Organometal halide perovskite absorbers such as methylammonium lead iodide chloride (CH3NH3PbI3-xClx), have emerged as an exciting new material family for photovoltaics due to its appealing features that include suitable direct bandgap with intense light absorbance, band gap tunability, ultra-fast charge carrier generation, slow electron-hole recombination rates, long electron and hole diffusion lengths, microsecond-long balanced carrier mobilities, and ambipolarity. The standard method of preparing CH3NH3PbI3-xClx perovskite precursors is a tedious process involving multiple synthesis steps and, the chemicals being used (hydroiodic acid and methylamine) are quite expensive. This work describes a novel, single-step, simple, and cost-effective solution approach to prepare CH3NH3PbI3-xClx thin films by the direct reaction of the commercially available CH3NH3Cl (or MACl) and PbI2. A detailed analysis of the structural and optical properties of CH3NH3PbI3-xClx thin films deposited by aerosol assisted chemical vapor deposition is presented. Optimum growth conditions have been identified. It is shown that the deposited thin films are highly crystalline with intense optical absorbance. Charge carrier separation of these thin films can be enhanced by establishing a local internal electric field that can reduce electron-hole recombination resulting in increased photo current. The intrinsic ferroelectricity in nanoparticles of Barium Titanate (BaTiO3 -BTO) embedded in the solar absorber can generate such an internal field. A hybrid structure of CH3NH3PbI3-xClx perovskite and ferroelectric BTO nanocomposite FTO/TiO2/CH3NH3PbI3-xClx: BTO/P3HT/Cu as a new type of photovoltaic device is investigated. Aerosol assisted chemical vapor deposition process that is scalable to large-scale manufacturing was used for the growth of the multilayer structure. TiO2 and P3HT with additives were used as ETL and HTL respectively. The growth process of the solar absorber layer includes the nebulization of a mixture of PbI2 and CH3NH3Cl perovskite precursors and BTO nanoparticles dissolved in DMF, and injection of the aerosol into the growth chamber and subsequent deposition on TiO2. While high percentage of BTO in the film increases the carrier separation, it also leads to reduced carrier generation. A model was developed to guide the optimum BTO nanoparticle concentration in the nanocomposite films. Characterization of perovskite solar cells indicated that ferroelectric polarization of BTO nanoparticles leads to the increase of the width of depletion regions in the perovskite layer hence the photo current was increased by one order of magnitude after poling the devices. The ferroelectric polarization of BTO nanoparticles within the perovskite solar absorber provides a new perspective for tailoring the working mechanism and photovoltaic performance of perovskite solar cells.

No description available.

Perovskite based artificial superlattices has recently been extensively investigated due to the immense promise in various device applications. The major applications include non-volatile random access memories, microwave devices, phase shifters voltage tunable capacitor applications etc. In this thesis we have taken up the investigation of two different types of symmetric superlattices, viz. BaZrO3/BaTiO3 and SrTiO3/BaZrO3, with possible applicability to voltage tunable devices. Chapter 1 deals with the introduction to the perovskite based functional oxides. Their various applications and the specific requirements for voltage tunable device applications has also been discussed in detail. The basic properties of BaTiO3 and SrTiO3, which are well documented in the literature, have been reviewed. The fundamental physics of interfacial interactions that influence the properties of superlattices is also discussed using existing models. The reason behind the choice of constructing artificial superlattices of BaZrO3/BaTiO3 and SrTiO3/BaZrO3 and the motivation behind this thesis is outlined. Chapter 2 gives a brief description of the basic characterization techniques that has been employed for studying the thin films. These include pulsed laser deposition of oxide thin films, structural characterization using X-Ray Diffraction and Atomic Force Microscope and electrical characterization of thin film metal-insulator-metal structures. The basic principle behind the techniques has also been included in various sections of this chapter. Chapter 3 introduces the reader to basic properties of the less studied perovskite material BaZrO3, one of the parent components of Ba(Zr,Ti)O3 based ceramics for high frequency applications. BaZrO3 is the common material in both the types of superlattices studied in this thesis. Initially the growth of polycrystalline BaZrO3 on (111)Pt/TiO2/SiO2/Si has been elaborated in this chapter. After characterizing the crystalline quality of the films and optimizing the growth conditions, epitaxial BaZrO3 films has been grown on (001) SrTiO3 substates. Dielectric properties of epitaxial BaZrO3 film have been measured as a function of temperature and frequencies. The electric field tunability of BaZrO3 films has been calculated from capacitance-voltage data for comparison with superlattice structures. Chapter 4 deals with the basic considerations involving growth of artificial superlattices and multilayers using pulsed laser ablation technique. The fundamental differences between formation of multilayers and superlattices have also been discussed, and the basic considerations for optimizing growth parameters are analyzed in this chapter. X-ray θ-2θ and φ-scans have been performed to investigate crystal quality of superlattices. The growth rates calculated from the satellite reflections in X-ray θ-2θ scans indicate fair degree of control over the growth and φ-scans confirms epitaxial cube-on cube growth of both types of superlattices. Atomic Force microscopy has been used to hcaracterize the film quality and surface morphology of superlattice structures and it has been found that the films have a very smooth surface with rms roughness of the order of few nanometres. Chapter5 deals with the detailed electrical characterization of both types of superlattices structures. Dielectric response showed nearly temperature invariance for both types of superlattices. Polarization measurements show that the heterostructures are in paraelectric state. Even for paraelectric/ferroelectric BaZrO3/BaTiO3 superlattices, stress induced stabilization of the paraelectric state is exhibited in low period superlattices. Paraelectric/paraelectric-SrTiO3/BaZrO3 superlattices exhibited a tunability of ~20% at intermediate modulation periods and an extremely stable dissipation factor with respect to temperature which is very attractive for device application point of view. A maximum tunability of ~40% has been observed for lowest period BaZrO3/BaTiO3 superlattice. Relatively high Quality Factors has been observed for both type of superlattices and their dependence on the modulation periods has been analyzed. Dielectric relaxation data showed that Maxwell-Wanger type of behaviour is exhibited but the presence of a conductance component G had to be realized in the equivalent circuit representation, which originates from the observation of a square law dependence of the alternating current on the frequency. Finally DC electrical characteristics were investigated as a function of temperature to determine the type of conduction mechanism that is involoved. The data has been analyzed using existing theories of high field conduction in thin dielectric films and it has been found that at different temperature ranges, the conduction mechanism varied from bulk limited Poole-Frenkel to Space Charge limited conduction. The activation energy calculation indicate that the physical processes responsible for dielectric relaxation and dc conduction are identical.

A flexible nanofibrous PVDF-BaTiO3 composite material is prepared for impact sensing and biomechanical energy harvesting applications. Dielectric polyvinylidene fluoride (PVDF) and barium titanate (BaTiO3)-PVDF nanofibrous composites were made using the electrospinning process based on a design of experiments approach. The ultrasonication process was optimized using a 2k factorial DoE approach to disperse BaTiO3 particles in PVDF solution in DMF. Scanning electron microscopy was used to characterize the microstructure of the fabricated mesh. The FT-IR and Raman analysis were carried out to investigate the crystal structure of the prepared mesh. Surface morphology contribution to the adhesive property of the composite was explained through contact angle measurements. The capacitance of the prepared PVDF- BaTiO3 nanofibrous mesh was a more than 40% increase over the pure PVDF nanofibers. A comparative study of dielectric relaxation, thermodynamics properties and impact analysis of electrospun polyvinylidene fluoride (PVDF) and 3% BaTiO3-PVDF nanofibrous composite are presented. The frequency dependent dielectric properties revealed micro structural features of the composite material. The dielectric relaxation behavior is further supported by complex impedance analysis and Nyquist plots. The temperature dependence of electric modulus shows Arrhenius type behavior. The observed non-Debye dielectric relaxation in electric loss modulus follows a thermally activated process which can be attributed to a small polaron hopping effect. The particle induced crystallization is supported with thermodynamic properties from differential scanning calorimetric (DSC) measurements. The observed increase in piezoelectric response by impact analysis was attributed to the interfacial interaction between PVDF and BaTiO3. The interfacial polarization between PVDF and BaTiO3 was studied using density functional theory calculations and atomic charge density analysis. The results obtained indicates that electrospinning offers a potential way to produce nanofibers with desired crystalline nature which was not observed in molded samples. In addition, BaTiO3 can be used to increase the capacitance, desired surface characteristics of the PVDF nanofibers which can find potential application as flexible piezoelectric sensor mimicking biological skin for use in impact sensing and energy harvesting applications.

<p dir="ltr">Piezoelectric polymers and ceramics have applications throughout many fields, including their use as pressure sensors and transducers. Of the polymers, poly(vinylidene fluoride – trifluoroethylene) (P(VDF-TrFE)), has been the go-to for its high piezoelectric performance. With the addition of aluminum nanopowders (nAl), P(VDF-TrFE) acts as a binder and oxidizer, creating an energetic composite, a so-called piezoenergetic. However, this typically results in lower d₃₃ coefficients and can have lower reactivity since ideal mixtures may short when poled. Here, we develop and demonstrate single-layer and multilayer polymer composite films with high piezoelectric and energetic content. We prepared single-layer thin film piezoelectric energetic composites of nAl and P(VDF-TrFE) and a combination of thermal annealing and poling at elevated temperatures enabled full poling of 9 wt.% nAl/P(VDF-TrFE) films with d₃₃ of 22.7 pC/N that is comparable to P(VDF-TrFE) films. We also investigated the addition of barium titanate (BaTiO₃) particles as a piezoelectric ceramic to enhance the d₃₃ coefficient. In the neat polymer, BaTiO₃ had differing effects depending on the particle size, with 200 nm particles improving the d₃₃ coefficient more than the 1 μm particles. However, neither size of BaTiO₃ particle had a substantial effect on the piezoelectricity in the 9 wt.% nAl/P(VDF-TrFE) films. We also prepared hot-pressed, three-layer “sandwich” P(VDF-TrFE) – 30 wt.% nAl/P(VDF-TrFE) – P(VDF-TrFE) composites, which had marginally lower d₃₃ coefficients than the single-layer 9 wt.% nAl/P(VDF-TrFE) films. However, the 30 wt.% nAl/P(VDF-TrFE) sandwich films were far more energetic than the 9 wt.% nAl/P(VDF-TrFE) films, as confirmed by simultaneous differential scanning calorimetry and thermogravimetric analysis (DSC/TGA) and deflagration studies. The single films will often fail to fully sustain a deflagration, while the sandwich films burn completely. In addition, we can ignite the sandwich samples with an electrical discharge making these films also useful in ignition applications. To demonstrate the use of piezoenergetic films, 9 wt.% nAl/P(VDF-TrFE) single layer and 30 wt.% nAl/P(VDF-TrFE) sandwich films were calibrated as pressure gauges using a mini drop weight setup, and then demonstrated as a pressure gage. The improvements in the piezoelectric coefficient of the 9 wt.% nAl/P(VDF-TrFE) single layer films, as well as the energetic performance in the form of the 30 wt.% nAl/P(VDF-TrFE) sandwich films strongly amplify the existing potential of these multifunctional composites in energetic and pressure sensing applications.</p>

Made available in DSpace on 2017-07-24T19:37:53Z (GMT). No. of bitstreams: 1 Luis Lacerda.pdf: 6157407 bytes, checksum: 67f47ee9ce5d908521ba3d0455add580 (MD5) Previous issue date: 2015-03-09 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Semiconductors materials are largely employed on development of innumerous optical and electronic due to their electronic, optical, ferroelectric and structural properties. Among the semiconductors materials stand out the zinc oxide (ZnO) and the barium titanate (BaTiO3) once shows excellent properties allied to low cost to obtaining. The ZnO is a simple oxide used in technology and largely investigated as an alternative to replace high cost material on development of electronic devices. Similarly, the BaTiO3 has perovskite crystalline structure whose properties present great technological interest. This work evaluated the effect of Ba presence on wurtzite structure and the influence of Zn atoms on tetragonal BaTiO3 properties. The obtained results indicates that the Ba atoms changes drastically the band structure of ZnO, resulting in the decrease of band gap for low quantities and the semiconductor type modification for doping above 25 %. The insertion of such atoms in wurtzite also causes the improvement of ferroelectric properties and the increase of unit cell lattice parameters. In case of Zn-doped BaTiO3, the doping process reduces radically de band gap and the ferroelectric properties regarding to pure material. Likewise, the semiconductor type is also modified by the Zn atoms presence. Based on obtained results for both crystalline systems, was proposed their employed in formation of p-n heterojunction. The heterostructure was evaluated through of four models. The obtained results for each one of these models were used to describe the interface region of ZnO/BaTiO3 heterojunction, proving that the atoms intercalation occurs and is responsible for heterostructure properties. Such properties present this heterostructure as a potential alternative for development of electronic devices, mainly the development of memory devices. The obtained heterostructure requires a low amount energy to electronic conduction process and shows high compatibility between the structure of heterojunction and the SiO2 substrate which is used in development of such devices. / Materiais semicondutores são amplamente empregados no desenvolvimento de vários dispositivos ópticos e eletrônicos variados devido às suas propriedades eletrônicas, ópticas, ferroelétricas e estruturais. Dentre os materiais semicondutores, destacam-se o óxido de zinco (ZnO) e o Titanato de Bário (BaTiO3) uma vez que apresentam excelentes propriedades aliadas ao baixo custo de síntese. O ZnO é um óxido simples amplamente empregado na tecnologia e largamente investigado como uma alternativa para substituição de materiais de custo elevado no desenvolvimento de dispositivos eletrônicos. Por sua vez, o BaTiO3 é um material de estrutura cristalina perovskita cujas propriedades são de grande interesse tecnológico. No presente trabalho avaliou-se o efeito da presença de átomos de Ba na estrutura wurtzita do ZnO e a influência dos átomos de Zn sobre as propriedades do BaTiO3 tetragonal. Os resultados indicaram que os átomos de bário alteram drasticamente a estrutura de bandas do ZnO, resultando na diminuição do band gap para pequenas quantidades e a modificação do tipo de semicondutor para dopagens superiores a 25%. A inserção de tais átomos na estrutura wurtzita também é responsável pelo aprimoramento das propriedades ferroelétricas do material, bem como pelo aumento dos parâmetros de rede da célula unitária. No caso da estrutura do BaTiO3 dopada com Zn observou-se a redução drástica do band gap para o material e a modificação do caráter semicondutor do material; entretanto, ocorreu a redução das propriedades ferroelétricas em relação ao BaTiO3 puro. Com base nos resultados obtidos para ambos os sistemas cristalinos, propôs-se a sua utilização para formação de uma heterojunção do tipo p-n. A heteroestrutura foi avaliada por meio de quatro modelos diferentes. Os resultados obtidos para cada um destes modelos foram utilizados para descrição da estrutura eletrônica da região de interface da heterojunção, comprovando que a intercalação de átomos na interface é observada e mostra-se responsável pelas propriedades observadas para a heteroestrutura. Tais propriedades apontam a heterojunção ZnO/BaTiO3 como uma alternativa em potencial para aplicação no desenvolvimento de dispositivos eletrônicos e, principalmente, no desenvolvimento de dispositivos de armazenamento de dados, devido a diminuição de energia necessária para condução eletrônica.

Near-field optical microscopy allows the nondestructive examination of surfaces with a spatial resolution far below the diffraction limit of Abbe. In fact, the resolution of this kind of microscope is not at all dependent on the wavelength, but is typically in the range of 10 to 100 nanometers. On this scale, many materials are anisotropic, even though they might appear isotropic on the macroscopic length scale. In the present work, the previously never studied interaction between a scattering-type near-field probe and an anisotropic sample is examined theoretically as well as experimentally. In the theoretical part of the work, the analytical dipole model, which is well known for isotropic samples, is extended to anisotropic samples. On isotropic samples one observes an optical contrast between different materials, whereas on anisotropic samples one expects an additional contrast between areas with different orientations of the same dielectric tensor. The calculations show that this anisotropy contrast is strong enough to be observed if the sample is excited close to a polariton resonance. The experimental setup allows the optical examination in the visible and in the infrared wavelength regimes. For the latter, a free-electron laser was used as a precisely tunable light source for resonant excitation. The basic atomic force microscope provides a unique combination of different scanning probe microscopy methods that are indispensable in order to avoid artifacts in the measurement of the near-field signal and the resulting anisotropy contrast. Basic studies of the anisotropy contrast were performed on the ferroelectric single crystals barium titanate and lithium niobate. On lithium niobate, we examined the spectral dependence of the near-field signal close to the phonon resonance of the sample as well as its dependence on the tip-sample distance, the polarization of the incident light, and the orientation of the sample. On barium titanate, analogous measurements were performed and, additionally, areas with different types of domains were imaged and the near-field optical contrast due to the anisotropy of the sample was directly measured. The experimental results of the work agree with the theoretical predictions. A near-field optical contrast due to the anisotropy of the sample can be measured and allows areas with different orientations of the dielectric tensor to be distinguished optically. The contrast results from variations of the dielectric tensor components both parallel and perpendicular to the sample surface. The presented method allows the optical examination of anisotropies of a sample with ultrahigh resolution, and promises applications in many fields of research, such as materials science, information technology, biology, and nanooptics. / Die optische Nahfeldmikroskopie ermöglicht die zerstörungsfreie optische Unter- suchung von Oberflächen mit einer räumlichen Auflösung weit unterhalb des klas- sischen Beugungslimits von Abbe. Die Auflösung dieser Art von Mikroskopie ist unabhängig von der verwendeten Wellenlänge und liegt typischerweise im Bereich von 10-100 Nanometern. Auf dieser Längenskala zeigen viele Materialien optisch anisotropes Verhalten, auch wenn sie makroskopisch isotrop erscheinen. In der vorliegenden Arbeit wird die bisher noch nicht bestimmte Wechselwirkung einer streuenden Nahfeldsonde mit einer anisotropen Probe sowohl theoretisch als auch experimentell untersucht. Im theoretischen Teil wird das für isotrope Proben bekannte analytische Dipol- modell auf anisotrope Materialien erweitert. Während fÄur isotrope Proben ein reiner Materialkontrast beobachtet wird, ist auf anisotropen Proben zusätzlich ein Kontrast zwischen Bereichen mit unterschiedlicher Orientierung des Dielektrizitätstensors zu erwarten. Die Berechnungen zeigen, dass dieser Anisotropiekontrast messbar ist, wenn die Probe nahe einer Polaritonresonanz angeregt wird. Der verwendete experimentelle Aufbau ermöglicht die optische Untersuchung von Materialien im sichtbaren sowie im infraroten Wellenlängenbereich, wobei zur re- sonanten Anregung ein Freie-Elektronen-Laser verwendet wurde. Das dem Nahfeld- mikroskop zugrunde liegende Rasterkraftmikroskop bietet eine einzigartige Kombi- nation verschiedener Rastersondenmikroskopie-Methoden und ermöglicht neben der Untersuchung von komplementären Probeneigenschaften auch die Unterdrückung von mechanisch und elektrisch induzierten Fehlkontrasten im optischen Signal. An den ferroelektrischen Einkristallen Lithiumniobat und Bariumtitanat wurde der anisotrope Nahfeldkontrast im infraroten WellenlÄangenbereich untersucht. An eindomÄanigem Lithiumniobat wurden das spektrale Verhalten des Nahfeldsignals sowie dessen charakteristische Abhängigkeit von Polarisation, Abstand und Proben- orientierung grundlegend untersucht. Auf Bariumtitanat, einem mehrdomänigen Kristall, wurden analoge Messungen durchgeführt und zusätzlich Gebiete mit ver- schiedenen Domänensorten abgebildet, wobei ein direkter nachfeldoptischer Kon- trast aufgrund der Anisotropie der Probe nachgewiesen werden konnte. Die experimentellen Ergebnisse dieser Arbeit stimmen mit den theoretischen Vorhersagen überein. Ein durch die optische Anisotropie der Probe induzierter Nahfeldkontrast ist messbar und erlaubt die optische Unterscheidung von Gebie- ten mit unterschiedlicher Orientierung des Dielektriziätstensors, wobei eine Än- derung desselben sowohl parallel als auch senkrecht zur Probenoberfläche messbar ist. Diese Methode erlaubt die hochauflösende optische Untersuchung von lokalen Anisotropien, was in zahlreichen Gebieten der Materialwissenschaft, Speichertech- nik, Biologie und Nanooptik von Interesse ist.

Les propriétés physiques d’un matériau sont intimement liées à sa structure cristalline et dans le cas d’ions dopants aux sites qu’ils occupent. La première partie de ce travail est dédiée au matériau diphosphate de sodium et de zinc Na2ZnP2O7, cristallisé out vitreux et ceci pour les ions dopants Co2+, Ni2+, Mn2+ et Eu3+. Les phases cristallisées ont été obtenues par la méthode Czochralski, les verres par trempe à partir de l’état fondu. Un ensemble de caractéristiques physiques ont été mises en jeu (Raman, infrarouge, RPE, absorption optique, luminescence) pour déterminer les sites occupés par les ions dopants et l’influence sur les propriétés optiques. La deuxième partie de cet travail consiste à une meilleure connaissance des matériaux diélectriques sans plomb appartenant à la famille pérovskite et plus particulièrement à la solution solide NaNbO3-BaTiO3. Des monocistaux ont été obtenus par la méthode des flux et caractérisés en utilisant plusieurs techniques : diffraction X, microanalyse, évolution thermique des domaines ferroélectriques-ferroélastiques, mesures diélectriques, piézoélectriques et pyroélectriques. / Abstract The physical properties of a material are intimately related to its crystalline structure and in the case of doped ions they are dependent on to the sites they occupy. The first part of this work is dedicated to the diphosphate material of sodium and zinc Na2ZnP2O7, glassy and crystallized for doped ions of Co2+, Ni2+, Mn2+ and Eu3+. The crystallized phases were obtained by the Czochralski method whereas the glasses were obtained by quenching from the molten state. A set of physical characteristics were studied (Raman, infrared, EPR, optical absorption, luminescence) to determine the sites occupied by the doped ions and its influence on the optical properties. The second part of this work consists of a better knowledge of lead-free dielectric materials belonging to the family of Perovskite, more particularly to NaNbO3-BaTiO3 solid solution. Single crystals were obtained by the flux method and were characterized using several techniques: X-rays diffraction, microanalysis, thermal evolution of ferroelectric and ferroelastic domains; dielectric, piezoelectric and pyroelectric measurements.

Near-field optical microscopy allows the nondestructive examination of surfaces with a spatial resolution far below the diffraction limit of Abbe. In fact, the resolution of this kind of microscope is not at all dependent on the wavelength, but is typically in the range of 10 to 100 nanometers. On this scale, many materials are anisotropic, even though they might appear isotropic on the macroscopic length scale. In the present work, the previously never studied interaction between a scattering-type near-field probe and an anisotropic sample is examined theoretically as well as experimentally. In the theoretical part of the work, the analytical dipole model, which is well known for isotropic samples, is extended to anisotropic samples. On isotropic samples one observes an optical contrast between different materials, whereas on anisotropic samples one expects an additional contrast between areas with different orientations of the same dielectric tensor. The calculations show that this anisotropy contrast is strong enough to be observed if the sample is excited close to a polariton resonance. The experimental setup allows the optical examination in the visible and in the infrared wavelength regimes. For the latter, a free-electron laser was used as a precisely tunable light source for resonant excitation. The basic atomic force microscope provides a unique combination of different scanning probe microscopy methods that are indispensable in order to avoid artifacts in the measurement of the near-field signal and the resulting anisotropy contrast. Basic studies of the anisotropy contrast were performed on the ferroelectric single crystals barium titanate and lithium niobate. On lithium niobate, we examined the spectral dependence of the near-field signal close to the phonon resonance of the sample as well as its dependence on the tip-sample distance, the polarization of the incident light, and the orientation of the sample. On barium titanate, analogous measurements were performed and, additionally, areas with different types of domains were imaged and the near-field optical contrast due to the anisotropy of the sample was directly measured. The experimental results of the work agree with the theoretical predictions. A near-field optical contrast due to the anisotropy of the sample can be measured and allows areas with different orientations of the dielectric tensor to be distinguished optically. The contrast results from variations of the dielectric tensor components both parallel and perpendicular to the sample surface. The presented method allows the optical examination of anisotropies of a sample with ultrahigh resolution, and promises applications in many fields of research, such as materials science, information technology, biology, and nanooptics. / Die optische Nahfeldmikroskopie ermöglicht die zerstörungsfreie optische Unter- suchung von Oberflächen mit einer räumlichen Auflösung weit unterhalb des klas- sischen Beugungslimits von Abbe. Die Auflösung dieser Art von Mikroskopie ist unabhängig von der verwendeten Wellenlänge und liegt typischerweise im Bereich von 10-100 Nanometern. Auf dieser Längenskala zeigen viele Materialien optisch anisotropes Verhalten, auch wenn sie makroskopisch isotrop erscheinen. In der vorliegenden Arbeit wird die bisher noch nicht bestimmte Wechselwirkung einer streuenden Nahfeldsonde mit einer anisotropen Probe sowohl theoretisch als auch experimentell untersucht. Im theoretischen Teil wird das für isotrope Proben bekannte analytische Dipol- modell auf anisotrope Materialien erweitert. Während fÄur isotrope Proben ein reiner Materialkontrast beobachtet wird, ist auf anisotropen Proben zusätzlich ein Kontrast zwischen Bereichen mit unterschiedlicher Orientierung des Dielektrizitätstensors zu erwarten. Die Berechnungen zeigen, dass dieser Anisotropiekontrast messbar ist, wenn die Probe nahe einer Polaritonresonanz angeregt wird. Der verwendete experimentelle Aufbau ermöglicht die optische Untersuchung von Materialien im sichtbaren sowie im infraroten Wellenlängenbereich, wobei zur re- sonanten Anregung ein Freie-Elektronen-Laser verwendet wurde. Das dem Nahfeld- mikroskop zugrunde liegende Rasterkraftmikroskop bietet eine einzigartige Kombi- nation verschiedener Rastersondenmikroskopie-Methoden und ermöglicht neben der Untersuchung von komplementären Probeneigenschaften auch die Unterdrückung von mechanisch und elektrisch induzierten Fehlkontrasten im optischen Signal. An den ferroelektrischen Einkristallen Lithiumniobat und Bariumtitanat wurde der anisotrope Nahfeldkontrast im infraroten WellenlÄangenbereich untersucht. An eindomÄanigem Lithiumniobat wurden das spektrale Verhalten des Nahfeldsignals sowie dessen charakteristische Abhängigkeit von Polarisation, Abstand und Proben- orientierung grundlegend untersucht. Auf Bariumtitanat, einem mehrdomänigen Kristall, wurden analoge Messungen durchgeführt und zusätzlich Gebiete mit ver- schiedenen Domänensorten abgebildet, wobei ein direkter nachfeldoptischer Kon- trast aufgrund der Anisotropie der Probe nachgewiesen werden konnte. Die experimentellen Ergebnisse dieser Arbeit stimmen mit den theoretischen Vorhersagen überein. Ein durch die optische Anisotropie der Probe induzierter Nahfeldkontrast ist messbar und erlaubt die optische Unterscheidung von Gebie- ten mit unterschiedlicher Orientierung des Dielektriziätstensors, wobei eine Än- derung desselben sowohl parallel als auch senkrecht zur Probenoberfläche messbar ist. Diese Methode erlaubt die hochauflösende optische Untersuchung von lokalen Anisotropien, was in zahlreichen Gebieten der Materialwissenschaft, Speichertech- nik, Biologie und Nanooptik von Interesse ist.

Τα Νανοσύνθετα συστήματα πολυμερικής μήτρας – σιδηροηλεκτρικών ή πιεζοηλεκτρικών σωματιδίων (κεραμικά εγκλείσματα) αναμένεται να αποτελέσουν μια νέα γενιά υψηλού τεχνολογικού ενδιαφέροντος που θα επιδεικνύουν λειτουργικές ιδιότητες λόγω της ποικίλης πόλωσης των κεραμικών νανοσωματιδίων. Η διασπορά κεραμικών εγκλεισμάτων στο εσωτερικό πολυμερικής μήτρας προσδίδει στα σύνθετα συστήματα βελτιωμένη μηχανική και ηλεκτρική συμπεριφορά. Τέτοιου τύπου συστήματα υλικών, που έχουν υψηλή ηλεκτρική διαπερατότητα (high-Κ materials) χρησιμοποιούνται σε ηλεκτρονικές εφαρμογές, καθώς μειώνουν τα ρεύματα διαρροής και παράλληλα λειτουργούν ως ενσωματωμένοι νανο-πυκνωτές και αισθητήρες ακουστικών εκπομπών. Η ηλεκτρική απόκριση τους, εκφράζεται κυρίως μέσω της ηλεκτρικής διαπερατότητας και μπορεί να ρυθμιστεί, ελέγχοντας τον τύπο, το μέγεθος και την ποσότητα της κεραμικής ενίσχυσης. Η ενσωμάτωση σιδηροηλεκτρικών ή πιεζοηλεκτρικών κρυστάλλων, που επιδεικνύουν υψηλή πόλωση, σε μια πολυμερική μήτρα, όπως η εποξειδική ρητίνη – που εν γένει είναι ηλεκτρικός μονωτής- με χαμηλή ηλεκτρική διαπερατότητα και υψηλή διηλεκτρική αντοχή μπορεί να οδηγήσει στην ανάπτυξη ενός ευφυούς συστήματος. Σκοπός αυτής της εργασίας είναι η παρασκευή και ο χαρακτηρισμός σύνθετων πολυμερικών συστημάτων εποξειδικής ρητίνης – νανοσωματιδίων τιτανικού ψευδάργυρου (ZnTiO3) καθώς και σύνθετων υβριδικών συστημάτων εποξειδικής ρητίνης - νανοσωματιδίων τιτανικού ψευδάργυρου (ZnTiO3) και τιτανικού βαρίου (BaTiO3) ώστε να οδηγηθούμε σε ένα σύστημα υλικών με βέλτιστη συμπεριφορά. Στο θεωρητικό κομμάτι αυτής της εργασίας συζητούνται βασικές έννοιες και θεωρίες που αφορούν τα σύνθετα υλικά, τη θεωρία των διηλεκτρικών και ενεργών διηλεκτρικών, την ηλεκτρική συμπεριφορά σύνθετων υλικών με πολυμερική μήτρα καθώς και πειραματικές τεχνικές χαρακτηρισμού. Στο πειραματικό μέρος, νανοσύνθετα πολυμερικά συστήματα παρασκευάστηκαν από εποξειδική ρητίνη και νανοσωματίδια ZnTiO3 και BaTiO3. Η μέση διάμετρος σωματιδίων βάσει των προδιαγραφών του προμηθευτή ήταν λιγότερο από 100nm για το ZnTiO3 και στην περιοχή των 30 - 50nm για το BaTiO3. Στη συνέχεια τα νανοσύνθετα υποβλήθηκαν σε μορφολογικό, θερμικό και ηλεκτρικό χαρακτηρισμό. Η μορφολογία των δειγμάτων εξετάστηκε για τυχούσα παρουσία κενών (voids) και συσσωματωμάτων (clusters) μέσω του Ηλεκτρονικού Μικροσκοπίου Σάρωσης (SEM) και η θερμική τους απόκριση μέσω της Διαφορικής Θερμιδομετρίας Σάρωσης (DSC). Η διασπορά των κεραμικών εγκλεισμάτων θεωρήθηκε ικανοποιητική, παρόλο που συνυπάρχουν οι νανοδιασπορές με συσσωματώματα. Οι διηλεκτρικές ιδιότητες και τα σχετιζόμενα φαινόμενα διεργασιών χαλάρωσης μελετήθηκαν με χρήση της Διηλεκτρικής Φασματοσκοπίας Ευρέως Φάσματος (BDS) στο εύρος θερμοκρασιών -100 oC έως 160 oC και στο διάστημα συχνοτήτων 10-1 Hz έως 106 Hz. Η ανάλυση των πειραματικών αποτελεσμάτων διεξήχθη με τη χρήση των φορμαλισμών της ηλεκτρικής διαπερατότητας και του ηλεκτρικού μέτρου. Από τα πειραματικά αποτελέσματα προκύπτει πως παρατηρούνται διηλεκτρικές χαλαρώσεις που οφείλονται τόσο στην πολυμερική μήτρα, όσο και στην ενισχυτική φάση. Τα φάσματα των υβριδικών συστημάτων καταγράφουν τουλάχιστον τέσσερεις διακριτούς τρόπους χαλάρωσης. Αυτά αποδίδονται στη διεπιφανειακή πόλωση (Interfacial Polarization ή φαινόμενο MWS) μήτρας/εγκλεισμάτων, στην α- χαλάρωση λόγω υαλώδους μετάβασης του πολυμερούς και στην β- και γ- χαλάρωση εξαιτίας της κίνησης πλευρικών πολικών ομάδων και τοπικής κίνησης μικρών τμημάτων της πολυμερικής αλυσίδας. Η λειτουργικότητα των νανοσύνθετων σχετίζεται με την μεταβολή της πόλωσης, που σχετίζεται ευθέως με το πραγματικό μέρος της ηλεκτρικής διαπερατότητας, την εξάρτηση της ειδικής αγωγιμότητας από την θερμοκρασία και την περιεκτικότητα σε ενισχυτικό μέσο και την δυνατότητα αποθήκευσης ενέργειας. / Nanocomposite systems, which include ferroelectric or piezoelectric particles represent a novel class of materials which are expected to exhibit functional properties because of the varying polarization of the ceramic particles. Dispersing ceramic inclusions within a polymer matrix, results in enhanced mechanical and electrical behavior. Such material systems exhibiting enhanced electrical response are used in electronic applications, for the reduction of leakage currents, as integrated nano- capacitors and as acoustic emission sensors. The electrical response of these composites, namely dielectric permittivity and conductivity can be tailored, by controlling the type, the size and the amount of ceramic inclusions. The ceramic filler could be ferroelectric and/or piezoelectric crystal particles. Their high level of polarization can be combined with a polymer host, like an epoxy resin – which is, in general, electrical insulator – with low dielectric permittivity and high dielectric breakdown strength. This combination could lead in the development of a smart materials’ system. The aims of this work are the preparation and characterization of epoxy resin nanocomposites with embedded zinc titanate (ZnTiO3) and nanoparticles and in tandem hybrid system of epoxy resin– zinc titanate (ZnTiO3) and barium titanate (BaTiO3) nanoparticles. In the first part of this work basic aspects concerning composite materials, dielectric theory, electrical behaviour and characterization techniques of polymer matrix composites are presented. In the experimental part of this study, nanocomposites were prepared by employing commercially available materials such as epoxy resin, ceramic ZnTiO3 and BaTiO3 nanopowder. The mean particle diameter, as indicated by the supplier, was less than 100nm for ZnTiO3 and 30-50nm for BaTiO3 particles. Furthermore, morphology, thermal and electrical response of the produced specimens was examined. The morphology of the specimens was checked for voids and clusters, by means of Scanning Electron Microscopy and the thermal response via Differential Scanning Calorimetry (DSC). Ceramic particles distribution is considered as satisfactory, although clusters co-exist with nanodispersions in all the examined systems. The dielectric properties and the related relaxation phenomena were studied by means of Broadband Dielectric Spectroscopy (BDS) in the temperature range from -100 oC to 160 oC and frequency range from 10-1 Hz to 10-6 Hz. Experimental data analysis was conducted by means of dielectric permittivity and electric modulus formalisms. Based on the conducted analysis, the recorded relaxation phenomena include contributions from both the polymeric matrix and the reinforcing phase. In the spectra of hybrid nanocomposites at least four relaxation processes can be detected. They were attributed to Interfacial Polarization phenomenon (MWS effect), α-mode due to glass/rubber transition of the polymer and β- , γ- modes resulting from the motion of polar side groups and local motion of small segments of the polymer chain. The functionality of the nanocomposite systems is related to the variation of polarization, which is directly connected to the real part of dielectric permittivity, the dependence of conductivity on the temperature and the filler content, and the energy storage efficiency expressed by the density of energy.