O titanato de estrôncio é um dielétrico com elevada energia de gap entre a banda de va-lência e a banda de condução, porém quando alguns íons de oxigênio são removidos de sua estrutura cristalina, o composto se torna um semicondutor dopado do tipo n com um regime de ionização de impurezas diferente dos outros semicondutores convencionais. Além disto, o composto exibe uma supercondutividade anômala que diverge da teoria BCS no que diz respeito às interações elétron-fônon. Na medida em que o oxigênio é removido do cristal, a resistividade elétrica diminui no composto, sendo assim, este trabalho tem o objetivo de estudar a evolução do tratamento térmico que transforma o estado isolante em um semicondutor através de medidas de resistividade elétrica in situ durante o tratamento de desoxigenação de monocristais de titanatos de estrôncio crescidos pelo método Floating zone. Com o interesse de estudar as propriedades físicas do sistema Sr1-xCaxTiO3, amostras com diferentes teores de cálcio na faixa entre x = 0 e x = 0,05 foram preparadas e caracteriza-das por difratometria de raios X e medidas de calor específico. A cinética de desoxigena-ção é descrita por modelos matemáticos ajustados sobre pontos experimentais adquiridos nas medidas de resistividade elétrica in situ durante o tratamento térmico. Foi observado que a cinética de desoxigenação é de primeira ordem com energia de ativação de 1,4±0,1 eV, que concorda com os dados previamente reportados na literatura. / Strontium titanate is a dielectric material with large energy gap between valence and con-duction bands. However, when some oxygen ions are removed from the crystal structure it becomes n-type semiconductor with an impurity ionization regime which differs from conventional semiconductors. Furthermore, this compound exhibits non-conventional su-perconductivity which can not be described by electron-phonon interaction predicted by BCS theory. When oxygen gets out from the sample electrical resistivity decreases. The goal of this work is study the deoxygenation kinetics during annealing which turns an insulator into a semiconductor using in situ electrical resistivity measurements during the thermal an-nealing of titanate single crystals grown by Floating zone Method. In order to study physical properties of Sr1-xCaxTiO3 system, samples with different cal-cium contents between x = 0 and 0.05 were prepared and characterized by X-ray difratom-etry and heat capacity. Deoxygenation kinetics were analyzed by models with fits the experimental data acquired at in situ electrical resistivity measurements. It was observed that deoxygenation kinetics is of first order with energy activation of 1,4±0,1 eV The estimated value for activation energy agrees with previously reported data.

No description available.

Although the pairing mechanism in MgB2 is thought to be phonon mediated, there are still many experimental results that lack appropriate explanation. For example, there is no consensus about the magnitude of the energy gap, its temperature dependence, and whether it has only one-gap or not. Many techniques have been used to investigate this, like Raman spectroscopy, farinfrared transmission, specific heat, high-resolution photoemission and tunneling. Most tunneling data on MgB2 are obtained from mechanical junctions. Measurements of energy gap by these junctions have many disadvantages like the instability to temperature and field changes. On the other hand, sandwich-like planar junctions offer a stable and reliable measurement for temperature dependence of the energy gap, where any variation in the tunneling spectra can be interpreted as a direct result from the sample under study. To the best of our knowledge, we report the first energy gap temperature- and magnetic field-dependence of MgB2/Pb planar junctions. Study of the temperature-dependence shows that the small gap value (reported by many groups and explained as a result of surface degradation) is a real bulk property of MgB2. Moreover, our data is in favor of the two-gap model rather than the onegap, multi-gap, or single anisotropic gap models. The study of magnetic field effect on the junctions gave an estimation of the upper critical field of about 5.6 T. The dependence of energy gap on the field has been studied as well. Our junctions show stability against temperature changes, but "collapsed" when the magnetic field (applied normal to the junction barrier) is higher than 3.2 T. The irreversible structural change switched the tunnling mechanism from quisiparticle tunneling into Josephson tunneling. Josephson I-V curves at different temperatures have been studied and the characteristic voltages are calculated. The estimated MgB2 energy gap from supercurrent tunneling in weak link junctions agrees very well with that from quasiparticle tunneling. Reported properties on polycrystalline, single crystal and thin film MgB2 samples are widely varied, depending on the details of preparation procedure. MgB2 single crystals are synthesized mainly by heat treatment at high temperature and pressure. Single crystals prepared by this way have the disadvantages of Mg deficiency and shape irregularity. On the other hand, improving the coupling of grain boundaries in polycrystalline MgB2 (has the lowest normal state resistivity in comparison to many other practical superconductors) will be of practical interest. Consequently, we have been motivated to look for a new heat treatment to prepare high quality polycrystalline and single crystal MgB2 in the same process. The importance of our new method is its simplicity in preparing single crystals (neither high pressure cells nor very high sintering temperatures are required to prepare single crystals) and the quality of the obtained single crystal and polycrystalline MgB2. This method gives high quality and dense polycrystalline MgB2 with very low normal state resistivity (σ(40 ) = 0.28 cm). Single crystals have an average diagonal of 50 m and 10 m thickness with a unique shape that resembles the hexagonal crystal structure. Furthermore, preparing both forms in same process gives a great opportunity to study inconsistencies in their properties. On the other hand, magnesium diboride thin films have also been prepared by magnetron sputtering under new preparation conditions. The prepared thin films have a transition temperature of about 35.2 K and they are promising in fabricating tunnel junctions.

Fundação de Amparo à Pesquisa do Estado do Rio de Janeiro / Este trabalho teve por objetivo a realização do estudo das propriedades ópticas, magnéticas e estruturais do cristal elpasolita Cs2NaAlF6 dopado com as concentrações de 0,1%, 1,0%, 3,0%, 10,0%, 30,0% e 50,0% de Cr3+. O interesse no estudo deste sistema reside na existência de uma larga e intensa banda de luminescência na temperatura ambiente, que se estende do visível ao infravermelho próximo, podendo então ser utilizado como fonte de radiação sintonizável em dispositivos ópticos, optoeletrônicos e detectores, entre outros. Para a investigação das propriedades ópticas foram feitas medidas de luminescência, excitação e luminescência resolvida no tempo, na temperatura ambiente e a baixas temperaturas. Os resultados obtidos mostram largas bandas de luminescência atribuídas aos íons de Cr3+, ocupando dois sítios octaédricos não equivalentes. Os resultados também mostram que a intensidade integrada da luminescência, o baricentro da banda de emissão e o tempo de vida do estado luminescente variam com a concentração de impureza residente no sistema. Foram realizadas medidas de calor específico em função do campo magnético em uma larga faixa de temperatura, cujos resultados mostram o aparecimento do efeito Schottky a baixas temperaturas. Medidas de susceptibilidade magnética em funcão da temperatura também foram realizadas, e mostram um comportamento paramagnético, típico do íon impureza Cr3+, com um ordenamento magnético de curto alcance. Para a determinação das propriedades estruturais foram realizadas medidas de difração de nêutrons na temperatura ambiente. / This work is devoted to study the optical, magnetic and structural properties of the elpasolite crystal Cs2NaAlF6 with 0.1, 1.0, 3.0, 10.0, 30.0 and 50.0% of Cr3+ ions. The interest on this material lies on the fact that such system presents a broad, intense band in the visible and infrared regions at room temperature and therefore can be used as a tunable radiation source in optical, optoelectronic devices and detectors, among others. To investigate the optical properties luminescence, excitation and time-resolved luminescence measurements at room and low temperatures were realized. The results show broad bands attributed to the Cr3+ ions in two non-equivalent sites, both of them with octahedral coordination. The results also show that the luminescence integrated intensity, emission baricenter and luminescence lifetime change with the change of impurity doping. Specific heat measurements were performed as a function of magnetic field in a wide temperature range, whose results show the appearance of the Schottky effect at very low temperatures. The magnetic susceptibility measurements show a paramagnetic behavior, typical of the dopant ion Cr3+, with a short-range magnetic ordering. To determine the structural properties, neutron diffraction measurements were realized at room temperature.

Fundação de Amparo à Pesquisa do Estado do Rio de Janeiro / Este trabalho teve por objetivo a realização do estudo das propriedades ópticas, magnéticas e estruturais do cristal elpasolita Cs2NaAlF6 dopado com as concentrações de 0,1%, 1,0%, 3,0%, 10,0%, 30,0% e 50,0% de Cr3+. O interesse no estudo deste sistema reside na existência de uma larga e intensa banda de luminescência na temperatura ambiente, que se estende do visível ao infravermelho próximo, podendo então ser utilizado como fonte de radiação sintonizável em dispositivos ópticos, optoeletrônicos e detectores, entre outros. Para a investigação das propriedades ópticas foram feitas medidas de luminescência, excitação e luminescência resolvida no tempo, na temperatura ambiente e a baixas temperaturas. Os resultados obtidos mostram largas bandas de luminescência atribuídas aos íons de Cr3+, ocupando dois sítios octaédricos não equivalentes. Os resultados também mostram que a intensidade integrada da luminescência, o baricentro da banda de emissão e o tempo de vida do estado luminescente variam com a concentração de impureza residente no sistema. Foram realizadas medidas de calor específico em função do campo magnético em uma larga faixa de temperatura, cujos resultados mostram o aparecimento do efeito Schottky a baixas temperaturas. Medidas de susceptibilidade magnética em funcão da temperatura também foram realizadas, e mostram um comportamento paramagnético, típico do íon impureza Cr3+, com um ordenamento magnético de curto alcance. Para a determinação das propriedades estruturais foram realizadas medidas de difração de nêutrons na temperatura ambiente. / This work is devoted to study the optical, magnetic and structural properties of the elpasolite crystal Cs2NaAlF6 with 0.1, 1.0, 3.0, 10.0, 30.0 and 50.0% of Cr3+ ions. The interest on this material lies on the fact that such system presents a broad, intense band in the visible and infrared regions at room temperature and therefore can be used as a tunable radiation source in optical, optoelectronic devices and detectors, among others. To investigate the optical properties luminescence, excitation and time-resolved luminescence measurements at room and low temperatures were realized. The results show broad bands attributed to the Cr3+ ions in two non-equivalent sites, both of them with octahedral coordination. The results also show that the luminescence integrated intensity, emission baricenter and luminescence lifetime change with the change of impurity doping. Specific heat measurements were performed as a function of magnetic field in a wide temperature range, whose results show the appearance of the Schottky effect at very low temperatures. The magnetic susceptibility measurements show a paramagnetic behavior, typical of the dopant ion Cr3+, with a short-range magnetic ordering. To determine the structural properties, neutron diffraction measurements were realized at room temperature.

Magnesium alloys, owing to their low density and high specific strength, are potential candidates for structural applications in automotive and aerospace industry. While considerable research effort has been devoted in recent years to understand deformation twinning in these alloys and Mg single crystals, only few studies have been conducted on their fracture behavior. This issue assumes importance since some investigations have shown that Mg alloys may possess low fracture toughness (less than Al alloys). Therefore, a combined experimental and numerical study of fracture in Mg single crystals under mode-I loading is performed in this work. The fracture experiments are conducted using three point bend(TPB) specimens inside a scanning electron microscope(SEM) stage equipped with specially designed fixtures. Three crystallographic orientations are considered where c-axis [0001] is along the normal to the flat surface of the notch in the first two orientations, while in the third it is aligned with the notch front. In-situ electron back scattered diffraction (EBSD) observations are made in the region around the notch root to monitor the evolution of tensile twinning on the specimen free surface. Along with EBSD, optical metallography, fractography and surface profilometry are also performed on the specimens to obtain a comprehensive understanding on the micromechanics of fracture in Mg single crystals. From the EBSD data, it is noticed that all the orientations show profuse tensile twinning of {1012}-type. Further, in the first two orientations, basal and prismatic slip traces are identified along with secondary basal slip inside the twins. The growth of the most prominent twin is monitored as a function of load and it is found that its width saturates at around 120 -150 μm, while twins continue to nucleate farther away to accommodate plastic deformation. The 3D nature of twinning is examined by comparing distribution of twin traces and the average twin volume fraction at the free surface and the mid-plane. It is noted that in all the orientations crack initiation occurs before the attainment of peak load and the crack grows stably along twin-matrix interface. Further, zigzaging of the crack path occurs due to deflection of the crack at the twin-twin intersections. It is found that profuse tensile twinning is an important energy dissipating mechanism that enhances the toughness of the material. Indeed, the experimental results show that the energy release rate J versus load histories corroborate with evolution of average twin volume fraction around the notch root. In order to gain further insights on the mechanics of fracture in Mg single crystals, 3D finite element simulations are carried out using a crystal plasticity framework, which includes crystallographic slip and twinning. The predicted load-displacement curves, slip traces and tensile twinning activity from finite element analysis are in good corroboration with the experimental observations. The numerical results are used to understand the 3D nature of the crack tip stress, plastic slip and twin volume fraction distributions near the notch root. The occurrence of tensile twinning in all three orientations is rationalized from the distribution of nor-mal stress ahead of the notch tip. In particular, compressive normal stress beyond the plastic hinge point causes out-of-plane bulging that is accompanied by tensile twinning for the third orientation in which the c-axis is aligned along the specimen thickness. The above behavior emphasizes the importance of tensile twinning since this orientation has relevance to polycrystalline Mg alloys that have a basal texture.

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

With the soaring advancement of organolead halide perovskite solar cells rising from a power conversion efficiency of merely 3% to more than 22% shortly in five years, researchers’ interests on this big material family have been greatly spurred. So far, both in-depth studies on the fundamental properties of organolead halide perovskites and their extended applications such as photodetectors, light emitting diodes, and lasing have been intensively reported. The great successes have been ascribed to various superior properties of organolead halide hybrid perovskites such as long carrier lifetimes, high carrier mobility, and solution-processable high quality thin films, as will be discussed in Chapter 1. Notably, most of these studies have been limited to their polycrystalline thin films. Single crystals, as a counter form of polycrystals, have no grain boundaries and higher crystallinity, and thus less defects. These characteristics gift single crystals with superior optical, electrical, and mechanical properties, which will be discussed in Chapter 2. For example, organolead halide perovskite single crystals have been reported with much longer carrier lifetimes and higher carrier mobilities, which are especially intriguing for optoelectronic applications. Besides their superior optoelectronic properties, organolead halide perovskites have shown large composition versatility, especially their organic components, which can be controlled to effectively adjust their crystal structures and further fundamental properties. Single crystals are an ideal platform for such composition-structure-property study since a uniform structure with homogeneous compositions and without distraction from grain boundaries as well as excess defects can provide unambiguously information of material properties. As a major part of work of this dissertation, explorative work on the composition-structure-property study of organic-cation-alloyed organolead halide perovskites using their single crystals will be discussed in Chapter 3 and 4. Despite their outstanding charge transport characteristics, organolead halide perovskite single crystals grown by hitherto reported crystallization methods are not suitable for most optoelectronic devices due to their small aspect ratios and free standing growth. As the other major part of work of this dissertation, explorative work on growing organolead halide perovskite monocrystalline films and further their application in solar cells will be discussed in Chapter 5.

京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第20484号 / エネ博第353号 / 新制||エネ||70(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー変換科学専攻 / (主査)教授 木村 晃彦, 教授 星出 敏彦, 教授 今谷 勝次 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

<p> The interplay between superconductivity, magnetism and crystal structure is a central issue in the study of the high Tc cuprates. The transition metal compound La2-xBaxCuO4 (LBCO) was the very first high Tc superconductor, discovered by J. G. Bednorz and K. A. Muller in 1986. However, it has been much less extensively studied than other high Tc materials, due to the difficulty of growing large single crystals. With our Image Furnace facility, we have successfully grown high quality, large LBCO crystals (with x~0.095 , 0.08, 0.05 and 0.025) on the underdoped side of the well known 1/8 (x=0.125) anomaly in this material's phase diagram.</p> <p> Using our rotating anode X-ray source at McMaster University we have performed high-resolution X-ray diffraction studies on our x=0.095 and 0.08 samples and on a 1/8 doped LBCO (x=0.125) crystal grown by our collaborators. The X-ray study mapped out a sequence of tetragonal and orthorhombic crystal structures with temperature, which were known from earlier measurements.</p> <p>We have also performed neutron scattering studies at several Laboratories on x=0.095 , 0.08, 0.05 and 0.025 samples. We observed elastic spin incommensurate Bragg peaks in all samples, and inelastic measurements on the x=0.095 sample allowed us to explore the material's low energy spin fluctuations. The elastic neutron scattering results of higher doped samples (x=0.095 and 0.08) indicate that "collinear" static incommensurate magnetic ordering develops below the low temperature structural phase transition, and this order persists into the superconducting state. Static incommensurate magnetic order is also observed in the La2-xBaxCuO4 (x=0.05 and 0.025) compounds with ordering wavevectors which are rotated by 45° about the commensurate (0.5 ,0.5 ,0) position, with respect to that in the superconducting x=0.095 and 0.08 samples. These spin modulations are one dimensional in the x=0.05 and 0.025 samples, with ordering wavevectors lying along the orthorhombic b* direction. Such a rotation in the orientation of the static spin ordering as a function of increasing Ba doping, from diagonal to collinear is roughly coincident with the transition from an insulating to a superconducting ground state and is similar to that observed in the related La2-xSrxCuO4 system. The low energy, inelastic neutron scattering studies show that the dynamic spin susceptibility for x=0.095 is constant within the superconducting state and decreases as the temperature rises above Tc. </p> / Thesis / Doctor of Philosophy (PhD)