Engineered doping of organic semiconductors for enhanced thermoelectric efficiency

Significant improvements to the thermoelectric figure of merit ZT have emerged in recent years, primarily due to the engineering of material composition and nanostructure in inorganic semiconductors (ISCs). However, many present high-ZT materials are based on low-abundance elements that pose challenges for scale-up, as they entail high material costs in addition to brittleness and difficulty in large-area deposition. Here we demonstrate a strategy to improve ZT in conductive polymers and other organic semiconductors (OSCs) for which the base elements are earth-abundant. By minimizing total dopant volume, we show that all three parameters constituting ZT vary in a manner so that ZT increases; this stands in sharp contrast to ISCs, for which these parameters have trade-offs. Reducing dopant volume is found to be as important as optimizing carrier concentration when maximizing ZT in OSCs. Implementing this strategy with the dopant poly(styrenesulphonate) in poly(3,4-ethylenedioxythiophene), we achieve ZT  =  0.42 at room temperature.