Structural insights into Lewis acid- and F4TCNQ-doped conjugated polymers by solid-state magnetic resonance spectroscopy.

Molecular doping strategies facilitate orders of magnitude enhancement in the charge carrier mobility of organic semiconductors (OSCs). Understanding the different doping mechanisms and molecular-level constraints on doping efficiency related to the material energy levels is crucial to develop versatile dopants for OSCs. Given the compositional and structural heterogeneities associated with OSC thin films, insight into dopant-polymer interactions by long-range techniques such as X-ray scattering and electron microscopy is exceedingly challenging to obtain. This study employs short-range probes, solid-state (ss)NMR and EPR spectroscopy, to resolve local structures and intermolecular interactions between dopants such as F4TCNQ (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane), Lewis acid BCF (tris[pentafluorophenyl] borane) and Lewis base conjugated polymer, PCPDTBT (P4) (poly[2,6-(4,4-bis(2-hexadecyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7(2,1,3-benzothiadiazole)]). Analysis of 1H and 13C ssNMR spectra of P4, P4 : F4TCNQ and P4 : BCF blends indicates that the addition of dopants induces local structural changes in the P4 polymer, and causes paramagnetism-induced signal broadening and intensity losses. The hyperfine interactions in P4 : BCF and P4 : F4TCNQ are characterized by two-dimensional pulsed EPR spectroscopy. For P4 : F4TCNQ, 19F ssNMR analysis indicates that the F4TCNQ molecules are distributed and aggregated into different local chemical environments. By comparison, BCF molecules are intermixed with the P4 polymer and interact with traces of water molecules to form BCF-water complexes that serve as Brønsted acid sites, as revealed by 11B ssNMR spectroscopy. These results indicate that the P4-dopant blends exhibit complex morphology with different distributions of dopants, whereby the combined use of ssNMR and EPR provides essential insights into how higher doping efficiency is observed with BCF and a mediocre efficiency is associated with F4TCNQ molecules.

Efficiency of Thermally Activated Delayed Fluorescence Sensitized Triplet Upconversion Doubled in Three-Component System.

As in many fields, the most exciting endeavors in photon upconversion research focus on increasing the efficiency (upconversion quantum yield) and performance (anti-Stokes shift) while diminishing the cost of production. In this vein, studies employing metal-free thermally activated delayed fluorescence (TADF) sensitizers have garnered increased interest. Here, for the first time, the strategy of ternary photon upconversion is utilized with the TADF sensitizer 2,4,5,6-tetrakis(carbazol-9-yl)isophthalonitrile (4CzIPN), resulting in a doubling of the upconversion quantum yield in comparison to the binary system employing p-terphenyl as the emitter. In this ternary blend, the sensitizer 4CzIPN is paired with an intermediate acceptor, 1-methylnaphthalene, in addition to the emitter molecule, p-terphenyl, yielding a normalized upconversion quantum yield of 7.6% while maintaining the 0.83 eV anti-Stokes shift. These results illustrate the potential benefits of utilizing this strategy of energy-funneling, previously used only with heavy-metal based sensitizers, to increase the performance of these photon upconversion systems.

A High-Performance Solution-Processed Organic Photodetector for Near-Infrared Sensing.

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 nonfullerene 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 among 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 1012 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.

Understanding the High Performance of over 15% Efficiency in Single-Junction Bulk Heterojunction Organic Solar Cells.

The highly efficient single-junction bulk-heterojunction (BHJ) PM6:Y6 system can achieve high open-circuit voltages (VOC ) while maintaining exceptional fill-factor (FF) and short-circuit current (JSC ) values. With a low energetic offset, the blend system is found to exhibit radiative and non-radiative recombination losses that are among the lower reported values in the literature. Recombination and extraction dynamic studies reveal that the device shows moderate non-geminate recombination coupled with exceptional extraction throughout the relevant operating conditions. Several surface and bulk characterization techniques are 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 is achieved using photo-conductive atomic force microscopy, grazing-incidence wide-angle X-ray scattering, and solid-state 19 F magic-angle-spinning NMR spectroscopy. The synergy of multifaceted characterization and device physics is 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 reveals that the high performance of over 15% efficiency in this blend can be correlated to a beneficial morphology that allows high JSC and FF to be retained despite the low energetic offset.

Towards understanding the doping mechanism of organic semiconductors by Lewis acids.

Precise doping of organic semiconductors allows control over the conductivity of these materials, an essential parameter in electronic applications. Although Lewis acids have recently shown promise as dopants for solution-processed polymers, their doping mechanism is not yet fully understood. In this study, we found that B(C6F5)3 is a superior dopant to the other Lewis acids investigated (BF3, BBr3 and AlCl3). Experiments indicate that Lewis acid-base adduct formation with polymers inhibits the doping process. Electron-nuclear double-resonance and nuclear magnetic resonance experiments, together with density functional theory, show that p-type doping occurs by generation of a water-Lewis acid complex with substantial Brønsted acidity, followed by protonation of the polymer backbone and electron transfer from a neutral chain segment to a positively charged, protonated one. This study provides insight into a potential path for protonic acid doping and shows how trace levels of water can transform Lewis acids into powerful Brønsted acids.