以微電鍍法製備三維銅錫介金屬化合物微結構

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姓名

劉謹綸(Jin-Lun Liu) 查詢紙本館藏

畢業系所

材料科學與工程研究所

論文名稱

以微電鍍法製備三維銅錫介金屬化合物微結構
(Preparation of Three-dimensional Micro Structure of Cu-Sn Intermetallic Compound by Micro-electroplating)

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摘要(中)

本研究以微陽極導引電鍍法來製作銅錫介金屬化合物三維微結構物。電鍍系統採用線徑125 μm之白金線作為陽極，以線徑為0.643 mm之銅導線作為陰極，於含硫酸銅、硫酸亞錫、檸檬酸鈉與抗壞血酸之鍍浴中進行電鍍，希望製作出含銅、錫兩金屬元素之微柱與微螺旋。研究目標，首先探討鍍浴中添加抗壞血酸對陰極微柱析鍍物表面形貌、化學組成、晶體結構以及還原電位之影響，進而尋求製作最佳之含銅、錫二元金屬微柱之電鍍條件，隨後以此條件出發，探討製作微型螺旋之可行性，並研究微螺旋析鍍角度與製程參數對微型螺旋尺寸與線徑均勻度之影響。
結果顯示: 添加抗壞血酸至鍍浴後進行電鍍，可以達到改善析鍍微柱表面形貌之效果，促進其由顆粒分明之瘤狀外觀轉變為平坦光滑之表面。當兩極間之偏壓設定在3.50 V、兩極之間距控制在140 μm，電鍍所得之含銅、錫二元金屬微柱，其表面形貌最佳，且微柱之橫截面十分緻密，經分析其化學組成為含銅、錫(Cu: 65.9 ± 3.1 at. % 與Sn: 34.1 ± 3.1 at. %) 二元金屬之微柱，晶體結構分析顯示含Cu6Sn5相、Cu相二相。以奈米壓痕儀測量其機械性質，估計出其硬度為1.51 ± 0.10 GPa，簡化模數為73.31 ± 5.57 GPa；以電化學分析量測其抗蝕性能，測得腐蝕電流(Icorr)為0.04×10-2 mA/cm2，線性極化阻抗(RLP)為2877 ohm。
微型螺旋析鍍結果顯示: 微螺旋之第一圈線徑與第二圈線徑之電場強度變化量(△Ed12)越大且析鍍時間越短，析鍍出來之微螺旋線徑越均勻，析鍍角度15 °、製程參數2為含銅、錫二元金屬微螺旋之最佳析鍍參數，微螺旋線徑最為均勻，其d2/d1線徑比值為107 %，d3/d1線徑比值為127 %。

摘要(英)

In this study, micro-anode guided electroplating was used to manufacture three dimensional micro-structures of Cu-Sn intermetallic compound. The electroplating system uses a platinum wire with a wire diameter of 125 μm as an anode, and a copper wire with a diameter of 0.643 mm as a cathode, which is electroplated in an electroplating bath containing copper sulfate, stannous sulfate, sodium citrate and ascorbic acid to manufacture three dimensional micro-structure with two metal elements of copper and tin. The goal of this research is to firstly investigate the effect of adding ascorbic acid on the surface morphology, chemical composition, crystal structure and reduction potential of the micro-column in the plating bath, and then seek to find the best electroplating conditions of electroplating micro-columns with two metal elements of copper and tin. Then using these conditions to research the feasibility of making micro-helix, and studying the influence of micro-helix electroplating angle and process parameters on micro-helix size and the variation of wire diameter.
The results showed that after adding ascorbic acid to the electroplating bath not only improved the surface morphology of the micro-column, but also promotes the transformation from a grain-like appearance to a flat and smooth surface. When the bias is set at 3.50 V and the gap is controlled at 140 μm, the copper and tin binary metal micro-column obtained by electroplating have the best surface morphology. After analyzing, its chemical composition is Cu: 65.9 ± 3.1 at.% and Sn: 34.1 ± 3.1 at.%. The crystal structure analysis shows that the crystal structure is Cu6Sn5, Cu coexisting. The mechanical properties of the micro-column were measured by a nanoindenter. The hardness was estimated to be 1.51 ± 0.10 GPa and the reduced modulus was 73.31 ± 5.57 Gpa. The corrosion resistance was measured by electrochemical measurement. The corrosion current (Icorr) was 0.04×10-2 mA/cm2, linear polarization resistance (RLP) is 2877 ohm.
The results of electroplating micro-helix showed that the larger the changed in electric field strength (△Ed12) between the first coil diameter of the micro-helix and the second coil diameter is, the shorter the electrochemical deposition time is; and the more uniform the micro-helix diameter is, the result shows : electrochemical deposition angle 15 ° and process parameter 2 is the best electroplatimg parameter of copper-tin intermetallic compound helix because the diameter of helix wire d1、d2、d3 are the most close, the d2 / d1 ratio is 107 %, the d3 / d1 ratio is 127 %.

關鍵字(中)

★ 微陽極導引電鍍
★ 銅錫微柱
★ 銅錫微螺旋
★ 奈米壓痕

關鍵字(英)

★ Micro-anode guided electroplating
★ Copper-Tin micro-column
★ Copper-Tin micro-helix
★ Nano indentation

論文目次

目錄
摘要 i
ABSTRACT iii
誌謝 v
表目錄 viii
圖目錄 x
第一章、前言 - 1 -
1-1 研究背景 - 1 -
1-2 研究動機 - 2 -
1-3 研究目的 - 3 -
第二章、基礎理論與文獻回顧 - 4 -
2-1 電鍍原理 - 4 -
2-2 合金電鍍 - 4 -
2-3 銅錫合金電鍍 - 5 -
2-4 局部電化學沉積 - 6 -
2-5 局部電化學沉積之發展 - 7 -
2-6 奈米壓痕測試估計材料之硬度與楊氏模數 - 10 -
第三章、研究方法 - 12 -
3-1 研究方法流程 - 12 -
3-2 即時影像監控微陽極導引電鍍系統之架設 - 12 -
3-3 微陽極與陰極製備 - 14 -
3-4 鍍液調配 - 14 -
3-5 實驗步驟 - 15 -
3-5-1微柱析鍍參數探討 - 15 -
3-5-2微螺旋結構之析鍍角度與製程參數之探討 - 16 -
3-5-3形貌觀察 - 17 -
3-5-4 橫截面形貌觀察 - 17 -
3-5-5化學組成分析 - 17 -
3-5-6 晶體結構分析 - 18 -
3-5-7 奈米壓痕測試 - 18 -
3-5-8 陰極極化曲線量測 - 18 -
3-5-9 抗蝕性能量測 - 19 -
3-5-10 電場模擬 - 20 -
第四章、結果 - 21 -
4-1 銅錫介金屬化合物微柱析鍍參數探討 - 21 -
4-1-1添加抗壞血酸對析鍍銅錫介金屬化合物三維微結構之影響 - 21 -
4-1-1-1微柱形貌觀察 - 21 -
4-1-1-2 平均析鍍電流與平均析鍍速率之分析 - 22 -
4-1-1-3 化學組成分析 - 23 -
4-1-1-4 晶體結構分析 - 23 -
4-1-1-5 鍍液陰極極化量測 - 23 -
4-1-2微柱之析鍍參數探討-形貌觀察 - 24 -
4-1-3微柱之析鍍參數探討-橫截面觀察 - 25 -
4-1-4 微柱之析鍍參數探討-平均析鍍電流與平均析鍍速率之分析 - 26 -
4-1-5微柱之析鍍參數探討-化學組成分析 - 27 -
4-1-6微柱之析鍍參數探討-晶體結構分析 - 27 -
4-1-7微柱之析鍍參數探討-奈米壓痕測試 - 28 -
4-1-8 微柱之析鍍參數探討-抗蝕性能量測 - 29 -
4-1-9微柱之析鍍參數探討-電場強度模擬 - 30 -
4-2 微螺旋析鍍參數探討 - 31 -
4-2-1 微螺旋直徑與螺距量測 - 32 -
4-2-2 微螺旋線徑量測 - 32 -
4-2-3 微螺旋析鍍之電場強度模擬 - 33 -
第五章、討論 - 35 -
5-1 添加抗壞血酸對析鍍銅錫介金屬化合物微柱之影響 - 35 -
5-2 析鍍參數對析鍍微柱之影響 - 35 -
5-2-1析鍍偏壓以及析鍍間距與電場強度之關係 - 35 -
5-2-2 析鍍偏壓對微柱形貌之影響 - 36 -
5-2-3 析鍍參數對橫截面之影響 - 37 -
5-2-4 析鍍參數對機械性質之影響 - 37 -
5-2-5 析鍍參數對抗蝕性能之影響 - 38 -
5-2-6 最佳析鍍參數之選擇 - 39 -
5-3 析鍍角度與製程參數對析鍍微螺旋之影響 - 40 -
5-3-1 析鍍角度與製程參數對螺旋直徑與螺距之影響 - 40 -
5-3-2 電場強度與螺旋線徑均勻度之關係 - 40 -
第六章、結論與前瞻 - 43 -
參考文獻 - 45 -

參考文獻

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指導教授

林景崎(Jing-Chie Lin)

審核日期

2018-8-24

推文