The effect of caesium alloying on the ultrafast structural dynamics of hybrid organic-inorganic halide perovskites
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Author(s)
Type
Journal Article
Abstract
Hybrid inorganic–organic perovskites have attracted considerable attention over recent years as promising processable electronic materials. In particular, the rich structural dynamics of these ‘soft’ materials has become a subject of investigation and debate due to their direct influence on the perovskites' optoelectronic properties. Significant effort has focused on understanding the role and behaviour of the organic cations within the perovskite, as their rotational dynamics may be linked to material stability, heterogeneity and performance in (opto)electronic devices. To this end, we use two-dimensional IR spectroscopy (2DIR) to understand the effect of partial caesium alloying on the rotational dynamics of the methylammonium cation in the archetypal hybrid perovskite CH3NH3PbI3. We find that caesium incorporation primarily inhibits the slower ‘reorientational jump’ modes of the organic cation, whilst a smaller effect on the fast ‘wobbling time’ may be due to distortions and rigidisation of the inorganic cuboctahedral cage. 2DIR centre-line-slope analysis further reveals that while static disorder increases with caesium substitution, the dynamic disorder (reflected in the phase memory of the N–H stretching mode of methylammonium) is largely independent of caesium addition. Our results contribute to the development of a unified model of cation dynamics within organohalide perovskites.
Date Issued
2022-10-04
Date Acceptance
2022-10-04
Citation
Journal of Materials Chemistry A, 2022, 10 (42), pp.22408-22418
ISSN
2050-7488
Publisher
Royal Society of Chemistry
Start Page
22408
End Page
22418
Journal / Book Title
Journal of Materials Chemistry A
Volume
10
Issue
42
Copyright Statement
© The Royal Society of Chemistry 2022. This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.
License URL
Sponsor
The Royal Society
Commission of the European Communities
Identifier
https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000865820800001&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
Grant Number
UF130178
101018002
Subjects
Science & Technology
Physical Sciences
Technology
Chemistry, Physical
Energy & Fuels
Materials Science, Multidisciplinary
Chemistry
Materials Science
IODIDE PEROVSKITES
CATION DYNAMICS
LEAD
PHASE
REORIENTATION
EFFICIENCY
ROTATION
CARRIERS
FILMS
Publication Status
Published
Date Publish Online
2022-10-04