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

Reber, Arthur C.; Khanna, Shiv N.

doi:10.1038/s41524-018-0092-9

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

Journal Article · Fri Jul 13 00:00:00 EDT 2018 · npj Computational Materials

DOI:https://doi.org/10.1038/s41524-018-0092-9· OSTI ID:1459232

; Khanna, Shiv N.

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 ₆ Se 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 ₆ Se 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 ₆ Se 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.

View Journal Article

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

Sponsoring Organization:: USDOE; USDOE Office of Science (SC)

Grant/Contract Number:: SC0006420

OSTI ID:: 1459232

Alternate ID(s):: OSTI ID: 1501530

Journal Information:: npj Computational Materials, Journal Name: npj Computational Materials Journal Issue: 1 Vol. 4; ISSN 2057-3960

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United Kingdom

Language:: English

References (50)

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
Semiempirical GGA-type density functional constructed with a long-range dispersion correction Grimme, Stefan Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799 https://doi.org/10.1002/jcc.20495	journal	January 2006
Substitutional doping of amorphous silicon Spear, W. E.; Le Comber, P. G. Solid State Communications, Vol. 17, Issue 9 https://doi.org/10.1016/0038-1098(75)90284-7	journal	November 1975
Intrinsic limitations to the doping of wide-gap semiconductors Walukiewicz, W. Physica B: Condensed Matter, Vol. 302-303 https://doi.org/10.1016/S0921-4526(01)00417-3	journal	January 2001
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
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
Solution-Processed Doping of Trilayer WSe ₂ with Redox-Active Molecules Tsai, Meng-Yen; Zhang, Siyuan; Campbell, Philip M. Chemistry of Materials, Vol. 29, Issue 17 https://doi.org/10.1021/acs.chemmater.7b01998	journal	August 2017
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
Patterning Superatom Dopants on Transition Metal Dichalcogenides Yu, Jaeeun; Lee, Chul-Ho; Bouilly, Delphine Nano Letters, Vol. 16, Issue 5 https://doi.org/10.1021/acs.nanolett.6b01152	journal	April 2016
Building Diatomic and Triatomic Superatom Molecules Champsaur, Anouck M.; Velian, Alexandra; Paley, Daniel W. Nano Letters, Vol. 16, Issue 8 https://doi.org/10.1021/acs.nanolett.6b02471	journal	July 2016
Reversible Semiconducting-to-Metallic Phase Transition in Chemical Vapor Deposition Grown Monolayer WSe ₂ and Applications for Devices Ma, Yuqiang; Liu, Bilu; Zhang, Anyi ACS Nano, Vol. 9, Issue 7 https://doi.org/10.1021/acsnano.5b02399	journal	June 2015
“n-Doping” of Deltahedral Zintl Ions Gillett-Kunnath, Miriam M.; Oliver, Allen G.; Sevov, Slavi C. Journal of the American Chemical Society, Vol. 133, Issue 17 https://doi.org/10.1021/ja200520c	journal	May 2011
Air-Stable Surface Charge Transfer Doping of MoS ₂ by Benzyl Viologen Kiriya, Daisuke; Tosun, Mahmut; Zhao, Peida Journal of the American Chemical Society, Vol. 136, Issue 22 https://doi.org/10.1021/ja5033327	journal	May 2014
Ferromagnetic Ordering in Superatomic Solids Lee, Chul-Ho; Liu, Lian; Bejger, Christopher Journal of the American Chemical Society, Vol. 136, Issue 48 https://doi.org/10.1021/ja5098622	journal	November 2014
On the Structure of Thiolate-Protected Au ₂₅ Akola, Jaakko; Walter, Michael; Whetten, Robert L. Journal of the American Chemical Society, Vol. 130, Issue 12 https://doi.org/10.1021/ja800594p	journal	March 2008
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
Weaving Nanoscale Cloth through Electrostatic Templating Champsaur, Anouck M.; Mézière, Cécile; Allain, Magali Journal of the American Chemical Society, Vol. 139, Issue 34 https://doi.org/10.1021/jacs.7b07279	journal	August 2017
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
Initial and Final State Effects in the Ultraviolet and X-ray Photoelectron Spectroscopy (UPS and XPS) of Size-Selected Pd _n Clusters Supported on TiO ₂ (110) Roberts, F. Sloan; Anderson, Scott L.; Reber, Arthur C. The Journal of Physical Chemistry C, Vol. 119, Issue 11 https://doi.org/10.1021/jp512263w	journal	March 2015
Electronic Structure of Ligand-Passivated Gold and Silver Nanoclusters Aikens, Christine M. The Journal of Physical Chemistry Letters, Vol. 2, Issue 2 https://doi.org/10.1021/jz101499g	journal	December 2010
High-Performance Single Layered WSe₂ p-FETs with Chemically Doped Contacts Fang, Hui; Chuang, Steven; Chang, Ting Chia Nano Letters, Vol. 12, Issue 7, p. 3788-3792 https://doi.org/10.1021/nl301702r	journal	June 2012
Degenerate n-Doping of Few-Layer Transition Metal Dichalcogenides by Potassium Fang, Hui; Tosun, Mahmut; Seol, Gyungseon Nano Letters, Vol. 13, Issue 5, p. 1991-1995 https://doi.org/10.1021/nl400044m	journal	April 2013
Broad-Range Modulation of Light Emission in Two-Dimensional Semiconductors by Molecular Physisorption Gating Tongay, Sefaattin; Zhou, Jian; Ataca, Can Nano Letters, Vol. 13, Issue 6 https://doi.org/10.1021/nl4011172	journal	May 2013
Functionalization of Transition Metal Dichalcogenides with Metallic Nanoparticles: Implications for Doping and Gas-Sensing Sarkar, Deblina; Xie, Xuejun; Kang, Jiahao Nano Letters, Vol. 15, Issue 5 https://doi.org/10.1021/nl504454u	journal	April 2015
Evolution of Electronic Structure in Atomically Thin Sheets of WS ₂ and WSe ₂ Zhao, Weijie; Ghorannevis, Zohreh; Chu, Leiqiang ACS Nano, Vol. 7, Issue 1 https://doi.org/10.1021/nn305275h	journal	December 2012
High-Performance Chemical Sensing Using Schottky-Contacted Chemical Vapor Deposition Grown Monolayer MoS ₂ Transistors Liu, Bilu; Chen, Liang; Liu, Gang ACS Nano, Vol. 8, Issue 5 https://doi.org/10.1021/nn5015215	journal	April 2014
Doping semiconductor nanocrystals Erwin, Steven C.; Zu, Lijun; Haftel, Michael I. Nature, Vol. 436, Issue 7047 https://doi.org/10.1038/nature03832	journal	July 2005
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
Intercalation without altercation Khanna, Shiv N.; Reber, Arthur C. Nature Chemistry, Vol. 9, Issue 12 https://doi.org/10.1038/nchem.2895	journal	November 2017
Electronics and optoelectronics of two-dimensional transition metal dichalcogenides Wang, Qing Hua; Kalantar-Zadeh, Kourosh; Kis, Andras Nature Nanotechnology, Vol. 7, Issue 11, p. 699-712 https://doi.org/10.1038/nnano.2012.193	journal	November 2012
Electrically tunable excitonic light-emitting diodes based on monolayer WSe2 p–n junctions Ross, Jason S.; Klement, Philip; Jones, Aaron M. Nature Nanotechnology, Vol. 9, Issue 4 https://doi.org/10.1038/nnano.2014.26	journal	March 2014
Electrical control of second-harmonic generation in a WSe2 monolayer transistor Seyler, Kyle L.; Schaibley, John R.; Gong, Pu Nature Nanotechnology, Vol. 10, Issue 5 https://doi.org/10.1038/nnano.2015.73	journal	April 2015
Strong lowering of ionization energy of metallic clusters by organic ligands without changing shell filling Chauhan, Vikas; Reber, Arthur C.; Khanna, Shiv N. Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04799-0	journal	June 2018
A fundamental analysis of enhanced cross-coupling catalytic activity for palladium clusters on graphene supports Yang, Y.; Castano, C. E.; Gupton, B. Frank Nanoscale, Vol. 8, Issue 47 https://doi.org/10.1039/C6NR06793J	journal	January 2016
CO ligands stabilize metal chalcogenide Co ₆ Se ₈ (CO) _n clusters via demagnetization Chauhan, Vikas; Reber, Arthur C.; Khanna, Shiv N. Physical Chemistry Chemical Physics, Vol. 19, Issue 47 https://doi.org/10.1039/C7CP07606A	journal	January 2017
Influence of the exchange screening parameter on the performance of screened hybrid functionals Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F. The Journal of Chemical Physics, Vol. 125, Issue 22 https://doi.org/10.1063/1.2404663	journal	December 2006
Evidence of superatom electronic shells in ligand-stabilized aluminum clusters Andre Clayborne, P.; Lopez-Acevedo, Olga; Whetten, Robert L. The Journal of Chemical Physics, Vol. 135, Issue 9 https://doi.org/10.1063/1.3632087	journal	September 2011
Modulating electronic transport properties of MoS ₂ field effect transistor by surface overlayers Lin, Jiadan; Zhong, Jianqiang; Zhong, Shu Applied Physics Letters, Vol. 103, Issue 6 https://doi.org/10.1063/1.4818463	journal	August 2013
Symmetry and magnetism in Ni ₉ Te ₆ clusters ligated by CO or phosphine ligands Reber, Arthur C.; Chauhan, Vikas; Khanna, Shiv N. The Journal of Chemical Physics, Vol. 146, Issue 2 https://doi.org/10.1063/1.4973609	journal	January 2017
A unified view of ligand-protected gold clusters as superatom complexes Walter, M.; Akola, J.; Lopez-Acevedo, O. Proceedings of the National Academy of Sciences, Vol. 105, Issue 27 https://doi.org/10.1073/pnas.0801001105	journal	July 2008
Electronic structure of MoSe 2 , MoS 2 , and WSe 2 . II. The nature of the optical band gaps Coehoorn, R.; Haas, C.; de Groot, R. A. Physical Review B, Vol. 35, Issue 12 https://doi.org/10.1103/PhysRevB.35.6203	journal	April 1987
Synchrotron-induced surface-photovoltage saturation at intercalated Na/ WSe 2 interfaces Schellenberger, A.; Schlaf, R.; Pettenkofer, C. Physical Review B, Vol. 45, Issue 7 https://doi.org/10.1103/PhysRevB.45.3538	journal	February 1992
Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al(111) Neugebauer, Jörg; Scheffler, Matthias Physical Review B, Vol. 46, Issue 24 https://doi.org/10.1103/PhysRevB.46.16067	journal	December 1992
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
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Yellow Luminescence of Gallium Nitride Generated by Carbon Defect Complexes Demchenko, D. O.; Diallo, I. C.; Reshchikov, M. A. Physical Review Letters, Vol. 110, Issue 8 https://doi.org/10.1103/PhysRevLett.110.087404	journal	February 2013
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Formation of Al13I-: Evidence for the Superhalogen Character of Al13 Bergeron, D. E. Science, Vol. 304, Issue 5667 https://doi.org/10.1126/science.1093902	journal	April 2004
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

Similar Records

Transforming the electronic properties of phosphorene through charge transfer superatomic doping

Journal Article · Mon Feb 20 19:00:00 EST 2023 · Surface Science · OSTI ID:2419704

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

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

Citation Formats

References (50)

Similar Records

Related Subjects