中国科学院福建物质结构研究所黄小荥团队报道了空位对空位有序双钙钛矿衍生物的发光和水响应性能的影响。相关研究成果于2024年8月13日发表在《德国应用化学》。

空位有序钙钛矿及其衍生物代表了混合金属卤化物的一个重要亚类，在发光器件和光伏等应用中具有前景。了解空位-性能关系对于设计相关特定任务的材料至关重要，但该领域的研究仍然较少。

研究人员首次使用Connolly表面定量计算空位有序双钙钛矿衍生物（VDPDs）中的空位体积（V□，□=空位）。基于零维（0-D）[N（烷基）4]2Sb□Cl5□'型VDPD，建立了空位与结构、光致发光性能和湿度稳定性之间的关系。与更常用的A₂M（IV）X₆□型双钙钛矿（A=阳离子，M=金属离子，X=卤化物）相比，[N（烷基）₄]₂Sb□Cl₅□'具有双空位。结果表明，在0-D VDPDs中，光致发光量子产率与V□之间存在反比关系。

此外，首次报道了从A₂SbCl₅到A₃Sb₂Cl₉的结构转变，在此过程中，首次在VDPD中观察到新的“门打开”气体吸附现象，水蒸气的“S”形吸附等温线证明了这一点，表明了阳离子控制的水蒸气响应行为。开发了一种混合阳离子策略来调节VDPDs的湿度稳定性。A₂M（III）□X₅□’型材料具有可控的水响应行为和独特的“开-关-开”发光转化，在多层次信息防伪应用中显示出巨大的前景。

附：英文原文

Title: Vacancy Effect on the Luminescent and Water Responsive Properties of Vacancy-ordered Double Perovskite Derivatives

Author: Zeping Wang, Dandan Huang, Yi Liu, Haowei Lin, Zhizhuan Zhang, Abdusalam Ablez, Tinghui Zhuang, Kezhao Du, Jing Li, Xiao-Ying Huang

Issue&Volume: 2024-08-13

Abstract: Vacancy-ordered perovskites and derivatives represent an important subclass of hybrid metal halides with promise in applications including light emitting devices and photovoltaics. Understanding the vacancy-property relationship is crucial for designing related task-specific materials, yet research in this field remains sporadic. For the first time, we use the Connolly surface to quantitatively calculate the volume of vacancy (V□, □ = vacancy) in vacancy-ordered double perovskite derivatives (VDPDs). A relationship between void fraction and the structure, photoluminescent properties and humidity stability was established based on zero-dimensional (0-D) [N(alkyl)4]2Sb□Cl5□’-type VDPDs. Compared with the more commonly studied A2M(IV)X6□-type double perovskite (A = cation, M = metal ion, X = halide), [N(alkyl)4]2Sb□Cl5□’ features double vacancy sites. Our results demonstrate an inverse relationship between the photoluminescent quantum yield and V□ in 0-D VDPDs. Additionally, structural transformation from A2SbCl5 to A3Sb2Cl9 was first reported, during which the novel 'gate-opening' gas adsorption phenomenon was observed in VDPDs for the first time, as evidenced by 'S'-shaped sorption isotherms for water vapor, indicating a cation-controlled water-vapor response behavior. A mixed-cation strategy was developed to modulate the humidity stability of VDPDs. Characterized by controllable water-responsive behavior and unique 'on-off-on' luminescent switching, A2M(III)□X5□’-type materials show great promise for multi-level information anti-counterfeiting applications.

DOI: 10.1002/anie.202412346

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202412346