TW202223021A - 切晶黏晶膜 - Google Patents

切晶黏晶膜 Download PDF

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Publication number
TW202223021A
TW202223021A TW110141490A TW110141490A TW202223021A TW 202223021 A TW202223021 A TW 202223021A TW 110141490 A TW110141490 A TW 110141490A TW 110141490 A TW110141490 A TW 110141490A TW 202223021 A TW202223021 A TW 202223021A
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Taiwan
Prior art keywords
layer
die
mentioned
mass
metal layer
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TW110141490A
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English (en)
Inventor
谷口愁斗
市川智昭
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日商日東電工股份有限公司
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Priority claimed from JP2021142373A external-priority patent/JP2022080836A/ja
Application filed by 日商日東電工股份有限公司 filed Critical 日商日東電工股份有限公司
Publication of TW202223021A publication Critical patent/TW202223021A/zh

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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
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    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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Abstract

本發明之切晶黏晶膜具備於基材層上積層黏著劑層而成之切晶帶、及積層於該切晶帶之黏著劑層上之黏晶層，上述黏晶層包含基質樹脂、含硫醇基化合物、及導電性粒子。

Description

切晶黏晶膜
本發明係關於一種切晶黏晶膜。
已知先前於半導體裝置中，為了改善如功率半導體之處理電流量、發熱較大之半導體晶片之導電性、導熱性，使用設有金屬層之半導體晶圓(帶金屬層之半導體晶圓)，使與基板之接合面側為上述金屬層來製作帶金屬層之半導體晶片(例如下述專利文獻1)。
且說，已知關於用於進行切晶並且將藉由切晶所獲得之半導體晶片接著於基板之構件，使用切晶黏晶膜(例如下述專利文獻2)。 上述切晶黏晶膜具備於基材層上積層黏著劑層而成之切晶帶、及以可剝離之方式積層於該切晶帶之黏著劑層上之黏晶層。 上述切晶黏晶膜藉由使上述黏晶層含有導電性粒子，而與焊接同樣地發揮導電性。 [先前技術文獻] [專利文獻]
[專利文獻1]日本專利特開2015-95550號公報 [專利文獻1]日本專利特開2019-9203號公報
[發明所欲解決之問題]
且說，若上述黏晶層與上述帶金屬層之半導體晶圓之密接性較低，則還會導致於切晶時產生晶片飛散。 因此，對於上述黏晶層，要求提高與上述帶金屬層之半導體晶圓之密接性。
然而，對於提高上述黏晶層與上述帶金屬層之半導體晶圓之密接性，難以說對其進行了充分研究。
因此，本發明之課題在於提供一種能夠提高黏晶層與帶金屬層之半導體晶圓之密接性的切晶黏晶膜。 [解決問題之技術手段]
本發明之切晶黏晶膜具備： 於基材層上積層黏著劑層而成之切晶帶、及 積層於該切晶帶之黏著劑層上之黏晶層， 上述黏晶層包含基質樹脂、含硫醇基化合物、及導電性粒子。
較佳為於上述切晶黏晶膜中， 上述含硫醇基化合物為具有2個以上硫醇基之多官能硫醇化合物。
較佳為於上述切晶黏晶膜中， 上述黏晶層包含0.1質量%以上且30質量%以下之上述含硫醇基化合物。
較佳為於上述切晶黏晶膜中， 上述黏晶層於安裝在一面具備金屬層之矽晶圓之上述金屬層之狀態下，室溫下對於上述金屬層之剝離力為0.5 N/10 mm以上。
較佳為於上述切晶黏晶膜中， 上述黏晶層中之上述導電性粒子之粒子填充率P為70質量%以上且95質量%以下， 150℃下之上述黏晶層之黏度為30 kPa·s以上。
以下，對本發明之一實施方式進行說明。
[切晶黏晶膜] 如圖1所示，本實施方式之切晶黏晶膜20具備：於基材層1上積層黏著劑層2而成之切晶帶10、及積層於切晶帶10之黏著劑層2上之黏晶層3。 切晶黏晶膜20於黏晶層3上貼附半導體晶圓。本實施方式中，於黏晶層3上貼附一面(與電路面相反側之面)設置有金屬層之半導體晶圓(以下亦稱為帶金屬層之半導體晶圓)。 詳細而言，帶金屬層之半導體晶圓係以使金屬層與黏晶層3抵接之狀態進行貼附。 貼附於本實施方式之切晶黏晶膜20之帶金屬層之半導體晶圓係藉由刀片切割、DBG(Dicing Before Grinding、研磨前切割)或SDBG(Stealth Dicing Before Grinding、研磨前隱形切割)等而被割斷成複數個半導體晶片。並且，於如上所述之割斷時，黏晶層3亦與半導體晶圓一起被割斷。黏晶層3被割斷成與已單片化之複數個半導體晶片之尺寸相當的大小。 藉此，能夠得到複數個帶黏晶層3之半導體晶片，更具體而言，能夠得到金屬層安裝於黏晶層3之複數個半導體晶片。 再者，於帶金屬層之半導體晶圓中，金屬層係藉由於半導體晶圓之一面(與電路面相反側之面)塗覆金屬而形成。作為此種金屬，一般使用金、銀、銅等貴金屬。 作為將上述金屬塗覆於半導體晶圓之一面之方法，可例舉電漿氣相沈積、濺鍍、電子束蒸鍍等。 上述金屬層通常以1 μm以上且10 μm以下之厚度形成。
本實施方式之切晶黏晶膜20中，黏晶層3包含基質樹脂、含硫醇基化合物、及導電性粒子。 於本說明書中，導電性粒子意指按照JIS K 0130(2008)所測得之導電率為100 μS/cm以下之粒子。
本實施方式之切晶黏晶膜20中，重要的是黏晶層3包含含硫醇基化合物。 藉由使黏晶層3包含含硫醇基化合物，能夠提高黏晶層3與上述金屬層之密接性。 藉此，本實施方式之切晶黏晶膜20與帶金屬層之半導體晶圓之密接性得到提高。
黏晶層3較佳為具有熱硬化性。即，本實施方式之黏晶膜較佳為包含具有熱硬化性之樹脂作為基質樹脂，較佳為進而包含具有熱硬化性之樹脂之硬化劑。
作為具有熱硬化性之樹脂，例如可例舉：熱硬化性樹脂、具有熱硬化性官能基之熱塑性樹脂。
作為上述熱硬化性樹脂，例如可例舉：環氧樹脂、酚樹脂、胺基樹脂、不飽和聚酯樹脂、胺基甲酸酯樹脂、聚矽氧樹脂及熱硬化性聚醯亞胺樹脂等。上述熱硬化性樹脂可僅使用一種，亦可組合使用2種以上。 上述各種熱硬化性樹脂之中，較佳為使用環氧樹脂。
作為環氧樹脂，例如可例舉：雙酚A型、雙酚F型、雙酚S型、溴化雙酚A型、氫化雙酚A型、雙酚AF型、聯苯型、萘型、茀型、酚系酚醛清漆型、甲酚酚醛清漆型、鄰甲酚酚醛清漆型、三羥基苯基甲烷型、四酚基乙烷型、乙內醯脲型、異氰脲酸三縮水甘油酯型及縮水甘油胺型之環氧樹脂。其中，較佳為使用雙酚A型環氧樹脂及甲酚酚醛清漆型環氧樹脂中之至少一者，更佳為將雙酚A型環氧樹脂與甲酚酚醛清漆型環氧樹脂組合使用。 作為雙酚A型環氧樹脂，可例舉脂肪族改性雙酚A型環氧樹脂。
關於作為環氧樹脂之硬化劑之酚樹脂，例如可例舉：酚醛清漆型酚樹脂、可溶酚醛型酚樹脂、聯苯型酚樹脂、及聚對羥基苯乙烯等聚氧苯乙烯。
又，作為熱硬化性樹脂，亦可使用具有熱硬化性官能基之熱塑性樹脂。作為具有熱硬化性官能基之熱塑性樹脂，例如可例舉含熱硬化性官能基之丙烯酸樹脂。作為含熱硬化性官能基之丙烯酸樹脂中之丙烯酸樹脂，可例舉包含來源於(甲基)丙烯酸酯之單體單元者。 於具有熱硬化性官能基之熱塑性樹脂中，根據熱硬化性官能基之種類來選擇硬化劑。
黏晶層3可包含熱塑性樹脂作為基質樹脂。上述熱塑性樹脂係作為黏合劑發揮功能。 藉由使黏晶層3包含熱塑性樹脂，而即使於熱硬化後，亦能夠使黏晶層3具有相對較低之彈性。 作為上述熱塑性樹脂，例如可例舉：天然橡膠、丁基橡膠、異戊二烯橡膠、氯丁二烯橡膠、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸酯共聚物、聚丁二烯樹脂、聚碳酸酯樹脂、熱塑性聚醯亞胺樹脂、聚醯胺6、聚醯胺6,6等聚醯胺樹脂、苯氧基樹脂、丙烯酸樹脂、PET、PBT等飽和聚酯樹脂、聚醯胺醯亞胺樹脂、氟樹脂等。上述熱塑性樹脂可僅使用一種，亦可組合使用2種以上。作為上述熱塑性樹脂，就由於離子性雜質較少且耐熱性較高，故容易確保基於黏晶層之連接可靠性之觀點而言，較佳為丙烯酸樹脂。
上述丙烯酸樹脂較佳為包含來源於(甲基)丙烯酸酯之單體單元作為按質量比例計最多之單體單元的聚合物。作為(甲基)丙烯酸酯，例如可例舉：(甲基)丙烯酸烷基酯、(甲基)丙烯酸環烷基酯及(甲基)丙烯酸芳基酯等。上述丙烯酸樹脂亦可包含來源於可與(甲基)丙烯酸酯共聚之其他成分之單體單元。作為上述其他成分，例如可例舉：含羧基單體、酸酐單體、含羥基單體、含縮水甘油基單體、含磺酸基單體、含磷酸基單體、丙烯醯胺、丙烯腈等含官能基單體、及各種多官能性單體等。 上述丙烯酸樹脂較佳為含羧基之丙烯酸橡膠。
含硫醇基化合物既可為單官能硫醇化合物(具有1個硫醇基(SH)之硫醇化合物)，亦可為多官能硫醇化合物(具有2個以上硫醇基(SH)之硫醇化合物)，較佳為多官能硫醇化合物(具有2個以上硫醇基(SH)之硫醇化合物)。作為多官能硫醇化合物，可例舉：2官能硫醇化合物、3官能硫醇化合物、4官能硫醇化合物、6官能硫醇化合物等。 藉由具有2個以上硫醇基(SH)之多官能硫醇化合物，能夠更進一步提高黏晶層3與帶金屬層之半導體晶圓之密接性。 含硫醇基化合物可僅使用1種，亦可組合使用2種以上。
作為單官能硫醇化合物，為具有1個硫醇基(SH)之有機化合物即可，作為單官能硫醇化合物之市售品，可例舉：SC化學公司製造之BMPA、EHMP、MBMP、STMP等。 作為2官能硫醇化合物，為具有2個硫醇基(SH)之有機化合物即可，作為2官能硫醇化合物之市售品，可例舉：昭和電工公司製造之BD1，SC化學公司製造之EGMP-4、PXDT等。 作為3官能硫醇化合物，為具有3個硫醇基(SH)之有機化合物即可，作為3官能硫醇化合物之市售品，可例舉：昭和電工公司製造之TPMB、NR1，SC化學公司製造之TMMP、TMMP-LV、TEMPIC、PEPT等。 作為4官能硫醇化合物，為具有4個硫醇基(SH)之有機化合物即可，作為4官能硫醇化合物之市售品，可例舉：昭和電工公司製造之PE1，SC化學公司製造之PEMP、PEMP-1，四國化成公司製造之TS-G、C3TS-G等。 作為6官能硫醇化合物，為具有6個硫醇基(SH)之有機化合物即可，作為6官能硫醇化合物之市售品，可例舉：SC化學公司製造之DPMP等。
黏晶層3較佳為包含0.1質量%以上且30質量%以下之上述含硫醇基化合物。 黏晶層3更佳為包含0.2質量%以上且15質量%以下之上述含硫醇基化合物，進而較佳為包含0.3質量%以上且4.5質量%以下之上述含硫醇基化合物，尤佳為包含0.5質量%以上且2.0質量%以下之上述含硫醇基化合物。 藉由使黏晶層3以上述範圍包含上述含硫醇基化合物，能夠更進一步提高黏晶層3與帶金屬層之半導體晶圓之密接性。 藉此，使用切晶黏晶膜，能夠更進一步抑制於對上述帶金屬層之半導體晶圓切割後產生晶片飛散。 再者，上述含硫醇基化合物之含有比例意指於形成黏晶層3之組合物中之含有比率。
上述導電性粒子較佳為包含銀粒子。 作為上述銀粒子之形狀，例如可使用薄片狀、針狀、絲狀、球狀、扁平狀(包括鱗片狀)者。
上述銀粒子之體積平均粒徑D 50較佳為0.01 μm以上，更佳為0.1 μm以上，尤佳為0.5 μm以上。 藉由使上述銀粒子之體積平均粒徑D 50為0.01 μm以上，除使上述銀粒子相對易分散於上述黏晶層中以外，亦能夠抑制因上述銀粒子之比表面積過大而導致上述銀粒子之表面易被氧化，從而確保上述銀粒子之充分導電性。 藉由使上述銀粒子之體積平均粒徑D 50為0.1 μm以上，除使上述銀粒子更進一步易分散於上述黏晶層中以外，亦能夠更進一步確保上述銀粒子之導電性。 藉由使上述銀粒子之體積平均粒徑D 50為0.5 μm以上，除使上述銀粒子再進一步易分散於上述黏晶層中以外，亦能夠再進一步確保上述銀粒子之導電性。 又，上述銀粒子之體積平均粒徑D 50較佳為10 μm以下，更佳為5 μm以下，尤佳為1 μm以下。 藉由使上述銀粒子之體積平均粒徑D 50為10 μm以下，能夠於使上述熱硬化性樹脂硬化之程度之溫度(例如200℃)下，使上述銀粒子之外表面熔融至能夠燒結之程度。 藉由使上述銀粒子之體積平均粒徑D 50為5 μm以下，能夠於使上述熱硬化性樹脂硬化之程度之溫度下，更易使上述銀粒子之外表面熔融至能夠燒結之程度。 藉由使上述銀粒子之體積平均粒徑D 50為1 μm以下，能夠於使上述熱硬化性樹脂硬化之程度之溫度下，進一步易使上述銀粒子之外表面熔融至能夠燒結之程度。 進而，上述導電性粒子之體積平均粒徑D 50較佳為0.01 μm以上且10 μm以下，更佳為0.1 μm以上且5 μm以下，尤佳為0.5 μm以上且1 μm以下。
上述銀粒子之體積平均粒徑D 50例如可使用雷射繞射-散射式粒度測定裝置(MicrotracBEL公司製造、MICROTRAC MT3000II系列)，按體積基準來進行測定。
上述銀粒子既可為由銀元素及作為不可避免之雜質元素包含之其他元素(金屬元素等)構成之銀粒子，亦可為實施了表面處理(例如矽烷偶合處理)之銀粒子。作為銀粒子之表面處理劑，可例舉：脂肪酸系、胺系、環氧系等之被覆劑。作為經脂肪酸系被覆劑表面處理之銀粒子之市售品，可例舉DOWA Electronics公司製造之AG-2-8F等。 再者，以下有時將經脂肪酸系、胺系、環氧系等之被覆劑表面處理之銀粒子稱為被覆劑處理銀粒子。 本實施方式之黏晶層較佳為使用被覆劑處理銀粒子作為上述銀粒子。藉由使用被覆劑處理銀粒子作為上述銀粒子，能夠提高與上述所包含之樹脂成分(熱硬化性樹脂及熱塑性樹脂)之親和性，因此上述銀粒子易分散於上述黏晶層中。
上述導電性粒子除銀粒子以外，還可包含鎳粒子、銅粒子、鋁粒子、碳黑、奈米碳管、作為核(core)之金屬粒子之表面由金或銀等金屬鍍覆而成之粒子(以下亦稱為金屬鍍覆粒子)、及作為核(core)之樹脂粒子之表面由金屬被覆而成之粒子(以下亦稱為金屬被覆樹脂粒子)等。該等導電性粒子可僅使用一種，亦可組合使用2種以上。
作為金屬鍍覆粒子，例如可使用以鎳粒子或銅粒子為核且該核之表面由金、銀等金屬鍍覆而成之粒子。 作為金屬被覆樹脂粒子，例如可使用以樹脂粒子為核且該核之表面由鎳、金等金屬被覆而成之粒子。 於本實施方式之黏晶層包含除銀粒子以外之導電性粒子之情形時，作為該導電性粒子，較佳為使用金屬鍍覆粒子，作為金屬鍍覆粒子，較佳為使用以銅粒子為核且該核之表面由銀鍍覆而成之粒子(銀被覆銅粒子)。作為銀被覆銅粒子之市售品，可例舉：於三井金屬礦業公司製造之商品名1200YP(銅粒子)上塗覆有20質量%之銀粒子者、於三井金屬礦業公司製造之商品名MA-C03K(銅粒子)上塗覆有20質量%之銀粒子者、DOWA Electronics公司製造之商品名AOP-TCY-2(EN)等。 於本實施方式之黏晶層包含除銀粒子以外之導電性粒子之情形時，銀粒子於導電性粒子100質量%中所占之質量%較佳為10質量%以上且95質量%以下，更佳為20質量%以上且90質量%以下。
作為除銀粒子以外之導電性粒子之形狀，例如可使用薄片狀、針狀、絲狀、球狀、扁平狀(包括鱗片狀)者。 藉由使用球狀粒子作為除銀粒子以外之導電性粒子，能夠提高除銀粒子以外之導電性粒子於黏晶層中之分散性。
除銀粒子以外之導電性粒子之體積平均粒徑D 50較佳為0.01 μm以上，更佳為0.5 μm以上，尤佳為1.5 μm以上。 又，除銀粒子以外之導電性粒子之體積平均粒徑D 50較佳為20 μm以下，更佳為10 μm以下，尤佳為5 μm以下。 進而，除銀粒子以外之導電性粒子之體積平均粒徑D 50較佳為0.01 μm以上且20 μm以下，更佳為0.5 μm以上且10 μm以下，尤佳為1.5 μm以上且5 μm以下。 除銀粒子以外之導電性粒子之體積平均粒徑D 50亦可與上述銀粒子之體積平均粒徑D 50同樣地進行測定。
就使樹脂成分之硬化反應充分進行、或提高硬化反應速度之觀點而言，黏晶層3亦可含有熱硬化觸媒。作為熱硬化觸媒，例如可例舉：咪唑系化合物、三苯基膦系化合物、胺系化合物、及三鹵代硼烷系化合物。
本實施方式之切晶黏晶膜20中，黏晶層3於安裝在一面具備金屬層之矽晶圓之上述金屬層之狀態下，室溫下對於上述金屬層之剝離力較佳為0.5 N/10 mm以上，更佳為0.7 N/10 mm以上。 藉由使室溫下對於上述金屬層之剝離力為0.5 N/10 mm以上，能夠更進一步提高黏晶層與帶金屬層之半導體晶圓之密接性。 藉此，使用切晶黏晶膜，可更進一步抑制於對上述帶金屬層之半導體晶圓切割後產生晶片飛散。 又，室溫下對於上述金屬層之剝離力可為15 N/10 mm以下。 再者，於本說明書中，室溫意指23±2℃之溫度。
室溫下對於上述金屬層之剝離力可使用延伸試驗機(商品名：Autograph AG-X、島津製作所製造)，藉由於室溫、剝離角度180°及延伸速度300 mm/min之條件下之剝離試驗來測定。 具體而言，可以如下方式進行測定。 (1)於一面具備金屬層之矽晶圓(帶金屬層之矽晶圓)之具備上述金屬層之面重疊黏晶層，得到積層體。再者，上述矽晶圓為裸晶圓。 (2)將該積層體配置於加熱至70℃之加熱板上。再者，上述積層體係以上述帶金屬層之矽晶圓之不具備金屬層之面與加熱板之表面抵接的方式進行配置。 (3)藉由使用壓接輥(輥質量2kg)對上述積層體進行加壓，而形成上述帶金屬層之矽晶圓與上述黏晶層貼合的狀態，於加熱板上放置2分鐘。 (4)將經過放置之上述積層體自加熱板取出，於室溫(23±2℃)下放置20分鐘，藉此得到試驗體。 (5)對於上述試驗體，使用上述延伸試驗機，於上述條件下進行剝離試驗，藉此測定室溫下對於上述金屬層之剝離力。
關於本實施方式之切晶黏晶膜20，較佳為黏晶層3中之上述導電性粒子之粒子填充率P為70質量%以上且95質量%以下，且150℃下之黏晶層3之黏度為30 kPa·s以上。 藉由使粒子填充率P滿足上述數值範圍且使150℃下之黏晶層3之黏度滿足上述數值範圍，能夠更進一步提高黏晶層與帶金屬層之半導體晶圓之密接性。 藉此，使用切晶黏晶膜，能夠更進一步抑制於對上述帶金屬層之半導體晶圓切割後產生晶片飛散。 黏晶層3中之上述導電性粒子之粒子填充率P更佳為75質量%以上，進而較佳為80質量%以上。 又，黏晶層3中之上述導電性粒子之粒子填充率P更佳為90質量%以下，進而較佳為85質量%以下。 再者，黏晶層3中之上述導電性粒子之粒子填充率意指形成黏晶層3之組合物中上述導電性粒子之含有比率，於形成黏晶層3之組合物包含溶劑(例如甲基乙基酮(MEK)等)之情形時，意指將上述溶劑排除在外之組合物中上述導電性粒子之含有比率。 進而，150℃下之黏晶層3之黏度更佳為40 kPa·s以上，進而較佳為50 kPa·s以上。 又，150℃下之黏晶層3之黏度更佳為500 kPa·s以下，進而較佳為400 kPa·s以下。
150℃下之黏晶層3之黏度可使用流變儀(Thermo Fisher Scientific製造、旋轉式流變儀、HAAKE MARS)來進行評價。具體而言，可藉由於樣品尺寸8 mm
Figure 02_image001
、Gap250 μm、應變0.1%、及升溫速度10℃/min之條件下自30℃升溫至180℃時，讀取150℃之指示值而得到。
於本實施方式之切晶黏晶膜20中，黏晶層3之厚度較佳為5 μm以上，更佳為10 μm以上，進而較佳為20 μm以上。又，黏晶層3之厚度較佳為150 μm以下，更佳為100 μm以下，進而較佳為80 μm以下。 藉由使黏晶層3之厚度為150 μm以下，能夠進一步提高導熱性。 黏晶層3之厚度例如可藉由如下方式求出：使用度盤規(PEACOCK公司製造、型號R-205)測定隨機選擇出之任意5處之厚度，並將所測得之5處之厚度進行算術平均。
黏晶層3根據需要亦可含有1種或2種以上之其他成分。作為其他成分，例如可例舉：填料分散劑、阻燃劑、矽烷偶合劑及離子捕捉劑。
基材層1支持黏著劑層2及積層於黏著劑層2上之黏晶層3。基材層1包含樹脂。作為樹脂，可例舉：聚乙烯(PE)、聚丙烯(PP)、乙烯-丙烯共聚物等烯烴系樹脂；乙烯-乙酸乙烯酯共聚物(EVA)、離子聚合物樹脂、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯(無規、交替)共聚物等以乙烯作為單體成分之共聚物；聚對苯二甲酸乙二酯(PET)、聚萘二甲酸乙二酯(PEN)、聚對苯二甲酸丁二酯(PBT)等聚酯；丙烯酸樹脂；聚氯乙烯(PVC)；胺基甲酸酯；聚碳酸酯；聚苯硫醚(PPS)；聚醯胺、全芳香族聚醯胺(聚芳醯胺)等醯胺系樹脂；聚醚醚酮(PEEK)；聚醯亞胺；聚醚醯亞胺；聚偏二氯乙烯；ABS(丙烯腈-丁二烯-苯乙烯共聚物)；纖維素系樹脂；聚矽氧樹脂；氟樹脂等。 其中，較佳為包含聚乙烯。
基材層1可包含1種上述樹脂，亦可包含2種以上之上述樹脂。
作為基材層1之材料，可例舉上述樹脂之交聯物等聚合物(例如塑膠膜)。上述塑膠膜可以無延伸之狀態使用，亦可使用根據需要實施了單軸或雙軸延伸處理者。根據藉由延伸處理等而賦予了熱收縮性之樹脂片，藉由於切晶後使其基材層1熱收縮，可降低黏著劑層2與黏晶層3之接著面積，而謀求半導體晶片(半導體元件)之回收容易化。
對於基材層1之表面，亦可實施通常之表面處理，以提高與鄰接之層之密接性、保持性等。作為此種表面處理，可例舉：鉻酸處理、臭氧暴露、火焰暴露、高壓電擊暴露、電離放射線處理等化學或物理處理，利用底塗劑進行之塗覆處理等。
基材層1之厚度較佳為1 μm以上且1000 μm以下，更佳為10 μm以上且500 μm以下，進而較佳為20 μm以上且300 μm以下，尤佳為30 μm以上且200 μm以下。 基材層1之厚度與上述黏晶層3之厚度同樣地，可使用度盤規(PEACOCK公司製造、型號R-205)求出。
基材層1亦可包含各種添加劑。作為各種添加劑，例如可例舉：著色劑、填充劑、塑化劑、防老化劑、抗氧化劑、界面活性劑、阻燃劑等。
用於形成黏著劑層2之黏著劑並無特別限定，例如可使用丙烯酸系黏著劑、橡膠系黏著劑等通常之感壓性黏著劑。作為上述感壓性黏著劑，就半導體晶圓、玻璃等怕被污染之電子零件之利用超純水、醇等有機溶劑進行清洗之洗淨性等方面而言，較佳為以丙烯酸系聚合物作為基礎聚合物之丙烯酸系黏著劑。
作為上述丙烯酸系聚合物，例如可例舉使用(甲基)丙烯酸烷基酯及(甲基)丙烯酸環烷基酯中之1種或2種以上作為單體成分的丙烯酸系聚合物等。作為(甲基)丙烯酸烷基酯，例如可使用甲酯、乙酯、丙酯、異丙酯、丁酯、異丁酯、第二丁酯、第三丁酯、戊酯、異戊酯、己酯、庚酯、辛酯、2-乙基己酯、異辛酯、壬酯、癸酯、異癸酯、十一烷基酯、十二烷基酯、十三烷基酯、十四烷基酯、十六烷基酯、十八烷基酯、二十烷基酯等烷基之碳數為1～30、尤其是碳數為4～18之直鏈狀或支鏈狀之烷基酯等。作為(甲基)丙烯酸環烷基酯，例如可使用環戊酯、環己酯等。 再者，(甲基)丙烯酸酯意指丙烯酸酯及甲基丙烯酸酯中之至少一者，本發明之(甲基)全部表示與上述內容同樣之內容。
上述丙烯酸系聚合物根據需要亦可包含對應於可與上述(甲基)丙烯酸烷基酯或(甲基)丙烯酸環烷基酯共聚之其他單體成分的單元，以改善凝集力、耐熱性等。作為此種單體成分，例如可例舉：丙烯酸、甲基丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、伊康酸、馬來酸、富馬酸、巴豆酸等含羧基單體；馬來酸酐、伊康酸酐等酸酐單體；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯、(甲基)丙烯酸(4-羥甲基環己基)甲酯等含羥基單體；苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯氧基萘磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯醯氧基萘磺酸等含磺酸基單體；2-羥乙基丙烯醯基磷酸酯等含磷酸基單體；丙烯醯胺、丙烯腈等。該等可共聚之單體成分可使用1種或2種以上。該等可共聚之單體之用量較佳為全部單體成分之40質量%以下。
進而，上述丙烯酸系聚合物根據需要還可包含多官能性單體等作為共聚用單體成分以進行交聯。作為此種多官能性單體，例如可例舉：己二醇二(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、胺基甲酸酯(甲基)丙烯酸酯等。該等多官能性單體亦可使用1種或2種以上。就黏著特性等方面而言，多官能性單體之用量較佳為全部單體成分之30質量%以下。
上述丙烯酸系聚合物可藉由使單一單體或2種以上之單體混合物聚合而得到。聚合可藉由溶液聚合、乳化聚合、塊狀聚合、懸浮聚合等中之任一種方法進行。就防止污染潔淨之被黏著體等方面而言，較佳為低分子量物質之含量較少。就此方面而言，丙烯酸系聚合物之數量平均分子量較佳為30萬以上，更佳為40萬～300萬左右。
又，於上述黏著劑中可適當添加外部交聯劑，以提高作為基礎聚合物之丙烯酸系聚合物等之數量平均分子量。作為外部交聯方法之具體方法，可例舉添加多異氰酸酯化合物、環氧化合物、氮丙啶化合物、三聚氰胺系交聯劑等交聯劑來進行反應之方法。於使用外部交聯劑之情形時，其用量係考慮與要交聯之基礎聚合物之平衡及作為黏著劑之使用用途來適當決定。一般而言，相對於上述基礎聚合物100質量份，外部交聯劑較佳為調配約5質量份以下，更佳為調配0.1～5質量份。
黏著劑除了上述成分以外，根據需要還可包含各種公知之黏著賦予劑、防老化劑等添加劑。
黏著劑層2可藉由放射線硬化型黏著劑而形成。放射線硬化型黏著劑藉由照射紫外線等放射線會增大交聯度，而易使其黏著力降低。即，藉由利用放射線硬化型黏著劑形成黏著劑層2，而於切晶前可不對黏著劑層2照射放射線而預先使黏晶層3充分接著於黏著劑層2，於切晶後，對黏著劑層2照射放射線而使黏著劑層2之黏著力降低，藉此可容易地拾取(回收)半導體晶片(半導體元件)。
放射線硬化型黏著劑只要具有碳-碳雙鍵等放射線硬化性之官能基且顯示出黏著性，便可無特別限制地使用。作為放射線硬化型黏著劑，例如可例舉：於丙烯酸系黏著劑、橡膠系黏著劑等通常之感壓性黏著劑中調配放射線硬化性之單體成分、低聚物成分而成之添加型放射線硬化型黏著劑。
作為上述放射線硬化性之單體成分，例如可例舉：胺基甲酸酯(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇單羥基五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯等。又，作為上述放射線硬化性之低聚物成分，可例舉：胺基甲酸酯系、聚醚系、聚酯系、聚碳酸酯系、聚丁二烯系等各種低聚物，其分子量適宜為100～30000左右之範圍。上述放射線硬化性之單體成分、上述放射線硬化性之低聚物成分之調配量較佳為採用於照射放射線後能夠適宜地降低黏著劑層2之黏著力之量。通常，相對於構成黏著劑之丙烯酸系聚合物等基礎聚合物100質量份，上述放射線硬化性之單體成分、上述放射線硬化性之低聚物成分之調配量例如較佳為5～500質量份，更佳為40～150質量份。
此外，作為放射線硬化型黏著劑，除上述添加型之放射線硬化型黏著劑以外，還可例舉內在型之放射線硬化型黏著劑，其使用於聚合物側鏈或者主鏈中或主鏈末端具有碳-碳雙鍵者。上述內在型之放射線硬化型黏著劑無需含有作為低分子成分之低聚物成分等，或者上述低聚物成分等之含量相對較少。因此，於使用上述內在型之放射線硬化型黏著劑之情形時，可抑制上述低聚物成分等隨時間經過於黏著劑層2中移動。結果，能夠使黏著劑層2具有相對穩定之層結構。
上述具有碳-碳雙鍵之基礎聚合物只要具有碳-碳雙鍵且具有黏著性，則可無特別限制地使用。作為此種基礎聚合物，較佳為以丙烯酸系聚合物作為基本骨架之聚合物。作為丙烯酸系聚合物之基本骨架，可例舉上述丙烯酸系聚合物。
向上述丙烯酸系聚合物導入碳-碳雙鍵之方法並無特別限制，可採用各種方法，但若採用將碳-碳雙鍵導入至聚合物側鏈之方法，則易於進行分子設計。例如，可例舉如下方法：預先使丙烯酸系聚合物與具有官能基之單體進行共聚後，使具有可與該官能基反應之官能基及碳-碳雙鍵之化合物於維持了碳-碳雙鍵之放射線硬化性的狀態下，進行縮合反應或加成反應。
作為該等官能基之組合例，可例舉：羧酸基與環氧基、羧酸基與氮丙啶基、羥基與異氰酸基等。該等官能基之組合中，就追蹤反應之容易性之方面而言，適宜為羥基與異氰酸基之組合。又，該等官能基之組合只要為生成上述具有碳-碳雙鍵之丙烯酸系聚合物之組合，則所有官能基均可位於丙烯酸系聚合物側或上述具有碳-碳雙鍵之化合物側，但於上述較佳組合之情形時，適宜的是丙烯酸系聚合物具有羥基，上述具有碳-碳雙鍵之化合物具有異氰酸基。於該情形時，作為具有碳-碳雙鍵之異氰酸酯化合物，例如可例舉：異氰酸甲基丙烯醯基酯、異氰酸2-甲基丙烯醯氧基乙酯、異氰酸間異丙烯基-α,α-二甲基苄酯等。又，作為丙烯酸系聚合物，可使用使上述含羥基單體、2-羥乙基乙烯基醚、4-羥丁基乙烯基醚、二乙二醇單乙烯基醚之醚系化合物等共聚所得者。
上述內在型之放射線硬化型黏著劑可單獨使用上述具有碳-碳雙鍵之基礎聚合物(尤其是丙烯酸系聚合物)，亦可以不會使特性變差之程度調配上述放射線硬化性之單體成分、或上述放射線硬化性之低聚物成分。上述放射線硬化性之低聚物成分等相對於基礎聚合物100質量份，通常以30質量份以下之範圍包含，較佳為以1～10質量份之範圍包含。
於上述放射線硬化型黏著劑中，當藉由紫外線等進行硬化時含有光聚合起始劑。作為光聚合起始劑，例如可例舉：4-(2-羥基乙氧基)苯基(2-羥基-2-丙基)酮、α-羥基-α,α'-二甲基苯乙酮、2-甲基-羥基苯丙酮、1-羥基環己基苯基酮等α-酮醇系化合物；甲氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基苯乙酮、2-甲基-1-[4-(甲硫基)-苯基]-2-嗎啉基丙烷-1等苯乙酮系化合物；安息香乙醚、安息香異丙醚、大茴香偶姻甲醚(anisoin methyl ether)等安息香醚系化合物；苯偶醯二甲基縮酮等縮酮系化合物；2-萘磺醯氯等芳香族磺醯氯系化合物；1-苯酮-1,1-丙二酮-2-(鄰乙氧基羰基)肟等光活性肟系化合物；二苯甲酮、苯甲醯苯甲酸、3,3'-二甲基-4-甲氧基二苯甲酮等二苯甲酮系化合物；噻噸酮、2-氯噻噸酮、2-甲基噻噸酮、2,4-二甲基噻噸酮、異丙基噻噸酮、2,4-二氯噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮等噻噸酮系化合物；樟腦醌；鹵化酮；醯基氧化膦；醯基膦酸酯等。相對於構成黏著劑之丙烯酸系聚合物等基礎聚合物100質量份，光聚合起始劑之調配量例如為0.05～20質量份。
又，作為放射線硬化型黏著劑，例如可例舉日本專利特開昭60-196956號公報中所揭示之含有光聚合性化合物及光聚合起始劑之橡膠系黏著劑、丙烯酸系黏著劑等，上述光聚合性化合物係具有2個以上不飽和鍵之加成聚合性化合物、具有環氧基之烷氧基矽烷等，上述光聚合起始劑係羰基化合物、有機硫化合物、過氧化物、胺、鎓鹽系化合物等。
於照射放射線時因氧導致產生硬化阻礙之情形時，較為理想的是對於放射線硬化型之黏著劑層2之表面，利用某種方法來阻斷氧(空氣)。例如可例舉：用隔離膜被覆上述黏著劑層2之表面之方法；於氮氣氣氛中照射紫外線等放射線之方法等。
黏著劑層2之厚度並無特別限定，就兼顧防止晶片切斷面之缺損與黏晶層3之固定保持性之方面而言，較佳為1～50 μm，更佳為2～30 μm，進而較佳為5～25 μm。
本說明書所揭示之內容包括以下。
(1) 一種切晶黏晶膜，其具備： 於基材層上積層黏著劑層而成之切晶帶、及 積層於該切晶帶之黏著劑層上之黏晶層， 上述黏晶層包含基質樹脂、含硫醇基化合物、及導電性粒子。
根據該構成，能夠提高上述黏晶層與帶金屬層之半導體晶圓之密接性。
(2) 如上述(1)所記載之切晶黏晶膜，其中 上述含硫醇基化合物為具有2個以上硫醇基之多官能硫醇化合物。
根據該構成，能夠更進一步提高上述黏晶層與帶金屬層之半導體晶圓之密接性。
(3) 如上述(1)或(2)所記載之切晶黏晶膜，其中 上述黏晶層包含0.1質量%以上且30質量%以下之上述含硫醇基化合物。
根據該構成，能夠更進一步提高上述黏晶層與帶金屬層之半導體晶圓之密接性。
(4) 如上述(1)至(3)中任一項所記載之切晶黏晶膜，其中 上述黏晶層於安裝在一面具備金屬層之矽晶圓之上述金屬層之狀態下，室溫下對於上述金屬層之剝離力為0.5 N/10 mm以上。 (5) 如上述(1)至(4)中任一項所記載之切晶黏晶膜，其中 上述黏晶層於安裝在一面具備金屬層之矽晶圓之上述金屬層之狀態下，室溫下對於上述金屬層之剝離力為0.7 N/10 mm以上。 (6) 如上述(4)或(5)所記載之切晶黏晶膜，其中 上述黏晶層於安裝在一面具備金屬層之矽晶圓之上述金屬層之狀態下，室溫下對於上述金屬層之剝離力為15 N/10 mm以下。
根據該構成，能夠更進一步提高上述黏晶層與帶金屬層之半導體晶圓之密接性。
(7) 如上述(1)至(6)中任一項所記載之切晶黏晶膜，其中 上述黏晶層中之上述導電性粒子之粒子填充率P為70質量%以上且95質量%以下， 150℃下之上述黏晶層之黏度為30 kPa·s以上。 (8) 如上述(1)至(6)中任一項所記載之切晶黏晶膜，其中 上述黏晶層中之上述導電性粒子之粒子填充率P為70質量%以上且95質量%以下， 150℃下之上述黏晶層之黏度為40 kPa·s以上。 (9) 如上述(1)至(6)中任一項所記載之切晶黏晶膜，其中 上述黏晶層中之上述導電性粒子之粒子填充率P為70質量%以上且95質量%以下， 150℃下之上述黏晶層之黏度為50 kPa·s以上。 (10) 如上述(7)至(9)中任一項所記載之切晶黏晶膜，其中 上述黏晶層中之上述導電性粒子之粒子填充率P為70質量%以上且95質量%以下， 150℃下之上述黏晶層之黏度為500 kPa·s以下。 (11) 如上述(7)至(9)中任一項所記載之切晶黏晶膜，其中 上述黏晶層中之上述導電性粒子之粒子填充率P為70質量%以上且95質量%以下， 150℃下之上述黏晶層之黏度為400 kPa·s以下。
根據該構成，能夠更進一步提高上述黏晶層與帶金屬層之半導體晶圓之密接性。
再者，本發明之切晶黏晶膜並不限定於上述實施方式。又，本發明之切晶黏晶膜並不受上述作用效果限定。本發明之切晶黏晶膜可於不脫離本發明之要旨之範圍內進行各種變更。 實施例
繼而，例舉實施例對本發明進一步具體地進行說明。以下之實施例係用於進一步詳細地說明本發明者，並不限定本發明之範圍。
[實施例1] 使用混合攪拌機(基恩士股份有限公司製造、商品名：HM-500)，按以下表1之實施例1一項所示之質量比例將包含各材料之混合物以「攪拌模式」加以攪拌混合，而製備清漆。 利用上述混合攪拌機進行之攪拌混合係分2個階段進行。具體而言，藉由如下方式來進行：首先，對包含熱硬化性樹脂(酚樹脂、固體環氧樹脂及液體環氧樹脂)、導電性粒子(銀被覆銅粒子及銀粒子)及含硫醇基化合物之一次調配物進行3分鐘攪拌混合(一次攪拌)，繼而向上述一次調配物中加入熱塑性樹脂(丙烯酸樹脂溶液)、觸媒及溶劑(甲基乙基酮(MEK))，進而攪拌混合6分鐘(二次攪拌)。 將該清漆塗佈於離型處理膜(三菱化學股份有限公司製造、商品名：MRA50、厚度50 μm)之一面後，於溫度100℃下乾燥2分鐘，得到厚度30 μm之黏晶層。 再者，作為以下表1所示之各材料，使用以下材料。 ·酚樹脂 明和化成公司製造之MEHC-7851S(聯苯型酚樹脂、苯酚當量209 g/eq) ·固體環氧樹脂 新日鐵住金化學公司製造之KI-3000-4(甲酚酚醛清漆型多官能環氧樹脂、環氧當量200 g/eq) ·液體環氧樹脂 DIC公司製造之EXA-4816(脂肪族改性雙酚A型環氧樹脂(2官能型)、環氧當量403 g/eq) ·銀(Ag)被覆銅(Cu)粒子 於三井金屬礦業公司製造之1200YP上塗覆有10質量%之銀粒子者(經環氧系被覆材料表面處理者。粒子形狀為扁平狀。體積平均粒徑D 50為3.5 μm。長徑比為10) ·銀(Ag)粒子 三井金屬礦業公司製造之SPH02J(凝集奈米Ag粒子、不規則形狀、凝集體之體積平均粒徑D 50為1.8 μm) ·含硫醇基化合物 SC有機化學公司製造之PEMP(4官能硫醇化合物) ·丙烯酸樹脂溶液 長瀨化成公司製造之Teisan Resin SG-70L(含有MEK及甲苯作為溶劑、固形物成分12.5%、玻璃轉移溫度-13℃、質量平均分子量90萬、酸值5 mg/KOH、含羧基之丙烯酸系共聚物) ·觸媒 北興化學工業公司製造之TPP-MK(四苯基鏻四(4-甲基苯基)硼酸鹽) ·溶劑 甲基乙基酮(MEK)
[實施例2] 含硫醇基化合物採用SC有機化學公司製造之PEPT(3官能硫醇化合物)，除此之外與實施例1同樣進行，得到實施例2之黏晶層。 關於用於形成實施例2之黏晶層之清漆中所包含之各材料之質量比例，示於以下表1。
[實施例3] 含硫醇基化合物採用SC有機化學公司製造之EGMP-4(2官能硫醇化合物)，除此之外與實施例1同樣進行，得到實施例3之黏晶層。 關於用於形成實施例3之黏晶層之清漆中所包含之各材料之質量比例，示於以下表1。
[實施例4] 含硫醇基化合物採用SC有機化學公司製造之DPMP(6官能硫醇化合物)，除此之外與實施例1同樣進行，得到實施例4之黏晶層。 關於用於形成實施例4之黏晶層之清漆中所包含之各材料之質量比例，示於以下表1。
[實施例5] 含硫醇基化合物採用SC有機化學公司製造之TMMP(3官能硫醇化合物)，向一次調配物中加入作為溶劑之甲基異丁基酮(MIBK)，加入信越化學工業公司製造之KBE-846(雙(三乙氧基矽烷基丙基))四硫化物)作為偶合劑並進行二次攪拌，使清漆中所包含之各材料之質量比例如下述表1所示，除此之外與實施例1同樣進行，得到實施例5之黏晶層。
[實施例6] 含硫醇基化合物採用SC有機化學公司製造之TMMP(3官能硫醇化合物)，向一次調配物中加入作為溶劑之甲基異丁基酮(MIBK)，加入信越化學工業公司製造之KBE-846(雙(三乙氧基矽烷基丙基))四硫化物)作為偶合劑並進行二次攪拌，使清漆中所包含之各材料之質量比例如下述表1所示，除此之外與實施例1同樣進行，得到實施例6之黏晶層。
[比較例1] 含硫醇基化合物採用SC有機化學公司製造之TMMP(3官能硫醇化合物)，向一次調配物中加入作為溶劑之甲基異丁基酮(MIBK)，加入信越化學工業公司製造之KBE-846(雙(三乙氧基矽烷基丙基))四硫化物)作為偶合劑並進行二次攪拌，使清漆中所包含之各材料之質量比例如下述表1所示，除此之外與實施例1同樣進行，得到比較例1之黏晶層。
[比較例2] 不加入含硫醇基化合物，向一次調配物中加入作為溶劑之甲基異丁基酮(MIBK)，加入信越化學工業公司製造之KBE-846(雙(三乙氧基矽烷基丙基))四硫化物)作為偶合劑並進行二次攪拌，使清漆中所包含之各材料之質量比例如下述表1所示，除此之外與實施例1同樣進行，得到比較例2之黏晶層。
[表1]
   單位 實施例1 實施例2 實施例3 實施例4
酚樹脂 質量份 3.51 3.51 3.51 3.51
固體環氧樹脂 質量份 2.83 2.83 2.83 2.83
液體環氧樹脂 質量份 1.21 1.21 1.21 1.21
Ag被覆Cu粒子 質量份 35.69 35.69 35.69 35.69
Ag粒子 質量份 11.27 11.27 11.27 11.27
含硫醇基化合物 質量份 0.59 0.59 0.59 0.59
MIBK 質量份 - - - -
丙烯酸樹脂溶液 質量份 25.90 25.90 25.90 25.90
偶合劑 質量份 - - - -
觸媒 質量份 0.01 0.01 0.01 0.01
MEK 質量份 18.99 18.99 18.99 18.99
總質量份 100.00 100.00 100.00 100.00
   單位 實施例5 實施例6 比較例1 比較例2
酚樹脂 質量份 3.44 3.38 3.29 3.60
固體環氧樹脂 質量份 2.77 2.70 2.65 2.91
液體環氧樹脂 質量份 1.18 1.16 1.13 1.24
Ag被覆Cu粒子 質量份 34.90 34.26 33.35 35.48
Ag粒子 質量份 11.03 10.82 10.54 11.20
含硫醇基化合物 質量份 0.46 0.99 2.94 -
MIBK 質量份 1.69 1.66 1.61 1.77
丙烯酸樹脂溶液 質量份 25.33 24.86 24.21 26.62
偶合劑 質量份 0.28 0.27 0.26 0.29
觸媒 質量份 0.01 0.01 0.01 0.01
MEK 質量份 18.91 19.89 20.01 16.86
總質量份 100.00 100.00 100.00 100.00
＜黏晶層於150℃下之黏度＞ 各例之黏晶層於150℃下之黏度係使用流變儀(Thermo Fisher Scientific公司製造、旋轉式流變儀、HAAKE MARS)進行評價。具體而言，藉由如下方式來進行：以10℃/min之升溫速度自30℃升溫至180℃時，讀取150℃之指示值。 對於各例之黏晶層，求出150℃下之黏度，將所得之結果示於以下表2。
＜黏晶層之形狀維持性(片成膜性)之評價＞ 對黏晶層之形狀維持性進行評價。 具體而言，使用敷料器將各例之清漆塗佈於離型處理膜之一面時，以目視觀察是否成膜為片狀，藉此進行評價。 並且，將充分成膜為片狀者(將塗佈有清漆之離型處理膜傾斜時，成功維持片狀態者)評價為“良好”，將未能成膜為片狀者(將塗佈有清漆之離型膜傾斜時，未能維持片狀態者)評價為“不良”。 對於各例之黏晶層，評價黏晶層之形狀維持性，將所得之結果示於以下表2。
＜室溫下對於金屬層之剝離力＞ 對於各例之黏晶層，測定室溫(23±2℃)下對於一面具備金屬層之矽晶圓(帶金屬層之裸晶圓。金屬層係藉由鍍銀而形成)之剝離力。 室溫下對於帶金屬層之裸晶圓之剝離力係使用延伸試驗機(商品名：Autograph AG-X、島津製作所製造)，藉由於室溫、剝離角度180°及延伸速度300 mm/min下之剝離試驗來測定。 具體而言，以如下方式進行測定。 (1)於帶金屬層之裸晶圓之具備上述金屬層之面重疊黏晶層，得到積層體。 (2)將該積層體配置於加熱至70℃之加熱板上。再者，上述積層體係以上述帶金屬層之裸晶圓之不具備金屬層之面與加熱板之表面抵接的方式進行配置。 (3)使用壓接輥(輥質量2 kg)對上述積層體進行加壓，藉此形成上述帶金屬層之裸晶圓與上述黏晶層貼合之狀態，並於加熱板上放置2分鐘。 (4)將經過放置之上述積層體自加熱板取出，於室溫(23±2℃)下放置20分鐘，藉此得到試驗體。 (5)對於上述試驗體，使用上述延伸試驗機，於上述條件下進行剝離試驗，藉此測定室溫下對於上述金屬層之剝離力。 對於各例之黏晶層，測定對於帶金屬層之裸晶圓之剝離力，將所得之結果示於以下表2。
＜切晶中之剝離性＞ 切晶中之剝離性之評價係使用於切晶帶之黏著劑層上積層黏晶層而成之切晶黏晶膜、及帶金屬層之裸晶圓(金屬層藉由鍍銀而形成)來進行。 詳細而言，按照以下順序來進行。 (1)使用按壓機構(壓接輥)，將厚度100 μm、直徑8英吋(200 mm)之帶金屬層之裸晶圓邊進行按壓邊貼附於上述黏晶層上。再者，帶金屬層之裸晶圓係一邊以金屬層與上述黏晶層抵接之方式按壓一邊進行貼附。 (2)使用全自動切晶機(DISCO CORPORATION製造、FULLY AUTOMATIC DICING SAW、DFD6361)，於主軸轉速：45000 rpm(min -1)、進給速度：30 mm/s、間距：5 mm之條件下，對上述黏晶層及上述帶金屬層之裸晶圓進行刀片切割，得到積層有帶金屬層之裸晶片之複數個黏晶層。此時，未觀察到實用上構成問題之程度之帶金屬層之裸晶片自黏晶層的剝離之情形時，將切晶中之剝離性記為“良好”，只要有一個帶金屬層之裸晶片發生了實用上構成問題之程度之剝離(產生晶片飛散)，則將切晶中之剝離性記為“不良”。
再者，上述黏著劑層、切晶帶及切晶黏晶膜係以如下方式製作。
(黏著劑層之製作) 丙烯酸系聚合物之合成向具備冷卻管、氮氣導入管、溫度計及攪拌裝置之反應容器內加入下述原料，使得單體濃度約為55質量%，於氮氣氣流下以60℃進行10小時聚合反應。藉此，合成丙烯酸系聚合物中間物。 ·丙烯酸2-乙基己酯(2HEA)：100質量份 ·丙烯酸2-羥乙酯(HEA)：20質量份 ·聚合起始劑：適量 ·聚合溶劑：甲苯 於二月桂酸二丁基錫(0.1質量份)之存在下，使所合成之丙烯酸系聚合物中間物100質量份、及異氰酸2-甲基丙烯醯氧基乙酯(MOI)1.4質量份於空氣氣流中以50℃進行60小時加成反應，合成丙烯酸系聚合物。 黏著劑層之製作(1)得到包含下述原料之溶液，向該溶液中適當加入甲苯，藉此製備黏度為500 mPa·s之黏著劑溶液。 ·所合成之丙烯酸系聚合物：100質量份 ·多異氰酸酯化合物 (Nippon Polyurethane Industry公司製造、商品名「CORONATE L」)：1.1質量份 ·光聚合起始劑 (Ciba Specialty Chemicals公司製造、商品名「IRGACURE 184」)：3質量份 (2)準備PET系膜作為剝離片。使用敷料器，於該剝離片之單面塗佈以上述方式製備之黏著劑溶液。再者，對剝離片(PET系膜)之上述單面實施作為離型處理之聚矽氧處理。塗佈後，藉由於120℃下加熱2分鐘來實施乾燥處理，於上述剝離片上製作厚度30 μm之黏著劑層。
(切晶帶及切晶黏晶膜之製作) 切晶帶之製作使用層壓機，於室溫下，將包含厚度80 μm之聚乙烯膜之支持基材貼合於剝離片上所製作之黏著劑層之露出面，而製作切晶帶。 再者，對切晶帶之黏著劑層中之直徑8英吋之帶金屬層之裸晶圓的貼附預定部分，以強度300 mJ/cm 2照射紫外線，而使上述貼附預定部分紫外線硬化。 切晶黏晶膜之製作於紫外線硬化後之上述切晶帶之黏著劑層上配置黏晶層，使之和與剝離片之積層側相反側之面抵接，以0.8 mm/min之速度通過層壓機，而將上述黏晶層貼合於上述切晶帶後，去除上述剝離片，藉此製作於上述切晶帶上積層上述黏晶層而成之切晶黏晶膜。
對於各例之黏晶層，評價切晶中之剝離性，將結果示於以下表2。
[表2]
   實施例1 實施例2 實施例3 實施例4
導電性粒子之粒子填充率[wt%] 80.5 80.5 80.5 80.5
含硫醇基化合物種類 PEMP(4官能) PEPT(3官能) EGMP-4(2官能) DPMP(6官能)
含硫醇基化合物添加量[wt%] 1.0 1.0 1.0 1.0
黏晶層之形狀維持性 良好 良好 良好 良好
150℃下之黏度[kPa] 56 279 54 208
室溫下之剝離力[N/10mm] 8.9 7.5 6.0 7.5
切晶中之剝離性 良好 良好 良好 良好
   實施例5 實施例6 比較例1 比較例2
導電性粒子之粒子填充率[wt%] 80.5 80.5 80.5 80.0
含硫醇基化合物種類 TMMP(3官能) TMMP(3官能) TMMP(3官能) -
含硫醇基化合物添加量[wt%] 0.8 1.8 5.1 -
黏晶層之形狀維持性 良好 良好 良好 優秀
150℃下之黏度[kPa] 241 75 15 730
室溫下之剝離力[N/10 mm] 0.8 3.2 7.0 0.05
切晶中之剝離性 良好 良好 不良 不良
由表2可知，各實施例之黏晶層均切晶中之剝離性之評價為“良好”，相對於此，各比較例之黏晶層均切晶中之剝離性為“不良”。 由該結果可知，藉由使黏晶層包含基質樹脂、含硫醇基化合物、及導電性粒子，能夠抑制於安裝在帶金屬層之半導體晶片之狀態下之切晶中產生晶片飛散。 [關聯申請之相互參照]
本申請案主張日本專利特願2020-191769號及日本專利特願2021-142373號之優先權，且藉由引用而併入至本申請案說明書之記載中。
1:基材層 2:黏著劑層 3:黏晶層 10:切晶帶 20:切晶黏晶膜
圖1係表示本發明之一實施方式之切晶黏晶膜之構成的剖視圖。
1:基材層
2:黏著劑層
3:黏晶層
10:切晶帶
20:切晶黏晶膜

Claims (5)

  1. 一種切晶黏晶膜，其具備： 於基材層上積層黏著劑層而成之切晶帶、及 積層於該切晶帶之黏著劑層上之黏晶層， 上述黏晶層包含基質樹脂、含硫醇基化合物、及導電性粒子。
  2. 如請求項1之切晶黏晶膜，其中 上述含硫醇基化合物為具有2個以上硫醇基之多官能硫醇化合物。
  3. 如請求項1或2之切晶黏晶膜，其中 上述黏晶層包含0.1質量%以上且30質量%以下之上述含硫醇基化合物。
  4. 如請求項1或2之切晶黏晶膜，其中 上述黏晶層於安裝在一面具備金屬層之矽晶圓之上述金屬層之狀態下，室溫下對於上述金屬層之剝離力為0.5 N/10 mm以上。
  5. 如請求項1或2之切晶黏晶膜，其中 上述黏晶層中之上述導電性粒子之粒子填充率P為70質量%以上且95質量%以下， 150℃下之上述黏晶層之黏度為30 kPa·s以上。
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