Fingerprint Recognition Based on Molecular-Scale Conductance Response via Electrochemically Gated Quantum Tunnelling

Molecular-scale detection based on quantum tunnelling is promising for molecular electronics and high-sensitivity analysis, owing to its sensitivity to molecular structure and energy levels. However, conventional two-electrode tunnelling measurements suffer from overlapping conductivity of different molecules, limiting molecular discrimination in complex systems. To address this, we propose an electrochemical-gate-controlled nanoscale tunnelling strategy that expands the two-electrode system to a three-electrode configuration via a tunable gate potential, enabling the differentiation of distinct molecules at near-single-molecule sensitivity. Scanning the gate potential under constant tunnelling bias modulates the alignment between molecular orbitals and the electrode Fermi level, altering the statistical characteristics of molecular tunnelling transport. Experimental results show that target molecules induce a bimodal distribution of tunnelling current (background and molecule-correlated channels), with the second peak exhibiting distinct gate potential dependence. Comparative analysis of ascorbic acid (AA), acetylcholine (ACh), and uric acid (UA) reveals unique trajectories of characteristic peaks with gate potential, forming an electrochemical gate response fingerprint. This gate-dependent conductance trajectory provides a novel statistical dimension for molecular recognition, enabling differentiation of distinct molecules.