Robust Sub‐5 Nanometer bis(Diarylcarbene)‐Based Thin Film for Molecular Electronics and Plasmonics

In miniaturized electronic and optoelectronic circuits, molecular tunnel junctions have attracted enormous research interest due to their small footprint, low power consumption, and rich molecular functions. However, the most popular building blocks used in contemporary molecular tunnel junctions are thiol molecules, which attach to electrode surfaces via a metal‐thiolate (MS) bond, showing low stability and usually quick degradation within several days. To pave the way for more widely applicable and stable molecular tunnel junctions, there is a need to develop new molecular anchoring groups. Here, this work demonstrates robust and air‐stable molecular tunnel junctions with a sub‐5 nanometer bis(diarylcarbene)‐based thin film as the tunneling barrier, which anchors to the electrode surface via a AuC bond. The bis(diarylcarbene)‐based molecular tunnel junctions exhibit high thermal stability against heating up to 200 °C and long storage lifetime over 5 months in an ambient environment. Both electrical and optical performance of these bis(diarylcarbene)‐based molecular junctions are characterized systematically, showing similar behaviors to thiol‐based junctions as well as largely improved emission stability. This research highlights the excellent performance of bis(diarylcarbene)‐based molecular tunnel junctions, which could be useful for applications in molecular electronics and plasmonics. Robust and air‐stable molecular tunnel junctions with a sub‐5 nanometer bis(diarylcarbene)‐based thin film as the tunneling barrier are accessible, which anchors to the electrode surface via a AuC bond and shows promising applications in molecular electronics and plasmonics.