Sensitive detection of near-infrared (NIR) light enables many important applications in both research and industry. Current organic photodetectors suffer from low NIR sensitivity typically due to early absorption cutoff, low responsivity and/or large dark/noise current under bias. Herein, organic photodetectors based on a novel ultranarrow bandgap non-fullerene acceptor, CO1-4Cl, are presented, showcasing a remarkable responsivity over 0.5 A W-1 in the NIR spectral region (920-960 nm), which is the highest amongst organic photodiodes. By effectively delaying the onset of the space charge limited current and suppressing the shunt leakage current, the optimized devices show a large specific detectivity around 10 12 Jones for NIR spectral region up to 1010 nm, close to that of a commercial Si photodiode. The presented photodetectors can also be integrated in photoplethysmography for real-time heart rate monitoring, suggesting its potential for practical applications. Near-infrared (NIR) light usually corresponds to the region of electromagnetic radiation with wavelength spanning from about 750 nm to 1400 nm. [1] Despite being invisible to human visual perception, NIR sensing finds applications in a variety of technologies, including medical monitoring, [2] quality inspection, [3] machine vision, [4] and bio-imaging. [5] NIR sensing has been conventionally realized with detectors based on single-crystal inorganic semiconductor materials (e.g. Si, Ge, GaInAs), which typically have drawbacks including costly processing, mechanical inflexibility, and sensitivity to temperature. [6-8] Owing to the low cost, solution processing, material tunability, unique structure-property relationships and good mechanical flexibility, organic semiconductors emerged as an exciting candidate for integrated electronics, lighting, solar cells and photodetection. Particularly, photodetectors based on organic semiconductors have witnessed increasing research endeavor, Received: ((will be filled in by the editorial staff)) Revised: ((will be filled in by the editorial staff))

The highly efficient single-junction bulk-heterojunction (BHJ) PM6:Y6 system can achieve high open circuit voltages (V OC) while maintaining exceptional fill-factor (FF) and short-circuit current (J SC) values. With a low energetic offset, the blend system was found to exhibit radiative and nonradiative recombination losses that are among the lower reported values in the literature. Recombination and extraction dynamic studies revealed that the device shows moderate nongeminate recombination coupled with exceptional extraction throughout the relevant operating conditions. Several surface and bulk characterization techniques were employed to understand the phase separation, long-range ordering, as well as donor:acceptor (D:A) inter-and intramolecular interactions at an atomic-level resolution. This was achieved using photo-conductive atomic force microscopy (pc-AFM), grazing incidence wide angle x-ray scattering (GIWAXS), and solid-state 19 F Magic-Angle Spinning (MAS) NMR spectroscopy. The synergy of multifaceted characterization and device physics was used to uncover key insights, for the first time, on the structure-property relationships of this high performing BHJ blend. Detailed information about atomically resolved D:A interactions and packing revealed that the high performance of over 15% efficiency in this blend can be correlated to a beneficial morphology that allows high J SC and FF to be retained despite the low energetic offset.

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Some fundamental questions in the organic solar cell (OSC) community are related to the role of bulk and interfacial morphology on key processes such as charge generation, recombination, and extraction...

Even though significant breakthroughs with over 17% power conversion efficiencies (PCEs) in polymer:non-fullerene acceptor (NFA) bulk heterojunction organic solar cells (OSCs) have been achieved, not many studies have focused on acquiring a comprehensive understanding of the underlying mechanisms governing these systems. This is because it can be challenging to delineate device photophysics in polymer:NFA blends comprehensively, and even more complicated to trace the origins of the differences in device photophysics to the subtle differences in energetics and morphology. Here, a systematic study of a series of polymer:NFA blends was conducted to unify and correlate the cumulative effects of i) voltage losses ii) charge generation efficiencies, iii) nongeminate recombination and extraction dynamics, and iv) nuanced morphological differences with device performances. Most importantly, a deconvolution of the major loss processes in polymer:NFA blends and their connections to the complex BHJ morphology and energetics were established. An extension to advanced morphological techniques, such as solid-state NMR (for atomic level insights on the local ordering and donor:acceptor π-π interactions) and resonant soft x-ray scattering (for donor and acceptor interfacial area and domain spacings), provided detailed insights on how efficient charge generation, transport, and extraction processes can outweigh increased voltage losses to yield high PCEs.

The environmental impact of solution processed organic solar cells (OSCs) can be mitigated by introducing so‐called green solvents during the fabrication processes. However, the effects of such green solvents on the molecular‐level structures and optoelectronic properties lack in‐depth characterization. Here, insights into the structure–processing–property correlation of a PPDT2FBT:PC61BM bulk‐heterojunction (BHJ) system processed from a green solvent, ortho‐xylene (o‐XY), is investigated in comparison with the same blend processed from a traditional halogenated solvent, chlorobenzene (CB). The BHJ blends are characterized with various techniques probing at difference length scales, and an increased donor:acceptor (D:A) interfacial area as well as well‐mixed features in the bulk morphologies of the active layer are observed for the o‐XY processed BHJ blend. Furthermore, molecular‐level differences in the D–A intermolecular interactions at the BHJ interfaces in o‐XY and CB cast films are elucidated by 2‐dimensional solid‐state nuclear magnetic resonance (ssNMR) measurements and analysis. These results are consistent with the device properties, suggesting that the green‐solvent‐processed devices have longer charge carrier lifetimes and faster charge carrier extraction. The optimized PPDT2FBT:PC61BM devices processed from o‐XY can achieve a noteworthy higher power conversion efficiency (PCE) owing to a higher short‐circuit current density and fill factor.

Tetracyanoquinodimethane leads to trap-enhanced photoconductive gain and highly efficient broadband sensing for bulk heterojunction organic photodetectors.

The effect of the cross‐coupling catalyst tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4) on the performance of a model organic bulk‐heterojunction solar cell composed of a blend of 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}) (PTB7‐Th) donor and 3,9‐bis(2‐methylene‐((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 (IOTIC‐4F) non‐fullerene acceptor is investigated. The effect of intentional addition of different amounts of Pd(PPh3)4 on morphology, free charge carrier generation, non‐geminate bulk trap‐ and surface trap‐assisted recombination as well as bimolecular recombination and charge extraction is quantified. This work shows that free charge carrier generation is affected significantly, while the impact of Pd(PPh3)4 on non‐geminate recombination processes is limited because the catalyst does not facilitate efficient trap‐assisted recombination. The studied system shows substantial robustness towards the addition of Pd(PPh3)4 in small amounts.