A. Ya. Vul

The structure of diamond nanoclusters

A model describing the structure of diamond nanoclusters produced by explosive shocks is proposed. The model is based on experimental data obtained from x-ray diffraction and small-angle x-ray scattering. This model considers the diamond nanocluster as a crystalline diamond core coated by a carbon shell having a fractal structure. The shell structure depends both on the cooling kinetics of the detonation products and on the method used to extract from them the diamond fraction.

Diamond-graphite phase transition in ultradisperse-diamond clusters

A systematic study of the diamond-graphite structural phase transition in ultradisperse-diamond clusters obtained by the detonation technique is reported. Samples of two types, differing in the kinetics of detonation-product cooling, were investigated. The phase transition was achieved under heating in an inert atmosphere in the temperature range 720–1400 K. The transition was identified by Raman scattering and x-ray diffraction data. Raman and x-ray characterization showed the ultradisperse diamond, irrespective of the cooling rate used, to be cluster material possessing diamond structure with a characteristic nanocrystal size of 43 Å. The diamond-graphite phase transition in ultradisperse diamond is shown to start from the cluster surface inwards at Tpt≈1200 K, i.e. at substantially lower temperatures than is the case with bulk diamond single crystals.

Structure and defects of detonation synthesis nanodiamond

Abstract Characterization of the structure and defects in detonation synthesis, ultradisperse diamond (UDD) is reported. X-ray and proton nuclear magnetic resonance results on UDD powders are interpreted in terms of the different structure of the shell of UDD particles, produced under different conditions. In spite of the comparable contents of carbon and nitrogen atoms in the precursor, no (

Optical properties of nanodiamond layers

Thin ultradisperse diamond (UDD) layers deposited from a water suspension are studied by optical and x-ray photoelectron spectroscopy (XPS). The effective band gap determined by the 104-cm−1 criterion for ozone-cleaned UDD is 3.5 eV. The broad structureless photoluminescence band (380–520 nm) is associated with radiative recombination through a system of continuously distributed energy levels in the band gap of diamond nanoclusters. The optical absorption of the material at 250–1000 nm originates from absorption on the disordered nanocluster surface containing threefold-coordinated carbon. The surface of UDD clusters subjected to acid cleaning contains nitrogen-oxygen complexes adsorbed in the form of NO3− nitrate ions. Annealing in a hydrogen atmosphere results in desorption of the nitrate ions from the cluster surface. The evolution of the oxygen (O1s) and nitrogen (N1s) lines in the XPS spectra under annealing of a UDD layer is studied comprehensively.

Proton magnetic resonance study of diamond nanoparticles decorated by transition metal ions

We report on a 1H NMR study of diamond nanoparticles decorated by copper and cobalt. Increase in the 1H relaxation rate under decoration results from the interactions of hydrogen nuclear spins of the surface hydrocarbon and hydroxyl groups with paramagnetic copper and cobalt ions. This finding reveals the appearance of paramagnetic Cu2+ or Co2+ ions on the detonation nanodiamond (DND) surface rather than as a separate phase, which is consistent with the 13C NMR data of the same samples. Our results shed light on the mechanism of ion incorporation. A topological model for relative position of paramagnetic Cu2+ or Co2+ ions and hydrogen atoms on the DND surface is suggested. An application of the studied nanomaterials in the field of biomedicine is discussed.

Structure and magnetic properties of detonation nanodiamond chemically modified by copper

We report on detailed study of detonation nanodiamonds (DNDs) whose surface has been chemically modified by copper with the aid of ion exchange in water DND suspension. High resolution transmission electron microscopy, Raman, IR, electron magnetic resonance (EMR), nuclear magnetic resonance (NMR), and superconducting quantum interference device techniques were used for the characterization of DND. Carboxyl groups, appearing on the surface of a nanodiamond particle during its synthesis and purification processes, provide an effective binding of divalent copper ions to the surface. The binding results from the ion exchange between metal cations and protons of surface carboxyl groups in water solutions. IR data evidence the presence of multiple COC groups in the dried copper-modified DND product. Both EMR and C13 NMR provide direct evidences of the appearance of isolated Cu2+ ions on the surface of the 5 nm nanodiamond particles. EMR spectra reveal well-pronounced hyperfine structure due to C63,65u nuclear...

Luminescent isolated diamond particles with controllably embedded silicon-vacancy colour centres

A technique to fabricate isolated diamond particles with controllably embedded silicon-vacancy (Si-V) colour centres is described. Particle growth and Si doping are performed by microwave plasma-enhanced chemical vapour deposition (CVD) using silane as a source of impurity atoms. The Si-V centres have a strong narrow-band photoluminescence (PL) at room temperature. The dependence of PL intensity of the 738 nm zero-phonon line (ZPL) on silane concentration in the feed-gas mixture exhibits a pronounced maximum. A comparison of the PL and Raman spectra shows that there is an evident correlation between the ZPL intensity and the presence of structural defects and nondiamond carbon phases that act as nonradiative recombination centres suppressing radiative recombination. The results open the door for using the powerful CVD technique for large-scale production of photostable near-infrared single-photon emitters and noncytotoxic biomarkers.

Detonation Nanodiamonds as Catalyst Supports

The article reports on experimental study of catalytic properties of a new system: Pt on detonation nanodiamond (Pt/DND) for the carbon monoxide oxidation reaction. The catalytic activity of Pt/DND structures as a function of platinum content in the catalyst within the 7–80 wt % intervals was studied and the structure of the Pt/DND catalyst was investigated by X-ray diffraction and HRTEM. The Pt/DND catalysts developed demonstrate a high degree of conversion of CO to CO2 at room temperature, a feature making them attractive for commercial applications as catalytic systems for purification of air from carbon monoxide in houses and industrial areas. The new catalysts were incorporated in solid-state electrochemical CO gas sensors. A statement on efficiency of the detonation nanodiamonds as a support for catalytic metals of platinum groups has been done.

Ultradisperse Diamond Cluster Aggregation Studied by Atomic Force Microscopy

The structure of ultradisperse diamond (UDD) conglomerates was studied by scanning atomic-force microscopy (AFM). The UDD layers were prepared from a detonation carbon obtained by synthesis in an aqueous medium. The finest details in the AFM images of UDD layers are of the order of 10 nm, which does not allow individual 4.5-nm diamond clusters to be distinguished. The UDD conglomerates deposited and dried on a silicon substrate surface, exhibit certain deformation and differ from the initial (apparently, spherical) shape. This may imply that cohesion between the UDD nanoparticles is comparable with their adhesion to the silicon substrate.

Fractal structure of ultradisperse-diamond clusters

Ultradisperse-diamond clusters are shown to be fractal objects, and the character of variation of the fractal dimension in the course of the diamond-graphite phase transition under annealing in an inert atmosphere is studied.