TWI390621B - 半導體用接著片及切割膠帶一體型半導體用接著片 - Google Patents
半導體用接著片及切割膠帶一體型半導體用接著片 Download PDFInfo
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- TWI390621B TWI390621B TW097143118A TW97143118A TWI390621B TW I390621 B TWI390621 B TW I390621B TW 097143118 A TW097143118 A TW 097143118A TW 97143118 A TW97143118 A TW 97143118A TW I390621 B TWI390621 B TW I390621B
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Description
本發明是關於一種半導體用接著片及切割膠帶一體型半導體用接著片。
於先前,半導體元件與半導體元件搭載用支撐部件之接合主要使用銀漿(silver paste)。但是,隨著近年來半導體元件之小型化、高性能化,對所使用之支撐部件亦要求小型化、細密化。對於如此之要求,由於利用銀漿時會露出或是半導體元件之傾斜而引起打線接合(Wire Bonding)時產生異常、難以控制接著片之膜厚、以及接著片產生空隙等,因此不能很好地應對上述要求。因此,為了因應上述要求,近年來開始使用片狀之接著劑。
該接著片於單片貼附方式或者晶圓背面貼附方式中使用。使用前者之單片貼附方式的接著片來製造半導體裝置的情況下,藉由切割或者沖孔將捲筒狀之接著片切為單片之後,將該單片與支撐部件接著而獲得附有接著片之支撐部件,在其上接合藉由切割步驟而單片化之半導體元件,製作附有半導體元件之支撐部件,然後視需要進行打線接合步驟、密封步驟等,藉此獲得半導體裝置。然而,為了使用上述單片貼附方式之接著片。必需將接著片切為單片,將該單片與支撐部件接著的專用組裝裝置,因此相較於使用銀漿之方法而存在製造成本變高之問題。
另一方面,使用後者之晶圓背面貼附方式接著片來製造半導體裝置的情況下,首先於半導體晶圓之背面貼附接著片,進一步於接著片之另一面貼合切割膠帶;然後將上述晶圓切割而單片化為半導體元件;拾取單片化後之附有接著片之半導體元件而將其與支撐部件接合;然後進行加熱、硬化、打線接合等步驟,藉此獲得半導體裝置。該晶圓背面貼附方式接著片是將附有接著片之半導體元件與支撐部件接合,因此無需將接著片單片化之裝置,可以直接使用先前之銀漿用組裝裝置或者藉由附加熱盤等而改良裝置之一部分而使用。因此,在使用接著片之組裝方法中,可以抑制製造成本而較為便宜,因而受到關注。
然而,於使用晶圓背面貼附方式之接著片的方法中,於晶圓之切割步驟時亦必需切斷接著片。作為切斷該接著片之方法,存在如下之方法:使用金剛石刀片而切斷的接觸型切斷方法;對晶圓照射雷射而於晶圓內部選擇性形成改質部,然後進行延伸而沿著改質部切斷晶圓,同時切斷接著片之方法;或者於切斷之晶圓上貼附接著片,然後進行延伸而沿著晶圓切斷線將接著片切斷的方法(例如參照日本專利特開2006-093213號公報)等。然而,於任一種方法中,均難以用相同的步驟切斷無機物之堅硬的晶圓與有機物之柔軟的接著片,因此有效的是於接著片中添加無機填料而調整為適度之硬度以提高切斷性。
另外,搭載有以半導體元件為首之各種電子零件的封裝基板的最重要特性之一是具有可靠性。其中,對於熱疲勞(thermal fatigue)之連接可靠性直接關係到使用封裝基板之機器的可靠性,因此是非常重要的項目。使該連接可靠性降低的原因可列舉由於使用熱膨脹係數不同之各種材料而產生之熱應力。這是由於半導體元件之熱膨脹係數較小,約為4ppm/℃,相對於此,封裝電子零件之配線基板的熱膨脹係數較大,為15ppm/℃或15ppm/℃以上,因此對於熱衝擊產生熱應變,由於該熱應變產生熱應力,而此熱應力使連接可靠性降低。因此,緩和該熱應力成為接著片的課題。另外,如此之配線基板一般具有由於配線所產生之凹凸,於接合時埋入該配線基板中之凹凸對於接著片來說是必要的。自熱應力緩和性及配線基板之凹凸埋入性等觀點考慮,較理想的是半導體用接著片於硬化後之彈性模數低至某種程度,若為了提高接著片之切斷性而添加無機填料,則接著片一般會變為高彈性化,兼顧半導體封裝之可靠性與接著片之切斷性成為課題。
本發明之課題在於提供一種利用延伸進行單片化時的切斷性良好,並且在接合時於配線基板之凹凸中之埋入性良好且可靠性優異的半導體用接著片及切割膠帶一體型半導體用接著片。
先前的接著片,可利用延伸而進行接著片之單片化,因此於樹脂組合物中添加無機填料,可減少接著片於硬化前之斷裂伸長率,但硬化後之高溫彈性模數變高且配線基板的凹凸埋入性差。
本發明者等人進行銳意研究,結果發現可將硬化前之接著片於0℃下之斷裂伸長率保持為較小,且可降低硬化後之高溫彈性模數,從而完成本發明。
本發明是關於(1)一種半導體用接著片,其是包含含有高分子量成分及填料之樹脂組合物的半導體用接著片,其特徵在於:硬化前之接著片於0℃下之斷裂伸長率為40%或40%以下,硬化後之接著片於175℃下之彈性模數為0.1MPa~10MPa。
另外,本發明是關於(2)如上述(1)所述之半導體用接著片,其中上述高分子量成分之Tg(玻璃轉化溫度)為-10℃~60℃、重量平均分子量為2萬~100萬。
並且,本發明是關於(3)如上述(1)或(2)所述之半導體用接著片,其中上述樹脂組合物於將其總量設為100wt%之情形時,含有50wt%~65wt%之高分子量成分及35wt%~50wt%之填料。
並且,本發明是關於(4)如上述(3)所述之半導體用接著片,其中上述填料是含有一次粒子之平均粒徑為0.005μm~0.1μm的填料。
並且,本發明是關於(5)如上述(4)所述之半導體用接著片,其中於樹脂組合物中含有1wt%~15wt%的上述一次粒子之平均粒徑為0.005μm~0.1μm之填料。
並且,本發明是關於(6)如上述(1)~(5)中任一項所述之半導體用接著片,其中於上述樹脂組合物中含有低分子量聚合物。
並且,本發明是關於(7)如上述(6)所述之半導體用接著片,其中上述低分子量聚合物的重量平均分子量為0.1萬~1萬。
並且,本發明是關於(8)如上述(6)或(7)所述之半導體用接著片,其中上述低分子量聚合物是於末端具有羧基之丁二烯聚合物。
並且,本發明是關於(9)一種切割膠帶一體型半導體用接著片,其是將如上述(1)~(8)中任一項所述之半導體用接著片與切割膠帶積層而成。
根據本發明,可獲得於製造半導體裝置時的單片化為附有接著片之半導體元件之步驟中,利用延伸之接著片的切斷性良好,並且於接合時之於配線基板之凹凸的埋入性良好且可靠性優異之半導體用接著片及切割膠帶一體型半導體用接著片。
為讓本發明之上述特徵和優點能更明顯易懂,下文特舉實施例,並配合所附圖式作詳細說明如下。
本發明之半導體用接著片是包含含有高分子量成分及填料之樹脂組合物的半導體用接著片,其特徵在於硬化前之接著片於0℃下之斷裂伸長率為40%或40%以下,硬化後之接著片於175℃下之彈性模數為0.1MPa~10MPa。
其中,硬化前之接著片是指處於B-階段(B-stage)狀態之接著片。
本發明之半導體用接著片,重要的是硬化前之接著片於0℃下之斷裂伸長率為40%或40%以下,於超過40%之情形時利用延伸之接著片之切斷性變差。上述斷裂伸長率較好的是35%或35%以下,更好的是30%或30%以下。
上述斷裂伸長率可使用TENSILON(TOYO BALDWIN製造、UTM-III-500),於夾盤間距離為20mm、拉伸速度為3mm/min、溫度為0℃的條件下,拉伸硬化前之厚度為40μm之接著片,測定斷裂時接著片的長度,利用下式而求出。
斷裂伸長率(%)=(斷裂時接著片的長度(mm)-20)/20×100
於本發明之接著片中,可調整樹脂組合物中之高分子量成分及填料之含量以使硬化前之接著片於0℃下之斷裂伸長率為40%或40%以下。具體而言,較有效的是降低樹脂組合物中高分子量成分之含量,且提高填料之含量;更有效的是使樹脂組合物中高分子量成分之含量為65wt%或65wt%以下以及使填料之含量為35wt%或35wt%以上;特別有效的是使高分子量成分之含量為50wt%~65wt%以及使填料之含量為35wt%~50Wt%。
本發明之半導體用接著片,重要的是硬化後之接著片於175℃下之彈性模數為0.1MPa~10MPa,若未滿0.1MPa則可靠性降低,若超過10MPa則於配線基板之凹凸中的埋入性降低。上述彈性模數較好的是1MPa~9MPa,更好的是3MPa~8MPa。
上述彈性模數可使用動態黏彈性測定裝置(Rheology公司製造、DVE-V4),對接著片(寬4mm、厚40μm)於175℃下硬化3小時後所得之硬化物施加拉伸負荷(10g),於溫度依存性測定模式進行測定,該溫度依存性測定模式是夾盤間距離為20mm、頻率為10Hz、以3℃/min之升溫速度自25℃升溫至300℃下進行測定。
於本發明之接著片中,可調整樹脂組合物中之高分子量成分及填料的含量以使硬化後之接著片於175℃下之彈性模數成為0.1MPa~10MPa。具體而言,有效的是提高樹脂組合物中高分子量成分之含量,且降低填料之含量;更有效的是使樹脂組合物中高分子量成分之含量為50wt%或50wt%以上以及使填料之含量為50wt%或50wt%以下;特別有效的是使高分子量成分之含量為50wt%~65wt%以及使填料之含量為35wt%~50wt%。
本發明之接著片包含含有高分子量成分及填料之樹脂組合物。
高分子量成分的Tg(玻璃轉移溫度)較好的是-10℃~60℃,更好的是-5℃~10℃,特別好的是0℃~5℃。藉由使上述Tg為-10℃或-10℃以上,可防止於延伸時切割膠帶斷裂,藉由使上述Tg為60℃或60℃以下,可抑制接著片軟化,易於使延伸時接著片之切斷變良好。
上述高分子量成分的重量平均分子量較好的是2萬~100萬,更好的是10萬~90萬,特別好的是50萬~80萬。藉由使上述重量平均分子量為2萬或2萬以上,可抑制接著片之強度或可撓性降低,防止黏性增大;藉由使上述重量平均分子量為100萬或100萬以下,可並不降低於樹脂組合物之溶劑中之溶解性而使操作變容易。另外,重量平均分子量是利用凝膠滲透層析法(Gel Permeation Chromatography,GPC)使用標準聚苯乙烯之校準曲線的聚苯乙烯換算值。
上述高分子量成分之含量,於將樹脂組合物之總量設為100wt%之情形時,較好的是50wt%~65wt%,更好的是52wt%~63wt%,特別好的是53wt%~60wt%。若上述含量未滿50wt%,則硬化後之接著片於175℃下之彈性模數變高,存在於配線基板之凹凸中的埋入性降低之可能性。若上述含量超過65wt%,則硬化前之接著片於0℃下之斷裂伸長率變大,存在利用延伸之接著片的切斷性差,單片化變困難之可能性,並且存在硬化後之接著片於175℃下之彈性模數變低且可靠性降低之可能性。
本發明中使用之高分子量成分可列舉聚醯胺樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、丙烯酸系共聚物等,較好的是與環氧樹脂不相容的含有丙烯酸縮水甘油酯或甲基丙烯酸縮水甘油酯等官能性單體的含有環氧基之丙烯酸系共聚物。若使用包含丙烯酸等羧酸型或(甲基)丙烯酸羥基甲酯等羥基型作為官能性單體的丙烯酸系共聚物,則存在交聯反應容易進行,且於清漆狀態下凝膠化、在硬化前之狀態因硬化度上升而造成接著力降低等問題,因此並不好。
上述含有環氧基之丙烯酸系共聚物中含有的(甲基)丙烯酸縮水甘油酯之含量較好的是1wt%~6wt%,更好的是2wt%~5wt%。藉由使上述含量為1wt%或1wt%以上,可防止接著力降低;藉由使上述含量為6wt%或6wt%以下而較易抑制凝膠化。上述(甲基)丙烯酸縮水甘油酯之含量表示(甲基)丙烯酸縮水甘油酯之重量相對於構成共聚物之單體之總重量的比例。
上述含有環氧基之丙烯酸系共聚物的Tg較好的是-10℃~60℃。藉由使上述Tg為-10℃或-10℃以上,可防止硬化前之狀態下的接著劑層之黏性增大,操作性變良好。另一方面,藉由使上述Tg為60℃或60℃以下,可抑制接著片軟化,容易使延伸時接著片的切斷變良好。並且,上述含有環氧基之丙烯酸系共聚物的重量平均分子量,自耐熱性之觀點考慮,較好的是50萬或50萬以上,更好的是60萬~80萬。如此之含有環氧基之丙烯酸系共聚物並無特別之限制,可使用由長瀨化成股份有限公司市售之商品名HTR-860P-3DR等。並且,利用合成獲得含有環氧基之丙烯酸系共聚物的方法可列舉使用(甲基)丙烯酸縮水甘油酯與(甲基)丙烯酸乙酯或(甲基)丙烯酸丁酯或者這兩種化合物之混合物作為單體,利用珠狀聚合(pearl polymerization)法、溶液聚合法等公知之方法進行聚合的方法。
於本發明中,自耐熱性之觀點考慮,樹脂組合物含有填料。填料並無特別之限定,較好的是無機填料,例如可列舉氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、矽酸鈣、矽酸鎂、氧化鈣、氧化鎂、氧化鋁、氮化鋁、硼酸鋁晶鬚、氮化硼、結晶性二氧化矽、非晶形二氧化矽、氧化物銻等。為提高導熱性,較好的是氧化鋁、氮化鋁、氮化硼、結晶性二氧化矽、非晶形二氧化矽等。為了調整熔融黏度或者賦予搖變減黏性(thixotropic),較好的是氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、矽酸鈣、矽酸鎂、氧化鈣、氧化鎂、氧化鋁、結晶性二氧化矽、非晶形二氧化矽等。並且,為了提高耐濕性,較好的是氧化鋁、二氧化矽、氫氧化鋁、氧化物銻等。這些化合物中,自通用性之觀點考慮更好的是二氧化矽。
上述填料之含量,於將樹脂組合物之總量設為100wt%之情形時,較好的是35wt%~50wt%,更好的是27wt%~48wt%,特別好的是27wt%~40wt%。若上述含量未滿35wt%,則變得難以使硬化前之接著片於0℃下之斷裂伸長率減小;若超過50wt%,則接著片之潤濕性(wettability)降低,存在晶圓貼附性、可靠性降低之可能性。
上述填料之平均粒徑並無特別之限定,較好的是一次粒子之平均粒徑為0.005μm~10μm。藉由使上述平均粒徑為10μm或10μm以下,容易使接著片薄膜化;藉由使上述平均粒徑為0.005μm或0.005μm以上,可使作業性變良好。於提高填料之含量,使彈性模數及埋入性變良好之方面考慮,若為上述平均粒徑之範圍,則較好的是混合使用具有不同粒徑分佈之多種填料。為減少硬化前之接著片於0℃下之斷裂伸長率,較好的是含有一次粒子之平均粒徑為0.005μm~0.1μm的填料,更好的是含有一次粒子之平均粒徑為0.010μm~0.05μm的填料,特別好的是含有一次粒子之平均粒徑為0.015μm~0.03μm的填料。上述一次粒子之平均粒徑為0.005μm~0.1μm之填料的含量,較好的是於樹脂組合物中含有1wt%~15wt%,更好的是含有2wt%~13wt%。藉由使上述含量為1wt%或1wt%以上,可使斷裂伸長率容易變小;藉由使上述含量為15wt%或15wt%以下,可防止接著劑層之黏性降低,且使操作性變良好。
上述平均粒徑,例如可藉由使用雷射光繞射法之粒度分佈測定而進行測定。並且,平均粒徑可作為中值粒徑(Median particle size)而求出。
於本發明中,自接著性之觀點考慮,較好的是樹脂組合物含有樹脂成分。樹脂成分可列舉丙烯酸樹脂、甲基丙烯酸樹脂、苯氧樹脂、環氧樹脂、酚樹脂、苯甲酚樹脂、氰酸酯樹脂等,為提高耐熱性,較好的是含有熱硬化性之官能基,其中更好的是環氧樹脂。環氧樹脂例如可列舉Yuka Shell Epoxy Co.,Ltd.製造、商品名:Epikote 1001、1002、1003、1055、1004、1004AF、1007、1009、1003F、1004F、陶氏化學日本股份有限公司製造、商品名:D.E.R.661、662、663U、664、664U、667、642U、672U、673MF、668、669等雙酚A型環氧樹脂;東都化成股份有限公司製造、商品名:YDF-2004、YDF-8170C等雙酚P型環氧樹脂;日本化藥股份有限公司製造、商品名:EPPN-201等酚類酚醛清漆型環氧樹脂;Yuka Shell Epoxy Co.,Ltd.製造、商品名:Epikote 180S65、汽巴精化股份有限公司製造、商品名:Araldite ECN1273、1280、1299、東都化成股份有限公司製造、商品名:YDCN-701、702、703、704、700-10、日本化藥股份有限公司製造、商品名:EOCN-1020、102S、103S、104S、住友化學工業股份有限公司製造、商品名:ESCN-195X、200L、220等甲酚清漆型環氧樹脂;Yuka Shell Epoxy Co.,Ltd.製造、商品名:Epon 1031S、Epikote 1032H60、157S70、日本化藥股份有限公司製造、商品名:EPPN501H、502H等多官能環氧樹脂;汽巴精化股份有限公司製造、商品名:Araldite PT810等含有雜環之環氧樹脂等,但並不限定於這些環氧樹脂。
環氧樹脂之重量平均分子量並無特別之限定,較好的是400~10,000,更好的是500~5,000,特別好的是600~3,000。若上述重量平均分子量未滿400,則為低黏度之液狀的情況較多,且存在接著片之斷裂性降低之可能性。若上述重量平均分子量超過10000,則隨著高分子量化,由於樹脂間的分子相互纏繞,於溶劑中之溶解性降低,作業性容易降低。
於使用熱硬化性樹脂作為樹脂成分之情形時,較好的是併用硬化劑,更好的是併用硬化促進劑。
本發明中使用之硬化劑,若為通常用作熱硬化性樹脂之硬化劑的硬化劑,則並無特別之限定,例如可列舉胺類,聚醯胺,酸酐,聚硫醚,三氟化硼,雙酚A、雙酚F、雙酚S之類的於1分子中具有2個或2個以上酚性羥基之雙酚類、酚系酚醛清漆樹脂、雙酚A酚醛清漆樹脂或者甲酚清漆樹脂等酚樹脂等。
這些硬化劑中,自耐熱性之觀點考慮,較好的是酚樹脂,更好的是投入於85℃、濕度85%RH之恆溫恆濕槽中48小時後的吸水率為2wt%或2wt%以下之酚樹脂,特別好的是進一步用熱重量分析儀(TGA)測定的於350℃下之加熱重量減少率(升溫速度:5℃/min、環境:氮氣)未滿5wt%的酚樹脂。該酚樹脂可使酚化合物與2價連結基之苯二甲基化合物,於無觸媒或者酸觸媒之存在下進行反應而獲得。市售品有三井化學股份有限公司製造、商品名:Milex XLC-系列、XL系列等。
熱硬化性樹脂與硬化劑之調配比例並無特別之限定,自化學計量之觀點考慮,較好的是反應基當量相同。
另外,本發明中使用之硬化促進劑並無特別之限制,例如可使用四級鏻鹽類、四級銨鹽類、咪唑類、DBU脂肪酸鹽類、金屬螯合物類、金屬鹽類、三苯基膦類等。這些化合物可單獨使用一種或者併用2種或2種以上。這些硬化促進劑中,較好的是咪唑類,其具體例可列舉2-甲基咪唑、2-乙基-4-甲基咪唑、1-氰乙基-2-苯基咪唑、1-氰乙基-2-苯基咪唑鎓偏苯三甲酸鹽等。
硬化促進劑之添加量,相對於熱硬化性樹脂及硬化劑之總量100重量份,較好的是0.001重量份~5重量份,更好的是0.05重量份~3重量份。
於本發明中,自斷裂性之觀點考慮,較好的是樹脂組合物含有低分子量聚合物。低分子量聚合物之重量平均分子量並無特別之限定,較好的是0.1萬~1萬,更好的是0.2萬~1萬,特別好的是0.3萬~0.5萬。若上述重量平均分子量未滿0.1萬,則多為低黏度之液狀之情況,存在接著片之斷裂性降低之可能性。若上述重量平均分子量超過1萬,則隨著高分子量化,於樹脂間之分子相互纏繞,因此存在接著片之斷裂性降低之可能性。
本發明中使用之低分子量聚合物,較好的是含有於末端具有羧基之丁二烯的均聚物或共聚物,例如可適宜使用的低分子量聚合物可列舉末端具有羧基之丙烯腈聚丁二烯共聚物之Hycar CTB-2009×162、CTBN-1300×31、CTBN-1300×8、CTBN-1300×13、CTBNX-1300×9(均為宇部興產股份有限公司製造),或者末端具有羧基之液狀聚丁二烯之NISSO-PB-C-2000(日本曹達股份有限公司製造)等。這些化合物可單獨使用,或者組合2種或2種以上使用。
於本發明中,較好的是樹脂組合物含有各種偶合劑(coupling agent)以使不同種材料間的界面結合變良好。偶合劑可列舉矽烷系偶合劑、鈦系偶合劑、鋁系偶合劑等,最好的是矽烷系偶合劑。
矽烷系偶合劑並無特別之限制,例如可使用乙烯基三氯矽烷、乙烯基三(β-甲氧基乙氧基)矽烷、乙烯基三乙氧基矽烷、乙烯基三甲氧基矽烷等乙烯基矽烷類;γ-甲基丙烯醯氧基丙基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基-三甲氧基矽烷、甲基三(甲基丙烯醯氧基乙氧基)矽烷等甲基丙烯醯基矽烷類;β-(3,4-環氧基環己基)乙基三甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基甲基二甲氧基矽烷、γ-縮水甘油氧基丙基甲基二乙氧基矽烷、甲基三(縮水甘油氧基)矽烷等含有環氧基之矽烷類;N-β(胺基乙基)γ-胺基丙基三甲氧基矽烷、N-β(胺基乙基)γ-胺基丙基甲基二甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷、3-胺基丙基甲基二乙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基-三(2-甲氧基-乙氧基-乙氧基)矽烷、N-甲基-3-胺基丙基三甲氧基矽烷、三胺基丙基-三甲氧基矽烷、3-4,5-二氫咪唑-1-基-丙基三甲氧基矽烷、戊基三氯矽烷等胺基矽烷類:γ-巰基丙基三甲氧基矽烷、γ-巰基丙基三乙氧基矽烷、3-巰基丙基-甲基二甲氧基矽烷等巰基矽烷類;3-脲基丙基三乙氧基矽烷、3-脲基丙基三甲氧基矽烷等含有脲鍵之矽烷類;三甲基矽烷基異氰酸酯、二甲基矽烷基異氰酸酯、甲基矽烷基三異氰酸酯、乙烯基矽烷基三異氰酸酯、苯基矽烷基三異氰酸酯、矽烷四異氰酸酯、乙氧基矽烷異氰酸酯等含有異氰酸酯基之矽烷類;3-氯丙基-甲基二甲氧基矽烷、3-氯丙基-二甲氧基矽烷、3-氰基丙基-三乙氧基矽烷、六甲基二矽氮烷、N,O-雙(三甲基矽烷基)乙醯胺、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙基三氯矽烷、正丙基三甲氧基矽烷、異丁基三甲氧基矽烷、辛基三乙氧基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、N-β(N-乙烯基苄基胺基乙基)-γ-胺基丙基三甲氧基矽烷、十八烷基二甲基[3-(三甲氧基矽烷基)丙基]氯化銨、γ-氯丙基甲基二氯矽烷、γ-氯丙基甲基二甲氧基矽烷、γ-氯丙基甲基二乙氧基矽烷等。這些偶合劑可單獨使用一種或者併用2種或2種以上。
本發明之半導體用接著片可利用如下方法獲得:將含有高分子量成分及填料,以及視需要含有其他成分的樹脂組合物溶解或者分散於溶劑中製備清漆,塗佈於載體膜上,進行加熱除去溶劑。
上述載體膜可使用聚四氟乙烯膜、聚對苯二甲酸乙二酯膜、聚乙烯膜、聚丙烯膜、聚甲基戊烯膜、聚萘二甲酸乙二酯膜、聚醚碸膜、聚醚醯胺膜、聚醚醯胺醯亞胺膜、聚醯胺膜、聚醯胺-醯亞胺膜、聚醯亞胺膜等塑膠膜,並且亦可視需要對這些塑膠膜進行塗佈底塗劑、UV處理、電暈放電處理、研磨處理、蝕刻處理、脫模處理等表面處理。亦可於使用時剝離載體膜而僅使用接著劑層,亦可於載體膜與接著劑層積層之狀態下使用,然後除去載體膜。載體膜之厚度可並無特別限制地適宜選擇,較好的是10μm~100μm。
製備清漆時使用的溶劑,若為可使各成分均勻溶解、混練或分散之溶劑則並無限制,可使用先前公知之溶劑。例如,較好的是考慮製作接著片時之揮發性等,使用丁酮、丙酮、甲基異丁基酮、2-乙氧基乙醇、甲苯、二甲苯、丁基賽路蘇、甲醇、乙醇、2-甲氧基乙醇等沸點較低之溶劑。並且,為了提高塗膜性等,亦可添加二甲基乙醯胺、二甲基甲醯胺、N-甲基吡咯烷酮、環己酮等沸點較高的溶劑。
製備清漆時使用之溶劑的使用量並無特別之限制,溶劑是藉由加熱乾燥等自接著片中除去的,製備接著片後之溶劑量較好的是以總重量標準為2wt%或2wt%以下,自作業性之觀點考慮,更好的是以總重量標準為1wt%或1wt%以下。
樹脂組合物含有填料時清漆之製備,考慮到填料之分散性,較好的是使用擂潰機(mortar machine)、三輥研磨機(three roll mill)、球磨機(ball mill)及珠磨機等,亦可將它們組合使用。並且,亦可於將填料與低分子量物預先混合之後,調配高分子量物,由此縮短混合之時間。並且,於製備清漆後,亦可藉由真空除氣等而除去清漆中之氣泡。
於載體膜上塗佈清漆之方法可使用公知之方法,例如可列舉刀塗法、輥塗法、噴塗法、凹板印刷式塗佈法、棒式塗佈法、簾塗法等。
於載體膜上形成之接著劑層的厚度,B-階段狀態之膜厚較好的是1μm~100μm,對此並無限制。藉由使上述膜厚為1μm或1μm以上可使成膜性變良好,藉由使上述膜厚為100μm或100μm以下可以比較經濟。並且,本發明之接著片的接著劑層,為獲得所需之厚度,亦可貼合2片或2片以上。於此情形時,必需接著劑層之間並不產生剝離之貼合條件。
本發明之接著片的厚度較好的是1μm~100μm,對此並無限制。藉由將上述片材之厚度保持為1μm或1μm以上可容易地保持片材形狀;藉由使上述片材之厚度為100μm或100μm以下,可使斷裂性變良好。
本發明之接著片可以其自身使用,亦可用作將本發明之接著片積層於先前公知之切割膠帶上而成的割膠帶體型半導體用接著片而作為一實施形態。於此情形時,自於晶圓上的層壓步驟一次即可之觀點考慮,可使作業有效率。
本發明中使用之切割膠帶,例如可列舉聚四氟乙烯膜、聚對苯二甲酸乙二酯膜、聚乙烯膜、聚丙烯膜、聚甲基戊烯膜、聚醯亞胺膜等塑膠膜等。另外,亦可視需要進行塗佈底塗劑、UV處理、電暈放電處理、研磨處理、蝕刻處理等表面處理。切割膠帶必需具有黏著性,且亦可於切割膠帶之単面設置黏著劑層。該黏著劑層可藉由塗佈樹脂組合物加以乾燥而形成,該樹脂組合物是於黏著劑層之樹脂組合物中,特別是藉由調整液狀成分之比率、高分子量成分之Tg所獲得之具有適度之黏著強度(Tack Strength)的樹脂組合物。
切割膠帶之膜厚並無特別之限制,可根據接著片之膜厚或切割膠帶體型接著片之用途,基於本領域技術人員之知識而適宜決定,自經濟性良好,膜之操作性良好之方面考慮,為60μm~200μm,較好的是70μm~170μm。
並且,於製造半導體裝置時使用本發明之接著片之情形時,該接著片必需具有於切割時半導體元件並不飛散之接著力,且於其後拾取時可自切割膠帶上剝離。例如,接著片或切割膠帶之黏著性過高且使兩者貼合時之剝離強度為150N/m或150N/m以上之情形時,存在變得難以分離之現象。因此,較好的是適宜調整接著片之黏著強度,其方法可利用由於使接著片於室溫下之流動性上升,存在接著強度及黏著強度上升之傾向,且若流動性降低則存在接著強度及黏著強度亦降低之傾向的現象。例如,於使流動性上升之情形時,有使塑化劑之含量增加、使增黏劑之含量增加等方法。相反於使流動性降低之情形時,可減少上述塑化劑之含量。上述塑化劑例如可列舉單官能之壓克力單體(Acrylic monomer)、單官能環氧樹脂、液狀環氧樹脂、丙烯酸系樹脂、環氧系之所謂稀釋劑等。
積層接著片與切割膠帶而成之切割膠帶體型接著片於切割時之剝離強度較好的是未滿150N/m,更好的是50N/m或50N/m以下。於切割膠帶上積層接著片之方法,除印刷之外,亦可列舉將預先製作之接著片壓於切割膠帶上進行層壓的滾筒層壓方法,亦可視需要進行加熱。可連續地進行製造,自效率良好之方面考慮,較好的是滾筒層壓方法。
以下,利用實施例對本發明加以詳細之說明,但本發明並不限定於這些實施例。
實施例1~實施例3及比較例1~比較例8
於含有表1所示之規定量的環氧樹脂YDCN-700-10(東都化成股份有限公司製造之商品名、甲酚清漆型環氧樹脂、環氧當量為210)或YDF-8170C(東都化成股份有限公司製造之商品名、BPF型環氧樹脂、環氧當量為160)、酚樹脂Milex XLC-LL(三井化學股份有限公司製造之商品名、酚樹脂、羥基當量為175、吸水率為1.8%、於350℃下之加熱重量減少率為4%)或LF-2882(大日本油墨化學工業股份有限公司製造之商品名、苯酚酚醛清漆樹脂)、矽烷偶合劑A-1160(GE東芝股份有限公司製造之商品名、γ-脲基丙基三乙氧基矽烷)、填料SO-C2(Adomatech股份有限公司製造之商品名、二氧化矽、比表面積為7m2
/g、平均粒徑為0.4μm~0.6μm)或艾羅技R972(日本Aerosil股份有限公司製造之商品名、二氧化矽、平均粒徑為0.016μm)的組合物中,添加環己酮進行攪拌混合,進一步使用珠磨機混練90分鐘。
於其中混合入含有表1所示之規定量的高分子量成分HTR-860P-3DR(長瀨化成股份有限公司製造之商品名、重量平均分子量為70萬、Tg為5℃、含有2wt%~6wt%丙烯酸縮水甘油酯或甲基丙烯酸縮水甘油酯之丙烯酸橡膠)、低分子量聚合物CTBNX-1300×9(宇部興產股份有限公司製造之商品名、重量平均分子量為3500、於末端具有羧基之丙烯腈聚丁二烯共聚物)、硬化促進劑Curezol2PZ-CN(四國化成股份有限公司製造之商品名、1-氰乙基-2-苯基咪唑)並加以攪拌,進行真空除氣而獲得溶劑成分為20%之清漆。
將清漆塗佈於作為載體膜之厚度為75μm之進行了脫模處理之聚對苯二甲酸乙二酯膜上,於140℃下加熱乾燥5分鐘,形成膜厚為40μm之B-階段狀態(硬化前)之塗膜,製作具備載體膜之接著片。
於表1中表示實施例1~實施例3、比較例1~比較例8之各成分的調配重量份。
關於上述實施例1~實施例3、比較例1~比較例8中所得之各接著片,對以下項目進行評價。
(1)硬化前之斷裂伸長率
使用TENSILON(TOYO BALDWIN製造、UTM-III-500),於夾盤間距離為20mm、拉伸速度為3mm/分、溫度為0℃之條件下,拉伸剝離了載體膜之硬化前之厚度為40μm之接著片,測定斷裂時之片材之長度,藉由下式求出斷裂伸長率(%)。結果示於表1中。
斷裂伸長率(%)=(斷裂時接著片之長度(mm)一20)/20×100
(2)硬化後之彈性模數
使用動態黏彈性測定裝置(Rheology公司製造、DVE-V4),將接著片(寬度為4mm、厚度為40μm)於175℃下加熱硬化3小時後,對剝離載體膜所得之硬化物施加拉伸負荷(10g),於溫度依存性測定模式進行測定,而該溫度依存性測定模式是夾盤間距離為20mm、頻率為10Hz、以3℃/min之升溫速度自25℃升溫至300℃下進行測定。結果示於表1中。
(3)接著片之切斷性
使用自動立體測圖儀(島津製作所製造、AGS-1000G),將剝離了載體膜之接著片於80℃之溫度下熱層壓於晶圓上之後,用金剛石切割器於晶圓中央部切入,僅切斷晶圓。將具有切斷之晶圓的附有接著片之晶圓冷卻,安裝於自動立體測圖儀上,於0℃之狀態下進行延伸,目視觀察接著片之切斷性。延伸條件是延伸速度為50mm/分、延伸量為1mm。將可以切斷接著片時記為「○」,將不能切斷時記為「×」,示於表1中。
(4)於配線基板之凹凸中之埋入性
將上述實施例1~實施例3及比較例1~比較例8之接著片之接著劑層分別貼合於半導體晶圓上,視需要剝離載體膜之後,經由接著層將半導體晶圓貼合於市售之紫外線硬化型切割膠帶(古河電工股份有限公司製造之商品名:UC-334EP-710)上。該切割膠帶是於基材上形成了黏著劑層之切割膠帶,於貼合時,使切割膠帶之黏著劑層與接著片之接著劑層接合。繼而,使用切片機將半導體晶圓及接著劑層切割之後,自切割膠帶之基材側照射紫外線(500mJ/cm2
),使接著劑層與黏著劑層之間離開,由此獲得附有接著劑層之半導體元件。將所得之附有接著劑層之半導體元件,經由接著劑層,於具有平均約10μm凹凸之配線基材上,於150℃下施加0.4×9.8N之力3秒鐘而進行加熱壓著。其後,於高溫加熱之情形時,於170℃之加熱板上加熱1小時,施加與打線接合同等之熱歷程(thermal history)。
接著,使用環氧密封樹脂(日立化成工業股份有限公司製造之商品名:CEL-9700HF),於180℃、6.75MPa、90秒之條件下進行樹脂密封,製造半導體裝置之樣本。
對各樣本,使用超音波斷層掃描攝影裝置(Scanning Acoustic Tomograph),根據於接著劑層與配線基材之間有無空隙,評價樹脂密封後的於配線基板之凹凸中的埋入性。將未確認空隙時記為「○」,將確認空隙時記為「×」,示於表1中。
實施例1~實施例3之接著片,硬化前之斷裂伸長率少,接著片之切斷性良好,並且硬化後之彈性模數低,於配線基板之凹凸中之埋入性優異。硬化後之彈性模數較高之比較例1、比較例2、比較例3、比較例7及比較例8之接著片,於配線基板之凹凸中之埋入性差。硬化前之斷裂伸長率較大之比較例4~比較例6之接著片,接著片之切斷性差。
雖然本發明已以實施例揭露如上,然其並非用以限定本發明,任何所屬技術領域中具有通常知識者,在不脫離本發明之精神和範圍內,當可作些許之更動與潤飾,故本發明之保護範圍當視後附之申請專利範圍所界定者為準。
Claims (9)
- 一種半導體用接著片,其是包含含有高分子量成分以及填料之樹脂組合物的半導體用接著片,其中硬化前之接著片於0℃下之斷裂伸長率為40%或40%以下,硬化後之接著片於175℃下之彈性模數為0.1MPa~10MPa。
- 如申請專利範圍第1項所述之半導體用接著片,其中上述高分子量成分之玻璃轉移溫度Tg為-10℃~60℃、重量平均分子量為2萬~100萬。
- 如申請專利範圍第1項所述之半導體用接著片,其中上述樹脂組合物於將其總量設為100wt%之情形時,含有50wt%~65wt%之高分子量成分及35wt%~50wt%之填料。
- 如申請專利範圍第3項所述之半導體用接著片,其中上述填料是含有一次粒子之平均粒徑為0.005μm~0.1μm的填料。
- 如申請專利範圍第4項所述之半導體用接著片,其中於樹脂組合物中含有1wt%~15wt%的上述一次粒子之平均粒徑為0.005μm~0.1μm之填料。
- 如申請專利範圍第1項所述之半導體用接著片,其中於上述樹脂組合物中含有低分子量聚合物。
- 如申請專利範圍第6項所述之半導體用接著片,其中上述低分子量聚合物的重量平均分子量為0.1萬~1萬。
- 如申請專利範圍第6項所述之半導體用接著片,其中上述低分子量聚合物是於末端具有羧基之丁二烯聚合物。
- 一種切割膠帶一體型半導體用接著片,其是將如申請專利範圍第1項至第8項中任一項所述之半導體用接著片與切割膠帶積層而成。
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