TWI573497B - 抗高溫之銀塗覆基板及其製造方法 - Google Patents

抗高溫之銀塗覆基板及其製造方法 Download PDF

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TWI573497B
TWI573497B TW101126746A TW101126746A TWI573497B TW I573497 B TWI573497 B TW I573497B TW 101126746 A TW101126746 A TW 101126746A TW 101126746 A TW101126746 A TW 101126746A TW I573497 B TWI573497 B TW I573497B
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silver
nickel
tin
layer
copper
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貝格林吉爾 溫 張
瑪吉特 葛拉斯
麥可Ｐ 圖本
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羅門哈斯電子材料有限公司
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Description

抗高溫之銀塗覆基板及其製造方法
本發明係關於含有銅之抗高溫之銀塗覆基板。更具體言之，本發明係關於抗高溫之銀塗覆含銅基板，其係具有改良之銀塗層對含銅基板的黏著性。
由於銀之優異沉積特性，電鍍及無電鍍覆之銀塗層業經用於多種用途，如用於電連接器、印刷電路板、發光二極體之製造中，鍍覆於塑膠上及裝飾件上。當銀係鍍覆於包括銅或銅合金之基板上時，典型係於鍍覆銀之前，將鎳底層施用至該銅或銅合金上。鎳係用作阻擋，以防止銅擴散進入銀中，而且亦可提供改良之表面形貌。為了於鎳上達成黏著性銀層，典型係於鍍覆最終及較厚之銀塗層之前，將薄銀底鍍(strike)層施用於該鎳上。只要適宜地完成該鍍覆製程，典型地，於鍍覆之後短期內或於該元件之使用期內，不會出現鎳與銀間的黏著失敗。
近來，不同工業對於將銀塗層用於高溫用途，典型於150℃以上之溫度使用的興趣已增加。於此等高溫下，由於快速之銅擴散，使用鎳阻擋層是必要的。此外，於此等高溫條件下，可能容易出現銀下之鎳的氧化，導致鎳與銀間的黏著失敗。銀下之鎳於高溫下加速氧化之現象仍未被完全了解。通常，用以增強銀對鎳之黏著性如銀底鍍及鎳表面活化的典型方法尚不能克服於高溫用途中的氧化及黏著問題。
三菱原材料株式會社(Mitsubishi Materials Corp.)之日本專利申請案公開JP2003-293170號揭露了一種高溫電連接器，如用於燃料電池之電流抽取端子(current extraction terminal)，其可用於高溫環境。該導體基體材料可係鐵、鎳或鈷合金。鎳層係鍍覆於該導體基材上，之後將銀鍍覆於該鎳上。該專利公開案揭露該導體於500至960℃之高溫氣氛中不氧化且保持電連續性。儘管存在具有具銀及鎳層之鐵、鎳或鈷合金之基材的物件，且該物件中的鎳於高溫環境中並不氧化，仍需要含有處於鎳上之銀的物件，該物件可對抗於包括銅或銅合金之基材上之高溫用途。
物件係包括含有銅或銅合金之基板、與該含有銅或銅合金之基板相鄰的含鎳層、與該含鎳層相鄰的含錫層、及與該含錫層相鄰的銀層，該銀層係該含錫層之至少二倍厚度。
方法係包括提供含有銅或銅合金之基板；沉積與該含有銅或銅合金之基板相鄰的含鎳層；沉積與該含鎳層相鄰的含錫層；以及沉積與該含錫層相鄰的銀層，該銀層係至少為該錫層之兩倍厚度。
於沉積銀之前，施用與鎳或鎳合金相鄰之錫或錫合金的薄膜係抑制含鎳層之氧化，因此於高溫用途中抑制銀與含銅或銅合金之基板間的黏著失敗。據此，該等物件可用於高溫環境，且對於該銀層之黏著失敗有最小的顧慮。
如貫穿本說明書所使用者，術語「沉積」與「鍍覆」係可互換地使用。術語「組成物」與「浴」係可互換地使用。術語「相鄰」係意指毗鄰或緊靠及結合。不定冠詞「一(a)」和「一(an)」係欲以包括單數及複數兩者。除了上下文中明確另行指出者之外，下述縮寫係具有下述意義：℃=攝氏度；g=公克；ml=毫升；L=公升；ASD=A/dm2=安培/平方公寸；PVD=物理氣相沉積；CVD=化學氣相沉積；PCB=印刷電路板或印刷佈線板；SEM=掃描式電子顯微照片；EDX=EDS=能量分散性X射線光譜術；cm=公分；μm=微米；nm=奈米。
除了特別另行指出者外，全部百分率及比率係基於重量。全部範圍係包括上下限值且可以任何次序組合，除非此數值範圍受限制於邏輯上加總至高為100%。
物件可藉由第1圖表示，其係顯示含銅之基板1，具有與該銅系基板相鄰之含鎳之阻擋層2。含錫之底鍍層3係與該含鎳之阻擋層相鄰，而具有至少二倍於該含錫之底鍍層厚度的銀層4係與該含錫之底鍍層相鄰。視需要地，頂部銀層可具有抗鏽層(未顯示)。該等物件可作為用於多種電子裝置中之元件，諸如彼等其中該物件可曝露於150℃及更高之溫度，或諸如自200℃至600℃之溫度中且仍維持金屬層間良好黏著性的裝置。
一層或多層之鎳或鎳合金係沉積於包括銅之基板上。該鎳係作為阻擋層，以抑制銅擴散進入銀頂層。該基板可 實質上全銅，或可包括一種或多種銅合金，諸如，但不限於，錫/銅、銀/銅、金/銅、銅/鉍、銅/鋅、銅/鎳、錫/銀/銅及錫/銅/鉍。該基板可係具有銅或銅合金層之PCB或介電材料(諸如，塑膠或樹脂材料)。該鎳或鎳合金係沉積為使得該等層係與該基板之銅或銅合金層的表面相鄰，以與該基板之銅或銅合金表面形成介面。通常，該等鎳或鎳合金層係至少0.5μm厚。較佳地，該等鎳或鎳合金層係0.5μm至10μm厚，更佳為1μm至5μm厚。可藉由該技藝中用以將鎳或鎳合金沉積於基板上的傳統方法，而沉積一層或多層之鎳或鎳合金層。此等方法係包括，但不限於，PVD、CVD、電解及無電之金屬鍍覆。此等方法係該技藝及文獻中周知者。較佳地，電解金屬鍍覆係用以將鎳或鎳合金沉積於含銅之基板上。
通常，可於至少0.01 ASD之電流密度完成鎳或鎳合金之電鍍。典型之電流密度係自0.1 ASD至5 ASD，更典型係自0.5 ASD至2 ASD。可使用最少之實驗以調整用於特定基板之電流密度。所使用之電鍍製程係傳統製程。
可藉由使用任何適當之溶液可溶(solution-soluble)鎳化合物，典型係水溶性鎳鹽，而提供該鍍覆組成物中之鎳離子。此等鎳化合物係包括，但不限於，硫酸鎳、氯化鎳、胺基磺酸鎳及磷酸鎳。鎳化合物之混合物可用於該鍍覆組成物中。此等混合物可具有相同之金屬但為不同化合物的金屬化合物，如硫酸鎳與氯化鎳的混合物。該等鎳化合物係加入該鍍覆組成物中，其量係足以於該鍍覆組成物 中提供0.1 g/L至150 g/L，典型自0.5 g/L至100 g/L，且更典型自1 g/L至70 g/L的鎳離子濃度。
任何廣泛多種之電解質，包括酸及鹼，可用於鎳鍍覆組成物中。電解質係包括，而非限於，烷磺酸如甲烷磺酸、乙烷磺酸及丙烷磺酸；烷醇磺酸；芳基磺酸如甲苯磺酸、苯磺酸及酚磺酸；含胺基之磺酸如醯胺基磺酸；胺基磺酸；無機酸；羧酸如甲酸及鹵乙酸；氫鹵酸；以及焦磷酸鹽。酸式鹽及鹼式鹽亦可用作該電解質。再者，該電解質可含有酸之混合物、鹼之混合物、或一種或多種酸與一種或多種鹼之混合物。此等電解質係通常可自多種源如阿德瑞希化學公司(Aldrich Chemical Company,Milwaukee,Wisconsin)商購者。
視需要地，廣泛多種界面活性劑可用於鎳鍍覆組成物中。可使用任何之陰離子性、陽離子性、兩性及非離子性之界面活性劑，只要其不干擾鎳鍍覆之效能即可。所包括之界面活性劑可係傳統之量如該技藝中習知者。
視需要地，鎳鍍覆組成物可含有一種或多種額外成分。此等額外成分係包括，而非限於，光亮劑、晶粒細化劑及耐久性增強劑。此等額外成分係該技藝中習知者且可以傳統之量使用。
鎳鍍覆組成物可視需要含有緩衝劑。例示性緩衝劑係包括，但不限於，硼酸鹽緩衝劑(如硼砂)、磷酸鹽緩衝劑、檸檬酸鹽緩衝劑、碳酸鹽緩衝劑及氫氧化物緩衝劑。所使用之緩衝劑的用量係足以將鍍覆組成物之pH維持於所欲 水準的量，該量係熟識該技藝之人士所熟知者。
一種或多種合金化金屬可包括於鎳鍍覆組成物中。此等合金化金屬係包括，而非限於，錫、銅及鉍。鎳-磷係較佳之合金。此等金屬係以其為該技藝中周知之溶液可溶鹽而提供。可以傳統量可包括於該鎳鍍覆組成物中，以提供鎳合金沉積物。
適當之電解鎳鍍覆浴係可商購之，且多數係於文獻中揭露者。例示性可商購之電解鎳浴係NICKEL GLEAMTM電解鎳產品及NIKALTM SC電解鎳產品，兩者皆可自羅門哈斯電子材料公司(Rohm and Haas Electronic Materials,LLC,Marlborough,MA,U.S.A.)獲得。適當之電解鎳鍍覆浴之其他實例係於美國專利第3,041,255號中揭示之瓦特型浴(Watts-type baths)。
無電鎳鍍覆組成物可包括或不包括還原劑。典型地，無電鎳鍍覆組成物包括還原劑。此等還原劑係包括，但不限於，次磷酸鈉、次磷酸鉀、硫脲及硫脲衍生物、乙內醯脲及乙內醯脲衍生物、氫醌及氫醌衍生物、間苯二酚、以及甲醛及甲醛衍生物、DEA(正二乙基-胺硼烷)、硼氫化鈉及肼。此等還原劑可以傳統量使用，如自0.1 g/L至40 g/L。可商購之無電鎳組成物的實例係包括DURAPOSITTM SMT 88無電鎳及NIPOSITTM PM 980及PM 988無電鎳。全部係可自羅門哈斯電子材料公司購得。
鎳鍍覆組成物可具有範圍為1至14之pH(典型係自1至12，更典型係自1至8)。鎳鍍覆組成物於鍍覆過程中之 工作溫度可係自10℃至100℃，或諸如自20℃至50℃。
於鎳或鎳合金沉積之後，將一層或多層之錫或錫合金底鍍層相鄰於一層或多層之鎳或鎳合金沉積。可藉由該技藝中使用之傳統方法如電解、無電或浸潤之錫或錫合金鍍覆，而沉積錫或錫合金。較佳係將錫或錫合金電鍍或無電鍍覆而與該鎳或鎳合金相鄰。更佳係將錫或錫合金電鍍成與鎳或鎳合金層相鄰。錫或錫合金層係具有至少0.01μm之厚度，較佳係0.01μm至2μm，更佳係自0.1μm至1μm。
適當之錫及錫合金鍍覆浴可係酸性或鹼性。例示性酸性錫浴係含有一種或多種溶液可溶錫化合物、一種或多種酸性電解質、以及視需要之一種或多種添加劑。適當之錫化合物係包括，但不限於，鹽類，如鹵化錫、硫酸錫、烷磺酸錫如甲烷磺酸錫、芳基磺酸錫如苯磺酸錫、酚磺酸錫及甲苯磺酸錫及烷醇磺酸錫。典型地，該錫化合物係硫酸錫、氯化錫、烷磺酸錫或芳基磺酸錫，更典型係硫酸錫或甲烷磺酸錫。於此等組成物中，錫化合物之量典型係提供5 g/L至150 g/L，更典型30 g/L至80 g/L之範圍內之錫離子含量的量。可使用錫化合物之混合物。
任何溶液可溶酸性電解質係適用於生產安定之錫電解質，且不對所用之電解質組成物造成負面效應。適當之酸性電解質係包括，但不限於，烷磺酸，如甲烷磺酸、乙烷磺酸及丙烷磺酸，芳基磺酸，如苯磺酸、酚磺酸及甲苯磺酸，硫酸、胺基磺酸，鹽酸，氫溴酸，氟硼酸，及其混合 物。典型地，酸性電解質之量係自10 g/L至400 g/L之範圍(更典型自50 g/L至400 g/L)。
於錫合金鍍覆浴中，除了使用錫外，亦使用一種或多種合金化金屬化合物。適當之合金化金屬係包括，但不限於，鉛、鎳、銅、鉍、鋅、銀、銻及銦。可用之合金化金屬化合物係任何以可溶解形式將金屬提供給電解質組成物者。因此，該等金屬化合物係包括，但不限於，鹽，如金屬鹵化物、金屬硫酸鹽、金屬烷磺酸鹽如金屬甲烷磺酸鹽、金屬芳基磺酸鹽如金屬苯磺酸鹽及金屬甲苯磺酸鹽及金屬烷醇磺酸鹽。該合金化金屬化合物之選擇及電解質組成物中存在之該合金化金屬化合物的量係取決於，舉例而言，待沉積錫-合金，其係熟知該技藝之人士所周知者。典型之錫合金係錫/銅、錫/鉍、錫/銀、錫/鋅、錫/銀/銅及錫/銀/鉍。
一種或多種其他添加劑可用於錫或錫合金電鍍浴中，如還原劑、晶粒細化劑如羥基芳族化合物及其他濕潤劑、光亮劑及抗氧化劑。亦可使用添加劑之混合物。
還原劑可加入錫及錫-合金電解質組成物中，以輔助將錫保持為可溶性之二價狀態。適當之還原劑係包括，但不限於，氫醌及羥基化之芳族化合物，如間苯二酚及兒茶酚。適當之還原劑係，舉例而言，彼等於美國專利第4,871,429號中揭露者。該還原劑之量典型係自0.1 g/L至5 g/L。
可藉由將光亮劑加入錫及錫-合金電解質組成物中，而獲得光亮之沉積物。此等光亮劑係熟知該技藝自人士所周 知者。適當之光亮劑係包括，但不限於，芳族醛類如萘甲醛、苯甲醛、烯丙基苯甲醛、甲氧基苯甲醛及氯苯甲醛，芳族醛類之衍生物如苄基丙酮及亞苄基丙酮(benzylidine acetone)，脂族醛類如乙醛或戊二醛，以及酸類如丙烯酸、甲基丙烯酸及吡啶甲酸。典型地，光亮劑之用量係0.1 g/L至3 g/L。
適當之非離子性界面活性劑或濕潤劑係包括，但不限於，含有一個或多個最多具7個碳原子之烷基之脂族醇的相對低分子量之環氧乙烷(EO)衍生物，或最多具兩個芳環之芳族醇的環氧乙烷衍生物，其中該芳環可經稠合且其可經最多具6個碳原子之烷基取代。該脂族醇可係飽和或不飽和。呈環氧乙烷之衍生前，該芳族醇典型係具有最多20個碳原子。該脂族醇及芳族醇可進一步經，舉例而言，硫酸根基或磺酸根基取代。典型地，此等非離子性界面活性劑或濕潤劑之加入量係0.1 g/L至50 g/L。
羥基芳族化合物或其他濕潤劑可加入此等電解質組成物中，以提供進一步之晶粒細化。可加入此等細化劑，以進一步改良沉積物外觀及操作電流密度範圍。適當之其他濕潤劑係包括，但不限於，烷氧基化物如聚乙氧基化胺JEFFAMINETM T-403或TRITONTM RW，硫酸化烷基乙氧基化物如TRITONTM QS-15，以及明膠或明膠衍生物。此等晶粒細化劑之可用的量係熟知該技藝之人士所周知者，且典型係自0.01 ml/L至20 ml/L。
視需要地，電解質組成物中可採用抗氧化劑化合物， 以最小化或防止二價錫的氧化之發生，例如，從二價氧化變四價。適當之抗氧化劑化合物係包括，舉例而言，二羥基苯，及基於元素週期表之第IVB族、第VB族及第VIB族元素如釩、鈮、鉭、鈦、鋯及鎢的多價化合物。典型地，此等抗氧化劑化合物係以自0至2 g/L的量存在於電解質組成物中。
錫或錫合金係於自20℃至60℃，典型自35℃至45℃之溫度鍍覆。當電鍍該錫或錫合金時，電流密度典型係自0.5 ASD至10 ASD。
隨後，將一層或多層之銀沉積成與錫或錫合金層相鄰。銀層與錫或錫合金層之厚度比為至少2：1，較佳為2：1至30：1，更佳為5：1至25：1。典型地，銀之厚度為至少0.02μm，較佳為0.02μm至60μm，更佳為0.5μm至25μm。可使用傳統方法將銀沉積於錫或錫合金上。典型係藉由電解、無電或浸潤之鍍覆而沉積銀。較佳係藉由電解鍍覆而沉積銀。
可使用傳統之電鍍銀組成物。銀組成物可係含有氰化物之銀組成物或不含氰化物之銀組成物。較佳地，銀浴係含有氰化物之浴。銀離子之來源可包括，而非限於：氰化銀鉀、硝酸銀、硫代硫酸銀鈉、葡萄糖酸銀；銀-胺基酸錯合物，如銀-半胱胺酸錯合物；烷基磺酸銀，如甲烷磺酸銀。可使用銀化合物之混合物。於組成物中，銀離子之濃度典型係2 g/L至40 g/L之量。此等銀化合物通常可自多種來源如阿德瑞希化學公司商購之。可商用之銀鍍覆組成物的 實例係可為SILVER GLOTM 3K銀電鍍浴、SILVERJETTM 300銀電鍍浴、SILVER GLEAMTM 360銀電鍍浴、ENLIGHTTM Silver Plate 600及620自羅門哈斯電子材料公司購得者。
廣泛多種傳統界面活性劑如陰離子性、陽離子性、兩性及非離子性界面活性劑可用於銀鍍覆組成物中。可包括傳統量之界面活性劑。銀鍍覆組成物可含有一種或多種額外之傳統成分。此等額外成分係包括，而非限於，電解質、緩衝劑、光亮劑、晶粒細化劑、螯合劑、錯合劑、還原劑、流平劑及耐久性增強劑。此等額外之成分係該技藝中周知者且可以傳統之量使用。
銀鍍覆組成物可具有範圍為1至14之pH(典型係自1至12，且再更典型係自1至8)。於銀鍍覆過程中，銀鍍覆組成物之工作溫度係自10至100℃，或諸如自20至60℃。典型之電流密度係自0.1 ASD至50 ASD，更典型係自1 ASD至20 ASD。
視需要地，可將抗鏽層沉積於銀層上。可使用傳統抗鏽組成物。此等抗鏽材料之商業實例係NO-TARNTM PM 3抗鏽製劑、PORE BLOCKER 100抗鏽製劑及PORE BLOCKERTM 200抗鏽製劑(可自羅門哈斯電子材料公司購得)。
至少為相鄰之與鎳或鎳合金相鄰之錫或錫合金兩倍厚度的銀層抑制該鎳層之氧化，因此抑制於高溫用途中銀與基板間的黏著失敗。錫層與鎳層之介面處形成鎳/錫之金屬間化合物，且錫層與銀層之介面處形成錫/銀之金屬間化合物。未受縛於理論，錫/銀之金屬間化合物的形成可能改變 銀層之微結構，並防止氧到達鎳或鎳合金表面，而鎳/錫之金屬間化合物的形成可能增加鎳或鎳合金層之抗氧化性。可使用該技藝中周知之標準EDS或EDX分析方法來量測鎳或鎳合金層之氧化。該等物件可用於高溫環境中，而無需過多考慮銀層之黏著失敗。通常，該等物件可用作PCB、電連接器、發光二極體(LED)、電動車以及其中銀層可能曝露於150℃或更高溫度之其他用途的零件或元件。
[實施例]
下述實施例係用以例示性說明本發明，但並未欲以限制本發明之範疇。
實施例1(比較性)
將三片經清潔之銅系試片(銅或銅/鋅)2cm×5cm置於具有表1中揭露之配方的水性鎳電鍍浴中。
將該等試片連結至整流器，且相對電極係經鍍鉑之鈦電極。於鎳電鍍過程中，鎳鍍覆浴之溫度係維持於30℃。電流密度為1 ASD。進行電鍍，直至於每一銅試片上沉積2 μm厚之鎳層。自鍍覆浴中移除該等試片，於室溫以去離子水沖洗。
隨後，將該等試片置於包括作為銀離子來源之2 g/L氰化銀以及100 g/L氰化鉀之水性銀底鍍浴中。將鍍覆有鎳之銅試片連結至整流器。相對電極係經鍍鉑之鈦電極。於60℃及0.1 ASD之電流密度進行銀電鍍，直至於鎳上沉積0.1μm銀底鍍層。
隨後，將該等試片置於具有表2中揭露之配方的銀電鍍浴中。
將該等試片連結至整流器，且相對電極係經鍍鉑之鈦電極。該銀浴係維持於60℃之溫度。電流密度為2 ASD。進行銀電鍍，直至於銀底鍍層上沉積5μm厚之銀層。
將該等鍍覆有銀之試片自銀電鍍浴中移除，且以去離子水沖洗並於室溫風乾。隨後，使用標準十字割痕(cross-hatch)及膠帶測試來測試每一試片之銀層的黏著性。所測試之全部試片皆顯示良好黏著性。將膠帶自該塗覆有銀之試片剝離之後，未於膠帶上觀察到銀。
隨後，將該等試片於傳統對流烘箱中於200℃存儲1,000小時。藉由允許該等試片冷卻至室溫，隨後進行十字割痕及膠帶測試，而於每200小時檢查銀對試片的黏著性。於400小時之後，該等試片全部顯示差的銀黏著性訊號。於1000小時之後，將該等試片自烘箱移除，並予許其冷卻至室溫。
取每一試片之橫截面，並於配備來自蔡司公司(Zeiss)之EDX之SIGMA SEM掃描式電子顯微鏡下檢查。全部SEM皆顯示於鎳與銀層之介面處有縫隙。第2圖係所檢查之一片銅試片之橫截面的SEM。SEM之頂部係用以固定該樣本以進行橫截面分析的嵌入樹脂。經電鍍之銀層係位於該嵌入樹脂下方，且於高熱存儲過程中形成之該縫隙係見於該銀層與直接位於該銀層下方之鎳層的介面處。銅基材係直接位於該鎳層下方。
實施例2(比較性)
如以上實施例1中描述者製備三片銅系試片，除了將金底鍍層替代銀底鍍層而鍍覆於鎳層之上。該水性金底鍍浴係具有表3中之配方。
該金底鍍浴係維持於40℃之溫度和0.2 ASD之電流密度。進行金電鍍，直至於該鎳層上沉積0.1μm厚之金層。
隨後，使用以上表2中揭露之氰化銀浴，對每一試片電鍍5μm厚之銀層。使用與實施例1中相同之銀鍍覆條件。
將該等鍍覆有銀之試片自銀電鍍浴中移除，且以去離子水沖洗並於室溫風乾燥。隨後，使用標準十字割痕及膠帶測試來測試每一試片之銀層的黏著性。所測試之全部試片皆顯示良好黏著性。將膠帶自該塗覆有銀之試片剝離之後，未於膠帶上觀察到銀。
隨後，將該等試片於傳統對流烘箱中於200℃存儲1,000小時。每200小時，檢查銀對試片的黏著性。於400小時之後，試片全部顯示差的銀黏著性訊號。於1000小時之後，將該等試片自烘箱移除，並予許其冷卻至室溫。
取每一試片之橫截面，於掃描式電子顯微鏡下檢查。全部SEM皆顯示於鎳與金底鍍層之介面處有縫隙。第3圖係所檢查之一片銅試片之橫截面的SEM。SEM顯示於高熱存儲過程中，該銀層與鎳層之間有脫層。
實施例3(比較性)
如以上實施例1中描述者製備三片銅系試片，除了將鈀及鎳合金底鍍層替代銀底鍍層而鍍覆於鎳層之上。水性鈀及鎳合金底鍍浴係具有表4中之配方。
該鈀及鎳合金底鍍浴係維持於60℃之溫度和0.2 ASD之電流密度。進行鈀及鎳合金電鍍，直至於該鎳層上沉積0.1μm厚之合金層。
隨後，使用以上表2中揭露之氰化銀浴對每一試片電鍍5μm厚之銀層。使用與實施例1中相同之銀鍍覆條件。
將該等鍍覆有銀之試片自該銀電鍍浴中移除，且以去離子水沖洗並於室溫風乾。隨後，使用標準十字割痕及膠帶測試來測試每一試片之銀層的黏著性。所測試之全部試片皆顯示良好黏著性。將膠帶自該塗覆有銀之試片剝離之後，未於膠帶上觀察到銀。
隨後，將該等試片於傳統對流烘箱中於200℃存儲1,000小時。每200小時，檢查銀對試片的黏著性。於400小時之後，試片全部顯示差的銀黏著性訊號。於1000小時之後，將該等試片自烘箱移除，並將予許其冷卻至室溫。
取每一試片之橫截面，於掃描式電子顯微鏡下檢查。全部SEM皆顯示於鎳與鈀及鎳底鍍層之介面處有縫隙。第4圖係所檢查之一片銅試片之橫截面的SEM(圖式中未顯示銅基)。SEM顯示於高熱存儲過程中，該銀層與鎳層之間存 在脫層。
實施例4
如以上實施例1中描述者製備三片銅系試片，除了將錫底鍍層替代銀底鍍層而鍍覆於該鎳層之上。水性錫底鍍浴係具有表5中之配方。
該錫底鍍浴係維持於60℃之溫度和0.1 ASD之電流密度。進行錫電鍍，直至於該鎳層上沉積0.2μm厚之錫層。
隨後，使用以上表2中揭露之氰化銀浴，對每一試片電鍍5μm厚之銀層。使用與實施例1中相同之銀鍍覆條件。
將該等鍍覆有銀之試片自該銀電鍍浴中移除，且以去離子水沖洗並於室溫風乾。隨後，使用標準十字割痕及膠帶測試來測試每一試片之銀層的黏著性。所測試之全部試片皆顯示良好黏著性。將膠帶自該塗覆有銀之試片剝離之後，未於膠帶上觀察到銀。
隨後，將該等試片於傳統對流烘箱中於200℃存儲 1,000小時。每200小時，檢查銀對試片的黏著性。於任何200小時間隔內，皆未見該銀層與試片間黏著失敗的任何可觀察之證據。於1000小時之後，將該等試片自烘箱移除，並予許其冷卻至室溫。隨後，使用標準十字割痕及膠帶測試來測試每一試片之銀層的黏著性。未見銀與鎳層間黏著失敗之信號。所測試之全部試片具有良好黏著性。
取每一試片之橫截面，於掃描式電子顯微鏡下檢查。於任何SEM中，該等金屬層之介面處均無可觀察之縫隙。第5圖係所檢查之一片銅試片之橫截面的SEM。於該SEM中未觀察到銀與鎳間之脫層。於該銀層與鎳層間之介面處，形成鎳與錫、及錫與銀之金屬間化合物。
(1)‧‧‧含銅之基板
(2)‧‧‧含鎳之阻擋層
(3)‧‧‧含錫之底鍍層
(4)‧‧‧銀層
第1圖係具有自上至下之銀層、錫底鍍層、鎳阻擋層及銅系基板之物件的橫截面示意圖。
第2圖係於200℃存儲1000小時之後鎳上之銀層之橫截面的10,000X SEM，其顯示銀與鎳介面處的縫隙。
第3圖係於200℃存儲1000小時之後銀與鎳之間具有金底鍍層之鎳上之銀層之橫截面的10,000X SEM，其顯示金底鍍與鎳介面處的縫隙。
第4圖係於200℃存儲1000小時之後銀與鎳之間具有鈀/鎳合金底鍍層之鎳上之銀沉積物之橫截面的10,000X SEM，其顯示鈀/鎳合金與鎳介面處的縫隙。
第5圖係於200℃存儲1000小時之後於銀與鎳之間具有Sn/Ag及Sn/Ni金屬間化合物之鎳上之銀沉積物之橫截 面的10,000X SEM，且於該等層之介面處不存在任何可觀察的縫隙。
(1)‧‧‧含銅之基板
(2)‧‧‧含鎳之阻擋層
(3)‧‧‧含錫之底鍍層
(4)‧‧‧銀層

Claims (7)

  1. 一種銀塗覆物件，係包含：包含銅或銅合金之基板、與該基板之該銅或銅合金相鄰的鎳層、與該鎳層相鄰之錫層、及與該錫層相鄰之銀層，該銀層與該錫層之厚度比為5：1至25：1。
  2. 如申請專利範圍第1項所述之物件，其中，該錫層係至少0.01μm厚。
  3. 如申請專利範圍第1項所述之物件，其中，該銀層係至少0.02μm厚。
  4. 如申請專利範圍第1項所述之物件，其中，該物件係包含鎳與錫之金屬間化合物及錫與銀之金屬間化合物的一者或多者。
  5. 如申請專利範圍第1項所述之物件，其中，該物件係電連接器、印刷電路板、發光二極體或電動車之元件。
  6. 一種製造銀塗覆物件之方法，係包含：a)提供基板，該基板包含銅或銅合金；b)沉積與該基板之該銅或銅合金相鄰的鎳層；c)沉積與該鎳層相鄰的錫層；以及d)沉積與該錫層相鄰的銀層，該銀層與該錫層之厚度比為5：1至25：1。
  7. 如申請專利範圍第6項所述之方法，其中，該銀係自含有氰化物之浴沉積者。
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Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014237883A (ja) * 2013-06-10 2014-12-18 オリエンタル鍍金株式会社 めっき積層体の製造方法及びめっき積層体
WO2014199547A1 (ja) * 2013-06-10 2014-12-18 オリエンタル鍍金株式会社 めっき積層体の製造方法及びめっき積層体
WO2015083547A1 (ja) * 2013-12-04 2015-06-11 株式会社オートネットワーク技術研究所 電気接点およびコネクタ端子対
CN103882484B (zh) * 2014-04-04 2016-06-29 哈尔滨工业大学 高速电镀锡用镀液
DE102014117410B4 (de) * 2014-11-27 2019-01-03 Heraeus Deutschland GmbH & Co. KG Elektrisches Kontaktelement, Einpressstift, Buchse und Leadframe
JP7121881B2 (ja) 2017-08-08 2022-08-19 三菱マテリアル株式会社 銀皮膜付端子材及び銀皮膜付端子
JP2019096584A (ja) * 2017-11-28 2019-06-20 矢崎総業株式会社 接点めっき構造
CN108347836A (zh) * 2018-04-19 2018-07-31 昆山苏杭电路板有限公司 低能耗的线路板化镍电锡表面处理工艺
DE102018120357A1 (de) * 2018-08-21 2020-02-27 Umicore Galvanotechnik Gmbh Elektrolyt zur Abscheidung von Silber und Silberlegierungsüberzügen
JP7405827B2 (ja) 2018-08-21 2023-12-26 ウミコレ・ガルファノテフニック・ゲーエムベーハー 銀の非シアン系析出用電解質
JP7111000B2 (ja) * 2019-01-18 2022-08-02 株式会社オートネットワーク技術研究所 金属材および接続端子
DE102019107416A1 (de) * 2019-03-22 2020-09-24 RIAG Oberflächentechnik AG Zusammensetzung zur elektrolytischen Vernickelung und Verfahren zur elektrolytischen Vernickelung mit einer solchen Zusammensetzung
JP7302248B2 (ja) * 2019-04-09 2023-07-04 三菱マテリアル株式会社 コネクタ用端子材及びコネクタ用端子
JP2020187971A (ja) * 2019-05-16 2020-11-19 株式会社オートネットワーク技術研究所 コネクタ端子、端子付き電線、及び端子対
US11901659B2 (en) * 2019-08-09 2024-02-13 Mitsubishi Materials Corporation Terminal material for connectors
JP7040544B2 (ja) * 2020-02-20 2022-03-23 三菱マテリアル株式会社 コネクタ用端子材
US20230328899A1 (en) * 2022-04-12 2023-10-12 Ddp Specialty Electronic Materials Us, Llc Silver coating for high temperature applications
CN114959666A (zh) * 2022-05-12 2022-08-30 李正新 化学镀银液以及化学镀银新方法
CN117896914A (zh) * 2024-03-18 2024-04-16 江苏上达半导体有限公司 一种覆铜印刷线路板的表面处理方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200842212A (en) * 2007-03-27 2008-11-01 Furukawa Electric Co Ltd Silver-coated material for movable contact parts and method of producing the same

Family Cites Families (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3041255A (en) 1960-03-22 1962-06-26 Metal & Thermit Corp Electrodeposition of bright nickel
JPS5331452B2 (zh) 1974-09-20 1978-09-02
US4871429A (en) 1981-09-11 1989-10-03 Learonal, Inc Limiting tin sludge formation in tin or tin/lead electroplating solutions
JPS58221291A (ja) * 1982-06-16 1983-12-22 Furukawa Electric Co Ltd:The 電気接続用銀被覆銅材料
US4529667A (en) * 1983-04-06 1985-07-16 The Furukawa Electric Company, Ltd. Silver-coated electric composite materials
JPH062935B2 (ja) * 1985-04-05 1994-01-12 シチズン時計株式会社 表面に有色を呈する装身具
JPS6353287A (ja) * 1986-08-21 1988-03-07 Furukawa Electric Co Ltd:The Ａｇ被覆導体
JP3444245B2 (ja) * 1999-09-03 2003-09-08 日本電気株式会社 無電解ニッケル／金メッキへのはんだ付け方法、配線構造体、回路装置及びその製造方法
AUPQ653700A0 (en) * 2000-03-28 2000-04-20 Ceramic Fuel Cells Limited Surface treated electrically conductive metal element and method of forming same
JP2002124756A (ja) * 2000-10-18 2002-04-26 Nitto Denko Corp 回路基板および回路基板の端子部の接続構造
US6755958B2 (en) 2000-12-11 2004-06-29 Handy & Harman Barrier layer for electrical connectors and methods of applying the layer
EP1352993B1 (en) * 2001-01-19 2011-05-11 The Furukawa Electric Co., Ltd. A method for preparation of metal-plated material
US20020192492A1 (en) * 2001-05-11 2002-12-19 Abys Joseph Anthony Metal article coated with near-surface doped tin or tin alloy
US20020185716A1 (en) * 2001-05-11 2002-12-12 Abys Joseph Anthony Metal article coated with multilayer finish inhibiting whisker growth
DE10146274A1 (de) * 2001-09-19 2003-04-10 Bosch Gmbh Robert Metallische Oberfläche eines Körpers, Verfahren zur Herstellung einer strukturierten metallischen Oberfläche eines Körpers und dessen Verwendung
JP3918611B2 (ja) 2002-04-03 2007-05-23 三菱マテリアル株式会社 高温電気伝導体
JP3682654B2 (ja) * 2002-09-25 2005-08-10 千住金属工業株式会社 無電解Ｎｉメッキ部分へのはんだ付け用はんだ合金
JP3877717B2 (ja) * 2003-09-30 2007-02-07 三洋電機株式会社 半導体装置およびその製造方法
US7391116B2 (en) * 2003-10-14 2008-06-24 Gbc Metals, Llc Fretting and whisker resistant coating system and method
JP4739734B2 (ja) * 2003-11-28 2011-08-03 ヴィーラント ウェルケ アクチーエン ゲゼルシャフト 電子機械的構成要素用の複合材を製造するための連続層、その複合材及び使用方法
US7122894B2 (en) * 2004-03-05 2006-10-17 Ngk Spark Plug Co., Ltd. Wiring substrate and process for manufacturing the same
US20060068218A1 (en) * 2004-09-28 2006-03-30 Hooghan Kultaransingh N Whisker-free lead frames
US7233074B2 (en) * 2005-08-11 2007-06-19 Texas Instruments Incorporated Semiconductor device with improved contacts
US20070052105A1 (en) * 2005-09-07 2007-03-08 Rohm And Haas Electronic Materials Llc Metal duplex method
US7626274B2 (en) * 2006-02-03 2009-12-01 Texas Instruments Incorporated Semiconductor device with an improved solder joint
JP4934456B2 (ja) * 2006-02-20 2012-05-16 古河電気工業株式会社 めっき材料および前記めっき材料が用いられた電気電子部品
JP4986499B2 (ja) 2006-04-26 2012-07-25 Ｊｘ日鉱日石金属株式会社 Ｃｕ−Ｎｉ−Ｓｉ合金すずめっき条の製造方法
JP4834023B2 (ja) * 2007-03-27 2011-12-07 古河電気工業株式会社 可動接点部品用銀被覆材およびその製造方法
TWI347643B (en) * 2007-06-13 2011-08-21 Advanced Semiconductor Eng Under bump metallurgy structure and die structure using the same and method of manufacturing die structure
JP4698708B2 (ja) 2008-08-19 2011-06-08 新光電気工業株式会社 パッケージ部品及び半導体パッケージ
JP5851079B2 (ja) 2008-08-21 2016-02-03 大日本印刷株式会社 部品内蔵配線板
US7915741B2 (en) * 2009-02-24 2011-03-29 Unisem Advanced Technologies Sdn. Bhd. Solder bump UBM structure
US8955580B2 (en) 2009-08-14 2015-02-17 Wah Hong Industrial Corp. Use of a graphite heat-dissipation device including a plating metal layer
US20110079814A1 (en) 2009-10-01 2011-04-07 Yi-Chang Chen Light emitted diode substrate and method for producing the same
EP2330872A1 (en) 2009-12-03 2011-06-08 Yi-Chang Chen Light emitting diode substrate and method for producing the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200842212A (en) * 2007-03-27 2008-11-01 Furukawa Electric Co Ltd Silver-coated material for movable contact parts and method of producing the same

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US20150284864A1 (en) 2015-10-08
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