Evolutionary exploration of polytypism in lead halide perovskites

Zhenzhu Li, Ji Sang Park, Aron Walsh

Research output: Contribution to journalArticlepeer-review

10 Scopus citations


The regular ABX3cubic perovskite structure is composed of close-packed AX3layers stacked along the 〈111〉 axis. An equivalent hexagonal close-packed network can also be formed, in addition to a series of intermediate polytype sequences. Internally, these correspond to combinations of face- and corner-sharing octahedral chains that can dramatically alter the physical properties of the material. Here, we assess the thermodynamics of polytypism in CsPbI3and CsPbBr3. The total energies obtained from density functional theory are used to paramaterize an axial Ising-type model Hamiltonian that includes linear and cubic correlation terms of the pseudo-spin. A genetic algorithm is built to explore the polytype phase space that grows exponentially with the number of layers. The ground-state structures of CsPbX3polytypes are analysed to identify features of polytypism such as the distinct arrangements of layers and symmetry forbidden sequences. A number of polytypes with low ordering energies (around thermal energy at room temperature) are predicted, which could form distinct phases or appear as stacking faults within perovskite grains.

Original languageEnglish
Pages (from-to)12165-12173
Number of pages9
JournalChemical Science
Issue number36
StatePublished - 28 Sep 2021

Bibliographical note

Funding Information:
We thank Jacob N. Wilson for constructive discussions in the early stages of this project. We are grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194/1). Via our membership of the UK's HPC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202, EP/R029431), this work used the ARCHER UK National Supercomputing Service. This work was also supported by National Research Foundation of Korea (NRF) grants funded by the Korea government (MSIT) (No. 2020R1A5A1019131 and 2020R1F1A1053606).

Publisher Copyright:
© The Royal Society of Chemistry 2021.


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