Two-Level Electronic Switching in Individual Manganese-Phthalocyanine Molecules with Jahn–Teller Distortion

Understanding single molecular switches is a crucial step in designing and optimizing molecular electronic devices with highly nonlinear functionalities, e.g., gate voltage-dependent current switching. An atomically thin insulating template, in combination with scanning probe techniques, is an ideal platform to study such switches on the single-molecule level. In this study, we investigate manganese-phthalocyanine (MnPc) molecules on monolayer-thin epitaxial hexagonal boron nitride (h-BN) on Rh(111) by scanning tunneling microscopy (STM), spectroscopy (STS), and theoretical calculations. Several interesting phenomena are found: (1) high-resolution STM imaging of the molecular orbitals reveals symmetry breaking from D_4h to D_2h, observed in one type of MnPc. By comparison with simulations, this phenomenon can be attributed to the Jahn–Teller effect due to the negative charging of the molecule. (2) Ambipolar transitions at the molecule occur at fixed sample biases of about ±0.4 V, which manifest as negative differential conductance signatures in dI/dV spectroscopy. (3) The stochastic two-level switching, resulting in telegraphic noise in the tunneling current, manifests as a one-electron activated process. We present a two-level switching model to accurately describe a bias-dependent current-driven transition between the levels and reveal a first-order transition. The understanding and tailoring of molecular switches on the ultrathin insulating layer will be very helpful for future organic electronics design and application.