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 (Ii+). However, whereas Ii+ 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.
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- Jun 02, 2023
- Source ID
- 10.1002/adma.202302206
Entities
People
- Ahmad R Kirmani
- Ayala V. Cohen
- Barry P Rand
- John P. Murphy
- Joseph J. Berry
- Joseph M. Luther
- Kai Zhu
- Leeor Kronik
- Noel C Giebink
- Robert C. Cawthorn
- Ross A. Kerner
- So Yeon Park
- Steve P Harvey
- Zhaojian Xu
Organizations
- Defense Advanced Research Projects Agency
- National Renewable Energy Laboratory
- Office of Naval Research
- Pennsylvania State University
- Princeton University
- United States Department of Energy
- University of Colorado Boulder
- Weizmann Institute of Science