Photonic active diamond nanoparticles attract increasing attention from a wide community for applications in drug delivery and monitoring experiments as they do not bleach or blink over extended periods of time. To be utilized, the size of these diamond nanoparticles needs to be around 4 nm. Cluster formation is therefore the major problem. In this paper we introduce a new technique to modify the surface of particles with hydrogen, which prevents cluster formation in buffer solution and which is a perfect starting condition for chemical surface modifications. By annealing aggregated nanodiamond powder in hydrogen gas, the large (>100 nm) aggregates are broken down into their core ( approximately 4 nm) particles. Dispersion of these particles into water via high power ultrasound and high speed centrifugation, results in a monodisperse nanodiamond colloid, with exceptional long time stability in a wide range of pH, and with high positive zeta potential (>60 mV). The large change in zeta potential resulting from this gas treatment demonstrates that nanodiamond particle surfaces are able to react with molecular hydrogen at relatively low temperatures, a phenomenon not witnessed with larger (20 nm) diamond particles or bulk diamond surfaces.

A summary of photo- and electrochemical surface modifications applied on single-crystalline chemical vapour deposition (CVD) diamond films is given. The covalently bonded formation of amine- and phenyl-linker molecule layers is characterized using x-ray photoelectron spectroscopy, atomic force microscopy (AFM), cyclic voltammetry and field-effect transistor characterization experiments. Amine- and phenyl-layers are very different with respect to formation, growth, thickness and molecule arrangement. We detect a single-molecular layer of amine-linker molecules on diamond with a density of about 1014 cm−2 (10% of carbon bonds). Amine molecules are bonded only on initially H-terminated surface areas to carbon. In the case of electrochemical deposition of phenyl-layers, multi-layer formation is detected due to three-dimensional (3D) growths. This gives rise to the formation of typically 25 Å thick layers. The electrochemical grafting of boron-doped diamond works on H-terminated and oxidized surfaces.After reacting such films with hetero-bifunctional crosslinker molecules, thiol-modified ss-DNA markers are bonded to the organic system. Application of fluorescence and AFM on hybridized DNA films shows dense arrangements with densities of up to 1013 cm−2. The DNA is tilted by an angle of about 35° with respect to the diamond surface. Shortening the bonding time of thiol-modified ss-DNA to 10 min causes a decrease of DNA density to about 1012 cm−2. Application of AFM scratching experiments shows threshold removal forces of around 75 nN for DNA bonded on phenyl-linker molecules and of about 45 nN for DNA bonded to amine-linker molecules. DNA sensor applications using Fe(CN6)3−/4− mediator redox molecules, impedance spectroscopy and DNA-field effect transistor devices performances are introduced and discussed.

A summary of photo- and electrochemical surface modifications applied on single-crystalline chemical vapour deposition diamond films is given. The covalently bonded formation of amine and phenyl linker molecular layers is characterized using X-ray photoelectron spectroscopy, atomic force microscopy (AFM), cyclic voltammetry and field-effect transistor characterization experiments. Amine and phenyl layers are very different with respect to formation, growth, thickness and molecular arrangement. We deduce a sub-monolayer of amine linker molecules on diamond with approximately 10% coverage of 1.510(15) cm(-2) carbon bonds. Amine is bonded only on initially H-terminated surface areas. In the case of electrochemical deposition of phenyl layers, multilayer properties are detected with three-dimensional nitrophenyl growth properties. This leads to the formation of typically 25 A thick layers. The electrochemical bonding to boron-doped diamond works on H-terminated and oxidized surfaces. After reacting such films with heterobifunctional cross-linker molecules, thiol-modified ss-DNA markers are bonded to the organic system. Application of fluorescence and AFM on hybridized DNA films shows dense arrangements with densities up to 10(13) cm(-2). The DNA is tilted by an angle of approximately 35 degrees with respect to the diamond surface. Shortening the bonding time of thiol-modified ss-DNA to 10 min causes a decrease in DNA density to approximately 10(12) cm(-2). Application of AFM scratching experiments shows threshold removal forces of approximately 75 and 45 nN for the DNA bonded to the phenyl and the amine linker molecules, respectively. First, DNA sensor applications using Fe(CN6) 3-/4- mediator redox molecules and DNA field-effect transistor devices are introduced and discussed.

Boron-doped diamond is a promising transducer material for numerous devices which are designed for contact with electrolytes. For optimized electron transfer the surface of diamond needs to be hydrogen terminated. Up to now H-termination of diamond is done by plasma chemical vapor deposition techniques. In this paper, we show that boron-doped diamond can be H-terminated electrochemically by applying negative voltages in acidic solutions. Electrochemical H-termination generates a clean surface with virtually no carbon-oxygen bonds (x-ray photoelectron spectroscopy), a reduced electron affinity (scanning electron microscopy), a highly hydrophobic surface (water contact angle), and a fast electron exchange with Fe(CN)6(-3/-4)(cyclic voltammetry)

Total photoyield experiments are applied to characterize p-, intrinsic, and n-type diamond with hydrogen-terminated surfaces. On all hydrogen-terminated samples a photoelectron threshold energy of 4.4 eV is detected which is discussed in detail in this letter. We attribute this threshold to the energy gap between the valence-band maximum and the vacuum level, which is 1.1 eV below the conduction-band minimum, and generally referred to as ”negative electron affinity” (NEA). Hydrogen terminated p-type and intrinsic diamond show a rise of secondary photoyield in the excitation regime hν>5.47eV. However, this is not detected on n-type diamond. We ascribe this to the formation of an upward surface band bending in the vicinity of the n-type diamond surface which acts as an energy barrier for electrons.