Integrated circuit (IC) technology has evolved rapidly but the continual development of transistors and interconnects (the connection between the transistors) is facing greater and greater challenges, which require new materials and new processes. Research in nano-particles (or nanoscale clusters) creates possibilities for both new materials and new processes. This thesis explores the electrical properties of amorphous antimony clusters and develops a new copper cluster deposition technique for application to transistors and interconnects respectively. For amorphous antimony clusters, an electron diffraction technique was applied to identify the phase of the clusters prior to deposition on electrically contacted samples. The deposition process produced uniform cluster films suitable for electrical measurements. A consistent percolation exponent for conduction (t=1.85) was obtained. After deposition, the resistance of the films continued to increase because of coalescence. Although it was previously reported that amorphous antimony films were semiconducting, from linear I(V) curves, a low temperature coefficient of resistance (10⁻⁴ K⁻¹) and no observable gate effect, it was found that the antimony cluster films in this study were not semiconducting, possibly due to the effect of coalescence. The development of the copper clusters for the interconnects application was very successful. Trenches of sub-200 nm widths, with different diffusion barriers and seed layers, and up to 5:1 aspect ratios have been completely filled with copper clusters. Due to the propensity for reflection of clusters from the planar surfaces between trenches, the process results in selective deposition into the trenches and bottom up filling is demonstrated. After annealing in hydrogen or in vacuum, the clusters sinter into a copper seed layer. The resistivity measured by a thin film four-point probe (1.6 - 2.3 × 10⁻⁸ Ωm) meets the requirement by industry (2.2 × 10⁻⁸ Ωm). The process is therefore promising for industrial application, but further testing and investigation of integration issues is required.

Inorganic nanoscale clusters have garnered significant interest for many practical applications within the fields of materials chemistry, inorganic chemistry, geochemistry, and environmental chemistry. However, the fundamental inner workings of how these materials interact in the solid state and solution continues to be a very elusive problem for scientists. My dissertation focuses on taking non-traditional approaches and characterization techniques to further understand the dynamic interactions of some of the aforementioned clusters. Chapter I is a comprehensive survey and perspective on selected characterization techniques used to study Group 13 aqueous nanoscale clusters and other polyoxometalates in solution. Chapter II focuses on utilizing Raman spectroscopy, infrared spectroscopy, and quantum mechanical computations to unambiguously identify Group 13 tridecameric species in the solid state and aqueous solution. Chapter III discusses the first instance of transmetalation of aqueous aluminum clusters via salt addition of In(NO3)3 in aqueous or methanol. Chapters IV and V explore the effects that aprotic and protic solvents can have on the solution speciation of the flat aluminum tridecamer. Chapter VI discusses the utility of using electrochemically synthesized gallium tridecamer and its functional use as a thin film semiconductor. Chapter VII describes a unique graduate level chemistry course designed to allow students to conduct and generate publication-worthy research within the timeframe of the course. Chapter VIII ventures out beyond the group 13 cluster and introduces techniques used to study the formation and stability of aqueous hafnium clusters. Chapter IX details the synthesis and characterization of rhombic structured copper clusters in the solid state. Finally, chapter X highlights my unfinished projects that can propel future research within the lab. This dissertation includes previously published and unpublished co-authored material.