AVS 63rd International Symposium & Exhibition
    Plasma Science and Technology Tuesday Sessions
       Session PS+2D-TuA

Paper PS+2D-TuA7
Initiated Plasma Enhanced Chemical Vapor Deposition of Metalloporphyrins: A Simple Route towards the Deposition of Metal Organic Covalent Networks

Tuesday, November 8, 2016, 4:20 pm, Room 104B

Session: Plasma Processing for Nanomaterials and 2D Materials
Presenter: Nicolas BOSCHER, Luxembourg Institute of Science and Technology, Luxembourg
Authors: N. BOSCHER, Luxembourg Institute of Science and Technology, Luxembourg
M. WANG, Massachusetts Institute of Technology
K. GLEASON, Massachusetts Institute of Technology
Correspondent: Click to Email
Porphyrins and porphyrinoids are robust and versatile functional molecules with varying properties depending on their central metal ion and peripheral and axial substituents. They have proved to be useful in a wide range of applications, including the catalysis and photocatalysis of various chemical reactions, in molecular sensing, light harvesting applications, and for gas storage and gas separation applications. In addition to these functional assets, their rigidity and chemical stability make them ideal as building units for the formation of covalent and coordination metal-organic polymers, including metal-organic frameworks (MOFs). Nevertheless, the difficult processability of these poorly soluble and non-meltable materials makes difficult their integration into smart devices.

Provided the fact that the monomer to deposit possesses free-radical polymerizable bonds, initiated PECVD (iPECVD) promotes conventional chain-growth polymerisation pathways, ensuring an excellent retention of the monomer structure. Several works have highlighted the radical polymerizability of the exo-pyrrole double bond of the porphyrin rings. The propagation reaction occurs at the beta-position of the porphyrin ring, leading to the formation of a polymer of reduced porphyrins, i.e. chlorin. Based on this wet-chemistry result, we recently investigated the use of zinc (II) meso-tetraphenylporphyrin (ZnTPP) building units in an iPECVD process and formed a new kind of metal-organic covalent network (MOCN) thin films.