Charge-Transport Anisotropy in a Uniaxially Aligned Diketopyrrolopyrrole-Based Copolymer.

Aligned films of a semiconducting DPP-based copolymer exhibit highly anisotropic charge transport with a band-like temperature dependence along the alignment direction and hole mobilities of up to 6.7 cm(2) V(-1) s(-1) . X-ray diffraction measurements reveal an exceptional degree of in-plane alignment, high crystallinity, and a dominant face-on orientation of the polymer backbones. The surprising charge-transport properties are interpreted in a tie-chain model consistent with anisotropic activation energies.The authors gratefully acknowledge funding from the Engineering and Physical Sciences Research Council (EPSRC) through a program grant (EP/G060738/1). C.R.M. acknowledges support from the Australia Research Council (FT100100275 and DP130102616). This work was performed in part at the SAXS/WAXS[59] and soft X-ray[60] beam lines at the Australian Synchrotron. C.R.M. and E.G. thank Nigel Kirby of the Australian Synchrotron for technical assistance.This is the final version of the article. It first appeared from Wiley via http://dx.doi.org/10.1002/adma.20150243

Bottom-up growth of n-type monolayer molecular crystals on polymeric substrate for optoelectronic device applications.

Self-assembly of monolayers of functional molecules on dielectric surfaces is a promising approach for the development of molecular devices proposed in the 1970s. Substrate chemically bonded self-assembled monolayers of semiconducting conjugated molecules exhibit low mobility. And self-assembled monolayer molecular crystals are difficult to scale up and limited to growth on substrates terminated by hydroxyl groups, which makes it difficult to realize sophisticated device functions, particularly for those relying on n-type electron transport, as electrons suffer severe charge trapping on hydroxyl terminated surfaces. Here we report a gravity-assisted, two-dimensional spatial confinement method for bottom-up growth of high-quality n-type single-crystalline monolayers over large, centimeter-sized areas. We demonstrate that by this method, n-type monolayer molecular crystals with high field-effect mobility of 1.24 cm2 V-1 s-1 and band-like transport characteristics can be grown on hydroxyl-free polymer surface. Furthermore, we used these monolayer molecular crystals to realize high-performance crystalline, gate-/light-tunable lateral organic p-n diodes

A Simple and Robust Approach to Reducing Contact Resistance in Organic Transistors

Efficient injection of charge carriers from the contacts into the semiconductor layer is crucial for achieving high-performance organic devices. The potential drop necessary to accomplish this process yields a resistance associated with the contacts, namely the contact resistance. A large contact resistance can limit the operation of devices and even lead to inaccuracies in the extraction of the device parameters. Here, we demonstrate a simple and efficient strategy for reducing the contact resistance in organic thin-film transistors by more than an order of magnitude by creating high work function domains at the surface of the injecting electrodes to promote channels of enhanced injection. We find that the method is effective for both organic small molecule and polymer semiconductors, where we achieved a contact resistance as low as 200 Ωcm and device charge carrier mobilities as high as 20 cm2V−1s−1, independent of the applied gate voltage

Self-Assembly of ABC Bottlebrush Triblock Terpolymers with Evidence for Looped Backbone Conformations

Bottlebrush block copolymers offer rich opportunities for the design of complex hierarchical materials. As consequences of the densely grafted molecular architecture, bottlebrush polymers can adopt highly extended backbone conformations and exhibit unique physical properties. A recent report has described the unusual phase behavior of ABC bottlebrush triblock terpolymers bearing grafted poly(dl-lactide) (PLA), polystyrene (PS), and poly(ethylene oxide) (PEO) blocks (LSO). In this work, a combination of resonant soft X-ray reflectivity (RSoXR), near-edge X-ray absorption fine structure spectroscopy (NEXAFS), and self-consistent field theory (SCFT) was used to provide insight into the phase behavior of LSO and underlying backbone chain conformations. Consistent with SCFT calculations, RSoXR measurements confirm a unique mesoscopic ACBC domain connectivity and decreasing lamellar periods (d0) with increasing backbone length of the PEO block. RSoXR and NEXAFS demonstrate an additional unusual feature of brush LSO thin films: when the overall film thickness is ∼3.25d0, the film–air interface is majority PS (>80%). Because PS is the midblock, the triblocks must adopt looping configurations at the surface, despite the preference for the backbone to be extended. This result is supported by backbone concentrations calculated through SCFT, which suggest that looping midblocks are present throughout the film. Collectively, this work provides evidence for the flexibility of the bottlebrush backbone and the consequences of low-χ block copolymer design. We propose that PEO blocks localize at the PS/PLA domain interfaces to screen the highest χ contacts in the system, driving the formation of loops. These insights introduce a potential route to overcome the intrinsic penalties to interfacial curvature imposed by the bottlebrush architecture, enabling the design of unique self-assembled materials

Hole mobility of 3.56 cm2V-1s-1 accomplished using more extended dithienothiophene with furan flanked diketopyrrolopyrrole polymer

A highly extended dithienothiophene comonomer building block was used in combination with highly fused aromatic furan substituted diketopyrrolopyrrole for the synthesis of novel donor–acceptor alternating copolymer PDPPF-DTT. Upon testing PDPPF-DTT as a channel semiconductor in top contact bottom gate organic field effect transistors (OFETs), it was found to exhibit p-channel behaviour. The highest hole mobility of 3.56 cm2 V−1 s−1 was reported for PDPPF-DTT. To our knowledge, this is the highest mobility reported so far for the furan flanked diketopyrrolopyrrole class of copolymers using conventional device geometry with straightforward processing

In-Depth Understanding of the Morphology–Performance Relationship in Polymer Solar Cells

It is well-established that thermal annealing optimizes the morphology and improves the efficiency of P3HT-based organic solar cells, but the effects of different cooling rates after annealing are not well understood. In this paper, we use a model system based on poly­(3-hexylthiophene) (P3HT) and phenyl-C₆₁-butyric acid methyl ester (PCBM) to examine the relationship between morphology and device performance for annealing before (preannealing) and after (postannealing) the application of the electrode, with different cooling rates and in different device architectures. In the conventional structure, postannealing is confirmed to significantly enhance efficiency. The device prepared with a slow cooling rate (3.6%) shows a higher average power conversion efficiency than that prepared with a fast cooling rate (3.3%). The microstructural changes underlying this 10% increase in device performance and further effects of cooling rate, pre- and postannealing, and device architecture are comprehensively examined with a combination of synchrotron-based techniques, including grazing incidence wide-angle X-ray scattering, near-edge X-ray absorption fine structure spectroscopy, and X-ray photoelectron spectroscopy. The best device in the conventional architecture (postannealed with slow cooling rate) shows a more face-on orientation and narrower orientational distribution of P3HT crystallites. In addition, postannealing leads to PCBM diffusion toward the blend/top electrode interface. The enrichment of PCBM at the blend/top electrode interface plays a positive role in aiding electron collection at the electrode in the conventional structure, but it has a negative effect on the performance of the inverted structure, where hole collection at the top electrode instead is required. For this reason, in an inverted structure, preannealed films with slow cooling exhibit the best photovoltaic performance

9,9′-Bifluorenylidene-diketopyrrolopyrrole donors for non-polymeric solution processed solar cells

We have synthesised new materials comprised of 9,9′-bifluorenylidene and dithienodiketopyrrolopyrrole units. While 9,9′-bifluorenylidene has been primarily used in non-fullerene acceptors, when used in combination with the diketopyrrolopyrrole moiety it can form donor materials that can be used in conjunction with fullerene acceptors. The compounds differ in the substituents on the 9,9′-bifluorenylidene (protonated = 1A and dimethoxy = 1B) moiety. The structure of both the neat and blend films with PC BM were found to be strongly dependent on the processing solvent used. In particular, Grazing Incidence Wide Angle X-ray Scattering measurements of films of 1A or 1B blended with PC BM prepared from chloroform or chloroform with o-dichlorobenzene as an additive showed that the donor material had no particular ordering. However, when 1,8-diiodooctane was added to the processing solvent the 1A blends showed liquid crystalline ordering while 1B formed well-defined crystallites with three-dimensional ordering. The difference in film structure had a profound effect on the device properties. For 1A the optimised blend ratio with PC BM was 1:4, but when 1,8-diiodooctane was used as the additive the best ratio of 1A to fullerene was 1:1. The films containing the well-defined crystallites of 1B all performed poorly, which was ascribed to a lack of a percolation pathway for hole extraction. The best performing device was comprised of a 1:1 blend of 1A and PC BM, which had a power conversion efficiency of 2.6%