Precisely Regulating Intermolecular Interactions and Molecular Packing of Nonfused-Ring Electron Acceptors via Halogen Transposition for High-Performance Organic Solar Cells.

The structure of molecular aggregates is crucial for charge transport and photovoltaic performance in organic solar cells (OSCs). Herein, the intermolecular interactions and aggregated structures of nonfused-ring electron acceptors (NFREAs) are precisely regulated through a halogen transposition strategy, resulting in a noteworthy transformation from a 2D-layered structure to a 3D-interconnected packing network. Based on the 3D electron transport pathway, the binary and ternary devices deliver outstanding power conversion efficiencies (PCEs) of 17.46% and 18.24%, respectively, marking the highest value for NFREA-based OSCs.

Precisely Manipulating Molecular Packing via Tuning Alkyl Side-Chain Topology Enabling High-Performance Nonfused-Ring Electron Acceptors.

In the development of high-performance organic solar cells (OSCs), the self-organization of organic semiconductors plays a crucial role. This study focuses on the precisely manipulation of molecular assemble via tuning alkyl side-chain topology in a series of low-cost nonfused-ring electron acceptors (NFREAs). Among the three NFREAs investigated, DPA-4, which possesses an asymmetric alkyl side-chain length, exhibits a tight packing in the crystal and high crystallinity in the film, contributing to improved electron mobility and favorable film morphology for DPA-4. As a result, the OSC device based on DPA-4 achieves an excellent power conversion efficiency of 16.67 %, ranking among the highest efficiencies for NFREA-based OSCs.

Precise Methylation Yields Acceptor with Hydrogen-Bonding Network for High-Efficiency and Thermally Stable Polymer Solar Cells.

Utilizing intermolecular hydrogen-bonding interactions stands for an effective approach in advancing the efficiency and stability of small-molecule acceptors (SMAs) for polymer solar cells. Herein, we synthesized three SMAs (Qo1, Qo2, and Qo3) using indeno[1,2-b]quinoxalin-11-one (Qox) as the electron-deficient group, with the incorporation of a methylation strategy. Through crystallographic analysis, it is observed that two Qox-based methylated acceptors (Qo2 and Qo3) exhibit multiple hydrogen bond-assisted 3D network transport structures, in contrast to the 2D transport structure observed in gem-dichlorinated counterpart (Qo4). Notably, Qo2 exhibits multiple and stronger hydrogen-bonding interactions compared with Qo3. Consequently, PM6 : Qo2 device realizes the highest power conversion efficiency (PCE) of 18.4 %, surpassing the efficiencies of devices based on Qo1 (15.8 %), Qo3 (16.7 %), and Qo4 (2.4 %). This remarkable PCE in PM6 : Qo2 device can be primarily ascribed to the enhanced donor-acceptor miscibility, more favorable medium structure, and more efficient charge transfer and collection behavior. Moreover, the PM6 : Qo2 device demonstrates exceptional thermal stability, retaining 82.8 % of its initial PCE after undergoing annealing at 65 °C for 250 hours. Our research showcases that precise methylation, particularly targeting the formation of intermolecular hydrogen-bonding interactions to tune crystal packing patterns, represents a promising strategy in the molecular design of efficient and stable SMAs.

Improving the Performance of Layer-by-Layer Organic Solar Cells by n-Doping of the Acceptor Layer.

Molecular dopants can effectively improve the performance of organic solar cells (OSCs). Here, PM6/BTP-eC9-4Cl-based OSCs are fabricated by a layer-by-layer (LbL) deposition method, and the electron acceptor BTP-eC9-4Cl layer is properly doped by n-type dopant benzyl viologen (BV) or [4-(1,3-dimethyl-2,3-dihydro-1H-benzoimidazol-2-yl)phenyl]dimethyl-amine (N-DMBI-H). The power conversion efficiency (PCE) of OSCs increases from 16.80 to 17.61 or 17.84% when the acceptor layer is doped by BV (0.01 wt %) or N-DMBI-H (0.01 wt %), respectively. At the optimal doping concentration, the device exhibits more balanced charge transport, fewer bimolecular recombinations, faster charge separation and transfer, and better stability. This doping strategy has good universality; when the acceptor layer L8-BO of LbL OSCs is doped by 0.01 wt % BV or 0.01 wt % N-DMBI-H, the PCE increases from 17.49 to 18.35 or 18.25%, respectively. All in all, our studies have demonstrated that the doping strategy is effective in enhancing the performance of OSCs.

Improving the Performance of Layer-by-Layer Processed Organic Solar Cells via Introducing a Wide-Bandgap Dopant into the Upper Acceptor Layer.

The layer-by-layer (LbL) solution-processed organic solar cells (OSCs) are conductive to achieve vertical phase separation, tunable donor-acceptor (D/A) interfaces, and favorable charge-transport pathways. In this work, a wide-bandgap component poly(9-vinylcarbazole) (PVK) is added to the upper electron acceptor layer to improve the performance of LbL-processed OSCs. Results show that the PVK component can adjust the film morphology, dope the electron acceptor, increase the electron concentration, and improve charge transport. Such n-type doping is verified by Seebeck coefficient measurement, ultraviolet photoelectron spectroscopy, and electron paramagnetic resonance characterization. In addition, the fluorescence intensity and exciton lifetime of the PVK-doped acceptor film are increased, thus being beneficial for exciton diffusion to the D/A interface. Therefore, the power conversion efficiency (PCE) of LbL OSCs increases when 2.50 wt.% PVK is employed in the electron acceptor layer of commonly-used high-efficiency system and a maximum value of 19.05% can be achieved. The role of PVK played in the active layer is different from those of additives and ternary components reported previously, so the results provide an alternative way to enhance the device performance of LbL-processed OSCs.

High-Performance Organic Solar Cells Containing Pyrido[2,3-b]quinoxaline-Core-Based Small-Molecule Acceptors with Optimized Orbit Overlap Lengths and Molecular Packing.

The central core in A-DA1 D-A-type small-molecule acceptor (SMAs) plays an important role in determining the efficiency of organic solar cells (OSCs), while the principles governing the efficient design of SMAs remain elusive. Herein, we developed a series of SMAs with pyrido[2,3-b]quinoxaline (PyQx) as new electron-deficient unit by combining with the cascade-chlorination strategy, namely Py1, Py2, Py3, Py4 and Py5. The introduction of chlorine atoms reduces the intramolecular charge transfer effects but elevates the LUMO values. Density functional theory (DFT) reveals that Py2 with ortho chlorine substituted PyQx and Py5 with two chlorine atoms yield larger dipole moments and smaller π⋅⋅⋅π stacking distances, as compared with the other three acceptors. Moreover, Py2 shows the strongest light absorption capability induced by extended orbit overlap lengths and more efficient packing structures in the dimers. These features endow the best device performance of Py2 due to the better molecular packing and aggregation behaviors, more suitable domain sizes with better exciton dissociation and charge recombination. This study highlights the significance of incorporating large dipole moments, small π⋅⋅⋅π stacking distances and extended orbit overlap lengths in dimers into the development of high-performance SMAs, providing insight into the design of efficient A-DA1 D-A-type SMAs for OSCs.

Effect of Steric Hindrance at the Anthracene Core on the Photovoltaic Performance of Simple Nonfused Ring Electron Acceptors.

Solving the contradiction between good solubility and dense packing is a challenge in designing high-performance nonfullerene acceptors. Herein, two simple nonfused ring electron acceptors (o-AT-2Cl and m-AT-2Cl) carrying ortho- or meta-substituted hexyloxy side chains can be facilely synthesized in only three steps. The two ortho-substituted phenyl side chains in o-AT-2Cl cannot freely rotate due to a big steric hindrance, which endows the acceptor with good solubility. Moreover, o-AT-2Cl displays a more ordered packing than m-AT-2Cl as revealed by the absorption measurement. When blended with polymer donor D18 for the fabrication of organic solar cells (OSCs), o-AT-2Cl-based devices exhibit a favorable morphology, more efficient exciton dissociation, and better charge transport. Consequently, the optimal OSCs based on D18:o-AT-2Cl exhibit a power conversion efficiency (PCE) of 12.8%, which is significantly higher than the moderate PCE (7.66%) for D18:m-AT-2Cl-based devices. Remarkably, o-AT-2Cl shows a higher figure-of-merit value compared with classic high-efficiency fused ring electron acceptors. As a result, our research succeeds in obtaining nonfused ring acceptors with cost-effective photovoltaic performance and provides a valuable experience for simultaneously improving solubility as well as ensuring ordered packing of acceptors through regulating the steric hindrance via changing the position of substituents.

High-Performance Nonfused Ring Electron Acceptors with V-Shaped Side Chains.

Motivated by simplifying the synthesis of nonfullerene acceptor and establishing the relation between molecular structure and photovoltaic performance, two isomeric nonfused ring electron acceptors (o-TT-Cl and m-TT-Cl), whose properties can be adjusted by changing the side chains, are designed and synthesized with several high-yield steps. o-TT-Cl with V-shaped side chain induces a dominated J-aggregation and displays much better solubility and more ordered packing than m-TT-Cl with linear side chain. Thus, the o-TT-Cl-based blend film generates better phase morphology and charge transport than m-TT-Cl-based one. Finally, the power conversion efficiency of o-TT-Cl-based devices is 12.84%, which is much higher than that of m-TT-Cl-based ones (6.54%). This work highlights the importance of side chains engineering on improving photovoltaic performance of nonfused ring electron acceptors.

Designing High-Performance Nonfused Ring Electron Acceptors via Synergistically Adjusting Side Chains and Electron-Withdrawing End-Groups.

Three nonfused ring electron acceptors, Hexyl-0F, Isopropyl-0F, and Isopropyl-2F, are designed and synthesized. Unlike Hexyl-0F, Isopropyl-0F with two sterically hindered 2,4,6-triisopropyl-phenyl groups is highly soluble, which provides a good opportunity for solution processability. Compared with Isopropyl-0F, Isopropyl-2F with fluorinated end-groups exhibits red-shifted absorption. Due to these synergistic adjustment, Isopropyl-2F-based devices displayed a high power conversion efficiency of 12.55%, higher than that of Isopropyl-0F (9.49%). The result demonstrates that the introduction of large steric substituents in the π-bridge units and electron-withdrawing end-groups plays a positive role in the construction of high-efficiency nonfused ring electron acceptors.

High-Performance Simple Nonfused Ring Electron Acceptors with Diphenylamino Flanking Groups.

Four simple nonfused ring electron acceptors (H-2F, CH3-2F, OCH3-2F, and SCH3-2F) were designed and synthesized. The use of diphenylamine derivatives as the flanking group for the construction of nonfused ring electron acceptors can improve solubility, avoid the formation of oversized aggregates, and enhance the intramolecular charge-transfer effect to extend absorption spectra. The substituent group at the diphenylamine unit has a great impact on the absorption and energy level of acceptors, electron mobility and morphology of blend films. Unlike the other three acceptors, CH3-2F can form ordered molecular stacking and a face-on orientation in the donor/acceptor blend film. A single-crystal analysis demonstrates that CH3-2F can form a two-dimensional electron transport network. Among these four acceptors, CH3-2F-based organic solar cells provide the highest PCE of 12.28%. Our work has demonstrated that triarylamine is a helpful construction unit for low-cost and high efficiency nonfused ring electron acceptors.

Enhancing the Photovoltaic Performance of a Benzo[c][1,2,5]thiadiazole-Based Polymer Donor via a Non-Fullerene Acceptor Pairing Strategy.

As a well-known electron-withdrawing group, benzo[c][1,2,5]thiadiazole (BT) has been intensively studied and adopted to construct polymer donors with tunable band gaps. However, polymer solar cells (PSCs) with BT-based polymer donors, limited by the weak absorption and inflexible energy level of fullerene derivatives, usually suffer mediocre power conversion efficiencies (PCEs). Here, through subtly tailoring a BT unit with asymmetric fluoro and alkyloxy groups and judiciously pairing a BT-based polymer donor with three narrow band gap non-fullerene acceptors (e.g., IEICO-4F, ITOIC-2F, and IDTCN-O), active layers with complementary absorption spectra, small lowest unoccupied molecular orbital (LUMO) offsets, and preferred morphologies have been achieved. Consequently, PSCs with excellent Jsc values (over 20 mA/cm2) and high PCEs up to 12.33% have been obtained. To the best of our knowledge, the value of 12.33% is among the highest PCEs for BT-based polymers in binary PSCs so far. This work demonstrates that the cooperative effect of energy levels, absorption spectra, and morphologies between the donors and acceptors is crucial for governing the performance of organic photovoltaics.

Efficient Ternary Organic Solar Cells with a New Electron Acceptor Based on 3,4-(2,2-Dihexylpropylenedioxy)thiophene.

In this work, a ternary blend strategy based on PBDB-T and two small molecular acceptors (IDTT-OB and IDT-PDOT-C6) is demonstrated to simultaneously improve the photocurrent and reduce the voltage loss in organic solar cells (OSCs). The improved photocurrent is partially due to a broad absorption spectrum of the active layer. In addition, we find that the ternary system possesses a higher degree of crystallinity, smaller domain size, higher domain purity, and higher and more balanced charge-carrier mobilities in comparison with the two corresponding binary systems. The reduced voltage loss in the ternary device is mainly due to a lower energy loss (Eloss) of charge carriers. We achieve a Eloss of only 0.50 eV, which is one of the lowest values reported for the ternary nonfullerene OSCs. Our results have demonstrated that all photovoltaic parameters of ternary OSCs can be simultaneously improved by elaborately selecting the three active layer components.

PDI-Based Hexapod-Shaped Nonfullerene Acceptors for the High-Performance As-Cast Organic Solar Cells.

Three hexapod-shaped PDI-hexamers (PSM1, PSM2, and PSM3) with a diphenylmethylene-bridged triphenylamine (TPA) core and six peripheral PDI subunits have been designed and synthesized. The influence of different peripheral PDI subunits on the morphology and crystallinity of acceptors is investigated. Distinctly different from the previously reported PDI trimers with a TPA core, which exhibit amorphous morphologies, these hexapod-shaped acceptors display improved crystallinities and photophysical properties. Our studies have shown that PSM3 with six peripheral thiophene-fused PDI subunits gives the best result. The as-cast blend films of PBDB-T and PSM3, which possess appropriate phase separation and higher crystallinity, show high and balanced charge mobilities. As expected, OSCs with PBDB-T:PSM3 as the active layer achieve the highest power conversion efficiency of 6.71% among these three acceptors, which is the highest one in TPA-based acceptors and one of the best for the as-cast OSCs based on PDI derivatives.

Noncovalently fused-ring electron acceptors with near-infrared absorption for high-performance organic solar cells.

Non-fullerene fused-ring electron acceptors boost the power conversion efficiency of organic solar cells, but they suffer from high synthetic cost and low yield. Here, we show a series of low-cost noncovalently fused-ring electron acceptors, which consist of a ladder-like core locked by noncovalent sulfur-oxygen interactions and flanked by two dicyanoindanone electron-withdrawing groups. Compared with that of similar but unfused acceptor, the presence of ladder-like structure markedly broadens the absorption to the near-infrared region. In addition, the use of intramolecular noncovalent interactions avoids the tedious synthesis of covalently fused-ring structures and markedly lowers the synthetic cost. The optimized solar cells displayed an outstanding efficiency of 13.24%. More importantly, solar cells based on these acceptors demonstrate very low non-radiative energy losses. This research demonstrates that low-cost noncovalently fused-ring electron acceptors are promising to achieve high-efficiency organic solar cells.

Fluoro-Modulated Molecular Geometry in Diketopyrrolopyrrole-Based Low-Bandgap Copolymers for Tuning the Photovoltaic Performance.

Fluorination of conjugated polymers is an effective strategy to tune the energy levels for obtaining high power conversion efficiency (PCE) in organic solar cells. In this work, we have developed fluoro-modulated molecular geometries in diketopyrrolopyrrole based low-bandgap copolymers. In these polymers, planar conformation can be locked by intramolecular non-covalent interaction (intramolecular supramolecular interaction) between the sulfur atoms and the introduced F atoms (F···S interaction). By varying the fluorinated moieties, such a planarity can be disturbed and the molecular geometry is tuned. As a result, the polymer' properties can be modulated, including the ultraviolet-visible absorption spectrum to become broaden, charge mobility to be enhanced, open-circuit voltage (V oc) and short-circuited current (J sc) to be elevated, and thus photovoltaic performance to be improved. The photovoltaic device based on PCFB, one of the fluorinated terpolymers, exhibited a high PCE near 8.5% with simultaneously enhanced V oc and J sc relative to the non-fluorinated one (PCB).

Impact of the Bonding Sites at the Inner or Outer π-Bridged Positions for Non-Fullerene Acceptors.

Two A-π-D-π-A-type non-fullerene acceptors (IDT-ToFIC and IDT-TiFIC) with 5-hexylthienyl chains substituted at the inner and outer ß-positions of the thiophene π-bridge have been designed, respectively. Impacts of varied positional modifications are systematically studied. By utilizing PBDB-T as the donor, polymer solar cells are constructed with these two molecules as acceptors. Power conversion efficiencies of 11.09 and 9.46% are acquired for IDT-ToFIC- and IDT-TiFIC-based devices, respectively. Our studies have demonstrated that the use of thiophene spacers carrying one conjugated side chain at different positions can markedly enhance the photovoltaic properties relative to the corresponding control molecule IDTT2F.

Controlling Molecular Packing and Orientation via Constructing a Ladder-Type Electron Acceptor with Asymmetric Substituents for Thick-Film Nonfullerene Solar Cells.

A nonfullerene acceptor, IDTT-OB, employing indacenodithieno[3,2- b]thiophene (IDTT) decorated with asymmetric substituents as the core, is designedly prepared. In comparison with the analogue IDT-OB, extending the five-heterocyclic indacenodithiophene (IDT) core to seven-heterocyclic fused ring endows IDTT-OB with more broad absorption and elevated highest occupied molecular orbital energy level. In addition, IDTT-OB shows a more intense molecular packing and a higher crystalline behavior with a strong face-on orientation in the neat film and the PBDB-T:IDTT-OB blend film. Furthermore, an ideal nanomorphology with a domain size of 19 nm can be obtained, which is in favor of exciton diffusion and charge separation. Accordingly, PBDB-T:IDTT-OB-based polymer solar cells demonstrate a maximum power conversion efficiency (PCEmax) of 11.19% with an impressive fill factor of 0.74, comparable to the state-of-the-art acceptors with similar molecular backbones. More importantly, IDTT-OB-based devices show good tolerance to the film thickness, which maintain a high PCE of 10.20% with a 250 nm thick active layer, demonstrating that the asymmetric acceptor is profound for fabricating high-efficiency thick-film nonfullerene solar cells.

Effect of Non-fullerene Acceptors' Side Chains on the Morphology and Photovoltaic Performance of Organic Solar Cells.

Three indacenodithieno[3,2-b]thiophene (IT) cored small molecular acceptors (ITIC-SC6, ITIC-SC8, and ITIC-SC2C6) were synthesized, and the influence of side chains on their performances in solar cells was systematically probed. Our investigations have demonstrated the variation of side chains greatly affects the charge dissociation, charge mobility, and morphology of the donor:acceptor blend films. ITIC-SC2C6 with four branched side chains showed improved solubility, which can ensure the polymer donor to form favorable fibrous nanostructure during the drying of the blend film. Consequently, devices based on PBDB-ST:ITIC-SC2C6 demonstrated higher charge mobility, more effective exciton dissociation, and the optimal power conversion efficiency up to 9.16% with an FF of 0.63, a Jsc of 15.81 mA cm-2, and a Voc of 0.92 V. These results reveal that the side chain engineering is a valid way of tuning the morphology of blend films and further improving PCE in polymer solar cells.

Fused-Ring Acceptors with Asymmetric Side Chains for High-Performance Thick-Film Organic Solar Cells.

A kind of new fused-ring electron acceptor, IDT-OB, bearing asymmetric side chains, is synthesized for high-efficiency thick-film organic solar cells. The introduction of asymmetric side chains can increase the solubility of acceptor molecules, enable the acceptor molecules to pack closely in a dislocated way, and form favorable phase separation when blended with PBDB-T. As expected, PBDB-T:IDT-OB-based devices exhibit high and balanced hole and electron mobility and give a high power conversion efficiency (PCE) of 10.12%. More importantly, the IDT-OB-based devices are not very sensitive to the film thickness, a PCE of 9.17% can still be obtained even the thickness of active layer is up to 210 nm.

Induction of the Epstein-Barr virus latent membrane protein 2 antigen-specific cytotoxic T lymphocytes using human leukocyte antigen tetramer-based artificial antigen-presenting cells.

Cytotoxic T lymphocytes (CTLs) specific for the Epstein-Barr virus (EBV) latent membrane protein 2 (LMP2) antigen are important reagents for the treatment of some EBV-associated malignancies, such as EBV-positive Hodgkin's disease and nasopharyngeal carcinoma. However, the therapeutic amount of CTLs is often hampered by the limited supply of antigen-presenting cells. To address this issue, an artificial antigen-presenting cell (aAPC) was made by coating a human leukocyte antigen (HLA)-pLMP2 tetrameric complex, anti-CD28 antibody and CD54 molecule to a cell-sized latex bead, which provided the dual signals required for T cell activation. By co-culture of the HLA-A2-LMP2 bearing aAPC and peripheral blood mononuclear cells from HLA-A2 positive healthy donors, LMP2 antigen-specific CTLs were induced and expanded in vitro. The specificity of the aAPC-induced CTLs was demonstrated by both HLA-A2-LMP2 tetramer staining and cytotoxicity against HLA-A2-LMP2 bearing T2 cell, the cytotoxicity was inhibited by the anti-HLA class I antibody (W6/32). These results showed that LMP2 antigen-specific CTLs could be induced and expanded in vitro by the HLA-A2-LMP2-bearing aAPC. Thus, aAPCs coated with an HLA-pLMP2 complex, anti-CD28 and CD54 might be promising tools for the enrichment of LMP2-specific CTLs for adoptive immunotherapy.