臺灣博碩士論文加值系統

由於歐盟(European Union)決定於2006年7月起限制含鉛之電子、電器相關產品進入歐洲市場，產業界為此必須重新研發可取代含鉛的無鉛銲料(Pb-free solder) ，本文主要研究方向為針對替代錫鉛焊料之無鉛焊料(Pb-free)的應用；實驗本身先藉由直流電鍍法方式在酸性溶液下以檸檬酸(citric acid )和氨水(Ammonia Water)當錯合劑，利用SnCl4和Bi(NO3)3當前驅物成長錫、鉍金屬於鎳基材上，配合實驗設計法方式控制錫鉍組成並利用能量散射光譜儀(EDX)測量錫鉍金屬之組成；在材料分析方面則利用場發射電子顯微鏡(FE-SEM)及晶格繞射(XRD)分析不同條件下錫鉍鍍層的表面形態及結晶性變化，最後再針對錫鉍鍍層在腐蝕方面進行電化學行為之研究。
實驗先藉由實驗設計法方式控制錫鉍在最低共熔點(Eutectic point)附近之組成，並分析不同鍍層組成在材料特性上的差異，但由於製備低錫含量之鍍層時，其錫鉍成長至鎳基材上的效果並不理想；因此進一步藉由實驗設計法方式重新控制高錫含量之錫鉍鍍層的組成(Sn content>80wt%)，藉以改善低錫含量時鍍層易剝落的現象。
在實驗設計方面，包含利用部份因素實驗設計法及中心組合設計等方法來以控制高錫含量鍍層之最佳成長條件。根據實驗結果獲知，影響鍍層組成之主要因素包含：鍍浴濃度及[Sn4+]與[Bi3+]的莫耳百分比。由中心組合實驗設計得知，隨著增加鍍液濃度及鍍液中[Sn4+]/ [Bi3+]比例提高時，可使鍍層中錫含量增加。
在腐蝕方面的研究，為探討不同組成之錫鉍鍍層的抗腐蝕能力，藉由開環電位法量測不同鍍層在3wt% NaCl下的OCP以找出最佳之開環電位、較高腐蝕阻抗及較小腐蝕電流的錫鉍組成；在未經過高溫迴流的錫鉍鍍層而言，錫含量93.7 wt%則具有最佳的抗腐蝕能力。

European Union declares that the imported electronics should obey the RoSH since 1st July 2006, resulting in the urgent demanding for developing new Pb-free solders. For semiconductor industries, solder joint is an essential part of electronic devices. In order to replace SnPb solders, the deposition of tin-bismuth was investigated in this work.
First, the tin-bismuth deposits with various bismuth contents were electroplated on the nickel substrate in the acid precursor media containing ammonia and citric acid. The composition of tin-bismuth deposits was determined through the means of an energy-dispersive X-ray (EDX) spectroscope. The textures of tin-bismuth deposits were examined through X-ray diffraction (XRD) patterns and scanning electron microscope (SEM). Finally, the corrosion behavior of various tin-bismuth deposits was investigated in this work.
The fractional factorial design (FFD) was used to find the key factors and to control the composition of deposit. Thus, the Sn-Bi deposits with compositions close to the binary eutectic Sn-Bi are easily to be obtained. However those Sn-Bi deposits are Bi-rich, full of dendrite and poor mechanical strength. Accordingly , the content of Sn was controlled to be above 80wt% for practical application so to obtain the best electroplating conditions for Sn-rich deposits, the designs of experiment (DOE), including the fractional factorial design and central composition design, were employed. According to the results from DOE, the key variables affecting the Sn-Bi composition were concentration and the mole percentage of [Sn4+] and [Bi3+] in the plating baths.
The anticorrosion ability of tin-bismuth deposits with difference bismuth contents was compared with the electroplated tin deposits. The open circuit potential-time (OCP) measurement, linear sweep voltammetry (LSV), and Tafel polarization curves were used to investigate the corrosion behavior of tin-bismuth deposits in the 3wt% NaCl solution. The results show that the corrosion resistance of the Sn-6.3wt% Bi deposit is superior to that of other Sn-Bi and the pure tin deposits, which exhibits has the best corrosion potential and the lowest corrosion current.
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目錄

中文摘要………………………………………………………………………I
Abstract……………………………………………………………………III
目錄……………………………………………………………………………V
圖目錄………………………………………………………………………IX
表目錄………………………………………………………………………XV

第一章 緒論及理論基礎………………………………………………………1
1-1 電鍍的基本原理……………………………………………………1
1-1-1 前言…………………………………………………………………1
1-1-2 電鍍的原理…………………………………………………………2
1-1-3 合金電鍍……………………………………………………………11
1-1-4 電鍍的前處理………………………………………………………13
1-2 覆晶封裝的簡介……………………………………………………16
1-2-1 前言………………………………………………………………………16
1-2-2 凸塊接點製作……………………………………………………………18
1-2-3 凸塊製作技術……………………………………………………………19
1-3 實驗設計法……………………………………………………………23
1-3-1 前言…………………………………………………………………………23
1-3-2 部分因素實驗設計法………………………………………………………24
1-3-3 應答曲面設計………………………………………………………………28
1-3-4中心組合設計法……………………………………………………………30
1-3-5缺適度的檢驗………………………………………………………………32
1-4 腐蝕概論………………………………………………………………35
1-4-1 腐蝕的定義……….………………………………………………………36
1-4-2 腐蝕的電化學反應…………………………………………………………36
1-4-3 鈍化…………………………………………………………………………38
1-4-4 腐蝕電位和腐蝕電流………………………………………………………38
1-4-5腐蝕的種類……………………………………………………………………41
1-5錫鉍合金電鍍回顧………………………………………………………………43
1-6研究動機與本文大綱……………………………………………………………47

第二章 實驗步驟、藥品、實驗儀器………………………………………………49
2-1藥品………………………………………………………………………………49
2-2 實驗儀器…………………………………………………………………………50
2-2-1 實驗儀器規格…………………………………………………………………50
2-2-2 電化學分析儀器………………………………………………………………51
2-2-3材料分析儀器……………………………………………………………………51
2-3電極的製備.………………………………………………………………………54
2-4 電化學實驗.………………………………………………………………………56
2-4-1線性掃描伏安法法…………………………………………………………56
2-4-2 腐蝕測試…………………………………………………………………56
2-5 材料分析…………………………………………………………………………57
2-5-1 表面型態分析……………………………………………………………57
2-5-2 結晶性測試………………………………………………………………58

第三章 鎳基材上鉍錫鍍層之組成控制與材料分……………………………………59
3-1 前言…………………………………………………………………………………59
3-2 鎳基材製備條件……………………………………………………………………63
3-3部分因素實驗設計法………………………………………………………………65
3-4 材料特性……………………………………………………………………………74
3-4-1 表面型態…………………………………………………………………………74
3-4-2 結晶性……………………………………………………………………………80
3-5 結論…………………………………………………………………………………86

第四章 鎳基材上高錫含量錫鉍組成控制與材料分析………………………………87
4-1 前言…………………………………………………………………………………87
4-2部分因素實驗設計法………………………………………………………………89
4-3 材料分析……………………………………………………………………………99
4-3-1表面形態…………………………………………………………………………99
4-3-2結晶性……………………………………………………………………………104
4-4結論……………………………………………………………………………………107

第五章 錫鉍鍍層之腐蝕行為與材料特性………………………………………………108
5-1 前言……………………………………………………………………………………108
5-2錫鉍鍍層之腐蝕行為..………………………………………………………………108
5-3腐蝕下的表面形態與結晶性……………………………………………………………112
5-4熱處理後錫鉍鍍層之腐蝕行為…………………………………………………………117
5-5熱處理後腐蝕測試的表面形態與結晶性………………………………………………120
5-6結論………………………………………………………………………………………125

第六章 總結與展望…………………………………………………………………………126
6-1 總結……………………………………………………………………………………126
6-2 展望………………………………………………………………………………………128

參考文獻………………………………………………………………………………………130

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