116 research outputs found

    Molecule-Electrode Interface Energetics in Molecular Junction: a Transition Voltage Spectroscopy Study

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    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

    High on-off conductance switching ratio in optically-driven self-assembled conjugated molecular systems

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    A new azobenzene-thiophene molecular switch is designed, synthesized and used to form self-assembled monolayers (SAM) on gold. An "on/off" conductance ratio up to 7x1E3 (with an average value of 1.5x1E3) is reported. The "on" conductance state is clearly identified to the cis isomer of the azobenzene moiety. The high "on/off" ratio is explained in terms of photo-induced, configuration-related, changes in the electrode-molecule interface energetics (changes in the energy position of the molecular orbitals with respect to the Fermi energy of electrodes) in addition to changes in the tunnel barrier length (length of the molecules). First principles DFT calculations demonstrate a better delocalization of the frontier orbitals, as well as a stronger electronic coupling between the azobenzene moiety and the electrode for the cis configuration over the trans one. Measured photoionization cross-sections for the molecules in the SAM are close to the known values for azobenzene derivatives in solution.Comment: 1 file with main text, figure and suppementary informatio

    σ-π molecular dielectric multilayers for low-voltage organic thin-film transistors

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    Very thin (2.3-5.5 nm) self-assembled organic dielectric multilayers have been integrated into organic thin-film transistor structures to achieve sub-1-V operating characteristics. These new dielectrics are fabricated by means of layer-by-layer solution phase deposition of molecular silicon precursors, resulting in smooth, nanostructurally well defined, strongly adherent, thermally stable, virtually pinhole-free, organosiloxane thin films having exceptionally large electrical capacitances (up to ≈2,500 nF·cm(-2)), excellent insulating properties (leakage current densities as low as 10(-9) A·cm(-2)), and single-layer dielectric constant (k)of ≈16. These 3D self-assembled multilayers enable organic thin-film transistor function at very low source-drain, gate, and threshold voltages (<1 V) and are compatible with a broad variety of vapor- or solution-deposited p- and n-channel organic semiconductors
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