G. Gottardi

Optical absorption parameters of amorphous carbon films from Forouhi–Bloomer and Tauc–Lorentz models: a comparative study

Parametrization models of optical constants, namely Tauc-Lorentz (TL), Forouhi-Bloomer (FB) and modified FB models, were applied to the interband absorption of amorphous carbon films. The optical constants were determined by means of transmittance and reflectance measurements in the visible range. The studied films were prepared by rf sputtering and characterized for their chemical properties. The analytical models were also applied to other optical data published in the literature pertaining to films produced by various deposition techniques. The different approaches used to determine important physical parameters of the interband transition yielded different results. A figure-of-merit was introduced to check the applicability of the models and the results showed that FB modified for an energy dependence of the dipole matrix element adequately represents the interband transition in the amorphous carbons. Further, the modified FB model shows a relative superiority over the TL ones for concerning the determination of the band gap energy, as it is the only one to be validated by an independent, though indirect, gap measurement by x-ray photoelectron spectroscopy. Finally, the application of the modified FB model allowed us to establish some important correlations between film structure and optical absorption properties.

Intrinsic defects and their influence on the chemical and optical properties of TiO2−x films

In this work, TiO2 films produced by rf sputtering of a TiO2 target in argon and argon–oxygen plasmas were studied. The oxygen content in the feed gas was varied in a range 3–20%. The chemical composition and structure of films were characterized by Rutherford backscattering spectrometry, x-ray photoelectron spectroscopy (XPS) and x-ray diffraction. Important information about the intrinsic defects of the films and their effects on the optical properties as well as a scheme of the energy band structure of the films could be derived from a combined use of optical spectroscopy and XPS.

Low temperature growth study of nano-crystalline TiO2 thin films deposited by RF sputtering

Precise control of the various structural phases of TiO2 at a low temperature is particularly important for practical applications. In this work, the deposition conditions for the growth of anatase and rutile phase at a low temperature (≤300 °C) were optimized. TiO2 films were deposited by radio frequency (RF) sputtering of a ceramic TiO2 target in argon and argon-oxygen plasma (10 and 20% O2) at room temperature. For the films deposited in pure Ar and 20% O2, the growth temperature was varied from 25 to 400 °C. The plasma properties were investigated using optical emission spectroscopy (OES) in a wide range of values of gas composition (0–50% O2 in Ar-O2 mixture). The structural and chemical properties were characterized by means of x-ray diffraction (XRD) and x-ray photoelectron spectroscopy (XPS). The results indicate that O2 addition to the Ar-O2 gas mixture significantly changed the density of the plasma species (Ar, Ar+, Ti, Ti+ and O), which in turn influence the crystal structure and surface chemistry of the prepared films. Anatase phase was obtained for the films grown in Ar-O2 plasma over the whole range of temperature. In contrast, the films deposited in argon discharge largely persist in amorphous phase at temperature ≤200 °C and revealed the formation of single rutile phase at ≥300 °C. The oxygen vacancies detected by XPS analysis for the films deposited in Ar plasma facilitate the growth of a rutile phase at low temperature (~300 °C). Our results demonstrate that oxygen negative ions, oxygen vacancies and surface energy conditions at the substrate are the key parameters controlling the phase of the prepared films at low temperature.

Super-Hydrophilic PDMS and PET Surfaces for Microfluidic Devices

In this work the effect of air plasmas on wettability of Polydimethylsiloxane (PDMS) and polyethylene terephthalate (PET) was studied. These polymers are widely used materials in the fabrication of microfluidic devices. The microfluidic system fabricated from native PET and PDMS requires active pumping mechanism, due to a low hydrophilic surface behavior. To render hydrophilic and increase the capillary flow into the device, plasma treatments can be used. Air plasma treatment is an interesting technology for microfluidic fields due to simplicity of use and low cost. This study describes the effect of the working plasma pressure on wettability of polymers. The polymers were treated by RF plasma and the wettability was studied by means of sessile contact angle. The results established that the air plasma can increase the wettability of both polymers. Moreover we demonstrated that by optimizing the working pressure a superhydrophilic surface (with a contact angle less than 5°) can be obtained. The findings suggest that air plasma treatments are a suitable technology to enhance polymers surface wetting performance for microfluidic devices.

Production and characterization of thin a-C:(H) films for gas permeation barrier functionality against He, CO2, N2, O2 and H2O

This work reports on (i) the gas barrier properties of a-C:H films rf-sputtered in Ar-H(2) plasmas from a graphite target on polyethylene terephthalate (PET) and (ii) the influence of the film chemical structure and defect properties on the gas permeability. The intrinsic permeabilities of the films to He, CO(2), O(2), N(2) gases and H(2)O vapour were determined and found to be orders of magnitude lower than that of the bare PET. Indirect evidence was given to a solubility-diffusion process as the more probable permeation mechanism, over a gas flow through microdefects or gas transport through nanodefects by a Knudsen diffusion mechanism. The barrier capability of the films was found to scale as the gas molecular diameter within the He, CO(2), O(2) and N(2) series, and inversely with the gas critical temperature for the CO(2), O(2), N(2) and H(2)O series. A correlation between the film Urbach energy, E(u), and the gas permeability was established, except for H(2)O. Such findings further favour a bulk diffusion contributing mechanism to permeation over the gas state transport. Conversely, this E(u)-permeability relation shed more light on the origin of the valence band tailing of the amorphous carbon electron structure.

Interaction of the Helium, Hydrogen, Air, Argon, and Nitrogen Bubbles with Graphite Surface in Water

The interaction of the confined gas with solid surface immersed in water is a common theme of many important fields such as self-cleaning surface, gas storage, and sensing. For that reason, we investigated the gas-graphite interaction in the water medium. The graphite surface was prepared by mechanical exfoliation of highly oriented pyrolytic graphite (HOPG). The surface chemistry and morphology were studied by X-ray photoelectron spectroscopy, profilometry, and atomic force microscopy. The surface energy of HOPG was estimated by contact angle measurements using the Owens-Wendt method. The interaction of gases (Ar, He, H2, N2, and air) with graphite was studied by a captive bubble method, in which the gas bubble was in contact with the exfoliated graphite surface in water media. The experimental data were corroborated by molecular dynamics simulations and density functional theory calculations. The surface energy of HOPG equaled to 52.8 mJ/m2 and more of 95% of the surface energy was attributed to dispersion interactions. The results on gas-surface interaction indicated that HOPG surface had gasphilic behavior for helium and hydrogen, while gasphobic behavior for argon and nitrogen. The results showed that the variation of the gas contact angle was related to the balance between the gas-surface and gas-gas interaction potentials. For helium and hydrogen the gas-surface interaction was particularly high compared to gas-gas interaction and this promoted the favorable interaction with graphite surface.

Hydrogen Effect on Structure and Mechanical Properties of ZnO Films Deposited in Ar/H2 Plasma

In the present work the mechanical properties of ZnO thin films, deposited on Si (100) substrates, were studied using the nanoindentation technique. ZnO thin films were deposited by radiofrequency sputtering from a ZnO target with different H2/Ar gas mixtures. During the deposition the plasma species were in-situ monitored using optical emission spectroscopy (OES). The results showed that the introduction of H2 in the plasma phase had a strong effect on the material’s hardness and elastic modulus. The measured elastic modulus values were then related to the material density to estimate the porosity of the ZnO films. We found an increased film porosity when H2 was added to the sputtering gas, from 6% to 18% in volume. Moreover we found that the porosity was correlated by the emission intensity ratio of atomic Argon on atomic Hydrogen.

Efficient hydrogen generation from water using nanocomposite flakes based on graphene and magnesium

Water, through a metal–water reaction, is an appealing candidate to store and release hydrogen (H2), in particular as a portable, easy to use energy storage source. However, the release of hydrogen from the reaction of water with light metals can be violent or be inhibited by the formation of an oxide layer as is the case with magnesium (Mg). For this reason, we studied the use of graphene powder (Gr) as a nano-support to control the reactivity of Mg in water. Nanofilms and nanoparticles of Mg have been grown directly on graphene sheets inducing an increase of Mg surface area and the formation of metallic nanostructures that enhance the responsiveness of metal in water. We surprisingly observed that the water–Mg/Gr reaction happens at room temperature with impressive H2 production (the Mg/Gr hydrogen gravimetric density is 3%). Therefore, the hydrogen generated from water has been successfully used in a fuel cell proving that Mg/Gr is a promising material for on-demand H2 generation.

Graphene as Barrier to Prevent Volume Increment of Air Bubbles over Silicone Polymer in Aqueous Environment

The interaction of air bubbles with surfaces immersed in water is of fundamental importance in many fields of application ranging from energy to biology. However, many aspects of this topic such as the stability of surfaces in contact with bubbles remain unexplored. For this reason, in this work, we investigate the interaction of air bubbles with different kinds of dispersive surfaces immersed in water. The surfaces studied were polydimethylsiloxane (PDMS), graphite, and single layer graphene/PDMS composite. X-ray photoelectron spectroscopy (XPS) analysis allows determining the elemental surface composition, while Raman spectroscopy was used to assess the effectiveness of graphene monolayer transfer on PDMS. Atomic force microscopy (AFM) was used to study the surface modification of samples immersed in water. The surface wettability has been investigated by contact angle measurements, and the stability of the gas bubbles was determined by captive contact angle (CCA) measurements. CCA measurements show that the air bubble on graphite surface exhibits a stable behavior while, surprisingly, the volume of the air bubble on PDMS increases as a function of immersion time (bubble dynamic evolution). Indeed, the air bubble volume on the PDMS rises by increasing immersion time in water. The experimental results indicate that the dynamic evolution of air bubble in contact with PDMS is related to the rearrangement of surface polymer chains via the migration of the polar groups. On the contrary, when a graphene monolayer is present on PDMS, it acts as an absolute barrier suppressing the dynamic evolution of the bubble and preserving the optical transparency of PDMS.