簡易檢索 / 詳目顯示

回結果列表
研究生： 謝福昇
Hsieh fu-sheng
論文名稱： 結合溶膠凝膠法及網印法製作電致色變氧化鎢薄膜之研究
Fabrication of tungsten oxide electrochromic thin film by combing sol-gel and precision screen-printing technology
指導教授： 程金保
Cheng, Chin-Pao
宋蕙伶
Sung, Hui-Ling
學位類別： 碩士
Master
系所名稱： 機電工程學系
Department of Mechatronic Engineering
論文出版年： 2011
畢業學年度： 99
語文別： 中文
論文頁數： 94
中文關鍵詞： 氧化鎢薄膜 、電致色變 、溶膠凝膠法 、網版印刷
英文關鍵詞： tungsten oxide film, electrochromic, sol-gel method, screen-printing
論文種類： 學術論文
相關次數： 點閱：519  下載：25 
分享至:
查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報

    • 本研究以溶膠凝膠法及網版印刷氧化鎢電致色變層，應用於電致色變元件。本實驗分三部份進行，第一部份為製作出乙醯過氧鎢酸粉末，並量測粉末性質。由熱差示分析，粉末在430℃位置有放熱峰，經XRD分析此放熱峰為氧化鎢薄膜結晶產生，為三斜結構的結晶相，氧化鎢薄膜250℃以下為非晶結構。第二部份調配不同氧化鎢溶膠溶液，並以旋轉塗佈法製作出氧化鎢薄膜。溶膠凝膠法所製備氧化鎢薄膜，分別給予未退火、250℃、450℃退火，光穿透率在560nm波段分別為ΔT=39%、36%與10%，隨退火溫度上升，穿透率下降，這是因為氧化鎢晶粒會慢慢團聚，造成電致色變性質降低。添加4 wt.%二水草酸氧化鎢薄膜，由可以有效抑制退火造成團聚現象，在未退火、250℃、450℃退火，光穿透率在560nm分別為ΔT=53%、34%與32%。
    第三部份調配不同比例乙醯過氧鎢酸粉末與酒精，分別3:7、4:6與5:5，再將4wt.%乙基纖維素與二水草酸添加於氧化鎢溶膠凝溶液中，製作出網版印刷漿料，藉由網版印刷於出氧化鎢電致色變層，其光穿透率在560nm波段分別為ΔT=16%、36%與10%，4:6比例擁有最佳電致色變性質與光學性質。

    This study combines sol-gel method and screen-printing technology to fabricate tungsten oxide film which applied to electrochromic element.My study can be divided into three parts.First is fabricating APTA powder and then measure its properties.The APTA powder has exothermic peak at 430℃ by DSC analysis.We learned that exothermic peak is caused crystallization behaviors from WO3 film by XRD analysis.WO3 film is amorphous phase when temperature is lower than 250℃,then turns into monoclinc phase at 450℃.
    Secondly, a sol–gel derived APTA solution encompassing 0wt.% and 4 wt.% of oxalic acid dihydrate (OAD) has been employed for the deposition of tungsten oxide films by spin-coating technology. The transmittance modulation is 39% for films annealed at 100 ℃ and decreases to 36% and 10% for 250℃ and 450℃ annealing temperature for WO3 film with 0 wt.% OAD.Grain will aggregate with higher annealing temperature,and leads to dreasing of electrochromic properties. By adding 4wt.% OAD can efficiently keep grain from aggregate.Their transmittance modulation are 53%、34% and 32% for 100℃、250℃ and 450℃annealing temperature.
    The past prepared using Powder :EtOH formulations of 3:7、4:6 and 5:5,then adding 4wt.% ethyl cellulose and OAD. Their transmittance modulation are 53%、34% and 32% .The paste with a 4:6 ratio showed better electrochromic properties.

    摘要..............................................................................................I Abstract..............................................................................................................II 目錄..................................................................................................................III 圖目錄..............................................................................................................VI 表目錄............................................................................................................... X 第一章 序論.......................................................................................................1 1.1 研究背景..................................................................................................1 1.2 研究動機與目的......................................................................................3 第二章 文獻回顧...............................................................................................6 2.1 電致色變元件..........................................................................................6 2.2 電致色變材料..........................................................................................8 2.3 電致色變機制........................................................................................11 2.4 電致色變層製備方法............................................................................13 2.5 溶膠凝膠法製備氧化鎢薄膜................................................................15 2.5.1溶膠凝法..........................................................................................15 2.5.2溶膠凝膠法製備氧化鎢膜..............................................................16 2.6 電子印刷技術........................................................................................22 2.6. 1印刷技術應用於氧化鎢電致色變元件.........................................24 第三章 實驗方法與步驟.................................................................................26 3.1實驗藥品與耗材.....................................................................................26 3.2實驗流程規劃.........................................................................................27 3.2.1 前驅粉體備.....................................................................................28 3.2.2 基板清洗.........................................................................................29 3.2.3 氧化鎢溶膠溶液液製備氧化鎢電致色層.....................................29 3.2.4 網版印刷氧化鎢電致色變膜.......................................................31 3.2.5 電解液配.........................................................................................32 3.3性質鑑定.................................................................................................33 3.3.1前驅粉體分析..................................................................................33 3.3.2薄膜表面及微結構分析..................................................................33 3.3.3 X-ray繞射分析................................................................................33 3.3.4電化學析..........................................................................................34 3.3.5光學性質測......................................................................................34 第四章結果與討論...........................................................................................35 4.1前驅粉體成分分析.................................................................................35 4.2 XRD薄膜晶體結構分析........................................................................39 4.3 旋轉塗佈法製備氧化鎢膜....................................................................41 4.3.1 SEM表面形貌分析......................................................................41 4.3.2 AFM表面粗糙度.........................................................................47 4.3.3 循環伏安法分析.............................................................................53 4.3.4光學性質分析..................................................................................60 4.4網版印刷氧化鎢薄膜. ...........................................................................71 4.4.1 SEM表面形貌分析.........................................................................72 4.4.2循環伏安法分析..............................................................................74 4.4.3光學性質分析..................................................................................78 4.5 綜合討論................................................................................................82 第五章 結論與展望.........................................................................................85 5.1 結論........................................................................................................85 5.2 未來展望................................................................................................87 參考文獻...........................................................................................................88

    1. http://web2.moeaboe.gov.tw/ECW/Policy/EnergyMeeting/defalult.htm
    2. 鄭耕哲, ”電致色變智慧型節能窗之特性與發展現況”, 工業材料雜誌,290期 ,pp.102-109(2011)
    3. http://windows.lbl.gov/comm_perf/Electrochromic/ec_tech.html
    4. 內政部營建署,“建築節能法規解說”, (1998)
    5. http://www.zh-kv.com/Kaivo/Products.asp?ID=25
    6. C.G. Granqvist , A. Azens, J. Isidorsson, M. Kharrazi, L. Kullman, T. Lindstrtm,G.A. Niklasson, C.G. Ribbing, D. RiSnnow, M. Strmme Mattsson, M. Veszelei, “Towards the smart window: progress in electrochromics”, Journal of Non-Crystalline Solids , Vol. 218 , PP.273-279 (1997)
    7. J. Livage, D.Ganguli, ” Sol-gel electrochromic coatings and devices:A review”, Solar Energy Materials & Solar Cells, Vol. 68, PP. 365-381 (2001)
    8. S.K. Deb, “A Novel Electrophotographic system”, Appl.optics, Suppl.,Vol. 3, PP. 192 (1969)
    9. K.S. Bae, U. Cha, Y.J. Lee, Y.K. Moon, H.C. Choi, J.H. Kim, C.-J. Yu,” Single pixel transmissive and reflective liquid crystal display using broadband cholesteric liquid crystal film”, Optics Express, Vol. 19, PP. 8291-8296 (2011)
    10. R.M. Osuna, V. Hernndez, J.T. Navarrete, E. Kauppinen, V. Ruiz, ” Ultrafast and High-Contrast Electrochromism on Bendable Transparent Carbon Nanotube Electrodes”, J. Phys. Chem. Lett., Vol. 1, PP. 1367–1371 (2010)
    11. K. Bange, "Colouration of tungsten oxide films: A model for optically active coatings", Solar Energy Materials & Solar Cells, Vol. 58, PP. 1-131 (1999)
    12. H. Huanga, J. Tiana, W. K. Zhanga, Y. P. Gana, "Electrochromic properties of porous NiO thin film as a counter electrode for NiO /WO3 complementary electrochromic window", Electrochimica Acta, Vol. 56, PP.4281–4286 (2011)
    13. http://zh.wikipedia.org/wiki/%E4%B8%89%E6%B0%A7%E5%8C%96%E9%92%A8
    14. K. Bange, "Colouration of tungsten oxide films: A model for optically active coatings", Solar Energy Materials & Solar Cells, Vol. 58, PP. 1-131 (1999)
    15. Muller, “U. Inorganic Structural Chemistry; John Wiley & Sons: Chichester, U.K. (1993)
    16. E. Khoo, P.S. Lee, J. Ma,"Electrophoretic deposition (EPD) of WO3 nanorods for electrochromic application",Journal of the European Ceramic Society, Vol. 30, PP. 1139–1144 (2010)
    17. B. W. Faughnan, R. S. Crandall, P. M. Heyman, "Electrochromism in WO3 Amorphous Films", RCA Review, Vol. 36, PP. 177-197 (1975)
    18. J.M. Honig, in: S. Trasatti (Ed), Electrodes of Conductive Metallic
    Oxides, Elsevier, Amsterdam, (1980)
    19. S. K. Deb, "Optical and Photoelectric Properties and Color Centers in Thin Films of Tungsten Oxide", Philosophical Magazine, Vol. 27, PP. 801-822 (1973)
    20. A.K. Chawla, S. Singhal, H.O. Gupta, R. Chandra,” Effect of sputtering gas on structural and optical properties of nanocrystalline tungsten oxide films”, Thin Solid Films, Vol. 517, PP. 1042-1046 (2008)
    21. C. Trimble, M. DeVries, J.S. Hale1, D.W. Thompson, T.E. Tiwald, J.A. Woollam, “Infrared emittance modulation devices using electrochromic crystalline tungsten oxide, polymer conductor, and nickel oxide”, Thin Solid Films, Vol. 355, PP. 26 -34 (1999)
    22. A. Subrahmanyam, A. Karuppasamy, “Optical and electrochromic properties of oxygen sputtered tungsten oxide (WO3) thin film”, Solar Energy Materials & Solar Cells, Vol 91, pp. 266 – 274 (2007)
    23. S.A. Agnihotry, Rashmi, R. Ramchandran, S. Chandra, “Pre-existence of HxWO3 in e-beam deposited WO3 films”, Solar Energy Materials & Solar Cells, Vol. 36, PP. 289 – 294 (1995)
    24. J.L. Solisa, A. Hoel, V. Lantto, C.G. Granqvist, “Infrared spectroscopy study of electrochromic nanocrystalline tungsten oxide films made by reactive advanced gas deposition”, J. Appl. Phys., Vol. 89, PP. 2727 – 2732 (2001)
    25. D. Gogova, L. K.Thomas, B. Camin, “Comparative study of gasochromic and electrochromic effect in thermally evaporated tungsten oxide thin films”, Thin Solid Films, Vol. 517, PP. 3326-3331 (2009)
    26. M. Deepa , A.K. Srivastava, S.N. Sharma, Govind, S.M. Shivaprasad, ” Microstructural and electrochromic properties of tungsten oxide thin films produced by surfactant mediated electrodeposition”, Applied Surface Science , Vol. 254, PP. 2342–2352 (2008)
    27. 蔣孝撤，“溶膠凝膠製作與應用專輯”，化工，第4卷第5期，民88年，pp. 12-15。
    28. 陳慧英、黃定加、朱秦億，“溶膠凝膠法在製備薄膜上之應用”，化工技術，第七卷第十一期，民88年，pp. 152-166。
    29. N. Sharma, M. Deepa, P. Varshney, S.A. Agnihotry, ” FTIR and absorption edge studies on tungsten oxide based precursor materials synthesized by sol–gel technique”, Journal of Non-Crystalline Solids, Vol. 306, PP. 129–137 (2002)
    30. M. Regragui, M. Addou, A. Outzourhit, J.C. BerneAde, E.E. Idrissi,E. Benseddik, A. Kachouane, ” Preparation and characterization of pyrolytic spray deposited electrochromic tungsten trioxide films”, Thin Solid Films ,Vol. 358, PP.40-45 (2000)
    31. W. Cheng, E. Baudrin, B. Dunna, J.I. Zink, ” Synthesis and electrochromic properties of mesoporous tungsten oxide”, J. Mater. Chem., Vol. 11 PP. 92-97 (2001).
    32. Z.A.E.P. Vroon and C.I.M.A. Spee, “Sol-gel coating on large area glass sheets for electrochromic device, Journal of Non-Crystalline Solids, Vol. 218”, PP. 189-195 (1997)
    33. K.D. Lee, “Preparation and electrochromic properties of WO3 coating deposited by the sol-gel method”, Solar Energy Materials & Solar Cells, Vol. 57, PP. 21-30 (1999)
    34. A. Cremonesi, D. Bersani, P.P. Lottici, Y. Djaoued, P.V. Ashrit, “ WO3 thin films by sol-gel for electrochromic applications, Journal of Non-Crystalline Solids”, Vol. 345, PP. 500-504 (2004)
    35. V. Stanid, A.C. Pierre, T. H. Etsell, R.J. Mikula, “Preparation of tungsten sulfides by sol-gel processing”, Journal of Non-Crystalline Solids, Vol. 220, PP. 58-62 (1997)
    36. D. Isık , M. Ak , C. Durucan, “Structural, electrochemical and optical comparisons of tungsten oxide coatings derived from tungsten powder-based sols”, Thin Solid Films ,Vol. 518, PP.104–111 (2009)
    37. P.K. Biswas, N.C. Pramanik, M.K. Mahapatra, D. Ganguli, J. Livage, “Optical and electrochromic properties of sol–gel WO3 films on conducting glass, Materials Letters”, Vol. 57, PP. 4429 – 4432 (2003)
    38. M. Deepa, D. P. Singh, S. M. Shivaprasad, S. A. Agnihotry, “A comparison of electrochromic properties of sol–gel derived amorphous and nanocrystalline tungsten oxide films”, Current Applied Physics, Vol. 7, PP. 220-229 (2007)
    39. M. Deepa, M. Kar, D.P. Singh, A.K. Srivastava, “Influence of polyethyleneglycol template on microstructure and electrochromic properties of tungsten oxide”, Solar Energy Materials & Solar Cells, Vol. 92, PP.170-178 (2008)
    40. X. Sun , H. Cao, Z. Liu, J. Li,” Influence of annealing temperature on microstructure and optical properties of sol–gel derived tungsten oxide films” ,Applied Surface Science , Vol. 255, PP. 8629–8633 (2009 )
    41. N.Naseri, R.Azimirad, O.Akhavan, "Improved electrochromical properties of sol–gel WO3 thin films by doping gold nanocrystals",Thin Solid Films, Vol. 518, PP.2250–2257 (2010)
    42. M.Wang, G. Fang, L.Yuan, H.Huang, Z. Sun, N. Liu, S.Xia, X. Zhao， “High optical switching speed and flexibleelectrochromic display based on WO3 nanoparticles with ZnO nanorod arrays supported electrode”, Nanotechnology ,Vol. 20, PP. 2-6 (2009)
    43. 劉致中, ”印刷電子產品應用市場發展現況”, 工業材料雜誌, 293期, PP.140-145
    44. A. Sridhar, R. R. Baumann, ”印刷式智能物件於物聯網之應用”, 工業材料雜誌, 292期, PP.101-108
    45. L. N. Lewis, J. L. Spivack, S. Gasaway,E. D. Williams, J. Y. Gui, V. Manivannan, O. P. Siclovan, “A novel UV-mediated low-temperature sinteringof TiO2 for dye-sensitized solar cells”, Solar Energy Materials & Solar Cells, Vol. 90, PP.1041-1051 (2006)
    46. C. A. Marquette, M. F. Lawrence, L. J. Blum, ” DNA Covalent Immobilization onto Screen-Printed Electrode Networks for Direct Label-Free Hybridization Detection of p53 Sequences”, American Chemical Society, Vol. 78, pp. 959-964 (2006)
    47. J. P. Coleman, A.T. Lynch, P. Madhukar, J. H. Wagenknecht, “Printed, Flexible electrochromic displays using interdigitated electrodes”, Solar Energy Materials & Solar Cells, Vol. 56, PP. 395-418 (1999)
    48. R. S. Khadayate, R. B. Waghulde, “Ethanol vapour sensing properties of screen printed WO3 thick films”, Bull. Mater. Sci. , Vol. 30, PP.129-133 (2007)
    49. A.C. Arias, J. D. MacKenzie, I. McCulloch, “Materials and Applications for Large Area Electronics: Solution-Based Approaches”, American Chemical Society, Vol.110, PP. 3-24
    50. N.Sharma, M.Deepa, P.V arshney, S.A.Agnihotry, “FTIR investigations of tungsten oxide electrochromic films derived from organically modified peroxotungstic acid precursors”, Thin Solid Films Vol. 401, PP.45–51 (2001)
    51. J. Livage, G. Guzman, “Aqueous precursors for electrochromic tungsten oxide hydrates”, Solid State Ionics, Vol. 84, PP.205-2 11( 1996)
    52. M. Deepa, T.K. Saxena, D.P. Singh, K.N. Sood, S.A. Agnihotry, “Spin coated versus dip coated electrochromic tungsten oxide films:Structure, morphology, optical and electrochemical properties”, Electrochimica Acta, Vol. 51, PP. 1974–1989 (2006)
    53. K. Huang, J. Jia, Q. Pan, F. Yang, D. He, ” Optical, electrochemical and structural properties of long-term cycled tungsten oxide films prepared by sol–gel”, Physica B, Vol. 396 , PP.164–168 (2007)
    54. P.V. Ashrit, G. Bader, Vo-Van Truong, “Electrochromic properties of
    nanocrystalline tungsten oxide thin films”, Thin Solid Films, Vol. 320, PP. 324-328 (1998)
    55. C.G. Granqvist, Handbook of Inorganic Electrochromic Material, Elsevier,
    Amsterdam, 1995

    QR CODE