Fractional surface termination of diamond by electrochemical oxidation.

The crystalline form of sp(3)-hybridized carbon, diamond, offers various electrolyte-stable surface terminations. The H-termination-selective attachment of nitrophenyl diazonium, imaged by AFM, shows that electrochemical oxidation can control the fractional hydrogen/oxygen surface termination of diamond on the nanometer scale. This is of particular interest for all applications relying on interfacial electrochemistry, especially for biointerfaces.

Anisotropic diamond etching through thermochemical reaction between Ni and diamond in high-temperature water vapour.

Diamond possesses excellent physical and electronic properties, and thus various applications that use diamond are under development. Additionally, the control of diamond geometry by etching technique is essential for such applications. However, conventional wet processes used for etching other materials are ineffective for diamond. Moreover, plasma processes currently employed for diamond etching are not selective, and plasma-induced damage to diamond deteriorates the device-performances. Here, we report a non-plasma etching process for single crystal diamond using thermochemical reaction between Ni and diamond in high-temperature water vapour. Diamond under Ni films was selectively etched, with no etching at other locations. A diamond-etching rate of approximately 8.7 µm/min (1000 °C) was successfully achieved. To the best of our knowledge, this rate is considerably greater than those reported so far for other diamond-etching processes, including plasma processes. The anisotropy observed for this diamond etching was considerably similar to that observed for Si etching using KOH.

Diamond and biology.

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.

Inversion channel diamond metal-oxide-semiconductor field-effect transistor with normally off characteristics.

We fabricated inversion channel diamond metal-oxide-semiconductor field-effect transistors (MOSFETs) with normally off characteristics. At present, Si MOSFETs and insulated gate bipolar transistors (IGBTs) with inversion channels are widely used because of their high controllability of electric power and high tolerance. Although a diamond semiconductor is considered to be a material with a strong potential for application in next-generation power devices, diamond MOSFETs with an inversion channel have not yet been reported. We precisely controlled the MOS interface for diamond by wet annealing and fabricated p-channel and planar-type MOSFETs with phosphorus-doped n-type body on diamond (111) substrate. The gate oxide of Al2O3 was deposited onto the n-type diamond body by atomic layer deposition at 300 °C. The drain current was controlled by the negative gate voltage, indicating that an inversion channel with a p-type character was formed at a high-quality n-type diamond body/Al2O3 interface. The maximum drain current density and the field-effect mobility of a diamond MOSFET with a gate electrode length of 5 µm were 1.6 mA/mm and 8.0 cm(2)/Vs, respectively, at room temperature.

Selective growth of ag nanowires on Si(111) surfaces by electroless deposition.

Electroless deposition of Ag on atomically flat H-terminated Si(111) surfaces in aqueous alkaline solutions containing Ag ions produced two different sizes of Ag nanowires along atomic step edges: (1) a narrow nanowire of 10 nm in width and 0.5 nm in height and (2) a wide nanowire of 35 nm in width and 11 nm in height. The narrow and wide nanowires were formed by immersion in the solutions containing less than 1 ppb and 8 ppm dissolved-oxygen concentrations, respectively. This result indicates that the dissolved oxygen initiates the formation of Ag nucleation sites and that the fabrication method has a possibility of controlling the size of Ag nanowires.

The creation of a biomimetic interface between boron-doped diamond and immobilized proteins.

Immobilization of proteins on a solid electrode is to date done by chemical cross-linking or by addition of an adjustable intermediate. In this paper we introduce a concept where a solid with variable surface properties is optimized to mediate binding of the electron-transfer protein Cytochrome c (Cyt c) by mimicking the natural binding environment. It is shown that, as a carbon-based material, boron-doped diamond can be adjusted by simple electrochemical surface treatments to the specific biochemical requirements of Cyt c. The structure and functionality of passively adsorbed Cyt c on variously terminated diamond surfaces were characterized in detail using a combination of electrochemical techniques and atomic force microscopy with single-molecule resolution. Partially oxidized diamond allowed stable immobilization of Cyt c together with high electron transfer activity, driven by a combination of electrostatic and hydrophobic interactions. This surface mimics the natural binding partner, where coarse orientation is governed by electrostatic interaction of the protein's dipole and hydrophobic interactions assist in formation of the electron transfer complex. The optimized surface mediated electron transfer kinetics around 100 times faster than those reported for other solids and even faster kinetics than on self-assembled monolayers of alkanethiols.

Electrochemical grafting of boron-doped single-crystalline chemical vapor deposition diamond with nitrophenyl molecules.

The growth of covalently bonded nitrophenyl layers on atomically smooth boron-doped single-crystalline diamond surfaces is characterized using cyclic voltammetric attachment and constant-potential grafting by electrochemical reduction of aryl diazonium salts. We apply atomic force microscopy (AFM) in contact mode to remove phenyl layers and measure phenyl layer thicknesses by oscillatory AFM. Angle-resolved X-ray photoelectron spectroscopy is applied to reveal the bonding arrangement of phenyl molecules, and transient current measurements during the grafting are used to investigate the dynamics of chemical bonding. Nitrophenyl groups at an initial stage of attachment grow three-dimensional (3D), forming layers of varying heights and densities. Layer thicknesses of up to 80 A are detected for cyclic voltammetry attachment after five cycles, whereas the layer becomes denser and only about 25 A thick in the case of constant-potential attachment. No monomolecular closed layer can be detected. The data are discussed taking into account established growth models. Redox systems such as Fe(CN)63-/4- and Ru(NH3)62+/3+ are used to probe the electrochemical barrier properties of nitrophenyl groups grafted onto diamond.