Alternating Gyroid in Block Polymer Blends

Alternating gyroid is a lower symmetry variant of the double gyroid morphology, where the left-handed and right-handed chiral networks are physically distinct. This structure is of particular interest for photonic applications owing to predictions of a complete photonic band gap subject to the requirement of a large dielectric contrast between the individual networks and sufficient optical matching between one of the networks and the matrix. We provide evidence, via self-consistent field theory (SCFT), that stoichiometric blends of double-gyroid-forming AB and BC diblock copolymers with relatively immiscible A and C blocks should form an alternating gyroid morphology with complementary three-dimensional A and C networks that have a free energy that is nearly degenerate with two phase-separated double gyroid states. Solvent casting offers the potential for trapping this binary mixture of diblock copolymers in this metastable alternating gyroid phase. Theory further predicts that the addition of a minuscule amount (<1%) of ABC triblock terpolymer will open an alternating gyroid stability window in the resulting ternary-phase diagram. The surfactant-like stabilization produced by the triblock is relatively insensitive to its exact composition provided the B-block forms a sufficiently long bridge between the A-rich and C-rich networks. This blending strategy provides significant synthetic and material processing advantages compared to prevailing methods to produce an alternating gyroid phase in block polymers.