Conductivity of Poly(pyrrole)-Poly(styrene sulfonate) Core-Shell Nanoparticles

The dielectric properties of poly(styrene) nanoparticles decorated at their surfaces with poly(styrene sulfonate) [PSS] brushes and subsequently loaded with polypyrrole (PPy) were studied. These film-forming materials which may serve as hole-injection layers in organic light-emitting diodes, exhibit a core-shell-type morphology with a core of electrically insulating polystyrene and a shell consisting of a corona of PSS chains which form the matrix in which the electrically conducting complex of PPy and PSS is embedded. This conducting complex exists in form of domains of nanoscale dimensions. Thin compressed pellets of these nanoparticles were studied using mainly impedance spectroscopy. Measurements were carried out in the temperature range between 123 and 453 K and frequency range from 10(-1) to 10(6) Hz. While earlier studies were centered around the effect of polypyrrole volume fraction on the conductivity films and pellets composed of these nanoparticles, the present study reveals in which way the conductivity can be modified by exchange of the mobile inorganic counter ions of PSS. Besides the free-acid form (H+), the Li+-, Na+- and Cs+-salts of PSS were investigated. The PPy volume fraction was the same for all PPy/PSS core-shell nanoparticles. The distance for phonon-assisted hopping between next-neighbor polypyrrolium chains is influenced by the presence of these inorganic cations. For all samples containing PPy, a transition from insulating to conducting behavior in the range of 300-350 K was found. Using the fluctuation-induced tunneling model, the average tunneling distance, as well as the potential energy barrier separating neighboring conducting grains was estimated. Finally, a detailed analysis of the dielectric spectra suggests the localization length of the charge carriers to be about 0.33 nm.