Plasmonic Photochemistry as a Tool to Prepare Metallic Nanopores with Controlled Diameter for Optimized Detection of Single Entities

Abstract Plasmonic solid‐state nanopores with tunable hole diameters can be prepared via a photocatalytic effect resulting from the enhanced electromagnetic (EM) field inside a metallic ring on top of a dielectric nanotube. Under white light illumination, the plasmon‐enhanced EM‐field induces a site‐selective metal nucleation and growth within the ring. This approach is used to prepare Au and bimetallic Au–Ag nano‐rings and demonstrate the reduction of the initial inner diameter of the nanopore down to 4 nm. The tunability of the nanopore diameter can be used to enable optimized detection of single entities with different sizes. As a proof‐of‐concept, single object detection of double stranded DNA (dsDNA) and Au nanoparticles (AuNPs) with a diameter down to 15 nm is performed. Numerical simulations provide insights into the EM‐field distribution and confinement, showing that a field intensity enhancement of up to 10⁴ can be achieved inside the nanopores. This localized EM‐field can be used to perform enhanced optical measurements and generate local heating, thereby modifying the properties of the nanopore. Such a flexible approach also represents a valuable tool to investigate plasmon‐driven photochemical reactions, and it can represent an important step toward the realization of new plasmonic devices.