M.A. Signore

Physical properties evolution of sputtered zirconium oxynitride films: effects of the growth temperature

Zirconium oxynitride (ZrNO) films were deposited by RF reactive magnetron sputtering in water vapour–nitrogen atmosphere varying the deposition temperature from RT to 600 °C. Optical analysis, x-ray diffraction, x-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) are the employed characterization techniques to investigate the influence of the substrate temperature on the films physical properties. It was found that the variation of the substrate temperature from RT to 600 °C caused a structural transition from cubic phase of Zr2ON2 to ZrN one, as confirmed by TEM observations too. In particular, Forouhi–Bloomer dispersion equations for optical parameters (n and k) and deconvolution of XPS spectra allowed further chemical properties be elucidated. They also permitted identification of two oxynitride phases, γ phase (Eg = 1.94 eV) and β phase (Eg = 1.7 eV), and an over-stoichiometric nitride one. The use of [Ec − Ev] values helped to confirm further the distinction between (γ, β)-phases and N-rich zirconium nitride compound, which is unachievable by using only Eg values.

Optical function evolution of ion-assisted ZrN films deposited by sputtering

The optical functions (complex dielectric function, complex index of refraction, and complex conductivity) of sputtered zirconium nitride films are derived starting from optical reflectance measurements. Their evolution with the different bias voltages applied during the films growth is used to deduce information about the variations in the electronic structure influenced by a different oxygen and nitrogen content in the films. Improvement in the electrical conductivity is observed at increasing bias voltage due to a reduction in both oxygen contamination and nitrogen content. The separation of the different contributions (free conduction electrons and different electronic transitions) in the optical functions is achieved through the Drude–Lorentz model, allowing the detection of an unusual low-energy electronic transition in films grown at low bias voltages. Through considerations about the electronic structure and about the results coming from other characterization techniques, this transition can be as...

Investigation of the physical properties of ion assisted ZrN thin films deposited by RF magnetron sputtering

Ion bombardment during thin film growth is known to cause structural and morphological changes in the deposited films, thus affecting their physical properties. In this work zirconium nitride films have been deposited by the ion assisted magnetron sputtering technique. The ion energy is controlled by varying the voltage applied to the substrate in the range 0–25 V. The deposited ZrN films are characterized for their structure, surface roughness, oxygen contamination, optical reflectance and electrical resistivity. With increasing substrate voltage crystallinity of the films is enhanced with a preferential orientation of the ZrN grains having the (1 1 1) axis perpendicular to the substrate surface. At the same time, a decrease in electrical resistivity and oxygen contamination content is observed up to 20 V. A higher substrate voltage (25 V) causes an inversion in the observed experimental trends. The role of oxygen contamination decrease and generation of nitrogen vacancies due to ionic assistance have been considered as a possible explanation for the experimental results.

Effects of reducing interferers in a binary gas mixture on NO2 gas adsorption using carbon nanotube networked films based chemiresistors

Analysis of binary gas mixtures using chemiresistors based on carbon nanotubes (CNTs) networked films has been performed for chemical detection up to a sub-ppm level. The effects of individual interfering analytes of reducing H2S and NH3 gases on oxidizing NO2 gas adsorption in CNTs tangled films are considered. The CNTs are grown by plasma-enhanced chemical vapour deposition technology onto inexpensive alumina substrates, coated by cobalt nanosized catalyst. Charge transfer between adsorbed gas molecules and CNT networks, characterized by a semiconducting p-type electrical transport, occurs depending on opposite trend in the sensor response to the electron-donating interfering gases (H2S, NH3) and target electron-withdrawing NO2 gas causing a compensation of the charge transport, upon given working conditions. This compensated exchange of electrical charge affects the limit of detection of the targeted NO2 gas sensed in different real-world binary gas mixtures of reducing interferers of H2S and NH3. In addition, the functionalization of the CNT films with Au nanoclusters enhanced the sensitivity of the chemiresistor and tuned the compensation of electrical charge crossover in the selected binary oxido-reducing mixtures.

Metal-Functionalized and Vertically-Aligned Multiwalled Carbon Nanotube Layers for Low Temperature Gas Sensing Applications

Vertically-aligned carbon nanotubes (CNTs) films have been grown by radiofrequency plasma-enhanced chemical vapor deposition system onto alumina substrates, coated with 2.5 nm thick Fe catalyst, for NO2, H2 and C2H5OH gas sensing applications, at sensor temperatures from room-temperature to 150°C. The CNTs appear in the form of forest-like structure. Nanoclusters of noble metals with nominal thickness of 5 nm of Pt, Ru and Ag have been sputtered on the top-surface of the vertically-aligned CNTs layers to enhance the gas sensitivity. It was demonstrated that the gas sensitivity of the metal modified CNTs-sensors significantly improved by a factor up to an order of magnitude through a spillover effect, and a broader selectivity was provided. The gas sensing properties of the CNTs-sensors, including the metal-modified CNTs, are characterized by a change of the electrical conductivity in a model of the charge transfer with a semiconducting p-type character. The metal-functionalized CNTs-sensors exhibit high sensitivity, fast response, reversibility, good repeatability, sub-ppm range detection limit. A practical application of the CNTs-sensors for monitoring landfill gas is presented.