Esterification-Induced Spontaneous Deposition of Nanoparticle Monolayers on Substrates with Percolation Network Morphology

Nanoparticle monolayers (NPMLs) exhibit unique collective properties that are highly desirable for applications in sensors, catalysts, and optics. However, their practical use is often hindered by structural instability, especially when they are exposed to solvents. In this study, we developed a method for the spontaneous deposition of gold nanoparticle monolayers (AuNPMLs) on silicon substrates via covalent bonding interactions that provides excellent structural stability in solvents with varying polarities. The esterification reaction between carboxyl-functionalized gold nanoparticles and alkyl-chloride-functionalized silicon substrates spontaneously forms AuNPMLs on the substrate in which single-crystalline domains are interconnected, forming a percolation network morphology. The <i>ex situ</i> scanning electron microscopy measurements show that the surface coverage of AuNPMLs rapidly increases up to ca. 60% during the initial 10 min, followed by gradual growth and saturation at ca. 70% at 360 min of deposition time. On the other hand, the single-crystalline domain size reaches its maximum at 45 min and then gradually decreases, which may be attributed to the desorption of AuNPs by the hydrolysis of ester bonds. The reflectance spectra of AuNPMLs showed the red shift as the deposition time increases up to 45 min with a subsequent blue shift thereafter, which is consistent with the change of the single-crystalline domain size with the deposition time. The covalent bonding interaction-mediated nanoparticle deposition method can be used to form stable AuNPMLs with controlled surface coverage and domain size, allowing for fine control of the optical properties and possibly other properties. The excellent structural stability of AuNPMLs and their controlled properties may provide new opportunities for practical applications of NPMLs.