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Investigating Zigzag Film Growth Behaviors in Layer-by-Layer Self-Assembly of Small Molecules through a High-Gravity Technique.

The zigzag film growth behavior in the layer-by-layer (LbL) assembly method is a ubiquitous phenomenon for which the growth mechanism was rarely investigated, especially for small molecules. To interpret the zigzag increasing manner, we hypothesized that the desorption kinetics of small molecules was dominant for the film growth behavior and demonstrated this hypotheis by introducing the high-gravity technique into the LbL assembly of a typical polyelectrolyte/small molecule system of polyethylenimine (PEI) and meso-tetra(4-carboxyphenyl)porphine (Por). The results showed that the high-gravity technique remarkably accelerated the desorption process of Por; the high-gravity LbL assembly provides a good platform to reveal the desorption kinetics of Por, which is tedious to study in conventional situation. We found that as much as 50 min is required for Por molecules to reach desorption equilibrium from the substrate to the bulk PEI solution for the conventional dipping method; however, the process could be accelerated and require only 100 s if a high-gravity field is used. Nonequilibrated desorption at 10 min for normal dipping and at 30 s for high-gravity-field-assisted assembly both exhibited a zigzag film growth, but after reaching desorption equilibrium at 100 s under a high-gravity field, film growth began to cycle between assembly and complete disassembly instead of LbL assembly. For the first time we have proven that the high-gravity technique can also accelerate the desorption process and demonstrated the desorption-dependent mechanism of small molecules for zigzag film growth behaviors.