Noncollinear Electric Dipoles in a Polar Chiral Phase of CsSnBr3 Perovskite

Publikation: Beitrag in FachzeitschriftForschungsartikelBeigetragenBegutachtung

Beitragende

  • Douglas H. Fabini - , Max-Planck-Institut für Festkörperforschung, Massachusetts Institute of Technology (MIT) (Autor:in)
  • Kedar Honasoge - , Max-Planck-Institut für Festkörperforschung (Autor:in)
  • Adi Cohen - , Weizmann Institute of Science (Autor:in)
  • Sebastian Bette - , Max-Planck-Institut für Festkörperforschung (Autor:in)
  • Kyle M. McCall - , Northwestern University (Autor:in)
  • Constantinos C. Stoumpos - , Universität Kreta (Autor:in)
  • Steffen Klenner - , Westfälische Wilhelms-Universität Münster (Autor:in)
  • Mirjam Zipkat - , Ludwig-Maximilians-Universität München (LMU) (Autor:in)
  • Le Phuong Hoang - , Max-Planck-Institut für Festkörperforschung (Autor:in)
  • Jürgen Nuss - , Max-Planck-Institut für Festkörperforschung (Autor:in)
  • Reinhard K. Kremer - , Max-Planck-Institut für Festkörperforschung (Autor:in)
  • Mercouri G. Kanatzidis - , Northwestern University (Autor:in)
  • Omer Yaffe - , Weizmann Institute of Science (Autor:in)
  • Stefan Kaiser - , Max-Planck-Institut für Festkörperforschung (Autor:in)
  • Bettina V. Lotsch - , Max-Planck-Institut für Festkörperforschung, Ludwig-Maximilians-Universität München (LMU) (Autor:in)

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

OriginalspracheEnglisch
Seiten (von - bis)15701-15717
Seitenumfang17
FachzeitschriftJournal of the American Chemical Society
Jahrgang146
Ausgabenummer23
PublikationsstatusVeröffentlicht - 12 Juni 2024
Peer-Review-StatusJa
Extern publiziertJa

Externe IDs

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