Low temperature electrical transport in microwave plasma fabricated free-standing graphene and N-graphene sheets

Funding Information: This work was performed under the framework of the PEGASUS (Plasma Enabled and Graphene Allowed Synthesis of Unique nano-Structures) project, funded by the European Union’s Horizon research and innovation program under grant agreement No 766894. Work partially funded by Portuguese FCT - Fundação para a Ciência e a Tecnologia, through EAGER project (PTDC/NAN-MAT/30565/2017) and under projects UIDB/50010/2020 and UIDP/50010/2020. The authors would like to thank S. Russev for the SEM images. M A, E V, K K and Zh K thank the European Regional Development Fund within the Operational Programme ‘Science and Education for Smart Growth 2014–2020’ under the Project CoE ‘National center of mechatronics and clean technologies ‘BG05M2OP001-1.001-0008’. Publisher Copyright: © 2023 The Author(s). Published by IOP Publishing Ltd.In this paper, the electrical transport in free-standing graphene and N-graphene sheets fabricated by a microwave plasma-based method is addressed. Temperature-dependent resistivity/conductivity measurements are performed on the graphene/N-graphene sheets compressed in pellets. Different measurement configurations reveal directional dependence of current flow—the room-temperature conductivity longitudinal to the pellet’s plane is an order of magnitude higher than the transversal one, due to the preferential orientation of graphene sheets in the pellets. SEM imaging confirms that the graphene sheets are mostly oriented parallel to the pellet’s plane and stacked in agglomerates. The high longitudinal electrical conductivity with values on the order of 103 S/m should be noted. Further, the current flow mechanism revealed from resistivity-temperature dependences from 300K down to 10K shows non-metallic behavior manifested with an increasing resistivity with decreasing the temperature d ρ / d T < 0 usually observed for insulating or localized systems. The observed charge transport shows variable range hopping at lower temperatures and thermally activated behaviour at higher temperatures. This allows us to attribute the charge transport mechanism to a partially disordered system in which single graphene sheets are placed predominantly parallel to each other and stacked together.publishersversionpublishe

Tailored Modification of Plasma Polymerized Nanoparticles

International audienceReactive plasmas are an excellent source for dust particles with different characteristics. In the work presented herein the nanoparticles produced in such systems were post-processed by means of annealing, VUV/x-ray irradiation, and ion bombardment

Deposition and tuning of nanostructured hydrocarbon deposits From superhydrophobic to superhydrophilic and back

International audienceCarbonaceous fluorine free nanoparticles synthesized in a low temperature acetylene discharge are used in a first step for the production of (super)hydrophobic coatings. In a second step, the influence of different plasma and UV induced functionalizations on the wetting characteristics of these materials is investigated. The experiments show that the superhydrophobic surfaces can be turned continuously and reversibly into hydrophilic (superhydrophilic) surfaces by means of the different treatment methods. The reversibility of these processes is studied in a third step. It is shown that the changes of the surface which are induced by the plasma treatment can be undone by means of EUV irradiation. The switchability of the surface due to external stimuli can be easily used for the controlled production of patterned surfaces. This is demonstrated by means of one simple example

Deposition and tuning of nanostructured hydrocarbon deposits: From superhydrophobic to superhydrophilic and back

International audienceCarbonaceous fluorine free nanoparticles synthesized in a low temperature acetylene discharge are used in a first step for the production of (super)hydrophobic coatings. In a second step, the influence of different plasma and UV induced functionalizations on the wetting characteristics of these materials is investigated. The experiments show that the superhydrophobic surfaces can be turned continuously and reversibly into hydrophilic (superhydrophilic) surfaces by means of the different treatment methods. The reversibility of these processes is studied in a third step. It is shown that the changes of the surface which are induced by the plasma treatment can be undone by means of EUV irradiation. The switchability of the surface due to external stimuli can be easily used for the controlled production of patterned surfaces. This is demonstrated by means of one simple example

N Graphene Nanowalls via Plasma Nitrogen Incorporation and Substitution The Experimental Evidence

Incorporating nitrogen (N) atom in graphene is considered a key technique for tuning its electrical properties. However, this is still a great challenge, and it is unclear how to build N-graphene with desired nitrogen configurations. There is a lack of experimental evidence to explain the influence and mechanism of structural defects for nitrogen incorporation into graphene compared to the derived DFT theories. Herein, this gap is bridged through a systematic study of different nitrogen-containing gaseous plasma post-treatments on graphene nanowalls (CNWs) to produce N-CNWs with incorporated and substituted nitrogen. The structural and morphological analyses describe a remarkable difference in the plasma–surface interaction, nitrogen concentration and nitrogen incorporation mechanism in CNWs by using different nitrogen-containing plasma. Electrical conductivity measurements revealed that the conductivity of the N-graphene is strongly influenced by the position and concentration of C–N bonding configurations. These findings open up a new pathway for the synthesis of N-graphene using plasma post-treatment to control the concentration and configuration of incorporated nitrogen for application-specific properties. [Image: see text] ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (10.1007/s40820-020-0395-5) contains supplementary material, which is available to authorized users

N-Graphene-Metal-Oxide(Sulfide) hybrid Nanostructures: Single-step plasma-enabled approach for energy storage applications

Hybrid graphene-based nanostructures are considered promising materials for energy storage applications. However, the synthesis of high-quality hybrid graphene nanostructures at high yields is challenging. In the present work we propose a novel, single-step microwave plasma-enabled approach to synthetize customizable hybrid graphene-based nanostructures at high-yield while preserving their quality. Hybrid N-graphene (nitrogen-doped graphene) metal-based nanostructures, for instance, can be produced at a rate of ∼ 19 mg/min. The high energy density region of a microwave plasma provides sufficient energy and “building particles” fluxes towards the low-energy density plasma afterglow for the processes of assembly and growth of N-graphene sheets. Simultaneously, a controlled jet of metal-oxide(-sulfide) microparticles is sprayed into the plasma afterglow region where they bind to N-graphene sheets. Methane/methylamine are used as carbon and nitrogen precursors, combined with micron-sized MnO2 and oxy-MnS particles to synthesize the hybrid structures. As a result, nano-sized (∼10–30 nm) MnOx particles decorated N-graphene (4.6 at. N%) and oxidized metal sulfide anchored N-graphene sheets (3.1 at. N%) are produced at atmospheric conditions. High structural quality and distribution of metal-based nanostructures on N-graphene sheets are revealed using transmission and scanning electron microscopes and other advanced spectroscopic techniques. Finally, an electrode for supercapacitor based on the N-graphene-metal-oxide(sulfide) hybrid nanostructures is developed with promising specific capacitances (∼273 F.g−1 at 0.5 A.g−1). The described chemically engineered process is one of the fastest approaches reported for designing the high-quality hybrid nanostructures produced at a high-yield, and as such, is expected to provide a high impact on the design of electrode materials for sustainable energy storage systems.publishedVersio

N-Graphene-Metal-Oxide(Sulfide) hybrid Nanostructures: Single-step plasma-enabled approach for energy storage applications

Hybrid graphene-based nanostructures are considered promising materials for energy storage applications. However, the synthesis of high-quality hybrid graphene nanostructures at high yields is challenging. In the present work we propose a novel, single-step microwave plasma-enabled approach to synthetize customizable hybrid graphene-based nanostructures at high-yield while preserving their quality. Hybrid N-graphene (nitrogen-doped graphene) metal-based nanostructures, for instance, can be produced at a rate of ∼ 19 mg/min. The high energy density region of a microwave plasma provides sufficient energy and “building particles” fluxes towards the low-energy density plasma afterglow for the processes of assembly and growth of N-graphene sheets. Simultaneously, a controlled jet of metal-oxide(-sulfide) microparticles is sprayed into the plasma afterglow region where they bind to N-graphene sheets. Methane/methylamine are used as carbon and nitrogen precursors, combined with micron-sized MnO2 and oxy-MnS particles to synthesize the hybrid structures. As a result, nano-sized (∼10–30 nm) MnOx particles decorated N-graphene (4.6 at. N%) and oxidized metal sulfide anchored N-graphene sheets (3.1 at. N%) are produced at atmospheric conditions. High structural quality and distribution of metal-based nanostructures on N-graphene sheets are revealed using transmission and scanning electron microscopes and other advanced spectroscopic techniques. Finally, an electrode for supercapacitor based on the N-graphene-metal-oxide(sulfide) hybrid nanostructures is developed with promising specific capacitances (∼273 F.g−1 at 0.5 A.g−1). The described chemically engineered process is one of the fastest approaches reported for designing the high-quality hybrid nanostructures produced at a high-yield, and as such, is expected to provide a high impact on the design of electrode materials for sustainable energy storage systems

Towards large-scale in free-standing graphene and N-graphene sheets

Abstract One of the greatest challenges in the commercialization of graphene and derivatives is production of high quality material in bulk quantities at low price and in a reproducible manner. The very limited control, or even lack of, over the synthesis process is one of the main problems of conventional approaches. Herein, we present a microwave plasma-enabled scalable route for continuous, large-scale fabrication of free-standing graphene and nitrogen doped graphene sheets. The method’s crucial advantage relies on harnessing unique plasma mechanisms to control the material and energy fluxes of the main building units at the atomic scale. By tailoring the high energy density plasma environment and complementarily applying in situ IR and soft UV radiation, a controllable selective synthesis of high quality graphene sheets at 2 mg/min yield with prescribed structural qualities was achieved. Raman spectroscopy, scanning electron microscopy, high resolution transmission electron microscopy, X-ray photoelectron spectroscopy and Near Edge X-ray-absorption fine-structure spectroscopy were used to probe the morphological, chemical and microstructural features of the produced material. The method described here is scalable and show a potential for controllable, large-scale fabrication of other graphene derivatives and promotes microwave plasmas as a competitive, green, and cost-effective alternative to presently used chemical methods