High surface area tungsten oxynitride samples have been prepared by the temperature programmed reaction (TPR) of W0₃ with NH₃. All samples were characterized by X-ray diffraction (XRD), nitrogen physisorption, and CO chemisorption. In addition, some sample compositions were determined by elemental analysis. Samples were prepared at various heating rates (β), allowing a Redhead analysis to be carried out giving an activation energy of nitridation of 109 kJ mol⁻¹. A heating rate of 0.016 K S⁻¹ gave optimum synthesis conditions. Solid state intermediates were studied by interruption of the temperature program at various stages. No distinct suboxide phases formed along the synthesis path were found using XRD. An increase in surface area, CO uptake and nitrogen weight content, were found to occur as the reaction progressed. Reactivity experiments showed reasonable hydro deoxygenation (HDO) and hydrodenitrogenation (HDN) activities, but little hydrogenation (HYD) or hydrodesulfurization (HDS) activities. / Master of Science

The integration of copper (Cu) and dielectric materials has been outlined in the International Technology Roadmap for Semiconductors (ITRS) as a critical goal for future microelectronic devices. A necessity toward achieving this goal is the development of diffusion barriers that resolve the Cu and dielectric incompatibility. The focus of this research examines the potential use of tungsten nitride as a diffusion barrier by characterizing the interfacial properties with Cu and evaluating its process capability for industrial use. Tungsten nitride (β-W2N) development has been carried out using a plasma enhanced chemical vapor deposition (PECVD) technique that utilizes tungsten hexafluoride (WF6), nitrogen (N2), hydrogen (H2), and argon (Ar). Two design of experiments (DOE) were performed to optimize the process with respect to film stoichiometry, resistivity and uniformity across a 200 mm diameter Si wafer. Auger depth profiling showed a 2:1 W:N ratio. X-ray diffraction (XRD) showed a broad peak centered on the β-W2N phase. Film resistivity was 270 mohm-cm and film uniformity < 3 %. The step coverage (film thickness variance) across a structured etched dielectric (SiO2, 0.35 mm, 3:1 aspect ratio) was > 44 %. Secondary ion mass spectroscopy (SIMS) measurements showed good barrier performance for W2N between Cu and SiO2 with no intermixing of the Cu and silicon when annealed to 390o C for 3 hours. Cu nucleation behavior and thermal stability on clean and nitrided tungsten foil (WxN = δ-WN and β-W2N phases) have been characterized by Auger electron spectroscopy (AES) and thermal desorption spectroscopy (TDS) under controlled ultra high vacuum (UHV) conditions. At room temperature, the Auger intensity ratio vs. time plots demonstrates layer by layer Cu growth for the clean tungsten (W) surface and three-dimensional nucleation for the nitride overlayer. Auger intensity ratio vs. temperature measurements for the Cu/W system indicates a stable interface up to 1000 K. For the Cu /WxN/W system, initial Cu diffusion into the nitride overlayer is observed at 550 K.

The objective of this doctoral thesis is to develop, engineer and investigate an amorphous metal tungsten nitride (aWNx) and to study its functionality for applications focused on electromechanical system at the nano-scale. Charge transport based solid state device oriented complementary metal oxide semiconductor (CMOS) electronics have reached a level where they are scaled down to nearly their fundamental limits regarding switching speed, off state power consumption and the on state power consumption due to the fundamental limitation of sub-threshold slope (SS) remains at 60 mV/dec. NEM switch theoretically and practically offers the steepest sub-threshold slope and practically has shown zero static power consumption due to their physical isolation originated from the nature of their mechanical operation. Fundamental challenges remain with NEM switches in context of their performance and reliability: (i) necessity of lower pull-in voltage comparable to CMOS technology; (ii) operation in ambient/air; (iii) increased ON current and decreased ON resistance; (iv) scaling of devices and improved mechanical and electrical contacts; and (v) high endurance. The “perfect” NEM switch should overcome all the above-mentioned challenges. Here, we show such a NEM switch fabricated with aWNx to show (i) sub-0.3-volt operation; (ii) operation in air and vacuum; (iii) ON current as high as 0.5 mA and ON resistance lower than 5 kΩ; (iv) improved mechanical contact; and the most importantly (v) continuous switching of 8 trillion cycles for more than 10 days with the highest switching speed is 30 nanosecond without hysteresis. In addition, tungsten nitride could be the modern life vine by fulfilling the demand of biodegradable material for sustainable life regime. Transient electronics is a form of biodegradable electronics as it is physically disappearing totally or partially after performing the required function. The fabricated aWNx suites this category very well, despite not being a universal bio-element. It has been found that aWNx dissolves in ground water with a rate of ≈ 20-60 nm h-1. This means that a 100 nm thick aWNx disappears in ground water in less than a day and three days are enough to dissolve completely a 300 nm thickness device.

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