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Thermal Disorder‐Induced Strain and Carrier Localization Activate Reverse Halide Segregation

Mussakhanuly, Nursultan [Univ. of New South Wales, Sydney, NSW (Australia)] (ORCID:0009000349149607)·Soufiani, Arman Mahboubi [Helmholtz-Zentrum Berlin (HZB), (Germany). German Research Centre for Materials and Energy]·Bernardi, Stefano [Univ. of Sydney, NSW (Australia)]·Gan, Jianing [Pennsylvania State Univ., University Park, PA (United States)]·Bhattacharyya, Saroj Kumar [Univ. of New South Wales, Sydney, NSW (Australia)]·Chin, Robert Lee [Univ. of New South Wales, Sydney, NSW (Australia)]·Muhammad, Hanif [Univ. of New South Wales, Sydney, NSW (Australia)]·Dubajic, Milos [Univ. of Cambridge (United Kingdom)]·Gentle, Angus [Univ. of New South Wales, Sydney, NSW (Australia); Univ. of Sydney, NSW (Australia)]·Chen, Weijian [Univ. of New South Wales, Sydney, NSW (Australia)]·Zhang, Meng [Univ. of New South Wales, Sydney, NSW (Australia); Southwest Petroleum Univ., Chengdu (China)]·Nielsen, Michael P. [Univ. of New South Wales, Sydney, NSW (Australia)]·Huang, Shujuan [Macquarie Univ., NSW (Australia)]·Asbury, John [Pennsylvania State Univ., University Park, PA (United States)]·Widmer‐Cooper, Asaph [Univ. of Sydney, NSW (Australia)]·Yun, Jae Sung [Univ. of New South Wales, Sydney, NSW (Australia); Univ. of Surrey, Guildford (United Kingdom)]·Hao, Xiaojing [Univ. of New South Wales, Sydney, NSW (Australia)] (ORCID:0000000159034481)
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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.

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36 MATERIALS SCIENCEChemistryMaterials SciencePhysicsScience & Technology - Other Topicscarrier localizationhalide segregation/reversalmixed-halide wide-bandgap perovskitestrainthermal/dynamic-disorder

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Mussakhanuly, Nursultan [Univ. of New South Wales, Sydney, NSW (Australia)] (ORCID:0009000349149607), Soufiani, Arman Mahboubi [Helmholtz-Zentrum Berlin (HZB), (Germany). German Research Centre for Materials and Energy], Bernardi, Stefano [Univ. of Sydney, NSW (Australia)], Gan, Jianing [Pennsylvania State Univ., University Park, PA (United States)], Bhattacharyya, Saroj Kumar [Univ. of New South Wales, Sydney, NSW (Australia)], Chin, Robert Lee [Univ. of New South Wales, Sydney, NSW (Australia)], Muhammad, Hanif [Univ. of New South Wales, Sydney, NSW (Australia)], Dubajic, Milos [Univ. of Cambridge (United Kingdom)], Gentle, Angus [Univ. of New South Wales, Sydney, NSW (Australia); Univ. of Sydney, NSW (Australia)], Chen, Weijian [Univ. of New South Wales, Sydney, NSW (Australia)], Zhang, Meng [Univ. of New South Wales, Sydney, NSW (Australia); Southwest Petroleum Univ., Chengdu (China)], Nielsen, Michael P. [Univ. of New South Wales, Sydney, NSW (Australia)], Huang, Shujuan [Macquarie Univ., NSW (Australia)], Asbury, John [Pennsylvania State Univ., University Park, PA (United States)], Widmer‐Cooper, Asaph [Univ. of Sydney, NSW (Australia)], Yun, Jae Sung [Univ. of New South Wales, Sydney, NSW (Australia); Univ. of Surrey, Guildford (United Kingdom)], Hao, Xiaojing [Univ. of New South Wales, Sydney, NSW (Australia)] (ORCID:0000000159034481). 2023-12-07. Thermal Disorder‐Induced Strain and Carrier Localization Activate Reverse Halide Segregation. https://doi.org/10.1002/adma.202311458

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