Volatile Memristive Devices with Analog Resistance Switching Based on Self-Assembled Squaraine Microtubes as Synaptic Emulators

In this work, the discovery of volatile memristive devices that exhibit analog resistive switching (RS) and synaptic emulation based on squaraine materials is presented. Specifically, organic microtubes (MTs) based on 2,4-bis-[(4-(N,N-diisobutyl)-2-6-hydroxyphenyl]-squaraine (SQ) are prepared by evaporation-induced self-assembly (EISA). The MTs are ca. 2 mu m in diameter (aspect ratio: 10-130). While powder X-ray diffraction data for MTs identify monoclinic and orthorhombic polymorphs, optical data report the monoclinic phase with energetic disorder. By favorable energetic alignment of the Au work function with the SQ HOMO energy, unipolar (hole-only) symmetric metal-insulator-metal devices are formed by EISA of MT meshes on interdigitated electrodes. The DC I-V characteristics acquired exhibit pinched hysteretic I-V loops, indicative of memristive behavior. Analysis indicates Ohmic transport at low bias with carrier extraction by thermionic emission. At high bias, space-charge-limited conduction in the presence of traps distributed in energy, enhanced by a Poole-Frenkel effect and with carrier extraction by Fowler-Nordheim tunneling, is observed. These data indicate purely electronic conduction. I-V hysteresis attenuates at smaller voltage windows, suggesting that carrier trapping/detrapping underpins the hysteresis. By applying triangular voltage waveforms, device conductance gradually increases sweep-on-sweep, with wait-time-erase or voltage-erase options. Using square waveforms, repeated erase-write-read of multiple distinct conductance states is achieved. Such analog RS behavior is consistent with trap filling/emptying effects. By waveform design, volatile conductance states may also be written so that successive conductance states exhibit identical current levels, indicating forgetting of previously written states and mimicking the forgetting curve. Finally, advanced synaptic functions, i.e., excitatory postsynaptic current, paired-pulse facilitation, pulse-dependent plasticity, and a transition from short- to long-term memory driven by post-tetanic potentiation, are demonstrated.