Effect of transition metal salts on the initiated chemical vapor deposition of polymer thin films

Abstract

In this work, the effect of transition metal salts on the initiated chemical vapor deposition of polymer thin films was studied using x-ray photoelectron spectroscopy. The polymerizations of 4-vinyl pyridine and 1H,1H,2H,2H-perfluorodecyl acrylate were studied using copper(II) chloride (CuCl2) and iron(III) chloride (FeCl3) as the transition metal salts. It was found that the surface coverages of both poly(4-vinyl pyridine) (P4VP) and poly(1H,1H,2H,2H-perfluorodecyl acrylate) were decreased on CuCl2, while the surface coverage of only P4VP was decreased on FeCl3. The decreased polymer surface coverage was found to be due to quenching of the propagating radicals by the salt, which led to a reduction of the oxidation state of the metal. The identification of this reaction mechanism allowed for tuning of the effectiveness of the salts to decrease the polymer surface coverage through the adjustment of processing parameters such as the filament temperature. Additionally, it was demonstrated that the ability of transition metal salts to decrease the polymer surface coverage could be extended to the fabrication of patterned cross-linked coatings, which is important for many practical applications such as sensors and microelectronics.

Nanotopographical control of surfaces using chemical vapor deposition processes

“…The inhibition of chain growth by transition metals was also demonstrated for different types of monomers by Kwong et al [19,23]. Various metals and metal salts were found to inhibit the growth of acrylate-based polymers and poly(4-vinylpyridine) (P4VP).…”

“…Permissions: (a) was reproduced with permission from [16], copyright 2006 The Royal Society of Chemistry, (b) was reprinted with permission from [18], copyright 2000 American Chemical Society, and (c) was reprinted with permission from [19], copyright 2015, American Vacuum Society.…”

Roll-to-Roll Surface Modification of Cellulose Paper via Initiated Chemical Vapor Deposition

“…We demonstrated that the module could also be used to apply various polymer functionalities onto the rolling substrates by depositing x PMAA, which enables the large-scale production of paper-based microfluidic channels in a single deposition. The use of the roll-to-roll module can be extended to other applications such as large-scale patterning through the use of polymer inhibition , or UV-responsive polymers . Although we demonstrated the process for a roll of several meters, the length of the substrate can be further increased by increasing the height of the reactor with an extension collar.…”

Micro- and nano-surface structures based on vapor-deposited polymers

“…A required pore-sealing process for porous dielectrics was also performed using selectively deposited parylene™ N to avoid the deposition on sub-45 nm copper nodes [ 79 ]. The copolymer poly(4-vinyl pyridine- co -divinyl benzene) was selectively deposited on a chromatography paper with screen-printed copper(II) chloride patterns [ 80 ]. A comprehensive study further examined the deposition of a wide range of functionalized poly( p -xylylenes) on high-energy metal surfaces.…”