What Determines the Sign Reversal of Magnetoresistance in a Molecular Tunnel Junction?

The observations of both positive and negative signs in tunneling magnetoresistance (TMR) for the same organic spin-valve structure have baffled researchers working in organic spintronics. In this article, we provide an answer to this puzzle by exploring the role of metal–molecule interface on TMR in a single molecular spin-valve junction. A planar organic molecule sandwiched between two nickel electrodes is used to build a prototypical spin-valve junction. A parameter-free, single-particle Green’s function approach in conjunction with a posteriori, spin-unrestricted density functional theory involving a hybrid orbital-dependent functional is used to calculate the spin-polarized current. The effect of external bias is explicitly included to investigate the spin-valve behavior. Our calculations show that only a small change in the interfacial distance at the metal–molecule junction can alter the sign of the TMR from a positive to a negative value. By changing the interfacial distance by 3%, the number of participating eigenchannels as well as their orbital characteristics changes for the antiparallel configuration, leading to the sign reversal in TMR.