Robert Bogdanowicz

Effect of nitrogen doping on TiOxNy thin film formation at reactive high-power pulsed magnetron sputtering

The paper is focused on a study of formation of TiOxNy thin films prepared by pulsed magnetron sputtering of metallic Ti target. Oxygen and nitrogen were delivered into the discharge in the form of reactive gases O2 and N2. The films were deposited by high-power impulse magnetron sputtering working with discharge repetition frequency f = 250 Hz at low (p = 0.75 Pa) and high (p = 10 Pa) pressure. The substrates were on floating potential and thermally stabilized at room temperature during the deposition process. Post-deposition thermal annealing was not employed. The chemical composition from x-ray photoelectron spectroscopy diagnostic reveals formation of TiOxNy structure at low flow rate of oxygen in the discharge gas mixture. This result is confirmed by XRD investigation of N elements incorporation into the Ti–O lattice. Decrease in band-gap to values Eg ~ 1.6 eV in TiOxNy thin film is attributed to formed Ti–N bonds. The discharge properties were investigated by time-resolved optical emission spectroscopy. Time evolution of particular spectral lines (Ar+, Ti+, Ti) is presented together with peak discharge current.

Physical properties of homogeneous TiO2 films prepared by high power impulse magnetron sputtering as a function of crystallographic phase and nanostructure

Optical, photo-electrochemical, crystallographic and morphological properties of TiO2 thin films prepared by high power impulse magnetron sputtering at low substrate temperatures (<65 °C) without post-deposition thermal annealing are studied. The film composition—anatase, rutile or amorphous TiO2—is adjusted by the pressure (p ~ 0.75–15 Pa) in the deposition chamber. The different crystallographic phases were determined with grazing incidence x-ray diffractometry. The surface morphology and size of TiO2 grains/clusters were imaged with atomic force microscopy. Basic plasma parameters were determined by means of the time-resolved Langmuir probe technique. The power density influx on the substrate was estimated from calorimetric probe measurement. The data from calorimetric probe measurements and time-resolved Langmuir probe served as input parameters for the calculation of influx contributions of particular species. The band-gap energy Eg depends on the film composition and crystallographic phase. Optical parameters (refractive index n + ik, transmittance T, reflectance R and absorbance A) are measured as functions of photon energy in the UV–Vis range by spectroscopic ellipsometry. For the rutile and anatase films agreement with the respective bulk phase is found. Incident photon-current conversion efficiency determined by photo-electrochemical measurements reached the highest values (0.312) for the anatase film.

Local impedance imaging of boron-doped polycrystalline diamond thin films

Local impedance imaging (LII) was used to visualise surficial deviations of AC impedances in polycrystalline boron-doped diamond (BDD). The BDD thin film electrodes were deposited onto the highly doped silicon substrates via microwave plasma-enhanced CVD. The studied boron dopant concentrations, controlled by the [B]/[C] ratio in plasma, ranged from 1 × 1016 to 2 × 1021 atoms cm−3. The BDD films displayed microcrystalline structure, while the average size of crystallites decreased from 1 to 0.7 μm with increasing [B]/[C] ratios. The application of LII enabled a direct and high-resolution investigation of local distribution of impedance characteristics within the individual grains of BDD. Such an approach resulted in greater understanding of the microstructural control of properties at the grain level. We propose that the obtained surficial variation of impedance is correlated to the areas of high conductance which have been observed at the grain boundaries by using LII. We also postulate that the origin of high conductivity is due to either preferential boron accumulation, the presence of defects, or sp2 regions in the intragrain regions. The impedance modulus recorded by LII was in full agreement with the bulk impedance measurements. Both variables showed a decreasing trend with increasing [B]/[C] ratios, which is consistent with higher boron incorporation into BDD film.

Plasma diagnostics of low pressure high power impulse magnetron sputtering assisted by electron cyclotron wave resonance plasma

This paper reports on an investigation of the hybrid pulsed sputtering source based on the combination of electron cyclotron wave resonance (ECWR) inductively coupled plasma and high power impulse magnetron sputtering (HiPIMS) of a Ti target. The plasma source, operated in an Ar atmosphere at a very low pressure of 0.03 Pa, provides plasma where the major fraction of sputtered particles is ionized. It was found that ECWR assistance increases the electron temperature during the HiPIMS pulse. The discharge current and electron density can achieve their stable maximum 10 μs after the onset of the HiPIMS pulse. Further, a high concentration of double charged Ti++ with energies of up to 160 eV was detected. All of these facts were verified experimentally by time-resolved emission spectroscopy, retarding field analyzer measurement, Langmuir probe, and energy-resolved mass spectrometry.

Application of BDD thin film electrode for electrochemical decomposition of heterogeneous aromatic compounds

The aim of the presented study is to investigate the applicability of electrochemical oxidation of aromatic compounds containing heteroatoms, e.g. waste from production of pesticides or pharmaceutics, at a borondoped diamond (BDD) electrode. The BDD electrodes were synthesized by microwave plasma enhanced chemical vapour deposition (MW PE CVD). Investigation of the electrode surface by optical microscopy and scanning electron microscopy (SEM) confirmed that the synthesized layer was continuous and formed a densely packed grain structure with an average roughness of less than 0:5 μm. The influence of important electrochemical parameters: current density, kind of reactor, pH or mixing operation, on the efficiency of the oxidation was investigated. The fouling of electrode’s surface caused by the deposition of organic material was observed during CV and galvanostatic experiments. At low current density the oxidation rate constant k was low, but the current efficiency was relatively high. The BDD can be used successfully to remove heterogeneous aromatic compounds existing either as molecules or cations. During 4 h of electrolysis 95% of aromatic compounds were electrochemically decomposed to mineral forms. It was observed that the influence of the initial pH on mineralization was marginal.

Ellipsometric investigation of nitrogen doped diamond thin films grown in microwave CH4/H2/N2 plasma enhanced chemical vapor deposition

The influence of N2 concentration (1%–8%) in CH_4/H_2/N_2 plasma on structure and optical properties of nitrogen doped diamond (NDD) films was investigated. Thickness, roughness, and optical properties of the NDD films in the VIS–NIR range were investigated on the silicon substrates using spectroscopic ellipsometry. The samples exhibited relatively high refractive index (2.6 ± 0.25 at 550 nm) and extinction coefficient (0.05 ± 0.02 at 550 nm) with a transmittance of 60%. The optical investigation was supported by the molecular and atomic data delivered by Raman studies, bright field transmission electron microscopy imaging, and X-ray photoelectron spectroscopy diagnostics. Those results revealed that while the films grown in CH_4/H_2 plasma contained micron-sized diamond grains, the films grown using CH_4/H_2/(4%)N_2 plasma exhibited ultranano-sized diamond grains along with n-diamond and i-carbon clusters, which were surrounded by amorphous carbon grain boundaries.

Surface-Plasmon-Coupled Emission of Rhodamine 110 in a Silica Nanolayer

The first observation of strong directional surface-plasmon-coupled emission (SPCE) of Rhodamine 110 in silica nanofilms deposited on silver nanolayers is reported. The preparation of the material is described in detail. The intensity of SPCE exceeds 10 times that of free space fluorescence and total linear light polarization in the SPCE ring is observed. A new experimental setup and an original data collection method is presented. Our material completely preserves its fluorescence properties for at least eight months.

Boron-Enhanced Growth of Micron-Scale Carbon-Based Nanowalls: A Route toward High Rates of Electrochemical Biosensing

In this study, we have demonstrated the fabrication of novel materials called boron-doped carbon nanowalls (B:CNWs), which are characterized by remarkable electrochemical properties such as high standard rate constant (k°), low peak-to-peak separation value (ΔE) for the oxidation and reduction processes of the [Fe(CN)6]3-/4- redox system, and low surface resistivity. The B:CNW samples were deposited by the microwave plasma-assisted chemical vapor deposition (CVD) using a gas mixture of H2/CH4/B2H6 and N2. Growth results in sharp-edged, flat, and long CNWs rich in sp2 as well as sp3 hybridized phases. The achieved high values of k° (1.1 × 10-2 cm s-1) and ΔE (85 mV) are much lower compared to those of the glassy carbon or undoped CNWs. The enhanced electrochemical performance of the B:CNW electrode facilitates the simultaneous detection of DNA purine bases: adenine and guanine. Both separated oxidation peaks for the independent determination of guanine and adenine were observed by means of cyclic voltammetry or differential pulse voltammetry. It is worth noting that the determined sensitivities and the current densities were about 1 order of magnitude higher than those registered by other electrodes.

Surface Plasmon-Coupled Emission of Rhodamine 110 Aggregates in a Silica Nanolayer

First analysis of strong directional surface plasmon-coupled emission (SPCE) of ground-state formed intermolecular aggregates of Rhodamine 110 (R110) in silica nanofilms deposited on silver nanolayers is reported. Until now, the processes of energy transport and its trapping due to aggregate formation have not been studied in the presence of SPCE. A new approach to multicomponent systems with weakly and strongly fluorescent centers making use of fluorophore-surface plasmon interaction is presented. The analysis is based on comparison of experimental free-space emission spectra (F-SE), experimental SPCE with theoretical surface plasmon resonance spectra (SPR). It is shown that, due to the dispersion of SPCE, the detection of weak aggregate emission is straightforward if only the monomers and aggregates fluorescence spectra are somewhat spectrally shifted. SPCE studies confirmed the formation of weakly fluorescent higher order aggregates of R110 in silica films. The results indicate that the increase of energy transfer from monomers to aggregates is due to fluorophore-plasmon interaction.

Optically transparent boron-doped nanocrystalline diamond films for spectroelectrochemical measurements on different substrates

Fabrication process of optically transparent boron nanocrystalline diamond (B- NCD) electrode on silicon and quartz substrate was shown. The B-NCD films were deposited on the substrates using Microwave Plasma Assisted Chemical Vapor Deposition (MWPACVD) at glass substrate temperature of 475 °C. A homogenous, continuous and polycrystalline surface morphology with high sp3 content in B-NCD films and film thickness depending from substrate in the range of 60-300 nm was obtained. The high refraction index and transparency in visible (VIS) wavelength range was achieved. Moreover, cyclic voltammograms (CV) were recorded to determine reaction reversibility at the B-NCD electrode. CV measurements in aqueous media consisting of 1 mM K3[Fe(CN)6] in 0.5 M Na2SO4 demonstrated relatively fast kinetics expressed by a redox peak splitting below 503 mV for B-NCD/silicon and 110 mv for B-NCD/quartz.