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Title: Density of States Broadening in CH3NH3PbI3 Hybrid Perovskites Understood from ab Initio Molecular Dynamics Simulations

Abstract

Lead-halide perovskites are promising materials in optoelectronic devices for their unique properties including direct band gap, strong light absorption, high carrier mobility, and low fabrication cost. Here, by using ab inito molecular dynamics and electronic structure calculations, we report a systematic study on the broadening density of states (DOS) deep in the valence bands that has been experimentally observed but absent in static calculations. We quantify the broadening DOS reduction from the cubic phase to lower-temperature tetragonal and orthorhombic phases and attribute observed effects to the molecular vibrations and the anharmonicity of iodine atoms motion. Specifically, the MA cations’ vibrations are strongly linked to the moderate C–N stretch and CH3 bend, as well as the strong CH3 and NH3+ stretches. Furthermore, these results present a theoretical perspective on the structural dynamics in lead-halide perovskites which may be valuable for future studies toward desired functionalities in perovskite-based optoelectronic devices.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2];  [3]; ORCiD logo [4];  [5]; ORCiD logo [1]; ORCiD logo [4]; ORCiD logo [4]; ORCiD logo [1]
+ Show Author Affiliations
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Univ. of South Dakota, Vermillion, SD (United States)
  3. North Dakota State Univ., Fargo, ND (United States)
  4. Univ Rennes, Rennes (France)
  5. Hamad Bin Khalifa Univ., Doha (Qatar)
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1480040
Report Number(s):
LA-UR-18-20635
Journal ID: ISSN 2380-8195
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
ACS Energy Letters
Additional Journal Information:
Journal Volume: 3; Journal Issue: 4; Journal ID: ISSN 2380-8195
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Material Science

Citation Formats

Zhou, Liujiang, Neukirch, Amanda J., Vogel, Dayton J., Kilin, Dmitri S., Pedesseau, Laurent, Carignano, Marcelo A., Mohite, Aditya D., Even, Jacky, Katan, Claudine, and Tretiak, Sergei. Density of States Broadening in CH3NH3PbI3 Hybrid Perovskites Understood from ab Initio Molecular Dynamics Simulations. United States: N. p., 2018. Web. doi:10.1021/acsenergylett.8b00166.
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Zhou, Liujiang, Neukirch, Amanda J., Vogel, Dayton J., Kilin, Dmitri S., Pedesseau, Laurent, Carignano, Marcelo A., Mohite, Aditya D., Even, Jacky, Katan, Claudine, & Tretiak, Sergei. Density of States Broadening in CH3NH3PbI3 Hybrid Perovskites Understood from ab Initio Molecular Dynamics Simulations. United States. https://doi.org/10.1021/acsenergylett.8b00166
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Zhou, Liujiang, Neukirch, Amanda J., Vogel, Dayton J., Kilin, Dmitri S., Pedesseau, Laurent, Carignano, Marcelo A., Mohite, Aditya D., Even, Jacky, Katan, Claudine, and Tretiak, Sergei. Tue . "Density of States Broadening in CH3NH3PbI3 Hybrid Perovskites Understood from ab Initio Molecular Dynamics Simulations". United States. https://doi.org/10.1021/acsenergylett.8b00166. https://www.osti.gov/servlets/purl/1480040.
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@article{osti_1480040,
title = {Density of States Broadening in CH3NH3PbI3 Hybrid Perovskites Understood from ab Initio Molecular Dynamics Simulations},
author = {Zhou, Liujiang and Neukirch, Amanda J. and Vogel, Dayton J. and Kilin, Dmitri S. and Pedesseau, Laurent and Carignano, Marcelo A. and Mohite, Aditya D. and Even, Jacky and Katan, Claudine and Tretiak, Sergei},
abstractNote = {Lead-halide perovskites are promising materials in optoelectronic devices for their unique properties including direct band gap, strong light absorption, high carrier mobility, and low fabrication cost. Here, by using ab inito molecular dynamics and electronic structure calculations, we report a systematic study on the broadening density of states (DOS) deep in the valence bands that has been experimentally observed but absent in static calculations. We quantify the broadening DOS reduction from the cubic phase to lower-temperature tetragonal and orthorhombic phases and attribute observed effects to the molecular vibrations and the anharmonicity of iodine atoms motion. Specifically, the MA cations’ vibrations are strongly linked to the moderate C–N stretch and CH3 bend, as well as the strong CH3 and NH3+ stretches. Furthermore, these results present a theoretical perspective on the structural dynamics in lead-halide perovskites which may be valuable for future studies toward desired functionalities in perovskite-based optoelectronic devices.},
doi = {10.1021/acsenergylett.8b00166},
journal = {ACS Energy Letters},
number = 4,
volume = 3,
place = {United States},
year = {Tue Mar 06 00:00:00 EST 2018},
month = {Tue Mar 06 00:00:00 EST 2018}
}
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https://doi.org/10.1021/acsenergylett.8b00166
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