Role of Lead Vacancies for Optoelectronic Properties of Lead-Halide Perovskites

Vogel, Dayton J.; Inerbaev, Talgat M.; Kilin, Dmitri S.

doi:10.1021/acs.jpcc.7b05375

Title: Role of Lead Vacancies for Optoelectronic Properties of Lead-Halide Perovskites

Journal Article · 18 December 2017 · Journal of Physical Chemistry. C

DOI: https://doi.org/10.1021/acs.jpcc.7b05375 · OSTI ID:1480500

Vogel, Dayton J. ^[1]; Inerbaev, Talgat M. ^[2]; Kilin, Dmitri S. ^[3]

Univ. of South Dakota, Vermillion, SD (United States). Dept. of Chemistry
L.N. Gumilyov Eurasian National Univ., Astana (Kazakhstan); National Univ. of Science and Technology, Moscow (Russia)
Univ. of South Dakota, Vermillion, SD (United States). Dept. of Chemistry; North Dakota State Univ., Fargo, ND (United States). Dept. of Chemistry and Biochemistry

Methylammonium lead iodide perovskite materials have been shown to be efficient in photovoltaic devices. The current fabrication process has not been perfected, leaving defects such as site vacancies, which can trap charge and have a detrimental effect on photogenerated charge carriers. Here focus is placed on the effect a Pb site vacancy has on the charge-carrier dynamics following photoexcitation. The electronic structure of materials with vacancies is often found in open-shell configurations with unpaired electrons in the conduction/valence bands To accurately describe unpaired electrons, spin-polarized and noncollinear spin calculations are performed on both neutral and charged vacancy systems. This work presents spin-polarized and noncollinear spin ground-state electronic structures and nonradiative rates of charge-carrier relaxation and introduces an extension to a novel procedure to compute photoluminescence spectra for open-shell models. This study describes nonadiabatic dynamics of MAPbI₃ models within a Redfield formalism focusing on the role of a Pb vacancy defect on electronic relaxation processes. Results show the vacancy of the Pb ion introducing a new energy state within the unblemished material band gap region. Finally, this additional unoccupied state is expected to increase the nonradiative relaxation lifetime of the excited electron, allowing for a longer lifetime of the charge carrier and increased opportunity for secondary relaxation mechanisms or collection to take place.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

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

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1480500

Journal Information:: Journal of Physical Chemistry. C, Vol. 122, Issue 10; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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