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Hafnium and Zirconium based gate dielectrics are considered potential candidates to replace SiO2 or SiON as the gate dielectric in CMOS processing. Furthermore, the addition of nitrogen into this pseudo-binary alloy has been shown to improve their thermal stability, electrical properties, and reduce dopant penetration. Because CMOS processing requires high temperature anneals (up to 1050 °C), it is important to understand the diffusion properties of any metal associated with the gate dielectric in silicon at these temperatures. In addition, dopant penetration from the doped polysilicon gate into the Si channel at these temperatures must also be studied. Impurity outdiffusion (Hf, Zr) from the dielectric, or dopant (B, As, P) penetration through the dielectric into the channel region would likely result in deleterious effects upon the carrier mobility. In this dissertation extensive thermal stability studies of alternate gate dielectric candidates ZrSixOy and HfSixOy are presented. Dopant penetration studies from doped-polysilicon through HfSixOy and HfSixOyNz are also presented. Rutherford backscattering spectroscopy (RBS), heavy ion RBS (HI-RBS), x-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (HR-TEM), and time of flight and dynamic secondary ion mass spectroscopy (ToF-SIMS, D-SIMS) methods were used to characterize these materials. The dopant diffusivity is calculated by modeling of the dopant profiles in the Si substrate. In this disseration is reported that Hf silicate films are more stable than Zr silicate films, from the metal interdiffusion point of view. On the other hand, dopant (B, As, and P) penetration is observed for HfSixOy films. However, the addition of nitrogen to the Hf - Si - O systems improves the dopant penetration properties of the resulting HfSixOyNz films.

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Electronic devices are used for tasks such as keeping people connected, figuring out the contents of a package or detecting impurities in the air. The use of electronic sensors in short life cycle products has also begun to increase with the field of smart packaging. For example, RFID tags are used everyday in sorting facilities to identify packages and then discarded when the packaging is thrown away. Every year the world generates millions of tons of E-waste and most of it is exported, incinerated, or put in landfills. To mitigate the impact of electronics on the environment, it is essential that the next generation of disposable electronic devices are fabricated using environmentally friendly materials. For these materials to be considered for high throughput fabrication they need to be solution processable and biodegradable, all while having the necessary mechanical and electrical properties. This thesis focuses on the development of novel environmentally friendly dielectrics that can be used in capacitors and thin film transistors. A common environmentally friendly and biodegradable material used as a polymer dielectric is poly(vinyl alcohol) (PVA). Although PVA has a high capacitance it also has its drawbacks. Being mostly processed from aqueous solutions it is hard to form uniform thin films of PVA and it is sensitive to moisture which changes its capacitance. PVA is also a polar material which can cause charge trapping at the semiconductor/dielectric interface when used as a dielectric in the fabrication of organic thin film transistors (OTFTs). In this thesis we use different strategies such as blending dielectrics and stacking them to help improve the performance of PVA as a dielectric in OTFTs. In the first study, I demonstrate how low weight percentages of cellulose nanocrystals can be used to increase the viscosity of PVA without negatively impacting its dielectric properties. This led to better film uniformity and a larger number of functioning OTFTs. The second study focused on using a toluene diisocyanate terminated polycaprolactone (TPCL) polymer as a low-k barrier between PVA and the semiconductor. The TPCL led to an increase in OTFT performance and a large reduction in moisture sensitivity. For the third study, I improved the shelf life of the TPCL materials by replacing the toluene diisocyanate end units with UV crosslinking end units. The UV end units were protected unlike the TPCL end units allowing the polymer to remain stable under ambient conditions. The UV-PCL demonstrates similar resistance to moisture and dielectric properties to TPCL while being more stable and easier to use in traditional printing processes. My last study, investigates the use of a poly(lactic acid) (PLA) layer as a third layer in the TPCL/PVA/PLA dielectric system. The PLA layer acted as an intermediate between the substrate and PVA increasing the adhesion of PVA. Further the PLA layer improved OTFT performance and allowed for n-type single walled carbon nanotube transistors under ambient conditions. Finally, this work has demonstrated ways to improve the performance of PVA so that it can be used as an environmentally friendly dielectric in thin film, flexible and printed electronic applications.