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Thermal Disorder-Induced Strain and Carrier Localization Activate Reverse Halide Segregation.

Published version
Peer-reviewed

Repository DOI


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Authors

Mussakhanuly, Nursultan  ORCID logo  https://orcid.org/0009-0003-4914-9607
Soufiani, Arman Mahboubi 
Bernardi, Stefano 
Gan, Jianing 
Bhattacharyya, Saroj Kumar 

Abstract

The reversal of halide ions is studied under various conditions. However, the underlying mechanism of heat-induced reversal remains unclear. This work finds that dynamic disorder-induced localization of self-trapped polarons and thermal disorder-induced strain (TDIS) can be co-acting drivers of reverse segregation. Localization of polarons results in an order of magnitude decrease in excess carrier density (polaron population), causing a reduced impact of the light-induced strain (LIS - responsible for segregation) on the perovskite framework. Meanwhile, exposing the lattice to TDIS exceeding the LIS can eliminate the photoexcitation-induced strain gradient, as thermal fluctuations of the lattice can mask the LIS strain. Under continuous 0.1 W cm⁻2 illumination (upon segregation), the strain disorder is estimated to be 0.14%, while at 80 °C under dark conditions, the strain is 0.23%. However, in situ heating of the segregated film to 80 °C under continuous illumination (upon reversal) increases the total strain disorder to 0.25%, where TDIS is likely to have a dominant contribution. Therefore, the contribution of entropy to the system's free energy is likely to dominate, respectively. Various temperature-dependent in situ measurements and simulations further support the results. These findings highlight the importance of strain homogenization for designing stable perovskites under real-world operating conditions.

Description

Publication status: Published


Funder: Australian Government; doi: http://dx.doi.org/10.13039/100015539


Funder: Government of Western Australia; doi: http://dx.doi.org/10.13039/501100011025

Keywords

carrier localization, halide segregation/reversal, mixed-halide wide-bandgap perovskite, strain, thermal/dynamic-disorder

Journal Title

Adv Mater

Conference Name

Journal ISSN

0935-9648
1521-4095

Volume Title

Publisher

Wiley
Sponsorship
Australian Research Council (FT190100756, CE170100026)