Surface pattern based on an azobenzene-containing copolymer thin film and its light-driven morphology modulation

A type of azobenzene-containing block copolymer polymethyl methacrylate-b-poly (n-butylmethacrylate-co-6-(4-(phenylazo) benzoate) hexyl methacrylate) (PMMA-b-(PnBMA-co-PAzoMA)) was synthesized by the atom transfer radical polymerization (ATRP). Macroinitiator polymethyl methacrylate (PMMA) was prepared by ATRP and used to initiate the copolymerization of monomer n-butyl methacrylate (nBMA) and azobenzene-based methacrylate monomer (AzoMA). Herein, three block copolymers with different molecular weights and block volume fractions were obtained and spin-coated on a silicon substrate or quartz plate before annealing at 180 °C for 14 h. The surface morphologies in these annealed copolymer films were observed by atomic force microscopy (AFM). Bicontinuous stripe or island patterns with different sizes were formed dependent on the film thickness. These ordered patterns are considered to be formed arising from the dewetting process of the surface layer in the copolymer film. Photoisomerization of azobenzene units in the copolymer films changed the dewetting behaviors of the surface layer of the thin film. Therefore, some copolymer annealed films showed a reversible morphology conversion between bicontinuous stripe and island structure when exposed to UV light and upon being stored in the dark. It was found that the composition of the block copolymer had obvious influences on the photoinduced morphology conversion behaviors in these copolymer thin films. When the volumes of PnBMA and PAzoMA phases in the block copolymer were large enough, the surface morphology could be modulated by UV light irradiation and storage in the dark. This work proposes a new possibility for photoinduced control and design of the dewetting processes of thin films using a linear block copolymer.