TW201716460A - 半導體密封用熱硬化性樹脂組成物 - Google Patents
半導體密封用熱硬化性樹脂組成物 Download PDFInfo
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- TW201716460A TW201716460A TW105121390A TW105121390A TW201716460A TW 201716460 A TW201716460 A TW 201716460A TW 105121390 A TW105121390 A TW 105121390A TW 105121390 A TW105121390 A TW 105121390A TW 201716460 A TW201716460 A TW 201716460A
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Abstract
本發明的課題為提供一種半導體密封用熱硬化性樹脂組成物,其係耐水性、研磨性良好,即使使用大型晶圓進行密封,亦流動性優異,彎曲小,通用性高。本發明的解決手段係一種半導體密封用熱硬化性樹脂組成物,其係包含(A)於1分子中具有2個以上氰氧基(cyanato)之氰酸酯化合物、(B)包含間苯二酚型酚樹脂之酚硬化劑、(C)硬化促進劑、及(D)包含球狀之無機質填充材。
Description
本發明係關於半導體密封用熱硬化性樹脂組成物、及以該樹脂組成物密封之半導體裝置。
近年來,半導體裝置正迎接卓越技術革新。智慧型手機、平板等之便攜式信息、通信終端係以將大容量的信息可高速處理的方式,使用TSV(through silicon via(矽穿孔))技術多層連接半導體元件,於8英寸~12英寸的矽中介層連接倒裝晶片後,由熱硬化樹脂,對每一個複數個搭載多層連接之半導體元件的中介層進行密封。可研磨半導體元件上不要的硬化樹脂後,進行單片化而得到薄型且小型、多機能且可高速處理之半導體裝置。
使用8英寸左右大小之徑晶圓等之基板的情況即使於現狀亦可沒什麼問題進行密封成形。惟,12英寸以上,近年來於20英寸晶圓、或超過20英寸之面板的成形,由於密封後環氧樹脂等之收縮應力較大,有半導體元件從金屬等之基板剝離的問題,無法量產化。伴隨晶圓或玻璃基板、金屬基板的大口徑化為了解決如上述的問
題,必須於樹脂填充90質量%以上填料、或以樹脂之低彈性化縮小硬化時之收縮應力(專利文獻1)。
然而,於矽中介層上全面密封熱硬化樹脂時,由於矽與熱硬化性樹脂的熱膨脹係數不同而產生較大的彎曲。彎曲較大時,由於不適用在之後的研磨步驟或單片化步驟,故彎曲的防止成為一重大技術課題。進而於近年來,伴隨半導體元件的層合化,由於密封層增厚,研磨密封之樹脂層,成為薄型之半導體裝置逐漸成為主流(專利文獻2)。
以往,於使用環氧樹脂與酸酐或酚樹脂等之硬化劑的組成物填充85質量%以上填料,為了緩和應力,已使用摻合橡膠或熱可塑性樹脂之密封材。於這般的組成物,從藉由3D包裝之步驟之熱履歷,產生變更彎曲,由此彎曲損傷半導體元件、或晶圓本身破裂的問題。另一方面,於以往之矽氧化合物所代表之低彈性樹脂的材料,由於樹脂柔軟,有於研磨時產生樹脂堵塞、或在信賴性試驗產生樹脂裂縫的問題(專利文獻3)。
[專利文獻1]日本特開2012-209453號公報
[專利文獻2]日本特開2014-229771號公報
[專利文獻3]日本特開平11-289034號公報
本發明係以提供一種密封半導體裝置的情況下,耐水性、研磨性良好,即使使用大型晶圓密封,亦流動性優異,彎曲小,通用性高之半導體密封用熱硬化性樹脂組成物作為目的。
本發明者們為了解決上述課題經努力研究的結果發現,組合特定之氰酸酯化合物、與特定之酚硬化劑、與特定之無機質填充材的熱硬化性樹脂組成物可達成上述目的,而完成本發明。即,本發明係提供下述之半導體密封用熱硬化性樹脂組成物及使用該組成物之硬化物的樹脂密封型半導體裝置之製造方法。
一種半導體密封用熱硬化性樹脂組成物,其係包含下述(A)~(D)成分:(A)於1分子中具有2個以上氰氧基(cyanato)之氰酸酯化合物,其包含以JIS K7117-1:1999記載之方法,使用B型回轉黏度計測定在23℃之黏度為50Pa.s以下之下述式(1)表示之氰酸酯化合物,
(式(1)中,R1及R2係表示氫原子或碳數1~4之烷基,R3係選自由下述式(2)~(5)所構成之群組中之2價連接基,n=0或1之整數)
(B)包含下述式(6)表示之間苯二酚型酚樹脂之酚硬化劑
(式(6)中,n係表示0以上10以下之整數,R1及R2分別獨立表示選自由氫原子、碳數1~10之烷基、烯丙基及乙烯基所構成之群組中之1價之基)
(C)硬化促進劑
(D)以雷射繞射法測定之平均粒徑為1~20μm之球狀,以下述式(7)表示之矽烷偶合劑表面處理之無機質填充材【化4】R1 a(OR2)(3-a)Si-C3H6-R3 (7)
(式(7)中,R1為甲基或乙基,R2為碳數1~3之烷基,R3係選自由下述式(8)~(11)表示之含氮官能基所構成之群組中之基,a為0~3之整數)
相對於(A)及(B)成分之合計100質量份為1,200
~2,200質量份。
如[1]之半導體密封用熱硬化性樹脂組成物,其中,在前述(A)成分中,式(1)表示之氰酸酯化合物相對於(A)成分全體的摻合量為90質量%以上未滿100質量%,且包含2種以上之氰酸酯化合物。
如[1]或[2]之半導體密封用熱硬化性樹脂組成物,其中,在前述(B)成分中,式(6)表示之間苯二酚型酚樹脂相對於(B)成分全體的摻合量為10質量%以上100質量%以下,且相對於(B)成分之酚硬化劑中之羥基1當量,(A)成分之氰酸酯化合物中之氰氧基為0.5~100當量。
如[1]~[3]中任一項之半導體密封用熱硬化性樹脂組成物,其中,根據JIS K 7197:2012所記載之方法,使用5×5×15mm之試驗片,以昇溫5℃/分鐘、荷重19.6mN測定時之線膨脹係數為3.0~5.0ppm/℃的範圍。
一種樹脂密封型半導體裝置之製造方法,其係具有將
載置1個以上半導體元件之面積200~1500cm2的矽晶圓或基板全體,以如[1]~[4]中任一項之半導體密封用熱硬化性樹脂組成物的硬化物一次密封之步驟,且密封後之矽晶圓或基板的彎曲量為2mm以下。
如[5]之樹脂密封型半導體裝置之製造方法,其中,在一次密封之步驟中,將半導體密封用熱硬化性樹脂組成物於按壓下進行被覆、或於真空環境下進行減壓被覆,加熱硬化該樹脂組成物,密封半導體元件。
根據本發明,可提供一種即使將1個以上之半導體元件以接著劑(晶粒接合材)密封搭載於無機基板、金屬基板或有機基板上之半導體元件陣列、或形成半導體元件之大徑矽晶圓,亦幾乎不會產生於加熱硬化後冷卻時之彎曲,且耐熱性、耐濕性優異之半導體裝置,且以晶圓水準可一次密封且可輕易研磨、切割密封樹脂。
[圖1]表示玻璃轉移溫度之決定方法之圖。
以下,雖針對本發明進行詳細說明,但本發明並非被限定於此等。
(A)成分為本發明之組成物的主成分,係具有2個以上氰氧基之氰酸酯化合物,包含上述式(1)表示之化合物。
(式(1)中,R1及R2係表示氫原子或碳數1~4之烷基,R3係選自由下述式(2)~(5)所構成之群組中之2價連接基,n=0或1之整數)
上述式(1)表示之化合物係以JIS K7117-1:1999記載之方法,使用B型回轉黏度計測定在23℃之
黏度為50Pa.s以下,特佳為20Pa.s以下。超過50Pa.s時,由於無法再高填充無機質填充材,膨脹係數增大,成形於12英寸以上之晶圓的情況下有彎曲變大,無法形成片狀之虞。
式(1)之化合物的摻合量較佳為相對於氰酸酯化合物全體為包含90質量%以上。該摻合量未滿90質量%時,無法再高填充無機質填充材,有無法形成片狀之虞。
於本發明,可混合1種以上式(1)之氰酸酯化合物、與2種以上其他氰酸酯化合物來使用。作為具有2個以上氰氧基之式(1)以外的氰酸酯化合物,一般可使用周知者,例如可列舉雙(4-氰氧苯基)甲烷、雙(3-甲基-4-氰氧苯基)甲烷、雙(3,5-二甲基-4-氰氧苯基)甲烷、1,1-雙(4-氰氧苯基)乙烷、2,2-雙(4-氰氧苯基)丙烷、2,2-雙(4-氰氧苯基)-1,1,1,3,3,3-六氟丙烷、二(4-氰氧苯基)硫醚、1,3-二氰氧苯、1,4-二氰氧苯、2-tert-丁基-1,4-二氰氧苯、2,4-二甲基-1,3-二氰氧苯、2,5-二-tert-丁基-1,4-二氰氧苯、四甲基-1,4-二氰氧苯、1,3,5-三氰氧苯、2,2’-二氰氧聯苯、4,4’-二氰氧聯苯、3,3’,5,5’-四甲基-4,4’-二氰氧聯苯、1,3-二氰氧萘、1,4-二氰氧萘、1,5-二氰氧萘、1,6-二氰氧萘、1,8-二氰氧萘、2,6-二氰氧萘、2,7-二氰氧萘、1,3,6-三氰氧萘、1,1,1-1參(4-氰氧苯基)乙烷、雙(4-氰氧苯基)醚、4,4’-(1,3-伸苯基二異亞丙基)二苯基氰酸酯、雙(4-氰氧苯基)硫醚、雙(4-
氰氧苯基)碸、參(4-氰氧基-苯基)膦、酚酚醛清漆型氰酸酯、甲酚酚醛清漆型氰酸酯、二環戊二烯酚醛清漆型氰酸酯等。
(A)成分之氰酸酯化合物的組成物樹脂全體中之摻合量較佳為80~99質量%,更佳為85~99質量%,最佳為90~97質量%。
(B)成分係包含下述式(6)表示之間苯二酚型酚樹脂之酚硬化劑。
(式(6)中,n係表示0以上10以下之整數,R1及R2分別獨立表示選自由氫原子、碳數1~10之烷基、烯丙基及乙烯基所構成之群組中之1價之基)。
上述式(6)之n從熔融流動性的觀點來看,較佳為0以上10以下。n超過10時,於100℃以下無法熔融,而降低樹脂組成物的流動性。(B)成分可混合2種以上n之值不同的間苯二酚型酚樹脂(式(6))使用,可使用具有分布於n之值之間苯二酚型酚樹脂(式(6))。上述式(6)之R1及R2較佳為選自由原子、碳
數1以上10以下之烷基、烯丙基及乙烯基所構成之群組中之1價之基,特佳為選自由氫原子、碳原子數1~4之烷基、烯丙基及乙烯基所構成之群組中之1價之基。R1及R2可為相異之官能基。尚,使用碳原子數超過10之基時,脂肪族基的情況下,得不到充分之耐熱性,芳基的情況下,會降低熔融時之流動性。
(B)酚硬化劑與(A)成分之摻合比,相對於式(2)之間苯二酚型酚樹脂中之羥基(OH基)1當量,較佳為(A)成分之具有2個以上氰氧基(CN基)之氰酸酯化合物中之氰氧基(CN基)成為0.5~100當量的量,更佳為成為1~50當量的量,再更佳為成為5~35當量的量。超過100當量時,硬化變不夠充分,未滿0.5當量時,有損害氰酸酯化合物本身的耐熱性之虞。
酚硬化劑可藉由包含上述式(6)表示之間苯二酚型酚樹脂,使熔融時之樹脂黏度降低,同時可促進氰酸酯化合物的硬化反應。進而由於間苯二酚型酚樹脂本身的耐熱性高,可得到具有優異耐熱性之硬化物。
作為(C)成分,可列舉1,8-二氮雜雙環[5.4.0]十一碳烯-7(DBU)、1,5-二氮雜雙環[4.3.0]壬烯-5(DBN)、此等之N-烷基取代體、N-芳基取代體及此等含氮雜環化合物之鹽、以及胺系硬化促進劑等。(C)成分之硬化促進劑的摻合量相對於(A)具有2個以上氰氧基之氰酸
酯樹脂100質量份,較佳為5質量份以下,更佳為0.01~5質量份。
作為DBU之鹽之具體例,可列舉DBU之酚鹽、辛酸鹽、p-甲苯磺酸鹽、蟻酸鹽、鄰苯二甲酸鹽、偏苯三酸酐鹽、酚酚醛清漆樹脂鹽、四苯基硼酸鹽。另一方面,作為DBN之鹽之具體例,可列舉DBN之酚鹽、辛酸鹽、p-甲苯磺酸鹽、蟻酸鹽、鄰苯二甲酸鹽、偏苯三酸酐鹽、酚酚醛清漆樹脂鹽、四苯基硼酸鹽。
作為胺系硬化促進劑,可列舉3,3’-二乙基-4,4’-二胺基二苯基甲烷、3,3’,5,5’-四甲基-4,4’-二胺基二苯基甲烷、3,3’,5,5’-四乙基-4,4’-二胺基二苯基甲烷、2,4-二胺基甲苯、1,4-伸苯基二胺、1,3-伸苯基二胺、二乙基甲苯二胺、3,4’-二胺基二苯基醚、3,3’-二胺基二苯基甲烷、3,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基甲烷、3,3’-二胺基聯苯胺(benzidine)、鄰聯甲苯胺(o-tolidine)、3,3’-二甲基-4,4’-二胺基二苯基甲烷、2,6-二胺基甲苯、1,8-二胺基萘等之芳香族胺系硬化促進劑;N,N’-雙(3-胺基丙基)乙烯二胺、3,3-二胺基二丙基胺、1,8-二胺基辛烷、1,10-二胺基癸烷、3,3-二胺基二丙基胺、二乙烯三胺、三乙烯四胺、四乙烯五胺等之鏈狀脂肪族聚胺;1,4-雙(3-胺基丙基)哌嗪、N-(2-胺基乙基)哌嗪、N-(2-胺基乙基)嗎啉、N-胺基乙基哌嗪、異佛爾酮二胺等之環狀脂肪族聚胺;聚醯胺胺;咪唑系硬化促進劑;及胍系硬化促進劑。前述聚醯胺胺係藉由二聚酸與聚
胺的縮合而生成者,例如可列舉己二酸二醯肼、7,11-十八碳二烯-1,18-二卡肼。作為前述咪唑系硬化促進劑,可列舉2-甲基咪唑、2-乙基-4-甲基咪唑、1,3-雙(肼基羰乙基)-5-異丙基乙內醯脲。作為前述胍系硬化促進劑,可列舉1,3-二苯基胍、1,3-o-三胍等之脂肪族胺。特佳為使用第3級胺、第3級胺鹽、或咪唑系硬化促進劑。
本發明之組成物所摻合之無機質填充材,可使用環氧樹脂組成物通常所摻合之者。作為無機質填充材之具體例,例如可列舉熔融二氧化矽、結晶性二氧化矽等之二氧化矽類、氧化鋁、氮化矽、氮化鋁、氮化硼、氧化鈦、玻璃纖維等。
無機質填充材藉由雷射繞射法測定之平均粒徑為1~20μm,尤其是以平均粒徑3~15μm,且球狀較佳,特佳為這般的平均粒徑及形狀的熔融二氧化矽。進而,此無機質填充材係藉由下述式(7)所示之矽烷偶合劑進行表面處理。
【化9】R1 a(OR2)(3-a)Si-C3H6-R3 (7)
(式(7)中,R1為甲基或乙基,R2為碳數1~3之烷基,R3係選自由下述式(8)~(11)表示之含氮官能基所構成之群組中之基,a為0~3之整數)
藉由此處理,係與氰酸酯的親和性優異,可增強與無機質填充材的結合,且可使組成物的流動性顯著提昇。針對於該偶合劑之表面處理方法,可使用周知之方法,並未特別限制。
作為式(7)表示之矽烷偶合劑的摻合量,相對於無機質填充材100質量份,較佳為0.2~0.5質量份。矽烷偶合劑的摻合量少時,有氰酸酯與無機質填充材無法充分結合、或組成物的流動性無法充分得到的情況。矽烷偶合劑的摻合量多時,有膨脹係數增大的情況。
(D)成分之摻合量相對於(A)及(B)成分之合計100質量份,較佳為1,200~2,200質量份,更佳為1,400~2,000質量份。未滿上述下限時,成形後之彎曲增大,無法得到充分之強度,超過上述上限時,流動性顯著惡化,不能完成子安裝(Sub mount)上所配列之半導
體元件的完全密封。
本發明之耐熱性樹脂組成物雖藉由摻合上述成分(A)~(D)之預定量而得到,但如有必要可將其他添加劑在不損及本發明之目的、效果的範圍添加。作為該添加劑,可列舉無機填充材、脫模劑、阻燃劑、離子阱劑、抗氧化劑、接著性賦予劑、低應力劑、著色材等。
阻燃劑係以賦予阻燃性為目的而添加。該阻燃劑可全部使用周知者,例如可使用偶磷氮(Phosphazene)化合物、矽氧化合物、鉬酸鋅載持滑石、鉬酸鋅載持氧化鋅、氫氧化鋁、氫氧化鎂、氧化鉬等。
離子阱劑係以捕捉樹脂組成物中包含之離子雜質,防止熱劣化或吸濕劣化為目的而添加。離子阱劑可全部使用周知者,例如可使用水滑石類、氫氧化鉍化合物、稀土類氧化物等。
接著性賦予劑係以賦予對於密封之晶片或基材之接著性為目的而添加。該接著性賦予劑可全部使用周知者,例如可列舉於分子內具有乙烯基、胺基、環氧基、(甲基)丙烯醯基、巰基等之接著性官能基與水解性矽烷基之矽烷化合物、聚矽氧烷化合物等。
作為矽烷化合物之例,可列舉乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧
基矽烷、γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基三乙氧基矽烷、γ-環氧丙氧基丙基甲基二乙氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、γ-丙烯醯氧基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、γ-胺基丙基三甲氧基矽烷、γ-巰基丙基三甲氧基矽烷等。又,聚矽氧烷化合物可為環狀、鏈狀、網目鏈狀之任一者。
(E)成分之摻合量雖因組成物的用途而相異,但通常為組成物全體之20質量%以下的量。
本發明之熱硬化性樹脂組成物之製造方法
本發明之熱硬化性樹脂組成物例如可用如以下所示之方法調製。
首先,藉由將(A)氰酸酯化合物與(B)酚硬化劑同時或分別如有必要邊進行加熱處理邊混合、攪拌及/或分散,而得到(A)及(B)成分之混合物。於(A)及(B)成分之混合物藉由混合、攪拌及/或分散(C)硬化促進劑,而得到(A)~(C)成分之混合物。而且於(A)~(C)成分之混合物藉由混合、攪拌及/或分散(D)無機質填充材,而得到(A)~(D)成分之混合物。視使用用途,可於(A)及(B)成分之混合物、(A)~(C)成分之混合物、(A)~(D)成分之混合物摻合脫模劑、阻燃劑及離子阱劑的添加劑當中至少1種來混合。
混合、攪拌、分散等之裝置雖並未特別限定,但具體而言,可使用具備攪拌及加熱裝置之破碎機、雙輥、三輥、球磨機、連續擠出機、行星式混合機、融碎機(Masscolloider)等,可適當組合此等之裝置使用。
本發明之熱硬化性樹脂組成物雖可利用以往之壓縮成形或層壓成形來成形,但特佳為進行壓縮成形。此情況下,以組成物的成形溫度為160~180℃進行300~600秒,後固化於160~180℃進行1~6小時較佳。
本發明之組成物可縮小於8英寸、12英寸及20英寸晶圓上所成形時之彎曲。又,本發明之組成物的硬化物係機械強度、絕緣性優異,以該硬化物密封之半導體裝置係長期信賴性優異。進而,本發明之組成物在以往之壓縮、或層壓成形時所使用之裝置及成形條件,由於未產生流痕或未填充之成形不佳,從生產性的觀點來看亦優異。
在本說明書所謂流痕,係指從成形物之中心面向外側於放射狀所殘留之白色流動痕。產生流痕時,有外觀不佳、或因二氧化矽不均勻分散導致硬化物的物性不均勻、或伴隨其擔心而降低信賴性等。
在本說明書所謂未填充,係指於晶圓外周部所產生之樹脂的欠缺。產生未填充時,於後步驟運輸晶圓時,傳感器將未填充部誤認為缺口,擔心配合位置之特性降低。
於以下雖展示本發明之實施例,但本發明並非被限定於此。尚,在本說明書所謂黏度,係指以JIS K7117-1:1999記載之方法使用B型回轉黏度計測定在23℃之黏度。
藉由將熱硬化性樹脂組成物所包含之以下所示之各成分以表1所示之比例混合,以雙輥混錬,而得到熱硬化組成物。表示表1中之摻合比之數值的單位為「質量份」。
將前述所得之熱硬化性樹脂組成物的混合物以厚度成為100μm的方式,塗佈在實施熱輥與脫模處理之聚酯薄膜(保護層)表面,製造實施例1~8及比較例1~6之片狀硬化物。比較例4及6係樹脂與無機質填充材的潤濕性不良,無法成為片狀。使用可成為片狀之組成物進行以下所示之試驗及評估。
(A)氰酸酯化合物
(A1)下述式(12)表示之1,1-雙(4-氰氧苯基)乙烷(黏度:0.08Pa.s)(商品名LECY、LOZNA(股)製)
(A2)下述式(13)表示之酚酚醛清漆型氰酸酯(n=0~2)(黏度:250Pa.s)(商品名PT30、LOZNA(股)製)
(B)酚硬化劑
(B1)下述式(14)表示之間苯二酚型酚樹脂(n=0~4、R1及R2為烯丙基,重量平均分子量450~600,當量107)(商品名MEH-8400、明和化成股份有限公司製)
(B2)下述式(14)表示之間苯二酚型酚樹脂(n=5~7、R1及R2為烯丙基,重量平均分子量800~1100,當量132)(明和化成股份有限公司製)
(B3)下述式(14)表示之間苯二酚型酚樹脂(n=0~4、R1及R2為n-丙基,重量平均分子量450~600,當量
107)(明和化成股份有限公司製)
(B4)下述式(14)表示之間苯二酚型酚樹脂(n=0~4、R1及R2為乙烯基,重量平均分子量450~600,當量107)(明和化成股份有限公司製)
(B5)芳基酚酚醛清漆(商品名MEH-8000H、明和化成股份有限公司製、當量141)
(C)硬化促進劑
(C1)DBU系四苯基硼酸鹽(商品名U-CAT 5002、Sun Apro公司製)
(D)無機質填充材
(D1)處理二氧化矽
對於基底球狀熔融二氧化矽(平均粒徑12μm之球狀熔融二氧化矽(龍森製))100質量份,以0.3質量份之N-苯基-3-胺基丙基三甲氧基矽烷(商品名KBM573、信越化學工業股份有限公司製)進行乾式表面處理,調製處理
二氧化矽(D1)。
(D2)處理二氧化矽
又,對於球狀熔融二氧化矽(平均粒徑12μm之球狀熔融二氧化矽(龍森製))100質量份,以0.3質量份之γ-環氧丙氧基丙基三甲氧基矽烷(商品名KBM403、信越化學工業股份有限公司製)進行乾式表面處理,調製處理二氧化矽(D2)。
(D3)處理二氧化矽
對於基底球狀熔融二氧化矽(平均粒徑0.8μm之球狀二氧化矽(龍森製))100質量份,以0.3質量份之N-苯基-3-胺基丙基三甲氧基矽烷(商品名KBM573、信越化學工業股份有限公司製)進行乾式表面處理,調製處理二氧化矽(D3)。
(D4)無處理二氧化矽
並非將(D1)使用之球狀熔融二氧化矽(平均粒徑12μm、龍森製)進行表面處理而是以無處理的狀態使用。
(E)其他添加劑
(E1)接著性賦予劑:γ-環氧丙氧基丙基三甲氧基矽烷(商品名KBM403、信越化學工業股份有限公司製)
(E2)著色材:碳黑(商品名三菱CAN3230MJ、三菱化學製)
根據JIS K 7197:2012所記載之方法,將在實施例及比較例製造之片狀的硬化物分別於5×5×15mm之試驗片加工後,將該等之試驗片設定在熱膨脹計TMA8140C(理學股份有限公司製)。而且以昇溫5℃/分鐘之加熱、與加入19.6mN之一定荷重般來設定,測定從25℃至300℃之間試驗片的尺寸變化。將此尺寸變化與溫度的關係描繪在圖表。從如此進行所得之尺寸變化與溫度的圖表,由下述所說明之玻璃轉移溫度的決定方法,求得在實施例及比較例之玻璃轉移溫度。
在圖1,將於變曲點之溫度以下得到尺寸變化-溫度曲線之切線的任意溫度2點定為T1及T2,將於變曲點之溫度以上得到同樣之切線的任意溫度2點定為T1’及T2’。將在T1及T2之尺寸變化分別定為D1及D2,將結合點(T1、D1)與點(T2、D2)之直線、與在T1’及T2’之尺寸變化分別定為D1’及D2’,將與結合點(T1’、D1’)與點(T2’、D2’)之直線的交點定為玻璃轉移溫度(Tg)。將T1~T2之斜率定為Tg以下之線膨脹係數(線膨脹係數1),將T1’~T2’之斜率定為Tg以上之線膨脹係數(線膨脹係數2)。
將液狀樹脂組成物於175℃ 600秒,壓縮成形成樹脂厚度300μm後,在180℃/1小時使其完全硬化(後固化)。然後,由外觀目視評估流痕及未填充的有無。
使用矽晶圓12英寸/775μm厚,在APIC YAMADA公司製晶圓模組,將液狀樹脂組成物於175℃ 600秒,壓縮成形成樹脂厚度300μm後,在180℃/1小時使其完全硬化(後固化)。然後測定彎曲(mm)。
於厚度200μm之8英寸矽晶圓,將晶粒接合材SFX-513M1(信越化學工業股份有限公司製)使用厚膜絲網印刷機(THICK FILM PRINTER型MC212)進行印刷成20μm厚,於B階段狀態於7mm平方大使用切割裝置進行切割,來準備半導體晶片。
其次,於厚度200μm之8英寸矽晶圓上使用倒裝晶片鍵合機(Panasonic NM-SB50A),以厚度220μm將7mm平方之附晶粒接合材之半導體晶片以10N/150℃/1.0秒的條件進行晶粒接合,而得到搭載半導體晶片之厚度200μm之矽晶圓。
將附半導體晶片之厚度200μm矽晶圓設定在壓縮成形機,適量承載液狀樹脂組成物,於成形壓力最大
從30MPa至15MPa之間於110℃ 10分鐘進行硬化,而得到矽晶圓。液狀樹脂組成物的量以成形後之樹脂厚度成為400μm±10μm的方式來調整。將其矽晶圓於150℃、2小時烤箱進行熱處理再進行後硬化。然後,再次使用切割裝置切割成7.1mm平方,而得到厚度400μm之單片化樹脂搭載半導體晶片。
將單片化樹脂搭載半導體晶片於BT基板上使用倒裝晶片鍵合機(Panasonic NM-SB50A),以10N/150℃/1.5秒的條件以晶粒接合材SFX-513S(信越化學工業股份有限公司製)晶粒接合。然後於150℃、4小時烤箱進行熱處理,再進行後硬化,而得到附樹脂搭載半導體晶片之BT基板。
於附樹脂搭載半導體晶片之BT基板上將模複合物材料使用轉移成形機(G-LINEPress APIC YAMADA公司製),以175℃、90秒、9MPa的成形條件成形成1.5mm厚。然後再次使用切割裝置,切割成10.0mm平方,而得到附單片化模複合物樹脂搭載半導體晶片之BT基板(半導體裝置)。
將上述半導體裝置以85℃、85%RH的條件進行168小時吸濕處理。將此於以最大溫度260℃、255~260℃之時間成為30秒±3秒的方式預先設定之回流烤箱通過3次進行焊接耐熱試驗(剝離檢査)。在超音波探傷裝置(Sonics公司製QUANTUM350)以75MHz之探測器,無破壞檢査半導體晶片內部之剝離狀態,將無剝離及
裂縫的情況評估為「良好」,有剝離及裂縫的情況評估為「NG」。
將附單片化之模複合物樹脂搭載半導體晶片之BT基板使用ESPEC公司製小型冷熱衝撃裝置TSE-11,進行-55℃/15分鐘+125℃/15分鐘(自動)的循環。首先,在超音波探傷裝置(Sonics公司製QUANTUM350)使用75MHz之探測器,無破壞檢査0循環之半導體晶片內部的剝離狀態。其次,於250循環後、500循環後及700循環後進行同樣之檢査。將此檢査結果示於表1。相對於半導體晶片之面積之剝離面積的合計,將約未滿5%(微小剝離)的情況評估為「OK(無剝離)」,將剝離面積的合計為5%以上的情況評估為「NG(有剝離)」。
對於(B)成分之酚硬化劑,使用間苯二酚型酚樹脂(B1~B4)以外之酚硬化劑(B5)的情況下,彎曲量(mm)增大(比較例1)。又,即使將酚硬化劑(B5)的使用量增加至2倍,與實施例1~8進行比較,彎曲量(mm)較大。對於(A)成分之氰酸酯化合物,降低1,1-雙(4-氰氧苯基)乙烷(A1)的摻合量時,產生未填充(比較例3)。對於(D)成分之無機質填充材,使用D2的情況(比較例4)、或於過剩高填充D1的情況(比較例6),無法將樹脂組成物成為片狀。尚,降低無機質填充材的摻合量時,彎曲量增大,產生剝離或裂縫(比較例5)。
由上述結果,瞭解到本發明之樹脂組成物係玻璃轉移溫度、流動性及耐熱性高,且彎曲、膨脹及收縮縮小,可形成成片狀。
Claims (6)
- 一種半導體密封用熱硬化性樹脂組成物,其係包含下述(A)~(D)成分:(A)於1分子中具有2個以上氰氧基(cyanato)之氰酸酯化合物,其包含以JIS K7117-1:1999記載之方法,使用B型回轉黏度計測定在23℃之黏度為50Pa.s以下之下述式(1)表示之氰酸酯化合物,
- 如請求項1之半導體密封用熱硬化性樹脂組成物,其中,在前述(A)成分中,式(1)表示之氰酸酯化合物相對於(A)成分全體的摻合量為90質量%以上未滿100質量%,且包含2種以上之氰酸酯化合物。
- 如請求項1或2之半導體密封用熱硬化性樹脂組成物,其中,在前述(B)成分中,式(6)表示之間苯二酚型酚樹脂相對於(B)成分全體的摻合量為10質量%以上100質量%以下,且相對於(B)成分之酚硬化劑中之羥基1當量,(A)成分之氰酸酯化合物中之氰氧基為0.5~100當量。
- 如請求項1或2之半導體密封用熱硬化性樹脂組成物,其中,根據JIS K 7197:2012所記載之方法,使用5×5×15mm之試驗片,以昇溫5℃/分鐘、荷重19.6mN測定時之線膨脹係數為3.0~5.0ppm/℃的範圍。
- 一種樹脂密封型半導體裝置之製造方法,其係具有將載置1個以上半導體元件之面積200~1500cm2的矽晶圓或基板全體,以如請求項1~4中任一項之半導體密封用熱硬化性樹脂組成物的硬化物一次密封之步驟,且密封後之矽晶圓或基板的彎曲量為2mm以下。
- 如請求項5之樹脂密封型半導體裝置之製造方法,其中,在一次密封之步驟中,將半導體密封用熱硬化性樹脂組成物於按壓下進行被覆、或於真空環境下進行減 壓被覆,加熱硬化該樹脂組成物,密封半導體元件。
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JP2012209453A (ja) | 2011-03-30 | 2012-10-25 | Sumitomo Bakelite Co Ltd | 液状樹脂組成物、半導体パッケージ、および半導体パッケージの製造方法 |
US20140242394A1 (en) * | 2011-07-11 | 2014-08-28 | Mitsubishi Gas Chemical Company, Inc. | Curable resin composition and method for manufacturing cured product using the same |
JP5673496B2 (ja) * | 2011-11-07 | 2015-02-18 | 信越化学工業株式会社 | 樹脂組成物、樹脂フィルム及び半導体装置とその製造方法 |
JP6236222B2 (ja) * | 2012-06-11 | 2017-11-22 | 株式会社日本触媒 | シアネートエステル系組成物及びその用途 |
JP6116852B2 (ja) * | 2012-10-12 | 2017-04-19 | 株式会社日本触媒 | 液状硬化性樹脂組成物及びその用途 |
JP5735036B2 (ja) | 2013-05-23 | 2015-06-17 | 日東電工株式会社 | 電子部品装置の製造方法、及び、積層シート |
JP5977717B2 (ja) * | 2013-07-29 | 2016-08-24 | 信越化学工業株式会社 | 半導体封止用基材付封止材、半導体封止用基材付封止材の製造方法、及び半導体装置の製造方法 |
JP5881179B2 (ja) * | 2013-08-28 | 2016-03-09 | 信越化学工業株式会社 | 半導体封止用樹脂組成物及びその硬化物を備えた半導体装置 |
KR102219584B1 (ko) * | 2013-08-29 | 2021-02-23 | 신에쓰 가가꾸 고교 가부시끼가이샤 | 반도체 밀봉용 수지조성물 및 그 경화물을 구비한 반도체 장치 |
JP6231344B2 (ja) * | 2013-10-10 | 2017-11-15 | 信越化学工業株式会社 | ウエハの封止方法及びウエハレベル封止用樹脂組成物 |
JP6304073B2 (ja) * | 2014-06-05 | 2018-04-04 | 信越化学工業株式会社 | 熱硬化性樹脂組成物 |
JP2016121294A (ja) * | 2014-12-25 | 2016-07-07 | 信越化学工業株式会社 | 半導体封止用液状アンダーフィル材組成物及びフリップチップ型半導体装置 |
JP6520872B2 (ja) * | 2016-09-01 | 2019-05-29 | 信越化学工業株式会社 | 半導体封止用熱硬化性樹脂組成物 |
-
2015
- 2015-07-07 JP JP2015135799A patent/JP6369405B2/ja active Active
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2016
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- 2016-07-05 EP EP16177990.5A patent/EP3115393A1/en not_active Withdrawn
- 2016-07-06 TW TW105121390A patent/TWI681985B/zh active
- 2016-07-06 US US15/202,870 patent/US20170009007A1/en not_active Abandoned
- 2016-07-07 CN CN201610534439.1A patent/CN106336510B/zh active Active
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2018
- 2018-02-26 US US15/905,039 patent/US10407536B2/en active Active
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JP6369405B2 (ja) | 2018-08-08 |
JP2017014472A (ja) | 2017-01-19 |
CN106336510B (zh) | 2020-06-02 |
KR20170006266A (ko) | 2017-01-17 |
US20170009007A1 (en) | 2017-01-12 |
US20180186925A1 (en) | 2018-07-05 |
US10407536B2 (en) | 2019-09-10 |
EP3115393A1 (en) | 2017-01-11 |
KR102541769B1 (ko) | 2023-06-09 |
CN106336510A (zh) | 2017-01-18 |
TWI681985B (zh) | 2020-01-11 |
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