TW201842137A - 固化性有機聚矽氧烷組成物以及半導體裝置 - Google Patents

固化性有機聚矽氧烷組成物以及半導體裝置 Download PDF

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TW201842137A
TW201842137A TW107104333A TW107104333A TW201842137A TW 201842137 A TW201842137 A TW 201842137A TW 107104333 A TW107104333 A TW 107104333A TW 107104333 A TW107104333 A TW 107104333A TW 201842137 A TW201842137 A TW 201842137A
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organic polysiloxane
mass
composition
component
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TW107104333A
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TWI767988B (zh
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山崎亮介
西嶋一裕
飯村智浩
須藤学
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日商道康寧東麗股份有限公司
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
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    • C08K3/36—Silica
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Abstract

本發明提供一種對於半導體元件之接著性優異且形成之固化物中氣泡少之固化性有機聚矽氧烷組成物。 一種固化性有機聚矽氧烷組成物，其至少由下述(A)、(B)以及(C)構成；(A)一分子中具有至少2個烯基之有機聚矽氧烷；(B)以平均單元式：(R1 3SiO1/2)a(R1 2SiO2/2)b(R2SiO3/2)c(SiO4/2)d(式中，R1為相同或不同之不具有脂肪族不飽和碳鍵之一價烴基或者氫原子，其中，一分子中至少2個R1為氫原子，R2為不具有脂肪族不飽和鍵之一價烴基，a、b、c分別為滿足0<a<1、0<b<1、0
Figure TW201842137A_A0001
c<0.2、0<d<1、其中，0.6
Figure TW201842137A_A0002
a/d
Figure TW201842137A_A0003
1.5、1.5
Figure TW201842137A_A0004
b/d

Description

固化性有機聚矽氧烷組成物以及半導體裝置
本發明涉及一種固化性有機聚矽氧烷組成物以及藉由該組成物之固化物將半導體元件接著而成之半導體裝置。
具有光耦合器、發光二極體、固態成像元件等半導體元件之半導體裝置中，為接著該半導體元件使用有固化性有機聚矽氧烷組成物。作為此種固化性有機聚矽氧烷組成物，例如專利文獻1及2中提出有一種實質上由直鏈狀或環狀之含有烯基之有機聚矽氧烷、支鏈狀之含有烯基之有機聚矽氧烷、具有與分子鏈中之矽原子鍵結之氫原子之直鏈狀之有機聚矽氧烷、具有矽原子鍵結氫原子之支鏈狀之有機聚矽氧烷、具體而言，以平均單元式：[H(CH3)2SiO1/2]0.67(SiO4/2)0.33表示之有機聚矽氧烷樹脂或以平均單元式：[H(CH3)2SiO1/2]0.50[(CH3)3SiO1/2]0.17(SiO4/2)0.33表示之有機聚矽氧烷樹脂、以及矽氫化反應用催化劑構成之固化性有機聚矽氧烷組成物，專利文獻3中提出有一種由一分子中具有至少2個烯基之直鏈狀之有機聚矽氧烷、一分子中具有至少2個烯基之支鏈狀之有機聚矽氧烷、一分子中具有至少2個矽原子鍵結氫原子之支鏈狀之有機聚矽氧烷、具體而言，以平均單元式：[H(CH3)2SiO1/2]0.44(SiO4/2)0.56表示之有機聚矽氧烷樹脂、以平均單元式：[H(CH3)2SiO1/2]0.25[(CH3)3SiO1/2]0.25(SiO4/2)0.50表示之有機聚矽氧烷樹脂、或者以 平均單元式：[(CH3)3SiO1/2]0.20[H(CH3)SiO2/2]0.40(SiO4/2)0.40表示之有機聚矽氧烷樹脂以及矽氫化反應用催化劑構成之固化性有機聚矽氧烷組成物。
上述固化性有機聚矽氧烷組成物中，為調整可獲得之固化物之機械強度及硬度，配伍有具有矽原子鍵結氫原子之有機聚矽氧烷樹脂，但此種固化性有機聚矽氧烷組成物存有以下課題，即對於半導體元件之接著性不充分，此外，還會於該固化物中產生氣泡，使接著力降低。
〔習知技術文獻〕
〔專利文獻】〕
〔專利文獻1〕日本特開2012-012433號公報
〔專利文獻2〕日本特開2012-012434號公報
〔專利文獻3〕日本特開2016-155967號公報
本發明之目的在於，提供一種對於半導體元件之接著性優異且形成之固化物中氣泡少之固化性有機聚矽氧烷組成物。並且，本發明之另一目的在於，提供一種可靠性優異之半導體裝置。
本發明之固化性有機聚矽氧烷組成物至少由下述(A)、(B)以及(C)構成；(A)一分子中具有至少2個烯基之有機聚矽氧烷；(B)以平均單元式：(R1 3SiO1/2)a(R1 2SiO2/2)b(R2SiO3/2)c(SiO4/2)d (式中，R1為相同或不同之不具有脂肪族不飽和碳鍵之一價烴基或者氫原子，其中，一分子中至少2個R1為氫原子，R2為不具有脂肪族不飽和鍵之一價烴基，a、b、c分別為滿足0<a<1、0<b<1、0c<0.2、0<d<1，其中0.6a/d1.5、1.5b/d3並且a+b+c+d=1之數)表示之有機聚矽氧烷樹脂{相對於(A)成分中之烯基，(B)成分中之矽原子鍵結氫原子之莫耳比為0.5~5之量}；(C)矽氫化反應用催化劑(足以使本組成物固化之量)。
並且，本組成物優選相對於(A)~(C)成分之合計100質量份，還含有1~20質量份之(D)BET比表面積為20~200m2/g之發煙二氧化矽(fumed silica)。
並且，本組成物優選相對於(A)~(C)成分之合計100質量份，還含有0.001~5質量份之(E)矽氫化反應抑制劑。
並且，本組成物優選相對於(A)~(C)成分之合計100質量份，還含有0.01~10質量份之(F)接著促進劑。
並且，本組成物還可含有(G)以平均式：R3R4 2SiO(R4 2SiO)m(R4HSiO)nSiR4 2R3(式中，R3為相同或不同之不具有脂肪族不飽和碳鍵之一價烴基或者氫原子，R4為相同或不同之不具有脂肪族不飽和碳鍵之一價烴基，m為0~50之數、n為0~50之數，其中，n為0時，R3為氫原子)表示之有機聚矽氧烷，相對於(A)成分中之烯基，(G)成分中之矽原子鍵結氫原子之莫耳比最多為0.3。
此種本組成物優選為固化後形成JIS K 6253所規定之D型硬度計硬度為30~70之固化物者。
此外，本組成物適用於半導體元件之接著劑。
並且，本發明之半導體裝置之特徵在於，半導體元件係以上述固化性有機聚矽氧烷組成物之固化物接著。
本發明之固化性有機聚矽氧烷組成物之特徵在於，對於半導體元件之接著性優異，且形成之固化物中氣泡少。此外，本發明之半導體裝置之特徵在於，可靠性優異。
1‧‧‧聚鄰苯二甲醯胺(PPA)樹脂製框體
2‧‧‧內部引線
3‧‧‧模墊
4‧‧‧接著材料
5‧‧‧發光二極體(LED)晶片
6‧‧‧接合線
7‧‧‧密封材料
圖1係本發明之半導體裝置之一例，即表面安裝型發光二極體(LED)裝置之剖面圖。
(A)成分係一分子中具有至少2個烯基之有機聚矽氧烷。作為(A)成分中之烯基，可例示乙烯基、丙烯基、丁烯基、戊烯基、己烯基、庚烯基、辛烯基、壬烯基、癸烯基、十一烯基以及十二烯基等碳原子數為2~12之烯基，優選為乙烯基。此外，作為(A)成分中烯基以外之與矽原子鍵結之基團，可例示甲基、乙基、丙基、異丙基、丁基、異丁基、叔丁基、戊基、新戊基、己基、環己基、庚基、辛基、壬基、癸基、十一基、十二基等碳原子數為1~12之烷基；苯基、甲苯基、二甲苯基、萘基等碳原子數為6~20之芳基；芐基、苯乙基、苯丙基等碳原子數為7~20之芳烷基；以及利用氟原子、氯原子、溴原子等鹵素原子將該等基團之氫原子部分或全部取代之基團。再者，(A)成分中之矽原子上，於不損害本發明之目的之範圍內，亦可具有少量羥基及甲氧基、乙氧基等烷氧基。
(A)成分之分子構造並無特別限定，例如可列舉直鏈狀、具有部分分枝之直鏈狀、支鏈狀、環狀或者三維網狀構造。(A)成分可為具有該等分子構造之單獨之有機聚矽氧烷或者具有該等分子構造之二種以上之有機聚矽氧烷之混合物。
直鏈狀、具有部分分枝之直鏈狀或者環狀之有機聚矽氧烷以平均單元式：(R5 3SiO1/2)e(R5 2SiO2/2)f(R5SiO3/2)g(SiO4/2)h(HO1/2)i表示。
式中，R5為相同或不同之一價烴基，具體而言，可例示甲基、乙基、丙基、異丙基、丁基、異丁基、叔丁基、戊基、新戊基、己基、環己基、庚基、辛基、壬基、癸基、十一基、十二基等碳原子數為1~12之烷基；乙烯基、烯丙基、丁烯基、戊烯基、己烯基、庚烯基、辛烯基、壬烯基、癸烯基、十一烯基以及十二烯基等碳原子數為2~12之烯基；苯基、甲苯基、二甲苯基、萘基等碳原子數為6~20之芳基；芐基、苯乙基、苯丙基等碳原子數為7~20之芳烷基；以及利用氟原子、氯原子、溴原子等鹵素原子將該等基團之氫原子部分或全部取代之基團。其中，一分子中至少2個R5為所述烯基，優選為乙烯基。
此外，式中e、f、g、h以及i係表示矽氧烷構造單元之比率及羥基之比率之數，且滿足0e0.05、0.9f1、0g0.03、0h0.03、0i0.2並且e+f+g+h=1。其原因在於，e超過上述範圍之上限時，該有機聚矽氧烷之黏度會過低，可獲得之組成物之操作作業性會降低或固化物之硬度會降低。此外，g及h超過上述範圍之上限時，該有機聚矽氧烷之黏度會過高，可獲得之組成物之操作作業性會降低或可獲得之固化物會變脆。f之範圍由e、g以及h決定，但f小於上述範圍之下限時，無法向可獲得之組成物賦予適當之黏度或無法向固化 物賦予適當之硬度及機械強度。此外，該有機聚矽氧烷優選於25℃時為液狀，具體而言，25℃時之黏度優選為3~100,000mPa．s之範圍內或者5~5,000mPa．s之範圍內。其原因在於，該黏度為上述範圍之下限以上時，可獲得之固化物之機械強度會提高，另一方面，該黏度為上述範圍之上限以下時，可獲得之組成物之操作作業性會提高。
作為此種有機聚矽氧烷，可例示以下述平均單元式表示之有機聚矽氧烷。再者，式中Vi表示乙烯基，Me表示甲基，Ph表示苯基。
(ViMe2SiO1/2)0.012(Me2SiO2/2)0.988
(ViMe2SiO1/2)0.007(Me2SiO2/2)0.993
(Me3SiO1/2)0.007(Me2SiO2/2)0.983(MeViSiO2/2)0.010
(Me3SiO1/2)0.01(MeViSiO1/2)0.01(Me2SiO2/2)0.96(MeSiO3/2)0.02
(ViMe2SiO1/2)0.005(Me2SiO2/2)0.895(MePhSiO2/2)0.100
並且，亦可例示以下述平均式表示之有機聚矽氧烷。再者，式中Vi及Me與上述相同。
(MeViSiO2/2)3
(MeViSiO2/2)4
(MeViSiO2/2)5
另一方面，支鏈狀或三維網狀構造之有機聚矽氧烷以平均單元式：(R5 3SiO1/2)j(R5 2SiO2/2)k(R5SiO3/2)l(SiO4/2)p(HO1/2)q表示。
式中，R5為相同或不同之一價烴基，可例示與上述相同之基團。其中，一分子中至少2個R5為所述烯基，優選為乙烯基。
此外，式中j、k、l、p以及q為表示矽氧烷構造單元之比率及羥 基之比率之數，滿足0.4j0.6、0k0.05、0l0.05、0.4p0.6、0q0.05並且j+k+l+p=1。其原因在於，j小於上述範圍之下限時，固化物之機械強度會降低，另一方面，j超過上述範圍之上限時，無法向固化物賦予充分之硬度。此外，k超過上述範圍之上限時，無法向固化物賦予充分之硬度。此外，l超過上述範圍之上限時，固化物之機械強度會降低。此外，p小於上述範圍之下限時，無法向固化物賦予充分之硬度，另一方面，p超過上述範圍之上限時，於可獲得之組成物中之分散性會降低，無法向固化物賦予充分之機械強度。該25℃時之性狀並無特別限定，只要與上述鏈狀、具有部分分枝之直鏈狀或者環狀之有機聚矽氧烷具有相溶性，則可為液體亦可為固體。
作為此種有機聚矽氧烷，可例示以下述平均組成式表示之有機聚矽氧烷。再者，式中Vi、Me及Ph與上述相同。
(ViMe2SiO1/2)0.10(Me3SiO1/2)0.33(SiO4/2)0.57(HO1/2)0.03
(ViMe2SiO1/2)0.13(Me3SiO1/2)0.35(SiO4/2)0.52(HO1/2)0.02
(ViMePhSiO1/2)0.10(Me3SiO1/2)0.45(SiO4/2)0.45(HO1/2)0.03
(ViMe2SiO1/2)0.09(Me3SiO1/2)0.31(SiO4/2)0.60(HO1/2)0.04
(ViMe2SiO1/2)0.10(Me3SiO1/2)0.40(SiO4/2)0.50(HO1/2)0.03
(A)成分優選由上述鏈狀、具有部分分枝之直鏈狀或者環狀之有機聚矽氧烷15~100質量%以及上述支鏈狀或者三維網狀構造之有機聚矽氧烷0~85重量%構成。其原因在於，上述有機聚矽氧烷之含量為上述範圍之下限以上時，能夠向可獲得之固化物賦予充分之可撓性。
考慮到操作作業性良好，此種(A)成分優選25℃時為液狀，具體而言，25℃時之黏度優選為100~5,000,000mPa．s之範圍內或者500~100,000mPa．s之範圍內。
(B)成分係以平均單元式： (R1 3SiO1/2)a(R1 2SiO2/2)b(R2SiO3/2)c(SiO4/2)d表示之有機聚矽氧烷樹脂。
式中，R1為相同或不同之不具有脂肪族不飽和碳鍵之一價烴基或者氫原子。作為R1之一價烴基，可例示甲基、乙基、丙基、異丙基、丁基、異丁基、叔丁基、戊基、新戊基、己基、環己基、庚基、辛基、壬基、癸基、十一基、十二基等碳原子數為1~12之烷基；苯基、甲苯基、二甲苯基、萘基等碳原子數為6~20之芳基；芐基、苯乙基、苯丙基等碳原子數為7~20之芳烷基；以及利用氟原子、氯原子、溴原子等鹵素原子將該等基團之氫原子部分或全部取代之基團。其中，一分子中至少2個R1為氫原子。
此外，式中R2為不具有脂肪族不飽和鍵之一價烴基，可例示與所述R1相同之基團。
此外，式中a、b、c分別為0<a<1、0<b<1、0c<0.2、0<d<1，其中，0.6a/d1.5、1.5b/d3並且a+b+c+d=1之數，優選為滿足0.7a/d1.5、1.5b/d2.5之數、滿足0.7a/d1.4、1.6b/d2.5之數或者滿足0.8a/d1.4、1.6b/d2之數。其原因在於，a/d之值為上述範圍之下限以上時，可獲得之組成物之黏度不會過高，另一方面，a/d之值為上述範圍之上限以下時，可獲得之固化物之接著特性會良好。此外，b/d之值為上述範圍內時，可獲得之固化物之接著特性良好。
此種(B)成分之重均分子量(Mw)優選為6,000以上、8,000以上、甚至10,000以上。其原因在於，(B)成分之重均分子量為上述下限以上時，可獲得之固化物之接著力良好，此外，能夠抑制固化物中氣泡之產生。
作為此種(B)成分，可例示以平均單元式：(Me3SiO1/2)0.23(MeHSiO2/2)0.51(SiO4/2)0.26表示之有機聚矽氧烷、以平均單元式： (Me3SiO1/2)0.24(MeHSiO2/2)0.49(SiO4/2)0.27表示之有機聚矽氧烷以及以平均單元式：(Me3SiO1/2)0.24(Me2SiO2/2)0.10(MeHSiO2/2)0.40(SiO4/2)0.26表示之有機聚矽氧烷。
考慮到可獲得之固化物之硬度、機械特性以及接著性良好，(B)成分之含量為，相對於(A)成分中之烯基之合計1莫耳，(B)成分中之矽原子鍵結氫原子之量為0.5~5莫耳之範圍內，優選為0.5~3莫耳之範圍內或者0.5~2莫耳之範圍內。
(C)成分係用來促進本組成物之矽氫化反應之矽氫化反應用催化劑。此種(C)成分優選鉑族元素催化劑、鉑族元素化合物催化劑，可例示鉑系催化劑、銠系催化劑以及鈀系催化劑，優選為鉑系催化劑。作為鉑系催化劑，可例示鉑微粉、鉑黑、氯化鉑酸、氯化鉑酸之醇改性物、氯化鉑酸與二烯烴之錯合物、鉑-烯烴錯合物、鉑雙(乙醯乙酸)、鉑雙(乙醯丙酮)等鉑-羰基錯合物、氯化鉑酸二乙烯基四甲基二矽氧烷錯合物、氯化鉑酸．四乙烯基四甲基環四矽氧烷錯合物等氯化鉑酸．烯基矽氧烷錯合物、鉑．二乙烯基四甲基二矽氧烷錯合物、鉑．四乙烯基四甲基環四矽氧烷錯合物等鉑．烯基矽氧烷錯合物以及氯化鉑酸與乙炔醇類之錯合物，尤其是，考慮到矽氫化反應性能良好，優選為鉑-烯基矽氧烷錯合物。
作為該烯基矽氧烷，可例示1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷、1,3,5,7-四甲基-1,3,5,7-四乙烯基環四矽氧烷、利用乙基、苯基等將該等烯基矽氧烷之甲基部分取代之烯基矽氧烷寡聚物以及利用烯丙基、己烯基等將該等烯基矽氧烷之乙烯基取代之烯基矽氧烷寡聚物。尤其是，考慮到生成之鉑-烯基矽氧烷錯合物之穩定性良好，優選為1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷。
此外，為提高鉑-烯基矽氧烷錯合物之穩定性，優選將該等鉑- 烯基矽氧烷錯合物溶解於1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷、1,3-二烯丙基-1,1,3,3-四甲基二矽氧烷、1,3-二乙烯基-1,3-二甲基-1,3-二苯基二矽氧烷、1,3-二乙烯基-1,1,3,3-四苯基二矽氧烷、1,3,5,7-四甲基-1,3,5,7-四乙烯基環四矽氧烷等烯基矽氧烷寡聚物及二甲基矽氧烷寡聚物等有機矽氧烷寡聚物中，尤其優選溶解於烯基矽氧烷寡聚物中。
(C)成分之含量係用來促進本組成物之固化之量即可，並無限定，具體而言，相對於本組成物，本成分中之鉑族金屬原子、尤其是鉑原子以質量單元計優選為0.01~500ppm之範圍內、0.01~100ppm之範圍內或者0.1~50ppm之範圍內。其原因在於，(C)成分之含量為上述範圍之下限以上時，可獲得之組成物之固化性良好，另一方面，(C)成分之含量為上述範圍之上限以下時，可獲得之固化物不易產生著色等問題。
為提高操作作業性及接著性，本組成物中優選含有(D)BET比表面積為20~200m2/g之發煙二氧化矽。(D)成分之含量並無限定，但考慮到可獲得之固化物之機械特性良好，相對於上述(A)~(C)成分之合計100質量份，優選為1~20質量份之範圍內。
為延長常溫時之可使用時間並提高保存穩定性，本組成物中優選含有(E)矽氫化反應抑制劑。作為(E)成分，可例示1-乙炔基環己烷-1-醇、2-甲基-3-丁炔-2-醇、3,5-二甲基-1-己炔-3-醇、2-苯基-3-丁炔-2-醇等之炔醇；3-甲基-3-戊烯-1-炔、3,5-二甲基-3-己烯-1-炔等烯炔化合物；1,3,5,7-四甲基-1,3,5,7-四乙烯基環四矽氧烷、1,3,5,7-四甲基-1,3,5,7-四己烯環四矽氧烷等甲基烯基矽氧烷寡聚物；二甲基雙(3-甲基-1-丁炔-3-氧)矽烷、甲基乙烯基雙(3-甲基-1-丁炔-3-氧)矽烷等烯氧基矽烷；甲基三(1-甲基-1-苯基-丙炔氧基)矽烷、二甲基雙(1-甲基-1-苯基-丙炔氧基)矽烷、甲基三(1,1-二甲基-丙炔氧基)矽烷、二甲基雙(1,1-二甲基-丙炔氧基)矽烷等烯氧基矽烷化合物；以及其他苯并三唑。
(E)成分之含量並無限定，考慮到於(A)成分、(B)成分及(C)成分混合時抑制凝膠化或固化所需之充分之量，且向本組成物賦予充分之適用期，相對於(A)成分~(C)成分之合計100質量份，優選為0.0001~5質量份之範圍內、0.01~5質量份之範圍內或者0.01~3質量份之範圍內。
此外，本組成物中，為了進一步提高與固化中接觸之基材之接著性，優選含有(F)接著促進劑。作為該接著促進劑，能夠使用可添加至藉由矽氫化反應而固化之固化性有機聚矽氧烷組成物中的眾所周知者。
作為此種(F)成分，可列舉三烷氧基矽氧基(例如三甲氧基矽氧基、三乙氧基矽氧基)或三烷氧基甲矽烷基烷基(例如三甲氧基甲矽烷基乙基、三乙氧基甲矽烷基乙基)、氫化甲矽烷基或具有烯基(例如乙烯基、烯丙基)之有機矽烷、或矽原子數為4~20左右之直鏈狀構造、分支狀構造或環狀構造之有機矽氧烷寡聚物；具有三烷氧基矽氧基或三烷氧基甲矽烷基烷基及甲基丙烯醯氧基烷基(例如，3-甲基丙烯醯氧基丙基)之有機矽烷、或矽原子數為4~20左右之直鏈狀構造、分支狀構造或環狀構造之有機矽氧烷寡聚物；具有三烷氧基矽氧基或三烷氧基甲矽烷基烷基及環氧基鍵結烷基(例如3-縮水甘油氧基丙基、4-縮水甘油氧基丁基、2-(3,4-環氧環己基)乙基、3-(3,4-環氧環己基)丙基)之有機矽烷或矽原子數為4~20左右之直鏈狀構造、分支狀構造或者環狀構造之有機矽氧烷寡聚物；以及胺烷基三烷氧基矽烷與環氧基鍵結烷基三烷氧基矽烷之反應物、含有環氧基之聚矽酸乙酯，具體而言，可列舉乙烯基三甲氧基矽烷、烯丙基三甲氧基矽烷、烯丙基三乙氧基矽烷、氫基三乙氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷與3-氨基丙基三乙氧基矽烷之反應物、矽醇基封端甲基乙烯基矽氧烷寡聚物與3-縮水甘油氧基丙基三甲 氧基矽烷之縮合反應物、矽醇基封端甲基乙烯基矽氧烷寡聚物與3-甲基丙烯醯氧基丙基三乙氧基矽烷之縮合反應物以及三(3-三甲氧基甲矽烷基丙基)異氰尿酸基。
此種(F)成分之含量並無限定，但為避免促進固化特性及固化物之變色，相對於(A)成分~(C)成分之合計100質量份，優選為0.01~10質量份之範圍內或0.01~5質量份之範圍內。
本組成物中亦可根據需要含有上述(B)成分以外之具有矽原子鍵結氫原子之有機聚矽氧烷。作為此種有機聚矽氧烷，可例示(G)以平均式：R3R4 2SiO(R4 2SiO)m(R4HSiO)nSiR4 2R3表示之有機聚矽氧烷。
式中，R3為相同或不同之不具有脂肪族不飽和碳鍵之一價烴基或者氫原子。作為R3之一價烴基，可例示與所述R1相同之一價烴基。
此外，式中R4為相同或不同之不具有脂肪族不飽和碳鍵之一價烴基，可例示與所述R1相同之一價烴基。
此外，式中m為0~50之數，n為0~50之數，其中，n為0時，R3為氫原子。
作為此種有機聚矽氧烷，可例示具有下述平均結構式之有機聚矽氧烷。再者，式中Me及Ph與上述相同。
Me3SiO(MeHSiO)10SiMe3
HMe2SiO(Me2SiO)10SiMe2H
Me3SiO(MeHSiO)80SiMe3
Me3SiO(Me2SiO)30(MeHSiO)30SiMe3
Me2PhSiO(MeHSiO)35SiMe2Ph
此種有機聚矽氧烷之含量並無限定，但考慮到接著性良好且獲 得不易產生氣泡之固化物，相對於(A)成分中之烯基之合計1莫耳，(G)成分中之矽原子鍵結氫原子之量優選為最多0.5莫耳或者最多0.3莫耳。
本組成物中，於不損害本發明之目的之範圍內，作為其他任意成分，亦可添加(D)成分以外之二氧化矽、玻璃、氧化鋁、氧化鋅等無機質充填劑；矽橡膠粉末；矽樹脂、聚甲基丙烯酸酯樹脂等樹脂粉末；以及耐熱劑、染料、顏料、阻燃添加劑、溶劑等。
考慮到操作作業性之觀點，本組成物優選於25℃時為液狀，25℃時之黏度優選為10~1,000,000mPa．s之範圍內。本組成物用作半導體元件之接著劑時，25℃時之黏度優選為1,000~500,000mPa．s之範圍內。
本組成物藉由室溫放置或加熱來進行固化，但為使其迅速固化，優選實施加熱。加熱溫度優選為50~200℃之範圍內。
此種本組成物對於鋼、不銹鋼、鋁、銅、銀、鈦、鈦合金等金屬；矽半導體、磷酸鎵系半導體、砷化鎵系半導體、氮化鎵系半導體等半導體元件；陶瓷、玻璃、熱固化性樹脂、具有極性基之熱可塑性樹脂等之初期接著性、接著耐久性、尤其是經歷冷熱循環時之接著耐久性優異。
本組成物優選固化後形成JIS K 6253所規定之D型硬度計硬度為30~70之固化物。其原因在於，硬度小於上述範圍之下限時，凝集力不足，無法獲得充分之強度及接著性，另一方面，硬度超過上述範圍之上限時，固化物會變脆，無法獲得充分之接著性。
以下，詳細說明本發明之半導體裝置。
本發明之半導體裝置之特徵在於，藉由由上述組成物構成之接著劑之固化物接著框體內之半導體元件。作為該半導體元件，具體而言，可例示發光二極體(LED)、半導體雷射、光電二極體、光電晶體管、固態成像、光耦合器用發光體及受光體，尤其優選發光二極體(LED)。
發光二極體(LED)時，會自半導體之上下左右產生發光，因此構成裝置之部件不宜採用會吸收光線者，應選擇透光率高或反射率高之材料。搭載光半導體元件之基板亦不例外。作為該基板，可例示銀、金、銅等導電性金屬；鋁、鎳等非導電性金屬；PPA及LCP等混合有白色顏料之熱可塑性樹脂；環氧樹脂、BT樹脂、聚醯亞胺樹脂及矽樹脂等含有白色顏料之熱固化性樹脂；以及氧化鋁、氮化鋁等陶瓷。本組成物相對於光半導體元件以及基板具有良好之接著性，因此能夠提高可獲得之光半導體裝置之可靠性。
藉由圖1詳細說明本發明之半導體裝置。圖1係半導體裝置之代表例即單個表面安裝型發光二極體(LED)裝置之剖面圖。圖1之發光二極體(LED)裝置藉由接著材料4將發光二極體(LED)晶片5接著至聚鄰苯二甲醯胺(PPA)樹脂製框體1內之模墊3上，藉由接合線6將該發光二極體(LED)晶片5與內部引線2進行線結合，並藉由密封材料7將其與該框體內壁一同密封。本發明之半導體裝置中，作為形成接著材料4之組成物，使用本發明之固化性有機聚矽氧烷組成物。
〔實施例〕
藉由實施例及比較例，詳細說明本發明之固化性有機聚矽氧烷組成物以及半導體裝置。再者，實施例及比較例中之黏度為25℃時之值，此外，為配製實施例及比較例中之固化性有機聚矽氧烷組成物，使用有以下成分。再者，式中Vi表示乙烯基，Me表示甲基。此外，表中SiH/Vi之比率表示組成物中相對於(a-1)成分~(a-7)成分之乙烯基之合計1莫耳，(b-1)成分~(b-6)成分之矽原子鍵結氫原子之合計莫耳數之值。
(a-1)成分：以平均單元式：(Me2ViSiO1/2)0.042(Me2SiO2/2)0.958表示之黏度60mPa．s之有機聚矽氧烷(乙烯基之含量=1.53質量%)
(a-2)成分：以平均單元式：(Me2ViSiO1/2)0.012(Me2SiO2/2)0.988表示之黏度550mPa．s之有機聚矽氧烷(乙烯基之含量=0.45質量%)
(a-3)成分：以平均式：(MeViSiO)4表示之黏度4mPa．s之環狀甲基乙烯基聚矽氧烷(乙烯基之含量=30質量%)
(a-4)成分：以平均式：HO(MeViSiO)20H表示之黏度30mPa．s之甲基乙烯基聚矽氧烷(乙烯基之含量=30質量%)
(a-5)成分：以平均單元式：(Me2ViSiO1/2)0.55(Me3SiO1/2)0.05(SiO4/2)0.40表示之室溫時為固體之有機聚矽氧烷(乙烯基之含量=19.0質量%)
(a-6)成分：以平均單元式：(Me2ViSiO1/2)0.09(Me3SiO1/2)0.43(SiO4/2)0.48(HO1/2)0.03表示之室溫時為固體之有機聚矽氧烷(乙烯基之含量=3.0質量%)
(a-7)成分：以平均單元式：(Me2ViSiO1/2)0.10(Me3SiO1/2)0.45(SiO4/2)0.45(HO1/2)0.02表示之室溫時為固體之有機聚矽氧烷(乙烯基之含量=3.0質量%)
(b-1)成分：黏度為2000mPa．s且以平均單元式：(Me3SiO1/2)0.23(MeHSiO2/2)0.51(SiO4/2)0.26表示之有機聚矽氧烷(重均分子量=18000、矽原子鍵結氫原子之含量=0.78質量%)
(b-2)成分：黏度為510mPa．s且以平均單元式：(Me3SiO1/2)0.24(MeHSiO2/2)0.49(SiO4/2)0.27表示之有機聚矽氧烷(重均分子量=16300、矽原子鍵結氫原子之含量=0.75質量%)
(b-3)成分：黏度為640mPa．s且以平均單元式：(Me3SiO1/2)0.24(Me2SiO2/2)0.10(MeHSiO2/2)0.40(SiO4/2)0.26表示之有機聚矽氧烷(重均分子量=15400、矽原子鍵結氫原子之含量=0.78質量%)
(b-4)成分：黏度為230mPa．s且以平均單元式：(HMe2SiO1/2)0.51(Me2SiO2/2)0.15(SiO4/2)0.34(HO1/2)0.03表示之有機聚矽氧烷(重均分子量=2100、矽原子鍵結氫原子之含量=0.80質量%)
(b-5)成分：黏度為120mPa．s且以平均單元式：(HMe2SiO1/2)0.67(SiO4/2)0.33表示之有機聚矽氧烷(重均分子量=1310、矽原子鍵結氫原子之含量=0.95質量%)
(b-6)成分：黏度為10mPa．s且以平均式：Me3SiO(MeHSiO)10SiMe3表示之有機聚矽氧烷(重均分子量=8800、矽原子鍵結氫原子之含量=1.6質量%)
(c)成分：鉑金屬之含量約為4重量%之鉑之1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物之1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷溶液
(d)成分：BET比表面積為115~165m2/g且其表面藉由六甲基二矽氮烷實施過疏水化處理之發煙二氧化矽(日本Aerosil公司製之商品名：RX200)
(e)成分：1-乙炔基環己烷-1-醇
(f)成分：25℃時之黏度為30mPa．s且分子鏈兩末端由矽醇基封端之甲基乙烯基矽氧烷寡聚物與3-縮水甘油氧基丙基三甲氧基矽烷之縮合反應物
此外，如下測定將實施例及比較例中之固化性有機聚矽氧烷組成物固化後獲得之固化物之硬度、晶片抗切強度以及固化物中之氣泡數。
[固化物之硬度]
藉由將固化性有機聚矽氧烷組成物於150℃下沖壓成型1小時，製成片狀固化物。藉由JIS K 6253中規定之D型硬度計測定該片狀固化物之硬 度。
[晶片抗切強度(die shear strength)]
於25mm×75mm之鍍銀鋼板上，藉由塗佈機將固化性有機聚矽氧烷組成物分別以約300mg塗佈至5處。接著，於該組成物上覆蓋厚度為1mm之10mm方形玻璃製晶片，於藉由1kg板壓接之狀態下，於150℃下加熱2小時，使其固化。然後，冷卻至室溫，藉由剪切強度測定裝置(西進商事株式會社製之Bond Tester SS-100KP)測定晶片抗切強度。
[固化物內之氣泡數]
目視計數藉由所述方法製成之晶片抗切試驗片內之氣泡數。
[實施例1~6、比較例1~3]
以表1所示之混合比，配製固化性有機聚矽氧烷組成物。如上所述測定固化物之各特性，並將其結果示於表1。
【產業上之可利用性】
本發明之固化性有機聚矽氧烷組成物可作為發光二極體(LED)、半導體雷射、光電二極體、光電晶體管、固態成像、光耦合器用發光體及受光體等半導體元件之接著劑發揮作用。此外，本發明之半導體裝置具有優異之可靠性，因此可作為光學裝置、光學機器、照明機器、照明裝置等光半導體裝置發揮作用。

Claims (8)

  1. 一種固化性有機聚矽氧烷組成物，至少由下述(A)、(B)以及(C)構成；(A)一分子中具有至少2個烯基之有機聚矽氧烷；(B)以平均單元式：(R 1 3SiO 1/2) a(R 1 2SiO 2/2) b(R 2SiO 3/2) c(SiO 4/2) d(式中，R 1為相同或不同之不具有脂肪族不飽和碳鍵之一價烴基或者氫原子，其中，一分子中至少2個R 1為氫原子，R 2為不具有脂肪族不飽和鍵之一價烴基，a、b、c分別為滿足0<a<1、0<b<1、0 c<0.2、0<d<1，其中0.6 a/d 1.5、1.5 b/d 3並且a+b+c+d=1之數)表示之有機聚矽氧烷樹脂{相對於(A)成分中之烯基，(B)成分中之矽原子鍵結氫原子之莫耳比為0.5~5之量}；(C)矽氫化反應用催化劑(足以使本組成物固化之量)。
  2. 如請求項1所述之固化性有機聚矽氧烷組成物，其中，相對於(A)~(C)成分之合計100質量份，還含有1~20質量份之(D)BET比表面積為20~200m 2/g之發煙二氧化矽(fumed silica)。
  3. 如請求項1或2所述之固化性有機聚矽氧烷組成物，其中，相對於(A)~(C)成分之合計100質量份，還含有0.001~5質量份之(E)矽氫化反應抑制劑。
  4. 如請求項1至3中任一項所述之固化性有機聚矽氧烷組成物，其中，相對於(A)~(C)成分之合計100質量份，還含有0.01~10質量份之(F)接著促進劑。
  5. 如請求項1至4中任一項所述之固化性有機聚矽氧烷組成物，其中，還含有(G)以平均式： R 3R 4 2SiO(R 4 2SiO) m(R 4HSiO) nSiR 4 2R 3(式中，R 3為相同或不同之不具有脂肪族不飽和碳鍵之一價烴基或者氫原子，R 4為相同或不同之不具有脂肪族不飽和碳鍵之一價烴基，m為0~50之數、n為0~50之數，其中，n為0時，R 3為氫原子)表示之有機聚矽氧烷，相對於(A)成分中之烯基，(G)成分中之矽原子鍵結氫原子之莫耳比最多為0.5。
  6. 如請求項1至5中任一項所述之固化性有機聚矽氧烷組成物，其固化後形成JIS K 6253所規定之D型硬度計硬度為30~70之固化物。
  7. 如請求項1至6中任一項所述之固化性有機聚矽氧烷組成物，其為半導體元件之接著劑。
  8. 一種半導體裝置，其半導體元件係以請求項1至6中任一項所述之固化性有機聚矽氧烷組成物之固化物接著。
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