Micrometer-Scale Ordering of Silicon-Containing Block Copolymer Thin Films via High-Temperature Thermal Treatments

Block copolymer (BCP) self-assembly is expected to complement conventional optical lithography for the fabrication of next-generation microelectronic devices. In this regard, silicon-containing BCPs with a high Flory-Huggins interaction parameter (χ) are extremely appealing because they form high-resolution nanostructures with characteristic dimensions below 10 nm. However, due to their slow self-assembly kinetics and low thermal stability, these silicon-containing high-χ BCPs are usually processed by solvent vapor annealing or in solvent-rich ambient at a low annealing temperature, significantly increasing the complexity of the facilities and of the procedures. In this work, the self-assembly of cylinder-forming polystyrene-block-poly(dimethylsiloxane-random-vinylmethylsiloxane) (PS-b-P(DMS-r-VMS)) BCP on flat substrates is promoted by means of a simple thermal treatment at high temperatures. Homogeneous PS-b-P(DMS-r-VMS) thin films covering the entire sample surface are obtained without any evidence of dewetting phenomena. The BCP arranges in a single layer of cylindrical P(DMS-r-VMS) nanostructures parallel-oriented with respect to the substrate. By properly adjusting the surface functionalization, the heating rate, the annealing temperature, and the processing time, one can obtain correlation length values larger than 1 μm in a time scale fully compatible with the stringent requirements of the microelectronic industry.