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
(Q
22 ≈ 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.