Superatomic molecules with internal electric fields for light harvesting
Abstract
Traditional p–n junctions used for photovoltaics require an interface where a light induced electron–hole pair is separated by an electric field. Developing alternative strategies for forming strong internal electric fields for electron–hole pair separation offers the possibility for better performance. We demonstrate that fusing two superatomic clusters with donor/acceptor ligands on opposite sides of the cluster leads to such a strong internal electric field. In two fused metal–chalcogenide Re6S8Cl2(L)4 clusters with donor PMe3 ligands and acceptor CO ligands on the opposite sides of the fused clusters, the electronic levels undergo shifts analogous to band bending in traditional p–n junctions. The fused cluster has a large dipole moment, and an optical spectrum that strongly absorbs excitation above the HOMO–LUMO gap of the fused clusters, but is optically very weak for the lowest energy excitation that can lead to electron–hole pair recombination. This is because the electron is localized on the CO portion of the fused cluster, while the electron–hole pair is localized on the PMe3 side of the cluster. It is shown that the electronic states localized on each side of the cluster can be aligned/misaligned by applying a voltage in different directions, offering diode like characteristics.
- Publication Date:
- Research Org.:
- Virginia Commonwealth Univ., Richmond, VA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1601432
- Alternate Identifier(s):
- OSTI ID: 1599258
- Grant/Contract Number:
- SC0006420
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nanoscale
- Additional Journal Information:
- Journal Volume: 12; Journal Issue: 7; Journal ID: ISSN 2040-3364
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 14 SOLAR ENERGY; 74 ATOMIC AND MOLECULAR PHYSICS; Superatoms, Superatomic Molecules, light harvesting, Internal electric fields, band engineering
Citation Formats
Reber, Arthur C., Chauhan, Vikas, Bista, Dinesh, and Khanna, Shiv N. Superatomic molecules with internal electric fields for light harvesting. United States: N. p., 2020.
Web. https://doi.org/10.1039/c9nr09229c.
Reber, Arthur C., Chauhan, Vikas, Bista, Dinesh, & Khanna, Shiv N. Superatomic molecules with internal electric fields for light harvesting. United States. https://doi.org/10.1039/c9nr09229c
Reber, Arthur C., Chauhan, Vikas, Bista, Dinesh, and Khanna, Shiv N. Tue .
"Superatomic molecules with internal electric fields for light harvesting". United States. https://doi.org/10.1039/c9nr09229c. https://www.osti.gov/servlets/purl/1601432.
@article{osti_1601432,
title = {Superatomic molecules with internal electric fields for light harvesting},
author = {Reber, Arthur C. and Chauhan, Vikas and Bista, Dinesh and Khanna, Shiv N.},
abstractNote = {Traditional p–n junctions used for photovoltaics require an interface where a light induced electron–hole pair is separated by an electric field. Developing alternative strategies for forming strong internal electric fields for electron–hole pair separation offers the possibility for better performance. We demonstrate that fusing two superatomic clusters with donor/acceptor ligands on opposite sides of the cluster leads to such a strong internal electric field. In two fused metal–chalcogenide Re6S8Cl2(L)4 clusters with donor PMe3 ligands and acceptor CO ligands on the opposite sides of the fused clusters, the electronic levels undergo shifts analogous to band bending in traditional p–n junctions. The fused cluster has a large dipole moment, and an optical spectrum that strongly absorbs excitation above the HOMO–LUMO gap of the fused clusters, but is optically very weak for the lowest energy excitation that can lead to electron–hole pair recombination. This is because the electron is localized on the CO portion of the fused cluster, while the electron–hole pair is localized on the PMe3 side of the cluster. It is shown that the electronic states localized on each side of the cluster can be aligned/misaligned by applying a voltage in different directions, offering diode like characteristics.},
doi = {10.1039/c9nr09229c},
journal = {Nanoscale},
number = 7,
volume = 12,
place = {United States},
year = {2020},
month = {2}
}
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Works referenced in this record:
Transforming Redox Properties of Clusters Using Phosphine Ligands
journal, March 2019
- Reber, Arthur C.; Bista, Dinesh; Chauhan, Vikas
- The Journal of Physical Chemistry C, Vol. 123, Issue 14
Superatomic Two-Dimensional Semiconductor
journal, January 2018
- Zhong, Xinjue; Lee, Kihong; Choi, Bonnie
- Nano Letters, Vol. 18, Issue 2
Direct Observation of Surface-Mediated Electron−Hole Pair Recombination in TiO 2 (110)
journal, February 2010
- Zhang, Zhen; Yates, John T.
- The Journal of Physical Chemistry C, Vol. 114, Issue 7
Depletion-Layer Photoeffects in Semiconductors
journal, October 1959
- Gärtner, Wolfgang W.
- Physical Review, Vol. 116, Issue 1
More than just a support: Graphene as a solid-state ligand for palladium-catalyzed cross-coupling reactions
journal, April 2018
- Yang, Yuan; Reber, Arthur C.; Gilliland, Stanley E.
- Journal of Catalysis, Vol. 360
Controlling the Band Gap Energy of Cluster-Assembled Materials
journal, June 2013
- Mandal, Sukhendu; Reber, Arthur C.; Qian, Meichun
- Accounts of Chemical Research, Vol. 46, Issue 11
Synthesis, structure and band gap energy of covalently linked cluster-assembled materials
journal, January 2012
- Mandal, Sukhendu; Reber, Arthur C.; Qian, Meichun
- Dalton Transactions, Vol. 41, Issue 40
Highly Emissive Hexanuclear Rhenium(III) Clusters Containing the Cubic Cores [Re 6 S 8 ] 2+ and [Re 6 Se 8 ] 2+
journal, December 1999
- Gray, Thomas G.; Rudzinski, Christina M.; Nocera, Daniel G.
- Inorganic Chemistry, Vol. 38, Issue 26
Relativistic regular two-component Hamiltonians
journal, February 1996
- van Lenthe, E.; van Leeuwen, R.; Baerends, E. J.
- International Journal of Quantum Chemistry, Vol. 57, Issue 3
Accurate and simple density functional for the electronic exchange energy: Generalized gradient approximation
journal, June 1986
- Perdew, John P.; Yue, Wang
- Physical Review B, Vol. 33, Issue 12
[Cd 2 (H 2 O) 4 ][Re 6 S 8 (CN) 6 ]·14H 2 O: A Cyano-Bridged Cluster−Cluster Framework Solid with Accessible Cubelike Cavities
journal, April 1999
- Shores, Matthew P.; Beauvais, Laurance G.; Long, Jeffrey R.
- Inorganic Chemistry, Vol. 38, Issue 8
An investigation of surface states at a silicon/silicon oxide interface employing metal-oxide-silicon diodes
journal, September 1962
- Terman, L. M.
- Solid-State Electronics, Vol. 5, Issue 5
Single-crystal-to-single-crystal intercalation of a low-bandgap superatomic crystal
journal, August 2017
- O'Brien, Evan S.; Trinh, M. Tuan; Kann, Rose L.
- Nature Chemistry, Vol. 9, Issue 12
Chemistry with ADF
journal, January 2001
- te Velde, G.; Bickelhaupt, F. M.; Baerends, E. J.
- Journal of Computational Chemistry, Vol. 22, Issue 9, p. 931-967
Surface effects on p-n junctions: Characteristics of surface space-charge regions under non-equilibrium conditions
journal, August 1966
- Grove, A. S.; Fitzgerald, D. J.
- Solid-State Electronics, Vol. 9, Issue 8
Superatoms: Electronic and Geometric Effects on Reactivity
journal, January 2017
- Reber, Arthur C.; Khanna, Shiv N.
- Accounts of Chemical Research, Vol. 50, Issue 2
Nanoscale Atoms in Solid-State Chemistry
journal, June 2013
- Roy, X.; Lee, C. -H.; Crowther, A. C.
- Science, Vol. 341, Issue 6142
Two-Dimensional Hierarchical Semiconductor with Addressable Surfaces
journal, July 2018
- Choi, Bonnie; Lee, Kihong; Voevodin, Anastasia
- Journal of the American Chemical Society, Vol. 140, Issue 30
Orientational order controls crystalline and amorphous thermal transport in superatomic crystals
journal, September 2016
- Ong, Wee-Liat; O’Brien, Evan S.; Dougherty, Patrick S. M.
- Nature Materials, Vol. 16, Issue 1
Substitution of the Terminal Chloride Ligands of [Re 6 S 8 Cl 6 ] 4− with Triethylphosphine: Photophysical and Electrochemical Properties of a New Series of [Re 6 S 8 ] 2+ Based Clusters
journal, December 2010
- Szczepura, Lisa F.; Cedeño, David L.; Johnson, Dean B.
- Inorganic Chemistry, Vol. 49, Issue 24
Cluster-Assembled Materials
journal, January 2009
- Claridge, Shelley A.; Castleman, A. W.; Khanna, Shiv N.
- ACS Nano, Vol. 3, Issue 2
Geometry optimizations in the zero order regular approximation for relativistic effects
journal, May 1999
- van Lenthe, Erik; Ehlers, Andreas; Baerends, Evert-Jan
- The Journal of Chemical Physics, Vol. 110, Issue 18
Superatom Fusion and the Nature of Quantum Confinement
journal, June 2018
- Champsaur, Anouck M.; Hochuli, Taylor J.; Paley, Daniel W.
- Nano Letters, Vol. 18, Issue 7
Molecular control of quantum-dot internal electric field and its application to CdSe-based solar cells
journal, October 2011
- Yaacobi-Gross, Nir; Soreni-Harari, Michal; Zimin, Marina
- Nature Materials, Vol. 10, Issue 12
The effect of chalcogen and metal on the electronic properties and stability of metal–chalcogenides clusters, TM6Xn(PH3)6 (TM = Mo, Cr, Re, Co, Ni; X = Se, Te; n = 8,5)
journal, November 2018
- Reber, Arthur C.; Khanna, Shiv N.
- The European Physical Journal D, Vol. 72, Issue 11
ZnO p-n junction light-emitting diodes fabricated on sapphire substrates
journal, January 2006
- Jiao, S. J.; Zhang, Z. Z.; Lu, Y. M.
- Applied Physics Letters, Vol. 88, Issue 3
Phase-transition–induced p-n junction in single halide perovskite nanowire
journal, August 2018
- Kong, Qiao; Lee, Woochul; Lai, Minliang
- Proceedings of the National Academy of Sciences, Vol. 115, Issue 36
Strong Effect of Organic Ligands on the Electronic Structure of Metal-Chalcogenide Clusters
journal, June 2018
- Chauhan, Vikas; Khanna, Shiv N.
- The Journal of Physical Chemistry A, Vol. 122, Issue 28
Atomic clusters: Building blocks for a class of solids
journal, May 1995
- Khanna, S. N.; Jena, P.
- Physical Review B, Vol. 51, Issue 19
Metal Chalcogenide Clusters with Closed Electronic Shells and the Electronic Properties of Alkalis and Halogens
journal, January 2017
- Chauhan, Vikas; Reber, Arthur C.; Khanna, Shiv N.
- Journal of the American Chemical Society, Vol. 139, Issue 5
Electron donor-acceptor properties of phosphorus ligands. Substituent additivity
journal, May 1970
- Tolman, Chadwick A.
- Journal of the American Chemical Society, Vol. 92, Issue 10
Dynamics of electron-hole pair recombination in semiconductor clusters
journal, May 1990
- O'Neil, M.; Marohn, J.; McLendon, G.
- The Journal of Physical Chemistry, Vol. 94, Issue 10
Chemistry of Lewis Acid–Base Pairs on Oxide Surfaces
journal, April 2012
- Metiu, Horia; Chrétien, Steeve; Hu, Zhenpeng
- The Journal of Physical Chemistry C, Vol. 116, Issue 19
Epitaxial growth of a monolayer WSe2-MoS2 lateral p-n junction with an atomically sharp interface
journal, July 2015
- Li, M. -Y.; Shi, Y.; Cheng, C. -C.
- Science, Vol. 349, Issue 6247
Tuning the electronic properties of hexanuclear cobalt sulfide superatoms via ligand substitution
journal, January 2019
- Liu, Gaoxiang; Pinkard, Andrew; Ciborowski, Sandra M.
- Chemical Science, Vol. 10, Issue 6
Transforming Ni 9 Te 6 from Electron Donor to Acceptor via Ligand Exchange
journal, August 2016
- Chauhan, Vikas; Reber, Arthur C.; Khanna, Shiv N.
- The Journal of Physical Chemistry A, Vol. 120, Issue 33
A simplified relativistic time-dependent density-functional theory formalism for the calculations of excitation energies including spin-orbit coupling effect
journal, October 2005
- Wang, Fan; Ziegler, Tom
- The Journal of Chemical Physics, Vol. 123, Issue 15
Optimized Slater-type basis sets for the elements 1-118
journal, May 2003
- Van Lenthe, E.; Baerends, E. J.
- Journal of Computational Chemistry, Vol. 24, Issue 9
Effect of N- and P-Type Doping on the Oxygen-Binding Energy and Oxygen Spillover of Supported Palladium Clusters
journal, August 2014
- Reber, Arthur C.; Khanna, Shiv N.
- The Journal of Physical Chemistry C, Vol. 118, Issue 35
Co6Se8(PEt3)6 superatoms as tunable chemical dopants for two-dimensional semiconductors
journal, July 2018
- Reber, Arthur C.; Khanna, Shiv N.
- npj Computational Materials, Vol. 4, Issue 1
Detailed Balance Limit of Efficiency of p‐n Junction Solar Cells
journal, March 1961
- Shockley, William; Queisser, Hans J.
- Journal of Applied Physics, Vol. 32, Issue 3, p. 510-519
van der Waals Solids from Self-Assembled Nanoscale Building Blocks
journal, January 2016
- Choi, Bonnie; Yu, Jaeeun; Paley, Daniel W.
- Nano Letters, Vol. 16, Issue 2
Synthesis and investigation of cobalt chalcogenide clusters with thienyl phosphine ligands as new acceptor materials for P3HT
journal, January 2015
- Reeves, B. J.; Shircliff, D. M.; Shott, J. L.
- Dalton Transactions, Vol. 44, Issue 2
Molecular Clusters: Nanoscale Building Blocks for Solid-State Materials
journal, March 2018
- Pinkard, Andrew; Champsaur, Anouck M.; Roy, Xavier
- Accounts of Chemical Research, Vol. 51, Issue 4
Ball and Socket Assembly of Binary Superatomic Solids Containing Trinuclear Nickel Cluster Cations and Fulleride Anions
journal, August 2017
- Shott, Jessica L.; Freeman, Matthew B.; Saleh, Nemah-Allah
- Inorganic Chemistry, Vol. 56, Issue 18
The electric field under a STM tip apex: implications for adsorbate manipulation
journal, February 1993
- Girard, C.; Joachim, C.; Chavy, C.
- Surface Science, Vol. 282, Issue 3
Biicosahedral Gold Clusters [Au 25 (PPh 3 ) 10 (SC n H 2 n +1 ) 5 Cl 2 ] 2+ ( n = 2−18): A Stepping Stone to Cluster-Assembled Materials
journal, June 2007
- Shichibu, Yukatsu; Negishi, Yuichi; Watanabe, Takahito
- The Journal of Physical Chemistry C, Vol. 111, Issue 22
Conductance of Single Cobalt Chalcogenide Cluster Junctions
journal, June 2011
- Boardman, Brycelyn M.; Widawsky, Jonathan R.; Park, Young S.
- Journal of the American Chemical Society, Vol. 133, Issue 22