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室温下透明层状钙钛矿PEAPbBr中的高对比度热致变色,其高温诱导带隙变化率为0.8 meV/K。

High-Contrast Thermochromism in Room-Temperature Transparent Layered Perovskite PEAPbBr with a High Temperature-Induced Bandgap Change Rate of 0.8 meV/K.

作者信息

Song Xiaoyu, Liu Xinsheng, Zhang Danwen, Liao Jingyan, Zhu Siqi, Zheng Wei

机构信息

School of Materials, Sun Yat-sen University, Shenzhen, Guangdong 518107, China.

出版信息

J Am Chem Soc. 2024 Sep 4;146(35):24670-24680. doi: 10.1021/jacs.4c09090. Epub 2024 Aug 20.

Abstract

Two-dimensional organic-inorganic hybrid layered perovskites have emerged as a new generation of optoelectronic materials. However, the thermochromism in organic-inorganic hybrid layered perovskites has been rarely explored in depth. A further understanding of the mechanism is necessary and favorable for the application. Here, transparent centimeter-sized single crystals of the organic-inorganic hybrid layered perovskite (CHCHNH)PbBr (PEAPbBr) were synthesized using an improved evaporation method. As a typical organic-inorganic hybrid layered perovskite, the PEAPbBr single crystal shows high-contrast and progressive thermochromism exhibiting a change from colorlessness and transparency to lemon yellow in a wide temperature range of 200-450 K. Based on the calculation through the Varshni equation, the temperature-induced bandgap change rate directly associated with the high-contrast thermochromism of PEAPbBr reaching 0.8 meV/K. This value is higher than that of many three-dimensional perovskites and traditional IV-III semiconductors. Furthermore, the temperature-dependent 193 nm photoluminescence spectra suggest that this high temperature-induced bandgap change rate of PEAPbBr is a result of the competitive interaction between lattice thermal expansion and electron-phonon coupling (Fröhlich coupling coefficient Γ = 2.215). Based on the characteristics introduced above, PEAPbBr as an organic-inorganic hybrid layered perovskite has a better performance in achieving the balance between high-contrast and high room-temperature transmittance. Therefore, PEAPbBr is a material with great potential in applications like temperature-indicating labels. This work provides valuable insights into the thermochromism of layered perovskites, offering a new material system and approach for developing thermochromic materials with higher sensitivity and efficiency.

摘要

二维有机-无机杂化层状钙钛矿已成为新一代光电子材料。然而,有机-无机杂化层状钙钛矿中的热致变色现象尚未得到深入研究。进一步了解其机制对于应用而言是必要且有益的。在此,采用改进的蒸发法合成了厘米级透明的有机-无机杂化层状钙钛矿(CHCHNH)PbBr(PEAPbBr)单晶。作为典型的有机-无机杂化层状钙钛矿,PEAPbBr单晶在200-450K的宽温度范围内呈现出高对比度且渐进的热致变色现象,表现为从无色透明变为柠檬黄。通过Varshni方程计算得出,与PEAPbBr高对比度热致变色直接相关的温度诱导带隙变化率达到0.8 meV/K。该值高于许多三维钙钛矿和传统IV-III族半导体。此外,温度依赖的193nm光致发光光谱表明,PEAPbBr这种高温诱导的带隙变化率是晶格热膨胀与电子-声子耦合(弗罗利希耦合系数Γ = 2.215)之间竞争相互作用的结果。基于上述特性,PEAPbBr作为有机-无机杂化层状钙钛矿在实现高对比度与高室温透过率之间的平衡方面具有更好的性能。因此,PEAPbBr在温度指示标签等应用中具有巨大潜力。这项工作为层状钙钛矿的热致变色提供了有价值的见解,为开发具有更高灵敏度和效率的热致变色材料提供了新的材料体系和方法。

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