Multilevel Investigation of Charge Transport in Conjugated Polymers

Conjugated polymers have attracted the world's attentions since their discovery due to their great promise for optoelectronic devices. However, the fundamental understanding of charge transport in conjugated polymers remains far from clear. The origin of this challenge is the natural disorder of polymers with complex molecular structures in the solid state. Moreover, an effective way to examine the intrinsic properties of conjugated polymers is absent. Optoelectronic devices are always based on spin-coated films. In films, polymers tend to form highly disordered structures at nanometer to micrometer length scales due to the high degree of conformational freedom of macromolecular chains and the irregular interchain entanglement, thus typically resulting in much lower charge transport properties than their intrinsic performance. Furthermore, a subtle change of processing conditions may dramatically affect the film formation-inducing large variations in the morphology, crystallinity, microstructure, molecular packing, and alignment, and finally varying the effective charge transport significantly and leading to great inconsistency over an order of magnitude even for devices based on the same polymer semiconductor. Meanwhile, the charge transport mechanism in conjugated polymers is still unclear and its investigation is challenging based on such complex microstructures of polymers in films. Therefore, how to objectively evaluate the charge transport and probe the charge transport mechanism of conjugated polymers has confronted the world for decades. In this Account, we present our recent progress on multilevel charge transport in conjugated polymers, from disordered films, uniaxially aligned thin films, and single crystalline micro- or nanowires to molecular scale, where a derivative of poly(para-phenylene ethynylene) with thioacetyl end groups (TA-PPE) is selected as the candidate for investigation, which could also be extended to other conjugated polymer systems. Our systematic investigations demonstrated that 3-4 orders higher charge transport properties could be achieved with the improvement of polymer chain order and confirmed efficient charge transport along the conjugated polymer backbones. Moreover, with downscaling to molecular scale, many novel phenomena were observed such as the largely quantized electronic structure for an 18 nm-long TA-PPE and the modulation of the redox center of tetrathiafulvalene (TTF) units on tunneling charge transport, which opens the door for conjugated polymers used in nanometer quantum devices. We hope the understanding of charge transport in PPE and its related conjugated polymer at multilevel scale in this Account will provide a new method to sketch the charge transport properties of conjugated polymers, and new insights into the combination of more conjugated polymer materials in the multilevel optoelectronic and other related functional devices, which will offer great promise for the next generation of electronic devices.