Tuning The Double Gyroid Phase Window In Block Copolymers Via Polymer Chain Conformation Near The Interface

Block copolymer network morphologies have been proven interesting for applications ranging from mechanical to transport and optical properties. The shape of the polymer chain and its ability to stretch across an interface can be used as handles to target these network morphologies. Here, we show that the double gyroid phase window is broadened when there is a flexible segment near the interface and narrowed when a more constrained segment is placed there by using a series of poly(styrene-b-peptoid) block copolymers in which the polypeptoid block chain conformation can be tuned to adopt either a helical or a coil conformation (NRpe(6) vs Npe(6)). The double gyroid phase is accessed in both block copolymer series, while the phase boundaries are shifted toward larger polypeptoid volume fractions in the helix-forming PS-(NRpe(6) Nme(y)) series, due to the more compact helix segment (i.e., the helix segment has the same chain volume as its random coil counterpart but occupies less space). The space-filling difference between the helix and coil segment is further confirmed by the smaller domain spacing of PS-(NRpe(6)Nme(39)) compared to PS-(Npe(6)Nme(36)) (13.9 nm vs 14.3 nm) despite the former having a longer polypeptoid block. Furthermore, a broadened double gyroid phase window is accessed in the PS-(Npe(6)Nme(y)) series that has a flexible coil segment near the interface. These results demonstrate the possibility of tuning the double gyroid phase in linear block copolymers by chain conformation near the interface alone, highlighting chain conformation as a versatile handle in block copolymer design.