Surfaces — Open Access Journal

Polycrystalline anatase thin films, (001)- and (101)-oriented anatase TiO${}_2$ single crystals and (001)- and (110)-oriented rutile TiO${}_2$ single crystals with various surface treatments were studied by photoelectron spectroscopy to obtain their surface potentials. Regardless of orientations and polymorph, a huge variation of the Fermi level and work function was achieved by varying the surface condition. The most strongly oxidized surfaces are obtained after oxygen plasma treatment with a Fermi level ∼2.6 eV above the valence band maximum and ionization potentials of up to 9.5 eV (work function 7.9 eV). All other treated anatase surfaces exhibit an ionization potential independent of surface condition of $7.96\pm 0.15$ eV. The Fermi level positions and the work functions vary by up to 1 eV. The ionization potential of rutile is ∼0.56 eV lower than that of anatase in good agreement with recent band alignment studies. Full article

Silicon nitride and silicon oxynitride thin films are widely used in microelectronic fabrication and microelectromechanical systems (MEMS). Their mechanical properties are important for MEMS structures; however, these properties are rarely reported, particularly the fracture toughness of these films. In this study, silicon nitride and silicon oxynitride thin films were deposited by plasma enhanced chemical vapor deposition (PECVD) under different silane flow rates. The silicon nitride films consisted of mixed amorphous and crystalline Si₃N₄ phases under the range of silane flow rates investigated in the current study, while the crystallinity increased with silane flow rate in the silicon oxynitride films. The Young’s modulus and hardness of silicon nitride films decreased with increasing silane flow rate. However, for silicon oxynitride films, Young’s modulus decreased slightly with increasing silane flow rate, and the hardness increased considerably due to the formation of a crystalline silicon nitride phase at the high flow rate. Overall, the hardness, Young modulus, and fracture toughness of the silicon nitride films were greater than the ones of silicon oxynitride films, and the main reason lies with the phase composition: the SiN_x films were composed of a crystalline Si₃N₄ phase, while the SiO_xN_y films were dominated by amorphous Si–O phases. Based on the overall mechanical properties, PECVD silicon nitride films are preferred for structural applications in MEMS devices. Full article

Adhesion of polymers to surfaces is of the upmost importance in timely applications such as protective coatings, biomaterials, sensors, new power sources and soft electronics. In this context, this work examines the role of molecular interactions in the adhesion of polypyrrole thin films to flexible Indium Tin Oxide (ITO) electrodes grafted with aryl layers from various diazonium salts, namely 4-carboxybenzenediazonium (ITO-CO₂H), 4-sulfonicbenzenediazonium (ITO-SO₃H), 4-N,N-dimethylbenzenediazonium (ITO-N(CH₃)₂), 4-aminobenzenediazonium (ITO-NH₂), 4-cyanobenzenediazonium (ITO-CN) and 4-N-phenylbenzenediazonium (ITO-NHPh). It was demonstrated that PPy thin layers were adherent to all aryl-modified surfaces, whereas adhesive failure was noted for bare ITO following simple solvent washing or sonication. Adhesion of polypyrrole was investigated in terms of hydrophilic/hydrophobic character of the underlying aryl layer as probed by contact angle measurements. It was found that sulfonic acid-doped polypyrrole (PPy-BSA) thin films were preferably deposited on the most hydrophobic surfaces. More importantly, the redox properties and electrochemical impedance of PPy were closely related to the hydrophobic character of the aryl layers. This work demonstrates that diazonium compounds are unique molecular glues for conductive polymers and permit to tune their interfacial properties. With robust, diazonium-based architectured interfaces, one can design high performance materials for e.g., sensors, printed soft electronics and flexible thermoelectrics. Full article

The passivation of metal electrodes covered by self-assembled monolayers of long-chain thiols is well known. The disappearance of the voltammetric peak of redox species in solution is a classical test for the formation of full layers of thiols. Similar studies on semiconductors are still very limited. We used silver surfaces covered by an ultrathin layer of CdS as substrate for self-assembling of n-hexadecanethiol (C₁₆SH), and we compared the experimental results with those obtained by using the bare silver surface as substrate. The strong insulating effect of C₁₆SH deposited on Ag(III) is shown by the inhibition of the voltammetric peak of Ru(NH₃)₆^3+/2+. On the contrary, the voltammogram obtained on CdS-covered Ag(III) is very similar to that obtained on the bare Ag(III) electrode, thus suggesting that the presence of CdS exerts a contrasting effect on the passivation of the silver electrode. A crucial point of our work is to demonstrate the effective formation of C₁₆SH monolayers on Ag(III) covered by CdS. The formation of full layers of C₁₆SH was strongly suggested by the inhibition of the stripping peak of Cd from the CdS deposit covered by C₁₆SH. The presence of C₁₆SH was confirmed by electrochemical quartz crystal microbalance (EQCM) measurements as well as by Auger electron spectroscopy (AES) analysis. Full article

The modelling of long-range ordered nanostructures is still a major issue for the scientific community. In this work, the self-assembly of redox-active tetra(N-methyl-4-pyridyl)-porphyrin cations (H₂TMPyP) on an iodine-modified Au(100) electrode surface has been studied by means of Cyclic Voltammetry (CV) and in-situ Electrochemical Scanning Tunneling Microscopy (EC-STM) with submolecular resolution. While the CV measurements enable conclusions about the charge state of the organic species, in particular, the potentio-dynamic in situ STM results provide new insights into the self-assembly phenomena at the solid-liquid interface. In this work, we concentrate on the regime of positive electrode potentials in which the adsorbed molecules are not reduced yet. In this potential regime, the spontaneous adsorption of the H₂TMPyP molecules on the anion precovered surface yields the formation of up to five different potential-dependent long-range ordered porphyrin phases. Potentio-dynamic STM measurements, as a function of the applied electrode potential, show that the existing ordered phases are the result of a combination of van der Waals and electrostatic interactions. Full article

Organic electrosynthesis is going through its renaissance but its scope in surface science as a tool to introduce specific molecular signatures at an electrode/electrolyte interface is under explored. Here, we have investigated an electrochemical approach to generate in situ surface-tethered and highly-reactive carbocations. We have covalently attached an alkoxyamine derivative on an Si(100) electrode and used an anodic bias stimulus to trigger its fragmentation into a diffusive nitroxide (TEMPO) and a surface-confined carbocation. As a proof-of-principle we have used this reactive intermediate to trap a nucleophile dissolved in the electrolyte. The nucleophile was ferrocenemethanol and its presence and surface concentration after its reaction with the carbocation were assessed by cyclic voltammetry. The work expands the repertoire of available electrosynthetic methods and could in principle lay the foundation for a new form of electrochemical lithography. Full article