Interface control of surface photochemical reactivity in ultrathin epitaxial ferroelectric films

Asymmetrical electrical boundary conditions in (001)-oriented Pb(Zr 0.2TiO0.8)O3 (PZT) epitaxial ultrathin ferroelectric films are exploited to control surface photochemical reactivity determined by the sign of the surface polarization charge. It is shown that the preferential orientation of polarization in the as-grown PZT layer can be manipulated by choosing an appropriate type of bottom electrode material. PZT films deposited on the SrRuO3 electrodes exhibit preferential upward polarization (C) whilst the same films grown on the (La,Sr)CoO 3-electrodes are polarized downward (C-). Photochemical activity of the PZT surfaces with different surface polarization charges has been tested by studying deposition of silver nanoparticles from AgNO3 solution under UV irradiation. PZT surfaces with preferential C orientation possess a more active surface for metal reduction than their C- counterparts, evidenced by large differences in the concentration of deposited silver nanoparticles. This effect is attributed to band bending at the bottom interface which varies depending on the difference in work functions of PZT and electrode materials.

Deterministic control of structural and optical properties of plasma-grown vertical graphene nanosheet networks via nitrogen gas variation

The effect of nitrogen on the growth of vertically oriented graphene nanosheets on catalyst-free silicon and glass substrates in a plasma-assisted process is studied. Different concentrations of nitrogen were found to act as versatile control knobs that could be used to tailor the length, number density and structural properties of the nanosheets. Nanosheets with different structural characteristics exhibit markedly different optical properties. The nanosheet samples were treated with a bovine serum albumin protein solution to investigate the effects of this variation on the optical properties for biosensing through confocal micro-Raman spectroscopy and UV-Vis spectrophotometry. © 2012 Optical Society of America.

Control of ion density distribution by magnetic traps for plasma electrons

The effect of a magnetic field of two magnetic coils on the ion current density distribution in the setup for low-temperature plasma deposition is investigated. The substrate of 400 mm diameter is placed at a distance of 325 mm from the plasma duct exit, with the two magnetic coils mounted symmetrically under the substrate at a distance of 140 mm relative to the substrate centre. A planar probe is used to measure the ion current density distribution along the plasma flux cross-sections at distances of 150, 230, and 325 mm from the plasma duct exit. It is shown that the magnetic field strongly affects the ion current density distribution. Transparent plastic films are used to investigate qualitatively the ion density distribution profiles and the effect of the magnetic field. A theoretical model is developed to describe the interaction of the ion fluxes with the negative space charge regions associated with the magnetic trapping of the plasmaelectrons. Theoretical results are compared with the experimental measurements, and a reasonable agreement is demonstrated.

Property-performance control of multidimensional, hierarchical, single-crystalline ZnO nanoarchitectures

Diverse morphologies of multidimensional hierarchical single-crystalline ZnO nanoarchitectures including nanoflowers, nanobelts, and nanowires are obtained by use of a simple thermal evaporation and vapour-phase transport deposition technique by placing Au-coated silicon substrates in different positions inside a furnace at process temperatures as low as 550 °C. The nucleation and growth of ZnO nanostructures are governed by the vapour–solid mechanism, as opposed to the commonly reported vapour–liquid–solid mechanism, when gold is used in the process. The morphological, structural, compositional and optical properties of the synthesized ZnO nanostructures can be effectively tailored by means of the experimental parameters, and these properties are closely related to the local growth temperature and gas-phase supersaturation at the sample position. In particular, room-temperature photoluminescence measurements reveal an intense near-band-edge ultraviolet emission at about 386 nm for nanobelts and nanoflowers, which suggests that these nanostructures are of sufficient quality for applications in, for example, optoelectronic devices.

Plasma control of morpho-dimensional selectivity of hematite nanostructures

Highly controllablefabrication of the nanowire, nanocone, and mixed nanowire/nanowall arrays of iron oxide (hematite, α-Fe2O3) nanostructures in a simple, environment-friendly process is achieved by exposing the metal foils to low-temperature oxygen plasmas. Very dense forests of thin (≈50 nm) and long (up to several μm) nanowires are grown on the electrically biased substrates, whereas the use of the electrically insulated substrate resulted in the formation of a mixed array of nanowires and nanowalls. The proposed mechanism of the nanostructure growth is supported by the numerical simulations demonstrating the key role of the plasma environment in the growth morphology selection.

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.

Control of energy and matter at nanoscales : challenges and opportunities for plasma nanoscience in a sustainability age

Plasma nanoscience is an emerging multidisciplinary research field at the cutting edge of a large number of disciplines including but not limited to physics and chemistry of plasmas and gas discharges, materials science, surface science, nanoscience and nanotechnology, solid-state physics, space physics and astrophysics, photonics, optics, plasmonics, spintronics, quantum information, physical chemistry, biomedical sciences and related engineering subjects. This paper examines the origin, progress and future perspectives of this research field driven by the global scientific and societal challenges. The future potential of plasma nanoscience to remain a highly topical area in the global research and technological agenda in the age of fundamental-level control for a sustainable future is assessed using a framework of the five Grand Challenges for Basic Energy Sciences recently mapped by the US Department of Energy. It is concluded that the ongoing research is very relevant and is expected to substantially expand to competitively contribute to the solution of all of these Grand Challenges. The approach to controlling energy and matter at nano- and subnanoscales is based on identifying the prevailing carriers and transfer mechanisms of the energy and matter at the spatial and temporal scales that are most relevant to any particular nanofabrication process. Strong accent is made on the competitive edge of the plasma-based nanotechnology in applications related to the major socio-economic issues (energy, food, water, health and environment) that are crucial for a sustainable development of humankind. Several important emerging topics, opportunities and multidisciplinary synergies for plasma nanoscience are highlighted. The main nanosafety issues are also discussed and the environment- and human health-friendly features of plasma-based nanotech are emphasized.

Nanoscale control of energy and matter in plasma–surface interactions : toward energy- and matter-efficient nanotech

The approach to control the elementary processes of plasma–surface interactions to direct the fluxes of energy and matter at nano- and subnanometer scales is introduced. This ability is related to the solution of the grand challenge of directing energy and matter at nanoscales and is critical for the renewable energy and energy-efficient technologies for a sustainable future development. The examples of deterministic synthesis of self-organized arrays of metastable nanostructures in the size range beyond the reach of the present-day nanofabrication are considered to illustrate this possibility. By using precisely controlled and kinetically fast nanoscale transfer of energy and matter under nonequilibrium conditions and harnessing numerous plasma-specific controls of species creation, delivery to the surface,nucleation, and large-scale self-organization of nuclei and nanostructures, the arrays of metastable nanostructures can be created, arranged, stabilized, and further processed to meet the specific requirements of the envisaged applications.

3-Orders-of-magnitude density control of single-walled carbon nanotube networks by maximizing catalyst activation and dosing carbon supply

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. © 2011 The Royal Society of Chemistry.

Control of dense carbon nanotube arrays via hierarchical multilayer catalyst

Effective control of dense, high-quality carbon nanotube arrays using hierarchical multilayer catalyst patterns is demonstrated. Scanning/transmission electron microscopy, atomic force microscopy, Raman spectroscopy, and numerical simulations show that by changing the secondary and tertiary layers one can control the properties of the nanotube arrays. The arrays with the highest surface density of vertically aligned nanotubes are produced using a hierarchical stack of iron nanoparticles and alumina and silica layers differing in thickness by one order of magnitude from one another. The results are explained in terms of the catalyst structure effect on carbon diffusivity.

Magnetic control of breakdown : toward energy-efficient hollow-cathode magnetron discharges

Characteristics of electrical breakdown of a planar magnetron enhanced with an electromagnet and a hollow-cathode structure, are studied experimentally and numerically. At lower pressures the breakdown voltage shows a dependence on the applied magnetic field, and the voltage necessary to achieve the self-sustained discharge regime can be significantly reduced. At higher pressures, the dependence is less sensitive to the magnetic field magnitude and shows a tendency of increased breakdown voltage at the stronger magnetic fields. A model of the magnetron discharge breakdown is developed with the background gas pressure and the magnetic field used as parameters. The model describes the motion of electrons, which gain energy by passing the electric field across the magnetic field and undergo collisions with neutrals, thus generating new bulk electrons. The electrons are in turn accelerated in the electric field and effectively ionize a sufficient amount of neutrals to enable the discharge self-sustainment regime. The model is based on the assumption about the combined classical and near-wall mechanisms of electron conductivity across the magnetic field, and is consistent with the experimental results. The obtained results represent a significant advance toward energy-efficient multipurpose magnetron discharges.

Control of morphology and nucleation density of iron oxide nanostructures by electric conditions on iron surfaces exposed to reactive oxygen plasmas

The possibility to control the morphology and nucleation density of quasi-one-dimensional, single-crystalline α -Fe2 O3 nanostructures by varying the electric potential of iron surfaces exposed to reactive oxygen plasmas is demonstrated experimentally. A systematic increase in the oxygen ion flux through rf biasing of otherwise floating substrates and then an additional increase of the ion/neutral density resulted in remarkable structural transformations of straight nanoneedles into nanowires with controlled tapering/aspect ratio and also in larger nucleation densities. Multiscale numerical simulations relate the microscopic ion flux topographies to the nanostructure nucleation and morphological evolution. This approach is applicable to other metal-oxide nanostructures.

Control of core-shell structure and elemental composition of binary quantum dots

The possibility of initial stage control of the elemental composition and core/shell structure of binary SiC quantum dots by optimizing temporal variation of Si and C incoming fluxes and surface temperatures is shown via hybrid numerical simulations. Higher temperatures and influxes encourage the formation of a stoichiometric outer shell over a small carbon-enriched core, whereas lower temperatures result in a larger carbon-enriched core, Si-enriched undershell, and then a stoichiometric SiC outer shell. This approach is generic and is applicable to a broad range of semiconductor materials and nanofabrication techniques. © 2007 American Institute of Physics.

Hydrogen in plasma-nanofabrication : selective control of nanostructure heating and passivation

The possibility of independent control of the surface fluxes of energy and hydrogen-containing radicals, thus enabling selective control of the nanostructure heating and passivation, is demonstrated. In situ energy flux measurements reveal that even a small addition of H2 to low-pressure Ar plasmas leads to a dramatic increase in the energy deposition through H recombination on the surface. The heat release is quenched by a sequential addition of a hydrocarbon precursor while the surface passivation remains effective. Such selective control offers an effective mechanism for deterministic control of the growth shape, crystallinity, and density of nanostructures in plasma-aided nanofabrication. © 2010 American Institute of Physics.