用于低浓度H2S室温稳定监测的CsPbBr3@TiO2异质结微晶气体传感器

摘要/Abstract

摘要： 通过简单的溶液法用TiO(Acac)₂原位包覆CsPbBr₃全无机钙钛矿材料,在400 ℃加热后直接制成了CsPbBr₃@TiO₂核壳结构微晶,使用X射线衍射(XRD)、扫描电子显微镜(SEM)、高倍透射电子显微镜(HRTEM)及X射线光电子能谱(XPS)对CsPbBr₃@TiO₂微晶的晶体结构、微观形貌、化学组成进行表征。结果表明,原位金属氧化物包覆钙钛矿形成分散良好、大小为4~8 μm的球壳结构。用旋涂法在掺氟氧化锡(FTO)电极上构筑了CsPbBr₃@TiO₂薄膜气体传感器,在室温下测试其对H₂S气体的检测灵敏度,结果发现,该传感器对H₂S气体的检测下限达25 ppb(1 ppb=10^-9),对100 ppb H₂S响应/恢复时间为24/21 s,灵敏度为0.59,响应曲线具有良好的循环稳定性。另外,传感器暴露在空气中30 d内的稳定性高于90%,且具有优异的气体选择性和抗湿度干扰性。通过光致发光(PL)光谱、时间分辨光致发光(TRPL)光谱、紫外-可见漫反射光谱(UV-Vis)及紫外光电子能谱(UPS)测试分析了其能带位置、电荷动力学和配位机理,并用氧吸附原理对其传感机理进行了解释。该工作为室温下低浓度H₂S气体的稳定监测提供了一种新的思路。

关键词: CsPbBr₃, 钙钛矿, 核壳结构, 异质结, H₂S气体传感器, 氧吸附原理

Abstract: Through a simple solution method, TiO(Acac)₂ was used to in-situ coat the all-inorganic perovskite material CsPbBr₃. After heating at 400 ℃, CsPbBr₃@TiO₂ core-shell structure microcrystals were directly prepared. The crystal structure, microscopic morphology, and chemical composition of CsPbBr₃@TiO₂ microcrystals were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and X-ray photoelectron spectroscopy (XPS). It was confirmed that the in-situ metal oxide coating on the perovskite formed well-dispersed spherical shell structures with sizes of 4~8 μm. A CsPbBr₃@TiO₂ thin film gas sensor was constructed on a fluorine-doped tin oxide (FTO) electrode using spin-coating method. The sensitivity of the sensor to H₂S gas was tested at room temperature. The results show that the sensor has a detection limit of 25 ppb (1 ppb=10^-9) for H₂S gas, with a response and recovery time of 24/21 s to 100 ppb H₂S, and a sensitivity of 0.59. The response curve exhibits good cyclic stability. Moreover, the sensor maintains over 90% stability within 30 d of exposure in air and possesses excellent gas selectivity and humidity resistance. Photoluminescence (PL) spectroscopy, time-resolved photoluminescence (TRPL) spectroscopy, ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis), and ultraviolet photoelectron spectroscopy (UPS) were employed to analyze the band positions, charge dynamics, and coordination mechanisms. The sensing mechanism was elucidated using the oxygen adsorption principle. This work provides a new approach for the stable monitoring of low concentrations of H₂S gas at room temperature.

Key words: CsPbBr₃, perovskite, core-shell structure, heterojunction, H₂S gas sensor, oxygen adsorption principle

中图分类号:

逯江浩, 黄胜, 陈露, 程永超, 高莎莎, 陶雪钰, 顾修全. 用于低浓度H₂S室温稳定监测的CsPbBr₃@TiO₂异质结微晶气体传感器[J]. 人工晶体学报, 2024, 53(10): 1815-1826.

LU Jianghao, HUANG Sheng, CHEN Lu, CHENG Yongchao, GAO Shasha, TAO Xueyu, GU Xiuquan. CsPbBr₃@TiO₂ Heterojunction Microcrystals Gas Sensor for Low-Concentration H₂S Stability Monitoring at Room Temperature[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(10): 1815-1826.

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用于低浓度H₂S室温稳定监测的CsPbBr₃@TiO₂异质结微晶气体传感器

CsPbBr₃@TiO₂ Heterojunction Microcrystals Gas Sensor for Low-Concentration H₂S Stability Monitoring at Room Temperature

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