Tuning the electrical conductivity of Pt-containing granular metals by postgrowth electron irradiation

We have fabricated Pt-containing granular metals by focused electron beam induced deposition from the $(CH_3)_3CH_3C_5H_4Pt$ precursor gas. The granular metals are made of platinum nanocrystallites embedded in a carbonaceous matrix. We have exposed the as-grown nanocomposites to low energy electron beam irradiation and we have measured the electrical conductivity as a function of the irradiation dose. Postgrowth electron beam irradiation transforms the matrix microstructure and thus the strength of the tunneling coupling between Pt nanocrystallites. For as-grown samples (weak tunnel coupling regime) we find that the temperature dependence of the electrical conductivity follows the stretched exponential behavior characteristic of the correlated variable-range hopping transport regime. For briefly irradiated samples (strong tunnel coupling regime) the electrical conductivity is tuned across the metal-insulator transition. For long-time irradiated samples the electrical conductivity behaves like that of a metal. In order to further analyze changes of the microstructure as a function of the electron irradiation dose we have carried out transmission electron microscope (TEM), micro-Raman and atomic force microscopy (AFM) investigations. TEM pictures reveal that the crystallites' size of long-time irradiated samples is larger than that of as-grown samples. Furthermore we do not have evidence of microstructural changes in briefly irradiated samples. By means of micro-Raman we find that by increasing the irradiation dose the matrix changes following a graphitization trajectory between amorphous carbon and nanocrystalline graphite. Finally, by means of AFM measurements we observe a reduction of the volume of the samples with increasing irradiation time which we attribute to the removal of carbon molecules.