Thermal Disorder-Induced Strain and Carrier Localization Activate Reverse Halide Segregation,Advanced Materials

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Thermal Disorder-Induced Strain and Carrier Localization Activate Reverse Halide Segregation
Advanced Materials ( IF 27.4 ) Pub Date : 2023-12-07 , DOI: 10.1002/adma.202311458
Nursultan Mussakhanuly ₁ , Arman Mahboubi Soufiani ₂ , Stefano Bernardi ₃ , Jianing Gan ₄ , Saroj Kumar Bhattacharyya ₅ , Robert Lee Chin ₁ , Hanif Muhammad ₁ , Milos Dubajic ₆ , Angus Gentle _{1,

7} , Weijian Chen ₁ , Meng Zhang _{1,

8} , Michael P Nielsen ₁ , Shujuan Huang ₉ , John Asbury ₄ , Asaph Widmer-Cooper _{3,

10} , Jae Sung Yun _{1,

11} , Xiaojing Hao ₁

Affiliation

Australian Centre for Advanced Photovoltaics, School of Photovoltaic and Renewable Energy Engineering, University of New South Wales (UNSW), Sydney, 2052, Australia.
Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Division Solar Energy, 12489, Berlin, Germany.
Australian Research Council Centre of Excellence in Exciton Science, School of Chemistry, University of Sydney, Sydney, 2006, Australia.
Department of Chemistry, The Pennsylvania State University, University Park, PA, 16802, USA.
Solid State and Elemental Analysis Unit (SSEAU), Mark Wainwright Analytical Centre, UNSW Sydney, Sydney, NSW, 2052, Australia.
Department of Chemical Engineering and Biotechnology, University of Cambridge, Philippa Fawcett Drive, Cambridge, CB3 0AS, UK.
School of Mathematical and Physical Sciences, University of Technology Sydney, Sydney, 2007, Australia.
School of New Energy and Materials, Southwest Petroleum University, Chengdu, 610500, China.
School of Engineering, Macquarie University, Sydney, 2109, Australia.
The University of Sydney Nano Institute, The University of Sydney, Sydney, NSW, 2052, Australia.
Advanced Technology Institute, Department of Electrical and Electronic Engineering, University of Surrey, Guildford, Surrey, GU2 7XH, UK.

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.

中文翻译：

热紊乱引起的应变和载流子定位激活反向卤化物偏析

在各种条件下研究了卤化物离子的逆转。然而，热诱导逆转的潜在机制仍不清楚。这项工作发现，动态无序诱导的自陷极化子定位和热无序诱导应变（TDIS）可以共同驱动反向偏析。极化子的局域化导致过量载流子密度（极化子数量）下降一个数量级，从而减少光致应变（LIS - 负责偏析）对钙钛矿框架的影响。同时，将晶格暴露于超过 LIS 的 TDIS 中可以消除光激发引起的应变梯度，因为晶格的热波动可以掩盖 LIS 应变。在连续 0.1 W cm⁻ ²照明（偏析时）下，应变紊乱估计为 0.14%，而在 80 °C 黑暗条件下，应变为 0.23%。然而，在连续照明（反转后）下将隔离膜原位加热至 80 °C 会使总应变紊乱增加至 0.25%，其中 TDIS 可能占主导地位。因此，熵对系统自由能的贡献可能分别占主导地位。各种与温度相关的原位测量和模拟进一步支持了结果。这些发现强调了应变均质化对于在实际操作条件下设计稳定钙钛矿的重要性。

更新日期：2023-12-07

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