JP2008147641A - Adhesive sheet for semiconductor, and adhesive sheet for dicing integrated semiconductor - Google Patents
Adhesive sheet for semiconductor, and adhesive sheet for dicing integrated semiconductor Download PDFInfo
- Publication number
- JP2008147641A JP2008147641A JP2007294705A JP2007294705A JP2008147641A JP 2008147641 A JP2008147641 A JP 2008147641A JP 2007294705 A JP2007294705 A JP 2007294705A JP 2007294705 A JP2007294705 A JP 2007294705A JP 2008147641 A JP2008147641 A JP 2008147641A
- Authority
- JP
- Japan
- Prior art keywords
- adhesive sheet
- semiconductor
- molecular weight
- elastic modulus
- mpa
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 140
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 140
- 239000004065 semiconductor Substances 0.000 title claims abstract description 78
- 238000005259 measurement Methods 0.000 claims abstract description 26
- 239000000945 filler Substances 0.000 claims description 19
- 229920001187 thermosetting polymer Polymers 0.000 claims description 13
- 238000010030 laminating Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 abstract description 11
- 239000000470 constituent Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- -1 661 Chemical compound 0.000 description 16
- 239000003822 epoxy resin Substances 0.000 description 16
- 229920000647 polyepoxide Polymers 0.000 description 16
- 238000005520 cutting process Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000005011 phenolic resin Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000002966 varnish Substances 0.000 description 8
- 229920000800 acrylic rubber Polymers 0.000 description 7
- 125000003700 epoxy group Chemical group 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 229920000058 polyacrylate Polymers 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229920006243 acrylic copolymer Polymers 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 229910002026 crystalline silica Inorganic materials 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-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
- 230000000052 comparative effect Effects 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000000518 rheometry Methods 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 230000008646 thermal stress Effects 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- 238000000576 coating method Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 238000005304 joining Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000011417 postcuring Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 2
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002460 imidazoles Chemical class 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
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000306 polymethylpentene Polymers 0.000 description 2
- 239000011116 polymethylpentene Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- CLYUOMVYYFJUBR-UHFFFAOYSA-N 2-[methyl-bis[2-(2-methylprop-2-enoyloxy)ethoxy]silyl]oxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCO[Si](C)(OCCOC(=O)C(C)=C)OCCOC(=O)C(C)=C CLYUOMVYYFJUBR-UHFFFAOYSA-N 0.000 description 1
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- HOZMLTCHTRHKRK-UHFFFAOYSA-N 2-methyl-1-silylprop-2-en-1-one Chemical class CC(=C)C([SiH3])=O HOZMLTCHTRHKRK-UHFFFAOYSA-N 0.000 description 1
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- IHDMWJVVHWITIM-UHFFFAOYSA-N 3-(4,5-dihydroimidazol-1-yl)propyl-trimethoxysilane Chemical compound CO[Si](OC)(OC)CCCN1CCN=C1 IHDMWJVVHWITIM-UHFFFAOYSA-N 0.000 description 1
- GHWPPBZDJQYMDI-UHFFFAOYSA-N 3-[3-[benzyl(ethenyl)amino]propoxy-dimethoxysilyl]propan-1-amine Chemical compound NCCC[Si](OC)(OC)OCCCN(C=C)CC1=CC=CC=C1 GHWPPBZDJQYMDI-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- PJURIXUDYDHOMA-UHFFFAOYSA-N 3-[tris[2-(2-methoxyethoxy)ethoxy]silyl]propan-1-amine Chemical compound COCCOCCO[Si](CCCN)(OCCOCCOC)OCCOCCOC PJURIXUDYDHOMA-UHFFFAOYSA-N 0.000 description 1
- KEZMLECYELSZDC-UHFFFAOYSA-N 3-chloropropyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(OCC)CCCCl KEZMLECYELSZDC-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
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- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical compound CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 description 1
- VGIURMCNTDVGJM-UHFFFAOYSA-N 4-triethoxysilylbutanenitrile Chemical compound CCO[Si](OCC)(OCC)CCCC#N VGIURMCNTDVGJM-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 150000002605 large molecules Chemical class 0.000 description 1
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Landscapes
- Adhesive Tapes (AREA)
- Die Bonding (AREA)
- Dicing (AREA)
Abstract
Description
本発明は、半導体用接着シート及びダイシング一体型半導体用接着シートに関する。 The present invention relates to a semiconductor adhesive sheet and a dicing integrated semiconductor adhesive sheet.
従来、半導体素子と半導体素子搭載用支持部材の接合には銀ペーストが主に使用されていた。しかし、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いる。こうした要求に対して、銀ペーストでは、はみ出しや半導体素子の傾きに起因するワイヤボンディング時における不具合の発生、接合部の厚さの制御困難性、および接合部におけるボイド発生などにより前記要求に対処しきれなくなってきている。そのため、前記要求に対処するべく、近年、シート状の接着剤、即ち接着シートが使用されるようになってきた。 Conventionally, a silver paste has been mainly used for joining a semiconductor element and a semiconductor element mounting support member. However, with the recent miniaturization and high performance of semiconductor elements, the support members used are required to be small and fine. In response to these demands, silver paste addresses such demands by the occurrence of defects during wire bonding due to protrusions and inclination of semiconductor elements, difficulty in controlling the thickness of the joint, and the occurrence of voids in the joint. I can't understand. Therefore, in order to cope with the above demand, in recent years, a sheet-like adhesive, that is, an adhesive sheet has been used.
この接着シートは、個片貼付け方式あるいはウェハ裏面貼付け方式において使用されているが、前者の個片貼付け方式の接着シートを用いて半導体装置を製造する場合、リール状の接着シート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前記接着シート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、封止工程などを経ることによって半導体装置が得られることとなる。しかし、前記個片貼付け方式の接着シートを用いるためには、接着シート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った。 This adhesive sheet is used in an individual sticking method or a wafer back surface sticking method. When manufacturing a semiconductor device using the former individual sticking method adhesive sheet, the reel-like adhesive sheet is cut or punched. After cutting out into individual pieces, the individual pieces are bonded to a supporting member, and the semiconductor element separated by the dicing process is joined to the supporting member with the adhesive sheet to produce a supporting member with a semiconductor element, and then as necessary. A semiconductor device is obtained through a wire bonding process, a sealing process, and the like. However, in order to use the adhesive sheet of the piece pasting method, a dedicated assembly device that cuts out the adhesive sheet and adheres it to the support member is necessary, so that the manufacturing cost is higher than the method using silver paste. There was a problem of becoming.
一方、後者のウェハ裏面貼付け方式の接着シートを用いて半導体装置を製造する場合、まず半導体ウェハの裏面に接着シートを貼付け、さらに接着シートの他面にダイシングテープを貼り合わせ、その後前記ウェハからダイシングによって半導体素子を個片化し、個片化した接着シート付き半導体素子をピックアップしそれを支持部材に接合し、その後の加熱、硬化、ワイヤボンドなど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。このウェハ裏面貼付け方式の接着シートは、接着シート付き半導体素子を支持部材に接合するため接着シート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など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、接着シート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 sheet, the adhesive sheet is first bonded to the back surface of the semiconductor wafer, and then a dicing tape is bonded to the other surface of the adhesive sheet, and then dicing is performed from the wafer. A semiconductor device can be obtained by separating the semiconductor element into individual pieces, picking up the separated semiconductor element with an adhesive sheet, joining it to a support member, and subsequent processes such as heating, curing, and wire bonding. Become. This wafer back surface bonding type adhesive sheet does not require an apparatus for separating the adhesive sheet to join the semiconductor element with the adhesive sheet to the supporting member, and the conventional assembly apparatus for silver paste is added as it is or a heating plate is added. It can be used by improving a part of the apparatus such as. Therefore, it has been attracting attention as a method in which the manufacturing cost can be kept relatively low among the assembling methods using the adhesive sheet.
ウェハ裏面貼り付け方式の接着シートを用いる方法にあっては、ウェハのダイシング工程時に接着シートも切断することが必要であるが、これには（ｉ）従来のダイヤモンドブレードを用いて切断する接触型の切断方法に加え、（ｉｉ）ウェハにレーザを照射することによりウェハ内部に選択的に改質部を形成し、その後エキスパンドすることにより改質部に沿ってウェハを切断する時に同時に接着シートを切断する方法、または（ｉｉｉ）切断されたウェハに接着シートを貼り付け、その後エキスパンドすることによりウェハ切断ラインに沿って接着シートを切断する方法（例えば、特許文献１参照）がある。 In the method using the wafer back surface bonding type adhesive sheet, it is necessary to cut the adhesive sheet at the time of the wafer dicing process. For this purpose, (i) a contact type in which cutting is performed using a conventional diamond blade. In addition to the cutting method of (ii), (ii) by selectively irradiating the wafer with a laser, a modified portion is selectively formed inside the wafer, and then expanding to cut the wafer along the modified portion at the same time, There is a method of cutting, or (iii) a method of cutting an adhesive sheet along a wafer cutting line by attaching an adhesive sheet to a cut wafer and then expanding the wafer (see, for example, Patent Document 1).
しかし、上記（ｉ）〜（ｉｉｉ）の方法はいずれも、無機物で固いウェハと有機物で柔らかい接着シートの固さの異なる２種類の材料を同じ工程で切断する。この場合、エキスパンドによる接着シートの個片化が困難となる。そこで、エキスパンドによる接着シートの個片化を容易にするためには、有機物である接着シートに無機フィラを添加することが有効である。 However, in any of the above methods (i) to (iii), two types of materials having different hardnesses of a hard wafer made of an inorganic material and a soft adhesive sheet made of an organic material are cut in the same step. In this case, it is difficult to divide the adhesive sheet by the expand. Therefore, in order to facilitate the separation of the adhesive sheet by the expand, it is effective to add an inorganic filler to the organic adhesive sheet.
一方、半導体素子をはじめとする各種電子部品を搭載した実装基板として最も重要な特性の一つとして信頼性がある。その中でも、熱疲労に対する接続信頼性は実装基板を用いた機器の信頼性に直接関係するため非常に重要な項目である。この接続信頼性を低下させる原因として、熱膨張係数の異なる各種材料を用いていることから生じる熱応力が挙げられる。具体的には、半導体素子の熱膨張係数が約４ｐｐｍ／℃と小さいのに対し、電子部品を実装する配線基板の熱膨張係数が１５ｐｐｍ／℃以上と大きいことから熱衝撃に対して熱ひずみが発生し、その熱ひずみによって熱応力が発生し、この熱応力が接続信頼性を低下させる。このため、この応力を緩和させることが接着シートとしての課題である。 On the other hand, reliability is one of the most important characteristics as a mounting board on which various electronic components such as semiconductor elements are mounted. Among them, the connection reliability against thermal fatigue is a very important item because it is directly related to the reliability of the equipment using the mounting substrate. As a cause of lowering the connection reliability, there is a thermal stress generated by using various materials having different thermal expansion coefficients. Specifically, the thermal expansion coefficient of the semiconductor element is as small as about 4 ppm / ° C., whereas the thermal expansion coefficient of the wiring board on which the electronic component is mounted is as large as 15 ppm / ° C. And thermal stress is generated by the thermal strain, and this thermal stress lowers the connection reliability. For this reason, it is a subject as an adhesive sheet to relieve this stress.
また上記のような配線基板は配線による凹凸を一般に有しており、この配線基板における凹凸を埋め込めることも、接続信頼性の観点から、接着シートには必要である。上記の応力緩和性や基板凹凸埋込性の点から、半導体用接着シートは、硬化後の弾性率がある程度低くなるものが望ましい。 Moreover, the wiring board as described above generally has unevenness due to wiring, and from the viewpoint of connection reliability, it is necessary for the adhesive sheet to be able to bury the unevenness in the wiring board. From the viewpoint of the above-described stress relaxation property and substrate unevenness embedding property, it is desirable that the adhesive sheet for a semiconductor has a somewhat low elastic modulus after curing.
ところが、エキスパンドによる接着シートの切断性向上のため上記のように接着シートに無機フィラを添加すると、一般的に接着シートが硬化後に高弾性化することが分かっており、半導体パッケージの信頼性と接着シートの切断性の両立が課題となっている。
本発明は、特に、エキスパンドによる個片化が可能であり、且つモールド時に基板凹凸への埋込性が優れる半導体用接着シート及びダイシング一体型半導体用接着シートを提供することを目的とする。 In particular, an object of the present invention is to provide a semiconductor adhesive sheet and a dicing integrated semiconductor adhesive sheet that can be singulated by expanding and have excellent embeddability in substrate irregularities during molding.
本発明者らは、上記のように、従来の接着シートでは、エキスパンドによる接着シートの個片化を可能にするため、Ｂステージ状態での９００Ｈｚにおける動的粘弾性測定による弾性率が高くなり、硬化後の弾性率も高くなってしまうことを見出した。そして、本発明者らは、さらに鋭意研究を重ねた結果、以下の発明により、Ｂステージ状態での９００Ｈｚにおける動的粘弾性測定による弾性率を高く保ち、且つ硬化後の弾性率を低くできることを見出した。 As described above, in the conventional adhesive sheet, in order to enable individualization of the adhesive sheet by expanding, the elastic modulus by dynamic viscoelasticity measurement at 900 Hz in the B stage state is increased, It has been found that the elastic modulus after curing is also increased. And, as a result of further earnest research, the inventors of the present invention can maintain a high modulus of elasticity by dynamic viscoelasticity measurement at 900 Hz in the B-stage state and can reduce the modulus of elasticity after curing. I found it.
すなわち、本発明は以下の通りである。
１．高分子量成分を少なくとも含有する半導体用接着シートであって、０℃で９００Ｈｚにおける動的粘弾性測定によるＢステージ状態の弾性率が４０００〜１０００００ＭＰａとなり、２００℃で１０Ｈｚにおける動的粘弾性測定による硬化後の弾性率が１〜１０ＭＰａとなることを特徴とする半導体用接着シート。
２．高分子量成分を少なくとも含有する半導体用接着シートであって、−１０〜１５℃の範囲で９００Ｈｚにおける動的粘弾性測定によるＢステージ状態の弾性率が４０００〜１０００００ＭＰａであり、２００℃で１０Ｈｚにおける動的粘弾性測定による硬化後の弾性率が１〜１０ＭＰａとなることを特徴とする半導体用接着シート。
３．Ｔｇが−３０℃〜１５℃で、重量平均分子量が５万〜１００万である高分子量成分を含むことを特徴とする項１または２記載の半導体用接着シート。
４．前記高分子量成分の含有量が５０重量％以上であることを特徴とする項３に記載の半導体用接着シート。
５．熱硬化性成分をさらに含み、その熱硬化性成分が前記高分子量成分と異なることを特徴とする項１又は２に記載の半導体用接着シート。
６．さらにフィラを５〜７０重量％含むことを特徴とする項１〜５のいずれか一項に記載の半導体用接着シート。
７．上記項１〜６のいずれか一項に記載の半導体用接着シートと、ダイシングテープとを積層してなるダイシング一体型半導体用接着シート。
That is, the present invention is as follows.
1. A semiconductor adhesive sheet containing at least a high molecular weight component, having a B-stage elastic modulus of 4000 to 100,000 MPa by dynamic viscoelasticity measurement at 900 ° C. at 0 ° C. and curing by dynamic viscoelasticity measurement at 200 ° C. at 10 Hz. The adhesive sheet for semiconductors characterized by a later elastic modulus of 1 to 10 MPa.
2. A semiconductor adhesive sheet containing at least a high molecular weight component, wherein the elastic modulus in a B-stage state is 4,000 to 100,000 MPa by dynamic viscoelasticity measurement at 900 Hz in the range of −10 to 15 ° C., and the dynamics at 10 Hz at 200 ° C. An adhesive sheet for semiconductor, wherein the elastic modulus after curing by mechanical viscoelasticity measurement is 1 to 10 MPa.
3. Item 3. The semiconductor adhesive sheet according to Item 1 or 2, comprising a high molecular weight component having a Tg of -30 ° C to 15 ° C and a weight average molecular weight of 50,000 to 1,000,000.
4). Item 4. The semiconductor adhesive sheet according to Item 3, wherein the content of the high molecular weight component is 50% by weight or more.
5. Item 3. The semiconductor adhesive sheet according to Item 1 or 2, further comprising a thermosetting component, wherein the thermosetting component is different from the high molecular weight component.
6). Furthermore, 5-70 weight% of fillers are included, The adhesive sheet for semiconductors as described in any one of claim | item 1 -5 characterized by the above-mentioned.
7). 7. A dicing integrated semiconductor adhesive sheet obtained by laminating the semiconductor adhesive sheet according to any one of items 1 to 6 and a dicing tape.
本発明によれば、半導体装置を製造する際の接着シート付半導体素子を個片化する工程において、エキスパンドによる接着シートの個片化が可能で、且つモールド時に基板凹凸への埋込性が優れる半導体用接着シート及びダイシング一体型半導体用接着シートが得られる。 According to the present invention, in the step of dividing the semiconductor element with an adhesive sheet when manufacturing a semiconductor device, the adhesive sheet can be singulated by expanding, and the embedding in the substrate unevenness is excellent at the time of molding. A semiconductor adhesive sheet and a dicing integrated semiconductor adhesive sheet are obtained.
本発明は、高分子量成分を少なくとも含有する半導体用接着シートであって、０℃で９００Ｈｚにおける動的粘弾性測定によるＢステージ状態の弾性率が４０００〜１０００００ＭＰａとなり、２００℃で１０Ｈｚにおける動的粘弾性測定による硬化後の弾性率が１〜１０ＭＰａとなる半導体用接着シートに関する。 The present invention is an adhesive sheet for a semiconductor containing at least a high molecular weight component, and has an elastic modulus in a B-stage state of 4000 to 100,000 MPa by dynamic viscoelasticity measurement at 900 ° C. at 0 ° C., and dynamic viscosity at 10 Hz at 200 ° C. The present invention relates to a semiconductor adhesive sheet having an elastic modulus of 1 to 10 MPa after curing by elasticity measurement.
Ｂステージ状態での、０℃で９００Ｈｚにおける動的粘弾性測定による弾性率が４０００ＭＰａ未満では、エキスパンド時の接着シートの破断性が十分でなく、１０００００ＭＰａを超えると、接着シートが脆く、取扱い性が低下する。また、上記弾性率が１０００００ＭＰａを超えると、基板凹凸への埋込性が低下したり、半導体素子と支持部材とを接着シートで接合する場合に、熱応力の緩和を吸収しきればくなる。 If the elastic modulus measured by dynamic viscoelasticity measurement at 900 ° C. at 0 ° C. in the B stage state is less than 4000 MPa, the breakability of the adhesive sheet at the time of expansion is not sufficient. descend. Moreover, when the said elasticity modulus exceeds 100,000 MPa, the embedding property to a board | substrate unevenness | corrugation falls, or when joining a semiconductor element and a supporting member with an adhesive sheet, it will have to absorb the relaxation | moderation of a thermal stress.
以上の点から、本発明では、Ｂステージ状態での、０℃で９００Ｈｚにおける動的粘弾性測定による弾性率は、４０００〜１００００ＭＰａとされており、４５００〜８０００ＭＰａであることが好ましく、５０００〜７０００ＭＰａであることが特に好ましい。本発明の半導体用接着シートの弾性率測定は、動的粘弾性測定装置（レオロジ社製 ＤＶＥ−Ｖ４）を使用し、接着シートを半硬化させてなるＢステージ状態のものに引張り荷重をかけて、周波数９００Ｈｚ、速度０℃で行われるものである。ここで、半硬化とは、ＤＳＣによる反応熱測定を行い、原材料の発熱量に対し、発熱量が５０〜９９％である状態を言うものとする。 From the above points, in the present invention, the elastic modulus in the B stage state by dynamic viscoelasticity measurement at 900 ° C. at 0 ° C. is 4000 to 10000 MPa, preferably 4500 to 8000 MPa, preferably 5000 to 7000 MPa. It is particularly preferred that The elastic modulus of the adhesive sheet for semiconductor of the present invention is measured by using a dynamic viscoelasticity measuring device (DVE-V4 manufactured by Rheology) and applying a tensile load to the one in the B stage state obtained by semi-curing the adhesive sheet. , Performed at a frequency of 900 Hz and a speed of 0 ° C. Here, semi-curing refers to a state in which the calorific value is 50 to 99% with respect to the calorific value of the raw material by measuring the reaction heat by DSC.
本発明の半導体用接着シートの硬化後の２００℃での弾性率は、１〜１０ＭＰａであり、２〜９ＭＰａであることが好ましく、３〜８ＭＰａであることがより好ましい。硬化後の２００℃弾性率が１ＭＰａ未満では、信頼性が低下する可能性があり、１０ＭＰａを超えると、基板凹凸への埋込性が低下する可能性がある。本発明の半導体用接着シートの弾性率測定は、動的粘弾性測定装置（レオロジ社製 ＤＶＥ−Ｖ４）を使用し、接着シートの完全硬化物に引張り荷重をかけて、周波数１０Ｈｚ、昇温速度３〜１０℃／ｍｉｎで−５０℃から３００℃まで測定する温度依存性測定モードで行われるものである。ここで、完全硬化とは、ＤＳＣによる反応熱測定を行い、原材料の発熱量に対し、１０％以下の発熱量である状態を言う。 The elastic modulus at 200 ° C. after curing of the adhesive sheet for semiconductor of the present invention is 1 to 10 MPa, preferably 2 to 9 MPa, and more preferably 3 to 8 MPa. If the 200 ° C. elastic modulus after curing is less than 1 MPa, the reliability may decrease, and if it exceeds 10 MPa, the embeddability in the substrate unevenness may decrease. The elastic modulus measurement of the adhesive sheet for semiconductor of the present invention uses a dynamic viscoelasticity measuring device (DVE-V4 manufactured by Rheology), applies a tensile load to the completely cured product of the adhesive sheet, and has a frequency of 10 Hz and a heating rate. This is performed in a temperature-dependent measurement mode in which measurement is performed from −50 ° C. to 300 ° C. at 3 to 10 ° C./min. Here, complete curing refers to a state in which the calorific value of the raw material is 10% or less of the calorific value of the raw material measured by DSC.
また、本発明は、高分子量成分を少なくとも含有する接着シートであって、−１０〜１５℃の範囲で９００Ｈｚにおける動的粘弾性測定によるＢステージ状態の弾性率が４０００〜１０００００ＭＰａとなり、２００℃で１０Ｈｚにおける動的粘弾性測定による硬化後の弾性率が１〜１０ＭＰａとなることを特徴とする半導体用接着シートに関する。温度範囲が−１０℃未満では、エキスパンド時にダイシングテープが破断する可能性があり好ましくない。また１５℃を超えると高分子量成分のＴｇを超えることで、接着シートが軟化するため、エキスパンド時に接着シートを良好に切断できない。温度範囲は、−５〜１０℃が好ましく、０〜５℃がより好ましい。 Further, the present invention is an adhesive sheet containing at least a high molecular weight component, wherein the elastic modulus in the B stage state by dynamic viscoelasticity measurement at 900 Hz in the range of −10 to 15 ° C. becomes 4000 to 100000 MPa, at 200 ° C. The present invention relates to an adhesive sheet for semiconductor, wherein the elastic modulus after curing by dynamic viscoelasticity measurement at 10 Hz is 1 to 10 MPa. If the temperature range is less than −10 ° C., the dicing tape may break during expansion, which is not preferable. Moreover, since it exceeds Tg of a high molecular weight component when it exceeds 15 degreeC, since an adhesive sheet softens, an adhesive sheet cannot be cut | disconnected favorable at the time of an expansion. The temperature range is preferably -5 to 10 ° C, more preferably 0 to 5 ° C.
２００℃で１０Ｈｚにおける動的粘弾性測定による硬化後の弾性率が１〜１０ＭＰａとなるようにした理由は上記と同様である。 The reason why the elastic modulus after curing by dynamic viscoelasticity measurement at 200 ° C. and 10 Hz is 1 to 10 MPa is the same as described above.
（フィラ）
本発明の接着シートは、フィラを含有することが好ましい。また限定するものでは無いが、フィラとしては無機フィラが挙げられ、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、ホウ酸アルミウイスカ、窒化ホウ素、結晶性シリカ、非晶性シリカ、アンチモン酸化物などが挙げられる。熱伝導性向上のためには、アルミナ、窒化アルミニウム、窒化ホウ素、結晶性シリカ、非晶性シリカ等が好ましい。溶融粘度の調整やチクソトロピック性の付与の目的には、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、非晶性シリカ等が好ましい。また、耐湿性を向上させるためにはアルミナ、シリカ、水酸化アルミニウム、アンチモン酸化物が好ましいが、汎用性からシリカがより好ましい。
(Fira)
The adhesive sheet of the present invention preferably contains a filler. Although not limited, the filler includes inorganic fillers, such as aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, alumina, aluminum nitride, Examples thereof include aluminum borate whisker, boron nitride, crystalline silica, amorphous silica, and antimony oxide. In order to improve thermal conductivity, alumina, aluminum nitride, boron nitride, crystalline silica, amorphous silica and the like are preferable. For the purpose 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, non-crystalline silica Crystalline silica and the like are preferred. In order to improve moisture resistance, alumina, silica, aluminum hydroxide, and antimony oxide are preferable, but silica is more preferable in view of versatility.
フィラの粒径は、特に限定するものでは無いが、１次平均粒径が大きすぎると、接着シートの薄膜化が困難であるため、平均粒径が１０μｍ以下であることが好ましい。また上記範囲で、異なる粒径分布をもつ複数種のフィラを混合して使用しても良い。 The particle size of the filler is not particularly limited, but if the primary average particle size is too large, it is difficult to reduce the thickness of the adhesive sheet. Therefore, the average particle size is preferably 10 μm or less. Further, in the above range, a plurality of types of fillers having different particle size distributions may be mixed and used.
本発明の半導体用接着シート中のフィラ量は、５〜７０重量％であることが好ましく、１０〜５０重量％であることがより好ましく、１２〜４０重量％であることが特に好ましく、１５〜３０重量％が最も好ましい。配合量が少ないと接着シートの高弾性化が難しく、多いと接着シートの濡れ性が低下し、ウェハ貼付性、信頼性が低下する可能性がある。 The amount of filler in the semiconductor adhesive sheet of the present invention is preferably from 5 to 70% by weight, more preferably from 10 to 50% by weight, particularly preferably from 12 to 40% by weight. 30% by weight is most preferred. When the blending amount is small, it is difficult to increase the elasticity of the adhesive sheet. When the blending amount is large, the wettability of the adhesive sheet is lowered, and the wafer sticking property and reliability may be lowered.
（熱硬化性成分）
本発明の半導体用接着シートに含有される熱硬化性成分としては、環球式で測定した軟化点が５０℃以上の樹脂であり上記高分子量成分とも、後述する高分子量化合物とも異なるものであれば特に制限はなく、エポキシ樹脂、シアネート樹脂等が挙げられる。これらのうち、耐熱性が高い点で、エポキシ樹脂が好ましく、例えば、油化シェルエポキシ（株）製 エピコート１００１、１００２、１００３、１０５５、１００４、１００４ＡＦ、１００７、１００９、１００３Ｆ、１００４Ｆ、ダウケミカル日本（株）製 Ｄ．Ｅ．Ｒ．６６１、６６２、６６３Ｕ、６６４、６６４Ｕ、６６７、６４２Ｕ、６７２Ｕ、６７３ＭＦ、６６８、６６９等のビスフェノールＡ型エポキシ樹脂、東都化成（株）製 ＹＤＦ−２００４等のビスフェノールＦ型エポキシ樹脂、日本化薬（株）製 ＥＰＰＮ−２０１等のフェノールノボラック型エポキシ樹脂、油化シェルエポキシ（株）製 エピコート １８０Ｓ６５、チバスペシャリティーケミカルズ社製 アラルダイト ＥＣＮ１２７３、１２８０、１２９９、東都化成（株）製 ＹＤＣＮ−７０１、７０２、７０３、７０４、７００−１０、日本化薬（株）製 ＥＯＣＮ−１０２０、１０２Ｓ、１０３Ｓ、１０４Ｓ、住友化学工業（株）製 ＥＳＣＮ−１９５Ｘ、２００Ｌ、２２０等のクレゾールノボラックエポキシ樹脂、油化シェルエポキシ（株）製 Ｅｐｏｎ １０３１Ｓ、エピコート １０３２Ｈ６０、１５７Ｓ７０、日本化薬（株）製 ＥＰＰＮ ５０１Ｈ、５０２Ｈ等の多官能エポキシ樹脂、チバスペシャリティーケミカルズ社製 アラルダイトＰＴ８１０等の複素環含有エポキシ樹脂等が挙げられるが、熱硬化性成分は、これらに限定されるものではない。
(Thermosetting component)
The thermosetting component contained in the adhesive sheet for semiconductor of the present invention is a resin having a softening point measured by ring-and-ball type of 50 ° C. or higher and different from the above high molecular weight component and the high molecular weight compound described later. There is no restriction | limiting in particular, An epoxy resin, cyanate resin, etc. are mentioned. Of these, epoxy resins are preferred because of their high heat resistance. For example, Epicoat 1001, 1002, 1003, 1055, 1004, 1004AF, 1007, 1009, 1003F, 1004F, Dow Chemical Japan manufactured by Yuka Shell Epoxy Co., Ltd. D. E. R. Bisphenol A type epoxy resins such as 661, 662, 663U, 664, 664U, 667, 642U, 672U, 673MF, 668, 669, etc., bisphenol F type epoxy resin such as YDF-2004 manufactured by Tohto Kasei Co., Ltd., Nippon Kayaku ( Phenol novolac type epoxy resin such as EPPN-201 manufactured by Co., Ltd., Epicoat 180S65 manufactured by Yuka Shell Epoxy Co., Ltd., Araldite ECN1273, 1280, 1299 manufactured by Ciba Specialty Chemicals, YDCN-701, 702 manufactured by Toto Kasei Co., Ltd. 703, 704, 700-10, Nippon Kayaku Co., Ltd. EOCN-1020, 102S, 103S, 104S, Sumitomo Chemical Co., Ltd. ESCN-195X, 200L, 220, etc. Cresol novolac epoxy resin, oiled shell epoxy (stock Epoxy 1031S, Epicoat 1032H60, 157S70 manufactured by Nippon Kayaku Co., Ltd. EPPN 501H, 502H and other polyfunctional epoxy resins, Ciba Specialty Chemicals Inc. Araldite PT810 and other heterocyclic ring-containing epoxy resins, etc. are mentioned. The sex component is not limited to these.
（硬化剤）
本発明の半導体用接着シートには、熱硬化性成分を硬化させる硬化剤を含んでもよい。このような硬化剤としては、例えばフェノール樹脂が挙げられる。フェノール樹脂は、特に制限は無く、８５℃、８５％ＲＨの恒温恒湿槽に４８時間投入後の吸水率が２重量％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重量％未満のものを使用することができる。このようなフェノール樹脂は、例えば、フェノール化合物と２価の連結基であるキシリレン化合物を、無触媒または酸触媒の存在下に反応させて得られる。この様にして製造されているフェノール樹脂として代表的なものに、三井化学（株）製ミレックスＸＬＣ−シリーズ、ＸＬシリーズなどがある。
(Curing agent)
The adhesive sheet for semiconductor of the present invention may contain a curing agent that cures the thermosetting component. An example of such a curing agent is a phenol resin. The phenolic resin is not particularly limited, and has a water absorption of 2% by weight or less after being put into a constant temperature and humidity chamber of 85 ° C. and 85% RH for 48%, and is heated at 350 ° C. measured with a thermogravimetric analyzer (TGA). A material having a mass reduction rate (temperature increase rate: 5 ° C./min, atmosphere: nitrogen) of less than 5% by weight can be used. Such a phenol resin is obtained, for example, by reacting a phenol compound and a xylylene compound which is a divalent linking group in the presence of no catalyst or an acid catalyst. Typical examples of the phenol resin produced in this way include Mitex Chemical Co., Ltd.'s Millex XLC-series and XL series.
（硬化促進剤）
また、本発明の半導体用接着シートには、硬化促進剤を添加することもできる。硬化促進剤には、特に制限が無く、各種イミダゾール類を用いることができる。イミダゾール類としては、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１種又は２種以上を併用することもできる。
(Curing accelerator)
Moreover, a hardening accelerator can also be added to the adhesive sheet for a semiconductor of the present invention. There is no restriction | limiting in particular in a hardening accelerator, Various imidazoles can be used. Examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, and the like. Two or more kinds can be used in combination.
硬化促進剤の添加量は、熱硬化性成分としてのエポキシ樹脂、および硬化剤としてのフェノール樹脂の総量１００重量部に対して０．００１〜５重量部が好ましく、０．０５〜３重量部がより好ましい。添加量が０．００１重量部未満だと硬化性が劣る傾向があり、５重量部を超えると保存安定性が低下する傾向がある。 The addition amount of the curing accelerator is preferably 0.001 to 5 parts by weight, and 0.05 to 3 parts by weight with respect to 100 parts by weight of the total amount of the epoxy resin as the thermosetting component and the phenol resin as the curing agent. More preferred. When the addition amount is less than 0.001 part by weight, the curability tends to be inferior, and when it exceeds 5 parts by weight, the storage stability tends to decrease.
（カップリング剤）
また、本発明の半導体用接着シートには、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、シラン系、チタン系、アルミニウム系などが挙げられるが、シラン系カップリング剤が最も好ましい。
(Coupling agent)
Various coupling agents can also be added to the semiconductor adhesive sheet of the present invention in order to improve interfacial bonding between different materials. Examples of the coupling agent include silane-based, titanium-based, and aluminum-based, and silane-based coupling agents are most preferable.
シラン系カップリング剤としては、特に制限は無く、例えば、ビニルトリクロルシラン、ビニルトリス（β−メトキシエトキシ）シラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン等のビニルシラン類、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、３−メタクリロキシプロピル−トリメトキシシラン、メチルトリ（メタクリロイルオキエトキシ）シラン等のメタクリロイルシラン類、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、メチルトリ（グリシジルオキシ）シラン等のエポキシ基含有シラン類、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ‐フェニル−γ−アミノプロピルトリメトキシシラン、３−アミノプロピルメチルジエトキシシラン、３−アミノプロピルトリメトキシシラン、３−アミノプロピル−トリス（２−メトキシ−エトキシ−エトキシ）シラン、Ｎ−メチル−３−アミノプロピルトリメトキシシラン、トリアミノプロピル−トリメトキシシラン、３−４，５−ジヒドロイミダゾール−１−イル−プロピルトリメトキシシラン、アミルトリクロロシラン等のアミノシラン類、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシラン、３−メルカプトプロピル−メチルジメトキシシラン等のメルカプトシラン類、３−ウレイドプロピルトリエトキシシラン、３−ウレイドプロピルトリメトキシシラン等の尿素結合含有シラン類、トリメチルシリルイソシアネート、ジメチルシリルイソシアネート、メチルシリルトリイソシアネート、ビニルシリルトリイソシアネート、フェニルシリルトリイソシアネート、テトライソシアネートシラン、エトキシシランイソシアネート等のイソシアネート基含有シラン類、３−クロロプロピル−メチルジメトキシシラン、３−クロロプロピル−ジメトキシシラン、３−シアノプロピル−トリエトキシシラン、ヘキサメチルジシラザン、Ｎ，Ｏ−ビス（トリメチルシリル）アセトアミド、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリクロロシラン、ｎ−プロピルトリメトキシシラン、イソブチルトリメトキシシラン、オクチルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、Ｎ−β（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリメトキシシラン、オクタデシルジメチル〔３−（トリメトキシシリル）プロピル〕アンモニウムクロライド、γ−クロロプロピルメチルジクロロシラン、γ−クロロプロピルメチルジメトキシシラン、γ−クロロプロピルメチルジエトキシシランなどを使用することができ、これらの１種又は２種以上を併用することもできる。 There is no restriction | limiting in particular as a silane coupling agent, For example, vinyl silanes, such as vinyl trichlorosilane, vinyl tris ((beta) -methoxyethoxy) silane, vinyl triethoxysilane, vinyltrimethoxysilane, (gamma) -methacryloxypropyl trimethoxysilane , Γ-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyl-trimethoxysilane, methacryloylsilanes such as methyltri (methacryloyloxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- Contains epoxy groups such as glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, methyltri (glycidyloxy) silane Orchids, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltri Methoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl-tris (2-methoxy-ethoxy-ethoxy) silane, N-methyl-3-aminopropyltrimethoxysilane, tri Aminosilanes such as aminopropyl-trimethoxysilane, 3-4,5-dihydroimidazol-1-yl-propyltrimethoxysilane, amyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 3 -Merca Mercaptosilanes such as topropyl-methyldimethoxysilane, urea-containing silanes such as 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, trimethylsilyl isocyanate, dimethylsilyl isocyanate, methylsilyl triisocyanate, vinylsilyl triisocyanate Isocyanate group-containing silanes such as phenylsilyl triisocyanate, tetraisocyanate silane, ethoxysilane isocyanate, 3-chloropropyl-methyldimethoxysilane, 3-chloropropyl-dimethoxysilane, 3-cyanopropyl-triethoxysilane, hexamethyldi Silazane, N, O-bis (trimethylsilyl) acetamide, methyltrimethoxysilane, methyltriethoxysilane, ethyltri Chlorosilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, octyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, N-β (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, octadecyl Dimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldichlorosilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, etc. can be used, one of these Or 2 or more types can also be used together.
（高分子量成分）
本発明の半導体用接着シートに含まれる高分子量成分は、Ｔｇが−３０℃〜１５℃、重量平均分子量が５万〜１００万であり、さらに官能基としてエポキシ樹脂と非相溶である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に由来する構造単位を０．５〜６重量％含むエポキシ基含有アクリル共重合体を含むことが好ましい。
(High molecular weight component)
The high molecular weight component contained in the adhesive sheet for a semiconductor of the present invention is a glycidyl acrylate having a Tg of −30 ° C. to 15 ° C., a weight average molecular weight of 50,000 to 1,000,000 and incompatible with an epoxy resin as a functional group. Or it is preferable that the epoxy group containing acrylic copolymer which contains 0.5 to 6 weight% of structural units derived from glycidyl methacrylate is included.
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に由来する構造単位を０．５〜６重量％含み且つ重量平均分子量が１０万以上であるエポキシ基含有アクリル共重合体としては、特に制限が無く、帝国化学産業（株）製 ＨＴＲ―８６０Ｐ−３等を用いることができる。官能基モノマーが、カルボン酸タイプのアクリル酸や、水酸基タイプのヒドロキシメチル（メタ）アクリレートを用いると、橋架け反応が進行しやすく、ワニス状態でのゲル化、Ｂステージ状態での硬化度の上昇による接着力の低下等の問題が生じうる。また、官能基モノマーとして用いるグリシジル（メタ）アクリレートに由来する構造単位の量は、２〜６重量％の共重合体比とすることが好ましい。２重量％未満だと接着力が低下する可能性があり、６重量％を超えるとゲル化する可能性がある。残部にはエチル（メタ）アクリレートやブチル（メタ）アクリレートまたは両者の混合物を用いることができるが、混合比率は、エポキシ基含有アクリル共重合体のガラス転移温度（以下Ｔｇと略す）を考慮して決定する。エポキシ基含有アクリル共重合体のＴｇは、−１０℃以上であることが好ましい。Ｔｇが−１０℃未満であるとＢステージ状態での接着シートのタック性が大きくなり取扱い性が悪化する可能性がある。 The epoxy group-containing acrylic copolymer containing 0.5 to 6% by weight of structural units derived from glycidyl acrylate or glycidyl methacrylate and having a weight average molecular weight of 100,000 or more is not particularly limited, and Teikoku Chemical Industry Co., Ltd. HTR-860P-3 manufactured by Hama, etc. can be used. When the functional group monomer is carboxylic acid type acrylic acid or hydroxyl group type hydroxymethyl (meth) acrylate, the crosslinking reaction is likely to proceed, gelation in the varnish state, and increase in the degree of cure in the B stage state Problems such as a decrease in adhesive strength due to the occurrence of the above may occur. Moreover, it is preferable that the quantity of the structural unit derived from the glycidyl (meth) acrylate used as a functional group monomer shall be a copolymer ratio of 2 to 6 weight%. If it is less than 2% by weight, the adhesive strength may be reduced, and if it exceeds 6% by weight, gelation may occur. Ethyl (meth) acrylate or butyl (meth) acrylate or a mixture of both can be used for the balance, but the mixing ratio takes into consideration the glass transition temperature (hereinafter abbreviated as Tg) of the epoxy group-containing acrylic copolymer. decide. The Tg of the epoxy group-containing acrylic copolymer is preferably −10 ° C. or higher. When Tg is less than −10 ° C., the tackiness of the adhesive sheet in the B-stage state is increased, and the handleability may be deteriorated.
重合方法は特に制限が無く、パール重合、溶液重合等を使用することができる。 The polymerization method is not particularly limited, and pearl polymerization, solution polymerization and the like can be used.
エポキシ基含有アクリル共重合体の重量平均分子量は、３０万〜３００万であることが好ましく、５０万〜２００万であることがより好ましい。重量平均分子量が３０万未満だと、シート状、フィルム状での強度や可とう性の低下やタック性が増大する可能性がある。また、重量平均分子量が３００万を超えると、フロー性（流動性）が小さく配線の回路充填性（回路配線間の空間への接着シートの充填性）が低下する可能性がある。エポキシ基含有アクリル共重合体の配合量は、熱硬化性成分及びその硬化剤の総量１００重量部に対して、１０〜５００重量部とすることが好ましい。この配合量が１０重量部未満だと、弾性率の低減及び成形時のフロー性抑制効果が少ない傾向があり、５００重量部を超えると、高温での取り扱い性が低下する傾向がある。 The weight average molecular weight of the epoxy group-containing acrylic copolymer is preferably 300,000 to 3,000,000, and more preferably 500,000 to 2,000,000. When the weight average molecular weight is less than 300,000, there is a possibility that the strength and flexibility in sheet form and film form and the tackiness are increased. Further, if the weight average molecular weight exceeds 3 million, the flowability (fluidity) is small, and the circuit filling property of the wiring (filling property of the adhesive sheet into the space between the circuit wirings) may be lowered. It is preferable that the compounding quantity of an epoxy-group-containing acrylic copolymer shall be 10-500 weight part with respect to 100 weight part of total amounts of a thermosetting component and its hardening | curing agent. When the blending amount is less than 10 parts by weight, there is a tendency that the elastic modulus is reduced and the flowability suppressing effect at the time of molding is less, and when it exceeds 500 parts by weight, the handleability at high temperature tends to be lowered.
本発明の半導体用接着シートは、前記熱硬化性成分、前記高分子量成分、前記フィラ、前記カップリング剤などを溶剤に溶解あるいは分散してワニスとし、支持体フィルム上に塗布、加熱し溶剤を除去することによって得ることができる。 The adhesive sheet for a semiconductor of the present invention is obtained by dissolving or dispersing the thermosetting component, the high molecular weight component, the filler, the coupling agent, etc. in a solvent to form a varnish, which is applied onto a support film and heated to apply the solvent. It can be obtained by removing.
なお、本発明の半導体用接着シートは、アクリルゴム等の高分子量成分を少なくとも含んでいれば得ることが可能であるが、アクリルゴム等の高分子量成分のほか、フィラをさらに含有していると容易に得ることができる。これは、以下の理由によるものである。 The semiconductor adhesive sheet of the present invention can be obtained as long as it contains at least a high molecular weight component such as acrylic rubber. However, in addition to a high molecular weight component such as acrylic rubber, it further contains a filler. Can be easily obtained. This is due to the following reason.
即ち、アクリルゴム等の高分子量成分が多すぎると、硬化後の半導体用接着シートが低弾性となるものの、Ｂステージ状態での弾性率が低いものとなる場合がある。一方、フィラは、硬化後の半導体用接着シートを低弾性にしにくいものの、Ｂステージ状態での弾性率を高いものとすることができる。従って、アクリルゴム等の高分子量成分とフィラとをバランスよく配合すると、本発明の半導体用接着シートを容易に得ることができる。例えば、アクリルゴム等の高分子量成分を５０〜６０重量％、フィラを２５〜４０重量％の範囲で配合すれば、本発明の半導体用接着シートを容易に得ることができる。 That is, when there are too many high molecular weight components, such as an acrylic rubber, the adhesive sheet for semiconductors after hardening will become low elasticity, but the elasticity modulus in a B stage state may become low. On the other hand, the filler can make the elastic sheet in the B-stage state high although it is difficult to make the cured adhesive sheet for semiconductors low elastic. Therefore, when a high molecular weight component such as acrylic rubber and filler are blended in a balanced manner, the adhesive sheet for semiconductor of the present invention can be easily obtained. For example, if a high molecular weight component such as acrylic rubber is blended in the range of 50 to 60% by weight and filler in the range of 25 to 40% by weight, the adhesive sheet for semiconductor of the present invention can be easily obtained.
前記支持体フィルムとしては、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、ポイエチレンフィルム、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などのプラスチックフィルムを使用することができ、これらプラスチックフィルムは表面を離型処理して使用しることもできる。支持体フィルムは、使用時に剥離して接着剤層のみを使用することもできるし、支持体フィルムとともに使用し、後で除去することもできる。 As the support film, a plastic film such as a polytetrafluoroethylene film, a polyethylene terephthalate film, a polyethylene film, a polypropylene film, a polymethylpentene film, or a polyimide film can be used. It can also be processed and used. The support film can be peeled off at the time of use and only the adhesive layer can be used, or it can be used together with the support film and removed later.
前記ワニス化の溶剤としては、特に制限は無いが、フィルム作製時の揮発性等を考慮し、メチルエチルケトン、アセトン、メチルイソブチルケトン、２−エトキシエタノール、トルエン、キシレン、ブチルセルソルブ、メタノール、エタノール、２−メトキシエタノールなど比較的低沸点の溶媒を使用するのが好ましい。また、塗膜性を向上させるなどの目的で、ジメチルアセトアミド、ジメチルホルムアミド、Ｎ−メチルピロリドン、シクロヘキサノンなど比較的高沸点の溶媒を加えることもできる。 The varnishing solvent is not particularly limited, but considering the volatility during film production, methyl ethyl ketone, acetone, methyl isobutyl ketone, 2-ethoxyethanol, toluene, xylene, butyl cellosolve, methanol, ethanol, It is preferable to use a solvent having a relatively low boiling point such as 2-methoxyethanol. In addition, for the purpose of improving the coating property, a solvent having a relatively high boiling point such as dimethylacetamide, dimethylformamide, N-methylpyrrolidone, cyclohexanone can be added.
熱硬化成分、その硬化剤、高分子量成分、フィラ以外の添加物を含む組成物にフィラを添加した際のワニスの製造には、フィラの分散性を考慮して、らいかい機、３本ロール、ボールミル及びビーズミルなどを使用するのが好ましく、これらを組み合せて使用することもできる。また、フィラと、熱硬化成分及びその硬化剤などの低分子量物をあらかじめ混合した後、高分子量物（高分子量成分など）を配合することによって、混合する時間を短縮することも可能となる。また、ワニスとした後、真空脱気等によってワニス中の気泡を除去することもできる。 In the manufacture of varnish when filler is added to a composition containing a thermosetting component, its curing agent, high molecular weight component, and additives other than filler, It is preferable to use a ball mill, a bead mill or the like, and these may be used in combination. In addition, it is possible to shorten the mixing time by mixing a filler, a low-molecular weight material such as a thermosetting component and a curing agent thereof in advance, and then blending a high-molecular weight material (such as a high-molecular weight component). Further, after the varnish is formed, the bubbles in the varnish can be removed by vacuum degassing or the like.
支持体フィルムへのワニスの塗布方法としては、公知の方法を用いることができ、例えば、ナイフコート法、ロールコート法、スプレーコート法、グラビアコート法、バーコート法、カーテンコート法等が挙げられる。 As a method for applying the varnish to the support film, a known method can be used, and examples thereof include a knife coating method, a roll coating method, a spray coating method, a gravure coating method, a bar coating method, and a curtain coating method. .
半導体用接着シートの厚みは、１〜１００μｍが好ましいが、これに制限されるものでは無い。１μｍより薄いと成膜性が困難であり、１００μｍより厚いと経済的でなくなる。また、本発明の半導体用接着シートは、所望の厚さを得るために、２枚以上を貼り合わせることもできる。この場合には、接着シート同士の剥離が発生しないような貼合せ条件が必要である。 The thickness of the semiconductor adhesive sheet is preferably 1 to 100 μm, but is not limited thereto. If it is thinner than 1 μm, film formation is difficult, and if it is thicker than 100 μm, it is not economical. Moreover, in order to obtain desired thickness, the adhesive sheet for semiconductors of this invention can also bond 2 or more sheets. In this case, it is necessary to have a bonding condition that does not cause peeling between the adhesive sheets.
また、上記の接着シート（半導体用接着シート）はダイシングテープと予め貼り合わせたダイシングテープ一体型接着シートとしても使用される。この場合、ウェハへのラミネート工程が一回で済む点で、作業の効率化が可能である。 Moreover, said adhesive sheet (adhesive sheet for semiconductors) is also used as a dicing tape-integrated adhesive sheet bonded in advance with a dicing tape. In this case, the efficiency of the operation can be improved in that the laminating process on the wafer is performed only once.
本発明に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などのプラスチックフィルム等が挙げられる。また、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良い。ダイシングテープは粘着性を有することが必要であり、ダイシングテープの片面に粘着剤層を設けても良い。これは、粘着剤層の樹脂組成物において、特に液状成分の比率、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。 Examples of the dicing tape used in the present invention include plastic films such as a polytetrafluoroethylene film, a polyethylene terephthalate film, a polyethylene film, a polypropylene film, a polymethylpentene film, and a polyimide film. Further, surface treatment such as primer coating, UV treatment, corona discharge treatment, polishing treatment and etching treatment may be performed as necessary. The dicing tape needs to have adhesiveness, and an adhesive layer may be provided on one side of the dicing tape. This 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 in the resin composition of the pressure-sensitive adhesive layer.
また、半導体装置を製造する際にダイシングテープを用いた場合、ダイシング時には半導体素子が飛散しない程度の接着力を有し、その後ピックアップ時には半導体素子がダイシングテープから剥離できることが必要である。例えば、接着シートやダイシングテープの粘着性が高すぎて両者を張り合わせたときのピール強度が１５０Ｎ／ｍ以上の場合、分離が困難になることがある。そのため、適宜、接着シートのタック強度を調節することが好ましく、その方法としては、接着シートの室温における流動性を上昇させることにより、接着強度及びタック強度も上昇する傾向があり、流動性を低下させれば接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。例えば、流動性を上昇させる場合には、可塑剤の含有量の増加、粘着付与材含有量の増加等の方法がある。逆に流動性を低下させる場合には、前記化合物の含有量を減らせばよい。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、エポキシ系のいわゆる希釈剤等が挙げられる。 Further, when a dicing tape is used when manufacturing a semiconductor device, it is necessary that the semiconductor element has an adhesive force that does not scatter during dicing, and that the semiconductor element can be peeled off from the dicing tape during pick-up thereafter. For example, separation may be difficult when the adhesive strength of the adhesive sheet or dicing tape is too high and the peel strength when they are laminated is 150 N / m or more. For this reason, it is preferable to appropriately adjust the tack strength of the adhesive sheet, and as a method for this, by increasing the fluidity of the adhesive sheet at room temperature, the adhesive strength and the tack strength tend to increase, and the fluidity is lowered. If this is done, the fact that the adhesive strength and tack strength tend to decrease may be utilized. For example, in order to increase fluidity, there are methods such as increasing the plasticizer content and increasing the tackifier content. Conversely, when the fluidity is lowered, the content of the compound may be reduced. Examples of the plasticizer include monofunctional acrylic monomers, monofunctional epoxy resins, liquid epoxy resins, acrylic resins, and epoxy-based so-called diluents.
本発明の接着シートは、それ自体で用いても構わないが、本発明の接着シートを従来公知のダイシングテープ上に積層したダイシングテープ一体型接着シートとして用いることもできる。接着シートとダイシングテープを積層したダイシングテープ一体型接着シートの、ダイシングの際のピール強度は、１５０Ｎ／ｍ以下が好ましく、より好ましくは５０Ｎ／ｍ以下である。ダイシングテープ上に接着シートを積層する方法としては、印刷のほか、予め作成した接着シートをダイシングテープ上にホットロールでプレスしてラミネートするホットロールラミネート法が挙げられるが、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法が好ましい。尚、ダイシングテープの膜厚は、特に制限はなく、接着シートの膜厚やダイシングテープ一体型接着シート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、テープの取扱い性が良い点で、好ましくは６０〜１５０μｍ、より好ましくは７０〜１３０μｍである。 The adhesive sheet of the present invention may be used by itself, but can also be used as a dicing tape-integrated adhesive sheet in which the adhesive sheet of the present invention is laminated on a conventionally known dicing tape. The peel strength of the dicing tape integrated adhesive sheet obtained by laminating the adhesive sheet and the dicing tape is preferably 150 N / m or less, and more preferably 50 N / m or less. As a method of laminating the adhesive sheet on the dicing tape, in addition to printing, there is a hot roll laminating method in which a pre-made adhesive sheet is pressed with a hot roll on the dicing tape and laminated, but it can be continuously produced, A hot roll laminating method is preferable in terms of efficiency. In addition, the film thickness of the dicing tape is not particularly limited, and is appropriately determined based on the knowledge of a person skilled in the art depending on the film thickness of the adhesive sheet and the application of the dicing tape-integrated adhesive sheet. The tape is preferably 60 to 150 [mu] m, more preferably 70 to 130 [mu] m, in terms of good handleability of the tape.
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＞
エポキシ樹脂としてＹＤＣＮ−７００−１０（東都化成（株）製商品名、クレゾールノボラック型エポキシ樹脂、エポキシ当量２１０）、フェノール樹脂としてミレックスＸＬＣ−ＬＬ（三井化学（株）製商品名、フェノール樹脂、水酸基当量１７５、吸水率１．８％、３５０℃における加熱質量減少率４％）、これら熱硬化成分及び硬化剤の総量１００重量部に対して、シランカップリング剤としてＡ−１１６０（ＧＥ東芝（株）製商品名、γ―ウレイドプロピルトリエトキシシラン）、フィラとして、ＳＯ−Ｃ２（（株）アドマテック製商品名、シリカ、比表面積７ｍ２／ｇ、平均粒径０．４〜０．６μｍ）からなる組成物に、シクロヘキサノンを加えて攪拌混合し、さらにビーズミルを用いて９０分混練した。このとき、組成物の組成は、表１に示す通りとした。
<Example 1>
YDCN-700-10 (trade name, manufactured by Toto Kasei Co., Ltd., cresol novolac type epoxy resin, epoxy equivalent 210) as an epoxy resin, and Millex XLC-LL (trade name, manufactured by Mitsui Chemicals, Ltd., phenol resin, hydroxyl group) as a phenol resin Equivalent 175, water absorption rate 1.8%, heating mass reduction rate at 350 ° C. 4%), A-1160 (GE Toshiba Corporation) as silane coupling agent with respect to 100 parts by weight of the total amount of these thermosetting component and curing agent ) Product name, γ-ureidopropyltriethoxysilane), as filler, from SO-C2 (product name made by Admatech, silica, specific surface area 7 m 2 / g, average particle size 0.4-0.6 μm) Cyclohexanone was added to the resulting composition, mixed with stirring, and further kneaded for 90 minutes using a bead mill. At this time, the composition of the composition was as shown in Table 1.
これにグリシジルメタクリレートに由来する構造単位を３重量％を含むアクリルゴムＨＴＲ−８６０Ｐ−３（ナガセケムテック（株）製商品名、重量平均分子量１００万）、硬化促進剤としてキュアゾール２ＰＺ−ＣＮ（四国化成（株）製商品名、１−シアノエチル−２−フェニルイミダゾール）を下記表１に示す配合量で混合攪拌し、真空脱気した。こうしてワニスを得た。 Acrylic rubber HTR-860P-3 (trade name, manufactured by Nagase Chemtech Co., Ltd., weight average molecular weight 1 million) containing 3% by weight of a structural unit derived from glycidyl methacrylate, and Curazole 2PZ-CN (Shikoku) as a curing accelerator. Kasei Co., Ltd. trade name, 1-cyanoethyl-2-phenylimidazole) was mixed and stirred at the blending amounts shown in Table 1 below, and vacuum degassed. A varnish was thus obtained.
次に、このワニスを、離型処理した厚さ７５μｍのポリエチレンテレフタレートフィルム（キャリアフィルム）上に塗布し、接着シートを得た。そして、この接着シートを１４０℃で５分間加熱乾燥して、膜厚が２５μｍのＢステージ状態の塗膜を形成し、キャリアフィルムを備えたＢステージ状態の接着シートを作製した。なお、表１に示される数値の単位は重量部である。
＜実施例２及び比較例１〜４＞
エポキシ樹脂、フェノール樹脂、フィラ、カップリング剤、アクリルゴム、硬化促進剤を表１に示す組成としたこと以外は実施例１と同様にして接着シートを得た。そして、この接着シートを実施例１と同様にして半硬化させ、Ｂステージ状態の接着シートを得た。なお、表１中、エポキシ樹脂としてのＹＤ−８１２５は、ＹＤ−８１２５（東都化成（株）製商品名、ＢＰＡ型エポキシ樹脂、エポキシ当量１７３）を言い、フェノール樹脂としてのＬＦ−２８８２は、ＬＦ−２８８２（大日本インキ化学工業（株）製商品名、フェノールノボラック樹脂）を言い、シリカフィラとしてのＲ９７２とは、アエロジルＲ９７２（日本アエロジル（株）製商品名、シリカ、平均粒径０．０１６μｍ）のことを言う。
<Example 2 and Comparative Examples 1-4>
An adhesive sheet was obtained in the same manner as in Example 1 except that the epoxy resin, phenol resin, filler, coupling agent, acrylic rubber, and curing accelerator had the composition shown in Table 1. This adhesive sheet was semi-cured in the same manner as in Example 1 to obtain an adhesive sheet in a B stage state. In Table 1, YD-8125 as an epoxy resin means YD-8125 (trade name, BPA type epoxy resin, epoxy equivalent 173 manufactured by Toto Kasei Co., Ltd.), and LF-2882 as a phenol resin is LF. -2882 (trade name, manufactured by Dainippon Ink & Chemicals, Inc., phenol novolac resin), and R972 as silica filler is Aerosil R972 (trade name, manufactured by Nippon Aerosil Co., Ltd., silica, average particle size 0.016 μm) )
＜接着シートの評価方法＞
（Ｂステージ弾性率）
動的粘弾性測定装置（レオロジ社製 ＤＶＥ−Ｖ４）を使用し、Ｂステージの接着シートに対し、引張り荷重をかけて、周波数９００Ｈｚ、温度０℃で測定を行った。結果を表２に示す。
<Evaluation method of adhesive sheet>
(B stage elastic modulus)
Using a dynamic viscoelasticity measuring device (DVE-V4 manufactured by Rheology), a tensile load was applied to the adhesive sheet of the B stage, and the measurement was performed at a frequency of 900 Hz and a temperature of 0 ° C. The results are shown in Table 2.
（引っ張り分割性）
オートグラフ（島津製作所製 ＡＧＳ−１０００Ｇ）を使用し、実施例１〜２及び比較例１〜４におけるＢステージ状態の接着シートを、８０℃の温度でウェハに熱ラミネートした後、ウェハ中央部にダイヤモンドカッターで切込みを入れ、ウェハのみを分割した。分割された接着シート付ウェハを冷却し、オートグラフに取り付け、０℃の状態でエキスパンドを行い、接着シートの分割性を観察した。結果を表２に示す。エキスパンド条件は、エキスパンド速度１０００ｍｍ／ｍｉｎ、エキスパンド量３ｍｍとした。なお、表２において、接着シートを分割できた場合は「○」、分割できない場合は「×」とした。
(Tensile splitting)
Using an autograph (AGS-1000G manufactured by Shimadzu Corporation), the B-staged adhesive sheets in Examples 1 and 2 and Comparative Examples 1 to 4 were thermally laminated to the wafer at a temperature of 80 ° C. A notch was made with a diamond cutter, and only the wafer was divided. The divided wafer with an adhesive sheet was cooled, attached to an autograph, expanded at 0 ° C., and the splitting property of the adhesive sheet was observed. The results are shown in Table 2. The expanding conditions were an expanding speed of 1000 mm / min and an expanding amount of 3 mm. In Table 2, “◯” indicates that the adhesive sheet can be divided, and “x” indicates that the adhesive sheet cannot be divided.
（高温弾性率）
硬化後の弾性率は、動的粘弾性測定装置（レオロジ社製 ＤＶＥ−Ｖ４）を使用し、Ｂステージ状態の接着シートを１７０℃、２時間の条件で熱硬化させ、硬化後の接着シートに対して引張り荷重をかけて、周波数１０Ｈｚ、昇温速度３〜１０℃／ｍｉｎで−５０℃から３００℃まで測定する温度依存性測定モードで行った。結果を表２に示す。
For the elastic modulus after curing, a dynamic viscoelasticity measuring device (DVE-V4 manufactured by Rheology) was used, and the B-staged adhesive sheet was thermally cured at 170 ° C. for 2 hours to obtain a cured adhesive sheet. On the other hand, a tensile load was applied, and the measurement was performed in a temperature dependency measurement mode in which measurement was performed from −50 ° C. to 300 ° C. at a frequency of 10 Hz and a temperature increase rate of 3 to 10 ° C./min. The results are shown in Table 2.
表２に示すように、実施例１、２は、Ｂステージ弾性率が高く、接着シート切断性が良好であり、且つ硬化後弾性率が低く、モールド時の基板凹凸埋込性に優れていた。比較例１、２は、フィラ配合量、或いはエポキシ樹脂及びフェノール樹脂配合量が多いため、Ｂステージ弾性率が高く、接着シート切断性は良好だが、硬化後弾性率が高く、モールド時の基板凹凸埋込性が劣る。比較例３、４は、硬化後弾性率が低いため、モールド時の基板凹凸埋込性は良好と思われるが、Ｂステージ弾性率が低く、接着シート切断性が劣る。 As shown in Table 2, Examples 1 and 2 had high B-stage elastic modulus, good adhesive sheet cutting property, low post-curing elastic modulus, and excellent substrate unevenness embedding property at the time of molding. . Comparative Examples 1 and 2 have a high blending amount of filler or epoxy resin and phenolic resin, so that the B-stage elastic modulus is high and the adhesive sheet cutting property is good, but the post-curing elastic modulus is high, and the substrate unevenness during molding Poor embeddability. Since Comparative Examples 3 and 4 have low post-curing elastic modulus, the substrate unevenness embedding property during molding seems to be good, but the B-stage elastic modulus is low and the adhesive sheet cutting property is inferior.
以上、本発明について実施例を用いて説明してきたが、以下の作用効果を奏することが分かった。即ち本発明の接着シートは、半導体装置を製造する際のダイシング工程において、エキスパンドによる個片化が可能であり、且つモールド時に基板凹凸への埋込性が優れる半導体用接着シートが得られる。 As mentioned above, although this invention has been demonstrated using the Example, it turned out that there exist the following effects. That is, the adhesive sheet of the present invention can be singulated by expanding in a dicing process when manufacturing a semiconductor device, and an adhesive sheet for a semiconductor that is excellent in embedding in substrate irregularities during molding can be obtained.
Claims (7)
０℃で９００Ｈｚにおける動的粘弾性測定によるＢステージ状態の弾性率が４０００〜１０００００ＭＰａとなり、２００℃で１０Ｈｚにおける動的粘弾性測定による硬化後の弾性率が１〜１０ＭＰａとなることを特徴とする半導体用接着シート。 A semiconductor adhesive sheet containing at least a high molecular weight component,
The elastic modulus of the B stage state by dynamic viscoelasticity measurement at 900 Hz at 0 ° C. is 4000 to 100,000 MPa, and the elastic modulus after curing by dynamic viscoelasticity measurement at 10 Hz at 200 ° C. is 1 to 10 MPa. Adhesive sheet for semiconductors.
−１０〜１５℃の範囲で９００Ｈｚにおける動的粘弾性測定によるＢステージ状態の弾性率が４０００〜１０００００ＭＰａとなり、２００℃で１０Ｈｚにおける動的粘弾性測定による硬化後の弾性率が１〜１０ＭＰａとなることを特徴とする半導体用接着シート。 A semiconductor adhesive sheet containing at least a high molecular weight component,
The elastic modulus in the B stage state by dynamic viscoelasticity measurement at 900 Hz in the range of −10 to 15 ° C. becomes 4000 to 100,000 MPa, and the elastic modulus after curing by dynamic viscoelasticity measurement at 200 Hz at 10 Hz becomes 1 to 10 MPa. The adhesive sheet for semiconductors characterized by the above-mentioned.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009060927A1 (en) * | 2007-11-08 | 2009-05-14 | Hitachi Chemical Company, Ltd. | Adhesive sheet for semiconductor, and dicing tape integrated adhesive sheet for semiconductor |
| JP2012104716A (en) * | 2010-11-11 | 2012-05-31 | Sekisui Chem Co Ltd | Adhesive sheet for processing semiconductor and packaging method of semiconductor chip |
| JP2012160489A (en) * | 2011-01-28 | 2012-08-23 | Kyocera Chemical Corp | Manufacturing method of electronic component |
| JP2013021221A (en) * | 2011-07-13 | 2013-01-31 | Nitto Denko Corp | Adhesive film for semiconductor device, backing film for flip-chip semiconductor, and backing film for semiconductor with integrated dicing tape |
| WO2023085167A1 (en) * | 2021-11-15 | 2023-05-19 | 株式会社レゾナック | Thermosetting adhesive composition, multilayer film, bonded body and method for producing same |
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|---|---|---|---|---|
| JP2005303275A (en) * | 2004-03-15 | 2005-10-27 | Hitachi Chem Co Ltd | Dicing/die boding sheet |
| JP2006299226A (en) * | 2005-03-23 | 2006-11-02 | Furukawa Electric Co Ltd:The | Dicing die bond sheet |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005303275A (en) * | 2004-03-15 | 2005-10-27 | Hitachi Chem Co Ltd | Dicing/die boding sheet |
| JP2006299226A (en) * | 2005-03-23 | 2006-11-02 | Furukawa Electric Co Ltd:The | Dicing die bond sheet |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009060927A1 (en) * | 2007-11-08 | 2009-05-14 | Hitachi Chemical Company, Ltd. | Adhesive sheet for semiconductor, and dicing tape integrated adhesive sheet for semiconductor |
| US9969909B2 (en) | 2007-11-08 | 2018-05-15 | Hitachi Chemical Company, Ltd. | Adhesive sheet for semiconductor, and dicing tape integrated adhesive sheet for semiconductor |
| JP2012104716A (en) * | 2010-11-11 | 2012-05-31 | Sekisui Chem Co Ltd | Adhesive sheet for processing semiconductor and packaging method of semiconductor chip |
| JP2012160489A (en) * | 2011-01-28 | 2012-08-23 | Kyocera Chemical Corp | Manufacturing method of electronic component |
| JP2013021221A (en) * | 2011-07-13 | 2013-01-31 | Nitto Denko Corp | Adhesive film for semiconductor device, backing film for flip-chip semiconductor, and backing film for semiconductor with integrated dicing tape |
| KR101920083B1 (en) | 2011-07-13 | 2018-11-19 | 닛토덴코 가부시키가이샤 | Adhesive film for semiconductor device, film for back surface of flip-chip semiconductor and dicing-tape-integrated film for back surface of flip-chip semiconductor |
| WO2023085167A1 (en) * | 2021-11-15 | 2023-05-19 | 株式会社レゾナック | Thermosetting adhesive composition, multilayer film, bonded body and method for producing same |
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