JP4254265B2 - Epoxy resin composition and semiconductor device - Google Patents
Epoxy resin composition and semiconductor device Download PDFInfo
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- JP4254265B2 JP4254265B2 JP2003039619A JP2003039619A JP4254265B2 JP 4254265 B2 JP4254265 B2 JP 4254265B2 JP 2003039619 A JP2003039619 A JP 2003039619A JP 2003039619 A JP2003039619 A JP 2003039619A JP 4254265 B2 JP4254265 B2 JP 4254265B2
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- epoxy resin
- resin composition
- coupling agent
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- semiconductor
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- 229920000647 polyepoxide Polymers 0.000 title claims description 49
- 239000003822 epoxy resin Substances 0.000 title claims description 48
- 239000000203 mixture Substances 0.000 title claims description 30
- 239000004065 semiconductor Substances 0.000 title claims description 25
- 239000005011 phenolic resin Substances 0.000 claims description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 13
- 239000011256 inorganic filler Substances 0.000 claims description 9
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 9
- 238000005538 encapsulation Methods 0.000 claims description 7
- -1 thiazoline compound Chemical class 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 13
- 229910000679 solder Inorganic materials 0.000 description 12
- 239000000126 substance Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 description 7
- 125000004434 sulfur atom Chemical group 0.000 description 7
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000013329 compounding Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 238000001721 transfer moulding Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 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
- 238000007789 sealing Methods 0.000 description 3
- 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-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
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 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 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 1
- 150000003549 thiazolines Chemical class 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、半導体封止用エポキシ樹脂組成物、及びこれを用いた半導体装置に関するものである。
【０００２】
【従来の技術】
ＩＣ、ＬＳＩ等の半導体素子の封止方法として、エポキシ樹脂組成物のトランスファー成形が低コスト、大量生産に適しており、採用されて久しく、信頼性の点でもエポキシ樹脂や硬化剤であるフェノール樹脂の改良により特性の向上が図られてきた。しかし、近年の電子機器の小型化、軽量化、高性能化の市場動向において、半導体の高集積化も年々進み、また半導体装置の表面実装化が促進されるなかで、半導体封止用エポキシ樹脂組成物への要求は益々厳しいものとなってきている。このため、従来からのエポキシ樹脂組成物では解決出来ない問題点も出てきている。
その最大の問題点は、表面実装の採用により半導体装置が半田浸漬或いは半田リフロー工程で急激に２００℃以上の高温にさらされ、吸湿した水分が爆発的に気化する際の応力により、半導体装置内、特に半導体素子、リードフレーム、インナーリード上の金メッキや銀メッキ等の各種メッキされた各接合部分とエポキシ樹脂組成物の硬化物の界面で剥離が生じたりして、信頼性が著しく低下する現象である。
【０００３】
半田処理による信頼性低下を改善するために、エポキシ樹脂組成物中の無機質充填材の充填量を増加させることで低吸湿化、高強度化、低熱膨張化を達成し耐半田性を向上させ、低溶融粘度の樹脂を使用して、成形時に低粘度で高流動性を維持させる手法がある（例えば、特許文献１参照。）。この手法を用いることにより耐半田性がかなり改良されるが、無機充填材の充填割合の増加と共に、流動性が犠牲になりパッケージ内に空隙が生じやすくなる欠点があった。またメッキ部分とエポキシ樹脂組成物の界面での剥離を防止する為、アミノシランやメルカプトシラン等の各種カップリング剤を添加して流動性と耐半田性の両立を図る手法も提案されている（例えば、特許文献２参照。）が、この方法でも十分に良好な半導体封止用エポキシ樹脂組成物は得られるには至らなかった。
【０００４】
【特許文献１】
特開昭６４−６５１１６号公報（２〜７頁）
【特許文献２】
特開平９−２５５８５２号公報（２〜７頁）
【０００５】
【発明が解決しようとする課題】
本発明は、流動性、耐半田性に優れた半導体封止用エポキシ樹脂組成物、及びこれを用いた半導体装置を提供するものである。
【０００６】
【課題を解決するための手段】
本発明は、
［１］ （Ａ）エポキシ樹脂、（Ｂ）フェノール樹脂、（Ｃ）硬化促進剤、（Ｄ）無機充填材、（Ｅ）一般式（１）で表されるシランカップリング剤、及び（Ｆ）チアゾリン化合物を必須成分とすることを特徴とする半導体封止用エポキシ樹脂組成物、
【化３】
【０００７】
［２］ （Ｅ）一般式（１）で表されるシランカップリング剤の構造が一般式（２）で表されるシランカップリング剤である第［１］項記載の半導体封止用エポキシ樹脂組成物、
【化４】
［３］ 第［１］又は［２］項に記載の半導体封止用エポキシ樹脂組成物を用いて半導体素子を封止してなることを特徴とする半導体装置、
である。
【０００８】
【発明の実施の形態】
本発明に用いるエポキシ樹脂としては、１分子内にエポキシ基を２個以上有するモノマー、オリゴマー、ポリマー全般を言い、その分子量、分子構造は特に限定するものではないが、例えばビフェニル型エポキシ樹脂、ビスフェノール型エポキシ樹脂、スチルベン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、アルキル変性トリフェノールメタン型エポキシ樹脂、トリアジン核含有エポキシ樹脂、ジシクロペンタジエン変性フェノール型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂（フェニレン骨格、ビフェニレン骨格等を有する）等が挙げられ、これらは単独でも混合して用いても差し支えない。
【０００９】
本発明に用いるフェノール樹脂としては、１分子内にフェノール性水酸基を２個以上有するモノマー、オリゴマー、ポリマー全般を言い、その分子量、分子構造を特に限定するものではないが、例えばフェノールノボラック樹脂、クレゾールノボラック樹脂、ジシクロペンタジエン変性フェノール樹脂、テルペン変性フェノール樹脂、トリフェノールメタン型樹脂、フェノールアラルキル樹脂（フェニレン骨格、ビフェニレン骨格等を有する）等が挙げられ、これらは単独でも混合して用いても差し支えない。
【００１０】
エポキシ樹脂とフェノール樹脂の配合量としては、全エポキシ樹脂のエポキシ基数と全フェノール樹脂のフェノール性水酸基数の比が０．８〜１．３であることが好ましく、この範囲を外れると、エポキシ樹脂組成物の硬化性の低下、或いは硬化物のガラス転移温度の低下、耐湿信頼性の低下等が生じる可能性がある。
【００１１】
本発明に用いる硬化促進剤としては、エポキシ基とフェノール性水酸基との硬化反応を促進させるものであればよく、一般に封止材料に使用するものを用いることができる。例えば、１，８−ジアザビシクロ（５，４，０）ウンデセン−７、トリフェニルホスフィン、２−メチルイミダゾール、テトラフェニルホスホニウム・テトラフェニルボレート等が挙げられ、これらは単独でも混合して用いても差し支えない。
【００１２】
本発明に用いる無機充填材としては、一般に半導体封止用エポキシ樹脂組成物に使用されているものを用いることができる。例えば、溶融シリカ、結晶シリカ、タルク、アルミナ、窒化珪素等が挙げられ、最も好適に使用されるものとしては、球状の溶融シリカである。これらの無機充填剤は、単独でも混合して用いても差し支えない。無機充填材の配合量は、特に限定されないが、全エポキシ樹脂組成物中７８〜９６重量％が好ましい。下限値を下回ると十分な耐半田性が得られない可能性があり、上限値を超えると十分な流動性が得られない可能性がある。
【００１３】
本発明において一般式（１）で表されるシランカップリング剤は必須であり、さらには一般式（２）で表されるシランカップリング剤を用いた場合、流動性及び耐半田性を改良する効果が大きく好ましい。一般式（１）で表されるシランカップリング剤は１種類を単独で使用しても２種類以上を併用してもよい。また配合量は、特に限定されないが、全エポキシ樹脂組成物中０．０１〜３重量％が望ましく、より好ましくは０.０５〜１重量％である。上記の下限値を下回ると十分な流動性が得られない可能性があり、上限値を超えると硬化性が低下する可能性がある。
【００１４】
本発明において１分子中にＳ原子とＮ原子を各１個以上含む化合物は必須であり、その分子量、分子構造は特に限定されないが、化合物中にＳ−Ｃ−Ｎ構造を有する化合物である場合、メッキ部分との密着の効果が大きくなり好ましい。このような化合物として例えば、チアゾリン、チアゾール等がある。このような化合物の中では、密着強度が大きいことから、チアゾリン化合物がより好ましい。１分子中にＳ原子とＮ原子を各１個以上含む化合物は１種類を単独で使用しても２種類以上を併用してもよい。また、１分子中にＳ原子とＮ原子を各１個以上含む化合物の配合量は特に限定されないが、全エポキシ樹脂組成物中０．０１〜３重量％が望ましく、より好ましくは０.０５〜１重量％である。下限値を下回るとメッキ部分と十分な密着性が得られない可能性があり、上限値を超えると硬化性が低下する可能性がある。
【００１５】
本発明において一般式（１）で表されるシランカップリング剤と、１分子中にＳ原子とＮ原子を各１個以上含む化合物は併用することが必須であり、どちらか一方だけ配合していても、流動性及び耐半田性が十分でない。
【００１６】
（Ａ）エポキシ樹脂、（Ｂ）フェノール樹脂、（Ｃ）硬化促進剤、（Ｄ）無機充填材、（Ｅ）一般式（１）で表されるシランカップリング剤、及び（Ｆ）１分子中にＳ原子とＮ原子を各１個以上含む化合物を必須成分とする
本発明のエポキシ樹脂組成物は、エポキシ樹脂、フェノール樹脂、硬化促進剤、無機充填材、一般式（１）で表されるシランカップリング剤、及び分子中にＳ原子とＮ原子を各１個以上含む化合物を必須成分とし、更にこれ以外に必要に応じて、一般式（１）で表される以外のアミノシラン、エポキシシラン、メルカプトシラン、アルキルシラン、ウレイドシラン、ビニルシラン等のシランカップリング剤や、チタネートカップリング剤、アルミニウムカップリング剤、アルミニウム／ジルコニウムカップリング剤等のカップリング剤、カーボンブラック等の着色剤、天然ワックス、合成ワックス等の離型剤及び、ゴム等の低応力添加剤、臭素化エポキシ樹脂や三酸化アンチモン、水酸化アルミニウム、水酸化マグネシウム、ほう酸亜鉛、モリブデン酸亜鉛、フォスファゼン等の難燃剤等の添加剤を適宜配合しても差し支えない。
【００１７】
また、本発明のエポキシ樹脂組成物は、ミキサー等を用いて原料を充分に均一に混合した後、更に熱ロール又はニーダー等で溶融混練し、冷却後粉砕して得られる。
本発明のエポキシ樹脂組成物を用いて、半導体素子等の各種の電子部品を封止し、半導体装置を製造するには、トランスファーモールド、コンプレッションモールド、インジェクションモールド等の従来からの成形方法で硬化成形すればよい。
【００１８】
【実施例】
以下に本発明の実施例を示すが、本発明はこれらに限定されるものではない。配合割合は重量部とする。
なお、実施例、及び比較例で用いたカップリング剤及び１分子中にＳ原子とＮ原子を各１個以上含む化合物について、以下に示す。
カップリング剤１：式（３）で示されるカップリング剤（信越化学（株）製、ＫＢＭ−５７３）
【化５】
【００１９】
カップリング剤２：式（４）で示されるカップリング剤（信越化学（株）製、Ｘ１２−８０６）
【化６】
【００２０】
カップリング剤３：式（５）で示されるカップリング剤（信越化学（株）製、ＫＢＭ−４０３）
【化７】
【００２１】
カップリング剤４：式（６）で示されるカップリング剤（信越化学（株）製、ＫＢＭ−８０３）
【化８】
【００２２】
カップリング剤５：式（７）で示されるカップリング剤（信越化学（株）製、ＫＢＥ−９０３）
【化９】
【００２３】
Ｓ、Ｎ含有化合物１：式（８）で示される化合物（関東化学、一級試薬）
【化１０】
【００２４】
Ｓ、Ｎ含有化合物２：式（９）で示される化合物（関東化学、一級試薬）
【化１１】
【００２６】
実施例１
エポキシ樹脂１：式（１１）を主成分とするエポキシ樹脂（ジャパンエポキシレジン（株）製、ＹＸ−４０００、エポキシ当量１９０ｇ／ｅｑ、融点１０５℃、以下、Ｅ−１という） ４９重量部
【化１３】
【００２７】
フェノール樹脂２：式（１２）で示されるフェノール樹脂（三井化学（株）製、ＸＬＣ−ＬＬ、水酸基当量１６５ｇ／ｅｑ、軟化点７９℃、以下Ｈ−１という） ４２重量部
【化１４】
【００２８】
１，８−ジアザビシクロ（５，４，０）ウンデセン−７（以下、ＤＢＵという） ５重量部
溶融球状シリカ（平均粒径２１μｍ） ８９０重量部
カップリング剤１ ３重量部
Ｓ、Ｎ含有化合物１ ３重量部
カーボンブラック ３重量部
カルナバワックス ５重量部
をミキサーにて混合し、熱ロールを用いて、９５℃で８分間混練して冷却後粉砕し、エポキシ樹脂組成物を得た。得られたエポキシ樹脂組成物を、以下の方法で評価した。結果を表１に示す。
【００２９】
評価方法
スパイラルフロー：ＥＭＭＩ−１−６６に準じたスパイラルフロー測定用金型を用いて、金型温度１７５℃、圧力６．９ＭＰa、硬化時間１２０秒で測定した。単位はｃｍ。
密着強度：トランスファー成形機を用いて、金型温度１７５℃、注入圧力９．８ＭＰａ、硬化時間１２０秒の条件で、リードフレーム上に２ｍｍ×２ｍｍ×２ｍｍの密着強度試験片を成形した。リードフレームには銅フレームに銀メッキしたもの（フレーム１）とＮｉＰｄ合金フレームに金メッキしたもの（フレーム２）の２種類を用いた。その後、自動せん断強度測定装置（ＤＡＧＥ社製、ＰＣ２４００）を用いて、エポキシ樹脂組成物の硬化物とフレームとのせん断強度を測定した。単位はＮ／ｍｍ2。
耐半田クラック：低圧トランスファー成形機を用いて、成形温度１７５℃、圧力８．３ＭＰａ、硬化時間１２０秒で、８０ｐＱＦＰ（ＮｉＰｄ合金フレームに金メッキしたフレーム、チップサイズ６．０ｍｍ×６．０ｍｍ）を成形し、アフターベークとして１７５℃、８時間加熱処理した後、８５℃、相対湿度８５％で１２０時間の加湿処理を行った後、２６０℃のＩＲリフロー処理をした。パッケージ内部の剥離とクラックを超音波探傷機で確認した。１０個のパッケージ中の不良パッケージ数を示す。
【００３０】
実施例２〜６、比較例１〜５
表１の配合に従い、実施例１と同様にしてエポキシ樹脂組成物を得て、実施例１と同様にして評価した。結果を表１に示す。
実施例１以外で用いた原材料を以下に示す。
エポキシ樹脂２：式（１３）で示されるエポキシ樹脂（日本化薬（株）製、ＮＣ３０００Ｐ、軟化点５８℃、エポキシ当量２７３、以下、Ｅ−２という）
【化１５】
【００３１】
フェノール樹脂２：式（１４）で示されるフェノール樹脂（明和化成（株）製、ＭＥＨ−７８５１ＳＳ、軟化点１０７℃、水酸基当量２０４、以下、Ｈ−２という）
【化１６】
【００３２】
【表１】
【００３３】
【発明の効果】
本発明に従うと、流動性、耐半田性に優れた半導体封止用エポキシ樹脂組成物、及び半導体装置を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an epoxy resin composition for semiconductor encapsulation and a semiconductor device using the same.
[0002]
[Prior art]
As a sealing method for semiconductor elements such as IC and LSI, transfer molding of an epoxy resin composition is suitable for mass production at low cost and has been adopted for a long time, and a phenol resin that is an epoxy resin or a curing agent in terms of reliability. Improvements have been made to improve the characteristics. However, due to the recent trend toward smaller, lighter, and higher performance electronic devices, semiconductors have been increasingly integrated and the surface mounting of semiconductor devices has been promoted. The demand for compositions has become increasingly severe. For this reason, the problem which cannot be solved with the conventional epoxy resin composition has also come out.
The biggest problem is that by adopting surface mounting, the semiconductor device is suddenly exposed to a high temperature of 200 ° C. or higher in the solder dipping or solder reflow process, and the moisture when moisture absorbed explosively evaporates. In particular, a phenomenon in which reliability is remarkably reduced due to peeling at the interface between various plated joints such as gold plating and silver plating on semiconductor elements, lead frames, and inner leads and the cured product of the epoxy resin composition. It is.
[0003]
In order to improve reliability degradation due to solder processing, increase the amount of inorganic filler in the epoxy resin composition to achieve low moisture absorption, high strength, low thermal expansion, improve solder resistance, There is a technique of using a low melt viscosity resin to maintain a high fluidity at a low viscosity during molding (see, for example, Patent Document 1). Although solder resistance is considerably improved by using this method, there is a drawback that fluidity is sacrificed and voids are easily generated in the package as the filling ratio of the inorganic filler increases. In addition, in order to prevent peeling at the interface between the plated portion and the epoxy resin composition, a method has been proposed in which various coupling agents such as aminosilane and mercaptosilane are added to achieve both fluidity and solder resistance (for example, However, even with this method, a sufficiently good epoxy resin composition for encapsulating a semiconductor could not be obtained.
[0004]
[Patent Document 1]
JP-A 64-65116 (pages 2 to 7)
[Patent Document 2]
Japanese Patent Laid-Open No. 9-255852 (pages 2 to 7)
[0005]
[Problems to be solved by the invention]
The present invention provides an epoxy resin composition for semiconductor encapsulation excellent in fluidity and solder resistance, and a semiconductor device using the same.
[0006]
[Means for Solving the Problems]
The present invention
[1] (A) epoxy resin, (B) phenol resin, (C) curing accelerator, (D) inorganic filler, (E) silane coupling agent represented by general formula (1), and (F) An epoxy resin composition for semiconductor encapsulation, comprising a thiazoline compound as an essential component;
[Chemical 3]
[0007]
[2] (E) Epoxy resin for semiconductor encapsulation according to item [1 ] , wherein the structure of the silane coupling agent represented by the general formula (1) is a silane coupling agent represented by the general formula (2) Composition,
[Formula 4]
[3] A semiconductor device comprising a semiconductor element sealed using the epoxy resin composition for semiconductor sealing according to the item [1] or [2] ,
It is.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The epoxy resin used in the present invention refers to monomers, oligomers, and polymers in general having two or more epoxy groups in one molecule, and the molecular weight and molecular structure are not particularly limited. For example, biphenyl type epoxy resin, bisphenol Type epoxy resin, stilbene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenolmethane type epoxy resin, alkyl-modified triphenolmethane type epoxy resin, triazine nucleus-containing epoxy resin, dicyclopentadiene modified phenol type epoxy Examples thereof include resins, phenol aralkyl type epoxy resins (having a phenylene skeleton, a biphenylene skeleton, etc.), and these may be used alone or in combination.
[0009]
The phenol resin used in the present invention includes monomers, oligomers, and polymers in general having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited. For example, phenol novolak resin, cresol Examples include novolak resins, dicyclopentadiene-modified phenol resins, terpene-modified phenol resins, triphenolmethane type resins, phenol aralkyl resins (having a phenylene skeleton, biphenylene skeleton, etc.), and these may be used alone or in combination. Absent.
[0010]
As a compounding quantity of an epoxy resin and a phenol resin, it is preferable that the ratio of the number of epoxy groups of all epoxy resins and the number of phenolic hydroxyl groups of all phenol resins is 0.8 to 1.3. There is a possibility that the curability of the composition is lowered, the glass transition temperature of the cured product is lowered, and the moisture resistance reliability is lowered.
[0011]
As a hardening accelerator used for this invention, what is necessary is just to accelerate | stimulate the hardening reaction of an epoxy group and a phenolic hydroxyl group, and what is generally used for a sealing material can be used. Examples thereof include 1,8-diazabicyclo (5,4,0) undecene-7, triphenylphosphine, 2-methylimidazole, tetraphenylphosphonium / tetraphenylborate and the like, and these may be used alone or in combination. Absent.
[0012]
As an inorganic filler used for this invention, what is generally used for the epoxy resin composition for semiconductor sealing can be used. Examples thereof include fused silica, crystalline silica, talc, alumina, silicon nitride and the like, and the most preferably used is spherical fused silica. These inorganic fillers may be used alone or in combination. Although the compounding quantity of an inorganic filler is not specifically limited, 78 to 96 weight% is preferable in all the epoxy resin compositions. If the lower limit is not reached, sufficient solder resistance may not be obtained, and if the upper limit is exceeded, sufficient fluidity may not be obtained.
[0013]
In the present invention, the silane coupling agent represented by the general formula (1) is essential, and when the silane coupling agent represented by the general formula (2) is used, fluidity and solder resistance are improved. The effect is large and preferable. The silane coupling agent represented by the general formula (1) may be used alone or in combination of two or more. Moreover, although a compounding quantity is not specifically limited, 0.01 to 3 weight% is desirable in all the epoxy resin compositions, More preferably, it is 0.05 to 1 weight%. If the lower limit is not reached, sufficient fluidity may not be obtained, and if the upper limit is exceeded, curability may be reduced.
[0014]
In the present invention, a compound containing at least one S atom and one N atom in each molecule is essential, and the molecular weight and molecular structure are not particularly limited, but the compound has a S—C—N structure in the compound. It is preferable because the effect of adhesion with the plated portion is increased. Examples of such compounds include thiazoline and thiazole. Among these compounds, thiazoline compounds are more preferable because of their high adhesion strength. A compound containing one or more each of S and N atoms in one molecule may be used alone or in combination of two or more. Moreover, the compounding quantity of the compound which contains one or more each of S atom and N atom in 1 molecule is not specifically limited, However, 0.01-3 weight% is desirable in all the epoxy resin compositions, More preferably, it is 0.05-. 1% by weight. If the lower limit is not reached, sufficient adhesion to the plated portion may not be obtained, and if the upper limit is exceeded, the curability may be lowered.
[0015]
In the present invention, it is essential to use the silane coupling agent represented by the general formula (1) and the compound containing one or more S atoms and N atoms in one molecule, and only one of them is blended. However, fluidity and solder resistance are not sufficient.
[0016]
(A) epoxy resin, (B) phenol resin, (C) curing accelerator, (D) inorganic filler, (E) silane coupling agent represented by general formula (1), and (F) in one molecule The epoxy resin composition of the present invention comprising a compound containing at least one S atom and at least one N atom as an essential component is represented by an epoxy resin, a phenol resin, a curing accelerator, an inorganic filler, and the general formula (1). A silane coupling agent and a compound containing at least one S atom and one N atom in the molecule are essential components, and in addition to this, aminosilanes and epoxysilanes other than those represented by the general formula (1) as necessary Silane coupling agents such as mercaptosilane, alkyl silane, ureido silane, vinyl silane, titanate coupling agent, aluminum coupling agent, aluminum / zirconium coupling agent, etc. Coloring agents such as pulling agents, carbon black, release agents such as natural wax and synthetic wax, and low stress additives such as rubber, brominated epoxy resins and antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, Additives such as flame retardants such as zinc molybdate and phosphazene may be appropriately blended.
[0017]
The epoxy resin composition of the present invention can be obtained by mixing the raw materials sufficiently uniformly using a mixer or the like, then melt-kneading with a hot roll or a kneader, cooling and pulverizing.
The epoxy resin composition of the present invention is used to encapsulate various electronic components such as semiconductor elements, and to manufacture semiconductor devices by conventional molding methods such as transfer molding, compression molding, and injection molding. do it.
[0018]
【Example】
Examples of the present invention are shown below, but the present invention is not limited thereto. The blending ratio is parts by weight.
In addition, it shows below about the coupling agent used by the Example and the comparative example, and the compound which each contains one or more S atoms and N atoms in 1 molecule.
Coupling agent 1: Coupling agent represented by formula (3) (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-573)
[Chemical formula 5]
[0019]
Coupling agent 2: Coupling agent represented by formula (4) (Shin-Etsu Chemical Co., Ltd., X12-806)
[Chemical 6]
[0020]
Coupling agent 3: Coupling agent represented by formula (5) (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403)
[Chemical 7]
[0021]
Coupling agent 4: Coupling agent represented by formula (6) (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-803)
[Chemical 8]
[0022]
Coupling agent 5: Coupling agent represented by formula (7) (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903)
[Chemical 9]
[0023]
S, N-containing compound 1: compound represented by formula (8) (Kanto Chemical Co., Ltd., primary reagent)
[Chemical Formula 10]
[0024]
S, N-containing compound 2: Compound represented by formula (9) (Kanto Chemical, first grade reagent)
Embedded image
[0026]
Example 1
Epoxy resin 1: Epoxy resin mainly composed of formula (11) (manufactured by Japan Epoxy Resin Co., Ltd., YX-4000, epoxy equivalent 190 g / eq, melting point 105 ° C., hereinafter referred to as E-1) 49 parts by weight 13]
[0027]
Phenolic resin 2: phenolic resin represented by formula (12) (Mitsui Chemicals, XLC-LL, hydroxyl group equivalent 165 g / eq, softening point 79 ° C., hereinafter referred to as H-1) 42 parts by weight
[0028]
1,8-diazabicyclo (5,4,0) undecene-7 (hereinafter referred to as DBU) 5 parts by weight fused spherical silica (average particle size 21 μm) 890 parts by weight coupling agent 1 3 parts by weight S, N-containing compound 1 3 Part by weight Carbon black 3 parts by weight Carnauba wax 5 parts by weight were mixed in a mixer, kneaded at 95 ° C. for 8 minutes using a hot roll, cooled and ground to obtain an epoxy resin composition. The obtained epoxy resin composition was evaluated by the following methods. The results are shown in Table 1.
[0029]
Evaluation Method Spiral Flow: Using a mold for spiral flow measurement according to EMMI-1-66, measurement was performed at a mold temperature of 175 ° C., a pressure of 6.9 MPa, and a curing time of 120 seconds. The unit is cm.
Adhesion strength: Using a transfer molding machine, a 2 mm × 2 mm × 2 mm adhesion strength test piece was molded on a lead frame under conditions of a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, and a curing time of 120 seconds. Two types of lead frames were used: a silver plated copper frame (frame 1) and a gold plated NiPd alloy frame (frame 2). Thereafter, the shear strength between the cured product of the epoxy resin composition and the frame was measured using an automatic shear strength measuring apparatus (manufactured by DAGE, PC2400). The unit is N / mm 2 .
Solder crack resistance: Molding 80pQFP (NiPd alloy frame gold-plated, chip size 6.0mm x 6.0mm) at a molding temperature of 175 ° C, a pressure of 8.3MPa, and a curing time of 120 seconds using a low-pressure transfer molding machine. Then, after heat treatment at 175 ° C. for 8 hours as an after bake, a humidification treatment was performed at 85 ° C. and a relative humidity of 85% for 120 hours, followed by an IR reflow treatment at 260 ° C. Peeling and cracks inside the package were confirmed with an ultrasonic flaw detector. The number of defective packages among the 10 packages is shown.
[0030]
Example 2-6, Comparative Examples 1-5
According to the composition of Table 1, an epoxy resin composition was obtained in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The results are shown in Table 1.
The raw materials used other than Example 1 are shown below.
Epoxy resin 2: Epoxy resin represented by formula (13) (manufactured by Nippon Kayaku Co., Ltd., NC3000P, softening point 58 ° C., epoxy equivalent 273, hereinafter referred to as E-2)
Embedded image
[0031]
Phenol resin 2: Phenol resin represented by formula (14) (Maywa Kasei Co., Ltd., MEH-7851SS, softening point 107 ° C., hydroxyl equivalent 204, hereinafter referred to as H-2)
Embedded image
[0032]
[Table 1]
[0033]
【The invention's effect】
According to the present invention, an epoxy resin composition for semiconductor encapsulation and a semiconductor device excellent in fluidity and solder resistance can be obtained.
Claims (3)
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