Molecular origin of structural defects in the zinc phthalocyanine film.

Controlling the growth of thin phthalocyanine films is a long-term challenge for the science of applied nanomaterials. So, this contribution deals with films of unsubstituted zinc phthalocyanine (ZnPc) and seeks to acquire structural information that is unavailable via physical experiments, thus, finding out how the film morphology can be seriously improved. A model of the vapor-deposited film has been created using the molecular dynamics method. Specifically, the ZnPc molecules are dosed into the simulation box under normal conditions, reproducing key features of the real film, such as the trimolecular wetting layer and the island-like three-dimensional (3D) phase that is structured like the α-polymorph; then all film fragments are characterized via their radial distribution functions and mean-squared displacements. The simulation model indicates that the 3D phase starts to develop smoothly through multimolecular cofacial stacking but finally becomes fragmental because the wetting layer is too meager to be a good platform for regular film growth. Accordingly, the film morphology may be improved if the wetting layer is thickened via restraining the vertical development of the 3D phase. Following this idea, uniform ZnPc films impaired by neither grain boundaries nor coarser defects were deposited from solutions and visualized at the nanometer scale.

Amine-assisted solubilization of unsubstituted zinc phthalocyanine for film deposition purposes.

Typical zinc phthalocyanines (ZnPc) exhibit poor solubility in common solvents and, hence, are processed into thin films mostly from the vapor phase. The present work discloses how these limitations can be effectively overcome. Specifically, highly concentrated molecular solutions of unsubstituted ZnPc are prepared by combining a weakly structured ZnPc polymorph with binary liquid systems composed of a π-accepting solvent and a simple nitrogenous base, such as ammonia or tertiary aliphatic amine. The amine-assisted solubilization of ZnPc is rationalized by quantitative analysis of optical spectra and electrostatic potential maps of the dye molecule. A volatile aminoalcohol is proposed in order to rationally modify the habit of ZnPc crystallites and concurrently to produce uniform deposition of the crystallites by drop-casting the dye solutions onto a glass substrate. Finally, a versatile algorithm for wet-processed ZnPc films is declared.