TWI555860B - Welding wire and manufacturing method thereof - Google Patents

Welding wire and manufacturing method thereof Download PDF

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Publication number
TWI555860B
TWI555860B TW102102164A TW102102164A TWI555860B TW I555860 B TWI555860 B TW I555860B TW 102102164 A TW102102164 A TW 102102164A TW 102102164 A TW102102164 A TW 102102164A TW I555860 B TWI555860 B TW I555860B
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TW
Taiwan
Prior art keywords
wire
core material
welding
copper
palladium
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TW102102164A
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English (en)
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TW201350595A (zh
Inventor
Ryo Togashi
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Nippon Micrometal Corp
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0227Rods, wires
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21CMANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C1/00Manufacture of metal sheets, metal wire, metal rods, metal tubes by drawing
    • B21C1/02Drawing metal wire or like flexible metallic material by drawing machines or apparatus in which the drawing action is effected by drums
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21CMANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/04Manufacture 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
    • B21C37/042Manufacture of coated wire or bars
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21CMANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C9/00Cooling, heating or lubricating drawing material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/30Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/302Cu as the principal constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/40Making wire or rods for soldering or welding
    • B23K35/404Coated rods; Coated electrodes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/01Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/018Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of a noble metal or a noble metal alloy
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08Changing 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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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/04Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
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Description

焊接用線材及其製造方法
本發明係有關於焊接用線材及其製造方法,尤其係有關於具有以銅為主成分之芯材、與鈀被覆層或鈀及金之被覆層的焊接用線材及其製造方法。
自以往,已知以鈀被覆以銅為主成分之芯材的鈀被覆銅焊接用線材(例如,參照專利文獻1)。
在市面上所使用之鈀被覆銅焊接用線材係都是對半導體元件上之鋁接線座將在氮氣環境氣體中藉電漿電弧加熱而熔化凝固所形成的球進行超音波熱壓接所接合。在氮氣環境氣體中形成球的情況,下工夫在銅芯材添加成為脫氧劑的磷,防止在形成球時銅露出之情況的氧化,並維持球之表面的表面張力,將熔化球維持成正球形至凝固。
累積這種工夫的結果,在最近,應用於鈀被覆銅線之封裝變得多種,亦使用於如要求高可靠性之封裝的事例逐漸增加。
【先行專利文獻】 【專利文獻】
[專利文獻1]日本專利4158928號公報
可是,在使用鈀被覆銅焊接用線材之QFN(Quad Flat No-lead)或BGA(Plastic Ball Grid Array),因為樹脂密封係僅基板上的一側,所以耐濕性差,在壓力鍋測試(Pressure Cooker Test,以下稱為「PCT」)或超加速高温高濕測試(Highly Accelerated Temperature and Humidity Stress Test,以下稱為「HAST」)等之在提高濕度與壓力下所進行之水分易侵入封裝內之條件下的可靠性測試,觀察到壽命變成比裸銅線更短之現象。本發明者們等之調查的結果,得知在球接合部銅露出的情況,鋁接線座之球接合界面的腐蝕顯著,因鋁氧化而成為導電不良。在裸銅線的情況,得知因為在形成球時之氣體環境氣體係含有4~5Vol%之氫的氮氣環境氣體比氮氣環境氣體中更避免球之表面的氧化,所以在PCT或HAST可靠性之易受到水分或氧氣的影響之評估的可靠性變高,而在鈀被覆銅線,得知反而可靠性降低。
本發明者們進一步調查時,得知在含有4~5Vol%之氫的氮氣中,在鈀被覆銅線藉電漿電弧放電形成球時,觀察到在球的表面銅露出、或尖端不會充分熔化而無法得到既定尺寸之球徑的小球不良、或在球的表面觀察到如桃子果實之凹下等球之外觀異常。
推測在氮氣中含有4~5Vol%之氫的混合氣體環境氣體中,以電漿電弧對線尖端加熱的情況和未含氫氣之100%氮氮相比,因為電漿溫度成為高温,所以鈀之熔點因與銅之合金化而降低時,發生鈀膜熔化並熔入銅球內部、或一部分之鈀 膜熔化而在球的表面銅露出、或在球的表面產生段差等之球的外觀不良,而接合性變差,或因銅之電流腐蝕而HAST可靠性降低。
又,認為該鈀膜之對球內部的熔入係因為熔化時間長而在鈀膜之熔化大上亦是原因之一。認為該鈀膜的熔化係形成球後球迅速地被冷卻,藉由維持焊接用線材之原本的構造而可防止。
因此,本發明之目的在於提供焊接用線材及其製造方法,該焊接用線材係抑制形成球時鈀膜的熔化,提高以鈀被覆銅焊接用線材形成球之形狀的真球度,而可抑制在含有4~5Vol%之氫的氮氣中的放電所形成球表面的銅露出,在濕度所影響之HAST可靠性良好。
為了達成該目的,本發明之一實施形態的焊接用線材係具有以銅為主成分之芯材、與鈀被覆層或鈀及金之被覆層的焊接用線材,其特徵在於:在該芯材的中心具有銅在軸向所延伸之纖維狀組織。
該本發明之焊接用線材之製造方法的特徵為具有以下的步驟:芯材產生步驟,係藉連續鑄造,產生該芯材;第1拉線步驟,係至使該芯材減面至既定減面率,使用減面率10%以下的模具進行拉線加工,減面至該既定減面率後,使用減面率大於10%的模具進行拉線加工;電鍍步驟,係在藉該第1拉線步驟拉線加工後之該芯材的周圍電鍍,而形成被覆銅線;及第2拉線步驟,係對該被覆銅線進行拉線加工至成為既定線徑。
又,在該第1拉線步驟與該電鍍步驟之間更具有軟化熱處理步驟,該軟化熱處理步驟係對藉該第1拉線步驟拉線加工後之該芯材在再結晶開始溫度以上且再結晶終了溫度以下的溫度進行軟化熱處理較佳。
在此,該既定減面率係95.0~99.5%較佳。
此外,亦可該第1拉線步驟係將一個模具配置於供給該芯材的供給絞盤與捲繞該芯材的捲繞絞盤之間,藉由使用一個模具重複進行拉抽的拉線加工來進行。
若依據本發明,在焊線時,可適當地維持焊接用線材的構造、形狀。
9‧‧‧銅板
10‧‧‧芯材
11‧‧‧纖維狀組織
12‧‧‧再結晶區域
13‧‧‧鈀膜
14‧‧‧被覆銅線
15‧‧‧焊接用線材
20‧‧‧連續鑄造裝置
21‧‧‧室
22‧‧‧漏斗
23‧‧‧鑄模
24‧‧‧水套
25‧‧‧輥
30~35‧‧‧絞盤
40~45、90~97‧‧‧模具
50‧‧‧加熱器
60、61‧‧‧導輥
70、71、72‧‧‧捲軸
80‧‧‧前處理槽
81‧‧‧電鍍槽
第1圖係表示本發明之第1實施形態的焊接用線材之一例的剖面構成圖。
第2圖係表示比較例之焊接用線材的剖面構成圖。
第3圖係表示本發明之實施形態的焊接用線材之製造方法的芯材產生步驟之一例的圖。第3(A)圖係表示芯材產生步驟所使用之材料之一例的圖。第3(B)圖係表示連續鑄造之一例的圖。第3(C)圖係表示藉芯材產生步驟所產生之芯材之一例的圖。
第4圖係表示本發明之實施形態的焊接用線材之製造方法的鑄造後拉線步驟之一例的圖。
第5圖係表示本發明之實施形態的焊接用線材之製造方法 的粗拉線步驟之一例的圖。
第6圖係表示本發明之實施形態的焊接用線材之製造方法的軟化熱處理步驟之一例的圖。
第7圖係表示已拉線加工之金屬線之對加熱的斷裂強度與伸長率的變化、再結晶開始溫度及再結晶終了溫度的圖。
第8圖係表示本發明之實施形態的焊接用線材之製造方法的電鍍步驟之一例的圖。
第9圖係表示本實施形態的焊接用線材之製造方法的最終拉線步驟之一例的圖。
第10圖係用以說明本發明之第1~11實施例及第1~11比較例的焊接用線材之在焊線時的球截面之鈀濃度變換結果之評估方法的圖。第10(A)圖係表示使用良品之焊接用線材的球截面之鈀濃度變換結果之一例的圖。第10(B)圖係表示使用良品之焊接用線材的球截面之鈀濃度變換結果之其他的例子的圖。第10(C)圖係表示使用不良品之焊接用線材的球截面之鈀濃度變換結果之一例的圖。第10(D)圖係表示使用不良品之焊接用線材的球截面之鈀濃度變換結果之其他的例子的圖。
以下,參照圖面,說明本發明之實施形態。
第1圖係表示本發明之第1實施形態的焊接用線材之一例的剖面構成圖。在第1圖,本實施形態之焊接用線材15具有芯材10與鈀膜13。芯材10係以銅為主成分所構成,在組織構造上,具有纖維狀組織11與再結晶區域12。鈀膜13係被覆芯材10的金屬膜。即,本實施形態之焊接用線材15係 在以銅為主成分之芯材10的周圍具有以鈀膜13所被覆之構造的鈀被覆銅焊接用線材。
本實施形態之焊接用線材15之製造方法的細節將後述,本實施形態之焊接用線材15係對在純度99.99%以上之銅,熔解添加元素並進行熔解鑄造所得之銅鑄錠,使其通過模具而進行拉抽之拉線加工時,藉由使纖維狀組織11殘留所得到。在拉線加工後,因應於需要進行軟化熱處理,作成既定線徑後,實施各種的化學洗淨,使銅組織在線材表面露出後,實施鈀電鍍,因應於需要再鍍金。然後,再進行拉線加工,縮徑至既定線徑後,進行軟化熱處理。在那時,調整軟化溫度,可得到纖維狀組織11形成於芯材中心之鈀被覆銅焊接用線材。
在此,纖維狀組織11係鑄造時之結晶在拉線方向伸長,即使以後被加熱,再結晶化或結晶粒之粗大化亦不顯著,意指殘留成纖維狀的金屬組織。在剖面觀察,如第1圖所示,相對線表面附近之結晶再結晶化,而成為粒狀的再結晶區域12,易觀察到中心部分係作為在線長度方向所伸長之纖維狀組織11。進行硬度測量時,因為觀察到纖維狀組織11之硬度比再結晶粒高,所以根據硬度測量,亦可確認纖維狀組織11的存在。
纖維狀組織係芯材中存在0.5~90質量%較佳,尤其存在1~80質量%更佳,存在4~50質量%最佳。
又,纖維狀組織係在將芯材之半徑設為R時,存在於距中心0.8R以內較佳,存在於0.5R以內最佳。
該纖維狀組織11殘留於中心的焊接用線材15係 在焊接時形成球時,以纖維狀組織11吸收熱能,使球迅速地冷卻,而可抑制鈀膜13之熔解。即,因為纖維狀組織11係未再結晶化的粗組織,所以藉由施加熱能,發生再結晶化,可消耗所施加的熱能。藉此,在形成球時之球熔解時或凝固時,促進熔解溫度的降低或凝固時間的縮短,而可抑制鈀膜的熔解所造成之對球內部的熔入。
依此方式,在本實施形態的焊接用線材15,藉由使纖維狀組織11殘留於芯材10的內部,迅速吸收在焊線時所產生之球的熱,而可良好地進行焊線。
第2圖係表示比較例之焊接用線材的剖面構成圖。比較例之焊接用線材115係芯材110全部由再結晶區域12所構成,而成為纖維狀組織11完全未殘留的構造。在該構成,在形成球時,因為消耗球熔解之熱能的區域不存在,所以鈀膜113係熔解後,對球內部熔入,而芯材110之銅露出的可能性變高。
另一方面,因為本實施形態的焊接用線材15能以纖維狀組織11消耗熱能,所以防止鈀膜13對球內部熔入,因為可抑制銅之露出,所以防止表面之氧化,而可提高以後之連接可靠性。
其次,使用第3圖~第9圖,說明本發明之實施形態之焊接用線材的製造方法。
第3圖係表示本發明之實施形態的焊接用線材之製造方法的芯材產生步驟之一例的圖。第3(A)圖係表示芯材產生步驟所使用之材料之一例的圖,第3(B)圖係表示連續鑄造之 一例的圖,第3(C)圖係表示藉芯材產生步驟所產生之芯材之一例的圖。
如第3(A)圖所示,在金屬產生步驟,例如,以板狀的銅板9供給成為芯材10之材料的銅。此外,在需要添加物的情況,亦一樣地準備添加物的金屬板。
如第3(B)圖所示,芯材10的產生係使用連續鑄造裝置20進行。連續鑄造裝置20包含室21、漏斗22、鑄模23、水套24及輥25。在連續鑄造裝置,在被收容於室21內的漏斗22內將銅板9熔解後,使所熔解之銅板9通過具有水套24的鑄模23,再藉輥25拉出,而產生芯材10。此外,室21內係例如亦可以氮氣充滿。又,除了銅板9以外,亦可添加物亦在漏斗22內熔解後供給。此外,亦可因應於需要,設置用以供給在漏斗22內所熔解之銅板9的澆桶、或具有複數種功用之輥25。
第3(C)圖表示藉連續鑄造所產生之芯材10的一例,剛鑄造後的芯材10具有遠比最終之焊接用線材15粗的線徑,例如具有數mm的線徑。
第4圖係表示本發明之實施形態的焊接用線材之製造方法的鑄造後拉線步驟之一例的圖。在鑄造後拉線步驟,進行芯材10的拉線加工,而芯材10減面(縮徑)。如第4圖所示,在鑄造後拉線步驟,使用一對絞盤30、31與一個模具40,進行芯材10的拉線。芯材10具有數mm的粗細,因為使其插穿模具40所需的力亦大,所以僅將一個模具40設置於絞盤30、31之間,供給充分的力,進行拉線加工。鑄造後拉線步驟 係重複複數次,進行將芯材10作成既定線徑。例如,在鑄造後拉線步驟,亦可芯材10係作成約1mm的線徑。
可是,在對剛鑄造後之芯材10進行拉線加工的鑄造後拉線步驟,最初以大的減面率進行縮徑時,在第1圖所說明之纖維狀組織11不會殘留,而金屬組織可能會被拉斷。
因此,在本實施形態之焊接用線材的製造方法,至芯材10的累積減面率達到既定減面率為止,以減面率10%以下進行拉線加工。在此,減面率係以數學式(1)表示。此外,減面率亦可稱為縮徑率,亦可稱為減縮率。
以減面率10%以下持續進行拉線加工之既定減面率係設定成纖維狀組織11殘留於芯材10之中心的適當值這係95.0~99.5%較佳,96%最佳。在最初之剛鑄造後之芯材10的直徑為8mm的情況,減面至直徑1.6mm時,符合96%。例如,在使以銅為主成分之芯材10從8mm減面至1.6mm的情況,纖維狀組織11殘留,這已藉本發明者們的實驗所確認。此外,關於這一點的實施例將後述。
第5圖係表示本發明之實施形態的焊接用線材之製造方法的粗拉線步驟之一例的圖。在粗拉線步驟,使用一對絞盤32、33與複數個模具41~45,進行拉線加工。在粗拉線步驟,因為芯材10的直徑比鑄造後拉線步驟的更細,所以拉抽所需的力亦比鑄造後拉線步驟的小,使用複數個模具 41~45,可高效率地進行拉線加工。藉該粗拉線步驟,芯材10被加工成數100μm位準的芯材10。此外,亦可因應於需要,設置粗拉線步驟。
第6圖係表示本發明之實施形態的焊接用線材之製造方法的軟化熱處理步驟之一例的圖。在軟化熱處理步驟,使用導輥60、61,使芯材10通過圓筒形的加熱器50。藉此,進行芯材10的熱處理,使芯材10軟化,而調整成在焊線時不會損害接線座等之硬度。此外,已進行軟化熱處理的芯材10係捲繞於捲軸70。
在此,在本實施形態之焊接用線材的製造方法,在再結晶開始溫度以上至再結晶終了溫度以下的溫度進行軟化熱處理步驟。
第7圖係表示已拉線加工之金屬線之對加熱的斷裂強度與伸長率的變化、再結晶開始溫度及再結晶終了溫度的圖。
在第7圖,橫軸表示溫度,縱軸表示金屬線之斷裂強度與伸長率,一般對鑄造之狀態下之銅的芯材10進行拉線加工時,隨著加工度,斷裂強度上升,又伸長率降低,並逐漸變成飽和,但是對其加熱時,有伸長率急速上升之溫度,將其稱為再結晶開始溫度(第7(A)圖)。又,將伸長率成為最大的溫度稱為再結晶終了溫度(第7(B)圖)。在再結晶終了溫度以上的溫度加熱時,一般結晶係整體變成粗大,作為焊接用材料,可得到充分軟化之狀態。在本實施形態之焊接用線材的製造方法,藉由將加熱溫度設為再結晶開始溫度以上,使芯材10產 生再結晶,並藉由將加熱溫度設為再結晶終了溫度以下,在全直徑不會產生再結晶化。藉此,進行芯材10的軟化,在全直徑不會產生再結晶化,並使一部分殘留為纖維狀組織11。
如第6圖所示,因為加熱器50係從芯材10的外周面進行加熱,所以芯材10的外側再結晶化,成為再結晶區域12,軸附近的中心不會再結晶化,成為纖維狀組織11殘留的構造,得知與第1圖的構造一致。
依此方式,在本實施形態之焊接用線材的製造方法,藉由在再結晶開始溫度以上至再結晶終了溫度以下的溫度進行軟化熱處理步驟,可作成使芯材10軟化,同時使纖維狀組織11殘留於中心的構造。
此外,軟化熱處理步驟係在芯材10之硬度無問題的情況不必進行,亦可作成因應於需要進行。
第8圖係表示本發明之實施形態的焊接用線材之製造方法的電鍍步驟之一例的圖。如第8圖所示,在電鍍步驟,捲出捲軸70所捲繞之芯材10並供給至前處理槽80、電鍍槽81,藉電鍍將鈀膜13形成於芯材10的周圍。又,電鍍後之鈀被覆銅線14係被捲繞於設置於出口側的捲軸71。又,亦可因應於需要,將金層電鍍槽鈀被覆層上。金層之電鍍步驟亦與鈀電鍍一樣,準備與第8圖類似的電鍍設備,或亦可接著鈀電鍍,繼續進行連續電鍍。
此外,電鍍前處理步驟係具有複數個處理步驟,前處理槽80係未必是一個,在第8圖,由於紙面上的緣故,在模式上表示一個前處理槽80。
電鍍前處理步驟係具有:脫脂步驟,係除去芯材10之油脂;鹽酸洗淨步驟,係除去芯材10之表面的氧化膜;化學研磨步驟,係薄薄地溶化芯材10的表面後研磨;及硫酸洗淨步驟,係以硫酸洗淨芯材10。經由該前處理步驟,除去芯材10之周圍的雜質等,而洗淨芯材10的表面,成為易於進行電鍍步驟之狀態。
鈀電鍍步驟係對以銅為主成分之芯材10的周圍實施鈀電鍍,而形成鈀膜13的步驟。電鍍步驟係只要將鈀膜13形成於芯材10的周圍,可進行各種的電鍍處理,例如亦可包含薄膜電鍍步驟與正式電鍍步驟之2個步驟。觸擊電鍍步驟及正式電鍍步驟係電鍍,陽極設置於電鍍槽81內,芯材10係藉供電輥(未圖示)等被陰極通電。而且,將被陰極通電之芯材10浸泡於包含鈀離子Pd2+的鈀電鍍液,而將陽離子之鈀離子Pd2+電沈積於芯材10,實施電鍍。
在觸擊電鍍步驟,在短時間以高電流密度通電,例如以10A/dm2以上的電流密度通電。另一方面,使電流密度比觸擊電鍍更降低,例如以約3~5A/dm2長時間電鍍。依此方式,例如經由觸擊電鍍步驟與正式電鍍步驟之2步驟對銅之芯材10進行鈀電鍍,而將鈀膜13形成於芯材10的周圍。又,電鍍完成之鈀被覆銅線14係捲繞於捲軸71。
鍍金步驟係因應於需要在該鈀電鍍之後實施。亦可與鈀電鍍一樣地藉電鍍進行。
第9圖係表示本實施形態的焊接用線材之製造方法的最終拉線步驟之一例的圖。在最終拉線步驟,進行鈀被覆 銅線或金-鈀被覆銅線14之拉線加工,縮徑成既定線徑。此外,在最終拉線步驟,進行拉線加工至與最終製品相同的線徑。
如第9圖所示,最終拉線步驟亦以捲繞於2個絞盤34、35的方式供給被捲繞於捲軸71的被覆銅線14,在2個絞盤34、35之間,被覆銅線14依序通過複數個模具90~97,藉此,進行拉線加工。在第9圖,設置8個模具90~97。一般,因為最終拉線步驟係將被覆銅線14拉線至最終製品直徑,而作成最終製品之焊接用線材15的最終拉線步驟,所以設置比至目前為止之拉線步驟更多的模具90~97。藉此,能以大的減面率進行縮徑。
依此方式,若依據本發明之實施形態之焊接用線材的製造方法,可製造在芯材10之中心具有纖維狀組織11的焊接用線材15。
實施例
其次,在與比較例比較下說明本發明之實施例之焊接用線材及其製造方法。
第1表表示本發明之第1~11實施例之焊接用線材及其製造方法與第1~11比較例之焊接用線材及其製造方法的實施內容。
如第1表所示,至芯材整體之縮徑率(減面率)為96%,第1~11實施例之焊接用線材及其製造方法係將各模具的縮徑率設定成7%或10%。又,在芯材整體的縮徑率為96~99.9%之範圍,將各模具的縮徑率設定成12%或10%。
另一方面,在第1~11比較例,至芯材整體之縮徑率為96%,將各模具的縮徑率設定成18%或12%。又,在芯材整體的縮徑率為96~99.9%之範圍,將各模具的縮徑率設定成12%或10%。即,第1~11實施例與第1~11比較例係將至芯材整體之縮徑率為96%之各模具的縮徑率設定成相異。
又,在第1~11實施例與第1~11比較例,作為成為芯材的銅原料,使用對市面上之4N純度的無氧銅或4N電性銅再進行電解精製之6N純度的電性銅。磷係使用市面上之15%磷銅底金。熱處理1(軟化熱處理)係在線徑約1mm,在氮氣環境氣體中以再結晶開始溫度以上再結晶終了溫度以下的 溫度進行60分鐘。此外,軟化熱處理係有實施的情況與不實施的情況,在第1表,以「實施」表示實施的情況,以「不實施」表示不實施的情況。在電鍍後,以既定加工縮徑率拉線至最終線徑,在氮氣環境氣體中退火成使伸長率成為焊線用途為主之9~10.5%、與成為突起(bump)線為主之4~4.5%。
第10圖係用以說明本發明之第1~11實施例及第1~11比較例的焊接用線材之在焊線時的球截面之鈀濃度變換結果之評估方法的圖。第10(A)圖係表示使用良品之焊接用線材的球截面之鈀濃度變換結果之一例的圖,第10(B)圖係表示使用良品之焊接用線材的球截面之鈀濃度變換結果之其他的例子的圖。第10(C)圖係表示使用不良品之焊接用線材的球截面之鈀濃度變換結果之一例的圖,第10(D)圖係表示使用不良品之焊接用線材的球截面之鈀濃度變換結果之其他的例子的圖。
在第10圖之實施例,具體而言,關於鈀之球表面分布,在氮氣環境氣體中或含有4~5Vol%之氫的氮氣環境氣體中形成具有線徑之1.6倍之直徑的球,以離子抛光機形成球截面後,藉EPMA分析變換鈀濃度後表示。此外,在第10圖,以白或灰所表示之處是鈀所分布之處。
在第10(A)圖,因為鈀膜分布於球的表面,所以是芯材10之銅不會露出,而與鋁端子不接觸。因此,是OK。以OK1表達這種情況。
在第10(B)圖,鈀稍微擴散至球的內部,但是鈀亦殘留於球的表面。因此,位於OK之範圍。以OK2表達這種情 況。
在第10(C)圖,鈀存在於球的根部,但是從正中央至尖端部分,鈀幾乎不存在。因此,可認為銅露出,係NG。
在第10(D)圖,鈀已擴散至球的內部。又,鈀幾乎未殘留於球的表面。因此,可認為銅露出,係NG。
第2表表示本發明之第1~11實施例之焊接用線材及其製造方法與第1~11比較例之焊接用線材及其製造方法的實施結果。
如第2表所示,在100%氮氣環境氣體下,第1~11實施例及第1~11比較例之雙方都鈀分布是OK1或是OK2,但是在混入氫氣之氮氣環境氣體下,鈀分布係在第1~11實施例是OK1或是OK2,但是在第1~11比較例成為NG。
又,關於球外觀,將在50個球的表面未觀察到銅露出、凹下、變尖之不良的情況評估為OK(良品),在只要觀察到一個的情況評估為NG(不良品),在第1~11實施例全部OK,而在第1~11比較例成為全部NG的評估。
若依據第1~11實施例,在氮氣含有4~5Vol%之混合氣體環境氣體中,以電流值50mA以上的電漿電弧對線尖端加熱,對形成於線尖端之熔融球的截面以EPMA變換鈀分布後觀察的情況,顯示在球表面附近之幾乎整個區域鈀濃縮。
依此方式,若依據本實施形態及本實施例之焊接用線材的製造方法,在鈀被覆銅焊接用線材,在焊線時可防止銅露出。
以上,詳細說明了本發明之較佳實施形態及實施例,但是本發明係未限制為上述之實施形態及實施例,可在不超出本發明之範圍下對上述之實施形態及實施例實施各種變形及替換。
【工業上的可應用性】
本發明係可利用於半導體組裝之焊線。
10‧‧‧芯材
11‧‧‧纖維狀組織
12‧‧‧再結晶區域
13‧‧‧鈀膜
15‧‧‧焊接用線材

Claims (6)

  1. 一種焊接用線材,其具有以銅為主成分之芯材與鈀被覆層,其特徵在於:在該芯材的中心具有銅在軸向所延伸之纖維狀組織;並且該芯材在該纖維狀組織的周圍具有結晶經再結晶化而成的粒狀再結晶區域。
  2. 如申請專利範圍第1項之焊接用線材,其中在鈀被覆層上更具有金被覆層。
  3. 一種焊接用線材之製造方法,製造如申請專利範圍第1或2項之焊接用線材,其特徵在於具有以下的步驟:芯材產生步驟,係藉連續鑄造,產生該芯材;第1拉線步驟,係至使該芯材減面至既定減面率,使用減面率10%以下的模具進行拉線加工,減面至該既定減面率後,使用減面率大於10%的模具進行拉線加工;電鍍步驟,係在藉該第1拉線步驟拉線加工後之該芯材的周圍電鍍,而形成被覆銅線;及第2拉線步驟,係對該被覆銅線進行拉線加工至成為既定線徑。
  4. 如申請專利範圍第3項之焊接用線材的製造方法,其中在該第1拉線步驟與該電鍍步驟之間更具有軟化熱處理步驟,該軟化熱處理步驟係對藉該第1拉線步驟拉線加工後 之該芯材在再結晶開始溫度以上且再結晶終了溫度以下的溫度進行軟化熱處理。
  5. 如申請專利範圍第3項之焊接用線材的製造方法,其中該既定減面率係95.0~99.5%。
  6. 如申請專利範圍第3至5項中任一項之焊接用線材的製造方法,其中該第1拉線步驟係將一個模具配置於供給該芯材的供給絞盤與捲繞該芯材的捲繞絞盤之間,藉由使用一個模具重複進行拉抽的拉線加工來進行。
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