Conductivity switching and electronic memory effect in polymers with pendant azobenzene chromophores

Electronic memory devices having the indium-tin oxide/polymer/Al sandwich structure were fabricated from polymers containing pendant azobenzene chromophores in donor-acceptor structures. The reversibility, or rewritability, of the high-conductivity (ON) state was found to be dependent on the terminal moiety of the azobenzene chromophore. While the polymers with electron-accepting terminal moieties (-Br or -NO2) in the pendant azobenzene exhibit write-once, read-many-times (WORM) type memory behavior, those with electron-donating terminal moieties (-OCH3) exhibit rewritable (FLASH) memory behavior. The WORM memory devices have low switching ("write") voltages below -2 V and high ON/OFF current ratios of about 10(4)-10(6). The polarity of the "write" voltage can be reversed by using an electrode with a higher work function than Al, thus excluding metallic filamentary conduction as a cause of the bistable switching phenomenon. The FLASH memory devices have low "write" and "erase" voltages of about -1.7 to -1.8 V and 2.0 to 2.2 V, respectively, and ON/OFF current ratios of about 10(3)-10(4). The electrical bistability observed can be attributed to charge trapping at the azobenzene chromophores, resulting in the charge-separated, high-conductivity state. The proposed mechanism is supported experimentally by a red shift and peak broadening in the UV-visible absorption spectra of the polymer films resulting from the OFF-to-ON electrical transition.