TWI577771B - An adhesive composition, an adhesive sheet using the adhesive composition, a semiconductor device protection material, and a semiconductor device - Google Patents
An adhesive composition, an adhesive sheet using the adhesive composition, a semiconductor device protection material, and a semiconductor device Download PDFInfo
- Publication number
- TWI577771B TWI577771B TW102113461A TW102113461A TWI577771B TW I577771 B TWI577771 B TW I577771B TW 102113461 A TW102113461 A TW 102113461A TW 102113461 A TW102113461 A TW 102113461A TW I577771 B TWI577771 B TW I577771B
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- Prior art keywords
- adhesive composition
- group
- composition according
- epoxy resin
- adhesive
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- C—CHEMISTRY; METALLURGY
- 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
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- C—CHEMISTRY; METALLURGY
- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C—CHEMISTRY; METALLURGY
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
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Description
本發明關於一種黏著劑組成物,尤其關於一種黏著劑組成物,該黏著劑組成物可適宜用於使用倒裝片(flip chip)構裝方式之半導體裝置的製造。進而,關於一種具有使用該黏著劑組成物而形成的黏著劑層之黏著片材及半導體裝置保護用材料、以及具備該黏著劑組成物的硬化物之半導體裝置。
近年來,伴隨著電子設備的小型化及高性能化,強烈要求半導體裝置的高密度化及高積體化,且IC封裝體的大容量化及高密度化正在發展。目前為止,連接半導體晶片與基板時,廣泛適用使用金屬細線之引線接合方式。然而,為與半導體裝置的高密度化及高積體化之要求相對應,於半導體晶片上形成稱為凸塊之導電性突起,且直接連接基板電極與半導體晶片的凸塊之倒裝片構裝方式正在成為主流。
一般而言,於倒裝片構裝方式中,以增強連接部分或提高半導體裝置的可靠性等為目的,利用底部填充劑(底層充填材料,underfill agent)來密封半導體晶片與電路板的間
隙。在利用底部填充劑來進行密封之方法中,一般採用毛細管底部填膠方式。毛細管底部填膠方式,是向晶片的一邊或複數面上塗佈底部填充劑,並利用毛細管現象使底部填充劑流入電路板與晶片的間隙中來填充之方法(專利文獻1)。然而,近年來,半導體裝置的高密度化及高積體化的要求越發強烈,凸塊之間的間距、及晶片之間的間隔不斷變得狹小,填充底部填充劑時會發生空氣易於捲入、空隙產生、及可靠性受損之問題。
又,在毛細管底部填膠方式中,需要第8圖所示之步驟(a)~(g)。以下說明各步驟。
步驟(a):將助焊劑21塗佈於電路板20上之步驟
步驟(b):經由(隔著)助焊劑21將形成有凸塊22a之半導體晶圓22裝配至電路板20上之步驟
步驟(c):經由助焊劑21接合半導體晶片22與電路板20之步驟(接合部23)
步驟(d):利用清洗來去除助焊劑21之步驟
步驟(e):向半導體晶片22的一邊或複數面上塗佈底部填充劑24之步驟
步驟(f):利用毛細管現象使底部填充劑24流入電路板20與半導體晶片22的間隙中之步驟
步驟(g):硬化經填充之底部填充劑(24a),並進行樹脂密封之步驟
如上述及第8圖所示,毛細管底部填膠方式的步驟煩雜,又,助焊劑清洗時需處理清洗廢液。進而,由於步
驟(f)中利用毛細管現象,因此,填充時間會較長,且半導體裝置的生產率會產生問題。
作為解決該等問題之方法,提案有以下方法:於具有複數個凸塊之晶片上的形成有凸塊之面上,形成黏著劑層後,連同黏著劑層一起切割晶片,並對附有黏著劑層之半導體晶片進行單片化(singulation)。利用切割而單片化之附有黏著劑層之半導體晶片,與其他半導體晶片、或基板黏結,並經由凸塊作電性接合。作為在該種晶片上所形成之黏著劑層所使用之黏著劑組成物,記載有一種黏著劑組成物,其具有熱硬化性化合物、含有可與前述熱硬化性化合物反應之官能基之聚合物、及熱硬化劑,且黏結溫度下的熔融黏度為10Pa.s以上且15000Pa.s以下(專利文獻2)。
[先前技術文獻]
(專利文獻)
專利文獻1:日本特開2007-217708號公報
專利文獻2:日本特開2011-157529號公報
然而,在專利文獻2所記載之黏著劑組成物中,黏結時若欲抑制空隙之產生,則存在構裝時產生凸塊的位置偏移、不能獲得導通之問題。又,相反地,若以不產生凸塊的位置偏移之方式進行構裝,則接合後晶片間會產生空隙。因此,在專利文獻2所揭示之方法中,無法充分達成增強半導體晶片與電路板的連接部分或提高半導體裝置的可靠性等
目的。因此,強烈期望開發一種黏著劑組成物,該黏著劑組成物可提供一種半導體裝置,其黏結時不產生空隙、凸塊不發生位置偏移,且於焊接結束後亦不產生空隙、連接可靠性優異。
本發明是有鑒於上述問題點而完成,其目的在於提供一種可適宜用於半導體裝置的製造之黏著劑組成物,尤其是提供一種黏著劑組成物,其在黏結時凸塊之間難以產生空隙、難以引起凸塊的位置偏移,且於焊接結束後亦難以產生空隙。
為了解決上述課題,本發明提供一種黏著劑組成物,其特徵在於:含有下述(A)、(B)及(C)成分;並且,最低熔融黏度不足500Pa.s,成為該最低熔融黏度之溫度不足200℃,且200℃時的熔融黏度為500Pa.s以上,(A)具有反應性官能基之聚合物、(B)熱硬化性樹脂、(C)具有助焊劑活性之化合物。
若為該種組成物,則成為一種可適宜用於半導體裝置的製造之黏著劑組成物,尤其是成為一種黏著劑組成物,在接合時凸塊間難以產生空隙、難以引起凸塊的位置偏移,且在焊接結束後亦難以產生空隙。
此時,前述(A)具有反應性官能基之聚合物,較佳為矽酮樹脂(silicone resin)。
若(A)成分為矽酮樹脂,則成為一種黏著劑組成物,其聚
合物的分子量、反應性官能基種類、反應性官能基量等的控制性、和作為黏著劑組成物之黏著性、耐熱性、絕緣可靠性更為優異。
又,前述反應性官能基,較佳為羥基及環氧基中的至少1個。
由於羥基或環氧基,可提高與(B)成分亦即熱硬化性樹脂之反應性、或作為黏著劑組成物之保存穩定性,因而(A)成分的聚合物所具有之反應性官能基,較佳為該等基中的至少1個。
又,前述(B)熱硬化性樹脂,較佳為環氧樹脂。
若(B)成分為環氧樹脂,則由於使黏著劑組成物硬化時,(B)成分的熱硬化性樹脂與(A)成分的具有反應性官能基之聚合物交聯反應,因此,使用該黏著劑組成物而形成之黏著劑層的黏著性、及硬化物的連接可靠性將進一步提高。
進而,較佳為含有環氧樹脂硬化劑及環氧樹脂硬化促進劑中的至少1種。
藉由含有該等硬化劑及/或硬化促進劑,可恰當且均勻地促進硬化反應。
又,前述(C)具有助焊劑活性之化合物,較佳為具有羧基或酚性羥基之化合物。
若(C)成分為具有羧基或酚性羥基之化合物,則對黏著有黏著劑組成物之半導體晶片的功能面進行焊接等時,利用加熱等去掉該功能面上存在之凸塊的金屬氧化膜之效果,會變得特別好。
又,本發明提供一種具有使用前述黏著劑組成物而形成之黏著劑層之黏著片材、及一種具有使用前述黏著劑組成物而形成之黏著劑層之半導體裝置保護用材料。
這些本發明的半導體裝置保護用材料或黏著片材,具有優異的黏著性、耐熱性、及耐濕性等。
又,本發明提供一種具備前述黏著劑組成物的硬化物之半導體裝置。
此種本發明的半導體裝置的連接可靠性和絕緣可靠性優異。
如上所述,本發明的黏著劑組成物,藉由含有具有反應性官能基之聚合物,可形成柔軟性優異之黏著劑層。又,利用具有反應性官能基之聚合物與熱硬化性樹脂的熱硬化反應可形成交聯結構,且可確保作為半導體保護用材料所需之耐熱性、黏著性、及可靠性。此種本發明的黏著劑組成物,可作為黏著片材及半導體保護用材料的黏著劑層而適宜使用,且可提供一種連接可靠性及絕緣可靠性得以保證之半導體裝置。
又,由於本發明的黏著劑組成物含有具有助焊劑活性之化合物,因此,將形成具有利用加熱等去掉金屬氧化膜之效果(助焊劑活性)之黏著劑層。藉此,可提供一種連接可靠性優異之半導體裝置。又,藉由該黏著劑層在接合半導體晶片與電路板時作為助焊劑發揮功能,在將半導體晶片向基板上進行倒裝片構裝時,無需將助焊劑向電路板上塗佈
等之步驟(第8圖:步驟(a))、清洗助焊劑之步驟(第8圖:步驟(d))、在半導體晶片的一邊或複數面上塗佈底部填充劑之步驟(第8圖:步驟(e))、及利用毛細管現象在電路板與晶片的間隙中流入底部填充劑之步驟(第8圖:步驟(f)),並可提高半導體裝置的生產率。
進而,本發明的黏著劑組成物,由於不足200℃時存在成為最低熔融黏度之溫度,進而該最低熔融黏度不足500Pa.s,且200℃時的熔融黏度為500Pa.s以上,因此,即使在有凹凸之基板或在凸塊上黏結晶片亦不會捲入空氣,又由於可將利用助焊劑成分與凸塊或金屬端子表面上存在之金屬氧化膜的反應而生成之水(水蒸氣)封入,因此,若使用此種本發明的黏著劑組成物進行黏結,則可無空隙地進行黏結,而難以引起凸塊的位置偏移,且構裝後亦不產生空隙。
1‧‧‧保護層
2‧‧‧黏著劑層
2’‧‧‧黏著片材
3‧‧‧半導體晶圓
4‧‧‧半導體加工用保護膠帶
5‧‧‧晶圓環
6‧‧‧砂輪
7‧‧‧經磨削(研磨)之半導體晶圓
8‧‧‧切割刀片
9‧‧‧切割台
10‧‧‧基底基板
11‧‧‧凸塊
12‧‧‧經單片化之半導體晶片
13‧‧‧電極
14‧‧‧半導體晶片與基板的接合部
20‧‧‧電路板
21‧‧‧助焊劑
22‧‧‧半導體晶片
22a‧‧‧半導體晶片的凸塊
23‧‧‧半導體晶片與基板的接合部
24‧‧‧底部填充劑
24a‧‧‧底部填充劑的硬化物
30‧‧‧黏結強度試驗機的測定治具
31‧‧‧黏結強度試驗機的測定治具移動方向
第1圖是表示將具有使用本發明的黏著劑組成物而形成之黏著劑層之黏著片材,壓接至半導體晶圓上之態樣。
第2圖是表示經由具有使用本發明的黏著劑組成物而形成之黏著劑層之黏著片材,將半導體晶圓載持於半導體加工用保護膠帶上之態樣。
第3圖是表示磨削半導體晶圓之態樣。
第4圖是表示切割半導體晶圓之態樣。
第5圖是表示拾取(pick up)經切斷之半導體晶片之態樣。
第6圖是表示將拾取之半導體晶片在基底基板上定位並
載持之態樣。
第7圖是表示半導體晶片與基底基板被焊接之態樣。
第8圖是表示毛細管底部填膠方式中的倒裝片構裝步驟之流程圖。
第9圖是測定黏著劑層的對基板之黏著力之試驗的實施態樣。
以下,更詳細地說明本發明。
如上所述,利用先前的黏著劑組成物,無法充分達成增強半導體晶片與電路板的連接部分或提高半導體裝置的可靠性等目的,強烈期望開發一種黏著劑組成物,該黏著劑組成物,可適宜用於半導體裝置的製造,尤其可提供一種半導體裝,其在黏結時不產生空隙、不產生凸塊的位置偏移,且在焊接結束後亦不產生空隙、連接可靠性優異。
本發明人為了達成上述課題而反復深入研究,結果發現:由具有反應性官能基之聚合物、熱硬化性樹脂、及具有助焊劑活性之化合物所組成之黏著劑組成物,亦即最低熔融黏度不足500Pa.s,且成為該最低熔融黏度之溫度不足200℃,進而200℃時的熔融黏度為500Pa.s以上之黏著劑組成物,可適宜地用於半導體裝置的製造,尤其是抑制在黏結時及凸塊接合後的空隙,且即使在狹小凸塊間距的構裝中亦不產生位置偏移,因而完成本發明。
亦即,本發明的黏著劑組成物的特徵在於:含有下述(A)、(B)及(C)成分;並且,最低熔融黏度不足500Pa.s,
成為該最低熔融黏度之溫度不足200℃,且200℃時的熔融黏度為500Pa.s以上,
(A)具有反應性官能基之聚合物、
(B)熱硬化性樹脂、
(C)具有助焊劑活性之化合物。
以下,更具體地說明本發明,但本發明並不限定於該等。
(A)成分的反應性官能基並不特別限定,可列舉例如氨基、氨基甲酸酯基(urethane group)、醯亞胺基、羥基、羧基、及環氧基等。自與(B)成分亦即熱硬化性樹脂之反應性或作為黏著劑組成物之保存穩定性之觀點來看,在該等基中,具有羥基及環氧基中的至少1個之聚合物較佳。
作為上述具有反應性官能基之聚合物,若為末端及/或側鏈上具有反應性官能基之聚合物,則並不特別限定,可列舉例如丙烯樹脂、聚醯亞胺樹脂、苯氧基樹脂、苯乙烯樹脂、聚酯樹脂、矽酮樹脂、及聚氨基甲酸酯樹脂等。自聚合物的分子量、反應性官能基種類、反應性官能基量等的控制性、及黏著性、耐熱性、絕緣可靠性之優異性來看,在該等樹脂中,最期望使用矽酮樹脂。
該等(A)成分的聚合物,可單獨使用,亦可並用2種以上。
作為上述(A)具有反應性官能基之聚合物,可列舉例如如下所述之具有反應性官能基之矽酮樹脂。
[上述通式(1)中,R1~R4表示可相同亦可不同之碳數1~8的1價烴基;又,m為1~100之整數,a、b、c、及d為0或正數,且滿足0<(c+d)/(a+b+c+d)≦1.0;進而,X、Y分別為由下述通式(2)或(3)表示之2價有機基團。
(上述通式(2)中,Z為選自
之2價有機基團,n為0或1;又,R5、R6分別為碳數1~4的烷基或烷氧基,可彼此不同亦可相同;k為0、1、或2)
(上述通式(3)中,V為選自
之2價有機基團,p為0或1;又,R7,R8分別為碳數1~4的烷基或烷氧基,可彼此不同亦可相同;h為0、1、或2)]。
由上述通式(1)表示之具有具有重複單元之反應性官能基之矽酮樹脂,賦予黏著劑組成物壓接時的黏著性、黏著劑層形成時的薄膜形成性、及機械特性等,且絕緣可靠性亦優異。
上述通式(1)中,R1~R4表示可相同亦可不同之碳數1~8的1價烴基,較佳為表示碳數1~6的1價烴基。具體而言,可列舉:甲基、乙基、丙基、異丙基、正丁基、叔丁基、環己基等直鏈狀、支鏈狀或環狀的烷基;乙烯基、烯丙基、丙烯基、丁烯基、己烯基、環己烯基等直鏈狀、支鏈狀或環狀的烯基;苯基、甲苯基等芳基;及,苄基、苯乙基等芳烷基等。
又,上述通式(1)中,m為1~100之整數,較佳為1~80之整數。
進而,上述通式(1)中的a、b、c、d為0或正數,且滿足0<(c+d)/(a+b+c+d)≦1.0,自對基板之密接性、電性質、及可靠性之觀點來看,較佳為滿足0.1≦(c+d)/(a+b+c+d)≦0.5,進而較佳為滿足0.15≦(c+d)/(a+b+c+d)≦0.25。除此之外,上述通式(1)中的c較佳為滿足0.05≦c/(a+b+c+d)≦0.3,尤其較佳為滿足0.1≦c/(a+b+c+d)≦0.15。又,除此之外,上述通式(1)中的d較佳為滿足0.05≦d/(a+b+c+d)≦0.3,尤其較佳為滿足0.2≦d/(a+b+c+d)≦0.25。進而,上述通式(1)中的a、b較佳為滿足0.4≦a/(a
+b+c+d)≦0.9、0.4≦b/(a+b+c+d)≦0.9。
進而,上述通式(1)中,X為由上述通式(2)表示之2價有機基團,Y為由上述通式(3)表示之2價有機基團。上述通式(2)或(3)中的Z或V為選自
之2價有機基團,n或p為0或1。
上述通式(2)中的R5、R6為碳數1~4的烷基或烷氧基,可彼此不同亦可相同。作為R5、R6的具體例,可列舉甲基、乙基、異丙基、叔丁基、甲氧基、乙氧基、及異丙氧基(isopropyl oxy group)等。
上述通式(3)中的R7、R8為碳數1~4的烷基或烷氧基,可彼此不同亦可相同。作為R7、R8的具體例,可列舉與上述通式(2)中的R5、R6同樣的基團。
又,上述通式(2)或(3)中的k或h為0、1、或2。
作為本發明中的(A)成分具有適宜的反應性官能基之矽酮樹脂,自壓接時的黏著性、黏著劑層形成時的薄膜形成性、機械特性、及熔融黏度特性之觀點來看,重量平均分子量較佳為3,000~100,000,更佳為5,000~80,000。再者,重量平均分子量為利用凝膠滲透層析術(gel permeation chromatography,GPC)之聚苯乙烯換算值。
由上述通式(1)表示之具有反應性官能基之矽酮樹脂,可藉由將下述通式(4)的氫矽亞苯基(hydrogen silphenylene)(1,4-雙(二甲基甲矽烷基)苯)、
及/或下述通式(5)的二氫有機矽氧烷、
(式中,R1~R4、及m與上述相同)
由下述通式(6)表示之具有二烯丙基之苯酚化合物、
(式中,V、R7、R8、p、h與上述相同)
進而,根據需要由下述通式(7)表示之具有二烯丙基之苯酚化合物,在催化劑的存在下,進行所謂的矽氫加成聚合反應來製造。
(式中,Z、R5、R6、n、k與上述相同。)
再者,藉由對進行上述矽氫加成聚合反應之由上述通式(6)及上述通式(7)表示之具有二烯丙基之苯酚化合物
的烯丙基的總數,與由上述通式(4)表示之氫矽亞苯基及由上述通式(5)表示之二氫有機矽氧烷的氫矽烷基的總數之比(烯丙基的總數/氫矽烷基的總數)進行調整,可容易地控制具有由上述通式(1)表示之反應性官能基之矽酮樹脂的重量平均分子量。或者,藉由在由上述通式(6)及上述通式(7)表示之具有二烯丙基之苯酚化合物,與由上述通式(4)表示之氫矽亞苯基及由上述通式(5)表示之二氫有機矽氧烷進行矽氫加成聚合時,將例如如同鄰烯丙基苯酚之單烯丙基化合物、或如同三乙基氫矽烷之單氫矽烷或單氫矽氧烷作為分子量調整劑使用,可容易地控制由上述通式(1)表示之矽酮樹脂的重量平均分子量。
作為上述矽氫加成聚合反應中的催化劑,可列舉例如:鉑(包含鉑黑)、銠、鈀等鉑族金屬載體;H2PtCl4‧xH2O、H2PtCl6‧xH2O、NaHPtCl6‧xH2O、KHPtCl6‧xH2O、Na2PtCl6‧xH2O、K2PtCl4‧xH2O、PtCl4‧xH2O、PtCl2‧xH2O、Na2HPtCl4‧xH2O(式中,x較佳為0~6之整數,尤其較佳為0或6)等氯化鉑、氯鉑酸及氯鉑酸鹽;醇改質氯鉑酸(美國專利第3,220,972號公報);氯鉑酸與烯烴之絡合物(美國專利第3,159,601號公報、美國專利第3,159,662號公報、及美國專利第3,775,452號公報);將鉑黑或鈀等鉑族金屬在氧化鋁、矽石、及碳等支載於載體上者;銠-烯烴絡合物;三(三苯基膦)氯化銠(所謂的威爾金森(Wilkinson)催化劑);氯化鉑、氯鉑酸或氯鉑酸鹽與含有乙烯基之矽氧烷(尤其係含有乙烯基之環狀矽氧烷)之絡合物等。其使用量為催化劑量,通常
作為鉑族金屬,相對於上述通式(4)~(7)的聚合反應物的總質量,較佳為0.001質量%至0.1質量%。
在上述矽氫加成聚合反應中,亦可根據需要使用溶劑。作為溶劑,較佳為例如甲苯、二甲苯等烴系溶劑。
作為上述矽氫加成聚合條件,自催化劑不失活,且可在短時間內結束聚合之觀點來看,聚合溫度為例如40~150℃,尤其較佳為60~120℃。
又,聚合時間亦取決於上述通式(4)~(7)的聚合反應物的種類及量,但為避免濕氣介入於聚合反應系統中,聚合時間大約為0.5~100小時,尤其較佳為0.5~30小時以內。以此方式結束矽氫加成聚合反應後,當使用溶劑時,藉由將其餾出,可獲得由上述通式(1)表示之矽酮樹脂。
[(B)熱硬化性樹脂]
含有(B)成分,以提高黏著劑組成物的黏著性、及硬化物的連接可靠性。在本發明中,熱硬化性樹脂並不特別限定,可列舉例如環氧樹脂、酚醛樹脂、密胺樹脂、聚氨基甲酸酯樹脂、及聚酯樹脂等。其中,較佳為環氧樹脂。環氧樹脂可與(A)具有反應性官能基之聚合物所含有之官能基(例如酚性羥基或羧基等)交聯反應。因此,若熱硬化性樹脂為環氧樹脂,則使黏著劑組成物硬化時,由於熱硬化性樹脂與(A)具有反應性官能基之聚合物進行交聯反應,因此,黏著劑層的黏著性、及硬化物的連接可靠性進一步提高。
環氧樹脂,可列舉例如:雙酚A型環氧樹脂、雙酚F型環氧樹脂、或向該等中加氫者;苯酚清漆型環氧樹脂、
甲酚清漆型環氧樹脂等縮水甘油醚系環氧樹脂;六氫鄰苯二甲酸二縮水甘油酯、二聚酸縮水甘油酯等縮水甘油酯系環氧樹脂;及,異氰尿酸三縮水甘油酯、四縮水甘油基二氨基二苯基甲烷等縮水甘油胺系環氧樹脂等;較佳可列舉雙酚A型環氧樹脂、雙酚F型環氧樹脂、苯酚清漆型環氧樹脂、及甲酚清漆型環氧樹脂。作為該等的市售品,可列舉例如商品名為jER1001(三菱化學(Mitsubishi Chemical Corporation)製造)、EPICLON830S(迪愛生(DIC Corporation,DIC)製造)、jER517(三菱化學製造)、及EOCN103S(日本化藥(Nippon Kayaku Co.,Ltd)製造)等。
又,亦可使用酚醛樹脂作為熱硬化性樹脂。作為該酚醛樹脂,可列舉例如將苯酚或雙酚A、對叔丁基苯酚、辛酚、對枯基苯酚等烷基酚、對苯基苯酚、甲酚等作為原料調製之甲階酚醛樹脂(resol)型酚醛樹脂及/或清漆型酚醛樹脂。熱硬化性樹脂可單獨使用1種,亦可並用2種以上。
熱硬化性樹脂的調配量並不特別限定,但相對於(A)成分100質量份,可為5~100質量份,較佳為10~50質量份。若熱硬化性樹脂的調配量在上述範圍內,則將黏著劑組成物或黏著劑層壓接於基材上時的黏著性提高。又,該黏著劑組成物的硬化物為連接可靠性優異之硬化物,因此較佳。
又,較佳為,除前述環氧樹脂以外,本發明的黏著劑組成物進而含有環氧樹脂硬化劑及環氧樹脂硬化促進劑中的至少1種。藉由含有環氧樹脂硬化劑及環氧樹脂硬化促進劑中的至少1種,可恰當且均勻地推進硬化反應。當調配
該等時,環氧樹脂硬化劑的調配量,相對於(A)成分100質量份,可為3~20質量份,較佳為5~10質量份;環氧樹脂硬化促進劑的調配量,相對於(A)成分100質量份,可為0.1~5質量份,較佳為0.3~3質量份。
環氧樹脂硬化劑,為通常使用者即可,並不特別限定,但自耐熱性之觀點來看,更佳為芳香族系硬化劑或脂環式硬化劑。作為該環氧樹脂硬化劑,可列舉例如胺系硬化劑、酸酐系硬化劑、三氟化硼胺錯鹽、及酚醛樹脂等。作為胺系硬化劑,可列舉例如:二伸乙三胺(diethylenetriamine)、三伸乙四胺(triethylenetetramine)、四伸乙五胺(tetraethylenepentamine)等脂肪族胺系硬化劑;異佛爾酮二胺等脂環式胺系硬化劑;二胺二苯甲烷(diaminodiphenyl methane)、苯二胺(phenylene diamine)等芳香族胺系硬化劑;及,二氰二胺(dicyandiamide)等。其中,較佳為芳香族胺系硬化劑。作為酸酐系硬化劑,可列舉例如鄰苯二甲酸酐、均苯四甲酸酐、偏苯三酸酐、及六氫鄰苯二甲酸酐等。
上述環氧樹脂硬化劑,可單獨使用1種,亦可並用2種以上。
環氧樹脂硬化促進劑,可列舉例如,2-甲基咪唑、2-乙基咪唑、2-乙基-4-甲基咪唑、及該等化合物的異氰酸乙酯化合物;2-苯基咪唑、2-苯基-4-甲基咪唑、2-苯基-4-甲基-5-羥甲基咪唑(2-phenyl-4-methyl-5-hydroxymethyl imidazole)、2-苯基-4,5-二羥甲基咪唑等咪唑化合物;1,8-二氮雜雙環(5.4.0)十一碳-7-烯(DBU);1,5-二氮雜雙環(4.3.0)壬-5-烯
(DBN);DBU的有機酸鹽、DBU的酚醛樹脂鹽、DBU衍生物的四苯硼酸鹽等DBU系化合物;三苯膦(triphenyl phosphine)、三丁膦(tributyl phosphine)、三(對甲苯基)膦、三(對甲氧苯基)膦、三(對乙氧苯基)膦、三苯基膦/三苯基硼酸酯、四苯基膦/四苯基硼酸酯等三有機膦類;季鏻鹽;三乙烯銨基(triethylene ammonium)/三苯基硼酸酯等叔胺、及其四苯硼酸鹽等。
上述環氧樹脂硬化促進劑,可單獨使用1種,亦可並用2種以上。
[(C)具有助焊劑活性之化合物]
若(C)具有助焊劑活性之化合物具有利用加熱等還原去掉金屬氧化膜之效果(助焊劑活性),則並不特別限定,可列舉例如活性松香、具有羧基之有機酸、胺、苯酚、醇、及氮苯(azine)等。
本發明的黏著劑組成物中之具有助焊劑活性之化合物,尤其較佳為分子中具有羧基或酚性羥基之化合物。再者,具有助焊劑活性之化合物可為液狀亦可為固體。若具有助焊劑活性之化合物為分子中具有羧基或酚性羥基之化合物,則對黏著有黏著劑組成物之半導體晶片的功能面進行焊接等時,利用加熱等去掉該功能面上存在之凸塊的金屬氧化膜之效果會變得特別好,因此較佳。
作為具有羧基之化合物,可列舉例如脂肪族酸酐、脂環式酸酐、芳香族酸酐、脂肪族羧酸、及芳香族羧酸等。又,作為前述具有酚性羥基之化合物,可列舉例如苯酚類。
作為脂肪族酸酐,可列舉例如琥珀酐(succinic anhydride)、聚己二酸酐(poly adipic anhydride)、聚壬二酸酐(polyazelaic polyanhydride)、及聚癸二酸酐等。
作為脂環式酸酐,可列舉例如甲基四氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、甲基納迪克酸酐、六氫鄰苯二甲酸酐、四氫鄰苯二甲酸酐、三烷基四氫鄰苯二甲酸酐、及甲基環己烷二羧酸酐等。
作為芳香族酸酐,可列舉例如鄰苯二甲酸酐、偏苯三酸酐、苯均四酸二酐(pyromellitic dianhydride)、二苯甲酮四羧酸酐(benzophenonetetracarboxylic anhydride)、乙二醇雙偏苯三酸酯(ethylene glycol bis trimelitate)、及甘油三偏苯三酸酯(glycerol tris trimelitate)等。
作為脂肪族羧酸,可列舉例如戊二酸、己二酸、庚二酸、及癸二酸等。又,作為其他脂肪族羧酸,可列舉甲酸、乙酸、丙酸、丁酸、戊酸、三甲基乙酸、己酸、辛酸、月桂酸、肉豆蔻酸、棕櫚酸、硬脂酸、丙烯酸、甲基丙烯酸、巴豆酸(crotonic acid)、油酸(oleic acid)、反丁烯二酸(fumaric acid)、順丁烯二酸、草酸(oxalic acid)、丙二酸(malonic acid)、及琥珀酸等。
作為芳香族羧酸,可列舉例如苯甲酸、鄰苯二甲酸、異苯二甲酸(isophthalic acid)、對苯二甲酸(terephthalic acid)、1,2,3-苯三甲酸(hemimellitic acid)、偏苯三酸(trimellitic acid)、1,3,5-苯三甲酸(trimesic acid)、1,2,3,5-苯四甲酸(mellophanic acid)、1,2,3,4-苯四甲酸(prehnitic acid)、1,2,4,5-
苯四甲酸(pyromellitic acid)、苯六甲酸(mellitic acid)、茬甲酸(xylic acid)、2,3-二甲苯甲酸(hemellitic acid)、3,5-二甲苯甲酸(mesitylenic acid)、2,3,4-三甲苯甲酸(prehnitylic acid)、甲苯甲酸(toluic acid)、桂皮酸(cinnamic acid)、柳酸(salicylic acid)、2,3-二羥基苯甲酸、2,4-二羥基苯甲酸、龍膽酸(2,5-二羥基苯甲酸)(gentisic acid)、2,6-二羥基苯甲酸、3,5-二羥基苯甲酸、沒食子酸(3,4,5-三羥基苯甲酸)(gallic acid)、1,4-二羥基-2-萘甲酸、及3,5-二羥基-2-萘甲酸等萘甲酸衍生物、及雙酚酸(diphenolic acid)等。
作為具有酚性羥基之化合物,可列舉例如含有苯酚、鄰甲酚、2,6-二甲苯酚、對甲酚、間甲酚、o-乙苯酚、2,4-二甲苯酚、2,5-二甲苯酚、間乙苯酚、2,3-二甲苯酚、2,6-二甲基-2-庚醇(dimetol)、3,5-二甲苯酚、對叔丁基苯酚(p-tertiarybutyl phenol)、鄰苯二酚(catechol)、對叔戊基苯酚、間苯二酚(resorcinol)、對辛基苯酚(p-octylphenol)、對苯基苯酚、雙酚A、雙酚F、雙酚AF、聯苯酚(biphenol)、二烯丙基雙酚F、二烯丙基雙酚A、三苯酚(trisphenol)、及四苯酚、酚酞等酚性羥基之單體(monomer)類。
又,(C)具有助焊劑活性之化合物,較佳為可與(A)成分及(B)成分的至少一方交聯反應。藉由與(A)成分或(B)成分反應,可將具有助焊劑活性之化合物三維地放入至交聯結構中。尤其較佳為具有助焊劑活性之樹脂硬化劑。作為該具有助焊劑活性之樹脂硬化劑,可列舉例如1分子中具有至少2個酚性羥基與至少1個直接鍵結於芳香族之羧基之化合物。
具體而言,可列舉:2,3-二羥基苯甲酸、2,4-二羥基苯甲酸、龍膽酸(2,5-二羥基苯甲酸)、2,6-二羥基苯甲酸、3,4-二羥基苯甲酸、沒食子酸(3,4,5-三羥基苯甲酸)等苯甲酸衍生物;1,4-二羥基-2-萘甲酸、3,5-二羥基-2-萘甲酸、3,7-二羥基-2-萘甲酸等萘甲酸衍生物;酚酞;及,雙酚酸等。
藉由將具有助焊劑活性之化合物三維地放入至交聯結構中,可抑制具有助焊劑活性之化合物的殘渣自硬化物的三維交聯結構析出。藉此,可抑制來自於該化合物的殘渣之枝晶(dendrite)的成長,可進一步提高硬化物的絕緣可靠性(遷移抗性)。
(C)具有助焊劑活性之化合物的調配量,並不特別限定,但相對於(A)成分及(B)成分的合計100質量份,可為1~20質量份,較佳為2~15質量份。若(C)具有助焊劑活性之化合物的含有量在上述下限值以上,則可充分獲得助焊劑活性之效果;又,若在上述上限值以下,則不會成為在倒裝片構裝步驟後導致具有助焊劑活性之化合物自交聯結構析出並使枝晶成長之原因。又,若具有助焊劑活性之化合物的調配量在上述範圍內,則可充分去掉金屬表面的氧化膜,因此,焊接時可獲得強度較大且良好的接合。
[其他成分]
除上述(A)~(C)成分以外,本發明的黏著劑組成物,亦可根據需要,添加其他成分。作為其他成分,可列舉無機填充劑、矽烷偶合劑等。
[無機填充劑]
本發明的黏著劑組成物可含有無機填充劑,以獲得耐熱性、尺寸穩定性、及耐濕性等特性。作為無機填充劑,可列舉例如:滑石、煆燒黏土(calcined clay)、未煆燒黏土、雲母、玻璃等矽酸鹽;氧化鈦、氧化鋁、熔融矽石(熔融球狀矽石、熔融破碎矽石)、晶矽石(crystalline silica)等的粉末等氧化物;碳酸鈣、碳酸鎂、水滑石(hydrotalcite)等碳酸鹽;氫氧化鋁、氫氧化鎂、氫氧化鈣等氫氧化物;硫酸鋇、硫酸鈣、亞硫酸鈣等硫酸鹽或亞硫酸鹽;硼酸鋅、偏硼酸鋇(barium metaborate)、硼酸鋁、硼酸鈣、硼酸鈉等硼酸鹽;及,氮化鋁、氮化硼、氮化矽等氮化物等。
該等無機填充劑,可單獨混合1種,亦可同時混合2種以上。在該等中,較佳為熔融矽石、晶矽石等矽石粉末,尤其較佳為熔融球狀矽石。
藉由含有無機填充劑,可提高硬化本發明的黏著劑組成物後之耐熱性、耐濕性、及強度等,且可在使用本發明的黏著劑組成物而形成之黏著劑層與保護層積層而成之黏著片材中,提高黏著劑層對保護層之剝離性。再者,無機填充劑的形狀,並不特別限定,較佳為圓球狀,藉此可形成無各向異性之黏著劑層。
無機填充劑的平均粒徑,並不特別限定,但較佳為0.01μm以上0.5μm以下,尤其較佳為0.01μm以上0.3μm以下。若無機填充劑的平均粒子徑在上述下限值以上,則無機填充劑難以集聚,且強度提高,因此較佳。又,若在上述上限值以下,則黏著劑層的透明度提高,容易辨識半導體晶
片表面的對位標記,因而半導體晶片與基板的對位更為容易,因此較佳。
無機填充劑的含有量,並不特別限定,但較佳為,相對於本發明的黏著劑組成物的總質量,為5質量%以上60質量%以下,較佳為10質量%以上50質量%以下。若無機填充劑的含有量在上述上限值以下,則黏著劑層的透明性及黏性提高,且熔融黏度不會上升,因此較佳。
[矽烷偶合劑]
本發明的黏著劑組成物亦可包含矽烷偶合劑。藉由包含矽烷偶合劑,則可進一步提高黏著劑層對被黏著體之密接性。作為矽烷偶合劑,可列舉環氧基矽烷偶合劑、含有芳香族之氨基矽烷偶合劑等。該等可單獨使用,亦可組合使用2種以上。矽烷偶合劑的含有量,並不特別限定,但較佳為本發明的黏著劑組成物的總質量的0.01質量%以上5質量%以下。
又,本發明的黏著劑組成物,進而亦可包含除上述以外之成分。例如,亦可適當添加各種添加劑,以提高具有反應性官能基之聚合物(A)與熱硬化性樹脂(B)之相溶性,或者提高黏著劑組成物的儲藏穩定性或可操作性等各種特性。可添加例如脂肪酸酯/甘油酸酯(glycerate)/硬脂酸鋅/硬脂酸鈣等內部脫模劑;及,苯酚系、磷系、或硫磺系抗氧化劑等。
其他任意成分,可在無溶劑情況下向本發明的黏著劑組成物中添加,亦可溶解或分散於有機溶劑中,作為溶液或分散液進行調製後添加。作為用於調製黏著劑組成物的
分散液之溶劑,可使用以下說明之有機溶劑。
本發明的黏著劑組成物的最低熔融黏度不足500Pa.s,進而需成為該最低熔融黏度之溫度不足200℃,且200℃時的熔融黏度為500Pa.s以上。
當使用最低熔融黏度不足500Pa.s,且成為該最低熔融黏度(不足500Pa.s)之溫度不足200℃之組成物進行黏結時,即使在有凹凸之基板或凸塊上黏結晶片亦不會捲入空氣,因此,可無空隙地進行黏結,又,亦可防止晶片的位置偏移。另一方面,當使用最低熔融黏度為500Pa.s以上的組成物、或即使最低熔融黏度不足500Pa.s但成為該最低熔融黏度之溫度為200℃以上之組成物進行黏結時,黏結時雖然可防止空氣捲入,但無法防止晶片的位置偏移。
又,當200℃時的熔融黏度為500Pa.s以上時,由於可將利用助焊劑成分與凸塊或金屬端子表面上存在之金屬氧化膜之反應而生成之水(水蒸氣)封入,因此,構裝後不產生空隙。另一方面,當200℃時的熔融黏度不足500Pa.s時,無法將生成之水(水蒸氣)封入,則構裝時產生空隙。
再者,本說明書中的黏結,意味著:在半導體晶圓或晶片上形成黏著劑組成物,並經由該黏著劑組成物,接合於其他半導體晶圓或晶片、或者基板之步驟;於其後,邊控制荷重或位置邊進行加熱,以進行凸塊的連接之步驟。又,本說明書中的黏結溫度,係將形成有黏著劑組成物之晶圓或晶片,經由該黏著劑組成物,接合於其他半導體晶圓或晶片、或者基板之步驟的溫度。該種黏結溫度為例如100~180℃,
期望為在黏著劑組成物的熔融黏度成為10Pa.s~500Pa.s之溫度下進行黏結。
又,本說明書中,熔融黏度意味著:使用熔融黏度計,邊以升溫速度10℃/分自40℃升溫至260℃,邊以1Hz頻率利用圓板的切變所測定之熔融黏度。
[黏著劑組成物的調製]
本發明的黏著劑組成物,係藉由邊根據需要同時或分別對具有反應性官能基之聚合物(A)、熱硬化性樹脂(B)、具有助焊劑活性之化合物(C)、及根據期望添加之其他任意成分、以及根據需要添加之有機溶劑加以加熱處理,邊進行攪拌、溶解、混合、及分散而調製。該等操作所使用之裝置並不特別限定,但可使用具備攪拌、加熱裝置之磨碎攪拌機(raikai mixer)、三輥研磨機(Three-Rollers Milling Machine)、球磨機、及行星攪拌器等。又,亦可適當組合該等裝置。有機溶劑作為用於調製黏著劑組成物的分散液之溶劑,為以下說明之有機溶劑即可。
可調整本發明的黏著劑組成物為,25℃時的溶液黏度為10~3000mPa.s,較佳為100~2000mPa.s。可使用旋轉型黏度計測定黏度。
當使用本發明的黏著劑組成物形成黏著劑層時,較佳為作為使黏著劑組成物分散至有機溶劑中之溶液使用。作為有機溶劑,可列舉N,N-二甲基乙醯胺、甲基乙基酮、N,N-二甲基甲醯胺、環己酮(cyclohexanone)、環戊酮(cyclopentanone)、N-甲基-2-吡咯烷酮、甲苯、甲醇、乙醇、
異丙醇、丙酮、丙二醇單甲醚(propylene glycol monomethyl ether)、及丙二醇單甲醚乙酸酯等,較佳為可列舉甲基乙基酮、環戊酮、丙二醇單甲醚、丙二醇單甲醚乙酸酯。該等有機溶劑,可單獨使用1種,亦可並用2種。可調配有機溶劑為,固體成分濃度為30~70質量%,較佳為40~65質量%。
<黏著片材>
本發明提供一種具有使用上述黏著劑組成物而形成之黏著劑層之黏著片材。作為黏著片材,可列舉例如,將由本發明的黏著劑組成物形成之黏著劑層與覆蓋該黏著劑層之保護層(脫模基材)積層所獲得之黏著片材。
[黏著片材的製造]
本發明的黏著片材的製造方法的一例如下所示。
使用逆轉輥塗佈機(reverse roll coater)、缺角輪塗佈機(comma coater)等,將黏著劑組成物分散至有機溶劑中所獲得之溶液塗佈於保護層(脫模基材)上。使塗佈有前述黏著劑組成物的分散液之保護層(脫模基材)通過直列式乾燥機(in-line dryer),在80~160℃時、經2~20分鐘去除有機溶劑並使其乾燥而形成黏著劑層,作為具有黏著劑層之黏著片材。又,亦可根據需要,藉由使用輥式層壓機(roll laminater)將另一保護層(脫模基材)壓接並積層於前述黏著劑層上,從而作為黏著片材。黏著片材上所形成之黏著劑層的厚度較佳為5~150μm,尤其較佳為10~100μm。
若用於黏著片材的製造之保護層(脫模基材)為可自黏著劑層剝離而不損害黏著劑層形態者,則並不特別限
定。可使用例如聚乙烯(polyethylene,PE)薄膜、聚丙烯(Polypropylene,PP)薄膜、聚甲基戊烯(polymethylpentene,TPX)薄膜、經過脫模處理之聚酯薄膜等塑膠薄膜等。
[黏著片材的使用]
具有使用本發明的黏著劑組成物而形成之黏著劑層之黏著片材,可用於例如直接連接半導體晶圓上所設置之凸塊、基板上所設置之電極之倒裝片構裝。又,亦可用於連接具有貫通電極之半導體元件彼此。
使用具有使用本發明的黏著劑組成物而形成之黏著劑層之黏著片材來構裝半導體晶圓之態樣的一例示於第1圖~第7圖。以下說明各步驟。
(步驟1:第1圖)
將保護層1與黏著劑層2積層所形成之黏著片材2’利用加熱壓接方式等貼合至預先形成有凸塊11(第6圖:第1圖~第5圖中未圖示)之半導體晶圓3的功能面(凸塊形成面)上。加熱壓接通常是在溫度80~130℃、壓力0.01~1MPa、時間5~300秒下進行。或,可藉由在真空下以50~1300Pa貼合黏著片材後恢復至大氣壓,來進行壓接。
(步驟2:第2圖)
將半導體晶圓3上所貼合之黏著片材2’的保護層1側的面貼付至半導體加工用保護膠帶4上,並利用晶圓環5來支持。半導體加工用保護膠帶4可使用一般所使用者(例如名為背面研磨膠帶、切割膠帶(dicing tape)等之市售膠帶),根據用途適當選擇即可。再者,半導體加工用保護膠帶4與黏
著劑層2亦可直接貼合而不經由保護層1。將黏著片材貼付至膠帶上之步驟,通常溫度為20~40℃,線性負載為5~50N/cm,壓接時間為5~60秒。該步驟亦可使用黏著膠帶進行。又,可藉由在真空下以50~1300Pa貼合後恢復至大氣壓,來進行壓接。
(步驟3:第3圖)
其次,將半導體加工用保護膠帶4固定於磨削(研磨)台(未圖示)上,利用砂輪6磨削(研磨)半導體晶圓3。具有砂輪之磨削(研磨)裝置,並不特別限定,使用通常所使用者即可。此處,磨削(研磨)後的半導體晶圓7(第4圖)的厚度,並不特別限定,但較佳為30~600μm左右。
(步驟4:第4圖)
磨削(研磨)後的半導體晶圓7被設置於切割台9上,以接連半導體加工用保護膠帶4側的面與切割台9。使用具備切割刀片8之切割機(dicing saw)(未圖示),將研削(研磨)後的半導體晶圓7與保護層1及黏著劑層2一起切斷。切割時的主軸轉數及切斷速度適當選擇即可,但通常主軸轉數為25,000~45,000rpm,切斷速度為10~50mm/sec。
(步驟5:第5圖)
將半導體加工用保護膠帶4利用平展裝置拉伸,在各個與黏著片材2’一起經單片化之半導體晶片12之間,作出一定縫隙。將黏著劑層2與保護層1之間剝離,並將具備黏著劑層之半導體晶片12拾取。
(步驟6:第6圖)
使用倒裝片接合器(未圖示),將經切斷之半導體晶片12的功能面上具備之凸塊11與基底基板10上的電極13對位,在基底基板10上載持半導體晶片12。
(步驟7:第7圖)
利用加熱壓接方式,將經切斷之半導體晶片12的功能面上具備之凸塊11與基底基板10上的電極13進行接合(接合部14)。加熱壓接通常係在溫度100~280℃、荷重1~500N、時間1~30秒下進行。之後,進行加熱來硬化黏著劑組成物,並密封半導體晶片12與基底基板10之間的間隙。黏著劑組成物的硬化,通常在160~240℃,尤其在180~220℃、0.5~6小時,尤其在1~4小時下進行。
如上所述,藉由使用具有使用本發明的黏著劑組成物而形成之黏著劑層之黏著片材,可省略毛細管底部填膠方式(第8圖)中之步驟(a)、步驟(d)、步驟(e)及步驟(f)。又,使用本發明的黏著劑組成物而形成之黏著劑層,具有壓接時對於基底基板之優異黏著性。又,硬化後的黏著劑層的連接可靠性及絕緣可靠性優異。
<半導體裝置保護用材料>
又,本發明提供一種具有使用上述黏著劑組成物而形成之黏著劑層之半導體裝置保護用材料。作為半導體裝置保護用材料的使用態樣,可列舉例如使用本發明的黏著劑組成物而形成之黏著劑層,與半導體加工用保護膠帶所積層之保護片材。藉由將該保護片材的黏著劑層面貼付至半導體裝置的被保護面上,剝離保護膠帶後,使黏著劑層面硬化來作為保
護膜,從而可保護半導體裝置的表面。由於本發明的黏著劑組成物的硬化物的連接可靠性及絕緣可靠性優異,因此,可作為半導體裝置、及二極管、晶體管、IC、及LSI等電子部件的保護膜而適宜地發揮功能。作為保護膜的使用態樣,可列舉例如:二極管、晶體管、IC、及LSI等半導體元件表面的接合保護用塗層膜(junction coating film)、鈍化膜(passivation film)及緩衝塗層膜(buffer coating film);LSI等α射線屏蔽膜;多層配線的層間絕緣膜;印刷電路板的保角塗層(conformal coating);離子植入遮罩(ion implantation mask);及,太陽電池的表面保護膜等。
<半導體裝置>
進而,本發明提供一種具備上述黏著劑組成物的硬化物之半導體裝置。
如上所述,作為該種本發明的半導體裝置的製造方法的一態樣,可列舉經由使用本發明的黏著劑組成物而形成之黏著劑層,將半導體晶片載持於基底基板上後,使黏著劑組成物硬化之方法。又,作為另一態樣,可列舉將具有使用本發明的黏著劑組成物而形成之黏著劑層之半導體裝置保護用材料,貼付在半導體裝置(被黏著物)的保護面上後,硬化黏著劑組成物而形成保護膜之方法。由於本發明的黏著劑組成物的薄膜形成性及對基板的黏著性優異,且可提供高溫高濕條件下的連接可靠性及絕緣可靠性(遷移抗性)優異之硬化物,因此,可適宜利用,以應用於半導體裝置的高密度化、高積體化。
[實施例]
以下示出作為本發明中的(A)具有反應性官能基之聚合物的矽酮樹脂的合成例、本發明的黏著劑組成物的實施例及比較例,更詳細地說明本發明,但本發明並不限定於該等。
作為本發明中的(A)具有反應性官能基之聚合物的矽酮樹脂的合成例1及合成例2中使用之化合物(M-1)~(M-6)的化學結構式如下所示。
在合成例中,各聚合體的重量平均分子量,係使用GPC色譜柱TSKgel Super HZM-H(東曹股份有限公司(TOSOH CORPORATION)製造),以流量0.6毫升/分、洗提溶媒四氫呋喃、色譜柱溫度40℃之分析條件,利用以單分散聚苯乙烯為標準之凝膠滲透層析術(GPC)來進行測定。又,各
聚合體的1H-NMR分析,係使用JNM-LA300WB(日本電子股份有限公司(JEOL Ltd.)製造),作為測定溶媒使用氘代氯仿來實施。
[合成例1]
說明作為本發明中的(A)具有反應性官能基之聚合物的矽酮樹脂的合成例1。在具備攪拌機、溫度計、氮氣置換裝置及回流冷凝器之5L燒瓶內,將化合物(M-1)220.5g、化合物(M-3)225.0g溶解於甲苯1,875g後,加入化合物(M-4)949.6g、化合物(M-5)6.1g並加溫至60℃。之後,投入碳載鉑催化劑(5質量%)2.2g,並確認內部反應溫度升溫至65℃~67℃後,進而加溫至90℃後保持3小時,再次冷卻至60℃,進而投入碳載鉑催化劑(5質量%)2.2g,並花費1小時將化合物(M-6)107.3g滴下至燒瓶內。此時燒瓶內溫度上升至80℃。化合物(M-6)滴下結束後,進而在90℃保持3小時後,冷卻至室溫,加入甲基異丁酮(methyl isobutyl ketone,MIBK)1,700g,通過將本反應溶液利用過濾器進行加壓過濾,來去掉碳載鉑催化劑,從而獲得矽酮樹脂溶液。進而,向所獲得之矽酮樹脂溶液中加入純水760g,並進行攪拌、靜置、及分液,去除下層的水層。將該分液水洗操作重複6次,去掉矽酮樹脂溶液中的微量酸性成分。之後,將矽酮樹脂溶液中的溶劑減壓餾出,同時添加950g環戊酮,獲得固體成分濃度60質量%之以環戊酮為主溶劑之矽酮樹脂溶液(A-1)。利用GPC測定該矽酮樹脂溶液中的(A)矽酮樹脂的分子量後,利用聚苯乙烯換算之重量平均分子量為75,000,且(c+d)/(a+b+c+d)=
0.50。
[合成例2]
說明作為本發明中的(A)具有反應性官能基之聚合物的矽酮樹脂的合成例2。在具備攪拌機、溫度計、氮氣置換裝置及回流冷凝器之5L燒瓶內,將化合物(M-1)352.8g、化合物(M-2)116.1g溶解於甲苯1,875g後,加入化合物(M-4)949.6g、化合物(M-5)6.1g並加溫至60℃。之後,投入碳載鉑催化劑(5質量%)2.2g,並確認內部反應溫度升溫至65℃~67℃後,進而加溫至90℃後保持3小時,再次冷卻至60℃,投入碳載鉑催化劑(5質量%)2.2g,並花費1小時將化合物(M-6)107.3g滴下至燒瓶內。此時燒瓶內溫度上升至73℃。滴下結束後,進而在90℃保持3小時後,冷卻至室溫後,加入甲基異丁酮(MIBK)1,700g,通過將本反應溶液利用過濾器進行加壓過濾,來去掉碳載鉑催化劑,從而獲得矽酮樹脂溶液。進而,向所獲得之矽酮樹脂溶液中加入純水760g,並進行攪拌、靜置、及分液,去除下層的水層。將該分液水洗操作重複6次,去掉矽酮樹脂溶液中的微量酸性成分。之後,將該矽酮樹脂中的溶劑減壓餾出,同時添加940g環戊酮,獲得固體成分濃度60質量%之以環戊酮為主溶劑之矽酮樹脂溶液(A-2)。利用GPC測定該矽酮樹脂溶液中的(A)矽酮樹脂的分子量後,利用聚苯乙烯換算之重量平均分子量為55,000,且(c+d)/(a+b+c+d)=0.20。
[實施例1~實施例5及比較例1~比較例4]
[黏著劑組成物的調製]
以表1中記載之組成,調配(A)上述合成例1~合成例2中合成之具有反應性官能基之聚合物(矽酮樹脂)、(B)熱硬化性樹脂、(C)具有助焊劑活性之化合物、及其他任意成分。進而,添加使固體成分濃度為50質量%之量的環戊酮,使用球磨機攪拌,進行混合及溶解,從而調製黏著劑組成物的分散液。再者,表示表1中的調配量之數值的單位為「質量份」。
用於黏著劑組成物的調製之各成分如下所示。
[(B)熱硬化性樹脂]
‧jER1001(商品名)(三菱化學製造,環氧當量:450~500)
進而,使用以下所示之環氧樹脂硬化劑及環氧樹脂硬化促進劑。
‧環氧樹脂硬化劑:Phenolite TD-2093(商品名)(DIC製造,OH當量:104)
‧環氧樹脂硬化促進劑:Curezol 2MZA-PW(商品名)(四國化成(Shikoku Chemicals Corporation)製造,2,4-二氨基-6-[2’-甲基咪唑-(1’)]-乙基-s-三嗪)
Curezol 2P4MZ(商品名)(四國化成製造,2-苯基-4-甲基咪唑)
[C具有助焊劑活性之化合物]
‧癸二酸(和光純藥工業(Wako Pure Chemical Industries,Ltd.)製造)
[其他任意成分]
‧無機填充劑:矽石(Admatechs(Admatechs Company Limited)製造,SE1050,平均粒徑0.25μm)
[黏著片材的製作]
藉由在利用敷貼器(applicator)施以脫模處理之聚酯薄膜(保護層,東洋紡績(Toyobo Co.,Ltd.)製造)表面上,塗佈黏著劑組成物的分散液,以使乾燥後的厚度為25μm,並在130℃時在送風烘箱內乾燥5分鐘,來形成黏著劑層,製作具有黏著劑層之黏著片材。按照下述評價方法來評價各黏著片材的特性。結果示於表1。
[評價1:黏著劑層的熔融黏度測定]
將各黏著片材(黏著劑層厚度25μm)利用可調節溫度之輥式層壓機疊加,直至黏著劑層厚度為500μm。
使用熔融黏度計(HAAKE公司製造,MARS),邊以升溫速度10℃/分自40℃升溫至260℃,邊以1Hz頻率利用圓板的切變來測定所獲得之黏著片材的熔融黏度,分別獲得成為最低熔融黏度之溫度、最低熔融黏度、及200℃時的熔融黏度。所獲得之結果示於表1。
[評價2:半導體封裝體構裝後的空隙有無(SAT及光學顯微鏡)]
根據上述之黏著片材的製作方法,製作黏著劑層的厚度為40μm之黏著片材。使用真空薄膜層壓機(溫度:110℃,壓力:80Pa),將具備凸塊之半導體晶圓(8英寸,厚度725μm)的凸塊附著面與各黏著片材的黏著劑層面貼合(第1圖)。之後,在線性負載約10N/cm、室溫之條件下,將具備
黏著片材之半導體晶圓的保護層面貼合至由晶圓環所支持之背面研磨膠帶(電氣化學工業(Denki Kagaku Kogyo Kabushiki Kaisha)製造)上。
繼而,使用具備切割刀片之切割機,將半導體晶圓切斷成5mm×6mm的四方形(第4圖,但此處半導體晶圓並未被削薄),拾取單片化之半導體晶片(第5圖),獲得具備黏著劑層之半導體晶片(在凸塊直徑25μm、凸塊高度10μm的Cu上製作凸塊高度15μm的Sn-Ag凸塊,且合計高度為25μm,凸塊間距50μm,凸塊數2,200)(相當於第6圖的2、11、12)。切割時的主軸轉數為30,000rpm,切斷速度為25mm/sec。
繼而,使用具備切割刀片之切割機,將以與上述晶片相對應之方式配置有凸塊之半導體晶圓(8英寸,厚度725μm,凸塊直徑25μm,Cu凸塊高度10μm,凸塊間距50μm,凸塊數2,200)切斷成11mm×11mm的四方形,獲得單片化之半導體基板(相當於第6圖的10、13)。切割時的主軸轉數為30,000rpm,切斷速度為25mm/sec。
繼而,使用倒裝片接合器,將具備前述黏著劑層之半導體晶片(相當於第6圖的2、11、12)對位至單片化之半導體基板(相當於第6圖的10、13),在表1所示之接合溫度下,以10sec、50N載持後,以在255℃保持10N荷重15秒之方式加熱壓接,各製作10個半導體封裝體(第7圖)。之後,將該封裝體在180℃加熱1小時,使黏著劑層硬化。
在以此方式所獲得之半導體封裝體中,使用超音
波成像裝置(SAT)(日立工程與服務股份有限公司(Hitachi Engineering & Services Co.,Ltd.)製造,FS300III)確認空隙之有無,將確認無空隙之情況評為○,將確認有空隙之情況評為×,來進行空隙的評價。結果示於表1。將○判定為合格。
又,將所獲得之半導體封裝體自半導體晶片側與晶片水平地研磨直至晶片消失,利用光學顯微鏡進行空隙觀察。將確認無25μm以上空隙之情況評為○,將確認有大於25μm空隙之情況評為×,來進行空隙的評價。結果示於表1。將○判定為合格。
[評價3:半導體封裝體構裝後的晶片偏移(X射線及光學顯微鏡)]
對以與評價2同樣的方法獲得之各10個半導體封裝體,利用三維計測X射線CT裝置(大和科學股份有限公司(Yamato Scientific Co.,Ltd.)製造,TDM1000-IS)來確認晶片偏移的產生。將朝向半導體晶片及半導體基板所具有之凸塊的水平方向之最大偏移量不足5μm之情況評為○,將5μm以上、不足10μm之情況評為△,將10μm以上之情況評為×,來進行晶片偏移的評價。結果示於表1。將○判定為合格。進而,在結束X射線觀察之半導體封裝體中,在與半導體晶片及半導體基板相垂直的方向上研磨斷面,利用光學顯微鏡來確認上下凸塊彼此是否接合。將上下凸塊彼此接合之情況評為○,將未接合之情況評為×,來進行評價。結果示於表1。將○判定為合格。
[評價4:黏著劑層的黏著力]
使用真空薄膜層壓機(溫度:110℃,壓力:80Pa,TEAM-100,日本高鳥股份有限公司(Takatori Corporation)製造),將各黏著片材(黏著劑層厚度25μm)貼合至6英寸半導體晶圓(厚度625μm,信越半導體股份有限公司(Shin-Etsu Handotai Co.,Ltd.)製造)上(第1圖)。其次,將該黏著片材所具有之聚酯薄膜面在線性負載約10N/cm、室溫之條件下貼付至由晶圓環所支持之切割膠帶(電氣化學工業製造)上(第2圖)。使用具備切割刀片之切割機(DAD685,日本DISCO股份有限公司(DISCO Corporation)製造),將半導體晶圓及黏著片材切斷成2mm×2mm四方形的大小(第4圖)。將黏著劑層與聚酯薄膜之間剝離,拾取單片化之半導體晶片,獲得具備黏著劑層之半導體晶片(第5圖)。切割時的主軸轉數為30,000rpm,切斷速度為25mm/sec。將前述單片化之各半導體晶片經由黏著劑層,在成為最低熔融黏度之溫度下,以50mN荷重貼合至15mm×15mm四方形的矽晶片(基底基板)上。之後,在180℃加熱1小時使黏著劑組成物硬化,從而獲得試樣。各製造5個試樣,以供以下黏著力測定試驗所用。
使用黏結強度試驗機(Dage series 4000-PXY:Dage公司製造),測定半導體晶片(2mm×2mm)自基底基板(15mm×15mm四方形的矽晶片)剝離時需要之電阻,評價黏著劑層的黏著力。在檢驗速度200μm/sec、檢驗高度50μm之檢驗條件下進行。黏著力測定試驗的實施圖示於第9圖。在第9圖中,將黏結強度試驗機的測定治具(符號30)的移
動方向用箭頭表示(符號31)。結果示於表1。表1所示之數值表示各5個試驗體的測定值的平均值,數值越高黏著片材的黏著力越高。
[評價5:連接可靠性]
根據上述之黏著片材的製作方法,製作黏著劑層厚度為65μm之黏著片材。使用真空薄膜層壓機(溫度:110℃,壓力:80Pa),將具備凸塊之半導體晶圓(8英寸,厚度725μm)的凸塊附著面與各黏著片材的黏著劑層面貼合(第1圖)。之後,將具備黏著片材之半導體晶圓的保護層面,在線性負載約10N/cm、室溫之條件下,貼至由晶圓環所支持之背面研磨膠帶(電氣化學工業製造)上(第2圖),使用磨削(研磨)裝置(DAG810,日本DISCO股份有限公司製造)磨削(研磨)直至半導體晶圓厚度為100μm(第3圖)。
繼而,使用具備切割刀片之切割機將半導體晶圓切斷成10mm×10mm的四方形(第4圖),並拾取單片化之半導體晶片(第5圖),獲得具備黏著劑層之半導體晶片(直徑80μm,Sn-3Ag-0.5Cu凸塊,凸塊高度50μm,間距150μm,凸塊數3,844)。切割時的主軸轉數為40,000rpm,切斷速度為25mm/sec。
在以阻焊劑(solder resist)(太陽油墨(Taiyo Ink Mfg.Co.,Ltd.)製造,PSR4000 AUS703)塗層之雙馬來醯亞胺三嗪(Bismaleimide-Triazine,BT)樹脂基板(厚度0.94mm)上,使用倒裝片接合器,對具備前述黏著劑層之半導體晶片進行對位,在表1所示之黏結溫度下,以10sec、60N載持
後(第6圖),以在255℃保持10N荷重15秒之方式進行加熱壓接,製作倒裝片封裝體(各10個)。之後,將該封裝體在180℃加熱1小時,使黏著劑層硬化。再者,該BT樹脂基板,在半導體晶片電性接合時,用銅來進行配線以與半導體晶片內的金屬配線成為菊鏈,可確認所獲得之半導體封裝體的導通(連接電阻)。
測定根據上述方法製造之半導體封裝體各10個的連接電阻,確認初期的導通。之後,將該封裝體供給至熱循環試驗(將-25℃保持10分鐘、125℃保持10分鐘之循環重複1000次)中,並確認熱循環試驗後的導通。將均能取得導通者評為○,將初期能取得導通但熱循環試驗後不能取得導通者評為△,將初期不能取得導通者評為×,來評價連接可靠性。結果示於表1。將○判定為合格。
[評價6:絕緣可靠性(遷移抗性)]
在玻璃基板上製作Cu厚度5μm、線寬/空間寬度=20μm/20μm的梳形電路,使用真空薄膜層壓機(溫度:110℃,壓力:80Pa),以用黏著片材的黏著劑層面覆蓋梳形電路之方式貼合(端子部利用遮罩膠帶(masking tape)進行遮罩)。繼而,將黏著片材的保護層剝離,藉由在180℃加熱1小時來使黏著劑層硬化,從而製作絕緣可靠性評價用樣品(各5個)。針對各試樣,在溫度85℃、相對濕度85%之條件下,在電路的兩極外加10V直流電壓,使用遷移檢驗儀(migration tester)(IMV公司(IMV Corporation)製造,MIG-86)來評價絕緣可靠性。外加電壓後,將1,000小時以內導體之間產生短路(電
阻值降低)之情況、或可看到枝晶成長之情況評價為「不良」並用×表示;將經過1,000小時後亦維持電阻值,且不產生枝晶之情況評價為「良」並用○表示。結果示於表1。
關於實施例1~實施例5、及比較例3的半導體
封裝體構裝後的空隙有無,對各10個封裝體全體之評價均為○。關於比較例1及比較例4的半導體封裝體構裝後的空隙有無,對10個封裝體全體之評價均為×。
關於實施例1~實施例5、比較例1的半導體封裝體構裝後的晶片偏移,對各10個封裝體全體之評價均為○。關於比較例3~比較例4的半導體封裝體構裝後的晶片偏移,對各10個封裝體全體之評價均為×。
關於實施例1~實施例5、及比較例3的連接可靠性,對各10個封裝體全體之評價均為○。關於比較例1及比較例4的連接可靠性,對10個封裝體全體之評價均為△。
關於實施例1~實施例5、比較例1~比較例4的絕緣可靠性,對各5個試樣全體之評價均為○。
根據表1,不滿足本發明必要條件亦即200℃時的熔融黏度為500Pa.s以上之條件之比較例1,在半導體封裝體構裝後,可發現產生空隙。比較例1的黏著劑組成物,依照JIS C2161 B測定之凝膠時間在黏結溫度亦即150℃時為90秒,又240℃時的凝膠時間為10秒,且黏結溫度時的熔融黏度為60Pa.s,由上可確認,其為滿足日本特開2011-157529號公報中記載之必要條件之黏著劑組成物,但產生空隙。又,可確認,在比較例1中,因構裝後空隙的影響,連接可靠性亦為不合格。
可確認,由於比較例3的黏著劑組成物不滿足本發明必要條件亦即最低熔融黏度不足500Pa.s之條件,因此,在半導體封裝體構裝後產生晶片偏移。
又,可確認,由於比較例4不滿足本發明必要條件亦即200℃時的熔融黏度為500Pa.s以上之條件,因此,在半導體封裝體構裝後,可發現產生空隙,因構裝後空隙的影響,連接可靠性亦為不合格。進而可確認,由於比較例4亦不滿足本發明必要條件亦即成為最低熔融黏度之溫度不足200℃之條件,因此,在半導體封裝體構裝後產生晶片偏移。
與此相對,使用本發明的黏著劑組成物而形成之黏著劑層,在構裝後未發現產生空隙,亦未確認到晶片偏移。又,黏著力優異,連接可靠性及絕緣可靠性亦優異。又,由本發明的黏著劑層所保護之半導體裝置的連接可靠性以及絕緣可靠性得以保證。
本發明的黏著劑組成物可提供一種硬化物,該硬化物,在半導體封裝體構裝後,未發現空隙產生及晶片偏移,對基板之黏著性優異,且高溫高濕條件下的連接可靠性及絕緣可靠性(遷移抗性)優異。因此,可期待,適宜利用本發明的黏著劑組成物,以應用於半導體裝置的高密度化、高積體化。
再者,本發明並不限定於上述實施形態。上述實施形態為示例,具有與本發明的申請專利範圍所記載之技術思想實質相同的構成,並發揮同樣作用效果之所有發明,均包含在本發明的技術範圍內。
1‧‧‧保護層
2‧‧‧黏著劑層
2’‧‧‧黏著片材
3‧‧‧半導體晶圓
Claims (16)
- 一種黏著劑組成物,其特徵在於:含有下述(A)、(B)及(C)成分;並且,最低熔融黏度不足500Pa.s,成為該最低熔融黏度之溫度不足200℃,且200℃時的熔融黏度為500Pa.s以上,(A)具有反應性官能基之矽酮樹脂、(B)熱硬化性樹脂:相對於(A)成分100質量份,為5~100質量份、(C)具有助焊劑活性之化合物:相對於(A)成分及(B)成分的合計100質量份,為1~20質量份。
- 如請求項1所述之黏著劑組成物,其中,前述(A)具有反應性官能基之矽酮樹脂為具有以下述通式(1)表示的反應性官能基之矽酮樹脂:
- 如請求項1所述之黏著劑組成物,其中,前述反應性官能基為羥基及環氧基中的至少1個。
- 如請求項2所述之黏著劑組成物,其中,前述反應性官能基為羥基及環氧基中的至少1個。
- 如請求項1所述之黏著劑組成物,其中,前述(B)熱硬化性樹脂為環氧樹脂。
- 如請求項2所述之黏著劑組成物,其中,前述(B)熱硬化性樹脂為環氧樹脂。
- 如請求項3所述之黏著劑組成物,其中,前述(B)熱硬化性樹脂為環氧樹脂。
- 如請求項4所述之黏著劑組成物,其中,前述(B)熱硬化性樹脂為環氧樹脂。
- 如請求項5所述之黏著劑組成物,其中,進而含有環氧樹脂硬化劑及環氧樹脂硬化促進劑中的至少1種。
- 如請求項6所述之黏著劑組成物,其中,進而含有環氧樹脂硬化劑及環氧樹脂硬化促進劑中的至少1種。
- 如請求項7所述之黏著劑組成物,其中,進而含有環氧樹脂硬化劑及環氧樹脂硬化促進劑中的至少1種。
- 如請求項8所述之黏著劑組成物,其中,進而含有環氧樹脂硬化劑及環氧樹脂硬化促進劑中的至少1種。
- 如請求項1~請求項12中的任一項所述之黏著劑組成物,其中,前述(C)具有助焊劑活性之化合物為具有羧基或酚性羥基之化合物。
- 一種黏著片材,其具有黏著劑層,該黏著劑層是使用如請求項1~請求項12中的任一項所述之黏著劑組成物而形成。
- 一種半導體裝置保護用材料,其具有黏著劑層,該黏著劑層是使用如請求項1~請求項12中的任一項所述之黏著劑組成物而形成。
- 一種半導體裝置,其具備如請求項1~請求項12中的任一項所述之黏著劑組成物的硬化物。
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2012
- 2012-04-25 JP JP2012100387A patent/JP5739372B2/ja active Active
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2013
- 2013-04-01 US US13/854,469 patent/US8808865B2/en active Active
- 2013-04-16 TW TW102113461A patent/TWI577771B/zh active
- 2013-04-23 KR KR1020130044808A patent/KR101802425B1/ko active IP Right Grant
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TW200923039A (en) * | 2007-11-20 | 2009-06-01 | Nat Starch Chem Invest | Low-voiding die attach film, semiconductor package, and processes for making and using same |
TW200942594A (en) * | 2008-02-07 | 2009-10-16 | Sumitomo Bakelite Co | Film for semiconductor, method for manufacturing semiconductor device and semiconductor device |
Also Published As
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US20130289225A1 (en) | 2013-10-31 |
KR101802425B1 (ko) | 2017-11-28 |
JP2013227429A (ja) | 2013-11-07 |
US8808865B2 (en) | 2014-08-19 |
KR20130120403A (ko) | 2013-11-04 |
JP5739372B2 (ja) | 2015-06-24 |
TW201348373A (zh) | 2013-12-01 |
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