AbstractIn this paper we present the design and synthesis of 25 new low band gap polymers. The polymers were characterized by UV-vis spectroscopy which showed optical band gaps of 2.0–0.9 eV. The polymers which were soluble enough were applied in organic photovoltaics, both small area devices with a spin coated active layer and in large area modules where all layers including the active layer were either roll-to-roll coated or printed. These experiments showed that the design of polymers compatible with roll-toroll coating is not straightforward and that there are various issues such as donor/acceptor fitting within the polymer, side chains to ensure solubility and HOMO/LUMO level alignment with the acceptor (e.g. [60]PCBM) to take into consideration.

Continuous flow methods are utilized in conjunction with direct arylation polymerization (DArP) for the scaled synthesis of the roll-to-roll compatible polymer, poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt-(4,7-di(thiophen-2-yl)-benzo[c][1,2,5]thiadiazole)] (PPDTBT). PPDTBT is based on simple, inexpensive, and scalable monomers using thienyl-flanked benzothiadiazole as the acceptor, which is the first β-unprotected substrate to be used in continuous flow via DArP, enabling critical evaluation of the suitability of this emerging synthetic method for minimizing defects and for the scaled synthesis of high-performance materials. To demonstrate the usefulness of the method, DArP-prepared PPDTBT via continuous flow synthesis is employed for the preparation of indium tin oxide (ITO)-free and flexible roll-coated solar cells to achieve a power conversion efficiency of 3.5% for 1 cm2 devices, which is comparable to the performance of PPDTBT polymerized through Stille cross coupling. These efforts demonstrate the distinct advantages of the continuous flow protocol with DArP avoiding use of toxic tin chemicals, reducing the associated costs of polymer upscaling, and minimizing batch-to-batch variations for high-quality material.

The passage of time from laboratory demonstration of a technology-enabling efficiency value and until methodology and preparative means are in place is explored in this work for the polymer solar cell. Long technical strides need to be taken and efforts much beyond the laboratory solar cell need to be dedicated to bringing new solar cell material discoveries to service as an industrial technology. This includes scaled materials preparation, scaled manufacturing platforms, scaled installation platforms, as well as scaled electronics, monitoring, and control systems. We epitomize this as the "scaling lag'' and highlight its importance when wishing to progress new solar cell materials from science to technology. The scaling gap is an observable element that can be extracted directly from experimental data and can be taken as a sign of technological maturity that can aid early-phase investors in their decision of when to invest in product development based on new technology.

Direct arylation polymerization (DArP) is used to synthesize a variety of carbazole-based copolymers for evaluation in solar cells.

This review summarizes the recent progress in the stability and lifetime of organic photovoltaics (OPVs). In particular, recently proposed solutions to failure mechanisms in different layers of the device stack are discussed comprising both structural and chemical modifications. Upscaling is additionally discussed from the perspective of stability presenting the challenges associated with device packaging and edge protection. An important part of device stability studies is the characterization, and this review provides a short overview of the most advanced techniques for stability characterization reported recently. Lifetime testing and determination is another challenge in the field of organic solar cells and the final sections of this review discuss the testing protocols as well as the generic marker for device lifetime and the methodology for comparing all the lifetime landmarks in one common diagram. These tools were used to determine the baselines for OPV lifetime tested under different ageing conditions. Finally, the current status of lifetime for organic solar cells is presented and predictions are made for progress in the near future.

The position and nature of side chains in the donor–acceptor copolymer were investigated in terms of stability in polymer solar cells.

The stability of polymer solar cells (PSCs) can be influenced by the introduction of particular moieties on the conjugated polymer side chains. In this study, two series of donor-acceptor copolymers, based on bis(thienyl)dialkoxybenzene donor and benzo[c][1,2,5]thiadiazole (BT) or thiazolo[5,4-d]thiazole (TzTz) acceptor units, were selected toward effective device scalability by roll-coating. The influence of the partial exchange (5% or 10%) of the solubilizing 2-hexyldecyloxy by alternative 2-phenylethoxy groups on efficiency and stability was investigated. With an increasing 2-phenylethoxy ratio, a decrease in solar cell efficiency was observed for the BT-based series, whereas the efficiencies for the devices based on the TzTz polymers remained approximately the same. The photochemical degradation rate for PSCs based on the TzTz polymers decreased with an increasing 2-phenylethoxy ratio. Lifetime studies under constant sun irradiance showed a diminishing initial degradation rate for the BT-based devices upon including the alternative side chains, whereas the (more stable) TzTz-based devices degraded at a faster rate from the start of the experiment upon partly exchanging the side chains. No clear trends in the degradation behavior, linked to the copolymer structural changes, could be established at this point, evidencing the complex interplay of events determining PSCs’ lifetime.

The mechanical properties of low-band-gap polymers are important for the long-term survivability of roll to-roll processed organic electronic devices. Such devices, e.g., solar cells, displays, and thin-film transistors, must survive the rigors of roll-to-roll coating and also thermal and mechanical forces in the outdoor environment and in stretchable and ultraflexible form factors. This paper measures the stiffness (tensile modulus), ductility (crack-onset strain), or both of a combinatorial library of 51 low-band-gap polymers. The purpose of this study is to systematically screen a library of low-band-gap polymers to better understand the connection between molecular structures and mechanical properties in order to design conjugated polymers that permit mechanical robustness and even extreme deformability. While one of the principal conclusions of these experiments is that the structure of an isolated molecule only partially determines the mechanical properties another important codeterminant is the packing structure some general trends can be identified. (1) Fused rings tend to increase the modulus and decrease the ductility. (2) Branched side chains have the opposite effect. Despite the rigidity of the molecular structure, the most deformable films can be surprisingly compliant (modulus >= 150 MPa) and ductile (crack-onset strain <= 68%). This paper concludes by proposing a new composite merit factor that combines the power conversion efficiency in a fully solution processed device obtained via roll and roll-to-roll coating and printing (as measured in an earlier paper) and the mechanical deformability toward the goal of producing modules that are both efficient and mechanically stable.

The electron work function, hole concentration and diffusion length were compared for poly(3-hexylthiophene) polymer (P3HT) that is commonly used for construction of solar cells, and two types of native polythiophene (PT) samples which are prospective candidates for this purpose. The polythiophene samples were prepared from 2 different precursors by thermal or chemical treatment at room temperature. Cyclic voltammetry and work function measurements were used for estimating the concentration of holes. The measured data were evaluated assuming the validity of band theory based on the tight-binding model. Published data on the valence bandwidth were used for calculating the value of the overlap integral which is related to the hole effective mass. Energy band diagrams were constructed for all 3 materials. Finally, the exciton diffusion length, which is a critical parameter for the application of conjugated polymer materials in solar cells, was measured by a modified surface photovoltage method. The approach allowed us to identify the differences in the material properties related to the processing method. Morphology of the samples determined by AFM was another tool showing these differences. It is stated that a native polythiophene prepared by treatment with acids is a prospective material for solar cells and shows a similar quality as that produced by a thermal process. (C) 2015 Elsevier Ltd. All rights reserved.

ABSTRACTDespite the emergence of direct arylation polymerization (DArP) as an alternative method to traditional cross‐coupling routes like Stille polymerization, the exploration of DArP polymers in practical applications like polymer solar cells (PSCs) is limited. DArP polymers tend to have a reputation for being marginally inferior to Stille counterparts due to the increased presence of defects that result from unwanted side reactions in direct arylation, such as unselective C‐H bond activation and homocoupling. We report ten DArP protocols across the three major classes of DArP to generate poly[(2,5‐bis(2‐hexyldecyloxy)phenylene)‐alt‐(4,7‐di(thiophen‐2‐yl)benzo[c][1,2,5]thiadiazole)] (PPDTBT). Through evaluation of the method and resulting photophysical and electronic properties, we show not all DArP methods are suitable for generating device‐quality alternating copolymers. When DArP PPDTBT was synthesized in superheated THF with Cs2CO3, neodecanoic acid, and P(o‐anisyl)3, it generated polymers of exceptional quality that performed comparably to Stille counterparts in both roll coated ITO‐free and spin‐coated ITO devices. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 2907–2918

A novel isoindigo containing D–A polymer was developed for large area single junction and tandem solar cells.

Continuous flow methods are employed for the controlled polymerization of the roll‐to‐roll (R2R) compatible polymer PBDTTTz‐4 including optimization and upscaling experiments. The polymerization rate and materials’ quality can be increased significantly with the continuous flow method where reaction times down to 10 min afforded PBDTTTz‐4 with high molecular weight and a constant quality. The flow method enables full control of the molecular weight via tuning of the flow speed, catalyst loading, and temperature and avoids variation in materials’ quality associated with conventional batch synthesis. Upscaling from 300 mg batch synthesis to 10 g flow synthesis affords PBDTTTz‐4 with a production rate of up to 120 g day −1 for a very simple in‐house build flow reactor. An average power conversion efficiency (PCE) of 3.5% is achieved on a small scale (1 cm 2 ) and an average PCE of 3.3% is achieved on a large scale (29 cm 2 ). This shows that small device efficiencies can be scaled when using full R2R processing of flexible and encapsulated carbon‐based modules without the use of vacuum, indium‐tin‐oxide, or silver, with the best achieving a PCE of 3.8% PCE.

Jens W. Andreasen and co-workers identify and surmount the challenges of fast and scalable manufacture of polymer tandem solar cells as reported in article number 1400736. This is accomplished by combining in situ X-ray scattering and the high resolution 3D X-ray vision provided by coherent synchrotron radiation diffractive imaging.

Large area, fullerene-free organic solar cells with improved stability and efficiency of up to 1% are fabricated by the roll-coating process on indium tin oxide free and flexible substrates, under ambient conditions.

Department of Chemistry and Bioscience, A DK-9220, Aalborg East, Denmark. E-mail: yu Sino-Danish Centre for Education and Rese Aarhus, Denmark Department of Energy Conversion and Sto Frederiksborgvej 399, DK-4000, Roskilde, De Department of Engineering, Aarhus Universi † Electronic supplementary informa 10.1039/c4tc02877e ‡ These authors contributed equally to th Cite this: J. Mater. Chem. C, 2015, 3, 1633

Fully roll-coated ITO-free flexible organic solar cells based on a non-fullerene small molecule acceptor with a PCE of 0.65% were fabricated.

The realization of a complete tandem polymer solar cell under ambient conditions using only printing and coating methods on a flexible substrate results in a fully scalable process but also requires accurate control during layer formation to succeed. The serial process where the layers are added one after the other by wet processing leaves plenty of room for error and the process development calls for an analytical technique that enables 3D reconstruction of the layer stack with the possibility to probe thickness, density, and chemistry of the individual layers in the stack. The use of ptychography on a complete 12‐layer solar cell stack is presented and it is shown that this technique provides the necessary insight to enable efficient development of inks and processes for the most critical layers in the tandem stack such as the recombination layer where solvent penetration in fully solution processed 12‐layer stacks is critical in eleven of the steps.

ABSTRACTA screening of direct arylation conditions on a model small molecule system is carried out to develop suitable conditions for the direct arylation polymerization (DArP) of fluorinated copolymers, which are incompatible with conditions previously utilized successfully for nonfluorinated systems. The model system features a coupling between a 2‐substituted thiophene and a pentafluorobenzene, where one of the partners was brominated. A substantial difference in reactivity is observed, demonstrating that the optimal functionalization for direct arylation between a thiophene‐based donor and a highly fluorinated acceptor is a halogenated thiophene and an unfunctionalized fluorinated unit, which is opposite of typical cross coupling reactions, where the acceptor is typically halogenated. The best conditions are applied to the copolymerization of 1,2,4,5‐tetrafluorobenzene and 2,2'‐(2,5‐bis((2‐hexyldecyl)oxy)−1,4‐phenylene)dithiophene. Polymers are free of β‐defects and significant homocoupling. This work further underscores the attractive simplicity, relevance, and ease of DArP while reconfirming its broad compatibility with increasingly popular fluorinated copolymers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 2598–2605