Evidence of T-type structures of hard square boards in capillary confinement

We employ Onsager's second virial density functional theory combined with the Parsons-Lee theory within the restricted orientation (Zwanzig) approximation to examine the phase structure of hard square boards of dimensions (L×D×D) uniaxially confined in narrow slabs. Depending on the wall-to-wall separation (H), we predict a number of distinctly different capillary nematic phases, including a monolayer uniaxial or biaxial planar nematic, homeotropic with a variable number of layers, and a T-type structure. We determine that the favored phase is homotropic, and we observe first-order transitions from the homeotropic structure with n layers to n+1 layers as well as from homeotropic surface anchoring to a monolayer planar or T-type structure involving both planar and homeotropic anchoring at the pore surface. By increasing the packing fraction, we further demonstrate a reentrant homeotropic-planar-homeotropic phase sequence in a particular range (i.e., H/D=1.1 and 0.25≤L/D<0.26). We find that the T-type structure is more stable when the pore is wide enough with respect to the planar phase. The enhanced stability of the mixed-anchoring T-structure is unique for square boards and becomes manifest at pore width exceeding L+D. More specifically, the biaxial T-type structure emerges directly from the homeotropic state without intervention of a planar layer structure as observed for other convex particle shapes.