High-mobility semiconducting polymers offer the opportunity to develop flexible and large-area electronics for several applications, including wearable, portable and distributed sensors, monitoring and actuating devices. An enabler of this technology is a scalable printing process achieving uniform electrical performances over large area. As opposed to the deposition of highly crystalline films, orientational alignment of polymer chains, albeit commonly achieved by non-scalable/slow bulk alignment schemes, is a more robust approach towards large-area electronics. By combining pre-aggregating solvents for formulating the semiconductor and by adopting a room temperature wired bar-coating technique, here we demonstrate the fast deposition of submonolayers and nanostructured films of a model electron-transporting polymer. Our approach enables directional self-assembling of polymer chains exhibiting large transport anisotropy and a mobility up to 6.4 cm2 V−1 s−1, allowing very simple device architectures to operate at 3.3 MHz. Thus, the proposed deposition strategy is exceptionally promising for mass manufacturing of high-performance polymer circuits.

A highly efficient, simple, and environmentally friendly protocol for the synthesis of an alternating naphthalene diimide bithiophene copolymer (PNDIT2) via direct arylation polycondensation (DAP) is presented. High molecular weight (MW) PNDIT2 can be obtained in quantitative yield using aromatic solvents. Most critical is the suppression of two major termination reactions of NDIBr end groups: nucleophilic substitution and solvent end-capping by aromatic solvents via C-H activation. In situ solvent end-capping can be used to control MW by varying monomer concentration, whereby end-capping is efficient and MW is low for low concentration and vice versa. Reducing C-H reactivity of the solvent at optimized conditions further increases MW. Chain perfection of PNDIT2 is demonstrated in detail by NMR spectroscopy, which reveals PNDIT2 chains to be fully linear and alternating. This is further confirmed by investigating the optical and thermal properties as a function of MW, which saturate at Mn ≈ 20 kDa, in agreement with controls made by Stille coupling. Field-effect transistor (FET) electron mobilities μsat up to 3 cm(2)/(V·s) are measured using off-center spin-coating, with FET devices made from DAP PNDIT2 exhibiting better reproducibility compared to Stille controls.

Recent reports on high-mobility organic field-effect transistors (FETs) based on donor-acceptor semiconducting co-polymers have indicated an apparently strong deviation from the paradigm, valid for a series of semi-crystalline polymers, which has been strictly correlating charges mobility to crystalline order. This poses a severe limit on the control of mobility and a fundamental question on the critical length scale which is dominating charge transport. Here we focus on a well-known model material for electron transport, a naphthalene-diimide based copolymer, and we demonstrate that mobility can be controlled over two orders of magnitude, with maximum saturation mobility exceeding 1 cm2/Vs at high gate voltages, by controlling the extent of orientational domains through a deposition process as simple as spin-coating. High mobility values can be achieved by adopting solvents inducing a higher amount of pre-aggregates in the solution, which through the interaction with the substrate, provide the polymer with liquid-crystalline like ordering properties.

Polymer semiconductors have been experiencing a remarkable improvement in electronic and optoelectronic properties, which are largely related to the recent development of a vast library of high-performance, donor-acceptor copolymers showing alternation of chemical moieties with different electronic affinities along their backbones. Such steady improvement is making conjugated polymers even more appealing for large-area and flexible electronic applications, from distributed and portable electronics to healthcare devices, where cost-effective manufacturing, light weight, and ease of integration represent key benefits. Recently, a strong boost to charge carrier mobility in polymer-based field-effect transistors, consistently achieving the range from 1.0 to 10 cm V s for both holes and electrons, has been given by uniaxial backbone alignment of polymers in thin films, inducing strong transport anisotropy and favoring enhanced transport properties along the alignment direction. Herein, an overview on this topic is provided with a focus on the processing-structure-property relationships that enable the controlled and uniform alignment of polymer films over large areas with scalable processes. The key aspects are specific molecular structures, such as planarized backbones with a reduced degree of conformational disorder, solution formulation with controlled aggregation, and deposition techniques inducing suitable directional flow.

Direct arylation (DA) is emerging as a highly promising method to construct inexpensive conjugated materials for large-area electronics from simple and environmentally benign building blocks. Here, we show that exclusive α-C–H selectivity is feasible in the DA of π-extended monomers having unsubstituted thiophene or furan units, leading to fully linear materials. Two new naphthalene diimide-based conjugated copolymers—P(FuNDIFuF₄) and P(ThNDIThF₄), composed of naphthalene diimide (NDI), furan (Fu) or thiophene (Th), and tetrafluorobenzene (F₄)—are synthesized. Insight into structure–function relationships is given by density functional theory (DFT) calculations and variety of experimental techniques, whereby the effect of the heteroatom on the optical, structural, and electronic properties is investigated. The use of furan (Fu) allows for enhanced solubilities, a smaller dihedral angle between NDI and Fu as a result of the smaller size of Fu, and a smaller π–π-stacking distance in the solid state. P(FuNDIFuF₄) also exhibits a more edge-on orientation compared to P(ThNDIThF₄). Despite these advantageous properties of P(FuNDIFuF₄), P(ThNDIThF₄) exhibits the highest electron mobility: ∼1.3 cm²/(V s), which is a factor of ∼3 greater than that of P(FuNDIFuF₄). The enhanced OFET performance of P(ThNDIThF₄) is explained by reduced orientational disorder and the formation of a terrace-like thin-film morphology

Defect structures in high-performance conjugated polymers are generally known but still challenging to characterize on a quantitative basis. Here, we present a detailed analysis of backbone topology of a series of copolymers PDPPTh 2 F 4 having alternating dithienyldiketopyrrolopyrrole (DPPTh 2 ) and tetrafluorobenzene (F 4 ) units made by direct arylation polycondensation (DAP). In contrast to early expectations of unselective C−H activation during the DAP of monomers with multiple C−H bonds, detailed structure analysis by high-temperature 1 H NMR spectroscopy reveals welldefined and alternating backbones with a quantifiable amount of 0−12% DPPTh 2 homocouplings as the only defect structure in the main chain. Homocoupled −DPPTh 2 −DPPTh 2 − structural units are additionally characterized by UV−vis spectroscopy. While −DPPTh 2 −H end groups are inert to other side reactions, −F 4 −Br end groups are weakly susceptible to both dehalogenation and reaction with toluene. However, despite the presence of DPPTh 2 homocouplings, high field-effect transistor electron mobilities up to ∼0.6 cm 2 /(V s) are achieved. This study highlights both that DPPTh 2 homocouplings pose a prevalent structural defect in DPPTh 2 -based conjugated polymers made by DAP and that a very simple four-step DAP protocol can yield materials with varying molar mass and excellent n-type transistor performance.

Naphthalenediimide (NDI)-based polymers co-polymerized with thienyl units are an interesting class of polymer semiconductors because of their good electron mobilities and unique film microstructure. Despite these properties, understanding how the extension of the thienyl co-monomer affects charge transport properties remains unclear. With this goal in mind, we have synthesized a series of NDI derivatives of the parent poly{[N,N′-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-bithiophene) (P(NDI2OD-T2)), which exhibited excellent electron mobility. The strategy comprises both the extension of the donor o-conjugation length and the heteroatomic fusion of the thiophene rings. These newly synthesized compounds are characterized experimentally and theoretically vis-à-vis with P(NDI2OD-T2) as the reference. UV-vis data and cyclic-voltammetry are adopted to assess the effect of the donor modification on the frontier energy levels and on the bandgap. Intra-molecular polaronic effects are accounted for by computing the internal reorganization energy with density functional theory (DFT) calculations. Finally electrons and holes transport is experimentally investigated in field-effect transistors (FETs), by measuring current-voltage characteristics at variable temperatures. Overall we have identified a regime where inter-molecular effects, such as the wavefunction overlap and the degree of energetic disorder, induced by the different donor group prevail over polaronic effects and are the leading factors in determining electrons mobility

Interdependence of chemical structure, thin-film morphology, and transport properties is a key, yet often elusive aspect characterizing the design and development of high-mobility, solution-processed polymers for large-area and flexible electronics applications. There is a specific need to achieve >1 cm 2 V −1 s −1 field-effect mobilities (μ) at low processing temperatures in combination with environmental stability, especially in the case of electron-transporting polymers, which are still lagging behind hole transporting materials. Here, the synthesis of a naphthalene-diimide based donor-acceptor copolymer characterized by a selenophene vinylene selenophene donor moiety is reported. Optimized field-effect transistors show maximum μ of 2.4 cm 2 V −1 s −1 and promising ambient stability. A very marked film structural evolution is revealed with increasing annealing temperature, with evidence of a remarkable 3D crystallinity above 180 °C. Conversely, transport properties are found to be substantially optimized at 150 °C, with limited gain at higher temperature. This discrepancy is rationalized by the presence of a surface-segregated prevalently edge-on packed polymer phase, dominating the device accumulated channel. This study therefore serves the purpose of presenting a promising, high-electron-mobility copolymer that is processable at relatively low temperatures, and of clearly highlighting the necessity of specifically investigating channel morphology in assessing the structure-property nexus in semiconducting polymer thin films.