Control and diagnostics of inductively coupled plasmas for chemical vapour deposition of nanocomposite carbon nitride-based films

Control and diagnostics of low-frequency (∼ 500 kHz) inductively coupled plasmas for chemical vapor deposition (CVD) of nano-composite carbon nitride-based films is reported. Relation between the discharge control parameters, plasma electron energy distribution/probability functions (EEDF/EEPF), and elemental composition in the deposited C-N based thin films is investigated. Langmuir probe technique is employed to monitor the plasma density and potential, effective electron temperature, and EEDFs/EEPFs in Ar + N2 + CH4 discharges. It is revealed that varying RF power and gas composition/pressure one can engineer the EEDFs/EEPFs to enhance the desired plasma-chemical gas-phase reactions thus controlling the film chemical structure. Auxiliary diagnostic tools for study of the RF power deposition, plasma composition, stability, and optical emission are discussed as well.

Reactive species in RF plasma sputtering deposition of nanocrystalline calcium phosphate bio-active films

Optical emission of reactive plasma species during the synthesis of functionally graded calcium phosphate-based bioactive films has been investigated. The coatings have been deposited on Ti-6Al-4V orthopedic alloy by co-sputtering of hydroxyapatite (HA) and titanium targets in reactive plasmas of Ar + H2O gas mixtures. The species, responsible for the Ca-P-Ti film growth have been non-intrusively monitored in situ by a high-resolution optical emission spectroscopy (OES). It is revealed that the optical emission originating from CaO species dominates throughout the deposition process. The intensities of CaO, PO and CaPO species are strongly affected by variations of the operating pressure, applied RF power, and DC substrate bias. The optical emission intensity (OEI) of reaction species can efficiently be controlled by addition of H2O reactant.

Magnetic fields and uniformity of radio frequency power deposition in low-frequency inductively coupled plasmas with crossed internal oscillating currents

Radial and axial distributions of magnetic fields in a low-frequency (∼460 kHz)inductively coupled plasmasource with two internal crossed planar rf current sheets are reported. The internal antenna configuration comprises two orthogonal sets of eight alternately reconnected parallel and equidistant copper litz wires in quartz enclosures and generates three magnetic (H z, H r, and H φ) and two electric (E φ and E r) field components at the fundamental frequency. The measurements have been performed in rarefied and dense plasmas generated in the electrostatic(E) and electromagnetic (H)discharge modes using two miniature magnetic probes. It is shown that the radial uniformity and depth of the rf power deposition can be improved as compared with conventional sources of inductively coupled plasmas with external flat spiral (“pancake”) antennas. Relatively deeper rf power deposition in the plasma source results in more uniform profiles of the optical emission intensity, which indicates on the improvement of the plasma uniformity over large chamber volumes. The results of the numerical modeling of the radial magnetic field profiles are found in a reasonable agreement with the experimental data.

Self-organization and dynamics of nanoparticles in chemically active plasmas for low-temperature deposition of silicon and carbon-based nanostructured films

Self-organization and dynamic processes of nano/micron-sized solid particles grown in low-temperature chemically active plasmas as well as the associated physico-chemical processes are reviewed. Three specific reactive plasma chemistries, namely, of silane (SiH4), acetylene (C 2H2), and octafluorocyclobutane (c-C4F 8) RF plasma discharges for plasma enhanced chemical vapor deposition of amorphous hydrogenated silicon, hydrogenated and fluorinated carbon films, are considered. It is shown that the particle growth mechanisms and specific self-organization processes in the complex reactive plasma systems are related to the chemical organization and size of the nanoparticles. Correlation between the nanoparticle origin and self-organization in the ionized gas phase and improved thin film properties is reported. Self-organization and dynamic phenomena in relevant reactive plasma environments are studied for equivalent model systems comprising inert buffer gas and mono-dispersed organic particulate powders. Growth kinetics and dynamic properties of the plasma-assembled nanoparticles can be critical for the process quality in microelectronics as well as a number of other industrial applications including production of fine metal or ceramic powders, nanoparticle-unit thin film deposition, nanostructuring of substrates, nucleating agents in polymer and plastics synthesis, drug delivery systems, inorganic additives for sunscreens and UV-absorbers, and several others. Several unique properties of the chemically active plasma-nanoparticle systems are discussed as well.

Plasma-enhanced chemical vapor deposition of graphene nanostructures

Graphene has received great interest from researchers all over the world owing to its unique properties. Much of the excitement surrounding graphene is due to its remarkable properties and inherent quantum effects. These effects and properties make it a desirable material for the fabrication of new devices. Graphene has a plethora of potential uses including gas and molecular sensors, electronics, spintronics and optics [1-7]. Interestingly, some of these properties have been known about since before the material was even isolated due to a considerable amount of theoretical work and simulations. The material was to some extent a condensed matter modelers "toy" as it was used as a benchmark 2D material Graphene had been used for a long time as the fundamental building block of many other carbon structures...

Effect of plasma environment on synthesis of vertically aligned carbon nanofibers in plasma-enhanced chemical vapor deposition

We present a theoretical model describing a plasma-assisted growth of carbon nanofibers (CNFs), which involves two competing channels of carbon incorporation into stacked graphene sheets: via surface diffusion and through the bulk of the catalyst particle (on the top of the nanofiber), accounting for a range of ion- and radical-assisted processes on the catalyst surface. Using this model, it is found that at low surface temperatures, Ts, the CNF growth is indeed controlled by surface diffusion, thus quantifying the semiempirical conclusions of earlier experiments. On the other hand, both the surface and bulk diffusion channels provide a comparable supply of carbon atoms to the stacked graphene sheets at elevated synthesis temperatures. It is also shown that at low Ts, insufficient for effective catalytic precursor decomposition, the plasma ions play a key role in the production of carbon atoms on the catalyst surface. The model is used to compute the growth rates for the two extreme cases of thermal and plasma-enhanced chemical vapor deposition of CNFs. More importantly, these results quantify and explain a number of observations and semiempirical conclusions of earlier experiments.

3D-hybrid networks with controllable electrical conductivity from the electrochemical deposition of terthiophene-functionalized polyphenylene dendrimers

(Figure Presented) Unusual conductivity effects: Suitably functionalized dendrimers (see picture) are capable of forming truly covalent three-dimensional networks with remarkably high conductivity on electrochemical doping. Depending on the charging level of the electroactive components used as building blocks for the dendrimer core and the perimeter, two separated regimes of electrical conductivity can be observed.

Particle size distribution effects on preferential deposition areas in metal foam wrapped tube bundle

This paper presents a numerical model for understanding particle transport and deposition in metal foam heat exchangers. Two-dimensional steady and unsteady numerical simulations of a standard single row metal foam-wrapped tube bundle are performed for different particle size distributions, i.e. uniform and normal distributions. Effects of different particle sizes and fluid inlet velocities on the overall particle transport inside and outside the foam layer are also investigated. It was noted that the simplification made in the previously-published numerical works in the literature, e.g. uniform particle deposition in the foam, is not necessarily accurate at least for the cases considered here. The results highlight the preferential particle deposition areas both along the tube walls and inside the foam using a developed particle deposition likelihood matrix. This likelihood matrix is developed based on three criteria being particle local velocity, time spent in the foam, and volume fraction. It was noted that the particles tend to deposit near both front and rear stagnation points. The former is explained by the higher momentum and direct exposure of the particles to the foam while the latter only accommodate small particles which can be entrained in the recirculation region formed behind the foam-wrapped tubes.

Rapid and highly efficient growth of graphene on copper by chemical vapor deposition of ethanol

The growth of graphene by chemical vapor deposition on metal foils is a promising technique to deliver large-area films with high electron mobility. Nowadays, the chemical vapor deposition of hydrocarbons on copper is the most investigated synthesis method, although many other carbon precursors and metal substrates are used too. Among these, ethanol is a safe and inexpensive precursor that seems to offer favorable synthesis kinetics. We explored the growth of graphene on copper from ethanol, focusing on processes of short duration (up to one min). We investigated the produced films by electron microscopy, Raman and X-ray photoemission spectroscopy. A graphene film with high crystalline quality was found to cover the entire copper catalyst substrate in just 20 s, making ethanol appear as a more efficient carbon feedstock than methane and other commonly used precursors.

Electrocatalytic and SERS activity of Pt rich Pt-Pb nanostructures formed via the utilisation of in-situ underpotential deposition of lead

The controlled synthesis of nanostructured materials remains an ongoing area of research, especially as the size, shape and composition of nanomaterials can greatly influence their properties and applications. In this work we present the electrodeposition of highly dendritic platinum rich platinum-lead nanostructures, where lead acetate acts as an inorganic shape directing agent via underpotential deposition on the growing electrodeposit. It was found that these nanomaterials readily oxidise at potentials below monolayer oxide formation, which significantly impacts on the methanol electrooxidation reaction and correlates with the incipient hydrous oxide adatom mediator (IHOAM) model of electrocatalysis. Additionally these materials were tested for their surface enhanced Raman scattering (SERS) activity, where the high density of sharp tips provides promise for their application as SERS substrates.

Nanoscale texture on glass and titanium substrates by physical vapor deposition process

The aim of the paper is to give a feasibility study on the material deposition of Nanoscale textured morphology of titanium and titanium oxide layers on titanium and glass substrates. As a recent development in nanoscale deposition, Physical Vapor Deposition (PVD) based DC magnetron sputtering has been the choice for the deposition process. The nanoscale morphology and surface roughness of the samples have been characterized using Atomic Force Microscope (AFM). The surface roughnesses obtained from AFM have been compared using surface profiler. From the results we can say that the roughness values are dependent on the surface roughness of the substrate. The glass substrate was relatively smoother than the titanium plate and hence lower layer roughness was obtained. From AFM a unique nano-pattern of a boomerang shaped titanium oxide layer on glass substrate have been obtained. The boomerang shaped nano-scale pattern was found to be smaller when the layer was deposited at higher sputtering power. This indicated that the morphology of the deposited titanium oxide layer has been influenced by the sputtering power.

Methotrexate-conjugated PEGylated dendrimers show differential patterns of deposition and activity in tumour-burdened lymph nodes after intravenous and subcutaneous administration in rats

The current study sought to explore whether the subcutaneous administration of lymph-targeted dendrimers, conjugated with a model chemotherapeutic (methotrexate, MTX), was able to enhance anticancer activity against lymph node metastases. The lymphatic pharmacokinetics and antitumour activity of PEGylated polylysine dendrimers conjugated to MTX [D-MTX(OH)] via a tumour-labile hexapeptide linker was examined in rats and compared to a similar system where MTX was α-carboxyl O-tert-butylated [D-MTX(OtBu)]. The latter has previously been shown to exhibit longer plasma circulation times. D-MTX(OtBu) was well absorbed from the subcutaneous injection site via the lymph, and 3 to 4%/g of the dose was retained by sentinel lymph nodes. In contrast, D-MTX(OH) showed limited absorption from the subcutaneous injection site, but absorption was almost exclusively via the lymph. The retention of D-MTX(OH) by sentinel lymph nodes was also significantly elevated (approximately 30% dose/g). MTX alone was not absorbed into the lymph. All dendrimers displayed lower lymph node targeting after intravenous administration. Despite significant differences in the lymph node retention of D-MTX(OH) and D-MTX(OtBu) after subcutaneous and intravenous administration, the growth of lymph node metastases was similarly inhibited. In contrast, the administration of MTX alone did not significantly reduce lymph node tumour growth. Subcutaneous administration of drug-conjugated dendrimers therefore provides an opportunity to improve drug deposition in downstream tumour-burdened lymph nodes. In this case, however, increased lymph node biodistribution did not correlate well with antitumour activity, possibly suggesting constrained drug release at the site of action.

Cyclic Salinity Model for deposition of large-scale coal deposits

Existing field data for Rangal coals (Late Permian) of the Bowen Basin, Queensland, Australia, are inconsistent with the depositional model generally accepted in the current geological literature to explain coal deposition. Given the apparent unsuitability of the current depositional model to the Bowen Basin coal data, a new depositional model, here named the Cyclic Salinity Model, is proposed and tested in this study.

Phase-selective hydrothermal synthesis of Cu2ZnSnS4nanocrystals: The effect of the sulphur precursor

High quality Cu2ZnSnS4 (CZTS) films with uniform thickness and smooth surface were prepared using nanocrystals synthesized by a one-step hydrothermal method. It is found that the nature of the sulphur precursor used in the hydrothermal reaction influences both the compositional purity and the crystal structure of the synthesized hydrothermal product significantly. The CZTS material consisting of both wurtzite and kesterite crystal structures was obtained when using an organic sulfur precursor such as thioacetamide and thiourea in the precursor solution of the hydrothermal reaction while the pure kesterite phase CZTS nanocrystals were made when Na2S was employed as the sulphur precursor. CZTS thin films deposited on a Mo–soda lime glass substrate with uniform thickness (1.7 μm) were made by a simple doctor-blading method. The investigation of the effect of thermal treatment on the film has indicated that the wurtzite CZTS material was completely transformed to the kesterite phase when the material was annealed at 550 °C. Large grains (around 2 μm in size) were found on the surface of the CZTS film which was annealed at 600 °C. The evaluation of the photoresponse of the CZTS thin films has showed that a higher and very stable photocurrent was generated by the film annealed at 600 °C compared to the film annealed at 550 °C.

Influence of pipe length and flow rate on nano-particle deposition in laminar circular pipe flows

The Lagrangian particle tracking provides an effective method for simulating the deposition of nano- particles as well as micro-particles as it accounts for the particle inertia effect as well as the Brownian excitation. However, using the Lagrangian approach for simulating ultrafine particles has been limited due to computational cost and numerical difficulties. The aim of this paper is to study the deposition of nano-particles in cylindrical tubes under laminar condition using the Lagrangian particle tracking method. The commercial Fluent software is used to simulate the fluid flow in the pipes and to study the deposition and dispersion of nano-particles. Different particle diameters as well as different pipe lengths and flow rates are examined. The results show good agreement between the calculated deposition efficiency and different analytic correlations in the literature. Furthermore, for the nano-particles with higher diameters and when the effect of inertia has a higher importance, the calculated deposition efficiency by the Lagrangian method is less than the analytic correlations based on Eulerian method due to statistical error or the inertia effect.