<p>The newfound capability of creating moisture sensitive interference multilayered thin films (MLTFs) comprising microfibrillated cellulose and polymers has not previously been possible to implement on surfaces other than silicon wafer strips. Being able to incorporate interference MLTFs on fibre-based materials would introduce the possibility for new applications within authentication, sensing and customer attraction for the paper and packaging industry. By using trichloro (1H, 1H, 2H, 2H-perfluorooctyl) silane we were able to hydrophobically modify silicon substrates, enabling interference MLTF lift-off and thus the creation of free-standing MLTFs of approximately 400 nm thickness. Contact dried MLTFs approximately 250 nm thick, were successfully transferred to copy- and filter paper as well as to cellulose-based dialysis membranes. We can also report on the successful synthesis of interference MLTFs directly on a fibre composite material and on aluminium. Initial tests of a method to quantify the pull-off conditions of the MLTFs from the fluorinated surfaces using the Micro Adhesion Measurement Apparatus showed promising results.</p>

In this paper it is shown that a completely analytical theory based on the extended Hertzian approach together with additional considerations taking into account the geometrical conditions of a curved surface provide an appropriate model for the theoretical “simulation” of a variety of asperity contact problems. This model yields relatively fast and easy to use tools for the analysing of contact problems arising in connection with rough surfaces. In this study the results are shown on the example of a 3µm-DLC-coating on a steel substrate with asperities of about 100µm in diameter and 15µm height. It is found, that – under a general average pressure of 1GPa – the ideal asperity tip contact situation would lead to severe damage due to plastic flow within the steel substrate. On the other hand a rather conforming contact situation appears to be completely non critical.

L'électronique transparente est actuellement limitée par la difficulté de construire une jonction p-n transparente, en raison du manque d'oxyde transparent conducteur (TCO) de type p réellement performant. L'oxyde cuivreux Cu2O est un TCO de type p prometteur, mais sa bande interdite relativement étroite pour un TCO (2,1 eV), limite sa transmittance dans le domaine visible. Dans le cadre de cette thèse, nous cherchons à augmenter cette valeur. Pour cela, nous explorons la méthode MOCVD comme technique de dépôt pour le dopage au strontium et au calcium de l’oxyde cuivreux. Ce dopage est supposé élargir la bande interdite du Cu2O d'après des calculs ab initio effectués à l'institut Tyndall, à Cork. Dans le chapitre I, nous présentons le contexte de cette thèse. Après avoir expliqué les conditions que doit remplir un matériau pour être un TCO de type p, nous présentons l'état de l'art concernant le Cu2O. Dans le chapitre II, nous présentons l'ensemble des techniques utilisées dans le cadre de cette thèse, de l'élaboration (MOCVD, recuits thermiques) à la caractérisation (MEB, MET, AFM, DRX, spectroscopie FTIR, spectroscopie Raman, XPS, spectroscopie UV-vis-NIR, mesures 4 pointes et mesures d'effet Hall). Au cours du chapitre III, l'influence des paramètres de la MOCVD sur la composition et la morphologie a été analysée pour l’élaboration de couches de Cu2O pures, non dopées en vue d'établir les conditions optimales de dépôt. Nous obtenons des couches continues sur substrat de Si/SiO2, alors qu'elles sont systématiquement hétérogènes avec des zones sans dépôt sur silicium. En outre, nous mettons en évidence le risque d'obtenir la phase cuivre métallique lorsque la concentration de précurseur est élevée, la pression partielle d'oxygène faible et/ou la température élevée. Partant de ces conditions optimales, nous étudions dans le chapitre IV l'influence du dopage au strontium sur les propriétés fonctionnelles des couches (résistivité, largeur de bande interdite et transmittance dans le visible). Une chute de la résistivité a été observée lors du dopage au strontium. Les couches non dopées ont des résistivités de l'ordre de 103 Ω.cm ou plus, contre 10 Ω.cm pour les couches contenant entre 6 et 15% de strontium. La conductivité est bien de type p avec une mobilité de l’ordre de 10 cm2.V-1.s-1 et une densité de porteur de quelques 1016 cm-3. L’écart très grand entre cette densité de porteur et la teneur globale en Sr est lié à la présence d’une contamination des couches par du carbonate et du fluorure de strontium mis en évidence par FTIR et XPS. L’influence réelle de ces impuretés n’a pu être déterminée. Enfin il n'a pas été constaté de variation significative des propriétés optiques, la bande interdite restant large d'environ 2,4 eV et la transmittance moyenne entre 500 et 1000 nm de l'ordre de 55%. Des tendances similaires sont observées dans le chapitre V qui aborde le dopage au calcium, avec comme particularité le fait pour un fort taux de dopage et sous assistance UV, d'aboutir à la présence d'espaces vides localisés à l'interface substrat/Cu2O qui pourrait être lié à la décomposition du carbonate de calcium. Finalement, nous procédons à des recuits thermiques des couches, dopées ou non, dans le chapitre VI. Pour les couches non dopées, cela permet de diminuer la résistivité jusqu’à des valeurs de 10-100 Ω.cm. Pour les couches dopées, cela permet aux couches ayant une résistivité initiale de 10 Ω.cm de descendre jusqu'à 1 Ω.cm. Au cours de cette thèse, nous avons établi les effets du dopage au Sr ou Ca qui conduisent à une forte chute de résistivité sans impact sur les propriétés optiques à la différence des résultats prévus par les calculs ab initio. Nous sommes ainsi parvenus à améliorer les propriétés des couches Cu2O transparentes de type p. / Transparent electronic is currently limited by the lack of a really performant p-type transparent conducting oxide (TCO), which makes the elaboration of a transparent p-n junction challenging. Cuprous oxide Cu2O is a promising p-type TCO, but its optical transmittance in the visible spectrum is limited by its relatively low band gap (2.1 eV). In this thesis, we aim at increasing this value. To achieve that, we explore MOCVD as the growth method for strontium and calcium doping of cuprous oxide. According to ab-initio calculations performed at Tyndall Institute in Cork, doping with these elements is supposed to increase the band gap of Cu2O. In chapter I, we introduce the context of this thesis. After explaining the required conditions that a material must fulfil to be a p-type TCO, we present the state of the art of Cu2O. In chapter II, we present all the techniques used in this work, from the elaboration (MOCVD, thermal annealing) to characterization (SEM, TEM, AFM, XRD, FTIR, Raman spectroscopy, XPS, UV-vis-NIR spectroscopy, 4 point probe and Hall effect measurement). In chapter III, our objective is to synthesize pure, undoped Cu2O thin films. We explore the influence of the MOCVD parameters on the films composition and morphology. We get homogenous films on Si/SiO2 substrates, while we get heterogeneous films with un-deposited parts on silicon substrate. In addition, we show the risk to get the metallic copper phase when precursor concentration is high, oxygen partial pressure is low, and/or temperature is high. This enables us to determine the optimal deposition conditions. Starting from those optimal conditions, we study the influence of strontium doping on the functional properties of the films (resistivity, band gap and visible light transmittance) in chapter IV. A decrease of resistivity was observed with strontium doping. While undoped films show resistivity values of 103 Ω.cm or more, films doped from 6 to 15% strontium show resistivity values of about 10 Ω.cm. P-type conductivity was confirmed through Hall effect measurements, with a mobility close to 10 cm2.V-1.s-1 and a charge carrier density of about 1016 cm-3. The large difference between this carrier density and the Sr concentration can be linked with the presence of a strontium carbonate and fluoride contamination that was detected by FTIR and XPS. The exact influence of those impurities is not well known. In addition, no significant variation of optical properties was observed, the band gap remained close to 2.4 eV and average transmittance in the 500-1000 nm range was about 55%. Similar tendencies were observed for calcium doping, addressed in chapter V. Calcium doping showed the particularity of leading to the presence of cavities localized at the substrate/Cu2O interface, for a high dopant concentration and under UV assistance. Eventually, we performed thermal annealing on some samples, doped and undoped, in chapter VI. For undoped samples, it allowed to decrease resistivity in the 10-100 Ω.cm range. For doped samples, it allows samples showing initial resistivity of about 10 Ω.cm to decrease it to 1 Ω.cm. No impact of thermal annealing on sample morphology or composition was observed. In this thesis, we successfully established the effects of Sr or Ca doping, which lead to a significant decrease of the resistivity without impact on the optical properties, unlike what was predicted by the ab initio calculations. We were thus able to improve the p-type transparent Cu2O thin films properties.

In der vorliegenden Arbeit wird dargestellt, wie sich mit Methoden der nuklearen Festkörperphysik Defekte und Deformationen selbst in kristallographisch komplexen Materialien wie den MAX-Phasen, einer Klasse von Komplexcarbiden bzw. -nitriden, in-situ nachweisen lassen. Die sensitive Messgröße bildet dabei der elektrische Feldgradient (EFG), der ein Maß für die Asymmetrie der den jeweiligen Sondenkern umgebenden Ladungsverteilung darstellt. Es werden zwei Wechselwirkungsmechanismen zwischen Defekt und EFG diskutiert: Einerseits die langreichweitigen Auswirkungen elastischer Verzerrungen, andererseits der direkte Einfluss eines Defektes auf seine lokale elektronische Umgebung. Die Bestimmung der elastischen Antwort des Feldgradienten erfolgt mittels Ab-initio-Methoden im Rahmen der Dichtefunktionaltheorie. Der dabei vorgestellte Ansatz erlaubt es, die Ursachen der Dehnungsabhängigkeit zu klären und andere, speziellere Dehnungsabhängigkeiten wie die Volumenabhängigkeit oder die Strukturabhängigkeit des Feldgradienten zu bestimmen. Die in der Umgebung bestimmter Defekte oder Deformationen auftretenden EFG-Verteilungen werden anhand der allgemeinen Dehnungsabhängigkeit mittels Monte-Carlo-Simulationen bestimmt. Die so vorhergesagten Verteilungen werden durch ein Experiment im Rahmen der gestörten $\gamma$-$\gamma$-Winkelkorrelation (PAC) sichtbar gemacht, indem polykristalline MAX-Phasen unter uniaxialer Last verformt werden. Eine quantitative Auswertung erlaubt es schließlich, Defektdichten in-situ abzuschätzen. Die lokalen Auswirkungen auf den EFG werden anhand verschiedener MAX-Phasen-Mischkristalle systematisch untersucht. Im Zuge dessen wird die Synthese eines bisher unbekannten MAX-Phasen-Mischkristalls, Ti$_2$(Al$_{0,5}$,In$_{0,5}$)C, beschrieben. Die Zugehörigen Gitterkonstanten werden mittels Röntgendiffraktometrie im Rahmen der Rietveld-Methode bestimmt.

Diese Arbeit behandelt mögliche Ursachen der reversiblen Änderung des elektrischen Widerstandes von Praseodym-Kalzium-Manganat (PCMO) durch elektrische Spannungspulse. Für diesen Widerstandsschalteffekt werden entweder chemische oder rein strukturelle Änderungen im PCMO angenommen. In den Experimenten liegt das PCMO als gesputterter Dünnfilm in einem Sandwichkontakt zwischen zwei Edelmetallelektroden vor, wobei die Kontaktflächen durch Strukturierung nur wenige µm² betragen. Um insbesondere die elektrischen Transporteigenschaften der Kontakte und den Einfluss der Grenzflächen zwischen Oxid und Elektroden zu untersuchen, wurden elektrische Charakterisierungen der Sandwichkontakte bei verschiedenen elektrischen Feldstärken, Temperaturen und Magnetfeldern für verschiedene Herstellungsparameter des PCMOs und der Elektroden durchgeführt. Entgegen der üblichen Annahme von Raumladungszonen als bestimmender Faktor des Grenzflächenwiderstandes wurde sowohl in den Grenzflächenwiderständen als auch im Volumenanteil des Films ein elektrischer Transport durch kleine Polaronen beobachtet, wie er von PCMO-Volumenproben bekannt ist. Die damit verbundene Spannungsabhängigkeit der polaronischen Leitfähigkeit, die Änderungen durch elektrisch bzw. magnetisch induzierte kolossale Widerstandseffekte (CER bzw. CMR) sowie negativ-differentielle Effekte in Widerstand bzw. Leitfähigkeit durch Joulesche Erwärmung konnten in den komplexen, stark nicht-linearen Kennlinien zugeordnet werden. Die Befunde legen ein heterogenes Modell für den Grenzflächenwiderstand nahe: Präparationsbedingte, erhöhte Defektdichten, wie z.B. durch Sauerstoffleerstellen, führen lokal zu einem defektinduzierten Metall-Isolator-Übergang und damit zu elektrisch isolierenden Bereichen. Die verbleibenden Bereiche zeigen hingegen noch die Transporteigenschaften von nahezu defektfreien, gut leitfähigem PCMO und bestimmen über ihren effektiven Querschnitt den Grenzflächenwiderstand. Die bei hohen elektrischen Spannungen auftretenden remanenten Schalteffekte konnten einem einzigen Schaltmechanismus mit klar definierter Schaltpolarität zugeordnet werden, obwohl er an beiden Grenzflächen auch gleichzeitig auftreten und sich damit zusammen mit Relaxation- bzw. Akkumulationseffekten in komplexen Widerstandsänderungen überlagern kann. Weder die Wahl der Herstellungsparameter für die PCMO-Schicht noch der Oberelektrode verändern den generellen Schaltmechanismus, wodurch ein struktureller Mechanismus z.B. auf Basis einer empfindlichen langreichweitigen Ladungsordnung im Vergleich zu einer chemischen Änderung sehr unwahrscheinlich wird. Die gemachten Beobachtungen, insbesondere Schaltpolarität und Zeitabhängigkeiten, sind prinzipiell kompatibel mit einer feldgetriebenen Sauerstoff(leerstellen)migration. Hierzu könnte auch die experimentell beobachtete, im Einklang mit Simulationsergebnissen stehende, starke Joulesche Erwärmung während des Schaltens beitragen. Durch eine Änderung der Sauerstoffleerstellenverteilung könnten lokal an den Grenzflächen defektinduzierte Metall-Isolator-Übergänge auftreten, so dass der Widerstandhub als eine Änderung des effektiven Querschnitts der leitfähigen Bereiche an den Grenzflächen zu interpretieren wäre.

M. Tech. Digital Technology. / This dissertation reports on an optical-based two-dimensional position sensor for use in Active Magnetic Bearings (AMB) to measure the position of the levitated rotor. The motivation for the deployment of optical technology is the well-known advantage of high precision contactless displacement measurement. The radial and axial edges of the rotor are illuminated by red and green laser beams respectively. The position of the rotor is determined from its image projected on a Charge Coupled Device (CCD) sensor. The measuring principle is demonstrated as a position sampler in the closed loop control of an active magnetic bearing model. The image representing the position is processed with a real-time algorithm on a Field Programmable Logic Gate Array. The principle of operation of a CCD as a position sensor is analysed in order to establish how the image captured by the CCD can be processed to determine the position of the rotor. A simple AMB is modelled in which the sensor acts as a feedback position device. The main objective of the model is to evaluate the accuracy of the system. The purpose of the overall sensing technique to be used is to achieve highly accurate and precise measurements with CCD-based optical metrology.

A metallic hole array of a rectangular converging-diverging channel (RCDC) shape exhibits extraordinary transmission for wavelengths larger than the periodicity of the holes. We use a three-dimensional (3D) finite element method to analyze the transmission characteristics of two-dimensional metallic hole arrays (2D-MHA) with RCDC. For a straight channel MHA, when the aperture size is reduced, the transmission peaks have a blue-shift. The same result is observed for a smaller gap throat for the RCDC structure. For the rectangular holes with a high length-width ratio, a similar blue-shift in the transmission peaks as well as a narrower full width at half maximum (FWHM) are observed. The asymmetry from the rectangular shape gives this structure high selectivity for light with different polarizations. Furthermore, the RCDC shape gives extra degrees of geometrical variables to 2D-MHA for tuning the location of the transmission peak and the FWHM. Tunable extraordinary transmission via changing temperature of a porous metallic layer on top of a thin layer of dielectric strontium titanate (STO) is then studied. The metallic layer has a through-hole array and each hole has a circular converging-diverging channel (CDC) shape, which induces the excitation of surface plasmon polaritons (SPPs) and then results in a controllable extraordinary optical transmission in the terahertz (THz) frequency range. We use a three-dimensional (3D) finite element method to analyze the transmission characteristics of the structure. Location and magnitude of the transmission peaks can be adjusted by the hole size, converging angle, and thicknesses of metal and STO layers. Remarkably, the suggested structure presents a strong transmission dependency on temperature, which offers a new approach to actively and externally tune the transmission. Currently, the performances of thin film solar cells are limited by poor light absorption and carrier collection. In this research, large, broadband, and polarization-insensitive light absorption enhancement is realized via integrating with unique metallic nanogratings. Through simulation, three possible mechanisms are identified to be responsible for such an enormous enhancement. A test for totaling the absorption over the solar spectrum shows an up to ~30% broadband absorption enhancement when comparing to bare thin film cells. Overall performance of a thin film solar cell is determined by the efficiency of conversing photons to electrons that include light absorption, carrier generation and carrier collection processes. Photon management via hybrid designing has been emerging as a powerful means to further boost the conversion efficiency. Here a new nanograting solar cell design, which can be universal and a new solar cell platform technology, is proposed with goals to achieve large enhancement on broadband light absorption and carrier generation, most importantly, under the much reduced usage of active and non-earth-abundant materials. A test for the short circuit current density in CuIn[subscript x]Ga([subscript 1-x])Se₂ (CIGS) thin film solar cells shows an up to ~250% enhancement when comparing to the corresponding bare thin film cells. Besides that, by placing metal strips on top of the nanograting, which act as the top electrode, this design is able to reduce the use of non-earth-abundant materials such as indium that is normally used in both active and transparent conducting materials. / text

The newfound capability of creating moisture sensitive interference multilayered thin films (MLTFs) comprising microfibrillated cellulose and polymers has not previously been possible to implement on surfaces other than silicon wafer strips. Being able to incorporate interference MLTFs on fibre-based materials would introduce the possibility for new applications within authentication, sensing and customer attraction for the paper and packaging industry. By using trichloro (1H, 1H, 2H, 2H-perfluorooctyl) silane we were able to hydrophobically modify silicon substrates, enabling interference MLTF lift-off and thus the creation of free-standing MLTFs of approximately 400 nm thickness. Contact dried MLTFs approximately 250 nm thick, were successfully transferred to copy- and filter paper as well as to cellulose-based dialysis membranes. We can also report on the successful synthesis of interference MLTFs directly on a fibre composite material and on aluminium. Initial tests of a method to quantify the pull-off conditions of the MLTFs from the fluorinated surfaces using the Micro Adhesion Measurement Apparatus showed promising results.

CdS is conventionally used as a buffer layer in Cu(In,Ga)Se2, CIGS, solar cells. The aim of this thesis is to substitute CdS with cadmium-free, more transparent and environmentally benign alternative buffer layers and to analyze how the material properties of alternative layers affect the solar cell performance. The alternative buffer layers have been deposited using Atomic Layer Deposition, ALD. A theoretical explanation for the success of CdS is that its conduction band, Ec, forms a small positive offset with that of CIGS. In one of the studies in this thesis the theory is tested experimentally by changing both the Ec position of the CIGS and of Zn(O,S) buffer layers through changing their gallium and sulfur contents respectively. Surprisingly, the top performing solar cells for all gallium contents have Zn(O,S) buffer layers with the same sulfur content and properties in spite of predicted unfavorable Ec offsets. An explanation is proposed based on observed non-homogenous composition in the buffer layer. This thesis also shows that the solar cell performance is strongly related to the resistivity of alternative buffer layers made of (Zn,Mg)O. A tentative explanation is that a high resistivity reduces the influence of shunt paths at the buffer layer/absorber interface. For devices in operation however, it seems beneficial to induce persistent photoconductivity, by light soaking, which can reduce the effective Ec barrier at the interface and thereby improve the fill factor of the solar cells. Zn-Sn-O is introduced as a new buffer layer in this thesis. The initial studies show that solar cells with Zn-Sn-O buffer layers have comparable performance to the CdS reference devices. While an intrinsic ZnO layer is required for a high reproducibility and performance of solar cells with CdS buffer layers it is shown in this thesis that it can be thinned if Zn(O,S) or omitted if (Zn,Mg)O buffer layers are used instead. As a result, a top conversion efficiency of 18.1 % was achieved with an (Zn,Mg)O buffer layer, a record for a cadmium and sulfur free CIGS solar cell. / Felaktigt tryckt som Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 717

科学研究費補助金 研究種目:基盤研究(A)(2) 課題番号:09355002 研究代表者:後藤 俊夫 研究期間:1997-1999年度