TWI413671B - 黏著劑、黏著片、多層黏著片及電子構件之製法 - Google Patents

黏著劑、黏著片、多層黏著片及電子構件之製法 Download PDF

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TWI413671B
TWI413671B TW96139197A TW96139197A TWI413671B TW I413671 B TWI413671 B TW I413671B TW 96139197 A TW96139197 A TW 96139197A TW 96139197 A TW96139197 A TW 96139197A TW I413671 B TWI413671 B TW I413671B
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Taiwan
Prior art keywords
adhesive
wafer
acrylate
adhesive sheet
meth
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TW96139197A
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English (en)
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TW200918623A (en
Inventor
Takeshi Saito
Tomomichi Takatsu
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Denki Kagaku Kogyo Kk
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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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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
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    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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Description

黏著劑、黏著片、多層黏著片及電子構件之製法
本發明係有關於一種黏著劑、使用黏著劑之黏著片、使用黏著片之多層黏著片、及使用多層黏著片電子構件之製法。
IC等電子構件的製法，已知有將半導體晶圓或絕緣物基板作為母材來製造晶片，並將晶片拾起，且使用接著劑等固定於導線框架等，然後使用樹脂等密封而成為電子構件之方法。電子構件的製法有一種廣泛被使用的方法(參照非專利文獻1)，係在矽、鎵－砷等半導體晶圓或絕緣物基板上形成電路圖案作為電子構件集合體，並將該電子構件集合體貼於在黏著片上，且固定於環框後切斷分離(dicing)成一個一個的晶片，然後按照必要拉伸薄膜(擴張)，並拾起晶片，且使用接著劑將晶片固定在導線框架之方法。
有提案揭示一種使用多層黏著片(晶粒黏貼膠膜整體型片)之方法，該多層黏著片兼具接著劑的功能，用以將切割用的黏著片與晶片固定在導線框架。晶粒黏貼膠膜整體型片係將黏著片與晶粒黏貼膠膜整體化而成之多層黏著片。藉由將晶粒黏貼膠膜整體型片使用於製造電子構件，能夠省略接著劑的塗布步驟。
晶粒黏貼膠膜整體型片與使用接著劑之方法比較時，具有能夠抑制在接著劑部分的厚度控制或抑制接著劑擠出之優點。晶粒黏貼膠膜整體型片能夠使用於晶片尺寸大小封裝、推疊封裝、及系統級封裝(System－In－Package)等半導體封裝的製造(參照專利文獻1~3)。
在切割電子構件集合體時所使用的黏著片的黏著劑，已知有一種方法(參照專利文獻4)，係使用在(甲基)丙烯酸與含羥基聚合性單體之共聚物，具有2個以上不飽和鍵之放射線聚合性化合物之方法。
丙烯酸黏著劑已知有含有具有重量平均分子量為20萬以上、Tg(玻璃轉移溫度)為－60℃~－30℃的各種官能基之丙烯酸化合物、及丙烯酸胺基甲酸酯寡聚物等之物(參照專利文獻5)。
[專利文獻1]特開平02－248064號公報[專利文獻2]特開平08－053655號公報[專利文獻3]特開2004－186429號公報[專利文獻4]特許第3410202號公報[專利文獻5]特開平11－293201號公報
[非專利文獻1]小澤他、“古河電工時報”、第106期、第31頁、古河電工股份公司、(2000年7月)
但是，隨著電子構件的高積體化，晶片尺寸大幅度地變薄，切割後的晶片之拾起作業變為困難的情況增加。而且，因為和黏著片與半導體晶圓間的親和性比較時，黏著片與晶粒黏貼膠膜間的親和性較高，即便照射電子射線/紫外線後亦無法謀求黏附力充分降低，會有在拾起時的剝離容易性差，而造成拾起不良的情形。
本發明係鑒於上述情形而進行，本發明的目的係提供一種黏著劑、使用黏著劑之黏著片、使用黏著片之多層黏著片、及使用多層黏著片電子構件之製法，該黏著劑拾起時黏著片與晶粒黏貼膠膜之間的剝離容易，如此，在切割後之晶片的拾起作業能夠容易地進行。
依照本發明，能夠提供一種黏著劑，其含有(甲基)丙烯酸酯聚合物、具有4個以上乙烯基之丙烯酸胺基甲酸酯寡聚物、及聚矽氧接枝聚合物。
使用該黏著劑時，因為在切割後進行拾起晶片時，在晶粒黏貼膠膜與黏著片的黏著劑層之剝離容易，所以能夠抑制晶片的拾起不良。而且在切割時之晶片保持性優良，同時因微少的殘糊對晶粒黏貼膠膜污染性低。因此該黏著劑能夠適合使用於晶粒黏貼膠膜整體型片的黏著劑層。
又，上述的黏著劑係本發明的一個態樣，使用本發明的黏著劑之黏著片、使用黏著片之多層黏著片、及使用多層黏著片電子構件之製法等，亦具有同樣的技術特徵，且能夠達成同樣的作用效果。
依照本發明，因為使用由特定組成所構成的黏著劑，所以拾起作業時晶片容易剝離，另一方面，在切割時之晶片保持性良好。而且，因為在切割後晶粒黏貼膠膜未受到污染，能夠抑制黏附有晶粒黏貼膠膜之晶片與導線框架產生黏著不良。
以下，使用圖示說明本發明的實施形態，又，在全部圖示，同樣的構成要素係附加同樣的符號而省略適當的說明。
<用語說明>
在本說明書，單體係指單體本身或是來自單體的結構。本說明書的份及%若未特別記載時係質量基準。在本說明書，(甲基)丙烯醯基係指丙烯醯基及甲基丙烯醯基之總稱。(甲基)丙烯酸等含有(甲基)之化合物等亦同樣地，係名稱中具有「甲基」之化合物與未具有「甲基」之化合物的總稱。丙烯酸胺基甲酸酯寡聚物的官能基數係指每1個丙烯酸胺基甲酸酯寡聚物分子之乙烯基數。
<實施形態的概要>
第1圖係說明本實施形態的多層黏著片的構成之剖面圖。
本實施形態的多層黏著片(晶粒黏貼膠膜整體型片)100係如第1圖(1)所示，具備：基材薄膜106；黏著劑層103，其係在該基材薄膜106塗布後述的黏著劑而構成；及晶粒黏貼膠膜105其係層積在該黏著劑層103上而構成。
在此，將上述基材薄膜106、及在該基材薄膜106塗布後述的黏著劑而構成之黏著劑層103合併稱為黏著片110。亦即，多層黏著片100係具備黏著片110、及層積該黏著片110的黏著劑層103側而構成之晶粒黏貼膠膜105。
而且，上述黏著劑層103係藉由在基材薄膜106塗布含有(甲基)丙烯酸酯聚合物、具有4個以上乙烯基之丙烯酸胺基甲酸酯寡聚物、及聚矽氧接枝聚合物之黏著劑而形成。
使用上述組成所構成的黏著劑之多層黏著片100在晶片108的拾起作業時晶粒黏貼膠膜105與黏著片110的黏著劑層103之剝離容易。又，因為如此的多層黏著片100之晶片保持性亦優，能夠抑制在切割時晶片108剝離掉(所謂「晶片飛散」)。
而且，使用該多層黏著片100之電子構件的製法，係在切割矽晶圓101後於在晶片108的背面黏附有晶粒黏貼膠膜105的狀態將晶片108拾起，且直接將晶片108黏貼並使其黏著於導線框架111等。此時，因微少的殘糊對晶粒黏貼膠膜105污染性低，所以能夠抑制產生黏著不良。
<黏著劑層>
黏著劑層103係由含有(甲基)丙烯酸酯聚合物、具有4個以上乙烯基之丙烯酸胺基甲酸酯寡聚物、及聚矽氧接枝聚合物之黏著劑所構成。由如此的黏著劑所構成的黏著劑層103，在晶片108的拾起作業時晶粒黏貼膠膜105容易與黏著劑層103剝離。又，在切割時之晶片保持性良好，且對晶粒黏貼膠膜105的污染性低。
(甲基)丙烯酸酯聚合物係聚合(甲基)丙烯酸酯單體而成的聚合物。又，(甲基)丙烯酸酯聚合物亦可含有(甲基)丙烯酸酯單體以外的乙烯基化合物單體。
(甲基)丙烯酸酯的單體可舉出例如(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)丙烯酸十三烷酯、(甲基)丙烯酸肉豆蔻酯、(甲基)丙烯酸十六烷酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸環己酯、異佛爾酮(甲基)丙烯酸、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸苄酯、(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、及(甲基)丙烯酸乙氧基正丙酯、(甲基)丙烯酸－2－羥基乙酯、(甲基)丙烯酸－2－羥基丙酯、及(甲基)丙烯酸－2－羥基丁酯等。
具有乙烯基化合物單體以使用具有選自由羥基、羧基、環氧基、醯胺基、胺基、羥甲基、磺酸基、胺基磺酸基、及(亞)磷酸酯基所組成官能基群組之1種以上之物為佳。
具有羥基之乙烯基化合物單體可舉出例如乙烯醇等。
具有羧基之單體可舉出例如(甲基)丙烯酸、巴豆酸、順丁烯二酸、順丁烯二酸酐、伊康酸、反丁烯二酸、丙烯醯胺－N－二醇酸、及桂皮酸等。
具有環氧基之單體可舉出例如烯丙基環氧丙基醚、及(甲基)丙烯酸環氧丙基醚等。
具有醯胺基之單體可舉出例如(甲基)丙烯醯胺等。
具有胺基之單體可舉出例如(甲基)丙烯酸－N,N－二甲胺基乙酯。
具有羥甲基之單體可舉出例如N－羥甲基丙烯醯胺等。
(甲基)丙烯酸酯聚合物的製法，能夠使用乳化聚合、及溶液聚合等。因為放射線照射後能夠使黏著片110與晶粒黏貼膠膜105容易剝離，以使用乳化聚合來製造丙烯酸橡膠為佳。
具有4個以上乙烯基之丙烯酸胺基甲酸酯寡聚物(以下亦簡稱「丙烯酸胺基甲酸酯寡聚物」)，若是具有4個以上乙烯基、且在分子內具有胺甲酸酯鍵之(甲基)丙烯酸酯寡聚物時沒有特別限定。
丙烯酸胺基甲酸酯寡聚物的製法沒有特別限定，可舉出例如使含有羥基及複數個(甲基)丙烯酸酯基之(甲基)丙烯酸酯化合物、與具有複數個異氰酸酯基之化合物(例如二異氰酸酯化合物)反應而成為丙烯酸胺基甲酸酯寡聚物之方法。又，亦藉由在具有複數個羥基末端之多元醇寡聚物，過量地添加具有複數個異氰酸酯基之化合物(例如二異氰酸酯化合物)而使其反應而成為具有複數個異氰酸酯末端之寡聚物，進而使其與含有羥基及複數個(甲基)丙烯酸酯基之(甲基)丙烯酸酯化合物反應而成為丙烯酸胺基甲酸酯寡聚物。
含有羥基及複數個(甲基)丙烯醯基之(甲基)丙烯酸酯化合物可舉出例如羥丙基化三羥甲基丙烷三丙烯酸酯、新戊四醇三丙烯酸酯、二新戊四醇-羥基-五丙烯酸酯、雙(新戊四醇)-四丙烯酸酯、四羥甲基甲烷-三丙烯酸酯、去水甘油-二丙烯酸酯、或使此等的丙烯酸酯基的一部分或全部成為甲基丙烯酸酯基之化合物等。
具有複數個異氰酸酯基之異氰酸酯可舉出例如芳香族異氰酸酯、脂環族異氰酸酯、及脂肪族異氰酸酯等。具有複數個異氰酸酯基之異氰酸酯之中，以使用芳香族異氰酸酯為佳。異氰酸酯成分的形態有單體、二聚物、三聚物，以使用三聚物為佳。
芳香族二異氰酸酯可舉出例如二異氰酸甲苯酯、4,4－二苯基甲烷二異氰酸甲苯酯、及二異氰酸苯二甲酯等。
脂環族二異氰酸酯可舉出例如異佛爾酮二異氰酸酯、亞甲基雙(4－環己基異氰酸酯)等。
脂肪族二異氰酸酯可舉出例如六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯等。
具有複數個羥基末端之多元醇寡聚物可舉出例如聚(環氧丙烷)二醇、聚(環氧丙烷)三醇、共聚合(環氧乙烷－環氧丙烷)二醇、聚(環氧丁烷)二醇、環氧化雙酚A、環氧化雙酚S螺乙二醇、己內酯改性二醇、及碳酸酯二醇等。
丙烯酸胺基甲酸酯寡聚物的乙烯基數少於4個時，在照射放射線後晶粒黏貼膠膜105與黏著劑層103不容易剝離，致使晶片108的拾起性有下降的情形。另一方面，雖然在丙烯酸胺基甲酸酯寡聚物之乙烯基數的上限沒有特別限定，但考慮容易取得性或製造成本等，較佳是15個左右為止。
雖然丙烯酸胺基甲酸酯寡聚物的調配量沒有特別限定，但相對於100質量份(甲基)丙烯酸酯聚合物，以20質量份以上200質量份以下為佳。具有4個以上乙烯基之丙烯酸胺基甲酸酯寡聚物的調配量小於20質量份時，在照射紫外線及/或放射線後，會有黏著片110與晶粒黏貼膠膜105無法容易地剝離，而產生晶片108的拾起性的問題。又，過量地調配量大於200質量份時，因在切割時產生糊電子構件側面往上攏而造成拾起性不良的情形，同時因反應殘渣產生微小的殘糊，會有因將附著有晶粒黏貼膠膜105的晶片108裝載於導線框架111時的加溫，產生黏著不良的情形。
聚矽氧接枝聚合物除了係聚合在聚矽氧分子鏈的末端具有乙烯基的單體(以下，稱為「聚矽氧大分子單體」)而成之物以外，沒有特別限定，可舉出例如聚矽氧大分子單體的同元聚合物、或聚矽氧大分子單體與其他的乙烯化合物之共聚物。聚矽氧大分子單體以使用聚矽氧分子鏈的末端係(甲基)丙烯醯基或苯乙烯基等的乙烯基之化合物為佳(參照專利文獻6)。
由於與調配在黏著劑之其他聚合物的相溶性高，前述其他的乙烯基化合物以(甲基)丙烯酸單體為佳。因為使用相溶性高之物時，黏著劑整體變為均勻的緣故。
(甲基)丙烯酸單體沒有特別限定，可舉出例如(甲基)丙烯酸烷酯、(甲基)丙烯酸羥基烷酯、改性羥基(甲基)丙烯酸酯、及(甲基)丙烯酸酯等，為了防止稱為微粒之微小的殘糊，以使用具有反應性之(甲基)丙烯酸羥基烷酯、或改性羥基(甲基)丙烯酸酯為佳。
(甲基)丙烯酸烷酯可舉出例如(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)丙烯酸羥基甲酯等。
(甲基)丙烯酸羥基烷酯可舉出例如(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、及(甲基)丙烯酸羥基丁酯等。
改性羥基(甲基)丙烯酸酯可舉出例如環氧乙烷改性羥基(甲基)丙烯酸酯、及己內酯改性羥基(甲基)丙烯酸酯等。
雖然聚矽氧接枝聚合物中的聚矽氧大分子單體單位的比率沒有特別限定，但在100質量份聚矽氧接枝聚合物中，聚矽氧大分子單體單位以15質量份以上50質量份以下為佳。聚矽氧大分子單體單位的含量小於15質量份時，會有在照射放射線後，黏著片110與晶粒黏貼膠膜105無法容易地剝離，致使晶片108的拾起性降低之情形。又，大於50質量份而過量時，會有滲出黏著劑層103的表面，而污染晶粒黏貼膠膜105，將黏附有晶粒黏貼膠膜105之晶片108裝載在導線框架111上時，在加溫時會有產生黏著不良的情形。
聚矽氧接枝聚合物的調配量沒有特別限定，相對於100質量份(甲基)丙烯酸酯，以0.1質量份以上10質量份以下為佳。聚矽氧接枝聚合物的調配量小於0.1質量份，在照射紫外線及/放射線後，黏著片110與晶粒黏貼膠膜105無法容易地剝離，致使晶片108的拾起性降低之情形。又，大於10質量份而過量地調配時，會有初期的黏附力降低，致使在切割時從環框102剝離的情形。
為了調整黏著強度，亦可在黏著劑添加黏著賦予樹脂。黏著賦予樹脂沒有特別限定，可舉出例如松香樹脂、松香酯樹脂、萜烯樹脂、萜烯苯酚樹脂、苯酚樹脂、二甲苯樹脂、香豆酮樹脂、香豆酮茚樹脂、苯乙烯樹脂、脂肪族石油樹脂、芳香族石油樹脂、脂肪族芳香族共聚合石油樹脂、脂環族烴樹脂、及此等的改性品、衍生物、及加氫品等。
黏著賦予樹脂的調配量沒有特別限定，相對於100質量份(甲基)丙烯酸酯聚合物為200質量份以下，以30質量份以下為佳。
亦可在黏著劑添加例如硬化劑、聚合引發劑、軟化劑、抗老化劑、填料、紫外線吸收劑、及光安定劑等各種添加劑。
黏著劑層103的厚度以1微米以上為佳，以2微米以上為特佳。又，黏著劑層103的厚度以100微米以下為佳，以40微米以下為特佳。黏著劑層103的厚度小於1微米時，黏附力下降，在切割時的晶片保持性下降，同時會有在環框102與多層黏著片100之間產生剝離的情形。又，黏著劑層103的厚度比100微米厚時，會有黏附力過高而產生拾起不良的情形。
<黏著片>
由基材薄膜106、及在該基材薄膜106上層積而構成的黏著劑層103所構成的黏著片110，係藉由在基材薄膜106上塗布黏著劑而製造。基材薄膜106的厚度以30微米以上為佳，以60微米以上為更佳。又，基材薄膜106的厚度以300微米以下為佳，以200微米以下為更佳。
基材薄膜106的原料沒有特別限定，可舉出例如聚氯乙烯、聚對酞酸乙二酯、乙烯－乙酸乙烯酯共聚物、乙烯－丙烯酸－丙烯酸酯薄膜、乙烯－丙烯酸乙酯共聚物、聚乙烯、聚丙烯、乙烯－丙烯酸共聚物、及將乙烯－(甲基)丙烯酸共聚物或乙烯－(甲基)丙烯酸－(甲基)丙烯酸酯共聚物等以金屬離子交聯而成的離子聚合物樹脂。基材薄膜106亦可使用此等樹脂的混合物、共聚物、及多層薄膜等。
基材薄膜106的原料以使用離子聚合物樹脂為佳。離子聚合物樹脂之中，因為抑制產生鬍鬚狀切削屑的效果顯著，以使用藉由Na＋ 、K＋ 、Zn2＋ 等金屬離子使具有乙烯單位、(甲基)丙烯酸單位、及(甲基)丙烯酸烷酯單位之共聚物進行交聯而成之離子聚合物樹脂為佳。
基材薄膜106的成型方法沒有特別限定，可舉出例如壓延、T模頭擠壓、吹塑、及鑄型等。
基材薄膜106為了防止在剝離晶粒黏貼膠膜105時帶靜電，亦可在基材薄膜106的晶粒黏貼膠膜105接觸面及/或非接觸面施加防靜電處理。防靜電劑亦可摻合在樹脂中。防靜電處理可使用四級胺鹽單體等防靜電劑。
四級胺鹽單體可舉出例如(甲基)丙烯酸二甲基胺基乙酯四級氯化物、(甲基)丙烯酸二乙基胺基乙酯四級氯化物、(甲基)丙烯酸甲基乙基胺基乙酯四級氯化物、對二甲基胺基苯乙烯四級氯化物、及對二乙基胺基苯乙烯四級氯化物等，以使用(甲基)丙烯酸二甲基胺基乙酯四級氯化物為佳。
滑劑及防靜電劑的使用方法沒有特別限定，例如可在基材薄膜106的一面塗布黏著劑，並在該背面塗布滑劑及/或防靜電劑，亦可在基材薄膜106的樹脂中摻合滑劑及/或防靜電劑並加以薄片化。
可以在基材薄膜106的一面側的黏著劑層103上層積晶粒黏貼膠膜105，並使另外的面為平均表面粗糙度(Ra)為0.3微米以上1.5微米以下的壓花面。藉由在擴張裝置(未圖示)的機械平台側設置壓花面，在切割後的擴張步驟能夠容易地將基材薄膜106擴張。
為了更提高切割後的擴張性，能夠在基材薄膜106之晶粒黏貼膠膜105非接觸面施加滑劑，或在基材薄膜106摻合滑劑。
滑劑若是能夠降低黏著片110與擴張裝置(未圖示)的摩擦係數之物質時沒有特別限定，可舉出例如聚矽氧樹脂、或(改性)矽油等聚矽氧化合物、氟樹脂、六方晶氮化硼、碳黑、及二硫化鉬等。此等滑劑亦可混合複數成分。因為電子構件的製造係在潔淨室進行，滑劑以使用聚矽氧化合物或氟樹脂為佳。因為與防靜電層的相溶性良好，且為了謀求防靜電性與擴張性的平衡，聚矽氧化合物之中以使用具有聚矽氧大分子單體單位之共聚物為特佳。
為了提升黏著片110與晶粒黏貼膠膜105之間的剝離性，基材薄膜106之晶粒黏貼膠膜105接觸面的算術平均Ra以0.5微米以上1.5微米以下為佳。
為了使黏著片110與晶粒黏貼膠膜105的剝離性變為 容易，亦可在基材薄膜106之晶粒黏貼膠膜105接觸面施加脫膜處理。該脫膜處理能夠使用醇酸樹脂、聚矽氧樹脂、氟樹脂、不飽和聚酯樹脂、蠟等脫模劑。
在基材薄膜106上形成黏著劑層103而作為黏著片110的方法沒有特別限定，可舉出例如凹版塗布器、刮刀式塗布器(comma coater)、棒塗布器、刮刀塗布器(knife coater)、或是輥塗布器等塗布器在基材薄膜106上直接塗布黏著劑之方法。亦可使用凸版印刷、凹版印刷、平版印刷、柔版印刷、膠版印刷、或網版印刷等在基材薄膜106上印刷黏著劑。
雖然黏著片110亦可使用於切割時或背面研磨時之電子構件固定用，但是較佳是積層晶粒黏貼膠膜105與黏著片110成為多層黏著片100，該多層黏著片100能夠使用於切割步驟之電子構件固定、及對導線框架111之固定步驟雙方。
<晶粒黏貼膠膜>
晶粒黏貼膠膜105係將黏著劑或接著劑成形為薄膜狀而成之物。晶粒黏貼膠膜105係以在由PET等樹脂等所構成的剝離用薄膜等層積接著劑或黏著劑而成的狀態銷售，能夠將接著劑或黏著劑轉印至被黏著物。
晶粒黏貼膠膜105的材質能夠使用通常所使用的黏著劑或接著劑。黏著劑可舉出例如環氧樹脂、聚醯胺、丙烯酸、及聚醯亞胺等。接著劑可舉出例如丙烯酸、乙酸乙酯、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸酯共聚物、聚醯胺、聚乙烯、聚碸、環氧樹脂、聚醯亞胺、聚醯胺酸、聚矽氧、苯酚、橡膠共聚物、氟共聚物、及氟樹脂等。以使用聚醯亞胺為佳。
又，晶粒黏貼膠膜105亦能夠使用該等黏著劑或接著劑的混合物、共聚物、及積層體等。晶粒黏貼膠膜105亦可按照必要添加光聚合引發劑、防靜電劑、交聯促進劑等的添加劑。
<電子構件的製法>
電子構件的製造以使用在黏著片110的黏著劑塗布面層積晶粒黏貼膠膜105而構成的多層黏著片100之方法為佳。使用本實施形態的多層黏著片100之電子構件的製法沒有特別限定，可舉出例如第1圖所示之下述順序。
(1)將矽晶圓101貼在多層黏著片100而固定，並將該多層黏著片100固定於環框102。
(2)使用切割刀片104切割矽晶圓101。
(3)從多層黏著片100的基材薄膜106側照紫外線及/或放射線(未圖示)，接著，將多層黏著片100放射狀地擴大，來擴展晶片108的間隔後，使用針等(未圖示)將晶片108往上推。然後藉由真空筒夾或空氣小鑷子等(未圖示)吸附晶片108，並在黏著片110與晶粒黏貼膠膜105之間進行剝離，且拾起黏附有晶粒黏貼膠膜105之晶片108。
(4)將黏附有晶粒黏貼膠膜105之晶片108搭載(安裝)在導線框架111或電路基板上。然後，加熱晶粒黏貼膠膜105，來將晶片108與導線框架111或電路基板加熱黏著。最後，使用樹脂(未圖示)將搭載在導線框架111或電路基板之晶片108模塑。
在該製法，亦可用形成有電路圖案之電路基板等來代替導線框架111。
紫外線及/或放射線的光源沒有特別限定，能夠使用眾所周知之物。紫外線源可舉出低壓水銀燈、高壓水銀燈、超高壓水銀燈、金屬鹵燈等。放射線以使用電子射線、α射線、β射線、γ射線為佳。
藉由照射紫外線及/或放射線，能夠使構成黏著劑層103之化合物分子內的乙烯基三維網狀化，來使黏著劑層103的黏附力降低。藉此，在照射紫外線/放射線之前，因為黏著劑層103具有初期的高黏附力，能夠顯示優良的晶片保持性，因為在照射紫外線及/或放射線，黏著劑層103的黏附力降低，晶粒黏貼膠膜105與黏著劑層103之剝離變為容易，能夠提高晶片108的拾起性。
上述實施形態係說明了在矽晶圓101與黏著片110之間存在有晶粒黏貼膠膜105之形態，但是亦可以使用糊狀接著劑來代替晶粒黏貼膠膜105。
使用糊狀接著劑時，典型地係在矽晶圓101的背面亦即在為了與導線框架111或電路基板黏著的電路非形成面，全面塗布糊狀接著劑，並加熱使其半硬化成薄片狀，來形成接著劑半硬化層。在此所形成的接著劑半硬化層具有與上述晶粒黏貼膠膜105同樣的功能。將形成有接著劑半硬化層之矽晶圓101、與由黏著劑層103及基材薄膜106所構成的黏著片110，以接著劑半硬化層與黏著劑層103接觸的方式貼合時，係成為與第1圖(1)同樣的構成。隨後，能夠與使用晶粒黏貼膠膜105時同樣地，使用切割刀片104進行切割，然後將黏附有接著劑半硬化層之晶片拾起，使其黏貼於導線框架111或電路基板並加熱黏著。
糊狀接著劑除了熱硬化性以外，沒有特別限定，可舉出例如丙烯酸、乙酸乙烯酯、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸酯共聚物、聚醯胺、聚乙烯、聚碸、環氧樹脂、聚醯亞胺、聚醯胺酸、聚矽氧、苯酚、橡膠聚合物、氟橡膠聚合物、及氟樹脂等之一種或複數種的混合物。
<作用效果>
以下，邊參照第1圖邊說明本實施形態的多層黏著片100的作用效果。
本實施形態的多層黏著片100係如第1圖(1)所示，具備基材薄膜106、在該基材薄膜106塗布後的黏著劑而構成的黏著劑層103、在該黏著劑層103層積而構成的晶粒黏貼膠膜105。
而且，上述的黏著劑層103係由含有(甲基)丙烯酸酯聚合物、具有4個以上乙烯基之丙烯酸胺基甲酸酯寡聚物、及聚矽氧接枝聚合物之黏著劑所構成。
使用如此的黏著劑時，因為照射紫外線及/或放射線後，黏著劑層103與晶粒黏貼膠膜105之剝離變為容易，所以能夠良好地進行如第1圖(3)所示之晶片108的拾起作業。又，使用如此的黏著劑時，因為照射紫外線及/或放射 線前的晶片保持性亦優良，所以在第1圖(2)所示的切割時，能夠抑制晶片108剝離掉(晶片飛散)。而且，使用如此的黏著劑時，因為微少的殘糊對晶粒黏貼膠膜105的污染低，所以如第1圖(4)所示，將黏附有晶粒黏貼膠膜105之晶片108黏貼在導線框架111上並加溫而黏著時，能夠抑制因污染所產生的黏著不良。
又，上述的黏著劑以含有100質量份(甲基)丙烯酸酯聚合物、20質量份以上200質量份以下具有4個以上乙烯基之丙烯酸胺基甲酸酯寡聚物、及0.1質量份以上10質量份以下聚矽氧接枝聚合物為佳。
這是因為在照射紫外線及/或放射線後，不只是黏著片110與晶粒黏貼膠膜105的剝離變為容易，且更佳是能夠抑制在切割時產生糊往上攏或因反應殘渣而產生微小的殘渣，同時在切割時能夠抑制多層黏著片100從環框102剝離。
又，上述的黏著劑之聚矽氧接枝聚合物以將(甲基)丙烯酸酯單體作為構成單體之一而聚合而成之為佳。
此時，因為能夠使黏著劑均質的緣故。
又，上述的黏著劑若採用(甲基)丙烯酸酯單體作為構成單體之一時，該(甲基)丙烯酸酯單體以具有羥基之物為佳。
這是因為能夠使黏著劑均質化，並且亦能夠藉由羥基至少與丙烯酸胺基甲酸酯寡聚物的反應殘渣之異氰酸酯基或異氰酸酯硬化劑之異氰酸酯基反應，能夠抑制聚矽氧接枝聚合物產生污染的緣故。
又，黏著片110以具備塗布上述黏著劑而構成的黏著劑層103為佳，該黏著片110以電子構件固定用為更佳。又，多層黏著片100以具備該黏著片110、及在該黏著片110的黏著劑層103側層積而構成的晶粒黏貼膠膜105為佳。
這是因為使用如此的黏著片110或多層黏著片100時，在照射紫外線及/或放射線後，與晶粒黏貼膠膜105的剝離變為容易，能夠使晶片108的拾起作業良好地進行之緣故。又，使用如此的黏著片110或多層黏著片100時，因為在照射紫外線及/或放射線的晶片保持性亦優良，在切割時，能夠抑制晶片108剝離掉。而且，因為對晶粒黏貼膠膜105之污染性低(黏著劑層103能夠降低污染晶粒黏貼膠膜105)，將黏附有晶粒黏貼膠膜105之晶片108黏貼在導線框架111上並加溫黏著時，能夠抑制因污染而產生之黏著不良。
又，以使用包含以下步驟之電子構件的製法為佳，包含：在上述多層黏著片100的晶粒黏貼膠膜105表面貼合矽晶圓101之步驟；在貼合於該多層黏著片100之狀態，對矽晶圓101進行切割之步驟；及在切割後，藉由剝離晶粒黏貼膠膜105與黏著劑層103，來將矽晶圓101與黏附於該矽晶圓101的背面之晶粒黏貼膠膜105一同拾起之步驟。
因為此時矽晶圓101在切割後，藉由從多層黏著片100的基材薄膜106側照射紫外線及/或放射線(未圖示)，在晶片108的背面黏附有晶粒黏貼膠膜105的狀態能夠容易地將晶片108拾起，而且能夠直接將晶片108黏貼在導線框架111而使其黏著。又，使用如此的電子構件的製法時，因為照射紫外線及/或放射線前的晶片保持性亦優良，在切割時能夠抑制晶片108剝離掉(晶片飛散)。而且，使用如此的電子構件製法時，因為微少的殘糊對晶粒黏貼膠膜105的污染性低，在將黏附有晶粒黏貼膠膜105之晶片108藉由黏貼並加溫來使其黏著於導線框架111上時，能夠抑制因污染而產生黏著不良。
又，引用第1圖的DAF使用步驟的圖來說明時，以使用包含以下步驟之電子構件的製法為佳，包含：在矽晶圓101的背面全面塗布糊狀黏著劑105之步驟(未圖示)；加熱該糊狀接著劑105使其半硬化來形成接著劑半硬化層105之步驟(未圖示)；貼合該矽晶圓101的接著劑半硬化層105與上述黏著片110的黏著劑層103之步驟(第1圖(1))；在貼合於該黏著片110的狀態，對矽晶圓101進行切割之步驟(第1圖(2))；及在切割後，藉由剝離接著劑半硬化層105與黏著劑層103，來將矽晶圓101及黏附於該矽晶圓101的背面之接著劑半硬化層105一起拾起之步驟(第1圖(3))。
因為此時在切割矽晶圓101後，藉由從黏著片110的基材薄膜106側照射紫外線及/或放射線(未圖示)，能夠在晶片108的背面黏附有接著劑半硬化層105的狀態，容易地將晶片108拾起，而且能夠將晶片108直接黏貼在導線框架111等而使其黏著。而且，依照該電子構件的製法時，因為能夠降低黏著劑層103污染接著劑半硬化層105，所以在將黏附有接著劑半硬化層105之晶片108黏貼於導線框架111上並加溫黏著時，能夠抑制因污染所產生的黏著不良。
以上，參照圖示，敘述了本發明的實施形態，但是此等係本發明例示，本發明亦可採用上述以外之各式各樣的構成。
例如，雖然在上述實施形態，晶圓的種類係矽晶圓101，但是並沒有特定限定的意思，任何種類的晶圓(例如GAN晶圓等)都可以採用。因為不管任何種類的晶圓都存在有適合將該晶圓切斷之切割刀片104，使用該切割刀片104能夠實行與上述實施形態同樣的電子構件製法，此時亦能夠得到同樣的作用效果。
[實施例]
以下，藉由實施例來進一步說明本發明，但是本發明未限定於此等。
<實驗材料的調製>
實施例中之黏著劑、黏著片、及多層黏著片等各種實驗材料係依下列的配方製造。
1.多層黏著片的材料係備齊以下之物。
．(甲基)丙烯酸酯聚合物A：係54%丙烯酸乙酯、22%丙烯酸丁酯、及24%甲氧基丙烯酸乙酯之共聚物、且藉由懸浮聚合所得到之物(本公司合成品)。
．(甲基)丙烯酸酯聚合物B：係95%丙烯酸－2－乙基己酯、及5%丙烯酸－2－羥基乙酯之共聚物、且藉由溶液聚合所得到之物(本公司合成品)。
．丙烯酸胺基甲酸酯寡聚物A：在使聚(環氧丙烷)二醇的末端與六亞甲基二異氰酸酯(脂肪族二異氰酸酯)的三聚物反應而構成之末端異氰酸酯寡聚物，更與二新戊四醇五丙烯酸酯反而成構成之末端丙烯酸酯寡聚物。數量平均分子量(Mn)為3,700、且丙烯酸酯官能基為15個(15官能)之丙烯酸胺基甲酸酯寡聚物(本公司合成品)。
．丙烯酸胺基甲酸酯寡聚物B：在使聚(環氧丙烷)二醇的末端與二異氰酸甲苯酯(芳香族二異氰酸酯)反應而構成之末端異氰酸酯寡聚物，更與二新戊四醇五丙烯酸酯反而成構成之末端丙烯酸酯寡聚物。數量平均分子量(Mn)為3,800、且丙烯酸酯官能基為10個(10官能)(本公司合成品)。
．丙烯酸胺基甲酸酯寡聚物C：在使聚(環氧乙烷)二醇的末端與異佛爾酮二異氰酸甲苯酯(脂環族二異氰酸酯)的三聚物反應而構成之末端異氰酸酯寡聚物，更與二新戊四醇五丙烯酸酯反而成構成之末端丙烯酸酯寡聚物。數量平均分子量(Mn)為2,800、且每1分子之丙烯酸酯官能基為10個(10官能)(本公司合成品)。
．丙烯酸胺基甲酸酯寡聚物D：在使聚(環氧丙烷)二醇的末端與六亞甲基二異氰酸酯的三聚物反應而構成之末端異氰酸酯寡聚物，更與二丙烯酸2－羥基乙酯反而成構成之末端丙烯酸酯寡聚物。數量平均分子量(Mn)為3,400、且每1分子之乙烯基數為2個(2官能)(本公司合成品)。
．聚矽氧接枝聚合物A：係使30質量份聚矽氧接枝寡聚物、20質量份丙烯酸丁酯、30質量份甲基丙烯酸甲酯、及20質量份甲基丙烯酸-2-羥基甲酯聚合而構成之聚矽氧接技聚合物(本公司合成品)。聚矽氧接枝寡聚物係使用在聚矽氧分子鏈的末端具有甲基丙烯醯基之聚矽氧接枝寡聚物(本公司合成品)。
．聚矽氧接枝聚合物B：係使30質量份聚矽氧接枝寡聚物、20質量份丙烯酸丁酯、20質量份甲基丙烯酸甲酯、20質量份甲基丙烯酸-2-羥基甲酯、及10質量份甲基丙烯酸聚合，進而使甲基丙烯酸環氧丙酯加成聚合而構成之聚矽氧接技聚合物(本公司合成品)。聚矽氧接枝寡聚物係使用在聚矽氧分子鏈的末端具有甲基丙烯醯基之聚矽氧接枝寡聚物(本公司合成品)。
．聚矽氧化合物A：矽油(信越化學公司製、製品名KF-96)
．光聚合引發劑：苄基二甲基縮酮(CIBA SPECIALTY CHEMICALS公司製、製品名IRGACURE 651)。
．硬化劑：1,6-二異氰酸環己酯的三羥甲基丙烷加成物(NIPPON POLYURETHANE INDUSTRY公司製、製品名CORONATE HL)
對應各實驗號碼之黏著劑的主要成分及其調配量係如表1及表2所示，在調製各黏著劑時係添加該等表所示之成分，並調配3質量份光聚合引發劑及3質量份硬化劑。又，為了簡潔地表示表1及表2所調配化合物的種類及其調配量，例如調配100質量份(甲基)丙烯酸酯聚合物A時， 係將該欄簡單地以「A100」表示。因此，例如實驗號碼1之黏著劑係含有100質量份(甲基)丙烯酸酯聚合物A、100質量份丙烯酸胺基甲酸酯寡聚物、1質量份聚矽氧接枝聚合物A，並且含有3質量份光聚合引發劑、及3質量份硬化劑。
接著，將黏著劑塗布於PET分離膜上，以乾燥的黏著劑層的厚度為10微米之方式塗布，並層積於PE 100微米的基材薄膜而得到黏著片。將30微米厚度的晶粒黏貼膠膜層壓於黏著片的黏著劑層上而成為多層黏著片。
基材薄膜係由以乙烯-甲基丙烯酸-甲基丙烯酸烷酯共聚物的Zn鹽作為主體之離子聚合物樹脂所構成，熔融流速(MFR)為1.5克/10分鐘(JIS K7210、210℃)、熔點為96℃，並含有Zn2+ 離子之薄膜(MITSUI-DUPONT POLYCHEMICALS公司製、製品名HAIMIRAN 1650)。
2.晶粒黏貼膠膜係備齊以下之物。
晶粒黏貼膠膜：厚度為30微米的薄膜，其組成為聚醯亞胺接著劑及環氧接著劑的混合物。
3.電子構件集合體係備齊以下之物。
電子構件的製造係使用形成有模擬電路圖案之直徑6英吋×厚度0.4毫米的矽晶圓。
<切割步驟>
黏著片切入量為30微米。切割係以10毫米×10毫米的晶片尺寸來進行。
切割裝置係使用DISCO公司製DAD341。切割刀片係使用DISCO公司製NBC－ZH205O－27HEEE。
切割刀片形狀：外徑55.56毫米、刀刃寬度35微米、內徑19.05毫米切割刀片轉數：40,000rpm切割刀片前進速度：80毫米/秒切削水溫度：25℃。切削水量：1.0升/分鐘
<擴張步驟>
使用多層黏著片而將矽晶圓切割後，使用擴張裝置進行擴張。
擴張裝置：HUGLE公司製ELECTRONICS HS－1800型垂伸量：20毫米垂伸速度：20毫米/秒加溫條件：40℃×1分鐘
<實驗結果的評價>
1.多層黏著片的黏附力：將多層黏著片貼合於已預先加熱至80℃之矽晶圓上，並以2公斤輥壓黏1來回，在壓黏1天後，使用以300mJ/cm2 紫外線照射前後之試料並將黏著片與晶粒黏貼膠膜的界面剝離。結果如表1、表2所示。
剝離方法：以180°剝離拉伸速度：300毫米/分鐘
2.晶片保持性：以前述條件切割半導體晶圓時，如第2圖所示，評價晶片被保持在多層黏著片之數目。結果如表1、表2所示。
◎(優)：保持於多層黏著片之晶片數目為95%以上。
○(良)：保持於多層黏著片之晶片數目為90%以上小於95%。
×(差)：保持於多層黏著片之晶片數目為小於90%。
3.拾起性：以前述條件切割半導體晶圓後，如第3圖所示，評價在黏附有晶粒黏貼膠膜之狀態能夠拾起的晶片數目。結果如表1、表2所示。
◎(優)：95%以上的晶片能夠拾起。
○(良)：80%以上小於95%的晶片能夠拾起。
×(差)：小於80%的晶片能夠拾起。
4.污染性：將黏著片貼在矽製鏡面晶圓上，在20分鐘後使用高壓水銀燈以300mJ/cm2 照射紫外線後，將黏著片剝離。使用微粒計算器測定在矽製鏡面晶圓(5英吋)上所殘留之0.28微米以上粒子數。結果如表1、2所示。
◎(優)：微粒為少於500個。
○(良)：微粒為少於2000個。
×(差)：微粒為2000個以上。
<實驗的考察>
從表1及表2所示的實驗結果能夠知道，使用本發明之黏著劑之多層黏著片，在切割時的晶片保持性優良、在拾起作業時晶粒黏貼膠膜與黏著劑層容易剝離，且微少的殘糊之污染性低。
以上，基於實施例說明本發明。該實施例到底是例示性，該業者應當理解能夠有各種變形例且如此的變形例亦在本發明的範圍內。
[產業上之利用可能性]
因為使用本發明之黏著劑之多層黏著片，在切割時的晶片保持性優良、在拾起作業時晶片容易剝離，且微少的殘糊之污染性低之效果，所以適合使用於在切割後，能夠在晶片背面黏附有晶粒黏貼膠膜層的狀態進行拾起，且黏貼並使其黏著於導線框架等之電子構件的製法。
100．．．多層黏著片
101．．．矽晶圓
102．．．環框
103．．．黏著劑層
104．．．切割刀片
105．．．晶粒黏貼膠膜
106．．．基材薄膜
107．．．切入
108．．．晶片
110．．．黏著片
111．．．導線框架
第1圖係為了說明一實施形態的多層黏著片的構成的剖面之概略圖。
第2圖係為了說明晶片保持性之照片。
第3圖係為了說明拾起性之概念圖。
100．．．多層黏著片
101．．．矽晶圓
102．．．環框
103．．．黏著劑層
104．．．切割刀片
105．．．晶粒黏貼膠膜
106．．．基材薄膜
107．．．切入
108．．．晶片
110．．．黏著片
111．．．導線框架

Claims (9)

  1. 一種黏著劑，其含有：包含丙烯酸乙酯、丙烯酸丁酯與甲氧基丙烯酸乙酯之(甲基)丙烯酸酯聚合物、藉由使含有羥基及複數個(甲基)丙烯酸酯基之(甲基)丙烯酸酯化合物與異氰酸酯三聚物反應而形成之具有4個以上乙烯基之丙烯酸胺基甲酸酯寡聚物、及聚矽氧接枝聚合物，相對於100質量份的該(甲基)丙烯酸酯聚合物，含有20質量份以上200質量份以下的該具有4個以上乙烯基之丙烯酸胺基甲酸酯寡聚物，並含有0.05質量份以上20質量份以下的該聚矽氧接枝聚合物。
  2. 如申請專利範圍第1項之黏著劑，其中該聚矽氧接枝聚合物係以(甲基)丙烯酸酯單體作為聚合前的調配物之一。
  3. 如申請專利範圍第2項之黏著劑，其中該(甲基)丙烯酸酯單體係具有羥基。
  4. 如申請專利範圍第1項之黏著劑，其中該丙烯酸胺基甲酸酯寡聚物具有10或15個乙烯基。
  5. 一種黏著片，其具備基材薄膜、及使用如申請專利範圍第1至4項中任一項之黏著劑塗布該基材薄膜而構成的黏著劑層。
  6. 如申請專利範圍第5項之黏著片，其係電子構件固定用。
  7. 一種多層黏著片，其係具備如申請專利範圍第6項之黏著片、及層積於該黏著片的該黏著劑層側而構成的晶粒黏貼膠膜。
  8. 一種電子構件的製法，其係切割晶圓而得到的電子構件之製法，其包含以下步驟：在如申請專利範圍第7項之多層黏著片的該晶粒黏貼膠膜表面貼合晶圓之步驟；在貼合於該多層黏著片之狀態，對該晶圓進行切割之步驟；及在切割後，藉由剝離晶粒黏貼膠膜與黏著劑層，來將該晶圓與黏附於該晶圓的背面之晶粒黏貼膠膜一同拾起之步驟。
  9. 一種電子構件的製法，其係切割晶圓而得到的電子構件之製法，其包含以下步驟：在晶圓的背面全面塗布糊狀黏著劑之步驟；加熱該糊狀接著劑使其半硬化來形成接著劑半硬化層之步驟；貼合該晶圓的接著劑半硬化層與如申請專利範圍第6項之黏著片的黏著劑層之步驟；在貼合於該黏著片的狀態，對晶圓進行切割之步驟；及在切割後，藉由剝離接著劑半硬化層與黏著劑層，來將該晶圓及黏附於該晶圓的背面之接著劑半硬化層一起拾起之步驟。
TW96139197A 2007-10-16 2007-10-19 黏著劑、黏著片、多層黏著片及電子構件之製法 TWI413671B (zh)

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