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<p>With the emergence of 5G/mm-Wave communication, there is a growing need for novel front-end electromechanical devices in filtering and carrier generation applications. CMOS-MEMS resonators fabricated using state-of-the-art Integrated Circuit (IC) manufacturing processes provide a significant advantage for power, area and cost savings. In this work, a comprehensive physics-based compact model capable of capturing the non-linear behaviour and other non-idealities has been developed for MEMS resonators seamlessly integrated in CMOS. As the first large signal model for CMOS-embedded resonators, it enables holistic design of MEMS components with advanced CMOS circuits as well as system-level performance evaluation within the framework of modern IC design tools. Global Foundries 14nm FinFET (GF14LPP) Resonant Body Transistors (fRBT) operating at 11.8 GHz are demonstrated and benchmarked against this large-signal electromechanical model. </p> <p><br></p> <p>Additionally, there is a growing interest in CMOS-integrable ferroelectric materials such as Hafnium Dioxide (HfO2) and Aluminum Scandium Nitride (AlScN) for next-generation memory and computation, as well as electromechanical transduction in CMOS-MEMS devices. This work also explores the performance of 700 MHz Ferroelectric Capacitor-based resonators in the Texas Instruments HPE035 process under high-power operating conditions. Identification of previously unreported characteristics, together with the first nonlinear large signal model for integrated ferroelectric resonators, provides insights on the design of frequency references and acoustic filters using ferroelectric transducers. </p> <p><br></p> <p>Extending the range of unreleased CMOS-MEMS resonators to lower frequency using novel design, we also investigate embedded transducers in chip-scale devices for physical sensing. We have simulated and modeled the transducer coupling for low-frequency propagating modes and benchmarked their projected performance against state-of-the-art conventional MEMS sensors. A new approach to phononic crystal (PnC) Interdigitated Transducers (IDTs) is presented emulating the acoustic dispersion in conventional ICs. Unloaded quality factors up to 15,000 have been measured in $\sim$80 MHz resonators, demonstrating their capacity for resonant rotation sensing. We present a unique methodology to amplify and collimate acoustic waves using CMOS-design-rule-compliant Graded Index (GRIN) Phononic IDTs. Ultimately, the CMOS-MEMS techniques presented in this work for both RF applications and physical sensing can facilitate additional functionality in standard CMOS and emerging 3D heterogeneously integrated (3DHI) ICs with minor or no modifications to manufacturing and packaging. This enables new paradigms in next-generation communications, internet of things (IoT), and hardware security.</p>

Ferroelectric-reinforced metal matrix composites (FR-MMCs) offer the potential to improve damping characteristics of structural materials. Many structural materials are valued based on their stiffness and strength; however, stiff materials typically have limited inherent ability to dampen mechanical or acoustic vibrations. The addition of ferroelectric ceramic particles may also augment the strength of the matrix, creating a multifunctional composite. The damping behavior of two FR-MMC systems has been examined. One involved the incorporation of barium titanate (BaTiO3) particles into a Cu- 10w%Sn (bearing bronze) matrix and the other incorporating them into an electroformed Ni matrix. Here the damping properties of the resulting ferroelectric reinforced metal matrix composites (FR-MMCs) have been investigated versus frequency, temperature (above and below the Curie temperature of the reinforcement), and number of strain cycles. FR-MMCs currently represent a material system capable of exhibiting increased damping ability, as compared to the structural metal matrix alone. Dynamic mechanical analysis and neutron diffraction have shown that much of this added damping ability can be attributed to the ferroelectric/ferroelastic nature of the reinforcement. / Ph. D.

Ferroelectric (piezoelectric) and ferromagnetic materials have extensively permeated in modern industry. (Na1/2Bi1/2)TiO3-BaTiO3 (NBT-x%BT) single crystals and K1/2Na1/2NbO3 (KNN) textured ceramics are top environment-friendly candidates which have potential to replace the commercial lead zirconate titanate or PZT. High magnetostrictive strain (up to 400 ppm) of Fe-xat.%Ga makes this alloys promising alternatives to existing magnetostrictive materials, which commonly either contain costly rare-earth elements or have undesirable mechanical properties for device applications. These systems have common characteristics: compositional/thermal/ electrical dependent structural heterogeneity and chemical disorder on sub-micron or nano scale, resulting in diverse local structures and different physical properties. In this work, I have investigated domain and local structures of NBT-x%BT crystals, KNN ceramics and Fe-xat.%Ga alloys under various conditions, mainly by scanning probe and electron transmission techniques. In NBT-x%BT single crystals, polarized light, piezo-response force (PFM) and transmission electron (TEM) microscopies were used to study domain structures and oxygen octahedral tiltings. Hierarchical domain structures were found in NBT: a high-temperature tetragonal ferroelastic domain structure is elastically inherited into a lower temperature rhombohedral ferroelectric phase. Nanoscale domain engineering mechanism was found to still work in NBT-x%BT system and a modified phase diagram was proposed based on domain observations. An increased intensity of octahedral in-phase tilted reflections and a decrease in the anti-phase ones was observed, with increasing x as the morphotropic phase boundary (MPB) is approached. It was also found that Mn substituents favor the formation of long range ordered micro-sized ferroelectric domains and octahedral in-phase tilted regions near the MPB. Nano-size heterogeneous regions were observed within submicron domain structure, indicating that the nanoscale polarization dynamics are not confined by domain boundaries, and the high piezoelectricity of NBT-x%BT is due to a polarization dynamics with high sensitivity to electric field and a broadened relaxation time distribution. In KNN textured ceramics, an aging effect was found to exist in the orthorhombic single phase field, not only in the orthorhombic and tetragonal two-phase field as previously reported. No variation of phase structure was revealed between before and after aging states. However, pronounced changes in domain morphology were observed by both PFM and TEM: more uniform and finer domain structures were then found with aging. These changes were even more pronounced after poling the aged state. A large number of sub-micron lamellar domains within micron-domains were observed: suggesting a domain origin for improved piezoelectric properties. In Fe-xat.%Ga alloys, an underlying inhomogeneity from Ga atoms embedded into the α-Fe matrix was believed to be the origin of giant magneostrictive properties. I have systematically investigated the phase structure and nano-size heterogeneity of Fe-xat.%Ga alloys subjected to different thermal treatments using standard TEM and high resolution TEM for 10<x<30. Nano-precipitates were observed in all specimens studied: A2, D03 and B2 phases were found depending on x. Nano-precipitates of D03 were observed to be dominant for compositions near the magnetostriction peaks in the phase diagram. Quenching was found to increase the volume fraction of nanoprecipitates for x=19, near the first magnetostriction peak. With increasing x to 22.5, nanoprecipitates were observed to undergo a D03 – B2 transformation. A high density of D03 precipitates of nanoscale size was found to be the critical factor for the first maximum in the magnetostriction. / Ph. D.

Piezoelectric materials find applications in multitude of devices such as sensors, actuators and energy harvesters. However, most of these piezoelectric materials utilize lead-based systems which are becoming serious problem owing to the restrictions imposed by regulatory agencies across the globe. In the functional ceramics community, currently there is no problem more important than to find a replacement for lead-based piezoelectrics used for actuators. The electromechanical properties required for actuators (high piezoelectric constant, high coupling factor, low loss, and high transition temperatures) for known lead-free compositions are, however, far inferior to those of lead-based systems. There are three lines of research for addressing this fundamental problem "C (i) search for new systems through a combination of theory-based prediction followed by experimental effort (doping, solid solutions having a morphotropic (M) or polymorphic (P) phase boundary (PB), (iii) stabilization of metastable phases or finding the high temperature triclinic systems, and (iii) improving the properties of known compositions through microstructure optimization, domain engineering and multilayering. All these approaches are challenging and require innovation to make a significant impact on the current state-of-the-art. In this thesis, the later line of research was focused which is promising for near future applications, as it builds upon the known material systems with high depoling temperatures that have demonstrated the potential to be practical. In the first chapter, a novel method for the synthesis of lead-free (1-x)(Na0.5Bi0.5)TiO₃ "C xBaTiO3 piezoelectric ceramics was investigated. Initially, multiple compositions around morphotrpic phase boundary (MPB) were synthesized to identify the optimum composition 0.93Na0.5Bi0.5TiO3-0.07BaTiO3 (NBT-BT) for electromechanical effect. The new synthesis method starts with the synthesis of Na2Ti6O13 (NTO) whiskers which are then transformed into lead-free NBT-BT ceramics. Synthesis of NTO whiskers was performed using molten salt synthesis (MSS) method. Tape casting method was used to align the whiskers in base matrix powder and subjected to various processing temperatures to elucidate the microstructure and texture evolution. For this, scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), atomic force microscopy (AFM) and energy dispersive spectroscopy (EDS) analysis were used as principal tools. The sintering process can be understood by dividing it into three stages, namely (i) transformation of monoclinic whiskers in to NBT-BT perovskite phase through topochemical reaction (<800°C), (ii) localized sintering confined on single whisker (800-1050°C), and (iii) liquid phase sintering as densification and grain growth occurs in the whole matrix (>1050°C). The concentric growth ledges observed on grain surfaces were found to be preferably confined on the corners of cubical grains indicating <111> growth direction. The Lotgering factor (f100) for the sintered matrix was found to decrease with increase in sintering temperature. The longitudinal piezoelectric constant (d33) of samples sintered for 20h at 1175°C, 1200°C and 1225°C was measured to be ~153 pC/N, ~216 pC/N and ~180 pC/N, respectively. Next, a novel method was developed for the synthesis of nanostructured lead-free ferroelectric NBT-BT whiskers with high aspect ratio using NTO as a host structure. High energy x-ray diffraction coupled with atomic pair distribution function (PDF) and Raman scattering analyses were used to confirm the average structure of lead-free NBT-BT whiskers as rhombohedral, i.e. a ferroelectricity enabling type. The HRTEM analysis revealed local monoclinic-type structural distortions indicating a modulated structure at the nanoscale in the MPB composition of lead-free NBT-BT whiskers. The structural rearrangement during the synthesis of lead-free NBT-BT whiskers was found to occur via translation of edge shared octahedra of NTO into a corner sharing coordination. The high temperature morphological changes depicting disintegration of isolated whiskers into individual grains due to higher grain boundary energy have been found to occur in a close analogy with Rayleigh-type instability. In lead-based ABO3 compounds, with B-site disorder, the origin of enhancement of piezoelectric properties near MPB has been associated with the presence of an intermediate monoclinic/orthorhombic state that bridges the adjacent ferroelectric rhombohedral and tetragonal phases. However, the origin of high piezoelectric response in lead-free ABO3 compounds with A-site disorder has not been conclusively established. In this thesis, a microscopic model derived from comparative analyses of HR-TEM and neutron diffraction was developed that explains the origin of high piezoelectric response in lead "C free MPB compositions of NBT-BT. Direct observation of nanotwins with monoclinic symmetry confirmed the presence of an intermediate bridging phase that facilitates a pathway for polarization reorientation. Monoclinic distortions of an average rhombohedral phase were attributed to localized displacements of atoms along the non-polar directions. These results provide new insight towards design of high performance lead "C free piezoelectric materials. Microstructure and domain structure play dominant role towards controlling the magnitude of piezoelectric coefficient and hysteretic losses in perovskites. Brick-wall like microstructure with large grain size and small domain size can provide significant enhancement in the magnitude of piezoelectric coefficient. A synthesis technique for lead-free piezoelectric NBT-BT system that can provide [001]pc/[012]Rh grain oriented ceramics with large grain size and an electrical poling technique that results in smaller domain size will have significant impact on the electromechanical response. In this research, a synthesis technique was developed and the processing variables that play deterministic role in achieving the large grain brick-wall like microstructure were explained. Interfaces in the microstructure were found to be coherent at the atomic scale facilitating the domain wall motion with applied electric field. The piezoelectric response was found to increase monotonously with the incease in the degree of texturing and optimized microstructure was found to provide 200% enhancement in the magnitude of piezoelectric coefficient as compared to its random form. In order to understand the mechanism of enhanced piezoelectric response in textured NBT-BT, in-situ neutron diffraction experiments revealed that characteristically different structural responses are induced in textured and randomly-oriented NBT-BT ceramics upon application of electric fields (E), which are likely related to the varying coherence lengths of polar nano regions and internal stresses induced by domain switching. In conjunction to focus on NBT-BT, new lead-free piezoelectric materials with enhanced piezoelectric response were synthesized. This study provides fundamental understanding of the enhanced piezoelectric instability in lead-free piezoelectric (1-x) BaTiO₃-xA(Cu1/3Nb2/3)O3₃ (A: Sr, Ba and Ca and x = 0.0-0.03) solid solutions. These compositions were found to exhibit large d33 of ~330 pC/N and electromechanical planar coupling constant (kp)~ 46% at room temperature. The piezoelectric instability in these compositions was found to increase with x despite monotonous decrease in the long range polar ordering. High energy X-ray diffraction coupled with PDFs indicated increase in local polarization. Raman scattering analysis revealed that substitutions on A and B-site both substantially perturbed the local octahedral dynamics and resulted in localized nano polar regions with lower symmetry. These localized polar distortions were found to persist much above the Curie temperature (Tc). Polarization "C electric field (P-E) hysteresis loop analysis indicated presence of the internal bias that was found to be correlated with the formation of polar defects. This defect structure was found to modulate the domain structure resulting in nano domains and broad domain walls with higher mobility as revealed through analysis from HR-TEM and piezoresponse force microscopy (PFM). The presence of nano domains and local structural distortions smears the Curie peak resulting in diffuse order-disorder type phase transitions. The electron paramagnetic resonance (EPR) investigations revealed that substitution of Cu²⁺ takes place on octahedral sites that are distorted due to Jahn-Teller effect. The A-sites were distorted by substitution of Sr and Ca on Ba-site possessing different ionic radii and electronegativity. The effect of these distortions on the variations in physical property was modeled and analyzed within the context of nanodomains and phase transitions. As an application, the solid solution with nominal composition of (1-x)BaTiO₃-xBa(Cu1/3Nb2/3)O₃ (BCN) (x = 0, 0.025) was synthesized by conventional mixed oxide route, followed by compositional modification with varying concentration of Sn, as given by the formulation: 0.975 BaTi1-ySnyO₃ "C 0.025 Ba(Cu1/3Nb2/3)O₃ (y = 0.05, 0.06, 0.075, 0.1). Room temperature XRD patterns showed decrease in tetragonality of BT after modifying with BCN (BT-BCN). Modifications with Sn lead to further decrement in tetragonality and the room temperature structure became cubic at 6.0 at% doping level. The decrement in tetragonality was accompanied by lowering of Tc.  BT-BCN doped with 6 and 7.5 at% Sn were found to exhibit diffuse phase transition accompanied by high dielectric constant "Ý 7000, low loss tangent "Ü 1% and grain size in the submicron regime ("Ü 1 "Ìm). These compositions were found to be promising for Y5V type multilayer ceramic capacitors (MLCCs). Lastly, the dielectric and ferroelectric responses of compositionally graded bilayer and trilayer composites consisting of BT and 0.975BaTiO₃-0.025Ba(Cu1/3Nb2/3)O₃ (BT-BCN) were investigated. Two types of graded bilayer samples were synthesized, one with same thickness of BT and BT-BCN while other with different layer thicknesses. The graded trilayer sample consisted of BT layer sandwiched between two BT-BCN layers of equal thickness. SEM and TEM images showed a sharp interface with needle-shape domains across the interface. The domain size on BT-side was found to be larger than that on BT-BCN-side. The temperature dependence of dielectric response for all composite systems was found to exhibit shifting of characteristic Curie peak compared to constituent material which was associated to coupling between layers. Moreover, the differences in grain size, tetragonality, domain mobility of each layer was found to perturb the electrical response of composite. The polarization mismatch between uncoupled BT and BT-BCN established internal electric field in composite specimen and defined new polarization states in each layer by perturbing free energy functional of the composite specimen. Dynamic hysteresis behaviors and power-law scaling relations of all specimens were determined from P"CE field hysteresis loop measurements as a function of frequency. All systems were found to exhibit similar dynamic scaling relationships. Hysteresis area, Pr and EC decreased with increasing frequency due to delayed response, but increased with increasing applied electric field due to enhancement of driving force. Trilayer system was found to exhibit strong internal-bias field and double hysteresis behavior. The coupling effect resulting due to polarization mismatch between layers had substantial influence on the dynamic hysteresis behavior and power-law scaling relations. / Ph. D.

Multiferroics have attracted lots of research interest due to their potential in numerous multifunctional applications. The multiferroic materials could simultaneously exhibit two or more ferroic order parameters, and the coupling effects between ferroelectricity and ferromagnetism are named as magnetoelectric (ME) effect. Recently, with the development of thin film growth techniques, the multiferroics magnetoelectric composite heterostructures exhibit a very promising future prospects. This dissertation focused on the design, fabrication and characterization of new multiferroics magnetoelectric composite heterostructures. First, based on the specific phase architectures in BFO-CFO self-assembled thin films grown on variously oriented STO substrates and the epitaxial film growth knowledge, I designed two kinds of new film heterostructures: (i) I utilized self-assembled BFO nanopillars in a BFO-CFO two phase layer on (111) STO as a seed layer on which to deposit a secondary top BiFeO3 layer. The growth mechanism and multiferroic properties of these new heterostructures were investigated. (ii) I demonstrated the formation of a new quasi-(0-3) heterostructure by alternately growing (2-2) and (1-3) layers within the film. I proposed a new concept to overcome limitations of both the (2-2) and (1-3) phase connectivities and identified an indirect ME effect by the switching the characteristics of the piezoresponse for the new heterostructure. Second, for the option for candidates thin film materials with a high piezoelectric coefficient, which is a critical factor for ME composite films, I utilized the simple compositional BaSn0.11Ti0.89O3 bulk ceramic material as a target to grow films with the large piezoelectric properties. The grown high qualify lead-free epitaxial thin films had a chemical constituent similar to the reported giant piezoelectric ceramics near the MPB and with the QP. Both coherent and incoherent regions were observed in the interface and a larger piezoelectric coefficient d33 was achieved in this film. Finally, with respect to their characteristics and potential, I redirected from two-dimensional thin film materials to one-dimensional nanowire materials. By utilizing vertically aligned templates, I fabricated a new type of coaxial two-phase composite nanowires. Multiferroic properties of these new one-dimensional materials have been investigated. All these multiferroics magnetoelectric composite herterostructures would provide lots of potential in applications. / PHD

Nonlinear optics and ferroelectrics have been recognized for several decades as promising fields with important applications in the area of opto-electronics, photonics, memory devices, etc. High performance electro-optical switching elements for telecommunications and optical information processing are based on the material properties. Hence, there is always a continuous search for new and better materials. In this thesis we have investigated the growth and physical properties of four crystals viz. two NLO and two ferroelectric crystals. This thesis consists of eight chapters. The first chapter gives an overview of historical perspectives of nonlinear optical phenomenon, ferroelectricity and materials developed therein. The second chapter gives a brief description of the underlying theories of crystal growth, nonlinear optics and ferroelectricity. A major portion of this chapter consists of gist of the earlier work carried out on compounds of our interest viz. urea L-malic acid, sodium p-nitrophenolate dihydrate, glycine phosphite and lithium niobate. Synthesis, growth, crystal structure details and some physical properties of these materials are briefed. The third chapter describes the experimental techniques needed to grow as well as characterize these crystals. The experiments are performed on single crystals grown in the laboratory using the solution growth setup and Czochralski crystal puller. These growth units are described in detail. Preliminary characterization techniques like powder Xray diffraction, optical transmission, scanning electron microscopy, Vickers and Knoop hardness are described briefly. Various experimental methods viz. dielectric, polarization reversal, photoacoustic spectroscopy and laser induced damage for characterizing the grown crystals are explained. Urea L-malic acid (ULMA) is a new NLO organic material which is reported to exhibit second harmonic efficiency three times that of the widely used inorganic crystal, KDP. Hence, this material is selected for detailed investigation and the results obtained are discussed in chapter 4. This chapter contains details of single crystal growth and characterization of ULMA. The crystals are grown by slow cooling technique. The complete morphology of the crystal is evaluated using optical goniometry. The grown crystals are characterized for their optical and thermal properties. The defect content in the grown crystal is evaluated by chemical etching. As the surface damage of the crystal by high power lasers limits its performance in NLO applications, a detailed laser induced damage studies are performed on ULMA. Both single shot and multiple shot damage threshold values for 1064 nm and 532 nm laser radiation are determined and correlated with the mechanical hardness. In addition, the thermal diffusivity and thermal conductivity of ULMA along various crystallographic orientations are evaluated using laser induced photoacoustic spectroscopy and the results are interpreted in terms of crystal bonding environment. Another NLO crystal taken up for study is sodium p-nitrophenolate dihydrate (NPNa 2H2O), a semiorganic material. This crystal is a very efficient NLO material and has the advantages of both organics and inorganics. Earlier investigations on growth of NPNa.2H2O in various solvents have shown methanol as the most suitable solvent for growth. Growth from aqueous solution was discarded as it did not yield crystals which are stable. In the present investigation, stable, NLO active NPNa.2H2O crystals are obtained using aqueous solution itself by varying the crystallization conditions and exploring the suitable temperature range. The details of growth and characterization form the subject of fifth chapter. The grown crystals are characterized using optical transmission, XRD and thermo gravimetric analysis. Later, laser induced damage threshold is evaluated for both 1064 nm and 532 nm laser radiation and compared wit the methanol grown ones. A possible mechanism of damage is given. The sixth and seventh chapters deal with growth and characterization of ferroelectric materials namely glycine phosphite and lithium niobate respectively. Glycine phosphite is a low temperature ferroelectric crystal which is well studied in terms of its dielectric and ferroelectric properties. But very few radiation damage studies are reported. The effect of ionizing radiation on ferroelectrics is of considerable interest as it significantly modifies the physical properties of these materials. In the present investigation, effects of X-ray irradiation (_ = 1.5418 °A) on the lattice parameters, dielectric constant, loss tangent, polarization switching characteristics and domain dynamics of glycine phosphite are investigated. X-ray irradiation is performed in the non-polar phase of the sample. The effect as a function of duration of exposure is studied. X-ray irradiation in GPI has resulted in drastic reduction in _ values and shift in transition temperature towards lower temperatures. X-ray irradiation on polarization switching properties of the crystal are also investigated. The activation energy and threshold field of switching increase with the irradiation time. The behaviour of domain wall mobility is quite different from that exhibited by other well known ferroelectrics. These results are discussed in chapter 6 and a possible explanation for the unusual behaviour of domain wall mobility is given. The defect generated is identified as PO32− radical by electron paramagnetic measurement. Lithium niobate (LiNbO3) is an extensively studied material in terms of its NLO and ferroelectric properties. This material has high piezoelectric coupling coefficients along certain directions which makes it suitable for wide band surface acoustic wave applications. Hence there is a demand for good quality, single domain YZ-LiNbO3 substrates. Chapter 7 describes the growth of Z-pulled congruent LiNbO3 using Czochralski technique. Large single crystals of diameter 30 mm and length 80 mm are grown from congruent composition employing Czochralski technique. The grown crystals are multidomain and hence electric field poling is performed to get single domain crystals. Their subsequent characterization for SAW devices upto 200 MHz was performed and compared with the imported substrate. The general conclusions are given in chapter 8 along with possible future work that could be performed on these crystals.

Piezoelectric materials find use as actuators and sensors in automotive, aerospace and other related industries. Automotive applications such as fuel injection nozzles and engine health monitoring systems require operating temperatures as high as 300-500 oC. The commercially used piezoelectric material PbZr1-xTixO3 (PZT) is limited to operating temperatures as low as 200 oC due to the temperature induced depolarization effects. PZT, in the undoped state exhibits a piezoelectric coefficient (d33) of 223 pC/N and ferroelectric-paraelectric transition temperature (Tc) of 386 oC. The enhanced properties of PZT occur at a region between the tetragonal and rhombohedral phases, called the Morphotropic Phase Boundary (MPB). Therefore, search for new materials with higher thermal stability and better sensing capabilities were focused on systems that exhibit a PZT-like MPB. This led to the discovery of (x)BiScO3-(1-x)PbTiO3 (BSPT), which exhibits an MPB with enhanced Tc (450 oC) and exceptionally high piezoelectric response (d33 = 460 pC/N). Theoretical studies have shown that the mechanism of enhanced piezoresponse in ferroelectric systems is related to the anisotropic flattening of the free energy profiles. An alternative view point attributes the anomalous piezoelectric response to the presence of high density of low energy domain walls near an inter-ferroelectric transition. Diffraction is a versatile tool to study the structural and microstructural changes of ferroelectric systems upon application of electric field. However, characterization of electric field induced structural and microstructural changes is not a trivial task, since in situ electric field dependent diffraction studies almost invariably give diffraction patterns laden with strong preferred orientation effects, due to the tendency of the ferroelectric/ferroelastic domains to align along the field direction. Additionally, diffraction profiles of MPB compositions exhibit severe overlap of Bragg peaks of the coexisting phases, and hence, it is difficult to ascertain with certainty, if the alteration in the intensity profiles upon application of electric field is due to change in phase fraction of the coexisting phases or due to preferred orientation induced in the different phases by the electric field. The characterization of electric field induced phase transformation in MPB systems, has therefore eluded researchers and has been considered of secondary importance, presumably due to the difficulties in unambiguously establishing the structural changes upon application of electric field. In fact, majority of the in situ electric field dependent diffraction studies have been carried out on compositions just outside the MPB range, i.e. on single phase compositions. In such studies, the focus has been mainly on explaining the piezoelectric response in terms of motions of the non-180° domain walls and field induced lattice strains. In this dissertation, the BSPT system has been systematically investigated with the view to understand the role of different contributing factors to the anomalous piezoelectric response of compositions close to the MPB. Using a comparative in situ electric field dependent diffraction study on a core MPB composition exhibiting highest piezoelectric response and a single phase monoclinic (pseudo-rhombohedral) composition just outside the MPB, it is demonstrated that, inspite of the significantly large domain switching and lattice strain (obtained from peak shifts) in the single phase composition, as compared to the MPB composition, the single phase composition shows considerably low piezoelectric response. This result clearly revealed that the anomalous piezoelectric response of the MPB composition is primarily associated with field induced inter-ferroelectric transformation and the corresponding field induced interphase boundary motion. A simple strategy has been employed to establish the field induced structural transformation for the MPB compositions, by overcoming the experimental limitation of in situ electric field dependent diffraction studies. The idea stemmed from the fact that, if the specimens for diffraction study can be used in powder form instead of pellet, the problems associated with preferred orientation effects can be eliminated, and the nature of field induced structural changes can be accurately determined. A comparative study of the diffraction profiles from poled (after subjecting the specimen to electric field) and unpoled (before subjecting the specimen to electric field) powders could precisely establish the nature of electric field induced phase transformation for the MPB compositions of BSPT and provided a direct correlation between the electric field induced structural changes and the enhanced piezoelectric response. A new ‘powder poling’ technique was devised, which involves application of electric field to powder form of the specimen. Using this technique, it was possible to study separately, the effect of stress and electric field on the nature of structural transformation. A unique outcome of this study was, it could demonstrate for the first time, analogous nature of the stress and electric field induced structural transformation. A comparative study of the dielectric response of poled and unpoled samples was used to show a counterintuitive phenomenon of field induced decrease in polarization coherence for the MPB compositions. This approach was used to suggest that the criticality associated with the MPB extends beyond the composition boundary conventionally reported in literature based on bulk diffraction techniques (x-ray and neutron powder diffraction). The layout of the dissertation is as follows: Chapter 1 gives a brief introduction of the fundamental concepts related to ferroelectric materials. The theories that explain the enhanced piezoresponse of MPB based ferroelectric systems have been outlined. Detailed information of the existing literature is presented in the relevant chapters. Chapter 2 presents the details of the solid state synthesis of BSPT compositions and structural analysis using diffraction studies. The dielectric measurements were used to establish the Tc for the different compositions. The enhanced ferroelectric and piezoelectric properties were observed for the MPB compositions, which were shown to exhibit coexistence of tetragonal and monoclinic phases from structural studies. The critical MPB composition exhibiting highest piezoelectric and ferroelectric properties was established to be x = 0.3725. The thermal stability of the critical MPB composition was established to be 400 oC using ex situ thermal depolarization studies. The common approach of structural analysis in the unpoled state failed to provide a unique relationship between the anomalous piezoelectric response and the structural factors at the MPB, emphasizing the need to characterize these system using electric field dependent structural studies. Chapter 3 presents the results of in situ electric field dependent diffraction measurements carried out at Argonne National Laboratory, USA. The quasi-static field measurements could successfully quantify the non-180o domain switching fractions and the field induced lattice strains. The changes in the integrated intensities were used to obtain the non-180o domain switching fraction and the shift in peak positions were used to quantify the field induced lattice strains. The in situ studies could successfully explain the macroscopic strain response for the single phase pseudo-rhombohedral (monoclinic) composition on the basis of domain switching mechanisms and field induced lattice strains. The MPB compositions were shown to have additional contributions from interphase boundary motion, resulting from change in phase fraction of the coexisting phases. The results emphasized the need to investigate the electric field induced transformation for MPB compositions, in order to give a comprehensive picture of the various contributions to the macroscopic piezoreponse. While Rietveld analysis could be used to investigate the phase transformation behaviour upon application of electric field, textured diffraction profiles obtained using in situ studies, in addition to the severely overlapping Bragg reflections of the coexisting phases for the MPB compositions hindered reliable estimation of the structural parameters. An alternate approach to investigate the field induced phase transformation is presented in Chapter 4. The stroboscopic measurements on the MPB composition showed evidence of non-180o domain wall motion even at sub-coercive field amplitudes as low as 0.1 kV/mm. Chapter 4 presents the results of the ex situ electric field dependent structural study, wherein the diffraction profiles collected from poled powders is compared to that of unpoled powders. The diffraction profiles from the poled powders did not exhibit any field induced crystallographic texture and could successfully be analyzed using Rietveld analysis. High resolution synchrotron diffraction studies (ESRF, France) carried out on closely spaced compositions revealed that, the composition exhibiting the highest piezoelectric response is the one, which exhibits significantly enhanced lattice polarizability of both the coexisting (monoclinic and tetragonal) phases. The enhanced lattice polarizability manifests as significant fraction of the monoclinic phase transforming irreversibly to the tetragonal phase after electric poling. The monoclinic to tetragonal transformation suggested the existence of a low energy polarization rotation pathway towards the [001]pc direction in the (1 1 0)pc pseudocubic plane of the monoclinic phase. The results are discussed on the basis of the existing theories that explain piezoresponse in MPB systems and are in support of the Polarization rotation model, in favor of a genuine monoclinic phase. Chapter 5 discusses the ferroelectric-ferroelectric stability of the MPB compositions in response to externally applied stress and electric field independently. Using the newly developed ‘powder poling’ technique, which is based on the concept of exploiting the irreversible structural changes that occur after application of electric field and stress independently, it was possible to ascertain that, both moderate stress and electric field induce identical structural transformation - a fraction of the monoclinic phase transforms irreversibly to the tetragonal phase. The powder poling technique was also used to demonstrate field induced inter-ferroelectric transformation at sub-coercive field amplitudes. In addition, the analysis of the dielectric response before and after poling revealed a counterintuitive phenomenon of poling induced decrease in the spatial coherence of polarization for compositions around the MPB and not so for compositions far away from the MPB range. Exploiting the greater sensitivity of this technique, it was demonstrated that, the criticality associated with the inter-ferroelectric transition spans a wider composition range than what is conventionally reported in the literature based on bulk x-ray/neutron powder diffraction techniques. Chapter 6 presents the closure and important conclusions from the present work and summarizes the key results, highlighting the proposed mechanism of enhanced piezoresponse in BSPT. The last part of the chapter deals with suggestions for future work from the ideas evolved in the present study. vi

Microwave tubes are the choice of a wide range of high power and millimeter wave applications in radar, electronic warfare and communication systems. Advances in these devices are due to device innovation, improved modeling, and development of advanced materials. In a microwave tube, electron emitter is the source of electron beam and it is one of the vital components determining the life & performance of the device. High power, high frequency microwave tubes require electron emitters with high emission density. The present thesis aims at developing the materials for high emission density electron emitters. It is aimed to improve the emission density of thermionic cathodes for use in conventional microwave tubes and to develop cold emitters like ferroelectric cathodes for high power microwave devices. The work reported in the present thesis is a modest attempt of the author towards this aim. The thesis is organized in six chapters. Chapter 1 gives a brief introduction of thermionic and ferroelectric emitters. Different types of electron emission mechanisms and a brief background of thermionic and ferroelectricemitters are discussed in this chapter. The genesis of the problem taken up and its importance as well as the plan and scope of the work is also given in this chapter. In Chapter 2, the basic experimental techniques used in the present work are discussed. Preparation of mixed metal matrix and M- type dispenser cathodes and their characterization techniques has been discussed in this chapter. Subsequently, ferroelectric materials preparation and characterization for their material properties and electron emission has been discussed. A brief introduction to FEM software ANSYS, used for thermal analysis of dispenser cathodes and electrostatic field analysis of ferroelectric cathodes, has been given at the end of this chapter. Thermal analysis, development process, emission characterization, work function distribution, of W-Ir mixed metal matrix (MM type) cathodes and a simple innovative technique to estimate the barium evaporation rate from the emission data of the dispenser cathodes is presented in Chapter 3. Under normal microwave tube operating conditions, the cathode of the electron gun has to be heated up to 1050°C to obtain stable thermionic electron emission. Thermal analysis is a first step in the development process of cathodes, optimizing its structure for improved performance with respect to its operating power, warm-up time and efficiency. Thermal analysis of a dispenser cathode in electron gun environment using the FEM software ANSYS and its experimental validation are presented. Development of porous W-Ir mixed metal matrix material required for dispenser cathode applications has been discussed. Determination of pore size, pore density and pore uniformity has been carried out. The performance of the cathodes made with these pellets is at par with the results reported in the literature. The surface of mixed metal pellet is an inherently two-phase structure consisting of tungsten solid solution phase and W-Ir ε phase causing more spread in the spatial distribution of work function. W-Ir mixed metal matrix cathodes have been realized and their work function distribution has been determined form the measured I-V characteristics. Also in this chapter, a novel technique for estimation of barium evaporation rate for dispenser cathodes from their I-V characteristics is presented. Results of life test carried out on these cathodes are given at the end of the chapter. In Chapter 4, work carried out on enhancing the emission properties of mixed metal matrix cathodes by suitably modifying the impregnant mix is discussed. W-Ir MM type cathodes discussed in the previous chapter give a emission current density of ~ 7.5A/cm2 with a work function of 1.99 eV. Thesevalues are very close to that of B-type cathode. In this chapter, it is explored to suitably dope the 5BaO:3CaO:2Al2O3 impregnant mix to reduce the work function of W-Ir cathodes. Lithium and Scandium oxides have been added to the 5:3:2 imp regnant mix. Lithium oxide doped impregnated MM type cathodes have given more than 30 A/cm2 current density at 1050oC. For scandium oxide doped MM type cathodes current density has increased to 15 A/cm2 at the same temperature. In Chapter 5, Electron emission from the ferroelectric cathodes has been discussed. FEM simulation of Ferroelectric cathodes to study the electrical excitation effects on emission. Triple point electric field in FE Cathodes is very large and can lead to field emission from the metallic grid at triple points. FEM simulation has been carried out to find out the effect of grid thickness on triple junction electric field using ANSYS software. From FEM modeling it is also seen that if a dielectric layer of lower dielectric constant (εr≤10) is placed between the grid and the ferroelectric material the triple junction electric field increases three fold. Use of dielectric layer can also reduce the secondary electron coefficient (δ) and surface plasma generation. Lanthanum doped PZT has been chosen for the study and these materials have been tested in diode configuration for emission characterization in demountable vacuum systems. Repeatable electron emission has been achieved for all the three compositions of PLZT (x/65/35) material (x = 7, 8, 9). However, it has been observed that when the ferroelectric is subjected to repetitive unipolar electrical excitation, fatigue is set in and cathode material is cracking. To study the effect of domain switching on the residual stress in the ferroelectric material, XRD studies have been carried out. Shift in XRD peaks for fresh and emission tested samples has been used to calculate the residual stress developed in the samples. Details of High current switch realized using ferroelectric cathodes have been discussed. Chapter 6 gives the Summary of the work done and suggestions for further research on W-Ir mixed metal matrix cathodes and ferroelectric cathodes.