Thesis (Ph. D.)--University of Texas at Austin, 2005. / Vita. Includes bibliographical references.

Thesis (Ph. D.)--University of Texas at Austin, 2004. / Supervisor: Jack C. Lee. Vita. Includes bibliographical references.

Thesis (Ph. D.)--University of Texas at Austin, 2004. / Supervisor: Jack C. Lee. Vita. Includes bibliographical references.

Thesis (Ph. D.)--University of Texas at Austin, 2007. / Vita. Includes bibliographical references.

The material class of hafnium oxide-based ferroelectrics adds an unexpected and huge momentum to the long-known phenomenon of pyroelectricity. In this thesis, a comprehensive study of pyroelectric and electrocaloric properties of this novel ferroelectric material class is conducted. hafnium oxide is a lead-free, non-toxic transition metal oxide, and abundant in the manufacturing of semiconductor devices. The compatibility to existing fabrication processes spawns the possibility of on-chip infrared sensing, energy harvesting, and refrigeration solutions, for which this dissertation aims to lay a foundation. A screening of the material system with respect to several dopants reveals an enhanced pyroelectric response at the morphotropic phase boundary between the polar orthorhombic and the non-polar tetragonal phase. Further, a strong pyroelectric effect is observed when applying an electric field to antiferroelectric-like films, which is attributed to a field-induced transition between the tetragonal and orthorhombic phases. Primary and secondary pyroelectric effects are separated using high-frequency temperature cycles, where the effect of frequency-dependent substrate clamping is exploited. The piezoelectric response is determined by comparing primary and secondary pyroelectric coefficients, which reproduces the expected wake-up behavior in hafnium oxide films. Further, the potential of hafnium oxide for thermal-electric energy conversion is explored. The electrocaloric temperature change of only 20 nm thick films is observed directly by using a specialized test structure. By comparing the magnitude of the effect to the pyroelectric response, it is concluded that defect charges have an important impact on the electrocaloric effect in hafnium oxide-based ferroelectrics. Energy harvesting with a conformal hafnium oxide film on a porous, nano-patterned substrate is performed, which enhances the power output. Further, the integration of a pyroelectric energy harvesting device in a microchip for waste heat recovery and more energy-efficient electronic devices is demonstrated. High dielectric breakdown fields of up to 4 MV/cm in combination with a sizable pyroelectric response and a comparably low dielectric permittivity illustrate the prospect of hafnium oxide-based devices for future energy conversion applications.

<p>As a scalable and CMOS compatible novel ferroelectric material, the ferroelectric HZO thin film has been the promising material for various applications and continues to attract the attention of researchers. Achieving strong ferroelectricity and fast switching speed in ultrathin FE HZO film are crucial challenges for its applications towards scaled devices.</p> <p>The ferroelectric and anti-ferroelectric properties of HZO are investigated systematically down to 3 nm. The ferroelectric polarization, switching speed and the impact of ALD tungsten nitride electrodes are studied. Record high Pr on FE HZO and record high PS on AFE HZO are achieved with WN electrodes, especially in ultrathin sub-10 nm regime. The polarization switching speed of FE and AFE HZO, associated with C-V frequency dispersion, are also qualitatively studied. On the other side of the scaling limit, ferroelectric/dielectric stack superlattice structure is found to enhance the ferroelectricity in thick films which would have severely degraded.</p> <p>Ultrafast direct measurement on the transient ferroelectric polarization switching is used to study the switching speed in FE HZO with a crossbar MFM structure. Sub-nanosecond characteristic switching time of 925 ps was achieved, supported by the nucleation limited switching model. The impact of electric field, film thickness and device area on the polarization switching speed is systematically studied. The ferroelectric switching speed is significantly improved compared to previous reports and more importantly is approaching GHz regime, suggesting FE HZO to be competitive in high-speed non-volatile memory technology. Record fast polarization switch speed of 360 ps is obtained in sub-μm crossbar array FE HZO MFM devices. It also unveils that domain wall propagation speed in HZO is the limiting factor for switch speed and more aggressively scaled devices will offer much faster switch speed.</p> <p>The first experimental determination of nucleation time and domain wall (DW) velocity by studying switching dynamics of ferroelectric (FE) hafnium zirconium oxide (HZO) was performed. Experimental data and simulation results were used to quantitatively study the switching dynamics. The switching speed is degraded in high aspect ratio devices due to the longer DW propagation time or with dielectric interfacial layer due to the required additional tunneling and trapping time by the leakage current assist switch mechanism.</p>

No description available.

The unprecedented ability of plasmonic metal nano-structures to concentrate light into deep-subwavelength volumes has propelled their use in a vast array of nanophotonics technologies and research endeavors. They are used in sensing, super-resolution imaging, SPP lithography, SPP assisted absorption, SPP-based antennas, light manipulation, etc. To take full advantage of the attractive capabilities of CMOS compatible low-cost plasmonic structures based on Al and Cu, nanolaminate coatings are investigated to improve their long-term stability in corrosive physiological environments. The structures are fabricated using phase-shifting PDMS masks, e-beam deposition, RIE, Atomic Layer Deposition and Rapid Thermal Annealing. An alternate approach using Nanosphere Lithography (NSL) was also investigated. Films were examined using ellipsometry, atomic force microscopy and transmission measurements. Accelerated in-situ tests of Hafnium Oxide/Aluminum Oxide nanolaminate shells in a mildly pH environment with temperatures akin to physiological environments emulated using PBS show greatly enhanced endurance, with stable structures that last for more than one year. / Master of Science / When light (electromagnetic radiation) interacts with the free (conduction) electrons of a metallic nanostructure it leads to a coupling resulting in collective excitations (oscillations) that lead to strong enhancements of the local electromagnetic fields surrounding the nanoparticles, this phenomenon is called Localized Surface Plasmon Resonance (LSPR) and plasmonics are structures that are capable of exhibiting this phenomenon. The condition for LSPR to occur is that the dimension scale of the structure is less than the wavelength of the electromagnetic radiation interacting with it. This implies that the structure has to be in nanoscale dimensions. LSPR based plasmonic structures are compact, sensitive and can be integrated with electronic devices and can be used in various applications like implantable biological sensors (blood pH sensing, diabetics sensing, etc.), devices that integrate several laboratory testing functionalities on a single chip, studies to determine the dynamics of chemical reactions, increasing the efficiency of solar power generation, etc. LSPR is exhibited by metallic nano-particles like gold, silver, copper and aluminum. Metals like copper corrode at a rapid rate in water at room temperature and hence nano scale structures made from them that can exhibit LSPR cannot be used in higher temperature ionic environments without a protective coating. High density, uniform coatings with less defect density can be deposited using Atomic layer deposition (ALD). In this research Atomic Layer Deposited Aluminum Oxide and Hafnium Oxide nanolaminate structures are explored to increase the long-term stability of plasmonic structures in physiological solutions. In-situ tests are carried out in a Phosphate-buffered Saline (PBS) solution with a pH value of 7.2 (simulating physiological conditions) at a temperature of 37℃ (physiological temperature) and 85.1℃ (accelerated testing). The results demonstrate that the dielectric nano coatings investigated in this project can increase the stability of the plasmonic structures in the corrosive physiological environment from a few days to more than one year.

<p>Due to the constantly decreasing dimensions of electronic devices, the conventional dielectric material in transistors and capacitors, SiO₂, has to be replaced by a material with higher dielectric constant. Some of the most promising candidates are tantalum oxide,Ta₂O₅, zirconium oxide, ZrO₂ and hafnium oxide, HfO₂.</p><p>This thesis describes new chemical vapour deposition (CVD) and atomic layer deposition (ALD) processes for deposition of Ta₂O₅, ZrO₂ and HfO₂ using the metal iodides as starting materials. The layer-by-layer growth in ALD was also studied in real time with a quartz crystal microbalance (QCM) to examine the process characteristics and to find suitable parameters for film deposition.</p><p>All the processes presented here produced high-purity films at low deposition temperatures. It was also found that films deposited on Pt substrates generally crystallise at lower temperature, or with lower thickness, than on silicon and single-crystalline oxide substrates. Films grown on MgO(001) and α-Al₂O₃(001) substrates were strongly textured or epitaxial. For example, monoclinic HfO₂ deposited on MgO(001) were epitaxial for deposition temperatures of 400-500 C in ALD and 500-600 C in CVD. Electrical characterisation showed that the crystallinity of the films had a strong effect on the dielectric constant, except in cases of very thin films, where the dielectric constant was more dependent on layer thickness.</p>

Due to the constantly decreasing dimensions of electronic devices, the conventional dielectric material in transistors and capacitors, SiO2, has to be replaced by a material with higher dielectric constant. Some of the most promising candidates are tantalum oxide,Ta2O5, zirconium oxide, ZrO2 and hafnium oxide, HfO2. This thesis describes new chemical vapour deposition (CVD) and atomic layer deposition (ALD) processes for deposition of Ta2O5, ZrO2 and HfO2 using the metal iodides as starting materials. The layer-by-layer growth in ALD was also studied in real time with a quartz crystal microbalance (QCM) to examine the process characteristics and to find suitable parameters for film deposition. All the processes presented here produced high-purity films at low deposition temperatures. It was also found that films deposited on Pt substrates generally crystallise at lower temperature, or with lower thickness, than on silicon and single-crystalline oxide substrates. Films grown on MgO(001) and α-Al2O3(001) substrates were strongly textured or epitaxial. For example, monoclinic HfO2 deposited on MgO(001) were epitaxial for deposition temperatures of 400-500 C in ALD and 500-600 C in CVD. Electrical characterisation showed that the crystallinity of the films had a strong effect on the dielectric constant, except in cases of very thin films, where the dielectric constant was more dependent on layer thickness.