稀土含氧氢化物光致变色薄膜研究现状

李明; 金平实; 曹逊

doi:10.7498/aps.71.20221046

摘要

光致变色材料作为一种自适应型智能材料, 在智能窗户、光电传感器、光学存储等领域均有广泛的应用. 稀土含氧氢化物(REH_xO_y)薄膜作为一种新型光致变色材料, 自发现以来, 就以其高效可逆的变色性能、简单可重复的制备方法、快速的着褪色时间受到了大量的关注. 本文基于近年来针对稀土含氧氢化物光致变色薄膜的结构组成、变色机理、性能调控的研究现状进行了综述. REH_xO_y薄膜可以响应紫外光和可见光的激发, 对全光谱波段透过率进行大幅调节. 光致变色机理可归类为晶格收缩机制、氧交换机制、局部金属相变、氢迁移机制4种解释. 目前可以通过控制薄膜形貌、设计化学组分、提高衬底适配、多层膜结构设计等方式进行性能调控. 最后对薄膜之后的研究重点进行了展望.

关键词:

Abstract

Photochromic material, as an adaptive smart material, has a wide range of applications in smart windows, photoelectric sensors, optical storage, etc. Oxygen-containing rare-earth metal hydride (REH_xO_y) film, a new type of photochromic material, has attracted the attention of researchers for its efficient and reversible color-changing properties, simple and reproducible preparation methods, and fast darkening-bleaching time. In this paper we review the current research status of structural composition, color change mechanism, and property modulation of oxygen-containing rare-earth metal hydride films. Exposure to visible light and ultraviolet (UV) light can lead the optical transmission of visible and infrared (IR) light to degrade. The photochromic mechanisms can be grouped into four mechanisms: lattice contraction mechanism, oxygen exchange mechanism, local metal phase change, and hydrogen migration mechanism. Currently, performance can be tuned by controlling film morphology, designing chemical components, improving substrate adaptation, multilayer film structure design, etc. Finally, the future research focus of thin film is prospected.

Keywords:

作者及机构信息

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.
中国科学院大学材料科学与光电工程中心, 北京　100049

通信作者: 曹逊, cxun@mail.sic.ac.cn

基金项目: 中国科学院ANSO国际合作专项(批准号: ANSO-CR-KP-2021-01)和国家自然科学基金(批准号: 51972328, 62175248)资助的课题.

Authors and contacts

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

2.
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: Cao Xun, cxun@mail.sic.ac.cn

Funds: Project supported by ANSO International Cooperation Project of Chinese Academy of Sciences (Grant No. ANSO-CR-KP-2021-01) and the National Natural Science Foundation of China (Grant Nos. 51972328, 62175248).

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参考文献

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施引文献

图 1 REH_xO_y薄膜的光致变色机理、制备方法及应用展望

Fig. 1. Photochromic mechanism, preparation method and application prospect of REH_xO_y film.

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图 2 REH_xO_y薄膜(YH_xO_y和GdH_xO_y)的结构模型　(a)晶格能计算GdH_xO_y立方相结构模型; (b) DFT理论预测YH_xO_y 17种结构相图^[19,20]

Fig. 2. Structural models of REH_xO_y (YH_xO_y and GdH_xO_y) films: (a) Lattice energy calculation GdH_xO_y cubic phase structure model; (b) DFT predicts 17 structural phase diagrams of YH_xO_y^[19,20].

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图 3 氧浓度对薄膜带隙的影响　(a)梯度氧含量制备样品; (b)横向尺度上O/Y化学计量比; (c)横向尺度上带隙变化^[24]

Fig. 3. Effect of oxygen concentration on the band gap of thin films: (a) Samples prepared with gradient oxygen content; (b) the O/Y stoichiometric ratio in the horizontal direction; (c) the band gap variation in the horizontal direction^[24].

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图 4 YH_xO_y薄膜光学性能和电学性能　(a)光照前后样品透过率、反射率和光学密度的变化^[13]; (b) Tauc-plot法计算样品直接带隙与间接带隙^[29]; (c)光照前后样品的电阻变化^[28]

Fig. 4. Optical and electrical properties of YH_xO_y films: (a) The changes in transmission, reflection, and optical density of YH_xO_y films before and after light exposure^[13]; (b) the direct and indirect bandgap of YH_xO_y films^[29]; (c) the changes in resistivity of YH_xO_y films under light induction^[28].

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图 5 (a), (b)不同波长和强度光照下薄膜的光致变色响应^[30]; (c), (d)不同温度下薄膜的光致变色响应^[33]

Fig. 5. (a), (b) Photochromic response of thin films under different wavelengths and intensities of light^[30]; (c), (d) photochromic response of samples at different temperatures^[33].

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图 6 (a)同步X射线原位表征光照下样品晶格变化^[37]; (b)光照之后拉曼光谱中出现金属相峰位^[40]; (c)不同气氛下样品光照后的褪色速度^[41]; (d)光致变色前后薄膜成分变化^[32]

Fig. 6. (a) Simultaneous X-ray in situ characterization of sample lattice changes under illumination^[37]; (b) appearance of metal phase peaks in Raman spectra after illumination^[40]; (c) recovery rate of samples under different atmospheres after illumination^[41]; (d) the change in film composition before and after photochromic^[32].

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图 7 双相结构下光子诱导氢转移^[44]

Fig. 7. Photon-induced hydrogen transfer in a two-phase structure^[44].

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图 8 光照后“双聚氢”结构的形成^[18]

Fig. 8. Formation of the dihydrogen structure after illumination^[18]

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图 9 (a)不同衬底样品的光致变色响应^[52]; (b) 不同厚度样品的光致变色响应^[47]; (c)不同稀土元素样品的光致变色响应^[14]; 不同溅射压力样品(d) YH_xO_y薄膜和(e) GdH_xO_y薄膜的光致变色响应^[15], 以及(f)光致变色性能与化学组分之间的关系^[15]

Fig. 9. (a) Photochromic response of samples with different substrates^[52]; (b) photochromic response of samples with different thicknesses^[47]; (c) photochromic response of different rare earth element samples^[14]. The photochromic response of different sputtering pressure samples: (d) YH_xO_y film; (e) GdH_xO_y film^[15]; (f) relationship between photochromic properties and chemical components^[15].

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图 10 光学设计的高透过率和高发射率模型^[55]

Fig. 10. High transmittance and high emissivity models for optical design^[55].

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图 11 YH_xO_y与VO₂复合薄膜的四态调控^[31]

Fig. 11. Four-state modulation of spectral changes in YH_xO_y and VO₂ composite films^[31].

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表 1 部分有机无机光致变色材料总结^[1]

Table 1. Summary of some organic and inorganic photochromic materials^[1].

Type of the material		Name of material	Photochromism principle	Method of bleaching	Color change
Organic		Diarylethenes	Photocyclization reaction	Expose to visible light	Colorless → red
		Fulgide	Photochemical conrotatory	Expose to visible light	Pale yellow → red
		Spriopyran	Hetetolytic cleavage/photocyclization	Expose to visible light/heating	Colorless → purple
		Naphthopyarn	Hetetolytic cleavage/photocyclization	Removing UV	Colorless → gray
Inorganic	TMOs	WO₃	Photon prompted redox reaction	Removing UV	Colorless → blue
		TiO₂	Photon prompted redox reaction	Removing UV and exposing to air	Faint yellow → black
		MoO₃	Intercalation-deintercalation of univalent cations	Removing UV	White → blue
	Metal halides	Lead chloride [Pb₃Cl₆(CV)]H₂O]_n	Light-triggered electron transfer	Removing UV/ anneal in air	Pale yellow → blue
	Metal halides	AgCl	Light-triggered reversible decomposition	Removing UV	Transparent → brown

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表 2 已有报道稀土元素的性质

Table 2. Properties of reported rare earth element.

Element	Atomic mass	Ion size/nm	Sputtering pressure/Pa	Band gap/eV	ΔT/%	文献
Y	89	0.090	0.4	2.6	37	[14]
Gd	157.25	0.094	0.6	2.25	45	[14]
Dy	162.5	0.091	0.6	2.25	33	[14]
Er	167.26	0.088	0.6	2.4	35	[14]

下载: 导出CSV

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[31]	Shao Z, Cao X, Zhang Q, Long S, Chang T, Xu F, Jin P. 2019 Sol. Energy Mater. Sol. Cells 200 110044 Google Scholar
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