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    Sequentially Processed P3HT/CN6-CP•−NBu4+ Films: Interfacial or Bulk Doping?
    (Weinheim : Wiley-VCH, 2020) Karpov, Yevhen; Kiriy, Nataliya; Formanek, Petr; Hoffmann, Cedric; Beryozkina, Tetyana; Hambsch, Mike; Al-Hussein, Mahmoud; Mannsfeld, Stefan C.B.; Büchner, Bernd; Debnath, Bipasha; Bretschneider, Michael; Krupskaya, Yulia; Lissel, Franziska; Kiriy, Anton
    Derivatives of the hexacyano-[3]-radialene anion radical (CN6-CP•−) emerge as a promising new family of p-dopants having a doping strength comparable to that of archetypical dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-quinodimethane (F4TCNQ). Here, mixed solution (MxS) and sequential processing (SqP) doping methods are compared by using a model semiconductor poly(3-hexylthiophene) (P3HT) and the dopant CN6-CP•−NBu4 + (NBu4 + = tetrabutylammonium). MxS films show a moderate yet thickness-independent conductivity of ≈0.1 S cm−1. For the SqP case, the highest conductivity value of ≈6 S cm−1 is achieved for the thinnest (1.5–3 nm) films whereas conductivity drops two orders of magnitudes for 100 times thicker films. These results are explained in terms of an interfacial doping mechanism realized in the SqP films, where only layers close to the P3HT/dopant interface are doped efficiently, whereas internal P3HT layers remain essentially undoped. This structure is in agreement with transmission electron microscopy, atomic force microscopy, and Kelvin probe force microscopy results. The temperature-dependent conductivity measurements reveal a lower activation energy for charge carriers in SqP samples than in MxS films (79 meV vs 110 meV), which could be a reason for their superior conductivity. © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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    Charge Carrier Mobility Improvement in Diketopyrrolopyrrole Block-Copolymers by Shear Coating
    (Basel : MDPI, 2021) Ditte, Kristina; Kiriy, Nataliya; Perez, Jonathan; Hambsch, Mike; Mannsfeld, Stefan C.B.; Krupskaya, Yulia; Maragani, Ramesh; Voit, Brigitte; Lissel, Franziska
    Shear coating is a promising deposition method for upscaling device fabrication and enabling high throughput, and is furthermore suitable for translating to roll-to-roll processing. Although common polymer semiconductors (PSCs) are solution processible, they are still prone to mechanical failure upon stretching, limiting applications in e.g., electronic skin and health monitoring. Progress made towards mechanically compliant PSCs, e.g., the incorporation of soft segments into the polymer backbone, could not only allow such applications, but also benefit advanced fabrication methods, like roll-to-roll printing on flexible substrates, to produce the targeted devices. Tri-block copolymers (TBCs), consisting of an inner rigid semiconducting poly-diketo-pyrrolopyrrole-thienothiophene (PDPP-TT) block flanked by two soft elastomeric poly(dimethylsiloxane) (PDMS) chains, maintain good charge transport properties, while being mechanically soft and flexible. Potentially aiming at the fabrication of TBC-based wearable electronics by means of cost-efficient and scalable deposition methods (e.g., blade-coating), a tolerance of the electrical performance of the TBCs to the shear speed was investigated. Herein, we demonstrate that such TBCs can be deposited at high shear speeds (film formation up to a speed of 10 mm s−1). While such high speeds result in increased film thickness, no degradation of the electrical performance was observed, as was frequently reported for polymer−based OFETs. Instead, high shear speeds even led to a small improvement in the electrical performance: mobility increased from 0.06 cm2 V−1 s−1 at 0.5 mm s−1 to 0.16 cm2 V−1 s−1 at 7 mm s−1 for the TBC with 24 wt% PDMS, and for the TBC containing 37 wt% PDMS from 0.05 cm2 V−1 s−1 at 0.5 mm s−1 to 0.13 cm2 V−1 s−1 at 7 mm s−1. Interestingly, the improvement of mobility is not accompanied by any significant changes in morphology.