Aggregation of the polydopamine (PDA) molecular building
blocks
at the air/water interface leads to obtaining large surface nanometric-thin
films. This mechanism follows two possible pathways, namely, covalent
or non-covalent self-assembly, which result in a different degree
of structure order and, consequently, different structural properties.
Control of this mechanism could be vital for applications that require
true self-support PDA free-standing films, for example, electrochemical
sensing or membrane technology. Here, we are considering the impact
of boric acid (BA) and Cu2+ ions on the mentioned mechanism
exclusively for the free-standing films from the air/water interface.
We have employed and refined our own spectroscopic reflectometry method
to achieve an exceptionally high real-time control over the thickness
growth. It turned out that BA and Cu2+ ions significantly
impact the film growth process. Reduction of the nanoparticles size
and their number was examined via UV–vis spectroscopy and transmission
electron microscopy, showing a colossal reduction in the mean diameter
of nanoparticles in the case of BA and a moderate reduction in the
case of Cu2+. This modification is leading to significant
enhancement of the process efficiency through moderation of the topological
properties of the films, as revealed by atomic force microscopy. Next,
applying infrared, Raman, and X-ray photoelectron spectroscopy, we
presented small amounts of metal (B or Cu) in the final structure
of PDA and simultaneously their vital role in the oxidation mechanism
and cross-linking through covalent or non-covalent bonds. Therefore,
we revealed the possibility of synthesizing films via the expected
self-assembly mechanism which has hitherto been out of control. Moreover,
modification of mechanical properties toward exceptionally elastic
films through the BA-assisted synthesis pathway was shown by achieving
Young’s modulus value up to 24.1 ± 5.6 and 18.3 ±
6.4 GPa, using nanoindentation and Brillouin light scattering, respectively.