Nanoscale Effects in One-Dimensional Columnar Supramolecular Ferroelectrics.

Organic ferroelectrics have been actively developed with the goal of fabricating environmentally friendly and low-cost memory devices. The remanent polarization of hydrogen-bonded organic ferroelectrics approaches that of the inorganic ones. Nanoscale fabrication of organic ferroelectrics is an essential aspect of high-density memory devices. A pyrene derivative with four tetradecylamide (-CONHC14 H29 ) chains (1) formed an amide-type N-H⋅⋅⋅O hydrogen-bonded one-dimensional (1D) column, which demonstrated ferroelectricity in the discotic hexagonal columnar (Colh ) liquid crystalline phase through the inversion of the orientation of the hydrogen-bonded chains. On the contrary, similar chiral pyrene derivatives bearing 3,7-dimethyl-1-octhylamide chains (S-2 and R-2) did not indicate the Colh phase and ferroelectricity. Homogeneous mixed liquid crystals (1)1-x (S-2)x (i.e., between the ferroelectric 1 and the non-ferroelectric S-2) enable the control of the nanoscale aggregation state of the organic ferroelectrics, resulting in a nanoscale effect of the 1D supramolecular ferroelectrics. Ferroelectric mixed liquid crystals (1)1-x (S-2)x were observed at x≦0.03, where one S-2 molecule was inserted after every thirty-three 1 molecule in the mixed liquid crystal (1)33 (S-2). An average (1)34 length of approximately 12 nm was required to maintain the 1D ferroelectricity, which was similar to the nanoscale limit of inorganic ferroelectrics, such as hafnium oxide thin film (≈15 nm).