Electrochemical Hole Injection Selectively Expels Iodide from Mixed Halide Perovskite Films
Abstract
Halide ion mobility in metal halide perovskites remains an intriguing phenomenon, influencing their optical and photovoltaic properties. Selective injection of holes through electrochemical anodic bias has allowed us to probe the effect of hole trapping at iodide (0.9 V) and bromide (1.15 V) in mixed halide perovskite (CH3NH3PbBr1.5I1.5) films. Upon trapping holes at the iodide site, the iodide gradually gets expelled from the mixed halide film (as iodine and/or triiodide ion), leaving behind re-formed CH3NH3PbBr3 domains. The weakening of the Pb-I bond following the hole trapping (oxidation of the iodide site) and its expulsion from the lattice in the form of iodine provided further insight into the photoinduced segregation of halide ions in mixed halide perovskite films. Transient absorption spectroscopy revealed that the iodide expulsion process leaves a defect-rich perovskite lattice behind as charge carrier recombination in the re-formed lattice is greatly accelerated. The selective mobility of iodide species provides insight into the photoinduced phase segregation and its implication in the stable operation of perovskite solar cells.
- Authors:
-
[1];
[3];
[4];
[5];
[6]
- Department of Physical Chemistry and Materials Science, Interdisciplinary Excellence Centre, University of Szeged, Rerrich Square 1, Szeged, H-6720, Hungary, ELI-ALPS Research Institute, Dugonics Square 13, Szeged, 6720, Hungary, Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, United States
- Department of Physical Chemistry and Materials Science, Interdisciplinary Excellence Centre, University of Szeged, Rerrich Square 1, Szeged, H-6720, Hungary
- Department of Chemistry, Biology and Biotechnology, University of Perugia, Via Elce di Sotto, 8I-06123 Perugia, Italy, Computational Laboratory for Hybrid/Organic Photovoltaics (CLHYO), CNR-ISTM, Via Elce di Sotto 8, 06123 Perugia, Italy, CompuNet, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy
- Computational Laboratory for Hybrid/Organic Photovoltaics (CLHYO), CNR-ISTM, Via Elce di Sotto 8, 06123 Perugia, Italy, CompuNet, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy
- Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, United States, Radiation Laboratory, University of Notre Dame, Notre Dame, Indiana 46556, United States
- Department of Physical Chemistry and Materials Science, Interdisciplinary Excellence Centre, University of Szeged, Rerrich Square 1, Szeged, H-6720, Hungary, ELI-ALPS Research Institute, Dugonics Square 13, Szeged, 6720, Hungary
- Publication Date:
- Research Org.:
- Univ. of Szeged (Hungary)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1530479
- Alternate Identifier(s):
- OSTI ID: 1542124
- Grant/Contract Number:
- FC02-04ER15533
- Resource Type:
- Published Article
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Name: Journal of the American Chemical Society Journal Volume: 141 Journal Issue: 27; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Samu, Gergely F., Balog, Ádám, De Angelis, Filippo, Meggiolaro, Daniele, Kamat, Prashant V., and Janáky, Csaba. Electrochemical Hole Injection Selectively Expels Iodide from Mixed Halide Perovskite Films. United States: N. p., 2019.
Web. doi:10.1021/jacs.9b04568.
Samu, Gergely F., Balog, Ádám, De Angelis, Filippo, Meggiolaro, Daniele, Kamat, Prashant V., & Janáky, Csaba. Electrochemical Hole Injection Selectively Expels Iodide from Mixed Halide Perovskite Films. United States. https://doi.org/10.1021/jacs.9b04568
Samu, Gergely F., Balog, Ádám, De Angelis, Filippo, Meggiolaro, Daniele, Kamat, Prashant V., and Janáky, Csaba. Wed .
"Electrochemical Hole Injection Selectively Expels Iodide from Mixed Halide Perovskite Films". United States. https://doi.org/10.1021/jacs.9b04568.
@article{osti_1530479,
title = {Electrochemical Hole Injection Selectively Expels Iodide from Mixed Halide Perovskite Films},
author = {Samu, Gergely F. and Balog, Ádám and De Angelis, Filippo and Meggiolaro, Daniele and Kamat, Prashant V. and Janáky, Csaba},
abstractNote = {Halide ion mobility in metal halide perovskites remains an intriguing phenomenon, influencing their optical and photovoltaic properties. Selective injection of holes through electrochemical anodic bias has allowed us to probe the effect of hole trapping at iodide (0.9 V) and bromide (1.15 V) in mixed halide perovskite (CH3NH3PbBr1.5I1.5) films. Upon trapping holes at the iodide site, the iodide gradually gets expelled from the mixed halide film (as iodine and/or triiodide ion), leaving behind re-formed CH3NH3PbBr3 domains. The weakening of the Pb-I bond following the hole trapping (oxidation of the iodide site) and its expulsion from the lattice in the form of iodine provided further insight into the photoinduced segregation of halide ions in mixed halide perovskite films. Transient absorption spectroscopy revealed that the iodide expulsion process leaves a defect-rich perovskite lattice behind as charge carrier recombination in the re-formed lattice is greatly accelerated. The selective mobility of iodide species provides insight into the photoinduced phase segregation and its implication in the stable operation of perovskite solar cells.},
doi = {10.1021/jacs.9b04568},
journal = {Journal of the American Chemical Society},
number = 27,
volume = 141,
place = {United States},
year = {2019},
month = {6}
}
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Figures / Tables:
Figure 1: (A) Linear sweep voltammograms of FTO/MAPbBrxI3−x films in 0.1 M Bu4NPF6/DCM electrolyte (5 mV s−1 sweep rate). (B) Band diagram of MAPbBr1.5I1.5 together with the peak onset of the observed Faradaic events. (C) Variation of the peak currents of the first two redox waves as a function ofmore »
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