Diese Dissertation beschäftigt sich mit der Grenzflächenausbildung von dünnen Tantal- und Titan-basierenden Schichten zu den piezoelektrischen Substratmaterialien Lithiumniobat sowie Lithiumtantalat, als Teil eines Schichtstapels für die Metallisierung akustischer Oberflächenbauelemente. Ziel ist es das grundlegende Verständnis für die chemischen Wechselwirkungen beim Aufwachsen der Schichten, ihrer thermischen und zeitlichen Stabilität sowie ihrer Effekte auf das Schichtwachstum einer Deckschicht bestehend aus Aluminium zu gewinnen. Ein Schwerpunkt war die Präparation der Substratoberflächen hinsichtlich einer Oberflächenreinigung und -modifikation. Zu diesem Zweck wurden neben verschiedenen Standard-Verfahren auch eine eigens angefertigte plasmagestützte Oberflächenbehandlung systematisch analysiert. Auf derart präparierten Substraten fanden im Folgenden die Schichtabscheidung und die Analyse des Schichtwachstums, hauptsächlich mit winkelaufgelöster Photoelektronenspektroskopie, statt. Anhand von thermischen Belastungen sowie zeitlicher Veränderungen der Schichten im Vakuum konnten grundlegende Aussagen zur Stabilität der Grenzflächen gewonnen werden. Zur Komplettierung des Schichtstapels wurden auf ausgewählten Substrat-Schicht Kombinationen das Wachstum von Aluminiumschichten hinsichtlich ihrer unterschiedlicher Texturbildung analysiert und Aussagen zur Relevanz chemischer Ursachen getroffen. / This dissertation addresses the interface formation between thin Tantalum and Titanium based layers onto the piezoelectric substrate materials Lithiumniobate and Lithiumtantalate as part of a metallisation stack for surface acoustic wave devices. The goal is to extend the fundamental knowledge of chemical interactions during layer growth, its thermal and temporal stability plus its effects on the layer growth of an Aluminium cover layer. One focus lies on the preparation of the substrate surfaces for cleaning and modification purpose. For this, besides standard procedures a specially built plasma-based device was systematically evaluated for surface treatment. The following layer deposition was then implemented onto these prepared substrate surfaces and mainly analysed by angle-resolved photoelectron spectroscopy. By the means of thermal load and temporal alteration of the layers in vacuum essential knowledge about the interface stability was gained. For the completion of a whole layer stack selected substrate-layer combinations were covered with Aluminum and its layer growth was analysed with respect to the different formation of texture and its potential chemical cause.

In this thesis, we have explored the possibilities to realize a Graphene Based Hybrid structures (GBHs) by the functionalization of a graphene layer on both sides. The first chapter gives a general introduction about graphene and a literature review of different metal intercalations on graphene. The second chapter explains the experimental techniques used in this work. In chapter 3, we studied the functionalization of epitaxial graphene on SiC(0001) by gold intercalation. With the help of Scanning Tunneling Microscopy, we have evidenced and characterized different intercalation modes such as the formation of aggregates of individual gold atoms and the formation of a continuous gold layer between the top graphene and the buffer layer. The free standing nature of the intercalated gold atoms was examined by differential charge density plot, projected density of states calculations and further by X-ray photoelectron spectroscopy. The band structure modification of graphene due to these intercalated gold atoms was evidenced by Angle-resolved photoemission spectroscopy, which reveals a strong Van Hove extension and an increase of the Fermi velocity. Extend to this research, to obtain an extended Van Hove singularity usually observed in highly doped graphene; we studied highly electron donor molecules, TetraThioFullvalene (TTF) on pristine and gold intercalated graphene and on graphite (chapter 4). The dependence of charge transfer of these molecules with their conformation and the reactivity of photochromic with conjugated molecules on graphene were also discussed. To understand the structural properties of these molecules photophysical measurements were performed in chapter 5.

Mn5Ge3 suscite de l'intérêt pour des applications dans le domaine de l'électronique de spin car il a une température de Curie élevée (≈300 K) et il peut croître épitaxialement sur des substrats Ge(111) permettant ainsi d'injecter directement dans le semi-conducteur Ge un courant polarisé en spin.Nous avons étudié par photoémission résolue en angle et en spin (ARPES, SARPES), utilisant le rayonnement synchrotron, des films minces de Mn5Ge3(001), obtenus par croissance sur la surface reconstruites Ge(111)-c(2x8).Les résultats ARPES, obtenus dans les plans GALM et GAHK, sont en accord avec des simulations faites sur la base de calculs de structure de bandes faisant appel à la théorie de la fonctionnelle de la densité.Les mesures SARPES faites en plusieurs points du plan GALM sont aussi bien reproduites par ces simulations.D'une façon globale, nos résultats apportent une validation remarquable de la description des propriétés électroniques de Mn5Ge3 par le modèle de bandes. Seule l'intensité spectrale au niveau de Fermi n'est pas bien expliquée par la simulation. Cette différence est attribuée à la nature tridimensionnelle de l'échantillon et à des effets de corrélation. / Mn5Ge3 attracts strong interest for spintronics applications because it has a high Curie-temperature (≈300 K) and it can be grown epitaxially on Ge(111) substrates, permitting direct injection of a spin-polarized current into the Ge semiconductor.Mn5Ge3(001) thin films grown on Ge(111)-c(2x8) reconstructed surface were studied by angle- and spin- resolved photoemission (ARPES, SARPES) using synchrotron radiation. ARPES results, obtained in the GALM and GAHK planes, are in agreement with simulations done with the help of band structure calculations based on the density functional theory, taking into account lifetime broadening and broadening caused by correlation effects.SARPES measurements done at several k-points of the GALM plane are also well acounted for by these simulations.Overall our results provide a remarkable validation of the band structure model for a proper description of the electronic properties of Mn5Ge3. Only the spectral intensity at the Fermi level is not well explained by the simulation. This departure is attributed to the 3D nature of the sample and to correlation effects.

This thesis is focused on the electronic, spin-dependent and dynamical properties of thin magnetic systems. Photoemission-related techniques are combined with synchrotron radiation to study the spin-dependent properties of these systems in the energy and time domains. In the first part of this thesis, the strength of electron correlation effects in the spin-dependent electronic structure of ferromagnetic bcc Fe(110) and hcp Co(0001) is investigated by means of spin- and angle-resolved photoemission spectroscopy. The experimental results are compared to theoretical calculations within the three-body scattering approximation and within the dynamical mean-field theory, together with one-step model calculations of the photoemission process. From this comparison it is demonstrated that the present state of the art many-body calculations, although improving the description of correlation effects in Fe and Co, give too small mass renormalizations and scattering rates thus demanding more refined many-body theories including nonlocal fluctuations. In the second part, it is shown in detail monitoring by photoelectron spectroscopy how graphene can be grown by chemical vapour deposition on the transition-metal surfaces Ni(111) and Co(0001) and intercalated by a monoatomic layer of Au. For both systems, a linear E(k) dispersion of massless Dirac fermions is observed in the graphene pi-band in the vicinity of the Fermi energy. Spin-resolved photoemission from the graphene pi-band shows that the ferromagnetic polarization of graphene/Ni(111) and graphene/Co(0001) is negligible and that graphene on Ni(111) is after intercalation of Au spin-orbit split by the Rashba effect. In the last part, a time-resolved x-ray magnetic circular dichroic-photoelectron emission microscopy study of a permalloy platelet comprising three cross-tie domain walls is presented. It is shown how a fast picosecond magnetic response in the precessional motion of the magnetization can be induced by means of a laser-excited photoswitch. From a comparision to micromagnetic calculations it is demonstrated that the relatively high precessional frequency observed in the experiments is directly linked to the nature of the vortex/antivortex dynamics and its response to the magnetic perturbation. This includes the time-dependent reversal of the vortex core polarization, a process which is beyond the limit of detection in the present experiments. / Diese Dissertation beschäftigt sich mit den elektronischen, spinabhängigen und dynamischen Eigenschaften dünner magnetischer Systeme. Auf dem Photoeffekt basierende Untersuchungsmethoden werden zusammen mit Synchrotronstrahlung eingesetzt, um die spinabhängigen Eigenschaften dieser Systeme im Energie- und Zeitbereich zu untersuchen. Im ersten Teil dieser Arbeit wird mit spin- und winkelaufgelöster Photoemission die Stärke von Elektronenkorrelationseffekten in der spinabhängigen elektonischen Struktur von ferromagnetischerm bcc Fe(110) und hcp Co(0001) untersucht. Die experimentellen Ergebnisse werden verglichen mit theoreteischen Berechnungen im Rahmen der Näherung der Drei-Körper-Streuung und der dynamischen Molekularfeldtheorie, zusammen mit Berechnungen des Photoemissionsprozesses im Rahmen des Ein-Stufen-Modells. Ausgehend von diesem Vergleich wird gezeigt, dass die gegenwärtig fortgeschrittensten Rechnung, obgleich sie die Beschreibung von Korrelationseffekten in Fe und Co verbessern, zu kleine Massenrenormalisierungen und Streuraten ergeben, was zu der Forderung nach verfeinerten Vielteilchentheorien unter Einbeziehung von nichtlokalen Fluktuationen führt. Im zweiten Teil wird unter Kontrolle durch die Photoelektronenspektroskopie im Detail gezeigt, wie Graphen durch chemische Gasphasenabscheidung auf den Übergangsmetall-Oberflächen Ni(111) und Co(0001) aufgebracht und mit einer Monolage Au interkaliert werden kann. Für beide Systeme wird eine lineare E(k)-Dispersion masseloser Dirac-Fermionen im Graphen-pi-Band in der Nähe der Fermi-Energie beobachtet. Spinaufgelöste Photoemission des Graphen-pi-Bandes zeigt, dass die ferromagnetische Polarisation von Graphen/Ni(111) und Graphen/Co(0001) vernachlässigbar ist und dass Graphen/Ni(111) nach Interkalation mit Au eine Spin-Bahn-Aufspaltung aufgrund des Rashba-Effekts zeigt. Im letzten Teil wird eine zeitaufgelöste Studie des Röntgenzirkulardichroismus mit Photoelektronenmikroskopie präsentiert, die an einer Permalloy-Probe durchgeführt wurde, die drei als Stachelwände ausgebildete Domänenwände enthält. Es wird gezeigt, wie eine schnelle magnetische Antwort auf der Pikosekundenskala in der Präzessionsbewegung der Magnetisierung durch einen laserangesteuerten Photoschalter erzeugt werden kann. Durch Vergleich mit einer mikromagnetischen Rechnung wird gezeigt, dass die relativ hohe Präzessionsfrequenz, die im Experiment beobachtet wird, in unmittelbarer Beziehung steht zu den Eigenschaften der Vortex/Antivortex-Dynamik und ihrer Antwort auf die magnetische Störung. Das schließt die zeitabhängige Umkehr der Vortexkernpolarisation ein, einem Vorgang der jenseits der Nachweisgrenze der gegenwärtigen Experimente liegt.

The experimental work presented in this thesis is based on a wide assortment of very advanced and highly sophisticated photoelectron spectroscopy (PES) techniques. The objective of the present study has been to reveal and understand the electronic structure and electron dynamics in a broad spectrum of materials, ranging from wide band gap oxides, via semiconductors along with metals, and finally high-temperature superconductors. The first part of the thesis concerns laser-based pump-and-probe PES. This unique experimental technique has permitted a study of the excited electronic structure and the electron dynamics of several semiconductor surfaces. An insight into details of the adatom to restatom charge-transfer of the Ge(111)c(2x8) surface is presented, as well as an estimate for the timescale in which the dynamic adatoms of the Ge(111):Sn(sqrt3xsqrt3)R30deg surface operate. Further results comprise a novel unoccupied surface state at the GaSb(001) surface as well as a time-resolved study of the charge accumulation layer at the InAs(111)A/B surfaces. In the second part, high-resolution synchrotron based angle-resolved PES (ARPES) data from the cuprate high-temperature superconductor La(2-x)Sr(x)CuO(4) (LSCO) is presented. This extensive study, reveals detailed information about how the Fermi surface and electronic excitations evolve with doping in the superconducting state. The results comprise support for a connection between high- and low-energy electronic responses, the characteristics of the superconducting gap, and indication of a quantum phase transition between two different superconducting phases. In the third group of experiments we move away from the two-dimensional systems and concentrate on fully three-dimensional compounds. By the use of soft x-ray ARPES it is possible to extract the three-dimensional electronic structure in a straightforward manner with increased k(perpendicular)-resolution. As a result the first high-quality ARPES data from Cu2O is presented, as well as a novel method for extracting the (real space) electron density by ARPES. These experiments clearly display the advantages of using soft x-ray ARPES. If the material and type of experiment is chosen wisely, the benefit of the increased k||-window and the free electron final state, surpass the drawbacks of decreased count-rate and inferior energy resolution. Finally we return to the high-temperature superconductors (NCCO & Nd-LSCO) and make use of the increased bulk-sensitivity. From an evident change in the shape of the Fermi surface when moving from low to high photon energies, the durface to bulk difference in electronic structure is highlighted. / QC 20100810

The development and characterization of experimental setups for angle-resolved photoelectron spectroscopy (ARPES) and spin- and angle-resolved photoelectron spectroscopy (SARPES) is described. Subsequently, the two techniques are applied to studies of the electronic band structure in topologically non-trivial materials. The laser-based ARPES setup works at a photon energy of 10.5 eV and a typical repetition rate in the range 200 kHz to 800 kHz. By using a time-of-flight electron energy analyzer electrons emitted from the sample within a solid angle of up to ±15 degrees can be collected and analyzed simultaneously. The SARPES setup is equipped with a traditional hemispherical electron energy analyzer in combination with a mini-Mott electron polarimeter. The system enables software-controlled switching between angle-resolved spin-integrated and spin-resolved measurements, thus providing the possibility to orient the sample by mapping out the electronic band structure using ARPES before performing spin-resolved measurements at selected points in the Brillouin zone. Thin films of the topological insulators (TIs) Bi2Se3, Bi2Te3 and Sb2Te3 are grown using e-beam evaporation and their surface states are observed by means of ARPES. By using a combination of low photon energies and cryogenic sample temperatures the topological states originating from both the vacuum interface (surface) and the substrate interface are observed in Bi2Se3 films and Bi2Se3/Bi2Te3 heterostructures, with total thicknesses in the ultra-thin limit (six to eight quintuple layers), grown on Bi-terminated Si(111) substrates. Band alignment between Si and Bi2Se3 at the interface creates a band bending through the films. The band bending is found to be independent of the Fermi level (EF) position in the bulk of the substrate, suggesting that the surface pinning of EF in the Si(111) substrate remains unaltered after deposition of the TI films. Therefore, the type and level of doping of the substrate does not show any large influence on the size of the band bending. Further, we provide experimental evidence for the realization of a topological crystalline insulator (TCI) phase in the narrow-band semiconductor Pb1−xSnxSe. The TCI phase exists for temperatures below the transition temperature Tc and is characterized by an inverted bulk band gap accompanied by the existence of non-gapped surface states crossing the band gap. Above Tc the material is in a topologically trivial phase where the surface states are gapped. Thus, when lowering the sample temperature across Tc a topological phase transition from a trivial insulator to a TCI is observed. SARPES studies indicate a helical spin structure of the surface states both in the topologically trivial and the TCI phase. / <p>QC 20130507</p>

As feature sizes in semiconductor devices become smaller and newer materials are incorporated, current methods for photoresist and post plasma etch residue removal face several challenges. A cleaning process should be environmentally benign, compatible with dielectric materials and copper, and provide residue removal from narrow and high aspect ratio features. In this work, sub-critical CO2 based mixtures have been developed to remove the etch residues; these mixtures satisfy the above requirements and can potentially replace the two step residue removal process currently used in the integrated circuit (IC) industry. Based on the chemical nature of the residue being removed, additives or co-solvents to CO2 have been identified that can remove the residues without damaging the dielectric layers. Using the phase behavior of these additives as a guide, the composition of the co-solvent was altered to achieve a single liquid phase at moderate pressures without compromising cleaning ability. The extent of residue removal has been analyzed primarily by x-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Various techniques such as attenuated total reflection - Fourier transform infrared (ATR-FTIR) spectroscopy, angle-resolved XPS (ARXPS), and interferometry were used to probe the interaction of cleaning fluids with residues. Model films of photoresists and plasma deposited residues were used to assist in understanding the mechanism of residue removal. From these studies, it was concluded that residue removal takes place primarily by attack of the interface between the residue and the substrate; a solvent rinse then lifts these residues from the wafer. It has been shown that transport of the additives to the interface is enhanced in the presence of CO2. From positronium annihilation lifetime spectroscopy (PALS) studies on a porous dielectric film, it has been shown that these high pressure fluids do not cause significant changes to the pore sizes or the bonding structure of the film. Hence, this method can be used to remove post etch residues from low-k dielectric films.

In this thesis the charge dynamics of correlated electron systems, in which a metallic phase lies in close proximity to an ordered phase, are investigated by means of angle resolved photoemission spectroscopy (ARPES). The analysis of the experimental data is complemented by electronic structure calculations within the framework of density functional theory (DFT). First the charge dynamics of the colossal magnetoresistant bilayer manganites are studied. The analysis of the ARPES spectra based on DFT calculations and a Peierls type charge density wave model, suggests that charge, orbital, spin and lattice degrees of freedom conspire to form a fluctuating two dimensional local order that produces a large pseudo gap of about 450 meV in the ferromagnetic metallic phase and that reduces the expected bilayer splitting. Next, the interplay of Kondo physics and (magnetic) order in the heavy fermion superconductor URu2Si2 is investigated. The low energy electronic structure undergoes strong changes at 17.5 K, where a second order phase transition occurs whose phenomenology is well characterized, but whose order parameter could not yet be unambigeously identified. Below THO, non-dispersive quasi particles with a large scattering rate suddenly acquire dispersion and start to hybridize with the conduction band electrons. Simultaniously the scattering rate drops sinificantly and a large portion of the Fermi surface vanishes due to the opening of a gap within the band of heavy quasi particles. The observed behaviour is in stark contrast to conventional heavy fermion systems where the onset of hybridization between localized and itinerant carriers happens in a crossover type transition rather than abruptly. These experimental results suggest that Kondo screening and the hidden order parameter work together to produce the unusual thermodynamic signatures observed in this compound. Finally, the influence of charge doping and impurity scattering on the superconducting porperties of the transition metal substituted iron pnictide superconductor Ba(Fe1-xTMx)2As2 (TM = Co, Ni) is studied. Here, resonant soft X-ray ARPES is applied to see element selective the contribution of the 3d states of the TM substitute to the Fe 3d host bands. The spectroscopic signatures of the substitution are found to be well reproduced by DFT supercell and model impurity calculations. Namely, the hybridization of the dopant with the host decreases with increasing impurity potential and the electronic states of the impurtiy become increasingly localized. Simultaniously, in all simulated cases a shift of the Fermi level due to electron doping is observed. The magnitude of the shift in the chemical potential that accurs in BaFe2As2, however, is in stark contrast to the marginal doping values obtained for the impurity model, where the shift of the chemical potential is largely compensated by the influence of the increasing impurity potential. This suggests that the rigid band behaviour of TM substituded BaFe2As2 is a peculiarity of the compound, which has strong implications for the developement of superconductivity. / In dieser Arbeit wird die Ladungstraegerdynamik in korrelierten Elektronensystemen, in denen eine metallische Phase in direkter Nachbarschaft zu einer geordneten Phase liegt, mit Hilfe von winkelaufgeloester Photoelektronenspektroskopie (ARPES) untersucht. Die Analyse der experimentellen Daten wird ergaenzt durch lektronenstrukturrechnungen im Rahmen der Dichtefunktionaltheorie (DFT). Zuerst wird die Ladungstraegerdynamik in gemischtvalenten zweischichtmanganaten mit kolossalem Magnetiwiderstand studiert. Die Analyse der Photoemissionsspektren basierend auf DFT Rechnungen und einem Peierls artigem Ladungsdichtewellenmodell, legt nahe, dass die Freiheitsgrade von Ladung, Orbitalen, Spin und des Ionengitters konspirieren, um eine fluktuierende zweidimensionale lokale Ordnung zu bilden, die verantwortlich ist fuer die beobachtete Pseudobandluecke von 450 meV, und die zur Reduktion der erwarteten Zweischichtaufspaltung beitraegt. Als naechstes wird das Zusammenspiel von Kondo Physik und (magnetischer) Ordung im Schwerfermionensupraleiter URu2Si2 untersucht. Die iedrigenergetische elektronische Struktur zeigt starke Veraenderungen bei 17.5 K, wo ein Phasenuebergang zweiter Ordnungstattfindet, der phenomenologisch gut charakterisiert ist, aber dessen Ordungsparameter nocht nicht eindeutig identifiziert werden konnte. Unterhalb von THOerlangen nicht dispergierende Quasiteilchen mit gro en Streuraten abrupt Dispersion und hybridisieren mit den Leitungselektronen. Gleichzeitig sinkt die Streurate und ein gro er Teil der Fermiflaeche verschwindet durch das Oeffnen einer Bandluecke innehalb des Bandes schwerer Quasiteilchen. Das beobachtete Verhalten steht in starkem Kontrast zu dem von konventionellen Schwerfermionensystemen, in denen die Hybridisierung zwischen lokalisierten und itineranten Ladungstraegern in einem kontinuierlichen Uebergang ablaeuft, anstatt abrubt. Diese experimentellen Befunde lassen den Schluss zu, dass das zusammenspiel zwischen Kondo Abschirmung und dem unbekannten Ordnungsparameter die ungewoehnlichen thermodynamischen Signaturen in dieser Verbindung hervorruft. Abschliessend wird das Zusammenwirken von Ladungstraegerdotierung und Streuung an Stoeratomen auf die Supraleitung uebergangsmetalldotierter Eisenpniktid Supraleiter Ba(Fe1-xTMx)2As2 (TM = Co, Ni) untersucht. Mit Hilfe von resonantem Weichenroentgen ARPES gelingt es, elementselektiv den Beitrag der 3d Zustaende des TM Substituenten zu den Eisen 3d Wirtsbaendern zu beobachten. Die spektroskopischen Signaturen der Substitution sind mit Hilfe von DFT Rechnungen und Modelrechnungen mit zufaellig verteilten Stoeratomen gut zu reproduzieren. Insbesondere nimmt die Hybridisierung des dotierten Uebergangsmetalls und der Eisenbaender mit zunehmender Kernladungszahl ab und die elektronischen Zustaende der Stoeratome werden zunehmen lokalisiert. Gleichzeitig wird in allen gerechneten Faellen eine Verschiebung des Fermi Niveaus durch Elektronendotierung beobachtet. Der Betrag der Verschiebung des chemischen Potentials in BaFe2As2 steht allerdings in starkem Kontrast zu den Werten, die man im Falle der Modellrechnungen erhaelt, wo die Verschiebung des Fermi Niveaus durch den Einfluss des Potentials der Stoeratome groesstenteils kompensiert wird. Dies legt nahe, dass das beobachtete "rigid band" Verhalten von TM substituiertem BaFe2As2 eine Besonderheit dieser Verbindung ist, welches starke Auswirkungen auf die Ausbildung von Supraleitung hat.

This thesis establishes methods to locally and effciently detect the fluorescence from photonic crystals (PCs) in dependence on wavelength and direction. These are applied to three dimensional (3D) PCs grown by vertical deposition of polystyrene beads. The experiments allow conclusions about the local 3D structure of a sample, about defects in its volume and about spatial structural variations. They thus provide more information than typical spectroscopy measurements that average over large areas and methods that only image the surface structure like scanning electron microscopy. A focused laser is used to excite emitters in the sample only locally. The fluorescence is then collected by a microscope objective. Every point in this objective’s back focal plane (BFP) corresponds to a certain direction. This property is utilized in two ways. When observing a small spectral range of the emission in the BFP, stop bands appear as intensity minima since they hinder the emission into the corresponding directions. Thus, back focal plane imaging (BFPI) allows to visualize stop bands of many directions at the same time. The detected patterns permit to find the in-plane and out-of-plane orientation of the PC lattice and to conclude on the presence of stacking faults. Spatial variations of the structure are observed on a length scale of a few micrometers. The depth of the stop band is reduced at sample positions, where structural changes occur. In back focal plane spectroscopy (BFPS), a slit selects light from certain points in the BFP, which is spectrally dispersed subsequently. This allows to record spectra from many directions simultaneously. From them, a lattice compression along the sample normal of about 4% is found. Small deformations are also observed for other directions. Scattering at defects redistributes the emission. This increases the detected intensity compared to homogeneous media at some stop band edges in a broad spectral range for samples thicker than the scattering mean free path. Thinner samples show a narrow enhancement due to an increase in the fractional density of optical states and thus in emission. BFPI and BFPS are also used to observe the growth of PCs from drying droplets. The experiments show that the beads initially form a non-close packed lattice. This causes stress as the lattice constant decreases, which is released by cracking of the PCs.

A novel strategy for the intercalation of antimony (Sb) under the (6√3 × 6√3)R30° reconstruction, also known as buffer layer, on SiC(0001) is reported. Using X-ray photoelectron spectroscopy, low-energy electron diffraction, and angle-resolved photoelectron spectroscopy, it is demonstrated that, while the intercalation of the volatile Sb is not possible by annealing the Sb-coated buffer layer in ultrahigh vacuum, it can be achieved by annealing the sample in an atmosphere of Ar, which suppresses Sb desorption. The intercalation leads to a decoupling of the buffer layer from the SiC(0001) surface and the formation of quasi-freestanding graphene. The intercalation process paves the way for future studies of the formation of quasi-freestanding graphene by intercalation of high-vapor-pressure elements, which are not accessible by previously known intercalation techniques, and thus provides new avenues for the manipulation of epitaxial graphene on SiC.