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Zgrabik, Christine

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Zgrabik

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Zgrabik, Christine

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    Wide Tunability of Magnetron Sputtered Titanium Nitride and Titanium Oxynitride for Plasmonic Applications
    (2016-05-17) Zgrabik, Christine; Hu, Evelyn; Clarke, David; Loncar, Marko
    Transition metal nitrides have recently garnered much interest as alternative materials for robust plasmonic device architecture including potential applications in solar absorbers, photothermal medical therapy, and heat-assisted magnetic recording. Titanium nitride (TiN) is one such potential candidate. One advantage of the transition metal nitrides is that their optical properties are tunable according to the deposition conditions. The controlled achievement of tunability, however, is also a challenge. Although the formation of TiN has been the subject of numerous previous studies, a thorough analysis of the deposition parameters necessary to form metallic TiN films optimized for plasmonic applications had not been demonstrated. Similarly, such TiN films had not been subjected to detailed optical measurements which could be used in FDTD device simulations to optimize plasmonic device designs. To be able to design, simulate and build robust and optimal device structures, in this work a systematic and thorough examination of the effect of varied substrates, temperatures, and reactive gas compositions on magnetron sputtered TiN was conducted. In addition, the effects of application of an additional substrate bias were studied. The resulting optical properties at visible to near-infrared frequencies were the focus of this thesis. The optical properties of each film were measured via spectroscopic ellipsometry with more "metallic” films demonstrating a larger negative value of the real part of the permittivity. These optical measurements were correlated with both the films’ deposition conditions and microstructural measurements including x-ray photoelectron spectroscopy (XPS), x-ray diffraction (XRD), and transmission electron microscopy (TEM) measurements; the different deposition conditions resulted in TiN and TiOxNy films with widely tunable optical responses. By sputtering under different conditions, the value of the real part of the permittivity was tuned from small positive values, through small and moderate negative values, and finally all of the way to large negative values which are comparable to those measured in gold. It was determined that both the chemical composition as well as the film crystallinity had a significant effect on the resulting properties with the most metallic films in general exhibiting a Ti:N ratio close to 1:1, low oxygen incorporation, more N bound as TiN rather than in oxynitride form, and better crystallinity. Increased substrate temperature in general increased the metallic character while application of a substrate bias reduced crystalline order, however also reduced oxygen incorporation and allowed for deposition of metallic TiN at room temperature. The close lattice match of TiN and MgO allowed for heteroepitaxial growth on this substrate under carefully controlled conditions. Finally, to demonstrate the viability of the optimized TiN thin films for plasmonic applications, three benchmark plasmonic structures were simulated using the measured, optimized optical properties including a plasmonic grating coupler, infrared nanoantennas, and a nanopyramidal array. The devices were successfully fabricated and preliminary measurements show promise for plasmonic applications for example in solar conversion and photothermal medical therapy.