Alpha T. N'diaye

Two-dimensional Ir cluster lattice on a graphene Moiré on Ir(111)

Lattices of Ir clusters have been grown by vapor phase deposition on graphene moirés on Ir(111). The clusters are highly ordered, and spatially and thermally stable below 500 K. Their narrow size distribution is tunable from 4 to about 130 atoms. A model for cluster binding to the graphene is presented based on scanning tunneling microscopy and density functional theory. The proposed binding mechanism suggests that similar cluster lattices might be grown of materials other than Ir.

Growth of graphene on Ir(111)

Catalytic decomposition of hydrocarbons on transition metals attracts a renewed interest as a route toward high-quality graphene prepared in a reproducible manner. Here we employ two growth methods for graphene on Ir(111), namely room temperature adsorption and thermal decomposition at 870–1470u2009K (temperature programmed growth (TPG)) as well as direct exposure of the hot substrate at 870–1320u2009K (chemical vapor deposition (CVD)). The temperature- and exposure-dependent growth of graphene is investigated in detail by scanning tunneling microscopy. TPG is found to yield compact graphene islands bounded by C zigzag edges. The island size may be tuned from a few to a couple of tens of nanometers through Smoluchowski ripening. In the CVD growth, the carbon in ethene molecules arriving on the Ir surface is found to convert with probability near unity to graphene. The temperature-dependent nucleation, interaction with steps and coalescence of graphene islands are analyzed and a consistent model for CVD growth is developed.

Structure of epitaxial graphene on Ir(111)

A graphene monolayer has been prepared on an Ir(111) single crystal via pyrolytic cleavage of ethylene (C2H4). The resulting superstructure has been examined with scanning tunneling microscopy (STM) and low energy electron diffraction. It has been identified as a well aligned, incommensurate (9.32?9.32) pattern, which is described as a moir?. This pattern shows three distinct regions resulting from different local configurations of the carbon adlayer with respect to the Ir-substrate. These regions are imaged differently by STM and differ strongly in their ability to bind metal deposits.

Dirac Cones and Minigaps for Graphene on Ir(111)

Epitaxial graphene on Ir(111) prepared in excellent structural quality is investigated by angle-resolved photoelectron spectroscopy. It clearly displays a Dirac cone with the Dirac point shifted only slightly above the Fermi level. The moiré resulting from the overlaid graphene and Ir(111) surface lattices imposes a superperiodic potential giving rise to Dirac cone replicas and the opening of minigaps in the band structure.

Graphene on Ir(111): physisorption with chemical modulation.

The nonlocal van der Waals density functional approach is applied to calculate the binding of graphene to Ir(111). The precise agreement of the calculated mean height h = 3.41u2009u2009Å of the C atoms with their mean height h = (3.38±0.04)u2009u2009Å as measured by the x-ray standing wave technique provides a benchmark for the applicability of the nonlocal functional. We find bonding of graphene to Ir(111) to be due to the van der Waals interaction with an antibonding average contribution from chemical interaction. Despite its globally repulsive character, in certain areas of the large graphene moiré unit cell charge accumulation between Ir substrate and graphene C atoms is observed, signaling a weak covalent bond formation.

A versatile fabrication method for cluster superlattices

On the graphene moire on Ir(111) a variety of highly perfect cluster superlattices can be grown as shown for Ir, Pt, W and Re. Even materials that do not form cluster superlattices upon room temperature deposition may be grown into such by low-temperature deposition or the application of cluster seeding through Ir as shown for Au, AuIr and FeIr. Criteria for the suitability of a material to form a superlattice are given and largely confirmed. It is proven that at least Pt and Ir form epitaxial cluster superlattices. The temperature stability of the cluster superlattices is investigated and understood on the basis of positional fluctuations of the clusters around their sites of minimum potential energy. The binding sites of Ir, Pt, W and Re cluster superlattices are determined and the ability to cover samples macroscopically with a variety of superlattices is demonstrated.

In?situ observation of stress relaxation in epitaxial graphene

Upon cooling, branched line defects develop in epitaxial graphene grown at high temperature on Pt(111) and Ir(111). Using atomically resolved scanning tunneling microscopy we demonstrate that these defects are wrinkles in the graphene layer, i.e. stripes of partially delaminated graphene. With low energy electron microscopy (LEEM) we investigate the wrinkling phenomenon in situ. Upon temperature cycling we observe hysteresis in the appearance and disappearance of the wrinkles. Simultaneously with wrinkle formation a change in bright field imaging intensity of adjacent areas and a shift in the moire spot positions for micro diffraction of such areas takes place. The stress relieved by wrinkle formation results from the mismatch in thermal expansion coefficients of graphene and the substrate. A simple one-dimensional model taking into account the energies related to strain, delamination and bending of graphene is in qualitative agreement with our observations.

Selecting a single orientation for millimeter sized graphene sheets

We have used low energy electron microscopy and photo emission electron microscopy to study and improve the quality of graphene films grown on Ir(111) using chemical vapor deposition (CVD). CVD at elevated temperature already yields graphene sheets that are uniform and of monatomic thickness. Besides domains that are aligned with respect to the substrate, other rotational variants grow. Cyclic growth exploiting the faster growth and etch rates of the rotational variants, yields films that are 99% composed of aligned domains. Precovering the substrate with a high density of graphene nuclei prior to CVD yields pure films of aligned domains extending over millimeters. Such films can be used to prepare cluster-graphene hybrid materials for catalysis or nanomagnetism and can potentially be combined with lift-off techniques to yield high-quality, graphene based, electronic devices.

Interplay of Wrinkles, Strain, and Lattice Parameter in Graphene on Iridium

Following graphene growth by thermal decomposition of ethylene on Ir(111) at high temperatures we analyzed the strain state and the wrinkle formation kinetics as function of temperature. Using the moiré spot separation in a low energy electron diffraction pattern as a magnifying mechanism for the difference in the lattice parameters between Ir and graphene, we achieved an unrivaled relative precision of ±0.1 pm for the graphene lattice parameter. Our data reveals a characteristic hysteresis of the graphene lattice parameter that is explained by the interplay of reversible wrinkle formation and film strain. We show that graphene on Ir(111) always exhibits residual compressive strain at room temperature. Our results provide important guidelines for strategies to avoid wrinkling.

Perpendicular magnetic anisotropy of cobalt films intercalated under graphene

Magnetic properties of nanometer-thick Co films intercalated at the graphene/Ir(111) interface are investigated using spin-polarized low-energy electron microscopy and Auger electron spectroscopy. We show that the graphene top layer promotes perpendicular magnetic anisotropy in the Co film underneath, even for relatively thick intercalated deposits. The magnetic anisotropy energy is significantly larger for the graphene/Co interface than for the free Co surface. Hybridization of the graphene and Co electron orbitals is believed to be at the origin of the observed perpendicular magnetic anisotropy.