Surfaces — Open Access Journal

This minireview aims at providing a complete survey concerning the use of X-ray absorption spectroscopy (XAS) for time-resolved studies of electrochemical and photoelectrochemical phenomena. We will see that time resolution can range from the femto-picosecond to the second (or more) scale and that this joins the valuable throughput typical of XAS, which allows for determining the oxidation state of the investigated element, together with its local structure. We will analyze four different techniques that use different approaches to exploit the in real time capabilities of XAS. These are quick-XAS, energy dispersive XAS, pump & probe XAS and fixed-energy X-ray absorption voltammetry. In the conclusions, we will analyze possible future perspectives for these techniques. Full article

In magnetic hard disk drives, it is important to evaluate the replenishment effect of a submonolayer lubricant film under a more severe condition that the head–disk spacing has to be reduced from the current 0.7 nm to ~0.5 nm. In contrast to the prevailing conventional diffusion equation validated for multilayer liquid film, the author has already proposed a new diffusion equation more suitable for submonolayer film by intuitively incorporating the density reduction effect in the submonolayer liquid film. This paper presents a rigorous derivation of the disjoining pressure (DP) from Lennard–Jones potential (LJP) and formulated the diffusion equation incorporating the DP. The difference in the rigorous DP and diffusion equation from the previous versions is negligibly small except in a small film thickness less than the van der Waals (vdW) distance. The theoretical relationship between the vdW distance in the DP and the molecular force equilibrium distance in the LJP is elucidated. Rigorous derivations of the DP and diffusion equation for multilayer liquid film from the LJP are also presented. The superiority of the submonolayer diffusion equation over the conventional equation in the submonolayer film regime is demonstrated by comparing their theoretical diffusion coefficients with Waltman’s experimental data. Full article

Lanthanide ion-doped upconversion nanoparticles (UCNPs) that can convert low-energy infrared photons into high-energy visible and ultraviolet photons, are becoming highly sought-after for advanced biomedical and biophotonics applications. Their unique luminescent properties enable UCNPs to be applied for diagnosis, including biolabeling, biosensing, bioimaging, and multiple imaging modality, as well as therapeutic treatments including photothermal and photodynamic therapy, bio-reductive chemotherapy and drug delivery. For the employment of the inorganic nanomaterials into biological environments, it is critical to bridge the gap in between nanoparticles and biomolecules via surface modifications and subsequent functionalisation. This work reviews the various ways to surface modify and functionalise UCNPs so as to impart different functional molecular groups to the UCNPs surfaces for a broad range of applications in biomedical areas. We discussed commonly used base functionalities, including carboxyl, amino and thiol moieties that are typically imparted to UCNP surfaces so as to provide further functional capacity. Full article

We report the modulation of the specific metal gation properties of a peptide and demonstrate a highly selective sensor for copper(II) ion. The neuropeptide oxytocin (OT) is reported for its high affinity towards Zn²⁺ and Cu²⁺ at physiological pH. The binding of the metal ions to OT is tuned by altering the pH of the medium. OT was self-assembled on glassy carbon electrode using surface chemistry, and electrochemical impedance spectroscopy (EIS) was used to probe the binding of Cu²⁺. Our results clearly indicate that at pH 10.0, the binding of Cu²⁺ to OT is increased compared to that at pH 7.0, while the binding to Zn²⁺ becomes almost negligible. This proves that the selectivity of OT towards each of the ions can be regulated simply by controlling the pH of the medium and hence allows the preparation of a sensing device with selectivity to Cu²⁺. Full article

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