Sculpting the Plasmonic Responses of Nanoparticles by Directed Electron Beam Irradiation

Abstract Spatial confinement of matter in functional nanostructures has propelled these systems to the forefront of nanoscience, both as a playground for exotic physics and quantum phenomena and in multiple applications including plasmonics, optoelectronics, and sensing. In parallel, the emergence of monochromated electron energy loss spectroscopy (EELS) has enabled exploration of local nanoplasmonic functionalities within single nanoparticles and the collective response of nanoparticle assemblies, providing deep insight into associated mechanisms. However, modern synthesis processes for plasmonic nanostructures are often limited in the types of accessible geometry, and materials and are limited to spatial precisions on the order of tens of nm, precluding the direct exploration of critical aspects of the structure‐property relationships. Here, the atomic‐sized probe of the scanning transmission electron microscope is used to perform precise sculpting and design nanoparticle configurations. Using low‐loss EELS, dynamic analyses of the evolution of the plasmonic response are provided. It is shown that within self‐assembled systems of nanoparticles, individual nanoparticles can be selectively removed, reshaped, or patterned with nanometer‐level resolution, effectively modifying the plasmonic response in both space and energy. This process significantly increases the scope for design possibilities and presents opportunities for unique structure development, which are ultimately the key for nanophotonic design.