Dry and bright: To mimic the wings of the displayed Morpho butterfly, a new decorative material that exhibits both structural color and superhydrophobicity (the “lotus effect”) was developed by taking advantage of the unique structural properties of an inverse opal film, which was fabricated by the self‐assembly of polystyrene spheres and silica nanoparticles.

Identification of charge transfer and trapping sites on semiconducting oxide surfaces is of fundamental importance in furthering the field of heterogeneous photocatalysts. Using scanning tunneling microscopy, electron energy loss spectroscopy, and photodesorption, we observed both electron trapping and hole transfer events on the (110) surface of TiO2 rutile. UV irradiation of a saturated monolayer of trimethyl acetate (TMA) on TiO2(110) at room temperature resulted in hole transfer to the carboxylate group, followed by (CH3)3C-COO bond cleavage and desorption of CO2 and isobutene/isobutane. Hole transfer to TMA proceeded in the absence of a gas-phase electron scavenger (which is typically O2) because the accompanying photogenerated electrons could be trapped at the surface as Ti3+ cations bound to bridging OH groups. The extent of electron trapping, gauged by electron spectroscopy, correlated directly with the yields of photodesorption fragments resulting from the hole transfer channel. Charge at the Ti3+ sites was titrated in the dark via a reaction between O2 and the Ti3+-OH groups.

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.

Vertically aligned diamond nanowires with controlled geometrical properties like length and distance between wires were fabricated by use of nanodiamond particles as a hard mask and by use of reactive ion etching. The surface structure, electronic properties, and electrochemical functionalization of diamond nanowires were characterized by atomic force microscopy (AFM) and scanning tunneling microscopy (STM) as well as electrochemical techniques. AFM and STM experiments show that diamond nanowire etched for 10 s have wire-typed structures with 3-10 nm in length and with typically 11 nm spacing in between. The electrode active area of diamond nanowires is enhanced by a factor of 2. The functionalization of nanowire tips with nitrophenyl molecules is characterized by STM on clean and on nitrophenyl molecule-modified diamond nanowires. Tip-modified diamond nanowires are promising with respect to biosensor applications where controlled biomolecule bonding is required to improve chemical stability and sensing significantly.

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.

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Photoinduced oxidation of trimethyl acetate (TMA) was examined on an atomically flat surface of rutile TiO2. The macroscopic rate of reaction (the partial pressure of desorption products) was temporary modulated when a TMA-covered surface was UV-irradiated in oxygen gas. Scanning tunneling microscope imaging revealed spatially modulated distribution of TMA and OH on that surface. The limited surface mobility of electrons photoexcited and trapped at OH-associated Ti sites was proposed to cause the temporal and spatial modulations. The characteristic length of the spatial modulation, i.e., the lateral dimension of electron confinement, was a few lattice constants of the oxide.