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Title: 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.

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 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. 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. 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 = {2019},
month = {3}
}

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Works referencing / citing this record:

CCDC 1891648: Experimental Crystal Structure Determination
dataset, January 2019


Influence of organic cation planarity on structural templating in hybrid metal-halides
journal, January 2019

  • Oswald, Iain W. H.; Ahn, Hyochul; Neilson, James R.
  • Dalton Transactions, Vol. 48, Issue 43
  • DOI: 10.1039/c9dt03207j

CCDC 1892854: Experimental Crystal Structure Determination
dataset, January 2019


CCDC 1892855: Experimental Crystal Structure Determination
dataset, January 2019


CCDC 1892856: Experimental Crystal Structure Determination
dataset, January 2019


CCDC 1892857: Experimental Crystal Structure Determination
dataset, January 2019


CCDC 1892858: Experimental Crystal Structure Determination
dataset, January 2019


Influence of organic cation planarity on structural templating in hybrid metal-halides
journal, January 2019

  • Oswald, Iain W. H.; Ahn, Hyochul; Neilson, James R.
  • Dalton Transactions, Vol. 48, Issue 43
  • DOI: 10.1039/c9dt03207j

Crystal structure and luminescence properties of lead-free metal halides (C 6 H 5 CH 2 NH 3 ) 3 MBr 6 (M = Bi and Sb)
journal, January 2020

  • Chen, Da; Dai, Fulong; Hao, Shiqiang
  • Journal of Materials Chemistry C
  • DOI: 10.1039/d0tc00562b