Chalcogen Atoms Regulate the Organic Solar Cell Performance of B-N-Based Polymer Donors.

Donor polymers play a key role in the development of organic solar cells (OSCs). B-N-based polymer donors, as new types of materials, have attracted a lot of attention due to their special characteristics, such as high E(T1), small ΔEST, and easy synthesis, and they can be processed with real green solvents. However, the relationship between the chemical structure and device performance has not been systematically studied. Herein, chalcogen atoms that regulate the OSCs performance of B-N-based polymer donors were systematically studied. Fortunately, the substitution of a halogen atom did not affect the high E(T1) and small ΔEST character of the B-N-based polymer. The absorption and energy levels of the polymer were systematically regulated by O, S, and Se atom substitution. The PBNT-TAZ:Y6-BO-based OSCs device demonstrated a high power conversion efficiency of 15.36%. Moreover, the layer-by-layer method was applied to further optimize the device performance, and the PBNT-TAZ/Y6-BO-based OSCs device yielded a PCE of 16.34%. Consequently, we have systematically demonstrated how chalcogen atoms modulated the electronic properties of B-N-based polymers. Detailed and systematic structure-performance relationships are important for the development of next-generation B-N-based materials.

Sensitive Organic Photodetectors With Spectral Response up to 1.3 µm Using a Quinoidal Molecular Semiconductor.

Detecting short-wavelength infrared (SWIR) light has underpinned several emerging technologies. However, the development of highly sensitive organic photodetectors (OPDs) operating in the SWIR region is hindered by their poor external quantum efficiencies (EQEs) and high dark currents. Herein, the development of high-sensitivity SWIR-OPDs with an efficient photoelectric response extending up to 1.3 µm is reported. These OPDs utilize a new ultralow-bandgap molecular semiconductor featuring a quinoidal tricyclic electron-deficient central unit and multiple non-covalent conformation locks. The SWIR-OPD achieves an unprecedented EQE of 26% under zero bias and an even more impressive EQE of up to 41% under a -4 V bias at 1.10 µm, effectively pushing the detection limit of silicon photodetectors. Additionally, the low energetic disorder and trap density in the active layer lead to significant suppression of thermal-generation carriers and dark current, resulting in excellent detectivity (Dsh *) exceeding 1013 Jones from 0.50 to 1.21 µm and surpassing 1012 Jones even at 1.30 µm under zero bias, marking the highest achievements for OPDs beyond the silicon limit to date. Validation with photoplethysmography measurements, a spectrometer prototype in the 0.35-1.25 µm range, and image capture under 1.20 µm irradiation demonstrate the extensive applications of this SWIR-OPD.

An electron acceptor with an intrinsic quinoidal core for bulk-heterojunction organic solar cells and photodetectors.

An electron acceptor based on a quinoidal dipyrrolopyrazinedione core was synthesized for organic solar cells and photodetectors. A power conversion efficiency of 6.7% and a specific detectivity of 4.1 × 1013 Jones at 800 nm have been obtained, suggesting the promising prospects of quinoidal molecules for optoelectronic devices.

Wide Bandgap Conjugated Polymers Based on Difluorobenzoxadiazole for Efficient Non-Fullerene Organic Solar Cells.

Wide bandgap polymers with a donor-acceptor alternating structure play a key role in constructing high-efficiency organic solar cells (OSCs). However, only a handful of high-performance polymers are available owing to the limited choices of acceptor units. 5,6-Difluorobenzo[c][1,2,5]oxadiazole (ffBX) is a promising acceptor unit with high ionization potential, and can afford high charge carrier mobility and strong aggregation for the resulting polymers. Historically, ffBX is successfully used in constructing high-performance polymer donors for fullerene-based OSCs. However, this unit is far less been explored in non-fullerene OSCs. In this work, three ffBX-based wide bandgap polymers (Oc00, Oc25, and Oc50) with varied solubilizing side chain content for application in non-fullerene OSCs are reported. The polymers show matched energy levels and complementary optical absorption with the state-of-the-art non-fullerene acceptor Y6. Moreover, the polymer solubility, solid state packing, and bulk-heterojunction morphology are finely tuned via side chain engineering. Encouragingly, a decent efficiency of 14.25% is realized by the polymer Oc25 when blended with Y6 due to the efficient charge transport and favorable active layer morphology. These results suggest the promising prospect of ffBX in constructing high-performance polymer donors for non-fullerene OSCs.

N-Type Quinoidal Polymers Based on Dipyrrolopyrazinedione for Application in All-Polymer Solar Cells.

Conjugated molecules and polymers with intrinsic quinoidal structure are promising n-type organic semiconductors, which have been reported for application in field-effect transistors and thermoelectric devices. In principle, the molecular and electronic characteristics of quinoidal polymers can also enable their application in organic solar cells. Herein, two quinoidal polymers, named PzDP-T and PzDP-ffT, based on dipyrrolopyrazinedione were synthesized and used as electron acceptors in all-polymer solar cells (all-PSCs). Both PzDP-T and PzDP-ffT showed suitable energy levels and wide light absorption range that extended to the near-infrared region. When combined with the polymer donor PBDB-T, the resulting all-PSCs based on PzDP-T and PzDP-ffT exhibited a power conversion efficiency (PCE) of 1.33 and 2.37 %, respectively. This is the first report on the application of intrinsic quinoidal conjugated polymers in all-PSCs. The photovoltaic performance of the all-PSCs was revealed to be mainly limited by the relatively poor and imbalanced charge transport, considerable charge recombination. Detailed investigations on the structure-performance relationship suggested that synergistic optimization of light absorption, energy levels, and charge transport properties is needed to achieve more successful application of intrinsic quinoidal conjugated polymers in all-PSCs.

A Facile Synthesized Polymer Featuring B-N Covalent Bond and Small Singlet-Triplet Gap for High-Performance Organic Solar Cells.

High-efficiency organic solar cells (OSCs) largely rely on polymer donors. Herein, we report a new building block BNT and a relevant polymer PBNT-BDD featuring B-N covalent bond for application in OSCs. The BNT unit is synthesized in only 3 steps, leading to the facile synthesis of PBNT-BDD. When blended with a nonfullerene acceptor Y6-BO, PBNT-BDD afforded a power conversion efficiency (PCE) of 16.1 % in an OSC, comparable to the benzo[1,2-b:4,5-b']dithiophene (BDT)-based counterpart. The nonradiative recombination energy loss of 0.19 eV was afforded by PBNT-BDD. PBNT-BDD also exhibited weak crystallinity and appropriate miscibility with Y6-BO, benefitting of morphological stability. The singlet-triplet gap (ΔEST ) of PBNT-BDD is as low as 0.15 eV, which is much lower than those of common organic semiconductors (≥0.6 eV). As a result, the triplet state of PBNT-BDD is higher than the charge transfer (CT) state, which would suppress the recombination via triplet state effectively.