Organic cation rotation and immobilisation in pure and mixed methylammonium lead-halide perovskites
File(s)Paper_MixedPerovskites_revised_v4.docx (1.01 MB)
Accepted version
Author(s)
Type
Journal Article
Abstract
Three-dimensional lead-halide perovskites have attracted a lot of attention due to their ability to combine solution processing with outstanding optoelectronic properties. Despite their soft ionic nature these materials demonstrate a surprisingly low level of electronic disorder resulting in sharp band edges and narrow distributions of the electronic energies. Understanding how structural and dynamic disorder impacts the optoelectronic properties of these perovskites is important for many applications. Here we combine ultrafast two-dimensional vibrational spectroscopy and molecular dynamics simulations to study the dynamics of the organic methylammonium (MA) cation orientation in a range of pure and mixed trihalide perovskite materials. For pure MAPbX3 (X = I, Br, Cl) perovskite films, we observe that the cation dynamics accelerate with decreasing size of the halide atom. This acceleration is surprising given the expected strengthening of the hydrogen bonds between the MA and the smaller halide anions, but can be explained by the increase in the polarizability with the size of halide. Much slower dynamics, up to partial immobilization of the organic cation, are observed in the mixed MAPb(ClxBr1–x)3 and MAPb(BrxI1–x)3 alloys, which we associate with symmetry breaking within the perovskite unit cell. The observed dynamics are essential for understanding the effects of structural and dynamical disorder in perovskite-based optoelectronic systems.
Date Issued
2017-02-27
Date Acceptance
2017-02-27
Citation
Journal of the American Chemical Society, 2017, 139 (11), pp.4068-4074
ISSN
1520-5126
Publisher
American Chemical Society
Start Page
4068
End Page
4074
Journal / Book Title
Journal of the American Chemical Society
Volume
139
Issue
11
Copyright Statement
© 2017 American Chemical Society
Sponsor
The Royal Society
Identifier
https://pubs.acs.org/doi/10.1021/jacs.6b12239
Grant Number
UF130178
Subjects
Science & Technology
Physical Sciences
Chemistry, Multidisciplinary
Chemistry
CHARGE-CARRIER DYNAMICS
SOLAR-CELLS
HYBRID PEROVSKITES
INORGANIC PEROVSKITES
TRANSPORT-PROPERTIES
IODIDE PEROVSKITES
ROOM-TEMPERATURE
WATER
SPECTROSCOPY
CH3NH3PBI3
General Chemistry
03 Chemical Sciences
Publication Status
Published
Date Publish Online
2017-03-09