TWI596176B - 各向異性導電膜組成物、各向異性導電膜以及半導體元件 - Google Patents
各向異性導電膜組成物、各向異性導電膜以及半導體元件 Download PDFInfo
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- TWI596176B TWI596176B TW101146075A TW101146075A TWI596176B TW I596176 B TWI596176 B TW I596176B TW 101146075 A TW101146075 A TW 101146075A TW 101146075 A TW101146075 A TW 101146075A TW I596176 B TWI596176 B TW I596176B
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- H01B1/20—Conductive material dispersed in non-conductive organic material
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- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
- H01L23/49866—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials
- H01L23/49883—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials the conductive materials containing organic materials or pastes, e.g. for thick films
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Description
本發明係有關於各向異性導電膜組成物,其包括乙烯-醋酸乙烯酯共聚物、聚胺甲酸酯樹脂和有機微粒子,以及包括該組成物的膜。
更特別地,本發明係有關於各向異性導電膜組成物,其包括乙烯-醋酸乙烯酯共聚物、聚胺甲酸酯樹脂和有機微粒子以具有良好的流動性,藉此提供該膜組成物之平順的填充,抑制由於收縮和膨脹之熱變形以具有較少的氣泡,且展現出傑出的黏著力,以及包括該組成物的膜。
一般而言,各向異性導電膜(ACFs)係提及膜狀的黏著劑,其中導電粒子,例如金屬顆粒(包括鎳或金顆粒)或是金屬塗覆的聚合物顆粒,係分散於樹脂內,例如環氧樹脂內。各向異性導電膜意思是具有電各向異性與黏著性質的聚合物層,其於該膜的厚度方向上展現出導電性質且於其表面的方向上展現出絕緣性質。當一種各向異性導電膜係配置於待連接的電路板之間並接受特定的條件下之加熱和壓擠時,電路板之電路終端係通過導電粒子而電氣地連接以及絕緣黏合樹脂充滿於鄰接的電路終端之間的空間內以使導電粒子彼此隔離,藉此提供電路終端之間高的絕緣性能。
隨著朝大面板且擴大的佈線之近來擴大的趨勢,介於電極之間的空間變得更寬闊。因而,當連接基板由於在接合時於熱和壓力下的壓製而膨脹且在接合之後收縮回去,黏著劑組成物會膨脹且收縮達嚴重的程度,造成產生很多的氣泡以及黏著劑組成物之填充效果的劣化。
為了解決此等問題,一種方法是使用一種具有高的玻璃轉移溫度(Tg)之黏結劑樹脂。然而,甚至於膜被裝配成耐受熱之收縮和膨脹的情況中,該膜的填充由於樹脂低的流動性而不會平順地達成以及因而未填充的部分會繼續存在,導致嚴重的氣泡。
慣用的各向異性導電膜揭示於韓國專利公開案第10-2010-0014076號(於2010年二月10日公開)和第10-2010-0100792號(於2010年九月15日公開)之內。
以上的公開案揭示包括有機微粒子之各向異性導電膜。此等公開案僅僅描述藉由將該有機微粒子添加至一般的膜組成物而得到的功效,但是未提及起因於該有機微粒子與特定的黏結劑樹脂之組合的增效效應。
為了解決前述的問題,本發明的發明人發展一種各向異性導電膜,其包括乙烯-醋酸乙烯酯共聚物、聚胺甲酸酯樹脂,及有機粒子以具有良好的流動性,藉此提供平順的填充該膜組成物,抑制由於收縮和膨脹之熱變形以產生較少的氣泡,以及展現出傑出的黏著力。
本發明旨在提供各向異性導電膜組成物,其包括乙烯-醋酸乙烯酯共聚物以具有低的熔化黏度,如此由於低溫下高的流動性而平順地填充電極之間的間隙,以及包括該組成物的膜。
此外,本發明旨在提供各向異性導電膜組成物,其包括聚胺甲酸酯樹脂和有機微粒子與乙烯-醋酸乙烯酯共聚物一起來控制該膜組成物之黏度,藉此在最終的壓製之後提供較小的氣泡面積且展現出傑出的黏著力,以及包括該組成物的膜。
再者,本發明旨在提供各向異性導電膜組成物,其抵抗由於收縮和膨脹之熱變形,藉此甚至於高溫和濕度下儲存長時間可維持氣泡面積和黏著於某範圍內且展現出優異的可靠度,以及包括該組成物的膜。
本發明係有關於一種各向異性導電膜,其包括乙烯-醋酸乙烯酯共聚物、聚胺甲酸酯樹脂,以及有機微粒子。
依據本發明的一個態樣,有提供各向異性導電膜組成物,其包括,a)乙烯-醋酸乙烯酯共聚物;b)聚胺甲酸酯樹脂;以及c)有機微粒子;其中該各向異性導電膜組成物於80℃下具有2,000至8,000 Pa.s的熔化黏度。
依據本發明的另一個態樣,該各向異性導電膜組成物可以包括,
a)5至50重量份的該乙烯-醋酸乙烯酯共聚物;b)10至70重量份的該聚胺甲酸酯樹脂;以及c)0.1至30重量份的該有機微粒子;以100重量份的固體含量之該各向異性導電膜組成物為基準。
依據本發明的另一個態樣,該有機微粒子可以包含選自於以下所構成的群組之至少一者:苯乙烯-二乙烯苯、氯化聚乙烯、二甲基聚矽氧烷、甲基丙烯酸甲酯-丙烯酸丁酯-二甲基矽氧烷共聚物、苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-丁二烯熱塑性彈性體、丁二烯橡膠、苯乙烯-丁二烯橡膠,以及乙烯甲基丙烯酸環氧丙酯(ethylene glycidyl methacrylate)。
依據本發明的另一個態樣,有提供一種該組成物所形成的各向異性導電膜。
依據本發明的另一個態樣,有提供一種各向異性導電膜,其包括,a)乙烯-醋酸乙烯酯共聚物;b)聚胺甲酸酯樹脂;以及c)有機微粒子;其中該各向異性導電膜在150℃和4MPa歷時4秒的壓製之後具有1,000gf/cm或是更大的黏著強度。
依據本發明的另一個態樣,各向異性導電膜在150℃和4MPa歷時4秒的壓製以及接而儲存於85℃和85% RH歷時500小時之後,可以具有800gf/cm或是更大的黏著強
度。
各向異性導電膜在150℃和4MPa歷時4秒的壓製以及接而儲存於85℃和85% RH歷時500小時之後,可以具有10%或更低的氣泡面積,以電極之間的空間面積為基準。
各向異性導電膜組成物可以具有於80℃下為2,000至8,000 Pa.s的熔化黏度。
依據本發明的再另一個態樣,有提供一種半導體元件,其包括一配線基板及一半導體晶片,其中該半導體元件係由各向異性導電膜所連接。
依據本發明的各向異性導電膜組成物和含括該組成物的該膜包括乙烯-醋酸乙烯酯共聚物、聚胺甲酸酯樹脂和有機粒子以具有良好的流動性,藉此提供該膜組成物之平順的填充,抑制由於收縮和膨脹之熱變形以產生較少的氣泡,以及展現出傑出的黏著力。
更特別地,該各向異性導電膜組成物和含括該組成物的該膜包括乙烯-醋酸乙烯酯共聚物以具有低的熔化黏度,因而由於低溫下高的流動性來平順地填充電極之間的間隙。
此外,該各向異性導電膜組成物和含括該組成物的該膜包括聚胺甲酸酯樹脂及有機微粒子與乙烯-醋酸乙烯酯共聚物一起而來控制該膜組成物之黏度,藉此在最終的壓製之後提供較小的氣泡面積以及展現出傑出的黏著力。
再者,該各向異性導電膜組成物和含括該組成物
的該膜抵抗由於收縮和膨脹之熱變形,藉此甚至於高溫和濕度下儲存長時間可維持氣泡面積和黏著於某範圍內以及展現出優異的可靠度。
本發明之例示性具體例現在將詳細地描述。對熟悉此藝者而言為顯而易見的細節將於本文中省略。而且於本文中,定冠詞“一(a)”、“一(an)”以及其之衍生物不會把複數排除在外。
本發明的一個態樣提供各向異性導電膜組成物,其包括,a)乙烯-醋酸乙烯酯共聚物;b)聚胺甲酸酯樹脂;以及c)有機微粒子;其中該各向異性導電膜組成物具有於80℃下為2,000至8,000 Pa.s的熔化黏度。
乙烯-醋酸乙烯酯(EVA)共聚物可包括本技藝中典型使用的任何EVA共聚物,無特別受限制。
於EVA共聚物內,乙烯和醋酸乙烯酯的量不特別受限制。舉例而言,乙烯可以以20至60重量份的量存在以及醋酸乙烯酯可以以40至80重量份的量存在,以100重量份
的該共聚物為基準。
關於聚合EVA共聚物的方法無特別的限制,以及可以使用本技藝中的任何聚合方法。
本發明中使用的EVA共聚物較佳可以為以40 vol%溶解於甲苯/甲基乙基酮內之EVA共聚物(EVA 700,Bayer)。
本發明中使用的EVA共聚物以100重量份的固體含量之各向異性導電膜組成物為基準,可以以5至50重量份的量存在,較佳為10至30重量份的量存在。於此範圍之內,該膜組成物於低溫下之熔化黏度可以控制在低位準以及因而展現出優異的流動性。
本發明中使用的聚胺甲酸酯樹脂可以包括本技藝中典型使用的任何聚胺甲酸酯樹脂,無特別受限制。
本發明中使用的聚胺甲酸酯樹脂可以為聚胺甲酸酯丙烯酸酯或聚酯胺甲酸酯樹脂。
本發明中可使用的聚胺甲酸酯丙烯酸酯可以由異氰酸酯、丙烯酸酯、多元醇及/或二醇、經由聚合作用來製備。
異氰酸酯可以包括芳香族、脂肪族、脂環族二異氰酸酯,以及其等之組合。此等異氰酸酯之實例可以包括異佛酮二異氰酸酯(IPDI)、四亞甲基-1,4-二異氰酸酯、六亞甲基-1,6-二異氰酸酯、二苯甲烷二異氰酸酯、伸環己基-1,4-二異氰酸酯、亞甲基 雙(4-環己基異氰酸酯)、二甲苯二異
氰酸酯、氫化二苯甲烷二異氰酸酯、萘二異氰酸酯,及2,4-或2,6-甲苯二異氰酸酯,其可單獨或是以其等之組合來使用。較佳地,可以使用芳香族二異氰酸酯,不限於該等。
丙烯酸酯可以包括羥基丙烯酸酯或胺基丙烯酸酯,不限於該等。
多元醇或二醇可以包括乙二醇、丙二醇、己二醇、新戊二醇、二乙二醇、三乙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、二丙二醇、二丁二醇、2-甲基-1,3-戊二醇、2,2,4-三甲基-1,3-戊二醇,以及1,4-環已烷二甲醇,不限於該等。
聚合作用可以經由本技藝中典型使用的任何方法來進行,無特別受限制。舉例來說,聚合作用可以於下列的條件下進行:使用50 vol%的甲基乙基酮作為溶劑,多元醇的量為60wt%,羥基(甲基)丙烯酸酯/異氰酸酯的莫耳比為1.0,以及反應係使用催化劑,例如二丁基二月桂酸錫,於90℃和1 atm下實施歷時5小時。
本發明中可使用的聚酯胺甲酸酯樹脂可以藉由聚酯多元醇和二異氰酸酯的反應來獲得。
聚酯多元醇係提及具有酯基和羥基的聚合物,不限於該等。合適的聚酯多元醇可以藉由二甲酸和二醇化合物的縮合反應來獲得。二甲酸化合物之實例可以包括酞酸、對酞酸、異酞酸、己二酸、癸二酸、琥珀酸、戊二酸、辛二酸、壬二酸、十二烷二甲酸、六氫酞酸、鄰苯二甲酸、四氯酞酸、1,5-萘二甲酸、反丁烯二酸、順丁烯二酸、衣康
酸、檸康酸、中康酸,以及四氫酞酸。
二醇之實例可以包括乙二醇、丙二醇、己二醇、新戊二醇、二乙二醇、三乙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、二丙二醇、二丁二醇、2-甲基-1,3-戊二醇、2,2,4-三甲基-1,3-戊二醇,以及1,4-環已烷二甲醇,不限於該等。
二異氰酸酯可以包括芳香族、脂肪族、脂環族二異氰酸酯以及其等之組合。二異氰酸酯之實例可以包括異佛酮二異氰酸酯(IPDI)、四亞甲基-1,4-二異氰酸酯、六亞甲基-1,6-二異氰酸酯、二苯甲烷二異氰酸酯、伸環己基-1,4-二異氰酸酯、亞甲基雙(4-環己基異氰酸酯)、二甲苯二異氰酸酯、氫化二苯甲烷二異氰酸酯、萘二異氰酸酯,以及2,4-或2,6-甲苯二異氰酸酯,其可單獨或是以其等之組合來使用。較佳地,使用芳香族二異氰酸酯,不限於該等。
本發明中使用的聚胺甲酸酯樹脂以100重量份的固體含量之該各向異性導電膜組成物為基準,可以以10至70重量份的量存在,較佳為20至50重量份的量存在。設若聚胺甲酸酯樹脂的量為低於10重量份,該膜無法展現出足夠的黏著力。設若量超過70重量份,該膜很可能經歷流動性之劣化,流動性之劣化使得不易維持穩定的連接。
本發明中可使用的有機微粒子可包括本技藝中典型使用的任何微粒子,無特別受限制。
有機微粒子之實例可以包括苯乙烯-二乙烯苯、
氯化聚乙烯、二甲基聚矽氧烷、甲基丙烯酸甲酯-丙烯酸丁酯-二甲基矽氧烷共聚物、苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-丁二烯熱塑性彈性體、丁二烯橡膠、苯乙烯-丁二烯橡膠,以及乙烯甲基丙烯酸環氧丙酯,其可單獨或是以其等之組合來使用。
有機微粒子可以為苯乙烯-二乙烯苯或苯乙烯-丁二烯橡膠。
有機微粒子可以具有0.1至20μm,較佳為0.1至10μm的顆粒尺寸。於此範圍之內,有機微粒子由於該膜減少的黏性而可以適當地分散以及有可能防止初步的壓製性能劣化。
有機微粒子以100重量份的固體含量之該各向異性導電膜組成物為基準,可以以0.1至30重量份的量存在,較佳為超過1至20重量份的量存在。於此範圍之內,有機微粒子有充分的功效以及可以防止膜的韌性過度增加,如此避免黏性減少。
依據本發明之各向異性導電膜組成物除前述的組份之外還可以進一步包括熱塑性樹脂、丙烯酸共聚物、可自由聚合性(radical polymerizable)材料、有機過氧化物,及/或導電粒子。
本發明中可使用的熱塑性樹脂可包括本技藝中典型使用的任何熱塑性樹脂,無特別受限制。
熱塑性樹脂之實例可包括選自於以下所構成的
群組之至少一者:丙烯腈、苯氧、丁二烯、丙烯酸、聚胺甲酸酯、聚胺甲酸酯丙烯酸酯、聚醯胺、烯烴、矽氧,以及丙烯腈-丁二烯橡膠(NBR)樹脂,不限於該等。
熱塑性樹脂可以具有1,000至1,000,000 g/mol的重量平均分子量。於此範圍之內,可以得到適宜的薄膜強度,不會發生相分離,以及黏著力不會由於黏著黏附體的減少而變差。
熱塑性樹脂以100重量份的固體含量之該各向異性導電膜組成物為基準,可以以0至60重量份的量存在,較佳為0至50重量份的量存在。於此範圍之內,可保證組成物內有機及/或導電粒子足夠的分散性以及可以防止由過度減少的流動性所引起的不穩定連接。
本發明中可使用的丙烯酸共聚物可包括本技藝中典型使用的任何丙烯酸共聚物,無特別受限制。
丙烯酸共聚物可以包括經由丙烯酸單體的聚合作用而獲得之丙烯酸共聚物,例如丙烯酸乙酯、丙烯酸甲酯、丙烯酸丙酯、丙烯酸丁酯、丙烯酸己酯、丙烯酸氧酯(oxyl acrylates)、丙烯酸十二烷基酯、丙烯酸月桂酯、丙烯酸酯、丙烯酸酯、甲基丙烯酸酯和其之經修飾的丙烯酸酯、丙烯酸、甲基丙烯酸、甲基丙烯酸甲酯、醋酸乙烯酯和其之經修飾的丙烯酸單體,不限於該等。
丙烯酸共聚物以100重量份的固體含量之該各向異性導電膜組成物為基準,可以以0至40重量份的量存在,
較佳為5至30重量份的量存在。於此範圍之內,可獲得初步的壓製之後優異的重加工性(reworkability)以及可防止初步的壓製時由於過度提升的硬度所引起之弱的黏性所致之分離。
本發明中可使用的可自由聚合性材料可以包括本技藝中典型使用的任何可自由聚合性材料,無特別受限制。
舉例而言,可自由聚合性材料可以包括丙烯酸酯、甲基丙烯酸酯和馬來亞醯胺化合物,其可以使用為單體、寡聚體或是單體和寡聚體之組合。
丙烯酸酯或甲基丙烯酸酯之實例可以包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸異丙酯、丙烯酸異丁酯、二丙烯酸乙二醇酯、二丙烯酸二乙二醇酯、三羥甲丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、四羥甲甲烷四丙烯酸酯、2-羥基-1,3-二丙烯酸氧丙烷(2-hydroxy-1,3-diacryloxypropane)、2,2-雙[4-(丙烯氧聚甲氧基)苯基]丙烷、2,2-雙[4-(丙烯氧聚乙氧基)苯基]丙烷、二環戊烯基丙烯酸酯、三環癸基丙烯酸酯,以及參(丙烯醯氧乙基)三聚異氰酸酯,不限於該等。此等丙烯酸酯或甲基丙烯酸酯可以單獨或是以其等之組合來使用。再者,可以使用具有磷酸酯結構之丙烯酸酯或甲基丙烯酸酯、三聚異氰酸酯丙烯酸酯(isocyanurate acrylates)以及雙酚A環氧丙烯酸酯樹脂來改善黏著性和室溫穩定性。
馬來亞醯胺化合物可以包括含有至少2個馬來亞醯胺基團之化合物,舉例而言,1-甲基-2,4-雙馬來亞醯胺苯、N,N'-間-伸苯基雙馬來亞醯胺、N,N'-對-伸苯基雙馬來亞醯胺、N,N'-間-甲伸苯基雙馬來亞醯胺、N,N'-4,4-伸聯苯基雙馬來亞醯胺、N,N'-4,4-(3,3'-二甲基伸聯苯基)雙馬來亞醯胺、N,N'-4,4-(3,3'-二甲基二苯甲烷)雙馬來亞醯胺、N,N'-4,4-(3,3'-二乙基二苯甲烷)雙馬來亞醯胺、N,N'-4,4-二苯甲烷雙馬來亞醯胺、N,N'-4,4-二苯丙烷雙馬來亞醯胺、N,N'-4,4-二苯醚雙馬來亞醯胺、N,N'-3,3-二苯碸雙馬來亞醯胺、2,2-雙[4-(4-馬來亞醯胺苯氧基)苯基]丙烷、2,2-雙[3-s-丁基-4-(4-馬來亞醯胺苯氧基)苯基]丙烷、1,1-雙[4-(4-馬來亞醯胺苯氧基)苯基]癸烷、4,4'-亞環己基-雙[1-(4-馬來亞醯胺苯氧基)-2-環己基]苯以及2,2-雙[4-(4-馬來亞醯胺苯氧基)苯基]六氟丙烷,不限於該等。此等馬來亞醯胺化合物可單獨或是以其等之組合來使用。
可自由聚合性材料以100重量份的固體含量之該各向異性導電膜組成物為基準,可以以1至40重量份的量存在,較佳為5至20重量份的量存在。於此範圍之內,可以維持最終的壓製後之適當的固化密度以保證優異的可靠度以及全面的流動性。於是,改善導電粒子和電路板之間的接觸,藉此提供優異的連接可靠度。
本發明中可使用的有機過氧化物可包括本技藝中典型使用的任何有機過氧化物,無特別受限制。
有機過氧化物之實例可包括過月桂酸三級丁酯、1,1,3,3-t-甲基丁基過氧-2-乙基已酸酯(1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanonate)、2,5-二甲基-2,5-二(2-乙基己醯基過氧)已烷、1-環己基-1-甲基乙基過氧-2-乙基已酸酯(1-cyclohexyl-1-methylethyl peroxy-2-ethylhexanonate)、2,5-二甲基-2,5-二(間-甲苯甲醯基過氧)已烷、三級丁基過氧異丙基碳酸酯、三級丁基過氧-2-乙基己基碳酸酯、三級己基過氧苯甲酸酯、三級丁基過氧乙酸酯、雙異苯丙基過氧化物、2,5-二甲基-2,5-二(三級丁基過氧)已烷、三級丁基異苯丙基過氧化物、三級己基過氧新癸酸酯、三級己基過氧-2-乙基已酸酯(t-hexylperoxy-2-ethylhexanonate)、三級丁基過氧-2-2-乙基已酸酯(t-butylperoxy-2-2-ethylhexanonate)、三級丁基過氧異丁酸酯、1,1-雙(三級丁基過氧)環已烷、三級己基過氧異丙基碳酸酯、三級丁基過氧-3,5,5-三甲基已酸酯(t-butylperoxy-3,5,5-trimethylhexanonate)、過氧異丁酸三級丁酯、異丙苯基過氧新癸酸酯、氫過氧化二異丙苯、氫過氧化異丙苯(cumene hydroperoxide)、過氧化異丁基、2,4-二氯苯甲醯過氧化物、3,5,5-三甲基己醯基過氧化物、過氧化辛醯基、過氧化月桂醯、過氧化硬脂醯、過氧化琥珀酸、過氧化苯甲醯、3,5,5-三甲基己醯基過氧化物、苯甲醯基過氧化甲苯、1,1,3,3-四甲基丁基過氧新癸酸酯、1-環己基-1-甲基乙基過氧新癸酸酯、過氧二碳酸二正丙酯、過氧碳酸二異丙酯、雙(4-三級丁基環己基)過氧二碳酸酯、過氧二碳
酸二-2-乙氧基甲氧酯、二(2-乙基己基過氧)二碳酸酯、過氧二碳酸二甲氧基丁酯、二(3-甲基-3-甲氧基丁基過氧)二碳酸酯、1,1-雙(三級己基過氧)-3,3,5-三甲基環已烷、1,1-雙(三級己基過氧)環已烷、1,1-雙(三級丁基過氧)-3,3,5-三甲基環已烷、1,1-(三級丁基過氧)環十二烷、2,2-雙(三級丁基過氧)癸烷、三級丁基三甲基矽基過氧化物、雙(三級丁基)二甲基矽基過氧化物、三級丁基三烯丙基矽基過氧化物、雙(三級丁基)二烯丙基矽基過氧化物,以及參(三級丁基)烯丙基矽基過氧化物,不限於該等。
有機過氧化物以100重量份的固體含量之該各向異性導電膜組成物為基準,可以以0.1至10重量份的量存在。於此範圍之內,可以得到最終的壓製之優異的性質以及防止固化後該膜的脆性之增加,因而在重加工期間完全地移除各向異性導電膜。
本發明中可使用的導電粒子可包括本技藝中典型使用的任何導電粒子,無特別受限制。
導電粒子之實例可包括金屬顆粒,例如,Au、Ag、Ni、Cu及焊錫顆粒;碳顆粒;塗覆金屬的樹脂顆粒,例如塗覆Au、Ag或Ni的聚乙烯、聚丙烯、聚酯、聚苯乙烯和聚乙烯醇以及其之經修飾的樹脂的顆粒;以及進一步塗覆絕緣顆粒之經絕緣處理的導電粒子。
導電粒子的尺寸可以決定於2至30μm的範圍內,取決於要使用的電路之間距以及目的。
導電粒子以100份重量計的固體含量之該各向異性導電膜組成物為基準,可以以0.1至10重量份的量存在。於此範圍之內,當在連接的期間未對準接頭時,可能不會發生由於連接面積的減少所致之缺陷連接及絕緣缺陷。
依據本發明之各向異性導電膜組成物可以具有於80℃為2,000至8,000 Pa.s的熔化黏度。於此範圍之內,該組成物具有優異的流動性,以及因而用該組成物之填充可以平順地進行。並且,既然可抑制由於收縮和膨脹之熱變形,所以產生較少的氣泡以及展現出傑出的黏著力。
設若熔化黏度於80℃為低於2,000 Pa.s,各向異性導電膜具有過度流動性,此使得各向異性導電膜不易填充連接的部分,藉此導致氣泡的產生以及黏著力減少。設若熔化黏度於80℃超過8,000 Pa.s,膜壓製無法適當地作用,導致連接可靠度的問題。
本發明的另一個態樣提供一種各向異性導電膜,其包括,a)乙烯-醋酸乙烯酯共聚物;b)聚胺甲酸酯樹脂;以及c)有機微粒子;其中該各向異性導電膜具有在150℃和4MPa歷時4秒的壓製之後為1,000 gf/cm或是更大的黏著強度。
關於形成各向異性導電膜的方法無特別的限制,以及可以使用本技藝中典型使用的任何方法。
不需要特定的儀器或是設備來形成各向異性導
電膜。舉例而言,各向異性導電膜可以藉由以下方式來獲得,使黏結劑樹脂溶解且液化於有機溶劑內,添加剩餘的成份至該處且攪拌溶液歷時某時間期間,塗覆溶液至離形膜達適當的厚度,舉例而言,10至50μm的厚度,以及使溶液乾燥以使有機溶劑揮發。
關於測量黏著強度的方法無特別的限制,以及可以使用本技藝中典型使用的任何方法。
舉例而言,黏著強度可以在150℃和4.0 MPa歷時4秒的壓製之後,藉由一種剝離強度測試器(H5KT,Tinius Olsen)、以90°的剝離角度以及50 mm/min的剝離速度來測量。
本發明的另一個態樣提供各向異性導電膜組成物,其在150℃和4MPa歷時4秒的壓製以及接而儲存於85℃和85% RH歷時500小時之後,具有800 gf/cm或是更大的黏著強度。
該膜組成物的物理性質在儲存於85℃和85% RH歷時500小時之後可以為平均可靠度(mean reliability)。
本發明的另一個態樣提供一種各向異性導電膜,其在150℃和4MPa歷時4秒的壓製以及接而儲存於85℃和85% RH歷時500小時之後,具有以電極之間的空間面積為基準為10%或更低的氣泡面積。
電極之間的空間為PCB內電極之間的間隙,於壓製期間用各向異性導電膜組成物來填滿電極之間的間隙。
關於測量氣泡面積的方法無特別的限制,以及可
以使用本技藝中典型使用的任何方法。舉例而言,氣泡面積可以是係被為藉由使用顯微鏡來觀察(或拍照)用該膜組成物來填充的電極之間的空間,接著使用影像分析儀或方格坐標計算氣泡面積而測量。
設若各向異性導電膜具有超過10%的氣泡面積,一種利用該膜來連接的半導體元件無法使用歷時長時間以及具有短的生命全期。
10%或更低的氣泡面積意謂著氣泡面積有(is has)接近0的下限,而不是意指氣泡面積完全不形成。
本發明的另一個態樣提供一種由各向異性導電膜連接的半導體元件。
半導體元件可以包括一種配線基板;一種附接至該配線基板的安裝晶片面之各向異性導電膜;以及一種安裝於該膜之上的半導體晶片。
本發明中使用的配線基板與半導體晶片不特別限制且可包括本技藝中典型使用的任何基板以及任何的半導體晶片。
製造本發明之半導體元件的方法不特別限制以及可以包括本技藝中典型使用的任何方法。
在下文,本發明將參照下列的實施例、比較實施例及實驗實施例予以詳細地描述。然而,此等實施例僅為了闡明的目的而提供以及不會被解釋為限制具體例的範疇。
各向異性導電膜組成物係使用下列的材料來製備:1)以40vol%溶解於甲苯/甲基乙基酮內的20重量份之EVA共聚物(EVA 700,Bayer)作為EVA共聚物;2)具有25,000g/mol的重量平均分子量之40重量份的聚胺甲酸酯丙烯酸酯作為聚胺甲酸酯樹脂,其係使用60 wt%的多元醇(聚四亞甲基乙二醇(polytetramethylene glycol))、13.53 wt%的1,4-丁二醇、26.14 wt%甲苯二異氰酸酯、0.3 wt%的甲基丙烯酸羥乙酯以及0.03 wt%的二丁基二月桂酸錫為催化劑來合成的(聚胺甲酸酯丙烯酸酯的方法為下列:首先,使多元醇、1,4-丁二醇,和甲苯二異氰酸酯起反應來合成具有異氰酸酯終端的預聚合物。繼而進一步地,使具有異氰酸酯終端的預聚合物與甲基丙烯酸羥乙酯起反應來生產聚胺甲酸酯丙烯酸酯樹脂。於此,聚合作用係以於預聚合物的終端之0.5莫耳比的甲基丙烯酸羥乙酯/異氰酸酯,以及於90℃和1 atm歷時5小時使用二丁基二月桂酸錫為催化劑來進行,藉此生產具有25,000 g/mol的重量平均分子量之聚胺甲酸酯丙烯酸酯);3)15重量份的苯乙烯-丁二烯熱塑性彈性體(ASAPRENE 420P,Asahi Kasei Chemicals)作為有機微粒子;4)以45vol%溶解於甲苯/甲基乙基酮內之具有
100,000g/mol的重量平均分子量之10重量份的丙烯酸樹脂(AOF7003,Aekyung Chemical)作為丙烯酸共聚物;5)10重量份的環氧丙烯酸酯(SP1509,Showa Highpolymer)作為可自由聚合性材料;6)2重量份的苯甲醯過氧化物(Hansol Chemical)作為有機的過氧化物;以及7)具有5μm的顆粒尺寸之3重量份的導電Ni顆粒作為導電粒子;以100份重量計的固體含量之該各向異性導電膜組成物為基準。
以不使導電粒子粉碎的速率來攪拌該組合,以及在室溫(25℃)下歷時60分鐘。該組合使用鑄刀而於已經接受矽脫模(release)表面處理之聚乙烯為基的膜之上形成為35 um厚的膜。該膜於60℃下乾燥歷時5分鐘。
一種各向異性導電膜係以如同實施例1中之相同的方式予以製備,除了使用30重量份的EVA共聚物以及5重量份的有機微粒子之外。
一種各向異性導電膜係以如同實施例1中之相同的方式予以製備,除了使用40重量份的EVA共聚物、30重量份的聚胺甲酸酯樹脂以及5重量份的有機微粒子之外。
一種各向異性導電膜係以如同實施例1中之相同
的方式予以製備,除了使用35重量份的EVA共聚物、30重量份的聚胺甲酸酯樹脂以及10重量份的有機微粒子之外。
一種各向異性導電膜係以如同實施例1中之相同的方式予以製備,除了使用1重量份的有機微粒子、18重量份的丙烯酸共聚物和16重量份的可自由聚合性材料之外。
一種各向異性導電膜係以如同實施例1中之相同的方式予以製備,除了不添加有機微粒子以及使用20重量份的丙烯酸共聚物和15重量份的可自由聚合性材料之外。
一種各向異性導電膜係以如同比較實施例1中之相同的方式予以製備,除了使用25 vol%溶解於甲苯/甲基乙基酮內之丙烯腈丁二烯共聚物(1072CGX,Zeon Chemical)作為熱塑性樹脂代替EVA共聚物之外。
一種各向異性導電膜係以如同實施例1中相同的方式予以製備,除了不添加EVA共聚物和有機微粒子,以及使用30重量份的聚胺甲酸酯樹脂和以25 vol%溶解於甲苯/甲基乙基酮內之40重量份的丙烯腈丁二烯共聚物(1072CGX,Zeon Chemical)作為熱塑性樹脂之外。
實施例1至5以及比較實施例1至3中使用的組成
物係根據重量份而列於表1和表2內。
為了測量如實施例1至5以及比較實施例1至3之各向異性導電膜的各者之熔化黏度,將各個膜製備成厚度140μm以及使用ARES(ARES G2,TA Instruments)來評估關於80℃下的黏度同時以10℃/min從30℃提高溫度至220℃(應變:5%,頻率:1 rad/s,平行板和鋁可棄式板之直徑:8 mm)。
為了測量如實施例1至5以及比較實施例1至3之各向異性導電膜的各者之黏著強度,將各膜於下列的條件下附接至印刷電路板(PCB,間距:200μm,終端:100μm,終端之間的距離:100μm,終端高度:35μm)及附接至覆晶薄膜(COF,間距:200μm,終端:100μm,終端之間的距離:100μm,終端高度:8μm)。
1)初步的壓製:70℃,1秒,1.0MPa
2)最終的壓製:150℃,4秒,4.0MPa
製備如上附接的各膜的5個樣本以及使用一種剝離強度測試器(H5KT,Tinius Olsen)以90°的剝離角度及50mm/min的剝離速度來評估關於黏著強度,接著計算平均值。
各膜的5個樣本於高溫和濕度下接受可靠度測試(儲存於85℃和85% RH歷時500小時)以及以如以上相同的方式來評估關於可靠度測試後之黏著強度值。
為了測量如實施例1至5以及比較實施例1至3之各向異性導電膜的各者之連接電阻,將各膜於下列的條件下附接至PCB(間距:200μm,終端:100μm,終端之間的距離:100μm,終端高度:35μm)及附接至COF(間距:200μm,終端:100μm,終端之間的距離:100μm,終端高度:8μm)。
1)初步的壓製:70℃,1秒,1.0 MPa
2)最終的壓製:200℃,4秒,4.0 MPa
製備如上附接的各膜的5個樣本以及使用4探針方法(根據ASTM F43-64T)來評估關於起始的連接電阻,接著計算平均值。
各膜的5個樣本於高溫和濕度下接受可靠度測試(儲存於85℃和85% RH歷時500小時)以及評估可靠度測試後之連接電阻(根據ASTM D117),接著計算平均值。
為了測量如實施例1至5以及比較實施例1至3之各向異性導電膜的各者內產生的氣泡面積,將各膜於下列的條件下附接至PCB(間距:200μm,終端:100μm,終端之間的距離:100μm,終端高度:35μm)及附接至覆晶薄膜(COF,間距:200μm,終端:100μm,終端之間的距離:100μm,終端高度:8μm)。
1)初步的壓製:70℃,1秒,1.0 MPa
2)最終的壓製:200℃,4秒,4.0 MPa
製備如上附接的各膜的5個樣本。在使用一光學顯微鏡取得各個樣本的10個點之照片之後,使用影像分析儀來測量電極之間的空間內產生的氣泡面積。
各膜的5個樣本於高溫和濕度下接受可靠度測試(儲存於85℃和85% RH歷時500小時)以及以如以上相同的方式來評估關於氣泡面積,接著計算平均值。
為了評估如實施例1至5以及比較實施例1至3之各向異性導電膜組成物的各者的溶液穩定性,將各個組成物在室溫(25℃)下以140rpm攪拌歷時60分鐘以致不使導電粒子粉碎。繼而,將產物再分成50 g的樣本,放置於小玻璃瓶內以及以肉眼觀察來測量發生相分離的時刻。
實驗實施例1至5的結果係闡明於表3和4內。
如表3和4內顯示的,可看到如實施例1至5之包括EVA、聚胺甲酸酯樹脂以及有機粒子的各向異性導電膜具有優於比較實施例1至3之不包括EVA和有機粒子的各向異性導電膜之物理性質,舉例而言,黏著強度、連接電阻以及氣泡面積。
再者,可看到含有EVA的之各向異性導電膜具有更低的熔化黏度以及因而展現出低溫下優異的流動性。並且,如實施例1至5之包括EVA、聚胺甲酸酯樹脂以及有機粒子的各向異性導電膜具有與比較實施例1至3之各向異性導電膜相比、明顯優異的溶液穩定性。
於此,亦可看到如實施例5之包括1重量份的有機微粒子之各向異性導電膜在熔化黏度、黏著強度、連接電阻、溶液穩定性以及起始的氣泡面積方面為優異的,但是具有比其他的實施例在可靠度測試後稍微更大的氣泡面積。認為原因是相對小量的有機粒子提供低功效的控制黏
度。
雖然本發明之詳細說明內已經提供一些具體例,熟悉此藝者顯然了解該等具體例僅僅提供作為實例,以及可以做出各種各樣的修飾、變化、改變,以及均等的具體例而不背離本發明的精神和範疇。本發明的範疇應該僅僅由附隨的申請專利範圍來限制。
Claims (7)
- 一種各向異性導電膜,其包含:a)20至40重量份的乙烯-醋酸乙烯酯共聚物;b)10至70重量份的聚胺甲酸酯樹脂;以及c)0.1至30重量份的有機微粒子;以100重量份的固體含量之該各向異性導電膜為基準;其中該各向異性導電膜具有於80℃下為2,000至8,000Pa˙s的熔化黏度,以及該膜在150℃和4MPa歷時4秒的壓製以及接而儲存於85℃和85% RH歷時500小時之後,具有10%或更低的氣泡面積,其係以電極之間的空間面積為基準。
- 如申請專利範圍第1項之各向異性導電膜,其中該有機微粒子包含選自於以下所構成的群組之至少一者:苯乙烯-二乙烯苯、氯化聚乙烯、二甲基聚矽氧烷、甲基丙烯酸甲酯-丙烯酸丁酯-二甲基矽氧烷共聚物、苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-丁二烯熱塑性彈性體、丁二烯橡膠、苯乙烯-丁二烯橡膠,以及乙烯甲基丙烯酸環氧丙酯(ethylene glycidyl methacrylate)。
- 一種各向異性導電膜,其包含:a)20至40重量份的乙烯-醋酸乙烯酯共聚物;b)10至70重量份的聚胺甲酸酯樹脂;以及c)0.1至30重量份的有機微粒子;以100重量份的固體含量之該各向異性導電膜為基 準;其中該各向異性導電膜具有在150℃和4MPa歷時4秒的壓製之後為1,000gf/cm或是更大的黏著強度,以及在150℃和4MPa歷時4秒的壓製以及接而儲存於85℃和85% RH歷時500小時之後,具有10%或更低的氣泡面積,其係以電極之間的空間面積為基準。
- 如申請專利範圍第3項之各向異性導電膜,其中該有機微粒子包含選自於以下所構成的群組之至少一者:苯乙烯-二乙烯苯、氯化聚乙烯、二甲基聚矽氧烷、甲基丙烯酸甲酯-丙烯酸丁酯-二甲基矽氧烷共聚物、苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-丁二烯熱塑性彈性體、丁二烯橡膠、苯乙烯-丁二烯橡膠,以及乙烯甲基丙烯酸環氧丙酯。
- 如申請專利範圍第3項之各向異性導電膜,其中該膜在150℃和4MPa歷時4秒的壓製以及接而儲存於85℃和85% RH歷時500小時之後,具有800gf/cm或是更大的黏著強度。
- 如申請專利範圍第3至5項中任一項之各向異性導電膜,其中該各向異性導電膜具有於80℃下為2,000至8,000Pa˙s的熔化黏度。
- 一種半導體元件,其包含:a)一配線基板;b)一附接至該配線基板的安裝晶片面之各向異性導電膜;以及 c)一安裝於該膜之上的半導體晶片;其中該各向異性導電膜為如申請專利範圍第1至6項中任一項之膜。
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