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

doi:10.15541/jim20200633

无机材料学报 ›› 2021, Vol. 36 ›› Issue (5): 479-484.DOI: 10.15541/jim20200633

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

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

贾汉祥¹^,²(), 邵泽伟¹^,², 黄爱彬¹, 金平实¹, 曹逊¹()

1.中国科学院上海硅酸盐研究所, 高性能陶瓷和超微结构国家重点实验室, 上海 200050
2.中国科学院大学, 北京 100049

收稿日期:2020-11-05 修回日期:2020-11-25 出版日期:2021-05-20 网络出版日期:2021-04-19
通讯作者: 曹逊, 研究员. E-mail: cxun@mail.sic.ac.cn
作者简介:贾汉祥(1993-), 男, 博士研究生. E-mail:jiahanxiang@student.sic.ac.cn

Sandwich Structured Electrolyte of High Sputtering Efficiency for All-solid-state Electrochromic Devices by Optical Design

JIA Hanxiang¹^,²(), SHAO Zewei¹^,², HUANG Aibin¹, JIN Pingshi¹, CAO Xun¹()

1. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2020-11-05 Revised:2020-11-25 Published:2021-05-20 Online:2021-04-19
Contact: CAO Xun, professor. E-mail: cxun@mail.sic.ac.cn
About author:JIA Hanxiang(1993-), male, PhD candidate. E-mail:jiahanxiang@student.sic.ac.cn
Supported by:
National Natural Science Foundation of China(51972328);National Natural Science Foundation of China(51903244);Youth Innovation Promotion Association, Chinese Academy of Sciences(2018288);Science Foundation for Youth Scholar of State Key Laboratory of High Performance Ceramics and Superfine Microstructures(SKL201703);Shanghai Pujiang Program(18PJD051);Key Research and Development Plan of Anhui Province(1804a09020061);Shanghai Sailing Program(19YF1454300)

摘要/Abstract

摘要：

全固态电致变色器件以其光学对比度高、响应速度快以及良好的循环稳定性等特点而广泛应用于节能窗、屏幕显示、多功能储能设备等诸多领域。然而, 传统的基于单层电解质体系的全固态电致变色器件常受限于光学透过率和溅射效率的不足。本工作利用反应直流磁控溅射技术成功制备了基于LiAlO_x/Ta₂O₅/LiAlO_x(ATA)三明治结构电解质的全固态电致变色器件。通过引入ATA三明治结构电解质, 所制得的七层体系电致变色器件(ITO/NiO/LiAlO_x/Ta₂O₅/LiAlO_x/WO₃/ITO)兼具了优异的透光率和可观的溅射效率。该全固态电致变色器件取得了令人满意的着色效率(79.6 cm²/C), 更快的响应速度(着色时间1.9 s, 褪色时间1.6 s)以及数百次循环的良好稳定性。此外, ATA三明治结构电解质充分利用了Ta₂O₅优异的离子传输速率和稳定性, 并提供了足够的锂离子以满足快速变色切换的需求。因而, 通过连续直流溅射制备的基于ATA三明治结构电解质的全固态电致变色器件有望为高性能电致变色器件的量产和实际应用提供重要的指导。

关键词: 无机全固态, 电致变色器件, 多层电解质, 溅射效率, 光学设计

Abstract:

The all-solid-state electrochromic devices (ECDs) have been widely developed for energy-saving windows, screen displays, multi-functional energy storage devices due to their characteristics such as large optical contrast, fast switching speed and good cycle stability. However, traditional all-solid-state ECDs based on monolayer electrolyte system are often limited by ordinary optical transmittance and inadequate sputtering efficiency. Herein, the all-solid- state ECDs integrated with LiAlO_x/Ta₂O₅/LiAlO_x (ATA) sandwich structured electrolyte were successfully fabricated by reactive DC magnetron sputtering technique. By means of introduction of ATA sandwich structured electrolyte, the prepared ECDs with seven layer (ITO/NiO/LiAlO_x/Ta₂O₅/LiAlO_x/WO₃/ITO) was endowed with superfine optical transmittance and substantial sputtering efficiency simultaneously. The ATA-based ECDs realized satisfactory coloration efficiency of 79.6 cm²/C, fast switching speed as short as 1.9 s for coloring and 1.6 s for bleaching, and excellent cycling stability over hundreds of cycles. Furthermore, ATA sandwich structured electrolyte makes full use of the excellent ionic conductivity and stability of Ta₂O₅, as well as enough lithium ions to meet the demand for fast color switching. Hence, ATA-based all-solid-state ECDs by continuous DC sputtering is expected to provide effective guidance for the mass production and practical application of the high-performance ECDs.

Key words: inorganic all-solid-state, electrochromic device, multilayer electrolyte, sputtering efficiency, optical design

中图分类号:

TQ174

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.

JIA Hanxiang, SHAO Zewei, HUANG Aibin, JIN Pingshi, CAO Xun. Sandwich Structured Electrolyte of High Sputtering Efficiency for All-solid-state Electrochromic Devices by Optical Design[J]. Journal of Inorganic Materials, 2021, 36(5): 479-484.

图/表 6

Table 1 Sputtering parameters for each layer of ECDs

Layer	Target	Pressure/Pa	Q_Ar : Q_O2	Power/W	Thickness/nm
LiAlO_x^a	Li-Al	2.0	40 : 10	200	~100
Ta₂O₅	Ta	0.7	45 : 5	200	~200
LiAlO_x^b	Li-Al	2.0	40 : 10	200	~100
WO_x	W	1.0	47 : 3	70	400
NiO	Ni	1.0	40 : 10	100	150
ITO	ITO	0.3	100 : 0	140	400

Fig. 1 AFM image of LiAlOx layer (a) and Ta2O5 layer (b) of sandwich structured electrolyte (ATA), cross-section SEM image of ATA (c) and partial enlarged detail of it (d), surface SEM image of ATA (e), and element distribution of cross-section of ECDs (f)

Fig. 2 UV-Vis-NIR spectra (a) of Ta2O5 films deposited under different O2 ratios of 0, 5%, 10%, 15%, respectively, optical modulation (b) of ECDs during -3 V to 3 V, experimental (c) and calculated (d) transmittance spectra of sandwich structured electrolyte, in which S1 and S2 refer to two parallel samples, LAO refers to LiAlOx, TO refer to Ta2O5, and LTO refer to Li+-inserted Ta2O5, optical design for optimized thickness of ATA via software of Essential Macleod (e)

Fig. 3 Comparison of sputtering efficiency parameters for several typical layers of ECDs

Table 2 Comparison of sputtering efficiency for several typical systems

Layer	Target	Power supply	Power density/(W·cm^-2)	Sputtering rate/ (nm·min^-1)	Sputtering efficiency/ ((nm·min^-1)/(W·cm^-2))	Ref.
Ta₂O₅	Ta₂O₅	RF	0.57	2.7	4.74	[23]
Ta₂O₅	Ta	DC	0.89	15	16.85	This work
LiTaO₃	LiTaO₃	RF	0.48	1.2	2.50	[24]
LiAlO_x	Li-Al	DC	0.16	1	6.25	This work
WO_x	WO₃	RF	1.78	5	2.81	[25]
WO_x	W	DC	0.40	16	40	This work
NiO	NiO	RF	0.64	3.6	5.63	[26]
NiO	Ni	DC	0.32	5	15.63	This work

Fig. 4 Schematic diagram of the ATA based seven-layer all-solid-state ECDs by optical design (a), color efficiency of ECDs with inset correspond to EC reaction of ECDs (b), switching speed (c) and cycle durability test (d) of ECDs

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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

Sandwich Structured Electrolyte of High Sputtering Efficiency for All-solid-state Electrochromic Devices by Optical Design

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