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Resolving the Physical Origin of Octahedral Tilting in Halide Perovskites

Published version
Peer-reviewed

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Authors

Lee, JH 
Bristowe, NC 
Lee, JH 
Lee, SH 
Bristowe, PD 

Abstract

Hybrid perovskites are currently the fastest growing photovoltaic technology, having reached a solar cell efficiency of over 20%. One possible strategy to further improve the efficiency of perovskite solar cells is to tune the degree of octahedral tilting of the halide frame, since this in turn affects the optical band gap and carrier effective masses. It is commonly accepted that the ion sizes are the main control parameter influencing the degree of tilting in perovskites. Here we re-examine the origin of octahedral tilts in halide perovskites from systematic first-principles calculations. We find that while steric effects dominate the tilt magnitude in inorganic halides, hydrogen bonding between an organic A-cation and the halide frame plays a significant role in hybrids. For example, in the case of MAPbI3, our calculations suggest that, without the contribution from hydrogen bonding, the octahedra would not tilt at all. These results demonstrate that tuning the degree of hydrogen bonding can be used as an additional control parameter to optimize the photovoltaic properties of perovskites.

Description

Keywords

34 Chemical Sciences, 3406 Physical Chemistry, 7 Affordable and Clean Energy

Journal Title

Chemistry of Materials

Conference Name

Journal ISSN

0897-4756
1520-5002

Volume Title

28

Publisher

American Chemical Society (ACS)
Sponsorship
Engineering and Physical Sciences Research Council (EP/K014560/1)
The work at POSTECH was supported by National Research Foundation (NRF) Grants funded by the Korea Government (MSIP) (Grants 2012R 1A1A2041628 and 2013R 1A2A2A01068274). At the University of Cambridge, the work was funded by the Winton Programme for the Physics of Sustainability. The work at Imperial College London was supported by the Royal Commission for the Exhibition of 1851 and Imperial College’s Junior Research Fellowships. The calculations were performed at the Cambridge HPCS and the UK National Supercomputing Service, ARCHER. Access to the latter was obtained via the UKCP consortium and funded by EPSRC under Grant EP/K014560/1.