Revealing the Physicochemical Basis of Organic Solid-Solid Wetting Deposition: Casimir-like Forces, Hydrophobic Collapse, and the Role of the Zeta Potential

摘要

Supramolecular self-assembly at the solid–solid interface enables the deposition and monolayer formation of insoluble organic semiconductors under ambient conditions. The underlying process, termed as the organic solid–solid wetting deposition (OSWD), generates two-dimensional adsorbates directly from dispersed three-dimensional organic crystals. This straightforward process has important implications in various fields of research and technology, such as in the domains of low-dimensional crystal engineering, the chemical doping and band gap engineering of graphene, and in the area of field-effect transistor fabrication. However, to date, lack of an in-depth understanding of the physicochemical basis of the OSWD prevented the identification of important parameters, essential to achieve a better control of the growth of monolayers and supramolecular assemblies with defined structures, sizes, and coverage areas. Here we propose a detailed model for the OSWD, derived from experimental and theoretical results that have been acquired by using the organic semiconductor quinacridone as an example system. The model reveals the vital role of the ζ potential and includes Casimir-like fluctuation-induced forces and the effect of dewetting in hydrophobic nanoconfinements. Based on our results, the OSWD of insoluble organic molecules can hence be applied to environmental friendly and low-cost dispersing agents, such as water. In addition, the model substantially enhances the ability to control the OSWD in terms of adsorbate structure and substrate coverage.