Carbon/molecule/metal molecular electronic junctions: the importance of "contacts".

Molecular electronic junctions fabricated by covalent bonding onto a graphitic carbon substrate were examined with Raman spectroscopy and characterized electronically. The molecular layer was a 4.5 nm thick multilayer of nitroazobenzene (NAB), and the top contact material was varied to investigate its effect on junction behavior. A 3.0 nm thick layer of copper, TiO2, or Al(III) oxide (AlO(x)) was deposited on top of the NAB layer, followed by a 7.0 nm thick layer of gold. Copper "contacts" yielded molecular junctions with low resistance and showed a strong dependence on molecular structure. Carbon/ NAB/AlO(x)/Au junctions exhibited high resistance, with current densities three orders of magnitude less than those for analogous Cu junctions. However, Raman spectroscopy revealed that the NAB layer was reduced when the carbon substrate was biased negative, to a product resembling that resulting from electrochemical reduction of NAB. Carbon/ NAB/TiO2/Au junctions showed rectifying J/V behavior, with high conductivity to electrons able to enter the TiO2 conduction band. Substitution of azobenzene for nitroazobenzene yielded junctions with similar spectroscopic and electronic behavior to NAB, indicating that the nitro group is not essential for rectification. The results are interpreted in terms of the energy levels of the molecule relative to those of TiO2. The combination of a covalently bonded molecular layer and a semiconducting oxide yields unusual electronic properties in a carbon/molecule/semiconductor/Au molecular junction.

In situ Raman spectroscopy of bias-induced structural changes in nitroazobenzene molecular electronic junctions.

Carbon/nitroazobenzene (NAB)/titanium/gold molecular electronic junctions with active thicknesses of 7-8 nm were constructed having partially transparent Ti/Au top contacts, which permitted in situ monitoring of molecular structure with Raman spectroscopy for applied biases between +3 and -3 V. Deposition of the Ti/Au top contacts resulted in spectral changes similar to those accompanying NAB reduction in a conventional spectroelectrochemical experiment. Upon application of +3 V (carbon relative to Ti), the spectrum indicated reoxidation of the NAB reduction product, and this redox cycle could be repeated at least three times. When a voltage excursion to -2 or -3 V occurred, the spectra indicated irreversible loss of the nitro group, and a dramatic but reversible decrease in Raman intensity over the entire shift range examined. Negative applied voltage causes formation of reduced NAB and a high oxidation state of titanium, while positive voltage forms oxidized NAB and injects electrons into the titanium oxide layer. The spectral changes were correlated with current/voltage curves in order to probe the mechanism of rectification and conductance switching reported previously. Overall, the combination of spectroscopic and voltammetric results implies a conduction mechanism involving both NAB and titanium oxide, possibly mediated by the injection of carriers into the semiconducting titanium oxide, or by reduction of an insulating titanium oxide to a more conductive form.

Ultraflat carbon film electrodes prepared by electron beam evaporation.

A facile method for the preparation of thin-film carbon electrodes by electron beam evaporation onto highly doped silicon is presented. The physical and electrochemical properties of these films both before and after postdeposition pyrolysis are investigated. Raman spectroscopy establishes the amorphous structure of the nonpyrolyzed carbon films and confirms the formation of graphitic carbon after pyrolysis at 1000 degrees C. Scanning force microscopy reveals the root-mean-square roughness of nonpyrolyzed films to be approximately 1 A, while pyrolyzed films exhibit an increased roughness of approximately 4 A. The electrochemical behavior of the electrodes resembles glassy carbon, with measured heterogeneous electron-transfer rate constants among the highest measured for thin carbon films. These carbon film electrodes will potentially find applications in such fields as molecular electronics and scanning probe microscopy of adsorbed species.

Characterization of carbon/nitroazobenzene/titanium molecular electronic junctions with photoelectron and Raman spectroscopy.

Molecular junctions consisting of nitroazobenzene (NAB) chemisorbed to a substrate of pyrolyzed photoresist film (PPF) and a top contact of vapor-deposited titanium were examined with Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). The thickness of the NAB layer varied from submonolayer to 4.5 nm, and a thin (1-3 nm) overlayer of Ti was deposited by electron beam deposition. Without Ti, the NAB surface Raman spectrum was sufficiently strong to observe previously unreported modes in the 500-1000-cm(-1) region, and the 1000-1700-cm(-1) region was sufficiently strong to observe the effects of metal deposition. Upon Ti deposition, the intensities of NAB modes associated with the nitro group decreased significantly, and the XPS indicated formation of a Ti-N bond. For the thicker NAB layers (1.9 and 4.5 nm), the intensities of the NO(2) Raman modes partially recovered over a several-day period, but they remain depressed or absent in the submonolayer sample. The results indicate a reaction between condensing Ti atoms and the terminal NO(2) group, probably to form a Ti-nitroso linkage between NAB and Ti. The result is a molecular junction with covalent bonding at both ends in the form of a C-C bond between PPF and NAB and a Ti-N bond to the top contact. The structural implications of the current results are interpreted in the context of recently reported functioning PPF/NAB/Ti molecular electronic junctions. In particular, the reaction between Ti and the nitro group appears to prevent short circuits resulting from incursion of Ti into the NAB layer.

Molecular rectification and conductance switching in carbon-based molecular junctions by structural rearrangement accompanying electron injection.

Molecular junctions were fabricated consisting of a 3.7 nm thick layer of nitroazobenzene (NAB) molecules between a pyrolyzed photoresist substrate (PPF) and a titanium top contact which was protected from oxidation by a layer of gold. Raman spectroscopy, XPS, and AFM revealed that the NAB layer was 2-3 molecules thick and was bonded to the two conducting contacts by C-C and N-Ti covalent bonds. The current/voltage behavior of the PPF/NAB(3.7)/Ti junctions showed strong and reproducible rectification, with the current at +2 V exceeding that at -2 V by a factor of 600. The observed current density at +3 V was 0.71 A/cm(2), or about 10(5) e(-)/s/molecule. The i/V response was strongly dependent on temperature and scan rate, with the rectification ratio decreasing for lower temperature and faster scans. Junction conductivity increased with time over several seconds at room temperature in response to positive voltage pulses, with the rate of increase larger for more positive potentials. Voltage pulses to positive potentials and back to zero volts revealed that electrons are injected from the Ti to the NAB, to the extent of about 0.1-1 e(-)/molecule for a +3 V pulse. These electrons cause an activated transition of the NAB into a more conductive quinoid state, which in turn causes an increase in conductivity. The transition to the quinoid state involves nuclear rearrangement which occurs on a submillisecond to several second time scale, depending on the voltage applied. The quinoid state is stable as long as the applied electric field is present, but reverts back to NAB within several minutes after the field is relaxed. The results are interpreted in terms of a thermally activated, potential dependent electron transfer into the 3.7 nm NAB layer, which brings about a conductivity increase of several orders of magnitude.