Noncollinear Electric Dipoles in a Polar Chiral Phase of CsSnBr3 Perovskite

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

  • Douglas H. Fabini - , Max Planck Institute for Solid State Research, Massachusetts Institute of Technology (MIT) (Author)
  • Kedar Honasoge - , Max Planck Institute for Solid State Research (Author)
  • Adi Cohen - , Weizmann Institute of Science (Author)
  • Sebastian Bette - , Max Planck Institute for Solid State Research (Author)
  • Kyle M. McCall - , Northwestern University (Author)
  • Constantinos C. Stoumpos - , University of Crete (Author)
  • Steffen Klenner - , University of Münster (Author)
  • Mirjam Zipkat - , Ludwig Maximilian University of Munich (Author)
  • Le Phuong Hoang - , Max Planck Institute for Solid State Research (Author)
  • Jürgen Nuss - , Max Planck Institute for Solid State Research (Author)
  • Reinhard K. Kremer - , Max Planck Institute for Solid State Research (Author)
  • Mercouri G. Kanatzidis - , Northwestern University (Author)
  • Omer Yaffe - , Weizmann Institute of Science (Author)
  • Stefan Kaiser - , Max Planck Institute for Solid State Research (Author)
  • Bettina V. Lotsch - , Max Planck Institute for Solid State Research, Ludwig Maximilian University of Munich (Author)

Abstract

Polar and chiral crystal symmetries confer a variety of potentially useful functionalities upon solids by coupling otherwise noninteracting mechanical, electronic, optical, and magnetic degrees of freedom. We describe two phases of the 3D perovskite, CsSnBr3, which emerge below 85 K due to the formation of Sn(II) lone pairs and their interaction with extant octahedral tilts. Phase II (77 K < T < 85 K, space group P21/m) exhibits ferroaxial order driven by a noncollinear pattern of lone pair-driven distortions within the plane normal to the unique octahedral tilt axis, preserving the inversion symmetry observed at higher temperatures. Phase I (T < 77 K, space group P21) additionally exhibits ferroelectric order due to distortions along the unique tilt axis, breaking both inversion and mirror symmetries. This polar and chiral phase exhibits second harmonic generation from the bulk and pronounced electrostriction and negative thermal expansion along the polar axis (Q22 ≈ 1.1 m4 C-2; αb = −7.8 × 10-5 K-1) through the onset of polarization. The structures of phases I and II were predicted by recursively following harmonic phonon instabilities to generate a tree of candidate structures and subsequently corroborated by synchrotron X-ray powder diffraction and polarized Raman and 81Br nuclear quadrupole resonance spectroscopies. Preliminary attempts to suppress unintentional hole doping to allow for ferroelectric switching are described. Together, the polar symmetry, small band gap, large spin-orbit splitting of Sn 5p orbitals, and predicted strain sensitivity of the symmetry-breaking distortions suggest bulk samples and epitaxial films of CsSnBr3 or its neighboring solid solutions as candidates for bulk Rashba effects.

Details

Original languageEnglish
Pages (from-to)15701-15717
Number of pages17
JournalJournal of the American Chemical Society
Volume146
Issue number23
Publication statusPublished - 12 Jun 2024
Peer-reviewedYes
Externally publishedYes

External IDs

PubMed 38819106
Mendeley 2b689f5f-c0ed-30fc-9983-6d9210e68646
ORCID /0000-0001-9862-2788/work/162348821