In this study, we demonstrate multilevel and multicomponent layer-by-layer (LbL) assembly as a convenient and generally applicable method for the fabrication of nanofibrillar films by exploiting the dynamic nature of polymeric complexes. The alternate deposition of poly(allylamine hydrochloride)-methyl red (PAH-MR) complexes with poly(acrylic acid) (PAA) produces nanofibrillar PAH-MR/PAA films, which involves the disassembly of PAH-MR complexes, the subsequent assembly of PAH with PAA, and the PAA-induced assembly of MR molecules into MR nanofibrils via a π-π stacking interaction. The aqueous solution of weak polyelectrolyte PAA with a low solution pH plays an important role in fabricating nanofibrillar PAH-MR/PAA films because proton transfer from acidic PAA to MR molecules induces the formation of MR nanofibrils. The generality of the multilevel and multicomponent LbL assembly is verified by alternate assembly of complexes of 1-pyrenylbutyric acid (PYA) and PAH with PAA to fabricate PAH-PYA/PAA films with organized nanofibrillar structures. Unlike the traditional static LbL assembly, the multilevel and multicomponent LbL assembly is dynamic and more flexible and powerful in controlling the interfacial assembly process and in fabricating composite films with sophisticated structures. These characteristics of multilevel and multicomponent LbL assembly will enrich the functionalities of the LbL-assembled films.
