Recent work in structure–processing relationships of polymer semiconductors have demonstrated the versatility and control of thin-film microstructure offered by meniscusguided coating (MGC) techniques. Here, we analyze the qualitative and quantitative aspects of solution shearing, a model MGC method, using coating blades augmented with arrays ofpillars. The pillars induce local regions of high strain rates—both shear and extensional—not otherwise possible with unmodified blades, and we use fluid mechanical simulations to modeland study a variety of pillar spacings and densities. We then perform a statistical analysis of 130 simulation variables to find correlations with three dependent variables of interest: thin-filmdegree of crystallinity and transistor field-effect mobilities for charge-transport parallel (Μpara) and perpendicular (Μperp) to the coating direction. Our study suggests that simple fluid mechanicalmodels can reproduce substantive correlations between the induced fluid flow and important performance metrics, providing a methodology for optimizing blade design. Polymer semiconductors have opened up a new frontier of electronics that can be flexible, stretchable, implantable, or biodegradable. While the chemical and electronic properties of these materials are important for their function as the active material in organic electronic devices, the manner by which these organic semiconductors are deposited onto a substrate can significantly influence its charge-transport properties. While a variety of techniques have been investigated to enhance charge-transport behavior, there are few reports approaching the issue in terms of the fluid dynamical considerations relevant during deposition from the solution phase. In this article, we analyze the fluid flow that occurs during thin-film deposition by solution shearing, a representative meniscusguided coating method amenable to high-throughput processing. We investigate a variety of variables related to fluid flow that can be estimated from fluid mechanical simulations of solution shearing with a coating blade patterned with a regular array of pillars used to induce higher fluid strain rates. We find correlations suggestive of underlying relationships between strain rates associated with certain directions and polymer charge-transport properties in the final deposited film. This article establishes a statistical approach using simulation data that can guide patterned blade design to enhance polymer deposition and realize high-performance devices.

Crucial to the development and refinement of organic electronics is a fundamental understanding of how deposition processes affect the active material’s resulting microstructure in the thin film. Meniscus-guided coating (MGC) methods are attractive because of their amenability to high-throughput, industrially relevant continuous processes like roll-to-roll deposition, but the mechanism of solid film formation has not been elucidated and is valuable for the precise control of thin-film morphology and thus ultimate device performance. In this work, we investigate the microstructural evolution of thin films of a diketopyrrolopyrrole–terthiophene donor–acceptor polymer semiconductor using both in situ and ex situ X-ray diffraction methods. On the basis of a comparison of disorder between the film bulk and the top surface and a depth profiling of the out-of-plane orientation of crystallites, we find that faster coating speeds introduce more disorder into the resulting films because the stochastic nucleation of...

Conventional semiconducting polymer synthesis typically involves transition metal-mediated coupling reactions that link aromatic units with single bonds along the backbone. Rotation around these bonds contributes to conformational and energetic disorder and therefore potentially limits charge delocalisation, whereas the use of transition metals presents difficulties for sustainability and application in biological environments. Here we show that a simple aldol condensation reaction can prepare polymers where double bonds lock-in a rigid backbone conformation, thus eliminating free rotation along the conjugated backbone. This polymerisation route requires neither organometallic monomers nor transition metal catalysts and offers a reliable design strategy to facilitate delocalisation of frontier molecular orbitals, elimination of energetic disorder arising from rotational torsion and allowing closer interchain electronic coupling. These characteristics are desirable for high charge carrier mobilities. Our polymers with a high electron affinity display long wavelength NIR absorption with air stable electron transport in solution processed organic thin film transistors.

The charge‐carrier mobility of organic semiconducting polymers is known to be enhanced when the energetic disorder of the polymer is minimized. Fused, planar aromatic ring structures contribute to reducing the polymer conformational disorder, as demonstrated by polymers containing the indacenodithiophene (IDT) repeat unit, which have both a low Urbach energy and a high mobility in thin‐film‐transistor (TFT) devices. Expanding on this design motif, copolymers containing the dithiopheneindenofluorene repeat unit are synthesized, which extends the fused aromatic structure with two additional phenyl rings, further rigidifying the polymer backbone. A range of copolymers are prepared and their electrical properties and thin‐film morphology evaluated, with the co‐benzothiadiazole polymer having a twofold increase in hole mobility when compared to the IDT analog, reaching values of almost 3 cm2 V−1 s−1 in bottom‐gate top‐contact organic field‐effect transistors.

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.

Wide‐bandgap conjugated polymers with a linear naphthacenodithiophene (NDT) donor unit are herein reported along with their performance in both transistor and solar cell devices. The monomer is synthesized starting from 2,6‐dihydroxynaphthalene with a double Fries rearrangement as the key step. By copolymerization with 2,1,3‐benzothiadiazole (BT) via a palladium‐catalyzed Suzuki coupling reaction, NDT‐BT co‐polymers with high molecular weights and narrow polydispersities are afforded. These novel wide‐bandgap polymers are evaluated as the semiconducting polymer in both organic field effect transistor and organic photovoltaic applications. The synthesized polymers reveal an optical bandgap in the range of 1.8 eV with an electron affinity of 3.6 eV which provides sufficient energy offset for electron transfer to PC70BM acceptors. In organic field effect transistors, the synthesized polymers demonstrate high hole mobilities of around 0.4 cm2 V–1 s–1. By using a blend of NDT‐BT with PC70BM as absorber layer in organic bulk heterojunction solar cells, power conversion efficiencies of 7.5% are obtained. This value is among the highest obtained for polymers with a wider bandgap (larger than 1.7 eV), making this polymer also interesting for application in tandem or multijunction solar cells.

Targeting flexible display backplanes and circuitry, BASF is developing high performance materials for Organic Field-Effect Transistors. Here we present our recent development focusing on directly photo-patternable semiconductors and dielectrics, as well as new semiconductors for solution-processed transistors with mobilities of up to 4 cm2/Vs.

The isolation of semiconducting single‐walled carbon nanotubes (sc‐SWNTs) with ideal diameter and high purity is highly desired for high‐performance electronic devices. However, current sorting methods for large‐diameter sc‐SWNTs suffer from either low purity (<99%) or long processing time (>20 h). Here, a backbone‐engineering strategy is reported for the polymer used for sorting to improve the purity of sorted sc‐SWNTs. Six diketopyrrolopyrrole (DPP)‐based conjugated polymers are used to systematically investigate their sorting ability for sc‐SWNTs. It is found that incorporation of more thiophenes building blocks in the repeating units of DPP polymer backbone leads to increased selectivity and yield for sc‐SWNTs. The DPP polymers can disperse sc‐SWNTs with 1.4–1.6 nm in diameter and high purity of 99.6% by a processing time as short as 1 h. Furthermore, a scalable film coating method named “solution shearing” is used to fabricate SWNT network thin‐film transistors (TFTs). The TFT devices exhibit both high mobilities over 50 cm 2 V −1 s −1 and high on/off ratios over 10 5 , which are among the highest performance for solution‐processed SWNT network TFTs.

Low-bandgap diketopyrrolopyrrole (DPP)-based polymers are used for the selective dispersion of semiconducting single-walled carbon nanotubes (s-SWCNTs). Through rational molecular design to tune the polymer-SWCNT interactions, highly selective dispersions of s-SWCNTs with diameters mainly around 1.5 nm are achieved. The influences of the polymer alkyl side-chain substitution (i.e., branched vs linear side chains) on the dispersing yield and selectivity of s-SWCNTs are investigated. Introducing linear alkyl side chains allows increased polymer-SWCNT interactions through close π-π stacking and improved C-H-π interactions. This work demonstrates that polymer side-chain engineering is an effective method to modulate the polymer-SWCNT interactions and thereby affecting both critical parameters in dispersing yield and selectivity. Using these sorted s-SWCNTs, high-performance SWCNT network thin-film transistors are fabricated. The solution-deposited s-SWCNT transistors yield simultaneously high mobilities of 41.2 cm(2) V(-1) s(-1) and high on/off ratios of greater than 10(4) . In summary, low-bandgap DPP donor-acceptor polymers are a promising class of polymers for selective dispersion of large-diameter s-SWCNTs.

The synthesis of a new thieno[3,2‐b]thiophene isoindigo (iITT) based monomer unit, and its subsequent incorporation into a series of alternating copolymers is reported. Copolymerisation with benzothiadiazole, bithiophene and thiophene comonomer units by palladium catalysed cross coupling gives three new narrow band gap semiconducting polymers for OFET applications. Extending the fused nature of the isoindigo core serves to further enhance molecular orbital overlap along the polymer backbones and facilitate good charge transport characteristics thus demonstrating the potential of extending the fused ring system that is attached to the isoindigo core. When used as the semiconducting channel in top‐gate/bottom‐contact OFET devices, good ambipolar properties are observed, with hole and electron mobilities up to 0.4 cm2/Vs and 0.7 cm2/Vs respectively. The three new polymers show good stability, with high temperature annealing showing an increase in the crystallinity of the polymers which corresponds directly to charge carrier mobility improvement as shown by X‐ray diffraction, atomic force microscopy and photothermal deflection spectroscopy.