14 research outputs found
Molecule-Electrode Interface Energetics in Molecular Junction: a Transition Voltage Spectroscopy Study
We assess the performances of the transition voltage spectroscopy (TVS)
method to determine the energies of the molecular orbitals involved in the
electronic transport though molecular junctions. A large number of various
molecular junctions made with alkyl chains but with different chemical
structure of the electrode-molecule interfaces are studied. In the case of
molecular junctions with clean, unoxidized electrode-molecule interfaces, i.e.
alkylthiols and alkenes directly grafted on Au and hydrogenated Si,
respectively, we measure transition voltages in the range 0.9 - 1.4 V. We
conclude that the TVS method allows estimating the onset of the tail of the
LUMO density of states, at energy located 1.0 - 1.2 eV above the electrode
Fermi energy. For oxidized interfaces (e.g. the same monolayer measured with Hg
or eGaIn drops, or monolayers formed on a slightly oxidized silicon substrate),
lower transition voltages (0.1 - 0.6 V) are systematically measured. These
values are explained by the presence of oxide-related density of states at
energies lower than the HOMO-LUMO of the molecules. As such, the TVS method is
a useful technique to assess the quality of the molecule-electrode interfaces
in molecular junctions.Comment: Accepted for publication in J. Phys. Chem C. One pdf file including
manuscript, figures and supporting informatio