An Ising transition of chessboard tilings in a honeycomb liquid crystal

We have designed a compound that forms square liquid crystal honeycomb patterns with a cell size of only 3 nm and with zero in-plane thermal expansion. The compound is a bolaamphiphile with a π-conjugated rod-like core and two mutually poorly compatible side-chains attached on each side of the rod at its centre. The system exhibits a unique phase transition between a “single colour” tiling pattern at high temperatures, where the perfluoroalkyl and the carbosilane chains are mixed in the square cells, to a “two-colour” or “chessboard” tiling where the two chain types segregate in their respective cells. Small-angle transmission and grazing incidence X-ray studies (SAXS and GISAXS) indicate critical behaviour both below and above the transition. Both phase types are of considerable interest for sub-5 nm nanopatterning. The temperature dependence of ordering of the side chains has been investigated using Monte Carlo (MC) simulation with Kawasaki dynamics. For a 3-dimensional system with 2 degrees of freedom, universality predicts that the transition falls into the 3d Ising class; MC was therefore used to calculate observables and determine the critical exponents accessible in experiment. Theoretical values of ν, γ and, perhaps most importantly, of the order parameter β have been calculated and then compared with those determined experimentally. β found experimentally is close to the theoretical value, but ν and γ values are significantly smaller than predicted. To explain the latter, the measured susceptibility above Tc is compared with those from simulations of different lattice sizes. The results suggest that the discrepancies result from a reduced effective domain size, possibly due to kinetic suppression of large scale fluctuations.