In this Thesis a set of functional solid oxides for industrial applications have been addressed by first principles and thermodynamical modelling. More specificially, measurable quantities such as Gibbs free energy, geometry and electronic structure have been calculated and compared when possible with experimental data. These are crystalline and amorphous aluminum oxide (Al2O3), Zirconia (ZrO2), magnesium oxide (MgO), indiumoxide (In2O3) and Kaolinite clay (Al2Si2O5(OH)4). The reader is provided a computation tool box, which contains a set of methods to calculate properties of oxides that are measurable in an experiment. There are three goals which we would like to reach when trying to calculate experimental quantities. The first is verification. Without verification of the theory we are utilizing, we cannot reach the second goal -prediction. Ultimately, this may be (and to some extent already is) the future of first principles methods, since their basis lies within the fundamental quantum mechanics and since they require no experimental input apart from what is known from the periodic table. Examples of the techniques which may provide verification are X-Ray Diffraction (XRD), X-ray Absorption and Emission Spectroscopy (XAS and XES), Electron Energy Loss Spectroscopy and Photo-Emission Spectroscopy (PES). These techniques involve a number of complex phenomena which puts high demands on the chosen computational method/s. Together, theory and experiment may enhance the understanding of materials properties compared to the standalone methods. This is the final goal which we are trying to reach -understanding. When used correctly, first principles theory may play the role of a highly resolved analysis method, which provides details of structural and electronic properties on an atomiclevel. One example is the use of first principles to resolve spectra of multicomponentsamples. Another is the analysis of low concentrations of defects. Thorough analysis of the nanoscale properties of products might not be possible in industry due to time and cost limitations. This leads to limited control of for example low concentrations of defects, which may still impact the final performance of the product. On example within cutting tool industry is the impact of defect contents on the melting point and stability of protective coatings. Such defects could be hardening elements such as Si, Mn, S, Ca which diffuse from a steel workpiece into the protective coating during high temperature machining. Other problems are the solving of Fe from the workpiece into the coating and reactions between iron oxide, formed as the workpiece surface is oxidized, and the protective coating. The second part of the computational toolbox which is provided to the reader is the simulation of solid oxide synthesis. Here, a formation energy formalism, most often applied to materials intended in electronics devices is applied. The simulation of Chemical Vapour Deposition (CVD) and Physical Vapor Deposition (PVD) requires good knowledge of the experimental conditions, which can then be applied in the theoretical simulations. Effects of temperature, chemical and electron potential, modelled concentration and choice of theoretical method on the heat of formation of different solid oxides with and without dopants are addressed in this work. A considerable part of this Thesis is based upon first principles calculations, more specifically, Density Functional Theory (DFT) After Kohn and Pople received the Nobel Prize in chemistry in 1998, the use of DFT for computational modelling has increased strikingly (see Fig. 1). The use of other first principles methods such as hybrid functionals and the GW approach (see abbreviations for short explanations and chapter 4.5 and 5.3.) have also become increasingly popular, due to the improved computational resources. These methods are also employed in this Thesis. / QC 20110201

The present thesis deals with a theoretical description of issues regarding chemical bonding, structure and stability of transition metal carbides and multilayered structures. First principles density functional theory has been used extensively to investigate the properties of alloyed solutions of transition metal carbides. Joint theoretical and experimental investigations have shown that there is a driving force for carbon to be released from these ternary carbide systems as a response to the alloying. This release of carbon was shown to yield favorable lubricating properties in the case of alloyed solutions of Ti-Al-C, that were not present in the case of pure TiC, a property that can be used to design new materials that combine high hardness with favorable tribological properties. From calculations of the activation energy of C diffusion in the vicinity of substitutional transition metal impurities (M) in TiC, it is found that the mobility of C atoms is increased due to the presence of the impurities. The lowering of the activation energy barriers suggests that the mobility of C in alloyed solutions of Ti-M-C is increased and will be more pronounced at lower temperature than for C diffusion in TiC. The magnetic properties of alloyed solutions of Ti-Fe-C has been investigated using both theory and experiment. Theoretical calculations reveal that the magnetic moment and the critical temperature increase when increasing the Fe content as well as when lowering the C content in the system. Furthermore, the magnetic exchange parameters between Fe atoms were found to clearly reflect changes in the chemical bonding when varying the C content. Experimentally the magnetic properties were found to be rather substantial. Furthermore, the magnetic properties changes upon annealing due to the formation of Fe-rich and Fe-poor regions in the system. After long enough annealing times precipitates of α-Fe are formed which is consistent with theoretical predictions. The interaction between TiC(111) surfaces and C in the form of graphite has also been investigated. For these systems it was found that graphite was rather strongly bonded to the carbide surface and that the atomic as well as electronic structure at the interface depend on the termination of the carbide surface. This research was motivated by the recent interest in graphene, but also to investigate how carbide grains interacts with C when dispersed in a carbon matrix. A model for the calculation of structural parameters in multilayer structures has been presented and evaluated. The model is based on classical elasticity theory and uses the elastic constants of the materials constituting the multilayer as the only input.

This thesis summarizes interrelated simulation studies of three different physical phenomena. The three topics are: simulation of work hardening of materials using dislocation dynamics, investigation of anomalous diffusion in supercooled liquids using molecular dynamics,and kinetic Monte-Carlo simulation of annealing of radiation damaged materials. All three topics require special algorithms in order to enable physically relevant simulations. The author's contributionconsists of development, implementation, and optimization of these algorithms, as well as interpretation of simulation results. / QC 20100805

Two-dimensional layered materials, namely monolayer hexagonal boron nitride and graphene were grown by CVD on various transition metals. The physical and chemical properties of these systems were characterized systematically using synchrotron-based spectroscopic techniques, scanning tunneling microscopy and low energy electron diffraction. It is learned that the overlayer–substrate interaction is caused by the overlayer π–substrate d band hybridization. The physical properties of these overlayers depend on the strength of interaction and the degree of lattice matching at the interface. The strength of interaction between the boron nitride and graphene overlayers and the transition metal substrates is increasing from Pt(111)–Ir(111)–Rh(111)–Ru(0001). For overlayers adsorbed on Rh and Ru, the interplay between these two parameters can result in corrugation of the overlayer, i.e. a surface with bonding and non-bonding areas. The amplitude of corrugation is increasing with the strength of interfacial interaction. The corrugated BN overlayer (BN nanomesh) was used as a template for the growth of two-dimensional and highly dispersive Au nanoparticles. In addition, the inert BN nanomesh was used as a substrate for the deposition of pentacene molecules that conform to the corrugated surface while preserving the herringbone crystal structure. The coadsorption of oxygen and Co clusters on the nanomesh was investigated. Oxygen was utilized to lower the Co surface energy, i.e. to prevent Co agglomeration. It is observed that the smaller Co clusters intercalate through the BN overlayer upon soft annealing. Beside the surface structure, the substrate induced surface reactivity of the MG overlayer was employed to promote the hydrogenation of graphene on Pt, Ir and Ni. The graphene layer adsorbed on Pt and Ir shows higher H uptake than MG/Ni. Furthermore the uptake increases with the size of the bonded graphene. The small H uptake for MG/Ni was attributed to the electron localization in the C-Ni bonds.

This thesis is a study of the static and dynamic behavior of the magne-tization in spin-flop bi-layers, which consist of two soft ferromagnetic layerscoupled by dipolar forces through a thin nonmagnetic spacer. The focus ofthe work is three fold: collective spin dynamics in the anti-parallel groundstate; resonant switching in the presence of thermal agitation; and static anddynamic behavior of the system in the vortex-pair state, with a particularemphasis on the interlayer core-core interaction. Two collective spin-flop resonance modes are observed and interpreted asacoustical and optical spin precessions, in which the moments of the two lay-ers oscillate in phase and out of phase, respectively. An analytical macrospinmodel is developed to analyze the experimental results and is found to ac-curately predict the resonance frequencies and their field dependence in thelow-field anti-parallel state and the high-field near saturated state. A micro-magnetic model is developed and successfully explains the static and dynamicbehavior of the system in the entire field range, including the C- and S-typespin-perturbed scissor state of the bi-layer at intermediate fields. The optical spin-flop resonance at 3-4 GHz is used to demonstrate resonantswitching in the system, in the range of the applied field where quasi-staticswitching is forbidden. An off-axis field of relatively small amplitude canexcite large-angle scissor-like oscillations at the optical resonance frequency,which can result in a full 180-degree reversal, with the two moments switchingpast each other into the mirror anti-parallel state. It is found that the switch-ing probability increases with increasing the duration of the microwave fieldpulse, which shows that the resonant switching process is affected by thermalagitation. Micromagnetic modeling incorporating the effect of temperature isperformed and is in good agreement with the experimental results. Vortex pair states in spin-flop bi-layers are produced using high amplitudefield pulses near the optical spin resonance in the system. The stable vortex-pair states, 16 in total, of which 4 sub-classes are non-degenerate in energy, areidentified and investigated using static and dynamic applied fields. For AP-chirality vortex-pair states, the system can be studied while the two vortexcores are coupled and decoupled in a single field sweep. It is found thatthe dynamics of the AP-chirality vortex pairs is critically determined by thepolarizations of the two vortex cores and the resulting attractive or repulsivecore-core interaction. The measured spin resonance modes in the system areinterpreted as gyrational, rotational, and vibrational resonances with the helpof the analytical and micromagnetic models developed herein. A significant effort during this project was made to build two instrumentsfor surface and transport characterization of magnetic nanostructures: a high-current Scanning Tunneling Microscope for studying transport in magneticpoint contacts, and a Current In Plane Tunneling instrument for characteriz-ing unpatterned magnetic tunnel junctions. The design and implementationof the instruments as well as the test data are presented. / QC 20101209

Monoatomic chain formation for Ag, Au, Pd and Pt has been investigated using a model for the tip structure. First-principles calculations, mostly spin polarized, were performed within the framework of the Density Functional theory. Results are presented and discussed on the basis of the electronic structure. Tendencies for chain formation were noted for Ag, Au and Pt.

The near-Fermi-energy energy band structure of carbon nanotubes is given by cross-sections of the graphene Dirac cones near the K and K' points. Using second-order perturbation theory and a nearest-neighbor approximated tight-binding model, curvature-induced corrections to the graphene-based effective model are derived. In addition to the already known Dirac-point shift, the curvature is shown to cause not only a warping of the Dirac cone, tantamount to a slight compression and a correction to the overall Fermi velocity, but also a tilting of the Dirac cone and the associated nanotube energy bands. This tilting results in a velocity asymmetry for left- and right-going waves and two different kinds of excitations, allowing for varying degeneracy in the same sample. Previous experiments have shown irregularities in the level degeneracy and should be reconsidered in this context. / Energibandstrukturen för kolnanorör ges av tvärsnitt av grafens Dirac-koner nära K- och K'-punkterna. Medelst andra ordningens störningsteori och en tight-binding-modell med närmaste-granne-approximationen härleds de kurvaturinducerade korrektionerna till den grafenbaserade effektiva modellen. Utöver det redan kända Dirac-punkt-skiftet så visas kurvaturen orsaka inte bara en förvrängning av Dirac-konen, liktydigt med en mild kompression och en korrektion till den övergripande fermihastigheten, utan också en lutning av Dirac-konen och de associerade nanorörsenergibanden. Denna lutning resulterar i en hastighetsasymmetri för vänster- och högergående vågor och två olika sorters excitationer, vilket tillåter för varierande degeneration i samma prov. Tidigare experiment har visat oregelbundenheter i nivådegenerationen och bör omprövas i denna kontext.

The purpose of this master thesis is to investigate theoretically the influence of a nanomagnet on the Josephson effect displayed by phase biased point contacts consisting of topological superconductors. The device is modeled using the nonequilibrium Keldysh Green’s function technique. First, the Gor’kov Green’s functions are calculated. From these Green’s functions, the quasi-classical ones, relevant for energies around the Fermi energy, are obtained. Transport properties such as charge currents are calculated and analyzed in terms of the junction’s density of states displaying Andreev and Majorana states. The combination of the nanomagnet coupling and the spin-momentum locking of the topological superconductors generates a magneto-electric effect causing the supercurrent to depend strongly on the nanomagnet’s direction.

8-band k.p theory was applied to bulk GaN and InN. The optical transitionintensity was computed and results show > 80-90% degree of polarization inthe direction of compression. Polarization switching is observed when strainwas reversed from compressive to tensile. 6 band k.p theory was used tostudy InGaN quantum dot/GaN elliptical pyramid structures. The opticaltransition intensity was calculated for different elongations of the pyramid.Elongation of the pyramid gives rise to a small polarization in the directionof the pyramid elongation. The optical transition intensity was calculatedfor elongated quantum dots and was strongly in uencing the polarization inthe direction of the quantum dot elongation, with a degree of polarization of >90%.

Today’s society is currently performing an exit from fossilfuel energy sources. The change to sustainable alternativesrequires inexpensive and environmentally friendly energy storagedevices. However, most current devices contain expensive,rare or toxic materials. These materials must be replaced bylow-cost, abundant, nontoxic components.In this thesis, I suggest the production of paper-based electricdouble-layer capacitors (EDLCs) to meet the demand oflow-cost energy storage devices that provide high power density.To fulfill the requirements of sustainable and environmentallyfriendly devices, production of EDLCs that consist of paper,graphite and saltwater is proposed. Paper can be used as aseparator between the electrodes and as a substrate for theelectrodes. Graphite is suited for use as an active material in theelectrodes, and saltwater can be employed as an electrolyte.Westudied and developed different methods for the productionof nanographite and graphene from graphite. Composites containingthese materials and similar advanced carbon materialshave been tested as electrode materials in EDLCs. I suggest theuse of cellulose nanofibers (CNFs) or microfibrillated cellulose(MFC) as a binder in the electrodes. In addition to improvedmechanical stability, the nanocellulose improved the stabilityof graphite dispersions and the electrical performance of theelectrodes. The influence of the cellulose quality on the electricalproperties of the electrodes and EDLCs was investigated.The results showed that the finest nanocellulose quality is notthe best choice for EDLC electrodes; MFC is recommended forthis application instead. The results also demonstrated thatthe capacitance of EDLCs can be increased if the electrodemasses are adjusted according to the size of the electrolyte ions.Moreover, we investigated the issue of high contact resistancesat the interface between porous carbon electrodes and metalcurrent collectors. To reduce the contact resistance, graphitefoil can be used as a current collector instead of metal foils.Using the suggested low-cost materials, production methodsand conceptual improvements, it is possible to reduce the material costs by more than 90% in comparison with commercialunits. This confirms that paper-based EDLCs are apromising alternative to conventional EDLCs. Our findings andadditional research can be expected to substantially supportthe design and commercialization of sustainable EDLCs andother green energy technologies. / I dagens samhälle pågår en omställning från användning avfossila energikällor till förnybara alternativ. Denna förändringkräver miljövänliga och kostnadseffektiva elektriska energilagringsenheterför att möjliggöra en kontinuerlig energileverans.Dagens energilagringsenheter innehåller ofta dyra, sällsyntaeller giftiga material som behöver bytas ut för att nå hållbaralösningar.I denna avhandling föreslås att tillverka pappersbaseradesuperkondensatorer som möter kraven för kostnadseffektivaelektriska energilagrare med hög effekttäthet. För att nå kravenpå miljömässigt hållbara enheter föreslås användning avendast papper, grafit och saltvatten. Papper kan användas somseparator mellan elektroder likväl som substrat vid elektrodbestrykning.Grafit kan användas som aktivt elektrodmaterialoch saltvatten fungerar som elektrolyt. Olika metoder har härutvecklats för att producera nanografit och grafen från grafit.Dessa material har tillsammans med liknande, kommersiellt tillgängliga,avancerade kolmaterial testats i elektrodkompositerför superkondensatorer. Som bindemedel i dessa kompositerföreslås nanofibrillerad eller mikrofibrillerad cellulosa. Jaghar demonstrerat att nanocellulosa ökar dispersionsstabilitetensamt förbättrar den mekaniska stabiliteten och dom elektriskaegenskaperna i elektroderna. Hur cellulosans kvalitet påverkarelektroderna har undersökts och visar att den finaste kvaliteteninte är det bästa valet för superkondensatorer, istället rekommenderasmikrofibrillerad cellulosa. Utöver detta demonstrerasmöjligheten att öka superkondensatorernas kapacitans genomatt balansera elektrodernas massa med hänsyn till jonernasstorlek i elektrolyten. I avhandlingen diskuteras även svårigheternamed hög kontaktresistans i gränssnittet mellan porösakolstrukturer och metallfolie och hur detta kan undvikas omgrafitfolie används som kontakt.Genom att använda de material, produktionstekniker ochkonceptförbättringar som föreslås i avhandlingen är det möjligtatt reducera materialkostnaderna med mer än 90% i jämförelsemed kommersiella superkondensatorer. Detta bekräftar att pappersbaserade superkondensatorer är ett lovande alternativoch våra resultat tillsammans med vidare utveckling harstor potential att stödja övergången till miljömässigt hållbarasuperkondensatorer och annan grön energiteknik. / <p>Vid tidpunkten för disputationen var följande delarbeten opublicerade: delarbete 6 inskickat.</p><p>At the time of the doctoral defence the following papers were unpublished: paper 6 submitted.</p>