Carrier–Carrier Repulsion Limits the Conductivity of N‐Doped Organic Semiconductors

Molecular doping is a key strategy to enhance the electrical conductivity of organic semiconductors. Typically, the electrical conductivity shows a maximum value upon increased doping, after which the conductivity decreases. This decrease in conductivity is commonly attributed to unfavorable changes in the morphology. However, in recent simulation work, has shown, that the conductivity-at high doping-is instead limited by electron-electron repulsion rather than by morphology, at least for some material combinations. Based on the simulations, this limitation is expected to show up in the dependence of the Seebeck coefficient versus carrier density: the Seebeck coefficient will follow Heike's formula if carrier-carrier repulsion limits the conductivity. Here, the electrical conductivity and Seebeck coefficient are measured as a function of doping for a series of n-type organic semiconductors. Additionally, the resulting carrier density is measured using metal-insulator-semiconductor diodes, which link dopant loading and the number of charge carriers. At high carrier densities, the Seebeck coefficient indeed follows Heike's formula, confirming that the conductivity is limited by carrier-carrier repulsion rather than by morphological effects. This study shows that current models of hopping transport in organic semiconductors may be incomplete. As a result, this study offers novel insights in the design of organic semiconductors.