Diverse configurations of columnar liquid crystals in cylindrical nano-and micropores

Using 2D X-ray diffraction and AFM we studied the configuration, in cylindrical confinement, of hexagonal columnar phases that anchor homeotropically, i.e. with the columns normal to the pore wall. A wide range of pore diameters, from 20 nm to 100 μm, were explored by employing anodic alumina membranes and glass capillaries. The compounds used were a small discotic, hexakis(hexyloxy)triphenylene (HAT6), a large discotic hexa-peri-hexabenzocoronene (HBC), and a T-shaped bolaamphiphile, forming a honeycomb-type columnar phase. It was found that in pores up to tens of μm in diameter the columns adopt the "logpile" configuration with parallel columns crossing the pore perpendicular to its axis. Starting with 20 nm pores, with increasing pore diameter up to 5 different configurations are observed, the sequence being the same for all three compounds in spite of their structural diversity. One of the {100} planes of the hexagonal logpile starts from being parallel to the pore axis, then rotates by 90° as the pore size increases, and eventually becomes tilted to the pore axis by (8.5 ± 1)° as the pore widens further. Finally, in glass capillaries of tens of μm and beyond, the columns become axially oriented, parallel to the capillary axis. This latter finding was particularly unexpected as common sense would suggest axial columns to be favoured by planar anchoring, where in fact, it was shown to be hard to achieve. The present findings should help in the design of low-dimensional semiconductor or ionic conductor devices based on oriented columnar phases.