Submitted by Eliseu Antonio Cavalini null (cavaliniea1356@ig.com.br) on 2017-01-08T01:45:41Z No. of bitstreams: 1 Tese Dout V Final.pdf: 2360887 bytes, checksum: 17f60dc9305936e9dd9ea3744d049148 (MD5) / Approved for entry into archive by Juliano Benedito Ferreira (julianoferreira@reitoria.unesp.br) on 2017-01-11T13:28:41Z (GMT) No. of bitstreams: 1 cavalini_ea_dr_guara.pdf: 2360887 bytes, checksum: 17f60dc9305936e9dd9ea3744d049148 (MD5) / Made available in DSpace on 2017-01-11T13:28:41Z (GMT). No. of bitstreams: 1 cavalini_ea_dr_guara.pdf: 2360887 bytes, checksum: 17f60dc9305936e9dd9ea3744d049148 (MD5) Previous issue date: 2016-12-09 / Plasmas de gases e / ou vapores orgânicos produzem filmes finos ou pós apresentando características poliméricas, especialmente quando os plasmas são derivados de monômeros das famílias dos hidrocarbonetos alcoóis, siloxanos, silazanos, e outro. Neste trabalho, os filmes finos foram obtidos a partir da mistura de ácido cítrico-etilenoglicol-metal complexador depositado a plasma, com 13,56 MHz de radiofrequência na potência de 10 a 50 W e pressão fixada a 10 Pa. Os resultados da análise de espectroscopia de infravermelho FTIR mostrou que os grupos vibracionais dos filmes estavam preservados, mas com modificações em suas estruturas moleculares. Foram observados nos resultados obtidos por espectroscopia fotoelétrica de raios-X modificações na composição química da ligação oxigênio-carbono e oxigênio-hidrogênio com variação da potência de 10 a 50 W. A taxa de deposição dos filmes finos diminuiu de 0,10 a 0,08 nm/minuto com o aumento da potência de 10 a 50 W. As propriedades óticas das amostras como o índice de refração, coeficiente de absorção, gap ótico foram investigados por espectroscopia UV- visível. Destas análises foram possíveis obter valores n de 1,54 a 1,50 e energia do gap entre 4,75 e 4,85 eV. A técnica de ângulos de contato e foi utilizada para investigar a molhabilidade das amostras, que apresentaram caráter hidrofílico em todas as condições de deposição dos filmes. A técnica de EDS foi usada para investigar as composições químicas das amostras. Além disso, os filmes obtidos apresentaram valores de condutividade elétrica superior a 10-8 (Ωcm)-1 e constantes dielétricas entre 2,4 e 2,7. / Plasmas from gases and / or organic vapors produce thin films or powders presenting polymeric characteristics, especially when the plasmas are derived from monomers of the families of hydrocarbons, alcohols, siloxanes, silazanes, and others. In this work, thin films were obtained by citric acid / ethylene glycol / complex metal deposited by 13.56 MHz RF plasma at 10 and 50 W fixed pressure 10 Pa. FTIR spectroscopy showed that the main vibrational groups of the films were preserved, but with modifications in their molecular structures. It was observed by X –ray photoelectron spectroscopy chemical composition modifications in oxygen – carbon and oxygen – hydrogen bond while the deposition power changed from 10 to 50 W. The deposition rate of the samples decreased from 0.10 to 0.08 nm / minute while the RF power increases from 10 to 50 W. The samples optical properties as refractive index n, absorption coefficient, optical gap Eg were investigated by UV – Visible spectroscopy. From these analysis were possible to obtain values of n from 1.54 to 1.50 and Eg between 4.75 and 4.85 eV. Contact angle and surface energy measurements were used to investigate the wettability of composite Polymer films, for all depositions conditions the films presented hydrophilic character. EDS was used investigate components of the samples. Moreover, the film showed electrical conductivity values greater than 10-8(Ωcm)-1 and dielectric constant between 2.2 and 2.7.

Materiais da família ACu3Ti4O12 (ACTO) são potenciais candidatos para aplicação como dielétricos em capacitores cerâmicos devido aos seus altíssimos valores de constante dielétrica (ε\'), podendo chegar a 105 à temperatura ambiente. Entretanto, a origem deste fenômeno, denominado constante dielétrica gigante (CDG), é ainda uma questão altamente discutida na literatura. Deste modo, para compreender melhor os mecanismos por trás da manifestação desta CDG, neste trabalho os compostos ACu3Ti4O12 (com A = Ca, Bi2/3) foram sintetizados por uma rota baseada no método dos precursores poliméricos, sendo as reações envolvidas durante a síntese investigadas por análise térmica diferencial (ATD) e termogravimentria (TG). O subsequente processamento cerâmico foi realizado via sinterização tanto convencional quanto não convencional, utilizando, neste último caso, sinterização a laser e assistida por campo elétrico. As características (micro)estruturais foram avaliadas por meio de difratometria de raios X (DRX), microscopia eletrônica de varredura (MEV) e espectroscopia de energia dispersiva de raios X (EDX). Já as propriedades (di)elétricas foram estudadas, em nível microestrutural, utilizando espectroscopia de impedância (EI). Destas caracterizações, verificou-se que tanto as características (micro)estruturais quanto as propriedades (di)elétricas são fortemente influenciadas pelas condições de processamento. Neste sentido, mostramos que estes materiais podem apresentar baixos valores de permissividade à temperatura ambiente (ε\' ~ 102), típicos da resposta do volume, quando possuem grãos resistivos. Em contrapartida, quando as cerâmicas apresentam grãos semicondutores, valores de constante dielétrica gigante (ε\' >103) são verificados à temperatura ambiente devido à manifestação de efeitos de polarização interfacial. O caráter semicondutor dos grãos surge de maneira termicamente assistida. Isto ocorre porque, em maiores temperaturas, há uma migração de Cu para as regiões intergranulares das cerâmicas e também uma reação de redução do Cu2+ em Cu+. Durante o resfriamento o Cu+ reoxida, dando origem a semicondutividade dos grãos (deficientes em Cu). Como as condições empregadas na sinterização influenciaram as propriedades finais das cerâmicas, incluindo tamanho médio de grãos, decidimos inovar no processamento cerâmico ao aplicar um campo elétrico durante o tratamento térmico partindo de um pó ainda amorfo. Isto levou à observação de dois cenários: i) em altos campos, o pó sai de seu estado amorfo, passa pela cristalização de fases intermediárias, seguida de síntese ultrarrápida (flash synthesis), sem densificação; ii) em baixos campos, o pó transita do estado amorfo à fase final (passando pela cristalização das fases intermediárias), acompanhada de sinterização ultrarrápida (flash sintering), com alta densificação, tudo isso em um único experimento (FAST O3S). Finalmente, mostramos assim que utilizar um campo elétrico durante o tratamento térmico pode acelerar significativamente as taxas tanto de síntese quanto de sinterização, o que abre um novo paradigma no processamento de materiais cerâmicos. / Materials of the ACu3Ti4O12 (ACTO) family are potential candidates for application as dielectric in ceramic capacitors due to their extremely large dielectric constant (ε\'), which can reach 105 at room temperature. However, the origin of such large ε\' values, known as giant dielectric constant (GDC), is still an open debate in the literature. In order to better understand the mechanisms behind the manifestation of the GDG phenomenon, in this work, the compounds ACu3Ti4O12 (with A = Ca, Bi2/3) were synthesized by applying a modified polymeric precursor method. The reactions taking place during the powders synthesis were investigated through differential thermal analysis (DTA) and thermogravimetry (TG). The ceramic processing was then performed via conventional as well as non-conventional sintering, using, in the latter case, both laser and electric field-assisted sintering. The (micro)structural characteristics were evaluated by X-ray diffraction (DRX), scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDX). Regarding the (di)electric properties, they were examined (at the microstructural level) using impedance spectroscopy (IS). We have shown from these characterizations that both (micro)structural and (di)electric features are strongly dependent on processing conditions. In this sense, we have demonstrated that these materials might present a low permittivity at room temperature (ε\' ~ 102), typical from the bulk response, when the ceramic grains are resistive. On the other hand, when the grains are semiconducting, giant dielectric constant values (ε\' >103) are verified at room temperature due to the manifestation of interfacial polarization effects. The semiconducting nature of the grains is promoted by a thermally-assisted mechanism, i.e., at higher temperatures there is Cu migration towards the ceramic intergranular areas and also a reduction of Cu2+ to Cu+. During cooling, the Cu+ re-oxidizes yielding the grain (Cu-deficient) semiconductivity. Since the conditions employed during the sintering have influenced the final ceramic properties, including the average grain size, we propose a novel approach to the ceramic processing by applying an electric field during the heat treatment starting from an amorphous powder, which led to the following scenarios: i) powder crystallization into the intermediate phases and then instantaneously into the final phase (flash synthesis), displaying no densification, at high fields; ii) powder transition from amorphous to the final phase (through crystallization into intermediate phases), followed by sintering with high densification, at low fields: this is the fast one-step synthesis plus sintering (FAST O3S) of materials, which ends with the so-called flash sintering. Finally, we have demonstrated that both synthesis and sintering rates can be enhanced by applying an electric field during the heat treatment, opening a new paradigm for ceramic processing.

Le présent travail a pour but d'évaluer les potentialités électrocatalytiques du cuivre sous différentes formes pour les réactions de réduction du dioxyde de carbone et de réduction de l'ion nitrate.<p><p>Dans la première partie du travail, nous avons comparé, à l’aide de la voltampérométrie, d’électrolyses à potentiel contrôlé et d’analyses chromatographiques, l'activité d'électrodes polycristalline et monocristallines de Cu et d'alliages AuxCuy de différentes orientations cristallines pour l'électroréduction de CO2.<p>Nous avons pu établir une étroite corrélation entre l'activité de l'électrode de Cu et l'arrangement atomique de sa surface. L'activité et la sélectivité pour CH4 de Cu décroissent selon la séquence :Cu (111) > Cu (100) > Cu (poly). La réduction du CO2 et la formation de CH4 sont favorisées sur les surfaces lisses et denses à l'échelle atomique.<p>La sélectivité des alliages AuxCuy est considérablement orientée vers CO quand la fraction superficielle de Au augmente. L'alliage de composition 50-50 conduit à la formation exclusive de CO.<p><p>La seconde partie de la thèse est consacrée à l'étude de l'activité d'électrodes massives de Cu polycristallin et monocristallin d’orientation (111) et de dispersions de Cu pour la réduction électrochimique de NO3-. <p>Nous avons mis en évidence l'importance des conditions de pH pour le déroulement des processus à l'électrode de cuivre. En milieu acide, NO3- est directement réduit en NH4+ alors qu’en milieu neutre, les réactions de réduction de NO3- en NO2- et de NO2- en NH4+ s’observent successivement en fonction du potentiel.<p>L'activité des dispersions de Cu dans un film de polyaniline dépend fortement des conditions de dépôt. Le cuivre incorporé au film sous sa forme réduite est plus actif que le cuivre incorporé au film initialement oxydé. Par ailleurs, nous avons montré que la concentration de H+ dans le polymère est limitée. En conséquence, le processus de réduction de NO3- sur le cuivre dispersé dans un film de polyaniline est modifié en milieu acide.<p>L’utilisation d’un film de poly-3,4-éthylènedioxythiophène déposé sur une surface de Pt s'est quant à elle révélée inadéquate comme support pour l'incorporation de Cu dans le cadre de l'étude de la réduction de NO3- en milieu acide.<p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

Die Magnetometerprospektion gilt mittlerweile als ein Standardverfahren der archäologischen Prospektion. Nicht selten jedoch werden Messergebnisse (Magnetogramme) dieser schnellen und oft ertragreichen Prospektionsmethode ohne eine notwendige Überprüfung im Labor interpretiert, was zu falschen Bewertungen der Magnetfeldanomalien in archäologischen und geoarchäologischen Kontexten führen kann. Die vorliegende Arbeit versucht diesem Problem entgegen zu treten und widmet sich dem Ziel Interpretationen von Magnetometermessungen zu verbessern und Verfahren weiter zu entwickeln, die zur schnellen und hinreichenden Klärung von Magnetfeldanomalien angewandt werden können. Hierfür werden in mehreren Untersuchungsgebieten magnetometrische und umweltmagnetische Messungen in Kombination mit bodenkundlich-sedimentologischen Kennwerten, ausgewertet. Als Untersuchungsgebiete und Umweltarchive stehen die braunen Plaggenesche am Übergang zwischen dem Unteren Weserbergland und der Dümmer-Geestniederung sowie die semiterrestrischen Sedimente des Karlsgrabens (Fossa Carolina) am Übergang zwischen dem fränkischen Keuper-Lias-Land und der fränkischen Alb im Fokus. Magnetometrisch prospektiert wird mit einem, sehr oft bei archäologischen Prospektionen eingesetzten, Vektor-Gradiometer (Bartington Grad601 dual). Als geophysikalische Leitgröße zur Identifizierung und ersten Charakterisierung magnetisch-auffälliger und Magnetfeldanomalien-erzeugender Bodenhorizonte und Sedimentschichten in betrachteten Umweltarchiven wird die magnetische Suszeptibilität herangezogen. Anhand der Curie-Temperatur-Messungen und Domänenstatusermittlungen werden die umweltmagnetischen Minerale und deren Korngrößen in magnetisch auffälligen Lagen und Horizonten charakterisiert. Ergebnisse aus der Kombination umweltmagnetischer Messungen mit Bodenkennwerten an brauen Plaggeneschen weisen darauf hin, dass die in den Plaggenauflagen detektierten, ferrimagnetischen Eisensulfide PSD-Greigite anthropogen induziert sein müssen. Außerdem deutet sich an, dass diese Greigite vom Sicker- und Grundwasser verändert und gegebenenfalls mobilisiert werden können. Ein Vergleich mit Greigiten aus der Literatur zeigt, dass die Plaggenesch-PSD-Greigite in einem Domänenstatus vorliegen, in dem bislang noch keine natürlichen Greigite gemessen wurden. Dieser Domänenstatus wird als ein Oxidationsstadium des ferrimagnetischen Eisensulfids zur Diskussion gestellt. In den Grabenverfüllungen bzw. Paläokanälen des Karlsgrabens wurden in Magnetfeldanomalien-erzeugenden Lagen authigene SD-Greigite nachgewiesen und damit die Annahme von Stanjek et al. (1994) bestätigt, dass die Greigite für die Magnetometerprospektion in semiterrestrischen Umgebungen von Bedeutung sein können. In flankierende Begleitstrukturen des Karlsgrabens wurden hingegen hocherhitzte, thermoremanente PSD-Titanomagnetite als Magnetfeldanomalien-Erzeuger ermittelt. Ihre Entstehung bleibt ungeklärt, jedoch wird eine natürliche Bildung dieser Magnetominerale vor Ort ausgeschlossen. Im Hinblick auf das Ziel der vorliegenden Arbeit hat sich die methodische Vorgehensweise am Karlsgraben als besonders effiziente und relativ kostengünstige Methode zur abgesicherten Klärung von Magnetfeldanomalien in den Magnetogrammen gezeigt.

Indiana University-Purdue University Indianapolis (IUPUI) / The prevalent applications of energy storage devices have incited wide-spread efforts on production of thin, flexible, and light-weight lithium-ion batteries. In this work, lithium-ion batteries using novel flexible paper-based current collectors have been developed. The paper-based current collectors were fabricated from carbon nanotube (CNT)-coated wood microfibers (CNT-microfiber paper). This thesis presents the fabrication of the CNT-microfiber paper using wood microfibers, coating electrode materials, design and assemblies of battery, testing methodologies, and experimental results and analyses. Wood microfibers were coated with carbon nanotubes and poly(3,4-ethylenedioxythiophene) (PEDOT) through an electrostatic layer-by-layer nanoassembely process and formed into a sheet, CNT-microfiber paper. The CNT loading of the fabricated paper was measured 10.1 μg/cm2 subsequently considered. Electrode material solutions were spray-coated on the CNT-microfiber paper to produce electrodes for the half and full-cell devices. The CNT current collector consists of a network structure of cellulose microfibers at the micro-scale, with micro-pores filled with the applied conductive electrode materials reducing the overall internal resistance for the cell. A bending test revealed that the paper-based electrodes, compared to metal ones, incurred fewer damages after 20 bends at an angle of 300o. The surface fractures on the paper-based electrodes were shallow and contained than metallic-based electrodes. The micro-pores in CNT-microfiber paper structure provides better adherence to the active material layer to the substrate and inhibits detachment while bending. Half-cells and full-cells using lithium cobalt oxide (LCO), lithium titanium oxide (LTO), and lithium magnesium oxide (LMO) were fabricated and tested. Coin cell assembly and liquid electrolyte was used. The capacities of half-cells were measured 150 mAh/g with LCO, 158 mAh/g with LTO, and 130 mAh/g with LMO. The capacity of the LTO/LCO full-cell also was measured 126 mAh/g at C/5 rate. The columbic efficiency of the LTO/LCO full-cell was measured 84% for the first charging cycle that increased to 96% after second cycle. The self-discharge test of the full-cell after charging to 2.7 V at C/5 current rate is showed a stable 2 V after 90 hours. The capacities of the developed batteries at lower currents are comparable to the metallic electrode-based devices, however, the capacities were observed to drop at higher currents. This makes the developed paper-based batteries more suitable for low current applications, such as, RFID tags, flexible electronics, bioassays, and displays. The capacities of the batteries at higher current can be improved by enhancing the conductivity of the fibers, which is identified as the future work. Furthermore, fabrication of an all solid state battery using solid electrolyte is also identified as the future work of this project.

Indiana University-Purdue University Indianapolis (IUPUI) / Due to the drastic increase in the cost of fossil fuels and other environmental issues, the demand for energy and its storage has risen globally. Rather than being dependent on intermittent energy sources like wind and solar energy, focus has been on alternative energy sources. To eliminate the need for fossil fuels, advances are being made to provide energy for hybrid electric vehicles (HEV), plug-in hybrid vehicles (PHEV) and pure electric vehicles (EV) thus providing scope for much greener environment. Hence, focus has been on development in lithium ion batteries to provide with materials that have high energy density and voltage. Ortho olivine lithium transitional metals are known to be abundant and inexpensive; these compounds are less noxious than other cathode materials. Advancement in research is being done in finding iron and manganese compounds as cathode materials for advanced technologies. However, Lithium manganese phosphates are known to suffer with poor electrochemical performances due the manganese dissolution in the organic liquid electrolyte due to Jahn-Teller Lattice distortion. This problem was tried to endorse in this thesis. In the second chapter by synthesizing nano sized cathode particles with good electronic conductivity, good performance was achieved. In the third chapter additive olivine cathode was synthesized my modified sol gel process. A wt. % of TMSP was added as an additive in the organic liquid electrolyte. By comparing the properties between the two kinds of electrolytes it was observed that by the addition of the additive in the organic electrolyte good electrochemical properties could be achieved hindering the Mn dissolution in the electrolyte. In the final chapter, a composite solid electrolyte was fabricated by using NASICON-type glass ceramic of Lithium aluminum titanium phosphate (LATP) with organic binder of Polyethylene oxide. The flexible solid electrolyte exhibited good ionic conductivity. An all solid state cell was fabricated using the composite solid electrolyte using LiMn2O4 as the symmetric electrodes. At different pressures, the performance of the solid state cell was studied.

Ferroelectric materials are very promising for a variety of applications such as high-permittivity capacitors, ferroelectric memories, pyroelctric sensors, piezoelectric and electrostrictive transducers and electro-optic devices, etc. In the area of ferroelectric ceramics, lead-based compounds, which include lead zirconatetitanate (PZT) solid solutions, occupy an important place because of their superior physical properties. However, due to the toxicity of lead, there is an increasing concern over recycling and disposing of the devices made out of these compounds, which has compelled the researchers around the globe to search for lead-free compounds with promising piezo and ferroelectric properties. Ferroelectric materials that belong to Aurivillius family of oxides have become increasingly important from the perspective of industrial applications because of their high Curie-temperatures, high resistivity, superior polarization fatigue resistanceand stable piezoelectric properties at high temperatures. These bismuth layer-structured ferroelectrics (BLSF) comprise an intergrowth of [Bi2O2]2+ layers and [An+1Bn O3n+1]2- pseudo-perovskite units, where ‘n’ represents the number of perovskite-like layers stacked along the c-axis. ‘A’ stands for a mono-, di- or trivalent ions or a combination of them, ‘B’ represents a small ion with high valencysuch as Ti4+, Nb5+, Ta5+or a combination of them.Ferroelectricity in the orthorhombic phase of these compounds was generally attributed to the cationic displacement along the polar a-axis and the tilting of octahedra around the a- and c-axes. Sr2Bi4Ti5O18(SBT) is ann = 5 member of the Aurivillius family and possess promising ferroelectric and piezoelectric properties that could be exploited for a wide range of applications, including ferroelectric random access memories (FeRAM), piezoelectric actuators, transducers and transformers. Reports in the literaturereveal that the ferroelectricand piezoelectric properties of these oxides can be tuned depending on synthesis routes vis-a-vis micro-structural aspects (texture, grain size) and site specific dopant substitutions.In the present study, textured SBT ceramics were fabricated using pre-reacted precursors and their anisotropic dielectric, piezoelectric and ferroelectric properties were demonstrated. Grain size tunability with regard to their physical properties was accomplished in the ceramics, fabricated using fine powders obtained from citrate assisted sol-gel synthesis. The grain size dependent second harmonic generation activity of SBT ceramics was investigated. Enhancement in the piezoelectric and ferroelectric properties of SBT ceramics was achieved by substituting A site ions (Sr2+) with a combination of Na+ and Bi3+. From the perspective of non-linear optical device applications, physical properties associated with the SBT crystallized in a transparent lithium borate glass matrix were studied. The results obtained in the present investigations are organized as follows, Chapter 1 gives a brief exposure to the field of ferroelectrics. The emphasis has been on the ferroelectric oxides belonging to the Aurivillius family. Structural aspects and the underlying phenomena associated with ferroelectricity in these compounds are discussed. A brief introduction to the glasses, thermodynamic aspects of glass formation and fabrication of glass- ceramics are included. Basic principles involved in the non-linear optical activities are highlighted. Chapter 2 describes the various experimental techniques that were employed to synthesize and characterize the materials under investigation. The experimental details pertaining to the measurement of various physical properties are included. Chapter 3 deals with the fabrication of Sr2Bi4Ti5O18 ceramics using the pre-reacted Bi4Ti3O12 and SrTiO3 powders viasolid-state reaction route. These in stoichiometric ratio were uniaxially pressed and sintered at 1130oC for 3 h resulting in textured Sr2Bi4Ti5O18 ceramics. The obtained dense ceramics exhibited crystallographic anisotropy with prominent c-axis oriented grains (Lotgering factor of 0.62) parallel to the uniaxially pressed direction. The resultant anisotropy in the ceramics was attributed to the reactive template-like behavior of Bi4Ti3O12 that was used as a precursor to fabricate Sr2Bi4Ti5O18 ceramics. Dielectric, ferro and piezoelectric properties measured on the ceramics in the direction perpendicular to the uniaxially pressed axis were found to be superior to that measured in the parallel direction. Chapter 4 reports the details pertaining to the synthesis of strontium bismuth titanate (Sr2Bi4Ti5O18) powders comprising crystallites of average sizes in the range of 94–1400 nm via citrate-assisted sol-gel route. X-ray powder diffraction, Transmission Electron Microscopy (TEM) and Raman spectroscopy were employed for the structural studies. A crystallite size-dependent variation in the lattice parameters and the shift in the Raman vibration modes were observed. Second harmonic signal (532 nm) intensity of the Sr2Bi4Ti5O18 powders increased with the increase in the average crystallite size and the maximum intensity obtained in the reflection mode was 1.4 times as high as that of the powdered KH2PO4. Piezo force microscopic analyses carried out on an isolated crystallite of size 74 nm, established its single domain nature with the coercive field as high as 347 kV/cm. There was a systematic increase in the d33 value with an increase in the size of the crystallite and a high piezoelectric coefficient of ~27 pm/V was obtained from an isolated crystallite of size 480 nm. Chapter 5 illustrates the details concerning the fabrication of Sr2Bi4Ti5O18(SBT) ceramics with different grain sizes (93 nm–1.42 μm) using nano-crystalline powders synthesized via citrate assisted sol-gel method. The grain growth in these powder compacts was found to be controlled via the grain boundary curvature mechanism, associated with anactivation energy of 181.9 kJ/mol. Interestingly with a decrease in grain size there was an increase in the structural distortion which resulted in a shift of Curie-temperature (phase transition) towards higher temperatures than that of conventional bulk ceramics. Extended Landau phenomenological theory for the ferroelectric particles was invoked to explain experimentally observed size dependent phase transition temperature and the critical size for SBT is predicted to be 11.3 nm. Grain size dependent dielectric, ferroelectric and piezoelectric properties of the SBT ceramics were studied and the samples comprising average grain size of 645 nm exhibited superior physical properties that include remnant polarization (2Pr) = 16.4 μC cm-2, coercive field (Ec) = 38 kV cm-1, piezoelectric coefficient (d33) = 22 pC N-1 and planar electromechanical coupling coefficient (kp) = 14.8 %. In Chapter 6, the studies pertaining to the fabrication of Sr(2-x)(Na0.5Bi0.5)xBi4Ti5O18 (SNBT) ceramics for various x values (0, 0.1, 0.25, 0.3, 0.4 and 0.5), using fine powders synthesized via sol-gel route are dealt with. X-ray powder diffraction, transmission electron microscopy and Raman spectroscopic studies were carried out to confirm composition dependent structural changes taking place in the SNBT ceramics. Scanning electron microscopic studies carried out on ceramics revealed that dopants played an important role in inhibiting the grain growth. Dielectric constants of the ceramics were found to decrease with an increase in ‘x’. The increase in Curie temperature with increase in ‘x’ is attributed to the decrease in the tolerance factor. Particularly,x = 0.3 composition of the SNBT ceramics exhibited better piezo and ferroelectric properties with a higher Curie-temperature (569 K). The piezoelectric coefficient (d33) and the planar electromechanical coupling coefficient (kp) of SNBT(x = 0.3) were enhanced by 25% and 42% respectively as compared to that of the undoped ceramics. Chapter 7 deals with the glasses in the system (100 –x) {Li2O + 2B2O3} ─x {2SrO + 2Bi2O3 +5TiO2} (where, x = 10, 25 and 35) fabricated via conventional melt-quenching technique. The amorphous and glassy characteristics of the samples were confirmed respectively using X-ray diffraction (XRD) and differential scanning calorimetric (DSC) methods. All the compositions under investigation exhibited two distinct crystallization peaks (exothermic peaks in the DSC traces): the first peak at ~ 545 °C and the second at ~610 °C that were found to be associated with the crystallization of the phases (as confirmed from the XRD studies) Sr2Bi4Ti5O18 (SBT)and Li2B4O7 (LBO) respectively. Non-isothermal crystallization kinetics (using modified Ozawa-type plots) for SBT crystallization in the LBO glass matrix for the compositions x = 10 and 35, indicated three dimensional growth of the crystallites from pre-existing nuclei present in the as-quenched samples and their effective activation energies for crystallization were found to be around 686 ± 85 kJ/mol and 365 ± 53 kJ/mol, respectively. The optical band gap of the as-quenched glasses for the composition x = 35 was 2.52 eV, is less than that of the composition x = 10 (2.91 eV). The Urbach energies for the as-quenched glasses of compositions x = 10, 25 and 35 were found to be 118 ± 2 meV, 119 ± 2 meV and 192 ± 1 meV respectively.The glasses associated with the composition x = 35, on controlled heat-treatment at 515 °C for various durations (1―20 h), yielded glass-ceramics comprising SBT nano-crystals (18―28 nm) embedded in the LBO glass matrix. Compressive strain in the nano-crystallites of SBT, analyzed using Williamson-Hall method was found to decrease with an increase in the crystallite size. The second harmonic generation signal (532 nm) intensity emanating from glass-nanocrystal composites comprising 22.1 nm SBT crystallites was nearly 0.3 times that of a KDP single crystal. Although each chapter is provided with conclusions and a list of references, thesis ends with a separate summary and conclusions.

Indiana University-Purdue University Indianapolis (IUPUI) / Fabrication and analysis of Copper Indium Gallium di-Selenide (CIGS) nanoparticles-based thin film solar cells are presented and discussed. This work explores non-traditional fabrication processes, such as spray-coating for the low-cost and highly-scalable production of CIGS-based solar cells. CIGS nanoparticles were synthesized and analyzed, thin CIGS films were spray-deposited using nanoparticle inks, and resulting films were used in low-cost fabrication of a set of CIGS solar cell devices. This synthesis method utilizes a chemical colloidal process resulting in the formation of nanoparticles with tunable band gap and size. Based on theoretical and experimental studies, 100 nm nanoparticles with an associated band gap of 1.33 eV were selected to achieve the desired film characteristics and device performances. Scanning electron microcopy (SEM) and size measurement instruments (Zetasizer) were used to study the size and shape of the nanoparticles. Electron dispersive spectroscopy (EDS) results confirmed the presence of the four elements, Copper (Cu), Indium (In), Gallium (Ga), and Selenium (Se) in the synthesized nanoparticles, while X-ray diffraction (XRD) results confirmed the tetragonal chalcopyrite crystal structure. The ultraviolet-visible-near infra-red (UV-Vis-NIR) spectrophotometry results of the nanoparticles depicted light absorbance characteristics with good overlap against the solar irradiance spectrum. The depositions of the nanoparticles were performed using spray-coating techniques. Nanoparticle ink dispersed in ethanol was sprayed using a simple airbrush tool. The thicknesses of the deposited films were controlled through variations in the deposition steps, substrate to spray-nozzle distance, size of the nozzle, and air pressure. Surface features and topology of the spray-deposited films were analyzed using atomic force microscopy (AFM). The deposited films were observed to be relatively uniform with a minimum thickness of 400 nm. Post-annealing of the films at various temperatures was studied for the photoelectric performance of the deposited films. Current density and voltage (J/V) characteristics were measured under light illumination after annealing at different temperatures. It was observed that the highest photoelectric effect resulted in annealing temperatures of 150-250 degree centigrade under air atmosphere. The developed CIGS films were implemented in solar cell devices that included Cadmium Sulfide (CdS) and Zinc Oxide (ZnO) layers. The CdS film served as the n-type layer to form a pn junction with the p-type CIGS layer. In a typical device, a 300 nm CdS layer was deposited through chemical bath deposition on a 1 $mu$m thick CIGS film. A thin layer of intrinsic ZnO was spray coated on the CdS film to prevent shorting with the top conductor layer, 1.5 μm spray-deposited aluminum doped ZnO layer. A set of fabricated devices were tested using a Keithley semiconductor characterization instrument and micromanipulator probe station. The highest measured device efficiency was 1.49%. The considered solar cell devices were simulated in ADEPT 2.0 solar cell simulator based on the given fabrication and experimental parameters. The simulation module developed was successfully calibrated with the experimental results. This module can be used for future development of the given work.