Superatomic molecules with internal electric fields for light harvesting

Reber, Arthur C.; Chauhan, Vikas; Bista, Dinesh; Khanna, Shiv N.

doi:10.1039/c9nr09229c

Title: Superatomic molecules with internal electric fields for light harvesting

Journal Article · 11 February 2020 · Nanoscale

DOI: https://doi.org/10.1039/c9nr09229c · OSTI ID:1601432

^[1]; Chauhan, Vikas ^[1];

^[1];

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Virginia Commonwealth Univ., Richmond, VA (United States). Dept. of Physics

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.

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Research Organization:: Virginia Commonwealth Univ., Richmond, VA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: SC0006420

OSTI ID:: 1601432

Alternate ID(s):: OSTI ID: 1599258

Journal Information:: Nanoscale, Vol. 12, Issue 7; ISSN 2040-3364

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 13 works

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References (48)

Transforming Redox Properties of Clusters Using Phosphine Ligands Reber, Arthur C.; Bista, Dinesh; Chauhan, Vikas The Journal of Physical Chemistry C, Vol. 123, Issue 14 https://doi.org/10.1021/acs.jpcc.9b00039	journal	March 2019
Superatomic Two-Dimensional Semiconductor Zhong, Xinjue; Lee, Kihong; Choi, Bonnie Nano Letters, Vol. 18, Issue 2 https://doi.org/10.1021/acs.nanolett.7b05278	journal	January 2018
Direct Observation of Surface-Mediated Electron−Hole Pair Recombination in TiO ₂ (110) Zhang, Zhen; Yates, John T. The Journal of Physical Chemistry C, Vol. 114, Issue 7 https://doi.org/10.1021/jp910404e	journal	February 2010
Depletion-Layer Photoeffects in Semiconductors Gärtner, Wolfgang W. Physical Review, Vol. 116, Issue 1 https://doi.org/10.1103/PhysRev.116.84	journal	October 1959
More than just a support: Graphene as a solid-state ligand for palladium-catalyzed cross-coupling reactions Yang, Yuan; Reber, Arthur C.; Gilliland, Stanley E. Journal of Catalysis, Vol. 360 https://doi.org/10.1016/j.jcat.2018.01.027	journal	April 2018
Controlling the Band Gap Energy of Cluster-Assembled Materials Mandal, Sukhendu; Reber, Arthur C.; Qian, Meichun Accounts of Chemical Research, Vol. 46, Issue 11 https://doi.org/10.1021/ar3002975	journal	June 2013
Synthesis, structure and band gap energy of covalently linked cluster-assembled materials Mandal, Sukhendu; Reber, Arthur C.; Qian, Meichun Dalton Transactions, Vol. 41, Issue 40 https://doi.org/10.1039/c2dt31286g	journal	January 2012
Highly Emissive Hexanuclear Rhenium(III) Clusters Containing the Cubic Cores [Re ₆ S ₈ ] ²⁺ and [Re ₆ Se ₈ ] ²⁺ Gray, Thomas G.; Rudzinski, Christina M.; Nocera, Daniel G. Inorganic Chemistry, Vol. 38, Issue 26 https://doi.org/10.1021/ic991195i	journal	December 1999
Relativistic regular two-component Hamiltonians van Lenthe, E.; van Leeuwen, R.; Baerends, E. J. International Journal of Quantum Chemistry, Vol. 57, Issue 3 https://doi.org/10.1002/(SICI)1097-461X(1996)57:3<281::AID-QUA2>3.0.CO;2-U	journal	February 1996
Accurate and simple density functional for the electronic exchange energy: Generalized gradient approximation Perdew, John P.; Yue, Wang Physical Review B, Vol. 33, Issue 12 https://doi.org/10.1103/PhysRevB.33.8800	journal	June 1986
[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 Shores, Matthew P.; Beauvais, Laurance G.; Long, Jeffrey R. Inorganic Chemistry, Vol. 38, Issue 8 https://doi.org/10.1021/ic9900408	journal	April 1999
An investigation of surface states at a silicon/silicon oxide interface employing metal-oxide-silicon diodes Terman, L. M. Solid-State Electronics, Vol. 5, Issue 5 https://doi.org/10.1016/0038-1101(62)90111-9	journal	September 1962
Single-crystal-to-single-crystal intercalation of a low-bandgap superatomic crystal O'Brien, Evan S.; Trinh, M. Tuan; Kann, Rose L. Nature Chemistry, Vol. 9, Issue 12 https://doi.org/10.1038/nchem.2844	journal	August 2017
Chemistry with ADF te Velde, G.; Bickelhaupt, F. M.; Baerends, E. J. Journal of Computational Chemistry, Vol. 22, Issue 9, p. 931-967 https://doi.org/10.1002/jcc.1056	journal	January 2001
Surface effects on p-n junctions: Characteristics of surface space-charge regions under non-equilibrium conditions Grove, A. S.; Fitzgerald, D. J. Solid-State Electronics, Vol. 9, Issue 8 https://doi.org/10.1016/0038-1101(66)90118-3	journal	August 1966
Superatoms: Electronic and Geometric Effects on Reactivity Reber, Arthur C.; Khanna, Shiv N. Accounts of Chemical Research, Vol. 50, Issue 2 https://doi.org/10.1021/acs.accounts.6b00464	journal	January 2017
Nanoscale Atoms in Solid-State Chemistry Roy, X.; Lee, C. -H.; Crowther, A. C. Science, Vol. 341, Issue 6142 https://doi.org/10.1126/science.1236259	journal	June 2013
Two-Dimensional Hierarchical Semiconductor with Addressable Surfaces Choi, Bonnie; Lee, Kihong; Voevodin, Anastasia Journal of the American Chemical Society, Vol. 140, Issue 30 https://doi.org/10.1021/jacs.8b05010	journal	July 2018
Orientational order controls crystalline and amorphous thermal transport in superatomic crystals Ong, Wee-Liat; O’Brien, Evan S.; Dougherty, Patrick S. M. Nature Materials, Vol. 16, Issue 1 https://doi.org/10.1038/nmat4739	journal	September 2016
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 Szczepura, Lisa F.; Cedeño, David L.; Johnson, Dean B. Inorganic Chemistry, Vol. 49, Issue 24 https://doi.org/10.1021/ic101348h	journal	December 2010
Cluster-Assembled Materials Claridge, Shelley A.; Castleman, A. W.; Khanna, Shiv N. ACS Nano, Vol. 3, Issue 2 https://doi.org/10.1021/nn800820e	journal	January 2009
Geometry optimizations in the zero order regular approximation for relativistic effects van Lenthe, Erik; Ehlers, Andreas; Baerends, Evert-Jan The Journal of Chemical Physics, Vol. 110, Issue 18 https://doi.org/10.1063/1.478813	journal	May 1999
Superatom Fusion and the Nature of Quantum Confinement Champsaur, Anouck M.; Hochuli, Taylor J.; Paley, Daniel W. Nano Letters, Vol. 18, Issue 7 https://doi.org/10.1021/acs.nanolett.8b01824	journal	June 2018
Molecular control of quantum-dot internal electric field and its application to CdSe-based solar cells Yaacobi-Gross, Nir; Soreni-Harari, Michal; Zimin, Marina Nature Materials, Vol. 10, Issue 12 https://doi.org/10.1038/nmat3133	journal	October 2011
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) Reber, Arthur C.; Khanna, Shiv N. The European Physical Journal D, Vol. 72, Issue 11 https://doi.org/10.1140/epjd/e2018-90223-7	journal	November 2018
ZnO p-n junction light-emitting diodes fabricated on sapphire substrates Jiao, S. J.; Zhang, Z. Z.; Lu, Y. M. Applied Physics Letters, Vol. 88, Issue 3 https://doi.org/10.1063/1.2166686	journal	January 2006
Phase-transition–induced p-n junction in single halide perovskite nanowire Kong, Qiao; Lee, Woochul; Lai, Minliang Proceedings of the National Academy of Sciences, Vol. 115, Issue 36 https://doi.org/10.1073/pnas.1806515115	journal	August 2018
Strong Effect of Organic Ligands on the Electronic Structure of Metal-Chalcogenide Clusters Chauhan, Vikas; Khanna, Shiv N. The Journal of Physical Chemistry A, Vol. 122, Issue 28 https://doi.org/10.1021/acs.jpca.8b03355	journal	June 2018
Atomic clusters: Building blocks for a class of solids Khanna, S. N.; Jena, P. Physical Review B, Vol. 51, Issue 19 https://doi.org/10.1103/PhysRevB.51.13705	journal	May 1995
Metal Chalcogenide Clusters with Closed Electronic Shells and the Electronic Properties of Alkalis and Halogens Chauhan, Vikas; Reber, Arthur C.; Khanna, Shiv N. Journal of the American Chemical Society, Vol. 139, Issue 5 https://doi.org/10.1021/jacs.6b09416	journal	January 2017
Electron donor-acceptor properties of phosphorus ligands. Substituent additivity Tolman, Chadwick A. Journal of the American Chemical Society, Vol. 92, Issue 10 https://doi.org/10.1021/ja00713a006	journal	May 1970
Dynamics of electron-hole pair recombination in semiconductor clusters O'Neil, M.; Marohn, J.; McLendon, G. The Journal of Physical Chemistry, Vol. 94, Issue 10 https://doi.org/10.1021/j100373a089	journal	May 1990
Chemistry of Lewis Acid–Base Pairs on Oxide Surfaces Metiu, Horia; Chrétien, Steeve; Hu, Zhenpeng The Journal of Physical Chemistry C, Vol. 116, Issue 19 https://doi.org/10.1021/jp301341t	journal	April 2012
Epitaxial growth of a monolayer WSe2-MoS2 lateral p-n junction with an atomically sharp interface Li, M. -Y.; Shi, Y.; Cheng, C. -C. Science, Vol. 349, Issue 6247 https://doi.org/10.1126/science.aab4097	journal	July 2015
Tuning the electronic properties of hexanuclear cobalt sulfide superatoms via ligand substitution Liu, Gaoxiang; Pinkard, Andrew; Ciborowski, Sandra M. Chemical Science, Vol. 10, Issue 6 https://doi.org/10.1039/C8SC03862G	journal	January 2019
Transforming Ni ₉ Te ₆ from Electron Donor to Acceptor via Ligand Exchange Chauhan, Vikas; Reber, Arthur C.; Khanna, Shiv N. The Journal of Physical Chemistry A, Vol. 120, Issue 33 https://doi.org/10.1021/acs.jpca.6b05701	journal	August 2016
A simplified relativistic time-dependent density-functional theory formalism for the calculations of excitation energies including spin-orbit coupling effect Wang, Fan; Ziegler, Tom The Journal of Chemical Physics, Vol. 123, Issue 15 https://doi.org/10.1063/1.2061187	journal	October 2005
Optimized Slater-type basis sets for the elements 1-118 Van Lenthe, E.; Baerends, E. J. Journal of Computational Chemistry, Vol. 24, Issue 9 https://doi.org/10.1002/jcc.10255	journal	May 2003
Effect of N- and P-Type Doping on the Oxygen-Binding Energy and Oxygen Spillover of Supported Palladium Clusters Reber, Arthur C.; Khanna, Shiv N. The Journal of Physical Chemistry C, Vol. 118, Issue 35 https://doi.org/10.1021/jp5045145	journal	August 2014
Co6Se8(PEt3)6 superatoms as tunable chemical dopants for two-dimensional semiconductors Reber, Arthur C.; Khanna, Shiv N. npj Computational Materials, Vol. 4, Issue 1 https://doi.org/10.1038/s41524-018-0092-9	journal	July 2018
Detailed Balance Limit of Efficiency of p‐n Junction Solar Cells Shockley, William; Queisser, Hans J. Journal of Applied Physics, Vol. 32, Issue 3, p. 510-519 https://doi.org/10.1063/1.1736034	journal	March 1961
van der Waals Solids from Self-Assembled Nanoscale Building Blocks Choi, Bonnie; Yu, Jaeeun; Paley, Daniel W. Nano Letters, Vol. 16, Issue 2 https://doi.org/10.1021/acs.nanolett.5b05049	journal	January 2016
Synthesis and investigation of cobalt chalcogenide clusters with thienyl phosphine ligands as new acceptor materials for P3HT Reeves, B. J.; Shircliff, D. M.; Shott, J. L. Dalton Transactions, Vol. 44, Issue 2 https://doi.org/10.1039/C4DT02570A	journal	January 2015
Molecular Clusters: Nanoscale Building Blocks for Solid-State Materials Pinkard, Andrew; Champsaur, Anouck M.; Roy, Xavier Accounts of Chemical Research, Vol. 51, Issue 4 https://doi.org/10.1021/acs.accounts.8b00016	journal	March 2018
Ball and Socket Assembly of Binary Superatomic Solids Containing Trinuclear Nickel Cluster Cations and Fulleride Anions Shott, Jessica L.; Freeman, Matthew B.; Saleh, Nemah-Allah Inorganic Chemistry, Vol. 56, Issue 18 https://doi.org/10.1021/acs.inorgchem.7b01259	journal	August 2017
The electric field under a STM tip apex: implications for adsorbate manipulation Girard, C.; Joachim, C.; Chavy, C. Surface Science, Vol. 282, Issue 3 https://doi.org/10.1016/0039-6028(93)90944-F	journal	February 1993
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 Shichibu, Yukatsu; Negishi, Yuichi; Watanabe, Takahito The Journal of Physical Chemistry C, Vol. 111, Issue 22 https://doi.org/10.1021/jp073101t	journal	June 2007
Conductance of Single Cobalt Chalcogenide Cluster Junctions Boardman, Brycelyn M.; Widawsky, Jonathan R.; Park, Young S. Journal of the American Chemical Society, Vol. 133, Issue 22 https://doi.org/10.1021/ja201334s	journal	June 2011

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