JP2015044898A - Semiconductor sealing epoxy resin composition and resin sealing type semiconductor device using the same - Google Patents
Semiconductor sealing epoxy resin composition and resin sealing type semiconductor device using the same Download PDFInfo
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- JP2015044898A JP2015044898A JP2013175397A JP2013175397A JP2015044898A JP 2015044898 A JP2015044898 A JP 2015044898A JP 2013175397 A JP2013175397 A JP 2013175397A JP 2013175397 A JP2013175397 A JP 2013175397A JP 2015044898 A JP2015044898 A JP 2015044898A
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- Prior art keywords
- epoxy resin
- hydrotalcite
- resin composition
- compound
- semiconductor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 63
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 63
- 239000004065 semiconductor Substances 0.000 title claims abstract description 45
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 238000007789 sealing Methods 0.000 title claims abstract description 16
- 229920005989 resin Polymers 0.000 title abstract description 12
- 239000011347 resin Substances 0.000 title abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000011256 inorganic filler Substances 0.000 claims abstract description 14
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 14
- 238000005538 encapsulation Methods 0.000 claims description 19
- 239000004593 Epoxy Substances 0.000 claims description 2
- 239000011342 resin composition Substances 0.000 claims 1
- 238000002441 X-ray diffraction Methods 0.000 abstract description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 19
- 229960001545 hydrotalcite Drugs 0.000 description 19
- 229910001701 hydrotalcite Inorganic materials 0.000 description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 16
- -1 chlorine ions Chemical class 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000012778 molding material Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 101000653510 Homo sapiens TATA box-binding protein-like 2 Proteins 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 102100030631 TATA box-binding protein-like 2 Human genes 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HIQAWCBKWSQMRQ-UHFFFAOYSA-N 16-methylheptadecanoic acid;2-methylprop-2-enoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(=C)C(O)=O.CC(=C)C(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O HIQAWCBKWSQMRQ-UHFFFAOYSA-N 0.000 description 1
- IEKHISJGRIEHRE-UHFFFAOYSA-N 16-methylheptadecanoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O IEKHISJGRIEHRE-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- KKOHCQAVIJDYAF-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O KKOHCQAVIJDYAF-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 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
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- AZZWZMUXHALBCQ-UHFFFAOYSA-N 4-[(4-hydroxy-3,5-dimethylphenyl)methyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(CC=2C=C(C)C(O)=C(C)C=2)=C1 AZZWZMUXHALBCQ-UHFFFAOYSA-N 0.000 description 1
- VGDAMJGKFYMEDE-UHFFFAOYSA-N 5-(dimethoxymethylsilyl)pentane-1,3-diamine Chemical compound NCCC(CC[SiH2]C(OC)OC)N VGDAMJGKFYMEDE-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- SRORDPCXIPXEAX-UHFFFAOYSA-N CCCCCCCCCCCCCP(CCCCCCCCCCCCC)(O)(OCCCCCCCC)OCCCCCCCC.CCCCCCCCCCCCCP(CCCCCCCCCCCCC)(O)(OCCCCCCCC)OCCCCCCCC Chemical compound CCCCCCCCCCCCCP(CCCCCCCCCCCCC)(O)(OCCCCCCCC)OCCCCCCCC.CCCCCCCCCCCCCP(CCCCCCCCCCCCC)(O)(OCCCCCCCC)OCCCCCCCC SRORDPCXIPXEAX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KNANZMNFPYPCHN-UHFFFAOYSA-N N'-[2-(dimethoxymethylsilyl)propan-2-yl]ethane-1,2-diamine Chemical compound COC(OC)[SiH2]C(C)(C)NCCN KNANZMNFPYPCHN-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- CRGRWBQSZSQVIE-UHFFFAOYSA-N diazomethylbenzene Chemical compound [N-]=[N+]=CC1=CC=CC=C1 CRGRWBQSZSQVIE-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 1
- XMQYIPNJVLNWOE-UHFFFAOYSA-N dioctyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OCCCCCCCC XMQYIPNJVLNWOE-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- VTIXMGZYGRZMAW-UHFFFAOYSA-N ditridecyl hydrogen phosphite Chemical compound CCCCCCCCCCCCCOP(O)OCCCCCCCCCCCCC VTIXMGZYGRZMAW-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 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
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- NEXSMEBSBIABKL-UHFFFAOYSA-N hexamethyldisilane Chemical compound C[Si](C)(C)[Si](C)(C)C NEXSMEBSBIABKL-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000005040 ion trap Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 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
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- QLAGHGSFXJZWKY-UHFFFAOYSA-N triphenylborane;triphenylphosphane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QLAGHGSFXJZWKY-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/02—Bonding areas; Manufacturing methods related thereto
- H01L2224/04—Structure, shape, material or disposition of the bonding areas prior to the connecting process
- H01L2224/05—Structure, shape, material or disposition of the bonding areas prior to the connecting process of an individual bonding area
- H01L2224/0554—External layer
- H01L2224/05599—Material
- H01L2224/056—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
- H01L2224/05617—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 400°C and less than 950°C
- H01L2224/05624—Aluminium [Al] as principal constituent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
- H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
- H01L2224/45001—Core members of the connector
- H01L2224/4501—Shape
- H01L2224/45012—Cross-sectional shape
- H01L2224/45015—Cross-sectional shape being circular
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
- H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
- H01L2224/45001—Core members of the connector
- H01L2224/45099—Material
- H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
- H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
- H01L2224/45144—Gold (Au) as principal constituent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
- H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
- H01L2224/45001—Core members of the connector
- H01L2224/45099—Material
- H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
- H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
- H01L2224/45147—Copper (Cu) as principal constituent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/485—Material
- H01L2224/48505—Material at the bonding interface
- H01L2224/48599—Principal constituent of the connecting portion of the wire connector being Gold (Au)
- H01L2224/486—Principal constituent of the connecting portion of the wire connector being Gold (Au) with a principal constituent of the bonding area being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
- H01L2224/48617—Principal constituent of the connecting portion of the wire connector being Gold (Au) with a principal constituent of the bonding area being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 400°C and less than 950 °C
- H01L2224/48624—Aluminium (Al) as principal constituent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/485—Material
- H01L2224/48505—Material at the bonding interface
- H01L2224/48799—Principal constituent of the connecting portion of the wire connector being Copper (Cu)
- H01L2224/488—Principal constituent of the connecting portion of the wire connector being Copper (Cu) with a principal constituent of the bonding area being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
- H01L2224/48817—Principal constituent of the connecting portion of the wire connector being Copper (Cu) with a principal constituent of the bonding area being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 400°C and less than 950 °C
- H01L2224/48824—Aluminium (Al) as principal constituent
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
本発明は、電気特性、耐湿性、耐マイグレーション性、信頼性に優れた半導体封止用エポキシ樹脂組成物及びそれを用いた樹脂封止型半導体装置に関する。 The present invention relates to an epoxy resin composition for semiconductor encapsulation excellent in electrical characteristics, moisture resistance, migration resistance and reliability, and a resin-encapsulated semiconductor device using the same.
従来、半導体パッケージには、Ａｕワイヤを使用するものが主流であった。しかし、金価格の高騰などにより、近年では、Ｃｕワイヤを使用する傾向にある。封止材中の原材料の一つであるエポキシ樹脂は、エピクロロヒドリンを使用して作製されるものがほとんどのため、封止材中には、その塩基残さが、ワイヤ腐食性不純物として残留してしまう。ＣｕはＡｕと比較して、化学的反応性に富んでいるため、塩素による腐食が激しく、信頼性に問題があった。不純物イオンをトラップするため、無機充填剤の一つである、ハイドロタルサイト様化合物が用いられることが多い。Ｃｕワイヤの信頼性を満足させるため、様々なイオントラップ剤が検討されており、抽出水塩素イオンの低減を目的とした、半焼成ハイドロタルサイトや、焼成ハイドロタルサイトなどが検討されてきた（例えば、特許文献１、２参照）。これらは、抽出水塩素イオンの低減、耐湿信頼性の問題を解決する手段として、有効な結果を示したが、バイアス印加耐湿信頼性を、必ずしもクリアーするものではなかった。 Conventionally, semiconductor packages using Au wires have been the mainstream. However, due to soaring gold prices, in recent years, there is a tendency to use Cu wire. Most of the epoxy resin, which is one of the raw materials in the sealing material, is produced using epichlorohydrin, so the base residue remains as a corrosive impurity in the sealing material. Resulting in. Since Cu is more chemically reactive than Au, corrosion by chlorine is severe and there is a problem in reliability. In order to trap impurity ions, a hydrotalcite-like compound, which is one of inorganic fillers, is often used. In order to satisfy the reliability of Cu wire, various ion trapping agents have been studied, and semi-calcined hydrotalcite and calcined hydrotalcite for the purpose of reducing extracted water chlorine ions have been studied ( For example, see Patent Documents 1 and 2). Although these showed effective results as means for solving the problems of reduction of extracted water chloride ions and moisture resistance reliability, they did not necessarily clear the bias applied moisture resistance reliability.
本発明は、バイアス印加を加えた、高温高湿化での、リーク不良、ワイヤ間ショート不良、ワイヤオープン不良が発生せず、信頼性に優れた半導体封止用エポキシ樹脂組成物及び、それを用いた樹脂封止型半導体装置を提供することを目的とする。 The present invention provides an epoxy resin composition for semiconductor encapsulation excellent in reliability without occurrence of leakage failure, wire-to-wire short-circuit failure, or wire-open failure at high temperature and high humidity with bias applied, and An object of the present invention is to provide a resin-encapsulated semiconductor device used.
本発明は、［１］ （Ａ）エポキシ樹脂、（Ｂ）硬化剤、（Ｃ）硬化促進剤、（Ｄ）下記一般式（１）で表されるハイドロタルサイト様化合物及び（Ｅ）無機充填材を必須成分として含有し、（Ｄ）成分のハイドロタルサイト様化合物が、２．４≦Ｍｇ／Ａｌ（２．４≦ａ／ｂ）で、焼成を施していない未焼成であることを特徴とする半導体封止用エポキシ樹脂組成物に関する。 The present invention provides: [1] (A) epoxy resin, (B) curing agent, (C) curing accelerator, (D) hydrotalcite-like compound represented by the following general formula (1), and (E) inorganic filling It contains a material as an essential component, and the hydrotalcite-like compound of component (D) is 2.4 ≦ Mg / Al (2.4 ≦ a / b) and is not fired yet. It relates to an epoxy resin composition for semiconductor encapsulation.
また、本発明は、［２］ （Ｄ）成分のハイドロタルサイト様化合物が、（Ａ）エポキシ樹脂１００質量部に対し、１〜１５質量部を配合する上記［１］に記載の半導体封止用エポキシ樹脂組成物に関する。
また、本発明は、［３］ （Ｄ）成分のハイドロタルサイト様化合物が、（Ａ）エポキシ樹脂１００質量部に対し、１０〜１５質量部を配合する上記［２］に記載の半導体封止用エポキシ樹脂組成物に関する。
また、本発明は、［４］ （Ｅ）無機充填材を７５〜９７質量％含有することを特徴とする上記［１］〜［３］のいずれかに記載の半導体封止用エポキシ樹脂組成物に関する。
また、本発明は、［５］ 上記［１］〜［４］のいずれかに記載の半導体封止用エポキシ樹脂組成物を用いて半導体素子を封止してなる樹脂封止型半導体装置に関する。
Moreover, this invention is [1] The semiconductor sealing as described in [1] above, wherein the hydrotalcite-like compound of component (D) is blended in an amount of 1 to 15 parts by mass with respect to 100 parts by mass of (A) epoxy resin. The present invention relates to an epoxy resin composition.
Moreover, this invention is [3] The semiconductor sealing as described in [2] above, wherein the hydrotalcite-like compound of component (D) is blended in an amount of 10 to 15 parts by mass with respect to 100 parts by mass of (A) epoxy resin. The present invention relates to an epoxy resin composition.
Moreover, this invention contains 75-97 mass% of [4] (E) inorganic fillers, The epoxy resin composition for semiconductor sealing in any one of said [1]-[3] characterized by the above-mentioned. About.
The present invention also relates to [5] a resin-encapsulated semiconductor device obtained by encapsulating a semiconductor element using the epoxy resin composition for encapsulating a semiconductor according to any one of [1] to [4].
本発明の半導体封止用エポキシ樹脂組成物を用いることにより、Ｃｕワイヤを使用してもＣｕワイヤが腐食し抵抗が上昇するのを抑制することができ、バイアス印加した、高温高湿化での、リーク不良、ワイヤ間ショート不良、ワイヤオープン不良が発生せず、信頼性に優れた半導体封止用エポキシ樹脂組成物及び、それを用いた樹脂封止型半導体装置を提供することができる。 By using the epoxy resin composition for semiconductor encapsulation of the present invention, it is possible to suppress the corrosion of the Cu wire and increase the resistance even when the Cu wire is used. In addition, it is possible to provide a highly reliable epoxy resin composition for encapsulating a semiconductor and a resin-encapsulated semiconductor device using the same without causing a leak defect, a short-circuit between wires, or a wire open defect.
本発明の半導体封止用エポキシ樹脂組成物は、（Ａ）エポキシ樹脂、（Ｂ）硬化剤、（Ｃ）硬化促進剤、（Ｄ）上記一般式（１）で表されるハイドロタルサイト様化合物及び（Ｅ）無機充填材を必須成分として含有し、（Ｄ）成分のハイドロタルサイト様化合物が、２．４≦Ｍｇ／Ａｌ（２．４≦ａ／ｂ）で、焼成を施していない未焼成（Ｘ線回折において、層方向ピークである００１面、００２面ピークが共に観察されるもの）であることを特徴とする。
以下に、本発明の半導体封止用エポキシ樹脂組成物について説明する。
The epoxy resin composition for semiconductor encapsulation of the present invention comprises (A) an epoxy resin, (B) a curing agent, (C) a curing accelerator, and (D) a hydrotalcite-like compound represented by the above general formula (1). And (E) containing an inorganic filler as an essential component, and the hydrotalcite-like compound of component (D) is 2.4 ≦ Mg / Al (2.4 ≦ a / b) and not fired It is characterized in that it is fired (both 001 plane and 002 plane peaks which are layer direction peaks are observed in X-ray diffraction).
Below, the epoxy resin composition for semiconductor encapsulation of this invention is demonstrated.
（Ａ）エポキシ樹脂
本発明の（Ａ）エポキシ樹脂は、特に限定されるものではなく、封止用エポキシ樹脂成形材料で一般に使用されているエポキシ樹脂を使用することができる。
それを例示すれば、フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂をはじめとするフェノール、クレゾール、キシレノール、レゾルシン、カテコール、ビスフェノールＡ、ビスフェノールＦ等のフェノール類及び／又はα−ナフトール、β−ナフトール、ジヒドロキシナフタレン等のナフトール類とホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ベンズアルデヒド、サリチルアルデヒド等のアルデヒド類とを酸性触媒下で縮合又は共縮合させて得られるノボラック樹脂をエポキシ化したもの、ビスフェノールＡ、ビスフェノールＡＤ、ビスフェノールＦ、ビスフェノールＳ、アルキル置換または非置換のビフェノール等のジグリシジルエーテル、フェノール・アラルキル樹脂をエポキシ化したもの、フェノール類とジシクロペンタジエンやテルペン類との付加物または重付加物をエポキシ化したもの、フタル酸、ダイマー酸などの多塩基酸とエピクロルヒドリンの反応により得られるグリシジルエステル型エポキシ樹脂、ジアミノジフェニルメタン、イソシアヌル酸等のポリアミンとエピクロルヒドリンの反応により得られるグリシジルアミン型エポキシ樹脂、オレフィン結合を過酢酸等の過酸で酸化して得られる線状脂肪族エポキシ樹脂、及び脂環族エポキシ樹脂などが挙げられ、これらを適宜何種類でも併用することができる。
(A) Epoxy resin The (A) epoxy resin of this invention is not specifically limited, The epoxy resin generally used with the epoxy resin molding material for sealing can be used.
For example, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin and other phenols, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F and other phenols and / or α-naphthol, β- Epoxidized novolak resin obtained by condensation or cocondensation of naphthols such as naphthol and dihydroxynaphthalene with aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, etc. in the presence of an acidic catalyst, bisphenol A, bisphenol Epoxidize AD, bisphenol F, bisphenol S, diglycidyl ethers such as alkyl-substituted or unsubstituted biphenol, and phenol / aralkyl resins , Epoxidized adduct or polyaddition product of phenol and dicyclopentadiene or terpene, glycidyl ester type epoxy resin obtained by reaction of polybasic acid such as phthalic acid and dimer acid and epichlorohydrin, diamino Examples include glycidylamine type epoxy resins obtained by reaction of polyamines such as diphenylmethane and isocyanuric acid with epichlorohydrin, linear aliphatic epoxy resins obtained by oxidizing olefinic bonds with peracids such as peracetic acid, and alicyclic epoxy resins. Any number of these can be used in combination.
これら（Ａ）成分のエポキシ樹脂の純度、特に加水分解性塩素量は、ＩＣなど素子上のアルミ配線、銅配線腐食に係わるため少ない方がよく、耐湿性の優れた半導体封止用エポキシ樹脂成形材料（半導体封止用エポキシ樹脂組成物）を得るためには５００ｐｐｍ以下であることが好ましい。ここで、加水分解性塩素量とは試料のエポキシ樹脂１ｇをジオキサン３０ｍｌに溶解し、１Ｎ−ＫＯＨメタノール溶液５ｍｌを添加して３０分間リフラックス後、電位差滴定により求めた値を尺度としたものである。 The purity of these (A) component epoxy resins, especially the amount of hydrolyzable chlorine, is better because it involves corrosion of aluminum wiring and copper wiring on devices such as ICs. Molding epoxy resin for semiconductor encapsulation with excellent moisture resistance In order to obtain a material (epoxy resin composition for semiconductor encapsulation), the content is preferably 500 ppm or less. Here, the amount of hydrolyzable chlorine is a value obtained by dissolving 1 g of an epoxy resin of a sample in 30 ml of dioxane, adding 5 ml of a 1N-KOH methanol solution and refluxing for 30 minutes, and then obtaining by potentiometric titration. is there.
（Ｂ）硬化剤
硬化剤は特に限定はないが、たとえば、半導体封止用エポキシ樹脂成形材料で一般に使用されているもので、フェノール、クレゾール、レゾルシン、カテコール、ビスフェノールＡ、ビスフェノールＦ等のフェノール類又はα−ナフトール、β−ナフトール、ジヒドロキシナフタレン等のナフトール類とホルムアルデヒド等のアルデヒド類とを酸性触媒下で縮合又は共縮合させて得られるノボラック樹脂、フェノール・アラルキル樹脂、ナフトール・アラルキル樹脂等があり、単独又は併用して用いることができる。中でも、耐リフロー性向上の観点から好適なものとして、フェノール・アラルキル樹脂が挙げられる。硬化剤は、エポキシ樹脂のエポキシ基１当量に対して、エポキシ基との反応基、例えば、上記ノボラック樹脂のフェノール性水酸基、が０．５〜１．５当量になるように配合されることが好ましく、特に、０．７〜１．２当量配合することが好ましい。
(B) Curing agent The curing agent is not particularly limited. For example, phenols such as phenol, cresol, resorcin, catechol, bisphenol A, and bisphenol F are generally used in epoxy resin molding materials for semiconductor encapsulation. There are novolak resins, phenol / aralkyl resins, naphthol / aralkyl resins, etc. obtained by condensation or cocondensation of naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene with aldehydes such as formaldehyde under an acidic catalyst. These can be used alone or in combination. Among them, a phenol / aralkyl resin is preferable from the viewpoint of improving reflow resistance. The curing agent may be blended so that the reactive group with the epoxy group, for example, the phenolic hydroxyl group of the novolak resin is 0.5 to 1.5 equivalents with respect to 1 equivalent of the epoxy group of the epoxy resin. It is particularly preferable to add 0.7 to 1.2 equivalents.
（Ｃ）硬化促進剤
硬化促進剤としては、特に制限はなく、例えば、１，８−ジアザ−ビシクロ（５，４，０）ウンデセン−７、１，５−ジアザ−ビシクロ（４，３，０）ノネン、５，６−ジブチルアミノ−１，８−ジアザ−ビシクロ（５，４，０）ウンデセン−７、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス（ジメチルアミノメチル）フェノール等の３級アミン類及びこれらの誘導体、２−メチルイミダゾール、２−フェニルイミダゾール、２−フェニル−４−メチルイミダゾール等のイミダゾール類及びこれらの誘導体、トリブチルホスフィン、メチルジフェニルホスフィン、トリフェニルホスフィン、ジフェニルホスフィン、フェニルホスフィン等の有機ホスフィン類及びこれらのホスフィン類に無水マレイン酸、ベンゾキノン、ジアゾフェニルメタン等のπ結合をもつ化合物を付加してなる分子内分極を有するリン化合物、テトラフェニルホスホニウムテトラフェニルボレート、トリフェニルホスフィンテトラフェニルボレート、２−エチル−４−メチルイミダゾールテトラフェニルボレート、Ｎ−メチルモテトラフェニルホスホニウム−テトラフェニルボレート、トリフェニルホスフィン、トリフェニルホスフィンとベンゾキノンの付加物、トリパラトリルフォスフィンとベンゾキノンの付加物、１，８−ジアザービシクロ（５，４，０）−ウンデセン−７，２−フェニル−４メチル−イミダゾール、トリフェニルホスホニウム−トリフェニルボラン等があり、単独又は併用して用いることができる。硬化促進剤は、エポキシ樹脂と硬化剤の合計量に対して、０．１〜８質量％使用することが好ましい。
(C) Curing accelerator The curing accelerator is not particularly limited, and for example, 1,8-diaza-bicyclo (5,4,0) undecene-7,1,5-diaza-bicyclo (4,3,0) 3) Nonene, 5,6-dibutylamino-1,8-diaza-bicyclo (5,4,0) undecene-7, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, etc. Secondary amines and their derivatives, imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and their derivatives, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenyl Organic phosphines such as phosphine and these phosphines Phosphorus compounds having intramolecular polarization formed by adding a compound having a π bond such as maleic anhydride, benzoquinone, diazophenylmethane, etc., tetraphenylphosphonium tetraphenylborate, triphenylphosphinetetraphenylborate, 2-ethyl-4 -Methylimidazole tetraphenylborate, N-methylmotetraphenylphosphonium-tetraphenylborate, triphenylphosphine, adduct of triphenylphosphine and benzoquinone, adduct of triparatolyphosphine and benzoquinone, 1,8-diazabicyclo ( 5,4,0) -undecene-7,2-phenyl-4methyl-imidazole, triphenylphosphonium-triphenylborane, and the like, which can be used alone or in combination. It is preferable to use 0.1-8 mass% of hardening accelerators with respect to the total amount of an epoxy resin and a hardening | curing agent.
（Ｄ）一般式（１）で表されるハイドロタルサイト様化合物
本発明で用いるハイドロタルサイト様化合物は、上記一般式（１）で表されるものである。その構造は層状の結晶構造を有し、ひとつひとつの結晶片は葉片状あるいは鱗状を呈している。構造の主骨格［Ｍｇ６Ａｌ２（ＯＨ）１６］はシート状の金属水酸化物であり、ハイドロタルサイトは、構造式［Ｍ２＋ １−ｘＭ３＋ ｘ（ＯＨ）２］［Ａｎ− ｘ／ｎ・ｍＨ２Ｏ］で表される様々な化合物のうちのひとつである。Ｍ２＋とＭ３＋は、２価および３価の金属イオンを、Ａｎ− ｘ／ｎは層間陰イオンを表し、［Ｍ２＋ １−ｘＭ３＋ ｘ（ＯＨ）２］が水酸化物シートで、金属イオンを６つのOHが取り囲んで形成する八面体が互いに稜を共有することによって作られている。水酸化物シートが何枚も重なってハイドロタルサイト様化合物の層状構造を形成し、シートとシートの間（層間）には陰イオンと水分子が入っている。ハイドロタルサイト様化合物の水酸化物シートは２価金属の一部を3価金属が置き換えているので全体として正に荷電する。静電的なバランスは、層間に陰イオンが取り込まれることによって保たれるとされている。この特徴を利用してイオントラップ剤として用いることが可能となる。近年、ハイドロタルサイト様化合物を焼成することで比表面積を増大させ、化合物表面でのトラップを可能にしたイオントラップ剤が作製されているが、これはハイドロタルサイト様化合物の特徴である層構造を破壊してしまうため、本発明で用いるハイドロタルサイト様化合物とは未焼成ハイドロタルサイトのことを示す。
(D) Hydrotalcite-like compound represented by general formula (1) The hydrotalcite-like compound used in the present invention is represented by the above general formula (1). The structure has a layered crystal structure, and each crystal piece has a leaf shape or a scale shape. The main skeleton [Mg 6 Al 2 (OH) 16 ] of the structure is a sheet-like metal hydroxide, and the hydrotalcite is represented by the structural formula [M 2+ 1-x M 3+ x (OH) 2 ] [A n− x / n · mH 2 O]. M 2+ and M 3+ are divalent and trivalent metal ions, A n- x / n represents an interlayer anion is a hydroxide sheet [M 2+ 1-x M 3+ x (OH) 2] The octahedron, which is formed by surrounding 6 OH with metal ions, is made by sharing a ridge with each other. A number of hydroxide sheets overlap to form a layered structure of a hydrotalcite-like compound, and anions and water molecules are contained between the sheets (interlayer). The hydrotalcite-like compound hydroxide sheet is positively charged as a whole because the trivalent metal replaces part of the divalent metal. The electrostatic balance is said to be maintained by incorporating anions between layers. Using this feature, it can be used as an ion trapping agent. In recent years, an ion trap agent that increases the specific surface area by firing a hydrotalcite-like compound and enables trapping on the surface of the compound has been produced. This is a layer structure that is a feature of hydrotalcite-like compounds. Therefore, the hydrotalcite-like compound used in the present invention means unfired hydrotalcite.
本発明で用いるハイドロタルサイト様化合物は、２．４≦Ｍｇ／Ａｌ（２．４≦ａ／ｂ）となるようにＭｇ塩とＡｌ塩のモル比を調整し作製する。得られたハイドロタルサイト様化合物は、焼成を施していないもので、Ｘ線回折において、層方向ピークである００１面、００２面ピークが共に５°〜４５°付近におよそ等間隔で観察される。
ハイドロタルサイト様化合物の二次粒子径は、２５０μｍ以上であることが好ましく、また、ＢＥＴ比表面積が１０〜１００ｍ２/ｇが好ましい。粒度測定には、ふるい分析装置に比べ再現性に優れ短時間で測定可能な、レーザー回折／散乱式粒度分布測定装置を用いるのが好ましい。比表面積は、正確に単分子吸着量が測定可能なＢＥＴ法を用いるのが好ましい。
（Ｄ）成分のハイドロタルサイト様化合物は、（Ａ）成分のエポキシ樹脂１００質量部に対し、１〜１５質量部を配合することが好ましい。１質量部未満では、添加効果に乏しく、１５質量部を超えると効果が飽和してくる。
The hydrotalcite-like compound used in the present invention is prepared by adjusting the molar ratio of Mg salt to Al salt so that 2.4 ≦ Mg / Al (2.4 ≦ a / b). The obtained hydrotalcite-like compound is not calcined, and in X-ray diffraction, the 001 plane and 002 plane peaks, which are layer direction peaks, are observed at approximately equal intervals in the vicinity of 5 ° to 45 °. .
The secondary particle size of the hydrotalcite-like compound is preferably 250 μm or more, and the BET specific surface area is preferably 10 to 100 m 2 / g. For the particle size measurement, it is preferable to use a laser diffraction / scattering particle size distribution measuring device which is excellent in reproducibility compared with a sieve analyzer and can be measured in a short time. For the specific surface area, it is preferable to use the BET method capable of accurately measuring the amount of adsorbed single molecules.
The hydrotalcite-like compound as the component (D) is preferably blended in an amount of 1 to 15 parts by mass with respect to 100 parts by mass of the epoxy resin as the component (A). If it is less than 1 part by mass, the effect of addition is poor, and if it exceeds 15 parts by mass, the effect is saturated.
（Ｅ）無機充填材
本発明で用いる無機充填材としては、吸湿性低減及び強度向上の観点から無機充填材を用いることが必要である。（Ｅ）成分の無機充填材は、（Ｃ）成分のハイドロタルサイト様化合物を除いたものであり、無機充填材としては、溶融シリカ、結晶シリカ、アルミナ、ジルコン、珪酸カルシウム、炭酸カルシウム、炭化珪素、窒化ホウ素、ベリリア、ジルコニア等の粉体、又はこれらを球形化したビーズ、チタン酸カリウム、炭化珪素、窒化珪素、アルミナ等の単結晶繊維、ガラス繊維等を１種類以上配合することができる。さらに、難燃効果のある無機充填材としては水酸化アルミニウム、硼酸亜鉛等が挙げられ、これらを単独または併用することができる。無機充填材の配合量としては、吸湿性、線膨張係数の低減、強度向上及び半田耐熱性の観点から、本発明おける半導体封止用エポキシ樹脂組成物全体に対して７５〜９７質量％の範囲内であることが好ましく、特に、８０〜９５質量％の範囲内であることが好ましい。上記の無機充填材の中で、線膨張係数低減の観点からは溶融シリカが、高熱伝導性の観点からはアルミナが好ましく、充填材形状は成形時の流動性及び金型摩耗性の点から球形が好ましい。
(E) Inorganic filler As an inorganic filler used by this invention, it is necessary to use an inorganic filler from a viewpoint of a hygroscopic reduction and an intensity | strength improvement. The (E) component inorganic filler is obtained by removing the hydrotalcite-like compound (C), and the inorganic filler includes fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, carbonized. One or more kinds of powders such as silicon, boron nitride, beryllia, zirconia, or beads made by spheroidizing these, single crystal fibers such as potassium titanate, silicon carbide, silicon nitride, alumina, glass fibers, and the like can be blended. . Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide and zinc borate, and these can be used alone or in combination. The blending amount of the inorganic filler is in the range of 75 to 97% by mass with respect to the entire epoxy resin composition for semiconductor encapsulation in the present invention, from the viewpoints of hygroscopicity, reduction of linear expansion coefficient, strength improvement and solder heat resistance. It is preferable that it is in the range of 80 to 95% by mass. Among the above inorganic fillers, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity, and the filler shape is spherical from the viewpoint of fluidity and mold wear during molding. Is preferred.
（カップリング剤）
本発明における半導体封止用エポキシ樹脂組成物には、カップリング剤を添加することができる。カップリング剤については、特に制限はなく、シランカップリング剤以外に従来公知のカップリング剤を併用してもよい。たとえば、ビニルトリクロロシラン、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、γ−メタクリロキシプロピルトリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、ビニルトリアセトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−［ビス（β−ヒドロキシエチル）］アミノプロピルトリエトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリメトキシシラン、γ−（β−アミノエチル）アミノプロピルジメトキシメチルシラン、Ｎ−（トリメトキシシリルプロピル）エチレンジアミン、Ｎ−（ジメトキシメチルシリルイソプロピル）エチレンジアミン、メチルトリメトキシシラン、メチルトリエトキシシラン、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリメトキシシラン、γ−クロロプロピルトリメトキシシラン、ヘキサメチルジシラン、γ−アニリノプロピルトリメトキシシラン、ビニルトリメトキシシラン、γ−メルカプトプロピルメチルジメトキシシラン等のシラン系カップリング剤、あるいはイソプロピルトリイソステアロイルチタネート、イソプロピルトリス（ジオクチルパイロホスフェート）チタネート、イソプロピルトリ（Ｎ−アミノエチル−アミノエチル）チタネート、テトラオクチルビス（ジトリデシルホスファイト）チタネート、テトラ（２，２−ジアリルオキシメチル−１−ブチル）ビス（ジトリデシル）ホスファイトチタネート、ビス（ジオクチルパイロホスフェート）オキシアセテートチタネート、ビス（ジオクチルパイロホスフェート）エチレンチタネート、イソプロピルトリオクタノイルチタネート、イソプロピルジメタクリルイソステアロイルチタネート、イソプロピルトリドデシルベンゼンスルホニルチタネート、イソプロピルイソステアロイルジアクリルチタネート、イソプロピルトリ（ジオクチルホスフェート）チタネート、イソプロピルトリクミルフェニルチタネート、テトライソプロピルビス（ジオクチルホスファイト）チタネート等のチタネート系カップリング剤を１種以上併用することができる。カップリング剤は、本発明おける半導体封止用エポキシ樹脂組成物全体に対して３質量％以下で使用することが好ましく、その効果を発揮させるためには０．１質量％以上使用することが好ましい。
(Coupling agent)
A coupling agent can be added to the epoxy resin composition for semiconductor encapsulation in the present invention. There is no restriction | limiting in particular about a coupling agent, You may use a conventionally well-known coupling agent together with a silane coupling agent. For example, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyl Trimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (aminoethyl) -Γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, Tiltrimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, γ-anilinopropyltrimethoxy Silane coupling agents such as silane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, or isopropyltriisostearoyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-aminoethyl-aminoethyl) titanate Tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dio Tylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoyl diacryl titanate, isopropyltri (dioctylphosphate) One or more titanate coupling agents such as titanate, isopropyl tricumylphenyl titanate, and tetraisopropyl bis (dioctyl phosphite) titanate can be used in combination. The coupling agent is preferably used in an amount of 3% by mass or less based on the entire epoxy resin composition for semiconductor encapsulation in the present invention, and is preferably used in an amount of 0.1% by mass or more in order to exert the effect. .
（離型剤）
また、本発明における半導体封止用エポキシ樹脂組成物には、離型剤を添加することができる。離型剤についても、特に制限はないが、高級脂肪酸、例えばカルナバワックス等とポリエチレン系ワックスを単独又は併用して用いることができる。離型剤は、エポキシ樹脂と硬化剤の合計量に対して、１０質量％以下で使用することが好ましく、その効果を発揮させるためには、０．５質量％以上が好ましい。
(Release agent)
Moreover, a mold release agent can be added to the epoxy resin composition for semiconductor sealing in this invention. The release agent is not particularly limited, and higher fatty acids such as carnauba wax and polyethylene wax can be used alone or in combination. The release agent is preferably used in an amount of 10% by mass or less based on the total amount of the epoxy resin and the curing agent, and 0.5% by mass or more is preferable in order to exert the effect.
（着色剤、改質剤）
本発明における半導体封止用エポキシ樹脂組成物には、着色剤（カーボンブラック等）、改質材（シリコーン、シリコーンゴム等）を用いることができる。着色剤としてカーボンブラック等の導電性粒子を併用する場合は、本発明の目的を達成するために、粒径１０μｍ以上の粒子が１質量％以下のものを用いることが好ましく、その添加量としては（Ａ）エポキシ樹脂と（Ｂ）硬化剤の合計量に対し３質量％以下が好ましい。
(Colorant, modifier)
In the epoxy resin composition for semiconductor encapsulation in the present invention, a colorant (carbon black and the like) and a modifier (silicone, silicone rubber and the like) can be used. When conductive particles such as carbon black are used in combination as a colorant, in order to achieve the object of the present invention, it is preferable to use particles having a particle size of 10 μm or more and 1% by mass or less. (A) 3 mass% or less is preferable with respect to the total amount of an epoxy resin and (B) hardening | curing agent.
以上のような原材料を用いて成形材料を作製する一般的な方法としては、所定の配合量の原材料混合物をミキサー等によって充分混合した後、熱ロール、押出機等によって混練し、冷却、粉砕、することによって成形材料（半導体封止用エポキシ樹脂組成物粉）を得ることができる。本発明で得られる半導体封止用エポキシ樹脂組成物を用いて電子部品（半導体素子）を封止する方法としては、低圧トランスファー成形法が最も一般的であるが、インジェクション成形、圧縮成形、注型等の方法によっても可能である。上記した手段を用いて製造したエポキシ樹脂組成物は、バイアス印加耐湿信頼性試験において、リーク不良、ワイヤ間ショート不良、ワイヤオープン不良が発生せず、信頼性に優れており、ＩＣ、ＬＳＩ等の封止に好適に用いることができる。 As a general method for producing a molding material using the raw materials as described above, a raw material mixture of a predetermined blending amount is sufficiently mixed by a mixer or the like, then kneaded by a hot roll, an extruder, etc., cooled, pulverized, By doing so, a molding material (epoxy resin composition powder for semiconductor encapsulation) can be obtained. As a method for sealing an electronic component (semiconductor element) using the epoxy resin composition for semiconductor sealing obtained in the present invention, the low pressure transfer molding method is the most common, but injection molding, compression molding, casting It is also possible by such a method. The epoxy resin composition produced by using the above-mentioned means is excellent in reliability without occurrence of a leak failure, a wire short-circuit failure, or a wire open failure in a bias applied moisture resistance reliability test. It can be suitably used for sealing.
以下に本発明の実施例について説明するが、本発明はこれに限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited thereto.
（実施例１〜４及び比較例１〜４）
表１中に示す各種の素材を予備混合（ドライブレンド）した後、二軸ロール（ロール表面約８０℃）で約１５分間混練し、冷却粉砕して半導体封止用エポキシ樹脂組成物粉を製造した。
(Examples 1-4 and Comparative Examples 1-4)
Various materials shown in Table 1 are premixed (dry blended), then kneaded with a biaxial roll (roll surface about 80 ° C.) for about 15 minutes, cooled and pulverized to produce an epoxy resin composition powder for semiconductor encapsulation. did.
Ｅ１：ＹＳＬＶ−８０ＸＹ（3，3´，5，5´−テトラメチル−4，4´−ジヒドロキシジフェニルメタンのエポキシ化合物）、新日鐵化学（株）商品名
Ｅ２：ＹＸ−４０００（ビフェニル型エポキシ樹脂）、油化シェルエポキシ（株）商品名
Ｅ３：ＨＰ−５０００（ナフタレン変性クレゾールノボラックエポキシ樹脂）、ＤＩＣ（株）商品名
Ｅ４：ＣＥＲ−３０００Ｌ（ビフェニルノボラック型エポキシ樹脂とビフェニル型エポキシ樹脂の混合物）、日本化薬（株）商品名
Ｅ５：ＹＳＬＶ−１２０ＴＥ（ジメチルジヒドロキシ・ジターシャリーブチルジフェニルスルフィド型エポキシ樹脂）、新日鐵化学（株）商品名
Ｅ６：ＮＣ−３０００（ビフェニル・アラルキル型エポキシ樹脂）、日本化薬（株）商品名
Ｈ１：ＨＥ９１０（多官能型フェノール樹脂）、エア・ウォータ（株）商品名
Ｈ２：ＨＥ２００Ｃ（ビフェニル・アラルキル型フェノール樹脂）、エア・ウォータ（株）商品名
Ｈ３：ＭＥＨ−７８００（フェノール・アラルキル樹脂）、明和化成（株）商品名
ＨＡ−１：ＴＢＰ２（トリブチルホスフィンとベンゾキノンの付加物）、黒金化成（株）商品名
ＨＡ−２：Ｐ−２（トリフェニルホスフィンとベンゾキノンの付加物）、北興化学工業（株）商品名
ＨＴ−１：ハイドロタルサイト、Ｍｇ／Ａｌ≒３．０、未焼成タイプ
ＨＴ−２：ハイドロタルサイト、Ｍｇ／Ａｌ≒２．５、焼成タイプ
E1: YSLV-80XY (epoxy compound of 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenylmethane), Nippon Steel Chemical Co., Ltd., trade name E2: YX-4000 (biphenyl type epoxy resin) ), Yuka Shell Epoxy Co., Ltd., trade name E3: HP-5000 (Naphthalene-modified cresol novolac epoxy resin), DIC Corporation, trade name E4: CER-3000L (mixture of biphenyl novolac type epoxy resin and biphenyl type epoxy resin) Nippon Kayaku Co., Ltd. trade name E5: YSLV-120TE (dimethyl dihydroxy ditertiary butyl diphenyl sulfide type epoxy resin), Nippon Steel Chemical Co., Ltd. trade name E6: NC-3000 (biphenyl aralkyl type epoxy resin) Nippon Kayaku Co., Ltd. trade name H1: HE910 (polyfunctional phenol) Fat), Air Water Co., Ltd. trade name H2: HE200C (biphenyl aralkyl type phenol resin), Air Water Co., Ltd. trade name H3: MEH-7800 (phenol aralkyl resin), Meiwa Kasei Co., Ltd. trade name HA-1: TBP2 (addition product of tributylphosphine and benzoquinone), Kurokin Kasei Co., Ltd. trade name HA-2: P-2 (addition product of triphenylphosphine and benzoquinone), Hokuko Chemical Co., Ltd. trade name HT -1: Hydrotalcite, Mg / Al≈3.0, unfired type HT-2: Hydrotalcite, Mg / Al≈2.5, fired type
上記で得られた半導体封止用エポキシ樹脂組成物粉を用い、トランスファー成形機により、金型温度１７５〜１８０℃、成形圧力１７ｋｇｆ／ｃｍ２(１．６７ＭＰａ)、硬化時間９０秒の条件で半導体を封止し下記の評価に用いる試験片を作製した。 Using the epoxy resin composition powder for semiconductor encapsulation obtained above, a transfer molding machine was used to form a semiconductor under conditions of a mold temperature of 175 to 180 ° C., a molding pressure of 17 kgf / cm 2 (1.67 MPa), and a curing time of 90 seconds. The test piece used for the following evaluation was produced.
性能評価；
＜ＨＡＳＴ（Highly Accelerated temperature and humidity Stress Test、超加速寿命試験）特性＞
電極には、Ａｌ／Ｓｉ／Ｃｕ＝９８．９％／０．８％／０．３％、幅６０μｍのパッドを使用し、ワイヤには純銅ワイヤ（直径２０μｍ）を用いた。この評価基板を１３０℃、湿度８５％雰囲気の高温高湿槽に入れ、電圧５Ｖを印加し、累計２４時間、４８時間、９６時間、１６８時間、３３６時間、槽内ＨＡＳＴ試験を行った。上記時間経過時、電気特性評価を行い、ワイヤオープンしたパッケージ(抵抗値上昇１００％)を「ＮＧ」、抵抗上昇値１００％未満のパッケージを「ＯＫ」と評価した。
Performance evaluation;
<HAST (Highly Accelerated temperature and humidity Stress Test) characteristics>
A pad of Al / Si / Cu = 98.9% / 0.8% / 0.3% and a width of 60 μm was used for the electrode, and a pure copper wire (diameter 20 μm) was used for the wire. This evaluation substrate was placed in a high-temperature and high-humidity tank having an atmosphere of 130 ° C. and a humidity of 85%, a voltage of 5 V was applied, and a total HAST test was performed for 24 hours, 48 hours, 96 hours, 168 hours, and 336 hours. When the time elapsed, electrical characteristics were evaluated, and a wire-open package (resistance value increase 100%) was evaluated as “NG”, and a package with a resistance increase value less than 100% was evaluated as “OK”.
表１で使用したハイドロタルサイト種は、ＨＴ−１(Ｍｇ／Ａｌ≒３．０かつ未焼成タイプ）、ＨＴ−２（Ｍｇ／Ａｌ≒２．５かつ焼成タイプ）を用いた。実施例１、比較例１はともに同種の樹脂系を選択し、ハイドロタルサイト様化合物種のみ変更してある。ＨＡＳＴの評価結果を表２に示した。Ｍｇ／Ａｌ比率が高く、未焼成タイプのハイドロタルサイト様化合物を使用した実施例１が、比較例１に比べ、ＨＡＳＴ試験結果が良好となった。同様に、樹脂系を変えて実施例２から実施例４まで、ＨＡＳＴの評価試験を行ったところ、全ての系で、比較例より良好な結果となった。 As hydrotalcite species used in Table 1, HT-1 (Mg / Al≈3.0 and unfired type) and HT-2 (Mg / Al≈2.5 and fired type) were used. In both Example 1 and Comparative Example 1, the same type of resin system was selected, and only the hydrotalcite-like compound type was changed. The evaluation results of HAST are shown in Table 2. The HAST test result of Example 1 using a non-fired hydrotalcite-like compound with a high Mg / Al ratio was better than that of Comparative Example 1. Similarly, when the HAST evaluation test was performed from Example 2 to Example 4 by changing the resin system, the results were better than the comparative example in all systems.
（実施例５、６及び比較例５−１〜５−３）
上記実施例と同様に表３に示した配合で半導体封止用エポキシ樹脂組成物粉を作製し、試験片を作製した。
(Examples 5 and 6 and Comparative Examples 5-1 to 5-3)
The epoxy resin composition powder for semiconductor sealing was produced by the mixing | blending shown in Table 3 similarly to the said Example, and the test piece was produced.
Ｅ２：YX-4000、油化シェルエポキシ（株）商品名
Ｈ１：HE910、エア・ウォータ（株）商品名
Ｈ２：HE200C、エア・ウォータ（株）商品名
ＨＡ−１：TBP2、黒金化成（株）商品名
ＨＴ−１：ハイドロタルサイト、Ｍｇ／Ａｌ≒３．０、未焼成タイプ
ＨＴ−３：ハイドロタルサイト、Ｍｇ／Ａｌ≒０．６、未焼成タイプ
ＨＴ−４：ハイドロタルサイト、Ｍｇ／Ａｌ≒１．８、未焼成タイプ
ＨＴ−５：ハイドロタルサイト、Ｍｇ／Ａｌ≒２．１、未焼成タイプ
ＨＴ−６：ハイドロタルサイト、Ｍｇ／Ａｌ≒２．７、未焼成タイプ
表３で使用したハイドロタルサイト種は、全て未焼成タイプである。また、ＨＴ−１のＭｇ／Ａｌ比率はおよそ３．０、ＨＴ−６はＭｇ／Ａｌ≒２．７であり、ＨＴ−３はＭｇ／Ａｌ≒０．６、ＨＴ−４はＭｇ／Ａｌ≒１．８、ＨＴ−５はＭｇ／Ａｌ≒２．１と徐々にＭｇ比率を上げたものを比較例としてある。ＨＡＳＴの評価結果を表４に示した。結果として、Ｍｇ比率が高いほどＨＡＳＴ試験で良好な結果を得られることがわかった。 The hydrotalcite species used in Table 3 are all unfired types. Further, the Mg / Al ratio of HT-1 is approximately 3.0, HT-6 is Mg / Al≈2.7, HT-3 is Mg / Al≈0.6, and HT-4 is Mg / Al≈. 1.8 and HT-5 are comparative examples in which the Mg ratio is gradually increased to Mg / Al≈2.1. The evaluation results of HAST are shown in Table 4. As a result, it was found that the higher the Mg ratio, the better the results obtained in the HAST test.
（実施例７〜８及び比較例６〜９）
上記実施例と同様に表５に示した配合で半導体封止用エポキシ樹脂組成物粉を作製し、試験片を作製した。
(Examples 7-8 and Comparative Examples 6-9)
The epoxy resin composition powder for semiconductor sealing was produced by the mixing | blending shown in Table 5 similarly to the said Example, and the test piece was produced.
Ｅ１：YSLV-80XY、新日鐵化学（株）商品名
Ｅ２：YX-4000、油化シェルエポキシ（株）商品名
Ｈ１：HE910、エア・ウォータ（株）商品名
Ｈ２：HE200C、エア・ウォータ（株）商品名
ＨＡ−１：TBP2、黒金化成（株）商品名
ＨＴ−１：ハイドロタルサイト、Ｍｇ／Ａｌ≒３．０、未焼成タイプ
ＨＴ−３：ハイドロタルサイト、Ｍｇ／Ａｌ≒０．６、未焼成タイプ
ＨＴ−６：ハイドロタルサイト、Ｍｇ／Ａｌ≒２．７、未焼成タイプ
ＨＴ−７：ハイドロタルサイト、Ｍｇ／Ａｌ≒３．０、焼成タイプ
ＨＴ−８：ハイドロタルサイト、Ｍｇ／Ａｌ≒０．６、焼成タイプ
ＨＴ−９：ハイドロタルサイト、Ｍｇ／Ａｌ≒２．７、焼成タイプ
E1: YSLV-80XY, Nippon Steel Chemical Co., Ltd. trade name E2: YX-4000, Yuka Shell Epoxy Co., Ltd. trade name H1: HE910, Air Water Co., Ltd. trade name H2: HE200C, Air Water ( Co., Ltd. Trade name HA-1: TBP2, Kurogane Kasei Co., Ltd. trade name HT-1: Hydrotalcite, Mg / Al≈3.0, Unfired type HT-3: Hydrotalcite, Mg / Al≈0 .6, unfired type HT-6: hydrotalcite, Mg / Al≈2.7, unfired type HT-7: hydrotalcite, Mg / Al≈3.0, fired type HT-8: hydrotalcite Mg / Al≈0.6, fired type HT-9: hydrotalcite, Mg / Al≈2.7, fired type
表５では、未焼成タイプ、焼成タイプの効力の違いを検証した。実施例７ではＨＴ−１を使用した系、比較例６はＨＴ−１の焼成タイプであるＨＴ−７を使用した系を検証した。同様に、Ｍｇ／Ａｌ比率を変更して同様の検証を行った。比較例７は、ＨＴ−３を使用した系、比較例８はＨＴ−３の焼成タイプであるＨＴ−８を使用した系を検証した。実施例８は、ＨＴ−６を使用した系、比較例９は、ＨＴ−６の焼成タイプであるＨＴ−９を使用した系を検証した。それぞれのＨＡＳＴ検証結果を表６に示した。結果としては、ハイドロタルサイト様化合物のＭｇ／Ａｌ比率が変わっても、焼成タイプより、未焼成タイプを使用した系が、バイアス印加ＨＡＳＴ試験では良好な結果が得られることがわかった。 In Table 5, the difference in efficacy between the unfired type and the fired type was verified. In Example 7, a system using HT-1 was tested, and in Comparative Example 6, a system using HT-7, which was a baked type of HT-1, was verified. Similarly, the same verification was performed by changing the Mg / Al ratio. The comparative example 7 verified the system which used HT-3, and the comparative example 8 verified the system which used HT-8 which is a baking type of HT-3. Example 8 verified the system using HT-6, and Comparative Example 9 verified the system using HT-9, which is a firing type of HT-6. The respective HAST verification results are shown in Table 6. As a result, it was found that even when the Mg / Al ratio of the hydrotalcite-like compound was changed, a system using an unfired type was better than a fired type in the bias applied HAST test.
従来から、不純物抽出液測定では、焼成タイプのハイドロタルサイト様化合物を使用した方が良好な結果が得られるため、ＨＡＳＴ試験には有効だとされてきた（例えば、特許文献１、２参照）。
それは、層間でイオンをトラップする未焼成タイプのハイドロタルサイト様化合物と比較して、焼成タイプは、焼成することにより表面部分にポーラスが多く発生し、表面積が非常に高くなり、表面トラップ能が高くなるためである。しかし、バイアスを印加するＨＡＳＴ試験では、トラップしたイオンの保持能力が高くなければならないため、表面トラップ能では不十分である。そのため、層間に不純物イオンをトラップできる未焼成タイプが、バイアス印加ＨＡＳＴ試験には有効と言える。
Conventionally, in the measurement of an impurity extract, it has been considered effective for a HAST test because a better result is obtained when a calcined hydrotalcite-like compound is used (for example, see Patent Documents 1 and 2). .
Compared with the uncalcined hydrotalcite-like compound that traps ions between layers, the calcined type generates a lot of porosity on the surface part when calcined, the surface area becomes very high, and the surface trapping ability is high. This is because it becomes higher. However, in the HAST test in which a bias is applied, the trapping ion retention capability must be high, so the surface trapping capability is insufficient. Therefore, it can be said that an unfired type capable of trapping impurity ions between layers is effective for the bias applied HAST test.
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| JP2021054883A (en) * | 2019-09-27 | 2021-04-08 | 小川香料株式会社 | Flavor improver for vanilla flavor beverage and food product |
| JP7472931B2 (en) | 2017-03-31 | 2024-04-23 | 株式会社レゾナック | Epoxy resin composition for sealing and electronic component device |
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