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Title: 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.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Virginia Commonwealth Univ., Richmond, VA (United States). Dept. of Physics
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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