Perpendicularly Aligned Nanodomains on Versatile Substrates Rapid Thermal Annealing Assisted by Liquid Crystalline Ordering in Block Copolymer Films

The highly ordered perpendicularly aligned cylindrical and lamellar microdomains within block copolymer (BCP) films have important applications in diverse fields. However, the fast normal orientation of self-assembled nanostructures on arbitrary substrates without tedious pre- and postprocessing has been a challenging issue in manufacturing miniaturized devices. Here, we outline the potential for extending the hierarchical self-assembly within azobenzene-containing PS--PMA(Az) films to inherently assist in the formation of normally aligned domains using a rapid thermal annealing process (140 °C for 5 min). Liquid crystalline (LC) mesogens in PS--PMA(Az) films self-assemble to form a parallelly aligned sematic phase after thermal annealing, as confirmed by grazing-incidence small-angle X-ray scattering (GISAXS), wide-angle X-ray diffraction (WAXD) and ultraviolet-visible (UV-vis) spectra. This sub-phase contributes to broadening of the PS-cylinder-phase window (0.083 ≤ < 0.49) and ∼12 nm PS cylinder structures. Perpendicular cylinders or lamellae are observed on various substrates, such as silicon wafers, flexible polyethylene terephthalate (PET) sheets and conductive aluminum foils. Additionally, the good reactive ion etching (RIE) rate difference between the two blocks makes these BCPs more attractive for advancing the field of BCP lithographic applications for fabricating flexible microelectronic devices.