The morphological evolution of cylinder-forming poly(styrene)-b-poly(methyl methacrylate) block copolymer (BCP) thick films treated at high temperatures in the rapid thermal processing (RTP) machine was monitored by means of in-depth grazing-incidence small-angle X-ray scattering (GISAXS). The use of this nondisruptive technique allowed one to reveal the formation of buried layers composed of both parallel- and perpendicular-oriented cylinders as a function of the film thickness (24 ≤ h ≤ 840 nm) and annealing time (0 ≤ t ≤ 900 s). Three distinct behaviors were observed depending on the film thickness. Up to h ≤ 160 nm, a homogeneous film consisting of perpendicular-oriented cylinders is observed. When h is between 160 and 700 nm, a decoupling process between both the air-BCP and substrate-BCP interfaces takes place, leading to the formation of mixed orientations (parallel and perpendicular) of the cylinders. Finally, for h > 700 nm, the two interfaces are completely decoupled, and the formation of a superficial layer of about 50 nm composed of perpendicular cylinders is observed. Furthermore, the through-film morphology affects the nanodomain long-range order, which substantially decreases in correspondence with the beginning of the decoupling process. When the thick samples are exposed to longer thermal treatments, an increase in the long-range order of the nanodomains occurs, without any sensible variation of the thickness of the superficial layer.
Keywords: GISAXS; PS-b-PMMA; block copolymers; rapid thermal processing; self-assembly.