Impact of the Doping Method on Conductivity and Thermopower in Semiconducting Polythiophenes

The development of organic semiconductors for use in thermoelectrics requires the optimization of both their thermopower and electrical conductivity. Here two fundamentally different doping mechanisms are used to investigate the thermoelectric properties of known high hole mobility polymers: poly 3‐hexylthiophene (P3HT), poly(2,5 ‐ bis(3‐tetradecylthiophen‐2‐yl)thieno[3,2‐b]thiophene) (PBTTT‐C 14 ), and poly(2,5‐bis(thiphen‐2‐yl)‐(3,7‐diheptadecantyltetrathienoacene)) (P2TDC 17 ‐FT4). The small molecule tetrafluorotetracyanoquinodimethane (F 4 TCNQ) is known to effectively dope these polymers, and the thermoelectric properties are studied as a function of the ratio of dopant to polymer repeat unit. Higher electrical conductivity and values of the thermoelectric power factor are achieved by doping with vapor‐deposited fluoroalkyl trichlorosilanes. The combination of these data reveals a striking relationship between thermopower and conductivity in thiophene‐based polymers over a large range of electrical conductivity that is independent of the means of electrical doping. This relationship is not predicted by commonly used transport models for semiconducting polymers and is demonstrated to hold for other semiconducting polymers as well.