Homojunction-induced thermopower enhancement in polymer films

Abstract

It has been more than twenty years since conductive polymers began to receive attention as an emerging thermoelectric material. However, the trade-off between electrical conductivity ({\sigma}) and thermopower (S) has proven to be a major challenge that has obstructed their use in actual devices. Here we report the discovery that the thermopower of the p- and n-type legs of organic thermogenerators can be substantially enhanced, without significant deterioration of {\sigma}, by constructing an in-plane segmented structure consisting of a homojunction with different doping levels on either side. In such segmented layers, the S is abnormally higher than the average value of the constituent parts when applying a forward temperature gradient (heating the heavily doped counterpart), while it is lower upon a reverse temperature gradient. Typically, for a two-stage segmented film of p-type PDPP-Se, an abnormally large S of 210 uV K-1 and {\sigma} of 2.5*10^4 S m-1 are obtained, resulting in a large power factor (PF) of 1100 uW m-1 K-2 and a record ZT of 1.36 at room temperature. The enhanced thermopower is attributed to an additional voltage developed at the homojunction under heating as explained by kinetic Monte Carlo simulations. This finding provides a breakthrough approach to the modulation of thermoelectric transport properties of conductive polymers.