Quasicubic model for metal halide perovskite nanocrystals

Sercel, Peter C.; Lyons, John L.; Bernstein, Noam; Efros, Alexander L.

doi:10.1063/1.5127528

Quasicubic model for metal halide perovskite nanocrystals

Journal Article · Fri Dec 20 23:00:00 EST 2019 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5127528· OSTI ID:1767718

^[1]; ^[2]; Bernstein, Noam ^[2]; ^[2]

California Institute of Technology (CalTech), Pasadena, CA (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Hybrid Organic-Inorganic Semiconductors for Energy (CHOISE); OSTI
Naval Research Lab. (NRL), Washington, DC (United States). Center for Computational Materials Science

In this work, we present an analysis of quantum confinement of carriers and excitons, and exciton fine structure, in metal halide perovskite (MHP) nanocrystals (NCs). Starting with coupled-band k · P theory, we derive a nonparabolic effective mass model for the exciton energies in MHP NCs valid for the full size range from the strong to the weak confinement limits. We illustrate the application of the model to CsPbBr₃ NCs and compare the theory against published absorption data, finding excellent agreement. We then apply the theory of electron-hole exchange, including both short- and long-range exchange interactions, to develop a model for the exciton fine structure. We develop an analytical quasicubic model for the effect of tetragonal and orthorhombic lattice distortions on the exchange-related exciton fine structure in CsPbBr₃, as well as some hybrid organic MHPs of recent interest, including formamidinium lead bromide (FAPbBr₃) and methylammonium lead iodide (MAPbI3). Testing the predictions of the quasicubic model using hybrid density functional theory (DFT) calculations, we find qualitative agreement in tetragonal MHPs but significant disagreement in the orthorhombic modifications. Moreover, the quasicubic model fails to correctly describe the exciton oscillator strength and with it the long-range exchange corrections in these systems. Introducing the effect of NC shape anisotropy and possible Rashba terms into the model, we illustrate the calculation of the exciton fine structure in CsPbBr₃ NCs based on the results of the DFT calculations and examine the effect of Rashba terms and shape anisotropy on the calculated fine structure.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Hybrid Organic-Inorganic Semiconductors for Energy (CHOISE)

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

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1767718

Alternate ID(s):: OSTI ID: 1579586

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 23 Vol. 151; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Quasicubic model for metal halide perovskite nanocrystals

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