Selective hydrogenation of graphene on Ir(111): an X-ray standing wave study.

A combined high resolution X-ray photoelectron spectroscopy and X-ray standing wave study into the adsorption structure of hydrogenated graphene on Ir(111) is presented. By exploiting the unique absorption profiles and significant modulations in signal intensity found within the X-ray standing wave results, we refine the fitting of the C 1s X-ray photoelectron spectra, allowing us to disentangle the contributions from hydrogenation of graphene in different high-symmetry regions of the moiré supercell. We clearly demonstrate that hydrogenation in the FCC regions results in the formation of a graphane-like structure, giving a standalone component that is separated from the component assigned to the similar structure in the HCP regions. The contribution from dimer structures in the ATOP regions is found to be minor or negligible. This is in contrast to the previous findings where a dimer structure was assumed to contribute significantly to the sp3 part of the C 1s spectra. The corrugation of the remaining pristine parts of the H-graphene is shown to increase with the H coverage, reflecting an increasing number and size of pinning centers of the graphene to the Ir(111) substrate with increasing H exposure.

Growth and electronic properties of bi- and trilayer graphene on Ir(111).

Interesting electronic properties arise in vertically stacked graphene sheets, some of which can be controlled by mutual orientation of the adjacent layers. In this study, we investigate the MBE grown multilayer graphene on Ir(111) by means of STM, LEED and XPS and we examine the influence of the substrate on the geometric and electronic properties of bilayer graphene by employing XSW and ARPES measurements. We find that the MBE method does not limit the growth to two graphene layers and that the wrinkles, which arise through extended carbon deposition, play a crucial role in the multilayer growth. We also find that the bilayer and trilayer graphene sheets have graphitic-like properties in terms of the separation between the two layers and their stacking. The presence of the iridium substrate imposes a periodic potential induced by the moiré pattern that was found to lead to the formation of replica bands and minigaps in bilayer graphene. From tight-binding fits to our ARPES data we find that band renormalization takes place in multilayer graphene due to a weaker coupling of the upper-most graphene layer to the iridium substrate.

Chemically-resolved determination of hydrogenated graphene-substrate interaction.

Functionalization of graphene on Ir(111) is a promising route to modify graphene by chemical means in a controlled fashion at the nanoscale. Yet, the nature of such functionalized sp3 nanodots remains unknown. Density functional theory (DFT) calculations alone cannot differentiate between two plausible structures, namely true graphane and substrate stabilized graphane-like nanodots. These two structures, however, interact dramatically differently with the underlying substrate. Discriminating which type of nanodots forms on the surface is thus of paramount importance for the applications of such prepared nanostructures. By comparing X-ray standing wave measurements against theoretical model structures obtained by DFT calculations we are able to exclude the formation of true graphane nanodots and clearly show the formation graphane-like nanodots.

Hydrogen interaction with graphene on Ir(1 1 1): a combined intercalation and functionalization study.

We demonstrate a procedure for obtaining a H-intercalated graphene layer that is found to be chemically decoupled from the underlying metal substrate. Using high-resolution x-ray photoelectron spectroscopy and scanning tunneling microscopy techniques, we reveal that the hydrogen intercalated graphene is p-doped by about 0.28 eV, but also identify structures of interfacial hydrogen. Furthermore, we investigate the reactivity of the decoupled layer towards atomic hydrogen and vibrationally excited molecular hydrogen and compare these results to the case of non-intercalated graphene. We find distinct differences between the two. Finally, we discuss the possibility to form graphane clusters on an iridium substrate by combined intercalation and H atom exposure experiments.

Enhancing Graphene Protective Coatings by Hydrogen-Induced Chemical Bond Formation.

Increased interactions at the graphene-metal interface are here demonstrated to yield an effective prevention of intercalation of foreign species below the graphene cover. Hereby, an engineering pathway for increasing the usability of graphene as a metal coating is demonstrated. Graphene on Ir(111) (Gr/Ir(111)) is used as a model system, as it has previously been well-established that an increased interaction and formation of chemical bonds at the graphene-Ir interface can be induced by hydrogen functionalization of the graphene from its top side. With X-ray photoelectron spectroscopy, it is shown that hydrogen-induced increased interactions at the Gr/Ir(111) interface effectively prevents intercalation of CO in the millibar range. The scheme leads to protection against at least 10 times higher pressure and 70 times higher fluences of CO, compared to the protection offered by pristine Gr/Ir(111).

Exciting H2 Molecules for Graphene Functionalization.

Hydrogen functionalization of graphene by exposure to vibrationally excited H2 molecules is investigated by combined scanning tunneling microscopy, high-resolution electron energy loss spectroscopy, X-ray photoelectron spectroscopy measurements, and density functional theory calculations. The measurements reveal that vibrationally excited H2 molecules dissociatively adsorb on graphene on Ir(111) resulting in nanopatterned hydrogen functionalization structures. Calculations demonstrate that the presence of the Ir surface below the graphene lowers the H2 dissociative adsorption barrier and allows for the adsorption reaction at energies well below the dissociation threshold of the H-H bond. The first reacting H2 molecule must contain considerable vibrational energy to overcome the dissociative adsorption barrier. However, this initial adsorption further activates the surface resulting in reduced barriers for dissociative adsorption of subsequent H2 molecules. This enables functionalization by H2 molecules with lower vibrational energy, yielding an avalanche effect for the hydrogenation reaction. These results provide an example of a catalytically active graphene-coated surface and additionally set the stage for a re-interpretation of previous experimental work involving elevated H2 background gas pressures in the presence of hot filaments.

Erratum: Self-assembly of ordered graphene nanodot arrays.

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Self-assembly of ordered graphene nanodot arrays.

The ability to fabricate nanoscale domains of uniform size in two-dimensional materials could potentially enable new applications in nanoelectronics and the development of innovative metamaterials. However, achieving even minimal control over the growth of two-dimensional lateral heterostructures at such extreme dimensions has proven exceptionally challenging. Here we show the spontaneous formation of ordered arrays of graphene nano-domains (dots), epitaxially embedded in a two-dimensional boron-carbon-nitrogen alloy. These dots exhibit a strikingly uniform size of 1.6 ± 0.2 nm and strong ordering, and the array periodicity can be tuned by adjusting the growth conditions. We explain this behaviour with a model incorporating dot-boundary energy, a moiré-modulated substrate interaction and a long-range repulsion between dots. This new two-dimensional material, which theory predicts to be an ordered composite of uniform-size semiconducting graphene quantum dots laterally integrated within a larger-bandgap matrix, holds promise for novel electronic and optoelectronic properties, with a variety of potential device applications.The nanoscale patterning of two-dimensional materials offers the possibility of novel optoelectronic properties; however, it remains challenging. Here, Camilli et al. show the self-assembly of large arrays of highly-uniform graphene dots imbedded in a BCN matrix, enabling novel devices.

Quantum Dots Embedded in Graphene Nanoribbons by Chemical Substitution.

Bottom-up chemical reactions of selected molecular precursors on a gold surface can produce high quality graphene nanoribbons (GNRs). Here, we report on the formation of quantum dots embedded in an armchair GNR by substitutional inclusion of pairs of boron atoms into the GNR backbone. The boron inclusion is achieved through the addition of a small amount of boron substituted precursors during the formation of pristine GNRs. In the pristine region between two boron pairs, the nanoribbons show a discretization of their valence band into confined modes compatible with a Fabry-Perot resonator. Transport simulations of the scattering properties of the boron pairs reveal that they selectively confine the first valence band of the pristine ribbon while allowing an efficient electron transmission of the second one. Such band-dependent electron scattering stems from the symmetry matching between the electronic wave functions of the states from the pristine nanoribbons and those localized at the boron pairs.

Symmetry-Driven Band Gap Engineering in Hydrogen Functionalized Graphene.

Band gap engineering in hydrogen functionalized graphene is demonstrated by changing the symmetry of the functionalization structures. Small differences in hydrogen adsorbate binding energies on graphene on Ir(111) allow tailoring of highly periodic functionalization structures favoring one distinct region of the moiré supercell. Scanning tunneling microscopy and X-ray photoelectron spectroscopy measurements show that a highly periodic hydrogen functionalized graphene sheet can thus be prepared by controlling the sample temperature (Ts) during hydrogen functionalization. At deposition temperatures of Ts = 645 K and above, hydrogen adsorbs exclusively on the HCP regions of the graphene/Ir(111) moiré structure. This finding is rationalized in terms of a slight preference for hydrogen clusters in the HCP regions over the FCC regions, as found by density functional theory calculations. Angle-resolved photoemission spectroscopy measurements demonstrate that the preferential functionalization of just one region of the moiré supercell results in a band gap opening with very limited associated band broadening. Thus, hydrogenation at elevated sample temperatures provides a pathway to efficient band gap engineering in graphene via the selective functionalization of specific regions of the moiré structure.

Investigations into the nature of spontelectrics: nitrous oxide diluted in xenon.

The recent discovery of a new class of solids displaying bulk spontaneous electric fields as high as 10(8) V m(-1), so-called 'spontelectrics', poses fundamental and unresolved problems in solid state physics. The purpose of the present work is to delve more deeply into the nature of the interactions which give rise to the spontelectric effect in films of nitrous oxide (N2O), by observing the variation of the spontaneous field as the N2O molecules are physically removed from one another by dilution in Xe. Data, obtained using the ASTRID storage ring, are presented for films diluted by factors ξ = Xe/N2O of 0.9 to 67, at deposition temperatures of 38 K, 44 K and 48 K, where films are laid down by deposition from a gas mixture. Results show that the spontelectric field decreases as ξ increases and that at ξ = 67 for 44 K deposition, the spontelectric effect is absent. Reflection-absorption infrared spectroscopy (RAIRS) data are also reported, providing insight into the structure of Xe/N2O films and specifically showing that N2O remains dispersed in the Xe/N2O films prepared here. A simplified theoretical model is developed which illustrates that electric fields can be understood in terms of dilution-dependent dipole orientation. This model is used to reproduce experimental data up to an average molecular separation, s, of ≥1.25 nm apart, ∼4 times that associated with pure solid N2O. The disappearance of the spontelectric effect at larger average distances of separation, between s = 1.25 nm and s = 1.75 nm, is a phenomenon which cannot be described by any existing model but which shows that dipole-dipole interactions are an essential ingredient for the creation of the spontelectric state.

Electric field structures in thin films: formation and properties.

A newly discovered class of molecular materials, so-called "spontelectrics", display spontaneous electric fields. Here we show that the novel properties of spontelectrics can be used to create composite spontelectrics, illustrating how electric fields in solid films may be structured on the nanoscale by combining layers of different spontelectric materials. This is demonstrated using the spontelectric materials nitrous oxide, toluene, isoprene, isopentane, and CF2Cl2. These yield a variety of tailored electric field structures, with individual layers harboring fields between 10(7) and 10(8) V/m. Fields may be of the same sign or of opposite sign, the latter enabling the creation of nanoscale potential wells. The formation of fields is followed using an established electron beam technique, employing the ASTRID synchrotron storage ring. The influence of temperature on heterolayer structures, displaying new Curie effects, and the nature of the interfacial region between different spontelectrics are also discussed.

Kinks in the σ band of graphene induced by electron-phonon coupling.

Angle-resolved photoemission spectroscopy reveals pronounced kinks in the dispersion of the σ band of graphene. Such kinks are usually caused by the combination of a strong electron-boson interaction and the cutoff in the Fermi-Dirac distribution. They are therefore not expected for the σ band of graphene that has a binding energy of more than ≈3.5 eV. We argue that the observed kinks are indeed caused by the electron-phonon interaction, but the role of the Fermi-Dirac distribution cutoff is assumed by a cutoff in the density of σ states. The existence of the effect suggests a very weak coupling of holes in the σ band not only to the π electrons of graphene but also to the substrate electronic states. This is confirmed by the presence of such kinks for graphene on several different substrates that all show a strong coupling constant of λ≈1.

Controlling hydrogenation of graphene on Ir(111).

Combined fast X-ray photoelectron spectroscopy and density functional theory calculations reveal the presence of two types of hydrogen adsorbate structures at the graphene/Ir(111) interface, namely, graphane-like islands and hydrogen dimer structures. While the former give rise to a periodic pattern, dimers tend to destroy the periodicity. Our data reveal distinctive growth rates and stability of both types of structures, thereby allowing one to obtain well-defined patterns of hydrogen clusters. The ability to control and manipulate the formation and size of hydrogen structures on graphene facilitates tailoring of its properties for a wide range of applications by means of covalent functionalization.

Spontaneous electric fields in films of CF3Cl, CF2Cl2 and CFCl3.

Data are presented showing the spontaneous formation of electric fields within solid films of the chlorofluorocarbons (CFCs) CF(3)Cl, CF(2)Cl(2) and CFCl(3) as a function of film deposition temperature from 40 K and above. Electric fields, which arise through dipole alignment and lie in the range of a few times 10(7) V m(-1) to a few times 10(6) V m(-1), decrease as the degree of chlorination increases. Maximum deposition temperatures for display of an electric field lie at ~50 K, ~65 K and ~52 K for CF(3)Cl, CF(2)Cl(2) and CFCl(3) respectively. CFCl(3) films possess electric fields which show an onset of temporal metastability between deposition temperatures of 46 K and 50 K. CF(3)Cl and CF(2)Cl(2) demonstrate temperatures of ~65 K and ~80 K at which the electric field in the film is removed by heating, so-called Curie points, with decay of the field spread over more than 10 K. CFCl(3) displays a comparatively sharp Curie point at 55 K. This variety of behaviour arises despite the resemblance of these three species in terms of electronic structure and gas phase dipole moment, emphasising the requirement for detailed chemical models of this phenomenon.

Graphene coatings: probing the limits of the one atom thick protection layer.

The limitations of graphene as an effective corrosion-inhibiting coating on metal surfaces, here exemplified by the hex-reconstructed Pt(100) surface, are probed by scanning tunneling microscopy measurements and density functional theory calculations. While exposure of small molecules directly onto the Pt(100) surface will lift the reconstruction, a single graphene layer is observed to act as an effective coating, protecting the reactive surface from O(2) exposure and thus preserving the reconstruction underneath the graphene layer in O(2) pressures as high as 10(-4) mbar. A similar protective effect against CO is observed at CO pressures below 10(-6) mbar. However, at higher pressures CO is observed to intercalate under the graphene coating layer, thus lifting the reconstruction. The limitations of the coating effect are further tested by exposure to hot atomic hydrogen. While the coating can withstand these extreme conditions for a limited amount of time, after substantial exposure, the Pt(100) reconstruction is lifted. Annealing experiments and density functional theory calculations demonstrate that the basal plane of the graphene stays intact and point to a graphene-mediated mechanism for the H-induced lifting of the reconstruction.

Spontaneous electric fields in films of cis-methyl formate.

A recent publication described a new group of spontaneously polarized materials in which electric fields in excess of 10(8) V m(-1) may be present. This phenomenon arises through dipole alignment in solid films formed by straightforward deposition from vapour and characterises a novel class of materials. Here we present further results for the properties of these materials, focusing on films of cis-methyl formate. These films are shown to display some notable new chemical physics. We find the novel result that the degree of dipole alignment and the corresponding electric field in films of cis-methyl formate can have a counter-intuitive temperature dependence, increasing six-fold between 80 K and 89 K, in sharp contrast to the pronounced and expected fall with deposition temperature seen both here between 50 K and 75 K and in numerous other species. A theoretical model demonstrates that the switch of gradient with rising temperature should be a general phenomenon and is associated with crossing of a singularity in the gradient occurring at a set of critical values of temperature and alignment.

A new form of spontaneously polarized material.

We report here the discovery of a new form of spontaneously polarized material. Examples of this material, in the form of films, demonstrate the property that they spontaneously harbour electric fields which may exceed 10(8) Vm(-1), achieving potentials of tens of volts on the film surface. The molecules presently identified form a diverse group, thus far of six species, with gas phase dipoles lying between 0.08 D and 0.5 D: propane (0.08 D), isopentane (0.13 D), nitrous oxide (0.167 D), isoprene (0.25 D), toluene (0.385 D) and CF(3)Cl (Freon-13; 0.5 D). Here we concentrate on an understanding of the nature of the interactions which give rise to the spontaneously polarized state, using the measured temperature dependence of the electric field in N(2)O as a diagnostic. We show that the polarized state can arise through a mechanism of non-linear dipole alignment in a single domain in which dipole alignment generates the electric field within the film and the field generates dipole alignment. Non-local interactions take place over the dimension of the thickness of the film and permeate the entire medium through the agency of the electric field. This new type of material may have wide ranging applications in devices and in nanotechnology.

Transmission and trapping of cold electrons in water ice.

Experiments are reported which show that currents of low energy ("cold") electrons pass unattenuated through crystalline ice at 135 K for energies between zero and 650 meV, up to the maximum studied film thickness of 430 bilayers, indicating negligible apparent trapping. By contrast, both porous amorphous ice and compact crystalline ice at 40 K show efficient electron trapping. Ice at intermediate temperatures reveals metastable trapping that decays within a few hundred seconds at 110 K. Our results are the first to demonstrate full transmission of cold electrons in high temperature water ice and the phenomenon of temperature-dependent trapping.

Bandgap opening in graphene induced by patterned hydrogen adsorption.

Graphene, a single layer of graphite, has recently attracted considerable attention owing to its remarkable electronic and structural properties and its possible applications in many emerging areas such as graphene-based electronic devices. The charge carriers in graphene behave like massless Dirac fermions, and graphene shows ballistic charge transport, turning it into an ideal material for circuit fabrication. However, graphene lacks a bandgap around the Fermi level, which is the defining concept for semiconductor materials and essential for controlling the conductivity by electronic means. Theory predicts that a tunable bandgap may be engineered by periodic modulations of the graphene lattice, but experimental evidence for this is so far lacking. Here, we demonstrate the existence of a bandgap opening in graphene, induced by the patterned adsorption of atomic hydrogen onto the Moiré superlattice positions of graphene grown on an Ir(111) substrate.