Lactone Backbone Density in Rigid Electron‐Deficient Semiconducting Polymers Enabling High n‐type Organic Thermoelectric Performance

Three lactone-based rigid semiconducting polymers were designed to overcome major limitations in the development of n-type organic thermoelectrics, namely electrical conductivity and air stability. Experimental and theoretical investigations demonstrated that increasing the lactone group density by increasing the benzene content from 0 % benzene (P-0), to 50 % (P-50), and 75 % (P-75) resulted in progressively larger electron affinities (up to 4.37 eV), suggesting a more favorable doping process, when employing (N-DMBI) as the dopant. Larger polaron delocalization was also evident, due to the more planarized conformation, which is proposed to lead to a lower hopping energy barrier. As a consequence, the electrical conductivity increased by three orders of magnitude, to achieve values of up to 12 S cm and Power factors of 13.2 μWm-1 K-2 were thereby enabled. These findings present new insights into material design guidelines for the future development of air stable n-type organic thermoelectrics.