Plasma-Driven Tuning of Dielectric Permittivity in Graphene.

Materials with tunable negative electromagnetic performance, i.e., where dielectric permittivity becomes negative, have long been pursued in materials research due to their peculiar electromagnetic (EM) characteristics. Here, this promising feature is reported in materials on the case of plasma-synthesized nitrogen-doped graphene sheets with tunable permittivity over a wide (1-40 GHz) frequency range. Selectively incorporated nitrogen atoms in a graphene scaffold tailor the electronic structure in a way that provides an ultra-low energy (0.5-2 eV) 2D surface plasmon excitation, leading to subunitary and negative dielectric constant values in the Ka-band, from 30 up to 40 GHz. By allowing the tailoring of structures at atomic scale, this novel plasma-based approach creates a new paradigm for designing 2D nanomaterials like nanocarbons with controllable and tunable permittivity, opening a path to the next generation of 2D metamaterials.

Advanced Carbon-Nickel Sulfide Hybrid Nanostructures: Extending the Limits of Battery-Type Electrodes for Redox-Based Supercapacitor Applications.

Transition-metal sulfides combined with conductive carbon nanostructures are considered promising electrode materials for redox-based supercapacitors due to their high specific capacity. However, the low rate capability of these electrodes, still considered "battery-type" electrodes, presents an obstacle for general use. In this work, we demonstrate a successful and fast fabrication process of metal sulfide-carbon nanostructures ideal for charge-storage electrodes with ultra-high capacity and outstanding rate capability. The novel hybrid binder-free electrode material consists of a vertically aligned carbon nanotube (VCN), terminated by a nanosized single-crystal metallic Ni grain; Ni is covered by a nickel nitride (Ni3N) interlayer and topped by trinickel disulfide (Ni3S2, heazlewoodite). Thus, the electrode is formed by a Ni3S2/Ni3N/Ni@NVCN architecture with a unique broccoli-like morphology. Electrochemical measurements show that these hybrid binder-free electrodes exhibit one of the best electrochemical performances compared to the other reported Ni3S2-based electrodes, evidencing an ultra-high specific capacity (856.3 C g-1 at 3 A g-1), outstanding rate capability (77.2% retention at 13 A g-1), and excellent cycling stability (83% retention after 4000 cycles at 13 A g-1). The remarkable electrochemical performance of the binder-free Ni3S2/Ni3N/Ni@NVCN electrodes is a significant step forward, improving rate capability and capacity for redox-based supercapacitor applications.

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.

Oriented Carbon Nanostructures by Plasma Processing: Recent Advances and Future Challenges.

Carbon, one of the most abundant materials, is very attractive for many applications because it exists in a variety of forms based on dimensions, such as zero-dimensional (0D), one-dimensional (1D), two-dimensional (2D), and-three dimensional (3D). Carbon nanowall (CNW) is a vertically-oriented 2D form of a graphene-like structure with open boundaries, sharp edges, nonstacking morphology, large interlayer spacing, and a huge surface area. Plasma-enhanced chemical vapor deposition (PECVD) is widely used for the large-scale synthesis and functionalization of carbon nanowalls (CNWs) with different types of plasma activation. Plasma-enhanced techniques open up possibilities to improve the structure and morphology of CNWs by controlling the plasma discharge parameters. Plasma-assisted surface treatment on CNWs improves their stability against structural degradation and surface chemistry with enhanced electrical and chemical properties. These advantages broaden the applications of CNWs in electrochemical energy storage devices, catalysis, and electronic devices and sensing devices to extremely thin black body coatings. However, the controlled growth of CNWs for specific applications remains a challenge. In these aspects, this review discusses the growth of CNWs using different plasma activation, the influence of various plasma-discharge parameters, and plasma-assisted surface treatment techniques for tailoring the properties of CNWs. The challenges and possibilities of CNW-related research are also discussed.