2D Coherent Charge Transport in Highly Ordered Conducting Polymers Doped by Solid State Diffusion

Doping is one of the most important methods to control charge carrier concentration in semiconductors. Ideally, the introduction of dopants should not perturb the ordered microstructure of the semiconducting host. In some systems, such as modulation-doped inorganic semiconductors or molecular charge transfer crystals, this can be achieved by spatially separating the dopants from the charge transport pathways. However, in conducting polymers dopants tend to be randomly distributed within the conjugated polymer and as a result the transport properties are strongly affected by the resulting structural and electronic disorder. Here, we show that in the highly ordered lamellar microstructure of a regioregular thiophene-based conjugated polymer a small-molecule p-type dopant can be incorporated by solid-state diffusion into the layers of solubilising side chains without disrupting the conjugated layers. In contrast to more disordered systems, this allows us to observe coherent, free-electron-like charge transport properties, including a nearly ideal Hall effect in a wide temperature range, a positive magneto-conductance due to weak localisation and Pauli paramagnetic spin susceptibility.The research leading to these results has received funding from the European Research Council under the European Union’s Seventh Framework Programme (FP7/2007-2013) / ERC grant agreement n 610115. K.K. thanks the Samsung Scholarship Foundation for financial support. S.W. thanks H. Matsui and J. Takeya of University of Tokyo for stimulating discussions, and is supported by Research Fellowships of Japan Society for the Promotion of Science for Young Scientists, and JST PRESTO. K.B. acknowledges funding by the German Research Foundation (BR 4869/1-1). S. K. and H. T. acknowledge funding from the Japan Society for the Promotion of Science (No. 25287073). The authors thank D. Venkateshvaran and A. Sadhanala of the University of Cambridge for help with the measurements. Part of this work is based upon research conducted at the Cornell High Energy Synchrotron Source (CHESS). CHESS is supported by the NSF & NIH/NIGMS via NSF award DMR-1332208. We thank D.-M. Smilgies, X. Sheng and J. Dolan for their help during the D1 experiment at CHESS. We thank A. Hexemer, R. Pandolfi and C. Zhu for supporting the data evaluation, who are supported by the U.S. Department of Energy under Contract No. DEAC02-05CH1123, the ECA award program and the LBNL LDRD ?TReXS?. The authors thank Professor Klaus M¨ullen of Max Planck Institue for Polymer Research for providing CDT-BTZ.This is the author accepted manuscript. It is currently under an indefinite embargo pending publication by the Nature Publishing Group