Nanocrystalline diamond coating on non-planar silicon substrates.

Micro and nanosystems-based products will be an important contributor to the industrial and economic future, as a key value adding element for many sectors. The adoption of micro and nano manufacturing technologies making use of a variety of materials, components and knowledge based technologies will most probably provide functionality and intelligence to highly miniaturised systems. Chemical Vapour Deposited (CVD) diamond is a hard material of high mechanical strength and thermal stability and therefore an ideal candidate for microelectromechanical devices. The latter, is already being used to manufacture sensors, resonators, actuators, biological devices or even plastic moulding impressions, by depositing the film on a structured substrate, by selective growth of diamond on Si using SiO2 masks, or by pattern etching on oxygen-containing plasma. The diamond shaping may also be performed by a fine tuning of the nucleation and growth process. In this paper, it is presented the results of diamond coated structures and an evaluation of its morphology variation with the substrate configuration. The grown films were characterized for quality, surface roughness and microstructure using scanning electron microscopy, Raman and X-ray diffraction spectroscopy and surface profilometry.

Direct nucleation of silver nanoparticles on graphene sheet.

Silver (Ag) nanoparticles were synthesized on the surface of graphene sheet by the simultaneous reduction of Ag+ and graphene oxide (GO) in the presence of simple reducing agent, hydrazine hydrate (N2H4 x H2O). Both the Ag+ and GO were reduced and Ag+ was nucleated onto graphene. GO flakes were prepared by conventional chemical exfoliation method and in the presence of strong acidic medium of potassium chlorate. Silver nanoparticles were prepared using 0.01 M AgNO3 solution. The reduced GO sheet decorated with Ag is referred as G-Ag sample. G-Ag was characterized by FTIR (Fourier transform infrared) spectroscopy using GO as standard. An explicit alkene peak appeared around 1625 cm(-1) was observed in G-Ag sample. Besides, the characteristic carbonyl and hydroxyl peaks shows well reduction of GO. The FTIR therefore confirms the direct interaction of Ag into Graphene. SEM (scanning electron microscopy) and TEM (transmission electron microscopy) analysis were performed for morphological probing. The average size of Ag nanoparticles was confirmed by around 5-10 nm by the high-resolution TEM (HRTEM). The Ag quantum dots incorporated nanocomposite material could become prominent candidate for diverse applications including photovoltaic, catalysis, and biosensors etc.

Tuning the conditions for the deposition of nanocrystalline diamond by hot filament chemical vapour deposition.

Although large focus has been placed into the deposition of nanocrystalline and ultra-nanocrystalline diamond films, most of this research uses microwave plasma assisted CVD systems. However, the growth conditions used in microwave systems cannot be directly used in hot-filament CVD systems. This paper, aims to enlarge the knowledge of the diamond film depositing process. H2/CH4/Ar gas mixtures have been used to deposit micro, nano and ultra-nanocrystalline diamond films by hot-filament CVD systems. Additionally, the distance between the filaments array and the substrate was varied, in order to observe its effect and consequently the effect of a lower substrate temperature in the nucleation density and deposition. All the samples were characterized for microstructure and quality, using scanning electron microscopy and Raman spectroscopy.

Nanocrystalline diamond coatings for mechanical seals applications.

A mechanical seal is a type of seal used in rotating equipment, such as pumps and compressors. It consists of a mechanism that assists the connection of the rotating shaft to the housings of the equipments, preventing leakage or avoiding contamination. A common cause of failure of these devices is end face wear out, thus the use of a hard, smooth and wear resistant coating such as nanocrystalline diamond would be of great importance to improve their working performance and increase their lifetime. In this paper, different diamond coatings were deposited by the HFCVD process, using different deposition conditions. Additionally, the as-grown films were characterized for, quality, morphology and microstructure using scanning electron microscopy (SEM) and Raman spectroscopy. The topography and the roughness of the films were characterized by atomic force microscopy (AFM).

Comparative study of nanocrystalline diamond deposition on WC-Ni and WC-Co substrates.

Tungsten carbide alloys possess a large number of applications, due to its high hardness, high resistance to heat and to wear, which makes it ideal to be used in wear parts of machinery or on surfaces liable to corrosion, abrasion or high temperatures. For practical applications, it is alloyed with cobalt (Co) or nickel (Ni) in order to improve its properties. The increasing demand of broadening the operation limits of some components, impose the need to improve its life time. Coating these parts with hard and smooth diamond thin film may improve the wear performance and decrease their roughness and friction coefficient. In this work, a comparative study of nanodiamond films deposit onto WC-Co and WC-Ni, by means of a hot-filament Chemical Vapour Deposition (HFCVD) system, is presented. The study was accomplished by varying the CH4/H2/Ar gas ratio of the deposition process. The substrate temperature was kept low (< 700 degrees C) to minimize the thermal stress in the coating-substrate system. The microstructure of the deposited diamond film was characterized using Scanning Electron Microscopy (SEM), Raman spectroscopy and X-ray diffraction spectroscopy. Roughness of the working surfaces were also accessed prior and after the depositions.

Evaluation of diamond coatings on optical fibre sensors for biological use.

The inscription of a Fibre Bragg Grating (FBG) in optical fibres allows them to be used as sensors, being capable of decoding small variations of strain; temperature; pressure; loading; bending; or even refractive index, by means of a shift in the reflected wavelength. Nevertheless, broadening their sensitivity and operation range would be desirable. This may be achieved by appropriated fibre coating. Diamond possesses a set of extreme properties, such as high thermal conductivity, hardness and resistance to hazard environments. Furthermore, it is known for its excellent biocompatible response, so it may be suitable to be used as a coating material for biological sensors. In this paper, the results of the optimization process of diamond coatings on optical fibre sensors is presented, considering their potential use for practical biological purposes.

Local piezoelectric properties of ZnO thin films prepared by RF-plasma-assisted pulsed-laser deposition method.

Zinc oxide (ZnO) thin films were grown on uncoated and zinc-coated Corning glass substrates by pulsed-laser deposition (PLD). X-ray diffraction measurements revealed that the as-deposited films are polycrystalline having preferential orientation along the [0002] and [[Formula: see text]] directions. Transmittance spectroscopy verified that the as-deposited films are transparent with a direct bandgap of about 3.28 eV at room temperature. Piezoresponse imaging and local hysteresis loop acquisition were performed to characterize the piezoelectric and possible ferroelectric properties of the films. The out-of-plane (effective longitudinal, d(parellel)) and in-plane (effective shear, d(perpendicular)) coefficients were estimated from the local piezoresponse based on the comparison with LiNbO(3) single crystals. Measurements of all three components of piezoresponse (one longitudinal and two shear signals) allowed constructing piezoelectric maps for polycrystalline ZnO and to relate the variation of piezoelectric properties to the crystallographic and grain structure of the films. A shifted piezoresponse hysteresis loop under high voltages hints at the possible pseudoferroelectricity, as discussed recently by Tagantsev (2008 Appl. Phys. Lett. 93 202905).

Investigation of the stiffness and yield behaviour of melt-intercalated poly(methyl methacrylate)/organoclay nanocomposites: characterisation and modelling.

The elastic modulus and yield stress behaviour of a melt intercalated Poly(methylmethacrylate)/ organoclay (PMMA/C30B and PMMA/C20A) were studied using uniaxial tensile tests at different temperatures and different strain rate. The stress-strain response was obtained for different loading rates and different test temperature. Both the stiffness and the yield stress were then clearly identified as function of strain rate and temperature. Our experimental results show that the yield stress and modulus of both PMMA/C20A and PMMA/C30B organoclay nanocomposites are very sensitive to clay concentration, strain rate and temperature. A micromechanically-based composite approach was used to predict the yield stress of both PMMA/C20A and PMMA/C30B organoclay nanocomposites. The results obtained from the model are in good agreement with our experimental results. As expected, the activation enthalpy of cooperative model increased slightly while the activation volume decreases slightly with the clay concentration.

Synthesis and field emission properties of ultra-nanocrystalline diamond fibers and helices.

We propose a novel template method for large scale synthesis of Ultra-Nanocrystalline Diamond (UNCD) fibres and helices with lengths of thousands of microns and diameters ranging from 0.5 to 5 microm: (i) Large quantities of submicrometer- or nanometer-diameter silica (a-SiO2) nanostructures, with lengths in the order of 2 to 4 mm, were synthesized by Vapor-Liquid-Solid (VLS) method; (ii) UNCD coating of as-synthesized a-SiO2 micro- or nanonanostructures by Microwave Plasma Chemical Vapour Deposition (MPCVD) technique in hydrogen-deficient condition. Electron Field Emission (EFE) of as-synthesized UNCD structures was observed with a threshold field of 3.4 V/microm. These micro- or nanostructures may find potential applications in high power electronics, vertical field-effect transistors in vacuum electronics, heat sinks in microelectronics and structural materials in Micro- and Nano-Electro-Mechanical Systems (MEMS/NEMS). The successful preparation of various types of UNCD structures suggests that this templating process can be used for a wide range of materials.

Effects of bias voltage on diamond like carbon coatings deposited using titanium isopropoxide (TIPOT) and acetylene/argon mixtures onto various substrate materials.

RF-PECVD was used to prepare amorphous of carbon (DLC) onto stainless steel 316 and glass substrates. The substrates were negatively biased at between 100 V to 400 V. Thin films of DLC have been deposited using C2H2 and titanium isopropoxide (TIPOT). Argon was used to generate the plasma in the PECVD system chamber. DEKTAK 8 surface stylus profilometer was used to measure the film thickness and the deposition rate was calculated. Micro Raman spectroscopy was employed to determine the chemical structure and bonding present in the films. Composition analysis of the samples was carried out using VGTOF SIMS (IX23LS) instrument. In addition, X-ray photoelectron spectroscopy (XPS) was used to analyze the composition and chemical state of the films. The wettability of the films was examined using the optical contact angle meter (CAM200) system. Two types of liquids with different polarities were used to study changes in the surface energy. The as-grown films were in the thickness range of 200-400 nm. Raman spectroscopy results showed that the I(D)/I(G) ratio decreased when the bias voltage on the stainless steel substrates was increased. This indicates an increase in the graphitic nature of the film deposited. In contrast, on the glass substrates the I(D)/I(G) ratio increased when the bias voltage was increased indicates a greater degree of diamond like character. Chemical composition determined using XPS showed the presence of carbon and oxygen in both samples on glass and stainless steel substrates. Both coatings the contact angle of the films decreased except for 400 V which showed a slight increase. The oxygen is thought to play an important role on the polar component of a-C.

Closed field unbalanced magnetron sputtering ion plating of Ni/Al thin films: influence of the magnetron power.

In this study NiAl thin films have been deposited using closed field unbalanced magnetron sputtering Ion plating (CFUBMSIP). The influence of magnetron power has been investigated using dense and humongous NiAl compound targets onto stainless steel and glass substrates. Potential applications include tribological, electronic media and bond coatings in thermal barrier coatings system. Several techniques has been used to characterise the films including surface stylus profilometry, energy dispersive spectroscopy (EDAX), X-Ray diffraction (XRD) Composition analysis of the samples was carried out using VGTOF SIMS (IX23LS) and Atomic force microscopy (AFM). Scratch tester (CSM) combined with acoustic emission singles during loading in order to compare the coating adhesion. The acoustic emission signals emitted during the indentation process were used to determine the critical load, under which the film begins to crack and/or break off the substrate. The average thickness of the films was approximately 1 um. EDAX results of NiAl thin films coating with various magnetron power exhibited the near equal atomic% Ni:Al. The best result being obtained using 300 W and 400 W DC power for Ni and Al targets respectively. XRD revealed the presence of beta NiAl phase for all the films coatings. AFM analysis of the films deposited on glass substrates exhibited quite a smooth surface with surface roughness values in the nanometre range. CSM results indicate that best adhesion was achieved at 300 W for Ni, and 400 W for Al targets compared to sample other power values. SIMS depth profile showed a uniform distribution of the Ni and Al component from the surface of the film to the interface.

Growth and characterisation of NiAl and N-doped NiAl films deposited by closed field unbalanced magnetron sputtering ion plating using elemental ni and Al targets.

Closed Field Unbalanced Magnetron Sputtering Ion Plating (CFUBMSIP) has been used to deposit undoped and nitrogen doped NiAI thin films onto glass and stainless steel 316 substrates. These films have potential applications in tribological, electronic media and thermal barrier coatings. The surface characteristics, composition, mechanical and structural properties have been investigated using stylus profilometry, X-ray diffraction (XRD), Energy dispersive spectroscopy (EDAX), Atomic force microscopy (AFM) and nanoindentation. The average thickness of the films was approximately 1 microm. The X-ray diffraction spectra revealed the presence of the beta NiAl phase. The EDAX results revealed that all of the undoped and nitrogen doped NiAl thin films exhibited the near equiatomic NiAl composition with the best results being achieved using 300 Watts DC power for Ni and 400 Watts DC power for Al targets respectively. AFM results of both types of films deposited on glass samples exhibited a surface roughness of less than 100 nm. The nanoindenter results for coatings on glass substrates displayed hardness and elastic modulus of 7.7 GPa and 100 GPa respectively. The hardest coatings obtained were obtained at 10% of nitrogen.

Ferromagnetic behaviour of nickel contacted multiwalled carbon nanotubes.

A novel method for the contact of ferromagnetic nano-nickel onto multiwalled carbon nanotubes (MWCNTs) is proposed in this work. The process involves the decomposition of the precursor: nickel carbonyl-Ni(CO)4 into nickel and CO by laser chemical vapour deposition at 150-200 degrees C and the deposition of nano-nickel onto MWCNTs. Field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), HR (High resolution) TEM, and Raman spectroscopy were employed for the detailed analysis of the nickel contacted MWCNTs. The ferro-magnetic nature of the sample was confirmed by Super-conducting Quantum Interference Device (SQUID) analysis.

UV emission from patterned growth of ZnO nanowires.

Patterned and high-density ZnO nanowires were fabricated on a large area P type silicon (100) through Vapor-Liquid-Solid approach. An aluminium mask was used for the patterned deposition of gold catalyst. ZnO nanowires grown with the aid of gold catalyst were well aligned and had dimensions of 30-80 nm diameter and 0.5-2 microm length. The perfect crystallinity and orientation [0002] of the nanowires were confirmed by high-resolution transmission electron microscopy (HR-TEM). Low-temperature photoluminescence spectrum exhibits an intensive UV emission at approximately 380 nm and a weak broad green band at approximately 530 nm which is detected under an optical excitation of 325 nm wavelength of He-Cd laser. These arrays of ZnO nanowires could have myriad applications in nanolasers, optoelectronic devices and optical interconnects.

Towards optimization of time modulated chemical vapour deposition for nanostructured diamond films on Ti6Al4V.

In this paper, we report the use of the TMCVD technique for the optimisation of deposited diamond films onto Ti6Al4V substrates. A number of samples were made varying the experimental parameters. The specimen surfaces were characterised using micro Raman spectra and SEM analyses. Results show that very different surface finish (from micro to nanostructures) and film characteristics can be obtained from the experimental parameters used. The quality of deposited diamond is very dependant on the experimental settings and process. It was found that lower residual stresses are developed using the TMCVD technique than with conventional CVD but depend on the structural diamond growth during the process. The quality of the deposited film was evaluated as a function of diamond to amorphous carbon ratio but showed no direct relation with the surface finish since it characterises the quality of the deposited diamond but not the quality of the film surface.

Hydrogen in chemical vapour deposited carbon nanotubes: an active site for functionalization.

The presence of hydrogen in as-grown carbon nanotubes (CNTs) synthesized by microwave plasma (MP) chemical vapour deposition (CVD) technique is demonstrated. Our results showed that the MPCVD, as-grown CNTs were hydrogenated consisting of C-H bonds; whereas, the tubes synthesized by arc discharge consisted of non-hydrogenated multi-walled CNTs. Fourier transform infrared spectroscopy (FTIR) and micro-Raman spectroscopy techniques were used to detect C-H bonding in the as-grown CNTs. The effective functionalization of as-grown hydrogenated CNTs grown using a microwave CVD process is first time demonstrated by laser assisted CVD process. It was found that the laser-assisted CVD process resulted in the termination of hydrogen and the oxidation of as-grown CNT structure leading to the carboxylic group attachment. The FTIR results show the presence of -OH and C=O bonds in the functionalized samples. However, the non-hydrogenated CNTs could not be effectively functionalized by the same process, probably due to the fact that it did not contain active sites pre-requisite for functionalization, as did the CVD grown samples. The functionalization of CVD grown tubes is believed to take place at the 'active' hydrogen-terminated sites on the CNT surfaces.

Hydrogen adsorption onto nickel modified carbon nanotubes.

The Hot Filament Chemical Vapour Deposition (HFCVD) method was employed to study hydrogen adsorption on multi-walled carbon nanotubes (MWCNTs) modified by nickel doping. Prior to the nickel doping, effective functionalisation of CNTs was achieved by treating them in HNO3/H2O2 medium. Samples were characterized using Scanning Electron Microscopy (SEM), Energy Dispersive X-ray (EDS), and Fourier Transform Infrared (FTIR) and Raman spectroscopy techniques. SEM analyses revealed the morphology of the samples and the presence of nickel was identified by EDS analyses. Raman analysis revealed the enhancement of defects on the CNTs after the nickel modification. The defects created along with the catalytic activity of nickel supplied more hydrogen access to the CNTs. This was inferred from highest intensity ratio of D and G band (ID/IG) for hydrogen treated samples. However, FTIR spectra did not exhibit any C-H related bands. This confirms that the adsorption of hydrogen onto CNTs is primarily by surface adsorption.

Selective growth of vertically aligned carbon nanotubes by double plasma chemical vapour deposition technique.

The selective growth of vertically aligned carbon nanotubes (VACNTs) on large area copper substrates was carried out using a double plasma hot-filament chemical vapour deposition system. Three independent power supplies were used to produce two glow discharges within the vacuum reactor. The generation of two glow discharges and the efficient utilization of the electric fields, by controlling the key process parameters, enabled the production of VACNTs. Morphology, density and structure of carbon nanotubes were characterized using Scanning Electron Microscopy and Raman Spectroscopy.

Prediction of the mechanical properties of hydroxyapatite/polymethyl methacrylate/carbon nanotubes nanocomposite.

In this work carbon nanotubes (CNTs) were used to increase the strength and toughness of the hydroxyapatite (HA) and consequently to reduce its brittleness. The combination of CNT, HA and polymethyl methacrylate (PMMA) has led to a new composite material, which has mechanical properties superior to those of conventional HA/PMMA for biomedical scaffold in tissue engineering. PMMA is a well known bone cement which is highly compatible with HA and also it can act as a functionalizing/linking material with HA. The mechanical properties of the new nanocomposite were predicted with a self-consistent computational model taking into account the structure morphology and the orientation of the CNTs. CNT reinforced HA composite is shown to be a promising coating material for high-load-bearing metal implants. The development of this new nanocomposite based on HA/PMMA and CNTs, may significantly contribute to the bond strength of the HA/PMMA metal interface and the overall mechanical properties of the HA/PMMA coating.

Surface engineering of artificial heart valve disks using nanostructured thin films deposited by chemical vapour deposition and sol-gel methods.

Pyrolytic carbon (PyC) is widely used in manufacturing commercial artificial heart valve disks (HVD). Although PyC is commonly used in HVD, it is not the best material for this application since its blood compatibility is not ideal for prolonged clinical use. As a result thrombosis often occurs and the patients are required to take anti-coagulation drugs on a regular basis in order to minimize the formation of thrombosis. However, anti-coagulation therapy gives rise to some detrimental side effects in patients. Therefore, it is extremely urgent that newer and more technically advanced materials with better surface and bulk properties are developed. In this paper, we report the mechanical properties of PyC-HVD, i.e. strength, wear resistance and coefficient of friction. The strength of the material was assessed using Brinell indentation tests. Furthermore, wear resistance and coefficient of friction values were obtained from pin-on-disk testing. The micro-structural properties of PyC were characterized using XRD, Raman spectroscopy and SEM analysis. Also in this paper we report the preparation of freestanding nanocrystalline diamond films (FSND) using the time-modulated chemical vapour deposition (TMCVD) process. Furthermore, the sol-gel technique was used to uniformly coat PyC-HVD with dense, nanocrystalline-titanium oxide (nc-TiO2) coatings. The as-grown nc-TiO2 coatings were characterized for microstructure using SEM and XRD analysis.