TWI496900B - Copper alloy bonding wire for semiconductors - Google Patents
Copper alloy bonding wire for semiconductors Download PDFInfo
- Publication number
- TWI496900B TWI496900B TW099120568A TW99120568A TWI496900B TW I496900 B TWI496900 B TW I496900B TW 099120568 A TW099120568 A TW 099120568A TW 99120568 A TW99120568 A TW 99120568A TW I496900 B TWI496900 B TW I496900B
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- Taiwan
- Prior art keywords
- wire
- copper alloy
- copper
- mass
- bonding wire
- Prior art date
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C1/00—Manufacture of metal sheets, metal wire, metal rods, metal tubes by drawing
- B21C1/003—Drawing materials of special alloys so far as the composition of the alloy requires or permits special drawing methods or sequences
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/04—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire
- B21C37/047—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire of fine wires
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- 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
- B23K35/0255—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in welding
- B23K35/0261—Rods, electrodes, wires
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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
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
本發明係關於為了連接半導體元件上的電極與電路配線基板的配線所利用的半導體用銅合金接合線。
目前,以線徑20~50μm(微米)左右的細線(接合線)為主,用作接合半導體元件上的電極與外部端子之間的接合線。接合線的接合,一般係超音波併用熱壓著方式,使用泛用接合裝置、在內部通過接合線用於連接的毛細管治具等。金屬線前端以弧形入熱加熱溶融,以表面張力形成球形後,在150~300℃的範圍內加熱的半導體元件的電極上壓著接合此球形部,之後在外部引線側以超音波壓著直接楔形接合接合線。
接合線的材料中,目前為止主要使用高純度4N系(純度>99.99的質量%)的金。不過,由於金係昂貴的,又電源系IC(積體電路)等中要求粗線的金屬線(線徑50~100μm左右)等,因此想要材料費廉價的其他金屬的接合線。
接合線技術的要求中,形成球形時,形成正球性良好的球形,球形部與電極之間的接合部的形狀最好儘量接近正圓,還要求充分的接合強度。又,為了對應接合溫度的低溫化、接合線的細線化等,引線端子、配線基板上的接合線以超音波壓著的楔形連接中,要求可以不發生剝離地連續接合,且得到充分的接合強度等。
如自動車用半導體等的高溫下放置的用途中,金接合線與鋁電極之間的接合部經常有長期可靠性的問題。根據高溫加熱試驗等的加速評估,產生上述接合部的接合強度下降、電阻上升等的不良。金/鋁接合部(金接合線與鋁電極之間的接合部)因高溫加熱的不良成為限制高溫使用半導體的主因。
為了提高如此高溫加熱中的接合可靠性,一般知道以銅為材料的銅接合線是有希望的,例如,非專利文件1等也有報告。指出銅/鋁接合部(銅接合線與鋁電極間的接合部)中的Cu-Al(銅鋁)系金屬間化合物的成長速度相較於金/鋁接合部中的Au-Al系金屬間化合物的成長速度,延遲至1/10以下等,係其中一個原因。
由於銅的材料費廉價、電氣傳導性比金高等的優點,專利文件1~3中揭示了開發銅接合線。不過,銅接合線中,球形部的硬度比Au(金)更高,焊墊電極上球形變形接合之際,對晶片有裂傷等的損傷的問題。關於銅接合線的楔形接合,與金相較,製造容限狹小,擔心量產性下降。又,如前述,金產生的問題,關於在高溫加熱下的接合可靠性,雖然確認銅良好,但不充分了解除此之外的過苛使用環境下的可靠性,要求傾向實用化的綜合使用性能、可靠性的確認及改善。
[專利文件1] 特開昭61-251062號公報
[專利文件2] 特開昭61-20693號公報
[專利文件3] 特開昭59-139663號公報
[專利文件4] 特開平7-70673號公報
[專利文件5] 特開平7-70675號公報
[非專利文件1]”The emergence of high volume copper ball bonding(發生大量銅球接合)”,M. Deley,L. Levine,IEEE/CPMT/SEMI 29th(第29期)International Electronics Manufacturing Technology Symposium,(2004) pp. 186-190.(國際電子製造技術評論集(2004)第186-190頁)
有關確保傾向實用化的綜合可靠性,對銅接合線的長期可靠性進行許多可靠性評估後,相對於最常利用的加熱測試,即在乾燥環境中的高溫保管評估係正常的,而高溼加熱評估中確認發生不良。進行PCT測試(壓力鍋測試)作為一般高溼加熱評估。其中,飽和型的PCT測試常用作較嚴的評估,代表的測試條件係溫度121℃、相對溼度100%RH(相對溼度),在2大氣壓下進行。關於PCT測試,金接合線幾乎沒有因金屬線材料產生問題,金接合線(金線)的PCT測試不受注目。開發階段的銅接合線在PCT測試的可靠性很少受到注目,目前為止PCT測試的不良幾乎未知。
本發明者的實驗中,連接銅接合線的半導體以樹脂封止後,進行飽和型的PCT測試時,確認發生接合強度下降、電阻增加等的不良。上述加熱條件中的不良發生時間為100小時到200小時,擔心實用上的問題。由於銅接合線在PCT測試中發生導通不良的頻率比金接合線高,為了活用於與金接合線同等的用途中,要求在PCT測試中提高壽命。
又,依照用途,除了上述的可靠性,可能再加上希望提高對熱循環的可靠性。根據溫度升降的熱循環測試(TCT:溫度循環測試)中,確認銅接合線(銅線)的不良發生頻率比金接合線高。TCT測試條件係以-55℃~150℃的範圍重覆溫度循環後,評估電阻、接合強度等。主要的不良處在第2接合部。原因被認為是樹脂、引導框架、矽晶片等的材料因熱膨脹差大而產生熱變形,接合線的第2接合部中發生破裂。金接合線的TCT測試,以通常的半導體封裝及使用環境不會有問題,只有在周邊部材的變化、過苛的加熱條件等的極稀少的情況下,考慮TCT測試發生不良的可能性。不過,銅接合線由於TCT測試不良發生頻率比金接合線高,用途受限,可能變得難以適應多樣的周邊部材。因此,作為更優良的銅接合線,要求對熱循環更加提高可靠性。
銅接合線在球形部接合至鋁電極上時,擔憂接合形狀的不良頻率比金接合高。廣泛使用的金接合線中,為了回應狹間距連接等LSI(大型積體電路)用途的嚴格要求,進行起正圓化球形接合形狀的開發。銅接合線中,由於減輕在接合部正下方的晶片損傷等的目的,材料中常使用高純度的銅,結果擔心接合形狀惡化。為了促進今後的狹間距連接等LSI用的銅接合線實用化,除了要求上述的可靠性,再加上更加改善球形接合形狀。
最近的接合技術、封裝構造等也急速進化,銅接合線的要求特性也在變化。以前,對銅接合線也期待與金接合線同樣地高強度化。不過,為了順應接合技術的提高、追趕量產性等的需求,銅接合線的要求特性中,更重視軟質化、接合安定性等。
本發明的目的係提供半導體用銅合金接合線,用以解決如上述習知技術的問題,改善高溼加熱PCT測試的可靠性,並以比金接合線更廉價的銅為主體。
根據申請專利範圍第1項的半導體用銅合金接合線,其特徵在於含有0.13~1.15質量%的Pd(鈀),且其餘部分為銅及不可避免的不純物構成的銅合金以伸線加工形成。
根據申請專利範圍第2項的半導體用銅合金接合線,其特徵在於申請專利範圍第1項中,金屬線表面的氧化銅的平均膜厚在0.0005~0.02μm(微米)的範圍。
根據申請專利範圍第3項的半導體用銅合金接合線,其特徵在於申請專利範圍第1及2項中,與金屬線長度方向平行並在金屬線剖面中的結晶粒的平均大小為2μm以上且在金屬線線徑的1.5倍以下。
根據申請專利範圍第4項的半導體用銅合金接合線,其特徵在於申請專利範圍第1至3項中的任一項中,上述銅合金更含有Ag、Au至少1種,總計0.0005~0.07質量%。
根據申請專利範圍第5項的半導體用銅合金接合線,其特徵在於申請專利範圍第1至4項中的任一項中,上述銅合金含有Ti(鈦):0.0005~0.01質量%、B(硼):0.0005~0.007質量%、P(磷):0.0005~0.02質量%中的至少1種,總計0.0005~0.025質量%。
根據本發明,可以提供材料費廉價、有關高溼加熱的接合部的長期可靠性優異的半導體用銅合金接合線。又,可以提供有關熱循環的可靠性優異的半導體用銅合金接合線。又,可以提供球形變形良好、量產性也優異的半導體用銅合金接合線。
接合線中,專心調查以銅為材料的銅接合線中含有成分的影響結果,銅中添加特定量的Pd(鈀),發現PCT測試的高溼加熱可靠性提高。專利文件4及5中,有關銅接合線,為了抑制球形形成時產生H2
(氫)、O2
(氧)、N2
(氮)、以及CO(一氧化碳),揭示添加包含Pd的元素群。不過,上述包含上述Pd的元素群的添加量,係0.001~2質量%的廣範圍,沒有記載或揭示有關本發明在特定範圍內添加Pd,提高高溼加熱可靠性,得到完全不同的作用效果。
又,藉由添加特定量的Pd,再加上Ag、Au(剩餘部分的銅以特定添加量的Ag或Au置換),改善球形變形形狀,或是,藉由添加特定量的Pd,再加上Ti、B、P(剩餘部分的銅以特定添加量的Ti、B、P置換),發現對提高TCT測試的熱循環可靠性有效。又,藉由添加上述的Pd,並控制於特定的組織,確認得到提高楔形接合性的高效果。
本發明的半導體用銅合金接合線,係含有濃度範圍為0.13~1.15質量%的Pd的銅合金構成的半導體用銅合金接合線。藉由在上述濃度範圍中添加Pd,可以提高PCT測試的高溼加熱可靠性。即,由於含有上述濃度範圍中的Pd,到PCT測試不良發生為止的壽命,相對於習知的銅接合線,可以提高至1.3~3倍。因此,可以在與金接合線同等的用途下利用銅接合線。即,銅接合線的用途可以擴大至目前之上。
連接習知的銅接合線的半導體的PCT測試中的不良形態係銅接合線與鋁電極之間的接合部中強度下降、以及電阻增加。本發明者明確此不良機構,在CU/Al接合界面(銅接合線與鋁電極之間的接合界面)中,腐蝕反應為主因。即,此主因係PCT測試中在接合界面中成長的CU/Al系的金屬間化合物與封止樹脂內所含的氣體成分或離子等產生腐蝕反應。本發明的半導體用銅合金接合線,由於銅接合線中含有上述濃度範圍內的Pd,Pd擴散或濃化至接合界面,達到影響Cu與Al間的相互擴散,被認為因而延遲了腐蝕反應。接合界面近旁的Pd的角色被認為是阻礙腐蝕反應物的移動的阻障功能、控制Cu、Al的相互擴散及金屬間化合物的成長等的功能。
如果Pd濃度在0.13~1.15質量%的範圍的話,得到控制接合界面中Cu、Al互相擴散的效果,PCT測試的接合部壽命提高至200小時以上。在此的接合部評估,PCT測試後將樹脂拆封除去,之後以拉力測試評估接合部的破裂狀況。此時,Pd濃度未達0.13質量%時,上述的PCT可靠性的改善效果小,不夠。另一方面,Pd濃度超過1.15質量%時,由於低溫接合中與鋁電極間的初期接合強度下降,PCT測試的長期可靠性下降,接合至BGA(球形柵極陣列)、CSP(晶片尺寸封裝)等的基板、膠帶等的量產容限變狹窄。更佳的是,上述Pd濃度在上述範圍0.2~1.1質量%的範圍的話,PCT測試的可靠性更加提高。例如,PCT測試到不良發生為止的壽命提高至500小時。這可能相當於習知的銅接合線的1.5倍以上的長壽命化,可以應付在過苛環境下使用。
又,必須檢討不降低半導體用銅合金接合線的使用性能,作為添加高濃度Pd之際的留意點。Pd濃度超過1.15質量%時,由於金屬線的常溫強度‧高溫強度等上升,產生環路形狀的偏離、楔形接合性的下降等變顯著。因此,Pd濃度在0.13~1.15質量%的範圍的話,環路高度的偏離減輕,變得容易確保良好的楔形接合性等。
如果是包含Pd在0.13~1.15質量%的濃度範圍的銅合金形成的半導體用銅合金接合線的話,其前端溶融形成的球形內部中,由於Pd大致均質固溶,得到PCT可靠性在量產水準中穩定並提高的效果。球形內部的Pd的角色被認為是延遲球形內部的腐蝕性離子擴散,阻礙接合界面的密著性提高產生的腐蝕性氣體移動,還有用作從上述球形內部擴散到接合界面的Pd供給源。上述量產水準的PCT可靠性提高時,高密度實裝中,每一晶片300~1800接腳等的多接腳系中連一接腳也不會產生接合部不良的穩定管理,或是,相當於壓著球徑在45μm以下的小接合部的界面中,連數μm的範圍也可以抑制腐蝕的嚴格控制的管理。對於如此的高度可靠性提高,Pd在球形內部中固溶也是有效的。
球形內部包含的Pd含有量為0.08~1.5質量%的範圍的話,PCT的接合可靠度以量產水準穩定提高的效果可以提高。此時,球形內部的Pd含有量的合適範圍與金屬線內部的含有量稍微不同的理由被認為係由於金屬線溶融‧凝固之際一部分的Pd擴散引起的球形表面濃化,產生球形內部的濃度不均,還有接合後的樹脂封止過程及可靠性測試等的加熱引起Pd擴散至接合界面近旁,發生Pd濃度的分布。即,如果是金屬線內部的Pd含有量為0.13~1.15質量%的濃度範圍的半導體用銅合金接合線的話,使球形內部的Pd含有量在0.08~1.5質量%的合適範圍變得容易,在此可以提高可靠性更穩定改善的效果。
如果是包含Pd在0.13~1.15質量%的濃度範圍的銅合金形成,金屬線的表面的氧化銅的平均膜厚在0.0005~0.02μm的範圍內的半導體用銅合金接合線的話,PCT可靠性以量產水準穩定提高的效果更加提高。金屬線表面的氧化銅的膜厚比0.02μm還厚時,含有Pd的銅合金形成的接合線的球形接合部的PCT可靠性的改善效果產生偏離,PCT加熱後的接合強度等有不穩定的傾向。此PCT可靠性偏離在線徑20μm以下的接合線中可能更有問題。含有Pd的銅合金表面的氧化銅是使PCT可靠性不穩定的主因,雖然還有不明點,但認為半導體用銅合金接合線的長度方向或金屬線表面開始往深度方向的Pd濃度分布不均,或是,球形內部的侵入氧或殘留氧化物可能阻礙Pd的PCT可靠性改善效果等。又,因為含有Pd的半導體用銅合金接合線得到表面氧化延遲的效果,氧化銅的平均厚度也變得容易控制在0.0005~0.02μm。包含Pd在0.13~1.15質量%的濃度範圍的半導體用銅合金接合線中,與高純度銅相較,確認在20~40℃左右的低溫區中具有延遲金屬線表面的氧化銅膜成長的作用。
金屬線表面的氧化銅的平均膜厚為0.0005~0.02μm的範圍的理由係:超過0.02μm時,如上所述,PCT可靠性的改善效果容易產生偏離,例如因為評估的接合數增加與產生改善效果偏離而變得不穩定的可能性提高。另一方面,為了穩定控制金屬線表面的氧化銅的平均厚度不到0.0005μm,必須特殊的表面處理、製品管理,於是接合性下降、成本上升,工業上的適應變得困難。例如,由於控制氧化銅的平均膜厚不到0.0005μm的目的,金屬線表面的防鏽劑的塗佈膜加厚時,有接合強度下降而接合性下降的問題。由於控制氧化銅的平均膜厚不到0.0005μm的目的,金屬線製品的大氣保管的保證壽命變極短的話,打線接合的量產製程中的作業變得困難,由於發生報廢問題,可能工業上不容許。
有關測量金屬線表面的氧化銅的平均膜厚,適合表面分析的AUGER(歐傑)分光分析有效,最好測量金屬線表面的隨機位置中最少3處以上,儘可能5處以上,使用氧化銅的膜厚平均值。氧濃度係使用對Cu、O、金屬元素的總計濃度的O濃度的比率。由於金屬線表面的代表性污染的有機物除外,上述濃度計算中不含C量。由於難以高精密度地要求氧化銅的膜厚絕對值,最好利用AUGER(歐傑)分光法中一般使用的SiO2
(二氧化矽)換算值,算出氧化銅膜厚。本說明書中,以氧濃度30質量%作為氧化銅及金屬銅之間的邊界。已知主要的氧化銅為Cu2
O、CuO,但含有Pd的銅合金的表面為低溫(25~500℃)時,由於常優先形成Cu2
O,以氧濃度30質量%為邊界。
金屬線表面的氧化銅的平均膜厚為0.0005~0.02μm的範圍內,作為用以管理量產水準的製造條件,必須抑制金屬線製程中的氧化。對於控制熱處理過程中的氧化銅形成,溫度(200~850℃)、熱處理過程中的非活性氣體流量的調整(1~8升/分)、爐內的氧濃度的管理等是有效的。氧濃度,在爐的中央部測量,調整其濃度範圍為0.1~6體積%是有效的。作為控制氧濃度在上述範圍中的方法,藉由合適的上述氣體流量、爐的入口出口等的形狀改變,可以管理防止大氣從外界捲入熱處理爐內等。還有量產水準中,最好也管理伸線製程,例如,水中的伸線製程1道次(pass)後,捲取金屬線前,以乾燥(吹40~60℃的溫風大氣)積極除去金屬線表面的水分、管理在製造過程中的保管溼度(2天以上的保管在相對溼度60%以下)等也有效。
半導體用銅合金接合線含有Pd 0.13~1.15質量%的濃度範圍,還有與半導體用銅合金接合線的長度方向(以下,稱作金屬線長度方向)平行的金屬線剖面中的結晶粒的平均大小(數個平均大小)最好在2μm以上75μm以下。由於上述結晶粒的平均大小在2μm以上,結晶方位的異方性減輕,促進半導體用銅合金接合線的軟質化。結果,得到環路形狀更穩定,楔形接合性更提高的效果。具體的效果為控制半導體用銅合金接合線的曲折、塑性變形,不限制連接方向地往四方向穩定控制複雜的環路形狀,又減低楔形接合中發生不著的不良(引線沒有黏著問題:NSOL),提高實裝良率的效果等。最近的接合技術、封裝構造等也急速進化,銅接合線的要求特性也在變化。以前,雖然期待銅接合線與金接合線同樣高強度化,但最近更重視軟質化、接合穩定性等。為了正好適應最新的封裝構造,抑制添加Pd的銅接合線的高強度化,且為了更提高環路控制、楔形接合性,放大結晶粒的平均尺寸是有效的。在此,結晶粒在2μm以上的話,充分得到上述的效果。例如,也可以充分適用環路高度不同的多段連接等的最先端的封裝。習知的金接合線的泛用品中,金接合線的組織為纖維狀,結晶粒的平均尺寸不到1μm。添加Pd的銅接合線中,由於結晶粒微細化的傾向強,擔心接合製程的良率下降。由於組合添加Pd與結晶粒的粗大化,得到更改善環路控制、楔形接合性的更高效果。結晶粒的平均尺寸最好在3μm以上,可以更提高楔形接合性的效果,主要在線徑20μm以下的細線中,得到特段的改善效果。為了得到上述效果,雖然結晶粒的平均尺寸沒有特別的上限,但由於半導體用銅合金接合線的生產性,上限為75μm。這相當於50μm徑的半導體用銅合金接合線的線徑1.5倍以下。線徑25μm以下的細線中,結晶粒的平均尺寸的上限最好在線徑1.5倍以下。超過上述上限時,由於過於粗大化而結晶粒成竹節狀,可能金屬線製造中線徑局部變細而生產性下降。在此,本發明的結晶粒的粒尺寸決定如下。
對於半導體用銅合金接合線的結晶粒觀察,可以利用包含金屬線軸在金屬線長度方向的金屬線剖面(軸剖面)或金屬線表面的觀察。如果是軸剖面的觀察,最好可以觀察也包含內部的半導體用銅合金接合線全體的組織。
為了以量產水準穩定製造含有Pd 0.13~1.15質量%的濃度範圍,還有與金屬線長度方向平行的金屬線剖面中的結晶粒的平均尺寸2μm以上、金屬線線徑的1.5倍以下的半導體用銅合金接合線,伸線加工與加熱處理條件的適當化是有效的。線徑20μm的極細線的一製造條件範例中,伸線製程的加工率在99.9%以上,平均伸線速度為200~400m(公尺)/分,熱處理過程中,使用均熱帶長度200mm的熱處理爐,溫度400~800℃、掃描速度20~100m(公尺)/分,非活性氣體流量在0.5~6L/分的範圍,藉此,即使難以品質穩定化的極細線也不會生產性下降,使結晶粒的平均尺寸在2μm以上、金屬線線徑的1.5倍以下穩定化在工業上變得容易。伸線製程途中,在加工率99.5~99.99%的範圍內,最好進行一回以上的熱處理(上述條件中溫度為300~600℃)。因此,固溶Pd的銅合金中,由於進行一部分的復原‧再結晶,得到抑制最終線徑中的結晶粒徑偏離的效果。
如以下特定晶結粒界(結晶粒之間的邊界),明確結晶粒的形狀以測量結晶粒的尺寸。以化學蝕刻法或CP(剖面拋光)法直接觀察結晶粒界的方法,或是以後方電子散亂圖形(以下稱EBSP)法解析結晶粒界的方法,確定上述的結晶粒界。如果是化學蝕刻的話,藉由選擇適合表皮層或芯材的材料、構造等的藥液、蝕刻條件,可以簡便地觀察結晶粒等的組織。例如,可以使用鹽酸、硝酸、硫酸、醋酸等的酸性水溶液作為上述藥液。選定所謂蝕刻條件的上述濃度(pH)與溫度、時間,藉由選擇性溶解粒界,或選擇性溶解特定的結晶面,確定結晶粒界,觀察結晶粒的形狀。根據CP法,使用例如2~6kV的加速電壓的氬離子寬電子束,形成試料剖面,明確結晶粒界,觀察結晶粒的形狀。根據EBSP法,由於可以測量各結晶粒的方位,可以確定結晶粒界。根據本發明,假設鄰接結晶粒的方位差15°以上的結晶粒界。
結晶粒的平均尺寸,係以數個平均算出的。至少5個以上的結晶粒尺寸的平均。又,根據本發明,不必全部上述分析方法所得到的結晶粒平均尺寸滿足本發明的規定範圍,1個分析方法所得到的結晶粒平均尺寸滿足本發明的規定範圍的話,就達到效果。
結晶粒的尺寸判定,可以利用根據光顯、SEM(掃描電子顯微鏡)、EBSP等拍的照片的判定方法、以及解析軟體的方法。上述的照片判定中,結晶粒非圓形而為不定形時,測量結晶粒的長徑與短徑再求出平均值的方法有效。後者的話,藉由利用EBSP裝置中裝備的解析軟體,比較容易同時與觀察求出。
含有Pd 0.13~1.15質量%的濃度範圍,且含有Ag、Au中至少一種總計0.0005~0.07質量%的半導體用銅合金接合線更佳。根據最近的高密度實裝要求的窄間距連接,球形接合部的變形形狀很重要,制止花瓣、偏芯等的異形,要求正圓化。與Pd併用,添加Ag、Au中至少一種,藉此球形變形可以容易等方,壓著形狀正圓化的效果提高。因此,確認50μm以下的窄間距連接也可以充分適應。使球形變形正圓化的效果,只有Ag、Au元素群的話很小,但確認與Pd組合可以更提高。詳細的結構雖不明,但認為球形部凝固之際,高融點金屬的Pd在球形表面近旁以較高濃度聚集,融點比Pd低的Ag、Au到球形內部為止均一固溶,藉此,以這些組合互補作用,對球形變形的正圓化可以發揮更優異的效果。作為在此互補作用的一範例,球形部的花瓣變形由球形表面近旁支配,而偏芯由球形內部支配,期待兩者同時改善的作用。也確認了Ag與Au的效果係同程度的。在此,有關Ag、Au的總計濃度範圍,未達0.0005質量%的話,容易正圓化球形變形的效果可能變小。超過0.07質量%的話,球形接合部的抗切強度可能下降。又,關於添加Ag、Au,不含Pd的情況下(雖然不是可以滿足高溼加熱的可靠性),添加Ag、Au產生的正圓化球形變形的效果變小,為了得到充分的效果,Ag、Au的濃度範圍總計必須達到2%質量以上的高濃度化。即,藉由Ag、Au中至少1種與Pd併用,得到正圓化球形變形的顯著效果。不過,含有Pd的情況下,即使控制在低的Ag、Au的添加濃度,也得到充分抑制對晶片損傷的壞影響的相乘效果。
又,由於含有Pd 0.13~1.15質量%,Ag、Au中至少一種總計0.0005~0.07質量%,與金屬線長度方向平行的金屬線剖面中的結晶粒的平均尺寸在2μm以上,可以正圓化球形形狀,得到更高的效果。雖然關於機械結構還留下不明點,但認為是由於結晶粒變大,楔形接合後的去尾形狀穩定化,以電弧溶融上述去尾部形成的球形部的組織均一化等。此正圓化效果,在線徑20μm以下的半導體用銅合金接合線的情況下更顯著。
含有Pd 0.13~1.15質量%的濃度範圍,且含有Ti:0.0005~0.01質量%、B:0.0005~0.007質量%、P:0.0005~0.02質量%其中至少1種,上述總計0.0005~0.025質量%的銅合金構成的半導體用銅合金接合線更佳。藉由添加Ti、B、P中至少一種與Pd併用,TCT測試等的熱循環評估中,得到降低楔形接合不良發生的高效果。由於添加Ti、B、P,金屬線大變形時,降低金屬線的加工硬化,提高促進楔形接合的金屬線變形的作用。又,即使由於TCT測試中的熱變形而半導體用銅合金接合線伸縮,也可以期待這些元素對楔形接合的半導體用銅合金接合線中微裂傷等的損傷的制止效果。確認TCT測試中更提高可靠性的效果只有Ti、B、P的元件群的話很小,如果與Pd組合就更提高。詳細的結構雖不明,但認為Pd在Cu中固溶,因為Ti、B、P在Cu中固溶度小而析出、偏析等,藉此,這些元素互補作用,對楔形接合的金屬線變形,可以發揮更優異的效果。在此,關於Ti、B、P的濃度,可能因為下限值未達0.0005質量%的話上述效果變小。又,上限濃度在Ti、B、P單獨分別超過Ti:0.01質量%、B:0.007質量%、P:0.02質量%,或是總計超過0.025質量%時,金屬線強度上升,台形環路的直線性下降,與鄰接的半導體用銅合金接合線的間隔往往變窄。
又,含有Pd 0.13~1.15質量%的濃度範圍,且含有Ti:0.0005~0.01質量%、B:0.0005~0.007質量%、P:0.0005~0.02質量%其中至少1種,以及含有這些中至少1種的Pd、Ti、B、P總計0.0005~0.025質量%,與金屬線長度方向平行的金屬線剖面中的結晶粒的平均尺寸在2μm以上的半導體用銅合金接合線更佳。以上述半導體用銅合金接合線,可以提高楔形接合性,得到更高的效果。認為是為了降低熱變形引起的楔形接合部中的破損發生,上述元素添加作用,加上與結晶粒的粗大化的相互作用,提高改善TCT測試的可靠性的效果。此改善效果在20μm以下的細線情況下更顯著。
本發明的半導體用銅合金接合線,在保存之際塗佈通常的防鏽劑,或密封在N2
(氮)氣體等的非活性氣體中,或是可以實施上述兩者。又,使用本發明的半導體用銅合金接合線之際,除了塗佈上述保存用的防鏽劑之外,即使在金屬線表面不實施特別的塗佈、鍍金,可以就這樣使用(單層金屬線),得到作用效果。
說明有關本發明的半導體用銅合金接合線的製造方法概要。
使用銅純度4N~6N(99.99~99.9999質量%)的高純度銅,溶解(熔解)含有必要濃度添加元件的銅合金而製作。此合金化有直接添加高純度成分的方法、以及利用含有添加元素10%左右的高濃度母合金的方法。利用母合金的方法對於含有低濃度並均一化元素分布有效。本發明的添加成分中,含有Pd 0.5質量%以上的較高濃度時,可以利用高純度的直接添加,為了穩定含有低濃度的Pd、Ag、Au、Ti、B、P等元素,添加母合金的方法是有利的。溶解是在真空中或氮氣或Ar(氬氣)的氣體中,以1100℃以上加熱。之後,在爐中慢慢冷卻,製作鑄塊。為了洗淨鑄塊表面,以酸洗淨及水洗淨,再乾燥。對於銅中的添加元素的濃度分析,ICP(感應耦合電漿)分析等有效。
粗徑以壓延加工,細線以伸線加工變細到最終線徑。壓延製程使用溝型鍛造或型鍛等。伸線製程使用可以裝配複數個鑽石塗佈的小晶片的連續伸線裝置。根據需要,加工的途中階段或最終線徑中實施熱處理。半導體用銅用合金接合線的製造過程中,為了形成與金屬線長度方向平行的金屬線剖面中的結晶粒的平均尺寸2μm以上的金屬組織,最好將加工與熱處理合適化。特別是最好分割熱處理過程為2個以上的過程。例如,伸線加工的途中實施中間燒鈍,再施加伸線並在最終線徑實施加工燒鈍的方法等,對於穩定控制結晶粒的尺寸有效。作為變更結晶粒尺寸的製造條件,調整施行中間燒鈍的線徑,此熱處理條件、此中間燒鈍前後的伸線製程中的加工條件、加工燒鈍的熱處理條件等是有效的。導入加工時的轉位、原子空孔等的格子缺陷,以及熱處理時格子缺陷作為核心,形成再結晶粒等,由於含有Pd 0.13~1.15質量%的範圍,變得比較容易。由於加工與熱處理的條件合適化,利用Cu中固溶的Pd元素與格子缺陷之間的相互作用,控制加工集合組織與再結晶集合組織,對於調整結晶粒尺寸有效。
以下說明關於實施例。
說明具體的製造過程。使用銅純度4N~6N(99.99~99.9999質量%)的高純度銅,添加必要的含有成分,在真空中或氮氣或Ar氣體的環境中,以1100℃以上溶解。之後在爐中慢慢冷卻,製作直徑6~30mm(毫米)的鑄塊。為了洗淨鑄塊表面,以酸洗淨及水洗,再乾燥。有關銅中的微量元素分析,對合金元素的濃度分析使用ICP裝置。
粗徑以壓延加工,細線以伸線加工變細到最終線徑的25μm或18μm。壓延製程使用溝型鍛造,線徑為0.5~1.5mm為止,以10~100m/min(公尺/分)的速度加工。伸線製程使用可以裝配複數個小晶片的連續伸線裝置,以及鑽石塗佈的小晶片,伸線速度以50~400m/min的範圍進行。以小晶片的內壁的清淨化為目的,使用前先作好超音波洗淨。
加工過程中進行2~4回的熱處理。線徑的500~40μm的範圍內進行1~3回的中間熱處理,最終線徑中進行1回最終熱處理。熱處理方法係使用具有10cm(公分)以上均熱帶的紅外線加熱爐,設定在250~800℃的爐中,速度為10~500m/min,掃描張力在2~30mN的範圍內一邊連續移動金屬線一邊施行熱處理。為了抑制金屬線表面的銅氧化,爐內非活性氣體(使用的氣體為純度4N的氮氣)以流量0.5~5L/分的範圍連續流動。作為金屬線表面的氧化銅形成的管理指標,在爐中央部測量氧濃度,調整其值為0.1~6體積%的範圍。對於氧濃度測量,使用市售的電流電池式氧感測器。調整最終線徑中的拉力測試的延長值為4~25%。根據需要,金屬線表面塗佈防鏽劑,保管時繞著半導體用銅合金接合線的線軸以保護袋覆蓋,密封在氮氣環境中。
對於測量金屬線表面的氧化銅的平均厚度,以AUGER(歐傑)分光分析進行深度分析,使用在金屬線表面隨機位置的最少3處以上測量的氧化銅的膜厚平均值。一邊以Ar離子濺鍍,一邊測量深度方向,深度的單位以SiO2
換算表示。氧濃度以30質量%為氧化銅與金屬銅間的邊界。在此的氧濃度,使用相對於銅、氧、金屬元素總計濃度的氧濃度比率。測量中使用SAM-670(PHI社製,FE型),電子束的加速電壓為5kV、測量區域為10nA,以Ar離子濺鍍的加速電壓3kV、濺鍍速度11nm(毫微米)/分,實施測量。氧化銅的平均膜厚的測量結果記載於表1、3的「金屬線表面的氧化銅膜厚」欄位中。
如上所述,製作以下的表1、2中記載的各半導體用銅合金接合線。
半導體用銅合金接合線的連接,使用ASM社製的泛用自動連線接合裝置,進行球形/楔形接合。如果是球形接合,金屬線前端以電弧放電形成球形部,此球形部以超音波併用的熱壓著接合至電極膜。為了抑制半導體用銅合金接合線在溶融時的氧化,金屬線前端以流過非活性氣體的狀態形成球形。非活性氣體中,使用N2
+5%H2
氣體。
接合的對象係矽基板上的電極膜的材料,使用厚度約0.8~3μm的Al(鋁)合金膜(Al-1%Si-0.5%Cu)。又,確認以Al-0.5%Cu也得到大致同樣的結果。楔形接合的對象,使用表面施加鍍銀(厚度:2-4μm)的引導框架。又,即使使用表面形成鍍銀/鍍鎳/銅配線的玻璃環氧樹脂基板,也確認了實施例與比較例之間的差。
關於製作的半導體用銅合金接合線,進行以下的可靠性評估測試。使用的線徑為18μm。壓著球形徑為32μm,接合溫度為175℃,接合對象的材質為Al-0.5%Cu,膜厚為1μm。接合連接試料的樹脂封止中使用的封止樹脂為不含Br(溴)等鹵素的綠色系的泛用封止樹脂。封止樹脂內含有的代表性不純物的鹽分析濃度為3~8質量ppm(百萬分之一)。
PCT測試(壓力鍋測試)係將連接40枝的半導體用銅合金接合線的試料,在飽和型的條件的溫度121℃、相對溼度100%、2大氣壓的高溫高溼環境中,預先加熱200、500小時。之後,評估上述連接的40枝的半導體用銅合金接合線的電氣特性。電阻上升初期的3倍以上的半導體用銅合金接合線的比例在30%以上(相對於40枝中的比例,以下相同)時,由於接合不良,在表1的「PCT可靠性」的欄位內記載×符號。電阻上升初期的3倍以上的半導體用銅合金接合線的比例在5%以上未達30%的範圍時,由於可靠性要求不嚴的IC可以使用,在表1的「PCT可靠性」的欄位內記載△符號。電阻上升3倍以上的半導體用銅合金接合線的比例未達5%,且電阻上升1.5倍以上的半導體用銅合金接合線的比例在5%以上未達30%時,由於沒有實用上的問題,在表1的「PCT可靠性」的欄位內記載○符號。電阻上升1.5倍以上的接合線的比例未達5%時,由於良好,表1的「PCT可靠性」的欄位內記載◎符號。
PCT測試中,加熱200、500小時後,評估100枝的半導體用銅合金接合線的球形接合部的抗切強度。有關PCT測試後的抗切強度平均值對加熱前的初期抗切強度平均值的比率,未達40%時,由於可靠性不良,符號為×,在40%以上未達60%的範圍時,由於可靠性要求不嚴的IC可以使用,符號為△,在60%以上未達80%時,由於沒有實用上的問題,符號為○,80%以上時,由於PCT可靠性良好,分別在表1的「PCT可靠性評估」的200、500小時的「抗切強度」欄位內記載◎符號。
又,有關PCT可靠性的偏離,對於PCT測試後的抗切強度平均值的標準偏差的比例(%),在9%以上時,強度偏離大,由於產生實用化的問題,符號為×,在6%以上未達9%的範圍時,雖然最好改善,但由於可靠性要求不嚴的IC可以使用,符號為△,在4%以上未達6%時,由於沒有實用上的問題,符號為○,0%以上未達4%時,由於PCT可靠性穩定,量產性也優異,分別在表1的「PCT可靠性評估」的200、500小時的「抗切強度」欄位內記載◎符號。
TCT測試使用市售的TCT測試裝置。預先提供連接400枝的半導體用銅合金接合線的試料給經歷過苛溫度條件(-5℃/30分~155℃/30分)的測試,測試後,進行電氣測量400枝的上述連接的半導體用銅合金接合線,評估電氣導通。不良率為零時,由於可靠性高,符號為◎,不良率未達2%的話,判斷在實用上沒有大的問題時,符號為○,不良率為2~5%的範圍的話,符號為△,不良率超過5%的話,由於必須改善,在表2中「TCT可靠性」的欄位內記載×符號。
施行上述可靠性的評估,以及下列的金屬線性能評估測試。
壓著球形部的接合形狀的判定,係觀察接合的球形200枝,評估形狀的正圓性、異常變形不良、尺寸精度等。使用線徑25μm與18μm 2種類的金屬線。從正圓移位的異方性、花瓣狀等不良球形狀6枝以上的話,判定不良,在表2中「球形接合形狀」的欄位內記載×符號。又,從異方性、花瓣狀等不良球形形狀有1~5枝時,分類為2,顯著的偏芯等的異常變形發生1枝以上的話,由於量產上最好改善,符號為△,不發生異常變形的話,由於可以使用,符號為○,不良球形形狀為0枝的話,由於良好,在表2中「球形接合形狀」的欄位內記載◎符號。
球形接合強度的評估中,為了在線徑25μm且球徑50~65μm的範圍,在階段溫度175℃中使用接合試料。進行20枝的球形接合部的抗切測試,測量此抗切強度的平均值,使用球形接合部的面積平均值來計算每單位面積的抗切強度,並使用每單位面積的抗切強度。每單位面積的抗切強度,如果未達70MPa(抗拉強度),由於接合強度不夠,符號為×,如果70MPa以上未達90MPa的範圍,由於藉由若干接合條件的變更可以改善,符號為△,如果是90MPa以上未達110Mpa的範圍的話,判斷為沒有實用上的問題,符號為○,如果是110Mpa以上的範圍的話,由於良好,在表2中「抗切強度」的欄位內記載◎符號。
楔形接合性的評估中,根據剝離不良的低負重、低溫中的連接,進行加速評估。連接溫度為160℃,接合對象使用鍍銀的Cu(銅)引導框架。在此使用線徑25μm與18μm 2種類的半導體用銅合金金屬線。評估2000枝的接合所產生的不著(Non-Stick-On-Lead:NSOL)的發生頻率。不著數在6枝以上時,由於必須改善,符號為×,不著數為3~5枝時,符號為△,不著數為1枝或2枝時,由於大致良好,符號為○,不著數數為0時,判斷為金屬線保管壽命良好,在表2中「楔形接合性」的欄位內顯示◎符號。
關於接合過程中的環路形狀穩定性,金屬線間隔(SPAN)為4mm的長間隔時,以2mm的泛用間隔製作500枝的環路。以投影機觀察環路,評估半導體用銅合金金屬線的環路高度的偏離、金屬線彎曲等。在此使用線徑25μm與18μm 2種類的半導體用銅合金金屬線。金屬線長以長4mm形成台形環狀,為了迴避接觸晶片端,必須控制更嚴的環路。在表2中「環路控制高度穩定性」的欄位內,金屬線長2mm,直線性、環路高度等的不良在5枝以上時,判斷為有問題,符號為×,金屬線長2mm,不良為2~4枝,且金屬線長4mm,不良為5枝以上時,判斷為必須改善,符號為△,金屬線長2mm,不良在1枝以下,且金屬線長4mm,不良為2~4枝時,由於環路形狀較良好,顯示符號為○,金屬線長4mm,不良在1枝以下時,判定環路形狀穩定,以◎符號表示。
為了評估台形環狀的直線性,以金屬線間隔為4mm的長間隔進行接合。線徑為25μm。30枝的半導體用銅合金接合線以投影機在上方觀察,對於連接球形側與楔形側之間的接合部的直線,測量半導體用銅合金接合線最遠離的部位差距作為彎曲量。在表2中「台形環路直線」的欄位內,彎曲量的平均,未達1枝份的線徑的話,判斷為良好,以◎符號表示,2枝份以上的話,由於必須改善,符號為△,在中間的話,由於通常不成問題,顯示符號為○。
表1、2中,有關申請專利範圍第1項所述的半導體用銅合金接合線相當於第1~50實施例,根據申請專利範圍第3項的半導體用銅合金接合線相當於第1~7、11~16、18、20~26、28~33、33~35、37~50實施例,根據申請專利範圍第4項的半導體用銅合金接合線相當於第11~20、36~40實施例,根據申請專利範圍第5項的半導體用銅合金接合線相相於第21~40實施例。又,比較例1~4相當於不滿足申請專利範圍第1項的半導體用銅合金接合線的情況。
第1~50實施例的半導體用銅合金接合線相當於根據申請專利範圍第1項的半導體用銅合金接合線,由於含有Pd 0.13~1.15質量%,確認加熱時間200小時的PCT可靠性良好。另一方面,比較例1~5中,不滿足含有Pd 0.13~1.15質量%的條件,確認即使200小時的短時間加熱,PCT可靠性也下降。第2~5、8~15、17、18、20、22~25、27~31、33~40、42~50實施例的半導體用銅合金接合線,由於含有Pd 0.2~1.1質量%,確認加熱時間500小時的PCT可靠性良好。
第1~7、11~16、18、20~26、28~33、35、37~50實施例的半導體用銅合金接合線相當於根據本發明申請專利範圍第3項的半導體用銅合金接合線,含有Pd 0.13~1.15質量%,與金屬線長度方向平行的金屬線剖面中的結晶粒的平均尺寸在2μm以上,確認環路高度的穩定性、楔形接合性良好。另一方面,第8~10、17、19、27、34、36實施例中,不滿足結晶粒的平均尺寸2μm以上的條件,確認是環路高度的穩定性、楔形接合性可以容許的範圍,但稍稍下降。第1~3、5、6、12~16、18、21~24、28、29、31、32、35、37~40、42~44、46~49實施例的半導體用銅合金接合線由於結晶粒的平均尺寸在3μm以上,確認環路高度的穩定性、楔形接合性更提高。
第11~20、36~40實施例的半導體用銅合金接合線相當於根據本發明申請專利範圍第4項的半導體用銅合金接合線,由於含有Pd 0.13~1.15質量%,Ag、Au中至少1種總計0.0005~0.07質量%,確認線徑25μm的球形接合形狀良好。又,第11~16、18、37~40實施例的銅合金接合線,由於含有Pd 0.13~1.15質量%,Ag、Au中至少1種總計0.0005~0.07質量%,且滿足結晶粒的平均尺寸2μm以上的條件,確認即使是線徑18μm細線的嚴格球形接合形狀的評估也是良好的結果。
第21~40實施例的半導體用銅合金接合線相當於根據本發明申請專利範圍第5項的半導體用銅合金接合線,含有Pd 0.13~1.15質量%的濃度範圍,且含有Ti:0.0005~0.01質量%、B:0.0005~0.007質量%、P:0.0005~0.02質量%其中至少1種,上述總計0.0005~0.025質量%,確認線徑25μm的TCT可靠性良好。又,也滿足結晶粒的平均尺寸2μm以上的條件的第21~26、28~33、35、37~40實施例的半導體用銅合金接合線,確認即使是線徑18μm細線的嚴格球形接合形狀的評估也是良好的結果。
表3顯示管理氧化銅膜厚的各半導體用銅合金接合線的評估結果。使用表1的實施例中製作的試料,管理、變更氧化銅的膜厚。有關試料記載,在試料號碼的末尾附記a係相當於表1的實施例所評估試料,末尾附記b、c、d係依據製造條件的變更變更氧化銅膜厚的試料。為了簡便地控制氧化膜厚,控制最終徑的熱處理過程中的加熱溫度、氮氣的流量、金屬線走間速度、爐內的氧濃度等。根據本發明申請專利範圍第2項的半導體用銅合金接合線相當於表1、2中第1~50實施例、表3中第2a、2c、3a、3b、4a、4b、4c、6a、6b、14a、14b、24a、24b、29a、29b實施例,比較例1a、1b相當於不滿足本發明申請專利範圍第1項的半導體用銅合金接合線的情況。
第2a、2c、3a、3b、4a、4b、4c、6a、6b、14a、14b、24a、24b、29a、29b實施例的半導體用銅合金接合線相當於根據本發明申請專利範圍第2項的半導體用銅合金接合線,由於含有Pd 0.13~1.15質量%的範圍,金屬線表面的氧化銅平均膜厚在0.0005~0.02μm的範圍,確認PCT可靠性的偏離減少而穩定的效果。
Claims (4)
- 一種半導體用銅合金接合線,其特徵在於:含有Pd 0.13~1.15質量%及Ag、Au至少1種,總計0.0005~0.07質量%;Ti(鈦):0.0005~0.01質量%、B(硼):0.0005~0.007質量%、以及P(磷):0.0005~0.02質量%中的至少1種,總計0.0005~0.025質量%;其餘部分為銅及不可避免的不純物構成的銅合金以伸線加工形成。
- 如申請專利範圍第1項所述的半導體用銅合金接合線,其中金屬線表面的氧化銅平均膜厚在0.0005~0.02μm的範圍。
- 如申請專利範圍第1項所述的半導體用銅合金接合線,其中與金屬線長度方向平行並在金屬線剖面中的結晶粒的平均大小為2μm以上且在金屬線線徑的1.5倍以下。
- 如申請專利範圍第2項所述的半導體用銅合金接合線,其中與金屬線長度方向平行並在金屬線剖面中的結晶粒的平均大小為2μm以上且在金屬線線徑的1.5倍以下。
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JP2012074706A (ja) | 2012-04-12 |
KR20120031005A (ko) | 2012-03-29 |
JP5360179B2 (ja) | 2013-12-04 |
US20120094121A1 (en) | 2012-04-19 |
EP2447380B1 (en) | 2015-02-25 |
EP2447380A1 (en) | 2012-05-02 |
US9427830B2 (en) | 2016-08-30 |
SG177358A1 (en) | 2012-02-28 |
TW201107499A (en) | 2011-03-01 |
KR101704839B1 (ko) | 2017-02-08 |
EP2447380A4 (en) | 2012-12-05 |
JP4866490B2 (ja) | 2012-02-01 |
JPWO2010150814A1 (ja) | 2012-12-10 |
CN106119595A (zh) | 2016-11-16 |
JP5246314B2 (ja) | 2013-07-24 |
WO2010150814A1 (ja) | 2010-12-29 |
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