HfO2 is a popular replacement for SiO2 in modern CMOS technology. It is used as the gate dielectric layer isolating the transistor channel from the gate. For this application, certain material property demands need to be met, most importantly, a high static dielectric constant is desirable as this positively influences the effectiveness and reliability of the device. Previous theoretical calculations have found that this property varies with the crystal structure of HfO2; specifically, the tetragonal structure possesses the highest dielectric constant (~70 from theoretical calculations) out of all possible stable structures at atmospheric pressure, with the cubic phase a far second (~29, also calculated). Following the results from previous experimental work on the phase formation of sputtered HfO2, this study investigates the possibility of producing thin films of HfO2 with the cubic or tetragonal structure by the addition of nitrogen to a reactive sputtering process at various deposition temperatures. Also, a new physical vapor deposition method known as High Power Impulse Magnetron Sputtering (HiPIMS) is employed for its reported deposition stability in the transition zone of metal-oxide compounds and increased deposition rate. Structural characterization of the produced films shows that films deposited at room temperature with a low N content (~6 at%) are mainly composed of amorphous HfO2 with mixed crystallization into t-HfO2 and c-HfO2, while pure HfO2 is found to be composed of amorphous HfO2 with signs of crystallization into m-HfO2. At 400o C deposition temperature, the crystalline quality is enhanced and the structure of N incorporated HfO2 is found to be c-HfO2 only, due to further ordering of atoms in the crystal lattice. Optical and dielectric characterization revealed films with low N incorporation (< 6 at%) to be insulating while these became conductive for higher N contents. For the insulating films, a trend of increasing static dielectric constant with increasing N incorporation is found.

In this study, the characteristics of Nickel-doped LPD-TiO2 films on silicon substrate were investigated. In our experiment, we do some measurement about physical, chemical and electrical properties for undoped and Nickel-doped LPD-TiO2 films and discussed with them. The TiO2 film thickness was characterized by field emission scanning electron microscopy ( FE-SEM ), structure was characterized by X-ray diffraction (XRD), chemical properties was characterized by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR) and electrical properties was characterized by leakage current: current-voltage (B1500A) and dielectric constant: capacitance-voltage (4980A). For the electrical property improvements, we investigated the Ni-doped LPD-TiO2 films by the post-anneal treatments in nitrogen, oxygen and nitrous oxide ambient. For nickel doping, the nickel chloride was used as the doping solution and the electrical characteristics were improved. After thermal annealing in nitrous oxide at 700 oC, the dielectric constant of polycrystalline titanium oxide film is 29 and can be improved to 94 with nickel doping.

An uniform titanium oxide film was grown on indium tin oxide/glass substrate with the aqueous solutions of ammonium hexafluoro-titanate and boric acid. The as-deposition titanium oxide film shows good electrochromic property because of fluorine passivation on defects and dangling bonds. The transmittance of as-grown titanium oxide on indium tin oxide/glass with a thickness of 270 nm is about 85% at the wavelength of 550 nm. By 50 times electrochromic cycling test, the transparency ratio of TiO2 film is kept at 45% between fully colored state and fully bleached state at the wavelength of 550 nm. Under ultraviolet illumination, the growth of titanium oxide film grown is enhanced. The root mean squared value of surface roughness is improved from 3.723 to 0.523 nm. Higher fluorine concentration from (NH4)2TiF6 passivate defects and dangling bonds of titanium oxide during the growth. After 50 times electrochromic cycling test, the transparency ratio UV-TiO2 is improved from 37.5% to 42.4% at the wavelength of 550 nm. The electrical characteristics of nickel-doped titanium oxide films on p-type (100) silicon substrate by liquid phase deposition were investigated. For nickel doping, the nickel chloride was used as the doping solution and the electrical characteristics were improved. After thermal annealing in nitrous oxide at 700 oC, the dielectric constant of polycrystalline titanium oxide film is 29 and can be improved to 94 with nickel doping. Uniform nickel oxide film was grown on a conducting glass substrate with the aqueous solution of saturated NiF2¡E4H2O solution and H3BO3. The quality of NiO is improved after thermal annealing at 300 oC in air from the decrease of oxygen vacancy and better F ion passivation on defects and dangling bonds. The transmittance of as-deposited NiO/ITO/glass with a thickness of 100 nm is about 78% and improved to 88% after annealing at the wavelength of 550 nm. By the electrochromic cycling test 50 times on annealed NiO film, the transparency ratio is kept at 48% between fully colored state and fully bleached state at the wavelength of 550 nm. By the memory time test, the annealed LPD-NiO film has shorter memory time. The growth of nickel oxide film grown on indium-tin oxide/glass substrate by liquid phase deposition is enhanced under ultraviolet photo-irradiation was studied. a-Ni(OH)2 dominates the composition of as-grown NiO film. After thermal treatment at 300 oC,a-Ni(OH)2 is transformed into NiO. For thermally treated NiO under ultraviolet photo-irradiation, the recrystallization and the colored and bleached transmittance after 50 times electrochromic test were improved. Both improvements come from fluorine passivation. Transparent and conductive thin films consisting of p-type nickel oxide (NiO) semiconductors were prepared by liquid phase deposition. A resistivity of 8 x 10-1 -cm was obtained for NiO films prepared at liquid phase deposition. The transmittance of NiO is almost 70 % in the 550 nm wavelength was obtained for a 384.3 nm thick NiO film.

This thesis contains four parts. In the first part, we investigate the post treatment of low-temperature-deposited high dielectric constant (high-k) thin films to enhance their properties. The high-pressure oxygen (O2 and O2+UV light) is employed to improve the properties of low-temperature-deposited metal oxide dielectric films and interfacial layer. In this study, 13nm HfO2 thin films are deposited by sputtering method at room temperature. Then, the oxygen treatments with a high-pressure of 1500 psi at 150 ¢J are performed to replace the conventional high temperature annealing. According to the XPS analyses, integration area of the absorption peaks of O-Hf and O-Hf-Si bonding energies apparently raise and the quantity of oxygen in deposited thin films also increases from XPS measurement. In addition, the leakage current density of standard HfO2 film after O2 and O2+UV light treatments can be improved from 3.12¡Ñ10-6 A/cm2 to 6.27¡Ñ10-7 and 1.3¡Ñ10-8 A/cm2 at |Vg| = 3 V. The leakage current density is significantly suppressed and the current transport mechanism is transformed from trap-assisted tunneling to Schottky-Richardson emission due to the passivation of traps inside HfO2 film and interfacial layer. The proposed treatment is applicable for the future flexible electronics. In the second part of this thesis, we study the memory characteristics of CoSi2 nanocrystals with SiO2 or Al2O3/HfO2 multiple layer tunnel oxide. Due to the property of high-k, it can provide thicker physics thickness than thermal oxide (SiO2) under identical equivalent oxide thickness (EOT) and enhances the reliability without reducing the programming speed. By engineering the different dielectric constant materials and the energy band structure, the performance of nonvolatile memory can be improved. The device that employs HfO2/Al2O3/HfO2 as tunnel oxide exhibits better memory window and carrier injection efficiency than the device employing thermal oxide. Furthermore, the device employs Al2O3/HfO2/Al2O3 as tunnel oxide present the better retention characteristics than the device employs HfO2/Al2O3/HfO2 as tunnel oxide. The corresponding mechanisms were also discussed. For the advanced nonvolatile application, high-k material - hafnium oxide was applied on the resistance switching nonvolatile memory device as resistive switching layer with TiN/Ti/HfO2/TiN structure in the third part of this thesis. By using a thin Ti layer as the reactive buffer layer into the anode side, the proposed device exhibits superior bistable characteristics. Since the Ti can easily absorb oxygen atoms from buried HfO2, the TiN/Ti bi-layer can greatly improve the resistive switching characteristics. The mechanism of the proposed device is dominated by the redox reaction between the Hf and HfOX. In addition, the proposed device has multi-bit storage ability to enhance the storage density. From the temperature-dependent measurements, the low ambient temperatures would cause the formation and rupture of the conduction path with discordant quality and quantity during every switching cycle, which give rise to a wide distribution of the HRS and LRS resistance and instability of resistive switching properties. In the fourth part of this thesis, we investigate the characteristics of an advanced Cu-induced resistance switching non-volatile memory with Pt/Cu/SiON/TiN/SiO2/Si structure. By inserting a Cu ultra thin film between the SiON layer and Pt top electrode, the device exhibits bipolar resistive switching characteristics after a forming process at 13.6 V. However, the forming and resistive switching process can not be observed in the device if the Cu thin film is omitted. Additionally, we employ a two-step forming process to reduce the forming voltage to 7.5 V. During the forming process, the bias-induced Cu could form a filament-like stretched electrode, but the ¡§set¡¨ and ¡§forming¡¨ voltage of the proposed device take place on different polarity. Therefore, we suppose a bipolar switching mechanism, and our device is dominated by the formation and rupture of the oxygen vacancies in a conduction path between the Cu filament and TiN button electrode. The device also demonstrates stable resistance states during 105 cycling bias pulse operations and acceptable retention characteristics after an endurance test at 85¢J. The I-V switching curves are analyzed to realize the carrier transport mechanisms in different bias regions and resistance states. Additionally, the effective thickness of the resistance switching layers (deff) for the samples with different SiON thickness is also extracted from the related mechanism and demonstrated that the deff is independent with the initial SiON thickness. The corresponding mechanisms and the deff verify the bipolar switching is dominated by the formation and rupture of the oxygen vacancies in conduction path between Cu filament and TiN bottom electrode.

Research in nanoparticle-reinforced composites is predicated by the promise for exceptional properties. However, to date the performance of nanocomposites has not reached its potential due to processing challenges such as inadequate dispersion and patterning of nanoparticles, and poor bonding and weak interfaces. The main objective of this dissertation is to improve the physical properties of polymer nanocomposites at low nanoparticle loading. The first step towards improving the physical properties is to achieve a good homogenous dispersion of carbon nanofibers (CNFs) and single wall carbon nanotubes (SWNTs) in the polymer matrix; the second step is to manipulate the well-dispersed CNFs and SWNTs in polymers by using an AC electric field. Different techniques are explored to achieve homogenous dispersion of CNFs and SWNTs in three polymer matrices (epoxy, polyimide and acrylate) without detrimentally affecting the nanoparticle morphology. The three main factors that influence CNF and SWNT dispersion are: use of solvent, sonication time, and type of mixing. Once a dispersion procedure is optimized for each polymer system, the study moves to the next step. Low concentrations of well dispersed CNFs and SWNTs are successfully manipulated by means of an AC electric field in acrylate and epoxy polymer solutions. To monitor the change in microstructure, alignment is observed under an optical microscope, which identifies a two-step process: rotation of CNFs and SWNTs in the direction of electric field and chaining of CNFs and SWNTs. In the final step, the aligned microstructure is preserved by curing the polymer medium, either thermally (epoxy) or chemically (acrylate). The conductivity and dielectric constant in the parallel and perpendicular direction increased with increase in alignment frequency. The values in the parallel direction are greater than the values in the perpendicular direction and anisotropy in conductivity increased with increase in AC electric field frequency. There is an 11 orders magnitude increase in electrical conductivity of 0.1 wt% CNF-epoxy nanocomposite that is aligned at 100 V/mm and 1 kHz frequency for 90 minutes. Electric field magnitude, frequency and time are tuned to improve and achieve desired physical properties at very low nanoparticle loadings.

Most engineering as well as pavement materials are composites composed of two or more components to obtain a variety of solid properties to support internal and external loading. The composite materials rely on physical or chemical properties and volume fraction of each component. While the properties can be identified easily, the volume fraction is hard to be estimated due to the volumetric variation during the performance in the field. Various test procedures have been developed to measure the volume fractions; however, they depend on subjective determination and judgment. As an alternative, electromagnetic technique using dielectric constant was developed to estimate the volume fraction. Empirical and mechanistic approaches were used to relate the dielectric constant and volume fraction. While the empirical models are not very accurate in all cases, the mechanistic models require assumptions of constituent dielectric constants. For those reasons, the existing approaches might produce less accurate estimate of volume fraction. In this study, a mechanistic-based approach using the self consistent scheme was developed to be applied to multiphase materials. The new approach was based on calibrated dielectric constant of components to improve results without any assumptions. Also, the system identification was used iteratively to solve for dielectric parameters and volume fraction at each step. As the validation performed to verify the viability of the new approach using soil mixture and portland cement concrete, it was found that the approach has produced a significant improvement in the accuracy of the estimated volume fraction.

The specific heat Cp has been showed at various temperatures in the literature, which shows a sharp increase labeled as the lambda-transition at the critical temperature. This transition has been observed previously among the phases of solid-nematic-isotropic liquid in p-azoxyanisole (PAA) and anisaldazine (AAD), and among the phases of solid-smectic-cholesteric-isotropic liquid in cholesteryl myristate (CM). In this thesis work, we analyze the experimental data for the temperature dependence of Cp and the thermal expansion alpha_p and also pressure dependence of alpha_p by a power-law formula. From the analysis of pressure dependence of alpha_p, we calculate the temperature dependencies of specific heat Cp and of the isothermal compressibility kappa_T for the phase transitions considered in PAA, AAD and CM. Our calculations for the temperature dependence of the p and kappa_T can be compared with the experimental data when available in the literature. Polarization, tilt angle and the dielectric constant have been reported in the literature at various temperatures close to the solid-smectic C*-smectic A-isotropic liquid transition in the ferroelectric liquid crystals of A7 and C7. The mean field model with the free energy expanded in terms of the order parameters (polarization and tilt angle) has been reported in the literature previously. In this thesis work, we apply the mean field model first time by fitting the expressions derived for the temperature dependence of the polarization, tilt angle and the dielectric constant to the experimental data for A7 and C7 from the literature. Since the mean field model studied here describes adequately the observed behaviour of A7 and C7, the expressions for the temperature dependence of the polarization, tilt angle and the dielectric constant which we derive, can also be applied to some other ferroelectric liquid crystals to explain their observed behaviour.

Radio wave absorbing materials (RAM) are commonly found amongst high-tech products such as LCD electronic devices, laptop and desktop computers. Electromagnetic wave absorbing materials are composed of dielectric materials mixed with ferrite, a magnetic material, with varying shapes and sizes. It should be capable of absorbing electromagnetic energy at normal and large incident angles over a wide range of frequencies. This requires the material to possess a large relative complex dielectric constant (permitivity £`r), as well as a large relative complex magnetic permeability constant (£gr). Due to the nature of the complexity of the RAM, which surpasses standard analysis techniques, we have derived, for this thesis, frequency-domain two-dimensional finite-difference formulas for modeling the electromagnetic behavior of RAM. This involves using a material that has a given £`r(1:10 range) and £gr(1:1000 range) which covers a vast range of indices of refraction. To reduce the computational domain, we took care of implementing the numerical absorbing boundary conditions, while also implementing material averaging schemes for the finite-difference coefficients that cover the region where sample medium changes. Simple numerical examples are included to verify our mathematical model. We also implemented an optimal one-dimensional multi-layered RAM design, designed by using a constrained optimization searching technique. Included in the thesis are two complete, practical, optimal designs considering available material parameters (finite loss tangent) as well as their actual manufacturing limitations (layer thickness).

Polyetherimide/(Ba0.8Sr0.2)(Ti0.9Zr0.1)O3 (PEI/BSTZ8291) composites are fabricated using PEI, dispersant, solvents, and BSTZ powder. The effects of the content of BSTZ8291 filler on the chemical, physical, mechanical and dielectric properties of PEI/BSTZ8291 composites are studied in this paper. As the content of BSTZ filler increases from 10 wt% to 70 wt%, the relative permittivity of PEI/BSTZ8291 composites at 1 MHz increase from 2.58 to 17.71. The measurement of relative permittivity of PEI/BSTZ8291 composites is developed using the ¡§Rectangular Cavity Resonator¡¨ method from 1 GHz to 13.5 GHz. The relative permittivity is calculated by observing the frequencies of resonant cavity modes. The relative permittivity of PEI/BSTZ8291 composites is almost unchanged as the measured frequency increases from 1 GHz to 13.5 GHz. The presented characteristics are better than those of polymer/BaTiO3 composites. The improvement in the tensile strength of PEI/BSTZ8291 composites may be caused by the increased interactions between neat PEI and BSTZ8291 ceramic powder, and no phase separation phenomenon occurred. The Young¡¦s modulus of the PEI/BSTZ8291 composites is improved by about 58% as the content of BSTZ8291 filler from 0 to 50 wt% and the elongation at break of the composites decreases as the content of BSTZ8291 filler increases, indicating that the composite becomes somewhat brittle as compared with neat PEI. PEI/BSTZ8291 composite substrates are developed for the applications of circularly polarized (CP) antennas. A CP antenna with a simple structure is developed as the ultra high frequency (UHF) band radio frequency identification (RFID) reader application. The fabricated antenna has an impedance bandwidth spanning from 901 to 949 MHz, which covers the entire band of Taiwan UHF-RFID frequency. The measured return loss, Smith chart, axial ratio, radiation patterns and CP gain characteristics of antennas fabricated on PEI/BSTZ8291 composites are excellent in the band of Taiwan UHF-RFID frequency. It is demonstrated that the CP antenna fabricated on PEI/BSTZ substrate has the better characteristics and small size than those fabricated on FR4 substrate.

In order to address the challenges of capacitive sensing in harsh environment, self resonant passive wireless sensors are studied. The capacitive sensing elements based on interdigitated capacitor (IDC) sensor are used. A semi-empirical model providing accurate capacitance calculation for IDCs over a wide range of dimensions and dielectric constants is developed. An equivalent circuit model based on electric field distribution is proposed, leading to a closed form approximation for IDC capacitance calculation. The conductivity of the material under test is also considered and a model is proposed to calculate effective capacitance as a function of conductivity and measurement frequency. The model is used to study the design optimization of IDC sensor and suggested design procedure is proposed. To wirelessly interrogate the capacitive sensor, it is connected to an inductive element to form a resonant circuit, while the measurement is made at remote reader coil. Advantages and disadvantages of different type of resonant structure design are analyzed. In order to assist the design process, a SPICE circuit model is developed to estimate the resonant frequency of the self resonant sensor. Miniaturized sensors with different dimensions are designed, fabricated and tested. The sensor is integrated with silicon nanowire fabric coated with polymer. Measurements are made to illustrate the enhancement in sensing capability by integrating chemical selective material. / text