abstract: The origins of carrier mobility (μe) were thoroughly investigated in hydrogenated indium oxide (IO:H) and zinc-tin oxide (ZTO) transparent conducting oxide (TCO) thin films. A carrier transport model was developed for IO:H which studied the effects of ionized impurity scattering, polar optical phonon scattering, and grain boundary scattering. Ionized impurity scattering dominated at temperatures below ~240 K. A reduction in scattering charge Z from +2 to +1 as atomic %H increased from ~3 atomic %H to ~5 atomic %H allowed μe to attain >100 cm^2/Vs at ~5 atomic %H. In highly hydrogenated IO:H, ne significantly decreased as temperature increased from 5 K to 140 K. To probe this unusual behavior, samples were illuminated, then ne, surface work function (WF), and spatially resolved microscopic current mapping were measured and tracked. Large increases in ne and corresponding decreases in WF were observed---these both exhibited slow reversions toward pre-illumination values over 6-12 days. A hydrogen-related defect was proposed as source of the photoexcitation, while a lattice defect diffusion mechanism causes the extended decay. Both arise from an under-coordination of the In. An enhancement of μe was observed with increasing amorphous fraction in IO:H. An increase in population of corner- and edge-sharing polyhedra consisting of metal cations and oxygen anions is thought to be the origin. This indicates some measure of medium-range order in the amorphous structure, and gives rise to a general principle dictating μe in TCOs---even amorphous TCOs. Testing this principle resulted in observing an enhancement of μe up to 35 cm^2/Vs in amorphous ZTO (a-ZTO), one of the highest reported a-ZTO μe values (at ne > 10^19 cm^-3) to date. These results highlight the role of local distortions and cation coordination in determining the microscopic origins of carrier generation and transport. In addition, the strong likelihood of under-coordination of one cation species leading to high carrier concentrations is proposed. This diverges from the historical indictment of oxygen vacancies controlling carrier population in crystalline oxides, which by definition cannot occur in amorphous systems, and provides a framework to discuss key structural descriptors in these disordered phase materials. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2020

Present doctoral thesis is focused on electron microscopy and spectroscopy investigation of novel metal-oxide anode catalyst for fuel cell application. Catalyst based on Pt- doped cerium oxide in form of thin layers prepared by simultaneous magnetron sputtering deposition on intermediate carbonaceous films grown on silicon substrate has been studied. The influence of catalyst support composition (a-C and CNx films), deposition time of CeOx layer and other deposition parameters, as deposition rate, composition of working atmosphere and Pt concentration on the morphology of Pt-CeOx layers has been investigated mainly by Transmission Electron Microscopy (TEM). The obtained results have shown that by suitable preparation conditions combination we are able to tune final morphology and composition of catalyst. Composition of carbonaceous films and Pt-CeOx layers was examined by complementary spectroscopy techniques - Energy Dispersive X-ray Spectroscopy (EDX), Electron Energy Loss Spectroscopy (EELS) and X-ray Photoelectron Spectroscopy (XPS). Such prepared porous structures of Pt-CeOx are of promising as anode catalytic material for real fuel cell application. Keywords: cerium oxide, platinum, fuel cell, magnetron sputtering, Transmission Electron Microscopy

Title: Controllable synthesis, treatment and characterization of anodes for Direct Formic Acid Fuell Cell Author: Mgr. Igor Bieloshapka Department/Institute: Department of Surface and Plasma Science, Faculty of Mathematics and Physics, Charles University Supervisor of the doctoral thesis: Ing. Petr Jiříček, CSc., Institute of Physics of the Czech Academy of Sciences, Division of Solid State Physics, Department of Optical Materials Abstract: At this doctoral thesis, anodes were prepared by novel DC magnetron sputtering technique for direct formic acid fuel cells (DFAFCs). Anode part consisted of support material and catalyst. Carbon cloth and polyaniline were used as a support. Palladium and palladium-copper bimetallic catalysts were deposited on the top of the support. Scanning electron microscope (SEM) and atomic force microscope (AFM) were used for investigation of the morphology of the anodes. Composition and chemical states on the anode part were studied by x-ray photoelectron spectroscopy (XPS). Transmission electron microscope (TEM) together with the XPS technique were used for characterizing graphene oxide (GO) and reduced graphene oxide (RGO) as a promising support for the polymer membrane fuel cells. For decreasing the role of substoichiometric PdCx phase and other contaminations on the surface of...

The L10 FePt phase belongs to the most promising hard ferromagnetic materials for high density recording media. The main challenges for thin FePt films are: (i) to lower the process temperature for the transition from the soft magnetic A1 to the hard magnetic L10 phase, (ii) to realize c-axes preferential oriented layers independently from the substrate nature and (iii) to control layer morphology supporting the formation of FePt - L10 self-organized isolated nanoislands towards an increase of the signal-to-noise ratio. In this study, dc magnetron sputtered FePt thin films on amorphous substrates were inve-stigated. The work is focalized on the correlation between structural and magnetic properties with respect to the influence of deposition parameters like growth mode (co-sputtering vs. layer – by - layer) and the variation of the deposition gas (Ar, Xe) or pressure (0.3 - 3 Pa). In low-pressure Ar discharges, high energetic particle impacts support vacancies formation during layer growth lowering the phase transition temperature to (320 +/- 20)°C. By reducing the particle kinetic energy in Xe discharges, highly (001) preferential oriented L10 - FePt films were obtained on a-SiO2 after vacuum annealing. L10 - FePt nano-island formation was supported by the introduction of an Ag matrix, or by random ballistic aggregation and atomic self shadowing realized by FePt depositions at very high pressure (3 Pa). The high coercivity (1.5 T) of granular, magnetic isotropic FePt layers, deposited in Ar discharges, was measured with SQUID magnetometer hysteresis loops. For non-granular films with (001) preferential orientation the coercivity decreased (0.6 T) together with an enhancement of the out-of- plane anisotropy. Nanoislands show a coercive field close to the values obtained for granular layers but exhibit an in-plane easy axis due to shape anisotropy effects. An extensive study with different synchrotron X-ray scattering techniques, mainly performed at the ESRF, BM-20 (ROBL-Beamline), pointed out the importance of in-situ investigations to clearly understand the kinetic mechanism of the A1 to L10 transition and ordering and to control FePt nanoclusters evolution.

Magister Philosophiae - MPhil / The fascinating optical properties of metallic nanostructures, dominated by collective oscillations of free electrons known as plasmons, open new opportunities for the development of devices fabrication based on noble metal nanoparticle composite materials. This thesis demonstrates a low-cost and versatile technique to produce stimuli-responsive ultrafast plasmonic nanostructures with reversible tunable optical properties. Albeit challenging, further control using thermal external stimuli to tune the local environment of gold nanoparticles embedded in V02 host matrix would be ideal for the design of responsive functional nanocomposites. We prepared Au-V02 nanocomposite thin films by the inverted cylindrical reactive magnetron sputtering (ICMS) known as hollow cathode magnetron sputtering for the first time and report the reversible tuning of surface plasmon resonance of Au nanoparticles by only adjusting the external temperature stimuli. The structural, morphological, interfacial analysis and optical properties of the optimized nanostructures have been studied. ICMS has been attracting much attention for its enclosed geometry and its ability to deposit on large area, uniform coating of smart nanocomposites at high deposition rate. Before achieving the aforementioned goals, a systematic study and optimization process of V02 host matrix has been done by studying the influence of deposition parameters on the structural, morphological and optical switching properties of V02 thin films. A reversible thermal tunability of the optical/dielectric constants of V02 thin films by spectroscopic ellipsometry has been intensively also studied in order to bring more insights about the shift of the plasmon of gold nanoparticles imbedded in V02 host matrix.

Title: Controllable synthesis, treatment, and characterization of anodes for Direct Formic Acid Fuel Cell Author: Igor Bieloshapka Department: Surface and Plasma Science, Faculty of Mathematics and Physics, Charles University Supervisor of the doctoral thesis: Ing. Petr Jiříček, CSc., Institute of Physics of the Czech Academy of Sciences, Division of Solid State Physics, Department of Optical Materials Abstract: This doctoral thesis concerns the preparation of anodes with Pd-based catalysts. Anodes were deposited on a support surface with magnetron sputtering. The prepared samples were tested in a direct formic acid fuel cell (DFAFC) station. Polyaniline, graphene oxide (GO) and reduced graphene oxide (RGO) have been additionally investigated as promising support material for polymer membrane fuel cells (FCs). A scanning electron microscope (SEM) and a transmission electron microscope (TEM) were used to observe the morphological differences between the prepared samples. Elemental composition and chemical states on the anode part were studied through X-ray photoelectron spectroscopy (XPS). The results show that the power density of the prepared anodes with 3 nm of palladium thickness is lower only by 30% in comparison with chemically prepared catalysts. The highest power density results were achieved for the...

<p>  </p> <p>Aluminum (Al) possesses a plenitude of remarkable properties, such as strong corrosion resistance, high thermal and electrical conductivity, and high specific strength. However, Al and its alloys are still remarkably weaker than most high strength steels and susceptible to drastic softening at high temperatures, preventing many applications where its low density would be beneficial. Severe plastic deformation can yield ultra-fine grained Al alloys with similar strengths as steels, although they are highly unstable even at room temperature. Nanotwinned (NT) metals have demonstrated concomitant strength and ductility, enabled by twin boundaries which simultaneously act to inhibit dislocation motion and generate partial dislocations that aid in plasticity. In spite of having a high stacking fault energy, nanotwins have been introduced into Al alloys using transition metal solutes during magnetron sputtering. This thesis aims to explore the impact Zr has on the microstructure, deformation, and thermal stability of nanotwins in NT Al.</p> <p>Our studies identify how Zirconium (Zr) aids in the formation of a significant volume fraction of 9R phase and an abundance of finely spaced incoherent twin boundaries, leading to a maximum hardness of 4.2GPa. They further uncover through <em>in-situ</em> micropillar compression that NT Al-Zr alloys are highly deformable and reach a flow stress of ~1.1GPa. Constant strain rate nanoindentation tests demonstrate the enhanced strain rate sensitivity in NT Al-Zr alloys. Zr is also identified to be a remarkable thermal stabilizer when incorporated into NT Al-Co alloys, with no apparent softening up to 450 °C (0.78 T­m). The influence of substrate texture on nanotwinned Al-Zr alloys microstructure was also thoroughly explored.</p>

No description available.

La pulvérisation cathodique magnétron est un procédé plasma très répandu dans l'industrie pour le dépôt de couches minces. Néanmoins, les exigences des nouvelles applications nécessitent de mieux comprendre, contrôler et maîtriser les processus fondamentaux gouvernant le transport de la matière pour optimiser le procédé. Ce travail de thèse porte sur l'étude du transport des atomes pulvérisés de tungstène (W) en décharge magnétron continu (DC direct current) et pulsée haute puissance (HiPIMS_high power impulse magnétron sputtering). La fluorescence induite par diode laser (TD-LIF) a été mise au point afin de mesurer les fonctions de distribution en vitesse des atomes W pulvérisés. Les mesures ont été calibrées par absorption laser et validées en corrélant avec les vitesses de dépôt. En procédé DC, l'étude de l’influence des paramètres de la décharge (puissance, tension, mélange gazeux Ar/He, distance par rapport à la cible, etc.) a mis en évidence l'évolution spatiale des régimes de transport balistique (atomes énergétiques), diffusif (atomes thermalisés), et mixte (balistique+diffusif). Pour l'étude du procédé HiPIMS, le plasma pulsé a nécessité de développer la TD-LIF résolue en temps (TR-TDLIF). Le degré de liberté supplémentaire qu'offre la dimension temporelle du plasma HiPIMS a permis de mieux comprendre le transport mixte qui représente le cas le plus compliqué. En effet, cela a permis de mesurer la cinétique du transport des atomes pulvérisés en ayant la possibilité de séparer les temps caractéristiques des différents processus / Magnetron sputter deposition is an established and widely used method for the growth of thin films. Nevertheless, the high level of expectations regarding new applications require a better understanding, controlling, mastering of basic processes governing atoms transport in the view of process optimization. This work consist in the study of transport of sputtered W atoms in direct current and high power impulse magnetron discharges (DC and HiPIMS). A tunable diode laser induced fluorescence technique (TD-LIF) has been developed, in order to measure W sputtered atom velocity distribution function. Measurements were calibrated using laser absorption and were corroborated by deposition rate. In DC, the study of the influence of discharge parameters (power, voltage, Ar/He gas mixture, and distance from target, etc.) highlighted spatial evolution of different regimes of transport: ballistic (energetic atoms), diffusive (thermalized atoms), and mixed (ballistic + diffusive). In HiPIMS, pulsed plasma required to develop a time resolved TD-LIF technique (TR-TDLIF). The additional degree of freedom, given by time dimension allowed for a better understanding of mixed transport which represents the most complicated situation. This technique allowed to measure the kinetic of sputtered W atoms while at the same time providing the possibility to separate characteristic time scales of different processes

This thesis reports on the development of low-temperature processes for transition metal carbide and MAX-phase thin film growth. Magnetron sputtering and evaporation, far from thermodynamical equilibrium, have been utilised to engineer the properties of the films by physical and chemical control. Deposition of W, W2C and β-WC1-x films with controlled microstructure, from nanocrystalline to epitaxial, is shown in the W-C system down to 100 oC. W films with upto 20 at% C exhibited an extreme solid-solution hardening effect, with a nanoindentation hardness maximum of 35 GPa. Furthermore, the design of epitaxial ternary carbide films is demonstrated in the Ti1-xVxCy system in the form of controlled unit-cell parameters, strain-free films with a perfect match to the substrate, and ternary epitaxial gradient films. Moreover, phase stabilisation and pseudomorphic growth can be tuned in (Nb,Mo)C and (Ti,W)C films. The results obtained can be used for example to optimise electrical contacts in SiC high-power semiconductor devices. A large part of this thesis focuses on the deposition of MAX-phases. These compounds constitute a family of thermally stable nanolaminates with composition Mn+1AXn, n=1, 2 or 3, where M is an early transition metal, A is generally a group 13-14 element, and X is C or N. They show a combination of typical ceramic and metallic properties and are also machinable by virtue of the unique deformation behaviour observed only in laminates. So far, the MAX-phases have almost exclusively been prepared by high-temperature sintering and studied in bulk form. However, this thesis establishes a patented seed layer approach for successful MAX-phase thin film depositions down to 750 oC. For the first time, single-phase and epitaxial films of Ti3SiC2, Ti3AlC2 and Ti2AlC have been grown. The method has also been used to synthesise a new MAX-phase, Ti4SiC3. In addition, two previously unreported intergrown MAX-type structures are presented, Ti5Si2C3 and Ti7Si2C5. Combined theoretical and experimental results show the possibility to deposit films with very low bulk resistivity and designed mechanical properties. Furthermore, the demonstration of MAX-phase and carbide multilayer films paves the way for macrostructure engineering, for example, in coatings for low-friction or wear applications.