Tripling of the scattering vector range of X-ray reflectivity on liquid surfaces using a double-crystal deflector.

The maximum range of perpendicular momentum transfer (q z) has been tripled for X-ray scattering from liquid surfaces when using a double-crystal deflector setup to tilt the incident X-ray beam. This is achieved by employing a higher-energy X-ray beam to access Miller indices of reflecting crystal atomic planes that are three times higher than usual. The deviation from the exact Bragg angle condition induced by misalignment between the X-ray beam axis and the main rotation axis of the double-crystal deflector is calculated, and a fast and straightforward procedure to align them is deduced. An experimental method of measuring scattering intensity along the q z direction on liquid surfaces up to q z = 7 Å-1 is presented, with liquid copper serving as a reference system for benchmarking purposes.

Operando Characterization and Molecular Simulations Reveal the Growth Kinetics of Graphene on Liquid Copper During Chemical Vapor Deposition.

In recent years, liquid metal catalysts have emerged as a compelling choice for the controllable, large-scale, and high-quality synthesis of two-dimensional materials. At present, there is little mechanistic understanding of the intricate catalytic process, though, of its governing factors or what renders it superior to growth at the corresponding solid catalysts. Here, we report on a combined experimental and computational study of the kinetics of graphene growth during chemical vapor deposition on a liquid copper catalyst. By monitoring the growing graphene flakes in real time using in situ radiation-mode optical microscopy, we explore the growth morphology and kinetics over a wide range of CH4-to-H2 pressure ratios and deposition temperatures. Constant growth rates of the flakes' radius indicate a growth mode limited by precursor attachment, whereas methane-flux-dependent flake shapes point to limited precursor availability. Large-scale free energy simulations enabled by an efficient machine-learning moment tensor potential trained to density functional theory data provide quantitative barriers for key atomic-scale growth processes. The wealth of experimental and theoretical data can be consistently combined into a microkinetic model that reveals mixed growth kinetics that, in contrast to the situation at solid Cu, is partly controlled by precursor attachment alongside precursor availability. Key mechanistic aspects that directly point toward the improved graphene quality are a largely suppressed carbon dimer attachment due to the facile incorporation of this precursor species into the liquid surface and a low-barrier ring-opening process that self-heals 5-membered rings resulting from remaining dimer attachments.

Superstructures, Commensurations, and Rotation of Single-Layer TaS2 on Au(111) Induced by Cs Intercalation/Deintercalation.

We use in situ synchrotron grazing incidence X-ray diffraction and X-ray reflectivity to investigate with high resolution the structure of a two-dimensional single layer of tantalum sulfide grown on a Au(111) surface and its evolution during intercalation by Cs atoms and deintercalation, which decouples and recouples the two materials, respectively. The grown single layer consists of a mixture of TaS2 and its S-depleted version, TaS, both aligned with gold, and forming moirés where 7 (respectively 13) lattice constants of the 2D layer almost perfectly match 8 (respectively 15) substrate lattice constants. Intercalation fully decouples the system by lifting the single layer by ∼370 pm and induces an increase of its lattice parameter by 1-2 picometers. The system gradually evolves, during cycles of intercalation/deintercalation assisted by an H2S atmosphere, toward a final coupled state consisting of the fully stoichiometric TaS2 dichalcogenide whose moiré is found very close to the 7/8 commensurability. The reactive H2S atmosphere appears necessary to achieve full deintercalation, presumably by preventing S depletion and the concomitant strong bonding with the intercalant. The structural quality of the layer improves during the cyclic treatment. In parallel, because they are decoupled from the substrate by the intercalation of cesium, some of the TaS2 flakes rotate by 30°. These produce two additional superlattices with characteristic diffraction patterns of different origins. The first is aligned with gold's high symmetry crystallographic directions and is a commensurate moiré ((6 × 6)-Au(111) coinciding with (3√3 × 3√3)R30°-TaS2). The second is incommensurate and corresponds to a near coincidence of (6 × 6) unit cells of 30°-rotated TaS2 with (4√3 × 4√3)Au(111) surface ones. This structure, which is less coupled to gold, might be related to the ∼(3× 3) charge density wave previously reported even at room temperature in TaS2 grown on noninteracting substrates. A (3 × 3) superstructure of 30°-rotated TaS2 islands is indeed revealed by complementary scanning tunneling microscopy.

Graphene at Liquid Copper Catalysts: Atomic-Scale Agreement of Experimental and First-Principles Adsorption Height.

Liquid metal catalysts have recently attracted attention for synthesizing high-quality 2D materials facilitated via the catalysts' perfectly smooth surface. However, the microscopic catalytic processes occurring at the surface are still largely unclear because liquid metals escape the accessibility of traditional experimental and computational surface science approaches. Hence, numerous controversies are found regarding different applications, with graphene (Gr) growth on liquid copper (Cu) as a prominent prototype. In this work, novel in situ and in silico techniques are employed to achieve an atomic-level characterization of the graphene adsorption height above liquid Cu, reaching quantitative agreement within 0.1 Å between experiment and theory. The results are obtained via in situ synchrotron X-ray reflectivity (XRR) measurements over wide-range q-vectors and large-scale molecular dynamics simulations based on efficient machine-learning (ML) potentials trained to first-principles density functional theory (DFT) data. The computational insight is demonstrated to be robust against inherent DFT errors and reveals the nature of graphene binding to be highly comparable at liquid Cu and solid Cu(111). Transporting the predictive first-principles quality via ML potentials to the scales required for liquid metal catalysis thus provides a powerful approach to reach microscopic understanding, analogous to the established computational approaches for catalysis at solid surfaces.

X-ray reflectivity from curved surfaces as illustrated by a graphene layer on molten copper.

The X-ray reflectivity technique can provide out-of-plane electron-density profiles of surfaces, interfaces, and thin films, with atomic resolution accuracy. While current methodologies require high surface flatness, this becomes challenging for naturally curved surfaces, particularly for liquid metals, due to the very high surface tension. Here, the development of X-ray reflectivity measurements with beam sizes of a few tens of micrometres on highly curved liquid surfaces using a synchrotron diffractometer equipped with a double crystal beam deflector is presented. The proposed and developed method, which uses a standard reflectivity θ-2θ scan, is successfully applied to study in situ the bare surface of molten copper and molten copper covered by a graphene layer grown in situ by chemical vapor deposition. It was found that the roughness of the bare liquid surface of copper at 1400 K is 1.25 ± 0.10 Å, while the graphene layer is separated from the liquid surface by a distance of 1.55 ± 0.08 Šand has a roughness of 1.26 ± 0.09 Å.

Real-Time Multiscale Monitoring and Tailoring of Graphene Growth on Liquid Copper.

The synthesis of large, defect-free two-dimensional materials (2DMs) such as graphene is a major challenge toward industrial applications. Chemical vapor deposition (CVD) on liquid metal catalysts (LMCats) is a recently developed process for the fast synthesis of high-quality single crystals of 2DMs. However, up to now, the lack of in situ techniques enabling direct feedback on the growth has limited our understanding of the process dynamics and primarily led to empirical growth recipes. Thus, an in situ multiscale monitoring of the 2DMs structure, coupled with a real-time control of the growth parameters, is necessary for efficient synthesis. Here we report real-time monitoring of graphene growth on liquid copper (at 1370 K under atmospheric pressure CVD conditions) via four complementary in situ methods: synchrotron X-ray diffraction and reflectivity, Raman spectroscopy, and radiation-mode optical microscopy. This has allowed us to control graphene growth parameters such as shape, dispersion, and the hexagonal supra-organization with very high accuracy. Furthermore, the switch from continuous polycrystalline film to the growth of millimeter-sized defect-free single crystals could also be accomplished. The presented results have far-reaching consequences for studying and tailoring 2D material formation processes on LMCats under CVD growth conditions. Finally, the experimental observations are supported by multiscale modeling that has thrown light into the underlying mechanisms of graphene growth.

Elaboration of Nanomagnet Arrays: Organization and Magnetic Properties of Mass-Selected FePt Nanoparticles Deposited on Epitaxially Grown Graphene on Ir(111).

The moiré pattern created by the epitaxy of a graphene sheet on an iridium substrate can be used as a template for the growth of 2D atomic or cluster arrays. We observed for the first time a coherent organization of hard magnetic preformed FePt nanoparticles on the 2D lattice of graphene on Ir(111). Nanoparticles of 2 nm diameter have been mass selected in a gas phase and deposited with low energy on the hexagonal moiré pattern. Their morphology and organization have been investigated using grazing incidence small angle x-ray scattering, while their magnetic properties have been studied by x-ray magnetic circular dichroism, both pointing to a FePt cluster-graphene surface specific interaction. The spatial coherence of the nanoparticles is preserved upon annealing up to 700 °C where the hard magnetic phase of FePt is obtained.

Beyond van der Waals Interaction: The Case of MoSe2 Epitaxially Grown on Few-Layer Graphene.

Van der Waals heterojunctions composed of graphene and transition metal dichalcogenides have gain much attention because of the possibility to control and tailor band structure, promising applications in two-dimensional optoelectronics and electronics. In this report, we characterized the van der Waals heterojunction MoSe2/few-layer graphene with a high-quality interface using cutting-edge surface techniques scaling from atomic to microscopic range. These surface analyses gave us a complete picture of the atomic structure and electronic properties of the heterojunction. In particular, we found two important results: the commensurability between the MoSe2 and few-layer graphene lattices and a band-gap opening in the few-layer graphene. The band gap is as large as 250 meV, and we ascribed it to an interface charge transfer that results in an electronic depletion in the few-layer graphene. This conclusion is well supported by electron spectroscopy data and density functional theory calculations. The commensurability between the MoSe2 and graphene lattices as well as the band-gap opening clearly show that the interlayer interaction goes beyond the simple van der Waals interaction. Hence, stacking two-dimensional materials in van der Waals heterojunctions enables us to tailor the atomic and electronic properties of individual layers. It also permits the introduction of a band gap in few-layer graphene by interface charge transfer.

Massless Dirac Fermions in ZrTe2 Semimetal Grown on InAs(111) by van der Waals Epitaxy.

Single and few layers of the two-dimensional (2D) semimetal ZrTe2 are grown by molecular beam epitaxy on InAs(111)/Si(111) substrates. Excellent rotational commensurability, van der Waals gap at the interface and moiré pattern are observed indicating good registry between the ZrTe2 epilayer and the substrate through weak van der Waals forces. The electronic band structure imaged by angle resolved photoelectron spectroscopy shows that valence and conduction bands cross at the Fermi level exhibiting abrupt linear dispersions. The latter indicates massless Dirac Fermions which are maintained down to the 2D limit suggesting that single-layer ZrTe2 could be considered as the electronic analogue of graphene.

Moiré induced organization of size-selected Pt clusters soft landed on epitaxial graphene.

Two-dimensional hexagonal arrays of Pt nanoparticles (1.5 nm diameter) have been obtained by deposition of preformed and size selected Pt nanoparticles on graphene. This original self-organization is induced, at room temperature, by the 2D periodic undulation (the moiré pattern) of graphene epitaxially grown on the Ir(111) surface. By means of complementary techniques (scanning tunneling microscopy, grazing incidence X ray scattering), the Pt clusters shapes and organization are characterized and the structural evolution during annealing is investigated. The soft-landed clusters remain quasi-spherical and a large proportion appears to be pinned on specific moiré sites. The quantitative determination of the proportion of organized clusters reveals that the obtained hexagonal array of the almost spherical nanoparticles is stable up to 650 K, which is an indication of a strong cluster-surface interaction.

Strains induced by point defects in graphene on a metal.

Strains strongly affect the properties of low-dimensional materials, such as graphene. By combining in situ, in operando, reflection high-energy electron diffraction experiments with first-principles calculations, we show that large strains, above 2%, are present in graphene during its growth by chemical vapor deposition on Ir(111) and when it is subjected to oxygen etching and ion bombardment. Our results unravel the microscopic relationship between point defects and strains in epitaxial graphene and suggest new avenues for graphene nanostructuring and engineering its properties through introduction of defects and intercalation of atoms and molecules between graphene and its metal substrate.

Effects of near-neighbor correlations on the diffuse scattering from a one-dimensional paracrystal.

The one-dimensional paracrystal model is generalized by folding the lattice sites with objects whose scattering lengths or sizes and separation display a spatial correlation from cell to cell. A general theory to calculate the diffuse scattering and the scattering-length autocorrelation function is developed. The investigated models of coupling along the paracrystalline chain are the correlations between (i) the sizes of the scatterers, (ii) the sizes of scatterers and their separations, and (iii) the sizes of scatterers and the fluctuation of their separation distances. In the first case (i), the size of a scatterer is, on average, linked to that of its neighbors. As a result, a continuous transition from the total lack of size correlation (known as decoupling approximation or DA) to the scattering from monodisperse domains (local monodisperse approximation or LMA) is obtained. In the second case of correlation (ii), the mean interobject distance is assumed to depend on the respective sizes of nearest neighbors. Depending on the introduced correlation parameter, aggregation or hard-core-type effects can be accounted for. Surprisingly, in some cases, it is possible to find a peak in the scattering curve without any structure in the total interference function. The size-separation correlations may also dramatically reduce the scattering intensity close to the origin compared to the completely uncorrelated case. The last model (iii) foresees a coupling between the sizes of neighboring objects and the variance of the separation between neighbors. Within this model, on average along the chain, the fluctuations of distances between scatterers become dependent on the respective sizes of neighbors, while the mean distance between objects remains constant.

Real-time monitoring of growing nanoparticles.

One challenge in the production of nanometer-sized objects with given properties is to control their growth at a macroscopic scale in situ and in real time. A dedicated ultrahigh-vacuum grazing-incidence small-angle x-ray scattering setup has been developed, yielding high sensitivity and dynamics. Its capabilities to derive the average particle shape and size and the film growth mode and ordering and to probe both surfaces and buried interfaces are illustrated for two prototypical cases: the model catalyst Pd/MgO(100) and the self-organized Co/Au(111) system. A wide range of technologically important systems can potentially be investigated in various gaseous environments.