Hybrid Charge-Transfer Semiconductors: (C7H7)SbI4, (C7H7)BiI4, and Their Halide Congeners
Abstract
Hybrid metal halides yield highly desirable optoelectronic properties and offer significant opportunity due to their solution processability. This contribution reports a new series of hybrid semiconductors, (C7H7)MX4 (M = Bi3+, Sb3+; X = Cl–, Br–, I–), that are composed of edge-sharing MX6 chains separated in space by π-stacked tropylium (C7H7+) cations; the inorganic chains resemble the connectivity of BiI3. The Bi3+ compounds have blue-shifted optical absorptions relative to the Sb3+ compounds that span the visible and near-IR region. Consistent with observations, DFT calculations reveal that the conduction band is composed of the tropylium cation and valence band primarily the inorganic chain: a charge-transfer semiconductor. The band gaps for both Bi3+ and Sb3+ compounds decrease systematically as a function of increasing halide size. Furthermore these compounds are a rare example of charge-transfer semiconductors that also exhibit efficient crystal packing of the organic cations, thus providing an opportunity to study how structural packing affects optoelectronic properties.
- Publication Date:
- Research Org.:
- Colorado State Univ., Fort Collins, CO (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
- OSTI Identifier:
- 1502430
- Grant/Contract Number:
- SC0016083
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 58; Journal Issue: 9; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Oswald, Iain W. H., Mozur, Eve M., Moseley, Ian P., Ahn, Hyochul, and Neilson, James R. Hybrid Charge-Transfer Semiconductors: (C7H7)SbI4, (C7H7)BiI4, and Their Halide Congeners. United States: N. p., 2019.
Web. doi:10.1021/acs.inorgchem.9b00170.
Oswald, Iain W. H., Mozur, Eve M., Moseley, Ian P., Ahn, Hyochul, & Neilson, James R. Hybrid Charge-Transfer Semiconductors: (C7H7)SbI4, (C7H7)BiI4, and Their Halide Congeners. United States. https://doi.org/10.1021/acs.inorgchem.9b00170
Oswald, Iain W. H., Mozur, Eve M., Moseley, Ian P., Ahn, Hyochul, and Neilson, James R. Fri .
"Hybrid Charge-Transfer Semiconductors: (C7H7)SbI4, (C7H7)BiI4, and Their Halide Congeners". United States. https://doi.org/10.1021/acs.inorgchem.9b00170. https://www.osti.gov/servlets/purl/1502430.
@article{osti_1502430,
title = {Hybrid Charge-Transfer Semiconductors: (C7H7)SbI4, (C7H7)BiI4, and Their Halide Congeners},
author = {Oswald, Iain W. H. and Mozur, Eve M. and Moseley, Ian P. and Ahn, Hyochul and Neilson, James R.},
abstractNote = {Hybrid metal halides yield highly desirable optoelectronic properties and offer significant opportunity due to their solution processability. This contribution reports a new series of hybrid semiconductors, (C7H7)MX4 (M = Bi3+, Sb3+; X = Cl–, Br–, I–), that are composed of edge-sharing MX6 chains separated in space by π-stacked tropylium (C7H7+) cations; the inorganic chains resemble the connectivity of BiI3. The Bi3+ compounds have blue-shifted optical absorptions relative to the Sb3+ compounds that span the visible and near-IR region. Consistent with observations, DFT calculations reveal that the conduction band is composed of the tropylium cation and valence band primarily the inorganic chain: a charge-transfer semiconductor. The band gaps for both Bi3+ and Sb3+ compounds decrease systematically as a function of increasing halide size. Furthermore these compounds are a rare example of charge-transfer semiconductors that also exhibit efficient crystal packing of the organic cations, thus providing an opportunity to study how structural packing affects optoelectronic properties.},
doi = {10.1021/acs.inorgchem.9b00170},
journal = {Inorganic Chemistry},
number = 9,
volume = 58,
place = {United States},
year = {Fri Mar 22 00:00:00 EDT 2019},
month = {Fri Mar 22 00:00:00 EDT 2019}
}
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