Charge Reservoirs in an Expanded Halide Perovskite Analog: Enhancing High–Pressure Conductivity through Redox–Active Molecules

Matheu, Roc; Ke, Feng; Breidenbach, Aaron; Wolf, Nathan R.; Lee, Young; Liu, Zhenxian; Leppert, Linn; Lin, Yu; Karunadasa, Hemamala I.

doi:10.1002/anie.202202911

Charge Reservoirs in an Expanded Halide Perovskite Analog: Enhancing High–Pressure Conductivity through Redox–Active Molecules

Journal Article · Thu Apr 14 00:00:00 EDT 2022 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202202911· OSTI ID:1874374

^[1]; Ke, Feng ^[2]; Breidenbach, Aaron ^[2]; Wolf, Nathan R. ^[3]; Lee, Young ^[2]; Liu, Zhenxian ^[4]; Leppert, Linn ^[5]; Lin, Yu ^[6]; ^[2]

Stanford Univ., CA (United States); University of Illinois Chicago
SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., CA (United States)
Stanford Univ., CA (United States)
Univ. of Illinois, Chicago, IL (United States)
Univ. of Twente, Enschede (The Netherlands)
SLAC National Accelerator Lab., Menlo Park, CA (United States)

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. Lastly, 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.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Univ. of Illinois, Chicago, IL (United States)

Sponsoring Organization:: National Science Foundation; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515; NA0003975; SC0012704

OSTI ID:: 1874374

Alternate ID(s):: OSTI ID: 1866277
OSTI ID: 1889848

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 25 Vol. 61; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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conductivity
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Charge Reservoirs in an Expanded Halide Perovskite Analog: Enhancing High–Pressure Conductivity through Redox–Active Molecules

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