Engineering thin films of magnetic alloys and semiconductor oxides at the nanoscale

The thesis aims to exploit properties of thin films for applications such as spintronics, UV detection and gas sensing. Nanoscale thin films devices have myriad advantages and compatibility with Si-based integrated circuits processes. Two distinct classes of material systems are investigated, namely ferromagnetic thin films and semiconductor oxides. To aid the designing of devices, the surface properties of the thin films were investigated by using electron and photon characterization techniques including Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), grazing incidence X-ray diffraction (GIXRD), and energy-dispersive X-ray spectroscopy (EDS). These are complemented by nanometer resolved local proximal probes such as atomic force microscopy (AFM), magnetic force microscopy (MFM), electric force microscopy (EFM), and scanning tunneling microscopy to elucidate the interplay between stoichiometry, morphology, chemical states, crystallization, magnetism, optical transparency, and electronic properties. Specifically, I studied the effect of annealing on the surface stoichiometry of the CoFeB/Cu system by in-situ AES and discovered that magnetic nanoparticles with controllable areal density can be produced. This is a good alternative for producing nanoparticles using a maskless process. Additionally, I studied the behavior of magnetic domain walls of the low coercivity alloy CoFeB patterned nanowires. MFM measurement with the in-plane magnetic field showed that, compared to their permalloy counterparts, CoFeB nanowires require a much smaller magnetization switching field , making them promising for low-power-consumption domain wall motion based devices. With oxides, I studied CuO nanoparticles on SnO2 based UV photodetectors (PDs), and discovered that they promote the responsivity by facilitating charge transfer with the formed nanoheterojunctions. I also demonstrated UV PDs with spectrally tunable photoresponse with the bandgap engineered ZnMgO. The bandgap of the alloyed ZnMgO thin films was tailored by varying the Mg contents and AES was demonstrated as a surface scientific approach to assess the alloying of ZnMgO. With gas sensors, I discovered the rf-sputtered anatase-TiO2 thin films for a selective and sensitive NO2 detection at room temperature, under UV illumination. The implementation of UV enhances the responsivity, response and recovery rate of the TiO2 sensor towards NO2 significantly. Evident from the high resolution XPS and AFM studies, the surface contamination and morphology of the thin films degrade the gas sensing response. I also demonstrated that surface additive metal nanoparticles on thin films can improve the response and the selectivity of oxide based sensors. I employed nanometer-scale scanning probe microscopy to study a novel gas senor scheme consisting of gallium nitride (GaN) nanowires with functionalizing oxides layer. The results suggested that AFM together with EFM is capable of discriminating low-conductive materials at the nanoscale, providing a nondestructive method to quantitatively relate sensing response to the surface morphology.

Advanced Analytical Microscopy at the Nanoscale: Applications in Wide Bandgap and Solid Oxide Fuel Cell Materials

The atomic-level structure and chemistry of materials ultimately dictate their observed macroscopic properties and behavior. As such, an intimate understanding of these characteristics allows for better materials engineering and improvements in the resulting devices. In our work, two material systems were investigated using advanced electron and ion microscopy techniques, relating the measured nanoscale traits to overall device performance. First, transmission electron microscopy and electron energy loss spectroscopy (TEM-EELS) were used to analyze interfacial states at the semiconductor/oxide interface in wide bandgap SiC microelectronics. This interface contains defects that significantly diminish SiC device performance, and their fundamental nature remains generally unresolved. The impacts of various microfabrication techniques were explored, examining both current commercial and next-generation processing strategies. In further investigations, machine learning techniques were applied to the EELS data, revealing previously hidden Si, C, and O bonding states at the interface, which help explain the origins of mobility enhancement in SiC devices. Finally, the impacts of SiC bias temperature stressing on the interfacial region were explored. In the second system, focused ion beam/scanning electron microscopy (FIB/SEM) was used to reconstruct 3D models of solid oxide fuel cell (SOFC) cathodes. Since the specific degradation mechanisms of SOFC cathodes are poorly understood, FIB/SEM and TEM were used to analyze and quantify changes in the microstructure during performance degradation. Novel strategies for microstructure calculation from FIB-nanotomography data were developed and applied to LSM-YSZ and LSCF-GDC composite cathodes, aged with environmental contaminants to promote degradation. In LSM-YSZ, migration of both La and Mn cations to the grain boundaries of YSZ was observed using TEM-EELS. Few substantial changes however, were observed in the overall microstructure of the cells, correlating with a lack of performance degradation induced by the H2O. Using similar strategies, a series of LSCF-GDC cathodes were analyzed, aged in H2O, CO2, and Cr-vapor environments. FIB/SEM observation revealed considerable formation of secondary phases within these cathodes, and quantifiable modifications of the microstructure. In particular, Cr-poisoning was observed to cause substantial byproduct formation, which was correlated with drastic reductions in cell performance.