JP5499772B2 - Adhesive member for semiconductor, adhesive composition for semiconductor, adhesive film for semiconductor, laminate and method for producing semiconductor device - Google Patents
Adhesive member for semiconductor, adhesive composition for semiconductor, adhesive film for semiconductor, laminate and method for producing semiconductor device Download PDFInfo
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- JP5499772B2 JP5499772B2 JP2010042053A JP2010042053A JP5499772B2 JP 5499772 B2 JP5499772 B2 JP 5499772B2 JP 2010042053 A JP2010042053 A JP 2010042053A JP 2010042053 A JP2010042053 A JP 2010042053A JP 5499772 B2 JP5499772 B2 JP 5499772B2
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- 239000004065 semiconductor Substances 0.000 title claims description 205
- 239000002313 adhesive film Substances 0.000 title claims description 151
- 230000001070 adhesive effect Effects 0.000 title claims description 111
- 239000000853 adhesive Substances 0.000 title claims description 110
- 239000000203 mixture Substances 0.000 title claims description 61
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000003822 epoxy resin Substances 0.000 claims description 43
- 229920000647 polyepoxide Polymers 0.000 claims description 43
- 239000000945 filler Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 34
- 229920005989 resin Polymers 0.000 claims description 27
- 239000011347 resin Substances 0.000 claims description 27
- 239000005011 phenolic resin Substances 0.000 claims description 24
- 229920001187 thermosetting polymer Polymers 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 125000000524 functional group Chemical group 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims 1
- 235000012431 wafers Nutrition 0.000 description 40
- 238000001723 curing Methods 0.000 description 23
- 239000000758 substrate Substances 0.000 description 18
- 239000002966 varnish Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000010410 layer Substances 0.000 description 14
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 125000003700 epoxy group Chemical group 0.000 description 11
- 239000004593 Epoxy Substances 0.000 description 8
- -1 acrylate ester Chemical class 0.000 description 8
- 239000007822 coupling agent Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000011164 primary particle Substances 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 6
- 229920006243 acrylic copolymer Polymers 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
- 150000001875 compounds Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 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 4
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000012790 confirmation Methods 0.000 description 4
- 229930003836 cresol Natural products 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000002985 plastic film Substances 0.000 description 4
- 229920006255 plastic film Polymers 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229920000800 acrylic rubber Polymers 0.000 description 3
- 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 3
- 229910002026 crystalline silica Inorganic materials 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000010419 fine particle 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
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000015654 memory Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000391 magnesium silicate Substances 0.000 description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 description 2
- 235000019792 magnesium silicate Nutrition 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000009974 thixotropic effect Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- JMMZCWZIJXAGKW-UHFFFAOYSA-N 2-methylpent-2-ene Chemical compound CCC=C(C)C JMMZCWZIJXAGKW-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical class [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 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
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- PEEDYJQEMCKDDX-UHFFFAOYSA-N antimony bismuth Chemical compound [Sb].[Bi] PEEDYJQEMCKDDX-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004849 latent hardener Substances 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Die Bonding (AREA)
- Dicing (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、半導体用接着部材、半導体用接着剤組成物、半導体用接着フィルム、積層体及び半導体装置の製造方法に関する。 The present invention relates to a semiconductor adhesive member, a semiconductor adhesive composition, a semiconductor adhesive film, a laminate, and a method for manufacturing a semiconductor device.
近年、電子機器の発達に伴い電子部品の搭載密度が高くなり、マルチチップスタックドパッケージ（以下ＭＣＰと略する）と呼ばれるような、半導体チップを積層していく半導体パッケージ等の新しい形式の実装方法が採用され始め、使用される半導体ウエハの厚みもさらなる薄膜化が進んでいる。 In recent years, with the development of electronic devices, the mounting density of electronic components has increased, and a new type of mounting method such as a semiconductor package in which semiconductor chips are stacked such as a multi-chip stacked package (hereinafter abbreviated as MCP). The thickness of semiconductor wafers used has been further reduced.
従来の半導体搭載基板に用いられる接着部材としては、液状接着剤あるいはフィルム状接着剤（以下、「接着フィルム」ともいう）が使用されるのが一般的であるが、近年の半導体素子の小型化・高性能化に伴い、使用される支持部材にも小型化・細密化が要求されるようになってきており、近年、微細加工が容易である接着フィルムが多く使われている。 In general, liquid adhesives or film adhesives (hereinafter also referred to as “adhesive films”) are used as adhesive members used in conventional semiconductor mounting substrates. -With high performance, the supporting members used are required to be miniaturized and densified, and in recent years, adhesive films that can be easily finely processed are often used.
この接着フィルムは、個片貼付け方式あるいはウエハ裏面貼付け方式において使用されている。前者の個片貼付け方式の接着フィルムを用いて半導体装置を製造する場合、リール状の接着フィルムをカッティングあるいはパンチングによって個片に切り出した後、その個片を支持部材に接着し、上記接着フィルム付き支持部材にダイシング工程によって個片化された半導体素子を接合して半導体素子付き支持部材を作製し、その後必要に応じてワイヤボンド工程、封止工程等を経ることによって半導体装置が得られることとなる。 This adhesive film is used in an individual piece bonding method or a wafer back surface bonding method. When manufacturing a semiconductor device using the former adhesive film of the individual piece attachment method, after cutting the reel-like adhesive film into individual pieces by cutting or punching, the individual pieces are adhered to a support member, and the adhesive film is attached. A semiconductor device can be obtained by joining a semiconductor element separated by a dicing process to a support member to produce a support member with a semiconductor element, and then performing a wire bonding process, a sealing process, and the like as necessary. Become.
しかし、上記個片貼付け方式の接着フィルムを用いるためには、接着フィルムを切り出して支持部材に接着する専用の組立装置が必要であることから、銀ペースト等の液状接着剤を使用する方法に比べて製造コストが高くなるという問題がある。 However, in order to use the adhesive film of the above-mentioned individual sticking method, a dedicated assembly device that cuts out the adhesive film and adheres it to the support member is necessary, so compared with a method using a liquid adhesive such as silver paste. Therefore, there is a problem that the manufacturing cost becomes high.
一方、後者のウエハ裏面貼付け方式の接着フィルムを用いて半導体装置を製造する場合、まず半導体ウエハの裏面に接着フィルムを貼付け、さらに接着フィルムの他方の面に半導体ウエハを固定するための粘着フィルムを貼り合わせ、その後上記ウエハからダイシングによって半導体素子を個片化し、個片化した接着フィルム付き半導体素子を粘着フィルムより剥離しそれを支持部材に接合し、その後の加熱、硬化、ワイヤボンド等の工程を経ることにより半導体装置が得られることとなる。このウエハ裏面貼付け方式の接着フィルムは、接着フィルム付き半導体素子を支持部材に接合するため、接着フィルムを個片化する装置を必要とせず、従来の銀ペースト用の組立装置をそのままあるいは熱盤を付加する等の装置の一部を改良することにより使用できる。そのため、接着フィルムを用いた組立方法の中で製造コストが比較的安く抑えられる方法として注目されている。 On the other hand, when manufacturing a semiconductor device using the latter wafer back surface bonding type adhesive film, an adhesive film is first attached to the back surface of the semiconductor wafer, and an adhesive film for fixing the semiconductor wafer to the other surface of the adhesive film. After bonding, the semiconductor element is separated from the wafer by dicing, and the separated semiconductor element with the adhesive film is peeled off from the adhesive film and bonded to the support member, and then the steps of heating, curing, wire bonding, etc. Through this process, a semiconductor device is obtained. This wafer back surface bonding type adhesive film joins the semiconductor element with the adhesive film to the support member, so it does not require an apparatus for separating the adhesive film into pieces, and the conventional silver paste assembling apparatus is used as it is or with a hot platen. It can be used by improving a part of the device such as adding. Therefore, it has been attracting attention as a method that can reduce the manufacturing cost relatively low among the assembling methods using the adhesive film.
このウエハ裏面貼付け方式の接着フィルムと共に用いられる粘着フィルムは、感圧型粘着フィルムと紫外線硬化型粘着フィルムに大別される。 The pressure-sensitive adhesive film used together with the wafer back surface bonding type adhesive film is roughly classified into a pressure-sensitive adhesive film and an ultraviolet curable adhesive film.
前者の感圧型粘着フィルムは通常、ポリ塩化ビニル系やポリオレフィン系のベースフィルムに粘着剤を塗布したものである。この粘着フィルムは、ダイシング工程における切断時にはダイシングソウの回転、あるいはレーザーの照射によって各素子が飛散しないような十分な粘着力が求められ、半導体用支持部材に接合する時には半導体素子を傷つけることなく基材層より剥離できる程度の低い粘着力が求められる。ところが、上記のような、相反する２つの性能を充分併せ持つ感圧型粘着フィルムがなかったことより、半導体素子のサイズや加工条件毎に粘着フィルムを切替える作業が行われていた。また素子のサイズや加工条件によって粘着力の制御が必要になることから粘着フィルムの在庫管理が複雑化している。さらに、近年、特にＣＰＵやメモリの大容量化が進んだ結果、半導体素子が大型化する傾向にあり、またＩＣカードあるいはメモリーカード等の製品にあっては使用されるメモリの薄型化が進んでいる。これらの半導体素子の大型化や薄型化に伴い、接着フィルムを剥離する際に素子が割れてしまう等の問題が生じている。 The former pressure-sensitive adhesive film is usually one obtained by applying an adhesive to a polyvinyl chloride or polyolefin base film. This adhesive film is required to have a sufficient adhesive strength so that each element does not scatter due to rotation of the dicing saw or laser irradiation when cutting in the dicing process, and when it is bonded to the semiconductor support member, it does not damage the semiconductor element. The adhesive strength is low enough to be peeled off from the material layer. However, since there was no pressure-sensitive adhesive film having sufficient two conflicting performances as described above, an operation of switching the adhesive film for each size and processing condition of the semiconductor element has been performed. Further, since the adhesive force needs to be controlled depending on the element size and processing conditions, the inventory management of the adhesive film is complicated. Furthermore, in recent years, especially as the capacity of CPUs and memories has increased, semiconductor elements tend to increase in size, and in products such as IC cards and memory cards, the memory used has become thinner. Yes. With the increase in size and thickness of these semiconductor elements, problems such as cracking of the elements when the adhesive film is peeled have arisen.
一方、後者の紫外線硬化型粘着フィルムはダイシング時には高粘着力を有するものの、接着フィルムを粘着フィルムより剥離する前に紫外線を照射することにより低粘着力になる。そのため、上記感圧型粘着フィルムが有する課題が改善されることより、広く採用されるに至っている。 On the other hand, the latter UV curable adhesive film has a high adhesive force during dicing, but has a low adhesive force when irradiated with ultraviolet rays before the adhesive film is peeled off from the adhesive film. Therefore, it has been widely adopted since the problems of the pressure-sensitive adhesive film are improved.
しかし、フィルム状接着剤を用いた上記のウエハ裏面貼付け方式においては、半導体ウエハのダイシングを行うまでに、フィルム状接着剤を半導体ウエハに貼付する工程とダイシングテープをフィルム状接着剤に貼付する工程との２つの貼付工程が必要である。そこで、このプロセスを簡略化するために、フィルム状接着剤とダイシングテープとを貼り合わせ、一枚で両方の機能を併せ持つダイシングテープ一体型接着フィルム（ダイボンドダイシングシート）が開発されている（例えば、特許文献１参照）。このようなダイシングテープ一体型接着フィルムは、例えば、剥離基材／接着フィルム／粘着フィルムの三層構造を有している。 However, in the wafer back surface pasting method using the film adhesive, the step of applying the film adhesive to the semiconductor wafer and the step of applying the dicing tape to the film adhesive before dicing the semiconductor wafer. And two pasting steps are required. Therefore, in order to simplify this process, a dicing tape-integrated adhesive film (die-bonded dicing sheet) having both functions combined in one sheet has been developed (for example, a die-bonded dicing sheet). Patent Document 1). Such a dicing tape-integrated adhesive film has, for example, a three-layer structure of release substrate / adhesive film / adhesive film.
また、このようなダイシングテープ一体型接着フィルムを、半導体素子を構成するウエハの形状にあらかじめ加工しておく方法（いわゆるプリカット加工）が知られている（例えば特許文献２参照）。かかるプリカット加工は、使用されるウエハの形状に合わせて樹脂層（接着フィルム及び粘着フィルム）を打ち抜き、ウエハを貼り付ける部分以外の樹脂層を剥離しておく方法である。 Further, there is known a method (so-called precut processing) in which such a dicing tape-integrated adhesive film is processed in advance into the shape of a wafer constituting a semiconductor element (see, for example, Patent Document 2). Such pre-cut processing is a method in which a resin layer (an adhesive film and an adhesive film) is punched in accordance with the shape of a wafer to be used, and a resin layer other than a portion to which the wafer is attached is peeled off.
プリカット加工が施されたダイシングテープ一体型接着フィルムは、例えば、剥離基材上に接着フィルムが積層され、その上にさらに粘着フィルムが、剥離基材側が粘着性を有する面となるようにして積層されている。なお、粘着フィルムは接着フィルムを覆い、且つ、接着フィルムの周囲で剥離基材に接するように積層されており、これにより、半導体ウエハのダイシングを行う際に、半導体ウエハの外周部のウエハリングに粘着フィルムを貼り付けてダイシングテープ一体型接着フィルムを固定することができるようになっている。 The dicing tape-integrated adhesive film that has been pre-cut is laminated, for example, by laminating an adhesive film on a release substrate, and further sticking an adhesive film on the release substrate so that the release substrate side has an adhesive surface. Has been. The adhesive film covers the adhesive film and is laminated so as to be in contact with the peeling substrate around the adhesive film, so that when dicing the semiconductor wafer, the wafer ring on the outer periphery of the semiconductor wafer is laminated. A dicing tape-integrated adhesive film can be fixed by attaching an adhesive film.
かかるプリカット加工を施す場合、上記のダイシングテープ一体型接着フィルムは一般的に、接着フィルムをウエハ形状に合わせてプリカット加工し、それと、粘着フィルムとなるダイシングテープとを貼り合わせた後、このダイシングテープに対してウエハリング形状に合わせたプリカット加工を施すか、又は、あらかじめウエハリング形状にプリカット加工したダイシングテープを、プリカット加工した接着フィルムと貼り合わせることによって作製される。 When performing such pre-cut processing, the above-mentioned dicing tape-integrated adhesive film is generally pre-cut by matching the adhesive film to the wafer shape, and this and the dicing tape that becomes the adhesive film are bonded together, and then the dicing tape The wafer is manufactured by applying a precut process that matches the wafer ring shape, or by bonding a dicing tape that has been precut to a wafer ring shape in advance with an adhesive film that has been precut.
半導体用接着フィルムは従来、接着フィルムを半導体用ウエハに貼り合せた後、ダイシングにより半導体素子を個片化し、接着フィルム付半導体素子を支持部材上に積層し、ワイヤをボンディングした後、封止材でモールドすることにより接着フィルムを完全に硬化させる。しかしながら、パッケージの種類によってはこのモールド工程を省略したり、また基板、ウエハ等の支持部材が薄くなることにより、高温で硬化をさせるとパッケージが反ったりすることで生産性、信頼性が低下することがある。 Conventionally, an adhesive film for a semiconductor is obtained by bonding an adhesive film to a semiconductor wafer, separating the semiconductor element by dicing, laminating the semiconductor element with an adhesive film on a support member, bonding a wire, and sealing material. The adhesive film is completely cured by molding with. However, depending on the type of package, this molding process may be omitted, or support members such as substrates and wafers may become thin, and the package may be warped when cured at high temperatures, thereby reducing productivity and reliability. Sometimes.
本発明は上記従来技術の有する課題を鑑みてなされたものであり、低温にて接着フィルム等の硬化がフルキュアまで進行する半導体用接着部材、半導体用接着剤組成物、半導体用接着フィルム、積層体及び半導体装置の製造方法を提供することを目的とする。 The present invention has been made in view of the above-described problems of the prior art, and an adhesive member for semiconductor, an adhesive composition for semiconductor, an adhesive film for semiconductor, and a laminate in which curing of an adhesive film or the like proceeds to a full cure at a low temperature. It is another object of the present invention to provide a method for manufacturing a semiconductor device.
本発明は以下の通りである。 The present invention is as follows.
（１）接着フィルムと基材層を備える接着部材であって、前記接着フィルムが、（Ａ）架橋性官能基を有する高分子量成分、（Ｂ）多官能エポキシ樹脂、（Ｃ）フェノール樹脂、（Ｄ）無機微粒子を含有し、且つ１２０℃２時間でフルキュアする接着剤組成物からなることを特徴とする半導体用接着部材。 (1) An adhesive member comprising an adhesive film and a base material layer, wherein the adhesive film is (A) a high molecular weight component having a crosslinkable functional group, (B) a polyfunctional epoxy resin, (C) a phenol resin, D) An adhesive member for a semiconductor comprising an adhesive composition containing inorganic fine particles and fully cured at 120 ° C. for 2 hours.
（２）熱硬化性樹脂及びフィラーを含有する接着剤組成物であって、前記熱硬化性樹脂が、（Ａ）架橋性官能基を有し、重量平均分子量が１０万〜１００万でありガラス転移温度が−５０℃〜５０℃である高分子量成分、（Ｂ）重量平均分子量５００以上の多官能エポキシ樹脂、及び、（Ｃ）フェノール樹脂を、質量比で、（Ａ）：（Ｂ）：（Ｃ）＝１５〜４０：５〜１５：３５〜５５の割合で含む半導体用接着剤組成物。 (2) An adhesive composition containing a thermosetting resin and a filler, wherein the thermosetting resin has (A) a crosslinkable functional group, and has a weight average molecular weight of 100,000 to 1,000,000. A high molecular weight component having a transition temperature of −50 ° C. to 50 ° C., (B) a polyfunctional epoxy resin having a weight average molecular weight of 500 or more, and (C) a phenol resin in a mass ratio of (A) :( B): (C) = 15-40: 5-15: 35-55 adhesive composition for semiconductors included.
（３）前記フィラーの配合割合が、前記熱硬化性樹脂１００質量部に対して３０〜１００質量部であり、平均粒径の異なる２種類以上のフィラーを含む上記（２）に記載の半導体用接着剤組成物。 (3) The compounding ratio of the filler is 30 to 100 parts by mass with respect to 100 parts by mass of the thermosetting resin, and includes two or more kinds of fillers having different average particle diameters. Adhesive composition.
（４）硬化前の８０℃における溶融粘度が２０００Ｐａ・ｓ以下である、上記（２）または（３）に記載の半導体用接着剤組成物。 (4) The adhesive composition for semiconductors according to (2) or (3) above, wherein the melt viscosity at 80 ° C. before curing is 2000 Pa · s or less.
（５）上記（２）〜（４）のいずれかに記載の半導体用接着剤組成物をフィルム状に成形してなる接着フィルムを備える、半導体用接着フィルム。 (5) An adhesive film for a semiconductor comprising an adhesive film formed by forming the adhesive composition for a semiconductor according to any one of (2) to (4) into a film.
（６）上記（５）に記載の半導体用接着フィルムと、粘着フィルムとからなる積層体。 (6) A laminate comprising the adhesive film for a semiconductor according to (5) above and an adhesive film.
（７）上記（６）に記載の積層体を、半導体用接着フィルム側の面から半導体ウエハに貼り付けて積層体付き半導体ウエハを得る貼り付け工程と、
前記積層体付き半導体ウエハを、前記接着フィルムと粘着フィルムとの界面までダイシングし、前記半導体ウエハを所定の大きさの半導体素子に切断するダイシング工程と、
前記積層体に高エネルギー線を照射して前記粘着フィルムの前記接着フィルムに対する粘着力を低下させた後、前記粘着フィルムから前記半導体素子を前記接着フィルムとともにピックアップし、接着フィルム付き半導体素子を得るピックアップ工程と、
前記接着フィルム付き半導体素子における前記半導体素子を、前記接着フィルムを介して被着体に接着する接着工程と、を含むことを特徴とする半導体装置の製造方法。
(7) An affixing step of adhering the laminate according to (6) above to a semiconductor wafer from the surface on the semiconductor adhesive film side to obtain a semiconductor wafer with a laminate,
Dicing the semiconductor wafer with the laminate to the interface between the adhesive film and the adhesive film, and cutting the semiconductor wafer into semiconductor elements of a predetermined size;
Pickup to obtain a semiconductor element with an adhesive film by irradiating the laminated body with high energy rays to reduce the adhesive force of the adhesive film to the adhesive film, and then picking up the semiconductor element together with the adhesive film from the adhesive film Process,
And a bonding step of bonding the semiconductor element in the semiconductor element with the adhesive film to an adherend through the adhesive film.
（８）前記被着体が、半導体素子搭載用の支持部材、又は、別の半導体素子であることを特徴とする上記（７）記載の半導体装置の製造方法。 (8) The method for manufacturing a semiconductor device according to (7), wherein the adherend is a support member for mounting a semiconductor element or another semiconductor element.
本発明によれば、低温硬化であるとともに接着強度や凹凸追従性に優れ、半導体装置の接続信頼性の向上を可能とする半導体用接着部材、半導体用接着剤組成物、積層体及び半導体装置の製造方法及び、これらを用いて得られる半導体装置を提供することができる。 According to the present invention, the adhesive member for semiconductor, the adhesive composition for semiconductor, the laminate, and the semiconductor device that are low-temperature cured and excellent in adhesion strength and unevenness followability, and can improve the connection reliability of the semiconductor device. A manufacturing method and a semiconductor device obtained by using these can be provided.
本発明の半導体用接着剤組成物は、熱硬化性樹脂及びフィラーを含有する接着剤組成物であって、前記熱硬化性樹脂が、（Ａ）架橋性官能基を有し、重量平均分子量が１０万〜１００万でありガラス転移温度が−５０℃〜５０℃である高分子量成分、（Ｂ）重量平均分子量５００以上の多官能エポキシ樹脂、及び、（Ｃ）フェノール樹脂を、質量比で、（Ａ）：（Ｂ）：（Ｃ）＝１５〜４０：５〜１５：３５〜５５の割合で含むことを特徴とする。 The adhesive composition for a semiconductor of the present invention is an adhesive composition containing a thermosetting resin and a filler, and the thermosetting resin has (A) a crosslinkable functional group and has a weight average molecular weight. 100,000 to 1,000,000 high molecular weight component having a glass transition temperature of −50 ° C. to 50 ° C., (B) a polyfunctional epoxy resin having a weight average molecular weight of 500 or more, and (C) a phenol resin in a mass ratio. (A) :( B) :( C) = 15-40: 5-15: 35-55.
また、本発明の半導体用接着部材は、接着フィルムと基材層を備える接着部材であって、前記接着フィルムが、（Ａ）架橋性官能基を有する高分子量成分、（Ｂ）多官能エポキシ樹脂、（Ｃ）フェノール樹脂、（Ｄ）無機微粒子を含有し、且つ１２０℃２時間でフルキュアする接着剤組成物からなることを特徴とする。 Moreover, the adhesive member for semiconductors of this invention is an adhesive member provided with an adhesive film and a base material layer, Comprising: The said adhesive film is a high molecular weight component which has (A) crosslinkable functional group, (B) Polyfunctional epoxy resin (C) It consists of an adhesive composition containing a phenol resin and (D) inorganic fine particles and being fully cured at 120 ° C. for 2 hours.
本発明において、「フルキュア」とは、ＤＳＣ等の装置を使用し、エポキシ由来の反応熱のピークが見られなくなる状態のことを示す。詳しくは後述する。 In the present invention, “full cure” refers to a state in which a peak of reaction heat derived from epoxy is not observed using an apparatus such as DSC. Details will be described later.
本発明の半導体用接着剤組成物は、熱硬化性樹脂及びフィラーを含有する接着剤組成物であって、フィラーの配合割合が、熱硬化性樹脂１００質量部に対して３０〜１００質量部であり、且つ、熱硬化性樹脂として、（Ａ）架橋性官能基を有し、重量平均分子量が１０万〜１００万でありガラス転移温度が−５０℃〜５０℃である高分子量成分、（Ｂ）重量平均分子量５００以上の多官能エポキシ樹脂、及び、（Ｃ）フェノール樹脂を質量比で、（Ａ）：（Ｂ）：（Ｃ）＝１５〜４０：５〜１５：３５〜５５の割合で含む。 The adhesive composition for semiconductor of the present invention is an adhesive composition containing a thermosetting resin and a filler, and the blending ratio of the filler is 30 to 100 parts by mass with respect to 100 parts by mass of the thermosetting resin. And (A) a high molecular weight component having a crosslinkable functional group, a weight average molecular weight of 100,000 to 1,000,000 and a glass transition temperature of −50 ° C. to 50 ° C. ) A polyfunctional epoxy resin having a weight average molecular weight of 500 or more and (C) a phenol resin in a mass ratio of (A) :( B) :( C) = 15-40: 5-15: 35-55 Including.
本発明の半導体用接着剤組成物は、熱硬化性樹脂及びフィラーを上記特定の割合で含有し、且つ、熱硬化性樹脂としての上記（Ａ）〜（Ｃ）成分を上記特定の割合で含有することにより、低溶融粘度でありながら優れた接着強度を発現することができる。このような本発明の半導体用接着剤組成物によれば、硬化前は良好な流動性により配線基板等の支持部材や半導体チップの凹凸を十分埋め込むことができ、硬化後は有機基板等の支持部材やシリコンチップ等に対して高い接着強度を発揮し得ることから、実装基板の接続信頼性の向上を図ることが可能となる。 The adhesive composition for a semiconductor of the present invention contains the thermosetting resin and the filler in the specific ratio, and contains the components (A) to (C) as the thermosetting resin in the specific ratio. By doing so, excellent adhesive strength can be expressed while having a low melt viscosity. According to such an adhesive composition for a semiconductor of the present invention, the support member such as a wiring board and the unevenness of the semiconductor chip can be sufficiently embedded with good fluidity before curing, and the organic substrate and the like are supported after curing. Since high adhesive strength can be exhibited with respect to a member, a silicon chip, etc., it becomes possible to improve the connection reliability of the mounting substrate.
また、本発明の半導体用接着剤組成物によれば、低温（具体的には、１２０℃２時間）での圧着実装のみで基板等の支持部材又は半導体チップの凹凸を十分埋め込むことができる。本発明の半導体用接着剤組成物は、上記フィラーとして、平均粒径が異なる２種以上のフィラーを含むことが好ましい。この場合、低溶融粘度であるとともに硬化後には優れた接着強度が得られるという特性を十分保持することが可能となる。 Moreover, according to the adhesive composition for a semiconductor of the present invention, it is possible to sufficiently bury the unevenness of a support member such as a substrate or a semiconductor chip only by pressure bonding at a low temperature (specifically, 120 ° C. for 2 hours). It is preferable that the adhesive composition for semiconductors of this invention contains 2 or more types of fillers from which an average particle diameter differs as said filler. In this case, it is possible to sufficiently retain the characteristics of having a low melt viscosity and an excellent adhesive strength after curing.
また、本発明の半導体用接着剤組成物は、上記の効果をより確実に得る観点から、平均一次粒径が０．１〜１．０μｍの範囲内にある第１のフィラー、及び、平均一次粒径が０．００５〜０．０３μｍの範囲内にある第２のフィラーを含むことが好ましい。詳細は後述する。 Moreover, the adhesive composition for semiconductors of this invention is the 1st filler in which the average primary particle diameter exists in the range of 0.1-1.0 micrometer, and an average primary from a viewpoint which acquires said effect more reliably. It is preferable that the 2nd filler which has a particle size in the range of 0.005-0.03 micrometer is included. Details will be described later.
また、本発明の半導体用接着剤組成物は、１２０℃２時間でフルキュアする熱重合性化合物（具体的には、エポキシ樹脂等）を更に含有することが好ましい。これにより、溶融粘度を下げることができ、なおかつ低温での硬化が可能となる。 Moreover, it is preferable that the adhesive composition for semiconductors of this invention further contains the thermopolymerizable compound (specifically epoxy resin etc.) which carries out a full cure at 120 degreeC for 2 hours. Thereby, melt viscosity can be lowered | hung and hardening at low temperature is attained.
なお、「１２０℃２時間でフルキュアする」とは、下記の条件でフルキュアすることであり、フルキュアの確認は、以下の様に行う。 “Full cure at 120 ° C. for 2 hours” means full cure under the following conditions, and confirmation of full cure is performed as follows.
まず、半導体用接着剤組成物をＰＥＴ基材（帝人デュポン（株）製のＡ５３）上に膜厚４０μｍとなるように塗工し、得られた基材付きサンプルフィルムを１２０℃で２０分間加熱乾燥し、その後、ＰＥＴ基材を引き剥がし、Ｂステージ状態のサンプルフィルムを得る。サンプルフィルムを１０ｍｇに切り出し、これを測定用試料とし、１２０℃で２時間硬化させ、ＤＳＣを使用し、エポキシ由来の反応熱のピークの有無でフルキュアか否かを判断する。 First, the adhesive composition for semiconductor was coated on a PET substrate (A53 manufactured by Teijin DuPont Co., Ltd.) so as to have a film thickness of 40 μm, and the obtained sample film with the substrate was heated at 120 ° C. for 20 minutes. After drying, the PET substrate is peeled off to obtain a B-stage sample film. A sample film is cut out to 10 mg, this is used as a measurement sample, cured at 120 ° C. for 2 hours, and DSC is used to determine whether or not the film is fully cured based on the presence or absence of an epoxy-derived reaction heat peak.
本発明の半導体用接着剤組成物は、硬化前の８０℃における溶融粘度が２０００Ｐａ・ｓ以下であることが好ましい。２０００Ｐａ・ｓを超える場合は、ウエハを有機基板に積層時に凹凸を十分に埋め込むことができない可能性がある。さらには、１０００Ｐａ・ｓ以下であることがより好ましい。 The adhesive composition for semiconductor of the present invention preferably has a melt viscosity at 80 ° C. before curing of 2000 Pa · s or less. When it exceeds 2000 Pa · s, there is a possibility that the unevenness cannot be sufficiently embedded when the wafer is laminated on the organic substrate. Further, it is more preferably 1000 Pa · s or less.
硬化前の８０℃における溶融粘度が２０００Ｐａ・ｓ以下とするには、１２０℃２時間でフルキュアする接着剤組成物を用いればよい。 In order for the melt viscosity at 80 ° C. before curing to be 2000 Pa · s or less, an adhesive composition that is fully cured at 120 ° C. for 2 hours may be used.
なお、硬化前の８０℃における溶融粘度は、下記のように測定する。上記のフルキュアの確認で用いたＢステージ状態のサンプルフィルムを、サイズ：径２５ｍｍ×厚み２００μｍに裁断し、これを測定用試料とし、これをズリ粘度計温度範囲：３５℃〜２００℃、昇温速度：５℃／ｍｉｎの条件でせん断方向への荷重をかけて測定したときの８０℃の値を測定する。 The melt viscosity at 80 ° C. before curing is measured as follows. The sample film in the B-stage state used for the above-mentioned full cure confirmation is cut into a size: diameter 25 mm × thickness 200 μm and used as a measurement sample, and this is a shear viscometer temperature range: 35 ° C. to 200 ° C. Speed: A value of 80 ° C. is measured when a load in the shearing direction is applied under the condition of 5 ° C./min.
また、本発明の半導体用接着フィルムは、上記本発明の半導体用接着剤組成物をフィルム状に成形してなる半導体用接着フィルムである。 Moreover, the adhesive film for semiconductors of this invention is an adhesive film for semiconductors formed by shape | molding the adhesive composition for semiconductors of the said invention in the shape of a film.
本発明の半導体用接着部材は、半導体用接着フィルムと基材層を備える接着部材であって、前記接着フィルムが、（Ａ）架橋性官能基を有する高分子量成分、（Ｂ）多官能エポキシ樹脂、（Ｃ）フェノール樹脂、（Ｄ）無機微粒子を含有し、且つ１２０℃２時間でフルキュアすることを特徴とする。 The adhesive member for a semiconductor of the present invention is an adhesive member comprising an adhesive film for a semiconductor and a base layer, wherein the adhesive film is (A) a high molecular weight component having a crosslinkable functional group, and (B) a polyfunctional epoxy resin. And (C) a phenol resin and (D) inorganic fine particles, and are fully cured at 120 ° C. for 2 hours.
そして、半導体素子と、該半導体素子を搭載する支持部材と、半導体素子及び支持部材間に設けられ、半導体素子及び支持部材を接着する前記接着フィルムと、を備えた半導体装置であって、前記接着フィルムが、上記の半導体用接着剤組成物の硬化物である半導体装置を提供することが可能である。 A semiconductor device comprising: a semiconductor element; a support member that mounts the semiconductor element; and the adhesive film that is provided between the semiconductor element and the support member and bonds the semiconductor element and the support member. It is possible to provide a semiconductor device in which the film is a cured product of the above adhesive composition for a semiconductor.
先ず、本発明の半導体用接着剤組成物について説明する。 First, the semiconductor adhesive composition of the present invention will be described.
本発明の半導体用接着剤組成物は、熱硬化性樹脂及びフィラーを含有する接着剤組成物であって、好ましくは、フィラーの配合割合が、熱硬化性樹脂１００質量部に対して３０〜１００質量部であり、且つ、熱硬化性樹脂として、（Ａ）架橋性官能基を有し、重量平均分子量が１０万〜１００万でありガラス転移温度が−５０℃〜５０℃である高分子量成分、（Ｂ）重量平均分子量５００以上の多官能エポキシ樹脂、及び、（Ｃ）フェノール樹脂を質量比で、（Ａ）：（Ｂ）：（Ｃ）＝１５〜４０：５〜１５：３５〜５５の割合で含む。 The adhesive composition for a semiconductor of the present invention is an adhesive composition containing a thermosetting resin and a filler, and preferably, the blending ratio of the filler is 30 to 100 with respect to 100 parts by mass of the thermosetting resin. A high molecular weight component having a mass part and (A) a crosslinkable functional group as a thermosetting resin, a weight average molecular weight of 100,000 to 1,000,000 and a glass transition temperature of -50 ° C to 50 ° C. (B) A polyfunctional epoxy resin having a weight average molecular weight of 500 or more and (C) a phenol resin by mass ratio, (A) :( B) :( C) = 15-40: 5-15: 35-55 Is included in the ratio.
上記高分子量成分（Ａ）としては、架橋性官能基としてエポキシ基、アルコール性またはフェノール性水酸基、カルボキシル基等を有する、ポリイミド樹脂、（メタ）アクリル樹脂、ウレタン樹脂、ポリフェニレンエーテル樹脂、ポリエーテルイミド樹脂、フェノキシ樹脂、変性ポリフェニレンエーテル樹脂等が挙げられる。ただし、これらに限定されるものではない。 The high molecular weight component (A) includes a polyimide resin, (meth) acrylic resin, urethane resin, polyphenylene ether resin, polyetherimide having an epoxy group, an alcoholic or phenolic hydroxyl group, a carboxyl group or the like as a crosslinkable functional group. Examples thereof include resins, phenoxy resins, and modified polyphenylene ether resins. However, it is not limited to these.
本発明で用いる高分子量成分（Ａ）としては、グリシジルアクリレート又はグリシジルメタクリレート等の官能性モノマーを含有するモノマーを重合して得た、重量平均分子量が１０万〜１００万であるエポキシ基含有（メタ）アクリル共重合体等が好ましい。更に、エポキシ基含有（メタ）アクリル共重合体としては、エポキシ基含有（メタ）アクリル酸エステル共重合体、エポキシ基含有アクリルゴム等を使用することができ、エポキシ基含有アクリルゴムがより好ましい。 As the high molecular weight component (A) used in the present invention, an epoxy group-containing compound (meta) having a weight average molecular weight of 100,000 to 1,000,000 obtained by polymerizing a monomer containing a functional monomer such as glycidyl acrylate or glycidyl methacrylate is used. ) Acrylic copolymer is preferred. Furthermore, as an epoxy group-containing (meth) acrylic copolymer, an epoxy group-containing (meth) acrylic acid ester copolymer, an epoxy group-containing acrylic rubber or the like can be used, and an epoxy group-containing acrylic rubber is more preferable.
エポキシ基含有アクリルゴムは、アクリル酸エステルを主成分とし、主として、ブチルアクリレートとアクリロニトリル等の共重合体や、エチルアクリレートとアクリロニトリル等の共重合体等からなるゴムである。 The epoxy group-containing acrylic rubber is a rubber mainly composed of an acrylate ester and mainly composed of a copolymer such as butyl acrylate and acrylonitrile, a copolymer such as ethyl acrylate and acrylonitrile, or the like.
高分子量成分（Ａ）のガラス転移温度Ｔｇは−５０℃〜５０℃の範囲内であることが必要である。高分子量成分のＴｇが５０℃を超えると、半導体用接着フィルムの柔軟性が低くなりすぎ、ウエハにラミネートする際の充分な密着性が得られにくくなる傾向にある。一方、高分子量成分のＴｇが−５０℃未満であると、半導体用接着フィルムの柔軟性が高くなりすぎるため、半導体ウエハダイシング時に半導体用接着フィルムが切断し難くなり、バリの発生によりダイシング性が悪化する場合がある。 The glass transition temperature Tg of the high molecular weight component (A) needs to be in the range of −50 ° C. to 50 ° C. When the Tg of the high molecular weight component exceeds 50 ° C., the flexibility of the adhesive film for a semiconductor becomes too low and sufficient adhesion when laminated on a wafer tends to be difficult to obtain. On the other hand, if the Tg of the high molecular weight component is less than −50 ° C., the flexibility of the adhesive film for semiconductor becomes too high, so that the adhesive film for semiconductor becomes difficult to cut at the time of semiconductor wafer dicing, and the dicing property is caused by the generation of burrs. It may get worse.
また、高分子量成分（Ａ）の重量平均分子量は、１０万〜１００万の範囲内であることが必要であるが、好ましくは２０万以上９０万以下、より好ましくは３０万以上８０万以下、特に好ましくは４０万以上６０万以下である。高分子量成分の重量平均分子量が１０万未満であると、接着剤樹脂組成物のフィルム成形性が悪化したり、半導体用接着フィルム（接着シート）の接着力や耐熱性の低下を引き起こしたりする場合があり、重量平均分子量が１００万を超えると未硬化の半導体用接着フィルムの流動性が低下する場合がある。 The weight average molecular weight of the high molecular weight component (A) needs to be in the range of 100,000 to 1,000,000, preferably 200,000 to 900,000, more preferably 300,000 to 800,000, Particularly preferably, it is 400,000 or more and 600,000 or less. When the weight average molecular weight of the high molecular weight component is less than 100,000, the film moldability of the adhesive resin composition is deteriorated, or the adhesive force or heat resistance of the adhesive film for semiconductor (adhesive sheet) is reduced. When the weight average molecular weight exceeds 1,000,000, the fluidity of the uncured semiconductor adhesive film may be lowered.
なお、本発明において、重量平均分子量とは、ゲルパーミュエーションクロマトグラフィー（ＧＰＣ）で測定し、標準ポリスチレン検量線を用いて換算した値を意味する。 In the present invention, the weight average molecular weight means a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve.
また、本発明で用いる高分子量成分（Ａ）は、半導体ウエハダイシング時に半導体用接着フィルムの切断が容易になり樹脂くずが発生し難くなる点、未硬化の半導体用接着フィルムの流動性が高くなる点、並びに、接着力及び耐熱性が高くなる点から、Ｔｇが−２０℃〜４０℃であり且つ重量平均分子量が１０万〜９０万であるものが好ましく、Ｔｇが−１０℃〜４０℃であり且つ重量平均分子量が２０万〜８０万であるものがより好ましい。 In addition, the high molecular weight component (A) used in the present invention is easy to cut the semiconductor adhesive film during semiconductor wafer dicing and hardly generates resin waste, and the fluidity of the uncured semiconductor adhesive film is increased. From the viewpoint of increasing the adhesive strength and heat resistance, it is preferable that Tg is −20 ° C. to 40 ° C. and the weight average molecular weight is 100,000 to 900,000, and Tg is −10 ° C. to 40 ° C. More preferred are those having a weight average molecular weight of 200,000 to 800,000.
重量平均分子量５００以上の多官能エポキシ樹脂（Ｂ）としては、硬化して接着作用を有するものであれば特に限定されないが、中でも１２０℃２時間で硬化が進行するものが好ましい。例えば、フェノールノボラック型エポキシ樹脂やクレゾールノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂等を使用することができる。 The polyfunctional epoxy resin (B) having a weight average molecular weight of 500 or more is not particularly limited as long as it is cured and has an adhesive action. Among them, a resin that cures at 120 ° C. for 2 hours is preferable. For example, a novolac type epoxy resin such as a phenol novolac type epoxy resin or a cresol novolac type epoxy resin can be used.
多官能であれば、グリシジルアミン型エポキシ樹脂、複素環含有エポキシ樹脂または脂環式エポキシ樹脂等、一般に知られているものを適用することができる。 If it is polyfunctional, generally known ones such as a glycidylamine type epoxy resin, a heterocyclic ring-containing epoxy resin or an alicyclic epoxy resin can be applied.
本発明の半導体用接着剤組成物は、多官能エポキシ樹脂（Ｂ）として、下記一般式（１）で表わされ、重量平均分子量８００以上であるエポキシ樹脂を含有することが好ましい。
（式（１）中、Ｒ１は水素原子、ハロゲン原子、直鎖状、分岐状若しくは環状のアルキル基、アラルキル基、アルケニル基、水酸基、又は、アリール基を示し、ｌは１〜３の整数を示し、ｍは２〜４の整数を示す。）
本発明の半導体用接着剤組成物は、重量平均分子量５００以上の多官能エポキシ樹脂を成分として含有するが、硬化物の耐熱性を更に向上させる観点から、一般式（１）で表され、重量平均分子量が８００〜３０００である多官能エポキシ樹脂が含有されることが特に好ましい。
(In the formula (1), R 1 represents a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, an aralkyl group, an alkenyl group, a hydroxyl group, or an aryl group, and l is an integer of 1 to 3. M represents an integer of 2 to 4.)
The adhesive composition for a semiconductor of the present invention contains a polyfunctional epoxy resin having a weight average molecular weight of 500 or more as a component, but is represented by the general formula (1) from the viewpoint of further improving the heat resistance of the cured product, and has a weight. It is particularly preferable that a polyfunctional epoxy resin having an average molecular weight of 800 to 3000 is contained.
また、上記一般式（１）で表され、重量平均分子量８００以上である多官能エポキシ樹脂は、８５℃、８５％ＲＨの恒温恒湿槽に４８時間投入後の吸水率が２質量％以下で、熱重量分析計（ＴＧＡ）で測定した３５０℃での加熱質量減少率（昇温速度：５℃／ｍｉｎ，雰囲気：窒素）が５質量％未満のものが好ましく使用できる。 Moreover, the polyfunctional epoxy resin represented by the general formula (1) and having a weight average molecular weight of 800 or more has a water absorption rate of 2% by mass or less after being put into a constant temperature and humidity chamber at 85 ° C. and 85% RH for 48 hours. Those having a heating mass reduction rate (heating rate: 5 ° C./min, atmosphere: nitrogen) at 350 ° C. measured by a thermogravimetric analyzer (TGA) of less than 5% by mass can be preferably used.
上記特性を満たす市販されているものとしては、東都化成（株）製のエポトートＹＤＦ−８１７０Ｃ等が好ましい。 As a commercially available product that satisfies the above characteristics, Epototo YDF-8170C manufactured by Toto Kasei Co., Ltd. is preferable.
また、本発明の半導体用接着剤組成物においては、Ｂステージ状態でのフィルムの可撓性を高める観点から、重量平均分子量５００以上の多官能エポキシ樹脂（Ｂ）以外のエポキシ樹脂として、重量平均分子量５００未満のエポキシ樹脂が更に含有されることが好ましく、重量平均分子量４００以下のエポキシ樹脂が更に含有されることがより好ましい。このようなエポキシ樹脂としては、ビスフェノールＡ型又はビスフェノールＦ型エポキシ樹脂といった二官能エポキシ樹脂等が好適に用いられる。 Moreover, in the adhesive composition for semiconductors of this invention, it is a weight average as epoxy resins other than the polyfunctional epoxy resin (B) of the weight average molecular weight 500 or more from a viewpoint of improving the flexibility of the film in a B stage state. It is preferable that an epoxy resin having a molecular weight of less than 500 is further contained, and it is more preferable that an epoxy resin having a weight average molecular weight of 400 or less is further contained. As such an epoxy resin, a bifunctional epoxy resin such as a bisphenol A type or a bisphenol F type epoxy resin is preferably used.
本発明の半導体用接着剤組成物の熱硬化性成分としてフェノール樹脂（Ｃ）を含有するが、フェノール樹脂（Ｃ）として、下記一般式（２）で表わされるフェノール樹脂を含有することが好ましい。
（式（２）中、Ｒ２は水素原子、ハロゲン原子、直鎖状、分岐状若しくは環状のアルキル基、アラルキル基、アルケニル基、水酸基、又は、アリール基を示し、ｑは１〜３の整数を示し、繰り返し単位の数を示すｐは１〜５０の範囲の整数を示す。）
また、上記一般式（２）で表されるフェノール樹脂は、８５℃、８５％ＲＨの恒温恒湿槽に４８時間投入後の吸水率が２質量％以下で、熱重量分析計（ＴＧＡ）で測定した３５０℃での加熱質量減少率（昇温速度：５℃／ｍｉｎ，雰囲気：窒素）が５質量％未満のものが好ましく使用できる。
(In the formula (2), R 2 represents a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, an aralkyl group, an alkenyl group, a hydroxyl group, or an aryl group, and q is an integer of 1 to 3. And p indicating the number of repeating units represents an integer in the range of 1 to 50.)
In addition, the phenol resin represented by the general formula (2) has a water absorption rate of 2% by mass or less after being put into a constant temperature and humidity chamber of 85 ° C. and 85% RH for 48 hours, and is measured by a thermogravimetric analyzer (TGA). The measured heating mass reduction rate at 350 ° C. (temperature increase rate: 5 ° C./min, atmosphere: nitrogen) is preferably less than 5% by mass.
上記特性を満たす市販されているものとしては、三井化学（株）製のミレックスＸＬＣ−ＬＬ、エアウォーター（株）製のＳＫレジンＨＥ２００Ｃ−１０等が挙げられる。 Examples of commercially available products that satisfy the above characteristics include Milex XLC-LL manufactured by Mitsui Chemicals, SK Resin HE200C-10 manufactured by Air Water, and the like.
本発明の半導体用接着剤組成物におけるエポキシ樹脂とフェノール樹脂との配合割合は、エポキシ当量と水酸基当量との当量比が０．７０／０．３０〜０．３０／０．７０となるように設定するのが好ましく、０．６５／０．３５〜０．３５／０．６５となるように設定するのがより好ましく、０．６０／０．４０〜０．４０／０．６０となるように設定するのがさらに好ましく、０．６０／０．４０〜０．５０／０．５０となるように設定するのが特に好ましい。エポキシ当量と水酸基当量との当量比が上記範囲外であると、半導体用接着フィルムの硬化性が劣る、又は、未硬化の半導体用接着フィルムの粘度が高くなり流動性に劣る傾向にある。 The compounding ratio of the epoxy resin and the phenol resin in the adhesive composition for semiconductor of the present invention is such that the equivalent ratio of epoxy equivalent and hydroxyl equivalent is 0.70 / 0.30 to 0.30 / 0.70. It is preferable to set the value, more preferably 0.65 / 0.35 to 0.35 / 0.65, and 0.60 / 0.40 to 0.40 / 0.60. Is more preferable, and it is particularly preferable to set it to be 0.60 / 0.40 to 0.50 / 0.50. When the equivalent ratio of the epoxy equivalent and the hydroxyl equivalent is outside the above range, the curability of the adhesive film for a semiconductor is inferior, or the viscosity of the uncured adhesive film for a semiconductor is increased and the fluidity tends to be inferior.
本発明の半導体用接着剤組成物にはフィラーが含有されており、これにより、Ｂステージ状態における半導体用接着フィルムのダイシング性の向上、半導体用接着フィルムの取扱い性の向上、熱伝導性の向上、溶融粘度の調整、チクソトロピック性の付与、接着力の向上を図ることが可能となっている。 The adhesive composition for semiconductors of the present invention contains a filler, thereby improving the dicing properties of the adhesive film for semiconductors in the B-stage state, improving the handleability of the adhesive film for semiconductors, and improving the thermal conductivity. It is possible to adjust melt viscosity, impart thixotropic properties, and improve adhesive strength.
本発明で用いるフィラーとしては、無機フィラーが好ましい。無機フィラーとしては特に制限は無く、例えば、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、ケイ酸カルシウム、ケイ酸マグネシウム、酸化カルシウム、酸化マグネシウム、アルミナ、窒化アルミニウム、ほう酸アルミウイスカ、窒化ホウ素、結晶性シリカ、非晶性シリカ、アンチモン酸化物等が使用できる。また、これらは単体あるいは２種類以上を混合して使用することもできる。 The filler used in the present invention is preferably an inorganic filler. The inorganic filler is not particularly limited, and examples thereof include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, alumina, aluminum nitride, aluminum borate whisker, and boron nitride. Crystalline silica, amorphous silica, antimony oxide and the like can be used. These can be used alone or in combination of two or more.
また、上記の無機フィラーのうち、熱伝導性向上の観点からは、アルミナ、窒化アルミニウム、窒化ホウ素、結晶性シリカ、非晶性シリカ等を用いることが好ましい。また、溶融粘度の調整やチクソトロピック性の付与の点からは、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、ケイ酸カルシウム、ケイ酸マグネシウム、酸化カルシウム、酸化マグネシウム、アルミナ、結晶性シリカ、非晶性シリカ等を用いることが好ましい。また、ダイシング性の向上の観点からは、アルミナ、シリカを用いることが好ましい。 Of the above inorganic fillers, alumina, aluminum nitride, boron nitride, crystalline silica, amorphous silica and the like are preferably used from the viewpoint of improving thermal conductivity. In terms of adjusting melt viscosity and imparting thixotropic properties, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, alumina, crystalline silica It is preferable to use amorphous silica or the like. From the viewpoint of improving dicing properties, it is preferable to use alumina or silica.
フィラーの含有割合は、半導体用接着フィルムのダイシング性が向上する点、半導体用接着フィルムの硬化後の貯蔵弾性率が１７０℃で２０〜１０００ＭＰａになりワイヤボンディング性が良好となる点から（詳細は後述する）、熱硬化性樹脂１００質量部に対して３０〜１００質量部であることが好ましく、さらには３５〜１００質量部であることが好ましい。 The content ratio of the filler is that the dicing property of the adhesive film for semiconductor is improved, and the storage elastic modulus after curing of the adhesive film for semiconductor is 20 to 1000 MPa at 170 ° C. and the wire bonding property is improved (for details, see It is preferably 30 to 100 parts by mass, more preferably 35 to 100 parts by mass with respect to 100 parts by mass of the thermosetting resin (described later).
また、フィラーの含有量が大きすぎると、フィルム成形性の悪化、未硬化の半導体用接着フィルムの流動性低下、接着剤の貯蔵弾性率の過剰な上昇、接着力の低下を引き起こしやすくなるため、フィラーの含有割合は、熱硬化性樹脂１００質量部に対して８０質量部以下であることがさらに好ましい。一方、フィラーの含有量が小さいと、半導体ウエハダイシング時に樹脂バリが発生しやすくなり、また接着力が低下する傾向にあるため、フィラーの含有割合は、熱硬化性樹脂１００質量部に対して３５質量部以上であることが好ましい。 In addition, if the filler content is too large, the film formability is deteriorated, the fluidity of the uncured semiconductor adhesive film is decreased, the storage modulus of the adhesive is excessively increased, and the adhesive force is decreased. The filler content is more preferably 80 parts by mass or less with respect to 100 parts by mass of the thermosetting resin. On the other hand, if the filler content is small, resin burrs are likely to occur during semiconductor wafer dicing, and the adhesive force tends to decrease. Therefore, the filler content is 35 parts per 100 parts by mass of the thermosetting resin. It is preferable that it is more than a mass part.
本発明の半導体用接着剤組成物は、上記フィラーとして、平均粒径が異なる２種以上のフィラーを含むことが好ましい。この場合、単一のフィラーを使用した場合に比べて、成膜前の原料混合物の粘度上昇若しくは低下を防止することが容易となり、良好な成膜性が得られやすくなるとともに、半導体用接着フィルムの硬化後には優れた接着強度を得られやすくなる。 It is preferable that the adhesive composition for semiconductors of this invention contains 2 or more types of fillers from which an average particle diameter differs as said filler. In this case, compared to the case where a single filler is used, it becomes easier to prevent an increase or decrease in the viscosity of the raw material mixture before film formation, and it becomes easier to obtain good film formability, and an adhesive film for semiconductors It becomes easy to obtain excellent adhesive strength after curing.
また、本発明の半導体用接着剤組成物は、上記の効果をより確実に得る観点から、平均一次粒径が０．１〜１．０μｍの範囲内にある第１のフィラー、及び、平均一次粒径が０．００５〜０．０３μｍの範囲内にある第２のフィラーを含むことが好ましい。さらには、ビーズミル処理によりシクロヘキサノンへ第１のフィラーを分散させた分散液をアセトン中へ滴下し、これを用いて測定した第１のフィラーの分散液中の平均一次粒径が０．１〜１．０μｍであることが好ましい。また、同様にして測定した第２のフィラーの分散液の平均一次粒径が０．０５〜０．３μｍであることが好ましい。 Moreover, the adhesive composition for semiconductors of this invention is the 1st filler in which the average primary particle diameter exists in the range of 0.1-1.0 micrometer, and an average primary from a viewpoint which acquires said effect more reliably. It is preferable that the 2nd filler which has a particle size in the range of 0.005-0.03 micrometer is included. Further, a dispersion in which the first filler is dispersed in cyclohexanone by bead mill treatment is dropped into acetone, and the average primary particle size in the dispersion of the first filler measured using this is 0.1 to 1. It is preferably 0.0 μm. Moreover, it is preferable that the average primary particle diameter of the dispersion liquid of the 2nd filler measured similarly is 0.05-0.3 micrometer.
平均一次粒径が０．１〜１．０μｍの範囲内にある第１のフィラーと平均一次粒径が０．００５〜０．０３μｍの範囲内にある第２のフィラーの比率は、１０：１〜２：１であることが好ましい。 The ratio of the first filler having an average primary particle size in the range of 0.1 to 1.0 μm and the second filler having an average primary particle size in the range of 0.005 to 0.03 μm is 10: 1. It is preferably ˜2: 1.
更に、本発明の半導体用接着剤組成物は、上記の効果をより確実に得る観点から、平均一次粒径が０．１〜１．０μｍの範囲内にあり且つ９９％以上の粒子が粒径０．１〜１．０μｍの範囲内に分布する第１のフィラー、及び、平均一次粒径が０．００５〜０．０３μｍの範囲内にあり且つ９９％以上の粒子が粒径０．００５〜０．１μｍの範囲内に分布する第２のフィラーを含むことが好ましい。 Furthermore, the adhesive composition for semiconductors of the present invention has an average primary particle size in the range of 0.1 to 1.0 μm and 99% or more of the particles have a particle size from the viewpoint of more reliably obtaining the above effect. The first filler distributed within the range of 0.1 to 1.0 μm and the average primary particle size within the range of 0.005 to 0.03 μm and 99% or more of the particles have a particle size of 0.005 to 0.005. It is preferable that the 2nd filler distributed in the range of 0.1 micrometer is included.
本発明の半導体用接着剤組成物における上記熱重合性化合物の含有割合は、熱硬化性樹脂１００質量部に対して３〜１０質量部であることが好ましい。含有割合が高すぎると未硬化半導体用接着フィルムのべたつきが高くなる傾向がある。 It is preferable that the content rate of the said thermopolymerizable compound in the adhesive composition for semiconductors of this invention is 3-10 mass parts with respect to 100 mass parts of thermosetting resins. If the content ratio is too high, the stickiness of the uncured semiconductor adhesive film tends to increase.
熱重合性成分を含む場合、更に硬化促進剤を添加してもよい。硬化促進剤としては、特に制限はなく、例えば、イミダゾール類等が挙げられる。具体的には、例えば、２−メチルイミダゾール、２−エチル−４−メチルイミダゾール、１−シアノエチル−２−フェニルイミダゾール、１−シアノエチル−２−フェニルイミダゾリウムトリメリテート等が挙げられ、これらは単独で又は二種類以上を組み合わせて使用することができる。また、これら硬化促進剤はマイクロカプセル型潜在性硬化剤を用いても良い。これら潜在性硬化剤は例えば旭化成エポキシ（株）製の商品名：ノバキュアＨＸ−３９４１等があげられる。 When a thermopolymerizable component is included, a curing accelerator may be further added. There is no restriction | limiting in particular as a hardening accelerator, For example, imidazole etc. are mentioned. Specific examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, and the like. Or in combination of two or more. These curing accelerators may be microcapsule type latent curing agents. Examples of these latent hardeners include trade name: NOVACURE HX-3941 manufactured by Asahi Kasei Epoxy Corporation.
この硬化促進剤の添加量は、熱重合性成分の総量１００質量部に対して１０質量部以下が好ましく、５質量部以下がより好ましい。この添加量が５質量部を超えると保存安定性が低下する傾向がある。 10 mass parts or less are preferable with respect to 100 mass parts of total amounts of a thermopolymerizable component, and, as for the addition amount of this hardening accelerator, 5 mass parts or less are more preferable. When this addition amount exceeds 5 parts by mass, the storage stability tends to decrease.
また、異種材料間の界面結合を良くするために、各種カップリング剤を添加することもできる。カップリング剤としては、例えば、シラン系、チタン系、アルミニウム系等が挙げられ、中でも効果が高い点でシラン系カップリング剤が好ましい。 Various coupling agents can also be added to improve interfacial bonding between different materials. Examples of the coupling agent include silane-based, titanium-based, and aluminum-based, and among them, a silane-based coupling agent is preferable because it is highly effective.
上記カップリング剤の使用量は、その効果や耐熱性及びコストの面から、半導体用接着剤組成物全量を基準として０．０１〜１０質量％とするのが好ましい。 It is preferable that the usage-amount of the said coupling agent shall be 0.01-10 mass% on the basis of the adhesive composition for semiconductors whole quantity from the surface of the effect, heat resistance, and cost.
更に、イオン性不純物を吸着して、吸湿時の絶縁信頼性を向上させるために、イオン捕捉剤を添加することもできる。このようなイオン捕捉剤としては特に制限はなく、例えば、トリアジンチオール化合物、ビスフェノール系還元剤等の、銅がイオン化して溶け出すのを防止するため銅害防止剤として知られる化合物、ジルコニウム系、アンチモンビスマス系マグネシウムアルミニウム化合物等の無機イオン吸着剤等が挙げられる。 Furthermore, an ion scavenger may be added to adsorb ionic impurities and improve insulation reliability during moisture absorption. Such an ion scavenger is not particularly limited. For example, a triazine thiol compound, a bisphenol-based reducing agent, etc., a compound known as a copper damage inhibitor to prevent copper from being ionized and dissolved, a zirconium-based compound, Examples include inorganic ion adsorbents such as antimony bismuth-based magnesium aluminum compounds.
上記イオン捕捉剤の使用量は、添加による効果や耐熱性、コスト等の点から、半導体用接着剤組成物全量を基準として０．１〜１０質量％が好ましい。 The amount of the ion scavenger used is preferably 0.1 to 10% by mass based on the total amount of the adhesive composition for semiconductors from the viewpoints of the effect of addition, heat resistance, cost, and the like.
また、本発明の半導体用接着剤組成物は、有機基板（例えば、銅張り積層板「Ｅ−６９７ＦＧ」（日立化成工業（株）製、４００μｍ厚）に回路形成し、「ＡＵＳ３０８」（太陽インキ（株）製）で被覆したもの）に対する硬化後の接着強度（ダイシェア強度）が、３．０ＭＰａ以上であることがより好ましい。 Moreover, the adhesive composition for semiconductors of the present invention forms a circuit on an organic substrate (for example, copper-clad laminate “E-697FG” (manufactured by Hitachi Chemical Co., Ltd., 400 μm thickness)), and “AUS308” (solar ink) It is more preferable that the adhesive strength (die shear strength) after curing with respect to (coated with Co., Ltd.) is 3.0 MPa or more.
本発明の半導体用接着部材は、例えば、以下の方法により作製することができる。先ず、上述の本発明の半導体用接着剤組成物を構成する各成分を有機溶媒中で混合、混練してワニスを調製し、このワニスの層を基材層上に形成させ、加熱により乾燥することにより半導体用接着部材を得ることができる。また、ワニス層の乾燥後に基材層を除去して、接着フィルムのみから構成される半導体用接着フィルムとしてもよい。上記の混合、混練は、通常の攪拌機、らいかい機、三本ロール、ボールミル等の分散機を適宜、組み合わせて行うことができる。上記の加熱乾燥の条件は、使用した溶媒が充分に揮散する条件であれば特に制限はないが、通常６０℃〜２００℃で、０．１〜９０分間加熱して行う。 The adhesive member for semiconductor of the present invention can be produced by the following method, for example. First, each component constituting the above-described adhesive composition for semiconductor of the present invention is mixed and kneaded in an organic solvent to prepare a varnish, and this varnish layer is formed on the base material layer and dried by heating. Thus, an adhesive member for a semiconductor can be obtained. Moreover, it is good also as an adhesive film for semiconductors comprised only from an adhesive film by removing a base material layer after drying a varnish layer. The above mixing and kneading can be carried out by appropriately combining dispersers such as ordinary stirrers, crackers, three rolls, and ball mills. The heating and drying conditions are not particularly limited as long as the used solvent is sufficiently volatilized, but the heating is usually performed at 60 to 200 ° C. for 0.1 to 90 minutes.
基材層としては、特に制限はなく、例えば、ポリエステルフィルム、ポリプロピレンフィルム、ポリエチレンテレフタレートフィルム、ポリイミドフィルム、ポリエーテルイミドフィルム、ポリエーテルナフタレートフィルム、メチルペンテンフィルム等が挙げられる。 There is no restriction | limiting in particular as a base material layer, For example, a polyester film, a polypropylene film, a polyethylene terephthalate film, a polyimide film, a polyetherimide film, a polyether naphthalate film, a methylpentene film etc. are mentioned.
上記ワニスの調製に用いる有機溶媒は、材料を均一に溶解、混練又は分散できるものであれば制限はなく、従来公知のものを使用することができる。このような溶剤としては、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒、ジメチルホルムアミド、ジメチルアセトアミド、Ｎメチルピロリドン、トルエン、キシレン等が挙げられる。乾燥速度が速く、価格が安い点でメチルエチルケトン、シクロヘキサノン等を使用することが好ましい。 The organic solvent used for the preparation of the varnish is not particularly limited as long as the material can be uniformly dissolved, kneaded or dispersed, and conventionally known ones can be used. Examples of such solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, dimethylformamide, dimethylacetamide, N methylpyrrolidone, toluene, xylene, and the like. It is preferable to use methyl ethyl ketone, cyclohexanone, etc. in terms of fast drying speed and low price.
接着フィルムの厚みは、基板の配線回路の凹凸を充填するため、１０〜２５０μｍであることが好ましい。この厚みが１０μｍよりも薄いと、凹凸の充填性が十分得られ難くなる他、応力緩和効果や接着性が低下する傾向があり、２５０μｍよりも厚いと経済的でなくなる上に、半導体装置の小型化の要求に応えることが困難となる傾向にある。更に、接着フィルムの厚みは、十分な接着性が得られるとともに半導体装置を薄型化できる点から、２０〜１００μｍがより好ましく、２０〜４０μｍが更に好ましい。 The thickness of the adhesive film is preferably 10 to 250 μm in order to fill the unevenness of the wiring circuit of the substrate. If the thickness is less than 10 μm, it is difficult to obtain sufficient filling of the unevenness, and the stress relaxation effect and adhesiveness tend to be reduced. If the thickness is more than 250 μm, it is not economical and the semiconductor device is small. It tends to be difficult to respond to the demands for making it easier. Furthermore, the thickness of the adhesive film is more preferably 20 to 100 μm, and still more preferably 20 to 40 μm from the viewpoint that sufficient adhesiveness can be obtained and the semiconductor device can be thinned.
ダイシング性が優れる点から、接着フィルムの硬化前（Ｂステージ状態）の３５℃における貯蔵弾性率は２００〜６０００ＭＰａであることが好ましい。更に、この貯蔵弾性率は、ダイシング性に優れ、かつ半導体ウエハとの密着性が優れる点で、２００〜３０００ＭＰａであることがより好ましい。 From the viewpoint of excellent dicing properties, the storage elastic modulus at 35 ° C. before curing of the adhesive film (B stage state) is preferably 200 to 6000 MPa. Furthermore, the storage elastic modulus is more preferably 200 to 3000 MPa in terms of excellent dicing properties and excellent adhesion to a semiconductor wafer.
また、良好なワイヤボンディング性を得る観点から、接着フィルムの硬化後（Ｃステージ状態）の１７０℃における貯蔵弾性率は、２０〜１０００ＭＰａであることが好ましい。 Further, from the viewpoint of obtaining good wire bonding properties, the storage elastic modulus at 170 ° C. after curing of the adhesive film (C stage state) is preferably 20 to 1000 MPa.
貯蔵弾性率の測定は、以下のようにして行う。 The storage elastic modulus is measured as follows.
フルキュアの確認で作製したＢステージ状態のサンプルフィルムを４ｍｍ×３０ｍｍのサイズに裁断したものを測定用試料とし、この試料を動的粘弾性測定装置（レオロジ社製、「ＤＶＥ−Ｖ４」）を用い、引張荷重をかけて、周波数１０Ｈｚ、昇温速度１０℃／分の条件で−５０℃から３００℃まで測定したときの温度３５℃及び１７０℃の値を測定する。 A B-stage sample film prepared by full cure confirmation was cut into a 4 mm x 30 mm size sample as a measurement sample, and this sample was used as a dynamic viscoelasticity measuring device ("DVE-V4" manufactured by Rheology). A value of 35 ° C. and 170 ° C. is measured when a tensile load is applied and measurement is performed from −50 ° C. to 300 ° C. under conditions of a frequency of 10 Hz and a heating rate of 10 ° C./min.
本発明の半導体用接着剤組成物及び半導体用接着フィルムは、それ自体で用いても構わないが、他の一実施態様として、本発明の半導体用接着剤組成物からなる接着フィルムを従来公知のダイシングテープ（粘着フィルム）上に設けてなるダイシング・ダイボンディング一体型接着シート（以下、「積層体」ともいう）として用いることもできる。この場合、半導体ウエハへのラミネート工程が一回で済むことから、作業を更に効率化することが可能となる。 The adhesive composition for semiconductors and the adhesive film for semiconductors of the present invention may be used as such, but as another embodiment, an adhesive film comprising the adhesive composition for semiconductors of the present invention is conventionally known. It can also be used as a dicing / die bonding integrated adhesive sheet (hereinafter also referred to as “laminate”) provided on a dicing tape (adhesive film). In this case, since the laminating process on the semiconductor wafer is performed only once, the work can be made more efficient.
本実施形態で使用するダイシングテープとしては、例えば、ポリテトラフルオロエチレンフィルム、ポリエチレンテレフタレートフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、ポリメチルペンテンフィルム、ポリイミドフィルム等のプラスチックフィルム等が挙げられる。また、これらのプラスチックフィルムには、必要に応じてプライマー塗布、ＵＶ処理、コロナ放電処理、研磨処理、エッチング処理等の表面処理を行ってもよい。 Examples of the dicing tape used in the present embodiment include a plastic film such as a polytetrafluoroethylene film, a polyethylene terephthalate film, a polyethylene film, a polypropylene film, a polymethylpentene film, and a polyimide film. In addition, these plastic films may be subjected to surface treatment such as primer application, UV treatment, corona discharge treatment, polishing treatment, and etching treatment as necessary.
ダイシングテープは粘着性を有することが好ましく、上述のプラスチックフィルムに粘着性を付与したものを用いてもよいし、上述のプラスチックフィルムの片面に粘着剤層を設けてもよい。この粘着剤層は、液状成分の比率、高分子量成分のＴｇを調整することによって得られる適度なタック強度を有する樹脂組成物を塗布乾燥することで形成可能である。 The dicing tape preferably has adhesiveness, and the above-mentioned plastic film provided with adhesiveness may be used, or an adhesive layer may be provided on one side of the above-mentioned plastic film. This pressure-sensitive adhesive layer can be formed by applying and drying a resin composition having an appropriate tack strength obtained by adjusting the ratio of the liquid component and the Tg of the high molecular weight component.
半導体用接着フィルムを半導体装置の製造に用いる場合、接着フィルムは、ダイシング時には半導体素子が飛散しない粘着力を有し、その後ピックアップ時にはダイシングテープから容易に剥離できることが好ましい。例えば、接着フィルムの粘着性が高すぎるとピックアップが困難になることがある。そのため、適宜、接着フィルムのタック強度を調節することが好ましい。その方法としては、接着フィルムの室温（２５℃）におけるフローを上昇させると粘着強度及びタック強度も上昇する傾向があり、一方、フローを低下させれば粘着強度及びタック強度も低下する傾向があることを利用すればよい。具体的には、フローを上昇させるには、例えば、接着剤組成物中の可塑剤の含有量の増加、粘着付与剤含有量の増加等の方法がある。逆にフローを低下させるには、前記化合物の含有量を減らせばよい。 When the semiconductor adhesive film is used for manufacturing a semiconductor device, it is preferable that the adhesive film has an adhesive force that prevents the semiconductor elements from scattering during dicing, and can be easily peeled off from the dicing tape during pickup. For example, picking up may be difficult if the adhesive film is too tacky. Therefore, it is preferable to appropriately adjust the tack strength of the adhesive film. As the method, if the flow of the adhesive film at room temperature (25 ° C.) is increased, the adhesive strength and tack strength tend to increase, while if the flow is decreased, the adhesive strength and tack strength tend to decrease. You can use that. Specifically, to increase the flow, for example, there are methods such as increasing the plasticizer content in the adhesive composition, increasing the tackifier content, and the like. Conversely, in order to reduce the flow, the content of the compound may be reduced.
前記可塑剤としては、例えば、単官能のアクリルモノマー、単官能エポキシ樹脂、液状エポキシ樹脂、アクリル系樹脂、エポキシ系樹脂のいわゆる希釈剤等が挙げられる。 Examples of the plasticizer include monofunctional acrylic monomers, monofunctional epoxy resins, liquid epoxy resins, acrylic resins, so-called diluents of epoxy resins, and the like.
ダイシングテープ上に接着フィルムを設ける方法としては、印刷のほか、予め作製した接着フィルムをダイシングテープ上にプレス、ホットロールラミネートする方法が挙げられるが、連続的に製造でき、効率が良い点でホットロールラミネートによって接着フィルムを設ける方法が好ましい。 As a method of providing an adhesive film on a dicing tape, in addition to printing, a method in which an adhesive film prepared in advance is pressed and hot-roll laminated on a dicing tape can be mentioned, but it can be manufactured continuously and is hot in terms of efficiency. A method of providing an adhesive film by roll lamination is preferable.
ダイシングテープの膜厚は、特に制限はなく、接着フィルムの膜厚や半導体用接着フィルムの用途によって適宜、当業者の知識に基づいて定められるものであるが、経済性がよく、フィルムの取扱い性が良い点で６０〜１５０μｍが好ましく、７０〜１３０μｍがより好ましい。 The film thickness of the dicing tape is not particularly limited, and is determined based on the knowledge of those skilled in the art as appropriate depending on the film thickness of the adhesive film and the application of the adhesive film for semiconductors. Is preferably 60 to 150 μm, more preferably 70 to 130 μm.
本発明は、半導体装置の製造方法にも関わる。詳しくは、本発明の半導体装置の製造方法は、本発明の積層体を、半導体用接着フィルム側の面から半導体ウエハに貼り付けて積層体付き半導体ウエハを得る貼り付け工程と、
前記積層体付き半導体ウエハを、前記接着フィルムと粘着フィルムとの界面までダイシングし、前記半導体ウエハを所定の大きさの半導体素子に切断するダイシング工程と、
前記積層体に高エネルギー線を照射して前記粘着フィルムの前記接着フィルムに対する粘着力を低下させた後、前記粘着フィルムから前記半導体素子を前記接着フィルムとともにピックアップし、接着フィルム付き半導体素子を得るピックアップ工程と、
前記接着フィルム付き半導体素子における前記半導体素子を、前記接着フィルムを介して被着体に接着する接着工程と、を含むことを特徴とする。
The present invention also relates to a method for manufacturing a semiconductor device. Specifically, in the method for manufacturing a semiconductor device of the present invention, the laminate of the present invention is attached to a semiconductor wafer from the surface on the semiconductor adhesive film side to obtain a semiconductor wafer with a laminate, and
Dicing the semiconductor wafer with the laminate to the interface between the adhesive film and the adhesive film, and cutting the semiconductor wafer into semiconductor elements of a predetermined size;
Pickup to obtain a semiconductor element with an adhesive film by irradiating the laminated body with high energy rays to reduce the adhesive force of the adhesive film to the adhesive film, and then picking up the semiconductor element together with the adhesive film from the adhesive film Process,
A bonding step of bonding the semiconductor element in the semiconductor element with the adhesive film to an adherend through the adhesive film.
また、本発明の半導体装置の製造方法においては、被着体が、半導体素子搭載用の支持部材、又は、別の半導体素子であることが好ましい。 Moreover, in the manufacturing method of the semiconductor device of this invention, it is preferable that a to-be-adhered body is a supporting member for mounting a semiconductor element, or another semiconductor element.
以下、本発明を実施例により詳細に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
（実施例１）
まず、重量平均分子量５００以上の多官能エポキシ樹脂（Ｂ）としてクレゾールノボラック型エポキシ樹脂（商品名：ＹＤＣＮ−７０３、東都化成（株）製、エポキシ当量：２２０）６０質量部、及び、（Ｂ）以外のエポキシ樹脂として、ビスフェノールＦ型エポキシ樹脂（商品名：ＹＤＦ−８１７０Ｃ、東都化成（株）製、重量平均分子量：３４０）１６０質量部、フェノール樹脂（Ｃ）として低吸水性フェノール樹脂（商品名：ＸＬＣ−ＬＬ、三井化学（株）製）２６０質量部に、シリカフィラー（商品名：ＳＣ２０５０、（株）アドマテックス製）２６０質量部、シクロヘキサノン１５００質量部を加えて撹拌混合した。
Example 1
First, as a polyfunctional epoxy resin (B) having a weight average molecular weight of 500 or more, cresol novolac type epoxy resin (trade name: YDCN-703, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: 220), 60 parts by mass, and (B) As an epoxy resin other than bisphenol F type epoxy resin (trade name: YDF-8170C, manufactured by Tohto Kasei Co., Ltd., weight average molecular weight: 340) 160 parts by mass, phenol resin (C) as a low water-absorbing phenol resin (trade name) : XLC-LL, manufactured by Mitsui Chemicals Co., Ltd.) 260 parts by mass, silica filler (trade name: SC2050, manufactured by Admatechs Co., Ltd.) 260 parts by mass and cyclohexanone 1500 parts by mass were added and mixed.
次に、このワニスに、カップリング剤としてγ−グリシドキシプロピルトリメトキシシラン（商品名：ＮＵＣ Ａ−１８９、日本ユニカー（株）製）０．５質量部、及び、γ−ウレイドプロピルトリエトキシシラン（商品名：ＮＣＵ Ａ−１１６０、日本ユニカー（株）製）４質量部を加えた。このワニスに、高分子量成分（Ａ）としてエポキシ基含有アクリル系共重合体（商品名：ＨＴＲ−８６０Ｐ−３、帝国化学産業（株）製、重量平均分子量：８０万）１１０質量部、及び、硬化促進剤として１−シアノエチル−２−フェニルイミダゾール（商品名：キュアゾール２ＰＺ−ＣＮ、四国化成工業（株）製）１．５質量部を加えて撹拌混合し、半導体用接着剤組成物ワニス１を調整した。 Next, 0.5 parts by mass of γ-glycidoxypropyltrimethoxysilane (trade name: NUC A-189, manufactured by Nihon Unicar Co., Ltd.) and γ-ureidopropyltriethoxy as a coupling agent were added to the varnish. 4 parts by mass of silane (trade name: NCU A-1160, manufactured by Nippon Unicar Co., Ltd.) was added. In this varnish, 110 parts by mass of an epoxy group-containing acrylic copolymer (trade name: HTR-860P-3, manufactured by Teikoku Chemical Industry Co., Ltd., weight average molecular weight: 800,000) as a high molecular weight component (A), and As a curing accelerator, 1 part of 1-cyanoethyl-2-phenylimidazole (trade name: Curezol 2PZ-CN, manufactured by Shikoku Kasei Kogyo Co., Ltd.) 1.5 parts by mass was added and mixed with stirring to obtain an adhesive composition varnish 1 for semiconductor. It was adjusted.
（実施例２）
実施例１の硬化促進剤に、キュアゾール２ＰＺ−ＣＮに代え、潜在性硬化剤（商品名：ノバキュアＨＸ−３９４１、旭化成エポキシ（株）製）を用いた以外は実施例１と同様の操作で半導体用接着剤組成物ワニス２を調整した。
(Example 2)
The semiconductor was operated in the same manner as in Example 1 except that a latent curing agent (trade name: NovaCure HX-3941, manufactured by Asahi Kasei Epoxy Co., Ltd.) was used instead of Curazole 2PZ-CN as the curing accelerator in Example 1. Adhesive composition varnish 2 was prepared.
（比較例１）
実施例１の、高分子量成分（Ａ）としてのエポキシ基含有アクリル系共重合体（商品名：ＨＴＲ−８６０Ｐ−３、帝国化学産業（株）製、重量平均分子量：８０万）を５００質量部添加した以外は実施例１と同様の操作で半導体用接着剤組成物ワニス３を調整した。
(Comparative Example 1)
500 parts by mass of the epoxy group-containing acrylic copolymer (trade name: HTR-860P-3, manufactured by Teikoku Chemical Industry Co., Ltd., weight average molecular weight: 800,000) as the high molecular weight component (A) of Example 1 A semiconductor adhesive composition varnish 3 was prepared in the same manner as in Example 1 except that it was added.
（比較例２）
重量平均分子量５００以上の多官能エポキシ樹脂（Ｂ）としてクレゾールノボラック型エポキシ樹脂（商品名：ＹＤＣＮ−７０３、東都化成（株）製、エポキシ当量：２２０）１２０質量部、及び、（Ｂ）以外のエポキシ樹脂として、ビスフェノールＦ型エポキシ樹脂（商品名：ＹＤＦ−８１７０Ｃ、東都化成（株）製、重量平均分子量：３４０）２１００質量部、フェノール樹脂（Ｃ）としてフェノール樹脂（商品名：ＸＬＣ−ＬＬ、ＤＩＣ（株）製）１５０質量部に、シリカフィラー（商品名：ＳＣ２０５０、（株）アドマテックス製）５００質量部シクロヘキサノン１５００質量部を加えて撹拌混合した。
(Comparative Example 2)
As a polyfunctional epoxy resin (B) having a weight average molecular weight of 500 or more, a cresol novolac type epoxy resin (trade name: YDCN-703, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: 220), 120 parts by mass, and (B) as the epoxy resin, bisphenol F type epoxy resin (trade name: YDF-8170C, manufactured by Tohto Kasei Co., Ltd., weight average molecular weight: 340) 2100 mass of a phenol resin (C) as a phenol resin (trade name: XLC-LL The silica filler (trade name: SC2050, manufactured by Admatechs Co., Ltd.) 500 parts by mass cyclohexanone 1500 parts by mass was added to 150 parts by mass of DIC Co., Ltd. and stirred and mixed.
次に、このワニスに、カップリング剤としてγ−グリシドキシプロピルトリメトキシシラン（商品名：ＮＵＣ Ａ−１８９、日本ユニカー（株）製）１．５質量部、及び、γ−ウレイドプロピルトリエトキシシラン（商品名：ＮＣＵ Ａ−１１６０、日本ユニカー（株）製）３質量部を加えた。このワニスに、高分子量成分（Ａ）としてエポキシ基含有アクリル系共重合体（商品名：ＨＴＲ−８６０Ｐ−３、帝国化学産業（株）製、重量平均分子量：８０万）１５０質量部、及び、硬化促進剤として１−シアノエチル−２−フェニルイミダゾール（商品名：キュアゾール２ＰＺ−ＣＮ、四国化成工業（株）製）０．５質量部を加えて撹拌混合し、半導体用接着剤組成物ワニス４を調整した。 Next, 1.5 parts by mass of γ-glycidoxypropyltrimethoxysilane (trade name: NUC A-189, manufactured by Nihon Unicar Co., Ltd.) as a coupling agent and γ-ureidopropyltriethoxy 3 parts by mass of silane (trade name: NCU A-1160, manufactured by Nippon Unicar Co., Ltd.) was added. In this varnish, 150 parts by mass of an epoxy group-containing acrylic copolymer (trade name: HTR-860P-3, manufactured by Teikoku Chemical Industry Co., Ltd., weight average molecular weight: 800,000) as a high molecular weight component (A), and As a curing accelerator, 0.5 part by mass of 1-cyanoethyl-2-phenylimidazole (trade name: Curezol 2PZ-CN, manufactured by Shikoku Kasei Kogyo Co., Ltd.) is added and mixed with stirring to obtain an adhesive composition varnish 4 for semiconductor. It was adjusted.
（比較例３）
重量平均分子量５００以上の多官能エポキシ樹脂（Ｂ）としてクレゾールノボラック型エポキシ樹脂（商品名：ＹＤＣＮ−７０３、東都化成（株）製、エポキシ当量：２２０）６０質量部、及び、フェノール樹脂（Ｃ）として低吸水性フェノール樹脂（商品名：ＸＬＣ−ＬＬ、三井化学（株）製、フェノールキシレングリコールジメチルエーテル縮合物）４０質量部に、シクロヘキサノン１５００質量部を加えて撹拌混合し、第１のワニスを調製した。
(Comparative Example 3)
As polyfunctional epoxy resin (B) having a weight average molecular weight of 500 or more, cresol novolac type epoxy resin (trade name: YDCN-703, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: 220), 60 parts by mass, and phenol resin (C) First, the first varnish is prepared by adding 1500 parts by mass of cyclohexanone to 40 parts by mass of a low water-absorbing phenol resin (trade name: XLC-LL, manufactured by Mitsui Chemicals, Inc., phenol xylene glycol dimethyl ether condensate). did.
次に、この第１のワニスに、カップリング剤としてγ−グリシドキシプロピルトリメトキシシラン（商品名：ＮＵＣ Ａ−１８９、日本ユニカー（株）製）１．５質量部、及び、γ−ウレイドプロピルトリエトキシシラン（商品名：ＮＣＵ Ａ−１１６０、日本ユニカー（株）製）３質量部を加え、更に無機物フィラーとしてシリカフィラー（商品名：Ｒ９７２Ｖ、日本アエロジル（株）製）３２質量部を加えて撹拌混合した後、ビーズミルにより分散処理を行うことで第２のワニスを調製した。次に、この第２のワニスに、高分子量成分（Ａ）としてエポキシ基含有アクリル系共重合体（商品名：ＨＴＲ−８６０Ｐ−３、帝国化学産業（株）製、重量平均分子量：３４０）２００質量部、及び、硬化促進剤として１−シアノエチル−２−フェニルイミダゾール（商品名：キュアゾール２ＰＺ−ＣＮ、四国化成工業（株）製）０．５質量部を加えて撹拌混合し、接着フィルム形成用ワニスを調整した。本ワニスを半導体用接着剤組成物ワニス５とする。 Next, 1.5 parts by mass of γ-glycidoxypropyltrimethoxysilane (trade name: NUC A-189, manufactured by Nippon Unicar Co., Ltd.) as a coupling agent, and γ-ureido as a coupling agent Add 3 parts by mass of propyltriethoxysilane (trade name: NCU A-1160, manufactured by Nippon Unicar Co., Ltd.), and add 32 parts by mass of silica filler (trade name: R972V, manufactured by Nippon Aerosil Co., Ltd.) as an inorganic filler. After stirring and mixing, a second varnish was prepared by performing a dispersion treatment with a bead mill. Next, an epoxy group-containing acrylic copolymer (trade name: HTR-860P-3, manufactured by Teikoku Chemical Industry Co., Ltd., weight average molecular weight: 340) 200 as a high molecular weight component (A) is added to the second varnish. For adding an adhesive film, 0.5 parts by mass of 1-cyanoethyl-2-phenylimidazole (trade name: Curesol 2PZ-CN, manufactured by Shikoku Kasei Kogyo Co., Ltd.) is added as a curing accelerator and stirred and mixed. The varnish was adjusted. This varnish is referred to as semiconductor adhesive composition varnish 5.
各種の測定は以下の通り行った。結果を表１に示した。 Various measurements were performed as follows. The results are shown in Table 1.
＜半導体用接着フィルムの作製＞
アプリケータ自動塗工機（テスター産業（株）製）を用いて、基材層としてのＰＥＴ基材（帝人デュポン（株）製 Ａ５３）上に、調製した実施例１〜２及び比較例１〜３の半導体用接着剤組成物ワニス１〜５をそれぞれ塗布し、ギャップを調整したアプリケータで塗工した。得られた半導体用接着フィルムを、オーブン中１２０℃／２０ｍｉｎの条件で加熱乾燥した。その後、ＰＥＴ基材を引き剥がすことで、膜厚４０μｍのＢステージ状態の半導体用接着フィルム１〜５を得た。
<Preparation of adhesive film for semiconductor>
Using an applicator automatic coating machine (manufactured by Tester Sangyo Co., Ltd.), Examples 1-2 and Comparative Examples 1-2 prepared on a PET base material (A53 manufactured by Teijin DuPont Co., Ltd.) as a base material layer. 3 was applied with an applicator having a gap adjusted, respectively. The obtained adhesive film for a semiconductor was heat-dried in an oven at 120 ° C./20 min. Then, the adhesive films 1-5 for semiconductors of a B stage state with a film thickness of 40 micrometers were obtained by peeling off a PET base material.
＜埋め込み率＞
半導体ウエハに上記で得られたＢステージ状態の半導体用接着フィルムをラミネートし、ダイシング装置上に固定して、１０ｍｍ／ｓｅｃの速度で５ｍｍ×５ｍｍにダイシングした後に、照度：１５〜１００ｍＷ／ｃｍ２で照射量２００ｍＪとなるように紫外線照射し、得られたチップを有機基板（ＰＳＲ−４０００、ＳＲ−ＡＵＳ５、０．２ｍｍｔ）に１２０℃−０．１ＭＰａ−５ｓｅｃの条件でダイボンディングし、ＳＡＴ（日立建機(株)製）にて埋め込まれた割合を面積比から算出した。
<Embedding rate>
After laminating the above-obtained B-stage semiconductor adhesive film on a semiconductor wafer, fixing it on a dicing machine and dicing to 5 mm × 5 mm at a speed of 10 mm / sec, the illuminance is 15 to 100 mW / cm 2. Then, the resulting chip was die-bonded to an organic substrate (PSR-4000, SR-AUS5, 0.2 mmt) under the conditions of 120 ° C.-0.1 MPa-5 sec, and SAT ( The ratio embedded in Hitachi Construction Machinery Co., Ltd.) was calculated from the area ratio.
＜ダイシェア強度＞
上記＜埋め込み率＞の条件にて得られたチップを４２アロイのリードフレーム上１２０℃−０．１ＭＰａ−５ｓｅｃの条件で圧着し、１２０℃１時間、１７０℃１時間の熱処理を加えた。この試験片を２５０℃の熱板上で２０ｓｅｃ保持した後、速度：５０μｍ／秒、高さ：５０μｍの測定条件でチップと有機基板との熱時接着力を「Ｓｅｒｉｅｓ４０００」（製品名、Ｄａｇｅ社製）により測定した。
<Die shear strength>
The chip obtained under the above conditions of <embedding ratio> was pressure-bonded on a 42 alloy lead frame under the conditions of 120 ° C.-0.1 MPa-5 sec and subjected to heat treatment at 120 ° C. for 1 hour and 170 ° C. for 1 hour. After holding this test piece on a hot plate at 250 ° C. for 20 seconds, the adhesive force during heating between the chip and the organic substrate under the measurement conditions of speed: 50 μm / second and height: 50 μm is “Series 4000” (product name, Dage). Manufactured).
＜フルキュアの確認（反応率）＞
＜半導体用接着フィルムの作製＞で得られたＢステージ状態の半導体用接着フィルムを１２０℃にて２時間硬化して得たサンプルフィルムをそれぞれ１０ｍｇ切り出し、ＤＳＣによりエポキシ樹脂の発熱量を測定した。このとき、硬化させていないフィルムの発熱量を１００とした時の発熱量の減少率から反応率を算出した。１００％は発熱量が１Ｊ／ｇ以下の状態を示す。
<Confirmation of full cure (reaction rate)>
10 mg each of the sample films obtained by curing the B-stage semiconductor adhesive film obtained in <Preparation of Semiconductor Adhesive Film> at 120 ° C. for 2 hours was measured for the calorific value of the epoxy resin by DSC. At this time, the reaction rate was calculated from the rate of decrease in the heat generation amount when the heat generation amount of the uncured film was taken as 100. 100% indicates a state where the calorific value is 1 J / g or less.
＜ピール強度＞
＜半導体用接着フィルムの作製＞で得られたＢステージ状態の半導体用接着フィルムを半導体ウエハにラミネートし、さらに２５ｍｍ×５０ｍｍに裁断したサンプルの、Ｔ字ピール強度を測定した。また、このサンプルに照度：１５〜１００ｍＷ／ｃｍ２で照射量２００ｍＪとなるように紫外線照射し、照射後の速度３００ｍｍ／ｓｅｃにてＴ字ピール強度を測定した。
<Peel strength>
The T-peel strength of the sample obtained by laminating the B-stage semiconductor adhesive film obtained in <Preparation of Semiconductor Adhesive Film> on a semiconductor wafer and further cutting to 25 mm × 50 mm was measured. In addition, this sample was irradiated with ultraviolet rays so that the irradiance was 15 to 100 mW / cm 2 and the irradiation amount was 200 mJ, and the T-peel strength was measured at a speed of 300 mm / sec after irradiation.
＜貯蔵弾性率＞
＜半導体用接着フィルムの作製＞で得られたＢステージ状態の半導体用接着フィルムを４ｍｍ×３０ｍｍのサイズに裁断したものを測定用試料とし、この試料を動的粘弾性測定装置（レオロジ社製、「ＤＶＥ−Ｖ４」）を用い、引張荷重をかけて、周波数１０Ｈｚ、昇温速度１０℃／分の条件で−５０℃から３００℃まで測定したときの温度３５℃及び１７０℃の値を測定した。
<Storage modulus>
The B-stage semiconductor adhesive film obtained in <Preparation of semiconductor adhesive film> was cut into a 4 mm × 30 mm size sample as a measurement sample, and this sample was used as a dynamic viscoelasticity measuring device (manufactured by Rheology, Using “DVE-V4”), the tensile load was applied, and the values at temperatures of 35 ° C. and 170 ° C. when measured from −50 ° C. to 300 ° C. under the conditions of a frequency of 10 Hz and a heating rate of 10 ° C./min were measured. .
＜溶融粘度＞
＜半導体用接着フィルムの作製＞で得られたＢステージ状態の半導体用接着フィルムをサンプルサイズ；径２５ｍｍ×厚み２００μｍに裁断したものを測定用試料とし、これをズリ粘度計温度範囲：３５℃〜２００℃，昇温速度：５℃／ｍｉｎの条件で測定したときの８０℃の値を測定した。
<Production of adhesive film for semiconductor> The B-stage semiconductor adhesive film obtained in <Production> was cut into a sample size; diameter 25 mm × thickness 200 μm as a measurement sample, and this was a shear viscometer temperature range: 35 ° C. to 35 ° C. A value of 80 ° C. when measured under the conditions of 200 ° C. and heating rate: 5 ° C./min was measured.
表１に示したように、実施例１、２の半導体用接着フィルムの反応率は１００％であり、１２０℃、２時間で硬化した（フルキュア）ことがわかる。また、比較例と比べ、実施例１，２は、埋め込み率、ダイシェア強度、ピール強度が優れていることがわかる。 As shown in Table 1, it can be seen that the reaction rates of the adhesive films for semiconductors of Examples 1 and 2 were 100% and were cured at 120 ° C. for 2 hours (full cure). Moreover, it turns out that Examples 1 and 2 are excellent in the embedding rate, die shear strength, and peel strength as compared with the comparative example.
本発明によれば、低温硬化であるとともに接着強度や凹凸追従性に優れ、半導体装置の接続信頼性の向上を可能とする半導体用接着部材、半導体用接着剤組成物、半導体用接着フィルム、積層体及び半導体装置の製造方法及び、これらを用いて得られる半導体装置を提供することができる。 According to the present invention, the adhesive member for semiconductor, the adhesive composition for semiconductor, the adhesive film for semiconductor, and the lamination, which are low-temperature curing and excellent in adhesion strength and unevenness followability and can improve the connection reliability of the semiconductor device. The manufacturing method of a body and a semiconductor device, and the semiconductor device obtained using these can be provided.
Claims (8)
前記接着フィルムが、（Ａ）架橋性官能基を有し、重量平均分子量が１０万〜１００万でありガラス転移温度が−５０℃〜５０℃である高分子量成分と、（Ｂ）重量平均分子量５００以上の多官能エポキシ樹脂と、（Ｃ）フェノール樹脂と、（Ｄ）フィラーとを含有した、１２０℃２時間でフルキュアする接着剤組成物からなり、
前記（Ｃ）フェノール樹脂が、下記一般式（２）で表わされるフェノール樹脂を含有し、
前記接着剤組成物が、前記（Ａ）、（Ｂ）、（Ｃ）成分を、質量比で（Ａ）：（Ｂ）：（Ｃ）＝１５〜４０：５〜１５：３５〜５５の割合で含む半導体用接着部材。
（式（２）中、Ｒ ２ は水素原子、ハロゲン原子、直鎖状、分岐状又は環状のアルキル基、アラルキル基、アルケニル基、水酸基、及び、アリール基からなる群から選択されるいずれかの基を示し、ｑは１〜３の整数を示し、ｐは１〜５０の範囲の整数を示す。） An adhesive member comprising an adhesive film and a base material layer,
The adhesive film, (A) have a crosslinkable functional group, and the weight average molecular weight of 100000-1000000 a and the glass transition temperature of Ru -50 ° C. to 50 ° C. der high molecular weight component, (B) a weight average a molecular weight of 500 or higher polyfunctional epoxy resin, (C) and the phenol resin, containing the (D) a filler, Ri Do from the adhesive composition Furukyua at 1 20 ° C. 2 hours,
The (C) phenol resin contains a phenol resin represented by the following general formula (2),
The said adhesive composition is the ratio of (A) :( B) :( C) = 15-40: 5-15: 35-55 by mass ratio with said (A), (B), (C) component. Adhesive member for semiconductors contained in
(In the formula (2), R 2 is any one selected from the group consisting of a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, an aralkyl group, an alkenyl group, a hydroxyl group, and an aryl group. And q represents an integer of 1 to 3, and p represents an integer in the range of 1 to 50.)
前記熱硬化性樹脂が、（Ａ）架橋性官能基を有し、重量平均分子量が１０万〜１００万でありガラス転移温度が−５０℃〜５０℃である高分子量成分と、（Ｂ）重量平均分子量５００以上の多官能エポキシ樹脂と、（Ｃ）フェノール樹脂とを、質量比で、（Ａ）：（Ｂ）：（Ｃ）＝１５〜４０：５〜１５：３５〜５５の割合で含み、
前記（Ｃ）フェノール樹脂が、下記一般式（２）で表わされるフェノール樹脂を含有する半導体用接着剤組成物。
（式（２）中、Ｒ ２ は水素原子、ハロゲン原子、直鎖状、分岐状又は環状のアルキル基、アラルキル基、アルケニル基、水酸基、及び、アリール基からなる群から選択されるいずれかの基を示し、ｑは１〜３の整数を示し、ｐは１〜５０の範囲の整数を示す。） An adhesive composition containing a thermosetting resin and (D) filler,
The thermosetting resin has (A) a high molecular weight component having a crosslinkable functional group, a weight average molecular weight of 100,000 to 1,000,000 and a glass transition temperature of −50 ° C. to 50 ° C., and (B) weight. A polyfunctional epoxy resin having an average molecular weight of 500 or more and ( C) a phenol resin are contained in a mass ratio of (A) :( B) :( C) = 15-40: 5-15: 35-55. See
(C) The adhesive composition for semiconductors in which the phenol resin contains a phenol resin represented by the following general formula (2) .
(In the formula (2), R 2 is any one selected from the group consisting of a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, an aralkyl group, an alkenyl group, a hydroxyl group, and an aryl group. And q represents an integer of 1 to 3, and p represents an integer in the range of 1 to 50.)
前記積層体付き半導体ウエハを、前記半導体用接着フィルムと前記粘着フィルムとの界面までダイシングし、前記半導体ウエハを所定の大きさの半導体素子に切断するダイシング工程と、
前記積層体に高エネルギー線を照射して前記粘着フィルムの前記半導体用接着フィルムに対する粘着力を低下させた後、前記粘着フィルムから前記半導体素子を前記半導体用接着フィルムとともにピックアップし、接着フィルム付き半導体素子を得るピックアップ工程と、
前記接着フィルム付き半導体素子における前記半導体素子を、前記半導体用接着フィルムを介して被着体に接着する接着工程と、を含む半導体装置の製造方法。 A pasting step of a laminate to obtain a semiconductor wafer with laminate stuck to the semiconductor wafer from the surface of the adhesive film for semiconductor side of claim 6,
A dicing step of the semiconductor wafer with laminate, dicing to the interface between the adhesive film and the adhesive film for semiconductor, cutting the semiconductor wafer into semiconductor devices having a predetermined size,
After said the laminate is irradiated with high energy radiation to lower the adhesive strength to the adhesive film for a semiconductor of the adhesive film, to pick up the semiconductor element with the adhesive film for the semiconductor from the adhesive film, the semiconductor film adhesive A pick-up process for obtaining an element;
Production method of the adhesive film-attached semiconductor wherein the device semiconductor device, the bonding step of bonding to the adherend via the adhesive film for semiconductor, a including semiconductors devices.
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