Graphene, a two dimensional single layer of graphite, attracts a lot of attention of researchers around the globe due to its remarkable physical properties and application potential. The origin can thereby be found in the peculiar electronic structure since graphene is a zero gap semi-conductor with a linear energy dispersion in the vicinity of the Fermi level. Consequently, the charge carriers in graphene mimic massless Dirac Fermions which brings principles of quantum electrodynamics and exotic effects like Klein tunneling into a bench-top experiment. Modifying the electronic and/or crystal structure structure by functionalization might therefore as well lead to new tantalizing physical properties, novel compound materials based on graphene like graphane (fully hydrogenated graphene) or flourographene (fluorinated graphene), and ultimately new applications. In this work, the influences on the electronic structure of graphene are investigated with photoemission spectroscopies after covalent functionalization by atomic hydrogen and ionic functionalization with potassium. Regarding hydrogenation, the formation of tunable bandgap is observed along with a full recovery of the electronic properties of graphene upon removing the hydrogen by thermal annealing. Using high resolution x-ray photoemission and molecular dynamics simulations, the formation of a C4H structure is predicted for substrate supported graphene at a saturation H-coverage of 25%, due to a preferential para- arrangement of hydrogen atoms. In fully electron doped, hydrogenated graphene the formation of dispersionless hydrogen impurity state is observed with angle-resolved photoemission spectroscopy. This flat state is extended over the whole Brillouin zone and according to calculations not localized. Potassium-doped graphene shows a similar doping level as its 3D parent component, the graphite intercalation compound KC8. Investigating the electron-phonon coupling in doped graphene, by direct derivation of the Eliashberg-function, shows an asymmetric coupling strength along the high-symmetry directions in the Brillouin Zone of graphene. In the K-M direction additional low energetic contributions could be identified which may originate from out-of-plane phonon modes. Regarding the electron-phonon-coupling strength of the high energy in-plane phonon modes a reasonable agreement with theoretical predictions is found.

Topological insulators (TI) are a new phase of matter with very exotic electronic properties on their surface. As a direct consequence of the topological order, the surface electrons of TI form bands that cross the Fermi surface odd number of times and are guaranteed to be metallic. They also have a linear energy-momentum dispersion relationship that satisfies the Dirac equation and are therefore called Dirac fermions. The surface Dirac fermions of TI are spin-polarized with the direction of the spin locked to momentum and are immune from certain scatterings. These unique properties of surface electrons provide a platform for utilizing TI in future spin-based electronics and quantum computation. The surface bands of 3D TI can be directly mapped by angle-resolved photoemission spectroscopy (ARPES) and the spin polarization can be determined by spin-resolved ARPES. These types of experiments are the first to establish the 3D topological order, which demonstrates the power of ARPES in probing the surface of strongly spin-orbit coupled materials. Extensive investigation of TI has ranged from understanding the fundamental electronic and lattice structure of various TI compounds to building TI-based devices in search of more exotic particles such as Majorana fermions and magnetic monopoles. Surface-sensitive techniques that can efficiently disentangle the charge and spin degrees of freedom have been crucially important in tackling the multi-faceted problems of TI. In this thesis, I show that laser-based ARPES in combination with a time-of-flight spectrometer is a powerful tool to study the spin structure and charge dynamics of the Dirac fermions on the surface of TI. Chapter 1 gives a brief introduction of TI. Chapter 2 describes the basic principles behind ARPES and time-resolved ARPES (TrARPES). Chapter 3 provides a detailed account of the experimental setup to perform laser-based ARPES and TrARPES. In Chapters 4 and 5, how these two techniques are effectively applied to investigate two unique electronic properties of TI is elaborated. Through these studies, I have obtained a complete mapping of the spin texture of several prototypical topological insulators and have uncovered the cooling mechanism governing the hot surface Dirac fermions. / Physics

This thesis is devoted to studies of high temperature superconductors and related materials using the angle-resolved photoemission spectroscopy (ARPES). Though there is no accepted theory of superconductivity, encompassing high-$T_{\\rm c}$ materials, there is enough evidence to believe that superconductivity can always be interpreted as stemming from pairing of electrons by interaction with bosons, and $T_{\\rm c}$ is determined by effectiveness of such a pairing. ARPES, owing to the possibility of recording energy- and momentum-resolved electronic spectrum, is a powerful probe of the normal-state electronic structure, which is an important prerequisite for the superconductivity, and implications of the electron pairing, such as emergence of the superconducting gap and finer features below $T_{\\rm c}$. Based on ARPES data one can quantify the electronic interactions by analysis of kinks in the dispersion curves, spectral line widths etc. In current work new methods of ARPES data analysis were developed and applied to the spectra taken from cuprate and iron-based high-$T_{\\rm c}$. The possibility to analyze the macroscopic response of solids in the normal state as well as in the superconducting and charge-density-wave phases basing on the experimentally measured renormalized band dispersion and anisotropic superconducting and charge-density-wave gap was shown. The thesis consists of five parts. Part 1 introduces the employed notions of electrons in solids and methods of their investigation. Part 2 describes the Voigt fitting procedure, allowed for purification of the spectra from resolution effects, and, consequently, for determination of the quasiparticle scattering rate with enhanced precision. In Part 3 the calculation of the temperature-dependent Hall coefficient in the charge-density-wave-bearing 2H-TaSe$_2$ from the band dispersion, measured in ARPES, is presented, and comparison to the independent magnetotransport measurements is shown. The extraction of the band dispersion of Ba$_{1-x}$K$_{x}$Fe$_2$As$_2$ and LiFeAs from ARPES data can be found in Part 4. Agreement with Hall effect measurements on the same samples is demonstrated. Part 5 introduces the extraction of the momentum-dependent superconducting gap in iron arsenides from fitting of ARPES spectra to Dynes function. The superfluid density was calculated from the band dispersion and the superconducting gap, measured in ARPES, and compared to the ones measured by different techniques.

Catalysts based on cerium oxide are ubiquitous in industrial-scale chemical conversion. Here, a thorough study of their fundamental properties is undertaken via a model system ap- proach with the goal of furthering rational design in heterogeneous catalysis. A focus is put on understanding the behavior of oxygen vacancies in cerium oxide with respect to atomic co-ordination and electronic structure perturbations. Utilizing state-of-the-art probing tech- niques, a scalable model system framework is developed that allows for control over both the oxygen vacancy concentration and local co-ordination. High precision of the innova- tive approach facilitated observation of new phases of substoichiometric cerium oxide and lead to a first-of-a-kind investigation of the electronic structure of cerium oxide throughout isostructural transition from CeO2 to Ce2O3. The acquired results advance fundamental understanding of essential properties of cerium oxide that are relevant to its utilization in heterogeneous catalysis and open new pathways for functionalization of cerium oxide-based materials. Furthermore, the methodology developed in the thesis is transferable to other important reducible oxides. 1

This thesis is devoted to studies of high temperature superconductors and related materials using the angle-resolved photoemission spectroscopy (ARPES). Though there is no accepted theory of superconductivity, encompassing high-$T_{\\rm c}$ materials, there is enough evidence to believe that superconductivity can always be interpreted as stemming from pairing of electrons by interaction with bosons, and $T_{\\rm c}$ is determined by effectiveness of such a pairing. ARPES, owing to the possibility of recording energy- and momentum-resolved electronic spectrum, is a powerful probe of the normal-state electronic structure, which is an important prerequisite for the superconductivity, and implications of the electron pairing, such as emergence of the superconducting gap and finer features below $T_{\\rm c}$. Based on ARPES data one can quantify the electronic interactions by analysis of kinks in the dispersion curves, spectral line widths etc. In current work new methods of ARPES data analysis were developed and applied to the spectra taken from cuprate and iron-based high-$T_{\\rm c}$. The possibility to analyze the macroscopic response of solids in the normal state as well as in the superconducting and charge-density-wave phases basing on the experimentally measured renormalized band dispersion and anisotropic superconducting and charge-density-wave gap was shown. The thesis consists of five parts. Part 1 introduces the employed notions of electrons in solids and methods of their investigation. Part 2 describes the Voigt fitting procedure, allowed for purification of the spectra from resolution effects, and, consequently, for determination of the quasiparticle scattering rate with enhanced precision. In Part 3 the calculation of the temperature-dependent Hall coefficient in the charge-density-wave-bearing 2H-TaSe$_2$ from the band dispersion, measured in ARPES, is presented, and comparison to the independent magnetotransport measurements is shown. The extraction of the band dispersion of Ba$_{1-x}$K$_{x}$Fe$_2$As$_2$ and LiFeAs from ARPES data can be found in Part 4. Agreement with Hall effect measurements on the same samples is demonstrated. Part 5 introduces the extraction of the momentum-dependent superconducting gap in iron arsenides from fitting of ARPES spectra to Dynes function. The superfluid density was calculated from the band dispersion and the superconducting gap, measured in ARPES, and compared to the ones measured by different techniques.

Graphene, a two dimensional single layer of graphite, attracts a lot of attention of researchers around the globe due to its remarkable physical properties and application potential. The origin can thereby be found in the peculiar electronic structure since graphene is a zero gap semi-conductor with a linear energy dispersion in the vicinity of the Fermi level. Consequently, the charge carriers in graphene mimic massless Dirac Fermions which brings principles of quantum electrodynamics and exotic effects like Klein tunneling into a bench-top experiment. Modifying the electronic and/or crystal structure structure by functionalization might therefore as well lead to new tantalizing physical properties, novel compound materials based on graphene like graphane (fully hydrogenated graphene) or flourographene (fluorinated graphene), and ultimately new applications. In this work, the influences on the electronic structure of graphene are investigated with photoemission spectroscopies after covalent functionalization by atomic hydrogen and ionic functionalization with potassium. Regarding hydrogenation, the formation of tunable bandgap is observed along with a full recovery of the electronic properties of graphene upon removing the hydrogen by thermal annealing. Using high resolution x-ray photoemission and molecular dynamics simulations, the formation of a C4H structure is predicted for substrate supported graphene at a saturation H-coverage of 25%, due to a preferential para- arrangement of hydrogen atoms. In fully electron doped, hydrogenated graphene the formation of dispersionless hydrogen impurity state is observed with angle-resolved photoemission spectroscopy. This flat state is extended over the whole Brillouin zone and according to calculations not localized. Potassium-doped graphene shows a similar doping level as its 3D parent component, the graphite intercalation compound KC8. Investigating the electron-phonon coupling in doped graphene, by direct derivation of the Eliashberg-function, shows an asymmetric coupling strength along the high-symmetry directions in the Brillouin Zone of graphene. In the K-M direction additional low energetic contributions could be identified which may originate from out-of-plane phonon modes. Regarding the electron-phonon-coupling strength of the high energy in-plane phonon modes a reasonable agreement with theoretical predictions is found.

Syftet med denna avhandling är att bidra till forskningen av befintliga TMD:er (på Engelska transition metal dichalcogenide-TMD) som visar laddningstäthetsvågor och supraledning vid låga temperaturer (som 2H-TaS2). 2H-TaS2 är också känt för att visa supraledning vid 2K. Dessutom kommer en betydande del av denna avhandling att ägnas åt analysen av den elektronstrukturen nära Ferminivån av Cu-interkalerad TiSe2 och speciellt dess laddningstäthets-beteende vid temperaturer under 200K. Medan de teoretiska modellerna överlåts till teoretikerna, är följande sidor tillägnad att ge ett kvalitativt perspektiv på materialen. Avhandlingen är uppdelad i fyra huvudavsnitt: grundläggande begrepp, experiment-ella tekniker, tidigare rön och dataanalys. Det första avsnittet syftar till att introducera de viktigaste relevanta begreppen för att spåra de många möjliga fenomen som händer i bulk-TMD, speciellt Fe-dopade TaS2 i 2H-fasen och Cu-interkalerade TiSe2 i 1T fas. Elektronisk dispersion i fasta ämnen kommer att diskuteras på ett inledande och fenomenologiskt sätt utan rigorösa härledningar och ska hjälpa läsaren att förstå kapitlen därefter. / Motivation: The family of transition metal dichalcogenides (TMDs) has captured the fascination of researchers worldwide due to their remarkable properties and vast potential for various applications. These 2D materials exhibit a wide range of electronic, optical, and mechanical characteristics, making them incredibly versatile. From semiconductors to superconductors, TMDs offer a rich playground for exploration in condensed matter physics and materials science. Their unique properties are paving the way for breakthroughs in electronics, optoelectronics, energy storage, and beyond. As we delve deeper into the world of TMDs, we uncover new opportunities to revolutionize technology and enhance our understanding of the fundamental principles governing the behavior of matter. Joining the journey of discovery within the TMD family promises exciting challenges and the potential to contribute to the forefront of scientific and technological advancement.  The aim of this thesis is to add to the canon of existing TMDs that display charge density waves and superconductivity at low temperatures (like 2H-TaS2). 2H-TaS2 is also known to display superconductivity at 2K. Additionally, a substantial part of this thesis will be dedicated to the analysis of the electronic structure near the Fermi level of Cu-intercalated TiSe2 and especially its charge-density behaviour at temperatures below 200K. While the theoretical models are left to the theoreticians, the following pages are dedicated to giving a qualitative perspective on the materials. Thesis Outline: The primary goal of this thesis is to provide an introduction to both widely utilized and cutting-edge experimental setups employed by physicists worldwide. This will enable the acquisition of practical experience, facilitating the mastery of best practices and analysis techniques within the realm of experimental condensed matter physics. The thesis is split into four main sections: fundamental concepts, experimental techniques, previous findings and data analysis. The first section is occupied to introduce the main relevant concepts to trace the many possible phenomena happening in bulk TMDs, specifically Fe-doped TaS2 in the 2H phase and Cu-intercalated TiSe2 in the 1T phase. Subjects such as electronic dispersion in solids will be discussed in a rather introductory and phenomenological manner without rigorous derivations and shall aid the reader in understanding the chapters thereafter.

The effect of spin-orbit coupling had once been thought to be a minor perturbation to the low energy band structure that could be ignored. Instead, a surge in recent theoretical and experimental efforts have shown spin-orbit interactions to have significant consequences. The main objective of this thesis is to investigate the role of the orbital sector and crystal symmetries in governing the spin texture in materials that have strong spin- orbit interactions. This can be accessed through a combination of spin- and angle-resolved photoemission spectroscopy (ARPES and spin-ARPES), both of which are powerful techniques for probing the one-electron band structure plus interactions, and supported by density functional theory calculations (DFT). We focus first on a globally inversion asymmetric material, the layered semiconductor BiTeI, which hosts a giant spin-splitting of its bulk bands. We show that these spin-split bands develop a previously undiscovered, momentum-space ordering of the atomic orbitals. We demonstrate this orbital texture to be atomic element specific by exploiting resonant enhancements in ARPES. These orbital textures drive a hierarchy of spin textures that are then tied to the constituent atomic layers. This opens routes to controlling the spin-splitting through manipulation of the atomic orbitals. This is contrasted against a material where inversion symmetry is globally upheld but locally broken within each monolayer of a two layer unit cell. Through our ARPES and spin-ARPES measurements of 2H-NbSe2, we discover the first experimental evidence for a strong out-of-plane spin polarisation that persists up to the Fermi surface in this globally inversion sym- metric material. This is found to be intrinsically linked to the orbital character and dimensionality of the underlying bands. So far, previous theories underpinning this (and related) materials' collective phases assume a spin- degenerate Fermi sea. We therefore expect this spin-polarisation to play a role in determining the underlying mechanism for the charge density wave phase and superconductivity. Through these studies, this thesis then develops the importance of global versus local inversion symmetry breaking and uncovers how this is intricately tied to the underlying atomic orbital configuration.

No description available.

In this dissertation different van der Waals heterostructures such as graphene-MoS2 and MoTe2-MoS2 were prepared and characterized. In the first heterostructure, polycrystalline graphene was synthesized by chemical vapor deposition and transferred on top of MoS2 single crystal. In the second heterostructure, MoTe2 monolayers were deposited on MoS2 by molecular beam epitaxy. Characterization of graphene-MoS2 heterostructures was conducted by spin and angle resolve spectroscopy which showed that the electronic structure of the bulk MoS2 and graphene in this van der Waals heterostructures is modified. For MoS2 underneath the graphene, a band structure renormalization and spin polarization are observed. The band structure of MoS2 is modified because the graphene induces screening which shifts the Г-point ~150 meV to lower binding compared to the sample without graphene. The spin polarization is explained by the dipole arising from band bending which breaks the symmetry at the MoS2 surface. For graphene, the band structure at lower binding energy shows that the Dirac cone remains intact with no significant doping. Instead, away from the Fermi level the formation of several gaps in the pi-band due to hybridization with states from the MoS2 is observed. For the heterostructures made depositing monolayer of MoTe2 on MoS2, the morphology, structure and electronic structure were studied. Two dimensional growth is observed under tellurium rich growth conditions and a substrate temperature of 200 °C but formation of a complete monolayer was not achieved. The obtained MoTe2 monolayer shows a high density of the mirror-twins grain boundaries arranged in a pseudo periodic wagon wheel pattern with a periodicity of ~2.6 nm. These grain boundary are formed due to Te-deficiency during the growth. The defect states from these domain boundary pin the Fermi level in MoTe2 and thus determine the band alignment in the MoTe2-MoS2 heterostructures.