A self-healing sulfur vulcanized natural rubber (NR) is here reported using the common ingredients in a traditional NR formulation. The dynamic character of the di- and polysulfide bonds naturally present in covalently cross-linked rubbers was found to be responsible for the healing ability and the full recovery of mechanical properties at moderate temperatures provided the material was employed in a nonfully cured starting state. Results show that a compromise between mechanical performance and healing capability can be reached by tailoring the amount of sulfur, the cross-linking density, and the disulfide/polysulfide ratio. The healing efficiency was found to depend on the postcuring storage time, the time between damage creation and re-establishment of mechanical contact, and the actual healing time. Furthermore, a dedicated electron spin resonance (ESR) test allowed establishing the underlying healing principle based on temperature-induced free sulfur radicals. The main observations presented here can serve as the basis for the design and preparation of other self-healing polymers with long-term durability based on di-/polysulfide bridges and other reversible moieties

Solar cells based on organic molecules or conjugated polymers attract great attention due to their unique advantages, such as low cost, and their use in flexible devices, but are still limited by their low power conversion efficiency (PCE). To improve the PCEs of polymer solar cells, more efforts have been made to increase short-circuit current (J sc ) or open-circuit voltage (V oc ). However, the trade-off between J sc and V oc in bulk heterojunctions solar cells makes it tricky to find a polymer with a low band gap to efficiently absorb photons in the visible and near infrared region of the solar spectrum, while maintaining a high V oc in solar cells. Therefore, it is crucial to design and synthesize polymers with energy levels aligning with the LUMO (lowest unoccupied molecular orbital) of an electron acceptor to minimize the LUMO level difference between donor and acceptor to keep enough driving force for charge generation, thereby maximizing photovoltage in solar cells. Here a novel copolymer APFO-Green 9 was synthesized. Polymer solar cells based on APFO-Green 9 blended with a derivative of fullerene demonstrate high photovoltage by fine tuning the HOMO and LUMO level of APFO-Green 9. Solar cells based on APFO-Green 9 and [6,6]-phenyl-C71-butyric acid methyl ester ([70]PCBM) present a photoresponse extended to 900 nm with J sc of 6.5 mA cm À2 , V oc of 0.81 V and PCE of 2.3% under illumination of AM1.5 with light intensity of 100 mW cm À2 . As a low band gap polymer with a V oc bigger than 0.8 V, APFO-Green 9 is a promising candidate for efficient tandem solar cells.

Alternating copolymers based on cyclopentadithiophene (CPDT) and five different electron‐deficient aromatic units with reduced optical band gaps are synthesized via Suzuki coupling. All polymers show a significant photovoltaic response when mixed with a fullerene acceptor. The frontier orbital levels of the new polymers are designed to minimize energy losses by increasing the open‐circuit voltage with respect to the optical band gap, while maintaining a high coverage of the absorption with the solar spectrum. The best cells are obtained for a copolymer of CPDT and benzooxadiazole (BO) with a band gap of 1.47 eV. This cell gives a short‐circuit current of 5.4 mA cm−2, an open‐circuit voltage of 0.78 V, and a fill factor of 0.6, resulting in a power conversion efficiency of about 2.5%.

with outstanding optoelectronic properties. [1] In 2009, these materials were introduced in solar cells and have since established a striking increase in performance, reaching over 22% in stateof-the-art devices. [2] Here, the perovskite absorber is sandwiched between two selective charge extraction layers, that transport the charges to the electrodes. [3] Although efficient inorganic hole transporting materials (HTMs) have been reported, [4] the most well-known HTMs are the organic materials 2,2′,7,7′-tetrakis-(N,N-di-4-methoxyphenylamino)-9,9′spirobifluorene (Spiro-OMeTAD) and polytriarylamine (PTAA). Alternatives that compete in performance have been published, [5][6][7] however, just like Spiro-OMeTAD and PTAA, most of these materials are synthesized in multistep synthetic procedures, involving (transition) metal catalyzed cross-coupling reactions, stringent reaction conditions and extensive product purification. This results in a relative high material cost, consequently leading to a significant contribution to the total device cost. [5,8,9] Additionally, the tedious synthesis hampers large State-of-the-art perovskite-based solar cells employ expensive, organic hole transporting materials (HTMs) such as Spiro-OMeTAD that, in turn, limits the commercialization of this promising technology. Herein an HTM (EDOT-Amide-TPA) is reported in which a functional amide-based backbone is introduced, which allows this material to be synthesized in a simple condensation reaction with an estimated cost of <$5 g −1 . When employed in perovskite solar cells, EDOT-Amide-TPA demonstrates stabilized power conversion efficiencies up to 20.0% and reproducibly outperforms Spiro-OMeTAD in direct comparisons. Time resolved microwave conductivity measurements indicate that the observed improvement originates from a faster hole injection rate from the perovskite to EDOT-Amide-TPA. Additionally, the devices exhibit an improved lifetime, which is assigned to the coordination of the amide bond to the Li-additive, offering a novel strategy to hamper the migration of additives. It is shown that, despite the lack of a conjugated backbone, the amide-based HTM can outperform state-of-the-art HTMs at a fraction of the cost, thereby providing a novel set of design strategies to develop new, low-cost HTMs.

In this work we report the effect of the hard block dianhydride structure on the overall properties of partially biobased semiaromatic polyimides. For the study, four polyimides were synthesized using aliphatic fatty dimer diamine (DD1) as the soft block and four different commercially available aromatic dianhydrides as the hard block: 4,4′-(4,4′-isopropylidenediphenoxy) bis(phthalic anhydride) (BPADA), 4,4′-oxidiphthalic anhydride (ODPA), 4,4′-(Hexafluoroisopropylidene) diphthalic anhydride (6FDA), and 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA). The polymers synthesized were fully organo-soluble thermoplastic branched polyimides with glass transition temperatures close to room temperature. The detailed analysis took into account several aspects of the dianhydrides structure (planarity, rigidity, bridging group between the phtalimides, and electronic properties) and related them to the results obtained by differential scanning calorimetry, rheology, fluorescence and broadband dielectric spectroscopy. Moreover, the effects of physical parameters (crystallization and electronic interactions) on the relaxation behavior are discussed. Despite the presence of the bulky branched soft block given by the dimer diamine, all polyimides showed intermolecular charge transfer complexes, whose extent depends on the electronic properties of the dianhydride hard block. Furthermore, the results showed that polyimides containing flexible and bulky hard blocks turned out fully amorphous while the more rigid dianhydride (BPDA) led to a nanophase separated morphology with low degree of crystallinity resulting in constrained segmental relaxation with high effect on its mechanical response with the annealing time. This work represents the first detailed report on the development and characterization of polyimides based on a biobased fatty dimer diamine. The results highlight the potential of polymer property design by controlled engineering of the aromatic dianhydride blocks.