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Hot Hole Cooling and Transfer Dynamics from Lead Halide Perovskite Nanocrystals Using Porphyrin Molecules

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    C: Physical Properties of Materials and Interfaces

    Hot Hole Cooling and Transfer Dynamics from Lead Halide Perovskite Nanocrystals Using Porphyrin Molecules
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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2021, 125, 10, 5859–5869
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    https://doi.org/10.1021/acs.jpcc.0c11289
    Published March 8, 2021
    Copyright © 2021 American Chemical Society
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    Abstract

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    A deep understanding of hot carrier (HC) dynamics is important to improve the performance of optoelectronic devices by reducing the thermalization losses. Here, we investigate the hot hole cooling and transfer dynamics of CsPbBr3 nanocrystals (NCs) using 5,10,15,20-tetra(4pyridyl) porphyrin (TpyP) molecules. Density functional theory (DFT) is used to elucidate the mechanism underlying charge extraction as well as the HC transfer process in the CsPbBr3–TpyP system. It is noted that the hot hole states are localized around the top surface of CsPbBr3, while the hot electron states are delocalized away from its top surface, indicating easy extraction of hot holes from the CsPbBr3 by TpyP molecules, as compared to the hot electrons. The significant drop of initial hot carrier temperature from 1140 to 638 K at 400 nm excitation confirms the hot hole transfer from CsPbBr3 NCs to TpyP molecules, which is dependent on the excitation energy, and the maximum transfer efficiency is found to be 42% (for 0.85 eV above band edge photoexcitation). In addition, the hot hole transfer rate is almost 11 times faster than the band edge hole transfer rate. Our findings are relevant for the development of next-generation perovskite-based optoelectronic devices.

    Copyright © 2021 American Chemical Society

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpcc.0c11289.

    • Calculation of PLQY, FTIR spectra, NMR spectra, TEM images, UV–visible absorption spectra, supercell of the modeled system, partial charge density states, TA spectra, 2D pseudo-color TA plot, TA kinetics, TA profiles of pure TpyP, EADS spectra, MB fitting, variation of carrier temperature with excitation energy, fitting parameters of PL decay, upconverted PL, excitation wavelength-dependent hot carrier cooling time, and bleach recovery kinetics (PDF)

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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2021, 125, 10, 5859–5869
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpcc.0c11289
    Published March 8, 2021
    Copyright © 2021 American Chemical Society
    Request reuse permissions

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