Charge trapping-induced current–voltage hysteresis in a squaraine nanowire mesh enables synaptic memristive functionality

Abstract

Nanowires (NWs) composed of 2,4-bis[(4-diethylamino)-2-hydroxyphenyl] squaraine were prepared by evaporation-induced self-assembly (EISA). NWs were ∼560 nm wide (aspect ratios: 10–90). X-ray diffraction analysis indicated polymorphism (monoclinic/triclinic). Optical data reported the triclinic phase with energetic disorder. Given the favorable alignment of the Au work function and squaraine HOMO energy, symmetric, unipolar metal–insulator–metal devices were formed by the EISA of NW meshes on inter-digitated Au electrodes. Room temperature DC I–V characteristics displayed hysteretic I–V loops, indicating memristive behavior. At low bias, data indicated Ohmic transport with carrier extraction facilitated by thermionic emission. At high biases, devices exhibited space-charge-limited conduction in the presence of shallow traps. At 77 K, data indicated Ohmic transport at low bias with carrier extraction by thermionic emission while, at high biases, trap-limited space-charge-limited conduction in the presence of traps distributed in energy, with carrier extraction by Fowler–Nordheim tunneling, was observed. The I–V hysteresis was eliminated at 77 K and attenuated by fast scan rates at room temperature, suggesting that carrier trapping/de-trapping underpinned the hysteresis. In impedance measurements, the device response fitted a Randles equivalent circuit indicating purely electronic conduction. By applying voltage waveforms, I–V hysteresis and analog resistive switching (memristive) functionality were observed. Device conductance could be increased sweep by sweep, giving conductance tuning through distinct states, with wait time- or voltage-erase options, consistent with trap filling/emptying effects. Repeated erase–write–read of multiple distinct states over many voltage cycles during continuous use in air was demonstrated. Finally, synaptic functions, e.g., pulse-dependent plasticity, and short- to long-term memory transition, were successfully emulated.