a b s t r a c tThe morphology and presence of impurities strongly influence mechanical, optical, electrical, and thermal properties of detonation nanodiamonds (DNDs). Here we report insights on the chemical composition and its effect on the optical properties of the DNDs obtained by rate-zonal density gradient ultracentrifugation. Herein, for the first time, a detailed valence band structure of as-prepared and oxidized DNDs is reported. Photoemission spectroscopy (PES) measurements demonstrate that the defects, originating from fullerene-like C bonding in the sp 2 shells of the DNDs, are governing the literature-reported loss of the emission spectral features arising from the nitrogen-vacancy (NV) center excitations. X-ray photoelectron spectroscopy (XPS) measurements reveal that nitrogen is present in the DNDs in the form of N-O bonded species located at the surface region/sp 2 shells, while in core of the DND it is in the form of N-C/N@C species.

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Size is a defining characteristic of nanoparticles; it influences their optical and electronic properties as well as their interactions with molecules and macromolecules. Producing nanoparticles with narrow size distributions remains one of the main challenges to their utilization. At this time, the number of practical approaches to optimize the size distribution of nanoparticles in many interesting materials systems, including diamond nanocrystals, remains limited. Diamond nanocrystals synthesized by detonation protocols - so-called detonation nanodiamonds (DNDs) - are promising systems for drug delivery, photonics, and composites. DNDs are composed of primary particles with diameters mainly <10 nm and their aggregates (ca. 10-500 nm). Here, we introduce a large-scale approach to rate-zonal density gradient ultracentrifugation to obtain monodispersed fractions of nanoparticles in high yields. We use this method to fractionate a highly concentrated and stable aqueous solution of DNDs and to investigate the size distribution of various fractions by dynamic light scattering, analytical ultracentrifugation, transmission electron microscopy and powder X-ray diffraction. This fractionation method enabled us to separate gram-scale amounts of DNDs into several size ranges within a relatively short period of time. In addition, the high product yields obtained for each fraction allowed us to apply the fractionation method iteratively to a particular size range of particles and to collect various fractions of highly monodispersed primary particles. Our method paves the way for in-depth studies of the physical and optical properties, growth, and aggregation mechanism of DNDs. Applications requiring DNDs with specific particle or aggregate sizes are now within reach.

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We present a facile method for the production of fluorescent diamond nanocrystals (DNCs) of different sizes and efficiently quantify the concentration of emitting defect color centers (DCCs) of each DNC size. We prepared the DNCs by ball-milling commercially available micrometer-sized synthetic (high pressure, high temperature (HPHT)) diamonds and then separated the as-produced DNCs by density gradient ultracentrifugation (DGU) into size-controlled fractions. A protocol to enhance the uniformity of the nitrogen-vacancy (NV) centers in the diamonds was devised by depositing the DNCs as a dense monolayer on amino-silanized silicon substrates and then subjecting the monolayer to He(+) beam irradiation. Using a standard confocal setup, we analyzed the average number of NV centers per crystal, and obtained a quantitative relationship between the DNC particle size and the NV number per crystal. This relationship was in good agreement with results from previous studies that used more elaborate setups. Our findings suggest that nanocrystal size separation by DGU may be used to control the number of defects per nanocrystal. The efficient approaches described herein to control and quantify DCCs are valuable to researchers as they explore applications for color centers and new strategies to create them.