Crystal Structure Evolution and Notable Thermal Expansion in Hybrid Perovskites Formamidinium Tin Iodide and Formamidinium Lead Bromide

Emily C. Schueller, Geneva Laurita, Douglas H. Fabini, Constantinos C. Stoumpos, Mercouri G Kanatzidis, Ram Seshadri

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Abstract

The temperature-dependent structure evolution of the hybrid halide perovskite compounds, formamidinium tin iodide (FASnI3, FA+ = CH[NH2]2+) and formamidinium lead bromide (FAPbBr3), has been monitored using high-resolution synchrotron X-ray powder diffraction between 300 and 100 K. The data are consistent with a transition from cubic Pm3m (No. 221) to tetragonal P4/mbm (No. 127) for both materials upon cooling; this occurs for FAPbBr3 between 275 and 250 K, and for FASnI3 between 250 and 225 K. Upon further cooling, between 150 and 125 K, both materials undergo a transition to an orthorhombic Pnma (No. 62) structure. The transitions are confirmed by calorimetry and dielectric measurements. In the tetragonal regime, the coefficients of volumetric thermal expansion of FASnI3 and FAPbBr3 are among the highest recorded for any extended inorganic crystalline solid, reaching 219 ppm K-1 for FASnI3 at 225 K. Atomic displacement parameters of all atoms for both materials suggest dynamic motion is occurring in the inorganic sublattice due to the flexibility of the inorganic network and dynamic lone pair stereochemical activity on the B-site. Unusual pseudocubic behavior is displayed in the tetragonal phase of the FAPbBr3, similar to that previously observed in FAPbI3.

Original languageEnglish
Pages (from-to)695-701
Number of pages7
JournalInorganic Chemistry
Volume57
Issue number2
DOIs
Publication statusPublished - Jan 16 2018

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Tin
Iodides
perovskites
iodides
Thermal expansion
bromides
thermal expansion
tin
Crystal structure
crystal structure
Tin compounds
tin compounds
Cooling
cooling
Calorimetry
Synchrotrons
X ray powder diffraction
sublattices
halides
flexibility

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Crystal Structure Evolution and Notable Thermal Expansion in Hybrid Perovskites Formamidinium Tin Iodide and Formamidinium Lead Bromide. / Schueller, Emily C.; Laurita, Geneva; Fabini, Douglas H.; Stoumpos, Constantinos C.; Kanatzidis, Mercouri G; Seshadri, Ram.

In: Inorganic Chemistry, Vol. 57, No. 2, 16.01.2018, p. 695-701.

Research output: Contribution to journalArticle

Schueller, Emily C. ; Laurita, Geneva ; Fabini, Douglas H. ; Stoumpos, Constantinos C. ; Kanatzidis, Mercouri G ; Seshadri, Ram. / Crystal Structure Evolution and Notable Thermal Expansion in Hybrid Perovskites Formamidinium Tin Iodide and Formamidinium Lead Bromide. In: Inorganic Chemistry. 2018 ; Vol. 57, No. 2. pp. 695-701.
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