@article{ce1e7f956f734b1c90405b6c4b867e56,
title = "Electrochemical Doping of Halide Perovskites by Noble Metal Interstitial Cations",
abstract = "Metal halide perovskites are an attractive class of semiconductors, but it has proven difficult to control their electronic doping by conventional strategies due to screening and compensation by mobile ions or ionic defects. Noble-metal interstitials represent an under-studied class of extrinsic defects that plausibly influence many perovskite-based devices. In this work, doping of metal halide perovskites is studied by electrochemically formed Au+ interstitial ions, combining experimental data on devices with a computational analysis of Au+ interstitial defects based on density functional theory (DFT). Analysis suggests that Au+ cations can be easily formed and migrate through the perovskite bulk via the same sites as iodine interstitials (I-i(+)). However, whereas I-i(+) compensates n-type doping by electron capture, the noble-metal interstitials act as quasi-stable n-dopants. Experimentally, voltage-dependent, dynamic doping by current density-time (J-t), electrochemical impedance, and photoluminescence measurements are characterized. These results provide deeper insight into the potential beneficial and detrimental impacts of metal electrode reactions on long-term performance of perovskite photovoltaic and light-emitting diodes, as well as offer an alternative doping explanation for the valence switching mechanism of halide-perovskite-based neuromorphic and memristive devices.",
author = "Kerner, {Ross A.} and Cohen, {Ayala V.} and Zhaojian Xu and Kirmani, {Ahmad R.} and Park, {So Yeon} and Harvey, {Steven P.} and Murphy, {John P.} and Cawthorn, {Robert C.} and Giebink, {Noel C.} and Luther, {Joseph M.} and Kai Zhu and Berry, {Joseph J.} and Leeor Kronik and Rand, {Barry P.}",
note = "This work was authored by the National Renewable Energy Laboratory, operated by Alliance for Sustainable Energy, LLC, for the U.S. Department of Energy (DOE) under Contract No. DE-AC36-08GO28308. Construction of device and samples along with TOF-SIMS measurements were supported by funding provided by U.S. Department of Energy Office of Energy Efficiency and Renewable Energy, Solar Energy Technologies Office (SETO) project “Advanced Perovskite Cells and Modules” program (DE-FOA-0000990) and device chronoamperometry and bias dependent characterizations were undertaken with support from the Center for Hybrid Organic Inorganic Semiconductors for Energy (CHOISE), an Energy Frontier Research Center funded by the DOE Office of Basic Energy Sciences, Office of Science. The views expressed in the article do not necessarily represent the views of the DOE or the U.S. Government. The U.S. Government retains and the publisher, by accepting the article for publication, acknowledges that the U.S. Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for U.S. Government purposes. Z.X. and B.P.R. acknowledge funding for this work by the Department of the Navy, Office of Naval Research under ONR award number N00014-21-1-2767. J.P.M., R.C.C., and N.C.G. acknowledge support from the Defense Advanced Research Projects Agency under award number NN66001-20-1-4052. A.V.C. and L.K. thank the Minerva Centre for Self-Repairing Systems for Energy & Sustainability for support. L.K. thanks the Mintzi and Aryeh Katzman Professorial Chair and the Helen and Martin Kimmel Award for Innovative Investigation.",
year = "2023",
month = jul,
day = "20",
doi = "https://doi.org/10.1002/adma.202302206",
language = "الإنجليزيّة",
volume = "35",
journal = "Advanced Materials",
issn = "0935-9648",
publisher = "Wiley-Blackwell",
number = "29",
}