M. Reghu et al., SUPERLOCALIZATION OF THE ELECTRONIC WAVE-FUNCTIONS IN CONDUCTIVE POLYMER BLENDS AT CONCENTRATIONS NEAR THE PERCOLATION-THRESHOLD, Macromolecules, 26(26), 1993, pp. 7245-7249
The ability to solution-process polyaniline (PANI) in the protonated c
onducting form through the use of surfactant counterions has enabled t
he fabrication of conductive polymer blends with a percolation thresho
ld at a volume fraction near 1 %. Electron micrographs of blends of PA
NI complexed with camphorsulfonic acid (CSA) in poly(methyl methacryla
te) show a tenuous interconnected network; for concentrations of PANI-
CSA near the percolation threshold, the network is self-similar. Digit
al analysis of the micrographs shows that in thin two-dimensional 'sli
ces' the PANI-CSA networks are fractal, with the area (S) of the condu
cting network varying as S is-proportional-to r(D), where D < 2 for co
ncentrations below 4 %. Near the threshold, we find D almost-equal-to
1.5, implying a fractal dimensionality in three dimensions of ca. 2.5.
The electrical conductivity of these blends follows the Mott-Deutsche
r model for variable-range hopping on a fractal network, sigma(T) appr
oximately exp[-(T0/T)gamma]. We find that gamma increases from gamma =
1/4 in pure PANI-CSA (indicting variable-range hopping among exponent
ially localized states) to gamma almost-equal-to 2/3 as the PANI-CSA c
oncentration is reduced to the percolation threshold, indicating varia
ble-range hopping among superlocalized states on the fractal structure
in the limit where the Coulomb interaction between the electron and t
he hole dominates the intersite hopping.