TWI638366B - Bonding wire for semiconductor device - Google Patents

Bonding wire for semiconductor device Download PDF

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Publication number
TWI638366B
TWI638366B TW105140437A TW105140437A TWI638366B TW I638366 B TWI638366 B TW I638366B TW 105140437 A TW105140437 A TW 105140437A TW 105140437 A TW105140437 A TW 105140437A TW I638366 B TWI638366 B TW I638366B
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Taiwan
Prior art keywords
wire
bonding
core material
bonding wire
less
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Application number
TW105140437A
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English (en)
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TW201717214A (zh
Inventor
山田隆
小田大造
榛原照男
大石良
齋藤和之
宇野智裕
Original Assignee
日鐵住金新材料股份有限公司
新日鐵住金高新材料股份有限公司
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Publication of TW201717214A publication Critical patent/TW201717214A/zh
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Publication of TWI638366B publication Critical patent/TWI638366B/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • H01L24/42—Wire connectors; Manufacturing methods related thereto
    • H01L24/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • 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
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0227—Rods, wires
    • 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
    • B23K35/3013—Au 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
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    • 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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract

本發明係於具有Cu合金芯材與形成於其表面之Pd被覆層之半導體裝置用接合導線，謀求175℃~200℃之HTS中之球接合部之接合可靠性提高、與耐力比(=最大耐力/0.2%耐力)：1.1~1.6之併存。
藉由於導線中含有Ni、Zn、Rh、In、Ir、Pt之1種以上總計0.03~2質量%，而提高HTS中之球接合部之接合可靠性，進而藉由於對於接合導線之垂直於導線軸之方向之芯材剖面測定結晶方位之結果中，將導線長度方向之結晶方位中、相對於導線長度方向而角度差為15度以下的結晶方位<100>之方位比率設為50%以上，且將接合導線之垂直於導線軸之方向之芯材剖面中之平均結晶粒徑設為0.9~1.3μm，而使耐力比為1.6以下。

Description

半導體裝置用接合導線
本發明係關於一種用以將半導體元件上之電極與外部引線等電路佈線基板之佈線連接之半導體裝置用接合導線。
當前，作為於半導體元件上之電極與外部引線之間進行接合之半導體裝置用接合導線(以下，稱為「接合導線」)，主要使用線徑15~50μm左右之細線。接合導線之接合方法一般為超音波併用熱壓接方式，使用通用接合裝置、使接合導線通向其內部而用於連接之毛細管治具等。接合導線之接合製程係藉由如下操作而完成：將導線前端利用電弧輸熱(arc heat)進行加熱熔融，藉由表面張力而形成球(FAB：Free Air Ball，無空氣球)後，將該球部壓接接合(以下，稱為「球接合」)於在150~300℃之範圍內加熱過之半導體元件之電極上，繼而於形成迴路之後，將導線部壓接接合(以下，稱為「楔形接合」)於外部引線側之電極。針對作為接合導線之接合對象的半導體元件上之電極，使用在Si基板上將以Al為主體之合金成膜之電極結構，針對外部引線側之電極使用實施過鍍Ag或鍍Pd之電極結構等。
迄今為止，接合導線之材料係以Au為主流，但正以LSI(Large Scale Integration，大型積體電路)用途為中心而發展為由Cu替代。另一方面，在近年來之電動汽車及油電混合車之普及的背景下，於車載用器件用途中，對自Au代替為Cu之需求亦正在升高。
針對Cu接合導線，提出有使用高純度Cu(純度：99.99質量%以 上)而成者(例如，專利文獻1)。Cu有比Au容易氧化之缺點，而存在接合可靠性、球形成性、楔形接合性等較差之問題。作為防止Cu接合導線之表面氧化之方法，提案有將Cu芯材之表面以Au、Ag、Pt、Pd、Ni、Co、Cr、Ti等金屬進行被覆之構造(專利文獻2)。又，提出有於Cu芯材之表面被覆Pd、並將其表面以Au、Ag、Cu或該等之合金進行被覆之構造(專利文獻3)。
[先前技術文獻] [專利文獻]
[專利文獻1]日本專利特開昭61-48543號公報
[專利文獻2]日本專利特開2005-167020號公報
[專利文獻3]日本專利特開2012-36490號公報
車載用器件與一般之電子機器相比，要求嚴酷之高溫高濕環境下之接合可靠性。尤其是將導線之球部接合於電極之球接合部之接合壽命成為最大問題。
於作為半導體裝置之封裝體之塑模樹脂(環氧樹脂)中，包含矽烷偶合劑。矽烷偶合劑具有提高有機物(樹脂)與無機物(矽或金屬)之密接性之作用，故而可提高與矽基板或金屬之密接性。進而，於要求更高溫度下之可靠性之適於車載之半導體等要求較高密接性之情形時，添加「含有硫之矽烷偶合劑」。塑模樹脂所包含之硫一旦於175℃以上(例如，175℃~200℃)之條件下使用，則會游離。而且，若於175℃以上之高溫下游離之硫與Cu接觸，則Cu之腐蝕變激烈，而產生硫化物(Cu2S)或氧化物(CuO)。若於使用了Cu接合導線之半導體裝置中產生Cu之腐蝕，則尤其會導致球接合部之接合可靠性降低。
作為對170℃以上之高溫環境下之球接合部之接合可靠性進行評 價之方法，使用HTS(High Temperature Storage Test)(高溫放置試驗)。對暴露於高溫環境中之評價用之樣品，測定球接合部之電阻值之經時變化，或測定球接合部之抗剪強度(shear strength)之經時變化，藉此評價球接合部之接合壽命。近年來，於車載用之半導體裝置中，要求175℃~200℃之HTS中之球接合部之接合可靠性提高。
於本發明中，若接合導線包含選自Ni、Zn、Rh、In、Ir、Pt之至少1種以上之元素，且相對於導線整體的上述元素之濃度以總計為0.03~2質量%，則判明：球接合部之高溫環境下之接合可靠性中、175℃以上之HTS中之成績有所改善。
此處，由下述(1)式定義耐力比。
耐力比=最大耐力/0.2%耐力 (1)
於楔形接合中，接合導線變形比較厲害。若於變形時導線加工硬化，則接合後之導線變硬，其結果為，楔形接合之接合強度降低。為了維持楔形接合強度，而由上述(1)式定義之耐力比較佳為1.6以下。但是，於為了提高175℃~200℃之HTS中之球接合部之接合可靠性而使導線中含有上述元素時，耐力比增大並超過1.6。因此，引起楔形接合之接合強度降低。
本發明之目的在於提供一種半導體裝置用接合導線，其係具有Cu合金芯材與形成於其表面之Pd被覆層者，且於導線中含有選自Ni、Zn、Rh、In、Ir、Pt之至少1種以上之元素總計0.03~2質量%，且可使由(1)式定義之耐力比為1.1~1.6。
即，本發明之主旨係如下所述。
(1)一種半導體裝置用接合導線，其係具有Cu合金芯材、與形成於上述Cu合金芯材之表面之Pd被覆層者，且其特徵在於：上述接合導線包含選自Ni、Zn、Rh、In、Ir、Pt之至少1種以上 之元素，相對於導線整體之上述元素之濃度以總計為0.03~2質量%，於對於上述接合導線之垂直於導線軸之方向之芯材剖面測定結晶方位之結果中，導線長度方向之結晶方位中、相對於導線長度方向而角度差為15度以下之結晶方位<100>之方位比率為50%以上，且上述接合導線之垂直於導線軸之方向之芯材剖面中之平均結晶粒徑為0.9~1.3μm。
(2)如上述(1)之半導體裝置用接合導線，其特徵在於：由下述(1)式定義之耐力比為1.1~1.6。
耐力比=最大耐力/0.2%耐力 (1)
(3)如上述(1)或(2)之半導體裝置用接合導線，其特徵在於：上述Pd被覆層之厚度為0.015~0.150μm。
(4)如上述(1)至(3)中任一項之半導體裝置用接合導線，其特徵在於：於上述Pd被覆層上進而具有包含Au與Pd之合金表皮層。
(5)如上述(4)之半導體裝置用接合導線，其特徵在於：上述包含Au與Pd之合金表皮層之厚度為0.0005~0.050μm。
(6)如上述(1)至(5)中任一項之半導體裝置用接合導線，其特徵在於：上述接合導線包含選自Ga、Ge、As、Te、Sn、Sb、Bi、Se之至少1種以上之元素，相對於導線整體之上述元素之濃度合計為0.1~100質量ppm，Sn≦10質量ppm，Sb≦10質量ppm，Bi≦1質量ppm。
(7)如上述(1)至(6)中任一項之半導體裝置用接合導線，其特徵在於：上述接合導線進而包含選自B、P、Mg、Ca、La之至少1種以上之元素，且相對於導線整體之上述元素之濃度分別為1~100質量ppm。
(8)如上述(1)至(7)中任一項之半導體裝置用接合導線，其特徵在於：於上述接合導線之最表面存在Cu。
本發明係一種具有Cu合金芯材與形成於其表面之Pd被覆層的半導體裝置用接合導線，其藉由於導線中含有選自Ni、Zn、Rh、In、Ir、Pt之至少1種以上之元素總計0.03~2質量%，而可提高175℃~200℃之HTS中之球接合部之接合可靠性，進而藉由於對於接合導線之垂直於導線軸之方向之芯材剖面測定結晶方位之結果中，將導線長度方向之結晶方位中、相對於導線長度方向而角度差為15度以下之結晶方位<100>之方位比率設為50%以上，且將接合導線之垂直於導線軸之方向之芯材剖面中之平均結晶粒徑設為0.9~1.3μm，而可使由(1)式定義之耐力比為1.1~1.6。
如上所述，於作為半導體裝置之封裝體之塑模樹脂(環氧樹脂)中，包含矽烷偶合劑。矽烷偶合劑具有提高有機物(樹脂)與無機物(矽或金屬)之密接性之作用，故而可提高與矽基板或金屬之密接性。進而，於要求更高溫度下之可靠性之適於車載之半導體等要求較高密接性之情形時，添加「含有硫之矽烷偶合劑」。塑模樹脂所包含之硫一旦於175℃以上(例如，175℃~200℃)之條件下使用，則會游離。而且，若175℃以上之高溫下游離之硫與Cu接觸，則Cu之腐蝕激烈，而產生硫化物(Cu2S)或氧化物(CuO)。若於使用了Cu接合導線之半導體裝置中產生Cu之腐蝕，則尤其會導致球接合部之接合可靠性降低。
如上所述，近年來，於車載用之半導體裝置中，要求175℃~200℃之HTS(High Temperature Storage Test)(高溫放置試驗)中之球接合部之接合可靠性提高。
本發明係以具有Cu合金芯材、與形成於上述Cu合金芯材之表面之Pd被覆層之半導體裝置用接合導線為對象。於本發明中，藉由該接 合導線包含選自Ni、Zn、Rh、In、Ir、Pt之至少1種以上之元素，且使相對於導線整體之上述元素之濃度總計0.03~2質量%，而關於球接合部之高溫環境下之接合可靠性，175℃以上之HTS中之成績有所改善。具有該特定之構成之本發明之接合導線可改善車載用器件所要求之高溫高濕環境下之球接合部之接合可靠性。
就改善球接合部之高溫環境下之接合可靠性(尤其是175℃以上之HTS中之成績)之觀點而言，相對於導線整體之上述元素之濃度總計較佳為0.030質量%以上，更佳為0.050質量%以上，進而較佳為0.070質量%以上，0.090質量%以上，0.10質量%以上，0.15質量%以上，或0.20質量%以上。
如上所述，由下述(1)式定義耐力比。
耐力比=最大耐力/0.2%耐力 (1)
於楔形接合中，接合導線變形比較厲害。若於變形時導線加工硬化，則接合後之導線變硬，其結果為，楔形接合之接合強度降低。 為了維持良好之楔形接合強度，而由上述(1)式定義之耐力比較佳為1.6以下。但是，於為了提高175℃~200℃之HTS中之球接合部之接合可靠性，而使導線中含有Ni、Zn、Rh、In、Ir、Pt之1種以上總計0.03質量%以上，此時，耐力比增大並超過1.6。可認為，於芯材之Cu中含有上述合金成分，結果為產生耐力比之增大、即硬度之增加。因此，引起楔形接合之接合強度降低。另一方面，於欲在先前之製造方法之範圍內降低耐力比時，結果耐力比未達1.1，楔形接合性較差。
因此，對接合導線即便含有上述合金成分亦可將(1)式之耐力比保持於1.1~1.6之較佳範圍內的結晶組織進行研究。其結果發現：於將(1)式之耐力比保持於較佳範圍內時，接合導線中之芯材之結晶結構、尤其是(i)對於接合導線之垂直於導線軸之方向之芯材剖面測定結晶方位之結果中之、導線長度方向之結晶方位中、相對於導線長度方 向而角度差為15度以下的結晶方位<100>之方位比率(以下，亦簡稱為「<100>方位比率」)、與(ii)接合導線之垂直於導線軸之方向之芯材剖面中之平均結晶粒徑(以下，亦簡稱為「平均結晶粒徑」)之控制較為重要。詳細而言，瞭解到若用通常之製造方法製造接合導線，則無法同時實現<100>方位比率為50%以上、與平均結晶粒徑為0.9μm以上且1.3μm以下，其結果為耐力比未達1.1或超過1.6。很明確，相對於此，藉由如下所述般設計製造方法，而可使接合導線之垂直於導線軸之方向的芯材剖面中之導線長度方向之結晶方位中、包括相對於導線長度方向而角度差至多為15度以內之<100>之方位比率為50%以上，使接合導線之垂直於導線軸之方向之芯材剖面中之平均結晶粒徑為0.9~1.3μm，其結果為可使(1)式之耐力比為1.1~1.6。
<100>方位比率為50%以上時，伴隨楔形接合時之變形之導線之加工硬化較小，故而可使耐力比為1.6以下。然而，即便於此情形時，平均結晶粒徑未達0.9μm時，0.2%耐力亦較高(缺乏延展性)，故而耐力比未達1.1，而楔形接合性較差。於平均結晶粒徑超過1.3μm之情形時，<100>方位比率未達50%，進而0.2%耐力較低，故而可推斷耐力比超過1.6，而楔形接合性較差。
再者，即便於關於導線之結晶結構滿足上述條件之情形時，若導線中之上述元素含量過多，則耐力比仍然會增大。就實現耐力比為1.6以下，抑制接合導線之硬質化而抑制楔形接合性之降低之觀點而言，相對於導線整體之選自Ni、Zn、Rh、In、Ir、Pt的至少1種以上之元素之濃度總計較佳為2.0質量%以下，1.8質量%以下，或1.6質量%以下。
於使接合導線中含有Ni、Zn、Rh、In、Ir、Pt時，即便採用使Cu芯材中含有該等元素之方法、使該等元素覆著於Cu芯材或導線表面而含有之方法之任一者，亦可發揮上述本發明之效果。該等成分之添 加量為極微量，故而添加方法之範圍廣泛，無論用何種方法進行添加，只要包含指定之濃度範圍之成分，便顯現效果。
於本發明之接合導線中，Pd被覆層之厚度就獲得良好之FAB形狀之觀點、及進一步改善車載用器件所要求之高溫高濕環境下之球接合部之接合可靠性之觀點而言，較佳為0.015μm以上，更佳為0.02μm以上，進而較佳為0.025μm以上，0.03μm以上，0.035μm以上，0.04μm以上，0.045μm以上，或0.05μm以上。另一方面，Pd被覆層之厚度過厚，則FAB形狀亦降低，故而Pd被覆層之厚度較佳為0.150μm以下，更佳為0.140μm以下，0.130μm以下，0.120μm以下，0.110μm以下，或0.100μm以下。
對上述接合導線之Cu合金芯材、Pd被覆層之定義進行說明。Cu合金芯材與Pd被覆層之邊界係以Pd濃度為基準進行判定。將Pd濃度為50原子%之位置設為邊界，將Pd濃度為50原子%以上之區域判定為Pd被覆層，將Pd濃度未達50原子%之區域判定為Cu合金芯材。該根據之原因在於：於Pd被覆層中，若Pd濃度為50原子%以上，則自Pd被覆層之結構能獲得特性之改善效果。Pd被覆層亦可包括Pd單層之區域、Pd與Cu於導線之深度方向具有濃度梯度之區域。於Pd被覆層中，形成該具有濃度梯度之區域之理由為存在Pd與Cu之原子因製造步驟中之熱處理等而擴散之情況。於本發明中，所謂濃度梯度，係指濃度向深度方向變化之程度於每0.1μm為10mol%以上。進而，Pd被覆層亦可包含不可避免之雜質。
本發明之接合導線亦可於Pd被覆層之表面進而具有包含Au與Pd之合金表皮層。藉此，本發明之接合導線可進一步提高接合可靠性，並且可進而改善楔形接合性。
對上述接合導線之包含Au與Pd之合金表皮層之定義進行說明。包含Au與Pd之合金表皮層與Pd被覆層之邊界係以Au濃度為基準進行 判定。將Au濃度為10原子%之位置設為邊界，將Au濃度為10原子%以上之區域判定為包含Au與Pd之合金表皮層，將未達10原子%之區域判定為Pd被覆層。又，即便是Pd濃度為50原子%以上之區域，只要Au存在10原子%以上，便判定為包含Au與Pd之合金表皮層。該等之根據之原因在於：若Au濃度為上述之濃度範圍，則自Au表皮層之結構可期待特性之改善效果。包含Au與Pd之合金表皮層為Au-Pd合金，將其設為包含Au與Pd於導線之深度方向具有濃度梯度之區域的區域。於包含Au與Pd之合金表皮層中，形成該具有濃度梯度之區域之理由為Au與Pd之原子因製造步驟中之熱處理等而擴散。進而，包含Au與Pd之合金表皮層亦可包含不可避免之雜質與Cu。
於本發明之接合導線中，包含Au與Pd之合金表皮層與Pd被覆層反應，可提高包含Au與Pd之合金表皮層、Pd被覆層、Cu合金芯材之間之密接強度，而抑制楔形接合時之Pd被覆層或包含Au與Pd之合金表皮層之剝離。藉此，本發明之接合導線可進而改善楔形接合性。就獲得良好之楔形接合性之觀點而言，包含Au與Pd之合金表皮層之厚度較佳為0.0005μm以上，更佳為0.001μm以上，0.002μm以上，或0.003μm以上。就抑制偏芯、獲得良好之FAB形狀之觀點而言，包含Au與Pd之合金表皮層之厚度較佳為0.050μm以下，更佳為0.045μm以下，0.040μm以下，0.035μm以下，或0.030μm以下。再者，包含Au與Pd之合金表皮層可藉由與Pd被覆層相同之方法而形成。
本發明之接合導線較佳為進而包含選自Ga、Ge、As、Te、Sn、Sb、Bi、Se之至少1種以上之元素，且相對於導線整體之上述元素之濃度合計為0.1~100質量ppm，Sn≦10質量ppm，Sb≦10質量ppm，Bi≦1質量ppm。藉此，可進而改善車載用器件所要求之高溫高濕環境下之球接合部之接合可靠性。尤其是提高溫度為130℃、相對濕度為85%之高溫高濕環境下之球接合部之接合壽命，改善接合可靠性，故 而較佳。相對於導線整體之上述元素之濃度合計較佳為0.1質量ppm以上，更佳為0.5質量ppm以上，進而較佳為1質量ppm以上，進而更佳為1.5質量ppm以上，2質量ppm以上，2.5質量ppm以上，或3質量ppm以上。另一方面，就獲得良好之FAB形狀之觀點而言，相對於導線整體之上述元素之濃度合計較佳為100質量ppm以下，更佳為95質量ppm以下，90質量ppm以下，85質量ppm以下，或80質量ppm以下。又，於Sn濃度、Sb濃度超過10質量ppm之情形時，或於Bi濃度超過1質量ppm之情形時，FAB形狀為不良，因此藉由設為Sn≦10質量ppm、Sb≦10質量ppm、Bi≦1質量ppm，而可進一步改善FAB形狀，故而較佳。
本發明之接合導線較佳為進而包含選自B、P、Mg、Ca、La之至少1種以上之元素，且相對於導線整體之上述元素之濃度分別為1~100質量ppm。藉此，可改善高密度封裝所要求之球接合部之壓扁形狀，即改善球接合部形狀之真圓性。相對於導線整體之上述元素之濃度分別較佳為1質量ppm以上，更佳為2質量ppm以上，3質量ppm以上，4質量ppm以上，或5質量ppm以上。就抑制球之硬質化、抑制球接合時之晶片損傷(chip damage)之觀點而言，相對於導線整體之上述元素之濃度分別較佳為100質量ppm以下，更佳為95質量ppm以下，90質量ppm以下，85質量ppm以下，或80質量ppm以下。
於如本發明般Pd被覆Cu接合導線含有特定量之Ni、Zn、Rh、In、Ir、Pt之情形時，若進而於接合導線之最表面存在Cu，則有接合部中之Cu9Al4金屬間化合物之產生進而得到抑制之傾向。於Pd被覆Cu接合導線含有特定量之Ni、Zn、Rh、In、Ir、Pt之情形時，若進而於接合導線之最表面存在Cu，則藉由接合導線所包含之Ni、Zn、Rh、In、Ir、Pt與Cu之相互作用，於FAB形成時FAB表面之Pd濃化得以促進，而球接合界面之Pd濃化更顯著地顯現。藉此，可推斷由Pd濃化層 帶來之Cu與Al之相互擴散抑制效果進而變強，因Cl之作用容易腐蝕之Cu9Al4之產生量變少，球接合部之高溫高濕環境下之接合可靠性進一步提高。
於Pd被覆層之最表面存在Cu之情形時，存在若Cu之濃度為30原子%以上，則導線表面之耐硫化性降低，接合導線之使用壽命降低，故而不適於實用之情況。因此，於在Pd被覆層之最表面存在Cu之情形時，Cu之濃度較佳為未達30原子%。
又，於在Au表皮層之最表面存在Cu之情形時，存在若Cu之濃度為35原子%以上，則導線表面之耐硫化性降低，接合導線之使用壽命降低，故而不適於實用之情況。因此，於在Au表皮層之最表面存在Cu之情形時，Cu之濃度較佳為未達35原子%。
此處，所謂最表面，係指在不實施濺鍍等之狀態下，藉由歐傑電子光譜裝置對接合導線之表面進行測定之區域。
針對Pd被覆層、包含Au與Pd之合金表皮層之濃度分析，自接合導線之表面朝向深度方向一面利用濺鍍等進行切削一面進行分析之方法、或使導線剖面露出而進行線分析、點分析等之方法較為有效。該等之濃度分析所使用之解析裝置係可利用掃描型電子顯微鏡或穿透式電子顯微鏡所設置之歐傑電子光譜分析裝置、能量分散型X射線分析裝置、電子探針微量分析器等。作為使導線剖面露出之方法，可利用機械研磨、離子蝕刻法等。關於接合導線中之Ni、Zn、Rh、In、Ir、Pt等之微量分析，可利用ICP(inductively coupled plasma，感應耦合電漿)發射光譜分析裝置或ICP質譜分析裝置對將接合導線用強酸溶解而成之液進行分析，以接合導線整體所包含之元素之濃度之形式進行檢測。
(製造方法)
繼而，對本發明之實施形態之接合導線之製造方法進行說明。 接合導線係藉由如下操作而獲得：於製造芯材所使用之Cu合金之後，較細地加工成線狀，形成Pd被覆層、Au層，並進行熱處理。亦存在形成Pd被覆層、Au層之後，再次進行拉線(wire drawing)與熱處理之情況。對Cu合金芯材之製造方法、Pd被覆層、包含Au與Pd之合金表皮層之形成方法、熱處理方法詳細地進行說明。
芯材所使用之Cu合金係藉由如下操作而獲得：將作為原料之Cu與所添加之元素一起熔解，並使之凝固。熔解時，可利用電弧加熱爐、高頻加熱爐、電阻加熱爐等。為了防止來自大氣中之O2、H2等氣體之混入，而較佳為於真空氛圍或Ar或N2等惰性氛圍中進行熔解。
於Cu合金芯材之表面形成Pd被覆層、Au層之方法有電鍍法、蒸鍍法、熔融法等。電鍍法可應用電解電鍍法、無電電鍍法之任一個。於稱作預電鍍、閃熔電鍍之電解電鍍中，電鍍速度較快，與基材之密接性亦為良好。將無電電鍍所使用之溶液分類為取代型與還原型，於厚度較薄之情形時，僅利用取代型電鍍便足夠，但於厚度較厚之情形時，在取代型電鍍之後階段性地實施還原型電鍍較為有效。
於蒸鍍法中，可利用濺鍍法、離子鍍覆法、真空蒸鍍等物理吸附、與電漿CVD(Chemical Vapor Deposition，化學氣相沈積)等化學吸附。均為乾式，而無需Pd被覆層、Au層形成後之洗淨，不用擔心洗淨時之表面污染等。
藉由於Pd被覆層、Au層形成後進行熱處理，而Pd被覆層之Pd擴散至Au層中，形成包含Au與Pd之合金表皮層。亦可並非於形成Au層之後藉由熱處理形成包含Au與Pd之合金表皮層，而從最初開始便覆著包含Au與Pd之合金表皮層。
針對Pd被覆層、包含Au與Pd之合金表皮層之形成，於拉線至最終線徑後形成之手法、與形成於粗徑之Cu合金芯材之後進行複數次拉線直至成為目標線徑為止之手法之任一者均有效。於前者之以最終 線徑形成Pd被覆層、包含Au與Pd之合金表皮層之情形時，製造、品質管理等較為簡便。於後者之將Pd被覆層、包含Au與Pd之合金表皮層與拉線組合之情形時，就與Cu合金芯材之密接性提高方面而言，較為有利。作為各個形成法之具體例，可列舉：一面於電解電鍍溶液中連續地掃動導線一面於最終線徑之Cu合金芯材形成Pd被覆層、包含Au與Pd之合金表皮層之手法、或於將較粗之Cu合金芯材浸漬於電解或無電解之電鍍浴中形成Pd被覆層、包含Au與Pd之合金表皮層之後對導線進行拉伸達到最終線徑之手法等。
於形成Pd被覆層、包含Au與Pd之合金表皮層之後，存在進行熱處理之情況。藉由進行熱處理，而於包含Au與Pd之合金表皮層、Pd被覆層、Cu合金芯材之間，原子擴散而密接強度提高，故而可抑制加工過程中之包含Au與Pd之合金表皮層或Pd被覆層之剝離，就生產性提高方面而言，較為有效。為了防止來自大氣中之O2之混入，較佳為於真空氛圍或Ar或N2等惰性氛圍中進行熱處理。
藉由如上所述調整對接合導線實施之擴散熱處理或退火熱處理之條件，而芯材之Cu藉由晶界擴散、晶內擴散等而於Pd被覆層或包含Au與Pd之表皮合金層中擴散，使Cu到達至接合導線之最表面，而可使最表面存在Cu。作為用以使最表面存在Cu之熱處理，可使用如上所述般用以形成包含Au與Pd之合金表皮層之熱處理。於進行用以形成合金表皮層之熱處理時，藉由選擇熱處理溫度與時間，而可使最表面存在Cu、或不存在Cu。進而，亦可將最表面之Cu濃度調整為特定之範圍(例如，1~50原子%之範圍)。亦可藉由除合金表皮層形成時以外進行之熱處理使Cu擴散至最表面。
如上所述，於使接合導線中含有Ni、Zn、Rh、In、Ir、Pt時，即便採用使Cu芯材中含有該等元素之方法、使該等元件覆著於Cu芯材或導線表面而含有之方法之任一者，亦可發揮上述本發明之效果。關 於Ga、Ge、As、Te、Sn、Sb、Bi、Se、B、P、Mg、Ca、La，亦為同樣。
作為上述成分之添加方法，最簡便之方法為向Cu合金芯材之起始材料中添加。例如，將高純度之銅與上述成分元素原料作為起始原料進行稱量後，將其於高真空下或氮氣或氬氣等惰性氛圍下加熱而熔解，藉此製成添加有目標濃度範圍之上述成分之錠，而製成包含目標濃度之上述成分元素之起始材料。因此，於較佳之一實施形態中，本發明之接合導線之Cu合金芯材係以相對於導線整體而選自Ni、Zn、Rh、In、Ir、Pt之至少1種以上之元素之濃度總計為0.03~2質量%之方式包含上述元素。該濃度之合計之較佳數值範圍係如上所述。於另一較佳之實施形態中，本發明之接合導線之Cu合金芯材係以相對於導線整體之選自Ga、Ge、As、Te、Sn、Sb、Bi、Se之至少1種以上之元素之濃度合計為0.1~100質量ppm、且Sn≦10質量ppm、Sb≦10質量ppm、Bi≦1質量ppm之方式包含上述元素。該濃度之較佳之數值範圍係如上所述。於較佳之一實施形態中，Cu合金芯材之Cu之純度為3N以下(較佳為2N以下)。於先前之Pd被覆Cu接合導線中，就黏結性(bondability)之觀點而言，有使用高純度(4N以上)之Cu芯材而避免使用低純度之Cu芯材之傾向。含有特定元素之本發明之接合導線於如上所述般使用Cu之純度較低之Cu合金芯材之情形時，尤佳地實現車載用器件所要求之高溫高濕環境下之球接合部之接合可靠性。於另一較佳之實施形態中，本發明之接合導線之Cu合金芯材係以相對於導線整體之選自B、P、Mg、Ca、La之至少1種以上之元素之濃度分別為1~100質量ppm之方式包含上述元素。該濃度之較佳之數值範圍係如上所述。
亦可於導線製造步驟之中途，藉由使上述成分覆著於導線表面而含有。於此情形時，於導線製造步驟之何處組入均可，亦可重複進 行複數次。亦可於複數個步驟中組入。可向Pd被覆前之Cu表面添加，可向Pd被覆後之Pd表面添加，可向Au被覆後之Au表面添加，亦可於各被覆步驟中組入。作為覆著方法，可自(1)水溶液之塗佈乾燥熱處理、(2)電鍍法(濕式)、(3)蒸鍍法(乾式)選擇。
於採用水溶液之塗佈乾燥熱處理之方法之情形時，首先，利用包含上述成分元素之水溶性之化合物製備適當濃度之水溶液。藉此，可將上述成分納入至導線材料中。於導線製造步驟之何處組入均可，亦可重複進行複數次。亦可於複數個步驟中組入。可向Pd被覆前之Cu表面添加，可向Pd被覆後之Pd表面添加，可向Au被覆後之Au表面添加，亦可於各被覆步驟中組入。
於使用電鍍法(濕式)之情形時，電鍍法可應用電解電鍍法、無電電鍍法之任一者。於電解電鍍法中，除通常之電解電鍍以外，亦可應用稱作閃熔電鍍之電鍍速度較快、與基材之密接性亦良好之電鍍法。無電電鍍所使用之溶液有取代型與還原型。一般於電鍍厚度較薄之情形時使用取代型電鍍，於較厚之情形時使用還原型電鍍，但可應用任一者，只要按照欲添加之濃度進行選擇，並調整電鍍液濃度、時間即可。電解電鍍法、無電電鍍法於導線製造步驟之何處組入均可，亦可重複進行複數次。亦可於複數個步驟中組入。可向Pd被覆前之Cu表面添加，可向Pd被覆後之Pd表面添加，可向Au被覆後之Au表面添加，亦可於各被覆步驟中組入。
於蒸鍍法(乾式)中，存在濺鍍法、離子鍍覆法、真空蒸鍍法、電漿CVD等。由於為乾式，故而特長為無需預處理、後處理，亦不用擔心污染。通常蒸鍍法之問題在於目標之元素之添加速度較慢，但由於上述成分元素之添加濃度相對較低，故而就本發明之目的而言，為適合之方法之一。
各蒸鍍法於導線製造步驟之何處組入均可，亦可重複進行複數 次。亦可於複數個步驟中組入。可向Pd被覆前之Cu表面添加，可向Pd被覆後之Pd表面添加，可向Au被覆後之Au表面添加，亦可於各被覆步驟中組入。
對如下製造方法進行說明，該製造方法係用以於對於接合導線之垂直於導線軸之方向之芯材剖面測定結晶方位之結果中，將導線長度方向之結晶方位中、相對於導線長度方向而角度差為15度以下之結晶方位<100>之方位比率設為50%以上，且將接合導線之垂直於導線軸之方向之芯材剖面中之平均結晶粒徑設為0.9~1.3μm。
本發明之接合導線係於Cu合金芯材中含有Ni、Zn、Rh、In、Ir、Pt之1種以上總計0.03質量%以上，故而導線之材料強度(硬度)變高。因此，於對Cu芯線之接合導線進行拉線加工時，將拉線時之減面率設為低為5~8%之減面率。又，於拉線後之熱處理中，硬度仍然較高，故而為了軟質化至可作為接合導線使用之等級，而於600℃以上之溫度下進行熱處理。由於為較高之熱處理溫度，故而導致導線長度方向之<100>方位比率未達50%，同時芯材剖面中之平均結晶粒徑超過1.3μm，耐力比超過1.6。另一方面，若欲降低耐力比而降低熱處理溫度，則導致芯材剖面中之平均結晶粒徑未達0.9μm，耐力比未達1.1，楔形接合性較差。
相對於此，於本發明中，於使用模具之拉線時，在總模具數中之一半以上之模具中，將減面率設為10%以上，進而將拉線後之熱處理中之熱處理溫度設為低為500℃以下之溫度。其結果為，可於對於接合導線之垂直於導線軸之方向之芯材剖面測定結晶方位之結果中，將導線長度方向之結晶方位中、相對於導線長度方向而角度差為15度以下之結晶方位<100>之方位比率設為50%以上，且將接合導線之垂直於導線軸之方向之芯材剖面中之平均結晶粒徑設為0.9~1.3μm。應用最新之拉線加工技術，作為潤滑劑，將潤滑劑所包含之非離子系 界面活性劑之濃度設計為高於先前，作為模具形狀，將模具之漸近角(Approach angle)設計為較先前之角度更和緩，將模具之冷卻水溫度設定為略低於先前，藉由如上等之協同效應，而儘管使Cu合金芯材中含有Ni等成分總計0.03質量%以上而硬質化，亦能實現減面率為10%以上之拉線加工。
於測定導線剖面之結晶方位時，較佳為使用電子背散射繞射法(EBSD，Electron Backscattered Diffraction)。EBSD法具有對觀察面之結晶方位進行觀察並可圖示鄰接之測定點間之結晶方位之角度差的特徵，即便為如接合導線之細線，亦可相對較簡便地並且高精度地觀察結晶方位。關於粒徑測定，可藉由針對利用EBSD法獲得之測定結果利用裝置所裝備之解析軟體而求出。本發明所規定之結晶粒徑係對測定區域內所包含之結晶粒之等效直徑(相當於結晶粒之面積之圓之直徑；圓等效直徑)進行算術平均而得者。
本發明並不限定於上述實施形態，可於本發明之主旨之範圍內適當進行變更。
[實施例]
以下，一面表示實施例，一面對本發明之實施形態之接合導線具體地進行說明。
(樣品)
首先，對樣品之製作方法進行說明。作為芯材之原材料之Cu使用純度為99.99質量%以上、剩餘部分由不可避免之雜質構成者。Au、Pd、Ni、Zn、Rh、In、Ir、Pt使用純度為99質量%以上、剩餘部分由不可避免之雜質構成者。以導線或芯材之組成成為目標組成之方式，向芯材中調配作為添加元素之Ni、Zn、Rh、In、Ir、Pt。關於Ni、Zn、Rh、In、Ir、Pt之添加，亦能以單體進行調配，但於為單體且高熔點之元素或添加量為極微量之情形時，亦可預先製作包含添加 元素之Cu母合金，並以成為目標添加量之方式進行調配。又，於下述表3所示之本發明例中，進而含有Ga、Ge、As、Te、Sn、Sb、Bi、Se、B、P、Mg、Ca、La之1種以上。
芯材之Cu合金係藉由連續鑄造以成為數mm之線徑之方式進行製造。對所得之數mm之合金，進行拉拔加工，製作0.3~1.4mm之導線。拉線時使用市售之潤滑劑，拉線速度設為20~150m/分。為了去除導線表面之氧化膜，而於進行過利用鹽酸等進行之酸洗處理之後，以覆蓋芯材之Cu合金之整個表面之方式形成1~15μm之Pd被覆層。進而，一部分之導線係於Pd被覆層之上形成0.05~1.5μm之包含Au與Pd之合金表皮層。針對Pd被覆層、包含Au與Pd之合金表皮層之形成，使用電解電鍍法。電鍍液使用市售之半導體用電鍍液。其後，主要使用減面率為10~21%之模具進行拉線加工，進而於中途，於200~500℃下進行1至3次之熱處理，藉此將直徑加工至20μm。於加工後，以最終斷裂伸長率約為5~15%之方式進行熱處理。熱處理方法係一面連續地掃動導線一面進行，一面流入N2或Ar氣體一面進行。將導線之輸送速度設為10~90m/分，將熱處理溫度設為350~500℃，將熱處理時間設為1~10秒。
(評價方法)
關於導線中之Ni、Zn、Rh、In、Ir、Pt、Ga、Ge、As、Te、Sn、Sb、Bi、Se、B、P、Mg、Ca、La含量，利用ICP發射光譜分析裝置，以接合導線整體所包含之元素之濃度之形式進行分析。
Pd被覆層、包含Au與Pd之合金表皮層之濃度分析中，一面自接合導線之表面朝向深度方向利用濺鍍等進行切削一面實施歐傑電子光譜分析。根據所得之深度方向之濃度分佈，求出Pd被覆層厚度、包含Au與Pd之合金表皮層厚度。
關於接合導線之垂直於導線軸之方向之芯材剖面中之導線長度 方向之結晶方位中、相對於導線長度方向而角度差為15度以下之結晶方位<100>之方位比率，係利用EBSD法對觀察面(即，垂直於導線軸之方向之芯材剖面)之結晶方位進行觀察之後而算出。EBSD測定資料之解析中，利用專用軟體(TSL Solutions製造之OIM analisis等)。關於垂直於導線軸之方向之芯材剖面中之平均結晶粒徑，係利用EBSD法對觀察面之結晶方位進行觀察之後而算出。EBSD測定資料之解析中利用專用軟體(TSL Solutions製造之OIM analisis等)。結晶粒徑係對測定區域內所包含之結晶粒之等效直徑(相當於結晶粒之面積之圓之直徑；圓等效直徑)進行算術平均而得者。
關於0.2%耐力與最大耐力，係藉由將標點間距離設為100mm進行拉伸試驗而評價。作為拉伸試驗裝置，使用英斯特朗公司製造之萬能材料試驗機5542型。0.2%耐力係使用裝置所裝備之專用之軟體而算出。又，將斷裂時之負荷設為最大耐力。根據下述(1)式算出耐力比。
耐力比=最大耐力/0.2%耐力 (1)
導線接合部中之楔形接合性之評價係於BGA(Ball Grid Array，球柵陣列)基板之楔形接合部進行1000根接合，並藉由接合部之剝離之產生頻度而進行判定。所使用之BGA基板係實施過鍍Ni及鍍Au者。於本評價中，假定較通常更為嚴格之接合條件，將載置台溫度設定為較一般之設定溫度區域低之150℃。於上述之評價中，在產生11個以上不良之情形時，判斷為有問題，設為×記號，若不良為6~10個，則判斷為可進行實用但稍微有問題，設為△記號，於不良為1~5個之情形時，判斷為無問題，設為○記號，於未產生不良之情形時，判斷為優異，設為◎記號，於表1之「楔形接合性」一欄中進行記載。
高溫高濕環境或高溫環境下之球接合部之接合可靠性係製作接合可靠性評價用之樣品，進行HTS評價，並藉由球接合部之接合壽命 而進行判定。接合可靠性評價用之樣品係對在一般之金屬框架上之Si基板上將厚度0.8μm之Al-1.0%Si-0.5%Cu之合金成膜而形成之電極，使用市售之打線機進行球接合，並藉由市售之環氧樹脂進行密封而製作。球係一面將N2+5%H2氣體以流量0.4~0.6L/min流入一面形成，其大小設為33~34μm之範圍。
關於HTS評價，係使用高溫恆溫器將製作而成之接合可靠性評價用之樣品暴露於溫度200℃之高溫環境中。球接合部之接合壽命係設為每500小時實施一次球接合部之抗剪試驗而抗剪強度之值成為初期所獲得之抗剪強度之1/2的時間。高溫高濕試驗後之抗剪試驗係藉由酸處理而去除樹脂，使球接合部露出後進行。
HTS評價之抗剪試驗機使用DAGE公司製造之試驗機。抗剪強度之值係使用隨機選擇之球接合部的10處之測定值之平均值。於上述之評價中，若接合壽命為500小時以上且未達1000小時，則判斷為可進行實用但要求改善，設為△記號，若為1000小時以上且未達3000小時，則判斷為實用上無問題，設為○記號，若為3000小時以上，則判斷為尤其優異，設為◎記號。
球形成性(FAB形狀)之評價係選取進行接合前之球並進行觀察，判定球表面有無氣泡、原本為真球之球有無變形。於產生上述任一情況之情形時，判斷為不良。為了抑制熔融步驟中之氧化，球之形成係一面以流量0.5L/min吹送N2氣體一面進行。球之大小設為34μm。針對1條件，觀察50個球。觀察係使用SEM(Scanning Electronic Microscope，掃描式電子顯微鏡)。於球形成性之評價中，在產生5個以上不良之情形時，判斷為有問題，設為×記號，若不良為3~4個，則判斷為可進行實用但稍微有問題，設為△記號，於不良為1~2個之情形時，判斷為無問題，設為○記號，於未產生不良之情形時，判斷為優異，設為◎記號，於表1之「FAB形狀」一欄中進行記載。
關於溫度為130℃、相對濕度為85%之高溫高濕環境下之球接合部之接合壽命，可利用以下之HAST評價進行評價。關於HAST評價，使用不飽和型壓力鍋試驗機將製作而成之接合可靠性評價用之樣品暴露於溫度130℃、相對濕度85%之高溫高濕環境中，施加5V之偏壓。球接合部之接合壽命係設為每48小時實施一次球接合部之抗剪試驗而抗剪強度之值成為初期所獲得之抗剪強度之1/2的時間。高溫高濕試驗後之抗剪試驗係藉由酸處理去除樹脂，使球接合部露出後進行。
HAST評價之抗剪試驗機係使用DAGE公司製造之試驗機。抗剪強度之值係使用隨機選擇之球接合部的10處之測定值之平均值。於上述之評價中，若接合壽命為144小時以上且未達288小時，則判斷為實用上無問題，設為○記號，若為288小時以上且未達384小時，則判斷為優異，設為◎記號，若為384小時以上，則判斷為尤其優異，設為◎◎記號，於表1之「HAST」一欄中進行記載。
球接合部之壓扁形狀之評價係自正上方觀察進行過接合之球接合部，藉由其真圓性進行判定。接合對象係使用於Si基板上將厚度1.0μm之Al-0.5%Cu之合金成膜之電極。觀察係使用光學顯微鏡，針對1條件，觀察200處。將為與真圓之偏差較大之橢圓狀者、於變形具有各向異性者判斷為球接合部之壓扁形狀為不良。於上述之評價中，在不良為1~3個之情形時，判斷為無問題，設為○記號，於全部獲得良好之真圓性之情形時，判斷為尤其優異，設為◎記號，於表1之「壓扁形狀」一欄中進行記載。
(評價結果)
表1之本發明例1~26之接合導線具有Cu合金芯材、與形成於Cu合金芯材之表面之Pd被覆層，且Pd被覆層之厚度處於較佳範圍即0.015~0.150μm之範圍內，FAB形狀均為良好。又，接合導線包含選自Ni、Zn、Rh、In、Ir、Pt之至少1種以上之元素，相對於導線整體之上述元素之濃度合計為0.03~2質量%，因此確認HTS評價之球接合部高溫可靠性為良好。
又，關於本發明例1~26，將拉線時之減面率設為10%以上，將拉線後之熱處理中之熱處理溫度設為低為500℃以下之溫度，故而於對於接合導線之垂直於導線軸之方向之芯材剖面測定結晶方位之結果中，可將導線長度方向之結晶方位中、相對於導線長度方向而角度差為15度以下之結晶方位<100>之方位比率設為50%以上，且可將接合導線之垂直於導線軸之方向之芯材剖面中之平均結晶粒徑設為0.9~1.3μm。其結果為，儘管導線中含有Ni、Zn、Rh、In、Ir、Pt，耐力比(=最大耐力/0.2%耐力)亦均處於1.1~1.6之範圍內。因此，楔形接合性均為良好之結果。
另一方面，表2之比較例4~6中，將熱處理溫度設為高為600℃以上之溫度，因此導線長度方向之<100>方位比率未達50%。又，比較例2、7~9中，將熱處理溫度設為高為620℃以上之溫度，因此導線長度方向之<100>方位比率未達50%，並且芯材剖面中之平均結晶粒徑超過1.3μm。因此，比較例2、4~9中，耐力比均超過1.6，楔形接合性均不良。
又，比較例1、3中，將模具之減面率設為未達10%，因此芯材剖面中之平均結晶粒徑未達0.9μm，耐力比未達1.1，楔形接合性均不良。

Claims (5)

  1. 一種半導體裝置用接合導線，其係具有Cu合金芯材、與形成於上述Cu合金芯材之表面之Pd被覆層者，且其特徵在於：上述接合導線包含選自Ni、Zn、Rh、In、Ir、Pt之至少1種以上之元素，且相對於導線整體之上述元素之濃度總計為0.03質量%以上2質量%以下，其中由下述(1)式定義之耐力比為1.1以上1.6以下，耐力比=最大耐力/0.2%耐力 (1)
  2. 如請求項1之半導體裝置用接合導線，其中上述Pd被覆層之厚度為0.015μm以上0.150μm以下。
  3. 如請求項1之半導體裝置用接合導線，其中於上述Pd被覆層上進而具有包含Au與Pd之合金表皮層。
  4. 如請求項3之半導體裝置用接合導線，其中上述包含Au與Pd之合金表皮層之厚度為0.0005μm以上0.050μm以下。
  5. 如請求項1至4中任一項之半導體裝置用接合導線，其中於上述接合導線之最表面存在Cu。
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