TY - JOUR
T1 - Charge Reservoirs in an Expanded Halide Perovskite Analog
T2 - Enhancing High-Pressure Conductivity through Redox-Active Molecules
AU - Matheu, Roc
AU - Ke, Feng
AU - Breidenbach, Aaron
AU - Wolf, Nathan R.
AU - Lee, Young
AU - Liu, Zhenxian
AU - Leppert, Linn
AU - Lin, Yu
AU - Karunadasa, Hemamala I.
N1 - Funding Information:
This work was supported by the Department of Energy (DOE), Office of Basic Energy Sciences (BES), Division of Materials Sciences and Engineering (DE‐AC02‐76SF00515). High‐pressure PXRD data were collected at beamline 12.2.2 at the Advanced Light Source, supported by the Office of Science, BES, DOE (DE‐AC02‐05CH11231). High‐pressure absorption measurements used beamline 22‐IR‐1 of the National Synchrotron Light Source II, a U.S. DOE Office of Science User Facility operated by the Brookhaven National Laboratory (DE‐SC0012704) and supported by COMPRES under the National Science Foundation (EAR 11‐57758) and the Carnegie DOE Alliance Center (DE‐FC03‐03N00144). N.R.W. was supported by a Stanford Interdisciplinary Graduate Fellowship. We thank Dr. Martin Kunz and Dr. Bora Kalkan for technical assistance, Dr. Rebecca Smaha for helpful discussions, and Prof. Wendy Mao for access to equipment.
Publisher Copyright:
© 2022 Wiley-VCH GmbH.
PY - 2022/6/20
Y1 - 2022/6/20
N2 - As halide perovskites and their derivatives are being developed for numerous optoelectronic applications, controlling their electronic doping remains a fundamental challenge. Herein, we describe a novel strategy of using redox-active organic molecules as stoichiometric electron acceptors. The cavities in the new expanded perovskite analogs (dmpz)[Sn2X6], (X=Br− (1Br) and I− (1I)) are occupied by dmpz2+ (N,N′-dimethylpyrazinium), with the LUMOs lying ca. 1 eV above the valence band maximum (VBM). Compressing the metal-halide framework drives up the VBM in 1I relative to the dmpz LUMO. The electronic conductivity increases by a factor of 105 with pressure, reaching 50(17) S cm−1 at 60 GPa, exceeding the high-pressure conductivities of most halide perovskites. This conductivity enhancement is attributed to an increased hole density created by dmpz2+ reduction. This work elevates the role of organic cations in 3D metal-halides, from templating the structure to serving as charge reservoirs for tuning the carrier concentration.
AB - As halide perovskites and their derivatives are being developed for numerous optoelectronic applications, controlling their electronic doping remains a fundamental challenge. Herein, we describe a novel strategy of using redox-active organic molecules as stoichiometric electron acceptors. The cavities in the new expanded perovskite analogs (dmpz)[Sn2X6], (X=Br− (1Br) and I− (1I)) are occupied by dmpz2+ (N,N′-dimethylpyrazinium), with the LUMOs lying ca. 1 eV above the valence band maximum (VBM). Compressing the metal-halide framework drives up the VBM in 1I relative to the dmpz LUMO. The electronic conductivity increases by a factor of 105 with pressure, reaching 50(17) S cm−1 at 60 GPa, exceeding the high-pressure conductivities of most halide perovskites. This conductivity enhancement is attributed to an increased hole density created by dmpz2+ reduction. This work elevates the role of organic cations in 3D metal-halides, from templating the structure to serving as charge reservoirs for tuning the carrier concentration.
KW - 3D Perovskite Analogs
KW - Conductivity
KW - Doping
KW - Halide Perovskite
KW - High Pressure
KW - 2023 OA procedure
UR - http://www.scopus.com/inward/record.url?scp=85129322841&partnerID=8YFLogxK
U2 - 10.1002/anie.202202911
DO - 10.1002/anie.202202911
M3 - Article
C2 - 35421260
AN - SCOPUS:85129322841
VL - 61
JO - Angewandte Chemie (international edition)
JF - Angewandte Chemie (international edition)
SN - 1433-7851
IS - 25
M1 - e202202911
ER -