TW201244867A - Electroconductive bonding material, method for bonding conductor, and method for manufacturing semiconductor device - Google Patents

Electroconductive bonding material, method for bonding conductor, and method for manufacturing semiconductor device Download PDF

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Publication number
TW201244867A
TW201244867A TW101103537A TW101103537A TW201244867A TW 201244867 A TW201244867 A TW 201244867A TW 101103537 A TW101103537 A TW 101103537A TW 101103537 A TW101103537 A TW 101103537A TW 201244867 A TW201244867 A TW 201244867A
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Taiwan
Prior art keywords
melting point
particles
point metal
bonding material
conductive bonding
Prior art date
Application number
TW101103537A
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English (en)
Inventor
Takatoyo Yamakami
Takashi Kubota
Kuniko Ishikawa
Masayuki Kitajima
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Fujitsu Ltd
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Publication date
Application filed by Fujitsu Ltd filed Critical Fujitsu Ltd
Publication of TW201244867A publication Critical patent/TW201244867A/zh

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    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • 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
    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • H01L24/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L24/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
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    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
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    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
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    • B23K1/0016—Brazing of electronic components
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    • B23K35/262—Sn as the principal constituent
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
    • C23C24/106—Coating with metal alloys or metal elements only
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    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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    • H01L2924/1579—Material with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy

Description

201244867 六、發明說明： c 明戶斤屬椅々貝^4 j 發明領域 以下實施例關於一種導電性接合材料，一種接合導體 之方法，及一種方法製造半導體裝置之方法。 C It 發明背景 為了將電子組件（諸如半導體裝置)接合至基材（諸如玻 璃環氧化物基材），已經提出各種方法來使用可變熔點類型 之低熔點金屬熔膏（其熔點可經由熱處理而改變）以抑制由 於電子組件與基材間熱膨脹係數不同而導致的扭曲作用， 並達到接合品質（參見日本專利早期公開案第2002-261105 號’ WO第2007/125861號單頁，日本專利早期公開案第 2006-102769號及日本專利早期公開案第2008-161881號）。 例如，如第1圖所示，可變熔點類型之低熔點金屬熔膏 !〇(其為傳統導電性接合材料）由高熔點金屬顆粒（Sn-Bi鍍 覆的Cu顆粒）1及低熔點金屬顆粒（sn-Bi顆粒）2之金屬組 份’以及助熔劑組份3組成。基於低熔點金屬顆粒（Sn-Bi顆 粒)之熔點’此可變熔點類型之低熔點金屬熔膏1〇的起始熔 點為139°C。當可變熔點類型之低熔點金屬熔膏1〇在15〇。匚 或更低溫加熱時’低熔點金屬顆粒(Sn-Bi顆粒)2中的Sn擴散 進入高熔點金屬顆粒（Sn-Bi鍍覆Cu顆粒）1中而形成Bi-隔離 層4及Cu-Sn為主的介金屬化合物5並被轉變為金屬性接合 狀態，藉此可變熔點類型之低熔點金屬熔膏10的熔點上升 201244867 至大約250°C或更高。 因為可變熔點類型之低熔點金屬熔膏（其為傳統導電 性接合材料）的熔點會經由熱處理而改變，所以在導電性接 合材料供應步驟中可以選擇的加熱溫度被限制於起始熔點 (其為低溶點金屬顆粒（Sn-Bi顆粒）之溶點）或更低。如第2圖 所示，當基材6及電子組件8彼此接合時，若可變熔點類型 之低熔點金屬熔膏10(其為傳統導電性接合材料)被供應至 基材電極7上且被加熱以沉積於基材電極上時，該低熔點組 份消失且熔點升至25〇。(：或更高。因此，無法選擇先前於供 應材料至電極上之時，沉積可變熔點類型之低熔點金屬熔 膏於基材電極上的導電性接合材料供應步驟，問題在於無 法在15G°C或更低之低溫下將電子組件安裝於電子組件之 基材上。 此外，如第3圖所示，當可變熔點類型之低熔點金屬熔 膏其為傳統導電性接合材料)被裝人鑽孔裝埋之鑽模31 的凹陷部分時’電子組件的端子被壓人舰膏，所得產品 C或更低下加熱，且炫膏被加熱/轉送（沉積)於電子組 件8之端子9上’赠點組份;肖失且熔讀至2贼或更高。 因此’―旦炫化導電轉合㈣及轉送材料至電子組件之 食而子的加熱及轉送步驟無法選擇，則問題在於該電子組件 U在150 C或更低之低溫下被安裝至電子組件之基材上。 依此因為傳統導電性接合材料中之低溶點組份由於 熱處理‘肖失且軸升至2贼或更高所以當供應材料至 電極上同時沉料電性接合材料於基材之電極上的導電性 201244867 接合材料供應步驟，以及一旦熔化導電性接合材料及轉送 材料至電子組件之端子上的轉送步驟無法選擇，而且150<^ 或更低下的低溫接合在現在環境下是困難的。 [文件1]曰本專利早期公開案第2002_261105號； [文件2] WO第2007/125861號單頁； [文件3]曰本專利早期公開案第20064〇2769號； [文件4]日本專利早期公開案第2〇〇8_161881號。 I：發明内容：J 發明概要 這些貫她例之目的為用以提供一種導電性接合材料， 其可有效率地在低溫下接合基材至電子組件；一種藉由使 用該導電性接合材料接合導體的方法；與一種製造半導體 裝置的方法。 根據實施例之一面向，其提供一種導電性接合材料， 其包括高熔.Ιέ金屬難、巾紅金屬胁及低熔點金屬顆 粒的金屬組份’聽點金屬顆粒具有第—熔點或更高；中 炼點金屬顆粒具有第二，熔點，其為第—溫度或更高，且第 /皿度或更低’第二溫度低於第_炼點但高於第一溫度； 低炫點金屬顆粒具有第三魅或更低，第三熔點低於第一 溫度。 圖式簡單說明 第1圖為顯示傳統導電性接合材料及導電性接合材料 已經進行加熱後之狀態的簡要圖； 第2圖顯示傳統導電性接合㈣被供應至基材之電 201244867 極，及電極被接合至電子組件之端子之狀態的簡要圖； 第3圖顯示傳統導電性接合材料被加熱且轉印至電子 組件上，及電子組件被接合至基材之電極的簡要圖； 第4圖顯示本發明導電性接合材料，及導電性接合材料 已經進行加熱後之狀態的簡要圖； 第5圖顯示本發明導電性接合材料之另一實例的簡要 圖； 第6A圖為經第二級熱處理後，導電性接合材料中之Bi 及 Sn的相圖（phase diagram); 第6B圖為經第二級熱處理後，導電性接合材料中Cu及 Sn的相圖； 第6C圖為經第二級熱處理後，導電性接合材料中Cu及 In的相圖； 第7圖顯示本發明接合導體之方法之一實例的簡要圖； 第8圖顯示本發明接合導體之方法之另一實例的簡要 圖；及 第9圖顯示製造實例18及19之半導體裝置之方法的簡 要圖； 第10圖顯示製造實例20之半導體裝置之方法的簡要 圖；及 第11圖顯示製造實例21之半導體裝置之方法的簡要 圖。 I：實施方式3 較佳實施例之說明 201244867 對於解決上述問題之方法的強力研究已在進行，而且 如後所述者，該方法已被找到。在一種含有高熔點金屬顆 粒（其具有150°C或更高的熔點），中熔點金屬顆粒（其具有8〇 C或更馬且139°C或更低的炫點），及低熔點金屬顆粒（其具 有79°C或更低的熔點）之金屬組份的導電性接合材料中，起 始狀態的熔點為79°C ’此為低熔點金屬顆粒的熔點；當此 導電性接合材料在79°C至138°C進行初級熱處理時，材料轉 換為金屬性接合狀態〇)，其中熔點為79。(3至139°C ;在此金 屬性接合狀態（1) ’保留熔點為139r或更低之低熔點組份； 接著，當金屬性接合狀態（1)中材料在^^匚或更高下進一步 進仃第二級熱處理時，低熔點金屬顆粒及中熔點金屬顆粒 擴政進入咼熔點金屬顆粒以形成Bi_隔離層，Cu_Sn為主的 介金屬化合物’ Cu-In為主的介金屬化合物及㈣如為主 的介金屬化合物，結屬性接合狀g⑴轉換為金屬性接合 狀態(2)，其中熔點變得25代或更高；依此，藉由使用含: 金屬化合物之導電性接合材料，該金壯合物㈣點l5〇t 或更高之高㈣金屬顆粒或更高且i3% 炫點金屬胁，贿點听或更低之麟點粒 且具有三個階段的如，即使在初級熱處理之後， ^點組份減可確定地”，依此使得當供應材料於電 ^同時，沉料魏於基材之職電 接合材料供應步驟，與—曰 等電性 料至電子組件之端子上的轉=:接合材料及轉送材 轉送步驟可被選擇，這太 統上是困難的，因而使得電子組件能夠幻听或更低^ 201244867 溫下被有效率地接合至基材上，而且在電子組件已經被安 裝於基材上之後也可以絲點改變至2贼或更高的高溫 區域。 (導電性接合材料） 本發明的導電性接合材料包括一種金屬組份，較佳地 包括助溶劑組份，及當需要時，更包括另外的組份。 <金屬組份> 上述金屬組份由高熔點金屬顆粒、中熔點金屬顆粒及 低熔點金屬顆粒形成。 <<高炼點金屬顆粒》 上述咼熔點金屬顆粒之熔點為150。(：或更高，較佳地為 300C或更高’及更佳地為细。c或更高。當上述高溶點金 屬顆粒之熔點低於15G°c時，其本身與中;^點金屬顆粒炼點 之間的差異變小’且在15G°C或更低之低溫接合作用變得困 難。 可例如以微差掃描熱量測定法(DSC)測定上述高熔點 金屬顆粒的熔點。 上述高熔點金屬顆粒之形狀、平均顆粒大小、結構等 等並不想被限制而且可根據目的為適當地選擇，只要高熔 點金屬顆粒為滿足上述炫點的金屬顆粒。 上述局熔點金屬顆粒包括，例如，Au顆粒、Ag顆粒、 Cu顆粒、Au鍍覆的Cu顆粒、Sn-Bi鍵覆的Cu顆粒及Ag鍍覆 的Cu顆粒。這些顆粒可以單獨使用，或是一起使用兩或更 多的顆粒。其中，Sn-Bi鑛覆的Cu顆粒、Ag鍵覆的Cu顆粒、 8 201244867 A u鍍覆的C u顆粒及C u顆粒從焊料可濕性的觀點而言是特 別佳的。 上述Sn-Bi鍍覆的Cu顆粒包括，例如，Sn-58Bi鍍覆的 Cu顆粒。 上述高熔點金屬顆粒的形狀包括，例如，球面形狀、 純粹球形及橄欖球形狀。 上述高熔點金屬顆粒之結構可為單層結構或疊層結 構。 上述高熔點金屬顆粒之平均顆粒大小較佳地為3 0 μ m 至50μηι，及更佳地為35μηι至45μιη。 上述金屬組份中上述高熔點金屬顆粒的含量較佳地為 80質量％至90質量％，更佳地為83質量％至87質量％。當上 述含量少於80質量％時，接合部之傳導電阻會增加，當含 量超過90質量％時，焊料的可濕性會惡化且傳導電阻會增 加。 上述高熔點金屬顆粒並不想成為限制，及可使用適當 製造之顆粒或使用商品化產品。製造上述高熔點金屬顆粒 之方法包括，例如，含有霧化製程的粉末化方法。 «中熔點金屬顆粒》 上述中熔點金屬顆粒之熔點為80°C或更高且139°C或 更低，較佳地為80°C至130°C。當上述中熔點金屬顆粒之熔 點低於80°C時，其本身與低熔點金屬顆粒熔點之間的差異 會消失。當上述中熔點金屬顆粒之熔點超過139°C時，其本 身與高熔點金屬顆粒熔點之間的差異會變小，可能無法選 201244867 擇導電性接合材料供應步驟及轉送步驟，且150°c或更低之 低溫接合作用變得困難。 中熔點金屬顆粒之熔點可以，例如，微差掃描熱量測 定法(DSC)測定。 上述中熔點金屬顆粒包括，例如，Sn-Bi顆粒及Sn-Bi-Ag 顆粒。 上述Sn-Bi顆粒包括，例如，Sn-58Bi顆粒。 上述Sn-Bi-Ag顆粒包括，例如，Sn-57Bi-lAg顆粒。 上述中炫點金屬顆粒之形狀包括，例如，球面形狀、 純粹球形及橄欖球形. 上述中炼點金屬顆粒之結構可為單層結構或疊層結 構。 上述中熔點金屬顆粒之平均顆粒大小較佳地為ΙΟμηι 至40μιη，及更佳地為20μηι至30μιη。 上述金屬組份中之中熔點金屬顆粒的含量較佳地為5 質量％至15質量％，更佳地為10質量％至15質量％。當上述 含量少於5質量％，焊料之可濕性會惡化且傳導電阻會增 加，當含量超過15質量％，在熔點改變時會發生問題。 上述中熔點金屬顆粒並不想成為限制，且可使用適當 製造的顆粒或使用商品化產品。製造上述中熔點金屬顆粒 之方法包括，例如，霧化製程。 «低熔點金屬顆粒》 上述低熔點金屬顆粒之熔點為79°C或更低，較佳地為 70°C至79°C。當上述熔點超過79°C，其本身與中熔點金屬 10 201244867 顆粒熔點之間的差異變小，可能無法選擇導電性接合材料 供應步驟及轉送步驟，且在15〇。(：或更低下的低溫接合作用 變得困難。 上述低熔點金屬顆粒之溶點町以，例如’微差掃描熱 量測定法(DSC)測定。 上述低熔點金屬顆粒包括，例如，Sn-Bi-In顆粒及 Sn-Bi-Ga顆粒。 上述Sn-Bi-In顆粒包括，例如，17Sn-58Bi-25In顆粒及 12Sn-41Bi-47In顆粒。 上述低熔點金屬顆粒之形狀包括，例如，球面形狀、 純粹球形及橄欖球形狀。 上述低熔點金屬顆粒之結構町為單層結構或疊層結 構。 上述低熔點金屬顆粒之平均賴粒大小較佳地為1〇μηι 至40μηι，更佳地為2〇pm至3〇gm。 上述金屬組份中低熔點金屬賴粒之含量較佳地為5質 量％至15質量％，更佳地為10質量％至15質量。/。。當上述含 畺少於5負量％時，焊料之可濕性會惡化且傳導電阻會增 加，當含量超過15質量時，熔點改變時會發生問題。 上述低熔點金屬顆粒並不想成為限制，且可使用適當 製造之顆粒或使用商品化產品。製造上述低熔點金屬顆粒 之方法包括，例如，霧化製程。 如上所述’上述金屬組份可使用上述⑽點金屬顆 粒、上述愤點金屬顆粒及上述低溶點金屬顆粒之金屬組 201244867 份’但也可使用非上述金屬顆粒的複層金屬顆粒，其依序 具有中@點金屬顆粒形成的中炫點金属層及低溶點金屬顆 粒（其形成於高炫點金屬顆粒表面上）形成的低熔點金屬 層。複層金屬顆粒較佳之處在於可因此獲得單一複層金屬 顆粒組成的導電性接合材料。當複層金屬顆粒依序具有低 熔點金屬顆粒形成的低熔點金屬層及中熔點金屬顆粒（其 形成於咼熔點金屬顆粒表面上）形成的中熔點金屬層時，因 為最外層表面上沒有低熔點金屬層，所以150。(：或更低的低 溫接合作用變得困難。 上述複層金屬顆粒並不想成為限制，且可使用適當製 造的顆粒或使用商品化產品。 上述高熔點金屬顆粒可使用與上述高熔點金屬顆粒相 同的金屬顆粒。 上述高熔點金屬顆粒之平均顆粒大小較佳地為4〇μιη 或更少，較佳地為30μιη至40μπι。當上述平均顆粒大小超過 40μπι，就接合作用中的精細接觸可能會發生問題。 中熔點金屬層之平均厚度較佳地為1 或更多，更佳 地為Ιμηι至當上述平均厚度少於1μηι,中熔點金屬之 女裝變小，且在150eC或更低之低溫接合變得困難。 上述中熔點金屬層可以，例如，無電極鍍覆技術或類 似技術形成。 上述低炫點金屬層之平均厚度較佳地為1(Im或更多， 更佳地為Ιμηι至5μηι。當上述平均厚度少於1μπι，低熔點金 屬之安裝變小：且在15()t或更低之低溫接合作用變得困 12 201244867 難。 、述低炼點金屬層可以’例如，無電極It覆技術或類 似技術形成。 上述金屬組份中導電性接合材料之含量並不想成為限 制丄且可根據目的適當地_;但較佳地為5Gf量％至95 質量。/。；更佳地為70質量％至90質量％。 <助熔劑組份> 上述助溶劑組份至少可使用環氧化物為主的助溶劑材 料及松㈣主的助_材料之任—者。於這些材料中環 氧化物為主的助炼劑材料係特別佳的，因為環氧化物為主 的輯劑材料可藉由固化環氧化物樹脂增強接合力道。 -環氧化物為主的助炼劑材料_ 上述裱氧化物為主的助熔劑材料包括環氧化物樹脂、 羧酸及溶劑，且當需要時，更包括另外組份。 上述環氧化物樹脂並不想成為限制，但可根據目的為 適當選擇，及包括’例如，熱固型環氧化物樹脂諸如雙齡A 型環氧化物樹脂，雙酚F型環氧化物樹脂，酚醛型環氧化物 樹脂及其等之改質環氧化物樹脂。這些環氧化物樹脂可單 獨使用’或是兩或更多環氧化物樹脂可一起使用。 上述羧酸較佳地選擇自由下述化合物組成的群組中： 飽和脂肪族為主的二羧酸、非飽和脂肪族為主的二羧酸、 環脂肪族為主的二綾酸、含胺基羧酸、含羥基羧酸、雜環 二羧酸及其等的混合物。特別地，羧酸包括琥珀酸、戊二 酸、已二酸、壬二酸、十二烷二酸、伊康酸、中康酸、環 13 201244867 丁烷二羧酸、L-麩胺酸、檸檬酸、蘋果酸、硫丙酸、硫二 丁酸及二硫乙醇酸。 上述溶劑包括，例如：醇類諸如甲醇、乙醇及丙醇； 二甘醇單己醚；及辛烷二醇。 添加劑，例如，諸如搖變減黏劑、螫合劑、表面活性 劑及抗氧化劑也可被加入環氧化物為主的助炼劑材料中， 作為上述的另外組份。 上述環氧化物為主的助熔劑材料並不想成為限制，及 可適當地使用合成材料或使用商品化產品。 -松香為主的助炫劑材料_ 上述松香為主的助炼劑材料包括松香樹脂、活性劑及 溶劑，且若需要時，更包括另外組份。 上述松香樹脂包括含有天然松香樹脂或改質松香樹脂 作為主組份的樹脂。上述改質松香樹脂包括，例如，經聚 合的松香、氫化的松香；酚-樹脂-改質松香及順丁烯二酸-改質松香。 上述活性劑包括無機活性劑及有機活性劑，及包括， 例如，鹵素為主的活性劑，諸如胺鹽酸鹽，與有機酸為主 的活性劑。 上述溶劑包括，例如，二甘醇單己醚及辛二醇。 添加劑，例如，諸如搖變減黏劑、螫合劑、表面活性 劑及抗氧化劑也可被加入松香為主的助炫劑材料中作為上 述的另外組份。 上述松香為主的助熔劑材料並不想成為限制，且可適 14 201244867 田地使用、,、t合成的材料或使用商品化產品。 上所述導電性接合材料中之上㈣_組份的含量較佳地為 巧量%至50質量％，更佳地為10質量。/。至30質量％。 «其他組份》 當需要時，上述導電性接合材料可含有上述金屬組份 及上述麟劑組份以外的組份。上述另外組份包括，例如， 分散劑及抗氧化劑。 此處’本發明導電性接合材料將參考圖式說明。 第4圖顯示本發明導電性接合材料20之—實例 的簡要圖。此導電性接合材料2()由高熔點金屬顆粒 (熔點1’083 C之Sn-58Bi鍍覆的Cu顆粒）2卜中炼點金 屬顆粒（㈣之㈤服顆粒)22及低炫點金屬顆粒 (熔點79t之17Sn-篇·251,顆粒)23的金屬組份，以及助熔 劑組份3組成。基於低熔點金屬顆粒（17Sn_58Bi 25in顆粒） 之熔點，導電性接合材料2〇之起始熔點為79。〇。 當此導電性接合材料2〇進行初級熱處理(79〇c至丨38。〇） 時’形成金屬性接合狀態（1)。基於中熔點金屬顆粒(Sn 58Bi 顆粒)22之溶點’此金屬性接合狀態〇)之熔點為79。匸至139 °C ’且熔點139°C或更低之低熔點組份留存。 接著，當此金屬性接合狀態（1)進行第二級熱處理（150 °C或更低）時’低熔點金屬顆粒（17Sn-58Bi-25In顆粒）23及中 熔點金屬顆粒(Sn_5 8Bi顆粒)22内之sn擴散進入高熔點金屬 顆粒（Sn-Bi鍍覆的Cu顆粒)21以形成Bi-隔離層4、Cu-Sn為主 的介金屬化合物5、Cu-In為主的介金屬化合物24及Cu-Sn-In 15 201244867 的第三級介金屬化合物25，金屬性接合狀態（1)轉換為 金屬性接合狀態(2)，且其熔點升至25G〇c或更高。 此外’第5圖為本發明導電性接合材料30之另一實例的 簡要圖。此導電性接合材料30由複層金屬顆粒與助熔劑組 知3'纟且成，該複層金屬顆粒依序具有高熔點金屬顆粒（熔點 1083 (:之Sn-58Bi鍍覆的Cu顆粒)2卜及由中熔點金屬顆粒 (炫點139°C之Sn-58Bi顆粒）形成之中熔點金屬層22,，與由 在此向熔點金屬顆粒表面上之低熔點金屬顆粒（熔點79〇c 之17Sn_58Bi-25In顆粒）形成之低熔點金屬層23,。 當此導電性接合材料30進行初級熱處理(79t至138°C) 時’形成金屬性接合狀態（1)。基於由中熔點金屬顆粒 (Sn-58Bi顆粒）形成之中熔點金屬層22ι的熔點，此金屬性接 合狀態（1)之熔點為79°C至139°C，且具有139°C或更低之熔 點的低炼點組份依然留存。 接著’當此金屬性接合狀態（1)進行第二級熱處理（15〇 °C或更低）時’低熔點金屬顆粒（17Sn_58Bi_25In顆粒)23及中 熔點金屬顆粒(Sn-58Bi顆粒)22中之Sn擴散進入高熔點金屬 顆粒（Sn-Bi鍍覆的Cu顆粒）21中以形成Bi-隔離層4、Cu-Sn 為主的介金屬化合物5、Cu-In為主的介金屬化合物24及 Cu-Sn-In為主的第三級介金屬化合物25，金屬性接合狀態（1) 轉換成金屬性接合狀態(2)，且其熔點升至250°C或更高。 此處，如上所述，初級熱處理後金屬性接合狀態（丨）中 之導電性接合材料進行第二級熱處理，然後Sn-Bi合金或 Sn-Bi-In合金中之Sn及Sn-Bi-In合金中之In擴散進入cu中。 201244867 隨著擴散作用，形成Bi-隔離層且金屬性接合狀態（1)轉換為 金屬性接合狀態（2)。因此已經發現’如第6A圖所示，藉由 設定Bi含量至95質量％或更多，Bi-隔離層熔點變得25〇°c或 更高’換言之’金屬性接合狀態（2)之熔點變得25〇t或更高。 此外’於導電性接合材料中，由於第二級熱處理，Sn 擴政進入Cu以形成Cu-Sn介金屬化合物層，且金屬性接合狀 態（1)轉換為金屬性接合狀態(2)。因此已經發現，如第6B圖 所示，藉由設定Cu含量為3質量％或更多，Cu-Sn為主的介 金屬化合物層之熔點變得25(rc或更高，換言之，金屬性接 合狀態(2)熔點變得25〇°c或更高。 此外’於導電性接合材料中，由於第二級熱處理，In 擴散進入Cii中以形成以也介金屬化合物層，且金屬性接合 狀態⑴轉換為金屬性接合狀態(2)。因此已經發現，如第6C 圖所示’藉由奴Cu含量為3f量％或更多，Μη為主的 介金屬化合物層之熔點變得2坑或更高，換言之，金屬性 接合狀態(2)之熔點變得25〇t*更高。 明導電性接合材料藉由混合上述金屬組份、上述 助炼劑組份及，當需要時，另外峰.備。上述混合方 法及條件不想㈣，且可根據目的適當地選擇。混合操作 已知'合裝置、檀掉裝置及類似裝置執行，且 車乂佳的疋在非氧化性大氣中均勻地攪拌各組份。 本叙月導電性接合材料使得能夠 件Μ在15Gt或更低的低溫下有效率地彼此 17 201244867 接合。佑μ 合材料之/、導電性接合㈣可使料各種洲導電性接 中，’但較佳地可被用於本發明接合導體的方法 (接人！《明製造半導體之方法中，其等將於稍後說明。 (接合導體之方法） &月接合導體之方法包括導電性接合材料供應步 、‘、、、處理步驟及第二級熱處理步驟，及當需要時， 更匕括另外步驟。 〈導電性接合材料供應步驟> 上述導電性接合材料供應步驟為供應本發明上述導電 ft接。材料至基材電極與電子組件端子巾任—者的步驟。 «基材》 述基材之形狀、結構、尺寸等等不享受限，且可根 據目的適當地選擇。上述形狀包括，例如，平面形狀。上 述結構可為單層結構或4層結構4述尺寸可依據上述電 極層或相似物之尺寸而適當地選擇。 上述基材包括，例如：玻璃基材、石英基材、矽基材 及Si02薄膜塗覆之⑪基材；及聚合物基材，諸如環氧化物 樹脂、酴樹脂、聚對苯二甲酸乙二醋基材、聚碳酸醋基材、 聚苯乙烯基材及聚f基丙烯酸甲酯基材。這些基材可單獨 使用，或是兩或更多基材一起使用。上述基材之中，玻璃 基材、石英基材、矽基材及Si〇2薄膜塗覆之矽基材係較佳 的選擇’且矽基材及Si〇2薄膜塗覆之矽基材係特別佳的。 上述基材可為經適當合成的基材或可使用商品化產 品0 18 201244867 上述基材之厚度並不想成為限制，且可根據目的適當 地選擇。厚度較佳地為刚帅或更多，更佳地為 更 多。 使用具有佈線圖案形成於其上之佈線電路板作為上述 基材。電路板可為單層電路板(單層印刷佈線板)或複層電路 板(複層印刷佈線板）。 構成上述電路板之電極的金屬包括，例如，諸如cu、 Ag、Au、Ni、Sn、A卜Ti、Pd及Si之金屬。於上述金屬中， Cu、Ag及Au係特別佳的。藉由各種處理(諸如電鍍及層化）， 這二金屬可形成為基材上電極金屬之表面部分。提供以下 田導電性接合材料被施用於基材之電極金屬上時， 基材上之電極金屬通常具有塗層，如此導電性接合材料可 被適Μ地連接至基材上之電極金屬。例如，銅電極可以形 成於電極上之薄膜（諸如Sn、Au及Ni)電鍵。除了 Au以外， 上述金屬之金屬表面特別容易氧化，依此，較佳的是，在 沣膏施加於金屬之前，以助熔劑或類似物處理金屬表面、 以助熔劑預塗覆金屬，以各種金屬電鍍金屬或以焊料塗覆 金屬。 電子組件- 上述電子組件不想受限’只要該電子組件具有端子。 電子組件可具有根據目的被適當地選擇之已知的構件及類 似物’且可用於半導體裝置及半導體封裝件，例如，較佳 地使用於各種領域中的快閃記憶體、DRAM、FRAM、MOS 電晶體等等。 19 201244867 〆端子》 上述端子並不想成為限制，可根據目的適當地選擇， 真包括’例如’佈線、金屬性佈線及含導電性料之印刷 佈線。 上述立而子之材料並不想成為限制，可根據目的適當地 邊擇’且包括，例如，諸如Cu、Ni、Au、A1、M。及cr之金 屬’諸如ITO及IZO之金屬氧化物，與其等的疊層體或複合 物。 -供應方法- 供應上述導電性接合材料之方法並不想成為限制，只 要導電性接合材料可被施用以形成具有固定厚度之薄膜， 或以固定之施用量施加的話。方法可根據目的適當地選 擇，且包括，例如，網板印刷、轉印印刷、分配及射出與 噴墨印刷。 上述網板印刷可使用具有遮罩盤用途之印刷機器。印 制機器典型上包括：固定基材或電子組件之機制；使金屬 遮罩與基材之電極或電子組件之端子對齊的機制；加壓熔 换遮罩盤至基材或電子組件的機制，與相對於基材電極或 遮罩下方之電子組件端子，從遮罩上方壓印導電性接合材 枓’通過具有橡膠滾軸（squeegee)之開孔而施用之機制。就 遮罩盤而言，存在著各種材料，諸如篩孔類遮罩及金屬類 遮罩’但廣泛對應顆粒尺寸且製程中容易清潔之金屬類遮 蕈一般上較廣泛使用。 上述轉印印刷為一種方法，其以具有固定清潔度之橡 20 201244867 膠/袞軸ι成經平坦施用的塗膜該經平坦施用之 口疋厚度之導電性接合材料，以壓模掘取塗暝、、具有 塗膜衝印於基材之電極或電子組件之端子上，及田掏取之 疋數置之導電性接合材料安置於基材之電極或電子=將固 知子上，以及使用專一的（dedicated)轉印印刷裝置 牛之 刷A置包括：形成經平坦施用之塗膜的施用機轉P印 材及對準基材之電極位置的機制；及三維驅動固疋基 塗膜且轉印及衝印經擷取塗膜的卿。相較於掏取 轉印印刷料在施賴量上變化，且在連續 P刷’ 之清潔管理)時需要小心注意。依此，網板印刷已 印刷。 』匕焱疋主流 上述分配及射出用於射出固定數量之導電性接合 7材上之電極或電子组件之端子上，且使用分 置。分配器為一種佑带出#丄 我 檀依需求藉由施加壓力（其係將針筒 之導電性接合材料射出所需）從針筒尖端上之針擠出固定 =Γ接t材料的農置，而且分配器藉由三維地驅 θ a及决疋基材上電極之位置射出及施加經要求數 量之導電性接合材料於電極上。相較於網板印刷，由於從 針射出之技術的緣故’上述分配作用具有―個缺點，就是 ㈣本身難以更細地散佈。然而，於製程中，該方法只造 成少量溶膏之漏失，可藉由程式變化射出之位置及數量， 及依此可施加導紐接合材料於基材及電作件上，該基 材及電子料具有軸㈣及具有印刷鮮飾絕被加壓 嫁接所造成之不平坦。 21 201244867 上述喷墨印刷用於從精細喷口中射出導電性接合材 料，及施加導電性接合材料至基材之電極或電子組件之端 子上。 <初級熱處理步驟> 上述初級熱處理步驟為在溫度低於中熔點金屬顆粒之 熔點下，將經供應之導電性接合材料進行熱處理，及沉積 經熱處理之導電性接合材料至上述基材之電極或電子組件 之端子任一者上的步驟。 上述初級熱處理步驟較佳地在低於中熔點金屬顆粒之 熔點的溫度下執行達5秒，特別地，較佳地在70°C至l〇〇°C 下執行達3秒至7秒。 上述初級熱處理並不想成為限制，可根據目的適當地 選擇，及可以例如，氮迴流裝置或類似裝置執行。 上述初級熱處理可在空氣中執行，但更佳地在氮氣中 執行。 <第二級熱處理步驟> 上述第二級熱處理步驟為加熱經沉積之導電性接合材 料，及接合基材之電極至電子組件之端子的步驟。 上述第二級熱處理步驟為施加固定溫度至導電性接合 材料的步驟，該導電性接合材料已被供應至基材之電極或 電子組件之端子及沉積於基材之電極或電子組件之端子 上，在此種電子組件或基材在火爐中排列及通常使用迴流 裝置之狀態下，具有火爐之高溫槽或類似裝置適合於焊料 熱處理。 22 201244867 I在使用上述迴流裝置之迴流熱處理中，紅外線施用 ‘、、、玉氣％用型及類似裝置是主流的加熱方法。有些案 例中二氣及氮氣用作迴流熱處理之火爐中的氣體，但是氮 乱中迴流火爐被廣泛用於最近高密度及高精確度封裝中， 、避免由於氧化所導致之電子組件及焊料經接合部分的崩 解。 一上述第二級熱處理較佳地在中熔點金屬顆粒熔點或更 门及150 C或更低之溫度下執行3Q分鐘或更久，及較佳地在 85 C至150°C下執行30分鐘至120分鐘。 上述第二級熱處理可在空氣中執行，但更佳地在氮氣 中執行。 此處，第7圖為本發明用以接合導體之方法之一實例的 簡要圖。 首先’本發明之導電性接合材料2〇以網板印刷被列印 在備置有Cu電極7之基材6上。本發明之導電性接合材料2〇 的起始熔點為79。(：。 接著，經列印的導電性接合材料2〇進行初級熱處理(79 C至139。〇,且經加熱之導電性接合材料2〇被沉積（預塗覆) 於基材之電極7上。即使於初級熱處理後，熔點139<^或更 低之低熔點組份仍然存留在導電性接合材料2〇中。 接著，備置有Au凸塊9之以晶片8被排列在具有導電性 接合材料20沉積於其上之基材6上，此組合體進行第二級熱 處理（150C)。藉此’備置有如凸塊9之以晶片8被安裝於基 材6上。由於此第二級熱處理，金屬性接合狀態改變且溶點 23 201244867 變得250°C或更高。 此外，第8圖為本發明接合導體之方法之另一實例的簡 要圖。 首先，本發明之導電性接合材料2〇以橡膠滾軸注入鑽 孔裝埋鑽模31的凹陷部内，及備置有Au凸塊9之&晶片_ 壓至導電性接合材料。然後，該裝配體與s丨晶片8一起進行 初級熱處理(79C至139。〇，及導電性接合材料2〇沉積（預塗 覆)於Si晶片8之Au凸塊9上。即使於初級熱處理後，熔點139 c或更低之低、熔點組份仍然存留於導電性接合材料2〇中。 接著，備置有Au凸塊9之Si晶片8(其含有導電性接合材 料20沉積於其上）被排列於其上備置有cu電極7之基材6 上，該裝配體進行第二級熱處理（150。〇，且備置有Au凸塊 9之Si晶片8面朝下被安裝於基材让。由於此第二級熱處理 之故’金屬性接合狀態改變且熔點變得25G°C或更高。 (製造半物|置之方法） 本發明製造半導體裝置之方法至少包括本發明接合導 體之上述步驟’及若需要時’更包括另外步驟。 接。導體之上述步驟可以與本發明接合導體之方法類 似的方式執行。 述之另外步驟並不想成為限制，可根據目的適當 選擇，及& # 枯，例如，圖案化金屬佈線之步驟及形成絕 膜之步驟。 本七明製造半導體裝置之方法可有效率地製造，例 如’包括快閃記憶體、DRAM及FRAM之各種半導體裝置。 24 201244867 [實例] 本發明參考實例將更特別地說明於下，但本發明不限 於這些實例。 資訊提供，在實例中，金屬顆粒之溶點、金屬顆粒之
平均顆粒大小及低魅金職與切點金屬層之平均厚度 以下述方式測定。 X <金屬顆粒熔點之測定> 以微差掃描熱置測定法(D S C)(由精工儀器公司製造之 DSC6·)測定金屬顆粒之熔點，條件是溫度梯纽w秒 且測定溫度範圍25°C至250。(：。 <金屬顆粒平均顆粒大小之測定> 使用顆粒尺寸分布計(S ALD_3 i 〇〇，SffiMADZU公司製 造之雷射繞射顆粒尺寸分布測定儀器），金屬顆粒之平均顆 粒大小藉由以下方法計算而得：在氣相中分散金屬顆粒， 以紅半導體-雷射光束照射經分散之金屬顆粒，比較由光接 收元件輸入之光線為顆粒繞射及散射之圖案與標準圖案， 分析結果，及總計顆粒尺寸及記數數目。 <低熔點金屬層及中熔點金屬層平均厚度之測定> 低熔點金屬層及中熔點金屬層之平均厚度以平均值表 示’此平均值藉由截面拋光（cross_secti〇n p〇Hshing)法 (Buehler公司製造之GRINOER-POLISHER(Beta))測定低炼 點金屬層及中溶點金屬層之厚度10次而獲得。 (實例1) -導電性接合材料之製備- 25 201244867 由80質量％之高熔點金屬顆粒（熔點l，〇83°C (Cu)及平 均顆粒大小40_之Sn-58Bi錄覆的Cu顆粒），10質量❶/。之中 溶點金屬顆粒（熔點139<)(：之％_58則顆粒）及1〇質量。/。之低 熔點金屬顆粒(熔點79°C之17Sn_58Bi-25In顆粒）形成的金屬 組份...90質量〇/〇 由環氧化物為主之助熔劑材料（富士通品質實驗室股 份有限公司製造之F-Stick FTLD5)組成的助熔劑組份·.. ！ 〇 質量％ 在非氧化性大氣中均勻攪拌上述金屬組份及上述助熔 劑組份以製備實例1導電性接合材料。 (實例2) -導電性接合材料之製備_ 實例2之導電性接合材料以與實例丨類似的方式製備， 除了使用之如實例1之金屬組份由8〇質量％之高熔點金屬 顆粒（熔點1，0831 (Cu)及平均顆粒大小4〇μΐΏ2Sn_58Bi鍍覆 的Cu顆粒），5質量％之中熔點金屬顆粒（熔點139。匚之
Sn_58Bi顆粒）及15質量％之低熔點金屬顆粒（熔點79t之 17Sn-58Bi-25In顆粒）組成之外。 (實例3) -導電性接合材料之製備- 實例3之導電性接合材料以與實例丨類似的方式製備， 除了使用之如貫例1之金屬組份由8 〇質量％之高熔點金屬 顆粒（熔點1，083°c (Cu)及平均顆粒大小4〇μηΐ2 Sn_58Bi鍍覆 的Cu顆粒），15質量％之熔點金屬顆粒（熔點139t2Sn_58Bi 26 201244867 顆粒）及5質量°/〇之低熔點金屬顆粒（熔點79。〇之 17Sn-58Bi-25In顆粒）組成之外。 (實例4) -導電性接合材料之製備- 實例3之導電性接合材料以與實例丨類似的方式製備， 除了使用之如實例1之金屬組份由85質量％之高熔點金屬 顆粒（熔點1，〇83°C (Cu)及平均顆粒大小4〇叫之Sn_58Bi鍍覆 的Cu顆粒），7.5質量°/。之中熔點金屬顆粒（熔點139。〇之 Sn-58Bi顆粒）及7.5質量％之低熔點金屬顆粒（熔點79〇c之 17Sn-58Bi-25In顆粒）組成之外。 (實例5) -導電性接合材料之製備- 實例5之導電性接合材料以與實例丨類似的方式製備， 除了使用之如實例1之金屬組份由9〇質量％之高熔點金屬 顆粒（炼點1，083°C (Cu)及平均顆粒大小仙㈣之Sn_58Bi鑛覆 的Cu顆粒），5質量°/。之中熔點金屬顆粒（熔點i39°c之 Sn-58Bi顆粒）及5質量％之低熔點金屬顆粒（熔點79〇c之 17Sn-58Bi-25In顆粒）組成之外。 (實例6) -導電性接合材料之製備- 實例6之導電性接合材料以與實例丨類似的方式製備， 除了使用之如實例1之金屬組份由95質量％之高熔點金屬 顆粒（溶點1，〇83 C (Cu)及平均顆粒大小jOpmiSn-SSBi鑛覆 的Cu顆粒）’ 2.5質量％之中熔點金屬顆粒（熔點i39°c之 27 201244867
Sn-58Bi顆粒）及2.5質量％之低熔點金屬顆粒（熔點79°C之 17Sn-58Bi-25In顆粒）組成之外。 (實例7) -導電性接合材料之製備- 實例7之導電性接合材料以與實例1類似的方式製備， 除了使用之如實例1之金屬組份由75質量％之高溶點金屬 顆粒（，熔點l，〇83°C(Cu)及平均顆粒大小4〇μηι之Sn-58Bi鍵覆 的Cu顆粒）’ 12.5質量％之中炫點金屬顆粒（炼點139。〇之 Sn-58Bi顆粒）及12.5質量％之低熔點金屬顆粒（溶點79。匚之 17Sn-58Bi-25In顆粒）組成之外。 (實例8) -導電性接合材料之製備- 實例8之導電性接合材料以與實例4類似的方式製備， 除了實例4之高熔點金屬顆粒（Sn_58Bi鍍覆的Cu顆粒）以高 熔點金屬顆粒（熔點1，083°C(CU)及平均顆粒大*4(^miAg 鍍覆的Cu顆粒）取代之外。 (實例9) -導電性接合材料之製備- 實例9之導電性接合材料以與實例4類似的方式製備， 除了實例4之高熔點金屬顆粒（Sn_58Bi鍍覆的Cu顆粒）以高 熔點金屬顆粒（熔點丨，083〇C (Cu)及平均顆粒大小牝卜爪之Au 鑛覆的Cu顆粒）取代之外。 (實例10) _導電性接合材料之製備_ 28 201244867 實例ίο之導電性接合材料以與實例4類似的方式製 備’除了實例4之中熔點金屬顆粒(溶點139。〇之％-58出顆粒) 以中熔點金屬顆粒(溶點139。(：之Sn-57Bi-1 Ag)取代之外。 (實例11) -導電性接合材料之製備_ 實例11之導電性接合材料以與實例4類似的方式製 備’除了實例4之低熔點金屬顆粒（熔點79它之 17Sn-58B卜251η顆粒）以低熔點金屬顆粒（熔點59之 12Sn-41Bi-47In)取代之外。 (實例12) -導電性接合材料之製備_ 實例11之導電性接合材料以與實例4類似的方式製 備，除了實例4之環氧化物為主的助熔劑材料以松香為主的 助溶劑材料（富士通品質實驗室股份有限公司製造之 F-StickFTLD4)取代之外。 (實例13) <導電性接合材料之製備> -複層金屬顆粒之製備_ 中炼點金屬顆粒（熔點139°C之Sn-58Bi顆粒）形成之中 ’熔點金属4以無電電錄方法形成於高溶點金屬顆粒(炫點 l，〇83C及平均顆粒大小仙叫之。顆粒）之各表面上以具有 平均厚度1 μηι。 接著’低溶點金屬顆粒（熔點79°C之17Sn-58Bi-25In顆 粒）之低熔點金制以無電電鑛方法形成於中熔點金属層 29 201244867 上以具有平均厚Ιμιη。藉由上述步驟，製備金屬組份之複 層金屬顆粒。 -導電性接合材料之製備-經製備之複層金屬顆粒…90質量％ 環氧化物為主的助熔劑材料（富士通品質實驗室股份 有限公司製造之F-Stick FTLD5).·· 10質量％ 實例13之導電性接合材料係在非氧化性大氣下均勻攪 拌上述金屬組份及上述助熔劑組份而製備。 (實例14) -導電性接合材料之製備- 實例14之導電性接合材料以與實例13類似的方式製 備，除了實例13之高熔點金屬顆粒(熔點l，〇83°C及平均顆粒 大小40μιη之Cu顆粒）以高熔點金屬顆粒（熔點1,083 °C及平 均顆粒大小35μηι之Cu顆粒）取代之外。 (實例15) -導電性接合材料之製備- 實例15之導電性接合材料以與實例13類似的方式製 備，除了實例13之高熔點金屬顆粒(熔點1,0 8 3 °C及平均顆粒 大小40μπι之Cu顆粒）以高熔點金屬顆粒（熔點1，083°C及平 均顆粒大小45μιη之Cu顆粒）取代之外。 (實例16) -導電性接合材料之製備- 實例16之導電性接合材料以與實例13類似的方式製 備，除了如實例13之中熔點金屬層及低熔點金屬層的平均 30 201244867 厚度設定於〇.5μηι之外。 (實例17) -導電性接合材料之製備- 實例17之導電性接合材料以與實例13類似的方式製 備，除了如實例13之低熔點金屬顆粒（熔點79 °C之 17Sn-58Bi-25In顆粒）形成之低熔點金屬層以無電電鍍方法 形成於各個高熔點金屬顆粒（熔點1,0 8 3 °C及平均顆粒大小 40μηι之Cu顆粒）上以具有平均厚度Ιμηι，及接著由中炫點金 屬顆粒（熔點139°C之Sn-58Bi顆粒）形成之中熔點金屬層以 無電電鍍方法形成於低熔點金屬層上以具有平均厚度Ιμηι 之外。 (比較例1) -導電性接合材料之製備- 比較例1之導電性接合材料以與實例1類似的方式製 備，除了如實例1之低熔點金屬顆粒（熔點79 °c之 nSn-58Bi-25In顆粒）未被加入金屬組份中之外。 (比較例2) -導電性接合材料之製備- 比較例2之導電性接合材料以與實例1類似的方式製 備，除了如實例1之中熔點金屬顆粒（熔點139°C之Sn-58Bi 顆粒）未被加入金屬組份中之外。 (比較例3) -導電性接合材料之製備- 比較例3之導電性接合材料以與實例1類似的方式製 31 201244867 備’除了如實例1之高熔點金屬顆粒（熔點1，083°C (Cu)及平 均顆粒大小4 〇 μιη之S η-5 8B i鍵覆的Cu顆粒）未被加入金屬組 份中之外。 接著’使用各個經製備之導電性接合材料以下述方式 6平估各種特性。結果顯示於第1表。 义當導電性接合材料已被供應時，其表現之評估> 藉由各個導電性接合材料以網板印刷將圖案列印（供 應)於基材上’根據以下準則決定網板印刷盤之釋放性，作 為當導電性接合材料已被供應時，其表現之評估。 [評估準則] 佳：印刷盤之充分釋放性及充分 —般：印刷盤之不良釋放性但處於實際上可使用程度 不良：印刷盤不良釋放性及不良 電子組件已被封裝時，其表現之評估> 藉由使用各個導電性接合材料肉眼檢測焊料可濕性， 作為當電子組件已被封裝時，材料表現之評估，且根據以 下準則評估。 [評估準則] 佳：焊料充分可濕性 —般：焊料可濕性有些低劣（處於實際上可使用程度） 不良.焊料不良可濕性 <半導體裝置表現之評估> <藉由使用各料電性接合材料製備提供㈣鍵(把電 他電子裝置連接成鏈，daisy chain)的TEG(測試儀器 32 201244867 集團），及半導體裝置之傳導狀態以傳導測試器檢測，且根 據以下準則評估，作為半導體裝置表現之評估。 [評估準則] 佳：充分傳導 一般：傳導有些低劣（處於實際上可使用程度） 不良：不良傳導 33 201244867 【ί_Ι5 實例 tn 1 12.5 12.5 〇 1 一般| Ό m ON 1 oi CN 〇 1 一般 一般 冢 1 in vn 〇 1 寸 in 00 1 in 〇 1 m § 1 in 〇 1 (N § 1 in 〇 1 § 1 〇 〇 ο 1 Sn-58Bi鍍覆的Cu顆粒 Ag錢覆的Cu顆粒 Sn-58Bi 顆粒(139°C) 17Sn-58Bi-25In 顆粒(79°C ) 金屬組份小計(質量％) 環氧化物為主的助熔劑材料 松香為主的助溶劑材料 xD ί寒 亨:发 - 當電子組件已被封裝時，其 表現之評估 半導體裝置之表現 高熔點金屬顆粒 中熔點金屬顆粒 低熔點金屬顆粒 評估 34 201244867 【<cn_i5 實例 CN 产— 00 1 1 1 in 1 1 Ο Η r-H 00 1 1 1 1 〇 I Ο r-H yn CO 1 1 t in 1 〇 r—Η I 1 1 in 00 in I 1 Ο r—Η I 00 1 00 1 ir； 1 in 1 Ο I Sn-58Bi鍍覆的Cu顆粒 Ag鍍覆的Cu顆粒 Au鑛覆的Cu顆粒 Sn-58Bi 顆粒(139°C) Sn-57Bi-lAg 顆粒(139°C) 17Sn-58Bi-25In 顆粒(79°C) 12Sn-41Bi-47In 顆粒(59°C) 金屬組份小計(質量％) 環氧化物為主的助溶劑材料 松香為主的助炫劑材料 篇電性接合材料已被供應時，其表現之 〇3 ι^ιΰ <0® 半導體裝置之表現 高溶點金屬顆粒 中熔點金屬顆粒 低熔點金屬顆粒 評估 35 201244867 【ΐι-Hs m 卜 o 1 i r_ Η 〇 i—Η o ο in ο 〇 ι—Η 一般 一般 们 > 1 i r-H Ο 一般 一般 一般 寸 yn ro ψ i Τ' 1 < Ο m 〇 ι Η ο 平均顆粒大小(μπι) 平均厚度(μπι) 平均厚度(μπι) 金屬組份小計(質量％) 環氧化物為主的助炼劑材料 Η tj 埤 ΙΪβ5 — <0® 當電子組件已被封裝時，其表現之評估 半導體裝置之表現 高熔點金屬顆粒(Cu顆粒） 中熔點金屬層(Sn-58Si) 低熔點金屬層（17Sn-5 8Bi-25In) 複層金屬顆粒 評估 36 201244867 【<tIs 比較例 cn 1 Ο Ο 〇 r ·Η 不良 (N 00 in 1 Ο ι—Η 不良 不良 m 00 1 〇 Ο r-H 不良 不良 Sn-58Bi鍍覆的Cu顆粒 Sn-58Bi 顆粒(139°C) 17Sn-58Bi-25In 顆粒(79°c) 金屬組份小計(質量％) 環氧化物為主的助熔劑材料 Me \f>(T〇 rplti <0® 當電子組件已被封裝時，其表現之評估 半導體裝置之表現 高溶點金屬顆粒 中溶點金屬顆粒 低熔點金屬顆粒 評估 37 201244867 (實例18) 實例18之製造半導體裝置的方法將將參考第9圖說明 於下。 (1)實例1之導電性接合材料2 0藉由網板印刷被列印（供 應）於其上備置有直徑3〇μιη之Cu電極7的基材（底膜基材）6 (2)經列印之導電性接合材料2〇k1〇〇°c下加熱5分鐘 (初級熱處理）’且經加熱之導電性接合材料2〇沉積（預塗覆） 於基材電極7上。 (3)備置有Au凸塊9之Si晶片8被排列於其上有導電性接 合材料20沉積之基材上，且該裝配體在15〇充加熱3〇分鐘 (第二級熱處理）。藉此，備置有如凸塊9之&晶片8面朝下安 裝於基材6上。 ()未充滿材料(環氧化物為主的熱固性材料)32被注入 基材6與Si晶片8之間。 電性接Γΐί滿㈣32於15G°C進㈣化製程(其作用為導 =:2。_的固化方式购、時3。分鐘，且 或=片8。於此時’導電性接合材料2。之炫點為25。。。 藉由以上步驟製造第9圖 的半導體裝置。 所不之其中封裝有倒裝晶片 (實例19) 貫例19之製造半導體裝 於下。 置的方法將將參考第9圖說明 38 201244867 (1) 貫例13之導電性接合材料2〇藉由網板印刷被列印 (仏應）於其上備置有直徑25μηι之Au鍍覆電極7的基材（底膜 基材）6上。 (2) 經列印之導電性接合材料20於100。(：下加熱5秒（初 級熱處理），且經加熱之導電性接合材料20沉積（預塗覆）於 基材電極7上。 (3) 備置有Au凸塊9之Si晶片8被排列於其上有導電性接 合材料20沉積之基材上，且該裝配體在15〇t加熱30分鐘 (第二級熱處理）。藉此，備置有Au凸塊9之Si晶片8面朝下安 裝於基材6上。 (4) 未充滿材料（環氧化物為主的熱固性材料)32被注入 基材6與Si晶片8之間。 (5) 該未充滿材料32於150°C進行固化製程（其作用為導 電性接合材料20熔點改變的固化方式）達1小時30分鐘，且 封裝Si晶片8。於此時，導電性接合材料20之熔點為250°C 或更高。 藉由以上步驟製造第9圖所示之其中封裝有倒裝晶片 的半導體裝置。 (實例20) 實例20之製造半導體裝置的方法將將參考第1〇圖說明 於下。 (1)實例1之導電性接合材料2〇以橡膠滾軸(金屬橡膠滚 軸）注入鑽孔裝埋鑽模(矽基材)31之凹陷部中，備置有直徑 25μιη之Au凸塊9的Si晶片8被壓至材料，且於100°C加熱該 39 201244867 裝配體達5秒(初級減理此，導電性接合材料2〇沉積 (預塗覆)於Si晶片8之Au凸塊9上。 ()備置有Au凸塊(其_L沉積著導電性接合材料抑的义 日曰片8破女排於其上備置著直徑3〇^m之Cu電極7的基材6 上，且該裝配體在⑽加熱30分鐘（第二級熱處理）。藉此， 備置有Au凸塊9之&晶片8面朝下安裝於基材（底膜基卵 上。 (3) 未充滿材料(環氧化物為主的熱固性材料)32被注入 基材6與Si晶片8之間。 (4) 該未充滿㈣册丨咐進·化製程(其作用為導 電性接合材料20炼點改變的固化方式）達h、_分鐘，且 封裝Si晶片8。於此時’導電性接合材料2()之魅為2贼 或更高。 藉由以上步驟製造第10圖所示之其中封裝有倒裝晶片 的半導體裝置。 (實例21) 實例21之製造半導體裝置的方法將將參考第丨丨圖說明 於下。 (1) 實例13之導電性接合材料3〇藉由網板印刷被列印 (供應)於其上備置有一對Cu電極33之基材（底膜基材）上。 (2) 於100°C下加熱經列印之導電性接合材料3〇達5秒 (初級熱處理）’且經加熱之導電性接合材料3〇沉積（預塗覆） 於基材之電極33上。 (3) 尺寸〇.6mm X 0.3mm之方形〇63〇SMD晶片8被排列 40 201244867 5亥對Cu電極33之間，且在150°C加熱該裝配體3〇分鐘（第二 級熱處理）。藉此，將SMD晶片8安裝於基材6上。於此時， 導電性接合材料之熔點為250。(：或更高。 藉由以上步驟製造第11圖所示之其中封裝有SMD晶片 的半導體裝置。 關於包括實例1至21之上述實施例，以下額外的請求項將會 進一步揭露。 此處§己載之所有實例及條件語言係為了教導的目的， 以幫助讀者了解本發明及發明者所貢獻的概念而增進本技 術領域，而且應被解釋為不受該等特別記載之實例及條件 所限制，而且此等實例於說明書中的編排整理也與本發明 優勢及劣勢之描繪無關。雖然本發明實施例已經詳細地說 明’應了解的是，就此處說明所為之各種改變、取代及修 改並未脫離本發明之精神與範圍。 【圖式簡單說^明】 第1圖為顯示傳統導電性接合材料及導電性接合材料 已經進行加熱後之狀態的簡圖； 第2圖顯示傳統導電性接合材料被供應至基材之電 極’及電極被接合至電子組件之端子之狀態的簡圖； 第3圖顯示傳統導電性接合材料被加熱且轉印至電子 組件上，及電子組件被接合至基材之電極的簡圖； 第4圖顯示本發明導電性接合材料，及導電性接合材料 已經進行加熱後之狀態的簡圖； 第5圖顯示本發明導電性接合材料之另—實例的簡圖；
S 41 201244867 第6A圖為經第二級熱處理後，導電性接合材料中之Bi 及 Sn的相圖（phase diagram); 第6B圖為經第二級熱處理後，導電性接合材料中Cu及 Sn的相圖； 第6C圖為經第二級熱處理後，導電性接合材料中Cu及 In的相圖， 第7圖顯示本發明接合導體之方法之一實例的簡圖； 第8圖顯示本發明接合導體之方法之另一實例的簡 圖；及 第9圖顯示製造實例18及19之半導體裝置之方法的簡 圖； 第10圖顯示製造實例20之半導體裝置之方法的簡圖； 及 第11圖顯示製造實例21之半導體裝置之方法的簡圖。 【主要元件符號說明】 1...高熔點金屬顆粒 20...導電性接合材料 2...低熔點金屬顆粒 21...高熔點金屬顆粒 3...助熔劑組份 22...中熔點金屬顆粒 4...Bi-隔離層 23...低熔點金屬顆粒 5...介金屬化合物 24...介金屬化合物 6...基材 25...介金屬化合物 7...電極 30...導電性接合材料 8...電子組件 31...鑽模 9...端子 32...未充滿材料 10...低熔點金屬熔膏 33...電極 42

Claims (1)

  1. 201244867 七、申請專利範圍： 1. 一種導電性接合材料，包括： 由高熔點金屬顆粒、中熔點金屬顆粒及低熔點金屬 顆粒形成之金屬組份， 高熔點金屬顆粒具有第一熔點或更高； 中熔點金屬顆粒具有第二熔點，其為第一溫度或更 高且第二溫度或更低，該第二溫度低於該第一熔點且高 於該第一溫度；及 低熔點金屬顆粒具有第三熔點或更低，該第三熔點 低於該第一溫度。 2. 如申請專利範圍第1項之導電性接合材料， 其中該金屬組份之高熔點金屬顆粒之熔點為150°C 或更高； 該中熔點金屬顆粒之熔點為80°C或更高且139°C或 更低；及 該低熔點金屬顆粒之熔點為7 9 °C或更低。 3. 如申請專利範圍第2項之導電性接合材料，其中該金屬 組份之高熔點金屬顆粒含量為80質量％至90質量％，該 金屬組份之中熔點金屬顆粒含量為5質量％至15質量 %，及該金屬組份之低熔點金屬顆粒含量為5質量％至15 質量％。 4. 如申請專利範圍第2項之導電性接合材料，其中該高熔 點金屬顆粒係選自由Au顆粒、Ag顆粒、Cu顆粒、Au鑛 覆的Cu顆粒、Sn-Bi鍍覆的Cu顆粒及Ag鍍覆的Cu顆粒組 43 201244867 成之群組的至少一顆粒。 5. 如申請專利範圍第2項之導電性接合材料，其中該高熔 點金屬顆粒係該Au鍍覆的Cu顆粒，該Sn-Bi鍍覆的Cu顆 粒及該Ag鍍覆的Cu顆粒之任一者。 6. 如申請專利範圍第2項之導電性接合材料，其中該低熔 點金屬顆粒為Sn-Bi-In顆粒及該中熔點金屬顆粒為 Sn-Bi顆粒。 7. 如申請專利範圍第2至6項中任一項之導電性接合材 料’其中該金屬組份為複層金屬顆粒，其依序具有該中 熔點金屬顆粒形成之中熔點金屬層及由該低熔點金屬 顆粒形成之低熔點金屬層，且該低熔點金屬顆粒形成於 s亥咼溶點金屬顆粒之表面上。 8. 如申請專利範圍第7項之導電性接合材料，其中該高熔 點金屬顆粒之平均顆粒大小為4〇μηι或更少，該中熔點 金屬層之平均厚度為1μηι或更多，及該低熔點金屬層之 平均厚度為Ιμηι或更多。 9·如申請專利範圍第2項之導電性接合材料，其中該金屬 組份之含量關於該導電性接合材料為5〇質量％至95質 量％ 〇 1〇_如u利範圍第i項之導電性接合材料’更包括一助 炼劑組份，其至少包括環氧化物為主的祕劑材料及松 香為主的助熔劑材料之任一者。 11.如申請專利範圍第1G項之導電性接合材料，其中該助熔 劑組伤之含量關於該導電性接合材料為5質量％至50質 44 201244867 量％。 12. —種接合導體之方法，包括： 供應該導電性接合材料至基材之電極及電子組件 之端子的任一者，該導電性接合材料包括： 由高熔點金屬顆粒、中熔點金屬顆粒及低熔點 金屬顆粒形成之金屬組份， 高熔點金屬顆粒之熔點為150°C或更高； 中熔點金屬顆粒之熔點為80°C或更高且139°C 或更低；及 低熔點金屬顆粒之熔點為79°C或更低；及 在低於該中熔點金屬顆粒之熔點的溫度下加熱該 經供應之導電性接合材料，及 沉積該經加熱之材料至該基材之電極及電子組件 之端子的任一者上。 13. 如申請專利範圍第12項之接合導體的方法，更包括： 加熱沉積於該基材之電極及電子組件之端子的任 一者上的該導電性接合材料，及接合該基材至該電子組 件。 14. 如申請專利範圍第13項之接合導體的方法，其中於該中 熔點金屬顆粒之熔點或更高且150°C或更低之溫度下加 熱該導電性接合材料。 15. —種製造具有基材及電子組件之半導體裝置的方法，該 方法包括： 供應導電性接合材料至該基材之電極及該電子組 45 201244867 件之端子的任一者，該導電性接合材料包括： 由高熔點金屬顆粒、中熔點金屬顆粒及低熔點 金屬顆粒形成之金屬組份，該高熔點金屬顆粒之熔 點為150°C或更高； 該中熔點金屬顆粒之熔點為80°C或更高且139 °0：或更低；及 該低熔點金屬顆粒之熔點為79°C或更低；及 在低於該中熔點金屬顆粒之熔點的溫度下加熱該 經供應之導電性接合材料，及 沉積該經加熱之材料至該基材之電極及該電子組 件之端子的任一者上。 46
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