Dielectric and Thermodynamic Signatures of Low-Temperature Glassy Dynamics in the Hybrid Perovskites CH3NH3PbI3 and HC(NH2)2PbI3

Douglas H. Fabini, Tom Hogan, Hayden A. Evans, Constantinos C. Stoumpos, Mercouri G Kanatzidis, Ram Seshadri

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Abstract

Hybrid main group halide perovskites hold great technological promise in optoelectronic applications and present rich and complex evolution of structure and dynamics. Here we present low-temperature dielectric measurements and calorimetry of APbI3 [A = CH3NH3 +, HC(NH2)2 +] that suggest glassy behavior on cooling. In both compounds, the dielectric loss displays frequency-dependent peaks below 100 K characteristic of a glassy slowing of relaxation dynamics, with HC(NH2)2PbI3 exhibiting greater glass fragility. Consistent with quenched disorder, the low-temperature heat capacity of both perovskites deviates substantially from the ∼T3 acoustic phonon contribution predicted by the Debye model. We suggest that static disorder of the A-site molecular cation, potentially coupled to local distortions of the Pb-I sublattice, is responsible for these phenomena. The distinct low-temperature dynamics observed in these two perovskites suggest qualitative differences in the interaction between the molecular cation and the surrounding inorganic framework, with potential implications for defect screening and device performance at ambient temperatures.

Original languageEnglish
Pages (from-to)376-381
Number of pages6
JournalJournal of Physical Chemistry Letters
Volume7
Issue number3
DOIs
Publication statusPublished - Feb 4 2016

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perovskites
signatures
Thermodynamics
thermodynamics
disorders
Cations
cations
Positive ions
dielectric loss
Temperature
sublattices
ambient temperature
halides
Calorimetry
screening
heat measurement
Dielectric losses
specific heat
Optoelectronic devices
Specific heat

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

Dielectric and Thermodynamic Signatures of Low-Temperature Glassy Dynamics in the Hybrid Perovskites CH3NH3PbI3 and HC(NH2)2PbI3 . / Fabini, Douglas H.; Hogan, Tom; Evans, Hayden A.; Stoumpos, Constantinos C.; Kanatzidis, Mercouri G; Seshadri, Ram.

In: Journal of Physical Chemistry Letters, Vol. 7, No. 3, 04.02.2016, p. 376-381.

Research output: Contribution to journalArticle

Fabini, Douglas H. ; Hogan, Tom ; Evans, Hayden A. ; Stoumpos, Constantinos C. ; Kanatzidis, Mercouri G ; Seshadri, Ram. / Dielectric and Thermodynamic Signatures of Low-Temperature Glassy Dynamics in the Hybrid Perovskites CH3NH3PbI3 and HC(NH2)2PbI3 In: Journal of Physical Chemistry Letters. 2016 ; Vol. 7, No. 3. pp. 376-381.
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