TWI334642B - - Google Patents

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Publication number
TWI334642B
TWI334642B TW098134952A TW98134952A TWI334642B TW I334642 B TWI334642 B TW I334642B TW 098134952 A TW098134952 A TW 098134952A TW 98134952 A TW98134952 A TW 98134952A TW I334642 B TWI334642 B TW I334642B
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TW
Taiwan
Prior art keywords
core material
copper
copper wire
ball
wire
Prior art date
Application number
TW098134952A
Other languages
English (en)
Other versions
TW201036131A (en
Inventor
Tsutomu Yamashita
Hideyuki Akimoto
Takeshi Kuwahara
Junichi Okazaki
Original Assignee
Tanaka Electronics Ind
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=41314369&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=TWI334642(B) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Tanaka Electronics Ind filed Critical Tanaka Electronics Ind
Publication of TW201036131A publication Critical patent/TW201036131A/zh
Application granted granted Critical
Publication of TWI334642B publication Critical patent/TWI334642B/zh

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    • 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
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/302—Cu as the principal constituent
    • 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
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0255—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in welding
    • B23K35/0261—Rods, electrodes, wires
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Description

1334642 六、發明說明： 【發明所屬之技術領域】 本發明是關於一種以球形接合連接半導體元件上的電 極與電路配線基板的配線所利用的被覆銅線。 【先前技術】
現在作爲以球接合進行接合半導體元件上的電極與外 部端子之間的接合線，主要使用著線徑20〜50 μιη左右的 金線製造。在該金線的接合一般爲超音波倂用熱壓接方 式，使用於通用接合裝置，將線徑其內部而使用於連接的 毛細管工模等。第1接合，爲以電弧入熱進行加熱熔融線 前端，而藉由表面張力進行形成球之後，將該球部壓接接 合於加熱在150〜300 °C的範圍的半導體元件的電極上。之 後，以毛細管工模，將所定迴路描繪於線之後在第2接 合，將線直接藉由超音波壓接接合經引拉撕裂於外部導線 側。 近年來，半導體安裝的構造材料連接技術等是急速地多 樣化’例如，在安裝構造中，除了使用現行的導線架的QFP (Quad Flat Packaging)以外，還有使用基板，聚醯亞胺帶等的 BGA(Ball Grid Array)、CSP(Chip Scale Packlaging)等的 新形態被實用化，被要求更提昇迴路性、接合性、量產使 用性等的接合線。 成爲接合線的接合對方的材質也多樣化，而在矽基板 上的配線’電極材料，除了習用的A1合金以外，還有適 -5- 1334642 用於更微細配線的Cu被實用化。又，在導線架上施加鏟 銀、鍍鈀等’又，在樹脂基板，帶等上面，施加Cu配 線’而在其上面施加金等的貴金屬元素及其合金的膜的情 形。因應於此些各種接合對方，被要求提昇線的接合性， 接合部信賴性。 替代以往的高純度4N系（純度爲99.99質量％以上）的 金線’起初爲考慮利用高純度3 N〜6 N系（純度9 9.9〜純度 99.9 9 99質量％以上）的銅線。但是銅線是容易氧化的缺 點。來自線接合技術的要求，在形成球時形成真球性良好 的球’而在其球部與電極之接合部作成得到充分的接合強 度很重要’惟尤其是在第1接合以形成熔融球時，熔融銅 是捲入大氣中的氧氣而氧化固化之故，因而球會變硬，有 把半導體晶片破裂的致命性缺陷。所以，高純度3 N〜6N 系的銅線是不得不使用在還原性環境，球形接合用被覆銅 線對於半導體裝置的應用範圍是被限定者。 另一方面，在Cu或Cu-Sn等的芯材外周設置0.002〜 0·5μηι的Pd，Pd-Ni、Pd-Co等的被覆層，而可改良耐蝕 性及強度的設計被提案（參照專利文獻1)。又，作爲防止 銅接合線的表面氧化的方法，以金、銀、白金、鈀、鎳、 鈷、鉻、鈦等的貴金屬或耐蝕性金屬來被覆銅的接合線被 提案（參照專利文獻2〜專利文獻4)。 專利文獻1 :曰本實開昭60-160554號公報 專利文獻2:日本特開昭62-97360號公報 專利文獻3:日本特開昭2005-167020號公報 1334642 的銅所含有的磷（p)的脫氧效果，利用在表皮層近旁濃縮 磷（p)，分斷消去芯材的銅的氧化部分，而在形成熔融球 時，可作成不會有芯材的銅的氧化部分的影響。 【實施方式】
本發明的被覆銅線的一種爲芯材由銅（Cu)-l〜500質 量ppm磷（P)合金所構成。欲含有1〜500質量ppm的憐 (P)，爲了分解除去藉由磷（P)的脫氧作用分解除去形成於 芯材的露出部的銅（Cu)的氧化膜。存在於熔融球表面上的 磷（P)是藉由氧化之際進行昇華。此時，磷（P)是藉由在芯 材表皮層近旁形成濃縮層，可抑制並延遲發生形成於芯材 表面的氧化銅，而與後述的金（A u)表皮層相輔相成而可將 銅（Cu)表面的氧化膜厚抑制成最低限度。 本發明的被覆銅線的一種爲芯材由銅（Cu)-l〜80質量 ppm隣（P)合金所構成。即使磷（P)是微量，將銅線的再結 晶溫度予以上昇，也具有將線本體的強度變硬的效果。 又，銅（Cu)的純度變愈高，則雜質及於磷（P)的雜質影響之 故，因此磷（P)的添加量較少就可以。 本發明的被覆銅線的一種爲芯材由銅（Cu)-200〜400 質量ppm磷（P)合金所構成。即使磷（P)以外的雜質元素存 在數十質量PPm左右，也可延遲抑制發生形成於芯材表面 的氧化銅。 但是，在芯材的銅（Cu)-磷（P)合金，磷（P)以外的雜質 元素是最好不含有較佳。此雜質元素與大氣中的氧氣反應 -9- 1334642 而形成氧化’把第1接合之際的熔融的銅球會變硬。相反 地’雜質元素愈少’即使將磷（p)的含有量增加至數百質 量ppm左右’也具有熔融的銅球不容易變硬的趨勢。具體 而言’磷（P)以外的芯材成分爲純度99.999質量％以上的 銅（Cu)較佳而純度99.9999質量％以上的銅（Cu)更佳。在 此’所謂「純度99.999質量％以上」，是指磷（P)及銅（cu) 以外的金屬的雜質爲不足0.001質量％的情形，而除掉存 在於銅（Cu)中的氧氣或氮氣或碳等的氣體狀元素者。 兩種被覆層中的中間層是由鈀（Pd)或白金（Pt)或鈀（Pd) 與白金（Pt)的合金所構成。鈀（Pd)的融點（1554 °C)及白金 (Pt)的融點（1770 °C)’都比銅（Cu)的融點（約1085度）還要 高。所以芯材的銅（C u)形成球狀的熔融球之最初階段，鈀 (Pd)或白金（Pt)成爲薄皮’或是鈀（Pd)與白金（Pt)的合金成 爲薄皮，而可防止並延遲來自熔融球的側面的氧化。 中間層的厚度是0.005〜〇.2μηι較佳，而〇.〇1〜Ο.ΐμπι 更佳。不足〇.〇〇5μιη的情形，作爲薄皮的氧化延遲效果有 未充分的趨勢’而超過〇·2μιη，則會降低銅（Cu)的純度， 而藉由銅球的合金化’有容易產生晶片破裂的趨勢。 但是’紀（Pd)或白金（Pt)的薄皮或絶（Pd)與白金（pt)的 合金的薄皮，是會被吸收在熔融銅球內部之故，因而，該 薄皮爲芯材的露出部，亦即’不會完全覆蓋到以電弧放電 形成於銅球的則端部的銅（Cu)的氧化膜。而且，最外層的 融點變更高’在電弧放電’成爲需要更大的能量之故，因 而線端面的氧化被促進’如此在芯材的銅（C u)形成熔融球 -10 - 1334642 中間層的鈀（Pd)或白金（pt)及表皮層的金（Au)，是即 使形成熔融球也不會氧化的元素。又，此些元素是如銀 (Ag)地不會與大氣中的硫（S)反應之故，因而對芯材的銅 (Cu)不會有不良影響。而且，鈀（Pd)或白金（Pt)的元素， 是對於含有於芯材的銅（Cu)的磷（P)也不會有不良影響，而 表皮層的金（Au)是與芯材的銅（Cu)完全地固溶。結果，在 第一接合中被熔融的銅球在凝固之過程，及於銅（Cu)球的 磷（P)的脫氧作用是不管有無被覆層，對於半導體晶片爲 同等。又，兩種被覆層的中間層與表皮層爲以貴金屬'所形 成之故，因而在第二接合的超音波接合之際，比芯材的銅 (Cu)直接接合於導線架。 藉由被覆層還可防止芯材的銅 (Cu)的氧化，而有提昇接合力的效果。 擬將金（Au)的表皮層及鈀（Pd)或白金（Pt)等的中間層 形成於芯材的表面，使用電鍍法較佳。電鍍法可能爲電解 電鑛、無電解電鎪、熔融鹽電鎪等。被稱爲觸擊電鍍，薄 鍍的可得到薄膜厚的電解電鍍是電鑛速度快速，與底質的 密接性良好之故，因而進行電解電鍍時較佳。使用於無電 解電鍍溶液是被分類成置換型與還原型，如金（Au)的表皮 層地膜薄時，則僅置換型電鍍就充分，惟如中間層的紀 (Pd)或白金（Pt).地形成某種程度厚的膜時，則在置換型電 鑛之後施以自觸媒型的®原型電鑛較有效。無電解法是裝 置等較簡便較容易，惟比電解法較費時。在電鍍浴，含有 磷酸或磷酸鹽較佳。藉由金（Au)或鈀（Pd)或白金（Pt)析出 時捲進磷（P)，在第一接合當芯材的.銅（Cu)溶融時，可將溶 -12- 133.4642 融銅（Cu)的球表面的磷（P)的脫氧效果更優異地發揮的效 果。具體而言，具有分解除去形成於芯材的露出部的銅 (Cu)的氧化膜的效果，又具有更延遲熔融銅（Cu)的氧化所 用的效果。
一方面，在物理性蒸鍍法，可利用濺鍍法，離子植入 法，真空蒸鑛等的物理吸附，及電漿CVD等的化學吸 咐。任一都是乾式，未考慮成本，則不需要膜形成後的洗 淨，而不會有洗淨時的表面污染等的顧慮。 針對施加電鍍或蒸鍍的階段，在粗徑的芯材形成電鍍 膜或蒸鍍膜之後，一直到目標的線徑爲止複數次沖模伸線 的手法有效。電鑛或蒸鍍的結晶組織藉由伸線加工變性成 被塑性加工的組織。較佳被覆手段是觸擊電鍍之後，在電 鍍電鍍浴中浸漬粗銅（Cu)芯線而形成中間層及表皮層的電 鍍膜之後，將此被覆銅線予以伸線而可到達至最終直徑的 手法等。必要時，進行依鈀（Pd)或白金（Pt)所致的觸擊電 鍍較佳。 表皮層形成兩種以上的金屬所成的複數層時，成爲藉 由電鍍法、蒸鏟法、熔融法等階段地形成複數不相同的金 屬層。這時候，全部形成不相同的金屬之後才進行熱處理 的方法，形成1層金屬層別地進行熱處理，依次積層的方 法等有效。 (實施例） 以下，針對於實施例加以說明。 -13- 1334642
將從含有所定量的磷（P)的純度的銅（Cu)錠經伸線加工 至500μιη的線徑的銅線作爲芯材。在其線表面施以觸擊電 鍍之後以通常方法進行電解電鍍。作爲中間層準備被覆鈀 (Pd)及/或白金（Pt)的三種類線材，而作爲表皮層將金（Au) 直接被覆於此三種類的線材。電鍍浴是使用在半導體用途 上市面販售的電鍍液電鍍浴。具體而言，鈀（Pd)是使用在 中性二硝基二氨鈀浴添加10 gW/Ι的磷酸鹽者，由白金（Pt) 是使用Pt-p鹽浴，金（Au)是使用在中性的氰化金浴添加 100 gW/Ι的磷酸鹽者。之後，將此被覆銅線沖模伸線至最 終直徑的2 5 μη!，最後除掉加之變形施以熱處理使得伸長 値成爲10%左右。最後的電鍍厚度等，是如表1。又，電 鍍厚度是以奧格電子分光法（AES : Auger election spectroscopy)進行測定。
-14- 133.4642 表1被覆銅線的各層的構造 實施例 比較例 表皮層 中間層(0內是先前所形成 芯材 Au表皮層 (jti m) Pd中間層 Pt中間層 ("m) Au中間層 (//m) Cu的純度 P含有量 (質量ppm) 1 0.007 0.02 Μ M 99.9999 10 2 0.08 Μ >*\、 0.05 並 y* w 99.9999 30 3 0.04 0.05 Μ M j\w 99.9999 20 4 0.008 Μ J\W 0.01 M /*w 99.9999 40 5 0.06 無 0.12 無 99.9999 70 6 0.02 0.08 te 组 y t、、 99.9999 100 7 0.006 /ττΤ /ι\\ 0.06 jfrrt. ΙΙΙΓ 99.9999 200 8 0.015 0.15 無 M /»、、 99.9999 400 9 0.09 ίΕΕ 0.05 無 99.9999 75 10 0.009 0.007 姐 /“、 並 /»、、 99.9999 350 11 0.12 Μ /1、、 0.22 無 99.9999 25 12 0.13 0.24 Μ Μ >*、、 99.9999 450 13 0.15 (0.15) 0.15 Μ j\w 99.9999 65 14 0.011 無 0.04 4nt m 99.999 90 15 0.07 0.14 無 Μ jw\ 99.999 280 16 0.008 Anf ιΤΤτΓ 0.013 Μ. /»>> 99.999 120 17 0.03 te yiw 0.06 並 yt\\ 99.999 250 18 0.095 0.16 Μ Μ /»w 99.999 210 19 0.006 0.02 (0.01) Μ 99.999 160 20 0.05 (0.10) 0.07 無 99.999 180 21 0.055 0.23 Μ y ι、Ν 姐 99.999 2 22 0.14 Μ '»、、 0.13 Μ y»、、 99.999 480 23 te 0.05 Arr 無 Μ 〆》、、 99.995 姐 24 Μ 0.3 Μ 姐 /t、\ 99.995 Μ y i \> 25 Μ Μ 0.01 無 99.9995 Μ 〆》、、 26 jfrrr ΙΙΙΓ Μ >1、、 0.1 姐 μ、、 99.9995 4rrT /»v? 27 0.8 Μ y»、\ •M、、 並 99.995 M '1、、 28 Μ >»、、 0.8 M /*»> (0.01) 99.995 M >»、、 29 ΛττΤ. lilt. y ι、、 並 0.1 0.005 99.995 M 30 Μ Μ /w\ Μ 99.9999 to
在接合線的連接，使用市面上販售的自動線接合線 [曰本新川股份有限公司製的超音波熱壓接線接合器 「UTC- 1 000型UTC-1 000(商品名稱）」，進行球/綴縫接 合。在氮氣環境中藉由電弧放電，將球製作於線前端，並 將其接合於矽基板上的〇·8μιη鋁（Al-0.5%Cu)電極模，又 -15- 1334642 將線另一端以頻率1/200週期，2kW進行楔形綴縫接合於 經4μιη鑛銀的200°C的導線架上。 又，第1接合的條件是如下。 (接合溫度：200°C。初期球直徑：40〜60μιη) 將試驗結果表示於表2。 在初期球形的觀察下，觀察20支接合前的球，判定 形狀是否真球’或是尺寸精度是否良否等。若異常形狀的 球有發生兩支以上，則爲不良而表示爲X記號，異形爲兩 支以下，惟球位置對於線的偏芯顯著的個數爲5個以上胃 表示爲△記號，若偏芯爲2〜4個而判斷牢用上沒有大問 題，則表示爲〇記號，而偏芯爲1個以下而尺寸精度也良 好時，球形成是良好之故，因而以◎記號表示。 在判定壓接球部的接合形狀，爲觀察500支所接合的 球，進行評價形狀的真圓性，尺寸精度等。球壓接直徑是 成爲選定線直徑的2〜3倍的範圍的條件。若來自真圓的 偏差大的向異性或橢圓狀等的不良球形狀爲5支以上，則 判定爲不良而表示X記號，若不良球形狀爲2〜4支，或是 花瓣狀等的球壓接部的外周部爲8支以上，則須改善爲 故，因而以△記號表示，若不良球形狀爲1支以下，且花 瓣狀變形爲3〜7支，則實用上判定沒有問題的位準而以 〇記號表示，若花瓣狀變形爲兩支以下，則爲良好之故， 因而以◎記號表示。 針對於熔融球的氧化，以5 0個晶片確認在球接合時 是否發生裂縫。在鹼溶解鋁（Α1)襯墊部之際所露出的矽晶 -16- 133.4642
圓發生裂縫的情形，表示其個數。 在綴縫接合的評價中’針對於超音波熱壓接於鍍銀 (Ag)的導線架的接合迴路，以牽引拉鈎垂直地引拉著其長 度從綴縫側20%的部分時計測到拉斷爲止的荷重。以+ mN 表示在5 0個的迴路計測的平均値。 在表2，表示本發明的被覆銅線的評價。 -17- 1334642 表2被覆銅線的實施評價
正球性 正圓性 晶圓損傷 綴縫拉力 全體評價 1 ◎ 〇 ◎ 89 ◎ 2 ◎ ◎ 〇 93 ◎ 3 〇 ◎ 〇 90 ◎ 4 ◎ ◎ ◎ 101 ◎ 5 〇 〇 Δ 88 〇 6 ◎ ◎ 〇 94 ◎ 7 ◎ ◎ 〇 99 ◎ 8 〇 ◎ Δ 81 〇 9 Δ 〇 〇 95 ◎ 實 10 〇 ◎ 〇 91 ◎ 施 11 Δ Δ 〇 76 Δ 例 12 Δ Δ X 63 Δ 13 Δ 〇 X 72 Δ 14 ◎ 〇 〇 86 ◎ 15 〇 〇 Δ 94 〇 16 ◎ ◎ 〇 90 ◎ 17 〇 ◎ ◎ 91 ◎ 18 Δ 〇 △ 89 〇 19 ◎ 〇 〇 93 ◎ 20 〇 〇 Δ 92 〇 21 〇 〇 Δ 72 〇 22 △ 〇 Δ 77 〇 23 Δ X X 87 X 24 X 〇 X 88 X 比 25 △ X Δ 90 X 較 26 〇 X Δ 93 X 例 27 X X 〇 74 X 28 Δ Δ X 85 X 29 △ Δ X 93 X 30 〇 X Δ 54 X
-18- 133.4642 第1被覆銅線的接合線（Au/Pd/CuP)是實施例1、3、 6、8、10、12、15、18及21，第2被覆銅線的接合線 (Au/Pt/CuP)是實施例 2、4、5、7、9、11、14、16、17 及 22，第3被覆銅線的接合線（Au/(Pt· Pd)/CviP)是實施例11 〜19及20’而將第3被覆銅線的接合線予以900 °C X20秒 鐘熱處理者[(Au/(Pt . Pd)/CuP)是相當·於實施例13。在表 1的比較例23〜30’表示未相當於本發明的申請專利範圍 φ 第的接合線的結果。 實施例 1〜4' 6、 7、 9、 10、 14、 16、 17 及 19’的接 合線確認了球部的正球性，正圓性上優異，無晶圓損傷，' ， 綴縫接合性’壓接形狀良好。此些特性是在比較例23〜30 * 的僅將未相當本發明的申請專利範圍的銅以外的元素膜形 Λ * 成於表面的Cu線並不充分。 實施例5' 8、15、18及20〜22的5〜10的接合線是 比上述實施例1〜5的接合線稍差者，惟確認了球部的正 球性，正圓性上優異，晶片損傷也少，綴縫接合性，壓接 形狀良好。 實施例1 1〜1 3的接合線是比上述實施例的接合線稍 . 差者’惟與實施例1〜5的接合線同樣地，確認了球部的 正球性，正圓性優異，及晶片損傷也少，沒有如比較例的 缺陷，楔形接合性，壓接形狀優異。又，實施例1 3的接 合線是表示與實施例11、12的接合線同樣的結果。 -19-

Claims (1)

133.4642 ff年ί β日修正木 七、申請專利範圍： J 第98 1 3 495 2號專利申請案 中文申請專利範圍修正本 民國99年8月25日修正
1. 一種球形接合用被覆銅線，屬於具有以銅（Cu)作爲 主要成分的芯材，及在該芯材上具有兩種的被覆層的球形 接合用被覆銅線，其特徵爲：上述芯材爲銅（Cu)-l〜500 質量ppm磷（P)合金所構成，且上述被覆層爲鈀（Pd)或白 金（Pt)的中間層及金（Au)的表皮層所構成。 2·—種球形接合用被覆銅線，屬於具有以銅（Cu)作爲 主要成分的芯材，及在該芯材上具有兩種的被覆層的球形 接合用被覆銅線，其特徵爲：上述芯材爲銅（Cu)-l〜80質 量ppm憐（P)合金所構成，且上述被覆層爲銷（Pd)或白金 (Pt)的中間層及金（Au)的表皮層所構成。 3. —種球形接合用被覆銅線，屬於具有以銅（Cu)作爲 主要成分的芯材，及在該芯材上具有兩種的被覆層的球形 接合用被覆銅線，其特徵爲：上述芯材爲銅（Cu)-200〜400 質量ppm磷（P)合金所構成，且上述被覆層爲鈀（P d)或白 金（Pt)的中間層及金（Au)的表皮層所構成。 4. 如申請專利範圍第1項至第3項中任一項所述的球 形接合用被覆銅線，其中，磷（P)以外的芯材的成分爲純 度99.999質量％以上的銅（Cu)。 5 .如申請專利範圍第1項至第3項中任一項所述的球 形接合用被覆銅線，其中，磷（P)以外的芯材的成分爲純 1334642 度99.9999質量％以上的銅（Cu)。 6. 如申請專利範圍第1項至第3項中任一項所述的球 形接合用被覆銅線，其中，中間層的厚度爲0.005〜〇.2μπι 者。 7. 如申請專利範圍第1項至第3項中任一項所述的球 形接合用被覆銅線，其中，中間層的厚度爲〇.〇1〜Ο.ΐμπι 者。 8 .如申請專利範圍第1項至第3項中任一項所述的球 形接合用被覆銅線，其中，表皮層的厚度爲 0.005〜 0 · 1 μηι ° 9.如申請專利範圍第1項至第3項中任一項所述的球 形接合用被覆銅線，其中，表皮層的厚度爲比中間層的厚 度還要薄者。 -2 -
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