TWI664257B - 半導體用黏著劑組成物、半導體用黏著膜以及切晶接合膜 - Google Patents

半導體用黏著劑組成物、半導體用黏著膜以及切晶接合膜 Download PDF

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TWI664257B
TWI664257B TW105113494A TW105113494A TWI664257B TW I664257 B TWI664257 B TW I664257B TW 105113494 A TW105113494 A TW 105113494A TW 105113494 A TW105113494 A TW 105113494A TW I664257 B TWI664257 B TW I664257B
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Taiwan
Prior art keywords
adhesive
film
resin
semiconductor
epoxy resin
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TW105113494A
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TW201704425A (zh
Inventor
金熹正
金思拉
金丁鶴
南承希
曺正鎬
李光珠
金榮國
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南韓商Ｌｇ化學股份有限公司
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Abstract

本發明是關於一種半導體用黏著劑組成物，包含：玻璃轉化溫度為-10℃至20℃之熱塑性樹脂；含有軟化點為70℃或大於70℃的酚樹脂之固化劑；固體環氧樹脂；以及液體環氧樹脂，其中固體環氧樹脂及液體環氧樹脂的總含量對熱塑性樹脂之重量比為1.6至2.6；一種包含半導體用黏著劑組成物之半導體用黏著膜；一種包含含半導體用黏著劑組成物之黏著層的切晶接合膜以及一種使用切晶接合膜切割半導體晶圓之方法。

Description

半導體用黏著劑組成物、半導體用黏著膜以及切晶接合膜
相關申請案的交叉引用
本申請案主張2015年4月29日在韓國智慧財產局申請的韓國專利申請案第10-2015-0060690號之權益，其揭露內容以全文引用的方式併入本文中。
本發明是關於一種半導體用黏著劑組成物、半導體用黏著膜以及切晶接合膜，且更特定言之，是關於具有低黏度，且仍具有高彈性、極佳機械特性以及高黏著強度的半導體用黏著劑組成物、半導體用黏著膜以及切晶接合膜。
最近，隨著電子裝置朝向小型化、高性能以及大容量之趨勢增加，對於高密度及高度整合半導體封裝之需求已快速增加，且因此半導體晶片之尺寸變得愈來愈大，且為了提高整合程度，愈來愈使用多級堆疊晶片之堆疊封裝方法。
在此類多級堆疊結構中，為了固定安置有電力連接下部 晶片與基板之下部接線的空間，在下部晶片與上部晶片之間的界面處引入隔片。在引入用於固定空間的此類隔片之情況下，封裝之總厚度變厚且增加了附接隔片之獨立過程。
為了解決問題，最近，使用一種填充諸如來自導線及類似物之不均勻度之方法，所述方法使用在高溫下具有低黏度之黏著劑代替隔片。然而，存在具有低黏度之黏著劑可能不確保高彈性且具有高斷裂伸長率之限制。另外，若黏著劑自身之彈性減小，則由於切割晶圓時產生之熱量，黏著劑可能經軟化而部分產生毛刺，且因此其可能污染晶圓，或可能通過與下部支撐膜之黏著劑混合使用，因此降低後續拾取效率。
另外，最近，由於半導體晶片變得較薄，存在晶片在現有刀片切割方法中損壞，因此降低產率之問題，且為了解決此問題，已推薦首先用刀片切割半導體晶片且接著拋光之製備方法。黏著劑應能夠經由低溫下之擴展方法切割以應用於此類製備方法。然而，具有低延展性之黏著劑在室溫下不易於切割，且當在切割之後使其在室溫下靜置時，由於低延展性而出現再黏著，因此降低半導體晶片之產率。
本發明之一個目標為提供一種具有低黏度，且仍具有高彈性、極佳機械特性以及高黏著強度之半導體用黏著劑組成物。
本發明之另一目標為提供一種具有低黏度，且仍具有高彈性、極佳機械特性以及高黏著強度之半導體用黏著膜。
本發明之另一目標為提供一種具有低黏度，且仍具有高彈性、極佳機械特性以及高黏著強度，且因此可預防毛刺產生且實現高拾取效率之切晶接合膜。
本發明之另一目標為提供一種使用切晶接合膜切割半導體晶圓之方法。
本文提供一種半導體用黏著劑組成物，包含玻璃轉化溫度為-10℃至20℃之熱塑性樹脂；含有軟化點為70℃或大於70℃的酚樹脂之固化劑；固體環氧樹脂；以及液體環氧樹脂，其中固體環氧樹脂及液體環氧樹脂的總含量對熱塑性樹脂之重量比為1.6至2.6。
在半導體用黏著劑組成物中，固體環氧樹脂及液體環氧樹脂之總含量對熱塑性樹脂之重量比可為1.7至2.5。
在半導體用黏著劑組成物中，酚樹脂對熱塑性樹脂、酚樹脂以及液體環氧樹脂的總重量之重量比可為0.280或大於0.280，或0.300至0.600。
液體環氧樹脂在25℃下之黏度可為500毫帕．秒至20,000毫帕．秒。
液體環氧樹脂之環氧當量可為100至1,000。
酚樹脂可具有80公克/當量至400公克/當量之羥基當量及70℃至160℃之軟化點。
酚樹脂之羥基當量可為100公克/當量至178公克/當量。
酚樹脂之軟化點可為大於100℃且為小於160℃，或105℃至150℃。
液體環氧樹脂與酚樹脂之重量比可為0.5至1.5。
固體環氧樹脂可包含由以下各者所構成的族群中選出之一或多種類型之樹脂：聯苯類環氧樹脂、雙酚A環氧樹脂、雙酚F環氧樹脂、甲酚酚醛環氧樹脂(cresol novolac epoxy resin)、酚醛環氧樹脂(phenol novolac epoxy resin)、四官能性環氧樹脂、三酚甲烷型環氧樹脂(triphenolmethane type of epoxy resin)、烷基改性三酚甲烷型環氧樹脂、萘型環氧樹脂、二環戊二烯型環氧樹脂以及二環戊二烯改性酚型環氧樹脂。
固體環氧樹脂之平均環氧當量可為100至1,000。
固體環氧樹脂之軟化點可為50℃至120℃。
熱塑性樹脂可包含由以下各者所構成的族群中選出之一或多種類型之聚合物樹脂：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、反應性丁二烯丙烯腈共聚物橡膠以及(甲基)丙烯酸酯類樹脂。
(甲基)丙烯酸酯類樹脂可為包含含有環氧類官能基的(甲基)丙烯酸酯類重複單元且玻璃轉化溫度為-10℃至20℃之(甲基)丙烯酸酯類樹脂。
(甲基)丙烯酸酯類樹脂可包含0.1重量%至10重量%的含有環氧類官能基之(甲基)丙烯酸酯類重複單元。
固化劑可更包含由以下各者所構成的族群中選出之一或多種類型之化合物：胺類固化劑及酸酐類固化劑。
半導體用黏著劑組成物可更包含離子清除劑，所述離子清除劑包含金屬氧化物，包含由以下各者所構成的族群中選出之一或多種金屬：鋯、銻、鉍、鎂以及鋁；多孔矽酸鹽；多孔鋁矽酸 鹽；或沸石。
半導體用黏著劑組成物可更包含由以下各者所構成的族群中選出之一或多種類型之固化催化劑：磷化合物、磷-硼化合物以及咪唑類化合物。
半導體用黏著劑組成物可更包含由以下各者所構成的族群中選出之一或多種類型之添加劑：偶合劑及無機填充劑。
半導體用黏著劑組成物可更包含10重量%至90重量%之有機溶劑。
另外，本文提供包含上文闡述的半導體用黏著劑組成物之半導體用黏著膜。
黏著膜的厚度可為1微米至300微米。另外，黏著膜的厚度可為1微米或大於1微米、3微米或大於3微米、5微米或大於5微米或10微米或大於10微米。另外，黏著膜的厚度可為300微米或小於300微米、100微米或小於100微米、90微米或小於90微米或70微米或小於70微米。
半導體用黏著膜可包含：連續相基底，包含玻璃轉化溫度為-10℃至20℃之熱塑性樹脂、含有軟化點為70℃或大於70℃的酚樹脂之固化劑以及液體環氧樹脂；及分散於連續相基底中之固體環氧樹脂。
固體環氧樹脂及液體環氧樹脂之總含量對熱塑性樹脂之重量比可為1.6至2.6、1.7至2.5、1.75至2.4或1.8至2.3。
在連續相基底中，酚樹脂對熱塑性樹脂、酚樹脂以及液體環氧樹脂之總重量之重量比可為0.280或大於0.280，或0.300至0.600。
另外，半導體用黏著膜可為晶粒接合膜。因此，半導體用黏著膜可包含：包含連續相基底之黏著層，所述連續相基底包含玻璃轉化溫度為-10℃至20℃之熱塑性樹脂、含有軟化點為70℃或大於70℃的酚樹脂之固化劑以及液體環氧樹脂；及分散於連續相基底作者固體環氧樹脂以及形成於黏著層的一側上之離型膜。
在室溫下在半導體用黏著膜的5%至10%伸長率下產生的模數可為50兆帕(MPa)或大於50兆帕。
另外，在室溫下的半導體用黏著膜之伸長率可為500%或小於500%。
另外，半導體用黏著膜可具有在110℃之溫度下1,000帕．秒至4,000帕．秒之熔融黏度及5弧度/秒之剪切率。
晶粒接合膜可更包含分散於連續相基底中之無機填充劑。
本文亦提供切晶接合膜，包含基底層；形成於基底膜上之黏性層；以及形成於黏性層上的包含半導體用黏著劑組成物之黏著層。
在室溫下在黏著層的5%至10%伸長率下產生之模數可為50兆帕或大於50兆帕。
另外，黏著層在室溫下之伸長率可為500%或小於500%。
基底膜的厚度為10微米至200微米，黏性層的厚度為1微米至600微米、3微米至500微米或5微米至300微米，且黏著膜的厚度為1微米至300微米。另外，黏著膜的厚度可為1微米或大於1微米、3微米或大於3微米、5微米或大於5微米或10微米或大於10微米。另外，黏著膜的厚度可為300微米或小於300 微米、100微米或小於100微米、90微米或小於90微米或70微米或小於70微米。
本文亦提供一種切割半導體晶圓之方法，包含以下步驟：部分預處理包含切晶接合膜之半導體晶圓；在切晶接合膜之至少一側上層合晶圓以使得經完全切割或可切割；以及向預處理半導體晶圓之基底膜照射UV且拾取藉由半導體切割分離之個別晶片。
根據本發明，提供一種具有低黏度且仍具有高彈性、極佳機械特性以及高黏著強度之半導體用黏著劑組成物及半導體用黏著膜，一種具有低黏度且仍具有高彈性、極佳機械特性以及高黏著強度且可預防毛刺產生且實現高拾取效率之切晶接合膜，以及一種使用切晶接合膜切割半導體晶圓之方法。
半導體用黏著劑組成物及半導體用黏著膜具有低黏度且仍具有高斷裂強度及低斷裂伸長率，且因此可應用於非接觸型黏著劑切割，例如DBG(Dicing before Grinding；研磨前切割)，以及使用刀片之晶圓切割，且甚至在低溫下具有極佳可切割性，且因此即使使其在室溫下靜置，再黏著之可能性變低，因此增加半導體製造方法中之可靠性及效率。
另外，半導體用黏著劑組成物或自其製備之黏著劑或黏著膜可確保改進的彈性及高機械特性，因此預防包含其之切晶接合膜及使用切晶接合膜切割半導體晶圓之方法中之毛刺產生，進一步增加切割方法之中拾取效率，且確保低溫及高溫下之高可切割性。
現將詳細解釋根據本發明之特定實施例之半導體用黏著劑組成物、晶粒接合膜、切晶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，提供一種半導體用黏著劑組成物，包含：玻璃轉化溫度為-10℃至20℃之熱塑性樹脂；含有軟化點為70℃或大於70℃的酚樹脂之固化劑；固體環氧樹脂；以及液體環氧樹脂，其中固體環氧樹脂及液體環氧樹脂之總含量對熱塑性樹脂之重量比為1.6至2.6。
本發明人對可用於黏著或封裝半導體裝置之組分進行研究，經由實驗確認黏著劑或使用以上實施例之半導體用黏著劑組成物製備之黏著膜可應用於半導體晶片之多級堆疊結構之封裝以實現更穩定結構及極佳機械特性，如耐熱性、抗衝擊性以及類似特性，且預防回流裂紋及類似物，且特定言之，即使長時間暴露於半導體製造方法中施加之高溫條件，可大體上不產生空隙，且完成本發明。
亦經由實驗確認由以上實施例之半導體用黏著劑組成物製備之黏著膜具有低黏度且仍具有高斷裂強度及低斷裂伸長率，且因此可應用於非接觸型黏著劑切割，例如DBG(研磨前切割)，以及使用刀片之晶圓切割，且甚至在低溫下具有極佳可切割性，且因此即使使其在室溫下靜置，再黏著之可能性變低，因此增加半導 體製造方法中之可靠性及效率，且完成本發明。
在半導體用黏著劑組成物中，固體環氧樹脂及液體環氧樹脂之總含量對熱塑性樹脂之重量比可為1.6至2.6、1.7至2.5、1.75至2.4或1.8至2.3。
由於半導體用黏著劑組成物包含固體環氧樹脂及液體環氧樹脂相比於熱塑性樹脂之上文闡述的範圍，由半導體用黏著劑組成物製備之黏著膜可具有高溫下的低黏度，且仍實現高彈性、極佳機械特性以及高黏著強度。
若固體環氧樹脂及液體環氧樹脂之總含量對熱塑性樹脂之重量比低於上文闡述的範圍，則由半導體用黏著劑組成物製備之黏著膜可展現高溫下的高黏度或展現低斷裂強度及高斷裂伸長率，且高溫剪切力亦可降低，且因此可能不充分地確保可切割性。
另外，若固體環氧樹脂及液體環氧樹脂之總含量對熱塑性樹脂之重量比大於2.6，則在室溫下的由半導體用黏著劑組成物製備的黏著膜之5%至10%伸長率下產生之模數可能變得顯著較高，或黏著膜在室溫下之伸長率可能顯著降低，因此在很大程度上抑制可加工性。另外，若在使用自其製備之黏著膜製造的切晶接合膜中，固體環氧樹脂及液體環氧樹脂之總含量對熱塑性樹脂之重量比大於2.6，則黏度增加速率可在固化方法中顯著增加，且因此可能難以移除膜內部之空隙，其可能阻礙半導體封裝之可靠性。
同時，環氧樹脂可連同玻璃轉化溫度為-10℃至20℃之熱塑性樹脂及含有軟化點為70℃或大於70℃的酚樹脂之固化劑形成黏著劑組分之基底(或基質)，且其允許半導體用黏著劑組成物或自其製備之黏著劑或黏著膜具有低黏度且仍具有高斷裂強度及低 斷裂伸長率。
酚樹脂可連同液體環氧樹脂及玻璃轉化溫度為-10℃至20℃之熱塑性樹脂形成黏著劑組分之基底(或基質)，其中酚樹脂較佳以黏著劑組分之基底中之某一水準以上的含量包含在內。特定言之，酚樹脂對熱塑性樹脂、酚樹脂以及液體環氧樹脂之總重量之重量比可為0.280或大於0.280、0.300或大於0.300，或0.300至0.600。
若半導體用黏著劑組成物中的酚樹脂對熱塑性樹脂、酚樹脂以及液體環氧樹脂之總重量之重量比小於0.280，則半導體用黏著膜可能未得到足夠固化程度，因此降低耐熱性，在室溫下在由半導體用黏著劑組成物製備的黏著膜之5%至10%伸長率下產生之模數可能顯著降低，且黏著膜在室溫下之伸長率可能顯著增加。另外，在使用黏著膜製造之切晶接合膜中，可能經由切割方法過度產生毛刺，且高溫剪切力亦可能減小，且因此可能不充分地確保可切割性。
液體環氧樹脂可連同玻璃轉化溫度為-10℃至20℃之熱塑性樹脂及含有酚樹脂之固化劑形成黏著劑組分之基底(或基質)，且允許黏著膜具有相對低黏度且仍具有針對半導體最佳化之極佳黏著強度及流動特性，且因此可有利於初始階段固化之界面處及晶粒黏接方法中之空隙移除。
液體環氧樹脂之特定種類及特性不顯著受限，但舉例而言，液體環氧樹脂在25℃下之黏度可為500毫帕．秒至20,000毫帕．秒。另外，液體環氧樹脂之環氧當量可為100至1,000。
在以上實施例之半導體用黏著劑組成物中，液體環氧樹 脂與酚樹脂之重量比可為0.5至1.5。
若液體環氧樹脂與酚樹脂之重量比過高，則半導體用黏著劑組成物或自其製備之黏著劑或黏著膜之斷裂強度可能顯著增加，在室溫下之拉伸模量可能降低，且低溫切割方法中之可切割性或效率可能降低。
另外，若液體環氧樹脂與酚樹脂之重量比過低，則在室溫下之伸長率下產生之模數可能變得過高，或在室溫下之伸長率可能顯著降低，因此顯著降低最終產物之產率，且半導體用黏著劑組成物或自其製備之黏著劑或黏著膜可能不具有與晶圓的足夠黏著，因此在製造方法中在晶圓與黏著膜之間產生去接合。
液體環氧樹脂之特定種類及特性不顯著受限，但舉例而言，液體環氧樹脂在25℃下之黏度可為500毫帕．秒(mPa．s)至20,000毫帕．秒。另外，液體環氧樹脂之環氧當量可為100至1,000。
同時，包含於半導體用黏著劑組成物中之固化劑可包含軟化點為70℃或大於70℃之酚樹脂。酚樹脂之軟化點可為70℃或大於70℃、80℃或大於80℃、70℃至160℃、大於100℃及160℃或小於160℃，或105℃至150℃。
以上實施例之半導體用黏著劑組成物可包含具有相對高軟化點之酚樹脂，且軟化點為70℃或大於70℃、80℃或大於80℃、70℃至160℃或大於100℃及160℃或小於160℃，或105℃至150℃之酚樹脂可連同液體環氧樹脂及玻璃轉化溫度為-10℃至20℃之熱塑性樹脂形成黏著劑組分之基底(或基質)，且對於由以上實施例之半導體用黏著劑組成物製備之黏著膜提供較高拉伸模量及室溫下的極佳黏著強度以及針對半導體最佳化之流動特性。
相反，若酚樹脂之軟化點小於上文闡述的範圍，則由以上實施例之半導體用黏著劑組成物製備之黏著膜在室溫下之拉伸模量可能降低或在室溫下之伸長率可能顯著增加，且黏著膜之熔融黏度可能減少或模數可能降低，且因此可能由切割方法中產生之熱量產生更多毛刺或可切割性或拾取效率可能降低。另外，若接合黏著膜之方法或黏著膜長期暴露於高溫條件，則可能產生大量滲出。
另外，酚樹脂之羥基當量可為80公克/當量至400公克/當量、90公克/當量至250公克/當量、100公克/當量至178公克/當量或210公克/當量至240公克/當量。由於酚樹脂具有上文闡述的羥基當量範圍，固化程度可甚至在短固化時間下增加，因此由以上實施例之半導體用黏著劑組成物製備之黏著膜獲得較高拉伸模量及極佳室溫下的黏著強度。
為了控制半導體用黏著劑組成物之固化程度或增加黏著效能及類似效能，黏著劑組成物可包含固體環氧樹脂。
固體環氧樹脂之特定實例可包含由以下各者所構成的族群中選出之一或多種類型之聚合物樹脂：聯苯類環氧樹脂、雙酚A環氧樹脂、雙酚F環氧樹脂、甲酚酚醛環氧樹脂、酚醛環氧樹脂、四官能性環氧樹脂、三酚甲烷型環氧樹脂、烷基改性三酚甲烷型環氧樹脂、萘型環氧樹脂、二環戊二烯型環氧樹脂以及二環戊二烯改性酚型環氧樹脂。
固體環氧樹脂之軟化點可為50℃至120℃。若固體環氧樹脂之軟化點過低，則半導體用黏著劑組成物之黏著強度可能增加而減少切割之後的晶片拾取，而若固體環氧樹脂之軟化點過高， 則半導體用黏著劑組成物之可流動性可能降低，且由半導體用黏著劑組成物製備之黏著膜之黏著強度可能降低。
固體環氧樹脂之環氧當量可為100至1,000。
如上文所解釋，半導體用黏著劑組成物可包含玻璃轉化溫度為-10℃至20℃之熱塑性樹脂。
熱塑性樹脂之實例不特定受限，但例如可包含聚醯亞胺、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、反應性丁二烯丙烯腈共聚物橡膠、(甲基)丙烯酸酯類樹脂、其兩種或大於兩種的混合物，或其兩種或大於兩種的共聚物。
特定言之，(甲基)丙烯酸酯類樹脂可為包含含環氧類官能基之(甲基)丙烯酸酯類重複單元且玻璃轉化溫度為-10℃至20℃之(甲基)丙烯酸酯類樹脂。
藉由使用包含含環氧類官能基之(甲基)丙烯酸酯類重複單元且玻璃轉化溫度為-10℃至20℃之(甲基)丙烯酸酯類樹脂，實施例之半導體用黏著劑組成物可用於黏著半導體或黏著包含於半導體中之組分，或用於半導體封裝，且在用於超薄晶圓之多級堆疊之情況下，可提供可確保高抗衝擊性且在半導體製造之後改良電特性之半導體用黏著膜或半導體封裝用黏著膜。
環氧類官能基可在構成(甲基)丙烯酸酯類樹脂之主鏈的重複單元處經取代一或多次。
環氧類官能基可包含環氧基或縮水甘油基。
包含0.1重量%至10重量%含量的含環氧類官能基之(甲基)丙烯酸酯類重複單元之(甲基)丙烯酸酯類樹脂之玻璃轉化溫度 可為-10℃至20℃，或-5℃至15℃。藉由使用具有上文闡述的玻璃轉化溫度之(甲基)丙烯酸酯類樹脂，半導體用黏著劑組成物可具有足夠流動性且最後製備之黏著膜可確保高黏著強度，且其易於製備呈薄膜及類似物形式的半導體用黏著劑組成物。
以上實施例之半導體用黏著劑組成物可包含按100重量份酚樹脂計的10重量份至1,000重量份熱塑性樹脂，及10重量份至1,000重量份固體環氧樹脂。
若熱塑性樹脂之含量過低，則樹脂組成物固化之後的模數可快速增加，且因此難以期望基板與晶圓之間的應力鬆弛效應。另外，若熱塑性樹脂之含量過高，則B階段之組合物黏度可能增加，且因此晶粒黏接方法中與基板之黏著可減少，且固化方法期間的空隙移除可變得困難，因此降低方法及最終產物之可靠性。
若含有酚樹脂之固化劑之含量過低，則可能難以確保足夠耐熱性。若含有酚樹脂之固化劑之含量過高，則即使固化完成，未反應的酚基團可能殘留而增大吸濕性，且因此，在半導體封裝方法中之濕氣吸收之後的回流過程中，可能引起基板與黏著劑之間的分層。
固化劑可更包含由以下各者所構成的族群中選出之一或多種類型之化合物：胺類固化劑及酸酐類固化劑。固化劑的用量可考慮最終製備之黏著膜之特性及類似因素恰當地選擇，且舉例而言，其可以按100重量份環氧樹脂計以10重量份至700重量份或30重量份至300重量份之量使用。
半導體用黏著劑組成物可更包含固化催化劑。
固化催化劑用於促進固化劑之作用或半導體用黏著劑組 成物之固化，且可使用已知用於製造半導體用黏著膜及類似物之任何固化催化劑而無顯著限制。舉例而言，作為固化催化劑，可使用由以下各者所構成的族群中選出之一或多種：磷化合物、硼化合物、磷-硼化合物以及咪唑類化合物。固化催化劑的用量可考慮黏著膜之特性及類似因素恰當地選擇，且舉例而言，其可以按100重量份液體及固體環氧樹脂、(甲基)丙烯酸酯類樹脂以及酚樹脂計以0.5重量份至10重量份的量使用。
半導體用黏著膜可更包含離子清除劑，所述離子清除劑包含金屬氧化物，其包含由以下各者所構成的族群中選出之一或多種金屬：鋯、銻、鉍、鎂以及鋁；多孔矽酸鹽；多孔鋁矽酸鹽；或沸石。
包含由鋯、銻、鉍、鎂以及鋁所構成的族群中選出之一或多種金屬之金屬氧化物之實例可包含氧化鋯、氧化銻、氧化鉍、氧化鎂、氧化鋁、銻鉍類氧化物、鋯鉍類氧化物、鋯鎂類氧化物、鎂鋁類氧化物、銻鎂類氧化物、銻鋁類氧化物、銻鋯類氧化物、鋯鋁類氧化物、鉍鎂類氧化物、鉍鋁類氧化物或其兩種或大於兩種之混合物。
離子清除劑可起吸附半導體用黏著劑組成物或自其製備之黏著膜內部存在之金屬離子或鹵素離子及類似物之作用，且因此可改良與黏著膜接觸之電線之電可靠性。
半導體用黏著劑組成物中之離子清除劑之含量不顯著受限，但考慮與過渡金屬離子之反應性、可加工性以及由樹脂組成物製造之黏著膜之特性，其可以按半導體用黏著劑組成物之總固體重量計以0.01重量%至20重量%，較佳0.01重量%至10重量%之 含量包含在內。
半導體用黏著劑組成物可更包含0.1重量%至50重量%，或0.1重量%至10重量%之有機溶劑。可考慮半導體用黏著劑組成物之特性或最終製備之黏著膜之特性或其製備方法確定有機溶劑之含量。
半導體用黏著膜可更包含由偶合劑及無機填充劑所構成的族群中選出之一或多種添加劑。偶合劑及無機填充劑之實例不受特定限制，且可使用已知可用於半導體封裝用黏著劑中之組分而無顯著限制。
根據本發明之另一實施例，提供包含以上半導體用黏著劑組成物之半導體用黏著膜。
黏著膜的厚度可為1微米至300微米。另外，黏著膜的厚度可為1微米或大於1微米、3微米或大於3微米、5微米或大於5微米或10微米或大於10微米。另外，黏著膜的厚度可為300微米或小於300微米、100微米或小於100微米、90微米或小於90微米或70微米或小於70微米。
半導體用黏著膜可應用於半導體晶片之多級堆疊結構之封裝以實現更穩定結構及極佳機械特性，如耐熱性、抗衝擊性以及類似特性，且預防回流裂紋及類似物，且特定言之，即使長時間暴露於半導體製造方法中施加之高溫條件，可大體上不產生空隙。
另外，半導體用黏著膜具有高斷裂強度及低斷裂伸長率，且因此可應用於非接觸型黏著劑切割，例如DBG(研磨前切割)，以及使用刀片之晶圓切割，且甚至在低溫下具有極佳可切割性，且因此即使使其在室溫下靜置，再黏著之可能性變低，因此增加半導 體製造方法中之可靠性及效率。
半導體用黏著膜可包含：連續相基底，其包含玻璃轉化溫度為-10℃至20℃之熱塑性樹脂、含有軟化點為70℃或大於70℃的酚樹脂之固化劑以及液體環氧樹脂；及分散於連續相基底中之固體環氧樹脂。
固體環氧樹脂及液體環氧樹脂之總含量對熱塑性樹脂之重量比可為1.6至2.6，或1.7至2.5、1.75至2.4或1.8至2.3。
在半導體用黏著膜中，若固體環氧樹脂及液體環氧樹脂之總含量對熱塑性樹脂之重量比低於上文闡述的範圍，則其可展現高溫下的高黏度或展現低斷裂強度及高斷裂伸長率，且高溫剪切力亦可降低，且因此可能不充分地確保可切割性。
另外，在半導體用黏著膜中，若固體環氧樹脂及液體環氧樹脂之總含量對熱塑性樹脂之重量比大於2.6，則在室溫下的黏著膜之5%至10%伸長率下產生之模數可能變得顯著較高，或黏著膜在室溫下之伸長率可能顯著降低，因此在很大程度上抑制可加工性。另外，若在使用半導體用黏著膜製造的切晶接合膜中，固體環氧樹脂及液體環氧樹脂之總含量對熱塑性樹脂之重量比大於2.6，則黏度增加速率可在固化過程中顯著增加，且因此可能難以移除膜內部之空隙，其可能阻礙半導體封裝之可靠性。
在包含於半導體用黏著膜中之連續相中，酚樹脂對熱塑性樹脂、酚樹脂以及液體環氧樹脂之總重量之重量比可為0.280或大於0.280、0.300或大於0.300或0.300至0.600。
若半導體用黏著膜中的酚樹脂對熱塑性樹脂、酚樹脂以及液體環氧樹脂之總重量之重量比小於0.280，則在室溫下在黏著 膜之5%至10%伸長率下產生之模數可能顯著降低，且黏著膜在室溫下之伸長率仍可能顯著增加。另外，在使用黏著膜製造之切晶接合膜中，可能經由切割方法過度產生毛刺，且高溫剪切力亦可減小，且因此可能不充分地確保可切割性。
半導體用黏著膜可為晶粒接合膜。因此，半導體用黏著膜可包含：包含連續相基質之黏著層，所述連續相基質包含玻璃轉化溫度為-10℃至20℃之熱塑性樹脂、含有軟化點為70℃或大於70℃的酚樹脂之固化劑以及液體環氧樹脂；及分散於連續相基質的固體環氧樹脂以及形成於黏著層的一側上之離型膜。
在室溫下在半導體用黏著膜的5%至10%伸長率下產生的模數可為50兆帕或大於50兆帕。由於在室溫下在半導體用黏著膜之5%至10%伸長率下產生之模數為50兆帕或大於50兆帕，或50兆帕至300兆帕，以上實施例之黏著膜可容易地應用於非接觸型切割方法，例如DBG(研磨前切割)，以及使用刀片之晶圓切割方法，且因此甚至在低溫下具有極佳可切割性。
若在室溫下在半導體用黏著膜之5%至10%伸長率下產生之模數小於50兆帕，則即使在低溫下進行擴展，可切割性可能不足夠；若使其在室溫下靜置，則可出現再黏著；且由於當切割黏著膜所接合的晶圓時產生之熱量，黏著劑可經軟化而在黏著膜中產生毛刺，因此污染半導體晶片之電路側。
此外，半導體用黏著膜可具有500%或小於500%、50%至500%或100%至400%的室溫下之伸長率。由於半導體用黏著膜具有相對高彈性且仍展現低伸長率及低斷裂伸長率，其可甚至在低溫具有極佳可切割性，且可即使在應用非接觸型切割方法，例如 DBG(研磨前切割)以及使用刀片之晶圓切割方法時確保極佳可切割性。
同時，若半導體用黏著膜展現大於500%之伸長率，則即使在低溫下進行擴展，可切割性可能不足夠；若使其在室溫下靜置，則可能出現再黏著；且由於當切割黏著膜所接合的晶圓時產生之熱量，黏著劑可經軟化而在黏著膜中產生毛刺，因此污染半導體晶片之電路側。
另外，半導體用黏著膜具有在110℃之溫度下1,000帕．秒至4,000帕．秒之熔融黏度及5弧度/秒之剪切率。由於黏著膜在約110℃之溫度下具有相對低黏度，其可具有針對半導體最佳化之極佳黏著強度及流動特性，其可有利於初始階段固化之界面處及晶粒黏接方法中之空隙移除，且在晶粒黏接之後，可在不顯著影響黏著膜之形狀或特性的情況下平滑地實現接線向周圍空間中之滲透。
另外，由於半導體用黏著膜具有在110℃之溫度下1,000帕．秒至4,000帕．秒之熔融黏度及5弧度/秒之剪切率，即使長時間暴露於在半導體製造方法中應用之高溫條件，可大體上不產生空隙，且當應用於切晶接合膜及類似物時，可確保足夠高溫剪切力，因此確保極佳可切割性。
黏著膜可用作晶粒接合黏接膜(DAF)以將引線框或基板與晶粒黏接或將晶粒與晶粒黏接。因此，黏著膜可以晶粒接合膜、切晶接合膜以及類似形式處理。
晶粒接合膜可更包含分散於連續相基底中之無機填充劑。
實施例之半導體用黏著劑組成物之細節包括上文闡述的細節。
同時，根據本發明之另一實施例，提供一種切晶接合膜，包含基底膜；形成於基底膜上之黏性層；以及形成於黏性層上且包含上文闡述的半導體用黏著劑組成物之黏著層。
由於黏著層包含上文闡述的實施例之半導體用黏著劑組成物，切晶接合膜可具有極佳機械特性，如耐熱性、抗衝擊性以及類似特性、高黏著強度以及低吸濕性，因此預防濕氣蒸發、基板與晶粒接合膜之間的分層或由蒸發及類似因素所致的回流裂紋。
半導體用黏著劑組成物之細節如上文所解釋。
在室溫下在半導體用黏著膜的5%至10%伸長率下產生的模數可為50兆帕或大於50兆帕。
另外，在室溫下的半導體用黏著膜之伸長率可為500%或小於500%。
另外，半導體用黏著膜可具有在110℃之溫度下1,000帕．秒至4,000帕．秒之熔融黏度及5弧度/秒之剪切率。
包含於切晶接合膜中之基底膜之種類不受特別限制，且舉例而言，可使用塑膠膜或金屬箔以及本領域中已知之類似物。
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、聚丙烯無規共聚物、聚丙烯嵌段共聚物、均聚丙烯、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-離聚物共聚物、乙烯-乙烯醇共聚物、聚丁烯、苯乙烯共聚物或其兩種或大於兩種之混合物。
包含兩種或大於兩種聚合物之混合物之基底膜包含多層膜，其中各膜層包含上文闡述的聚合物，及包含兩種或大於兩種上文闡述的聚合物之單層膜。
基底膜之厚度不受特別限制，且通常，其形成為10微米至200微米，且較佳50微米至180微米的厚度。若厚度小於10微米，則存在切割方法中的切割深度之控制可能不穩定之問題，且若其大於200微米，則可能在切割方法中產生大量毛刺且伸長率可能減小，且因此可能不精確實現擴展方法。
基底膜視需要可經受一般物理或化學處理，如消光處理、電暈放電、底塗劑處理、交聯以及類似處理。
同時，黏性層可包含UV可固化黏著劑或熱可固化黏著劑。在使用UV可固化黏著劑之情況下，UV自基底膜側照射以增大黏著劑之黏結性及玻璃轉化溫度，因此降低黏著強度，且在使用熱可固化黏著劑之情況下，溫度經增加以降低黏著強度。
此外，UV可固化黏著劑可包含(甲基)丙烯酸酯類樹脂、UV可固化化合物、光引發劑以及交聯劑。
(甲基)丙烯酸酯類樹脂之重量平均分子量可為100,000至1,500,000，較佳200,000至1,000,000。若重量平均分子量小於100,000，則可塗佈性或黏結性可能降低，且因此殘餘物可能在分層時殘留於黏附物中，或可能出現黏著劑破壞。另外，若重量平均分子量大於1,500,000，則基底樹脂可能阻礙UV可固化化合物之反應，且因此存在未能有效減小剝離強度的擔憂。
(甲基)丙烯酸酯類樹脂之實例可包含(甲基)丙烯酸酯類單體及含可交聯官能基單體之共聚物。本文中，(甲基)丙烯酸酯類 單體之實例可包含(甲基)丙烯酸烷酯，特定言之具有碳數為1至12之烷基之單體，如(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)丙烯酸十二烷酯、(甲基)丙烯酸癸酯或其混合物。由於單體之烷基之碳數變為較高，最終共聚物之玻璃轉化溫度變為較低，且因此可根據所需玻璃轉化溫度選擇適當單體。
含可交聯官能基單體之實例可包含含羥基單體、含羧基單體、含氮單體或其混合物。含羥基化合物之實例可包含(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯以及類似物，含羧基化合物之實例可包含(甲基)丙烯酸酯及類似物，且含氮單體之實例可包含(甲基)丙烯腈、N-乙烯吡咯啶酮、N-乙烯己內醯胺以及類似物，但不限於此。
在(甲基)丙烯酸酯類樹脂中，可另外包含含碳-碳雙鍵的低分子量化合物，如乙酸乙烯酯、苯乙烯、丙烯腈以及類似物以改良其他官能性，如相容性及類似者。
UV可固化化合物之種類不受特別限制，且舉例而言，可使用重量平均分子量為500至300,000之多官能性化合物(例如多官能性丙烯酸胺基甲酸酯、多官能性丙烯酸酯單體或寡聚物以及類似物)。所屬領域中具通常知識者可易於根據所需用途選擇適當化合物。
UV可固化化合物之含量可為按100重量份上文闡述的基底樹脂計之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，則固化之後的黏 著性減少可能不充分且因此存在降低拾取的問題，且若其大於400重量份，則UV照射之前的黏著劑之黏結性可能不足夠，或可能不易於實現與離型膜分層及類似者。
光引發劑之種類不受特別限制，且可使用本領域中通常已知的光引發劑，其中含量可為按100重量份UV可固化化合物計之0.05重量份至20重量份。若光引發劑之含量小於0.05重量份，則藉由UV照射之固化反應可變得不足夠而降低拾取，且若其大於20重量份，則可在固化方法中之短單位下發生交聯反應，可能產生非反應UV可固化化合物以在黏附表面上產生殘餘物，或固化之後的剝離強度可能過度減小而降低拾取。
另外，包含於黏著劑部分中以提供黏著性及黏結性之交聯劑之種類亦不受特定限制，且可使用通常使用之交聯劑，如異氰酸酯類化合物、氮丙啶類化合物、環氧類化合物、金屬螯合劑類化合物以及類似物。交聯劑可以按100重量份基底樹脂計以2重量份至40重量份，較佳2重量份至20重量份之含量包含在內。若含量小於2重量份，則黏著劑之黏結性可能不充分，且若其大於20重量份，則UV照射之前的黏著性可能不充分，且因此存在晶片散佈及類似問題。
另外，在黏性層中，可更包含增黏劑，如松香樹脂、萜樹脂、酚樹脂、苯乙烯樹脂、脂族石油樹脂、芳族石油樹脂、脂族芳族共聚物石油樹脂以及類似物。
在基底膜上形成包含以上組分之黏性層的方法不受特別限制，且舉例而言，可使用在基底膜上直接塗佈黏著劑組成物以形成黏性層之方法，或首先在可剝離基底上塗佈黏著劑組成物以製 備黏性層，接著使用可剝離基底將黏性層轉錄至基底膜之方法及類似方法。
本文中，塗佈及乾燥黏著劑組成物之方法不特定受限，且舉例而言，可使用按原樣塗佈包含以上組分之組合物，或將其稀釋於適當有機溶劑中且藉由已知工具，如缺角輪塗佈機(comma coater)、凹版塗佈機、壓模塗佈機、反向塗佈機以及類似工具塗佈，且接著在60℃至200℃之溫度下乾燥溶劑10秒至30分鐘之方法。另外，在以上方法中，可另外進行老化過程以進行黏著劑之足夠交聯。
儘管黏性層之厚度不顯著受限，舉例而言，其可在1微米至600微米、3微米至500微米或5微米至300微米範圍內。
如上文所解釋，黏著層形成於黏性層上，且可包含上文闡述的實施例之半導體用黏著膜。半導體用黏著膜之細節包括上文解釋之細節。
儘管黏著層之厚度不顯著受限，舉例而言，其可為1微米至300微米。另外，黏著膜的厚度可為1微米或大於1微米、3微米或大於3微米、5微米或大於5微米，或10微米或大於10微米。另外，黏著膜的厚度可為300微米或小於300微米、100微米或小於100微米、90微米或小於90微米或70微米或小於70微米。
切晶接合膜可更包括形成於黏著層上之離型膜。可使用的離型膜之實例可包含一或多種類型之塑膠膜，如聚對苯二甲酸伸乙酯膜、聚四氟乙烯膜、聚乙烯膜、聚丙烯膜、聚丁烯膜、聚丁二烯膜、氯乙烯共聚物膜、聚醯亞胺膜以及類似物。
離型膜之表面可用醇酸樹脂類、矽類、氟類、不飽和酯類、聚烯烴類或蠟類脫模劑中的一或多者處理，其中耐熱性醇酸樹脂類、矽類或氟類脫模劑可為較佳的。
離型膜可通常形成為10微米至500微米，較佳約20微米至200微米的厚度，但不限於此。
製造上文闡述的切晶接合膜之方法不受特別限制，且舉例而言，可使用在基底膜上依序形成黏性部分、黏著劑部分以及離型膜之方法，或分開製備切割膜(基底膜+黏性部分)及在上面形成有晶粒接合膜或黏著劑部分之離型膜，接著將其層合之方法，及類似方法。
層合方法不受特別限制，且可使用熱軋層合或層壓，其中就連續方法之可能性及效率而言，熱軋層合較佳。熱軋層合可在10℃至100℃之溫度及0.1公斤力/平方公分至10公斤力/平方公分之壓力下進行，但不限於此。
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：部分預處理包含切晶接合膜之半導體晶圓；在切晶接合膜之至少一側上層合晶圓以使得經完全切割或可切割；以及向預處理半導體晶圓之基底膜照射UV且拾取藉由半導體切割分離之個別晶片。
切晶接合膜之細節包含以上解釋之細節。
除了關於切割方法步驟之細節，可使用用於半導體晶圓及類似物之切割方法之通常已知設備及方法而無特定限制。
用於切割半導體晶圓之方法可更包含在預處理之後擴展半導體晶圓之步驟。在此狀況下，遵循如下方法：將UV照射至經 擴展半導體晶圓之基底膜且拾取藉由半導體晶圓切割分離之個別晶片。
藉由使用包含切割膜之切晶接合膜，可能在半導體晶圓之切割方法期間產生之毛刺可經最小化，因此預防半導體晶片之污染且改良半導體晶片之可靠性及使用期限。
本發明之特定實施例將詳細解釋於以下實例中。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至實例5及比較實例1至比較實例3：製備半導體用黏著劑組成物及半導體用黏著膜] 實例1 (1)製備半導體用黏著劑組成物之溶液
40公克酚樹脂KH-6021(由大日本油墨化學工業公司(DIC Corporation)生產，雙酚A酚醛清漆樹脂，羥基當量121公克/當量，軟化點：125℃)(其為環氧樹脂固化劑)、38公克環氧樹脂EOCN-104S(由日本化藥有限公司(Nippon Kayaku Co.,Ltd.)生產，甲酚酚醛型環氧樹脂，環氧當量214公克/當量，軟化點：83℃)、50公克液體環氧樹脂RE-310S(由日本化藥有限公司生產，雙酚A環氧樹脂，環氧當量180公克/當量)、40公克熱塑性丙烯酸酯樹脂KG-3015(Mw：900,000，玻璃轉化溫度：10℃)、5公克矽烷偶合劑A-187(GE東芝有機矽公司(GE Toshiba Silicone)，γ-縮水甘油氧基丙基三甲氧基矽烷)、0.1公克固化促進劑2PZ(四國化學品公司(Shikoku Chemicals Corporation)，2-苯基咪唑)以及100公克填充劑SC-2050(雅都瑪公司(Admatec Corporation)，球形二 氧化矽，平均粒徑約400奈米)在甲基乙基酮溶劑中混合以獲得半導體用黏著劑組成物之溶液(固體含量20重量%)。
(2)製備晶粒接合膜
以上製備的半導體用黏著劑組成物之溶液塗佈於離型處理之聚對苯二甲酸伸乙酯膜(厚度38微米)上，且接著在110℃下乾燥3分鐘以獲得厚度為約60微米的半導體用黏著膜(晶粒接合膜)。
實例2至實例5
藉由與實例1相同之方法獲得半導體用黏著劑組合物之溶液(固體含量20重量%)及半導體用黏著膜(晶粒接合膜)，不同處在於施用下表1中所述之組分及量。
比較例1及比較例2
藉由與實例1相同之方法獲得半導體用黏著膜(晶粒接合膜)，除了使用下表1之組分及含量製備半導體用黏著劑組成物之溶液(甲基乙基酮20重量%濃度)。
- KH-6021：雙酚A酚醛清漆樹脂(大日本油墨化學工業公司，軟化點：125℃)
- GPH-103：聯苯酚醛清漆樹脂(日本化藥有限公司，軟化點：103℃)
- HE200C-17：聯苯酚醛清漆樹脂(空氣水有限公司(Air Water Co.,Ltd.)，軟化點：75℃)
- KPH-3065：xyloc A酚醛清漆酚樹脂(科隆化學有限公司(Kolon Chemical Co.,Ltd.)，羥基當量：180公克/當量，軟化點67℃)
- KG-3015P：丙烯酸酯類樹脂(包含3重量%甲基丙烯酸縮水甘油酯類重複單元，玻璃轉化溫度：10℃，重量平均分子量900,000)
- EOCN-104S：甲酚酚醛清漆環氧樹脂(日本化藥有限公司，環氧當量：180公克/當量，軟化點：90℃)
- RE-310S：雙酚A環氧液體樹脂(日本化藥，環氧當量：約180公克/當量，25℃下之黏度：約13,000毫帕．秒至17,000毫帕．秒)
[實驗實例：評估半導體用黏著膜之特性] 實驗實例1：熔融黏度之量測
分別在實例及比較例中獲得之黏著膜堆疊至650微米的厚度，且接著使用覆膜機(roll laminator)在60℃下層合。此後，各樣本以直徑為10毫米之圓形形狀形成，且接著在40℃至160℃ 之溫度範圍、1赫茲及5弧度之剪切率以及20℃/分鐘之溫度上升率下，使用TA公司(TA Corporation)之先進流變擴展系統(ARES)量測根據溫度之熔融黏度。
實驗實例2：評估室溫拉伸特性
為了量測分別在實例及比較例中獲得之黏著膜之拉伸特性，使用質構分析儀(穩定微系統有限公司(Stable Micro System,Ltd.))。特定言之，分別在實例及比較例中獲得之黏著膜切割為寬度15mm及長度100毫米之尺寸以製備樣品，且兩端均貼上膠帶而留下50毫米的樣品中心部分。另外，貼上膠帶的樣品之兩端固定於設備，且在以0.3毫米/秒之速度拉長時，繪製拉伸曲線。自拉伸曲線量測5%伸長率處之梯度值以測定模數，且量測樣品經完全切割時的時間以測定伸長率。
實驗實例3：觀測毛刺產生 (1)製造切割膜
75公克丙烯酸2-乙基己酯、10公克甲基丙烯酸2-乙基己酯以及15公克丙烯酸2-羥基乙酯在300公克丙烯酸乙酯溶劑中共聚合以獲得重量平均分子量為850,000的共聚物(玻璃轉化溫度：10℃)，且接著向其中添加10公克光固化性物質異氰酸丙烯醯酯化合物，因此獲得反應物。此後，混合10公克多官能性異氰酸酯寡聚物及1公克作為光引發劑之達若可(Darocur)TPO以製備UV可固化黏著劑組成物。
UV可固化黏著劑組成物塗佈於厚度為38微米的離型處理聚酯膜上以使得乾燥之後的厚度變為10微米，且在110℃下乾燥3分鐘。乾燥黏性層在厚度為100微米的聚烯烴膜上層合以製 造切割膜。
(2)製造切晶接合膜
在以上方法中獲得之黏性層及在實例及比較例中獲得之各黏著膜(寬度：18毫米，長度：10公分)經層合以製造切晶接合用多層黏著膜。
(3)量測毛刺產生速率
上文製備的各切晶接合膜使用100微米晶圓及晶圓環安裝器在50℃下層合，且使用切割設備在40K轉/分及20毫米/秒之速度下切割為10毫米×10毫米晶片尺寸，且接著確認晶粒上產生之毛刺數量以量測毛刺產生速率。
實驗實例4：評估高溫剪切力
在厚度為約600微米至700微米的晶圓之鏡面(mirror side)上，分別在實例及比較例中獲得之黏著膜在60℃之條件下層合，且晶圓分段為5毫米×5毫米的尺寸以製備具有晶粒尺寸之黏著膜。另外，10毫米×10毫米尺寸之70微米晶圓鏡在130℃下定位於熱板上，且接著晶粒接合膜在2公斤晶圓晶粒及2秒之條件下黏接，在125℃下進行固化1小時，且在175℃下再次進行固化2小時。
另外，使用晶粒剪切測試儀DAGE 4000，在250℃下以0.05毫米/秒的速度推動晶圓晶粒時量測力以量測高溫剪切力。
實驗實例5：評估可切割性
在實例1至實例4及比較例1及比較例2中獲得之黏著劑層合至切割膜，因此製造切晶接合膜。
使用預先切割為5毫米×5毫米尺寸的50微米厚度之8 吋晶圓及晶圓環安裝器，上文製備的各切晶接合膜在60℃下層合，且接著使其在室溫下靜置30分鐘。此後，切晶接合膜所層合之晶圓安裝於低溫腔室中，且在-10℃下以100毫米/秒的速度進行低溫擴展至5毫米之高度。另外，晶圓轉移至熱收縮裝置，且以1毫米/秒擴展至4毫米，且接著經加熱以使切割膜熱收縮。此後，確認晶圓在室溫下的切割比。
如表2中所示，製備實例1至實例5之黏著膜，使得固體環氧樹脂及液體環氧樹脂之總含量對熱塑性樹脂之重量比變為1.6至2.6，且這些黏著膜具有如下物理特性：50兆帕至150兆帕的在室溫下在5%至10%伸長率下產生之模數、在110℃之溫度下1,000帕．秒至4,000帕．秒之熔融黏度及5弧度/秒之剪切率，以及在室溫下500%或小於500%之伸長率。確認由於實例之黏著膜具 有上文闡述的物理特性，即使在低溫下進行擴展方法，可確保100%可切割性。
亦確認在使用實例1至實例5之黏著膜製造之切晶接合膜中，大體上不經由切割方法產生毛刺，且實例1至實例5之黏著膜具有較高高溫剪切力且因此具有改良的耐熱性及黏著強度。
製備比較例1之黏著膜，使得固體環氧樹脂及液體環氧樹脂之總含量對熱塑性樹脂之重量比變得大於2.6，且酚樹脂對熱塑性樹脂、酚樹脂以及液體環氧樹脂之總重量之重量比變得小於0.280。如表2中所示，確認在比較例1之黏著膜的情況下，在室溫下在5%至10%伸長率下產生之模數小於40兆帕，且室溫下之伸長率大於550%。
亦確認在比較例2(其中使用具有低軟化點之酚樹脂)的情況下，在室溫下在5%至10%伸長率下產生之模數小於30兆帕，且室溫下之伸長率相當於750%。確認由於比較例1及比較例2之黏著膜在室溫下具有高伸長率，且其在低溫擴展方法中具有低可切割性，且因此難以確保足夠可切割性，如表2中所示。
另外，確認在使用比較例1及比較例2之黏著膜製造之切晶接合膜中，經由切割方法產生20%或大於20%的毛刺，且比較例1及比較例2之黏著膜不具有足夠高溫剪切力，且因此難以確保足夠黏著強度。

Claims (12)

  1. 一種半導體用黏著劑組成物，包括：熱塑性樹脂，玻璃轉化溫度為-10℃至20℃；固化劑，含有軟化點為大於100℃且小於160℃或等於160℃的酚樹脂；固體環氧樹脂；以及液體環氧樹脂，其中所述固體環氧樹脂及所述液體環氧樹脂的總含量對所述熱塑性樹脂之重量比為1.75至2.4，所述酚樹脂對所述熱塑性樹脂、所述酚樹脂以及所述液體環氧樹脂的總重量之重量比為0.300至0.600，且所述液體環氧樹脂在25℃下之黏度為13,000毫帕．秒至17,000毫帕．秒。
  2. 如申請專利範圍第1項所述之半導體用黏著劑組成物，其中所述液體環氧樹脂之環氧當量為100至1,000。
  3. 如申請專利範圍第1項所述之半導體用黏著劑組成物，其中所述酚樹脂之羥基當量為100公克/當量至178公克/當量。
  4. 如申請專利範圍第1項所述之半導體用黏著劑組成物，其中所述熱塑性樹脂包括由以下各者所構成的族群中選出之一或多種聚合物樹脂：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、苯氧基樹脂、反應性丁二烯丙烯腈共聚物橡膠以及(甲基)丙烯酸酯類樹脂。
  5. 如申請專利範圍第4項所述之半導體用黏著劑組成物，其中所述(甲基)丙烯酸酯類樹脂為包含含環氧類官能基之(甲基)丙烯酸酯類重複單元且玻璃轉化溫度為-10℃至20℃之(甲基)丙烯酸酯類樹脂。
  6. 如申請專利範圍第5項所述之半導體用黏著劑組成物，其中所述(甲基)丙烯酸酯類樹脂包括0.1重量%至10重量%的包含環氧類官能基之(甲基)丙烯酸酯類重複單元。
  7. 如申請專利範圍第1項所述之半導體用黏著劑組成物，更包括離子清除劑，其包含含由以下各者所構成的族群中選出之一或多種金屬之金屬氧化物：鋯、銻、鉍、鎂以及鋁；多孔矽酸鹽；多孔鋁矽酸鹽；或沸石。
  8. 一種半導體用黏著膜，包括如申請專利範圍第1項所述之半導體用黏著劑組成物。
  9. 如申請專利範圍第8項所述之半導體用黏著膜，其中所述黏著膜的厚度為1微米至300微米。
  10. 如申請專利範圍第8項所述之半導體用黏著膜，其中在室溫下所述黏著膜的5%至10%伸長率下產生的模數為50兆帕(MPa)或大於50兆帕。
  11. 一種切晶接合膜，包括基底膜；形成於所述基底膜上之黏性層；以及形成於所述黏性層上的包括如申請專利範圍第1項所述之半導體用黏著劑組成物之黏著膜。
  12. 如申請專利範圍第11項所述之切晶接合膜，其中所述基底膜的厚度為10微米至200微米，所述黏性層的厚度為1微米至600微米，以及所述黏著膜的厚度為1微米至300微米。
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