Reentrant Structural and Optical Properties and Large Positive Thermal Expansion in Perovskite Formamidinium Lead Iodide

Douglas H. Fabini, Constantinos C. Stoumpos, Geneva Laurita, Andreas Kaltzoglou, Athanassios G. Kontos, Polycarpos Falaras, Mercouri G Kanatzidis, Ram Seshadri

Research output: Contribution to journalArticle

32 Citations (Scopus)

Abstract

The structure of the hybrid perovskite HC(NH2)2PbI3 (formamidinium lead iodide) reflects competing interactions associated with molecular motion, hydrogen bonding tendencies, thermally activated soft octahedral rotations, and the propensity for the Pb2+ lone pair to express its stereochemistry. High-resolution synchrotron X-ray powder diffraction reveals a continuous transition from the cubic α-phase (Pm3m, #221) to a tetragonal β-phase (P4/mbm, #127) at around 285 K, followed by a first-order transition to a tetragonal γ-phase (retaining P4/mbm, #127) at 140 K. An unusual reentrant pseudosymmetry in the β-to-γ phase transition is seen that is also reflected in the photoluminescence. Around room temperature, the coefficient of volumetric thermal expansion is among the largest for any extended crystalline solid.

Original languageEnglish
Pages (from-to)15392-15396
Number of pages5
JournalAngewandte Chemie - International Edition
Volume55
Issue number49
DOIs
Publication statusPublished - Dec 5 2016

Fingerprint

Stereochemistry
Iodides
Synchrotrons
Perovskite
X ray powder diffraction
Thermal expansion
Structural properties
Photoluminescence
Hydrogen bonds
Optical properties
Lead
Phase transitions
Crystalline materials
Temperature
formamidine
perovskite

Keywords

  • perovskite phases
  • phase transitions
  • solid-state structures
  • structure elucidation
  • thermal expansion

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Fabini, D. H., Stoumpos, C. C., Laurita, G., Kaltzoglou, A., Kontos, A. G., Falaras, P., ... Seshadri, R. (2016). Reentrant Structural and Optical Properties and Large Positive Thermal Expansion in Perovskite Formamidinium Lead Iodide. Angewandte Chemie - International Edition, 55(49), 15392-15396. https://doi.org/10.1002/anie.201609538

Reentrant Structural and Optical Properties and Large Positive Thermal Expansion in Perovskite Formamidinium Lead Iodide. / Fabini, Douglas H.; Stoumpos, Constantinos C.; Laurita, Geneva; Kaltzoglou, Andreas; Kontos, Athanassios G.; Falaras, Polycarpos; Kanatzidis, Mercouri G; Seshadri, Ram.

In: Angewandte Chemie - International Edition, Vol. 55, No. 49, 05.12.2016, p. 15392-15396.

Research output: Contribution to journalArticle

Fabini, Douglas H. ; Stoumpos, Constantinos C. ; Laurita, Geneva ; Kaltzoglou, Andreas ; Kontos, Athanassios G. ; Falaras, Polycarpos ; Kanatzidis, Mercouri G ; Seshadri, Ram. / Reentrant Structural and Optical Properties and Large Positive Thermal Expansion in Perovskite Formamidinium Lead Iodide. In: Angewandte Chemie - International Edition. 2016 ; Vol. 55, No. 49. pp. 15392-15396.
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