New Perylene Diimide Ink for Interlayer Formation in Air-Processed Conventional Organic Photovoltaic Devices.

Roll-to-roll coating of conventional organic photovoltaic architectures in air necessitates low work function, electron-harvesting interlayers as the top interface, termed cathode interlayers. Traditional materials based on metal oxides are often not compatible with coating in air and/or green solvents, require thermal annealing, and are limited in feasibility due to interactions with underlying layers. Alternatively, perylene diimide materials offer easily tunable redox properties, are amenable to air coating in green solvents, and are considered champion organic-based cathode interlayers. However, underlying mechanisms of the extraction of photogenerated electrons are less well understood. Herein, we demonstrate the utilization of two N-annulated perylene diimide materials, namely, PDIN-H and CN-PDIN-H, in air-processed conventional organic photovoltaic devices, using the now standard PM6:Y6 photoactive layer. The processing ink formulation using cesium carbonate as a processing agent to solubilize the perylene diimides in suitable green solvents (1-propanol and ethyl acetate) for uniform film formation using spin or slot-die coating on top of the photoactive layer is critical. Cesium carbonate remains in the film, creating hybrid organic/metal salt cathode interlayers. Best organic photovoltaic devices have power conversion efficiencies of 13.2% with a spin-coated interlayer and 13.1% with a slot-die-coated interlayer, superior to control devices using the classic conjugated polyelectrolyte PFN-Br as an interlayer (ca. 12.8%). The cathode interlayers were found to be semi-insulating in nature, and the device performance improvements were attributed to beneficial interfacial effects and electron tunneling through sufficiently thin layers. The efficiencies beyond 13% achieved in air-processed organic photovoltaic devices utilizing slot-die-coated cathode interlayers are among the highest reported so far, opening new opportunities for the fabrication of large-area solar cell modules.

Development of Tetrameric N-Annulated Perylene Diimides Using "Click" Chemistry.

Herein, we report the design, synthesis, and characterization of two novel N-annulated perylene diimide (NPDI) tetramer arrays that were developed using copper catalyzed alkyne-azide cycloaddition. Despite the optoelectronic properties of both tetramers being nearly identical, the two tetramers exhibited very different molecular geometries. The twisted spirobifluorene NPDI tetramer (sbfNPDI4 ) was found to have an extended and flexible geometry, while the planar pyrene NPDI tetramer (pyrNPDI4 ) exhibited a highly congested and conformationally locked geometry. Organic photovoltaic devices were constructed to demonstrate the use of both new compounds as electron acceptor materials, where slightly higher power conversion efficiencies were achieved with pyrNPDI4 than sbfNPDI4 . This study highlights the viability of using "click" chemistry as a facile synthetic strategy towards the development of new multicomponent perylene diimide materials for organic electronic applications.

Tin Oxide Electron Transport Layers for Air-/Solution-Processed Conventional Organic Solar Cells.

Commercialization of organic solar cells (OSC) is imminent. Interlayers between the photoactive film and the electrodes are critical for high device efficiency and stability. Here, the applicability of SnO2 nanoparticles (SnO2 NPs) as the electron transport layer (ETL) in conventional OSCs is evaluated. A commercial SnO2 NPs solution in butanol is mixed with ethanol (EtOH) as a processing co-solvent to improve film formation for spin and slot-die coating deposition procedures. When processed with 200% v/v EtOH, the SnO2 NPs film presents uniform film quality and low photoactive layer degradation. The optimized SnO2 NPs ink is coated, in air, on top of two polymer:fullerene-based systems and a nonfullerene system, to form an efficient ETL film. In every case, addition of SnO2 NPs film significantly enhances photovoltaic performance, from 3.4 and 3.7% without the ETL to 6.0 and 5.7% when coated on top of PBDB-T:PC61BM and PPDT2FBT:PC61BM, respectively, and from 3.7 to 7.1% when applied on top of the PTQ10:IDIC system. Flexible, all slot-die-coated devices, in air, are also fabricated and tested, demonstrating the versatility of the SnO2 NPs ink for efficient ETL formation on top of organic photoactive layers, processed under ambient condition, ideal for practical large-scale production of OSCs.

Hybrid Tetrameric Perylene Diimide Assemblies.

Organic photovoltaics have found utility as indoor light recycling devices providing an opportunity for the sustainable powering of IoT sensors and related smart electronics. In the report, two organic π-conjugated molecules consisting of four perylene diimide (PDI) chromophores each are presented and used as non-fullerene acceptors in indoor photovoltaic devices. The new materials consist of a dimeric N-annulated PDI core with single PDIs grafted onto the pyrrolic N-atom positions of the core. Compounds PDI4 e and PDI4 i are PDI tetramers and differ with PDI4 e having the terminal N-annulated PDI with pyrrolic N-atom distal to the core and PDI4 i having the terminal N-annulated PDI with pyrrolic N-atom proximal to the core. The structural and optoelectronic properties were investigated using NMR spectroscopy, optical absorption and emission spectroscopy, and cyclic voltammetry. The compounds exhibit typical optical signatures for PDIs but notable is that the addition of grafted PDI molecules prevents significant aggregation of the dimeric PDI core, as compared to a reference dimer. Use as non-fullerene acceptors in ternary bulk-heterojunction blends with the polymer FBT and fullerene PC61 BM lead to increased open-circuit voltages and power conversion efficiencies upwards of 13.7 % at 2000 lux light intensity.

Slot-Die-Coated Ternary Organic Photovoltaics for Indoor Light Recycling.

Efficient organic photovoltaics (OPVs) based on slot-die-coated (SD) ternary blends were developed for low-intensity indoor light harvesting. For active layers processed in air and from eco-friendly solvents, our device performances (under 1 sun and low light intensity) are the highest reported values for fluoro-dithiophenyl-benzothiadiazole donor polymer-based OPVs. The N-annulated perylene diimide dimer acceptor was incorporated into a blend of donor polymer (FBT) and fullerene acceptor (PC61BM) to give ternary bulk heterojunction blends. SD ternary-based devices under 1 sun illumination showed enhanced power conversion efficiency (PCE) from 6.8 to 7.7%. We observed enhancement in the short-circuit current density and open-circuit voltage of the devices. Under low light intensity light-emitting device illumination (ca. 2000 lux), the ternary-based devices achieved a PCE of 14.0% and a maximum power density of 79 µW/cm2 compared to a PCE of 12.0% and a maximum power density of 68 µW/cm2 for binary-based devices. Under the same illumination conditions, the spin-coated (SC) devices showed a PCE of 15.5% and a maximum power density of 88 µW/cm2. Collectively, these results demonstrate the exceptional promise of a SD ternary blend system for indoor light harvesting and the need to optimize active layers based on industry-relevant coating approaches toward mini modules.

Synergistic Effects of Morphological Control and Complementary Absorption in Efficient All-Small-Molecule Ternary-Blend Solar Cells.

In this study, we combined two small-molecule donors-a diketopyrrolopyrrole-based small molecule (SMD) and a benzodithiophene-based molecule (BDT6T)-with [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) to form ternary blend solar cells. The power conversion efficiency of the binary SMD:PC61BM bulk heterojunction solar cell improved from 4.57 to 6.28% after adding an appropriate amount BDT6T as a guest. We attribute this 37% improvement in device performance to the complementary absorption behavior of BDT6T and SMD, as evidenced by the increase in the short circuit current. After addition of BDT6T to form the ternary blend, the crystallinity and morphology of the active layer were enhanced. For example, the features observed in the ternary active layers were finer than those in the binary blends. This means that BDT6T as a third component in the ternary blend has effective role on both the absorption and the morphology. In addition, adding BDT6T to form the ternary blend also led to an increase in the open-circuit voltage. Our findings suggest that the preparation of such simple all-small-molecule ternary blends can be an effective means of improving the efficiency of photovoltaic devices.