Dec 4, 2024
8:30am - 8:45am
Hynes, Level 3, Room 300
Prakriti Kayastha1,Erik Fransson2,Paul Erhart2,Lucy Whalley1
Northumbria University1,Chalmers University of Technology2
Prakriti Kayastha1,Erik Fransson2,Paul Erhart2,Lucy Whalley1
Northumbria University1,Chalmers University of Technology2
Chalcogenide perovskites, in particular BaZrS<sub>3</sub>, has gained a lot of popularity in the last few years due to its great potential as an alternative lead-free photovoltaic absorber material. This is due to promising optoelectronic properties such as defect tolerance, strong dielectric screening, and light absorption [1]. In our previous work, we demonstrated that phase pure synthesis of this material is challenging due to the coexistence of competing Ba<sub>n+1</sub>Zr<sub>n</sub>S<sub>3n+1 </sub>Ruddlesden-Popper (RP) phases [2]. The properties of these competing RP phases remain understudied, especially given that they are expected to affect the photovoltaic performance. For the n=2 phase, a high-temperature <i>I4/mmm</i> and a low-temperature <i>P4<sub>2</sub>/mnm </i>phase has been reported [3]. We have also shown that the high-temperature <i>I4/mmm</i> phases of n=1,2,3 RP phase have imaginary phonon modes at the X-point in reciprocal space, which indicates the existence of a stable lower symmetry structure [4].<br/><br/>In this work, we present our machine learning potential model trained on n=1 to n=6 RP phases and the n= perovskite phase with the neuroevolution potential method [5]. These models have been trained on properties derived from the HSE06 hybrid exchange-correlation functional, which is shown to provide more reliable phase transition temperatures for the perovskite phase compared to the traditionally used generalized gradient-based functionals [6].<br/><br/>Using molecular dynamics we study phase transitions in RP phases across a variety of n-values. Whilst cooling the high-temperature RP phases, octahedral tilting along the X-mode leads to a second-order phase transition. We consider 48 unique tilted structures to systematically investigate all possible ground-state structures. We observe long-range ordering of octahedral tiling in the perovskite layer and show the dependence of the phase transition temperature with increasing n-value. We find that small-n RP phases adopt a different long-range ordering pattern compared to that of large-n RP phases. We demonstrate a limit where the large-n RP phase transitions coincide with the transition of the n= ∞ perovskite.<br/><br/>References:<br/>[1] Sopiha et al, Adv. Opt. Mater. (2022) 10 2101704.<br/>[2] Kayastha et al, Solar RRL (2023) 7 2201078.<br/>[3] Niu et al, J Mater. Res. (2019) 22 3819.<br/>[4] Pallikara et al, Electron. Struct. (2022) 4 033002.<br/>[5] Fan et al, J Chem. Phys. (2022) 157 114801.<br/>[6] Kayastha et al, in preparation.