Molecularly Controlled Stark Effect Induces Significant Rectification in Polycyclic-Aromatic-Hydrocarbon-Terminated n-Alkanethiolates

The variation of the electronic structure of individual molecules as a function of the applied bias matters for the performance of molecular and organic electronic devices. Understanding the structure-electric-field relationship, however, remains a challenge because of the lack of in-operando spectroscopic technique and complexity arising from the ill-defined on-surface structure of molecules and organic-electrode interfaces within devices. We report that a reliable and reproducible molecular diode can be achieved by control of the conjugation length in polycyclic-aromatic-hydrocarbon (PAH)-terminated n-alkanethiolate (denoted as SC ₁₁ PAH), incorporated into liquid-metal-based large-area tunnel junctions in the form of a self-assembled monolayer. By taking advantage of the structural simplicity and tunability of SC ₁₁ PAH and the high-yielding feature of the junction technique, we demonstrate that the increase in the conjugation length of the PAH terminal group leads to a significant rectification ratio up to ∼1.7 × 10 ² at ±740 mV. Further study suggests that the Stark shift of the molecular energy resonance of the PAH breaks the symmetry of the energy topography across the junction and induces rectification in a temperature-independent charge-transport regime.