臺灣博碩士論文加值系統

本論文在探討鎳、錫電鍍層對銅導線遷移性之影響，以及Sn-3.5Ag BGA銲料在鍍金之鎳/銅銲墊上迴銲導致之金脆現象。銅導線表面電鍍2.5∼10µm鎳後，分別在蒸餾水、0.01M NaCl及(NH4)2SO4水溶液中，施以5V偏壓，進行遷移研究，結果顯示：表層鍍鎳之銅導線，具有抑制銅遷移之效果，隨鎳鍍層厚度增加(2.5∼10µm) 抗遷移性增強，但此鍍鎳銅導線在250°C持溫300秒後，抗遷移性顯著減弱。
銅導線表面電鍍1、2及3µm錫後，雖在蒸餾水及0.01M (NH4)2SO4水溶液中5V偏壓下不能抵抗遷移，但將鍍1µm錫之銅導線在250°C持溫300秒後，立即具有良好抗遷移性，顯然鍍錫銅導線因加熱處理而增強其抗遷移性。
在0.01M (NH4)2SO4水溶液中進行陽極動態極化掃描及定電位陽極反應，配合ESCA表面分析，得知鎳、錫鍍層抑制銅遷移的原因如下：鎳鍍層在銅導線表面因陽極鈍化而生成保護膜，此鈍化膜在鎳表層為NiO及Ni(OH)2；另一方面，經加熱後之錫鍍層生成SnO2，可以抑制底層銅的溶解及氧化。
金脆研究先在鍍鎳(5µm)銅銲墊上電鍍0.1、0.5及1µm金層，再分別與Sn-Pb(63/37)及Sn-3.5Ag銲球進行迴銲，迴銲後即進行剪力量測，結果顯示：Sn-3.5Ag銲料比Sn-Pb銲料有更好的抗剪力強度（因生成Ag3Sn介金屬強化相）；金鍍層愈厚，抗剪力強度愈差。

Effect of Ni and Sn coating on the migration of Cu-conductors, and gold-embrittlement induced by reflow of the Sn-3.5Ag BGA solder on the gold deposited Ni/Cu pads have been studied. The migration of the Cu-conductors in distilled water, 0.01M Nacl and (NH4)2SO4 solutions at a bias of 5V was inhibited by coating a layer of Ni in thickness of 2.5∼10µm. This inhibition is more efficient with increasing the thickness of the Ni-coats from 2.5 to 10µm. However, it is less efficient when the Ni-coated conductors have been heat-treated at 250℃ for 300s.
The migration inhibition is not so efficient in the case of Sn-coated Cu-conductors at the same conditions. However, heat treatment (at 250℃ for 300s) tremendously enhances the resistance of the Sn-coated conductors to migration, even though the thickness of the Sn-coat only at 1µm.
Electrochemical polarization such as potentiodynamic and potentiostatic experiments were conducted. The XPS analysis for the reaction products formed on the anode indicates that NiO and Ni(OH)2 are responsible for migration inhibition of the Ni-coated conductors, and SnO2 is for the heat-treated Sn-coating conductors.
Gold-embrittlement was estimated by conducting the shear test of the soldered system where Sn-Pb (63/37) and Sn-3.5Ag solders have been reflowed, respectively, onto the Au-deposited Ni/Cu pads. The thickness of Au-deposits is ranging from 0.1 to 1µm and that for Ni-coat is 5µm. It was found that the shear strength is stronger for the Sn-3.5Ag soldering bond than for the Sn-Pb soldering. Intermetallic phase (Ag3Sn) strengthens the soldering bond. The shear strength decreases with an increase of the thickness of gold coats.

摘要（中文）Ⅰ
摘要（英文）Ⅱ
誌謝Ⅲ
目錄Ⅳ
表目錄Ⅹ
圖目錄ⅩⅠ
一、前言 1
1-1研究背景1
1-1-1構裝簡界1
1-1-2 BGA緣起與介紹2
1-1-3銅墊(Cu pads)與鎳鍍層之電化學行為4
1-1-4銲料及迴銲5
1-1-5無鉛銲料之發展6
1-2研究目的8
二、文獻回顧與理論9
2-1金屬的遷移9
2-1-1遷移（migration）9
2-1-2金屬遷移的型態9
2-1-3金屬遷移的環境9
2-1-4金屬遷移的過程與現象11
2-2銅的遷移12
2-3銅的腐蝕14
2-4鎳的氧化15
2-5錫的氧化17
2-6合金的溶解18
2-7銲料間之界面反應19
2-7-1鎳-錫（Ni/Sn）19
2-7-2錫-銀銲料/鎳、銅（Sn-Ag solder/Ni、Cu）20
2-7-3錫銲料/金/鎳、銅（Sn solder/Au/Ni、Cu）21
2-8金的應用與衍生之問題22
2-8-1鍍金之原理22
2-8-2鍍金之應用23
2-8-3金脆性23
三、實驗裝置25
3-1試片製備25
3-1-1感光電路板製備25
3-1-2電路板圖樣25
3-1-3試片製作方法25
3-2電鍍及熱處理26
3-2-1銅線路電鍍鎳及熱處理26
3-2-2銅線路電鍍錫及熱處理28
3-2-3鍍鎳銅線路鍍金29
3-3電解槽環境30
3-3-1電解槽及實驗裝置30
3-3-2電解槽環境30
3-4實驗操作與試片準備31
3-4-1遷移性的比較31
3-4-2動態陽極極化曲線掃描32
3-4-3陽極定電位腐蝕32
3-5儀器分析33
3-5-1遷移電流量測及動態極化量測33
3-5-2 OM及SEM觀察33
3-5-3 AFM表面型態觀察及分析34
3-5-4 X-ray結晶分析34
3-5-5 ESCA表面氧化物成份分析34
3-6 BGA迴銲及金脆評估35
3-6-1試片製備35
3-6-2銲錫球與BGA迴銲之程序35
3-6-3推力測試36
四、結果37
(Ⅰ)銅線路鍍鎳37
4-1-1銅線路鍍鎳熱處理前後表面形態SEM觀察37
4-1-2銅線路鍍不同厚度鎳層後AFM表面粗糙度分析37
4-1-3熱處理對鍍鎳銅線路表面粗糙度之影響38
4-1-4銅線路鍍不同厚度鎳熱處理前後X-ray繞射分析39
4-1-5銅線路鍍鎳熱處理前後之SEI剖面圖及EDX分析40
4-1-6兩極在外加電壓5V時電流密度對時間的關係圖42
4-1-7陰極析出物觀察45
(Ⅱ) 銅線路鍍錫49
4-2-1銅線路鍍錫熱處理前後表面形態SEM觀察49
4-2-2銅線路鍍不同厚度錫熱處理前後X-ray繞射分析49
4-2-3銅線路鍍錫之SEI剖面圖51
4-2-4兩極在外加電壓5V時電流密度對時間的關係圖51
4-2-5陰極析出物觀察53
(Ⅲ) 鍍鎳銅線路鍍金54
4-3-1鍍鎳銅線路在鍍不同厚度金層後表面形態SEM觀察54
4-3-2鍍鎳銅線路在鍍不同厚度金後X-ray繞射分析55
4-3-3鍍鎳銅線路在鍍金後之SEI剖面圖及EDX分析55
(Ⅳ)鍍不同厚度金層之BGA與銲錫球迴銲56
4-4-1錫-鉛（63/37）銲球56
4-4-2 Sn-3.5Ag銲球57
五、討論59
(Ⅰ)銅線路鍍鎳59
5-1-1 NaCl水溶液中的動態陽極極化曲線分析59
5-1-2 (NH4)2SO4水溶液中的動態陽極極化曲線分析59
5-1-3銅線路鍍不同厚度鎳的動態陽極極化曲線分析64
5-1-4在0.01M (NH4)2SO4水溶液中定電位下的陽極電流比較65
5-1-5 ESCA表面氧化物成分分析66
(Ⅱ)銅線路鍍錫70
5-2-1 (NH4)2SO4水溶液中的動態陽極極化曲線分析70
5-2-2銅線路鍍不同厚度錫的動態陽極極化曲線分析74
5-2-3 ESCA表面氧化物成分分析75
(Ⅲ)鍍不同厚度金層之BGA與銲錫球迴銲78
5-3-1錫-鉛（63/37）銲球78
5-3-2 Sn-3.5Ag銲球79
六、結論81
七、參考文獻82

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