TWI531609B - 各向異性導電膜的組成物、各向異性導電膜及半導 體裝置 - Google Patents
各向異性導電膜的組成物、各向異性導電膜及半導 體裝置 Download PDFInfo
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- TWI531609B TWI531609B TW104107107A TW104107107A TWI531609B TW I531609 B TWI531609 B TW I531609B TW 104107107 A TW104107107 A TW 104107107A TW 104107107 A TW104107107 A TW 104107107A TW I531609 B TWI531609 B TW I531609B
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Description
本發明是有關於一種各向異性導電膜,其允許在初步熱壓後在低溫下快速固化並且展現充足的穩定性,同時保證結合(bonding)後優良的連線性質;和有關於一種使用所述各向異性導電膜的半導體裝置。
含有環氧樹脂的各向異性導電黏著劑用於如軟性印刷電路(flexible printed circuit,FPC)板、卷帶式自動結合(tape automated bonding,TAB)板、印刷電路板(printed circuit board,PCB)、玻璃電路板等等電路板上的電極之間的電連接,同時使所述電路板彼此結合(bonding)。需要這些黏著劑來保證電路板之間的電連接並且允許在相對較低溫度下快速固化,以便防止對電路板造成熱損傷。
這類各向異性導電黏著劑的組成物是由陽離子可聚合環
氧樹脂組成物組成。陽離子可聚合環氧樹脂組成物包含陽離子固化催化劑,所述陽離子固化催化劑借由熱和光引起陽離子聚合反應來生成質子。銻酸鋶錯合物被認為是這類陽離子固化催化劑。然而,銻酸鋶錯合物具有作為抗衡陰離子的SbF6-,其中氟原子鍵結到金屬銻,從而使氟離子大量生成並且在陽離子聚合反應期間發生異質金屬的遷移,由此導致金屬線或者連接墊受到腐蝕。因此,需要各種不會引起這一腐蝕問題同時展現能夠實現在低溫下快速固化的反應性的陽離子固化催化劑。另外,實現在低溫下快速固化的常規技術具有儲存穩定性不良的問題,並且需要改善穩定性。
因此,需要一種各向異性導電膜,其允許在低溫下快速固化並且展現充足的儲存穩定性,同時保證結合後優良的連線性質。
本發明的一個目標為提供一種各向異性導電膜,其允許在初步熱壓後在低溫下快速固化並且展現充足的穩定性,同時保證結合後優良的連線性質;和一種使用所述各向異性導電膜的半導體裝置。
根據本發明的一個實施例,提供一種各向異性導電膜,通過差示掃描熱量測定法(differential scanning calorimetry,DSC)測量且根據以下方程1計算,其在25℃下靜置170小時後熱量變
化率為35%或者小於35%:熱量變化率(%)=[(H0-H1)/H0]×100----(1),其中H0為各向異性導電膜在25℃下靜置0小時後通過DSC測量的熱量;並且H1為各向異性導電膜在25℃下靜置170小時後通過DSC測量的熱量。
根據本發明的另一個實施例,提供一種各向異性導電膜的組成物,其可能包含放熱峰值溫度為80℃至110℃的第一環氧樹脂和放熱峰值溫度為120℃至200℃的第二環氧樹脂,所述放熱峰值溫度通過DSC測量,其中按組成物的固體含量的總重量計,第一環氧樹脂和第二環氧樹脂以30重量%至50重量%的量存在,並且按第一環氧樹脂和第二環氧樹脂為100重量份計,第二環氧樹脂以60重量份至90重量份的量存在。
根據本發明的另一個實施例,提供一種通過各向異性導電膜或者通過由各向異性導電膜的組成物形成的各向異性導電膜連接的半導體裝置。
根據本發明的各向異性導電膜和包含所述各向異性導電膜的半導體裝置允許在100℃至150℃的低溫下快速固化並且展現充足的穩定性,同時保證結合後優良的連線性質。
3‧‧‧導電粒子
10‧‧‧黏著層
30‧‧‧半導體裝置
50‧‧‧第一連接部件
60‧‧‧第二連接部件
70‧‧‧第一電極
80‧‧‧第二電極
圖1為根據本發明的一個實施例的半導體裝置30的截面視
圖,包含第一連接部件50和第二連接部件60,其借助於各向異性導電黏著膜的黏著層10彼此連接並且分別包含第一電極70和第二電極80。
在下文中,將更詳細地描述本發明的實施例。為了清楚起見,將省略本領域的技術人員顯而易知的細節描述。
本發明的一個實施例提供一種各向異性導電膜的組成物,所述各向異性導電膜的組成物包含放熱峰值溫度為80℃至110℃的第一環氧樹脂和放熱峰值溫度為120℃至200℃的第二環氧樹脂,所述放熱峰值溫度通過差示掃描熱量測定法(DSC)測量。
在本文中,環氧樹脂的放熱峰值溫度可以在將由式1表示的陽離子固化催化劑添加到所述環氧樹脂中後,使用例如型號Q20(TA儀器(TA Instruments))的差示掃描式熱量計(differential scanning calorimeter)以10℃/min測量。
第一環氧樹脂的放熱峰值溫度為80℃至110℃,特定地為85℃至105℃。第二環氧樹脂的放熱峰值溫度為120℃至200℃,特定地為130℃至185℃。
在具有不同放熱峰值溫度的兩種類型的環氧樹脂的情況下,各向異性導電膜的組成物在低溫下可以通過調節固化率來快速固化,同時保證在室溫下的儲存穩定性。
第一環氧樹脂可能包含選自由以下組成的群組的至少一
種:環氧丙烷系環氧樹脂(propylene oxide-based epoxy resin)、氫化雙酚A環氧樹脂(hydrogenated bisphenol A epoxy resin)、環脂族環氧樹脂(cycloaliphatic epoxy resin)以及萘環氧樹脂(naphthalene epoxy resin)。特定地說,第一環氧樹脂可以是環氧丙烷系環氧樹脂或者氫化雙酚A環氧樹脂。
第二環氧樹脂可能包含選自由以下組成的群組的至少一種:雙酚A環氧樹脂(bisphenol A epoxy resin)、酚醛清漆環氧樹脂(novolac epoxy resin)、鄰苯二甲酸酯環氧樹脂(phthalate epoxy resin)以及聯苯環氧樹脂(biphenyl epoxy resin)。特定地說,第二環氧樹脂可以是雙酚A環氧樹脂(例如JER834,日本三菱化學(Mitsubishi Chemicals,Japan))或鄰苯二甲酸酯系環氧樹脂(phthalate-based epoxy resin)(例如EX721,日本長瀨(Nagase,Japan))。按組成物的固體含量的總重量計,第一環氧樹脂和第二環氧樹脂可能以30重量%至50重量%的量存在,並且按第一環氧樹脂和第二環氧樹脂為100重量份計,第二環氧樹脂可能以60重量份至90重量份的量存在。在這一範圍內,各向異性導電膜的組成物可以在100℃至150℃的低溫下快速固化,同時保證充足的儲存穩定性。
在一個實施例中,按組成物的固體含量的總量計,第二環氧樹脂可能以20重量%至40重量%的量存在。這一範圍的第二環氧樹脂就各向異性導電膜的組成物在室溫下的穩定性來說是有利的。
在本發明的另一個實施例中,各向異性導電膜的組成物可能包含陽離子固化催化劑。根據本發明,本領域中已知的任何陽離子固化催化劑均可以不受限制地使用。
陽離子固化催化劑可能包含鋶系陽離子固化催化劑(sulfonium-based cationic curing catalyst),特定地為硼酸鋶系陽離子固化催化劑(sulfonium borate-based cationic curing catalyst)。
硼酸鋶系陽離子固化催化劑的實例可能包含由式1表示的化合物:
其中R1至R5各自獨立地選自由以下組成的群組:氫原子、經取代或者未經取代的C1至C6烷基、乙醯基(acetyl group)、烷氧羰基(alkoxycarbonyl group)、苯甲醯基(benzoyl group)以及苯甲氧羰基(benzyloxycarbonyl group),並且R6和R7各自獨立地選自由以下組成的群組:烷基、苯甲基(benzyl group)、鄰甲基苯甲基(o-methylbenzyl group)、間甲基苯甲基(m-methylbenzyl group)、對甲基苯甲基(p-methylbenzyl group)以及萘甲基(naphthylmethyl group)。
由式1表示的陽離子固化催化劑可以防止在陽離子聚合反應期間生成大量的氟離子,由此防止金屬線或連接墊受到腐蝕。另外,由式1表示的陽離子固化催化劑能夠通過在較低的溫
度下生成陽離子來實現各向異性導電膜在例如150℃或者低於150℃,特定地140℃或者低於140℃,更特定地130℃的低溫下固化。
按各向異性導電膜的組成物的固體含量的總重量計,硼酸鋶類陽離子固化催化劑可能以1重量%至15重量%、特定地3重量%至10重量%的量存在。
根據本發明的另一個實施例,各向異性導電膜的組成物可能進一步包含黏合劑樹脂。
本發明不限於特定黏合劑樹脂,並且本領域中已知的任何典型黏合劑樹脂均可以不受限制地使用。
黏合劑樹脂的實例可能包含聚醯亞胺樹脂(polyimide resin)、聚醯胺樹脂(polyamide resin)、苯氧基樹脂(phenoxy resin)、環氧樹脂、聚甲基丙烯酸酯樹脂(polymethacrylate resin)、聚丙烯酸酯樹脂(polyacrylate resin)、聚氨基甲酸酯樹脂(polyurethane resin)、經丙烯酸酯改質的氨基甲酸酯樹脂(acrylate modified urethane resin)、聚酯樹脂(polyester resin)、聚酯氨基甲酸酯樹脂(polyester urethane resin)、聚乙烯醇縮丁醛樹脂(polyvinyl butyral resin)、苯乙烯-丁烯-苯乙烯(styrene-butylene-styrene,SBS)樹脂及其環氧化改質體、苯乙烯-乙烯-丁烯-苯乙烯(styrene-ethylene-butylene-styrene,SEBS)樹脂及其改質體、丙烯腈丁二烯橡膠(acrylonitrile butadiene rubber,NBR)或者其氫化化合物。這些可以單獨使用或者以其組合的形式使用。儘管較高重量平均分子量的黏合劑樹脂允許更容
易地成膜,但是本發明並不限於特定的重量平均分子量的黏合劑樹脂。舉例來說,黏合劑樹脂的重量平均分子量可能為5,000g/mol至150,000g/mol,更特定地為10,000g/mol至80,000g/mol。如果黏合劑樹脂的重量平均分子量小於5,000g/mol,那麼可能難以形成膜,並且如果黏合劑樹脂的重量平均分子量超過150,000g/mol,那麼可能出現與其它組份的相容性不佳的問題。按各向異性導電膜的組成物的固體含量的總量計,黏合劑樹脂可能以30重量%至70重量%、特定地30重量%至60重量%、更特定地35重量%至50重量%的量存在。在這一範圍內,組成物可能展現良好的成膜能力和黏著強度。
根據本發明的又一個實施例,各向異性導電膜的組成物可能進一步包含導電粒子。
本發明不限於特定導電粒子,並且用於本領域的任何典型導電粒子均可以不受限制地使用。
導電粒子的實例可能包含金屬粒子,如金(Au)、銀(Ag)、鎳(Ni)、銅(Cu)以及焊料粒子;碳粒子;樹脂粒子,如聚乙烯、聚丙烯、聚酯、聚苯乙烯、聚乙烯醇以及其塗覆有金屬(如金(Au)、銀(Ag)、鎳(Ni)、鈀(Pd)等等)的改質樹脂粒子;以及通過將絕緣粒子進一步塗覆到塗覆有金屬的聚合物樹脂粒子上所獲得的絕緣導電粒子,但不限於此。這些可以單獨使用或者以其組合的形式使用。
導電粒子的平均粒度可以視待使用的電路的間距(pitch)
而不同,並且可以視其目的在1μm至20μm的範圍內選擇。特定地說,導電粒子的平均粒度可能為1μm至10μm。
在一些實施例中,按組成物的固體含量的總量計,導電粒子可能以1重量%至30重量%、特定地1重量%至25重量%、更特定地1重量%至20重量%的量存在。
在導電粒子的這些範圍內,組成物可以保證穩定的連接可靠性,同時展現較低的連接電阻。
根據本發明的又一個實施例,各向異性導電膜的組成物可能進一步包含穩定劑。
穩定劑的實例可能包含鋶(sulfonium)、胺(amine)、酚(phenol)、冠酯(crown ester)、膦(phosphine)以及三嗪(triazine)等等。因為穩定劑的添加量可能視化合物的性質而不同,所以對於穩定劑的量不存在特定限制。在一些實施例中,按組成物的固體含量的總量計,穩定劑可能以0.01重量%至5重量%、特定地0.02重量%至3重量%的量存在。
根據本發明的又一個實施例,各向異性導電膜的組成物可能進一步包含矽烷偶合劑。
矽烷偶合劑可能包含選自由以下組成的群組的至少一種:含可聚合氟基的矽化合物,如乙烯基三甲氧基矽烷(vinyltrimethoxysilane)、乙烯基三乙氧基矽烷(vinyltriethoxysilane)、(甲基)丙烯氧基丙基三甲氧基矽烷((meth)acryloxypropyltrimethoxysilane)等等;含環氧基的矽化合物,如
3-縮水甘油氧基丙基三甲氧基矽烷(3-glycidoxypropyl trimethoxysilane)、3-縮水甘油氧基丙基甲基二甲氧基矽烷(3-glycidoxypropylmethyldimethoxysilane)、2-(3,4-環氧基環己基)-乙基三甲氧基矽烷(2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane)等等;含氨基的矽化合物,如3-氨基丙基三甲氧基矽烷(3-aminopropyltrimethoxysilane)、N-(2-氨基乙基)-3-氨基丙基三甲氧基矽烷(N-(2-aminoethyl)-3-aminopropyltrimethoxysilane)、N-(2-氨基乙基)-3-氨基丙基甲基二甲氧基矽烷(N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane)等等;以及3-氯丙基三甲氧基矽烷(3-chloropropyltrimethoxysilane),但不限於此。
按組成物的固體含量的總量計,矽烷偶合劑可能以1重量%至10重量%的量存在。
根據本發明的又一個實施例,各向異性導電膜的組成物可能進一步包含其它添加劑,如聚合抑制劑、抗氧化劑、熱穩定劑等等,以便賦予各向異性導電膜額外的性質而不使其基本性質退化。按組成物的固體含量的總量計,添加劑可能以0.01重量%至10重量%的量存在。
聚合抑制劑的實例可能包含氫醌(hydroquinone)、氫醌單甲基醚(hydroquinone monomethylether)、對苯醌(p-benzoquinone)、啡噻嗪(phenothiazine)或者其混合物。抗氧
化劑的實例可能包含酚系或者羥基肉桂酸酯物質。舉例來說,可以使用四-(亞甲基-(3,5-二-叔丁基-4-羥基肉桂酸酯)甲烷(tetrakis-(methylene-(3,5-di-t-butyl-4-hydroxycinnamate)methane)、3,5-雙(1,1-二甲基乙基)-4-羥基苯丙酸硫二-2,1-乙烷二基酯(3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid thiodi-2,1-ethanediyl ester)等等。
根據本發明的又一個實施例,提供一種由本發明實施例之一的組成物形成的各向異性導電膜。
各向異性導電膜可能包含由各向異性導電膜的組成物形成的各向異性導電黏著層和離型膜。離型膜可以在將各向異性導電膜初步壓到第一連接部件或者第二連接部件後去除。因此,各向異性導電膜可以與各向異性導電黏著層相容。
各向異性導電膜可能具有單層結構,其包含單一各向異性導電黏著層;雙層結構,其中不含有導電粒子的非導電黏著層和含有導電粒子的導電黏著層依次堆疊;或者三層結構,其中非導電黏著層堆疊在導電黏著層的相對兩側上。應該理解,根據本發明的各向異性導電膜的組成物可以用作非導電黏著層、導電黏著層或者用作非導電黏著層和導電黏著層兩者。
本發明的另一個實施例提供一種各向異性導電膜,其在25℃下靜置170小時後,通過差示掃描熱量測定法(DSC)來測量且根據以下方程1來計算,熱量變化率為35%或者小於35%。
熱量變化率(%)=[(H0-H1)/H0]×100----(1),其中H0為各向異性導電膜在25℃下靜置0小時後通過DSC測量的熱量;並且H1為各向異性導電膜在25℃下靜置170小時後通過DSC測量的熱量。
各向異性導電膜的熱量變化率可能為34%或者小於34%,特定地為25%或者小於25%。各向異性導電膜可能包含放熱峰值溫度為120℃至200℃的環氧樹脂,所述放熱峰值溫度通過差示掃描熱量測定法測量。或者,各向異性導電膜可能包含放熱峰值溫度為80℃至110℃的第一環氧樹脂和放熱峰值溫度為120℃至200℃的第二環氧樹脂,所述放熱峰值溫度通過差示掃描熱量測定法測量。
熱量變化率可以通過本領域中已知的任何典型方法來測量。舉例來說,熱量變化率可以通過以下方法(但不限於此)來測量。在這一方法中,在取1mg根據本發明的一個實施例的各向異性導電膜作為試樣後,使用例如型號Q20(TA儀器)的差示掃描式熱量計在25℃下在-50℃至250℃的溫度區中以10℃/min來測量試樣的初始熱量(H0)。然後將膜在25℃下靜置170小時,並且以相同方式測量膜的熱量(H1)。然後根據方程1來計算熱量變化率。
在熱量變化率的這一範圍內,各向異性導電膜可以展現良好的儲存穩定性並且可以防止附著力退化或者連接電阻增加。
各向異性導電膜可能具有62℃至90℃的差示掃描熱量測
定法起始溫度(DSC起始溫度(DSC onset temperature))和85℃至120℃的峰值溫度。特定地說,各向異性導電膜可能具有63℃至87℃的DSC起始溫度和89℃至110℃的峰值溫度。起始溫度和峰值溫度的這些範圍涉及各向異性導電膜在例如150℃或者低於150℃的低溫下的快速固化。在本文中,DSC起始溫度是指在測量各向異性導電膜取決於溫度變化的熱量時由於產生熱而使得DSC圖斜率第一次增加的時間點的溫度。此外,峰值溫度是指在熱量達到DSC圖中的最高點的時間點的溫度。
本發明的另一個實施例提供一種各向異性導電膜,當放在包含電極的玻璃基板與IC驅動器晶片或者IC晶片之間的各向異性導電膜在140℃至160℃下、在60MPa至80MPa負荷下壓縮並加熱3秒至7秒後立即在25℃下測量,所述各向異性導電膜具有3Ω或者小於3Ω的連接電阻,並且當已經在25℃下靜置170小時然後放在包含電極的玻璃基板與IC驅動器晶片或者IC晶片之間的各向異性導電膜在相同條件下壓縮並加熱後測量,所述各向異性導電膜具有7Ω或者小於7Ω的連接電阻。
當在壓縮並加熱後立即在25℃下測量,各向異性導電膜可能具有2.7Ω或者小於2.7Ω、特定地為2.5Ω或者小於2.5Ω的連接電阻。當在25℃下靜置170小時後測量,各向異性導電膜可能具有6.5Ω或者小於6.5Ω、特定地為6Ω或者小於6Ω的連接電阻。
可以通過本領域中所使用的任何典型方法來測量連接電
阻。舉例來說,可以通過以下方法測量連接電阻。在這一方法中,將具有1200μm2的凸塊區域和厚度為2000Å的氧化銦錫(indium tin oxide,ITO)電路的玻璃基板和具有1200μm2的凸塊區域且厚度為1.5mm的IC晶片放到各向異性導電膜的上表面和下表面上,隨後在150℃和70Mpa的條件下壓縮並加熱5秒,由此製備各向異性導電膜的試樣。然後通過4探針方法,使用電阻測試儀型號2000萬用表(吉時利有限公司(Keithley Co.,Ltd))通過施加1mA的測試電流來測量試樣的初始連接電阻。另外,在25℃下靜置170小時後,使各向異性導電膜在相同條件下經歷壓縮和加熱,以便製備試樣。然後以相同方式測量樣品的連接電阻。
在連接電阻的以上範圍內,各向異性導電膜具有良好的連接可靠性。
本發明的又一個實施例提供通過如上文所述的各向異性導電膜中的一種連接的半導體裝置。半導體裝置可能包含第一連接部件,其包含第一電極;第二連接部件,其包含第二電極;以及各向異性導電膜,其放在第一連接部件與第二連接部件之間,並且連接第一電極與第二電極。此處,各向異性導電膜與根據本發明實施例的各向異性導電膜,或者與由根據本發明實施例的各向異性導電膜的組成物形成的各向異性導電膜相同。此處,第一連接部件和第二連接部件不受特定限制,並且本領域中已知的任何連接部件均可以用作第一連接部件和第二連接部件。第二連接部件可能包含例如半導體矽晶片、IC晶片或者IC驅動器晶片。第
一連接部件可能包含例如上面形成有電極的玻璃基板、PCB(印刷電路板)或者fPCB(軟性印刷電路板)。參看圖1,如上文所述,根據本發明的一個實施例的半導體裝置30包含第一連接部件50,其包含第一電極70;第二連接部件60,其包含第二電極80;以及各向異性導電黏著層,其包含導電粒子3。此處,各向異性導電黏著層放在第一連接部件50與第二連接部件60之間,並且借助於導電粒子3連接第一電極70與第二電極80。用於製造根據本發明的半導體裝置的方法不受特定限制,並且可以使用本領域中已知的任何方法。
本發明的又一個實施例提供一種半導體裝置,當放在對應於第一連接部件的玻璃基板與對應於第二連接部件的IC驅動器晶片或者IC晶片之間的各向異性導電膜在140℃至160℃下、在60MPa至80MPa負荷下壓縮並加熱3秒至7秒後立即在25℃下測量,所述半導體裝置具有3Ω或者小於3Ω的連接電阻;並且當已經在25℃下靜置170小時然後置放在包含電極的玻璃基板與IC驅動器晶片或者IC晶片之間的各向異性導電膜在140℃至160℃以及60MPa至80MPa負荷的條件下壓縮並加熱3秒至7秒後測量,所述半導體裝置具有7Ω或者小於7Ω的連接電阻。
半導體裝置當在壓縮並加熱後立即在25℃下測量可能具有2.7Ω或者小於2.7Ω、特定地為2.5Ω或者小於2.5Ω的連接電阻。半導體裝置當在25℃下靜置170小時後測量可能具有6.5Ω或者小於6.5Ω、特定地為6Ω或者小於6Ω的連接電阻。
可以通過本領域中使用的任何典型方法來測量連接電阻。舉例來說,可以通過以下方法測量連接電阻。在這一方法中,將具有1200μm2的凸塊區域和厚度為2000Å的氧化銦錫(ITO)電路的玻璃基板和具有1200μm2的凸塊區域且厚度為1.5mm的IC晶片放到各向異性導電膜的上表面和下表面上,隨後在150℃和70Mpa的條件下壓縮並加熱5秒,由此製備各向異性導電膜的試樣。然後通過4探針方法,使用電阻測試儀型號2000萬用表(吉時利有限公司)通過施加1mA測試電流來測量試樣的初始連接電阻。另外,在25℃下靜置170小時後,使各向異性導電膜在相同條件下經歷壓縮和加熱,以便製備試樣。然後以相同方式測量樣品的連接電阻。
在連接電阻的以上範圍內,半導體裝置具有良好的連接可靠性。
接下來,本發明將參照一些實例作更詳細地描述。然而,應該理解,提供這些實例僅僅用於說明,並且不應該理解為以任何方式限制本發明。
實例和比較例
製備各向異性導電膜的組成物
實例1至實例3以及比較例1和比較例2的各向異性導電膜的組成物各自如表1中所列來製備。
實例1
通過以下來製備各向異性導電膜的組成物:混合40重量%的以40體積%的量溶解於二甲苯/乙酸乙酯共沸溶劑中的苯氧基樹脂(PKHH,美國英切摩裡斯)、13重量%的DSC放熱峰值溫度為90℃的環氧丙烷系環氧樹脂(EP-4000S,日本艾迪科)、17重量%的DSC放熱峰值溫度為130℃的雙酚A環氧樹脂(JER834,日本三菱化學)、5重量%的DSC放熱峰值溫度為180℃的鄰苯二甲酸酯環氧樹脂(EX721,日本長瀨)、5重量%的陽離子固化催化劑(Si-B2A,日本三信化學)以及20重量%的經過絕緣處理的導電粒子(AUL-704F,平均粒度:4μm,日本積水)。此處,苯氧基樹脂用作充當成形成膜基質的黏合劑系統,環氧樹脂用作固化反應的固化系統,並且導電粒子用作賦予各向異性導電膜導電性的填料。
關於通過添加5重量%陽離子固化催化劑SI-B2A到95重量%第一環氧樹脂或者第二環氧樹脂中所製備的環氧樹脂組成物,使用型號Q20(TA儀器)以10℃/min測量各環氧樹脂的DSC
放熱峰值溫度。
然後將所製備的各向異性導電膜的組成物沉積到白色離型膜上,隨後在乾燥器中在60℃下蒸發溶劑5分鐘,由此製備經乾燥的厚度為16μm的各向異性導電膜。
實例2
以與實例1相同的方式來製備各向異性導電膜,其中改用11重量%的環氧丙烷系環氧樹脂(EP-4000S,日本艾迪科)、14重量%的雙酚A環氧樹脂(JER834,日本三菱化學)以及10重量%的鄰苯二甲酸酯環氧樹脂(EX721,日本長瀨)。
實例3
以與實例1相同的方式來製備各向異性導電膜,其中改用9重量%的環氧丙烷系環氧樹脂(EP-4000S,日本艾迪科)、11重量%的雙酚A環氧樹脂(JER834,日本三菱化學)以及15重量%的鄰苯二甲酸酯環氧樹脂(EX721,日本長瀨)。
比較例1
以與實例1相同的方式來製備各向異性導電膜,其中改用23重量%的環氧丙烷系環氧樹脂(EP-4000S,日本艾迪科)、0重量%的雙酚A環氧樹脂(JER834,日本三菱化學)以及12重量%的鄰苯二甲酸酯環氧樹脂(EX721,日本長瀨)。
比較例2
以與實例1相同的方式來製備各向異性導電膜,其中改用35重量%環氧丙烷系環氧樹脂(EP-4000S,日本艾迪科)並且
未使用雙酚A環氧樹脂(JER834,日本三菱化學)和鄰苯二甲酸酯環氧樹脂(EX721,日本長瀨)。
實驗實例
各向異性導電膜的DSC起始溫度、峰值溫度、熱量變化率以及連接電阻
通過以下方法來測量實例和比較例中製備的各向異性導電膜各自的DSC起始溫度、峰值溫度、熱量變化率以及連接電阻。結果展示在表2和表3中。
(1)DSC起始溫度和峰值溫度
DSC起始溫度定義為在使用差示掃描式熱量計型號Q20(TA儀器)在氮氣氛圍下在0℃至300℃的溫度範圍內以10℃/min的速率測量關於各向異性導電膜的黏著層的熱量時,由於產生熱而使得DSC圖的斜率第一次增加的時間點的溫度。另外,峰值溫度定義為在熱量達到DSC圖中的最高點的時間點的溫度。
(2)在25℃下靜置170小時後的熱量變化率
在取各1mg的初始各向異性導電膜和在25℃下靜置170小時後的各向異性導電膜作為試樣之後,使用型號Q20(TA儀器)在25℃下在-50℃至250℃的溫度區中以10℃/min測量初始膜的初始熱量(H0)和所述膜在25℃下靜置170小時後的熱量(H1)。然後通過計算所述膜靜置170小時後的熱量比初始膜熱量的變化百分比來計算熱量變化率。
(3)在25℃下靜置170小時後的連接電阻
為了測定各向異性導電膜的電特性,將具有1200μm2的凸塊區域和厚度為2000Å的氧化銦錫(ITO)電路的玻璃基板和具有1200μm2的凸塊區域且厚度為1.5mm的IC晶片放在各向異性導電膜的上表面和下表面上,隨後在150℃和70Mpa的條件下壓縮並加熱5秒,由此製備各向異性導電膜的試樣。然後通過4探針方法,使用電阻測試儀型號2000萬用表(吉時利有限公司)通過施加1mA的測試電流來測量試樣的初始連接電阻。另外,在25℃下靜置170小時後,使各向異性導電膜在相同條件下經歷壓縮和加熱,以便製備試樣,然後以相同方式測量試樣的連接電阻。
在表2和表3中,實例1至實例3的各向異性導電膜具有在62℃至90℃範圍內的DSC起始溫度和在85℃至120℃範圍內的峰值溫度,因此允許在低溫下快速固化。實例1至實例3的各向異性導電膜具有35%或者小於35%的熱量變化率,因此展現
良好的儲存穩定性。相比之下,採用按環氧樹脂的總量計為60重量份或者低於60重量份的第二環氧樹脂的比較例1的各向異性導電膜和不採用第二環氧樹脂的比較例2的各向異性導電膜的熱量變化率均為35%或者大於35%,導致儲存穩定性退化。此外,各向異性導電膜在25℃下靜置170小時後的連線性質出現退化,使得難以測量連接電阻。
儘管本發明的一些實施例和特徵已經在上文中描述過,但是應該理解,這些實施例和特徵僅僅為了說明而給出,不應該理解為以任何方式限制本發明。因此,本發明的範圍和精神應該僅僅由所附申請專利範圍和其等效物來限定。
3‧‧‧導電粒子
10‧‧‧黏著層
30‧‧‧半導體裝置
50‧‧‧第一連接部件
60‧‧‧第二連接部件
70‧‧‧第一電極
80‧‧‧第二電極
Claims (14)
- 一種各向異性導電膜,其在25℃下靜置170小時後,通過差示掃描熱量測定法測量並且根據以下方程1計算,熱量變化率為35%或者小於35%,熱量變化率(%)=[(H0-H1)/H0]×100----(1),其中H0為所述各向異性導電膜在25℃下靜置0小時後通過差示掃描熱量測定法測量的熱量;並且H1為所述各向異性導電膜在25℃下靜置170小時後通過差示掃描熱量測定法測量的熱量,其中所述各向異性導電膜具有63℃至87℃的差示掃描熱量測定法起始溫度以及85℃至120℃的峰值溫度,其中所述各向異性導電膜包括放熱峰值溫度為80℃至110℃的第一環氧樹脂以及放熱峰值溫度為120℃至200℃的第二環氧樹脂,所述放熱峰值溫度通過差示掃描熱量測定法測量,其中按所述各向異性導電膜的組成物的固體含量的總重量計,所述第一環氧樹脂以及所述第二環氧樹脂以30重量%至50重量%的總量存在。
- 如申請專利範圍第1項所述的各向異性導電膜,其中所述第一環氧樹脂包括選自由以下組成的群組的至少一種:環氧丙烷系環氧樹脂、氫化雙酚A環氧樹脂、環脂族環氧樹脂以及萘環氧樹脂。
- 如申請專利範圍第1項所述的各向異性導電膜,其中所述第二環氧樹脂包括選自由以下組成的群組的至少一種:雙酚A 環氧樹脂、酚醛清漆環氧樹脂、鄰苯二甲酸酯環氧樹脂以及聯苯環氧樹脂。
- 如申請專利範圍第1至3項中任一項所述的各向異性導電膜,其中按所述第一環氧樹脂以及所述第二環氧樹脂為100重量份計,所述第二環氧樹脂以60重量份至90重量份的量存在。
- 如申請專利範圍第1至3項中任一項所述的各向異性導電膜,包括由式1表示的陽離子固化催化劑,
- 如申請專利範圍第1至3項中任一項所述的各向異性導電膜,其中當放在包含電極的玻璃基板與IC驅動器晶片或者IC晶片之間的所述各向異性導電膜在140℃至160℃下、在60MPa至80MPa負荷下壓縮並加熱3秒至7秒後立即在25℃下測量,所述各向異性導電膜具有3Ω或者小於3Ω的連接電阻,並且當已經在25℃下靜置170小時然後放在所述包括電極的玻璃基板與 所述IC驅動器晶片或者IC晶片之間的所述各向異性導電膜在140℃至160℃以及60MPa至80MPa負荷的條件下壓縮並加熱3秒至7秒後測量,所述各向異性導電膜具有7Ω或者小於7Ω的連接電阻。
- 一種用於各向異性導電膜的組成物,包括:放熱峰值溫度為80℃至110℃的第一環氧樹脂;以及放熱峰值溫度為120℃至200℃的第二環氧樹脂,所述放熱峰值溫度通過差示掃描熱量測定法測量,以及其中按所述組成物的固體含量的總重量計,所述第一環氧樹脂以及所述第二環氧樹脂以30重量%至50重量%的總量存在,並且按所述第一環氧樹脂以及所述第二環氧樹脂為100重量份計,所述第二環氧樹脂以60重量份至90重量份的量存在,其中由用於各向異性導電膜的組成物所製備的所述各向異性導電膜具有63℃至87℃的差示掃描熱量測定法起始溫度以及85℃至120℃的峰值溫度。
- 如申請專利範圍第7項所述的各向異性導電膜的組成物,進一步包括:黏合劑樹脂、陽離子固化催化劑以及導電粒子。
- 如申請專利範圍第7項所述的各向異性導電膜的組成物,包括:按所述組成物的固體含量的總重量計為30重量%至70重量%的黏合劑樹脂、為1重量%至15重量%的陽離子固化催化劑以及為1重量%至25重量%的導電粒子。
- 如申請專利範圍第7至9項中任一項所述的各向異性導 電膜的組成物,進一步包括:穩定劑。
- 如申請專利範圍第10項所述的各向異性導電膜的組成物,其中所述穩定劑包括選自由以下組成的群組的至少一種:鋶、胺、酚、冠酯、膦以及三嗪。
- 一種半導體裝置,包括:包含第一電極的第一連接部件;包含第二電極的第二連接部件;以及如申請專利範圍第1至3項中任一項所述的各向異性導電膜,或者如申請專利範圍第7至9項中任一項所述的各向異性導電膜的組成物形成的各向異性導電膜,其中所述各向異性導電膜被放在所述第一連接部件與所述第二連接部件之間,並且連接所述第一電極與所述第二電極。
- 如申請專利範圍第12項所述的半導體裝置,其中所述第一連接部件為玻璃基板,並且所述第二連接部件為IC驅動器晶片或者IC晶片,並且當放在所述玻璃基板與所述IC驅動器晶片或者IC晶片之間的所述各向異性導電膜在140℃至160℃下、在60MPa至80MPa負荷下壓縮並加熱3秒至7秒後立即在25℃下測量,所述半導體裝置具有3Ω或者小於3Ω的連接電阻。
- 如申請專利範圍第12項所述的半導體裝置,其中所述第一連接部件為玻璃基板,並且所述第二連接部件為IC驅動器晶片或者IC晶片,並且當已經在25℃下靜置170小時然後放在所述玻璃基板與所述IC驅動器晶片或者IC晶片之間的所述各向異性導 電膜在140℃至160℃以及60MPa至80MPa負荷的條件下壓縮並加熱3秒至7秒之後所測量,所述半導體裝置具有7Ω或者小於7Ω的連接電阻。
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