Effect of thickness-dependent microstructure on the out-of-plane hole mobility in poly(3-hexylthiophene) films

Regioregular poly(3-hexylthiophene) (RR-P3HT) is a widely used donor material for bulk heterojunction polymer solar cells. While much is known about the structure and properties of RR-P3HT films, important questions regarding hole mobilities in this material remain unresolved. Measurements of the out-of-plane hole mobilities, μ, of RR-P3HT films have been restricted to films in the thickness regime on the order of micrometers, beyond that generally used in solar cells, where the film thicknesses are typically 100 to 200 nm. Studies of in-plane carrier mobilities have been conducted in thinner films, in the thickness range 100-200 nm. However, the in-plane and out-of-plane hole mobilities in RR-P3HT can be significantly different. We show here that the out-of-plane hole mobilities in neat RR-P3HT films increase by an order of magnitude, from 10(-4) cm(2)/V·s, for a 80 nm thick film, to a value of 10(-3) cm(2)/V·s for films thicker than 700 nm. Through a combination of morphological characterization and simulations, we show that the thickness dependent mobilities are not only associated with the differences between the average morphologies of thick films and thin films, but specifically associated with changes in the local morphology of films as a function of distance from the interfaces.