Transformation of nano-diamonds to carbon nano-onions studied by X-ray diffraction and molecular dynamics

The transformation of ultra-dispersed diamond nanoparticles of about 50 Å in diameter into carbon nano-onions has been studied by high-energy X-ray diffraction and molecular dynamics simulations using the reactive empirical bond order potential. Structural models have been constructed for pristine nano-diamonds and nano-diamonds annealed at 1673 K, 1973 K and 2273 K. These models have been relaxed using the molecular dynamics method and the model based structure factors and the pair correlation functions are compared with the experimental data. All model relaxations and the X-ray diffraction experiments have been carried out at 300 K. Two starting models consisting of 5460 atoms with a single diamond core and an amorphous-like outer shell and for a twinned diamond core and a similar amorphous outer shell containing in total about 13,500 atoms reproduced correctly features of the experimental data. The atomic models of two intermediate and final fully graphitized structures, consisting of the same numbers of atoms and containing the series of defected icosahedral fullerenes describe satisfactorily the atomic arrangements for the samples annealed at 1673 K, 1973 K and 2273 K. The generated models of the nano-diamonds and the nano-onions are related to the previous observations by high-resolution transmission electron microscopy.     

The atomic scale structure of nanographene platelets studied by X-ray diffraction,high-resolution transmission electron microscopy and molecular dynamics

The atomic structure of commercially available nanographene platelets has been studied by high energy X-ray diffraction, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy and molecular dynamics simulations using the reactive empirical bond order potential. Atomic models of the structure have been constructed and then relaxed using the molecular dynamics method and the model based simulations are compared with the experimental data both in reciprocal and real space. All model relaxations and the X-ray diffraction experiments have been carried out at 300 K. The proposed models consisting of about 2500 carbon atoms arranged within four graphitic layers with a diameter of 46 Å, reproduced correctly all features of the experimental data. The atomic arrangement within an individual layer can be described in terms of the paracrystalline ordering, in which lattice distortions propagate proportionally to the square root of interatomic distances. The paracrystalline structure was simulated by introducing the topological point defects such as the Stone–Thrower–Wales defects, single- and double-vacancies, randomly distributed in the network. Such defects lead to curvature of individual layers and this effect was also analyzed. The generated models are related to the observations by high-resolution transmission electron microscopy.     

Real time investigation of diamond nucleation by laser scattering

Diamond nucleation onto diamond-free substrates remains a major challenge for most diamond films applications. In order to quickly form a continuous film across a given surface, several pre-treatments of the substrate have been developed to increase the nucleation density. Amongst those, Bias Enhanced Nucleation (BEN) has been used intensively for many applications, including for instance the synthesis of ultra-thin diamond films, heteroepitaxial diamond films, or nanodiamond films. The determination of the nucleation kinetics during the BEN pretreatment is particularly relevant in order to obtain fundamental informations about plasma/surface interactions and associated nucleation mechanisms. Besides, it is a key challenge to optimise the BEN step for specific applications, such as epitaxy or high nucleation density. The sequential approach which consists of interrupting the process at different time intervals for nucleation density measurement is time consuming and not accurate enough. We propose a real time investigation of diamond nucleation by laser scattering applied to the Bias Enhanced Nucleation (BEN) pre-treatment on silicon carbide. The Microwave Plasma Chemical Vapour Deposition (MPCVD) reactor was equipped with a laser reflectometry system associated with a lock-in laser intensity measurement. In parallel, a kinetics model of nucleation was drawn based on light diffusion of diamond nanoparticles according to their size and density. The modelling results were compared to the experimental data, and characteristic kinetic parameters were worked out for diamond nucleation on silicon carbide. In this study we demonstrated that using a model based on nanoparticles laser scattering it is possible to determine in real time the kinetics of diamond nucleation.     

Diamond nanoparticles to carbon onions transformation: X-ray diffraction studies

Carbon onions prepared by high temperature annealing of ultradispersed diamond nanoparticles of about 5 nm in average diameter have been studied by X-ray diffraction using synchrotron radiation. The X-ray diffraction patterns show transformation of the diamond nanoparticles with sp³ bonds into spherical carbon onions containing remaining diamond-like core and then into polyhedral onions with facets on their outer part and pure sp² graphitic bonds. The prepared onions form concentric-shell particles which comprise of about ten shells with an intershell distance of 0.35-0.36 nm. The large intershell distance suggests a considerable reduction in intershell interaction when compared to perfect graphite. The X-ray data are related to the previously performed studies by electron energy-loss spectroscopy and electron spin resonance.     

Etching mechanism of diamond by Ni nanoparticles for fabrication of nanopores

Nanopores in insulating solid state membranes have recently emerged as potential candidates for sorting, probing and manipulating biopolymers, such as DNA, RNA and proteins in their native environment. Here a simple, fast and cost-effective etching technique to create nanopores in diamond membrane by self-assembled Ni nanoparticles is proposed. In this process, a diamond film is annealed with thin Ni layers at 800–850 °C in hydrogen atmosphere. Carbon from the diamond–metal interface is removed as methane by the help of Ni nanoparticles as catalyst and consequently, the nanoparticles enter the crystal volume. In order to optimize the etching process and understand the mechanism the annealed polycrystalline and nanocrystalline diamond films were analyzed by X-ray photoelectron spectroscopy (XPS), and the gas composition during the process was investigated by quadrupole mass spectrometer. With this technique, nanopores with lateral size in the range of 15–225 nm and as deep as about 550 nm in diamond membrane were produced without any need for lithography process. A model for etching diamond with Ni explaining the mechanism is discussed.     

Computer-simulated diamond/graphite structure based on the diffraction pattern

Theoretical diffraction patterns have been computed with the use of a known spatial structure of a spherical two-phase nanocrystal particle consisting of a diamond core and an outer graphite shell. This approach not only allowed direct determination of the structure of nanosized crystals but also revealed more exactly its minor details, namely, the effect of the interface (distances between outer diamond core atoms and inner graphite shell atoms) on the diffraction of two-phase nanoparticles.     

Synthesis of large single crystal diamond plates by high rate homoepitaxial growth using microwave plasma CVD and lift-off process

A process of making a large, thick single crystal CVD diamond plates has been developed. This process consists of high rate homoepitaxial growth of CVD diamond and subsequent lift-off process using ion implantation. By using this process, single crystal CVD diamond plates with the size of about 10 × 10 × 0.2–0.45 mm³ have been successfully fabricated. The crystallinity of the CVD diamond plates has been evaluated by X-ray topography, polarized light microscopy and high resolution X-ray diffraction. The results indicate the pretreatment of the seed substrate has strong effect on the crystallinity of the CVD diamond plates.     

Processing–structure–adhesion relationship in CVD diamond films on titanium substrates

The hardness and adhesion properties of diamond films deposited on pure Ti and Ti–6Al–4V alloy are related to the structural characteristics of the films and of the intermediate layers formed at the film/substrate interface. Deposition experiments were performed by hot-filament CVD systematically varying the deposition temperature (650–850 °C) and time (60–360 min). The morphology and structure of the coatings and interfaces were investigated by optical and electron microscopy (SEM) and by the combined use of reflection diffraction (RHEED) and X-ray powder diffraction (XRPD), used also in the GID (Grazing Incidence Diffraction) mode. Hardness measurements (HV) of the deposits were made at a constant loading of 25 g on specifically prepared transversal sections of the specimen. Only small differences concerning the mechanical properties have been found for films grown on pure Ti and Ti–6Al–4V substrates. Adhesion of diamond on the substrate has been determined by the scratch test. The analysis of the micrographs of the indenter scratches and of the fracture-correlated acoustic emissions clearly indicates the occurrence of a multi-step detachment process, leading progressively to effective delamination of the diamond coatings.     

Are nanotubes and carbon nanostructures the precursors of coexisting graphite and micro-diamonds in UHP rocks?

A transmission electron microscopy study of garnet from diamond-grade gneisses of the Betic Cordillera (Spain) has revealed the presence of abundant, previously unrecognized, nanosized carbonaceous grains, coexisting with micrometer-sized graphite and diamond. The nanosized particles occur as multiwall nanotubes, and as polyhedral and quasi-spherical graphite + diamond nanoparticles, whereas larger graphite particles appear as rods and as tabular crystals. The topotactic relationships between graphite in nanoparticles and in micrometer-sized particles and the host garnet suggest that carbon nano- and microparticles precipitated from an originally homogeneous solid solution of carbon in the garnet. Based on orientation relationships and on experimental data it is suggested that the three main types of nanosized particles (nanospheres, polyhedral particles and nanotubes) were the precursor of the three main types of larger carbon phases (diamond, tabular and rod-shaped graphite particles, respectively). It is interpreted, as in the case of diamond-graphite nanocomposites, that diamond formation in the core of the nanoparticles is due to an increase of the cross-links between the layers, and then, to the collapse, at a certain point, of the whole graphite structure into diamond. This finding opens a new door for explaining the origin of some metamorphic diamonds and of coexisting graphite and diamond in ultrahigh pressure rocks.     

Extreme UV single crystal diamond Schottky photodiode in planar and transverse configuration

We report on the study of the performances of two extreme ultraviolet (EUV) photovoltaic single crystal diamond Schottky diodes based on metal/intrinsic/p-type diamond junction developed at the University of Rome “Tor Vergata” and having different contact geometries. One detector operates in transverse configuration with a semitransparent metallic contact evaporated on the intrinsic diamond surface, while the second one operates in planar configuration with an interdigitated contact structure on the growth surface of the intrinsic diamond layer. Both devices can work in an unbiased mode by using the built-in potential arising from the electrode–diamond interface and show excellent rectifying properties with a rectification ratio of about 10⁸.The devices have been characterized in the EUV spectral region by using He–Ne DC gas discharge radiation source and a toroidal grating vacuum monochromator, with a 5 Å wavelength resolution. The extremely good signal-to-noise ratio, the reproducibility of the device response, the absence of persistent photoconductivity and undesirable pumping effects suggest the high quality of our CVD diamond for UV applications. The external quantum efficiency (EQE) as well as the responsivity have been measured in the spectral range from 20 to 120 nm and opposite behaviours for the two different geometries proposed have been observed.     

Tuning the Properties of Ba-M Hexaferrite BaFe11.5Co0.5O19: A Road Towards Diverse Applications

The development of hexaferrite nanoparticles is scrutinized as potential sorbents for the removal of chromium (Cr) ions from aqueous chromium-containing solutions in a batch adsorption experiment. The transition metal Co doped BaFe₁₂O₁₉ hexaferrite compounds (BHF) have been synthesized successfully via citrate auto combustion technique. The structure, surface morphology and magnetic properties of the samples were studied. X-ray diffraction pattern ratifies the existence of hexagonal phase as a main phase for the prepared samples. The average crystallite sizes are found in the range of 47–49 nm. The high-resolution transmission electron microscopy (HRTEM), as well as the Fourier, transform infrared spectrophotometry results confirm an M-type hexagonal structure existing. The χ-T indicates the temperature-dependent ferromagnetic behavior of BHF nanoparticles. The derivative shows a single transition temperature Tc at 698 °C, and 710 °C for BHF and BCHF respectively. The prepared samples are utilized as an adsorbent for the removal of Cr (VI) from the aqueous solution. The maximum adsorption capacity (qm) of Cr (VI) on the nano hexaferrite is higher than that of various other adsorbents testified in the literature. The pseudo-second-order kinetic model gives a better fit to the experimental data.

     

Synthesis of Novel (Polymer Blend-Ceramics) Nanocomposites: Structural,Optical and Electrical Properties for Humidity Sensors

Fabrication of novel nanocomposites films of (PVA–CMC) blend and (PVA–CMC) blend doped by niobium carbide nanoparticles has been investigated. The structural, optical and electrical properties of (PVA–CMC–NbC) nanocomposites for humidity sensors have been studied. The (PVA–CMC–NbC) nanocomposites were prepared with different concentrations of (polyvinyl alcohol and carboxyl methyl cellulose) and Niobium carbide nanoparticles. The experimental results of optical properties for (PVA–CMC–NbC) nanocomposites showed that the absorbance, absorption coefficient, extinction coefficient, refractive index, real and imaginary dielectric constants and optical conductivity of (PVA–CMC) blend increase with increase in Niobium carbide nanoparticles concentrations. The transmittance and energy band gap decrease with increase in Niobium carbide nanoparticles concentrations. The DC electrical properties of (PVA–CMC–NbC) nanocomposites showed that the electrical conductivity of the blend increases with increase in NbC nanoparticles concentrations. The experimental results of novel (PVA–CMC–NbC) nanocomposites applications showed that the (PVA–CMC–NbC) nanocomposites have high sensitivity for relative humidity.     

Effect of the graphite perfection on the HP–HT diamond synthesis in a Ni–Mn–C system

Changes in the graphite structure used as precursor for diamond synthesis is a phenomenon observed during high pressure and high temperature processes in the presence of a solvent–catalyst metals. In this work, experimental results have shown that the initial structure of the graphite material has a significant influence on the yield and the possibility of formation of diamond. An association between the degree of structural perfection of the graphite and the success in producing diamond crystals was found to exist even for conditions outside the field of diamond stability in the carbon P–T equilibrium diagram.     

Structural,magnetic, and antimicrobial properties of zinc doped magnesium ferrite for drug delivery applications

In this study, drug loading and release ability of the ferrite nanoparticle coated with PEG (polyethylene glycol) have been investigated for biomedical applications. The zinc-magnesium ferrite (Zn_xMg_(1-x)Fe₂O₄) was synthesized using sol-gel route. The doping concentration of Zn was gradually increased from zero to maximum (x = 1). XRD (X-ray diffraction) analysis of the samples shows the single phase with a cubic spinel structure. The Debye-Scherer formula has been used to calculate the average crystallite size (30.51 nm). The dumbbell and spherical shaped morphology (40–50 nm average particle size) have been investigated from the secondary electron images of FESEM (Field Emission Scanning Electron Microscopy). The antimicrobial assay has been carried out against E. coli bacteria by gentamicin (drug) loaded ferrite nanoparticles. The significant zone of inhibition might suggest that the drug-loaded ferrite nanoparticles can be used in drug delivery applications. PL (Photoluminescence) of the spinel ferrite shows that all the samples are in the visible range, and peaks at around 430 nm. The result reveals the synthesis of high purity ferrite nanoparticles with significant potential for drug delivery applications.     

On the validity of the formation of crystalline carbon nitrides,C3N4

X-ray powder diffraction patterns were simulated for five structures proposed for C₃N₄ — i.e., β-, α-, defect zincblend-type and cubic C₃N₄ — with lattice constants and structure parameters reported in the literature. The comparison of experimental X-ray and electron diffraction patterns assigned to crystalline carbon nitrides with simulated ones has led us to conclude that no work has yet presented unambiguous evidence for the crystallization of carbon nitrides with the proposed structures. Disordered polytypic diamond has been proposed as the most probable candidate for part of the products which have hitherto been regarded as C₃N₄.     

Calculated X-ray Diffraction Data for Diamond Polytypes

Calculated X-ray diffraction pattern data for diamond polytypes are presented, which provides the required parameters for the characterization of the proposed diamond polytypes. The literature on diamond polytypes contains some small but significant errors with respect to the details of the crystal structure, including space groups, the atom positions in the unit cell, and the atomic layer stacking. In this paper, the crystal structures of four different hexagonal diamond and two different rhombohedral diamond polytypes are theoretically calculated to provide correct crystallographic information with which the diamond polytypes in a given sample can be characterized.     

The orientation effect of silicon grains on diamond deposition

Diamond deposition on mirror-polished polycrystalline silicon substrates which have grains in various orientations has been investigated using electron backscatter diffraction (EBSD) method with scanning electron microscopy (SEM). Diamond was deposited by microwave plasma chemical vapor deposition with application of a negative bias voltage on the substrate. The evidence from systematic SEM observations shows that silicon orientation determined by EBSD has a strong effect on diamond nucleation. In general, the diamond nucleation density on Si grains oriented close to <100> is the highest, while it is the lowest for those grains close to <111>, under the same experimental conditions for deposition. The same phenomena have been observed in the range of methane concentration from 2% to 4% in hydrogen.     

Localised states in CVD diamond, explored by transient photoconductivity and residual field measurements

Chemical vapour deposited (CVD) diamond is attracting increasing interest as a potentially high performance semiconductor. However, in optimising the material for device applications, detailed information is often required on the properties of localised states within the energy gap. Although data are accumulating concerning mid-gap states, little has been published in respect of the shallower centres which often limit carrier drift mobility and other electronic properties.

This paper presents and analyses data from a detailed exploration of the presence and influence of such states, as obtained for the first time using transient photoresponse techniques. It is demonstrated that such procedures constitute a powerful vehicle for the study of localised states in CVD diamond. In particular, measurements show that even in very good quality CVD diamond films, an energetically broad but structured collection of localised states exists. The energy distribution of these has been computed using techniques developed, refined and proven in prior studies of other disordered solids.

During the course of our transient photodecay measurements, we have also established that specimens subjected to an applied field can accumulate a considerable space-charge-related residual field. This is obviously of significance to the operation of many potential devices. A new variant of the transient photoresponse system allows the decay of this field to be monitored as a function of time following the removal of an applied voltage. Such data provide further information on the localised states in which the space charge is trapped, and are shown to be at least qualitatively consistent with the localised state distribution computed from our transient photodecay measurements. Moreover, a simple model for the relaxation of the residual field is shown to be in excellent agreement with the experimental data.     

Recent advances in high-growth rate single-crystal CVD diamond

There have been important advances in microwave plasma chemical vapor deposition (MPCVD) of large single-crystal CVD diamond at high growth rates and applications of this diamond. The types of gas chemistry and growth conditions, including microwave power, pressure, and substrate surface temperatures, have been varied to optimize diamond quality and growth rates. The diamond has been characterized by a variety of spectroscopic and diffraction techniques. We have grown single-crystal CVD diamond over ten carats and above 1 cm in thickness at growth rates of 50–100 μm/h. Colorless and near colorless single crystals up to two carats have been produced by further optimizing the process. The nominal Vickers fracture toughness of this high-growth rate diamond can be tuned to exceed 20 MPa m^1/2 in comparison to 5–10 MPa m^1/2 for conventional natural and CVD diamond. Post-growth high-pressure/high-temperature (HPHT) and low-pressure/high-temperature (LPHT) annealing have been carried out to alter the optical, mechanical, and electronic properties. Most recently, single-crystal CVD diamond has been successfully annealed by LPHT methods without graphitization up to 2200 °C and < 300 Torr for periods of time ranging from a fraction of minute to a few hours. Significant changes observed in UV, visible, infrared, and photoluminescence spectra are attributed to changes in various vacancy centers and extended defects.     

Comparative electron diffraction study of the diamond nucleation layer on Ir(001)

The carbon layer formed during the bias enhanced nucleation (BEN) procedure on iridium has been studied by different electron diffraction techniques. In reflection high energy electron diffraction (RHEED) and low energy electron diffraction (LEED) the carbon nucleation layer does not give any indication of crystalline diamond even if the presence of domains proves successful nucleation. In contrast, X-ray photoelectron diffraction (XPD) shows a clear C 1s pattern when domains are present after BEN. The anisotropy in the Ir XPD patterns is reduced after BEN while the fine structure is essentially identical compared to a single crystal Ir film. The change in the Ir XPD patterns after BEN can be explained by the carbon layer on top of a crystallographically unmodified Ir film. The loss and change in the fine structure of the C 1s patterns as compared to a single crystal diamond film are discussed in terms of mosaicity and a defective structure of the ordered fraction within the carbon layer. The present results suggest that the real structure of the BEN layer is more complex than a pure composition of small but perfect diamond crystallites embedded in an amorphous matrix.