Direct Experimental Evidence for Substrate Adatom Incorporation into a Molecular Overlayer

Philip J. Mousley; Luke A. Rochford; Paul T.P. Ryan; Philip Blowey; James Lawrence; David A. Duncan; Hadeel Hussain; Billal Sohail; Tien Lin Lee; Gavin R. Bell; Giovanni Costantini; Reinhard J. Maurer; Christopher Nicklin; D. Phil Woodruff

doi:10.1021/acs.jpcc.2c01432

Direct Experimental Evidence for Substrate Adatom Incorporation into a Molecular Overlayer

Philip J. Mousley, Luke A. Rochford, Paul T.P. Ryan, Philip Blowey, James Lawrence, David A. Duncan, Hadeel Hussain, Billal Sohail, Tien Lin Lee, Gavin R. Bell, Giovanni Costantini, Reinhard J. Maurer, Christopher Nicklin, D. Phil Woodruff^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

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Abstract

While the phenomenon of metal substrate adatom incorporation into molecular overlayers is generally believed to occur in several systems, the experimental evidence for this relies on the interpretation of scanning tunneling microscopy (STM) images, which can be ambiguous and provides no quantitative structural information. We show that surface X-ray diffraction (SXRD) uniquely provides unambiguous identification of these metal adatoms. We present the results of a detailed structural study of the Au(111)-F₄TCNQ system, combining surface characterization by STM, low-energy electron diffraction, and soft X-ray photoelectron spectroscopy with quantitative experimental structural information from normal incidence X-ray standing wave (NIXSW) and SXRD, together with dispersion-corrected density functional theory (DFT) calculations. Excellent agreement is found between the NIXSW data and the DFT calculations regarding the height and conformation of the adsorbed molecule, which has a twisted geometry rather than the previously supposed inverted bowl shape. SXRD measurements provide unequivocal evidence for the presence and location of Au adatoms, while the DFT calculations show this reconstruction to be strongly energetically favored.

Original language	English
Pages (from-to)	7346-7355
Number of pages	10
Journal	Journal of Physical Chemistry C
Volume	126
Issue number	16
Early online date	19 Apr 2022
DOIs	https://doi.org/10.1021/acs.jpcc.2c01432
Publication status	Published - 28 Apr 2022

Bibliographical note

Funding Information:
The authors thank Diamond Light Source for allocations SI14884-1 and SI4884-2 of beam time at beamline I09 and SI19105 at I07 that contributed to the results presented here. P.J.M. and P.T.P.R. acknowledge financial support from Diamond Light Source and EPSRC. G.C. acknowledges financial support from the EU through the ERC Grant “VISUAL-MS” (Project ID: 308115). B.S. and R.J.M. acknowledge doctoral studentship funding from the EPSRC and the National Productivity Investment Fund (NPIF). R.J.M. acknowledges financial support via a UKRI Future Leaders Fellowship (MR/S016023/1). The authors acknowledge computing resources provided by the EPSRC-funded HPC Midlands+ Computing Centre (EP/P020232/1) and the EPSRC-funded Materials Chemistry Consortium (EP/R029431/1) for the ARCHER2 U.K. National Supercomputing Service ( http://www.archer2.ac.uk).

ASJC Scopus subject areas

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

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https://eprints.whiterose.ac.uk/186914/Licence: Creative Commons: Attribution (CC BY)

Cite this

Mousley, P. J., Rochford, L. A., Ryan, P. T. P., Blowey, P., Lawrence, J., Duncan, D. A., Hussain, H., Sohail, B., Lee, T. L., Bell, G. R., Costantini, G., Maurer, R. J., Nicklin, C., & Woodruff, D. P. (2022). Direct Experimental Evidence for Substrate Adatom Incorporation into a Molecular Overlayer. Journal of Physical Chemistry C, 126(16), 7346-7355. https://doi.org/10.1021/acs.jpcc.2c01432

@article{410d3060340842fd980c002239cf0fcf,

title = "Direct Experimental Evidence for Substrate Adatom Incorporation into a Molecular Overlayer",

abstract = "While the phenomenon of metal substrate adatom incorporation into molecular overlayers is generally believed to occur in several systems, the experimental evidence for this relies on the interpretation of scanning tunneling microscopy (STM) images, which can be ambiguous and provides no quantitative structural information. We show that surface X-ray diffraction (SXRD) uniquely provides unambiguous identification of these metal adatoms. We present the results of a detailed structural study of the Au(111)-F4TCNQ system, combining surface characterization by STM, low-energy electron diffraction, and soft X-ray photoelectron spectroscopy with quantitative experimental structural information from normal incidence X-ray standing wave (NIXSW) and SXRD, together with dispersion-corrected density functional theory (DFT) calculations. Excellent agreement is found between the NIXSW data and the DFT calculations regarding the height and conformation of the adsorbed molecule, which has a twisted geometry rather than the previously supposed inverted bowl shape. SXRD measurements provide unequivocal evidence for the presence and location of Au adatoms, while the DFT calculations show this reconstruction to be strongly energetically favored.",

author = "Mousley, {Philip J.} and Rochford, {Luke A.} and Ryan, {Paul T.P.} and Philip Blowey and James Lawrence and Duncan, {David A.} and Hadeel Hussain and Billal Sohail and Lee, {Tien Lin} and Bell, {Gavin R.} and Giovanni Costantini and Maurer, {Reinhard J.} and Christopher Nicklin and Woodruff, {D. Phil}",

note = "Funding Information: The authors thank Diamond Light Source for allocations SI14884-1 and SI4884-2 of beam time at beamline I09 and SI19105 at I07 that contributed to the results presented here. P.J.M. and P.T.P.R. acknowledge financial support from Diamond Light Source and EPSRC. G.C. acknowledges financial support from the EU through the ERC Grant “VISUAL-MS” (Project ID: 308115). B.S. and R.J.M. acknowledge doctoral studentship funding from the EPSRC and the National Productivity Investment Fund (NPIF). R.J.M. acknowledges financial support via a UKRI Future Leaders Fellowship (MR/S016023/1). The authors acknowledge computing resources provided by the EPSRC-funded HPC Midlands+ Computing Centre (EP/P020232/1) and the EPSRC-funded Materials Chemistry Consortium (EP/R029431/1) for the ARCHER2 U.K. National Supercomputing Service ( http://www.archer2.ac.uk).",

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doi = "10.1021/acs.jpcc.2c01432",

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Mousley, PJ, Rochford, LA, Ryan, PTP, Blowey, P, Lawrence, J, Duncan, DA, Hussain, H, Sohail, B, Lee, TL, Bell, GR, Costantini, G, Maurer, RJ, Nicklin, C & Woodruff, DP 2022, 'Direct Experimental Evidence for Substrate Adatom Incorporation into a Molecular Overlayer', Journal of Physical Chemistry C, vol. 126, no. 16, pp. 7346-7355. https://doi.org/10.1021/acs.jpcc.2c01432

TY - JOUR

T1 - Direct Experimental Evidence for Substrate Adatom Incorporation into a Molecular Overlayer

AU - Mousley, Philip J.

AU - Rochford, Luke A.

AU - Ryan, Paul T.P.

AU - Blowey, Philip

AU - Lawrence, James

AU - Duncan, David A.

AU - Hussain, Hadeel

AU - Sohail, Billal

AU - Lee, Tien Lin

AU - Bell, Gavin R.

AU - Costantini, Giovanni

AU - Maurer, Reinhard J.

AU - Nicklin, Christopher

AU - Woodruff, D. Phil

N1 - Funding Information: The authors thank Diamond Light Source for allocations SI14884-1 and SI4884-2 of beam time at beamline I09 and SI19105 at I07 that contributed to the results presented here. P.J.M. and P.T.P.R. acknowledge financial support from Diamond Light Source and EPSRC. G.C. acknowledges financial support from the EU through the ERC Grant “VISUAL-MS” (Project ID: 308115). B.S. and R.J.M. acknowledge doctoral studentship funding from the EPSRC and the National Productivity Investment Fund (NPIF). R.J.M. acknowledges financial support via a UKRI Future Leaders Fellowship (MR/S016023/1). The authors acknowledge computing resources provided by the EPSRC-funded HPC Midlands+ Computing Centre (EP/P020232/1) and the EPSRC-funded Materials Chemistry Consortium (EP/R029431/1) for the ARCHER2 U.K. National Supercomputing Service ( http://www.archer2.ac.uk).

PY - 2022/4/28

Y1 - 2022/4/28

N2 - While the phenomenon of metal substrate adatom incorporation into molecular overlayers is generally believed to occur in several systems, the experimental evidence for this relies on the interpretation of scanning tunneling microscopy (STM) images, which can be ambiguous and provides no quantitative structural information. We show that surface X-ray diffraction (SXRD) uniquely provides unambiguous identification of these metal adatoms. We present the results of a detailed structural study of the Au(111)-F4TCNQ system, combining surface characterization by STM, low-energy electron diffraction, and soft X-ray photoelectron spectroscopy with quantitative experimental structural information from normal incidence X-ray standing wave (NIXSW) and SXRD, together with dispersion-corrected density functional theory (DFT) calculations. Excellent agreement is found between the NIXSW data and the DFT calculations regarding the height and conformation of the adsorbed molecule, which has a twisted geometry rather than the previously supposed inverted bowl shape. SXRD measurements provide unequivocal evidence for the presence and location of Au adatoms, while the DFT calculations show this reconstruction to be strongly energetically favored.

AB - While the phenomenon of metal substrate adatom incorporation into molecular overlayers is generally believed to occur in several systems, the experimental evidence for this relies on the interpretation of scanning tunneling microscopy (STM) images, which can be ambiguous and provides no quantitative structural information. We show that surface X-ray diffraction (SXRD) uniquely provides unambiguous identification of these metal adatoms. We present the results of a detailed structural study of the Au(111)-F4TCNQ system, combining surface characterization by STM, low-energy electron diffraction, and soft X-ray photoelectron spectroscopy with quantitative experimental structural information from normal incidence X-ray standing wave (NIXSW) and SXRD, together with dispersion-corrected density functional theory (DFT) calculations. Excellent agreement is found between the NIXSW data and the DFT calculations regarding the height and conformation of the adsorbed molecule, which has a twisted geometry rather than the previously supposed inverted bowl shape. SXRD measurements provide unequivocal evidence for the presence and location of Au adatoms, while the DFT calculations show this reconstruction to be strongly energetically favored.

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U2 - 10.1021/acs.jpcc.2c01432

DO - 10.1021/acs.jpcc.2c01432

M3 - Article

AN - SCOPUS:85128635278

SN - 1932-7447

VL - 126

SP - 7346

EP - 7355

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

IS - 16

ER -

Direct Experimental Evidence for Substrate Adatom Incorporation into a Molecular Overlayer

Abstract

Bibliographical note

ASJC Scopus subject areas

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