Plasma-Induced Nanogap Narrowing and Morphological Transformation in Gold Nanoparticle Assemblies

The plasmonic properties of gold nanoparticle (AuNP) assemblies are critically influenced by the nanogaps between particles. Here, we demonstrate that plasma treatment effectively narrows these nanogaps and ultimately merges the nanoparticles. This process induces a sequential redshift, weakening, broadening, and eventual blueshift of the plasmon coupling peak in UV–vis spectra, indicating transitions from classical to quantum regimes and finally to contact modes. Surface-enhanced Raman spectroscopy reveals an initial increase in intensity as the nanogaps narrow, followed by a decline as linker molecules are removed. Transmission electron microscopy images further show significant deformation of AuNPs after 5 min of plasma treatment. Based on these combined observations, we propose that oxidative desorption of thiol linkers causes the collapse of self-assembled monolayers, leading to the gradual narrowing of nanogaps and eventual particle fusion. This plasma-induced transformation also enables the creation of novel AuNP shapes, such as nano-snowmen and particles with protruding morphologies, by merging heterodimers or core-satellite structures. Our findings not only deepen the understanding of plasma effects on nanoparticle assemblies but also expand the utility of plasma treatment for controlling nanogap distances and fabricating exotic nanoparticle shapes.