Abstract
Metal phthalocyanines (MPcs) are an abundant class of small molecules comprising of a highly conjugated cyclic structure with a central chelated metal ion. Due to their remarkable chemical, mechanical, and thermal stability MPcs have become popular for a multitude of applications since their discovery in 1907. The potential for peripheral and axial functionalization affords structural tailoring to create bespoke MPc complexes for various next generation applications. Specifically, thin-films of MPcs have found promising utility in medical and electronic applications where the need to understand the relationship between chemical structure and the resulting thin-film properties is an important ongoing field. This review aims to compile the fundamental principles of small molecule thin-film formation by physical vapour deposition and solution processing focusing on the nucleation and growth of crystallites, thermodynamic and kinetic considerations, and effects of deposition parameters on MPc thin-films. Additionally, the structure-property relationship of MPc thin-films is examined by film microstructure, morphology and physical properties. The topics discussed in this work will elucidate the foundations of MPc thin-films and emphasize the critical need for not only molecular design of new MPcs but the role of their processing in the formation of thin-films and how this ultimately governs the performance of the resulting application.
Highlights
In the simplest form, Metal phthalocyanines (MPcs) (C32H18N8M) consist of four isoindole groups connected by nitrogen atoms forming an 18 pelectron ring structure, with two covalent bonds and two coordination bonds chelating a metal or metalloid center (Fig. 1).Rosemary R
An important advantage of the atomistic models is that nucleation can be expressed in terms of measurable parameters such as deposition rate and substrate temperature, instead of quantities such as DG* and gi, whose values cannot be known with certainty or estimated.[17,20,21]
Vm is the molar volume of the liquid solvent, DSvap is the entropy of vapourization of the solvent, Tb is the boiling point of the solvent at atmospheric pressure, and A is a single tting parameter combining all temperature independent variables.[77,78]
Summary
In the simplest form, MPcs (C32H18N8M) consist of four isoindole groups connected by nitrogen atoms forming an 18 pelectron ring structure, with two covalent bonds and two coordination bonds chelating a metal or metalloid center (Fig. 1). Cranston received her BASc in Chemical Engineering from the University of Ottawa in 2019 and is currently pursuing her PhD in the Lessard Research Group. Her current research focuses on characterizing thin- lm formation of axially substituted silicon phthalocyanines, and their implementation in solution processed n-type organic thin- lm transistors. Benoıt Lessard obtained his PhD (2012) from McGill University in Polymer synthesis and reaction engineering. He completed an NSERC Banting Postdoctoral Fellowship at the University of Toronto studying crystal engineering and engineering organic photovoltaics and organic light emitting diodes. The nal section reviews some of the most relevant and promising synchrotron based X-ray techniques which can be used to characterize and study MPc thin- lms
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