臺灣博碩士論文加值系統

電致變色材料可用來製作智慧節能玻璃、飛機窗戶或顯示器等，其中大面積智慧節能玻璃的製程技術開發更能有效用來阻止太陽熱輻射，減少空調的使用量來減低全球暖化嚴重問題。三氧化鎢是常見的無機電致變色材料，現今有許多研究成果，然而為提高其電致變色效能，亦有將三氧化鎢混合其它材料之複合型電致變色元件之開發，以提升電化學與光學特性。
本實驗將藉由導線電爆炸機製備三氧化鎢 (tungsten trioxide, WO3)及三氧化鉬 (molybdenum trioxide, MoO3)奈米材料水溶液，加入由還原氧化石墨烯片 (reduce graphene oxide sheet)，再利用噴霧塗佈法在大氣下將材料噴灑於 300°C 的透明氧化銦錫 (indium tin oxide)導電基板上，製作出複合型電致變色薄膜，本論文準備四種樣品來探討
薄膜的電化學性質與光學特性。
我們使用 X 光繞射儀 (X-ray diffraction, XRD)、穿透式電子顯微鏡 (transmission electron microscope, TEM)等儀器分析奈米顆粒形貌與晶體結構，在製作成薄膜後，又利用掃描式電子顯微鏡 (scanning electron microscope, SEM)分析薄膜表面形貌，再以恆電位儀 (potentiostat)與紫外光/可見光光譜分析儀 (UV-VIS spectrometer)，在液態硫酸電解質中測量電致變色薄膜的擴散係數、響應時間、氧化還原回復率、著色前後的光學穿透率變化、光學密度以及著色效率。
最後，再以膠態電解質封裝成電致變色元件，並展示其變色前後的顏色差異。本實驗之電致變色元件製備流程簡單、生產成本低，且相較於許多傳統製程而言，能夠非常簡易的混合其它材料以及製作大面積的電致變色元件。

Electrochromic devices have been widely used in the applications of smart windows, aircraft windows, and digital displays. The most important goal is to produce a large-area smart window to block solar radiation. With this technology, energy can be saved so as to reduce the global warming problem. Tungsten trioxide (WO3) is the most promising inorganic electrochromic material. Currently, many researches are exploring composite materials based on WO3 to raise the performance of electrochromic devices.
We prepare composite materials consisting of WO3, molybdenum trioxide (MoO3) and reduced graphene oxide to make electrochromic films. The WO3 and MoO3 nanomaterials are fabricated by electro explosion. We spray the blended materials on a transparent ITO conductive substrate at 300 °C. In this study, four kinds of samples are prepared, including pure WO3, WO3 with rGO, WO3/rGO/25% MoO3, and WO3/rGO/50% MoO3. We explore the difference of electrochromic performance among those samples.
The structure and morphology of the nanomaterials were inspected using X-ray diffraction (XRD) and transmission electron microscope (TEM). After the nanomaterials are deposited to form the electrochromic films, the surface morphology of the films was studied using scanning electron microscope (SEM). The electrochemical characterization was carried out in a three-electrode system containing 0.1 M H2SO4 as electrolyte, Ag/AgCl as a reference electrode and Pt as the counter electrode. The transmittance spectra in colored and bleached states were recorded using a UV-VIS spectrometer over the wavelength range 300-1100 nm.
We also demonstrate the fabrication of a small smart window with solid state electrolyte to operate between the coloring and the bleaching states. The facile method used in this experiment shows the advantage of simple preparation, low cost, easily mixing with other materials and large-area fabrication.

摘要 I
Abstract II
致謝 IV
目錄 V
圖目錄 VII
表目錄 X
第一章 緒論 1
1-1 研究背景 1
1-2 研究動機與目的 1
第二章 文獻回顧 3
2-1 電致變色發展簡述 3
2-2 電致變色材料種類 4
2-3 三氧化鎢奈米複合型電致變色研究成果 5
2-3-1 二氧化鈦/三氧化鎢電致變色元件 5
2-3-2 三氧化鉬/三氧化鎢電致變色元件 7
2-3-3 奈米碳管/三氧化鎢電致變色元件 10
2-3-4 還原氧化石墨烯/三氧化鎢電致變色元件 12
2-4 複合型電致變色薄膜製造方法 15
2-5電致變色元件結構 19
第三章 實驗儀器與實驗方法 21
3-1 實驗儀器介紹 21
3-1-1 導線電爆炸機 21
3-1-2 噴霧塗佈系統 22
3-1-3 X光繞射儀 23
3-1-4 掃描式電子顯微鏡 24
3-1-5 穿透式電子顯微鏡 25
3-1-6 恆電位儀 25
3-1-7 紫外光/可見光光譜分析儀 26
3-1 實驗步驟 27
3-2-1 材料製備 27
3-2-2 ITO玻璃基板前處理 27
3-2-3 樣品製備 28
3-2-4 電致變色元件量測 29
3-2-5 膠態電解質封裝之元件 29
3-3 電致變色特性分析基礎 30
3-3-1 電化學性質分析 30
3-3-2 光學特性分析 31
第四章 結果與討論 33
4-1 材料與薄膜分析 33
4-1-1 材料外觀 33
4-1-2 XRD結構分析 34
4-1-3 TEM 影像分析 34
4-1-4 SEM表面形貌分析 36
4-2 電致變色元件效能分析 37
4-2-1 電化學性質 37
4-2-2 光學特性 43
4-3 膠態電解質封裝之元件成果 46
第五章 結論 48
參考文獻 49

1. M. Layani, P. Darmawan, W. L. Foo, L. Liu, A. Kamyshny, D. Mandler, S. Magdassi and P. S. Lee, Nanoscale, 2014, 6, 4572-4576.
2. A. Enesca, L. Andromic, A. Duta, and S. Manolache, Rom. J. Inf. Sci. Tech., 2007, 10, 269-277.
3. 江亞蓁，以電爆炸法製備三氧化鎢奈米顆粒並探討其電致變色特性，國立交通大學，碩士論文，2017。
4. G.-f. Cai, X.-l. Wang, D. Zhou, J.-h. Zhang, Q.-q. Xiong, C.-d. Gu and J.-p. Tu, RSC Adv., 2013, 3, 6896-6905.
5. R. R. Kharade, S. S. Mali, S. S. Mohite, V. V. Kondalkar, P. S. Patil and P. N. Bhosale, Electroanalysis, 2014, 26, 2388-2397.
6. P. M. Kadam, N. L. Tarwal, S. S. Mali, H. P. Deshmukh and P. S. Patil, Electrochim. Acta, 2011, 58, 556-561.
7. C. Fu, C. Foo and P. S. Lee, Electrochim. Acta, 2014, 117, 139-144.
8. K. S. Novoselov, V. I. Fal′ko, L. Colombo, P. R. Gellert, M. G. Schwab and K. Kim, Nature, 2012, 490, 192-200.
9. L.-L. Xu, S.-W. Bian and K.-L. Song, J. Mater. Sci., 2014, 49, 6217-6224.
10. T. Hori, T. Shibata, V. Kittichungchit, H. Moritou, J. Sakai, H. Kubo, A. Fujii and M. Ozaki, Thin Solid Films, 2009, 518, 522-525.
11. K. Galatsis, Y. X. Li, W. Wlodarski, E. Comini, G. Sberveglieri, C. Cantalini, S. Santucci and M. Passacantando, Sens. Actuators, B, 2002, 83, 276-280.
12. R. S. Patil, M.D. Uplane, and P. S. Patil, Int. J. Electrochem. Sci., 2008, 3, 259-265.
13. B. W. Faughnan and R. S. Crandall, Appl. Phys. Lett., 1977, 31, 834-836.
14. K. A. Gesheva and T. Ivanova, Chem. Vap. Deposition, 2006, 12, 231-238.
15. S. Jiang, G. Yuan, C. Hua, S. Khan, Z. Wu, Y. Liu, J. Wang, C. Song and G. Han, J. Electrochem. Soc., 2017, 164, 896-902.
16. J. R. Platt, J. Chem. Phys., 1961, 34, 862-863.
17. S. K. Deb, Appl. Opt., 1969, 8, 192-195.
18. S. K. Deb and R. F. Shaw, US Patent 3,521,941, 1970.
19. S. K. Deb, Philos. Mag. A, 1973, 27, 801-822.
20. B. W. Faughnan, R. S. Crandall, US Patent 4,009,935, 1977.
21. B. W. Faughnan, R. S. Crandall and M. A. Lampert, Appl. Phys. Lett., 1975, 27, 275-277.
22. J. P. Randin, J. Electron. Mater., 1978, 7, 47-63.
23. S. K. Mohapatra, J. Electrochem. Soc., 1978, 125, 284-288.
24. J. P. Randin, J. Electrochem. Soc, 1982, 129, 1215-1220.
25. J. S. E. M. Svensson and C. G. Granqvist, SPIE, 1984, 502, 30-37.
26. M. Pittaluga, G. Loddo, G. P. Cossu and D. Ludoni, IASH, 2010, 37, 1–8.
27. P. R. Somani and S. Radhakrishnan, Mater. Chem. Phys., 2003, 77, 117-133.
28. R. A. Patil, R. S. Devan, J.-H. Lin, Y.-R. Ma, P. S. Patil and Y. Liou, Sol. Energy Mater. Sol. Cells, 2013, 112, 91-96.
29. L. M. Schiavone, W. C. Dautremont‐Smith, G. Beni and J. L. Shay, Appl. Phys. Lett., 1979, 35, 823-825.
30. A. Ghicov, H. Tsuchiya, R. Hahn, J. M. Macak, A. G. Muñoz and P. Schmuki, Electrochem. Commun., 2006, 8, 528-532.
31. K. Nagase, Y. Shimizu, N. Miura and N. Yamazoe, Appl. Phys. Lett., 1992, 60, 802-804.
32. T. Yoshino and N. Baba, Sol. Energy Mater. Sol. Cells, 1995, 39, 391-397.
33. V. D. Neff, J. Electrochem. Soc., 1978, 125, 886-887.
34. R. J. Mortimer, Chem. Soc. Rev., 1997, 26, 147-156.
35. N. R. Kalidindi, F. S. Manciu and C. V. Ramana, ACS Appl. Mater. Inter., 2011, 3, 863-868.
36. A. Abdellaoui, G. Lévêque, A. Donnadieu, A. Bath and B. Bouchikhi, Thin Solid Films, 1997, 304, 39-44.
37. A. Agrawal, J. P. Cronin and R. Zhang, Sol. Energy Mater. Sol. Cells, 1993, 31, 9-21.
38. T. Sawatsuk, A. Chindaduang, C. Sae-kung, S. Pratontep and G. Tumcharern, Diamond Relat. Mater., 2009, 18, 524-527.
39. X. Chang, S. Sun, L. Dong, X. Hu and Y. Yin, Electrochim. Acta, 2014, 129, 40-46.
40. G.-f. Cai, J.-p. Tu, J. Zhang, Y.-j. Mai, Y. Lu, C.-d. Gu and X.-l. Wang, Nanoscale, 2012, 4, 5724-5730.
41. S.-I. Park, Y.-J. Quan, S.-H. Kim, H. Kim, S. Kim, D.-M. Chun, C. S. Lee, M. Taya, W.-S. Chu and S.-H. Ahn, Int. J. Pr. Eng. Man-gt., 2016, 3, 397-421.
42. T. Ivanova, K. Gesheva, F. Hamelmann, G. Popkirov, M. Abrashev, M. Ganchev and E. Tzvetkova, Vacuum, 2004, 76, 195-198.
43. M. Zhi, W. Huang, Q. Shi, M. Wang and Q. Wang, RSC Adv., 2016, 6, 67488-67494.
44. M. A. Arvizu, G. A. Niklasson and C. G. Granqvist, Chem. Mater., 2017, 29, 2246-2253.
45. P. R. Patil and P. S. Patil, Thin Solid Films, 2001, 382, 13-22.
46. 黃文昌，科學發展，2018，549，67-72。
47. S.-T. Wang, Y.-F. Lin, Y.-C. Li, P.-C. Yeh, S.-J. Tang, B. Rosenstein, T.-H. Hsu, X. Zhou, Z. Liu, M.-T. Lin and W.-B. Jian, Appl. Phys. Lett., 2012, 101, 183110.