AZO與ITO等透明導電氧化薄膜之電化學行為

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彭彥鈞(Yeh-Chun Peng) 查詢紙本館藏

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機械工程學系

論文名稱

AZO與ITO等透明導電氧化薄膜之電化學行為
(Electrochemical behavior of transparent conductive Al-doped zinc oxide(AZO) and tin-doped indium oxide(ITO) films)

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摘要(中)

本研究在探討Al-doped zinc oxide(AZO)、Tin-doped indium oxide(ITO)、摻雜微量鈧之AZO及經300℃熱處理1小時後之AZO透明導電氧化薄膜等在3.5%NaCl溶液中，及不同pH之緩衝溶液中之電化學行為。研究方法採用開路電位量測、線性極化掃描、循環伏安法(CV)及交流阻抗頻譜測試(EIS)來探討它們的電化學現象，進而利用定電位還原反應在不同時間下來研究其表面之生成物。
上述之透明導電氧化薄膜在3.5%NaCl中，其抗腐蝕能力由大而小依序為：經300℃熱處理之AZO＞ITO＞Sc-doped AZO＞AZO。摻雜微量鈧有利於AZO薄膜提升其抗腐蝕能力，當鈧摻雜量在0~1.7wt%時，其抗腐蝕性由大而小依序為：0.242wt%＞0.134wt%＞0.006wt%＞0wt%，亦即鈧摻雜量愈高，其抗蝕能力愈強。
測量AZO透明導電薄膜在緩衝溶液下之開路電位，顯示在1500秒後才達穩定之電位。AZO薄膜在酸性(pH=4.10)及鹼性(pH =11.58)之緩衝溶液下，以不同掃瞄速率進行循環伏安(CV)電化學測試顯示：在50mV/s之掃瞄速率下，有明顯之氧化還原特性峰值。經300℃熱處理1小時之AZO薄膜在緩衝溶液中，其氧化還原特性電流皆比未熱處理之AZO低，顯示AZO薄膜在300℃熱處理後使AZO之活性下降，因而提升其抗腐蝕能力。定電位實驗有助於解析氧化及還原狀態之相關化學反應方程式。

摘要(英)

The electrochemical behavior of Al-doped zinc oxide(AZO)、Tin-doped indium oxide(ITO)、Sc-doped AZO and AZO annealed at 300℃ for 1hr were immersed in 3.5%NaCl and in different buffer solutions varying with pH were investigated in this work. Electrochemical techniques such as measurement of open circuit potential, linear polarization, cyclic voltammograms, electrochemical impedance spectroscopy were employed. Reaction products on the surface of oxides under different potentials were examined for those produced on a variety of potentials in different duration.
The corrosion resistance of difference oxide films to 3.5%NaCl solution decreases in the order: annealed 300℃ AZO＞ITO＞Sc-doped AZO＞AZO. Sc-doped tends to in increase the corrosion resistance of the AZO thin films. The corrosion resistance to 3.5%NaCl for Sc-doped AZO decreases with decreasing the concentration of Sc-doped：0.242wt%＞0.134wt%＞0.006wt%＞0wt%.
The electrochemical behavior of AZO and the AZO anneal at 300℃ for 1h in various buffer solutions was studied using cyclic voltammetry under a scan rate of 50mV/s. The reduction current and characteristic oxidation current are lower in the annealed AZO then the usual AZO, this fact reflects that annealed AZO is more resistance to corrosion in buffer solutions.

關鍵字(中)

★ 熱處理
★ 線性極化
★ 鋁摻雜氧化鋅
★ 緩衝溶液
★ 循環伏安法

關鍵字(英)

★ AZO
★ linear polarization
★ Sc-doped AZO
★ annealed
★ cyclic

論文目次

摘要 I
摘要(英文) III
致謝 IV
目錄 V
表目錄 IX
圖目錄 X
第一章前言…………………………………………………1
1. 1 研究背景……………………………………………1
1. 1. 1透明導電氧化膜由來…………………………1
1. 1. 2薄膜濺鍍系統…………………………………3
1. 2 研究目的……………………………………………4
第二章原理與文獻回顧………………………………………5
2. 1 導電薄膜發展及製程原理…………………………5
2. 2 電化學腐蝕原理……………………………………7
2. 2. 1 腐蝕型態……………………………………7
2. 2. 2 腐蝕速率測試………………………………10
第三章實驗方法……………………………………………14
3. 1 電極備製……………………………………………14
3. 1. 1 工作電極之製作……………………………14
3. 1. 2 相對電極及參考電極………………………15
3. 1. 3 電化學試驗環境……………………………15
3. 2 實驗流程……………………………………………16
3. 3 電化學實驗方法……………………………………16
3. 3. 1 開路電位(Open circuit potential)…16
3. 3. 2 線性極化測試(Linear polarization)…17
3. 3. 3 交流阻抗法(EIS)…………………………17
3. 3. 4 動態極化掃瞄(Potentiodynamic)………18
3. 3. 5 循環伏安測試(Cyclic voltammograms)…18
3. 4 分析儀器……………………………………………19
3. 4. 1 AFM表面粗糙度分析………………………19
3. 4. 2 SEM表面形貌觀察…………………………19
3. 4. 3 X-ray結晶分析……………………………19
第四章實驗結果……………………………………………21
4. 1透明導電氧化膜表面形貌分析…………………21
4. 1. 1 AZO薄膜……………………………………21
4. 1. 2 經300℃熱處理之AZO薄膜………………21
4. 2 透明導電氧化膜電化學分析………………………21
4. 2. 1 開路電位比較………………………………21
4. 2. 1-1 3.5%NaCl溶液……………………………21
4. 2. 1-2 不同pH值之緩衝溶液…………………23
4. 2. 2 線性極化電阻比較…………………………25
4. 2. 3 動態極化比較…………………………26
4. 2. 4-1 ITO薄膜…………………………………28
4. 2. 4-2 AZO薄膜…………………………………29
4. 2. 4-3 經300℃熱處理之AZO薄膜……………31
4. 2. 5 定電位實驗比較……………………………31
4. 2. 6 交流阻抗實驗比較…………………………33
4. 2. 7 AFM表面粗糙度Ra值比較………………34
4. 2. 8 SEM表面形貌比較及EDS分析……………35
第五章討論………………………………………………38
5. 1 電化學實驗討論……………………………………38
5. 1. 1 開路電位討論………………………………38
5. 1. 2 腐蝕電流討論………………………………39
5. 1. 3 動態極化討論………………………………39
5. 1. 4 交流阻抗討論………………………………40
5. 1. 5 表面粗糙度Ra比較值討論………………40
5. 1. 6 腐蝕後SEM表面形貌……………………41
5. 2透明導電氧化膜循環伏安研究……………………41
5. 2. 1 掃瞄速率影響………………………………41
5. 2. 2 XRD晶粒大小………………………………42
5. 3還原機制探討………………………………………44
5. 3. 1 ITO還原機制………………………………44
5. 3. 2 AZO還原機制………………………………45
第六章結論…………………………………………………46
第七章未來展望……………………………………………48
參考文獻………………………………………………………49

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指導教授

林景崎(Jing-Chie Lin)

審核日期

2007-7-18

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