When block copolymer self-assembly in hierarchically ordered honeycomb films depicts the breath figure process.

Nowadays, a challenge in the preparation of hierarchically ordered materials is the control of concomitant and interacting self-organization processes occurring in time at different length scales. In the present paper, the breath figure process is combined with block copolymer nano-phase segregation to elaborate hierarchically structured honeycomb porous films. Copolymer ordering, at the nanometer length scale, is observed and described in detail with respect to the array of pores of micrometer dimension, hence pointing out the structural interplays between both length-scales. The study is focused on two diblock copolymers made of polystyrene and poly(tert-butyl acrylate) (PS-b-PtBA) with compositions producing lamellae or hexagonal packing of cylinders at thermodynamical equilibrium. Transmission Electron Microscopy completed with Small and Ultra-Small Angle Scattering are performed to evidence the inner morphologies of the honeycomb. The structural data are discussed in the light of the honeycomb film formation process establishing the interest in using kinetically trapped block copolymer self-organization as an imprint to elucidate the complex breath figure process.