Tuning charge transport dynamics via clustering of doping in organic semiconductor thin films

A significant challenge in the rational design of organic thermoelectric materials is to realize simultaneously high electrical conductivity and high induced-voltage in response to a thermal gradient, which is represented by the Seebeck coefficient. Conventional wisdom posits that the polymer alone dictates thermoelectric efficiency. Herein, we show that doping-in particular, clustering of dopants within conjugated polymer films-has a profound and predictable influence on their thermoelectric properties. We correlate Seebeck coefficient and electrical conductivity of iodine-doped poly(3-hexylthiophene) and poly[2,5-bis(2-octyldo-decyl) pyrrolo[3,4-c] pyrrole-1,4(2H,5H)-dione-3,6-diyl)-alt-(2,2'; 5',2 '';5 '',2'''-quaterthiophen-5,5 '''-diyl)] films with Kelvin probe force microscopy to highlight the role of the spatial distribution of dopants in determining overall charge transport. We fit the experimental data to a phonon-assisted hopping model and found that the distribution of dopants alters the distribution of the density of states and the Kang-Snyder transport parameter. These results highlight the importance of controlling dopant distribution within conjugated polymer films for thermoelectric and other electronic applications.