We investigated the correlation between the polymer backbone structural regularity and the charge transport properties of poly{[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} [P(NDI2OD-T2)], a widely studied semiconducting polymer exhibiting high electron mobility and an unconventional micromorphology. To understand the influence of the chemical structure and crystal packing of conventional regioregular P(NDI2OD-T2) [RR-P(NDI2OD-T2)] on the charge transport, the corresponding regioirregular polymer RI-P(NDI2OD-T2) was synthesized. By combining optical, X-ray, and transmission electron microscopy data, we quantitatively characterized the aggregation, crystallization, and backbone orientation of all of the polymer films, which were then correlated to the electron mobilities in electron-only diodes. By carefully selecting the preparation conditions, we were able to obtain RR-P(NDI2OD-T2) films with similar crystalline structure along the three crystallographic axes but with different orientations of the polymer chains with respect to the substrate surface. RI-P(NDI2OD-T2), though exhibiting a rather similar LUMO structure and energy compared with the regioregular counterpart, displayed a very different packing structure characterized by the formation of ordered stacks along the lamellar direction without detectible π-stacking. Vertical electron mobilities were extracted from the space-charge-limited currents in unipolar devices. We demonstrate the anisotropy of the charge transport along the different crystallographic directions and how the mobility depends on π-stacking but is insensitive to the degree or coherence of lamellar stacking. The comparison between the regioregular and regioirregular polymers also shows how the use of large planar functional groups leads to improved charge transport, with mobilities that are less affected by chemical and structural disorder with respect to classic semicrystalline polymers such as poly(3-hexylthiophene).

Polymer transistors are being intensively developed for next-generation flexible electronics. Blends comprising a small amount of semiconducting polymer mixed into an insulating polymer matrix have simultaneously shown superior performance and environmental stability in organic field-effect transistors compared with the neat semiconductor. Here we show that such blends actually perform very poorly in the undoped state, and that mobility and on/off ratio are improved dramatically upon moderate doping. Structural investigations show that these blend layers feature nanometre-scale semiconductor domains and a vertical composition gradient. This particular morphology enables a quasi three-dimensional spatial distribution of semiconductor pathways within the insulating matrix, in which charge accumulation and depletion via a gate bias is substantially different from neat semiconductor, and where high on-current and low off-current are simultaneously realized in the stable doped state. Adding only 5 wt% of a semiconducting polymer to a polystyrene matrix, we realized an environmentally stable inverter with gain up to 60.

Efficiency, current throughput, and speed of electronic devices are to a great extent dictated by charge carrier mobility. The classic approach to impart high carrier mobility to polymeric semiconductors has often relied on the assumption that extensive order and crystallinity are needed. Recently, however, this assumption has been challenged, because high mobility has been reported for semiconducting polymers that exhibit a surprisingly low degree of order. Here, we show that semiconducting polymers can be confined into weakly ordered fibers within an inert polymer matrix without affecting their charge transport properties. In these conditions, the semiconducting polymer chains are inhibited from attaining longrange order in the π-stacking or alkyl-stacking directions, as demonstrated from the absence of significant X-ray diffraction intensity corresponding to these crystallographic directions, yet still remain extended along the backbone direction and aggregate on a local length scale. As a result, the polymer films maintain high mobility even at very low concentrations. Our findings provide a simple picture that clarifies the role of local order and connectivity of domains.organic electronics | conjugated polymers | aggregation | charge transport C onjugated polymers have received significant scientific attention as the active material in devices for printed and flexible organic electronics (1, 2). Owing to their versatile chemical synthesis, inexpensive processability from solution, and unique mechanical flexibility, these materials are in fact promising for a vast array of devices in future low-cost and distributed technologies, such as integrated systems for electronic labels targeting safety, security, and surveillance applications (3). The rational design of new organic semiconductors has been guided by a thorough investigation of their limitations in charge transport, leading to the development of high-performance materials for next-generation electronic applications such as low-cost displays, solar cells, sensors, and logic circuits (4, 5). For more than a decade research has primarily focused on increasing the long-range order and the crystallinity of conjugated polymers as a strategy to improve the solid-state charge transport properties. As a result, the charge carrier mobility has increased by several orders of magnitude through the design and synthesis of highly ordered polymers. However, recent studies have suggested that the key to designing high-mobility polymers is not to increase their crystallinity but rather to improve their tolerance for disorder by allowing more efficient intra-and intermolecular charge transport pathways (6). This observation explains why mobility values obtained from recently designed seemingly disordered organic semiconductors often exceed those of polymers having a high degree of crystallinity (∼1 cm 2 ·V -1 ·s -1 ) (7-10). Indeed, polymers may exhibit little longrange order, as measured by X-ray diffraction (XRD), and yet display a remarkable degree of short-range or...

Using X-ray diffraction-based pole figures, we present quantitative analysis of the microstructure of poly(3-hexylthiophene) thin films of varying thicknesses, which allows us to determine the crystallinity and microstructure at the semiconductor-dielectric interface. We find that the interface is approximately one fourth as crystalline as the bulk of the material. Furthermore, the use of a self-assembled monolayer (SAM) enhances the density of interface-nucleated crystallites by a factor of $20. Charge transport measurements as a function of film thickness correlate with interface crystallinity. Hence, we establish the crucial role of SAMs as nucleating agents for increasing carrier mobility in field-effect devices.

A series of alternating oligothiophene (nT)-isoindigo (I) copolymers (PnTI) were synthesized to investigate the influence of the oligothiophene block length on the photovoltaic (PV) properties of PnTI:PCBM bulkheterojunction blends. Our study indicates that the number of thiophene rings (n) in the repeating unit alters both polymer crystallinity and polymer-fullerene interfacial energetics, which results in a decreasing open-circuit voltage (V oc ) of the solar cells with increasing n. The short-circuit current density (J sc ) of P1TI:PCBM devices is limited by the absence of a significant driving force for electron transfer. Instead, blends based on P5TI and P6TI feature large polymer domains, which limit charge generation and thus J sc . The best PV performance with a power conversion efficiency of up to 6.9% was achieved with devices based on P3TI, where a combination of a favorable morphology and an optimal interfacial energy level offset ensures efficient exciton separation and charge generation. The structureproperty relationship demonstrated in this work would be a valuable guideline for the design of high performance polymers with small energy losses during the charge generation process, allowing for the fabrication of efficient solar cells that combine a minimal loss in V oc with a high J sc . Broader contextPolymer solar cells (PSCs) have emerged as promising candidates for low-cost, environmentally friendly energy conversion. However, a low power conversion efficiency (PCE) is still the main bottleneck for their commercial applications. In order to further improve their PCE, a detailed understanding of the underlying structure-property relationships that govern these materials is crucial. In this work, a series of alternating oligothiophene (nT)-isoindigo (I) copolymers (PnTI) were synthesized to investigate the inuence of the oligothiophene block length on the photovoltaic (PV) properties of PnTI:PCBM bulk-heterojunction blends. The driving force for the PSCs can be ne-tuned in a small range of 0-0.1 eV by changing the conjugated length of the oligothiophene block. This is a valuable guideline for polymer design to achieve high-efficiency PSCs with optimum photovoltage and photocurrent.

The performance of polymer:fullerene solar cells is strongly affected by the active layer morphology and polymer microstructure. In this Perspective, we review ongoing research on how structural factors influence the photogeneration and collection of charge carriers as well as charge carrier recombination and the related open-circuit voltage. We aim to highlight unexplored research opportunities and provide some guidelines for the synthesis of new conjugated polymers for high-efficiency solar cells.

Model semiconducting polymer blends of wellcontrolled molecular weight distributions are fabricated and demonstrated to be a simple method to control intermolecular disorder without affecting intramolecular order or degree of aggregation. Mobility measurements exhibit that even small amounts of low molecular weight material are detrimental to charge transport. Trends in charge carrier mobility can be reproduced by a simple analytical model which indicates that carriers have no preference for high or low molecular weight chains and that charge transport is limited by interchain hopping. These results quantify the role of long polymer tie-chains and demonstrate the need for controlled polydispersity for achieving high carrier mobilities.

Although a strong link between the molar mass of conjugated polymers and the performance of the resulting polymer:fullerene bulk heterojunction organic solar cells has been established on numerous occasions, a clear understanding of the origin of this connection is still lacking. Moreover, the usual description of molar mass and polydispersity does not include the shape of the polymer distribution, although this can have a significant effect on the device properties. In this work, the effect of molar mass distribution on photovoltaic performance is investigated using a combination of structural and electro-optical techniques for the state-of-the-art low bandgap copolymer PTB7. Some of the studied commercial PTB7 batches exhibit a bimodal distribution, of which the low molar mass fraction contains multiple homocoupled oligomer species, as identified by MALDI-TOF analysis. This combination of low molar mass and homocoupling drastically reduces device performance, from 7.0 to 2.7%. High molar mass batches show improved charge carrier transport and extraction with much lower apparent recombination orders, as well as a more homogeneous surface morphology. These results emphasize the important effect of molar mass distributions and homocoupling defects on the operation of conjugated polymers in photovoltaic devices.