A study is presented detailing experimental investigations of magnetization dynamics in nanostructured systems which are coupled magnetically. This work seeks to characterize the anisotropy of such systems through experimental techniques which probe microwave resonant absorption in the materials. A custom-built experimental setup, designed and assembled in our labs, is explained in detail. This setup allows for angular-dependent ferromagnetic resonance (FMR) measurements in the sample plane through vector network analyzer spectroscopy and is adaptable to two different types of coplanar waveguides. This technique has proven effective for characterization of multiple types of magnetic systems, including multilayered structures as detailed here, with different types of anisotropies while allowing us to draw analogies with more common characterization techniques. The angular FMR setup has been used to study coupled systems, such as those coupled through the Ruderman–Kittel–Kasuya–Yosida interaction as well as exchange-biased structures. These types of coupled systems have technological impacts and are highly applied in the components of magnetoresistive random access memory. Using this new characterization technique, properties of synthetic antiferromagnets have been revealed which had not been observed before. In addition to these experiments, magnetic susceptibility and FMR in exchange biased systems have been investigated at temperatures as low as 2 K. This investigation used a new FMR spectrometer and was one of the first studies to use this instrument. For the first time a new method of identifying several types of coupling which can be present in layered nanostructures is presented and supported through comparison with known techniques, thus connecting a new characterization technique for layered structures with decades-old procedures. Many results within this work are also supported theoretically with computer simulations.

In the presented work, first principle studies on electronic structure, stability, and magnetic properties of metal chalcogenide, CrnTem clusters have been carried out within a density functional framework using generalized gradient functions to incorporate the exchange and correlation effects. The energetic and electronic stability was investigated, and it was found that they are not always correlated as seen in the cluster Cr6Te8 which has smaller gap between its HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital) and a high electron affinity of 3.39 eV indicating lower electronic stability whereas higher fragmentation energy indicating energetic stability. The high electron affinity shows that the stability of Cr6Te8 cluster can be enhanced by adding charge donating ligands including PEt3 to form stable Cr6Te8(PEt3)6 clusters as seen in experiments. The other cluster of interest was Cr4Te6 in which energetic stability was accompanied with electronic inertness marked by its large HOMO-LUMO gap, non-magnetic ground state and high fragmentation energy.

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

Optical properties of single-wall carbon nanotubes (SWCNTs) have been extensively studied during the last decade, and much basic knowledge has been accumulated on how light emission, scattering, and absorption occur in the realm of linear optics. However, their nonlinear optical properties remain largely unexplored. Here, we have observed strong third harmonic generation from highly aligned SWCNTs with intense mid-infrared radiation. Through power dependent experiments, we have determined the absolute value of the third-order nonlinear optical susceptibility, ‡ (3) , of our SWCNT film to be 6.92 × 10 -12 esu, which is three orders of magnitude larger than that of the fused silica reference sample we used. Furthermore, through polarization-dependent third harmonic generation experiments, all the nonzero tensor elements of ‡ (3) have also been extracted. The contribution of the weaker tensor elements to the overall ‡ (3) signal has been calculated to be approximately 1/6 of that of the dominant [Special characters omitted.] component. These results open up new possibilities for application of carbon nanotubes in optoelectronics.

Key dynamic processes at nano-scale, such as graphene hydrogenation and fluorination, and carbon nanotube (CNT) growth, cannot be observed in situ in real time. Nevertheless, such processes can be studied through complementary computational methods. This work simulates three important catalytic processes representing the growth of graphitic structures and functionalized graphene. The spillover phenomenon, which has been considered promising for efficient hydrogen storage, includes transfer of H from a metal catalyst to a graphitic receptor, to finally form a graphane island. Although, the spillover is energetically unfavorable to occur on pristine graphene, catalyst saturation provides a way for hydrogen adsorption on the receptor. Ab initio calculations show that the H chemical potential can be increased to a spillover favorable range. Unlike in graphane, upon graphene fluorination different stoichiometric phases form without a nucleation barrier, with the complete CF phase being thermodynamically most stable. After fluorination, graphene electronic properties are transformed from metallic to semiconducting. First-principles and tight-binding methods are used to investigate the patterning of nanoroads and quantum dots on these phases, combining metallic and semiconducting properties on the same sheet. In catalyzed CNT growth the metallic catalyst plays a fundamental role in cap nucleation. Such a mechanism cannot be seen in experiment, nor can it be simulated by first-principles due to its time-scale, yet it can be simulated through molecular dynamics. Tuning the metal-C interaction controls the condition for growth or encapsulation: Surface carbon-diffusion limits the growth below 600 K, and at higher temperatures they depend on cap lift-off. Such tuning can be done through catalyst alloying, as shown through ab initio simulations for Ni-Fe and Cu-Fe bimetallic catalysts. Catalyst shape also plays an important role in CNT growth. The minimization of the Ni surface energy defines the equilibrium crystal shape. Catalyst reshaping is analyzed through C adsorption by first-principles and reactive force fields. The Wulff-construction suggests a significant reduction of the surface energy anisotropy upon C adsorption, based on which a continuum phenomenological model that considers catalyst reshaping in CNT nucleation is formulated. This thesis explains the growth of graphitic structures and functionalized graphene at nano-scale through computational simulations.

The quantum Spin Hall Insulator (QSHI) is a two-dimensional variant of a novel class of materials characterized by topological order, whose unique properties have recently triggered much interest and excitement in the condensed matter community. Most notably, the topological properties of these systems hold great promise in mitigating the difficult problem of decoherence in implementations of quantum computers. Although QSHI has been theoretically predicted in a few different materials, prior to the work presented in this thesis, only the HgTe/CdTe semiconductor system has shown direct evidence for the existence of this phase. Ideally insulating in the bulk, QSHI is characterized by one-dimensional channels at the sample perimeter, which have a helical property, with carrier spin tied to the carrier direction of motion, and protected from elastic back-scattering by time-reversal symmetry. In this thesis we present low temperature transport measurements, showing strong evidence for the existence of proposed helical edge channels in InAs/CaSb quantum wells, which thus emerge as an important alternate to HgTe/CdTe quantum wells in studies of two-dimensional topological insulators and superconductors. Surprisingly, edge modes persist in spite of comparable bulk conduction of non-trivial origin and show only weak dependence on magnetic field in mesoscopic devices. We elucidate that the seeming independence of edge on bulk transport comes due to the disparity in Fermi wave-vectors between the bulk and the edge, leading to a total internal reflection of the edge modes. Furthermore, low Schottky barrier of this material system and good interface to superconductors allows us to probe topological properties of helical channels in Andreev reflection measurements, opening a promising route towards the realization of topologically superconducting phases hosting exotic Majorana modes.