Our reliance on semiconductors is on the rise with the ever growing use of electronics in our daily life. Organic-inorganic hybrid lead halide perovskites have emerged as a prime alternative to current standard and expensive semiconductors because of its use of abundant elements and the ease of solution processing. This thesis has shed light on the ink-to-solid conversion during the one-step solution process of hybrid perovskite formulations from DMF. We utilize a suite of in situ diagnostic probes including high speed optical microscopy, optical reflectance and absorbance, and grazing incidence wide angle x-ray scattering (GIWAXS), all performed during spin coating, to monitor the solution thinning behavior, changes in optical absorbance, and nucleation and growth of crystalline phases of the precursor and perovskite. The starting formulation experiences solvent-solute interactions within seconds of casting, leading to the formation of a wet gel with nanoscale features visible by in situ GIWAXS. The wet gel subsequently gives way to the formation of ordered precursor solvates (equimolar iodide and chloride solutions) or disordered precursor solvates (equimolar bromide or 3:1 chloride), depending upon the halide and MAI content. The ordered precursor solute phases are stable and retain the solvent for long durations, resulting in consistent conversion behavior to the perovskite phase and solar-cell performance. In this thesis, we develop a firm understanding of the solvent engineering process in which an anti-solvent is used during the coating process through the solvent mixture of GBL and DMSO in different ratios. It has been shown that solvent engineering produce pin hole-free films, justifying its wide adoption across the field. We then translate our learnings from the lab scale spin coating process to the industrial friendly blade coating process. Here we compare the ink solidification and film formation mechanisms of CH3NH3PbI3 in solutions we used to understand the key scientific insights through spin coating. We observe high-quality film formation for T > 100oC, namely in conditions which inhibit the formation of the crystalline intermediate complex phases. In doing so, we achieve fast and direct formation of the perovskite phase with solar cells yielding PCE > 17%.

No description available.

Ces travaux, effectués dans le cadre de la 4e année polaire internationale et à partir des mesures in-situ obtenues durant le projet POLARCAT-France, ont pour objectifs de fournir, dans un premier temps, une climatologie des panaches de pollution transportés depuis les continents sources (Amérique du Nord, Europe et Asie) vers l’Arctique. La climatologie contient des informations sur les propriétés physique, chimique et optique des particules d’aérosols, l’origine des panaches ayant été déterminée à l’aide du modèle lagrangien de rétro-trajectoire FLEXPART. Dans un second temps, les processus qui influent sur les propriétés des particules de pollution durant leur transport vers l’Arctique ont été étudiés. Si au cours de la campagne d’été au Groenland, il a été montré que la totalité des panaches rencontrés ont subit un processus de dépôt humide durant leur transport vers l’Arctique, la campagne de printemps au nord de la Suède a permis de mettre en avant l’évolution d’un même panache échantillonné lors de 3 vols consécutifs ainsi que des propriétés de mélange entre les contributions anthropiques et naturelles de deux panaches asiatiques. / The aims of this thesis were, in a first step, to build a climatology of pollution plumes transported from source continents to the Arctic as measured during the POLARCAT-France campaigns performed in spring and summer 2008, in the frame of the 4th International Polar Year. The climatology is including informations on aerosol particle physical, chemical and optical properties and is organized as a function of pollution plume origins (determined with the Lagrangian transport model FLEXPART). In a second step, aerosol processes which influenced aerosol properties during transport to the Arctic were studied. During the summer campaign, the whole plumes encounter experienced wet scavenging processes on their pathway to Groenland. In spring, a plume was sampled during three consecutive days and thus, its ageing was characterised. Finally, two Asian plumes allowed us to highlight the external mixing between anthropogenic and biomass burning contributions transported to northern scandinavia.

京都大学 / 0048 / 新制・課程博士 / 博士(人間・環境学) / 甲第19072号 / 人博第725号 / 新制||人||174(附属図書館) / 26||人博||725(吉田南総合図書館) / 32023 / 京都大学大学院人間・環境学研究科相関環境学専攻 / (主査)教授 内本 喜晴, 教授 加藤 立久, 教授 吉田 寿雄 / 学位規則第4条第1項該当 / Doctor of Human and Environmental Studies / Kyoto University / DGAM

Master of Science / Department of Geology / Abdelmoneam Raef / In this study, laboratory measurements of ultrasonic frequency P- and S-wave velocities were collected and analyzed from two sets of cores. The first set is from a near surface study in southeastern Kansas, and the second set was from the deep subsurface and obtained from a newly drilled well (Wellington KGS 1-32) in Sumner County, KS. Ultrasonic velocities acquired from the second set of cores were then compared with in situ sonic and dipole sonic frequencies of P- and S-waves from well logs. Well log data, core data, and ultrasonic velocity measurements were integrated for Gassmann fluid replacement modeling. The understanding of the velocity and elastic moduli variations at ultrasonic frequencies, along with the comparison of well log velocities can potentially provide improved understanding to establish a beneficial calibration relationship. It could also allow for estimation of shear wave velocities for wells lacking dipole sonic log data. The ability to utilize cost-effective ultrasonic measurements of velocities and elastic moduli in the laboratory, for fluid replacement modeling (Gassmann) in CO[subscript]2-sequestration, as well as, enhanced oil recovery (EOR) projects, would be a significant advance. Potential alternative use of ultrasonic velocities for determining the effects of fluid replacement using Gassmann modeling, when log data is lacking, is an ongoing effort. In this study, the fluid replacement modeling is executed based on sonic and dipole sonic P- and S-wave velocities and compared with results from theoretical modeling. The significance of this work lies in the potential of establishing a calibration relationship for the representative lithofacies of the carbon geosequestration target zone of the Wellington KGS 1-32 well in Sumner County, and enabling the use of ultrasonic measurements of body wave velocities and elastic moduli in Gassmann fluid replacement modeling. This work, when integrated with continuing effort in mapping lithofacies of the Arbuckle and Mississippian groups, would potentially be of great importance to fluid flow simulation efforts and time-lapse seismic monitoring. This study will utilize Gassmann modeling and a range of measurements and data, which include: well logs and ultrasonic laboratory P- and S-wave measurements and core analysis data.

The primary goal of this work is to measure the acoustic properties of a surface in situ. This generally involves sound pressure measurements and a calculation of the acoustic reflection factor of a surface, which may then be used to calculate the acoustic impedance or the acoustic absorption coefficient. These quantities are of use in acoustic simulations, architectural design, room acoustics and problems in noise control. It is of great interest to determine the performance of a particular surface where it is used, as opposed to measurements conducted in a laboratory. In situ measurements are not trivial, caution must be taken to ensure that high signal-to-noise levels are achieved and that the reflections of sound from the measurement environment are taken into consideration. This study presents five measurement methods that may be applied in situ. The acoustic absorption coefficient is calculated for each method on various surfaces spanning the whole range of absorption. Emphasis is placed on frequency resolution, in order to determine absorption characteristics in the bass region (50 Hz to 200 Hz). Advantages and disadvantages of each method are demonstrated and discussed. Finally, the in situ implementation of the surface pressure method is presented and measurements are made in order to test the limitations of this approach.

The primary goal of this work is to measure the acoustic properties of a surface in situ. This generally involves sound pressure measurements and a calculation of the acoustic reflection factor of a surface, which may then be used to calculate the acoustic impedance or the acoustic absorption coefficient. These quantities are of use in acoustic simulations, architectural design, room acoustics and problems in noise control. It is of great interest to determine the performance of a particular surface where it is used, as opposed to measurements conducted in a laboratory. In situ measurements are not trivial, caution must be taken to ensure that high signal-to-noise levels are achieved and that the reflections of sound from the measurement environment are taken into consideration. This study presents five measurement methods that may be applied in situ. The acoustic absorption coefficient is calculated for each method on various surfaces spanning the whole range of absorption. Emphasis is placed on frequency resolution, in order to determine absorption characteristics in the bass region (50 Hz to 200 Hz). Advantages and disadvantages of each method are demonstrated and discussed. Finally, the in situ implementation of the surface pressure method is presented and measurements are made in order to test the limitations of this approach.

We are interested in measuring the in situ antenna performance in analog land mobile radio (LMR) FM systems. The gain (efficiency and directivity) and self-impedance of an antenna sufficiently characterize its performance and a number of traditional methods exist to measure these quantities. However it is hard to do antenna gain measurements using these methods. Furthermore, it turns out that volumetric antenna gain measurements are not quite relevant for understanding in situ performance. In this thesis, we present a novel approach for directly measuring the in situ performance of antennas in analog LMR systems. The procedure involves receiving an FM signal simultaneously using the antenna under test (AUT) and a reference antenna. Both received signals are demodulated to audio using separate but identical receivers. Then a convenient method for characterizing the audio signal quality is to analyze the private line (PL) tone. The PL tone signal-to-noise ratio (SNR) is calculated by measuring the power of the tone relative to the sub-audio noise power. The PL tone SNR for both antenna systems is compared as it provides a ``bottom line'' evaluation of the antenna performance. The audio SNR can also be mapped to RF SNR using a theoretical method. From simulation and experimental studies, we conclude that the RF SNR estimated using this technique is within 0.5 dB of the actual value for RF SNR values between +3 and +36 dB. Finally, we demonstrate this procedure in actual in situ LMR antenna measurements. / Master of Science

Neste trabalho foram desenvolvidas metodologias para a determinação de substâncias de interesse, como metais pesados (micronutrientes e contaminantes), macronutrientes e pesticidas em solo e águas naturais com ultramicroeletrodo de irídio recoberto com filme de Hg eletrodepositado (UME Ir-Hg) e técnicas voltamétricas, utilizando uma cápsula porosa de cerâmica como cela eletroquímica. As metodologias de medidas com os ultramicroeletrodos foram desenvolvidas inicialmente em condições controladas e posteriormente aplicadas a medidas in-situ, com experimentos com águas naturais e solos, conduzidos em laboratório e também com posteriores medidas em amostras reais. Segundo os resultados obtidos foi possível explorar as metodologias voltamétricas, principalmente as de pulso e redissolução anódica, como ferramentas para estudos in-situ dos metais Cd(II), Pb(II) e Cu(II) e do inseticida organofosforado paration metílico, substâncias de grande interesse, obtendo-se um bom nível de repetibilidade e sensibilidade, com limites de detecção em amostras reais de centenas de ppb\'s. / In this work a methodology for determination of metallic ions (micronutrients and contaminants), macronutrients and pesticides in soil and natural waters was developed using an Hg plated iridium based ultramicroelectrode and voltammetric techniques, using a ceramic capsule as an electrochemical cell. The measurement procedures were developed initially in controlled conditions and therefore applied to in-situ measurements, in soil and natural waters, performed in lab and with real field samples. Regarding the obtained results it was possible do explore the voltammetric techniques, mainly the pulsed and stripping ones, as tools for in-situ determination of Cd(II), Pb(II), Cu(II) and the insecticide methyl parathion, with good reproducibility and sensibility, with detection limits in the order of hundreds of parts per billion.

A previsão de áreas suscetíveis a escorregamentos translacionais rasos tem como fundamental etapa a investigação dos fatores condicionantes e dos mecanismos de ruptura. Algumas destas propriedades, como os parâmetros físicos e hidrológicos dos solos, são determinantes para a instabilização de encostas que estão sujeitas a eventos pluviométricos intensos. Uma destas propriedades é a condutividade hidráulica saturada, cujo comportamento pode influenciar no desenvolvimento de poro-pressão positiva ou levar à perda de sucção dos solos, ocasionando rupturas. Desta forma, o objetivo principal desta pesquisa foi analisar a distribuição lateral e vertical da condutividade hidráulica saturada (Ksat) dos solos e sua influência nos escorregamentos translacionais rasos na Serra do Mar (SP). Para tanto, foi selecionada uma bacia representativa da Serra do Mar e nela foram escolhidas três cicatrizes acessíveis e com limites bem preservados para a realização dos ensaios in situ. As profundidades onde foram realizados os ensaios foram definidas a partir da caracterização morfológica dos mantos de alteração nas trincheiras abertas no topo, no centro e na lateral das cicatrizes (0.25, 0.50, 1.00, 1.50, 2.00 e 2.50 m). Finamente, foram realizados os ensaios in situ utilizando-se o Permeâmetro de Guelph, utilizando-se duas cargas hidráulicas H para a que fosse possível calcular a Ksat empregando-se as equações de Richards, Laplace e a análise de Elricket al. (1989), embora tenha sido utilizada esta última para a análise da variação dos valores. A partir dos valores de Ksat, das propriedades físicas dos materiais (distribuição granulométrica, micro e macroporosidade, porosidade total. Além disso, foi analisada a tendência de variação entre 10-4 e 10-7 m/s, predominando da Ksat com a profundidade. Foram obtidos 41 valores de Ksat, os quais variaram entre as ordens de grandeza 10-5 e 10-6 m/s (82,5% dos valores), que mostraram a pequena variabilidade da Ksat nos perfis de alteração investigados, se comparada às diferenças observadas nas propriedades dos solos e corroboram com os trabalhos desenvolvidos na Serra do Mar. Quando confrontado com as propriedades físicas dos materiais (por exemplo, granulometria e porosidade total), observou-se, principalmente, a correlação positiva com a fração areia. De forma geral, foi possível identificar uma tendência de aumento da Ksat com a profundidade, assim como a existência de algumas descontinuidades hidráulicas significativas, tanto de redução quanto de aumento brusco da Ksat em uma pequena profundidade. / The prediction of landslides-prone areas has as fundamental step researching controlling factors and failure mechanisms. Some of these properties, such as the physical and hydrological soil properties are crucial to the instability of slopes subject to intense rainfall events. One of these properties is the saturated hydraulic conductivity, whose behavior can influence and lead to the development of positive pore-pressure or the loss of soil suction, causing failures. The main objective of this research was to analyze the lateral and vertical hydraulic conductivity (Ksat) of soils and their influence on shallow landslides in the Serra do Mar (SP). Therefore, we selected a representative basin in the Serra do Mar and there three accessible scars, well preserved, were chosen for in situ measurements. Was also performed the topographical characterization of the scars (slope angle, curvature and orientation and contributing area). The depths where the measurements were performed were defined from the morphological characterization of soil profiles in opened trenches at the top, at the lateral and inside the scars (0.25, 0.50, 1.00, 1.50, 2.00 and 2.50 m). At last, were performed the in situ measurements using the Guelph Permeameter, using two heads H for calculating Ksat using Richards equations, Laplace equations and Elrick et al. (1989) analysis, although the latter has been used to analyze the range of values. From the Ksat values and physical soil properties (e. g. grain size distribution, micro and macroporosity, total porosity) we discussed the role played by them in Ksat values. Moreover was analyzed the trend of Ksat variation with depth. We obtained 41 Ksat values, which varied between 10-4 e 10-7 m/s, mostly among the orders of magnitude 10-5 e 10-6 m/s (82.5% values), that showed the small variability of Ksat in the soil profiles if compared to the observed differences in soil properties, and corroborate with studies developed in the Serra do Mar. When confronted with the physical properties of materials (eg, grain size and total porosity), we observed mainly the positive correlation with the sand content. In general, we observed a tendency of increase of Ksat with depth, as well as the existence of some significant hydraulic discontinuities, both the sudden decrease as the increase in Ksat in a small depth.