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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.

Graphene forms from a relatively dense, tightly-bound C-adatom gas, when elemental C is deposited on or segregates to the Ru(0001) surface. Nonlinearity of the graphene growth rate with C adatom density suggests that growth proceeds by addition of C atom clusters to the graphene edge. The generality of this picture has now been studied by use of low-energy electron microscopy (LEEM) to observe graphene formation when Ru(0001) and Ir(111) surfaces are exposed to ethylene. The finding that graphene growth velocities and nucleation rates on Ru have precisely the same dependence on adatom concentration as for elemental C deposition implies that hydrocarbon decomposition only affects graphene growth through the rate of adatom formation; for ethylene, that rate decreases with increasing adatom concentration and graphene coverage. Initially, graphene growth on Ir(111) is like that on Ru: the growth velocity is the same nonlinear function of adatom concentration (albeit with much smaller equilibrium adatom concentrations, as we explain with DFT calculations of adatom formation energies). In the later stages of growth, graphene crystals that are rotated relative to the initial nuclei nucleate and grow. The rotated nuclei grow much faster. This difference suggests first, that the edgeorientation of the graphene sheets relative to the substrate plays an important role in the growth mechanism, and second, that attachment of the clusters to the graphene is the slowest step in cluster addition, rather than formation of clusters on the terraces.

Cubic boron nitride (cBN) has a number of highly desirable mechanical, thermal, electrical, and optical properties. Because of this, there has been an extensive worldwide effort to synthesize thin films of cBN. Film synthesis is difficult in that without significant levels of ion bombardment during growth, only sp2-bonded BN forms, not sp3-bonded cBN. Recently there has been considerable progress in improving the deposition techniques and cBN film quality. In addition, progress has been made in understanding how energetic deposition conditions can lead to cBN formation. However, unanswered questions remain and process improvements are still needed. In this paper we critically and comprehensively review recent developments in cBN film synthesis and characterization. First, the structures and stability of the BN phases and characterization techniques are described. Next, the key experimental parameters controlling cBN film formation and synthesis techniques are discussed. Following a review of microstructure, the proposed mechanisms of cBN formation and the observed mechanical and electrical properties of cBN films are analyzed. We conclude by highlighting the current impediments to the practical realization of cBN-film technology. 0 1997 Published by Elsevier Science S.A.

Photoelectron spectroscopic measurements have the potential to provide detailed mechanistic insight by resolving chemical states, electrochemically active regions and local potentials or potential losses in operating solid oxide electrochemical cells (SOCs), such as fuel cells. However, high-vacuum requirements have limited X-ray photoelectron spectroscopy (XPS) analysis of electrochemical cells to ex situ investigations. Using a combination of ambient-pressure XPS and CeO(2-x)/YSZ/Pt single-chamber cells, we carry out in situ spectroscopy to probe oxidation states of all exposed surfaces in operational SOCs at 750 °C in 1 mbar reactant gases H(2) and H(2)O. Kinetic energy shifts of core-level photoelectron spectra provide a direct measure of the local surface potentials and a basis for calculating local overpotentials across exposed interfaces. The mixed ionic/electronic conducting CeO(2-x) electrodes undergo Ce(3+)/Ce(4+) oxidation-reduction changes with applied bias. The simultaneous measurements of local surface Ce oxidation states and electric potentials reveal the active ceria regions during H(2) electro-oxidation and H(2)O electrolysis. The active regions extend ~150 μm from the current collectors and are not limited by the three-phase-boundary interfaces associated with other SOC materials. The persistence of the Ce(3+)/Ce(4+) shifts in the ~150 μm active region suggests that the surface reaction kinetics and lateral electron transport on the thin ceria electrodes are co-limiting processes.