在電致變色的元件上，與奈米結構結合，可以提升元件反應的比表面積，從而提升電致變色性能。另外，鋁是一種具有良好導電性的材料，若將鋁結合進入氧化鋅奈米結構中，效率必能進一步提升。本文中實作了生長氧化鋅摻雜鋁(ZnO:Al)的奈米結構，並研究其結合氧化鎢於電致變色元件中的性能表現。
在實驗中，研究了ZnO:Al奈米結構的製程。其奈米結構使用水熱法生長，第一步先以適量的聚乙烯亞胺(PEI)、六亞甲基四胺(HMTA)與硝酸鋅六水合物(Zn(NO3)2·6H2O)加入200 ml的去離子水製成前驅液，硝酸鋅六水合物依據不同鋁濃度摻雜而調整比例。ZnO奈米結構的生長在160℃下進行30分鐘，隨後加入不同濃度的硝酸鋁九水合物繼續生長30分鐘，可得到具有不同濃度的ZnO:Al。隨著Al摻雜濃度的上升，提升了其電荷遷移量，在電化學穩定性上也有不錯的提升。
接著在ZnO:Al奈米結構上濺鍍三氧化鎢(WO3)，並對WO3進行了簡易的優化調整。使用射頻磁控濺鍍系統沉積WO3電致變色層，在固定的氬氣與氧氣氣氛中，進行濺鍍30分鐘，得到均勻薄膜。濺鍍完的薄膜為非晶態結構。非晶態與結晶態的薄膜具有不同優缺點，非晶薄膜的離子傳輸快但穩定性差，結晶態則與之相反，為了平衡其優劣，對薄膜進行了後退火處理，再增加穩定性的同時，盡可能保留了非晶態離子遷移容易的優勢。
在元件進行後退火處理後，電荷遷移量有明顯的提升。觀察其響應時間也可以發現隨著後退火溫度的提升，有逐漸結晶的趨勢，雖然XRD圖中無出現明顯的WO3衍射峰，但響應時間的增加表示出了結構的重組，整齊有序的原子降低了其離子的遷移率。

In this study, we combined electrochromic elements with nanoscale structures to enhance the specific surface area and improve the electrochromic performance of the device. Additionally, we investigated the potential enhancement of efficiency by incorporating aluminum (Al), a highly conductive material, into zinc oxide (ZnO) nanoscale structures. We implemented ZnO doped with aluminum (ZnO:Al) nanoscale structures and studied their performance in conjunction with tungsten oxide (WO3) in electrochromic devices.

During the experiment, we focused on the fabrication process of ZnO:Al nanoscale structures. The nanoscale structures were grown using a hydrothermal method. Initially, a precursor solution was prepared by adding an appropriate amount of polyethyleneimine (PEI), hexamethylenetetramine (HMTA), and zinc nitrate hexahydrate (Zn(NO3)2·6H2O) to 200 ml of deionized water. The proportion of zinc nitrate hexahydrate was adjusted according to the desired aluminum doping concentration. The growth of ZnO nanoscale structures occurred at 160℃ for 30 minutes. Subsequently, different concentrations of aluminum nitrate nonahydrate were added for an additional 30 minutes of growth, resulting in varying concentrations of ZnO:Al. As the aluminum doping concentration increased, the charge transfer amount was enhanced, leading to improved electrochemical stability.

Next, we sputter-deposited tungsten trioxide (WO3) onto the ZnO:Al nanoscale structures and performed simple optimization adjustments for WO3. The sputter deposition was carried out using a radio frequency magnetron sputtering system, and the WO3 electrochromic layer was deposited in a fixed argon and oxygen atmosphere for 30 minutes, producing a uniform thin film. The as-deposited film exhibited an amorphous structure. Both amorphous and crystalline films have distinct advantages and disadvantages; amorphous films have fast ion transport but lower stability, while crystalline films offer the opposite. To balance these advantages and disadvantages, we subjected the thin film to post-annealing, enhancing stability while attempting to retain the advantages of fast ion transport in the amorphous state.

After the annealing treatment, there was a noticeable improvement in charge transfer. The observation of response time indicated a gradual trend towards crystallization with increasing annealing temperature. Although there were no significant WO3 diffraction peaks in the XRD pattern, the increase in response time suggested structural reorganization, where orderly atomic arrangements reduced the ion mobility.

摘要 IV
Abstract VI
致謝 IX
目錄 XI
圖目錄 XIV
表目錄 XIX
第一章 緒論 1
1.1 前言 1
1.2 研究動機與目的 3
1.3 文獻探討 5
第二章 基礎理論 12
2.1 電致變色介紹 12
2.1.1 電致變色元件結構 13
2.1.2 電致變色機制 15
2.2 電解質 18
2.2.1 離子傳輸 20
2.2.2 電解質系統 21
2.3 副反應 24
2.3.1 透明電極失效 24
2.3.2 電解質失效 24
2.3.3 電致變色層失效 24
2.3.4 封裝失敗 25
2.4 薄膜製程方法 26
2.4.1 物理氣相沉積法 26
2.4.2 化學氣相沉積法 29
2.4.3 溶液法 30
2.4.4 電化學沉積法 34
2.5 氧化鋅 36
2.5.1 光學性質 36
2.5.2 電學性質 37
2.6 三氧化鎢 40
第三章 實驗方法與量測系統 41
3.1 實驗材料 41
3.1.1 製備ZnO摻雜Al奈米結構 41
3.1.2 製備WO3電致變色層 41
3.1.3 製備電解質 41
3.2 實驗流程 42
3.2.1 ZnO摻雜Al奈米結構之製備 42
3.2.2 WO3電致變色層之製備 44
3.2.3 電解液之製備 44
3.3 實驗步驟 46
3.3.1 基板前處理 46
3.3.2 製備AZO種晶層 46
3.3.3 製備ZnO:Al奈米結構 47
3.3.4 製備WO3電致變色薄膜 49
3.4 量測系統 49
3.4.1 X光繞射儀（X-ray Diffractometer，XRD） 49
3.4.2 場發射型掃描式電子顯微鏡(Field-Emission Scanning Electron Microscope，FE-SEM) 51
3.4.3 能量分散X射線光譜儀(Energy-Dispersive X-ray Spectroscopy，EDS) 52
3.4.4 紫外光/可見光分光光度計(Ultraviolet/Visible Spectrophotometer) 53
3.4.5 電化學工作站(Electrochemical Workstation) 54
第四章 結果與討論 57
4.1 元件A-WO3非晶薄膜濺鍍時間對ECD之結構分析和電致變色特性 58
4.1.1 表面型態分析 59
4.1.2 材料元素分析 59
4.1.3 X光繞射分析 59
4.1.4 紫外/可見光光譜分析 60
4.1.5 電致變色特性分析 61
4.2 元件B-兩階段水熱法生長ZnO:Al奈米結構對ECD之結構分析和電致變色特性 80
4.2.1 表面型態分析 81
4.2.2 材料元素分析 82
4.2.3 X光繞射分析 83
4.2.4 紫外/可見光光譜分析 83
4.2.5 電致變色特性分析 84
4.3 元件C-不同溫度下後退火處理對ECD之結構分析和電致變色特性 105
4.3.1 表面型態分析 106
4.3.2 材料元素分析 106
4.3.3 X光繞射分析 106
4.3.4 紫外/可見光光譜分析 107
4.3.5 電致變色特性分析 107
第五章 結論 127
文獻參考 129

[1]P.V. Ashrit, Fernand E. Girouard, Vo-Van Truong, 1996, “Fabrication and testing of an all-solid state system for smart window application”, Solid State Ionics, vol. 89, pp. 65-73, August.
[2]M. Kateb, S. Safarian, M. Kolahdouz, M. Fathipour, V. Ahamdi, 2016, “ZnO–PEDOT core–shell nanowires: An ultrafast, high contrast and transparent electrochromic display”, Solar Energy Materials and Solar Cells, vol. 145, pp. 200-205, February.
[3]Y. Park, K. Kang, J. Kang, D. Lee, S. Na, S. Han, Y. Nah, D. Kim, 2022, "Structure and electrochromic properties of WO3 thin films by direct current, pulsed direct current, and radio frequency magnetron sputtering from metallic and ceramic targets ", Thin Solid Films, vol. 763, 139596, December.
[4]K. Tajima, T. Kubota, C. Jeong, 2022, "Preparation of electrochromic thin films by humidity-controlled spin coating", Thin Solid Films, vol. 758, 139412, September.
[5]J. Liu, S. Chiam, J. Pan, L. Wong, S. Li, Y. Ren, 2018, "Solution layer-by-layer uniform thin film dip coating of nickel hydroxide and metal incorporated nickel hydroxide and its improved electrochromic performance", Solar Energy Materials and Solar Cells, vol. 185, pp. 318-324, October.
[6]A. Prasad, J. Park, H. Jung, J. Kang, S. Kang, K. Ahn, 2023, "Electrochemical deposition of Ni-WO3 thin-film composites for electrochromic energy storage applications: Novel approach toward quantum-dot-sensitized solar cell-assisted Ni-WO3 electrochromic device", Journal of Industrial and Engineering Chemistry, vol. 117, pp. 500-509, January.
[7]J. Choi, G. Balamurugan, G. Pande, Y. Eom, H. Kim, D. Cha, J. Park, 2022, "Fully spray-coated electrochromic devices containing octa-viologen substituted polyhedral oligomeric silsesquioxane", Thin Solid Films, vol. 743, 139067, February.
[8]S. Tan, L. Gao, W. Wang, X. Gu, J. Hou, G. Su, 2022, "Preparation and black-white electrochromic performance of the non-contact ZnO@NiO core-shell rod array", Surfaces and Interfaces, vol. 30, 101889, June.
[9]Z. Bi, S. Zhang, X.e Xu, X. Hu, X. Li, X. Gao, 2015, "A novel nanocomposite of WO3 modified Al-doped ZnO nanowires with enhanced electrochromic performance", Materials Letters, vol. 160, pp. 186-189, December.
[10]H. Efkere, A. Gümrükçü, Y. Özen, B. Kınacı, S. Aydın, H. Ates, S Özçelik, 2021, "Investigation of the effect of annealing on the structural, morphological and optical properties of RF sputtered WO3 nanostructure", Physica B: Condensed Matter, vol. 622, 413350, December.
[11]X. Chen, W. Li, L. Wang, Y. Zhao, X. Zhang, Y. Li, J. Zhao, 2021, "Annealing effect on the electrochromic properties of amorphous WO3 films in Mg2+ based electrolytes", Materials Chemistry and Physics, vol. 270, 124745, September.
[12]魏嘉瑩, 林佳樺, 劉正毓, 2015, “釓摻雜氧化鋅鋁透明導電薄膜特性分析”, http://www.twiche.org.tw/ezfiles/0/1000/attach/85/pta_261_
1140471_13992.pdf
[13]M. Wang, Q. Liu, G. Dong, Y. He, X. Diao, 2017, "Influence of thickness on the structure, electrical, optical and electrochromic properties of AZO thin films and their inorganic all-solid-state devices", Electrochimica Acta, vol. 258, pp. 1336-1347, December.
[14]R. S. Crandall, B. W. Faughnan, 1975, “Measurement of the diffusion coefficient of electrons in WO3 films”, Applied Physics Letters, vol. 26, pp. 120.
[15]S.K. Deb, 1969, “A novel electrophotographic system”, Applied Optics, vol. 8, pp. 192-195.
[16]陳祐頎, 吳昱賢, 張家欽, 2019, “鋰離子電池電解質-鋰離子傳遞的橋樑”, https://ejournal.stpi.narl.org.tw/sd/download?source=10812-03.pdf&vlId=81c00b94ab824d3f8bae19957ea839e0&nd=1&ds=1
[17]P. V. Ashrit, G. Bader, V. V. Truong, 1998, “Electrochromic properties of nanocrystalline tungsten oxide thin films”, Thin Solid Films, vol. 320, pp. 324-328, May.
[18]X. Chen, Y. Zhao, W. Li, L. Wang, J. Xue, X. Zhang, Y. Li, 2022, "NiO films prepared by e-beam evaporation for Mg2+ based electrochromic devices", Optical Materials, vol. 124, 111959, February.
[19]J. Xue, Y. Zhu, M. Jiang, J. Su, Y. Liu, 2015, "Electrochromic WO3 thin films prepared by combining ion-beam sputtering deposition with post-annealing", Materials Letters, vol. 149, pp. 127-129, June.
[20]K. Gesheva, T. Ivanova, M. Kozlov, S. Boyadzhiev, 2010, "Atmospheric pressure chemical vapour deposition of electrochromic Mo–W thin oxide films: Structural, optoelectronic and vibration properties", Journal of Crystal Growth, vol. 312, Issue 8, pp. 1188-1192, April.
[21]K. Xu, L. Wang, S. Xiong, C. Ge, L. Wang, B. Wang, W. Wang, M. Chen, G. Liu, 2023, "Hydrothermally prepared ultra-stable multilayer nanoflake NiO-based electrochromic films", Electrochimica Acta, vol. 441, 141812, February.
[22]K. Vanheusden, W. L. Warren, C. H. Seager, D. R. Tallant, J. A. Voigt, B. E. Gnade, 1996, “Mechanisms behind green photoluminescence in ZnO phosphor powders”, Journal of Applied Physics, vol. 79, pp. 7983, June.
[23]O. Arslan, Y. Abalı, 2017, “Controlled modulation of 1D ZnO nano/micro structures: Evaluation of the various effects on the photocatalytic activity”, Journal of Physics and Chemistry of Solids, vol. 108, pp. 88-97, September.