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.

that residual gases in the electron beam evaporator were causing titanium oxide to form during titanium deposition. A lower back pressure and faster Ti deposition rate (4 × 10 -7 Torr and 0.1 nm/s) resulted in a significant change in the appearance of Figure 3, as shown below. XPS depth profiling showed the formation of Ti(II) and Ti(III) oxides using the previous conditions. These results imply that both a Ti/TiO x layer and the NAB/NAB -layer determine the electronic behavior of the junction.Current/voltage curves for PPF/NAB/Ti/Au junctions with Ti deposited under the original conditions (8 × 10 -6 Torr and 0.03 nm/s) and under "low oxide" conditions (4 × 10 -7 Torr and 0.1 nm/s). The scan rate was 1 V/s in both cases. See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

Pyrolyzed photoresist films (PPF) are introduced as planar carbon electrodes in a PDMS-quartz hybrid microchip device. The utility of PPF in electroanalytical applications is demonstrated by the separation and detection of various neurotransmitters. PPF is found to form a stable, low-capacitance, durable layer on quartz, which can then be used in conjunction with a microchip capillary electrophoretic device. Sinusoidal voltammetric detection at PPF electrodes is shown to be very sensitive, with a detection limit (S/N = 3) of 100 nM for dopamine, corresponding to a mass detection limit (S/N = 3) of 2 amol. The selectivity of analysis in the frequency domain is demonstrated by isolating each individual signal in a pair of analytes that are chromatographically unresolved. Effectively decoupling the electrophoresis and electrochemical systems allows the electrodes to be placed just inside the separation channel, which results in efficient separations (80 000-100 000 plates/m).