We use the spin polarized pseudofunction(PSF) method with the local-spin-density approximation (LSDA) to calculate the electronic structures and the total and partial charge densities (TDOS, PDOS) of bulk Ba1-xSrxTiO3 (BSTO) with x = 0, 0.25, 0.5, 0.75, and 1. We find that the calculated direct energy gap Eg bows up as a function of the Sr concentration, which is related to the bowling downward of the Ti-O bond length inferred from the experimental lattice constants. The calculated partial densities of unoccupied O-p derived states (PDOS) agree well with the features observed in the O K-edge XANES spectra of BaTiO3 and SrTiO3. The calculated total densities of valence-band states (TDOS) and the valence-band widths for BaTiO3 and SrTiO3 agree well with the UPS spectra.

Low temperature sintering has become a very important research area in ceramics processing and sintering as a promising process to obtain grain size below 100nm. For electronic ceramics, low temperature sintering is particularly difficult, because not only the required microstructure but also the desired electronic properties should be obtained. In this dissertation, the effect of liquid sintering aids and particle size (micrometer and nanometer) on sintering temperature and Positive Temperature Coefficient Resistivity (PTCR) property are investigated for Ba1-xSrxTiO3 (BST) doped with 0.2-0.3mol% Sb3+ (x = 0.1,0.2,0.3,0.4 and 0.5). Different sintering aids with low melting point are used as sintering aids to decrease the sintering temperature for micrometer size BST particles. Micrometer size and nanometer size Ba1-xSrxTiO3 (BST) particles are used to demonstrate the particle size effect on the sintering temperature for semiconducting BST. To reduce the sintering temperature, three processes are developed, i.e. 1 using sol-gel nanometer size Sb3+ doped powders with a sintering aid; 2 using micrometer size powders plus a sintering aid; and 3 using nanometer size Sb3+ doped powders with sintering aids. Grain size effect on PTCR characteristics is investigated through comparison between micrometer size powder sintered pellets and nanometer size powder sintered pellets. The former has lower resistivity at temperatures below the Curie temperature (Tc) and high resistivity at temperatures above the Curie temperature (Tc) along with higher ñmax/ñmin ratio (ñmax is the highest resistivity at temperatures above Tc, ñmin is the lowest resistivity at temperatures below Tc), whereas the latter has both higher ñmax and ñmin. Also, ñmax/ñmin is smaller than that of pellets with larger grain size. The reason is that the solid with small grain size has more grain boundaries than the solid with large grain size. The contribution z at room temperature and high temperature and a lower ñmax/ñmin ratio value.

Este trabalho, realizado junto ao Grupo de Novos Materiais e Dispositivos (GNMD) pertencente ao Laboratório de Microeletrônica (LME) da Universidade de São Paulo, teve como objetivo correlacionar algumas propriedades físico-químicas de filmes finos de Ba1-XSrxTiO3 (BST), obtidos pela técnica de pulverização catódica reativa (sputtering), com os parâmetros de deposição, visando a fabricação de defasadores inteligentes operando em 60 GHz. Propriedades como cristalinidade e composição química foram estudadas e relacionadas com o tipo de substrato sobre o qual os filmes finos de BST foram depositados, e com os diversos parâmetros de deposição variados. Foi observada uma forte influência dos parâmetros de deposição, principalmente da temperatura e do tipo de substrato, na cristalinidade dos filmes. Os filmes depositados sobre cobre são mais cristalinos do que aqueles depositados sobre Si. Já a composição química dos filmes não variou significativamente, mantendo-se próxima à do alvo de sputtering utilizado, independentemente do substrato ou das condições de deposição. As propriedades elétricas dos filmes fabricados foram extraídas de capacitores de placas paralelas construídos utilizando o BST como dielétrico linear. As curvas de capacitância vs tensão a 1 MHz destes capacitores permitiram determinar uma variação de tunabilidade de até 44 %, para uma permissividade elétrica relativa de 310, valores estes compatíveis com aqueles encontrados na literatura. As propriedades elétricas dos filmes produzidos permitiram projetar um defasador de 1,3 mm2, com uma figura de mérito de 30º/dB para uma defasagem de 360º. / This work, performed at the New Materials and Devices Group (GNMD) of the Microelectronics Laboratory of the Polytechnic School of the University of São Paulo, has the objective to correlate reactive sputtered-BST thin films to its deposition parameters, aiming to produce a 60 GHz tunable phase shifter. Thin film crystallinity and stoichiometry were correlated with sputtering deposition parameters and the type of substrate. A strong influence of the sputtering parameters was observed on BST crystallinity, mainly the temperature and the type of substrate. Thin films on copper are more crystalline than on Si (100). The stoichiometry, on the other hand, did not change as function of the deposition parameters or the substrate in both cases. The thin films electrical properties were obtained by capacitance vs voltage measurements, with the BST as linear dielectric of a parallel plate capacitor. The capacitors 1 MHz C-V characterization showed tunabilities as high as 44%, for an electrical permittivity of 310. These properties allowed a phase shifter project, resulting a 1,3 mm2 device with a figure of merit of 30 º/dB for 360 º phase shift.

Este trabalho, realizado junto ao Grupo de Novos Materiais e Dispositivos (GNMD) pertencente ao Laboratório de Microeletrônica (LME) da Universidade de São Paulo, teve como objetivo correlacionar algumas propriedades físico-químicas de filmes finos de Ba1-XSrxTiO3 (BST), obtidos pela técnica de pulverização catódica reativa (sputtering), com os parâmetros de deposição, visando a fabricação de defasadores inteligentes operando em 60 GHz. Propriedades como cristalinidade e composição química foram estudadas e relacionadas com o tipo de substrato sobre o qual os filmes finos de BST foram depositados, e com os diversos parâmetros de deposição variados. Foi observada uma forte influência dos parâmetros de deposição, principalmente da temperatura e do tipo de substrato, na cristalinidade dos filmes. Os filmes depositados sobre cobre são mais cristalinos do que aqueles depositados sobre Si. Já a composição química dos filmes não variou significativamente, mantendo-se próxima à do alvo de sputtering utilizado, independentemente do substrato ou das condições de deposição. As propriedades elétricas dos filmes fabricados foram extraídas de capacitores de placas paralelas construídos utilizando o BST como dielétrico linear. As curvas de capacitância vs tensão a 1 MHz destes capacitores permitiram determinar uma variação de tunabilidade de até 44 %, para uma permissividade elétrica relativa de 310, valores estes compatíveis com aqueles encontrados na literatura. As propriedades elétricas dos filmes produzidos permitiram projetar um defasador de 1,3 mm2, com uma figura de mérito de 30º/dB para uma defasagem de 360º. / This work, performed at the New Materials and Devices Group (GNMD) of the Microelectronics Laboratory of the Polytechnic School of the University of São Paulo, has the objective to correlate reactive sputtered-BST thin films to its deposition parameters, aiming to produce a 60 GHz tunable phase shifter. Thin film crystallinity and stoichiometry were correlated with sputtering deposition parameters and the type of substrate. A strong influence of the sputtering parameters was observed on BST crystallinity, mainly the temperature and the type of substrate. Thin films on copper are more crystalline than on Si (100). The stoichiometry, on the other hand, did not change as function of the deposition parameters or the substrate in both cases. The thin films electrical properties were obtained by capacitance vs voltage measurements, with the BST as linear dielectric of a parallel plate capacitor. The capacitors 1 MHz C-V characterization showed tunabilities as high as 44%, for an electrical permittivity of 310. These properties allowed a phase shifter project, resulting a 1,3 mm2 device with a figure of merit of 30 º/dB for 360 º phase shift.

There has been unprecedented growth in wireless technologies in recent years; wireless devices such as cellular telephones and wireless local area network (WLAN) transceivers are becoming ubiquitous. It is now common for a single hardware device, such as a cellular telephone, to be capable of multi-band operation. Implementing a dedicated radio frequency (RF) front-end for each frequency band increases the component count and therefore the cost of the device. Consequently, there is now a requirement to design RF and microwave circuits that can be reconfigured to operate at different frequency bands, as opposed to switching between several fixed-frequency circuits. Barium strontium titanate (BST) thin films show great promise for application in reconfigurable microwave circuits. The material has a high dielectric constant which can be controlled by the application of a quasi-static electric field, combined with relatively low losses at microwave frequencies. Tunable microwave components based on BST-thin films have the potential to replace several fixed components, thereby achieving useful size and cost reductions. This thesis is concerned with the growth and microwave circuit applications of BST thin films on c- and r-plane sapphire substrates. Sapphire is an ideal substrate for microwave integrated circuit fabrication due to its low cost and low loss. Electronically tunable capacitors (varactors) were fabricated by patterning interdigital electrode structures on top of the BST films. High capacitance tunabilities of 56% and 64% were achieved for the films grown on c-plane and r-plane sapphire, respectively, at 40 V bias. A novel electronically tunable 3 dB quadrature hybrid circuit was also developed. Prototypes of this circuit were initially implemented using commercial varactor diodes, in order to validate the design. An integrated version of the coupler was then fabricated using BST varactors on c-plane sapphire. The results achieved demonstrate the potential of sapphire-based BST thin films in practical microwave circuits.

Ferroelectric materials have received lots of attention thanks to their intriguing properties such as the piezoelectric and pyroelectric effects, as well as the large dielectric constants and the spontaneous polarization which can potentially be used for information storage. In particular, perovskite crystal has a very simple unit cell structure yet a very rich phase transition diagram, which makes it one of the most intensively studied ferroelectric materials. In this dissertation, we use effective Hamiltonian, a first-principles-based computational technique to study the finite-temperature properties of ferroelectric perovskites. We studied temperature-graded (BaxSr1-x )TiO3 (BST) bulk alloys as well as the dynamics of nanodomain walls (nanowalls) in Pb(ZrxTi1-x )O3 (PZT) ultra-thin films under the driving force of an AC field. Our computations suggest that, for the temperature-graded BST, the polarization responds to the temperature gradient (TG), with the "up" and "down" offset observed in polarization components along the direction of TG, in agreement with the findings from experiments. For the nanowalls in PZT, the dynamics can be described by the damped-harmonic-oscillator model, and we observed a size-driven transition from resonance to relaxational dynamics at a critical thickness of 7.2 nm. The transition originates from the change in the effective mass of a nanowall as a film thickness increases. Some of the findings may find potential applications in various devices, such as thermal sensors, energy converters, or novel memory units.

This dissertation shows a detailed investigation on reconfigurable low profile antennas using tunable high impedance surfaces (HIS). The specific class of HIS used in this dissertation is called a frequency selective surface (FSS). This type of periodic structure is fabricated to create artificial magnetic conductors (AMCs) that exhibit properties similar to perfect magnetic conductors (PMCs). The antennas are intended for radiometric sensing applications in the biomedical field. For the particular sensing application of interest in this dissertation, the performance of the antenna sub-system is the most critical aspect of the radiometer design where characteristics such as small size, light weight, conformability, simple integration, adjustment in response to adverse environmental loading, and the ability to block external radio frequency interference to maximize the detection sensitivity are desirable. The antenna designs in this dissertation are based on broadband dipole antennas over a tunable FSS to extend the usable frequency range. The main features of these antennas are the use of an FSS that does not include via connections to ground, their low profile and potentially conformal nature, high front-to-back radiation pattern ratio, and the ability to dynamically adjust the center frequency. The reduction of interlayer wiring on the tunable FSS minimizes the fabrication complexity and facilitates the use of flexible substrates. This dissertation aims to advance the state of the art in low profile tunable planar antennas. It shows a qualitative comparison between antennas backed with different unit cell geometries. It demonstrates the feasibility to use either semiconductor or ferroelectric thin film varactor-based tunable FSS to allow adjustment in the antenna frequency in response to environment loading in the near-field. Additionally, it illustrates how the coupling between antenna and HIS, and the impact of the varactor losses affect the antenna performance and it shows solutions to compensate these adverse effects. Novel hybrid manufacturing approaches to achieve flexibility on electrically thick antennas that could be transitioned to thin-film microelectronics are also presented. The semiconductor and ferroelectric varactor-based tunable low profile antennas demonstrated tunability from 2.2 GHz to 2.65 GHz with instantaneous bandwidths greater than 50 MHz within the tuning range. The antennas had maximum thicknesses of λ/45 at the central frequency and front to back-lobe radiation ratios of approximately 15dB. They also showed impedance match improvement in the presence of a Human Core Model (HCM) phantom at close proximity distances of the order of 10-20 mm. In addition, the use of thin film ferroelectric Barium Strontium Titanate (BST) varactors in the FSS layer enabled an antenna that had smaller size, lower cost and less weight compared to the commercially available options. The challenging problems of fabricating robust flexible antennas are also addressed and novel solutions are proposed. Two different types of flexible antennas were designed and built. A series of flexible microstrip antennas with slotted grounds which demonstrated to be robust and have 42% less mass than typically used technologies (e.g., microstrip antennas fabricated on Rogers® RT6010, RT/duroid® 5880, etc.); and flexible ferroelectric based tunable low profile antennas that showed tunability from 2.42 GHz to 2.66 GHz using overlapping metallic plates instead of a continuous ground plane. The bending test results demonstrated that, by placing cuts on the ground plane or using overlapping metallic layers that resemble fish scales, it was possible to create highly conductive surfaces that were extremely flexible even when attached to other solid materials. These new approaches were used to overcome limitations commonly encountered in the design of antennas that are intended for use on non-flat surfaces. The material presented in this dissertation represents the first investigation of reconfigurable low profile antennas using tunable high impedance surfaces where the desired electromagnetic performance as well as additional relevant features such as robustness, low weight, low cost and low complexity were demonstrated.

High performance miniaturized passives are of great importance for advanced nanoelectronic packages for several applications including efficient power delivery. Low cost thin film capacitors fabricated directly on package (and/or on-chip) are an attractive approach towards realizing such devices. This thesis aims to explore fundamental frequency dependent dielectric and insulating properties of thin film high-k dielectric constant in the perovskite and perovskite-related complex oxides. Throughout this thesis, we have successfully observed the role of structure, strain and oxygen stoichiometry on the dielectric properties of thin film complex oxides, allowing a greater understanding of processing conditions and polarization mechanisms. In the first section of the thesis, we explore novel processing methods in the conventional ferroelectric, barium strontium titanate, \(Ba_{1-x}Sr_xTiO_3 (BST)\), using ultraviolet enhanced oxidation techniques in order to achieve improvements in the dielectric properties. Using this method, we also explore the growth of BST on inexpensive non-noble metals such as Ni which presents technical challenges due to the ability to oxidize at high temperatures. We observe a significant lowering of the dielectric loss while also lowering the process temperature which allows us to maintain an intimate interface between the dielectric layer and the metal electrode. The second section of this thesis explores the novel dielectric material, Lanthanum Strontium Nickelate, \(La_{2-x}Sr_xNiO_4 (LSNO)\), which exhibits a colossal dielectric response. For the first time, we report on the colossal dielectric properties of polycrystalline and epitaxial thin film LSNO. We observe a significant polarization dependence on the microstructure due to the grain/grain boundary interaction with charged carriers. We next grew epitaxial films on various insulating oxide substrates in order to decouple the grain boundary interaction. Here we observed substrate dependent dielectric properties associated with induced strain. We also observe, due to the p-type carriers in LSNO, pn junction formation when grown epitaxially on the conducting oxide degenerate n-type Nb-doped \(SrTiO_3\). Finally we explore the growth mechanism of epitaxial LSNO as a function of high oxygen content. Due to the ability for LSNO to take in interstitial oxygen, a reoriented growth is observed at a critical thickness, thereby allowing us to vary anisotropy as a function of deposition conditions. / Engineering and Applied Sciences

Barium Strontium Titanate (BST) was deposited on Pt/ZrO2 / SiO2/Si substrates using liquid source metal organic chemical vapor deposition. A stoichiometry series was deposited with various GrII/Ti ratios (0.658 to 1.022) and a temperature series was deposited at 550 to 700°C. The thin films were characterized using transmission electron microscopy. Both series of samples contained cubic perovskite BST and an amorphous phase. The grain size increased and the volume fraction of amorphous phase decreased with increasing deposition temperature. The electrical and microstructural properties improved as the GrII/Ti ratio approached 1 and deteriorated beyond 1. This research demonstrates that BST thin films are a strong candidate for future MOS transistor gate insulator applications.

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