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Donor-acceptor (D-A) polymers are promising materials for organic electrochemical transistors (OECTs), as they minimize detrimental faradaic side-reactions during OECT operation, yet their steady-state OECT performance still lags far behind their all-donor counterparts. Here, we report three D-A polymers based on the diketopyrrolopyrrole unit that afford OECT performances similar to those of all-donor polymers, hence representing a significant improvement to the previously developed D-A copolymers. In addition to improved OECT performance, DFT simulations of the polymers and their respective hole polarons also revealed a positive correlation between hole polaron delocalization and steady-state OECT performance, providing new insights into the design of OECT materials. More importantly, we demonstrate how polaron delocalization can be tuned directly at the molecular level by selection of the building blocks comprising the polymers' conjugated backbone, thus paving the way for the development of even higher performing OECT polymers.

Solution-processed organic photodetectors (OPDs) sensitive to infrared (IR) light have the potential to be used in various technologies from health monitoring to communication. These detectors require low bandgap materials absorbing photons beyond 750 nm with high responsivity. In this work, an ultra-low bandgap non-fullerene acceptor (NFA) that absorbs light until 1020 nm is developed. Used in a bulk heterojunction (BHJ)-based device, the photodetector has a maximum responsivity of 0.50 A W−1 at 890 nm without bias voltage comparable with silicon-based detectors. Due to high and balanced mobilities of 10−4 cm2 V−1 s−1, the device has a fast speed of response to IR (i.e. rise and decay time less than 4 μs) and minor damping of 1 dB in the IR communication range (38–50 kHz). The organic photodetector transcripts with accuracy the message emitted around 910 nm from a commercial remote control, thus demonstrating the potential of organic electronics for infrared communication.

Three n-type fused lactam semiconducting polymers were synthesized for thermoelectric and transistor applications via a cheap, highly atom-efficient, and nontoxic transition-metal free aldol polycondensation. Energy level analysis of the three polymers demonstrated that reducing the central acene core size from two anthracenes (A-A), to mixed naphthalene-anthracene (A-N), and two naphthalene cores (N-N) resulted in progressively larger electron affinities, thereby suggesting an increasingly more favorable and efficient solution doping process when employing 4-(2,3-dihydro-1,3-dimethyl-1H-benzimidazol-2-yl)-N,N-dimethylbenzenamine (N-DMBI) as the dopant. Meanwhile, organic field effect transistor (OFET) mobility data showed the N-N and A-N polymers to feature the highest charge carrier mobilities, further highlighting the benefits of aryl core contraction to the electronic performance of the materials. Ultimately, the combination of these two factors resulted in N-N, A-N, and A-A to display power factors (PFs) of 3.2 μW m-1 K-2, 1.6 μW m-1 K-2, and 0.3 μW m-1 K-2, respectively, when doped with N-DMBI, whereby the PFs recorded for N-N and A-N are among the highest reported in the literature for n-type polymers. Importantly, the results reported in this study highlight that modulating the size of the central acene ring is a highly effective molecular design strategy to optimize the thermoelectric performance of conjugated polymers, thus also providing new insights into the molecular design guidelines for the next generation of high-performance n-type materials for thermoelectric applications.

Ternary organic solar cells based on polymer donor and nonfullerene acceptors (NFAs) are delivering high power conversion efficiencies (PCE). Now, further improvement needs to be directed to enhanc...

Recent advances in the development of organic photovoltaic (OPV) materials has led to significant improvements in device performance; now closing in on the 20% efficiency threshold. Despite these improvements in performance, the commercial viability of organic photovoltaic products remains elusive. In this perspective, the current limitations of high performing blends are uncovered, particularly focusing on the industrial upscaling considerations of these materials, such as synthetic scalability, active layer processing, and device stability. Moreover, a simplified metric, namely, the scalability factor (SF), is introduced to evaluate the scale-up potential of specific OPV materials and blends thereof. Of the most popular molecular design strategies investigated in recent times, it is found that the use of Y-series nonfullerene acceptors (NFAs) and synthetically simple materials, such as PTQ-10 and ternary blends, are most effective at maximizing the efficiency without negatively impacting the SF. Furthermore, the improvements that are needed, in terms of device processability and stability, are considered for industrial scale-up and final product application. Finally, an outlook of organic photovoltaics is provided both from a perspective of important research avenues and applications that can be exploited.

To date, many of the high-performance conjugated polymers employed as OECT channel materials make use of ethylene glycol (EG) chains to confer the materials with mixed ionic-electronic conduction properties, with limited emphasis placed on alternative hydrophilic moieties. While a degree of hydrophilicity is required to facilitate some ionic conduction in hydrated channels, an excess results in excessive swelling, with potentially detrimental effects on charge transport. This is therefore a subtle balance that must be optimised to maximise electrical performance. Herein a series of polymers based on a bithiophene-thienothiophene conjugated backbone was synthesised and the conventional EG chains substituted by their propylene and butylene counterparts. Specifically, the use of propylene and butylene chains was found to afford polymers with a more hydrophobic character, thereby reducing excessive water uptake during OECT operation and in turn significantly boosting the polymers' electronic charge carrier mobility. Despite the polymers' lower water uptake, the newly developed oligoether chains retained sufficiently high degrees of hydrophilicity to enable bulk volumetric doping, ultimately resulting in the development of polymers with superior OECT performance.

Summary Although non-fullerene small molecular acceptors (NF-SMAs) are dominating current research in organic solar cells (OSCs), measurements of thermodynamics drivers and kinetic factors determining their morphological stability are lacking. Here, we delineate and measure such factors in crystallizable NF-SMA blends and discuss four model systems with respect to their meta-stability and degree of vitrification. We determine for the first time the amorphous-amorphous phase diagram in an NF-SMA system and show that its deep quench depth can result in severe burn-in degradation. We estimate the relative phase behavior of four other materials systems. Additionally, we derive room-temperature diffusion coefficients and conclude that the morphology needs to be stabilized by vitrification corresponding to diffusion constants below 10−22 cm2/s. Our results show that to achieve stability via rational molecular design, the thermodynamics, glass transition temperature, diffusion properties, and related structure-function relations need to be more extensively studied and understood.

Molecular doping has been shown to improve the performance of various organic (opto)electronic devices. When compared to p-doped systems, research into n-doped organic small-molecules is relatively limited, primarily due to the lack of suitable dopants and the often encountered unfavourable microstructural effects. These factors have prevented the use of n-doping in a wider range of existing materials, such as non-fullerene acceptors (NFAs), that have already shown great promise for a range of (opto)electronic applications. Here, we show that several different molecular n-dopants, namely [1,2-b:2′,1′-d]benzo[i][2.5]benzodiazocine potassium triflate adduct (DMBI-BDZC), tetra-n-butylammonium fluoride (TBAF) and 4-(2,3-dihydro-1,3-dimethyl-1H-benzimidazol-2-yl)-N,N-dimethylbenzenamine (N-DMBI), can be used to n-dope the molecular semiconductor O-IDTBR, a promising NFA, and increase the electron field-effect mobility to >1 cm2 V−1 s−1. By combining complementary experimental techniques with computer simulations of doping and charge carrier dynamics, we show that improved charge transport arises from synergistic effects of n-type doping and morphological changes. Specifically, a new, previously unreported dopant-induced packing orientation results in one of the highest electron mobility values reported to-date for an NFA molecule. Overall, this work highlights the importance of dopant–semiconductor interactions and their impact on morphology, showing that dopant-induced molecular packing motifs may be generic and a key element of the charge transport enhancement observed in doped organics.

A critical bottleneck for improving the performance of organic solar cells (OSC) is minimising non-radiative losses in the interfacial charge-transfer (CT) state via the formation of hybrid energetic states. This requires small energetic offsets often detrimental for high external quantum efficiency (EQE). Here, we obtain OSC with both non-radiative voltage losses (0.24 V) and photocurrent losses (EQE > 80%) simultaneously minimised. The interfacial CT states separate into free carriers with ≈40-ps time constant. We combine device and spectroscopic data to model the thermodynamics of charge separation and extraction, revealing that the relatively high performance of the devices arises from an optimal adjustment of the CT state energy, which determines how the available overall driving force is efficiently used to maximize both exciton splitting and charge separation. The model proposed is universal for donor:acceptor (D:A) with low driving forces and predicts which D:A will benefit from a morphology optimization for highly efficient OSC., Understanding the mechanism of non-radiative losses in organic photovoltaics is crucial to improve the performance further. Here, the authors use combined device and spectroscopic data to reveal universal model to maximise exciton splitting and charge separation by adjusting the energy of charge transfer state.

It is well established that for organic photodetectors (OPDs) to compete with their inorganic counterparts, low dark currents at reverse bias must be achieved. Here, two rhodanine-terminated nonfullerene acceptors O-FBR and O-IDTBR are shown to deliver low dark currents at -2 V of 0.17 and 0.84 nA cm-2, respectively, when combined with the synthetically scalable polymer PTQ10 in OPD. These low dark currents contribute to the excellent sensitivity to low light of the detectors, reaching values of 0.57 μW cm-2 for PTQ10:O-FBR-based OPD and 2.12 μW cm-2 for PTQ10:O-IDTBR-based OPD. In both cases, this sensitivity exceeds that of a commercially available silicon photodiode. The responsivity of the PTQ10:O-FBR-based OPD of 0.34 AW-1 under a reverse bias of -2 V also exceeds that of a silicon photodiode. Meanwhile, the responsivity of the PTQ10:O-IDTBR of 0.03 AW-1 is limited by the energetic offset of the blend. The OPDs deliver high specific detectivities of 9.6 × 1012 Jones and 3.3 × 1011 Jones for O-FBR- and O-IDTBR-based blends, respectively. Both active layers are blade-coated in air, making them suitable for high-throughput methods. Finally, all three of the materials can be synthesized at low cost and on a large scale, making these blends good candidates for commercial OPD applications.

The performance of photovoltaic devices based on blends of conjugated polymers with nonfullerene acceptors depends on the phase behavior and microstructure of the binary, which in turn depends on the chemical structures of the molecular components and the blend composition. We investigate the correlation between the molecular structure, composition, phase behavior, and device performance of a model system consisting of semicrystalline poly-3-hexylthiophene (P3HT) as the donor polymer and three nonfullerene acceptors, two of which (O-IDTBR/EH-IDTBR) have a planar core with different side chains and one (O-IDFBR) of which has a twisted core. We combine differential scanning calorimetry with optical measurements including UV–Vis spectroscopy, photoluminescence, spectroscopic ellipsometry, and Raman spectroscopy and photovoltaic device performance measurements, all at varying blend composition. For P3HT:IDTBR blends, the crystallinity of polymer and acceptor is preserved over a wide composition range and the blend displays a eutectic phase behavior, with the optimum solar cell composition lying close to the eutectic composition. For P3HT:IDFBR blends, increasing acceptor content disrupts the polymer crystallinity, and the optimum device composition appears to be limited by polymer connectivity rather than being linked to the eutectic composition. The optical probes allow us to probe both the crystalline and amorphous phases, clearly revealing the compositions at which component mixing disrupts crystallinity., E.R. is grateful to the Fonds de Recherche du Quebec-Nature et technologies (FRQNT) for a postdoctoral fellowship and acknowledges the financial support from the European Cooperation in Science and Technology. J.N. acknowledges the financial support from the Engineering and Physical Science Research Council (grants nos. EP/P005543/1, EP/ R023581/1, and EP/P032591/1) and from the European Research Council for funding (grant agreement no. 742708). J.N. and E.R. thank the Helmholtz Foundation for a Helmholtz International Fellow Award. A.A.Y.G. thanks the EPSRC for a postdoctoral fellowship award (grant no. EP/P00928X/1). The authors at ICMAB would like to acknowledge the financial support from the Spanish Ministry of Economy, Industry and Competitiveness through the “Severo Ocho” Program for Centers of Excellence in R&D (SEV-2015-0496) and project reference PGC2018-095411-B-I00 as well as the European Research Council (ERC) under grant agreement no. 648901. I.M. acknowledges funding from KAUST, as well as EPSRC Project EP/G037515/1, EP/M005143/1, ECFP7 Project SC2 (610115), and EP/N509486/1 for the financial support.

A series of glycolated polythiophenes for use in organic electrochemical transistors (OECTs) is designed and synthesized, differing in the distribution of their ethylene glycol chains that are tethered to the conjugated backbone. While side chain redistribution does not have a significant impact on the optoelectronic properties of the polymers, this molecular engineering strategy strongly impacts the water uptake achieved in the polymers. By careful optimization of the water uptake in the polymer films, OECTs with unprecedented steady-state performances in terms of [mu C*] and current retentions up to 98% over 700 electrochemical switching cycles are developed. Funding Agencies|KAUSTKing Abdullah University of Science & Technology; King Abdullah University of Science and Technology Office of Sponsored Research (OSR) [OSR-2018-CARF/CCF-3079, OSR-2015-CRG4-2572, OSR-4106 CPF2019]; EC FP7 Project SC2 [610115]; EC H2020 [643791]; EPSRCEngineering & Physical Sciences Research Council (EPSRC) [EP/G037515/1, EP/M005143/1, EP/L016702/1]; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation; Wallenberg Wood Science Center [KAW 2018.0452]; Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoping University [2009-00971]; TomKat Center for Sustainable Energy at Stanford University

Replacing the alkyl side chains on conventional semiconducting polymers with ethylene glycol (EG)-based chains is a successful strategy in the molecular design of mixed conduction materials for bioelectronic devices, including organic electrochemical transistors (OECTs). Such polymers have demonstrated the capability to conduct both ionic and electronic charges and can offer superior performance compared to the most commonly used active material, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate). While many research efforts have been dedicated to optimizing OECT performance through the engineering of the semiconducting polymers’ conjugated backbones, variation of the EG chain length has been investigated considerably less. In this work, a series of glycolated polythiophenes with pendant EG chains spanning two to six EG repeat units was synthesized and the electrochemical and structural characteristics of the resulting films were characterized by experimental means and molecular dynamics simulations. OECTs were fabricated and tested, and their performance showed a strong correlation to the the EG side chain length, thereby elucidating important structure–property guidelines for the molecular design of future channel materials. Specifically, a careful balance in the EG length must be struck during the design of EG-functionalized conjugated polymers for OECTs. While minimizing the EG side chain length appears to boost both the capacitive and charge carrier transport properties of the polymers, the chosen EG side chain length must be kept sufficiently long to induce solubility for processing, and allow for the necessary ion interactions with the conjugated polymer backbone.

The polymer indacenodithiophene-co-benzothiadiazole (IDT-BT) has been thoroughly studied for its use in p-type organic thin-film transistors over the course of the past decade. While a variety of m...

Photocatalysts formed from a single organic semiconductor typically suffer from inefficient intrinsic charge generation, which leads to low photocatalytic activities. We demonstrate that incorporating a heterojunction between a donor polymer (PTB7-Th) and non-fullerene acceptor (EH-IDTBR) in organic nanoparticles (NPs) can result in hydrogen evolution photocatalysts with greatly enhanced photocatalytic activity. Control of the nanomorphology of these NPs was achieved by varying the stabilizing surfactant employed during NP fabrication, converting it from a core–shell structure to an intermixed donor/acceptor blend and increasing H2 evolution by an order of magnitude. The resulting photocatalysts display an unprecedentedly high H2 evolution rate of over 60,000 µmol h−1 g−1 under 350 to 800 nm illumination, and external quantum efficiencies over 6% in the region of maximum solar photon flux. Photocatalysts formed from a single organic semiconductor can suffer from inefficient charge generation leading to low photocatalytic activities. Incorporating a heterojunction between a donor polymer and non-fullerene acceptor in organic nanoparticles leads to enhanced photocatalytic hydrogen evolution.

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.

A novel fused heterocycle-flanked diketopyrrolopyrrole (DPP) monomer, thieno[2,3-b]pyridine diketopyrrolopyrrole (TPDPP), was designed and synthesized. When copolymerized with 3,4-difluorothiophene using Stille coupling polymerization, the new polymer pTPDPP-TF possesses a highly planar conjugated polymer backbone due to the fused thieno[2,3-b]pyridine flanking unit that effectively alleviates the steric hindrance with both the central DPP core and the 3,4-difluorothiophene repeat unit. This new polymer exhibits a high electron affinity (EA) of −4.1 eV and was successfully utilized as an n-type polymer semiconductor for applications in organic field-effect transistors (OFETs) and all polymer solar cells. A promising n-type charge carrier mobility of 0.1 cm2 V–1 s–1 was obtained in bottom-contact, top-gate OFETs, and a power conversion efficiency (PCE) of 2.72% with a high open-circuit voltage (VOC) of 1.04 V was achieved for all polymer solar cells using PTB7-Th as the polymer donor.

Funder: Imperial College London; Id: http://dx.doi.org/10.13039/501100000761, Air‐stable semiconducting inks suitable for complementary logic are key to create low‐power printed integrated circuits (ICs). High‐performance printable electronic inks with 2D materials have the potential to enable the next generation of high performance low‐cost printed digital electronics. Here, the authors demonstrate air‐stable, low voltage (

With chlorinated solvents unlikely to be permitted for use in solution-processed organic solar cells in industry, there must be a focus on developing nonchlorinated solvent systems. Here we report high-efficiency devices utilizing a low-bandgap donor polymer (PffBT4T-2DT) and a nonfullerene acceptor (EH-IDTBR) from hydrocarbon solvents and without using additives. When mesitylene was used as the solvent, rather than chlorobenzene, an improved power conversion efficiency (11.1%) was achieved without the need for pre- or post-treatments. Despite altering the processing conditions to environmentally friendly solvents and room-temperature coating, grazing incident X-ray measurements confirmed that active layers processed from hydrocarbon solvents retained the robust nanomorphology obtained with hot-processed chlorinated solvents. The main advantages of hydrocarbon solvent-processed devices, besides the improved efficiencies, were the reproducibility and storage lifetime of devices. Mesitylene devices showed better reproducibility and shelf life up to 4000 h with PCE dropping by only 8% of its initial value.

A fused donor, thienobenzo[

Nonfullerene acceptors (NFAs) dominate organic photovoltaic (OPV) research due to their promising efficiencies and stabilities. However, there is very little investigation into the molecular processes of degradation, which is critical to guiding design of novel NFAs for long‐lived, commercially viable OPVs. Here, the important role of molecular structure and conformation in NFA photostability in air is investigated by comparing structurally similar but conformationally different promising NFAs: planar O‐IDTBR and nonplanar O‐IDFBR. A three‐phase degradation process is identified: i) initial photoinduced conformational change (i.e., torsion about the core–benzothiadiazole dihedral), induced by noncovalent interactions with environmental molecules, ii) followed by photo‐oxidation and fragmentation, leading to chromophore bleaching and degradation product formation, and iii) finally complete chromophore bleaching. Initial conformational change is a critical prerequisite for further degradation, providing fundamental understanding of the relative stability of IDTBR and IDFBR, where the already twisted IDFBR is more prone to degradation. When blended with the donor polymer poly(3‐hexylthiophene), both NFAs exhibit improved photostability while the photostability of the polymer itself is significantly reduced by the more miscible twisted NFA. The findings elucidate the important role of NFA molecular structure in photostability of OPV systems, and provide vital insights into molecular design rules for intrinsically photostable NFAs.

With the emergence of nonfullerene electron acceptors resulting in further breakthroughs in the performance of organic solar cells, there is now an urgent need to understand their degradation mechanisms in order to improve their intrinsic stability through better material design. In this study, we present quantitative evidence for a common root cause of light-induced degradation of polymer:nonfullerene and polymer:fullerene organic solar cells in air, namely, a fast photo-oxidation process of the photoactive materials mediated by the formation of superoxide radical ions, whose yield is found to be strongly controlled by the lowest unoccupied molecular orbital (LUMO) levels of the electron acceptors used. Our results elucidate the general relevance of this degradation mechanism to both polymer:fullerene and polymer:nonfullerene blends and highlight the necessity of designing electron acceptor materials with sufficient electron affinities to overcome this challenge, thereby paving the way toward achieving long-term solar cell stability with minimal device encapsulation.

The authors declare no competing financial interests. The author CH Tan thanks Malaysian Government MyBrainSc for the funding and also Matthew Davies from Swansea University for providing PL excitation spectroscopy instrument. Funding from the KAUST project OSR-2015-CRG-2572 is gratefully acknowledged. The authors also thank KAUST for financial support and acknowledge EC FP7 Project SC2 (610115), EC H2020 (643791), and EPSRC Projects EP/G037515/1 and EP/M005143/1.

Organic semiconductors require an energetic offset in order to photogenerate free charge carriers efficiently, owing to their inability to effectively screen charges. This is vitally important in order to achieve high power conversion efficiencies in organic solar cells. Early heterojunction-based solar cells were limited to relatively modest efficiencies (

This work was partially supported by the National Science Foundation under Grant No. 1610899 and Intel. The authors thank Dr. Igal Deckman, Dr. Balthazar Lechene, and Dr. Adrien Pierre for helpful technical discussions.

Reducing contact resistance is critical to developing high-performance organic field-effect transistors (OFETs) since it impacts both the device mobility and switching speed. Charge injection and collection has been optimized by applying chemical treatments to the contacts, such as self-assembled monolayers (SAMs), oxide interlayers, or dopants. Here, we tested how flame annealing the surface of the electrodes impacts the interface and bulk components of the contact resistance, as well as the overall device performance. A butane micro torch was used to flash-anneal the gold electrodes, which allowed gold grains to crystallize into larger domains. We found that, along with the grain size, the surface roughness of the contacts was also increased. SAM treatment created a lower work function shift on a flame annealed electrode than when deposited on an untreated surface, due to the greater surface roughness. This resulted in a larger interface contact resistance. However, flame annealing also produced an order of magnitude reduction in the density of trap states in the semiconductor layer, which reduced the bulk contact resistance and channel resistance. These competing effects yielded OFETs with similar performance as untreated devices.

Fullerenes have formed an integral part of high performance organic solar cells over the last 20 years, however their inherent limitations in terms of synthetic flexibility, cost and stability have acted as a motivation to develop replacements; the so-called non-fullerene electron acceptors. A rapid evolution of such materials has taken place over the last few years, yielding a number of promising candidates that can exceed the device performance of fullerenes and provide opportunities to improve upon the stability and processability of organic solar cells. In this review we explore the structure-property relationships of a library of non-fullerene acceptors, highlighting the important chemical modifications that have led to progress in the field and provide an outlook for future innovations in electron acceptors for use in organic photovoltaics.

We report the synthesis of two barbiturate end-capped non-fullerene acceptors and demonstrate their efficient function in high voltage output organic solar cells. The acceptor with the lower LUMO level is shown to exhibit suppressed geminate recombination losses, resulting in enhanced photocurrent generation and higher overall device efficiency.

Nonfullerene solar cells have increased their efficiencies up to 13%, yet quantum efficiencies are still limited to 80%. Here we report efficient nonfullerene solar cells with quantum efficiencies approaching unity. This is achieved with overlapping absorption bands of donor and acceptor that increases the photon absorption strength in the range from about 570 to 700 nm, thus, almost all incident photons are absorbed in the active layer. The charges generated are found to dissociate with negligible geminate recombination losses resulting in a short-circuit current density of 20 mA cm−2 along with open-circuit voltages >1 V, which is remarkable for a 1.6 eV bandgap system. Most importantly, the unique nano-morphology of the donor:acceptor blend results in a substantially improved stability under illumination. Understanding the efficient charge separation in nonfullerene acceptors can pave the way to robust and recombination-free organic solar cells., The nonfullerene-based small molecules start to attract more attention for solar cell research than the fullerene acceptors due to their wider tunability. Here Baran et al. demonstrate nonfullerene-based solar cells with high power conversion efficiency of 12% and quantum efficiencies approaching 100%.

The field of organic photovoltaics has advanced a great deal over the last decade, with device efficiencies now exceeding 11%. A large part of this success can be attributed to the development of donor polymer materials, from their humble beginnings as homopolymers to the highly tuned push–pull copolymer and terpolymer materials that are now being reported on a regular basis. Through the careful use of chemical modification, it has been possible to design and synthesize a wide variety of donor polymers, allowing optimization of both the optoelectronic and structural properties of the materials. In doing so, more favourable active layer blends have been achieved and therefore significant improvements in device performance have been observed. Herein we discuss how the chemical design of donor polymers for organic photovoltaics has led to the emergence of high-performance materials.

A comparison of the efficiency, stability, and photophysics of organic solar cells employing poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3'″-di(2-octyldodecyl)-2,2';5',2″;5″,2'″-quaterthiophen-5,5'″-diyl)] (PffBT4T-2OD) as a donor polymer blended with either the nonfullerene acceptor EH-IDTBR or the fullerene derivative, [6,6]-phenyl C71 butyric acid methyl ester (PC71 BM) as electron acceptors is reported. Inverted PffBT4T-2OD:EH-IDTBR blend solar cell fabricated without any processing additive achieves power conversion efficiencies (PCEs) of 9.5 ± 0.2%. The devices exhibit a high open circuit voltage of 1.08 ± 0.01 V, attributed to the high lowest unoccupied molecular orbital (LUMO) level of EH-IDTBR. Photoluminescence quenching and transient absorption data are employed to elucidate the ultrafast kinetics and efficiencies of charge separation in both blends, with PffBT4T-2OD exciton diffusion kinetics within polymer domains, and geminate recombination losses following exciton separation being identified as key factors determining the efficiency of photocurrent generation. Remarkably, while encapsulated PffBT4T-2OD:PC71 BM solar cells show significant efficiency loss under simulated solar irradiation ("burn in" degradation) due to the trap-assisted recombination through increased photoinduced trap states, PffBT4T-2OD:EH-IDTBR solar cell shows negligible burn in efficiency loss. Furthermore, PffBT4T-2OD:EH-IDTBR solar cells are found to be substantially more stable under 85 °C thermal stress than PffBT4T-2OD:PC71 BM devices.

Optimization of the energy levels at the donor–acceptor interface of organic solar cells has driven their efficiencies to above 10%. However, further improvements towards efficiencies comparable with inorganic solar cells remain challenging because of high recombination losses, which empirically limit the open-circuit voltage (Voc) to typically less than 1 V. Here we show that this empirical limit can be overcome using non-fullerene acceptors blended with the low band gap polymer PffBT4T-2DT leading to efficiencies approaching 10% (9.95%). We achieve Voc up to 1.12 V, which corresponds to a loss of only Eg/q − Voc = 0.5 ± 0.01 V between the optical bandgap Eg of the polymer and Voc. This high Voc is shown to be associated with the achievement of remarkably low non-geminate and non-radiative recombination losses in these devices. Suppression of non-radiative recombination implies high external electroluminescence quantum efficiencies which are orders of magnitude higher than those of equivalent devices employing fullerene acceptors. Using the balance between reduced recombination losses and good photocurrent generation efficiencies achieved experimentally as a baseline for simulations of the efficiency potential of organic solar cells, we estimate that efficiencies of up to 20% are achievable if band gaps and fill factors are further optimized.

The research reported in this publication was supported by the Office of Sponsored Research (OSR) under the Grant Agreement FCS/1/3321/01 and by baseline funding from the King Abdullah University of Science and Technology (KAUST). M. A. A. is grateful to Saudi Basic Industries Corporation (SABIC) for funding received towards the PhD. H.N.M. thanks the KAUST SRSI program for support.J.I.K. and R.S.A. contributed equally to the work.

The authors acknowledge funding from KAUST and thank Engineering and Physical Sciences Research Council Projects EP/G037515/1, EP M−005143/1, ECFP7 Project SC2 (610115), EP/N509486/1 for the financial support. M.M. gratefully thanks the Imperial College Schrodinger Scholarship for financial support.

Technological deployment of organic photovoltaic modules requires improvements in device light-conversion efficiency and stability while keeping material costs low. Here we demonstrate highly efficient and stable solar cells using a ternary approach, wherein two non-fullerene acceptors are combined with both a scalable and affordable donor polymer, poly(3-hexylthiophene) (P3HT), and a high-efficiency, low-bandgap polymer in a single-layer bulk-heterojunction device. The addition of a strongly absorbing small molecule acceptor into a P3HT-based non-fullerene blend increases the device efficiency up to 7.7 ± 0.1% without any solvent additives. The improvement is assigned to changes in microstructure that reduce charge recombination and increase the photovoltage, and to improved light harvesting across the visible region. The stability of P3HT-based devices in ambient conditions is also significantly improved relative to polymer:fullerene devices. Combined with a low-bandgap donor polymer (PBDTTT-EFT, also known as PCE10), the two mixed acceptors also lead to solar cells with 11.0 ± 0.4% efficiency and a high open-circuit voltage of 1.03 ± 0.01 V. Ternary organic blends using two non-fullerene acceptors are shown to improve the efficiency and stability of low-cost solar cells based on P3HT and of high-performance photovoltaic devices based on low-bandgap donor polymers.

Solution-processed organic photovoltaics (OPV) offer the attractive prospect of low-cost, light-weight and environmentally benign solar energy production. The highest efficiency OPV at present use low-bandgap donor polymers, many of which suffer from problems with stability and synthetic scalability. They also rely on fullerene-based acceptors, which themselves have issues with cost, stability and limited spectral absorption. Here we present a new non-fullerene acceptor that has been specifically designed to give improved performance alongside the wide bandgap donor poly(3-hexylthiophene), a polymer with significantly better prospects for commercial OPV due to its relative scalability and stability. Thanks to the well-matched optoelectronic and morphological properties of these materials, efficiencies of 6.4% are achieved which is the highest reported for fullerene-free P3HT devices. In addition, dramatically improved air stability is demonstrated relative to other high-efficiency OPV, showing the excellent potential of this new material combination for future technological applications., In organic photovoltaics, the best performing devices usually involve low-bandgap polymers whose limited solubility and stability constrain the scalability of organic solar cells. Here, Holliday et al. develop a new acceptor and pair it with canonical P3HT to obtain 6.4% efficient and stable devices.