Surface-enhanced Raman spectroscopy (SERS) is a promising optical method for analyzing molecular samples of various nature. Most SERS studies are of an applied nature, indicating a serious potential for their application in analytical practice. Dendritelike nanostructures have great potential for SERS, but the lack of a method for their predictable production significantly limits their implementation. In this paper, a method for controllably obtaining spatially separated, self-organized, and highly-branched silver dendrites via template synthesis in pores of SiO₂/Si is proposed. The dendritic branches have nanoscale roughness, creating many plasmon-active “hotspots” required for SERS. The first held 3D modeling of the external electromagnetic wave interaction with such a dendrite, as well as experimental data, confirms this theory. Using the example of a reference biological analyte, which is usually used as a label for other biological molecules, the dendrites’ SERS-sensitivity up to 10⁻¹⁵M was demonstrated with an enhancement factor of 10⁸. The comparison of simulation results with SERS experiments allows distinguishing the presence of electromagnetic and chemical contributions, which have a different effect at various analyte concentrations.

The modern development of nanotechnology requires the discovery of simple approaches that ensure the controlled formation of functional nanostructures with a predetermined morphology. One of the simplest approaches is the self-assembly of nanostructures. The widespread implementation of self-assembly is limited by the complexity of controlled processes in a large volume where, due to the temperature, ion concentration, and other thermodynamics factors, local changes in diffusion-limited processes may occur, leading to unexpected nanostructure growth. The easiest ways to control the diffusion-limited processes are spatial limitation and localized growth of nanostructures in a porous matrix. In this paper, we propose to apply the method of controlled self-assembly of gold nanostructures in a limited pore volume of a silicon oxide matrix with submicron pore sizes. A detailed study of achieved gold nanostructures’ morphology, microstructure, and surface composition at different formation stages is carried out to understand the peculiarities of realized nanostructures. Based on the obtained results, a mechanism for the growth of gold nanostructures in a limited volume, which can be used for the controlled formation of nanostructures with a predetermined geometry and composition, has been proposed. The results observed in the present study can be useful for the design of plasmonic-active surfaces for surface-enhanced Raman spectroscopy-based detection of ultra-low concentration of different chemical or biological analytes, where the size of the localized gold nanostructures is comparable with the spot area of the focused laser beam.