Charge-Transfer-Driven Nonplanar Adsorption of F4TCNQ Molecules on Epitaxial Graphene

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Charge-Transfer-Driven Nonplanar Adsorption of F4TCNQ Molecules on Epitaxial Graphene. / Kumar, Avijit; Banerjee, Kaustuv; Dvorak, Marc; Schulz, Fabian; Harju, Ari; Rinke, Patrick; Liljeroth, Peter.

In: ACS Nano, Vol. 11, No. 5, 23.05.2017, p. 4960-4968.

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Kumar, Avijit ; Banerjee, Kaustuv ; Dvorak, Marc ; Schulz, Fabian ; Harju, Ari ; Rinke, Patrick ; Liljeroth, Peter. / Charge-Transfer-Driven Nonplanar Adsorption of F4TCNQ Molecules on Epitaxial Graphene. In: ACS Nano. 2017 ; Vol. 11, No. 5. pp. 4960-4968.

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@article{9d8ba04177174db3b503154994eef1e9,
title = "Charge-Transfer-Driven Nonplanar Adsorption of F4TCNQ Molecules on Epitaxial Graphene",
abstract = "π-conjugated organic molecules tend to adsorb in a planar configuration on graphene irrespective of their charge state. In contrast, here we demonstrate charging-induced strong structural relaxation of tetrafluorotetracyanoquinodimethane (F4TCNQ) on epitaxial graphene on Ir(111) (G/Ir(111)). The work function modulation over the graphene moir{\'e} unit cell causes site-selective charging of F4TCNQ. Upon charging, the molecule anchors to the face-centered cubic sites of the G/Ir(111) moir{\'e} through one or two cyano groups. The reaction is reversible and can be triggered on a single molecule by moving it between different adsorption sites. We introduce a model taking into account the trade-off between tilt-induced charging and reduced van der Waals interactions, which provides a general framework for understanding charging-induced structural relaxation on weakly interacting substrates. In addition, we argue that the partial sp3 rehybridization of the underlying graphene and the possible bonding mechanism between the cyano groups and the graphene substrate are also relevant for the complete understanding of the experiments. These results provide insight into molecular charging on graphene, and they are directly relevant for potential device applications where the use of molecules has been suggested for doping and band structure engineering.",
keywords = "DFT, epitaxial graphene, FTCNQ, Ir(111), Kondo effect, self-assembly, STM",
author = "Avijit Kumar and Kaustuv Banerjee and Marc Dvorak and Fabian Schulz and Ari Harju and Patrick Rinke and Peter Liljeroth",
year = "2017",
month = "5",
day = "23",
doi = "10.1021/acsnano.7b01599",
language = "English",
volume = "11",
pages = "4960--4968",
journal = "ACS Nano",
issn = "1936-0851",
publisher = "AMERICAN CHEMICAL SOCIETY",
number = "5",

}

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TY - JOUR

T1 - Charge-Transfer-Driven Nonplanar Adsorption of F4TCNQ Molecules on Epitaxial Graphene

AU - Kumar, Avijit

AU - Banerjee, Kaustuv

AU - Dvorak, Marc

AU - Schulz, Fabian

AU - Harju, Ari

AU - Rinke, Patrick

AU - Liljeroth, Peter

PY - 2017/5/23

Y1 - 2017/5/23

N2 - π-conjugated organic molecules tend to adsorb in a planar configuration on graphene irrespective of their charge state. In contrast, here we demonstrate charging-induced strong structural relaxation of tetrafluorotetracyanoquinodimethane (F4TCNQ) on epitaxial graphene on Ir(111) (G/Ir(111)). The work function modulation over the graphene moiré unit cell causes site-selective charging of F4TCNQ. Upon charging, the molecule anchors to the face-centered cubic sites of the G/Ir(111) moiré through one or two cyano groups. The reaction is reversible and can be triggered on a single molecule by moving it between different adsorption sites. We introduce a model taking into account the trade-off between tilt-induced charging and reduced van der Waals interactions, which provides a general framework for understanding charging-induced structural relaxation on weakly interacting substrates. In addition, we argue that the partial sp3 rehybridization of the underlying graphene and the possible bonding mechanism between the cyano groups and the graphene substrate are also relevant for the complete understanding of the experiments. These results provide insight into molecular charging on graphene, and they are directly relevant for potential device applications where the use of molecules has been suggested for doping and band structure engineering.

AB - π-conjugated organic molecules tend to adsorb in a planar configuration on graphene irrespective of their charge state. In contrast, here we demonstrate charging-induced strong structural relaxation of tetrafluorotetracyanoquinodimethane (F4TCNQ) on epitaxial graphene on Ir(111) (G/Ir(111)). The work function modulation over the graphene moiré unit cell causes site-selective charging of F4TCNQ. Upon charging, the molecule anchors to the face-centered cubic sites of the G/Ir(111) moiré through one or two cyano groups. The reaction is reversible and can be triggered on a single molecule by moving it between different adsorption sites. We introduce a model taking into account the trade-off between tilt-induced charging and reduced van der Waals interactions, which provides a general framework for understanding charging-induced structural relaxation on weakly interacting substrates. In addition, we argue that the partial sp3 rehybridization of the underlying graphene and the possible bonding mechanism between the cyano groups and the graphene substrate are also relevant for the complete understanding of the experiments. These results provide insight into molecular charging on graphene, and they are directly relevant for potential device applications where the use of molecules has been suggested for doping and band structure engineering.

KW - DFT

KW - epitaxial graphene

KW - FTCNQ

KW - Ir(111)

KW - Kondo effect

KW - self-assembly

KW - STM

UR - http://www.scopus.com/inward/record.url?scp=85019934993&partnerID=8YFLogxK

U2 - 10.1021/acsnano.7b01599

DO - 10.1021/acsnano.7b01599

M3 - Article

VL - 11

SP - 4960

EP - 4968

JO - ACS Nano

JF - ACS Nano

SN - 1936-0851

IS - 5

ER -

ID: 13642930