Hf₁₋ₓZrₓO₂ (x ∼ 0.5–0.7) has been the leading candidate of ferroelectric materials with a fluorite crystal structure showing highly promising compatibility with complementary metal oxide semiconductor devices. Despite the notable improvement in device performance and processing techniques, the origin of its ferroelectric crystalline phase (space group: Pca2₁) formation has not been clearly elucidated. Several recent experimental and theoretical studies evidently showed that the interface and grain boundary energies of the higher symmetry phases (orthorhombic and tetragonal) contribute to the stabilization of the metastable non-centrosymmetric orthorhombic phase or tetragonal phase. However, there was a clear quantitative discrepancy between the theoretical expectation and experiment results, suggesting that the thermodynamic model may not provide the full explanation. This work, therefore, focuses on the phase transition kinetics during the cooling step after the crystallization annealing. It was found that the large activation barrier for the transition from the tetragonal/orthorhombic to the monoclinic phase, which is the stable phase at room temperature, suppresses the phase transition, and thus, plays a critical role in the emergence of ferroelectricity.

Les principaux objectifs de cette thèse de doctorat ont été de réaliser la synthèse et la caractérisation structurale et dieléctrique des échantillons céramiques ferroélectriques appartenants au système Pb1-xRxZr0,40Ti0,60O3 avec R = Ba et La et x entre 0,00 à 0,50. Ce système a été choisi car il est un matériel ferroélectrique qui a des propriétés physiques intéressantes, comme haute constante diélectrique et piézo-électrique, ce qui les rend candidats potentiels pour des applications telles que les condensateurs à haute densité d'énergie et les actionneurs. Afin d'évaluer le comportement relaxor, les études ont été effectuées avec la variation de la composition, du type de dopage (par des atomes de la même ou différente valence – La ou Ba) et de la taille des particules de céramique, dès l'échelle micrométrique à l'échelle nanométrique. Les échantillons céramiques micrométriques ont été préparées par la méthode de réaction de l'état solide et la frittage dans un four électrique conventionnel. Les données fournies par la technique de diffraction des rayons X de cettes échantillons ont montré une transition de une phase tétragonal pour une phase cubique avec l'augmentation de la concentration de cations substituants. Ces changements ont été attribués à une diminution de distorsion dans le maille cristallographique en raison de l'apparition de défauts causés par l'incorporation de dopage. Les mesures électriques ont été obtenues par spectroscopie d'impédance et ont montré un comportement électrique relaxor à partir de compositions avec plus de 12% at. La et de 30% at. Ba pour les systèmes PLZT et PBZT, respectivement. Les mesures électriques de l'échantillon avec 12%, 13% et 14% at. La et 30% at. Ba présentent un comportement qui, selon la littérature, est liée à une transition de phase spontanée d'un comportement relaxor et au comportement d'un matérial ferroélectrique normal. La technique de diffraction des rayons X a également été utilisé pour surveiller le processus de transition de phase en fonction de la température pour échantillons PLZT et PBZT. Il est possible de voir le changement de structure tétragonal de groupe d'espace P4mm en structure cubique de groupe d'espace Pm-3m. En ce qui concerne la structure locale, nous avons effectué des mesures expérimentales avec la technique de spectroscopie d'absorption des rayons X dans le spectre XANES aux seuils d'absorption de différents éléments pour les échantillons PLZT et PBZT. Dans les cas de seuil d'absorption K du titane, l'intégration de La et Ba atomes de la structure du PZT entraîne une diminution dans le désordre local dans le octaèdre TiO6, vérifié par la réduction du déplacement statique de atome Ti au centre de l'octaèdre TiO6. Cette évolution est plus faible pour les échantillons que montrent le comportement relaxor. Les spectres d'absorption EXAFS au seuil LIII du plomb et seuil K du zirconium ont été effectués aussi et ces mesures indiquent que la structure locale autour des atomes de plomb ou de zirconium est également affectée par l'introduction des atomes de La et Ba dans la structure. Le comportement relaxor a été aussi étudié en fonction de la taille de grain dans une échelle nanométrique. Ainsi les échantillons de compostions PZT, PLZT11 et PBZT10 ont eté préparés en utilisant la méthode de synthèse chimique de polymères précurseurs et le processus de frittage par spark plasma. La caractérisation de ces échantillons par diffraction de rayons X montrent que les paramétres de maille réduisent en comparison avec les échantillons de même composition et taille de grain micrométrique. Pour l'échantillon de composition PLZT11, il est possible de constater le comportement relaxor par les mesures de la constante dieléctrique en fonction de la température. Les changements quand la taille de grain est dans une échelle nanométrique sont attribués à la limitation des frontières de grains, qui provoquent un systéme de tension, responsable de la diminuition des paramétres de maille, et provoquent l'apparition de domaines ferroélectriques nanométriques / The main objectives of this doctoral thesis were the synthesis and structural characterization of Pb1-xRxZr0.40Ti0.60O3 ferroelectric ceramic samples, with R = Ba and La and x between 0.00 to 0.50. This system was chosen because its interesting physical properties such as high dielectric and piezoelectric constant. These characteristics make it potential candidate for applications such as capacitors in high energy density and actuators. To evaluate the relaxor behavior, the studies were carried out with the change in the composition, type of doping (by atoms of the same or different valence – La or Ba) and the particle size of ceramics, from the micrometer to nanometer scale. Micrometric ceramic samples are prepared by the method of reaction of solid state and sintering in a conventional furnace. The characterization with X-ray diffraction technique of these samples showed a transition from tetragonal phase to a cubic phase with increase of the dopping cation concentration. These changes have been attributed to the appearance of defects caused by the incorporation of La or Ba cations. Electrical measurements were obtained by impedance spectroscopy and showed a electric relaxor behavior from compositions with more than 12 at. % of La and the 30 at. % of Ba for PLZT and PBZT systems, respectively. These measurements for the samples with 12 at. %, 13 at. % and 14 at. % of La and 30 at. % of Ba exhibit a behavior that, according to the literature, is related to a spontaneous phase transition from a relaxor behavior to a normal ferroelectric behsvior. The technique of X-ray diffraction also been used to monitor the phse transition phase as a function of the temperature for PLZT and PBZT samples. It is possible to note the change in a tetragonal structure with P4mm space group to a cubic structure with Pm-3m space group. Concerning the local structure, XANES spectra in the absorption edge of various elements in PLZT and PBZT samples were performed. In the cases of Ti K-edge absorption, the dopping of La and Ba atoms in the PZT structure leads to a decrease of the local disorder in the TiO6 octahedron and it is verified the reduction of static displacement of Ti atom in the center of the TiO6 octahedron. This displacement is lower for samples that show relaxor behavior. The EXAFS measurements in Pb LIII-edge and Zr K-edge were performed and also indicate that local structure around lead or zirconium atoms is also affected by the introduction of La and Ba atoms in the PZT structure. The relaxor behavior was also studied depending on the size of particle size in a nanometer scale. Thus samples PZT, PLZT11 and PBZT10 compositions were prepared using the synthesis method of precursor polymers and the process of sintering by spark plasma. Characterization of these samples by X-ray diffraction shows that the lattice parameters are reduced in comparison with samples of the same composition and micrometer particle size. For PLZT11 composition, it is possible to observe a relaxor behavior by measurement of the dielectric permittivity as a function of the temperature. These changes when the grain size is in a nanoscale are attributed to the grain boundaries, that are responsible for the decrease in the lattice parameters and the appearance of ferroelectric nanodomains

Transparent glasses embedded with TTB structured ferroelectric nano/micro crystals (K3Li2Nb5O15, Ba5Li2Ti2Nb8O30) were fabricated in various tellurite and borate based glass matrices and characterized for their physical properties. Nanocrystals of K3Li2Nb5O15 were successfully grown inside tellurite glass matrix via conventional heat-treatment route. Eventhough, tellurite glasses preferentially crystallize only on the surface, bulk uniform crystallization was achieved in the (100-x) TeO2 - x(1.5K2O-Li2O-2.5Nb2O5) system. Heat capacity studies revealed them to be thermodynamically less fragile than any other tellurite glasses ever reported in the literature. Pyroelectric and ferroelectric effects as well as second harmonic generation were demonstrated for the heat treated (glass nanocrystal composites) samples in this system. The conventional method of melt-quenching of constituent oxides could not yield Ba5Li2Ti2Nb8O30 crystallites. So, Ba5Li2Ti2Nb8O30 microcrystals were successfully formed in tellurite glass matrix by mixing pre-reacted Ba5Li2Ti2Nb8O30 ceramic powders with TeO2. The glass transition temperature was found to be the highest ever reported and this system was kinetically strong based on the fragility parameter. Dielectric studies revealed a frequency and temperature independent nature of the dielectric constant and very low dielectric loss. The SHG measurement which was carried out as a function of temperature demonstrated the incidence of blue second harmonic generation in the microcrystals present in the glass matrix. Ba5Li2Ti2Nb8O30 nanocrystals were successfully crystallized in the transparent glass system (100-x)Li2B4O7 – x(Ba5Li2Ti2Nb8O30). Dielectric constant increased while the dielectric loss decreased with the increase in Ba5Li2Ti2Nb8O30 content. Nuclear magnetic resonance spectroscopic studies were carried out to have an insight into the structure of this system. Transmission studies and refractive index measurements were performed and various optical parameters were calculated. Dielectric and transport properties were studied for the glasses and glass nano/microcrystal composites of all the systems reported in this thesis. Li+ ion was found to be responsible for conduction in all these systems. Evolution of self-organized nanopatterns of K3Li2Nb5O15 crystals has been demonstrated in the glass system (100-x) TeO2 - x(1.5K2O-Li2O-2.5Nb2O5) by excimer laser irradiation. The second harmonic signal observed by the Maker fringe technique has been attributed to the presence of well-aligned nano-sized grating structures in the glass system. Glasses belonging to the systems TeO2-K3Li2Nb5O15, TeO2-Ba5Li2Ti2Nb8O30 and V2Te2O9 undergo spinodal decomposition on exposing to KrF pulsed excimer laser. The spinodally phase separated structures were observed on all the surfaces of the samples. Ring shaped patterns were observed on several locations of the samples at higher frequency of laser pulses probably owing to the shock waves produced by the high intense laser beam. Line shaped patterns were found to originate on the sample surfaces when irradiated for longer periods.

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.

The present work aimed to laser sintering and physical characterization of barium titanate ceramics doped with lanthanum, Ba1-xLaxTiO3 (0.1 ≤ x ≤ 0.4) mol%, and co-doped with manganese, in order to study the PTC effect (Positive Temperature Coefficient of Resistance). In electrical and electronic equipments, materials that exhibit PTC effect are generally used in circuit protection, or as temperature sensors (thermistors), whose main advantages of thermistors are no contacts subject to corrosion, high resistance to mechanical shock, the long operating life, low cost and more stable than thermocouples. Additionally, the laser sintering process uses a CO2 laser as the main heating source. This process has been touted as a promising technology for the ceramic processing, which are subjected to extremely high heating and cooling rates (~ 2000 ° C / min). During the processes of synthesis and characterization Differential Thermal Analysis (DTA), Thermogravimetry (TG), Dilatometry, Differential Scanning Calorimetry, X-ray Diffraction, Scanning Electron Microscopy, Impedance Spectroscopy and Conductive Microscopy Atomic Force (CAFM) technique were used. Lanthanum doped barium titanate powders were produced via solid state reaction method and calcined at 1200 ° C for 4 hours. The laser sintering process was efficient to obtain ceramics with relative density of up to 95%. The sintered ceramics presented homogeny microstructure surface under the condition of Pmax = 5.5 W/mm2 for 60 seconds. The 02BT La sample showed the lowest room temperature resistivity (104 .cm). This value is roughly three orders of magnitude lower than that observed for conventionally sintered ceramic in electric furnace and with the same dopant concentration. Finally, it is clear that the sintering conditions strongly modify the PTC behavior of the like-BaTiO3 ceramics, thus allowing the fabrication of ceramic components for the thermistors manufacture with different characteristics. / O presente trabalho teve como objetivos a sinterização a laser e a caracterização físicas de cerâmicas de titanato de bário dopadas com lantânio, Ba1-xLaxTiO3 (0,1 ≤ X ≤ 0,4) mol%, e co-dopadas com manganês, visando estudar o efeito PTC (Coeficiente positivo de resistência com a elevação da temperatura). Em equipamentos eletro-eletrônicos os materiais que exibem o efeito PTC geralmente são utilizados na proteção de circuitos ou como sensores de temperatura (termistores), cujas principais vantagens dos termistores são a inexistência de contatos sujeitos à corrosão, a alta resistência a choques mecânicos, a longa vida de operação, baixo custo, e são mais estáveis que os termopares. Adicionalmente, o processo de sinterização a laser utiliza como principal fonte de calor um laser de CO2. Este processo tem sido apontado como uma técnica promissora no processamento de corpos cerâmicos, os quais são submetidos a taxas de aquecimento e resfriamento extremamente elevadas (~2000 °C/min), podendo provocar assim alterações em suas propriedades físicas. Durante os processos de síntese e caracterização fez-se uso das técnicas de Diferencial de Análise Térmica (DTA), Termogravimétria (TG), Dilatometria, Calorimétria Exploratória Diferencial, Difração de raios X, Microscopia Eletrônica de Varredura e Espectroscopia de Impedância e de Microscopia de Força Atômica em modo condutivo (CAFM). Pós de titanato de bário dopados com lantânio foram sintetizados pelo método da reação de estado sólido e calcinados a 1200 oC por 4 horas. O processo e sinterização a laser se mostrou eficiente para obtenção de cerâmicas com densidade relativa de até 95%. Foi obtida uma homogeneidade na microestrutura em toda a superfície da cerâmica, sob a condição de Pmax = 5,5 W/mm2 por 60s. A amostra 02BT:La apresentou menor valor de resistividade à temperatura ambiente, da ordem de 104 .cm. Este valor é aproximadamente três ordens de grandeza menor que o observado para a cerâmica sinterizada convencionalmente em forno elétrico e na mesma concentração de dopante. Finalmente, é possível afirmar que as condições de sinterização modificam fortemente o comportamento PTC em cerâmicas a base de BaTiO3, possibilitando dessa forma a confecção de cerâmicas para fabricação de componentes termistores com diferentes características.

After the prediction of magnetoelectric effect in Cr2O3, in early 1960's, D. Asrov became the first to experimentally verify this phenomenon. After the pioneering work on magnetoelectric materials in 1960's and 1970's, the discovery of large magnetoelectric effect in orthorhombic rare-earth manganite TbMnO3 has revived great interest in magnetoelectric materials, especially during the last decade. Magnetoelectric multiferroics have great potential in applications such as novel memory storage devices and sensors. As a result of extensive theoretical and experimental investigations conducted on rare-earth magnetoelectric manganites, TbMnO3 has become a prototype magnetoelectric multiferroic material. Orthorhombic rare-earth manganites RMnO3 (R = Gd, Tb and Dy) exhibit improper ferroelectricity where the origin of ferroelectricity is purely magnetic in nature. RMnO3 exhibit diverse and complex magnetic interactions and phases. Doped manganites of the type R1-xAxMnO3 (A = Ca, Sr and Ba) present a rich magnetic and electronic phase diagram. The doping concentration, average ion-size and size mismatch (i.e. disor-der) at A-site, all contribute to determine the ground state. A variety of magnetic phases, competing with each other, are responsible for many functional properties like magnetoelectric effect, colossal magnetoresistance (CMR), magnetostriction and magnetocaloric effect (MCE). In this context, studies of magnetoelectric materials are of great relevance from technical as well as fundamental aspects. Notably, complexity of electronic (and magnetic) phases and experimental difficulties in acquiring reliable measurement-data easily are the most concerning issues in establishing a clear understanding of magnetoelectric materials. In the magnetic phase diagram of RMnO3, GdMnO3 lies on the border between A-type antiferromagnetic and cycloidal antiferromagnetic ground states. Cycloidal spin arrangement is responsible for the induction of ferroelectricity in these materials. There are disparate opinions about the ground state of GdMnO3 (whether the ground state is ferroelectric or not). Understanding of the influence of rare-earth magnetic sublattice on magnetism in GdMnO3 (at low temperature) lacks clarity till date. Neutron scattering studies on GdMnO3 due to high absorption cross-section of Gd ion, yield little success in determining the nature of complex magnetic phases in this material. Interestingly, an earlier report on strontium-substituted gadolinium manganite Gd0.5Sr0.5MnO3 demonstrated the spontaneous electric polarization and related magnetoelectric effect. It was hypothesized that the observed ferroelectricity could be improper and electronic in nature. Strontium doping facilitates quenched disorder that leads to interesting magnetic phases and phase transitions. In order to understand the physical properties of gadolinium manganites and to unravel the relationship between them, it is essential to investigate high quality single crystals of these materials. This thesis deals with growth and investigation of several important physical phenomena of gadolinium manganites such as magnetic, electric, magnetoelectric and magnetocaloric properties. The thesis is organized in seven chapters. A brief summary of each chapter follows: Chapter:1 This chapter provides general introduction to magnetoelectric effect and multiferroicity. The term multiferroicity refers to simultaneous existence of magnetic and electric ordering in a single phase material. Magnetoelectric multiferroics have shown great potential for several applications. They exhibit cross coupling between the electronic and magnetic order parameters, hence basics of various magnetic interactions (and magnetism) are brie y discussed in the rst section of the chapter. It is followed by a brief discussion about the principle of magnetoelectric effect. Magnetoelctric coupling is broadly classified into two types namely, direct coupling and indirect coupling. In the former, the emphasis is given on linear magnetoelectric effect. The concept of multiferroicity is introduced in the next section followed by a brief overview and application potential of multiferroics. Further, classi cation scheme of multiferroic materials is discussed. The concept of improper ferroelectricity and description of subcategories namely, magnetic ferroelectric, geometric ferroelectric and electronic ferroelectric are documented. Magnetic ferroelectric category is considered the most relevant; featuring the type of ferroelectric material as GdMnO3 referred in this thesis. The microscopic theory for mechanism of ferroelectricity in spiral antiferromagnets is presented. While brie ng the thermodynamic background of the magnetocaloric effect, indirect estimation of two important characteristics namely, isothermal magnetic entropy change (∆SM ) and adiabatic change in temperature (∆Tad) under the application of magnetic field are dealt with. In the last part of the chapter, motivation and scope of the thesis is discussed. Chapter:2 This chapter outlines various experimental methodologies adopted in this work. It describes the basic principles of various experimental techniques and related experimental apparatuses used. The chapter starts with the synthesis tech-niques used in the preparation of different compounds studied. The principle of oat-zone method, employed for single-crystal growth, is described. Orientation of single crystals was determined using a home-built back- reflection Laue set up. The basics of Laue reflection and indexing procedure for recorded Laue photographs are described. Various physical properties (electric, magnetic, thermal, magnetoelectric and magnetocaloric properties) were studied using commercial as well as home-built experimental apparatuses. Design and working principle of all the experimental tools are outlined in this chapter. Fabrication details, interfacing of measurement instruments and calibration (standardization) of equipment used in this work are described in appropriate sections. Chapter:3 Chapter-3 describes the investigation of various physical properties of high quality single crystals of magnetoelectric multiferroics, GdMnO3. Synthesis of GdMnO3 is carried out using solid state synthesis route. Single phase nature of the material is confirmed by X-ray powder diffraction technique. Single crystals of GdMnO3 are grown in argon ambience using oat-zone method. As grown crystals are oriented with the help of back-reflection Laue method. GdMnO3 exhibits incommensurate collinear antiferromagnetic phase below 42 K and transforms to canted A-type antiferromagnetic phase below 23 K. Magnetic and specific heat studies have revealed very sharp features near the magnetic transitions which also confirm the high quality of the single crystal. dc magnetization studies illustrate the anisotropic behavior in canted A-type antiferromagnetic phase and clarifies the influence of rare-earth magnetic sub-lattice on overall magnetism (at low temperature). Application of magnetic field (above 10 kOe) along `b' axis helps formation of the cycloidal antiferromagnetic phase. Here, spontaneous electric polarization is induced along `a' axis. The temperature variation plot of dielectric constant, ϵa (under ap- plied magnetic field along `b' axis) shows sharp anomalies in the vicinity of magnetic ordering transitions suggesting magnetodielectric effects. Magnetic field tuning of electric polarization establish the magnetoelectric nature of GdMnO3. Magnetocaloric properties of single crystals of GdMnO3 are investigated using magnetic and magnetothermal measurements. The magnitude of the giant magnetocaloric effect observed is compared with that of other rare-earth manganite multiferroics. Magnetocaloric studies shed light on magnetic ordering of rare-earth ion Gd3+. The phenomenon of inverse magnetocaloric effect observed at low temperature and under low fields is possibly linked to the ordering of Gd3+ spins. Complex interactions between the 3d and 4f magnetic sublattices are believed to influence magnetocaloric properties. Chapter:4 The details of synthesis and single crystal growth of Gd0.5Sr0.5MnO3 using oat-zone method are presented in Chapter 4. Single phase nature of the material is veri ed by carrying out powder x-ray diffraction analysis and confirmation of single crystallinity and orientation through back-reflection Laue method. Electric transport studies reveal semiconductor-like nature of Gd0.5Sr0.5MnO3 until the lowest temperature achieved. This is due to charge localization process which occurs concurrently with decrease in temperature. Gd0.5Sr0.5MnO3 exhibits charge-ordered insulator (COI) phase below 90 K (ac-cording to an earlier report). It is found that under application of magnetic field above a critical value, charge ordering melts and the phase transforms to ferromagnetic metallic (FMM) phase. This transformation is first-order in nature with associated CMR (109%). The first-order phase transition (FOPT) occurs between competing COI and FMM phases and manifests as hysteresis across the FOPT. Strontium doping at A-site induces a large size mismatch at A-site resulting in high quenched disorder in Gd0.5Sr0.5MnO3. The disorder plays a significant role in CMR as well as glass-like dynamics within the low-temperature magnetic phase. ac susceptibility studies and dynamic scaling analysis reveal very slow dynamics inside the low-temperature magnetic phase (below 32 K). According to an earlier report, spontaneous electric polarization and magnetoelectric effect were pronounced near FOPT (at 4.5 K and 100 kOe) between COI and FMM phases. It is prudent to investigate FOPT across COI and FMM phases in Gd0.5Sr0.5MnO3 to understand complex magnetic phases present. Thermodynamic limits of the FOPT (in magnetic field - temperature (H-T) plane), such as supercooling and superheating, are experimentally determined from magnetization and magnetotransport measurements. Interestingly, thermomagnetic anomalies such as open hysteresis loops are observed while traversing the FOPT isothermally or isomagnetically in the H-T plane. These anomalies point towards incomplete phase transformation while crossing the FOPT. Phenomenological model of kinetic arrest is invoked to understand these anomalies. The model put for-ward the idea that while cooling across the FOPT, extraction of specific heat is easier than that of latent heat. In other words, phase transformation across FOPT is thermodynamically allowed but kinetics becomes very slow and phase transformation does not occur at the conventional experimental time scale. Magnetization relaxation measurements (at 89 kOe) with field-cooled magnetization protocol reveal that the relaxation time constant rst decreases with temperature and later, increases non-monotonically below 30 K. This qualita-tive behavior indicates glass-like arrest of the FOPT. Further, thermal cycling studies of zero field-cooled (ZFC) and eld-cooled (FC) magnetization indicate that a low temperature phase prepared with ZFC and FC protocols (at 89 kOe) is not at equilibrium. This confirms the kinetic arrest of FOPT and formation of magnetic phase similar to glass. Chapter:5 Chapter-5 deals with the investigation of the effect of an electric field on charge ordered phase in Gd0.5Sr0.5MnO3 single crystals. As discussed in the previous chapter, application of magnetic field above a critical value collapses the charge ordered phase which transforms to FMM phase. In this view, it is interesting to investigate effect of electric field on the charge ordering. There are various reports on doped manganites such as Pr1-xCaxMnO3 (x = 0:3 to 0:4) that claim melting of charge ordering under application of electric field (or current) above a critical value. In this thesis work, current - voltage (I - V) characteristics of Gd0.5Sr0.5MnO3 are studied at various constant temperatures. Preliminary measurements show that the I-V characteristics are highly non-linear and are accompanied by the onset of negative differential resistance (NDR) above a critical current value. However, we suspect a major contribution of Joule heating in realization of the NDR. Continual I - V loop measurements for five loops revealed thermal drag and that the onset of NDR shifts systematically towards high current values until it disappeared in the current window. Two strategies were employed to investigate the role of Joule heating in realization of NDR: 1) monitoring the sample surface temperature during electric transport measurement and 2) reducing of the Joule heating in a controlled manner by using pulsed current I - V measuremenets. By tuning the duty cycle of the current pulses (or in other words, by controlling the Joule heating in the sample), it was feasible to shift the onset of NDR to any desired value of the current. At low magnitude of the duty cycle in the current range upto 40 mA, the NDR phenomenon did not occur. These experiments concluded that the NDR in Gd0.5Sr0.5MnO3 is a consequence of the Joule heating. Chapter:6 `Chapter-6 deals with the thermal and magnetocaloric properties of Gd0.5Sr0.5MnO3 oriented single crystals. Magnetocaloric properties of Gd0.5Sr0.5MnO3 have been studied using magnetic and magnetothermal measurements. Tempera-ture variation of ∆SM is estimated for magnetic field change of 0 - 70 kOe. The eld 70 kOe is well below the critical magnetic eld required for FOPT between COI and FMM phases. Magnetzation - field (M-H) loop shows minimal hysteresis for measurements up to 70 kOe. The minimal hysteresis behavior al-lows one to make fairly accurate estimation of magnetocaloric properties. ∆Tad was separately estimated from specific heat measurements at different magnetic fields. Specific heat studies show the presence of Schottky-like anomaly at low temperature. Chapter:7 Finally, Chapter-7 summarizes various experimental results, analyses and conclusions. A broad outlook of the work in general with future scope of research in this area are outlined in this chapter.

Les matériaux composites prennent une place de plus en plus importante dans la conception et la fabrication des moyens de transport et notamment dans le domaine naval où ils sont particulièrement privilégiés. En effet, ces matériaux sont utilisés pour leur légèreté, insensibilité à la corrosion et leurs caractéristiques mécaniques. Dans le domaine militaire, où l'optimisation des moyens de communication et de protection électromagnétique est primordiale, le développement de matériaux composites dotés de propriétés de reconfigurabilité sous commande(s) externe(s), présente un atout opérationnel majeur pour les parois structurales exploitant ces matériaux. Afin d'explorer cette voie, DCNS et l'Institut d’Électronique et de Télécommunications de Rennes (IETR, UMR-6164) se sont associés. Les travaux de thèse engagés ont pour objectif d'étudier et de développer des matériaux composites présentant des fonctions de reconfigurabilité applicables aux systèmes navals tels que les radômes, les antennes et exploitables pour répondre aux problématiques de furtivité (SER). Une première étude a permis d'explorer les matériaux à base de carbone, présentant une potentielle agilité de leurs caractéristiques diélectriques sous actuateur électrique. Ces matériaux présentent également un fort pouvoir absorbant électromagnétique, tributaire des propriétés diélectriques, elles-mêmes potentiellement reconfigurables. La seconde étude engagée a étudié l'impact des matériaux ferroélectriques, c'est-à-dire des matériaux reconfigurables sous champ électrique, lorsqu'ils sont intégrés comme charge dans une résine d'imprégnation. Ce nouveau matériau composite présente alors une reconfigurabilité de ses caractéristiques diélectriques, rendant commandable en fréquence sa structure hôte. Une troisième étude, exploitant aussi le matériau ferroélectrique a permis l'obtention d'une reconfigurabilité des caractéristiques de réflectivité de panneaux composites grâce au développement de surfaces sélectives en fréquence reconfigurables. De nouvelles propriétés ont ainsi été mises en évidence en hyperfréquences. Enfin, les matériaux d'âmes et spécifiquement les nids d'abeilles diélectriques ont fait l'étude d'une fonctionnalisation pour des applications DC et hyperfréquences. / Composite materials are used for their lightness, high resistance to corrosion and high mechanical properties over large application areas, such as naval, ground and aerial. Collaboration between DCNS group and the Institute of Electronics and Telecommunications of Rennes (IETR, UMR-6164) has been initiated to develop smart composite materials with tunable properties at microwaves. Three different routes have been investigated during the thesis work. The first one is based on carbon composite material, its electromagnetic absorbing ability and its potential dielectric tunability. For this, we develop composite materials loaded with various carbon particles (carbon nanotube, graphene, black carbon). Next, to elaborate smart composite materials, a ferroelectric material has been used as filler. The dielectric characteristics of such materials can be tuned under external biasing for example. Thus we develop an active composite material under various external actuators for naval application, and especially for new reconfigurable frequency selective surface (RFSS). Finally dielectric honeycomb materials have been specifically elaborated and studied to develop smart properties for DC and microwave applications. During this work, three different prototypes improving composite materials in naval area have been performed: reconfigurable radome, RCS reduction, and antenna isolation.

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.

Ferroelectricity is very attractive for nonvolatile memories since it allows non-volatility paired with a field driven switching mechanism enabling a very low-power write operation. Non-volatile memories based on ferroelectric lead-zirconium-titanate (PZT) (see fig. la) are available on the market for more than a quarter of a century now [1]. Yet they are limited to niche applications due to the compatibility issues of the ferroelectric material with CMOS processes and the associated limited scalability [2]. The discovery of ferroelectricity in doped hafnium oxide has revived the activities towards a variety of scalable ferroelectric nonvolatile memory devices

Spontaneous Raman spectroscopy (SR) is a versatile method for analysis and visualization of ferroelectric crystal structures, including domain walls. Nevertheless, the necessary acquisition time makes SR impractical for in situ analysis and large scale imaging. In this work, we introduce broadband coherent anti-Stokes Raman spectroscopy (B-CARS) as a high-speed alternative to conventional Raman techniques and demonstrate its benefits for ferroelectric domain wall analysis. Using the example of poled lithium niobate, we compare the spectral output of both techniques in terms of domain wall signatures and imaging capabilities. We extract the Raman-like resonant part of the coherent anti-Stokes signal via a Kramers–Kronigbased phase retrieval algorithm and compare the raw and phase-retrieved signals to SR characteristics. Finally, we propose a mechanism for the observed domain wall signal strength that resembles a Cerenkov-like behavior, in close analogy to domain wall signatures obtained by secondharmonic generation imaging.We, thus, lay here the foundations for future investigations on other poled ferroelectric crystals using B-CARS.