Swati N. Rahane, Ganesh K. Rahane, Animesh Mandal, Yogesh Jadhav, Akshat Godha, Avinash Rokade, Shruti Shah, Yogesh Hase, Ashish Waghmare, Nilesh G. Saykar, Anurag Roy, Kranti N. Salgaonkar, Deepak Dubal, Surendra K. Makineni, Nelson Y. Dzade*, Sandesh R. Jadkar* and Sachin R. Rondiya*,
{"title":"Lead-Free Cs2AgBiCl6 Double Perovskite: Experimental and Theoretical Insights into the Self-Trapping for Optoelectronic Applications","authors":"Swati N. Rahane, Ganesh K. Rahane, Animesh Mandal, Yogesh Jadhav, Akshat Godha, Avinash Rokade, Shruti Shah, Yogesh Hase, Ashish Waghmare, Nilesh G. Saykar, Anurag Roy, Kranti N. Salgaonkar, Deepak Dubal, Surendra K. Makineni, Nelson Y. Dzade*, Sandesh R. Jadkar* and Sachin R. Rondiya*, ","doi":"10.1021/acsphyschemau.4c0000810.1021/acsphyschemau.4c00008","DOIUrl":null,"url":null,"abstract":"<p >Lead-free double perovskites (DPs) will emerge as viable and environmentally safe substitutes for Pb-halide perovskites, demonstrating stability and nontoxicity if their optoelectronic property is greatly improved. Doping has been experimentally validated as a powerful tool for enhancing optoelectronic properties and concurrently reducing the defect state density in DP materials. Fundamental understanding of the optical properties of DPs, particularly the self-trapped exciton (STEs) dynamics, plays a critical role in a range of optoelectronic applications. Our study investigates how Fe doping influences the structural and optical properties of Cs<sub>2</sub>AgBiCl<sub>6</sub> DPs by understanding their STEs dynamics, which is currently lacking in the literature. A combined experimental–computational approach is employed to investigate the optoelectronic properties of pure and doped Cs<sub>2</sub>AgBiCl<sub>6</sub> (Fe–Cs<sub>2</sub>AgBiCl<sub>6</sub>) perovskites. Successful incorporation of Fe<sup>3+</sup> ions is confirmed by X-ray diffraction and Raman spectroscopy. Moreover, the Fe–Cs<sub>2</sub>AgBiCl<sub>6</sub> DPs exhibit strong absorption from below 400 nm up to 700 nm, indicating sub-band gap state transitions originating from surface defects. Photoluminescence (PL) analysis demonstrates a significant enhancement in the PL intensity, attributed to an increased radiative recombination rate and higher STE density. The radiative kinetics and average lifetime are investigated by the time-resolved PL (TRPL) method; in addition, temperature-dependent PL measurements provide valuable insights into activation energy and exciton–phonon coupling strength. Our findings will not only deepen our understanding of charge carrier dynamics associated with STEs but also pave the way for the design of some promising perovskite materials for use in optoelectronics and photocatalysis.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":3.7000,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.4c00008","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Physical Chemistry Au","FirstCategoryId":"1085","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acsphyschemau.4c00008","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
Lead-free double perovskites (DPs) will emerge as viable and environmentally safe substitutes for Pb-halide perovskites, demonstrating stability and nontoxicity if their optoelectronic property is greatly improved. Doping has been experimentally validated as a powerful tool for enhancing optoelectronic properties and concurrently reducing the defect state density in DP materials. Fundamental understanding of the optical properties of DPs, particularly the self-trapped exciton (STEs) dynamics, plays a critical role in a range of optoelectronic applications. Our study investigates how Fe doping influences the structural and optical properties of Cs2AgBiCl6 DPs by understanding their STEs dynamics, which is currently lacking in the literature. A combined experimental–computational approach is employed to investigate the optoelectronic properties of pure and doped Cs2AgBiCl6 (Fe–Cs2AgBiCl6) perovskites. Successful incorporation of Fe3+ ions is confirmed by X-ray diffraction and Raman spectroscopy. Moreover, the Fe–Cs2AgBiCl6 DPs exhibit strong absorption from below 400 nm up to 700 nm, indicating sub-band gap state transitions originating from surface defects. Photoluminescence (PL) analysis demonstrates a significant enhancement in the PL intensity, attributed to an increased radiative recombination rate and higher STE density. The radiative kinetics and average lifetime are investigated by the time-resolved PL (TRPL) method; in addition, temperature-dependent PL measurements provide valuable insights into activation energy and exciton–phonon coupling strength. Our findings will not only deepen our understanding of charge carrier dynamics associated with STEs but also pave the way for the design of some promising perovskite materials for use in optoelectronics and photocatalysis.
期刊介绍:
ACS Physical Chemistry Au is an open access journal which publishes original fundamental and applied research on all aspects of physical chemistry. The journal publishes new and original experimental computational and theoretical research of interest to physical chemists biophysical chemists chemical physicists physicists material scientists and engineers. An essential criterion for acceptance is that the manuscript provides new physical insight or develops new tools and methods of general interest. Some major topical areas include:Molecules Clusters and Aerosols; Biophysics Biomaterials Liquids and Soft Matter; Energy Materials and Catalysis