R. Bartali

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.

Influence of hydrogen addition to an Ar plasma on the structural properties of TiO2−x thin films deposited by RF sputtering

The influence of hydrogen addition to an Ar plasma on the structural properties of TiO2−x films produced by RF sputtering of a TiO2 target at room temperature was studied. The structural properties of the films were characterized by x-ray photoelectron spectroscopy while the surface morphology was analysed using scanning electron microscopy (SEM). The valence band analysis showed the crystal field splitting of d states into doubly and triply degenerate states. H2 addition to the Ar plasma created additional d-state splitting due to distortions in the TiO2 structure by the Jahn–Teller mechanism. The occurrence of the Jahn–Teller split is well-correlated with oxygen vacancies in the TiO2−x films. Water adsorption at the TiO2−x surface and film hydroxylation were also addressed. The as-grown films were amorphous and SEM analysis showed a columnar structure for all the films but with a lower packing density of the columns after H2 introduction in the Ar plasma.

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.

Argon–hydrogen rf plasma study for carbon film deposition

In this work the effect of hydrogen addition on the physical properties and the sputtering efficiency of an radio-frequency (rf) (13.56 MHz) Ar plasma was investigated. The discharges in Ar–H2 were used to sputter-deposit carbon films from a graphite cathode, with a hydrogen concentration in the feed gas ranging from 0 to 100% (the useful range for film growth was however limited to 0–85%). The physical plasma parameters were determined using a Langmuir probe, which, coupled with a chemical modelling of the ion–molecule and electron–molecule reactions in gas phase, enabled us to define the energy flux conditions at the cathode. The results show that hydrogen exerts a positive effect on the film deposition rate at the lowest end of the hydrogen concentration range, an enhancing deposition effect correlated with a high density of ArH+ ions in the plasma and a high energy flux carried by the ions to the cathode. Nonetheless, an analysis of the processes at the cathode indicates that the sputtering mechanism was essentially physical in the low [H2] range (3–20%) but that a chemical assistance of the process should be considered too for the remaining [H2] range. Besides, even in the physical sputtering regime, the target material removal occurred with a reactive sputtering mechanism, which implies a chemical modification of the target surface layers and surface binding energy.

PDMS/Kapton Interface Plasma Treatment Effects on the Polymeric Package for a Wearable Thermoelectric Generator

The present work highlights the progress in the field of polymeric package reliability engineering for a flexible thermoelectric generator realized by thin-film technology on a Kapton substrate. The effects of different plasma treatments on the mechanical performance at the interface of a poly(dimethylsiloxane) (PDMS)/Kapton assembly were investigated. To increase the package mechanical stability of the realized wearable power source, the Kapton surface wettability after plasma exposure was investigated by static contact-angle measurements using deionized water and PDMS as test liquids. In fact, the well-known weak adhesion between PDMS and Kapton can lead to a delamination of the package with an unrecoverable damage of the generator. The plasma effect on the adhesion performances was evaluated by the scratch-test method. The best result was obtained by performing a nitrogen plasma treatment at a radio-frequency power of 20 W and a gas flow of 20 sccm, with a measured critical load of 1.45 N, which is 2.6 times greater than the value measured on an untreated Kapton substrate and 1.9 times greater than the one measured using a commercial primer.

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.

Mechanical characterization of thin TiO2 films by means of microelectromechanical systems-based cantilevers

The measurement of mechanical parameters by means of microcantilever structures offers a reliable and accurate alternative to traditional methods, especially when dealing with thin films, which are extensively used in microfabrication technology and nanotechnology. In this work, microelectromechanical systems (MEMS)-based piezoresistive cantilevers were realized and used for the determination of Youngs modulus and residual stress of thin titanium dioxide (TiO(2)) deposited by sputtering from a TiO(2) target using a rf plasma discharge. Films were deposited at different thicknesses, ranging from a few to a hundred nanometers. Dedicated silicon microcantilevers were designed through an optimization of geometrical parameters with the development of analytical as well as numerical models. Youngs modulus and residual stress of sputtered TiO(2) films were assessed by using both mechanical characterization based on scanning profilometers and piezoresistive sensing elements integrated in the silicon cantilevers. Results of MEMS-based characterization were combined with the tribological and morphological properties measured by microscratch test and x-ray diffraction analysis.

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.

Primary cortical neurons on PMCS TiO2 films towards bio-hybrid memristive device: A morpho-functional study

We report a comprehensive study of the biocompatibility and neurocompatibility of titanium dioxide films (TiO2) prepared by Pulsed Microplasma Cluster Source (PMCS). This technique uses supersonic pulsed beams seeded by clusters of the metal oxide synthesized in a plasma discharge. The final stoichiometry of the TiO2 thin films is tuned changing the gas mixture, achieving stoichiometric or oxygen overstoichiometric films. All the films showed consistent biocompatibility and a spontaneous absorption of poly-d-lysine (PDL) that favors the adhesion and growth of murine cortical neurons. Moreover, the bioelectrical activity of the neuronal culture grown on the TiO2 film can be modulated by changing the chemistry of the surface. This work paves the way to develop a bio-hybrid neuromorphic device, where viable nerve cells are grown directly over a titanium dioxide film showing a network of memristors.