TW201526031A - 使用具有嵌段共聚物塗層的導電粒子之固定陣列異向性導電膜 - Google Patents

使用具有嵌段共聚物塗層的導電粒子之固定陣列異向性導電膜 Download PDF

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TW201526031A
TW201526031A TW103130696A TW103130696A TW201526031A TW 201526031 A TW201526031 A TW 201526031A TW 103130696 A TW103130696 A TW 103130696A TW 103130696 A TW103130696 A TW 103130696A TW 201526031 A TW201526031 A TW 201526031A
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Taiwan
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block
conductive film
anisotropic conductive
particle
block copolymer
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TW103130696A
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TWI600032B (zh
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Rong-Chang Liang
Yu-Hao Sun
Zhi-Yao An
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Trillion Science Inc
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Abstract

本發明係關於一種異向性導電膜陣列之結構及製造程序，更具體而言，係將非隨機粒子移動至預定組態、形狀和維度的微共振腔室陣列。製造程序包含將以嵌段共聚物組成物進行表面處理之導電粒子射流填充至由預定微共振腔室陣列構成之基板或托架腹板上。將製造之填充導電微共振腔室陣列進而以黏著膜塗佈或分層。

Description

使用具有嵌段共聚物塗層的導電粒子之固定陣列異向性導電膜
本發明一般而言係關於一種異向性導電膜之結構及製造方法。更具體而言，本發明係關於一種具有改善的電性連接之解析度及可靠度的異向性導電膜之結構及製造程序，其中導電粒子係以包含二相嵌段共聚物類型的彈性體處理，該彈性體包含與異向性導電膜黏著劑不相容的片段。
異向性導電膜通常用於平板顯示驅動器積體電路接合。典型的異向性導電膜接合程序包含例如：第一步，將異向性導電膜貼附於面板玻璃的電極；第二步，驅動器積體電路接合墊與面板電極對齊；第三步，對接合墊施加壓力和熱在數秒內熔化並硬化異向性導電膜。異向性導電膜之導電粒子在面板電極和驅動器積體電路之間提供異向性導電性。近來，異向性導電膜亦廣泛用於如倒裝晶片接合和光伏打模組組裝體之應用。
傳統異向性導電膜之導電粒子通常會隨機分散於異 向性導電膜。由於X-Y導電性，此種分散系統的粒子密度會受限。在精細間距接合應用中，導電粒子密度必須高到足以使每個接合墊上街有適當數量的導電粒子接合。然而，由於高密度的導電粒子及隨機分散的特徵，在兩個接合墊之間的絕緣區域發生短路或不理想的高導電性之機率亦會增加。
近來，對於高解析度及/或高整合程度的顯示裝置之需求已經急遽增加。舉例而言，晶片玻璃接合裝置所需的典型最小接合區域已經從1200-1600平方微米下降到400-800平方微米。此係揭露於美國公告專利2012/0295098「使用經表面修改的導電粒子之固定陣列導電膜(FIXED-ARRAY CONDUCTIVE FILM USING SURFACE MODIFIED CONDUCTIVE PARTICLES)」，亦即在固定陣列異向性導電膜中使用耦合劑處理之導電粒子可大幅增進電極間隙區域之間的導電粒子分散穩定性並減少粒子積聚之風險和短路之機率。為了進一步減少接合區域，舉例而言，減少至低於400平方微米，且仍然在Z方向提供滿意的連接導電性，即使是高粒子捕捉率的固定陣列異向性導電膜，在接合之前亦可能需要高達50,000個/平方毫米的導電粒子濃度。假設粒子大小為3.0微米，在接合之前，粒子密度為50,000個/平方毫米，電極區域的粒子捕捉率為30-50%，接合區域為400平方微米，間隙區域為1000平方微米，間隙區域的粒子濃度可為高達60,000至64,000個/平方毫米，或總粒子橫斷面區域佔85-90%的間隙區域。若間隙區域為600平方微米，則接合之後，間隙區域的粒子濃度將增加成約66,667-73,333個/平方毫米，或總粒子橫斷面區域增加成佔94.2-103.6%的間隙區域。在所有情況下，間隙區域的粒子密度高於具有狹窄粒子大小分布之粒子的最大 包覆密度，且大部分粒子將堆疊於間隙區域，而無法避免粒子之累積或群聚現象出現。對於傳統的非固定陣列異向性導電膜，則間隙區域的粒子密度將更高，原因是電極/凸緣處具有明顯較低的粒子捕捉率。
如果要啟用超精細間距接合/連接，較佳為導電粒子即使在間隙區域呈聚集狀態亦具有高絕緣電阻，且在適度的接合壓力/溫度下接合之後，在連結的電極具有十分低的接觸電阻。
使用以溶劑可溶或可分散的聚合絕緣層預先塗佈的導電粒子所製造的異向性導電膜已揭露於以下參考文獻：Japan Kokai 10-134634(1998)(Y.Marukami)；62-40183(1987)(Choi II Ind)；及US 5,162,087(1992)(Soken Chemical & Engineering Co.)。導電粒子的絕緣塗層降低鄰近電極之間由於粒子在電極間隙或間距區域聚集而產生短路的風險。然而，溶劑可溶或可分散的聚合絕緣層通常會在儲存時或甚至在異向性導電層之射流製造或塗層期間脫附或溶解入黏著層。
以下參考文獻揭露在異向性導電膜中導電粒子表面上使用交聯或膠化聚合物層/粒子和無機粒狀物以降低絕緣層/粒子的脫附或溶解，並增進精細間距應用中的異向性導電膜接合成效：美國專利5,965,064；美國6,632,532；美國7,846,547；Sony Chemicals Corp.的美國專利8,309,224；美國公告專利2010/0327237；2012/0097902；Hitachi Chemical Co.的美國2012/0104333；美國專利7,252,883；Sekisui Chemical Co.的美國7,291,393；美國專利7,566,494；美國7,815,999；美國7,851,063；Cheil Industries,Inc.的美國8,129,023；JG Park,JB Jun,TS Bae and JH Lee的美國公告專 利2006/0263581。然而，在大多數情況下，導電粒子上的交聯或膠化絕緣層或粒狀物導致必須對在Z方向達到理想連結導電率所需的接合溫度及/或壓力進行取捨。在某些情況下，如果在接合程序中無法移除絕緣層以暴露粒子的導電(金屬化)表面，可能就無法達成相連電極之歐姆接觸。此外，從導電粒子的表面移除交聯或膠化保護材質之後，這些交聯或膠化保護材質通常會成為與黏著劑不相容的多餘添加物，甚至有害，而時常損害異向性導電膜的成效。
Liang等人(以下稱「Liang」)的美國專利說明書2010/0101700揭露導電粒子在固定陣列異向性導電膜中配置成預定陣列。在一實施形態中，微共振腔室陣列可直接形成在托架腹板或預先塗佈於托架腹板的腔室形成層，且粒子之間的距離藉由例如雷射剝蝕程序、凸印程序、沖壓程序或蝕刻程序而預定並受到良好控制。此種導電粒子的非隨機陣列可以在不產生短路的情況下進行超精細間距接合，並在電極或凸塊墊上提供十分高的粒子捕捉率，而在間隙區域產生遠低於傳統異向性導電膜的粒子濃度。此外，由於每一個接合墊上的粒子數量皆受到精密控制，因此亦大幅增進接觸電阻或阻抗的一致性。在一實施例中，可將粒子部分嵌入形成異向性導電膜的黏著膜。接觸電阻或阻抗的一致性對於進階高解析度影片速率平板，特別是有機發光二極體等目前的驅動裝置特別重要，而固定陣列異向性導電膜清楚顯示在此種應用中的優勢。
本揭露改進Liang的固定陣列異向性導電膜，方法是提供一種異向性導電膜，其中導電粒子係使用一組成物處理或塗佈，該組成物包含具有與異向性導電膜黏著劑不相容的至少一片段或嵌 段之二相嵌段共聚物，判定方式為比較不相容嵌段與異向性導電膜黏著劑之溶解度參數。在一實施例中，可將導電粒子部分嵌入於黏著樹脂，使得至少一部份表面未被黏著劑覆蓋。在一實施例中，將粒子嵌入至其直徑的約三分之一至四分之三的深度。在一特定未限制的實施例中，導電粒子係塗佈有一嵌段共聚物，其包含與黏著樹脂(例如環氧化物、氰酸酯或丙烯酸樹脂)不相容、且更具體而言大致可溶於多官能環氧化物、丙烯酸酯、甲基丙烯酸酯或氰酸酯的硬質(高Tg或Tm)嵌段或片段。
在另一實施例中，除了不相容的嵌段，熱塑性嵌段共聚物進一步包含相容於或部分相容於黏著樹脂的軟質嵌段或片段(低Tg或Tm)。
已知該嵌段共聚物，特別是包含與黏著劑組成物不相容之嵌段的嵌段共聚物，即使在導電粒子聚集時亦提供導電粒子優異的絕緣性質，而且可在適度的接合溫度/壓力情況下(例如80至200℃和<3MPa)輕易移除以在連接區域的導電粒子和電極之間形成真正的歐姆接觸。嵌段共聚物亦可輕易溶解於或分散於一般溶劑，且藉由例如添加非溶劑/添加劑或變更溫度，可在導電粒子的表面上形成保護性熱塑性彈性體層或粒狀物而有效率地包覆導電粒子。另外，對於包含以嵌段共聚物包覆的導電粒子之異向性導電膜，其接合距離大幅降低，且熱衝擊和高溫高濕環境穩定性等黏著劑性質大幅增進。在某些情況下，使用此種絕緣導電粒子亦減少微孔隙容量並增進可靠性和抗疲勞性。不限於理論，嵌段共聚物可作為黏著劑矩陣的耐衝擊改質劑或低收縮劑。嵌段共聚物不相容片段和黏著劑組成物之間的不相容性減少了包覆層在處理和存儲期間從導電粒子 脫附的可能性。而且，熱塑性特徵改善了包覆層在接合程序期間的移除情形，即使在適度接合條件下，亦允許在粒子和電極之間形成真正的歐姆接觸。
一般而言，用於異向性導電膜的導電粒子會使用絕緣聚合物塗佈以減少粒子表面互相接觸而在X-Y平面產生電性短路的傾向。然而，此絕緣層使異向性導電膜之組裝更形複雜，原因是為了達成Z方向的導電性，必須移除導電粒子表面上的絕緣層。此舉提高了必須施加到異向性導電膜以達成玻璃(晶片玻璃接合)或薄膜(晶片薄膜接合)基板及晶片裝置之間的電性接觸所需之溫度或壓力值(例如從壓力棒)，特別是將熱固性絕緣層用於保護導電粒子時。根據一實施例，藉由使用嵌段共聚物處理導電粒子，可減少短路發生的機率。同時，嵌段共聚物可大幅增進填充於非接觸區域或電極間之間隔的黏著劑中粒子的分散性，並減少粒子在此積聚的機率。因而可降低X-Y平面發生短路的可能性。此外，相較於熱固性絕緣層，嵌段共聚物更容易從粒子表面移除，確保相連電極形成真正的歐姆接觸。
圖示為以熱塑性彈性體塗佈導電粒子的實驗室規模裝置。
Liang等人的美國公告專利2010/0101700、2012/0295098和2013/0071636係完整整合於此作為參考。
先前所述用於異向性導電膜的任何導電粒子皆可用於執行本揭露。鍍金粒子係用於一實施例中。在一實施例中，導電粒子具有狹窄的粒子大小分布，其標準差少於10%，較佳為少於5%，更佳為少於3%。粒子大小較佳為介於約1至250微米，更佳為約2至50微米，進一步更佳為約3至10微米。在另一實施例中，導電粒子具有雙峰或多峰分布。在另一實施例中，導電粒子具有所謂的尖突表面。選擇微共振腔和導電粒子的大小時，使每一個微共振腔都具有僅容納一個導電粒子的有限空間。為了促進粒子填充和轉移，茲此採用具有傾斜壁使上方開口寬於底部的微共振腔。
在一實施例中，使用包含聚合物核心及金屬殼的導電粒子。實用的聚合核心包括但不限於聚苯乙烯、聚丙烯酸酯、聚甲基丙烯酸酯、聚乙烯、環氧樹脂、聚胺酯、聚醯胺、酚、聚二烯和聚烯烴，及胺基塑膠，例如三聚氰胺甲醛、尿素甲醛、苯胍胺甲醛及其低聚物、共聚物、摻合物或合成物。如果合成物材料係用於核心、奈米粒子或碳奈米管，較佳為在核心中使用矽、鋁、BN、TiO2及陶土作為核心填充物。適用於金屬殼的材料包括但不限於Au、Pt、Ag、Cu、Fe、Ni、Sn、Al、Mg及其合金。具有Ni/Au、Ag/Au、Ni/Ag/Au等穿插金屬殼的導電粒子適用於增加硬度、導電性和抗腐蝕性。具有堅硬尖突的Ni、碳、石墨等粒子適用於增進易於遭到侵蝕的連接電極之可靠性，方法是穿透至腐蝕薄膜(如果有的話)。此種粒子可從以下商品取得：Sekisui KK(Japan)，商品名 MICROPEARL；Nippon Chemical Industrial Co.,(Japan)，商品名BRIGHT；及Dyno A.S.(Norway)，商品名DYNOSPHERES。要形成尖突，可於乳膠粒子上參雜或沈積矽等小型外來粒子，然後進行Ni的無電式電鍍步驟之前，再以Au替換部分鎳層。
在一實施例中，要製造狹窄分散之聚合物粒子，可採用例如美國公告專利4,247,234、4,877,761、5,216,065中所述之種子乳化聚合以及Adv.,Colloid Interface Sci.,13,101(1980)、J.Polym.Sci.,72,225(1985)及"Future Directions in Polymer Colloids",ed.El-Aasser and Fitch,p.355(1987),Martinus Nijhoff Publisher中所述之Ugelstad膨脹粒子程序。在一實施例中，使用直徑約5微米的單分散聚苯乙烯乳膠粒子作為可變形彈性核心。首先將粒子在甲醇中微晃進行處理以移除多餘的介面活性劑，並在聚苯乙烯乳膠粒子上建立多孔表面。在包含PdCl2、HCl和SnCl2的溶液中活化處理過的粒子，然後使用清水沖洗並過濾以移除Sn4+，再浸入包含Ni複合物和亞磷酸氫鹽的90℃無電式Ni電鍍溶液(來自例如Surface Technology Inc,Trenton,N.J.)約30至50分。Ni電鍍的厚度由電鍍液濃度、電鍍溫度及時間所控制。在一實施例中，所形成的導電粒子具有尖突。這些尖突可形成為但不限於尖銳尖突或瘤狀。
按照一實施例，對導電粒子進行處理/塗層時，係使用熱塑性嵌段共聚物，較佳為二相熱塑性彈性體。基本上，硬質熱塑性相係以力學或化學方式與軟質熱塑性相耦合，使嵌段聚合物具有二相結合特性。若要詳細瞭解熱塑性彈性體嵌段聚合物，可參閱：J.G.Drobny,Handbook of Thermoplastic Elastomers(2007)；A.Calhoun,G.Holden and H.Krichedorf,Thermoplastic Eladtomers (2004)；G.Wolf,Thermoplastic Elastomers,(2004)；及P.Rader Handbook of Thermoplastic Elastomers(1988)。
在本發明多個實施例中，可用於包覆導電性粒子的實用嵌段共聚物包括但不限於ABA、AB、(AB)n和ABC嵌段共聚物，例如苯乙烯嵌段共聚物，其包含SBS(苯乙烯-丁二烯-苯乙烯嵌段共聚物)、SIS(苯乙烯-異戊二烯-苯乙烯)、聚苯乙烯、聚-α-甲基苯乙烯、聚丁二烯、聚異戊二烯、聚胺酯、聚矽氧烷嵌段共聚物、聚酯嵌段共聚物、聚醯胺嵌段共聚物、聚烯烴嵌段共聚物等。
特別實用的共聚物為包含與異向性導電膜黏著樹脂不相容之嵌段的嵌段共聚物。在通常用於異向性導電膜的熱固性黏著劑中，以環氧化物和丙烯酸為基礎的黏著劑(包括環氧化物或丙烯酸樹脂)特別實用。與以環氧樹脂為基礎的黏著劑不相容之聚合物嵌段代表範例包括聚苯乙烯、聚-α-甲基苯乙烯、聚丁二烯、聚異戊二烯、聚二甲基矽氧烷、聚(丙烯酸烷酯)和聚(甲基丙烯酸烷酯)，特別是具有含超過2個碳原子的烷基、聚烯烴、聚環烯烴等之嵌段。用於異向性導電膜環氧黏著劑的嵌段聚合物之不相容片段通常具有低於約9.2或高於約11.5的溶解度參數。與以丙烯酸樹脂為基礎的異向性導電膜黏著劑不相容之聚合物嵌段代表範例包括聚苯乙烯、聚-α-甲基苯乙烯、聚丁二烯、聚異戊二烯、聚二甲基矽氧烷、聚烯烴、聚環烯烴等。用於丙烯酸異向性導電膜黏著劑的嵌段共聚物之不相容片段通常具有低於約9.2或高於約11.5的溶解度參數。在另一實施例中，用於丙烯酸異向性導電膜黏著劑的嵌段共聚物之不相容片段較佳為具有低於約9.2的溶解度參數，而且無法與黏著劑共聚物形成酸基和氫鍵等強烈反應。
在本發明之一實施例中，嵌段共聚物中的不相容嵌段佔彈性體總重量的約5至95重量%，更具體而言，不相容聚合物嵌段佔彈性體總重量的約20至80重量%。在一較佳實施例中，該熱塑性嵌段共聚物為熱塑性彈性體。在一實施例中，軟質嵌段或片段具有低於約25℃的Tg或Tm(較佳為低於0℃)，而在一實施例中，硬質嵌段或片段具有低於約50℃的Tg或Tm(較佳為低於90℃)。相較於異向性導電膜黏著樹脂，嵌段共聚物的不相容嵌段或片段具有至少約1.2(Cal/cc) 1/2 的溶解度參數差距。
嵌段共聚物可單獨用做導電粒子的絕緣層。另外，由嵌段共聚物與可連同嵌段共聚物之硬質或軟質嵌段混合的熱塑性聚合物所組成的摻合物可用於增進包覆和處理能力。較佳為所使用的熱塑性聚合物添加劑與不相容於異向性導電膜黏著劑的硬質嵌段共聚物嵌段相容。在本發明的一實施例中，熱塑性聚合物添加劑為硬質或軟質嵌段任一者之同元聚合物。在本發明的另一實施例中，嵌段共聚物為苯乙烯嵌段共聚物，且熱塑性聚合物添加劑為聚苯乙烯。在一實施例中，嵌段共聚物和熱塑性聚合物之混合比率為嵌段共聚物：熱塑性聚合物約20：80至95：5重量%，較佳為約30：70至70：30重量%。在一實施例中，相較於異向性導電膜黏著劑，熱塑性聚合物具有至少約1.2(Cal/cc) 1/2 的溶解度差距。
在一實施例中，包含嵌段共聚物的絕緣層係施加至導電粒子以達到具有平均厚度0.03-0.5微米，較佳為0.05-0.2微米的保護層。在另一實施例中，絕緣層與導電粒子的體積比為從約0.2/10至3/10，更佳為從約0.5/10至2/10。在另一實施例中，絕緣層為苯乙烯嵌段共聚物與聚苯乙烯之摻合物，其中聚苯乙烯具有約20至 80重量%，較佳為40-60重量%。
絕緣層量可根據所需最小接合距離和最小接合區域而調整。藉由較高的絕緣層覆蓋率，可達成較低的最小接合距離，但會影響接合區域的接觸導電率。要調整絕緣層的Tg或熱變形溫度時，可藉由改變嵌段共聚物的軟質和硬質嵌段比率或更改添加劑熱塑性聚合物的濃度。
在本發明一實施例中，熱塑性彈性體出現在導電粒子的表面時，其表面覆蓋率為約5至100%，較佳為20至100%。
要製造固定陣列異向性導電膜時，可於微共振腔陣列上將導電粒子進行射流散佈，再採用轉移程序將粒子轉移到黏著層，如同Liang等人的美國公告專利2010/0101700、2012/0295098和2013/0071636所述，整合於此以供參考。微共振腔陣列可直接形成於托架腹板上或預先塗佈於托架腹板的共振腔形成層上。適用於腹板的材料包括但不限於聚酯，例如聚對苯二甲酸乙二酯和聚萘二甲酸乙二酯、聚碳酸酯、聚醯胺、聚丙烯酸酯、聚碸、聚醚、聚醯亞胺和液態晶體聚合物及其摻合物、複合物、層合物或多層薄膜。適用於共振腔形成層的材料可包括但不限於熱塑性材料、熱固性材料或其先驅物、正型或負型光阻、或無機材料。 若要達成高效率的粒子轉移，較佳為採用薄層離型材料處理托架腹板以降低微共振腔托架腹板和黏著層之間的黏著性。在微共振腔形成步驟之前或之後，可藉由塗佈、印刷、噴塗、汽相沈積、熱轉移、電漿聚合化/交聯施加離型層。適用於離型層的材料包括但不限於氟聚合物或低聚物、矽油、氟化矽、聚烯烴、蠟、聚(環氧乙烷)、聚(環氧丙烷)、含長鏈疏水性嵌段或支鏈的介面活性劑、其共聚物或摻合 物。
微共振腔可直接形成於具有或不具有額外共振腔形成層的塑膠腹板基板。另外，微共振腔亦可在無凸印模的情況下形成，例如藉由雷射剝蝕或使用光阻進行蝕刻製程，然後進行顯影，再選擇性進行蝕刻或電鑄步驟。 適用於共振腔形成層的材料包括但不限於熱塑性、熱固性或其先驅物、正型或負型光阻、無機或金屬材料。關於雷射剝蝕，一實施例產生用於剝蝕的深紫外線雷射光束，其功率介於約0.1瓦/平方公分至約200瓦/平方公分之間；運用約0.1赫茲至約500赫茲之間的脈衝頻率；並施加約1個脈衝至約100個脈衝。在一較佳實施例中，雷射剝蝕功率介於約1瓦/平方公分至約100瓦/平方公分之間；運用約1赫茲至約100赫茲之間的脈衝頻率；並施加約10個脈衝至50個脈衝。亦建議在真空環境中使用載送氣體移除碎屑。
為了提升轉移效率，導電粒子的直徑和共振腔的直徑具有特定允差。為了達成高轉移率，按照美國公告專利2010/0101700所述的理論基礎，共振腔直徑的特定允差應遵守低於約5%至約10%標準差之條件。
在另一實施例，可以採用單峰、雙峰和多峰形式提供非隨機異向性導電膜微陣列。在採用單峰粒子形式的實施例中，非隨機異向性導電膜微共振腔陣列可具有分布成約為單一平均粒子大小值的粒子大小範圍，通常介於約2微米至約6微米之間，其中展現狹窄分布的實施例包括與平均粒子大小相較之下具有標準差低於10%的狹窄粒子大小分布。在展現狹窄分布的其他實施例，狹窄粒子大小分布較佳為與平均粒子大小相較之下具有低於約5%的標準 差。一般而言，所選共振腔大小的共振腔係形成為可容納具有所選粒子大小的粒子，其中該所選粒子大小約等於所選共振腔大小。
因此，在單峰粒子形式中，非隨機異向性導電膜微共振腔陣列中的微共振腔可具有分布成約為單一平均共振腔大小值的共振腔大小範圍，通常介於約2微米至約6微米之間，其中展現狹窄分布的實施例包括與平均共振腔大小相較之下標準差低於10%的狹窄共振腔大小分布。在展現狹窄分布的其他實施例，狹窄共振腔大小分布較佳為與平均共振腔大小相較之下具有低於約5%的標準差。
在非隨機異向性導電膜微共振腔陣列的雙峰粒子形式中，異向性導電膜粒子可以有兩個異向性導電膜粒子大小範圍，其中每一個異向性導電膜粒子類型都有對應的平均異向性導電膜粒子大小值，且第一個平均異向性導電膜粒子大小不同於第二個平均異向性導電膜粒子大小。一般而言，每一個平均異向性導電膜粒子大小可介於約2微米至約6微米之間。在雙峰粒子形式的部分實施例中，對應到個別平均異向性導電膜粒子大小值的每一個模式皆可具有對應的狹窄粒子大小分布。在部分所選的實施例中，狹窄粒子大小分布之特徵可為具有與平均粒子大小相較之下低於10%的標準差。在其他所選的實施例中，狹窄粒子大小分布之特徵可為與平均粒子大小相較之下具有低於5%的標準差。
在多峰非隨機異向性導電膜微共振腔陣列的製造程序之實施例中，可選取粒子以提供：第一異向性導電膜粒子類型，具有呈現第一異向性導電膜粒子分布的第一平均異向性導電膜粒子大小；第二異向性導電膜粒子類型，具有呈現第二異向性導電膜粒 子分布的第二平均異向性導電膜粒子大小；及第三異向性導電膜粒子類型，具有呈現第三異向性導電膜粒子分布的第三平均異向性導電膜粒子大小。在本實施例中，第二異向性導電膜粒子類型的平均異向性導電膜粒子大小大於第一異向性導電膜粒子類型，而第三異向性導電膜粒子類型的平均異向性導電膜粒子大小大於第二異向性導電膜粒子類型。若要製造此種多峰非隨機異向性導電膜陣列，可選擇性在異向性導電膜微共振腔陣列基板上形成多峰微共振腔陣列以獲得上述三個異向性導電膜粒子類型：具有第一平均異向性導電膜共振腔大小的第一共振腔類型；具有第二平均異向性導電膜共振腔大小的第二共振腔類型；及具有第三平均異向性導電膜共振腔大小的第三共振腔類型。一製造方法可包含將較大的第三類型異向性導電膜粒子施加到微共振腔陣列，然後將中型的第二類型異向性導電膜粒子施加到微共振腔陣列，再將較小的第一類型異向性導電膜粒子施加到多峰異向性導電膜微共振腔陣列。可使用一或多個上述陣列形成技術施加異向性導電膜粒子。
在特定實施例中，本發明進一步揭露製造電子裝置的方法。本方法包含以下步驟：將複數導電粒子放置到微共振腔陣列，其中導電粒子包含核心材料與使用耦合劑或絕緣材料進行表面處理的導電殼，然後將黏著層塗佈或層疊至已填充的微共振腔上。在一實施例中，將表面經處理的複數導電粒子放入微共振腔陣列的步驟係包含運用射流粒子分布程序將每一個導電粒子捕捉至單一微共振腔的步驟。在填充及轉移導電粒子並將導電粒子部分嵌入於黏著層的程序中，微共振腔的深度扮演重要角色。若微共振腔較深(相較於導電粒子的大小)，則較易在將粒子轉移到環氧層之前使其保持在共 振腔中，然而，如此則較難轉移粒子。若共振腔較淺，則較易將粒子轉移到黏著層，然而，如此則較難在轉移粒子之前保持填充在共振腔內的粒子。
在一實施例中，粒子沈積可能會受到施加射流粒子分布和捕捉程序的影響，捕捉程序會將每一個導電粒子捕捉到微共振腔內。茲此可使用多個捕捉程序。例如，在Liang的公告專利所揭露的一實施例中，可使用新穎的滾筒對滾筒連續射流粒子分布程序以僅將一個導電粒子捕捉至每一個微共振腔內。被捕捉的粒子隨後可從微共振腔陣列轉移到黏著層上的預定位置。一般而言，此等轉移的導電粒子之間的距離必須大於展透閾值，亦即導電粒子會聚集的密度閾值。一般而言，展透閾值會對應到微共振腔陣列的結構以及導電粒子數量。
一種非隨機異向性導電膜陣列，可在與黏著層相同或相反側上包含超過一組的微共振腔，其中微共振腔通常具有預定大小和形狀。在一特定實施例中，與黏著膜在同一側上的微共振腔在Z方向(厚度方向)具有大致相同的高度。在另一實施例中，與黏著膜在同一側上的微共振腔具有大致相同的大小和形狀。異向性導電膜即使在與黏著劑相同側上亦可具有超過一組微共振腔。在一實施例中，要製造包含約6微米(直徑)、約4微米(深度)、約3微米(間隔)的微共振腔之微共振腔陣列時，可對約3密耳(mil)的熱穩定聚醯亞胺膜(該聚醯亞胺來自Du Pont)採用雷射剝蝕法以形成微共振腔腹板。按照一實施例的粒子填充程序範例如下所示：使用光滑棒狀物藉由導電粒子分散對聚醯亞胺微共振腔陣列腹板進行塗佈。要確保無未填充的微共振腔時，可重複該程序。已填充的微共振腔陣列可 置於約室溫下乾燥約1分，並使用例如橡膠刮刷器或浸泡過丙酮溶劑的軟質無棉絨布輕輕擦除多餘的粒子。要分析已填充之微共振腔陣列的微觀影像，可使用ImageTool 3.0軟體。在接受評估的幾乎所有微共振腔陣列中，皆觀察到超過約99%的填充率。要改變粒子密度時，可使用不同的微共振腔陣列設計。另外，要調整粒子密度時，可經由控制導電粒子分散密度或填充程序中的穿過次數來改變填充程度。
以下是兩個粒子填充和轉移的逐步程序範例：鎳粒子：採用上述範例所述的粒子填充程序，以約4微米Umicore Ni粒子填充具有6x2x4微米陣列形態的聚醯亞胺微共振腔片。所獲得的粒子填充百分比通常大於約99%。環氧薄膜係製造成約15微米的目標厚度。將微共振腔片和環氧膜以面對面的方式貼附於鋼板上。將鋼板推壓通過來自Think & Tinker的商業化HRL 4200乾燥薄膜滾筒積層機。將積層壓力設定成約6磅/平方英吋(約0.423克/平方公分)，且積層速度設定成約2.5公分/分。將粒子從聚醯亞胺微共振腔轉移到環氧膜，其效率大於約98%。使用Cherusal接合器(型號TM-101P-MKIII.)在兩個電極之間接合所得到的異向性導電膜薄膜之後，在預接合期間於約70℃觀測到可接受的黏著度，且在主接合後於約170℃觀察到可接受的導電率。
金粒子：同樣地，以單一分散3.2微米Au-Ni塗佈之橡膠粒子填充具有約6x2x4微米陣列形態的聚醯亞胺微共振腔片。所獲得的粒子填充百分比亦大於約99%。環氧薄膜係使用32號製線條料製造成約20微米的目標厚度。將兩者面對面放置在鋼板上。將微共振腔片和環氧薄膜以面對面的方式貼附於鋼板上。將鋼板推壓 通過來自Think & Tinker的商業化HRL 4200乾燥薄膜滾筒積層機。將積層壓力設定成約6磅/平方英吋(約0.423克/平方公分)，且積層速度設定成約2.5公分/分。可觀察到優異的粒子轉移效率(大於約98%)。使用Cherusal接合器(型號TM-101P-MKIII.)在兩個電極之間接合後，所得到的異向性導電膜薄膜顯示可接受的黏著度和導電率。
在一實施例中，使用旋臂滾筒將微共振腔環放置到粒子填充塗佈機。將3至6重量%的導電粒子分散於異丙醇中，藉由機械攪拌進行混合，並使用例如Cole Parmer的Masterflex泵通過L/S 13配管藉由狹縫或細縫塗佈模、遮幕或噴嘴以射流程序進行散佈。使用以100%聚酯刮刷器包覆的滾筒將導電粒子填充入微共振腔。使用Shima American Co.的聚胺酯滾筒小心移除微共振腔外的多餘粒子，並使用真空裝置回收導電粒子。可將回收的粒子收集或重新循環至供給料斗以重新用於腹板。在一實施例中，可使用超過一個散佈站點，確保將導電粒子捕捉到每一個微共振腔，而降低或減少不含粒子的微共振腔數量。
再者，可將被捕捉的粒子從微共振腔陣列轉移到黏著層上的預定位置。一般而言，此等轉移的導電粒子之間的距離必須大於展透閾值，亦即導電粒子連結或聚集的密度閾值。一般而言，展透閾值為微共振腔陣列結構之結構/圖案及導電粒子數量的函數。
較佳為運用一或多個程序移除多餘導電粒子，例如在射流組裝之後。滾筒對滾筒連續射流粒子分布程序可包含清潔程序以便將多餘的導電粒子從微共振腔陣列表面移除。清潔程序可為非 接觸清潔程序、接觸清潔程序或非接觸及接觸清潔程序的有效組合。
粒子清潔程序的部分代表實施例運用非接觸清潔程序，包括但不限於一或多個吸入程序、氣流程序或溶劑噴塗程序。可將移除的多餘導電粒子例如採用吸入裝置收集以回收或重新利用。可藉由給予清潔液體，例如但不限於藉由噴塗溶劑或溶劑混合物，進一步輔助非接觸吸入程序以增進清潔效率。本發明的部分其他代表實施例可運用接觸清潔程序將多餘導電粒子從微共振腔陣列表面移除。接觸清潔程序包括使用無縫毛氈、刮刷器、刮刀、黏著劑材料或膠黏軋輥。使用無縫毛氈時，亦可使用吸入程序從無縫毛氈表面回收導電粒子並清潔毛氈表面。在此毛氈/吸入程序中，毛細力和吸入力皆會吸引多餘導電粒子以移除並回收多餘粒子，其中吸入力由無縫毛氈內側施加。可藉由給予清潔液體、溶劑或溶劑混合物進一步輔助此吸入程序以改善清潔效率。
在射流填充步驟之後，可將微共振腔中的導電粒子轉移到以未硬化黏著劑預先塗佈或是在操作程序中進行塗佈的基板。藉由重複粒子填充及轉移步驟來重新使用微共振腔帶。
用於異向性導電膜的黏著劑可為熱塑性、熱固性或其先驅物。實用的黏著劑包括但不限於壓力敏感黏著劑、熱熔黏著劑、熱或輻射硬化黏著劑。黏著劑可包含例如環氧化物、苯氧基樹脂、酚樹脂、胺甲醛樹脂、聚苯并、聚胺酯、氰酸酯、丙烯酸、丙烯酸酯、甲基丙烯酸酯、乙烯聚合物、橡膠(例如聚(苯乙烯-共-丁二烯)及其嵌段共聚物)、聚烯烴、聚酯、未飽和聚酯、乙烯酯、聚己內酯、聚醚、矽樹脂及聚醯胺。環氧化物、氰酸酯和多官能丙烯酸 酯特別實用。催化劑或包括潛硬化劑等的硬化劑可用於控制黏著劑的硬化動力模式。適用於環氧樹脂的硬化劑包括但不限於二氰二胺、己二酸二醯肼、2-甲基咪唑及其包覆產物，例如Asahi Chemical Industry的分散於雙酚A環氧化物液體的Novacure HX；胺類，例如乙二胺、二伸乙三胺、三伸乙四胺、BF3胺加成物、Ajinomoto Co.,Inc的Amicure；及鋶鹽，例如二胺基二苯碸、異羥苯基苯甲基甲基鋶六氟銻酸鹽。
本發明藉由以下非限定的範例詳細闡述。
製造固定陣列異向性導電膜。
環氧化物黏著劑組成物包含：Aldrich的5.0份甘油三環氧丙醚、Japan Epoxy Resins,Tokyo的6.0份雙酚F類型環氧化物樹脂JER YL983U；InChem Phenoxy Resin,SC的29.66份PKFE；Arkema Inc,PA的4.24份M52N；CVC Thermoset Specialties,NJ的2.8份Epalloy 8330；Dow Chemicals,TX的2.8份ParaloidTM EXL-2335；Du Pont,DE的1.0份Ti-Pure R706；Asahi Chemicals,Tokyo的48.0份Novacure HXA 3922；及Momentive Performance Materials,Inc.,OH的0.2份Silwet L7622和0.3份Silquest A187。以上組成物分散於乙酸乙酯/乙酸異丙酯(6/4)溶液以獲得含約45重量%固體的塗佈液體。將最後得到的液體經由狹縫塗佈模塗佈至2密耳(mil)PET上得到約15.5 +/- 0.5微米的乾燥覆蓋物。
第1圖說明粒子包覆用的器具，如下所示：(1)400毫升燒杯；(2)折疊雙葉推進器；(3)攪拌器1，頂部攪拌器；(4)數位蠕動泵；(5)去磁器；(6)注射器針頭；(7)30毫升注射器；(8)超音波破碎儀；(9)底部附出口的1000毫升反應器；(10)三葉推進器；(11)攪 拌器2，強力攪拌器；(12)及配管。
導電粒子包覆
將1克以金屬塗佈的導電聚合物粒子(26GNR3.0-EHD，來自Nippon Chemical)及49克MEK(甲基乙基甲酮)先以超音波水浴再使用低剪力頂部攪拌器以240轉/分均勻混合於400毫升燒杯。對導電粒子分散液，加入含有0.2重量%的絕緣聚合物或聚合物摻合物之50克THF/MEK(比例15/85)溶液並予以徹底混合。
對最後得到的導電粒子混合物(I)，使用去磁器(Magnetool Inc.)去磁，並經由內徑為0.01英吋的25G BD Precision Glide注射器針頭以4.8毫升/分的流速連續計量供給至10毫升注射器。在10毫升注射器內將注射器針頭緊貼音波探針端(Fisher Scientific超音波破碎儀，型號100)，並以5瓦特功率音波連續振動注射器內的導電粒子流體。
如第1圖所示，將注射器部分沒入內含300毫升異丙醇(對於要塗佈至導電粒子上的絕緣聚合物為非溶劑)的1000毫升反應器內。將導電粒子混合物(I)計量供給至注射器中的非溶劑溶液，並經由10毫升注射器的底部注射到包含異丙醇的1000毫升反應器，使用裝有低剪力三葉推進器的頂部攪拌器以280轉/分連續攪拌。在包覆程序中，針頭和音波探測器尖端皆在液面下方並互相緊貼。雖然不應受限於理論，但一般認為將絕緣聚合物注射至注射器中的非溶劑浴時，會立即由鄰近的導電粒子吸附，因而形成小型(奈米大小)凝塊或膨脹聚合物粒子。音波探測器可協助減少聚合物凝塊的大小，強化對導電粒子上絕緣聚合物大小的控制，同時可協助保持已包覆之導電粒子的分散穩定性。
如同電子顯微鏡SEM(Hitachi，型號S2460N)所證實，由反應器底部收集之導電粒子上塗佈有薄質非黏性絕緣聚合物層。
可選擇性使用另一泵(未顯示)將其他非溶劑計量供給至注射器，以便在注射器中獲得精確的溶劑/非溶劑比例。另外，可使用注射器壁周圍有小孔洞(未顯示)的注射器允許非溶劑(異丙醇)連續流入注射器，對其中的溶劑/非溶劑比例維持精確控制。
範例1-9所使用的絕緣聚合物列於表1，其中所獲得的無絕緣層導電粒子用於第一控制組(控制組1)，而按照美國公告專利20120295098所述以耦合劑處理過的導電粒子用於第二控制組(控制組2)。
將製造之已微包覆的導電粒子填充至微共振腔帶，隨後轉移至黏著劑上方，如美國公告專利2013/0071636及美國公告專利13/678,935(多層粒子形貌)，美國公告專利13/796,873(影像加強層)及美國公告專利2011/0253943以獲得具有從17,500至50,000個/平方毫米之間粒子密度範圍且標準差低於3%的各種固定陣列異向性導電膜。接合電極之成效總結於表1和表2。在所有情況下，黏著劑厚度皆控制在15.5 +/- 0.5微米，且粒子上的包覆層平均覆蓋厚度控制在約0.1~0.2微米。
(13)保持在85℃及85% RH，7日後量測(14)評級基準為觀察到的小孔洞數量，評級10為最佳(無可觀察的微孔洞)。
作為進一步對比，包覆導電粒子時，使用三種苯氧基樹脂進行：InChem Phenoxy Resin的PKFE、PKHB和PKCP(範例10、11和12，未顯示在表中)，三者皆與用於異向性導電膜的環氧化物黏著劑組成物完全相容。事實上，PKFE係用於黏著劑中的固著劑。相較範例1-9，以上三個範例對於包覆效率、射流粒子分布程序及隨後的粒子轉移程序皆展現較狹窄的製程窗口。若使用與環氧化物黏著劑組成物高度相容的絕緣層，則較難以藉由絕緣粒子達成具有高粒子密度(例如大於約15,000個/平方毫米)及一致性的固定陣列異向性導電膜。
最小接合距離，亦即在不造成短路的情況下上下接合電極可達到的最小距離，係為異向性導電膜的其中一項重要特徵。較低的最小接合距離代表較寬的接合製程視窗或較高的可得解析度。
從表1可清楚看到，如美國公告專利20120295098所述使用經耦合劑處理的導電粒子(範例2)，或是絕緣聚合物(範例1-9)，會使固定陣列異向性導電膜的最小接合距離(範例1)急遽下降(例如從13毫米降至3-9毫米)。在所有情況下，即使經過熱衝擊和HHHT老化測試，亦可在相連電極觀察到可接受的接觸電阻(表2)。又，如先前所述，範例1-9中的所有塗層粒子皆顯示微射流分布程序提供理想的分散穩定性和處理性。
茲此亦發現塗佈有與環氧化物樹脂高度相容的絕緣聚合物之粒子(範例2和3)會導致較差的解析度或較高的最小接合 距離。不受限於理論，一般認為與黏著劑高度相容或具有低變形溫度的絕緣層較常因黏著劑組成物而塑化或遭移除，導致導電粒子的保護不足。對於環氧化物黏著劑中的主要原料之溶解度參數，固著劑(PKFE)和二環氧化物(雙酚A二氧化丙烯醚(diglycidyl ether)和雙酚F二氧化丙烯醚)分別為約10.68、10.4和10.9(Cal/cc)1/2(表3)。
溶解度參數在10.4 +/- 1.2(Cal/cc)1/2之間的聚合物通常與環氧化物黏著劑較為相容而較不理想。具有羰基、醚基、羥基、硫醇基、硫化物、胺基、醯胺基、醯亞胺基、聚胺酯、尿素等可與黏著劑中環氧化物或羥基形成氫鍵的官能基之聚合物通常可增進相容性而為較不理想的絕緣塗層。因此，相較聚苯乙烯(範例1，最小接合距離=3微米)，聚甲基丙烯酸甲酯及其共聚物(範例2、3和9)通常會有相對較大的接合距離(例如約4至7微米)。關於溶解度參數的詳細清單，可參閱"Polymer Handbook" by J.Brandrup,E.H.Immergut and E.A.Grulke(Wiley-Interscience)及"Prediction of Polymer Properties" by J.Bicerano(Marcel Dekker)。
雖然從溶解度參數判斷可知聚丁二烯和聚異戊二烯與環氧化物黏著劑較不相容，但兩者較低的Tgs(約-40至-70℃)通常 在異向性導電膜儲存條件下對於黏著劑材料具有較差的阻隔性。對於具有以含大量橡膠嵌段的嵌段共聚物塗佈之粒子的異向性導電膜(範例4和6)，其最小接合距離隨著將高分子量聚苯乙烯(如同嵌段共聚物的硬質嵌段)加入絕緣層(範例5和7)而減少，原因可能是在異向性導電膜儲存條件下(通常介於-10℃至25℃)絕緣層阻隔性增進之故。亦可加入與任一嵌段，特別是嵌段共聚物的不相容嵌段相容的其他聚合物，以增進絕緣塗層之阻隔性。另外，亦可使用具有與異向性導電膜黏著樹脂不相容的較高重量比硬質嵌段之嵌段共聚物來達成目的。
使用由嵌段共聚物及摻合物保護的粒子之異向性導電膜係列於範例4-9。特別實用者為包含以下項目的嵌段共聚物：軟質嵌段或片段，具有低於室溫的Tg或Tm，較佳為低於0℃；及硬質嵌段/片段，具有高於室溫的Tg或Tm，較佳為高於塗層或粒子轉移程序溫度(通常為50-90℃)。在範例4-9，所使用之軟質嵌段(聚丁二烯、聚異戊二烯和聚丙烯酸正丁酯)的Tgs低於室溫，且硬質嵌段(聚苯乙烯和聚甲基丙烯酸甲酯)的Tgs約為100℃。嵌段共聚物經過乾燥、塗層和澆鑄等處理後，硬質和軟質嵌段通常形成二相形態。
如第1圖所示，含以嵌段共聚物塗佈之粒子的異向性導電膜樣品展現出極低的最小接合距離。表2亦清楚顯示，相較只使用耦合劑(控制組2)及熱塑性聚合物(範例1、3)，使用由嵌段共聚物或其摻合物保護的粒子之異向性導電膜(範例5、7-9)即使經過加速老化及熱衝擊測試，在接合電極的總體剝離能量、最大剝離力及可觀測微孔洞評級上皆展現優異的成效。不限於理論，一般認為用 於範例5、7、8和9的嵌段共聚物之彈性特徵展現理想特性，可作為衝擊/振動改質劑增進黏著強度，或作為低收縮劑降低硬化黏著劑的收縮或翹曲。
相較苯乙烯-丁二烯-甲基丙烯酸甲酯嵌段共聚物(範例8)，甲基丙烯酸甲酯-丙烯酸丁酯-甲基丙烯酸甲酯嵌段共聚物(範例9)顯示較高最小接合距離，原因可能是相較聚苯乙烯或聚丁二烯嵌段，與異向性導電膜黏著劑較相容的聚甲基丙烯酸甲酯嵌段濃度較高之故。
不限於理論，一般認為包含與異向性導電膜黏著樹脂不相容的嵌段之嵌段共聚物在導電粒子上展現較高的吸附效率，使得絕緣層從非電極區域(間隙)的粒子脫附或脫落的機率大幅降低。因此，在X-Y平面發生短路的機率及最小接合距離大幅減少。相較傳統熱固性或凝膠絕緣層，連結電極區域的嵌段共聚物較易在接合程序中移除而顯露粒子的導電殼以提供高導電率之連結。從電極區域移除的嵌段共聚物亦發揮作為衝擊改質劑或低收縮劑的作用而降低硬化收縮率，使得黏著劑強度大幅增加，且減少損及連接裝置環境穩定性的微孔洞之形成。
按照以上說明、圖示和範例，本發明揭露一種異向性導電膜，其包含表面經絕緣層處理的複數導電粒子，其中該絕緣層包含的嵌段共聚物由與異向性導電膜黏著劑不相容的嵌段或片段構成。在一實施例中，相較異向性導電膜黏著樹脂，嵌段共聚物之不相容的嵌段或片段具有至少1.2(Cal/cc)1/2的溶解度參數差距。絕緣導電粒子係配置在預定非隨機粒子位置作為黏著層內或上的非隨機陣列，其中該隨機粒子位置對應微共振腔陣列的複數預定微共振腔 位置以便將導電粒子載運並轉移至黏著層。導電粒子會轉移到黏著層。
除了上述實施例，本發明進一步揭露一種電子裝置，其附有連結至本發明異向性導電膜的電子元件，其中異向性導電膜具有按照上述處理方法配置之表面經處理的非隨機導電粒子陣列。在特定實施例中，電子裝置包含顯示裝置。在另一實施例中，電子裝置包含半導體晶片。在另一實施例中，電子裝置包含具有印刷電路的印刷電路板。在另一實施例中，電子裝置包含具有印刷電路的彈性印刷電路板。
藉由詳細敘述本發明並提及特定實施例作為參考，可知在不偏離由以下申請專利範圍所定義的本發明範圍之情況下，能夠提供多個變形和修改。

Claims (47)

  1. 一種異向性導電膜(ACF)，其包含：(a)具有實質均勻厚度的黏著層；及(b)個別黏著於黏著層的複數個導電粒子，其中導電粒子係塗佈有包含嵌段共聚物之絕緣層，該嵌段共聚物係包含與異向性導電膜之黏著層的黏著樹脂不相容之嵌段或片段，且該複數個導電粒子係配置成具有X和Y方向的非隨機陣列。
  2. 如申請專利範圍第1項的異向性導電膜，其中該嵌段共聚物包含硬質及軟質嵌段或片段。
  3. 如申請專利範圍第1項的異向性導電膜，其中該軟質嵌段或片段具有低於約25℃的Tg或Tm。
  4. 如申請專利範圍第1項的異向性導電膜，其中該硬質嵌段或片段具有高於約50℃的Tg或Tm。
  5. 如申請專利範圍第1項的異向性導電膜，其中相較於該異向性導電膜黏著樹脂，該嵌段共聚物之不相容的嵌段或片段具有至少約1.2(Cal/cc)1/2的溶解度參數差距。
  6. 如申請專利範圍第1項的異向性導電膜，其中該絕緣層包含與該異向性導電膜黏著樹脂不相容的嵌段共聚物及熱塑性聚合物之摻合物。
  7. 如申請專利範圍第3項的異向性導電膜，其中該熱塑性聚合物與該嵌段共聚物的任一嵌段或片段相同或相容。
  8. 如申請專利範圍第6項的異向性導電膜，其中相較於該異向性導電膜樹脂，該熱塑性聚合物具有至少約1.2(Cal/cc)1/2的溶解度參數差距。
  9. 如申請專利範圍第1項的異向性導電膜，其中該嵌段共聚物包含 選自由苯乙烯、烯烴、聚醯胺、聚胺酯、聚酯、聚丙烯酸酯和聚甲基丙烯酸酯嵌段所組成群組的嵌段或片段。
  10. 如申請專利範圍第9項的異向性導電膜，其中該嵌段共聚物包含至少約10重量%的苯乙烯嵌段。
  11. 如申請專利範圍第1項的異向性導電膜，其中至少一部份導電粒子係部分嵌入於黏著層。
  12. 如申請專利範圍第1項的異向性導電膜，其中該嵌段共聚物以約5至100%表面覆蓋率出現於導電粒子表面上。
  13. 如申請專利範圍第1項的異向性導電膜，其中該嵌段共聚物以約20%至100%表面覆蓋率出現於導電粒子表面上。
  14. 如申請專利範圍第1項的異向性導電膜，其中該粒子配置成在X及/或Y方向具有約3至30微米之間距的陣列。
  15. 如申請專利範圍第1項的異向性導電膜，其中該粒子區域配置成在X及/或Y方向具有約5至12微米之間距的陣列。
  16. 如申請專利範圍第15項的異向性導電膜，其中大部分粒子區域在每1個粒子區域具有不超過1個導電粒子。
  17. 如申請專利範圍第1項的異向性導電膜，其中該導電粒子包含一層金屬、介金屬化合物或穿插型金屬(interpenetrating metal)化合物。
  18. 如申請專利範圍第1項的異向性導電膜，其中該嵌段共聚物為苯乙烯或丙烯酸嵌段共聚物。
  19. 如申請專利範圍第18項的異向性導電膜，其中該嵌段共聚物係選自由聚(苯乙烯-嵌段-丁二烯-嵌段-苯乙烯)、聚(苯乙烯-嵌段-異戊二烯-嵌段-苯乙烯)、聚(苯乙烯-嵌段-異戊二烯-嵌段-甲基丙烯酸甲酯)、聚(甲基丙烯酸甲酯-嵌段-丙烯酸丁酯-嵌段-甲基丙烯酸甲酯) 及其混合物所組成之群組。
  20. 如申請專利範圍第1項的異向性導電膜，其中該絕緣層為嵌段共聚物與熱塑性聚合物之摻合物，該熱塑性聚合物選自由聚苯乙烯、聚(α-甲基苯乙烯)、聚(甲基丙烯酸酯)、聚(丙烯酸酯)或其混合物或共聚物構成之組合。
  21. 如申請專利範圍第11項的異向性導電膜，其中少於約四分之三的粒子直徑係嵌入於黏著層。
  22. 如申請專利範圍第1項的異向性導電膜，其中該黏著劑包含環氧樹脂、苯氧基樹脂、丙烯酸樹脂或氰酸酯樹脂。
  23. 如申請專利範圍第1項的異向性導電膜，其中該黏著劑包含多官能環氧化物、多官能丙烯酸酯、多官能甲基丙烯酸酯或多官能氰酸酯。
  24. 如申請專利範圍第21項的異向性導電膜，其中少於約三分之二的粒子直徑係嵌入於黏著層。
  25. 如申請專利範圍第24項的異向性導電膜，其中約二分之一至三分之二的粒子直徑係嵌入於黏著層。
  26. 如申請專利範圍第1項的異向性導電膜，其中電子裝置接觸黏著層表面上的導電粒子。
  27. 如申請專利範圍第1項的異向性導電膜，其中該電子裝置為積體電路、印刷電路、發光二極體或顯示裝置。
  28. 如申請專利範圍第1項的異向性導電膜，其中該黏著層的厚度為約5至35微米。
  29. 如申請專利範圍第1項的異向性導電膜，其中該黏著層的厚度為約10至25微米。
  30. 一種使用保護殼進行絕緣處理之導電粒子，該保護殼包含嵌段共聚物，其包含與由丙烯酸酯或甲基丙烯酸酯形成之環氧樹脂或丙烯酸黏著樹脂不相容的嵌段或片段。
  31. 如申請專利範圍第30項的粒子，其中該嵌段或片段與雙酚A二氧化丙烯醚(diglycidyl ether)、雙酚F二氧化丙烯醚或其聚合物或共聚物不相容。
  32. 如申請專利範圍第30項的粒子，其中該嵌段共聚物包含與多官能丙烯酸酯或多官能甲基丙烯酸酯不相容的嵌段或片段。
  33. 如申請專利範圍第30項的粒子，其中該嵌段共聚物為ABA、AB、(AB)n或ABC類型的嵌段共聚物。
  34. 如申請專利範圍第33項的粒子，其中該嵌段共聚物包含聚苯乙烯或聚-α-甲基苯乙烯嵌段。
  35. 如申請專利範圍第33項的粒子，其中該嵌段共聚物包含聚丁二烯或聚異戊二烯嵌段。
  36. 如申請專利範圍第33項的粒子，其中該嵌段共聚物包含聚胺酯或聚酯嵌段。
  37. 如申請專利範圍第33項的粒子，其中該嵌段共聚物包含聚酯、聚醚或聚矽氧烷嵌段。
  38. 如申請專利範圍第30項的粒子，其中該嵌段共聚物包含聚(甲基丙烯酸烷酯)嵌段或聚(丙烯酸烷酯)嵌段，其中該烷基具有從1至30的碳數。
  39. 如申請專利範圍第38項的粒子，其中該嵌段共聚物包含與環氧樹脂不相容的嵌段。
  40. 如申請專利範圍第38項的粒子，其中該嵌段共聚物包含與雙酚A 二氧化丙烯醚、雙酚F二氧化丙烯醚或其聚合物或共聚物不相容的嵌段。
  41. 如申請專利範圍第30項的粒子，其中相較於該異向性導電膜黏著樹脂，該不相容的嵌段或片段具有至少約1.2(Cal/cc)1/2的溶解度參數差距。
  42. 如申請專利範圍第30項的粒子，其中該絕緣層包含嵌段共聚物及熱塑性聚合物之摻合物。
  43. 如申請專利範圍第42項的粒子，其中該熱塑性聚合物與任一嵌段共聚物嵌段或片段相容。
  44. 如申請專利範圍第43項的粒子，其中該嵌段聚合物選自由苯乙烯、聚雙烯、烯烴、聚醯胺、聚胺酯、聚酯、聚丙烯酸酯和聚甲基丙烯酸酯熱塑性彈性體所組成之群組。
  45. 如申請專利範圍第41項的粒子，其中該嵌段聚合物包含具有高於約50℃的Tg或Tm之硬質嵌段或片段。
  46. 如申請專利範圍第41項的粒子，其中該軟質嵌段或片段具有低於約25℃的Tg或Tm。
  47. 如申請專利範圍第45項的粒子，其中該嵌段聚合物包含至少約10%的苯乙烯嵌段。
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