Dissertations / Theses on the topic 'High dielectric materials'

Energy storage is currently gaining considerable attention due to the current energy crisis and severe air pollution. The development of new and clean forms of energy and related storing devices is in high demanded. Dielectric capacitors, exhibiting high power density, long life and cycling life, are potential candidates for portable devices, transport vehicles and stationary energy resources applications. However, the energy density of dielectric capacitors is relatively low compared to that of traditional batteries, which inhibits their future development. In the current work, three types of dielectrics, namely antiferroelectric samarium-doped BiFeO3 (Bi1-xSmxFeO3), linear dielectric (potential antiferroelectric) BiNbO4 and incipient ferroelectric TiO2, have been investigated to develop their potential as energy storage capacitors. For the samarium-doped BiFeO3 (Bi1-xSmxFeO3) system, the effect of samarium content in the A-site (x=0.15, 0.16, 0.165 and 0.18) on the structural phase transitions and electrical properties across the Morphotropic Phase Boundary (MPB) were studied. A complex coexistence of rhombohedral R3c, orthorhombic Pbam and orthorhombic Pnma was found in the selected compositions. The R3c phase is the structure of pure BiFeO3, the Pbam phase has a PbZrO3-like antiferroelectric structure and the Pnma phase has a SmFeO3-like paraelectric structure. The presence of the PbZrO3-like antiferroelectric structure was confirmed by the observation of the 14{110}, 14{001}, 12{011} and 12{111} superlattice reflections in the transmission electron microscopy diffraction patterns. The weight fractions of the three phases varied with different calcination conditions and Sm substitution level. By increasing the calcination temperature, the weight fractions of the Pbam increased, while that of the R3c decreased. The fraction of the Pnma phase is mainly derived by the Sm concentration and is barely affected by the calcination temperature. The increase of Sm concentration, determined an increase of the weight fraction of the Pnma phase and a decrease of the Pbam and the R3c phases. Temperature dependent dielectric measurements and high temperature XRD of Bi0.85Sm0.15FeO3 revealed several phase transitions. The drastic weight fraction change between the Pbam and the Pnma phase around 200 °C is assumed as the Curie transition of the antiferroelectric Pbam phase. The transition at 575 °C is related to the diminishing of the R3c phase and is suggested as the Curie transition of the ferroelectric R3c phase. The Curie point of the antiferroelectric Pbam phase and the ferroelectric R3c phase in the Bi1-xSmxFeO3 ceramics shifted towards lower temperature with an increase of the Sm concentration. Current peaks were obtained in current-electric field loops in Bi0.85Sm0.15FeO3, which are correlated to domain switching in the R3c phase. The ferroelectric behavior was suppressed in Bi1-xSmxFeO3 (x=0.16, 0.165, 0.18), which is due to the gradually diminished contribution from the R3c phase. The system Bi0.82Sm0.18FeO3 showed the highest energy density of 0.64 J cm-3 (error bar ±0.02). For the BiNbO4 system, single phase α-BiNbO4 (space group Pnna) and β-BiNbO4 (space group P-1) powder and ceramics were produced. The longstanding issue related to the sequence of the temperature-induced phase transitions has been clarified. It is demonstrated that the β phase powder could be converted back to the  phase when annealed in the temperature range 800 °C -1000 °C with certain incubation time. The β to  phase transition is a slow kinetic process because sufficient temperature and time are required for the transition. In bulk ceramics with β phase, this transformation is impeded by inner stress, while it is favored by graphite-induced reducing atmosphere. A high temperature  phase has been revealed and the structure has been resolved. The structure of the  phase is monoclinic with a space group of P21/c. The lattice parameters are: a = 7.7951(1) Å, b = 5.64993(9) Å, c = 7.9048(1) Å,  = 104.691(2) Z=4. The volume is 336.76 (2) Å3. The calculated density is 7.217 g cm-3. The phase relationships among ,  and  phases have been clarified. It was found that the  phase (for both powder and ceramic) transforms into the  phase at 1040 °C on heating, and that the  phase always transforms into the  phase at 1000 °C on cooling. Meanwhile, a reversible first-order  to  phase transition is observed at ca. 1000 °C for both powder and ceramic if no incubation is processed on heating. The electric properties of both α- and - BiNbO4 have been investigated. The breakdown field of both ceramics were too low to observe any possible field-induced transition. As a result, linear P-E loops were obtained in each phase. The energy densities of α- and - BiNbO4 ceramics are 0.03 and 0.04 J cm-3 (error bar ±0.001), respectively. For the TiO2 system, ceramics were produced by conventional sintering and spark plasma sintering (SPS). Compared to conventional sintering, SPS technique produced dense ceramics without using sintering aids and avoided abnormal grain growth. Relaxation behavior related to the oxygen hopping among vacant sites is observed in the temperature range of 200 to 600 °C. TiO2 exhibits ultra-low loss at terahertz frequencies due to the reduced contribution of oxygen vacancies relaxation. TiO2 has a high breakdown field, but still has low polarization. The highest energy density obtained inTiO2 ceramics is 0.3 J cm-3 (error bar ±0.01).

Thesis (Ph.D)--Materials Science and Engineering, Georgia Institute of Technology, 2009.
Committee Chair: Wong, C. P.; Committee Member: Jacob, Karl; Committee Member: Liu, M. L.; Committee Member: Tannenbaum, Rina; Committee Member: Wang, Z. L.. Part of the SMARTech Electronic Thesis and Dissertation Collection.

Materials exposed to the space plasma environment acquire electric charge, which can have harmful effects if it leads to arcing or electrostatic breakdown of important spacecraft components. In fact, spacecraft charging is the leading environmentally induced cause of spacecraft anomalies. This study focuses on measuring electron yield, a property of materials that describes how many electrons are ejected from a material under energetic electron bombardment, which can vary depending on the energy of incident electrons. Intrinsic electron yield is defined as the average number of electrons emitted per incident electron from an electrically neutral material. The specific aim of this work is to improve yield measurements for insulator materials, which can be difficult to test using conventional methods due to charge accumulation in insulators.Most studies of electron yield use a steady current electron beam in a vacuum chamber to irradiate materials to be tested. By comparing the amount of current deposited in the material to the total incident current, the emitted current can be calculated. This works well for conductors; however, insulators charge up quickly, which either repel incident electrons or reattract emitted electrons producing erroneous yield measurements. This study improves on methods that use a pulsed electron beam to measure yield with small amounts of charge per pulse, as well as neutralization methods to dissipate stored charge between pulse measurements.The improvements to instrumentation and data analysis techniques are quantified to demonstrate their validity. These improvements will allow for continued studies on extreme insulator materials. Future studies will provide new understanding of interactions between electron radiation and materials, which will allow for better modeling of spacecraft charging and the development of materials that meet desired electron emission specifications.

As the conventional scaling of Si-based MOSFETs would bring negligible or even negative merits for IC's beyond the 7-nm CMOS technology node, many perceive the use of high-mobility channels to be one of the most likely principle changes, in order to achieve higher performance and lower power. However, interface and oxide traps have become a major obstacle for high-mobility semiconductors (such as Ge, InGaAs, GaSb, GaN...) to replace Si CMOS technology.

In this thesis, the distinct properties of the traps in the high-k dielectric/high-mobility substrate system is discussed, as well as the challenges to characterize and passivate them. By modifying certain conventional gate admittance methods, both the fast and slow traps in Ge MOS gate stacks is investigated. In addition, a novel ac-transconductance method originated at Yale is introduced and demonstrated with several advanced transistors provided by collaborating groups, such as ultra-thin-body & box SO1 MOSFETs (CEA-LETI), InGaAs MOSFETs (IMEC, UT Austin, Purdue), and GaN MOS-HEMT (MIT).

By use of the aforementioned characterization techniques, several effective passivation techniques on high mobility substrates (Ge, InGaAs, GaSb, GeSn, etc.) are evaluated, including a novel Ba sub-monolayer passivation of Ge surface. The key factors that need to be considered in passivating high mobility substrates are revealed.

The techniques that we have established for characterizing traps in advanced field-effect transistors, as well as the knowledge gained about these traps by the use of these techniques, have been applied to the study of ionizing radiation effects in high-mobility-channel transistors, because it is very important to understand such effects as these devices are likely to be exposed to radiation-harsh environments, such as in outer space, nuclear plants, and during X-ray or UHV lithography. In this thesis, the total ionizing dose (TD) radiation effects of InGaAs-based MOSFETs and GaN-based MOS-HEMT are studied, and the results help to reveal the underlying mechanisms and inspire ideas for minimizing the TID radiation effects.

Conventionally discrete passive components like capacitors, resistors, and inductors are surface-mounted on top of the printed circuit boards (PCBs). To match the ever increasing demands of miniaturization, cost reduction, and high performance in microelectronic industry, a promising approach is to integrate passive components into the board during PCB manufacture. Because they are embedded inside multilayer PCBs, such components are called embedded passives. This work focuses on the materials design, development and processing of polymer-based dielectric nanocomposites for embedded capacitor applications. The methodology of this approach is to combine the advantages of the polymer and the filler to satisfy the electric, dielectric, mechanical, fabrication, and reliability requirements for embedded capacitors. Restrained by poor adhesion and poor thermal stress reliability at high filler loadings, currently polymer-ceramic composites can only achieve a dielectric constant of less than 50. In order to increase the dielectric constant to above 50, effects of high-k polymer matrix, bimodal fillers, and dispersing agent are systematically investigated. Surface functionalization of nanofiller particles and modification of epoxy matrix with a secondary rubberized epoxy to form sea-island structure are proposed to enhance the dielectric constant, adhesion and high-temperature thermal stress reliability of high-k composites. To obtain photodefinable high-k composites, fundamental understanding of the photopolymerization of the novel epoxy-ceramic composite photoresist is addressed. While the properties of high-k composites largely depend on the polymer matrix, the fillers can also drastically affect the material properties. Carbon black- and carbon nanotubes-filled ultrahigh-k polymer composites are investigated as the candidate materials for embedded capacitors. Dielectric composites based on percolation typically show a high dielectric constant, and a high dielectric loss which is not desirable for high frequency applications. To achieve a reproducible low-loss percolative composite, a novel low-cost core-shell particle filled high-k percolative composite is developed. The nanoscale insulating shells allow the electrons in the metallic core to tunnel through it, and thereby the composites exhibit a high dielectric constant as a percolation system; on the other hand, the insulating oxide layer restricts the electron transfer between filler particles, thus leading to a low loss as in a polymer-ceramic system.

The progress of the silicon-based complementary-metal-oxide-semiconductor (CMOS) technology is mainly contributed to the scaling of the individual component. After decades of development, the scaling trend is approaching to its limitation, and there is urgent needs for the innovations of the materials and structures of the MOS devices, in order to postpone the end of the scaling. Atomic layer deposition (ALD) provides precise control of the deposited thin film at the atomic scale, and has wide application not only in the MOS technology, but also in other nanostructures. In this dissertation, I study rapid thermal processing (RTP) treatment of thermally grown SiO2, ALD growth of SiO2, and ALD growth of high-k HfO2 dielectric materials for gate oxides of MOS devices. Using a lateral heating treatment of SiO2, the gate leakage current of SiO2 based MOS capacitors was reduced by 4 order of magnitude, and the underlying mechanism was studied. Ultrathin SiO2 films were grown by ALD, and the electrical properties of the films and the SiO2/Si interface were extensively studied. High quality HfO2 films were grown using ALD on a chemical oxide. The dependence of interfacial quality on the thickness of the chemical oxide was studied. Finally I studied growth of HfO2 on two innovative interfacial layers, an interfacial layer grown by in-situ ALD ozone/water cycle exposure and an interfacial layer of etched thermal and RTP SiO2. The effectiveness of growth of high-quality HfO2 using the two interfacial layers are comparable to that of the chemical oxide. The interfacial properties are studied in details using XPS and ellipsometry.

One of the most important electrical requirements in high performance electronic systems or high speed integrated circuits, is to process larger numbers of electrical signals at much higher speeds. Signal propagation delay must be minimized in order to maximize signal velocities. Therefore, material with low dielectric constant and low dissipation factor is being sought. In this thesis research measurements of dielectric constant and dissipation factor were performed on commercially available polyimides that are used in multilayer interconnect structures. Capacitor structures with a polyimide dielectric were measured up to a 1GHz frequency and 220°C temperature. Polyimides were concluded to be compatible for use in high performance systems such as multilayer interconnect structures.

The use of the microstrip antenna has grown rapidly for the last two decades, because of the increasing demand for a low profile antenna with small size, low cost, and high performance over a large spectrum of frequencies. However, despite the advantages microstrip antennas provide, a number of technical challenges remain to be solved for microstrip antennas to reach their full potential, particularly if they are to be interfaced with monolithic circuits. The objective of this thesis is to examine novel methods for integrating and constructing broadband microstrip antennas, particularly at high microwave and millimeter wave frequencies where dimensions get very small and fabrication tolerances are critical. The first stage of the thesis investigates techniques to reduce the spurious feed radiation and surface wave generation from edge-fed patch antennas. A technique to reduce the spurious radiation from the edge-fed patch antenna by using a dielectric filled cavity behind the radiating element is explored. From this, a single element edge-fed cavity backed patch antenna was developed. Measured results showed low levels of cross polarization, making it suitable for dual or circular polarization applications. A 2 x 2 edge-fed cavity backed patch antenna array was also developed, which benefited greatly from this new technique due to the extensive feed network required. Furthermore, investigation into edge-fed cavity backed patches on high dielectric materials was also conducted. The measured impedance bandwidth of this edge-fed cavity backed patch is three times greater than the conventional edge-fed patch, and the gain increases to 5.1 dBi compared to 3.6 dBi. Further bandwidth enhancement of the single element edge-fed cavity backed antenna on high dielectric material was achieved by applying the hi-lo substrate structure. The hi-lo substrate structure produced an increase in the bandwidth to 26% from the 1.7% of the single element edge-fed cavity backed patch, while maintaining pattern integrity and radiation efficiency. Next, the development of a flip-chip bonding technique was investigated to enhance the fabrication accuracy and robustness of multilayer antennas on high dielectric materials. This technique was proven through simulation and experiment to provide good impedance and radiation performance via the high accuracy placement of the superstrate layer. The single element flip-chip patch antenna uses a high dielectric constant material for both the base and the patch superstrate, whereas the stacked flip-chip patch again uses a high and low permittivity material combination to achieve efficient wideband performance. Due to the high permittivity feed material, these antennas display the attributes required for integration with MMICs. The measured 10 dB return loss bandwidth of the single element was 4% with a gain of 4.6 dBi, whereas the stacked flip-chip patch showed very broadband performance, with a bandwidth of 23% with a gain of 8.5 dBi. The high accuracy placement and rigid attachment of the upper superstrat e layer via the flip-chip bonding technique also enables these antennas to be scaled up to millimeter-wave operational frequencies. The final section of this thesis is focused on developing a fabrication technique to enable the creation of a low permittivity layer at a nominated thickness.

The demands for faster, smaller, and less expensive electronic equipments are basically the driving forces for improving the speed and increasing the packing density of microelectronic components. Down-scaling of the devices is the principal method to realize these requests. For future CMOS devices, new materials are required in the transistor structure to enable further scaling and improve the transistor performance. This thesis focuses on novel metal gate and high-κ dielectric materials for future CMOS technologies. Specifically, TiN and ZrN gate electrode materials were studied with respect to work function and thermal stability. High work function, suitable for pMOS transistors, was extracted from both C-V and I-V measurements for PVD and ALD TiN in TiN/SiO2/Si MOS capacitor structures. ZrNx/SiO2/Si MOS capacitors exhibited n-type work function when the low-resistivity ZrNx was deposited at low nitrogen gas flow. Further, variable work function by 0.6 eV was achieved by reactive sputter depositing TiNx or ZrNx at various nitrogen gas flow. Both metal-nitride systems demonstrate a shift in work function after RTP annealing, which is discussed in terms of Fermi level pinning due to extrinsic interface states. Still, the materials are promising in a gate last process as well as show potential as complementary gate electrodes. The dielectric constant of as-deposited (Ta2O5)1-x(TiO2)x thin films is around 22, whereas that of AlN is about 10. The latter is not dependent on the degree of crystallinity or on the measurement frequency up to 10 GHz. Both dielectrics exhibit characteristics appropriate for integrated capacitors. Finally, utilization of novel materials were demonstrated in strained SiGe surface-channel pMOSFETs with an ALD TiN/Al2O3 gate stack. The transistors were characterized with standard I-V, charge pumping, and low-frequency noise measurements. Correlation between the mobility and the oxide charge was found. Improved transistor performance was achieved by conducting low-temperature water vapor annealing, which reduced the negative charge in the Al2O3.

New VLSI and VHSIC devices require increased performance from electronic packages. The major challenge that must be met in materials/process development for high complexity and high speed integrated circuits is the processing of even larger amounts of signals with low propagation delay. Hence, materials with low dielectric constant and low dissipation factor are being sought. In this investigation the dielectric properties of the most commonly used composite materials for printed circuit boards, Teflon-glass and Epoxy-glass, were measured in the frequency and temperature intervals of 100 HZ-1 GHZ and 25-260°C, respectively. From the measured results, it is concluded that Teflon-glass is more suitable for the board level packaging of high performance circuits due to its lower dielectric constant and low dissipation factor.

A new family of dielectric materials has been studied, individually as thick-film capacitors and as buried components incorporated in second-order lowpass and bandpass RC active filter circuits. The materials were electrically characterized in terms of the variation of dielectric constant and dissipation factor with frequency. The performance of the filter circuit is related to the characteristics of the dielectric materials. An analysis of the circuit is developed which accounts for the capacitor losses.
Master of Science

京都大学
0048
新制・課程博士
博士(工学)
甲第22159号
工博第4663号
新制||工||1727(附属図書館)
京都大学大学院工学研究科材料工学専攻
(主査)教授 田中 功, 教授 中村 裕之, 教授 邑瀬 邦明
学位規則第4条第1項該当
Doctor of Philosophy (Engineering)
Kyoto University
DFAM

Ice Ih, formed by freezing liquid water below 273∼K at atmospheric pressure, is well-known and highly-studied, but some of its fundamental physical properties have mystified scientists since the early twentieth century. The thermal expansion is one of those properties; the low relative-resolution of past measurements has left questions regarding the structural isotropy and negative thermal expansion (NTE). Furthermore, the existence of relaxation phenomena near 100∼K, related to the residual entropy at 0∼K, may reveal itself through subtle features in the thermal expansion and, thus, warrants further investigation. Here we measure the thermal expansion of ultra-pure single crystal ice from 5–265∼K with 10⁶ times higher relative resolution than has previously been made. The data reveal a distinct crossover to NTE below 62∼K, and a third-order transition along the crystallographic \(c\)-axis near 100∼K, as evident by an unambiguous relaxational decrease in the thermal expansion coefficient on cooling. To further understand the nature of the transition, isotopic substitution and dielectric measurements were performed.

Three properties of the dielectric relaxation in ice were probed at temperatures between 80--250∼K; the thermally stimulated depolarization (TSD) current, static electrical conductivity, and dielectric relaxation time. The dielectric data agree with relaxation-based models and provide for the determination of activation energies which identify the dielectric relaxation in ice as being dominated by Bjerrum defects below 140∼K. An anisotropy was also found in the data which revealed that molecular reorientations, in the form of propagating Bjerrum point defects, are energetically favored along the \(c\)-axis between 80--140∼K. Furthermore, a similar relaxational effect to that observed in the thermal expansion was observed in the TSD along \(c\), providing a strong correlation between dielectric relaxation and inherent thermodynamic relaxation in ice. Finally, isotopic substitution in both measurement sets indicates the transition is related the movements of hydrogen nuclei, not those of the whole molecule, and provides details about the low-temperature phonon modes. These findings paint a picture of ice as a proton-disordered crystal which undergoes a partial ordering on cooling near 100∼K but, before an ordered equilibrium state is realized, the exponentially increasing relaxation time rapidly slows the ordering and ultimately freezes-in the residual entropy, causing a continuous decrease in the thermal expansion coefficient.

Thesis: Ph. D., Massachusetts Institute of Technology, Department of Materials Science and Engineering, 2020
Cataloged from student-submitted PDF of thesis. The "K̳̳" in title on title page appeared as subscript "K."
Includes bibliographical references (pages 127-134).
While high-[subscript K] dielectrics utilized in CMOS technology are noted for their highly insulating characteristics, they have demonstrated surprising electrolytic behavior as key components in a variety of thin film memory devices, including those based on magneto-ionic and memristive behavior. In this work, we focus on the rare earth sesquioxide, Gd₂O₃, a well-known high-κ dielectric that has exhibited a variety of electrolytic properties during the development and operation of the first magneto-ionic devices developed at MIT. Specifically, we focused our investigation on the defect chemistry and electrical properties of Gd₂O₃ in order to better understand the relationship between the structure, chemistry, processing conditions, and operating environment and the material's low-temperature ionic and electronic transport properties and the means for their optimization vis-à-vis memory device operation.
Phase (monoclinic and cubic) and dopant controlled (Ca, Ce, Sr, Zr) polycrystalline pellets of 8 different Gd₂O₃ systems were prepared to investigate various defect regimes in consideration of this material's polymorphism. We considered intrinsic anion-Frenkel disorder and electronic disorder, equilibration with the gas phase, water incorporation, and dopant incorporation in the defect modeling, taking into account the roles of crystallographic structure as well as oxygen ion defect and protonic generation. The primary method utilized to characterize the defect chemistry and transport properties of Gd₂O₃ was the analysis of the dopant, p0₂ and temperature dependencies of the electrical conductivity extracted from complex impedance spectra obtained over the p0₂ range of 1 to 10⁻¹⁵ atm, for 5 isotherms between 700 and 900 °C with 50 °C steps and for a range of acceptor and donor dopants.
Based on the p0₂ dependency of conductivities, in light of the defect modeling, the majority point defects in each system were identified. Electronic and ionic migration energies and thermodynamic parameters were extracted via the defect modeling and temperature dependencies of conductivities. In nearly all cases, the predominant charge carrier under oxidizing conditions at elevated temperatures was identified as the p-type electron-hole, largely due to oxygen excess non-stoichiometry in these systems. With decreasing p0₂, transport tended to switch from semiconducting towards ionic. Depending on phase, dopant type & concentration, temperature, and relative humidity, the predominant ionic conductivity was found to be via oxygen interstitials, oxygen vacancies, and/or protons, the latter given by the propensity of Gd₂O₃ to take up water in solid solution from the environment by the formation of OH[superscript .]species.
Unexpectedly, the ionic mobilities of defects in the denser and less symmetric monoclinic system exhibited higher ionic mobilities than the more open bixbyite structure. The hole electronic species in the investigated systems were found to migrate via the small polaron hopping mechanism with rather large hopping energies. This resulted in an inversion of hole and proton mobility magnitudes at reduced temperatures in the monoclinic system. Extrapolation of ionic and electronic defect conductivities to near room temperature, based on our derived defect and transport models, was not able to explain, on its own, the observed electrolytic properties of the Gd₂O₃ thin films utilized in magneto-ionic devices.
In an attempt to connect the transport properties obtained under equilibrium conditions at elevated temperatures with the behavior of Gd₂O₃ near room temperature, selected thin films Gd₂O₃, prepared by pulsed laser deposition or sputtering, were investigated by complex impedance spectroscopy over the temperature range of 20 - 170°C. While films prepared under dry conditions were indeed found to be highly electrically insulating, films exposed to water vapor exhibited dramatically higher proton conductivities (more than ~10⁸ x) than values extrapolated from high temperature. Parallel thermogravimetric analysis on Gd₂O₃ powder specimens, as a function of temperature, under high humidity conditions, demonstrated a correlation between uptake/loss of incorporated water and conductivity upon cooling and heating, respectively.
We can therefore conclude that the large disconnect between the electrical and electrolytic properties observed between high-κ dielectrics used in CMOS devices such as Gd₂O₃, and their much more highly conductive counterparts used in thin film memory devices, depends strategically on the thin film processing conditions. High-κ dielectrics are fabricated in carefully controlled environments with low relative humidity, while research on, for example, Gd₂O₃ - based magneto-ionic memory devices, is performed under ambient laboratory conditions, where significant water uptake becomes possible at surfaces and grain boundaries. The results and insights obtained in this study can be expected to be applied in achieving further progress in the understanding and optimization of magneto-ionic, memristive, and other devices that rely on proton gating.
by Sunho Kim.
Ph. D.
Ph.D. Massachusetts Institute of Technology, Department of Materials Science and Engineering

The development of efficient, high-performance materials for electrical energy storage and conversion applications has become a must to meet an ever-increasing need for electrical energy. Among devices developed for this purpose, capacitors have been used for pulsed power applications that require large power density with millisecond-scale charge and discharge. However, conventional polymeric films, which possess high breakdown strength, are limited due to low permittivity and hence compromise the energy storage capability of capacitors. In order to develop high energy density dielectric materials for pulsed power applications, two hurdles must be overcome: 1) the appropriate selection of materials that possess not only large permittivity but also high breakdown strength, 2) the optimization of material processing to improve morphology of dielectric films to minimize loss during energy extraction process. This thesis will present the development of novel dielectric material, with emphasis on the optimization of material and thin film processing toward improved morphology as ways to achieve high energy density at the material level. After first two chapters of introduction and experimental details, Chapter 3 will demonstrate the improvement of nanocomposite morphology via processing optimization and study its effect on the energy storage characteristics of nanocomposites thereof. Chapter 4 will investigate dielectric sol-gel materials containing dipolar cyano side groups, which are relatively a new class of material for pulsed power applications. Finally, Chapter 5 will discuss the effect of tunneling barrier layer on sol-gel films to mitigate charge carrier injection and associated conduction and breakdown phenomena, which would be significantly detrimental to the energy storage performance of dielectric sol-gel films.

Doctor of Philosophy
Department of Chemical Engineering
James H. Edgar
Gallium nitride is a promising semiconductor for fabricating field effect transistors for power electronics because of its unique physical properties of wide energy band gap, high electron saturation velocity, high breakdown field and high thermal conductivity. However, these devices are extremely sensitive to the gate leakage current which reduces the breakdown voltage and the power-added efficiency and increases the noise figures. To solve this problem, employing a gate dielectric is crucial to the fabrication of metal insulator semiconductor high electron mobility transistors (MISHEMTs), to reduce the leakage current and increase the magnitude of voltage swings possible. For this device to be successful, imperfections at the oxide-semiconductor interface must be suppressed to maintain the high electron mobility of the device. This research explored multiple high dielectric constant gate oxides (Al[subscript]2O[subscript]3, TiO[subscript]2, and Ga[subscript]2O[subscript]3), deposited on different crystalline orientations and polarities of GaN by atomic layer deposition (ALD) to form metal oxide semiconductor capacitors, including effects of pretreatment on N-polar GaN, ALD TiO[subscript]2/Al[subscript]2O[subscript]3 nano-laminate on thermal oxidized Ga-polar GaN and ALD Al[subscript]2O[subscript]3 on [Italic]c- and [Italic]m-plane GaN Surface pretreatments were shown to greatly alter the morphology of reactive N-polar GaN which is detrimental to the electrical properties. 14 nm thick ALD Al[subscript]2O[subscript]3 films were directly deposited on N-polar GaN without thermal or chemical pretreatments which yield a smooth surface (RMS=0.23 nm), low leakage current (2.09 x 10[superscript]-[superscript]8 A/cm[superscript]2) and good Al[subscript]2O[subscript]3/GaN interface quality, as indicated by the low electron trap density (2.47 x 10[superscript]10 cm[superscript]-[superscript]2eV[superscript]-[superscript]1). In the nano-laminate study, a high dielectric constant of 12.5 was achieved by integrating a TiO[subscript]2/Al[subscript]2O[subscript]3/Ga[subscript]2O[subscript]3 oxide stack layer, while maintaining a low interface trap density and low leakage current. There was a strong correlation between the surface morphology and electrical properties of the device discovered from comparing the ALD Al[subscript]2O[subscript]3 on [Italic]c- and [Italic]m-plane GaN, namely smooth surface lead to small hysteresis. These results indicate the promising potential of incorporation gate dielectric for future GaN devices.

Les matériaux de structure pérovskite de formule générale ABO3 sont les ferroélectriques les plus étudiés pour leurs propriétés intéressantes dans de nombreuses applications technologiques. Cependant leurs propriétés sont directement reliées à la structure et sont fortement conditionnées par les transitions de phases qui dépendent de la température, de la composition chimique et de la pression. Dans le manuscrit de thèse, le comportement sous haute pression de deux matériaux pérovskite SrTi1-xZrxO3 (STZ) et KNb1-XTaXO3 (KNT) est étudié et différentes techniques de frittage pour améliorer la densité des céramiques et optimiser les propriétés ferroélectriques des céramiques K(Nb0.40Ta0.60)O3 et (KxNa1-x)Nb0.6Ta0.4O3 sont examinées.Des analyses sous hautes pressions par spectroscopie Raman et diffraction des rayons X des poudres de SrTi1-xZrxO3 (x= 0.3, 0.4, 0.5, 0.6, 0.7) et KNb1-XTaXO3 (x=0.4, 0.5, 0.6, 0.9) en enclume diamant ont été réalisées. Les spectres Raman montrent une augmentation des modes Raman avec la pression pour les poudres de STZ indiquant que la pression induit des transitions de phases vers des symétries plus basses de la maille dans ces composés.De plus, les expériences de spectroscopie Raman ont fait apparaître une décroissance des modes Raman lorsque la pression est augmentée, montrant bien que la pression induit des transitions de phases vers des structure plus symétriques. L'évolution du mode Raman principal pour les phases orthorhombique et quadratique a été suivi jusqu'à ce que la phase cubique apparaîsse, ce qui nous a permis de proposer un diagramme de phase pression-composition pour les composés KNT.Trois différentes techniques de frittage, utilisation d'additifs, frittage en deux paliers et SPS ont été étudiées pour les céramiques de K(Nb0.4Ta0.6)O3 et (KxNa1-x)Nb0.6Ta0.4O3 . La constante diélectrique et les pertes en fonction de la température des céramiques ont été améliorées par l'utilisation du KF comme additif de frittage et par le frittage en deux paliers. Les échantillons densifiés par SPS présentent une microstructure fine et possèdent les plus fortes densités. Ils ont les meilleurs propriétés ferroélectriques. Aucun changement significatif de la température de Curie ne semble être induit par le taux de Na, et on observe cependant une augmentation de la constante diélectrique et des propriétés ferroélectriques suivant le taux de Na
Perovskite materials whose general chemical formula is ABO3 are one of the most study ferroelectrics due to the interesting properties that they have for technological applications. However, their properties are directly related to structural phase transitions that could depend of temperature, composition and pressure. In the studies presented here, we first examined the high-pressure behavior of two perovskite materials SrTi1-xZrxO3 (STZ) and KNb1-XTaXO3 (KNT), and we later continued to investigate different sintering techniques in order to improve the densification, dielectric and ferroelectric properties of K(Nb0.40Ta0.60)O3 and (KxNa1-x)Nb0.6Ta0.4O3 ceramics.High-pressure Raman scattering and X-ray diffraction investigations of SrTi1-xZrxO3 (x= 0.3, 0.4, 0.5, 0.6, 0.7) and KNb1-XTaXO3 (x=0.4, 0.5, 0.6, 0.9) powders were conducted in diamond anvil cells. Raman scattering experiments showed and increased of Raman modes with pressure for the STZ samples, which indicates that pressure induced phase transitions towards lower symmetry for these compounds.Moreover, high pressure Raman spectroscopy experiments showed a decrease of the Raman modes as the pressure was increased for the KNT samples, showing that pressure induced phase transitions towards higher symmetries. The evolution of the main Raman modes for the orthorhombic and tetragonal phases were followed until the cubic phase was reach, and allowed us to propose a pressure-composition phase diagram for the KNT compounds.Three different sintering techniques, sintered aids, two step sintering and spark plasma sintering, were used on K(Nb0.4Ta0.6)O3 and (KxNa1-x)Nb0.6Ta0.4O3 ceramics. The use of KF as sintered aid and the two step sintering method showed an improvement of the dielectric constant and dielectric losses of these samples. SPS samples presented a fine microstructure with the highest density and the best ferroelectric behavior. We did not detect any changes on the Curie temperature due the amount of Na but and increase of the dielectric constant and the ferroelectric properties was observed due to the amount of Na

Today’s thin-film passive components such as capacitors and inductors are limited to low volumetric density and large form-factors that pose as major roadblock to miniaturization of the power modules. These components are also placed far away from the IC’s leading to large interconnect parasitics and lower operating frequencies. Novel thin-film technologies with high densities and small form-factors are, therefore, required to enable miniaturization and performance at high frequencies. Glass- and silicon- based interposer technologies that utilize vertical through-via interconnections have shown way to improve power distribution network (PDN) performance with thin power-ground planes. However, integration of ultra-high density capacitors in such substrates has not yet been demonstrated. This thesis addresses these challenges with tantalum-based, silicon-integrated, ultrathin, high-density capacitors at higher operating frequencies with lower leakage properties (<0.01µA/µF). The anodization kinetics of tantalum pentoxide and the underlying leakage current mechanisms are investigated to provide optimal process guidelines. The thin-film Ta capacitors demonstrated capacitance density of 0.1 µF/mm2 at 1-10 MHz in form-factors of 50 µm, which corresponds to 6X higher volumetric density relative to commercial tantalum capacitors. An innovative approach to address incompatibility of tantalum electrodes with substrates is pursued by prefabricating the electrodes on a free-standing foil, which are then transferred onto the active wafer to form the capacitors on Si. The integration approach is designed to embed these thin tantalum capacitors on alternative substrates such as organic, glass or silicon, with copper via interconnections for lower parasitics. The thesis also explores titanium-based high-density capacitors with high-permittivity titania dielectric as a potential alternate high-density capacitor technology.

Los metamateriales (MTMs) representan una interesante área de investigación emergente que promete lograr un importante progreso tecnológico y científico en diversas áreas como las telecomunicaciones, la microelectrónica, radar, e imágenes médicas. La cantidad de artículos dedicados a la investigación en esta área (MTMs) se mantiene en pleno crecimiento en la actualidad. Las estructuras MTMs pueden sostener una fuerte resonancia electromagnética con longitudes de onda electricamente pequeñas y por lo tanto son potencialmente aplicables para la miniaturización de los componentes. La miniaturización, optimización del rendimiento del dispositivo mediante la eliminación de frecuencias espurias, y la posibilidad de controlar el ancho de banda del filtro para amplios márgenes de frecuencias es un reto para los presentes y futuros dispositivos de comunicación. Esta tesis se focaliza en el estudio de ambos temas (MTMs y miniaturización) centrándose en las nuevas estrategias para la miniaturización de componentes basados en MTMs. Desde la aparición de estos, los resonadores dieléctricos (DR) son un nuevo tipo de MTMs distinguidos por sus pequeñas pérdidas, así como su fácil combinación con estructuras externas; son la elección adecuada para todo proceso de desarrollo. La principal ventaja de utilizar una alta constante dieléctrica como DR es miniaturizar el tamaño del filtro. El tamaño del filtro de DR es considerablemente menor que la dimensión de la guía de ondas de otros filtros que operan a la misma frecuencia. Dada una constante dieléctrica, tanto la frecuencia de resonancia como el factor de calidad Q se definen a partir de las dimensiones del resonador dieléctrico. Cuanto mayor es la constante dieléctrica, menor es el espacio en el que se concentran los campos, y por lo tanto las dimensiones necesarias para trabajar a una frecuencia de operación definida quedan reducidas. Con el objetivo de miniaturizar las dimensiones del dispositivo, en este trabajo se propone un nuevo diseño para un filtro rechaza banda basado en la alta constante dieléctrica que proporciona una fina capa de pasta epoxy (TFDR) como material DRs excitado a través de una línea microstrip. Además, se propone un filtro pasa banda diseñado en base a los resonadores dieléctricos incrustados (EDR), esto constituye un nuevo enfoque en el campo de los resonadores miniaturizados adaptado a los metamateriales, logrando evitar la degradación del factor Q inherente al coeficiente de acoplamiento basado en partículas eléctricamente pequeñas. En esta tesis se propone también un nuevo filtro pasa de banda basado en resonadores de anillo dividido (SRRs), que es uno de los bloques de construcción MTMs más popular hoy en día. Los filtros de paso de banda basados en este concepto resultan prometedores para las aplicaciones donde la miniaturización y la compatibilidad con la tecnología de ondas planares milimétricas son los requisitos críticos del diseño. Además, para mayor miniaturización, tecnología DR de incrustado es reportada. Otro enfoque para la reducción de tamaño se basa en modificar el resonador tradicional para generar modos adicionales, los cuales hacen que el resonador se comporte como un resonador multimodal. Por último, se propone un filtro compacto paso banda de banda ultra ancha (UWB) utilizando un resonador de anillo abierto conectado a tierra empleado como un resonador multimodal (MMR). Esta propuesta permite utilizar cinco resonancias para producir un ancho de banda fraccional del 128% dentro de la banda ultra ancha. Para demostrar y validar la funcionalidad de los diseños, todos los dispositivos propuestos se han implementado y fabricado, con una excelente concordancia entre las simulaciones y las medidas experimentales. A través de estos métodos ha quedado demostrado que los modelos de sus circuitos equivalentes proporcionan una descripción precisa del comportamiento de las estructuras. En este trabajo se ha conseguido relacionar una relación directa entre las dimensiones físicas del dispositivo y su modelo equivalente eléctrico en forma de circuito.
Metamaterials (MTMs) represent an exciting emerging research area that promises to bring about important technological and scientific advancement in various areas such as telecommunication, radar, microelectronic, and medical imaging. The amount of research on this MTMs area has grown extremely quickly in this time. MTM structure are able to sustain strong sub-wavelength electromagnetic resonance and thus potentially applicable for component miniaturization. Miniaturization, optimization of device performance through elimination of spurious frequencies, and possibility to control filter bandwidth over wide margins are challenges of present and future communication devices. This thesis is focused on the study of both interesting subject (MTMs and miniaturization) which is new miniaturization strategies for MTMs component. Since, the dielectric resonators (DR) are new type of MTMs distinguished by small dissipative losses as well as convenient conjugation with external structures; they are suitable choice for development process. The primary advantage in using a high dielectric constant as a DR is to miniaturize the filter size. The size of DR filter is considerably smaller than the dimension of waveguide filters operate at the same frequency. For a given dielectric constant, both resonant frequency and Q-factor are defined according to the dielectric resonator dimensions. That, the higher the dielectric constant, the smaller the space within which the fields are concentrated, the lower the dimension at a defined frequency. To obtain the required compact sizes new stop-band filter is proposed in this work based on number of thick film high dielectric constant epoxy paste (TFDR) as DRs which excited with a microstrip line. In addition, a band-pass filter is proposed based on embedded dielectric resonators (EDR) constitutes a new approach to the miniaturized resonators suitable for metamaterials design without the Q degradation inherent to the coupling coefficient based on sub-wavelength particles. Also this thesis is proposed a new band-pass filter based on split ring resonators (SRRs), which is a one of the popular MTMs building blocks today. The band-pass filters based on this concept can be very promising for the applications where miniaturization and compatibility with planar millimeter wave technology are the important issues. Also, for further miniaturization, embedded DR technology is reported. Another approach for size reduction is modifying the traditional resonator to generate additional modes, which make the resonator to behave as a multimode resonator. Finally a compact ultra-wide band-pass (UWB) band-pass filter using grounded open ring resonator as a multimode resonator (MMR) is proposed. The approach allows using five resonances to produce a 128% fractional bandwidth into the ultra-wide band. A general theoretic framework has been established using transmission matrix description of the filter constituent components. To demonstrate and validate designs functionality, all the proposed devices are implemented and fabricated, which a good agreement between simulations and measurement are obtained. Through these methods it is demonstrated that their equivalent circuit models provide an accurate description of the considered structures. Indeed, a clear relationship between their equivalents circuit model and the layout physical dimensions were found.

Although 1.5 and 3 Tesla (T) magnetic resonance (MR) systems remain the clinical standard, the number of 7 T MR systems has increased over the past decade because of the promise of higher signal-to-noise ratio (SNR), which can translate to images with higher resolution, improved image quality and faster acquisition times. However, there are a number of technical challenges that have prevented exploiting the full potential of ultra-high field (≥ 7 T) MR imaging (MRI), such as the inhomogeneous distribution of the radiofrequency (RF) electromagnetic field and specific energy absorption rate (SAR), which can compromise image quality and patient safety.

To better understand the origin of these issues, we first investigated the dependence of the spatial distribution of the magnetic field associated with a surface RF coil on the operating frequency and electrical properties of the sample. Our results demonstrated that the asymmetries between the transmit (B₁⁺) and receive (B ₁^–) circularly polarized components of the magnetic field, which are in part responsible for RF inhomogeneity, depend on the electric conductivity of the sample. On the other hand, when sample conductivity is low, a high relative permittivity can result in an inhomogeneous RF field distribution, due to significant constructive and destructive interference patterns between forward and reflected propagating magnetic field within the sample.

We then investigated the use of high permittivity materials (HPMs) as a method to alter the field distribution and improve transmit and receive coil performance in MRI. We showed that HPM placed at a distance from an RF loop coil can passively shape the field within the sample. Our results showed improvement in transmit and receive sensitivity overlap, extension of coil field-of-view, and enhancement in transmit/receive efficiency. We demonstrated the utility of this concept by employing HPM to improve performance of an existing commercial head coil for the inferior regions of the brain, where the specific coil’s imaging efficiency was inherently poor. Results showed a gain in SNR, while the maximum local and head SAR values remained below the prescribed limits. We showed that increasing coil performance with HPM could improve detection of functional MR activation during a motor-based task for whole brain fMRI.

Finally, to gain an intuitive understanding of how HPM improves coil performance, we investigated how HPM separately affects signal and noise sensitivity to improve SNR. For this purpose, we employed a theoretical model based on dyadic Green’s functions to compare the characteristics of current patterns, i.e. the optimal spatial distribution of coil conductors, that would either maximize SNR (ideal current patterns), maximize signal reception (signal-only optimal current patterns), or minimize sample noise (dark mode current patterns). Our results demonstrated that the presence of a lossless HPM changed the relative balance of signal-only optimal and dark mode current patterns. For a given relative permittivity, increasing the thickness of the HPM altered the magnitude of the currents required to optimize signal sensitivity at the voxel of interest as well as decreased the net electric field in the sample, which is associated, via reciprocity, to the noise received from the sample. Our results also suggested that signal-only current patterns could be used to identify HPM configurations that lead to high SNR gain for RF coil arrays. We anticipate that physical insights from this work could be utilized to build the next generation of high performing RF coils integrated with HPM.

The continuous and aggressive dimensional miniaturization ofthe conventional complementary-metal-oxide semiconductor (CMOS)architecture has been the main impetus for the vast growth ofIC industry over the past decades. As the CMOS downscalingapproaches the fundamental limits, unconventional materials andnovel device architectures are required in order to guaranteethe ultimate scaling in device dimensions and maintain theperformance gain expected from the scaling. This thesisinvestigates both unconventional materials for the gate stackand the channel and a novel notched-gate device architecture,with the emphasis on the challenging issues in processintegration.

High-κ gate dielectrics will become indispensable forCMOS technology beyond the 65-nm technology node in order toachieve a small equivalent oxide thickness (EOT) whilemaintaining a low gate leakage current. HfO₂and Al₂O₃as well as their mixtures are investigated assubstitutes for the traditionally used SiO₂in our MOS transistors. These high-κ filmsare deposited by means of atomic layer deposition (ALD) for anexcellent control of film composition, thickness, uniformityand conformality. Surface treatments prior to ALD are found tohave a crucial influence on the growth of the high-κdielectrics and the performance of the resultant transistors.Alternative gate materials such as TiN and poly-SiGe are alsostudied. The challenging issues encountered in processintegration of the TiN or poly-SiGe with the high-k are furtherelaborated. Transistors with TiN or poly-SiGe/high-k gate stackare successfully fabricated and characterized. Furthermore,proof-of-concept strained-SiGe surface-channel pMOSFETs withALD high-κ dielectrics are demonstrated. The pMOSFETs witha strained SiGe channel exhibit a higher hole mobility than theuniversal hole mobility in Si. A new procedure for extractionof carrier mobility in the presence of a high density ofinterface states found in MOSFETs with high-κ dielectricsis developed.

A notched-gate architecture aiming at reducing the parasiticcapacitance of a MOSFET is studied. The notched gate is usuallyreferred to as a local thickness increase of the gatedielectric at the feet of the gate above the source/drainextensions. Two-dimensional simulations are carried out toinvestigate the influence of the notched gate on the static anddynamic characteristics of MOSFETs. MOSFETs with optimizednotch profile exhibit a substantial enhancement in the dynamiccharacteristics with a negligible effect on the staticcharacteristics. Notched-gate MOSFETs are also experimentallyimplemented with the integration of a high-κ gatedielectric and a poly-SiGe/TiN bi-layer gate electrode.

Key words:CMOS technology, MOSFET, high-κ, gatedielectric, ALD, surface pre-treatment, metal gate, poly-SiGe,strained SiGe, surface-channel, buried-channel, notchedgate.

Le sujet de cette thèse porte sur la compréhension et la modélisation du comportement électrique de système d'isolation soumis à un fort champ électrique continu. Les propriétés électriques du polymère sont directement pilotées par ses hétérogénéités chimiques et physiques présentes à plusieurs échelles. Dans cette étude, un nouveau modèle est développé ayant pour but de simuler l'évolution de la microstructure de polymère avec la température, le champ électrique et le temps et de simuler l'impact de cette évolution sur les propriétés électriques du polymère. Dans ce modèle, des matrices sont utilisées pour décrire la distribution de chacune des hétérogénéités et propriété électriques d'un polymère semi-cristallin. L'évolution de ces matrices de microstructure suit des lois génétiques dont la définition a été obtenue à partir d'une caractérisation fine des propriétés physicochimiques et électriques de matériaux spécifiques en fonction de la température et du champ électrique. Ces lois implémentées sont basés sur des calculs simples permettant un temps de résolution plus rapide comparativement aux autres modèles préexistants. Basée sur ces lois d'évolutions génétiques, le comportement électrique sous champ électrique continue de polymère isolant peut être simulé uniquement à partir d'une caractérisation physique et chimique de ce polymère. Le modèle est ainsi capable de reproduire le comportement électrique de plusieurs polymères semi-cristallins et de suivre les données expérimentales mesurées par ailleurs. Le modèle intègre plusieurs physiques tels que la diffusion, le transport ionique et le transport électronique, lui permettant ainsi de prendre en compte l'influence d'un grand nombre d'hétérogénéités
This thesis presents a research work on understanding and modeling the electrical behavior of insulation system in cables subjected to high DC constraints. Electrical properties of polymeric insulation are directly related to their chemical and physical heterogeneities present at several scales. In this work, a new model is developed to simulate the modification over time of the microstructure in insulation polymers under electric field and temperature as well as the subsequent impacts on electrical properties. In this model, matrices are used to describe the distribution of each heterogeneity and electrical property in semi-crystalline polymer. When stressed under electric field and at temperature, matrices of microstructure evolve from implemented genetic laws. This simulated microstructure evolution yields to the simulation of electrical property changes over time at transient and steady state. To define these genetic laws, a detailed characterization of the physical, chemical and electrical properties of specific materials as a function of temperature and electric field is experimentally performed. Genetic laws are notably implemented to take into account the impact of the semi-crystalline structure and the presence of chemical residues in polymer electrical properties. Based on these genetic evolution laws, this modeling approach allows simulating DC electrical behavior of polymers only from their physical and chemical characterizations and reproduce accurately experimental electrical behavior with a faster solving time compared to other simulation methods

Ce travail de thèse porte sur l'intégration de matériaux de haute constante diélectrique (High-k) en tant que diélectrique interpoly dans les mémoires non volatiles de type Flash. L'objectif est de déterminer quel matériaux High-k seraient des candidats probables au remplacement de l'empilement ONO utilisé en tant que diélectrique interpoly. Une gamme de matériaux high-k ont été étudiés via des caractérisations électriques (I-V, C-V, statistique de claquage…) et physiques (TEM, EDX, XPS…) afin d'éliminer les matériaux ne répondant pas au cahier des charges d'un diélectrique interpoly. Les difficultés et les obstacles liés a l'intégration de matériaux High-k dans une chaine de procédés de fabrication de mémoires Flash ont été pris en compte, et des solutions ont été proposées
The work of this thesis is on integration of high dielectric constant materials (High-k) as dielectric interpoly in Flash non volatile memories. The objective is to determine which High-k materials are suitable as interpoly dielectric in place of the ONO stack currently used. A range of High-k materials have been studied by electrical characterizations (I-V, C-V, breakdown statistics…) and physical characterizations (TEM, EDX, XPS…) in order to select those with the best properties for an interpoly dielectric. The difficulties in integration of High-k materials in a Flash memory process flow have been taken in account and solutions have been proposed

Doctor of Philosophy
Department of Chemical Engineering
James H. Edgar
The integration of high-κ dielectrics with silicon and III-V semiconductors is important due to the need for high speed and high power electronic devices. The purpose of this research was to find the best conditions for fabricating high-κ dielectrics (oxides) on GaN or Si. In particular high-κ oxides can sustain the high breakdown electric field of GaN and utilize the excellent properties of GaN. This research developed an understanding of how process conditions impact the properties of high-κ dielectric on Si and GaN. Thermal and plasma-assisted atomic layer deposition (ALD) was employed to deposit TiO₂ on Si and Al₂O₃ on polar (c-plane) GaN at optimized temperatures of 200°C and 280°C respectively. The semiconductor surface treatment before ALD and the deposition temperature have a strong impact on the dielectric’s electrical properties, surface morphology, stoichiometry, and impurity concentration. Of several etches considered, cleaning the GaN with a piranha etch produced Al₂O₃/GaN MOS capacitors with the best electrical characteristics. The benefits of growing a native oxide of GaN by dry thermal oxidation before depositing the high-κ dielectric was also investigated; oxidizing at 850°C for 30 minutes resulted in the best dielectric-semiconductor interface quality. Interest in nonpolar (m-plane) GaN (due to its lack of strong polarization field) motivated an investigation into the temperature behavior of Al₂O₃/m-plane GaN MOS capacitors. Nonpolar GaN MOS capacitors exhibited a stable flatband voltage across the measured temperature range and demonstrated temperature-stable operation.

Ce travail de thèse se situe dans le concept général de contrôler, améliorer et optimiser la performance électrique des matériaux composites par l'analyse systématique de la réponse diélectrique globale des matériaux composites pour différentes morphologies. Pour mener à des informations complètes, une corrélation entre trois approches indépendants a été réalisée: des simulations numériques, des calculs analytiques et des mesures diélectriques (spectromètre diélectrique de type Novo-contrôle). D'abord on a établie des lois d'échelles et la contribution originale de cette thèse est de réussir à mettre des lois d'échelle universelle pour la réponse diélectrique globales des matériaux composites qui sont censés de servir à la base pour les actuelles et futures études sur les propriétés électriques et diélectriques des matériaux composites. Comme application, ces lois d'échelles que nous avons dérivées nous ont permis de développer des applications, tel que la conception des matériaux multicouches à haute permittivité et faible pertes diélectriques au service des applications dans des domaines de stockage d'énergie, en ajustant les valeurs de conductivité et les fractions de volume des phases constituantes. Cet approche a été menée sur des composites en structure bicouches constitués d'une superposition de couches de polymères ayant des conductivités différentes. Et en plus, ces lois d'échelles ont été à la base pour la découverte pour la première fois, d'un critère de discrimination entre deux types différent de polarisation électriques: la polarisation interfaciale de type MWS et la polarisation d'électrode. Aussi, on a dérivé une nouvelle formule qui est valable à la fois pour la polarisation d'électrode et les effets de la polarisation interfaciale. Elle permet non seulement d'estimer l'épaisseur des couches interfaciales formées à l'électrode en raison des effets de polarisation mais aussi à développer une nouvelle méthode de mesure de la conductivité des matériaux sans contact direct qui a servi pour des mesures couplées diélectrique – mécanique
This research is significant in that it not only develops a generalized approach for modeling the electrical properties of multiphase composite materials but also introduces novel experimental applications in the domain of dielectric properties of composite materials. In order to get complete information: numerical simulations, analytical calculations and dielectric measurements by means of Broadband Dielectric Spectroscopy (BDS) were carried out in this study. First, we derived the scaling laws through a systematically study of global dielectric response of composite materials with different morphology and the original contribution of this thesis is to succeed to derive a universal scaling laws for the global dielectric response of composite materials. Based on these scaling laws three achievements are taken place: designing layered polymer materials with high values of permittivity and low dielectric losses, by adjusting the values of conductivity and the volume fraction of the constituent phases. Also, we discover a new discrimination criterion for electrical polarizations at external and internal interfaces: electrode polarization vs. (MWS) interfacial polarization effects in dielectric spectra of materials. This work opens the general perspective of finding discrimination criteria for different types of electrical polarization, which will represent a useful tool in disseminating the nature of different contributions appearing in the dielectric spectra of materials. Based on our analysis, we derive a new formula. This formula is valid for both electrode polarization and interfacial polarization effects. It allows one to determine the conductivity value from the frequency position of the Maxwell-Wagner-Sillars peak. Measurements of the conductivity values of samples without a direct contact are done. An excellent agreement between experiment and calculations is obtained. This results offer the opportunity to develop a new coupled electrical-mechanical approach, by electrical measurements performed during mechanical stretching

Recent advances in medical imaging have greatly improved the success of cardiovascular and intracardiac interventions. This research aims to improve capacitive micromachined ultrasonic transducers (CMUT) based imaging catheters for intravascular ultrasound (IVUS) and intra-cardiac echocardiography (ICE) for 3-D volumetric imaging through integration of high-k thin film material into the CMUT fabrication and array design. CMUT-on-CMOS integration has been recently achieved and initial imaging of ex-vivo samples with adequate dynamic range for IVUS at 20MHz has been demonstrated; however, for imaging in the heart, higher sensitivities are needed for imaging up to 4-5 cm depth at 20MHz and deeper at 10MHz. Consequently, one research goal is to design 10-20MHz CMUT arrays using integrated circuit (IC) compatible micro fabrication techniques and optimizing transducer performance through high-k dielectrics such as hafnium oxide (HfO2). This thin film material is electrically characterized for its dielectric properties and thermal mechanical stress is measured. Experiments on test CMUTs show a +6dB improvement in receive (Rx) sensitivity, and +6dB improvement in transmit sensitivity in (Pa/V) as compared to a CMUT using silicon nitride isolation (SixNy) layer. CMUT-on-CMOS with HfO2 insulation is successfully integrated and images of a pig-artery was successfully obtained with a 40dB dynamic range for 1x1cm2 planes. Experimental demonstration of side looking capability of single chip CMUT on CMOS system based FL dual ring arrays supported by large signal and FEA simulations was presented. The experimental results which are in agreement with simulations show promising results for the viability of using FL-IVUS CMUT-on-CMOS device with dual mode side-forward looking imaging. Three dimensional images were obtained by the CMUT-on-CMOS array for both a front facing wire and 4 wires that are placed perpendicular to the array surface and ~4 mm away laterally. For a novel array design, a dual gap, dual frequency 2D array was designed, fabricated and verified against the large signal model for CMUTs. Three different CMUT element geometries (2 receive, 1 transmit) were designed to achieve ~20MHz and ~40MHz bands respectively in pulse-echo mode. A system level framework for designing CMUT arrays was described that include effects from imaging design requirements, acoustical cross-talk, bandwidths, signal-to-noise (SNR) optimization and considerations from IC limitations for pulse voltage. Electrical impedance measurements and hydrophone measurements comparisons between design and experiment show differences due to inaccuracies in using SixNy homogenous material in simulation compared to fabricated thin-film stacks (HfO2-AlSi-SixNy). It is concluded that for “thin” membranes the effect of stiffness and mass of HfO2 and AlSi (top electrode) cannot be ignored in the simulation. Also, it is understood that aspect ratio (width to height) <10 will have up to 15% error for center frequency predicted in air when the thin-plate approximation is used for modelling the bending stiffness of the CMUT membrane.

La maîtrise de la communication et de l'information est un atout primordial dans les stratégies de pouvoir, qu'elles soient militaires, politiques ou commerciales. Celui qui est capable de transmettre l'information plus vite prend l'avantage sur les autres. Tel est le moteur de la croissance et du progrès dans le domaine des télécommunications. L'omniprésence grandissante des dispositifs communicants témoigne de l'expansion exponentielle qu'a connu ce domaine depuis les premières communications sans fil. À l'époque du all-in-one, la multiplication des applications au sein d'un même appareil nécessite l'utilisation de composants toujours plus performants et petits . Au cœur de ces systèmes, les filtres ont une importance grandissante. Dans un environnement spatial, les contraintes de fiabilité et d'encombrement sont particulièrement drastiques. Le choix des matériaux est par ailleurs limité, ce qui réduit les possibilités d'innovation. Cependant, l'amélioration de la précision et de la fiabilité dans les technologies de fabrication ouvre de nouvelles perspectives d'innovation et d'amélioration des composants. Ces travaux ont ainsi été motivés par ce souci d'apporter toujours plus de performance et de fiabilité, pour un encombrement moindre en tirant profit du potentiel offert par l'association du concept SIW et de la technologie LTCC. Les résultats mettent à jour de sérieuses dispersions technologiques. Cependant, le potentiel de l'association SIW/LTCC est démontré, et les difficultés rencontrées sont surmontables. Les filtres SIW en technologie LTCC présentent donc des atouts pour s'imposer comme une alternative sérieuse aux solutions existantes.

abstract: The mechanism of loss in high performance microwave dielectrics with complex perovskite structure, including Ba(Zn1/3Ta2/3)O3, Ba(Cd1/3Ta2/3)O3, ZrTiO4-ZnNb2O6, Ba(Zn1/3Nb2/3)O3, and BaTi4O9-BaZn2Ti4O11, has been investigated. We studied materials synthesized in our own lab and from commercial vendors. Then the measured loss tangent was correlated to the optical, structural, and electrical properties of the material. To accurately and quantitatively determine the microwave loss and Electron Paramagnetic Resonance (EPR) spectra as a function of temperature and magnetic field, we developed parallel plate resonator (PPR) and dielectric resonator (DR) techniques. Our studies found a marked increase in the loss at low temperatures is found in materials containing transition metal with unpaired d-electrons as a result of resonant spin excitations in isolated atoms (light doping) or exchange coupled clusters (moderate to high doping) ; a mechanism that differs from the usual suspects. The loss tangent can be drastically reduced by applying static magnetic fields. Our measurements also show that this mechanism significantly contributes to room temperature loss, but does not dominate. In order to study the electronic structure of these materials, we grew single crystal thin film dielectrics for spectroscopic studies, including angular resolved photoemission spectroscopy (ARPES) experiment. We have synthesized stoichiometric Ba(Cd1/3Ta2/3)O3 [BCT] (100) dielectric thin films on MgO (100) substrates using Pulsed Laser Deposition. Over 99% of the BCT film was found to be epitaxial when grown with an elevated substrate temperature of 635 C, an enhanced oxygen pressures of 53 Pa and a Cd-enriched BCT target with a 1 mol BCT: 1.5 mol CdO composition. Analysis of ultra violet optical absorption results indicate that BCT has a bandgap of 4.9 eV.
Dissertation/Thesis
Ph.D. Materials Science and Engineering 2013

博士
國立成功大學
電機工程學系碩博士班
98
Microwave dielectric resonators (DRs) which are fabricated by high dielectric constant, high quality factor, and good temperature stability of microwave dielectric materials are suitably applied in antennas, filters, oscillators, and diplexers. Recently, with the rapidly progress in the microwave communication systems, miniaturization and performance enhancement have become two main requirements of the microwave devices. Therefore, high quality factor dielectric materials can be utilized in designing high-performance microwave devices in communication system. Moreover, the integration of dielectric materials is also main method to carry out the miniaturization of microwave devices. In addition, to develop microwave dielectric materials, lower sintering temperatures plays an important role in the future. As mentioned above, the main study of this dissertation is divided five parts which preparation of high dielectric constant, high quality factor, low sintering temperature microwave dielectric materials, fabrication of high quality Mg4Ta2O9 dielectric thin films and their applications on microstrip bandpass filters. 1.Development of High Q Microwave Dielectric Materials [a]Study of Mg2TiO4 Ceramics: (1)Binary titanate ceramic Mg2TiO4 ( ~ 14, Q×f ~ 150,000 GHz, and τf ~ –50 ppm/°C), having extremely high quality factor, were reported as promising dielectric ceramics for microwave applications. Their low cost even brought much more attention. In fact, they have already been used as dielectric materials for GPS antennas and wireless LAN filters. Therefore, the spinel-structured Mg2TiO4 is worthy to investigate its microwave properties. In this dissertation, with partial replacement of Mg by Co or Ti by Sn, the Q×f of the dielectrics (Mg0.95Co0.05)2TiO4 ( ~ 15.7, Q×f ~ 286,000 GHz, and τf ~ –52.5 ppm/°C) and Mg2(Ti0.95Sn0.05)O4 ( ~ 15.57, Q×f ~ 318,000 GHz, and τf ~ –45.1 ppm/°C) can be easily boosted to a value higher than 250,000 GHz and retain compatible and τf. (2)In order to achieve temperature-stable materials, CaTiO3, Ca0.61Nd0.26TiO3, Ca0.6La0.8/3TiO3, Ca0.8Sm0.4/3TiO3, and Ca0.8Sr0.2TiO3 were added to (Mg0.95Co0.05)2TiO4 and Mg2(Ti0.95Sn0.05)O4 ceramics, respectively. Addition of compensators, having much smaller grain sizes in comparison with that of (Mg0.95Co0.05)2TiO4 and Mg2(Ti0.95Sn0.05)O4, could effectively hold back abnormal grain growth in the (Mg0.95Co0.05)2TiO4 and Mg2(Ti0.95Sn0.05)O4 matrixes. Hence, using the compensators can effectively lower the sintering temperature of the ceramic bulks. Dielectric characteristics and sintering behavior of these ceramic systems were investigated. A two-phase system, which was confirmed by the XRD patterns and the EDX analysis. Moreover, the microstructures of the sintered bulks were characterized by SEM. (3)As mentioned above, the optimal microwave dielectric properties are achieved in 0.92(Mg0.95Co0.05)2TiO4–0.08Ca0.8Sr0.2TiO3 ceramics sintered at 1300°C for 4 h with a dielectric constant ( ) value of 19.22, a quality factor (Q×f) value of 123,200 GHz, and a temperature coefficient of resonant frequency (τf) value of 2.8 ppm/°C. Furthermore, in order to lower the sintering temperature, sintering aid such as B2O3 was used to produce the liquid phase that degrades the sintering temperatures. The microstructures and the microwave dielectric properties with B2O3 additions were investigated. [b] Study of ZnX2O6 (X = Nb and Ta) Ceramics: (1)Partial Replacement of ZnNb2O6 Ceramics The effects of substituting Nb5+ with Ta5+ on the microwave dielectric properties of the ZnNb2O6 ceramics were investigated in this dissertation. The forming of Zn(Nb1-xTax)2O6 (x = 0–0.09) solid solution was confirmed by the measured lattice parameters and the EDX analysis. A fine combination of microwave dielectric properties ( ~ 24.57, Q×f ~ 152,000 GHz, and τf ~ –71.1 ppm/°C) was achieved for Zn(Nb0.95Ta0.05)2O6 solid solution sintered at 1175°C for 2 h. (2)Partial Replacement of ZnTa2O6 Ceramics ZnTa2O6 microwave dielectric materials have been developed as the microwave dielectric resonators in the past, because the dielectric resonators fabricated by ZnTa2O6 ceramics reveal the excellent microwave dielectric properties. However, the quality factor of ZnTa2O6 ceramic is still not good enough for the applications at the microwave frequency. In order to improve the microwave dielectric properties, with the partial replacement of ZnTa2O6 ceramics were investigated. The forming of (Zn0.95M2+0.05)Ta2O6 (M2+ = Co, Mn, Mg, and Ni) and Zn(Ta0.95Nb0.05)2O6 solid solutions were confirmed by the XRD patterns, HR-TEM lattice images, and the EDS analysis. 2.Research of High K Microwave Dielectric Materials Several complex perovskites ceramics A(B2+0.5B4+0.5)O3 (where A = La, Nd, and Sm; B2+ = Mg, Zn, and Co; B4+ = Ti and Sn) have been reported due to their excellent microwave dielectric properties. Among them, La(Mg0.5Ti0.5)O3 has a high dielectric constant ( ~ 29), a high quality factor (Q×f value ~ 75,500 GHz), and a large negative temperature coefficient of resonant frequency (τf ~ –65 ppm/°C). In order to compensate the negative τf of the La(Mg0.5Ti0.5)O3 ceramics, Ca0.8Sm0.4/3TiO3 and Ca0.8Sr0.2TiO3 perovskite which have positive τf had been added. The experiment result showed that 0.5La(Mg0.5Ti0.5)O3–0.5Ca0.8Sr0.2TiO3 have the best microwave dielectric properties, it’s ~ 47.12, Q×f ~ 35,000 GHz, and τf ~ –4.7 ppm/°C. In addition, the X-ray diffraction (XRD) patterning and scanning electron microscopy (SEM) analysis were also employed to study the crystal structures and microstructures of the ceramics. 3.Investigation of Low-Temperature Sintering Microwave Dielectrics Using CuO-Doped Zn(Nb0.95Ta0.05)2O6 Ceramics The influence of CuO additions on the sintering behavior and microwave dielectric properties of Zn(Nb0.95Ta0.05)2O6 ceramic and its chemical compatibility with Ag have been investigated. The CuO additions not only effectively lower the sintering temperature of Zn(Nb0.95Ta0.05)2O6 ceramics to 930°C, the optimized sintering temperatures also decrease with increasing CuO contents due to the liquid phase effect. The Q×f value is a function of the sintering temperature and the amount of CuO addition. With 4.5 wt% CuO addition, it varies from 8,500 to 77,200 GHz as the sintering temperature increases from 840°C to 930°C for 2 h. For low-firing multilayer applications, a combination of dielectric properties with an ~ 22.87, a Q×f ~ 77,200 GHz, and a τf ~ –70.8 ppm/°C can be achieved for 4.5 wt% CuO-doped Zn(Nb0.95Ta0.05)2O6 ceramic sintered at 930°C for 2 h. 4.Fabrication and Characteristics of Mg4Ta2O9 Dielectric Thin Films by RF Magnetron Sputtering Recently, high permittivity dielectric films with low leakage current and high break-down voltage are of the great importance for a variety of integrated devices, such as storage capacitors in dynamic random access memory (DRAM). In this dissertation, the Mg4Ta2O9 target was prepared and used for deposition. The crystal structure and surface morphology of the films affected by deposition conditions, such as RF power and sputtering time. The physical and electrical characteristics of the thin films were investigated. 5.Design and Fabrication of Microstrip Bandpass Filters The microstrip bandpass filters of SIR with a (skew-symmetric) feed structure and open-stubs are presented. In this dissertation, using high permittivity ceramic substrates to miniaturize the sizes of Butterworth bandpass filters are investigated. The selectivity and stopband rejction of the designed filters can be improved significantly by utilizing the feed structure and open-stubs. The responses of the bandpass filters using Al2O3 ( = 9.8, = 0.0005, 1.6-mm thickness), and 0.92(Mg0.95Co0.05)2TiO4–0.08Ca0.8Sr0.2TiO3 with 0.5 wt% B2O3 addition ( = 18.07, = 0.0001, 1.6-mm thickness) ceramic substrates are designed at a center frequency of 2.4 GHz. The compact size and high-performance of the filter are presented in this thesis.