Large-area Organic Solar Cells Research Articles

New Perylene Diimide Dyes and Inks for Large Area Roll-Coated Organic Solar Cells

Polycyclic aromatic molecules, especially perylene diimide based dyes, are widely used as electronic materials in photovoltaic devices.1 Our team at the University of Calgary has been actively developing modified perylene diimides for use in a range of solution processed electronic devices including organic solar cells,2 organic light emitting diodes,3 transistors and sensors,4 electrochromic films,5 and photo/electro cathodes.6 This presentation will detail the design and synthesis of several classes of modified perylene diimides for specific use in large area organic solar cell devices and modules, primarily as cathode interlayers in both conventional and inverted type cells, but also as non-fullerene acceptors. Structure-property relationships, the formation of functional large area films via slot-die coating using green solvents, and utility both small area devices and flexible modules will be discussed. Applications as indoor light recycling devices and integration into operational greenhouses will be presented.1 Journal of Materials Chemistry A, 2021, 9 6775-67892 Journal of Materials Chemistry C, 2020, 8, 13430-134383 Journal of Materials Chemistry C, 2020, 9, 2314-23194 Journal of Materials Chemistry C, 2021, 9, 13630-136345 Journal of Materials Chemistry C, 2024, 12, 1710-17176 Chemical Science, 2022, 13, 1049-1059

Inner/Outer Side Chain Engineering of Non-Fullerene Acceptors for Efficient Large-Area Organic Solar Modules Based on Non-Halogenated Solution Processing in Air.

Achieving efficient and large-area organic solar modules via non-halogenated solution processing is vital for the commercialization yet challenging. The primary hurdle is the conservation of the ideal film-formation kinetics and bulk-heterojunction (BHJ) morphology of large-area organic solar cells (OSCs). A cutting-edge non-fullerene acceptor (NFA), Y6, shows efficient power conversion efficiencies (PCEs) when processed with toxic halogenated solvents, but exhibits poor solubility in non-halogenated solvents, resulting in suboptimal morphology. Therefore, in this study, the impact of modifying the inner and outer side-chains of Y6 on OSC performance is investigated. The study reveals that blending a polymer donor, PM6, with one of the modified NFAs, namely N-HD, achieved an impressive PCE of 18.3% on a small-area OSC. This modified NFA displays improved solubility in o-xylene at room temperature, which facilitated the formation of a favorable BHJ morphology. A large-area (55 cm2) sub-module delivered an impressive PCE of 12.2% based on N-HD using o-xylene under ambient conditions. These findings underscore the significant impact of the modified Y6 derivatives on structural arrangements and film processing over a large-area module at room temperature. Consequently, these results are poised to deepen the comprehension of the scaling challenges encountered in OSCs and may contribute to their commercialization.

Controlling vertical phase separation and crystallization via solvent synergy strategy to empower layer-by-layer processed organic solar cells

The novel sequential layer-by-layer (LbL) processed organic solar cells (OSCs) have attracted continuous attention due to their advantages of ideal vertical phase separation, efficient charge transport and collection, and potentiality for large-scale production from laboratory to factory. Herein, a solvent synergy strategy is put forward to control morphology, crystallization and vertical phase distribution of blend films, which means the donor PM6 and acceptor Y6 treated by high/low boiling point solvents are fabricated using LbL solution process, respectively. Based on device with a configuration of ITO/ZnO/PM6:Y6/MoO3/Ag, OSCs derived from the solvent synergy strategy can obtain a remarkable power conversion efficiency (PCE) up to 15.03%, which is comparable to that of the bulk heterojunction devices prepared by conventional one-step solution method. This impressive result provides an insightful understanding of phase segregation and crystalllization in LbL processed OSCs assisted by the solvent synergy strategy. It lays the foundation for fabrication and optimization of high-performance, large-area OSCs in industrial production.

Heterogeneous Nucleating Agent for High-Boiling-Point Nonhalogenated Solvent-Processed Organic Solar Cells and Modules.

High-boiling-point nonhalogenated solvents are superior solvents to produce large-area organic solar cells (OSCs) in industry because of their wide processing window and low toxicity; while, these solvents with slow evaporation kinetics will lead excessive aggregation of state-of-the-art small molecule acceptors (e.g. L8-BO), delivering serious efficiency losses. Here, a heterogeneous nucleating agent strategy is developed by grafting oligo (ethylene glycol) side-chains on L8-BO (BTO-BO). The formation energy of the obtained BTO-BO; while, changing from liquid in a solvent to a crystalline phase, is lower than that of L8-BO irrespective of the solvent type. When BTO-BO is added as the third component into the active layer (e.g. PM6:L8-BO), it easily assembles to form numerous seed crystals, which serve as nucleation sites to trigger heterogeneous nucleation and increase nucleation density of L8-BO through strong hydrogen bonding interactions even in high-boiling-point nonhalogenated solvents. Therefore, it can effectively suppress excessive aggregation during growth, achieving ideal phase-separation active layer with small domain sizes and high crystallinity. The resultant toluene-processed OSCs exhibit a record power conversion efficiency (PCE) of 19.42% (certificated 19.12%) with excellent operational stability. The strategy also has superior advantages in large-scale devices, showing a 15.03-cm2 module with a record PCE of 16.35% (certificated 15.97%).

Morphological Homogeneity and Interface Modification as Determinant Factors of the Efficiency and Stability for Upscaling Organic Solar Cell.

Morphological homogeneity and interfacial traps are essential issues to achieve high-efficiency and stable large-area organic solar cells (OSCs). Herein, by the investigation of three quinoxaline-based acceptors, i.e., PM6:Qx-1, PM6:Qx-2, and PM6:Qx-p-4Cl, the performance degradation in up-scaling OSCs is explored. The inhomogeneous morphology in PM6:Qx-2 induces a nonuniform spatial distribution of charge generation, showing a rapid decline in efficiency and stability in large-area OSCs. In comparison, the homogeneous morphology in PM6:Qx-1 and PM6:Qx-p-4Cl alleviates the stability drop. When utilizing 2-phenylethylmercaptan to fill the interfacial traps, the stability drop disappears for PM6:Qx-1 and PM6:Qx-p-4Cl, while it persists for PM6:Qx-2. The PM6:Qx-1 large-are device yields a high efficiency of 13.47% and superior thermal stability (T80 = 2888h). Consequently, the interface modification dominates the performance degradation of large-area devices with homogeneous morphology, while it cannot eliminate the traps in inhomogeneous film. These results provide a clear understanding of degradation mechanisms in upscaling devices.

Unraveling the electrical energy loss in silver nanowire electrodes for flexible and Large-Area organic solar cells

Although the transparency and sheet resistance of silver nanowire (AgNW) electrodes are comparable to those of rigid indium-tin-oxide electrodes, flexible organic solar cells (FOSCs) are still less efficient than their rigid counterparts. Herein, by recording the microscopic photocurrent images of AgNW-based FOSCs in operation, it has been revealed that the limited lateral charge collection range of AgNW leads to inevitable electrical energy loss. The regulation of carrier mobility and energy level of adjacent ZnO electron transport layer increases the effective collection range of AgNWs by 1.8 times and uniform the electrical potential distribution in FOSCs. The D18:Y6:PC71BM-based FOSCs achieve a power conversion efficiency of approaching 18%. Moreover, the performance drop of large-area FOSCs is significantly reduced due to the improved charge collection on large area scale. This work provides an intuitive insight into the electrical energy loss mechanism of AgNW electrodes and demonstrates an electric field regulation strategy in FOSCs.

Regulating pre-aggregation in non-halogenated solvent to enhance the efficiency of organic solar cells

Optimizing the morphology of an active layer in organic solar cells (OSCs) through precise control of precursor solution aggregation is a crucial step in enhancing photovoltaic performance. However, the considerable difference in solubility among organic materials in environmentally friendly solvents, such as non-halogenated solvents, poses a challenge in simultaneously modulating the pre-aggregation of both donor and acceptor. Herein, we employ a synergistic approach that involves heat treatment and the addition of a solid additive to regulate the aggregation behavior of PM6 (donor) and BTP-ec9 (acceptor) within an o-xylene solvent. Our findings reveal that PM6 exhibits strong temperature-dependent aggregation tendencies, while the solid additive 1,4-diiodobenzene (DIB) notably influences the aggregation of BTP-ec9. Thus, treating the precursor solution at 90 °C and adding DIB result in a well-matched aggregation between donor and acceptor, effectively optimizing the crystallization and phase separation morphology of the active layer. This strategic intervention leads to an outstanding efficiency of 18.07%, with a fill factor of 78.65%, for the corresponding device, which ranks among the highest efficiencies for the non-halogenated solvent-processed OSCs. Importantly, this study also demonstrates the feasibility of fabricating thick-film and large-area OSCs by blade-coating, achieving efficiencies of 16.15% and 15.29%, showcasing substantial potential for commercial applications.

Multi-functionally ferroelectric polymer promotes highly-efficient large-area organic solar cells with excellent comprehensive performance

Developing high-performance active layer with excellent comprehensive performance is very crucial for the commercialization of organic solar cells (OSCs). Here, we demonstrate the multi-function of ferroelectric polymer polyvinylidene fluoride (PVDF) in improving the device comprehensive performance including device efficiency, stability, green-solvent large-area printing and mechanical property. Addition of PVDF not only enhances the build-in field to promote charge kinetics, but also develops robust network through strong interaction and chain entanglement between polymer donor and PVDF. Importantly, such robust network effectively protects the active layer from excessive flushing/swelling between D/A component to optimize layer-by-layer (LBL) deposition, induce a favorable vertical phase distribution and prolong the film-forming process, consequently facilitating green-solvent blade-coating printing, improving device efficiency and stability, and enhancing device mechanical flexibility. Due to the multiple advantages of PVDF, the PM6/BTP-eC9 obtains an excellent efficiency of 18.35% for BTP-eC9-based LBL devices. By blade-coating printing with green solvent, one of the highest efficiencies of 16.40% is achieved for large-area (1.21 cm2) binary device. Particularly, toughness is used to comprehensively evaluate mechanical property of OSCs, showing significant improvement with simultaneously enhanced fracture strength and tensile strain, and enabling small molecule-based system even have comparable mechanical flexibility and comprehensive performance to the all-polymer system.

Achieving efficient flexible and large-area organic solar cells via additive-assisted fluorous solvent soaking

Developing flexible and large-area organic solar cells (OSCs) is of vital importance for advancing the commercialization. However, using solvent additives during the film deposition is tricky and unpredictable for the large-area device. Furthermore, typical post-treatments like high-temperature thermal annealing might cause the undesired deformation of the flexible substrate, thus adversely affecting the photovoltaic performance. Herein, a new device engineering namely additive-assisted fluorous solvent soaking (AFSS), is developed as an alternative approach for OSCs fabrication. No solvent additive is used in the active layer deposition, providing more uniform films in large-area processing. The fresh-made film is subsequently soaked in a mixture of fluorous solvent and a tiny amount of solvent additive, wherein the cyclic movement of the fluorous solvent associated with the additive could facilitate the molecular reorganization at relatively low temperature (40 °C), and thus optimizing the morphology of the active layer. Compared with the traditional method, AFSS is more effective in various OSCs including the rigid or flexible substrates and the conventional or inverted device architectures. An ultra-flexible and large-area device fabricated by AFSS realizes a PCE of 12.63%. This work provides a robust and practical strategy to fabricate OSCs as well as other optoelectronic devices at low temperature.

Optimization of Large-Area PM6:D18-CL:Y6 Ternary Organic Solar Cells: The Influence of Film Thickness, Annealing Temperature, and Connection Configuration

This research focuses on the fabrication and optimization of large-area PM6:D18-CL:Y6 ternary organic solar cells, with a particular emphasis on film thickness, annealing temperature, and the connection configuration’s impact on device performance. The experimental findings indicate that an optimal film thickness of approximately 105 nm fosters the formation of a well-interconnected network, reducing defects and significantly improving both the fill factor, which reaches 46.2%, and the power conversion efficiency (PCE) at 7.2%. An annealing temperature of 110 °C stands out as the ideal condition, resulting in the highest PCE of 8.15%. Notably, excessively high annealing temperatures lead to material aggregation, compromising device performance. Regarding the connection configurations, the study demonstrates that the 5-series 4-parallel arrangement surpasses traditional setups, achieving an impressive output power of 0.11 W. In conclusion, the meticulous control of the film thickness and annealing temperature is paramount for achieving a high PCE in large-area PM6:D18-CL:Y6 ternary organic solar cells. The 5-series 4-parallel configuration exhibits considerable promise for an enhanced power output, offering valuable insights into the development and industrialization of large-area organic solar cells.

Hexanary blends: a strategy towards thermally stable organic photovoltaics

Non-fullerene based organic solar cells display a high initial power conversion efficiency but continue to suffer from poor thermal stability, especially in case of devices with thick active layers. Mixing of five structurally similar acceptors with similar electron affinities, and blending with a donor polymer is explored, yielding devices with a power conversion efficiency of up to 17.6%. The hexanary device performance is unaffected by thermal annealing of the bulk-heterojunction active layer for at least 23 days at 130 °C in the dark and an inert atmosphere. Moreover, hexanary blends offer a high degree of thermal stability for an active layer thickness of up to 390 nm, which is advantageous for high-throughput processing of organic solar cells. Here, a generic strategy based on multi-component acceptor mixtures is presented that permits to considerably improve the thermal stability of non-fullerene based devices and thus paves the way for large-area organic solar cells.

Impact of solvents on doctor blade coatings and bathocuproine cathode interlayer for large-area organic solar cell modules

Efforts to commercialize organic solar cells (OSCs) by developing roll-to-roll compatible modules have encountered challenges in optimizing printing processes to attain laboratory-level performance in fully printable OSC architectures. In this study, we present efficient OSC modules fabricated solely through printing methods. We systematically evaluated the impact of processing solvents on the morphology of crucial layers, such as the hole transport, photoactive, and electron transport layers, applied using the doctor blade coating method, with a particular focus on processability. Notably, deposition of charge transport layer using printing techniques is still a challenging task, mainly due to the hydrophobic characteristic of the organic photoactive layer. To overcome this issue, we investigated the solvent effect of a well-studied cathode interlayer, bathocuproine (BCP). We were able to form a uniform thin BCP film (∼10 nm) on a non-fullerene based organic photoactive layer using the doctor bladed coating method. Our results showed that the use of volatile alcohols in the BCP processing required a delicate balance between wettability and vaporization, which contrasted with the results for spin-coated films. These findings provide important insights into improving the efficiency of printing techniques for depositing charge transport layers. The fully printed OSC modules, featuring uniform and continuous BCP layer formation, achieved an impressive power conversion efficiency of 10.8% with a total area of 10.0 cm2 and a geometrical fill factor of 86.5%.

Trifluoromethyl-Substituted Conjugated Random Terpolymers Enable High-Performance Small and Large-Area Organic Solar Cells Using Halogen-Free Solvent.

The advancement of non-fullerene acceptors with crescent-shaped geometry has led to the need for polymer donor improvements. Additionally, there is potential to enhance the photovoltaic parameters in high-efficiency organic solar cells (OSCs). The random copolymerization method is a straightforward and effective strategy to further optimize photoactive morphology and enhance device performance. However, finding a suitable third component in terpolymers remains a crucial challenge. In this study, a series of terpolymer donors (PTF3, PTF5, PTF10, PTF20, and PTF50) is synthesized by introducing varying amounts of the trifluoromethyl-substituted unit (CF3) into the PM6 polymer backbone. Even subtle changes in the CF3 content can significantly enhance all the photovoltaic parameters due to the optimized energy levels, molecular aggregation/miscibility, and bulk-heterojunction morphology of the photoactive materials. Thus, the best binary OSC based on the PTF5:Y6-BO achieves an outstanding power conversion efficiency (PCE) of 18.2% in the unit cell and a PCE of 11.6% in the sub-module device (aperture size: 54.45 cm2 ), when using halogen-free solvent o-xylene. This work showcases the remarkable potential of the easily accessible CF3 unit as a key constituent in the construction of terpolymer donors in high-performance OSCs.

Deposition of large-area organic solar cells based on poly-3-hexylthiophene with double ETL

Solar cells with FTO/TiO2/PFN/P3HT:PC61BM/MoO3/Ag configuration were built with different areas: 0.03, 0.25, 1, 4, 9, 16, and 25 cm2. In addition, Solar devices of 4 and 25 cm2 of total area were built interconnecting solar cells of 1 cm2 of area. With the results obtained, it was possible to establish a correlation, and an efficiency trend line concerning the area was estimated. The cell with the highest efficiency was the one of size 0.03 cm2 with Jsc of 12.32 mA/cm2, Voc of 0.59 volts, FF of 0.58, PCE of 4.23 %, with an EQE of 33.5 %, Vbi of 0.60 volts, Rs of 52.15 ohms, Rsh of 212.40 × 103 ohms and Na-Nd of 0.07 × 1025 1/cm3. The largest cell (25 cm2) considerably decreased its efficiency, obtaining a PCE of 0.13 %, with Jsc of 0.92 mA/cm2, Voc of 0.58 volts, FF of 0.25, Vbi of 0.18 volts, Rs of 20.17 ohms, Rsh of 1.83 × 103 ohms and Na-Nd of 3889.09 × 1025 1/cm3. On the other hand, no difference was found in the efficiency between cells with an area of 4 cm2 and 25 cm2 with respect to the devices built with cells of 1 cm2 interconnected with a total area of the same size. Also, absorbance and transmission spectra, XRD and AFM of thin films are shown.

Enhancing the reproducibility of large-area organic solar cells via double-cable conjugated polymers

Flexibility and large-area feasibility are the key roadmaps for organic solar cells (OSCs) toward industrialization. However, the efficiency gap and low reproducibility between small-area and large-area devices have impeded their further development. Here, the origination of these issues is studied in detail and the different viscosities of the donor and acceptor are found as the key factor. Their distinct viscosities generate inhomogeneous thin films via solution process, resulting in significantly reduced efficiencies and deteriorated reproducibility. As an alternative, double-cable polymers are found to perfectly tackle these issues, since they can act as a single photoactive layer in OSCs. For example, when going from 0.04 cm2 to 1.0 cm2 devices, bulk-heterojunction OSCs exhibit decreaased averaged-efficiencies from 7.29% to 4.66% and increase standard deviations from 0.45 to 2.18, while double-cable polymer based single-component OSCs show the averaged-efficiencies from 9.56% to 8.49% and standard deviations from 0.18 to 0.57. In addition, it is found that 1-cm2 flexible single-component OSCs exhibit excellent mechanical and storage stability. All these results demonstrate that double-cable conjugated polymers as a single layer can alleviate the reproducibility gap within lab-to-manufacturing translation toward stable, large-area flexible OSCs.

A bottom-up understanding of the ligand-dominated formation of metallic nanoparticle electrodes with high broadband reflectance for enabling fully solution-processed large-area organic solar cells

Understanding the ligand-dominant impact on silver nanoparticles aids in the realization of compact-packed silver nanoparticle electrodes with high broadband reflectance, resulting in an evaporation-free large-area organic solar cell.

Area-dependent performance variation of ultrasonic spray-coated organic solar cells

Here, a comparative study has been performed to understand the scalability of as developed ultrasonic spray deposition process for large-area organic solar cell fabrication. It was observed that the performance of the devices reduces with increasing active area dimensions. The short circuit current density and power conversion efficiency got decreased by more than 70% on increasing the device area from 0.04 to 1.5 cm2. In the case of small-area devices, the low electrical resistance owing to fewer droplet boundaries and negligible pinholes of the spray-coated film leads to better device performance. Whereas, upon scaling up the device area, the non-uniformity of the spray-coated film starts dominating and is found to be responsible for the reduction in overall device performance. The non-homogeneous film morphology in the case of larger-area devices greatly affects the charge generation, as it decreased from 4.77 × 1021 to 1.92 × 1021 cm−3 s−1 for large-area devices compared to small-area ones. The results suggest that the spray-deposited films greatly suffer from the limitation of droplet boundaries and pin-holes, which need to be addressed further with post-deposition treatments, in order to fabricate commercially viable large-area devices.

Research progress of large-area organic solar cells

<p indent="0mm">In recent years, organic solar cells (OSCs) have been developed rapidly, and their power conversion efficiencies (PCEs) of small-area OSCs have exceeded 19%. However, the performance of large-area devices lags far behind the development of the small-area ones. In-depth research on the major challenges of large-area organic photovoltaic devices and the development of large-area printing technologies is of great significance for promoting the industrial application of organic solar cells. Compared with small-area devices, the film thickness tolerance of the active layer, the sheet resistance of the transparent electrode, and the processing method should be mainly concentrated. Although the preparation of the large-area and stable OSCs has made significant progress and how to fabricate efficient, stable, rigid/flexible and large-area solar cells still remains a great challenge. In this review, focused on rigid and flexible substrates of large-area solar cells, we briefly summarized the new active layer materials, coating process, cathode/anode materials, electrode materials, <italic>etc</italic>. Considering the current trend, we believe the high-efficiency large-area OSCs in the laboratory would very soon lead to the production of highly efficient large-scale organic devices on an industrial scale.

Environmentally Friendly and Roll-Processed Flexible Organic Solar Cells Based on PM6:Y6

Organic Solar Cells (OSCs) have reached the highest efficiencies using lab-scale device manufacturing on active areas far below 0.1 cm2. The most used fabrication technique is spin-coating, which has poor potential for upscaling and substantial material waste. This tends to widen the so-called “lab-to-fab gap”, which is one of the most important challenges to make OSCs competitive. Other techniques such as blade or slot-die coating are much more suitable for roll-to-roll manufacturing, which is one of the advantages the technology presents due to the huge potential for fast and low-cost fabrication of flexible OSCs. However, only a few studies report solar cells using these fabrication techniques, especially applied on a roll-platform. Additionally, for environmentally friendly large area OSCs, inks based on non-hazardous solvent systems are needed. In this work, slot-die coating has been chosen to coat a PM6:Y6 active layer, using o-xylene, a more environmentally friendly alternative than halogenated solvents, and without additives. The optimal coating process is defined through fine-tuning of the coating parameters, such as the drying temperature and solution concentration. Moreover, ternary devices with PCBM, and fully printed devices are also fabricated. Power conversion efficiencies of 6.3% and 7.2% are achieved for binary PM6:Y6 and ternary PM6:Y6:PCBM devices measured with an aperture area of ∼0.4 cm2 (total device area ∼0.8 cm2).

Glucose and Its Derivatives as Interfacial Materials for Inverted Organic Solar Cells.

Glucose, a widely distributed biomaterial in nature, is presented as a new cathode interfacial material for highly efficient inverted organic solar cells. The interactions between glucose and the indium tin oxide (ITO) substrate as well as the formation mechanisms of the glucose interlayer were investigated by molecular dynamics simulation and relevant experimental tests. The results revealed that the In-OH coordination between the oxygen atom of glucose and the indium of ITO is the key factor for the formation of interfacial dipoles, thereby reducing the work function of the ITO cathode for efficient charge transfer. With PM6:Y6 as the active layer, the power conversion efficiency (PCE) of the organic solar cells was significantly increased from 1.99 to 15.42% after ITO was modified by a glucose interlayer through the traditional spin-coating method. More importantly, glucose can be adsorbed on the ITO surface by a simple immersion process, and the devices based on the modified ITO by immersed glucose achieved a PCE of 14.48%, which is comparable to that of the traditional spin-coating method. Furthermore, we found that the OSCs with the ITO cathodes modified with glucose derivatives including sorbitol and sodium gluconate by different preparation methods also exhibited high performance. The overall performance of the devices with ITO modified by a simple and low-cost immersion method can be maintained at more than 93% of that prepared with the traditional spin-coating method. The results demonstrated that low-price glucose and its derivatives are good candidates as ITO interlayer materials for OSCs, and the effectiveness of the immersion process paves a way for simplifying the manufacture of low-cost and large-area organic solar cells.