臺灣博碩士論文加值系統

微陽極引導電鍍(MAGE)可在含鎳的鍍浴中，製造三維的鎳微結構。在本研究中，使用125μm 的鉑微陽極，經樹脂鑲埋後，在拋光銅基材上，引導局部電鍍的進行。在實驗過程中，控制兩極電壓強度與波形，以及兩極之間的間距，進行微陽極引導電鍍，並對析鍍過程中的電壓電流的變化進行監測。待微結構析鍍完畢後，以電子顯微鏡(SEM)觀察析鍍鎳微結構的表面與截面。在本研究中亦探討了微陽極引導電鍍(MAGE)的起鍍條件，並找出適當的析鍍條件。在兩極間距為10μm情形下，如果析鍍速率低於0.02μm/s時，析鍍速率太慢可視為不適合用於微陽極引導電鍍。另一方面，當電壓大於6.6V時，雖然析鍍速率增加至0.667μm/s，但是析鍍物的表面會變得粗糙。
結果顯示，不同電場情形下，表面型態與截面結構都有所不同，當析鍍電壓為6V間距為10μm時，微結構表面將會十分平滑，且內部為實心結構。當析鍍電壓升至7V以上，則微結構表面會變得粗糙且內部亦出現空孔結構。在實驗進行中，進行即時的電壓與電流監測，所得的數據將有助於微電鍍結果的分析。除了表面與截面的觀察之外，本研究亦探討了微鎳柱的電化學性質，結果顯示，在間距為10μm情形下，相較於7.4V析鍍的鎳微結構，6V電壓下析鍍的鎳微結構，有較好的抗腐蝕性質。

Microanode guided electroplating (MAGE) has been used to fabricate a three-dimensional microscale nickel column in nickel-containing baths. A Pt wire (125μm in diameter) was mounted with epoxy resin to expose a tip to act as a microanode that was moved to guide localized electroplating on a polished copper surface. Parameters, such as the dc-voltage bias, the waveforms of the bias and the gap between the electrodes were explored.
In this work, the morphology on the top-view and cross-section of the microclumn was examined using scanning electron microscope (SEM). Current or potential was monitored when MAGE was performed in different conditions controlled by varying the experimental parameter. The threshold strength of the electric field to start deposition for the MAGE process was found out. In an inter-electrode gap of 10μm, the deposition rate of the MAGE process was too slow (<0.02μm/s) to put in use. On the other hand, the deposition rate could increase to 0.667μm/s when the applied voltage reached 6.6V, but the surface morphology of the columns deposited was very rough.
The surface morphology and internal structure of the micro-columns deposition by MAGE process were determined by the strength of electric field. The nickel micro-columns prepared by MAGE at applied voltage 6V with an inter-electrode gap of 10μm was smooth in surface morphology and filled density in the internal structure. The surface morphology became rougher and few pores were involved in the internal structure when the applied voltage increased to 7V. The higher the applied voltage the rougher in surface morphology and the greater pores size and number in the internal structure.
Current and voltage in the MAGE process was in-situ monitored. The monitored data were useful for further adjustment to obtain nickel columns in high quality.
Electrochemical impedance spectroscopy and polarization resistance were investigated to examine the corrosion behavior of the nickel micro-columns prepared by MAGE process. The nickel micro-columns prepared at 6V with 10μm were more resistant to corrosion than that prepared at 7V with the same inter-electrode gap.

Contents
Abstract I
Acknowledgement Ⅲ
Contents Ⅳ
List of Tables Ⅷ
List of Figures Ⅸ
Chapter 1 Introdction1
1.1.What is Microanode Guided Electroplating (MAGE)?1
1.2.Why MAGE?1
1.2.1. The LIGA procedure2
1.2.2. Advantages taken by MAGE over than LIGA process3
1.3. Goals of this work4
Chapter 2 Literature Survey and Fundamental Theory5
2.1.Literature survey5
2.1.1. Micro-fabrication technologies5
2.1.2. Localized electrochemical deposition5
2.1.3 Microanode-guide electroplating (MAGE)7
2.2. Principles and Fundamental Theories9
2.2.1. Electrode Kinetics of Bulk Electrochemical reactions9
2.2.1.1. Kinetics of Interfacial Charge Transfer9
2.2.1.2Mass Transfer Controlled Current Potential Curves 10
2.2.1.3. Reaction Controlled Current Voltage Curves 12
2.2.1.4.Combined Activation and Mass Transport Control 12
2.2.2.Mass Transport of Bulk Solution 14
2.2.2.1. Diffusion 14
2.2.2.2. Convection 14
2.2.2.3. Migration 15
2.2.2.4. Nernst plank equation 17
2.2.3. Microelectrode 17
2.2.3.1. What is a microelectrode? 18
2.2.3.2. Micro- and Macrokinetics of Electrochemical Reactions 19
2.2.3.3. Properties and Advantages of Microelectrodes 20
2.2.3.4. Experimental aspects of Microelectrodes 26
2.3.Electric field consideration 27
2.3.1. The electric field 27
2.3.2. The electric potential 28
2.3.3. Lines of force 29
2.4.Electrochemical Examination 31
2.4.1. Linear Polarization 31
2.4.2. Electrochemical Impedance Spectroscopy (EIS) 32
Chapter 3 Experimental Details 35
3.1. Setup of experiment 35
3.1.1.Experimental Preparations 35
3.1.1.1. Anode preparation 35
3.1.1.2. Cathode preparation 35
3.1.1.3. Electrolyte 36
3.1.2. Guiding apparatus 37
3.1.2.1 Personal computer 37
3.1.2.2. Deposition and movement controlling card 37
3.1.2.3. Step motion motor 38
3.1.2.4. Direct current (DC) power supply 38
3.1.3. Bath heating and circulating systems 38
3.2. Experimental process 39
3.2.1. Performance of MAGE process to fabricate the nickel micro-columns. 39
3.2.2. Surface morphologies and cross-section observation 41
3.2.3. In-situ recording of data 41
3.2.4. Deposition model and electric field simulation 41
3.2.5. Electrochemical Examination 42
3.2.5.1 EIS measurement 43
3.2.5.2 Linear polarization 43
Chapter 4 Results 44
4.1. The nickel column deposited by MAGE 44
4.1.1. Effect of applied voltage on the SEM morphologies of the nickel micro-columns 44
4.1.2. Effect of inter-electrode gap on the SEM morphologies of the nickel micro-columns 47
4.2. The in-situ measurement result using Pt-wire as reference electrode 48
4.3. The growth rate of Ni micro-column 48
4.3.1. Effect of bias on the growth rate of Ni micro-column 48
4.3.2. Effect of inter-electrode gap on the growth rate of Ni micro-column 50
4.4. The pulse MAGE 50
4.5. The electrochemical properties of nickel column 514.5.1.Electrochemical impedance spectroscopy (EIS) results 52
4.5.2. Linear polarization results 52
Chapter 5 Discussion 54
5.1. Parameters related to the threshold of MAGE 54
5.1.1. The electric field on the threshold of MAGE 54
5.1.2. Bias needed on the threshold of MAGE 55
5.2. Dependence of the micro-column morphology on the parameters of MAGE 56
5.2.1. The effect of applied voltage on the column
morphologies. 57
5.2.2. The effect of inter-electrode gap on the column morphologies. 57
5.2.3. The effect of growth rate on the column cross-section. 61
5.3. The possibility of Pt-wire used as local reference electrodes. 62
5.3.1. Electrode potentials measured against reference electrodes SCE and Pt. 62
5.3.2. Effect of cathode area on the electrode potential measured against SCE and Pt. 64
5.4. Advantages of pulse MAGE. 66
5.5. The effect of morphologies on properties of nickel column. 67
Chapter 6 Conclusions 68
Chapter 7 Future Work 70
References 71

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