Self-Patterning Polyelectrolyte Multilayer Films: Influence of Deposition Steps and Drying in a Vacuum

Typically, laterally patterned films are fabricated by lithographic techniques, external fields, or di-block copolymer self-assembly. We investigate the self-patterning of polyelectrolyte multilayers, poly(diallyldimethylammonium) (PDADMA)/poly(styrenesulfonate) (PSS)_short. The low PSS molecular weight (M_w(PSS_short) = 10.7 kDa) is necessary because PSS_short is somewhat mobile within a PDADMA/PSS_short film, as demonstrated by the exponential growth regime at the beginning of the PDADMA/PSS_short multilayer build-up. No self-patterning was observed when the PDADMA/PSS film consisted of only immobile polyelectrolytes. Atomic force microscopy images show that self-patterning begins when the film consists of seven deposited PDADMA/PSS_short bilayers. When more bilayers are added, the surface ribbing evolved into bands, and circular domains were finally observed. The mean distance between the surface structures increased monotonously with the film thickness, from 70 to 250 nm. Scanning electron microscopy images showed that exposure to vacuum resulted in thinning of the film and an increase in the mean distance between domains. The effect is weaker for PSS_short-terminated films than for PDADMA-terminated films. The mechanism leading to domain formation during film build-up and the effect of post-preparation treatment are discussed.