Cometary Dust.

This review presents our understanding of cometary dust at the end of 2017. For decades, insight about the dust ejected by nuclei of comets had stemmed from remote observations from Earth or Earth's orbit, and from flybys, including the samples of dust returned to Earth for laboratory studies by the Stardust return capsule. The long-duration Rosetta mission has recently provided a huge and unique amount of data, obtained using numerous instruments, including innovative dust instruments, over a wide range of distances from the Sun and from the nucleus. The diverse approaches available to study dust in comets, together with the related theoretical and experimental studies, provide evidence of the composition and physical properties of dust particles, e.g., the presence of a large fraction of carbon in macromolecules, and of aggregates on a wide range of scales. The results have opened vivid discussions on the variety of dust-release processes and on the diversity of dust properties in comets, as well as on the formation of cometary dust, and on its presence in the near-Earth interplanetary medium. These discussions stress the significance of future explorations as a way to decipher the formation and evolution of our Solar System.

Epitaxially Self-Assembled Alkane Layers for Graphene Electronics.

The epitaxially grown alkane layers on graphene are prepared by a simple drop-casting method and greatly reduce the environmentally driven doping and charge impurities in graphene. Multiscale simulation studies show that this enhancement of charge homogeneity in graphene originates from the lifting of graphene from the SiO2 surface toward the well-ordered and rigid alkane self-assembled layers.

Band Alignment in MoS2/WS2 Transition Metal Dichalcogenide Heterostructures Probed by Scanning Tunneling Microscopy and Spectroscopy.

Using scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS), we examine the electronic structure of transition metal dichalcogenide heterostructures (TMDCHs) composed of monolayers of MoS2 and WS2. STS data are obtained for heterostructures of varying stacking configuration as well as the individual monolayers. Analysis of the tunneling spectra includes the influence of finite sample temperature, yield information about the quasi-particle bandgaps, and the band alignment of MoS2 and WS2. We report the band gaps of MoS2 (2.16 ± 0.04 eV) and WS2 (2.38 ± 0.06 eV) in the materials as measured on the heterostructure regions and the general type II band alignment for the heterostructure, which shows an interfacial band gap of 1.45 ± 0.06 eV.

Dopant segregation in polycrystalline monolayer graphene.

Heterogeneity in dopant concentration has long been important to the electronic properties in chemically doped materials. In this work, we experimentally demonstrate that during the chemical vapor deposition process, in contrast to three-dimensional polycrystals, the substitutional nitrogen atoms avoid crystal grain boundaries and edges over micron length scales while distributing uniformly in the interior of each grain. This phenomenon is universally observed independent of the details of the growth procedure such as temperature, pressure, substrate, and growth precursor.

Interstellar dust. Evidence for interstellar origin of seven dust particles collected by the Stardust spacecraft.

Seven particles captured by the Stardust Interstellar Dust Collector and returned to Earth for laboratory analysis have features consistent with an origin in the contemporary interstellar dust stream. More than 50 spacecraft debris particles were also identified. The interstellar dust candidates are readily distinguished from debris impacts on the basis of elemental composition and/or impact trajectory. The seven candidate interstellar particles are diverse in elemental composition, crystal structure, and size. The presence of crystalline grains and multiple iron-bearing phases, including sulfide, in some particles indicates that individual interstellar particles diverge from any one representative model of interstellar dust inferred from astronomical observations and theory.

Edge structures for nanoscale graphene islands on Co(0001) surfaces.

Low-temperature scanning tunneling microscopy measurements and first-principles calculations are employed to characterize edge structures observed for graphene nanoislands grown on the Co(0001) surface. Images of these nanostructures reveal straight well-ordered edges with zigzag orientation, which are characterized by a distinct peak at low bias in tunneling spectra. Density functional theory based calculations are used to discriminate between candidate edge structures. Several zigzag-oriented edge structures have lower formation energy than armchair-oriented edges. Of these, the lowest formation energy configurations are a zigzag and a Klein edge structure, each with the final carbon atom over the hollow site in the Co(0001) surface. In the absence of hydrogen, the interaction with the Co(0001) substrate plays a key role in stabilizing these edge structures and determines their local conformation and electronic properties. The calculated electronic properties for the low-energy edge structures are consistent with the measured scanning tunneling images.

Segregation of sublattice domains in nitrogen-doped graphene.

Atomic-level details of dopant distributions can significantly influence the material properties. Using scanning tunneling microscopy, we investigate the distribution of substitutional dopants in nitrogen-doped graphene with regard to sublattice occupancy within the honeycomb structure. Samples prepared by chemical vapor deposition (CVD) using pyridine on copper exhibit well-segregated domains of nitrogen dopants in the same sublattice, extending beyond 100 nm. On the other hand, samples prepared by postsynthesis doping of pristine graphene exhibit a random distribution between sublattices. On the basis of theoretical calculations, we attribute the formation of sublattice domains to the preferential attachment of nitrogen to the edge sites of graphene during the CVD growth process. The breaking of sublattice symmetry in doped graphene can have important implications in its electronic applications, such as the opening of a tunable band gap in the material.

Local atomic and electronic structure of boron chemical doping in monolayer graphene.

We use scanning tunneling microscopy and X-ray spectroscopy to characterize the atomic and electronic structure of boron-doped and nitrogen-doped graphene created by chemical vapor deposition on copper substrates. Microscopic measurements show that boron, like nitrogen, incorporates into the carbon lattice primarily in the graphitic form and contributes ~0.5 carriers into the graphene sheet per dopant. Density functional theory calculations indicate that boron dopants interact strongly with the underlying copper substrate while nitrogen dopants do not. The local bonding differences between graphitic boron and nitrogen dopants lead to large scale differences in dopant distribution. The distribution of dopants is observed to be completely random in the case of boron, while nitrogen displays strong sublattice clustering. Structurally, nitrogen-doped graphene is relatively defect-free while boron-doped graphene films show a large number of Stone-Wales defects. These defects create local electronic resonances and cause electronic scattering, but do not electronically dope the graphene film.

Substrate level control of the local doping in graphene.

Graphene exfoliated onto muscovite mica is studied using ultrahigh vacuum scanning tunneling microscopy (UHV-STM) techniques. Mica provides an interesting dielectric substrate interface to measure the properties of graphene due to the ultraflat nature of a cleaved mica surface and the surface electric dipoles it possesses. Flat regions of the mica surface show some surface modulation of the graphene topography (24 pm) due to topographic modulation of the mica surface and full conformation of the graphene to that surface. In addition to these ultraflat regions, plateaus of varying size having been found. A comparison of topographic images and STS measurements show that these plateaus are of two types: one with characteristics of water monolayer formation between the graphene and mica, and the other arising from potassium ions trapped at the interfacial region. Immediately above the water induced plateaus, graphene is insulated from charge doping, while p-type doping is observed in areas adjacent to these water nucleation points. However, above and in the neighborhood of interfacial potassium ions, only n-type doping is observed. Graphene regions above the potassium ions are more strongly n-doped than regions adjacent to these alkali atom plateaus. Furthermore, a direct correlation of these Fermi level shifts with topographic features is seen without the random charge carrier density modulation observed in other dielectric substrates. This suggests a possible route to nanoscopic control of the local electron and hole doping in graphene via specific substrate architecture.

Slow gold adatom diffusion on graphene: effect of silicon dioxide and hexagonal boron nitride substrates.

We examine the nucleation kinetics of Au clusters on graphene and explore the relationship with layer number and underlying supporting substrate of graphene. Using the mean field theory of diffusion-limited aggregation, morphology patterns are semiquantitatively analyzed to obtain Au adatom effective diffusion constants and activation energies. Under specified assumptions, the Au adatom diffusion constant for single-layer graphene supported on SiO2 is ∼50 times smaller than that for hexagonal boron nitride (h-BN)-supported graphene and on the order of 800 times smaller than that for multilayer graphite. Bilayer graphene on SiO2 shows a Au adatom diffusion constant similar to single-layer graphene on h-BN. Scanning probe data show that single-layer graphene is far flatter on h-BN than on SiO2. Two factors are proposed as contributing to the observed lower diffusion constants on single-layer graphene: local surface roughness and homogeneous loss of dispersion/van der Waals electronic stability in multilayers. Graphene Raman spectroscopy shows little charge transfer between Au nanoparticles and graphene.

Scanning tunneling microscopy and theoretical study of water adsorption on Fe3O4: implications for catalysis.

The reduced surface of a natural Hematite single crystal α-Fe(2)O(3)(0001) sample has multiple surface domains with different terminations, Fe(2)O(3)(0001), FeO(111), and Fe(3)O(4)(111). The adsorption of water on this surface was investigated via Scanning Tunneling Microscopy (STM) and first-principle theoretical simulations. Water species are observed only on the Fe-terminated Fe(3)O(4)(111) surface at temperatures up to 235 K. Between 235 and 245 K we observed a change in the surface species from intact water molecules and hydroxyl groups bound to the surface to only hydroxyl groups atop the surface terminating Fe(III) cations. This indicates a low energy barrier for water dissociation on the surface of Fe(3)O(4) that is supported by our theoretical computations. Our first principles simulations confirm the identity of the surface species proposed from the STM images, finding that the most stable state of a water molecule is the dissociated one (OH + H), with OH atop surface terminating Fe(III) sites and H atop under-coordinated oxygen sites. Attempts to simulate reaction of the surface OH with coadsorbed CO fail because the only binding sites for CO are the surface Fe(III) atoms, which are blocked by the much more strongly bound OH. In order to promote this reaction we simulated a surface decorated with gold atoms. The Au adatoms are found to cap the under-coordinated oxygen sites and dosed CO is found to bind to the Au adatom. This newly created binding site for CO not only allows for coexistence of CO and OH on the surface of Fe(3)O(4) but also provides colocation between the two species. These two factors are likely promoters of catalytic activity on Au/Fe(3)O(4)(111) surfaces.

Perspective: The dawning of the age of graphene.

Graphene is a single sheet of carbon atoms that constitutes the basic building block of macroscopic graphite crystals. Held together by a backbone of overlapping sp(2) hybrids, graphene's 2p orbitals form π state bands that delocalize over an entire 2-dimensional macroscopic carbon sheet leading to a number of unusual characteristics that include large electrical and thermal conductivities. Recent discoveries have provided simple methods (e.g., mechanical cleavage of graphite) for preparing laboratory scale samples that can be used to investigate the fundamental physical and chemical characteristics of graphene. In addition, a number of techniques have emerged that show promise for producing large-scale samples with the ultimate goal of developing devices that take advantage of graphene's unusual properties. As large samples become available, the possibility grows for applications of this material in solar cell technology (as flexible, transparent electrodes), in composite material development, and in electronic devices.

Visualizing individual nitrogen dopants in monolayer graphene.

In monolayer graphene, substitutional doping during growth can be used to alter its electronic properties. We used scanning tunneling microscopy, Raman spectroscopy, x-ray spectroscopy, and first principles calculations to characterize individual nitrogen dopants in monolayer graphene grown on a copper substrate. Individual nitrogen atoms were incorporated as graphitic dopants, and a fraction of the extra electron on each nitrogen atom was delocalized into the graphene lattice. The electronic structure of nitrogen-doped graphene was strongly modified only within a few lattice spacings of the site of the nitrogen dopant. These findings show that chemical doping is a promising route to achieving high-quality graphene films with a large carrier concentration.

Scanning tunneling microscopy and X-ray photoelectron spectroscopy studies of graphene films prepared by sonication-assisted dispersion.

We describe scanning tunneling microscopy and X-ray photoelectron spectroscopy studies of graphene films produced by sonication-assisted dispersion. Defects in these samples are not randomly distributed, and the graphene films exhibit a "patchwork" structure where unperturbed graphene areas are adjacent to heavily functionalized ones. Adjacent graphene layers are likely in poor mechanical contact due to adventitious species trapped between the carbon sheets of the sample.

Atmospheric oxygen binding and hole doping in deformed graphene on a SiO2 substrate.

Using micro-Raman spectroscopy and scanning tunneling microscopy, we study the relationship between structural distortion and electrical hole doping of graphene on a silicon dioxide substrate. The observed upshift of the Raman G band represents charge doping and not compressive strain. Two independent factors control the doping: (1) the degree of graphene coupling to the substrate and (2) exposure to oxygen and moisture. Thermal annealing induces a pronounced structural distortion due to close coupling to SiO2 and activates the ability of diatomic oxygen to accept charge from graphene. Gas flow experiments show that dry oxygen reversibly dopes graphene; doping becomes stronger and more irreversible in the presence of moisture and over long periods of time. We propose that oxygen molecular anions are stabilized by water solvation and electrostatic binding to the silicon dioxide surface.

Ultraflat graphene.

Graphene, a single atomic layer of carbon connected by sp(2) hybridized bonds, has attracted intense scientific interest since its recent discovery. Much of the research on graphene has been directed towards exploration of its novel electronic properties, but the structural aspects of this model two-dimensional system are also of great interest and importance. In particular, microscopic corrugations have been observed on all suspended and supported graphene sheets studied so far. This rippling has been invoked to explain the thermodynamic stability of free-standing graphene sheets. Many distinctive electronic and chemical properties of graphene have been attributed to the presence of ripples, which are also predicted to give rise to new physical phenomena that would be absent in a planar two-dimensional material. Direct experimental study of such novel ripple physics has, however, been hindered by the lack of flat graphene layers. Here we demonstrate the fabrication of graphene monolayers that are flat down to the atomic level. These samples are produced by deposition on the atomically flat terraces of cleaved mica surfaces. The apparent height variation in the graphene layers observed by high-resolution atomic force microscopy (AFM) is less than 25 picometres, indicating the suppression of any existing intrinsic ripples in graphene. The availability of such ultraflat samples will permit rigorous testing of the impact of ripples on various physical and chemical properties of graphene.

Structure and electronic properties of graphene nanoislands on Co(0001).

We have grown well-ordered graphene adlayers on the lattice-matched Co(0001) surface. Low-temperature scanning tunneling microscopy measurements demonstrate an on-top registry of the carbon atoms with respect to the Co(0001) surface. The tunneling conductance spectrum shows that the electronic structure is substantially altered from that of isolated graphene, implying a strong coupling between graphene and cobalt states. Calculations using density functional theory confirm that structures with on-top registry have the lowest energy and provide clear evidence for strong electronic coupling between the graphene pi-states and Co d-states at the interface.

Scanning tunneling microscopy images of alkane derivatives on graphite: role of electronic effects.

Scanning tunneling microscopy (STM) images of self-assembled monolayers of close-packed alkane chains on highly oriented pyrolitic graphite often display an alternating bright and dark spot pattern. Classical simulations suggest that a tilt of the alkane backbone is unstable and, therefore, unlikely to account for the contrast variation. First principles calculations based on density functional theory show that an electronic effect can explain the observed alternation. Furthermore, the asymmetric spot pattern associated with the minimum energy alignment is modulated depending on the registry of the alkane adsorbate relative to the graphite surface, explaining the characteristic moiré pattern that is often observed in STM images with close packed alkyl assemblies.

Graphene oxidation: thickness-dependent etching and strong chemical doping.

Patterned graphene shows substantial potential for applications in future molecular-scale integrated electronics. Environmental effects are a critical issue in a single-layer material where every atom is on the surface. Especially intriguing is the variety of rich chemical interactions shown by molecular oxygen with aromatic molecules. We find that O 2 etching kinetics vary strongly with the number of graphene layers in the sample. Three-layer-thick samples show etching similar to bulk natural graphite. Single-layer graphene reacts faster and shows random etch pits in contrast to natural graphite where nucleation occurs at point defects. In addition, basal plane oxygen species strongly hole dope graphene, with a Fermi level shift of approximately 0.5 eV. These oxygen species desorb partially in an Ar gas flow, or under irradiation by far UV light, and readsorb again in an O 2 atmosphere at room temperature. This strongly doped graphene is very different from "graphene oxide" made by mineral acid attack.