Resolving the physical origin of octahedral tilting in halide perovskites
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Accepted version
Published version
Author(s)
Type
Journal Article
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 whilst 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 optimise the photovoltaic properties of perovskites.
Date Issued
2016-05-27
Date Acceptance
2016-05-27
Citation
Chemistry of Materials, 2016, 28 (12), pp.4259-4266
ISSN
1520-5002
Publisher
American Chemical Society
Start Page
4259
End Page
4266
Journal / Book Title
Chemistry of Materials
Volume
28
Issue
12
Copyright Statement
This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
License URL
Sponsor
Royal Commission for the Exhibition of 1851
Subjects
Materials
03 Chemical Sciences
09 Engineering
Publication Status
Published