Inner/Outer Side Chain Engineering of Non-Fullerene Acceptors for Efficient Large-Area Organic Solar Modules Based on Non-Halogenated Solution Processing in Air.

Achieving efficient and large-area organic solar modules via non-halogenated solution processing is vital for the commercialization yet challenging. The primary hurdle is the conservation of the ideal film-formation kinetics and bulk-heterojunction (BHJ) morphology of large-area organic solar cells (OSCs). A cutting-edge non-fullerene acceptor (NFA), Y6, shows efficient power conversion efficiencies (PCEs) when processed with toxic halogenated solvents, but exhibits poor solubility in non-halogenated solvents, resulting in suboptimal morphology. Therefore, in this study, the impact of modifying the inner and outer side-chains of Y6 on OSC performance is investigated. The study reveals that blending a polymer donor, PM6, with one of the modified NFAs, namely N-HD, achieved an impressive PCE of 18.3% on a small-area OSC. This modified NFA displays improved solubility in o-xylene at room temperature, which facilitated the formation of a favorable BHJ morphology. A large-area (55 cm2) sub-module delivered an impressive PCE of 12.2% based on N-HD using o-xylene under ambient conditions. These findings underscore the significant impact of the modified Y6 derivatives on structural arrangements and film processing over a large-area module at room temperature. Consequently, these results are poised to deepen the comprehension of the scaling challenges encountered in OSCs and may contribute to their commercialization.

Morphology Control for Efficient Nonfused Acceptor-Based Organic Photovoltaic Cells.

Non-fused electron acceptors have huge advantages in fabricating low-cost organic photovoltaic (OPV) cells. However, morphology control is a challenge as non-fused C─C single bonds bring more molecular conformations. Here, by selecting two typical polymer donors, PBDB-TF and PBQx-TF, the blend morphologies and its impacts on the power conversion efficiencies (PCEs) of non-fused acceptor-based OPV cells are studied. A selenium-containing non-fused acceptor named ASe-5 is designed. The results suggest that PBQx-TF has a lower miscibility with ASe-5 when compared with PBDB-TF. Additionally, the polymer networks may form earlier in the PBQx-TF:ASe-5 blend film due to stronger preaggregation performance, leading to a more obvious phase separation. The PBQx-TF:ASe-5 blend film shows faster charge transfer and suppressed charge recombination. As a result, the PBQx-TF:ASe-5-based device records a good PCE of 14.7% with a higher fill factor (FF) of 0.744, while the PBDB-TF:ASe-5-based device only obtains a moderate PCE of 12.3% with a relatively low FF of 0.662. The work demonstrates that the selection of donors plays a crucial role in controlling the blend morphology and thus improving the PCEs of non-fused acceptor-based OPV cells.

Design of Chlorinated Indaceno[1,2-b:5,6-b']dithiophene Acceptors toward Efficient Organic Photovoltaics.

Chlorinated modifications have been extensively employed to modulate the optoelectronic properties of π-conjugated materials. Herein, the Cl substitution in designing nonfullerene acceptors (NFAs) with various bandgaps is studied. Four narrow-bandgap electron acceptors (GS-40, GS-41, GS-42, and GS-43) were synthesized by tuning the electrostatic potential distributions of the molecular conjugated backbones. The optical absorption onset of these NFAs ranges from 900 to 1030 nm. Compared to the nonchlorinated analogue, the introduction of Cl atoms on the core of indaceno[1,2-b:5,6-b'] dithiophene (IDT) and π spacer results in an upward shift of the lowest unoccupied molecular orbital levels and induces a blue shift in the absorption spectra of the NFAs. This alteration facilitates achieving appropriate energy-level alignment and favorable bulk heterojunction morphology when blended with the widely used donor PBDB-TF. The PBDB-TF:GS-43-based solar cells show an optimal power conversion efficiency of 13.3%. This work suggests the potential of employing chlorine-modified IDT and thiophene units as fundamental building blocks for developing high-performance photoactive materials.

Morphology and Performance Enhancement through the Strong Passivation Effect of Amphoteric Ions in Tin-based Perovskite Solar Cells.

Despite the optoelectronic similarities between tin and lead halide perovskites, the performance of tin-based perovskite solar cells remains far behind, with the highest reported efficiency to date being ≈14%. This is highly correlated to the instability of tin halide perovskite, as well as the rapid crystallization behavior in perovskite film formation. In this work, l-Asparagine as a zwitterion plays a dual role in controlling the nucleation/crystallization process and improving the morphology of perovskite film. Furthermore, tin perovskites with l-Asparagine show more favorable energy-level matching, enhancing the charge extraction and minimizing the charge recombination, leading to an enhanced power conversion efficiency of 13.31% (from 10.54% without l-Asparagine) with remarkable stability. These results are also in good agreement with the density functional theory calculations. This work not only provides a facile and efficient approach to controlling the crystallization and morphology of perovskite film but also offers guidelines for further improved performance of tin-based perovskite electronic devices.

Non-Fullerene Acceptors with Benzodithiophene-Based Fused Planar Ring Cores for Organic Solar Cells.

Fused aromatic rings are widely employed in organic solar cell (OSC) materials due to their planarity and rigidity. Here, we designed and synthesized four two-dimensional non-fullerene acceptors, D6-4F, D6-4Cl, DTT-4F, and DTT-4Cl, based on two new fused planar ring structures of f-DTBDT-C6 and f-DTTBDT. Owing to the desirable phase separation formed in the blend films and the higher energy levels induced by the extra alkyl groups, PM6:D6-4F-based devices achieved a high VOC = 0.91 V with PCE = 11.10%, FF = 68.54%, and JSC = 17.75 mA/cm2. Because of the longer π-conjugation of the f-DTTBDT core with nine fused rings, DTT-4F and DTT-4Cl showed high molar extinction coefficients and broad absorption bands that enhanced the current density of OSCs. Finally, the PM6:DTT-4F-based devices achieved a JSC = 19.82 mA/cm2 with PCE = 9.68%, VOC = 0.83 V, and FF = 58.85%.

Large Steric Hindrance Enhanced Molecular Planarity for Low-Cost Non-Fused Electron Acceptors.

Designing efficient non-fused ring electron acceptors is of great importance in decreasing the material cost of organic photovoltaic cells (OPVs). It is a challenge to construct a planar molecular skeleton in non-fused molecules as there are many torsions between adjacent units. Here, we design two non-fused electron acceptors based on bithieno[3,2-b]thiophene units as core structures and study the impact of steric hindrance of substituents on molecular planarity. We use 2,4,6-triisopropylphenyl and 4-hexylphenyl groups to prepare ATTP-1 and ATTP-2, respectively. Our results suggest that the enhanced steric hindrance is beneficial for obtaining a more planar molecular configuration, which significantly increases the optical absorption and charge transport properties. The power conversion efficiency (PCE) of PBDB-TF:ATTP-1 combination (11.3%) is superior to that of PBDB-TF:ATTP-2 combination (3.7%). In addition, an impressive PCE of 10.7% is recorded in ATTP-1-based devices when a low-cost polythiophene donor PDCBT is used, which is an outstanding value in OPVs fabricated by non-fused donor/acceptor combinations. Our work demonstrates that modulation of the steric hindrance effect is of great significance to control the molecular planarity and thus obtain excellent photovoltaic performance of low-cost non-fused electron acceptors.

Ladder-Type Fused Benzodithiophene Extended along the Short-Axis Direction as a New Donor Building Block for Efficient Organic Solar Cells.

Ladder-type fused aromatic systems are important core structures of small molecule acceptors for organic solar cells (OSCs). In this study, a new ladder-type donor building block, based on the benzo[1,2-b:4,5-b']dithiophene (BDT) unit where the 3,7 positions of the BDT thiophene rings and the 3' position of the thiophene rings of the vertical BDT were fused to construct a seven-ring core structure named f-DTBDT, was investigated. In the f-DTBDT structure, the fusion of the BDT core and the thiophene rings at the 4,8 positions of BDT constrains all of the aromatic rings in a coplanar structure. The newly designed f-DTBDT was successfully employed as a core donor building block and conjugated with three electron-withdrawing acceptors (2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene) malononitrile (2HIC), 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (2FIC), and 2-(5,6-dichloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (2ClIC)) as acceptor-donor-acceptor (A-D-A)-type acceptor materials for OSCs. Characterization results showed that the three synthesized A-D-A acceptors of DTBDT-IC, DTBDT-4F, and DTBDT-4Cl have high absorption behavior in the vis-NIR region as result of an intramolecular charge transfer interaction engendered by f-DTBDT and the ending group. The absorption regions of the acceptors were complementary with that of polymer PM6. Also, the frontier orbital energy levels of the new acceptors and wide-band-gap PM6 are well matched. Bulk heterojunction OSCs were fabricated using PM6 and the acceptors, and the highest power conversion efficiency (PCE) of 10.15% was obtained when using PM6:DTBDT-4F as the active layer.

Highly Efficient and Photostable Ternary Organic Solar Cells Enabled by the Combination of Non-Fullerene and Fullerene Acceptors with Thienopyrrolodione-based Polymer Donors.

Two polymer donors, PFBDT-8ttTPD and PClBDT-8ttTPD, consisting of halogenated thiophene-substituted benzo[1,2-b:4,5-b']dithiophene and alkyl-substituted thieno[3,2-b]thiophene linked thieno[3,4-c]pyrrole-4,6(5H)-dione, were designed and synthesized for the evaluation of photovoltaic performances. The fabricated IT-4F-based organic solar cells (OSCs) exhibited maximum power conversion efficiency (PCE) values of 12.81 and 11.12% for PFBDT-8ttTPD and PClBDT-8ttTPD, respectively. Furthermore, PFBDT-8ttTPD:Y6 showed significantly improved PCE (15.05%) due to the extended light harvesting in the broad solar spectrum, whereas the PClBDT-8ttTPD:Y6 displayed relatively low PCE (10.02%). A ternary system incorporating PC71BM as the third component into bulk-heterojuction composites (PFBDT-8ttPTD:non-fullerene) was investigated with the aim of utilizing the advantages of PC71BM. As a result, PFBDT-8ttTPD:IT-4F:PC71BM exhibited an improved PCE (13.67%) compared to that of the corresponding binary OSC. In particular, ternary OSC of PFBDT-8ttTPD:Y6:PC71BM showed outstanding photovoltaic performance (PCE = 16.43%) as well as photostability, retaining approximately 80% of the initial PCE after 500 h under continuous illumination. The introduction of a small amount of PC71BM resulted in favorable and dense molecular packing with improved crystallinity as well as enhanced charge carrier mobility for efficient OSC.