Magnetic-State Controlled Molecular Vibrational Dynamics at Buried Molecular–Metal Interfaces

Abstract

Self-assembled molecular structures have been intensively used in molecular electronics and spintronics. However, detailed nature of the interfaces between molecular layers and extended metallic contacts used to bias the real devices remains unclear. Buried interfaces greatly restrict application of standard techniques such as Raman or scanning electron microscopies. Here we introduce low frequency noise spectroscopy as a tool to characterize buried molecular-metal interfaces. We take advantage of vibrational heating of the molecules with incomplete contacts to the interface. Electrons, being the main spin and charge carriers propagating through the interfaces involving self-assembled molecules, interact inelastically with charged atomic ions. Such interactions produce quantum molecular vibrations (phonons). Detailed investigation of both conductance and conductance fluctuations in magnetic tunnel junctions with few nm Perylenetetracarboxylic dianhydride (PTCDA) allows to map vibrational heating at specific biases taking place in 'hot spots' where self-assembled layers weaker contact the metallic electrodes. We follow this effect as a function of PTCDA thickness and find the best molecular-metal order for the lowest (3-5 monolayers) barriers. Moreover, we unveil interplay between spin and phonons at interface showing experimentally and by modelling spin-control over molecular vibrational heating. We find that vibrational heating related low frequency noise essentially depends on the relative alignment of the electrodes with noise changes well beyond expectations from fluctuation-dissipation theorem.