TW202242152A - 銀合金線材 - Google Patents

銀合金線材 Download PDF

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TW202242152A
TW202242152A TW110113667A TW110113667A TW202242152A TW 202242152 A TW202242152 A TW 202242152A TW 110113667 A TW110113667 A TW 110113667A TW 110113667 A TW110113667 A TW 110113667A TW 202242152 A TW202242152 A TW 202242152A
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alloy wire
wire
alloy
silver
surface coating
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TW110113667A
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TWI778583B (zh
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莊安琪
蔡幸樺
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樂金股份有限公司
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Priority to CN202111392079.3A priority patent/CN115223974A/zh
Priority to DE102022100875.4A priority patent/DE102022100875A1/de
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Abstract

本發明揭示一種合金線材，其組成包含Ag-Pt-Ge三種元素，其中Pt含量為0.1至3wt%，Ge含量為1ppm至2wt%，此合金線材可再添加取自下列元素至少其中一種:Ca、Cu、In、Mg、Si、Ti、Sc，其總添加量為1ppm至0.1wt%。此合金線材亦包含在上述組成的核心線材外面再加上含Au、Pd或Pt的表面鍍層，此表面鍍層的厚度0.01至10μm。本發明所揭示之合金線材的形狀可為圓形或扁帶形。

Description

銀合金線材
本發明係有關於一種合金線材，且特別關於用於電子封裝打線接合的合金線材。
打線接合為積體電路（IC）及發光二極體（LED）封裝製程的主要內連線（interconnection）方法。打線接合線材除了提供晶片與基材之間的訊號與功率傳輸，亦可兼具散熱功能。因此打線接合線材必須有高導電性、高導熱性、足夠的強度及延展性。但為了避免打線接合之熱壓過程導致晶片破裂，同時使線材與銲墊接觸良好以確保良好的接合性，線材的硬度不能太高。由於封裝之高分子封膠常含有腐蝕性氯離子，且高分子封膠本身具環境吸濕性，線材必須有良好的抗氧化性與耐腐蝕性。
在打線接合過程，首先要將線材末端以高壓放電方式燒熔(Electric Flame Off, EFO)，利用表面張力形成結球(Free Air Ball, FAB)，再將結球經由瓷嘴銲針下壓而與一銲墊接合形成第一銲點，而線材的另一端則會被牽拉至另一導電銲墊處，並與另一導電銲墊接合，形成第二銲點，藉此構成一電路的導通。結球的形狀決定後續第一球銲點(ball bond)的品質。此外，第一球銲點與半導體晶片銲墊的接合界面會形成介金屬化合物(intermetallic compounds)。這些介金屬化合物可確保界面接合性，但過量的介金屬化合物會造成界面脆裂及產生科肯達孔洞(Kirkendall voids)。另外，線材本身的抗氧化及腐蝕性更是決定電子產品可靠度的要件。
當半導體或發光二極體封裝完成，產品在使用過程，通過線材的高電流密度也可能帶動內部原子產生電遷移現象（Electron Migration），使得線材一端形成孔洞，因而降低導電性與導熱性，甚至造成斷線及產品失效；通電流也可能使封裝線材局部燒熔，使電壓急速上升，最後同樣導致斷線及產品失效，此問題對於高電壓大電流電子產品的封裝尤其嚴重，是影響這些電子產品可靠度的主要因素。
目前常見的封裝導線，例如包括下列幾種選擇：
(1)金線：金線可具有低電阻率，但是金線與鋁墊打線接合界面會大量的形成脆性介金屬化合物(包括Au2Al、AuAl4、Au5Al2等)，使得導電性降低。此外，金/鋁界面介金屬反應會伴隨產生許多柯肯達孔洞(Kirkendall voids)，更加提高接合界面電阻率，而導致接點的可靠度降低。
(2)銅線：近年來，封裝產業開始採用銅線作為半導體及發光二極體打線接合的線材。銅線雖具有較佳的導電性，但卻很容易氧化，故在線材儲存及運送過程均需要密封保護，打線接合製程更需要昂貴的氮氣加氫氣輔助，且在後續封裝電子產品可靠度試驗仍然會遭遇氧化及腐蝕性的問題。此外，銅線材質太硬，打線接合容易造成晶片破裂等問題。雖然在一些研究中提出在銅線表面鍍上其他金屬鍍層以改善易氧化及腐蝕問題的方法(例如參照美國專利US 7645522B2、US 2003/0173659A1、US 7820913B2)，但由於銅線本身硬度高，造成打線接合步驟易失敗，故仍無法達到高電壓大電流電子產品封裝時所需的可靠度。
(3)銀線：銀是在所有材料中電阻率最低的元素，但是純銀在含硫的環境會有硫化腐蝕的問題，同時純銀線在鋁墊上打線接合時也會生成脆性的介金屬化合物(Ag 2Al或Ag 4Al)。此外，純銀線在含水氣的封裝材料內部很容易發生電解離子遷移現象(Ion Migration)。亦即，純銀在含水氣環境會經由電流作用水解溶出銀離子，再與氧反應成為不穩定的氧化銀(AgO)，此氧化銀因而會進行去氧化作用(Deoxidize)形成銀原子，並向正極成長出樹葉紋理狀(leaf vein)的銀鬚，最後造成正負電極的短路（請參考：H. Tsutomu, Metal Migration on Electric Circuit Boards, Three Bond Technical News, Dec. 1, 1986.）。此外，在一些研究中提出在銀線表面鍍上其他金屬鍍層以改善硫化腐蝕及銀離子遷移的問題的方法(例如參照美國專利US 6696756)，但所形成的線材仍無法達到理想的可靠度及電阻率。
(4)合金線：合金線例如包括以金為主的合金以及以銀為主的合金。這些合金例如更包括銅、鉑、錳、鉻、鈣、銦等元素，然而這些合金線仍然無法同時兼具低阻抗及高可靠度的性質。
綜上所述，現有的各種純金屬線材、表面鍍金屬的複合線材、以及添加元素的合金線材在封裝上無法滿足全部的需求，因此，目前仍需一種具高可靠度的線材。
本揭露的一些實施例提供一種合金線材，其組成包含Ag-Pt-Ge三種元素，其中包括0.1至3wt%的Pt，1ppm至2wt%的Ge以及餘量的Ag。
在一些實施例中，合金線材更包括取自 Ca、Cu、In、Mg、Si、Ti或Sc中至少一者的添加元素，該添加元素的總添加量為1ppm至0.1wt%，且該添加元素的各別添加量小於Pt或Ge的含量。
在一些實施例中，合金線材為圓形線材。
在一些實施例中，合金線材的直徑為10μm至300μm。
在一些實施例中，合金線材為扁帶形線材。
在一些實施例中，合金線材的厚度為20μm至300μm。
在一些實施例中，合金線材的寬度為100μm至2000μm。
在一些實施例中，合金線材更包括表面鍍層，該表面鍍層含Au、Pd、Pt、其合金或其組合，且該表面鍍層的厚度為0.01至10μm。
以下揭露提供了許多的實施例或範例，用於實施所提供的標的物之不同元件。各元件和其配置的具體範例描述如下，以簡化本發明實施例之說明。當然，這些僅僅是範例，並非用以限定本發明實施例。舉例而言，敘述中若提及第一元件形成在第二元件之上，可能包含第一和第二元件直接接觸的實施例，也可能包含額外的元件形成在第一和第二元件之間，使得它們不直接接觸的實施例。此外，本發明實施例可能在各種範例中重複參考數值或字母。如此重複是為了簡明和清楚之目的，而非用以表示所討論的不同實施例或配置之間的關係。
再者，其中可能用到與空間相對用詞，例如「在……之下」、「下方」、「較低的」、「上方」、「較高的」等類似用詞，是為了便於描述圖式中一個（些）部件或特徵與另一個（些）部件或特徵之間的關係。空間相對用詞用以包括使用中或操作中的裝置之不同方位，以及圖式中所描述的方位。當裝置被轉向不同方位時（旋轉90度或其他方位），其中所使用的空間相對形容詞也將依轉向後的方位來解釋。
此處所使用的用語「約」、「近似」等類似用語描述數字或數字範圍時，該用語意欲涵蓋的數值是在合理範圍內包含所描述的數字，例如在所描述的數字之+/- 10％之內，或本發明所屬技術領域中具有通常知識者理解的其他數值。例如，用語「約5 nm」涵蓋從4.5nm至5.5nm的尺寸範圍。
本文所用用語僅用以闡釋特定實施例，而並非旨在限制本發明概念。除非表達在上下文中具有明確不同的含義，否則以單數形式使用的所述表達亦涵蓋複數形式的表達。在本說明書中，應理解，例如「包含」、「具有」、及「包括」等用語旨在指示本說明書中所揭露的特徵、數目、步驟、動作、組件、部件或其組合的存在，而並非旨在排除可存在或可添加一或多個其他特徵、數目、步驟、動作、組件、部件或其組合的可能性。
本揭露提供一種合金線材，包括三元Ag-Pt-Ge三種元素，提升線材的抗硫化性、抗高溫潛變性及在打線接合過程的結球性，使打線良率提高。
US 8101123B2專利揭示一種Ag-Au-Pd組成的銀合金線材，雖然其在Ag合金組成內添加Au與Pd可改善純銀線的機械性質與抗氧化性，添加Pd更可減緩銀的離子遷移問題，然而此種組成之合金線材在EFO結球過程常會發生偏心球或筆尖球等異常現象，導致打線良率下降，此外線材的抗高溫潛變性不佳，且其光澤性及抗硫化性亦較差。US20130171470專利揭示一種Ag-Au-Pd組成且其晶粒結構呈現大量退火孿晶的銀合金線材，雖然其孿晶結構可提升線材的電遷移壽命，但是在結球性、抗高溫潛變性、光澤性及抗硫化性亦均不足。JP1997275120、US20080240975A1、CN10215454A、US20130126934、TWI 408787及US10840208B2等專利則在Ag合金內添加Pt及其他微量元素，然而這些習知技術的銀合金線材同樣在打線接合過程的結球性不佳，抗高溫潛變性不足，而且其光澤性及抗硫化性亦均較差。
而本案的銀合金線材中添加Ge，可有效提升此線材的抗硫化性，同時可以提高銲點的接合強度，但是鍺的含量過高時，則會使線材延展性降低。另外，適量的鉑(Pt)可增強線材的抗氧化、硫化性及氯離子腐蝕性，並對於銀的離子遷移現象亦有明顯抑制效應，同時也減少銀合金線與鋁墊形成介金屬化合物，然而當鉑的含量過高時，則會使線材的電阻率明顯提高。實施例亦證明僅須添加微量Ge，此三元Ag-Pt-Ge銀合金線較二元Ag-Pt銀合金線的抗高溫潛變性大幅提升，此外，在EFO過程，此三元Ag-Pt-Ge銀合金線的結球(FAB)非常完美，優於目前習知任何銀合金線材，因此其打線接合所形成的第一球銲點形狀與品質亦極佳。此外，實施例證明此三元Ag-Pt-Ge銀合金線打線接合及後續可靠度試驗後的界面介金屬成長較傳統金線慢，相較於銅線或鍍鈀銅線較不會發生介金屬不足，無法通過殘金試驗(metal residue test)的問題，其接合後推球強度(ball shear strength)及線材拉線強度(wire pull strength)亦均有極佳表現，再添加第四元微量元素則可以使前述有益效應再增強。
根據一些實施例，第1圖為本揭露第一形態之圓形合金線材10。第1圖是圓形合金線材10的一部分線段，圓形合金線材10的材質為在銀基材中同時添加Pt及Ge所形成的Ag-Pt-Ge三元合金組成，其中銀基材為實質上的純銀，且圓形合金線材10包括約0.1至約3wt%的Pt，例如約1至約2wt%或約0.5至約1.5wt%，約1ppm至2wt%的Ge，例如約100ppm至約1wt%或約500ppm至約1.5wt%，以及餘量的Ag。圓形合金線材10的直徑為約10μm至約300μm，例如約100μm至200μm或約50μm至250μm。在其他實施例中，圓形合金線材10也可包括其他元素，但應避免所添加的元素與銀形成介金屬相的析出物，造成材質脆化、腐蝕性提高、或導電性降低等問題。因此，所添加的元素較佳可以銀原子完全互溶而不會有析出物的形成，以確保線材的延展性。例如，在一些實施例中，圓形合金線材10可包含取自Ca、Cu、In、Mg、Si、Ti或Sc中至少一種的添加元素，且上述添加元素的總添加量為約1ppm至約0.1wt%，例如約10ppm至約0.05wt%或約5ppm至約0.01wt%，上述添加元素的各別添加量小於Pt或Ge。在一些實施例中，圓形合金線材10不含另外的添加元素，即圓形合金線材10只有在銀基材中添加Pt及Ge。應注意的是，在一些實施例中，上述圓形合金線材亦可在外層上均勻被覆表面鍍層，如第2A圖至第2B圖所示，且第2B圖為第2A圖的長度方向的縱切面圖。其中表面鍍層22可包括實質上的純金、實質上的純鈀、實質上的純鉑、其合金或其組合。可以適當之鍍層方法形成表面鍍層22(例如：電鍍、濺鍍及真空蒸鍍)。藉由表面鍍層22的材質的化學惰性，可保護其內的圓形合金線材20而避免其受到腐蝕，同時在抽線成形時發揮潤滑效果，且表面鍍層22的厚度約0.01至約10μm，例如約0.1μm至約5μm或約1μm至約8μm。
根據一些實施例，第3圖為本揭露第二形態之扁帶形合金線材30。第3圖是扁帶形合金線材30的一部分線段，扁帶形合金線材30的材質及其添加元素可以參照第1圖所示的圓形合金線材10，在此不再贅述。根據一些實施例，扁帶形合金線材30的厚度為約20μm至約300μm，例如約50μm至約125μm或約100μm至約250μm。根據一些實施例，扁帶形合金線材30的寬度為約100μm至約2000μm，例如約500μm至約1400μm或約1000μm至約1800μm。值得注意的是，在一些實施例中，上述扁帶形合金線材亦可在外層上均勻被覆表面鍍層，如第4A圖至第4B圖所示，其中第4B圖為第4A圖的長度方向的縱切面圖。其中表面鍍層42可包括實質上的純金、實質上的純鈀、實質上的純鉑、其合金或其組合。可以適當之鍍層方法形成表面鍍層42(例如：電鍍、濺鍍及真空蒸鍍)，且表面鍍層42的厚度為約0.01至約10μm，例如約0.1μm至約5μm或約1μm至約8.5μm。
關於說明書所述實質上的純金屬，以純銀為例，係指在設計上期望為完全不含其他元素、化合物等的雜質的純銀，但在實際冶煉、精煉、鍍膜等的過程中卻難以完全除去上述雜質而達成數學上或理論上含100%的純銀，就視為「實質上的純銀」，因此，在其他實施例中，合金線材及／或其鍍層可更包括其他金屬、非金屬元素、或其他雜質成分，而當上述雜質含量的範圍落於對應的標準或規格所訂定的允收範圍內。本發明所屬技術領域中具有通常知識者應當瞭解依據不同的性質、條件、需求等等，上述對應的標準或規格會有所不同，故文中並未列出特定的標準或規格。
另外，其他金屬元素的添加需視應用上的需要調整，以避免影響合金線材的性質。例如，在上述合金線材中加入銅時，固然會產生材質強化效應，但是銅元素會使合金線材的抗氧化及硫化腐蝕性能大幅降低。此外，銅也會使合金的硬度增高變脆，使得抽線製程困難，同時在打線接合過程也容易造成晶片擊穿。
另外，雖然添加稀土元素可以使合金的晶粒細化，但對於封裝打線接合的線材應用需求，細晶粒有較多晶界，這些晶界會阻礙電子傳輸，使合金電阻率提高，故不適用於高速運作及高頻積體電路電子產品之封裝需求。此外，稀土的化學活性會提高其氧化及腐蝕破壞，使得封裝線材在通電流時較容易熔斷，而不利於電子產品的可靠度。再者，在合金中添加鈣會使材料延展性變差；在合金中添加低熔點的銦或錫會形成低溫相，使線材耐溫性變差，持續通電流容易造成線材融斷；添加鈹(Be)為具毒性之易燃性固體，乾燥粉塵或煙霧都是有毒的；添加釕(Ru)、銠(Rh)、鋨(Os)、銥(Ir)時，其熔點(分別為2310°C、1965°C、3045°C和2410°C)均遠高於銀的沸點(2212°C)，因此其熔煉極為困難，且會大幅增加電阻率。又，部分添加元素在相平衡圖上會與銀形成介金屬相的析出物(Precipitation)，而造成材質的脆化及較高腐蝕性，更會降低線材的導電性。
Ag、Pt、Ge之選擇是因為這三種元素在相平衡圖上可以完全互相固溶(Solid Solution)，不會產生任何脆性的介金屬相析出物，故所形成的合金線材可具有較佳的延展性，且Pt、Ge的添加也不會對Ag的電阻率有太大的影響。
在一些實施例中，上述合金線材的形成方法為先形成合金粗線材，再交替進行複數道冷加工成形步驟及複數道退火步驟，以逐次縮減該粗線材的線徑。粗線材的形成方法係將Ag、Pt及Ge加熱熔融後，經澆鑄而成為鑄錠。而後，對鑄錠進行冷加工，以形成上述至少由Ag、Pt及Ge所形成之粗線材。在另一實施例中，則是將Ag、Pt及Ge加熱熔融後，以連續鑄造的方式形成上述粗線材。在一些實施例中，上述冷加工成形步驟包括抽線、擠型或前述之組合。或者，上述冷加工成形步驟及退火步驟可為任何已知或未來發展的冷加工/退火方式。
以上概述數個實施例之特徵，以使本發明所屬技術領域中具有通常知識者可更易理解本發明實施例的觀點。本發明所屬技術領域中具有通常知識者應理解，可輕易地以本發明實施例為基礎，設計或修改其他製程和結構，以達到與在此介紹的實施例相同之目的及／或優勢。在本發明所屬技術領域中具有通常知識者也應理解，此類等效的製程和結構並無悖離本發明的精神與範圍，且可在不違背本發明之精神和範圍之下，做各式各樣的改變、取代和替換。
10:圓形合金線材 20:圓形合金線材 22:表面鍍層 30:扁帶形合金線材 40:扁帶形合金線材 42:表面鍍層
以下將配合所附圖示詳述本揭露之各面向。應注意的是，依據在業界的標準做法，各種特徵並未按照比例繪製且僅用以說明例示。事實上，可能任意地放大或縮小元件的尺寸，以清楚地表現出本揭露的特徵。 第1圖係根據一些實施例，繪示出圓形合金線材的一部分線段。 第2A圖係根據一些實施例，繪示出被覆表面鍍層的圓形合金線材的一部分線段。 第2B圖係根據一些實施例，繪示出沿著平行於第2A圖所示被覆表面鍍層的圓形合金線材的長度方向之縱切面圖。 第3圖係根據一些實施例，繪示出扁帶形合金線材的一部分線段。 第4A圖係根據一些實施例，繪示出被覆表面鍍層的扁帶形合金線材的一部分線段。 第4B圖係根據一些實施例，繪示出沿著平行於第4A圖所示被覆表面鍍層的扁帶形合金線材的長度方向之縱切面圖。
20:圓形合金線材
22:表面鍍層

Claims (8)

  1. 一種合金線材，其組成包含Ag-Pt-Ge三種元素，其中包括0.1至3wt%的Pt，1ppm至2wt%的Ge以及餘量的Ag。
  2. 如申請專利範圍第1項所述之合金線材，其更包括取自 Ca、Cu、In、Mg、Si、Ti或Sc中至少一者的添加元素，該添加元素的總添加量為1ppm至0.1wt%，且該添加元素的各別添加量小於Pt或Ge的含量。
  3. 如申請專利範圍第1項所述之合金線材，其中該合金線材為一圓形線材。
  4. 如申請專利範圍第3項所述之合金線材，其中該合金線材的直徑為10μm至300μm。
  5. 如申請專利範圍第1項所述之合金線材，其中該合金線材為一扁帶形線材。
  6. 如申請專利範圍第5項所述之合金線材，其中該合金線材的厚度為20μm至300μm。
  7. 如申請專利範圍第5項所述之合金線材，其中該合金線材的寬度為100μm至2000μm。
  8. 如申請專利範圍第1至7項中任一項所述之合金線材，更包括一表面鍍層，該表面鍍層含Au、Pd、Pt、其合金或其組合，且該表面鍍層的厚度為0.01至10μm。
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US6696756B2 (en) 2001-07-16 2004-02-24 Tao-Kuang Chang Gold wire for use in semiconductor packaging and high-frequency signal transmission
TWI287282B (en) 2002-03-14 2007-09-21 Fairchild Kr Semiconductor Ltd Semiconductor package having oxidation-free copper wire
WO2006073206A1 (ja) 2005-01-05 2006-07-13 Nippon Steel Materials Co., Ltd. 半導体装置用ボンディングワイヤ
DE102005011028A1 (de) 2005-03-08 2006-09-14 W.C. Heraeus Gmbh Kupferbonddraht mit verbesserten Bond- und Korrosionseigenschaften
KR101001700B1 (ko) 2007-03-30 2010-12-15 엠케이전자 주식회사 반도체 패키지용 은합금 와이어
US8101123B2 (en) 2009-03-23 2012-01-24 Lee Jun-Der Composite alloy bonding wire and manufacturing method thereof
KR101323246B1 (ko) 2011-11-21 2013-10-30 헤레우스 머티어리얼즈 테크놀로지 게엠베하 운트 코 카게 반도체 소자용 본딩 와이어, 그 제조방법, 반도체 소자용 본딩 와이어를 포함하는 발광다이오드 패키지
CN102912176B (zh) * 2012-09-21 2014-12-17 宁波康强电子股份有限公司 高端封装银合金键合丝及其制备方法
TWI555155B (zh) * 2014-04-17 2016-10-21 光洋應用材料科技股份有限公司 銀合金線材
JP6516465B2 (ja) 2014-12-17 2019-05-22 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
KR101812943B1 (ko) * 2016-10-20 2017-12-28 엠케이전자 주식회사 본딩 와이어

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