pH-Controlled Assembly and Properties of LbL Membranes from Branched Conjugated Poly(alkoxythiophene sulfonate) and Various Polycations

We report on multilayer layer-by-layer (LbL) films of the conjugated polymer sodium poly[2-(3-thienyl)ethyloxy-4-butylsulfonate] (PTH) assembled with polycations: poly(diallyldimethylammonium chloride) (PDDA), 20% quaternized poly(N-ethyl-4-vinylpyridinium bromide) (Q20), poly(ethylene imine) (PEI), and poly(allylamine hydrochloride) (PAH). These films were prepared through spin-assisted LbL assembly under various pH conditions. We demonstrated a crucial role of the deposition pH in formation of PTH/polycation films and showed that decrease in the deposition pH from 7.5 to 2.5 limits the PTH multilayer formation to Q20/PTH and PDDA/PTH films due to reduced charge density in the poly(thiophene) chains. We show that optical and surface properties of the resulting PTH/polycation films can be tuned by varying a polycation component and/or by varying the deposition pH. The fluorescence properties of the Q20/PTH, PEI/PTH, and PDDA/PTH films are pH-dependent, and the films exhibit the drastic changes in photoluminescent intensity when transferred into solutions with different pH values, which may find useful in optical sensing applications.