Effect of the Gas Temperature on Agglomeration of Au Nanoparticles Synthesized by Spark Discharge and Their Application in Surface-Enhanced Raman Spectroscopy

Abstract

In this work, we have, for the first time, experimentally verified the hypothesis of reducing the agglomeration rate of aerosol nanoparticles produced by spark discharge upon decreasing the carrier gas temperature in the range of 24 °C to –183 °C. The synthesis of nanoparticles was implemented as a result of spark ablation of electrodes manufactured from Au with a purity of 99.998% installed in a specially designed gas chamber dipped into liquid nitrogen (−196 °C) to cool down the carrier gas supplied through one of hollow electrodes. It follows from the analysis of transmission electron microscopy images that both the average size of primary nanoparticles and the degree of their sintering become lower if the gas is cooled. For example, in the case of using nitrogen as a carrier gas, the average size of primary nanoparticles decreases from 9.4 nm to 6.6 nm as the gas temperature decreases from 24 °C to –183 °C. This also causes the aggregates to become more branched, manifested by the reduction in their solidity from 92% to 76%. The agglomeration model of Feng based on Smoluchowski theory was employed to calculate particle size distributions that were found to be consistent with the experimental data. The gold nanoparticles synthesized at room and cryogenic temperatures of the carrier gas (N₂, Ar + H₂, He) were used to pattern plasmonic nanostructures on ceramic alumina substrates by using aerosol jet printing technology for the purpose of demonstrating the possibility of their application in surface-enhanced Raman spectroscopy (SERS). The SERS enhancement factor was estimated at 2 × 106 from the analysis of SERS and normal Raman spectra of 1,2-bis(4-pyridyl)ethylene used as an analyte.