arXiv subjects

Gilles Renaud

Publications and source records attributed to Gilles Renaud.

11 recordsLinked to original sources

arXiv2024

In Situ Characterisation of Graphene Growth on Liquid Copper-Gallium Alloys: Paving the Path for Cost-Effective Synthesis

Liquid metal catalysts (LMCats), primarily molten copper, have demonstrated their efficiency in the chemical vapour deposition (CVD) approach for synthesising high-quality, large-area graphene. However, their high melting temperatures limit broader applications. Reducing the temperature of graphene production on LMCats would lead to a more efficient and cost-effective process. Here, we investigated the effects of alloying copper with a low-melting temperature metal on graphene growth in real-time. We examined a set of liquid copper-gallium alloy systems using two complementary in situ techniques: radiation-mode optical microscopy and synchrotron X-ray reflectivity (XRR). Microscopy observations revealed reduced catalytic activity and graphene quality degradation in compositions with gallium domination. The XRR confirmed the formation of single-layer graphene on alloys with up to 60 wt% of gallium. Additionally, we detected a systematic increase in adsorption height on the alloys' surface, suggesting a weaker graphene adhesion on gallium. These findings propose a trade-off between layer quality and production cost reduction is feasible. Our results offer insights into the CVD synthesis of graphene on bimetallic liquid surfaces and underscore the potential of gallium-copper alloys for enabling the direct transfer of graphene from a liquid substrate, thereby addressing the limitations imposed by high melting temperatures of conventional LMCats.

physics.app-ph↗

arXiv2024

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.

cond-mat.mtrl-sci↗

arXiv2022

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

We achieved a tripling of the maximum range of perpendicular momentum transfer (q_z) of X-ray scattering from liquid surfaces using a double crystal deflector setup to tilt the incident X-ray beam. This is obtained by using Miller indices of the reflecting crystal atomic planes that are three times higher than usual. We calculate the deviation from the exact Bragg angle condition induced by a misalignment between the X-ray beam axis and the main rotation axis of the double crystal deflector and deduce a fast and straightforward procedure to align them. We show measurements of X-ray reflectivity up to q_z=7A^(-1) on the bare surface of liquid copper and on graphene on liquid copper.

cond-mat.mtrl-sci↗

arXiv2020

Decoupling Molybdenum Disulfide from its Substrate by Cesium Intercalation

Intercalation of alkali atoms within the lamellar transition metal dichalcogenides is a possible route toward a new generation of batteries. It is also a way to induce structural phase transitions authorizing the realization of optical and electrical switches in this class of materials. The process of intercalation has been mostly studied in three-dimensional dichalcogenide films. Here, we address the case of a single-layer of molybdenum disulfide (MoS$_2$), deposited on a gold substrate, and intercalated with cesium (Cs) in ultra-clean conditions (ultrahigh vacuum). We show that intercalation decouples MoS$_2$ from its substrate. We reveal electron transfer from Cs to MoS$_2$, relative changes in the energy of the valence band maxima, and electronic disorder induced by structural disorder in the intercalated Cs layer. Besides, we find an abnormal lattice expansion of MoS$_2$, which we relate to immediate vicinity of Cs. Intercalation is thermally activated, and so is the reverse process of de-intercalation. Our work opens the route to a microscopic understanding of a process of relevance in several possible future technologies, and shows a way to manipulate the properties of two-dimensional dichalcogenides by "under-cover" functionalization.

cond-mat.mtrl-sci↗

arXiv2016

Molecular Beam Epitaxy of thin HfTe2 semimetal films

Epitaxial thin films of 1T-HfTe2 semimetal are grown by MBE on AlN(0001) substrates. The measured in-plane lattice parameter indicates an unstrained film which is also azimuthally aligned with the AlN substrate, albeit with an in-plane mosaic spread, as it would be expected for van der Waals epitaxy. Angle resolved photoemission spectroscopy combined with first principles electronic band structure calculations show steep linearly dispersing conduction and valence bands which cross near the Brillouin zone center, providing evidence that HfTe2 /AlN is an epitaxial topological Dirac semimetal.

cond-mat.mtrl-sci↗

arXiv2015

Topography of the graphene/Ir(111) moir{é} studied by surface x-ray diffraction

The structure of a graphene monolayer on Ir(111) has been investigated {\it in situ} in the growth chamber by surface x-ray diffraction including the specular rod, which allows disentangling the effect of the sample roughness from that of the nanorippling of graphene and iridium along the moir{é}-like pattern between graphene and Ir(111). Accordingly we are able to provide precise estimates of the undulation associated with this nanorippling, which is small in this weakly interacting graphene/metal system and thus proved difficult to assess in the past. The nanoripplings of graphene and iridium are found in phase, i.e. the in-plane position of their height maxima coincide, but the amplitude of the height modulation is much larger for graphene ($0.379 \pm 0.044$ Å) than, {\it e.g.}, for the topmost Ir layer ($0.017 \pm 0.002$ Å). The average graphene-Ir distance is found to be $3.38 \pm 0.04$ Å.

cond-mat.mtrl-sci↗

arXiv2014

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

Two-dimensional hexagonal arrays of Pt nanoparticles (1.45 nm diameter) have been obtained by deposition of preformed and size selected Pt80 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.

cond-mat.mes-hall↗

arXiv2013

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.

cond-mat.mtrl-sci↗

arXiv2012

Local deformations and incommensurability of high quality epitaxial graphene on a weakly interacting transition metal

We investigate the fine structure of graphene on iridium, which is a model for graphene weakly interacting with a transition metal substrate. Even the highest quality epitaxial graphene displays tiny imperfections, i.e. small biaxial strains, ca. 0.3%, rotations, ca. 0.5^{\circ}, and shears over distances of ca. 100 nm, and is found incommensurate, as revealed by X-ray diffraction and scanning tunneling microscopy. These structural variations are mostly induced by the increase of the lattice parameter mismatch when cooling down the sample from the graphene preparation temperature to the measurement temperature. Although graphene weakly interacts with iridium, its thermal expansion is found positive, contrary to free-standing graphene. The structure of graphene and its variations are very sensitive to the preparation conditions. All these effects are consistent with initial growth and subsequent pining of graphene at steps.

cond-mat.mtrl-sci↗

arXiv2010

Twins and their boundaries during homoepitaxy on Ir(111)

The growth and annealing behavior of strongly twinned homoepitaxial films on Ir(111) has been investigated by scanning tunneling microscopy, low energy electron diffraction and surface X-ray diffraction. In situ surface X-ray diffraction during and after film growth turned out to be an efficient tool for the determination of twin fractions in multilayer films and to uncover the nature of side twin boundaries. The annealing of the twin structures is shown to take place in a two step process, reducing first the length of the boundaries between differently stacked areas and only then the twins themselves. A model for the structure of the side twin boundaries is proposed which is consistent with both the scanning tunneling microscopy and surface X-ray diffraction data.

cond-mat.mtrl-sci↗

arXiv2002

Structure determination of the (3sqrt{3}x3sqrt{3}) reconstructed alpha-Al_2O_3(0001)

Grazing-incidence X-ray diffraction data are combined with energy-minimization calculations to analyse the atomic structure of the Al-rich (3sqrt{3} x 3sqrt{3})R 30 deg reconstructed surface of sapphire alpha-Al_2O_3(0001). The experiments on the BM32 beamline of the ESRF provide the non-integer-order diffraction intensities and, after Fourier transform, an incomplete Patterson map. The computer simulations are implemented to obtain structural information from this map. In the simulations, the interactions between the Al overlayer atoms were described with the Sutton-Chen potential and the interactions between the overlayer and the sapphire substrate with a laterally modulated Lennard-Jones potential. We have shown that the hexagonal reconstructed unit cell is composed of triangles where the two layers of Al adatoms are FCC(111) ordered whereas between the triangles the stacking is FCC(001).

cond-mat.mtrl-sci↗