instruments Corp.). After the composition was prepared and then left to stand for 24 hours at 25°C, the viscosity was measured by the same method and compared with the initial viscosity.
[0070]
[(3) Evaluation of heat resistance of cured silicone of curable silicone composition]
The produced optical semiconductor device was left for 20 minutes in a 300°C oven, and the degree of discoloration of the sealing agent was checked visually.
[0071] The cured silicones and sealing agents using in each of Practical Examples and Comparative Examples will now be specifically described. Note that in the formulae, Me, Ph, Vi, and Ep represent a methyl group, a phenyl group, a vinyl group, and a 3- glycidoxypropyl group, respectively.
[0072]
[Production Example 1 - Preparation of curable silicone composition 1 which forms cured silicone]
100.0 parts by mass of a methylvinylphenylpolysiloxane represented by the average unit formula:
(Me2ViSiO,/2)o.2o(PhSi03/2)o.80(H01/2)0.02;
8.0 parts by mass of 1 ,3, 5, 7-tetramethyl-l , 3, 5, 7-tetravinylcyclotetrasiloxane represented by the formula:
(MeViSiO)4;
20.0 parts by mass of a dimethylvinylsiloxy-terminated methylphenylpolysiloxane represented by the average formula:
ViMe2SiO(MePhSiO)17 5SiViMe2;
35.0 parts by mass of 1 ,1 ,5, 5-tetramethyl-3,3-diphenyltrisiloxane represented by the formula:
(HMe2SiO)2SiPh2
(amount resulting in 0.76 mol of silicon-bonded hydrogen atoms in this component relative to 1 mol of total vinyl groups in the aforementioned methylvinylphenylpolysiloxane, l ,3,5,7-tetramethyl-l,3,5,7-tetravinylcyclotetrasiloxane, and dimethylvinylsiloxy- terminated methylphenylpolysiloxane.);
7.5 parts by mass of a silicon-bonded hydrogen atom-containing methylphenylpolysiloxane represented by the average unit formula:
(Me2HSiOi/2)o.6(P Si03/2)o.4
(amount resulting in 0.18 mol of silicon-bonded hydrogen atoms in this component relative to 1 mol of total vinyl groups in the aforementioned methylvinylphenylpolysiloxane, 1 ,3, 5, 7-tetramethyl-l ,3, 5, 7-tetravinylcyclotetrasiloxane, and dimethylvinylsiloxy- terminated methylphenylpolysiloxane.); l,3-divinyl-l ,l ,3,3-tetramethyldisiloxane solution of l ,3-divinyl-l ,l ,3,3-tetramethyldisiloxane complex of platinum (in an amount such that ing in 5 ppm by mass of the platinum metal in the present composition); 1-ethynyl-l- cyclohexanol (amount resulting in 250 ppm by mass in the present composition); 1 10 parts by mass of titanium oxide having 0.2 μιη average primary particle diameter (SX-3103, manufactured by Sakai Chemical Industry Co., Ltd.); 100 parts by mass of crushed quartz powder having 5 μιη average particle diameter (SILICIC SAB-500, manufactured by Yamamori Tsuchimoto Mining Co., Ltd.); and 180 parts by mass of spherical silica having 15 μηι average particle diameter (HS-202, manufactured by Nippon Steel & Sumikin
Materials Co., Ltd.) were homogeneously blended to prepare curable silicone composition 1.
[0073]
[Production Example 2 - Preparation of curable silicone composition 2 which forms cured silicone]
100.0 parts by mass of a methylvinylphenylpolysiloxane represented by the average unit formula:
(Me2ViSi01/2)o.2o(PhSi03/2)0.8o(H01/2)o.02;
8.0 parts by mass of l ,3,5,7-tetramethyl-l,3,5,7-tetravinylcyclotetrasiloxane represented by the formula:
(MeViSiO)4;
20.0 parts by mass of a dimethylvinylsiloxy-terminated methylphenylpolysiloxane represented by the average formula:
ViMe2SiO(MePhSiO)i7 5SiViMe2;
35.0 parts by mass of 1 ,1 ,5,5-tetramethyl-3,3-diphenyltrisiloxane represented by the formula:
(HMe2SiO)2SiPh2
(amount resulting in 0.76 mol of silicon-bonded hydrogen atoms in this component relative to 1 mol of total vinyl groups in the aforementioned methylvinylphenylpolysiloxane, 1 ,3,5,7-tetramethyl-l ,3,5,7-tetravinylcyclotetrasiloxane, and dimethylvinylsiloxy- terminated methylphenylpolysiloxane); 7.5 parts by mass of a silicon-bonded hydrogen atom-containing methylphenylpolysiloxane represented by the average unit formula:
(Me2HSi01/2)o.6(PhSi03/2)o.4
(amount resulting in 0.18 mol of silicon-bonded hydrogen atoms in this component relative to 1 mol of total vinyl groups in the aforementioned methylvinylphenylpolysiloxane, l,3,5,7-tetramethyl-l ,3,5,7-tetravinylcyclotetrasiloxane, and dimethylvinylsiloxy- terminated methylphenylpolysiloxane); l ,3-divinyl-l ,l ,3,3-tetramethyldisiloxane solution of l ,3-divinyl-l ,l ,3,3-tetramethyldisiloxane complex of platinum (amount resulting in 10 ppm by mass of the platinum metal in the present composition); 1-ethynyl-l-cyclohexanol (amount resulting in 250 ppm by mass in the present composition); 1 10 parts by mass of titanium oxide having 0.2 μηι average primary particle diameter (SX-3103, manufactured by Sakai Chemical Industry Co., Ltd.); 100 parts by mass of crushed quartz powder having 5 μηι average particle diameter (SILICIC SAB-500, manufactured by Yamamori
Tsuchimoto Mining Co., Ltd.); and 180 parts by mass of spherical silica having 15 μ ι average particle diameter (HS-202, manufactured by Nippon Steel & Sumikin Materials Co., Ltd.) were homogeneously blended to prepare curable silicone composition 2.
[0074]
[Production Example 3 - Preparation of curable silicone composition 3 which forms cured silicone]
100.0 parts by mass of a methylvinylphenylpolysiloxane represented by the average unit formula:
(Me2ViSiOi/2)o.2o(PhSi03/2)0.8o(H01/2)o.o2;
8.0 parts by mass of l ,3,5,7-tetramethyl-l ,3,5,7-tetravinylcyclotetrasiloxane represented by the formula:
(MeViSiO)4;
20.0 parts by mass of a dimethylvinylsiloxy-terminated methylphenylpolysiloxane represented by the average formula:
ViMe2SiO(MePhSiO)i7 5SiViMe2;
35.0 parts by mass of l,l ,5,5-tetramethyl-3,3-diphenyltrisiloxane represented by the formula:
(HMe2SiO)2SiPh2
(amount resulting in 0.76 mol of silicon-bonded hydrogen atoms in this component relative to 1 mol of total vinyl groups in the aforementioned methylvinylphenylpolysiloxane, 1 ,3,5,7-tetramethyl-l ,3,5,7-tetravinylcyclotetrasiloxane, and dimethylvinylsiloxy- terminated methylphenylpolysiloxane); 7.5 parts by mass of a silicon-bonded hydrogen atom-containing methylphenylpolysiloxane represented by the average unit formula:
(Me2HSi01 /2)o.6(PhSi03/2)0.4
(amount resulting in 0.18 mol of silicon-bonded hydrogen atoms in this component relative to 1 mol of total vinyl groups in the aforementioned methylvinylphenylpolysiloxane, 1 ,3,5,7-tetramethyl- 1 ,3,5,7-tetravinylcyclotetrasiloxane, and dimethylvinylsiloxy- terminated methylphenylpolysiloxane); l ,3-divinyl-l ,l ,3,3-tetramethyldisiloxane solution of l,3-divinyl-l ,l ,3,3-tetramethyldisiloxane complex of platinum (amount resulting in 10 ppm by mass of the platinum metal in the present composition); and 1 -ethynyl- 1 - cyclohexanol (amount resulting in 250 ppm by mass in the present composition) were homogeneously blended to prepare curable silicone composition 3.
[0075]
[Production Example 4 - Preparation of curable silicone composition 4 which forms cured silicone]
48.4 parts by mass of a methylvinylphenylpolysiloxane represented by the average unit formula:
(MeViSi02/2)o.25(Ph2Si02/2)o.3o(PhSi03/2)o.45(H01/2)o.02;
51.6 parts by mass of a methylvinylphenylpolysiloxane represented by the average unit formula:
(Me2ViSiOi/2)o.2o(PhSi03/2)0.80(H01/2)o.0i;
12.9 parts by mass of a dimethylvinylsiloxy-terminated methylphenylpolysiloxane represented by the average formula:
ViMe2SiO(MePhSiO) l7 5Si ViMe2;
29.0 parts by mass of 1 ,1 ,5, 5-tetramethyl-3,3-diphenyltrisiloxane represented by the formula:
(HMe2SiO)2SiPh2
(amount resulting in 0.94 mol of silicon-bonded hydrogen atoms in this component relative to 1 mol of total vinyl groups in the aforementioned methylvinylphenylpolysiloxanes and dimethylvinylsiloxy-terminated methylphenylpolysiloxane); 1 ,3-divinyl- 1 , 1 ,3,3- tetramethyldisiloxane solution of l ,3-divinyl-l ,l,3,3-tetramethyldisiloxane complex of platinum (amount resulting in 5 ppm by mass of the platinum metal in the present composition); 1-ethynyl-l-cyclohexanol (amount resulting in 250 ppm by mass in the present composition); 1 18 parts by mass of titanium oxide having 0.2 μιη average primary particle diameter (SX-3103, manufactured by Sakai Chemical Industry Co., Ltd.); and 213 parts by mass of spherical silica having 15 μιη average particle diameter (HS-202, manufactured by Nippon Steel & Sumikin Materials Co., Ltd.) were homogeneously blended to prepare curable silicone composition 4.
[0076]
[Production Example 5 - Preparation of curable silicone composition 5 which forms cured silicone]
48.4 parts by mass of a methylvinylphenylpolysiloxane represented by the average unit formula:
(MeViSi02/2)o.25(Ph2Si02/2)o.30(PhSi03/2)0.45(HO,/2)o.o2;
51.6 parts by mass of a methylvinylphenylpolysiloxane represented by the average unit formula:
(Me2ViSiOi 2)o.2o(PhSi03 2)o.8o(HOi 2)o.oi;
12.9 parts by mass of a dimethylvinylsiloxy-terminated methylphenylpolysiloxane represented by the average formula:
ViMe2SiO(MePhSiO)i7.5SiViMe2;
29.0 parts by mass of 1 ,1 ,5,5-tetramethyl-3,3-diphenyltrisiloxane represented by the formula:
(HMe2SiO)2SiPh2
(amount resulting in 0.94 mol of silicon atom-bonded hydrogen atoms in this component relative to 1 mol of total vinyl groups in the aforementioned
methylvinylphenylpolysiloxanes and dimethylvinylsiloxy-terminated
methylphenylpolysiloxane); l,3-divinyl-l,l,3,3-tetramethyldisiloxane solution of 1 ,3- divinyl-l ,l,3,3-tetramethyldisiloxane complex of platinum (amount resulting in 10 ppm by mass of the platinum metal in the present composition); 1-ethynyl-l-cyclohexanol (amount resulting in 250 ppm by mass in the present composition); 118 parts by mass of titanium oxide having 0.2 μηι average primary particle diameter (SX-3103, manufactured by Sakai Chemical Industry Co., Ltd.); and 213 parts by mass of spherical silica having 15 μηι average particle diameter (HS-202, manufactured by Nippon Steel & Sumikin Materials Co., Ltd.) were homogeneously blended to prepare curable silicone composition 5.
[0077]
[Production Example 6 - Preparation of curable silicone composition 6 as sealing agent] 100 parts by mass of a methylvinylphenylpolysiloxane represented by the average unit formula:
(Me2ViSiOi/2)o.2o(PhSi03a)o.8o(HOi/2)o.02;
0.35 parts by mass of l ,3,5,7-tetramethyl-l ,3,5,7-tetravinylcyclotetrasiloxane represented by the formula:
(MeViSiO)4;
30.4 parts by mass of a dimethylvinylsiloxy-terminated methylphenylpolysiloxane represented by the average formula:
ViMe2SiO(MePhSiO)17.5SiViMe2;
4.17 parts by mass of an epoxy group-containing polysiloxane represented by the average unit formula:
(Me2ViSi01/2)o.2(Ph2Si02/2)o. (EpSi03/2)o.4;
34.7 parts by mass of l,l ,5,5-tetramethyl-3,3-diphenyltrisiloxane represented by the
formula:
(HMe2SiO)2SiPh2
(amount resulting in 1.03 mol of silicon-bonded hydrogen atoms in this component relative to 1 mol of total vinyl groups in the aforementioned methylvinylphenylpolysiloxane, 1 ,3,5,7-tetramethyl-l ,3,5,7-tetravinylcyclotetrasiloxane, dimethylvinylsiloxy-terminated methylphenylpolysiloxane, and epoxy group-containing polysiloxane); and 4.17 parts by mass of a silicon-bonded hydrogen-containing methylphenylpolysiloxane represented by the average unit formula: -
(Me2HSi01/2)o.6(PhSi03/2)o.4
(amount resulting in 0.14 mol of silicon-bonded hydrogen atoms in this component relative to 1 mol of total vinyl groups in the aforementioned methylvinylphenylpolysiloxane, 1 ,3,5,7-tetramethyl-l ,3,5, 7-tetravinylcyclotetrasiloxane, dimethylvinylsiloxy-terminated methylphenylpolysiloxane, and epoxy group-containing polysiloxane) were
homogeneously blended to obtain curable silicone composition 6 having viscosity of 2,400 mPa s. After the curable silicone composition 6 was left to stand for 24 hours at 25°C, its viscosity was 2,400 mPa s.
[0078]
[Production Example 7 - Preparation of curable silicone composition 7 as sealing agent] 100 parts by mass of a methylvinylphenylpolysiloxane represented by the average unit formula:
(Me2ViSi01/2)o.2o(PhSi03/2)o.8o(H01/2)o.o2;
1.59 parts by mass of l ,3,5,7-tetramethyl-l,3,5,7-tetravinylcyclotetrasiloxane represented by the formula:
(MeViSiO)4;
21.4 parts by mass of a dimethylvinylsiloxy-terminated methylphenylpolysiloxane represented by the average formula:
ViMe2SiO(MePhSiO)i7.5SiViMe2;
3.94 parts by mass of an epoxy group-containing polysiloxane represented by the average unit formula:
(Me2ViSiOi 2)o.2(Ph2SiOM)o.4(EpSi03/2)o.4;
28.7 parts by mass of 1 ,1 ,5, 5-tetramethyl-3,3-diphenyltrisiloxane represented by the formula:
(HMe2SiO)2SiPh2
(amount resulting in 0.82 mol of silicon-bonded hydrogen atoms in this component relative to 1 mol of total vinyl groups in the aforementioned methylvinylphenylpolysiloxane, 1 ,3,5,7-tetramethyl-l ,3,5,7-tetravinylcyclotetrasiloxane, dimethylvinylsiloxy-terminated methylphenylpolysiloxane, and epoxy group-containing polysiloxane); and 3.44 parts by mass of a silicon-bonded hydrogen-containing methylphenylpolysiloxane represented by the average unit formula:
(Me2HSiOI/2)o.6(PhSi03/2)o.4
(amount resulting in 0.1 1 mol of silicon-bonded hydrogen atoms in this component relative to 1 mol of total vinyl groups in the aforementioned methylvinylphenylpolysiloxane, l,3,5,7-tetramethyl-l ,3,5,7-tetravinylcyclotetrasiloxane, dimethylvinylsiloxy-terminated methylphenylpolysiloxane, and epoxy group-containing polysiloxane) were
homogeneously blended to obtain curable silicone composition 7 having viscosity of 4,600 mPa-s. After the curable silicone composition 7 was left to stand for 24 hours at 25°C, its viscosity was 4,600 mPa s.
[0079]
[Production Example 8 - Preparation of curable silicone composition 8 as sealing agent]
100 parts by mass of a methylvinylphenylpolysiloxane represented by the average unit formula:
(Me2ViSiO !/2)o.2o(PhSi03 2)o.8o(HO 1/2)0.02;
0.35 parts by mass of 1 ,3,5, 7-tetramethyl- 1,3,5, 7-tetravinylcyclotetrasiloxane represented by the formula:
(MeViSiO)4;
30.4 parts by mass of a dimethylvinylsiloxy-terminated methylphenylpolysiloxane represented by the average formula:
ViMe2SiO(MePhSiO)i7.5SiViMe2;
4.17 parts by mass of an epoxy group-containing polysiloxane represented by the average unit formula:
(Me2ViSi01/2)o.2(Ph2Si02/2)0.4(EpSi03/2)o.4;
34.7 parts by mass of l,l ,5,5-tetramethyl-3,3-diphenyltrisiloxane represented by the formula:
(HMe2SiO)2SiPh2
(amount resulting in 1.03 mol of silicon-bonded hydrogen atoms in this component relative to 1 mol of total vinyl groups in the aforementioned methylvinylphenylpolysiloxane,
1 ,3,5,7-tetramethyl-l ,3,5,7-tetravinylcyclotetrasiloxane, dimethylvinylsiloxy-terminated methylphenylpolysiloxane, and epoxy group-containing polysiloxane); 4.17 parts by mass of a silicon-bonded hydrogen-containing methylphenylpolysiloxane represented by the average unit formula:
(Me2HSi01/2)o.6(PhSi03/2)o.4
(amount resulting in 0.14 mol of silicon-bonded hydrogen atoms in this component relative to 1 mol of total vinyl groups in the aforementioned methylvinylphenylpolysiloxane, 1 ,3,5,7-tetramethyl- 1 ,3,5,7-tetravinylcyclotetrasiloxane, dimethylvinylsiloxy-terminated methylphenylpolysiloxane, and epoxy group-containing polysiloxane); and 1-ethynyl-l- cyclohexanol (amount resulting in 250 ppm by mass in the present composition) were homogeneously mixed to obtain curable silicone composition 8 having viscosity of 2,400 mPa s. After the curable silicone composition 8 was left to stand for 24 hours at 25°C, its viscosity was 2,400 mPa-s.
[0080]
[Production Example 9 - Preparation of curable silicone composition 9 as sealing agent] 100 parts by mass of a methylvinylphenylpolysiloxane represented by the average unit formula:
(Me2ViSiOi/2)o.20(PhSi03/2)o.8o(HOi/2)o.02;
1.59 parts by mass of l ,3,5,7-tetramethyl-l,3,5,7-tetravinylcyclotetrasiloxane represented by the formula:
(MeViSiO)4;
21.4 parts by mass of a dimethylvinylsiloxy-terminated methylphenylpolysiloxane represented by the average formula:
ViMe2SiO(MePhSiO)i7.5SiViMe2;
3.94 parts by mass of an epoxy group-containing polysiloxane represented by the average unit formula:
(Me2ViSiOi/2)0.2(Ph2Si02/2)o.4(EpSi03/2)0.4;
28.7 parts by mass of l ,l ,5,5-tetramethyl-3,3-diphenyltrisiloxane represented by the formula:
(HMe2SiO)2SiPh2
(amount resulting in 0.82 mol of silicon-bonded hydrogen atoms in this component relative to 1 mol of total vinyl groups in the aforementioned methylvinylphenylpolysiloxane, l ,3,5,7-tetramethyl-l ,3,5,7-tetravinylcyclotetrasiloxane, dimethylvinylsiloxy-terminated
methylphenylpolysiloxane, and epoxy group-containing polysiloxane); 3.44 parts by mass of a silicon-bonded hydrogen-containing methylphenylpolysiloxane represented by the average unit formula:
(Me2HSi01/2)o.6(PhSi03/2)o.4
(amount resulting in 0.11 mol of silicon atom-bonded hydrogen atoms in this component relative to 1 mol of total vinyl groups in the aforementioned
methylvinylphenylpolysiloxane, 1 ,3,5,7-tetramethyl-l ,3,5,7-tetravinylcyclotetrasiloxane, dimethylvinylsiloxy-terminated methylphenylpolysiloxane, and epoxy group-containing polysiloxane); and 1-ethynyl-l-cyclohexanol (amount resulting in 250 ppm by mass in the present composition) were homogeneously mixed to obtain curable silicone composition 9 having viscosity of 4,600 mPa s. After the curable silicone composition 4 was left to stand for 24 hours at 25°C, its viscosity was 4,600 mPa s.
[0081]
[Production Example 10 - Preparation of curable silicone composition 10 as sealing agent] 100 parts by mass of a methylvinylphenylpolysiloxane represented by the average unit formula:
(Me2ViSi01/2)o.2o(PhSi03/2)o.8o(HO,/2)0.02;
0.35 parts by mass of l ,3,5,7-tetramethyl-l ,3,5,7-tetravinylcyclotetrasiloxane represented by the formula:
(MeViSiO)4;
30.4 parts by mass of a dimethylvinylsiloxy-terminated methylphenylpolysiloxane represented by the average formula:
ViMe2SiO(MePhSiO)i7 5SiViMe2;
4.17 parts by mass of an epoxy group-containing polysiloxane represented by the average unit formula:
(Me2ViSi01/2)o.2(Ph2Si02/2)0.4(EpSi03/2)o.4;
34.7 parts by mass of l ,l ,5,5-tetramethyl-3,3-diphenyltrisiloxane represented by the formula:
(HMe2SiO)2SiPh2
(amount resulting in 1.03 mol of silicon-bonded hydrogen atoms in this component relative to 1 mol of total vinyl groups in the aforementioned methylvinylphenylpolysiloxane, 1 ,3,5,7-tetramethyl-l ,3,5, 7-tetravinylcyclotetrasiloxane, dimethylvinylsiloxy-terminated methylphenylpolysiloxane, and epoxy group-containing polysiloxane); 4.17 parts by mass
of a silicon-bonded hydrogen-containing methylphenylpolysiloxane represented by the average unit formula:
(Me2HSiO,/2)0.6(PhSiO3/2)0.4
(amount resulting in 0.14 mol of silicon-bonded hydrogen atoms in this component relative to 1 mol of total vinyl groups in the aforementioned methylvinylphenylpolysiloxane, 1 ,3,5,7-tetramethyl- 1 ,3,5,7-tetravinylcyclotetrasiloxane, dimethylvinylsiloxy-terminated methylphenylpolysiloxane, and epoxy group-containing polysiloxane); 1 ,3-divinyl-l , 1 ,3,3- tetramethyldisiloxane solution of 1 ,3-divinyl-l, 1 ,3, 3-tetramethyldisiloxane complex of platinum (amount resulting in 5 ppm by mass of the platinum metal in the present composition); and 1-ethynyl-l-cyclohexanol (amount resulting in 250 ppm by mass in the present composition) were homogeneously mixed to obtain curable silicone composition 10 having viscosity of 2,400 mPa-s. After the curable silicone composition 10 was left to stand for 24 hours at 25°C, its viscosity was 5,800 mPa s.
[0082]
[Production Example 1 1 - Preparation of curable silicone composition 1 1 as sealing agent] 100 parts by mass of a methylvinylphenylpolysiloxane represented by the average unit formula:
(Me2ViSi01/2)o.2o(PhSi03/2)o.8o(HOi/2)o.o2;
1.59 parts by mass of 1 ,3,5, 7-tetramethyl-l , 3,5, 7-tetravinylcyclotetrasiloxane represented by the formula:
(MeViSiO)4;
21.4 parts by mass of a dimethylvinylsiloxy-terminated methylphenylpolysiloxane represented by the average formula:
ViMe2SiO(MePhSiO)17 5SiViMe2;
3.94 parts by mass of an epoxy group-containing polysiloxane represented by the average unit formula:
(Me2ViSiOi/2)0.2(Ph2Si02/2)0.4(EpSi03/2)o.4;
28.7 parts by mass of 1,1 ,5, 5-tetramethyl-3,3-diphenyltrisiloxane represented by the formula:
(HMe2SiO)2SiPh2
(amount resulting in 0.82 mol of silicon-bonded hydrogen atoms in this component relative to 1 mol of total vinyl groups in the aforementioned methylvinylphenylpolysiloxane,
1 ,3, 5, 7-tetramethyl-l ,3, 5, 7-tetravinylcyclotetrasiloxane, dimethylvinylsiloxy-terminated
methylphenylpolysiloxane, and epoxy group-containing polysiloxane); 3.44 parts by mass of a silicon-bonded hydrogen-containing methylphenylpolysiloxane represented by the average unit formula:
(Me2HSiOi/2)o.6(PhSi03/2)0.4
(amount resulting in 0.1 1 mol of silicon-bonded hydrogen atoms in this component relative to 1 mol of total vinyl groups in the aforementioned methylvinylphenylpolysiloxane, 1 ,3,5,7-tetramethyl-l ,3,5,7-tetravinylcyclotetrasiloxane, dimethylvinylsiloxy-terminated methylphenylpolysiloxane, and epoxy group-containing polysiloxane); l ,3-divinyl-l ,l,3,3- tetramethyldisiloxane solution of l ,3-divinyl-l ,l ,3,3-tetramethyldisiloxane complex of platinum (amount resulting in 5 ppm by mass of the platinum metal in the present composition); and 1-ethynyl-l-cyclohexanol (amount resulting in 250 ppm by mass in the present composition) were homogeneously mixed to obtain curable silicone composition 1 1 having viscosity of 4,600 mPa s. After the curable silicone composition 11 was left to stand for 24 hours at 25°C, its viscosity was 10,600 mPa s.
[0083]
[Practical Example 1]
The curable silicone composition 1 prepared in Production Example 1 was molded integrated with a lead frame for 2 minutes at 150°C, and then post-cured for 1 hour in a 150°C oven to obtain a light reflection material. This was filled by dispensing the curable silicone composition 6 prepared in Production Example 6 and then curing was performed for a prescribed time in a 150°C oven, and curability was assessed according to surface tack. The obtained optical semiconductor device was put in a 300°C oven, and a heat resistance test was performed for 20 minutes. The degree of discoloration of the sealing agent was checked visually. Results of the evaluation are shown in Table 1.
[0084]
[Practical Example 2]
The curable silicone composition 1 prepared in Production Example 1 was molded integrated with a lead frame for 2 minutes at 150°C, and then post-cured for 1 hour in a 150°C oven to obtain a light reflection material. This was filled by dispensing the curable silicone composition 7 prepared in Production Example 7 and then curing was performed for a prescribed time in a 150°C oven, and curability was assessed according to surface tack. The obtained optical semiconductor device was put in a 300°C oven, and a heat resistance test was performed for 20 minutes. The degree of discoloration of the sealing
agent was checked visually. Results of the evaluation are shown in Table 1.
[0085]
[Practical Example 3]
The curable silicone composition 2 prepared in Production Example 2 was molded integrated with a lead frame for 2 minutes at 150°C, and then post-cured for 1 hour in a 150°C oven to obtain a light reflection material. This was filled by dispensing the curable silicone composition 6 prepared in Production Example 6 and then curing was performed for a prescribed time in a 150°C oven, and curability was assessed according to surface tack. The obtained optical semiconductor device was put in a 300°C oven, and a heat resistance test was performed for 20 minutes. The degree of discoloration of the sealing agent was checked visually. Results of the evaluation are shown in Table 1.
[0086]
[Practical Example 4]
The curable silicone composition 2 prepared in Production Example 2 was molded integrated with a lead frame for 2 minutes at 150°C, and then post-cured for 1 hour in a
150°C oven to obtain a light reflection material. This was filled by dispensing the curable silicone composition 7 prepared in Production Example 7 and then curing was performed for a prescribed time in a 150°C oven, and curability was assessed according to surface tack. The obtained optical semiconductor device was put in a 300°C oven, and a heat resistance test was performed for 20 minutes. The degree of discoloration of the sealing agent was checked visually. Results of the evaluation are shown in Table 1.
[0087]
[Practical Example 5]
The curable silicone composition 3 prepared in Production Example 3 was molded integrated with a lead frame for 2 minutes at 150°C, and then post-cured for 1 hour in a
150°C oven to obtain a light reflection material. This was filled by dispensing the curable silicone composition 6 prepared in Production Example 6 and then curing was performed for a prescribed time in a 150°C oven, and curability was assessed according to surface tack. The obtained optical semiconductor device was put in a 300°C oven, and a heat resistance test was performed for 20 minutes. The degree of discoloration of the sealing agent was checked visually. Results of the evaluation are shown in Table 1.
[0088]
[Practical Example 6]
The curable silicone composition 4 prepared in Production Example 4 was molded integrated with a lead frame for 2 minutes at 150°C, and then post-cured for 1 hour in a 150°C oven to obtain a light reflection material. This was filled by dispensing the curable silicone composition 6 prepared in Production Example 6 and then curing was performed for a prescribed time in a 150°C oven, and curability was assessed according to surface tack. The obtained optical semiconductor device was put in a 300°C oven, and a heat resistance test was performed for 20 minutes. The degree of discoloration of the sealing agent was checked visually. Results of the evaluation are shown in Table 1.
[0089]
[Practical Example 7]
The curable silicone composition 4 prepared in Production Example 4 was molded integrated with a lead frame for 2 minutes at 150°C, and then post-cured for 1 hour in a 150°C oven to obtain a light reflection material. This was filled by dispensing the curable silicone composition 7 prepared in Production Example 7 and then curing was performed for a prescribed time in a 150°C oven, and curability was assessed according to surface tack. The obtained optical semiconductor device was put in a 300°C oven, and a heat resistance test was performed for 20 minutes. The degree of discoloration of the sealing agent was checked visually. Results of the evaluation are shown in Table 1.
[0090]
[Practical Example 8]
The curable silicone composition 5 prepared in Production Example 5 was molded integrated with a lead frame for 2 minutes at 150°C, and then post-cured for 1 hour in a 150°C oven to obtain a light reflection material. This was filled by dispensing the curable silicone composition 6 prepared in Production Example 6 and then curing was performed for a prescribed time in a 150°C oven, and curability was assessed according to surface tack. The obtained optical semiconductor device was put in a 300°C oven, and a heat resistance test was performed for 20 minutes. The degree of discoloration of the sealing agent was checked visually. Results of the evaluation are shown in Table 1.
[0091]
[Practical Example 9]
The curable silicone composition 5 prepared in Production Example 5 was molded integrated with a lead frame for 2 minutes at 150°C, and then post-cured for 1 hour in a 150°C oven to obtain a light reflection material. This was filled by dispensing the curable
silicone composition 7 prepared in Production Example 7 and then curing was performed for a prescribed time in a 150°C oven, and curability was assessed according to surface tack. The obtained optical semiconductor device was put in a 300°C oven, and a heat resistance test was performed for 20 minutes. The degree of discoloration of the sealing agent was checked visually. Results of the evaluation are shown in Table 1.
[0092]
[Practical Example 10]
The curable silicone composition 1 prepared in Production Example 1 was molded integrated with a lead frame for 2 minutes at 150°C, and then post-cured for 1 hour in a 150°C oven to obtain a light reflection material. This was filled by dispensing the curable silicone composition 8 prepared in Production Example 8 and then curing was performed for a prescribed time in a 150°C oven, and curability was assessed according to surface tack. The obtained optical semiconductor device was put in a 300°C oven, and a heat resistance test was performed for 20 minutes. The degree of discoloration of the sealing agent was checked visually. Results of the evaluation are shown in Table 1.
[0093]
[Practical Example 1 1]
The curable silicone composition 2 prepared in Production Example 2 was molded integrated with a lead frame for 2 minutes at 150°C, and then post-cured for 1 hour in a 150°C oven to obtain a light reflection material. This was filled by dispensing the curable silicone composition 9 prepared in Production Example 9 and then curing was performed for a prescribed time in a 150°C oven, and curability was assessed according to surface tack. The obtained optical semiconductor device was put in a 300°C oven, and a heat resistance test was performed for 20 minutes. The degree of discoloration of the sealing agent was checked visually. Results of the evaluation are shown in Table 1.
[0094]
[Comparative Example 1]
The curable silicone composition 4 prepared in Production Example 4 was molded integrated with a lead frame for 2 minutes at 150°C, and then post-cured for 1 hour in a 150°C oven to obtain a light reflection material. This was filled by dispensing the curable silicone composition 10 prepared in Production Example 10 and then curing was performed for a prescribed time in a 150°C oven, and curability was assessed according to surface tack. The obtained optical semiconductor device was put in a 300°C oven, and a
heat resistance test was performed for 20 minutes. The degree of discoloration of the sealing agent was checked visually. Results of the evaluation are shown in Table 1.
[0095]
[Comparative Example 2]
The curable silicone composition 5 prepared in Production Example 5 was molded integrated with a lead frame for 2 minutes at 150°C, and then post-cured for 1 hour in a 150°C oven to obtain a light reflection material. This was filled by dispensing the curable silicone composition 1 1 prepared in Production Example 11 and then curing was performed, for a prescribed time in a 150°C oven, and curability was assessed according to surface tack. The obtained optical semiconductor device was put in a 300°C oven, and a heat resistance test was performed for 20 minutes. The degree of discoloration of the sealing agent was checked visually. Results of the evaluation are shown in Table 1.
[0096] [Table 1]
Practical Practical Practical Practical Practical Example 1 Example 2 Example 3 Example 4 Example 5
Production O — — — Example 1 O
Production
— — —
Example 2 0 O
Light
Production
reflection — — — —
Example 3 O material
Production
— — — — —
Example 4
Production
— — — — —
Example 5
Production
—
Example 6 o o — o
Production
—
Example 7 o — o —
Production
— — — — —
Sealing Example 8
agent Production
— — — — —
Example 9
Production
— — — — —
Example 10
Production
— — — — —
Example 1 1
Curability of sealing
agent (150°C cured tack- 30 30 10 10 10 free time)
Discoloration of sealing
No No No No No agent at 300°C x 10
discoloration discoloration discoloration discoloration discoloration minutes
[0097] [Table 1] Continued
discoloration discoloration discoloration discoloration discoloration
[0098] [Table 1] Continued
[0099] From the results shown in Table 1 it is seen that Practical Examples 1 to 1 1 exhibit results superior to those of Comparative Examples 1 and 2 with regard to discoloration of the sealing agent. As a result, in the optical semiconductor devices pertaining to the Practical Examples produced by the method of the present invention, discoloration at high, temperature caused by the hydrosilylation reaction catalyst can be inhibited, and also, because the curable silicone composition curing reaction itself is effectively performed by the hydrosilylation reaction catalyst in the cured silicone that contacts the sealing agent, a sealing agent that assures the desired heat resistance and storage stability can be formed.
Industrial Applicability
[0100] According to the present invention, a method of manufacturing an optical semiconductor device of which the sealing agent realizes storage stability, has good heat resistance, and can greatly resist discoloration can be provided; and an optical semiconductor device obtained by the manufacturing method can be provided.
Description of Symbols
[0101]
1 Optical semiconductor element
2 Lead frame
3 Lead frame
4, 4' Bonding wire
5 Light reflection material composed of cured silicone
6 Sealing agent
7 Substrate having cured silicone
8 Dam material composed of cured silicone
9 Frame material
10 Fluorescent substance-containing sheet composed of cured silicone
Claims
A method of manufacturing an optical semiconductor device comprising:
a step of sealing an optical semiconductor element using a curable silicone composition; the curable silicone composition, although cured by a hydrosilylation reaction, being hydrosilylation reaction catalyst free or, if containing a hydrosilylation reaction catalyst, a content of the hydrosilylation reaction catalyst being insufficient to cure the composition; and
the optical semiconductor element being sealed in a state in which the curable silicone composition contacts a cured silicone that contains a hydrosilylation reaction catalyst.
The method of manufacturing an optical semiconductor device according to claim 1, wherein the curable silicone composition comprises:
(A) at least one type of organopolysiloxane having not less than two silicon-bonded alkenyl groups per molecule; and
(B) at least one type of organopolysiloxane having not less than two silicon-bonded hydrogen atoms per molecule,
and is hydrosilylation reaction catalyst free, or, if contains a hydrosilylation reaction catalyst, a content of a hydrosilylation reaction catalyst is insufficient to cure the composition.
The method of manufacturing an optical semiconductor device according to claim 1 or 2, wherein the cured silicone is a light reflection material, a substrate, a dam material, or a fluorescent body- containing sheet.
The method of manufacturing an optical semiconductor device according to any one of claims 1 to 3, wherein the hydrosilylation reaction catalyst is a platinum-based catalyst.
The method of manufacturing an optical semiconductor device according to any one of claims 1 to 4, wherein the curable silicone composition does not contain a hydrosilylation reaction inhibitor.
The method of manufacturing an optical semiconductor device according to any one of claims 1 to 5, wherein the cured silicone contains at least one type of white pigment selected from the group consisting of titanium oxide, zinc oxide, barium titanate, barium sulfate, and zirconium oxide.
7. The method of manufacturing an optical semiconductor device according to any one of claims 1 to 6, wherein the cured silicone contains at least one type of inorganic filler selected from the group consisting of non-spherical silica, spherical silica, and glass fibers.
8. An optical semiconductor device manufactured by the manufacturing method described in any one of claims 1 to 7.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-184438 | 2013-09-05 | ||
| JP2013184438 | 2013-09-05 |
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| WO2015034073A1 true WO2015034073A1 (en) | 2015-03-12 |
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ID=52628533
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2014/073592 WO2015034073A1 (en) | 2013-09-05 | 2014-08-29 | Method of manufacturing optical semiconductor device and optical semiconductor device |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2020184641A (en) * | 2016-04-18 | 2020-11-12 | オスラム オプト セミコンダクターズ ゲゼルシャフト ミット ベシュレンクテル ハフツングＯｓｒａｍ Ｏｐｔｏ Ｓｅｍｉｃｏｎｄｕｃｔｏｒｓ ＧｍｂＨ | Manufacturing method of optoelectronic component and optoelectronic component |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009024117A (en) * | 2007-07-23 | 2009-02-05 | Sony Corp | Curable resin material-fine particle composite material, method for producing the same, optical material, and light emitting device |
| JP2009203475A (en) * | 2008-02-28 | 2009-09-10 | Mitsubishi Chemicals Corp | Sealing resin and method of producing the same |
| JP2010070719A (en) * | 2008-09-22 | 2010-04-02 | Nitto Denko Corp | Thermosetting composition and photosemiconductor device |
-
2014
- 2014-08-29 WO PCT/JP2014/073592 patent/WO2015034073A1/en active Application Filing
- 2014-09-05 TW TW103130890A patent/TW201526296A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009024117A (en) * | 2007-07-23 | 2009-02-05 | Sony Corp | Curable resin material-fine particle composite material, method for producing the same, optical material, and light emitting device |
| JP2009203475A (en) * | 2008-02-28 | 2009-09-10 | Mitsubishi Chemicals Corp | Sealing resin and method of producing the same |
| JP2010070719A (en) * | 2008-09-22 | 2010-04-02 | Nitto Denko Corp | Thermosetting composition and photosemiconductor device |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020184641A (en) * | 2016-04-18 | 2020-11-12 | オスラム オプト セミコンダクターズ ゲゼルシャフト ミット ベシュレンクテル ハフツングＯｓｒａｍ Ｏｐｔｏ Ｓｅｍｉｃｏｎｄｕｃｔｏｒｓ ＧｍｂＨ | Manufacturing method of optoelectronic component and optoelectronic component |
| JP7168615B2 (en) | 2016-04-18 | 2022-11-09 | エイエムエス－オスラム インターナショナル ゲーエムベーハー | Optoelectronic component manufacturing method, and optoelectronic component |
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