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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.

A novel approach to significantly enhance and comprehensively assess the level of nanochannel ordering in self-assembled nanoporous membranes is proposed and tested. An advanced technique based on a two-step anodization and two-step chemical treatment was used to prepare the perfect through membranes by opening channels from the bottom via electrochemical enlargement, and chemical removal of a residual metal and barrier alumina layer. The influence of the process parameters on the self-assembled ordering was studied, and various methods of order assessment were proposed and tested, such as distributions of equivalent disc radii, 2D Fourier transformations, autocorrelation, Hough transformations, Minkowski connectivity, and distributions of nanochannel centre positions. We have demonstrated that self-assembled ordering in nanoscaled membranes could be efficiently tuned by the process parameters, and different assessment methods should be used to comprehensively characterize the order of nanochannels in the nanoporous membranes. To demonstrate the potential of this technique, we show simulations of the narrowing of plasmon spectra in these materials. The proposed fabrication and assessment methods could be used to drastically enhance the properties of nanoporous membranes for nanoelectronics, filters, sensors, bio-active devices and other advanced emerging applications. Finally, our approach could be used for enhancing and tailoring other self-assembled systems and devices of considerable complexity.

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

Although extremely chemically reactive, oxygen plasmas feature certain properties that make them attractive not only for material removal via etching and sputtering, but also for driving and sustaining nucleation and growth of various nanostructures in plasma bulk and on plasma-exposed surfaces. In this minireview, a number of representative examples is used to demonstrate key mechanisms and unique capabilities of oxygen plasmas and how these can be used in present-day nano-fabrication. In addition to modification and functionalisation processes typical for oxygen plasmas, their ability to catalyse the growth of complex nanoarchitectures is emphasized. Two types of technologies based on oxygen plasmas, namely surface treatment without a change in the size and shape of surface features, as well as direct growth of oxide structures, are used to better illustrate the capabilities of oxygen plasmas as a powerful process environment. Future applications and possible challenges for the use of oxygen plasmas in nanofabrication are discussed. NRF (Natl Research Foundation, S’pore) MOE (Min. of Education, S’pore)

Plasma-enhanced synthesis and modification of polymers is a field that continues to expand and become increasingly more sophisticated. The highly reactive processing environments afforded by the inherently dynamic nature of plasma media are often superior to ambient or thermal environments, offering substantial advantages over other processing methods. The fluxes of energy and matter toward the surface enable rapid and efficient processing, whereas the charged nature of plasma-generated particles provides a means for their control. The range of materials that can be treated by plasmas is incredibly broad, spanning pure polymers, polymer-metal, polymer-wood, polymer-nanocarbon composites, and others. In this review, we briefly outline some of the recent examples of the state-of-the-art in the plasma-based polymer treatment and functionalization techniques.

Three dimensional vertically-oriented carbon nanoflakes grown on carbon and gold nanoparticles by the hot filament chemical vapor deposition in CH4 environment demonstrate quite similar structure and composition, but drastically different room temperature photoluminescent properties. The interfacial interactions were asserted to be the main reason for the differences in the optical emission. The mechanisms of highly oriented growth, generation and enhancement of photoluminescence were investigated, and it was demonstrated that the formation of oriented nanoflakes resulted from the stress produced in the carbon layers on carbon and gold nanoparticles. Specifically, deformation of nanoparticles and difference in the expansion rates of carbon layer, gold and carbon nanoparticles are the main causes for the stress formation. The oriented growth of carbon nanoflakes is maintained by the repulsion effect between the carbon nanoflakes due to the net charge produced from the hydrocarbon radicals on the edges of carbon nanoflakes via charge transfer between H and C atoms. The photoluminescence generation of carbon nanoflakes is related to the sp2 carbon clusters on the edges of carbon nanoflakes. Stronger green photoluminescent emission from the carbon nanoflake/gold nanoparticle system than from the carbon nanoflake/carbon nanoparticle system is the result of the intense plasmon emission from gold nanoparticles.

The role of reactive environment and hydrogen specifically in growth and structure of molybdenum selenide (MoSe2) nanomaterials is presently debated, and it is not clear whether hydrogen can promote the growth of MoSe2 sheets and alter their electronic properties. To find efficient, convenient methods for controlling the nucleation, growth and resultant properties of MoSe2 nanomaterials, MoSe2 nanoflakes were synthesized on silicon substrates by hot filament chemical vapor deposition using molybdenum trioxide and selenium powders in pure hydrogen, nitrogen gases and hydrogen-nitrogen mixtures. The structures and composition of synthesized MoSe2 nanoflakes were studied using the advanced characterization instruments including field emission scanning electron microscopy, micro-Raman spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy and energy dispersive X-ray spectrometry. The analysis of the growth process indicates that hydrogen can improve the formation of MoSe2 nanoflakes and significantly alter their properties due to the high reduction capacity of hydrogen and the creation of more nucleation centers of MoSe2 nanoflakes on the silicon surface. The study of photoluminescent (PL) properties reveals that the MoSe2 nanoflakes can generate a strong PL band at about 631 nm, differently from the plain MoSe2 nanoflakes. The major difference in the PL properties may be related to the edges of MoSe2 nanoflakes. These results can be used to control the growth and structure of MoSe2-based nanomaterials and contribute to the development of advanced MoSe2-based optoelectronic devices.

Theoretical studies of the complex, doped BN/carbon pillar hybrid networks have revealed their great potential for energy and power conversion, nanoelectronics, optoelectronics and electric propulsion devices. Demonstration of the technique to synthesize such networks and control the structure is critical for their applications. Here we report on the successful fabrication of complex, hybrid pillar networks consisting of carbon- and oxygen-doped BN nanoflakes and nitrogenated carbon nanorods. The complex, hybrid, structure-controlled pillar networks were grown directly on the carbon nanorods in N2-H2 plasma using B4C as the boron and carbon sources. The characterization by scanning and transmission electron microscopy, micro-Raman, Fourier transform infrared and X-ray photoelectron spectroscopies has confirmed that the carbon- and oxygen-doped BN crystalline nanoflakes indeed grow on the amorphous nitrogenated carbon nanorods and form the pillar hybrid networks. The photoluminescence measurements have revealed that the pillar hybrid networks generate ultraviolet, blue, green, and red photoluminescence bands. In particular, the photoluminescence properties of the pillar hybrid networks can be effectively tuned by changing the network structure. These outcomes can contribute to the synthesis of novel nanostructures and the development of next generation optoelectronic nanodevices and power devices.

C and O doped BN nanoflakes and hybrid nanoflake-nanowire structures were synthesized in N2+H2 environment using plasma-enhanced hot filament chemical vapour deposition with solid B4C as boron and carbon precursor. Structure and chemical composition of the C and O doped BN nanoflakes and hybrid nanoflake-nanowire hybrid structures were systemically studied using advanced characterization instruments including high resolution transmission electron microscope, micro-Raman spectroscope, Fourier transform infrared spectroscope, X-ray diffractometer, field emission scanning electron microscope, and X-ray photoelectron spectroscope. The obtained results evidence that the C and O doped BN nanowires nucleate and grow directly on the tops of C and O doped BN nanoflakes due to the presence of dangling bonds on the surfaces of tips of C and O doped BN nanoflakes, which were formed by the ion bombardment in plasma. The photoluminescence (PL) properties of C and O doped BN nanoflakes and C and O doped BN nanoflake-nanowire hybrid structures were studied at room temperature using a micro-Raman system with the 325 nm line of He-Cd laser as the excitation source. The results of PL measurements indicate that the PL properties of C and O doped BN nanoflake-nanowire hybrid structures significantly change with the length of C and O doped BN nanostructures due to the interface zones caused by the nanowire length. Thus, the PL properties can be efficiently tuned by the length of nanowires. These achievements can contribute to the synthesis of novel BN-based hybrid nanostructures and the development of the next generation BN-based optoelectronic nanodevices.

The underlying physical and chemical mechanisms and role of the plasma species in the synthesis of hydrogenated amorphous silicon (a-Si:H) thin films were studied numerically with the aim to reveal the key growth processes and, hence, to ensure a much higher level of control over the film structure and properties. A sophisticated multiscale model developed on the basis of self-consistent surface and plasma kinetics sub-models, including one-dimensional plasma sheath formalization, was used to study the nucleation, growth, and structure formation of amorphous hydrogenated silicon films in a reactive low temperature plasma environment containing a mixture of silane, hydrogen, and argon gases. The model considers a whole range of key processes, and the effect of surface temperature, ion flux, energy and other plasma-sheath parameters are examined in detail. The leading role of hydrogen in structure formation is confirmed and moreover, key processes critically important for designing and discovering novel materials with important properties are identified. The dominant role of SiH3 as the main precursor in the deposition of amorphous hydrogenated silicon films is proved, and routes for the efficient, technique-enabled control are specified. The presented results were compared with the experimental data, and a good agreement with the experimental findings obtained for the deposition of amorphous hydrogenated films has been demonstrated.

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.

Driven by the innate tendency of the system to attain a local energy minimum, self-organization enables the creation of complex systems out of relatively simple parts and elements. The ability to form hierarchical, multicomponent systems that may be difficult, or even impossible, to fabricate using pre-set, template-enabled processes makes self-organisation very attractive for the synthesis and assembly of advanced material systems across multiple length scales. Yet, driving and controlling such self-organisation processes is not a trivial task as they often arise from a complex interplay of physical and chemical processes. These in turn depend on the environment in which self-organisation takes place. In this topical review, we focus on one such environment and outline unique opportunities, salient characteristics and challenges presented by self-organization on surfaces exposed to partially ionised gases, i.e. plasmas. Using a select number of recent examples, we aim to show how salient features of plasma environments, particularly high fluxes of energy and matter from the plasma to the surface, enable functionalization and growth of complex nanostructures and metamaterials via self-organization on plasma-exposed surfaces. We will show how by controlling different physical and chemical parameters of the plasma environment and how it interacts with surfaces, it is possible to control self-organization processes at multiple length scales, making it a promising enabling platform for nanosynthesis. We will discuss examples starting from the self-driven growth of perfect crystalline lattices, such as nano-diamonds and graphenes at the nanoscale, all the way to template- and pattern-free synthesis of large, highly ordered arrays of nanostructures at millimetre and even centimetre scales. We will outline the key enabling features of plasmas that drive these processes at respective scales, focusing predominantly on plasma-induced electric fields at the surface or in the plasma-nanostructure sheath, as well as charge-related effects. The outlook section summarizes advantages of plasma-driven self-organization, and outlines principal challenges and opportunities for the development of this field. NRF (Natl Research Foundation, S’pore) MOE (Min. of Education, S’pore)

We report on the fabrication of bi-dimensional alumina/palladium nanowire nanoarchitectures for hydrogen detection, storage and controlled release. This nanostructured material was fabricated by growing the palladium nanowires directly in the nanosized channels of nanoporous alumina membrane followed by atmospheric-plasma jet treatment to fabricate the interconnected surface structure mostly suitable for hydrogenrelated applications such as controlled release and sensing. Several interesting properties are demonstrated, including high sensitivity levels (up to 0.1% of H2 in air) and short response times. Large resistance response reaching 100% for 0.5% of H2 in air makes it possible to use the fabricated sensors without complex and expensive amplifying circuits. Copyright © 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Atmospheric-pressure discharge in the tubular capillary plasma jet was studied to reveal the possibility to accelerate anodization of aluminum foils and fabricate alumina nanoparticles in liquid acids. Two different positions of the atmospheric pressure plasma jet relatively to the acid electrolyte and aluminum electrode were studied. Whereas at larger distances, only slight oxidation was obtained, the nanoporous surface and alumina nanoparticles were produced at closer (3–5 mm) distances. The mode with arcing (sparking) resulted in the film of alumina nanoparticles. The obtained results could be useful for the cheap and convenient synthesis of nanoparticles and nanostructured surfaces for various applications, including medical, biological, energy conversion, and nanoelectronic devices.

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.

Increasingly intricate in their composition and structural organization, hierarchical multicomponent metamaterials with nonlinear spatially reconfigurable functionalities challenge the intrinsic constraints of natural materials, revealing tremendous potential for the advancement of biochemistry, nanophotonics, and medicine. Recent breakthroughs in high-resolution nanofabrication utilizing ultranarrow, precisely controlled ion or laser beams have enabled assembly of architectures of unprecedented structural and functional complexity, yet costly, time- and energy-consuming high-resolution sequential techniques do not operate effectively at industry-required scale. Inspired by the fictional Baron Munchausen's fruitless attempt to pull himself up, it is demonstrated that metamaterials can undergo intrinsically driven self-assembly, metaphorically pulling themselves up into existence. These internal drivers hold a key to unlocking the potential of metamaterials and mapping a new direction for the large-area, cost-efficient self-organized fabrication of practical devices. A systematic exploration of these efforts is presently missing, and the driving forces governing the intrinsically driven self-assembly are yet to be fully understood. Here, recent progress in the self-organized formation and self-propelled growth of complex hierarchical multicomponent metamaterials is reviewed, with emphasis on key principles, salient features, and potential limitations of this family of approaches. Special stress is placed on self-assembly driven by plasma, current in liquid, ultrasonic, and similar highly energetic effects, which enable self-directed formation of metamaterials with unique properties and structures.

ZnO nanostructures were grown under different deposition conditions from Zn films pre-deposited onto Si substrates in O2-Ar plasma, ignited in an advanced custom-designed plasma-enhanced horizontal tube furnace deposition system. The morphology and structure of the synthesized ZnO nanostructures were systematically and extensively investigated by scanning and transmission electron microscopy, Raman spectroscopy, and atomic force microscopy. It is shown that the morphology of ZnO nanostructures changes from the hybrid ZnO/nanoparticle and nanorod system to the mixture of ZnO nanosheets and nanorods when the growth temperature increases, and the density of ZnO nanorods increases with the increase of oxygen flow rate. The formation of ZnO nanostructures was explained in terms of motion of Zn atoms on the Zn nanoparticle surfaces, and to the local melting of Zn nanoparticles or nanosheets. Moreover, the photoluminescence properties of ZnO nanostructures were studied, and it was revealed that the photoluminescence spectrum features two strong ultraviolet bands at about 378 and 399 nm and a series of weak blue bands within a range of 440–484 nm, related to the emissions of free excitons, near-band edge, and defects of ZnO nanostructures. The obtained results enrich our knowledge on the synthesis of ZnO-based nanostructures and contribute to the development of ZnO-based optoelectronic devices.

Simple, rapid, plasma-assisted synthesis of large-area arrays of vertically-aligned carbon nanowalls on highly-porous, transparent bare and gold-coated alumina membranes with the two pore sizes is reported. It is demonstrated that the complex patterns of vertically aligned nanowalls can nucleate and form different morphologies in the low-temperature plasmas. The process is stable, and the twofold change in the gas flow (10 and 20 sccm) does not noticeably influence the morphology of the nanowall pattern. Application of a thin (5 nm) gold layer to nanoporous membrane prior to the nanowall growth allows controlling the network morphology.

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.

This work was supported by the Royal Society International Exchange Scheme (IE120884), the Leverhulme International Network (IN-2012-136), EPSRC (EP/K022237/1 and EP/ M024938/1) and EU-FP7 (award n.606889). S. A. and A. U. H. thank the financial support of the University of Ulster Vice- Chancellor Studentship and EU-funded ITN, respectively (award n.606889). IL and KO acknowledge financial support from CSIRO and Australian Research Council. I. L. acknowledges support from the School of Chemistry, Physics and Mechanical Engineering, Science and Engineering Faculty, Queensland University of Technology. Highly size-controllable synthesis of free-standing perfectly crys- talline silicon carbide nanocrystals has been achieved for the first time through a plasma-based bottom-up process. This low-cost, scalable, ligand-free atmospheric pressure technique allows fabri- cation of ultra-small (down to 1.5 nm) nanocrystals with very low level of surface contamination, leading to fundamental insights into optical properties of the nanocrystals. This is also confirmed by their exceptional photoluminescence emission yield enhanced by more than 5 times by reducing the nanocrystals sizes in the range of 1–5 nm, which is attributed to quantum confinement in ultra-small nanocrystals. This method is potentially scalable and readily extendable to a wide range of other classes of materials. Moreover, this ligand-free process can produce colloidal nano- crystals by direct deposition into liquid, onto biological materials or onto the substrate of choice to form nanocrystal films. Our simple but efficient approach based on non-equilibrium plasma environment is a response to the need of most efficient bottom-up processes in nanosynthesis and nanotechnology. Postprint

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.

Controlled self-organized growth of vertically aligned carbon nanocone arrays in a radio frequency inductively coupled plasma-based process is studied. The experiments have demonstrated that the gaps between the nanocones, density of the nanocone array, and the shape of the nanocones can be effectively controlled by the process parameters such as gas composition (hydrogen content) and electrical bias applied to the substrate. Optical measurements have demonstrated lower reflectance of the nanocone array as compared with a bare Si wafer, thus evidencing their potential for the use in optical devices. The nanocone formation mechanism is explained in terms of redistribution of surface and volumetric fluxes of plasma-generated species in a developing nanocone array and passivation of carbon in narrow gaps where the access of plasma ions is hindered. Extensive numerical simulations were used to support the proposed growth mechanism.

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.

Mankind faces several global challenges such as chronic and acute hunger, global poverty, energy deficiency and environment conservation. Common biotechnologies based on batch, fluidbed and other similar processes are now extensively used for the production of a wide range of products such as antibiotics, biofuels, cultured and fermented food products. Unfortunately, these processes suffer from low efficiency, high energy demand, low controllability and rapid biocatalyst degradation by microbiological attack, and thus still are not capable of seriously addressing the global hunger and energy deficiency challenges. Moreover, sustainable future technologies require minimizing the environmental impact of toxic by-products by implementing the "life produces organic matter, organic matter sustains life" principle. Nanostructure-based biotechnology is one of the most promising approaches that can help to solve these challenges. In this work we briefly review the unique features of the carbon-based nanostructured platforms, with some attention paid to other nanomaterials. We discuss the main building blocks and processes to design and fabricate novel platforms, with a focus on dense arrays of the vertically-aligned nanostructures, mainly carbon nanotubes and graphene. Advantages and disadvantages of these systems are considered.

Highly efficient solar cells (conversion efficiency 11.9%, fill factor 70%) based on the vertically aligned single-crystalline nanostructures are fabricated without any pre-fabricated p-n junctions in a very simple, single-step process of Si nanoarray formation by etching p-type Si(100) wafers in low-temperature environment-friendly plasmas of argon and hydrogen mixtures.

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.

Given the vast number of strategies used to control the behavior of laboratory and industrially relevant plasmas for material processing and other state-of-the-art applications, a potential user may find themselves overwhelmed with the diversity of physical configurations used to generate and control plasmas. Apparently, a need for clearly defined, physics-based classification of the presently available spectrum of plasma technologies is pressing, and the critically summary of the individual advantages, unique benefits, and challenges against key application criteria is a vital prerequisite for the further progress. To facilitate selection of the technological solutions that provide the best match to the needs of the end user, this work systematically explores plasma setups, focusing on the most significant family of the processes—control of plasma fluxes—which determine the distribution and delivery of mass and energy to the surfaces of materials being processed and synthesized. A novel classification based on the incorporation of substrates into plasma-generating circuitry is also proposed and illustrated by its application to a wide variety of plasma reactors, where the effect of substrate incorporation on the plasma fluxes is emphasized. With the key process and material parameters, such as growth and modification rates, phase transitions, crystallinity, density of lattice defects, and others being linked to plasma and energy fluxes, this review offers direction to physicists, engineers, and materials scientists engaged in the design and development of instrumentation for plasma processing and diagnostics, where the selection of the correct tools is critical for the advancement of emerging and high-performance applications.

Ag nanoparticles and Fe-coated Si micrograins were separately deposited onto Si(1 0 0) surfaces and then exposed to an Ar + CH4 microplasma at atmospheric pressure. For the Ag nanoparticles, self-organized carbon nanowires, up to 400 nm in length were produced, whereas for the Fe-coated Si micrograins carbon connections with the length up to 100mu m were synthesized on the plasma-exposed surface area of about 0.5 mm(2). The experiment has revealed that long carbon connections and short nanowires demonstrate quite similar behavior and structure. While most connections/nanowires tended to link the nearest particles, some wires were found to `dissolve' into the substrate without terminatingat the second particle. Both connections and nanowires are mostly linear, but long carbon connections can form kinks which were not observed in the carbon nanowire networks. A growth scenario explaining the carbon structure nucleation and growth is proposed. Multiscale numerical simulations reveal that the electric field pattern around the growing connections/nanowires strongly affects the surface diffusion of carbon adatoms, the main driving force for the observed self-organization in the system. The results suggest that themicroplasma-generated surface charges can be. used as effective controls for the self-organized formation of complex carbon-based nano-networks for integrated nanodevices. Crown Copyright (C) 2009 Published by Elsevier Ltd. All rights reserved.

The formation of long self-organized carbon connections (where the length is much greater than the diameter) between Ag nanoparticles on a Si(1 0 0) surface in atmospheric pressure Ar + CH4 microplasmas is demonstrated. A growth scenario explaining the connection nucleation and growth is proposed, and this is supported by numerical simulations which reveal that the electric field pattern around the growing connections affects the surface diffusion of carbon adatoms, the main driving force for the observed self-organization. Results suggest that the microplasma-generated surface charges can be used as effective controls for the self-organized formation of complex carbon-based nano-networks for integrated nanodevices.

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.

Examples of successful fabrication of low-dimensional semiconducting nanomaterials in the Integrated Plasma-Aided Nanofabrication Facility are shown. Self-assembled size-uniform ZnO nanoparticles, ultra-high-aspect ratio Si nanowires, vertically aligned cadmium sulfide nanostructures, and quarternary semiconducting SiCAlN nanomaterial have been synthesized using inductively coupled plasma-assisted RF magnetron sputtering deposition. The observed increase in crystallinity and growth rates of the nanostructures are explained by using a model of plasma-enhanced adatom surface diffusion under conditions of local energy exchange between the ion flux and the growth surface. Issues related to plasma-based growth of low-dimensional semiconducting nanomaterials are discussed as well. © 2007 Elsevier B.V. All rights reserved.

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.

The self-organized growth of uniform carbon nanocone arrays using low-temperature non-equilibrium Ar + H2 + CH4 plasma-enhanced chemical vapor deposition (PECVD) is studied. The experiment shows that size-, shape-, and position-uniform carbon nanocone arrays can develop even from non-uniformly fragmented discontinuous nickel catalyst films. A three-stage scenario is proposed where the primary nanocones grow on large catalyst particles during the first stage, and the secondary nanocones are formed between the primary ones at the second stage. Finally, plasma-related effects lead to preferential growth of the secondary nanocones and eventually a uniform nanopattern is formed. This does not happen in a CVD process with the same gas feedstock and surface temperature. The proposed three-stage growth scenario is supported by the numerical experiment which generates nanocone arrays very similar to the experimentally synthesized nanopatterns. The self-organization process is explained in terms of re-distribution of surface and volumetric fluxes of plasma-generated species in a developing nanocone array. Our results suggest that plasma-related self-organization effects can significantly reduce the non-uniformity of carbon nanostructure arrays which commonly arises from imperfections in fragmented Ni-based catalyst films.

The results of numerical simulation of plasma-based, porous, template-assisted nanofabrication of Au nanodot arrays on highly-doped silicon taking into account typical electron density of low-temperature plasma of 10 17 -10 18 m -3 and electron temperature of 2-5 eV are reported here. Three-dimensional microscopic topography of ion flux distribution over the outer and inner surfaces of the nanoporous template is obtained via numerical simulation of Au ion trajectories in the plasma sheath, in the close proximity of, and inside the nanopores. It is shown that, by manipulating the electron temperature, the cross-sheath potential drop, and by additionally altering the structure of the nanoporous template, one can control the ion fluxes within the nanopores, and eventually maximize the ion deposition onto the top surface of the developing crystalline Au nanodots (see top panel in the figure). In the same time, this procedure allows one to minimize amorphous deposits on the sidewalls that clutter and may eventually close the nanopores, thus disrupting the nanodot growth process, as it is shown in the bottom panel in the figure on the right.

Multiscale hybrid simulations that bridge the nine-order-of-magnitude spatial gap between the macroscopic plasma nanotools and microscopic surface processes on nanostructured solids are described. Two specific examples of carbon nanotip-like and semiconductor quantum dot nanopatterns are considered. These simulations are instrumental in developing physical principles of nanoscale assembly processes on solid surfaces exposed to low-temperature plasmas.

We report on the chemical synthesis of the arrays of silicon oxide nanodots and their self-organization on the surface via physical processes triggered by surface charges. The method based on chemically active oxygen plasma leads to the rearrangement of nanostructures and eventually to the formation of groups of nanodots. This behavior is explained in terms of the effect of electric field on the kinetics of surface processes. The direct measurements of the electric charges on the surface demonstrate that the charge correlates with the density and arrangement of nanodots within the array. Extensive numerical simulations support the proposed mechanism and prove a critical role of the electric charges in the self-organization. This simple and environment-friendly self-guided process could be used in the chemical synthesis of large arrays of nanodots on semiconducting surfaces for a variety of applications in catalysis, energy conversion and storage, photochemistry, environmental and biosensing, and several others.

The distribution of flux of carbon-bearing cations over nanopatterned surfaces with conductive nanotips and nonconductive nanoislands is simulated using the Monte-Carlo technique. It is shown that the ion current is focused to nanotip surfaces when the negative substrate bias is low and only slightly perturbed at higher substrate biases. In the low-bias case, the mean horizontal ion displacement caused by the nanotip electric field exceeds 10 nm. However, at higher substrate biases, this value reduces down to 2 nm. In the nonconductive nanopattern case, the ion current distribution is highly nonuniform, with distinctive zones of depleted current density around the nanoislands. The simulation results suggest the efficient means to control ion fluxes in plasma-aided nanofabrication of ordered nanopatterns, such as nanotip microemitter structures and quantum dot or nanoparticle arrays.