Christophe Donnet

Electrochemical boron-doped diamond film microcells micromachined with femtosecond laser: application to the determination of water framework directive metals.

Planar electrochemical microcells were micromachined in a microcrystalline boron-doped diamond (BDD) thin layer using a femtosecond laser. The electrochemical performances of the new laser-machined BDD microcell were assessed by differential pulse anodic stripping voltammetry (DPASV) determinations, at the nanomolar level, of the four heavy metal ions of the European Water Framework Directive (WFD): Cd(II), Ni(II), Pb(II), Hg(II). The results are compared with those of previously published BDD electrodes. The calculated detection limits are 0.4, 6.8, 5.5, and 2.3 nM, and the linearities go up to 35, 97, 48, and 5 nM for, respectively, Cd(II), Ni(II) Pb(II), and Hg(II). The detection limits meet with the environmental quality standard of the WFD for three of the four metals. It was shown that the four heavy metals could be detected simultaneously in the concentration ratio usually measured in sewage or runoff waters.

Study of plasma expansion induced by femtosecond pulsed laser ablation and deposition of diamond-like carbon films

Abstract Diamond-like carbon (DLC) films were deposited in high vacuum conditions at room temperature, by ablating graphite targets with femtosecond laser pulses. The structure of the films deposited onto silicon substrates were characterized by Raman spectroscopy and X-ray absorption near edge spectroscopy (XANES). Films exhibit unusual structure, Raman spectra showing the presence of nanocrystalline diamond in amorphous matrix. Plasma plume was imaged by a gated ICCD camera in the UV-Visible range. The behavior of the plume shape as well as the kinetic energy of the particles are investigated. The behavior of the expansion dynamics of the plume and the properties of thin films are studied in order to determine the optimal growth conditions for femtosecond pulsed laser deposition of DLC films.

Structure of diamondlike carbon films deposited by femtosecond and nanosecond pulsed laser ablation

The characterization of diamondlike carbon (DLC) films is a challenging subject, considering the diversity of carbon-based nanostructures depending on the deposition process. We propose to combine multiwavelength (MW) Raman spectroscopy and electron energy-loss spectroscopy (EELS) to probe the structural disorder and the carbon hybridizations of DLC films deposited by pulsed laser ablation performed either with a nanosecond laser (film labeled ns-DLC), either with a femtosecond laser (film labeled fs-DLC). Such deposition methods allow to reach a rather high carbon sp3 hybridization but with some significant differences in terms of structural disorder and carbonaceous chain configurations. MW Raman investigations, both in the UV and visible range, is a popular and nondestructive way to probe the structural disorder and the carbon hybridizations. EELS allows the determination of the carbon plasmon energy in the low-loss energy region of the spectra, as well as the fine structure of the ionization threshold...

Characterization of different diamond-like carbon electrodes for biosensor design.

Diamond-like carbon (DLC) films are gaining big interest in electrochemistry research area. DLC electrodes made with different ratio of sp(3)/sp(2) carbon hybridization or doped with different percentages of nickel were characterized electrochemically by cyclic voltammetry and by amperometric measurements towards hydrogen peroxide. SiCAr1 and SiCNi5% were chosen as sensitive transducers for the elaboration of amperometric glucose biosensors. Immobilization of glucose oxidase was carried out by cross-linking with glutaraldehyde. Measurements were made at a fixed potential+1.0V in 40mM phosphate buffer pH 7.4. SiCAr1 seems to be more sensitive for glucose, 0.6875muA/mM, than SiCNi5%, 0.3654muA/mM. Detections limits were 20muM and 30muM, respectively. Apparent Michaelis-Menten constants were found around 3mM. Forty-eight percent and 79% of the original response for 0.5mM glucose remained after 10 days for both biosensors, respectively.

Robust Electrografting on Self-Organized 3D Graphene Electrodes

Improving graphene-based electrode fabrication processes and developing robust methods for its functionalization are two key research routes to develop new high-performance electrodes for electrochemical applications. Here, a self-organized three-dimensional (3D) graphene electrode processed by pulsed laser deposition with thermal annealing is reported. This substrate shows great performance in electron transfer kinetics regarding ferrocene redox probes in solution. A robust electrografting strategy for covalently attaching a redox probe onto these graphene electrodes is also reported. The modification protocol consists of a combination of diazonium salt electrografting and click chemistry. An alkyne-terminated phenyl ring is first electrografted onto the self-organized 3D graphene electrode by in situ electrochemical reduction of 4-ethynylphenyl diazonium. Then the ethynylphenyl-modified surface efficiently reacts with the redox probe bearing a terminal azide moiety (2-azidoethyl ferrocene) by means of Cu(I)-catalyzed alkyne-azide cycloaddition. Our modification strategy applied to 3D graphene electrodes was analyzed by means of atomic force microscopy, scanning electron microscopy, Raman spectroscopy, cyclic voltammetry, and X-ray photoelectron spectroscopy (XPS). For XPS chemical surface analysis, special attention was paid to the distribution and chemical state of iron and nitrogen in order to highlight the functionalization of the graphene-based substrate by electrochemically grafting a ferrocene derivative. Dense grafting was observed, offering 4.9 × 10(-10) mol cm(-2) surface coverage and showing a stable signal over 22 days. The electrografting was performed in the form of multilayers, which offers higher ferrocene loading than a dense monolayer on a flat surface. This work opens highly promising perspectives for the development of self-organized 3D graphene electrodes with various sensing functionalities.

Graphene-based textured surface by pulsed laser deposition as a robust platform for surface enhanced Raman scattering applications

We have developed a surface enhanced Raman scattering (SERS)-active substrate based on gold nanoparticles-decorated few-layer (fl) graphene grown by pulsed laser deposition. Diamond-Like Carbon film has been converted to fl-graphene after thermal annealing at low temperature. The formation of fl-graphene was confirmed by Raman spectroscopy, and surface morphology was highlighted by scanning electron microscopy. We found that textured fl-graphene film with nanoscale roughness was highly beneficial for SERS detection. Rhodamine 6G and p-aminothiophenol proposed as test molecules were detected with high sensitivity. The detection at low concentration of deltamethrin, an active molecule of a commercial pesticide was further demonstrated.

In situ diagnostic of the size distribution of nanoparticles generated by ultrashort pulsed laser ablation in vacuum

We aim to characterize the size distribution of nanoparticles located in the ablation plume produced by femtosecond laser interaction. The proposed method relies on the use of white-light extinction spectroscopy setup assisted by ultrafast intensified temporal gating. This method allows measurement of optical absorbance of a nickel nanoparticles cloud. Simulation of the extinction section of nickel nanoparticles size distributions has been developed in order to compare the measured optical absorbance to the optical extinction by theoretical and experimental nanoparticles size distributions (measured by scanning electron microscopy). A good agreement has been found between the in situ measured optical absorbance and the optical extinction cross section calculated from ex situ nanoparticles size distribution measurements.

Depth-dependence of electrical conductivity of diamondlike carbon films

The electrical behavior of diamondlike carbon (DLC) has been measured as a function of depth. The amorphous carbon (a-C) films are deposited by pulsed laser deposition using two complementary setups: a femtosecond (fs) and a nanosecond (ns) pulse lasers. It is demonstrated through four probe resistance measurements and contact resistance mapping that the fs DLC are electrically heterogeneous in thickness. The presence of a thick sp2 rich layer on top is evidenced for fs a-C and is apparently away in the sp3 rich ns a-C. It is attributed to different subplantation processes between ns and fs a-C films.

Nano-Architecture of nitrogen-doped graphene films synthesized from a solid CN source

New synthesis routes to tailor graphene properties by controlling the concentration and chemical configuration of dopants show great promise. Herein we report the direct reproducible synthesis of 2-3% nitrogen-doped ‘few-layer’ graphene from a solid state nitrogen carbide a-C:N source synthesized by femtosecond pulsed laser ablation. Analytical investigations, including synchrotron facilities, made it possible to identify the configuration and chemistry of the nitrogen-doped graphene films. Auger mapping successfully quantified the 2D distribution of the number of graphene layers over the surface, and hence offers a new original way to probe the architecture of graphene sheets. The films mainly consist in a Bernal ABA stacking three-layer architecture, with a layer number distribution ranging from 2 to 6. Nitrogen doping affects the charge carrier distribution but has no significant effects on the number of lattice defects or disorders, compared to undoped graphene synthetized in similar conditions. Pyridinic, quaternary and pyrrolic nitrogen are the dominant chemical configurations, pyridinic N being preponderant at the scale of the film architecture. This work opens highly promising perspectives for the development of self-organized nitrogen-doped graphene materials, as synthetized from solid carbon nitride, with various functionalities, and for the characterization of 2D materials using a significant new methodology.