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Title: Spectroscopic Comparison of Thermal Transport at Organic–Inorganic and Organic-Hybrid Interfaces Using CsPbBr3 and FAPbBr3 (FA = Formamidinium) Perovskite Nanocrystals

Abstract

Thermal transport across interfaces depends on the matching of vibrational structure at the interface. This work examines the transfer of thermal excitation from an organic ligand coating to either all-inorganic cesium lead tribromide (CsPbBr3) nanocrystals or hybrid organic-inorganic formamidinium lead tribromide (FAPbBr3) nano crystals using selective infrared optical excitation. Here, these two semiconductors are directly compared because they (or similar semiconductors) are currently envisioned as strong candidates in many optoelectronic technologies and they differ due to the presence of an organic or inorganic cation, which introduces substantial differences in the phonon density of states in otherwise quite similar semiconductors. Infrared excitation of C-H vibrations of surface-bound ligands generates a temperature gradient between the organic ligand shell and nanocrystal core, which results in heat flow, measured by probing changes of the semiconductor band gap. Heat transfer to both perovskite compositions of comparable sizes is similar (25-30 ps), due to fast intramolecular vibrational relaxation and similar matching of low-energy phonons with the organic ligand, but FAPbBr3 samples show a slow bleaching kinetic on the order of 1 ns. This slow, heat-induced change in the semiconductor band gap is attributed not to interfacial heat transfer but instead to thermal equilibration between the organicmore » and inorganic sublattices of FAPbBr3. Ab initio molecular dynamics simulations support the hypothesis that low-energy inorganic sublattice phonon modes are populated initially in the heat transfer process, with a slow thermal population of the higher-energy phonon modes associated primarily with the organic cation. Slow thermal equilibration of FAPbBr3 is likely to substantially impact the time-dependent response of optoelectronic devices that heat the semiconductor active layer and provide further evidence that the poor bulk thermal transport of hybrid perovskite materials extends to microscopic thermal processes.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Argonne National Lab. (ANL), Lemont, IL (United States); Northwestern Univ., Evanston, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
OSTI Identifier:
1591766
Grant/Contract Number:  
AC02-06CH11357; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 19; Journal Issue: 11; Journal ID: ISSN 1530-6984
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; heat transfer

Citation Formats

Diroll, Benjamin T., Mannodi-Kanakkithodi, Arun, Chan, Maria K. Y., and Schaller, Richard D. Spectroscopic Comparison of Thermal Transport at Organic–Inorganic and Organic-Hybrid Interfaces Using CsPbBr3 and FAPbBr3 (FA = Formamidinium) Perovskite Nanocrystals. United States: N. p., 2019. Web. doi:10.1021/acs.nanolett.9b03502.
Diroll, Benjamin T., Mannodi-Kanakkithodi, Arun, Chan, Maria K. Y., & Schaller, Richard D. Spectroscopic Comparison of Thermal Transport at Organic–Inorganic and Organic-Hybrid Interfaces Using CsPbBr3 and FAPbBr3 (FA = Formamidinium) Perovskite Nanocrystals. United States. doi:10.1021/acs.nanolett.9b03502.
Diroll, Benjamin T., Mannodi-Kanakkithodi, Arun, Chan, Maria K. Y., and Schaller, Richard D. Fri . "Spectroscopic Comparison of Thermal Transport at Organic–Inorganic and Organic-Hybrid Interfaces Using CsPbBr3 and FAPbBr3 (FA = Formamidinium) Perovskite Nanocrystals". United States. doi:10.1021/acs.nanolett.9b03502.
@article{osti_1591766,
title = {Spectroscopic Comparison of Thermal Transport at Organic–Inorganic and Organic-Hybrid Interfaces Using CsPbBr3 and FAPbBr3 (FA = Formamidinium) Perovskite Nanocrystals},
author = {Diroll, Benjamin T. and Mannodi-Kanakkithodi, Arun and Chan, Maria K. Y. and Schaller, Richard D.},
abstractNote = {Thermal transport across interfaces depends on the matching of vibrational structure at the interface. This work examines the transfer of thermal excitation from an organic ligand coating to either all-inorganic cesium lead tribromide (CsPbBr3) nanocrystals or hybrid organic-inorganic formamidinium lead tribromide (FAPbBr3) nano crystals using selective infrared optical excitation. Here, these two semiconductors are directly compared because they (or similar semiconductors) are currently envisioned as strong candidates in many optoelectronic technologies and they differ due to the presence of an organic or inorganic cation, which introduces substantial differences in the phonon density of states in otherwise quite similar semiconductors. Infrared excitation of C-H vibrations of surface-bound ligands generates a temperature gradient between the organic ligand shell and nanocrystal core, which results in heat flow, measured by probing changes of the semiconductor band gap. Heat transfer to both perovskite compositions of comparable sizes is similar (25-30 ps), due to fast intramolecular vibrational relaxation and similar matching of low-energy phonons with the organic ligand, but FAPbBr3 samples show a slow bleaching kinetic on the order of 1 ns. This slow, heat-induced change in the semiconductor band gap is attributed not to interfacial heat transfer but instead to thermal equilibration between the organic and inorganic sublattices of FAPbBr3. Ab initio molecular dynamics simulations support the hypothesis that low-energy inorganic sublattice phonon modes are populated initially in the heat transfer process, with a slow thermal population of the higher-energy phonon modes associated primarily with the organic cation. Slow thermal equilibration of FAPbBr3 is likely to substantially impact the time-dependent response of optoelectronic devices that heat the semiconductor active layer and provide further evidence that the poor bulk thermal transport of hybrid perovskite materials extends to microscopic thermal processes.},
doi = {10.1021/acs.nanolett.9b03502},
journal = {Nano Letters},
number = 11,
volume = 19,
place = {United States},
year = {2019},
month = {10}
}

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This content will become publicly available on October 11, 2020
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