Martensitic-like transition between liquid crystalline and crystalline phases of prototypical discotic organic semiconductor

Abstract

Phase transitions between crystalline solids occur either through the nucleation and growth mechanism, a process that is slow and destructive or through the diffusion-less and order preserving Martensitic route. In both organic and inorganic materials, Martensitic transformations are known to occur only between phases with crystalline symmetry. We demonstrate here that for canonical discotic organic semiconductor HAT6, the transition between the liquid crystalline columnar hexagonal phase (ColH) and the crystalline solid can occur through a mechanism that exhibits the hallmarks of Martensitic transformations: orientational correlations between parent and daughter phases, structural reversibility, and ultrafast kinetics. To access Martensitic-like solidification, the ColH phase of HAT6 is biaxially aligned in lithographically defined microchannels and crystallization is induced on deep supercooling. The transition mechanism is studied using a combination of polarized optical microscopy and X-ray scattering. At the largest accessible supercooling, the ColH - Crystal phase transition occurs at speeds of ~100 micrometer/s, a value that is seven orders of magnitude greater than the theoretical prediction for growth from isotropic melts. Our work suggests that Martensitic-like transformations can occur even between liquid crystals and crystals and are therefore more general than previously believed. Further, our work demonstrates that Martensitic-like transformations of anchored liquid crystals can be used to grow biaxially aligned crystals of organic molecules over arbitrarily long distances. As lattice alignment over large areas is desirable for devices like field-effect transistors and as several high-performance molecular semiconductors exhibit a ColH phase, our results hold general significance for organic electronics.