Deposition of metal clusters on single-layer graphene/Ru(0001): Factors that govern cluster growth

Abstract Fabrication of nanoclusters on a substrate is of great interest in studies of model catalysts. The key factors that govern the growth and distribution of metal on graphene have been studied by scanning tunneling microscopy (STM) based on different behaviors of five transition metals, namely Pt, Rh, Pd, Co, and Au supported on the template of a graphene moire pattern formed on Ru(0001). Our experimental findings show that Pt and Rh form finely dispersed small clusters located at fcc sites on graphene while Pd and Co form large clusters at similar coverages. These results, coupled with previous findings that Ir forms the best finely dispersed clusters, suggest that both metal–carbon (M–C) bond strength and metal cohesive energies play significant roles in the cluster formation process and that the M–C bond strength is the most important factor that affects the morphology of clusters at the initial stages of growth. Furthermore, experimental results show Au behaves differently and forms a single-layer film on graphene, indicating other factors such as the effect of substrate metals and lattice match should also be considered. In addition, the effect of annealing Rh on graphene has been studied and its high thermal stability is rationalized in terms of a strong interaction between Rh and graphene as well as sintering via Ostwald ripening.

[1]  D. Goodman,et al.  Investigations of Graphitic Overlayers Formed from Methane Decomposition on Ru(0001) and Ru(11.hivin.20) Catalysts with Scanning Tunneling Microscopy and High-Resolution Electron Energy Loss Spectroscopy , 1994 .

[2]  P. Feibelman Onset of three-dimensional Ir islands on a graphene/Ir(111) template , 2009 .

[3]  Noureddine Abidi,et al.  Wettability and surface free energy of graphene films. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[4]  S. N. Sahu,et al.  Liquid-drop model for the size-dependent melting of low-dimensional systems , 2002 .

[5]  Yi Cui,et al.  Fabrication of metal nanoclusters on graphene grown on Ru(0001) , 2009 .

[6]  Andrew G. Glen,et al.  APPL , 2001 .

[7]  M. Bocquet,et al.  Graphene on metal surfaces , 2009 .

[8]  Weihong Qi,et al.  Surface-area-difference model for thermodynamic properties of metallic nanocrystals , 2005 .

[9]  A. Cervellino,et al.  Graphene on Ru(0001): a 25 x 25 supercell. , 2008, Physical review letters.

[10]  Two-dimensional Ir cluster lattice on a graphene moiré on Ir(111). , 2006, Physical review letters.

[11]  P. Feibelman Pinning of graphene to Ir(111) by flat Ir dots , 2008 .

[12]  S. Marchini,et al.  Scanning tunneling microscopy of graphene on Ru(0001) , 2007 .

[13]  J. M. Simoes,et al.  Transition metal-hydrogen and metal-carbon bond strengths: the keys to catalysis , 1990 .

[14]  J. Giber,et al.  The Surface Free Energies of Solid Chemical Elements: Calculation from Internal Free Enthalpies of Atomization , 1982 .

[15]  Andre K. Geim,et al.  The rise of graphene. , 2007, Nature materials.

[16]  Mitch Jacoby GRAPHENE : CARBON AS THIN AS CAN BE , 2009 .

[17]  Han‐Ki Kim,et al.  The cluster size dependence of thermal stabilities of both molybdenum and tungsten nanoclusters , 2002 .

[18]  T. Michely,et al.  A versatile fabrication method for cluster superlattices , 2009, 0908.3800.

[19]  Hongjun Gao,et al.  Directed self-assembly of monodispersed platinum nanoclusters on graphene Moiré template , 2009 .

[20]  Andre K. Geim,et al.  Electric Field Effect in Atomically Thin Carbon Films , 2004, Science.

[21]  J. Flege,et al.  Epitaxial graphene on ruthenium. , 2008, Nature materials.

[22]  M. A. Turchanin,et al.  Cohesive energy, properties, and formation energy of transition metal alloys , 2008 .