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High-temperature plasmonics deals with optically active nanostructures that can withstand high temperatures. A conventional approach relying on standalone noble metal nanoparticles fails to deliver refractory plasmonic nanomaterials, and an alternative route envisions metal nitrides. The main challenge remains the development of advanced synthesis techniques and the insight into thermal stability under real-life application conditions. Here, hafnium nitride nanoparticles (HfN NPs) can be produced by gas aggregation using reactive magnetron sputtering, a technique with a small environmental footprint are shown. As-deposited NPs are of 10 nm mean size and consist of stoichiometric, crystalline fcc HfN. They are characterized by optical absorption below 500 nm caused by interband transitions and in the red/near-infrared (NIR) region due to intraband transitions and localized surface plasmon resonance (LSPR). The optical response can be engineered by tuning the NP composition as predicted by finite-difference time-domain (FDTD) calculations. Going beyond the state-of-the-art, the HfN NP thermal stability is focued under ultrahigh vacuum (UHV) and in air. During UHV annealing to 850 °C, the NPs retain their morphology, chemical and optical properties, which makes them attractive in space mission and other applications. During air annealing to 800 °C, HfN NPs remain stable until 250 °C, which sets a limit for air-mediated use.

Plasma polymer films typically consist of very short fragments of the precursor molecules. That rather limits the applicability of most plasma polymerisation/plasma-enhanced chemical vapour deposition (PECVD) processes in cases where retention of longer molecular structures is desirable. Plasma-assisted vapour thermal deposition (PAVTD) circumvents this limitation by using a classical bulk polymer as a high molecular weight “precursor”. As a model polymer in this study, polylactic acid (PLA) has been used. The resulting PLA-like films were characterised mostly by X-ray photoelectron spectroscopy (XPS) and nuclear magnetic resonance (NMR) spectroscopy. The molecular structure of the films was found to be tunable in a broad range: from the structures very similar to bulk PLA polymer to structures that are more typical for films prepared using PECVD. In all cases, PLA-like groups are at least partially preserved. A simplified model of the PAVTD process chemistry was proposed and found to describe well the observed composition of the films. The structure of the PLA-like films demonstrates the ability of plasma-assisted vapour thermal deposition to bridge the typical gap between the classical and plasma polymers. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.

In this work, composite layers of hexamethyldisilazane (HMDSN) and lactic acid (LA) were prepared using chemical vapor deposition process by a nitrogen atmospheric pressure plasma jet source. The HMDSN vapours were introduced into the plasma jet. Varying LA admixture was added into the jet in the form of aerosol. The chemical composition, morphology and wettability of resulting films were studied. Infrared spectra and XPS analysis show both Si-O like and hydrocarbon structures. With increasing amount of LA admixture, the oxidation of the layers increases. The morphology of the films was measured with SEM. The films prepared with no LA have a foam-like structure. With increasing amount of LA the structure changes into more fractal-like. The X-ray diffraction analysis suggests the presence of amorphous SiO2 domains in the films. The films exhibited superhydrophobic properties that can be modified by the post-treatment of the samples in DBD discharge. © NANOCON 2019.All right reserved.

Polyester urethane polymer was synthesized as linked biocompatible poly (lactide)/poly (ethylene oxide) polymers. The bulk polymer was subsequently used as precursor material for plasma assisted vapour thermal deposition of thin plasma polymer films under varying RF discharge power. The effect of plasma polymerization on the final physico-chemical characteristics was investigated. The chemical analysis of the films was performed using X-ray photoelectron spectroscopy and infrared spectroscopy. Structural analysis of plasma polymer thin film revealed the similar molecular structure as in case of precursor since PEU-characteristic bonds were preserved after the plasma polymerization. Surface properties analysed by a contact angle measurement revealed an increase of wettability in the samples prepared at higher RF power. At the same time a surface energy evaluated according to acid-base model decreased. The results indicate that plasma polymer films properties could be tuned depending on applied deposition conditions. © NANOCON 2019.All right reserved.

Poly(ethylene oxide) (PEO)-like thin films were successfully prepared by plasma-assisted vapor thermal deposition (PAVTD). PEO powders with a molar weight (Mw) between 1500 g/mol and 600,000 g/mol were used as bulk precursors. The effect of Mw on the structural and surface properties was analyzed for PEO films prepared at a lower plasma power. Fourier transform (FTIR-ATR) spectroscopy showed that the molecular structure was well preserved regardless of the Mw of the precursors. The stronger impact of the process conditions (the presence/absence of plasma) was proved. Molecular weight polydispersity, as well as wettability, increased in the samples prepared at 5 W. The influence of deposition plasma power (0-30 W) on solubility and permeation properties was evaluated for a bulk precursor of Mw 1500 g/mol. The rate of thickness loss after immersion in water was found to be tunable in this way, with the films prepared at the highest plasma power showing higher stability. The effect of plasma power deposition conditions was also shown during the permeability study. Prepared PEO films were used as a cover, and permeation layers for biologically active nisin molecule and a controlled release of this bacteriocin into water was achieved. © 2020 by the authors.

Classical “wet“chemistry methods can produce polymers with well-defined molecular structure, but many types of polymers are difficult to prepare with significant degree of crosslinking without residues of the crosslinking agent. On the other hand, plasma polymers usually have very high degree of crosslinking but nearly random molecular structure. Plasma assisted vapour thermal deposition combines both methods. Classical polymers are heated in a crucible at low pressure and the released oligomeric fragments of the polymer chain are repolymerized in a glow discharge into a thin film. The number of well-preserved monomeric units between the crosslinks can be tuned e.g. from units to tens. Poly-lactic acid (PLA) belongs to a special class of biodegradable polymeric materials. In this work, plasma assisted vapour thermal deposition was utilized to prepare PLA plasma polymers. Molar weights and chemical composition of the “precursor” polymer and of the thin films have been characterized. As the measure of degradability, behaviour of the polymers during hydrolysis has been studied using spectroscopic ellipsometry and liquid chromatography. Possibility to prepare plasma polymer films with controlled degradability was demonstrated. © 2018 TANGER Ltd. All Rights Reserved.