TWI763878B - 半導體裝置用接合線 - Google Patents

半導體裝置用接合線

Info

Publication number
TWI763878B
TWI763878B TW107122893A TW107122893A TWI763878B TW I763878 B TWI763878 B TW I763878B TW 107122893 A TW107122893 A TW 107122893A TW 107122893 A TW107122893 A TW 107122893A TW I763878 B TWI763878 B TW I763878B
Authority
TW
Taiwan
Prior art keywords
wire
bonding
bonding wire
less
core material
Prior art date
Application number
TW107122893A
Other languages
English (en)
Other versions
TW201835343A (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
日商日鐵新材料股份有限公司
日商日鐵化學材料股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日商日鐵新材料股份有限公司, 日商日鐵化學材料股份有限公司 filed Critical 日商日鐵新材料股份有限公司
Publication of TW201835343A publication Critical patent/TW201835343A/zh
Application granted granted Critical
Publication of TWI763878B publication Critical patent/TWI763878B/zh

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Classifications

    • 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
    • H—ELECTRICITY
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    • 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
    • B23K35/22—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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    • B32B15/00—Layered products comprising a layer of metal
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B15/018—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of a noble metal or a noble metal alloy
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Abstract

一種半導體裝置用接合線，其係具有Cu合金芯材及形成於上述Cu合金芯材表面之Pd被覆層者，且其特徵在於：上述接合線包含賦予高溫環境下之連接可靠性之元素，下述(1)式所定義之耐力比為1.1～1.6。 耐力比＝最大耐力/0.2%耐力 (1)

Description

半導體裝置用接合線
本發明係關於一種半導體裝置用接合線，其係用於將半導體元件上之電極與外部導線等電路配線基板之配線連接。
目前，作為將半導體元件上之電極與外部導線之間接合之半導體裝置用接合線(以下稱為「接合線」)，主要使用線徑15～50 μm左右之細線。接合線之接合方法通常為超音波併用熱壓接方式，可使用通用接合裝置、使接合線通過其內部而用於連接之毛細工具等。接合線之接合製程係藉由如下方式完成：利用電弧熱輸入將線頂端加熱熔融，藉由表面張力而形成球(FAB：Free Air Ball)後，將該球部加壓接合(以下稱為「球接合」)於在150～300℃之範圍內經加熱之半導體元件之電極上，繼而形成迴路後，將線部加壓接合(以下稱為「楔接合」)於外部導線側之電極上。關於作為接合線之接合對象的半導體元件上之電極，可使用將以Al作為主體之合金成膜於Si基板上之電極結構，關於外部導線側之電極，可使用實施有鍍Ag或鍍Pd之電極結構等。 迄今為止，接合線之材料係以Au為主流，但以LSI(Large Scale Integration，大規模積體電路)用途作為中心而逐步替換為Cu。另一方面，以近年來之電動汽車或油電混合車之普及為背景，於汽車用元件用途中，對由Au替換為Cu之需求亦不斷提高。 關於Cu接合線，已提出有使用高純度Cu(純度：99.99質量%以上)者(例如專利文獻1)。與Au相比，Cu有容易被氧化之缺點，存在接合可靠性、球形成性、楔接合性等較差之問題。作為防止Cu接合線之表面氧化之方法，提出有以Au、Ag、Pt、Pd、Ni、Co、Cr、Ti等金屬將Cu芯材之表面被覆之結構(專利文獻2)。又，提出有於Cu芯材之表面被覆Pd並以Au、Ag、Cu或該等之合金將其表面被覆之結構(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
[發明所欲解決之問題] 與通常之電子機器相比，汽車用元件需求嚴酷之高溫高濕環境下之接合可靠性。尤其是將線之球部接合於電極上之球接合部之接合壽命成為最大問題。 作為對高溫高濕環境下之球接合部之接合可靠性進行評價之具代表性之評價方法，有HAST(Highly Accelerated Temperature and Humidity Stress Test，高溫高濕環境暴露試驗)。於利用HAST對球接合部之接合可靠性進行評價之情形時，將評價用之球接合部暴露於溫度為130℃、相對濕度為85%之高溫高濕環境下，測定接合部的電阻值之經時變化，或者測定球接合部之剪切強度之經時變化，藉此對球接合部之接合壽命進行評價。 又，作為對170℃以上之高溫環境下之球接合部的接合可靠性進行評價之手段，使用HTS(High Temperature Storage Test，高溫放置試驗)。於藉由HTS對球接合部之接合可靠性進行評價之情形時，對於暴露於高溫環境下之評價用樣品，測定球接合部之電阻值之經時變化，或者測定球接合部之剪切強度之經時變化，藉此對球接合部之接合壽命進行評價。 根據本發明者等人之研究判明，於接合線包含例如Ni、Zn、Rh、In、Ir、Pt等賦予高溫環境下之連接可靠性的元素之情形時，與不包含該元素者相比，130℃以上之高溫環境下之球接合部之接合可靠性提昇。另一方面，於楔接合中，接合線劇烈地變形。若於變形時線加工硬化，則接合後之線變硬，其結果，楔接合之接合強度下降。於接合線中含有上述元素時，根據其含量而存在如下情況：於楔接合中，接合線劇烈地變形，於變形時線加工硬化，由此接合後之線變硬，其結果，楔接合之接合強度下降。 本發明之目的在於提供一種半導體裝置用接合線，其係具有Cu合金芯材及形成於其表面之Pd被覆層者，且可兼顧高溫下之球接合部的接合可靠性之提昇與楔接合性。 [解決問題之手段] 本發明者為了解決上述問題而進行了潛心研究，結果獲得如下見解：藉由在接合線中含有賦予高溫環境下之連接可靠性之元素，並且將下述式(1)所定義之耐力比設為1.1～1.6，可兼顧高溫下之球接合部的接合可靠性之提昇與楔接合性。本發明係基於該新穎之見解而成者。 耐力比＝最大耐力/0.2%耐力 (1) 即，本發明之主旨如下所述。 [1]一種半導體裝置用接合線，其係具有Cu合金芯材及形成於上述Cu合金芯材之表面之Pd被覆層者，且其特徵在於：上述接合線包含賦予高溫環境下之連接可靠性之元素，下述(1)式所定義之耐力比為1.1～1.6。 耐力比＝最大耐力/0.2%耐力 (1) [2]如上述[1]所記載之半導體裝置用接合線，其特徵在於：上述Pd被覆層之厚度為0.015～0.150 μm。 [3]如上述[1]或[2]所記載之半導體裝置用接合線，其特徵在於：於上述Pd被覆層上進而具有包含Au及Pd之合金表皮層。 [4]如上述[3]所記載之半導體裝置用接合線，其特徵在於：上述包含Au及Pd之合金表皮層之厚度為0.050 μm以下。 [5]如上述[1]至[4]中任一項所記載之半導體裝置用接合線，其特徵在於：上述接合線包含選自Ni、Zn、Rh、In、Ir、Pt中之至少1種以上之元素，上述元素相對於線整體之濃度總計為0.011～2質量%。 [6]如上述[1]至[5]中任一項所記載之半導體裝置用接合線，其特徵在於：上述接合線包含選自Ga、Ge中之1種以上之元素，上述元素相對於線整體之濃度合計為0.011～1.5質量%。 [7]如上述[1]至[6]中任一項所記載之半導體裝置用接合線，其特徵在於：上述接合線包含選自As、Te、Sn、Sb、Bi、Se中之至少1種以上之元素，上述元素相對於線整體之濃度合計為0.1～100質量ppm，Sn≦10質量ppm、Sb≦10質量ppm、Bi≦1質量ppm。 [8]如上述[1]至[7]中任一項所記載之半導體裝置用接合線，其特徵在於：上述接合線進而包含選自B、P、Mg、Ca、La中之至少1種以上之元素，上述元素相對於線整體之濃度分別為1～200質量ppm。 [9]如上述[1]至[8]中任一項所記載之半導體裝置用接合線，其特徵在於：於上述接合線之最表面存在Cu。 [發明之效果] 根據本發明，可提供一種半導體裝置用接合線，其係具有Cu合金芯材及形成於其表面之Pd被覆層者，且可兼顧高溫下之球接合部的接合可靠性之提昇與楔接合性。
本發明之半導體裝置用接合線具有Cu合金芯材及形成於上述Cu合金芯材之表面之Pd被覆層。本發明中，接合線之特徵在於：包含賦予高溫環境下之連接可靠性之元素，下述(1)式所定義之耐力比為1.1～1.6。 耐力比＝最大耐力/0.2%耐力 (1) 於作為半導體裝置之封裝之塑模樹脂(環氧樹脂)中，於分子骨架中包含氯(Cl)。於作為HAST評價條件之130℃、相對濕度為85%之高溫高濕環境下，分子骨架中之Cl水解而以氯化物離子(Cl- )之形式溶出。於將不具有Pd被覆層之Cu接合線接合於Al電極上之情形時，若將Cu/Al接合界面置於高溫下，則Cu與Al相互擴散，最終形成作為金屬間化合物之Cu9 Al4 。Cu9 Al4 容易受到Cl等鹵素之腐蝕，因自塑模樹脂溶出之Cl而進行腐蝕，導致接合可靠性之下降。於Cu線具有Pd被覆層之情形時，Pd被覆Cu線與Al電極之接合界面成為Cu/Pd濃化層/Al之結構，故而若與不具有Pd被覆層之Cu線相比，則抑制Cu9 Al4 金屬間化合物之生成，但汽車用元件所要求之高溫高濕環境下之接合可靠性不充分。 相對於此，可認為若如本發明般含有賦予高溫環境下之連接可靠性之元素，則有進一步抑制接合部中之Cu9 Al4 金屬間化合物的生成之傾向。 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中的成績)之觀點而言，賦予高溫環境下之連接可靠性之元素相對於線整體的濃度總計較佳為0.011質量%以上，更佳為0.030質量%以上，進而較佳為0.050質量%以上、0.070質量%以上、0.09質量%以上、0.10質量%以上、0.15質量%以上或0.20質量%以上。關於賦予高溫環境下之連接可靠性之元素的詳細說明如下所述。 如上所述，於楔接合中，接合線劇烈地變形。若於變形時線加工硬化，則接合後之線變硬，其結果楔接合之接合強度下降。為了維持良好之楔接合強度，下述(1)式所定義之耐力比較佳為1.6以下，更佳為1.55以下，進而較佳為1.50以下、1.45以下或1.40以下。就可發揮良好之楔接合性之觀點而言，耐力比較佳為1.1以上。 耐力比＝最大耐力/0.2%耐力 (1) 作為將(1)式之耐力比保持於適當範圍之手段，例如可列舉控制以下參數：(i)對接合線之垂直於線軸之方向的芯材剖面測定結晶方位而獲得之結果中，於線長度方向之結晶方位中，相對於線長度方向的角度差為15度以下之結晶方位＜100＞的方位比率(以下亦簡稱為「＜100＞方位比率」)；及(ii)接合線之垂直於線軸之方向的芯材剖面之平均結晶粒徑(以下亦簡稱為「平均結晶粒徑」)。若藉由通常之製造方法而製造接合線，則耐力比成為未達1.1或超過1.6，但藉由如下所述般設法改進製造方法，可將於接合線之垂直於線軸之方向的芯材剖面之線長度方向之結晶方位中，相對於線長度方向而角度差包含15度的＜100＞之方位比率設為30%以上，且將接合線之垂直於線軸之方向的芯材剖面之平均結晶粒徑設為0.9～1.5 μm，其結果表明，可將(1)式之耐力比設為1.1～1.6。 於＜100＞方位比率為30%以上時，伴隨著楔接合時之變形的線之加工硬化較小，故可將耐力比設為1.6以下。然而，即便於該情形時，於平均結晶粒徑未達0.9 μm時，0.2%耐力亦較高(缺乏延展性)，故而耐力比未達1.1而楔接合性較差。於平均結晶粒徑超過1.5 μm之情形時，＜100＞方位比率未達30%，進而0.2%耐力較低，故而推測耐力比超過1.6而楔接合性較差。 就伴隨著楔接合時之變形的線之加工硬化較小之觀點而言，＜100＞方位比率較佳為30%以上，更佳為35%以上，進而較佳為40%以上、45%以上。＜100＞方位比率之上限並無特別限定，例如亦可設為90%以下、80%以下、70%以下、60%以下、50%以下、未達50%(例如49%以下)。 就抑制耐力比之增大之觀點而言，較佳為將接合線之垂直於線軸之方向的芯材剖面之平均結晶粒徑設為0.9 μm以上且1.5 μm以下。接合線之垂直於線軸之方向的芯材剖面之平均結晶粒徑之下限值可設為1.0 μm以上、1.1 μm以上、1.3 μm以上、超過1.3 μm(例如1.35 μm以上)。 再者，即便於線之結晶結構滿足上述條件之情形時，若線中之賦予高溫環境下之連接可靠性的元素之含量過多，亦存在耐力比增大之情況。就實現耐力比1.6以下，抑制接合線之硬質化而抑制楔接合性之下降之觀點而言，賦予高溫環境下之連接可靠性的元素相對於線整體之濃度總計較佳為2.0質量%以下、1.8質量%以下或1.6質量%以下。 於使賦予高溫環境下之連接可靠性之元素包含於接合線中時，無論採用使該等元素包含於Cu芯材中之方法、被覆於Cu芯材或線表面而含有的方法中之哪一者，均可發揮上述本發明之效果。該等成分之添加量為極微量，因此添加方法之變化廣泛，無論以何種方法添加，只要包含該成分則均表現出效果。 於本發明之接合線中，就獲得良好之FAB形狀之觀點及進一步改善汽車用元件所要求之高溫高濕環境下的球接合部之接合可靠性之觀點而言，Pd被覆層之厚度較佳為0.015 μm以上，更佳為0.02 μm以上，進而較佳為0.025 μm以上、0.03 μm以上、0.035 μm以上、0.04 μm以上、0.045 μm以上或0.05 μm以上。另一方面，若Pd被覆層之厚度過厚，則FAB形狀亦下降，因此Pd被覆層之厚度較佳為0.150 μm以下，更佳為0.140 μm以下、0.130 μm以下、0.120 μm以下、0.110 μm以下或0.100 μm以下。 對上述接合線之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濃度作為基準而進行判定。以Pd濃度為50原子%之位置作為邊界，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。其依據在於：若於Pd被覆層中，Pd濃度為50原子%以上，則由Pd被覆層之結構而獲得特性之改善效果。Pd被覆層亦可包含Pd單層之區域、Pd與Cu於線之深度方向上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在於：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。本發明中，所謂濃度梯度，係指深度方向上之濃度變化之程度係每0.1 μm為10 mol%以上。進而，Pd被覆層亦可包含不可避免之雜質。 本發明之接合線亦可於Pd被覆層之表面進而具有包含Au及Pd之合金表皮層。藉此，本發明之接合線可進一步提高接合可靠性，並且可進一步改善楔接合性。 對上述接合線之包含Au及Pd之合金表皮層之定義進行說明。包含Au及Pd之合金表皮層與Pd被覆層之邊界係以Au濃度作為基準而進行判定。以Au濃度為10原子%之位置作為邊界，將Au濃度為10原子%以上之區域判定為包含Au及Pd之合金表皮層，將未達10原子%之區域判定為Pd被覆層。又，即便係Pd濃度為50原子%以上之區域，若存在10原子%以上之Au，則亦判定為包含Au及Pd之合金表皮層。該等之依據在於：若Au濃度為上述濃度範圍，則可由Au表皮層之結構而期待特性之改善效果。包含Au及Pd之合金表皮層為Au-Pd合金，且係設為包含Au與Pd於線之深度方向上具有濃度梯度之區域的區域。於包含Au及Pd之合金表皮層中形成該具有濃度梯度之區域之理由在於：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及Pd之合金表皮層亦可包含不可避免之雜質及Cu。 於本發明之接合線中，包含Au及Pd之合金表皮層可與Pd被覆層反應而提高包含Au及Pd之合金表皮層、Pd被覆層、Cu合金芯材間之密接強度，抑制楔接合時之Pd被覆層或包含Au及Pd之合金表皮層的剝離。藉此，本發明之接合線可進一步改善楔接合性。就獲得良好之楔接合性之觀點而言，包含Au及Pd之合金表皮層之厚度較佳為0.0005 μm以上，更佳為0.001 μm以上、0.002 μm以上或0.003 μm以上。就抑制偏芯而獲得良好之FAB形狀之觀點而言，包含Au及Pd之合金表皮層之厚度較佳為0.050 μm以下，更佳為0.045 μm以下、0.040 μm以下、0.035 μm以下或0.030 μm以下。再者，包含Au及Pd之合金表皮層可藉由與Pd被覆層相同之方法而形成。 本發明中，作為賦予高溫環境下之連接可靠性之元素，例如可列舉：元素週期表第9族之元素(Co、Rh、Ir)、元素週期表第10族之元素(Ni、Pd、Pt)、元素週期表第11族之元素(Ag、Au等)、元素週期表第12族之元素(Zn等)、元素週期表第13族之元素(Al、Ga、In等)、元素週期表第14族之元素(Ge、Sn等)、元素週期表第15族之元素(P、As、Sb、Bi等)、元素週期表第16族之元素(Se、Te等)等。該等元素可單獨一種或組合兩種以上而包含於接合線中。 本發明中，接合線較佳為包含選自Ni、Zn、Rh、In、Ir、Pt中之至少1種以上之元素作為賦予高溫環境下之連接可靠性之元素。該等元素相對於線整體之濃度較佳為總計0.011～2質量%。 於作為半導體裝置之封裝之塑模樹脂(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)之密接性之功能，故而可提昇與矽基板或金屬之密接性。進而，於要求更高溫下之可靠性之面向汽車之半導體等要求較高密接性之情形時，添加「含硫矽烷偶合劑」。塑模樹脂中含之硫若於175℃以上(例如175℃～200℃)之條件下使用則游離。而且，於175℃以上之高溫下游離之硫若與Cu接觸，則Cu之腐蝕變得劇烈，生成硫化物(Cu2 S)或氧化物(CuO)。若於使用Cu接合線之半導體裝置中產生Cu之腐蝕，則尤其是球接合部之接合可靠性下降。 此處，接合線包含選自Ni、Zn、Rh、In、Ir、Pt中之至少1種以上之元素，且將上述元素相對於線整體之濃度設為總計0.011～2質量%，藉此可提昇高溫環境下的接合可靠性(尤其是175℃以上之HTS中之成績)。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中的成績)之觀點而言，上述元素相對於線整體之濃度總計較佳為0.011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。於以下之說明中，將選自Ni、Zn、Rh、In、Ir、Pt中之至少1種以上之元素亦稱為「元素MA 」。 本發明中，接合線較佳為包含選自Ga、Ge中之1種以上之元素作為賦予高溫環境下之連接可靠性之元素，上述元素相對於線整體之濃度合計為0.011～1.5質量%。再者，於線中，亦可代替元素MA 或與元素MA 一起包含選自Ga、Ge中之1種以上之元素。於以下之說明中，將選自Ga、Ge中之1種以上之元素亦稱為「元素MB 」。 於形成球接合部之FAB時，線中之Ga、Ge亦於Pd被覆層中擴散。可認為球接合部之Cu與Al界面之Pd濃化層中存在之Ga、Ge進一步提高由Pd濃化層所得的Cu與Al之相互擴散抑制效果，結果抑制容易於高溫高濕環境下腐蝕之Cu9 Al4 之生成。又，線中所含之Ga、Ge亦存在具有直接妨礙Cu9 Al4 之形成的效果之可能性。 進而，使用含有特定量之選自Ga、Ge中之至少1種以上的Pd被覆Cu接合線形成球部，並利用掃描式電子顯微鏡(SEM：Scanning Electron Microscope)觀察FAB，結果於FAB之表面發現大量直徑數十nm
Figure 02_image001
左右之析出物。若藉由能量分散型X射線分析(EDS：Energy Dispersive X-ray Spectroscopy)對析出物進行分析，則確認到Ga、Ge濃化。根據如上狀況，可認為雖詳細之機制不明，但FAB中所觀察到之該析出物存在於球部與電極之接合界面，由此溫度為130℃、相對濕度為85%之高溫高濕環境下的球接合部之接合可靠性顯著提昇。 作為Ga、Ge之存在部位，較佳為Cu合金芯材中，但藉由包含於Pd被覆層或下述包含Au及Pd之合金表皮層中，亦可獲得充分之作用效果。於Cu合金芯材中添加Ga、Ge之方法容易進行準確之濃度管理，線生產性、品質穩定性提昇。又，因由熱處理所引起之擴散等而於Pd被覆層或合金表皮層中亦含有Ga、Ge之一部分，藉此各層界面之密接性優化，亦可進一步提昇線生產性。 另一方面，就獲得良好之FAB形狀之觀點、抑制接合線之硬質化而獲得良好的楔接合性之觀點而言，Ga、Ge相對於線整體之濃度合計為1.5質量%以下，較佳為1.4質量%以下，更佳為1.3質量%以下或1.2質量%以下。 本發明中，接合線較佳為包含選自As、Te、Sn、Sb、Bi、Se中之1種以上之元素，上述元素相對於線整體之濃度合計為0.1～100質量ppm，Sn≦10質量ppm、Sb≦10質量ppm、Bi≦1質量ppm。再者，於線中，亦可代替元素MA 及/或元素MB 或者與元素MA 及/或元素MB 一起包含選自As、Te、Sn、Sb、Bi、Se中之1種以上之元素。於以下之說明中，將選自As、Te、Sn、Sb、Bi、Se中之1種以上之元素亦稱為「元素MC 」。 本發明中，可認為接合線含有特定量之選自As、Te、Sn、Sb、Bi、Se中之至少1種以上之元素作為賦予高溫環境下之連接可靠性的元素之情形時，亦有進而抑制接合部之Cu9 Al4 金屬間化合物的生成之傾向。若含有特定量之該等元素，則於形成球時，芯材之Cu與被覆層之Pd的界面張力下降，界面之潤濕性優化，故而更顯著地表現出球接合界面之Pd濃化。因此推測，由Pd濃化層所得的Cu與Al之相互擴散抑制效果進而變強，結果容易因Cl之作用而腐蝕的Cu9 Al4 之生成量變少，球接合部於高溫高濕環境下之接合可靠性顯著地提昇。 若接合線包含選自As、Te、Sn、Sb、Bi、Se中之至少1種以上之元素，上述元素相對於線整體之濃度合計為0.1～100質量ppm，Sn≦10質量ppm、Sb≦10質量ppm、Bi≦1質量ppm，則可進一步改善汽車用元件所要求的高溫高濕環境下之球接合部之接合可靠性。尤其使溫度為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提昇，改善接合可靠性，因此較佳。上述元素相對於線整體之濃度合計較佳為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，上述元素相對於線整體之濃度合計較佳為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，或者Bi濃度超過1質量ppm之情形時，FAB形狀變得不良，因此藉由設為Sn≦10質量ppm、Sb≦10質量ppm、Bi≦1質量ppm，可進一步改善FAB形狀，因此較佳。 本發明之接合線較佳為進而包含選自B、P、Mg、Ca、La中之至少1種以上之元素，上述元素相對於線整體之濃度分別為1～200質量ppm。藉此，可改善高密度安裝所要求之球接合部之壓扁形狀，即改善球接合部形狀之正圓性。上述元素相對於線整體之濃度分別較佳為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。就抑制球之硬質化而抑制球接合時之晶片損傷之觀點而言，上述元素相對於線整體之濃度分別較佳為200質量ppm以下，更佳為150質量ppm以下、120質量ppm以下、100質量ppm以下、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接合線含有提昇高溫環境下之連接可靠性之元素之情形時，若進而於接合線之最表面存在Cu，則有進而抑制接合部的Cu9 Al4 金屬間化合物之生成之傾向。於Pd被覆Cu接合線含有提昇高溫環境下之連接可靠性之元素之情形時，若進而於接合線之最表面存在Cu，則藉由接合線中所含有的上述元素與Cu之相互作用，於形成FAB時促進FAB表面之Pd濃化，更顯著地表現出球接合界面之Pd濃化。推測，藉此而由Pd濃化層所得的Cu與Al之相互擴散抑制效果進而變強，容易因Cl之作用而腐蝕的Cu9 Al4 之生成量變少，球接合部之高溫高濕環境下之接合可靠性進一步提昇。 於Pd被覆層之最表面存在Cu之情形時，若Cu之濃度成為30原子%以上，則線表面之耐硫化性下降，接合線之使用壽命下降，故而有時不適於實用。因此，於Pd被覆層之最表面存在Cu之情形時，較佳為Cu之濃度未達30原子%。 又，於Au表皮層之最表面存在Cu之情形時，若Cu之濃度成為35原子%以上，則線表面之耐硫化性下降，接合線之使用壽命下降，故而有時不適於實用。因此，於Au表皮層之最表面存在Cu之情形時，較佳為Cu之濃度未達35原子%。 此處，所謂最表面，係指於不實施濺鍍等之狀態下利用歐傑電子分光裝置測定接合線之表面的區域。 於Pd被覆層、包含Au及Pd之合金表皮層之濃度分析中，以下方法較為有效：一面自接合線之表面向深度方向利用濺鍍等進行切削一面進行分析之方法，或者使線剖面露出而進行線分析、點分析等之方法。用於該等濃度分析之分析裝置可利用安裝於掃描式電子顯微鏡或穿透式電子顯微鏡上之歐傑電子分光分析裝置、能量分散型X射線分析裝置、電子束微量分析器等。作為使線剖面露出之方法，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)發光分光分析裝置或ICP質量分析裝置對以強酸溶解接合線而成之溶液進行分析，以接合線整體中所含的元素之濃度之形式而檢測。 (製造方法) 其次，對本發明之實施形態之接合線之製造方法進行說明。接合線係藉由如下方式獲得：製造用於芯材之Cu合金後，細細地加工成線狀而形成Pd被覆層、Au層，並進行熱處理。形成Pd被覆層、Au層後，亦存在再次進行拉線與熱處理之情況。對Cu合金芯材之製造方法、Pd被覆層、包含Au及Pd之合金表皮層之形成方法、熱處理方法進行詳細說明。 用於芯材之Cu合金係藉由如下方式獲得：將成為原料之Cu與添加之元素一起熔解並使其凝固。熔解可利用電弧加熱爐、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，較佳為於真空環境或者Ar或N2 等惰性環境中進行熔解。 於Cu合金芯材之表面形成Pd被覆層、Au層之方法有鍍敷法、蒸鍍法、熔融法等。鍍敷法可應用電鍍法、無電電鍍法之任一者。被稱為衝擊電鍍、閃熔電鍍之電鍍係鍍敷速度較快，與基底之密接性亦良好。用於無電電鍍之溶液被分為置換型與還原型，於厚度較薄之情形時，僅置換型鍍敷亦足矣，但於厚度較厚之情形時，有效的是於置換型鍍敷後階段性地實施還原型鍍敷。 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，無需Pd被覆層、Au層後形成之洗淨，無需擔心洗淨時之表面污染等。 藉由在形成Pd被覆層、Au層後進行熱處理，Pd被覆層之Pd於Au層中擴散，形成有包含Au及Pd之合金表皮層。亦可於形成Au層後不利用熱處理形成包含Au及Pd之合金表皮層，而自最初開始被覆包含Au及Pd之合金表皮層。 對於Pd被覆層、包含Au及Pd之合金表皮層之形成，以下方法均較為有效：拉線至最終線徑後形成之方法；及於形成為粗徑之Cu合金芯材後，進行複數次拉線直至目標線徑之方法。於前者之以最終徑形成Pd被覆層、包含Au及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及Pd之合金表皮層與拉線組合之情形時，就提昇與Cu合金芯材之密接性之方面而言較為有利。作為各形成方法之具體例，可列舉：於最終線徑之Cu合金芯材上，一面於電鍍溶液中對線進行連續地掃描一面形成Pd被覆層、包含Au及Pd之合金表皮層的方法；或者將較粗之Cu合金芯材浸漬於電解或無電解之鍍敷浴中而形成Pd被覆層、包含Au及Pd之合金表皮層後，對線進行拉線而到達最終線徑之方法等。 形成Pd被覆層、包含Au及Pd之合金表皮層後，有進行熱處理之情形。藉由進行熱處理而使原子於包含Au及Pd之合金表皮層、Pd被覆層、Cu合金芯材之間擴散，密接強度提昇，故而可抑制加工中之包含Au及Pd之合金表皮層或Pd被覆層的剝離，就生產性提昇之方面而言較為有效。為了防止來自大氣中之O2 之混入，較佳為於真空環境或者Ar或N2 等惰性環境中進行熱處理。 藉由如上所述般調整對接合線實施之擴散熱處理或退火熱處理之條件，可藉由晶界擴散、粒內擴散等使芯材之Cu於Pd被覆層或包含Au及Pd之表皮合金層中擴散，使Cu到達接合線之最表面，使Cu存在於最表面。作為用以使Cu存在於最表面之熱處理，可如上所述般使用用以形成包含Au及Pd之合金表皮層之熱處理。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，可使Cu存在或不存在於最表面。進而，亦可將最表面之Cu濃度調整至特定範圍(例如1～50原子%之範圍)。亦可藉由除了形成合金表皮層時以外進行之熱處理而使Cu擴散至最表面。 如上所述般，於使賦予高溫環境下之連接可靠性之元素包含於接合線中時，無論採用使該元素包含於Cu芯材中之方法、被覆於Cu芯材或線表面而含有之方法之哪一者，均可發揮上述本發明之效果。B、P、Mg、Ca、La亦同樣。 作為上述成分之添加方法，最簡便的是預先添加至Cu合金芯材之初始材料中之方法。例如稱量高純度之銅與上述成分元素原料作為初始原料後，立即對其於高真空下、氮氣或氬氣等惰性環境下進行加熱而溶解，由此製成添加有目標濃度範圍之上述成分之鑄錠，成為包含目標濃度之上述成分元素之初始材料。因此，於較佳之一實施形態中，本發明之接合線之Cu合金芯材以如下方式包含選自Ni、Zn、Rh、In、Ir、Pt中之至少1種以上之元素，即，上述元素相對於線整體的濃度總計成為0.011～2質量%。該濃度之合計之較佳數值範圍如上所述。於其他較佳之一實施形態中，本發明之接合線之Cu合金芯材以如下方式包含選自Ga、Ge中之1種以上之元素，即，上述元素相對於線整體之濃度總計成為0.011～1.5質量%。該濃度之合計之較佳數值範圍如上所述。於其他較佳之一實施形態中，本發明之接合線之Cu合金芯材以如下方式包含選自As、Te、Sn、Sb、Bi、Se中之至少1種以上之元素，即，上述元素相對於線整體之濃度合計成為0.1～100質量ppm，且Sn≦10質量ppm、Sb≦10質量ppm、Bi≦1質量ppm。該濃度之較佳數值範圍如上所述。於較佳之一實施形態中，Cu合金芯材之Cu之純度為3 N以下(較佳為2 N以下)。關於先前之Pd被覆Cu接合線，就接合性之觀點而言，有使用高純度(4 N以上)之Cu芯材而避免使用低純度之Cu芯材之傾向。關於含有特定元素之本發明之接合線，尤其適於如上所述般使用Cu之純度較低的Cu合金芯材之情形，實現了汽車用元件所要求之高溫高濕環境下之球接合部之接合可靠性。於其他較佳之一實施形態中，本發明之接合線之Cu合金芯材以如下方式包含選自B、P、Mg、Ca、La中之至少1種以上之元素，即，上述元素相對於線整體之濃度分別成為1～200質量ppm。該濃度之較佳數值範圍如上所述。於其他較佳之一實施形態中，本發明之接合線之Cu合金芯材以總計成為0.1～3.0質量%之方式包含元素週期表第10族之金屬元素。該濃度之較佳數值範圍如上所述。 線製造步驟之中途，亦可藉由被覆而使上述成分包含於線表面。於該情形時，可併入至線製造步驟之任一處，亦可反覆進行複數次。亦可併入至複數個步驟中。可添加至Pd被覆前之Cu表面，亦可添加至Pd被覆後之Pd表面，亦可添加至Au被覆後之Au表面，亦可併入至各被覆步驟中。作為被覆方法，可自(1)水溶液之塗佈⇒乾燥⇒熱處理、(2)鍍敷法(濕式)、(3)蒸鍍法(乾式)中選擇。 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化合物製備適當濃度之水溶液。藉此，可將上述成分摻入至線材料中。可併入至線製造步驟之任一處，亦可反覆進行複數次。亦可併入至複數個步驟中。可添加至Pd被覆前之Cu表面，亦可添加至Pd被覆後之Pd表面，亦可添加至Au被覆後之Au表面，亦可併入至各被覆步驟中。 於使用鍍敷法(濕式)之情形時，鍍敷法可使用電鍍法、無電電鍍法之任一者。於電鍍法中，除通常之電鍍以外，亦可使用被稱為閃熔電鍍之鍍敷速度較快且與基底之密接性亦良好之鍍敷法。用於無電電鍍之溶液存在置換型與還原型。通常於鍍敷厚度較薄之情形時，使用置換型鍍敷，於較厚之情形時，使用還原型鍍敷，可使用任一方法，只要根據欲添加之濃度而選擇並調整鍍敷液濃度、時間即可。電鍍法、無電電鍍法均可併入至線製造步驟之任一處，亦可反覆進行複數次。亦可併入至複數個步驟中。可添加至Pd被覆前之Cu表面，亦可添加至Pd被覆後之Pd表面，亦可添加至Au被覆後之Au表面，亦可併入至各被覆步驟中。 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，故而其優點在於：無需預處理後處理，無需擔心污染。通常蒸鍍法之問題在於目標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，因此為適於本發明之目的之方法之一。 各蒸鍍法可併入至線製造步驟之任一處，亦可反覆進行複數次。亦可併入至複數個步驟中。可添加至Pd被覆前之Cu表面，亦可添加至Pd被覆後之Pd表面，亦可添加至Au被覆後之Au表面，亦可併入至各被覆步驟中。 對用以實現如下情況之製造方法進行說明：對接合線之垂直於線軸之方向的芯材剖面測定結晶方位，結果於線長度方向之結晶方位中，將相對於線長度方向之角度差為15度以下之結晶方位＜100＞的方位比率設為30%以上，且將接合線之垂直於線軸之方向的芯材剖面之平均結晶粒徑設為0.9～1.5 μm。 若於接合線中使賦予高溫環境下之連接可靠性之元素包含於Cu合金芯材中，則線之材料強度(硬度)變高。因此，於對Cu芯線之接合線進行拉線加工時，將拉線時之減縮率設為5～8%之較低之減縮率。又，於拉線後之熱處理中，因硬度仍然較高，故而為了使其軟質化至可用作接合線之水準，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，故而線長度方向之＜100＞方位比率未達30%，同時芯材剖面之平均結晶粒徑超過1.5 μm，耐力比超過1.6。另一方面，若為了降低耐力比而降低熱處理溫度，則芯材剖面之平均結晶粒徑未達0.9 μm，耐力比未達1.1，楔接合性變得較差。 相對於此，於本發明中，使用模具進行拉線時，於模具總數中之一半以上之模具中將減縮率設為10%以上，進而將拉線後之熱處理的熱處理溫度設為500℃以下之較低溫度。其結果，可於對接合線之垂直於線軸之方向的芯材剖面測定結晶方位之結果中，於線長度方向之結晶方位中，將相對於線長度方向之角度差為15度以下之結晶方位＜100＞的方位比率設為30%以上，且將接合線之垂直於線軸之方向的芯材剖面之平均結晶粒徑設為0.9～1.5 μm。應用最新之拉線加工技術，藉由作為潤滑液而將潤滑液中所含之非離子系界面活性劑之濃度設計為較先前更高、作為模具形狀而將模具之接近角度設計為較先前者更緩和、且將模具之冷卻水溫度設定為較先前更低等之協同效果，儘管於Cu合金芯材中含有總計0.03質量%以上之Ni等成分而硬質化，亦可進行減縮率10%以上之拉線加工。 於對線剖面之結晶方位進行測定時，較佳為使用背向散射電子束折射法(EBSD，Electron Backscattered Diffraction)。EBSD法具有對觀察面之結晶方位進行觀察且可對相鄰測定點間之結晶方位的角度差進行圖示之特徵，即便為如接合線般之細線，亦可相對簡便且高精度地觀察結晶方位。關於粒徑測定，可藉由對由EBSD法所獲得之測定結果利用裝置所配備之分析軟體而求出。本發明中所規定之結晶粒徑係對測定區域內所含之結晶粒之等效直徑(相當於結晶粒之面積的圓之直徑；近似圓的直徑)進行算術平均而獲得者。 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變更。 [實施例] 以下，一面示出實施例一面對本發明之實施形態之接合線進行具體說明。 ＜本發明例1～59及比較例1～16＞ (樣品之製作) 首先，對樣品之製作方法進行說明。成為芯材之原材料之Cu係使用純度為99.99質量%以上且剩餘部分由不可避免之雜質所構成者。Au、Pd、Ni、Zn、Rh、In、Ir、Pt係使用純度為99質量%以上且剩餘部分由不可避免之雜質所構成者。以線或芯材之組成成為目標組成之方式，調配作為向芯材中添加之元素的Ni、Zn、Rh、In、Ir、Pt。關於Ni、Zn、Rh、In、Ir、Pt之添加，雖亦能以單體之形式調配，但於單體為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。於本發明例27～47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之線徑之方式製造。對於所獲得之數mm之合金，進行抽拉加工而製作
Figure 02_image001
0.3～1.4 mm之線。拉線係使用市售之潤滑液，拉線速度係設為20～150 m/分。為了去除線表面之氧化膜而利用鹽酸等進行酸洗處理後，以覆蓋芯材之Cu合金的表面整體之方式形成1～15 μm之Pd被覆層。進而，一部分線係於Pd被覆層上形成0.05～1.5 μm之包含Au及Pd之合金表皮層。Pd被覆層、包含Au及Pd之合金表皮層之形成係使用電鍍法。鍍敷液係使用市售之半導體用鍍敷液。其後，主要使用減縮率10～21%之模具進行拉線加工，進而中途於200～500℃下進行1至3次熱處理，藉此加工至直徑20 μm。加工後，以斷裂伸長率最終成為約5～15%之方式進行熱處理。熱處理方法係一面連續掃描線一面進行，且一面流通N2 或Ar氣體一面進行。線之輸送速度係設為10～90 m/分，熱處理溫度係設為350～500℃，且熱處理時間係設為1～10秒。 (評價方法) 關於線中之Ni、Zn、Rh、In、Ir、Pt、Ga、Ge、As、Te、Sn、Sb、Bi、Se、B、P、Mg、Ca、La含量，利用ICP發光分光分析裝置，以接合線整體所含之元素之濃度之形式進行分析。 關於Pd被覆層、包含Au及Pd之合金表皮層之濃度分析，一面利用濺鍍等自接合線之表面向深度方向進行切削一面實施歐傑電子分光分析。根據所獲得之深度方向之濃度分佈求出Pd被覆層厚度、包含Au及Pd之合金表皮層厚度。 關於接合線之垂直於線軸之方向的芯材剖面之線長度方向之結晶方位中，相對於線長度方向之角度差為15度以下之結晶方位＜100＞的方位比率，係利用EBSD法對觀察面(即，垂直於線軸之方向的芯材剖面)之結晶方位進行觀察後算出。EBSD測定資料之分析係利用專用軟體(TSL solutions製造之OIM analisis等)。垂直於線軸之方向的芯材剖面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後算出。EBSD測定資料之分析係利用專用軟體(TSL solutions製造之OIM analisis等)。結晶粒徑係對測定區域內所含之結晶粒之等效直徑(相當於結晶粒之面積的圓之直徑；近似圓的直徑)進行算術平均而獲得者。 0.2%耐力與最大耐力係藉由將標距設為100 mm進行拉伸試驗而評價。作為拉伸試驗裝置，使用Instron公司製造之萬能材料試驗機5542型。0.2%耐力係使用裝置所配備之專用軟體而算出。又，將斷裂時之荷重設為最大耐力。根據下述(1)式算出耐力比。 耐力比＝最大耐力/0.2%耐力 (1) 線接合部之楔接合性之評價係於BGA(Ball Grid Array，球柵陣列)基板之楔接合部進行1000條之接合，根據接合部之剝離之發生頻度而進行判定。所使用之BGA基板係實施有鍍Ni及Au者。本評價中，設想較通常更嚴格之接合條件，將工作台溫度設為較通常之設定溫度範圍更低之150℃。於上述評價中，於產生11個以上之不良之情形時，判斷為有問題並記作×記號，若不良為6～10個，則判斷為雖可實用但稍有問題而記作△記號，於不良為1～5個之情形時，判斷為無問題並記作〇記號，於未產生不良之情形時，判斷為優異並記作◎記號，記載於表1～表4之「楔接合性」之欄中。 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樣品並進行HTS評價，根據球接合部之接合壽命而判定。接合可靠性評價用樣品係如下而製作：使厚度0.8 μm之Al-1.0%Si-0.5%Cu之合金於通常之金屬框架上的Si基板上成膜而形成電極，使用市售之打線接合機對該電極進行球接合，利用市售之環氧樹脂進行密封。球係一面以流量0.4～0.6 L/min流通N2 ＋5%H2 氣體一面形成，其大小係設為
Figure 02_image001
33～34 μm之範圍。 關於HTS評價，使用高溫恆溫器將所製作之接合可靠性評價用樣品暴露於溫度200℃之高溫環境下。球接合部之接合壽命係每500小時實施球接合部之剪切試驗，設為剪切強度之值成為初期所獲得的剪切強度之1/2之時間。高溫高濕試驗後之剪切試驗係利用酸處理去除樹脂而使球接合部露出後進行。 HTS評價之剪切試驗機係使用DAGE公司製造之試驗機。剪切強度之值係使用隨機選擇之球接合部之10處的測定值之平均值。於上述評價中，若接合壽命為500小時以上且未達1000小時，則判斷為可實用但需要改善並記作△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並記作〇記號，若為3000小時以上，則判斷為特別優異並記作◎記號，記載於表1～表4之「HTS」之欄中。 球形成性(FAB形狀)之評價係採取進行接合前之球進行觀察，判定球表面的氣泡之有無、原本為圓球之球的變形之有無。於產生上述任一者之情形時，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0.5 L/min吹送氮氣一面進行。球之大小係設為34 μm。於1條件下觀察50個球。觀察係使用SEM。於球形成性之評價中，於產生5個以上之不良之情形時，判斷為有問題並記作×記號，若不良為3～4個，則判斷為可實用但稍有問題並記作△記號，於不良為1～2個之情形時，判斷為無問題並記作〇記號，於未產生不良之情形時，判斷為優異並記作◎記號，記載於表1～表4之「FAB形狀」之欄中。 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，可藉由以下之HAST評價而進行評價。關於HAST評價，使用不飽和型壓力鍋試驗機將所製作之接合可靠性評價用樣品暴露於溫度130℃、相對濕度85%之高溫高濕環境下並施加5 V之偏壓。球接合部之接合壽命係每48小時實施球接合部之剪切試驗，設為剪切強度之值成為初期所獲得之剪切強度的1/2之時間。高溫高濕試驗後之剪切試驗係利用酸處理去除樹脂而使球接合部露出後進行。 HAST評價之剪切試驗機係使用DAGE公司製造之試驗機。剪切強度之值係使用隨機選擇之球接合部之10處的測定值之平均值。於上述評價中，若接合壽命為144小時以上且未達288小時，則判斷為於實用上無問題並記作〇記號，若為288小時以上且未達384小時，則判斷為優異並記作◎記號，若為384小時以上，則判斷為特別優異並記作◎◎記號，記載於表1～表4之「HAST」之欄中。 球接合部之壓扁形狀之評價係自正上方觀察進行了接合之球接合部，根據其正圓性而判定。接合對象係使用將厚度1.0 μm之Al-0.5%Cu之合金於Si基板上成膜而成之電極。觀察係使用光學顯微鏡，於1條件下觀察200處。關於與正圓之偏差較大之楕圓狀者、變形具有各向異性者，判斷為球接合部之壓扁形狀不良。於上述評價中，於不良為1～3個之情形時，判斷為無問題並記作〇記號，於全部獲得了良好之正圓性之情形時，判斷為特別優異並記作◎記號，記載於表1～表4之「壓扁形狀」之欄中。 [表1]
Figure 107122893-A0304-0001
 [表2]
Figure 107122893-A0304-0002
 [表3]
Figure 107122893-A0304-0003
 [表4]
Figure 107122893-A0304-0004
 (評價結果) 本發明例1～59之接合線係於線中含有0.011～1.2質量%之Ni、Zn、Rh、In、Ir、Pt，並且耐力比(＝最大耐力/0.2%耐力)均為1.1～1.6之範圍內，藉由HTS評價之球接合部高溫可靠性及楔接合性均成為良好之結果。關於本發明之接合線，可認為由於將拉線時之減縮率設為10%以上，且將拉線後之熱處理中的熱處理溫度設為500℃以下之較低之溫度，因此於對接合線之垂直於線軸之方向的芯材剖面測定結晶方位的結果中，可於線長度方向之結晶方位中，將相對於線長度方向之角度差為15度以下之結晶方位＜100＞的方位比率設為30%以上，且將接合線之垂直於線軸之方向的芯材剖面之平均結晶粒徑設為0.9～1.5 μm，從而可將耐力比設為上述範圍。 又，本發明例之接合線具有Cu合金芯材及形成於Cu合金芯材之表面之Pd被覆層，Pd被覆層之厚度在作為適當範圍之0.015～0.150 μm之範圍內，FAB形狀均良好。 另一方面，關於耐力比未達1.1之比較例1、3、10、11，楔接合性均不良，關於耐力比超過1.6之比較例2、4～9、12～16，楔接合性不良或存在問題。尤其於比較例15及16中，由於線中不含賦予高溫環境下之連接可靠性之元素，因此HTS、HAST之結果亦不良。可認為於比較例1、3、10、11中耐力比變低之一個原因在於：將模具之減縮率設為未達10%，因此芯材剖面之平均結晶粒徑成為未達0.9 μm。可認為於比較例2、4～9、12～14中耐力比增大之一個原因在於：將熱處理溫度設為600℃以上之較高之溫度，因此線長度方向之＜100＞方位比率成為未達30%，尤其可認為於比較例2、6、8、9、14中耐力比增大之一個原因在於：將熱處理溫度設為620℃以上之較高之溫度，因此芯材剖面的平均結晶粒徑成為超過1.5 μm。 ＜本發明例2-1～2-40＞ (樣品) 首先，對樣品之製作方法進行說明。成為芯材之原材料之Cu係使用純度為99.99質量%以上且剩餘部分由不可避免之雜質所構成者。Ga、Ge、Ni、Ir、Pt、Pd、B、P、Mg係使用純度為99質量%以上且剩餘部分由不可避免之雜質所構成者。以線或芯材之組成成為目標組成之方式，調配作為向芯材添加之元素的Ga、Ge、Ni、Ir、Pt、Pd、B、P、Mg。關於Ga、Ge、Ni、Ir、Pt、Pd、B、P、Mg之添加，雖亦能以單體之形式調配，但於單體為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。 芯材之Cu合金係藉由如下方式製作：於經加工成直徑為
Figure 02_image001
3～6 mm之圓柱型之碳坩鍋中裝填原料，使用高頻爐於真空中或者氮氣或氬氣等惰性環境下加熱至1090～1300℃而熔解後，進行爐內冷卻。對於所獲得之
Figure 02_image001
3～6 mm之合金，進行抽拉加工而加工至
Figure 02_image001
0.9～1.2 mm後，使用模具連續地進行拉線加工等，藉此製作
Figure 02_image001
300～600 μm之線。拉線係使用市售之潤滑液，拉線速度係設為20～150 m/分。為了去除線表面之氧化膜而利用鹽酸進行酸洗處理後，以覆蓋芯材之Cu合金之表面整體之方式形成1～15 μm之Pd被覆層。進而，一部分線係於Pd被覆層上形成0.05～1.5 μm之包含Au及Pd之合金表皮層。Pd被覆層、包含Au及Pd之合金表皮層之形成係使用電鍍法。鍍敷液係使用市售之半導體用鍍敷液。其後，藉由反覆進行200～500℃之熱處理與拉線加工而加工至直徑20 μm。加工後，以斷裂伸長率最終成為約5～15%之方式一面流通氮氣或氬氣一面進行熱處理。熱處理方法係一面連續地掃描線一面進行，且一面流通氮氣或氬氣一面進行。線之輸送速度係設為20～200 m/分，熱處理溫度係設為200～600℃，且熱處理時間係設為0.2～1.0秒。 關於Pd被覆層、包含Au及Pd之合金表皮層之濃度分析，一面自接合線之表面朝深度方向利用Ar離子進行濺鍍一面使用歐傑電子分光分析裝置進行分析。被覆層及表皮合金層之厚度係根據所獲得之深度方向之濃度分佈(深度之單位為SiO2 換算)而求出。將Pd之濃度為50原子%以上且Au之濃度未達10原子%之區域設為Pd被覆層，將存在於Pd被覆層表面之Au濃度為10原子%以上之範圍的區域設為合金表皮層。將被覆層及合金表皮層之厚度及Pd最大濃度分別記載於表5及表6。Cu合金芯材中之Pd之濃度係藉由如下方法進行測定：使線剖面露出，利用設置於掃描式電子顯微鏡上之電子束微量分析器進行線分析、點分析等之方法。作為使線剖面露出之方法，利用機械研磨、離子蝕刻法等。接合線中之Ga、Ge、Ni、Ir、Pt、B、P、Mg之濃度係利用ICP發光分光分析裝置、ICP質量分析裝置對以強酸溶解接合線而成之溶液進行分析，以接合線整體中所含之元素之濃度之形式而測出。 將以上述順序製作之各樣品之構成示於下述表5及表6。 [表5]
Figure 107122893-A0304-0005
 [表6]
Figure 107122893-A0304-0006
 (評價方法) 以線表面作為觀察面而進行結晶組織之評價。作為評價方法，使用背向散射電子束折射法(EBSD，Electron Backscattered Diffraction)。EBSD法係具有對觀察面之結晶方位進行觀察而可對相鄰測定點間之結晶方位的角度差進行圖示之特徵，即便如接合線般之細線，亦可相對簡便並且高精度地觀察結晶方位。 於以如線表面般之曲面作為對象而實施EBSD法之情形時，必需加以注意。若對曲率較大之部位進行測定，則精度較高之測定變得困難。然而，將供於測定之接合線以平面形式固定於直線上，測定該接合線之中心附近之平坦部，藉此可進行精度較高之測定。具體而言，亦可設為如下測定區域。圓周方向之尺寸係以線長度方向之中心作為軸而設為線徑之50%以下，線長度方向之尺寸係設為100 μm以下。較佳為若將圓周方向之尺寸設為線徑之40%以下，將線長度方向之尺寸設為40 μm以下，則可藉由縮短測定時間而提高測定效率。為了進一步提高精度，較理想為測定3處以上，獲得考慮到不均之平均資訊。測定部位亦可以不接近之方式相距1 mm以上。 關於接合線之垂直於線軸之方向的芯材剖面之線長度方向之結晶方位中，相對於線長度方向之角度差為15度以下之結晶方位＜100＞的方位比率，及垂直於線軸之方向的芯材剖面之平均結晶粒徑(μm)，係藉由與本發明例1～59相同之方法而求出。又，關於0.2%耐力及最大耐力，藉由與本發明例1～59相同之方法進行評價，根據上述(1)式而算出耐力比。 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樣品並進行HAST及HTS評價，根據各試驗中之球接合部之接合壽命而進行判定。接合可靠性評價用樣品係使用市售之打線接合機對將厚度0.8 μm之Al-1.0%Si-0.5%Cu之合金於通常之金屬框架上的Si基板上成膜而形成之電極進行球接合，利用市售之環氧樹脂進行密封而製作。球係一面以流量0.4～0.6 L/min流通N2 ＋5%H2 氣體一面形成，其大小係設為
Figure 02_image001
33～34 μm之範圍。 關於HAST評價，使用不飽和型壓力鍋試驗機將所製作之接合可靠性評價用樣品暴露於溫度130℃、相對濕度85%之高溫高濕環境下，施加7 V之偏壓。球接合部之接合壽命係每48小時實施球接合部之剪切試驗，設為剪切強度之值成為初期獲得之剪切強度的1/2之時間。高溫高濕試驗後之剪切試驗係藉由酸處理而去除樹脂，使球接合部露出後進行。 HAST評價之剪切試驗機係使用DAGE公司製造之試驗機。剪切強度之值係使用隨機選擇之球接合部之10處的測定值之平均值。於上述評價中，若接合壽命未達96小時，則判斷為於實用上有問題並記作×記號，若為96小時以上且未達144小時，則判斷為可實用但稍有問題並記作△記號，若為144小時以上且未達288小時，則判斷為於實用上無問題並記作〇記號，若為288小時以上，則判斷為特別優異並記作◎記號，記載於表5及表6之「HAST」之欄中。 關於HTS評價，使用高溫恆溫器將所製作之接合可靠性評價用樣品暴露於溫度200℃之高溫環境下。球接合部之接合壽命係每500小時實施球接合部之剪切試驗，設為剪切強度之值成為初期獲得之剪切強度的1/2之時間。高溫高濕試驗後之剪切試驗係藉由酸處理而去除樹脂，使球接合部露出後進行。 HTS評價之剪切試驗機係使用DAGE公司製造之試驗機。剪切強度之值係使用隨機選擇之球接合部之10處的測定值之平均值。於上述評價中，若接合壽命為500小時以上且未達1000小時，則判斷為可實用但有改善之需求並記作△記號，若為1000小時以上且未達3000小時，則判斷為於實用上無問題並記作〇記號，若為3000小時以上，則判斷為特別優異並記作◎記號。 球形成性(FAB形狀)之評價係採取進行接合前之球進行觀察，判定球表面之氣泡之有無、原本為圓球之球的變形之有無。於產生上述任一者之情形時，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0.5 L/min吹送氮氣一面進行。球之大小係設為34 μm。於1條件下觀察50個球。觀察係使用SEM。於球形成性之評價中，於產生5個以上之不良之情形時，判斷為有問題並記作×記號，若不良為3～4個，則判斷為可實用但稍有問題並記作△記號，於不良為1～2個之情形時，判斷為無問題並記作〇記號，於未產生不良之情形時，判斷為優異並記作◎記號，記載於表5及表6之「FAB形狀」之欄中。 線接合部之楔接合性之評價係對導線框架的導線部分進行1000條之接合，根據接合部之剝離之發生頻度而進行判定。導線框架係使用實施有1～3 μm之鍍Ag之Fe-42原子%Ni合金導線框架。於本評價中，設想較通常更嚴格之接合條件，將工作台溫度設為較通常之設定溫度範圍更低之150℃。於上述評價中，於產生11個以上之不良之情形時，判斷為有問題並記作×記號，若不良為6～10個，則判斷為可實用但稍有問題並記作△記號，於不良為1～5個之情形時，判斷為無問題並記作〇記號，於未產生不良之情形時，判斷為優異並記作◎記號，記載於表5及表6之「楔接合性」之欄中。 球接合部之壓扁形狀之評價係自正上方觀察進行了接合之球接合部，根據其正圓性而進行判定。接合對象係使用將厚度1.0 μm之Al-0.5%Cu之合金於Si基板上成膜而成之電極。觀察係使用光學顯微鏡，於1條件下觀察200處。關於與正圓之偏差較大之楕圓狀者、變形具有各向異性者，判斷為球接合部之壓扁形狀不良。於上述評價中，於產生6個以上之不良之情形時，判斷為有問題並記作×記號，若不良為4～5個，則判斷為可實用但稍有問題並記作△記號，於1～3個之情形時，判斷為無問題並記作〇記號，於全部獲得了良好之正圓性之情形時，判斷為特別優異並記作◎記號，記載於表5及表6之「壓扁形狀」之欄中。 [偏斜] 於評價用導線框架上，以迴路長度5 mm、迴路高度0.5 mm接合100條。作為評價方法，自晶片水平方向觀察線直立部，根據通過球接合部之中心之垂線與線直立部的間隔最大時之間隔(偏斜間隔)而進行評價。於偏斜間隔小於線徑之情形時，判斷為偏斜良好，於較大之情形時，直立部傾斜，故而判斷為偏斜不良。利用光學顯微鏡對100條經接合之線進行觀察，對偏斜不良之條數進行計數。於產生7個以上之不良之情形時，判斷為有問題並記作×記號，若不良為4～6個，則判斷為可實用但稍有問題並記作△記號，於不良為1～3個之情形時，判斷為無問題並記作〇記號，於未產生不良之情形時，判斷為優異並記作◎記號，記載於表5及表6之「偏斜」之欄中。 (評價結果) 如表5及表6所示，本發明例2-1～2-40之接合線具有Cu合金芯材及形成於Cu合金芯材表面之Pd被覆層，接合線包含選自Ga、Ge中之1種以上之元素，上述元素相對於線整體之濃度合計為0.011～1.5質量%。藉此確認到，本發明例2-1～2-40之接合線於溫度為130℃、相對濕度為85%之高溫高濕環境下之HAST試驗中可獲得球接合部可靠性。 進而確認到，本發明例2-1～2-40之接合線藉由耐力比為1.1～1.6而可獲得優異之楔接合性。 於接合線進而包含選自Ni、Ir、Pt、Pd中之至少1種以上之元素的本發明例中，確認到由HTS評價所得之球接合部高溫可靠性更良好。 接合線進而包含選自B、P、Mg中之至少1種以上之元素的本發明例中，藉由上述元素相對於線整體之濃度分別為1～200質量ppm，球接合部之壓扁形狀良好。 ＜本發明例3-1～3-56＞ (樣品) 首先，對樣品之製作方法進行說明。成為芯材之原材料之Cu係使用純度為99.99質量%以上且剩餘部分由不可避免之雜質所構成者。As、Te、Sn、Sb、Bi、Se、Ni、Zn、Rh、In、Ir、Pt、Ga、Ge、Pd、B、P、Mg、Ca、La係使用純度為99質量%以上且剩餘部分由不可避免之雜質所構成者。以線或芯材之組成成為目標組成之方式，調配作為向芯材中添加之元素的As、Te、Sn、Sb、Bi、Se、Ni、Zn、Rh、In、Ir、Pt、Ga、Ge、Pd、B、P、Mg、Ca、La。關於As、Te、Sn、Sb、Bi、Se、Ni、Zn、Rh、In、Ir、Pt、Ga、Ge、Pd、B、P、Mg、Ca、La之添加，雖亦能以單體之形式調配，但於單體為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母合金而以成為目標添加量之方式調配。 芯材之Cu合金係藉由如下方式製造：於經加工成直徑為
Figure 02_image001
3～6 mm之圓柱型的碳坩鍋中裝填原料，使用高頻爐於真空中或者氮氣或氬氣等惰性環境下加熱至1090～1300℃而熔解後，進行爐內冷卻。對於所獲得之
Figure 02_image001
3～6 mm之合金，進行抽拉加工而加工至
Figure 02_image001
0.9～1.2 mm後，使用模具連續地進行拉線加工等，藉此製作
Figure 02_image001
300～600 μm之線。拉線係使用市售之潤滑液，拉線速度係設為20～150 m/分。為了去除線表面之氧化膜而利用鹽酸進行酸洗處理後，以覆蓋芯材之Cu合金之表面整體之方式形成1～15 μm之Pd被覆層。進而，一部分線係於Pd被覆層上形成0.05～1.5 μm之包含Au及Pd之合金表皮層。Pd被覆層、包含Au及Pd之合金表皮層之形成係使用電鍍法。鍍敷液係使用市售之半導體用鍍敷液。其後，藉由反覆進行200～500℃之熱處理與拉線加工而加工至直徑20 μm。加工後，以斷裂伸長率最終成為約5～15%之方式一面流通氮氣或氬氣一面進行熱處理。熱處理方法係一面連續掃描線一面進行，且一面流通氮氣或氬氣一面進行。線之輸送速度係設為20～200 m/分，熱處理溫度係設為200～600℃，且熱處理時間係設為0.2～1.0秒。 關於Pd被覆層、包含Au及Pd之合金表皮層之濃度分析，一面利用濺鍍等自接合線之表面朝深度方向進行切削一面實施歐傑電子分光分析。根據所獲得之深度方向之濃度分佈求出Pd被覆層之厚度、包含Au及Pd之合金表皮層之厚度及Pd最大濃度。 關於本發明例3-1～3-50，使選自As、Te、Sn、Sb、Bi、Se中之元素包含於芯材中。關於本發明例3-51～3-56，芯材使用純度為99.99質量%以上之Cu，於線製造步驟之中途，利用電鍍法使As、Te、Sn、Sb、Bi、Se被覆於線表面(被覆層)而包含該等元素。 關於本發明例3-34～3-44，使Cu存在於接合線之最表面。此處，於表8中設置「線表面Cu濃度」之欄，記載利用歐傑電子分光裝置對接合線之表面進行測定而獲得之結果。藉由選擇接合線之熱處理溫度與時間而使特定濃度之Cu包含於最表面。關於本發明例3-1～3-33、3-45～3-56，設定為不使Cu存在於最表面之熱處理條件，即便利用歐傑電子分光裝置，亦未檢測出Cu。 將上述順序中所製作之各樣品之構成示於表7及表8。 [表7]
Figure 107122893-A0304-0007
 [表8]
Figure 107122893-A0304-0008
 (評價方法) 以線表面作為觀察面而進行結晶組織之評價。作為評價方法，使用背向散射電子束折射法(EBSD，Electron Backscattered Diffraction)。EBSD法具有對觀察面之結晶方位進行觀察且可對相鄰測定點間之結晶方位的角度差進行圖示之特徵，即便為如接合線般之細線，亦可相對簡便且高精度地觀察結晶方位。 於以如線表面般之曲面作為對象實施EBSD法之情形時，必需加以注意。若對曲率較大之部位進行測定，則精度較高之測定變得困難。然而，於供於測定之接合線以平面形式固定於直線上，測定該接合線之中心附近之平坦部，藉此可進行精度較高之測定。具體而言，亦可設為如下測定區域。圓周方向之尺寸係以線長度方向之中心作為軸而設為線徑之50%以下，線長度方向之尺寸係設為100 μm以下。較佳為若將圓周方向之尺寸設為線徑之40%以下，將線長度方向之尺寸設為40 μm以下，則可藉由縮短測定時間而提高測定效率。為了進一步提高精度，較理想為測定3處以上，獲得考慮到不均之平均資訊。測定部位亦可以不接近之方式相距1 mm以上。 關於接合線之垂直於線軸之方向的芯材剖面之線長度方向之結晶方位中，相對於線長度方向之角度差為15度以下之結晶方位＜100＞的方位比率，及垂直於線軸之方向的芯材剖面之平均結晶粒徑(μm)，係藉由與本發明例1～59相同之方法而求出。又，關於0.2%耐力及最大耐力，藉由與本發明例1～59相同之方法進行評價，根據上述(1)式算出耐力比。 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樣品並進行HAST及HTS評價，根據各試驗中之球接合部之接合壽命而進行判定。接合可靠性評價用樣品係使用市售之打線接合機對將厚度0.8 μm之Al-1.0%Si-0.5%Cu之合金於通常之金屬框架上的Si基板上成膜而形成之電極進行球接合，利用市售之環氧樹脂進行密封而製作。球係一面以流量0.4～0.6 L/min流通N2 ＋5%H2 氣體一面形成，其大小係設為
Figure 02_image001
33～34 μm之範圍。 關於HAST評價，使用不飽和型壓力鍋試驗機將所製作之接合可靠性評價用樣品暴露於溫度130℃、相對濕度85%之高溫高濕環境下，施加5 V之偏壓。球接合部之接合壽命係每48小時實施球接合部之剪切試驗，設為剪切強度之值成為初期獲得之剪切強度的1/2之時間。高溫高濕試驗後之剪切試驗係藉由酸處理而去除樹脂，使球接合部露出後進行。 HAST評價之剪切試驗機係使用DAGE公司製造之試驗機。剪切強度之值係使用隨機選擇之球接合部之10處的測定值之平均值。於上述評價中，若接合壽命未達96小時，則判斷為於實用上有問題並記作×記號，若為96小時以上且未達144小時，則判斷為可實用但稍有問題並記作△記號，若為144小時以上且未達288小時，則判斷為於實用上無問題並記作〇記號，若為288小時以上且未達384小時，則判斷為優異並記作◎記號，若為384小時以上，則判斷為特別優異並記作◎◎記號，記載於表7及表8之「HAST」之欄中。 關於HTS評價，使用高溫恆溫器將所製作之接合可靠性評價用樣品暴露於溫度200℃之高溫環境下。球接合部之接合壽命係每500小時實施球接合部之剪切試驗，設為剪切強度之值成為初期獲得之剪切強度的1/2之時間。高溫高濕試驗後之剪切試驗係藉由酸處理而去除樹脂，使球接合部露出後進行。 HTS評價之剪切試驗機係使用DAGE公司製造之試驗機。剪切強度之值係使用隨機選擇之球接合部之10處的測定值之平均值。於上述評價中，若接合壽命為500小時以上且未達1000小時，則判斷為雖可實用但有改善之需求而記作△記號，若為1000小時以上且未達3000小時，則判斷為於實用上無問題並記作〇記號，若為3000小時以上，則判斷為特別優異並記作◎記號，記載於表7及表8之「HTS」之欄中。 球形成性(FAB形狀)之評價係採取進行接合前之球而進行觀察，判定球表面之氣泡之有無、原本為圓球的球之變形之有無。於產生上述任一者之情形時，判斷為不良。為了抑制熔融步驟中之氧化，球之形成係一面吹送流量0.5 L/min之氮氣一面進行。球之大小係設為34 μm。於1條件下觀察50個球。觀察係使用SEM。於球形成性之評價中，於產生5個以上之不良之情形時，判斷為有問題並記作×記號，若不良為3～4個，則判斷為可實用但稍有問題並記作△記號，於不良為1～2個之情形時，判斷為無問題並記作〇記號，於未產生不良之情形時，判斷為優異並記作◎記號，記載於表7及表8之「FAB形狀」之欄中。 線接合部之楔接合性之評價係於導線框架的導線部分進行1000條之接合，根據接合部之剝離之發生頻度而進行判定。導線框架係使用實施有1～3 μm之鍍Ag之Fe-42原子%Ni合金導線框架。於本評價中，設想較通常更嚴格之接合條件，將工作台溫度設為較通常之設定溫度範圍更低之150℃。於上述評價中，於產生11個以上之不良之情形時，判斷為有問題並記作×記號，若不良為6～10個，則判斷為可實用但稍有問題並記作△記號，於不良為1～5個之情形時，判斷為無問題並記作〇記號，於未產生不良之情形時，判斷為優異並記作◎記號，記載於表7及表8之「楔接合性」之欄中。 球接合部之壓扁形狀之評價係自正上方觀察進行接合之球接合部，根據其正圓性而判定。接合對象係使用將厚度1.0 μm之Al-0.5%Cu合金於Si基板上成膜而成之電極。觀察係使用光學顯微鏡，於1條件下觀察200處。關於與正圓之偏差較大之楕圓狀者、變形具有各向異性者，判斷為球接合部之壓扁形狀不良。於上述評價中，於產生6個以上之不良之情形時，判斷為有問題並記作×記號，若不良為4～5個，則判斷為可實用但稍有問題並記作△記號，於為1～3個之情形時，判斷為無問題並記作〇記號，於全部獲得了良好之正圓性之情形時，判斷為特別優異並記作◎記號，記載於表7及表8之「壓扁形狀」之欄中。 [偏斜] 於評價用導線框架上，以迴路長度5 mm、迴路高度0.5 mm接合100條。作為評價方法，自晶片水平方向觀察線直立部，根據通過球接合部之中心之垂線與線直立部的間隔最大時之間隔(偏斜間隔)進行評價。於偏斜間隔小於線徑之情形時，判斷為偏斜良好，於較大之情形時，直立部傾斜，故而判斷為偏斜不良。利用光學顯微鏡觀察100條接合之線，對偏斜不良之條數進行計數。於產生7個以上之不良之情形時，判斷為有問題並記作×記號，若不良為4～6個，則判斷為可實用但稍有問題並記作△記號，於不良為1～3個之情形時，判斷為無問題並記作〇記號，於未產生不良之情形時，判斷為優異並記作◎記號，記載於表7及表8之「偏斜」之欄中。 (評價結果) 本發明例3-1～3-56之接合線具有Cu合金芯材及形成於Cu合金芯材表面之Pd被覆層，接合線包含選自As、Te、Sn、Sb、Bi、Se中之至少1種以上之元素，上述元素相對於線整體之濃度合計為0.1～100質量ppm。藉此確認到，本發明例3-1～3-50之接合線於溫度為130℃、相對濕度為85%之高溫高濕環境下之HAST試驗中可獲得球接合部可靠性。 關於在Pd被覆層上進而具有包含Au及Pd之合金表皮層之本發明例，確認到包含Au及Pd之合金表皮層的層厚為0.0005～0.050 μm，藉此可獲得優異之楔接合性。 關於本發明例3-21～3-33、3-35、3-37、3-39～3-44，確認到接合線進而包含選自Ni、Zn、Rh、In、Ir、Pt、Ga、Ge中之至少1種以上之元素，上述元素相對於線整體之濃度分別為0.011～1.2質量%，Cu合金芯材中所含之Pd之濃度為0.05～1.2質量%，藉此由HTS評價所獲得之球接合部高溫可靠性良好。 關於本發明例3-22～3-26、3-29～3-32，接合線進而包含選自B、P、Mg、Ca、La中之至少1種以上之元素，上述元素相對於線整體之濃度分別為1～100質量ppm，藉此FAB形狀良好並且楔接合性良好。 關於本發明例3-34～3-44，線含有As、Te、Sn、Sb、Bi、Se並且於線之最表面存在Cu。藉此，本發明例3-34～3-44之HAST評價結果為◎◎或◎，表現出使Cu存在於最表面之效果。

Claims (8)

  1. 一種半導體裝置用接合線，其係具有Cu合金芯材及形成於上述Cu合金芯材表面之Pd被覆層之線徑為15μm以上且50μm以下者，且下述(1)式所定義之耐力比為1.1以上且1.6以下，上述接合線包含選自Ni、Zn、In、Ir、Pt中之至少1種以上之元素，上述接合線進而包含選自B、P、Mg、Ca、La中之至少1種以上之元素，耐力比=最大耐力/0.2%耐力 (1)。
  2. 一種半導體裝置用接合線，其係具有Cu合金芯材及形成於上述Cu合金芯材表面之Pd被覆層之線徑為15μm以上且50μm以下者，且下述(1)式所定義之耐力比為1.1以上且1.6以下，上述接合線包含選自Ni、Zn、In、Ir、Pt中之至少1種以上之元素，上述接合線進而包含選自B、P、Mg、Ca、La中之至少1種以上之元素，上述選自B、P、Mg、Ca、La中之至少1種以上之元素相對於線整體之濃度分別為1質量ppm以上且200質量ppm以下，耐力比=最大耐力/0.2%耐力 (1)。
  3. 如請求項1之半導體裝置用接合線，其中上述Pd被覆層之厚度為 0.015μm以上且0.150μm以下。
  4. 如請求項2之半導體裝置用接合線，其中上述Pd被覆層之厚度為0.015μm以上且0.150μm以下。
  5. 如請求項1之半導體裝置用接合線，其中上述選自Ni、Zn、In、Ir、Pt中之至少1種以上之元素相對於線整體之濃度總計為0.050質量%以上且2質量%以下。
  6. 如請求項2之半導體裝置用接合線，其中上述選自Ni、Zn、In、Ir、Pt中之至少1種以上之元素相對於線整體之濃度總計為0.050質量%以上且2質量%以下。
  7. 如請求項1至6中任一項之半導體裝置用接合線，其中上述Pd被覆層上進而具有包含Au及Pd之合金表皮層。
  8. 如請求項7之半導體裝置用接合線，其中上述包含Au及Pd之合金表皮層之厚度為0.050μm以下。
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