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Title: Co6Se8(PEt3)6 superatoms as tunable chemical dopants for two-dimensional semiconductors

Abstract

Electronic, optoelectronic, and other functionalities of semiconductors are controlled by the nature and density of carriers, and the location of the Fermi energy. Developing strategies to tune these parameters holds the key to precise control over semiconductors properties. We propose that ligand exchange on superatoms can offer a systematic strategy to vary these properties. We demonstrate this by considering a WSe 2 surface doped with ligated metal chalcogenide Co 6Se 8(PEt 3) 6 clusters. These superatoms are characterized by valence quantum states that can readily donate multiple electrons. We find that the WSe 2 support binds more strongly to the Co 6Se 8 cluster than the PEt 3 ligand, so ligand exchange between the phosphine ligand and the WSe 2 support is energetically favorable. The metal chalcogenide superatoms serves as a donor that may transform the WSe 2 p-type film into an n-type semiconductor. The theoretical findings complement recent experiments where WSe 2 films with supported Co 6Se 8(PEt 3) 6 are indeed found to undergo a change in behavior from p- to n-type. We further show that by replacing the PEt 3 ligands by CO ligands, one can control the electronic character of the surface and deposited species.

Authors:
ORCiD logo;
Publication Date:
Research Org.:
Virginia Commonwealth Univ., Richmond, VA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1459232
Alternate Identifier(s):
OSTI ID: 1501530
Grant/Contract Number:  
SC0006420
Resource Type:
Journal Article: Published Article
Journal Name:
npj Computational Materials
Additional Journal Information:
Journal Name: npj Computational Materials Journal Volume: 4 Journal Issue: 1; Journal ID: ISSN 2057-3960
Publisher:
Nature Publishing Group
Country of Publication:
United Kingdom
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Reber, Arthur C., and Khanna, Shiv N. Co6Se8(PEt3)6 superatoms as tunable chemical dopants for two-dimensional semiconductors. United Kingdom: N. p., 2018. Web. doi:10.1038/s41524-018-0092-9.
Reber, Arthur C., & Khanna, Shiv N. Co6Se8(PEt3)6 superatoms as tunable chemical dopants for two-dimensional semiconductors. United Kingdom. doi:10.1038/s41524-018-0092-9.
Reber, Arthur C., and Khanna, Shiv N. Fri . "Co6Se8(PEt3)6 superatoms as tunable chemical dopants for two-dimensional semiconductors". United Kingdom. doi:10.1038/s41524-018-0092-9.
@article{osti_1459232,
title = {Co6Se8(PEt3)6 superatoms as tunable chemical dopants for two-dimensional semiconductors},
author = {Reber, Arthur C. and Khanna, Shiv N.},
abstractNote = {Electronic, optoelectronic, and other functionalities of semiconductors are controlled by the nature and density of carriers, and the location of the Fermi energy. Developing strategies to tune these parameters holds the key to precise control over semiconductors properties. We propose that ligand exchange on superatoms can offer a systematic strategy to vary these properties. We demonstrate this by considering a WSe2 surface doped with ligated metal chalcogenide Co6Se8(PEt3)6 clusters. These superatoms are characterized by valence quantum states that can readily donate multiple electrons. We find that the WSe2 support binds more strongly to the Co6Se8 cluster than the PEt3 ligand, so ligand exchange between the phosphine ligand and the WSe2 support is energetically favorable. The metal chalcogenide superatoms serves as a donor that may transform the WSe2 p-type film into an n-type semiconductor. The theoretical findings complement recent experiments where WSe2 films with supported Co6Se8(PEt3)6 are indeed found to undergo a change in behavior from p- to n-type. We further show that by replacing the PEt3 ligands by CO ligands, one can control the electronic character of the surface and deposited species.},
doi = {10.1038/s41524-018-0092-9},
journal = {npj Computational Materials},
issn = {2057-3960},
number = 1,
volume = 4,
place = {United Kingdom},
year = {2018},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1038/s41524-018-0092-9

Citation Metrics:
Cited by: 8 works
Citation information provided by
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Figures / Tables:

Fig. 1 Fig. 1: Structure of WSe2, Co6Se8(PEt3)6, Co6Se8(PEt3)5 on WSe2, and Co6Se8(PEt3)6 on WSe2

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      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.