Of the emerging photovoltaic technologies, perovskite solar cells (PSCs) are arguably among the most promising candidates for commercialization. Worldwide interest has prompted researchers to produce tens of thousands of studies on the topic, making PSCs one of the most active research topics of the past decade. Unfortunately, the rapid output of a substantial number of publications has made the traditional literature review process and research plans cumbersome tasks for both the novice and expert. In this dissertation, a data-driven analysis utilizing a novel text mining and natural language processing pipeline is applied on the perovskite literature to help decipher the field, uncover emerging research trends, and delineate an experimental research plan of action for this dissertation. The analysis led to the selection and exploration of two experimental projects on single-crystal PSCs, which are devices based on micrometers-thick grain-boundary-free monocrystalline films with long charge carrier diffusion lengths and enhanced light absorption (relative to polycrystalline films). First, a low-temperature crystallization approach is devised to improve the quality of methylammonium lead iodide (MAPbI3) single-crystal films, leading to devices with markedly enhanced open-circuit voltages (1.15 V vs 1.08 V for controls) and power conversion efficiencies (PCEs) of up to 21.9%, among the highest reported for MAPbI3-based devices. Second, mixed-cation formamidinium (FA)-based single-crystal PSCs are successfully fabricated with PCEs of up to 22.8% and short-circuit current values exceeding 26 mA cm-2, achieved by a significant expansion of the external quantum efficiency band edge, which extends past that of the state-of-the-art polycrystalline FAPbI3-based solar cells by about 50 meV — only 60 meV larger than that of the top-performing photovoltaic material, GaAs. These figures of merit not only set new record values for SC-PSCs, but also showcase the potential of adopting data-driven techniques to guide the research process of a data-rich field.

The work presented in this thesis is divided into two research areas. In part I, the synthesis and guest intercalation of inorganic-organic metal halide ammonium layered perovskites is discussed. Comparisons are made between the solid matrix before and after the intercalations, and all solids are characterized using thermogravimetric analysis (TGA) and powder X-ray diffraction (XRD). In part II, “templateree” hydrothermal synthesis of tin oxide spheres in the presence of different ortho-substituted anilines is discussed. The aim is to determine whether there are differences in the structures, shapes and surface morphology of the tin oxide spheres that correspond to the identity/shape of the ortho-substituent on the anilines. Solids were characterized by XRD, transmission electron microscopy (TEM) and scanning electron microscopy (SEM) techniques.

No description available.

No description available.

No description available.

The physics of doped transition metal perovskite has been an area of intense research in the last few decades due to their interesting magnetic and transport properties. Various exciting phenomena such as, colossal magneto resistance, high Tc superconductivity, multiferroicity, ferroelectricity, high temperature ferromagnetism, etc., have made these systems more fascinating in terms of fundamental study as well as technological applications. There are several intrinsic material characteristics in these perovskite oxides that can impact their magnetic properties. Lattice distortion and chemical in homogeneity are two important ones. Changes in valence and ionic radius in rare earth (A- site) and transition metal (B- site) directly result in structural modification through internal pressure. Consequently, atomic distances and bond angles between the transition metals vary. This, intern, influences the nearest neighbour exchange coupling energy and magnetic interaction. A detailed investigation has been carried out on two A-site doped perovskite namely, La0.85Sr0.15CoO3 & La0.5Sr0.5CoO3 and two B-site doped perovskite, LaMn0.5Co0.5O3 & LuMn0.5Ni0.5O3 with a view to study the impact of chemical in homogeneity and lattice distortion on their respective magnetic ground states. The thesis is organized in seven chapters. A brief summary of each is given below: Chapter 1: Provides a brief introduction about the perovskite structure. Origins of lattice distortions and its effect on the magnetic properties are discussed. It includes a discussion on different types of indirect magnetic interactions involved in perovskite oxide structure. The chapter concludes with a description of spin-glass, phase separation/ cluster-glass, memory effect in glassy magnetism, critical behaviour at phase transition and specific heat in magnetic systems. Chapter 2: This chapter outlines basic principles of the experimental techniques employed for the work presented in this thesis. Chapter 3: Details macroscopic as well as microscopic investigations carried out to understand the glassy magnetic anomalies in La0.85Sr0.15CoO3 samples. The origin of phase separation (PS) has been reinvestigated. Since the magnetic behavior of La0.85Sr0.15CoO3 (LSCO15) lies in the border of spin glass (SG) and ferromagnetic (FM) region in the x-T phase diagram, it is subject to controversial debate for the last several years. While some research groups favour PS, others regard SG behaviour as the dominant phenomenon. In-depth investigation carried out to elucidate these views is outlined in this chapter in two sections. The first section deals with the glassy magnetic anomalies in single crystals of LSCO15 grown by optical floating zone method. Since the sample crystallizes from melt, it possesses good compositional homogeneity and the phase purity is confirmed by XRD pattern. Many characteristics of canonical SG systems are discernible in the magnetic study, such as, kink in field-cooling curve below Tf, frequency-dependent peak shift and the time dependent memory effect. The relaxation time in sub-pico second range (~10-13 s) is very similar to that of the typical SG systems. Time dependent transport relaxation study exhibits memory effect and the time evolution of resistance scales with magnetization and strictly adheres to the stretched exponential behaviour as commonly expected for a SG-like disordered system. However, a detailed study on transport mechanism and temperature-dependent inverse susceptibility reveals the existence of nanoscopic PS in the sample. In the second section, the origin of PS has been examined through a comprehensive study on two sets of LSCO15 polycrystalline samples prepared from the same initial mixture but subjected to different heat treatment processes. This study depicts the dependence of PS on the preparation conditions. The contrasting magnetic behaviour of PS and SG was resolved by experiments of dc magnetization, linear & non-linear ac susceptibility, neutron depolarization and field-cooled magnetic relaxation. Both samples conform to the general characteristics of a glassy behaviour: a kink in FC magnetization, frequency-dependent peak shift (Vogel–Fulcher law), dc bias-dependent peak shift in accordance with de Almeida–Thouless relation, and characteristic relaxation time in the range of 10-13/10-14 s. This is despite their internal spin structure and interaction being much different at a microscopic level. It is found that the sample processed through a proper homogenization process mimics the SG behaviour, whereas the sample prepared by the conventional method behaves like the PS phase. It is confirmed from neutron depolarization experiments that no ferromagnetic correlation exists in the SG phase of La0.85Sr0.15CoO3, a result in contrast to that of PS phase. Higher harmonic ac susceptibility measurement complements the above observation by the evidence that of 2nd order harmonics are not present in the SG phase of La0.85Sr0.15CoO3. The field-cooled magnetic relaxation study makes a distinct reference to the relaxation process and the strength of interaction between PS and SG like phases. In essence, a concerted effect is made to identify and resolve the spin-glass phase from phase-separated/ cluster-glass. This work shows that chemical in homogeneity is a key factor responsible for phase separation in La0.85Sr0.15CoO3; also intrinsic differences between PS and SG are identified that can serve as guiding tools for research in other similar magnetic oxide systems. It is concluded that the true ground state magnetic property of La0.85Sr0.15CoO3 is spin-glass in nature. Chapter 4: This chapter contains two sections. In the first part, the origin of the re-entrant spin-glass (RSG) behaviour in La0.5Sr0.5CoO3 has been investigated using the conventional magnetometer measurements. Polycrystalline samples prepared by the conventional solid-state synthesis exhibit RSG characteristics with a glassy transition at 190 K. The nature of frequency dependence of χ″(T), a pronounced memory effect and the sluggish response in dc magnetization measurement, all of which clearly indicate the re-entrant behaviour. But, once the sample is taken through a rigorous homogenization procedure of repeated grinding and annealing, its phase turns into pure ferromagnetic one. During the course of this homogenization process, the sample loses oxygen with concurrent degeneration of TC to a lower level. In order to regain the oxygen stoichiometry, it is necessary to anneal the sample in oxygen environment at 900 oC, which triggers deleterious ageing effect by which TC falls progressively with time. In the second part, the effect of oxygen stoichiometry on La0.5Sr0.5CoO3 (LSCO50) thin-films has been investigated. The highest TC reported so far for LSCO50 thin film is 250 K, which is significantly less compared to the bulk TC (262 K) of an oxygen stoichiometric compound. This work focuses on achieving the highest ferromagnetic transition temperature (TC) for LSCO50 films under optimized growth conditions. The analysis of experimental data suggests that the Curie temperature can be enhanced to 262 K, irrespective of whether or not, (a) the film on LAO or STO or (b) any induced strain occurs in the LSCO50 film. Apart from different thin-film growth parameters such as oxygen pressure and substrate temperature during the growth, and post-growth annealing temperature and oxygen pressure, the profile of the laser beam used for ablation of bulk material profile also plays an important role. The elevation of Curie temperature observed in thin-films to that close to the bulk value is believed to be a result of improved stoichiometric composition of oxygen facilitated during thin film growth. However, the strong ageing effect seen is quite close to that is observed in oxygen-annealed polycrystalline sample. Chapter 5: Of the three segments constituting this chapter, the first outlines different magnetic anomalies induced by lattice distortion in LaMn0.5Co0.5O3 (LMCO) single crystals. Single crystals of LMCO compound [(100) orientation] have been successfully grown using the optical floating zone method. Powder as well as single crystal x-ray diffraction analyses provides evidence of large strain dependent structural distortion in as-grown crystals. Spatially resolved 2-D Raman scan reveals that the strain generates a distribution of octahedral distortion in the lattice. While some are compressive in nature, others in the nearby territory relate to tensile distortion. The ac susceptibility measurement elucidates distinct changes in the ferromagnetic transition temperature (TC) in the as grown (strained) crystal. It is possible to release strain by rigorous annealing process. Which also results in a uniform TM-O octahedral deformation. Room temperature 2-D Raman spectra bears testimony to this. Upon annealing, the single crystalline order is diminuend by the atomic rearrangement. This causes tilting of the oxygen octahedra, by decreasing intra-octahedral angle θTM-O-TM, and lowering of exchange energy Jex between the magnetic ions. The transition temperature falls and the magnetic phase merges with that in the strain-free polycrystalline material. A detailed critical analysis performed in the vicinity of paramagnetic to ferromagnetic phase transition in both the samples establishes that the ground state magnetic behaviour, assigned to the strain-free LMCO crystal is of 3D Heisenberg type. But the local octahedral distortion present in the as-grown crystal causes mean field like magnetic interaction at few local sites. This serves as a key drive for the critical exponents to distance from the 3D Heisenberg model towards the mean-field type. The second part of this chapter concerns the anomalous re-entrant glassy magnetic behaviour observed in LMCO single crystals. The ac susceptibility study illustrates the low temperature anomalous glassy magnetic ordering in these crystals. The material behaves like a normal magnetic glass, (frequency-dependent peak-shift in ac susceptibility) in conformance with the phenomenological Vogel-Fulcher law, of spin flips time: ~10-4 s. However, the crystal does not respond to the external dc bias and just as well remains free from memory effect. Anomalous behaviour of this kind is rare in magnetic oxides. The magneto-dielectric effect in LMCO is discussed in the third section of this chapter. The real part of dielectric permittivity (ε′) has a colossal value of 1800 at 220 K and 10 kHz. However as the sample is cooled further, ε′ decreases slowly; followed by dielectric relaxation in the region, 120 - 150 K. Detailed analysis of the temperature dependence of the imaginary part of the dielectric permittivity (ε″) show that there is no relaxor-like phenomena in this compound. The frequency dependence of ε″ reveals that the low frequency region is dominated by Maxwell-Wagner relaxation, whereas, at high frequency, a Debye type relaxation persists. The temperature dependent full-width at half-maximum for this Debye relaxation, peaks at the corresponding TC. The temperature variation of the relaxation time has two domains of different slopes. At zero external field, ε″(ω) has a low activation energy (U = 46.4 meV) in the ferromagnetic region, compared to that in the paramagnetic (60.1 meV) phase. The boundary lies near the corresponding TC. In the presence of external applied field 5 T, U remains unchanged in the ferromagnetic region, but decreases ( U ~ 5 meV) in the paramagnetic phase. These results signify the existence of strong magneto-dielectric coupling in LMCO crystals. The field variation of ε′(ω) at fixed temperature and specific frequency highlights the rise in magnetodielectricity (MD) as well as magneto-loss (ML) with increasing magnetic field. It is perceived that this variation is not due to the magneto resistance of LMCO or caused by LMCO - electrode interfaces. The influence of extrinsic parasitic contributions cannot be ruled out entirely, but the presence of positive MD as well as ML at frequencies above the time constant suggests that the relaxation process and the magneto-dielectric coupling are intrinsic to the LaMn0.5Co0.5O3 system. Chapter 6: This chapter describes the successful synthesis of a new perovskite oxide compound, LuMn0.5Ni0.5O3. The structural characterization employs the Rietveld refinement of powder X-ray diffraction pattern. The compound crystallizes in orthorhombic Pbnm crystal structure. dc magnetization reveals ferromagnetic ordering in the sample. However the low temperature glassy phase spotted in the ac susceptibility measurement might classify it as a re-entrant spin-glass compound. But the display of memory effect until the ferromagnetic transition indicates that intrinsic ant ferromagnetic interaction prevails over the dominant ferromagnetic interaction. A critical behaviour study was carried out in the vicinity of the ferromagnetic to paramagnetic phase transition, which provided the critical exponents: α = 0.37, β = 0.241 ± 0.003, γ = 1.142 ± 0.003 and δ = 5.77 ± 0.03. Interestingly, this set of critical exponents does not match with any of the conventional theories of mean field, 3D Heisenberg, and 3D Ising. Rather it fits quite well with data calculated for the stacked triangular 3D version of the (Z2 × S1) model [α = 0.34 ± 0.06, β = 0.25 ± 0.01, γ = 1.13 ± 0.05 and δ = 5.47 ± 0.27]. This study indicates that the magnetic ground state of LuMn0.5Ni0.5O3 is canted ferromagnetic. Chapter 7: Various important results are summarized in this chapter. It also provides a broad outlook in this area of research.

This thesis details the development of a novel photovoltaic device based on organometal halide perovskites. The initial focus of this thesis begins with the study of lighttrapping strategies in solid-state dye-sensitised solar cells (detailed in chapter 3). While I report enhancement in device performance through the application of near and far-field light-trapping techniques, I find that improvements remain step-wise due to fundamental limitations currently employed in dye-sensitised solar cell technology— notably, the available light-sensitising materials. I found a promising yet under researched family of materials in the methyl ammonium tri-halide plumbate perovskite (detailed in chapter 4). The perovskite light-sensitiser was applied to the traditional mesoscopic sensitised solar cell device architecture as a replacement to conventional dye yielding world-record breaking photo-conversion e!ciencies for solid-state sensitised solar cells as high as 8.5%. The system was further developed leading to the conception of a novel device architecture, termed the mesoporous superstructured solar cell (MSSC), this new architecture replaces the conventional mesoporous titanium dioxide semiconductor with a porous insulating oxide in aluminium oxide, resulting in very low fundamental losses evidenced through high photo-generated open-circuit voltages of over 1.1 V. This development has delivered striking photo-conversion ef- ficiencies of 10.9% (detailed in chapter 6).

Dans ce travail, nous avons étudié la croissance de films d’oxydes Bi2FeCrO6 (BFCO) en utilisant les techniques de sol-gel et dépôt par laser pulsé (PLD). Dans le cas de la voie chimique, des précurseurs en solution ont été préparés, puis déposés par centrifugation sur des substrats de silicium (100) ou de quartz. Les nombreuses analyses structurelles (DRX) et d'imagerie (SEM, TEM) effectuées sur ces films BFCO ont montré que les films sont assez homogènes mais présentent de nombreuses phases parasites qui peuvent être éliminés partiellement par recuit thermique rapide. Des dispositifs tests à base de films BFCO par sol-gel ont été préparés et qui ont montré des propriétés électriques limitées à cause des nombreux défauts. Des films BFCO ont également été produits par la technique PLD sur des substrats STO et NbSTO. Les propriétés structurelles, optiques et électriques sont présentées. La diffusion épitaxiale de haute qualité et les films en phase pure sont démontrés par diffraction des rayons X. Nous avons étudié l'évolution de paramètres tels que la bande interdite en fonction des conditions de croissance, montrant qu'elle peut être ajustée de 1, 9 à 2,6 eV. Ce comportement a été corroboré par des calculs théoriques sur l’arrangement atomique dans la structure BFCO. Les propriétés ferroélectriques sont étudiées par microscopie à force piézoélectrique. La lumière s'est avérée avoir un effet sur la polarisation. Il a également été démontré que la mémoire de la polarisation affecte la réponse photovoltaïque. Enfin, des dispositifs basés sur BFCO sont fabriqués et leurs propriétés photovoltaïques sont analysées. Des valeurs de tension de circuit ouvert de 600mV sont encourageantes pour la nouvelle génération de cellules solaires. / In this work, we have produced Bi2FeCrO6 oxides (BFCO) by sol-gel technique and pulsed laser deposition (PLD). By sol-gel, precursors in solution were prepared, which are then deposited by centrifugation on silicon or quartz substrates. The numerous structural (XRD) and optical images (SEM, TEM) analyses carried out on these BFCO films show that the films are fairly homogeneous but exhibit many parasitic phases, which they can be partly eliminated by rapid thermal annealing. Finally, we present the first results obtained on BFCO-SG perovskite devices. On the other hand, BFCO films were deposited on STO and Nb:STO substrates. Their structural, optical and electrical properties are presented. High-quality epitaxial growth and pure-phase films are demonstrated by X-ray diffraction. We show that the band gap of the PLD-BFCO films can be tuned from 1, 9 to 2.6 eV thanks to the variation of growth conditions. Theoretical calculations has confirmed the observed behavior and highlight the importance of the ordering phase. The ferroelectric properties of the PLD films are studied by the piezoresponse force microscopy. Illumination is shown to have a strong effect on polarization. We show that the polarization memory affects the photovoltaic response. Finally, devices based on BFCO are manufactured and their photovoltaic properties are analyzed.

To design an efficient solar energy conversion device, theoretical input is extremely important to provide the basic guideline for experimental scientists, to fabricate the most efficient, cheap, and stable device with less efforts. This desire can be made possible if computational scientist use a proper theoretical protocol, design an energy material, then the experimentalist will only invest weeks or months on the synthetic effort. This thesis highlights my recent efforts in this direction. Monoclinic BiVO4 is has been using as a photocatalyst due to its stability, cheap, easily synthesizable, narrow band gap and ideal VB (-6.80 eV vs vacuum) but inappropriate CB (-4.56 eV vs vacuum) edge position, responsible for its low efficiency. We have carried out a comprehensive experimental and periodic density functional theory (DFT) simulations of the pristine, Oxygen defective (Ov), Se doped monoclinic BiVO4 and heterojunction with Selenium (Se-BiVO4), to improve not only its CB edge position but photocatalytic and charge carrier properties. It is found that Ov (1% Oxygen vacancy) and mild doped BiVO4 (1 to 2% Se) are thermodynamically stable, have ideal band edges ~ -4.30 eV), band gaps (~1.96 eV), and small effective masses of electrons and holes. We have also investigated the contribution of Se to higher performance by effecting morphology, light absorption and charge transfer properties in heterojunction. Finally, it is found that Se makes a direct Z-scheme (band alignments) with BiVO4 where the photoexcited electron of BiVO4 recombine with the VB of Se, consequences electron-hole separation at Se and BiVO4, respectively, as a result, enhanced photocurrent is obtained. Theoretical study of β-TaON in the form of primitive unit cell, supercell and its N, Ta, and O terminated surfaces are carried out with the help of periodic DFT. Optical and electronic properties of all these different species are simulated, which predict TaON as the best candidate for photocatalytic water splitting contrast to their Ta2O5 and Ta3N5 counterparts. The calculated bandgap, valence band, and conduction band edge positions predict that β-TaON should be an efficient photoanodic material. The valence band is made up of N 2p orbitals with a minor contribution from O 2p, while the conduction band is made up of Ta 5d. Turning to thin films, the valence band maximum; VBM (−6.4 eV vs. vacuum) and the conduction band minimum; CBM (−3.3 eV vs. vacuum) of (010)-O terminated surface are respectively well below and above the redox potentials of water as required for photocatalysis. Charge carriers have smaller effective masses than in the (001)-N terminated film (VBM −5.8 and CBM −3.7 eV vs. vacuum). However, due to wide band gap (3.0 eV) of (010)-O terminated surface, it cannot absorb visible wavelengths. On the other hand, the (001)-N terminated TaON thin film has a smaller band gap in the visible region (2.1 eV) but the bands are not aligned to the redox potential of water. Possibly a mixed phase material would produce an efficient photoanode for solar water splitting, where one phase performs the oxidation and the other reduction. Computational study of an optically transparent, near-infrared-absorbing low energy gap conjugated polymer, donor−acceptor−donor (D-A-D) with promising attributes for photovoltaic application is reported herein. The D and A moiety on the polymeric backbone have been found to be responsible for tuning the band gap, optical gap, open circuit (Voc) and short-circuit current density (Jsc) in the polymers solar cells (PSC). Reduction in the band gap, high charge transformation, and enhanced visible light absorption in the D-A-D system is because of strong overlapping of molecular orbitals of D and A. In addition, the enhanced planarity and weak steric hindrance between adjacent units of D-A-D, resulted in red-shifting of its onset of absorption. Finally, PSC properties of the designed D-A-D was modeled in the bulk heterojunction solar cell, which gives theoretical Voc of about 1.02 eV. DFT study has been carried out to design a new All-Solid-State dye-sensitized solar cell (SDSC), by applying a donor-acceptor conjugated polymer instead of liquid electrolyte. The typical redox mediator (I1−/I3−) is replaced with a narrow band gap, hole transporting material (HTM). A unique “upstairs” like band energy diagram is created by packing N3 between HTM and TiO2. Our theoretical simulations prove that the proposed configuration will be highly efficient as the HOMO level of HTM is 1.19 eV above the HOMO of sanitizer (dye); providing an efficient pathway for charge transfer. High short-circuit current density and power conversion efficiency is promised from the strong overlapping of molecular orbitals of HTM and sensitizer. A low reorganization energy of 0.21 eV and exciton binding energy of 0.55 eV, confirm the high efficiency of HTM. Theoretical and experimental studies of a series of four porphyrin-furan dyads were designed and synthesized, having anchoring groups, either at meso-phenyl or pyrrole-β position of a zinc porphyrin based on donor–π–acceptor (D–π–A) approach. The porphyrin macrocycle acts as donor, furan hetero cycle acts as π-spacer and either cyanoacetic acid or malonic acid group acts as acceptor. Optical bandgap, natural bonding, and molecular bonding orbital (HOMO–LUMO) analysis confirm the high efficiency pyrrole-β substituted zinc porphyrins contrast to meso-phenyl dyads. DFT study of polypyrrole-TiO2 composites has been carried out to explore their optical, electronic and charge transfer properties for the development of an efficient photocatalyst. Titanium dioxide (Ti16O32) was interacted with a range of pyrrole (Py) oligomers to predict the optimum composition of nPy-TiO2 composite with suitable band structure for efficient photocatalytic properties. The study has revealed that Py-Ti16O32 composites have narrow band gap and better visible light absorption capability compared to individual constituents. A red-shifting in λmax, narrowing band gap, and strong intermolecular interaction energy (-41 to −72 kcal/mol) of nPy-Ti16O32 composites confirm the existence of strong covalent type interactions. Electron−hole transferring phenomena are simulated with natural bonding orbital analysis where Py oligomers found as donor and Ti16O32 as an acceptor in nPy-Ti16O32 composites. Sensitivity and selectivity of polypyrrole (PPy) towards NH3, CO2 and CO have been studied at DFT. PPy oligomers are used both, in the doped (PPy+) and neutral (PPy) form, for their sensing abilities to realize the best state for gas sensing. Interaction energies and amount of charges (NBO and Mulliken charge analysis) are simulated which reveal the sensing ability of PPy towards these gases. PPy, both in doped and neutral state, is more sensitive to NH3 compared to CO2 and CO. More interestingly, NH3 causes doping of PPy and de-doping of PPy+, providing evidence that PPy/PPy+ is an excellent sensor for NH3 gas. UV-vis and UV-vis-near-IR spectra of nPy, nPy+, and nPy/nPy+-X complexes demonstrate strong interaction of PPy/PPy+ with these atmospheric gases. The applications of graphene (GR) and its derivatives in the field of composite materials for solar energy conversion, energy storage, environment purification and biosensor applications have been reviewed. The vast coverage of advancements in environmental applications of GR-based materials for photocatalytic degradation of organic pollutants, gas sensing and removal of heavy metal ions is presented. Additionally, the presences of graphene composites in the bio-sensing field have been also discussed in this review.

Submitted by Rosivalda Pereira (mrs.pereira@ufma.br) on 2017-06-06T17:54:56Z No. of bitstreams: 1 ManoelCastroJunior.pdf: 27945516 bytes, checksum: 6ae82c3bdbaa01509138f1674855826a (MD5) / Made available in DSpace on 2017-06-06T17:54:56Z (GMT). No. of bitstreams: 1 ManoelCastroJunior.pdf: 27945516 bytes, checksum: 6ae82c3bdbaa01509138f1674855826a (MD5) Previous issue date: 2008-07-11 / Fundação de Amparo à Pesquisa e ao Desenvolvimento Científico e Tecnológico do Maranhão (FAPEMA) / In this work were performed investigations about the vibrational and electric properties of the double ordered complex perovskite Ba2BiSbO6 , for diferent values of temperature, hydrostatic pressure and oscillating field frequency. The vibrational properties were investigated using Raman spectroscopy and the classical phonon calculation by FG Wilson method. The Raman spectra were acquired in the temperature range between 10 K and 573 K and at pressures up to 7.67 GPa. Both structural phase transition observed by Neutrons and X-ray difraction investigations were observed in the temperature dependent Raman spectra. The phase transition R3(S26)→Fm3m (O5h) was observed at around 515 K by the extinction of a mode of the rhombohedral phase localized at around 63 cm-1 and subtle changes in the temperature dependence of the wavenumbers and integrated area of the observed modes. The R3(S26)→I2/m(C52h) phase transition was observed between 250 and 260 K by the change in the intensities of the stretching and bending SbO7-6 octahedral modes. At 10 K was observed a new mode belonging to the monoclinic phase and assigned as Ag. The assignment of the modes in the rhombohedral, monoclinic and cubic phases was performed with basis on the classical phonons calculations by the FG Wilson method. Under hydrostatic pressure the R3(S26)→I2/m(C52h) phase transition was observed by the change in the slope of the temperature dependence of the wavenumbers of the observed modes. The electrical properties were obtained by impedance spectroscopy between room temperature and 560 K. The analysis of the frequency dependence of the imaginary part of the electrical modulus and impedance show that, at low temperatures, only a relaxation process due to the bulk is observed whose the relaxation frequency is thermally activated and follows an Arrhenius law behavior. When the temperature arises, a second relaxation process, whose relaxation frequency is also thermally activated, is observed due, probably, to the grain boundary. The phase transition R3(S26)→Fm3m (O5h) was not observed at high temperatures in the dielectric constant. / Neste trabalho foram investigadas as propriedades vibracionais e elétricas da perovskita dupla ordenada Ba2BiSbO6 em função da temperatura, pressão hidrostática e freqüência do campo oscilante. As propriedades vibracionais do Ba2BiSbO6 foram investigadas por espectroscopia Raman e pelo cálculo clássico de fônons através do método FG de Wilson. Os espectros Raman foram determinados no intervalo de temperatura compreendido entre 10 K e 573 K e para pressões hidrostáticas até 7,67 GPa. Em função da temperatura os espectros Raman mostraram ambas as transições de fase sofridas pelo material propostas pela difração de nêutrons e raios-X em amostras policristalinas. A transição de fase R3(S26)→Fm3m (O5h) foi observada por volta de 515 K através do desaparecimento de um modo da fase romboédrico localizado em torno de 63 cm-1 e por sutis anomalias na dependência do número de onda e área integrada dos modos com a temperatura. A transição de fase R3(S26)→I2/m(C52h) foi observada entre 250 e 260 K pela troca de intensidades entre os modos de stretching e bending do octaedro de SbO7-6 . Para T = 10 K um novo modo em 670 cm-1 foi claramente observado e caracterizado como modo da fase monoclínica de simetria Ag. A classificação dos modos da fase monoclínica, romboédrica e cúbica foi feita com base no cálculo clássico dos fônons pelo método FG de Wilson. Em função da pressão hidrostática, a transição R3(S26)→I2/m(C52h) foi observada através da mudança de inclinação na dependência com a temperatura do número de onda dos modos. As propriedades elétricas do Ba2BiSbO6 foram obtidas através da espectroscopia de impedância no intervalo compreendido entre a temperatura ambiente e 560 K. A análise do módulo elétrico e impedância mostrou que para baixas temperaturas há apenas um processo de relaxação devido ao bulk, termicamente ativado, cuja freqüência de relaxação segue uma lei de Arrhenius. Para altas temperaturas foi observado um novo processo de relaxação, com freqüência de relaxação também crescente, seguindo uma lei de Arrhenius, provavelmente devido a efeitos de contorno de grãos. A transição de fase R3(S26)→Fm3m (O5h) não foi observada através de anomalias na constante dielétrica.