Experimental absence of the non-perovskite ground state phases of MaPbI3 explained by a Funnel Hopping Monte Carlo study based on a neural network potential

Abstract

Methylammonium lead iodide is a material known for its exceptional opto-electronic properties that make it a promising candidate for many high performance applications, such as light emitting diodes or solar cells. A recent computational structure search revealed two previously unknown non-perovskite polymorphs, that are lower in energy than the experimentally observed perovskite phases. To investigate the elusiveness of the non-perovskite phases in experimental studies, we extended our Funnel Hopping Monte Carlo (FHMC) method to periodic systems and performed extensive MC simulations driven by a machine learned potential. FHMC simulations that also include these newly discovered non-perovskite phases show that above temperatures of 200 K the perovskite phases are thermodynamically preferred. A comparison with the quasi-harmonic approximation highlights the importance of anharmonic effects captured by FHMC.