Laurent Baraton

On the mechanisms of precipitation of graphene on nickel thin films

Growth on transition metal substrates is becoming a method of choice to prepare large-area graphene foils. In the case of nickel, where carbon has a significant solubility, such a growth process includes at least two elementary steps: 1) carbon dissolution into the metal, and 2) graphene precipitation at the surface. Here, we dissolve calibrated amounts of carbon in nickel films, using carbon ion implantation, and annealing at 725°C or 900°C. We then use transmission electron microscopy to analyse the precipitation process in detail: the latter appears to imply carbon diffusion over large distances and at least two distinct microscopic mechanisms.

Synthesis of few-layered graphene by ion implantation of carbon in nickel thin films

The synthesis of few-layered graphene is performed by ion implantation of carbon species in thin nickel films, followed by high temperature annealing and quenching. Although ion implantation enables a precise control of the carbon content and of the uniformity of the in-plane carbon concentration in the Ni films before annealing, we observe thickness non-uniformities in the synthesized graphene layers after high temperature annealing. These non-uniformities are probably induced by the heterogeneous distribution/topography of the graphene nucleation sites on the Ni surface. Taken altogether, our results indicate that the number of graphene layers on top of Ni films is controlled by the nucleation process on the Ni surface rather than by the carbon content in the Ni film.

Covalent grafting onto self-adhesive surfaces based on aryldiazonium salt seed layers

The chemistry of aryldiazonium salts has been thoroughly used in recent years to graft in a very simple and robust way ultrathin polyphenylene-like films on a broad range of surfaces. We show here that the same chemistry can be used to obtain “self-adhesive surfaces”. This target was reached in a simple way by coating various surfaces with chemisorbed organic films containing active aryldiazonium salts. These “self-adhesive surfaces” are then put into contact with various species (molecules, polymers, nanoparticles, nanotubes, graphene flakes, etc.) that react either spontaneously or under activation with the immobilized aryldiazonium salts. Our self-adhesive surfaces were synthesized following a simple aqueous two-step protocol based on p-phenylenediamine diazotisation. The first diazotisation step results in the robust grafting of thin polyaminophenylene (PAP) layers onto the surface. The second diazotisation step changed the grafted PAP film into a “poly-aryldiazonium polymer” (PDP) film. The covalent grafting between those self-adhesive surfaces and the target species was achieved by direct contact or by immersion of the self-adhesive surfaces in solution. We present in this preliminary work the grafting of multi-wall carbon nanotubes (MWCNTs), flakes of highly oriented pyrolytic graphite (HOPG), various organic compounds and copper nanoparticles. We also tested these immobilized aryldiazonium salts as electropolymerization initiators for the grafting-to process.

A new approach to grafting a monolayer of oriented Mn12 nanomagnets on silicon

The functionalisation of a Si(100) silicon wafer allows for the oriented grafting of a monolayer of Mn12 nanomagnets using a two-step procedure.

Grafting a Monolayer of Superparamagnetic Cyanide-Bridged Coordination Nanoparticles on Si(100)

The grafting of a monolayer of 6 nm superparamagnetic cyanide-bridged CsNiCr nanoparticles was achieved on a Ni(II)-functionalized Si(100) substrate; magnetic studies reveals that the grafted nanoparticles are nearly magnetically isolated within the monolayer.

Dual graphene films growth process based on plasma-assisted chemical vapor deposition

Graphene has been given great attention to overcome current physical limits in electronic devices and its synthesis routes are developing rapidly. However, graphene film manufacturing is still hindered by either low throughput or low material quality. Here, we present a low temperature PE-CVD assisted graphene growth process on nickel thin films deposited on silicon oxide. Furthermore, our process leads to the formation of two separated graphene films, one at the nickel surface and the other at the Ni/SiO2 interface. A mixture of methane and hydrogen was employed as carbon precursor and activated by DC plasma. We found that the number of graphene layers on top of nickel can be controlled by carbon exposure time, from 1 to around 10 layers. Further annealing process of samples allowed us to achieve improved graphene films by the dissolution and segregation-crystallization process.

Growth of graphene films by plasma enhanced chemical vapour deposition

Since it was isolated in 2004, graphene, the first known 2D crystal, is the object of a growing interest, due to the range of its possible applications as well as its intrinsic properties. From large scale electronics and photovoltaics to spintronics and fundamental quantum phenomena, graphene films have attracted a large community of researchers. But bringing graphene to industrial applications will require a reliable, low cost and easily scalable synthesis process. In this paper we present a new growth process based on plasma enhanced chemical vapor deposition. Furthermore, we show that, when the substrate is an oxidized silicon wafer covered by a nickel thin film, graphene is formed not only on top of the nickel film, but also at the interface with the supporting SiO2 layer. The films grown using this method were characterized using classical methods (Raman spectroscopy, AFM, SEM) and their conductivity is found to be close to those reported by others.

Study of Graphene Growth Mechanism on Nickel Thin Films

Since chemical vapor deposition of carbon-containing precursors onto transition metals tends to develop as the preferred growth process for the mass production of graphene films, the deep understanding of its mechanism becomes mandatory. In the case of nickel, which represents an economically viable catalytic substrate, the solubility of carbon is significant enough so that the growth mechanism proceeds in at least two steps: the dissolution of carbon in the metal followed by the precipitation of graphene at the surface. In this work, we use ion implantation to dissolve calibrated amounts of carbon in nickel thin films and grow graphene films by annealing. Observations of those graphene films using transmission electron microscopy , directly on the growth substrate as well as transfered on TEM grids, allowed us to precisely study the mechanisms that lead to their formation.