Exciton and Free Charge Dynamics of Methylammonium Lead Iodide Perovskites Are Different in the Tetragonal and Orthorhombic Phases

He Wang, Luisa Whittaker-Brooks, Graham R. Fleming

Research output: Contribution to journalArticle

51 Citations (Scopus)

Abstract

The small exciton binding energy of perovskite suggests that the long-lived photoluminescence and slow recovery of the ground state bleaching of the tetragonal phase at room temperature results primarily from the decay of free charges rather than the decay of the initially created excitons. Here we demonstrate the ground state bleaching recovery of the orthorhombic phase of methylammonium lead iodide (CH3NH3PbI3) is much faster than that of the tetragonal phase using temperature dependent transient absorption spectroscopy. The distribution in orientation of the methylammonium group which is disordered in the tetragonal phase and ordered in the orthorhombic phase results in smaller dielectric constant and larger exciton binding energy in the latter phase. We observe the recovery of the ground state bleaching in the orthorhombic phase to be comprised of decays of both excitons and free charges. Our findings suggest CH3NH3PbI3 behaves like a nonexcitonic semiconductor in the tetragonal phase and an excitonic semiconductor in the orthorhombic phase. (Figure Presented).

Original languageEnglish (US)
Pages (from-to)19590-19595
Number of pages6
JournalJournal of Physical Chemistry C
Volume119
Issue number34
DOIs
StatePublished - Aug 27 2015
Externally publishedYes

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Iodides
perovskites
Excitons
iodides
bleaching
Bleaching
Lead
excitons
Ground state
recovery
Binding energy
Recovery
ground state
decay
binding energy
Semiconductor materials
Absorption spectroscopy
Perovskite
Photoluminescence
absorption spectroscopy

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

Exciton and Free Charge Dynamics of Methylammonium Lead Iodide Perovskites Are Different in the Tetragonal and Orthorhombic Phases. / Wang, He; Whittaker-Brooks, Luisa; Fleming, Graham R.

In: Journal of Physical Chemistry C, Vol. 119, No. 34, 27.08.2015, p. 19590-19595.

Research output: Contribution to journalArticle

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abstract = "The small exciton binding energy of perovskite suggests that the long-lived photoluminescence and slow recovery of the ground state bleaching of the tetragonal phase at room temperature results primarily from the decay of free charges rather than the decay of the initially created excitons. Here we demonstrate the ground state bleaching recovery of the orthorhombic phase of methylammonium lead iodide (CH3NH3PbI3) is much faster than that of the tetragonal phase using temperature dependent transient absorption spectroscopy. The distribution in orientation of the methylammonium group which is disordered in the tetragonal phase and ordered in the orthorhombic phase results in smaller dielectric constant and larger exciton binding energy in the latter phase. We observe the recovery of the ground state bleaching in the orthorhombic phase to be comprised of decays of both excitons and free charges. Our findings suggest CH3NH3PbI3 behaves like a nonexcitonic semiconductor in the tetragonal phase and an excitonic semiconductor in the orthorhombic phase. (Figure Presented).",
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AU - Fleming, Graham R.

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N2 - The small exciton binding energy of perovskite suggests that the long-lived photoluminescence and slow recovery of the ground state bleaching of the tetragonal phase at room temperature results primarily from the decay of free charges rather than the decay of the initially created excitons. Here we demonstrate the ground state bleaching recovery of the orthorhombic phase of methylammonium lead iodide (CH3NH3PbI3) is much faster than that of the tetragonal phase using temperature dependent transient absorption spectroscopy. The distribution in orientation of the methylammonium group which is disordered in the tetragonal phase and ordered in the orthorhombic phase results in smaller dielectric constant and larger exciton binding energy in the latter phase. We observe the recovery of the ground state bleaching in the orthorhombic phase to be comprised of decays of both excitons and free charges. Our findings suggest CH3NH3PbI3 behaves like a nonexcitonic semiconductor in the tetragonal phase and an excitonic semiconductor in the orthorhombic phase. (Figure Presented).

AB - The small exciton binding energy of perovskite suggests that the long-lived photoluminescence and slow recovery of the ground state bleaching of the tetragonal phase at room temperature results primarily from the decay of free charges rather than the decay of the initially created excitons. Here we demonstrate the ground state bleaching recovery of the orthorhombic phase of methylammonium lead iodide (CH3NH3PbI3) is much faster than that of the tetragonal phase using temperature dependent transient absorption spectroscopy. The distribution in orientation of the methylammonium group which is disordered in the tetragonal phase and ordered in the orthorhombic phase results in smaller dielectric constant and larger exciton binding energy in the latter phase. We observe the recovery of the ground state bleaching in the orthorhombic phase to be comprised of decays of both excitons and free charges. Our findings suggest CH3NH3PbI3 behaves like a nonexcitonic semiconductor in the tetragonal phase and an excitonic semiconductor in the orthorhombic phase. (Figure Presented).

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