Microstructure and mechanical properties of physical vapor deposited Cu/W nanoscale multilayers: Influence of layer thickness and temperature

Based on our previous knowledge on Cu/Nb nanoscale metallic multilayers (NMMs), Cu/WNMMs show a good potential for applications as heat skins in plasma experiments and armors, and it could be expected that the substitution of Nb byWwould increase the strength, particularly at high temperatures. To check this hypothesis, Cu/WNMMs with individual layer thicknesses ranging between 5 and 30 nm were deposited by physical vapour deposition, and their mechanical properties were measured by nanoindentation. The results showed that, contrary to Cu/Nb NMMs, the hardness was independent of the layer thickness and decreased rapidlywith temperature, especially above 200 °C. This behavior was attributed to the growth morphology of theWlayers aswell as the jagged Cu/W interface, both a consequence of the lowW adatom mobility during deposition. Therefore, future efforts on the development of Cu/Wmultilayers should concentrate on optimization of theWdeposition parameters via substrate heating and/or ion assisted deposition to increase the W adatom mobility during deposition.

Structural characteristics of GaSB / GaAs nanowire heterostructures grown by metal-organic chemical vapor deposition

Highly lattice mismatched (7.8%) GaAs/GaSb nanowire heterostructures were grown by metal-organic chemical vapor deposition and their detailed structural characteristics were determined by electron microscopy. The facts that (i) no defects have been found in GaSb and its interfaces with GaAs and (ii) the lattice mismatch between GaSb/GaAs was fully relaxed suggest that the growth of GaSb nanowires is purely governed by the thermodynamics. The authors believe that the low growth rate of GaSb nanowires leads to the equilibrium growth. (c) 2006 American Institute of Physics.

Synthesis, characterization and chemical vapor deposition of transition metal di(tert-butyl)amido compounds

Although the transition metal chemistry of many dialkylamido ligands has been well studied, the chemistry of the bulky di(tert-butyl)amido ligand has been largely overlooked. The di(tert-butyl)amido ligand is well suited for synthesizing transition metal compounds with low coordination numbers; such compounds may exhibit interesting structural, physical, and chemical properties. Di(tert-butyl)amido complexes of transition metals are expected to exhibit high volatilities and low decomposition temperatures, thus making them well suited for the chemical vapor deposition of metals and metal nitrides. Treatment of MnBr₂(THF)₂, FeI₂, CoBr₂(DME), or NiBr₂(DME) with two equivalents of LiN(t-Bu)2 in benzene affords the two-coordinate complex M[N(t-Bu)₂]₂, where M is Mn, Fe, Co, or Ni. Crystallographic studies show that the M-N distances decrease across the series: 1.9365 (Mn), 1.8790 (Fe), 1.845 (Co), 1.798 Å (Ni). The N-M- N angles are very close to linear for Mn and Fe (179.30 and 179.45°, respectively), but bent for Co and Ni (159.2 and 160.90°, respectively). As expected, the d⁵ Mn complex has a magnetic moment of 5.53 μΒ that is very close to the spin only value. The EPR spectrum is nearly axial with a low E/D ratio of 0.014. The d⁶ Fe compound has a room temperature magnetic moment of 5.55 μΒ indicative of a large orbital angular momentum contribution. It does not exhibit a Jahn-Teller distortion despite the expected doubly degenerate ground state. Applied field Mössbauer spectroscopy shows that the effective internal hyperfine field is unusually large, Hint = 105 T. The magnetic moments of Co[N(t-Bu)₂]₂ and Ni[N(t-Bu)₂]₂ are 5.24 and 3.02 μΒ respectively. Both are EPR silent at 4.2 K. Treatment of TiCl₄ with three equivalents of LiN(t-Bu)2 in pentane affords the briding imido compound Ti₂[μ-N(t-Bu)]₂Cl₂[N(t-Bu)₂]₂ via a dealkylation reaction. Rotation around the bis(tert-butyl)amido groups is hindered, with activation parameters of ΔH‡ = 12.8 ± 0.6 kcal mol-1 and ΔS‡ = -8 ± 2 cal K-1 ·mol-1, as evidenced by variable temperature 1H NMR spectroscopy. Treatment of TiCl₄ with two equivalents of HN(t-Bu)₂ affords Ti₂Cl₆[N(t-Bu)₂]₂. This complex shows a close-contact of 2.634(3) Å between Ti and the carbon atom of one of the CH₃ substituents on the tert-butyl groups. Theoretical considerations and detailed structural comparisons suggest this interaction is not agostic in nature, but rather is a consequence of interligand repulsions. Treatment of NiI₂(PPh3)₂ and PdCl₂(PPh₃)₂ with LiN(t-Bu)₂in benzene affords Ni[N(t-Bu)₂](PPh₃)I and Pd₃(μ₂-NBut₂)2(μ₂-PPh₂)Ph(PPh₃) respectively. The compound Ni[N(t-Bu)₂](PPh₃)I has distorted T-shape in geometry, whereas Pd₃(μ₂-NBut₂)₂(μ₂-PPh₂)Ph(PPh₃) contains a triangular palladium core. Manganese nitride films were grown from Mn[N(t-Bu)₂]₂ in the presence of anhydrous ammonia. The growth rate was several nanometers per minute even at the remarkably low temperature of 80⁰C. As grown, the films are carbon- and oxygen-free, and have a columnar morphology. The spacings between the columns become smaller and the films become smoother as the growth temperature is increased. The composition of the films is consistent with a stoichiometry of Mn₅N₂.

Formation and electron field emission of graphene films grown by hot filament chemical vapor deposition

Graphene films with different structures were catalytically grown on the silicon substrate pre-deposited with a gold film by hot filament chemical vapor deposition under different conditions, where methane, hydrogen and nitrogen were used as the reactive gases. The morphological and compositional properties of graphene films were studied using advanced instruments including field emission scanning electron microscopy, micro-Raman spectroscopy and X-ray photoelectron spectroscopy. The results indicate that the structure and composition of graphene films are changed with the variation of the growth conditions. According to the theory related to thermodynamics, the formation of graphene films was theoretically analyzed and the results indicate that the formation of graphene films is related to the fast incorporation and precipitation of carbon. The electron field emission (EFE) properties of graphene films were studied in a high vacuum system of ∼10-6 Pa and the EFE results show that the turn-on field is in a range of 5.2-5.64 V μm-1 and the maximum current density is about 63 μ A cm-2 at the field of 7.7 V μm-1. These results are important to control the structure of graphene films and have the potential applications of graphene in various nanodevices.

Room-temperature photoluminescence from nitrogenated carbon nanotips grown by plasma-enhanced hot filament chemical vapor deposition

Nitrogenated carbon nanotips with a low atomic concentration of nitrogen have been synthesized by using a custom-designed plasma-enhanced hot-filament plasma chemical vapor deposition system. The properties (including morphology, structure, composition, photoluminescence, etc.) of the synthesized nitrogenated carbon nanotips are investigated using advanced characterization tools. The room-temperature photoluminescence measurements show that the nitrogenated carbon nanotips can generate two distinct broad emissions located at ∼405 and ∼507 nm, respectively. Through the detailed analysis, it is shown that these two emission bands are attributed to the transition between the lone pair valence and bands, which are related to the sp3 and sp2 C-N bonds, respectively. These results are highly relevant to advanced applications of nitrogenated carbon nanotips in light emitting optoelectronic devices.

Tailoring carbon nanotips in the plasma-assisted chemical vapor deposition: Effect of the process parameters

Carbon nanotips have been synthesized from a thin carbon film deposited on silicon by bias-enhanced hot filament chemical vapor deposition under different process parameters. The results of scanning electron microscopy indicate that high-quality carbon nanotips can only be obtained under conditions when the ion flux is effectively drawn from the plasma sustained in a CH4 + NH3 + H2 gas mixture. It is shown that the morphology of the carbon nanotips can be controlled by varying the process parameters such as the applied bias, gas pressure, and the NH3 / H2 mass flow ratios. The nanotip formation process is examined through a model that accounts for surface diffusion, in addition to sputtering and deposition processes included in the existing models. This model makes it possible to explain the major difference in the morphologies of the carbon nanotips formed without and with the aid of the plasma as well as to interpret the changes of their aspect ratio caused by the variation in the ion/gas fluxes. Viable ways to optimize the plasma-based process parameters to synthesize high-quality carbon nanotips are suggested. The results are relevant to the development of advanced plasma-/ion-assisted methods of nanoscale synthesis and processing.

Analysis of photoluminescence background of Raman spectra of carbon nanotips grown by plasma-enhanced chemical vapor deposition

Carbon nanotips with different structures were synthesized by plasma-enhanced hot filament chemical vapor deposition and plasma-enhanced chemical vapor deposition using different deposition conditions, and they were investigated by scanning electron microscopy and Raman spectroscopy. The results indicate that the photoluminescence background of the Raman spectra is different for different carbon nanotips. Additionally, the Raman spectra of the carbon nanotips synthesized using nitrogen-containing gas precursors show a peak located at about 2120 cm-1 besides the common D and G peaks. The observed difference in the photoluminescence background is related to the growth mechanisms, structural properties, and surface morphology of a-C:H and a-C:H:N nanotips, in particular, the sizes of the emissive tips.

Graphitization of nanocrystalline carbon microcoils synthesized by catalytic chemical vapor deposition

Graphitization, a common process involving the transformation of metastable nongraphitic carbon into graphite is one of the major present-day challenges for micro- and nanocarbons due to their unique structural character and highly unusual thermal activation. Here we report on the successful graphitization of nanocrystalline carbon microcoils prepared by catalytic chemical vapor deposition and post-treated in argon atmosphere at temperatures ∼2500 °C for 2 h. The morphology, microstructure, and thermal properties of the carbon microcoils are examined in detail. The graphitization mechanism is discussed by invoking a model of structural transformation of the carbon microcoils. The results reveal that after graphitization the carbon microcoils are prominently purified and feature a clear helical morphology, as well as a more regular and ordered microstructure. The interlayer spacing of the carbon microcoils decreases from 0.36 to 0.34 nm, whereas the mean crystal sizes in the c - and a -directions increase from 1.64 to 2.04 nm and from 3.86 to 7.21 nm, respectively. Thermal treatment also substantially improves the antioxidation properties of the microcoils by lifting the oxidation onset temperature from 550 to 672 °C. This process may be suitable for other nongraphitic micro- and nanomaterials.

Carbon nanofiber growth in plasma-enhanced chemical vapor deposition

A theoretical model to describe the plasma-assisted growth of carbon nanofibers (CNFs) is proposed. Using the model, the plasma-related effects on the nanofiber growth parameters, such as the growth rate due to surface and bulk diffusion, the effective carbon flux to the catalyst surface, the characteristic residence time and diffusion length of carbon atoms on the catalyst surface, and the surface coverages, have been studied. The dependence of these parameters on the catalyst surface temperature and ion and etching gas fluxes to the catalyst surface is quantified. The optimum conditions under which a low-temperature plasma environment can benefit the CNF growth are formulated. These results are in good agreement with the available experimental data on CNF growth and can be used for optimizing synthesis of related nanoassemblies in low-temperature plasma-assisted nanofabrication. © 2008 American Institute of Physics.

Influence of hydrogen dilution on the growth of nanocrystalline silicon carbide films by low-frequency inductively coupled plasma chemical vapor deposition

Nanocrystalline silicon carbide (nc-SiC) films are prepared by low-frequency inductively coupled plasma chemical vapor deposition from feedstock gases silane and methane diluted with hydrogen at a substrate temperature of 500 °C. The effect of different hydrogen dilution ratios X [hydrogen flow (sccm) / silane + methane flow (sccm)] on the growth of nc-SiC films is investigated by X-ray diffraction, scanning electron microscopy, Fourier transform infrared (FTIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). At a low hydrogen dilution ratio X, cubic silicon carbide is the main crystal phase; whereas at a high hydrogen dilution ratio X, hexagonal silicon carbide is the main crystal phase. The SiC crystal phase transformation may be explained by the different surface mobility of reactive Si-based and C-based radicals deposited at different hydrogen dilution ratios X. The FTIR and XPS analyses show that the Si-C bonds are the main bonds in the films and elemental composition of SiC is nearly stoichiometric with almost equal share of silicon and carbon atoms.

Simulation of gas-phase nanoparticle dynamics in the plasma-enhanced chemical vapor deposition of carbon nanostructures

The results of 1D simulation of nanoparticle dynamics in the areas adjacent to nanostructured carbon-based films exposed to chemically active complex plasma of CH4 + H2 + Ar gas mixtures are presented. The nanoparticle-loaded near-substrate (including sheath and presheath) areas of a low-frequency (0.5 MHz) inductively coupled plasma facility for the PECVD growth of the ordered carbon-based nanotip structures are considered. The conditions allowing one to predict the size of particles that can pass through the plasma sheath and softly land onto the surface are formulated. The possibility of soft nano-cluster deposition without any additional acceleration common for some existing nano-cluster deposition schemes is demonstrated. The effect of the substrate heating power and the average atomic mass of neutral species is studied numerically and verified experimentally.

E and H regimes of plasma enhanced chemical vapor deposition of diamond-like carbon film in low frequency inductively coupled plasma reactor

This paper reports on the efficient deposition of hydrogenated diamond-like carbon (DLC) film in a plasma reactor that features both the capacitively and inductively coupled operation regimes. The hydrogenated DLC films have been prepared on silicon wafers using a low-frequency (500 kHz) inductively coupled plasma (ICP) chemical vapor deposition (CVD) system. At low RF powers, the system operates as an asymmetric capacitively coupled plasma source, and the film deposition process is undertaken in the electrostatic (E) discharge regime. Above the mode transition threshold, the high-density inductively coupled plasma is produced in the electromagnetic (H) discharge regime. It has been shown that the deposition rate and hardness of the DLC film are much higher in the H-mode deposition regime. For a 2.66-Pa H-mode CH4 + Ar gas mixture discharge, the deposited DLC film exhibits a mechanical hardness of 18 GPa, Young's modulus of 170 GPa, and compressive stress of 1.3 GPa.

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.