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Temperature-dependent anomalous Mn2+ emission and excited state dynamics in Mn2+-doped MAPbCl3-xBrx nanocrystals

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Abstract

In hybrid perovskites, MAPbI3 and MAPbBr3 have been extensively studied for their optical and photovoltaic properties, but MAPbCl3 is significantly less investigated for its optical and photovoltaic properties due to its low photoluminescence quantum yield (PL QY) and a large band gap. However, the large band gap makes it a suitable host for doping transition metal ions to explore new optical properties. We synthesized nanocrystals (NCs) of MAPbCl3 doped with Mn2+ by simple ligand assisted reprecipitation method. The reaction temperature and Pb to Mn feed ratio were optimized by preparing a series of Mn2+-doped MAPbCl3 NCs. The prepared NCs show bright Mn2+ emission with ~13% PL QY suggesting an efficient energy transfer from host NCs to Mn2+. Since the large bandgap of MAPbCl3 precludes the possibility of investigating temperature-dependent PL and lifetime measurements to understand the excited state dynamics, we carried out these experiments on Mn2+ doped MAPbCl2.7Br0.3 with the Br concentration adjusted to bring the bandgap of the alloyed system within the limits of the experimental technique. Our studies establish an anomalous behavior of Mn2+ PL emission in this host. These results reveal the origin of a temperature mediated energy transfer from exciton to Mn2+ and provide an understanding of the underlying mechanisms of PL properties of this new class of NCs.

Graphical abstract

SYNOPSIS: Nanocrystals (NCs) of MAPbCl3-xBrx doped with Mn2+ were prepared by simple ligand assisted reprecipitation method. Reaction temperature and Mn2+ concentrations were optimized to achieve maximum Mn2+ emission. The temperature-dependent photoluminescence results reveal the origin of temperature mediated energy transfer from exciton to Mn2+ in MAPbCl3-xBrx NCs.

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Acknowledgements

The authors thank Mr. Vasudeva from JNCASR for help during ICP-AES measurements. BPK acknowledges UGC, India, for a D.S. Kothari Postdoctoral Fellowship. The authors thank the Science and Engineering Research Board and the Department of Science and Technology, Government of India for support of their research. DDS thanks Jamsetji Tata Trust for support.

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  1. Solid State and Structural Chemistry Unit, Indian Institute of Science, Bengaluru, 560 012, India

    Bhushan P Kore, Shyamashis Das & D D Sarma

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  1. Bhushan P Kore
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Correspondence to D D Sarma.

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Kore, B.P., Das, S. & Sarma, D.D. Temperature-dependent anomalous Mn2+ emission and excited state dynamics in Mn2+-doped MAPbCl3-xBrx nanocrystals. J Chem Sci 133, 64 (2021). https://doi.org/10.1007/s12039-021-01919-0

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