Thickness dependent hierarchical meso/nano scale morphologies of a metal-containing block copolymer thin film induced by hybrid annealing and their pattern transfer abilities

In this paper we describe dewetting phenomena in organic (polystyrene, PS)/inorganic (polyferrocenyldimethylsilane, PFS) block copolymer thin films. Mesoscale dendritic structures are induced when the spin-cast thin film of this polymer is subjected to so-called hybrid annealing, which involves both thermal and solvent annealing. We show that the development and arrangement of these mesoscale dendritic structures depends on the initial film thickness in addition to the annealing time. Importantly, there are two criteria that must be fulfilled to achieve these mesoscale morphologies: (i) the film has to be subjected to hybrid annealing, i. e. either only thermal or only solvent annealing does not produce any notable mesostructures and (ii) both PS and PFS blocks must be present during the thermal and solvent annealing procedures; if one of the blocks, for instance PS, is removed before annealing then there is no mesostructure. Various possible mechanisms for the formation of these structures are discussed and results indicate that the PFS block dominates the structure formation. We also observe a ring-or worm-like nanostructure which develops only when the film is subjected to hybrid annealing at a particular film thickness. Apart from these results, here we demonstrate that mesoscale structures can be successfully transferred onto underlying substrates.