TWI574279B - Connecting wires for semiconductor devices - Google Patents

Connecting wires for semiconductor devices Download PDF

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Publication number
TWI574279B
TWI574279B TW105101101A TW105101101A TWI574279B TW I574279 B TWI574279 B TW I574279B TW 105101101 A TW105101101 A TW 105101101A TW 105101101 A TW105101101 A TW 105101101A TW I574279 B TWI574279 B TW I574279B
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TW
Taiwan
Prior art keywords
wire
core material
coating layer
less
concentration
Prior art date
Application number
TW105101101A
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English (en)
Other versions
TW201705152A (zh
Inventor
Takashi Yamada
Daizo Oda
Ryo Oishi
Tomohiro Uno
Original Assignee
Nippon Micrometal Corp
Nippon Steel & Sumikin Materials Co Ltd
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=55541238&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=TWI574279(B) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Nippon Micrometal Corp, Nippon Steel & Sumikin Materials Co Ltd filed Critical Nippon Micrometal Corp
Publication of TW201705152A publication Critical patent/TW201705152A/zh
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    • H—ELECTRICITY
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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
    • H—ELECTRICITY
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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
    • H01L24/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire 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
    • 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
    • B23K35/302—Cu as the principal constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/04—Alloys based on a platinum group metal
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Description

半導體裝置用接合導線
本發明係關於一種為了將半導體元件上之電極與外部連接端子連接而使用之半導體裝置用接合導線。
半導體元件上之電極與外部連接端子之間係使用半導體用接合導線(以下亦稱為「接合導線」)而連接。為了使接合導線接合至作為半導體元件之矽晶片上之電極，一直進行併用超音波之熱壓接方式之球形接合。另一方面，於將接合導線連接至引線或焊墊等外部連接端子之情形時，通常進行不形成球形部而將接合導線直接接合於電極之所謂2nd接合。
作為接合導線，先前主要使用線徑為15~50μm左右且材質為高純度4N(4-Nine，純度為99.99質量%以上)之Au(金)之Au接合導線(金接合導線)。
另外，伴隨著最近之資源價格之高漲，成為Au接合導線之原料之金之價格亦暴漲，作為代替Au之低成本之導線原材料，正在對Cu(銅)進行研究。然而，Cu與Au相比容易被氧化，因此單純之Cu接合導線難以實現長期之保管，2nd接合特性亦並不良好。又，於在此種單純之Cu接合導線之前端形成球形部時，必須設定為還原氛圍，以便球形部不會氧化。
因此，為了解決Cu接合導線之氧化之課題，提出有於Cu導線之表面上被覆貴金屬而成之Cu接合導線。於專利文獻1中，揭示有於高 純度Cu極細線之表面上被覆Au、Pd等貴金屬而成之Cu接合導線。
於Cu導線之表面上被覆貴金屬而成之Cu接合導線係Cu接合導線之氧化得到抑制，故而導線之長期保管或2nd接合特性優異。尤其對於在Cu導線之表面上被覆Pd而成之Cu接合導線而言，於導線前端形成球形部時，球形部氧化之擔憂得到大幅改善，即便不使用作為危險氣體之氫氣而僅使用純氮氣將球形部周邊設定為氮氣氛圍，亦可形成圓球之球形部。
[先前技術文獻]
[專利文獻1]日本專利特開昭62-97360號公報
迄今為止之引線框架之表面通常經鍍銀，與此相對，最近正在推進經鍍Pd之引線框架之使用。於在Cu導線之表面上被覆Pd而成之Cu接合導線之情形時，發現如下新問題：雖於迄今為止之鍍銀引線框架中不明顯，但對經鍍Pd之引線框架之2nd接合性變得不充分之情況變多。對於在鍍Pd上實施鍍Au而成之引線框架而言亦相同。於為了解決該問題而進行研究之過程中，本發明者等人發現，藉由使用如下之接合導線可少許減輕該問題：於Cu導線之表面上被覆Pd，於該Pd被覆層之表面上具有包含Au及Pd之合金層的接合導線。然而，對2nd接合性要求進一步之改善。尤其要求改善剝落、即經2nd接合之狀態之接合導線之接合部剝離的現象。又，伴隨著由微間距所引起之細線化，要求進一步改善2nd接合之魚尾狀(魚之尾鰭)之壓接部對稱性。本發明之第1目的在於：對於具有Pd被覆層之Cu導線，進一步改善對經鍍Pd之引線框架或者於鍍Pd上實施鍍Au而成之引線框架之2nd接合性、2nd接合之魚尾狀(魚之尾鰭)之壓接部對稱性。
又，關於Cu接合導線之長期可靠性，即便為於作為最多地利用 之加熱試驗之乾燥氛圍中之高溫保管評估中不特別產生問題的情形，若進行高濕加熱評估，則亦存在發生不良之情形。作為通常之高濕加熱評估，已知有PCT試驗(Pressure Cooker Test，壓力鍋試驗)。其中，飽和型PCT試驗常被用作相對較嚴格之評估，關於具代表性之試驗條件，於溫度121℃、相對濕度100%RH(Relative Humidity)、兩個大氣壓下進行試驗。對於具有Pd被覆層之Cu導線而言，得知可減少高濕加熱評估之不良，但若進行更嚴格之HAST試驗(High Accelerated Temperature and humidity Stress Test，高加速溫濕度試驗)(溫度130℃、相對濕度85%RH(Relative Humidity)、5V)作為高濕加熱評估，則與Au導線相比較，不良之發生率仍較高。本發明之第2目的在於：對具有Pd被覆層之Cu導線進一步減少高濕加熱評估之不良。
本發明者等人發現，藉由在具有以Cu為主成分之芯材、位於該芯材之表面上且以Pd為主成分之被覆層、及位於該被覆層之表面上且包含Au與Pd之表皮合金層的接合導線中，使以Cu為主成分之芯材中含有特定量之元素週期表第10族之金屬元素，並且將導線最表面之Cu濃度設定為1at%以上，可進一步改善對經鍍Pd之引線框架或者於鍍Pd上實施鍍Au而成之引線框架之2nd接合性、2nd接合之魚尾狀(魚之尾鰭)之壓接部對稱性。
又，本發明者等人發現，藉由使以Cu為主成分之芯材中含有特定量之元素週期表第10族之金屬元素，於如HAST試驗般之嚴酷之高濕加熱評估中亦可減少不良之發生。
本發明係基於上述見解而完成者，其主旨如下。
(1)一種半導體裝置用接合導線，其包含：芯材，其係以Cu為主成分，且含有總計為0.1~3.0質量%之元素週期表第10族之金屬元素；被覆層，其係設置於該芯材表面上，且以Pd為主成分；及表皮合 金層，其係設置於該被覆層表面上，且包含Au與Pd；上述半導體裝置用接合導線之特徵在於：導線最表面之Cu濃度為1~10at%。
(2)如(1)所記載之半導體裝置用接合導線，其中上述元素週期表第10族之金屬元素為選自由Ni、Pd及Pt所組成之群中之1種以上。
(3)如(1)或(2)所記載之半導體裝置用接合導線，其中上述元素週期表第10族之金屬元素包含Ni。
(4)如(1)至(3)中任一項所記載之半導體裝置用接合導線，其中上述以Pd為主成分之被覆層之厚度為20~90nm，上述包含Au與Pd之表皮合金層之厚度為0.5~40nm，Au之最大濃度為15~75at%。
(5)如(1)至(4)中任一項所記載之半導體裝置用接合導線，其中上述芯材更含有Au，芯材中之Ni、Pd、Pt、Au之總計超過0.1質量%且為3.0質量%以下。
(6)如(1)至(5)中任一項所記載之半導體裝置用接合導線，其中上述接合導線更含有P、B、Be、Fe、Mg、Ti、Zn、Ag、Si中之1種以上，占導線總體之該等元素之濃度總計為0.0001~0.01質量%的範圍。
(7)如(1)至(6)中任一項所記載之半導體裝置用接合導線，其中於上述芯材與上述被覆層之交界部、及上述被覆層與上述表皮合金層之交界部具有擴散區域。
(8)如(1)至(7)中任一項所記載之半導體裝置用接合導線，其中於對與上述接合導線之導線軸為垂直方向之芯材截面(以下稱為「垂直截面」)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°以下之結晶方位<100>的方位比率為30%以上。
本發明藉由在具有以Cu為主成分之芯材、設置於該Cu合金芯材 之表面上且以Pd為主成分之被覆層、及設置於該被覆層之表面上且包含Au與Pd之表皮合金層的半導體裝置用接合導線中，使以Cu為主成分之芯材中含有特定量之元素週期表第10族之金屬元素，並且將導線最表面之Cu濃度設為1~10at%，可進一步改善對經鍍Pd之引線框架或於鍍Pd上實施鍍Au而成之引線框架之2nd接合性。又，藉由使以Cu為主成分之芯材中含有特定量之元素週期表第10族之金屬元素，對於接合導線與電極之間之球形接合部而言，即便於高濕加熱條件下亦可實現優異之球形接合性。
以下，根據本發明之較佳實施形態詳細地對本發明進行說明。以下，與濃度、厚度、比率相關而示出之數值係若未另行明示，則表示平均值。
本發明之半導體裝置用接合導線之特徵在於包含：芯材，其係以Cu為主成分，且含有總計為0.1~3.0質量%之元素週期表第10族之金屬元素；被覆層，其係設置於該芯材之表面上，且以Pd為主成分；及表皮合金層，其係設置於該被覆層之表面上，且包含Au與Pd；並且導線最表面之Cu濃度為1~10at%。
首先，對以Cu為主成分、且含有總計為0.1~3.0質量%之元素週期表第10族之金屬元素的芯材(以下亦稱為「Cu合金芯材」)進行說明。
Cu容易被氧化，故包含Cu之接合導線係長期保管或2nd接合特性較差，但若於Cu合金芯材之表面上形成以Pd為主成分之被覆層，則Cu合金芯材之氧化得到抑制，故上述長期保管或2nd接合特性優異。
又，於使用表面上具有Pd被覆層之Cu導線於Al電極上進行球形 接合之情形時，於在導線前端形成球時，於經熔融之球表面上形成Pd濃化層。因如上所述般於球表面上形成Pd濃化層，故於Al電極上進行球形接合時，與不具有Pd被覆層之Cu導線相比，高濕加熱評估之不良減少。
然而，關於在Cu芯材上設置Pd被覆層而成之Cu接合導線之長期可靠性，若進行HAST試驗(High Accelerated Temperature and humidity Stress Test)(溫度130℃、相對濕度85%RH(Relative Humidity)、5V)作為高濕加熱評估，則與Au導線相比，不良之發生率仍較高。
關於在球形接合時形成之球表面之Pd濃化層，存在如下情形：並非一直於整個球表面上形成Pd濃化層，而僅於球之側面形成Pd濃化層，於球之前端部未形成Pd濃化層。而且，本發明者等人發現，於未於球前端部形成Pd濃化層之情形時，高濕加熱評估中之不良發生頻率增大。其原因在於：Cu接合導線中所含之Pd量不足。因此，作為增加Pd量之方法，考慮到使以Pd為主成分之被覆層變厚，但如下所述，就減少晶片損傷等觀點而言，Pd被覆層之厚度存在較佳之上限，使該被覆層變厚而增加Pd量存在極限。
若於未於球前端部形成Pd濃化層之狀況下於Al電極上進行球形接合，則以Cu為主成分之芯材於球前端部之表面上露出，該部分與Al電極直接接觸而形成接合部。於該情形時，在高濕加熱評估試驗中，於Cu/Al接合界面(Cu接合導線與Al電極之接合界面)上Cu-Al系之金屬間化合物成長，該Cu-Al系之金屬間化合物與密封樹脂中所含之氯等氣體成分或離子等發生腐蝕反應。其結果導致高濕加熱評估試驗中之不良。
與此相對，於本發明中，使用以Cu為主成分且含有特定量之元素週期表第10族之金屬元素的Cu合金芯材。可認為，藉此Cu合金芯材中之元素週期表第10族之金屬元素於球形接合時擴散或濃化至接合 界面，影響Cu與Al之相互擴散，由此使腐蝕反應變慢。接合界面附近之元素週期表第10族之金屬元素之作用可想到：妨礙腐蝕反應物之移動之障壁功能，控制Cu、Al之相互擴散及金屬間化合物之成長等之功能等。於本發明中，Cu合金芯材中之元素週期表第10族之金屬元素較佳為選自由Ni、Pd及Pt所組成之群中之1種以上。於較佳之一實施形態中，Cu合金芯材包含Ni作為元素週期表第10族之金屬元素。例如，Cu合金芯材可單獨含有Ni作為元素週期表第10族之金屬元素，亦可組合含有Ni與Pd、Pt中之一者或兩者。於另一較佳之實施形態中，Cu合金芯材包含Pd、Pt中之一者或兩者作為元素週期表第10族之金屬元素。
若Cu合金芯材中之元素週期表第10族之金屬元素之濃度總計為0.1質量%以上，則可充分地控制接合界面上之Cu、Al之相互擴散，即便於作為嚴酷之高濕加熱評估試驗之HAST試驗中，接合部之壽命亦提高至380小時以上。作為此處之接合部之評估，於HAST試驗後將樹脂開封去除，此後藉由拉力試驗(pull test)評估接合部之斷裂狀況。就充分地獲得上述HAST試驗可靠性之改善效果之觀點而言，Cu合金芯材中之元素週期表第10族之金屬元素之濃度總計為0.1質量%以上，較佳為0.2質量%以上，更佳為0.3質量%以上、0.4質量%以上、0.5質量%以上、或0.6質量%以上。又，就低溫接合時與Al電極之初始接合強度良好，獲得HAST試驗中之長期可靠性或對BGA(Ball Grid Array，球狀柵格陣列)、CSP(Chip Size Package，晶片尺寸封裝體)等之基板、帶等的接合之量產裕度優異的接合導線之觀點，減少晶片損傷之觀點而言，Cu合金芯材中之元素週期表第10族之金屬元素之濃度總計為3.0質量%以下，較佳為2.5質量%以下、或2.0質量%以下。若Cu合金芯材中之元素週期表第10族之金屬元素之濃度總計超過3.0質量%，則存在如下情形：需要以低負重進行球形接合以不產生晶片 損傷，與電極之初始之接合強度下降，結果HAST試驗可靠性劣化。本發明之接合導線藉由將Cu合金芯材中之元素週期表第10族之金屬元素之濃度之總計設定為上述較佳範圍，HAST試驗中之可靠性進一步提高。例如，可實現HAST試驗之直至發生不良為止的壽命超過450小時之接合導線。該情況有時亦相當於先前之Cu接合導線之1.5倍以上之長壽命化，亦可對應於嚴酷環境下之使用。再者，作為由接合導線製品求出Cu合金芯材中所含之上述元素之濃度之方法，例如可列舉如下方法：使接合導線之截面露出，對Cu合金芯材之區域進行濃度分析之方法；一面藉由濺鍍等而自接合導線之表面向深度方向切削，一面對Cu合金芯材之區域進行濃度分析之方法。例如，於Cu合金芯材包含具有Pd之濃度梯度之區域之情形時，只要對接合導線之截面進行線分析，對不具有Pd之濃度梯度之區域(例如，深度方向上之Pd之濃度變化之程度為每0.1μm未達10mol%之區域，Cu合金芯材之軸心部)進行濃度分析即可。關於濃度分析之方法，將於下文中進行敍述。
於本發明中，亦可使Cu合金芯材中更含有Au。若使Cu合金芯材中更含有Au，則再結晶溫度上升，防止拉線加工中之動態再結晶，故而加工組織變均勻，調質後之晶粒尺寸相對變均勻。藉此，導線之斷裂伸長率提高，於接合時可形成穩定之導線迴路。於更含有Au之情形時，較佳為以芯材中之Ni、Pd、Pt、Au之總計成為超過0.1質量%且3.0質量%以下之方式設定含量。芯材中之Ni、Pd、Pt、Au之總計之下限更佳為0.2質量%以上、0.3質量%以上、0.4質量%以上、0.5質量%以上、或0.6質量%以上，該總計之上限更佳為2.5質量%以下、或2.0質量%以下。
本發明之接合導線較佳為更含有選自P、B、Be、Fe、Mg、Ti、Zn、Ag、Si中之1種以上之元素，且占導線總體之該等元素之濃度之 總計為0.0001~0.01質量%的範圍。藉此，可實現更良好之球形狀。該等元素濃度之總計之下限更佳為0.0003質量%以上、0.0005質量%以上、或0.001質量%以上，該等元素濃度之上限更佳為0.009質量%以下、或0.008質量%以下。於本發明之接合導線含有該等元素之情形時，該等元素可包含於Cu合金芯材中，亦可包含於下文將述之被覆層、表皮合金層中。
Cu合金芯材中含有之成分除了以元素週期表第10族之金屬元素為首之上述成分以外，剩餘部分為Cu及不可避免之雜質。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)。先前之Pd被覆Cu接合導線就接合性(bondability)之觀點而言，係使用高純度(4N以上)之Cu芯材，有避免使用低純度之Cu芯材之傾向。與此相對，對於具有Cu合金芯材、設置於該Cu合金芯材之表面上且以Pd為主成分之被覆層、及設置於該被覆層之表面上且包含Au與Pd之表皮合金層並且導線最表面之Cu濃度為1~10at%之本發明之接合導線而言，特別適於如上所述般使用Cu之純度相對較低之Cu合金芯材之情形，實現了對經鍍Pd之引線框架或於鍍Pd上實施鍍Au而成之引線框架的2nd接合性之進一步改善、及如HAST試驗般之嚴酷之高濕加熱評估中之優異的球形接合性。
其次，對以Pd為主成分之被覆層進行說明。
如上所述，為了抑制Cu合金芯材之氧化，形成於Cu合金芯材之表面上且以Pd為主成分之被覆層的厚度較佳為20~90nm。若被覆層之厚度為20nm以上，則抑制氧化之效果變充分，2nd接合性及FAB(FreeAir Ball，無空氣焊球)形狀變良好，故而較佳。再者，所謂FAB形狀係指圓球性、有無偏芯、及有無收縮。被覆層之厚度更佳為25nm以上、或30nm以上。又，若被覆層之厚度為90nm以下，則晶片損傷減少，並且FAB形狀變良好，進而，於球形部之表面上產生直 徑為數μm之大小之氣泡之情況較少，因而較佳。被覆層之厚度更佳為85nm以下、或80nm以下。
此處，以Pd為主成分之被覆層中除了Pd以外所含之元素為Pd之不可避免之雜質、構成被覆層之內側之芯材之成分、構成被覆層之表面側之表皮合金層之元素。其原因在於存在以下情形：由於下文將述之熱處理，於芯材與被覆層之間、表皮合金層與被覆層之間發生各層之構成元素之相互擴散。即，若著眼於被覆層，則其原因在於：存在構成芯材之元素及構成表皮合金層之元素向被覆層擴散之情形。因此，於一實施形態中，本發明之接合導線於芯材與被覆層之交界部、及被覆層與表皮合金層之交界部具有擴散區域。因此，於本發明中，芯材與被覆層之交界係設定為Pd濃度為50at%之位置，被覆層與表皮合金層之交界係設定為Au為10at%之位置，將該等交界之間設定為被覆層之厚度。
關於以Pd為主成分之被覆層之Pd之最大濃度，就可進一步享有本發明之效果之觀點而言，較佳為60at%以上，更佳為70at%以上、80at%以上、或90at%以上。被覆層之Pd之最大濃度較佳為100at%，但對於使用包含特定量之元素週期表第10族之金屬元素之Cu合金芯材並且導線最表面的Cu濃度為1~10at%之本發明之接合導線而言，即便於被覆層之Pd之最大濃度未達100at.%，例如為99.9at.%以下、99.8at.%以下、99.7at.%以下、99.6at.%以下、99.5at.%以下、99.0at.%以下、98.5at.%以下、98at.%以下、97at.%以下、96at.%以下、或95at.%以下之情形時，亦可達成所期望之效果。
於本發明之接合導線中，Pd被覆層中之Pd濃度為99.0at.%以上之區域之厚度可為40nm以下，例如亦可為35nm以下、30nm以下、25nm以下、20nm以下、15nm以下、10nm以下、或5nm以下。
其次，對包含Au及Pd之表皮合金層進行說明。
如上所述，僅於Cu合金芯材之表面上具有以Pd為主成分之被覆層之構成的情況下，無法於鍍Pd引線框架上確保良好之2nd接合性。於本發明中，於以Pd為主成分之被覆層之表面上進而形成包含Au及Pd之表皮合金層。包含Au及Pd之表皮合金層之厚度較佳為0.5~40nm。若導線之最表面之區域為Au與Pd之合金層，則於使導線於鍍Pd引線框架上進行2nd接合時，構成導線之最表面之表皮合金層中之Au優先向鍍Pd引線框架上之Pd擴散，容易於接合導線與鍍Pd引線框架兩者之間形成合金層。因此，與鍍Pd引線框架之2nd接合性提高。又，於經閃熔鍍Au之鍍Pd引線框架上，亦同樣地確認到2nd接合性提高，可認為該情形是由引線框架上之極薄閃熔鍍敷之Au與表皮合金層中之Au彼此之密接性促進效果所致。就改善鍍Pd引線框架或於鍍Pd上實施鍍Au而成之引線框架的2nd接合性之觀點而言，表皮合金層之厚度較佳為0.5nm以上，更佳為1nm以上、2nm以上、或3nm以上。另一方面，若表皮合金層之厚度過厚，則存在FAB形狀劣化之情形，又，昂貴之Au之使用量增加而成本變高，因此表皮合金層之厚度較佳為40nm以下，更佳為35nm以下、或30nm以下。
又，藉由在具有上述被覆層及上述表皮合金層之導線之Cu合金芯材中含有元素週期表第10族之金屬元素，與在未經Pd被覆之裸Cu中含有元素週期表第10族之金屬元素之情形相比，除了上述接合可靠性提高以外，HAST評估結果進一步提高。可認為其原因在於：於形成於球表面上之Pd濃化層中，導線表面之被覆層之Pd、與Cu合金芯材中所含有之元素週期表第10族之金屬元素兩者組合，由此Pd濃化層中之元素週期表第10族之金屬元素之合計濃度上升，促進控制接合界面上之Cu、Al之相互擴散及金屬間化合物之成長等的功能。
先前之Pd被覆Cu導線存在如下情形：Pd層與毛細管內壁之滑動阻抗較高，於接合動作時Pd被切削。於反覆進行接合之過程中，在毛 細管上附著切削屑等異物，若其量變多則必須更換毛細管。與此相對，藉由更具有包含Au及Pd之表皮合金層，導線最表面之摩擦阻抗變低。又，如上所述，藉由向芯材中添加元素週期表第10族之金屬元素而確保適當之強度。由於該等效果，毛細管內壁與導線之滑動阻抗下降而進行順利之接合動作，即便反覆進行接合，亦可將因異物對毛細管之附著所引起之污染抑制得較少，從而毛細管壽命提高。又，作為毛細管內壁與導線之滑動阻抗下降之結果，迴路穩定性或偏斜特性提高。
進而可認為，表皮合金層中所含之Au元素提高以下作用，即，於球表面上穩定地形成由導線表面之被覆層之Pd及Cu合金芯材中的元素週期表第10族之金屬元素兩者所形成之Pd濃化層；又，促進電極之Al自接合界面向球方向擴散之現象，促進僅元素週期表第10族之金屬元素之情況下變慢的接合界面上之相互擴散速度，促進對腐蝕之耐性較高之金屬間化合物之成長。
就改善對鍍Pd引線框架或於鍍Pd上實施鍍Au而成之引線框架之2nd接合性之觀點而言，包含Au及Pd之表皮合金層中之Au之最大濃度較佳為15at%以上。表皮合金層之剩餘部分為Pd及不可避免之雜質。再者，於表皮合金層之最表面上，如下所述般Cu濃化。就改善對鍍Pd引線框架等之2nd接合性之觀點而言，表皮合金層中之Au之最大濃度更佳為20at%以上，進而較佳為25at%以上、30at%以上、35at%以上、或40at%以上。就特別改善對鍍Pd引線框架或者於鍍Pd上實施鍍Au而成之引線框架之2nd接合性之觀點而言，Au之最大濃度較佳為40at%以上。另一方面，若Au之最大濃度超過75at%，則存在如下情形：於在導線前端形成球形部時，包含Au及Pd之表皮合金層中之Au優先熔融，由此形成扁癟球形部之危險性增加，FAB形狀變得不良。與此相對，若表皮合金層中之Au之最大濃度為75at%以下，則於在導 線前端形成球形部時，不存在僅Au優先熔融而形成扁癟球形部之危險性，不會損及球形部之圓球性或尺寸精度，故而較佳。就提高球形部之圓球性或尺寸精度之觀點而言，表皮合金層中之Au之最大濃度較佳為75at%以下，更佳為70at%以下，進而較佳為65at%以下、60at%以下、或55at%以下。就提高球形部之圓球性或尺寸精度，實現特別良好之FAB形狀之觀點而言，Au之最大濃度較佳為55at%以下。
本發明之接合導線之特徵在於：導線最表面之Cu濃度為1~10at%。所謂導線最表面係指包含Au及Pd之表皮合金層之表面。導線最表面之Cu濃度變高之區域(以下稱為「Cu濃化部」)較佳為其厚度為2~9nm。Cu濃化部之厚度係設定為自導線最表面至Cu濃度成為導線最表面之一半的位置為止之厚度。
如上所述，於具有以Cu為主成分之芯材、位於該芯材之表面上且以Pd為主成分之被覆層、及位於該被覆層之表面上且包含Au與Pd之合金層之接合導線中，使以Cu為主成分之芯材中含有特定量之元素週期表第10族之金屬元素，並且將導線最表面之Cu濃度設定為特定之範圍，藉此可進一步改善對經鍍Pd之引線框架或於鍍Pd上實施鍍Au而成之引線框架之2nd接合性，且同時提高2nd接合之魚尾狀(魚之尾鰭)之壓接部之對稱性。關於該作用，藉由將上述特定之Cu合金芯材、與導線最表面之Cu濃化部/包含Au及Pd之表皮合金層/以Pd為主成分之被覆層的被覆構造組合使用，可獲得明顯之改善效果。可認為，藉由發揮上述特定之Cu合金芯材、表皮合金層、及Cu濃化部之組合的協同作用，而進一步改善2nd接合性，2nd接合中之導線變形之對稱性提高。
Cu具有如下性質：於包含於其他金屬中之情形時，在高溫下容易因晶粒內擴散、晶界擴散等而擴散。於具有Cu合金芯材、位於該Cu合金芯材之表面上且以Pd為主成分之被覆層、及進而位於該被覆 層之表面上且包含Au與Pd之表皮合金層之本發明中，若如下所述般進行擴散熱處理或退火熱處理，則芯材之Cu於被覆層或表皮合金層中擴散，可使Cu到達表皮合金層之最表面。可認為，導線最表面之上述Cu之狀態係表面濃化或表面偏析，但亦可一部分Cu氧化，或亦可於表皮合金層之包含Au及Pd之合金中上述濃度範圍之Cu一部分固熔。
如上所述，於Cu芯材之表面上僅具有以Pd為主成分之被覆層的先前之Pd被覆Cu接合導線使用高純度(4N以上)之Cu芯材，有避免使用低純度之Cu芯材之傾向。於此種先前之Pd被覆Cu接合導線中，若於導線最表面上Cu濃化，則可見FAB形狀變得不良之現象。所謂FAB形狀係指圓球性、有無偏芯、及有無收縮。又，對於2nd接合性，亦可見不充分之性能進一步下降之現象。與此相對，於本發明作為對象之包含以Cu為主成分且含有特定量之元素週期表第10族之金屬元素的特定之Cu合金芯材、設置於該Cu合金芯材之表面上且以Pd為主成分之被覆層、及設置於該被覆層之表面上且包含Au與Pd之表皮合金層之半導體裝置用接合導線中，未出現因Cu於導線最表面上濃化所引起之性能之下降，相反地首次發現，藉由在導線最表面上含有1at%以上之Cu，可大幅度地改善對經鍍Pd之引線框架之2nd接合性、特別是剝落性。就可進一步改善2nd接合性之觀點而言，於本發明之接合導線中，導線最表面之Cu濃度較佳為1.5at%以上，更佳為2at%以上、2.5at%以上、或3at%以上。
然而，若表皮合金層之表面、即導線最表面之Cu濃度過高，則存在產生如下問題之情形：2nd接合性及FAB形狀變得不良，進而導線表面容易氧化，品質經時性地下降。就實現良好之2nd接合性及FAB形狀之觀點、抑制導線表面之氧化而抑制品質之經時劣化之觀點而言，於本發明之接合導線中，導線最表面之Cu濃度為10at%以下， 較佳為9.5at%以下、或9at%以下。
作為包含Au及Pd之表皮合金層之形成方法，較佳為於Cu合金芯材之表面上被覆Pd，進而於其表面上覆著Au，此後對導線進行熱處理而使Pd與Au相互擴散，形成包含Au及Pd之表皮合金層。使被覆層之Pd以到達表皮合金層之表面為止之方式擴散，且以表面之Pd濃度成為25at%以上之方式進行擴散，藉此表皮合金層表面之Au濃度成為75at%以下。例如，於在Cu合金芯材之表面上被覆Pd並實施鍍Au後，進行拉線而以導線直徑200μm及100μm共計進行2次適當之熱處理，藉此最終線徑之表面之Pd濃度成為25at%以上。此時，構成Pd濃度自表皮合金層之最表面向導線之中心依次增大之濃度梯度。藉此，可將表皮合金層之Au之最大濃度設定為15at%~75at%。此處，將Au濃度成為10at%之位置定義為表皮合金層與以Pd為主成分之被覆層之交界。
再者，藉由使Pd擴散至表皮合金層中之上述熱處理，於Cu合金芯材與以Pd為主成分之被覆層之間亦引起相互擴散。其結果，存在如下情形：於Cu合金芯材與被覆層之交界附近，形成Pd濃度自表面側向中心依次減少並且Cu濃度增大之區域之情形；或於上述交界部形成厚度為20nm以下之Pd-Cu金屬間化合物層之情形；於本發明中，將任一情形均稱為擴散區域。
對本發明之導線之成分組成之評估方法進行說明。
於被覆層、表皮合金層之濃度分析、Cu合金芯材中之Ni、Pd、Pt、Au之濃度分析時，以下方法有效：一面藉由濺鍍等自接合導線之表面向深度方向切削一面進行分析之方法，或者使導線截面露出而進行線分析、點分析等之方法。前者係於表皮合金層、被覆層較薄之情形時有效，但若該表皮合金層、被覆層變厚，則過度地耗費測定時間。後者之截面之分析係於表皮合金層、被覆層較厚之情形時有效，又，其優點在於截面總體之濃度分佈、或數個部位之再現性之確認等 相對較為容易，但於表皮合金層、被覆層較薄之情形時，精度下降。亦可對接合導線進行傾斜研磨，使表皮合金層、被覆層、芯材及其等之交界部之擴散區域之厚度擴大而進行測定。
截面之情況下，線分析相對較簡便，但於欲提高分析之精度時，進行使線分析之分析間隔變窄、或聚集於界面附近之欲觀察之區域的點分析之情形亦有效。
用於該等濃度分析中之解析裝置可利用掃描式電子顯微鏡(SEM)或穿透式電子顯微鏡(TEM)所具備之奧傑電子光譜分析(AES)裝置、能量分散型X射線分析(EDX)裝置、電子束微量分析儀(EPMA(Electron Probe Micro Analyzer，電子探針微量分析儀))等。作為使導線截面露出之方法，可利用機械研磨、離子蝕刻法等。尤其使用AES裝置之方法因空間解析度較高，故對於最表面之較薄區域之濃度分析有效。
關於接合導線中之P、B、Be、Fe、Mg、Ti、Zn、Ag、Si之分析，可利用ICP(Inductively Coupled Plasma，感應耦合電漿)發光光譜分析裝置或ICP質量分析裝置對以強酸溶解接合導線所得之液體進行分析，以接合導線總體中所包含之元素之濃度之形式進行檢測。又，於平均組成之調查等中，亦能以酸等自表面部開始階段性地溶解，根據該溶液中所含之濃度求出溶解部位之組成等。
關於形成於被覆層與芯材之交界之Pd-Cu化合物，利用EPMA、EDX裝置、AES裝置、TEM等，於導線之研磨截面中進行夾持芯材與被覆層之界面之線分析，藉此可獲知擴散區域之厚度、組成等。
以下，將與接合導線之導線軸為垂直方向之芯材截面稱為「垂直截面」。於垂直截面中測定結晶方位，藉此可評估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°以下之結晶方位<100>的方位比率。於本發明中，較佳為於芯材之垂直截面中，導 線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°以下之結晶方位<100>之方位比率係設定為30%以上。藉由芯材具有此種結晶組織，可抑制偏斜不良，並且於球形接合時形成之球形部軟質化，球形接合時之晶片損傷減少。又，由於導線軟質化，故可改善2nd接合性。就抑制偏斜不良之觀點、減少晶片損傷之觀點、更進一步改善2nd接合性之觀點而言，上述結晶方位<100>之方位比率更佳為35%以上，進而較佳為40%以上、45%以上、50%以上、或55%以上。
於上述芯材之垂直截面中觀察到之結晶方位可利用設置於TEM觀察裝置中之微小區域X射線法或者背散射電子束繞射法(EBSD，Electron Backscattered Diffraction)等進行測定。其中，EBSD法具有對觀察面之結晶方位進行觀察，且可將相鄰測定點間之結晶方位之角度差圖示的特徵，即便為如接合導線般之細線，亦可相對較簡便且精度良好地觀察結晶方位，因此更佳。又，關於相對於導線長度方向而角度差為15°以下之結晶方位<100>之方位比率，於微小區域X射線法中可根據各結晶方位之X射線強度以結晶方位之體積比率的形式求出，又，EBSD法中可根據上述觀察到之結晶方位直接算出。為了算出垂直截面之方位比率，於與接合導線之拉線方向垂直之方向上觀察接合導線之截面全域。關於結晶方位比率之算出方法，為了將無法測定結晶方位之部位、或即便可進行測定但方位解析之可靠度亦較低之部位等除外而進行計算，於測定區域內，僅將能以專用軟體中設定之可靠度為基準進行鑑定之結晶方位之面積設定為母集團。只要由上述任一方法所得之厚度或組成為本發明之範圍內，則可獲得本發明之作用效果。
本發明之半導體裝置用接合導線之線徑亦取決於半導體裝置之所期望的設計，可為10~80μm之範圍，通常為10~50μm之範圍。
其次，對本發明之半導體裝置用接合導線之製造方法進行說明。
首先，根據Cu合金芯材之組成稱量高純度之Cu(純度99.99%以上)及添加元素原料作為起始原料後，將其於高真空下或者氮氣或氬氣(Ar)等惰性氛圍下加熱而熔解，藉此獲得含有特定之成分且剩餘部分為Cu及不可避免之雜質的直徑為約2~10mm之錠。供於製造本發明之接合導線之錠係以Cu為主成分且含有總計為0.1~3.0質量%的元素週期表第10族之金屬元素之直徑為約2~10mm之銅合金錠。該銅合金錠可含有之其他成分如對本發明之接合導線之銅合金芯材所說明，該等成分之含量之較佳之範圍亦如上述內容。對該銅合金錠進行鑄造、軋壓、拉線而製作供形成被覆層之直徑為約0.3~1.5mm之銅合金導線。本發明亦提供此種供於半導體裝置用接合導線之銅合金錠及銅合金導線。
作為於Cu合金芯材之表面上形成以Pd為主成分之被覆層之方法，可利用電解鍍敷、無電鍍敷、蒸鍍法等，利用可穩定地控制膜厚之電解鍍敷於工業上而言最佳。藉由該等方法於Cu合金芯材表面上形成以Pd為主成分之被覆層後，於上述被覆層之表面上形成包含Au及Pd之表皮合金層。形成表皮合金層之方法可為任一方法，為了於形成上述被覆層後進而於該被覆層之表面上形成Au膜作為表皮層，將所覆著之Au製成包含Au及Pd之合金層，只要藉由熱處理以Pd到達Au之表面為止之方式使Pd擴散即可。作為該方法，如下方法可確實地控制合金之組成及厚度，因此較佳：以固定之爐內溫度於電爐中在固定之速度下將導線連續地掃描，藉此促進合金化。再者，作為於上述被覆層之表面上形成Au膜之方法，可利用電解鍍敷、無電鍍敷、蒸鍍法等，根據上述原因，利用電解鍍敷於工業上而言最佳。關於在Cu合金芯材之表面上覆著被覆層及表皮合金層之階段，若於拉線至最終 之Cu合金芯材之直徑為止後進行則最佳，亦可於Cu合金芯材之拉線中途階段中於拉線至特定之線徑為止之時間點進行覆著，此後拉線至最終線徑為止。於該情形時，作為半成品而獲得含有以Cu為主成分且含有總計為0.1~3.0質量%之元素週期表第10族之金屬元素之芯材、設置於該芯材表面上且以Pd為主成分之被覆層、及設置於該被覆層表面上且以Au為主成分之表皮層(較佳為包含Au及Pd之表皮合金層)的直徑為約100~700μm之複層導線。又，被覆層及表皮合金層亦可於錠之階段中進行覆著。
於用以進行表皮合金層之合金化之加熱時，考慮到原料之污染而將爐內之氛圍設定為氮氣或氬氣等惰性氛圍，進而，與先前之接合導線之加熱法不同，將氛圍中所含之氧濃度設定為5000ppm以下。更佳為若於惰性氣體中混入至少500ppm之氫氣等還原性氣體，則防止導線之原料之污染的效果進一步提高，因此良好。又，爐內之適當之溫度或掃描導線之速度亦根據導線之組成而不同，若將爐內溫度設為大致210℃~700℃之範圍，且將掃描導線之速度設為例如20~40m/min左右，則可實現穩定之操作，可獲得穩定品質之接合導線，因此較佳。用以進行表皮合金層之合金化之加熱若於拉線至最終之芯材之直徑為止後進行，則可兼作拉線後之導線之退火，因此較佳。當然，亦可於拉線至中間階段之直徑為止時，進行用以進行表皮合金層之合金化之加熱。藉由按以上方式進行加熱，Cu合金芯材之Cu於被覆層或表皮合金層中擴散，可使Cu到達表皮合金層之最表面。藉由在上述較佳範圍內適當地選擇加熱溫度及時間，可將導線最表面之Cu濃度設定為1~10at%之範圍。
為了個別地控制表皮合金層之厚度、及上述被覆層之厚度，與簡單之一次熱處理相比，於在Cu合金芯材之表面上被覆Pd後實施熱處理，進而於覆著Au後實施熱處理之情況有效。於該情形時，有針 對各熱處理條件之爐內溫度、導線之掃描速度可個別地設定之優點。
形成表皮合金層、被覆層後之加工步驟係根據目的而選擇、區分使用輥軋壓、旋鍛、模具拉線等。根據加工速度、壓下率或模具減縮率等而控制加工組織、位錯、晶界之缺陷等之情況下，亦對表皮合金層、被覆層之構造、密接性等造成影響。
加工後之熱處理步驟係要求以最終之導線直徑進行，但僅此難以獲得所期望之合金層、被覆層之厚度、Au之最大濃度、表面之Cu濃度。於該情形時，於加工中途實施2至3次熱處理步驟之情況有效。
尤其Au與Pd係熔點及加工容易度(強度)均不同，故而重要的是預先於加工度較低之階段中進行熱處理，遍及導線全周而形成Au-Pd之合金層。又，為了於表面上使Cu濃化，有效的是並非簡單地提高熱處理溫度，而是預先勉強提高經惰性氣體填充之熱處理爐中之氧濃度。然而，若氧濃度過高，則擔心Cu合金芯材中之Cu之氧化，故氧濃度較理想的是設定為0.2%~0.7%，除此之外之熱處理中以預先將氧濃度降至ppm等級為宜。
為了形成所期望之組成及膜厚之被覆層、表皮合金層、最表面之Cu濃化部，有效的是根據初始形成之膜厚、複數次熱處理條件等，利用菲克(Fick)之定律等通常之相互擴散之知識進行估算。進而為了提高精度，根據上述估算而試製導線1次左右，藉由表面解析求出實際之擴散現象而製備熱處理裝置等之條件，藉此即便為不同之膜厚、組成，應對亦變容易。
關於Cu合金芯材之垂直截面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°以下之結晶方位<100>之方位比率，可藉由在最終拉線後進行之熱處理之條件進行控制。即，若將熱處理溫度設定為相對較低之溫度、例如350~550℃，則發生用以去除加工應變之再結晶(一次再結晶)，但粗大之晶粒之成長(二次再結晶) 可抑製得較少。雖然一次再晶粒之<100>結晶方位之比率較多，但二次再晶粒之<100>結晶方位之比率較少。藉此，可將Cu合金芯材之垂直截面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°以下之結晶方位<100>之方位比率設定為30%以上。
[實施例]
作為接合導線之原材料，為了製造Cu合金芯材，準備純度為99.99質量%以上之Cu及作為添加元素之Ni、Pd、Pt、Au、P、B、Be、Fe、Mg、Ti、Zn、Ag、Si，被覆層形成用係準備純度為99.99質量%以上之Pd，表皮合金層形成用係準備純度為99.99質量%以上之Au。於稱量Cu及添加元素原料作為起始原料後，將其於高真空下加熱而熔解，藉此獲得直徑為10mm左右之銅合金錠。此後，對該錠進行鑄造、軋壓、拉線而製作直徑為500μm之Cu合金導線。其次，以如下方式實施電解鍍敷而獲得複層導線：於Cu合金導線表面上，使Pd被覆層成為1~3μm厚，於被覆層之表面上，使Au表皮層成為0.05~0.2μm厚。將Pd被覆層、Au-Pd表皮合金層之最終厚度記載於表1、表2。此處，芯材與被覆層之交界係設定為Pd濃度為50at%之位置，被覆層與表皮合金層之交界係設定為Au濃度為10at%之位置。此後，以拉線速度為100~700m/min且模具減縮率為8~30%進行連續拉線加工，調整為表1、表2中所記載之最終線徑。表皮合金層之厚度、Au最大濃度、表面Cu濃度、被覆層之厚度係藉由在拉線加工之期間中實施2次至3次熱處理而控制。關於此時之條件，於導線直徑為200~250μm時，溫度為500~700℃且速度為10~70m/min，於導線直徑為70~100μm時，溫度為450~650℃且速度為20~90m/min，於最終線徑較細之情形時，進而於導線直徑為40~70μm時，溫度為300~500℃且速度為30~100m/min。此後，以最終線徑以表1、表2之溫度、速度30~120m/min實施熱處理。又，為了使Cu擴散至表面為 止，僅1次熱處理係將熱處理爐中之氧濃度設定為0.2~0.7%而較通常更高。該熱處理較佳為儘可能於最後進行，其原因在於，若於Cu於表面上出現後反覆進行拉線加工，則容易引起Cu之氧化。除此之外之熱處理係藉由將熱處理爐中之氧濃度設定為未達0.2%，而一面抑制表皮合金層之過度氧化，一面控制穩定之厚度、組成等。以此種方式獲得直徑為15~25μm之接合導線。
關於被覆層、表皮合金層之濃度分析、Cu合金芯材之Ni、Pd、Pt、Au之濃度分析，一面利用Ar離子自接合導線之表面向深度方向進行濺鍍，一面使用AES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(profile)(深度之單位為SiO2換算)而求出。於觀察元素分佈時，亦進行利用EPMA、EDX裝置等之分析。將Pd之濃度為50at%以上且Au之濃度未達10at%之區域設為被覆層，將位於被覆層之表面上且Au濃度為10at%以上之範圍之區域設為表皮合金層。將被覆層及表皮合金層之厚度及組成記載於表1、表2。接合導線中之P、B、Be、Fe、Mg、Ti、Zn、Ag、Si之濃度係藉由ICP發光光譜分析裝置、ICP質量分析裝置等而測定。
於接合導線之連接時，使用市售之自動打線接合機。於即將進行接合前，藉由電弧放電於接合導線之前端製作球形部，其直徑係以成為接合導線之直徑之1.7倍之方式選擇。製作球形部時之氛圍係設定為氮氣。
作為接合導線之接合對象，分別使用形成於Si晶片上之厚度為1μm之Al電極、及表面經鍍Pd之引線框架之引線。於將所製作之球形部與經加熱至260℃之上述電極進行球形接合後，將接合導線之母線部與經加熱至260℃之上述引線進行2nd接合而再次製作球形部，藉此連續地反覆接合。迴路長度係設定為3mm及5mm兩種，迴路高度係設定為0.3mm及0.5mm兩種。
關於接合導線之2nd接合性，對裕度、剝落、強度、魚尾對稱性進行評估。關於裕度，在將2nd接合時之負重以10gf為單位自20gf起增加至90gf為止、將超音波以10mA為單位自60mA起增加至120mA為止之56個條件下實施100根連續接合，對可實現連續接合之條件進行計數。將可實現連續接合之條件為40以上視為◎，將30以上且未達40視為○，將未達30視為×。關於剝落，觀察100根經2nd接合之狀態之接合導線之接合部，將接合部剝離者計數為NG。關於魚尾對稱性，觀察100根經2nd接合之狀態之接合導線之接合部，對其對稱性進行評估。測量自魚尾狀壓接部之中央至左端為止之長度、至右端為止長度，將其差為10%以上者計數為NG。剝落及魚尾對稱性係將NG為0個視為◎，將1~10個視為○，將11個以上視為×。關於強度，於2nd接合部正上方抓持經2nd接合之狀態之接合導線，向上方提拉至切斷為止，讀取於該切斷時獲得之斷裂負重。因強度受到線徑之影響，故而利用強度/導線拉伸強度之比率。該比率若為85%以上則為良好，故視為◎，70~85%係判斷為無問題而視為○，55~70%係判斷為存在發生不良之情形而視為△，55%以下係判斷為不良而視為×，標記於表3、表4之「2nd接合強度」之欄中。
關於接合導線之1st接合性(球形接合性)，對HAST試驗、球形狀、FAB形狀、晶片損傷進行評估。為了評估HAST試驗中之球形接合部之健全性，對於已進行接合之半導體裝置，放置於溫度為130℃、相對濕度為85%RH(Relative Humidity)、5V之高溫高濕爐中，每隔48小時取出並進行評估。作為評估方法，測定電阻，將電阻上升者視為NG。將直至成為NG為止之時間為480小時以上視為◎，將384小時以上且未達480小時視為○，將未達384小時視為×。
關於球形狀，利用光學顯微鏡觀察100個球形接合部，將接近正圓者視為OK，將成為花瓣狀者視為NG，並對其數量進行計數。關於 FAB形狀，於引線框架上製作100個FAB，利用SEM進行觀察。將圓球狀者視為OK，將偏芯、收縮視為NG，並對其數量進行計數。球形狀及FAB形狀係將NG為0個視為◎，將1~5個視為○，將6~10個視為△，將11個以上視為×。◎及○為合格，△雖為合格但品質略微不良。
於晶片損傷之評估中，對20個球形接合部進行截面研磨，若電極產生龜裂則判斷為不良，不良為4個以上之情形係以×記號標記，3個以下之情形係以△記號標記，1~2個之情形為○，若未觀察到龜裂則視為良好而標記為◎記號，標記於表3、表4之「晶片損傷」欄中。○及◎為合格，△雖為合格但品質略微不良。
關於偏斜評估，對於迴路長度：3mm及5mm、迴路高度：0.3mm及0.5mm各者，於進行接合後，各試樣均係利用光學顯微鏡觀察100根迴路，僅於0~2根迴路中觀察到偏斜不良之情形為良好而以◎記號標記，僅於3~4根迴路中觀察到偏斜不良之情形為實用上無問題之水準而以○記號標記，5~7根之情形係以△記號標記，若於8根以上之迴路中觀察到偏斜不良則為差而以×記號標記，標記於表3、表4之「偏斜」欄中。△、○、◎為合格。
關於芯材之垂直截面中觀察到之相對於導線長度方向而角度差為15°以下之結晶方位<100>之方位比率，於藉由EBSD法對觀察面之結晶方位進行觀察後算出。於EBSD測定資料之解析中，利用專用軟體(TSL製造之OIM analysis等)。於進行算出時，選擇接合導線之全域，對各試樣均分別以3視場進行觀察。將芯材之垂直截面中相對於導線長度方向而角度差為15°以下之結晶方位<100>之方位比率記入至表3、表4之「垂直截面」之「結晶方位<100>」之欄中。
於表2中，對偏離本發明範圍之數值附註下劃線。
關於本發明例1~35，於所評估之所有品質指標中，可實現合格水準之品質實績。
比較例1係導線最表面之Cu濃度未達下限，故而2nd接合之剝落及魚尾對稱性不良，且被覆層之厚度超過較佳範圍之上限，故而晶片損傷及FAB形狀雖合格但品質略微不良。比較例2係導線最表面之Cu濃度未達下限，故而2nd接合之剝落及魚尾對稱性不良，且被覆層之厚度未達較佳範圍之下限，故而FAB形狀雖合格但品質略微不良。比較例3及7係作為必要元素之添加元素1之添加量未達下限，故而高濕加熱條件下之球形接合性(HAST評估)不良，進而2nd接合之裕度及強度不良，且被覆層之厚度未達較佳範圍之下限，故而FAB形狀雖合格但品質略微不良。比較例4係導線最表面之Cu濃度未達下限，故而2nd接合之剝落及魚尾對稱性不良，且表皮合金層之厚度及Au之最大濃度超過較佳範圍之上限，故而FAB形狀雖合格但品質略微不良。
比較例5係導線最表面之Cu濃度超過本發明之上限，2nd接合之裕度及強度與FAB形狀不良。
再者，關於比較例5，<100>結晶方位偏離本發明之較佳範圍，故而偏斜為△之結果，雖為合格之範圍但性能略微下降。
使用高純度(4N以上)之Cu芯材且作為必要元素之添加元素1之添加量未達下限之比較例6係2nd接合之剝落及魚尾對稱性不良。

Claims (7)

  1. 一種半導體裝置用接合導線，其包含：芯材，其係以Cu為主成分，且含有總計為0.1質量%以上3.0質量%以下之元素週期表第10族之金屬元素；被覆層，其係設置於該芯材表面上，且以Pd為主成分；及表皮合金層，其係設置於該被覆層表面上，且包含Au及Pd；上述半導體裝置用接合導線之特徵在於：導線最表面之Cu濃度為1at%以上10at%以下；上述元素週期表第10族之金屬元素包含Ni。
  2. 如請求項1之半導體裝置用接合導線，其中上述元素週期表第10族之金屬元素進而包含Pd、Pt中之一者或兩者。
  3. 如請求項1之半導體裝置用接合導線，其中上述以Pd為主成分之被覆層之厚度為20nm以上90nm以下，上述包含Au及Pd之表皮合金層之厚度為0.5nm以上40nm以下，Au之最大濃度為15at%以上75at%以下。
  4. 如請求項1之半導體裝置用接合導線，其中上述芯材更含有Au，芯材中之Ni、Pd、Pt、Au之總計超過0.1質量%且為3.0質量%以下。
  5. 如請求項1之半導體裝置用接合導線，其中上述接合導線更含有P、B、Be、Fe、Mg、Ti、Zn、Ag、Si中之1種以上，占導線總體之該等元素濃度之總計為0.0001質量%以上0.01質量%以下之範圍。
  6. 如請求項1之半導體裝置用接合導線，其中構成上述芯材之元素及構成上述表皮合金層之元素向上述被覆層擴散。
  7. 如請求項1至6中任一項之半導體裝置用接合導線，其中於對與上述接合導線之導線軸為垂直方向之芯材截面測定結晶方位之 結果中，導線軸方向之結晶方位中，相對於導線軸方向而角度差為15°以下之結晶方位<100>之方位比率為30%以上。
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