Single crystal CVD diamond growth strategy by the use of a 3D geometrical model: Growth on (113) oriented substrates

The quality of single crystal diamond obtained by microwave CVD processes has been drastically improved in the last 5 years thanks to surface pretreatment of the substrates [A. Tallaire, J. Achard, F. Silva, R.S. Sussmann, A. Gicquel, E. Rzepka, Physica Status Solidi (A) 201, 2419-2424 (2004); G. Bogdan, M. Nesladek, J. D'Haen, J. Maes, V.V. Moshchalkov, K. Haenen, M. D'Olieslaeger, Physica Status Solidi (A) 202, 2066-2072 (2005); M. Yamamoto, T. Teraji, T. Ito, Journal of Crystal Growth 285, 130-136 (2005)]. Additionally, recent results have unambiguously shown the occurrence of (110) faces on crystal edges and (113) faces on crystal corners [F. Silva, J. Achard, X. Bonnin, A. Michau, A. Tallaire, O. Brinza, A. Gicquel, Physica Status Solidi (A) 203, 3049-3055 (2006)]. We have developed a 3D geometrical growth model to account for the final crystal morphology. The basic parameters of this growth model are the relative displacement speeds of (111), (110) and (113) faces normalized to that of the (100) faces, respectively alpha, beta, and gamma. This model predicts both the final equilibrium shape of the crystal (i.e. after infinite growth time) and the crystal morphology as a function of alpha, beta, gamma, and deposition time.

An optimized operating point, deduced from the model, has been validated experimentally by measuring the growth rate in (100), (111), (110), and (113) orientations. Furthermore, the evolution of alpha, beta, gamma as a function of methane concentration in the gas discharge has been established. From these results, crystal growth strategies can be proposed in order, for example, to enlarge the deposition area. In particular, we will show, using the growth model, that the only possibility to significantly increase the deposition area is, for our growth conditions, to use a (113) oriented substrate. A comparison between the grown crystal and the model results will be discussed and characterizations of the grown film (Photoluminescence spectroscopy, EPR, SEM) will be presented. (C) 2008 Elsevier B.V. All rights reserved.

Multilayered micro/nanocrystalline CVD diamond coatings for biotribology

In the present work multilayered micro/nanocrystalline (MCD/NCD) diamond coatings were developed by Hot Filament Chemical Vapour Deposition (HFCVD). The aim was to minimize the surface roughness with a top NCD layer, to maximize adhesion onto the Si3N4 ceramic substrates with a starting MCD coating and to improve the mechanical resistance by the presence of MCD/NCD interfaces in these composite coatings. This set of features assures high wear resistance and low friction coefficients which, combined to diamond biocompatibility, set this material as ideal for biotribological applications. The deposition parameters of MCD were optimized using the Taguchi method, and two varieties of NCD were used: NCD-1, grown in a methane rich gas phase, and NCD-2 where a third gas, Argon, was added to the gas mixture. The best combination of surface pre-treatments in the Si3N4 substrates is obtained by polishing the substrates with a 15 μm diamond slurry, further dry etching with CF4 plasma for 10 minutes and final ultrasonic seeding in a diamond powder suspension in ethanol for 1 hour. The interfaces of the multilayered CVD diamond films were characterized with high detail using HRTEM, STEM-EDX and EELS. The results show that at the transition from MCD to NCD a thin precursor graphitic film is formed. On the contrary, the transition of the NCD to MCD grade is free of carbon structures other than diamond, as a result of the richer atomic hydrogen content and of the higher substrate temperature for MCD deposition. At those transitions, WC nanoparticles were found due to contamination from the filament, being also present at the first interface of the MCD layer with the silicon nitride substrate. In order to study the adhesion and mechanical resistance of the diamond coatings, indentation and particle jet blasting tests were conducted, as well as tribological experiments with homologous pairs. Indentation tests proved the superior behaviour of the multilayered coatings that attained a load of 800 N without delamination, when compared to the mono and bilayered ones. The multilayered diamond coatings also reveal the best solid particle erosion resistance, due to the MCD/NCD interfaces that act as crack deflectors. These results were confirmed by an analytical model on the stress field distribution based on the von Mises criterion. Regarding the tribological testing under dry sliding, multilayered coatings also exhibit the highest critical load values (200N for Multilayers with NCD-2). Low friction coefficient values in the range μ=0.02- 0.09 and wear coefficient values in the order of ~10-7 mm3 N-1 m-1 were obtained for the ball and flat specimens indicating a mild wear regime. Under lubrication with physiological fluids (HBSS e FBS), lower wear coefficient values ~10-9-10-8 mm3 N-1 m-1) were achieved, governed by the initial surface roughness and the effective contact pressure.

Self-mated tribological systems based on multilayer micro/nanocrystalline CVD diamond coatings

The tribological response of multilayer micro/nanocrystalline diamond coatings grown by the hot filament CVD technique is investigated. These multigrade systems were tailored to comprise a starting microcrystalline diamond (MCD) layer with high adhesion to a silicon nitride (Si3N4) ceramic substrate, and a top nanocrystalline diamond (NCD) layer with reduced surface roughness. Tribological tests were carried out with a reciprocating sliding configuration without lubrication. Such composite coatings exhibit a superior critical load before delamination (130–200 N), when compared to the mono- (60–100 N) and bilayer coatings (110 N), considering ∼10 µm thick films. Regarding the friction behaviour, a short-lived initial high friction coefficient was followed by low friction regimes (friction coefficients between 0.02 and 0.09) as a result of the polished surfaces tailored by the tribological solicitation. Very mild to mild wear regimes (wear coefficient values between 4.1×10−8 and 7.7×10−7 mm3 N−1 m−1) governed the wear performance of the self-mated multilayer coatings when subjected to high-load short-term tests (60–200 N; 2 h; 86 m) and medium-load endurance tests (60 N; 16 h; 691 m).

Micromorphologic assessment of CVD (chemical vapor deposition) and conventional diamond tips and their cutting effectiveness

The aim of this study was to compare the micromorphology of CVD diamond tips coupled to ultrasound with conventional high speed diamond tips after cavity preparations, and to measure the width and depth of the cavities obtained. Two hundred bovine teeth were divided into 20 subgroups. Each of the diamond tips (10 CVD and 10 conventional) were used to prepare 10 standardized cavities, using an apparatus that controlled the time (t: 27 s), speed (5.3 mm/s) and load (0.012 KGF) of the tip against the teeth during preparation. The unused and the used (after one, five and 10 preparations) tips were analyzed by scanning electronic microscopy. The images were randomly assessed by 3 examiners with regard to the presence or absence of micromorphologic alterations. Cavity measurements were made after visualization under a stereoscopic microscope. Cavity widths and depths were analyzed by the ANOVA Factorial test (p < 0.05). The CVD diamond tips presented less wear than the conventional tips after all the cavity preparations performed, but produced shallower cavities that were equivalent in width to those made by conventional tips after the fifth preparation. CVD diamond tips may be suggested as an alternative to conventional diamond tips due to their conservative preparation and greater longevity.

Cutting characteristics of dental diamond burs made with CVD technology

The aim of this study was to determine the cutting ability of chemical vapor deposition (CVD) diamond burs coupled to an ultrasonic dental unit handpiece for minimally invasive cavity preparation. One standard cavity was prepared on the mesial and distal surfaces of 40 extracted human third molars either with cylindrical or with spherical CVD burs. The cutting ability was compared regarding type of substrate (enamel and dentin) and direction of handpiece motion. The morphological characteristics, width and depth of the cavities were analyzed and measured using scanning electron micrographs. Statistical analysis using the Kruskal-Wallis test (p < 0.05) revealed that the width and depth of the cavities were significantly greater when they were prepared on dentin. Wider cavities were prepared when the cylindrical CVD bur was used, and deeper cavities resulted from preparation with the spherical CVD bur. The direction of handpiece motion did not influence the size of the cavities, and the CVD burs produced precise and conservative cutting.

Influence of CVD diamond tips and Er:YAG laser irradiation on bonding of different adhesive systems to dentin

Aim: The aim of this study was to compare the microtensile bond strength of three adhesive systems, using different methods of dentin preparation. Materials and methods: A hundred and eight bovine teeth were used. The dentin from buccal face was exposed and prepared with three different methods, divided in 3 groups: Group 1 (DT)- diamond tip on a high-speed handpiece; Group 2 (CVD)-CVD tip on a ultrasonic handpiece; Group 3 (LA)-Er: YAG laser. The teeth were divided into 3 subgroups, according adhesive systems used: Subgroup 1-Adper Single Bond Plus/3M ESPE (SB) total-etch adhesive; Subgroup 2-Adper Scotchbond SE/3M ESPE (AS) selfetching adhesive; Subgroup 3-Clearfil SE Bond/Kuraray (CS) selfetching adhesive. Blocks of composite (Filtek Z250-3M ESPE) 4 mm high were built up and specimens were stored in deionized water for 24 hours at 37°C. Serial mesiodistal and buccolingual cuts were made and stick-like specimens were obtained, with transversal section of 1.0 mm2. The samples were submitted to microtensile test at 1 mm/min and load of 10 kg in a universal testing machine. Data (MPa) were subjected to ANOVA and Tukey's tests (p < 0.05). Results and conclusion: Surface treatment with Diamond or CVD tips associated with Clearfil SE Bond adhesive produced significantly lower bond strength values compared to other groups. Surface treatment with Er: YAG laser associated with Single Bond Plus or Clearfil SE Bond adhesives and surface treatment with CVD tip associated with Adper Scotchbond SE adhesive produced significantly lower bond strength values compared to surface treatment with diamond or CVD tips associated with Single Bond Plus or Adper Scotchbond SE adhesives. Clinical significance: Interactions between laser and the CVD tip technologies and the different adhesive systems can produce a satisfactory bonding strength result, so that these associations may be beneficial and enhance the clinical outcomes.

Self-supporting CVD diamond charge state conversion surfaces for high resolution imaging of low-energy neutral atoms in space plasmas

Two polycrystalline diamond surfaces, manufactured by chemical vapour deposition (CVD) technique, are investigated regarding their applicability as charge state conversion surfaces (CS) for use in a low energy neutral atom imaging instrument in space research. The capability of the surfaces for converting neutral atoms into negative ions via surface ionisation processes was measured for hydrogen and oxygen with particle energies in the range from 100 eV to 1 keV and for angles of incidence between 6 deg and 15 deg. We observed surface charging during the surface ionisation processes for one of the CVD samples due to low electrical conductivity of the material. Measurements on the other CVD diamond sample resulted in ionisation efficiencies of ~2 % for H and up to 12 % for O. Analysis of the angular scattering revealed very narrow and almost circular scattering distributions. Comparison of the results with the data of the CS of the IBEX-Lo sensor shows that CVD diamond has great potential as CS material for future space missions.

A novel Mo-W interlayer approach for CVD diamond deposition on steel

Steel is the most widely used material in engineering for its cost/performance ratio and coatings are routinely applied on its surface to further improve its properties. Diamond coated steel parts are an option for many demanding industrial applications through prolonging the lifetime of steel parts, enhancement of tool performance as well as the reduction of wear rates. Direct deposition of diamond on steel using conventional chemical vapour deposition (CVD) processes is known to give poor results due to the preferential formation of amorphous carbon on iron, nickel and other elements as well as stresses induced from the significant difference in the thermal expansion coefficients of those materials. This article reports a novel approach of deposition of nanocrystalline diamond coatings on high-speed steel (M42) substrates using a multi-structured molybdenum (Mo) - tungsten (W) interlayer to form steel/Mo/Mo-W/W/diamond sandwich structures which overcome the adhesion problem related to direct magnetron sputtering deposition of pure tungsten. Surface, interface and tribology properties were evaluated to understand the role of such an interlayer structure. The multi-structured Mo-W interlayer has been proven to improve the adhesion between diamond films and steel substrates by acting as an effective diffusion barrier during the CVD diamond deposition.

Interface properties and capacitance-voltage behaviour of diamond devices prepared by microwave-assisted CVD

Free standing diamond films were used to study the effect of diamond surface morphology and microstructure on the electrical properties of Schottky barrier diodes. By using free standing films both the rough top diamond surface and the very smooth bottom surface are available for post-metal deposition. Rectifying electrical contacts were then established either with the smooth or the rough surface. The estimate of doping density from the capacitance-voltage plots shows that the smooth surface has a lower doping density when compared with the top layers of the same film. The results also show that surface roughness does not contribute significantly to the frequency dispersion of the small signal capacitance. The electrical properties of an abrupt asymmetric n(+)(silicon)-p(diamond) junction have also been measured. The I-V curves exhibit at low temperatures a plateau near zero bias, and show inversion of rectification. Capacitance-voltage characteristics show a capacitance minimum with forward bias, which is dependent on the environment conditions. It is proposed that this anomalous effect arises from high level injection of minority carriers into the bulk.

Electrical characterization of CVD diamond-n(+) silicon junctions

The electrical characteristics of CVD-diamond/n(+)-Si heterojunction devices are reported. Below 250 K the diodes show an unusual inversion of their rectification properties. This behavior is attributed to an enhanced tunneling component due to interface states, which change their occupation with the applied bias. The temperature dependence of the loss tangent shows two relaxation processes with different activation energies. These processes are likely related with two parallel charge transport mechanisms, one through the diamond grain, and the other through the grain boundary. (C) 2001 Elsevier Science B.V. Ah rights reserved.

Interface properties and capacitance-voltage behaviour of diamond devices prepared by microwave-assisted CVD

Free standing diamond films were used to study the effect of diamond surface morphology and microstructure on the electrical properties of Schottky barrier diodes. By using free standing films both the rough top diamond surface and the very smooth bottom surface are available for post-metal deposition. Rectifying electrical contacts were then established either with the smooth or the rough surface. The estimate of doping density from the capacitance-voltage plots shows that the smooth surface has a lower doping density when compared with the top layers of the same film. The results also show that surface roughness does not contribute significantly to the frequency dispersion of the small signal capacitance. The electrical properties of an abrupt asymmetric n(+)(silicon)-p(diamond) junction have also been measured. The I-V curves exhibit at low temperatures a plateau near zero bias, and show inversion of rectification. Capacitance-voltage characteristics show a capacitance minimum with forward bias, which is dependent on the environment conditions. It is proposed that this anomalous effect arises from high level injection of minority carriers into the bulk.

On natures of sub-gap photoelectric and optical spectra in nitrogen-contaminated nanocrystalline diamond

Experimentally observed optical and photoelectrical spectra of nitrogen-contaminated (unintentionally doped) nano-crystalline CVD diamond films are simulated using semi-empirical adiabatic General Skettrup Model (GSM), which presumes dominant contributions of defect states from sp 3-coordinated intra-granular carbon atoms to intra-band single electron spectrum N(E) of the material. This picture disagrees with a common viewpoint that the N(E) spectrum of the gap states in diamond powders and polycrystalline CVD films mainly originates from π and π* bonds of sp2-coordinated carbon atoms, which are distributed nearly uniformly over outer surfaces and/or interfaces of the diamond grains. The GSM predicts as well strong effect of granular morphology on the density of intra-band defect states in polycrystalline diamonds.