Hierarchical Structure of TPPS₄ J-Aggregates on Substrate Revealed by Atomic Force Microscopy

Abstract

The spatial structure of the J-aggregates of meso-tetra(4-sulfonatophenyl)porphine (TPPS4) formed in acidic aqueous solutions and coated on silicon substrates was analyzed by means of atomic force microscopy (AFM). The AFM experiments indicate the presence of the stripelike J-aggregate structures on the surface. The size of the individual stripes ranged from 4.5 × 40 × 200 to 4.5 × 40 × 1000 nm3 (height × width × length). The length of the stripelike structures varied, whereas stripe width and thickness remained unchanged. The stripes stacked into larger domains, "fibers", containing typically 2−20 stripes aligned parallel with a longitudinal shift with respect to each other. The size of individual stripes remained the same when interacting side-by-side in fibers. At lower magnification it is clearly seen that fibers form a network-like structure. The J-aggregates assemble into large (up to several millimeters) bushlike structures. It takes several weeks to form such structures in acidic aqueous solutions. On the basis of our experimental findings, it is also suggested that the stripes consist of rings that form nanotube-like TPPS4 J-aggregates, which are flattened as a result of attractive interactions with the substrate.