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The alteration of the properties of single-molecule magnets (SMMs) due to the interaction with metallic electrodes is detrimental to their employment in spintronic devices. Conversely, herein we show that the terbium(iii) bis-phthalocyaninato complex, TbPc2, maintains its SMM behavior up to 9 K on a graphene/SiC(0001) substrate, making this alternative conductive layer highly promising for molecular spintronic applications.

The magnetic properties of some single molecule magnets (SMM) on surfaces can be strongly modified by the molecular packing in nanometric films/aggregates or by interactions with the substrate, which affect the molecular orientation and geometry. Detailed investigations of the magnetism of thin SMM films and nanostructures are necessary for the development of spin-based molecular devices, however this task is challenged by the limited sensitivity of laboratory-based magnetometric techniques and often requires access to synchrotron light sources to perform surface sensitive X-ray magnetic circular dichroism (XMCD) investigations. Here we show that low-temperature magnetic force microscopy is an alternative powerful laboratory tool able to extract the field dependence of the magnetization and to identify areas of in-plane and perpendicular magnetic anisotropy in microarrays of the SMM terbium(III) bis-phthalocyaninato (TbPc2) neutral complex grown as nanosized films on SiO2 and perylene-3,4,9,10-tetracarbox...

We perform on-surface synthesis of single-ion molecular magnets on an Ag(111) surface and characterize their morphology, chemistry, and magnetism. The first molecule we synthesize is TbPc2 to enable comparison with chemically synthesized and subsequently surface adsorbed species. We demonstrate the formation of TbPc2 with a yield close to 100% and show that on-surface synthesis leads to identical magnetic and morphological properties compared to the previously studied chemically synthesized species. Moreover, exposure of the surface adsorbed TbPc2 molecules to air does not modify their magnetic and morphological properties. To demonstrate the versatility of our approach, we synthesize novel Tb double deckers using tert-butyl-substituted phthalocyanine (tbu-2H-Pc). The Tb(tbu-Pc)(2) molecules exhibit magnetic hysteresis and therefore are the first purely on-surface synthesized single ion magnet.

Lanthanides (Ln) bis-phthalocyanine (Pc), the so-called LnPc2double decker, are a promising class of molecules with a well-defined magnetic anisotropy. In this work, we investigate the magnetic properties of LnPc2 molecules UHV-deposited on a graphene/Ni(111) substrate and how they modify when an Au layer is intercalated between Ni and graphene. X-ray absorption spectroscopy (XAS), and linear and magnetic circular dichroism (XLD and XMCD) were used to characterize the systems and probe the magnetic coupling between LnPc2 molecules and the Ni substrate through graphene, both gold-intercalated and not. Two types of LnPc2 molecules (Ln = Tb, Er) with a different magnetic anisotropy (easy-axis for Tb, easy-plane for Er) were considered. XMCD shows an antiferromagnetic coupling between Ln and Ni(111) even in the presence of the graphene interlayer. Au intercalation causes the vanishing of the interaction between Tb and Ni(111). In contrast, in the case of ErPc2, we found that the gold intercalation does not perturb the magnetic coupling. These results, combined with the magnetic anisotropy of the systems, suggest the possible importance of the magnetic dipolar field contribution for determining the magnetic behaviour.

International audience; The remarkable properties of graphene have shown promise for new perspectives in future electronics, notably for nanometer scale devices. Here we grow graphene epitaxially on an off-axis 4H-SiC(0001) substrate and demonstrate the formation of periodic arrangement of monolayer graphene on planar (0001) terraces and Bernal bilayer graphene on (112 — 0) nanofacets of SiC. We investigate these lateral superlattices using Raman spectroscopy, atomic force microscopy/ electrostatic force microscopy (AFM/EFM) and X-ray and angle resolved photoemission spectroscopy (XPS/ARPES). The correlation of EFM and ARPES reveals the appearance of permanent electronic band gaps in AB-stacked bilayer graphene on (112 — 0) SiC nanofacets of 150 meV. This feature is confirmed by density functional theory (DFT) calculations. The charge transfer between the substrate and graphene bilayer results in an asymmetric charge distribution between the top and the bottom graphene layers opening an energy gap. This surface organization can be thus defined as self-organized metal–semiconductor graphene.

In-plane heteroatom substitution of graphene is a promising strategy to modify its properties. The ability to dope graphene with electron-donor nitrogen heteroatoms is highly important for modulating electrical properties of graphene. Here we demonstrate a transfer-free method to directly grow large area quasi free-standing N-doped graphene bilayers on an insulating substrate (Si3N4). Electron-bombardment heating under nitrogen flux results in simultaneous growth of N-doped graphene and a Si3N4 layer on the SiC surface. The decoupling of N-doped graphene from the substrate and the presence of Si3N4 are identified by X-ray photoemission spectroscopy and low-energy electron diffraction. The substitution of nitrogen atoms in the graphene planes was confirmed using high resolution X-ray photoemission spectroscopy which reveals several atomic configurations for the nitrogen atoms: Graphitic-like, pyridine-like, and pyrroliclike. Furthermore, we demonstrated for the first time that N-doped graphene could be used to efficiently probe oxygen molecules via nitrogen atom defects. Open image in new window

International audience; The stacking order of multilayer graphene has a profound influence on its electronic properties. In particular, it has been predicted that a rhombohedral stacking sequence displays a very flat conducting surface state: the longer the sequence, the flatter the band. In such a flat band, the role of electron electron correlation is enhanced, possibly resulting in high T-c superconductivity, magnetic order, or charge density wave order. Here we demonstrate that rhombohedral multilayers are easily obtained by epitaxial growth on 3C-S1C(111) on a 2 degrees off-axis 6H-SiC(0001). The resulting samples contain rhombohedral sequences of five layers on 70% of the surface. We confirm the presence of the flat band at the Fermi level by scanning tunneling spectroscopy and angle-resolved photoemission spectroscopy, in close agreement with the predictions of density functional theory calculations.

International audience; Nitrogen doping of graphene is of great interest for both fundamental research to explore the effect of dopants on a 2D electrical conductor and applications such as lithium storage, composites, and nanoelectronic devices. Here, we report on the modifications of the electronic properties of epitaxial graphene thanks to the introduction, during the growth, of nitrogen-atom substitution in the carbon honeycomb lattice. High-resolution transmission microscopy and low-energy electron microscopy investigations indicate that the nitrogen-doped graphene is uniform at large scale. The substitution of nitrogen atoms in the graphene planes was confirmed by high-resolution X-ray photoelectron spectroscopy, which reveals several atomic configurations for the nitrogen atoms: graphitic-like, pyridine-like, and pyrrolic-like. Angle-resolved photoemission measurements show that the N-doped graphene exhibits large n-type carrier concentrations of 2.6 x 10(13) cm(-1), about 4 times more than what is found for pristine graphene, grown under similar pressure conditions. Our experiments demonstrate that a small amount of dopants (

International audience; Structural and electronic properties of epitaxial graphene on 4H-SiC were studied before and after an atomic oxidation process. X-ray photoemission spectroscopy indicates that oxygen penetrates into the substrate and decouples a part of the interface layer. Raman spectroscopy demonstrates the increase of defects due to the presence of oxygen. Interestingly, we observed on the near edge x-ray absorption fine structure spectra a splitting of the pi* peak into two distinct resonances centered at 284.7 and 285.2 eV. This double structure smears out after the oxidation process and permits to probe the interface architecture between graphene and the substrate. (C) 2014 AIP Publishing LLC.

International audience; Epitaxial nanographene grown on SiC substrate is of great interest for electronic and optoelectronic applications. The shape and the size of nanographene dictates its electrical, optical, magnetic, and chemical properties including possible edge states and quantum confinement. Here, we report the epitaxial growth of nanographene on 3C-SiC(100) on silicon substrates. Raman spectroscopy determines the nanographene size to be around 20 nm, making it an ideal high edge density sample. Near edge x-ray absorption fine structure of nanographene reveals the appearance of an additional state located at the Fermi level, interpreted as an empty state corresponding to graphene edges