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The ability of metal surfaces to dissociate hydrogen molecules is key to many ways that metals react to their environment. Often, the barrier to dissociation is linked to the formation of surface hydrogen adatoms. Here, we show that hydrogen can be more strongly bound to water-covered surfaces in the form of hydronium ions than as adatoms. Density functional theory reveals that the hydronium binding is proportional to the surface electronic work function. For the case of Pt(111), a particularly high work function surface, the proton affinity of adsorbed water films can be 0.4 eV larger than that of the bare metal surface. This binding is large enough to make the water films susceptible to the formation of hydroxyl and hydronium ion pairs. We present evidence from scanning tunneling microscopy for the existence of hydronium ions in water films on Pt(111). This new insight into the stability of hydronium-containing water layers provides a basis for more realistic models of the chemical reactivity of water films on metals.

Noble gases are generated within solids in nuclear environments and coalesce to form gas stabilized voids or cavities. Ion implantation has become a prevalent technique for probing how gas accumulation affects microstructural and mechanical properties. Transmission electron microscopy (TEM) allows measurement of cavity density, size, and spatial distributions post-implantation. While post-implantation microstructural information is valuable for determining the physical origins of mechanical property degradation in these materials, dynamic microstructural changes can only be determined by in situ experimentation techniques. We present in situ TEM experiments performed on Pd, a model face-centered cubic metal that reveals real-time cavity evolution dynamics. Observations of cavity nucleation and evolution under extreme environments are discussed.

We study the structure of the threading edge dislocations, or ``elbows,'' which are an essential component of the well-known herringbone reconstruction of the (111) surface of Au. Previous work had shown that these dislocations can be stabilized by long-range elastic relaxations into the bulk. However, the validity of the harmonic spring model that had been used to estimate the energies of the dislocations is uncertain. To enable a more refined model of the dislocation energetics, we have imaged the atomic structure of these dislocations using scanning tunneling microscopy. We find that the harmonic spring model does not adequately reproduce the observed structure. We are able to reproduce the structure, however, with a two-dimensional Frenkel-Kontorova (FK) model that uses a pairwise Morse potential to describe the interactions between the top layer Au atoms on a rigid substrate. The parameters of the potential were obtained by fitting the energy of uniaxially compressed phases, or ``stripes'', computed with density functional theory, as a function of surface Au density. Within this model, the formation of the threading dislocations remains unfavorable. However, the large forces on the substrate atoms near the threading-dislocation cores, render the assumption of a completely rigid substrate questionable. Indeed, if the FK parameters are modified to account for the relaxation of just one more atomic layer, threading dislocations can, in principle, become favorable, even without bulk elastic relaxations. Additional evidence for a small elbow energy is that our computed change in the Au(111) surface stress tensor caused by the $(\sqrt{3}\ifmmode\times\else\texttimes\fi{}22)$ reconstruction is considerably smaller than previous estimates.

We present and analyze a three-dimensional (3D) volume of nanoscale helium bubbles in a tritium-exposed palladium alloy that we have reconstructed by transmission electron tomography. Helium nanobubbles commonly form within metals during exposure to radiation and radioactive substances. The radioactive decay of tritium stored in metal tritides often results in a high density of these nanoscale helium bubbles. A persistent question about the mechanisms of bubble nucleation and growth has been the role of lattice defects and impurities. To address this matter, we have determined the 3D positions of helium nanobubbles in a palladium–nickel alloy exposed to tritium for 3.8 years. We introduce methods to determine the 3D shapes, volumes, and spatial positions of helium bubbles as small as 1 nm within solids. We find that the size and spacing of observed nanobubbles are not correlated. Our results suggest that previous models, which hypothesize initial, rapid homogeneous nucleation of nanobubbles followed by di...

8 pags., 7 figs., We have used low-energy electron microscopy (LEEM) to study how misfit dislocations evolve in the first atomic layer of Cu deposited on Ru(0001). At equilibrium the Cu islands are pseudomorphic and dislocation-free. However, the islands develop dislocation networks as they grow during deposition. These dislocations are metastable: after deposition ceases, the dislocated area shrinks as adatoms ejected from the network travel to the Cu-island edges. We analyze the dislocation decay rate and find no evidence of a significant energetic barrier for Cu adatoms to exchange with the dislocated phases. Instead, the metastable film's decay is consistent with adatom diffusion being the rate-limiting factor. A small barrier for changing misfit-dislocation density has a consequence – as a film's chemical environment changes during catalysis, its dislocation density can rapidly respond., This research was partly supported by the Office of Basic EnergySciences, Division of Materials Sciences, U.S. Department of Energy,and by the Spanish Ministry of Economy and Competitiveness ProjectNo. MAT2015-64110-C02-1-P. Sandia National Laboratories is a mul-timission laboratory managed and operated by National Technology and Engineering Solutions of Sandia LLC, a wholly owned subsidiary of Honeywell International Inc. for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA0003525

Helium bubbles are a severe form of radiation damage that has been frequently observed. It would be possible to understand the complex processes that cause bubble formation if suitable interatomic potentials were available to enable molecular dynamics simulations. In this paper, Pd-H-He embedded-atom method potentials based on both Daw-Baskes and Finnis-Sinclair formalisms have been developed to enable modeling of He bubbles formed by the radioactive decay of tritium in Pd. Our potentials incorporate helium into an existing Pd-H potential while addressing two challenging paradoxes: (a) Interstitial He atoms can dramatically lower their energies by forming dimers and larger clusters in Pd but are only bound by weak van der Waals forces in the gas phase. (b) He atoms diffuse readily in Pd yet significantly distort the Pd lattice with large volume expansions. We demonstrate that both of our potentials reproduce density functional theory results for (b). However, the Daw-Baskes formalism fails to resolve paradox (a) because it cannot reproduce the experimental helium equation of state. We resolved this problem through a modification of the Finnis-Sinclair formalism in which a (fictitious) negative embedding charge density is produced by Pd at the He binding sites. In addition to molecular statics validation of static properties, molecular dynamics simulation tests establish that our Finnis-Sinclair potential leads to the nucleation of helium bubbles from an initial random distribution of helium interstitial atoms.

The earliest stages of soot formation in flames are believed to involve the formation of small, nanoscale clusters of polycyclic aromatic hydrocarbon molecules. The structure of these clusters is still highly uncertain, however, impeding the construction of quantitative models of soot inception and growth. To provide insight into the structure of incipient soot, we produced nanoclusters of hydrocarbon molecules by annealing coronene films deposited on Pt(111), and examined them with scanning tunneling microcopy. We find that clusters containing ∼20–100 molecules, are disordered agglomerations of stacks that are ∼5–6 molecules tall. These structures are quite distinct from crystalline coronene, but bear a striking resemblance to recently proposed models for the equilibrium structure of similarly-sized clusters that are assumed to initiate soot formation. In contrast to mature soot, the surfaces of these clusters contain very few molecules with graphitic planes oriented parallel to the surface.

We have used scanning tunneling microscopy and density functional theory calculations to study molecular layers of coronene on Cu(111). The structure and stability of these layers is determined by the balance between coronene-substrate and coronene-coronene interactions. Here, we characterize this balance by measuring the maximum coverage before coronene dewets the substrate to form three-dimensional islands. We find that coronene molecules lie parallel to the substrate at the maximum coverage, in contrast to previous observations of tilted coronene on metal surfaces. We attribute this previously reported tilt to a metastability caused by an activation barrier to nucleate three-dimensional islands.

Author(s): Bartelt, NC; Li, Y; Sugar, JD; Fenton, K; Kilcoyne, ALD; Shapiro, DA; Tyliszczak, T; Chueh, WC; El Gabaly, F | Abstract: Incorporation of ions into battery electrodes can lead to phase transformations. When multiparticle phase-transforming electrodes charge or discharge, two processes must occur in each particle: the new phase must nucleate, and then grow until the particle is fully charged or discharged. A fundamental question is which of these two processes is rate limiting. Here we construct a simple stochastic model that shows how the relative rate of nucleation compared with growth determines the particle state-of-charge distributions in the electrode. We find that the number of particles that are partially charged at any time increases as the relative nucleation rate increases. The maximum number of particles that are actively charging occurs just before the time when the first particles are becoming completely charged. By comparing measured state-of-charge distributions with the model, we determine the relative rate of nucleation. We apply this procedure to measurements of the evolution of particles in LiFePO4 cathodes and show we can account for the particle state-of-charge distribution as a function of the electrode state of charge.

Many battery electrodes contain ensembles of nanoparticles that phase-separate on (de)intercalation. In such electrodes, the fraction of actively intercalating particles directly impacts cycle life: a vanishing population concentrates the current in a small number of particles, leading to current hotspots. Reports of the active particle population in the phase-separating electrode lithium iron phosphate (LiFePO4; LFP) vary widely, ranging from near 0% (particle-by-particle) to 100% (concurrent intercalation). Using synchrotron-based X-ray microscopy, we probed the individual state-of-charge for over 3,000 LFP particles. We observed that the active population depends strongly on the cycling current, exhibiting particle-by-particle-like behaviour at low rates and increasingly concurrent behaviour at high rates, consistent with our phase-field porous electrode simulations. Contrary to intuition, the current density, or current per active internal surface area, is nearly invariant with the global electrode cycling rate. Rather, the electrode accommodates higher current by increasing the active particle population. This behaviour results from thermodynamic transformation barriers in LFP, and such a phenomenon probably extends to other phase-separating battery materials. We propose that modifying the transformation barrier and exchange current density can increase the active population and thus the current homogeneity. This could introduce new paradigms to enhance the cycle life of phase-separating battery electrodes.

The atomistic mechanism for lithiation/delithiation in all-solid-state batteries is still an open question, and the ‘holy grail’ to engineer devices with extended lifetime. Here, by combining real-time scanning electron microscopy in ultra-high vacuum with electrochemical cycling, we quantify the dynamic degradation of Al anodes in Li-ion all-solid-state batteries, a promising alternative for ultra lightweight devices. We find that AlLi alloy mounds are formed on the top surface of the Al anode and that degradation of battery capacity occurs because of Li trapped in them. Our approach establishes a new platform for probing the real-time degradation of electrodes, and can be expanded to other complex systems, allowing for high throughput characterization of batteries with nanoscale resolution.

We demonstrate an ex situ method for analyzing the chemistry of battery electrode particles after electrochemical cycling using the transmission electron microscope (TEM). The arrangement of particles during our analysis is the same as when the particles are being cycled. We start by sectioning LiFePO 4 battery electrodes using an ultramicrotome. We then show that mapping of the Fe 2+ and Fe 3+ oxidation state using energy-filtered TEM (EFTEM) and multivariate statistical analysis techniques can be used to determine the spatial distribution of Li in the particles. This approach is validated by comparison with scanning transmission X-ray microscopy (STXM) analysis of the same samples [Chueh et al. Nanoletters, 13 (3) (2013) 866–72]. EFTEM uses a parallel electron beam and reduces the electron-beam dose (and potential beam-induced damage) to the sample when compared to alternate techniques that use a focused probe (e.g. STEM–EELS). Our analysis confirms that under the charging conditions of the analyzed battery, mixed phase particles are rare and thus Li intercalation is limited by the nucleation of new phases.

The exceptional properties of graphene originate from its two-dimensional polymeric structure of sp2-bonded carbon. This feature also causes graphene to grow on metal substrates through mechanisms that are strikingly different from those of conventional heteroepitaxy. We provide here a brief review of graphene growth on metals, a subject with a rich history even before the recent explosion of interest in graphene. The current activities related to graphene growth on metals have been motivated by the need to develop low-cost, scalable processes for graphene synthesis and to understand how graphene–metal interfaces behave in devices. In this article, we examine the current state of the art, emphasizing the basic processes that distinguish graphene growth from normal crystal growth.

We elucidate how graphene bilayers form on Ir(111). Low-energy electron diffraction (LEED) reveals that the two graphene layers are not always rotationally aligned. Monitoring this misalignment during growth shows that second-layer islands nucleate between the existing layer and the substrate. This mechanism occurs both when C segregates from the Ir and when elemental C is deposited from above. Low-energy electron microscopy (LEEM) and angle-resolved photoemission spectroscopy (ARPES) show that second-layer nucleation occurs preferentially under the first-layer rotational variants that are more weakly bound to the substrate. New-layer nucleation tends to occur inhomogeneously at substrate defects. Thus new-layer nucleation should be rapid on substrates that weakly bind graphene, making growth unstable toward mound formation initiated at substrate defects. In contrast, stronger binding permits layer-by-layer growth, as for Ru(0001). ARPES shows that bilayer graphene has two slightly p-doped π-bands. The work function of bilayer graphene is dominated by the orientation of the bottom layer.

We have observed the growth of monolayer graphene on Cu foils using low-energy electron microscopy. On the (100)-textured surface of the foils, four-lobed, 4-fold-symmetric islands nucleate and grow. The graphene in each of the four lobes has a different crystallographic alignment with respect to the underlying Cu substrate. These "polycrystalline" islands arise from complex heterogeneous nucleation events at surface imperfections. The shape evolution of the lobes is well explained by an angularly dependent growth velocity. Well-ordered graphene forms only above ∼790 °C. Sublimation-induced motion of Cu steps during growth at this temperature creates a rough surface, where large Cu mounds form under the graphene islands. Strategies for improving the quality of monolayer graphene grown on Cu foils must address these fundamental defect-generating processes.

We measure the concentration of carbon adatoms on the Ru(0 0 0 1) surface that are in equilibrium with C atoms in the crystal’s bulk by monitoring the electron reflectivity of the surface while imaging. During cooling from high temperature, C atoms segregate to the Ru surface, causing graphene islands to nucleate. Using low-energy electron microscopy (LEEM), we measure the growth rate of individual graphene islands and, simultaneously, the local concentration of C adatoms on the surface. We find that graphene growth is fed by the supersaturated, two-dimensional gas of C adatoms rather than by direct exchange between the bulk C and the graphene. At long times, the rate at which C diffuses from the bulk to the surface controls the graphene growth rate. The competition among C in three states – dissolved in Ru, as an adatom, and in graphene – is quantified and discussed. The adatom segregation enthalpy determined by applying the simple Langmuir–McLean model to the temperature-dependent equilibrium concentration seriously disagrees with the value calculated from first-principles. This discrepancy suggests that the assumption in the model of non-interacting C is not valid.

Scanning transmission electron microscope tomography and atom-probe tomography are both three-dimensional techniques on the nanoscale. We demonstrate here the combination of the techniques by analyzing the very same volume of an Al-Ag alloy specimen. This comparison allows us to directly visualize the theoretically known artifacts of each technique experimentally, providing insight into the optimal parameters to use for reconstructions and assessing the quality of each reconstruction. The combination of the techniques for accurate morphology and compositional information in three dimensions at the nanoscale provides a route for a new level of materials characterization and understanding.

Ice plays an important role in many naturally occurring phenomena. For example, most rainfall in temperate climates is triggered by the nucleation of ice around μm-sized particles in atmospheric clouds. Another reason to be interested in ice is that thin supported ice films provide excellent model systems for studying the interaction of water with solid surfaces. Despite the importance of water-solid interactions for catalysis, corrosion, water purification and fuel cells, even the basics of this interaction are poorly understood. In fact, the best theoretical models often fail to predict even the simplest phenomena. A fundamental question, for example, is whether water/ice wets a given substrate, i.e., whether the substrate is covered up by a uniformly thick water/ice film. (In the case of non-wetting an ice film would break up into separate three-dimensional (3D) crystallites of varying height, exposing the substrate.)

Carbon nanostructures, such as nanotubes and graphene, are of considerable interest due to their unique mechanical and electrical properties. The materials exhibit extremely high strength and conductivity when defects created during synthesis are minimized. Atomistic modeling is one technique for high resolution studies of defect formation and mitigation. To enable simulations of the mechanical behavior and growth mechanisms of C nanostructures, a high-fidelity analytical bond-order potential for the C is needed. To generate inputs for developing such a potential, we performed quantum mechanical calculations of various C structures.

Next generation metal-ion conducting membranes are key to developing energy storage and utilization technologies like batteries and fuel ce lls. Sodium super-ionic conductors (aka NaSICON) are a class of compounds with AM 1 M 2 (PO 4 ) 3 stoichiometry where the choice of "A" and "M" cation varies widely. This report, which de scribes substitutional derivatives of NZP (NaZr 2 P 3 O 12 ), summarizes the accomplishments of a Laboratory D irected Research and Development (LDRD) project to analyze transport mec hanisms using a combination of in situ studies of structure, composition, and bonding, com bined with first principles theory and modeling. We developed an experimental platform and applied methods, such as synchrotron- based X-ray spectroscopies, to probe the electronic structure of compositionally well-controlled NaSICON films while in operation ( i.e ., conducting Na ions exposed to oxygen or water va por atmospheres). First principles theory and modeling were used to interpret the experimental observations and develop an enhanced understanding of atomistic processes that give rise to, and affect, ion conduction.

The electrochemical reactions of solid oxide fuel cells occur in the region where gas-phase species, electrode, and electrolyte coincide. When the electrode is an ionic insulator and the electrolyte is an electronic insulator, this triple phase boundary is assumed to have atomic dimensions. Here we use photoemission electron microscopy to show that the reduced surface of the electrolyte yttria-stabilized zirconia (YSZ) has a sharp electronic metal-insulator boundary near Pt negative electrodes. The electronic conductivity of the reduced YSZ allows for oxygen reduction, allowing the reduced YSZ to behave as an extended triple phase boundary. This extended triple phase boundary can be many microns in size, depending on oxygen pressure, temperature, applied voltage, and time.

In this project we developed t he atomistic models needed to predict how graphene grows when carbon is deposited on metal and semiconductor surfaces. We first calculated energies of many carbon configurations using first principles electronic structure calculations and then used these energies to construct an empirical bond order potentials that enable s comprehensive molecular dynamics simulation of growth. We validated our approach by comparing our predictions to experiments of graphene growth on Ir, Cu and Ge. The robustness of ou r understanding of graphene growth will enable high quality graphene to be grown on novel substrates which will expand the number of potential types of graphene electronic devices.

We have used low-energy electron diffraction and microscopy to compare the growth of graphene on hydrogen-free Ge(111) and Ge(110) from an atomic carbon flux. Growth on Ge(110) leads to significantly better rotational alignment of graphene domains with the substrate. To explain the poor rotational alignment on Ge(111), we have investigated experimentally and theoretically how the adatom reconstructions of Ge interact with graphene. We find that the ordering transition of the Ge(111) adatom reconstruction is not significantly perturbed by graphene. Density functional theory calculations show that graphene on reconstructed Ge(110) has large-amplitude corrugations, whereas it is remarkably flat on reconstructed Ge(111). We argue that the absence of corrugations prevents graphene islands from locking into a preferred orientation.

We have studied the dislocation structures that occur in films of Ag, Au, and Ag0.5Au0.5 alloy on a Ru(0 0 0 1) substrate. Monolayer (ML) films form herringbone phases while films two or more layers thick contain triangular patterns of dislocations. We use scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED) to determine how the film composition affects the structure and periodicity of these ordered structures. One layer of Ag forms two different herringbone phases depending on the exact Ag coverage and temperature. Low-energy electron microscopy (LEEM) establishes that a reversible, first-order phase transition occurs between these two phases at a certain temperature. We critically compare our 1 ML Ag structures to conflicting results from an X-ray scattering study [H. Zajonz et al., Phys. Rev. B 67 (2003) 155417]. Unlike Ag, the herringbone phases of Au and AgAu alloy are independent of the exact film coverage. For two layer films in all three systems, none of the dislocations in the triangular networks thread into the second film layer. In all three systems, the in-plane atomic spacing of the second film layer is nearly the same as in the bulk. Film composition does, however, affect the details of the two layer structures. Ag and Au films form interconnected networks of dislocations, which we refer to as “trigons.” In 2 ML AgAu alloy, the dislocations form a different triangular network that shares features of both trigon and moire structures. Yet another well-ordered structure, with square symmetry, forms at the boundaries of translational trigon domains in 2 ML Ag films but not in Au films.

We have used scanning tunneling microscopy and low-energy electron microscopy to measure the thermal decay of two-dimensional Cu, Pb-overlayer, and Pb–Cu alloy islands on Pb–Cu(1 1 1) surface alloys. Decay rates covering 6–7 orders of magnitude are accessible by applying the two techniques to the same system. We find that Cu adatom diffusion across the surface alloy is rate-limiting for the decay of both Pb and Pb–Cu islands on the surface alloy and that this rate decreases monotonically with increasing Pb concentration in the alloy. The decrease is attributed to repulsive interactions between Cu adatoms and embedded Pb atoms in the surface alloy. The measured temperature dependences of island decay rates are consistent with first-principles calculations of the Cu binding and diffusion energies related to this “site-blocking” effect.

We use low-energy electron microscopy to study the mechanisms of thermal smoothing on Rh(001) surfaces at high temperature. By examining the change of areas of two-dimensional islands as a function of time and temperature, we find that smoothing from 1210 K to 1450 K is limited by the rate of surface diffusion on terraces and not by bulk vacancy diffusion as observed in other systems in the same temperature range. However, the activation energy we measure for island decay is inconsistent with previous measurements and calculations of the activation energy of surface diffusion and the adatom formation energy. This inconsistency combined with an unexpectedly large activation entropy suggests a surface transport mechanism other than simple hopping of adatoms across the surface.

Using low-energy electron microscopy, we show that de-wetting of Ag and Cu films on Ru(0 0 0 1) occurs by 3-D islands migrating across step edges in the “downhill” direction. We have observed islands thicken by more than 50 atomic layers in this manner. The island migration allows 3-D growth to occur in a way that avoids the nucleation barrier associated with forming 2-D islands on top of 3-D islands. Indeed, without substrate steps this nucleation barrier is not surmounted, and no 3-D islands are formed in the films studied.

We use low-energy electron microscopy to image the reversible transformation of the TiO 2 (1 1 0) surface between a high-temperature 1 × 1 structure and a low-temperature 1 × 2 structure. The reconstruction dynamics are novel: 1 × 2 bands nucleated during cooling at the steps of the starting 1 × 1 surface and then grew laterally from the steps. The transformation kinetics are dominated by mass flow from the surface to the bulk, a process that facilitates converting the high-density 1 × 1 phase to the lower-density 1 × 2 phase. We have also imaged how the 1 × 1 surface reconstructs to 1 × 2 phase after sufficient oxygen is removed from the crystal’s bulk during vacuum annealing. 1 × 2 bands also nucleated and grew laterally from the initial 1 × 1-surface’s steps. However, because this isothermal 1 × 1-to-1 × 2 transition occurs largely by mass redistribution on the surface, the steps of the initial 1 × 1 surface and final 1 × 2 surface are offset. We propose models of mass redistribution during the 1 × 1/1 × 2 phase transition to explain this effect. We conclude that the phase transition is first-order because it always occurred by the nucleation and growth of discrete phases. Finally, we show that quenching can roughen TiO 2 ’s surface by forming pits and that changing temperature causes step motion on 1 × 2 surfaces.

We study the diffusion of Pb atoms embedded in a Cu(0 0 1) surface using atom-tracking scanning tunneling microscopy. By comparing these observations with simulations based on first-principles electronic structure calculations, we deduce that the diffusion occurs by a vacancy-mediated mechanism in which the vacancy is attracted by the embedded Pb atom.

The influence of oxygen and sulfur on the dislocation patterns of the strained two monolayer Cu film on Ru was observed by scanning tunneling microscopy. Both oxygen and sulfur adsorption lead to the formation of vacancies that aggregate over existing dislocations in the film, thereby modifying the dislocation structure. With increasing adsorbate coverage the overall dislocation structure and pattern are transformed. The atomic mechanisms and general nature of this transformation can be explained in terms of generic dislocation reactions. This interpretation is also supported by atomistic simulations.

We use low-energy electron diffraction and low-energy electron microscopy (LEEM) to show that the TiO 2 (1 1 0) surface can reversibly transform between a high-temperature 1×1 phase and a low-temperature 1×2 phase. We find that the 1×1/1×2 transition occurs for a range of stoichiometry in oxygen-deficient crystals. To be quantitative about the stoichiometry dependence of the transition temperature, we accurately measure the crystal stoichiometry by using LEEM to determine the temperature at which crystallographic shear planes disappear from the bulk. In this way we show that the transition temperature increases with decreasing bulk oxygen content. By applying the Claperyon equation, we argue that this temperature dependence implies that the 1×1 and 1×2 surface phases have significantly different stoichiometries, with the 1×2 phase being Ti-rich compared to the 1×1 phase.

Using low-energy electron microscopy, we find that Cu and Pb, arranged in single atomic layers on the Cu(111) surface, self-assemble into ordered, nanoscale domain patterns. The pattern type, feature size, and degree of long-range order vary controllably with surface composition and temperature. The continuous evolution of the domain structures from circular islands to stripes to `inverted' islands with increasing Pb coverage agrees with theoretical predictions and simulations based on the existence of competing long- and short-range interactions. The details of the self-assembly process depend on a number of factors including temperature, surface morphology, and the presence of small amounts of sulfur.

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.

Graphene films grown by vapour deposition tend to be polycrystalline due to the nucleation and growth of islands with different in-plane orientations. Here, using low-energy electron microscopy, we find that micron-sized graphene islands on Ir(111) rotate to a preferred orientation during thermal annealing. We observe three alignment mechanisms: the simultaneous growth of aligned domains and dissolution of rotated domains, that is, ‘ripening'; domain boundary motion within islands; and continuous lattice rotation of entire domains. By measuring the relative growth velocity of domains during ripening, we estimate that the driving force for alignment is on the order of 0.1 meV per C atom and increases with rotation angle. A simple model of the orientation-dependent energy associated with the moiré corrugation of the graphene sheet due to local variations in the graphene–substrate interaction reproduces the results. This work suggests new strategies for improving the van der Waals epitaxy of 2D materials., Understanding the factors that control island orientation in the growth of two-dimensional materials is likely to improve their quality. Here, using low-energy electron microscopy, the authors show that post-nucleation annealing of 2D materials can improve rotational order.

We examined the growth and stability of ice layers on Ni(111) up to ∼7 molecular layers (ML) thick using scanning tunneling microscopy. At low coverage, films were comprised of ∼1 nm wide two-dimensional (2D) clusters. Only above ∼0.5 ML did patches of continuous 2D layers emerge, coexisting with the clusters until the first ML was complete. The structure of the continuous layer is clearly different from that of the 2D clusters. Subsequently, a second molecular layer grew on top of the first. 3D crystallites started to form only after this 2nd ML was complete. 2D clusters re-appeared when thicker films were partially evaporated, implying that these clusters represent the equilibrium configuration at low coverage. Binding energies and image simulations computed with density functional theory suggest that the 2D clusters are partially dissociated and surrounded by H adatoms. The complete 2D layer contains only intact water molecules because of the lack of favorable binding sites for H atoms. We propose molecular structures for the 2D layer that are composed of the same pentagon-heptagon binding motif and water density observed on Pt(111). The similarity of the water structures on Pt and Ni suggests a general prescription for generating low-energy configurations on close-packed metal substrates.

New discoveries on collective processes in materials fabrication and performance are emerging in the mesoscopic size regime between the nanoscale, where atomistic effects dominate, and the macroscale, where bulk-like behavior rules. For semiconductor electronics and photonics, dimensional control of the architecture in this regime is the limiting factor for device performance. Epitaxial crystal growth is the major tool enabling simultaneous control of the dimensions and properties of such architectures. Although size-dependent effects have been studied for many small-scale systems, they have not been reported for the epitaxial growth of Si crystalline surfaces. Here, we show a strong dependence of epitaxial growth rates on size for nano to microscale radial wires and planar stripes. A model for this unexpected size-dependent vapor phase epitaxy behavior at small dimensions suggests that these effects are universal and result from an enhanced surface desorption of the silane (SiH4) growth precursor near facet edges. Introducing phosphorus or boron dopants during the silicon epitaxy further decreases the growth rates and, for phosphorus, gives rise to a critical layer thickness for single crystalline epitaxial growth. This previously unknown mesoscopic size-dependent growth effect at mesoscopic dimensions points to a new mechanism in vapor phase growth and promises greater control of advanced device geometries.

Using scanning tunneling microscopy (STM) and first-principles local-spin-density-approximation calculations to study submonolayer films of $\mathrm{Co}{}_{1\ensuremath{-}c}\mathrm{Ag}{}_{c}/\mathrm{Ru}(0001)$ alloys, we have discovered a novel phase-separation mechanism. When the Ag concentration $c$ exceeds 0.4, the surface phase separates between a dislocated, pure Ag phase and a pseudomorphically strained $\mathrm{Co}{}_{0.6}\mathrm{Ag}{}_{0.4}$ surface alloy. We attribute the phase separation to the competition between two stress relief mechanisms: surface alloying and dislocation formation. The agreement between STM measurements and our calculated phase diagram supports this interpretation.

Structural and thermodynamic properties of thermally equilibrated Pd-Au/Ru(0001) surface alloys are studied within the framework of lattice models based upon first-principles total energy calculations and scanning-tunneling-microscopy imaging of atomic structure. Pd-rich alloys form pseudomorphic solid-solution phases with pronounced chemical short-range order (SRO), consistent with the prediction of a low-temperature order-disorder transition to a ({radical}(3){times}{radical}(3) )-R30{degree} ground state structure. Calculated and measured SRO parameters are found to be in excellent agreement and are quantitatively described by a lattice-model Hamiltonian dominated by short-ranged interactions. {copyright} {ital 1999} {ital The American Physical Society}

Vacancy islands formed during room-temperature exposure to sulfur of a submonolayer Ag film on Ru(0001) order spontaneously to form a triangular lattice at an island area fraction just above 20%. A normal mode decomposition of the thermal vibrations of this vacancy island crystal, measured with time-resolved scanning tunneling microscopy, obtains Lame coefficients in the range of 10 8 N m −2 . We show that these estimates are consistent with stabilizing forces derived from long-range elastic interactions between the islands.

Strained thin films often contain ordered networks of misfit dislocations which can determine their chemical and mechanical properties. We consider the reaction of sulfur with two-monolayer films of Cu on Ru(0001). These films contain a network of parallel partial dislocations, separating regions of fcc and hcp stacking, with threading edge dislocations where partial dislocations meet. Sulfur reacts with the threading dislocations and dissociates them. The increase in the threading dislocation density is accommodated by modifying the dislocation network.

We have used the low energy electron microscope (LEEM) to investigate step faceting and striped phase formation on heavily boron-doped Si(001) surfaces. Measurements of thermal fluctuations along the steps, equilibrium island shapes, and the angle of triangular facets provide quantitative information on the step formation energies. We find that a simple, systematic temperature dependence of the spatial anisotropy of the free energy of isolated steps is sufficient to account for the observed faceting of the B type steps. These results suggest that the proliferation of straight A step edges at lower temperature is caused by the energy of isolated A steps becoming vanishingly small. We show that rapid cooling of the samples leads to the nucleation and growth of a high density of vacancy islands on the surfaces. Based on these results, we propose a qualitative model for mass transport during stripe formation.

We describe Monte Carlo simulations and diffusion equation analysis which are useful in deriving kinetic parameters from low energy electron microscopy experiments. An analysis of the etching of the Si(001) surface with molecular oxygen is made, illustrating the power of these techniques.

We have used low-energy electron microscopy to study the etching of large terraces on Si(001) with molecular oxygen. By imaging the etching process in situ, and comparing the results to detailed kinetic models, we determine and quantify the dominant mechanisms by which oxygen attacks the surface. We find that the etch rate follows an Arrhenius form with an activation energy of $2.0\ifmmode\pm\else\textpm\fi{}0.4\mathrm{eV}$, significantly lower than estimates reported in modulated beam investigations.

The interaction of a model strained metal film with oxygen is studied by scanning tunneling microscopy. Two monolayers of copper on Ru(0001) present a well-defined dislocation network composed of threading dislocations and Shockley partial dislocations separating areas of fcc and hcp stacking. We find that oxygen first reacts with these threading dislocations. Then, for exposures up to ~0.4 L O 2 , new threading dislocation arrays appear on the surface. With the addition of more oxygen, the mesoscopic structure of the film changes from a striped array of Shockley partials to a disordered array of triangular fcc regions bounded by dislocations, as oxygen proceeds to etch away the hcp areas of the copper film. © 1998 Published by Elsevier Science B.V. All rights reserved.

We have used scanning tunneling microscopy to study grain boundary motion in oxygen films adsorbed on Ru(0001). Starting from an analysis of atomically resolved images of the thermal motion of oxygen atoms within the grain boundaries, we are able to successfully predict the future of complicated configurations of grains involving several hundred thousand atoms over several hours. The detail to which theory can reproduce experimental histories shows the precision to which previously hypothetical models of surface kinetics can now be verified. {copyright} {ital 1998} {ital The American Physical Society}