Wet-processed films of crystalline metal phthalocyanines (MPc’s) are constructed from compact islands surrounded by disordered dye matter, which limits the physical properties of MPc films and, thus, requires much structural improvement. The present work considers this problem through the prism of a model compound, namely, highly symmetrical copper tetra-tert-butylporphyrazine (C4h-CuPaz) that readily crystallizes irrespective of experimental conditions. Specifically, the film-forming properties of C4h-CuPaz were examined in both an individual dye sample and a mixture of C4h-CuPaz with the asymmetrical isomers. The dye films deposited by using the Langmuir–Schaefer technique were characterized by Brewster angle microscopy, scanning electron microscopy, small-angle X-ray scattering, and optical spectroscopy. The experimental data were integrated to construct a comprehensive scenario of the crystalline film growth starting from colloidal aggregates preassembled on the water surface. Finally a stratagem for improving the morphology of solution-processed MPc films is proposed: to obtain properly structured crystalline films, a stable hybrid phase composed of two MPc’s with different phase behaviors should be designed as a physical substitute for the disordered dye matter.
