TW201437310A - 各向異性導電膜及半導體裝置 - Google Patents

各向異性導電膜及半導體裝置 Download PDF

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Publication number
TW201437310A
TW201437310A TW103102682A TW103102682A TW201437310A TW 201437310 A TW201437310 A TW 201437310A TW 103102682 A TW103102682 A TW 103102682A TW 103102682 A TW103102682 A TW 103102682A TW 201437310 A TW201437310 A TW 201437310A
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Taiwan
Prior art keywords
anisotropic conductive
conductive film
acrylate
meth
weight
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TW103102682A
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English (en)
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TWI546362B (zh
Inventor
Youn-Jo Ko
Hye-Su Ki
Ie-Ju Kim
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Cheil Ind Inc
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Publication of TWI546362B publication Critical patent/TWI546362B/zh

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    • H—ELECTRICITY
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    • B60—VEHICLES IN GENERAL
    • B60N—SEATS SPECIALLY ADAPTED FOR VEHICLES; VEHICLE PASSENGER ACCOMMODATION NOT OTHERWISE PROVIDED FOR
    • B60N2/00—Seats specially adapted for vehicles; Arrangement or mounting of seats in vehicles
    • B60N2/24—Seats specially adapted for vehicles; Arrangement or mounting of seats in vehicles for particular purposes or particular vehicles
    • B60N2/26—Seats specially adapted for vehicles; Arrangement or mounting of seats in vehicles for particular purposes or particular vehicles for children
    • B60N2/28—Seats readily mountable on, and dismountable from, existing seats or other parts of the vehicle
    • B60N2/2803—Adaptations for seat belts
    • B60N2/2806—Adaptations for seat belts for securing the child seat to the vehicle
    • B60N2/2809—Adaptations for seat belts for securing the child seat to the vehicle with additional tether connected to the top of the child seat and passing above the top of the back-rest
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B60N—SEATS SPECIALLY ADAPTED FOR VEHICLES; VEHICLE PASSENGER ACCOMMODATION NOT OTHERWISE PROVIDED FOR
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    • B60N2/2851—Seats readily mountable on, and dismountable from, existing seats or other parts of the vehicle provided with head-rests
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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
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Abstract

此處揭露一種各向異性導電膜，其係使用至少二種於其結構中具有不同數量的反應基團之自由基聚合材料製備，以提供低透濕度及低吸濕度，同時展現優異之長期可靠性；及一包含此各向異性導電膜之半導體裝置。特別地，此各向異性導電膜係使用含有一具有一或二個(甲基)丙烯酸酯反應基團之材料及一具有至少三個(甲基)丙烯酸酯反應基團之材料的自由基聚合材料製備，以改良長期可靠性。

Description

各向異性導電膜及半導體裝置 發明領域
本發明係有關於一種具有低透濕度及吸濕度同時展現優異長期可靠性之各向異性導電膜，及一種與使用此各向異性導電膜有關之半導體裝置。
相關技藝說明
一般，各向異性導電膜(ACF)係指其中諸如包含鎳或金之顆粒的金屬顆粒或以金屬塗覆之聚合物顆粒的導電顆粒分散於一諸如環氧樹脂之樹脂中的膜形黏著劑。各向異性導電膜係由具有電各向異性及黏著性之聚合物層形成，且於此膜之厚度方向展現導電性及於其表面方向展現絕緣性。
當一各向異性導電膜被置於電路板之間且接受於特定條件下之加熱及壓縮時，此等電路板之電路端子經由導電顆粒電連接，且一絕緣黏著樹脂填充相鄰電路端子間之空間，以使導電顆粒彼此隔離，藉此，於電路端子間提供高絕緣性。
具有對於一具有優異長期可靠性之各向異性導 電膜的需求，此可克服於產品使用時連續電流及曝露於高溫及高濕度條件的問題。特別地，隨著最近發現輕、薄、小且短的IT裝置及增加平板顯示裝置的解析度，裝置之電路寬度於相關技藝係逐漸變窄，因此，置於電極間用以連接電路之導電顆粒的數量減少，因此，增加長期可靠性之重要性。
為增強包含於一附接電路元件之各向異性導電 膜之各向異性導電膜的長期可靠性，使用無機顆粒已於相關技藝中研究(韓國專利第10-0652915號案等)。當添加至一用於各向異性導電膜之組成物時，無機顆粒可降低此等膜之透濕度及吸濕度。但是，無機顆粒使各向異性導電膜之固有黏著性惡化，造成此膜與一基材間之界面處嚴重起泡，因此，使長期可靠性惡化。
因此，需要一種經由調整膜之透濕度及吸濕度而 具有優異長期可靠性且不會使各向異性導電膜之黏著性惡化的各向異性導電膜。
發明概要
本發明之一目的係提供一種各向異性導電膜，其係使用至少二種於其結構中具有不同數量之反應基團的自由基聚合材料製備，以提供低透濕度及低吸濕度，同時展現優異的長期可靠性。
特別地，本發明之目標在於提供一種各向異性導電膜，其係使用包含一於其結構中具有一或二個(甲基)丙烯 酸酯反應基團之材料及一於其結構中具有至少三個(甲基)丙烯酸酯反應基團之材料的自由基聚合材料製備，以改良長期可靠性。
本發明提供一種各向異性導電膜，其係使用至少 二種於其結構中具有不同數量之反應基團的自由基聚合材料製備，以提供低透濕度及低吸濕度，同時展現優異的長期可靠性。
依據本發明之一方面，一種各向異性導電膜包 含：a)一結合劑樹脂；b)一於其結構中具有一或二個(甲基)丙烯酸酯反應基團之第一自由基聚合材料，及一於其結構中具有至少三個(甲基)丙烯酸酯反應基團之第二自由基聚合材料；及c)導電顆粒，其中，此膜具有170g/m2/24hr或更少之透濕度及2%或更少之吸濕度。
依據本發明實施例之各向異性導電膜具有低透 濕度及低吸濕度，因此，以可靠性連接電阻、可靠性黏著強度或可靠性起泡性質而言係展現優異可靠性，即使於高溫及/或高濕度之條件下使用一段長時間之後。
作為一電路之一元件，由於此各向異性導電膜之 優異性質，一使用此各向異性導電膜製備之半導體裝置提供長時期之半導體功效。
10‧‧‧各向異性導電膜
40‧‧‧導電顆粒
50‧‧‧第一連接元件
60‧‧‧第二連接元件
70‧‧‧第一電極
80‧‧‧第二電極
圖式簡要說明
圖1係一半導體裝置之截面圖，其包含一具有一第一電極70之第一連接元件50，及一具有一第二電極80之 第二連接元件60，其中，第一及第二連接元件50，60係經由一依據本發明一實施例之各向異性導電膜10彼此連接。 當各向異性導電膜10於含有第一電極70之第一連接元件50與含有第二電極80之第二連接元件60之間壓縮時，第一電極70係經由導電顆粒40與第二電極80電連接。
發明之詳細說明
以下，本發明之實施例將更詳細說明。對熟習此項技藝者明顯之詳細說明為了清楚會被省略。
本發明提供一各向異性導電膜，其係使用至少二種於其結構具有不同數量的反應基團之自由基聚合材料製備，以提供低透濕度及低吸濕度，同時展現優異的長期可靠性。
依據本發明之一實施例，一各向異性導電膜包含：(a)一結合劑樹脂；(b)一第一自由基聚合材料，其於其結構具有一或二個(甲基)丙烯酸酯反應基團，及一第二自由基聚合材料，其於其結構中具有至少三個(甲基)丙烯酸酯反應基團；及(c)導電顆粒，其中，此膜具有170g/m2/24hr或更少之透濕度及2%或更少之吸濕度。
其次，依據本發明實施例之一各向異性導電膜的個別組份將更詳細地說明。此處，每一組份之含量係以一各向異性導電膜組組成物之總重量為基準。再者，於製備各向異性導電膜，此等組份之每一者係溶於一有機溶劑中且沉積於一離型膜上，其後乾燥一預定時間以便蒸發有機 溶劑。因此，一固體各向異性導電膜亦可含有此各向異性導電膜組成物之個別組份。
a)結合劑樹脂
於本發明中，典型上用於此項技藝之任何結合劑樹脂可不受限地使用。
結合劑樹脂之例子可包含丙烯腈-丁二烯橡膠(NBR)樹脂、聚胺基甲酸酯樹脂、丙烯酸樹脂、聚酯胺基甲酸酯樹脂等。
此處，丙烯腈-丁二烯橡膠樹脂係指經由丙烯腈及丁二烯之乳化聚合製備之共聚物。於此共聚物，丙烯腈及丁二烯之含量不受特別限制，且任何聚合方法可不受限地使用。丙烯腈-丁二烯橡膠樹脂可具有50,000克/莫耳至1,000,000克/莫耳之重量平均分子量，但不限於此。
於此處，聚胺基甲酸酯樹脂係指具有一胺基甲酸酯鍵之一聚合物樹脂，且可經由，例如，異佛爾酮二異氰酸酯、聚四亞甲基二醇等之聚合而製備，旦不受於此。聚胺基甲酸酯樹脂具有10,000克/莫耳至200,000克/莫耳之重量平均分子量，但不限於此。
於此處，丙烯酸樹脂丙烯酸單體及/或可與其聚合之其它單體聚合而製備。例如，丙烯酸樹脂可藉由選自由含有C2至C10烷基基團之(甲基)丙烯酸酯、(甲基)丙烯酸、乙酸乙烯酯，及自其改質之丙烯酸單體所組成之組族之至少一單體之聚合而製備。任何聚合方法可不受限地使用。丙烯酸樹脂可具有10,000克/莫耳至200,000克/莫耳之重量 均分子量，但不限於此。
於此處使用時，聚酯胺基甲酸酯樹脂可為經由聚 酯多元醇及二異氰酸酯反應而製備之樹脂。
聚酯多元醇係指具有複數個酯基團及複數個羥 基基團之聚合物。聚酯多元醇可經由二羧酸及二元醇之縮合反應而獲得。
二羧酸之例子可包含脂族或芳香族二羧酸，諸 如，鄰苯二甲酸、對苯二甲酸、異苯二甲酸、己二酸、癸二酸、丁二酸、戊二酸、辛二酸、壬二酸、十二烷二羧酸、六氫酞酸、四氯酞酸、1,5-萘二羧酸、福馬酸、馬來酸、伊康酸、檸康酸、中康酸，及四氫酞酸，但不限於此等。
二元醇之例子可包含二醇類，諸如，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，及1,4-環己烷二甲醇，但不限於此等。
二共氰酸酯之例子可包含芳香族、脂環狀，或脂 族二異氰酸酯，諸如，異佛爾酮二異氰酸酯(IPDI)、4,4'-二苯基甲烷二異氰酸酯(MDI)、1,6-六亞甲基二異氰酸酯(HDI)、二甲苯二異氰酸酯、經氫化之二苯基甲烷二異氰酸酯、萘二異氰酸酯、2,4-甲苯二異氰酸酯，及2,6-甲苯二異氰酸酯，但不限於此等。
聚酯胺基甲酸酯樹脂可具有10,000克/莫耳至 200,000克/莫耳，特別是50,000克/莫耳至100,000克/莫耳之 重量平均分子量，但不限於此等。
此等結合劑樹脂可單獨或以二或更多種具有不 同重量平均分子量之結合劑樹脂之組合而使用。當使用二或更多種具有不同重量平均分子量之結合劑樹脂時，可避免於僅使用一具有高重量平均分子量之結合劑之情況時發生之過度膜硬化問題，及於僅使用一具有低重量平均分子量之結合劑之情況時發生之膜形成困難的問題。此外，與單獨使用一具有中間重量平均分子量之結合劑的情況相比，依據本發明之各向異性導電膜組成物可經由具有不同重量平均分子量之結合劑樹脂間的相互補充形成一具有優異性質之各向異性導電膜。
於一實施例，結合劑樹脂可為一包含丙烯腈-丁 二烯橡膠樹脂、聚胺基甲酸酯樹脂，及丙烯酸樹脂之樹脂組成物。
於某些實施例，樹脂組成物可包含1重量%(wt%) 至10wt%之丙烯腈-丁二烯橡膠樹脂，20wt%至40wt%之聚胺基甲酸酯樹脂，及10wt%至30wt%之丙烯酸樹脂。於此等組份之此等含量範圍內，樹脂組成物可提供優異之膜形成性及黏著性。
於某些實施例，以固體含量而言，以各向異性導 電膜之總量為基準，結合劑樹脂可以30wt%至80wt%，特別是40wt%至70wt%，例如，50wt%至70wt%之量存在。於此範圍內，結合劑樹脂可提供優異之膜形成性及黏著性。
b)自由基聚合材料
於本發明之實施例，自由基聚合材料包含一於其 結構具有一或二個(甲基)丙烯酸酯反應基團之第一自由基聚合材料，及一於其結構具有至少三個(甲基)丙烯酸酯反應基團之第二自由基聚合材料。
此處，第一自由基聚合材料之例子可包含(甲基) 丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十二烷酯、(甲基)丙烯酸C12-C15烷酯、(甲基)丙烯酸正十八烷酯、(甲基)丙烯酸正丁氧基乙酯、丁氧基二乙二醇(甲基)丙烯酸酯、甲氧基三乙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸2-苯氧基乙酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸二乙基胺基乙酯、(甲基)丙烯酸、2-(甲基)丙烯醯氧基乙基丁二酸、2-(甲基)丙烯醯氧基乙基六氫酞酸酯、2-(甲基)丙烯醯氧基乙基-2-羥基丙基酞酸酯、(甲基)丙烯酸縮水甘油酯、2-(甲基)丙烯醯氧基乙酸酞酸、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、丙三醇二(甲基)丙烯酸酯、2-羥 基-3-丙烯醯氧基丙基(甲基)丙烯酸酯、二甲羥基三環癸烷二(甲基)丙烯酸酯、(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸全氟辛基乙酯、丙烯酸異戊酯、雙酚A之環氧乙烷加成物之二(甲基)丙烯酸酯、雙酚A之氧丙烷加成物之二(甲基)丙烯酸酯、三甲羥基丙烷-苯甲酸酯-(甲基)丙烯酸酯、雙酚A二縮水甘油基二(甲基)丙烯酸酯、甲苯二異氰酸酯及2-羥基-3-苯氧基丙基(甲基)丙烯酸酯之加成物，但不限於此等。此等可單獨或以其組合使用。
於某些實施例，以固定含量而言，以各向異性導 電膜之總量為基準，第一自由基聚合材料可以5wt%至40wt%，特別是7wt%至40wt%，例如，10wt%至40wt%之量存在。於此範圍內，第一自由基聚合材料能使一固化產物之整體形成一足夠之丙烯酸酯固化結構，且能避免固化產物之硬度過度增加及剝離強度與黏著性惡化。
另外，第二自由基聚合材料之例子可包含三羥甲 基丙烷三(甲基)丙烯酸酯、經環氧乙烷改質之三羥甲基丙烷的三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯及六亞甲基二異氰酸酯之加成物、季戊四醇三(甲基)丙烯酸酯及甲苯二異氰酸酯之加成物、季戊四醇三(甲基)丙烯酸酯及異佛爾酮二異氰酸酯之加成物，及二季戊四醇五(甲基)丙烯酸酯及六亞甲基二異氰酸酯之加成物，但不限於此等。此等可單獨或以其組合使用。
於某些實施例，以固體含量而言，以各向異性導 電膜之總量為基準，第二自由基聚合材料可以wt%至20wt%，特別是1wt%至15wt%，例如，1wt%至10wt%之量存在。於此範圍內，第二自由基聚合材料可充份地增加固化速率且可經由一三維固化結構提供高可靠性。另外，於此範圍內，第二自由基聚合材料可避免由於組成物反應性過度增加而使固化產物之硬度過度增加，剝離強度及黏著性惡化，及貯存安定性惡化。
於某些實施例，以固體含量而言，以各向異性導 電膜之總量為基準，自由基聚合材料可以6wt%至60wt%，特別是10wt%至50wt%，例如，20wt%至40wt%之總量存在。 於此範圍內，自由基聚合材料能使一固化產物之整體形成一足夠之丙烯酸酯固化結構，且能避免固化產物之硬度過度增加及剝離強度與黏著性惡化。
於某些實施例，第一自由基聚合材料及第二自由 基聚合材料可以1至10，特別是1至7，例如，1至5，更特別是2至4之重量比率(第一自由基聚合材料/第二自由基聚合材料)混合。
於此第一自由基聚合材料對第二自由基聚合材 料之重量比率內，自由基聚合材料可與結合劑形成一緻密網狀交聯，而非一線性形狀，藉此，提供低透濕度及低吸濕度，同時以連接電阻、黏著性、起泡性質等而言維持優異可靠性。
c)導電顆粒
於本發明中，典型上於此項技藝中已知之任何導 電顆粒可不受限地使用。
導電顆粒之例子可包含金屬顆粒，諸如，金 (Au)、銀(Ag)、鎳(Ni)、銅(Cu)，及焊料顆粒；碳顆粒；樹脂顆粒，諸如，聚乙烯、聚丙烯、聚酯、聚苯乙烯、聚乙烯醇，及以金屬(諸如，金(Au)、銀(Ag)、鎳(Ni)等)電鍍之其等的經改質之樹脂顆粒；及藉由於以金屬塗覆之聚合物樹脂顆粒上進一步塗覆絕緣顆粒而獲得之經色緣的導電顆粒，但不限於此等。此等可單獨或以其組合而使用。
導電顆粒可具有依電路間距而定之各種平均顆 粒直徑，且導電顆粒之平均顆粒直徑可依需要於1μm至30μm之範圍選擇。
於某些實施例，以固定含量而定，以各向異性導 電膜之總量為基準，導電顆粒可以0.1wt%至30wt%，特別是1wt%至20wt%，更特別是1wt%至10wt%之量存在。於此含量範圍內，各向異性導電膜可藉由避免結合及/或隔離失效而展現優異結合特徵。
於其它實施例，除a)、b)及c)組份外，各向異性 導電膜可進一步包含無機顆粒。當進一步包於用於各向異性導電膜之組成物中時，於各向異性導電膜對電極壓縮時，無機顆粒可均勻分佈壓力，且可降低各向異性導電膜之透濕度及吸濕度，同時改良黏著性及連接可靠性。
無機顆粒的例子可包含選自二氧化矽、Al2O3、 TiO2、ZnO、MgO、ZrO2、PbO、Bi2O3、MoO3、V2O5、Nb2O5、Ta2O5、WO3，及In2O3之陶瓷顆粒的任一種，但不限於此等。
二氧化矽顆粒可具有0.01μm至10μm，特別是 0.05μm至5μm，更特別是0.1μm至1μm之平均顆粒直徑，但不限於此等。
以固定含量而言，以各向異性導電膜之總量為基 準，二氧化矽顆粒可以0.1t%至20wt%，特別是0.1wt%至10wt%之量存在。於此範圍內，無機顆粒可均勻分佈施加至電極的壓力，且可降低各向異性導電膜之透濕度及吸濕度，同時改良黏著性及連接可靠性。
各向異性導電膜可進一步包含一固化起始劑。
於本發明中，此項技藝已知之任何典型固化起始 劑可不受限地使用。固化起始劑之例子可包含以過氧化物(有機過氧化物)及以偶氮為主之起始劑，但不限於此等。
以過氧化物為主之起始劑的例子可包含乙醯基 丙酮過氧化物、甲基環己酮過氧化物、甲基乙基酮過氧化物、1,1-雙(第三丁基過氧)環己酮、1,1-雙(第三丁基過氧)-2-甲基環己酮、1,1-雙(第三丁基過氧)-3,3,5-三甲基環己酮、正丁基-4,4-雙(第三丁基過氧)戊酸酯、2,2-雙(第三丁基過氧)丁烷、第三丁過氧化氫、對-薄荷烷過氧化氫、1,1,3,3-四甲基丁基過氧化氫、α',α'-雙(第三丁基過氧)二異丙基苯、2,5-二甲基-2,5-雙(第三丁基過氧)己烷、2,5-二甲基-2,5-雙(第三丁基過氧)己炔-3、過氧苯甲醯、月桂基過氧化物、過氧化硬脂醯、丁二酸過氧化物、3,5,5-三甲基己醯基過氧化物、二-2-乙氧基乙基過氧二碳酸酯、二異丙基過氧碳酸酯、二-3-甲氧基丁基過氧二碳酸酯、二-2-乙基己基過氧二碳酸 酯、雙(4-第三丁基環己基)過氧二碳酸酯、第三丁基過氧乙酸酯、第三丁基過氧-2-乙基己基單碳酸酯、第三丁基過氧異丙基單碳酸酯、第三丁基過氧月桂酸酯、第三丁基過氧馬來酸、第三丁基過氧新癸酸酯、第三丁基過氧-2-乙基己酸酯、第三丁基過氧特戊酸酯、第三丁基過氧苯甲酸酯、第三丁基過氧-間-甲苯酸酯/苯甲酸酯、第三丁基過氧-3,3,5-三甲基己酸酯、α',α'-雙(新癸醯基過氧)二異丙基苯、枯基過氧新癸酸酯、1-環己基-1-甲基乙基過氧新癸酸酯、2,5-二甲基-2,5-雙(間-甲苯醯基過氧)己烷(2,5-二甲基-2,5-雙(間-甲苯醯基過氧)己烷)、2,5-二甲基-2,5-雙(2-乙基己醯基過氧)己烷、2,5-二甲基-2,5-雙(苯甲醯基過氧)己烷、第三己基過氧異丙基單碳酸酯、第三丁基過氧新癸酸酯、第三己基過氧-2-乙基己酸酯、第三己基過氧特戊酸酯、1,1,3,3-四甲基丁基過氧-2-乙基己酸酯，及3,3',4,4'-四(第三丁基過氧羰基)二苯甲酮，但不限於此等。此等可單獨或以其組合而使用。
以偶氮為主之起始劑的例子可包含2,2'-偶氮雙 (4-甲氧基-2,4-二甲基戊腈)、二甲基2,2'-偶氮雙(2-甲基丙酸酯)，及2,2'-偶氮雙(N-環己基-2-甲基丙酸酯)，但不限於此等。此等可單獨或以其組合而使用。
於某些實施例，以固體含量而言，以各向異性導 電膜之總重量為基準，固化起始劑可以0.1wt%至20wt%，特別是0.1wt%至15wt%，更特別是1wt%至10wt%之量存在。於此含量範圍內，組成物可於短時間充份固化且具有 良好相容性，因此，能有效率形成各向異性導電膜。
於其它實施例，於未使此膜之基本性質惡化下， 各向異性導電膜可進一步含有添加劑，諸如，聚合反應抑制劑、抗氧化劑、熱安定劑、固化加速劑、偶合劑等，以便提供此膜另外性質。添加之此等添加劑的量可依據此膜之目的及所欲功效以各種方式決定，且係熟習此項技藝者已知。
製備依據本發明實施例之各向異性導電膜的方 法未特別限制，且此項技藝已知之任何典型方法可不受限地使用。
形成此各向異性導電膜無需特別裝設或設備。例 如，此各向異性導電膜可藉由使一結合劑樹脂溶於一有機溶劑中，添加用於此各向異性導電膜之其它組份，以不會造成導電顆粒聚合反應之速率使混合物攪拌一段特定時間，使此混合物塗敷至一離型膜至一適合厚度，例如，10μm至50μm，及使混合物乾燥足夠時間以使有機溶劑揮發而製備。因此，各向異性導電膜可包含一各向異性導電膜及一離型膜。
依據本發明之各向異性導電膜可具有 170g/m2/24hr或更少，特別是160g/m2/24hr或更少，更特別是150g/m2/24hr或更少之透濕度。於此範圍內，以黏著性、連接電阻等而言，各向異性導電膜可展現優異可靠性，即使於高溫及/或高濕度下使用一長期時間後。
透濕度可不受限地藉由此項技藝所知之任何方 法測量。例如，一各向異性導電膜切成一具有5cm直徑及200μm厚度之樣品，且於200℃固化1小時。其後，經固化之樣品置於一含有20克氯化鈣的瓶子之入口處，瓶子被密封，且瓶子之起始重量被測量及記錄。其後，瓶子於85℃及85% RH(相對濕度)置放24小時，且水分自樣品表面移除，其後測量瓶子重量。最後，記錄重量增加。
依據本發明之各向異性導電膜可具有2%或更少，特別是1.5%或更少，更特別是1.2%或更少之吸濕度。於此範圍內，以黏著性、連接電阻、起泡性質等各向異性導電膜可展現優異可靠性，即使於高溫及/或高濕度下使用一長期時間後。
吸濕度可不受限地藉由此項技藝所知之任何方法測量。例如，一各向異性導電膜切成一具有2cm×2cm x 200μm(長，寬，厚)之尺寸的樣品，且於200℃固化1小時，其後，測量此樣品之起始重量。其後，樣品於85℃及85% RH留置24小時，且水分自樣品表面移除，其後測量樣品重量。最後，記錄重量增加。
於某些實施例，各向異性導電膜可具有400gf/cm或更多，特別是450gf/cm或更多，更特別是500gf/cm或更多，例如，530gf/cm或更多之可靠性黏著強度。可靠性黏著強度係指接受預壓縮及主要壓縮且於85℃及85% RH留置500小時，且自其移除離型膜後測量之黏著強度。
預壓縮可於60℃至80℃，於1.0MPa至4.0MPa之條件下實施1秒至3秒，且主要壓縮可於170℃至200℃， 於2.5MPa至7MPa之條件下實施1秒至7秒。例如，可靠性黏著強度可藉由下列方法測量：製備之各向異性導電膜於室溫(25℃)留置1小時，且複數個樣本係使用金屬電極玻璃(Mo/Al/Mo結構，Samsung Electronics Co.,Ltd.)及COF(Samsung Electronics Co.,Ltd.)經由於約70℃之測量溫度於1MPa之條件下預壓縮1秒，其後，於185℃於4.5MPa主要壓縮4秒，且自各向異性導電膜移除離型膜而製備。每一樣本於85℃及85% RH留置500小時，其後，使用一剝離強度測試器H5KT(Tinius Olsen)以90°剝離角度及50mm/分鐘之剝離速率測量平均剝離強度。
於某些實施例，包含於各向異性導電膜內之各向 異性導電膜可具有可靠性3Ω或更少，特別是2.6Ω或更少之連接電阻。可靠性連接電阻係指於接受預壓縮及主要壓縮且於85℃及85% RH留置500小時，且自其移除一離型膜後測量之連接電阻。於此範圍內，各向異性導電膜具有低電阻，即使於高溫及/或高濕度下使用一長期時間後，因此，提供優異可靠性。
例如，可靠性連接電阻強度可藉由下列方法測 量：製備之各向異性導電膜於室溫(25℃)留置1小時，且每一各向異性導電膜之10個樣品係藉由使各向異性導電膜與藉由於以一1000Å厚之ITO層塗覆之一0.5t無圖案之玻璃板上形成一圖案(其能4-探針測量)而製備之COF(Samsung Electronics Co.,Ltd.)連接，經由於70℃之測量溫度，1秒及1MPa之條件下預壓縮，及於185℃，4秒及4.5MPa之條件 下主要壓縮，且自各向異性導電膜移除離型膜而製備。於每一各向異性導電膜之10個樣本於85℃及85% RH留置500小時以於高溫及高濕度條件下評估可靠性後，每一樣本之可靠性連接電阻被測量(依據ASTM D117)，且計算一平均值。
於某些實施例，包含於各向異性導電膜中之各向 異性導電膜可具有20%或更少，特別是15%或更少之可靠性起泡面積。可靠性起泡面積係指於接受預壓縮及主要壓縮且於85℃及85% RH留置500小時，且自其移除一離型膜後測量之起泡面積。於此範圍內，各向異性導電膜具有窄起泡面積，即使於高溫及/或高濕度下使用一長期時間後，因此，提供優異之黏著性及可靠性。
例如，可靠性起泡面積可藉由下列方法測量：製 備之各向異性導電膜於室溫(25℃)留置1小時，且複數個樣本係使用金屬電極玻璃(Mo/Al/Mo結構，Samsung Electronics Co.,Ltd.)及COF(Samsung Electronics Co.,Ltd.)，經由於70℃之測量條件於1MPa之條件下預壓縮1秒，其後，於185℃於4.5MPa主要壓縮4秒，且自各向異性導電膜移除一離型膜而製備。
每一各向異性導電膜之10個樣本於85℃及85% RH留置500小時，以於高溫及高濕度下評估可靠性，且且每一樣品之10個點使用一光學顯微鏡照相。其後，起泡面積對電極間之空間的面積之比率係使用一影像分析器測量，且計算一平均值。
依據本發明之另一實施例，一半導體裝置包含： 一第一連接元件，其具有一第一電極；一第二連接元件，其具有一第二電極；及依據本發明之各向異性導電膜，其係設置於第一及第二連接元件之間，且使第一及第二電極彼此電連接。
參考圖1，依據此實施例之半導體裝置包含一第 一連接元件50，其具有一第一電極70；一第二連接元件60，其具有一第二電極80；及一各向異性導電膜10，其含有導電顆粒40。當置於具有第一電極70之第一連接元件50與具有第二電極80之第二連接元件60間的各向異性導電膜10被壓縮，第一電極70及第二電極80係經由導電顆粒40彼此連接。於此實施例，以材料、厚度、尺寸及相互連接性而言，第一及第二連接元件50，60可具有相似結構。第一及第二連接元件50，60具有從約20μm至約100μm之厚度。
於另一實施例，以材料、厚度、尺寸及相互連接 性而言，第一及第二連接元件可具有不同結構及功能。第一連接元件或第二連接元件可由玻璃、PCB(印刷電路板)、fPCB、COF、TCP、ITO玻璃等形成，但不限於此等。第一電極或第二電極可為一凸電極或一平電極。當第一及第二電極係凸電極，此等電極可具有約2.50μm至約10μm之高度(H)，約50μm至約100μm之寬度(W)，及約50μm至約110μm之電極間的間隙(G)。較佳地，此等電極具有約2.50μm至約9μm之高度(H)，約50μm至約100μm之寬度(W)，及約60μm至約100μm之電極間的間隙(G)。
當第一及第二電極係平電極，此等電極可具有約 500Å至約1200Å之厚度，且可由ITO、銅、矽、IZO等形成，但不限於此等。
平電極可具有從800Å至1200Å之厚度，且凸電極 可具有從6μm至10μm之高度。此處，當一絕緣層具有從4μm至12μm之厚度，可確保充份黏著。更佳地，平電極具有1000Å之厚度，且凸電極具有8μm之高度。此處，絕緣層具有從6μm至10μm之厚度。
依據本發明，此項技藝已知之任何方法可不受限地用以製備一半導體裝置。
其次，本發明會參考某些範例作更詳細說明。但是，需瞭解此等範例係僅提供作為例示，且不以任何方式作為限制本發明而闡釋。
範例1
5wt%之一丙烯腈-丁二烯橡膠樹脂(N-34，Nippon Zeon)，35wt%之一聚胺基甲酸酯樹脂(NPC7007T，Nanux)，20wt%之一丙烯酸樹脂(AOF-7003，Aekyung Chemical)，13wt%之丙烯酸4-羥基丁酯，13wt%之二羥甲基二環癸烷二丙烯酸酯，8wt%之季戊四醇三丙烯酸酯，3wt%之導電顆粒(3μm之平均顆粒直徑，Sekisui)，及3wt%之月桂基過氧化物被混合製備一用於各向異性導電膜之組成物。
組成物於室溫(25℃)以導電顆粒未粉碎之攪拌速率攪拌60分鐘。一35μm厚之膜係使用此組成物於一經矽氧樹脂離型表面處理之聚乙烯基材膜上形成，且使用一鑄 製刀形成膜。此膜於60℃乾燥5分鐘。
範例2
一各向異性導電膜係以與範例1相同之方式製備，除了使用10wt%之丙烯酸4-羥基丁酯，10wt%之二羥甲基三環癸烷二丙烯酸酯，及9wt%之季戊四醇三丙烯酸酯，且加外使用5wt%之二氧化矽顆粒(0.5μm，Denka)。
範例3
一各向異性導電膜係以與範例1相同之方式製備，除了使用26wt%之二羥甲基三環癸烷二丙烯酸酯替代丙烯酸4-羥基丁酯。
比較例1
一各向異性導電膜係以與範例1相同方式製備，除了使用9wt%之丙烯酸4-羥基丁酯及25wt%之二氧化矽顆粒(0.5μm，Denka)，且未使用二羥甲基三環癸烷二丙烯酸酯及季戊四醇三丙烯酸酯。
比較例2
一各向異性導電膜係以與範例1相同方式製備，除了使用17wt%之丙烯酸4-羥基丁酯及17wt%之二羥甲基三環癸烷二丙烯酸酯，且未使用季戊四醇三丙烯酸酯。
比較例3
一各向異性導電膜係以與範例1相同方式製備，除了使用7wt%之丙烯酸4-羥基丁酯，7wt%之二羥甲基二環癸烷二丙烯酸酯，及20wt%之季戊四醇三丙烯酸酯。
比較例4
一各向異性導電膜係以與範例1相同方式製備，除了使用16wt%之丙烯酸4-羥基丁酯，16wt%之二羥甲基三環癸烷二丙烯酸酯，及2wt%之季戊四醇三丙烯酸酯。
範例1至3及比較例1至4製備之各向異性導電膜之組成物係如表1中所示。
實驗例1：測量透濕度
範例1至3及比較例1至4製備之各向異性導電膜之每一者的透濕度係如下般測量。
每一各向異性導電膜切成一具有5cm直徑及200μm厚度之樣本，且於200℃固化1小時。其後，經固化之樣品置於一含有20克氯化鈣之瓶子的入口，且瓶子被密封，且瓶子之起始重量被測量及記錄。
其後，瓶子於85℃及85% RH留置24小時，且水分自樣品表面移除，其後，測量瓶子子量。最後，記錄重量增加。
實驗例2：測量吸濕度
範例1至3及比較例1至4製備之各向異性導電膜的每一者之吸濕度係如下般測量。
每一各向異性導電膜切成一具有2cm×2cm x 200μm(長，寬，厚)之尺寸的樣品，且於200℃固化1小時，其後，測量樣品之起始重量。
其後，樣品於85℃及85% RH留置24小時，且水分自樣品表面移除，其後測量樣品重量。最後，記錄重量增加。
實驗例3：測量可靠性連接電阻
範例1至3及比較例1至4製備之各向異性導電膜 之每一者的可靠性連接電且係如下般測量。
每一各向異性導電膜於室溫(25℃)留置1小時， 且每一各向異性導電膜之10個樣品係藉由使各向異性導電膜與藉由於以一1000Å厚之ITO層塗覆之一0.5t無圖案之玻璃板上形成一圖案(其能4-探針測量)而製備之COF(Samsung Electronics Co.,Ltd.)連接，經由於70℃之測量溫度，1秒及1MPa之條件下預壓縮，及於185℃，4秒及4.5MPa之條件下主要壓縮，且自各向異性導電膜移除離型膜而製備。
於每一各向異性導電膜之10個樣本於85℃及 85% RH留置500小時以於高溫及高濕度條件下評估可靠性後，每一樣本之可靠性連接電阻被測量(依據ASTM D117)，且計算一平均值。
實驗例4：測量可靠性黏著強度
範例1至3及比較例1至4製備之各向異性導電膜之每一者的可靠性黏著強度係如下般測量。
每一各向異性導電膜於室溫(25℃)留置1小時，且每一各向異性導電膜之10個樣本係使用金屬電極玻璃(Mo/Al/Mo結構，Samsung Electronics Co.,Ltd.)及COF(Samsung Electronics Co.,Ltd.)經由於約70℃之測量溫度於1MPa之條件下預壓縮1秒，其後，於185℃於4.5MPa主要壓縮4秒，且自各向異性導電膜移除離型膜而製備。
10個樣本之每一者於85℃及85% RH留置500小時以評估於高溫及高濕度條件下之可靠性，其後，使用一 剝離強度測試器H5KT(Tinius Olsen)以90°剝離角度及50mm/分鐘之剝離速率測量平均剝離強度。
實驗例5：測量可靠性起泡面積
範例1至3及比較例1至4製備之各向異性導電膜之每一者的可靠性起泡面積係如下般測量。
每一各向異性導電膜於室溫(25℃)留置1小時，且每一各向異性導電膜之10個樣本係使用金屬電極玻璃(Mo/Al/Mo結構，Samsung Electronics Co.,Ltd.)及COF(Samsung Electronics Co.,Ltd.)，經由於70℃之測量條件於1MPa之條件下預壓縮1秒，其後，於185℃於4.5MPa主要壓縮4秒，且自各向異性導電膜移除一離型膜而製備。
每一各向異性導電膜之10個樣本於85℃及85% RH留置500小時，以於高溫及高濕度下評估可靠性，且且每一樣品之10個點使用一光學顯微鏡照相。其後，起泡面積對電極間之空間的面積之比率係使用一影像分析器測量，且計算一平均值。
實驗例1至5之實驗結果係顯示於表2。
雖然一些實施例已被揭露，但對於熟習此項技藝者明顯的是此等實施例僅係作為例示，且各種修改、變化、改變，及等化實施例可於未偏離本發明之精神及範圍為之。本發明之範圍需僅受限於所附申請專利範圍。
10‧‧‧各向異性導電膜
40‧‧‧導電顆粒
50‧‧‧第一連接元件
60‧‧‧第二連接元件
70‧‧‧第一電極
80‧‧‧第二電極

Claims (13)

  1. 一種各向異性導電膜，包含：a)一結合劑樹脂；b)一於其結構中具有一或二個(甲基)丙烯酸酯反應基團之第一自由基聚合材料，及一於其結構中具有至少三個(甲基)丙烯酸酯反應基團之第二自由基聚合材料；及c)導電顆粒；其中，該各向異性導電膜具有170g/m2/24hr或更少之透濕度及2%或更少之吸濕度。
  2. 如請求項1之各向異性導電膜，其中，該各向異性導電膜具有400gf/cm或更多之可靠性黏著強度，其係於接受於60℃至80℃於1.0MPa至4.0MPa之條件下預壓縮1秒至3秒，及於170℃至200℃於2.5MPa至7MPa之條件下主要壓縮1秒至7秒，且自該經預壓縮之各向異性導電膜移除一離型膜，且於85℃之溫度及85%之相對濕度留置500小時後測量。
  3. 如請求項1之各向異性導電膜，其中，該各向異性導電膜具有3Ω或更少之可靠性連接電阻，其係於接受於60℃至80℃於1.0MPa至4.0MPa之條件下預壓縮1秒至3秒，及於170℃至200℃於2.5MPa至7MPa之條件下主要壓縮1秒至7秒，且自該經預壓縮之各向異性導電膜移除一離型膜，且於85℃之溫度及85%之相對濕度留置500小時後測量。
  4. 如請求項1之各向異性導電膜，其中，該各向異性導電 膜具有20%或更少之可靠性起泡面積，其係於接受於60℃至80℃於1.0MPa至4.0MPa之條件下預壓縮1秒至3秒，及於170℃至200℃於2.5MPa至7MPa之條件下主要壓縮1秒至7秒，且自該經預壓縮之各向異性導電膜移除一離型膜，且於85℃之溫度及85%之相對濕度留置500小時後測量。
  5. 如請求項1之各向異性導電膜，其中，以固體含量而言，該各向異性導電膜包含：30wt%至80wt%之該(a)結合劑樹脂；6wt%至60wt%之該(b)自由基聚合材料；及0.1wt%至20wt%之該(c)導電顆粒。
  6. 如請求項1之各向異性導電膜，其中，該第一自由基聚合材料對該第二自由基聚合材料之重量比率範圍係從1至10。
  7. 如請求項1之各向異性導電膜，其中，該(a)結合劑樹脂包含至少二種具有不同重量平均分子量之樹脂。
  8. 如請求項7之各向異性導電膜，其中，該(a)結合劑樹脂包含至少二種選自由丙烯腈-丁二烯橡膠樹脂、聚胺基甲酸酯樹脂，及丙烯酸樹脂所組成組群之樹脂。
  9. 如請求項1之各向異性導電膜，其中，該第一自由基聚合材料包含選自由(甲基)丙烯酸羥基丁酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸2-羥基丙酯，及(甲基)丙烯酸縮水甘油酯所組成組群之至少一者。
  10. 如請求項1之各向異性導電膜，其中，該第二自由基聚 合材料包含選自由季戊四醇三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、經環氧乙烷改質之三羥甲基丙烷之三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯，及二季戊四醇六(甲基)丙烯酸酯所組成組群之至少一者。
  11. 如請求項1之各向異性導電膜，其中，該各向異性導電膜進一步包含無機顆粒。
  12. 如請求項11之各向異性導電膜，其中，以固體含量而言，以該各向異性導電膜之總重量為基準，該無機顆粒係以0.1wt%至20wt%之量存在。
  13. 一種半導體裝置，包含：一第一連接元件，其含有一第一電極；一第二連接元件，其含有一第二電極；及如請求項1至12中任一項之各向異性導電膜，該各向異性導電膜係設置於該第一連接元件與該第二連接元件之間且使該第一電極與該第二電極結合。
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