High-power pulsed magnetron discharges have drawn an increasing interest as an approach to produce highly ionized metallic vapor. In this paper we propose to study how the plasma composition and the deposition rate are influenced by the pulse duration. The plasma is studied by time-resolved optical emission and absorption spectroscopies and the deposition rate is controlled thanks to a quartz microbalance. The pulse length is varied between 2.5 and 20 s at 2 and 10 mTorr in pure argon. The sputtered material is titanium. For a constant discharge power, the deposition rate increases as the pulse length decreases. With 5 s pulse, for an average power of 300 W, the deposition rate is ϳ70% of the deposition rate obtained in direct current magnetron sputtering at the same power. The increase of deposition rate can be related to the sputtering regime. For long pulses, self-sputtering seems to occur as demonstrated by time-resolved optical emission diagnostic of the discharge. In contrary, the metallic vapor ionization rate, as determined by absorption measurements, diminishes as the pulses are shortened. Nevertheless, the ionization rate is in the range of 50% for 5 s pulses while it lies below 10% in the case of a classical continuous magnetron discharge.

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The influence of the capacitive (E)-to-inductive transition (H) in inductively coupled plasma discharges is investigated for propanethiol plasma polymerization. In the E mode, at low plasma density, the sulfur content in the layers, measured by XPS, is quite high and strongly decreases after aging in the air. This phenomenon is attributed to the desorption of trapped sulfur-based molecules (e.g., H 2 S). In the H mode, presumably higher surface temperature prevents the trapping scenario during the layer growth and, as a consequence, yields a lower sulfur content which is stable after aging. Mass spectrometry measurements reveal important variations of the plasma chemistry depending on the discharge mode. The major change concerns the complete disappearance of the precursor in the H mode accompanied by the large production of CS 2 molecules. Furthermore, a linear correlation is found between the concentration of the CS 2 species and the atomic sulfur content in the Hmode synthesized layers. In addition, based on DFT calculations, different pathways of fragmentation are proposed as a function of the plasma parameters. The whole set of results highlight the importance of the E−H transition for the growth of thiol-based plasma polymers.

Multi-walled carbon nanotubes (MWNTs) are placed under atomic nitrogen flow formed through an Ar + N 2 microwave plasma in order to functionalize covalently their side walls with nitrogen-containing groups. The MWNT surface analyzed by X-ray photoelectron spectroscopy shows the presence of amides, oximes and mainly amine and nitrile functions grafted in this way. In order to highlight the actual location of the amine functions grafted on MWNTs, they were considered as initiation species in ring-opening polymerization of e-caprolactone using triethylaluminium as activator. The so-generated poly(e-caprolactone) chains remain grafted on the MWNTs via amide bonds and form polyester islets along the nanotubes surface. TEM images of these MWNT surfaces grafted with poly(e-caprolactone) show a good amino-sidewall distribution. This work demonstrates the side-wall amino-functionalization of carbon nanotubes readily achieved by microwave plasma with the possibility to reach within a short time period very high contents in nitrogen-based functions (y10 at.%).