用于低浓度H_(2)S室温稳定监测的CsPbBr_(3)@TiO_(2)异质结微晶气体传感器  

CsPbBr_(3)@TiO_(2)Heterojunction Microcrystals Gas Sensor for Low-Concentration H_(2)S Stability Monitoring at Room Temperature

作　　者：逯江浩 黄胜[1] 陈露 程永超 高莎莎 陶雪钰[1] 顾修全[1,2] LU Jianghao;HUANG Sheng;CHEN Lu;CHENG Yongchao;GAO Shasha;TAO Xueyu;GU Xiuquan(School of Materials Science and Physics,China University of Mining and Technology,Xuzhou 221116,China;State Key Laboratory of Silicon and Advanced Semiconductor Materials,Zhejiang University,Hangzhou 310027,China)

机构地区：[1]中国矿业大学材料与物理学院,徐州221116 [2]浙江大学硅及先进半导体材料全国重点实验室,杭州310027

出　　处：《人工晶体学报》2024年第10期1815-1826,共12页Journal of Synthetic Crystals

基　　金：国家自然科学基金青年科学基金(52303356);江苏省自然科学青年基金(BK20210494)。

摘　　要：通过简单的溶液法用TiO(Acac)_(2)原位包覆CsPbBr_(3)全无机钙钛矿材料,在400℃加热后直接制成了CsPbBr_(3)@TiO_(2)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CsPbBr_(3)@TiO_(2)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4~8μm的球壳结构。用旋涂法在掺氟氧化锡(FTO)电极上构筑了CsPbBr_(3)@TiO_(2)薄膜气体传感器,在室温下测试其对H_(2)S气体的检测灵敏度,结果发现,该传感器对H_(2)S气体的检测下限达25 ppb(1 ppb=10-9),对100 ppb H_(2)S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H_(2)S气体的稳定监测提供了一种新的思路。Through a simple solution method,TiO(Acac)_(2) was used to in-situ coat the all-inorganic perovskite material CsPbBr_(3).After heating at 400℃,CsPbBr_(3)@TiO_(2)core-shell structure microcrystals were directly prepared.The crystal structure,microscopic morphology,and chemical composition of CsPbBr_(3)@TiO_(2)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 4~8μm.A CsPbBr_(3)@TiO_(2)thin film gas sensor was constructed on a fluorine-doped tin oxide(FTO)electrode using spin-coating method.The sensitivity of the sensor to H_(2)S gas was tested at room temperature.The results show that the sensor has a detection limit of 25 ppb(1 ppb=10-9)for H_(2)S gas,with a response and recovery time of 24/21 s to 100 ppb H_(2)S,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 H_(2)S gas at room temperature.

关 键 词：CsPbBr_(3) 钙钛矿 核壳结构 异质结 H_(2)S气体传感器 氧吸附原理 

分 类 号：O753.1[理学—晶体学] TP212[自动化与计算机技术—检测技术与自动化装置]