Water-assisted microphase separation of cationic random copolymers into sub-5 nm lamellar materials and thin films

Imai, Sahori*; Arakawa, Masato*; Nakanishi, Yohei*; Takenaka, Mikihito*; Aoki, Hiroyuki  ; Ouchi, Makoto*; Terashima, Takaya*

Microphase separation of copolymers is a key technique to produce polymer bulk materials or thin films with ordered nanostructures for applications in various research fields including nanotechnologies, electronic devices, among many others. Herein, we report water-assisted microphase separation of amphiphilic random copolymers bearing quaternary ammonium cations and hydrophobic alkyl or oleyl groups in the solid state and the thin films. We investigated the effects of sample preparation protocols and the hydrophobic pendants (a butyl group: C4 - octadecyl or oleyl group: C18), composition, and molecular weight of the copolymers on the microphase separation behavior. By annealing under humid conditions, the copolymers bearing alkyl groups longer than an octyl group (C8) formed sub-5 nm lamellar structures comprising cationic layers and hydrophobic layers. Water hardly remained in the resulting lamellar materials under ambient conditions. The domain spacing was controlled between 3.7 and 5.3 nm by tuning the length of the hydrophobic pendants and composition and was independent of the molecular weight and molecular weight distribution. The cationic random copolymers carrying amorphous hydrophobic pendants provided transparent or translucent polymer materials containing small lamellar structures. The random copolymers further formed multilayered lamellar thin films on silicon substrates by spin-coating the copolymer solutions, followed by a humid annealing process. The layered lamellae were directly observed as terrace structures with about 4-5 nm steps by atomic force microscopy.