TW201802257A - 半導體裝置用銅合金接合線 - Google Patents

半導體裝置用銅合金接合線 Download PDF

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Publication number
TW201802257A
TW201802257A TW106120320A TW106120320A TW201802257A TW 201802257 A TW201802257 A TW 201802257A TW 106120320 A TW106120320 A TW 106120320A TW 106120320 A TW106120320 A TW 106120320A TW 201802257 A TW201802257 A TW 201802257A
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Taiwan
Prior art keywords
wire
bonding wire
bonding
mass
copper alloy
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TW106120320A
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English (en)
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TWI714779B (zh
Inventor
小田大造
山田隆
江藤基稀
榛原照男
宇野智裕
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日鐵住金新材料股份有限公司
新日鐵住金高新材料股份有限公司
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Publication of TW201802257A publication Critical patent/TW201802257A/zh
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • 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
    • H01—ELECTRIC ELEMENTS
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    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/49—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions wire-like arrangements or pins or rods
    • 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
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • C21D9/525—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length for wire, for rods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
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    • C22C—ALLOYS
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    • C22C9/04—Alloys based on copper with zinc as the next major constituent
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    • C22C—ALLOYS
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    • 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
    • C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • 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
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    • 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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Abstract

本發明之半導體裝置用銅合金接合線實現高溫高濕環境下之球部接合壽命之提高。 本發明係一種半導體裝置用銅合金接合線，其特徵在於含有總計為0.03質量%以上且3質量%以下之選自Ni、Zn、Ga、Ge、Rh、In、Ir、Pt之至少1種以上之元素(第1元素)，且剩餘部分包含Cu及不可避免之雜質。藉由含有特定量之第1元素，而抑制於線接合界面生成高溫高濕環境下易腐蝕之金屬間化合物，提高球部接合壽命。

Description

半導體裝置用銅合金接合線
本發明係關於一種用以連接半導體元件上之電極與外部引線等電路配線基板之配線的半導體裝置用銅合金接合線。
現在，作為將半導體元件上之電極與外部引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。接合線向半導體裝置之電極之接合方法一般為超音波熱壓接併用方式，使用有通用接合裝置、及將接合線通過其內部用於連接之毛細管治具等。接合線之接合製程係藉由如下方式完成：以電弧熱輸入將線前端加熱熔融，藉由表面張力而形成球(FAB：Free Air Ball，無空氣焊球)之後，將該球部壓接接合(以下，稱為「球接合」)於在150～300℃之範圍內加熱之半導體元件之電極上，其次，形成迴路後，將線部壓接接合(以下，稱為「楔接合」)於外部引線側之電極。作為接合線之接合對象的半導體元件上之電極係使用於Si基板上成膜有以Al為主體之合金之電極構造，外部引線側之電極係使用實施過鍍Ag或鍍Pd之電極構造等。 迄今為止，接合線之材料雖以金(Au)為主流，但以LSI(Large Scale Integration，大型積體電路)用途為中心正不斷替換成銅(Cu)。另一方面，近年來於電動汽車或油電混合車普及之背景下，車載用器件用途上對將Au替換成Cu之需求亦不斷提高。 關於銅接合線，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)。於使用銅接合線之情形時，亦於高密度安裝中要求較高之接合可靠性或迴路之穩定性。接合可靠性評價係為了評價實際之半導體器件之使用環境下之接合部壽命而進行。一般而言，接合可靠性評價中利用有高溫放置試驗、高溫高濕試驗。高溫高濕試驗一般係使用於溫度為121℃、相對濕度為100%之條件下進行之被稱作PCT(Pressure Cooker Test，壓力鍋測試)之試驗。 於專利文獻2中，記載有包含以0.13～1.15質量%之濃度範圍含有Pd之銅合金的半導體用銅合金接合線。藉由以上述濃度範圍添加Pd，可提高由PCT試驗測得之高濕加熱可靠性。 [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]國際公開第2010/150814號
[發明所欲解決之問題] 與一般電子機器相比，車載用器件要求嚴苛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的球接合部之接合壽命成為最大問題。關於評價高溫高濕環境下之接合可靠性之方法提出有一些方法，但近年來，作為代表性之評價方法，逐漸使用HAST(Highly Accelerated Temperature and Humidity Stress Test)(高溫高濕環境暴露試驗)。HAST具有如下特徵：對評價封裝之吸濕均勻，評價結果之再現性較高。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，對球接合部之接合壽命進行評價。又，藉由施加偏壓電壓，可進行較PCT更嚴格之評價。最近，於在此種條件下之HAST中，要求100小時以上之接合壽命。 本發明之目的在提供一種改善接合線於高溫高濕環境下之球接合部之接合可靠性，且適用於車載用器件的半導體裝置用接合線。具體而言，本發明發現了最適合於即便於作為更嚴格之評價方法的施加偏壓電壓之HAST中亦具有充分之接合可靠性之銅合金接合線的添加元素及該等之最適合之添加濃度。 [解決問題之技術手段] 即，本發明之主旨如下。 (1)一種半導體裝置用銅合金接合線，其特徵在於含有總計為0.03質量%以上且3質量%以下之選自Ni、Zn、Ga、Ge、Rh、In、Ir、Pt之至少1種以上之元素，且剩餘部分包含Cu及不可避免之雜質。 (2)如(1)所記載之半導體裝置用銅合金接合線，其特徵在於：若將線之線徑設為R(μm)，則上述銅合金接合線之垂直於線軸之方向之芯材剖面中之平均結晶粒徑(μm)為 0.02×R＋0.4以上 (1a) 0.1×R＋0.5以下 (1b)。 (3)如(1)或(2)所記載之半導體裝置用銅合金接合線，其特徵在於：線表面之氧化銅之平均膜厚為0.0005～0.02 μm之範圍。 (4)如(1)至(3)中任一項所記載之半導體裝置用銅合金接合線，其特徵在於：上述銅合金接合線進而含有相對於線整體分別為0.0001～0.050質量%之選自Ti、B、P、Mg、Ca、La、As、Te、Se之至少1種以上之元素。 (5)如(1)至(4)中任一項所記載之半導體裝置用銅合金接合線，其特徵在於：上述銅合金接合線進而含有相對於線整體總計為0.0005～0.5質量%之選自Ag、Au之至少1種以上之元素。 (6)如(1)至(5)中任一項所記載之半導體裝置用銅合金接合線，其特徵在於：上述銅合金接合線進而含有1.15質量%以下之Pd。 (7)如(1)至(6)中任一項所記載之半導體裝置用銅合金接合線，其特徵在於：上述銅合金接合線含有2種以上之選自Ni、Zn、Ga、Ge、Rh、In、Ir、Pt之元素。 [發明之效果] 根據本發明，於半導體裝置用銅合金接合線中含有總計為0.03質量%以上且3質量%以下之選自Ni、Zn、Ga、Ge、Rh、In、Ir、Pt之至少1種以上之元素，藉此，可提高於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1元素及其效果》 本發明之半導體裝置用銅合金接合線(以下，亦簡稱為「接合線」)之特徵在於： 其係將銅合金拉線而成，該銅合金含有總計為0.03質量%以上且3質量%以下之選自Ni、Zn、Ga、Ge、Rh、In、Ir、Pt之至少1種以上之元素(亦稱為「第1元素」)，且剩餘部分包含Cu及不可避免之雜質。由於本發明之接合線係以銅為主體之合金，故而亦稱為「銅合金接合線」。本發明之半導體裝置用銅合金接合線係不具有以銅以外之金屬為主成分之被覆層的接合線，亦稱為「裸Cu合金線」。本發明之接合線可改善車載用器件所要求之高溫高濕環境下之球接合部之接合可靠性。 於作為半導體裝置之封裝的塑模樹脂(環氧樹脂)中，分子骨架含有氯(Cl)。於HAST評價條件即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，以氯化物離子(Cl- )之形式溶出。於將銅合金接合線接合於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Cu9 Al4 。Cu9 Al4 易受因Cl等鹵素引起之腐蝕，會因自塑模樹脂溶出之Cl產生腐蝕，導致接合可靠性降低。因此，於先前之銅合金接合線中，HAST評價下之球接合部壽命並不充分。 相對於此，藉由如本發明般使銅合金接合線含有總計為0.03質量%以上之第1元素(選自Ni、Zn、Ga、Ge、Rh、In、Ir、Pt之至少1種以上之元素)，使用該銅合金接合線之球接合部於HAST評價下之球接合部壽命提高。認為若含有總計為0.03質量%以上之第1元素，則有可抑制接合部中之Cu9 Al4 金屬間化合物之生成之傾向。認為存在於球接合部中之Cu與Al界面之第1元素提高Cu與Al之相互擴散抑制效果，結果，抑制於高溫高濕環境下易腐蝕之Cu9 Al4 之生成。又，線所包含之第1元素亦可能有直接阻礙Cu9 Al4 之形成之效果。認為接合界面附近之第1元素之作用為阻礙誘發腐蝕之鹵素之移動的障壁功能、及控制Cu、Al之相互擴散及金屬間化合物之成長等之功能等。 進而，使用含有特定量第1元素之銅合金接合線形成球部，利用掃描式電子顯微鏡(SEM：Scanning Electron Microscope)觀察FAB時，於FAB之表面觀察到大量直徑數十nm左右之析出物。利用能量分散型X射線分析(EDS：Energy Dispersive X-ray Spectroscopy)進行分析，可確認第1元素濃集。根據如上所述之狀況，認為在FAB上觀察到之該析出物藉由存在於球部與電極之接合界面，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尤為提高，但詳細之機制尚不明確。根據本發明之接合線於作為較PCT評價更嚴格之條件的HAST評價中獲得良好之結果，可明白於PCT評價中亦可獲得良好之結果。 就提高溫度為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，改善接合可靠性之觀點而言，線中之第1元素之含量(亦稱為「濃度」)總計為0.03質量%以上，較佳為0.050質量%以上，更佳為0.070質量%以上，進而較佳為0.090質量%以上、0.100質量%以上、0.150質量%以上、或0.200質量%以上。若線中之第1元素之濃度總計為0.100質量%以上，則可對應更嚴格之針對接合可靠性之要求。 另一方面，就獲得良好之FAB形狀之觀點而言、就抑制接合線之硬質化而獲得良好之楔接合性之觀點而言，線中之第1元素之濃度總計為3質量%以下，較佳為2.5質量%以下，更佳為2.0質量%以下，進而較佳為1.9質量%以下，或1.5質量%以下。又，藉由如此規定第1元素之含量之上限，而就獲得低溫接合下與Al電極之初始接合強度良好，HAST試驗中之長期可靠性、或對BGA(Ball Grid Array，球柵陣列)、CSP(Chip Size Package，晶片尺寸封裝)等基板、帶等之接合之量產範圍優異之接合線的觀點而言，亦就減少晶片損傷之觀點而言，均可獲得良好之結果。若第1元素之含量超過3.0質量%，則必須以不產生晶片損傷之方式以低負荷進行球接合，存在與電極之初始接合強度降低，結果HAST試驗可靠性變差之情形。於本發明之接合線中，藉由將第1元素之含量(濃度)之總計設為上述較佳之範圍，可進一步提高HAST試驗中之可靠性。例如，可實現至HAST試驗產生不良前之壽命超過250小時之接合線。亦存在其相當於壽命增長至先前之Cu接合線之1.5倍以上之情形，亦可對應嚴苛之環境下之使用。 就實現溫度為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顯著優異之銅合金接合線之觀點而言，本發明之半導體裝置用Cu合金接合線較佳為含有2種以上選自Ni、Zn、Ga、Ge、Rh、In、Ir、Pt之元素(第1元素)。其中，作為第1元素之組合，較佳為Ni與Zn、Ni與Ga、Ni與Ge、Ni與In、Pt與Zn、Pt與Ga、Pt與Ge、Pt與In、Ir與Zn、Ir與Ge、Rh與Ga、Rh與In、Ni與Pt與Zn、Ni與Pt與Ga、Ni與Pt與Ge、Ni與Pt與In、Pt與Ir與Zn、Pt與Ir與Ga、Ir與Rh與Ge、Ir與Rh與In等之組合。 《接合線之平均粒徑》 評價接合線中之結晶粒徑對線品質產生之影響。其結果，判明接合線之垂直於線軸之方向之芯材剖面中之平均結晶粒徑有較佳範圍，將線之線徑設為R(μm)時，平均結晶粒徑(μm)為 0.02×R＋0.4以上 (1a) 0.1×R＋0.5以下 (1b) 時，球接合部之壓扁形狀、或楔接合性變得尤其良好。 測定結晶粒徑時，較佳為使用背向散射電子束繞射法(EBSD，Electron Backscattered Diffraction)。關於粒徑測定，可將由EBSD法所獲得之測定結果藉由利用裝置所配備之解析軟體求出。本發明中所規定之結晶粒徑係將測定區域內所含之晶粒之等效直徑(相當於晶粒之面積之圓之直徑)進行算術平均而獲得者。 《線表面之氧化銅之平均膜厚》 於本發明中，較佳為將線表面之氧化銅之平均膜厚設為0.0005～0.02 μm之範圍。於以總計為0.03～3質量%之濃度範圍含有第1元素之銅合金接合線中，若線表面之氧化銅之平均膜厚為0.0005～0.02 μm之範圍，則可進一步提高以量產級別穩定地提昇HAST可靠性之效果。若線表面之氧化銅之膜厚厚於0.02 μm，則有包含含有第1元素之銅合金之接合線的球接合部之HAST可靠性之改善效果產生偏差，HAST加熱後之接合強度等變得不穩定的傾向。該HAST可靠性之偏差於線徑為20 μm以下之接合線中更可能成為問題。關於含有第1元素之銅合金之表面之氧化銅使HAST可靠性變得不穩定之主要原因，尚有不明確之方面，認為銅合金接合線之長度方向或自線表面起深度方向上之第1元素之濃度分佈不均勻，或球內部之滲入之氧或殘留氧化物可能阻礙第1元素之HAST可靠性提高效果等。由於藉由含有第1元素之銅合金接合線可獲得延緩表面氧化之效果，故而容易將氧化銅之平均膜厚控制於作為較薄之範圍的0.0005～0.02 μm。亦確認以總計為0.03～3質量%之濃度範圍含有第1元素之銅合金接合線相較於高純度銅，具有延緩線表面之氧化銅膜於20～40℃左右之低溫區域中之成長之作用。 若線表面之氧化銅之平均膜厚超過0.02 μm，則如上所述，HAST評價之改善效果容易產生偏差，例如，若增加進行評價之接合數，則改善效果產生偏差而變得不穩定之可能性提昇，因此，線表面之氧化銅之平均膜厚之上限較佳為設為0.02 μm。關於線表面之氧化銅之平均膜厚，就可減少改善效果之偏差之觀點而言，較佳為0.02 μm以下，更佳為0.015 μm以下，進而較佳為0.013 μm以下。另一方面，為了將線表面之氧化銅之平均膜厚穩定地抑制於未達0.0005 μm，必須進行特殊之表面處理、製品管理等，存在誘發接合性降低、成本增加等而難以適合工業生產之情況，故而線表面之氧化銅之平均膜厚之下限較佳為設為0.0005 μm。例如，若為了將氧化銅之平均膜厚抑制於未達0.0005 μm而增厚線表面之防銹劑之塗佈膜，則存在接合強度降低而連續接合性降低之問題。又，若為了將氧化銅之平均膜厚抑制於未達0.0005 μm而極端縮短線製品之大氣保管下之保證壽命，則亦有因難以進行線接合之量產步驟中之操作或產生碎屑問題等而不允許工業生產之情況。關於線表面之氧化銅之平均膜厚，就可提供適合工業生產之接合線之觀點而言，較佳為0.0005 μm以上，更佳為0.0008 μm以上，進而較佳為0.001 μm以上。 關於線表面之氧化銅之平均膜厚之測定，有效的是適合表面分析之歐傑(Auger)能譜分析，較理想為使用於線表面之隨機位置之最少3處以上、若可能5處以上測得之氧化銅之膜厚之平均值。氧濃度係使用O濃度相對於Cu、O、金屬元素之總計濃度之比率。由於作為線表面之代表性之污染的有機物不包括在內，故而上述濃度計算中不含C量。由於難以高精度地求出氧化銅之膜厚之絕對值，因此較理想為使用歐傑能譜法中一般所使用之SiO2 換算值算出氧化銅膜厚。於本發明中，將氧濃度為30質量%設為氧化銅與金屬銅之邊界。已知主要之氧化銅為Cu2 O、CuO，但於含有第1元素之銅合金之表面，於低溫(25～500℃)下多數情形下優先形成Cu2 O，因此，將氧濃度為30質量%設為邊界。 《第2元素及其效果》 本發明之接合線較佳為進而含有相對於線整體分別為0.0001～0.050質量%之選自Ti、B、P、Mg、Ca、La、As、Te、Se之至少1種以上之元素(亦稱為「第2元素」)。藉此，可改善高密度安裝所要求之球接合部之壓扁形狀，即可改善球接合部形狀之真圓性。又，藉此，可實現更良好之球形狀。關於第2元素之含量(濃度)，就可提高使球接合部之壓接形狀真圓化之效果之觀點而言，較佳為總計為0.0001質量%以上，更佳為0.0002質量%以上，進而較佳為0.0003質量%以上。又，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，第2元素之含量較佳為0.050質量%以下，更佳為0.045質量%以下，進而較佳為0.040質量%以下。又，藉由含有分別為0.0005質量%以上之該第2元素，可獲得減少楔接合部產生不良之效果，因此更佳。藉由添加第2元素，可提高線發生變形時減少線之加工硬化而促進楔接合之線變形的作用。詳細之機制尚不明確，認為由於第1元素固溶於Cu中，第2元素因於Cu中之固溶度較小而析出、偏析，故而該等元素互補地發揮作用，可對楔接合之線變形發揮更優異之效果。 《第3元素及其效果》 本發明之接合線較佳為進而含有總計為0.0005～0.5質量%之選自Ag、Au之至少1種以上之元素(亦稱為「第3元素」)。於最近之高密度安裝所要求之窄間距連接中，球接合部之變形形狀為重要，要求抑制花瓣狀、偏芯等異形，使之真圓化。藉由將第3元素與第1元素併用而添加，可容易地各向同性地進行球變形，可提高使壓接形狀真圓化之效果。確認藉此亦可充分適應50 μm以下之窄間距連接。若第3元素含量總計為0.0005質量以上，則可更有效地發揮該效果。關於第3元素之含量，就可提高使球接合部之壓接形狀真圓化之效果之觀點而言，較佳為總計為0.0005質量%以上，更佳為0.0007質量%以上，進而較佳為0.001質量%以上。又，就獲得良好之FAB形狀之觀點而言，第3元素之含量較佳為0.5質量%以下，更佳為0.4質量%以下，進而較佳為0.3質量%以下。另一方面，若第3元素之含量總計超過0.5質量%，則有FAB形狀變差之虞。若使接合線含有Au，則再結晶溫度上升而防止拉線加工中之動態再結晶，因此加工組織變得均勻，熱處理後之晶粒尺寸相對變均勻。藉此，線之斷裂伸長率提昇，接合時可形成穩定之線迴路。於進而含有Au之情形時，較佳為以線中之第1元素之總計超過0.1質量%之方式規定含量。本發明之接合線可於包含第2元素之同時包含第3元素，亦可含有第3元素代替第2元素。 《Pd之含有及其效果》 本發明之接合線較佳為進而以1.15質量%以下之範圍含有Pd。藉此，可進而提高球接合部之高濕加熱可靠性。認為藉由於接合線中以上述濃度範圍含有Pd，Pd擴散或濃集至接合界面，對Cu與Al之相互擴散造成影響，藉此延緩成長於球接合部接合界面之Cu-Al系金屬間化合物之腐蝕反應。關於Pd之含量，就顯著提高HAST可靠性之觀點而言，較佳為1.15質量%以下，更佳為1.0質量%以下，進而較佳為0.9質量%以下。另一方面，若Pd濃度超過1.15質量%，則因線之常溫強度、高溫強度等上升，而存在可見產生迴路形狀之偏差、降低楔接合性等情況，因此Pd含量上限較佳為設為1.15質量%。本發明之接合線可於包含第2元素及/或第3元素之同時包含Pd，亦可包含Pd代替第2元素及第3元素之任一者或兩者。 《接合線之製造方法》 對本發明之半導體裝置用接合線之製造方法之概要進行說明。 使用銅純度為4 N～6 N(99.99～99.9999質量%)之高純度銅，藉由熔解製作含有所需濃度之添加元素之銅合金。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，較佳為於真空氣氛或Ar或N2 等惰性氣氛中進行熔解。其後，於爐中緩冷，製作鑄錠(鑄塊)。為了洗淨鑄錠表面，進行酸洗及水洗，並使之乾燥。關於銅中之添加元素之濃度分析，有效的是ICP(Inductively Coupled Plasma，感應耦合電漿)分析等。 於該合金化中，有直接添加高純度成分之方法、及利用以1%左右之高濃度含有添加元素之母合金的方法。利用母合金之方法對為了低濃度地含有並使元素分佈均勻化而言有效。於本發明之添加成分中，於含有0.5質量%以上之相對高濃度之第1元素之情形時，可利用高純度之直接添加，於對以低濃度穩定地含有第1元素及第2元素而言，添加母合金之方法較有利。 於接合線中含有第1元素、第2元素、第3元素、及其他元素時，除了如上所述，於熔解時含有該等元素之方法以外，採用使合金元素覆著於接合線表面而含有之方法亦可發揮上述本發明之效果。 亦可於線製造步驟之中途，藉由使合金成分覆著於線表面而含有。於該情形時，可組入至線製造步驟之任意處，亦可反覆進行複數次。亦可組入至複數個步驟。作為覆著方法，可自(1)水溶液之塗佈⇒乾燥⇒熱處理、(2)鍍覆法(濕式)、(3)蒸鍍法(乾式)中選擇。 所製造之銅合金塊首先藉由壓延加工為大徑，其次藉由拉線加工使之變細直至最終線徑。於壓延步驟中，使用槽形輥或型鍛等。於拉線步驟中，使用可安裝複數個經金剛石塗佈之模具之連續拉線裝置。視需要，於加工中途階段或最終線徑時實施熱處理。 若使銅合金接合線含有第1元素，則線之材料強度(硬度)變高。因此，對接合線進行拉線加工時，將拉線時之縮面率設為低如5～8%之縮面率。又，於拉線後之熱處理中，由於硬度依然較高，故而為了軟質化至可用作接合線之級別，而以700℃以上之溫度進行熱處理。因較高之熱處理溫度，故而芯材剖面中之平均結晶粒徑(μm)超過(0.1×R＋0.5)(R為線之線徑(μm))，楔接合性降低一些。另一方面，若降低熱處理溫度，則芯材剖面中之平均結晶粒徑(μm)未達(0.02×R＋0.4)，結果球接合部之壓扁形狀降低一些。 因此，於本發明中，於使用模具進行拉線時，較佳為於全部模具數中之一半以上之模具中將縮面率設為10%以上，進而將拉線後之熱處理時之熱處理溫度設為低如600℃以下之溫度。其結果，可將接合線之垂直於線軸之方向之芯材剖面中之平均結晶粒徑(μm)設為較佳之範圍(0.02×R＋0.4以上且0.1×R＋0.5以下)(R為線之線徑(μm))。應用最新之拉線加工技術，潤滑液係將潤滑液所含之非離子系界面活性劑之濃度設計為高於先前，模具形狀係將模具之前進角設計為緩於先前，且將模具之冷卻水溫度設定為低於先前等，藉由該等之協同效應，儘管於銅合金接合線中含有總計為0.03質量%以上之第1元素成分而硬質化，亦可進行縮面率10%以上之拉線加工。 作為用於以量產級別將線表面之氧化銅之平均膜厚管理成0.0005～0.02 μm之範圍內之製造條件，較佳為抑制線製造步驟中之氧化。為了控制熱處理步驟中之氧化銅之形成，有效的是調整溫度(200～850℃)及熱處理步驟中之惰性氣體流量(1～8 L/min)、管理爐內之氧濃度等。氧濃度係於爐之中央部測定，有效的是以其濃度範圍為0.1～6體積%之方式進行調整。作為將氧濃度控制於上述範圍之方法，可藉由適量化上述氣體流量、改變爐之入口、出口等之形狀，而防止自外界向熱處理爐內帶入大氣等。進而，於量產級別中，較理想為亦對拉線步驟進行管理，例如，藉由於在水中之拉線步驟之1行程後於捲取線之前進行乾燥(吹送40～60℃之溫風大氣)而積極地去除線表面之水分、以及管理製造步驟中途之保管濕度(保管2天以上之情況下相對濕度為60%以下)等亦有效。 [實施例] 以下，一面展示實施例，一面對本發明之實施形態之接合線具體地進行說明。 (樣品) 首先對樣品之製作方法加以說明。成為芯材之原材料之Cu係使用純度為99.99質量%以上(於本實施例中使用6 N(濃度為99.9999質量%以上者))且剩餘部分包含不可避免之雜質者。第1元素、第2元素、第3元素及Pd係使用純度為99質量%以上且剩餘部分包含不可避免之雜質者。以線或芯材之組成成為目標組成之方式，調合作為向芯材添加之元素的第1元素、第2元素、第3元素、Pd之合金元素。關於各元素之添加，亦可調合單一成分，但是於單一成分為高熔點之元素或添加量極其微量之情形時，亦可預先製作包含添加元素之Cu母合金，以成為目標之添加量之方式進行調合。 銅合金係藉由連續鑄造而以成為數mm之線徑之方式製造。對所獲得之數mm之合金進行拉伸加工而製作
Figure TW201802257AD00001
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/min。除了一部分實施例外，為了去除線表面之氧化膜而利用鹽酸等進行酸洗處理，其後使用全部模具數中之一半以上之模具之縮面率為10～21%之模具，進行拉線加工，進而中途以200～600℃進行1至3次熱處理，藉此，加工至直徑20 μm或直徑18 μm。加工後以最終斷裂伸長率成為約5～15%之方式進行熱處理。熱處理方法係一面連續地拂掠線一面進行，且一面通入氮氣或氬氣一面進行。將線之進給速度設為10～90 m/min，將熱處理溫度設為350～600℃，將熱處理時間設為1～10秒。關於實施例6、10、11、23、55、56、62、77之製造方法，於實施例11、56中將熱處理溫度設為低如300℃以下之溫度，於實施例6、10、55、62、77中將熱處理溫度設為高如700℃以上之溫度。 (評價方法) [元素之含量] 關於線中之各合金元素之含量，利用ICP發射光譜分析裝置進行分析。 [結晶粒徑] 關於結晶粒徑，藉由EBSD法進行評價。EBSD測定資料之解析係利用專用軟體(TSL Solutions公司製造之OIM Analysis等)。結晶粒徑係將測定區域內所含之晶粒之等效直徑(相當於晶粒之面積之圓之直徑)進行算術平均而得者。 [氧化銅之平均膜厚] 線表面之氧化銅之平均膜厚之測定係利用歐傑能譜分析進行深度分析，使用於線表面之隨機位置之最少3處以上測得之氧化銅之膜厚之平均值。一面以Ar離子進行濺射一面於深度方向進行測定，深度之單位係以SiO2 換算表示。將氧濃度為30質量%設為氧化銅與金屬銅之邊界。此處所謂氧濃度係使用氧濃度相對於Cu、氧、金屬元素之總計濃度之比率。測定係使用SAM-670(PHI公司製造，FE型)，將電子束之加速電壓設為5 kV，將測定區域設為10 nA，於Ar離子濺射之加速電壓為3 kV，濺射速度為11 nm/min下進行測定。將氧化銅之平均膜厚之測定結果記載於各表之「氧化銅平均膜厚」欄。 [HAST] 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，進行HAST評價並根據球接合部之接合壽命進行判定。接合可靠性評價用樣品係以下述方式製作：於在一般之金屬框架上之Si基板上成膜厚度0.8 μm之Al-1.0%Si-0.5%Cu之合金而形成之電極上，使用市售之打線接合機進行球接合，並利用市售之環氧樹脂進行密封。一面以流量0.4～0.6 L/min通入氮氣＋5%氫氣一面形成球，將其大小設為
Figure TW201802257AD00002
33～34 μm之範圍。 關於HAST評價，使用不飽和型壓力鍋試驗試驗機，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。每隔48小時實施球接合部之剪切試驗，將球接合部之接合壽命設為剪切強度之值成為初始所獲得之剪切強度之1/2之時間。高溫高濕試驗後之剪切試驗係於藉由酸處理去除樹脂，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處之測定值之平均值。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，標記為×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，標記為△記號，若為144小時以上且未達192小時則判斷為實用上無問題，標記為○記號，若為192小時以上則判斷為優異，標記為◎記號，記於各表之「HAST」欄。僅×為不合格，除此以外均為合格。 [FAB形狀] 球部之球形成性(FAB形狀)之評價係採取進行接合前之球進行觀察，判定球表面有無氣泡，原本為真球之球有無變形。於發生上述任一情況之情形時判斷為不良。關於球之形成，為了抑制熔融步驟中之氧化，係一面以流量0.5 L/min吹送氮氣一面進行。將球之直徑設為線之線徑之1.7倍。對於1個條件觀察50個球。觀察係使用SEM。於球形成性之評價中，於不良發生5個以上之情形時，判斷為有問題，標記為×記號，若不良有3～4個則判斷為可實用但稍有問題，標記為△記號，於不良有1～2個之情形時判斷為無問題，標記為○記號，於未發生不良之情形時判斷為優異，標記為◎記號，記於各表之「FAB形狀」欄。僅×為不合格，除此以外均為合格。 [楔接合性] 線接合部之楔接合性之評價係於引線框架之引線部分接合1000根，根據接合部發生剝離之頻度進行判定。引線框架係使用實施過1～3 μm之鍍Ag之Fe-42原子%Ni合金引線框架。於本評價中，假定較通常更嚴格之接合條件，將載台溫度設為低於一般設定溫度區域之150℃。於上述評價中，於不良產生11個以上之情形時判斷為有問題，標記為×記號，若不良有6～10個則判斷為可實用但稍有問題，標記為△記號，於不良為1～5個之情形時判斷為無問題，標記為○記號，於未發生不良之情形時判斷為優異，標記為◎記號，記於各表之「楔接合性」欄。僅×為不合格，除此以外均為合格。 [壓扁形狀] 球接合部之壓扁形狀之評價係自正上方對進行了接合之球接合部進行觀察，根據其真圓性進行判定。接合對象係使用於Si基板上成膜厚度1.0 μm之Al-0.5%Cu之合金而成之電極。觀察係使用光學顯微鏡，對於1個條件觀察200處。將從真圓改變較大之橢圓狀者、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，於不良發生6個以上之情形時判斷為有問題，標記為×記號，若不良為4～5個，則作為可實用但稍有問題，標記為△記號，於1～3個之情形時判斷為無問題，標記為○記號，於全部獲得良好之真圓性之情形時，判斷為特別優異，標記為◎記號，記於各表之「壓扁形狀」欄。 [表1]
Figure TW201802257AD00003
 [表2]
Figure TW201802257AD00004
 [表3]
Figure TW201802257AD00005
 [表4]
Figure TW201802257AD00006
 [表5]
Figure TW201802257AD00007
 [表6]
Figure TW201802257AD00008
 (評價結果) 如表1、2所示，確認：於第1元素之濃度合計為0.03～3.0質量%之實施例1～103之銅合金接合線中，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。 又，線表面之氧化銅之平均膜厚為0.0005～0.02 μm之範圍的實施例1～103之接合線之HAST評價結果均良好。 又，實施例之接合線中，於在全部模具數中之一半以上之模具中將拉線時之縮面率設為10%以上，將拉線後之熱處理時之熱處理溫度設為低如600℃以下之溫度的實施例1～5、7～9、12～22、24～54、57～61、63～69、71～76、78～103之接合線中，接合線之垂直於線軸之方向之芯材剖面中之平均結晶粒徑(μm)為0.02×R＋0.4以上且0.1×R＋0.5以下之範圍內(R為線之線徑(μm))。此處，若比較第1元素之含量為0.8～1.0質量%之實施例7～14之評價結果，則發現平均結晶粒徑為上述範圍內之接合線(實施例7～9、實施例12～14)相較於平均結晶粒徑為上述範圍外之接合線(實施例10、11)，楔接合性與球接合部之壓扁形狀更良好。根據該結果可知，若接合線之垂直於線軸之方向之芯材剖面中之平均結晶粒徑(μm)為0.02×R＋0.4以上且0.1×R＋0.5以下之範圍內(R為線之線徑(μm))，則楔接合性與球接合部之壓扁形狀良好。 於實施例11中，由於將熱處理溫度設為低如300℃以下，故而平均結晶粒徑未達較佳範圍之下限，結果楔接合性為「△」而降低一些。 於實施例10中，由於將熱處理溫度設為高如700℃以上之溫度，故而平均結晶粒徑超過較佳範圍之上限，其結果，於實施例10中，壓扁形狀為「△」而降低一些。 於包含2種以上第1元素之實施例24～43之接合線中，相較於僅包含1種第1元素且其含量為相同程度之實施例7～14之接合線，HAST試驗之結果進一步良好。根據該結果可知，於包含2種以上第1元素之接合線中，於溫度為130℃、相對濕度為85%之高溫高濕環境下之HAST試驗中，球接合部可靠性進一步良好。 於實施例之接合線中，於進而含有分別為0.0001～0.050質量%之第2元素之實施例44～66之接合線中，球接合部之壓扁形狀良好。 於實施例之接合線中，於進而含有總計為0.0005～0.5質量%之選自Ag、Au之至少1種以上之元素(第3元素)的實施例67～92之接合線中，球接合部之壓扁形狀良好。 於實施例之接合線中，於進而含有1.15質量%以下之Pd之實施例93～103之接合線中，確認於溫度為130℃、相對濕度為85%之高溫高濕環境下之HAST試驗中，球接合部可靠性進一步良好。 於實施例之接合線中，於除了第1元素之外，進而含有分別為0.0001～0.050質量%之第2元素、及總計為0.0005～0.07質量%之選自Ag、Au之至少1種以上之元素(第3元素)的實施例75、76、84、85、90～92之接合線中，可獲得HAST評價結果、楔接合性、及球接合部之壓扁形狀均良好之較佳結果。其中，於包含2種以上第1元素之實施例75及76中，HAST評價結果尤其良好。 又，於實施例之接合線中，於除了第1元素以外進而含有分別為0.0001～0.050質量%之第2元素、及1.15質量%以下之Pd的實施例98～99之接合線中，可獲得HAST評價結果進一步良好，FAB形狀、楔接合性、及球接合部之壓扁形狀良好之較佳結果。 另一方面，於比較例之接合線中，於第1元素合計濃度小於0.03質量%之比較例3、4之接合線中，於HAST試驗中無法獲得球接合部可靠性，於第1元素合計濃度大於3質量%之比較例1、2、5、6之接合線中，FAB形狀及楔接合性不良。
無

Claims (7)

  1. 一種半導體裝置用銅合金接合線，其特徵在於含有總計為0.03質量%以上且3質量%以下之選自Ni、Zn、Ga、Ge、Rh、In、Ir、Pt之至少1種以上之元素，且剩餘部分包含Cu及不可避免之雜質。
  2. 如請求項1之半導體裝置用銅合金接合線，其中若將線之線徑設為R(μm)，則上述銅合金接合線之垂直於線軸之方向之芯材剖面中之平均結晶粒徑(μm)為 0.02×R＋0.4以上 (1a) 0.1×R＋0.5以下 (1b)。
  3. 如請求項1或2之半導體裝置用銅合金接合線，其中線表面之氧化銅之平均膜厚為0.0005～0.02 μm之範圍。
  4. 如請求項1至3中任一項之半導體裝置用銅合金接合線，其中上述銅合金接合線進而含有相對於線整體分別為0.0001～0.050質量%之選自Ti、B、P、Mg、Ca、La、As、Te、Se之至少1種以上之元素。
  5. 如請求項1至4中任一項之半導體裝置用銅合金接合線，其中上述銅合金接合線進而含有相對於線整體總計為0.0005～0.5質量%之選自Ag、Au之至少1種以上之元素。
  6. 如請求項1至5中任一項之半導體裝置用銅合金接合線，其中上述銅合金接合線進而含有1.15質量%以下之Pd。
  7. 如請求項1至6中任一項之半導體裝置用銅合金接合線，其中上述銅合金接合線含有2種以上之選自Ni、Zn、Ga、Ge、Rh、In、Ir、Pt之元素。
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