TWI534227B - 切割膜黏著層形成用組成物、切割膜、切割晶片接合膜及切割半導體晶圓之方法 - Google Patents

切割膜黏著層形成用組成物、切割膜、切割晶片接合膜及切割半導體晶圓之方法 Download PDF

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TWI534227B
TWI534227B TW103144041A TW103144041A TWI534227B TW I534227 B TWI534227 B TW I534227B TW 103144041 A TW103144041 A TW 103144041A TW 103144041 A TW103144041 A TW 103144041A TW I534227 B TWI534227 B TW I534227B
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group
acrylate
adhesive layer
dicing
meth
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TW103144041A
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TW201529780A (zh
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金榮國
金熹正
金思拉
曺正鎬
金丁鶴
南承希
李光珠
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Ｌｇ化學股份有限公司
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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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
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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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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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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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  • Engineering & Computer Science (AREA)
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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesive Tapes (AREA)
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切割膜黏著層形成用組成物、切割膜、切割晶片接合膜及切割半導體晶圓之方法
本發明是關於一種切割膜黏著層形成用組成物及一種切割膜。
一般而言，製造半導體晶片之製程包含在晶圓上形成微圖案，且將晶圓拋光以便滿足最終裝置及封裝之標準。
封裝製程包含：檢測半導體晶片之缺陷的晶圓檢測製程；切削晶圓以分成個別晶片之切割製程；將分開之晶片附接至引線框架或電路膜之安裝板的晶片接合製程；使用電連接構件(諸如導線)將裝備於半導體晶片上之晶片墊與引線框架或電路膜之電路圖案連接的線接合製程；用封裝物覆蓋外部以便保護半導體晶片之內部電路及其他組件的模製製程；切削擋隔桿連接引線之修整製程；使引線彎曲成所需形狀之成型製程；以及檢測完成之 封裝之缺陷的檢測成品製程，以及其類似製程。
在切割製程中，使用金剛石砂輪及其類似物將晶圓切至預定厚度。本文中，為了固定晶圓，在適當條件下將切割膜層壓至晶圓之背側，且隨後進行所述製程。為了將經切割之個別晶片附接至電路板，使用晶片接合膜。
同時，切割製程包含以下步驟：用切割刀切削半導體晶圓，將UV照射至半導體晶圓之基底膜，且拾取藉由切削半導體晶圓分開之個別晶片，但在拾取製程期間發生膜之間的固定問題，及由於膜之間的過度剝落強度導致的問題，因此拾取晶片之成功率降低或在拾取期間產生晶片裂紋。
本發明之一個目標為提供一種切割膜黏著層形成用組成物以便提供一種切割晶片接合膜，所述切割晶片接合膜可防止切割製程中膜之間的固定以增加拾取成功率，且展示相對較高的晶片剪切強度(die shear strength)以防止因黏著強度劣化所致之分層。
本發明之另一目標為提供切割晶片接合膜。
本發明之又一目標為提供一種使用切割晶片接合膜切割半導體晶圓之方法。
提供一種切割膜黏著層形成用組成物，包含：包含至少一種由含有(甲基)丙烯酸酯系官能基及非極性官能基之聚合物、含 有至少一個氟之(甲基)丙烯酸酯系聚合物以及含有反應性官能基之矽改質之(甲基)丙烯酸酯系聚合物所構成的族群中選出之聚合物的聚合物添加劑；黏著黏合劑；以及光起始劑，其中所述聚合物添加劑與所述黏著黏合劑之重量比為0.01%至4.5%。
含有(甲基)丙烯酸酯系官能基及非極性官能基之聚合物可包含以下化學式1之重複單元。
在化學式1中，R1為氫或碳數為1至20之烷基；R2為氫、碳數為1至20之烷基、聚酯基或聚醚基；且n為1至300之整數。
含有至少一個氟之(甲基)丙烯酸酯系聚合物可包含經碳數為1至10之全氟烷基或碳數為1至10之氟化烯基取代的(甲基)丙烯酸酯系聚合物。
含有反應性官能基之矽改質之(甲基)丙烯酸酯系聚合物可包含經至少一個由以下所構成的族群中選出之反應性官能基取代之矽改質之(甲基)丙烯酸酯系聚合物：羥基、碳數為1至10之伸烷基醇、環氧基、胺基、巰基以及羧基。
聚合物添加劑可更包含至少一種由以下所構成的族群中選出之有機溶劑：醇、醚、乙酸酯或酮。
以1重量%至50重量%之有機溶劑計，含有(甲基)丙烯酸酯系官能基及非極性官能基之聚合物及含有反應性官能基之矽改質之(甲基)丙烯酸酯系聚合物的酸值可分別為10毫克KOH/克至50毫克KOH/克。
黏著黏合劑可包含未經取代或經至少一個由羥基、異氰酸酯基、乙烯基以及(甲基)丙烯酸酯基所構成的族群中選出之官能基取代的(甲基)丙烯酸酯聚合物或(甲基)丙烯酸酯共聚物。
黏著黏合劑可包含添加有丙烯酸酯之嵌入黏著黏合劑，所述嵌入黏著黏合劑具有碳碳雙鍵作為(甲基)丙烯酸酯樹脂之側鏈。舉例而言，作為嵌入黏著黏合劑，可使用添加有1重量%至45重量%(甲基)丙烯酸酯官能基作為連接至(甲基)丙烯酸酯基底樹脂主鏈之側鏈的聚合物樹脂。
黏著黏合劑可包含重量平均分子量為100,000至1,500,000之聚合物。
光起始劑可包含至少一種由以下所構成的族群中選出之物質：安息香及其烷基醚、苯乙酮、蒽醌、硫代黃嘌呤、縮酮、二苯甲酮、α-胺基苯乙酮(α-aminoacetophenone)、氧化醯基膦以及肟酯(oxime ester)。
以100重量份黏著黏合劑計，組成物可包含0.01重量份至5重量份光起始劑。
切割膜黏著層形成用組成物可更包含固化劑。
固化劑可包含至少一種由以下所構成的族群中選出之物質：異氰酸酯化合物、氮丙啶化合物、環氧化合物以及金屬螯合化合物。
以100重量份黏著黏合劑計，切割膜黏著層形成用組成物可包含0.1重量份至30重量份固化劑。
亦提供一種包含基底膜及形成於所述基底膜之至少一側上之黏著層的切割膜，其中所述黏著層包含上文說明之切割膜黏著層形成用組成物。
基底膜之厚度可為10微米至200微米，且黏著層之厚度可為0.5微米至50微米。
亦提供一種切割晶片接合膜，包含切割膜及形成於所述切割膜之至少一側上之接合層。
亦提供一種切割半導體晶圓之方法，包含以下步驟：藉由部分處理包含切割晶片接合膜及層壓於所述切割晶片接合膜之至少一側上之晶圓的半導體晶圓來進行預處理以使得其完全切削或其可切削；在所述預處理步驟之後擴展所述半導體晶圓；以及將UV照射至所述擴展之半導體晶圓的基底膜，且拾取藉由切削所述半導體晶圓分開之個別晶片。
提供一種切割膜黏著層形成用組成物以便提供一種切割晶片接合膜，可防止切割製程中膜之間的固定以增加拾取成功率且展示相對較高的晶片剪切強度以防止因黏著強度劣化所致之分層；一種包含黏著層之切割膜，所述黏著層包含所述組成物；一種包含所述切割膜之切割晶片接合膜；以及一種使用所述切割晶片接合膜切割半導體晶圓之方法。
下文將詳細說明根據特定實施例之切割膜、切割晶片接合膜以及切割半導體晶圓之方法。
根據本發明之一個實施例，提供一種切割膜黏著層形成用組成物，包含：包含至少一種由含有(甲基)丙烯酸酯系官能基及非極性官能基之聚合物、含有至少一個氟之(甲基)丙烯酸酯系聚合物以及含有反應性官能基之矽改質之(甲基)丙烯酸酯系聚合物所構成的族群中選出之聚合物的聚合物添加劑；黏著黏合劑；以及光起始劑，其中所述聚合物添加劑與所述黏著黏合劑之重量比為0.01%至4.5%。
先前，存在由於在切割製程中拾取製程期間膜之間的固定及過度剝落強度，拾取晶片之成功率降低之問題。
因此，本發明者經由實驗確認，若使用包含自切割膜黏著層形成用組成物形成之黏著層的切割膜，所述組成物以特定含量包含：包含至少一種由含有(甲基)丙烯酸酯系官能基及非極性官能基之聚合物、含有至少一個氟之(甲基)丙烯酸酯系聚合物以及含有反應性官能基之矽改質之(甲基)丙烯酸酯系聚合物所構成的族群中選出之聚合物的聚合物添加劑，則可防止膜之間的固定且可降低膜之間的剝落強度以改良拾取晶片之成功率，可展示相對較高晶片剪切強度以防止因黏著強度劣化所致之分層，且可改良半導體製造方法之可靠性且完成本發明。
可將含有(甲基)丙烯酸酯系官能基及非極性官能基之聚 合物、含有至少一個氟之(甲基)丙烯酸酯系聚合物以及含有反應性官能基之矽改質之(甲基)丙烯酸酯系聚合物分別暴露於自所述組成物製備之黏著層之頂部以得到可釋放性及滑動特性，同時具有與黏著層表面上之黏著黏合劑的較大相容性且因此易於混合。
因此，聚合物添加劑可與黏著黏合劑反應以使轉錄最小化，且同時上述非極性部分位於黏著層表面上以有效提供可釋放性及滑動特性。
特定言之，以黏著黏合劑計，可以0.01重量%至4.5重量%，或0.1重量%至2重量%之量使用聚合物添加劑，且儘管相對較低之使用量，其可顯著降低自以上實施例之切割膜黏著層形成用組成物製備之切割膜黏著層的剝落強度，例如在UV照射之前/之後的180度剝落強度及黏力，以及SUS剝落強度。
若聚合物添加劑與黏著黏合劑之重量比過低，則自根據以上實施例之切割膜黏著層形成用組成物製備之切割膜黏著層可具有顯著增加之剝落強度，例如在UV照射之前/之後顯著增加的180度剝落強度及黏力以及SUS剝落強度。
另外，若聚合物添加劑與黏著黏合劑之重量比過高，儘管自根據以上實施例之切割膜黏著層形成用組成物製備之切割膜黏著層的剝落強度可在一些程度上降低，但黏著層之晶片剪切強度可顯著降低，產生因黏著強度劣化所致之分層，且因此在半導體製造方法中可靠性可能降低。
含有(甲基)丙烯酸酯系官能基及非極性官能基之聚合物可包含以下化學式1之重複單元。
[化學式1]
在化學式1中，R1為氫或碳數為1至20之烷基；R2為氫、碳數為1至20之烷基、聚酯基或聚醚基；且n為1至300之整數。
含有(甲基)丙烯酸酯系官能基及非極性官能基之聚合物的特定實例可包含(但不限於)畢克(BYK)0-350、畢克-352、畢克-354、畢克-355、畢克-356、畢克-358N、畢克-361N、畢克-380、畢克-392、畢克-394以及其類似者。
含有至少一個氟之(甲基)丙烯酸酯系聚合物可包含經碳數為1至10之全氟烷基或碳數為1至10之氟化烯基取代的(甲基)丙烯酸酯系聚合物。
含有至少一個氟之(甲基)丙烯酸酯系聚合物之市售產品的特定實例可包含(但不限於)菲特金特(Ftergent)222F(由尼歐斯株式會社(NEOS Co.Ltd.)製造)、F470(DIC公司)、F489(DIC公司)、V-8FM以及其類似者。
含有反應性官能基之矽改質之(甲基)丙烯酸酯系聚合物可包含經至少一個由以下所構成的族群中選出之反應性官能基取代之矽改質之(甲基)丙烯酸酯系聚合物：羥基、碳數為1至10之伸烷基醇、環氧基、胺基、巰基或羧基。
含有反應性官能基之矽改質之(甲基)丙烯酸酯系聚合物的特定實例可包含羥基官能改質之聚丙烯酸酯，且其市售產品之 特定實例可包含(但不限於)畢克-希爾克林(BYK-SILCLEAN)3700及其類似者。
包含至少一種由含有(甲基)丙烯酸酯系官能基及非極性官能基之聚合物、含有至少一個氟之(甲基)丙烯酸酯系聚合物以及含有反應性官能基之矽改質之(甲基)丙烯酸酯系聚合物所構成的族群中選出之聚合物的聚合物添加劑可更包含至少一種由以下所構成的族群中選出之有機溶劑：醇、醚、乙酸酯或酮。
聚合物添加劑可包含1重量%至50重量%的上述聚合物及剩餘量之有機溶劑。
以1重量%至50重量%之有機溶劑計，含有(甲基)丙烯酸酯系官能基及非極性官能基之聚合物及含有反應性官能基之矽改質之(甲基)丙烯酸酯系聚合物的酸值可分別為10毫克KOH/克至50毫克KOH/克，或20毫克KOH/克至40毫克KOH/克。
同時，可在無特別限制之情況下使用已知用於形成切割膜黏著層之聚合物樹脂作為黏著黏合劑，且例如可使用經特定反應性官能基取代之聚合物樹脂或具有包含反應性官能基之主鏈之聚合物樹脂。
特定言之，黏著黏合劑可包含未經取代或經至少一個由羥基、異氰酸酯基、乙烯基以及(甲基)丙烯酸酯基所構成的族群中選出之官能基取代的(甲基)丙烯酸酯聚合物或(甲基)丙烯酸酯共聚物。
另外，黏著黏合劑可為添加有丙烯酸酯之嵌入黏著黏合劑，所述嵌入黏著黏合劑具有碳碳雙鍵作為(甲基)丙烯酸酯樹脂之側鏈。舉例而言，作為嵌入黏著黏合劑，可使用添加有1重量% 至45重量%(甲基)丙烯酸酯官能基作為連接至(甲基)丙烯酸酯基底樹脂主鏈之側鏈的聚合物樹脂。
黏著黏合劑可包含重量平均分子量為100,000至1,500,000之聚合物樹脂。
特定言之，未經取代或經至少一個由羥基、異氰酸酯基、乙烯基以及(甲基)丙烯酸酯基所構成的族群中選出之官能基取代之(甲基)丙烯酸酯聚合物或(甲基)丙烯酸酯共聚物的重量平均分子量可為100,000至1,500,000。
如本文所用，(甲基)丙烯酸酯意謂包含丙烯酸酯及(甲基)丙烯酸酯兩者。
(甲基)丙烯酸酯聚合物或(甲基)丙烯酸酯共聚物之實例可包含(甲基)丙烯酸酯單體與含有可交聯官能基之單體的聚合物或共聚物。
本文中，(甲基)丙烯酸酯單體之實例可包含(甲基)丙烯酸烷酯(alkyl(meth)acrylate)，且更特定言之，具有C1-20烷基之單體之實例可包含(甲基)丙烯酸戊酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸十二烷基酯、或(甲基)丙烯酸癸酯或其兩種或多於兩種類別之混合物。因為使用烷基數較高之單體，所以最終共聚物之玻璃轉化溫度降低，且因此可根據所需玻璃轉化溫度選擇適當單體。
含有可交聯官能基之單體的實例可包含含有羥基之單體、含有羧基之單體、含氮單體或其兩種或多於兩種類別之混合 物。含有羥基之化合物的實例可包含(但不限於)(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯以及其類似者，含有羧基之化合物的實例可包含(但不限於)(甲基)丙烯酸及其類似者，且含氮單體之實例可包含(但不限於)(甲基)丙烯腈、N-乙烯吡咯啶酮(N-vinyl pyrrolidone)、N-乙烯己內醯胺(N-vinyl caprolactam)以及其類似者。就諸如相容性及其類似者之其他效能改良而言，(甲基)丙烯酸酯系樹脂可更包含乙酸乙烯酯、苯乙烯或含有丙烯腈碳碳雙鍵之低分子量化合物以及其類似者。
添加有丙烯酸酯之嵌入黏著黏合劑的重量平均分子量可為100,000至1,500,000，所述嵌入黏著黏合劑具有碳碳雙鍵作為(甲基)丙烯酸酯樹脂之側鏈。
若包含於黏著黏合劑中之聚合物樹脂之重量平均分子量過低，則根據以上實施例之切割膜黏著層形成用組成物之可塗佈性或內聚性可劣化，且當使自所述組成物形成之黏著層分層時，殘餘物可能保留在黏著物中或黏著層可能斷裂。
若包含於黏著黏合劑中之聚合物樹脂之重量平均分子量過高，則根據以上實施例之切割膜黏著層形成用組成物之UV固化可不充分發生，且因此自所述組成物形成之黏著層的剝落強度可能不充分降低以降低拾取成功率。
切割膜黏著層形成用組成物可更包含UV可固化化合物。
UV可固化化合物之類別不受特別限制，且例如可使用重量平均分子量為約500至300,000之多官能化合物(例如多官能胺基甲酸酯丙烯酸酯、多官能丙烯酸酯單體或寡聚物以及其類似者)。於本領域具有通常知識者可易於根據所需用途選擇適當化合 物。
以100重量份的上述黏著黏合劑計，UV可固化化合物之含量可為5重量份至400重量份，較佳10重量份至200重量份。若UV可固化化合物之含量小於5重量份，則在固化之後黏著強度降低可能不充分且因此拾取可能劣化，且若其大於400重量份，則在UV照射之前黏著劑之內聚性可能不足夠，或存在可能不易於實現離型膜分層及其類似者之問題。
包含於切割膜黏著層形成用組成物中之光起始劑的特定實例不受特別限制，且可在無特別限制之情況下使用通常已知之光起始劑。作為實例，作為光起始劑，可使用安息香及其烷基醚、苯乙酮、蒽醌、硫代黃嘌呤、縮酮、二苯甲酮、α-胺基苯乙酮、氧化醯基膦、肟酯或其兩種或多於兩種類別之混合物。
可在考慮所製備之黏著層之物理特性及特徵以及所使用之黏著黏合劑之類別及特徵以及其類似者的情況下確定光起始劑之量，且例如以100重量份黏著黏合劑計，切割膜黏著層形成用組成物可包含0.01重量份至8重量份光起始劑。
切割膜黏著層形成用組成物可更包含固化劑。當將切割膜黏著層形成用組成物塗佈於基底膜上時，固化劑可在室溫下或在30℃至50℃之溫度下與黏著黏合劑之反應性基團反應以形成交聯。包含於固化劑中之特定反應性基團可保持未反應，且可在拾取之前經由UV照射進一步交聯，因此降低黏著層之黏著強度。
固化劑可包含至少一種由以下所構成的族群中選出之物質：異氰酸酯化合物、氮丙啶化合物、環氧化合物以及金屬螯合化合物。
可在考慮所製備之黏著層之物理特性及特徵以及所使用之黏著黏合劑之類別及特徵以及其類似者的情況下確定固化劑之量，且例如以100重量份黏著黏合劑計，切割膜黏著層形成用組成物可包含0.1重量份至30重量份固化劑。
根據另一實施例，提供一種包含基底膜及形成於所述基底膜之至少一側上之黏著層的切割膜，其中所述黏著層包含根據上述實施例之切割膜黏著層形成用組成物。
基底膜之類別不受特別限制，且例如可使用本領域中已知之塑膠膜或金屬箔以及其類似者。舉例而言，基底膜可包含低密度聚乙烯、直鏈聚乙烯、中等密度聚乙烯、高密度聚乙烯、超低密度聚乙烯、聚丙烯無規(random)共聚物、聚丙烯嵌段共聚物、均聚丙烯(homopolypropylene)、聚甲基戊烯、乙烯-乙酸乙烯酯共聚物、乙烯-甲基丙烯酸共聚物、乙烯-甲基丙烯酸甲酯共聚物、乙烯-離子體共聚物、乙烯-乙烯醇共聚物、聚丁烯、苯乙烯共聚物或其兩種或多於兩種類別之混合物。包含兩種或多於兩種類別之聚合物之混合物的基底膜包含兩個或多於兩個膜之堆疊結構，所述膜分別包含上述聚合物；及單層之膜，所述膜包含兩種或多於兩種類別之上述聚合物。
基底膜之厚度不受特別限制，且通常其可形成為10微米至200微米，較佳50微米至180微米之厚度。若厚度小於10微米，則在切割製程中切削深度之控制可能不穩定，且若其大於200微米，則可能在切割製程中產生大量毛邊，或伸長率可能降低，且因此可能不精確實現擴展製程。
基底膜視需要可經受常見物理或化學處理，諸如消光處 理、電暈(corona)放電、底塗劑處理、交聯以及其類似處理。
黏著層之厚度可為0.5微米至50微米，或5微米至30微米。
包含於黏著層中之切割膜黏著層形成用組成物之細節包含上述所有內容。
根據本發明之又一實施例，提供一種切割晶片接合膜，包含切割膜及形成於所述切割膜之至少一側上之接合層。
切割膜之細節包含上述所有內容。
接合層可包含環氧樹脂、低彈性高分子量樹脂以及用於接合層之固化劑。環氧樹脂可包含本領域中已知之用於黏著劑之常見環氧樹脂，且例如可使用分子中含有兩個或多於兩個環氧基且重量平均分子量為100至5000之環氧樹脂。
環氧樹脂可經由固化製程形成硬交聯結構以展示突出的黏著特性、耐熱性以及機械強度。
更特定言之，尤其較佳使用環氧當量為100至1000之環氧樹脂作為環氧樹脂。若環氧樹脂之環氧當量小於100，則交聯密度可能變得過高，且因此接合膜可能展示一般偏硬特性，且若環氧樹脂之環氧當量大於1000，則耐熱性可能劣化。
環氧樹脂之特定實例可包含(但不限於)：雙官能環氧樹脂，諸如雙酚A環氧樹脂或雙酚F環氧樹脂以及其類似者；或具有3個或多於3個官能基之多官能環氧樹脂，諸如甲酚酚醛清漆環氧樹脂、苯酚酚醛清漆環氧樹脂、四官能環氧樹脂、聯苯型環氧樹脂、三苯酚甲烷型環氧樹脂、烷基改質之三苯酚甲烷型環氧樹脂、萘型環氧樹脂、二環戊二烯型環氧樹脂、二環戊二烯改質 之苯酚型環氧樹脂以及其類似者，或其兩種或多於兩種類別之混合物。
較佳使用雙官能環氧樹脂與多官能環氧樹脂之混合樹脂作為環氧樹脂。
「多官能環氧樹脂」意謂具有3個或多於3個官能基之環氧樹脂。亦即，雙官能環氧樹脂一般具有極好可撓性及高溫流動性以及其類似者，但具有較差耐熱性及固化速度，而具有3個或多於3個官能基之多官能環氧樹脂由於較高交聯密度具有快速的固化速度且展示突出的耐熱性，但具有較差可撓性及流動性。因此，藉由適當混合兩種類別之樹脂，可在切割製程中抑制晶片分散或毛邊發生，同時控制接合層之彈性及黏性特性。
低彈性高分子量樹脂可在黏著劑中形成軟區段(segment)以在高溫下得到應力鬆弛。可使用任何樹脂作為高分子量樹脂，只要其在與環氧樹脂摻合以形成膜時不誘導斷裂、可在形成交聯結構之後展示黏彈性、且具有與其他組分之極好相容性及儲存穩定性即可。
特定類別之低彈性高分子量樹脂不受特別限制，只要其滿足上述特性即可，但例如可使用聚醯亞胺、聚醚醯亞胺、聚酯醯亞胺、聚醯胺、聚醚碸、聚醚酮、聚烯烴、聚氯乙烯、苯氧基、反應性丙烯腈丁二烯橡膠、(甲基)丙烯酸酯系樹脂以及其類似者或其兩種或多於兩種類別之混合物。
(甲基)丙烯酸酯系樹脂之特定實例可包含丙烯醯基系(acryl based)共聚物，其包含(甲基)丙烯酸及其衍生物，其中(甲基)丙烯酸及其衍生物之實例可包含(甲基)丙烯酸，含有C1-12烷 基之(甲基)丙烯酸烷基酯，諸如(甲基)丙烯酸甲酯或(甲基)丙烯酸乙酯以及其類似者；(甲基)丙烯腈或(甲基)丙烯醯胺以及其他可共聚單體。
(甲基)丙烯酸酯系樹脂可包含一種類別或兩種或多於兩種類別之官能基，諸如縮水甘油基、羥基、羧基、胺基以及其類似基團，其可藉由使諸如(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸羥酯、(甲基)丙烯酸羥乙酯、羧基(甲基)丙烯酸酯或其類似者之單體共聚來引入。
可包含於黏著劑組成物中之固化劑不受特別限制，只要其可與環氧樹脂及/或低彈性高分子量樹脂反應形成交聯結構即可。舉例而言，可使用能夠與兩種組分反應形成交聯結構之固化劑，且此類固化劑分別與黏著劑中之軟區段及硬區段形成交聯結構以改良耐熱性，且同時在其界面處充當兩個區段之交聯劑以改良半導體封裝之可靠性。
儘管不受特別限制，但接合層之厚度可為例如1微米至100微米，或3微米至50微米。
根據本發明之另一實施例，提供一種切割半導體晶圓之方法，包含以下步驟：藉由部分處理包含以上切割晶片接合膜及層壓於所述切割晶片接合膜之至少一側上之晶圓的半導體晶圓來進行預處理以使得其完全切削或其可切削；在所述預處理步驟之後擴展所述半導體晶圓；以及將UV照射至所述擴展之半導體晶圓的基底膜，且拾取藉由切削所述半導體晶圓分開之個別晶片。
切割晶片接合膜之細節包含上述所有內容。
除切割方法之步驟之細節外，可在無特別限制之情況下 使用用於切割半導體晶圓之通常已知設備、切割方法以及其類似者。
藉由使用包含切割膜之切割晶片接合膜，可在半導體晶圓之切割製程期間使毛邊之發生最小化以防止半導體晶片的污染且改良半導體晶片之可靠性及壽命。
本發明之特定實施例將詳細說明於以下實例中。然而，這些實例僅為了說明本發明之特定實施例，且本發明之範疇不限於此。
實例1
以100重量份光可固化黏著黏合劑樹脂計，將2重量份異氰酸酯系固化劑(多官能異氰酸酯寡聚物)、0.2重量份畢克-希爾克林(畢克公司)以及1重量份作為光起始劑之達若可蒂波(DAROCUR TPO)混合以製備UV可固化黏著劑組成物。使用添加有20重量%丙烯酸酯官能基作為連接至丙烯酸系基底樹脂主鏈之側鏈的聚合物樹脂(Mw 300,000)作為光可固化黏著黏合劑樹脂。
將UV可固化黏著劑組成物塗佈於100微米聚烯烴膜之一側上且乾燥以製備包含10微米厚黏著層之切割膜。
實例2
以100重量份光可固化黏著黏合劑樹脂計，將2重量份異氰酸酯系固化劑(多官能異氰酸酯寡聚物)、0.2重量份畢克-希爾克林394(畢克公司)以及1重量份作為光起始劑之達若可蒂波混合以製備UV可固化黏著劑組成物。使用添加有20重量%丙烯酸酯官能基作為連接至丙烯酸系基底樹脂主鏈之側鏈的聚合物樹 脂(Mw 300,000)作為光可固化黏著黏合劑樹脂。
將UV可固化黏著劑組成物塗佈於100微米厚聚烯烴膜之一側上且乾燥以製備包含10微米厚黏著層之切割膜。
比較例1
以100重量份光可固化黏著黏合劑樹脂計，將2重量份異氰酸酯系固化劑(多官能異氰酸酯寡聚物)及1重量份作為光起始劑之達若可蒂波混合以製備UV可固化黏著劑組成物。使用添加有20重量%丙烯酸酯官能基作為連接至丙烯酸系基底樹脂主鏈之側鏈的聚合物樹脂(Mw 300,000)作為光可固化黏著黏合劑樹脂。
將UV可固化黏著劑組成物塗佈於100微米厚聚烯烴膜之一側上且乾燥以製備包含10微米厚黏著層之切割膜。
比較例2
以100重量份光可固化黏著黏合劑樹脂計，將2重量份異氰酸酯系固化劑(多官能異氰酸酯寡聚物)、5重量份畢克-希爾克林3700(畢克公司)以及1重量份作為光起始劑之達若可蒂波混合以製備UV可固化黏著劑組成物。使用添加有20重量%丙烯酸酯官能基作為連接至丙烯酸系基底樹脂主鏈之側鏈的聚合物樹脂(Mw 300,000)作為光可固化黏著黏合劑樹脂。
將UV可固化黏著劑組成物塗佈於100微米厚聚烯烴膜之一側上且乾燥以製備包含10微米厚黏著層之切割膜。
比較例3
以100重量份光可固化黏著黏合劑樹脂計，將2重量份異氰酸酯系固化劑(多官能異氰酸酯寡聚物)、0.5重量份矽化合 物油L-7500(史威特公司(Silvet Company))以及1重量份作為光起始劑之達若可蒂波混合以製備UV可固化黏著劑組成物。使用添加有20重量%丙烯酸酯官能基作為連接至丙烯酸系基底樹脂主鏈之側鏈的聚合物樹脂(Mw 300,000)作為光可固化黏著黏合劑樹脂。
將UV可固化黏著劑組成物塗佈於100微米厚聚烯烴膜之一側上且乾燥以製備包含10微米厚黏著層之切割膜。
實驗實例
如下量測在實例1及實例2以及比較例1至比較例3中製備之切割膜之剝落強度、黏力以及拾取成功率，且結果顯示於以下表1及表2中。
1.量測晶片接合膜/切割膜之間的180度剝落強度(在UV固化之前/之後)
為了量測晶片接合膜與PSA層之間的剝落強度，在室溫下將接合膜與切割膜一起層壓，使其靜置1小時，製造寬度為25毫米之樣品，且在300毫米/分鐘之速度下量測180度剝落強度，且另外量測在UV固化之後的值。每一份樣品進行三次或多於三次量測，且記錄平均值。
2.量測SUS/切割膜之間的90度剝落強度(在UV固化之前)
製備寬度為25毫米之切割膜，且將其附接至SUS 304之黏著物。在固化1小時之後，在300毫米/分鐘之速度下量測90度剝落強度。每一份樣品進行三次或多於三次量測，且記錄平均值。
3.黏性測試(在UV固化之前/之後)
將切割膜放置於板上以使得黏著層面朝上，且使用直徑為1吋之球型探針量測黏力。本文中，施加至探針之力為800公克力，接觸時間為0.01秒，撕掉探針之量測速度為1毫米/秒，且用於量測之設備為質構儀(Texture Analyzer)。
4.量測拾取成功率
在70℃下將自實例及比較例之切割膜製備之切割晶片接合膜與晶圓一起層壓。隨後，在以下條件下使用切割設備(由內翁公司(NEON Company)製造)進行切割製程，且隨後在以下條件下將UV照射至切割膜側。其後，用晶片接合機(新川株式會社(Shinkawa Co.Ltd.))拾取200個晶片，且量測未拾取晶片之數目且以百分比形式記錄。
[切割條件]
刀片：27HEDD
刀片旋轉速度：40,000轉/分鐘
速度：30毫米/秒
晶片尺寸：10毫米×10毫米
切削深度：70微米
[UV照射條件]
燈：金屬鹵化物型
照明強度：70毫瓦/平方公分(用UV計量測)
照射量：200毫焦/平方公分或多於200毫焦/平方公分(用UV計量測)
[拾取條件]
擴展：4毫米
針高度：0.15毫米
拾取強度：100公克力
5.晶片剪切強度
將厚度為500微米之塗佈有二氧化物層之晶圓切成5毫米×5毫米之尺寸，且在60℃下與切割晶片接合膜一起層壓，隨後UV照射以移除切割膜且切削以僅留下晶片尺寸之接合膜。將5毫米×5毫米尺寸之上晶片放置於10毫米×10毫米尺寸之下晶片上，且隨後在130℃下於熱板上用2公斤力之力按壓2秒，隨後在125℃下固化1小時。將以上製造之測試件在175℃下固化2小時，且隨後在250℃下量測上晶片之晶片剪切強度。
如表1及表2中所示，確認與在比較例1中製備之切割膜相比，在實例1及實例2中製備之切割膜展示相對較低之在UV固化之前/之後的180度剝落強度及黏力、相對較低之SUS剝落強 度以及較高之拾取成功率。
此外，確認與在比較例2及比較例3中製備之切割膜相比，在實例1及實例2中製備之切割膜展示相對較高之晶片剪切強度以防止因黏著強度降低所致之分層，因此抑制回焊裂紋且改良半導體製造方法之可靠性。

Claims (18)

  1. 一種切割膜黏著層形成用組成物，包括：聚合物添加劑，包括至少一種聚合物，所述聚合物由含有(甲基)丙烯酸酯系官能基及非極性官能基之聚合物、含有至少一個氟之(甲基)丙烯酸酯系聚合物以及含有反應性官能基之矽改質之(甲基)丙烯酸酯系聚合物所構成的族群中選出；黏著黏合劑；以及光起始劑，其中所述黏著黏合劑為添加有1重量%至45重量%(甲基)丙烯酸酯官能基作為連接至(甲基)丙烯酸酯基底樹脂主鏈之側鏈的聚合物樹脂，且所述聚合物添加劑與所述黏著黏合劑之重量比為0.01%至4.5%。
  2. 如申請專利範圍第1項所述之切割膜黏著層形成用組成物，其中所述含有(甲基)丙烯酸酯系官能基及非極性官能基之聚合物包含以下化學式1之重複單元： 其中，在化學式1中，R1為氫或碳數為1至20之烷基，R2為氫、碳數為1至20之烷基、聚酯基或聚醚基，且n為1 至300之整數。
  3. 如申請專利範圍第1項所述之切割膜黏著層形成用組成物，其中所述含有至少一個氟之(甲基)丙烯酸酯系聚合物包含經碳數為1至10之全氟烷基或碳數為1至10之氟化烯基取代的(甲基)丙烯酸酯系聚合物。
  4. 如申請專利範圍第1項所述之切割膜黏著層形成用組成物，其中所述含有反應性官能基之矽改質之(甲基)丙烯酸酯系聚合物包含經至少一個由以下所構成的族群中選出之反應性官能基取代之矽改質之(甲基)丙烯酸酯系聚合物：羥基、碳數為1至10之伸烷基醇、環氧基、胺基、巰基或羧基。
  5. 如申請專利範圍第1項所述之切割膜黏著層形成用組成物，其中所述聚合物添加劑更包括至少一種由以下所構成的族群中選出之有機溶劑：醇、醚、乙酸酯或酮。
  6. 如申請專利範圍第5項所述之切割膜黏著層形成用組成物，其中以1重量%至50重量%之所述有機溶劑計，所述含有(甲基)丙烯酸酯系官能基及非極性官能基之聚合物及所述含有反應性官能基之矽改質之(甲基)丙烯酸酯系聚合物的酸值分別為10毫克KOH/克至50毫克KOH/克。
  7. 如申請專利範圍第1項所述之切割膜黏著層形成用組成物， 其中所述黏著黏合劑包含未經取代或經至少一個由羥基、異氰酸酯基、乙烯基以及(甲基)丙烯酸酯基所構成的族群中選出之官能基取代的(甲基)丙烯酸酯系聚合物或(甲基)丙烯酸酯系共聚物。
  8. 如申請專利範圍第1項所述之切割膜黏著層形成用組成物，其中所述黏著黏合劑包含添加有丙烯酸酯之嵌入黏著黏合劑，所述嵌入黏著黏合劑具有碳碳雙鍵作為(甲基)丙烯酸酯樹脂之側鏈。
  9. 如申請專利範圍第1項所述之切割膜黏著層形成用組成物，其中所述黏著黏合劑包含重量平均分子量為100,000至1,500,000之聚合物樹脂。
  10. 如申請專利範圍第1項所述之切割膜黏著層形成用組成物，其中所述光起始劑包含至少一種由以下所構成的族群中選出之物質：安息香及其烷基醚、苯乙酮、蒽醌、硫代黃嘌呤、縮酮、二苯甲酮、α-胺基苯乙酮、氧化醯基膦以及肟酯。
  11. 如申請專利範圍第1項所述之切割膜黏著層形成用組成物，其中以100重量份所述黏著黏合劑計，所述切割膜黏著層形成用組成物包括0.01重量份至8重量份所述光起始劑。
  12. 如申請專利範圍第1項所述之切割膜黏著層形成用組成物，更包括固化劑。
  13. 如申請專利範圍第12項所述之切割膜黏著層形成用組成物，其中所述固化劑包含至少一種由以下所構成的族群中選出之物質：異氰酸酯化合物、氮丙啶化合物、環氧化合物以及金屬螯合化合物。
  14. 如申請專利範圍第12項所述之切割膜黏著層形成用組成物，其中以100重量份所述黏著黏合劑計，所述切割膜黏著層形成用組成物包括0.1重量份至30重量份所述固化劑。
  15. 一種切割膜，包括基底膜及形成於所述基底膜之至少一側上之黏著層，其中所述黏著層包括如申請專利範圍第1項所述之切割膜黏著層形成用組成物。
  16. 如申請專利範圍第15項所述之切割膜，其中所述基底膜之厚度為10微米至200微米，且所述黏著層之厚度為0.5微米至50微米。
  17. 一種切割晶片接合膜，包括如申請專利範圍第15項所述之切割膜，及形成於所述切割膜之至少一側上之接合層。
  18. 一種切割半導體晶圓之方法，包括以下步驟：進行預處理，藉由部分處理包括如申請專利範圍第17項所述之切割晶片接合膜及層壓於所述切割晶片接合膜之至少一側上之晶圓的半導體晶圓，以使得所述半導體晶圓完全切削或所述半導體晶圓可切削；在所述預處理之後擴展所述半導體晶圓；以及 將UV照射至擴展之所述半導體晶圓的基底膜，且拾取藉由切削所述半導體晶圓分開之個別晶片。
TW103144041A 2013-12-19 2014-12-17 切割膜黏著層形成用組成物、切割膜、切割晶片接合膜及切割半導體晶圓之方法 TWI534227B (zh)

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