From plasma to nanoparticles: optical and particle emission of a spark discharge generator

The increased demand for high purity nanoparticles (NPs) of defined geometry necessitates the continuous development of generation routes. One of the most promising physical techniques for producing metal, semiconductor or alloy NPs in the gas phase is spark discharge NP generation. The technique has a great potential for up-scaling without altering the particles. Despite the simplicity of the setup, the formation of NPs in a spark discharge takes place via complex multi-scale processes, which greatly hinders the investigation via conventional NP measurement techniques. In the present work, time-resolved optical emission spectroscopy (OES) was used to provide information on the species present in the spark from as early as approximately 100 ns after the initiation of the discharge. We demonstrate that operando emission spectroscopy can deliver valuable insights into NP formation. The emission spectra of the spark are used to identify, among others, the main stages of material erosion and to calculate the quenching rate of the generated metal vapour. We demonstrate that the alteration of key control parameters, that are typically used to optimize NP generation, clearly affect the emission spectra. We report for Cu and Au NPs that the intensity of spectral lines emitted by metal atoms levels off when spark energy is increased above an energy threshold, suggesting that the maximum concentration of metal vapour produced in the generator is limited. This explains the size variation of the generated NPs. We report a strong correlation between the optical and particle emission of the spark discharge generator, which demonstrate the suitability of OES as a valuable characterization tool that will allow for the more deliberate optimization of spark-based NP generation.