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

Diroll, Benjamin T.; Mannodi-Kanakkithodi, Arun; Chan, Maria K. Y.; Schaller, Richard D.

doi:10.1021/acs.nanolett.9b03502

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 »« less

Authors:

^[1];

^[2]

Argonne National Lab. (ANL), Lemont, IL (United States)
Argonne National Lab. (ANL), Lemont, IL (United States); Northwestern Univ., Evanston, IL (United States)

Publication Date:: 2019-10-11

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). 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.

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                    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.  https://doi.org/10.1021/acs.nanolett.9b03502

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                    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.  https://doi.org/10.1021/acs.nanolett.9b03502.  https://www.osti.gov/servlets/purl/1591766.

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@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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https://doi.org/10.1021/acs.nanolett.9b03502

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Cited by: 4 works

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Figure 1: Visible absorption spectra for series of (a) CsPbBr₃ and (b) FAPbBr₃ NCs. (c, d) Typical TEM images of cubic (c) 7.4 nm CsPbBr₃ and (d) 11.1 nm FAPbBr₃ NCs. (e, f) Infrared optical absorption of drop-cast solid films on glass of typical CsPbBr₃ and FAPbBr₃NCs. (g, h)more »

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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

Citation Formats

Figures / Tables:

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