Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第16849号 / 工博第3570号 / 新制||工||1539(附属図書館) / 29524 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 河合 潤, 教授 白井 泰治, 教授 乾 晴行 / 学位規則第4条第1項該当

This master's thesis deals with deposition of cobalt nanostructures using Electron Beam Induced Depositon (EBID). The thesis firstly describes theoretical background regarding EBID. In the following experimental part, the deposition process is optimized via analysis of exposition parameters and their influence on the final shape of nanostructures. These are analyzed via Atomic Force Microscopy (AFM). Optimized exposure parameters are then applied to the deposition of functional 3-dimensional nanostrucutres. In particular, the deposition of cobalt spheres. The elemental composition is analyzed by the means of element composition using Energy-dispersive X-ray Spectroscopy (EDX) and the nanostructures of desired morphologies are studied with Magnetic Force Microscopy (MFM) and Magneto-Optical Kerr Microscope).

Understanding fuel use is important in researching ancient communities. This project developed methods to identify archaeological fuel from midden, hearth, and ash samples using comparison to modern analogues. Modern analogue fuels were ashed at 2000C, 4000C, and 9000C then analysed with a suite of methods, the results were then used to inform the development of an approach for the identification of archaeological fuels. These methods were tested using samples from Ness of Brodgar, Knowe of Swandro, and Smerquoy/Muckquoy in Orkney. Magnetic susceptibility, scanning electron microscopy with energy dispersive X-ray spectroscopy, pH and Munsell colour assignment were chosen based upon previous archaeological, biofuel, and soil pollution research. The methodologies were refined with the analysis of ash from fuels including peat, seaweed, driftwood, willow, hazel, heather, grasses, cow dung, sheep dung, and bone. Modern analogue fuels at increasing temperatures showed an intensification in magnetism and alkalinity, and an alteration to mineral components during the chemical reaction of combustion that is indicative of fuel type and temperature. Principal components analysis confirmed matches between archaeological samples and modern ash, indicating a strong relationship between peat fuels and the archaeological samples. A correlation is also demonstrated between some of the archaeological samples and sheep dung, driftwood, willow, and animal bone. It is evident that each archaeological site has unique patterns of both fuel type and temperature. This shows that in the absence of abundant traditional wood fuel resources, the occupants of these sites used a combination of alternative fuels.

Enactment of regulatory standards for respirable coal mine dust (RCMD) concentration and crystalline silica content, and advancements in mine ventilation and dust controls led to a steady decline of occupational lung disease among US coal miners between the early 1970s and the mid-1990s. Since that time, there has been an alarming resurgence of disease especially in central Appalachia—with little hard data to pinpoint the causative factors in the mine environment. This situation has emphasized the knowledge gap surrounding specific dust characteristics and their sources. Key observations from many disease cases have suggested that dust constituents sourced from the rock strata in the mine (i.e., the rock layers that surround the target coal seam) may be particularly important; and this fits with the general tendency to extract thinner coal seams, and thus more rock, in many central Appalachian mines. To explore the characteristics of rock-strata sourced dust and its possible influence on the overall RCMD, this thesis reports two primary research efforts: Chapter 1 encompasses a case study conducted in an underground coal mine in West Virginia. (This chapter was previously published in the proceedings of the 18th North American Mine Ventilation Symposium, and is being reproduced with permission of the licensor through.) Following precedent from other studies, respirable dust samples were collected from key locations including in the intake airway, downwind an operating roof bolter, and adjacent to the feeder breaker. Additionally, three locations downwind the production face were simultaneously sampled during four individual continuous miner cuts—which was a unique feature of the current study. Dust was analyzed using previously established methods, including scanning electron microscopy with energy dispersive X-ray (SEM-EDX) to determine particle size and mineralogy distributions. Where comparable, results were generally consistent with those from other central Appalachian mines. However, the unique production sampling scheme offered new insights regarding the shift in particle characteristics as dust moves downwind from the generation point. Changes in size and mineralogy suggested that rock-strata sourced particles, especially aluminosilicates, might interfere with the SEM-EDX classification of other particles, especially coal. To explore the issue of aluminosilicate interference with coal classification, and the possible reasons, Chapter 2 covers two main lines of study. First, existing RCMD samples and SEM-EDX metadata were re-examined. Results suggested that particle loading effects could be at least partly responsible for the appearance of inordinately high aluminosilicate abundance (and conversely low coal) in some samples (i.e., the mineral particles might deposit on the sample filter in close proximity to the coal). Additionally, the presence of coal-mineral microagglomerates (MAGs) was demonstrated. The second line of study in Chapter 2 was therefore to explore whether MAG formation could be due to the RCMD generation process or environmental conditions—rather than merely an artifact of the sampling procedure—and the dispersibility of MAGs, which may have important implications with respect to dust exposure and biological response. Laboratory-generated samples collected passively demonstrated that coal-mineral MAGs can indeed occur without influence from typical RCMD sampling equipment. MAGs were significantly dispersed by sonication in deionized water, though gentle swirling did not yield consistent results. Moreover, in a surfactant solution that mimics natural lung fluid, MAGs were also dispersed. Compared to deionized water, the surfactant may promote more dispersion of coal particles in particular. / Master of Science / Occupational illnesses such as black lung in underground coal mining are still a worrisome issue in the industry. This research was aimed at gaining insight into rock-strata sourced dust and its possible influence on the overall characteristics of respirable coal mine dust (RCMD). The rock strata surrounding the coal seam is often rich in silicates and silica. A case study of RCMD was conducted in a thin-seam mine in West Virginia. Samples were collected in various locations and analyzed using electron microscopy among other methods. Results indicated that mineral dust, especially aluminosilicates, can be very abundant near the production face and might interfere with the measurement of coal dust. To explore such interference, a follow-up study was performed by revisiting a subset of RCMD samples examined in prior work. This approach yielded evidence of coal-mineral microagglomerates. Additional efforts in the laboratory recreated agglomerate formation and demonstrated their dispersibility. Results suggested that the occurrence of microagglomerates is not entirely a direct consequence of the sampling methodology and highlighted their potential importance within the context of exposure assessment and possible biological response.

A dentina esclerosada é um substrato comumente encontrado em pacientes idosos. No entanto, existem poucos estudos comparativos entre dentina humana e bovina esclerosadas. O objetivo deste estudo foi comparar os componentes inorgânicos e orgânicos da dentina saudável e esclerosada humana e bovina, através de cinco parâmetros: nanodureza, módulo de elasticidade, análise quantitativa da concentração de Cálcio (Ca) e Fósforo (P), densidade tubular e morfologia do colágeno. Trinta dentes humanos e 30 bovinos foram distribuídos em 4 grupos experimentais (n=15 por grupo): dentina humana saudável (DHS), esclerosada humana (DEH), bovina saudável (DBS), e bovina esclerosada (DBE). Os dentes saudáveis foram preparados na mesma altura e inclinação dos dentes esclerosados expondo níveis similares da dentina e obtendo fragmentos com 2mm de espessura. Foram realizadas 3 medições por espécime em 3 áreas pré determinadas de dentina intertubular com a utilização do Nanoindentador (carga de 500N por 5 s). Cinco espécimes de cada grupo foram preparados para Microscopia Eletrônica de Varredura (MEV). Com o auxílio da Energia Dispersiva por Raios-X EDX foram obtidos os valores (em percentagem) das concentrações de Ca e P e calculada a relação Ca:P. A contagem dos túbulos por área foi realizada em todas as eletromicrografias. Após descalcificação e preparo, o restante dos espécimes foi analisado em Microscopia Eletrônica de Transmissão (MET). DBS obteve maiores valores de nanodureza comparada à DBE e DHS. DHE sem diferenças com DHS e DBE (p=0,0008). DBS exibiu maiores valores de módulo de elasticidade somente comparada à DHS (p=0,000). A análise estatística não demonstrou diferenças estatisticamente significantes (p=0,71) entre as concentrações de Ca e P. Quanto à densidade tubular (número de túbulos/mm²), os grupos saudáveis foram maiores que os esclerosados e os humanos maiores que os bovinos. As fibras colágenas da DBS mostraram-se mais compactadas e mais desorganizadas que as demais. Pôde se concluir que apenas as concentrações de Ca e P foram similares e que as dentinas esclerosadas humana e bovina mostraram similaridade. Esta pesquisa teve suporte da Fapesp sob o número 2008/10290-8. / The sclerotic dentin has been commonly found in elderly patients. However, there are scarce reports in the literature comparing on the use of human and bovine sclerotic dentins. The objective of this study was to compare inorganic and organic components of healthy and sclerotic dentins from human and bovine. Five parameters were analyzed: nanohardness, elastic modulus, quantitative analysis of Calcium (Ca) and Phosphorous (P) concentrations, tubular density and ultrastructural morphology. Thirty human teeth plus 30 bovine teeth were distributed in 4 experimental groups (n=15 per group): human healthy dentin (HHD), human sclerotic dentin (HSD), bovine healthy dentin (BHD) and bovine sclerotic dentin (BSD). Healthy teeth were cut in the same level and inclination of the sclerotic superficial dentins. The nanohardness and elastic modulus (GPa) of three pre determined areas of each exposed dentin was measured using a nanoindenter (500N for 5s). Five samples of each group were prepared for scanning electron microscopy (SEM) examination. Energy Dispersive X-ray (EDX) was used for obtaining the Ca/P ratio. The tubular density was obtained by counting the tubules in scanning electron micrographs taken in the same magnification and work distance. Data were statistically analyzed by ANOVA complemented by the Tukeys test (p0.05). The ultrastructure of the dentins was observed in specimens processed for transmission electron microscopy (TEM). BHD exhibited significant higher nanohardness than BSD and HHD. HSD nanohardness was similar to those of HHD and BSD (p=0,0008). BHD exhibited significant higher elastic modulus than HHD (p=0,000). The Ca:P ratios were similar amongst all groups (p=0.71). The tubular densities were higher in the healthy dentins than in the sclerotic for both human and bovine. The human dentins presented higher tubular densities than bovine dentins (p=0.000). The intertubular dentin of BHD showed short collagen fibers distributed in a condensed fashion; whereas the other dentins exhibited well-organized long bundles of collagen fibers. It was concluded that sclerotic dentins of human and bovine share most morphological and structural characteristics. This research was supported by Fapesp grants number 2008/10290-8.

La séparation et la purification de biomolécules à partir de milieux bruts, végétaux ou biologiques, est un sujet vaste etcomplexe. De sa compréhension et de son développement dépendent des enjeux industriels, et notamment le completdéveloppement des procédés biotechnologiques, les procédés de séparation, ou downstream processes, constituant environ 80% des coûts totaux de ces procédés. Ce travail se veut une contribution à ces problématiques. Il a été motivé par des résultatsobtenus au préalable dans le laboratoire qui montraient qu’il est possible de récupérer une protéine de très grande taille àpartir d’un milieu réel végétal par l’application d’une seule opération chromatographique (Kerfai, 2011). Suite à ce résultat,des hypothèses ont été énoncées, auxquelles ce travail essaie de répondre : quel(s) mécanisme(s) peuvent expliquer cerésultat ? Existe-t-il une localisation spécifique pour la fixation de la molécule sur l’échangeur d’ions qui rend plus simple etefficace sa récupération lors de l’étape d’élution ? Ainsi, notre objectif a été de progresser dans la connaissance des aspectsfondamentaux de la chromatographie d’échange d’ions appliquée à la séparation des protéines à partir d’un milieu brut.Notamment, l’influence de la présence d’autres protéines dans le milieu a été analysée, et ce dans le cas particulier deprotéines de poids moléculaire très différents, comme c’était le cas dans le travail précédemment cité. Des approches variées,théoriques et expérimentales à différentes échelles sur des milieux réels ou synthétiques, ont été appliquées et parfoisdéveloppées, pour essayer de répondre à ces questions. A l’échelle du procédé, une méthode statistique d’analyse desdonnées (Analyse en Composantes Principales ou ACP) a été menée, dont l’exploitation reste délicate. A l’échelle dulaboratoire, l’étude de l’équilibre et de la cinétique d’échange d’ions a été menée sur des solutions synthétiques de deuxprotéines : la sérum albumine bovine (BSA) (en tant que protéine de référence, couramment étudiée) et la ferritine (protéinede stockage du fer) de point isoélectrique proche de celui de la BSA mais de masse molaire plus élevée. Les résultatsmontrent que des modèles relativement classiques peuvent être appliqués, y compris pour les protéines de très grandes tailles,pour expliquer les aspects cinétiques de l’échange. Le couplage des flux de matière des protéines à l’intérieur des particulesde l’échangeur est très probable, malgré des diffusivités très différentes. Interpréter les résultats d’équilibre reste bien plusardu. La concentration en sel ou la présence de la BSA n’ont que très peu d’effet sur la rétention de la ferritine à l’équilibre.En revanche, la présence de la ferritine affecte très fortement la rétention de la BSA (pourtant plus favorable). Parmi lesphénomènes suggérés dans la littérature, l’effet Vroman a été recherché, mais il n’a pas été constaté dans le système pour lesconditions de travail utilisées. Les isothermes d’adsorption en conditions compétitives n’ont pas pu être simulées par lesmodèles habituels (comme l’isotherme multi-constituants de Langmuir), alors que celles des protéines seules sont tout à faitclassiques. En outre, un blocage partiel des pores de la résine par la ferritine reste probable, empêchant la diffusion de laBSA. Afin de vérifier ce dernier point, une méthodologie a été développée afin d’observer à l’échelle microscopique lesprofils de concentration des éléments représentatifs du système (P, Fe, Cl…) dans les particules. Cette méthode qui se trouveà un stade très avancé de développement, n’a pas encore permis de conclure faute de sensibilité suffisante des sondes àdisposition. / Bioseparations from crude media, vegetable or biological, is a large and complex subject. Future industrial issues depend ontheir understanding and development, namely for biotechnological processes as downstream processes represent up to 80 %of their total cost. This work hopes to contribute to these general questions. It is justified by previous results obtained in thelaboratory showing that it is possible to recover a high molecular weight (HMW) protein from a complex vegetal juice in justone chromatographic operation. Hypotheses have been formulated, to which this work tries to answer: what mechanism couldexplain this behaviour? Is-there a specific location inside particles for the uptake of such protein, facilitating the recoveryduring elution step? Our objective has been to progress on the knowledge of fundamental questions concerning ion-exchangechromatography and their applications for proteins recovery from complex media. The effect of the other proteins in solutionhas been analysed, specifically in the situation where both proteins have a very different molecular weight, as in the previouscited work. Theoretical and experimental approaches, at various scales, have been applied or developed on real or syntheticsystems in order to answer some of these questions. At the process scale, a statistical method for data analysis (PrincipalComponent Analysis or PCA) has been applied. The complete interpretation of its results remains very hard. At thelaboratory scale, equilibrium and kinetics of ion exchange have been studied for synthetic solutions of two proteins: bovineserum albumin (BSA) (as reference protein widely studied), and ferritin (iron storage protein) having similar isoelectric pointas BSA but with higher molecular weight. Classical models for ion-exchange kinetics can explain the experimental results,even for HMW proteins. Mass transfer fluxes seem to be coupled for both proteins, even if they have usually very differentdiffusivities. The interpretation of equilibrium results is much more difficult. Equilibrium uptake of ferritin is not, or lightly,influenced by salt concentration or BSA content. Nevertheless, the presence of ferritin in the medium affects strongly BSAequilibrium uptake (however more favourable). Among the phenomena suggested in the literature, the Vroman effect hasbeen researched but it does not take place under the experimental conditions applied. Simulation of multi-componentisotherms has not been possible by classical models (such as multi-component Langmuir isotherm), while protein isothermsin single solution are standard. Besides, a partial blockage of the resin pores by ferritin is possible, preventing BSA diffusion.Therefore, a methodology has been developed at the microscopic scale, with the aim to observe concentration profiles forrepresentatives elements (P, Fe, Cl …) inside particles. The method, well developed, does not allow to conclude for themoment, because the probes used were not sensible enough.

Submitted by Rafael Santana (rafael.silvasantana@ufpe.br) on 2017-05-11T18:23:17Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Tese de Doutorado - Thiago Oliveira dos Santos.pdf: 7279959 bytes, checksum: 0f1baf3b46416fbe6259c440b1dba2da (MD5) / Made available in DSpace on 2017-05-11T18:23:17Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Tese de Doutorado - Thiago Oliveira dos Santos.pdf: 7279959 bytes, checksum: 0f1baf3b46416fbe6259c440b1dba2da (MD5) Previous issue date: 2016-02-29 / CNPQ. CNEN / Tem aumentado nas últimas décadas o interesse sobre questões relacionadas à conservação ambiental, sendo a poluição atmosférica um dos principais problemas de saúde pública nos grandes centros urbanos. Grande parte dessa contaminação atmosférica é causada por poluentes gasosos e material particulado inalável. Uma das principais fontes é a queima de combustíveis fósseis emitidos, principalmente, por veículos automotores. Alguns organismos, como liquens e bromélias atmosféricas, possuem a habilidade de acumular elementos químicos em seus tecidos, o que os torna excelentes ferramentas em estudos de monitoração da qualidade do ar. O presente trabalho avaliou a qualidade do ar na Região Metropolitana do Recife (RMR) utilizando o líquen Cladonia verticillaris e a bromélia Tillandsia recurvata por meio da quantificação de elementos químicos associados ao tráfego de veículos. Os biomonitores foram alocados em 40 pontos distribuídos na Região Metropolitana do Recife com diferentes intensidades de tráfego de veículos. Após o período de exposição de seis meses, Al, Ba, Ca, Cd, Cl, Fe, K, Mg, Mn, P, Pb, Sb, Sr, Th, V e Zn foram quantificados por meio de Fluorescência de Raios-X por Dispersão de Energia (EDXRF) e Espectrometria de Massa com Plasma Indutivamente Acoplado (ICP-MS). Os organismos foram complementares, sendo ferramentas adequadas para monitoração da qualidade do ar. Assim, o tráfego de veículos foi considerado um dos principais agentes para o incremento de elementos químicos na atmosfera urbana da RMR. / The interest on questions related to environmental conservation has increased in recent decades, being air pollution one of the main public health problems in huge urban centers. Major part of this atmospheric contamination is caused by gaseous pollutants and inhalable particulate matter. One of the main sources is the burning of fossil fuels mainly emitted by motor vehicles. Some organisms, like lichen and atmospheric bromeliad, are able to accumulate chemical elements in their tissues, thereby becoming excellent tools for air quality studies of monitoring. The present work evaluated the air quality in the Metropolitan Region of Recife (RMR) using the lichen Cladonia verticillaris and the bromeliad Tillandsia recurvata, through the quantification of chemical elements associated to vehicles traffic. The biomonitors were transferred to 40 points distributed in the RMR with different intensities of the vehicle traffic. After the exposition period of six months, Al, Ba, Ca, Cd, Cl, Fe, Mg, Mn, P, Pb, Sb, Sr, Th, V and Zn were quantified by Energy Dispersive X-Ray Fluorescence (EDXRF) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The organisms were complementary, being appropriated tools for monitoring the air quality. The vehicle traffic was considered one of the major contributor for increasing chemical elements in the RMR urban atmosphere.

A dentina esclerosada é um substrato comumente encontrado em pacientes idosos. No entanto, existem poucos estudos comparativos entre dentina humana e bovina esclerosadas. O objetivo deste estudo foi comparar os componentes inorgânicos e orgânicos da dentina saudável e esclerosada humana e bovina, através de cinco parâmetros: nanodureza, módulo de elasticidade, análise quantitativa da concentração de Cálcio (Ca) e Fósforo (P), densidade tubular e morfologia do colágeno. Trinta dentes humanos e 30 bovinos foram distribuídos em 4 grupos experimentais (n=15 por grupo): dentina humana saudável (DHS), esclerosada humana (DEH), bovina saudável (DBS), e bovina esclerosada (DBE). Os dentes saudáveis foram preparados na mesma altura e inclinação dos dentes esclerosados expondo níveis similares da dentina e obtendo fragmentos com 2mm de espessura. Foram realizadas 3 medições por espécime em 3 áreas pré determinadas de dentina intertubular com a utilização do Nanoindentador (carga de 500N por 5 s). Cinco espécimes de cada grupo foram preparados para Microscopia Eletrônica de Varredura (MEV). Com o auxílio da Energia Dispersiva por Raios-X EDX foram obtidos os valores (em percentagem) das concentrações de Ca e P e calculada a relação Ca:P. A contagem dos túbulos por área foi realizada em todas as eletromicrografias. Após descalcificação e preparo, o restante dos espécimes foi analisado em Microscopia Eletrônica de Transmissão (MET). DBS obteve maiores valores de nanodureza comparada à DBE e DHS. DHE sem diferenças com DHS e DBE (p=0,0008). DBS exibiu maiores valores de módulo de elasticidade somente comparada à DHS (p=0,000). A análise estatística não demonstrou diferenças estatisticamente significantes (p=0,71) entre as concentrações de Ca e P. Quanto à densidade tubular (número de túbulos/mm²), os grupos saudáveis foram maiores que os esclerosados e os humanos maiores que os bovinos. As fibras colágenas da DBS mostraram-se mais compactadas e mais desorganizadas que as demais. Pôde se concluir que apenas as concentrações de Ca e P foram similares e que as dentinas esclerosadas humana e bovina mostraram similaridade. Esta pesquisa teve suporte da Fapesp sob o número 2008/10290-8. / The sclerotic dentin has been commonly found in elderly patients. However, there are scarce reports in the literature comparing on the use of human and bovine sclerotic dentins. The objective of this study was to compare inorganic and organic components of healthy and sclerotic dentins from human and bovine. Five parameters were analyzed: nanohardness, elastic modulus, quantitative analysis of Calcium (Ca) and Phosphorous (P) concentrations, tubular density and ultrastructural morphology. Thirty human teeth plus 30 bovine teeth were distributed in 4 experimental groups (n=15 per group): human healthy dentin (HHD), human sclerotic dentin (HSD), bovine healthy dentin (BHD) and bovine sclerotic dentin (BSD). Healthy teeth were cut in the same level and inclination of the sclerotic superficial dentins. The nanohardness and elastic modulus (GPa) of three pre determined areas of each exposed dentin was measured using a nanoindenter (500N for 5s). Five samples of each group were prepared for scanning electron microscopy (SEM) examination. Energy Dispersive X-ray (EDX) was used for obtaining the Ca/P ratio. The tubular density was obtained by counting the tubules in scanning electron micrographs taken in the same magnification and work distance. Data were statistically analyzed by ANOVA complemented by the Tukeys test (p0.05). The ultrastructure of the dentins was observed in specimens processed for transmission electron microscopy (TEM). BHD exhibited significant higher nanohardness than BSD and HHD. HSD nanohardness was similar to those of HHD and BSD (p=0,0008). BHD exhibited significant higher elastic modulus than HHD (p=0,000). The Ca:P ratios were similar amongst all groups (p=0.71). The tubular densities were higher in the healthy dentins than in the sclerotic for both human and bovine. The human dentins presented higher tubular densities than bovine dentins (p=0.000). The intertubular dentin of BHD showed short collagen fibers distributed in a condensed fashion; whereas the other dentins exhibited well-organized long bundles of collagen fibers. It was concluded that sclerotic dentins of human and bovine share most morphological and structural characteristics. This research was supported by Fapesp grants number 2008/10290-8.

Die steigende Nachfrage nach erneuerbarer elektrischer Energie erfordert neue photovoltaische Technologien. Effiziente organische Solarzellen mit gemischten, absorbierenden organischen Molekülen wandeln Sonnenlicht in Elektrizität um und die jüngsten Rekorde des Wirkungsgrads zeigen das Potenzial für eine alternative Energieerzeugung. Trotz dieser Durchbrüche führt die Verwendung komplexer organischer Moleküle, die zu einer selbstorganisierten Absorberschicht zusammengemischt werden, zu komplizierten Morphologien, die bisher nur unzureichend abgebildet werden konnten. Die Morphologie hat jedoch einen entscheidenden Einfluss auf die Umwandlung von Photonen in Elektronen und auf den Photostrom, was sich auf die Gesamtleistung der Solarzelle auswirkt. Diese Dissertation ist eine Studie über die Morphologie organischer Dünnfilm-Mischschichten in verschiedenen organischen Solarzellen unter Verwendung analytischer Elektronenmikroskopietechniken (REM, TEM, EDX). In einem weiteren Schritt werden auch die Einflüsse der Mikrostruktureigenschaften dieser im Vakuum abgeschiedenen organischen Solarzellen auf ihre elektronischen Eigenschaften untersucht. Diese Studie umfasst bekannte Zinkphthalocyanin- (ZnPc) und Fulleren (C60) Mischschichten (ZnPc:C60) sowie neu entwickelte Materialien, DTDCTB und NGX gemischt mit C60. Auf mikroskopischer Skala wurde der Einfluss der Abscheidung der oben genannten Schichten auf unterschiedlich erhitzte Substrate, sowie deren Auswirkungen auf die elektronische Leistungsfähigkeit untersucht. Es wurden drei sehr unterschiedliche Wachstumssysteme beobachtet: • Filme mit guter Phasentrennung (ZnPc:C60) • Gut gemischte dünne Schichten (DTDCTB:C60) • Selbstorganisierende Nanodrähte (NGX:C60) Um die gewachsene Mikrostruktur zu erklären werden thermodynamische Modelle zur Erklärung der experimentellen Ergebnisse eingesetzt. Diese Arbeit bietet daher einen Rahmen, der die Planung zukünftiger Experimente leiten kann. Für die in dieser Arbeit untersuchten Schichtsysteme konnte die Korrelation zwischen den Präparationsbedingungen und der Leistungsfähigkeit der Solarzellen durch die beobachtete Mikrostruktur und die Phasenseparation von Donor und Akzeptor gut erklärt werden.:1 MOTIVATION AND INTRODUCTION 5 2 THEORETICAL FUNDAMENTALS 2.1 BASICS OF ORGANIC SOLAR CELLS 2.1.1 Organic semiconductors materials 2.1.2 Working principle of organic solar cells 2.1.3 Characteristic curves of solar cells 2.1.4 Concept of bulk heterojunction 2.1.5 Morphology and phase separation 2.2 RELEVANT LENGTH SCALES IN THE STUDY OF ORGANIC SOLAR CELLS 2.3 THE SCANNING ELECTRON MICROSCOPE 2.3.1 Introduction and working principle 2.3.2 Interaction of primary electrons with sample 2.3.3 Detecting SE and BSE electrons 2.3.4 SEM tool with FIB 2.4 THE TRANSMISSION ELECTRON MICROSCOPE 2.4.1 Working principle and components of TEM 2.4.2 Scattering in TEM 2.4.3 Operation modes in TEM 2.5 ANALYTICAL ELECTRON MICROSCOPY 2.5.1 EDX in TEM 2.5.2 EDX with high-tech detectors 2.6 CHALLENGES OF ELECTRON MICROSCOPY ON ORGANIC MATERIALS 2.6.1 Contrast formation and electron scattering 2.6.2 Damage induced by electron beam 2.6.3 Contrast formation and electron scattering 2.6.4 Necessity of low energy microscopy 3 MATERIALS AND METHODS 3.1 DONORS AND ACCEPTOR 3.1.1 The donor ZnPc 3.1.2 The donor DTDCTB 3.1.3 The donor NGX 3.1.1 The acceptor C60 3.2 FABRICATION OF ORGANIC SOLAR CELL DEVICES AND THIN FILMS 3.2.1 Vacuum deposition 3.2.2 Solar cell devices 3.2.3 Electrical Characterization 3.2.4 Organic thin films on the substrate 3.3 ELECTRON MICROSCOPES AND SAMPLE PREPARATION 3.3.1 Cross-sections using focused ion beam 3.3.2 Experimental details used in TEM/SEM 4 RESULTS AND DISCUSSIONS 4.1 ZNPC AS DONOR MATERIAL 4.1.1 Morphology of ZnPc:C60 thin films 4.1.2 Solar cell devices with ZnPc:C60 active layer 4.1.3 Conclusions and discussion 4.2 DTDCTB AS DONOR MATERIAL 4.2.1 Peculiar performance of the solar cell 4.2.2 Morphology of DTDCTB:C60 thin films 4.2.3 Solar cell devices with DTDCTB:C60 active layer 4.2.4 Conclusions and discussion 4.3 NGX AS DONOR MATERIAL 4.3.1 Morphology of NGX:C60 thin films 4.3.2 Conclusions and discussion 5 CONCLUSION AND OUTLOOK 6 APPENDIX A1 NEAREST NEIGHBOR DISTANCE A2 FROM DARK FIELD TEM IMAGES TO THE ELEMENTAL MAP A3 COMPARING THE COMPOSITION OF DARK AND BRIGHT POINTS IN THE EDX-ELEMENTAL A4 ROUGHNESS MEASUREMENTS FROM EDX IMAGES A5 SPECTROSCOPY MEASUREMENTS ON DTDCTB:C60 7 LISTS 7.1 ABBREVIATIONS 1.: Acronyms B2.: Materials B3.: Symbols 7.2 LIST OF FIGURES 7.3 LIST OF TABLES BIBLIOGRAPHY

Les travaux réalisés dans le cadre de la présente thèse se positionnent dans le contexte de la caractérisation des propriétés de surface des particules. La forme ainsi que les propriétés de surface sont fortement reliées aux propriétés fonctionnelles et à la réactivité des poudres alimentaires. Toutefois, le nombre de techniques disponibles pour l'étude et la caractérisation de la surface d'une particule alimentaire sont très réduites. Ainsi, l'objectif de ce travail a été de développer de nouvelles techniques et protocoles de caractérisation de la forme et de la surface des particules de poudre de lait et de semoule. L'objectif ultime est de mettre en relation les propriétés de surface et la réactivité des particules. Le fil conducteur de ce travail est une approche multi-échelle mettant en jeu différentes techniques d'analyse et de caractérisation. A l'échelle atomique, des techniques pour caractériser la surface et le coeur des particules par EDX ont été développées (permettant de sonder la particule à 1 µm de profondeur). L'adaptation de l'EDX couplé à l'XPS (5 nm de profondeur) permet de remonter à des valeurs de composition de surface (lactose, lipides, protéines) à partir des pourcentages atomiques. A l'échelle moléculaire, les gradients de composition par couplage de l'EDX et l'XPS ainsi que les différentes fractions de matière grasse (matière grasse libre, encapsulée et totale) ont été étudiés. En parallèle, un protocole de caractérisation a permis d'évaluer les propriétés de forme à l'aide d'un granumorpholomètre. L'énergie libre de surface a été déterminée par la CGI et la Monté Capillaire. Ces techniques novatrices dans le domaine des poudres alimentaires ont démontré leur intérêt. Finalement, à l'échelle de la microstructure, la modification de la surface par des contraintes externes a été étudié. Ainsi, les interactions particule/eau et la modification de la surface par enrobage à sec ont été étudiés Pour cela, des composants purs comme enrobant (carbohydrates ou protéines) ont été utilisés / The work carried out on this PhD thesis is positioned in the context of the characterization of the food particle surface properties. The shape and surface characteristics are strongly related to the functional properties and reactivity of food powders. However, the number of techniques available, to perfromethe study and characterization of food particles surface is reduced. Thus, the objective of this work was to develop new techniques and protocols in order to characterize the shape and surface of milk powder and semolina particles. The ultimate goal is to relate the particle surface properties and reactivity. A multi-scale approach raised in this work involves different analytical techniques and characterization. At the atomic scale, techniques to characterize the surface and the heart of particles by EDX were developed (exploration of the particle at 1 micron depth). The adaptation of the EDX coupled to the XPS (5 nm depth) permit figure out the values of surface composition (lactose, fat, protein) from atomic percentages. At the molecular level, the composition gradients studied by coupling the EDX and XPS as well as different fractions of fat (fat free, encapsulated and total) were studied. In parallel, a characterization protocol was used to evaluate the shape properties using a granumorpholometer. The surface free energy was determined by IGC and Capillary rise. These innovative techniques in the field of food powders have demonstrated to be of interest. Finally,a at the microstructural scale, the surface modification by external contraintswas studied. Thus, interactions particle / water and surface modification by dry coating,to do it, pure components as coating (carbohydrates or proteins) were used