TW201339273A - 用於半導體之黏合劑組成物、黏合劑薄膜以及半導體裝置 - Google Patents

用於半導體之黏合劑組成物、黏合劑薄膜以及半導體裝置 Download PDF

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Publication number
TW201339273A
TW201339273A TW101150119A TW101150119A TW201339273A TW 201339273 A TW201339273 A TW 201339273A TW 101150119 A TW101150119 A TW 101150119A TW 101150119 A TW101150119 A TW 101150119A TW 201339273 A TW201339273 A TW 201339273A
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Taiwan
Prior art keywords
curing
weight
resin
parts
adhesive film
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TW101150119A
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English (en)
Inventor
Kyoung-Tae Wi
Sang-Jin Kim
Cheol-Su Kim
Seung-Yong Yang
Jae-Won Choi
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Cheil Ind Inc
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Publication of TW201339273A publication Critical patent/TW201339273A/zh

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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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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    • 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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    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/20—Presence of organic materials
    • C09J2400/22—Presence of unspecified polymer
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Abstract

本發明係有關於一種用於半導體之黏合劑組成物、一種黏合劑薄膜，及半導體裝置。更特別地，本發明係有關於一種黏合劑組成物，其經由增加固化率使用高結合特徵，能容許省略PCB烘烤方法及PCB電漿方法，且於應用在線上方法(in-line process)時於引線接合期間被部份固化，以降低處理時間，藉此，能省略或減少固化方法(或半固化或B-階段)。對於本發明之黏合劑組成物，一酚類樹脂及一胺固化樹脂被一起用作為固化劑以容許省略或減少固化方法，且一咪唑固化劑或一微膠囊型潛固化劑被用作為固化加速劑以增加固化率。

Description

用於半導體之黏合劑組成物、黏合劑薄膜以及半導體裝置 發明領域
本發明係有關於一種用於半導體之黏合劑組成物，及包含此組成物之一種黏合劑薄膜。更特別地，本發明係有關於一種黏合劑組成物，其經由增加固化率而使用高結合特性能容許省略PCB烘烤方法及PCB電漿方法，且於應用於線上方法(in-line process)時於引線結合期間部份固化，以降低處理時間，藉此，能省略或降低固化方法(或半固化或B-階段)。對於本發明之黏合劑組成物，一酚類樹脂及一胺固化樹脂被一起作為固化劑，以容許省略或降低固化方法，且一咪唑固化劑或一微膠囊型潛固化劑被作為一固化加速劑以增加固化率。
相關技藝說明
一半導體裝置之高容量以量而言可藉由電路積體化(其中，每單位面積之元件數增加)，或以品質而言可藉由封裝(其中，晶片被彼此堆疊)而達成。
於封裝技術中，普遍使用係多晶片封裝(其後係“MCP”)，其中，數個晶片係經由黏合劑彼此堆疊，且經由 引線接合彼此電連接。
於晶片接合方法中為確保一晶片與一印刷電路板(PCB)間之足夠接合力，實施PCB烘烤及PCB電漿方法。此外，於120℃晶片接合數秒後，需實行一固化方法(或半固化或B-階段)以於引線接合時確保足夠接合力。然後，於150℃引線接合2至20分鐘後，形成物接受EMC(環氧模製固化)模製，其後於175℃後模製固化(PMC)2小時。
PCB烘烤方法、PCB電漿方法、後固化方法(或半固化或B-階段方法)，及後模製固化方法皆係個別方法，難以降低操作者之時間及數量，因此，降低生產力。
因此，為了改良製造半導體之生產力，不斷增加地需要一種線上方法，其中，於一PCB於軌道上轉移時，晶片接合及引線接合係連續地進行。因此，需要發展一種用於半導體之新穎接合薄膜，其可被應用於線上方法。特別地，於線上方法，因為用於使一接合層形成一足夠交聯結構之一熱程序被顯著降低，因此需要一種能快速固化之組成物，即使於固化方法(或半固化或B-階段方法)及/或PMC方法被省略或固化方法之時間降低之條件下，此得接合失效、晶片分離，及可靠度惡化於引線接合期間不會發生。
韓國專利申請案第2010-0075212及2010-0067915號案揭示黏合劑薄膜組成物，其包含一熱塑性樹脂、一環氧樹脂、一酚類環氧樹脂固化劑、一固化加速劑、一偶合劑，及填料。但是，此等黏合劑薄膜組成物 僅使用一酚固化樹脂作為固化劑，且固化方法緩慢進行，因此，此等黏合劑薄膜組成物不適於其中固化方法(或半固化或B-階段方法)及/或PMC方法被省略之如本發明般的方法。
發明概要
本發明之一方面係提供一種黏合劑薄膜，其僅經由一晶片接合方法展現足夠黏合強度，能省略PCB烘烤方法及PCB電漿方法。
本發明之另一方面係提供一種用於半導體之黏合劑組成物，其展現被應用於線上方法之足夠的黏合強度及彈性，即使於其中晶片接合後之固化方法(或半固化或B-階段方法)被省略或減少之情況，及提供包含此組成物之一種黏合劑薄膜。
本發明之另一方面係提供一種用於半導體之黏合劑組成物，其能省略PMC方法(於175℃持續2小時)，及提供包含此組成物之一種黏合劑薄膜。
本發明一方面提供一種黏合劑組成物，具有於120℃晶片接合5秒時為4 kgf/晶片或更多之晶粒剪切強度，及於150℃固化20分鐘後於150℃為2×106達因/公分2或更多之貯存模量。
本發明另一方面係提供一種黏合劑薄膜，其包含一熱塑性樹脂、一環氧樹脂、一酚類固化樹脂、一胺固化樹脂，及一固化加速劑，且於120℃晶片接合5秒時具有4 kgf/晶片或更多之晶粒剪切強度。
本發明之另一方面係提供一種黏合劑組成物，其以固體含量而言，以100重量份之黏合劑組成物為基準，包含(a)51至80重量份之熱塑性樹脂，(b)5至20重量份之環氧樹脂，(c)2至10重量份之酚類固化樹脂，(d)2至10重量份之胺固化樹脂，及(e)0.1至10重量份之固化加速劑。
依據本發明之用於半導體之黏合劑組成物僅經由一晶片接合方法展現足夠接合力，因此，能省略PCB烘烤方法及PCB電漿方法。
此外，依據本發明之用於半導體之黏合劑組成物能省略或減少晶片接合後之固化方法(或半固化或B-階段方法)及/或PMC方法，因此，改良製造效率及生產力。
再者，依據本發明之黏合劑組成物滿足用於接合同種類半導體晶片所需之加工性及可靠度，即使省略晶片接合後之固化方法及/或PMC方法。
發明詳細說明
本發明之實施例現將詳細說明。需瞭解下列實施例僅係提供作為例示說明，且不以任何方式被作為限制本發明而闡釋。
於一方面，本發明係有關於一種用於半導體之黏合劑薄膜，其於120℃晶片接合5秒時具有4 kgf/晶片或更多 之晶粒剪切強度，及於150℃固化20分鐘後於150℃具有2×106達因/公分2或更多之貯存模量。傳統上，PCB烘烤及PCB電漿方法被進行，以於晶片接合方法於一晶片與一PCB間提供足夠接合力。於本發明，晶粒剪切強度係考量晶片接合方法而判定。依據本發明之黏合劑薄膜僅經由於120℃晶片接合5秒具有4 kgf/晶片或更多，較佳係5 kgf/晶片或更多之晶粒剪切強度，使得足夠接合力可經由晶片接合獲得，藉此，能省略PCB烘烤及PCB電漿方法。
晶粒剪切強度可藉由將具有5mm x 5mm尺寸且於60℃層合於一黏合劑薄膜之一晶片置於具有10mm x 10mm尺寸之一530μm厚晶圓上，其後使此晶片於120℃之一熱板上於10 kgf之載重下壓製5秒而測量。
依據本發明之用於半導體之黏合劑薄膜於150℃固化20分鐘及於175℃模製120秒後具有10%或更少之孔隙面積比率，較佳係7%或更少，更佳係5%或更少。為獲得此孔隙面積比率，於其一側提供依據本發明之用於半導體之黏合劑薄膜之一晶片(黏合劑+晶片)(10 mm x 10 mm)係於120℃於1 kgf之載重下附接至一經預處理之PCB持續1秒，且於150℃之熱板上固化20分鐘，其後於175℃進行EMC模製120秒。熱後，此模製樣品之一黏合劑層被露出且以一顯微鏡(25x放大率)照相，以經由影像分析檢視孔隙存在。為計數孔隙數量，使用柵格計數方法。特別地，總面積於縱向區分成10個柵格且於橫向區分成10個柵格，且含有孔隙之柵格數量被計數且轉換成百分率(%)(孔隙面積比率)。
孔隙面積比率=(孔隙面積/總面積)x 100%
依據本發明，用於半導體之黏合劑薄膜於150℃固化20分鐘後於150℃具有2×106達因/公分2或更多之貯存模量。此貯存模量係考量晶片接合方法後之引線接合方法而判定。傳統上，固化方法(或半固化或B-階段方法)需於120℃至150℃進行約30分鐘至1小時，以於引線接合時提供足夠接合力。依據本發明，用於半導體之黏合劑薄膜於模擬引線接合方法(於150℃固化20分鐘)後具有2×106達因/公分2或更多之高貯存模量，較佳係3×106達因/公分2或更多，更佳係4×106達因/公分2或更多，使得孔隙或可靠度失效不會發生，即使當固化方法(或半固化或B-階段方法)被省略或減少。
於本發明中，貯存模量可藉由於60℃堆疊數片黏合劑薄膜，將黏合劑薄膜堆疊物切成具有400μm至450μm厚度及8 mm直徑之一圓形樣品，使樣品於一熱板上於150℃加熱20分鐘，其後於從30℃至200℃之溫度範圍以10℃/分鐘之溫度增加條件下使用ARES(Advanced Rheometric Expansion System)測量而測量。
依據本發明，黏合劑薄膜特徵在於在150℃加熱20分鐘及接受於250℃之紅外線(IR)回流3分鐘後為6 kgf/晶片或更多之晶粒剪切強度。此狀況係經由模擬其中焊料球(SBA)係於引線接合後立即實施而未實施PMC(後模製固化)方法之方法而判定。藉此，黏合劑薄膜於150℃加熱20分鐘且接受於250℃之紅外線(IR)回流3分鐘後，具有6 kgf/晶片 或更多，較佳係7 kgf/晶片或更多之晶粒剪切強度，因此，能省略PMC方法。
依據本發明，黏合劑薄膜具有20%或更少之固化殘餘率，其係藉由差式掃瞄量熱術(DSC)判定。即，於一熱板上於150℃加熱20分鐘且接受於250℃之峰值溫度之IR-回後3分鐘後產生之熱量係固化前之熱量的20%或更少。
以固體含量而言，以100重量份之黏合劑薄膜為基準，依據本發明之黏合劑薄膜可包括(a)51至80重量份之一熱塑性樹脂；(b)5至20重量份之一環氧樹脂；(c)2至10重量份之一酚類固化樹脂；(d)2至10重量份之一胺固化樹脂；及(e)0.1至10重量份之一固化加速劑，其中，(a)：[(b)+(c)+(d)]之重量比率範圍可為從51至80重量份：9至40重量份，環氧樹脂(b)、酚類固化樹脂(c)，及胺固化樹脂(d)係存在作為固化系統。
於另一方面，本發明係有關於一種黏合劑薄膜，其包含一熱塑性樹脂、一環氧樹脂、一酚類固化樹脂、一胺固化樹脂，及一固化加速劑，且於120℃晶片接合5秒時具有4 kgf/晶片或更多之晶粒剪切強度。
於此方面，黏合劑薄膜具有少於130℃，較佳係少於120℃之固化起始溫度。固化起始溫度可定義為當黏合劑組成物以10℃/分鐘之溫度上升速率從0℃掃瞄到300℃時，放熱峰值開始出現時之溫度。
於此方面，胺固化樹脂較佳係一芳香族胺固化樹脂，更佳係以化學式1表示之一芳香族胺固化樹脂： 其中，A係一單鍵或係選自由-CH2-、-CH2CH2-、-SO2-、-NHCO-、-C(CH3)2-，及-O-所構成之族群；且R1至R10每一者獨立地係氫、一C1-C4烷基基團、一C1-C4烷氧基基團，及胺基團，附帶條件係R1至R10包含至少一胺基團。
於此方面，酚類固化樹脂可包於主鏈中包含一聯苯基團，較佳係以化學式6表示之一酚類固化樹脂： 其中，R1及R2每一者獨立地係一C1-C6烷基基團，且n範圍係從2至100。
於此方面，固化加速劑可包含一咪唑或微膠囊型潛固化劑，較佳係一微膠囊型潛固化劑。
咪唑固化加速劑之例子包括2-甲基咪唑、2-乙基-4-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苯甲基-2-甲基咪唑、2-乙基咪唑、2-異丙基咪唑、2-苯基-4-苯甲基咪唑、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑、2-苯基-4-苯甲基-5-羥基甲基咪唑、4-4'-亞甲基雙-(2-乙基-5-甲基咪唑)、2-胺基乙基-2-甲基咪唑，及1-氰基乙基-2-苯基-4,5-二(氰基乙氧基甲基)咪唑，且不限於此等。可購得之咪唑固化 加速劑的例子包括2MZ、2E4MZ、C11Z、C17Z、2PZ、2PZ-CN、2P4MZ、1B2MZ、2EZ、2IZ、2P4BZ、2PH2-PW、2P4MHZ、2P4BHZ、2E4MZ-BIS、AMZ及2PHZ-CN(Asahi Kasei Corporation)，且不限於此等。特別地，2-苯基-4,5-二羥基甲基咪唑或2-苯基-4-甲基咪唑可有利地作為咪唑固化加速劑。
於本發明中，此項技藝已知之任何微膠囊型潛固化劑可不受特別限制地使用。例如，微膠囊型潛固化劑包括於韓國專利公開第10-2010-0072030A號案中揭示之微膠囊型潛固化劑，其中，核包含胺加成物，且膠囊包含含有異氰酸酯之化合物與活性氫基團及/或水之反應產物；於韓國專利公開第2011-0100235號案揭示之微膠囊固化劑，其中，核包含咪唑化合物，且殼包含有機聚合物、無機化合物，或二者，且覆蓋此核之表面；及於韓國專利公開第2008-0040793號案中揭示之微膠囊潛固化劑，且不限於此。較佳地，可使用Novacure® HX-3721、HX-3748、HX-3741、HX-3613、HX-3722、HX-3742、HX-3088、HX-3792、HX-3921HP、HX-4921HP、HX-3922HP，及HX-3932HP。特別較佳地，可使用HX-3741、HX-3088，及HX-3792。
於另一方面，本發明係有關於一種黏合劑組成物，其以固體含量而言，以100重量份之黏合劑組成物為基準，包含(a)51至80重量份之一熱塑性樹脂；(b)5至20重量份之一環氧樹脂；(c)2至10重量份之一酚類固化樹脂；(d)2 至10重量份之一胺固化樹脂，及(e)0.1至10重量份之一固化加速劑。於此方面，黏合劑組成物可進一步包含一矽烷偶合劑及/或填料。以固體含量而言，以100重量份之黏合劑組成物為基準，矽烷偶合劑可以0.01至5重量份之量存在，且填料可以5至20重量份之量存在。
其次，用於半導體之黏合劑組成物之每一組份，諸如，熱塑性樹脂、環氧樹脂、酚類固化樹脂、胺固化樹脂，及固化加速劑，將詳細說明。
熱塑性樹脂
適用於黏合劑組成物之熱塑性樹脂的例子可包括聚醯亞胺樹脂、聚苯乙烯樹脂、聚乙烯樹脂、聚酯樹脂、聚醯胺樹脂、丁二烯橡膠、丙烯系橡膠、(甲基)丙烯酸酯樹脂、胺甲酸酯樹脂、聚醚醯亞胺樹脂、苯氧樹脂、聚碳酸酯樹脂、聚苯醚樹脂、經改質之聚苯醚樹脂，及其等之混合物，且不限於此等。較佳地，熱塑性樹脂含有一環氧基團。於某些實施例，含有環氧基團之(甲基)丙烯系共聚物可作為熱塑性樹脂。
熱塑性樹脂可具有-30℃至80℃，較佳係5℃至60℃，更佳係5℃至35℃之玻璃轉移溫度。熱塑性樹脂於此範圍內，組成物可確保高流動性以展現優異之孔隙移除能力，且提供高黏合性及可靠度。
於某些實施例，熱塑性樹脂可具有50,000克/莫耳至5,000,000克/莫耳之重量平均分子量。
以固體含量而言，以100重量份之組成物為基 準，熱塑性樹脂可以51~80重量份之量存在，較佳係55~75重量份，更佳係60~72重量份。當熱塑性樹脂之量少於51重量份，以孔隙產生及可靠度而言係非欲所欲的。
再者，熱塑性樹脂(a)對作為固化系統之環氧樹脂(b)、酚類固化劑(c)及胺固化劑(d)之混合物的重量比率，即，(a)：[(b)+(c)+(d)]之重量比率，範圍可為從51~80重量份：9~40重量份，較佳係55~75重量份：15~30重量份。此等組分於此範圍內，孔隙產生可被有利地抑制。
環氧樹脂
環氧樹脂係可固化且用以賦予組成物黏合性。環氧樹脂可為液體環氧樹脂、固體環氧樹脂，或其等之混合物。
適合液體環氧樹脂之例子包括雙酚A型液體環氧樹脂、雙酚F型液體環氧樹脂、三或更多官能性之液體環氧樹脂、經橡膠改質之液體環氧樹脂、經胺甲酸酯改質之液體環氧樹脂、經丙烯系改質之液體環氧樹脂，及光敏性液體環氧樹脂。此等液體環氧樹脂可單獨或以其等之混合物使用。更佳地，使用雙酚A型液體環氧樹脂。
液體環氧樹脂可具有約100 g/eq.至約1500 g/eq.之環氧當量。液體環氧樹脂較佳係具有從約150 g/eq.至約800 g/eq.，更佳係從約150 g/eq.至約400 g/eq.之環氧當量。於此範圍內，可獲得具有良好黏合性及耐熱性同時維持玻璃轉移溫度之固化產物。
液體環氧樹脂具有範圍從100至1,000克/莫耳之 重量平均分子量。以高流動性而言，此範圍係有利。
固體環氧樹脂可為於室溫係固體或似固體者，且具有一或多個官能基團。固體環氧樹脂可具有30℃至100℃之軟化點(Sp)。適合固體環氧樹脂之例子包括雙酚環氧樹脂、酚醛清漆環氧樹脂、鄰-甲酚酚醛清漆環氧樹脂、多官能性環氧樹脂、胺環氧樹脂、雜環環氧樹脂、經取代之環氧樹脂、以萘酚為主之環氧樹脂、以聯苯為主之環氧樹脂，及其等之衍生物。
作為可購得之固體環氧樹脂，雙酚環氧樹脂之例子包括YD-017H、YD-020、YD020-L、YD-014、YD-014ER、YD-013K、YD-019K、YD-019、YD-017R、YD-017、YD-012、YD-011H、YD-011S、YD-011、YDF-2004、YDF-2001(Kukdo Chemical Co.,Ltd.)等。酚醛清漆環氧樹脂之例子包括EPIKOTE 152及EPIKOTE 154(Yuka Shell Epoxy Co.,Ltd.)；EPPN-201(Nippon Kayaku Co.,Ltd.)；DN-483(Dow Chemical Company)；YDPN-641、YDPN-638A80、YDPN-638、YDPN-637、YDPN-644、YDPN-631(Kukdo Chemical Co.,Ltd.)等。鄰-甲酚酚醛清漆環氧樹脂之例子包括：YDCN-500-1P、YDCN-500-2P、YDCN-500-4P、YDCN-500-5P、YDCN-500-7P、YDCN-500-8P、YDCN-500-10P、YDCN-500-80P、YDCN-500-80PCA60、YDCN-500-80PBC60、YDCN-500-90P、YDCN-500-90PA75(Kukdo Chemical Co.,Ltd.)；EOCN-102S、EOCN-103S、EOCN-104S、EOCN-1012、 EOCN-1025、EOCN-1027(Nippon Kayaku Co.,Ltd.)；YDCN-701、YDCN-702、YDCN-703、YDCN-704(Tohto Kagaku Co.,Ltd.)；Epiclon N-665-EXP(Dainippon Ink and Chemicals,Inc.)等。雙酚清漆環氧樹脂之例子包括KBPN-110、KBPN-120、KBPN-115(Kukdo Chemical Co.,Ltd.)等。多官能性環氧樹脂之例子包括Epon 1031S(Yuka Shell Epoxy Co.,Ltd.)；Araldite 0163(Ciba Specialty Chemicals)；Detachol EX-611、Detachol EX-614、Detachol EX-614B、Detachol EX-622、Detachol EX-512、Detachol EX-521、Detachol EX-421、Detachol EX-411、Detachol EX-321(NAGA Celsius Temperature Kasei Co.,Ltd.)；EP-5200R、KD-1012、EP-5100R、KD-1011、KDT-4400A70、KDT-4400、YH-434L、YH-434、YH-300(Kukdo Chemical Co.,Ltd.)等。胺環氧樹脂之例子包括EPIKOTE 604(Yuka Shell Epoxy Co.,Ltd.)；YH-434(Tohto Kagaku Co.,Ltd.)；TETRAD-X及TETRAD-C(Mitsubishi Gas Chemical Company Inc.)；ELM-120(Sumitomo Chemical Industry Co.,Ltd.)等。雜環環氧樹脂之例子包括PT-810(Ciba Specialty Chemicals)。經取代之環氧樹脂的例子包括：ERL-4234、ERL-4299、ERL-4221、ERL-4206(UCC Co.,Ltd.)等。萘酚環氧樹脂的例子包括：Epiclon HP-4032、Epiclon HP-4032D、Epiclon HP-4700，及Epiclon HP-4701(Dainippon Ink and Chemicals,Inc.)。非酚類之環氧樹脂的例子包括YX-4000H(Japan Epxoy Resin)、YSLV-120TE、 GK-3207(Nippon steel chemical)、NC-3000(Nippon Kayaku)等。此等環氧樹脂可單獨或以混合物使用。
以固體含量而言，以100重量份之組成物為基準，環氧樹脂可以5至20重量份，較佳係7至15重量份存在。於此範圍內，可達成高可靠度及優異機械性質。
固化劑
適用於此黏合劑組成物之固化劑可為二種具有不同反應溫度區之固化劑。
於某些實施例，固化劑係酚類固化劑及胺固化劑。
雖然此項技藝已知之任何酚類固化劑可不受限地使用，但可使用於單一分子中含有二或更多個酚羥基基團且於水解時展現優異耐電解腐蝕性之雙酚樹脂，諸如，雙酚A、雙酚F、雙酚S等；酚醛清漆樹脂；雙酚A酚醛清漆樹脂；及酚樹脂，諸如，二甲苯、甲酚酚醛清漆、聯苯樹脂等。作為可購得之酚類固化劑，酚類固化劑的例子包括H-1、H-4、HF-1M、HF-3M、HF-4M，及HF-45(Meiwa Plastic Industries Co.,Ltd.)；對二甲苯酚類固化劑之例子包括MEH-78004S、MEH-7800SS、MEH-7800S、MEH-7800M、MEH-7800H、MEH-7800HH，及MEH-78003H(Meiwa Plastic Industries Co.,Ltd.)、PH-F3065(Kolong Industries Co.,Ltd.)；聯苯固化劑之例子包括MEH-7851SS、MEH-7851S、MEH-7851M、MEH-7851H、MEH-78513H、MEH-78514H(Meiwa Plastic Industries Co.,Ltd.)，及 KPH-F4500(Kolong Industries Co.,Ltd.)；且三苯基甲基固化劑之例子包括MEH-7500、MEH-75003S、MEH-7500SS、MEH-7500S、MEH-7500H(Meiwa Plastic Industries Co.,Ltd.)等。此等可單獨或以其等之混合物使用。
適用於黏合劑組成物之酚類固化劑可具有以化學式6表示之一結構： 其中，R1及R2每一者獨立地係一C1-C6烷基基團，且n範圍從2至100。
酚類固化劑之例子不需受限制地包括MEH-7851SS、MEH-7851S、MEH-7851M、MEH-7851H，及MEH-78514H，其等係可購自Meiwa Plastic Industries Co.,Ltd.。
以固體含量而言，以100重量份之黏合劑組成物為基準，酚類固化劑可以2至10重量份之量存在。
以固化率調整而言，胺固化劑可為一芳香族胺固化劑。較佳地，胺固化樹脂係於單一分子中具有二或更多個胺基團之一芳香族化合物，不限於此且以，例如，化學式1至5表示： 其中，A係一單鍵或係選自由-CH2-、-CH2CH2-、-SO2-、-NHCO-、-C(CH3)2-，及-O-所構成之族群；且R1至R10每一者獨立地係氫、一C1-C4烷基基團、一C1-C4烷氧基基團，及胺基團，附帶條件係R1至R10包含至少二個胺基團。
其中，R11至R18包含至少一或多個胺基團，且係一C1至C4烷基基團、一烷氧基基團、一羥基基團、一氰化物基團，或鹵素。
其中，Z1係氫、一C1至C4烷基基團、一烷氧基基團，或一羥基基團；R19至R33包含至少一或多個胺基團，且係氫、一C1至C4烷基基團、一烷氧基基團、一羥基基團、一氰化物基團，或鹵素。
其中，R34至R41包含至少一或多個胺基團，且係氫、一C1至C4烷基基團、一烷氧基基團、一羥基基團、一氰化物基團，或鹵素。
其中，X3係選自由-CH2-、-NH-、-SO2-、-S-，及-O-所構成族群之一者；且R42至R49包含至少一或多個胺基團，且係氫、一C1至C4烷基基團、一烷氧基基團、一羥基基團、一氰化物基團，或鹵素。
具化學式1之固化劑的例子包括3,3'-二胺基聯苯胺、4,4'-二胺基二苯基甲烷、4,4'或3,3'-二胺基二苯基碸、4,4'-二胺基二苯基酮、對苯二胺、間苯二胺、間甲苯二荌、4,4'-二胺基二苯基醚、4,4'或3,3'-二胺基二苯基酮、1,4'或1,3'-雙(4或3-胺基異丙苯基)苯、1,4'雙(4或3-胺基苯氧基)苯、2,2'-雙[4-(4或3-胺基苯氧基)苯基]丙烷、雙[4-(4或3-胺基苯氧基)苯基]碸、2,2'-雙[4-(4或3-胺基苯氧基)苯基]六氟 碸、2,2'-雙[4-(4或3-胺基苯氧基)苯基]六氟丙烷、4,4'-二胺基-3,3',5,5'-四丁基二苯基酮、4,4'-二胺基-3,3',5,5'-四乙基二苯基酮、4,4'-二胺基-3,3',5,5'-四正亞丙基二苯基酮、4,4'-二胺基-3,3',5,5'-四異丙基二苯基酮、4,4'-二胺基-3,3',5,5'-四甲基二苯基酮、4,4'-二胺基-3,3',5,5'-四正丙基二苯基甲烷、4,4'-二胺基-3,3'5,5-四甲基二苯基甲烷、4,4'-二胺基-3,3'5,5'-四異丙基二苯基甲烷、4,4'-二胺基-3,3'5,5'-四乙基二苯基甲烷、4,4'-二胺基-3,3'-二甲基-5,5'-二乙基二苯基甲烷、4,4'-二胺基-3,3'-二甲基-5,5'-二異丙基二苯基甲烷、4,4'-二胺基-3,3'-二乙基-5,5'-二乙基二苯基甲烷、4,4'-二胺基-3,5'-二甲基-3',5'-二乙基二苯基甲烷、4,4'-二胺基-3,5-二甲基-3',5'-二異丙基二苯基甲烷、4,4'-二胺基-3,5-二乙基-3',5'-二丁基二苯基甲烷、4,4'-二胺基-3,5-二異丙基-3',5'-二丁基二苯基甲烷、4,4'-二胺基-3,3'-二異丙基-5,5'-二丁基二苯基甲烷、4,4'-二胺基-3,3'-二甲基-5',5'-二丁基二苯基甲烷、4,4'-二胺基-3,3'-二乙基-5',5'-二丁基二苯基甲烷、4,4'-二胺基-3,3'-二甲基二苯基甲烷、4,4'-二胺基-3,3'-二乙基二苯基甲烷、4,4'-二胺基-3,3'-二正丙基二苯基甲烷、4,4'-二胺基-3,3'-二異丙基二苯基甲烷、4,4'-二胺基-3,3'-二丁基二苯基甲烷、4,4'-二胺基-3,3',5-三甲基二苯基甲烷、4,4'-二胺基-3,3',5-三乙基二苯基甲烷、4,4'-二胺基-3,3',5-三正丙基二苯基甲烷、4,4'-二胺基-3,3',5-三異丙基二苯基甲烷、4,4'-二胺基-3,3',5-三丁基二苯基甲烷、4,4'-二胺基-3-甲基-3'-乙基二苯基甲烷、4,4'-二胺基-3-甲基-3'-異丙基二苯基甲烷、4,4'- 二胺基-3-甲基-3'-丁基二苯基甲烷、4,4'-二胺基-3-異丙基-3'-丁基二苯基甲烷、2,2-雙(4-胺基-3,5-二甲基苯基)丙烷、2,2-雙(4-胺基-3,5-二乙基苯基)丙烷、2,2-雙(4-胺基-3,5-二正丙基苯基)丙烷、2,2-雙(4-胺基-3,5-二異丙基苯基)丙烷、2,2-雙(4-胺基-3,5-二丁基苯基)丙烷、4,4'-二胺基-3,3',5,5'-四甲基二苯基苯甲醯苯胺、4,4'-二胺基-3,3',5,5'-四乙基二苯基苯甲醯苯胺、4,4'-二胺基-3,3',5,5'-四正丙基二苯基苯甲醯苯胺、4,4'-二胺基-3,3',5,5'-四異丙基二苯基苯甲醯苯胺、4,4'-二胺基-3,3',5,5'-四丁基二苯基苯甲醯苯胺、4,4'-二胺基-3,3',5,5'-四甲基二苯基碸、4,4'-二胺基-3,3',5,5'-四乙基二苯基碸、4,4'-二胺基-3,3',5,5'-四正丙基二苯基碸、4,4'-二胺基-3,3',5,5'-四異丙基二苯基碸、4,4'-二胺基-3,3',5,5'-四甲基二苯基醚、4,4'-二胺基-3,3',5,5'-四乙基二苯基醚、4,4'-二胺基-3,3',5,5'-四正丙基二苯基醚、4,4'-二胺基-3,3',5,5'-四異丙基二苯基醚、4,4'-二胺基-3,3',5,5'-四丁基二苯基醚、3,3'-二胺基二苯基酮、3,4-二胺基二苯基酮、3,3'-二胺基二苯基醚、3,3'-二胺基二苯基甲烷、3,4'-二胺基二苯基甲烷、2,2'-二胺基-1,2-二苯基乙烷或4,4'-二胺基-1,2-二苯基乙烷、2,4-二胺基二苯基胺、4,4'-二胺基八氟聯苯、鄰-二甲氧苯胺等。
具化學式2之固化劑之例子包括1,5-二胺基萘、1,8-二胺基萘、2,3-二胺基萘等。具化學式3之固化劑的例子包括p,p’,p”-三胺三苯甲醇等。具化學式4之固化劑的例子包括1,2-二胺基蒽醌、1,4-二胺基蒽醌、1,5-二胺基蒽醌、2,6- 二胺基蒽醌、1,4-二胺基-2,3-二氯蒽醌、1,4-二胺基-2,3-二氰基-9,10-蒽醌、1,4-二胺基-4,8-二羥基-9,10-蒽醌等。具化學式5之固化劑的例子包括3,7-二胺基-2,8-二甲基二苯并噻吩碸、2,7-二胺基芴、3,6-二胺基咔唑等。
以固體含量而言，以100重量份之黏合膜組成物為基準，胺固化樹脂可以2至10重量份之量存在。
固化加速劑
用於半導體之黏合劑組成物可包含一固化加速劑。適用於依據本發明之組成物之固化加速劑係用以降低半導體方法期間環氧樹脂之固化時間。雖然此項技藝已知之任何固化加速劑可被使用，但可使用三聚氰胺、咪唑或微膠囊型潛固化催化劑，及三苯基膦固化催化劑。較佳地，係使用咪唑或微膠囊型潛固化劑，且特別較佳地，係使用微膠囊型潛固化劑。
適用於依據本發明之組成物的咪唑固化加速劑之例子包括2-甲基咪唑、2-乙基-4-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苯甲基-2-甲基咪唑、2-乙基咪唑、2-異丙基咪唑、2-苯基-4-苯甲基咪唑、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑、2-苯基-4-苯甲基-5-羥基甲基咪唑、4-4'-亞甲基雙-(2-乙基-5-甲基咪唑)、2-胺基乙基-2-甲基咪唑、1-氰基乙基-2-苯基-4,5-二(氰基乙氧基甲基)咪唑等。可購得之咪唑固化加速劑的例子包括2MZ、2E4MZ、C11Z、C17Z、2PZ、2PZ-CN、2P4MZ、1B2MZ、2EZ、2IZ、2P4BZ、 2PH2-PW、2P4MHZ、2P4BHZ、2E4MZ-BIS、AMZ，及2PHZ-CN(Asahi Kasei Corporation)，且不限於此等。特別地，2-苯基-4,5-二羥基甲基咪唑或2-苯基-4-甲基咪唑可有利地作為咪唑固化加速劑。
適用於依據本發明之組成物之微膠囊型潛固化劑之例子包括於韓國專利公開第10-2010-0072030A號案中揭示之微膠囊型潛固化劑，其中，核包含胺加成物，且膠囊包含含有異氰酸酯之化合物與活性氫基團及/或水之反應產物；於韓國專利公開第2011-0100235號案揭示之微膠囊固化劑，其中，核包含咪唑化合物，且殼包含有機聚合物、無機化合物，或二者，且覆蓋此核之表面；及於韓國專利公開第2008-0040793號案中揭示之微膠囊潛固化劑，且不限於此(需瞭解此等揭示內容之全部在此併入本案以為參考資料)。較佳地，可使用Novacure® HX-3721、HX-3748、HX-3741、HX-3613、HX-3722、HX-3742、HX-3088、HX-3792、HX-3921HP、HX-4921HP、HX-3922HP，及HX-3932HP。特別較佳地，可使用HX-3741、HX-3088，及HX-3792。
以膦為主之固化催化劑之例子包括TBP、TMTP、TPTP、TPAP、TPPO、DPPE、DPPP、DPPB，其得可購自Hokko Chemical Industry Co.,Ltd.。
以100重量份之黏合劑組成物為基準，固化加速劑可以0.1至10重量份，較佳係0.3~7重量份之量存在。固化加速劑於此範圍內，可達成高耐熱性、流動性及連接性能， 且不會造成環氧樹脂快速反應。
矽烷偶合劑
用於半導體的黏合劑組成物可進一步包含矽烷偶合劑。矽烷偶合劑係作為黏合促進劑，以於組成物摻合期間經由其間之化學偶合增強諸如填料之無機材料與有機材料表面間之黏合。
此項技藝已知之任何矽烷偶合劑可用於本發明之組成物，且其例子包括：含環氧基團之矽烷偶合劑，諸如，2-(3,4-環氧環己基)-乙基三甲氧基矽烷、3-環氧丙氧基三甲氧基矽烷，及3-環氧丙氧基丙基三乙氧基矽烷；含胺基團之矽烷偶合劑，諸如，N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基矽烷基-N-(1,3-二甲基亞丁基)丙胺，及N-苯基-3-胺基丙基三甲氧基矽烷；含巰基之矽烷偶合劑，諸如，3-巰基丙基甲基二甲氧基矽烷，及3-巰基丙基三乙氧基矽烷；及含異氰酸酯之矽烷偶合劑，諸如，3-異氰酸酯丙基三乙氧基矽烷。此等矽烷偶合劑可單獨或以其等之混合物使用。
以固體含量而言，以100重量份之黏合劑組成物為基準，偶合劑可以0.01至5重量份，較佳係0.1至3重量份，更佳係0.5至2重量份存在。於此範圍內，可獲得高黏合可靠度，且氣泡發生可降低。
填料
本發明之組成物可進一步包括填料。
適用於本發明之組成物的填料之例子包括：金屬粉末，諸如，金、銀、銅及鎳粉末；及非金屬，諸如，氧化鋁、氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、矽酸鈣、矽酸鎂、氧化鈣、氧化鎂、氧化鋁、氮化鋁、二氧化矽、氮化硼、二氧化鈦、玻璃、氧化鐵，及陶瓷。較佳係使用二氧化矽。
填料的形狀及尺寸並無特別限制。球形二氧化矽或非結晶二氧化矽典型上被作為填料。二氧化矽之顆粒尺寸範圍可為從約5 nm至20 μm。
以100重量份之黏合劑組成物為基準，填料係以1至30重量份，較佳係5~25重量份之量存在。於此範圍內，可獲得高流動性、成膜性質，及黏合性。
溶劑
黏合劑組成物可進一步包括溶劑。溶劑係用以降低黏合劑組成物之黏度，藉此，增進黏合劑薄膜形成。適用於黏合劑組成物之溶劑的特別例子包括有機溶劑，諸如，甲苯、二甲苯、丙二醇單甲醚乙酸酯、苯、丙酮、甲乙酮、四氫呋喃、二甲基甲醯胺，及環己酮，且不限於此等。
本發明之另一方面係有關於一種用於半導體之黏合劑薄膜，其包含依據本發明之黏合劑組成物。不需要特別裝置或設備用以使用依據本發明之黏恰劑組成物形成用於半導體之一黏合劑薄膜，且此項技藝普遍所知之任何 方法可用於製造此黏合劑薄膜。例如，個別之組份溶於一溶劑，且使用一珠磨機充份捏合，其後，將形成物沉積於一聚對苯二甲酸乙二酯(PET)薄膜，其接受脫離處理，且於100℃之爐內乾燥10~30分鐘，製備具有適合厚度之一黏合劑薄膜。
於一實施例，用於半導體之黏合劑薄膜可包括一基底薄膜、一黏合層、一結合層，及一保護薄膜，其等係以此順序依序堆疊。
黏合劑薄膜較佳係具有5 μm至200 μm之厚度，更佳係10 μm至100 μm。於此範圍內，黏合劑薄膜展現足夠黏合性，同時提供具經濟性之可行性。更佳地，黏合劑薄膜具有15 μm至60 μm之厚度。
其次，本發明參考下列範例將變得更明顯，且需瞭解下列範例僅係提供作為例示說明，且非限制僅藉由申請專利範圍及其等化物所限制之本發明範圍。
範例
範例1-2：製備用於半導體之黏合劑組成物
溶劑(環己烷)添加至如表1中所列示之一熱塑性樹脂、一環氧樹脂、一酚類固化劑、一胺固化劑、一固化加速劑、填料，及一矽烷偶合劑，使得溶液中之固體含量係20重量%，其後使用一珠磨機充份捏合，藉此，製備一用於半導體之黏合劑組成物。
比較例1-3：製備用於半導體之黏合劑組成物
除了表2中列示之某些組份外，用於半導體之黏 合劑組成物係以與範例1及2相同方式製備。
範例及比較例使用之個別組份之說明係如下。
製備黏合劑薄膜
範例1及2與比較例1、2及3製備之黏合劑組成物 之每一者沉積於一PET膜上，其接受使用一塗敷器之脫離處理，其後於100℃之爐內乾燥10~30分鐘，藉此，提供一60 um厚黏合膜。
實驗例：評估使用範例及比較例之黏合劑組成物製備之黏合劑薄膜之物理性質
使用範例1及2與比較例1、2及3之黏合劑組成物製備之黏合劑薄膜之每一者的物理性質係藉由下列方法評估，且結果係顯示於表2。
(1)晶粒剪切強度：一530 μm厚之晶圓切成具有5 mm x 5 mm尺寸之晶片。此等晶片以每一黏合劑薄膜於60℃層合，且被切割而僅留下一接合部份。具有5x5 mm尺寸之一上晶片被置於具有10x10 mm尺寸之一晶圓上，其後，於120℃之一熱板上施加10 kgf之力量持續5秒。然後，晶粒剪切強度使用DAGE 4000測量。結果顯示於表2。
(2)固化起始溫度：用於固化製得之黏合劑組成物而產生之熱量係使用DSC，於從0℃至300℃掃瞄，以10℃/分鐘之溫度上升速率至放熱峰值出現時而測量。
(3)貯存模量：數片黏合劑薄膜於60℃層合，且切割製成具有8 mm直徑之一圓形樣品。此樣品具有約400~450μm之厚度。然後，樣品於150℃之一熱板上加熱20分鐘，且樣品之貯存模量係於從30℃至200℃之溫度範圍使用ARES測量。於150℃之貯存模量係顯示於表2。此處，溫度上升速率係10℃/分鐘。
回流後之晶粒剪切強度：於製備用於測量晶粒剪切強度(1)之樣品後，此樣品於150℃之一熱板上加熱20分鐘，且接受於250℃峰值溫度之IR回流3分鐘。然後，晶粒剪切強度於260℃使用Dage 4000測量。
(5)固化殘餘率：製得之黏合劑組成物於150℃之一熱板上加熱20分鐘，且接受於250℃峰值溫度之IR回流3分鐘。然後，固化期間產生之熱量使用DSC測量，且除以用於固化之起始熱量而計算固化殘餘劑。黏合劑組成物之起始熱量係於150℃之熱板上固化20前使用DSC測量。
(6)模製後孔隙面積比率：以置於一安裝機的一熱板上且接受使用異丙醇(IPA)移除外來物質之經拋光的晶圓，此晶圓之一鏡面置於一黏合劑薄膜之一黏著表面上。此處，安裝機溫度設為60℃，其係一般表面溫度。晶圓-黏合劑薄膜之組件藉由鋸切切成10x10 mm之晶片尺寸，且於120℃及1 kgf/1sec與一已於表3之條件下接受預處 理之PCB附接，藉此，製備晶片，每一者於其一側上具有黏著劑。
然後，製得之樣品接受1週期之於150℃之一熱板上固化20分鐘，且EMC模製於表4之條件下實施，其後測量孔隙比率。
然後，形成物使用一切割鋸切成個別單元，其後移除PCB且使用一研磨機研磨至黏合劑薄膜之黏合劑層露出為止，以測量模製後之孔隙比率。此處，為促進孔隙觀察，形成物被研磨，使得部份留下之PCB之一焊料阻劑層至半透明程度。
研磨後，露出之黏合劑層使用一顯微鏡(放大率：25x)照相，且孔隙之存在經由影像分析檢測。為使孔隙數量數位化，使用柵格計數方法。特別地，樣品總面積區分成10個柵格列及10個柵格行，含有孔隙之柵格數被計量且轉化成%(孔隙面積比率)。
孔隙面積比率=(孔隙面積/總面積)x100%
(7)熔融黏度：數片黏合劑薄膜於60℃層合，且切割製備具有8 mm直徑之一圓形樣品。樣品具有約 400~450 um厚度。然後，樣品於150℃之一熱板上加熱20分鐘，且熔融黏度係於30℃至200℃溫度範圍使用ARES測量。
如表2所示，可見到範例1及2之黏合劑組成物僅經由120℃晶片接合5秒具有4 kgf/晶片或更多之晶粒剪切強度，且於模擬引線接合(於150℃固化20分鐘)後具有2×106達因/公分2或更多之高貯存模量，因此，僅單獨經由晶片接合而提供足夠黏合，或能省略PCB烘烤及PCB電漿方法。此外，即使於省略或減少固化方法(或半固化或B-階段方法)之情況，無孔隙產生或可靠度惡化。再者，因為範例1及2之黏合劑組成物於150℃加熱20分鐘，然後接受於250℃之IR回流3分鐘後具有6 kgf/晶片或更多之晶粒剪切強度，可省略PMC方法。
相反地，對於使用胺固化劑之單一固化系統之比較例1之黏合劑組成物，及使用酚類固化劑之單一固化系統之比較例2之黏合劑組成物，一足夠交聯結構未經由於150℃不足夠加熱20分鐘而形成，且貯存模量低，因此，於耐回流測試造成破裂。再者，以孔隙產生及可靠度而言，使用51重量%或更少之熱塑性樹脂之比較例3之黏合劑組成物遭遇失效。
雖然某些實施例已結合圖式而提供，但對於熟習此項技藝者明顯地係此等實施例僅提供當作例示說明，且各種修改、改變、變化，及等效實施例可於未偏離本發明之精神及範圍而進行。本發明之範圍需僅受限於所附之申 請專利範圍及其等效物。

Claims (14)

  1. 一種用於半導體之黏合劑薄膜，具有於120℃晶片接合5秒時為4 kgf/晶片或更多之晶粒剪切強度，及於150℃固化20分鐘後於150℃為2×106達因/公分2或更多之貯存模量。
  2. 如申請專利範圍第1項之用於半導體之黏合劑薄膜，其中，該黏合劑薄膜於150℃加熱20分鐘及於250℃之紅外線回流3分鐘後具有6 kgf/晶片或更多之晶粒剪切強度。
  3. 如申請專利範圍第1項之用於半導體之黏合劑薄膜，其中，該黏合劑薄膜於150℃固化20分鐘及於175℃模製120秒後具有10%或更少之孔隙面積比率。
  4. 如申請專利範圍第1項之用於半導體之黏合劑薄膜，其中，以固體含量而言，以100重量份之該黏合劑薄膜為基準，該黏合劑薄膜包含：(a)51至80重量份之一熱塑性樹脂；(b)5至20重量份之一環氧樹脂；(c)2至10重量份之一酚類固化樹脂；(d)2至10重量份之一胺固化樹脂；及(e)0.1至10重量份之一固化加速劑。
  5. 如申請專利範圍第4項之用於半導體之黏合劑薄膜，其中，(a)對[(b)+(c)+(d)]之重量比率範圍從51至80重量份：9至40重量份，該環氧樹脂(b)、該酚類固化樹脂(c)，及該胺固化樹脂(d)係存在作為固化系統。
  6. 一種用於半導體之黏合劑薄膜，包含一熱塑性樹脂、一環氧樹脂、一酚類固化樹脂、一胺固化樹脂，及一固化加速劑，其中，該黏合劑薄膜於120℃晶片接合5秒時具有4 kgf/晶片或更多之晶粒剪切強度。
  7. 如申請專利範圍第6項之用於半導體之黏合劑薄膜，其中，該黏合劑薄膜具有少於130℃之固化起始溫度。
  8. 如申請專利範圍第6項之用於半導體之黏合劑薄膜，其中，該胺固化樹脂包含一芳香族胺固化樹脂。
  9. 如申請專利範圍第8項之用於半導體之黏合劑薄膜，其中，該芳香族胺固化樹脂係以化學式1表示： 其中，A係一單鍵或係選自由-CH2-、-CH2CH2-、-SO2-、-NHCO-、-C(CH3)2-，及-O-所構成之族群；且R1至R10每一者獨立地係氫、一C1-C4烷基基團、一C1-C4烷氧基基團，及胺基團，附帶條件係R1至R10包含至少二個胺基團。
  10. 如申請專利範圍第6至9項中任一項之用於半導體之黏合劑薄膜，其中，該酚類固化樹脂係以化學式6表示： 其中，R1及R2每一者獨立地係一C1-C6烷基基團，且n 範圍係從2至100。
  11. 如申請專利範圍第6至9項中任一項之用於半導體之黏合劑薄膜，其中，該固化加速劑包含選自咪唑固化加速劑及微膠囊型潛固化劑之至少一者或多者。
  12. 一種用於半導體之黏合劑組成物，以固體含量而言，以100重量份之該黏合劑組成物為基準，包含：(a)51至80重量份之一熱塑性樹脂；(b)5至20重量份之一環氧樹脂；(c)2至10重量份之一酚類固化樹脂；(d)2至10重量份之一胺固化樹脂；及(e)0.1至10重量份之一固化加速劑。
  13. 如申請專利範圍第12項之用於半導體之黏合劑組成物，其中，該固化加速劑包含選自咪唑固化加速劑及微膠囊型潛固化劑之至少一者或多者。
  14. 一種半導體裝置，其係使用如申請專利範圍第1至5項中任一項之用於半導體之黏合劑薄膜或如申請專利範圍第6至13項中任一項之用於半導體之黏合劑組成物連接。
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