Increasing the Content of Edge-On Orientation to Improve the Hole Mobility of IDTBT Film by the van der Waals Interaction between the Side Chain and Alkane Additives

The molecular orientation in the conjugated polymer film critically impacts the performance of organic electronic devices. As for organic field-effect transistors (OFETs), the edge-on orientation is beneficial for efficient interchain charge transport. However, for the near amorphous indacenodithiophene-co-benzothiadiazole (IDTBT) film, the face-on orientation was dominated in the drop cast thin film. Herein, we proposed a strategy to increase the edge-on orientation in IDTBT films by inserting n-hexadecane (16C) additives with a high boiling point between the side chains. Because the 16C additives had a similar structure to that of the side chain, the 16C additives were distributed around the side chain in the nucleation stage. Then, the backbone aggregated quickly with the nuclei formation speed (k) nearly twice as high as that without the 16C additives. In the growth stage, some face-on nuclei turned to edge-on nuclei due to the van der Waals interactions between the side chain and 16C additives. This was verified by the results of in situ GIWAXS, where the intensity of (010) decreased and the intensity of (100) increased in the out-of-plane direction. The edge-on orientation content of the film with 16C additives reached 57%, higher than that of the neat film (33%). Moreover, compared to the neat IDTBT film, the lamellar packing distance of the film with 16C additives increased the lamellar packing distance from 16.97 to 23.26 Å and the π-π stacking distance decreased from 4.36 to 4.19 Å. The hole mobility of the film with 16C additives (3.24 ± 0.19 cm² V^-1 s^-1) was higher than that of the neat film (0.94 ± 0.07 cm² V^-1 s^-1).