Short contacts between chains enhancing luminescence quantum yields and carrier mobilities in conjugated copolymers

Abstract: Efficient conjugated polymer optoelectronic devices benefit from concomitantly high luminescence and high charge carrier mobility. This is difficult to achieve, as interchain interactions, which are needed to ensure efficient charge transport, tend also to reduce radiative recombination and lead to solid-state quenching effects. Many studies detail strategies for reducing these interactions to increase luminescence, or modifying chain packing motifs to improve percolation charge transport; however achieving these properties together has proved elusive. Here, we show that properly designed amorphous donor-alt-acceptor conjugated polymers can circumvent this problem; combining a tuneable energy gap, fast radiative recombination rates and luminescence quantum efficiencies >15% with high carrier mobilities exceeding 2.4 cm2/Vs. We use photoluminescence from exciton states pinned to close-crossing points to study the interplay between mobility and luminescence. These materials show promise towards realising advanced optoelectronic devices based on conjugated polymers, including electrically-driven polymer lasers

Limits for Recombination in a Low Energy Loss Organic Heterojunction

Donor–acceptor organic solar cells often show high quantum yields for charge collection, but relatively low open-circuit voltages (V$_{OC}$) limit power conversion efficiencies to around 12%. We report here the behavior of a system, PIPCP:PC$_{61}$BM, that exhibits very low electronic disorder (Urbach energy less than 27 meV), very high carrier mobilities in the blend (field-effect mobility for holes >10$^{-2}$ cm$^{2}$ V$^{-1}$ s$^{-1}$), and a very low driving energy for initial charge separation (50 meV). These characteristics should give excellent performance, and indeed, the V$_{OC}$ is high relative to the donor energy gap. However, we find the overall performance is limited by recombination, with formation of lower-lying triplet excitons on the donor accounting for 90% of the recombination. We find this is a bimolecular process that happens on time scales as short as 100 ps. Thus, although the absence of disorder and the associated high carrier mobility speeds up charge diffusion and extraction at the electrodes, which we measure as early as 1 ns, this also speeds up the recombination channel, giving overall a modest quantum yield of around 60%. We discuss strategies to remove the triplet exciton recombination channel.SMM, RHF, MKR, SAA, and JLB acknowledge support from the KAUST Competitive Research Grant Program. MKR, SAA, and JLB also acknowledge generous support of their work by KAUST and the Office of Naval Research Global (Award N62909­15­1­2003); they thank the KAUST IT Research Computing Team and Supercomputing Laboratory for providing computational and storage resources. NAR, MW, TQN, and GCB acknowledge support from the Department of the Navy, Office of Naval Research (Award Nos. N00014-14-1-0580 and N00014-16-1-25200. AS would like to acknowledge the funding and support from the India-UK APEX project. HLS acknowledges support from the Winton Programme for the Physics of Sustainability. MN and HS gratefully acknowledge financial support from the Engineering and Physical Sciences Research Council though a Programme Grant (EP/M005141/1)

The effect of ring expansion in thienobenzo[b]indacenodithiophene polymers for organic field-effect transistors

A fused donor, thienobenzo[b]indacenodithiophene (TBIDT), was designed and synthesized using a novel acid-promoted cas-cade ring closure strategy, and copolymerized with a benzothiadiazole (BT) monomer. The backbone of TBIDT is an expan-sion of the well-known indacenodithiophene (IDT) unit and was expected to enhance the charge carrier mobility, by improving backbone planarity and facilitating short-contacts between polymer chains. However, the optimized field-effect transistors demonstrated an average saturation hole mobility of 0.9 cm2 V−1s−1, lower than the performance of IDT-BT (~1.5 cm2 V−1s−1). Mobilities extracted from time-resolved microwave conductivity (TRMC) measurements were consistent with the trend in hole mobilities in OFET devices. Scanning Tunneling Microscopy (STM) measurements and computational modelling illustrated that TBIDT-BT exhibits a less ordered microstructure in comparison to IDT-BT. This reveals that a regular side chain pack-ing density, independent of conformational isomers, is critical to avoid local free volume due to irregular packing, which can host trapping impurities. DFT calculations indicated that TBIDT-BT, despite containing a larger, planar unit, showed less stabilization of planar backbone geometries, in comparison to IDT-BT. This is due to the reduced electrostatic stabilizing inter-actions between the peripheral thiophene of the fused core with the BT unit, resulting in a reduction of the barrier to rotation around the single bond. These insights provide a greater understanding of the general structure-property relationships required for semiconducting polymer repeat units to ensure optimal backbone planarization, as illustrated with IDT-type units, guiding the design of novel semiconducting polymers with extended fused backbones for high-performance field-effect transistors

Mesaconate is synthesized from itaconate and exerts immunomodulatory effects in macrophages.

peer reviewedSince its discovery in inflammatory macrophages, itaconate has attracted much attention due to its antimicrobial and immunomodulatory activity1-3. However, instead of investigating itaconate itself, most studies used derivatized forms of itaconate and thus the role of non-derivatized itaconate needs to be scrutinized. Mesaconate, a metabolite structurally very close to itaconate, has never been implicated in mammalian cells. Here we show that mesaconate is synthesized in inflammatory macrophages from itaconate. We find that both, non-derivatized itaconate and mesaconate dampen the glycolytic activity to a similar extent, whereas only itaconate is able to repress tricarboxylic acid cycle activity and cellular respiration. In contrast to itaconate, mesaconate does not inhibit succinate dehydrogenase. Despite their distinct impact on metabolism, both metabolites exert similar immunomodulatory effects in pro-inflammatory macrophages, specifically a reduction of interleukin (IL)-6 and IL-12 secretion and an increase of CXCL10 production in a manner that is independent of NRF2 and ATF3. We show that a treatment with neither mesaconate nor itaconate impairs IL-1β secretion and inflammasome activation. In summary, our results identify mesaconate as an immunomodulatory metabolite in macrophages, which interferes to a lesser extent with cellular metabolism than itaconate

Universal three-dimensional crosslinker for all-photopatterned electronics

All-solution processing of large-area organic electronics requires multiple steps of patterning and stacking of various device components. Here, we report the fabrication of highly integrated arrays of polymer thin-film transistors and logic gates entirely through a series of solution processes. The fabrication is done using a three-dimensional crosslinker in tetrahedral geometry containing four photocrosslinkable azide moieties, referred to as 4Bx. 4Bx can be mixed with a variety of solution-processable electronic materials (polymer semiconductors, polymer insulators, and metal nanoparticles) and generate crosslinked network under exposure to UV. Fully crosslinked network film can be formed even at an unprecedentedly small loading, which enables preserving the inherent electrical and structural characteristics of host material. Because the crosslinked electronic component layers are strongly resistant to chemical solvents, micropatterning the layers at high resolution as well as stacking the layers on top of each other by series of solution processing steps is possible

Low-Voltage, Dual-Gate Organic Transistors with High Sensitivity and Stability toward Electrostatic Biosensing

High levels of performance and stability have been demonstrated for conjugated polymer thin-film transistors in recent years, making them promising materials for flexible electronic circuits and displays. For sensing applications, however, most research efforts have been focusing on electrochemical sensing devices. Here we demonstrate a highly stable biosensing platform using polymer transistors based on the dual-gate mechanism. In this architecture a sensing signal is transduced and amplified by the capacitive coupling between a low-k bottom dielectric and a high-k ionic elastomer top dielectric that is in contact with an analyte solution. The new design exhibits a high signal amplification, high stability under bias stress in various aqueous environments, and low signal drift. Our platform, furthermore, while responding expectedly to charged analytes such as the protein bovine serum albumin, is insensitive to changes of salt concentration of the analyte solution. These features make this platform a potentially suitable tool for a variety of biosensing applications.M.N. acknowledges financial support from the European Commission through a Marie-Curie Individual Fellowship (EC Grant Agreement No. 747461). A.F. and Z.B. acknowledge support from the Stanford Catalyst Program for Collaborative Research and a seed grant from the Stanford Precision Health and Integrated Diagnosis (PHIND) program. D.S. acknowledges support by the Engineering and Physical Sciences Research Council (Grant No. EP/L015889/1).Peer reviewe

The effect of the dielectric end groups on the positive bias stress stability of N2200 organic field effect transistors

Bias stress degradation in conjugated polymer field-effect transistors is a fundamental problem in these disordered materials and can be traced back to interactions of the material with environmental species,1,2,3 as well as fabrication-induced defects.4,5 However, the effect of the end groups of the polymer gate dielectric and the associated dipole-induced disorder on bias stress stability has not been studied so far in high-performing n-type materials, such as N2200.6,7 In this work, the performance metrics of N2200 transistors are examined with respect to dielectrics with different end groups (Cytop-M and Cytop-S8). We hypothesize that the polar end groups would lead to increased dipole-induced disorder, and worse performance.1,9,10 The long-time annealing scheme at lower temperatures used in the paper is assumed to lead to better crystallization by allowing the crystalline domains to reorganize in the presence of the solvent.11 It is hypothesized that the higher crystallinity could narrow down the range at which energy carriers are induced and thus decrease the gate dependence of the mobility. The results show that the dielectric end groups do not influence the bias stress stability of N2200 transistors. However, long annealing times result in a dramatic improvement in bias stress stability, with the most stable devices having a mobility that is only weakly dependent on or independent of gate voltage.Comment: The following article has been accepted by APL Materials. After it is published, it will be found at https://doi.org/10.1063/5.004478

Performance Improvements in Conjugated Polymer

Data on the stability of conjugated polymer OFETs. The data set contains all the data presented in the paper (Figures 1 through 4) and consists of transistor transfer and output characteristics as well as the extracted field-effect mobility for some devices (For others it can directly be extraxted from the containing raw data) and photothermal absorption spectroscopy (PDS) data