Publisher's Note: Si Nanoribbons on Ag(110) Studied by Grazing-Incidence X-Ray Diffraction, Scanning Tunneling Microscopy, and Density-Functional Theory: Evidence of a Pentamer Chain Structure [Phys. Rev. Lett. 117, 276102 (2016)].

This corrects the article DOI: 10.1103/PhysRevLett.117.276102.

Si Nanoribbons on Ag(110) Studied by Grazing-Incidence X-Ray Diffraction, Scanning Tunneling Microscopy, and Density-Functional Theory: Evidence of a Pentamer Chain Structure.

We report a combined grazing incidence x-ray diffraction (GIXD), scanning tunneling microscopy (STM), and density-functional theory (DFT) study which clearly elucidates the atomic structure of the Si nanoribbons grown on the missing-row reconstructed Ag(110) surface. Our study allows us to discriminate between the theoretical models published in the literature, including the most stable atomic configurations and those based on a missing-row reconstructed Ag(110) surface. GIXD measurements unambiguously validate the pentamer model grown on the reconstructed surface, obtained from DFT. This pentamer atomistic model accurately matches the high-resolution STM images of the Si nanoribbons adsorbed on Ag(110). Our study closes the long-debated atomic structure of the Si nanoribbons grown on Ag(110) and definitively excludes a honeycomb structure similar to that of freestanding silicene.

Anomalous intralayer growth of epitaxial Si on Ag(111).

The epitaxial growth of silicene has been the subject of many investigations, controversies and non-classical results. In particular, the initially promising deposition of Si on a metallic substrate such as Ag(111) has revealed unexpected growth modes where Si is inserted at the beginning of the growth in the first atomic plane of the substrate. In order to rationalize this anomalous growth mode, we develop an out-of-equilibrium description of a lattice-based epitaxial growth model, which growth dynamics are analyzed via kinetic Monte-Carlo simulations. This model incorporates several effects revealed by the experiments such as the intermixing between Si and Ag, and surface effects. It is parametrized thanks to an approach in which we show that relatively precise estimates of energy barriers can be deduced by meticulous analysis of atomic microscopy images. This analysis enables us to reproduce both qualitatively and quantitatively the anomalous growth patterns of Si on Ag(111). We show that the dynamics results in two modes, a classical sub-monolayer growth mode at low temperature, and an inserted growth mode at higher temperatures, where the deposited Si atoms insert in the first layer of the substrate by replacing Ag atoms. Furthermore, we reproduce the non-standard [Formula: see text] shape of the experimental plot of the island density as a function of temperature, with a shift in island density variation during the transition between the submonoloyer and inserted growth modes.

Double-pentagon silicon chains in a quasi-1D Si/Ag(001) surface alloy.

Silicon surface alloys and silicide nanolayers are highly important as contact materials in integrated circuit devices. Here we demonstrate that the submonolayer Si/Ag(001) surface reconstruction, reported to exhibit interesting topological properties, comprises a quasi-one-dimensional Si-Ag surface alloy based on chains of planar double-pentagon Si moieties. This geometry is determined using a combination of density functional theory calculations, scanning tunnelling microscopy, and grazing incidence x-ray diffraction simulations, and yields an electronic structure in excellent agreement with photoemission measurements. This work provides further evidence of pentagonal geometries in 2D materials and heterostructures and elucidates the importance of surface alloying in stabilizing their formation.

Epitaxial growth and structural properties of silicene and other 2D allotropes of Si.

Since the breakthrough of graphene, considerable efforts have been made to search for two-dimensional (2D) materials composed of other group 14 elements, in particular silicon and germanium, due to their valence electronic configuration similar to that of carbon and their widespread use in the semiconductor industry. Silicene, the silicon counterpart of graphene, has been particularly studied, both theoretically and experimentally. Theoretical studies were the first to predict a low-buckled honeycomb structure for free-standing silicene possessing most of the outstanding electronic properties of graphene. From an experimental point of view, as no layered structure analogous to graphite exists for silicon, the synthesis of silicene requires the development of alternative methods to exfoliation. Epitaxial growth of silicon on various substrates has been widely exploited in attempts to form 2D Si honeycomb structures. In this article, we provide a comprehensive state-of-the-art review focusing on the different epitaxial systems reported in the literature, some of which having generated controversy and long debates. In the search for the synthesis of 2D Si honeycomb structures, other 2D allotropes of Si have been discovered and will also be presented in this review. Finally, with a view to applications, we discuss the reactivity and air-stability of silicene as well as the strategy devised to decouple epitaxial silicene from the underlying surface and its transfer to a target substrate.

The Ground State of Epitaxial Germanene on Ag(111).

Two-dimensional (2D) honeycomb lattices beyond graphene, such as germanene, appear very promising due to their outstanding electronic properties, such as the quantum spin Hall effects. While there have been many claims of germanene monolayers up to now, no experimental evidence of a honeycomb structure has been provided up to now for these grown monolayers. Using scanning tunneling microscopy (STM), surface X-ray diffraction (SXRD), and density functional theory, we have elucidated the Ge-induced (109×109)R±24.5° reconstruction on Ag(111). We demonstrate that a powerful algorithm combining SXRD with STM allows us to solve a giant surface reconstruction with more than a hundred atoms per unit cell. Its extensive unit cell indeed consists of 98 2-fold or 3-fold coordinated Ge atoms, forming a periodic arrangement of pentagons, hexagons, and heptagons, with the inclusion of six dispersed Ag atoms. By analogy, we show that the (77×77)R±19.1° reconstruction obtained by segregation of Ge through an epitaxial Ag/Ge(111) film possesses a similar structure, i.e., Ge pentagons/hexagons/heptagons with a few Ag atoms. Such an organization is more stable than that of pure Ge monolayers and can be assigned to the ground state of epitaxial germanene.

Transport Properties of Methyl-Terminated Germanane Microcrystallites.

Germanane is a two-dimensional material consisting of stacks of atomically thin germanium sheets. It's easy and low-cost synthesis holds promise for the development of atomic-scale devices. However, to become an electronic-grade material, high-quality layered crystals with good chemical purity and stability are needed. To this end, we studied the electrical transport of annealed methyl-terminated germanane microcrystallites in both high vacuum and ultrahigh vacuum. Scanning electron microscopy of crystallites revealed two types of behavior which arise from the difference in the crystallite chemistry. While some crystallites are hydrated and oxidized, preventing the formation of good electrical contact, the four-point resistance of oxygen-free crystallites was measured with multiple tips scanning tunneling microscopy, yielding a bulk transport with resistivity smaller than 1 Ω·cm. When normalized by the crystallite thickness, the resistance compares well with the resistance of hydrogen-passivated germanane flakes found in the literature. Along with the high purity of the crystallites, a thermal stability of the resistance at 280 °C makes methyl-terminated germanane suitable for complementary metal oxide semiconductor back-end-of-line processes.

Wafer-sized WS2 monolayer deposition by sputtering.

We demonstrate that tungsten disulphide (WS2) with thicknesses ranging from monolayer (ML) to several monolayers can be grown on SiO2/Si, Si, and Al2O3 by pulsed direct current-sputtering. The presence of high quality monolayer and multilayered WS2 on the substrates is confirmed by Raman spectroscopy since the peak separations between the A1g-E2g and A1g-2LA vibration modes exhibit a gradual increase depending on the number of layers. X-ray diffraction confirms a textured (001) growth of WS2 films. The surface roughness measured with atomic force microscopy is between 1.5 and 3 Å for the ML films. The chemical composition WSx (x = 2.03 ± 0.05) was determined from X-ray Photoelectron Spectroscopy. Transmission electron microscopy was performed on a multilayer film to show the 2D layered structure. A unique method for growing 2D layers directly by sputtering opens up the way for designing 2D materials and batch production of high-uniformity and high-quality (stochiometric, large grain sizes, flatness) WS2 films, which will advance their practical applications in various fields.

Nonwetting Behavior of Al-Co Quasicrystalline Approximants Owing to Their Unique Electronic Structures.

Good wetting is generally observed for liquid metals on metallic substrates, while poor wetting usually occurs for metals on insulating oxides. In this work, we report unexpected large contact angles for lead on two metallic approximants to decagonal quasicrystals, namely, Al5Co2 and Al13Co4. Intrinsic surface wettability is predicted from first principles, using a thermodynamic model based on the Young equation, and validated by the good agreement with experimental measurements performed under ultra-high vacuum by scanning electron microscopy. The atomistic details of the atomic and electronic structures at the Pb-substrate interface, and the comparison with Pb(111)/Al(111), underline the influence of the specific electronic structures of quasicrystalline approximants on wetting. Our work suggests a possible correlation of the contact angles with the density of states at the Fermi energy and paves the way for a better fundamental understanding of wettability on intermetallic substrates, which has potential consequences in several applications such as supported catalysts, protective coatings, or crystal growth.

Gas-induced selective re-orientation of Au-Cu nanoparticles on TiO2 (110).

Au-Cu bimetallic nanoparticles (NPs) grown on TiO2(110) have been followed in situ using grazing incidence X-ray diffraction and X-ray photoemission spectroscopy from their synthesis to their exposure to a CO/O2 mixture at low pressure (P < 10-5 mbar) and at different temperatures (300 K-470 K). As-prepared samples are composed of two types of alloyed NPs: randomly oriented and epitaxial NPs. Whereas the introduction of CO has no effect on the structure of the NPs, an O2 introduction triggers a Cu surface segregation phenomenon resulting in the formation of a Cu2O shell reducible by annealing the sample over 430 K. A selective re-orientation of the nanoparticles, induced by the exposure to a CO/O2 mixture, is observed where the randomly oriented NPs take advantage of the mobility induced by the Cu segregation to re-orient their Au-rich core relatively to the TiO2(110) substrate following specifically the orientation ((111)NPs//(110)TiO2) when others epitaxial relationships were observed on the as-prepared sample.

Transition from silicene monolayer to thin Si films on Ag(111): comparison between experimental data and Monte Carlo simulation.

Scanning tunneling microscopy (STM), Auger electron spectroscopy (AES) and low energy electron diffraction have been used to follow the growth of Si films on Ag(111) at various temperatures. Using a simple growth model, we have simulated the distribution of film thickness as a function of coverage during evaporation, for the different temperatures. In the temperature regime where multilayer silicene has been claimed to form (470-500 K), a good agreement is found with AES intensity variations and STM measurements within a Ag surfactant mediated growth, whereas a model with multilayer silicene growth fails to reproduce the AES measurements.

Resolving the Controversial Existence of Silicene and Germanene Nanosheets Grown on Graphite.

The highly oriented pyrolytic graphite (HOPG) surface, consisting of a dangling bond-free lattice, is regarded as a potential substrate for van der Waals heteroepitaxy of two-dimensional layered materials. In this work, the growth of silicon and germanium on HOPG is investigated with scanning tunneling microscopy by using typical synthesis conditions for silicene and germanene on metal surfaces. At low coverages, the deposition of Si and Ge gives rise to tiny and sparse clusters that are surrounded by a honeycomb superstructure. From the detailed analysis of the superstructure, its comparison with the one encountered on the bare and clean HOPG surface, and simulations of the electron density, we conclude that the superstructure is caused by charge density modulations in the HOPG surface. At high coverages, we find the formation of clusters, assembled in filamentary patterns, which indicates a Volmer-Weber growth mode instead of a layer-by-layer growth mode. This coverage-dependent study sets the stage for revisiting recent results alleging the synthesis of silicene and germanene on the HOPG surface.

Promoter effect of hydration on the nucleation of nanoparticles: direct observation for gold and copper on rutile TiO2 (110).

Direct observation of the promoting effect of hydration on the nucleation of gold and copper nanoparticles supported on partially reduced rutile TiO2 (110) is achieved by combined scanning tunneling microscopy experiments and density functional theory calculations. The experiments show a clear difference between the two metals. Gold nanoparticles grow at the vicinity of the surface hydroxyl domains, whereas the nucleation of copper is not substantially affected by hydration. The nucleation of gold on surface oxygen vacancies is observed although this is not the only preferential site. Theoretical calculations of the coadsorbed phases of gold, copper and hydroxyl species on stoichiometric and reduced TiO2 (110) surfaces under relevant conditions of temperature and pressure support the experimental interpretation. Surface hydration tends to stabilize significantly gold adsorption on the stoichiometric support, while its influence on copper adsorption is not pronounced. The theoretical analysis shows that the early stages of the nucleation on hydrated stoichiometric surfaces correspond to mono-hydroxylated metallic species co-chemisorbed with hydroxyl species, whereas those on hydrated reduced surfaces are metallic atoms bound to oxygen vacancies and weakly perturbed by surface hydration.

Ostwald-Driven Phase Separation in Bimetallic Nanoparticle Assemblies.

The compositional stability of bimetallic nanoparticles (NPs) is crucial for many applications. We have studied the coarsening of amorphous carbon-supported Au-Pd NPs during annealing at 873 K. Using scanning transmission electron microscopy and energy-dispersive spectroscopy measurements, we show that, despite a complete miscibility of the two metals, the particle assembly undergoes a phase separation during annealing, which leads to two distinct populations: Au-rich NPs with a mean radius of 3.5 nm and large Pd-rich NPs with a mean radius of 25 nm. Thermodynamic calculations and kinetic Monte Carlo simulations explain this behavior that is driven by the competition between surface and mixing energy and by the different mobilities of the two atomic species.