Electron transport across metal/discotic liquid crystal interfaces

Electron transport across micron thick films of columnar hexagonal discotic liquid crystal phases homeotropically aligned between metal electrode surfaces has been studied both experimentally and theoretically. These molecules are unique in their combination of charge transport along individual molecular columns with liquidlike self-organization. Typical of organic insulators, a high resistance Ohmic regime is evident at fields of less than 0.05 MV cm−1, due to a low concentration of chemical impurities (n<109 cm−3), and a space-charge injection regime at higher fields. Breakdown fields are reasonably high: in hexakis(hexyloxy)triphenylene they reach ∼5 MV cm−1 at room temperature. Our results show that triphenylene-based discotics form an excellent class of highly ordered optically transparent insulators. At high temperatures and high fields the current is injection controlled and exhibits typical tunneling and space charge limited, nonlinear I–V characteristics. Dramatic jumps in injection currents are observed at phase transitions. The change at the crystalline to liquid crystalline phase transition is mainly due to more efficient “wetting” of the electrode surface in the liquid crystalline phase, whilst at the liquid crystalline to isotropic phase transition it arises from the enhancement in the molecular mobility. The concepts of semiconducting gaps, band mobilities, and carrier injection rates are extended to these new materials. The experimental observations are interpreted in a framework which takes into account the important role played by liquidlike dynamics in establishing the microscopic structural order in, what is, otherwise a highly anisotropic and weakly bonded “molecular crystal.”