Mechanism of rectification and negative differential resistance in single-molecule junctions with asymmetric anchoring groups: a DFT study.

Abstract

This study aims to investigate the electronic transport properties of tetracene molecule connected to gold (Au) electrodes with asymmetric anchoring groups. More specifically, we investigate the effect of asymmetric electrode coupling on the rectification ratio of tetracene-based molecular device. To introduce coupling asymmetry in these junctions, one end of the tetracene molecule is terminated with thiol (-SH) or isocyanide (-NC) while the other end with amine (-NH2) or nitro (-NO2) anchoring group. The results indicate that the electronic transport behavior is affected by the nature of molecule-electrode coupling, and the rectification ratio can be modulated by a proper choice of the anchoring groups. We reveal that the tetracene molecule when connected with isocyanide and amine combination exhibits remarkable rectifying performance (with a rectification ratio of 74) in contrast with other configurations. Furthermore, a prominent negative differential resistance (NDR) feature is observed when the molecule is connected with thiol as one of the anchors. Our present findings with excellent rectifying performance and negative differential resistance pave a new roadmap for designing multifunctional molecular devices. By applying non-equilibrium Green's function (NEGF) formalism combined with density functional theory (DFT) Atomistic Tool Kit software package, the electronic transport properties of tetracene molecule connected to gold electrodes with asymmetric anchoring groups have been investigated. The calculations were performed using the Perdew-Burke-Ernzerhof (PBE) parameterization of DFT within generalized gradient approximation (GGA) exchange-correlation functional. To improve calculation precision and save computational efforts, the molecule and anchor groups were double-ζ (DZ) polarized, while single-ζ (SZ) polarized basis set was used for gold electrodes.