(Invited) Organic Memristors for Mimicking Synaptic Plasticity

Since the introduction of a concept of memristor by Leon Chua in 1971 as the fourth fundamental passive component in electronic circuits, and its functional prototype introduced by HP Lab in 2008, research has increasingly concentrated on exploring its application ability in electronic circuits. First, the memristor principles have been exploited in various memory devices within a classical von Neumann computer architecture. The properties of memristor were found particularly suitable for resistive random-access memories (ReRAM).1 Contrary to the classical von Neumann architecture based on the binary logic, advanced methods like neuromorphic computing require an electronic element with continuously varying states depending on previous input signals. The input signal consists of a sequence of voltage spikes that stimulate the device, similarly as a neural synapse does in biological systems. These trains of spikes change the output state of the device continuously to a lower resistance state, mimicking a learning process. Having these functionalities, memristors are considered to be possible building blocks of brain-inspired neuromorphic computing and artificial neural networks.2 Memristors with neurosynaptic functionality take a continuity of resistance values with synaptic weights modulated by the number and frequency of homogeneous spikes. In order to mimic the neural synapse, memristors must exhibit analog properties including non-abrupt switching transitions, memory loss, continuously variable resistance states, and predictable response. We present such functionality on thin films of two kinds of organic materials: (i) A newly synthesized poly(methacrylamide) derivative with carbazole charge transporting group separated from the polymer backbone by an alkyl chain, was synthesized recently and found to behave as a bistable resistive memory.3 Thin films of the polymer, sandwiched between Al and ITO electrodes, exhibit rewritable flash memory behavior with bistable conductivity, with the set switching voltage ranging from 2 to 4.5 V, and the current ON/OFF ratio exceeding 100. The device demonstrates a remarkable lifetime and remains persistent for more than 104 seconds under the static voltage of 0.5 V. The main physical mechanisms driving the resistive switching have been attributed to the electric field-induced reorientation of heterocycles, which modulates charge transport, and trapping/detrapping of charges in localized states within the bulk of the polymer. Memory persistence is strengthened by the physical crosslinking caused by hydrogen bonds between amide and carbonyl groups in the side chains. Depending on the layer thickness, electrode material and applied voltage range the electrical characteristics can change from bistable to analog behavior showing memristive properties. (ii) Ditopic π-conjugated bis-terpyridine (tpy-) ligands form supramolecular structures in which the ligands are interconnected by complexation with metal ions. These molecules offer a low energy operation with improved reproducibility of memristive characteristics. They possess low-lying molecular energy levels and relatively narrow bandgap enabling the low-power consuming resistive switching and longer stability. We used a newly synthesized bis-terpyridine ligands based on 9-phenyl carbazole, Cbz, and its complex with cobalt Co2+ as an active layer of a memristor device. A two-terminal memristor architecture was employed, consisting of the ligand or its cobalt complex deposited on an ITO substrate, and aluminum, gold, or gallium as a top electrode. We show that Cbz as a memristor active layer exhibits an excellent nonvolatile bistable memory behavior, while Co-Cbz exhibits both electronic memory and synaptic plasticity. The ligand exhibited bi-stable conduction and non-volatile memory effect with persistence over 18 hours, while its cobalt complex displayed a synaptic effect characterized by subsequent potentiation and depression cycles. Voltage-induced modulation of synaptic weight was observed with a low applied voltage below 500 mV and short pulse duration below 20 ms. Pair pulse facilitation and pair pulse depression demonstrated significant synaptic weight changes, showing the cobalt complex ability to emulate biological neurons. The operational mechanism was attributed to a combination of the redox effect in the ligand and complex, and to the voltage-induced migration of perchlorate counter ions and subsequent redox processes, altering the metal-to-ligand charge transfer band and changing the conducting state of the active layer. Acknowledgments: The work was financially supported by the Czech Science Foundation, project 24-10384S, and MEYS of the Czech Republic, project LUAUS24032. Strukov, D. B., Snider, G. S., Stewart, D. R. & Williams, R. S. The missing memristor found. Nature 453, 80–83 (2008). Chang, T., Jo, S. H. & Lu, W. Short-term memory to long-term memory transition in a nanoscale memristor. ACS Nano 5, 7669–7676 (2011). Panthi, Y.R, Pfleger, J., Vyprachticky, D., Pandey, A., Thottappali, M.A., Sedenkova, I., Konefal, M. & Foulger, S.H. Rewritable resistive memory effect in poly[N-(3-(9H-carbazol-9-yl)propyl)-methacrylamide] memristor. Mater. Chem. C 11, 17093 (2023).