Photothermal Determination of Absorption and Scattering Spectra of Silver Nanoparticles

This work reports on photothermal lens spectra of silver nanoparticles of different dimensions in the spectral region of 370-730 nm performed using an arc-lamp-based photothermal spectrophotometer. We show that the photothermal and extinction cross-section spectra of the samples are similar for nanoparticles of reduced dimensions where scattering effects are small. The results differ substantially for nanoparticles of a diameter larger than 30 nm for which scattering becomes relevant. We demonstrate that the photothermal spectrum corresponds to the absorption component of the particle's extinction. Photothermal spectra show a clear picture of the plasmonic peaks of the nanoparticle even in the presence of high scattering. By subtracting the photothermal component from the total extinction, we extract the scattering cross-section spectra of the nanoparticles. The technique allows determination of the absorption and scattering components of the extinction providing a better understanding of the particle's optical properties. The results agree well with the Mie approximation, which is valid for a single spherical nanoparticle. We discuss and demonstrate the application of the method to characterize particles of arbitrary shape and dimensions.