Kaikai Liu

We report the synthesis of a family of multifluorine substituted oligomers and the corresponding polymer that have the same backbones but different conjugation lengths and amounts of fluorine atoms on the backbone. The physical properties and photovoltaic performances of these materials were systematically investigated using optical absorption, charge mobility, atomic force microscopy, transmission electron microscopy, grazing incidence X-ray diffraction, resonant soft X-ray scattering methods, and photovoltaic devices. The power conversion efficiencies (PCEs) based on oligomers were much higher than that in the polymer. Moreover, the devices based on BIT6F and BIT10F, which have an axisymmetric electron-deficient difluorobenzothiadiazole as the central unit, gave slightly higher PCEs than those with centrosymmetric electron-rich indacenodithiophene (IDT) as the central unit (BIT4F or BIT8F). Using proper solvent vapor annealing (SVA), particularly using thermal annealing (TA) followed by SVA, the device performance could be significantly improved. Notably, the best PCE of 9.1% with a very high FF of 0.76 was achieved using the medium-sized oligomer BIT6F with the optimized film morphology. This efficiency is the highest value reported for organic solar cells from small-molecules without rhodanine terminal group. More excitingly, devices from the shortest oligomer BIT4F showed an impressively high FF of 0.77 (the highest FF value reported for solution-processed small-molecule organic solar cells). These results indicate that photovoltaic performances of oligomers can be modulated through successive change in chain-length and fluorine atoms, alternating spatial symmetric core, and combined post-treatments.

Abstract Reactive oxygen species (ROS) are generated in the body and related to many pathophysiological processes. Hence, detection of ROS is indispensable in understanding, diagnosis, and treatment of many diseases. Here, near‐infrared (NIR) chemiluminescent (CL) carbon nanodots (CDs) are fabricated for the first time and their CL quantum yield can reach 9.98 × 10 −3 einstein mol −1 , which is the highest value ever reported for CDs until now. Nanointegration of NIR CDs and peroxalate (P‐CDs) through the bridging effect of amphiphilic triblock copolymer can serve as turn‐on probes for the detection and imaging of hydrogen peroxide (H 2 O 2 ). Considering high efficiency and large penetration depth of NIR photons, the P‐CDs are employed in bioimaging H 2 O 2 in vitro and in vivo, and the detection limit can reach 5 × 10 −9 m , among the best reported of CDs‐based sensors. Moreover, imaging of inflammatory H 2 O 2 in a mouse model of peritonitis is achieved by employing the P‐CDs as sensors. The results may provide a clue for the diagnosis and treatment of inflammation or cancers employing CL CDs as sensors.

Red/near-infrared (NIR) emissive carbon nanodots (CNDs) with photoluminescence (PL) quantum yield (QY) of 57% are prepared via an in situ solvent-free carbonization strategy for the first time. 1-Photon and 2-photon cellular imaging is demonstrated by using the CNDs as red/NIR fluorescence agent due to the high PL QY and low biotoxicity. Further study shows that the red/NIR CNDs exhibit multiphoton excited (MPE) upconversion fluorescence under excitation of 800-2000 nm, which involves three NIR windows (NIR-I, 650-950 nm; NIR-II, 1100-1350; NIR-III, 1600-1870 nm). 2-Photon, 3-photon, and 4-photon excited fluorescence of the CNDs under excitation of different wavelengths is achieved. This study develops an in situ solvent-free carbonization method for efficient red/NIR emissive CNDs with MPE upconversion fluorescence, which may push forward the application of the CNDs in bioimaging.

A new electron-rich central core (SeT) based on a fused selenopheno[3,2-b]thiophene unit and two nonfullerene small-molecule acceptors is synthesized for organic solar cells. Compared with SeTIC, chlorinated SeTIC4Cl exhibits a stronger near-infrared absorption with a smaller bandgap (1.44 eV), down-shifted highest occupied molecular orbital/lowest unoccupied molecular orbital energy levels, and improved crystallinity with higher electron mobility owing to the stronger intramolecular charge-transfer effect. Therefore, SeTIC4Cl/PM6 blend films exhibited significantly higher power conversion efficiency owing to broader light absorption range, more balanced charge mobility, and desirable nanoscale phase separation for exciton dissociation and reduced geminate recombination. As a result, the optimized device based on SeTIC4Cl/PM6 shows a higher power conversion efficiency (PCE) of 13.32%, which is the highest value to date for selenophene-containing nonfullerene acceptor (NFA)-based binary organic solar cells. Equally important, the PCE of SeTIC4Cl is insensitive to the variation in thickness of the active layer to 300 nm. Our results demonstrate the great potential of the selenopheno[3,2-b]thiophene unit for designing high-performance NFAs.

Organic solar cells (OSCs) have advanced rapidly due to the development of new photovoltaic materials. However, the long-term stability of OSCs still poses a severe challenge for their commercial deployment. To address this issue, a dimer acceptor (dT9TBO) with flexible linker is developed for incorporation into small-molecule acceptors to form molecular alloy with enhanced intermolecular packing and suppressed molecular diffusion to stabilize active layer morphology. Consequently, the PM6 : Y6 : dT9TBO-based device displays an improved power conversion efficiency (PCE) of 18.41 % with excellent thermal stability and negligible decay after being aged at 65 °C for 1800 h. Moreover, the PM6 : Y6 : dT9TBO-based flexible OSC also exhibits excellent mechanical durability, maintaining 95 % of its initial PCE after being bended repetitively for 1500 cycles. This work provides a simple and effective way to fine-tune the molecular packing with stabilized morphology to overcome the trade-off between OSC efficiency and stability.