We
report temperature-dependent photoluminescence
(PL) in polycrystalline ASnI3 perovskites (A = Cs+, CH3NH3
+, and HC(NH2)2
+), demonstrating extremely robust emission
up to very high temperatures (523 K for CsSnI3). The PL
peak energy (E
PL) monotonically blueshifts
with increasing temperature, indicating band gap widening. Variable
temperature synchrotron powder X-ray diffraction analysis confirms
that these changes are associated with progressive emphanitic off-centering
and dynamic fluctuations of the perovskite lattice. In CsSnI3, three different temperature gradients of E
PL are defined (0.29 meV K–1 below 200 K,
0.17 meV K–1 from 200 to 400 K, and 0.48 meV K–1 above 400 K), commensurate with the onset of dynamic
structural disorder at 200 K and its saturation at 400 K as the Cs+ atoms rattle independently of the [SnI3]− perovskite lattice. These results explain how solution-processed
perovskites with massive defect concentrations can yield high optoelectronic
performance at elevated temperatures.