Dapeng Jing

Self-assembly of metal nanostructures on binary alloy surfaces

Deposition of metals on binary alloy surfaces offers new possibilities for guiding the formation of functional metal nanostructures. This idea is explored with scanning tunneling microscopy studies and atomistic-level analysis and modeling of nonequilibrium island formation. For Au/NiAl(110), complex monolayer structures are found and compared with the simple fcc(110) bilayer structure recently observed for Ag/NiAl(110). We also consider a more complex codeposition system, (Ni + Al)/NiAl(110), which offers the opportunity for fundamental studies of self-growth of alloys including deviations for equilibrium ordering. A general multisite lattice-gas model framework enables analysis of structure selection and morphological evolution in these systems.

Nanoscale “Quantum” Islands on Metal Substrates: Microscopy Studies and Electronic Structure Analyses

Confinement of electrons can occur in metal islands or in continuous films grown heteroepitaxially upon a substrate of a different metal or on a metallic alloy. Associated quantum size effects (QSE) can produce a significant height-dependence of the surface free energy for nanoscale thicknesses of up to 10–20 layers. This may suffice to induce height selection during film growth. Scanning STM analysis has revealed remarkable flat-topped or mesa-like island and film morphologies in various systems. We discuss in detail observations of QSE and associated film growth behavior for Pb/Cu(111), Ag/Fe(100), and Cu/fcc-Fe/Cu(100) [A/B or A/B/A], and for Ag/NiAl(110) with brief comments offered for Fe/Cu3Au(001) [A/BC binary alloys]. We also describe these issues for Ag/5-fold i-Al-Pd-Mn and Bi/5-fold i-Al-Cu-Fe [A/BCD ternary icosohedral quasicrystals]. Electronic structure theory analysis, either at the level of simple free electron gas models or more sophisticated Density Functional Theory calculations, can provide insight into the QSE-mediated thermodynamic driving force underlying height selection.

Weak bonding of Zn in an Al-based approximant based on surface measurements

We have studied two surfaces of a new Al–Pd–Zn approximant using mass spectrometry, X-ray photoemission spectroscopy (XPS) and scanning tunneling microscopy (STM). Zn is bonded weakly in this approximant, perhaps as weakly as in elemental Zn. This is based upon three observations: (1) the low vapor pressure of Zn above the approximant (detectable in the gas phase at 600 K), (2) preferential sputtering of Zn (contrary to the usual preferential sputtering of Al in Al-rich quasicrystals), and (3) preferential surface segregation of Zn. We further show that preferential segregation – and perhaps incipient evaporation – causes the surface to roughen, preventing it from forming a terrace-step morphology. Finally, our data show that at low O2 pressures, Al oxidizes. In air, Zn oxidizes as well. All results and conclusions are similar for the two-fold and pseudo-10-fold surfaces.

Temperature-dependent growth shapes of Ni nanoclusters on NiAl(110)

Scanning tunneling microscopy studies reveal that two-dimensional nanoscale Ni islands formed by deposition of Ni on NiAl(110) between 200-400 K exhibit far-from-equilibrium growth shapes which change systematically with temperature. Island structure reflects the two types of adsorption sites available for Ni adatoms, and island shapes are controlled by the details of adatom diffusion along island edges accounting for numerous local configurations. The temperature dependence of the island shapes is captured and elucidated by kinetic Monte Carlo simulation of a realistic atomistic-level multisite lattice-gas model incorporating precise diffusion barriers. These barriers are obtained by utilizing density functional theory to probe energetics not just at adsorption sites but also at transition states for diffusion. This success demonstrates a capability for predictive atomistic-level modeling of nanocluster formation and shape selection in systems that have a high level of energetic and kinetic complexity.

From Initial to Late Stages of Epitaxial Thin Film Growth: STM Analysis and Atomistic or Coarse-Grained Modeling

Epitaxial thin film growth by vapor deposition or molecular beam epitaxy under ultra‐high vacuum conditions generally occurs in two stages: (i) nucleation and growth of well‐separated islands on the substrate; (ii) subsequent formation of a thicker continuous film with possible kinetic roughening. For homoepitaxial growth, two‐dimensional (2D) monolayer islands are formed during submonolayer deposition. Typically, the presence of a step‐edge barrier inhibits downward transport and leads to the formation of mounds (multilayer stacks of 2D islands) during multilayer growth. For heteroepitaxial growth, islands formed in the initial stages of deposition sometimes have a 2D monolayer structure. However, they may instead exhibit bilayer or 3D multilayer structure due to, e.g., a high film surface energy, strain, or quantum size effects. Various growth modes are possible for thicker films. Atomistic modeling provides the most detailed picture of film growth. For coherent (defect‐free) epitaxial films, lattice‐ga...

Reverse-engineering of graphene on metal surfaces: a case study of embedded ruthenium

Using scanning tunneling microscopy, x-ray photoelectron spectroscopy, and x-ray absorption spectroscopy, we show that Ru forms metallic nanoislands on graphite, covered by a graphene monolayer. These islands are air-stable, contain 2-4 layers of Ru, and have diameters on the order of 10 nm. To produce these nanoislands two conditions must be met during synthesis. The graphite surface must be ion-bombarded, and subsequently held at an elevated temperature (1000-1180 K) during Ru deposition. A coincidence lattice forms between the graphene overlayer and the Ru island top. Its characteristics-coincidence lattice constant, corrugation amplitude, and variation of carbon lattice appearance within the unit cell-closely resemble the well-established characteristics of single-layer graphene on the (0001) surface of bulk Ru. Quantitative analysis of the graphene lattice in relation to the coincidence lattice on the island tops show that the two-dimensional lattice constant of the underlying metal equals that of bulk Ru(0001), within experimental error. The embedded Ru islands are energetically favored over on-top (adsorbed) islands, based on density-functional-theory calculations for Ru films with 1-3 Ru layers. We propose a formation mechanism in which Ru atoms intercalate via defects that act as entry portals to the carbon galleries, followed by nucleation and growth in the galleries. In this model, high deposition temperature is necessary to prevent blockage of entry portals.

Thermally activated diffusion of copper into amorphous carbon

Using x-ray photoelectron spectroscopy, the authors characterize the thermally activated changes that occur when Cu is deposited on amorphous carbon supported on Si at 300 K, then heated to 800 K. The authors compare data for Cu on the basal plane of graphite with pinning defects, where scanning tunneling microscopy reveals that coarsening is the main process in this temperature range. Coarsening begins at 500–600 K and causes moderate attenuation of the Cu photoelectron signal. For Cu on amorphous carbon, heating to 800 K causes Cu to diffuse into the bulk of the film, based on the strong attenuation of the Cu signal. Diffusion into the bulk of the amorphous carbon film is confirmed by changes in the shape of the Cu 2p inelastic tail, and by comparison of attenuation between Cu 2p and Cu 3p lines. The magnitude of the photoelectron signal attenuation is compatible with Cu distributed homogeneously throughout the amorphous carbon film, and is not compatible with Cu at or below the C–Si interface under the...