Restricting Conformational Space: A New Blueprint for Electrically Switchable Self‐Assembled Monolayers

Tunnel junctions comprising self‐assembled monolayers (SAMs) from liquid crystal‐inspired molecules show a pronounced hysteretic current–voltage response, due to electric field‐driven dipole reorientation in the SAM. This renders these junctions attractive device candidates for emerging technologies such as in‐memory and neuromorphic computing. Here, the novel molecular design, device fabrication, and characterization of such resistive switching devices with a largely improved performance, compared to the previously published work are reported. Those former devices suffer from a stochastic switching behavior limiting reliability, as well as from critically small read‐out currents. The present progress is based on replacing Al/AlOₓ with TiN as a new electrode material and as a key point, on redesigning the active molecular material making up the SAM: a previously present, flexible aliphatic moiety has been replaced by a rigid aromatic linker, thereby introducing a molecular "ratchet". This restricts the possible molecular conformations to only two major states of opposite polarity. The above measures have resulted in an increase of the current density by five orders of magnitude as well as in an ON/OFF conductance ratio which is more than ten times higher than the individual scattering ranges of the high and low resistance states.