Design and synthesis of a solution-processed redox-active bis(formazanate) zinc complex for resistive switching applications

Abstract

In this paper, we report the synthesis and characterization of a mononuclear zinc complex (1) containing a redox-active bis(4-antipyrinyl) derivative of the 3-cyanoformazanate ligand. Complex 1 was readily obtained by refluxing zinc acetate with 3-cyano-1,5-(4-antipyrinyl)formazan (LH) in a methanolic solution. Single-crystal X-ray diffraction analysis of complex 1 shows that the formazanate ligands bind to the zinc center in a five-member chelate “open” form via the 1- and 4-positions of the 1,2,4,5-tetraazapentadienyl formazanate backbone leading to the formation of the mononuclear bis(formazanate) zinc complex exhibiting a distorted octahedral geometry. We also report the study of resistive-switching random access memory application of this solution-processable bis(formazanate) Zn(II) complex to facilitate the practical implementation of transition metal complex-based molecular memory devices. The complex demonstrated high conductance switching with a large ON–OFF ratio, good stability, and a long retention time. A trap-controlled space charge limited current mechanism is proposed for the observed resistive switching behavior of the device, wherein the role played by the [Zn^IIL₂] complex that comprises the extended redox-active conjugated ligand backbone is revealed by corroborating electrochemical studies, spectrochemical experiments, and DFT calculations. In addition to providing significant insights into the molecular design of transition metal complexes for memory applications, this study also presents the utilization of Zn^IIL₂ towards the realization of non-volatile resistive random access memory (RRAM) devices with inorganic/organic hybrid active layers that are highly cost-effective and sustainable. These devices exhibited multilevel switching and low current operation, both of which are desirable for advanced memory applications.