TWI452638B - A semiconductor device, a method of manufacturing the same, and an assembly structure for assembling the semiconductor element - Google Patents

A semiconductor device, a method of manufacturing the same, and an assembly structure for assembling the semiconductor element Download PDF

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Publication number
TWI452638B
TWI452638B TW097133726A TW97133726A TWI452638B TW I452638 B TWI452638 B TW I452638B TW 097133726 A TW097133726 A TW 097133726A TW 97133726 A TW97133726 A TW 97133726A TW I452638 B TWI452638 B TW I452638B
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Taiwan
Prior art keywords
barrier metal
metal layer
layer
phosphorus
conductive
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TW097133726A
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English (en)
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TW200915457A (en
Inventor
Kenichi Kato
Yoshio Shimoaka
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Kyocera Corp
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Publication of TW200915457A publication Critical patent/TW200915457A/zh
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Publication of TWI452638B publication Critical patent/TWI452638B/zh

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Description

半導體元件、其製造方法及組裝該半導體元件之組裝構造體 技術領域
本發明係有關於一種具有焊料凸塊等導電性凸塊的半導體元件、其製造方法及組裝該半導體元件之組裝構造體。
 背景技術
近年來，由於要求半導體封裝的高密度組裝，故已從採用絲焊(wire bonding)的COB(板上連接式晶片)組裝法轉為採用倒裝焊接(face down bonding)的倒裝晶片組裝法。
藉由前述倒裝晶片組裝法組裝於配線基板的半導體晶片包括具有半導體基板、電極、鈍化層、障壁金屬層、及焊料凸塊者。該電極位於半導體基板上。該鈍化層位於電極上，且具有往厚度方向貫穿之開口部。該障壁金屬層在鈍化層之開口部下方位於電極上，且含有磷(P)。該焊料凸塊形成於障壁金屬層上。
通常，如前述般所構成之半導體晶片的障壁金屬層，於其焊料凸塊側之表面部具有富磷部位。該富磷部位係指磷含有率相對較大的部位。然而，富磷部位的機械性強度比起其他部位相對較低。因此，若障壁金屬層的富磷部位之厚度增大，則焊料凸塊與障壁金屬層之接合部分的機械性強度會降低。藉此，例如熱應力反覆作用在組裝半導體晶片的配線基板時，會有該接合部分產生裂痕，進而使焊料凸塊剝離的情形產生。為了改善前述問題，用以整體地 控制富磷部位之厚度的技術已公開於專利文獻1。
具體而言，根據專利文獻1，可如下述所示地製造出半導體晶片。首先，於半導體基板上形成電極墊。該電極墊係由例如鋁等導電性材料所形成。接著，形成鈍化膜以覆蓋半導體基板的電極墊形成面當中，未經該電極墊覆蓋之部位及該電極墊之外周部。然後，藉由無電電鍍鎳，於電極墊上的未經鈍化膜覆蓋之部位形成鎳層。接著，藉由無電電鍍金，於鎳層上形成金層。然後，藉由於金層上配設焊料並加熱來形成焊料凸塊。如此一來，可製造出具有凸塊的半導體晶片。另外，鎳層與金層係可發揮作為焊料凸塊基底之障壁金屬層的功能者。
若藉由專利文獻1記載之製造方法製造半導體晶片，在形成焊料凸塊時，可藉由金層減少構成鎳層之鎳往焊料凸塊內擴散的情形。藉此，可減少相對較脆的金屬間化合物層厚厚地形成在鎳與焊料之界面的情形，而可提高信賴性。
【專利文獻1】特開2004－273959號公報
 發明揭示
然而，前述半導體晶片中，若整體地縮小富磷層之厚度，則會有半導體晶片之耐腐蝕性降低的情形產生。這是因為磷偏析的領域(富P層)比起鎳層之其他部位具有高耐腐蝕性的緣故。尤其是鈍化膜的開口部附近，外部空氣容易從該鈍化層與鎳層之間侵入，故會有容易產生腐蝕的傾向。
本發明係在前述情形下所想出者，其目的在於提供一種在機械性信賴性及電性信賴性兩方面均優異的半導體元件、其製造方法及該半導體元件之組裝構造體。
本發明之第1半導體元件具有基板、導電層、保護層、障壁金屬層、及導電性凸塊。該導電層設於基板上。該保護層設於導電層上且具有開口部。該障壁金屬層在前述開口部中接合於導電層。該導電性凸塊形成於障壁金屬層上。又，前述障壁金屬層含有磷，且包含前述磷含有率大於其他部分的富磷部位。該富磷部位位於導電性凸塊側之表面部，且導電性凸塊的形成領域之周緣部的厚度大於該形成領域之中央部的厚度。
本發明之第2半導體元件具有基板、導電層、保護層、障壁金屬層、及導電性凸塊。該導電層設於基板上。該保護層設於導電層上且具有開口部。該障壁金屬層在前述開口部中接合於導電層。該導電性凸塊形成於障壁金屬層上。又，前述障壁金屬層含有磷，且包含前述磷含有率大於其他部分的富磷部位。該富磷部位位於導電性凸塊側之表面部，且僅位於導電性凸塊的形成領域之周緣部。
本發明之組裝構造體具有本發明之半導體元件及具有配線電極之基體。該基體上裝設有電性連接於前述配線電極之墊部。該墊部與本發明之半導體元件之導電性凸塊接合。
本發明之半導體元件之製造方法包含有導電層形成步 驟、保護層形成步驟、障壁金屬層形成步驟、有機被膜形成步驟、導電性構件配置步驟、及凸塊形成步驟。在該導電層形成步驟中，於基板主面形成導電層。在該保護層形成步驟中，形成覆蓋導電層且於導電層上具有開口部的保護層。在該障壁金屬層形成步驟中，形成在開口部中接合於導電層的障壁金屬層。在該有機被膜形成步驟中，於障壁金屬層上形成有機被膜。在該導電性構件配置步驟中，於有機被膜上配置導電性構件。該導電性構件的熔點低於有機被膜之蒸發溫度。在該凸塊形成步驟中，使導電性構件熔融並且使有機被膜揮發，於障壁金屬層上形成導電性凸塊。
本發明之半導體元件、其製造方法及組裝構造體可成為在機械性信賴性及電性信賴性兩方面均優異者。
圖式簡單說明
第1A圖係顯示本發明第1實施態樣之半導體元件之概略構造的主要部分截面圖。
第1B圖係放大顯示第1A圖之一部分的截面圖。
第2圖係顯示第1A圖所示之半導體元件之概略構造的平面視圖。
第3A圖係顯示第1A圖所示之半導體元件之製造過程之一步驟的主要部分截面圖。
第3B圖係顯示第3A圖之下一步驟的主要部分截面圖。
第3C圖係顯示第3B圖之下一步驟的主要部分截面圖。
第4A圖係顯示第3C圖之下一步驟的主要部分截面圖。
第4B圖係顯示第4A圖之下一步驟的主要部分截面圖。
第4C圖係顯示第4B圖之下一步驟的主要部分截面圖。
第5A圖係顯示第4C圖之下一步驟的主要部分截面圖。
第5B圖係顯示第5A圖之下一步驟的主要部分截面圖。
第5C圖係顯示第5B圖之下一步驟的主要部分截面圖。
第6A圖係顯示本發明第2實施態樣之半導體元件之概略構造的主要部分截面圖。
第6B圖係放大顯示第6A圖之一部分的截面圖。
第7A圖係顯示第6A圖所示之半導體元件之製造過程之一步驟的主要部分截面圖。
第7B圖係顯示第7A圖之下一步驟的主要部分截面圖。
第8圖係顯示本發明第3實施態樣之組裝構造體之概略構造的主要部分截面圖。
第9A圖係顯示本發明第1實施態樣之半導體元件之變形例的主要部分截面圖。
第9B圖係放大顯示第9A圖之一部分的截面圖。
第10A圖係顯示本發明第1實施態樣之半導體元件之其他變形例的主要部分截面圖。
第10B圖係放大顯示第10A圖之一部分的截面圖。
第11圖係顯示本發明第1實施態樣之半導體元件之另一不同變形例的主要部分截面圖。
第12圖係顯示藉由本發明第4實施態樣之製造方法製作的半導體元件之該略構造的主要部分放大截面圖。
 實施發明之最佳態樣
以下，邊參照圖式邊說明本發明之實施態樣。
<第1實施態樣>
第1A圖係顯示本發明第1實施態樣之半導體元件X1之概略構造的主要部分截面圖。第1B圖係放大顯示第1A圖之一部分的截面圖。第2圖係顯示半導體元件X1之概略構造的平面圖。
半導體元件X1具有半導體基板10、導電層20、作為保護層之鈍化層30、障壁金屬層40、焊料凸塊50。
半導體基板10係藉由例如矽(Si)等半導體材料所形成。該半導體基板10在其表面及內部形成有積體電路(未圖示)。另外，半導體基板10不僅限於單層構造亦可為多數層之積層構造。
導電層20位於半導體基板10之領域20a上。該導電層20相對於構成該半導體基板10之積體電路的配線圖案電性連接著。形成導電層20的材料可舉例如：鋁(Al)、銅(Cu)、Al－Cu、Al－Si、及Al－Si－Cu等金屬材料。導電層20的形成厚度設定為例如0.2[μm]以上2.0[μm]以下。
鈍化層30係可發揮作為降低半導體元件X1之腐蝕的保護層的功能者。該鈍化層30除了位於導電層20之形成領域20a上的開口部30A以外，幾乎遍及整面。該開口部30A往厚度方向貫穿鈍化層30。該開口部30A的平面視形狀，就緩和應力的觀點來看可為略圓形狀，而就製造成本的觀點來 看則可為n角形狀(n為4以上之自然數)。形成鈍化層30的材料可舉例如：氮化硅、氧化硅、及聚醯亞胺等電性絕緣材料。在第1實施態樣中，鈍化層30形成為亦可覆蓋導電層20之一部分(外周領域)。
障壁金屬層40設於導電層20上。該障壁金屬層40隔著開口部30A電性連接於導電層20。第1實施態樣的障壁金屬層40係含有磷的鎳(Ni)的單層構造。該障壁金屬層40係構造成其上面40a位於較鈍化層30之上面30a更為上方之處。又，第1實施態樣的障壁金屬層40亦往開口部30A周緣之鈍化層30上延伸。該障壁金屬層40中，相對於鈍化層30之上面30a的厚度，係從平面視的周端往中央增大。另外，障壁金屬層40的磷含有率為5[wt%]以上10[wt%]以下(暨所謂的中磷鎳)。該範圍的障壁金屬層40的硬度，在例如維氏硬度中係為500[HV]以上600[HV]以下。該維氏硬度係經JIS規格Z2244：2003所規定，且該規格係以ISO規格6507－1：1997為依據。
又，第1實施態樣的障壁金屬層40係構造成使富磷部位40A(磷含有率為10[wt%]以上之部位)少量存在於其焊料凸塊50側之表面部，且該富磷部位40A係藉由構成該障壁金屬層40之鎳的一部分往焊料凸塊50側擴散而產生者。該富磷部位40A之厚度係形成為，焊料凸塊50的形成領域(障壁金屬層40之上面40a與焊料凸塊50相對的領域)之周緣部40c的厚度大於焊料凸塊50的形成領域之中央部40b的厚度。例如，該富磷部位40A中，中央部40b的厚度平均值設定為 10[nm]以上150[nm]以下，且周緣部40c的厚度平均值設定為300[nm]以上800[nm]以下。又，該富磷部位40A之平面視的周端40Aa亦往開口部30A周緣之鈍化層30上延伸。該焊料凸塊50的形成領域之中央部40b可舉，在相對於障壁金屬層40之上面40a的焊料凸塊50的領域當中，包含障壁金屬層40的中心，且障壁金屬層40對導電層20的厚度T40 大致一定的部位之上面40a。在此，大致一定係指，相對於在平面視中位於鈍化層30之開口部30A內側的障壁金屬層40的厚度T40 之平均值，厚度T40 的值為80%以上120%以下的範圍。該焊料凸塊50的形成領域之周緣部40c係，在相對於障壁金屬層40之上面40a的焊料凸塊50的領域當中，位於從周端40Aa到鈍化層30之開口部30A內側附近之間的部位。該周緣部40c的位置可舉，從周端40Aa往鈍化層30之開口部30A中心側移動2.5[μm]以下的領域。
該富磷部位40A比起障壁金屬層40含有更多的磷，因此電阻率會增大，故若以例如電子掃描型顯微鏡(SEM)觀察，則可觀察出其發光度不同。又，就更提高對外在環境之耐腐蝕性的觀點來看，該富磷部位40A的厚度中，位於鈍化層30之上面30a之部位的厚度最好是比位於開口部30A上之部位的厚度大。另外，本發明之障壁金屬層40亦會有例如，磷含有率雖比其他部位相對較大，但磷含有率卻不到10[wt%]，使得富磷部位40A實質上不存在的情形，或是僅形成薄薄地一部分富磷部位40A的情形。
第1實施態樣中，使用電場發射式奧杰電子能譜法 (Field Emission Auger Electron Spectroscopy；FE－AES)測定形成障壁金屬層40之組成原子的各別含有量。更具體而言，首先，從半導體元件X1取出部分半導體基板10、部分導電層20、部分鈍化層30、及一組障壁金屬層40及焊料凸塊50，來作為測定試料。接著，露出該測定試料之截面，使之包含平面視中的焊料凸塊50之中心。然後，對該測定試料之截面照射電子線，並使用AES法進行該截面的表面分析，來測定形成障壁金屬層40之組成原子的各別含有量。如此一來，即可測出形成障壁金屬層40之組成原子的各別含有量。
焊料凸塊50位於障壁金屬層40上。該焊料凸塊50相對於障壁金屬層40電性連接著。該焊料凸塊50形成為可覆蓋障壁金屬層40之表面全體。就導電性及對障壁金屬層40之密著性的觀點來看，形成焊料凸塊50的材料可舉例如：Pb－Sn(錫)系焊料等含鉛焊料；含有Sn、Ag、Cu、Bi(鉍)、In(銦)、Zn(鋅)、Ni、Ge(鍺)、及Au等任一種金屬而構成之無鉛焊料；銀硬焊；銅硬焊；磷銅硬焊；黃銅硬焊；鋁硬焊；鎳硬焊。就接合強度或耐環境性的觀點來看，形成焊料凸塊50的該等材料當中，特別是以無鉛焊料為佳。在此，無鉛焊料係指鉛含有量為0.10[wt%]以下的焊料，且該數值係JIS規格Z3282：2006或ISO/TC44/SC12所規定者。該焊料凸塊50的尺寸可舉例如平面視的直徑為25[μm]以上85[μm]以下的範圍。
又，第1實施態樣的障壁金屬層40與焊料凸塊50之間， 設有金屬間化合物層60。該金屬間化合物層60係藉由形成障壁金屬層40之鎳與形成焊料凸塊50之焊料擴散而形成的。該金屬間化合物層60的厚度係在可確保適當接合之範圍內，例如，4.0[μm]以下，形成相當小的厚度。另外，形成金屬間化合物層60的材料，例如，在採用含有磷的Ni作為障壁金屬層40，且採用含有銅的無鉛焊料作為焊料凸塊50的情況下，可舉(Cu,Ni)6 Sn5 。
在本說明書中，將障壁金屬層40之上面40a當中隔著金屬間化合物層60接合於焊料凸塊50的部分稱為焊料凸塊50的形成領域。在焊料凸塊50覆蓋障壁金屬層40之表面全體的理想狀態下，該上面40a全體會成為焊料凸塊50的形成領域。
半導體元件X1具有半導體基板10、位於半導體基板10之主面上的導電層20、設於導電層20上並且具有往厚度方向貫穿之開口部30A的鈍化層30、設置成用以堵塞開口部30A並且隔著開口部30A接合於導電層20的障壁金屬層40、及形成於障壁金屬層40上的焊料凸塊50。
在此，尤其是第1實施態樣中，障壁金屬層40位於焊料凸塊50側之表面部，且含有磷含有率相對較大的富磷部位40A。該富磷部位40A中，焊料凸塊50的形成領域之周緣部40c的厚度大於該形成領域之中央部40b的厚度，而具有下述所示之特有效果。
即，半導體元件X1中，藉由相對縮小富磷部位40A在外部空氣相對較難侵入的中央部40b的厚度，可充分確保障 壁金屬層40與焊料凸塊50之接合部分的機械性強度。
又，藉由相對增大富磷部位40A在外部空氣相對較易侵入的周緣部40c的厚度，亦可充分確保障壁金屬層40(甚至是導電層20)的耐腐蝕性。
因此，半導體元件X1可成為在機械性信賴性及電性信賴性兩方面均優異者。
在半導體元件X1中，如第1A圖所示，障壁金屬層40以亦往開口部30A周緣之鈍化層30上延伸形成為佳，藉此，可更減少外部空氣從障壁金屬層40與鈍化層30之間侵入的情形，而可減少障壁金屬層40(甚至是導電層20)產生腐蝕的情形。如此一來，藉由令障壁金屬層40亦往開口部30A周緣之鈍化層30上延伸形成，即可在半導體元件X1中，進一步提高電性信賴性。
在半導體元件X1中，以藉由無電電鍍鎳形成障壁金屬層40為佳，藉此，可減少形成障壁金屬層40上所形成之焊料凸塊50的導電性材料往導電層20擴散的情形。
以下，邊參照第3A圖~第5C圖邊說明第1實施態樣之半導體元件X1的製造方法。另外，第1實施態樣中，採用鋁作為形成導電層20的材料，且採用無電電鍍鎳層作為障壁金屬層40，並採用焊料膏P作為導電性構件來進行說明。
<導電層形成步驟>
半導體元件X1的製造方法中，首先，如第3A圖所示，於半導體基板10上形成導電層20，以使該導電層20相對於構成該半導體基板10之積體電路的配線圖案(未圖示)電性 連接。具體而言，首先，藉由成膜技術形成導電膜。接著，藉由微細加工技術將該導電膜加工成期望的圖案，以形成導電層20。在此，成膜技術可舉例如濺鍍法、蒸著法，且微細加工技術可舉例如使用光刻的方法。
<鈍化層形成步驟(保護層形成步驟)>
如第3B圖所示，於半導體基板10及導電層20上形成具有往厚度方向貫穿之開口部30A的鈍化層30。具體而言，首先，藉由成膜技術形成鈍化層30，以使該鈍化層30覆蓋半導體基板10及導電層20全體。接著，藉由微細加工技術於鈍化層30形成開口部30A，並使電極層20之一部分露出，以形成具有開口部30A的鈍化層30。在此，成膜技術可舉例如濺鍍法、蒸著法，且微細加工技術可舉例如使用光刻的方法。
<殘渣除去步驟>
如第3C圖所示，藉由例如濕式蝕刻法除去殘留於形成有導電層20及鈍化層30之半導體基板10的無機殘渣或有機殘渣。具體而言，係藉由於蝕刻液中浸漬預定時間來進行各種殘渣的除去。另外，用以除去無機殘渣的蝕刻液可舉例如含有氟化氫、硫酸、及氯化氫的溶液，且，用以除去有機殘渣的溶液可舉例如，乙醇、異丙醇、及丙酮等溶液。另外，亦可藉由O2 灰化法等取代濕式蝕刻法來進行有機殘渣的除去。
<第1水洗步驟>
如第4A圖所示，對業經殘渣除去步驟的半導體基板10 進行水洗。具體而言，係藉由將業經殘渣除去步驟的半導體基板10浸漬於洗淨用水中來進行水洗。
<著鋅處理步驟>
如第4B圖所示，對業經第1水洗步驟的半導體基板10施行著鋅處理。具體而言，係將業經第1水洗步驟的半導體基板10於著鋅處理液中浸漬預定時間。該著鋅處理液中含有鋅，使開口部30A的導電層20的鋁取代成鋅之後，再使鋅堆積，藉此在該導電層20之表面形成鋅膜21。另外，亦可反覆進行著鋅處理直到鋅膜21堆積至預定膜厚為止。
<障壁金屬層形成步驟>
如第4C圖所示，於施有著鋅處理之半導體基板10的導電層20上形成作為障壁金屬層40之無電電鍍鎳層。具體而言，係將施有著鋅處理之半導體基板10於無電電鍍鎳液中浸漬預定時間。在該無電電鍍鎳液中，使導電層20之表面所形成之鋅膜21的鋅與無電電鍍鎳液中的鎳進行取代之後，再使鎳堆積，藉此在該導電層20上形成無電電鍍鎳層(障壁金屬層40)。另外，無電電鍍鎳液可舉例如，含有作為還原劑之次亞磷酸納等，並且含有作為鎳鹽之硫酸鎳或氯化鎳等的溶液。就減少對半導體之影響的觀點來看，該無電電鍍鎳液中，以含有作為鎳鹽之硫酸鎳的溶液為佳。又，就更有效率地進行無電電鍍鎳的觀點來看，無電電鍍鎳液的氫離子指數(pH)的值最好是藉由氨等pH調整劑將pH值調整至4以上5以下的範圍。
<第2水洗步驟>
與第1水洗步驟同樣地，對業經障壁金屬層形成步驟的半導體基板10進行水洗。具體而言，係藉由將業經障壁金屬層形成步驟的半導體基板10浸漬於洗淨用水中來進行水洗。
<有機被膜形成步驟>
如第5A圖所示，於形成有無電電鍍鎳層(障壁金屬層40)之半導體基板10的該無電電鍍鎳層上形成有機被膜70。具體而言，首先，將形成有無電電鍍鎳層(障壁金屬層40)之半導體基板10於有機溶液中浸漬預定時間。接著，在使有機溶液附著於障壁金屬層40之表面的狀態下進行乾燥，藉此形成有機被膜70。有機溶液可舉例如，含有純水、脂環族酸、及脂肪族胺衍生物的溶液。第1實施態樣中，該有機溶液的蒸發溫度設定為例如200[℃]以上240[℃]以下。另外，有機被膜70的蒸發溫度的測定係藉由示差掃描熱析儀(型號：DSC－6200、Seiko Instruments製)，以10[℃/min]之昇溫速度在空氣環境中進行。
<導電性構件配置步驟>
如第5B圖所示，於業經有機被膜形成步驟的半導體基板10的有機被膜70上配置(或塗佈)作為導電性構件之焊料膏P。具體而言，藉網板引刷等進行印刷，藉此令焊料膏P配置於位於業經有機被膜形成步驟的半導體基板10之障壁金屬層40上的有機被膜70上。焊料膏P可舉融點低於有機被膜70之蒸發溫度者。該焊料膏P的融點溫度可採用例如160[℃]以上230[℃]以下的範圍當中，低於有機被膜70之蒸 發溫度的溫度。又，就耐環境性的觀點來看，焊料膏P以Sn/3.0Ag/0.5Cu等無鉛焊料為佳。另外，焊料膏P的融點採用的是固相線溫度的值。
<凸塊形成步驟>
如第5C圖所示，以預定溫度加熱業經導電性構件配置步驟的半導體基板10，藉此在障壁金屬層40上形成焊料凸塊50。具體而言，首先，將塗佈有焊料膏P的半導體基板10配置於裝設有加熱器的迴焊爐內，並藉由該加熱器進行加熱。在該迴焊爐內以例如245[℃]以上的溫度進行加熱，以形成略球狀的焊料凸塊50，加熱時間為例如可使有機被膜70全部揮發的所需時間。
根據本半導體元件X1的製造方法，由於障壁金屬層40之中央部40b上所形成之有機被膜70的周圍被障壁金屬層40及焊料膏P所包圍，故比起位於靠近外在環境之處的周緣部40c上所形成之有機被膜70，可相對延長揮發所需時間。因此，根據本半導體元件X1的製造方法，比起周緣部40c，可減少構成中央部40b的障壁金屬層40的例如Ni等金屬往焊料凸塊50內擴散的情形，故中央部40b的富磷部位40A之厚度可形成比周緣部40c小的厚度。因此，本半導體元件X1的製造方法中，可縮小障壁金屬層40之中央部40b的富磷部位40A之厚度，並且周緣部40c的富磷部位40A之厚度可形成比中央部40b大的厚度。
又，根據第1實施態樣之製造方法，可減少相對較脆的金屬間化合物層60(例如(Cu,Ni)6 Sn5 )過厚地形成在障壁金 屬層40與焊料凸塊50之界面的情形。藉此，可更提高所製造之半導體元件X1的信賴性。
<第2實施態樣>
第6A圖係顯示本發明第2實施態樣之半導體元件X2之概略構造的主要部分截面圖。第6B圖係放大顯示第6A圖之一部分的截面圖。
半導體元件X2在具有取代半導體元件X1之障壁金屬層40的障壁金屬層41的這點上與半導體元件X1不同。關於半導體元件X2的其他構造，均與前述半導體元件X1相同。
障壁金屬層41形成於鈍化層30之開口部30A的導電層20上。該障壁金屬層41相對於導電層20電性連接著。第2實施態樣之障壁金屬層41係第1層42與第2層43之積層構造，該第1層42係以第1磷含有率含有磷的鎳，且該第2層43係以第2磷含有率含有磷的鎳。該第2磷含有率小於第1磷含有率。又，障壁金屬層41係構造成其最上面41a位於較鈍化層30之上面30a更為上方之處。在此，第1磷含有率宜設定為10[wt%]以下。
又，第2實施態樣的障壁金屬層41之第1層42及第2層43以亦往開口部30A周緣之鈍化層30上延伸形成為佳。另外，障壁金屬層41之第1層42的磷含有率(第1磷含有率)設定為例如5[wt%]以上10[wt%]以下(暨所謂的中磷鎳)。該範圍的障壁金屬層41之第1層42的硬度，在例如維氏硬度中係為500[HV]以上600[HV]以下。又，障壁金屬層41之第2層43的磷含有率(第2磷含有率)設定為例如1[wt%]以上5[wt%]以 下(暨所謂的低磷鎳)。該範圍的障壁金屬層41之第2層43的硬度，在例如維氏硬度中係為700[HV]以上1000[HV]以下。
又，第2實施態樣的障壁金屬層41係構造成使富磷部位41A(磷含有率為10[wt%]以上之部位)少量存在於其焊料凸塊50側之表面部，且該富磷部位41A係藉由構成該障壁金屬層41之鎳的一部分往焊料凸塊50側擴散而產生者。
在第2實施態樣之半導體元件X2中，障壁金屬層41的磷含有率比富磷部位41A小，且具有第1層42及第2層43。該第1層42的磷含有率比第2層43大。又，該第1層42在鈍化層30之開口部30A中，位於較第2層43更靠近導電層20側之處。如此一來，令位於導電層20側的第1層42的磷含有率大於第2層43的磷含有率，可在半導體元件X2中更提高障壁金屬層41的耐腐蝕性。又，半導體元件X2中，過度縮小磷含有率可減少障壁金屬層41之硬度過度提高的情形，且可減少在鈍化層30產生裂痕或剝落的情形。因此，半導體元件X2在提高機械性信賴性及電性信賴性方面是合適的。又，本構造在減少富磷層41A之厚度增大的情形方面亦是合適的。
又，第6A圖等所示之半導體元件X2中，障壁金屬層41之第1層42液形成於開口部30A周緣之鈍化層30上，故可充分減少焊料凸塊50的形成領域之周緣部41c的耐腐蝕性降低的情形。
以下，邊參照第7A圖、第7B圖邊說明第2實施態樣之半導體元件X2的製造方法。半導體元件X2的製造方法中，形成半導體元件X2之障壁金屬層41的障壁金屬層形成步驟 與半導體元件X1的製造方法不同。關於半導體元件X2的其他步驟，均與前述半導體元件X1的製造方法相同。
<障壁金屬層形成步驟>
首先，如第7A圖所示，於施有著鋅處理之半導體基板10的導電層20上形成作為障壁金屬層41之第1層42的無電電鍍鎳層。具體而言，首先，將施有著鋅處理之半導體基板10於第1無電電鍍鎳液中浸漬預定時間。在該無電電鍍鎳液中，使導電層20之表面所形成之鋅膜的鋅與無電電鍍鎳液中的鎳進行取代之後，再使鎳堆積，藉此在該導電層20上形成無電電鍍鎳層(障壁金屬層41之第1層42)。另外，第1無電電鍍鎳液可舉，含有作為還原劑之次亞磷酸納等，並且含有作為鎳鹽之硫酸鎳或氯化鎳等的溶液等。就減少對半導體之影響的觀點來看，該無電電鍍鎳液中，以含有作為鎳鹽之硫酸鎳的溶液為佳。又，就更有效率地進行無電電鍍鎳的觀點來看，第1無電電鍍鎳液的氫離子指數(pH)的值最好是藉由氨等pH調整劑將pH值調整至4以上5以下的範圍。
接著，如第7B圖所示，於第1層42上形成作為第2層43之無電電鍍鎳層。具體而言，除了採用第2無電電鍍鎳液取代第1無電電鍍鎳液以外，均與前述障壁金屬層41之第1層42的形成方法相同。第2無電電鍍鎳液可舉，含有作為還原劑之次亞磷酸納等，並且含有作為鎳鹽之硫酸鎳或氯化鎳等的溶液等。就減少對半導體之影響的觀點來看，該無電電鍍鎳液中，以含有作為鎳鹽之硫酸鎳的溶液為佳。又， 第2無電電鍍鎳液與第1無電電鍍鎳液不同，係調合成可降低析出之磷的比例。此外，就更有效率地進行無電電鍍鎳的觀點來看，第2無電電鍍鎳液的pH的值最好是藉由氨等pH調整劑將pH值調整至6~7的範圍。
第2實施態樣之半導體元件X2的製造方法可發揮與第1實施態樣之半導體元件X1的製造方法相同的效果。
<第3實施態樣>
第8圖係顯示本發明第3實施態樣之組裝構造體Y之概略構造的主要部分截面圖。
第3實施態樣之組裝構造體Y係將第1實施態樣之半導體元件X1組裝於電路基板80者。該組裝構造體Y包含有半導體元件X1及電路基板80。另外，第3實施態樣中，係採用半導體元件X1舉例說明，但亦可將半導體元件X1更換成半導體元件X2。
在此，電路基板80具有基板81、電路圖案82、墊部83、功能元件(未圖示)。
基板81係可發揮作為電路圖案82及墊部83之支撐母材的功能者。
電路圖案82電性連接於未圖示之功能元件，並形成於基板81上。形成電路圖案82之材料可舉例如：Al、Cu、Al－Cu、Al－Si、及Al－Si－Cu等金屬材料。
墊部83係具有電性連接於半導體元件X1之導電部20之功能的部位。該墊部83電性連接於電路圖案82。於該墊部83隔著焊料凸塊50組裝有半導體元件X1。
由於組裝構造體Y組裝著半導體元件X1，故可享有半導體元件X1具有的效果。因此，組裝構造體Y可成為在機械性信賴性及電性信賴性兩方面均優異者。
以上，表現出本發明之具體的第1~第3實施態樣，但本發明不受限於此，可在不脫離發明思想的範圍內進行各種變更。
本發明之第1實施態樣之半導體元件X1中，障壁金屬層40之富磷部位40A在中央部40b具有大略均勻之厚度。本發明之半導體元件X1不受限於前述構造。例如，如第9A圖、第9B圖所示，障壁金屬層40之富磷部位40A亦可在中央部40b具有具預定厚度的第1部位40Ab1 及厚度比該第1部位40Ab1 小的第2部位40Ab2 。
又，如第10A圖及第10B圖所示，鈍化層30之富磷部位40A以外的部位亦可貫穿富磷部位40A並接合於金屬間化合物層60。此種情況下，可在該領域40d中更提高障壁金屬層40與焊料凸塊50之接合部分的機械性強度，故可成為機械性信賴性更優異者。
本發明之第1實施態樣之半導體元件X1中，富磷部位40A形成於障壁金屬層40之焊料凸塊50側。本發明之半導體元件X1不受限於前述構造，例如，如第11圖所示，富磷部位40A亦可僅位於周緣部40c。即使是在此種情況下，亦可發揮與半導體元件X1相同的效果。再加上，此種情況下，富磷部位40A並未設於中央部40b，可更進一步提高障壁金屬層40與焊料凸塊50之接合部分的機械性強度。
以上第1~第3實施態樣中，說明了具有富磷部位之半導體元件。
然而，第1實施態樣中說明的製造方法亦可應用於製造在障壁金屬層40未具有富磷部位的半導體元件，此種情況下，可使金屬間化合物層60之厚度變薄。
以下，將其具體內容作為第4實施態樣來說明。
<第4實施態樣>
本發明之第4實施態樣之半導體元件X3的製造方法包含有：於障壁金屬層40上形成有機被膜70的有機被膜形成步驟；於有機被膜70上配置熔點低於有機被膜70之蒸發溫度的焊料膏P的導電性構件配置步驟；使焊料膏P熔融並且使有機被膜70揮發，於障壁金屬層40上形成焊料凸塊50的凸塊形成步驟。
因此，第4實施態樣之製造方法中，即使焊料膏P熔解，在有機被膜70揮發之前的這段期間，亦可減少障壁金屬層40的形成成分(例如，鎳)從障壁金屬層40往焊料膏P擴散的情形。因此，第4實施態樣之製造方法中，可減少相對較脆的金屬間化合物層60(例如(Cu,Ni)6 Sn5 )過厚地形成在障壁金屬層40與焊料凸塊50之界面的情形。藉此，根據第4實施態樣之製造方法可提高所製造之半導體元件X3的信賴性。
第12圖係顯示藉由第4實施態樣之製造方法製作的半導體元件X3之該略構造的主要部分放大截面圖。
又，根據第4實施態樣之製造方法，由於障壁金屬層40上形成有有機被膜70，故無需在作為障壁金屬層40之無電 電鍍鎳層上設置作為防氧化層之金層，即使是僅由無電電鍍鎳層所構成之障壁金屬層40，亦可減少其氧化。
此外，根據第4實施態樣之製造方法，障壁金屬層40無需設置金層，故可減少構成金層的金往焊料凸塊50擴散，使該焊料凸塊50的可濕性降低的情形。
本製造方法係以使障壁金屬層40上的有機被膜70全部揮發為佳，故可減少因過度殘留有機被膜70而降低焊料膏P的可濕性的情形。
本製造方法係形成有機被膜70，以被覆障壁金屬層40全體，故可減少障壁金屬層40全體的氧化，而可減少對焊料膏P之可濕性降低的情形。
本製造方法中，亦於鈍化層30的開口部30A之周緣部上形成障壁金屬層40，故可減少導電層20的腐蝕等產生。
本製造方法中，障壁金屬層40係藉由無電電鍍鎳所形成，故可減少形成障壁金屬層40之鎳成分往該障壁金屬層40上所形成之焊料凸塊50側擴散的情形。又，由於障壁金屬層40含有磷，故可提高形成障壁金屬層40之無電電鍍鎳的耐腐蝕性。
又，在藉由第4實施態樣之製造方法所製作的半導體元件X3中，焊料凸塊50與障壁金屬層40之間雖存在有藉由形成焊料凸塊50之焊料與形成障壁金屬層40之鎳擴散而形成的金屬間化合物層60，但可使其厚度變薄。即，該金屬間化合物層60的厚度並非過厚的厚度(例如4.0[μm]以上)，而是在可確保適當接合之範圍內的相當薄的厚度(例如2.0[μ m]以下)。又，可減少如以往般會形成局部性厚塊的情形，故可更提高厚度均勻性。另外，形成金屬間化合物層60的材料可舉例如(Cu,Ni)6 Sn5 。
以上，藉由具體的第4實施態樣表現出本發明，但本發明不受限於此，可在不脫離發明思想的範圍內進行各種變更。
例如，在第4實施態樣之製造方法中，亦可使焊料凸塊50含有有機被膜70之揮發成分。此種製造方法亦可發揮與前述相同的效果。又，若在該情況中含有作為有機被膜70之揮發成分的脂環族胺，則構成胺的N可發揮與松香焊劑相同的功能，故可得到與使用松香焊劑時相同的效果。
10‧‧‧半導體基板
20‧‧‧導電層
20a‧‧‧形成領域
21‧‧‧鋅膜
30‧‧‧鈍化層
30a‧‧‧上面
30A‧‧‧開口部
40‧‧‧障壁金屬層
40A‧‧‧富磷部位
40Aa‧‧‧周端
40Ab1 ‧‧‧第1部位
40Ab2 ‧‧‧第2部位
40a‧‧‧上面
40b‧‧‧中央部
40c‧‧‧周緣部
40d‧‧‧領域
41‧‧‧障壁金屬層
41A‧‧‧富磷部位
41a‧‧‧最上面
41c‧‧‧周緣部
42‧‧‧第1層
43‧‧‧第2層
50‧‧‧焊料凸塊
60‧‧‧金屬間化合物層
70‧‧‧有機被膜
80‧‧‧電路基板
81‧‧‧基板
82‧‧‧電路圖案
83‧‧‧墊部
P‧‧‧焊料膏
T40 ‧‧‧厚度
X1‧‧‧半導體元件
X2‧‧‧半導體元件
X3‧‧‧半導體元件
Y‧‧‧組裝構造體
第1A圖係顯示本發明第1實施態樣之半導體元件之概略構造的主要部分截面圖。
第1B圖係放大顯示第1A圖之一部分的截面圖。
第2圖係顯示第1A圖所示之半導體元件之概略構造的平面視圖。
第3A圖係顯示第1A圖所示之半導體元件之製造過程之一步驟的主要部分截面圖。
第3B圖係顯示第3A圖之下一步驟的主要部分截面圖。
第3C圖係顯示第3B圖之下一步驟的主要部分截面圖。
第4A圖係顯示第3C圖之下一步驟的主要部分截面圖。
第4B圖係顯示第4A圖之下一步驟的主要部分截面圖。
第4C圖係顯示第4B圖之下一步驟的主要部分截面圖。
第5A圖係顯示第4C圖之下一步驟的主要部分截面圖。
第5B圖係顯示第5A圖之下一步驟的主要部分截面圖。
第5C圖係顯示第5B圖之下一步驟的主要部分截面圖。
第6A圖係顯示本發明第2實施態樣之半導體元件之概略構造的主要部分截面圖。
第6B圖係放大顯示第6A圖之一部分的截面圖。
第7A圖係顯示第6A圖所示之半導體元件之製造過程之一步驟的主要部分截面圖。
第7B圖係顯示第7A圖之下一步驟的主要部分截面圖。
第8圖係顯示本發明第3實施態樣之組裝構造體之概略構造的主要部分截面圖。
第9A圖係顯示本發明第1實施態樣之半導體元件之變形例的主要部分截面圖。
第9B圖係放大顯示第9A圖之一部分的截面圖。
第10A圖係顯示本發明第1實施態樣之半導體元件之其他變形例的主要部分截面圖。
第10B圖係放大顯示第10A圖之一部分的截面圖。
第11圖係顯示本發明第1實施態樣之半導體元件之另一不同變形例的主要部分截面圖。
第12圖係顯示藉由本發明第4實施態樣之製造方法製作的半導體元件之該略構造的主要部分放大截面圖。
X1‧‧‧半導體元件
10‧‧‧半導體基板
20‧‧‧導電層
30‧‧‧鈍化層
30a‧‧‧上面
40‧‧‧障壁金屬層
50‧‧‧焊料凸塊
60‧‧‧金屬間化合物層

Claims (15)

  1. 一種半導體元件，包含有：基板；導電層，係設於前述基板上者；保護層，係設於前述導電層上且具有開口部者；障壁金屬層，係在前述開口部中接合於前述導電層者；及導電性凸塊，係形成於前述障壁金屬層上者，又，前述障壁金屬層含有磷，且包含前述磷含有率大於其他部分的富磷部位，前述富磷部位位於前述導電性凸塊側之表面部，且前述導電性凸塊的形成領域之周緣部中的前述富磷部位的厚度大於前述形成領域之中央部中的前述富磷部位的厚度。
  2. 如申請專利範圍第1項之半導體元件，其中前述障壁金屬層與前述導電性凸塊之間更包含有金屬間化合物層，該金屬間化合物層係含有前述障壁金屬層之構成材料及前述導電性凸塊之構成材料而構成者，且，前述障壁金屬層中，前述富磷部位以外之部位貫穿前述富磷部位並連接於前述金屬間化合物層。
  3. 一種半導體元件，包含有：基板；導電層，係設於前述基板上者；保護層，係設於前述導電層上且具有開口部者； 障壁金屬層，係在前述開口部中接合於前述導電層者；及導電性凸塊，係形成於前述障壁金屬層上者，又，前述障壁金屬層含有磷，且包含前述磷含有率大於其他部分的富磷部位，前述富磷部位位於前述導電性凸塊側之表面部，且僅位於前述導電性凸塊的形成領域之周緣部。
  4. 如申請專利範圍第1項之半導體元件，其中前述障壁金屬層亦形成於前述開口部周緣之前述保護層上。
  5. 如申請專利範圍第1項之半導體元件，其中前述障壁金屬層的富磷部位以外之部位包含第1部位及第2部位，且磷含有率比前述富磷部位小，前述第1部位位於前述導電層側之表面部，且磷含有率比前述第2部位小。
  6. 一種組裝構造體，包含有：半導體元件，係申請專利範圍第1至5項中任一項者；及基體，係具有配線電極者，且，前述基體上裝設有電性連接於前述配線電極之墊部，又，前述墊部與前述半導體元件之前述導電性凸塊接合。
  7. 一種半導體元件之製造方法，包含有：導電層形成步驟，係於基板主面形成導電層； 保護層形成步驟，係形成覆蓋前述導電層且於前述導電層上具有開口部的保護層；障壁金屬層形成步驟，係形成在前述開口部中接合於前述導電層的障壁金屬層；有機被膜形成步驟，係於前述障壁金屬層上形成有機被膜；導電性構件配置步驟，係於前述有機被膜上配置熔點低於前述有機被膜之蒸發溫度的導電性構件；及凸塊形成步驟，係使前述導電性構件熔融並且使前述有機被膜揮發，於前述障壁金屬層上形成導電性凸塊。
  8. 如申請專利範圍第7項之半導體元件之製造方法，係使前述導電性凸塊含有前述有機被膜之揮發成分。
  9. 如申請專利範圍第8項之半導體元件之製造方法，其中前述有機被膜之揮發成分含有脂環族酸及脂肪族胺衍生物。
  10. 如申請專利範圍第7項之半導體元件之製造方法，係使前述障壁金屬層上的前述有機被膜全部揮發。
  11. 如申請專利範圍第7項之半導體元件之製造方法，係形成前述有機被膜，以被覆前述障壁金屬層全體。
  12. 如申請專利範圍第7項之半導體元件之製造方法，係於前述保護層的前述開口部之周緣部上亦形成前述障壁金屬層。
  13. 如申請專利範圍第7項之半導體元件之製造方法，係藉 由無電電鍍鎳形成前述障壁金屬層。
  14. 如申請專利範圍第13項之半導體元件之製造方法，其中前述障壁金屬層含有磷。
  15. 如申請專利範圍第14項之半導體元件之製造方法，其中前述障壁金屬層形成步驟包含有：第1部位形成步驟，係形成在前述開口部中接合於前述導電層的第1部位；及第2部位形成步驟，係於前述第1部位上形成磷含有率比第1部位小的第2部位。
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