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Graphene-based nanomaterials that combine significant photocatalytic, antioxidant and antibacterial activity are very attractive candidates for biomedical and environmental applications. Conventional chemical synthesis routes may contaminate the resultant materials with toxic molecules, compromising their properties and limiting their use in biomedical applications. Ideally, to avoid any contamination, the nanomaterials should be synthesized from non-toxic precursors and reagents, e.g. foodstuff via a simple technology that does not rely on the use of hazardous chemicals yet produces materials of high quality. Here, we report an environmentally friendly, low cost reduced graphene oxide-silver-silver oxide nanocomposite with strong photocatalytic, antioxidant and antibacterial activity for environmental remediation. The reduced graphene oxide (FRGO) is synthesized from edible sunflower oil via a simple flame synthesis method. Next, silver nanoparticles (Ag/AgO/Ag2O) are produced by phytochemical reduction of AgNO3 using a reducing agent based on flavonoids from Coleus aromaticus (Mexican mint), also used in food industry. Thus-obtained FRGO-Ag/AgO/Ag2O composite is characterized using X-ray diffraction spectroscopy, scanning electron microscopy, fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy. The degradation of anionic textile dye Methylene blue (MB) is used as a measure of photocatalytic activity of FRGO and FRGO/Ag/AgO/Ag2O, with solution pH, initial dye concentration, and quantity of the catalyst considered as influencing factors. FRGO-Ag/AgO/Ag2O composites show strong antioxidant activity, with improved radical inhibition as well as dye degradation properties when compared to pristine FRGO.

Environmental concerns regarding the use of potentially harmful chemicals and fossil fuels stimulate research efforts on the multifunctional hybrid nanocomposites produced from biowastes via simple environmentally friendly processes. Such nanomaterials could help to combat the escalating environmental issues related to environmental remediation and energy storage, as a step to the renewable energy technology of the future. This work discusses the synthesis of novel nickel-based reduced graphene oxide (rGO) nanostructured composites with superior energy storage and photocatalytic properties. Using a facile hydrothermal method, rGO nanoflakes were synthesized from the negative value coconut coir biowaste and then decorated with functional NiO and NiFe2O4 nanoparticles to produce hierarchical functional nanocomposites. Benefiting from the synergies arising from the concomitant use of NiFe2O4 nanoparticles and rGO nanoflakes, the resultant nanocomposites yielded excellent specific capacitance of 599.9 F/g at current density of 1 Ag-1 and retention rate of 86.5% even after 2000 cycles. Moreover, the composite exhibited excellent efficiency of visible light driven photocatalytic degradation of 96.5%. Thus, our material is essentially multifunctional and importantly, it demonstrates quite pronounced electrochemical and photocatalytic activities when produced in a simple, single technological route. These findings confirm that the developed multifunctional nanostructured composite is a strong candidate material for energy and environmental remediation applications.

Graphene and its derivatives have acquired substantial research attention in recent years because of their wide range of potential applications. Implementing sustainable technologies for fabricating these functional nanomaterials is becoming increasingly apparent, and therefore, a wide spectrum of naturally derived precursors has been identified and reformed through various established techniques for the purpose. Nevertheless, most of these methods could only be considered partially sustainable because of their complexity as well as high energy, time, and resource requirements. Here, we report the fabrication of carbon nano-onion-interspersed vertically oriented multilayer graphene nanosheets through a single-step, environmentally benign radio frequency plasma-enhanced chemical vapor deposition process from a low-cost carbon feedstock, the oil from the peel of Citrus sinensis orange fruits. C. sinensis essential oil is a volatile aroma liquid principally composed of nonsynthetic hydrocarbon limonene. Transmission electron microscopy studies on the structure unveiled the presence of hollow quasi-spherical carbon nano-onion-like structures incorporated within graphene layers. The as-fabricated nano-onion-incorporated graphene films exhibited a highly hydrophobic nature showing a water contact angle of up to 129(0). The surface energies of these films were in the range of 41 to 35 mJ.m(-2). Moreover, a chemiresistive sensor directly fabricated using C. sinensis-derived onion-structured graphene showed a p-type semiconductor nature and a promising response to acetone at room temperature. With its unique morphology, surface properties, and electrical characteristics, this material is expected to be useful for a wide range of applications.

Supercapacitors and other innovative devices for electric energy generation and storage could significantly improve ecological situation in large densely populated cities. However, for this to become reality, supercapacitors should be produced en masse via a clean, green technology from the ecologically friendly material, preferably from abundant, sustainable resources, such as agricultural waste that is a by-product of other technological cycles. Many types of agricultural waste could be considered as an abundant, low-cost carbon source for large-scale fabrication of graphene-type materials. Here, we demonstrate that widely available coconut waste can be efficiently converted into reduced graphene oxide via simple catalytic oxidation using ferrocene as an efficient and low-cost catalyst. The structure and morphology of the as-prepared materials were characterized by XRD, SEM, and TEM techniques. The results confirmed the formation of high-quality reduced graphene oxide. The as-prepared graphene oxide was then analyzed as an electrode material for supercapacitor applications. We have found that the material exhibits high performance as an electric double layer capacitor (EDLC) and demonstrates excellent cyclic stability. Therefore, the reduced graphene oxide prepared via a simple, green process from this type of agricultural waste could be a good candidate of the supercapacitor electrodes.

Tunability and fine control of structure and morphology in the patterns of vertically-oriented graphenes is of high importance for their efficient functionalization and application. In this work, we present an experimental and simulation insight into the formation of graphene structures. Detailed simulations by an ad hoc model based on a large number of interacting elemental processes were implemented to ensure a deeper insight into the processes which cannot be directly measured and assessed in the experiments, such as relative densities of adsorbed species and density of ion current at the nanostructures. The combination of the experimental and simulation approaches provided a new level of understanding of the processes that govern formation of the graphene network morphology. Moreover, the potential of novel analytical techniques such as Hough transformations, fractal dimension distributions and Minkovski connectivity, 2D FFT transforms, Hough transformation spectra and others for analysis of the graphene array morphology was successfully demonstrated. The evolution of surface morphology of graphene derived from cold-pressed Citrus sinensis oil, a by-product of orange juice production by centrifugation, synthesised via a catalyst‒free process, was investigated using experimental analyses, Raman spectroscopy, scanning electron microscopy and X‒ray photoelectron spectroscopy, and numerous advanced analytical techniques such as distributions of fractal dimensions. National Research Foundation (NRF) This work was supported in part by the following funds and organizations: 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 programme under grant agreement No. 766894; OSTIn-SRP/EDB, National Research Foundation, and AcRF (Rp6/16 Xs) Singapore; I. L. acknowledges support from the School of Chemistry, Physics and Mechanical Engineering, Science and Engineering Faculty, Queensland University of Technology. K.B. acknowledges support from the Australian Research Council.

Oil spills into ocean or coastal waters can result in significant damage to the environment via pollution of aquatic ecosystems. Absorbents based on reduced graphene oxide (rGO) foams have the capacity to remove minor or major oil spills. However, conventional chemical synthesis of rGO often uses petrochemical precursors, potentially harmful chemicals, and requires special processing conditions that are expensive to maintain. In this work, an alternative cost-effective and environmentally friendly approach suitable for large-scale production of high-quality rGO directly from used cooking sunflower oil is discussed. Thus, produced flaky graphene structures are effective in absorbing used commercial sunflower oil and engine oil, via monolayer physisorption in the case of used sunflower and engine oils facilitated by van der Waals forces, π–π stacking and hydrophobic interactions, π-cation (H+) stacking and radical scavenging activities. From adsorption kinetic models, first-order kinetics provides a better fit for used sunflower oil adsorption (R2 = 0.9919) and second-order kinetics provides a better fit for engine oil adsorption (R2 = 0.9823). From intra-particle diffusion model, R2 for USO is 0.9788 and EO is 0.9851, which indicates that both used sunflower and engine oils adsorption processes follow an intra-particle diffusion mechanism. This study confirms that waste-derived rGO could be used for environmental remediation.

Nitrogen-doped graphene-based aerogels with three levels of hierarchically organized pores were prepared via a simple environmentally friendly process, and successfully tested in supercapacitor applications. Mesopores and macropores were formed during the aerogel preparation followed by carbonization and its chemical activation by potassium hydroxide (KOH). These mesopores and macropores consist of amorphous carbon and a 3D graphene framework. Thermal treatment at 700 &deg, C, 800 &deg, C, 900 &deg, C in N2 atmosphere was done to etch out the amorphous carbon and obtain a stable N-doped 3D graphene. Specific capacitance values obtained from the electrochemical measurements are in the range of 232&ndash, 170 F&times, g&minus, 1. The thus fabricated structures showed excellent cyclic stability, suggesting that these materials have potential as electrodes for solid asymmetric supercapacitors.

An integrated microcontroller-based data acquisition and robotic actuation suite comprising digital electronics, microcontrollers, custom-made hardware, and accessorial software for diagnostics, and characterization of electric propulsion thrusters in a large vacuum space environment simulator is designed, built, and tested. The components of the characterization suite have been aggregated into modular add-on units for rapid rearrangement and easy customization to suit various applications. The modules include a force calibration system for accurate thrust measurements in various thrust stands, and spatially resolved measurements in a multiprobe array comprising Langmuir and Faraday probes for plume diagnostics of plasma thrusters. Plume and thrust characteristics of a miniaturized Hall-type thruster were successfully measured in situ, enabling users to vary process controls and efficiently optimize the thruster performance. The system revealed a further potential for real-time flight mission diagnostics and control.

In austere environments, for example, in outer space, on surfaces of extra-terrestrial bodies (Moon, Mars, etc.), or under water, technologies that can enable continuous, reliable, and authentic monitoring of movement of human operators and devices can be critical. We report here the production and human body test of wearable, flexible graphene oxide stress sensors suitable for real-time monitoring of body parameters, state and position of humans, and automatic equipment. These sensors have excellent sensitivity and signal strength across a wide strain range, alleviating the need for additional instrumentation for signal processing and amplification. Their low cost makes them virtually disposable, which may benefit such applications as smart clothing. The sensors were fabricated by a concomitant reduction and N-doping of graphene oxide on polydimethylsiloxane in N2-H2 plasma. The direct bias and other plasma parameters have a significant effect on the reduction and properties of graphene oxide sensors, as shown by optical emission, Raman and X-ray photoelectron spectroscopies, and X-ray diffraction. Optical emission showed different excitation and ionization processes involving atomic and molecular species in the N2-H2 discharge. The photoelectron spectroscopy has confirmed the graphene reduction and introduction of nitrogen doping into the reduced graphene oxide. The bias efficiently controls plasma-induced electric fields, and plasma-related effects determine the N-doping levels. The reduced graphene oxides demonstrate excellent tensile properties, which make them suitable for efficient but cheap stress sensors. This eco-friendly, fast, room-temperature method shows a great potential for fabrication of efficient, flexible sensors.

Two-dimensional BN/CN nanomaterials of various composition and morphology were synthesized in N2 H2 plasma by plasma-enhanced hot filament chemical vapor deposition, with B4C used as precursor. The results of field emission scanning electron microscopy, X-ray diffractometer, transmission electron microscopy, micro-Raman and X-ray photoelectron spectroscopy evidence that the hexagonal boron nitride nanowalls with carbon and oxide phases were synthesized under about 1:1 ratio of H2 to N2, while the CN nanorods with boron and oxide phases are formed under other ratios of H2 to N2, and the nanowires made of oxide phases are grown without the plasma. Efficient control over the nanostructure composition and morphology was demonstrated, thus proposing a cheap and convenient fabrication technique for the advanced composite boron nitride/graphene materials. The photoluminescence properties of the synthesized BN and CN nanomaterials were also studied using the 325 nm line of He Cd laser as the excitation source. The fabricated nanomaterials can generate the ultraviolet, blue and green multi-PL bands, which are associated to the defects formed in these nanomaterials and the carbon clusters, respectively. These outcomes can make a great contribution to the design of functional BN- and CN-nanomaterials of various morphologies and compositions for the applications in various electronic and carbon-based optoelectronic nanodevices.

Carbon nanotube (CNT) growth has been demonstrated recently using a number of nonmetallic semiconducting and metal oxide nanoparticles, opening up pathways for direct CNT synthesis from a number of more desirable templates without the need for metallic catalysts. However, CNT growth mechanisms using these nonconventional catalysts has been shown to largely differ and reamins a challenging synthesis route. In this contribution we show CNT growth from partially oxidized silicon nanocrystals (Si NCs) that exhibit quantum confinement effects using a microwave plasma enhanced chemical vapor deposition (PECVD) method. On the basis of solvent and a postsynthesis frgamentation process, we show that oxidation of our Si NCs can be easily controlled. We determine experimentally and explain with theoretical simulations that the Si NCs morphology together with a necessary shell oxide of ∼1 nm is vital to allow for the nonmetallic growth of CNTs. On the basis of chemical analysis post-CNT-growth, we give insight into possible mechanisms for CNT nucleation and growth from our partially oxidized Si NCs. This contribution is of significant importance to the improvement of nonmetallic catalysts for CNT growth and the development of Si NC/CNT interfaces.

The results of systematic numerical studies of graphene flakes growth in low-temperature arc discharge plasmas are presented. Diffusion-based growth model was developed, verified using the previously published experiments, and used to investigate the principal effects of the process parameters such as plasma density, electron temperature, surface temperature and time of growth on the size and structure of the plasma-grown graphene flakes. It was demonstrated that the higher growth temperatures result in larger graphene flakes reaching 5 μm, and simultaneously, lead to much lower density of the carbon atoms adsorbed on the flake surface. The low density of the carbon adatoms reduces the probability of the additional graphene layer nucleation on surface of growing flake, thus eventually resulting in the synthesis of the most valuable single-layered graphenes.

We describe a simple, efficient plasma-chemical technique for the synthesis of hybrid structures formed by vertically oriented BNCO nanowalls and vertically oriented graphene nanoflakes (BNCONW/GNFs), as well as their structure and photoluminescence properties. The BNCONW/GNF hybrid structures were fabricated by the synthesis of vertically oriented BNCO nanowalls in N2–H2 plasma using the plasma-enhanced hot filament chemical vapour deposition technique, followed by the direct synthesis of vertically oriented graphene nanoflakes on the BNCO nanowalls in a methane environment using a hot filament chemical vapour deposition method, where the B4C compound was used as the boron and carbon source. The results of field emission scanning electron microscopy, transmission electron microscopy, micro-Raman spectroscopy and X-ray photoelectron spectrometry measurements indicated that the BNCONW/GNF hybrid structures were composed of vertically oriented BNCO nanowalls and vertically oriented graphene nanoflakes. The photoluminescence studies of the vertically oriented BNCONW/GNF hybrid structures using a Ramalog system equipped with a 325 nm He–Cd laser demonstrated the possibility to efficiently tune the photoluminescence properties of the BNCONW/GNF structures by growing the graphene nanoflakes on the vertically oriented BNCONWs. Our findings can contribute to the designing of complex hybrid graphene–semiconductor structures suitable for applications in advanced next-generation optoelectronic nanodevices.

A simple and efficient method for synthesizing complex graphene-inspired BNCO nanoflakes by plasma-enhanced hot filament chemical vapour deposition using B4C as a precursor and N2/H2 reactive gases is reported. The results of the field emission scanning electron microscopy, X-ray diffractometer, micro-Raman spectroscopy, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy have evidenced that the BNCO nanostructures are composed of graphene-like hexagonal boron nitride nanoflakes with carbon and oxygen admixtures. The photoluminescence properties of the BNCO nanoflakes were studied in a Ramalog system using a He–Cd laser, and the results have demonstrated that the BNCO nanoflakes can generate strong green photoluminescence in the range of 515–569 nm, which was attributed to the aggregation of carbon atoms in the BNCO nanoflakes. The growth mechanism of the BNCO nanoflakes was also studied to show that the NH3+ ions generated in plasma play an important role in the formation of the BNCO nanoflakes. The results propose a novel and efficient method for the synthesis of BN-based nanomaterials using B4C precursors, and contribute to the design of the functional BN-based nanomaterials for various applications including optoelectronics, nanoelectronics, medical equipment, and wear-resistant materials for acceleration channels of electric propulsion thrusters.

Two Minkowski functionals were tested in the capacity of morphological descriptors to quantitatively compare the arrays of vertically-aligned graphene flakes grown on smooth and nanoporous alumina and silica surfaces. Specifically, the Euler-Poincare characteristic and fractal dimension graphs were used to characterize the degree of connectivity and order in the systems, i.e. in the graphene flake patterns of petal-like and tree-like morphologies on solid substrates, and meshlike patterns (networks) grown on nanoporous alumina treated in low-temperature inductivelycoupled plasma. It was found that the Minkowski functionals return higher connectivity and fractal dimension numbers for the graphene flakepatterns with more complex morphologies, and indeed can be used as morphological descriptors to differentiate among various configurations of vertically-aligned graphene flakes grown on surfaces.

Carbon nanotubes (CNTs) can be fabricated with an ordered microstructure by controlling their growth process. Unlike dispersed carbon nanotubes, these vertically-aligned arrays have the ability to support or inhibit bacteria biofilms. Here, we show that by treating the carbon nanotube arrays with plasma, different effects on biofilms of Gram-positive (Bacillus subtilis, Staphylococcus epidermidis) and Gram-negative bacteria (Escherichia coli, Pseudomonas aeruginosa) can be observed.

The enhanced large-scale model and numerical simulations are used to clarify the growth mechanism and the differences between the plasma- and neutral gas-grown carbon nanotubes, and to reveal the underlying physics and the key growth parameters. The results show that the nanotubes grown by plasma can be longer due to the effects of hydrocarbon ions with velocities aligned with the nanotubes. We show that the low-temperature growth is possible when the hydrocarbon ion flux dominates over fluxes of other species. We have also analysed the dependencies of the nanotube growth rates on nanotube and process parameters. The results are verified by a direct comparison with the experimental data. The model is generic and can be used for other types of carbon nanostructures such as carbon nanowalls, vertical graphenes, etc.

A novel platform consisting of a multilayered substrate, activated graphite-like carbon film, and dense forest of long, vertically-aligned multiwall carbon nanotubes grown by the chemical vapor deposition is designed, fabricated, and tested for covalent immobilization of enzymatic biocatalysts with the aim of protecting them from shear forces and microbial attacks present in bioreactors. The covalent bonding ensures enzyme retention in a flow, while the dense nanotube forest may serve as a protection of the enzymes from microbial attack without impeding the flow of reactants and products. This platform was demonstrated for the two reference enzymes, horseradish peroxidase and catalase, which were immobilized without degrading their biological activity. This combination of an activated carbon layer for an efficient immobilization of biocatalysts with a protective layer of inert carbon nanotubes could dramatically improve the efficiency and longevity of enzymatic bio-catalysis employed in a large variety of advanced biotechnological processes.

Graphene, a newly discovered and extensively investigated material, has many unique and extraordinary properties which promise major technological advances in fields ranging from electronics to mechanical engineering and food production. Unfortunately, complex techniques and high production costs hinder commonplace applications. Scaling of existing graphene production techniques to the industrial level without compromising its properties is a current challenge. This article focuses on the perspectives and challenges of scalability, equipment, and technological perspectives of the plasma-based techniques which offer many unique possibilities for the synthesis of graphene and graphene-containing products. The plasma-based processes are amenable for scaling and could also be useful to enhance the controllability of the conventional chemical vapour deposition method and some other techniques, and to ensure a good quality of the produced graphene. We examine the unique features of the plasma-enhanced graphene production approaches, including the techniques based on inductively-coupled and arc discharges, in the context of their potential scaling to mass production following the generic scaling approaches applicable to the existing processes and systems. This work analyses a large amount of the recent literature on graphene production by various techniques and summarizes the results in a tabular form to provide a simple and convenient comparison of several available techniques. Our analysis reveals a significant potential of scalability for plasma-based technologies, based on the scaling-related process characteristics. Among other processes, a greater yield of 1 g × h(-1) m(-2) was reached for the arc discharge technology, whereas the other plasma-based techniques show process yields comparable to the neutral-gas based methods. Selected plasma-based techniques show lower energy consumption than in thermal CVD processes, and the ability to produce graphene flakes of various sizes reaching hundreds of square millimetres, and the thickness varying from a monolayer to 10-20 layers. Additional factors such as electrical voltage and current, not available in thermal CVD processes could potentially lead to better scalability, flexibility and control of the plasma-based processes. Advantages and disadvantages of various systems are also considered.

Simple, rapid, catalyst-free synthesis of complex patterns of long, vertically aligned multiwalled carbon nanotubes, strictly confined within mechanically-written features on a Si(1 0 0) surface is reported. It is shown that dense arrays of the nanotubes can nucleate and fully fill the features when the low-temperature microwave plasma is in a direct contact with the surface. This eliminates additional nanofabrication steps and inevitable contact losses in applications associated with carbon nanotube patterns.

A novel approach to large-scale production of high-quality graphene flakes in magnetically-enhanced arc discharges between carbon electrodes is reported. A non-uniform magnetic field is used to control the growth and deposition zones, where the Y-Ni catalyst experiences a transition to the ferromagnetic state, which in turn leads to the graphene deposition in a collection area. The quality of the produced material is characterized by the SEM, TEM, AFM, and Raman techniques. The proposed growth mechanism is supported by the nucleation and growth model.

Recently, a variety high-aspect-ratio nanostructures have been grown and profiled for various applications ranging from field emission transistors to gene/drug delivery devices. However, fabricating and processing arrays of these structures and determining how changing certain physical parameters affects the final outcome is quite challenging. We have developed several modules that can be used to simulate the processes of various physical vapour deposition systems from precursor interaction in the gas phase to gas-surface interactions and surface processes. In this paper, multi-scale hybrid numerical simulations are used to study how low-temperature non-equilibrium plasmas can be employed in the processing of high-aspect-ratio structures such that the resulting nanostructures have properties suitable for their eventual device application. We show that whilst using plasma techniques is beneficial in many nanofabrication processes, it is especially useful in making dense arrays of high-aspect-ratio nanostructures.

This contribution provides arguments why and in which cases low-temperature plasmas should be used for nanoscale surface and interface engineering and discusses several advantages offered by plasma-based processes and tools compared to neutral gas fabrication routes. Relevant processes involve nanotexturing (etching, sputtering, nanostructuring, pre-patterning, etc.) and composition/structure control at nanoscales (phases, layering, elemental presence, doping, functionalization, etc.) and complex combinations thereof. A case study in p-Si/n-Si solar cell junction exemplifies a successful use of inductively coupled plasma-assisted RF magnetron sputtering for nanoscale fabrication of a bi-layered stack of unconventionally doped highly-crystalline silicon nanofilms with engineered high-quality interfaces.

Many properties of single-walled carbon nanotube (SWCNT) arrays are determined by the size and surface coverage of the metal catalyst islands from which they are nucleated. Methods using thermal fragmentation of continuous metal films frequently fail to produce size-uniform islands. Hybrid numerical simulations are used to propose a new approach to controlled self-assembly of Ni islands of the required size and surface coverage using tailored gas-phase generated nanocluster fluxes and adjusted surface temperatures. It is shown that a maximum surface coverage of 0.359 by 0.96-1.02 nm Ni catalyst islands can be achieved at a low surface temperature of 500 K. Optimized growth of Ni catalyst islands can lead to fabrication of size-uniform SWCNT arrays, suitable for numerous nanoelectronic applications. This approach is deterministic and is applicable to a range of nanoassemblies where high surface coverage and island size uniformity are required.

The paper presents an investigation of self-organizational and -assembly processes of nanostructure growth on surfaces exposed to low-temperature plasmas. We have considered three main growth stages-initial, or sub-monolayer growth stage, separate nanostructure growth stage, and array growth stages with the characteristic sizes of several nm, several tens of nm, and several hundreds of nm, respectively, and have demonstrated, by the experimental data and hybrid multiscale numerical simulations, that the plasma parameters can strongly influence the surface processes and hence the kinetics of self-organization and -assembly. Our results show that plasma-controlled self-organization is a promising way to assemble large regular arrays of nanostructures.

Highly controllable electronic properties (carrier mobility and conductivity) were obtained in the sophisticatedly devised, structure-controlled, boron-doped microcrystalline silicon structure. Variation of plasma parameters enabled fabrication of films with the structure ranging from a highly crystalline (89.8%) to semi-amorphous (45.4%) phase. Application of the innovative process based on custom-designed, optimized, remote inductively coupled plasma implied all advantages of the plasma-driven technique and simultaneously avoided plasma-intrinsic disadvantages associated with ion bombardment and overheating. The high degree of SiH4, H2 and B2H6 precursor dissociation ensured very high boron incorporation into the structure, thus causing intense carrier scattering. Moreover, the microcrystalline-to-amorphous phase transition triggered by the heavy incorporation of the boron dopant with increasing B2H6 flow was revealed, thus demonstrating a very high level of the structural control intrinsic to the process. Control over the electronic properties through variation of impurity incorporation enabled tailoring the carrier concentrations over two orders of magnitude (1018–1020 cm−3). These results could contribute to boosting the properties of solar cells by paving the way to a cheap and efficient industry-oriented technique, guaranteeing a new application niche for this new generation of nanomaterials.

Control over nucleation and growth of multi-walled carbon nanotubes in the nanochannels of porous alumina membranes by several combinations of posttreatments, namely exposing the membrane top surface to atmospheric plasma jet and application of standard S1813 photoresist as an additional carbon precursor, is demonstrated. The nanotubes grown after plasma treatment nucleated inside the channels and did not form fibrous mats on the surface. Thus, the nanotube growth mode can be controlled by surface treatment and application of additional precursor, and complex nanotube-based structures can be produced for various applications. A plausible mechanism of nanotube nucleation and growth in the channels is proposed, based on the estimated depth of ion flux penetration into the channels. PACS 63.22.Np Layered systems; 68. Surfaces and interfaces; Thin films and nanosystems (structure and non-electronic properties); 81.07.-b Nanoscale materials and structures: fabrication and characterization

Carbon nanotubes (CNTs) and graphene are low-dimensional nanomaterials that have attracted tremendous scientific and industrial interest in the last two decades. Besides the traditional electronic and optical applications, they also hold a great promise in the biological and medical fields. This chapter summarizes the recent progress of CNTs and graphene in biological applications and presents some of the most intriguing examples, including biosensors, diagnostic and imaging tools, therapeutic drug delivery systems, anti-cancer research, tissue engineering scaffolds and neuron prosthesis. It attempts to demonstrate the advantages and challenges in the current development of CNT- and graphene-based biomedical devices, as well as to shed light on better utilizing these materials by possibly controlling their structure and functionalities.

Large arrays and networks of carbon nanotubes, both single- and multi-walled, feature many superior properties which offer excellent opportunities for various modern applications ranging from nanoelectronics, supercapacitors, photovoltaic cells, energy storage and conversation devices, to gas- and biosensors, nanomechanical and biomedical devices etc. At present, arrays and networks of carbon nanotubes are mainly fabricated from the pre-fabricated separated nanotubes by solution-based techniques. However, the intrinsic structure of the nanotubes (mainly, the level of the structural defects) which are required for the best performance in the nanotube-based applications, are often damaged during the array/network fabrication by surfactants, chemicals, and sonication involved in the process. As a result, the performance of the functional devices may be significantly degraded. In contrast, directly synthesized nanotube arrays/networks can preclude the adverse effects of the solution-based process and largely preserve the excellent properties of the pristine nanotubes. Owing to its advantages of scale-up production and precise positioning of the grown nanotubes, catalytic and catalyst-free chemical vapor depositions (CVD), as well as plasma-enhanced chemical vapor deposition (PECVD) are the methods most promising for the direct synthesis of the nanotubes.

We report on the comparative study of magnetotransport properties of large-area vertical few-layer graphene networks with different morphologies, measured in a strong (up to 10 T) magnetic field over a wide temperature range. The petal-like and tree-like graphene networks grown by a plasma enhanced CVD process on a thin (500 nm) silicon oxide layer supported by a silicon wafer demonstrate a significant difference in the resistance–magnetic field dependencies at temperatures ranging from 2 to 200 K. This behaviour is explained in terms of the effect of electron scattering at ultra-long reactive edges and ultra-dense boundaries of the graphene nanowalls. Our results pave a way towards three-dimensional vertical graphene-based magnetoelectronic nanodevices with morphology-tuneable anisotropic magnetic properties.

Transition between different plasma configurations is studied in a system with negative biased cylindrical target in crossed E×B fields. It was found that the diffuse plasma torus formed around the cylindrical target in relatively small magnetic field (0.02T on target surface) changes the shape with magnetic field to form a thin disk with a width lower than 1cm when target voltage is less than −400V. The target current decreases sharply when the magnetic field reaches some critical value. When the target voltage exceeds 400V, the target current increases with the magnetic field and the plasma has always toroidal shape. The plasma behavior can be understood taking in account the interaction of the drift currents and the magnetic field.

Material processing techniques utilizing low-temperature plasmas as the main process tool feature many unique capabilities for the fabrication of various nanostructured materials. As compared with the neutral-gas based techniques and methods, the plasma-based approaches offer higher levels of energy and flux controllability, often leading to higher quality of the fabricated nanomaterials and sometimes to the synthesis of the hierarchical materials with interesting properties. Among others, nanoscale biomaterials attract significant attention due to their special properties towards the biological materials (proteins, enzymes), living cells and tissues. This review briefly examines various approaches based on the use of low-temperature plasma environments to fabricate nanoscale biomaterials exhibiting high biological activity, biological inertness for drug delivery system, and other features of the biomaterials make them highly attractive. In particular, we briefly discuss the plasma-assisted fabrication of gold and silicon nanoparticles for bio-applications; carbon nanoparticles for bioimaging and cancer therapy; carbon nanotube-based platforms for enzyme production and bacteria growth control, and other applications of low-temperature plasmas in the production of biologically-active materials.

Major characteristics of the nanoscaled high-temperature metamaterial capable of reversal heat transmission are calculated, and two design variants are proposed and discussed. Specifically, the basic design has been proposed involving the solid-state highly emissive cathode material, and the modification with a liquid-state emissive material (e.g., cesium) filling the nanoporous structure such as previously synthesized alumina membrane or nanobottle structure. The performance characteristics of the proposed metamaterial have also been analyzed based on the three electron emission materials typical for the low-, medium-, and high-temperature emission regimes. The geometrical size, temperature ranges, powers, cooling efficiency, and performance factors of the considered design are examined. In particular, it has been demonstrated that the working potential difference reached 2–10 V at the current density 100 A cm−2 and interelectrode distance ranging from 3 to 10 μm. The electron cooling efficiency determined as the ratio of a heat flux taken off the cathode by the emitted electrons to the total heat flux to the cathode surface from the interelectrode space can reach 10−25, depending on cathode material and temperature, with the coefficient of performance reaching 8 when the cathode and anode materials are sophisticatedly selected. The future trends in the development of nanoscaled high-temperature metamaterial are discussed.

Owing to their unique mechanical, electrical, optical, and thermal properties, carbon nanostructures including carbon nanotubes and graphenes show great promise for advancing the fields of biology and medicine. Many reports have demonstrated the promise of these carbon nanostructures and their hybrid structures (composites with polymers, ceramics, and metal nanoparticles, etc.) for a variety of biomedical areas ranging from biosensing, drug delivery, and diagnostics, to cancer treatment, tissue engineering, and bioterrorism prevention. However, the issue of the safety and toxicity of these carbon nanostructures, which is vital to their use as diagnostic and therapeutic tools in biomedical fields, has not been completely resolved. This paper aims to provide a summary of the features of carbon nanotube and graphene-based materials and current research progress in biomedical applications. We also highlight the current opinions within the scientific community on the toxicity and safety of these carbon structures.

Tailoring the density of random single-walled carbon nanotube (SWCNT) networks is of paramount importance for various applications, yet it remains a major challenge due to the insufficient catalyst activation in most growth processes. Here we report on a simple and effective method to maximise the number of active catalyst nanoparticles using catalytic chemical vapor deposition (CCVD). By modulating short pulses of acetylene into a methane-based CCVD growth process, the density of SWCNTs is dramatically increased by up to three orders of magnitude without increasing the catalyst density and degrading the nanotube quality. In the framework of a vapor–liquid–solid model, we attribute the enhanced growth to the high dissociation rate of acetylene at high temperatures at the nucleation stage, which can be effective in both supersaturating the larger catalyst nanoparticles and overcoming the nanotube nucleation energy barrier of the smaller catalyst nanoparticles. These results are highly relevant to numerous applications of random SWCNT networks in next-generation energy, sensing and biomedical devices.

The unique properties of graphene and carbon nanotubes made them the most promising nanomaterials attracting enormous attention, due to the prospects for applications in various nanodevices, from nanoelectronics to sensors and energy conversion devices. Here we report on a novel deterministic, single-step approach to simultaneous production and magnetic separation of graphene flakes and carbon nanotubes in an arc discharge by splitting the high-temperature growth and low-temperature separation zones using a non-uniform magnetic field and tailor-designed catalyst alloy, and depositing nanotubes and graphene in different areas. Our results are very relevant to the development of commercially-viable, single-step production of bulk amounts of high-quality graphene.

The paper presents results of comparative investigation of carbon nanotubes growth processes in dense low-temperature plasma and on substrate surface. Hybrid/Monte-Carlo numerical simulations were used to demonstrate the differences in the ion fluxes, growth rates and kinetics of adsorbed atoms re-distribution on substrate and nanotubes surfaces. We show that the plasma parameters significantly affect the nanotubes growth kinetics. We demonstrate that the growth rates of the nanotubes in plasma and on surface can differ by three orders, and the specific fluxes to the nanotube in the plasma can exceed the flux to surface-grown nanotube by six orders. We also show that the metal catalyst used for the nanotubes production on surface and in arc is a subject to very different conditions and this may be a key factor for the nanotube growth mode. The obtained dependencies for the ion fluxes to the nanotubes and nanotubes growth rates on the plasma parameters may be useful for selection of the production methods.

Graphene and carbon nanotubes are the most promising nanomaterials for application in various modern nanodevices. The successful production of the nanotubes and graphene in a single process was achieved by using a magnetically enhanced arc discharge in helium atmosphere between carbon and metal electrodes. A 3-D fluid model has been used to investigate the discharge parameters.

Using the advanced radio-frequency plasma-assisted magnetron deposition system, various nanostructures such as nanoflowers of carbon nanotubes, ZnO nanobelts, and silicon nanotrees were successfully synthesized. In this paper, we present the photographs of ICP and magnetron discharges, the photograph of a complex plasma structure, and the SEM images of various nanostructures synthesized in the system with magnetron and ICP sources operating simultaneously.

Arc discharge ablation with a catalyst-filled carbon anode in a helium background was used for the synthesis of graphene and carbon nanotubes. In this paper, we present the results of the numerical simulation of the distribution of various plasma parameters in discharge, as well as the distribution of carbon flux on the nanotube surface, for the typical discharge with an arc current of 60 A and a background gas pressure of 68 kPa.

© 2014 National Institute for Materials Science. Various morphologies of the vertically-aligned graphene flakes were fabricated on the nanoporous templates treated with metal ions in solutions, as well as coated with a thin gold layer and activated in the low-temperature Ar plasma. The thickness and level of structural defects in the graphene flakes could be effectively controlled by a proper selection of the pre-treatment method. We have also demonstrated that various combinations of the flake thickness and defect levels can be obtained, and the morphology and density of the graphene pattern can be effectively controlled. The result obtained could be of interest for various applications requiring fabrication of large graphene networks with controllable properties.

Back Cover The growth mechanism was clarified and differences between the plasma- and neutral gas-grown carbon nanotubes were explained by using an enhanced large-scale model and numerical simulation technique. The nanotubes synthesized by plasma process can be longer than those synthesized by neutral gas technique. The low-temperature growth of the nanotube array is also possible when the hydrocarbon ion flux to the nanotubes dominates over fluxes of other species. Further details can be found in the article Gennady Burmaka et al. on page 798.

Nucleation and growth of highly crystalline silicon nanoparticles in atmospheric-pressure low-temperature microplasmas at gas temperatures well below the Si crystallization threshold and within a short (100 μs) period of time are demonstrated and explained. The modeling reveals that collision-enhanced ion fluxes can effectively increase the heat flux on the nanoparticle surface and this heating is controlled by the ion density. It is shown that nanoparticles can be heated to temperatures above the crystallization threshold. These combined experimental and theoretical results confirm the effective heating and structure control of Si nanoparticles at atmospheric pressure and low gas temperatures.

Using Monte Carlo simulation technique, we have calculated the distribution of ion current extracted from low-temperature plasmas and deposited onto the substrate covered with a nanotube array. We have shown that a free-standing carbon nanotube is enclosed in a circular bead of the ion current, whereas in square and hexagonal nanotube patterns, the ion current is mainly concentrated along the lines connecting the nearest nanotubes. In a very dense array (with the distance between nanotubes/nanotube-height ratio less than 0.05), the ions do not penetrate to the substrate surface and deposit on side surfaces of the nanotubes.

Plasma-based techniques offer many unique possibilities for the synthesis of various nanostructures both on the surface and in the plasma bulk. In contrast to the conventional chemical vapor deposition and some other techniques, plasma-based processes ensure high level of controllability, good quality of the produced nanomaterials, and reduced environmental risk. In this work, the authors briefly review the unique features of the plasma-enhanced chemical vapor deposition approaches, namely, the techniques based on inductively coupled, microwave, and arc discharges. Specifically, the authors consider the plasmas with the ion/electron density ranging from 1010 to 1014 cm−3, electron energy in the discharge up to ∼10 eV, and the operating pressure ranging from 1 to 104 Pa (up to 105 Pa for the atmospheric-pressure arc discharges). The operating frequencies of the discharges considered range from 460 kHz for the inductively coupled plasmas, and up to 2.45 GHz for the microwave plasmas. The features of the direct-current arc discharges are also examined. The authors also discuss the principles of operation of these systems, as well as the effects of the key plasma parameters on the conditions of nucleation and growth of the carbon nanostructures, mainly carbon nanotubes and graphene. Advantages and disadvantages of these plasma systems are considered. Future trends in the development of these plasma-based systems are also discussed.

The primary goal in hard tissue engineering is to combine high-performance scaffold materials with living cells to develop biologically active substitutes that can restore tissue functions. This requires relevant knowledge in multidisciplinary fields encompassing chemical engineering, material science, chemistry, biology and nanotechnology. Here we present an overview on the recent progress of how two representative carbon nanostructures, namely, carbon nanotubes and graphene, aid and advance the research in hard tissue engineering. The article focuses on the advantages and challenges of integrating these carbon nanostructures into functional scaffolds for repairing and regenerative purposes. It includes, but is not limited to, the critical physico-chemical properties of carbon nanomaterials for enhanced cell interactions such as adhesion, morphogenesis, proliferation and differentiation; the novel designs of two- and three-dimensional nanostructured scaffolds; multifunctional hybrid materials; and the biocompatible aspects of carbon nanotubes and graphene. Perspectives on the future research directions are also given, in an attempt to shed light on the innovative and rational design of more effective biomedical devices in hard tissue engineering.

An advanced inductively coupled plasma (ICP)-assisted rf magnetron sputtering deposition method is developed to synthesize regular arrays of pear-shaped ZnO nanodots on a thin SiNx buffer layer pre-deposited onto a silicon substrate. It is shown that the growth of ZnO nanodots obey the cubic root-law behavior. It is also shown that the synthesized ZnO nanodots are highly-uniform, controllable by the experimental parameters, and also feature good structural and photoluminescent properties. These results suggest that this custom-designed ICP-based technique is very effective and highly-promising for the synthesis of property- and size-controllable highly-uniform ZnO nanodots suitable for next-generation light emitting diodes, energy storage, UV nanolasers, and other applications. Published version

The formation of clearly separated vertical graphenenanosheets on silicon nanograss support is demonstrated. The plasma-enabled, two-stage mask-free process produced self-organized vertical graphenes of a few carbon layers (as confirmed by advanced microanalysis), prominently oriented in the substrate center–substrate edge direction. It is shown that the width of the alignment zone depends on the substrate conductivity, and thus the electric field in the vicinity of the growth surface is responsible for the graphene alignment. This finding is confirmed by the Monte Carlo simulations of the ion flux distribution in the silicon nanograss pattern.