From short pulses to short breaks : exotic plasma bullets via residual electron control

Plasma plumes with exotically segmented channel structure and plasma bullet propagation are produced in atmospheric plasma jets. This is achieved by tailoring interruptions of a continuous DC power supply over the time scales of lifetimes of residual electrons produced by the preceding discharge phase. These phenomena are explained by studying the plasma dynamics using nanosecond-precision imaging. One of the plumes is produced using 2-10μs interruptions in the 8kV DC voltage and features a still bright channel from which a propagating bullet detaches. A shorter interruption of 900ns produces a plume with the additional long conducting dark channel between the jet nozzle and the bright area. The bullet size, formation dynamics, and propagation speed and distance can be effectively controlled. This may lead to micrometer-and nanosecond-precision delivery of quantized plasma bits, warranted for next-generation health, materials, and device technologies.

Vertical graphene gas- and bio-sensors via catalyst-free, reactive plasma reforming of natural honey

A rapid reforming of natural honey exposed to reactive low-temperature Ar + H2 plasmas produced high-quality, ultra-thin vertical graphenes, without any metal catalyst or external heating. This transformation is only possible in the plasma and fails in similar thermal processes. The process is energy-efficient, environmentally benign, and is much cheaper than common synthesis methods based on purified hydrocarbon precursors. The graphenes retain the essential minerals of natural honey, feature reactive open edges and reliable gas- and bio-sensing performance.

Ion impact distribution over plasma exposed nanocone arrays

The effect of an ordered array of nanocones on a conducting substrate immersed in the plasma on the transport of the plasma ions is investigated. The real conical shape of the cones is rigorously incorporated into the model. The movement of 10^5 CH3+ ions in the plasma sheath modified by the nanocone array is simulated. The ions are driven by the electric fields produced by the sheath and the nanostructures. The surface charge density and the total charge on the nanotips with different aspect ratios are computed. The ion transport simulation provides important characteristics of the displacement and velocity of the ions. The relative ion distribution along the lateral surfaces of the carbon nanotips is computed as well. It is shown that a rigorous account of the realistic nanostructure shape leads to very different distribution of the ion fluxes on the nanostructured surfaces compared to the previously reported works. The ion flux distribution is a critical factor in the nucleation process on the substrate and determines the nanostructure growth patterns.

Inactivation of a 25.5 µm Enterococcus faecalis biofilm by a room-temperature, battery-operated, handheld air plasma jet

Effective biofilm inactivation using a handheld, mobile plasma jet powered by a 12 V dc battery and operated in open air without any external gas supply is reported. This cold, room-temperature plasma is produced in self-repetitive nanosecond discharges with current pulses of ~100 ns duration, current peak amplitude of ~6 mA and repetition rate of ~20 kHz. It is shown that the reactive plasma species penetrate to the bottom layer of a 25.5 µm-thick Enterococcus faecalis biofilm and produce a strong bactericidal effect. This is the thickest reported biofilm inactivated using room-temperature air plasmas.

Plasma-enabled, catalyst-free growth of carbon nanotubes on mechanically-written Si features with arbitrary shape

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. Using metal catalyst has long been considered essential for the nucleation and growth of surface-supported carbon nanotubes (CNTs) [1] and [2]. Only very recently, the possibility of CNT growth using non-metallic (e.g., oxide [3] and SiC [4]) catalysts or artificially created carbon-enriched surface layers [5] has been demonstrated. However, successful integration of carbon nanostructures into Si-based nanodevice platforms requires catalyst-free growth, as the catalyst nanoparticles introduce contact losses, and their catalytic activity is very difficult to control during the growth [6]. Furthermore, in many applications in microfluidics, biological and molecular filters, electronic, sensor, and energy conversion nanodevices, the CNTs need to be arranged in specific complex patterns [7] and [8]. These patterns need to contain the basic features (e.g., lines and dots) written using simple procedures and fully filled with dense arrays of high-quality, straight, yet separated nanotubes. In this paper, we report on a completely metal or oxide catalyst-free plasma-based approach for the direct and rapid growth of dense arrays of long vertically-aligned multi-walled carbon nanotubes arranged into complex patterns made of various combinations of basic features on a Si(1 0 0) surface written using simple mechanical techniques. The process was conducted in a plasma environment [9] and [10] produced by a microwave discharge which typically generates the low-temperature plasmas at the discharge power below 1 kW [11]. Our process starts from mechanical writing (scribing) a pattern of arbitrary features on pre-treated Si(1 0 0) wafers. Before and after the mechanical feature writing, the Si(1 0 0) substrates were cleaned in an aqueous solution of hydrofluoric acid for 2 min to remove any possible contaminations (such as oil traces which could decompose to free carbon at elevated temperatures) from the substrate surface. A piece of another silicon wafer cleaned in the same way as the substrate, or a diamond scriber were used to produce the growth patterns by a simple arbitrary mechanical writing, i.e., by making linear scratches or dot punctures on the Si wafer surface. The results were the same in both cases, i.e., when scratching the surface by Si or a diamond scriber. The procedure for preparation of the substrates did not involve any possibility of external metallic contaminations on the substrate surface. After the preparation, the substrates were loaded into an ASTeX model 5200 chemical vapour deposition (CVD) reactor, which was very carefully conditioned to remove any residue contamination. The samples were heated to at least 800 °C to remove any oxide that could have formed during the sample loading [12]. After loading the substrates into the reactor chamber, N2 gas was supplied into the chamber at the pressure of 7 Torr to ignite and sustain the discharge at the total power of 200 W. Then, a mixture of CH4 and 60% of N2 gases were supplied at 20 Torr, and the discharge power was increased to 700 W (power density of approximately 1.49 W/cm3). During the process, the microwave plasma was in a direct contact with the substrate. During the plasma exposure, no external heating source was used, and the substrate temperature (∼850 °C) was maintained merely due to the plasma heating. The features were exposed to a microwave plasma for 3–5 min. A photograph of the reactor and the plasma discharge is shown in Fig. 1a and b.

Plasma enables edge-to-center-oriented graphene nanoarrays on Si nanograss

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.

Control of density of self-organized carbon nanotube arrays by catalyst pretreatment through plasma immersion ion implantation

A simple and effective method of controlling the growth of vertically aligned carbon nanotube arrays in a lowerature plasma is presented. Ni catalyst was pretreated by plasma immersion ion implantation prior to the nanotube growth by plasma-enhanced chemical vapor deposition. Both the size distribution and the areal density of the catalyst nanoparticles decrease due to the ion-surface interactions. Consequently, the resulting size distribution of the vertically aligned carbon nanotubes is reduced to 50 ∼ 100 nm and the areal density is lowered (by a factor of ten) to 10 8 cm -2, which is significantly different from the very-high-density carbon nanotube forests commonly produced by thermal chemical vapor deposition. The efficiency of this pretreatment is compared with the existing techniques such as neutral gas annealing and plasma etching. These results are highly relevant to the development of the next-generation nanoelectronic and optoelectronic devices that require effective control of the density of nanotube arrays.

Control of morphology and electrical properties of self-organized graphenes in a plasma

The possibility of effective control of morphology and electrical properties of self-organized graphene structures on plasma-exposed Si surfaces is demonstrated. The structures are vertically standing nanosheets and can be grown without any catalyst and any external heating upon direct contact with high-density inductively coupled plasmas at surface temperatures not exceeding 673–723 K. Study of nucleation and growth dynamics revealed the possibility to switch-over between the two most common (turnstile- and maze-like) morphologies on the same substrates by a simple change of the plasma parameters. This change leads to the continuous or discontinuous native oxide layer that supports self-organized patterns of small carbon nanoparticles on which the structures nucleate. It is shown that by tailoring the nanoparticle arrangement one can create various three-dimensional architectures and networks of graphene nanosheet structures. We also demonstrate effective control of the degree of graphitization of the graphene nanosheet structures from the initial through the final growth stages. This makes it possible to tune the electrical resistivity properties of the produced three-dimensional patterns/networks from strongly dielectric to semiconducting. Our results contribute to enabling direct integration of graphene structures into presently dominant Si-based nanofabrication platform for next-generation nanoelectronic, sensor, biomedical, and optoelectronic components and nanodevices.

Plasma-made silicon nanograss and related nanostructures

Plasma-made nanostructures show outstanding potential for applications in nanotechnology. This paper provides a concise overview on the progress of plasma-based synthesis and applications of silicon nanograss and related nanostructures. The materials described here include black silicon, Si nanotips produced using a self-masking technique as well as self-organized silicon nanocones and nanograss. The distinctive features of the Si nanograss, two-tier hierarchical and tilted nanograss structures are discussed. Specific applications based on the unique features of the silicon nanograss are also presented.

Self-organized vertically aligned single-crystal silicon nanostructures with controlled shape and aspect ratio by reactive plasma etching

The formation of vertically aligned single-crystalline silicon nanostructures via "self-organized" maskless etching in Ar+ H 2 plasmas is studied. The shape and aspect ratio can be effectively controlled by the reactive plasma composition. In the optimum parameter space, single-crystalline pyramid-like nanostructures are produced; otherwise, nanocones and nanodots are formed. This generic nanostructure formation approach does not involve any external material deposition. It is based on a concurrent sputtering, etching, hydrogen termination, and atom/radical redeposition and can be applied to other nanomaterials.

Standing surface waves in a dust-contaminated large-area planar plasma source

The effect of charged particulates or dusts on surface wave produced microwave discharges is studied. The frequencies of the standing electromagnetic eigenmodes of large-area flat plasmas are calculated. The dusts absorb a significant amount of the plasma electrons and can lead to a modification of the electromagnetic field structure in the discharge by shifting the originally excited operating mode out of resonance. For certain given proportions of dusts, mode conversion is found to be possible. The power loss in the discharge is also increased because of dust-specific dissipations, leading to a decrease of the operating mode quality factor.

Reactive oxygen plasma-enabled synthesis of nanostructured CdO : tailoring nanostructures through plasma–surface interactions

Plasma-assisted synthesis of nanostructures is one of the most precise and effective approaches used in nanodevice fabrication. Here we report on the innovative approach of synthesizing nanostructured cadmium oxide films on Cd substrates using a reactive oxygen plasma-based process. Under certain conditions, the surface morphology features arrays of crystalline CdO nano/micropyramids. These nanostructures grow via unconventional plasma-assisted oxidation of a cadmium foil exposed to inductively coupled plasmas with a narrow range of process parameters. The growth of the CdO pyramidal nanostructures takes place in the solid-liquid-solid phase, with the rates determined by the interaction of plasma-produced oxygen atoms and ions with the surface. It is shown that the size of the pyramidal structures can be effectively controlled by the fluxes of oxygen atoms and ions impinging on the cadmium surface. The unique role of the reactive plasma environment in the controlled synthesis of CdO nanopyramidal structures is discussed as well.

Monoclinic β-MoO3 nanosheets produced by atmospheric microplasma : application to lithium-ion batteries

Porous high surface area thin films of nanosheet-shaped monoclinic MoO 3 were deposited onto platinized Si substrates using patch antenna-based atmospheric microplasma processing. The films were characterized by high resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM) and electrochemical analysis. The electrochemical analysis shows original redox peaks and high charge capacity, and also indicates a reversible electrochemical behaviour particularly beneficial for applications in Li-ion batteries. SEM shows that the films are highly porous and consist of nanosheets 50-100 nm thick with surface dimensions in the micrometre range. HRTEM reveals that the MoO3 nanosheets consist of the monoclinic beta phase of MoO3. These intricate nanoarchitectures made of monoclinic MoO3 nanosheets have not been studied previously in the context of applications in Li-ion batteries and show superior structural and morphological features that enable effective insertion of Li ions.

Two-surface wave decay : controlling power transfer in plasma-surface interactions

Controlled interaction of high-power pulsed electromagnetic radiation with plasma-exposed solid surfaces is a major challenge in applications spanning from electron beam accelerators in microwave electronics to pulsed laser ablation-assisted synthesis of nanomaterials. It is shown that the efficiency of such interaction can be potentially improved via an additional channel of wave power dissipation due to nonlinear excitation of two counterpropagating surface waves, resonant excitations of the plasma-solid system.Physics.

Low-frequency, high-density, inductively coupled plasma sources : operation and applications

Operation regimes, plasma parameters, and applications of the low-frequency (∼500 kHz) inductively coupled plasma (ICP) sources with a planar external coil are investigated. It is shown that highly uniform, high-density (ne∼9×1012 cm-3) plasmas can be produced in low-pressure argon discharges with moderate rf powers. The low-frequency ICP sources operate in either electrostatic (E) or electromagnetic (H) regimes in a wide pressure range without any Faraday shield or an external multipolar magnetic confinement, and exhibit high power transfer efficiency, and low circuit loss. In the H mode, the ICP features high level of uniformity over large processing areas and volumes, low electron temperatures, and plasma potentials. The low-density, highly uniform over the cross-section, plasmas with high electron temperatures and plasma and sheath potentials are characteristic to the electrostatic regime. Both operation regimes offer great potential for various plasma processing applications. As examples, the efficiency of the low-frequency ICP for steel nitriding and plasma-enhanced chemical vapor deposition of hydrogenated diamond-like carbon (DLC) films, is demonstrated. It appears possible to achieve very high nitriding rates and dramatically increase micro-hardness and wear resistance of the AISI 304 stainless steel. It is also shown that the deposition rates and mechanical properties of the DLC films can be efficiently controlled by selecting the discharge operating regime.