Molecular adsorbates as probes of the local properties of doped graphene.
Graphene-based sensors are among the most promising of graphene's applications. The ability to signal the presence of molecular species adsorbed on this atomically thin substrate has been explored from electric measurements to light scattering. Here we show that the adsorbed molecules can be used to sense graphene properties. The interaction of porphyrin molecules with nitrogen-doped graphene has been investigated using scanning tunneling microscopy and ab initio calculations. Molecular manipulation was used to reveal the surface below the adsorbed molecules allowing to achieve an atomic-scale measure of the interaction of molecules with doped graphene. The adsorbate's frontier electronic states are downshifted in energy as the molecule approaches the doping site, with largest effect when the molecule sits over the nitrogen dopant. Theoretical calculations showed that, due to graphene's high polarizability, the adsorption of porphyrin induces a charge rearrangement on the substrate similar to the image charges on a metal. This charge polarization is enhanced around nitrogen site, leading to an increased interaction of molecules with their image charges on graphene. Consequently, the molecular states are stabilized and shift to lower energies. These findings reveal the local variation of polarizability induced by nitrogen dopant opening new routes towards the electronic tuning of graphene.
MPQ, Université Paris Diderot-Paris 7, Sorbonne Paris Cité, CNRS, UMR 7162, 10, rue A. Domon et L. Duquet, 75205 Paris 13, France.
Van Dong
VD
Pham
Research Center in Physics of Matter and Radiation (PMR), Université de Namur, 61 Rue de Bruxelles, 5000 Namur, Belgium.
Frédéric
F
Joucken
MPQ, Université Paris Diderot-Paris 7, Sorbonne Paris Cité, CNRS, UMR 7162, 10, rue A. Domon et L. Duquet, 75205 Paris 13, France.
Vincent
V
Repain
MPQ, Université Paris Diderot-Paris 7, Sorbonne Paris Cité, CNRS, UMR 7162, 10, rue A. Domon et L. Duquet, 75205 Paris 13, France.
Cyril
C
Chacon
MPQ, Université Paris Diderot-Paris 7, Sorbonne Paris Cité, CNRS, UMR 7162, 10, rue A. Domon et L. Duquet, 75205 Paris 13, France.
Amandine
A
Bellec
MPQ, Université Paris Diderot-Paris 7, Sorbonne Paris Cité, CNRS, UMR 7162, 10, rue A. Domon et L. Duquet, 75205 Paris 13, France.
Yann
Y
Girard
MPQ, Université Paris Diderot-Paris 7, Sorbonne Paris Cité, CNRS, UMR 7162, 10, rue A. Domon et L. Duquet, 75205 Paris 13, France.
Sylvie
S
Rousset
Research Center in Physics of Matter and Radiation (PMR), Université de Namur, 61 Rue de Bruxelles, 5000 Namur, Belgium.
Robert
R
Sporken
Instituto de Física Universidade de São Paulo 05508-090, São Paulo, SP, Brazil.
Maria Cristina
MC
dos Santos
MPQ, Université Paris Diderot-Paris 7, Sorbonne Paris Cité, CNRS, UMR 7162, 10, rue A. Domon et L. Duquet, 75205 Paris 13, France.
Jérôme
J
Lagoute