多彩氧化钨薄膜的红外电致变色性能研究

doi:10.15541/jim20200463

无机材料学报 ›› 2021, Vol. 36 ›› Issue (5): 485-491.DOI: 10.15541/jim20200463

所属专题：电致变色材料与器件；电致变色专栏2021

• 专栏:电致变色材料与器件(特邀编辑:王金敏,刁训刚) • 上一篇下一篇

多彩氧化钨薄膜的红外电致变色性能研究

武琦¹^,²(), 丛杉¹, 赵志刚¹()

1.中国科学院苏州纳米技术与纳米仿生研究所, 苏州 215123
2.中国科学技术大学纳米科学技术学院, 苏州 215123

收稿日期:2020-08-13 修回日期:2020-09-25 出版日期:2021-05-20 网络出版日期:2021-04-19
通讯作者: 赵志刚, 研究员. E-mail:zgzhao2011@sinano.ac.cn
作者简介:武琦(1997-), 女, 硕士研究生. E-mail:qwu2019@sinano.ac.cn
基金资助:
国家自然科学基金(51772319);国家自然科学基金(51772320);国家自然科学基金(51972331);江西省自然科学基金(20181ACB20011);中国科学院对外合作项目(121E32KYSB20190008);江苏省六大人才高峰(XCL-170);中国科学院青年创新促进会(2018356);江西省杰出青年基金(20192BCBL23027)

Infrared Electrochromic Property of the Colorful Tungsten Oxide Films

WU Qi¹^,²(), CONG Shan¹, ZHAO Zhigang¹()

1. Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou 215123, China
2. Nano Science and Technology Institute, University of Science and Technology of China, Suzhou 215123, China

Received:2020-08-13 Revised:2020-09-25 Published:2021-05-20 Online:2021-04-19
Contact: ZHAO Zhigang, professor. E-mail:zgzhao2011@sinano.ac.cn
About author:WU Qi(1997-), female, Master candidate. E-mail:qwu2019@sinano.ac.cn
Supported by:
National Natural Science Foundation of China(51772319);National Natural Science Foundation of China(51772320);National Natural Science Foundation of China(51972331);Natural Science Foundation of Jiangxi Province(20181ACB20011);External Cooperation Program of the Chinese Academy of Sciences(121E32KYSB20190008);Six Talent Peaks Project of Jiangsu Province(XCL-170);Youth Innovation Promotion Association of Chinese Academy of Sciences(2018356);Outstanding Youth Fund of Jiangxi Province(20192BCBL23027)

摘要/Abstract

摘要：

电致变色材料能够在可见-红外宽频谱范围内对吸收率、透过率、反射率和发射率进行动态调节, 是人工调制材料光谱特征的有效手段。在实际应用场合, 对于色彩(可见光)与热辐射(红外线)可控调节的需求往往并存, 利用单一电致变色器件实现可见、红外双波段的光学调制性能具有重要意义。现阶段对于电致变色材料的设计主要集中于可见光谱的调节能力及颜色转变, 忽略了对材料红外光谱的探究。本研究选取具有法布里-铂罗(F-P)空腔结构的多彩氧化钨薄膜进行可见-红外宽频谱电致变色探究, 具有F-P空腔结构的氧化钨薄膜材料在可见光区呈现多样化、明亮的颜色, 再对多彩薄膜进行图案化设计, 即可得到具有各种图案的多彩薄膜, 并且在外加偏压的作用下可以实现多样化的颜色转变。同时, 多彩氧化钨薄膜的红外反射率也可获得明显的可控调制效果, 在中波段(Medium Wave, MW)3.5 μm左右处不同颜色薄膜均可获得高于25.00%的红外调制率。本研究表明, 多彩氧化钨薄膜可以实现可见-红外宽频谱的分立、可控调节, 在智能窗、热管理、辐射制冷等应用领域有巨大潜力, 可达到光、热性能协同调制的效果。

关键词: 多彩氧化钨, 电致变色, 红外调制

Abstract:

Electrochromic materials are capable in a dynamically modulation over their absorption, transmission, reflection and emissivity covering the visible and infrared regions, which is recognized as one of the most effective strategies for an artificial control over the optical spectrum. In practical devices, the modulations for color (visible light) and heat (near-infrared irradiation) are both in demand, and thus it is of significant importance to achieve the dual-band control within single electrochromic device. However, the present design of electrochromic materials mainly focuses on the adjustment ability of visible spectrum or color transformation, while leaving the modulation of infrared spectra often negligible. In this study, a multi-color tungsten oxide film with F-P cavity structure is selected to explore the wide-spectrum electrochromism of visible and infrared spectral regions. The tungsten oxide film material with F-P cavity structure presents diversified and bright colors in the visible region with various color patterns, and diversified color alternation can be realized under applied biases. At the same time, the infrared reflectance of colorful tungsten oxide films can also be modulated significantly, for example, infrared modulation rates higher than 25.00% can be obtained in the middle wavelength (around 3.5 μm) in the colored films. The research shows that the multi-color tungsten oxide film can realize the discrete and controllable adjustment of the visible and infrared spectral region in the wide spectrum, and has great potential in the application of smart window, thermal management, radiative cooling and other fields, which can even achieve the in-demand cooperative modulation of light and heat performance.

Key words: colorful tungsten oxide film, electrochromism, infrared modulation

中图分类号:

TQ174

武琦, 丛杉, 赵志刚. 多彩氧化钨薄膜的红外电致变色性能研究[J]. 无机材料学报, 2021, 36(5): 485-491.

WU Qi, CONG Shan, ZHAO Zhigang. Infrared Electrochromic Property of the Colorful Tungsten Oxide Films[J]. Journal of Inorganic Materials, 2021, 36(5): 485-491.

图/表 6

图1 多彩膜的结构示意图(a), 断面SEM照片(b), 实拍薄膜样品和图案化样品(c), 以及七种颜色的反射率曲线(d)

Fig. 1 Schematic illustration of the colorful film (a), cross- sectional SEM image (b), optical images of the electrochromic electrodes with different colors and the patterned samples (c), and reflectance spectra of electrode films with seven colors (d)

图2 多彩氧化钨薄膜在不同电压下电致变色的光学图片(a)和黄色、紫色、绿色三种薄膜在不同电压下反射率曲线变化(b-d)

Fig. 2 Optical images of electrochromic films at different applied potentials (a), variation of reflectance spectra of yellow, purple and green films at different applied potential (b-d)

图3 多彩氧化钨薄膜在中红外区(3~13 μm)的反射率曲线

Fig. 3 Reflectance spectra of the tungsten oxide film in the mid-infrared region (3-13 μm)

图4 黄色、紫色、绿色三种薄膜在不同电压下的中红外反射率曲线(a~c)和不同W厚度的绿色薄膜的红外反射率曲线(d)

Fig. 4 Variation of mid-infrared reflectance spectra of yellow, purple and green films at different applied potentials (a-c), mid-infrared reflectance spectra of green films with different W thicknesses (d) Solid and dotted lines in (d) are the samples before and after coloration, respectively, wherein the applied voltage is fixed at -0.6 V

表1 薄膜在MW和LW的反射率调制

Table 1 Reflectance modulation of films in MW and LW

Color	Band	ΔR
Yellow	MW	25.61%
Yellow	LW	6.67%
Violet	MW	33.68%
Violet	LW	8.91%
Green	MW	46.00%
Green	LW	15.39%

图5 不同颜色的氧化钨薄膜的红外热成像图像(a), 对绿色薄膜加不同负压的红外热成像图像(b)、光学图像(c)及对应的反射率曲线变化(d)

Fig. 5 Infrared thermal imaging of tungsten oxide films of different colors (a), infrared thermal imaging photos of green films with different negative potentials (b), optical images (c) and their corresponding reflectance curve changes (d)

参考文献 26

[1]	GRANQVIST C G. Handbook of Inorganic Electrochromic Materials. Amsterdam: Elsevier, 1995: 9-13.
[2]	MORTIMER R J, ROSSEINSKY D R, MONK P M S. Electrochromic Materials and Devices. New York: Wiley-VCH Verlag GmbH & Co. KGaA. 2015: 3-33.
[3]	MORTIME R J. Electrochromic materials. Annual Review of Materials Research, 2011,41(1):241-268.
[4]	WANG ZHEN, WANG XIAO-YU, CONG SHAN, et al. Fusing electrochromic technology with other advanced technologies: a new roadmap for future development. Materials Science and Engineering: R-Reports, 2020, 140: 100524-1-26.
[5]	LI NA, LI YAO, YIN YA-DONG, et al. Dynamically switchable multicolor electrochromic films. Small. Dynamically switchable multicolor electrochromic films. Small, 2019, 15(7): 1804974-1-7. DOI URL PMID
[6]	XIAO LI-LI, LÜ YING, LIU XING-YUAN, et al. WO₃-based electrochromic distributed Bragg reflector: toward electrically tunable microcavity luminescent device. Advanced Optical Materials, 2017,6(1): 1700791-1-8.
[7]	LI HAI-ZENG, FIRBY C J, ELEZZABI A Y, et al. Rechargeable aqueous electrochromic batteries utilizing Ti-substituted tungsten molybdenum oxide based Zn²+ ion intercalation cathodes. Advanced Materials, 2019, 31(15): 1807065-1-9. URL PMID
[8]	ROGALSKI A, CHRZANOWSKI K. Infrared devices and techniques. Opto-Electronics Review, 2002,10(2):111-136.
[9]	XU CHENG-YI, STIUBIANU G T, GORODETSKY A A. Adaptive infrared-reflecting systems inspired by cephalopods. Science, 359(6383):1495-1500. DOI URL PMID
[10]	PENG LIANG, LIU DONG-QING, ZU MEI, et al. A multilayer film based selective thermal emitter for infrared stealth technology. Advanced Optical Materials, 2018, 6(23): 1801006-1-8.
[11]	LYU J, LIU ZENG-WEI, ZHANG XUE-TONG,et al. Nanofibrous Kevlar aerogel films and their phase-change composites for highly efficient infrared stealth. ACS Nano, 2019,13:2236-2245. DOI URL PMID
[12]	CAI GUO-FA, WANG JIANG-XIN, LEE P S. Next-generation multifunctional electrochromic devices. Accounts of Chemical Research, 2016,49(8):1469-1476. DOI URL PMID
[13]	CAI GUO-FA, CUI MENG-QI, LEE P S,et al. Ultra-large optical modulation of electrochromic porous WO₃ film and the local monitoring of redox activity. Chemical Science, 2016,7(2):1373-1382. DOI URL PMID
[14]	CONG SHAN, GENG FENG-XIA, ZHAO ZHI-GANG,et al. Single-crystalline tungsten oxide quantum dots for fast pseudocapacitor and electrochromic applications. Advanced Materials, 2014,26(25):4260-4267. URL PMID
[15]	WANG ZHEN, ZHANG QING-ZHU, ZHAO ZHI-GANG, et al. Using intrinsic intracrystalline tunnels for near-infrared and visible- light selective electrochromic modulation. Advanced Optical Materials, 2017, 5(11): 1700194-1-6. DOI URL PMID
[16]	ZHAO JIAN-CUN, LEI DANG-YUAN, YU YI-TING, et al. Defining deep-subwavelength-resolution, wide-color-gamut, and large-viewing-angle flexible subtractive colors with an ultrathin asymmetric Fabry-Perot lossy cavity. Advanced Optical Materials, 2019, 7(23): 1900646-1-8.
[17]	YANG ZHENG-MEI, ZHOU YAN-MING, DUAN HUI-GAO, et al. Reflective color filters and monolithic color printing based on asymmetric Fabry-Perot cavities using nickel as a broadband absorber. Advanced Optical Materials, 2016,4(8):1196-1202.
[18]	YANG ZHENG-MEI, JI CHEN-GANG, LIU DONG, et al. Enhancing the purity of reflective structural colors with ultrathin bilayer media as effective ideal absorbers. Advanced Optical Materials, 2019, 7(21): 1900739-1-9. URL PMID
[19]	LEE K T, HAN S Y, PARK H J. Omnidirectional flexible transmissive structural colors with high-color-purity and high- efficiency exploiting multicavity resonances. Advanced Optical Materials, 2017, 5(14): 1700284-1-9.
[20]	WANG ZHEN, WANG XIAO-YU, ZHAO ZHI-GANG, et al. Towards full-colour tunability of inorganic electrochromic devices using ultracompact Fabry-Perot nanocavities. Nature Communications, 2020, 11(1): 302-1-9.
[21]	CHEN JIAN, WANG ZHEN, ZHAO ZHI-GANG, et al. Fabry-Perot cavity-type electrochromic supercapacitors with exceptionally versatile color tunability. Nano Letters, 2020,20(3):1915-1922. URL PMID
[22]	SAUVET K, SAUQUES L, ROUGIER A. IR electrochromic WO₃ thin films: from optimization to devices. Solar Energy Materials and Solar Cells, 2009,93(12):2045-2049.
[23]	SALISBURY J W, WALD A, D'ARIA D M. Thermal-infrared remote sensing and Kirchhoff's law 1. laboratory measurements. Journal of Geophysical Research: Solid Earth, 1994,99(B6):11897-11911.
[24]	KORB A R, SALISBURY J W, D'ARIA D M. Thermal-infrared remote sensing and Kirchhoff's law: 2. field measurements. Journal of Geophysical Research: Solid Earth, 1999,104(B7):15339-15350.
[25]	ZHANG XIANG, TIAN YAN-LONG, LI YAO, et al. Preparation and performances of all-solid-state variable infrared emittance devices based on amorphous and crystalline WO₃ electrochromic thin films. Solar Energy Materials and Solar Cells, 2019,200: 109916-1-6.
[26]	CHONG S V, INGHAM B, TALLON J L. Novel materials based on organic-tungsten oxide hybrid systems I: synthesis and characterization. Current Applied Physics, 2004,4:197-201.

多彩氧化钨薄膜的红外电致变色性能研究

Infrared Electrochromic Property of the Colorful Tungsten Oxide Films

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 6

参考文献 26

相关文章 15

编辑推荐

Metrics

本文评价

[1]	张家强, 邹馨蕾, 王能泽, 贾春阳. 两步电沉积法制备Zn-Fe PBA薄膜及其在电致变色器件中的性能研究[J]. 无机材料学报, 2022, 37(9): 961-968.
[2]	张笑宇, 刘永盛, 李然, 李耀刚, 张青红, 侯成义, 李克睿, 王宏志. 基于Cu₃(HHTP)₂薄膜的离子液体电致变色电极[J]. 无机材料学报, 2022, 37(8): 883-890.
[3]	黄郅航, 滕官宏伟, 铁鹏, 范德松. 钙钛矿陶瓷薄膜的电致变色特性[J]. 无机材料学报, 2022, 37(6): 611-616.
[4]	王天悦, 王梦颖, 黄庆姣, 杨佳明, 王顺花, 刁训刚. 溶胶-凝胶旋涂法制备电致变色智能窗用钛酸锂薄膜[J]. 无机材料学报, 2021, 36(5): 471-478.
[5]	贾汉祥, 邵泽伟, 黄爱彬, 金平实, 曹逊. 光学设计用于全固态电致变色器件的高溅射效率三明治结构电解质[J]. 无机材料学报, 2021, 36(5): 479-484.
[6]	王金敏, 后丽君, 马董云. 氧化钼电致变色材料与器件[J]. 无机材料学报, 2021, 36(5): 461-470.
[7]	张翔, 李文杰, 王乐滨, 陈曦, 赵九蓬, 李垚. 无机电致变色材料反射特性研究进展[J]. 无机材料学报, 2021, 36(5): 451-460.
[8]	钟晓岚, 刘雪晴, 刁训刚. 基于氧化钨和氧化镍的电致变色器件研究进展[J]. 无机材料学报, 2021, 36(2): 128-139.
[9]	方华靖, 赵泽天, 武文婷, 汪宏. 柔性电致变色器件研究进展[J]. 无机材料学报, 2021, 36(2): 140-151.
[10]	周开岭, 汪浩, 张倩倩, 刘晶冰, 严辉. WO₃电致变色薄膜离子传输动力过程及其循环稳定性[J]. 无机材料学报, 2021, 36(2): 152-160.
[11]	赵起, 乔科, 姚勇吉, 陈长, 陈东初, 高彦峰. 基于高电导率的疏水气相SiO₂复合凝胶电解质的高性能电致变色器件[J]. 无机材料学报, 2021, 36(2): 161-167.
[12]	范宏伟, 李克睿, 侯成义, 张青红, 李耀刚, 王宏志. 多功能电致变色器件:从多器件到单器件集成[J]. 无机材料学报, 2021, 36(2): 115-127.
[13]	贾汉祥, 曹逊, 金平实. 无机全固态电致变色材料与器件研究进展[J]. 无机材料学报, 2020, 35(5): 511-524.
[14]	陈钧,马培华,张诚,劳伦·鲁尔曼,吕耀康. 新型多功能无机/有机复合薄膜的制备及电化学性能研究[J]. 无机材料学报, 2020, 35(2): 217-223.
[15]	王金敏, 于红玉, 马董云. 纳米二氧化锰的制备及其应用研究进展[J]. 无机材料学报, 2020, 35(12): 1307-1314.