TWI754721B - 液狀環氧樹脂封止材及半導體裝置 - Google Patents
液狀環氧樹脂封止材及半導體裝置 Download PDFInfo
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- TWI754721B TWI754721B TW107105135A TW107105135A TWI754721B TW I754721 B TWI754721 B TW I754721B TW 107105135 A TW107105135 A TW 107105135A TW 107105135 A TW107105135 A TW 107105135A TW I754721 B TWI754721 B TW I754721B
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- epoxy resin
- liquid epoxy
- sealing material
- resin sealing
- antioxidant
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- 239000004850 liquid epoxy resins (LERs) Substances 0.000 title claims abstract description 76
- 239000003566 sealing material Substances 0.000 title claims abstract description 63
- 239000004065 semiconductor Substances 0.000 title claims abstract description 26
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 45
- 150000001412 amines Chemical class 0.000 claims abstract description 39
- 239000004848 polyfunctional curative Substances 0.000 claims abstract description 36
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 30
- 239000011256 inorganic filler Substances 0.000 claims abstract description 30
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 30
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- RQEOBXYYEPMCPJ-UHFFFAOYSA-N 4,6-diethyl-2-methylbenzene-1,3-diamine Chemical compound CCC1=CC(CC)=C(N)C(C)=C1N RQEOBXYYEPMCPJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 15
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- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
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- 238000003860 storage Methods 0.000 description 19
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- 238000002156 mixing Methods 0.000 description 10
- -1 peroxy radicals Chemical class 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
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- 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 7
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
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- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- CXXSQMDHHYTRKY-UHFFFAOYSA-N 4-amino-2,3,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1=C(O)C(CC2OC2)=C(CC2OC2)C(N)=C1CC1CO1 CXXSQMDHHYTRKY-UHFFFAOYSA-N 0.000 description 1
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- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- MFIBZDZRPYQXOM-UHFFFAOYSA-N [dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silyl]oxy-dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound C1OC1COCCC[Si](C)(C)O[Si](C)(C)CCCOCC1CO1 MFIBZDZRPYQXOM-UHFFFAOYSA-N 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- IPHKNOWSJUHYSE-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) 3-methylcyclohexane-1,2-dicarboxylate Chemical compound CC1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 IPHKNOWSJUHYSE-UHFFFAOYSA-N 0.000 description 1
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 description 1
- HGXHJQLDZPXEOG-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,4-dicarboxylate Chemical compound C1CC(C(=O)OCC2OC2)CCC1C(=O)OCC1CO1 HGXHJQLDZPXEOG-UHFFFAOYSA-N 0.000 description 1
- LMMDJMWIHPEQSJ-UHFFFAOYSA-N bis[(3-methyl-7-oxabicyclo[4.1.0]heptan-4-yl)methyl] hexanedioate Chemical compound C1C2OC2CC(C)C1COC(=O)CCCCC(=O)OCC1CC2OC2CC1C LMMDJMWIHPEQSJ-UHFFFAOYSA-N 0.000 description 1
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- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- AVKNGPAMCBSNSO-UHFFFAOYSA-N cyclohexylmethanamine Chemical compound NCC1CCCCC1 AVKNGPAMCBSNSO-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KEZAKPHSMMMPQD-UHFFFAOYSA-N methylsulfanyl-(2-methylsulfanylphenyl)methanediamine Chemical compound CSC1=CC=CC=C1C(N)(N)SC KEZAKPHSMMMPQD-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 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
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- PORDPJGBVVCHKZ-UHFFFAOYSA-N spiro[4,7,10-trioxatricyclo[7.1.0.03,5]decane-2,1'-cyclohexane] Chemical compound C12(CCCCC1)C1C(COCC3C2O3)O1 PORDPJGBVVCHKZ-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
-
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Abstract
本發明之課題係提供可抑制底部填充劑硬化物於高溫有氧下放置時發生之圓角裂紋(fillet crack)的液狀環氧樹脂封止材及使用其之半導體裝置。 解決手段係液狀環氧樹脂封止材及使用其之半導體裝置,該液狀環氧樹脂封止材含有(A)液狀環氧樹脂,(B)胺硬化劑,(C)無機填充劑及(D)下述式所示之抗氧化劑,相對於(A)液狀環氧樹脂及(B)胺硬化劑之合計100質量份,含0.5~10質量份之前述(D)抗氧化劑。
Description
[0001] 本發明有關液狀環氧樹脂封止材及半導體裝置。
[0002] 隨著電子機器之小型化、輕量化及高性能化,半導體之安裝形態亦自金屬線黏合型變化至覆晶型。 覆晶型之半導體裝置具有透過凸塊電極將基板上之電極部與半導體元件連接之構造。該構造之半導體裝置於施加溫度循環等之熱附加時,因環氧樹脂等之有機材料製基板與半導體元件之熱膨脹係數差,而對凸塊電極施加應力。因此,有於凸塊電極發生龜裂等缺陷之問題。為了抑制該缺陷發生,已廣泛進行使用稱為底部填料之半導體密封材,將半導體元件與基板之間的間隙密封。如此,藉由使兩者相互固定,可提高耐熱循環性。 [0003] 作為底部填充材之供給方法首先將半導體元件與基板上之電極部連接。隨後,沿著半導體元件外周塗佈(分佈)底部填充材。此時,一般採用利用毛細管現象,於兩者之間隙注入底部填充材之稱為毛細管流動之手法。底部填充材之注入後,藉由使該底部填充材加熱硬化而使兩者之接著部位補強。 [0004] 底部填充材被要求優異特性例如注入性、接著性、硬化性及保存安定性。且,以底部填充材密封之部位亦被要求優異特性例如耐濕性及耐熱循環性。 [0005] 為了滿足上述要求,作為底部填充材使用之液狀封止材廣泛使用以環氧樹脂為主劑之液狀封止材。 為了提高由液狀封止材密封之部位之耐濕性及耐熱循環性,尤其是耐熱循環性,已知有藉由於液狀封止材中添加由如氧化矽填充劑之無機物質所成之填充材(以下稱為「填充劑」)。藉此,有效地進行環氧樹脂等之有機材料製基板與半導體元件之熱膨脹係數差的控制,及可補強凸塊電極(參考專利文獻1)。 [先前技術文獻] [專利文獻] [0006] [專利文獻1]日本特開平10-130374號公報
[0007] 如上述,提高由液狀封止材密封之部位之耐熱循環性為課題。耐熱循環性不充分時,會發生於半導體元件與基板上之電極部的藉面產生龜裂之問題。 本發明人等發現即使提高耐熱循環性,底部填充材硬化物於100℃以上之高溫有氧下放置時,觀察到與耐熱循環試驗時不同之特異圓角裂紋(fillet crack)。該圓角裂紋自底部填充材硬化物表面朝厚度方向行進。發生此圓角裂紋時,發生損及作為底部填充材之功能的問題。
本揭示之液狀環氧樹脂封止材,為解決上述先前技術之問題,目的在於提供可抑制底部填充劑硬化物於高溫有氧下放置時發生之圓角裂紋的底部填充用之液狀環氧樹脂封止材。
上述圓角裂紋係於高溫有氧化發生。但,即使保持於相同溫度而於氮氣下則未發生。因此推測有氧熱劣化為圓角裂紋發生之原因。
本發明人等,為了抑制因有氧熱劣化所致之圓角裂紋發生,而嘗試添加受阻酚系抗氧化劑。選擇受阻酚系抗氧化劑之理由如以下記載。
受阻酚系抗氧化劑分類為一次抗氧化劑。藉由自動氧化而直接作用於生成之自由基,而顯示優異之抗氧化能。作為一次抗氧化劑,亦可使用受阻胺系抗氧化劑。然而,受阻胺系抗氧化劑有著色問題。另一方面,被區分為二次抗氧化劑之磷系抗氧化劑及硫系抗氧化劑具有過氧化物分解能。此係作用於因一次抗氧化劑而自自由基轉換而成之過氧化物。因此,該等抗氧化劑大多與一次抗氧化劑併用。
有氧熱劣化反應係進行自由基連鎖反應。該連鎖反應係由其反應初期階段產生之自由基R.生成反應活性過氧自由基ROO.。受阻酚系抗氧化劑係如下述式所
示,有捕捉過氧自由基,而轉換為準安定氫過氧化物ROOH之作用。
本發明人等經積極檢討之結果,發現為了抑制因有氧熱劣化所致之圓角裂紋發生,有必要添加特定構造之受阻酚系抗氧化劑。
本揭示之液狀環氧樹脂封止材係基於上述見解而達成。依據本揭示,提供液狀環氧樹脂封止材,其含有(A)液狀環氧樹脂,(B)胺硬化劑,(C)無機填充劑及(D)下述式所示之抗氧化劑。該液狀環氧樹脂封止材相對於(A)液狀環氧樹脂及(B)胺硬化劑及(D)抗氧化劑之合計100質量份,含0.5~10質量份之前述(D)抗氧化劑。
本揭示之液狀環氧樹脂封止材中,(B)胺硬化劑較好包含3,5-二乙基甲苯-2,4-二胺及3,5-二乙基甲苯-2,6-二胺。
[0013] 本揭示之液狀環氧樹脂封止材中,(C)無機填充劑之添加量,較好相對於液狀環氧樹脂封止材總量為55~70質量份。又,較好(A)液狀環氧樹脂與(B)胺硬化劑之當量比為0.7~1.2。 [0014] 又,依據本揭示,提供半導體裝置,其具有使用本揭示之液狀環氧樹脂封止材封止之覆晶型半導體元件。
[0015] 本揭示之液狀環氧樹脂封止材可抑制因有氧熱劣化所致之圓角裂紋發生。 且,本揭示之液狀環氧樹脂封止材於室溫具有良好之保存安定性。
[0016] 以下,針對本揭示詳細說明。 本揭示之液狀環氧樹脂封止材含有以下所示之(A)~(D)成分。 [0017] (A)液狀環氧樹脂 (A)成分之液狀環氧樹脂係成為本揭示之液狀環氧樹脂封止材的主劑之成分。 本揭示中,所謂液狀環氧樹脂意指於常溫為液狀之環氧樹脂。 作為本揭示之液狀環氧樹脂之例,可舉例為平均分子量約400以下之雙酚A型環氧樹脂;如對-縮水甘油氧基苯基二甲基參-雙酚A縮水甘油醚之分支狀多官能雙酚A型環氧樹脂;雙酚F型環氧樹脂;平均分子量約570以下之酚酚醛清漆型環氧樹脂;如乙烯基(3,4-環己烯)二氧化物、3,4-環氧基環己基羧酸(3,4-環氧基環己基)甲酯、己二酸雙(3,4-環氧基-6-甲基環己基甲基)酯、2-(3,4-環氧基環己基)5,1-螺(3,4-環氧基環己基)-間-二噁烷等之脂環式環氧樹脂;如3,3',5,5'-四甲基-4,4'-二縮水甘油氧基聯苯之聯苯型環氧樹脂;如六氫鄰苯二甲酸二縮水甘油酯、3-甲基六氫鄰苯二甲酸二縮水甘油酯、六氫對苯二甲酸二縮水甘油酯之縮水甘油酯型環氧樹脂;如二縮水甘油基苯胺、二縮水甘油基甲苯胺、三縮水甘油基-對-胺基酚、四縮水甘油基-間-二甲苯二胺、四縮水甘油基雙(胺基甲基)環己烷之縮水甘油胺型環氧樹脂;以及如1,3-二縮水甘油基-5-甲基-5-乙基乙內醯脲之乙內醯脲型環氧樹脂;含萘環之環氧樹脂。且,亦可使用如1,3-雙(3-縮水甘油氧基丙基)-1,1,3,3-四甲基二矽氧烷之具有矽氧骨架之環氧樹脂。作為進一步之例,可舉例為如(聚)乙二醇二縮水甘油醚、(聚)丙二醇二縮水甘油醚、丁二醇二縮水甘油醚、新戊二醇二縮水甘油醚、環己烷二甲醇二縮水甘油醚之二環氧化合物;及如三羥甲基丙烷三縮水甘油醚、甘油三縮水甘油醚之三環氧化合物。 該等液狀環氧樹脂中,較好使用液狀雙酚型環氧樹脂、液狀胺基酚型環氧樹脂、矽氧改質環氧樹脂、萘型環氧樹脂。進而更好使用液狀雙酚A型環氧樹脂、液狀雙酚F型環氧樹脂、對-胺基酚型液狀環氧樹脂、1,3-雙(3-縮水甘油氧基丙基)四甲基二矽氧烷。 作為(A)成分,可使用單獨之液狀環氧樹脂。或者,亦可並用2種以上之液狀環氧樹脂。 且,即使常溫為固體之環氧樹脂,若藉由該樹脂與液狀環氧樹脂併用而可形成液狀混合物者,則亦可使用。 [0018] (B)胺硬化劑 本揭示之液狀環氧樹脂封止材中,作為環氧樹脂之硬化劑係使用胺硬化劑。其理由為胺硬化劑之耐濕性及耐熱循環性優異。 胺硬化劑並未特別限定。所用之胺硬化劑可自習知胺硬化劑廣泛選擇。 作為胺硬化劑之具體例舉例為三伸乙基四胺、四伸乙基五胺、間-二甲苯二胺、三甲基六亞甲基二胺、2-甲基五亞甲基二胺等之脂肪族多胺、異佛酮二胺、1,3-雙胺基甲基環己烷、雙(4-胺基環己基)甲烷、降冰片烯二胺、1,2-二胺基環己烷等之脂環式多胺、N-胺基乙基哌啶、1,4-雙(2-胺基-2-甲基丙基)哌啶等之哌啶型多胺、3,5-二乙基甲苯-2,4-二胺及3,5-二乙基甲苯-2,6-二胺等之二乙基甲苯二胺、二甲硫基甲苯二胺、4,4'-二胺基-3,3'-二乙基二苯基甲烷、雙(甲硫基)甲苯二胺、二胺基二苯基甲烷、間-苯二胺、二胺基二苯基碸、二乙基甲苯二胺、三亞甲基雙(4-胺基苯甲酸酯)、聚氧化四亞甲基-二-對胺基苯甲酸酯等之芳香族多胺類。且,作為市售品之例舉例為T-12(商品名,三洋化成工業製)(胺當量116)。 [0019] 該等胺硬化劑中,較好為包含3,5-二乙基甲苯-2,4-二胺或3,5-二乙基甲苯-2,6-二胺之胺硬化劑。若為該等胺硬化劑,則可將所添加之液狀樹脂封止材之玻璃轉移點(Tg)設定為較高,再者,可減低液狀樹脂封止材黏度。 [0020] 作為(B)成分可使用單獨之胺硬化劑。或者,亦可併用2種以上之胺硬化劑。 [0021] 本揭示之液狀環氧樹脂封止材中,(B)成分之胺硬化劑之摻合比例並未特別限定。例如摻合比例相對於(A)成分之環氧樹脂之環氧基1當量,較好為0.7~1.2當量,更好為0.7~1.1當量。 [0022] (C):無機填充劑 (C)成分之無機填充劑係基於提高經封止部位之耐濕性及耐熱循環性,尤其是耐熱循環性之目的而添加於液狀環氧樹脂封止材。藉由添加無機填充劑,而提高耐熱循環性。此係因為藉由降低線膨脹係數,而可抑制熱循環所致之液狀環氧樹脂封止材硬化物之膨脹或收縮。 [0023] (C)成分之無機填充劑只要具有藉由添加而降低線膨脹係數之效果,則未特別限定。可使用各種無機填充劑。作為具體例舉例為非晶質氧化矽、結晶性氧化矽、氧化鋁、氮化硼、氮化鋁及氮化矽。 該等中,較好為氧化矽,特別是非晶質之球狀氧化矽。該等氧化矽於將本揭示之液狀環氧樹脂封止材使用作為底部填充材時,可獲得優異流動性,進而可減低硬化物之線膨脹係數。 又,本文所稱之氧化矽亦可為具有源自製造原料的有機基例如甲基或乙基等之烷基的氧化矽。 非晶質之球狀氧化矽可藉由熔融法、燃燒法或溶凝膠法等之習知製造方法獲得。可根據期望粒度、雜質含量及表面狀態等之特性,適當選擇其製造方法。 且,作為無機填充劑使用之氧化矽亦可使用日本特開2007-197655號公報中記載之製造方法獲得之含氧化矽組成物。 [0024] 又,無機填充劑亦可藉矽烷偶合劑等施以表面處理。使用施以表面處理之無機填充劑時,可期待防止無機填充劑凝集之效果。藉此,可期待提高本揭示之液狀環氧樹脂封止材之保存安定性。 [0025] 作為(C)成分之無機填充劑的平均粒徑較好為0.1~10μm,更好為0.2~2μm。 此處,無機填充劑之形狀並未特別限定。例如亦可使用球狀、不定形及鱗片狀之任一形態的無機填充劑。又,無機填充劑之形狀為球狀以外時,無機填充劑之平均粒徑意指該無機填充劑之平均最大徑。 [0026] (C)成分之無機填充劑之含量,相對於環氧樹脂封止材總量,亦即所有成分之合計100質量份,較好為55~70質量份。含量為55~70質量份時,將液狀環氧樹脂封止材作為底部填充劑使用時,可減低液狀環氧樹脂封止材之線膨脹係數,且可避免注入性惡化。更好之含量為60~70質量份。 [0027] (D):下述式表示之抗氧化劑如上述,有氧熱劣化反應易以自由基連鎖反應進行。自反應初期階段產生之自由基R.生成反應活性過氧自由基ROO.。受阻酚系抗氧化劑具有捕捉該過氧自由基,而將其轉換為準安定氫過氧化物ROOH之作用。 本發明人等發現藉由添加受阻酚系抗氧化劑中以上述式表示之抗氧化劑,可有效地抑制因有氧熱劣化之圓角裂紋發生。此優異之抑制圓角裂紋發生之效果可藉由後述實施例等中,與含其他構造之受阻酚系抗氧化劑的液狀環氧樹脂組成物進行比較而確認。 藉由添加上述式所示之抗氧化劑,而可抑制因有氧熱劣化之圓角裂紋發生之理由尚不清楚。但作為其理由可推測以下機制。
上述式所示之抗氧化劑係於1個碳原子鍵結4個受阻酚基。因此,推測捕捉過氧自由基,並轉變為準安定之氫過氧化物ROOH之作用高。其結果,抑制有氧熱劣化進行之效果高。藉此,推測可抑制圓角裂紋發生。
本揭示之液狀環氧樹脂封止材,相對於(A)液狀環氧樹脂及(B)胺硬化劑及(D)抗氧化劑之合計100質量份,含0.5~10質量份之(D)抗氧化劑。
(D)抗氧化劑未達0.5質量份時,未充分抑制因有氧熱劣化之圓角裂紋發生。(D)抗氧化劑超過10質量份時,由於常溫之保存安定性降低,故可用壽命變短。
(D)抗氧化劑含量較好為0.5~5質量份。
本揭示之液狀環氧樹脂封止材中,亦可根據需要進而含有上述(A)~(D)成分以外之成分。
如此,作為可摻合成分之具體例可舉例為偶合劑、調平劑、硬化促進劑、表面改質劑、消泡劑、離子捕捉劑、彈性體及碳等之著色劑。各摻合劑種類及摻合量係如常用方法。
本揭示之液狀環氧樹脂封止材之調製係將上述(A)~(D)成分及根據需要摻合之其他摻合劑混合。其次,藉由攪拌所得混合物,而調製液狀環氧樹脂封止材。混合
攪拌時可使用輥磨機。當然,混合攪拌手段不限定於輥磨機。(A)成分之環氧樹脂為固體時,較好混合藉由加熱等而液狀化或流動化之環氧樹脂。
上述各成分可同時混合。但,亦可先混合成分之一部分,其餘成分於隨後混合等之加入變更。
其次針對本揭示之液狀環氧樹脂封止材特性加以描述。
本揭示之液狀環氧樹脂封止材抑制了因有氧熱劣化所致之圓角裂紋之發生。以後述順序測定之高溫放置試驗時之裂紋發生數較好為20條以下,更好為15條以下。
本揭示之液狀環氧樹脂封止材由於於室溫具有良好保存安定性,故使用壽命優異。以後述實施例中記載之順序測定之增黏率較好未達2倍,更好為1.8倍以下。
因該等特性,本揭示之液狀環氧樹脂封止材可較好地使用作為底部填充劑。本揭示之液狀環氧樹脂封止材亦可使用於毛細管型之底部填充劑(以下稱為"毛細管底部填充劑")及先塗佈型之底部填充劑之任一者。
又,本揭示之液狀環氧樹脂封止材亦可使用於半導體裝置之製造時使用之接著劑。
其次針對本揭示之液狀環氧樹脂封止材之使用方法提及使用作為毛細管底部填充劑為例加以說明。
本揭示之液狀環氧樹脂封止材使用作為毛細管底部填充劑時,藉以下順序於基板與半導體元件之間之間隙填充本揭示之液狀環氧樹脂封止材。 邊將基板於例如70~130℃加熱,於半導體元件之一端塗佈本揭示之液狀環氧樹脂封止材。如此,藉由毛細管現象,於基板與半導體元件之間之間隙填充本揭示之液狀環氧樹脂封止材。此時,為使填充本揭示之液狀環氧樹脂封止材需要之時間縮短,亦可將基板傾斜。或者,亦可於間隙內外產生壓力差。 於該間隙填充本揭示之液狀環氧樹脂封止材後,將基板於特定溫度加熱特定時間,具體為於80~200℃加熱0.2~6小時,使液狀環氧樹脂封止材加熱硬化,而封止該間隙。 [0036] 本揭示之半導體裝置係藉由使用本揭示之液狀環氧樹脂封止材作為底部填充劑,以上述順序將封止部位亦即基板與半導體元件之間的間隙予以封止。此處進行封止之半導體元件並未特別限定。若舉例則為「積體電路、大型積體電路、電晶體、閘流體、二極體及電容器」。 [實施例] [0037] 以下,藉由實施例詳細說明本揭示。但本揭示不限定於此。 [0038] (實施例1~12、比較例1~4) 以下述表1所示之摻合比例摻合之原料以輥磨機混練。藉此,調製實施例1~12及比較例1~4之液狀環氧樹脂封止材。又,關於表中各組成之數值表示質量份。 [0039] (A)液狀環氧樹脂 環氧樹脂A-1:雙酚F型液狀環氧樹脂,製品名YDF8170,新日鐵化學股份有限公司製,環氧當量158g/eq 環氧樹脂A-2:胺基雙酚型液狀環氧樹脂,製品名jER630D,三菱化學股份有限公司製,環氧當量94g/eq (B)胺硬化劑 胺硬化劑B-1:含有3,5-二乙基甲苯-2,4-二胺及3,5-二乙基甲苯-2,6-二胺,製品名ETHACURE 100,ALBEMARLE Co., Ltd.製 胺硬化劑B-2:4,4’-二胺基-3,3'-二乙基二苯基甲烷,製品名KAYAHARD A-A(HDAA),日本化藥股份有限公司製 胺硬化劑B-3:二甲硫基甲苯二胺(包含改質芳香族胺),製品名EH105L,ADEKA股份有限公司製 (C)無機填充劑 無機填充劑C-1:矽烷偶合劑(3-縮水甘油氧基丙基三甲氧基矽烷)表面處理氧化矽填充劑(平均粒徑0.5μm),製品名SE2200-SEE,ADMATECHS股份有限公司製
無機填充劑C-2:矽烷偶合劑(3-縮水甘油氧基丙基三甲氧基矽烷)表面處理氧化矽填充劑(平均粒徑1.5μm),製品名SE5200-SEE,ADMATECHS股份有限公司製
抗氧化劑D-1:受阻酚系抗氧化劑,製品名IRGANOX1010
(下述式),BASF公司製
抗氧化劑D-2:受阻酚系抗氧化劑,製品名IRGANOX1035
(下述式),BASF公司製
抗氧化劑D-3:受阻酚系抗氧化劑,製品名IRGANOX1076
(下述式),BASF公司製
使用布魯克菲爾德公司製旋轉黏度計HBDV-1(使用轉子SC4-14)於50rpm測定由上述順序調製之液狀環氧樹脂封止材於25℃之黏度(Pa.s)。所得測定值定義為初期黏度。其次,藉以下順序求出成為樹脂組成物之使用壽命指標之增黏率(1天保存後增黏率)。首先,將經調製之樹脂組成物於密閉容器中,於25℃、濕度50%之環境下保存1天。以相同順序測定於該時點之該樹脂組成物黏度。算出所得黏度相對於剛調製後之黏度的倍率。算出被率定義為增黏率。
使用具有PI保護層晶粒(Passivation die)(晶粒尺寸10mm×10mm厚×0.725mm)、Sn/3Ag/0.5Cu凸塊(凸塊間距150μm,凸塊數3721)之測試元件群(TEG)。此處,PI保護層晶粒係形成於塗佈有阻焊劑(PSR-4000 AUS703)之高耐熱(高-Tg)FR-4基板(基板尺寸30mm×30mm厚×0.8mm)上。以上述順序獲得之液狀環氧樹脂封止材注入上述TEG之晶粒部分。藉由於150℃加入120分鐘,使液狀環氧樹脂封止材硬化。該TEG於保持於大氣下、190℃之乾燥機內放置1000小時。隨後,計算於圓角發生之裂紋數。 [0042][0043][0044] 實施例1~12之液狀環氧樹脂封止材的高溫放置試驗後之裂紋發生數為20條以下。因有氧熱劣化所致之圓角裂紋發生受到抑制。且,1天保存後增黏率未達2.0倍。於室溫之保存安定性良好。又,實施例2~5中,變更實施例1之抗氧化劑D-1之摻合比例。抗氧化劑D-1之摻合比例多時,高溫放置試驗後之裂紋發生數減少。然而,1天保存後增黏率上升。未摻合抗氧化劑D-1之比較例1中,高溫放置試驗後之裂紋發生數為29條。另一方面,摻合超過10質量份之抗氧化劑D-1的比較例2,1天保存後增黏率為2.0而較高。 使用具有與抗氧化劑D-1不同構造之受阻酚系抗氧化劑D-2及D-3之比較例3及4中,高溫放置試驗後之裂紋發生數高於未摻合抗氧化劑D-1之比較例。此推測係除了因有氧熱劣化所致之圓角裂紋發生的抑制效果低以外,高溫放置實驗中發生之抗氧化劑D-2及D-3之熱分解產物造成不良影響。 實施例6及7中,係變更實施例3之胺硬化劑B-1之環氧當量。並未見到胺硬化劑B-1之環氧當量變更對高溫放置試驗後之裂紋發生數及1天保存後增黏率造成影響。 實施例8及9中,係變更實施例3之無機填充劑C-1之摻合比例。實施例8中,無機填充劑C-1之摻合比例低於實施例1。該實施例8中,高溫放置試驗後之裂紋發生數增加。此推測係高溫放置時因樹脂硬化物收縮所致之影響。 實施例10及11中,係變更實施例4之胺硬化劑種類。亦即實施例4中,使用胺硬化劑B-1,相對地實施例10中,併用胺硬化劑B-1及B-2。同樣,實施例11中,併用胺硬化劑B-2及B-3。並未見到胺硬化劑之差異對高溫放置試驗後之裂紋發生數及1天保存後增黏率造成影響。
實施例12中,係變更實施例4之無機填充劑之平均粒徑。具體而言,相對於使用平均粒徑0.5μm之氧化矽填充劑(無機填充劑C-1)的實施例4,實施例12中使用平均粒徑1.5μm之氧化矽填充劑(無機填充劑C-2)。並未見到無機填充劑之平均粒徑差異對高溫放置試驗後之裂紋發生數及1天保存後增黏率造成影響。
Claims (4)
- 如請求項1之液狀環氧樹脂封止材,其中前述(C)無機填充劑之添加量,相對於液狀環氧樹脂封止材總量為55~70質量份。
- 如請求項1或2之液狀環氧樹脂封止材,其中(A)液狀環氧樹脂與(B)胺硬化劑之當量比為0.7~1.2。
- 一種半導體裝置,其具有使用如請求項1~3中任一項之液狀環氧樹脂封止材封止之覆晶型半導體元件。
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