基于多孔ITO电极的WO3薄膜的制备及其电致变色性能

doi:10.15541/jim20240531

无机材料学报 ›› 2025, Vol. 40 ›› Issue (7): 781-789.DOI: 10.15541/jim20240531

基于多孔ITO电极的WO₃薄膜的制备及其电致变色性能

杨光(), 张楠, 陈舒锦, 王义(), 谢安, 严育杰()

厦门理工学院材料科学与工程学院, 福建省功能材料及应用重点实验室, 厦门 361024

收稿日期:2024-12-23 修回日期:2025-01-23 出版日期:2025-07-20 网络出版日期:2025-03-19
通讯作者: 严育杰, 副教授. E-mail: yujieyan@xmut.edu.cn;
王义, 讲师. E-mail: yiwang@xmut.edu.cn
作者简介:杨光(2000-), 男, 硕士研究生. E-mail: yangguang@stu.xmut.edu.cn
基金资助:
国家自然科学基金(62304189);福建省自然科学基金(2023J011450);福建省自然科学基金(2024J011211)

WO₃ Films Based on Porous ITO Electrodes: Preparation and Electrochromic Property

YANG Guang(), ZHANG Nan, CHEN Shujin, WANG Yi(), XIE An, YAN Yujie()

Fujian Key Laboratory of Functional Materials and Applications, School of Materials Science and Engineering, Xiamen University of Technology, Xiamen 361024, China

Received:2024-12-23 Revised:2025-01-23 Published:2025-07-20 Online:2025-03-19
Contact: YAN Yujie, associate professor. E-mail: yujieyan@xmut.edu.cn;
WANG Yi, lecturer. E-mail: yiwang@xmut.edu.cn
About author:YANG Guang (2000-), male, Master candidate. E-mail: yangguang@stu.xmut.edu.cn
Supported by:
National Natural Science Foundation of China(62304189);Natural Science Foundation of Fujian Province(2023J011450);Natural Science Foundation of Fujian Province(2024J011211)

摘要/Abstract

摘要：

电致变色智能窗可通过调制电致变色材料的光学透过率来调控室外入射光进而实现节能建筑。由于磁控溅射技术具有大面积和均匀沉积的优势, 利用其所制备的非晶三氧化钨(Tungsten Oxide, WO₃)最有实现商业化的潜力。然而, 磁控溅射制备的WO₃薄膜本征致密原子结构导致较低的离子传输效率, 因此其电致变色性能远低于溶液法。本研究提出了基于埋层多孔电极制备微结构磁控溅射基WO₃薄膜的方法, 从而提高材料的光学调制幅度和响应时间。实验结果表明, 与致密WO₃薄膜相比, 通过该方法制备的多孔WO₃薄膜展现出显著提升的电致变色性能。当多孔WO₃薄膜厚度增加到300 nm时, 获得了高达79.08%的光学调制幅度, 2.6 s的着色时间和2.0 s的褪色时间, 以及高达52.5 cm²/C的着色效率。性能提升主要归因于多孔氧化铟锡(Indium Tin Oxide, ITO)电极和多孔WO₃薄膜的协同作用。多孔ITO电极可增加与WO₃组分的接触面积, 使更多电荷注入WO₃薄膜中, 进而促进氧化还原反应过程。此外, 多孔WO₃薄膜也增加了与电解液的接触面积, 随之增加了反应活性位点以及缩短了离子扩散路径, 进而加速了离子扩散和迁移过程, 实现了高效的氧化还原反应和快速的离子传输。本工作为制备高性能微纳结构磁控溅射电致变色薄膜提供了一种有效的方法。

关键词: 电致变色, 磁控溅射, ITO电极, 多孔WO₃

Abstract:

Electrochromic smart windows can regulate indoor light through modulating optical transmittance of electrochromic materials to realize energy-saving buildings. Amorphous tungsten oxide (WO₃) film fabricated by magnetron sputtering technology is the most likely to be industrialized due to its advantages of large-area and uniform deposition. However, electrochromic characteristics of the sputtered WO₃ film lag behind those of the solution-process approach due to inefficient ion transport arising from its intrinsically dense atomic structure. In this work, a strategy to develop microstructured magnetron-sputtered WO₃ films by introducing the buried porous electrodes to improve the optical modulation and response time was proposed. The results demonstrate that the porous sputtered WO₃ films prepared by this method exhibit significantly enhanced electrochromic characteristics compared with the dense WO₃ films. When thickness of the porous WO₃ increased to 300 nm, the optimized electrochromic characteristics were achieved, with a remarkable optical modulation of up to 79.08%, coloring and bleaching times of only 2.6 and 2.0 s, and a high coloring efficiency of 52.5 cm²/C. The improved performance is mainly attributed to synergistic effect of the porous indium tin oxide (ITO) electrode and the porous WO₃ film. The porous ITO electrode can increase the surface area with the increased WO₃ component and then increase electronic charges, facilitating the redox reaction process. Moreover, the porous WO₃ film offers a larger surface area for the electrolyte, increases reactive active sites and shortens ion diffusion pathway, which accelerates the ion diffusion and migration process, realizing efficient redox reactions and fast ion transport. This work provides an effective method for preparing high-performance micro- and nano-structured sputtered electrochromic films.

Key words: electrochromism, magnetron sputtering, ITO electrode, porous WO₃

中图分类号:

TQ174

杨光, 张楠, 陈舒锦, 王义, 谢安, 严育杰. 基于多孔ITO电极的WO₃薄膜的制备及其电致变色性能[J]. 无机材料学报, 2025, 40(7): 781-789.

YANG Guang, ZHANG Nan, CHEN Shujin, WANG Yi, XIE An, YAN Yujie. WO₃ Films Based on Porous ITO Electrodes: Preparation and Electrochromic Property[J]. Journal of Inorganic Materials, 2025, 40(7): 781-789.

图/表 6

图1 基于多孔ITO电极的WO3薄膜的制备工艺流程图

Fig. 1 Preparation process flow chart of WO3 films based on porous ITO electrodes

图2 多孔ITO薄膜与多孔和致密WO3薄膜的SEM照片

Fig. 2 SEM images of the porous ITO film and porous and dense WO3 film (a) SEM image of porous ITO film; (b, c) SEM-EDS images of In and Sn elements in ITO film; (d) SEM image of porous WO3 film; (e, f) SEM-EDS images of W and O elements in WO3 film; (g) SEM image of porous WO3 film; (h) Cross-sectional SEM image of FTO/ITO/WO3; (i) SEM image of dense WO3 film

图3 多孔与致密WO3薄膜的电化学和电致变色性能

Fig. 3 Electrochemical and electrochromic properties of the porous and dense WO3 films (a) CV curves at 50 mV/s; (b) Transmittance spectra at the colored and bleached states; (c) In-situ transmittance spectra at 700 nm; (d) Optical density (ΔOD) variations with respect to the charge density at 700 nm

图4 不同厚度多孔WO3薄膜的电化学和电致变色性能

Fig. 4 Electrochemical and electrochromic properties of the porous WO3 films with different thicknesses (a) CV curves at 50 mV/s; (b) Transmittance spectra at the colored and bleached states; (c) In-situ transmittance spectra at 700 nm; (d) ΔOD variations with respect to the charge density at 700 nm; (e) Digital photos of the coloring and bleaching states. Colorful figures are available on website

图5 不同直径PS微球制备的多孔WO3薄膜的电化学和电致变色性能

Fig. 5 Electrochemical and electrochromic properties of the porous WO3 films prepared from PS microspheres with different diameters (a) CV curves at 50 mV/s; (b) Transmittance spectra at the colored and bleached states; (c) In-situ transmittance spectra at 700 nm; (d) ΔOD variations with respect to the charge density at 700 nm. Colorful figures are available on website

图6 多孔与致密WO3薄膜的离子与电荷传输示意图以及EIS曲线

Fig. 6 Schematic diagrams of ion and charge transport in dense bulk and porous WO3 films and related EIS curves (a) Dense bulk WO3 film; (b) Porous WO3 film; (c) EIS curves of dense bulk and porous WO3 films. Colorful figures are available on website

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基于多孔ITO电极的WO₃薄膜的制备及其电致变色性能

WO₃ Films Based on Porous ITO Electrodes: Preparation and Electrochromic Property

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