201237191 六、發明說明： 【發明所屬之技術領域】 本發明是關於一種用以連接半導體的積體電路元件上 的電極（腳位：pad)與連接於電路配線基板的電極（外部導 線）所使用的半導體元件的打線接合用的金（Au)合金接合 線，更具體而言，是關於一種抑制微量元素的表面偏析的 直徑20μιη以下的被伸長線加工的金（Au)合金接合線》 【先前技術】 習知，作爲使用於半導體裝置的半導體晶片上的腳位 與連接外部導線的線徑2 5〜3 5 μιη程度的線，大都使用純 度99.99質量％以上的高純度金所成的金（Au)合金接合線 〇 通常，在連接金（Au)合金接合線的方法中，在第一接 合主要使用著超音波併用熱壓接接合法。 在此方法，利用微小放電進行加熱熔融由毛細管前端 所露出的線前端，又利用表面張力形成球形之後，將球部 予以壓接接合（球形接合）於在150.〜3 00°C的範圍內經加熱 的半導體元件的電極上，在之後的第二接合，將接合線利 用超音波壓接直接接合（楔形接合）於外部導線側。 爲了使用作爲電晶體或1C等的半導體裝置，在上述 接合線所致的接合之後，以保護半導體晶片，接合線，及 安裝有半導體晶片的部分之導線架等的目的，使用環氧樹 脂進行封閉。 -5- 201237191 最近，要求提昇半導體裝置的小型化，薄型化，高功 能化及高信賴性化之中，金接合線所必須的特性也成爲各 式各樣，而爲了對應於半導體晶片之多針腳化及隨著此之 狹窄間距化，即使更細線化金接合線，也被要求所需要的 強度，或是提昇第一接合的壓接球的圓度或第二接合的接 合信賴性等，甚至於接合的長期信賴性。 尤其是，隨著半導體裝置的一層的小型化，薄型化及 高功能化，使得半導體裝置的大小變小。隨著此，每一單 位面積的輸出入端子數會增大，而墊片間距（墊片中心間 距離）的大小也從ΙΟΟμιη減小至80μιη，60μηι。因此，接合 線線徑也從25μιη開始變細至20μιη以下，在一部分也嘗 試作1 5μιη以下之線徑。 然而，若接合線的線徑變細，則使得線本身的絕對性 的剛性降低而且熔融球的直徑也變小之故，因而會發生如 在25μιη線徑不會成爲問題的傾向（leaning)或壓接球的接 合強度不足，接合的長期信賴性不足等的不方便。在此， 「傾向」是指張掛第一接合與第二接合之間的線朝左右傾 倒的現象，其結果，會產生鄰接的線彼此間間隔變狹窄， 或會接觸的不方便。 於是，如例示於專利文獻1地，揭示著對於相對應於 高密度化的50μιη的狹窄而針對於線徑爲20μιη接合線， 提昇利用含有Ρ化合物，氫氧化物的環境調和封閉樹脂所 封閉的接合信賴性之故，因而由Cu，Pd，Pt，Zn，Ag(第 一元素群）所選擇的至少一種以上的元素的總計濃度（Cl)爲 -6- 201237191 0.005 〜1 .5 質量 ％的範圍，由 Ca，Ce，Eu，Dy，Y(第二 元素群）所選擇的至少一種以上的元素的總計濃度（C2)爲 0.001 〜0.06 質量 ％ 的範圍，由 La，Mg，Gd，Tb，Ni(第 3 元素群）所選擇的至少一種以上的元素的總計濃度（C3)爲 0.001〜0.05質量％，剩餘部分爲金及不可避的不純物所成 的金合金接合線（段落026)。 然而，將微量元素予以添加於金（Au)合金線時，與金 (Au)合金線相比較，若將微量元素作成愈高濃度，則金 (Au)合金線的絕對性剛性愈高，會提昇各種性能，另一方 面，也有出現不希望的性能的情形。 將具提昇環路形成性之傾向的微量元素予以添加於金 (Au)合金基質時，則有金（Au)球的形成性會變壞，或楔形 接合性變壞的情形。又，含有於金（Au)合金基質的添加元 素析出於熔融球表面的線表面而會氧化，或是稱爲氣孔的 凹處發生於球前端。若添加元素析出或氧化於線表面，則 在半導體裝置上的墊片進行球形接合[金（Au)與鋁（A1)之接 合]之際，或是在外部導線進行楔形接合[金（Au)與銀（Ag) 之接合等]之際’成爲無法金屬性地接合而產生接合不良 的原因。又，在熔融球產生氣孔之狀態下若仍然於半導體 裝置上的墊片進行球形接合，則在稱爲中間遺漏的壓接部 之中央產生無法金屬性地接合的領域，也會發生全體性地 降低接合強度的現象。 又，因壓接球的形狀成爲變形，使得狹窄間距間隔的 球形接合變成困難等的問題，或是球的硬度上昇，因此有 201237191 晶片裂開，或墊片損傷（墊片從底層剝落，或是將稱爲A1 濺射的A1趕出至墊片外而減少膜厚等的不方便）的發生比 率有上昇的問題，而無法多量地添加微量元素。 例如，單獨添加鈣（Ca)而欲確保強度時，則鈣（Ca)是 會局部性地被析出於極細線之表面，該表面析出的鈣（Ca) 被氧化而形成表面氧化膜之結果，因第一接合的球形狀或 接合性不穩定，因此有將壓接球的圓度變壞，或將第二接 合的楔形接合性變壞的情形。 又’若所添加的元素多種類成爲複雜，則在金（Au)合 金中此些元素複雜地發揮功能而被析出於熔融球之表面之 故，因而無法得到良好的初期接合，會加強無法得到高信 賴性的第一接合與第二接合的接合性的趨勢。所以，如專 利文獻2所述地，開發了調整合金元素的種類與添加量而 即使在大氣中進行球形接合，也不會在其熔融球或極細線 之表面形成氧化膜，接合性良好，金屬間化合物生成的趨 勢也經時性地低的接合線。 專利文獻1 :日本特開2003- 1 33362公報 專利文獻2 : W02006-3 5 803公報 【發明內容】 然而，若線徑成爲20μιη以下的細線，則比線徑爲 23μιη的細線還必須將線的機械性強度更提昇30%以上， 惟若提昇機械性強度，則一般線的屈曲性變低。所以，即 使使用機械性強度高的線而自第一接合描繪環路至第二接 201237191 合時’則於第一接合的壓接球的根兒也容易發生龜裂，而 發生成爲所謂頸損傷或頸破斷之原因的問題。 此爲’如專利文獻1的段落0033〜0034所述地，藉 由在將Ca等的第二元素，La等的第三元素添加所定量於 含有IE (Pd)等的第一元素群的金合金的接合線被改善的提 昇接合性或球形狀的圓度也無法解決。 鈣（C a)或鈹（Be)或稀土類元素是添加微量，則與鋅 (Zn)等相比較，爲不會過度析出於熔融球表面的元素。 但是’若在大氣中連續進行球形接合好幾十萬次，則 於毛細管表面或前端部積蓄著析出物或其氧化物之故，因 而將第一接合或第二接合的壓接形狀變壞而產生接合強度 不足或未到等的不方便，或是使得毛細管表面或前端部的 光滑性變壞之故，因而於第一接合後的形成環路時有應力 施加於壓接球的根兒，而容易發生龜裂。又，若毛細管的 光滑性變壞，則除了傾向以外，還有環路高度異常或S形 彎曲等的環路形成性的惡化，又，也成爲以作爲其結果的 環氧樹脂封閉時的線流動之原因。此些是隨著最近的半導 體裝置的小型化，高密度化，發展成鄰接於至今以上的線 彼此間的間隔變狹窄，或會接觸的不方便的主要原因。又 ，提昇接合機的性能，而且也增加接合速度（每一單位時 間的接合數），惟若增加接合速度，則也增加毛細管表面 的光滑性的惡化（增加滑動阻力），惟若增加接合速度，則 毛細管表面或前頭部的光滑惡化（增加滑動阻力）所產生的 影響是更顯著地出現。 -9 _ 201237191 本發明是提供一種即使線徑爲20μιη以下的細線，在 金（Au)_鈀（Pd)等的金（Au)合金基質中也不會偏析有微量元 素而均勻地分佈，又，即使有微量之析出物，藉由光滑地 保持毛細管表面或前端部，也不會增加滑動阻力，又不會 產生頸損傷或形成環路時的不方便等的接合線作爲課題。 此些課題是也符合在全微量元素的添加量爲lOOppm 以下的情形。 本發明人等重複專心硏究須解決上述課題之結果，終 於完成本發明。 亦即，依照本發明，提供表示於以下的金（Au)合金接 合線。 (1) 一種金（Au)合金接合線，其特徵爲：在將99.9質量 %以上的高純度的鈀（Pd)，白金（Pt)及銅（Cu)中至少一種以 合計含有0.05〜2質量％於99.999質量％以上的高純度金 (Au)的金（Au)合金基質中含有微量元素的合金所成的直徑 2 0μιη以下的被伸長線加工的球形接合用的極細線，該微量 兀素爲5〜50質量ppm的錦（Ca) ’及5〜50質量ppm的錶（Mg) ，及5〜50質量ppm的鑭（La)所成》 (2) —種金（Au)合金接合線，其特徵爲··在將99.9質量 %以上的高純度的鈀（Pd)，白金（Pt)及銅（Cu)中至少一種以 合計含有〇.〇5〜2質量％於99.999質量％以上的高純度金 (Au)的金（Au)合金基質中含有微量元素的合金所成的直徑 2 0μιη以下的被伸長線加工的球形接合用的極細線，該微量 元素爲5〜50質量ppm的鈣（C a)，及5〜50質量ppm的鎂（Mg) -10- 201237191 ，及5〜50質量ppm的鑭（La)，及1〜20質量ppm的鈹（Be)所 成。 (3) —種金（Au)合金接合線，其特徵爲：在將99.9質量 %以上的高純度的鈀（Pd)，白金（Pt)及銅（Cu)中至少一種以 合計含有〇.〇5〜2質量％於99.999質量％以上的高純度金 (Au)的金（Au)合金基質中含有微量元素的合金所成的直徑 2 0μπι以下的被伸長線加工的球形接合用的極細線，該微量 元素爲5〜50質量ppm的耗（Ca)，及5〜50質量ppm的鎂（Mg) ，及5〜50質量ppm的鑭（La)，及將鈽（Ce)，紀（Y)，及銪 (Eu)內的至少一種以合計含有1〜30質量ppm所成。 (4) 一種金（Au)合金接合線，其特徵爲：在將99.9質量 %以上的高純度的鈀（Pd)，白金（Pt)及銅（Cu)中至少一種以 合計含有0.05〜2質量％於99.999質量％以上的高純度金 (Au)的金（Au)合金基質中含有微量元素的合金所成的直徑 20μιη以下的被伸長線加工的球形接合用的極細線，該微量 元素爲5〜50質量ppm的|5(Ca)，及5〜50質量ppm的鎂（Mg) ’及5〜50質量ppm的鑭（La)，及1〜20質量ppm的鈹（Be)， 及將鈽（Ce)，釔（Y)及銪（Eu)內的至少一種以合計含有1〜 30質量ppm所成。 (5) 如申請專利範圍第1項至第4項中任一項所述的金 (Au)合金接合線，其中，全微量元素的合計爲100質量 ppm以下。 依照本發明的金（Au)合金的成分組成，即使接合線的 線徑成爲20μιη以下的細線徑，也具有可防止將毛細管的 -11 - 201237191 表面性惡化作爲原因的壓接球的頸損傷的效果。 又，本發明的金（Au)合金的成分組成是提昇比至今還 要更高機械性強度之故，因而與超過23μιη的線徑時同樣 地都具有傾向的抑制效果，線流動抑制效果。 又，依照本發明的金（Au)合金的成分組成，熔融球爲 真球的效果，以及壓接球成爲真圓的效果是仍然兼備。 又，在本發明中，藉由儘量減少微量元素或不純物， 又藉由抑制毛細管的表面性惡化，在第一接合及第二接合 中，不會有壓接形狀的惡化或未到的發生，在大氣中也可 更確實地連續進行接合好幾十萬次》 【實施方式】 本發明的金（Au)合金接合線是（i)99.999質量％以上的 高純度金（An)及（ii)將99.9質量％以上的高純度的鈀（Pd)， 白金（Pt)及銅（Cu)中至少一種以合計含有0.05〜2質量％， 作爲基質合金，而藉由調整，選定含有於其基質合金中的 微量元素，可得到所期望的性能。 鈀（Pd)，白金（Pt)及銅（Cu)的元素是與金（Au)完全地固 溶，惟成爲稀薄的二元合金時，此些元素是對於金（Au)成 爲容易表面偏析的元素。於是，此些元素的含有量爲最大 2質量％之故，因而將純度作爲99.9質量％以上。純度是 期盼儘量高者’而爲了避免不純物的影響’較佳爲99.99 質量％以上。尤其是’銅（Cu)是作成純度99.999質量％以 上較佳。此些元素中鈀（Pd)與白金（Pt)是在大氣中不會氧 -12- 201237191 化而即使在形成熔融球時蒸發，也不會污染毛細管之故， 因此比銅（Cu)更適用。 又，鈀（Pd)是比白金（Pt)還要容易氧化，惟毛細管對 於陶瓷的析出物或氧化物的防止堆積效果比白金（Pt)還要 高之故因而最適用。在基質合金中，共添加鈀（Pd)與白金 (Pt)及銅（Cu)內的任兩種以上時，則對添加比例之比並未 特別地加以限制。鈀（Pd)或白金（Pt)對於金（Au)都可發揮 同等的基質效果。 在本發明中，在將鈀（Pd)，白金（Pt)及銅（Cu)中的至 少一種以合計不足0.05質量％，接近於純度99.99質量％ 以上的純金線，作成直徑20μιη以下的極細線時，則接合 線的機械性強度並不充分，而會發生傾向。爲了發揮穩定 之效果，其合計的下限是0.05質量％以上，較佳爲0.08 質量％以上。又，若此些稀薄的合金化元素的合計超過2 質量％，則進行球形接合之際，與以往同樣地使得熔融球 變過硬而成爲容易產生晶片裂開，而且因壓接球的接合強 度成爲並不充分，因此其合計的上限是2質量％以下。爲 了發揮穩定之效果，較佳爲1.5質量％以下。 本發明的金（Au)合金接合線，是作爲微量元素，（i)以 鈣（Ca)與鎂（Mg)及鑭（La)的共添加作爲必需，（ii)以鈹（Be) 作爲任意的第一添加元素，（iii)以铈（Ce)，紀（Y)及銪（Eu) 的任一種作爲第二群的任意添加元素者。 藉由以鈣（Ca)與鎂（Mg)及鑭（La)的共添加作爲必須成 分，不但可抑制接合線的熔融球的表面偏析又不會惡化毛 -13- 201237191 細管表面性。毛細管表面惡化的防止效果，是追加第一群 與第二群的任意添加元素也被維持》 藉由此毛細管的表面性惡化被防止，來抑制通過毛細 管內的接合線的滑動阻力上昇。結果，即使進行好幾十萬 次接合之後，也可防止接合線的頸損傷。 在本發明中，以⑴鈣（Ca)與鎂（Mg)及鑭（La)的共添加 作爲必須成分，乃依據以下的理由。 鈣（Ca)與鎂（Mg)及鑭（La)是都具有提昇第二接合的楔 形接合性之效果。作成20μπι以下的細線化時，有第二接 合性容易變低之趨勢之故，因而需要共添加。尤其是，鎂 (Mg)是提昇添加所產生的第二接合的接合性的效果較顯著 。將鎂（Mg)的下限作爲5質量ppm，爲在不足此値，則無 法提昇第二接合性的效果。又，鎂（Mg)的純度是分別99.9 質量％以上，較佳爲99.99質量％以上。即使共添加此些元 素，在金（Au)與鈀（Pd)，白金（Pt)與銅（Cu)的稀薄的二元合 金中也不會有表面偏析的情形。尤其是，鈣（Ca)是在金 (Au)單體金屬中爲有表面偏析的元素，惟在本發明的稀薄 的二元合金中並未有表面偏析。又，及於本發明的稀薄二 元合金中的表面偏析的鈣（Ca)與鎂（Mg)及鑭（La)的3元素 的互相作用是未被看出。因此，即使連續進行好幾十萬次 ，也不會進行著毛細管的表面性惡化或前端對線出口近旁 內部的析出物或其氧化物的堆積，而毛細管及於線的滑動 阻力或及於壓接球的壓接力或從壓接球所奪取的熱能是經 常成爲一定。所以，若將初期的接合條件適當地加以設定 -14- ⑧ 201237191 ，即使進行好幾十萬次接合之後，也仍然維持著初期的接 合條件，而在接合時的壓接球不會留下頸損傷的情形。 又，此些元素中，鈣（Ca)與鑭（La)是提高機械性強度 。亦即，在伸長線加工時此些添加元素是利用相輔相乘效 果會提昇極細線的表皮層的機械性強度之故，因而線愈細 使得線中心部的機械性強度的影響愈沒有，而表皮層的機 械性強度會直接成爲線全體的機械性強度。將鈣（C a)與鑭 (La)的下限分別作爲5質量ppm，乃在不足此値則無法提 昇被伸長線的極細線的機械性強度。又，鑭（La)的純度是 99.9質量％以上，較佳爲99.99質量％以上。鈣（Ca)的純度 是99質量％以上，較佳是99.5質量％以上》 又，此些元素是形成真球狀的熔融球，形成真圓狀的 壓接球。亦即，在金（Au)合金基質的熔融球中此些元素， 是在壓接時不會惡化毛細管表面性或堆積在前端部。又， 即使共添加鈣（Ca)與鎂（Mg)及鑭（La)，也與其他金屬元素 同樣，在壓接金（Au)合金線時，則在毛細管表面會看到一 些堆積。但是，此些共添加元素是表面性之惡化極少，即 使進行接合好幾十萬次，也不會惡化毛細管的表面性，或 是析出物或其氧化物堆積在前端部的情形。將鈣（Ca)與鎂 (Mg)及鑭（La)分別作成50質量ppm ’爲若超過此値’則將 直徑20μιη以極細線進行球形接合之際，無法得到真球狀 的熔融球，或無法得到真圓狀的壓接球。要更確實地得到 真球狀的熔融球與真圓狀的壓接球，鈣（Ca)與鎂（Mg)及鑭 (La)的上限分別爲40質量ppm，且此些的合計爲1〇〇質量 -15- 201237191 ppm以下較佳。又，全微量元素的合計爲100質量ppm以 下更佳。若上述金（Au)合金基質中的全微量元素的總合計 超過1 00質量ppm，則在熔融球表面容易生成氧化物之故 ，因而有第一接合的接合性偶發性地變壞，或是會有惡化 毛細管的表面性之可能性。 又，鎂（Mg)或鑭（La)時，若分別超過50質量ppm，則 會降低直徑20μπι以下的極細線的第二接合的楔形接合性。 在本發明中，將鈹（Be)作爲任意的第一添加元素，乃 依據以下的理由。 鈹（Be)是在鈣（Ca)與鎂（Mg)及鑭（La)的必須成分元素 的共存下壓接金（Au)與鈀（Pd)，白金（Pt)及銅（Cii)的稀薄的 二元合金時具有不會惡化毛細管表面性的效果的元素。所 以，在鈹（Be)與必須成分元素之共存下接合好幾十萬次稀 薄的二元合金的接合線之後，也不會惡化第一接合或第二 接合的形狀，或發生未到，或在接合時的壓接球產生頸損 傷的情形。 又，鈹（Be)是在與本發明的必須成分元素，尤其是在 與鑭（La)之共存下，可更提昇壓接球的圓度。又，鈹（Be) 的純度是在99質量％以上，較佳是99.9質量％以上。又， 鈹（Be)是在與本發明的必須成分元素，尤其是在與鈣（Ca) 的共存下可更提昇稀薄的二元合金的伸長線加工所產生的 極細線表皮層的機械性強度，而即使在直徑20μιη以下的 極細線，也可更防止接合時的線之傾向。將鈹（Be)的下限 作成1質量ppm，乃爲在不足此値時未能看到提昇鈹（Be) -16- ⑧ 201237191 所產生的機械性強度的效果。 另一方’鈹（Be)是把熔融球的硬度變硬。若極細線變 細，則熔融球也會變小，而球形接合之際的給與腳位的晶 片損傷會變大。將鈹（Be)的上限作爲20質量ppm，乃若 超過此値’則將直徑20μηι以下的極細線進行球形接合之 際會把熔融球變過硬而成爲容易產生晶片裂開。又，也有 在毛細管表面或前端部堆積有析出物或其氧化物。爲了發 揮穩定的效果，較佳爲15質量ppm以下。 在本發明中，將姉（Ce)，釔（Y)及銪（Eu)的任一種作爲 第二群的任意添加元素，乃依據如下理由》 此些稀土類元素是在與必須成分元素的共存下具有在 壓接本發明的稀薄二元合金時不會惡化毛細管的表面性的 效果的元素。亦即，此些稀土類元素是與鑭（La)同樣地不 會惡化毛細管表面性，或是進行著析出物或其氧化物的堆 積。所以即使連續接合好幾十萬次，也不會進行著惡化第 一接合或第二接合的形狀或惡化毛細管的表面性等之故， 因而頸損傷不會留著進行接合時的壓接球》惡化毛細管的 表面性等，是鈽（Ce)及釔（Y)的惡化比銪（Eu)還要少。又， 姉（Ce)，釔（Y)及銪（Eu)的純度是分別爲99.9質量％以上， 較佳爲99.99質量％以上。 又，此些的稀土類元素是在必須成分元素，尤其是在 與鑭（La)之共存下藉由本發明的稀薄二元合金的伸長線加 工更提昇極細線的表皮層的機械性強度，即使直徑20μιη 以下的極細線，也可更防止接合時的線的傾向。亦即，如 -17- 201237191 前所眾知地，藉由增加極細線本身的剛性，爲可維持環路 形成性，而且可維持第一接合的壓接球的圓度的元素。此 些的效果是與鈹（Be)同樣。將此些稀土類元素的下限作成 1質量ppm，爲在不足此値，則與鈹（Be)同樣，無法得到 提昇機械性強度的效果。又，將此些稀土類元素的上限作 成20質量ppm，爲與鈹（Be)同樣，則在超過此値，若接 合直徑20μιη以下的極細線之際會把熔融球變硬而容易產 生晶片裂開》 在本發明中，可合倂添加將鈹（Be)作爲任意的第一添 加元素，而將姉（Ce)，釔（Y)及銪（Eu)的任一種作爲第二群 的任意添加元素。即使倂用鈹（Be)與第二群的任意添加元 素，也不會在本發明的稀薄二元合金中產生表面偏析。又 ，第二群的任意稀土類元素，是在本發明的稀薄二元合金 中發揮與鑭（La)同樣的效果者》 實施例 以下，利用實施例及比較例來詳述本發明。 [實施例1〜44] 在表1表示實施例（No. 1〜44)的各試料的成分組成。 在純度99.999質量％的高純度（Au)，純度99.99質量 %的高純度鈀（Pd)，白金（Pt)或純度99.999質量％的高純度 銅（Cu)的稀薄二元金（Au)合金，作爲微量元素調配微量元 素成爲如表1所述的數値（質量ppm)地，使用真空熔解爐 -18 - ⑧ 201237191 進行熔解鑄造。 連續伸長線加工此，線徑爲1 5 μιη及1 8 μηι經最後熱 處理而將伸長率調整成4%。 [表1] 實施例的金合金線的成分組成 η 施 例 基質合金 (單位是質量％) 微量添加元素 (單 βϋ!質 ippm) 必須成分 任意成分 No. Au Pd Pt Cu Ca Mg La Be Υ Ce Eu 1 剩餘部分 0.10 10 40 10 2 剩餘部分 0.10 20 30 15 3 剩餘部分 0.10 30 20 20 4 剩餘部分 0.25 10 10 15 5 剩餘部分 0.25 10 30 20 6 剩餘部分 0.25 15 35 25 7 剩餘部分 0.50 15 10 40 8 剩餘部分 0.50 25 30 30 9 剩餘部分 0.50 30 15 35 10 剩餘部分 0.75 30 30 35 11 剩餘部分 0.75 40 10 -15 12 剩餘部分 0.75 40 35 20 13 剩餘部分 1.00 15 10 10 14 剩餘部分 1.00 25 15 10 15 剩餘部分 1.00 10 10 15 5 16 剩餘部分 1.50 10 30 20 15 17 剩餘部分 1.50 15 35 25 10 18 剩餘部分 1.50 15 10 40 25 19 剩餘部分 0.10 1.00 25 30 30 15 20 剩餘部分 0.25 0.10 30 15 35 10 21 剩餘部分 0.75 0.25 30 20 30 15 22 剩餘部分 0.75 0.75 40 10 14 5 23 剩餘部分 0.10 0.10 0.10 35 15 10 25 24 剩餘部分 0.03 0.03 0.03 30 10 15 5 . 10 25 剩餘部分 0.10 25 15 10 10 10 10 26 剩餘部分 0.10 20 25 20 10 27 剩餘部分 0.10 15 10 30 15 10 28 剩餘部分 0.25 20 30 10 15 10 29 剩餘部分 0.25 25 15 20 5 25 30 剩餘部分 0.25 10 20 25 8 5 15 31 剩餘部分 0.50 40 10 15. 10 11 32 剩餘部分 0.50 30 20 10 5 25 33 剩餘部分 0.50 10 10 15 5 5 5 34 剩餘部分 0.75 10 30 20 β 15 5 35 剰餘部分 0.75 15 30 15 15 5 5 10 36 剩餘部分 0.75 15 10 40 5 5 10 5 37 剩餘部分 1.00 45 40 · 40 38 剩餘部分 1.00 35 45 . 40 39 剩餘部分 1.00 30 35 45 40 剩餘部分 1.50 40 30 40 10 20 41 剩餘部分 1.50 45 35 25 25 42 剩餘部分 1,50 30 30 30 15 10 15 43 剩餘部分 0.10 1.00 25 40 40 10 5 10 10 44 剩餘部分 0.30 0.10 45 30 1〇 10 10 5 -19- 201237191 [比較例No.1〜5] 將與實施例僅微量元素的成分組成不相同的稀薄二$ 金（Au)合金的比較例的各試料的組成表示於表2。稀薄= 元金（Au)合金的極細線是與實施例同樣地，在線徑爲 18μιη及15μιη處施以最後熱處理，將伸長率調整成4% ’ 而與實施例同樣地進行評價。 m2] 比較例的金合金線的成分組成 比 較 例 挪合金 脑添加元索 必挪分 mm No. Au Pd Pt Cu Ca Mg La Βθ .Y Ce Eu 1 剩餘部分 0.03 2 剩餘部分 1.00 1.00 1.00 3 剩餘部分 0.50 1.00 3 30 75 4 剩餘部分 1.00 15 20 .10 40 5 剩餘部分 0.10 40 10 15 25 80 60 此些極細線爲在大氣中藉由依超音波倂用熱壓接方式 的球形接合法連續進行第一次接合於Si晶片上50μιη方形 的Α1腳位（膜厚：約Ιμιη，之後在與由被鍍銀的42合金 所成的導線之間藉由依超音波倂用熱壓拉方式的楔方式接 合法進行第二次接合予以結線。在第一接合中所有球被形 成在50μιη的Α1腳位內。 實施例及比較例的各接合線的頸強度評價是如下地進 行。環路跨距是3mm，而環路高度是作成200μηι。頸強度 是利用變更接合時的參數，反向動作的數値來進行。反向 動作是指爲了形成環路形狀，第一接合後，由第一接合正 -20- 201237191 上方移動毛細管至1C晶片中央側的動作。來自第一接合 正上方的移動距離成爲反向動作。這時候，頸部成爲支點 而會使線彎曲。若其他參數相同，則反向動作値愈.小，彎 曲角是變小，而反向動作値大，彎曲角是變大，亦即，給 予頸部的應力是變大。將其評價結果是表示於表3及表4 。在以反向動作値ΙΟΟΟμηι接合200條而無頸破斷時以◎ 記號表示，在以反向動作値500μιη接合200條而無頸破斷 時以〇記號表示，又在以反向動作値500μηι接合200條而 即使有一條發生時頸破斷時則以△記號表示。 評價將實施例及比較例的各接合線予以線接合50萬 條時的未到發生數。在此評價中，將環路跨距作爲2mm。 將其評價結果表示於表3及表4。未到數是合計第一接合 與第二接合的未到數，將未到數爲零時以◎記號表示，5 條以下時以〇記號表示，而超過5條時以△記號表示。又 ’第一接合與第二接合的未到數連續發生，而無法繼續進 行接合，中止評價時以X記號表示。 實施例及比較例的各接合線的連接特性是利用以下的 牽引測試特性分別加以評價。 牽引測試是使用Dage公司所製造的製品名稱「萬能 接合測試機（BT)(型式4000) j ，以鈎朝上方抬高剛開始連 續接合之後的接合樣品的環路跨距的中央附近，進行測定 破斷荷重。將評價結果表示於表3及表4。 評價「接合之良否」是針對於平均20條的破斷荷重 ’線徑爲18μιη時，將3.5xl0mN以上作爲◎記號，將1.5 -21 - 201237191 xlO〜3.5xl0mN範圍作爲〇記號，而將不足1.5xl0mN作 爲△記號。 又，線徑爲15μιη時，將2.5xl0mN以上作爲◎記號 ，將1.0x10〜2.5xl0mN範圍作爲◦記號，而將不足1·0χ 10mN作爲△記號》 以下，實施例及比較例的各接合線的50萬支線接合 後的連接性是作成如下地分別進行評價。 針對於50萬條線連續接合後的接合樣，與剛開始接 合之後的樣品同樣地進行牽引荷重測定》將評價結果表示 於表3及表4。 在線徑爲18μιη時，15μιη的任一種，也比較20條的 牽引荷重値測定的平均値與剛開始接合之後的牽引荷重値 ，是否降低牽引荷重値，若爲20%以內以◎記號表示，將 50〜20%範圍內者以〇記號表示，而將超過50%者以△記 號表示。又，5萬條線接合數未達到50萬條而無法評價者 以X記號表示。 使用日本島津製作所所製造的製品名稱「電子線微分 析器（ΕΡΜΑ(型式[ΕΡΜΑ-1 600])以2000倍進行元素分析與 面掃描評價線接合50萬次實施例與比較例的各接合線之 後的毛細管表面的則端部。將以面掃描使得微量元素被濃 縮，而覆蓋底子的毛細管部分的元素合倂表示於表3及表 4 〇 -22- 201237191 [表3] 實施例的金合金線的評價結果 實 施 例 No. 線的評價結果 毛細管 表面檢測元素 頸強度 50萬次線 接合結果 初期 牽引測定 齢後 牽引測定 1 ◎ 〇 〇 〇 ifnf. m 2 ◎ ◎ ◎ ◎ 無 3 ◎ ◎ ◎ ◎ 撕 4 ◎ ◎ ◎ ◎ Arrf. 挑 5 ◎ ◎ ◎ ◎ «ftrt! 撕 6 ◎ ◎ ◎ ◎ 無 7 ◎ 〇 0 〇 無 Θ ◎ 〇 ◎ ◎ 無 9 ◎ ◎ ◎ ◎ 無 10 ◎ 〇 © 〇 無 .11 ◎ 〇 0 〇 無 12 ◎ 〇 0 〇 無 13 ◎ ◎ ◎ ◎ 無 14 ◎ ◎ ◎ .◎ ΛττΤ. 挑 15 ◎ ◎ ◎ ◎ m 16 ◎ 0 〇 0 Jtrrf. m 17 ◎ 〇 ◎ ◎ 無 18 ◎ 〇 0 〇 無 19 ◎ 〇 ◎ 〇 Aj£ m 20 ◎ 〇 ◎ 〇 撕 21 ◎ 〇 ◎ 〇 無 22 ◎ 〇 〇 〇 無 23 ◎ 〇 ◎ ◎ Art Μ 24 ◎ ◎ ◎ ◎ ^hrf m 25 ◎ ◎ ◎ ◎ jfnt m 26 〇 ◎ ◎ ◎ 無 27 ◎ ◎ ◎ ◎ 無 28 0 • 0 ◎ ◎ 並 29 ◎ 〇 ◎ 〇 無 30 〇 ◎ ◎ ◎ Λητ. m 31 ◎ 〇 〇 〇 無 32 〇 〇 .◎ 〇 無 33 ◎ ◎ ◎ ◎ 無 34 〇 〇 ◎ ◎ 無 35 〇 〇 〇 〇 無 36 〇 〇 0 〇 無 37 ◎ 〇 〇 〇 無 3S © 〇 〇 〇 無 39 ◎ 〇 0 〇 無 40 〇 〇 〇 〇 無 41 ◎ 〇 0 〇 無 42 〇 〇 〇 〇 無 43 0 〇 〇 〇 無 44 〇 〇 〇 〇 無 [表4] 比i 绞例的金合金線的評價結果 比 較 例 No. 線的 評價結果 毛細管表面 檢測元素 頸強度 線接合結果 初期牽引測定 接合後牽引測定 1 Δ 〇 Δ Δ /fm* Ί1ΙΓ 2 〇 Δ 〇 Δ Μ 3 Δ X Δ X La 4 Δ X Δ X Be 5 Δ X Δ X Ce · Eu 201237191 由上述實施例就可明瞭地知道本發明的金（Au)合金接 合線是若微量元素的添加量爲規定値內，極細線的線徑是 即使成爲1 8μιη以下，也得到可連續進行接合的效果。 對於此，在比較例中，藉由如以下所述的理由，都無 法得到所期望的性能。 比較例1是因在本發明的必須元素的鈀（Pd)未達到規 定量。 比較例2是因在本發明的必須元素的鈀（Pd)，白金 (Pt)及銅（Cu)的合計値含有超過規定量。 比較例3是因在本發明的必須微量元素鈣（Ca)未達到 規定量，且必須微量元素的鑭（La)含有超過規定量。 比較例4是因在本發明的必須微量元素鈹（Be)含有超 過規定量。 比較例5是因在本發明的任意微量元素铈（Ce)及銪 (Eu)分別含有超過規定量。 ⑧ 201237191 於是，比較例3〜5是藉由此些的過剩微量元素的表 面偏析，此些的析出物或其氧化物的堆積都產生在毛細管 表面。 [產業上的利用可能性] 本發明的合金特別適用於汽車裝載用的半導體元件， 被容易成爲高溫的環境下所使用的接合線。 -25-201237191 VI. Description of the Invention: Technical Field The present invention relates to an electrode (foot: pad) on an integrated circuit component for connecting a semiconductor and an electrode (external wire) connected to a circuit wiring substrate. A gold (Au) alloy bonding wire for wire bonding of a semiconductor element, more specifically, a gold (Au) alloy bonding wire processed by an elongation line having a diameter of 20 μm or less which suppresses surface segregation of a trace element. [Technology] It is known that the line on the semiconductor wafer used in the semiconductor device and the wire having a wire diameter of 5 5 to 3 5 μm connected to the external wire are mostly used with a purity of 99. Gold (Au) alloy bonding wire made of high-purity gold of 99% by mass or more. Generally, in the method of joining gold (Au) alloy bonding wires, ultrasonic waves are mainly used in the first bonding and thermocompression bonding is used. In this method, a small discharge is used to heat and melt the front end of the line exposed by the front end of the capillary, and after the surface tension is formed into a spherical shape, the ball portion is crimp-bonded (spherical bonded) at 150. On the electrode of the heated semiconductor element in the range of 〜300 °C, the bonding wire is directly bonded (wedge-bonded) to the external lead side by ultrasonic bonding in the subsequent second bonding. In order to use a semiconductor device such as a transistor or a 1C, after bonding by the bonding wires, an epoxy resin is used for the purpose of protecting a semiconductor wafer, a bonding wire, and a lead frame on which a semiconductor wafer is mounted. . -5- 201237191 Recently, in order to increase the size, thickness, high functionality, and high reliability of semiconductor devices, the characteristics necessary for gold bonding wires have become various, and in order to correspond to the number of semiconductor wafers With the stitching and the narrower pitch, even if the thinner gold bonding wire is required, the required strength is required, or the roundness of the first joined crimping ball or the bonding reliability of the second joining is improved. Even the long-term reliability of the joint. In particular, as the thickness of one layer of the semiconductor device is reduced, the size and thickness of the semiconductor device are reduced. Along with this, the number of input and output terminals per unit area is increased, and the size of the spacer pitch (distance between the centers of the spacers) is also reduced from ΙΟΟμιη to 80 μm, 60 μm. Therefore, the wire diameter of the bonding wire is also reduced from 25 μm to 20 μm or less, and a wire diameter of 15 μm or less is also tried in some cases. However, if the wire diameter of the bonding wire is thinned, the absolute rigidity of the wire itself is lowered and the diameter of the molten ball is also reduced, so that a tendency such as a wire diameter of 25 μm is not problematic or The joint strength of the crimp ball is insufficient, and the long-term reliability of the joint is insufficient. Here, the "prone" refers to a phenomenon in which the line between the first joint and the second joint is tilted to the left and right, and as a result, the interval between the adjacent lines is narrowed, or the contact is inconvenient. Then, as exemplified in Patent Document 1, it is disclosed that for a narrow line of 50 μm corresponding to a high density, a bonding wire having a wire diameter of 20 μm is lifted, and the sealing is closed by an environmentally-regulating sealing resin containing a cerium compound or a hydroxide. Bonding reliability, the total concentration (Cl) of at least one or more elements selected from Cu, Pd, Pt, Zn, Ag (first element group) is -6 - 201237191 0. 005 ~1 . In the range of 5 % by mass, the total concentration (C2) of at least one or more elements selected from Ca, Ce, Eu, Dy, Y (second element group) is 0. 001 ~0. 06% of the range, the total concentration (C3) of at least one element selected from La, Mg, Gd, Tb, Ni (Group 3 element) is 0. 001~0. 05% by mass, the remainder being gold alloy bond wires made of gold and unavoidable impurities (paragraph 026). However, when a trace element is added to a gold (Au) alloy wire, the higher the absolute concentration of the gold (Au) alloy wire, the higher the absolute density of the gold (Au) alloy wire is compared with the gold (Au) alloy wire. Improve various performances, on the other hand, there are cases where undesired performance occurs. When a trace element having a tendency to enhance loop formation is added to a gold (Au) alloy matrix, the formation of gold (Au) balls may be deteriorated, or the wedge bondability may be deteriorated. Further, the additive element contained in the gold (Au) alloy matrix is oxidized by the surface of the surface of the molten spherical surface, or a recess called a pore occurs at the front end of the ball. If the added element is precipitated or oxidized on the surface of the wire, the spacer on the semiconductor device is subjected to a spherical bond [joining of gold (Au) and aluminum (A1)], or wedge bonding is performed on the external wire [Gold (Au)] When joining with silver (Ag), etc., the metal bond is not bonded and causes a joint failure. Further, when the slab is still spherically joined to the spacer on the semiconductor device in the state in which the swell is generated in the molten ball, a region in which the metal bond is not bonded in the center of the crimp portion called the intermediate leak occurs, and the entire region is also formed. Reduce the phenomenon of joint strength. Further, since the shape of the crimping ball is deformed, the spherical joint at a narrow pitch interval becomes difficult or the like, or the hardness of the ball rises, so that the 201237191 wafer is cracked, or the gasket is damaged (the gasket is peeled off from the bottom layer, or There is a problem that the rate of occurrence of inconvenience such as the fact that A1 is thrown out to the outside of the gasket and the film thickness is reduced, and the trace element cannot be added in a large amount. For example, when calcium (Ca) is added alone and strength is to be ensured, calcium (Ca) is locally deposited on the surface of the ultrafine line, and calcium (Ca) precipitated on the surface is oxidized to form a surface oxide film. Since the spherical shape or the jointability of the first joint is unstable, there is a case where the roundness of the crimped ball is deteriorated or the wedge-shaped jointability of the second joint is deteriorated. Further, if a plurality of types of elements to be added are complicated, such elements are complicatedly functioning in the gold (Au) alloy and are deposited on the surface of the molten ball, so that excellent initial bonding cannot be obtained, and reinforcement cannot be obtained. The tendency of the highly reliable first joint and the second joint. Therefore, as described in Patent Document 2, it has been developed to adjust the type and amount of alloying elements, and even if spherical bonding is performed in the atmosphere, an oxide film is not formed on the surface of the molten ball or the ultrafine line, and the bonding property is good. The tendency of inter-compound formation is also a time-dependently low bond line. [Patent Document 1] Japanese Patent Laid-Open Publication No. JP-A No. 2003-13533. The mechanical strength is increased by more than 30%, but if the mechanical strength is increased, the buckling of the general line becomes lower. Therefore, even if a line with a high mechanical strength is used, from the first engagement drawing loop to the second connection 201237191, the root of the first joined crimping ball is prone to cracking, and the so-called neck damage occurs. Or the cause of the neck fracture. In the case where the third element such as Ca or the third element such as La is added to the third element containing IE (Pd) or the like, gold is added as described in paragraphs 0033 to 0034 of Patent Document 1. The improved bonding of the bonding wires of the alloy or the roundness of the spherical shape cannot be solved. Calcium (C a) or bismuth (Be) or a rare earth element is added in a trace amount, and is an element which does not excessively precipitate on the surface of the molten sphere as compared with zinc (Zn) or the like. However, if the spherical joint is continuously performed in the atmosphere for several hundred thousand times, the precipitate or the oxide is accumulated on the surface or the tip end portion of the capillary, so that the pressure-bonded shape of the first joint or the second joint is deteriorated. Inconvenience that the joint strength is insufficient or not, or the smoothness of the capillary surface or the front end portion is deteriorated, so that stress is applied to the root of the crimping ball at the time of forming the loop after the first joining, It is prone to cracking. In addition, when the smoothness of the capillary is deteriorated, the loop formation property such as the abnormality of the loop height or the S-bend is deteriorated, and the line at the time of sealing the epoxy resin as a result thereof is also obtained. The reason for the flow. As a result of the recent miniaturization of the semiconductor device and the increase in density, it has become a factor of inconvenience that the distance between the lines adjacent to the present and the above is narrowed or contacted. Moreover, the performance of the bonding machine is improved, and the joining speed (the number of joints per unit time) is also increased. However, if the joining speed is increased, the smoothness of the capillary surface is also increased (increasing the sliding resistance), but the joining speed is increased. The effect of the smooth deterioration of the capillary surface or the anterior head (increasing the sliding resistance) is more pronounced. -9 _ 201237191 The present invention provides a fine wire having a wire diameter of 20 μm or less, and does not segregate a trace element in a gold (Au) alloy matrix such as gold (Au)_palladium (Pd) to be uniformly distributed, and Even if there is a trace amount of precipitates, the smoothness of the capillary surface or the tip end portion does not increase the sliding resistance, and there is no problem such as neck damage or inconvenience in forming a loop. These problems are also in the case where the amount of all trace elements added is 100 ppm or less. The inventors of the present invention have repeatedly completed their efforts to solve the above problems, and have finally completed the present invention. That is, according to the present invention, a gold (Au) alloy bonding wire shown below is provided. (1) A gold (Au) alloy bonding wire characterized in that it is 99. 9% by mass or more of high-purity palladium (Pd), at least one of platinum (Pt) and copper (Cu) in a total of 0. 05~2% by mass in 99. 999 mass% or more of a high-purity gold (Au) gold (Au) alloy matrix containing a trace element alloy having a diameter of 20 μm or less, which is an ultrafine wire for ball bonding which is processed by an elongation line, and the microelement is 5 ~50 mass ppm of brocade (Ca)' and 5 to 50 mass ppm of the meter (Mg), and 5 to 50 mass ppm of lanthanum (La) (2) - gold (Au) alloy bonding wire, The feature is ··· will be 99. 9% by mass or more of high-purity palladium (Pd), platinum (Pt) and copper (Cu) at least one of which contains yttrium. 〇 5~2% by mass in 99. 999 mass% or more of a high-purity gold (Au) gold (Au) alloy matrix containing a trace element alloy having a diameter of 20 μm or less, which is an ultrafine line for ball bonding which is processed by an elongation line, and the trace element is 5~ 50 ppm by mass of calcium (C a), and 5 to 50 ppm by mass of magnesium (Mg) -10- 201237191, and 5 to 50 ppm by mass of lanthanum (La), and 1 to 20 ppm by mass of bismuth (Be) to make. (3) - Gold (Au) alloy bonding wire, characterized by: 99. 9% by mass or more of high-purity palladium (Pd), platinum (Pt) and copper (Cu) at least one of which contains yttrium. 〇 5~2% by mass in 99. 999 mass% or more of a high-purity gold (Au) gold (Au) alloy matrix containing a trace element alloy having a diameter of 20 μm or less and an extremely fine wire for spherical bonding processed by an elongated wire, the trace element being 5~ 50 mass ppm of consumption (Ca), and 5 to 50 mass ppm of magnesium (Mg), and 5 to 50 mass ppm of lanthanum (La), and lanthanum (Ce), Ji (Y), and yttrium (Eu) At least one of them is contained in a total amount of 1 to 30 ppm by mass. (4) A gold (Au) alloy bonding wire, characterized in that it is 99. 9% by mass or more of high-purity palladium (Pd), at least one of platinum (Pt) and copper (Cu) in a total of 0. 05~2% by mass in 99. 999 mass% or more of a high-purity gold (Au) gold (Au) alloy matrix containing a trace element alloy having a diameter of 20 μm or less and an extremely fine line for spherical bonding processed by an elongation line, the trace element being 5 to 50 Mass ppm of |5 (Ca), and 5 to 50 ppm by mass of magnesium (Mg) 'and 5 to 50 ppm by mass of lanthanum (La), and 1 to 20 ppm by mass of bismuth (Be), and 钸 (Ce At least one of yttrium (Y) and yttrium (Eu) is contained in a total amount of 1 to 30 ppm by mass. (5) The gold (Au) alloy bonding wire according to any one of the above claims, wherein the total amount of the total trace elements is 100 ppm by mass or less. In the composition of the gold (Au) alloy according to the present invention, even if the wire diameter of the bonding wire is 20 μm or less, it is possible to prevent the neck of the crimping ball from being deteriorated by the deterioration of the surface of the capillary -11 - 201237191. effect. Further, since the composition of the gold (Au) alloy of the present invention is higher in mechanical strength than the conventional one, it has a tendency to suppress the same effect as the wire diameter exceeding 23 μm, and has a line flow suppressing effect. Further, according to the composition of the gold (Au) alloy of the present invention, the effect that the molten ball is a true ball and the effect that the crimped ball becomes a true circle are still possessed. Further, in the present invention, by suppressing the deterioration of the surface properties of the capillary by minimizing trace elements or impurities, there is no deterioration or failure of the pressure-bonding shape in the first bonding and the second bonding. It is also possible to continuously join hundreds of thousands of times in the atmosphere. [Embodiment] The gold (Au) alloy bonding wire of the present invention is (i) 99. 999 mass% or more of high purity gold (An) and (ii) will be 99. 9% by mass or more of high-purity palladium (Pd), at least one of platinum (Pt) and copper (Cu) in a total of 0. 05 to 2% by mass, as a matrix alloy, the desired properties can be obtained by adjusting the trace elements contained in the matrix alloy. The elements of palladium (Pd), platinum (Pt) and copper (Cu) are completely solid solution with gold (Au), but when they become a thin binary alloy, these elements are easy to surface segregate for gold (Au). element. Therefore, the content of such elements is at most 2% by mass, and thus the purity is taken as 99. 9% by mass or more. The purity is expected to be as high as possible, and in order to avoid the influence of impurities, it is preferably 99. 99% by mass or more. In particular, 'copper (Cu) is made to a purity of 99. More than 999 mass% is preferred. Among these elements, palladium (Pd) and platinum (Pt) are not in the atmosphere and are not oxidized in the atmosphere, and even if they evaporate when forming a molten sphere, they do not pollute the capillary, so they are more suitable than copper (Cu). . Further, palladium (Pd) is more easily oxidized than platinum (Pt), and the capillary is more suitable for preventing deposition of precipitates or oxides of ceramics than platinum (Pt). When a total of two or more kinds of palladium (Pd), platinum (Pt) and copper (Cu) are added to the matrix alloy, the ratio of the addition ratio is not particularly limited. Palladium (Pd) or platinum (Pt) exerts the same matrix effect on gold (Au). In the present invention, at least one of palladium (Pd), platinum (Pt) and copper (Cu) is less than 0 in total. 05% by mass, close to the purity of 99. When a pure gold wire of 99% by mass or more is formed into an ultrafine wire having a diameter of 20 μm or less, the mechanical strength of the bonding wire is insufficient and tends to occur. In order to achieve a stable effect, the lower limit of the total is 0. 05% by mass or more, preferably 0. 08% by mass or more. In addition, when the total amount of the thin alloying elements is more than 2% by mass, when the spherical bonding is performed, the molten ball is hardened in the same manner as in the related art, and wafer cracking is likely to occur, and the bonding strength of the crimping ball becomes It is not sufficient, so the upper limit of the total is 2% by mass or less. In order to exert a stable effect, it is preferably 1. 5 mass% or less. The gold (Au) alloy bonding wire of the present invention is required as a trace element, (i) co-addition of calcium (Ca) with magnesium (Mg) and lanthanum (La), and (ii) arbitrarily (Be) The first added element, (iii) is any one of 第二 (Ce), 纪 (Y), and 铕 (Eu) as the arbitrarily added element of the second group. By co-addition of calcium (Ca) with magnesium (Mg) and lanthanum (La) as an essential component, not only the surface segregation of the molten ball of the bonding wire but also the surface property of the capillary can be suppressed. The effect of preventing the deterioration of the capillary surface is to prevent the addition of any of the additive elements of the first group and the second group, whereby the deterioration of the surface properties of the capillary is prevented, and the increase in the sliding resistance of the bonding wire passing through the capillary is suppressed. As a result, neck damage of the bonding wire can be prevented even after several hundred thousand joints are performed. In the present invention, (1) co-addition of calcium (Ca) with magnesium (Mg) and lanthanum (La) is an essential component for the following reasons. Calcium (Ca), magnesium (Mg) and lanthanum (La) all have the effect of improving the wedge bondability of the second joint. When the thin line is formed to be 20 μm or less, the second bonding property tends to be low, so that it is necessary to add a total amount. In particular, magnesium (Mg) is more effective in enhancing the bondability of the second joint produced by the addition. When the lower limit of magnesium (Mg) is 5 mass ppm, the effect of the second bondability cannot be improved if it is less than this. Moreover, the purity of magnesium (Mg) is 99. 9% by mass or more, preferably 99. 99% by mass or more. Even if these elements are added together, there is no surface segregation in the thin binary alloy of gold (Au) and palladium (Pd), platinum (Pt) and copper (Cu). In particular, calcium (Ca) is an element having surface segregation in the gold (Au) monomer metal, but there is no surface segregation in the thin binary alloy of the present invention. Further, the interaction between the surface segregated calcium (Ca) and the three elements of magnesium (Mg) and lanthanum (La) in the thin binary alloy of the present invention is not seen. Therefore, even if it is continuously performed several hundred thousand times, the surface property of the capillary is not deteriorated, or the deposition of precipitates or oxides in the vicinity of the front end of the wire outlet is not performed, and the sliding resistance of the capillary and the wire or the pressure is suppressed. The crimping force of the catching ball or the heat energy taken from the crimping ball is often constant. Therefore, if the initial joining conditions are appropriately set -14 - 8 201237191, even after several hundred thousand joints are performed, the initial joining conditions are maintained, and the crimping balls at the time of joining do not leave the neck. The situation of injury. Further, among these elements, calcium (Ca) and lanthanum (La) increase mechanical strength. That is to say, in the processing of the elongation line, the additive elements use the complementary multiplication effect to increase the mechanical strength of the skin layer of the ultrafine line, and thus the thinner the line, the less the mechanical strength of the center portion of the line is affected. The mechanical strength of the skin layer directly becomes the mechanical strength of the entire line. The lower limit of calcium (C a) and lanthanum (La) is 5 mass ppm, respectively, and if it is less than this, the mechanical strength of the ultrafine line of the stretched wire cannot be increased. Also, the purity of lanthanum (La) is 99. 9 mass% or more, preferably 99. 99% by mass or more. The purity of calcium (Ca) is 99% by mass or more, preferably 99. 5 mass% or more. Further, these elements are formed into a true spherical molten ball to form a true round crimp ball. That is, such elements in the molten ball of the gold (Au) alloy matrix do not deteriorate the capillary surface properties or accumulate at the front end portion during crimping. Further, even if calcium (Ca), magnesium (Mg) and lanthanum (La) are added in common, similarly to other metal elements, when the gold (Au) alloy wire is crimped, some accumulation is observed on the surface of the capillary. However, such a co-added element has little deterioration in surface properties, and even if it is bonded several hundred thousand times, the surface properties of the capillary are not deteriorated, or the precipitate or the oxide thereof is deposited on the tip end portion. When calcium (Ca), magnesium (Mg), and lanthanum (La) are respectively 50 mass ppm, 'when it exceeds this 値', when a diameter of 20 μm is spherically joined by a very thin wire, a true spherical molten ball cannot be obtained, or Unable to get a true round crimp ball. In order to obtain a true spherical molten ball and a true round crimping ball more reliably, the upper limits of calcium (Ca) and magnesium (Mg) and lanthanum (La) are respectively 40 mass ppm, and the total of these is 1 〇. 〇 Quality -15- 201237191 ppm is preferred. Further, the total amount of all trace elements is preferably 100 ppm by mass or less. When the total amount of the total trace elements in the gold (Au) alloy matrix exceeds 100 ppm by mass, oxides are easily formed on the surface of the molten sphere, and thus the joint property of the first joint is occasionally deteriorated, or There is a possibility of deteriorating the surface properties of the capillary. Further, when magnesium (Mg) or lanthanum (La) exceeds 50 ppm by mass, the wedge bondability of the second joint of the ultrafine wires having a diameter of 20 μm or less is lowered. In the present invention, 铍 (Be) is an arbitrary first additive element for the following reasons. Be (Be) is a thinning of gold (Au) and palladium (Pd), platinum (Pt) and copper (Cii) in the coexistence of calcium (Ca) and magnesium (Mg) and lanthanum (La) essential components. The binary alloy has an effect of not deteriorating the surface properties of the capillary. Therefore, after joining the bonding wires of hundreds of thousands of thin binary alloys in the coexistence of beryllium (Be) and the essential component elements, the shape of the first bonding or the second bonding is not deteriorated, or the occurrence of the first bonding or the second bonding does not occur, or The crimping ball at the time of joining produces a neck damage. Further, beryllium (Be) enhances the roundness of the crimp ball in addition to the essential component elements of the present invention, particularly in the presence of lanthanum (La). Further, the purity of bismuth (Be) is 99% by mass or more, preferably 99. 9% by mass or more. Further, beryllium (Be) is a mechanical strength of the ultrafine line skin layer which is produced by the elongation line processing of the rare binary alloy in the coexistence with the essential component elements of the present invention, especially in the presence of calcium (Ca). Further, even in the case of extremely thin wires having a diameter of 20 μm or less, the tendency of the wires at the time of joining can be further prevented. The lower limit of 铍(Be) was made to be 1 mass ppm, which was the effect of not improving the mechanical strength generated by the 铍(Be) -16-8 201237191 when it was less than this. The other side, Be, hardens the hardness of the molten ball. If the extremely thin line is thinned, the molten ball will also become small, and the damage to the wafer for the foot when the ball is joined will become large. When the upper limit of the bismuth (Be) is 20 ppm by mass, if the ultrafine wire having a diameter of 20 μm or less is spherically joined, the molten ball is hardened and the wafer is easily broken. Further, precipitates or oxides thereof may be deposited on the surface or the tip end portion of the capillary. In order to achieve a stable effect, it is preferably 15 ppm by mass or less. In the present invention, any one of cerium (Ce), yttrium (Y) and lanthanum (Eu) is used as an optional element of the second group, based on the following reasons: These rare earth elements are coexisting with essential component elements. There is an element having an effect of not deteriorating the surface properties of the capillary when the rare binary alloy of the present invention is crimped. That is, these rare earth elements do not deteriorate the capillary surface properties or the deposition of precipitates or oxides thereof as in the case of lanthanum (La). Therefore, even if the joint is continuously joined for several hundred thousand times, the shape of the first joint or the second joint is deteriorated or the surface property of the capillary is deteriorated, and the neck damage does not leave the crimping ball at the time of joining. Deteriorating the surface properties of the capillary, etc., is that the deterioration of cerium (Ce) and yttrium (Y) is less than that of 铕 (Eu). Moreover, the purity of 姊(Ce), 钇(Y) and 铕(Eu) is 99. 9 mass% or more, preferably 99. 99% by mass or more. Further, such rare earth elements are mechanical strengths which enhance the skin layer of the ultrafine lines by the elongation line processing of the rare binary alloy of the present invention in the presence of an essential component element, particularly in the presence of lanthanum (La), even if The extremely thin wire having a diameter of 20 μm or less can also prevent the tendency of the wire at the time of joining. That is, as previously known from -17 to 201237191, by increasing the rigidity of the ultrafine wire itself, it is an element which can maintain loop formation and maintain the roundness of the first joined crimp ball. The effect of these is the same as 铍 (Be). When the lower limit of the rare earth element is 1 ppm by mass, if it is less than this, the effect of improving the mechanical strength cannot be obtained similarly to the beryllium (Be). In addition, the upper limit of the rare earth element is 20 ppm by mass, and when it is more than 铍 (Be), when the ultrafine wire having a diameter of 20 μm or less is joined, the molten ball is hardened and wafer cracking is likely to occur. In the present invention, 铍(Be) may be added as an arbitrary first additive element, and any one of 姊(Ce), 钇(Y) and 铕(Eu) may be used as any additional element of the second group. . Even if Be (Be) and any of the added elements of the second group are used, surface segregation does not occur in the rare binary alloy of the present invention. Further, any rare earth element of the second group exhibits the same effect as lanthanum (La) in the rare binary alloy of the present invention. EXAMPLES Hereinafter, the present invention will be described in detail by way of examples and comparative examples. [Examples 1 to 44] Table 1 shows an example (No. 1 to 44) The composition of each sample. In purity 99. 999 mass% high purity (Au), purity 99. 99% by mass of high purity palladium (Pd), platinum (Pt) or purity of 99. 999 mass% of high-purity copper (Cu) thin binary gold (Au) alloy, which is used as a trace element to prepare trace elements to a number of 値 (mass ppm) as shown in Table 1, using a vacuum melting furnace -18 - 8 201237191 Melt casting. The continuous elongation line was processed to have a wire diameter of 15 μm and 1 8 μηι, and the elongation was adjusted to 4% by the final heat treatment. [Table 1] Composition of gold alloy wire of the example η Example Matrix alloy (unit: mass%) Trace additive element (single βϋ! mass ippm) Required component Any component No. Au Pd Pt Cu Ca Mg La Be Υ Ce Eu 1 The remaining part 0. 10 10 40 10 2 Remaining part 0. 10 20 30 15 3 Remaining part 0. 10 30 20 20 4 Remaining part 0. 25 10 10 15 5 Remaining part 0. 25 10 30 20 6 Remaining part 0. 25 15 35 25 7 Remaining part 0. 50 15 10 40 8 Remaining part 0. 50 25 30 30 9 Remaining part 0. 50 30 15 35 10 Remaining part 0. 75 30 30 35 11 Remaining part 0. 75 40 10 -15 12 Remaining part 0. 75 40 35 20 13 Remaining part 1. 00 15 10 10 14 Remaining part 1. 00 25 15 10 15 Remaining part 1. 00 10 10 15 5 16 Remaining part 1. 50 10 30 20 15 17 Remaining part 1. 50 15 35 25 10 18 Remaining part 1. 50 15 10 40 25 19 Remaining part 0. 10 1. 00 25 30 30 15 20 The rest 0. 25 0. 10 30 15 35 10 21 Remaining part 0. 75 0. 25 30 20 30 15 22 Remaining part 0. 75 0. 75 40 10 14 5 23 Remaining part 0. 10 0. 10 0. 10 35 15 10 25 24 Remaining part 0. 03 0. 03 0. 03 30 10 15 5 . 10 25 Remaining part 0. 10 25 15 10 10 10 10 26 Remaining part 0. 10 20 25 20 10 27 Remaining part 0. 10 15 10 30 15 10 28 Remaining part 0. 25 20 30 10 15 10 29 Remaining part 0. 25 25 15 20 5 25 30 The remaining part 0. 25 10 20 25 8 5 15 31 The remaining part 0. 50 40 10 15. 10 11 32 The remaining part 0. 50 30 20 10 5 25 33 The remaining part 0. 50 10 10 15 5 5 5 34 The remaining part 0. 75 10 30 20 β 15 5 35 surplus part 0. 75 15 30 15 15 5 5 10 36 Remaining part 0. 75 15 10 40 5 5 10 5 37 Remaining part 1. 00 45 40 · 40 38 Remaining part 1. 00 35 45 . 40 39 Remaining part 1. 00 30 35 45 40 Remaining part 1. 50 40 30 40 10 20 41 Remaining part 1. 50 45 35 25 25 42 Remaining part 1,50 30 30 30 15 10 15 43 Remaining part 0. 10 1. 00 25 40 40 10 5 10 10 44 The remaining part 0. 30 0. 10 45 30 1〇 10 10 5 -19- 201237191 [Comparative Example No. 1 to 5] The composition of each sample of the comparative example of the thin two-gold (Au) alloy which is different from the composition of the trace elements of the examples is shown in Table 2. In the same manner as in the Example, the ultrafine line of the elemental alloy (Au) was evaluated by the same heat treatment as in the case where the wire diameter was 18 μm and 15 μm, and the elongation was adjusted to 4%'. M2] The composition of the gold alloy wire of the comparative example is compared with the case of the alloy. Au Pd Pt Cu Ca Mg La Βθ . Y Ce Eu 1 The remaining part 0. 03 2 Remaining part 1. 00 1. 00 1. 00 3 The remaining part 0. 50 1. 00 3 30 75 4 Remaining part 1. 00 15 20 . 10 40 5 The remaining part 0. 10 40 10 15 25 80 60 These extremely thin wires are continuously bonded to the 50 μm square Α1 pin on the Si wafer by the ball bonding method in the atmosphere by ultrasonic bonding. (Film thickness: approx. Ιμιη, and then a second bonding is performed by a wedge bonding method using a hot-pressing method according to ultrasonic waves with a wire made of a silver-plated 42 alloy. All the balls are formed in the first bonding. In the Α1 position of 50 μm, the neck strength of each of the bonding wires of the examples and the comparative examples was evaluated as follows: the loop span was 3 mm, and the loop height was made 200 μm. The neck strength was changed by the parameters at the time of bonding. The reverse action is performed by the number of reverse operations. The reverse action refers to the action of moving the capillary from the first bonding positive -20-201237191 to the center side of the 1C wafer after the first bonding in order to form the loop shape. The moving distance directly above becomes the reverse action. At this time, the neck becomes a fulcrum and the line is bent. If the other parameters are the same, the reverse action is healed. Small, the bending angle is small, and the reverse action is large, and the bending angle is enlarged, that is, the stress applied to the neck is increased. The evaluation results are shown in Tables 3 and 4. When 200 pieces are joined by the reverse action 値ΙΟΟΟμηι and the neck is not broken, it is indicated by a ◎ mark, and when 200 pieces are joined by a reverse action 値500 μm without a neck break, it is indicated by a 〇 mark, and in a reverse action 値500μηι When 200 pieces are joined, the △ mark is indicated even if one of the necks breaks. The number of occurrences when the bonding wires of the examples and the comparative examples were bonded to 500,000 pieces was evaluated. In this evaluation, the loop span was taken as 2 mm. The evaluation results are shown in Tables 3 and 4. The number of misses is the sum of the first joint and the second joint, and is represented by a ◎ mark when the number is not zero, a 〇 mark when five or less, and a △ mark when it exceeds five. Further, the number of the first joint and the second joint is continuously generated, and the joining cannot be continued, and the evaluation is stopped by the X mark. The connection characteristics of the bonding wires of the examples and the comparative examples were evaluated by the following traction test characteristics. The traction test was carried out by using the product name "Universal Bonding Tester (BT) (type 4000) j manufactured by Dage, and raising the hook near the center of the loop span of the joined sample immediately after the continuous joining. The load was broken. The results of the evaluation are shown in Tables 3 and 4. The evaluation of "goodness of joining" is for the average breaking load of 20 pieces, and the wire diameter is 18 μm. 5xl0mN or more as the ◎ mark, will be 1. 5 -21 - 201237191 xlO~3. The 5xl0mN range is used as the 〇 mark, but will be less than 1. 5xl0mN is used as the △ mark. Also, when the wire diameter is 15μιη, it will be 2. 5xl0mN or more as the ◎ mark, will be 1. 0x10~2. The range of 5x10mN is used as the ◦ mark, and less than 1·0 χ 10mN is used as the Δ mark. Hereinafter, the connectivity after the joining of the 500,000 spurs of the bonding wires of the examples and the comparative examples was evaluated as follows. The traction load measurement was performed in the same manner as the sample immediately after the start of joining with the bonded sample after the continuous bonding of 500,000 lines. The evaluation results are shown in Tables 3 and 4. When the wire diameter is 18μηη, any of 15μιη, and the average 値 measured by the traction load 20 of 20 and the traction load 刚 after the initial engagement are compared, whether the traction load 降低 is reduced, and if it is within 20%, it is indicated by the ◎ mark. Those in the range of 50 to 20% are indicated by 〇 marks, and those exceeding 50% are indicated by △ marks. In addition, the number of 50,000 wire joints is less than 500,000, and those who cannot be evaluated are indicated by X marks. Using the name of the product manufactured by Shimadzu Corporation of Japan, the electron micro-analyzer (ΕΡΜΑ (type [ΕΡΜΑ-1 600]), the elemental analysis and the surface scan evaluation line were joined by 2,000 times, and the bonding wires of the example and the comparative example were bonded 500,000 times. The end of the capillary surface is then scanned by surface scanning so that the trace elements are concentrated, and the elements of the capillary portion covering the substrate are shown in Table 3 and Table 4 〇-22- 201237191 [Table 3] Gold alloy of the example Line evaluation result Example No. Evaluation results of the line Capillary Surface detection element Neck strength 500,000 times line Bonding results Initial traction measurement Post-mortem traction measurement 1 ◎ 〇 〇 〇 ifnf. m 2 ◎ ◎ ◎ ◎ None 3 ◎ ◎ ◎ ◎ 撕 4 ◎ ◎ ◎ ◎ Arrf. Pick 5 ◎ ◎ ◎ ◎ « ftrt! tear 6 ◎ ◎ ◎ ◎ no 7 ◎ 〇 0 〇 no Θ ◎ 〇 ◎ ◎ no 9 ◎ ◎ ◎ ◎ no 10 ◎ 〇 © 〇 no . 11 ◎ 〇 0 〇 no 12 ◎ 〇 0 〇 no 13 ◎ ◎ ◎ ◎ no 14 ◎ ◎ ◎ ◎ . ◎ ΛττΤ. Pick 15 ◎ ◎ ◎ ◎ m 16 ◎ 0 〇 0 Jtrrf. m 17 ◎ 〇 ◎ ◎ No 18 ◎ 〇 0 〇 no 19 ◎ 〇 ◎ 〇 Aj £ m 20 ◎ 〇 ◎ 〇 21 21 ◎ 〇 ◎ 〇 no 22 ◎ 〇〇〇 no 23 ◎ 〇 ◎ ◎ Art Μ 24 ◎ ◎ ◎ ◎ ^hrf m 25 ◎ ◎ ◎ ◎ jfnt m 26 〇 ◎ ◎ ◎ No 27 ◎ ◎ ◎ ◎ No 28 0 • 0 ◎ ◎ and 29 ◎ 〇 ◎ 〇 no 30 〇 ◎ ◎ ◎ Λ ητ. m 31 ◎ 〇 〇 〇 no 32 〇 〇 . ◎ 〇 no 33 ◎ ◎ ◎ ◎ no 34 〇〇 ◎ ◎ no 35 〇〇〇〇 no 36 〇〇 0 〇 no 37 ◎ 〇〇〇 no 3S © 〇〇〇 no 39 ◎ 〇 0 〇 no 40 〇〇〇〇 None 41 ◎ 〇0 〇 no 42 〇〇〇〇 no 43 0 〇〇〇 no 44 〇〇〇〇 no [Table 4] Comparison of the evaluation results of the gold alloy wire of the example of i. Evaluation results of the line capillary surface detection element neck strength line bonding result initial traction measurement post-join traction measurement 1 Δ 〇 Δ Δ /fm* Ί1ΙΓ 2 〇Δ 〇Δ Μ 3 Δ X Δ X La 4 Δ X Δ X Be 5 Δ X Δ X Ce · Eu 201237191 It is apparent from the above examples that the gold (Au) alloy bonding wire of the present invention is such that the amount of the trace element added is within the predetermined crucible, and the wire diameter of the ultrafine line is equal to or less than 18 μm. The effect of continuous joining is obtained. In this regard, in the comparative example, the desired performance could not be obtained for the reasons described below. Comparative Example 1 is that the palladium (Pd) which is an essential element in the present invention did not reach the specification. In Comparative Example 2, the total amount of palladium (Pd), platinum (Pt) and copper (Cu) contained in the essential element of the present invention exceeded a predetermined amount. In Comparative Example 3, the essential trace element calcium (Ca) in the present invention did not reach a predetermined amount, and the amount of lanthanum (La) contained in the trace element was required to exceed a predetermined amount. In Comparative Example 4, the necessary trace element cerium (Be) in the present invention contained more than a predetermined amount. In Comparative Example 5, any of the trace elements C(Ce) and 铕(Eu) in the present invention contained more than a predetermined amount. 8 201237191 Thus, Comparative Examples 3 to 5 are surface segregation of such excess trace elements, and deposition of such precipitates or oxides thereof is generated on the surface of the capillary. [Industrial Applicability] The alloy of the present invention is particularly suitable for use in a semiconductor element for mounting an automobile, and is easily used as a bonding wire used in a high-temperature environment. -25-