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.

Narrow bandgap n-type molecular semiconductors are relevant as key materials components for the fabrication near-infrared organic solar cells (OSCs) and organic photodetectors (OPDs). We thus designed nearly isostructural nonfullerene electron acceptors, except for the choice of solubilizing units, which absorb from 600 to 1100 nm. Specific molecules include CTIC-4F, CO1-4F, and COTIC-4F, whose optical bandgaps are 1.3, 1.2, and 1.1 eV, respectively. Modulation of intramolecular charge transfer characteristics was achieved by replacing alkoxy groups with alkyl groups on thiophene spacers that connect an electron-rich cyclopentadithiophene core to peripheral electron-poor fragments. OSCs incorporating CTIC-4F and CO1-4F with PTB7-Th achieve power conversion efficiencies of over 10% with short-circuit current densities as high as ∼25 mA·cm–2. The same blends achieve OPD responsivities of 0.52 A·W–1 at ∼920 nm. These findings highlight outstanding opportunities to tune further molecular design so that OPDs may ultimately compete with their silicon counterparts.

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...

the continued research has led to power conversion efficiencies (PCEs) over 11% for single-junction devices. [7,8] Be that as it may, difficulties in tuning the molecular structure and electronic properties, as well as the comparatively high cost of production of fullerene-based acceptors are drawbacks that have triggered the search for nonfullerene acceptors (NFAs) as an alternative. [9][10][11][12][13][14][15][16] Noteworthy improvements have been made over the last few years, and state-of-the-art NFA-OSCs have been reported with PCEs over 16 %, thus outperforming their fullerene-based counterparts. [17,18] In tandem and ternary systems, PCEs reaching even up to 17.3% have been recently achieved. [19,20] Additionally, the reduction in the bandgap of NFAs opens up the possibility to fabricate semitransparent OSCs that could be applied in building-integrated photovoltaics or power generating greenhouses. [21][22][23][24] To further improve the performance of OSCs, loss-processes such as nongeminate recombination, the recombination of electrons and holes which do not originate from the same exciton, have to be curtailed. This includes bimolecular recombination (also known as Langevin recombination), where charge carriers recombine directly from band to band, as well as trap-assisted recombination (also known as Shockley-Read-Hall recombination), where states deep in the bandgap act as efficient recombination centers. A detailed understanding of these mechanisms responsible for the aforementioned recombination losses is required. [25] Whether or not there are considerable differences in recombination dynamics between NFA-OSCs and fullerene-based OSCs, has yet to be understood since most research in regard to recombination dynamics was performed only with OSCs employing fullerene acceptors. [26][27][28] Furthermore, the majority of studies describe recombination dynamics based on a numerical, drift-diffusion model under the assumption of an effective-medium for the BHJ active layer. [29][30][31][32][33][34][35][36][37][38] The concentration of charge carriers is the key differential parameter in the theory of recombination dynamics. However, only integral parameters (electrical conductivity, impedance, open-circuit voltage, V OC ) can be directly measured by experiments. Therefore, the primary challenge of the theoretical background of any method developed to quantify recombination processes in photovoltaic devices is based on finding the appropriate relationship between the measured In this study, a comprehensive analytical model to quantify the total nongeminate recombination losses, originating from bimolecular as well as bulk and surface trap-assisted recombination mechanisms in nonfullerene-based bulk heterojunction organic solar cells is developed. This proposed model is successfully employed to obtain the different contributions to the recombination current of the investigated solar cells under different illumination intensities. Additionally, the model quantitatively describes the experimentally measured ope...