An analyzed substance’s signal intensity and detection sensitivity in surface-enhanced Raman spectroscopy (SERS) significantly depend on the size and agglomeration degree of nanoparticles (NPs) forming the enhancing structure. Structures were manufactured by aerosol dry printing (ADP), where NPs’ agglomeration depends on printing conditions and additional particle modification techniques. The influence of agglomeration degree on SERS signal enhancement was studied in three types of printed structures using the methylene blue model molecule as an analyte. We demonstrated that the ratio between individual NPs and agglomerates in a studied structure strongly affects SERS signal amplification, and structures formed mainly from non-agglomerated NPs enhance the signal better. In this sense, aerosol NPs modified by pulsed laser radiation provide better results than thermally modified NPs, since in laser modification a larger number of individual NPs is observed due to the absence of secondary agglomeration effects in the gas stream. However, increasing gas flow may minimize the secondary agglomeration, since the time allotted for the agglomeration processes is reduced. In this paper, we show how different NPs’ agglomeration tendencies influence SERS enhancement to demonstrate the process of using ADP to form inexpensive and highly efficient SERS substrates with huge application potential.

In this paper, we investigated the interaction of nanosecond pulsed-periodic infrared (IR) laser radiation at a 50 and 500 Hz repetition rate with aerosol platinum (Pt) and silver (Ag) nanoparticles agglomerates obtained in a spark discharge. Results showed the complete transformation of Pt dendrite-like agglomerates with sizes of 300 nm into individual spherical nanoparticles directly in a gas flow under 1053 nm laser pulses with energy density 3.5 mJ/cm². Notably, the critical energy density required for this process depended on the size distribution and extinction of agglomerates nanoparticles. Based on the extinction cross-section spectra results, Ag nanoparticles exhibit a weaker extinction in the IR region in contrast to Pt, so they were not completely modified even under the pulses with energy density up to 12.7 mJ/cm². The obtained results for Ag and Pt laser sintering were compared with corresponding modification of gold (Au) nanoparticles studied in our previous work. Here we considered the sintering mechanisms for Ag, Pt and Au nanoparticles agglomerates in the aerosol phase and proposed the model of their laser sintering based on one-stage for Pt agglomerates and two-stage shrinkage processes for Au and Ag agglomerates.