TWI243847B - Anisotropic electrically conductive binding material and connecting method - Google Patents

Anisotropic electrically conductive binding material and connecting method Download PDF

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Publication number
TWI243847B
TWI243847B TW090106169A TW90106169A TWI243847B TW I243847 B TWI243847 B TW I243847B TW 090106169 A TW090106169 A TW 090106169A TW 90106169 A TW90106169 A TW 90106169A TW I243847 B TWI243847 B TW I243847B
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Taiwan
Prior art keywords
anisotropic conductive
adhesive material
conductive particles
electronic component
conductive adhesive
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TW090106169A
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English (en)
Inventor
Yasuhiro Suga
Motohide Takeichi
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Sony Chemicals Corp
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Publication of TWI243847B publication Critical patent/TWI243847B/zh

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    • 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
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    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
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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
    • 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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    • H01B1/20—Conductive material dispersed in non-conductive organic material
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    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • 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
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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Conductive Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Wire Bonding (AREA)
  • Non-Insulated Conductors (AREA)

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1243847 A7 •_____B7__ 五、發明說明（/ ) 【發明之詳細說明】 【發明所屬之技術領域】 本發明係關於異向性導電接著材料及連接方法。 【習知技術】 近年來盛行著，將具有金凸塊或焊料凸塊(突起狀電極 )之裸1C晶片，在1C搭載用基板上的電極墊上直接進行覆 晶（flip-chip)構裝，或者是加工成晶片尺寸構裝（CSP) 之形態而進行構裝。在像這樣之構裝時，於裸1C晶片之突 起狀電極和1C搭載用基板之間，夾入配合有環氧樹脂等之 熱固性樹脂和導電性粒子之薄膜狀、糊狀或液狀之異向性 導電接著材料，而進行加熱加壓處理。 但是，在金凸塊的情形，會有所謂材料成本非常昂貴 之問題發生。此外，在焊料凸塊的情形，雖可藉由電解電 鍍法來製造出微細且均一之凸塊，但是，不僅需要阻劑製 程，且在進行鎪焊料之前，須形成底層金屬層（Ti/Cu) ，接著形成障蔽用金屬多層鍍層（Cu/Ni/Au)等，而有 需要複雜的電解電鍍製程之問題發生。 因此’嘗試使用材料成本低、能夠以比較單純之電解 電鑛作業來形成之鎳凸塊。 【發明所欲解決之課題】 但是’由於鎳凸塊之硬度高於金凸塊或焊料凸塊之硬 度，鎳凸塊會擠碎異向性導電接著材料中之導電性粒子而 使其發生塑性變形，對於裸1C晶片之鎳凸塊和IC搭載用 基板之鼠極塾將無法保持女疋之接觸狀態，而導致連接可 4 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ·裝--------訂---------線# (請先閲讀背面之注意事項再填寫本頁) 1243847 A7 _ B7___ •五、發明說明（Y) 靠性降低之問題發生° (請先閱讀背面之注意事項再填寫本頁) 本發明係用以解決以上習知技術之問題；本發明之目 的，係提供一種異向性導電接著材料，在將具有突起狀電 極之裸1C晶片等之電子元件和配線基板之連接墊施以異向 性導電連接時，即使是在使用鎳凸塊等之比較硬之凸塊來 作爲突起狀電極的情形，也可以確保不遜於習知之異向性 導電連接(使用金凸塊或焊料凸塊)之連接可靠性。 【用以解決課題之手段】 本案發明人等發現到：異向性導電連接時之連接可靠 性與異向性導電接著材料中之導電性粒子之10%壓縮彈性 模數（Ε)、電子元件之突起狀電極之縱向彈性模數（Ε’） 有密切之關係存在，且藉由調整（Ε’）對於（Ε)之比値在 特定之範圍內，可提高連接可靠性，而完成本發明。 也就是說，本發明係提供一種異向性導電接著材料， 係將導電性粒子分散於熱固性樹脂所構成者；其特徵在於 該導電性粒子之10%壓縮彈性模數（Ε)和應藉由該 異向性導電接著材料來連接之電子元件之突起狀電極之縱 向彈性模數（Ε’），係滿足以下之關係式（1): 0·02^Ε/Ε，^0·5·"⑴。 此外，本發明提供一種異向性導電接著材料之連接方 法，係藉由在電子元件之突起狀電極和配線基板之連接用 焊墊之間，夾住將導電性粒子分散於熱固性樹脂所構成之 異向性導電接著材料，藉由加熱加壓，以在確保電子元件 5 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1243847 A7 • ____B7___ 五、發明說明（^) 和配線基板間之導通下進行連接；其特徵在於： 作爲異向性導電接著材料，係使用導電性粒子之10% 壓縮彈性模數（E)和電子元件之突起狀電極之縱向彈性模 數（E’）滿足前述關係式（1)者。 【發明之實施形態】 以下，詳細說明本發明。 本發明之異向性導電接著材料，係將導電性粒子分散 於熱固性樹脂而成之薄膜狀、糊狀或液狀之接著材料；導 電性粒子之10%壓縮彈性模數（E)和應藉由該異向性導 電接著材料來連接之電子元件之突起狀電極之縱向彈性模 數（E’），必須滿足以下之關係式（1): 0·02$Ε/Ε’$0·5·" ( 1)。此乃基於，在 Ε/Ε’低於 0.02時，由於導電性粒子之復原力小，將無法確保充分之 連接可靠性；在Ε/Ε’超過0.5之時，則導電性粒子將無法 充分地變形，還是無法確保充分之連接可靠性。 在此，可依據JIS Ζ2241之試驗方法來測定突起狀電極 之縱向彈性模數（Ε’）。此外，導電性粒子之10%壓縮彈 性模數（Ε)，係對應於蘭德利布茲理論物理學課程-「彈 性理論」（東京圖書1972年發行）第42頁之所定義之Κ 値。該Κ値之意義，正如以下所敘述的。 在使壓縮半徑分別爲R、R’之2個彈性球體於壓縮狀 態下互相接觸之時，藉由下式⑴、（ii)來決定h : h=F2/3[D2(l/R+l/R，）r3···⑴ D= (3/4) [ ( 1-σ2) /E+ ( 1-σ，2) /E，]…（ii) 6 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） -----------裝--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 1243847 A7 .______B7____ .五、發明說明（j) Ο 在此，h代表R + R’和兩球之中心間之距離差，F代表 壓縮力，E和E，代表2個彈性球體之彈性模數，σ和σ ’代 表彈性球體之泊松比（Poisson rate)。 另一方面，在將彈性球體替換成爲剛體板並從兩側實 施壓縮的情形，於R，->〇〇、E》E’之時，可以近似地得到 下式（iii): F= (21V3) (S3/2) (E · R1/2) ( I— σ2)…（iii) ο 在此，S代表壓縮變形量。若定義K値成爲式（iv) 時，則能以式（v)表示K値： K=E/ ( 1— σ 2)…（iv) K= (3/ 2 ) · F · S —3/2 · R-i/2··· ( ν)。 該K値係可普遍且定量地表示球體之硬度者。藉由使 用該Κ値（也就是10%壓縮彈性模數（Ε))，可定量且 單一意義地表示微球體或分隔物（以下稱爲分隔物等）之 適當硬度。有關於Κ値之具體測定方法，則在本說明書之 實施例中進行詳細說明。 此外，導電性粒子之10%壓縮彈性模數（Ε)本身之 數値，過小時在連接可靠性試驗中成爲連接不良之可能性 變高，過大時有在初期連接無法形成導通之危險性、或是 對突起狀電極以外之回路部造成損傷之危險性存在，因此 一般定爲3〜30GPa。此外，電子元件之突起狀電極之縱向 彈性模數（E’）本身之數値，過小時當連接時導電性粒子 7 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------裝--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 1243847 A7 .____B7 _ ，五、發明說明) 會滑入至突起狀電極，而有連接不良之危險性存在，過大 時在連接時之壓力高的情形，會有破壞基板側之回路電極 等之危險性存在，因此一般定爲40〜200GPa。 本發明之異向性導電接著材料雖具有以上之特徵，但 是就其他之構造而言，則可以相同於習知之異向性導電接 著材料。 例如，作爲熱固性樹脂，可以列舉環氧樹脂、聚氨酯 樹脂和不飽和聚酯樹脂等。此外，熱固性樹脂，也可以具 有丙烯酸酯殘基或甲基丙烯酸酯殘基等之光反應性官能基 。其中，最好使用在常溫呈固態之環氧樹脂。在該狀態下 ’也可以合倂使用常溫呈液狀之環氧樹脂。可配合成爲薄 膜狀之異向性導電接著材料之性能要求，而適當地決定在 常溫呈液狀之環氧樹脂對於在常溫呈固態之環氧樹脂之混 合比例。此外，爲進一步提高以上之固態或液狀環氧樹脂 所構成之薄膜之可撓性程度，藉以提高異向性導電接著材 料之剝離強度之時，特別是最好在這些環氧樹脂之外，還 合倂使用可撓性環氧樹脂。這時，在本發明之異向性導電 接著材料中所使用之可撓性環氧樹脂之含有量，過少時並 無法充分地得到可撓性環氧樹脂之添加效果，過多時會導 致耐熱性降低，因此較佳爲5〜35重量％，更佳爲5〜25 重量％。 作爲本發明中之所使用之導電性粒子，可以由例如習 知之異向性導電接著材料所使用之材料中，適當地選擇使 用能滿足前述之式（1)者。可以使用例如焊料粒子、鎳粒 8 本紙張尺度適用家標準（CNS)A4規格（21〇 ；； 297公p 裝--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 1243847 A7 • ____Β7 •五、發明說明（1?) 子等之金屬粒子，或者是在苯乙烯樹脂等之樹脂芯表面上 形成金屬鍍膜而成之樹脂芯金屬被覆粒子’藉由雜交（ hybridization)而在樹脂芯之周圍附著二氧化矽等之無機粉 體、再用金屬鍍膜被覆而成之複合粒子。 導電性粒子之平均粒徑，可按照連接對象之電子元件 之凸塊材料或凸塊高度等來適當地決定，在以高密度進行 裸1C晶片之覆晶構裝等時，較佳爲1〜10//m之大小。 導電性粒子之配合量，可按照連接對象之電子元件之 凸塊面積或配線基板之連接墊面積等來適當地決定；過少 時無法在上下之電極間夾入導電性粒子，而成爲導通不良 ，過多時因導電性粒子之凝集而造成鄰接之電極間之短路 原因，因此相對於本發明之異向性導電接著材料之樹脂固 形分100重量份，導電性粒子之配合量較佳爲3〜30重量 份。 本發明之異向性導電接著材料中，按照需要可添加習 知之異向性導電接著材料中之所配合之公然周知之添加劑 ，例如異氰酸酯系交聯劑、環氧矽烷化合物等之結合劑、 環氧變性矽酮樹脂或苯氧樹脂等之熱固性絕緣性樹脂。 本發明之異向性導電接著材料，係將前述之熱固性樹 脂和導電性粒子按照需要而在甲苯等之溶媒中均一地混合 ，藉以g周製出。可以直接地使用液狀或糊狀者，或者是成 膜成熱固性異向性導電接著薄膜來使用亦可。 本發明之異向性導電接著材料能良好地適用於下述異 向性導電連接方法，即在電子元件之突起狀電極和配線基 9 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） -----------裝--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) A7 1243847 _____Β7 _ 五、發明說明（7) (請先閱讀背面之注意事項再填寫本頁) 板之連接墊之間，夾住將導電性粒子分散於熱固性樹脂所 構成之異向性導電接著材料，藉由加熱加壓，以在確保電 子元件和配線基板間之導通下進行連接。 在此之電子元件，係以具有突起狀電極之元件爲對象 。例如可列舉裸1C晶片、LSI晶片等。作爲突起狀電極， 可列舉金凸塊和焊料凸塊等，其中，最好可以使用硬度高 且材料成本相對低之鎳凸塊。 【實施例】 以下，藉由以下之實驗例，而具體地說明本發明。 此外，如以下所說明般測定導電性粒子之10%壓縮彈 性模數（E)(也就是K値）。 (導電性粒子之10%壓縮彈性模數（E) (K値）之 測定方法） 在具有平滑表面之鋼板上散布導電性粒子，從其中選 擇1個導電性粒子。接著，使用粉體壓縮試驗機（PCT_200 型、島津製作所製），藉由鑽石製之直徑50//m之圓柱形 之平滑端面壓縮導電性粒子（試驗負荷= 0.0098N ( lOgrf) 、壓縮速度（定負荷速度壓縮方式）=2·6Χ10·3Ν (0.27grf )/秒、測定溫度= 20°C )。此時，把壓縮負荷當作電磁 力而以電氣方式來檢測出，並且，把壓縮移位當作致動變 壓器所造成之移位而以電氣方式來檢測出，以求出圖1 (a )所示之壓縮移位-負荷之關係。由該圖分別求出導電性 粒子之10%壓縮變形下之負荷値和壓縮移位，根據這些數 値和式（v)如圖1 (b)所示般，不僅求出壓縮應變，並 10 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1243847 A7 .______ Β7_ .五、發明說明（t ) 求出K値（10%壓縮彈性模數（E))。其中之壓縮應變 ，係將壓縮移位除以導電性粒子之粒徑所得的値，並用％ 表示者。 實施例1 在混合環氧樹脂（Epik〇te-1009，油化硯殻環氧（股） 公司製）50重量份和潛在性硬化劑（HX3721，旭化成（股 )公司製）45重量份而成之熱固性絕緣性接著劑中，均勻 地分散對球狀鎳粒子施加鍍金處理而成之導電性粒子（曰 本化學工業（股）公司製、平均粒徑6/zm、10%壓縮彈性 模數（E) =41.6GPa) 5重量份，並且，進行成膜處理以 製造出35//m厚度之異向性導電接著薄膜。 在半導體晶片（凸塊材質=Nl、凸塊高度= 20//m、 凸塊面積= 10000//m2、縱向彈性模數（E，）=98GPa、E/ E’ = 0.42、外形= 6.3mmE])和玻璃環氧基板（配線材質= Cu、配線厚度= 18//m、鍍Ni/Au)之間，夾住該異向性 導電接著薄膜，且在180°C、147N ( 15kgf)、20sec之條件 下進行熱壓處理，以將前述兩者予以連接。所得之連接體 之每一端子之初期導通電阻爲5〜ΙΟιηΩ ’而成爲良好之連 接狀態。此外，還對連接體進行1〇〇小時之壓力鍋測試（ PCT · Pressure-Cooker-Test) ( 121°C ' 0.213MPa (2.1atm) 、在飽和濕度環境下），在PCT後之導通電阻値和初期導 通電阻値之間並未發生大的變動。 實施例2 在實施例1之所調製出之熱固性絕緣性接著劑中，均 11 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公餐） -----------裝--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 1243847 A7 • __B7 .五、發明說明（°J ) (請先閱讀背面之注意事項再填寫本頁) 勻地分散對球狀苯並鳥糞胺樹脂粒子施加鍍金處理而成之 導電性粒子（日本化學工業（股）公司製、平均粒徑5//m 、10% 壓縮彈性模數（E) =4.7GPa、E/E’ = 0.048 ) 5 重 量份，進行成膜以製造出35//m厚度之異向性導電接著薄 膜。使用該異向性導電接著薄膜，相同於實施例1般將半 導體晶片和玻璃環氧基板予以連接而得到連接體。所得之 連接體之每一端子之初期導通電阻爲5〜ΙΟπιΩ，而成爲良 好之連接狀態。此外，還對連接體進行100小時之壓力鍋 測試（PCT) (121°C、0.213MPa(2.1atm)、在飽和濕度 環境下），在PCT後之導通電阻値和初期導通電阻値之間 並未發生大的變動。 實施例3 在實施例1之所調製出之熱固性絕緣性接著劑中，均 勻地分散經二氧化矽被覆之球狀苯並鳥糞胺樹脂、並在其 外側施加鍍金處理而成之導電性粒子（日本化學工業（股 )公司製、平均粒徑7//m、10%壓縮彈性模數（E)= 21.6GPa、E/E’ = 0.22) 5重量份，進行成膜處理以製造出 35//m厚度之異向性導電接著薄膜。使用該異向性導電接 著薄膜，相同於實施例1而將半導體晶片和玻璃環氧基板 予以連接而得到連接體。所得之連接體之每一端子之初期 導通電阻爲5〜ΙΟιηΩ，而成爲良好之連接狀態。此外，還 對連接體進行100小時之壓力鍋測試（PCT) (121°C、 0.213MPa U.latm)、在飽和濕度環境下），在PCT後之 導通電阻値和初期導通電阻値之間，並未發生大的變動。 12 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1243847 A7 • ______B7___ 、五、發明說明（/D) 比較例1 在實施例1之所調製出之熱固性之絕緣性接著劑中’ 均勻地分散對球狀聚苯乙烯樹脂施加鍍金處理而成之導電 性粒子（日本化學工業（股）公司製、平均粒徑5//m、10 %壓縮彈性模數（E) =1.5GPa、Ε/Ε’ = 0·015) 5重量份 ，進行成膜處理以製造出35//m厚度之異向性導電接著薄 膜。使用該異向性導電接著薄膜’相同於實施例1而將半 導體晶片和玻璃環氧基板予以連接時，被夾在電極間之導 電性粒子成爲擠碎狀態（也就是破壞導電性粒子之狀態） ，所得之連接體之每一端子之初期導通電阻爲5〜ΙΟιηΩ。 但在對連接體進行100小時之壓力鍋測試（PCT) (121°C 、0.213MPa (2.1atm)、在飽和濕度環境下）時，PCT後之 導通電阻値，係由初期導通電阻値開始大幅上升’而導致 連接可靠性大幅降低。 比較例2 在半導體晶片（凸塊材質=Au、凸塊高度= 20//m、 凸塊面積=1〇〇〇〇#1112、縱向彈性模數^’）=76.40?3^ /E，= 0.54、外形= 和玻璃環氧基板（配線材質 =Cu、配線厚度=18/zm、Ni/Au電鍍）之間，夾住實施 例1所製造出之異向性導電接著薄膜，在180°C、147N ( 15kgf)、20sec之條件下進行熱壓處理，以將前述兩者予 以連接。 所得之連接體之每一端子之初期導通電阻爲5〜ΙΟιηΩ ，而成爲良好之連接狀態。但在對連接體進行1〇〇小時之 13 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------裝--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 1243847 A7 ._B7_ .五、發明說明（（1) 壓力鍋測試（PCT) ( 121°C、0.213MPa ( 2.1atm)、在飽 和濕度環境下）時，PCT後之導通電阻値，係由初期導通 電阻値開始大幅上升，而導致連接可靠性大幅降低。 【發明之效果】 依據本發明之異向性導電接著材料，在將具有突起狀 電極之裸1C晶片等之電子元件和配線基板之連接墊施以異 向性導電連接時，即使在使用鎳凸塊等之比較硬的凸塊作 爲突起狀電極的情形，也可以確保不遜於習知之異向性導 電連接(使用金凸塊或焊料凸塊)之連接可靠性。 【圖式之簡單說明】 圖1係負荷和壓縮移位間之關係圖（圖1 (a))，以 及壓縮應變和K値間之關係圖（圖1 (b))。 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）

Claims (1)

  1. 7™i,· Γφ ; 24隨 rL· 六、申請專利範圍 1·一種異向性導電接著材料，係將導電性粒子分散於 熱固性樹脂中而構成者；其特徵在於： 該導電性粒子之10%壓縮彈性模數（E)和應藉由該 異向性導電接著材料來連接之電子元件之突起狀電極之縱 向彈性模數（E，），係滿足以下關係式（1): 0.02SE/ES0.5.·· (1); 且該電子元件之突起狀電極，係由鎳所構成。 2·如申請專利範圍第1項之異向性導電接著材料，其 中·該導電性粒子之平均粒徑，係丨〜10//111。 3·—種連接方法，係在電子元件之突起狀電極和配線 基板之連接墊之間，夾住將導電性粒子分散於熱固性樹脂 中而構成之異向性導電接著材料，藉由加熱加壓，以在確 保電子元件和配線基板間的導通下進行連接；其特徵在於 作爲異向性導電接著材料，係使用導電性粒子之10% 壓縮彈性模數（E)和電子元件之突起狀電極之縱向彈性模 數（E’）滿足以下關係式（1)者： 0.02-E/ES0.5.·· ( 1); 且該電子元件之突起狀電極，係由鎳所構成。 本纸張尺度適用中國國家標準（CNS)A4規格(210 X 297公釐) -------------------------裝·..............訂................線 (請先閲讀背面之注意事項再塡寫本頁)
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