Andriy Romanyuk

The electronic surface barrier of boron-doped diamond by anodic oxidation

It was shown that a strong anodic oxidation of 100-oriented diamond induces the electronic surface states, which pin the surface Fermi level at about 3.6 eV above the valence-band maximum. The characteristics of the electronic surface barrier were evaluated from the analysis of boron-doped diamond electrodes and correlated with the four-point probe measurements of an oxidized diamond resistor with a boron delta-doped channel. The same evaluation procedure applied to the case of a wet chemical oxidation yielded a surface barrier of 1.9 eV, which is consistent with the data in the literature. The characteristics of the 3.6 eV barrier by the anodic oxidation remained stable after subsequent chemical treatments even at elevated temperatures, and were also not degraded in air for a long time. The x-ray photoemission spectroscopy study showed that the anodic oxidation generates complex oxygen functionalities, like polycarbonate groups, and also C-O-C bridging bond structures with possible contribution of an add...

Surface chemistry of rare-earth oxide surfaces at ambient conditions: reactions with water and hydrocarbons

Rare-earth (RE) oxide surfaces are of significant importance for catalysis and were recently reported to possess intrinsic hydrophobicity. The surface chemistry of these oxides in the low temperature regime, however, remains to a large extent unexplored. The reactions occurring at RE surfaces at room temperature (RT) in real air environment, in particular, in presence of polycyclic aromatic hydrocarbons (PAHs), were not addressed until now. Discovering these reactions would shed light onto intermediate steps occurring in automotive exhaust catalysts before reaching the final high operational temperature and full conversion of organics. Here we first address physical properties of the RE oxide, nitride and fluoride surfaces modified by exposure to ambient air and then we report a room temperature reaction between PAH and RE oxide surfaces, exemplified by tetracene (C18H12) on a Gd2O3. Our study evidences a novel effect – oxidation of higher hydrocarbons at significantly lower temperatures (~300 K) than previously reported (>500 K). The evolution of the surface chemical composition of RE compounds in ambient air is investigated and correlated with the surface wetting. Our surprising results reveal the complex behavior of RE surfaces and motivate follow-up studies of reactions between PAH and catalytic surfaces at the single molecule level.

Use of ultrasound for metal cluster engineering in ion implanted silicon oxide

This letter presents an approach to metal cluster engineering in silicon oxide that uses ultrasound vibration applied in situ during implantation. Analysis by transmission electron microscopy has demonstrated that in situ applied acoustic vibrations result in a lowering of the clustering threshold and an increase in cluster size after subsequent annealing. The results are interpreted in terms of the interaction between ultrasonic vibrations and point defects leading to the formation of vacancy-rich regions, as determined by deuterium decoration method. The excess of vacancies in the precipitation region facilitates nucleation and stimulates cluster growth due to enhanced diffusion of metal species.

Influence of in situ ultrasound treatment during ion implantation on formation of silver nanoparticles in silica

We report on the effect of in situ ultrasound treatment on the clustering process of silver atoms in ion-implanted SiO2. Cross-sectional transmission electron microscopy shows single-crystal Ag spheres with an increased cluster size when prepared using ultrasound vibrations. Time-of-flight secondary-ion-mass spectrometry demonstrates an enhanced yield of [Ag2]216 complexes in structures treated with acoustic waves. An analysis of the influence of ultrasound on defect reaction kinetics as well as on different stages of the clustering process is performed.

Surface damages in diamond by Ar/O2 plasma and their effect on the electrical and electrochemical characteristics of boron-doped layers

Epitaxial single crystal and boron-doped diamond layers were exposed to reactive ion etching in Ar/O2 plasma (rf power of 25 W and self-bias of 100 V); and the electrical, structural, and electrochemical characteristics of the exposed surface were investigated. Angle-resolved x-ray photoemission spectroscopy (XPS) measurements revealed a nonuniform layer of amorphous carbon at the exposed surface with an average thickness of approximately 4 nm, as confirmed also by atomic force microscopy profiling of selectively etched areas. On highly boron-doped diamond, the plasma-induced damages resulted also in a nonconductive surface layer. This damaged and insulating surface layer remained resistant to graphite-etching chemicals and to rf oxygen plasma but it was removed completely in microwave hydrogen plasma at 700 °C. The surface characteristics after the H-plasma process followed by wet chemical oxidation were restored back to the initial state, as confirmed by XPS. Such “recovery” treatment had been applied t...

Initial stages of ITO/Si interface formation: In situ x-ray photoelectron spectroscopy measurements upon magnetron sputtering and atomistic modelling using density functional theory

Initial stages of indium tin oxide (ITO) growth on a polished Si substrate upon magnetron sputtering were studied experimentally using in-situ x-ray photoelectron spectroscopy measurements. The presence of pure indium and tin, as well as Si bonded to oxygen at the ITO/Si interface were observed. The experimental observations were compared with several atomistic models of ITO/Si interfaces. A periodic model of the ITO/Si interface was constructed, giving detailed information about the local environment at the interface. Molecular dynamics based on density functional theory was performed, showing how metal-oxygen bonds are broken on behalf of silicon-oxygen bonds. These theoretical results support and provide an explanation for the present as well as previous ex-situ and in-situ experimental observations pointing to the creation of metallic In and Sn along with the growth of SiOx at the ITO/Si interface.

Bias-stimulated nucleation of silver prepared by pulsed arc deposition on silicon oxide

The nucleation and interface formation between Ag films and native silicon oxide have been studied with x-ray and ultraviolet photoelectron spectroscopies. Silver was deposited stepwise onto silicon native oxide by pulsed arc deposition technique onto grounded and biased substrates resulting in kinetic energy of incident silver ions of 95 and 720eV, respectively. We show that an increase in the kinetic energy of silver ions leads to more homogeneous nucleation and earlier coalescence of Ag films due to surface defect generation and preferential sputtering of oxygen. In addition, deposition from high energy beam results in the formation of an extended transition layer containing a mixture of Ag and Si oxide that might be beneficial in improving adhesion of Ag films.

Feeling Smooth: Psychotribological Probing of Molecular Composition

The aim of this study was to evaluate whether smooth surfaces varying in surface chemistry could be perceptually distinguished with the sense of touch. A set of ten glass surfaces was prepared which varied systematically in terms of the molecular composition of a thin coating of low topography. The contact angle, contact angle hysteresis, and surface energy were evaluated as objective physical parameters characterizing each coating. Additionally, the interaction forces between a human finger and the different coatings were quantified and compared in terms of tactile friction coefficients. The surfaces were evaluated psychophysically in terms of perceived similarities and were then ranked according to pleasantness. The participants could perceptually distinguish between surfaces varying in surface chemistry and a primary and secondary perceptual dimension were identified as sufficient to distinguish them. The primary dimension correlates with surface free energy, but both tactile friction and surface energy contribute to this dimension depending on whether the coatings are organic or inorganic. The secondary dimension could not be identified explicitly in terms of a physical quantity but is discussed in terms of recent developments in the literature. Coated glass is characterized by high friction coefficient upon interaction with a human finger as well as significant hysteresis in the stroking directions (lower applied load and higher friction in the backward stroke). Despite the complexity of the tribology, pleasantness can be clearly linked to it, where low friction (high contact angle) materials receive a higher ranking.