RESUMO
Misty plasma processes based on colloidal solutions sprayed into low-pressure plasmas have recently shown great potential for multifunctional thin film deposition. In such processes, nanoparticle accumulation in ring-shaped structures remains the main obstacle to the synthesis of high-quality coatings containing abundant, small-scale, and evenly dispersed nanoparticles. These local buildups appear after a colloidal droplet evaporates from a substrate. Accordingly, controlling the droplets' size in the spray is of key importance to ensure a uniform nanoparticle content in the plasma-deposited nanocomposite film. In this work, it is shown that the use of more volatile solvents produces finer droplets on the substrate, thereby improving nanoparticle dispersion in the matrix. A one-dimensional evaporation model is further developed and used to show that, contrary to what one might expect, this result cannot be attributed to faster evaporation during droplet transport in the low-pressure plasma. Instead, a so-called "flash" boiling atomization mechanism is discussed to support the experimental findings.
RESUMO
This work investigates the effect of plasma treatment on the morphology and composition of 15 × 15 mm2silver nanoparticle (70-80 nm) thin films. The silver nanoparticles are deposited onto thermal silica (SiO2/Si) substrates by spin-coating, then they are treated by an open-to-air microwave argon plasma jet characterized by a neutral gas temperature of 2200 ± 200 K. Scanning electron microscopy analysis reveals that the number of isolated nanoparticles in the film sample decreases after exposure to multiple jet passes, and that polygonal structures with sharp corners and edges are produced. Similar structures with much rounder edges are obtained after conventional thermal annealing at temperatures up to 1300 K. Based on localized surface plasmon resonance analysis in the range of 350-800 nm, the main extinction band of silver nanoparticles experiences a redshift after treatment with the plasma jet or with thermal annealing. Moreover, both treatments induce surface oxidation of the nanoparticles, as evidenced by x-ray photoelectron spectroscopy. However, only the plasma-exposed samples exhibit a significant rise in the surface-enhanced Raman scattering (SERS) signal of oxidized silver at 960 cm-1. 29×29µm2mappings of hyperspectral Raman IMAging (RIMA) and multivariate curve resolution analysis by log-likelihood maximization demonstrate that the SERS signal is controlled by large-scale micrometer domains that exhibit sharp corners and edges.
RESUMO
Photocatalytic surfaces have the potentiality to respond to many of nowadays societal concerns such as clean H2 generation, CO2 conversion, organic pollutant removal or virus inactivation. Despite its numerous superior properties, the wide development of TiO2 photocatalytic surfaces suffers from important drawbacks. Hence, the high temperature usually required (> 450 °C) for the synthesis of anatase TiO2 is still a challenge to outreach. In this article, we report the development and optimisation of an ECWR-PECVD process enabling the deposition of anatase TiO2 thin films at low substrate temperature. Scanning of experimental parameters such as RF power and deposition time was achieved in order to maximise photocatalytic activity. The careful selection of the deposition parameters (RF power, deposition time and plasma gas composition) enabled the synthesis of coatings exhibiting photocatalytic activity comparable to industrial references such as P25 Degussa and Pilkington Activ at a substrate temperature below 200 °C. In addition, to further decrease the substrate temperature, the interest of pulsing the plasma RF source was investigated. Using a duty cycle of 50%, it is thus possible to synthesise photocatalytic anatase TiO2 thin films at a substrate temperature below 115 °C with a deposition rate around 10 nm/min.
