TY - THES A1 - Krivenkov, Maxim T1 - Spin textures and electron scattering in nanopatterned monolayer graphene N2 - The current thesis is focused on the properties of graphene supported by metallic substrates and specifically on the behaviour of electrons in such systems. Methods of scanning tunneling microscopy, electron diffraction and photoemission spectroscopy were applied to study the structural and electronic properties of graphene. The purpose of the first part of this work is to introduce the most relevant aspects of graphene physics and the methodical background of experimental techniques used in the current thesis. The scientific part of this work starts with the extensive study by means of scanning tunneling microscopy of the nanostructures that appear in Au intercalated graphene on Ni(111). This study was aimed to explore the possible structural explanations of the Rashba-type spin splitting of ~100 meV experimentally observed in this system — much larger than predicted by theory. It was demonstrated that gold can be intercalated under graphene not only as a dense monolayer, but also in the form of well-periodic arrays of nanoclusters, a structure previously not reported. Such nanocluster arrays are able to decouple graphene from the strongly interacting Ni substrate and render it quasi-free-standing, as demonstrated by our DFT study. At the same time calculations confirm strong enhancement of the proximity-induced SOI in graphene supported by such nanoclusters in comparison to monolayer gold. This effect, attributed to the reduced graphene-Au distance in the case of clusters, provides a large Rashba-type spin splitting of ~60 meV. The obtained results not only provide a possible mechanism of SOI enhancement in this particular system, but they can be also generalized for graphene on other strongly interacting substrates intercalated by nanostructures of heavy noble d metals. Even more intriguing is the proximity of graphene to heavy sp-metals that were predicted to induce an intrinsic SOI and realize a spin Hall effect in graphene. Bismuth is the heaviest stable sp-metal and its compounds demonstrate a plethora of exciting physical phenomena. This was the motivation behind the next part of the current thesis, where structural and electronic properties of a previously unreported phase of Bi-intercalated graphene on Ir(111) were studied by means of scanning tunneling microscopy, spin- and angle-resolved photoemission spectroscopy and electron diffraction. Photoemission experiments revealed a remarkable, nearly ideal graphene band structure with strongly suppressed signatures of interaction between graphene and the Ir(111) substrate, moreover, the characteristic moiré pattern observed in graphene on Ir(111) by electron diffraction and scanning tunneling microscopy was strongly suppressed after intercalation. The whole set of experimental data evidences that Bi forms a dense intercalated layer that efficiently decouples graphene from the substrate. The interaction manifests itself only in the n-type charge doping (~0.4 eV) and a relatively small band gap at the Dirac point (~190 meV). The origin of this minor band gap is quite intriguing and in this work it was possible to exclude a wide range of mechanisms that could be responsible for it, such as induced intrinsic spin-orbit interaction, hybridization with the substrate states and corrugation of the graphene lattice. The main origin of the band gap was attributed to the A-B symmetry breaking and this conclusion found support in the careful analysis of the interference effects in photoemission that provided the band gap estimate of ~140 meV. While the previous chapters were focused on adjusting the properties of graphene by proximity to heavy metals, graphene on its own is a great object to study various physical effects at crystal surfaces. The final part of this work is devoted to a study of surface scattering resonances by means of photoemission spectroscopy, where this effect manifests itself as a distinct modulation of photoemission intensity. Though scattering resonances were widely studied in the past by means of electron diffraction, studies about their observation in photoemission experiments started to appear only recently and they are very scarce. For a comprehensive study of scattering resonances graphene was selected as a versatile model system with adjustable properties. After the theoretical and historical introduction to the topic of scattering resonances follows a detailed description of the unusual features observed in the photoemission spectra obtained in this work and finally the equivalence between these features and scattering resonances is proven. The obtained photoemission results are in a good qualitative agreement with the existing theory, as verified by our calculations in the framework of the interference model. This simple model gives a suitable explanation for the general experimental observations. The possibilities of engineering the scattering resonances were also explored. A systematic study of graphene on a wide range of substrates revealed that the energy position of the resonances is in a direct relation to the magnitude of charge transfer between graphene and the substrate. Moreover, it was demonstrated that the scattering resonances in graphene on Ir(111) can be suppressed by nanopatterning either by a superlattice of Ir nanoclusters or by atomic hydrogen. These effects were attributed to strong local variations of tork function and/or destruction of long-range order of thephene lattice. The tunability of scattering resonances can be applied for optoelectronic devices based on graphene. Moreover, the results of this study expand the general understanding of the phenomenon of scattering resonances and are applicable to many other materials besides graphene. N2 - Die vorliegende Arbeit beschäftigt sich mit den Eigenschaften von Graphen auf metallischen Substraten und speziell mit dem Verhalten von Elektronen in solchen Systemen. Der wissenschaftliche Teil dieser Arbeit beginnt mit der umfassenden Untersuchung von Nanostrukturen, die in Au-interkaliertem Graphen auf Ni(111) auftreten, mittels Rastertunnelmikroskopie (RTM). Diese Studie zielte darauf ab, die möglichen strukturellen Erklärungen der experimentell in diesem System beobachteten Rashba- Spin-Aufspaltung von ~100 meV zu untersuchen — die viel größer als theoretisch vorhergesagt ist. Es wurde gezeigt, dass Gold unter Graphen nicht nur als dichte Monolage interkaliert werden kann, sondern auch in Form von exakt periodischen Anordnungen von Nanoclustern, einer Struktur, die bisher nicht beschrieben wurde. Solche Nanocluster-Arrays können Graphen von dem stark wechselwirkenden Ni-Substrat entkoppeln und es quasi freistehend machen, wie unsere Dichtefunktionaltheorie-Studie zeigt. Gleichzeitig bestätigen die Dichtefunktionaltheorie-Rechnungen eine starke Erhöhung der durch Proximity induzierten Spin-Bahn-Wechselwirkung (SBW) in Graphen durch solche Nanocluster im Vergleich zu einer homogenen Gold-Monolage. Dieser Effekt, der im Falle von Clustern auf den verringerten Graphen-Au-Abstand zurückgeführt wird, liefert eine große Spinaufspaltung vom Rashba-Typ von ~60 meV. Die erhaltenen Ergebnisse liefern nicht nur einen möglichen Mechanismus zur Erhöhung der SBW in diesem speziellen System, sondern können auch auf Graphen auf anderen stark wechselwirkenden Substraten verallgemeinert werden, die mit Nanostrukturen von schweren Edelmetallen interkaliert sind. Noch faszinierender ist die Nähe von Graphen zu schweren sp-Metallen, von denen vorhergesagt wurde, dass sie eine intrinsische SBW induzieren und einen Spin-Hall-Effekt in Graphen realisieren. Wismut ist das schwerste stabile sp-Metall und seine Verbindungen zeigen eine Vielzahl aufregender physikalischer Phänomene. Dies war die Motivation für den nächsten Teil der vorliegenden Arbeit, in dem strukturelle und elektronische Eigenschaften einer bisher nicht beschriebenen Phase von Bismuth-interkaliertem Graphen auf Ir(111) untersucht werden. Experimente ergaben eine nahezu ideale Graphenbandstruktur mit stark unterdrückten Wechselwirkungssignaturen zwischen Graphen und dem Ir(111)-Substrat. Die gesamten experimentellen Daten belegen, dass Bi eine dichte interkalierte Schicht bildet, die Graphen effizient vom Substrat entkoppelt. Die Wechselwirkung manifestiert sich nur in der Ladungsdotierung vom n-Typ (~0,4 eV) und einer Bandlücke am Dirac-Punkt (~190 meV). Den Ursprung dieser Bandlücke zu ermitteln ist sehr komplex, und in dieser Arbeit konnte eine Vielzahl von Mechanismen ausgeschlossen werden, die dafür verantwortlich sein könnten, wie etwa induzierte intrinsische SBW, Hybridisierung mit den Substratzuständen und Riffelung des Graphen-Gitters. Der Hauptursprung der Bandlücke wurde einem Bruch der A-B -Symmetrie zugeschrieben, und diese Schlussfolgerung stützte sich auf eine eingehende Analyse der Interferenzeffekte bei der Photoemission, die eine Abschätzung der Bandlücke von ~140 meV lieferte. Während sich die vorherigen Kapitel auf die Anpassung der Eigenschaften von Graphen durch die Nähe zu Schwermetallen konzentrierten, ist Graphen allein ein großartiges Objekt, um verschiedene physikalische Effekte an Kristalloberflächen zu untersuchen. Der letzte Teil dieser Arbeit befasst sich mit der Photoemissionsspektroskopie Untersuchung von Oberflächenstreuresonanzen, deren Effekt sich in einer deutlichen Modulation der Photoemissionsintensität manifestiert. Obwohl Streuresonanzen in der Vergangenheit häufig mittels Elektronenbeugung untersucht wurden, erschienen einige wenige Studien über ihre Beobachtung in Photoemissionsexperimenten erst vor kurzem. Für eine umfassende Untersuchung der Streuresonanzen wurde Graphen als vielseitiges Modellsystem mit einstellbaren Eigenschaften ausgewählt. Das Kapitel beginnt mit einer historischen Einführung in das Thema Streuresonanzen, gefolgt von der Beschreibung der ungewöhnlichen Photoemissionsspektralmerkmale, die in dieser Arbeit erhalten wurden. Schließlich wird die Äquivalenz zwischen diesen Merkmalen und Streuresonanzen bewiesen. Die erhaltenen Photoemissionsergebnisse stimmen qualitativ gut mit der bestehenden Theorie überein, wie unsere Berechnungen im Rahmen des Interferenzmodells belegen. Dieses einfache Modell liefert eine geeignete Erklärung für die Gesamtheit der experimentellen Beobachtungen. Möglichkeiten, die Streuresonanzen zu modifizieren wurden ebenfalls untersucht. Eine systematische Untersuchung von Graphen auf einer Vielzahl von Substraten ergab, dass die Energieposition der Resonanzen in direktem Zusammenhang mit der Größe des Ladungstransfers zwischen Graphen und Substrat steht. Darüber hinaus wurde gezeigt, dass die Streuresonanzen in Graphen auf Ir(111) durch Nanostrukturierung entweder durch ein Übergitter von Ir-Nanoclustern oder durch atomaren Wasserstoff unterdrückt werden können. Diese Effekte wurden auf starke lokale Variationen der Austrittsarbeit und/oder die Zerstörung der langreichweitigen Ordnung des Graphengitters zurückgeführt. Die Abstimmbarkeit von Streuresonanzen kann für optoelektronische Bauelemente auf der Basis von Graphen verwendet werden. Darüber hinaus erweitern die Ergebnisse dieser Studie das allgemeine Verständnis des Phänomens der Streuresonanzen und sind neben Graphen auch auf viele andere Materialien anwendbar. T2 - Spin-Texturen und Elektronenstreuung in nanostrukturiertem Monolage-Graphen KW - graphene KW - spin texture KW - scattering resonances KW - Rashba effect KW - bismuth KW - Rashba-Effekt KW - Wismut KW - Graphen KW - Streuresonanzen KW - Spin Textur Y1 - 2020 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-487017 ER - TY - JOUR A1 - Krivenkov, Maxim A1 - Golias, Evangelos A1 - Marchenko, Dmitry A1 - Sanchez-Barriga, Jaime A1 - Bihlmayer, Gustav A1 - Rader, Oliver A1 - Varykhalov, Andrei T1 - Nanostructural origin of giant Rashba effect in intercalated graphene JF - 2D Materials N2 - To enhance the spin-orbit interaction in graphene by a proximity effect without compromising the quasi-free-standing dispersion of the Dirac cones means balancing the opposing demands for strong and weak graphene-substrate interaction. So far, only the intercalation of Au under graphene/Ni(111) has proven successful, which was unexpected since graphene prefers a large separation (similar to 3.3 angstrom) from a Au monolayer in equilibrium. Here, we investigate this system and find the solution in a nanoscale effect. We reveal that the Au largely intercalates as nanoclusters. Our density functional theory calculations show that the graphene is periodically stapled to the Ni substrate, and this attraction presses graphene and Au nanoclusters together. This, in turn, causes a Rashba effect of the giant magnitude observed in experiment. Our findings show that nanopatterning of the substrate can be efficiently used for engineering of spin-orbit effects in graphene. KW - quasi-free-standing graphene KW - Ni(111) KW - gold intercalation KW - spin-orbit interaction KW - nanoclusters KW - STM KW - DFT Y1 - 2017 U6 - https://doi.org/10.1088/2053-1583/aa7ad8 SN - 2053-1583 VL - 4 IS - 3 PB - IOP Publ. Ltd. CY - Bristol ER - TY - JOUR A1 - Krivenkov, Maxim A1 - Marchenko, Dimitry A1 - Sánchez-Barriga, Jaime A1 - Golias, Evangelos A1 - Rader, Oliver A1 - Varykhalov, Andrei T1 - Origin of the band gap in Bi-intercalated graphene on Ir(111) JF - 2D Materials N2 - Proximity to heavy sp-elements is considered promising for reaching a band gap in graphene that could host quantum spin Hall states. The recent report of an induced spin-orbit gap of 0.2 eV in Pb-intercalated graphene detectable by spin-resolved photoemission has spurred renewed interest in such systems (Klimovskikh et al 2017 ACS Nano 11, 368). In the case of Bi intercalation an even larger band gap of 0.4 eV has been observed but was assigned to the influence of a dislocation network (Warmuth et al 2016 Phys. Rev. B 93, 165 437). Here, we study Bi intercalation under graphene on Ir(111) and report a nearly ideal graphene dispersion without band replicas and no indication of hybridization with the substrate. The band gap is small (0.19 eV) and can be tuned by +/- 25 meV through the Bi coverage. The Bi atomic density is higher than in the recent report. By spin-resolved photoemission we exclude induced spin-orbit interaction as origin of the gap. Quantitative agreement of a photoemission intensity analysis with the measured band gap suggests sublattice symmetry breaking as one of the possible band gap opening mechanisms. We test several Bi structures by density functional theory. Our results indicate the possibility that Bi intercalates in the phase of bismuthene forming a graphene-bismuthene van der Waals heterostructure. KW - graphene KW - bismuth KW - Ir(111) KW - spin-orbit interaction KW - ARPES KW - STM KW - bismuthene Y1 - 2021 U6 - https://doi.org/10.1088/2053-1583/abd1e4 SN - 2053-1583 VL - 8 IS - 3 PB - IOP Publ. Ltd. CY - Bristol ER - TY - JOUR A1 - Sajedi, Maryam A1 - Krivenkov, Maxim A1 - Marchenko, Dmitry A1 - Varykhalov, Andrei A1 - Sanchez-Barriga, Jaime A1 - Rienks, Emile D. L. A1 - Rader, Oliver T1 - Absence of a giant Rashba effect in the valence band of lead halide perovskites JF - Physical review : B, Condensed matter and materials physics N2 - For hybrid organic-inorganic as well as all-inorganic lead halide perovskites a Rashba effect has been invoked to explain the high efficiency in energy conversion by prohibiting direct recombination. Both a bulk and surface Rashba effect have been predicted. In the valence band of methylammonium (MA) lead bromide a Rashba effect has been reported by angle-resolved photoemission and circular dichroism with giant values of 7-11 eV angstrom. We present band dispersion measurements of MAPbBr(3) and spin-resolved photoemission of CsPbBr3 to show that a large Rashba effect detectable by photoemission or circular dichroism does not exist and cannot be the origin of the high effciency. Y1 - 2020 U6 - https://doi.org/10.1103/PhysRevB.102.081116 SN - 2469-9950 SN - 2469-9969 VL - 102 IS - 8 PB - American Institute of Physics; American Physical Society (APS) CY - Woodbury, NY ER - TY - GEN A1 - Varykhalov, Andrei A1 - Freyse, Friedrich A1 - Aguilera, Irene A1 - Battiato, Marco A1 - Krivenkov, Maxim A1 - Marchenko, Dmitry A1 - Bihlmayer, Gustav A1 - Blugel, Stefan A1 - Rader, Oliver A1 - Sanchez-Barriga, Jaime T1 - Effective mass enhancement and ultrafast electron dynamics of Au(111) surface state coupled to a quantum well T2 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - We show that, although the equilibrium band dispersion of the Shockley-type surface state of two-dimensional Au(111) quantum films grown on W(110) does not deviate from the expected free-electron-like behavior, its nonequilibrium energy-momentum dispersion probed by time- and angle-resolved photoemission exhibits a remarkable kink above the Fermi level due to a significant enhancement of the effective mass. The kink is pronounced for certain thicknesses of the Au quantum well and vanishes in the very thin limit. We identify the kink as induced by the coupling between the Au(111) surface state and emergent quantum-well states which probe directly the buried gold-tungsten interface. The signatures of the coupling are further revealed by our time-resolved measurements which show that surface state and quantum-well states thermalize together behaving as dynamically locked electron populations. In particular, relaxation of hot carriers following laser excitation is similar for both surface state and quantum-well states and much slower than expected for a bulk metallic system. The influence of quantum confinement on the interplay between elementary scattering processes of the electrons at the surface and ultrafast carrier transport in the direction perpendicular to the surface is shown to be the reason for the slow electron dynamics. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 1354 KW - AG KW - films Y1 - 2020 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-549892 SN - 1866-8372 IS - 1 ER - TY - JOUR A1 - Varykhalov, Andrei A1 - Freyse, Friedrich A1 - Aguilera, Irene A1 - Battiato, Marco A1 - Krivenkov, Maxim A1 - Marchenko, Dmitry A1 - Bihlmayer, Gustav A1 - Blugel, Stefan A1 - Rader, Oliver A1 - Sanchez-Barriga, Jaime T1 - Effective mass enhancement and ultrafast electron dynamics of Au(111) surface state coupled to a quantum well JF - Physical Review Research N2 - We show that, although the equilibrium band dispersion of the Shockley-type surface state of two-dimensional Au(111) quantum films grown on W(110) does not deviate from the expected free-electron-like behavior, its nonequilibrium energy-momentum dispersion probed by time- and angle-resolved photoemission exhibits a remarkable kink above the Fermi level due to a significant enhancement of the effective mass. The kink is pronounced for certain thicknesses of the Au quantum well and vanishes in the very thin limit. We identify the kink as induced by the coupling between the Au(111) surface state and emergent quantum-well states which probe directly the buried gold-tungsten interface. The signatures of the coupling are further revealed by our time-resolved measurements which show that surface state and quantum-well states thermalize together behaving as dynamically locked electron populations. In particular, relaxation of hot carriers following laser excitation is similar for both surface state and quantum-well states and much slower than expected for a bulk metallic system. The influence of quantum confinement on the interplay between elementary scattering processes of the electrons at the surface and ultrafast carrier transport in the direction perpendicular to the surface is shown to be the reason for the slow electron dynamics. KW - AG KW - Flims Y1 - 2020 U6 - https://doi.org/10.1103/PhysRevResearch.2.013343 SN - 0031-9007 VL - 2 IS - 1 SP - 1 EP - 9 PB - American Physical Society CY - Ridge, NY ER -