TWI550638B - Connecting wires for semiconductor devices - Google Patents

Connecting wires for semiconductor devices Download PDF

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Publication number
TWI550638B
TWI550638B TW104118465A TW104118465A TWI550638B TW I550638 B TWI550638 B TW I550638B TW 104118465 A TW104118465 A TW 104118465A TW 104118465 A TW104118465 A TW 104118465A TW I550638 B TWI550638 B TW I550638B
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TW
Taiwan
Prior art keywords
wire
bonding
bonding wire
concentration
coating layer
Prior art date
Application number
TW104118465A
Other languages
English (en)
Other versions
TW201631601A (zh
Inventor
Daizo Oda
Motoki Eto
Takashi Yamada
Teruo Haibara
Ryo Oishi
Tomohiro Uno
Tetsuya Oyamada
Original Assignee
Nippon Micrometal Corp
Nippon Steel & Sumikin Mat Co
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 Nippon Micrometal Corp, Nippon Steel & Sumikin Mat Co filed Critical Nippon Micrometal Corp
Publication of TW201631601A publication Critical patent/TW201631601A/zh
Application granted granted Critical
Publication of TWI550638B publication Critical patent/TWI550638B/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
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    • H01L24/42—Wire connectors; Manufacturing methods related thereto
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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Description

半導體裝置用接合導線
本發明係關於一種用於將半導體元件上之電極與外部引線等電路配線基板之配線加以連接的半導體裝置用接合導線。
目前，作為將半導體元件上之電極與外部引線之間加以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，可使用通用接合裝置、使接合導線通過其內部而用於連接之毛細治具等。接合導線之接合製程係藉由如下方式完成，即，藉由電弧熱輸入將導線前端加熱熔融，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℃之範圍內經加熱之半導體元件之電極上，繼而形成迴路後，對外部引線側之電極壓接接合(以下稱為「楔形接合」)導線部。關於作為接合導線之接合對象的半導體元件上之電極，一直採用使以Al為主體之合金於Si基板上成膜所得之電極構造、對外部引線側之電極實施鍍Ag或鍍Pd處理所得之電極構造等。
迄今為止，接合導線之材料係Au為主流，但以LSI(Large Scale Integration，大規模積體電路)用途為中心而逐漸用Cu代替Au。另一方面，近年來於電動汽車或油電混合車普及之背景下，於車載裝置用途中以Cu代替Au之需求亦提高。
關於Cu接合導線，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)。Cu與Au相比有易被氧化之缺點，存在接合可靠性、球形成性、楔形接合性等較差之課題。作為防止Cu接合導線之表面氧化之方法，已提出有以Au、Ag、Pt、Pd、Ni、Co、Cr、Ti等金屬將Cu芯材表面被覆之構造(專利文獻2)。又，已提出有於Cu芯材表面上被覆Pd且由Au、Ag、Cu或該等之合金將該表面被覆之構造(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
車載裝置與通常之電子機器相比，要求嚴酷之高溫高濕環境下之接合可靠性。尤其將導線之球部接合於電極上而成之球接合部之接合壽命成為最大問題。關於對高溫高濕環境下之接合可靠性加以評價之方法，已提出有若干方法，作為具代表性之評價法，有HAST(Highly Accelerated Temperature and Humidity Stress Test)(高溫高濕環境暴露試驗)。於藉由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130℃、相對濕度85%之高溫高濕環境下，測定接合部之電阻值之經時變化，或測定球接合部之剪切強度之經時變化，藉此評價球接合部之接合壽命。近來，於此種條件下之HAST中逐漸要求100小時以上之接合壽命。
使用先前之具有Pd被覆層之Cu接合導線與純Al電極進行接合，將第一接合設為球接合、第二接合設為楔形接合，以模塑樹脂加以密封後，進行上述HAST條件下之評價，結果存在球接合部之接合壽命 未達100小時之情況，得知車載裝置所要求之接合可靠性不充分。
本發明之目的在於提供一種對表面具有Pd被覆層之Cu接合導線改善高溫高濕環境下之球接合部之接合可靠性而適於車載裝置的接合導線。
即，本發明之要旨如下所述。
(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合金芯材之表面上之Pd被覆層者，其特徵在於： 上述接合導線包含In，In相對於導線整體之濃度為0.011~1.2質量%，上述Pd被覆層之厚度為0.015~0.150μm。
(2)如上述(1)記載之半導體裝置用接合導線，其特徵在於：上述Cu合金芯材包含選自Pt、Pd、Rh、Ni中之至少1種以上之元素，上述Cu合金芯材所含之上述元素之濃度分別為0.05~1.2質量%。
(3)如上述(1)或(2)記載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Au表皮層。
(4)如上述(3)記載之半導體裝置用接合導線，其特徵在於：上述Au表皮層之厚度為0.0005~0.050μm。
(5)如上述(1)至(4)中任一項記載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、Ga、Ge中之至少1種以上之元素，上述元素相對於導線整體之濃度分別為1~100質量ppm。
(6)如上述(1)至(5)中任一項記載之半導體裝置用接合導線，其特徵在於：於測定上述接合導線表面之結晶方位時之測定結果中，相對於上述接合導線長度方向而角度差為15度以下之結晶方位<111>之存在比率以面積率計為30~100%。
根據本發明，於具有Cu合金芯材、與形成於Cu合金芯材之表面上之Pd被覆層的半導體裝置用接合導線中，接合導線包含0.011~1.2質量%之In，藉此可延長高溫高濕環境下之球接合部之接合壽命，改善接合可靠性。
第一，本發明之接合導線係具有Cu合金芯材、與形成於上述Cu合金芯材之表面上之Pd被覆層的半導體裝置用接合導線，其中，接合導線包含In，In相對於導線整體之濃度為0.011~1.2質量%，上述Pd被覆層之厚度為0.015~0.150μm。藉此，接合導線可改善車載裝置所要求之高溫高濕環境下之球接合部之接合可靠性。
若使用本發明之接合導線藉由電弧放電而形成球，則於接合導線熔融而凝固之過程中，於球表面形成Pd濃度高於球內部之合金層。若使用該球與Al電極進行接合並實施高溫高濕試驗，則接合界面上成為Pd濃化狀態。該Pd濃化所形成之濃化層可抑制高溫高濕試驗中接合界面上之Cu、Al之擴散，使易腐蝕性化合物之成長速度降低。藉此，接合導線可提高接合可靠性。另一方面，於Pd被覆層之厚度未達0.015μm之情形時，上述濃化層未充分形成，無法提高接合可靠性。Pd被覆層之厚度更佳為0.02μm以上。另一方面，若Pd被覆層厚度超過0.150μm，則FAB形狀劣化之傾向明顯，因此將上限設為0.150μm。
形成於球表面之Pd濃度較高之合金層由於耐氧化性優異，故而可減少於球形成時球之形成位置相對於接合導線之中心而發生偏移等不良。
本發明中，進而接合導線包含In，In相對於導線整體之濃度為 0.011質量%以上，藉此可進一步延長溫度為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。
使用含有In之Pd被覆Cu接合導線形成球部，利用掃描式電子顯微鏡(SEM：Scanning Electron Microscope)觀察FAB，結果於FAB之表面觀察到多個直徑數十nm左右之析出物。若利用能量分散型X射線分析(EDS：Energy Dispersive X-ray Spectroscopy)對析出物加以分析，則確認到In濃化。儘管詳細機制尚且不明，但根據如上所述之情況而認為，於FAB上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%之高溫高濕環境下之球接合部之接合可靠性提高。更佳為In相對於導線整體之濃度為0.031質量%以上。若In之濃度為0.031質量%以上，則可進一步延長高溫高濕環境下之球接合部之接合壽命。又，In含量進而較佳為0.100質量%以上。若In之濃度為0.100質量%以上，則可進一步延長高溫高濕環境下之球接合部之接合壽命，可應對更嚴格之對接合可靠性之要求。
作為半導體裝置之封裝材料之模塑樹脂(環氧樹脂)於其分子骨架中包含氯(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發生水解而以氯化物離子(Cl-)之形式溶出。於將Cu接合導線接合於Al電極之情形時，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Cu9Al4。Cu9Al4易受到Cl等鹵素之腐蝕，由自模塑樹脂中溶出之Cl致使腐蝕進行，導致接合可靠性下降。於Cu導線具有Pd被覆層之情形時，Pd被覆Cu導線與Al電極之接合界面成為Cu/Pd濃化層/Al之構造，因此與Cu導線相比抑制Cu9Al4金屬間化合物之生成，但車載裝置所要求之高溫高濕環境下之接合可靠性並不充分。
相對於此，可認為若如本發明般於Pd被覆Cu導線中含有In，則存在進一步抑制於接合部生成Cu9Al4金屬間化合物之傾向。認為於球 接合部之FAB形成時，導線中之In亦向Pd被覆層中擴散。於球接合部之Cu與Al界面之Pd濃化層中所存在之In具有抑制Cu與Al之相互擴散之效果，結果抑制Cu9Al4之生成。又，亦有具有以下效果之可能性：導線所含之In直接妨礙Cu9Al4之形成。
作為In之存在部位，較佳為Cu芯材中，但藉由包含於Pd被覆層、Au表皮層中亦可獲得充分之作用效果。於Cu芯材中添加In之方法易於進行準確之濃度管理，導線生產性、品質穩定性提高。又，利用由熱處理所致之擴散等使一部分In亦包含於Pd被覆層或Au表皮層中，藉此亦可改良各層界面之密接性，進一步提高導線生產性。
另一方面，若導線中之In含量過剩而In相對於導線整體之濃度大於1.2質量%，則FAB形狀劣化，並且接合導線發生硬質化而導線接合部之變形不充分，楔形接合性之下降成問題。
附帶而言，有於Pd被覆層之最表面存在Cu之情形。若Cu之濃度為30原子%以上，則存在導線表面之耐硫化性下降，接合導線之使用壽命縮短故不適於實用之情況。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%。此處，所謂最表面係指於未實施濺鍍等之狀態下藉由歐傑電子分光裝置測定接合導線之表面所得之區域。
作為半導體裝置之封裝材料之模塑樹脂(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，因此可提高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高密接性之情形時，添加「含硫矽烷偶合劑」。模塑樹脂所含之硫於HAST中之溫度條件即130℃左右之條件下不游離，但若於175℃~200℃以上之條件下使用則游離。並且，若於175℃以上之高溫下游離之硫與Cu接觸，則加劇Cu之腐蝕，生成硫化物(Cu2S)或氧化物(CuO)。若於使用Cu接合導線之半 導體裝置中發生Cu之腐蝕，則尤其球接合部之接合可靠性下降。
作為對175℃以上之高溫環境下之球接合部可靠性進行評價之方法，採用HTS(High Temperature Storage Test)(高溫放置試驗)。對於暴露於高溫環境下之評價用樣品，測定接合部之電阻值之經時變化，或測定球接合部之剪切強度之經時變化，藉此評價球接合部之接合壽命。近年來，對於汽車用半導體裝置，要求175℃~200℃之HTS中之球接合部之可靠性提高。
本發明之接合導線較佳為Cu合金芯材包含選自Pt、Pd、Rh、Ni中之至少1種以上之元素，Cu合金芯材所含之上述元素之濃度分別為0.05~1.2質量%。藉由Cu合金芯材含有該等元素，於球接合部之於高溫環境下之接合可靠性中，175℃以上之HTS中之成績改善。若Cu合金芯材所含之該等成分之濃度分別未達0.05質量%，則無法獲得上述效果，若高於1.2質量%，則FAB形狀劣化，並且接合導線發生硬質化而導線接合部之變形不充分，楔形接合性之下降成問題。進而，藉由以上述含量範圍含有上述元素，可提高迴路形成性，即，可減少於高密度安裝中成問題之偏斜(leaning)。其原因在於：藉由Cu合金芯材包含Pt、Pd、Rh、Ni，接合導線之降伏強度提高，可抑制接合導線之變形。Cu合金芯材所含之上述元素之濃度更佳為0.1質量%以上、0.2質量%以上、0.3質量%以上、或0.5質量%以上。又，Cu合金芯材所含之上述元素之濃度更佳為1質量%以下、或0.8質量%以下。再者，作為由接合導線製品求出Cu合金芯材所含之上述元素之濃度的方法，例如可列舉：使接合導線之剖面露出，對Cu合金芯材之區域進行濃度分析之方法；一面藉由濺鍍等自接合導線之表面朝向深度方向切削，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，只要對接合導線之剖面進行線分析，且對不具有Pd之濃度梯度之區域(例如深度方向上之Pd之濃 度變化程度為每0.1μm未達10mol%之區域)進行濃度分析即可。關於濃度分析之方法，將於下文中說明。
本發明之接合導線可於Pd被覆層上進而具有Au表皮層。例如本發明之接合導線可於Pd被覆層之表面上進而形成0.0005~0.050μm之Au表皮層。藉此，接合導線可改善楔形接合性。
Au表皮層可與Pd被覆層反應，提高Au表皮層、Pd被覆層、Cu合金芯材間之密接強度，抑制楔形接合時Pd被覆層或Au表皮層之剝離。藉此，接合導線可改善楔形接合性。若Au表皮層之厚度未達0.0005μm，則無法獲得上述效果，若厚於0.050μm，則FAB形狀出現偏芯。Au表皮層之厚度較佳為0.0005μm以上，更佳為0.001μm以上、0.003μm以上、或0.005μm以上。又，Au表皮層之厚度較佳為0.050μm以下。再者，Au表皮層可藉由與Pd被覆層相同之方法形成。
附帶而言，有於Au表皮層之最表面存在Cu之情形。若Cu之濃度為35原子%以上，則存在導線表面之耐硫化性下降，接合導線之使用壽命縮短之現象因而不適於實用之情況。因此，於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，所謂最表面係指於未實施濺鍍等之狀態下藉由歐傑電子分光裝置測定接合導線之表面所得之區域。
接合導線進而包含選自B、P、Mg、Ga、Ge中之至少1種以上之元素，上述元素相對於導線整體之濃度分別為1~100質量ppm，藉此可改善高密度安裝所要求之球接合部之壓塌形狀，即，改善球接合部形狀之正圓性。其原因在於：藉由添加上述元素，可使球之結晶粒徑微細化，可抑制球之變形。若上述元素相對於導線整體之濃度未達1質量ppm，則無法獲得上述效果，若大於100質量ppm，則球發生硬質化，球接合時之晶片損傷成問題，因此不適於實用。上述元素相對於導線整體之濃度分別更佳為3質量ppm以上、或5質量ppm以上。上述 元素相對於導線整體之濃度分別更佳為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。
再者，於接合導線之Cu合金芯材、Pd被覆層、Au表皮層之界面上，存在因製造步驟中之熱處理等而使原子擴散，形成具有濃度梯度之合金層之情況。於如上所述之情形時，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，以Pd濃度為50原子%作為邊界，將Pd濃度為50原子%以上之區域判定為Pd被覆層，將未達50原子%之區域判定為Cu合金芯材。其根據在於：若Pd濃度為50原子%以上，則可由Pd被覆層之構造而期待特性之改善效果。又，Pd被覆層與Au表皮層之邊界係以Au濃度為基準進行判定。以Au濃度為10原子%作為邊界，將Au濃度為10原子%以上之區域判定為Au表皮層，將未達10原子%之區域判定為Pd被覆層。其根據在於：若Au濃度為10原子%以上，則可由Au表皮層之構造期待特性之改善效果。
關於Pd被覆層、Au表皮層之濃度分析、Cu合金芯材中之Pt、Pd、Rh、Ni之濃度分析，有效的是一面利用濺鍍等自接合導線之表面朝向深度方向切削一面進行分析之方法，或者使導線剖面露出而進行線分析、點分析等之方法。關於該等濃度分析所使用之解析裝置，可利用掃描式電子顯微鏡或穿透式電子顯微鏡所帶有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。作為使導線剖面露出之方法，可利用機械研磨、離子蝕刻法等。又，關於In、B、P、Mg、Ga、Ge等微量成分，可利用ICP(Inductively Coupled Plasma，感應耦合電漿)發射分光分析裝置或ICP質量分析裝置，以接合導線整體所含之元素之濃度的形式進行分析。
若接合導線表面之導線長度方向之結晶方位中，包含相對於導線長度方向而角度差為15度以內之結晶方位<111>之存在比率以面積率計為30~100%，則可提高迴路形成性，即，減少於高密度安裝 中成問題之偏斜。其原因在於：若表面結晶方位一致，則對橫向變形之耐受性增強，抑制橫向變形，因而可抑制偏斜不良。因此，於一實施形態中，於測定接合導線表面之結晶方位時之測定結果中，相對於上述接合導線長度方向而角度差為15度以下之結晶方位<111>之存在比率以面積率計為30~100%。就抑制偏斜不良之觀點而言，上述結晶方位<111>之存在比率以面積率計更佳為35%以上，進而較佳為40%以上、45%以上、50%以上、或55%以上。
(製造方法)
其次，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方式獲得，即，製造用於芯材之Cu合金後，細細地加工成導線狀，形成Pd被覆層、Au表皮層，進行熱處理。亦存在形成Pd被覆層、Au表皮層後再次進行拉絲與熱處理之情況。對Cu合金芯材之製造方法、Pd被覆層及Au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合金係藉由將成為原料之Cu與添加元素一起熔解、凝固而獲得。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等氣體混入，較佳為於真空環境或者Ar或N2等惰性氣體環境中熔解。
於Cu合金芯材之表面上形成Pd被覆層、Au表皮層之方法有鍍敷法、蒸鍍法、熔融法等。鍍敷法可應用電解鍍敷法、無電解鍍敷法之任一種。對於被稱為觸擊鍍敷、閃熔鍍敷之電解鍍敷而言，鍍敷速度較快，與基底之密接性亦良好。用於無電解鍍敷之溶液分為置換型與還原型，於厚度較薄之情形時，僅進行置換型鍍敷便足矣，於厚度較厚之情形時，有效的是分階段於置換型鍍敷後實施還原型鍍敷。
關於蒸鍍法，可利用濺鍍法、離子鍍覆法、真空蒸鍍等物理吸附及電漿CVD(Chemical Vapor Deposition，化學氣相沈積)等化學吸 附。該等均為乾式，於Pd被覆層、Au表皮層形成後無需洗淨而無洗淨時之表面污染等擔憂。
對於Pd被覆層、Au表皮層之形成而言，拉絲至最終線徑後形成該等層之方法、與於粗徑之Cu合金芯材上形成該等層後進行複數次拉絲直至達成目標線徑之方法均有效。於前者之以最終徑之狀態形成Pd被覆層、Au表皮層之情形時，便於製造、品質管理等。於後者之將Pd被覆層、Au表皮層與拉絲加以組合之情形時，於與Cu合金芯材之密接性提高之方面有利。作為各形成法之具體例，可列舉：一面於電解鍍敷溶液中連續地掃描導線，一面於最終線徑之Cu合金芯材上形成Pd被覆層、Au表皮層之方法；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形成Pd被覆層、Au表皮層後，將導線拉絲至最終線徑之方法等。
於形成Pd被覆層、Au表皮層後，存在進行熱處理之情形。藉由進行熱處理，於Au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，因此可抑制加工中之Au表皮層或Pd被覆層之剝離，於生產性提高之方面有效。為了防止來自大氣中之O2混入，較佳為於真空環境或者Ar或N2等惰性氣體環境中進行熱處理。
使接合導線表面之導線長度方向之結晶方位中包含相對於導線長度方向而角度差為15度以內之結晶方位<111>之存在比率以面積率計成為30~100%之方法如下所述。即，藉由增大Pd被覆層形成後、或形成Pd被覆層與Au表皮層後之加工率，可使導線表面上具有方向性之集合組織(結晶方位與拉絲方向一致之集合組織)成長壯大。具體而言，藉由使Pd被覆層形成後、或形成Pd被覆層與Au表皮層後之加工率為90%以上，可使接合導線表面之導線長度方向之結晶方位中包含相對於導線長度方向而角度差為15度以內之結晶方位<111>之存在比率以面積率計成為30%以上。此處，以「加工率(%)=(加工 前之導線剖面面積-加工後之導線剖面面積)/加工前之導線剖面面積×100」表示。
為了求出導線表面之導線長度方向之結晶方位中包含相對於導線長度方向而角度差為15度以內之結晶方位<111>之存在比率(面積率)，將導線表面作為觀察面而進行結晶組織之評價。作為評價方法，可使用背向散射電子繞射法(EBSD：Electron Backscattered Diffraction)。EBSD法具有對觀察面之結晶方位進行觀察且可於圖中示出相鄰測定點間之結晶方位之角度差之特徵，即便為如接合導線般之細線，亦可相對簡便且精度良好地觀察結晶方位。
表面<111>方位比率係藉由如下方式求出，即，將可由專用軟體特定之所有結晶方位作為母集團，算出導線長度方向之結晶方位中包含相對於導線長度方向而角度差為15°以內之結晶方位<111>之存在比率(面積率)。
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]
以下一面揭示實施例一面對本發明之實施形態之接合導線進行具體說明。
(樣品)
首先，對樣品之製作方法進行說明。成為芯材原材料之Cu係使用純度為99.99質量%以上且其餘部分由不可避免之雜質構成者。In、Pt、Pd、Rh、Ni、B、P、Mg、Ga、Ge係使用純度為99質量%以上且其餘部分由不可避免之雜質構成者。以芯材之Cu合金組成成為目標組成之方式調配作為添加元素之In、Pt、Pd、Rh、Ni、B、P、Mg、Ga、Ge。關於In、Pt、Pd、Rh、Ni、B、P、Mg、Ga、Ge之添加，可以單體形態進行調配，於單體形態下為高熔點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母合金後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造，即，將原料裝填至經加工成直徑為3~8mm之圓柱型之碳坩鍋內，使用高頻爐，於真空中或者氮氣或氬氣等惰性氣體環境下加熱至1090~1300℃而熔解後，進行爐冷。對所獲得之3~8mm之合金進行抽拉加工而製作0.3~1.4mm之導線。拉絲時使用市售之潤滑液，拉絲速度係設為20~400m/min。為了將導線表面之氧化膜去除而使用硫酸進行酸洗處理後，以將芯材之Cu合金整個表面被覆之方式形成1~15μm之Pd被覆層。進而，對一部分導線於Pd被覆層上形成0.01~1.5μm之Au表皮層。Pd被覆層、Au表皮層之形成係採用電解鍍敷法。鍍敷液係使用市售之半導體用鍍敷液。其後，藉由反覆進行200~700℃之熱處理與拉絲加工而將直徑加工至20μm。加工後，以最終斷裂伸長率成為約7~15%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導線一面進行，且一面流通氮氣或氬氣一面進行。導線之傳送速度係設為10~200m/min，熱處理溫度係設為200~700℃且熱處理時間係設為0.05~1.5秒。
藉由對Pd被覆層形成後、或形成Pd被覆層與Au表皮層後之加工率進行調整，可對接合導線表面之導線長度方向之結晶方位中包含相對於導線長度方向而角度差為15度以內之結晶方位<111>之存在比率(面積率)進行調整。
關於In、B、P、Mg、Ga、Ge，利用ICP發射分光分析裝置，以接合導線整體所含之元素之濃度的形式進行分析。
關於Pd被覆層、Au表皮層之濃度分析、Cu合金芯材中之Pt、Pd、Rh、Ni之濃度分析，一面利用濺鍍等自接合導線之表面朝向深度方向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、Au表皮層厚、Cu合金芯材中之Pt、Pd、Rh、Ni之濃度。
將依據上述順序所製作之各樣品之構成示於表1。表1中，對超出本發明之範圍之項目標註底線。
(評價方法)
將導線表面作為觀察面，進行結晶組織之評價。作為評價方法，使用背向散射電子繞射法(EBSD：Electron Backscattered Diffraction)。EBSD法具有對觀察面之結晶方位進行觀察且可於圖中示出相鄰測定點間之結晶方位之角度差之特徵，即便為如接合導線般之細線，亦可相對簡便且精度良好地觀察結晶方位。
將如導線表面般之曲面作為對象實施EBSD法之情形時需要注意。若測定曲率較大之部位，則難以進行高精度之測定。然而，藉由將供於測定之接合導線以平面固定於直線上，並測定該接合導線之中心附近之平坦部，可進行高精度之測定。具體而言，設定為如下測定區域即可。圓周方向之尺寸係以導線長度方向之中心作為軸而設為線徑之50%以下，導線長度方向之尺寸係設為100μm以下。較佳為圓周方向之尺寸係設為線徑之40%以下，導線長度方向之尺寸係設為40μm以下，若如此則可藉由縮短測定時間而提高測定效率。進而為了提高精度，較理想的是對3處以上進行測定而獲得考慮到不均之平均資訊。測定部位只要以不靠近之方式隔開1mm以上即可。
表面<111>方位比率係藉由如下方式求出，即，將可由專用軟體特定之所有結晶方位作為母集團，算出導線長度方向之結晶方位中包含相對於導線長度方向而角度差為15°以內之結晶方位<111>之存在比率(面積率)。
關於高溫高濕環境或高溫環境下之球接合部之接合可靠性，製作接合可靠性評價用樣品，進行HAST及HTS評價，根據各試驗中之 球接合部之接合壽命進行判定。關於接合可靠性評價用樣品，於通常之金屬框架上之Si基板上成膜厚度0.8μm之Al-1.0%Si-0.5%Cu之合金而形成電極，對所形成之電極使用市售之打線接合機進行球接合，藉由市售之模塑樹脂加以密封而製作。球係一面以0.4~0.6L/min之流量流通氮氣+5%氫氣一面形成，其大小係設為34μm。
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5V之偏壓。關於球接合部之接合壽命，每隔48小時對球接合部實施剪切試驗，設定為剪切強度之值成為初期獲得之剪切強度之1/2的時間。高溫高濕試驗後之剪切試驗係藉由酸處理將樹脂去除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。剪切強度之值係採用隨意選取之球接合部之10處測定值之平均值。於上述評價中，若接合壽命未達96小時則判斷為實用上有問題而標註記號“×”，若為96~144小時則判斷為可實用但稍有問題而標註記號“△”，若為144~288小時則判斷為實用上無問題而標註記號“○”，若為288小時以上則判斷為特別優異而標註記號“◎”，記載於表1之「HAST」欄。
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。關於球接合部之接合壽命，每隔500小時對球接合部實施剪切試驗，設定為剪切強度之值成為初期獲得之剪切強度之1/2的時間。高溫高濕試驗後之剪切試驗係藉由酸處理將樹脂去除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。剪切強度之值係採用隨意選取之球接合部之10處測定值之平均值。上述評價中，若接合壽命為500~1000小時則判斷為可實用但仍需改善而標註 記號“△”，若為1000~3000小時則判斷為實用上無問題而標註記號“○”，若為3000小時以上則判斷為特別優異而標註記號“◎”。
關於球形成性(FAB形狀)之評價，採集進行接合前之球進行觀察，判定於球表面有無氣泡、原本呈圓球狀之球有無變形。將產生上述任一情況之情形判斷為不良。關於球之形成，為了抑制熔融步驟中之氧化，一面以0.5L/min之流量吹送氮氣一面進行。球之大小係設為34μm。於一條件下觀察50個球。觀察時使用SEM。球形成性之評價中，產生5個以上之不良之情形時判斷為有問題而標註記號“×”，不良為3~4個之情形時判斷為可實用但稍有問題而標註記號“△”，不良為1~2個之情形時判斷為無問題而標註記號“○”，未產生不良之情形時判斷為優異而標註記號“◎”，記載於表1之「FAB形狀」欄。
關於導線接合部之楔形接合性之評價，於引線框架之引線部分接合1000根導線，根據接合部之剝離之發生頻度而判定。引線框架係使用經1~3μm之鍍Ag處理之Fe-42wt%Ni合金引線框架。該評價中，設想較通常更嚴酷之接合條件，將平台溫度設定為低於一般設定溫度域之150℃。上述評價中，產生11個以上之不良之情形時判斷為有問題而標註記號“×”，不良為6~10個之情形時判斷為可實用但稍有問題而標註記號“△”，不良為1~5個之情形時判斷為無問題而標註記號“○”，未產生不良之情形時判斷為優異而標註記號“◎”，記載於表1之「楔形接合性」欄。
關於球接合部之壓塌形狀之評價，對經接合之球接合部自其正上方進行觀察，根據其正圓性而判定。接合對象係使用於Si基板上成膜厚度1.0μm之Al-0.5wt%Cu之合金所得之電極。觀察係使用光學顯微鏡，於一條件下觀察200處。將與正圓偏差較大之橢圓狀者、變形具有異向性者判斷為球接合部之壓塌形狀不良。上述評價中，產生6個以上之不良之情形時判斷為有問題而標註記號“×”，不良為4~5個 之情形時判斷為可實用但稍有問題而標註記號“△”，不良為1~3個之情形時判斷為無問題而標註記號“○”，均獲得良好正圓性之情形時判斷為特別優異而標註記號“◎”，記載於表1之「壓塌形狀」欄。
[偏斜]
於評價用引線框架上以迴路長度5mm、迴路高度0.5mm接合100根導線。作為評價方法，自晶片水平方向觀察導線直立部，以通過球接合部中心之垂線與導線直立部之間隔為最大時之間隔(偏斜間隔)進行評價。偏斜間隔小於導線徑之情形時判斷為偏斜良好，大於導線徑之情形時由於直立部傾斜故判斷為偏斜不良。利用光學顯微鏡觀察100根經接合之導線，對偏斜不良之根數進行計數。產生7個以上之不良之情形時判斷為有問題而標註記號“×”，不良為4~6個之情形時判斷為可實用但稍有問題而標註記號“△”，不良為1~3個之情形時判斷為無問題而標註記號“○”，未產生不良之情形時判斷為優異而標註記號“◎”，記載於表1之「偏斜」欄。
(評價結果)
本發明例1~111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，接合導線包含In，In相對於導線整體之濃度為0.011~1.2質量%，Pd被覆層之厚度為0.015~0.150μm。確認到藉此本發明例1~111之接合導線於溫度為130℃、相對濕度為85%之高溫高濕環境下施加5V偏壓之HAST試驗中可獲得球接合部可靠性。根據本發明例12、13確認到：若In相對於導線整體之濃度為0.031質量%以上則HAST試驗中之球接合可靠性之判定成為○，為更佳之濃度範圍。又，根據本發明例14-24、47-111確認到：若In相對於導線整體之濃度為0.100質量%以上則HAST試驗中之球接合可靠性之判定成為◎，為進而較佳之濃度範圍。
另一方面，比較例1~3、7~9中，In濃度超出下限，HAST試驗中未獲得球接合部可靠性。比較例4~6、10~13中，In濃度超出上限，FAB形狀與楔形接合性不良。比較例1、4、7、19中，Pd被覆層之厚度超出下限，FAB形狀不良。
關於Pd被覆層上進而具有Au表皮層之本發明例，確認到藉由Au表皮層之層厚為0.0005~0.050μm，可獲得優異之楔形接合性。
關於實施例25~36、47~74、81~111，確認到藉由Cu合金芯材進而包含Pt、Pd、Rh、Ni且導線中所含之該等元素之濃度為0.05~1.2質量%，HTS評價中之球接合部高溫可靠性良好，並且偏斜良好。
實施例37~46、59~106、108、109、111中，藉由接合導線進而包含選自B、P、Mg、Ga、Ge中之至少1種以上之元素，且上述元素相對於導線整體之濃度為1質量ppm以上，球接合部之壓塌形狀良好。

Claims (6)

  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合金芯材之表面上之Pd被覆層者，其特徵在於：上述接合導線包含In，In相對於導線整體之濃度為0.031質量%以上、1.2質量%以下，上述Pd被覆層之厚度為0.015μm以上、0.150μm以下。
  2. 如請求項1之半導體裝置用接合導線，其中上述Cu合金芯材包含選自Pt、Pd、Rh、Ni中之至少1種以上之元素，上述Cu合金芯材所含之上述元素之濃度分別為0.05質量%以上、1.2質量%以下。
  3. 如請求項1之半導體裝置用接合導線，其於上述Pd被覆層上進而具有Au表皮層。
  4. 如請求項3之半導體裝置用接合導線，其中上述Au表皮層之厚度為0.0005μm以上、0.050μm以下。
  5. 如請求項1之半導體裝置用接合導線，其中上述接合導線進而包含選自B、P、Mg、Ga、Ge中之至少1種以上之元素，上述元素相對於導線整體之濃度分別為1質量ppm以上、100質量ppm以下。
  6. 如請求項1至5中任一項之半導體裝置用接合導線，其中於測定上述接合導線表面之結晶方位時之測定結果中，在上述接合導線長度方向之結晶方位中相對於上述接合導線長度方向而角度差為15度以下之結晶方位<111>之存在比率為30%以上、100%以下。
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