TWI643897B - Liquid epoxy resin composition for semiconductor sealing and resin sealed semiconductor device - Google Patents
Liquid epoxy resin composition for semiconductor sealing and resin sealed semiconductor device Download PDFInfo
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- TWI643897B TWI643897B TW103143891A TW103143891A TWI643897B TW I643897 B TWI643897 B TW I643897B TW 103143891 A TW103143891 A TW 103143891A TW 103143891 A TW103143891 A TW 103143891A TW I643897 B TWI643897 B TW I643897B
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- Taiwan
- Prior art keywords
- epoxy resin
- group
- resin composition
- mass
- liquid epoxy
- Prior art date
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 67
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 title claims abstract description 33
- 229920005989 resin Polymers 0.000 title claims description 30
- 239000011347 resin Substances 0.000 title claims description 30
- 238000007789 sealing Methods 0.000 title claims description 18
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011256 inorganic filler Substances 0.000 claims abstract description 20
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 20
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 10
- 239000007822 coupling agent Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 8
- 238000005538 encapsulation Methods 0.000 claims abstract description 7
- 239000000945 filler Substances 0.000 claims abstract description 6
- 238000007561 laser diffraction method Methods 0.000 claims abstract description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 50
- 239000003822 epoxy resin Substances 0.000 claims description 49
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- -1 phosphorus compound Chemical class 0.000 claims description 18
- 150000002430 hydrocarbons Chemical group 0.000 claims description 15
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 239000011342 resin composition Substances 0.000 claims description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 238000004381 surface treatment Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 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 claims description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 3
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 claims description 3
- BVURNMLGDQYNAF-UHFFFAOYSA-N dimethyl(1-phenylethyl)amine Chemical compound CN(C)C(C)C1=CC=CC=C1 BVURNMLGDQYNAF-UHFFFAOYSA-N 0.000 claims description 3
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 claims description 3
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 3
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 claims description 3
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007517 polishing process Methods 0.000 claims description 2
- IUURMAINMLIZMX-UHFFFAOYSA-N tris(2-nonylphenyl)phosphane Chemical compound CCCCCCCCCC1=CC=CC=C1P(C=1C(=CC=CC=1)CCCCCCCCC)C1=CC=CC=C1CCCCCCCCC IUURMAINMLIZMX-UHFFFAOYSA-N 0.000 claims description 2
- 235000012431 wafers Nutrition 0.000 description 32
- 229910000420 cerium oxide Inorganic materials 0.000 description 22
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 22
- 239000007788 liquid Substances 0.000 description 12
- 238000011282 treatment Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000004848 polyfunctional curative Substances 0.000 description 6
- 238000000748 compression moulding Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- MFAWEYJGIGIYFH-UHFFFAOYSA-N 2-[4-(trimethoxymethyl)dodecoxymethyl]oxirane Chemical compound C(C1CO1)OCCCC(C(OC)(OC)OC)CCCCCCCC MFAWEYJGIGIYFH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 229920002098 polyfluorene Polymers 0.000 description 3
- 229920006324 polyoxymethylene Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- 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 2
- WGCKYCGUJYPRCV-UHFFFAOYSA-N 4,5-dimethyl-7-(2-methylprop-1-enyl)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound CC(C)=CC1C=C(C)C(C)C2C(=O)OC(=O)C12 WGCKYCGUJYPRCV-UHFFFAOYSA-N 0.000 description 2
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 2
- DBJFSFSBHGPDPG-UHFFFAOYSA-N C(C(=C)C)(=O)OCCCC(C(OC)(OC)OC)CCCCCCCC Chemical compound C(C(=C)C)(=O)OCCCC(C(OC)(OC)OC)CCCCCCCC DBJFSFSBHGPDPG-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 241001050985 Disco Species 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 101100016034 Nicotiana tabacum APIC gene Proteins 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000005040 ion trap Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- AIVVXPSKEVWKMY-UHFFFAOYSA-N 4-(3,4-dicarboxyphenoxy)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 AIVVXPSKEVWKMY-UHFFFAOYSA-N 0.000 description 1
- OAWZPHCPLADLAD-UHFFFAOYSA-N 4-(trimethoxymethyl)dodecyl prop-2-enoate Chemical compound C(C=C)(=O)OCCCC(C(OC)(OC)OC)CCCCCCCC OAWZPHCPLADLAD-UHFFFAOYSA-N 0.000 description 1
- IWXCYYWDGDDPAC-UHFFFAOYSA-N 4-[(3,4-dicarboxyphenyl)methyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C(C(O)=O)=C1 IWXCYYWDGDDPAC-UHFFFAOYSA-N 0.000 description 1
- GEYAGBVEAJGCFB-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)propan-2-yl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1C(C)(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 GEYAGBVEAJGCFB-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 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
- ASILGOSHTWOLCO-UHFFFAOYSA-N C(=CC)C(C(C(OC)(OC)OC)CCCOC)CCCCCCC Chemical compound C(=CC)C(C(C(OC)(OC)OC)CCCOC)CCCCCCC ASILGOSHTWOLCO-UHFFFAOYSA-N 0.000 description 1
- OMOASQRFVYVGSY-UHFFFAOYSA-H C(C1=CC(C(=O)[O-])=CC=C1)(=O)[O-].[Bi+3].C(C1=CC(C(=O)[O-])=CC=C1)(=O)[O-].C(C1=CC(C(=O)[O-])=CC=C1)(=O)[O-].[Bi+3] Chemical compound C(C1=CC(C(=O)[O-])=CC=C1)(=O)[O-].[Bi+3].C(C1=CC(C(=O)[O-])=CC=C1)(=O)[O-].C(C1=CC(C(=O)[O-])=CC=C1)(=O)[O-].[Bi+3] OMOASQRFVYVGSY-UHFFFAOYSA-H 0.000 description 1
- GNELLERHHJENHV-UHFFFAOYSA-N CC=CC=C.CC(=C)C(O)=O.C=Cc1ccccc1 Chemical compound CC=CC=C.CC(=C)C(O)=O.C=Cc1ccccc1 GNELLERHHJENHV-UHFFFAOYSA-N 0.000 description 1
- QHJSCTNRFWNYID-UHFFFAOYSA-N CCC=COCCCC(C(OC)(OC)OC)CCCCCCCC Chemical compound CCC=COCCCC(C(OC)(OC)OC)CCCCCCCC QHJSCTNRFWNYID-UHFFFAOYSA-N 0.000 description 1
- XEEHRQPQNJOFIQ-UHFFFAOYSA-N N(C1=CC=CC=C1)CCCC(C(OC)(OC)OC)CCCCCCCC Chemical compound N(C1=CC=CC=C1)CCCC(C(OC)(OC)OC)CCCCCCCC XEEHRQPQNJOFIQ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- NMLRKAYBZCNQBX-UHFFFAOYSA-H [Bi+3].[Bi+3].[O-]C(=O)CCCCC([O-])=O.[O-]C(=O)CCCCC([O-])=O.[O-]C(=O)CCCCC([O-])=O Chemical compound [Bi+3].[Bi+3].[O-]C(=O)CCCCC([O-])=O.[O-]C(=O)CCCCC([O-])=O.[O-]C(=O)CCCCC([O-])=O NMLRKAYBZCNQBX-UHFFFAOYSA-H 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
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- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
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- BCZWPKDRLPGFFZ-UHFFFAOYSA-N azanylidynecerium Chemical compound [Ce]#N BCZWPKDRLPGFFZ-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical class [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
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Abstract
本發明係關於一種半導體密封用液狀環氧樹脂組成物,其係含有下述(A)~(D)而成,(A)於分子中未包含矽氧烷鍵之液狀環氧樹脂、(B)酸酐系硬化劑、(C)表面處理球狀無機質填充材,其係以雷射繞射法所測定之平均粒徑0.1~10μm之球狀無機質填充材來作為無機質填充材,相對於(C)成分之球狀無機質填充材100質量份,其表面藉由(甲基)丙烯酸官能性矽烷偶合劑,以0.5~2.0質量份之比例經表面處理之表面處理球狀無機質填充材、(D)硬化促進劑,根據本發明,可賦予耐熱性、耐濕性優異之半導體裝置。
Description
本發明係關於以半導體密封用液狀環氧樹脂組成物、及該樹脂組成物的硬化物進行密封之半導體裝置以及樹脂密封型半導體裝置的製造方法。
近年來,半導體裝置正迎向卓越的技術革新。
智慧型手機、平板等手提式資訊、通訊終端如可將大容量的資訊以高速進行處理般,多層連接使用TSV(直通矽穿孔(Through-silicon-via))技術之半導體元件,與8英寸~12英寸之矽中介層連接倒裝晶片後,藉由熱硬化樹脂,連同搭載複數個經多層連接之半導體元件之中介層一起密封。研磨半導體元件上不需要之硬化樹脂後,進行單片化,可得到以薄型之小型、多功能且可高速處理之半導體裝置。
使用8英寸左右之小徑晶圓等之基板時,雖然即使於現狀亦無多大問題即可密封成形,但於12英寸以上之徑,由於密封後環氧樹脂等之收縮應力較大,發生
半導體元件從金屬等之基板剝離的問題,無法量產化。隨著晶圓或金屬基板的大口徑化,為了解決如上述之問題,有必要填充90質量%以上之填料、或降低以樹脂之低彈性化硬化時之收縮應力。
然而,全面密封熱硬化樹脂於矽中介層上時,因為矽與熱硬化性樹脂的熱膨脹係數不同而發生大幅翹曲。翹曲大時,無法適用於隨後之研磨步驟或單片化步驟,成為一大技術課題。
進而於近年來,由於隨著半導體元件之層合化,密封層增厚,研磨經密封之樹脂層成為薄型之半導體裝置逐漸成為主流。研磨經密封之樹脂層時,藉由使用填充90質量%以上之填料的密封材時,切片裝置之刀片易損傷故交換頻率高,而成為高成本的原因。又由於必須提高拋光壓力進行研磨,產生半導體元件損傷、或是晶圓本身破裂的問題。另外,由於以往之聚矽氧化合物所代表之低彈性樹脂的材料,樹脂柔和,研磨時發生樹脂阻塞或是產生樹脂裂紋的問題。
尚,作為有關於本發明之先前技術可列舉下述者。
[專利文獻1]日本特開2008-266512號公報
[專利文獻2]國際公開第2009/142065號
[專利文獻3]日本特開2012-149111號公報
本發明係鑑於上述事情而完成者,係以提供一種流動性優異,減低經硬化時之翹曲的同時,賦予信賴性高之硬化物的半導體密封用液狀環氧樹脂組成物、以其硬化物密封之半導體裝置、及樹脂密封型半導體裝置的製造方法作為目的。
本發明者們為了達成上述目的,經努力研討的結果,發現使用使用了特定之填料表面處理材料進行表面處理之球狀無機質填充材之液狀環氧樹脂組成物,進行密封半導體裝置時,係耐水性、研磨性良好,即使使用大型晶圓進行密封,亦能流動性優異,減低翹曲,一般為泛用性高者,而完成本發明。
據此,本發明係提供下述之半導體密封用液狀環氧樹脂組成物、半導體裝置、及樹脂密封型半導體裝置的製造方法。
〔1〕一種半導體密封用液狀環氧樹脂組成物,其係含有下述(A)~(D)而成,(A)於分子中未包含矽氧烷鍵之液狀環氧樹脂、(B)酸酐系硬化劑、
(C)表面處理球狀無機質填充材,其係以雷射繞射法所測定之平均粒徑0.1~10μm之球狀無機質填充材來作為無機質填充材,相對於(C)成分之球狀無機質填充材100質量份,其表面藉由下述式(1)所示之(甲基)丙烯酸官能性矽烷偶合劑,以0.5~2.0質量份的比例經表面處理之表面處理球狀無機質填充材:相對於(A)、(B)成分的合計100質量份為600~1,000質量份,
[式中,a為0~3之整數、R1為碳數1~4之1價飽和烴基、R2為碳數1~10之2價飽和烴基、R3為單鍵或碳數1~10之2價飽和烴基、R4為氫原子或甲基、A為單鍵或下述式所示之任一個之基,
(式中,R5為碳數1~4之1價飽和烴基,B為O或S);
(式中,R6為碳數1~4之1價飽和烴基)];(D)硬化促進劑。
〔2〕如〔1〕記載之液狀環氧樹脂組成物,其中,(A)成分係選自雙酚A型環氧樹脂、雙酚F型環氧樹脂、萘型環氧樹脂、脂環式環氧樹脂及下述式所示之環氧樹脂中之1種以上,
〔3〕如〔1〕或〔2〕記載之半導體密封用液狀環氧樹脂組成物,其中,(B)成分係選自下述式表示之酸酐中之1種以上,
(式中,Me表示甲基,i-Pr表示異丙基)。
〔4〕如〔1〕~〔3〕中任一項所記載之液狀環氧樹脂組成物,其係相對於(A)成分100質量份,將下述平
均組成式(2)所示之聚矽氧改質環氧樹脂摻合1~50質量份而成,
(式中,R7為氫原子或碳數1~4之烷基、R8為碳數1~4之烷基、Q為碳數3~6之伸烷基、氧基伸烷基、或羥基氧基伸烷基,r為4~199之整數、p為1~10之整數、q為1~10之整數)。
〔5〕如〔1〕~〔4〕中任一項所記載之液狀環氧樹脂組成物,其中,(D)成分係選自磷系化合物、第3級胺化合物、咪唑化合物中之1以上,其量相對於(A)及(B)成分的合計100質量份為0.1~15質量份。
〔6〕如〔5〕所記載之液狀環氧樹脂組成物,其中,(D)成分係選自三苯膦、三丁基膦、三(p-甲基苯基)膦、三(壬基苯基)膦、三苯膦.三苯硼烷、四苯基膦.四苯基硼酸酯、三乙基胺、苄基二甲基胺、α-甲基苄基二甲基胺、1,8-二氮雜雙環[5.4.0]十一烯-7、2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑中之1以上。
〔7〕如〔1〕~〔6〕中任一項所記載之液狀環氧樹脂組成物,其中,以JIS K 7117-1所記載之方法測定之在25℃之黏度為5~1000Pa.s。
〔8〕一種半導體裝置,其係以如〔1〕~〔7〕中任一項所記載之液狀環氧樹脂組成物的硬化物密封。
〔9〕一種樹脂密封型半導體裝置的製造方法,其係樹脂密封型半導體裝置的製造方法,其特徵為將形成一個以上之半導體元件之矽晶圓或基板整體以半導體密封用環氧樹脂組成物的硬化物進行一起密封時,於形成一個以上之半導體元件之矽晶圓或基板的單面,將如〔1〕~〔7〕中任一項所記載之半導體密封用液狀環氧樹脂組成物於按壓下進行被覆、或於真空氛圍下進行減壓被覆,加熱硬化該樹脂組成物並密封半導體元件,隨後,並藉由研磨加工、切片硬化樹脂層進行單片化。
〔10〕如〔9〕記載之樹脂密封型半導體裝置的製造方法,其係使用直徑12英寸以上且20英寸以下之矽晶圓。
根據本發明之半導體密封用液狀環氧樹脂組成物,即使將一個以上之半導體元件以接著劑(接合劑)密封搭載於無機基板、金屬基板或有機基板上之半導體元件陣列、或形成半導體元件之大徑的矽晶圓,加熱硬化後,幾乎未發生進行冷卻時之翹曲,且可賦予耐熱性、耐
濕性優異之半導體裝置,尚且,可以晶圓水準一起密封且可輕易研磨、切片密封樹脂。
[圖1]表示玻璃轉移溫度以下及以上之線膨脹係數的求取方法之說明圖。
以下,針對本發明更進一步詳細說明。
作為本發明組成物所使用之(A)液狀環氧樹脂,若於室溫為液狀則可使用任一種之環氧樹脂,例如可列舉雙酚A型環氧樹脂及雙酚F型環氧樹脂等之雙酚型環氧樹脂;酚酚醛清漆型環氧樹脂及甲酚酚醛清漆型環氧樹脂等之酚醛清漆型環氧樹脂;萘型環氧樹脂;聯苯型環氧樹脂;環戊二烯型環氧樹脂、脂環式環氧樹脂等、及此等之混合物。
上述液狀環氧樹脂當中,特佳為雙酚A型環氧樹脂、雙酚F型環氧樹脂、脂環式環氧樹脂及萘型環氧樹脂,以該等之JIS K 7117-1所記載之方法測定之黏度(25℃)較佳為0.1~500Pa.s,更佳為1~200Pa.s。
又,較佳亦使用下述式表示之環氧樹脂。
尚,使用具有上述式之環氧樹脂時,其含量推薦為(A)成分整體之25~100質量%,更佳為50~100質量%,再更佳為75~100質量%。未達25質量%時,恐有上昇組成物之黏度、或是降低硬化物之耐熱性之虞。
(A)成分之液狀環氧樹脂係水解性氯為1000ppm以下,尤其是500ppm以下,以鈉及鉀分別為10ppm以下較佳。水解性氯超過1000ppm、或是鈉或鉀超過10ppm時,將半導體裝置於高溫高濕下長時間放置時,有耐濕性劣化的情況。
本發明所使用之(B)硬化劑若為酸酐系,可硬化(A)成分者雖並未特別限定,但較佳為於室溫為液狀、或溶解於(A)成分而成為液狀者。例如可列舉3,4-二甲基-6-(2-甲基-1-丙烯基)-1,2,3,6-四氫苯二甲酸酐、1-異丙基-4-甲基-雙環[2.2.2]辛基-5-烯-2,3-二羧酸酐、甲基四氫苯二甲酸酐、甲基六氫苯二甲酸酐、六氫苯二甲酸酐、甲基腐植酸酐、苯均四酸二酐、馬來酸化別羅勒烯(Alloocimene)、二苯甲酮四羧酸二酐、3,3’,4,4’-聯苯四雙二苯甲酮四羧酸二酐、(3,4-二羧基苯基)醚二酐、雙(3,4-二羧基苯基)甲烷二酐、2,2-雙(3,4-二羧基苯基)丙烷二酐等,此等可以單獨或以2種以上之組合使
用。
於提昇信賴性的點來看,較佳為使用下述式表示之酸酐或此等之2種以上之混合物。下述式中,Me表示甲基,Pr表示丙基。
上述較佳酸酐當中,使用3,4-二甲基-6-(2-甲基-1-丙烯基)-1,2,3,6-四氫苯二甲酸酐及1-異丙基-4-甲基-雙環[2.2.2]辛基-5-烯-2,3-二羧酸酐之混合物時,上述混合物的量期望為(B)成分整體之5~75質量%。未達5質量%時,有降低密著性,在PCT等之高溫多濕下劣化的情況。超過75質量%時,有雖提昇密著性,但在熱衝撃試驗等之試驗發生裂紋的情況。
作為上述混合物之市售例,例如可列舉日本環氧樹脂公司製之YH306、YH307(商品名)及新日本理化股份有限公司製之MH700(商品名)。
(B)成分包含5~75質量%之上述混合物時,作為殘留之硬化劑,雖並未特別限制,但較佳係於室溫為液
狀、或溶解於(A)成分而成為液狀者,例如可列舉上述所列舉之酸酐。特佳為選自甲基四氫苯二甲酸酐、甲基六氫苯二甲酸酐及六氫苯二甲酸酐中之1種以上。尚,可併用雙氰胺或己二酸醯肼、異苯二甲酸醯肼等之羧酸醯肼。
(B)成分的量係為了使(A)成分硬化之有效的量,雖因(B)成分的種類而有所不同,但將上述之酸酐作為(B)成分使用時,相對於環氧樹脂中之環氧基,由硬化劑中之酸酐基(-CO-O-CO-)所衍生之羧酸基的當量比適合以成為0.5~1.5的範圍來選擇。未達上述下限時,殘存未反應之環氧基,恐有降低玻璃轉移溫度,又降低密著性之虞。超過前述上限值時,硬化物變硬且脆,恐有迴流時或溫度循環試驗時發生裂紋之虞。
作為本發明組成物所摻合之(C)球狀無機質填充材,可使用通常摻合於環氧樹脂組成物者。例如可列舉熔融二氧化矽、結晶性二氧化矽等之二氧化矽類、氧化鋁、氮化矽、氮化鋁、氮化硼、氧化鈦、玻璃纖維等。
無機質填充材之平均粒徑及形狀係藉由雷射繞射法所測定之平均粒徑(累積重量平均值或中位徑)0.1~10μm,較佳為平均粒徑1~5μm之球狀,特佳為具有如此之平均粒徑及形狀之熔融二氧化矽。
(C)成分的量相對於(A)及(B)成分的合計100質量份為600~1,000質量份,較佳為700~900質量份。未達上述下限時,成形後之翹曲變大,無法得到充分之強度,超過上述上限時,流動性顯著惡化,排列於副支架上
之半導體元件無法完全密封。
於此,無機質填充材由於環氧樹脂與無機質填充材的相溶性良好,且結合強度增強,故使用以下述式(1)表示1種或2種以上之矽烷偶合劑進行預先表面處理者。
此情況下,a較佳為0~3,更佳為0~1。作為R1,較佳為甲基、乙基。
R2較佳為碳數1~10,特佳為1~3之伸烷基,R3較佳為單鍵或碳數1~10,特佳為1~2之伸烷基。
A雖如上所述,但R5較佳為甲基、乙基,又R6較佳為甲基、乙基。
作為如此之矽烷偶合劑之例,除了可列舉3-甲基丙烯醯氧基丙基三甲氧基矽烷(KBM503:信越化學工業股份有限公司製)、3-丙烯醯氧基丙基三甲氧基矽烷(KBM5103:信越化學工業股份有限公司製)等之外,雖可列舉下述式所示者,但並非被限定於此等。
對於表面處理所用之矽烷偶合劑的表面處理方法雖並未特別限定,但對於矽烷偶合劑處理量,相對於添加於半導體密封用熱硬化性樹脂組成物之(C)成分之球狀無機質填充材100質量份,較佳為0.5~2.0質量份,更佳為0.5~1.5質量份。
又,本發明中,係(D)成分之硬化促進劑較佳係以下表示者。可使用三苯膦、三丁基膦、三(p-甲基苯基)膦、三(壬基苯基)膦、三苯膦.三苯硼烷、四苯基膦.四苯基硼酸酯等之磷系化合物、三乙基胺、苄基二
甲基胺、α-甲基苄基二甲基胺、1,8-二氮雜雙環[5.4.0]十一烯-7等之第3級胺化合物、2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑等之咪唑化合物等。
硬化促進劑的量係為了促進環氧樹脂與硬化劑的硬化反應之有效的量,較佳係相對於(A)及(B)成分的合計100質量份為0.1~15質量份,更佳為0.5~10質量份。
本發明之液狀環氧樹脂組成物以減低硬化物的應力為目的,以不阻礙本發明之目的的量,可摻合周知之聚矽氧改質環氧樹脂、聚矽氧樹膠、聚矽氧油、聚矽氧凝膠、液狀之聚丁二烯樹膠、甲基丙烯酸甲基-丁二烯-苯乙烯等之可撓性樹脂。
作為聚矽氧改質環氧樹脂,以下述式(2)所示之樹脂較佳。
上述式中,R7為氫原子或碳數1~4之烷基,較佳為氫原子或甲基,R8為碳數1~4之烷基,較佳為甲
基。Q為碳數3~6之伸烷基、氧基伸烷基、或羥基氧基伸烷基,例如為-CH2CH2CH2-、-OCH2-CH(OH)-CH2-O-CH2CH2CH2-或-O-CH2CH2CH2-。r為4~199之整數,較佳為19~130,更佳為70~109之整數,p為1~10之整數,q為1~10之整數,較佳為2~5之整數。
摻合該聚矽氧改質環氧樹脂時,相對於(A)環氧樹脂100質量份,雖可作為1~50質量份之摻合量,但尤其是以二有機基矽氧烷單元包含1~20質量份、特佳為包含2~15質量份來進行摻合為佳,因此,可降低硬化物之應力,亦可提昇對基板的密著性。於此,二有機聚矽氧烷量可由下述式所求得。
聚矽氧烷量=(聚矽氧烷部分之分子量/聚矽氧改質環氧樹脂之分子量)×添加量
本發明之密封樹脂組成物中,進而如有必要可摻合脫模劑、難燃劑、離子阱劑、抗氧化劑、接著賦予劑、低應力劑、著色劑等各種之添加劑。
作為難燃劑並未特別限制,可使用所有周知者。其中較佳係使用偶磷氮化合物、聚矽氧化合物、鉬酸鋅載持滑石、鉬酸鋅載持氧化鋅、氫氧化鋁、氫氧化鎂、氧化鉬。
作為離子阱劑並未特別限制,可使用所有周知者。較佳係使用水滑石類、氫氧化鉍化合物、稀土類氧化物等。
本發明之半導體密封用液狀環氧樹脂組成物中,進而如有必要可摻合各種之添加劑。例如將具有如3-縮水甘油氧基丙基三甲氧基矽烷之環氧基之有機矽系的接著性提昇劑、乙炔黑、爐黑等之各種碳黑等之著色劑等作為添加劑,於不損及本發明的效果的範圍內可任意添加進行摻合。
本發明之組成物可用如以下所示之方法進行製造。例如因應需要同時或個別將環氧樹脂、硬化劑與硬化促進劑邊進行加熱處理邊攪拌、溶解、混合、使其分散,視情況,加入無機質填充材於此等之混合物,可藉由混合、攪拌、使其分散而獲得。此情況下,混合、攪拌、分散等之裝置雖並未特別限定,但具體而言,可使用具備攪拌、加熱裝置之軋碎機、雙輥、三輥、球磨機、連續擠出機、行星式混合機、或磨碎機(Masscolloider)等,亦可適當組合此等之裝置來使用。
如此進行所得之本發明之環氧樹脂組成物,自以往所採用之成形法,例如雖可利用傳遞成形、壓縮成形、注射成形、注型法等來進行,特別是期望進行壓縮成形。
此情況下,環氧樹脂組成物之成形溫度期望於100~180℃下進行45~600秒,後硬化(Postcure)係於140~180℃下進行1~6小時。
本發明之環氧樹脂組成物可縮小成形於8英寸及12英寸晶圓上時之翹曲。又,機械強度、絕緣性優
異,以其硬化物密封之半導體裝置係長期信賴性優異。又,作為以往傳遞成形、壓縮成形材料,即使使用與一般所使用之環氧樹脂組成物同樣之裝置、成形條件,由於未發生成為流痕或未填充之成形不佳,故生產性亦優異。
所謂流痕,係指從成形物之中心面對外側之放射狀所殘留之白色流動痕。發生流痕時,擔心外觀不佳、或由於二氧化矽不均勻分散造成之硬化物物性的變異、或伴隨其之信賴性降低等。
所謂未填充,係指發生於晶圓外周圍部分之樹脂的裂痕。發生未填充時,於後步驟搬送晶圓時,擔心傳感器將未填充部誤認為缺口(Notch),使對準位置之特性降低。
以下,雖顯示實施例及比較例具體說明本發明,但本發明並非限制於下述實施例者。尚,各例中之份皆為質量份,%為質量%。又,將各例之評價方法示於以下。
(1)環氧樹脂A1:雙A型環氧樹脂(Epikote828:日本環氧樹脂股份有限公司製)
(2)環氧樹脂A2:萘型環氧樹脂(HP4032D:DIC股份有限公司製)
(3)環氧樹脂A3:脂環式環氧樹脂(Celloxide2021P:Daicel化學工業公司製)
(1)硬化劑B1:下述式所示之酸酐的混合物(YH307:日本環氧樹脂股份有限公司製)
硬化劑B2:下述式所示之酸酐的混合物(MH700:新日本理化股份有限公司製)
硬化劑B3:3,3’-二乙基-4,4’-二胺基二苯甲烷(商品名:KAYAHARD AA、日本化藥(股)製)、胺當量63.5
對於基底球狀熔融二氧化矽(Admatechs製、平均粒徑5μm)100份,以0.75份之矽烷偶合劑進行乾式表面處
理,作成下述處理二氧化矽A~G。尚,比較例6中,使用無處理之上述二氧化矽。
處理二氧化矽A:以3-甲基丙烯醯氧基丙基三甲氧基矽烷(KBM503:信越化學工業股份有限公司製)表面處理之二氧化矽
處理二氧化矽B:以3-丙烯醯氧基丙基三甲氧基矽烷(KBM5103:信越化學工業股份有限公司製)表面處理之二氧化矽
處理二氧化矽C:以下述式所示之矽烷偶合劑表面處理之二氧化矽
處理二氧化矽D:以下述式所示之矽烷偶合劑表面處理之二氧化矽
處理二氧化矽E:以γ-縮水甘油氧基丙基三甲氧基矽烷(KBM403:信越化學工業股份有限公司製)表面處理之二氧化矽
處理二氧化矽F:以N-苯基-3-胺基丙基三甲氧基矽烷(KBM573:信越化學工業股份有限公司製)表面處理之二氧化矽
進而對於基底球狀熔融二氧化矽(龍森製、平均粒徑12μm)100份,以3-甲基丙烯醯氧基丙基三甲氧基矽烷(KBM503:信越化學工業股份有限公司製)0.75份進行乾式表面處理,作成處理二氧化矽G。
(D)硬化促進劑:NovacureHX3088(旭磷化E-Materials公司製)
(1)碳黑:Denka Black(電化學工業製)
(2)接著性向上劑:γ-縮水甘油氧基丙基三甲氧基矽烷(KBM403:信越化學工業股份有限公司製)
(3)聚矽氧改質環氧樹脂
於常溫(25℃)之黏度測定,以Brookfield programmable rheometer形式:在DV-III超黏度計(Cone spindleCP-51/1.0rpm)進行。
將5×5×15mm之試片設定於熱膨脹計(Rigaku TMA8140C),以昇溫5℃/分鐘、荷重19.6mN測定從25℃至300℃。作成尺寸變化與溫度之圖表,選擇於反曲點之溫度以下得到尺寸變化-溫度曲線之切線的2點任意溫度A1、A2,於反曲點之溫度以上得到切線之任意2點B1、B2,將連結A1、A2之直線與連結B1、B2之直線的交點作為玻璃轉移溫度。將A1~A2之傾斜作為Tg以下之線膨脹係數,將B1~B2之傾斜作為Tg以上之線膨脹係數(圖1)。
液狀樹脂組成物之壓縮成形後的翹曲測定,係使用晶圓8英寸/725μm厚,在APIC YAMADA公司製晶圓模(MZ407-1)將樹脂厚度設定為200μm,以壓縮時間600秒在120℃下成形後,在150℃/1小時使其完全硬化(後硬化),並確認翹曲。
將液狀樹脂組成物於120℃下600秒,壓縮成形為樹脂厚度400μm後,在150℃/1小時使其完全硬化(後硬化)後,藉由外觀目視來評價流痕、未填充的有無。
將液狀樹脂組成物於120℃下600秒,壓縮成形為樹脂厚度400μm後,在150℃/1小時使其完全硬化(後硬化)後,進行研磨性之確認,以下述之基準評價。
在條件Grinding 1.0μm/s、Spindle speed 4,800rpm、Stage speed 300rpm進行。
良好:600網孔研磨為可能,且研磨時之負荷電流值穩定為8.0A以下。
NG:無法穩定進行600網孔研磨。
將液狀樹脂組成物或顆粒狀樹脂組成物於120℃下600秒,壓縮成形為樹脂厚度400μm後,在150℃/1小時使其完全硬化(後硬化)後,進行切片性之確認,以下述之基準評價。
良好:觀察剖面,未發生矽切屑、或於樹脂與矽界面剝離的情況
NG:觀察剖面,發生矽切屑、或於樹脂與矽界面剝離的情況
於厚度200μm、8英寸晶圓使用20μm厚之接合材SFX-513M1(信越化學工業股份有限公司製),進行印刷(厚膜絲網印刷機THICK FILM PRINTER型MC212),在B階段狀態於7mm平方大之切片裝置進行切片的同時,並準備半導體晶片。
其次,於厚度200μm、8英寸晶圓上使用倒裝晶片接合器(Panasonic NM-SB50A),將附厚度220μm、7mm平方之接合材的半導體晶片以10N/150℃/1.0秒之條件進行接合,而得到搭載半導體晶片之200μm晶圓。
將附半導體晶片之200μm晶圓設定於壓縮成形機,適量載放液狀樹脂組成物,以成形壓力最大從30MPa至15MPa,並於110℃、10分鐘進行硬化,而得到晶圓。液狀樹脂組成物的量,以成形後之樹脂厚度成為400μm±10μm來調整。將其晶圓於150℃、烤箱進行2小時之熱處理後並進行硬化後,再度在切片裝置切片成7.1mm平方,而得到搭載經單片化之厚度400μm之樹脂之半導體晶片。
將經單片化之樹脂搭載半導體晶片於BT底座上,在
倒裝晶片接合器(Panasonic NM-SB50A)以10N/150℃/1.5秒之條件,以接合材SFX-513S(信越化學工業股份有限公司製)進行接合,於150℃、烤箱進行4小時熱處理,並進行後硬化,而得到附樹脂搭載半導體晶片之BT基板。
附樹脂搭載半導體晶片之BT基板上將成形複合物材料進行傳遞成形(G-LINE Press APIC YAMADA公司製),以成形條件175℃、90秒、9MPa成形成1.5mm厚,再度在切片裝置切片成10.0mm平方,而得到經單片化之附成形複合物樹脂搭載半導體晶片之BT基板(半導體裝置)。
將經單片化之上述半導體裝置,以85℃、85%RH之條件進行168小時吸濕處理。將此3次通過迴流烤箱,該迴流烤箱係以最大溫度260℃、255~260℃的時間預先設定成如30秒±3秒,並進行焊錫耐熱試驗(剝離檢査),以目視評價。
將經單片化之附成形複合物樹脂搭載半導體晶片之BT基板,使用ESPEC公司製小型冷熱衝撃裝置TSE-11,進行-55℃/15分鐘+125℃/15分鐘(自動)之循環。首先,以0次使用在超音波探傷裝置(Sonics公司製QUANTUM350)之75MHz之探測器,將半導體晶片內部之剝離狀態以無破壞確認。其次於250循環後進行同樣之
檢査,重複進行與500循環後、700循環後同樣的檢査。將結果示於表1。
對於半導體晶片之面積,剝離面積的合計約略未達5%時,評價為微小剝離「無剝離(OK)」,有5%以上之剝離面積時評價為「有剝離(NG)」。
Claims (10)
- 一種半導體密封用液狀環氧樹脂組成物,其係含有下述(A)~(D)而成,(A)於分子中未包含矽氧烷鍵之液狀環氧樹脂、(B)酸酐系硬化劑、(C)表面處理球狀無機質填充材,其係以雷射繞射法所測定之平均粒徑0.1~10μm之球狀無機質填充材來作為無機質填充材,相對於(C)成分之球狀無機質填充材100質量份,其表面藉由下述式(1)所示之(甲基)丙烯酸官能性矽烷偶合劑,以0.5~2.0質量份之比例經表面處理之表面處理球狀無機質填充材:相對於(A)、(B)成分的合計100質量份為600~1,000質量份,
- 如請求項1之液狀環氧樹脂組成物,其中,(A)成分係選自雙酚A型環氧樹脂、雙酚F型環氧樹脂、萘型環氧樹脂、脂環式環氧樹脂及下述式所示之環氧樹脂中之1種以上,
- 如請求項1或2之半導體密封用液狀環氧樹脂組成物,其中,(B)成分係選自下述式表示之酸酐中之1種以上,
- 如請求項1或2之液狀環氧樹脂組成物,其係相對於(A)成分100質量份,將下述平均組成式(2)所示之聚矽氧改質環氧樹脂摻合1~50質量份而成,
- 如請求項1或2之液狀環氧樹脂組成物,其中, (D)成分係選自磷系化合物、第3級胺化合物、咪唑化合物中之1種以上,其量相對於(A)及(B)成分的合計100質量份為0.1~15質量份。
- 如請求項5之液狀環氧樹脂組成物,其中,(D)成分係選自三苯膦、三丁基膦、三(p-甲基苯基)膦、三(壬基苯基)膦、三苯膦.三苯硼烷、四苯基膦.四苯基硼酸酯、三乙基胺、苄基二甲基胺、α-甲基苄基二甲基胺、1,8-二氮雜雙環[5.4.0]十一烯-7、2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑中之1種以上。
- 如請求項1或2之液狀環氧樹脂組成物,其中,以JIS K 7117-1所記載之方法測定在25℃之黏度為5~1000Pa.s。
- 一種半導體裝置,其係以如請求項1~7中任一項所記載之液狀環氧樹脂組成物的硬化物密封。
- 一種樹脂密封型半導體裝置的製造方法,其特徵為將形成一個以上之半導體元件之矽晶圓或基板整體以半導體密封用環氧樹脂組成物的硬化物進行一起密封時,於形成一個以上之半導體元件之矽晶圓或基板的單面,將如請求項1~7中任一項所記載之半導體密封用液狀環氧樹脂組成物於按壓下進行被覆、或於真空氛圍下進行減壓被覆,加熱硬化該樹脂組成物並密封半導體元件,隨後,並藉由研磨加工、切片硬化樹脂層進行單片化。
- 如請求項9之樹脂密封型半導體裝置的製造方法,其矽晶圓是使用直徑12英寸以上且20英寸以下。
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