Modulation of Photoinduced Iodine Expulsion in Mixed Halide Perovskites with Electrochemical Bias

DuBose, Jeffrey T.; Mathew, Preethi S.; Cho, Junsang; Kuno, Masaru; Kamat, Prashant V.

doi:10.1021/acs.jpclett.1c00367

Modulation of Photoinduced Iodine Expulsion in Mixed Halide Perovskites with Electrochemical Bias

Journal Article · Tue Mar 09 00:00:00 EST 2021 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.1c00367· OSTI ID:1774774

^[1]; Mathew, Preethi S. ^[2]; ^[2]; ^[3]; ^[2]

Univ. of Notre Dame, IN (United States). Notre Dame Radiation Lab.; University of Notre Dame
Univ. of Notre Dame, IN (United States). Notre Dame Radiation Lab.
Univ. of Notre Dame, IN (United States)

Hole trapping at iodine (I) sites in MAPbBr_1.5I_1.5 mixed halide perovskites (MHP) is responsible for iodine migration and its eventual expulsion into solution. We have now modulated the photoinduced iodine expulsion in MHP through an externally applied electrochemical bias. At positive potentials, electron extraction at TiO₂/MHP interfaces becomes efficient, leading to hole buildup within MHP films. This improved charge separation, in turn, favors iodine migration as evident from the increased apparent rate constant of iodine expulsion (k_expulsion = 0.0030 s^–1). Conversely, at negative potentials (-0.3 V vs Ag/AgCl) electron–hole recombination is facilitated within MHP, slowing down iodine expulsion by an order of magnitude (k_expulsion = 0.00018 s^–1). The tuning of the EFermi level through external bias modulates electron extraction at the TiO₂/MHP interface and indirectly controls the buildup of holes, ultimately inducing iodine migration/expulsion. Suppressing iodine migration in perovskite solar cells is important for attaining greater stability since they operate under internal electrical bias.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Notre Dame, IN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: FC02-04ER15533; SC0014334

OSTI ID:: 1774774

Alternate ID(s):: OSTI ID: 1830770
OSTI ID: 1909219

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 10 Vol. 12; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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