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Non-fullerene acceptors have recently revolutionized indoor organic photovoltaics (OPVs) with power conversion efficiencies exceeding 30% in laboratory scale. Nevertheless, transferring their superior performance to larger-scale prototyping, i.e., air-processing via roll-to-roll compatible techniques, still shows severe challenges. Herein, the industrial potential of the PM6:IO4Cl blend, which is one of the most successful indoor OPV photoactive layers (PALs), is thoroughly investigated. The corresponding thick and semitransparent laminated devices are fabricated entirely in air, by blade and slot-die coating. Their current–voltage (J–V) characteristics show anomalous features depending on the illumination side, with the cathode side generally outperforming the anode counterpart. Electrical and optical modeling reveal that a plausible cause of such a phenomenon is a dead layer that forms at the PAL/anode contact interface that does not contribute to the photocurrent. Said layer becomes undetectable when the PALs are made thin enough (

Recent advances in organic solar cells based on non-fullerene acceptors (NFAs) come with reduced non-radiative voltage losses (ΔVnr). Here we show that, in contrast to the energy-gap-law dependence observed in conventional donor:fullerene blends, the ΔVnr values in state-of-the-art donor:NFA organic solar cells show no correlation with the energies of charge-transfer electronic states at donor:acceptor interfaces. By combining temperature-dependent electroluminescence experiments and dynamic vibronic simulations, we provide a unified description of ΔVnr for both fullerene- and NFA-based devices. We highlight the critical role that the thermal population of local exciton states plays in low-ΔVnr systems. An important finding is that the photoluminescence yield of the pristine materials defines the lower limit of ΔVnr. We also demonstrate that the reduction in ΔVnr (for example

n/a Funding Agencies|Knut and Alice Wallenberg Foundation (KAW) through a Wallenberg Scholar grant

A small molecular donor TiC12 with asymmetric thieno[3,2-c]isochromene unit is incorporated into the PM6:Y6 system as the third component for constructing ternary organic solar cells (OSCs). It was found that TiC12 played an outstanding role in improvement of open-circuit voltage (Voc), short-circuit current (Jsc) and fill factor (FF) for the OSCs. The effects of TiC12 on absorption, exciton dissociation, charge extraction, bimolecular recombination and morphology of active layer are analyzed in detail. The synergetic improvement of Jsc, Voc and FF parameters is realized to generate an advanced power conversion efficiency (PCE) of 17.25% in the optimized PM6:TiC12:Y6 (0.9:0.1:1.2) ternary device. Furthermore, the Voc is increased in proportion to the added amount of TiC12 in the ternary devices due to a reduced disorder and nonradiative energy loss, although the guest donor TiC12 exhibited a higher HOMO level than PM6. This study provides an effective and innovative approach to elevate Voc and thus PCE for ternary OSCs by introducing a guest small molecular donor with a higher HOMO level and better miscibility with acceptor.

In this article, a natural biological porous material, from living diatoms, is used to prepare new UV-protection hybrid materials with an Eu3+-complex. By removing the organic protoplasm of living diatoms, the exoskeleton with a regular pore structure arrangement was obtained. The Eu3+-complex was chemically bonded to the exoskeleton modified by the silane coupling agent (3-aminopropyl)trimethoxy silane (APTMS). Compared with pure Eu3+-complexes, the fluorescence intensity of this hybrid material was increased by approximately 10 times. For illustrating its applications in the field of UV-protection, we mixed the USDU with polyacrylonitrile to produce flexible and transparent polymer films. The hybrid composite film (USDU@PAN) achieved partial absorption of ultraviolet light between 200 and 400 nm. At the same time, it also emits visible fluorescence and the intensity of the fluorescence is greatly increased. Therefore, the USDU@PAN film has wide application prospects in areas such as photoelectric sensors and UV-protection devices. More importantly, we transform natural organisms into materials with excellent optical properties. Therefore, it can be used in the field of UV-protection.

Deoxyribonucleic acid (DNA) and a self-doped conjugated polyelectrolyte, poly(4-(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl-methoxy)-1-butanesulfonic acid (PEDOT-S), are assembled for organic optoelectronics and bioelectronics. The DNA’s helix–coil phase transition in water is studied as a function of composition by thermo-optical analysis. DNA and PEDOT-S are functionalized by using a surfactant, cetyltrimethylammonium chloride (CTMA), and DNA:CTMA, PEDOT-S:CTMA, and DNA:CTMA:PEDOT-S:CTMA complexes were characterized regarding thermal, optical, morphological, and structural properties. Finally, DNA and DNA:PEDOT-S mixtures are processed in water for fabricating organized films through brushing. The electrical properties of these films are characterized using an interdigitated electrode. The films show an electronic conductivity of ∼10–6–10–5 S/cm in a range of semiconductors.

Transparent organic electrodes printed from high-conductivity PEDOT:PSS have become essential for upscaling all-carbon based, low-cost optoelectronic devices. In the printing process, low-work-function PEDOT:PSS electrodes (cathode) are achieved by coating an ultra-thin, non-conjugated polyelectrolyte that is rich in amine groups, such as poly(ethylene imine) (PEI) or its ethoxylated derivative (PEIE), onto PEDOT:PSS surfaces. Here, we mapped the physical and chemical processes that occur at the interface between thin PEIx (indicating either PEI or PEIE) and PEDOT:PSS during printing. We identify that there is a dedoping effect of PEDOT induced by the PEIx. Using infrared spectroscopy, we found that the amine-rich PEIx can form chemical bonds with the dopant, PSS. At lower PSS concentration, PEIx also shows an electron-transfer effect to the charged PEDOT chain. These interface reactions lock the surface morphology of PEDOT:PSS, preventing the redistribution of PSS, and reduce the work function. Subsequent exposure to oxygen during the device fabrication process, on the other hand, can result in redoping of the low-work-function PEDOT:PSS interface, causing problems for printing reproducible devices under ambient conditions. Funding Agencies|Swedish Energy AgencySwedish Energy Agency; Swedish Science Council; Swedish Strategic Research Foundation through the project SiOs; Knut and Alice Wallenberg foundation (KAW) through Wallenberg Scholar grant; Knut and Alice Wallenberg foundation (KAW) through Proof of Concept project for upscaling organic solar cells

Charge separation dynamics after the absorption of a photon is a fundamental process relevant both for photosynthetic reaction centers and artificial solar conversion devices. It has been proposed that quantum coherence plays a role in the formation of charge carriers in organic photovoltaics, but experimental proofs have been lacking. Here we report experimental evidence of coherence in the charge separation process in organic donor/acceptor heterojunctions, in the form of low frequency oscillatory signature in the kinetics of the transient absorption and nonlinear two-dimensional photocurrent spectroscopy. The coherence plays a decisive role in the initial ~200 femtoseconds as we observe distinct experimental signatures of coherent photocurrent generation. This coherent process breaks the energy barrier limitation for charge formation, thus competing with excitation energy transfer. The physics may inspire the design of new photovoltaic materials with high device performance, which explore the quantum effects in the next-generation optoelectronic applications., Although coherent vibrational motion in donor-acceptor blends may contribute to photogeneration generation in organic solar cells (OSCs), proof of a direct correlation is still lacking. Here, the authors report the role of vibrational coherence on photocurrent generation in ternary OSC blends.

1-Chloronaphthalene (CN) has been a common solvent additive in both fullerene-and nonfullerene-based organic solar cells. In spite of this, its working mechanism is seldom investigated, in particular, during the drying process of bulk heterojunctions composed of a donor:acceptor mixture. In this work, the role of CN in all-polymer solar cells is investigated by in situ spectroscopies and ex situ characterization of blade-coated PBDB-T:PF5-Y5 blends. Our results suggest that the added CN promotes self-aggregation of polymer donor PBDB-T during the drying process of the blend film, resulting in enhanced crystallinity and hole mobility, which contribute to the increased fill factor and improved performance of PBDB-T:PF5-Y5 solar cells. Besides, the nonradiative energy loss of the corresponding device is also reduced by the addition of CN, corresponding to a slightly increased open-circuit voltage. Overall, our observations deepen our understanding of the drying dynamics, which may guide further development of all-polymer solar cells. Funding Agencies|Knut and Alice Wallenberg Foundation [2016.0059, 2017.0186]; Swedish Government Strategic Research Area in Material Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [200900971]; Swedish Research Council [2017-04123, 2016-06146, 2019-04683, 2021-04798]; China Scholarship Council; Swedish Research Council Formas; Swedish Energy Agency [48598]; Research Grants Council (RGC) of Hong Kong [14303519]

In electrochemical energy storage devices (ESDs), organic electrolytes are typically used for wide operational potential window, yet they suffer with cost, environmental, flammability issues, and low ionic conductivity when compared with water-based electrolytes. Hence, for large-scale applications that require high power and safety, presently there is no true solution. Though water-based electrolytes have higher ionic conductivities, and are cost-effective and nonflammable, their high self-discharge rate with organic/carbon-based electrodes impedes their commercialization. It is found out that highly concentrated polymer electrolytes on the concept of "water-in-salt electrolyte" lead to extremely low leakage current within the electrochemical stability window (ESW) of water, thus solving the issue of self-discharge in organic/carbon-based ESDs. Herein, potassium polyacrylate (PAAK) is prepared as "water-in-polymer salt electrolyte" (WIPSE) and tested for one of most abundant wood-based biopolymer lignin and polyimide as positive and negative electrodes, respectively, in both half-cell and full-cell. The device shows an open-circuit voltage drops Funding Agencies|Proof-of-Concept project "Paper Batteries" - Knut and Alice Wallenberg (KAW) foundation; "high-voltage aqueous electrolytes" - Knut and Alice Wallenberg (KAW) foundation; "Wood Wallenberg Science Center" - Knut and Alice Wallenberg (KAW) foundation; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009-00971]; Wallenberg Scholar grants from KAW

The desired attributes of organic photovoltaics (OPV) as a low cost and sustainable energy harvesting technology demand the use of non-halogenated solvent processing for the photoactive layer (PAL) materials, preferably of low synthetic complexity (SC) and without compromising the power conversion efficiency (PCE). Despite their record PCEs, most donor–acceptor conjugated copolymers in combination with non-fullerene acceptors are still far from upscaling due to their high cost and SC. Here we present a non-halogenated and low SC ink formulation for the PAL of organic solar cells, comprising PTQ10 and PC61BM as donor and acceptor materials, respectively, showing a record PCE of 7.5% in blade coated devices under 1 sun, and 19.9% under indoor LED conditions. We further study the compatibility of the PAL with 5 different electron transport layers (ETLs) in inverted architecture. We identify that commercial ZnO-based formulations together with a methanol-based polyethyleneimine-Zn (PEI-Zn) chelated ETL ink are the most suitable interlayers for outdoor conditions, providing fill factors as high as 74% and excellent thickness tolerance (up to 150 nm for the ETL, and >200 nm for the PAL). In indoor environments, SnO2 shows superior performance as it does not require UV photoactivation. Semi-transparent devices manufactured entirely in air via lamination show indoor PCEs exceeding 10% while retaining more than 80% of the initial performance after 400 and 350 hours of thermal and light stress, respectively. As a result, PTQ10:PC61BM combined with either PEI-Zn or SnO2 is currently positioned as a promising system for industrialisation of low cost, multipurpose OPV modules., The authors are thankful to Prof. Hans Arwin (Linköping University) for his valuable help in ellipsometry measurements and their corresponding optical modelling. The authors acknowledge Dr Luis Ever Aguirre (Epishine AB) for the acquisition of the indoor LED spectrum employed with laminated devices and Prof. Fengling Zhang (Linköping University) for lending the QE-Pro spectrometer. X. R.-M., S. R.-G., J. C. and O. I. acknowledge the Knut and Alice Wallenberg foundation for funding. The authors thank Dr Bernhard Dörling for building the electronic controller to make the speed profiles with the blade coater, and M. Gibert-Roca for designing and building the multiplexor for the sequential and rapid measurement of the 24 pixels in each sample. M. C. Q. greatly acknowledges funding by the Ministry of Science and Innovation through grants (CEX2019-000917-S) and PGC2018-095411-B-I00, and by the European Research Council through grant agreement no. 648901., With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).

A green, though black, sustainable and low-cost carbon material-charcoal produced from wood-is developed for electricity storage. Charcoal electrodes are fabricated by ball-milling charcoal and adding protein nanofibril binders. The charcoal electrode presents a capacitance of 360 F g(-1) and a conductivity of 0.2 S m(-1). A pair of redox peaks is observed in the cyclic voltammetry and assigned to originate from quinone groups. Compared with other wooden electrodes, these charcoal electrodes display better cycling stability with 88% capacity retention after 1000 cycles. Their discharge capacity is 2.5 times that of lignosulfonate/graphite hybrid electrodes. Funding Agencies|Knut and Alice Wallenberg Foundation (KAW)Knut & Alice Wallenberg Foundation; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]

The integration of organic photovoltaic (OPV) modules on greenhouses is an encouraging practice to offset the energy demands of crop growth and provide extra functionality to dedicated farmland. Nevertheless, such OPV devices must meet certain optical and stability requirements to turn net zero energy greenhouse systems a reality. Here a donor:acceptor polymer blend is optimized for its use in laminated devices while matching the optical needs of crops. Optical modeling is performed and a greenhouse figure-of-merit is introduced to benchmark the trade-off between photovoltaic performance and transparency for both chloroplasts and humans. Balanced donor:acceptor ratios result in better-performing and more thermally stable devices than acceptor-enriched counterparts. The optimized polymer blend and state-of-the-art polymer:small-molecule blends are next transferred to 25 cm2 laminated modules processed entirely from solution and in ambient conditions. The modules are mounted on a greenhouse as standalone or 4-terminal tandem configurations and their outdoor stability is tracked for months. The study reveals degradation modes undetectable under laboratory conditions such as module delamination, which accounts for 10–20% loss in active area. Among the active layers tested, polymer:fullerene blends are the most stable and position as robust light harvesters in future building-integrated OPV systems., X.R.-M., S.R.-G., and O.I. acknowledge the Knut and Alice Wallenberg Foundation for funding. S.R.-G. is thankful to the Marie Sklodowska-Curie Actions (H2020-MSCA-IF-2020) for grant agreement No. 101025608, IDEAL. The authors acknowledge Dr. Bernhard Dörling for building the electronic controller of the accelerated blade coater and Dr. M. Gibert-Roca for designing the corresponding multiplexor. M.C.-Q. thanks to the Spanish Ministry of Science and Innovation for funding through ISOSCELLES project (PID2021-128924OB-I00). The table of contents figure contains freely available resources from https://flaticon.com.

Spin-cast intermolecular interactions in conjugated polymer films lead to the formation of excited states delocalized over a few oriented and tightly packed conjugated segments. The optoelectronic ...

Organic photovoltaic cells are potential candidates to drive low power consumption off-grid electronics for indoor applications. However, their power conversion efficiency is still limited by relat ...

The contributions of Jean-Luc Bredas to the science of organic optoelectronics are immense, and so are the skills of communication in his talks and papers. They have been very influential and shaped the development of organic optoelectronics over a long period of time. This Festschrift contribution is a narrative of the impact of his work on my own scientific and technological studies and a way of acknowledging his great influence. Thanks!

We report pulsed terahertz (THz) emission from solution-processed metal halide perovskite films with electric field 1 order of magnitude lower than p-InAs, an efficient THz emitter. Such emission is enabled by a unique combination of efficient charge separation, high carrier mobilities, and more importantly surface defects. The mechanism of generation was identified by investigating the dependence of the THz electric field amplitude on surface defect densities, excess charge carriers, excitation intensity and energy, temperature, and external electric field. We also show for the first time THz emission from a curved surface, which is not possible for any crystalline semiconductor and paves the way to focus high-intensity sources. These results represent a possible new direction for perovskite optoelectronics and for THz emission spectroscopy as a complementary tool in investigating surface defects on metal halide perovskites, of fundamental importance in the optimization of solar cells and light-emitting diodes. Funding Agencies|ERC Starting Grant [717026]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkping University (Faculty Grant SFO-Mat-LiU) [2009-00971]; European Union Marie Curie ITN Project NOTEDEV [607521]; China Scholarship Council; Knut and Alice Wallenberg Foundation (KAW); Swedish Foundation for Strategic Research (SSF) [RIF14-055]

The efficiency of bulk heterojunction (BHJ) based organic solar cells is highly dependent on the morphology of the blend film, which is a result of a fine interplay between donor, acceptor, and solvent during the film drying. In this work, a versatile set-up of in situ spectroscopies is used to follow the morphology evolution during blade coating of three iconic BHJ systems, including polymer:fullerene, polymer:nonfullerene small molecule, and polymer:polymer. the drying and photoluminescence quenching dynamics are systematically study during the film formation of both pristine and BHJ films, which indicate that the component with higher molecular weight dominates the blend film formation and the final morphology. Furthermore, Time-resolved photoluminescence, which is employed for the first time as an in situ method for such drying studies, allows to quantitatively determine the extent of dynamic and static quenching, as well as the relative change of quantum yield during film formation. This work contributes to a fundamental understanding of microstructure formation during the processing of different blend films. The presented setup is considered to be an important tool for the future development of blend inks for solution-cast organic or hybrid electronics. Funding Agencies|Knut and Alice Wallenberg Foundation through the project "Mastering Morphology for Solutionborne Electronics" [2016.0059]; Wallenberg Scholar grant from the Knut and Alice Wallenberg Foundation; Swedish Government Strategic Research Area in Material Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [200900971]; Swedish Research CouncilSwedish Research CouncilEuropean Commission [2017-04123]; China Scholarship CouncilChina Scholarship Council

Lignin has been proposed as electricity storage materials due to the redox activity of quinone (Q) and hydroquinone (QH(2)) groups, which can be formed in lignin. Scalable and low-cost lignosulfonate (LS)/graphite hybrid material electrodes have been developed. It is important to investigate the self discharge mechanism for these electrodes since a high self-discharge rate was observed, which results in loss of energy density and power density. In this work, self-discharge measurements and models are applied to clarify the self-discharge mechanism of the LS/graphite electrodes. A combination of diffusion controlled, activation controlled and charge equilibration mechanisms are indicated during the self discharge process at different charging voltages, due to the faradaic reactions of the Q/QH(2) confined in the electrodes. Our work contributes deeper understanding of the structure and the self-discharge mechanisms of the biopolymer/graphite hybrid electrodes. (C) 2021 The Author(s). Published by Elsevier Ltd.

Obtaining both high open-circuit voltage (V-oc) and short-circuit current density (J(sc)) has been a major challenge for efficient all-polymer solar cells (all-PSCs). Herein, we developed a polymer acceptor PF5-Y5 with excellent optical absorption capability (onset extending to similar to 880 nm and maximum absorption coefficient exceeding 105 cm(-1) in a film), high electron mobility (3.18 x 10(3) cm(2) V-1 s(-1)) and high LUMO level (-3.84 eV) to address such a challenge. As a result, the PBDB-T:PF5-Y5-based all-PSCs achieved a high power conversion efficiency of up to 14.45% with both a high Voc (0.946 V) and a high Jsc (20.65 mA cm(-2)), due to the high and broad absorption coverage, small energy loss (0.57 eV) and efficient charge separation and transport in the device, which are among the best values in the all-PSC field. In addition, the all-PSC shows a similar to 15% improvement in PCE compared to its counterpart small molecule acceptor (Y5)-based device. Our results suggest that PF5-Y5 is a very promising polymer acceptor candidate for applications in efficient all-PSCs. Funding Agencies|Swedish Research CouncilSwedish Research Council [2015-04853, 2016-06146, 2019-04683]; Swedish Research Council FormasSwedish Research CouncilSwedish Research Council Formas; Wallenberg Foundation [2017.0186, 2016.0059]; Innovation fund Denmark (INKA project); Sino-Danish Centre for Education and Research (SDC); King Abdullah University of Science and Technology (KAUST)King Abdullah University of Science & Technology [OSR-2018-CARF/CCF-3079]; Office of Sponsored Research (OSR) [OSR-2018-CARF/CCF-3079]; Jinan University Postdoctoral Science Foundation; China Postdoctoral Science FoundationChina Postdoctoral Science Foundation [2020M673054]; National Natural Science Foundation of ChinaNational Natural Science Foundation of China (NSFC) [22005121, 61805009]

Internet-of-things which requires electronics, energy convertor and storage must be low-cost, recyclable and environmentally friendly. In the development of printed batteries, ideally all the components (electrode and electrolyte) must be printable to ensure low-cost manufacturing via printing technologies. Most of the printed batteries suffer with low power. One of the reasons is the poor ionic conductivity of the electrolyte due to the high viscosity needed for printing relatively thick layers. In the present work we have demonstrated a new class of electrolyte promising for printed organic batteries following the concept of water-in-polymer salt electrolytes (WIPSEs). These highly concentrated electrolytes of potassium polyacrylate are non-flammable, low cost and environmentally friendly. They possess high ionic conductivities (45-87 mS/cm) independent on the macroscopic viscosities varying from 7 to 33000 cP. The decoupling between ionic transport and macroscopic viscosity enables us to demonstrate organic batteries based on WIPSEs that can deliver a high and constant power (similar to 4.5 kW/kg; 7.1-11 mW/cm(2)) independent on the viscosity of the electrolytes. The tunability of the viscosity presents a prerequisite for printed technology manufacturing and compatibility with printed batteries. Funding Agencies|Proof-of-Concept project "Paper Batteries"; "Wallenberg Wood Science Center" - Knut and Alice Wallenberg (KAW) foundation; Swedish Research Council [201605990]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009-00971]; Wallenberg Scholar grants from KAW

The dissociation of hybrid local exciton and charge transfer excitons (LE-CT) in efficient bulk-heterojunction nonfullerene solar cells contributes to reduced nonradiative photovoltage loss, a mechanism that still remains unclear. Herein we studied the energetic and entropic contribution in the hybrid LE-CT exciton dissociation in devices based on a conjugated terpolymer. Compared with reference devices based on ternary blends, the terpolymer devices demonstrated a significant reduction in the nonradiative photovoltage loss, regardless of the acceptor molecule, be it fullerene or nonfullerene. Fourier transform photocurrent spectroscopy revealed a significant LE-CT character in the terpolymer-based solar cells. Temperature-dependent hole mobility and photovoltage confirm that entropic and energetic effects contribute to the efficient LE-CT dissociation. The energetic disorder value measured in the fullerene- or nonfullerene-based terpolymer devices suggested that this entropic contribution came from the terpolymer, a signature of higher disorder in copolymers with multiple aromatic groups. This gives new insight into the fundamental physics of efficient LE-CT exciton dissociation with smaller nonradiative recombination loss.

The organic Eu3+-complex [Eu(TTA)3Phen] has been incorporated into the channels of surface-modified frustules from diatoms as a key material to absorb and convert UV-photons to visible luminescence. Systematic investigation results indicate that the organic Eu3+-complex encapsulated in the functionalized diatomite channels exhibits enhanced luminescence and longer lifetime, owning to the Eu(TTA)3Phen complex interacting with its surrounding silylating agents. The organic Eu3+-complex-anchored porous diatomite hybrid luminescent material was compounded with polyethylene terephthalate (PET) by using a mini-twin screw extruder to prepare a self-supporting film of the hybrid material. Besides, the UV absorption properties of the composite films were investigated. These films will potentially be related to the UV protection of photovoltaic devices., Graphical abstract

The key figure-of-merit for materials in stationary energy storage applications, such as large-scale energy storage for buildings and grids, is the cost per kilo per electrochemical cycle, rather than the energy density. In this regard, forest-based biopolymers such as lignin, are attractive, as they are abundant on Earth. Here, we explored lignin as an electroactive battery material, able to store two electrons per hydroquinone aromatic ring, with the targeted operation in aqueous electrolytes. The impact of the sulfonation level of lignin on the performance of its composite electrode with carbon was investigated by considering three lignin derivatives: lignosulfonate (LS), partially desulfonated lignosulfonate (DSLS), and fully desulfonated lignin (KL, lignin produced by the kraft process). Partial desulfonation helped in better stability of the composite in aqueous media, simultaneously favoring its water processability. In this way, a route to promote ionic conductivity within the lignin/carbon composite electrodes was developed, facilitating the access to the entire bulk of the volumetric electrodes. Electrochemical performance of DSLS/C showed highly dominant Faradaic contribution (66%) towards the total capacity, indicating an efficient mixed ionic-electronic transport within the lignin-carbon phase, displaying a capacity of 38 mAh/g at 0.25 A/g and 69% of capacity retention after 2200 cycles at a rate of 1 A/g.

Microfluidic technologies are highly adept at generating controllable compositional gradients in fluids, a feature that has accelerated the understanding of the importance of chemical gradients in biological processes. That said, the development of versatile methods to generate controllable compositional gradients in the solid‐state has been far more elusive. The ability to produce such gradients would provide access to extensive compositional libraries, thus enabling the high‐throughput exploration of the parametric landscape of functional solids and devices in a resource‐, time‐, and cost‐efficient manner. Herein, the synergic integration of microfluidic technologies is reported with blade coating to enable the controlled formation of compositional lateral gradients in solution. Subsequently, the transformation of liquid‐based compositional gradients into solid‐state thin films using this method is demonstrated. To demonstrate efficacy of the approach, microfluidic‐assisted blade coating is used to optimize blending ratios in organic solar cells. Importantly, this novel technology can be easily extended to other solution processable systems that require the formation of solid‐state compositional lateral gradients., The authors would like to acknowledge financial support from the Spanish Ministry of Economy, Industry and Competitiveness through the “Severo Ochoa” Programme 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. J.P.‐L. acknowledges the European Research Council Starting Grant microCrysFact (ERC‐2015‐STG No. 677020) and the Swiss National Science Foundation (200021_181988) and ETH Zürich. R. R.‐T. acknowledges the support from Generalitat de Catalunya and the COFUND programme of the Marie Curie Actions of the 7th R&D Framework Programme of the European Union (BP‐B 00256). X.R.‐M. acknowledges the departments of Physics, Chemistry and Geology of the Autonomous University of Barcelona (UAB) as coordinators of the PhD programme in Materials Science. X.R.‐M. and C.F. acknowledge Nicole Kleger‐Schai from ETH Zürich for her valuable help in using the rheometer. X.R.‐M. and M.C.‐Q. acknowledge Dr. Joan M. Cabot from the University of Tasmania for fruitful discussions on 3D printing. D.B.A. thanks the University of Nottingham Beacon Propulsion Futures.

The mass implementation of renewable energies is limited by the absence of efficient and affordable technology to store electrical energy. Thus, the development of new materials is needed to improve the performance of actual devices such as batteries or supercapacitors. Herein, the facile consecutive chemically oxidative polymerization of poly(1-amino-5-chloroanthraquinone) (PACA) and poly(3,4-ethylenedioxythiophene (PEDOT) resulting in a water dispersible material PACA-PEDOT is shown. The water-based slurry made of PACA-PEDOT nanoparticles can be processed as film coated in ambient atmosphere, a critical feature for scaling up the electrode manufacturing. The novel redox polymer electrode is a nanocomposite that withstands rapid charging (16 A g−1) and delivers high power (5000 W kg−1). At lower current density its storage capacity is high (198 mAh g−1) and displays improved cycling stability (60% after 5000 cycles). Its great electrochemical performance results from the combination of the redox reversibility of the quinone groups in PACA that allows a high amount of charge storage via Faradaic reactions and the high electronic conductivity of PEDOT to access to the redox-active sites. These promising results demonstrate the potential of PACA-PEDOT to make easily organic electrodes from a water-coating process, without toxic metals, and operating in non-flammable aqueous electrolyte for large scale pseudocapacitors.

PEDOT:PSS is a well studied organic conductor, commonly used as a transparent electrode material in printed organic devices such as organic solar cells. PEDOT:PSS thin films are known to be uniaxially anisotropic and exhibit a lower extinction coefficient and lower refractive index in the out of plane direction. To determine the maximum attainable photocurrent in thin film solar cells, the optical power dissipation can be calculated by the transfer matrix method. However, until now the anisotropic properties of PEDOT:PSS films have not been included in the model. In this work we have included an uniaxial anisotropic treatment of PEDOT:PSS films. We investigate reversed and semitransparent solar cells, with aluminum and PEDOT:PSS respectively as the second electrode and PEDOT:PSS as the top electrode, as compared to devices with isotropic PEDOT:PSS electrodes. For p-polarized light at large oblique incidence the inclusion of anisotropy shows a gain of over 7% for the maximum photocurrent in reversed solar ...

In recent years, all-polymer solar cells (all-PSCs), incorporating active layers based on blends of electron-donor (D) and acceptor (A) polymers, have drawn attention because of the advantages they hold in the flexibility of choosing the D:A combinations to modulate their energy levels and to improve their overall open-circuit voltages (V oc ) and power conversion efficiencies (PCE)s. V oc is one of the key parameters for the determination of the PCEs of PSCs. In this work, we synthesized six donor polymers with three different side chains appended to the 4,8-di(thiophen-2-yl)benzo[1,2-b:4,5-b′]dithiophene (BDT) units. By substituting carbon with sulfur and silicon atoms at the 5-position of the thiophenes attached to the BDT units, the highest occupied molecular orbital (HOMO) levels of the donor polymers could be successfully lowered. As anticipated, the V oc values of the resulting all-PSCs increased along with the lowering of the HOMO levels of the donor polymers. Among the six all-PSCs, the PBDT-BDD:PNDI-T10 all-PSC realized a balance between the photovoltage and photocurrent, where a decent PCE of 5.6% was obtained with a V oc of 0.9 V and a photocurrent of 10.5 mA/cm 2 .

In organic photovoltaics, efficient charge generation relies on our ability to convert excitons into free charges. Efficient charge separation from “energetic excitons” has been understood to be governed by delocalization effects promoted by molecular aggregation. A remaining puzzle is, however, the mechanism underlying charge generation via relaxed interfacial charge-transfer (CT) excitons that also exhibit an internal quantum efficiency close to unity. Here, we provide evidence for efficient charge generation via CT state absorption over a temperature range of 50–300 K, despite an intrinsically strong Coulomb binding energy of about 400 meV that cannot be modified by fullerene aggregation. We explain our observation by entropy-driven charge separation, with a key contribution from energy disorder. The energy disorder reduces the charge generation barrier by substantially gaining the entropy as electron–hole distance increases, resulting in efficient CT exciton dissociation. Our results underline an emer...

Scalable production methods and low-cost materials with low embodied energy are key to success for organic solar cells. PEDOT(PSS) electrodes meet these criteria and allow for low-cost and all solution-processed solar cells. However, such devices are prone to shunting. In this work we introduce a roll-to-roll lamination method to construct semitransparent solar cells with a PEDOT(PSS) anode and an polyethyleneimine (PEI) modified PEDOT(PSS) cathode. We use the polymer:PCBM active layer coated on the electrodes as the lamination adhesive. Our lamination method efficiently eliminates any shunting. Extended exposure to ambient degrades the laminated devices, which manifests in a significantly reduced photocurrent extraction when the device is illuminated through the anode, despite the fact that the PEDOT(PSS) electrodes are optically equivalent. We show that degradation-induced electron traps lead to increased trap-assisted recombination at the anode side of the device. By limiting the exposure time to ambient during production, degradation is significantly reduced. We show that lamination using the active layer as the adhesive can result in device performance equal to that of conventional sequential coating.

We demonstrate that voltage losses due to both radiative and non-radiative recombination of charge carriers are strongly dependent on D/A phase separation. By processing the active layer with various solvent additives, we create distinct morphologies that lead to significantly different device open-circuit voltages (VOC), even though the charge transfer state energy (ECT) of the D/A blend remains rather constant. We find that radiative recombination losses are significantly increased for a finely intermixed morphology, due to the large D/A interface area. This leads to a total recombination loss of ECT − qVOC ≈ 0.7 eV. However, considerably smaller losses (0.5 eV), due to suppressed non-radiative recombination, are possible in solar cells where the D/A materials are organized to only allow for selective charge carrier extraction. Using a drift diffusion model, we show that the origin of the reduced non-radiative recombination losses is related to an effect which has not been considered for ‘optimized’ solar cells – the suppression of minority carrier diffusion to the ‘wrong’ contact. Our results suggest that the built-in field is not sufficiently strong even in ‘optimized’ organic solar cells and that selective carrier extraction is critical for further improvements in VOC.

Vapour phase polymerized (VPP) PEDOT obtained using triblock copolymer PEG–PPG–PEG:Fe(III) tosylate polymeric oxidative layers has shown record-high conductivity and unique thermoelectric properties. These properties are related to the molecular weight, morphology and doping of PEDOT. Here we show that in its unwashed condition, the PEDOT chain adopts a neutral benzenoid conformation. The polymer chain converts into the charged quinoid structure after the removal of oxidizers with solvent washing. X-ray diffraction results suggest that the dopant is also incorporated into the packed polymer after the washing process. The changes in the chain structure and doping lead to the characteristic polaron and bipolaron absorption in the 800 and 1200 nm range. We observed a large contraction of the film after washing that is likely due to these changes, along with the removal of excessive polymer:oxidizer trapped in the PEDOT matrix. The contraction of films can be completely suppressed by mechanical clamping. PEDOT films without contraction show both a higher conductivity and higher optical transparency.

In this work, we demonstrate all-polymer solar cells where all the layers are made from polymers. We use PEDOT:PSS as the semitransparent anode and polyethyleneimine modified PEDOT:PSS as the semitransparent cathode, both of which are slot-die printed on polyethylene terephthalate (PET). Active layers are deposited on the cathode and anode surfaces by spin coating separately. These layers are then joined through a roll-to-roll compatible lamination process. This results in a semitransparent and flexible solar cell. We have used two polymer-polymer systems and several combinations, and the highest power conversion efficiency (PCE) obtained is 2.3% with a mean transparency amp;gt;35% within the visible light range. By laminating a thin layer acceptor polymer to a thick polymer-polymer blend, we can improve the performance by reducing recombination, compared to laminating blend to blend, which is verified by the trap-limited charge transport, CELIV and electroluminescence. Funding Agencies|Swedish Energy Agency; Knut and Alice Wallenberg foundation (KAW); China Scholarship Council (CSC)

The search for the alternatives to expensive synthesized conjugated polymers as interfaces in polymer solar cells (PSCs), which could largely decrease the cost and promote the commercialization process of PSCs, is now highly relevant. To introduce natural polymer as the interface layer for the high-efficiency PSCs would be a potential choice. In this study, a purely natural polysaccharide from ocean without any conjugated structure, sodium alginate (SA), is utilized as efficient electron transport layer (ETL) to replace the conjugated star molecule, poly [(9,9-bis(3'-(N,NdiMethyl)-NethylaMMoiniuM-propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)]dibroMide (PFN–Br), and modify the aluminum (Al) electrode in conventional PSCs. The reduction of the work function of Al is successfully achieved by SA forming a dipole and keeping the ohmic contact at the interface. Meantime, the ideal charge transfer and exciton dissociation are realized, along with decreasing charge recombination, resulting in a comparable power conversion efficiency (PCE) with devices of PFN-Br as ETL. For poly([2,6′-4,8-di(5-ethylhexylthienyl)benzo[1,2-b; 3,3-b]dithiophene]3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl):[6,6]-phenyl-C71-butyric acid methyl ester (PTB7-Th:PC71BM) system, PCE is increased to 9.5% and for Poly[(2,6-(4,8-bis(5-(2-ethylhexyl-3-fluoro)thiophen-2-yl)-benzo[1,2-b:4,5-b’]dithio-phene))-alt-(5,5-(1′,3′-di-2-thienyl-5′,7′-bis(2-ethylhexyl)benzo[1′,2′-c:4′,5′-c’]dithio-phene-4,8-dione)]:3,9-bis(2methylene-((3-(1,1-dicyanomethylene)-6,7-difluoro)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2′,3′-d']-s-indaceno[1,2-b:5,6-b'] dithiophene (PM6:IT-4F) system, PCE 13.4%, respectively, which illustrates a promising future for photovoltaic research of natural alginate non-conjugated polyelectrolyte in conventional PSCs.

All-polymer blends are promising materials for organic electronics. Their performance critically depends on the quality of mixing of the electron donor and acceptor polymers and on the local chain organization. We investigated spatially resolved photoluminescence properties of as-prepared and annealed blends of poly[2,3-bis(3-octyloxyphenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5-diyl] (TQ1) and poly(N,N-bis-2-octyldodecyl-naphtalene-1,4,5,8-bisdicarboximide-2,6-diyl-alt-5,5–2,2-bithiophene) (N2200) using two-dimensional polarization imaging (2D POLIM). N2200 is known to aggregate into fiber-like morphologies with a few hundreds of nanometers lateral extensions. Our findings suggest a highly parallel chain organization within individual domains. Comparing blends differing in the batch of the N2200 component, we could relate decreased power conversion efficiencies of the corresponding devices to aggregation of N2200 in tens of micrometer-sized elongated structures. TQ1 showed less sensitivity to preparation...

Counterion exchange has been introduced as a method to modify properties of anionic conjugated polyelectrolyte (CPE) blends. Blending of two self-doped CPEs having metallic and semiconducting behavior has been achieved from two different solvents, by exchanging the counterion of the metallic component. Different blending conditions lead to films exhibiting different optical properties, depending on the aggregation states of the CPEs. Conductance responses for the blends showed the opportunity to tune threshold voltage of the films both by blending and counterion exchange. Therefore, the blends have been exploited for the fabrication of accumulation mode organic electrochemical transistors. These devices exhibit short switching times and high transconductance, up to 15.3 mS, as well as high stability upon fast pulsed cycles, retaining 88% of the drain currents after 2 × 103 cycles.

Current all polymer solar cells still suffer from low fill factors (FF) and short-circuit current density (Jsc) compared with the conventional polymer/fullerene system. Herein in this work, devices using PTP8 as the electron donor and [70]PCBM as well as widely used polymer N2200 as the electron acceptor were systematically studied and compared. The major loss mechanisms in the all polymer solar cells were investigated to understand their relatively lower performance than the PTP8/fullerene system. By performing in-depth analysis on ultrafast transient transmission spectroscopy results, we estimated that in PTP8/N2200 device nearly half of the charges recombine geminately, which is confirmed as the major factor hindering the device performance of all polymer solar cells compared with polymer/fullerene system. Through thorough morphology analysis, the low charge generation efficiency is attributed to the reduced crystallinity of N2200 in the blend film and the unfavorable face-to-edge orientation at the donor/acceptor heterojunction. Coupling these results with knowledge from efficient polymer/fullerene systems, the future design of new polymers can devote to increase the attraction between the π face of donor and acceptor, leading to enhanced face-to-face orientation at the heterojunction, while maintaining a high π-π stacking order for each polymer.

This paper presents the work carried out within the European project RENAISSANCE-ITN, which was dedicated to the development of innovative polyelectrolytes for energy and environmental applications. Within the project different types of innovative polyelectrolytes were synthesized such as poly(ionic liquid)s coming from renewable or natural ions, thiazolium cations, catechol functionalities or from a new generation of cheap deep eutectic monomers. Further, macromolecular architectures such as new poly(ionic liquid) block copolymers and new (semi)conducting polymer/polyelectrolyte complexes were also developed. As the final goal, the application of these innovative polymers in energy and the environment was investigated. Important advances in energy storage technologies included the development of new carbonaceous materials, new lignin/conducting polymer biopolymer electrodes, new iongels and single-ion conducting polymer electrolytes for supercapacitors and batteries and new poly(ionic liquid) binders for batteries. On the other hand, the use of innovative polyelectrolytes in sustainable environmental technologies led to the development of new liquid and dry water, new materials for water cleaning technologies such as flocculants, oil absorbers, new recyclable organocatalyst platforms and new multifunctional polymer coatings with antifouling and antimicrobial properties. All in all this paper demonstrates the potential of poly(ionic liquid)s for high-value applications in energy and enviromental areas. © 2017 Society of Chemical Industry

Herein we utilize insulin to prepare amyloid based chiral heliceswith either right or left handed helicity. We demonstrate that thehelices can be utilized as structural templates for the conductingpolymer alkoxysulfonate poly(ethylenedioxythiophene) (PEDOT-S).The chirality of the helical assembly is transferred to PEDOT-S asdemonstrated by polarized optical microscopy (POM) and CircularDichroism (CD). Analysis of the helices by conductive atomic force(c-AFM) shows significant conductivity. In addition the morphologyof the template structure is stabilized by PEDOT-S. Theseconductive helical structures represent promising candidates in ourquest for THz resonators. Funding agencies: Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [SFO-Mat-LiU 2009-00971]; Strategic Research Foundation through the project OPEN; Knut and Alice Wallenberg foundation; Wallenberg Scholar gran

Thin film solar cells, and in particular printed organic solar cells, offer a potential route to a low cost power generation from sunlight. However, manufacturing these solar cells rapidly generate ...

The interface between electron-donating (D) and electron-accepting (A) materials in organic photovoltaic (OPV) devices is commonly probed by charge-transfer (CT) electroluminescence (EL) measurements to estimate the CT energy, which critically relates to device open-circuit voltage. It is generally assumed that during CT-EL injected charges recombine at close-to-equilibrium energies in their respective density of states (DOS). Here, we explicitly quantify that CT-EL instead originates from higher-energy DOS site distributions significantly above DOS equilibrium energies. To demonstrate this, we have developed a quantitative and experimentally calibrated model for CT-EL at organic D/A heterointerfaces, which simultaneously accounts for the charge transport physics in an energetically disordered DOS and the Franck–Condon broadening. The 0–0 CT-EL transition lineshape is numerically calculated using measured energetic disorder values as input to 3-dimensional kinetic Monte Carlo simulations. We account for vibrational CT-EL overtones by selectively measuring the dominant vibrational phonon-mode energy governing CT luminescence at the D/A interface using fluorescence line-narrowing spectroscopy. Our model numerically reproduces the measured CT-EL spectra and their bias dependence and reveals the higher-lying manifold of DOS sites responsible for CT-EL. Lowest-energy CT states are situated ∼180 to 570 meV below the 0–0 CT-EL transition, enabling photogenerated carrier thermalization to these low-lying DOS sites when the OPV device is operated as a solar cell rather than as a light-emitting diode. Nonequilibrium site distribution rationalizes the experimentally observed weak current-density dependence of CT-EL and poses fundamental questions on reciprocity relations relating light emission to photovoltaic action and regarding minimal attainable photovoltaic energy conversion losses in OPV devices.

Lignin is a promising candidate for energy storage because of its abundance, wide geographic distribution, and low cost as it is mainly available as a low value product from processing of wood into paper pulp. Lignin contains large amounts of potential quinone groups, which can be oxidized and reduced in a two electron process. This redox reaction makes lignin suitable for charge storage. However, lignin is insulating and therefore conductive materials are necessary in lignin electrodes, for whom the cost of the conductive materials hinders the scalable application. Among the organic conductive materials, graphite is one of the cheapest and is easily acquired from nature. In this work, we combine graphite and lignosulfonate (LS) and fabricate LS/graphite organic electrodes under a solvent-free mechanical milling method, without additives. The graphite is sheared into small particles with a size range from 50 nm to 2000 nm. Few-layer graphene is formed during the ball milling process. The LS/graphite hybrid material electrodes with primary stoichiometry of 4/1 (w/w) gives a conductivity of 280 S m