skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

This content will become publicly available on March 22, 2020

Title: Hybrid Charge-Transfer Semiconductors: (C 7H 7)SbI 4, (C 7H 7)BiI 4, 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, (C 7H 7)MX 4 (M = Bi 3+, Sb 3+; X = Cl , Br , I ), that are composed of edge-sharing MX 6 chains separated in space by π-stacked tropylium (C 7H 7 +) cations; the inorganic chains resemble the connectivity of BiI 3. The Bi 3+ compounds have blue-shifted optical absorptions relative to the Sb 3+ 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 Bi 3+ and Sb 3+ 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.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1];  [1]; ORCiD logo [1]
  1. Colorado State Univ., Fort Collins, CO (United States)
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 Name: Inorganic Chemistry; 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. doi: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. doi:10.1021/acs.inorgchem.9b00170.
@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 = ,
volume = ,
place = {United States},
year = {2019},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on March 22, 2020
Publisher's Version of Record

Save / Share: