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:
-
- 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. 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}
}
Web of Science
Works referenced in this record:
Detection of gamma photons using solution-grown single crystals of hybrid lead halide perovskites
journal, July 2016
- Yakunin, Sergii; Dirin, Dmitry N.; Shynkarenko, Yevhen
- Nature Photonics, Vol. 10, Issue 9
Conducting tin halides with a layered organic-based perovskite structure
journal, June 1994
- Mitzi, D. B.; Feild, C. A.; Harrison, W. T. A.
- Nature, Vol. 369, Issue 6480, p. 467-469
Conducting Layered Organic-inorganic Halides Containing <110>-Oriented Perovskite Sheets
journal, March 1995
- Mitzi, D. B.; Wang, S.; Feild, C. A.
- Science, Vol. 267, Issue 5203, p. 1473-1476
Organic-Inorganic Hybrid Materials as Semiconducting Channels in Thin-Film Field-Effect Transistors
journal, October 1999
- Kagan, C. R.; Mitzi, D. B.; Dimitrakopoulos, C. D.
- Science, Vol. 286, Issue 5441, p. 945-947
Sequential deposition as a route to high-performance perovskite-sensitized solar cells
journal, July 2013
- Burschka, Julian; Pellet, Norman; Moon, Soo-Jin
- Nature, Vol. 499, Issue 7458, p. 316-319
Formation of Long-Lived Color Centers for Broadband Visible Light Emission in Low-Dimensional Layered Perovskites
journal, December 2017
- Booker, Edward P.; Thomas, Tudor H.; Quarti, Claudio
- Journal of the American Chemical Society, Vol. 139, Issue 51
One-dimensional organic lead halide perovskites with efficient bluish white-light emission
journal, January 2017
- Yuan, Zhao; Zhou, Chenkun; Tian, Yu
- Nature Communications, Vol. 8, Issue 1
Electron-hole diffusion lengths > 175 μm in solution-grown CH 3 NH 3 PbI 3 single crystals
journal, January 2015
- Dong, Qingfeng; Fang, Yanjun; Shao, Yuchuan
- Science, Vol. 347, Issue 6225
Long-Range Balanced Electron- and Hole-Transport Lengths in Organic-Inorganic CH3NH3PbI3
journal, October 2013
- Xing, G.; Mathews, N.; Sun, S.
- Science, Vol. 342, Issue 6156, p. 344-347
Bismuth Based Hybrid Perovskites A 3 Bi 2 I 9 (A: Methylammonium or Cesium) for Solar Cell Application
journal, September 2015
- Park, Byung-Wook; Philippe, Bertrand; Zhang, Xiaoliang
- Advanced Materials, Vol. 27, Issue 43
Perovskites: The Emergence of a New Era for Low-Cost, High-Efficiency Solar Cells
journal, October 2013
- Snaith, Henry J.
- The Journal of Physical Chemistry Letters, Vol. 4, Issue 21, p. 3623-3630
Formamidinium lead trihalide: a broadly tunable perovskite for efficient planar heterojunction solar cells
journal, January 2014
- Eperon, Giles E.; Stranks, Samuel D.; Menelaou, Christopher
- Energy & Environmental Science, Vol. 7, Issue 3
A Bismuth-Halide Double Perovskite with Long Carrier Recombination Lifetime for Photovoltaic Applications
journal, February 2016
- Slavney, Adam H.; Hu, Te; Lindenberg, Aaron M.
- Journal of the American Chemical Society, Vol. 138, Issue 7
Crystal and Electronic Structures of Complex Bismuth Iodides A 3 Bi 2 I 9 ( A = K, Rb, Cs) Related to Perovskite: Aiding the Rational Design of Photovoltaics
journal, October 2015
- Lehner, Anna J.; Fabini, Douglas H.; Evans, Hayden A.
- Chemistry of Materials, Vol. 27, Issue 20
Templating and structural engineering in organic–inorganic perovskites
journal, January 2001
- Mitzi, David B.
- Journal of the Chemical Society, Dalton Transactions, Issue 1
Spatial Electron-hole Separation in a One Dimensional Hybrid Organic–Inorganic Lead Iodide
journal, February 2016
- Savory, Christopher N.; Palgrave, Robert G.; Bronstein, Hugo
- Scientific Reports, Vol. 6, Issue 1
Preparation and properties of tetrathiafulvalene (ttf) and tetramethyltetraselenafulvalene salts of tin(IV) halide anions and X-ray crystal structure of [ttf]3[SnCl6]
journal, January 1984
- Kondo, Kensuke; Matsubayashi, Gen-etsu; Tanaka, Toshio
- Journal of the Chemical Society, Dalton Transactions, Issue 3
Mono- and Mixed-Valence Tetrathiafulvalene Semiconductors (TTF)BiI 4 and (TTF) 4 BiI 6 with 1D and 0D Bismuth-Iodide Networks
journal, December 2016
- Evans, Hayden A.; Labram, John G.; Smock, Sara R.
- Inorganic Chemistry, Vol. 56, Issue 1
Intracation and Interanion–Cation Charge-Transfer Properties of Tetrathiafulvalene-Bismuth-Halide Hybrids
journal, August 2018
- Zhang, Xuan; Zhang, Ping; Weng, Yi-Gang
- Inorganic Chemistry, Vol. 57, Issue 17
(TTF)Pb 2 I 5 : A Radical Cation-Stabilized Hybrid Lead Iodide with Synergistic Optoelectronic Signatures
journal, May 2016
- Evans, Hayden A.; Lehner, Anna J.; Labram, John G.
- Chemistry of Materials, Vol. 28, Issue 11
Structure Tunable Organic–Inorganic Bismuth Halides for an Enhanced Two-Dimensional Lead-Free Light-Harvesting Material
journal, June 2017
- Li, Mu-Qing; Hu, Yue-Qiao; Bi, Le-Yu
- Chemistry of Materials, Vol. 29, Issue 13
Design, Structure, and Optical Properties of Organic−Inorganic Perovskites Containing an Oligothiophene Chromophore
journal, December 1999
- Mitzi, David B.; Chondroudis, Konstantinos; Kagan, Cherie R.
- Inorganic Chemistry, Vol. 38, Issue 26
Organic−Inorganic Perovskites Containing Trivalent Metal Halide Layers: The Templating Influence of the Organic Cation Layer
journal, December 2000
- Mitzi, David B.
- Inorganic Chemistry, Vol. 39, Issue 26
The Solvent Sensitivity of the Charge-Transfer Band of Tropylium Iodide
journal, April 1964
- Kosower, Edward M.
- The Journal of Organic Chemistry, Vol. 29, Issue 4
Hybrid Inorganic–Organic Materials with an Optoelectronically Active Aromatic Cation: (C 7 H 7 ) 2 SnI 6 and C 7 H 7 PbI 3
journal, December 2014
- Maughan, Annalise E.; Kurzman, Joshua A.; Neilson, James R.
- Inorganic Chemistry, Vol. 54, Issue 1
General atomic and molecular electronic structure system
journal, November 1993
- Schmidt, Michael W.; Baldridge, Kim K.; Boatz, Jerry A.
- Journal of Computational Chemistry, Vol. 14, Issue 11, p. 1347-1363
Comparison of silver and molybdenum microfocus X-ray sources for single-crystal structure determination
journal, January 2015
- Krause, Lennard; Herbst-Irmer, Regine; Sheldrick, George M.
- Journal of Applied Crystallography, Vol. 48, Issue 1
SHELXT – Integrated space-group and crystal-structure determination
journal, January 2015
- Sheldrick, George M.
- Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8
A short history of SHELX
journal, December 2007
- Sheldrick, George M.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
Single-crystal structure validation with the program PLATON
journal, January 2003
- Spek, A. L.
- Journal of Applied Crystallography, Vol. 36, Issue 1, p. 7-13
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Norm-conserving and ultrasoft pseudopotentials for first-row and transition elements
journal, October 1994
- Kresse, G.; Hafner, J.
- Journal of Physics: Condensed Matter, Vol. 6, Issue 40
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008
- Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I.
- Physical Review Letters, Vol. 100, Issue 13
High-throughput electronic band structure calculations: Challenges and tools
journal, August 2010
- Setyawan, Wahyu; Curtarolo, Stefano
- Computational Materials Science, Vol. 49, Issue 2
sumo: Command-line tools for plotting and analysis of periodic ab initio calculations
journal, August 2018
- M. Ganose, Alex; J. Jackson, Adam; O. Scanlon, David
- Journal of Open Source Software, Vol. 3, Issue 28
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011
- Momma, Koichi; Izumi, Fujio
- Journal of Applied Crystallography, Vol. 44, Issue 6
General Synthesis Principles for Ruddlesden–Popper Hybrid Perovskite Halides from a Dynamic Equilibrium
journal, November 2018
- Oswald, Iain W. H.; Koegel, Alexandra A.; Neilson, James R.
- Chemistry of Materials, Vol. 30, Issue 23
Interaction of Organic Cation with Water Molecule in Perovskite MAPbI 3 : From Dynamic Orientational Disorder to Hydrogen Bonding
journal, October 2016
- Zhu, Zhuan; Hadjiev, Viktor G.; Rong, Yaoguang
- Chemistry of Materials, Vol. 28, Issue 20
Significance tests on the crystallographic R factor
journal, May 1965
- Hamilton, W. C.
- Acta Crystallographica, Vol. 18, Issue 3
Vibronic Structure in Room Temperature Photoluminescence of the Halide Perovskite Cs 3 Bi 2 Br 9
journal, September 2016
- Bass, Kelsey K.; Estergreen, Laura; Savory, Christopher N.
- Inorganic Chemistry, Vol. 56, Issue 1
Dynamic Stereochemical Activity of the Sn 2+ Lone Pair in Perovskite CsSnBr 3
journal, September 2016
- Fabini, Douglas H.; Laurita, Geneva; Bechtel, Jonathon S.
- Journal of the American Chemical Society, Vol. 138, Issue 36
Synthesis, crystal structure, and properties of a perovskite-related bismuth phase, (NH 4 ) 3 Bi 2 I 9
journal, March 2016
- Sun, Shijing; Tominaka, Satoshi; Lee, Jung-Hoon
- APL Materials, Vol. 4, Issue 3
Stereochemistry of post-transition metal oxides: revision of the classical lone pair model
journal, January 2011
- Walsh, Aron; Payne, David J.; Egdell, Russell G.
- Chemical Society Reviews, Vol. 40, Issue 9
First-principles indicators of metallicity and cation off-centricity in the IV-VI rocksalt chalcogenides of divalent Ge, Sn, and Pb
journal, March 2003
- Waghmare, U. V.; Spaldin, N. A.; Kandpal, H. C.
- Physical Review B, Vol. 67, Issue 12
Anomalous Band Gap Behavior in Mixed Sn and Pb Perovskites Enables Broadening of Absorption Spectrum in Solar Cells
journal, May 2014
- Hao, Feng; Stoumpos, Constantinos C.; Chang, Robert P. H.
- Journal of the American Chemical Society, Vol. 136, Issue 22
Hybrid Germanium Iodide Perovskite Semiconductors: Active Lone Pairs, Structural Distortions, Direct and Indirect Energy Gaps, and Strong Nonlinear Optical Properties
journal, May 2015
- Stoumpos, Constantinos C.; Frazer, Laszlo; Clark, Daniel J.
- Journal of the American Chemical Society, Vol. 137, Issue 21
Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties
journal, July 2013
- Stoumpos, Constantinos C.; Malliakas, Christos D.; Kanatzidis, Mercouri G.
- Inorganic Chemistry, Vol. 52, Issue 15, p. 9019-9038
Electronic structure and photovoltaic application of BiI 3
journal, September 2015
- Lehner, Anna J.; Wang, Hengbin; Fabini, Douglas H.
- Applied Physics Letters, Vol. 107, Issue 13
Relativistic GW calculations on CH3NH3PbI3 and CH3NH3SnI3 Perovskites for Solar Cell Applications
journal, March 2014
- Umari, Paolo; Mosconi, Edoardo; De Angelis, Filippo
- Scientific Reports, Vol. 4, Issue 1
Works referencing / citing this record:
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
Additive-assisted synthesis and optoelectronic properties of (CH 3 NH 3 ) 4 Bi 6 I 22
journal, January 2020
- Sharma, Manila; Yangui, Aymen; Lusson, Alain
- Inorganic Chemistry Frontiers, Vol. 7, Issue 7