Dynamic Disorder, Band Gap Widening, and Persistent Near-IR Photoluminescence up to at Least 523 K in ASnI3 Perovskites (A = Cs+, CH3NH3 + and NH2-CHNH2 +)

Athanassios G. Kontos; Andreas Kaltzoglou; Michalis K. Arfanis; Kyle M. McCall; Constantinos C. Stoumpos; Bruce W Wessels; Polycarpos Falaras; Mercouri Kanatzidis

doi:10.1021/acs.jpcc.8b10218

Dynamic Disorder, Band Gap Widening, and Persistent Near-IR Photoluminescence up to at Least 523 K in ASnI₃ Perovskites (A = Cs⁺, CH₃NH₃ ⁺ and NH₂-CHNH₂ ⁺)

Athanassios G. Kontos, Andreas Kaltzoglou, Michalis K. Arfanis, Kyle M. McCall, Constantinos C. Stoumpos, Bruce W Wessels, Polycarpos Falaras^*, Mercouri Kanatzidis

^*Corresponding author for this work

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

28 Scopus citations

Abstract

We report temperature-dependent photoluminescence (PL) in polycrystalline ASnI₃ perovskites (A = Cs⁺, CH₃NH₃ ⁺, and HC(NH₂)₂ ⁺), demonstrating extremely robust emission up to very high temperatures (523 K for CsSnI₃). The PL peak energy (E_PL) monotonically blueshifts with increasing temperature, indicating band gap widening. Variable temperature synchrotron powder X-ray diffraction analysis confirms that these changes are associated with progressive emphanitic off-centering and dynamic fluctuations of the perovskite lattice. In CsSnI₃, three different temperature gradients of E_PL are defined (0.29 meV K^-1 below 200 K, 0.17 meV K^-1 from 200 to 400 K, and 0.48 meV K^-1 above 400 K), commensurate with the onset of dynamic structural disorder at 200 K and its saturation at 400 K as the Cs⁺ atoms rattle independently of the [SnI₃]^- perovskite lattice. These results explain how solution-processed perovskites with massive defect concentrations can yield high optoelectronic performance at elevated temperatures.

Original language	English (US)
Pages (from-to)	26353-26361
Number of pages	9
Journal	Journal of Physical Chemistry C
Volume	122
Issue number	46
DOIs	https://doi.org/10.1021/acs.jpcc.8b10218
State	Published - Nov 21 2018

Funding

This work was also supported by the Department of Energy, Office of Science, Basic Energy Sciences under Grant SC0012541 (synthesis and characterization of materials diffraction studies, interpretation of data M.G.K.). Use of the Advanced Photon Source at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
General Energy
Physical and Theoretical Chemistry
Surfaces, Coatings and Films

Access to Document

10.1021/acs.jpcc.8b10218

Cite this

Kontos, A. G., Kaltzoglou, A., Arfanis, M. K., McCall, K. M., Stoumpos, C. C., Wessels, B. W., Falaras, P., & Kanatzidis, M. (2018). Dynamic Disorder, Band Gap Widening, and Persistent Near-IR Photoluminescence up to at Least 523 K in ASnI₃ Perovskites (A = Cs⁺, CH₃NH₃ ⁺ and NH₂-CHNH₂ ⁺). Journal of Physical Chemistry C, 122(46), 26353-26361. https://doi.org/10.1021/acs.jpcc.8b10218

@article{367f70df1a4648eaaf4f5b1fdd958ff8,

title = "Dynamic Disorder, Band Gap Widening, and Persistent Near-IR Photoluminescence up to at Least 523 K in ASnI3 Perovskites (A = Cs+, CH3NH3 + and NH2-CHNH2 +)",

abstract = "We report temperature-dependent photoluminescence (PL) in polycrystalline ASnI3 perovskites (A = Cs+, CH3NH3 +, and HC(NH2)2 +), demonstrating extremely robust emission up to very high temperatures (523 K for CsSnI3). The PL peak energy (EPL) monotonically blueshifts with increasing temperature, indicating band gap widening. Variable temperature synchrotron powder X-ray diffraction analysis confirms that these changes are associated with progressive emphanitic off-centering and dynamic fluctuations of the perovskite lattice. In CsSnI3, three different temperature gradients of EPL are defined (0.29 meV K-1 below 200 K, 0.17 meV K-1 from 200 to 400 K, and 0.48 meV K-1 above 400 K), commensurate with the onset of dynamic structural disorder at 200 K and its saturation at 400 K as the Cs+ atoms rattle independently of the [SnI3]- perovskite lattice. These results explain how solution-processed perovskites with massive defect concentrations can yield high optoelectronic performance at elevated temperatures.",

author = "Kontos, {Athanassios G.} and Andreas Kaltzoglou and Arfanis, {Michalis K.} and McCall, {Kyle M.} and Stoumpos, {Constantinos C.} and Wessels, {Bruce W} and Polycarpos Falaras and Mercouri Kanatzidis",

note = "Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

year = "2018",

month = nov,

day = "21",

doi = "10.1021/acs.jpcc.8b10218",

language = "English (US)",

volume = "122",

pages = "26353--26361",

journal = "Journal of Physical Chemistry C",

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Kontos, AG, Kaltzoglou, A, Arfanis, MK, McCall, KM, Stoumpos, CC, Wessels, BW, Falaras, P & Kanatzidis, M 2018, 'Dynamic Disorder, Band Gap Widening, and Persistent Near-IR Photoluminescence up to at Least 523 K in ASnI₃ Perovskites (A = Cs⁺, CH₃NH₃ ⁺ and NH₂-CHNH₂ ⁺)', Journal of Physical Chemistry C, vol. 122, no. 46, pp. 26353-26361. https://doi.org/10.1021/acs.jpcc.8b10218

Dynamic Disorder, Band Gap Widening, and Persistent Near-IR Photoluminescence up to at Least 523 K in ASnI₃ Perovskites (A = Cs⁺, CH₃NH₃ ⁺ and NH₂-CHNH₂ ⁺). / Kontos, Athanassios G.; Kaltzoglou, Andreas; Arfanis, Michalis K. et al.
In: Journal of Physical Chemistry C, Vol. 122, No. 46, 21.11.2018, p. 26353-26361.

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

TY - JOUR

T1 - Dynamic Disorder, Band Gap Widening, and Persistent Near-IR Photoluminescence up to at Least 523 K in ASnI3 Perovskites (A = Cs+, CH3NH3 + and NH2-CHNH2 +)

AU - Kontos, Athanassios G.

AU - Kaltzoglou, Andreas

AU - Arfanis, Michalis K.

AU - McCall, Kyle M.

AU - Stoumpos, Constantinos C.

AU - Wessels, Bruce W

AU - Falaras, Polycarpos

AU - Kanatzidis, Mercouri

PY - 2018/11/21

Y1 - 2018/11/21

N2 - We report temperature-dependent photoluminescence (PL) in polycrystalline ASnI3 perovskites (A = Cs+, CH3NH3 +, and HC(NH2)2 +), demonstrating extremely robust emission up to very high temperatures (523 K for CsSnI3). The PL peak energy (EPL) monotonically blueshifts with increasing temperature, indicating band gap widening. Variable temperature synchrotron powder X-ray diffraction analysis confirms that these changes are associated with progressive emphanitic off-centering and dynamic fluctuations of the perovskite lattice. In CsSnI3, three different temperature gradients of EPL are defined (0.29 meV K-1 below 200 K, 0.17 meV K-1 from 200 to 400 K, and 0.48 meV K-1 above 400 K), commensurate with the onset of dynamic structural disorder at 200 K and its saturation at 400 K as the Cs+ atoms rattle independently of the [SnI3]- perovskite lattice. These results explain how solution-processed perovskites with massive defect concentrations can yield high optoelectronic performance at elevated temperatures.

AB - We report temperature-dependent photoluminescence (PL) in polycrystalline ASnI3 perovskites (A = Cs+, CH3NH3 +, and HC(NH2)2 +), demonstrating extremely robust emission up to very high temperatures (523 K for CsSnI3). The PL peak energy (EPL) monotonically blueshifts with increasing temperature, indicating band gap widening. Variable temperature synchrotron powder X-ray diffraction analysis confirms that these changes are associated with progressive emphanitic off-centering and dynamic fluctuations of the perovskite lattice. In CsSnI3, three different temperature gradients of EPL are defined (0.29 meV K-1 below 200 K, 0.17 meV K-1 from 200 to 400 K, and 0.48 meV K-1 above 400 K), commensurate with the onset of dynamic structural disorder at 200 K and its saturation at 400 K as the Cs+ atoms rattle independently of the [SnI3]- perovskite lattice. These results explain how solution-processed perovskites with massive defect concentrations can yield high optoelectronic performance at elevated temperatures.

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U2 - 10.1021/acs.jpcc.8b10218

DO - 10.1021/acs.jpcc.8b10218

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