Band Alignments, Electronic Structure, and Core-Level Spectra of Bulk Molybdenum Dichalcogenides (MoS2, MoSe2, and MoTe2)

Leanne A.H. Jones; Zongda Xing; Jack E.N. Swallow; Huw Shiel; Thomas J. Featherstone; Matthew J. Smiles; Nicole Fleck; Pardeep K. Thakur; Tien Lin Lee; Laurence J. Hardwick; David O. Scanlon; Anna Regoutz; Tim D. Veal; Vinod R. Dhanak

doi:10.1021/acs.jpcc.2c05100

Band Alignments, Electronic Structure, and Core-Level Spectra of Bulk Molybdenum Dichalcogenides (MoS₂, MoSe₂, and MoTe₂)

Leanne A.H. Jones, Zongda Xing, Jack E.N. Swallow, Huw Shiel, Thomas J. Featherstone, Matthew J. Smiles, Nicole Fleck, Pardeep K. Thakur, Tien Lin Lee, Laurence J. Hardwick, David O. Scanlon, Anna Regoutz, Tim D. Veal^*, Vinod R. Dhanak

^*Corresponding author for this work

Chemistry

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Abstract

A comprehensive study of bulk molybdenum dichalcogenides is presented with the use of soft and hard X-ray photoelectron (SXPS and HAXPES) spectroscopy combined with hybrid density functional theory (DFT). The main core levels of MoS₂, MoSe₂, and MoTe₂are explored. Laboratory-based X-ray photoelectron spectroscopy (XPS) is used to determine the ionization potential (IP) values of the MoX₂series as 5.86, 5.40, and 5.00 eV for MoSe₂, MoSe₂, and MoTe₂, respectively, enabling the band alignment of the series to be established. Finally, the valence band measurements are compared with the calculated density of states which shows the role of p-d hybridization in these materials. Down the group, an increase in the p-d hybridization from the sulfide to the telluride is observed, explained by the configuration energy of the chalcogen p orbitals becoming closer to that of the valence Mo 4d orbitals. This pushes the valence band maximum closer to the vacuum level, explaining the decreasing IP down the series. High-resolution SXPS and HAXPES core-level spectra address the shortcomings of the XPS analysis in the literature. Furthermore, the experimentally determined band alignment can be used to inform future device work.

Original language	English
Pages (from-to)	21022-21033
Number of pages	12
Journal	Journal of Physical Chemistry C
Volume	126
Issue number	49
Early online date	1 Dec 2022
DOIs	https://doi.org/10.1021/acs.jpcc.2c05100
Publication status	Published - 15 Dec 2022

Bibliographical note

Funding Information:
This work was supported by the Engineering and Physical Sciences Research Council (EPSRC) (grant no. EP/N015800/1). L.A.H.J., N.F., and H.S.’s studentships were funded by the EPSRC Doctoral Training Partnership (grant nos. EP/R513271/1 and EP/N509693/1). J.E.N.S., T.J.F., and M.J.S. acknowledge studentship support from the EPSRC Centre for Doctoral Training in New and Sustainable Photovoltaics (grant no. EP/L01551X/1). The authors acknowledge Diamond Light Source for time on Beamline I09 under Proposal No. SI25980-2. They thank Dave McCue, I09 beamline technician, for his support of the experiments. Through our membership of the UK’s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202, EP/R029431, EP/T022213), this work used the ARCHER UK National Supercomputing Service ( http://www.archer.ac.uk ) and the ARCHER2 UK National Supercomputing Service ( https://www.archer2.ac.uk ). The authors also thank the UK Materials and Molecular Modelling Hub for computational resources that is partially funded by EPSRC (EP/P020194 and EP/T022213). A.R. acknowledges support from the Analytical Chemistry Trust Fund for her CAMS Fellowship.

Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
General Energy
Physical and Theoretical Chemistry
Surfaces, Coatings and Films

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Cite this

Jones, L. A. H., Xing, Z., Swallow, J. E. N., Shiel, H., Featherstone, T. J., Smiles, M. J., Fleck, N., Thakur, P. K., Lee, T. L., Hardwick, L. J., Scanlon, D. O., Regoutz, A., Veal, T. D., & Dhanak, V. R. (2022). Band Alignments, Electronic Structure, and Core-Level Spectra of Bulk Molybdenum Dichalcogenides (MoS₂, MoSe₂, and MoTe₂). Journal of Physical Chemistry C, 126(49), 21022-21033. https://doi.org/10.1021/acs.jpcc.2c05100

@article{311fafabb1854de6aaff6ce034f6ba4b,

title = "Band Alignments, Electronic Structure, and Core-Level Spectra of Bulk Molybdenum Dichalcogenides (MoS2, MoSe2, and MoTe2)",

abstract = "A comprehensive study of bulk molybdenum dichalcogenides is presented with the use of soft and hard X-ray photoelectron (SXPS and HAXPES) spectroscopy combined with hybrid density functional theory (DFT). The main core levels of MoS2, MoSe2, and MoTe2are explored. Laboratory-based X-ray photoelectron spectroscopy (XPS) is used to determine the ionization potential (IP) values of the MoX2series as 5.86, 5.40, and 5.00 eV for MoSe2, MoSe2, and MoTe2, respectively, enabling the band alignment of the series to be established. Finally, the valence band measurements are compared with the calculated density of states which shows the role of p-d hybridization in these materials. Down the group, an increase in the p-d hybridization from the sulfide to the telluride is observed, explained by the configuration energy of the chalcogen p orbitals becoming closer to that of the valence Mo 4d orbitals. This pushes the valence band maximum closer to the vacuum level, explaining the decreasing IP down the series. High-resolution SXPS and HAXPES core-level spectra address the shortcomings of the XPS analysis in the literature. Furthermore, the experimentally determined band alignment can be used to inform future device work.",

author = "Jones, {Leanne A.H.} and Zongda Xing and Swallow, {Jack E.N.} and Huw Shiel and Featherstone, {Thomas J.} and Smiles, {Matthew J.} and Nicole Fleck and Thakur, {Pardeep K.} and Lee, {Tien Lin} and Hardwick, {Laurence J.} and Scanlon, {David O.} and Anna Regoutz and Veal, {Tim D.} and Dhanak, {Vinod R.}",

note = "Funding Information: This work was supported by the Engineering and Physical Sciences Research Council (EPSRC) (grant no. EP/N015800/1). L.A.H.J., N.F., and H.S.{\textquoteright}s studentships were funded by the EPSRC Doctoral Training Partnership (grant nos. EP/R513271/1 and EP/N509693/1). J.E.N.S., T.J.F., and M.J.S. acknowledge studentship support from the EPSRC Centre for Doctoral Training in New and Sustainable Photovoltaics (grant no. EP/L01551X/1). The authors acknowledge Diamond Light Source for time on Beamline I09 under Proposal No. SI25980-2. They thank Dave McCue, I09 beamline technician, for his support of the experiments. Through our membership of the UK{\textquoteright}s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202, EP/R029431, EP/T022213), this work used the ARCHER UK National Supercomputing Service ( http://www.archer.ac.uk ) and the ARCHER2 UK National Supercomputing Service ( https://www.archer2.ac.uk ). The authors also thank the UK Materials and Molecular Modelling Hub for computational resources that is partially funded by EPSRC (EP/P020194 and EP/T022213). A.R. acknowledges support from the Analytical Chemistry Trust Fund for her CAMS Fellowship. Publisher Copyright: {\textcopyright} 2022 American Chemical Society. All rights reserved.",

year = "2022",

month = dec,

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doi = "10.1021/acs.jpcc.2c05100",

language = "English",

volume = "126",

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journal = "Journal of Physical Chemistry C",

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Jones, LAH, Xing, Z, Swallow, JEN, Shiel, H, Featherstone, TJ, Smiles, MJ, Fleck, N, Thakur, PK, Lee, TL, Hardwick, LJ, Scanlon, DO, Regoutz, A, Veal, TD & Dhanak, VR 2022, 'Band Alignments, Electronic Structure, and Core-Level Spectra of Bulk Molybdenum Dichalcogenides (MoS₂, MoSe₂, and MoTe₂)', Journal of Physical Chemistry C, vol. 126, no. 49, pp. 21022-21033. https://doi.org/10.1021/acs.jpcc.2c05100

TY - JOUR

T1 - Band Alignments, Electronic Structure, and Core-Level Spectra of Bulk Molybdenum Dichalcogenides (MoS2, MoSe2, and MoTe2)

AU - Jones, Leanne A.H.

AU - Xing, Zongda

AU - Swallow, Jack E.N.

AU - Shiel, Huw

AU - Featherstone, Thomas J.

AU - Smiles, Matthew J.

AU - Fleck, Nicole

AU - Thakur, Pardeep K.

AU - Lee, Tien Lin

AU - Hardwick, Laurence J.

AU - Scanlon, David O.

AU - Regoutz, Anna

AU - Veal, Tim D.

AU - Dhanak, Vinod R.

N1 - Funding Information: This work was supported by the Engineering and Physical Sciences Research Council (EPSRC) (grant no. EP/N015800/1). L.A.H.J., N.F., and H.S.’s studentships were funded by the EPSRC Doctoral Training Partnership (grant nos. EP/R513271/1 and EP/N509693/1). J.E.N.S., T.J.F., and M.J.S. acknowledge studentship support from the EPSRC Centre for Doctoral Training in New and Sustainable Photovoltaics (grant no. EP/L01551X/1). The authors acknowledge Diamond Light Source for time on Beamline I09 under Proposal No. SI25980-2. They thank Dave McCue, I09 beamline technician, for his support of the experiments. Through our membership of the UK’s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202, EP/R029431, EP/T022213), this work used the ARCHER UK National Supercomputing Service ( http://www.archer.ac.uk ) and the ARCHER2 UK National Supercomputing Service ( https://www.archer2.ac.uk ). The authors also thank the UK Materials and Molecular Modelling Hub for computational resources that is partially funded by EPSRC (EP/P020194 and EP/T022213). A.R. acknowledges support from the Analytical Chemistry Trust Fund for her CAMS Fellowship. Publisher Copyright: © 2022 American Chemical Society. All rights reserved.

PY - 2022/12/15

Y1 - 2022/12/15

N2 - A comprehensive study of bulk molybdenum dichalcogenides is presented with the use of soft and hard X-ray photoelectron (SXPS and HAXPES) spectroscopy combined with hybrid density functional theory (DFT). The main core levels of MoS2, MoSe2, and MoTe2are explored. Laboratory-based X-ray photoelectron spectroscopy (XPS) is used to determine the ionization potential (IP) values of the MoX2series as 5.86, 5.40, and 5.00 eV for MoSe2, MoSe2, and MoTe2, respectively, enabling the band alignment of the series to be established. Finally, the valence band measurements are compared with the calculated density of states which shows the role of p-d hybridization in these materials. Down the group, an increase in the p-d hybridization from the sulfide to the telluride is observed, explained by the configuration energy of the chalcogen p orbitals becoming closer to that of the valence Mo 4d orbitals. This pushes the valence band maximum closer to the vacuum level, explaining the decreasing IP down the series. High-resolution SXPS and HAXPES core-level spectra address the shortcomings of the XPS analysis in the literature. Furthermore, the experimentally determined band alignment can be used to inform future device work.

AB - A comprehensive study of bulk molybdenum dichalcogenides is presented with the use of soft and hard X-ray photoelectron (SXPS and HAXPES) spectroscopy combined with hybrid density functional theory (DFT). The main core levels of MoS2, MoSe2, and MoTe2are explored. Laboratory-based X-ray photoelectron spectroscopy (XPS) is used to determine the ionization potential (IP) values of the MoX2series as 5.86, 5.40, and 5.00 eV for MoSe2, MoSe2, and MoTe2, respectively, enabling the band alignment of the series to be established. Finally, the valence band measurements are compared with the calculated density of states which shows the role of p-d hybridization in these materials. Down the group, an increase in the p-d hybridization from the sulfide to the telluride is observed, explained by the configuration energy of the chalcogen p orbitals becoming closer to that of the valence Mo 4d orbitals. This pushes the valence band maximum closer to the vacuum level, explaining the decreasing IP down the series. High-resolution SXPS and HAXPES core-level spectra address the shortcomings of the XPS analysis in the literature. Furthermore, the experimentally determined band alignment can be used to inform future device work.

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