钛掺杂三氧化钨薄膜结构与电致变色性能研究

doi:10.15541/jim20160312

摘要/Abstract

摘要：

通过射频溅射法, 常温下制备了纯相WO₃和Ti掺杂WO₃薄膜, 采用XRD、SEM、Raman、电化学工作站、紫外-可见-近红外分光光度计等对薄膜的微观结构、循环稳定性、光学性能进行了表征和分析。研究发现: 钛掺杂对WO₃薄膜的表面形貌和光学常数影响不明显, 但使薄膜的晶化温度升高。电化学测试结果表明, Ti掺杂可以提高离子在薄膜中注入/抽出的可逆性, 提高薄膜的循环稳定性, 同时薄膜的响应速度和光学调制性能也得到提高, 掺杂后薄膜着色态和漂白态的响应时间分别由9.8、3.5 s减小为8.4、2.7 s, 因此Ti掺杂WO₃薄膜具有更好的电致变色性能。

关键词: 电致变色, 钛掺杂, 氧化钨薄膜, 结构

Abstract:

Pure and Ti-doped WO₃ thin films prepared by RF (radio-frequency) magnetron at room temperature were determined by XRD, Raman and SEM to analyze the micro-structure and the morphology of the films. In addition, electrochemical workstation and UN-Vis-NIR spectrophotometer were used to measure their cycling stability and optical property. Research results showed that Ti doping had little interference with the surface morphology and optical constants, but the film crystallization temperature could be increased by Ti doping. Electrochemical test results showed that Ti doping could improve reversibility of ion injection and extraction, and improve cycling performance of films. Meanwhile, the switching speed and optical modulation performance of films were enhanced. In detail, the switching time of colored and bleached states were shortened from 9.8 s and 3.5 s to 8.4 s and 2.7 s, respectively. Therefore, Ti doped WO₃ thin films has better electrochromic properties.

Key words: electrochromic, titanium-doped, WO3 thin films, structure

中图分类号:

TQ174

彭明栋, 章俞之, 宋力昕, 尹小富, 王盼盼, 吴岭南, 胡行方. 钛掺杂三氧化钨薄膜结构与电致变色性能研究[J]. 无机材料学报, 2017, 32(3): 287-292.

PENG Ming-Dong, ZHANG Yu-Zhi, SONG Li-Xin, YIN Xiao-Fu, WANG Pan-Pan, WU Ling-Nan, HU Xing-Fang. Structure and Electrochromic Properties of Titanium-doped WO₃Thin Film by Sputtering[J]. Journal of Inorganic Materials, 2017, 32(3): 287-292.

图/表 8

图1 薄膜的椭圆偏振光谱分析模型

Fig. 1 Stack model of the sample constructed for ellipsometry data analysis

图2 纯相WO3(a)和钛掺杂WO3薄膜(b)的SEM照片

Fig. 2 SEM images of pure WO3 (a) and Ti-doped WO3 thinfilms(b)

图3 不同温度退火纯相WO3(a)与Ti掺杂WO3薄膜(b)的XRD图谱

Fig. 3 XRD patterns of pure WO3 (a) and Ti-doped WO3 thin films (b) annealed at different temperatures

图4 不同温度退火的纯相WO3(a)与Ti掺杂WO3薄膜(b)的Raman光谱图

Fig. 4 Raman spectra of pure WO3 (a) and Ti-doped WO3 (b) thin films annealed at different temperatures

图5 纯相WO3与Ti掺杂WO3薄膜的光学常数曲线

Fig. 5 Optical constant curves of pure WO3 and Ti-doped WO3 thin films^(a) Extinction coefficient; (b) Refraction index

图6 纯相WO3 (a)与Ti掺杂WO3薄膜(b)的循环伏安曲线

Fig. 6 Cyclic voltammograms for pure WO3 (a) and Ti-doped WO3 thin films (b)

图7 纯相WO3与Ti掺杂WO3薄膜的注入与抽出的电荷量

Fig. 7 Inserted and extracted charge density of pure WO3 and Ti-doped WO3 thin films during voltammetric cycling times

图8 纯相WO3与Ti掺杂WO3薄膜着色态和漂白态透过率曲线

Fig. 8 Optical transmittance spectra of pure WO3 and Ti- doped WO3 thin films at different states

参考文献 20

[1]	TANG YI-KE, XU YAN, XU JING, et al.Current status and developmental trend of preparation of WO3 thinfilms.Journal of Chongqing University of Science and Technology, 2005, 1(7): 1-4.
[2]	ZHENG HAIDONG, OU JIANZHEN, MICHAEL S STRANO, HAIDONG, et al. Nanostructured tungsten oxide properties, synthesis, and applications.Advanced Functional Materials, 2011, 21: 2175-2196.
[3]	THAKUR V K, DING G, MA J, et al.Materials and polymer electrolytes for electrochromic device applications.Advanced Materials, 2012, 24(30): 4071-4096.
[4]	GRANQVIST C G.Electrochromic tungsten oxide films: review of progress 1993-1998.Solar Energy Materials & Solar Cells, 2000, 60(2000): 201-262.
[5]	KIM J, ONG G K, WANG Y, et al.Nanocomposite architecture for rapid, spectrally-selective electrochromic modulation of solar transmittance.Nano Lett., 2015, 15(8): 5574-5579.
[6]	LLORDÉS A, GARCIA G, GAZQUEZ J, et al. Tunable near-infrared and visible-light transmittance in nanocrystal-in-glass composites.Nature, 2013, 500(7462): 323-326.
[7]	TESFAMICHAEL T, PONZONI A, AHSAN M, et al.Gas sensing characteristics of Fe-doped tungsten oxide thin films.Sensors and Actuators B: Chemical, 2012, 168: 345-353.
[8]	ZENG X, ZHOU Y, JI S, et al.The preparation of a high performance near-infrared shielding CsxWO3/SiO2 composite resin coating and research on its optical stability under ultraviolet illumination.Journal of Materials Chemistry C, 2015, 3(31): 8050-8060.
[9]	BALOUKAS B, LAMARRE J M, MARTINU L.Electrochromic interference filters fabricated from dense and porous tungsten oxide films.Solar Energy Materials and Solar Cells, 2011, 95(3): 807-815.
[10]	HUANG ZHI-FENG, XU GANG, MIAO LEI, et al.Preparation and optical performance of WO3porous thin films.Journal of Materials Science and Engineering, 2009, 6(27): 855-858.
[11]	LU GANG, WU YONG-GANG, WU HE-YUN, et al.Preparation and characterization of WO3 thin films doped with TiO2 and Ag nano layer.Acta Optica Sinica, 2011, 31(11): 1231001-1231005.
[12]	KALIDINDI N R, MANCIU F S, RAMANA C V.Crystal structure, phase, and electrical conductivity of nanocrystalline W0.95Ti0.05O3 thin films. ACS Applied Materials & Interfaces, 2011, 3(3): 863-868.
[13]	KARUPPASAMY A S.Studies on electrochromic smart windows based on titanium doped WO3 thin films.Thin Solid Films, 2007, 516: 175-178.
[14]	ARVIZU M A, TRIANA C A, STEFANOVA B I, et al.Electrochromism in sputter-deposited W-Ti oxide films: durability enhancement due to Ti.Solar Energy Materials and Solar Cells, 2014, 125: 184-189.
[15]	MANCIU F S, YUN Y, DURRER W G, et al.Comparative microscopic and spectroscopic analysis of temperature-dependent growth of WO3 and W0.95Ti0.05O3 thin films.Journal of Materials Science, 2012, 47(18): 6593-6600.
[16]	冯媛媛, 杨晓红, 左佳奇. 纳米WO3基材料的研究进展. 重庆师范大学学报, 2015, 3(32): 139-147.
[17]	冯志鹏, 魏峰, 赵鸿滨, 等. 射频磁控溅射WO3薄膜电致变色性能研究. 稀有金属, 2015, 6(38): 283-288.
[18]	WEN R T, ARVIZU M A, NIKLASSON G A, et al.Electrochromics for energy efficient buildings: towards long-term durability and materials rejuvenation.Surface and Coatings Technology, 2015, 278: 121-125.
[19]	RAMANA C V, BAGHMAR G, EMSTO E J, et al.Optical constants of amorphous, transparent titanium-doped tungsten oxide thin films.ACS Applied Materials & Interfaces, 2013, 5: 4659-4666.
[20]	ARAGAS M V, RUBIO E J, GUTIERREZ A, et al.Spectroscopic ellipsometry determination of the optical constants of titanium- doped WO3 films made by co-sputter deposition. Journal of Applied Physics, 2014, 115: 133511-133516.