The work in this dissertation consists of a two-part study concerning molecular-based electronics and atomic layer deposition (ALD). As conventional “top-down” silicon-based technology approaches its expected physical and technical limits, researchers have paid considerable attention to “bottom-up” approaches including molecular-based electronics that self assembles molecular components and ALD techniques that deposit thin films with atomic layer control.

Reliable fabrication of molecular-based devices and a lack of understanding of the conduction mechanisms through individual molecules still remain critical issues in molecular-based electronics. Nanoparticle/molecule(s)/nanoparticle assemblies of “dimers” and “trimers”, consisting of two and three nanoparticles bridged by oligomeric ethynylene phenylene molecules (OPEs), respectively, are successfully synthesized by coworkers and applied to contact nanogap electrodes (< 70 nm) fabricated by an angled metal evaporation technique. We demonstrate successful trapping of nanoparticle dimers across nanogap electrodes by dielectrophoresis at 2 VAC, 1 MHz, and 60 s. The structures can be maintained electrically connected for long periods of time, enabling time- and temperature-dependent current-voltage (I-V) characterization. Conduction mechanisms through independent molecules are investigated by temperature dependent I-V measurements. An Arrhenius plot of log (I) versus 1/T exhibits a change of slope at ∼1.5 V, indicating the transition from direct tunneling to Fowler-Nordheim tunneling. Monitoring of the conductance is also performed in real-time during trapping as well as during other modification and exposure sequences after trapping over short-term and long-term time scales. The real-time monitoring of conductance through dimer structures during trapping offers immediate detection of a specific fault which is ascribed to a loss of active molecules and fusing of the nanoparticles in the junction occurring mostly at a high applied voltage (≥3 VAC). After successful trapping, the sample exposure to air reveals a small rapid decrease in current, followed by a slower exponential increase, and eventual current saturation.

This work also reports on the dependence of electron transport on molecular length (2 to 4.7 nm) and structure (linear-type in dimers and Y-type in trimers). The extracted electronic decay constant of ∼0.12 Å^-1 and effective contact resistance of ∼4 MΩ indicate a strong electronic coupling between the chain ends, facilitating electron transport over long distances. A three terminal molecular transistor is also demonstrated with trimers trapped across nanogap electrodes. The source-drain current is modulated within a factor of 2 with a gate bias voltage of -2 to +2 V. A subthreshold slope of ∼110 mV/decade is obtained.

Finally, we report on both fundamental understanding and application of atomic layer deposition. First, in situ analysis tools such as quartz crystal microbalance and electrical conductance measurements are combined to reveal direct links between surface reactions, charge transfer, and dopant incorporation during ZnO and ZnO:Al ALD. Second, the ability of ALD to form uniform and conformal coating onto complex nanostructures is explored to improve the ambient stability of single molecules/nanoparticle assemblies using Al₂O₃ ALD as an encapsulation layer. In addition, the ability to shield the surface polarity of ZnO nanostructures using Al ₂O₃ + ZnO ALD, leading to hierarchical morphology evolution from one-dimensional ZnO nanorods to three-dimensional ZnO nanosheets with branched nanorods during hydrothermal growth is investigated.