TWI500728B - 黏著薄片及電子零件 - Google Patents

黏著薄片及電子零件 Download PDF

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Publication number
TWI500728B
TWI500728B TW099141078A TW99141078A TWI500728B TW I500728 B TWI500728 B TW I500728B TW 099141078 A TW099141078 A TW 099141078A TW 99141078 A TW99141078 A TW 99141078A TW I500728 B TWI500728 B TW I500728B
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Taiwan
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meth
adhesive
acrylate
mass
parts
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TW099141078A
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English (en)
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TW201129670A (en
Inventor
Takeshi Saitoh
Tomomichi Takatsu
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Denki Kagaku Kogyo Kk
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    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
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    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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    • C08K3/38—Boron-containing compounds
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    • 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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    • C09J2301/314—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 layer and/or the carrier being conductive
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Description

黏著薄片及電子零件
本發明係關於一種黏著薄片及使用該黏著薄片之電子零件。更詳細言之，本發明係關於一種黏著薄片，係使用於製造封裝有半導體晶片之電子零件時之切割步驟及晶粒接合步驟中。
在由半導體晶圓切下晶片之切割步驟中，為了在切斷時保護及固定晶圓，且於拾取步驟之前固定切斷後之晶片，一般使用切割用黏著薄片(例如參照專利文獻1)。另一方面，該切下之半導體晶片在封裝於基板及引線架、或積層於其他半導體晶片時，係使用晶粒接合(黏晶)薄膜。
又，先前亦有提出積層型黏著薄片，其係藉由在黏著薄片上積層黏晶膠材，使其兼備切割用黏著薄片之功能、及使半導體晶片固定在引線架上之黏著劑功能(例如參照專利文獻2至5)。
在使用該積層型黏著薄片製造電子零件時，係例如將已固定半導體晶圓之黏著薄片安裝於環狀架上，再以切割刀切割半導體晶圓。之後，再使黏著薄片成放射狀擴大以使晶片間隔增大，再拾取在黏晶膠材薄膜上成附著狀態之半導體晶片，向基板及引線架等進行封裝。
[先前技術文獻] [專利文獻]
專利文獻1 日本專利特開2006-137816號公報
專利文獻2　日本專利特開2006-049509號公報
專利文獻3　日本專利特開2007-246633號公報
專利文獻4　日本專利特開2010-74144號公報
專利文獻5　日本專利特開2010-177699號公報
然而，在專利文獻2至5中所載之先前的黏著薄片中，若為賦予其導電性而使黏晶膠材薄膜含有導電性填充劑，又會產生減低半導體晶片之固定性及拾取性之問題。
因此，本發明之主要目的在提供一種黏晶膠材薄膜(die attach film)具有導電性、且對半導體晶片之固定性及拾取性優良之黏著薄片；以及使用該黏著薄片之電子零件。
本發明中之黏著薄片，係具備基材薄膜、積層在該基材薄膜之一面上之黏著層、及積層在該黏著層上而含有導電性填充劑之黏晶膠材薄膜，且前述黏著層中含有100質量份之(甲基)丙烯酸酯共聚物，其中含羧基單體之共聚合比率低於0.5%、及0.5至20質量份之多官能異氰酸酯硬化劑。
該黏著薄片中，前述黏著層中亦可再含有20至200質量份之含4個以上乙烯基之胺基甲酸酯丙烯酸酯寡聚物、及0.1至10質量份有機矽改性丙烯酸樹脂。
前述黏著層之厚度可例如為20至50μm。
前述導電性填充劑可使用例如銀、銅、氮化硼或氧化鋁之單體或其混合物。
<用語之說明>
其中之單體單位意指由單體而成之構造單位。其中之「份」及「%」為質量基準。(甲基)丙烯酸酯係丙烯酸酯及甲基丙烯酸酯之總稱。(甲基)丙烯酸等其中含(甲基)之化合物亦同樣為在其名稱中含「甲基」之化合物及不含「甲基」之化合物之總稱。
本發明中之電子零件，係使用前述黏著薄片製成者。
依發明，用於電子零件製造之黏著薄片中，可不降低半導體晶片之固定性及拾取性，而賦予黏晶膠材薄膜導電性。
[實施發明之形態]
以下參照所附之圖式，詳細說明用以實施本發明之形態。同時，本發明並不限定於以下說明之實施形態。
(第1實施形態)
首先說明本發明第1實施形態之黏著薄片。本實施形態中之黏著薄片之構造，係為在基材薄膜之一面上積層黏著層，於該黏著層再積層黏晶膠材薄膜。且在該黏晶膠材薄膜中摻混有導電性填充劑。構成該黏著層之黏著劑中含有100質量份之(甲基)丙烯酸酯共聚物、及0.5至20質量份之多官能異氰酸酯硬化劑，且其(甲基)丙烯酸酯共聚物中含羧基單體之共聚合比率低於0.5%。
〔基材薄膜〕
其中之基材薄膜之材質並無特別之限定，可列舉如聚氯乙烯、聚對苯二甲酸乙二酯、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸-丙烯酸酯、乙烯-丙烯酸乙酯共聚物、聚乙烯、聚丙烯、乙烯-丙烯酸共聚物，或乙烯-(甲基)丙烯酸共聚物及乙烯-(甲基)丙烯酸-(甲基)丙烯酸酯共聚物等經金屬離子交聯之離子聚合物樹脂等形成。基材薄膜可由此等樹脂之混合物或共聚物形成，亦可積層不同材質之薄膜而形成。
此等樹脂中以離子聚合物樹脂較佳，特別是含乙烯單位、(甲基)丙烯酸單位、及(甲基)丙烯酸烷酯單位之共聚物再經Na+ 、K+ 、Zn2+ 等金屬離子交聯之離子聚合物樹脂較佳。基材薄膜中使用此等離子聚合物樹脂時，可以抑制在切割時產生鬚狀之切削屑。
此外，基材薄膜最好再施予抗靜電處理。藉此，可以防止黏晶膠材薄膜在剝離時帶電。基材薄膜抗靜電處理之方法並無特別之限定，可例如(1)在構成基材薄膜之組成物中摻合抗靜電劑之處理、(2)在基材薄膜上積層黏晶膠材薄膜之側的面上塗布抗靜電劑之處理、(3)利用電暈放電進行之帶電處理等均可。
抗靜電劑可使用四級胺鹽單體等。作為四級胺鹽 單體之例可舉如(甲基)丙烯酸二甲胺基乙酯四級氯化物、(甲基)丙烯酸二乙胺基乙酯四級氯化物、(甲基)丙烯酸甲乙胺基乙酯四級氯化物、對二甲胺基苯乙烯四級氯化物、及對二乙胺苯乙烯四級氯化物等，其中特別以甲基丙烯酸二甲胺基乙酯四級氯化物較佳。
〔黏著層〕
構成黏著層之黏著劑，係對100質量份之(甲基)丙烯酸酯共聚物摻合多官能異氰酸酯硬化劑。又，(甲基)丙烯酸酯共聚物中含羧基單體之共聚合比率為低於0.5%。此外，構成黏著層之黏著劑中，以在前述各成分之外，再摻合20至200質量份其中含4個以上乙烯基之胺基甲酸酯丙烯酸酯寡聚物、及0.1至10質量份之有機矽改性丙烯酸樹脂為佳。
<(甲基)丙烯酸酯共聚物：100質量份>
本實施形態之黏著薄片之黏著層中所含之(甲基)丙烯酸酯共聚物，係由主單體之(甲基)丙烯酸酯與乙烯化合物單體共聚合所形成。該(甲基)丙烯酸酯共聚物係光硬化型壓感性黏著劑，藉由紫外光照射使其三次元網狀化，可容易地剝離黏晶膠材薄膜。
(甲基)丙烯酸酯主單體之例可舉如(甲基)丙烯酸丁酯、(甲基)丙烯酸2-丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸十三酯、(甲基)丙烯酸肉豆蔻酯、(甲基)丙烯酸鯨蠟酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯、(甲基)丙烯酸丁氧基甲酯、(甲基)丙烯酸乙氧正丙酯等。
乙烯化合物單體可使用例如其中含有選自羥基、羧基、環氧基、醯胺基、胺基、羥甲基、磺酸基、磺胺酸基、及(亞)磷酸酯基所構成之官能基群組中之1或2個以上之官能基之單體。
在此，含羥基單體之例可舉如(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、及(甲基)丙烯酸2-羥丁酯等。
含羧基單體之例可舉如(甲基)丙烯酸、丁烯酸、順丁烯二酸、順丁烯二酸酐、伊康酸、反丁烯二酸、丙烯醯胺-N-乙醇酸、及肉桂酸等。
含環氧基單體之例可舉如芳基環氧丙基醚及(甲基)丙烯酸環氧丙基醚等。
含醯胺基單體之例可舉如(甲基)丙烯醯胺等。
含胺基單體之例可舉如(甲基)丙烯酸N,N-二甲胺基乙酯等。
含羥甲基單體之例可舉如N-羥甲基丙烯醯胺等。
惟(甲基)丙烯酸酯共聚物中含羧基單體之共聚合比率為0.5%以上時，因其與黏晶膠材薄膜之相互作用，會提高其密著性，因此可能使拾取操作不良。因此，本實施形態中之黏著薄片係使用含羧基單體之共聚合比率低於0.5%之(甲基)丙烯酸酯共聚物。
前述(甲基)丙烯酸酯共聚物之製造方法，可舉如乳化聚合及溶液聚合等，其中以乳化聚合較佳。藉此，可抑制其與黏晶膠材薄膜相互作用，使黏晶膠材薄膜可容易地由黏著薄片上剝離。
<多官能異氰酸酯硬化劑：0.5至20質量份>
多官能異氰酸酯硬化劑，係含有2個以上之異氰酸酯基者，其例可舉如芳香族聚異氰酸酯、脂肪族聚異氰酸酯、及脂環族聚異氰酸酯等。
在此芳香族聚異氰酸酯之例可舉如1,3-苯二異氰酸酯、4,4'-二苯二異氰酸酯、1,4-苯二異氰酸酯、4,4'-二苯甲烷二異氰酸酯、2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、4,4'-甲苯胺二異氰酸酯、2,4,6-三異氰酸酯甲苯、1,3,5-三異氰酸酯苯、二甲氧基苯胺二異氰酸酯、4,4'-二苯醚二異氰酸酯、4,4',4"-三苯甲烷三異氰酸酯、ω,ω'-二異氰酸酯-1,3-二甲基苯、ω,ω'-二異氰酸酯-1,4-二甲基苯、ω,ω'-二異氰酸酯-1,4-二乙基苯、1,4-四甲二甲苯基二異氰酸酯、及1,3-四甲二甲苯基二異氰酸酯等。
脂肪族聚異氰酸酯之例可舉如三亞甲基二異氰酸酯、四亞甲基二異氰酸酯、六亞甲基二異氰酸酯、五亞甲基二異氰酸酯、1,2-丙基二異氰酸酯、2,3-丁基二異氰酸酯、1,3-丁基二異氰酸酯、十二甲基二異氰酸酯、及2,4,4-三甲基六甲基二異氰酸酯等。
脂環族聚異氰酸酯之例可舉如3-異氰酸酯甲基-3,5,5-三甲基環己異氰酸酯、1,3-環戊烷二異氰酸酯、1,3-環己烷二異氰酸酯、1,4-環己烷二異氰酸酯、甲基-2,4-環己烷二異氰酸酯、甲基-2,6-環己烷二異氰酸酯、4,4'-甲基雙(環己異氰酸酯)、1,4-雙(異氰酸甲酯)環己烷、及1,4-雙(異氰酸甲酯)環己烷等。
而且，聚異氰酸酯中，以1,3-苯二異氰酸酯、4,4'-二苯二異氰酸酯、1,4-苯二異氰酸酯、4,4'-二苯甲烷二異氰酸酯、2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、4,4'-甲苯胺二異氰酸酯、及六亞甲基二異氰酸酯較佳。
惟多官能異氰酸酯硬化劑之摻合量，在相對於100質量份之(甲基)丙烯酸酯共聚物為低於0.5質量份時，其黏著力變得過強，因此會發生拾取不良。又，多官能異氰酸酯硬化劑之摻合量，在相對於100質量份之(甲基)丙烯酸酯共聚物為高於20質量份時，其黏著力會降低，切割時會減低黏著薄片與環狀框架間之固定力。因此，本實施形態之黏著薄片中，多官能異氰酸酯硬化劑之摻合比例，相對於100質量份之(甲基)丙烯酸酯共聚物係設為0.5至20質量份。
藉此，不僅可抑制拾取不良之發生，同時可維持切割時黏著薄片與環狀框架間之固定性。多官能異氰酸酯硬化劑之摻合比例，以相對於100質量份之(甲基)丙烯酸酯共聚物為1.0至10質量份為更佳。
＜胺基甲酸酯丙烯酸酯寡聚物：20至200質量份＞
本實施形態之黏著薄片中，為使其易於由黏晶膠材薄膜上剝離，亦可於黏著層中摻合特定量之含4個以上乙烯基之胺基甲酸酯丙烯酸酯寡聚物。在此，所謂含4個以上乙烯基之胺基甲酸酯丙烯酸酯寡聚物(以下亦可單稱為胺基甲酸酯丙烯酸酯寡聚物。)，係指含4個以上之乙烯基，且分子內含胺基甲酸酯鍵結之(甲基)丙烯酸酯寡聚物。
如此，藉由摻合含乙烯基數4個以上之胺基甲酸酯丙烯酸酯寡聚物，可更提高黏晶膠材薄膜從經紫外線照射硬化之黏著劑層剝離之剝離性。其結果可容易地在黏晶膠材薄膜黏附狀態下拾取半導體晶片。黏著層中摻合含乙烯基數低於4個之胺基甲酸酯丙烯酸酯寡聚物時，會使其紫外線照射後黏著力之降低不充分，反而減低其拾取特性。
在摻合該胺基甲酸酯丙烯酸酯寡聚物時，其摻合量以相對於100質量份之(甲基)丙烯酸酯共聚物為20至200質量份為較佳。胺基甲酸酯丙烯酸酯寡聚物之摻合量為低於20質量份時，從紫外線照射後之黏著層剝離之剝離性無法充分地得到提高之效果。另一方面，胺基甲酸酯丙烯酸酯寡聚物之摻合量為高於200質量份時，不僅在切割時易發生糊沾黏使拾取不良，同時易隨反應殘渣而產生微量之糊殘留。其結果，黏晶膠材薄膜所附著之半導體晶片，在搭載於引線架上時，容易發生加溫時的接著不良。
在此，作為胺基甲酸酯丙烯酸酯寡聚物係指：(a)由含羥基及複數(甲基)丙烯酸酯基之(甲基)丙烯酸酯化合物、與含複數異氰酸酯基之化合物(例如二異氰酸酯化合物)反應製成者；(b)在含複數羥基末端之多元醇寡聚物中添加過剩量之含複數異氰酸酯基之化合物(例如二異氰酸酯化合物)反應，製成含複數異氰酸酯基末端之寡聚物，再使其與含羥基及複數之(甲基)丙烯酸酯基之(甲基)丙烯酸酯化合物反應所製成者。
作為(a)之胺基甲酸酯丙烯酸酯寡聚物中含羥基及複數(甲基)丙烯酸酯基之(甲基)丙烯酸酯化合物，可例舉如羥丙基化三羥甲丙烷三丙烯酸酯、三丙烯酸新戊四酯、羥基五丙烯酸二新戊四酯、四丙烯酸雙(新戊四)酯、四羥甲基甲烷三丙烯酸酯、二丙烯酸環氧丙酯、或此等丙烯酸酯基之部份或全部為甲基丙烯酸酯基之化合物等。
另一方面，作為含複數異氰酸酯基之化合物，可例舉如芳香族異氰酸酯、脂環族異氰酸酯、及脂肪族異氰酸酯等。
具體而言，芳香族二異氰酸酯之例可舉如甲苯二異氰酸酯、4,4-二苯基甲烷二異氰酸酯、二甲苯二異氰酸酯。
脂環族二異氰酸酯之例可舉如異佛酮二異氰酸酯、甲基-雙(4-環己基異氰酸酯)。
脂肪族二異氰酸酯之例可舉如六甲基二異氰酸酯、三甲基六甲基二異氰酸酯。
且此等異氰酸酯中，以含複數異氰酸酯基之芳香族異氰酸酯或脂環族異氰酸酯較佳。異氰酸酯成分之形態有單體、二聚體及三聚體，其中特別以三聚體較佳。
(b)之胺基甲酸酯丙烯酸酯寡聚物中，含複數羥基末端之多元醇寡聚物中之多元醇成分，可例舉如聚(環氧丙烷)二醇、聚(環氧丙烷)三醇、共聚(環氧乙烷-環氧丙烷)二醇、聚(四氫呋喃)二醇、乙氧基化雙酚A、乙氧基化雙酚S螺甘油、己內酯改性二醇及碳酸二醇酯等。
<有機矽改性丙烯酸樹脂：0.1至10質量份>
本實施形態之黏著薄片中，為使黏晶膠材薄膜更易於剝離，亦可在黏著層中與前述胺基甲酸酯丙烯酸酯寡聚物共同摻合特定量之有機矽改性丙烯酸樹脂。
作為摻合在構成黏著層之黏著劑中之有機矽改性丙烯酸樹脂，較佳為(甲基)丙烯單體與有機矽系巨分子單體之聚合物，該有機矽系巨分子單體在與聚二甲基矽氧烷鍵結之末端含乙烯基。更佳為有機矽系巨分子單體在與聚二甲基矽氧烷鍵結之末端為(甲基)丙烯醯基或苯乙烯基等乙烯基之化合物。
再者，有機矽改性丙烯酸樹脂中有機矽系巨分子單體單位之比例，以相對於100質量份之有機矽改性丙烯酸樹脂為15至50質量份較佳。如此，可提高黏晶膠材薄膜從紫外線照射後之黏著層剝離之剝離性，可提高半導體晶片之拾取性。此外，由於可抑制有機矽改性丙烯酸樹脂流出於黏著劑表面，因此在將黏附有黏晶膠材薄膜之半導體晶片搭載於引線架上時，不易發生加溫時的接著不良。
此外，作為有機矽改性丙烯酸樹脂，以使用其構成單位具有來自具反應性之(甲基)丙烯酸羥烷酯、改性(甲基)丙烯酸羥酯及乙烯基之單體中至少1者之有機矽改性丙烯酸樹脂較佳。若使用此等有機矽改性丙烯酸樹脂，則在拾取半導體晶片時，可防止稱為微粒(particle)之微小的糊殘留。藉此，在黏著層上積層黏晶膠材薄膜後，亦可防止有機矽改性丙烯酸樹脂移動至黏晶膠材薄膜中。
作為該有機矽改性丙烯酸樹脂的原料之(甲基)丙烯酸酯單體，可例舉如(甲基)丙烯酸烷酯、(甲基)丙烯酸羥烷酯、改性(甲基)丙烯酸羥酯及(甲基)丙烯酸等。
(甲基)丙烯酸烷酯之例可舉如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異莰酯及(甲基)丙烯酸羥烷酯等。
(甲基)丙烯酸羥烷酯之例可舉如(甲基)丙烯酸羥乙酯、(甲基)丙烯酸羥丙酯、及(甲基)丙烯酸羥丁酯等。
改性(甲基)丙烯酸羥酯之例可舉如環氧乙烷改性(甲基)丙烯酸羥酯及內酯改性(甲基)丙烯酸羥酯等。
在摻合前述有機矽改性丙烯酸樹脂時，其摻合量較佳為相對於100質量份之(甲基)丙烯酸酯為0.1至10質量份。有機矽改性丙烯酸樹脂之摻合量在低於0.1質量份時，無法充分得到提高由紫外線照射後之黏著層剝離之剝離性的效果。另一方面，有機矽改性丙烯酸樹脂之摻合量高於10質量份時，初期黏著力之降低程度會增大，因此切割時容易產生由環狀框架的剝離。
<其他成分>
本實施形態之黏著薄片中之黏著層，在不對其他成分造成影響之範圍下，亦可再含聚合起始劑、軟化劑、抗老化劑、填充劑、紫外線吸收劑及光安定劑等添加劑。
<厚度：5至100μm>
黏著層之厚度低於5μm時，會降低黏著力，而在切割時會降低黏著薄片與環狀框架之間的固定力。又，黏著層之厚度高於100μm時，黏著力會過強，可能會發生拾取不良。因此，黏著層之厚度以5至100μm較佳。再者，黏著層厚度更佳的範圍係20至50μm，藉此，半導體晶片之固定性及拾取性兩者，可在保持良好平衡下提高。
[黏晶膠材薄膜]
用於本實施形態黏著薄片之黏晶膠材薄膜，係接著劑組成物成形為薄膜狀者，且含有導電性填充劑。作為構成此黏晶膠材薄膜之組成物，可舉如丙烯酸系、聚醯胺系、聚乙烯系、聚碸系、環氧系、聚醯亞胺系、聚醯胺酸系、有機矽系、酚系、橡膠系聚合物、含氟橡膠系聚合物及含氟樹脂之單體、或此等之混合物或共聚物等。又，黏晶膠材薄膜亦可由不同材質之薄膜積層形成。再者，接著劑組成物中亦可再添加光聚合起始劑、抗靜電劑或交聯促進劑。
<導電性填充劑>
另一方面，摻合導電性填充劑係為了賦予黏晶膠材薄膜導電性，同時提高其放熱性。作為該導電性填充劑可使用如銀、銅、氮化硼、氧化鋁、金、鈀或鎳之單體或其混合物。此外，在可靠性、放熱特性及成本方面，導電性填充劑以使用銀、銅、氮化硼或氧化鋁較佳。
另一方面，導電性填充劑之摻合量，以相對於100質量份之構成黏晶膠材薄膜之接著劑組成物中之樹脂成分設為10至1900質量份較佳。導電性填充劑之摻合量低於10質量份時，放熱特性可能不充分，摻合量高於1900質量份時，可能變脆因此降低製膜性。
本實施形態之黏著薄片，可以例如在基材薄膜上塗佈黏著劑形成黏著層後，再藉由於該黏著層上黏著另外形成之黏晶膠材薄膜而製成。此時，必須調整黏晶膠材薄膜與黏著層間之黏著強度。該黏晶膠材薄膜與黏著層間之黏著強度大時，可能造成拾取不良，反之黏著強度小時，會降低晶片之固定。具體言之，黏晶膠材薄膜與黏著層間之黏著強度，以0.05至0.9N/20mm為佳。
如上述之詳細說明，由於本實施形態之黏著薄片，不只在黏晶膠材薄膜上含有導電性填充劑，同時在黏著層中所含(甲基)丙烯酸酯共聚物中含羧基單體之共聚合比率低於0.5%，因此可在不降低半導體晶片之固定性及拾取性下，賦予黏晶膠材薄膜導電性。
(第2實施形態)
其次，再說明本發明之第2實施形態之電子零件。本實施形態之電子零件，使用前述第1實施形態之黏著薄片而封裝有半導體晶片等。圖1(a)至(d)係顯示本實施形態之電子零件製造方法的步驟順序之斷面圖。
在製造本實施形態的電子零件時，首先，如圖1(a)所示，進行使矽晶圓101黏著固定在黏著薄片110上之貼附步驟、及使黏著薄片110固定在環狀框架102上之固定步驟(步驟S1)。其次，如圖1(b)所示，進行以切割刀104切割矽晶圓101製成半導體晶片108之切割步驟(步驟S2)。
之後，進行使黏著薄片110成放射狀擴大以使半導體晶片108之間隔增大之擴展步驟(步驟S3)，在此狀態下以真空套爪吸住半導體晶片108而拾取之(步驟S4)。在該步驟S4之拾取步驟中，如圖1(c)所示，使黏著層103與黏晶膠材薄膜105間剝離，並拾取附著有黏晶膠材薄膜105狀態之半導體晶片108。
其次，如圖1(d)所示，進行將附著有黏晶膠材薄膜105之半導體晶片108搭載於例如引線架111等之上之搭載步驟(步驟S5)。接著，進行加熱黏晶膠材薄膜105，而使半導體晶片108與引線架111加熱接著之加熱接著步驟(步驟S6)及將引線架111或搭載於電路基板之半導體晶片108以樹脂(未圖示)鑄模之鑄模步驟(步驟S7)。
本實施形態之電子零件中，由於使用前述第1實施形態之黏著薄片，故在其製造步驟中，半導體晶片之固定性及拾取性均良好。
[實施例]
以下，舉出本發明之實施例及比較例，具體說明本發明之效果。再者，本發明並不限定於此等實施例。本實施例中，係以如下所示之方法及條件，製造實施例1至13及比較例1至7中之黏著薄片，而評估其性能。
具體而言，先以下述表1及表2中所示摻合之黏著劑，塗佈於聚苯二甲酸乙二酯製之分離薄膜上，以使其乾燥後黏著層厚度成為20μm之方式來塗層。其次，使該黏著層積層於基材薄膜上之後，將黏晶膠材薄膜切為6.2吋φ之圓形，再層壓於黏著層上，得到實施例及比較例中之各黏著薄片。
此時，實施例及比較例中全部之基材薄膜係使用Du Pont-Mitsui Polychemicals公司製造之離子聚合物樹脂。具體而言，其係主體為乙烯-甲基丙烯酸-甲基丙烯酸烷酯共聚合物之Zn鹽，而含有Zn2+ 離子者，其MFR(熔融流動率)值為1.5g/10分鐘(JIS K7210，210℃)、熔點96℃、厚度80μm。
又，黏著層所含之各成分如下。
<(甲基)丙烯酸酯共聚物>
A：綜研化學公司製造SK-Dyne1496
丙烯酸2-乙基己酯：95質量%、與丙烯酸2-羥乙酯：5質量%，以溶液聚合所得之共聚物，其不含羧基。
B：日本Zeon公司製造AR53L
丙烯酸乙酯：40質量%、丙烯酸丁酯：23質量%、與丙烯酸甲氧基乙酯：37質量%，以懸浮聚合製成共聚物，其不含羧基。
C：綜研化學公司製造SK-Dyne1305H
丙烯酸丁酯：65質量%、丙烯酸甲酯：25質量%、丙烯酸：5質量%之共聚物，以溶液聚合得到，其含有羧基(單體之共聚合比率：5%)。
<多官能異氰酸酯硬化劑>
A：Nippon Polyurethane公司製造CORONATE L-45E(註冊商標)
2,4-甲苯基二異氰酸酯之三羥甲基丙烷加合物。
<含4個以上乙烯基之胺基甲酸酯丙烯酸酯寡聚物>
上述表1及表2中僅記載胺基甲酸酯丙烯酸酯寡聚物。
A：根上工業公司製造UN-3320HS
使異佛酮二異氰酸酯(脂環族二異氰酸酯)之三聚體反應製成之末端異氰酸酯寡聚物與五丙烯酸二新戊四醇酯(dipentaerythritol pentaacrylate)反應後生成之末端丙烯酸酯寡聚物。數量平均分子量為3700。丙烯酸酯官能基數為15個。
B：新中村化學公司製造UA-340P
使異佛酮二異氰酸酯與聚(丙二醇)二醇之末端反應而成之末端異氰酸酯寡聚物再與丙烯酸2-羥乙酯反應而成之末端丙烯酸酯寡聚物。數量平均分子量為13000。乙烯基數為每1分子2個。
＜有機矽改性丙烯酸樹脂＞
A：綜研化學公司製造UTMM-LS2
使有機矽分子鏈之末端含有帶(甲基)丙烯醯基之有機矽系寡聚物系單位，與由甲基丙烯酸甲酯等所構成之丙烯酸乙烯基單位聚合生成之有機矽系接枝共聚物。
＜黏晶膠材薄膜＞
A：相對於100質量份之其主體為環氧接著劑之樹脂成分，含有400質量份之銀填充劑。厚度為30μm。
B：相對於100質量份之其主體為環氧接著劑之樹脂成分，含有400質量份之氮化硼填充劑。厚度為30μm。
C：相對於100質量份之其主體為環氧接著劑之樹脂成分，含有400質量份之氧化鋁填充劑。厚度為30μm。
D：相對於100質量份之其主體為環氧接著劑之樹脂成分，含有400質量份之鎳填充劑。厚度為30μm。
＜光聚合起始劑＞
光聚合起始劑為苯甲二甲基縮酮，具體地為使用Ciba Speciality Chemicals公司製造之Irgacure 651(註冊商標)。
其次，使用以前述方法及條件製成之實施例及比較例中之各黏著薄片，以同前述第2實施形態電子零件之製造方法，進行如下所述之步驟S1至S7來製造電子零件。然後，針對實施例及比較例之各黏著薄片，評估其半導體晶片之固定性及拾取性。
步驟S1：
同時進行將矽晶圓101貼附於黏著薄片110上固定之貼附步驟、及將黏著薄片110固定於環狀框架102上之固定步驟(參照圖1(a))。此時，矽晶圓101係使用形成虛置電路圖案後之直徑8英吋×厚度0.3mm之矽晶圓。
步驟S2：
以切割刀104進行使矽晶圓101形成晶片大小為6mm×6mm之半導體晶片108之切割步驟(參照圖1(b))。切割之主要設定如下。
黏著薄片110上切割線107之量：15μm
切割裝置：DISCO公司製造DAD341
切割刀：DISCO公司製造NBC-ZH2050-27HEEE
切割刀形狀：外徑55.56mm、刀寬35μm、內徑19.05mm
切割刀轉速：40,000rpm
切割刀進給速度：50mm/秒鐘
切割水溫度：25℃
切割水量：1.0L/秒鐘
步驟S3：
進行使黏著薄片110成放射狀擴大，使半導體晶片108之間隔增大之擴展步驟(未圖示)。此時擴展之量為8mm。
步驟S4：
以針頭(未圖示)頂起後，再以真空套爪(未圖示)吸附半導體晶片108，使黏著層103與黏晶膠材薄膜105之間剝離，進行拾取附著有黏晶膠材薄膜105之半導體晶片108之拾取步驟(參照圖1(c))。拾取時之主要設定如下。
拾取裝置：Canon Machinery公司製造CAP-300II
針頭形狀：250μmR
針頭頂起高度：0.5mm
步驟S5：
進行將附著有黏晶膠材薄膜105之半導體晶片108搭載於引線架111之搭載步驟(參照圖1(d))。
步驟S6：
進行加熱黏晶膠材薄膜105，使半導體晶片108與引線架111加熱接著之加熱接著步驟(未圖示)。
步驟S7：
進行將搭載於引線架111之半導體晶片108以樹脂(未圖示)鑄模之鑄模步驟(未圖示)。
之後以以下所示之基準評估晶片之固定性及拾取性。
＜晶片固定性＞
晶片固定性，係在步驟S3之切割步驟之後，評估半導體晶片108固定在黏著薄片110上之半導體晶片108之殘存率。
◎(優)：晶片之脫離低於5%。
○(良)：晶片之脫離為5%以上、低於10%。
×(不可)：晶片之脫離為10%以上。
＜拾取性＞
拾取性係在步驟S5之拾取步驟中，評估可拾取之比例。
◎(優)：晶片95%以上為可拾取。
○(良)：晶片80%以上、低於95%為可拾取。
×(不可)：晶片低於80%為可拾取。
以上之結果一併表示於上述表1及表2中。如上述表1及表2中所示，在多官能異氰酸酯硬化劑之含量不足0.5質量份之比較例1之黏著薄片中，其拾取性不佳。另一方面，在多官能異氰酸酯硬化劑之含量高於20質量份之比較例2之黏著薄片中，其晶片固定性不佳。
又，在使用含羧基單體之共聚合比率為0.5%以上之(甲基)丙烯酸酯共聚物之比較例3及比較例7之黏著薄片中，其拾取性均不佳。另一方面，在添加高於200質量份之胺基甲酸酯丙烯酸酯寡聚物之比較例4之黏著薄片中，其晶片固定性及拾取性兩者均不佳。
此外，在添加了乙烯基數目少於4個之胺基甲酸酯丙烯酸酯寡聚物之比較例5之黏著薄片中，其拾取性不佳。同時，在添加了高於10質量份之有機矽改性丙烯酸樹脂之比較例6之黏著薄片中，其晶片固定性不佳。
相對地，在本發明之範圍內製作之實施例1至13之黏著薄片，其晶片固定性及拾取性均係良好。藉此，確認了依本發明可得到黏晶膠材薄膜具導電性、且半導體晶片之固定性及拾取性均良好的黏著薄片。
101‧‧‧矽晶圓
102‧‧‧環狀框架
103‧‧‧黏著層
104‧‧‧切割刀
105‧‧‧黏晶膠材薄膜
106‧‧‧基材薄膜
107‧‧‧切割線
108‧‧‧半導體晶片
110‧‧‧黏著薄片
111‧‧‧引線架
圖1(a)至(d)係顯示本發明第2實施形態中電子零件之製造方法中，步驟順序之斷面圖。
101‧‧‧矽晶圓
102‧‧‧環狀框架
103‧‧‧黏著層
104‧‧‧切割刀
105‧‧‧黏晶膠材薄膜
106‧‧‧基材薄膜
107‧‧‧切割線
108‧‧‧半導體晶片
110‧‧‧黏著薄片
111‧‧‧引線架

Claims (5)

  1. 一種黏著薄片，其係具備：基材薄膜，由離子聚合物樹脂形成；黏著層，積層於該基材薄膜的一面；及黏晶膠材薄膜，積層於該黏著層且含有導電性填充劑；前述黏著層係含有：100質量份之(甲基)丙烯酸酯共聚物，其中含羧基單體的共聚合比率低於0.5%；及0.5至20質量份之多官能異氰酸酯硬化劑。
  2. 如申請專利範圍第1項之黏著薄片，其中前述黏著層進一步含有20至200質量份之具有4個以上乙烯基之胺基甲酸酯丙烯酸酯寡聚物；及0.1至10質量份之有機矽改性丙烯酸樹脂。
  3. 如申請專利範圍第1或2項之黏著薄片，其中前述黏著層之厚度為20至50μm。
  4. 如申請專利範圍第1或2項之黏著薄片，其中前述導電性填充劑係銀、銅、氮化硼或氧化鋁單體或其混合物。
  5. 一種電子零件，其係使用如申請專利範圍第1至4項中任一項之黏著薄片而製成。
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