TW201631602A - 耐腐蝕及耐濕性之接合線 - Google Patents
耐腐蝕及耐濕性之接合線 Download PDFInfo
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Abstract
本發明揭示一種包括芯之線,該芯包括以下各項或由以下各項組成(a)鎳,其量處於自0.005wt.-%至5wt.-%之範圍中,(b)視情況,銀,其量處於自0.005wt.-%至1wt.-%之範圍中,(c)銅,其量處於自94wt.-%至99.98wt.-%之範圍中,及(d)0wt.-ppm至100wt.-ppm之其他組分,其中以wt.-%及wt.-ppm計之所有量皆係基於該芯之總重量,其中該芯具有處於自1.5μm至30μm之範圍中之平均晶粒大小,該平均大小係根據線截取方法而判定,其中該線具有處於自8μm至80μm之範圍中之平均直徑。
Description
本發明係關於一種包括銅芯、粗度為8μm至80μm之線,該銅芯包括:銅;鎳,其量處於自0.005wt.-%(重量-%、重量%)至5wt.-%之範圍中;及視情況,銀,其量處於自0.005wt.-%至1wt.-%之範圍中,其中以wt.-%計之所有量皆基於該芯之總重量;其中該銅芯具有處於自1.5μm至30μm之範圍中之平均晶粒大小。本發明進一步係關於一種用於製造此種線之程序。
接合線在電子應用及微電子應用中之使用係所習知的目前技術現狀。儘管在開始接合線係由金製成,但當今使用較不昂貴之材料,諸如銅。儘管銅線提供非常良好之導電性及導熱性,但銅線接合仍具有挑戰。此外,銅線易於受到腐蝕及氧化。
就線幾何形狀而言,最常用者係具有圓形剖面之接合線及具有大致矩形剖面之接合帶。兩種類型之線幾何形狀皆具有使其可用於特定應用之優點。
某些最新研發涉及具有銅芯之接合線。作為芯材料,因高導電性而選擇銅。已尋找銅材料之不同摻雜劑以使接合性質最佳化。舉例而言,US 7,952,028 B2闡述若干具有大量不同摻雜劑及濃度之基於銅之不同測試線。
然而,就接合線本身及接合程序而言,持續需要進一步改良接合線技術。
因此,本發明之一目標係提供改良之接合線。
本發明之另一目標係提供就針腳式接合而言展現極佳可接合性之接合線。
本發明之另一目標係提供具有改良之可靠性以及改良之耐腐蝕性及耐濕性之接合線。
本發明之另一目標係提供就球接合而言展現改良之可靠性及可接合性之接合線。
本發明之另一目標係提供就球楔接合而言展現改良之經接合球圓度及同心性之接合線。
已發現本發明之線至少解決改良耐腐蝕性及耐濕性之目標。此外,已找到用於製造此等線之程序。
類別形成請求項之標的物促成了上述目標之解決方案。類別形成請求項之附屬子請求項代表本發明之較佳實施例,該等附屬子請求項之標的物亦促進解決上文所提及之目標。
本發明之第一態樣係一種包括芯之線,該芯包括以下各項或由以下各項組成(a)鎳,其量處於自0.005wt.-%至5wt.-%、較佳0.1wt.-%至0.6wt.-%或甚至0.45wt.-%至0.55wt.-%之範圍中,(b)視情況,銀,其量處於自0.005wt.-%至1wt.-%、較佳0.1wt.-%至0.6wt.-%或甚至0.45wt.-%至0.55wt.-%之範圍中,(c)銅,其量處於自94wt.-%至99.98wt.-%、較佳98.5wt.-%至99.6wt.-%或甚至99.4wt.-%至99.6wt.-%之範圍中,及(d)0wt.-ppm至100wt.-ppm(重量-ppm、重量ppm)之其他組分,其中以wt.-%及wt.-ppm計之所有量皆基於該芯之總重量,其中該芯具有處於自1.5μm至30μm之範圍中之平均晶粒大小,該平均大小係根據線截取方法而判定,
其中該線具有處於自8μm至80μm或甚至12μm至55μm之範圍中之平均直徑。
該線較佳係用於微電子裝置中之接合之接合線。該線較佳係一體式物件。已知且出現了眾多適用於本發明之線之形狀。在剖面圖中,較佳形狀係圓形、橢圓形及矩形形狀。
平均直徑係藉由「大小測定方法」來獲得。根據此種方法,判定所界定長度之線之實體重量。基於此重量,使用線材料之密度(銅之密度:ρCu=8.92g/cm3)來計算線之直徑。將平均直徑作為在五次切割特定線時所得之五個量測值之算術平均值來計算。
對於本發明而言,術語「接合線」包括所有形狀之剖面及所有常用線直徑,但具有圓形剖面及細直徑之接合線係較佳的。
用於判定平均晶粒大小之線截取方法係標準金相實踐。此處,垂直於線的方向對線進行切割,且蝕刻由此產生之剖面。在本發明上下文中,晶粒之大小被界定為可通過晶粒之直線之所有剖面中之最長者。平均晶粒大小係芯/塊體材料中之至少七個晶粒量測值之算術平均值。測試係根據ASTM E112-96標準(第16.3章,第13頁)來執行。
如已提及,線芯包括(a)0.005wt.-%至5wt.-%之鎳及(c)94wt.-%至99.98wt.-%之銅。線芯可或可不包括組分(b),即銀。若線芯包括銀,則銀之量處於自0.005wt.-%至1wt.-%之範圍中。
本發明之線芯包括(d)0wt.-ppm至100wt.-ppm之其他組分。此等其他組分之低量確保線性質之良好再現性。在本發明上下文中,該等其他組分(常常亦稱作「不可避免的雜質」)係源自用於或來自線製造程序之原始材料中存在之雜質之微量化學元素及/或化合物。此等其他組分之實例係:Mn、Pt、Cr、Ca、Ce、Mg、La、Al、B、Zr、Ti、S、Fe。
換言之,該芯包括以下各項或由以下各項組成
(a)鎳,其量處於自0.005wt.-%至5wt.-%、較佳0.1wt.-%至0.6wt.-%或甚至0.45wt.-%至0.55wt.-%之範圍中,(b)銀,其量處於自0.005wt.-%至1wt.-%、較佳0.1wt.-%至0.6wt.-%或甚至0.45wt.-%至0.55wt.-%之範圍中,(c)銅,其量處於自94wt.-%至99.98wt.-%、較佳98.5wt.-%至99.6wt.-%或甚至99.4wt.-%至99.6wt.-%之範圍中,及(d)0wt.-ppm至100wt.-ppm之其他組分,或(a)鎳,其量處於自0.005wt.-%至5wt.-%、較佳0.1wt.-%至0.6wt.-%或甚至0.45wt.-%至0.55wt.-%之範圍中,(b)無銀,(c)銅,其量處於自94wt.-%至99.98wt.-%、較佳98.5wt.-%至99.6wt.-%或甚至99.4wt.-%至99.6wt.-%之範圍中,及(d)0wt.-ppm至100wt.-ppm之其他組分,其中以wt.-%及wt.-ppm計之所有量皆基於芯之總重量。
根據上述,本發明之實施例係一種包括以下各項之線:(a)鎳,(b)視情況,銀;及(c)銅,如上文所揭示。芯中存在之其他組分通常並非單獨地添加。其他組分之存在源自鎳、銀及銅中之一或多者中存在之雜質。
在一實施例中,本發明之線芯包括少於以下量之其他組分:(i)Mn,其<15wt.-ppm;(ii)Pt、Cr、Ca、Ce、Mg、La、Al、B、Zr、Ti中之任一者,其各自<2wt.-ppm;(iii)S、Fe中之任一者,其各自<10wt.-ppm。
形成芯之材料更佳滿足上述限值中之至少兩者,形成芯之材料最佳滿足所有限值。
在一實施例中,線芯包括元素磷作為摻雜劑,基於芯之總重量,其量處於自40wt.-ppm至80wt.-ppm之範圍中。
在本發明上下文中,線芯被界定為塊體材料之同質區域。因任一塊體材料始終具有可在一定程度上展現不同性質之表面區域,故線芯之性質應理解為塊體材料之同質區域之性質。塊體材料區域之表面可在形態、組成(例如氧含量)及其他特徵方面有所不同。表面可係線芯之外表面。在替代方案中,其可係線芯與疊置於線芯上之塗層之間的界面區域。
在本發明之上下文中,術語「疊置」用於闡述第一物項(例如銅芯)相對於第二物項(例如塗層)之相對位置。「疊置」表徵,其他物項(例如中間層)可(但無需)配置於第一物項與第二物項之間。較佳地,關於第一物項之總表面,第二物項至少部分地疊置於第一物項上,例如至少30%、50%、70%或至少90%。最佳地,第二物項完全疊置於第一物項上。
在本發明之上下文中,術語「中間層」係指芯與塗層之間的線區域。在此區域中,存在芯及塗層兩者之材料之組合。
在本發明之上下文中,術語「厚度」用於界定層在垂直於芯之縱軸之方向上之大小,該層至少部分地疊置於芯之表面上。
在一實施例中,芯直徑與平均晶粒大小之間的比率處於自2至14或甚至2至7之範圍中。
在一實施例中,線之平均直徑處於自15μm至28μm之範圍中。在此情形中,芯中之平均晶粒大小較佳處於自1.5μm至6μm之範圍中。
在另一實施例中,線之平均直徑處於自>28μm至38μm之範圍中。在此情形中,芯中之平均晶粒大小較佳處於自2μm至10μm之範圍中。
在另一實施例中,線之平均直徑處於自>38μm至50μm之範圍中。在此情形中,芯中之平均晶粒大小較佳處於自5μm至15μm之範圍中。
在另一實施例中,芯之平均直徑處於自>50μm至80μm之範圍中。在此情形中,芯中之平均晶粒大小較佳處於自7μm至30μm之範圍中。
在一實施例中,芯具有表面,其中塗層疊置於芯之表面上。
在一實施例中,相對於芯之總質量,塗層之質量不大於2.5wt.-%、較佳不大於2wt.-%或更小。當存在塗層時,相對於芯之總質量,其常常具有0.1wt.-%或更大或者0.5wt.-%或更大之最小質量。應用低量之材料作為塗層保存了由線芯之材料所界定之特性。另一方面,塗層為線表面賦予特定特性,諸如對環境呈惰性、耐腐蝕性、改良之可接合性等。舉例而言,對於平均直徑為18μm之線,塗層之厚度處於自60nm至70nm之範圍中。舉例而言,對於具有25μm之平均直徑之線,塗層可具有處於自90nm至100nm之範圍中之厚度。
在一實施例中,塗層係由選自由鈀、鉑及銀組成之群組之元素製成。該塗層可係該等元素中之一者之單層。在另一實施例中,該塗層可係若干個經疊置毗鄰層之多層,其中每一層係由選自由鈀、鉑及銀組成之群組之一種元素製成。作為塗層一部分之每一層係自上述純金屬元素中之一者個別地沈積。用於在芯上沈積此等元素之常見技術係鍍覆(諸如電鍍及無電極鍍覆)、自氣相沈積材料(諸如濺鍍、離子鍍覆、真空蒸鍍及物理氣相沈積)以及自熔體沈積材料。
在一實施例中,另一塗層疊置於該塗層上。在一實施例中,各相對於芯之總質量,另一塗層之質量不大於0.2wt.-%、較佳不大於0.1wt.-%。
舉例而言,對於具有18μm之平均直徑之線,該另一塗層之厚度
處於自2nm至4nm之範圍中。舉例而言,對於具有25μm之平均直徑之線,該另一塗層可具有自3.5nm至5.5nm之厚度。
在一實施例中,該另一塗層係金層。
在一實施例中,本發明之線至少由以下特徵中之一者來表徵:
α)耐腐蝕性具有至多0%經接合球剝離之值;參見如下文所述之「測試方法G」。
β)耐濕性具有至多0%經接合球剝離之值;參見如下文所述之「測試方法I」。
γ)線芯之硬度不大於120HV、較佳不大於115HV或不大於110HV;參見如下文所述之「測試方法J」。
δ)針腳式接合之程序窗面積具有至少40μm.g或至少90μm.g或至少120μm.g之值,每一值皆係在線具有18μm之平均直徑之前提下提供;參見如下文所述之章節「測試方法C」。
ε)線之電阻率不大於1.80μΩ.cm。
ζ)平均經接合球圓度具有至多0.0025μm或至多0.002μm或至多0.0018μm之值,每一值皆係在線具有18μm之平均直徑之前提下提供;參見如下文所述之章節「測試方法E」。
η)平均經接合球同心性具有至多0.00056μm或至多0.0005μm或至多0.0004μm之值,每一值皆係在線具有18μm之平均直徑之前提下提供;參見如下文所述之章節「測試方法E」。
本發明之第二態樣係一種用於製造上文所揭示實施例中之任一者中之線之程序。在其最一般實施例中,該程序至少包括以下程序步驟
(1)提供前驅物項,其包括以下各項或由以下各項組成:(a)鎳,其量處於自0.005wt.-%至5wt.-%、較佳0.1wt.-%至0.6wt.-%或甚至0.45wt.-%至0.55wt.-%之範圍中,
(b)視情況,銀,其量處於自0.005wt.-%至1wt.-%、較佳0.1wt.-%至0.6wt.-%或甚至0.45wt.-%至0.55wt.-%之範圍中,(c)銅,其量處於自94wt.-%至99.98wt.-%、較佳98.5wt.-%至99.6wt.-%或甚至99.4wt.-%至99.6wt.-%之範圍中,及(d)0wt.-ppm至100wt.-ppm之其他組分,其中以wt.-%及wt.-ppm計之所有量皆基於前驅物項之總重量,(2)將該前驅物項伸長以形成線前驅物,直至獲得線芯之所要直徑為止;以及(3)對在完成程序步驟(2)之後獲得之經伸長線前驅物進行退火。
如在程序步驟(1)中所提供之前驅物項可係藉由用所要量之鎳及視情況銀對銅進行合金化及/或摻雜而獲得。藉由產生該等組分與銅之熔體並使該熔體冷卻以形成一塊基於銅之同質前驅物項來實現合金化及摻雜。通常,此種前驅物項係呈直徑例如為2mm至25mm且長度例如為5m至100m之桿之形式。此種桿可係藉由在具有室溫之適當模具中鑄造包括以下各項或由以下各項組成之銅合金熔體、後續接著進行冷卻及凝固來製成:(a)鎳,其量處於自0.005wt.-%至5wt.-%之範圍中,(b)視情況,銀,其量處於自0.005wt.-%至1wt.-%之範圍中,(c)銅,其量處於自94wt.-%至99.98wt.-%之範圍中,及(d)0wt.-ppm至100wt.-ppm之其他組分,其中以wt.-%及wt.-ppm計之所有量皆基於銅合金熔體之總重量。可藉由熟習金屬合金技術者已知的習用程序來製備銅合金本身,舉例而言,藉由將銅、鎳及視情況銀以所要比率熔化在一起。如此一來,可利用習用銅-鎳及銅-銀母合金。舉例而言,可利用感應爐來執行熔化程序,且在真空下或在惰性氣體氛圍下工作係有利的。所使用材料可具有例如99.99wt.-%及更高之純度級。
若如針對本發明第一態樣之實施例中之某些實施例所揭示在線上存在一或多個塗層,則此等塗層較佳係施加至線前驅物。熟習此項
技術者知曉如何以針對線實施例所揭示之厚度(即,在將前驅物項與一或多個塗層一起伸長為線前驅物之後)來計算前驅物項上之此等塗層之厚度以獲得該等塗層。如上文已揭示,已知用於根據該等實施例在銅或銅合金表面上形成材料之塗層之眾多技術。較佳技術係鍍覆(諸如電鍍及無電極鍍覆)、呈氣相之材料之沈積(諸如濺鍍、離子鍍覆、真空蒸鍍及物理氣相沈積)以及熔融材料之沈積。
如針對本發明第一態樣之實施例中之某些實施例所揭示,為給線芯疊置單層或多層金屬塗層,一旦達到處於例如80μm至200μm之範圍中之某一前驅物直徑,中斷程序步驟(2)即為有利的。然後,可例如藉由一或多個電鍍程序步驟來施加單層或多層金屬塗層。此後,繼續程序步驟(2),直至獲得線芯之所要及最終直徑。
在程序步驟(2)中,將前驅物項伸長以形成線前驅物,直至獲得線芯之所要直徑為止。已知用以將前驅物項伸長以形成線前驅物的眾多技術且其在本發明之上下文中顯現為有用的。較佳技術係軋延、型鍛、模拉等,其中模拉尤其較佳。在後一情形中,以數個程序步驟拉製前驅物項,直至達到線芯之所要及最終直徑為止。
線芯之所要及最終直徑可處於自8μm至80μm之範圍中或較佳處於自12μm至55μm之範圍中。此種線模拉程序係熟習此項技術者眾所習知的。
可採用習用碳化鎢及金剛石拉模,且可採用習用拉製潤滑劑來支援拉製。舉例而言,可以8個主要階段來拉製前驅物項,且每一階段具有15至25個程序步驟,其中在每一拉製程序步驟中,執行將前驅物項之長度伸長自6%至18%之範圍。對於每一拉製程序步驟,伸長%可相同或不同。
在程序步驟(3)中,較佳在管式爐中將在完成程序步驟(2)之後獲得之經伸長線前驅物退火。較佳,退火係股線退火(最終退火),其為
一種用於允許以高再現性快速生產線之連續程序。股線退火意指,在使線前驅物移動穿過較佳管式退火爐並在離開該爐之後纏繞於捲軸上之同時以動態方式進行退火。退火係在例如440℃至700℃之範圍中之目標溫度下執行達0.1秒至0.4秒,較佳在470℃至650℃之範圍中之目標溫度下執行達0.1秒至0.3秒;此等溫度/時間條件允許達成或調整線芯之所要平均晶粒大小。
退火通常係藉由將經伸長線前驅物拉動穿過習用退火爐來執行,該退火爐通常呈具有給定長度之圓柱形管之形式且在給定退火速度下具有所界定溫度量變曲線,該給定退火速度可係在例如自4公尺/分鐘至30公尺/分鐘或自14公尺/分鐘至16公尺/分鐘之範圍中選擇。如此一來,可界定並設定退火時間/目標溫度參數。
關於本發明之實施例,已發現,在低於最大伸長率溫度之溫度下進行之退火可產生有益線性質,乃因可以積極方式影響線形態。此外,已發現,將退火溫度選擇為高於最大伸長率溫度同時維持退火時間常數具有進一步優點。舉例而言,可使用此製造原理將線之平均晶粒大小調整至(例如)較大平均晶粒大小。藉由此調整,可以積極方式影響其他性質,例如線硬度、球接合行為等。
因此,在一實施例中,退火係在高於最大伸長率溫度之溫度下執行,其中線在退火之後之伸長率值不大於最大伸長率值之98%。舉例而言,程序步驟(3)可係在比最大伸長率溫度T△L(max)至少高10℃、較佳至少高50℃或至少高80℃之溫度下執行。通常,程序步驟(3)中之溫度比T△L(max)高不超過200℃。最大伸長率溫度T△L(max)係藉由測試試樣(線)在不同溫度下斷裂時之伸長率來判定。以曲線圖來收集資料點,其展示隨溫度(℃)而變之伸長率(%)。所得曲線圖通常稱為「退火曲線」。在基於銅之線之情形中,觀察伸長率(%)達到最大值時之溫度。此即為最大伸長率溫度T△L(max)。圖1中展示實例,其根據樣品3
(表1)展示以鎳合金化之18μm銅線之實例性退火曲線。退火溫度係x軸之變數參數。該曲線圖展示線之斷裂負荷(BL,克)及伸長率(EL,%)之所量測值。藉由拉伸測試來判定伸長率。在所顯示實例中,伸長率量測值展現約10%之典型局部最大值,此係在大約470℃之退火溫度下達成。若根據樣品3之線並非係在此最大伸長率溫度下而是在560℃(其比最大伸長率溫度高90℃)下退火,則結果係約9.8%之伸長率值,其比最大伸長率值低2%。
該退火可係在惰性或還原氛圍中執行。眾多類型之惰性氛圍以及還原氛圍在此項技術中係已知的且用於清掃退火爐,該退火爐通常係管式退火爐。在已知惰性氛圍中,氮係較佳的。在已知還原氛圍中,氫係較佳的。另一較佳還原氛圍係氫氮混合物。較佳氫氮混合物係90vol.-%至98vol.-%氮及因此2vol.-%至10vol.-%氫,其中總vol.-%係100vol.-%。較佳氮/氫混合物等於93/7、95/5及97/3vol.-%/vol.-%,其各自係基於混合物之總體積。若線表面之某些部分易於被空氣中之氧進行氧化(例如,若線之銅被曝露於其表面),則在退火中應用還原氛圍係尤其較佳的。以該等類型之惰性氣體或還原氣體進行清掃較佳以處於43min-1至125min-1、更佳43min-1至75min-1、最佳50min-1至63min-1之範圍中之氣體交換速率(=氣體流率[升/分鐘]:內爐體積[升])執行。
據信,前驅物項材料之組成(其與成品線芯之組成相同)與在程序步驟(3)期間佔主導之程序參數之獨特組合對於獲得本發明之線係必不可少的。該等程序參數之一較佳組合係:目標溫度500℃至650℃,達0.1秒至0.3秒,較佳進一步結合使用90vol.-%至98vol.-%氮/2vol.-%至10vol.-%氫混合物作為清掃氣體,以處於50min-1至63min-1之範圍中之氣體交換速率。
在完成程序步驟(3)之後,即完成本發明之線。為了充分地自其
性質獲益,將該線立即用於線接合應用(即,無延遲地,例如,在完成程序步驟(3)之後不超過7天內)係有利的。另一選擇為,為了保持線之寬線接合程序窗性質且為了防止其受氧化或其他化學侵蝕,通常在完成程序步驟(3)之後立即(即,無延遲地,例如,在完成程序步驟(3)之後<1小時至5小時內)將成品線進行纏繞及真空密封且隨後儲存以供進一步用作接合線。以真空密封條件進行儲存不應超過6個月。在開啟真空密封之後,線應在不超過7天內用於線接合。
較佳地,所有程序步驟(1)至(3)以及纏繞及真空密封係在潔淨室條件(US FED STD 209E潔淨室標準,1k標準)下執行。
本發明之第三態樣係一種可藉由根據本發明第二態樣或其實施例之程序而獲得之線。已發現,該線非常適合用作線接合應用中之接合線。線接合技術係熟習此項技術者所習知的。在線接合過程中,通常形成球接合(第一接合)及針腳式接合(第二接合,楔接合)。在接合形成期間,在所施加擦洗幅度(通常以μm為單位來量測)的支援下,施加一特定力(通常以克為單位來量測)。在線接合程序中所施加力之上限與下限間之差與所施加擦洗幅度之下限與下限間之差的算術乘積界定線接合程序窗:(所施加力之上限-所施加力之下限).(所施加擦洗幅度之上限-所施加擦洗幅度之下限)=線接合程序窗。
線接合程序窗界定允許形成滿足規範(即,通過習用測試如習用拉力測試、球剪力測試及球拉力測試,此處僅列出幾個)之線接合之力/擦洗幅度組合之面積。
對於工業應用,出於線接合程序穩健性之原因,期望具有寬線接合程序窗(以g為單位之力對以μm為單位之擦洗幅度)。本發明之線展現相當寬之線接合程序窗。舉例而言,對於針腳式接合,本發明直徑為18μm之線展現處於例如40μm至120μm之範圍中之線接合程序
窗。
以下非限制性實例說明本發明。
測試方法A.至J.
所有測試及量測皆係在T=20℃及相對濕度RH=50%下進行。
A.藉由線截取方法得出平均晶粒大小:
使用標準金相技術(ASTM E112-96,第16.3章,第13頁)來判定晶粒大小。對線芯之樣品進行剖切且然後進行蝕刻。在本發明情形中,使用2g FeCl3及6ml濃HCl在200ml去離子水中之溶液來進行蝕刻。根據線截取原理來判定晶粒大小。在本發明上下文中,晶粒之大小被界定為通過晶粒之直線之所有剖面中之最長者。所量測平均晶粒大小係芯材料中之晶粒之至少七個量測值之算術平均值。
B.伸長率(EL):
使用Instron-5300儀器測試線之拉伸性質。以1英吋/分鐘速度在10英吋標距長度內對線進行測試。根據ASTM標準F219-96來獲取折斷(斷裂)時之負荷及伸長率。伸長率係線長度在拉伸測試之前及之後的差(△L/L),其係根據所記錄負荷對延伸拉伸曲線圖而計算出。
C.針腳式接合程序窗面積:
藉由標準程序來進行對接合程序窗面積之量測。測試線係使用KNS-iConn接合器工具(庫力索法工業公司,華盛頓堡,美國賓夕法尼亞州(Kulicke & Soffa Industries Inc,Fort Washington,PA,USA))而接合。第二接合(針腳式接合)程序窗面積係在接合時所使用之力之上限與下限之差與所施加擦洗幅度之上限與下限之差的乘積,其中所得接合必須滿足某些拉力測試規範,例如2.5克之拉力、引線上無非黏處等。程序窗值係基於具有18μm之平均直徑之線,其中線被接合至的引線指由銀組成。
藉由克服以下兩種主要故障模式來導出程序窗之四個拐角:(1)供應太低力及擦洗幅度會導致線之引線上非黏處(NSOL),及(2)供應太高力及擦洗幅度會導致短尾(SHTL)。
D.自由空氣球(FAB):
藉由以如下2種不同模式執行習用電火炬(EFO)點火來評估FAB:(a)標準點火-單個步驟,及(b)進階點火-兩個步驟,參見下表:
該表係根據自由空氣球KNS程序用戶指南(庫力索法工業公司,華盛頓堡,美國賓夕法尼亞州,2002,2009年5月31日)中所述之程序而得出。以μm標度使用光學顯微鏡在200X至500X放大率下來量測FAB直徑。使用掃描電子顯微鏡(SEM)來觀察FAB之形態。評估在針腳式接合之前懸掛於線端處之線材料熔融液滴之形狀及對稱性。
對FAB構形之效能之評估:
+,線熔融液滴凝固,但球大小小於規範及/或係尖狀的
++,線熔融液滴以球體形狀凝固,但球大小不符合規範及/或係傾斜的
+++,線熔融液滴以球體形狀且在規範之內凝固,但略微傾斜
++++,線熔融液滴以球體及軸對稱球狀形狀凝固,
E.平均經接合球圓度及同心性:
藉由量測平均圓度及同心性來量化經接合球(第一接合)形態。使用標準點火模式或進階點火模式而對線進行接合。4N裸露的以銅及鎳合金化之銅線係使用標準點火模式而接合,而以銀-鎳合金化之銅線係使用進階點火模式而接合。
在高倍率尼康顯微鏡MM40中以500X放大率來觀察經接合球。與顯微鏡互連之e-max軟體版本5.3針對16個所量測邊緣點藉由最小平方法來預測理論圓。求出每一邊緣與理論圓半徑之偏差。最大偏差值與最小偏差值之差被界定為DevE,即經接合球之平均圓度。圓度良好之球展示出0.001μm平均圓度且較差球展露0.003μm平均圓度。
在平均經接合球同心性之情形中,沿著外圓標記12個邊緣。e-max軟體藉由最小平方法來預測理論圓且求出外圓之中心。類似地,其預測內圓及其中心。計算外圓與內圓在X方向及Y方向兩者上之中
心差,根據此中心差按照來計算同心性。同心性良好之經接合球展示出0.0001μm,且最差球展露出0.0009μm。
F.對連續鑄造桿之鹽溶液浸泡測試:
分出長度為10mm之連續鑄造8mm桿並在85℃下將其浸泡於鹽溶液中達4天,使用DI水沖洗且稍後用丙酮沖洗。該鹽溶液含有溶於去離子(DI)水中之20wt.-%NaCl。在較低倍率鏡(立體鏡-SZX16)下以10X至100X放大率觀察該等桿之表面變色。自原始銅紅色變換至暗黑色之桿表面表明若干處縫隙腐蝕。對暗黑色表面進行之SEM-EDX展露氯峰、氧峰及銅峰。
評估:
+,100%鑄造桿表面自原始銅紅色變換至暗黑色,表明若干處縫隙腐蝕
++,<70%鑄造桿表面自原始銅紅色變換至黑色,表明縫隙腐蝕
+++,<40%鑄造桿表面自原始銅紅色變換至黑色,表明輕微縫隙腐蝕
++++,<10%鑄造桿表面自原始銅紅色變換至暗黑色,表明縫隙腐蝕較不顯著或不存在
G.對經接合球之鹽溶液浸泡測試:
將線球接合至Al-0.5wt.-%Cu接合墊。將帶有如此接合之線之測試裝置在25℃下浸泡於鹽溶液中達2、4、6、8及10分鐘,用DI水沖洗且稍後用丙酮沖洗。該鹽溶液含有溶於去離子(DI)水中之30wt.-ppm NaCl。在較低倍率鏡(立體鏡-SZX16)下以10X至100X放大率檢查經剝離球之數目。觀察到較高數目個經剝離球表明若干處界面電化腐蝕。
H.對連續鑄造桿之耐濕性測試:
分出長度為10mm之連續鑄造8mm桿並將其在130℃溫度、85%相對濕度(RH)下儲存於高度加速之應力測試(HAST)室中達4天。在低倍率鏡(立體鏡-SZX16)下以10X至100X放大率檢查經HAST測試樣品以查看表面變色。類似於鹽溶液浸泡測試,自原始銅紅色變換至暗黑色之桿表面表明若干處縫隙腐蝕。對暗黑色表面進行之SEM-EDX展露氧峰及銅峰。
評估:
+,100%鑄造桿表面自原始銅紅色變換至暗黑色,表明若干處縫隙腐蝕
++,<70%鑄造桿表面自原始銅紅色變換至黑色,表明縫隙腐蝕
+++,<40%鑄造桿表面自原始銅紅色變換至黑色,表明輕微縫隙腐蝕
++++,<10%鑄造桿表面自原始銅紅色變換至暗黑色,表明縫隙腐蝕較不顯著或不存在
I.對經接合球之耐濕性測試:
將線球接合至Al-0.5wt.-%Cu接合墊。將帶有如此接合之線之測試裝置在130℃溫度、85%相對濕度(RH)下儲存於高度加速之應力測試(HAST)室中達20小時,且稍後在較低倍率鏡(立體鏡-SZX16)下以10X至100X放大率檢查經剝離球之數目。觀察到較高數目個經剝離球表明若干處界面電化腐蝕。
J.維氏硬度:
使用具有維氏壓頭(Vickers indenter)之費氏(Fischer)鏡H110C測試設備來量測硬度。對測試線試樣施加10mN之力達5s之停留時間。該測試係對經退火線芯之中心執行。
實例1-10
將一定量之至少99.99%純度之銅材料(「4N銅」)在坩堝中熔化。將少量母合金添加至銅熔體並藉由攪拌來確定所添加組分之均勻分佈。使用以下母合金。
對於表1及表2之合金,添加母合金Cu-5wt.-%Ni、Cu-15wt.-%Ag及Cu-0.5wt.-%P之對應組合。然後,自熔體連續鑄造呈8mm桿形式之線前驅物。
以6個主要拉製階段(每一階段中具有22個程序步驟)拉製該等8mm桿,以形成圓形形狀且平均直徑為18μm之線,其中在每一程序步驟中對前驅物執行自6%至18%之長度伸長。在本文中所呈現之實例中,針對階段1實踐17%伸長,針對階段2至階段5實踐11%伸長,且針對階段6實踐8%伸長。在拉製期間採用增滑劑。
藉助於此種程序,製造銅-鎳及銅-鎳-銀合金線及一個比較性線線(Ref)之樣品。
使用Perkin Elmer ICP-OES 7100DV型號藉由ICP(電感耦合電漿)分析來控制銅、銅-鎳及銅-鎳-銀合金線之化學組成。將線溶於濃硝酸中且將溶液用於ICP分析。
表1展示平均直徑為18μm之發明性銅-鎳合金線之樣品1至6之組
成。線之鎳含量如所指示的那樣而變化,磷之量亦如所指示的那樣變化。比較性線(Ref)由4N銅組成。
表2展示各自具有18μm平均直徑之樣品線7至10之組成。該等線之銀、鎳及磷含量如所指示的那樣而變化。比較性線(Ref)由4N銅組成。
該等線係在最終退火程序步驟中被退火。該退火係藉由使該等線以1m/s之速度通過長度為30cm且退火溫度為560℃(線1-6)或650℃(線7-10)之管式退火爐而作為股線退火被動態地執行。在離開該爐之後,將該等線纏繞於捲軸上以供封裝。
在本發明實例中,退火時間係一段給定移動線在經加熱爐內之
曝露時間,其為0.3s。在爐區內,調整恆定溫度。
量測線樣品1至10之平均晶粒大小。對於樣品1至6,結果處於3μm至6μm之範圍中,且對於樣品7至10,結果處於1.5μm至6μm之範圍中。
下表3展示以樣品1至6之8mm桿及經接合線獲得之測試結果。
以下表4展示以8mm桿及樣品7至10之經接合線獲得之測試結果。
線1-6及7-10產生非常適合於工業應用之程序窗。至少對於處於0.5wt.-%至5wt.-%之範圍中之鎳含量或對於處於0.1wt.-%至0.5wt.-%之範圍中之銀與處於0.1wt.-%至0.5wt.-%之範圍中之鎳之組合,可觀察到所鑄造桿及經接合球之耐腐蝕性及耐濕性之顯著改良。
圖1係展示根據樣品3(表1)之鎳合金化之18μm銅線的實例性退火曲線。
Claims (15)
- 一種包括芯之線,該芯包括以下各項或由以下各項組成(a)鎳,其量處於自0.005wt.-%至5wt.-%之範圍中,(b)視情況,銀,其量處於自0.005wt.-%至1wt.-%之範圍中,(c)銅,其量處於自94wt.-%至99.98wt.-%之範圍中,及(d)0wt.-ppm至100wt.-ppm之其他組分,其中以wt.-%及wt.-ppm計之所有量皆係基於該芯之總重量,其中該芯具有處於自1.5μm至30μm之範圍中之平均晶粒大小,該平均大小係根據線截取方法而判定,其中該線具有處於自8μm至80μm之範圍中之平均直徑。
- 如請求項1之線,其中該平均直徑處於自12μm至55μm之範圍中。
- 如請求項1之線,其中該芯具有作為外表面之表面,或其中一塗層疊置於該芯之該表面上。
- 如請求項3之線,其中相對於該芯之總質量,該塗層之質量不大於2.5wt.-%。
- 如請求項3之線,其中該塗層係鈀、鉑或銀之單層或者若干個經疊置毗鄰層之多層,每一層皆係由選自由鈀、鉑及銀組成之群組之一種元素製成。
- 如請求項3、4或5之線,其中另一塗層疊置於該塗層上。
- 如請求項6之線,其中該另一塗層係金層。
- 如請求項1之線,其中該線芯包括元素磷作為摻雜劑,基於該芯之總重量,該元素磷之量處於自40wt.-ppm至80wt.-ppm之範圍中。
- 如請求項1之線,其中該芯之直徑與該芯中之該平均晶粒大小之間的比率處於自2至14之範圍中。
- 如請求項1之線,其至少由以下特徵中之一者表徵:α)耐腐蝕性具有至多0%經接合球剝離之值;β)耐濕性具有至多0%經接合球剝離之值;γ)該線芯之硬度不大於120HV;δ)倘若該線具有18μm之平均直徑,則針腳式接合之程序窗面積具有至少40μm.g之值;ε)該線之電阻率不大於1.80μΩ.cm;ζ)倘若該線具有18μm之平均直徑,則平均經接合球圓度具有至多0.0025μm之值;η)倘若該線具有18μm之平均直徑,則平均經接合球同心性具有至多0.00056μm之值。
- 一種用於製造如請求項1之線之方法,該方法包括至少以下程序步驟(1)提供前驅物項,該前驅物項包括以下各項或由以下各項組成:(a)鎳,其量處於自0.005wt.-%至5wt.-%之範圍中,(b)視情況,銀,其量處於自0.005wt.-%至1wt.-%之範圍中,(c)銅,其量處於自94wt.-%至99.98wt.-%之範圍中,及(d)0wt.-ppm至100wt.-ppm之其他組分,其中以wt.-%及wt.-ppm計之所有量皆係基於該前驅物項之總重量,(2)使該前驅物項伸長以形成線前驅物,直至獲得該線芯之所要直徑為止;及(3)將在完成程序步驟(2)之後獲得之該經伸長線前驅物退火。
- 如請求項11之方法,其中該退火係股線退火。
- 如請求項11之方法,其中該退火係在440℃至700℃之範圍中之目標溫度下執行達0.1秒至0.4秒。
- 如請求項11之方法,其中該退火係在高於最大伸長率溫度之溫度下執行,其中該線在退火之後之伸長率值不大於最大伸長率值之98%。
- 如請求項11之方法,其中該退火係在惰性或還原氛圍中執行。
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SG10201509913XA (en) * | 2015-12-02 | 2017-07-28 | Heraeus Materials Singapore Pte Ltd | Silver alloyed copper wire |
JPWO2021111908A1 (zh) | 2019-12-02 | 2021-06-10 | ||
TW202138572A (zh) | 2020-02-21 | 2021-10-16 | 日商日鐵新材料股份有限公司 | 銅接合導線 |
CN115836384B (zh) | 2021-06-25 | 2024-06-11 | 日铁新材料股份有限公司 | 半导体装置用接合线 |
JPWO2022270077A1 (zh) | 2021-06-25 | 2022-12-29 | ||
KR20240026929A (ko) | 2021-06-25 | 2024-02-29 | 닛데쓰마이크로메탈가부시키가이샤 | 반도체 장치용 본딩 와이어 |
JP7157279B1 (ja) | 2021-06-25 | 2022-10-19 | 日鉄マイクロメタル株式会社 | 半導体装置用ボンディングワイヤ |
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WO2022270050A1 (ja) | 2021-06-25 | 2022-12-29 | 日鉄マイクロメタル株式会社 | 半導体装置用ボンディングワイヤ |
WO2023248491A1 (ja) | 2022-06-24 | 2023-12-28 | 日鉄ケミカル&マテリアル株式会社 | 半導体装置用ボンディングワイヤ |
EP4365931A1 (en) | 2022-06-24 | 2024-05-08 | NIPPON STEEL Chemical & Material Co., Ltd. | Bonding wire for semiconductor device |
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JP4919364B2 (ja) * | 2010-08-11 | 2012-04-18 | 田中電子工業株式会社 | ボールボンディング用金被覆銅ワイヤ |
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