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Low-dimensional emissive states in non-stoichiometric methylammonium lead halide perovskites

Low-dimensional emissive states in non-stoichiometric methylammonium lead halide perovskites
Low-dimensional emissive states in non-stoichiometric methylammonium lead halide perovskites

Mixed-halide perovskites prepared from methylammonium iodide and lead chloride (MAPbI 3-x Cl x ) precursors are becoming increasingly well understood, however the effect of non-stoichiometry in this system is still not clear. Here, we create MAPbI 3-x Cl x perovskites from starting mixtures containing an excess of MAI, and study them using a variety of structural and optical probes. Using grazing incidence X-ray scattering (GIWAXS) we demonstrate the existence of non-perovskite structures, and show that addition of hydroiodic acid (HI) also leads to similar low-dimensional phase formation. Photoluminescence spectroscopy performed at cryogenic temperatures indicates the existence of multiple emissive states between 510 nm and 605 nm resulting from a low dimensional phase (LDP) or multiple phases. By mapping the distribution of luminescence across the surface with submicron resolution, we found strong co-localisation of LDP emissive states. At certain blend ratios, emission is seen from both LDP states and methylammonium lead iodide perovskite (around 770 nm). Photoluminescence excitation spectroscopy of mixed-phase films reveals energy transfer, or a cascade, between different LDP states, but this process only occurs inefficiently to the surrounding perovskite. Time-resolved photoluminescence measurements demonstrate that LDP excited-state lifetimes decrease as a function of increasing temperature; a process consistent with a thermally-activated charge transfer process. Our work suggests that non-stoichiometric materials prepared via this processing route can lead to the formation of metastable LDPs with unique material properties that merit further investigation.

2050-7488
11104-11116
Freestone, Benjamin G.
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Smith, Joel A.
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Piana, Giacomo
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Kilbride, Rachel C.
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Parnell, Andrew J.
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Sortino, Luca
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Coles, David M.
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Ball, Orianna B.
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Martsinovich, Natalia
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Thompson, Courtney J.
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Alanazi, Tarek I.
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Game, Onkar S.
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Tartakovskii, Alexander I.
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Lagoudakis, Pavlos
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Lidzey, David G.
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Freestone, Benjamin G.
93e89529-c13d-43eb-9766-7279eaaa4cfd
Smith, Joel A.
23670f98-336e-4c71-873f-294d34888703
Piana, Giacomo
26ddb373-9efe-43c4-a826-4f17f532d521
Kilbride, Rachel C.
f633149b-992b-403b-a999-f3ce9810c5e9
Parnell, Andrew J.
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Sortino, Luca
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Coles, David M.
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Ball, Orianna B.
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Martsinovich, Natalia
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Thompson, Courtney J.
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Alanazi, Tarek I.
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Game, Onkar S.
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Tartakovskii, Alexander I.
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Lagoudakis, Pavlos
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Lidzey, David G.
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Freestone, Benjamin G., Smith, Joel A., Piana, Giacomo, Kilbride, Rachel C., Parnell, Andrew J., Sortino, Luca, Coles, David M., Ball, Orianna B., Martsinovich, Natalia, Thompson, Courtney J., Alanazi, Tarek I., Game, Onkar S., Tartakovskii, Alexander I., Lagoudakis, Pavlos and Lidzey, David G. (2019) Low-dimensional emissive states in non-stoichiometric methylammonium lead halide perovskites. Journal of Materials Chemistry A, 7 (18), 11104-11116. (doi:10.1039/c8ta12184b).

Record type: Article

Abstract

Mixed-halide perovskites prepared from methylammonium iodide and lead chloride (MAPbI 3-x Cl x ) precursors are becoming increasingly well understood, however the effect of non-stoichiometry in this system is still not clear. Here, we create MAPbI 3-x Cl x perovskites from starting mixtures containing an excess of MAI, and study them using a variety of structural and optical probes. Using grazing incidence X-ray scattering (GIWAXS) we demonstrate the existence of non-perovskite structures, and show that addition of hydroiodic acid (HI) also leads to similar low-dimensional phase formation. Photoluminescence spectroscopy performed at cryogenic temperatures indicates the existence of multiple emissive states between 510 nm and 605 nm resulting from a low dimensional phase (LDP) or multiple phases. By mapping the distribution of luminescence across the surface with submicron resolution, we found strong co-localisation of LDP emissive states. At certain blend ratios, emission is seen from both LDP states and methylammonium lead iodide perovskite (around 770 nm). Photoluminescence excitation spectroscopy of mixed-phase films reveals energy transfer, or a cascade, between different LDP states, but this process only occurs inefficiently to the surrounding perovskite. Time-resolved photoluminescence measurements demonstrate that LDP excited-state lifetimes decrease as a function of increasing temperature; a process consistent with a thermally-activated charge transfer process. Our work suggests that non-stoichiometric materials prepared via this processing route can lead to the formation of metastable LDPs with unique material properties that merit further investigation.

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Low-dimensional emissive states in non-stoichiometric methylammonium lead halide perovskites - Accepted Manuscript
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Accepted/In Press date: 5 April 2019
e-pub ahead of print date: 5 April 2019
Published date: 15 May 2019
Additional Information: arXiv is AM

Identifiers

Local EPrints ID: 431638
URI: http://eprints.soton.ac.uk/id/eprint/431638
ISSN: 2050-7488
PURE UUID: f90fe7ab-90a6-4c4c-ada2-90287804f97e

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Date deposited: 11 Jun 2019 16:30
Last modified: 15 May 2020 04:01

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Contributors

Author: Benjamin G. Freestone
Author: Joel A. Smith
Author: Giacomo Piana
Author: Rachel C. Kilbride
Author: Andrew J. Parnell
Author: Luca Sortino
Author: David M. Coles
Author: Orianna B. Ball
Author: Natalia Martsinovich
Author: Courtney J. Thompson
Author: Tarek I. Alanazi
Author: Onkar S. Game
Author: Alexander I. Tartakovskii
Author: David G. Lidzey

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