Grazing incidence X‐ray diffraction (GI‐XRD) is used to characterize the crystallographic dynamics of low molecular weight (LMW) and high molecular weight (HMW) poly(3‐hexylselenophene) (P3HS) films and blend films of P3HS with [6‐6‐]‐phenyl‐C61‐butyric acid methyl ester (PCBM) as a function of ‘step‐by‐step’ thermal annealing, from room temperature to 250 °C. The temperature‐dependent GIXRD data show how the melting point of P3HS crystallites is decreased by the presence of PCBM. P3HS crystallite domain sizes dramatically increase upon annealing to the P3HS melting temperature. The formation of well‐oriented HMW P3HS crystallites with the (100) plane parallel to the substrate (edge‐on orientation), when cooled from melt, are observed. We compare the behaviour of P3HS pure and blend films with that of poly(3‐hexyl)thiophene (P3HT) pure and PCBM blended films and suggest that the similar temperature dependent behaviour we observe may be a common to polythiophene and related polymers and their blends.
