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Hybrid Perovskite Thin Film Formation: From Lab Scale Spin Coating to Large Area Blade CoatingMunir, Rahim 22 November 2017 (has links)
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%.
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Organisation et ségrégation lors de la formation de nanoalliages d'AgCo étudiés par diffusion aux petits et aux grands angles et effet anomal / Organization and segregation during the growth of AgCo nanoalloys studied by small and wide angle scattering and anomalous effectLemoine, Asseline 17 December 2015 (has links)
Ce travail de thèse a pour objectif d'étudier les rôles de la taille, de la composition et de la cinétique de croissance sur la morphologie, la structure, et l'état de mélange de l'argent et du cobalt dans des nanoparticules bimétalliques supportées AgCo. Dans ce but, des mesures in-situ et en temps réel par diffusion des rayons X aux petits et aux grands angles en géométrie d'incidence rasante, et en condition anomale, ont été effectuées au cours de la croissance des nanoparticules AgCo dans des conditions de dépôt simultané ou successif des métaux. Des recuits ont ensuite été réalisés afin d'étudier la stabilité des structures obtenues à température ambiante, et d'observer d'éventuelles transitions activées thermiquement. Pour l'ensemble des modes de dépôt, les nanoparticules (dans une gamme de taille comprise entre 2 et 7nm) présentent une configuration chimique ségrégée. Pour des dépôts successifs de Co puis d'Ag, les nanoparticules sont constituées d'un (ou plusieurs) domaine(s) d'Ag juxtaposé(s) à un domaine de Co, tandis que pour un dépôt d'Ag puis de Co les particules présentent une configuration de type coeur-coquille (Co-Ag). Pour les dépôts simultanés, la configuration cœur-coquille est obtenue à très faible composition en Ag (< ou =20%), au-delà la configuration multidomaines monométalliques est observée. Quelle que soit la configuration initiale, le recuit conduit à une séparation de phase des métaux sous forme de particules Janus et à des réorganisations structurales. / The aim of this work is to study the role of size, composition and growth kinetic conditions on the morphology, the structure and the chemical configuration of AgCo bimetallic supported nanoparticles. Thus, in-situ and in real-time anomalous grazing incidence small and wide angle X-ray scattering measurements were performed during AgCo nanoparticles growth. Two types of growth conditions were studied : simultaneous or successive deposition of the two metals. Samples were also annealed to study the stability of the structures observed at room temperature, and to investigate if structural transitions occur due to thermal activation. For all kind of deposition modes, the nanoparticles (in a size range between 2 and 7 nm) exhibit a segregated chemical configuration. For the deposition of Co followed by Ag deposition, the nanoparticles are constituted of one (or several) Ag domain(s) juxtaposed with a Co domain, whereas for Ag deposition followed by Co deposition, the nanoparticles present a (Co-Ag) core-shell configuration. For simultaneous depositions and Ag poor compositions (< or =20%), the core-shell configuration is obtained. For richer compositions, the multidomain configuration is observed. Whatever the initial configuration, annealing leads to a phase separation of the two metals towards Janus particles and some structural reorganizations occur.
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Interfacial and Solvent Processing Control of Phenyl-C61-Butyric Acid Methyl Ester (PCBM) Incorporated Polymer Thin FilmsHuq, Abul Fatha Md. Anisul 27 May 2015 (has links)
No description available.
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Hybrid Lead Halide Perovskite and Bismuth-Based Perovskite-Inspired Photovoltaics: An In Situ InvestigationTang, Ming-Chun 15 October 2019 (has links)
Ink-based semiconductors that come to mind today include conjugated molecules and polymers, colloidal quantum dots, metal halide hybrid perovskites, and transition metal oxides. These materials form an ink (solution/ suspension/ sol-gel) that can be applied and dried in ambient air to form high-quality films for optoelectronic devices. In this study, we will introduce the current understanding of ink-based lead and lead-free hybrid perovskite and perovskite-inspired thin films. Examples will be presented through time-resolved studies of the solidification to link the solid-state microstructure and device figures of merit to the ink’s formulation, drying, and solidification process. The perovskite crystallization kinetics characterized in situ during the solution process indicates an essential role by the inclusion of Cs+ and K+ alkali metal cations in perovskite inks. The film and device characterizations indicate the functions of mixed cation and halides in determining the optoelectronic properties. The further sophisticated design of perovskite inks enables significantly optimized charge dynamics, including exciton separation, inter-grain charge transfer, trap density, charge mobility, and charge collection efficiency. The considerably improved optoelectronic properties lead to higher charge collection efficiency and, therefore, better open-circuit voltage and fill factor for the Cs+-containing 3D perovskite devices in contrast to the control FAPbI3 one. Recent developments in ink formulation and processing that enable scalable ambient fabrication of high-quality perovskite semiconductor films will also be presented. These findings raise the possibility of developing more controlled perovskites for systematically addressing both charge dynamics and degradation mechanisms in concert for the timely commercialization of perovskite solar cells.
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Solution Processing of Small Molecule Organic Semiconductors: From In situ Investigation to the Scalable Manufacturing of Field Effect TransistorsNiazi, Muhammad Rizwan 05 1900 (has links)
Solution-processed organic field effect transistors (OFETs) have emerged in recent years as promising contenders to be part of electronic and optoelectronic circuits owing to their compatibility with low-cost high throughput roll-to-roll manufacturing technology. The stringent performance requirements for OFETs in terms of carrier mobility, switching speed, turn-on voltage and uniformity over large areas require the performance of single crystal-based OFETs, but these suffer from major scale-up challenges.
To achieve device performance approaching that of single crystals with scalable, high throughput and industry-compatible solution coating of OFETs requires understanding and ultimately controlling the crystallization of organic semiconductors (OSCs), and producing very low defect-density thin films. In this thesis, we develop an understanding of the process-structure-property-performance relationship in OSCs that bring fresh insights into the nature of solution crystallization and lead to novel ways to control OSC crystallization, and finally help achieve fabrication of high-performance OFETs by scalable, high throughput and industry-compatible blade coating method. We probe the solution crystallization of OSCs by employing a suite of ex & in situ characterization techniques. This leads us to an important finding that OSC molecules aggregate to form a dense amorphous intermediate state and nucleation happens from this intermediate state during blade coating under a wide window of coating conditions.
This phenomenon resembles the so-called two-step nucleation model. Two-step nucleation mediates the crystallization of a wide range of natural and synthetic products ranging from soft materials, such as proteins, biominerals, colloids and pharmaceutical molecules, to inorganic compounds. We go on to show that this nucleation mechanism is generally applicable to achieve formation of high-quality polycrystalline films in a variety of small molecule OSCs and their polymer blends. This phenomenon results in highly textured and well-connected domains, which exhibit reduced interfacial and bulk trap-state densities, helping raise the carrier mobility by one to two orders of magnitude in OFETs in comparison to direct nucleation. We extend the understanding developed for solution crystallization of various acenes and thiophene-based small molecule OSCs to the high-performance benzothieno-benzothiophene (BTBT) based small molecule OSCs. On this end, we develop protocols to fabricate high-quality thin films of BTBT based OSCs by blade coating at industrially compatible coating speeds (>100 mms-1). These films show massive single-domains with very few apparent defects when crystallized via multiple liquid-crystalline phases in two-step nucleation conditions, resulting in an average carrier mobility of ~10 cm2V-1s-1.
To sum up, this thesis develops an understanding of OSC solution crystallization and efficient protocols to control polycrystalline thin film quality for high-performance OFETs. These protocols involve a combination of two-step nucleation pathway, solvent mixtures, polymer blends and device-manufacturing conditions. Our efforts enable to realize high-performance OFETs based on high-quality polycrystalline OSC thin films at industry-compatible conditions.
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Insights into the influence of solvent polarity on the crystallization of poly(ethylene oxide) spin-coated thin films via in situ grazing incidence wide angle x-ray scatteringToolan, D.T.W., Isakova, A., Hodgkinson, R., Reeves-McLaren, N., Hammond, O.S., Edler, K.J., Briscoe, W.H., Arnold, T., Gough, Tim, Topham, P.D., Howse, J.R. 10 February 2016 (has links)
yes / Controlling polymer thin-film morphology and crystallinity is crucial for a wide range
of applications, particularly in thin-film organic electronic devices. In this work, the
crystallization behavior of a model polymer, poly(ethylene oxide) (PEO), during spincoating
is studied. PEO films were spun-cast from solvents possessing different
polarities (chloroform, THF and methanol) and probed via in situ grazing incidence
wide angle x-ray scattering. The crystallization behavior was found to follow the
solvent polarity order (where chloroform < THF < methanol) rather than the solubility
order (where THF > chloroform > methanol). When spun-cast from non-polar
chloroform, crystallization largely followed Avrami kinetics, resulting in the formation
of morphologies comprising large spherulites. PEO solutions cast from more polar
solvents (THF and methanol) do not form well-defined highly crystalline
morphologies and are largely amorphous with the presence of small crystalline
regions. The difference in morphological development of PEO spun-cast from polar
solvents is attributed to clustering phenomena that inhibit polymer crystallization.
This work highlights the importance of considering individual components of polymer
solubility, rather than simple total solubility, when designing processing routes for the
generation of morphologies with optimum crystallinities or morphologies.
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Propriétés structurales et magnétiques d'agrégats mixtes CoxPt1-x et CoAg. Effets de proximité et blocage de Coulomb via un agrégat isoléFAVRE, Luc 16 December 2004 (has links) (PDF)
Ce travail de thèse traite de la synthèse et de l'étude des propriétés d'agrégats mixtes magnétiques. Ils sont produits à l'aide d'une technique de co-dépôt utilisant source à vaporisation laser couplée avec une cellule d'évaporation. Les agrégats Co-Ag ont un diamètre moyen de 3,1 nm. L'argent ségrége pour former une structure coeur(Co)-coquille(Ag). Les agrégats CoPt ont une énergie d'anisotropie magnétique (MAE) supérieure à celle d'agrégats de cobalt pur. Ils possèdent un diamètre moyen de 2 nm et sont nanocristallisés dans une phase cfc chimiquement désordonnée. Des mesures de transport électronique à travers un agrégat CoPt isolé ont permis d'observer les effets du blocage de Coulomb et les niveaux d'énergie électroniques discrets de la particule. Nous avons également mesuré l'influence d'agrégats magnétiques sur la densité d'états locale d'une matrice supraconductrice de niobium. Nous avons pu mettre en évidence l'apparition d'états électroniques à l'intérieure de la bande interdite.
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