Kanimozhi, Catherine and Yaacobi-Gross, Nir and Burnett, Edmund K and Briseno, Alejandro L and Anthopoulos, Thomas D and Salzner, Ulrike and Patil, Satish (2014) Use of side-chain for rational design of n-type diketopyrrolopyrrole-based conjugated polymers: what did we find out? In: PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 16 (32). pp. 17253-17265.
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Abstract
The primary role of substituted side chains in organic semiconductors is to increase their solubility in common organic solvents. In the recent past, many literature reports have suggested that the side chains play a critical role in molecular packing and strongly impact the charge transport properties of conjugated polymers. In this work, we have investigated the influence of side-chains on the charge transport behavior of a novel class of diketopyrrolopyrrole (DPP) based alternating copolymers. To investigate the role of side-chains, we prepared four diketopyrrolopyrrole-diketopyrrolopyrrole (DPP-DPP) conjugated polymers with varied side-chains and carried out a systematic study of thin film microstructure and charge transport properties in polymer thin-film transistors (PTFTs). Combining results obtained from grazing incidence X-ray diffraction (GIXD) and charge transport properties in PTFTs, we conclude side-chains have a strong influence on molecular packing, thin film microstructure, and the charge carrier mobility of DPP-DPP copolymers. However, the influence of side-chains on optical properties was moderate. The preferential ``edge-on'' packing and dominant n-channel behavior with exceptionally high field-effect electron mobility values of >1 cm(2) V-1 s(-1) were observed by incorporating hydrophilic (triethylene glycol) and hydrophobic side-chains of alternate DPP units. In contrast moderate electron and hole mobilities were observed by incorporation of branched hydrophobic side-chains. This work clearly demonstrates that the subtle balance between hydrophobicity and hydrophilicity induced by side-chains is a powerful strategy to alter the molecular packing and improve the ambipolar charge transport properties in DPP-DPP based conjugated polymers. Theoretical analysis supports the conclusion that the side-chains influence polymer properties through morphology changes, as there is no effect on the electronic properties in the gas phase. The exceptional electron mobility is at least partially a result of the strong intramolecular conjugation of the donor and acceptor as evidenced by the unusually wide conduction band of the polymer.
Item Type: | Journal Article |
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Publication: | PHYSICAL CHEMISTRY CHEMICAL PHYSICS |
Publisher: | ROYAL SOC CHEMISTRY |
Additional Information: | Copy right for this article belongs to the ROYAL SOC CHEMISTRY, THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND |
Department/Centre: | Division of Chemical Sciences > Solid State & Structural Chemistry Unit |
Date Deposited: | 04 Sep 2014 10:52 |
Last Modified: | 04 Sep 2014 10:52 |
URI: | http://eprints.iisc.ac.in/id/eprint/49750 |
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