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

doi:10.1002/anie.201609538

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^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

153 Scopus citations

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 language	English (US)
Pages (from-to)	15392-15396
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	55
Issue number	49
DOIs	https://doi.org/10.1002/anie.201609538
State	Published - Dec 5 2016

Keywords

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

ASJC Scopus subject areas

Catalysis
General Chemistry

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@article{e661c7b76eeb41b598323e779f7bb0ba,

title = "Reentrant Structural and Optical Properties and Large Positive Thermal Expansion in Perovskite Formamidinium Lead Iodide",

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.",

keywords = "perovskite phases, phase transitions, solid-state structures, structure elucidation, thermal expansion",

author = "Fabini, {Douglas H.} and Stoumpos, {Constantinos C.} and Geneva Laurita and Andreas Kaltzoglou and Kontos, {Athanassios G.} and Polycarpos Falaras and Kanatzidis, {Mercouri G.} and Ram Seshadri",

note = "Publisher Copyright: {\textcopyright} 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2016",

month = dec,

day = "5",

doi = "10.1002/anie.201609538",

language = "English (US)",

volume = "55",

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T1 - Reentrant Structural and Optical Properties and Large Positive Thermal Expansion in Perovskite Formamidinium Lead Iodide

AU - Fabini, Douglas H.

AU - Stoumpos, Constantinos C.

AU - Laurita, Geneva

AU - Kaltzoglou, Andreas

AU - Kontos, Athanassios G.

AU - Falaras, Polycarpos

AU - Kanatzidis, Mercouri G.

AU - Seshadri, Ram

PY - 2016/12/5

Y1 - 2016/12/5

N2 - 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.

AB - 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.

KW - perovskite phases

KW - phase transitions

KW - solid-state structures

KW - structure elucidation

KW - thermal expansion

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JO - Angewandte Chemie - International Edition

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ER -

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

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