Layered crystals with magnetic elements as Co and Fe have been studied. In TlCo2Se2, where Co atoms in one sheet are separated by Tl and Se from the next Co sheet, magnetic interaction within and between the sheets have been studied. Samples doped with 4% 57Fe replaced Co, show a magnetic spiral character with hyperfine fields in a flower shape in the ab-plane. The magnetic moment of 0.46 μB per Co atom derived from the average field is in good agreement with the result from neutron diffraction. In TlCu1.73Fe0.27Se2 the easy axis of magnetisation is the c-axis. The magnetic moment calculated from the Mössbauer data and SQUID magnetrometry is 0.97 μB per Fe atom with TC = 55(5) K. Multilayers of different elements have been studied. The effect of vanadium atoms on iron atoms at the interface of FeNi/V multilayers has been determined and the intermixing at the interface has been calculated to be 2-3 monolayers. For FeNi/Co 1/1 monolayer the magnetic hyperfine field (Bhf) is 45° out-of-plane, while for superlattices containing 2 to 5 monolayers it is in the plane. An study on Fe/Co superlattice were done by experimental, theoretical and simulational methods. The Bhf is highest for the Fe at the second layer next to the interface and gets the bulk value in the centre of thicker Fe layers. Studied magnetic nanoparticles coated with a lipid bilayer (magnetoliposomes) are found to have the magnetite structure but being non-stoichiometric as a result of the manufacturing process. The composition was approximately 32% γ-Fe2O3 and 68% Fe3O4. The oxidation evolution and its effect on magnetic properties of Fe clusters were also studied by means of different techniques. The extraction and insertion mechanism of lithium in the cathode material Li2FeSiO4 has been monitored by in situ x-ray diffraction and Mössbauer spectroscopy during the first two cycles. The relative amount of Fe+3/ Fe+2 at each end state was in good agreement with the results obtained from electrochemical measurements. A possible explanation to the observed lowering of the potential plateau from 3.10 to 2.80 V occurring during the first cycle, involves a structural rearrangement process in which some of the Li ions and the Fe ions are interchanged. The behaviour of small amounts of Fe in brass is investigated using Mössbauer spectroscopy. It was shown that a heat treatment can increase the amount of the precipitates of γ-Fe and ~650° C is the optimal treatment for having the highest amount of this phase.

The dissociation of hydrogen molecules at surfaces is the first step in the absorption process. If the absorbing material is covered by an oxide, this layer will determine the effective uptake rate of an underlying absorbing material. This effect is illustrated when determining the rate of transport of hydrogen through amorphous aluminium oxide layers. The transport rate was determined to be strongly thickness dependent. Hydrogen absorbed in a transition metal causes a volume expansion generated by a strain field around the absorbed hydrogen. This strain field causes a self-trapping of the hydrogen and a temperature dependent distribution in the atomic distances. The local strain field generated by the self-trapping process is found to be crucial for understanding both the hydrogen induced volume expansion as well as the diffusion of hydrogen. Ab-initio molecular dynamics simulations were used to reveal the temperature dependence of the unbinding of the hydrogen and the local strain field and its influence on the diffusion rate. The symmetry of the local strain field is also important for phase formation in metallic films and superlattices which are clamped to a substrate. As the thicknesses reduced from 50 to 10 nm thick vanadium films, substantial finite size effects become apparent in the phase diagrams. The volume change associated with the strain field cannot be accurately measured using x-ray diffraction because of its sensitivity to local arrangements of atoms. X-ray and neutron reflectivity were found to be more reliable probes of global effects of the sumof the local strainfields. Finite size effects in extremely thin V layers were also explored in metallic superlattices composed of iron and vanadium. The co-existence region, composed of a hydrogen gas and a solid-like phase, was found to be suppressed by at least 100 K to below 300 K. The hydrogen-hydrogen interaction can also be influenced by the electronic states in the non hydrogen absorbing layers, as demonstrated when comparing hydrogen absorption in Fe/V and Cr/V superlattices. / Felaktigt tryckt som Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 728

In this thesis, we had studied the transmissivity of electromagnetic waves in onedimensional photonic structures composed by metamaterials in many ways. Applying the formalism of transfer matrix, comparing the transmission spectra between two systems: defective photonic superlattices composed of subwavelength slab widths and a simple photonic structures formed by three layers. Through the effective medium theory, with good accuracy, we had shown the equivalence of the above systems in the spectral region in which there are modes of resonant tunneling for both structures. Furthermore, we had derived a general condition which should be satisfied to observe the resonant modes. Our analytical results may be useful from a technological point of view to propitiate, in the design and development of photonic devices, adjustment or selection of resonant frequencies. Finally, we investigated the electromagnetic wave transmission properties through a multilayer system consisting of alternated layers of air and uniaxially anisotropic metamaterials. The optical axis of each heterostructure coincides with the direction of stacking of the layers. The components of the electric permittivity and magnetic permeability tensors that characterize the metamaterial are modeled by a Drude-type response and split-ring resonator metamaterial response, respectively. Different plasmon frequencies are considered for directions perpendicular and parallel to the optical axis. For oblique incidence, longitudinal plasmon polariton modes are found in the neighborhood of the plasmon frequency along the optical axis. The anisotropy leads to unfolding of nearly dispersionless plasmon-polariton bands either above or below the plasmon frequency. Moreover, it is shown that, even in the presence of loss /absorption, these plasmon polariton modes do survive and, therefore, should be experimentally detected. / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Nessa tese, estudamos a transmissividade de ondas eletromagnéticas em estruturas fotônicas unidimensionais formadas por metamateriais, sob vários aspectos. Aplicando o formalismo de matriz de transferência, comparamos os espectros de transmissão entre dois sistemas: redes defeituosas com camadas no regime de sub-comprimento de onda e simples estruturas fotônicas formadas por três camadas. Através da teoria do meio efetivo, com boa acurácia, mostramos a equivalência dos supracitados sistemas na região espectral em que há modos de tunelamento ressonante para ambas estruturas. Além disso, derivamos uma condição geral que deve ser satisfeita para observarmos os modos ressonantes. Nossos resultados analíticos podem ser úteis do ponto de vista tecnológico por propiciarem, na concepção e no desenvolvimento de dispositivos fotônicos, o ajuste ou seleção das frequências de ressonância. Por fim, investigamos as propriedades de transmissão de ondas eletromagnéticas através de sistemas multicamadas consistindo de camadas alternadas de ar e metamateriais uniaxialmente anisotrópicos. O eixo óptico de cada heteroestrutura coincide com a direção de empilhamento das camadas. As componentes dos tensores de permissividade elétrica e permeabilidade magnética que caracterizam os metamateriais são modeladas por respostas do tipo Drude e split-ring resonator, respectivamente. Diferentes frequências de plasmon são consideradas para as direções perpendiculares e paralela ao eixo óptico. Para incidência oblíqua, modos de plasmon polariton longitudinais são encontrados nas vizinhanças da frequência de plasmon ao longo do eixo óptico. A anisotropia leva ao desdobramento de bandas de plasmon polariton quase sem dispersão acima ou abaixo da frequência de plasmon. Além disso, mostramos que mesmo na presença de perdas/absorções, esses modos de plasmon polariton sobrevivem e, portanto, devem ser detectados experimentalmente.

The present work covers the fabrication and electrical and magnetic investigation of LaNiO3- and LaMnO3- based superlattices (SL). In recent years, several interesting theoretical predictions have been made in these SLs, for example, Mott insulators, metal-insulator transitions, superconductivity, topological insulators, and Chern insulators. Motivated by the promising theoretical predictions, four kinds of SLs with different designed structures and orientations were systematically studied in this thesis. The samples were grown by pulsed laser deposition with in-situ reflection high-energy electron diffraction to monitor the two-dimensional layer-by-layer growth process. In order to ensure the high-quality of SLs, growth parameters were optimised. Characteristic methods like X-ray diffraction, atomic force microscopy, and transmission electron microscopy were used. These measurements proved the high-quality of the SLs and provided the basis for electrical and magnetic measurements. The first studied SL is the (001)-oriented LaNiO3/LaAlO3 SL, which was predicted as a superconductor in theory. Temperature-dependent resistivity measurements revealed a metal-insulator transition by lowering the dimensionality of the LaNiO3 layers in the SLs from three dimensions to two dimensions. The second studied SL is the (111)-oriented LaNiO3/LaAlO3 SL, which was predicted as a topological insulator in theory. The polarity-controlled conductivity was observed and the intrinsic conductivity mechanisms were discussed by means of appropriate modeling. The third studied SL is LaMnO3/LaAlO3 SL, which was predicted as a Chern insulator in theory. By lowering the temperature, a paramagnetic-ferromagnetic phase transition and a thermal activated behavior were observed in the SLs. The last studied SL is the LaNiO3/LaMnO3 SL, in which an exchange bias effect was expected. The studies reveal the exchange bias exists in three kinds of SLs with different orientations.

In the present work, growth and structural characterization of CrB2/TiB2 superlattices on (0001) Al2O3 substrate is studied. The superlattices are grown using a direct current magnetron sputtering (DCMS) system with a base pressure of <9E-7 Torr. For structural characterization X-ray diffraction (XRD), X-ray reflectivity (XRR), transmission electron microscopy (TEM), selected area electron diffraction (SAED), energy dispersive X-ray spectroscopy (EDX), and scanning transmission electron microscopy (STEM) are used. Hardness is measured using nanoindentation technique. For growth of CrB2/TiB2 superlattices it is shown that the sputtering gas pressure of PAr= 4 mTorr, and substrate temperature of T= 600 °C are optimized parameters for growing well-structured superlattices with good interface quality. Superlattices with a layer thickness ratio of Γ= 0.43 (Γ= DTiB2/DCrB2+DTiB2) and a total thickness of 1 μm are deposited with different modulation periods Λ=1, 2, 6, 8, and 10 nm to see the layer-thickness affect on the quality of the structures. XRD and TEM results show that by increasing the modulation period, the quality of superlattices with smooth interfaces increases. The superlattices with modulation period Λ=8 nm is shown to be the best structure having coherent lattice and smooth interfaces up to ~20 periods. The STEM analysis shows that after about 20 periods, grains started to grow at slightly different orientations. A superlattice of TiB2/CrB2(having TiB2 as the first deposited layer) with modulation period Λ=8 nm shows an epitaxial growth of TiB2 on Al2O3 (0001) substrate, however, no big difference between the structure of TiB2/CrB2 and CrB2/TiB2 superlattices is seen. EDX maps and line profiles show that there is a diffusion of CrB2 into TiB2 layers which is a serious problem for obtaining sharp interfaces. STEM also shows that for a small modulation period of Λ=1 nm, there is a faint layered structure, whereas EDX, SAED and XRD indicates a homogenous textures Ti-Cr-B film in this sample. Finally, the hardness measurement shows a hardness value of 29-34 GPa for different modulation periods. The lowest hardness value is related to the sample with modulation period of Λ=1 nm with about 29 GPa, and the highest hardness is related to the sample with Λ=8 nm ith around 34 GPa.

This thesis discusses structural and ferroelectric properties of two well-known classes of materials, perovskite oxides and Hydrogen bonded ferroelectrics, using first-principles calculations. Certain aspects of first principles calculations are central to the problems presented in this thesis. Such as the ability to calculate polarization based on the modern theory of polarization and calculation of ferroelectric property under finite electric displacement field. Therefore, these fundamental theoretical approaches are discussed following an opening section on the basic methodology of density-functional theory. In addition to the discussion on theoretical methods, a brief review of different phenomena and techniques crucial to alter/enhance ferroelectric properties at the interfaces of perovskite materials has been presented along with examples. The first problem presented in this thesis proposes and validates an alternative quantitative measure of ferroelectric(FE) and antiferrodistortive(AFD) instabilities by means of calculating inverse capacitance and layer inverse capacitance of layered perovskites. The presented methodological approach is applied to BaTiO$_{3}$/CaTiO$_{3}$ and PbTiO$_{3}$/SrTiO$_{3}$ superlattices and it precisely estimates FE and AFD instabilities. Here we also present an approach to accurately predict the ferroelectric instabilities in large period superlattices from the statistical coefficients obtained from short period superlattices. In the second problem, we study ferroelectricity in an organic crystal(croconic acid) for which ferroelectric polarization is close to that of bulk BaTiO$_{3}$. We employ new meta-GGA functional named SCAN and revisit all structural and ferroelectric properties. Calculated X-ray absorption spectra(XAS) qualitatively and quantitatively agrees well with experimental O K-edge spectra. By discussing the origin of each XAS peak and their characteristic we demonstrate with a systematic approach the connection between ferroelectricity and XAS in croconic acid. Best to our knowledge such relation has not been realized in past. This study could prove XAS as a new way to measure ferroelectric instability in hydrogen-bonded organic ferroelectrics. / Physics

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Size and Shape Controlled Synthesis and Superparamagnetic Properties of Spinel Ferrites Nanocrystals Qing Song 216 pages Directed by Dr. Z. John Zhang The correlationship between magnetic properties and magnetic couplings is established through the investigations of various cubic spinel ferrite nanocrystals. The results of this thesis contribute to the knowledge of size and shape controlled synthesis of various spinel ferrites and core shell architectured nanocrystals as well as the nanomagnetism in spinel ferrites by systematically investigating the effects of spin orbital coupling, magnetocrystalline anisotropy, exchange coupling, shape and surface anisotropy upon superparamagnetic properties of spinel ferrite nanocrystals. A general synthetic method is developed for size and shape control of metal oxide nanocrystals. The size and shape dependent superparamagnetic properties are discussed. The relationship between spin orbital coupling and magnetocrystalline anisotropy is studied comparatively on variable sizes of spherical CoFe2O4 and Fe3O4 nanocrystals. It also addresses the effect of exchange coupling between magnetic hard phase and soft phase upon magnetic properties in core shell structured spinel ferrite nanocrystals. The role of anisotropic shapes of nanocrystals upon self assembled orientation ordered superstructures are investigated. The effect of thermal stability of molecular precursors upon size controlled synthesis of MnFe2O4 nanocrystals and the size dependent superparamagnetic properties are described.

Vad karaktäriserar en kristall? Svaret på denna till synes enkla fråga blir kanske att det är en anordning av atomer uppradade i periodiska mönster. Så ordnade strukturer kan studeras genom att det uppträder så kallade Braggtoppar i röntgendiffraktionsmönstret. Om frågan gäller elektrontäthetsfördelningen, kanske svaret blir att denna är periodisk och grundar sig på elektronvågor som genomtränger hela kristallen. I och med att nya typer av ordnade system, så kallade kvasikristaller, upptäcks och framställs på artificiell väg blir svaren på dessa frågor mer intrikata. En kristall behöver inte bestå av enheter upprepade periodiskt i rummet, och den klassiska metoden att karaktärisera strukturer via röntgendiffraktionsmönstret kanske inte alls är den allena saliggörande. I denna avhandling visas att ett ordnat gitter vars röntgendiffraktionsmönster saknar inre struktur, dvs är av samma diffusa typ som vad ett oordnat material uppvisar, fortfarande kan ha elektronerna utsträckta över hela strukturen. Detta implicerar att det inte finns något enkelt samband mellan diffraktionsmönstret från gittret och dess fysikaliska egenskaper såsom t ex lokalisering av vågfunktionerna. Man talar om lokalisering när en vågfunktion är begränsad inom en del av materialet och inte utsträckt över hela dess längd, vilket är av betydelse när man vill avgöra huruvida ett material är en isolator, halvledare eller ledare. Det vittnar samtidigt om behovet av att söka efter andra karakteristika när man försöker beskriva skillnaden mellan ett ordnat och ett oordnat material, där den senare kategorin kan uppvisa lokalisering. Resultaten utgör en klassificering av det svåröverskådliga området aperiodiska gitter i en dimension. Det leder till hypotesen att ideala kvasikristaller, genererade med bestämda regler, har kontinuerligt energispektrum av fraktal natur. I reella material spelar korrelation en viktig roll. Vid icke-linjär återkoppling till gittret kan man erhålla intrinsiskt lokaliserade vågor, som i många avseenden beter sig som partiklar, solitoner, vilka har visat sig ha viktiga tillämpningar inom bl a optisk telekommunikation. Sådana vågors roll for lagring och transport av energi har undersökts i teoretiska modeller for optiska vågledare och kristaller där ljuset har en förmåga att manipulera sig självt. / Spectral and dynamical properties of electrons, phonons, electromagnetic waves, and nonlinear coherent excitations in one-dimensional modulated structures with long-range correlations are investigated from a theoretical point of view. First a proof of singular continuous electron spectrum for the tight-binding Schrödinger equation with an on-site potential, which, in analogy with a random potential, has an absolutely continuous correlation measure, is given. The critical behavior of such a localization phenomenon manifests in anomalous diffusion for the time-evolution of electronic wave packets. Spectral characterization of elastic vibrations in aperiodically ordered diatomic chains in the harmonic approximation is achieved through a dynamical system induced by the trace maps of renormalized transfer matrices. These results suggest that the zero Lebesgue measure Cantor-set spectrum (without eigenvalues) of the Fibonacci model for a quasicrystal is generic for deterministic aperiodic superlattices, for which the modulations take values via substitution rules on finite sets, independent of the correlation measure. Secondly, a method to synthesize and analyze discrete systems with prescribed long-range correlated disorder based on the conditional probability function of an additive Markov chain is effectively implemented. Complex gratings (artificial solids) that simultaneously display given characteristics of quasiperiodic crystals and amorphous solids on the Fraunhofer diffraction are designated. A mobility edge within second order perturbation theory of the tight-binding Schrödinger equation with a correlated disorder in the dichotomic potential realizes the success of the method in designing window filters with specific spectral components. The phenomenon of self-localization in lattice dynamical systems is a subject of interest in various physical disciplines. Lattice solitons are studied using the discrete nonlinear Schrödinger equation with on-site potential, modeling coherent structures in, for example, photonic crystals. The instability-induced dynamics of the localized gap soliton is found to thermalize according to the Gibbsian equilibrium distribution, while the spontaneous formation of persisting intrinsic localized modes from the extended out-gap soliton reveals a phase transition of the solution.