TWI570746B - 包含導電黏著層之各向異性導電膜及半導體裝置 - Google Patents

包含導電黏著層之各向異性導電膜及半導體裝置 Download PDF

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TWI570746B
TWI570746B TW103111767A TW103111767A TWI570746B TW I570746 B TWI570746 B TW I570746B TW 103111767 A TW103111767 A TW 103111767A TW 103111767 A TW103111767 A TW 103111767A TW I570746 B TWI570746 B TW I570746B
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conductive
adhesive layer
particles
insulating
conductive film
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TW103111767A
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TW201445580A (zh
Inventor
朴憬修
權純榮
金智軟
朴永祐
韓在善
黃慈英
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第一毛織股份有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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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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    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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    • H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
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    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
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    • H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • 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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Description

包含導電黏著層之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各向異性導電膜，其包括一種含括導電粒子和絕緣粒子之導電黏著層，以及不含括導電粒子之絕緣黏著層，其中該導電黏著層之導電粒子和絕緣粒子具有每平方毫米(mm2)7.0 x 105/d2至10.0 x 105/d2(粒子)之總粒子密度(該處d為導電粒子以μm計之直徑)，以及製造該各向異性導電膜之方法。
發明背景
一般而言，各向異性導電膜(ACFs)係提及膜狀的黏著劑，其中導電顆粒，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，係分散於樹脂之內，以及其於z軸上展現出導電性質且於x-y平面方向上展現出絕緣性質。
當放置於電路元件之間的各向異性導電膜於預定條件下接受加熱和壓縮時，電路終端係通過導電粒子而彼此電氣地連接，以及用絕緣黏合樹脂填滿的鄰接電路之 間的空間以使導電粒子彼此獨立，藉此提供高的絕緣性能。各向異性導電膜一般係使用於液晶顯示器(LCD)面板和捲帶式載體封裝(TCPs)之間的電氣連接，或是於印刷電路板和TCP等等之間的電氣接連。於電氣連接製程方面，各向異性導電膜係配置於二個電路元件之間並藉由對其施用熱和壓力而壓縮。於此時，導電粒子會於二個電路元件之間移動，藉此造成對應終端間留住的導電粒子較少，以及鄰接的終端間的導電粒子數目增加。結果，各向異性導電膜於鄰接的終端之間遭受電氣連接和絕緣性質劣化的困擾。
根據顯示器領域近來大尺寸及薄的厚度之趨勢，介於電極及電路之間的間距已經逐漸變得小型化。特別地，為了滿足行動載具之高解析度，本技藝中待連接的終端面積及終端之間的距離係逐漸減小。於此等情況下，各向異性導電膜與相關技藝相比時，在連接和絕緣方面亦必須有最佳的性能。然而，一種典型的單層或多層各向異性導電膜於精細的電路終端方面有限制(舉例而言，韓國專利申請案案號2010-0140773及案號2010-0138216)。
可能會提議藉由減小導電粒子的大小同時增加導電粒子的密度，來製備一種各向異性導電膜，作為確保各向異性導電膜關於精細的電路終端之連接和絕緣性能的方法。然而，在此情況下，因為電路終端之間的間隙很窄，是以不容易減少短路發生，以及導電粒子的大小減小會提供小的連接點及對高度有偏差的元件會提供低的遮蓋能力，因此提供了劣化的連接性能。
發明概要
本發明已經構想出解決此等先前技藝的問題，以及提供一種各向異性導電膜，其能在連接有很小的終端面積及很小的終端之間的距離之精細電路，像是高解析度行動載具及類似物時，確保連接和絕緣的可靠度，以及一種由該各向異性導電膜連接的半導體裝置。
本發明的一個態樣係有關於一種各向異性導電膜，其包括一種含括導電粒子和絕緣粒子之導電黏著層，以及不含括導電粒子之絕緣黏著層，其中該導電黏著層之導電粒子和絕緣粒子具有每平方毫米(mm2)7.0 x 105/d2至10.0 x 105/d2(粒子)之總粒子密度(該處d為導電粒子以μm計之直徑)。
本發明的另一個態樣係有關於一種各向異性導電膜，其包括一含括導電粒子和絕緣粒子之導電黏著層，以及不含括導電粒子之絕緣黏著層，其中該導電黏著層之導電粒子和絕緣粒子係以該各向異性導電膜的總面積之80%或更大的總粒子面積比存在。
於一些具體例中，就固體含量而言，以該導電黏著層的總重量為基準，該導電粒子和該絕緣粒子可以以25wt%至60wt%的量存在。
於一些具體例中，該導電粒子對該絕緣粒子之體積比範圍可以從1.5：1至1：3.5。
於一些具體例中，該導電粒子可以具有從1μm 至10μm，較佳為從1μm至5μm之粒徑(d)。
於一些具體例中，該導電黏著層可以具有該導電粒子直徑之50%至150%的厚度。
於一些具體例中，該導電粒子對該絕緣粒子之直徑比範圍可以從1.2：1至1：1.2。
於一些具體例中，該絕緣黏著層可以形成於該導電黏著層的一個表面或二個表面之上。
於一些具體例中，導電粒子可以包括選自於以下的至少一類型粒子：金屬顆粒，包括Au、Ag、Ni、Cu、Pd、Al、Cr、Sn、Ti，及Pb之至少一者；碳顆粒；以及樹脂顆粒或是被塗覆金屬顆粒之其經修飾的樹脂顆粒。於此，樹脂顆粒包括苯胍(benzoguanamine)、聚乙烯、聚酯、聚苯乙烯和聚乙烯醇之至少一者。
於一些具體例中，該導電粒子或該絕緣粒子可以有突出件(protrusions)形成於其表面上。
於一些具體例中，絕緣粒子可以為無機粒子、有機粒子，或是有機與無機粒子之混合物，其中無機粒子可以包括選自於以下的至少一者：矽石(SiO2)、Al2O3、TiO2、ZnO、MgO、ZrO2、PbO、Bi2O3、MoO3、V2O5、Nb2O5、Ta2O5、WO3或In2O3；以及有機粒子可以包括選自於以下的至少一樹脂：丙烯酸共聚物、苯并鳥糞嘌呤(benzoguanine)、聚乙烯、聚酯、聚苯乙烯、聚乙烯醇、聚胺甲酸酯，和其之經修飾的樹脂。
於一些具體例中，該導電黏著層和該絕緣黏著層 之各者可以包括一種黏結劑樹脂及一種固化劑。於導電黏著層中，就固體含量而言，以該導電黏著層的總重量為基準，該黏結劑樹脂可以以10wt%至60wt%的量存在，及該固化劑可以以10至40wt%的量存在。於絕緣黏著層中，就固體含量而言，以該絕緣黏著層的總重量為基準，該黏結劑樹脂可以以30wt%至80wt%的量存在，及該固化劑可以以20至70wt%的量存在。
於一些具體例中，該絕緣黏著層對該導電黏著層之厚度比可以為大於1/5且小於10。
於一些具體例中，該導電黏著層之導電粒子和絕緣粒子可以以每平方毫米(mm2)7.0 x 105/d2至10.0 x 105/d2(粒子)之總粒子密度存在，該導電黏著層可以具有該導電粒子直徑之50%至150%的厚度，以及該導電粒子和該絕緣粒子的中心可以放置於實質相同的平面上。
本發明另外的態樣係有關於一種半導體裝置，其包括：a)一種配線基板；b)附接至該配線基板之如本發明具體例的各向異性導電膜之導電黏著層及絕緣黏著層；以及c)一種安裝於該導電黏著層或該絕緣黏著層之上的半導體晶片。
於一些具體例中，該導電黏著層內的該導電粒子對該絕緣粒子之體積比範圍可以從1.5：1至1：3.5。
於一些具體例中，該導電黏著層可以具有該導電粒子直徑之50%至150%的厚度。
於一些具體例中，該導電粒子對該絕緣粒子之直 徑比範圍可以從1.5：1至1：1.5。
依據本發明之各向異性導電膜能確保有關精細電路之鄰接的終端之間，傑出的電氣連接和穩定的絕緣性。
於依據本發明之各向異性導電膜中，均勻地混合該導電粒子和該絕緣粒子使粒子存在於彼此相鄰的單獨一層內，以便使粒子在熱壓中的移動減到最小，藉此增加幫助終端間連接的有效粒子數目，同時預防相鄰的終端間之短路。
1‧‧‧基膜
2‧‧‧導電黏著層
3‧‧‧絕緣黏著層
3'‧‧‧第一絕緣黏著層
3"‧‧‧第二絕緣黏著層
4‧‧‧導電粒子
5‧‧‧絕緣粒子
6‧‧‧各向異性導電膜
圖1為依據本發明的具體例之一種各向異性導電膜的截面圖。
圖2為一種含有導電黏著層之典型的各向異性導電膜的截面圖。
圖3為依據本發明的另一個具體例之一種各向異性導電膜的截面圖。
發明之詳細說明
本發明之具體例現在將予以詳細地描述。對熟悉此藝者而言為顯而易見的細節，為了清楚的目的將會省略。
本發明之一個具體例係有關於一種各向異性導電膜，其包括一種含括導電粒子和絕緣粒子之導電黏著層，以及不含括導電粒子之絕緣黏著層，其中該導電黏著層之 導電粒子和絕緣粒子具有每平方毫米(mm2)7.0 x 105/d2至10.0 x 105/d2(粒子)之總粒子密度(該處d為導電粒子以μm計之直徑)，該各向異性導電膜可以藉以使粒子在熱壓中的移動減到最小，藉此增加幫助終端間連接的有效粒子數目，同時預防相鄰的終端間之短路。
當使用於本文，該導電黏著層之導電粒子和絕緣粒子之「總粒子密度」一詞意指，包括導電粒子和絕緣粒子之所有粒子的密度。總粒子密度範圍可以從每平方毫米(mm2)7.0 x 105/d2至10.0 x 105/d2(粒子)，特別為每平方毫米(mm2)8.0 x 105/d2至10.0 x 105/d2(粒子)，更特別為每平方毫米(mm2)9.0 x 105/d2至10.0 x 105/d2(粒子)之總粒子密度(該處d為導電粒子以μm計之直徑)。
當該導電粒子和絕緣粒子之總粒子密度範圍從每平方毫米(mm2)7.0 x 105/d2至10.0 x 105/d2(粒子)時，有可能可預防連接性能及絕緣性能之劣化，在黏著層內之黏結劑樹脂等等於該導電黏著層內形成空間，而使導電粒子能於該空間內移動時會發生劣化，或者當導電粒子沒有配置在該導電黏著層的單一層內，而可於該黏著層內移動時會發生劣化。
該導電粒子可以具有從1μm至10μm，特別為從1μm至5μm之直徑(d)。
本發明的另一個具體例係有關於一種各向異性導電膜，其包括一種含括導電粒子和絕緣粒子之導電黏著層，以及不含括導電粒子之絕緣黏著層，其中該導電黏著 層之導電粒子和絕緣粒子係以該各向異性導電膜的總面積之80%或更大的總粒子面積比存在，藉以使導電粒子在熱壓中的移動減到最小，藉此增加終端間安置的有效導電粒子數目，同時預防相鄰的終端間之短路。
當使用於本文，該導電黏著層之導電粒子和絕緣粒子之「總粒子面積比」一詞意指，該導電粒子和絕緣粒子之總粒子面積對該各向異性導電膜於x-y平面方向上的總面積之比率。特別地，總粒子面積比可以為85%或更大，更特別為90%或更大，舉例而言95%或更大。該各向異性導電膜之z軸對應於半導體晶片和配線基板之間的導電粒子或絕緣粒子壓縮的方向，以及因而x-y平面方向的面積為垂直於壓縮方向的平面之面積。
該導電粒子和絕緣粒子之總粒子面積比於此範圍之內，有可能可預防連接性能及絕緣性能之劣化，劣化會發生在黏著層內之黏結劑樹脂等等於該導電黏著層內形成空間，而使導電粒子能於該空間內移動時，或者劣化會發生在當導電粒子沒有配置在該導電黏著層的單一層內，而可於該黏著層內移動時。
就固體含量而言，以該導電黏著層的總重量為基準，該導電粒子和該絕緣粒子可以以25wt%至60wt%的量存在。
在下文中，將參照附圖詳細說明本發明之例示性具體例。應該了解到下列具體例僅僅為了闡釋目的而提供以及本發明不限制於該等。
圖1為依據本發明的具體例之各向異性導電膜的截面圖。如圖1中所示，依據本發明的具體例之各向異性導電膜6包括絕緣黏著層3及導電黏著層2。依據此具體例，該各向異性導電膜6可以進一步包括一種基膜1。於此具體例中，導電粒子4和絕緣粒子5沒有餘隙(clearance)地配置在該導電黏著層2的單一層內，以及因而於連接時保持為實質固定的。此外，因為該導電粒子4和絕緣粒子5非常均勻地混合以形成該導電黏著層2，所以該導電粒子4和絕緣粒子5提供良好的分布剖面。以此種方式，因為該導電粒子4和絕緣粒子5沒有餘隙地配置在該導電黏著層2的單一層之內，所以有可能可以減少由於導電粒子4於該導電黏著層2內移動所造成之連接性能及或絕緣性能的劣化。圖3為依據本發明的另一個具體例之各向異性導電膜的截面圖，其中絕緣黏著層係形成於該導電黏著層的二個表面之上。參見圖3，依據此具體例的各向異性導電膜可以包括各別形成於導電黏著層2的二個表面之上的第一絕緣黏著層3'和第二絕緣黏著層3"。
另一方面，圖2為一種含有導電黏著層之典型的各向異性導電膜的截面圖。於此各向異性導電膜中，導電黏著層2提供很大的餘隙能讓該導電粒子4移動，藉以終端上有效導電粒子數目一旦壓縮便減少，從而造成連接性能及絕緣性能之劣化。
該導電粒子和絕緣粒子之總粒子密度可以，舉例而言藉由下列方法來計算。
首先，經由一種光學顯微鏡來觀察該各向異性導電膜。於此，觀察大約180μm×130μm(23,400μm2)的面積同時調整顯微鏡之放大倍數。計算此面積內導電粒子和絕緣粒子之總數以及除以測量的面積來計算每μm2之粒子密度。最後，從結果獲得每平方毫米(mm2)之總粒子密度(粒子)。
該導電粒子和絕緣粒子之總粒子面積比可以，舉例而言藉由下列方法來測量。
首先，經由一種光學顯微鏡來觀察該各向異性導電膜。於此，觀察大約180μm×130μm(23,400μm2)的面積同時調整顯微鏡之放大倍數。接而，使用一種影像分析程式(Image Analyzer，IMT i-Solution，產品名稱：i-Solution)來計算導電粒子和絕緣粒子相對於總面積所佔據之面積，以獲得導電粒子和絕緣粒子對總面積之粒子面積比百分比(%)。
該導電粒子對該絕緣粒子之體積比範圍可以從1.5：1至1：3.5，較佳為從1.2：1至1：3.2，更佳為從1：1至1：3。當體積比落在此1.5：1至1：3.5範圍內時，有可能可達到絕緣性能及連接性能二者之改良。
該導電黏著層可以具有該導電粒子直徑之50%至150%的厚度。依據本發明，該導電粒子或該絕緣粒子具有範圍從1μm至10μm之直徑，較佳為從1μm至5μm之直徑。因而，該導電黏著層可以具有0.5μm至15μm的厚度，較佳為0.5μm to 7.5μm的厚度。於此範圍之內，可以抑制導電 粒子在熱壓中的移動，藉此改良絕緣性能及連接性能。
該導電粒子對該絕緣粒子之直徑比範圍可以從1.5：1至1：1.5。較佳地，該導電粒子和絕緣粒子具有實質相同的直徑。
本發明另外的具體例係有關於一種各向異性導電膜，其包括一種含括導電粒子和絕緣粒子之導電黏著層，以及不含括導電粒子之絕緣黏著層，其中該導電黏著層之導電粒子和絕緣粒子具有每平方毫米(mm2)7.0 x 105/d2至10.0 x 105/d2(粒子)之總粒子密度(該處d為導電粒子以μm計之直徑)，或者其中該導電黏著層之導電粒子和絕緣粒子係以該各向異性導電膜的總面積之80%或更大的總粒子面積比存在，該導電黏著層具有該導電粒子直徑之50%至150%的厚度，以及該導電粒子和該絕緣粒子的中心係放置於實質相同的平面上。措辭“該導電粒子和該絕緣粒子的中心係放置於實質相同的平面上”，意指當導電粒子的重心連接至該絕緣粒子的重心時，會形成實質二維的平面。
於另一個具體例中，該導電黏著層之導電粒子和絕緣粒子可以具有每平方毫米(mm2)10.0 x 105/d2(粒子)之總粒子密度，以及該導電粒子和該絕緣粒子的中心可以放置於實質相同的平面上。
該絕緣黏著層可以形成於該導電黏著層的一個表面或二個表面之上。較佳地，該各向異性導電膜包括形成於該導電黏著層的二個表面之上之該絕緣黏著層。
導電粒子可以包括選自於以下的至少一類型粒 子：金屬顆粒，包括Au、Ag、Ni、Cu、Pd、Al、Cr、Sn、Ti，及Pb之至少一者；碳顆粒；以及樹脂顆粒或是被塗覆金屬顆粒之其經修飾的樹脂顆粒，不限於該等。於此，樹脂顆粒包括苯胍(benzoguanamine)、聚乙烯、聚酯、聚苯乙烯和聚乙烯醇之至少一者。
該導電粒子或該絕緣粒子可以有突出件形成於其表面上。
絕緣粒子可以為無機粒子、有機粒子，或是有機與無機粒子之混合物，其中無機粒子可以包括選自於以下的至少一者：矽石(SiO2)、Al2O3、TiO2、ZnO、MgO、ZrO2、PbO、Bi2O3、MoO3、V2O5、Nb2O5、Ta2O5、WO3或In2O3；以及有機粒子可以包括選自於以下的至少一樹脂：丙烯酸共聚物、苯并鳥糞嘌呤(benzoguanine)、聚乙烯、聚酯、聚苯乙烯、聚乙烯醇、聚胺甲酸酯，和其之經修飾的樹脂。有機與無機粒子之混合物的實例可以包括矽倍半氧烷(silsesquioxane)粒子。
該絕緣黏著層對該導電黏著層之厚度比可以為大於1/5且小於10。
較佳地，該絕緣黏著層對該導電黏著層之厚度比為大於2且小於8。於此種範圍之內，相鄰的電路之間的空間充分地填滿絕緣黏著層，藉此提供良好的絕緣性及黏著性。
於依據本發明之各向異性導電膜內，該導電黏著層及該絕緣黏著層各者可以進一步包括一種黏結劑樹脂及 一種固化劑。
該黏結劑樹脂可以為選自於以下所構成的群組：丙烯酸、環氧、胺甲酸酯丙烯酸酯、苯氧、丙烯腈、苯乙烯-丙烯腈、丁二烯、聚醯胺、烯烴、胺甲酸酯，以及矽氧樹脂。較佳地，該黏結劑樹脂係選自於以下所構成的群組：丙烯酸樹脂、環氧樹脂以及胺甲酸酯丙烯酸酯樹脂。
丙烯酸樹脂可以為經由選自於以下所構成的群組之(甲基)丙烯酸酯單體之共聚合作用而製備的共聚物：1,6-己二醇單(甲基)丙烯酸酯、2-羥乙基(甲基)丙烯酸酯、2-羥丙基(甲基)丙烯酸酯、2-羥丁基(甲基)丙烯酸酯、2-羥基-3-苯氧基丙基(甲基)丙烯酸酯(2-hydroxy-3-penyloxypropyl(meth)acrylate)、1,4-丁二醇(甲基)丙烯酸酯、2-羥基烷基(甲基)丙烯醯磷酸酯、4-羥基環己基(甲基)丙烯酸酯、新戊二醇單(甲基)丙烯酸酯、三羥甲基乙烷二(甲基)丙烯酸酯、三羥甲基丙烷二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、季戊四醇六(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、2-(2-乙氧基乙氧基)乙基(甲基)丙烯酸酯、硬脂醯(甲基)丙烯酸酯、月桂基(甲基)丙烯酸酯、2-苯氧乙基(甲基)丙烯酸酯、異基(甲基)丙烯酸酯、十三基(甲基)丙烯酸酯、乙氧化壬基酚(甲基)丙烯酸酯、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、t-乙二醇二(甲基)丙烯酸酯(t-ethylene glycol di(meth)acrylate)、聚乙二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、三丙二醇 二(甲基)丙烯酸酯、乙氧化雙酚-A二(甲基)丙烯酸酯、環己烷二甲醇二(甲基)丙烯酸酯、苯氧基-t-二醇(甲基)丙烯酸酯、2-甲基丙烯醯氧乙基磷酸酯、二(羥甲)三環癸烷二(甲基)丙烯酸酯、三羥甲基丙烷苯甲酸酯丙烯酸酯，以及茀(甲基)丙烯酸酯，不限於該等。
環氧樹脂可以包括一種共聚物，其具有選自於以下所構成的群組之至少一個結合結構：雙酚型、酚醛型、環氧丙基型以及脂環基團，不限於該等。舉例而言，環氧樹脂可以包括雙酚A或雙酚F或是經修飾的環氧樹脂、苯酚酚醛環氧樹脂、甲酚酚醛環氧樹脂、具有二環戊二烯主鏈之環氧樹脂、二體酸修飾的環氧樹脂、具有丙二醇主鏈之環氧樹脂，或是胺甲酸酯修飾的環氧樹脂，以及類似物。
胺甲酸酯丙烯酸酯樹脂可以包括由二異氰酸酯、多元醇、二醇，或丙烯酸酯單體來製備之樹脂。二異氰酸酯可以包括選自於以下所構成的群組之至少一者：四亞甲基-1,4-二異氰酸酯、六亞甲基-1,6-二異氰酸酯、伸環己基-1,4-二異氰酸酯、亞甲基雙(4-環己基異氰酸酯)、異佛酮二異氰酸酯(isophorone diisocyanate)，以及4-4-亞甲基雙(環己基二異氰酸酯)。多元醇之實例可以包括聚酯多元醇、聚醚多元醇，及聚碳酸酯多元醇，不限於該等。多元醇可以經由二甲酸化合物和二醇化合物的縮合作用來獲得。於此，二甲酸化合物之實例可以包括琥珀酸、戊二酸、異酞酸、己二酸、辛二酸、壬二酸、癸二酸、十二烷二甲酸、六氫酞酸、異酞酸、對酞酸、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、四氫酞酸，和類似物。二醇化合物之實例可以包括乙二醇、丙二醇、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、新戊二醇、二乙二醇、二丙二醇、三乙二醇、四乙二醇、二丁二醇、2-甲基-1,3-戊二醇、2,2,4-三甲基-1,3-戊二醇、1,4-環己烷二甲醇，以及類似物。二醇化合物之實例可以包括1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、新戊二醇、二乙二醇、二丙二醇、三乙二醇、四乙二醇、二丁二醇、2-甲基-1,3-戊二醇、2,2,4-三甲基-1,3-戊二醇、1,4-環己烷二甲醇，以及類似物。丙烯酸酯可以為經基丙烯酸酯或是胺基丙烯酸酯。
該黏結劑樹脂可以以10wt%至60wt%的量，較佳為15至40wt%的量存在於該導電黏著層內。該黏結劑樹脂可以以30wt%至80wt%的量，較佳為40至70wt%的量存在於該絕緣黏著層內。於此等黏結劑樹脂含量範圍之內，黏著組成物可以形成為一膜。該黏結劑樹脂可以具有30,000g/mol至1,000,000g/mol，較佳為50,000g/mol至850,000g/mol的重量平均分子量。
在固化劑方面，可以不受限地使用本技藝已知的任何固化劑。固化劑之實例可包括咪唑、苯甲醯基、酸酐、胺、醯肼、陽離子固化劑、潛性固化劑，以及其等之組合，不限於該等。
固化劑可以以10wt%至40wt%的量，較佳為15至30wt%的量存在於該導電黏著層內。此外，固化劑可以 以20wt%至70wt%的量，較佳為35至50wt%的量存在於該絕緣黏著層內。於此範圍之內，固化劑讓黏著組成物在預定的溫度範圍內加熱時可以與黏結劑樹脂一起固化，以便黏著組成物展現出黏合強度及具有穩固的結構，藉此改善可靠度。
本發明另外的具體例係有關於一種半導體裝置，其包括：a)一種配線基板；b)附接至該配線基板之如本發明具體例的各向異性導電膜之導電黏著層及絕緣黏著層；以及c)一種安裝於該導電黏著層或該絕緣黏著層之上的半導體晶片。
於該導電黏著層內，該導電粒子對該絕緣粒子之體積比範圍可以從1.5：1至1：3.5。
該導電黏著層可以具有該導電粒子直徑之50%至150%的厚度。
該導電粒子對該絕緣粒子之直徑比範圍可以從1.5：1至1：1.5。
本發明再另外的具體例係有關於一種製造一種各向異性導電膜之方法，該各向異性導電膜包括一種含括導電粒子和絕緣粒子之導電黏著層，以及不含括導電粒子之絕緣黏著層。該方法包括：i)形成該含括導電粒子和絕緣粒子之導電黏著層，其中該導電黏著層之導電粒子和絕緣粒子具有每平方毫米(mm2)7.0 x 105/d2至10.0 x 105/d2(粒子)之總粒子密度(該處d為導電粒子以μm計之直徑)，或者該導電黏著層之導電粒子和絕 緣粒子係以該各向異性導電膜的總面積之80%或更大的總粒子面積比存在；以及ii)形成該不含括導電粒子之絕緣黏著層於該導電黏著層之上，或者形成單獨的絕緣黏著層，接著組合該導電黏著層與該單獨的絕緣黏著層以形成該包括該導電黏著層及該絕緣黏著層之各向異性導電膜。
依據本發明之方法可以進一步包括於操作i)中均勻地混合該導電粒子和該絕緣粒子。
依據本發明之方法可以進一步包括於操作i)中確定該導電粒子和絕緣粒子之總粒子密度。此外，依據本發明之方法可以進一步包括於操作i)中確定該導電粒子和絕緣粒子之總粒子面積比。粒子密度之確定可以藉由經由一種光學顯微鏡來觀察該各向異性導電膜，同時調整光學顯微鏡之放大倍數。於此，觀察大約180μm×130μm(23,400μm2)的面積。計算此面積內導電粒子和絕緣粒子之總數以及除以測量的面積來計算每μm2之粒子密度。最後，從結果獲得每平方毫米(mm2)之總粒子密度(粒子)。該導電粒子和絕緣粒子之總粒子面積比之測量可以藉由經由一種光學顯微鏡來觀察該各向異性導電膜，同時調整光學顯微鏡之放大倍數。於此，觀察大約180μm×130μm(23,400μm2)的面積。接而，使用一種影像分析程式(Image Analyzer，IMT i-Solution，產品名稱：i-Solution)來計算導電粒子和絕緣粒子相對於總面積所佔據之面積，以獲得導電粒子和絕緣粒子對總面積之粒子面積比百分比(%)。
於操作i)之該導電黏著膜內，該導電粒子對該絕緣粒子之體積比範圍可以從1.5：1至1：3.5，較佳為從1.2：1至1：3.2，更佳為從1：1至1：3。當體積比落在此1.5：1至1：3.5範圍內時，有可能可達到絕緣性能及連接性能二者之改良。
該導電黏著層可以具有該導電粒子直徑之50%至150%的厚度。於此範圍之內，可以抑制導電粒子在熱壓中的移動，藉此改良絕緣性能及連接性能。
該導電粒子對該絕緣粒子之直徑比範圍可以從1.5：1至1：1.5。較佳地，該導電粒子和該絕緣粒子具有實質相同的直徑。
依據本發明之方法可以進一步包括，於操作ii)之後，形成第二絕緣黏著層於該導電黏著層之另一個表面上。
各向異性導電膜之導電黏著層及絕緣黏著層各者可以進一步包括選自於以下所構成的群組之至少一添加劑：溶劑、聚合化抑制劑、抗氧化劑、熱安定劑，以及固化加速劑。添加劑可以以1wt%至5wt%的量存在於各黏著層內。
關於溶劑，可以使用任何溶劑，例如甲苯或甲基乙基酮。聚合化抑制劑可以為選自於以下所構成的群組至少一者：羥醌、羥醌單甲醚、對苯醌、啡噻，以及其等之混合物，不限於該等。抗氧化劑可以用來防止該組成物因為熱而氧化，或是提供熱穩定性，以及可以選自於支鏈酚或羥基桂皮酸酯材料，不限於該等。固化加速劑可以包 括選自於以下的至少一者：固態咪唑固化加速劑，以及固態和液態胺固化加速劑，不限於該等。
形成依據本發明之各向異性導電膜不需要特定的裝置或者設備。舉例而言，該各向異性導電膜可以藉由以下方式來獲得：攪拌並混合該導電粒子和該絕緣粒子於溶劑之內來製備均勻的分散液，以及接而添加一種黏結劑樹脂及一種固化劑至該混合物，或是藉由以不會造成該導電粒子或該絕緣粒子粉碎的速率來攪拌該導電粒子、該絕緣粒子、該黏結劑樹脂和該固化劑歷時某時間期間，塗敷0.5μm至15μm的厚度之該混合物至一種脫模膜之上，接著乾燥該混合物歷時足夠的時間以使該溶劑揮發。
任擇地，一種絕緣黏著膜可以藉由以下方式來獲得：攪拌該黏結劑樹脂、該固化劑和溶劑歷時預定的時間期間，塗敷0.5μm至80μm的厚度之該混合物至一種脫模膜之上，接著乾燥該混合物歷時足夠的時間以使該溶劑揮發。接而，組合該導電黏著膜與該絕緣黏著膜以形成具有雙層或更多層結構之各向異性導電膜。
接著，本發明將參照一些實施例予以更詳盡地解釋。應該了解到此等實施例僅僅為了闡釋目的而提供以及無論如何不解釋為限制本發明。
本文中將省略對熟悉此藝者而言為顯而易見的細節。
實施例 1.實施例1至6之各向異性導電黏著劑之製備 實施例1
製備一種絕緣黏著層係使用就固體含量而言，35wt%的苯氧樹脂(Kukdo Chemical Co.,Ltd.)、20wt%的環氧樹脂EP-630(JER Co.,Ltd.)，及45wt%的潛性固化劑HP3941HP(Asahi Kasei,K.K.)，以及製備一種導電黏著層係使用就固體含量而言，20wt%的苯氧樹脂、4wt%的環氧樹脂EP-630、23wt%的潛性固化劑HP3841HP、具有3μm粒徑之38wt%的鍍鎳導電粒子，及由丙烯酸共聚物樹脂所形成且具有3μm粒徑之15wt%的絕緣粒子。於此，製備各組成物係經由溶解及分散該等組分於一種溶劑之內，以及將組成物塗覆至一種PET脫模膜之上，接著蒸發溶劑，藉此製備12μm厚的絕緣黏著層或1.5μm厚的導電黏著層。然後，組合該絕緣黏著層和該導電黏著層以形成實施例1之各向異性導電膜。
實施例2
實施例2的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，除了導電黏著層的厚度為4.5μm之外。
實施例3
實施例3的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，除了製備導電黏著層係使用就固體含量而言，26wt%的苯氧樹脂、4wt%的環氧樹脂EP-630、29wt%的潛性固化劑HP3841HP、具有3μm粒徑之19wt%的鍍鎳導電粒子，及由丙烯酸共聚物樹脂所形成且具有3 μm粒徑之22wt%的絕緣粒子之外。於此，製備組成物係經由溶解及分散該等組分於一種溶劑之內，以及將組成物塗覆至一種PET脫模膜之上，接著蒸發溶劑，藉此製備3μm的導電黏著層，組合該導電黏著層和該絕緣黏著層以形成各向異性導電膜。
實施例4
實施例4的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，除了製備導電黏著層係使用就固體含量而言，32wt%的苯氧樹脂、4wt%的環氧樹脂EP-630、36wt%的潛性固化劑HP3841HP、具有3μm粒徑之13wt%的鍍鎳導電粒子，及由丙烯酸共聚物樹脂所形成且具有3μm粒徑之15wt%的絕緣粒子之外。於此，製備組成物係經由溶解及分散該等組分於一種溶劑之內，以及將組成物塗覆至一種PET脫模膜之上，接著蒸發溶劑，藉此製備3μm的導電黏著層，組合該導電黏著層和該絕緣黏著層以形成各向異性導電膜。
實施例5
實施例5的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，除了製備導電黏著層係使用就固體含量而言，23wt%的苯氧樹脂、3wt%的環氧樹脂EP-630、25wt%的潛性固化劑HP3841HP、具有4μm粒徑之34wt%的鍍鎳導電粒子，及由丙烯酸共聚物樹脂所形成且具有4μm粒徑之15wt%的絕緣粒子之外。於此，製備組成物係經由溶解及分散該等組分於一種溶劑之內，以及將組成物塗 覆至一種PET脫模膜之上，接著蒸發溶劑，藉此製備4μm的導電黏著層，組合該導電黏著層和該絕緣黏著層以形成各向異性導電膜。
實施例6
實施例6的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，除了製備導電黏著層係使用就固體含量而言，21wt%的苯氧樹脂、2wt%的環氧樹脂EP-630、23wt%的潛性固化劑HP3841HP、具有3μm粒徑之39wt%的鍍鎳導電粒子，及由丙烯酸共聚物樹脂所形成且具有2.5μm粒徑之15wt%的絕緣粒子之外。於此，製備組成物係經由溶解及分散該等組分於一種溶劑之內，以及將組成物塗覆至一種PET脫模膜之上，接著蒸發溶劑，藉此製備3μm的導電黏著層，組合該導電黏著層和該絕緣黏著層以形成各向異性導電膜。
2.比較實施例1及2之各向異性導電黏著劑之製備 比較實施例1
比較實施例1的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，除了製備導電黏著層係使用就固體含量而言，17wt%的苯氧樹脂、3wt%的環氧樹脂EP-630、14wt%的潛性固化劑HP3841HP、具有3μm粒徑之51wt%的鍍鎳導電粒子，及由丙烯酸共聚物樹脂所形成且具有3μm粒徑之15wt%的絕緣粒子之外。於此，製備組成物係經由溶解及分散該等組分於一種溶劑之內，以及將組成物塗覆至一種PET脫模膜之上，接著蒸發溶劑，藉此製備3μm 的導電黏著層，組合該導電黏著層和該絕緣黏著層以形成各向異性導電膜。
比較實施例2
比較實施例2的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，除了製備導電黏著層係使用就固體含量而言，35wt%的苯氧樹脂、5wt%的環氧樹脂EP-630、39wt%的潛性固化劑HP3841HP、具有3μm粒徑之10wt%的鍍鎳導電粒子，及由丙烯酸共聚物樹脂所形成且具有3μm粒徑之11wt%的絕緣粒子之外。於此，製備組成物係經由溶解及分散該等組分於一種溶劑之內，以及將組成物塗覆至一種PET脫模膜之上，接著蒸發溶劑，藉此製備3μm的導電黏著層，組合該導電黏著層和該絕緣黏著層以形成各向異性導電膜。
3.各向異性導電黏著劑之性質評估
藉由下列方法來評估實施例1至6和比較實施例1及2內所製備的各向異性導電膜關於導電粒子對絕緣粒子之體積比、導電粒子和絕緣粒子之總粒子密度、連接電阻，以及絕緣電阻。結果係顯示於表1和表2內。
1)導電粒子對絕緣粒子之體積比
實施例1至6和比較實施例1及2內所製備的各個各向異性導電膜係經由一種光學顯微鏡BX51(OLYMPUS)來觀察。觀察大約180μm×130μm(23,400μm2)面積的導電膜同時調整顯微鏡之放大倍數。計算導電粒子和絕緣粒子之總數以計算體積比。
2)導電粒子和絕緣粒子之總粒子密度
實施例1至6和比較實施例1及2內所製備的各個各向異性導電膜係經由一種光學顯微鏡BX51(OLYMPUS)來觀察。觀察大約180μm×130μm(23,400μm2)面積的導電膜同時調整顯微鏡之放大倍數。計算此面積內導電粒子和絕緣粒子之總數以及除以測量的面積來計算每μm2之粒子密度。最後，從結果獲得每平方毫米(mm2)之總粒子密度(粒子)。
3)導電粒子和絕緣粒子之總粒子面積比
實施例1至6和比較實施例1及2內所製備的各個各向異性導電膜係經由一種光學顯微鏡BX51(OLYMPUS)來觀察。觀察大約180μm×130μm(23,400μm2)面積的導電膜同時調整顯微鏡之放大倍數。接而，使用一種影像分析程式(Image Analyzer，IMT i-Solution，產品名稱：i-Solution)來計算導電粒子和絕緣粒子相對於總面積所佔據之面積，以獲得導電粒子和絕緣粒子對總面積之粒子面積比百分比(%)。
4)連接電阻
將各個各向異性導電膜切成2mm x 25mm的大小且結合至一基板用於評估連接電阻。於此，透過於60℃及1MPa歷時1秒的條件下之預壓縮，將各向異性導電膜放在0.5mm厚的玻璃基板上，接著從各向異性導電膜移除一PET薄膜。隨後，將一晶片(晶片長度：19.5mm，晶片寬度：1.5mm，凸塊長度：100μm，凸塊寬度：12μm)對齊該薄膜，接著於200℃及90MPa歷時1秒的條件下進行主要壓縮。各向異 性導電膜的連接電阻係使用一種電阻試驗機、藉由4點探針方法來測量，其中使用連接至電阻試驗機的4個探針來測量4點之間的電阻。根據施加1mA至電阻試驗機時測量之電壓來計算連接電阻。
5)絕緣電阻
將各個各向異性導電膜切成2mm x 25mm的大小且結合至一基板用於評估絕緣電阻。於此，透過於60℃及1MPa歷時1秒的條件下之預壓縮，將各向異性導電膜放在0.5mm厚的玻璃基板上，接著從各向異性導電膜移除一PET薄膜。隨後，將一晶片(晶片長度：19.5mm，晶片寬度：1.5mm，凸塊間距：8μm)對齊該薄膜，接著於200℃及90MPa歷時1秒的條件下進行主要壓縮。藉由一種2點探針方法，透過施加50V之電壓至該處來檢查總計38個位置短路的發生情形。
如同表1和表2內顯示的，當該導電黏著層內導電粒子和絕緣粒子之總粒子密度在每平方毫米(mm2)7.0 x 105/d2至10.0 x 105/d2(粒子)之範圍時，該各向異性導電膜在連接電阻和絕緣電阻二者都有良好的性質。另一方面，於總粒子密度超過每平方毫10.0 x 105/d2(粒子)的比較實施例1之各向異性導電膜方面，導電粒子沒有配置在單一層內而讓粒子會移動，造成連接電阻增加，以及於總粒子密度小於每平方毫7.0 x 105/d2(粒子)的比較實施例2方面，各向異性導電膜有很大的移動空間，造成連接性能之增加。
此外，於實施例1至6中導電黏著層的導電粒子對 絕緣粒子之體積比在1：1至1：3之範圍時，該各向異性導電膜在連接電阻和絕緣電阻二者都有良好的性質，以及於體積比為2：1之比較實施例1方面，由於導電粒子過量所致之絕緣不充分會發生短路。
縱然已經揭示一些具體例，熟悉此藝者會明白該等具體例僅僅提供當作例示，以及可以做出各種各樣的修飾、改變、變更，和均等的具體例而不會背離本發明的精神和範疇。本發明的範疇應僅由附隨的申請專利範圍所限制。
1‧‧‧基膜
2‧‧‧導電黏著層
3‧‧‧絕緣黏著層
4‧‧‧導電粒子
5‧‧‧絕緣粒子
6‧‧‧各向異性導電膜

Claims (16)

  1. 一種各向異性導電膜，其包含一含括導電粒子和絕緣粒子之導電黏著層，以及一不含括導電粒子之絕緣黏著層，其中該導電黏著層之該導電粒子和該絕緣粒子具有每平方毫米7.0 x 105/d2至10.0 x 105/d2之總粒子密度，於此d為該導電粒子以μm(微米)計之直徑，以及該導電黏著層之該導電粒子對該絕緣粒子之體積比範圍係從1.5：1至1：3.5。
  2. 如請求項1之各向異性導電膜，其中就固體含量而言，以該導電黏著層的總重量為基準，該導電粒子和該絕緣粒子係以25wt%至60wt%的量存在。
  3. 如請求項1或2之各向異性導電膜，其中該導電粒子具有1μm至10μm之粒徑d。
  4. 如請求項1或2之各向異性導電膜，其中該導電黏著層具有該導電粒子直徑之50%至150%的厚度。
  5. 如請求項1或2之各向異性導電膜，其中該導電粒子對該絕緣粒子之直徑比範圍係從1.5：1至1：1.5。
  6. 如請求項1或2之各向異性導電膜，其中該絕緣黏著層係形成於該導電黏著層的一個表面或二個表面之上。
  7. 如請求項6之各向異性導電膜，其中該絕緣黏著層對該導電黏著層之厚度比為大於1/5且小於10。
  8. 一種各向異性導電膜，其包含一個含括導電粒子和絕緣 粒子之導電黏著層，以及一個不含括導電粒子之絕緣黏著層，其中該導電黏著層之該導電粒子和該絕緣粒子係以該各向異性導電膜的總面積之80%或更大的總粒子面積比存在，以及該導電黏著層之該導電粒子對該絕緣粒子之體積比範圍係從1.5：1至1：3.5。
  9. 如請求項8之各向異性導電膜，其中就固體含量而言，以該導電黏著層的總重量為基準，該導電粒子和該絕緣粒子係以25wt%至60wt%的量存在。
  10. 如請求項8或9之各向異性導電膜，其中該導電黏著層具有該導電粒子直徑之50%至150%的厚度。
  11. 如請求項1、2、8及9中任一項之各向異性導電膜，其中該導電黏著層或該絕緣黏著層包含黏結劑樹脂及固化劑。
  12. 如請求項11之各向異性導電膜，其中就固體含量而言，以該導電黏著層的總重量為基準，該黏結劑樹脂係以10wt%至60wt%的量存在，以及該固化劑係以10至40wt%的量存在。
  13. 如請求項11之各向異性導電膜，其中就固體含量而言，以該絕緣黏著層的總重量為基準，該黏結劑樹脂係以30wt%至80wt%的量存在，且該固化劑係以20至70wt%的量存在。
  14. 如請求項1、2、8及9中任一項之各向異性導電膜，其中該絕緣黏著層對該導電黏著層之厚度比為大於1/5且小 於10。
  15. 一種各向異性導電膜，其包含一個含括導電粒子和絕緣粒子之導電黏著層，以及一個不含括導電粒子之絕緣黏著層，其中該導電黏著層之該導電粒子和該絕緣粒子具有每平方毫米7.0 x 105/d2至10.0 x 105/d2之總粒子密度，於此d為該導電粒子以μm計之直徑，該導電黏著層具有該導電粒子直徑之50%至150%的厚度，且該導電粒子和該絕緣粒子的中心放置於實質相同的平面上，以及該導電黏著層之該導電粒子對該絕緣粒子之體積比範圍係從1.5：1至1：3.5。
  16. 一種顯示器裝置，其包含：a)一配線基板；b)如請求項1至15中任一項之各向異性導電膜之該導電黏著層及該絕緣黏著層，該各向異性導電膜係附接至該配線基板；以及c)安裝於該導電黏著層或該絕緣黏著層之上的半導體晶片。
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