Determination of Fundamental Morphological Parameters of Supported Nanoparticle Ensembles: Extracting the Functional Dependence Between Nanoparticle Shape and Size
F. Hubenthal, C. Hendrich, T.A. Vartanyan, F. Träger
A new model to extract important morphological parameters of noble metal nanoparticle ensembles with a broad size and shape distribution is presented. The technique is based on a rigorous simulation of the inhomogeneously broadened extinction profiles of nanoparticle ensembles. As input data, only experimentally accessible parameters, such as the amount of deposited material, the nanoparticle number density, and the relative size distribution of the nanoparticles, are used. The model can be applied to oblate nanoparticles, which exhibit a strong correlation between their shape and size, e.g., to supported nanoparticles generated, for example, by deposition of atoms and subsequent nucleation or by gas phase deposition. Both methods are standard preparation techniques to generate well-defined nanoparticle ensembles under ultra high vacuum conditions. We apply our model to gold and silver nanoparticles on sapphire and TiO2 supports and obtain a perfect agreement between the calculated and experimental data. More importantly, we could extract the functional dependence between the axial ratio and the radius of the nanoparticles within the ensemble and, therewith, the most probable axial ratio in the ensemble. In addition, the extinction spectrum of a nanoparticle ensemble irradiated with nanosecond pulsed laser light during growth has been successfully modeled. This demonstrates, that the model is able to describe shape changes of resonantly heated nanoparticles within the ensemble. By using the coverage as a free parameter, we could calculate from the extinction spectrum the average particle radius as well as the amount of desorbed atoms after irradiation with laser light. In summary, the model allows a fast, easy, but extensive morphological characterization of nanoparticle ensembles that exhibit a broad size and shape distribution.