Diamond growth by carbon ion implantation of diamond

Medium energy (5-25 keV) C-13(+) ion implantation into diamond (100) to a fluence ranging from 10(16) cm(-2) to 10(18) cm(-2) was performed for the study of diamond growth via the approach of ion beam implantation. The samples were characterized with Rutherford backscattering/channelling spectroscopy, Raman spectroscopy, X-ray photoemission spectroscopy and Auger electron spectroscopy. Extended defects are formed in the cascade collision volume during bombardment at high temperatures. Carbon incorporation indeed induces a volume growth but the diamond (100) samples receiving a fluence of 4 x 10(17) to 2 x 10(18) at. cm(-2) (with a dose rate of 5 x 10(15) at. cm(-2) s(-1) at 5 to 25 keV and 800 degrees C) showed no He-ion channelling. Common to these samples is that the top surface layer of a few nanometers has a substantial amount of graphite which can be removed by chemical etching. The rest of the grown layer is polycrystalline diamond with a very high density of extended defects.

Ion bombardment as the initial stage of diamond film growth

It is believed that during the initial stage of diamond film growth by chemical-vapor deposition (CVD), ion bombardment is the main mechanism in the bias-enhanced-nucleation (BEN) process. To verify such a statement, experiments by using mass-separated ion-beam deposition were carried out, in which a pure carbon ion beam, with precisely defined low energy, was selected for investigating the ion-bombardment effect on a Si substrate. The results are similar to those of the BEN process, which supports the ion-bombardment-enhanced-nucleation mechanism. The formation of sp(3) bonding is based on the presumption that the time of stress generation is much shorter than the duration of the relaxation process. The ion-bombarded Si is expected to enhance the CVD diamond nucleation density because the film contains amorphous carbon embedded with nanocrystalline diamond and defective graphite. (C) 2001 American Institute of Physics.

Growth-Parameter Spaces and Optical Properties of Cubic Boron Nitride Films on Si(001)

Cubic boron nitride (c-BN) films were deposited on Si(001) substrates in an ion beam assisted deposition (IBAD) system under various conditions, and the growth parameter spaces and optical properties of c-BN films have been investigated systematically. The results indicate that suitable ion bombardment is necessary for the growth of c-BN films, and a well defined parameter space can be established by using the P/a-parameter. The refractive index of BN films keeps a constant of 1.8 for the c-BN content lower than 50%, while for c-BN films with higher cubic phase the refractive index increases with the c-BN content from 1.8 at chi(c) = 50% to 2.1 at chi(c) = 90%. Furthermore, the relationship between n and rho for BN films can be described by the Anderson-Schreiber equation, and the overlap field parameter gamma is determined to be 2.05.

Violet/blue emission from hydrogenated amorphous carbon films deposited from energetic CH3+ ions and ion bombardment

Considering the complexity of the general plasma techniques, pure single CH3+ ion beams were selected for the deposition of hydrogenated amorphous (a) carbon films with various ion energies and temperatures. Photoluminescence (PL) measurements have been performed on the films and violet/blue emission has been observed. The violet/blue emission is attributed to the small size distribution of sp(2) clusters and is related to the intrinsic properties of CH3 terminals, which lead to a very high barrier for the photoexcited electrons. Ion bombardment plays an important role in the PL behavior. This would provide further insight into the growth dynamics of a-C:H films. (C) 2002 American Institute of Physics.

Growth of C36-films on diamond surface through molecular dynamics simulation

In this paper, the initial stage of films assembled by energetic C36 fullerenes on diamond (001)–(2 × 1) surface at low-temperature was investigated by molecular dynamics simulation using the Brenner potential. The incident energy was first uniformly distributed within an energy interval 20–50 eV, which was known to be the optimum energy range for chemisorption of single C36 on diamond (001) surface. More than one hundred C36 cages were impacted one after the other onto the diamond surface by randomly selecting their orientation as well as the impact position relative to the surface. The growth of films was found to be in three-dimensional island mode, where the deposited C36 acted as building blocks. The study of film morphology shows that it retains the structure of a free C36 cage, which is consistent with Low Energy Cluster Beam Deposition (LECBD) experiments. The adlayer is composed of many C36-monomers as well as the covalently bonded C36 dimers and trimers which is quite different from that of C20 fullerene-assembled film, where a big polymerlike chain was observed due to the stronger interaction between C20 cages. In addition, the chemisorption probability of C36 fullerenes is decreased with increasing coverage because the interaction between these clusters is weaker than that between the cluster and the surface. When the incident energy is increased to 40–65 eV, the chemisorption probability is found to increased and more dimers and trimers as well as polymerlike-C36 were observed on the deposited films. Furthermore, C36 film also showed high thermal stability even when the temperature was raised to 1500 K.

Effect of substrate roughness on growth of diamond by hot filament CVD

Polycrystalline diamond coatings are grown on Si (100) substrate by hot filament CVD technique. We investigate here the effect of substrate roughening on the substrate temperature and methane concentration required to maintain high quality, high growth rate and faceted morphology of the diamond coatings. It has been shown that as we increase the substrate roughness from 0.05 mu m to 0.91 mu m (centre line average or CLA) there is enhancement in deposited film quality (Raman peak intensity ratio of sp (3) to non-sp (3) content increases from 1.65 to 7.13) and the substrate temperature can be brought down to 640A degrees C without any additional substrate heating. The coatings grown at adverse conditions for sp (3) deposition has cauliflower morphology with nanocrystalline grains and coatings grown under favourable sp (3) condition gives clear faceted grains.

Diamond growth in combustion flames

Diamond crystallites were synthesized using various oxygen‐hydrocarbon flames. The flames have been profiled in real time using a nonintrusive diagnostic technique. Optical emission spectra for different zones have been recorded and the active species identified. Diamond growth was observed only in the thermodynamically unequilibriated primary combustion zone of the flames. Carbon‐bearing species, atomic hydrogen, and atomic oxygen, noted to be critical for diamond growth, were observed in the flames. The diamond growth was confirmed by x‐ray diffraction, laser‐Raman analysis, and scanning electron microscopy. The study offers the first insight into the flame spectra in the context of diamond synthesis at atmospheric pressures.

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.

The valuable role of renucleation rate in ultrananocrystalline diamond growth

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Atomic-scale characterization of diamond surfaces and fullerene self-assembly

In this thesis, elemental research towards the implantation of a diamond-based molecular quantum computer is presented. The approach followed requires linear alignment of endohedral fullerenes on the diamond C(100) surface in the vicinity of subsurface NV-centers. From this, four fundamental experimental challenges arise: 1) The well-controlled deposition of endohedral fullerenes on a diamond surface. 2) The creation of NV-centers in diamond close to the surface. 3) Preparation and characterization of atomically-flat diamondsurfaces. 4) Assembly of linear chains of endohedral fullerenes. First steps to overcome all these challenges were taken in the framework of this thesis. Therefore, a so-called “pulse injection” technique was implemented and tested in a UHV chamber that was custom-designed for this and further tasks. Pulse injection in principle allows for the deposition of molecules from solution onto a substrate and can therefore be used to deposit molecular species that are not stable to sublimation under UHV conditions, such as the endohedral fullerenes needed for a quantum register. Regarding the targeted creation of NV-centers, FIB experiments were carried out in cooperation with the group of Prof. Schmidt-Kaler (AG Quantum, Physics Department, Johannes Gutenberg-Universität Mainz). As an entry into this challenging task, argon cations were implanted into (111) surface-oriented CaF2 crystals. The resulting implantation spots on the surface were imaged and characterized using AFM. In this context, general relations between the impact of the ions on the surface and their valency or kinetic energy, respectively, could be established. The main part of this thesis, however, is constituted by NCAFM studies on both, bare and hydrogen-terminated diamond C(100) surfaces. In cooperation with the group of Prof. Dujardin (Molecular Nanoscience Group, ISMO, Université de Paris XI), clean and atomically-flat diamond surfaces were prepared by exposure of the substrate to a microwave hydrogen plasma. Subsequently, both surface modifications were imaged in high resolution with NC-AFM. In the process, both hydrogen atoms in the unit cell of the hydrogenated surface were resolved individually, which was not achieved in previous STM studies of this surface. The NC-AFM images also reveal, for the first time, atomic-resolution contrast on the clean, insulating diamond surface and provide real-space experimental evidence for a (2×1) surface reconstruction. With regard to the quantum computing concept, high-resolution NC-AFM imaging was also used to study the adsorption and self-assembly potential of two different kinds of fullerenes (C60 and C60F48) on aforementioned diamond surfaces. In case of the hydrogenated surface, particular attention was paid to the influence of charge transfer doping on the fullerene-substrate interaction and the morphology emerging from self-assembly. Finally, self-assembled C60 islands on the hydrogen-terminated diamond surface were subject to active manipulation by an NC-AFM tip. Two different kinds of tip-induced island growth modes have been induced and were presented. In conclusion, the results obtained provide fundamental informations mandatory for the realization of a molecular quantum computer. In the process it was shown that NC-AFM is, under proper circumstances, a very capable tool for imaging diamond surfaces with highest resolution, surpassing even what has been achieved with STM up to now. Particular attention was paid to the influence of transfer doping on the morphology of fullerenes on the hydrogenated diamond surface, revealing new possibilities for tailoring the self-assembly of molecules that have a high electron affinity.

High rate growth of nanocrystalline diamond films using high microwave power and pure nitrogen/methane/hydrogen plasma

In this work, we investigate the impact of minute amounts of pure nitrogen addition into conventional methane/hydrogen mixtures on the growth characteristics of nanocrystalline diamond (NCD) films by microwave plasma assisted chemical vapour deposition (MPCVD), under high power conditions. The NCD films were produced from a gas mixture of 4% CH4/H2 with two different concentrations of N2 additive and microwave power ranging from 3.0 kW to 4.0 kW, while keeping all the other operating parameters constant. The morphology, grain size, microstructure and texture of the resulting NCD films were characterized by using scanning electron microscope (SEM), micro-Raman spectroscopy and X-ray diffraction (XRD) techniques. N2 addition was found to be the main parameter responsible for the formation and for the key change in the growth characteristics of NCD films under the employed conditions. Growth rates ranging from 5.4 μm/h up to 9.6 μm/h were achieved for the NCD films, much higher than those usually reported in the literature. The enhancing factor of nitrogen addition on NCD growth rate was obtained by comparing with the growth rate of large-grained microcrystalline diamond films grown without nitrogen and discussed by comparing with that of single crystal diamond through theoretical work in the literature. This achievement on NCD growth rate makes the technology interesting for industrial applications where fast coating of large substrates is highly desirable.