Electroanalytical Performance of Nitrogen-Doped Graphene Films Processed in One Step by Pulsed Laser Deposition Directly Coupled with Thermal Annealing

Abstract

Graphene-based materials are widely studied to enable significant improvements in electroanalytical devices requiring new generations of robust, sensitive and low-cost electrodes. In this paper, we present a direct one-step route to synthetize a functional nitrogen-doped graphene film onto a Ni-covered silicon electrode substrate heated at high temperature, by pulsed laser deposition of carbon in the presence of a surrounding nitrogen atmosphere, with no post-deposition transfer of the film. With the ferrocene methanol system, the functionalized electrode exhibits excellent reversibility, close to the theoretical value of 59 mV, and very high sensitivity to hydrogen peroxide oxidation. Our electroanalytical results were correlated with the composition and nanoarchitecture of the N-doped graphene film containing 1.75 at % of nitrogen and identified as a few-layer defected and textured graphene film containing a balanced mixture of graphitic-N and pyrrolic-N chemical functions. The absence of nitrogen dopant in the graphene film considerably degraded some electroanalytical performances. Heat treatment extended beyond the high temperature graphene synthesis did not significantly improve any of the performances. This work contributes to a better understanding of the electrochemical mechanisms of doped graphene-based electrodes obtained by a direct and controlled synthesis process.

Raman study of the substrate influence on graphene synthesis using a solid carbon source via rapid thermal annealing

“…The combination of those resonances can appear without defects as the two phonons can verify momentum conservation, provided that they have opposite wavevectors. In the case of the D + G peak, also sometimes labeled D + D′, the excitation mechanisms are somewhat unclear, but they also appear in defective graphene‐like material . The insert in Figure b shows the deconvolution of the 2D peak from a spectrum from the graphene film obtained at 1,000°C on SiO 2 .…”

Pulsed Laser Deposited Films for Microbatteries

“…On the other hand, a N-doped graphene (NG) electrode prepared by PLD coupled with in-situ thermal annealing (PLD-TA) was achieved by Fortgang et al [338]. More recently, Bourquard et al used the PLD-TA process to form an N-doped graphene film by high temperature condensation of the laser-induced carbon plasma plume onto the Si electrode previously covered by an Ni catalytic film [339], using a protocol published by the same group [340] Carbon was ablated at 780 • C from the graphite target using a femtosecond laser (λ = 800 nm, pulse width of 60 ns, repetition rate of 1 kHz, and Φ = 5 J·cm −2 ) at a distance of 36 mm from the graphite target, with P N = 10 Pa in the vacuum chamber. The electrochemical properties were measured with the thus-obtained 40 nm-thick film with a nitrogen concentration of 1.75% as the working electrode and an active area of 0.07 cm 2 , saturated calomel electrode as the reference electrode, and platinum as the counter electrode, in a 0.5 mol·L −1 1,1 ferrocene-dimethanol solution of 0.1 mol·L −1 NaClO 4 .…”

Facile and controllable synthesis N-doping porous Graphene for high-performance Supercapacitor

“…Dut to the chemical interness, the N2 gas is not frequently used for N-doping , but here we observed N doping in PG nanosheets by N2. This is quite surprising, we speculate the reason is, the Ni and Co particle formed in the heating process can used as the catalysts, when the sample was heated to 800 °C, the N2 are decomposed, and during the pore generation process, the freshly formed edges and defect sites further decrease the energy barrier for N-doping [39,40]. A higher N content in PG-Ni could be explained by that, due to the fine particle size, a higher effective surface area and therefore more active sites during the nitrogen doping process are available to enable a high N-doping content in PG-Ni..…”