Permanent dielectric materials are integral to the fabrication of microelectronic devices and packaging. Dielectrics are used throughout devices to electrically and mechanically isolate conductive components. As such, they are required to have low electrical permittivity and robust mechanical properties. For packaging applications, dielectrics can be directly photo-definable. Dielectrics need to have excellent lithographic properties. These properties are pivotal for enabling high yield and low cost fabrication of reliable, energy efficient devices. The aim of this work was to develop new positive tone dielectrics which have improved or application-specific lithographic, mechanical, and electrical properties. To this end, several new dielectric polymers and chemistries were evaluated and characterized. Initially, it was desired to develop a positive tone, polynorbornene (PNB) dielectric that utilizes diazonaphthoquinone (DNQ) photochemistry. Cross-linking was achieved with epoxy cross-linkers during a thermal cure. Several DNQ-containing compounds were evaluated, but only one had good miscibility with PNB. The dissolution characteristics of PNB were measured with respect to polymer composition, DNQ loading, and cross-linker loading. PNB films exhibited unique dissolution properties, and these measurements allowed for an optimum formulation to be developed. A formulation with 20 pphr DNQ and 10 pphr epoxy cross-linker had sufficient inhibition in unexposed regions and fast dissolution in exposed regions. The resulting dielectric was the first positive tone, DNQ-based PNB dielectric. After achieving photo-definability, the cross-linking of the cured dielectric was evaluated by characterizing the mechanical properties. It was discovered that DNQ acted as a cross-linker in these films, and this insight was key to achieving good curing of the dielectric. Several experiments were performed to support this conclusions, and the reaction kinetics of this cross-linking reaction were evaluated. This effort produced a functional, positive tone dielectric with a sensitivity of 408 mJ cm-2 and contrast of 2.3. The modulus was 2.0 to 2.6 GPa and the dielectric constant of 3.7 to 3.9, depending on the curing conditions. The DNQ cross-linking results led to the investigation of other cross-linking chemistries for positive tone dielectrics. A chemically amplified (CA) photochemistry was utilized along with a Fischer esterification cross-linking reaction. Patterning and cross-linking were demonstrated with a methacrylate polymer. Successful positive tone lithography was demonstrated at a high sensitivity of 32.4 mJ cm-2 and contrast of 5.2. Cross-linking was achieved at 120°C as shown by residual stress and solubility measurements. The CA photochemistry and Fischer esterification cross-linking were also demonstrated using a PNB dielectric, which was shown to have improved lithographic properties: a sensitivity of 8.09 mJ cm-2 and contrast of ≥ 14.2. Work was performed to evaluate the effect of the polymer composition on the mechanical and electrical properties. A polymer with 60 mol% hexafluoroisopropanol norbornene and 40 mol% tert-butyl ester norbornene exhibited a dielectric constant of 2.78, which is lower than existing positive tone dielectrics. It also outperformed existing dielectrics in several other categories, including dark erosion, volume change, cure temperature, and in-plane coefficient of thermal expansion. However, a limitation of this dielectric was cracking in thick films. The final study was to improve the mechanical properties of this CA PNB dielectric specifically to enable 5 µm thick films. First, a terpolymer was tested that included a non-functional third monomer. The dielectric constant increased to 3.48 with 24 mol% of the third monomer. Second, low molecular weight additives were used to lower the modulus. Only one of the five tested additives enabled high quality, thick films. This additive did not significantly affect the dielectric constant at low loadings. An optimized formulation was made, and processing parameters were studied. The additive decreased the lithographic properties, lowering the sensitivity to 175 mJ cm-2 and lowering the contrast to 4.36. In all, this work produced three functional dielectrics with positive tone photo-definability and good lithographic properties. Each dielectric can serve a variety of purposes in microelectronics packaging.

Silicon and silicon-based materials have been investigated for the fabrication of electronic, optoelectronic, solar, and structural/mechanical devices. To enable the continuous use of silicon-based materials for next generation device applications, new and inexpensive ways of fabricating features of silicon, and silica-based materials are needed. This dissertation investigates: 1) novel techniques for the fabrication of silica and silicon nanofeatures with potential application in the electronics and optoelectronics industry; 2) new designs of photomodifiable material systems (resists) for maskless patterning of silica filled composites for structural/mechanical applications. Sub-micron and nano-scaled features were fabricated onto silicon and silicon oxide substrates using a technique combining block copolymers and laser interference ablation. The sacrificial block copolymers are loaded with metallic salt precursors and patterned with a UV laser to generate device-oriented nanofeatures. New photopolymerizable material systems (negative tone resists) were developed based on curcumin photosensitizer and an epoxy-acrylate, vinylether, and vinylether-acrylate silica¬-loaded material systems. The cationic and radical mechanisms employed by the monomeric systems under a high vapor pressure mercury lamp source were investigated with several materials characterization techniques.

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