The role of H-H interactions and impurities on the structure and energetics of H/Pd(111).

Understanding hydrogen incorporation into palladium requires detailed knowledge of surface and subsurface structure and atomic interactions as surface hydrogen is being embedded. Using density functional theory (DFT), we examine the energies of hydrogen layers of varying coverage adsorbed on Pd(111). We find that H-H and H-Pd interactions promote the formation of the well-known 3×3 phases but also favor an unreported (3 × 3) phase at high H coverages for which we present experimental evidence. We relate the stability of isolated H vacancies of the (3 × 3) phase to the need of H2 molecules to access bare Pd before they can dissociate. Following higher hydrogen dosage, we observe initial steps of hydride formation, starting with small clusters of subsurface hydrogen. The interaction between H and Pd is complicated by the persistent presence of carbon at the surface. X-ray photoelectron spectroscopy experiments show that trace amounts of carbon, emerging from the Pd bulk despite many surface cleaning cycles, become mobile enough to repopulate the C-depleted surface at temperatures above 200 K. When exposed to hydrogen, these surface carbon atoms react to form benzene, as evidenced by scanning tunneling microscopy observations interpreted with DFT.

Orientation-dependent growth mechanisms of graphene islands on Ir(111).

Using low-energy electron microscopy, we find that the mechanisms of graphene growth on Ir(111) depend sensitively on island orientation with respect to Ir. In the temperature range of 750-900 °C, we observe that growing rotated islands are more faceted than islands aligned with the substrate. Further, the growth velocity of rotated islands depends not only on the C adatom supersaturation but also on the geometry of the island edge. We deduce that the growth of rotated islands is kink-nucleation-limited, whereas aligned islands are kink-advancement-limited. These different growth mechanisms are attributed to differences in the graphene edge binding strength to the substrate.

Pentagons and heptagons in the first water layer on Pt(111).

Scanning tunneling topography of long-unexplained "square root of 37" and "square root of 39" periodic wetting arrangements of water molecules on Pt(111) reveals triangular depressions embedded in a hexagonal H2O-molecule lattice. Remarkably, the hexagons are rotated 30° relative to the "classic bilayer" model of water-metal adsorption. With support from density functional theory energetics and image simulation, we assign the depressions to clusters of flat-lying water molecules. 5- and 7-member rings of H2O molecules separate these clusters from surrounding "H-down" molecules.

Interpretation of high-resolution images of the best-bound wetting layers on Pt(111).

Two interpretations have been proposed of dark triangles observed in scanning tunneling microscopy (STM) images of the best bound, √37×√37-R25.3°, and √39×√39-R16.1° periodic water monolayers on Pt(111). In one, a "Y"-shaped tetramer of water molecules is removed, leaving a vacancy island behind; the other assumes the Y is replaced by a hexagon of H(2)O molecules, amounting to a di-interstitial. Consistent only with the di-interstitial model are thermal desorption and CO coadsorption data, STM line scans, and total energies obtained from density functional theory calculations.

Thermodynamics of surface morphology.

Classical thermodynamic descriptions of surfaces treat surface orientation as a thermodynamic degree of freedom and thus allow for the possibility of reversible changes in surface morphology as a function of temperature or impurity concentration. The existence of these transitions has been confirmed experimentally. Advances in surface diffraction and imaging techniques now make it possible to characterize such transitions quantitatively in terms of the atomic structure, and particularly in terms of the behavior of steps on surfaces. Statistical mechanical models can be used to analyze the observations to determine the fundamental energetic parameters governing the observed thermodynamic behavior.

Alloying at surfaces by the migration of reactive two-dimensional islands.

We have studied the formation kinetics of the copper-tin alloy bronze when tin is deposited on the (111) surface of copper at room temperature. Low-energy electron microscopy and atomic-resolution scanning tunneling microscopy reveal that bronze forms on the surface by a complicated, unanticipated cooperative mechanism: Ordered two-dimensional tin islands containing several hundred thousand atoms spontaneously sweep across the surface, leaving bronze alloys in their tracks. We propose that this process, driven by surface free energy, is a version of the "camphor dance" observed on liquid surfaces, and should be a general mechanism of surface alloying when surface diffusion is faster than exchange into the substrate.

Preparing arrays of large atomically flat regions on single crystal substrates.

We report a simple and general procedure to create arrays of atomically flat terraces on single crystal surfaces. Facets of three-dimensional (3D) metal islands formed after hetero-epitaxial growth are often flat and, through annealing or growth at elevated temperature, the formation of rather large (micron-scale) atomically flat-top facets can be promoted. We find that the step-free nature of top facets on such islands can be transferred to the substrate surface through room-temperature ion-sputter etching, followed by an annealing step. We use low-energy electron microscopy (LEEM) and Auger electron spectroscopy (AES) for in situ monitoring of the process steps while fabricating arrays of step-free surface regions on W(110), Ru(0001), Cu(100), and Fe(100) single crystals.

Observation of surface self-diffusion on ice.

To determine the role of surface diffusion on the morphology of ice surfaces we track the evolution with STM of 2D ice-island arrays on the basal surface of ice films on Pt(111) between 115 and 135 K. In contrast with previous measurements at higher temperatures, we find that the evolution is dominated by surface diffusion. The extracted surface self-diffusion coefficient has an activation energy of 0.4+/-0.1 eV, much less than the value previously measured for bulk diffusion.

Nanoscale periodicity in stripe-forming systems at high temperature: Au/W(110).

We observe using low-energy electron microscopy the self-assembly of monolayer-thick stripes of Au on W(110) near the transition temperature between stripes and the nonpatterned (homogeneous) phase. We demonstrate that the amplitude of this Au-stripe phase decreases with increasing temperature and vanishes at the order-disorder transition (ODT). The wavelength varies much more slowly with temperature and coverage than theories of stress-domain patterns with sharp boundaries would predict, and maintains a finite value of about 100 nm at the ODT. We argue that such nanometer-scale stripes should often appear near the ODT.

Spontaneous domain switching during phase separation of Pb on Ge(111).

Using low-energy electron microscopy (LEEM), we have discovered a novel phase separation mechanism for Pb on Ge(111). When the low Pb coverage (1 x 1) phase coexists with the high coverage beta phase, the surface consists of approximately 100 nm sized domains that spontaneously switch from one phase to the other. We argue this striking mechanism occurs because nanometer-scale domains can have density fluctuations comparable to the density difference between the two phases.

Evolution of a reactive surface via subsurface defect dynamics.

We find that the topography and composition of a reactive surface can evolve during epitaxy via motion of point and line defects within the material. We observe the response of a NiAl surface to an Al atom flux with low-energy electron microscopy. Initially, new NiAl layers grow as Al atoms exchange with bulk Ni atoms. When the surface is critically enriched in Al, condensation occurs at dislocations. They dissociate, move linearly, and leave tracks of altered composition and new atomic steps. We show how these dynamics depend on the identity and quantity of point defects near the surface.

Role of surface elastic relaxations in an O-induced nanopattern on Pt(110)-(1 x 2).

Scanning tunneling microscopy shows that a nanopattern forms as the Pt(110)-(1 x 2) surface is exposed to oxygen at room temperature or above. The nanopattern consists of [11[over]0] oriented O-induced stripes assembling into a (11 x 2) superstructure at high O coverage. The stripes form because the O adsorption energy increases by expanding the Pt lattice along the ridges of the surface as compared to the bulk. From interplay with density functional theory calculations, we show that the O-induced nanoscale periodicity is caused by short-ranged elastic relaxations confined to the surface.

How Pb-overlayer islands move fast enough to self-assemble on Pb-Cu surface alloys.

Low-energy electron microscopy reveals that two-dimensional, approximately 50 000 atom, Pb-overlayer and vacancy islands both have diffusion coefficients of 25.6+/-0.8 nm2/sec at 400 degrees C on Pb-Cu surface alloys. This high mobility, key to self-assembly in this system, results from the fast transport of Pb atoms on the surface alloy and of Cu through the Pb overlayer. A high Pb vacancy concentration, predicted by ab initio calculations, facilitates the latter.

Labyrinthine island growth during Pd/Ru(0001) heteroepitaxy.

Using low energy electron microscopy we observe that Pd deposited on Ru only attaches to small sections of the atomic step edges surrounding Pd islands. This causes a novel epitaxial growth mode in which islands advance in a snakelike motion, giving rise to labyrinthine patterns. Based on density functional theory together with scanning tunneling microscopy and low energy electron microscopy we propose that this growth mode is caused by a surface alloy forming around growing islands. This alloy gradually reduces step attachment rates, resulting in an instability that favors adatom attachment at fast advancing step sections.

Reversible shape transition of pb islands on Cu(111).

Using low-energy electron microscopy, we have observed a reversible transition in the shape of Pb adatom and vacancy islands on Cu(111). With increasing temperature, circular islands become elongated in one direction. In previous work we have shown that surface stress domain patterns are observed in this system with a characteristic feature size which decreases with increasing temperature. We show that the island shape transition occurs when the ratio of the island size to this characteristic feature size reaches a particular value. The observed critical ratio matches the value expected from stress domains.

Twin boundaries can be moved by step edges during film growth.

We track individual twin boundaries in Ag films on Ru(0001) using low-energy electron microscopy. The twin boundaries, which separate film regions whose close-packed planes are stacked differently, move readily during film growth but relatively little during annealing. The growth-driven motion of twin boundaries occurs as film steps advance across the surface--as a new atomic Ag layer reaches an fcc twin boundary, the advancing step edge carries along the boundary. This coupling of the microstructural defect (twin boundary) and the surface step during growth can produce film regions over 10 microm wide that are twin free.

Role of bulk thermal defects in the reconstruction dynamics of the TiO2(110) surface.

We use low-energy electron microscopy to show that changing the temperature of oxygen-deficient, rutile-structure crystals causes steps on the (110) surfaces to move. This motion occurs because the concentration of bulk oxygen vacancies changes with temperature, requiring that material be added to or subtracted from the surface. During cooling below a bulk-stoichiometry-dependent temperature, the surface reconstructs into a 1x2 structure in the regions surface steps have swept through, showing that the structural and compositional changes needed to form the 1x2 phase are facilitated by the surface-to-bulk mass flow.

Vacancies in solids and the stability of surface morphology.

Determining how thermal vacancies are created and destroyed in solids is crucial for understanding many of their physical properties, such as solid-state diffusion. Surfaces are known to be good sources and sinks for bulk vacancies, but directly determining where the exchange between the surface and the bulk occurs is difficult. Here we show that vacancy generation (and annihilation) on the (110) surface of an ordered nickel-aluminium intermetallic alloy does not occur over the entire surface, but only near atomic step edges. This has been determined by oscillating the sample's temperature and observing in real time the response of the surface structure as a function of frequency (a version of Angström's method of measuring thermal conductivity) using low-energy electron microscopy. Although the surface-exchange process is slow compared with bulk diffusion, the vacancy-generation rate nevertheless controls the dynamics of the alloy surface morphology. These observations, demonstrating that surface smoothing can occur through bulk vacancy transport rather than surface diffusion, should have important implications for the stability of fabricated nanoscale structures.

Diffusion kinetics in the Pd/Cu(001) surface alloy.

We use atom-tracking scanning tunneling microscopy to study the diffusion of Pd in the Pd/Cu(001) surface alloy as a function of temperature. By following the motion of individual Pd atoms incorporated in the surface, we show that Pd diffuses by a vacancy-exchange mechanism. We measure an activation energy for the diffusion of incorporated Pd atoms of 0.88 eV, which is in good agreement with our ab initio calculated energy of 0.94 eV.

Nanostructures. Self-assembled domain patterns.

The ordered domain patterns that form spontaneously in a wide variety of chemical and physical systems as a result of competing interatomic interactions can be used as templates for fabricating nanostructures. Here we describe a new self-assembling domain pattern on a solid surface that involves two surface structures of lead on copper. The evolution of the system agrees with theoretical predictions, enabling us to probe the interatomic force parameters that are crucial to the process.