Unidirectionally Aligned Donor–Acceptor Semiconducting Polymers in Floating Films for High‐Performance Unipolar n‐Channel Organic Transistors

Abstract The orientational control of semiconducting polymers (SCPs) in floating films offers several advantages over conventional solution‐processing methods for device fabrication, and the unidirectional floating film transfer method (UFTM) has been applied to fabricate large‐area oriented p‐type SCP films. Here, UFTM can be used to prepare high‐performance n‐type SCP films of P(NDI2OD‐T2) is reported. A strong correlation between the degree of polymer orientation and the solvent used for the preparation of P(NDI2OD‐T2) floating films is observed. In particular, the size of the nanofibers aligned along the orientation direction prepared using chloroform is dramatically increased by adding a small amount of chlorobenzene. Microstructural characterization reveals that the P(NDI2OD‐T2) floating films are uniaxially aligned with edge‐on orientation, whereas the spin‐coated films are isotropic with face‐on orientation. Notably, the floating films of P(NDI2OD‐T2) prepared with solvent blending have higher electron mobility with ambipolar‐like device characteristics and high threshold voltage (VTH) of ≈25 V. Finally, using the one‐step immersion process, the introduction of an interlayer of hexa(ethylene glycol)‐dithiol between the source/drain contacts and P(NDI2OD‐T2) film results in a drastic improvement in device, giving unipolar n‐channel transistor characteristics with a VTH of ≈0 V, on/off ratio of >105, and mobility reliability factor of almost 100%.