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The interplay between the nanostructure of a doped polythiophene with oligoether side chains and its electrical as well as mechanical properties is investigated. The degree of order of the polymer is found to strongly vary when co-processed with bistriflimidic acid (H-TFSI). The neat polythiophene as well as strongly oxidized material are largely disordered while intermediate concentrations of H-TFSI give rise to a high degree of pi-stacking. The structural disorder of strongly oxidized material correlates with a decrease in the kinetic fragility with H-TFSI concentration, suggesting that positive interactions between TFSI anions and the polymer reduce the ability to crystallize. The electrical conductivity as well as the Youngs modulus first increase upon the addition of 4-10 mol% of H-TFSI, while the loss of pi-stacking observed for strongly oxidized material more significantly affects the latter. As a result, material comprising 25 mol% H-TFSI displays an electrical conductivity of 58 S cm(-1) but features a relatively low Youngs modulus of only 80 MPa. Decoupling of the electrical and mechanical properties of doped conjugated polymers may allow the design of soft conductors that are in high demand for wearable electronics and bioelectronics., Funding Agencies|Swedish Research Council [2016-05990, 2018-03824]; European Union [955837]; Knut and Alice Wallenberg Foundation through a Wallenberg Academy Fellowship Prolongation grant

Molecular doping of a polythiophene with oligoethylene glycol side chains is found to strongly modulate not only the electrical but also the mechanical properties of the polymer. An oxidation level of up to 18% results in an electrical conductivity of more than 52 S cm(-1) and at the same time significantly enhances the elastic modulus from 8 to more than 200 MPa and toughness from 0.5 to 5.1 MJ m(-3). These changes arise because molecular doping strongly influences the glass transition temperature T-g and the degree of pi-stacking of the polymer, as indicated by both X-ray diffraction and molecular dynamics simulations. Surprisingly, a comparison of doped materials containing mono- or dianions reveals that - for a comparable oxidation level - the presence of multivalent counterions has little effect on the stiffness. Evidently, molecular doping is a powerful tool that can be used for the design of mechanically robust conducting materials, which may find use within the field of flexible and stretchable electronics., Funding Agencies|Swedish Research CouncilSwedish Research CouncilEuropean Commission [2018-03824, 2016-05990]; Knut and Alice Wallenberg Foundation through a Wallenberg Academy Fellowship Prolongation grant; project "Mastering Morphology of Solution-Borne Electronics; U.S. National Science FoundationNational Science Foundation (NSF) [DMR-1921854]; U.S. Army Research Office [W911NF19-2-0026]

While photovoltaic blends based on non-fullerene acceptors are touted for their thermal stability, this type of acceptor tends to crystallize, which can result in a gradual decrease in photovoltaic performance and affects the reproducibility of the devices. Two halogenated indacenodithienothiophene-based acceptors that readily co-crystallize upon mixing are studied, which indicates that the use of an acceptor mixture alone does not guarantee the formation of a disordered mixture. The addition of the donor polymer to the acceptor mixture readily suppresses the crystallization, which results in a fine-grained ternary blend with nanometer-sized domains that do not coarsen due to a highT(g)approximate to 200 degrees C. As a result, annealing at temperatures of up to 170 degrees C does not markedly affect the photovoltaic performance of ternary devices, in contrast to binary devices that suffer from acceptor crystallization in the active layer. The results indicate that the ternary approach enables the use of high-temperature processing protocols, which are needed for upscaling and high-throughput fabrication of organic solar cells. Further, ternary devices display a stable photovoltaic performance at 130 degrees C for at least 205 h, which indicates that the use of acceptor mixtures allows to fabricate devices with excellent thermal stability., Funding Agencies|King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research (OSR) [OSR-2018-CPF-4106]; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation [2016.0059]; European Research Council (ERC)European Research Council (ERC) [648901]; MCIU; Ikerbasque Foundation [PGC2018-094620-A-100, SEV-2015-0496, PGC2018-095411-B-100]; National Nature Science Foundation of ChinaNational Natural Science Foundation of China (NSFC) [NSFC 21905185]

While photovoltaic blends based on non-fullerene acceptors are touted for their thermal stability, this type of acceptor tends to crystallize, which can result in a gradual decrease in photovoltaic performance and affects the reproducibility of the devices. Two halogenated indacenodithienothiophene-based acceptors that readily co-crystallize upon mixing are studied, which indicates that the use of an acceptor mixture alone does not guarantee the formation of a disordered mixture. The addition of the donor polymer to the acceptor mixture readily suppresses the crystallization, which results in a fine-grained ternary blend with nanometer-sized domains that do not coarsen due to a highT(g)approximate to 200 degrees C. As a result, annealing at temperatures of up to 170 degrees C does not markedly affect the photovoltaic performance of ternary devices, in contrast to binary devices that suffer from acceptor crystallization in the active layer. The results indicate that the ternary approach enables the use of high-temperature processing protocols, which are needed for upscaling and high-throughput fabrication of organic solar cells. Further, ternary devices display a stable photovoltaic performance at 130 degrees C for at least 205 h, which indicates that the use of acceptor mixtures allows to fabricate devices with excellent thermal stability.

Doping of organic semiconductors is a powerful tool to optimize the performance of various organic (opto)electronic and bioelectronic devices. Despite recent advances, the low thermal stability of the electronic properties of doped polymers still represents a significant obstacle to implementing these materials into practical applications. Hence, the development of conducting doped polymers with excellent long-term stability at elevated temperatures is highly desirable. Here, we report on the sequential doping of the ladder-type polymer poly-(benzimidazobenzophenanthroline) (BBL) with a benzimidazole-based dopant (i.e., N-DMBI). By combining electrical, UV-vis/infrared, X-ray diffraction, and electron paramagnetic resonance measurements, we quantitatively characterized the conductivity, Seebeck coefficient, spin density, and microstructure of the sequentially doped polymer films as a function of the thermal annealing temperature. Importantly, we observed that the electrical conductivity of N-DMBI-doped BBL remains unchanged even after 20 h of heating at 190 degrees C. This finding is remarkable and of particular interest for organic thermoelectrics., Funding Agencies|Swedish Research CouncilSwedish Research Council [2016-03979]; AForsk [18-313, 19310]; Olle Engkvists Stiftelse [204-0256]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]; Finnish Cultural FoundationFinnish Cultural Foundation; Finnish Foundation for Technology Promotion; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation [Dnr KAW 2014.0041]

While photovoltaic blends based on non‐fullerene acceptors are touted for their thermal stability, this type of acceptor tends to crystallize, which can result in a gradual decrease in photovoltaic performance and affects the reproducibility of the devices. Two halogenated indacenodithienothiophene‐based acceptors that readily co‐crystallize upon mixing are studied, which indicates that the use of an acceptor mixture alone does not guarantee the formation of a disordered mixture. The addition of the donor polymer to the acceptor mixture readily suppresses the crystallization, which results in a fine‐grained ternary blend with nanometer‐sized domains that do not coarsen due to a high Tg ≈ 200 °C. As a result, annealing at temperatures of up to 170 °C does not markedly affect the photovoltaic performance of ternary devices, in contrast to binary devices that suffer from acceptor crystallization in the active layer. The results indicate that the ternary approach enables the use of high‐temperature processing protocols, which are needed for upscaling and high‐throughput fabrication of organic solar cells. Further, ternary devices display a stable photovoltaic performance at 130 °C for at least 205 h, which indicates that the use of acceptor mixtures allows to fabricate devices with excellent thermal stability.

Liquid chromophores constitute a rare but intriguing class of molecules that are in high demand for the design of luminescent inks, liquid semiconductors, and solar energy storage materials. The most common way to achieve liquid chromophores involves the introduction of long alkyl chains, which, however, significantly reduces the chromophore density. Here, strategy is presented that allows for the preparation of liquid chromophores with a minimal increase in molecular weight, using the important class of perylenes as an example. Two synergistic effects are harnessed: (1) the judicious positioning of short alkyl substituents, and (2) equimolar mixing, which in unison results in a liquid material. A series of 1-alkyl perylene derivatives is synthesized and it is found that short ethyl or butyl chains reduce the melting temperature from 278 degrees C to as little as 70 degrees C. Then, two low-melting derivatives are mixed, which results in materials that do not crystallize due to the increased configurational entropy of the system. As a result, liquid chromophores with the lowest reported molecular weight increase compared to the neat chromophore are obtained. The mixing strategy is readily applicable to other pi-conjugated systems and, hence, promises to yield a wide range of low molecular weight liquid chromophores.

Organic solar cells are thought to suffer from poor thermal stability of the active layer nanostructure, a common belief that is based on the extensive work that has been carried out on fullerene-based systems. We show that a widely studied non-fullerene acceptor, the indacenodithienothiophene-based acceptor ITIC, crystallizes in a profoundly different way as compared to fullerenes. Although fullerenes are frozen below the glass-transition temperature T-g of the photovoltaic blend, ITIC can undergo a glass-crystal transition considerably below its high T-g of similar to 180 degrees C. Nanoscopic crystallites of a low-temperature polymorph are able to form through a diffusion-limited crystallization process. The resulting fine-grained nanostructure does not evolve further with time and hence is characterized by a high degree of thermal stability. Instead, above T-g, the low temperature polymorph melts, and micrometer-sized crystals of a high-temperature polymorph develop, enabled by more rapid diffusion and hence long-range mass transport. This leads to the same detrimental decrease in photovoltaic performance that is known to occur also in the case of fullerene-based blends. Besides explaining the superior thermal stability of non-fullerene blends at relatively high temperatures, our work introduces a new rationale for the design of bulk heterojunctions that is not based on the selection of high-T-g materials per se but diffusion-limited crystallization. The planar structure of ITIC and potentially other non-fullerene acceptors readily facilitates the desired glass-crystal transition, which constitutes a significant advantage over fullerenes, and may pave the way for truly stable organic solar cells., Funding Agencies|Knut and Alice Wallenberg Foundation; Swedish Research Council [2016-06146]; Swedish Foundation for Strategic Research [RMA15-0052]; NSF [DMR-1332208]; German Federal Ministry for Education and Research (BMBF) through the InnoProfile project "Organische p-i-n Bauelemente 2.2" [03IPT602X]

While photovoltaic blends based on non-fullerene acceptors are touted for their thermal stability, this type of acceptor tends to crystallize, which can result in a gradual decrease in photovoltaic performance and affects the reproducibility of the devices. Two halogenated indacenodithienothiophene-based acceptors that readily co-crystallize upon mixing are studied, which indicates that the use of an acceptor mixture alone does not guarantee the formation of a disordered mixture. The addition of the donor polymer to the acceptor mixture readily suppresses the crystallization, which results in a fine-grained ternary blend with nanometer-sized domains that do not coarsen due to a highT(g)approximate to 200 degrees C. As a result, annealing at temperatures of up to 170 degrees C does not markedly affect the photovoltaic performance of ternary devices, in contrast to binary devices that suffer from acceptor crystallization in the active layer. The results indicate that the ternary approach enables the use of high-temperature processing protocols, which are needed for upscaling and high-throughput fabrication of organic solar cells. Further, ternary devices display a stable photovoltaic performance at 130 degrees C for at least 205 h, which indicates that the use of acceptor mixtures allows to fabricate devices with excellent thermal stability., Funding Agencies|King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research (OSR) [OSR-2018-CPF-4106]; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation [2016.0059]; European Research Council (ERC)European Research Council (ERC) [648901]; MCIU; Ikerbasque Foundation [PGC2018-094620-A-100, SEV-2015-0496, PGC2018-095411-B-100]; National Nature Science Foundation of ChinaNational Natural Science Foundation of China (NSFC) [NSFC 21905185]

While photovoltaic blends based on non-fullerene acceptors are touted for their thermal stability, this type of acceptor tends to crystallize, which can result in a gradual decrease in photovoltaic performance and affects the reproducibility of the devices. Two halogenated indacenodithienothiophene-based acceptors that readily co-crystallize upon mixing are studied, which indicates that the use of an acceptor mixture alone does not guarantee the formation of a disordered mixture. The addition of the donor polymer to the acceptor mixture readily suppresses the crystallization, which results in a fine-grained ternary blend with nanometer-sized domains that do not coarsen due to a highT(g)approximate to 200 degrees C. As a result, annealing at temperatures of up to 170 degrees C does not markedly affect the photovoltaic performance of ternary devices, in contrast to binary devices that suffer from acceptor crystallization in the active layer. The results indicate that the ternary approach enables the use of high-temperature processing protocols, which are needed for upscaling and high-throughput fabrication of organic solar cells. Further, ternary devices display a stable photovoltaic performance at 130 degrees C for at least 205 h, which indicates that the use of acceptor mixtures allows to fabricate devices with excellent thermal stability., Funding Agencies|King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research (OSR) [OSR-2018-CPF-4106]; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation [2016.0059]; European Research Council (ERC)European Research Council (ERC) [648901]; MCIU; Ikerbasque Foundation [PGC2018-094620-A-100, SEV-2015-0496, PGC2018-095411-B-100]; National Nature Science Foundation of ChinaNational Natural Science Foundation of China (NSFC) [NSFC 21905185]