Mechanisms of Plasma Polymerization – Reviewed from a Chemical Point of View

Abstract

Several reaction mechanisms have been proposed for the formation of plasma polymers, such as monomer fragmentation followed by poly‐recombination into randomly structured and crosslinked films; fragmentation, accompanied by the formation of acetylene or other film‐forming intermediates and deposition of polystyrene‐like material; plasma‐initiation of a radical chain‐growth polymerization; and ion‐molecule reactions, as well as ionic chain‐growth polymerization. The bulk structure of plasma polymers is completely irregular, far from that of conventional polymers. The retention of functional groups during plasma polymerization tends to be greater than that of the entire monomer structure found again as an intact repeat unit in the resulting plasma polymer. An alternative method for depositing ultra‐thin, pin‐hole free coatings, ones that possess regular structures, is by electrospray ionization (ESI) of pre‐fabricated polymers.

Non-thermal plasma assisted lithography for biomedical applications: an overview

“…In a series of first-order processes, these fragments will rearrange, reactivate and fragment again, resulting in low deposition rates. The deposited thin film will therefore have a monomer composition and structure that is barely recognisable [57,58,63,64]. In terms of biomedical applications, the atomic deposition regime is of less interest.…”

“…The reaction mechanisms behind the plasma polymerisation process have been a source of discussion among the leading scientists in the field for the last 50 years and many different models have been proposed. In 2011, Friedrich [58] wrote an excellent review on the subject, collecting and comparing the most popular models.…”

Photo-initiated chemical vapor deposition as a scalable particle functionalization technology (a practical review)

“…For example, Andrzejewska [72] and Friedrich [17] wrote impressive reviews exclusively on the photopolymerization kinetics. Boies et al, from the same research group as Zhang, have recently published a kinetic study of the PICVD applied to the coating of silver nanoparticles in the gas phase [47].…”

“…New solutions have to be proposed. This paper is not intended to be an extensive review from a fundamental point of view since this work has already been done many times by di↵erent groups [13,16,17]. However, by reading those reviews, one can be easily be distracted by the terminology which lacks standardization and classification.…”

Super-Adhesive Polymer–Silica Nanocomposite Layers

“…32,34 However, in this case there exist limitations due to high precursor vapour pressures/flow rates leading to plasma instabilities/inhomogeneity and eventual extinction. Such shortcomings can be overcome by utilizing an atomized spray of the precursor which limits perturbations to the plasma excitation medium by localizing the precursor molecules into concentrated fine droplets.…”