Quasi-freestanding and single-atom thick layer of hexagonal boron nitride as a substrate for graphene synthesis

We demonstrate that freeing a single-atom thick layer of hexagonal boron nitride (hbn) from tight chemical bonding to a Ni(111) thin film grown on a W(110) substrate can be achieved by intercalation of Au atoms into the interface. This process has been systematically investigated using angle-resolved photoemission spectroscopy, X-ray photoemission and absorption techniques. It has been demonstrated that the transition of the hbn layer from the "rigid" into the "quasi-freestanding" state is accompanied by a change of its lattice constant. Using chemical vapor deposition, graphene has been successfully synthesized on the insulating, quasi-freestanding hbn monolayer. We anticipate that the in situ synthesized weakly interacting graphene/hbn double layered system could be further developed for technological applications and may provide perspectives for further inquiry into the unusual electronic properties of graphene.Comment: in print in Phys. Rev.

Fermi surfaces of single layer dielectrics on transition metals

Single sheets of hexagonal boron nitride on transition metals provide a model system for single layer dielectrics. The progress in the understanding of h-BN layers on transition metals of the last 10 years are shortly reviewed. Particular emphasis lies on the boron nitride nanomesh on Rh(111), which is a corrugated single sheet of h-BN, where the corrugation imposes strong lateral electric fields. Fermi surface maps of h-BN/Rh(111) and Rh(111) are compared. A h-BN layer on Rh(111) introduces no new bands at the Fermi energy, which is expected for an insulator. The lateral electric fields of h-BN nanomesh violate the conservation law for parallel momentum in photoemission and smear out the momentum distribution curves on the Fermi surface.Comment: 14 pages, 6 figures, 1 table, 1 equation, Accepted for publication in the Special Surface Science issue in honor of Gerhard Ertl's Nobel Priz

Induced magnetism of carbon atoms at the graphene/Ni(111) interface

We report an element-specific investigation of electronic and magnetic properties of the graphene/Ni(111) system. Using magnetic circular dichroism, the occurrence of an induced magnetic moment of the carbon atoms in the graphene layer aligned parallel to the Ni 3d magnetization is observed. We attribute this magnetic moment to the strong hybridization between C $\pi$ and Ni 3d valence band states. The net magnetic moment of carbon in the graphene layer is estimated to be in the range of $0.05-0.1 \mu_B$ per atom.Comment: 10 pages, 3 figure

Reversible switching of surface texture by hydrogen intercalation

The interaction of atomic hydrogen with a single layer of hexagonal boron nitride on rhodium leads to a removal of the h-BN surface corrugation. The process is reversible as the hydrogen may be expelled by annealing to about 500 K whereupon the texture on the nanometer scale is restored. This effect is traced back to hydrogen intercalation. It is expected to have implications for applications, like the storage of hydrogen, the peeling of sp2-hybridized layers from solid substrates or the control of the wetting angle, to name a few.Comment: 4 pages and 4 figure

Spectroscopic characterization of graphene films grown on Pt (111) surface by chemical vapor deposition of ethylene

This work reports the peculiar properties of a graphene film prepared by the chemical vapor deposition (CVD) of ethylene in high vacuum on a well oriented and carefully cleaned Pt(111) crystal surface maintained at high temperature. In-situ and ex-situ characterization techniques (low energy electron diffraction, high resolution electron energy loss spectroscopy, scanning electron microscopy and Raman micro-spectroscopy) used here indicate the prevalence of single layer regions and the presence of two different orientations of the graphene sheets with respect to the Pt(111) substrate. In most of the deposited area evidence is found of a compressive stress for the graphene lattice, as a net result of the growth process on a metal substrate. This graphene film grown on Pt(111) exhibits a lower degree of order and of homogeneity with respect to the exfoliated graphene on Si/SiO2, as it is found generally for graphene on metals, but several characterization techniques indicates a better quality than in previous deposition experiments on the same metal substrate.Comment: 18 pages, 5 figures, Journal of Raman spectroscopy 201

The helicity amplitudes A1/2_{1/2} and A3/2_{3/2} for the D13(1520)_{13}(1520) resonance obtained from the γ⃗p⃗→pπ0\vec{\gamma} \vec{p} \to p \pi^0 reaction}

The helicity dependence of the $\vec{\gamma} \vec{p} \to p \pi^0$ reaction has been measured for the first time in the photon energy range from 550 to 790 MeV. The experiment, performed at the Mainz microtron MAMI, used a 4$\pi$-detector system, a circularly polarized, tagged photon beam, and a longitudinally polarized frozen-spin target. These data are predominantly sensitive to the $D_{13}(1520)$ resonance and are used to determine its parameters.Comment: 5 pages, 4 figure

Untersuchung der Helizitätsabhängigkeit der Einpionphotoproduktion am Proton

Die vorliegende Arbeit beschreibt den Aufbau, dieDurchfuehrung und die Analyse des ersten Experiments zurhelizitaetsabhaengigen Photoproduktion neutraler undgeladener Pionen im Energiebereich der ersten Nukleonresonanzen.Dieses Experiment wurde am Mainzer Mikrotron MAMI unterVerwendung longitudinal polarisierter Nukleonen und zirkularpolarisierter reeller Photonen durchgefuehrt. Die Nukleonenwurden in einem Frozen-Spin-Butanol-Target polarisiert.Polarisierte Photonen wurden durch Bremsstrahlunglongitudinal polarisierter Elektronen erzeugt. DieReaktionsprodukte wurden in einem Detektorsystem aus dreiKomponenten registriert. Die in dieser Arbeit analysiertenDaten wurden allein mit dem Detektor DAPHNE aufgenommen,der 94% des gesamten Akzeptanzbereiches ueberdeckt.Vor der Messung mit dem polarisierten Butanol-Targetwurden Eichmessungen mit reinen Wasserstoff- undDeuteriumtargets durchgefuehrt. Beide Kanaele zurPhotoproduktion eines Pions am Proton wurden analysiert. Dieunpolarisierten Wirkungsquerschnitte aus der Eichmessungstimmen gut mit existierenden Daten ueberein.Die helizitaetsabhaengige Wirkungsquerschnitte liefernneue Information sowohl im ersten, als auch zweitenResonanzgebiet. Bei Photonenenergien bis 450 MeV ist esmoeglich, unter Verwendung der gut bestimmten Datenbasis,eine Multipolanalyse durchzufuehren und somit die S- undP-Wellen Multipolamplituden zu bestimmen.Es wurde eine Diskrepanz zwischen unseren polarisiertendifferentiellen Wirkungsquerschnitten und theoretischenVorhersagen im Bereich der D_13(1520)-Resonanz gefunden.Eine deutlich bessere Uebereinstimmung kann durch eineAenderung der E2- und M2-Staerken im gN -> D_13(1520)Uebergang erzielt werden

First measurement of the Gerasimov-Drell-Hearn integral for Hydrogen from 200 to 800 MeV

A direct measurement of the helicity dependence of the total photoabsorption cross section on the proton was carried out at MAMI (Mainz) in the energy range 200 < E_gamma < 800 MeV. The experiment used a 4$\pi$ detection system, a circularly polarized tagged photon beam and a frozen spin target. The contributions to the Gerasimov-Drell-Hearn sum rule and to the forward spin polarizability $\gamma_0$ determined from the data are 226 \pm 5 (stat)\pm 12(sys) \mu b and -187 \pm 8 (stat)\pm 10(sys)10^{-6} fm^4, respectively, for 200 < E_\gamma < 800 MeV.Comment: 6 pages, 3 figures, 3 table

In Situ Observations during Chemical Vapor Deposition of Hexagonal Boron Nitride on Polycrystalline Copper.

Using a combination of complementary in situ X-ray photoelectron spectroscopy and X-ray diffraction, we study the fundamental mechanisms underlying the chemical vapor deposition (CVD) of hexagonal boron nitride (h-BN) on polycrystalline Cu. The nucleation and growth of h-BN layers is found to occur isothermally, i.e., at constant elevated temperature, on the Cu surface during exposure to borazine. A Cu lattice expansion during borazine exposure and B precipitation from Cu upon cooling highlight that B is incorporated into the Cu bulk, i.e., that growth is not just surface-mediated. On this basis we suggest that B is taken up in the Cu catalyst while N is not (by relative amounts), indicating element-specific feeding mechanisms including the bulk of the catalyst. We further show that oxygen intercalation readily occurs under as-grown h-BN during ambient air exposure, as is common in further processing, and that this negatively affects the stability of h-BN on the catalyst. For extended air exposure Cu oxidation is observed, and upon re-heating in vacuum an oxygen-mediated disintegration of the h-BN film via volatile boron oxides occurs. Importantly, this disintegration is catalyst mediated, i.e., occurs at the catalyst/h-BN interface and depends on the level of oxygen fed to this interface. In turn, however, deliberate feeding of oxygen during h-BN deposition can positively affect control over film morphology. We discuss the implications of these observations in the context of corrosion protection and relate them to challenges in process integration and heterostructure CVD.P.R.K. acknowledges funding from the Cambridge Commonwealth Trust and the Lindemann Trust Fellowship. R.S.W. acknowledges a research fellowship from St. John’s College, Cambridge. S.H. acknowledges funding from ERC grant InsituNANO (no. 279342), EPSRC under grant GRAPHTED (project reference EP/K016636/1), Grant EP/H047565/1 and EU FP7 Work Programme under grant GRAFOL (project reference 285275). The European Synchrotron Radiation Facility (ESRF) is acknowledged for provision of synchrotron radiation and assistance in using beamline BM20/ROBL. We acknowledge Helmholtz-Zentrum-Berlin Electron storage ring BESSY II for synchrotron radiation at the ISISS beamline and continuous support of our experiments.This is the final version. It was first published by ACS at http://pubs.acs.org/doi/abs/10.1021/cm502603