Unraveling the Implications of Macromolecular Orientation on the Planar and Vertical Charge Transport in Organic Electronic Devices

The role of film morphology of conjugated polymers (CPs) and their macromolecular conformation with respect to the substrate in governing charge transport and overall device performances has been a matter of debate. The nature of the macromolecular orientation of CPs in thin films has a pivotal role in controlling the performance of planar and sandwich devices. Thin-film characterizations unveiled that spin-coated films are isotropic with mixed edge-on/face-on conformation, whereas unidirectional floating film transfer method (UFTM) films are anisotropic with edge-on-oriented micrometer-sized ordered domains. To unravel the explicit role of molecular orientation on device performance, two types of devices, organic Schottky diodes (OSDs) for out-of-plane carrier transport and organic field-effect transistors (OFETs) for in-plane charge transport, were fabricated and characterized. Isotropic and relatively low crystalline spin-coated films exhibited superior transport characteristics in the out-of-plane direction than UFTM films irrespective of the crystallinity. On the other hand, edge-on-oriented UFTM thin films demonstrated remarkably enhanced in-plane charge transport with more than two orders of magnitude of enhancement in the field-effect mobility. The nature of molecular orientation of different films is significantly correlated with the performance of the OSDs and OFETs.