Thermal history controls the optoelectronic response of lead halide perovskites through structure and dynamics

@misc{dubajic2026thermal,
  title = {{Thermal history controls the optoelectronic response of lead halide perovskites through structure and dynamics}},
  author = {Milos Dubajic and Xia Liang and Johan Klarbring and Yang Lu and Thomas A. Selby and Erik Fransson and Philippe Holzhey and Benjamin M Gallant and Qichun Gu and Ganbaatar Tumen-Ulzii and Khasim Saheb Bayikadi and Isaiah Gilley and Martin v. Zimmermann and Christian Orr and Chwenhaw Liao and Josh S. Moon and Jacek Jasieniak and Makhsud Saidaminov and Michael P. Nielsen and Tom Wu and Stephen P. Bremner and Anita Ho-Baillie and Julia Wiktor and Paul Erhart and Steve Albrecht and Mercouri Kanatzidis and Henry J Snaith and Aron Walsh and Samuel D. Stranks},
  howpublished = {arXiv},
  year = {2026},
  month = sep,
  doi = {10.48550/arxiv.2609.03211},
  eprint = {2609.03211},
  archivePrefix = {arXiv},
  url = {https://arxiv.org/abs/2609.03211},
  note = {CC BY 4.0},
}

TY  - UNPB
TI  - Thermal history controls the optoelectronic response of lead halide perovskites through structure and dynamics
AU  - Milos Dubajic
AU  - Xia Liang
AU  - Johan Klarbring
AU  - Yang Lu
AU  - Thomas A. Selby
AU  - Erik Fransson
AU  - Philippe Holzhey
AU  - Benjamin M Gallant
AU  - Qichun Gu
AU  - Ganbaatar Tumen-Ulzii
AU  - Khasim Saheb Bayikadi
AU  - Isaiah Gilley
AU  - Martin v. Zimmermann
AU  - Christian Orr
AU  - Chwenhaw Liao
AU  - Josh S. Moon
AU  - Jacek Jasieniak
AU  - Makhsud Saidaminov
AU  - Michael P. Nielsen
AU  - Tom Wu
AU  - Stephen P. Bremner
AU  - Anita Ho-Baillie
AU  - Julia Wiktor
AU  - Paul Erhart
AU  - Steve Albrecht
AU  - Mercouri Kanatzidis
AU  - Henry J Snaith
AU  - Aron Walsh
AU  - Samuel D. Stranks
PY  - 2026
DA  - 2026/09/02
PB  - arXiv
DO  - 10.48550/arxiv.2609.03211
UR  - https://arxiv.org/abs/2609.03211
AB  - Lead halide perovskites are promising optoelectronic materials for photovoltaics, light emission and detection. Their efficiencies in PV now approach the detailed-balance limit, leaving stability as the principal barrier. The intrinsic instabilities studied to date centre on ionic motion within a fixed, homogeneous lattice. Here we identify a further source of intrinsic structural instability, hidden in the lattice dynamics. Mapping caesium, methylammonium and formamidinium-based compositions with Cl, Br, I and mixed X-sites through all accessible phases, using single crystal X-ray and neutron diffuse scattering, machine-learning-assisted molecular dynamics, a phenomenological octahedral tilt model and hyperspectral photoluminescence, we find that nearly every composition hosts equilibrium local structural fluctuations: dynamic nanodomains of correlated octahedral tilts, a few nanometres in size, that locally break the crystallographic symmetry. Three complementary levers control them. The A-site cation sets their symmetry, shape and anisotropy, from sparse, isotropic and tetragonal in formamidinium-based compositions to dense, anisotropic and orthorhombic in nominally cubic caesium-based ones, the most locally disordered we studied. The halide controls the dynamic disorder and the phase-transition sequence. Thermal history is the third: different ramp rates drive nominally identical compositions into distinct crystallographic phases, each with its own hidden local order. In MAPbI3, the heating rate alone changes the photoluminescence quantum efficiency across the phase transition. Because these transitions lie within device operating ranges, from terrestrial thermal cycling to the extremes of space, thermal history may shape the local structure, and hence the optoelectronic response, throughout fabrication and operation, establishing it as a design variable alongside composition.
ER  -