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ACS Appl Mater Interfaces. 2016 Apr 13;8(14):9285-96. doi: 10.1021/acsami.6b01607. Epub 2016 Mar 30.

Direct Uniaxial Alignment of a Donor-Acceptor Semiconducting Polymer Using Single-Step Solution Shearing.

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Department of Chemical Engineering, Stanford University , Stanford, California 94305, United States.
BASF Schweiz AG, GMV/BE, R-1059.5.09, Mattenstrasse, 4058 Basel, Switzerland.
Stanford Institute for Materials and Energy Sciences , SLAC National Accelerator Laboratory , 2575 Sand Hill Road, Menlo Park, California 94025, United States.
Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory , Menlo Park, California 94025, United States.
BASF SE, GMV/T, J542, 67056 Ludwigshafen, Germany.


The alignment of organic semiconductors (OSCs) in the active layers of electronic devices can confer desirable properties, such as enhanced charge transport properties due to better ordering, charge transport anisotropy for reduced device cross-talk, and polarized light emission or absorption. The solution-based deposition of highly aligned small molecule OSCs has been widely demonstrated, but the alignment of polymeric OSCs in thin films deposited directly from solution has typically required surface templating or complex pre- or postdeposition processing. Therefore, single-step solution processing and the charge transport enhancement afforded by alignment continue to be attractive. We report here the use of solution shearing to tune the degree of alignment in poly(diketopyrrolopyrrole-terthiophene) thin films by controlling the coating speed. A maximum dichroic ratio of ∼7 was achieved on unpatterned substrates without any additional pre- or postdeposition processing. The degree of polymer alignment was found to be a competition between the shear alignment of polymer chains in solution and the complex thin film drying process. Contrary to previous reports, no charge transport anisotropy was observed because of the small crystallite size relative to the channel length, a meshlike morphology, and the likelihood of increased grain boundaries in the direction transverse to coating. In fact, the lack of aligned morphological structures, coupled with observed anisotropy in X-ray diffraction data, suggests the alignment of polymer molecules in both the crystalline and the amorphous regions of the films. The shear speed at which maximum dichroism is achieved can be controlled by altering deposition parameters such as temperature and substrate treatment. Modest changes in molecular weight showed negligible effects on alignment, while longer polymer alkyl side chains were found to reduce the degree of alignment. This work demonstrates that solution shearing can be used to tune polymer alignment in a one-step deposition process not requiring substrate patterning or any postdeposition treatment.


donor−acceptor copolymers; field-effect transistors; organic semiconductors; polymer alignment; polymer semiconductors; solution processing; solution shearing


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