Self-assembling block copolymers generate nanostructured patterns which are useful for a wide range of applications. In this paper we demonstrate the capability to control the morphology of the self-assembling process of PS-b-PMMA diblock copolymer thin films on unpatterned surfaces by means of fast thermal treatment performed in a rapid thermal processing machine. The methodology involves the use of radiation sources in order to rapidly drive the polymeric film above the glass transition temperature. Highly ordered patterns were obtained for perpendicular-oriented cylindrical and lamellar PS-b-PMMA block copolymers in less than 60 s. This approach offers the unprecedented opportunity to investigate in detail the kinetics of the block copolymer self-assembly during the early stages of the process, providing a much deeper understanding of the chemical and physical phenomena governing these processes.

The pattern coarsening dynamics in symmetric polystyrene-b-polymethylmethacrylate (PS-b-PMMA) block copolymer thin films under conventional thermal treatments is extremely slow, resulting in limited correlation length values even after prolonged annealing at relatively high temperatures. This study describes the kinetics of symmetric block copolymer microphase separation when subjected to a thermal treatment based on the use of a Rapid Thermal Processing (RTP) system. The proposed methodology allows self-organization of symmetric PS-b-PMMA thin films in few seconds, taking advantage of the amount of solvent naturally trapped within the film during the spinning process. Distinct and self-registered morphologies, coexisting along the sample thickness, are obtained in symmetric PS-b-PMMA samples, with periodic lamellae laying over a hexagonal pattern of PMMA cylinders embedded in the PS matrix and perpendicularly oriented with respect to the substrate. The ordering dynamics and morphological evolution of the coexisting dual structures are delineated and the intimate mechanism of the self-assembly and coarsening processes is discussed and elucidated.

Determination of the SERS enhancement factor through the challenging measurement of the molecular surface density by reference-free X-ray fluorescence.