Molecular interaction induced dual fibrils towards organic solar cells with certified efficiency over 20.

The nanoscale fibrillar morphology, featuring long-range structural order, provides abundant interfaces for efficient exciton dissociation and high-quality pathways for effective charge transport, is a promising morphology for high performance organic solar cells. Here, we synthesize a thiophene terminated non-fullerene acceptor, L8-ThCl, to induce the fibrillization of both polymer donor and host acceptor, that surpasses the 20% efficiency milestone of organic solar cells. After adding L8-ThCl, the original weak and less continuous nanofibrils of polymer donors, i.e. PM6 or D18, are well enlarged and refined, whilst the host acceptor L8-BO also assembles into nanofibrils with enhanced structural order. By adapting the layer-by-layer deposition method, the enhanced structural order can be retained to significantly boost the power conversion efficiency, with specific values of 19.4% and 20.1% for the PM6:L8-ThCl/L8-BO:L8-ThCl and D18:L8-ThCl/L8-BO:L8-ThCl devices, with the latter being certified 20.0%, which is the highest certified efficiency reported so far for single-junction organic solar cells.

Brominated Quaternary Ammonium Salt-Assisted Hybrid Electron Transport Layer for High-Performance Conventional Organic Solar Cells.

Interlayer engineering is crucial for achieving efficient and stable organic solar cells (OSCs). Herein, by introducing a commercialized brominated quaternary ammonium salt, hexamethonium bromide (HB), into a perylene diimide (PDI)-structured electron transport layer (ETL), a PDINN:HB hybrid ETL with enhanced charge collection ability and environmental/operational stability is realized. Molecular dynamics simulations and Kelvin probe force microscopy indicate that strong polar bromine and amine groups can form extra interfacial dipoles in the hybrid interlayer, while X-ray photoelectron spectroscopy and electron paramagnetic resonance suggest the hybrid ETL can interact with the Ag cathode, thereby regulating the energy level arrangement at the interface. As for the results, the PDINN:HB hybrid ETL enables improved power conversion efficiency (PCE) from 17.8 to 18.4% and 18.8 to 19.4% in PM6:C5-16 bulk heterojunction- and PM6/L8-BO pseudobulk heterojunction-based OSCs, respectively. The versatility of this method is further verified by introducing a range of brominated quaternary ammonium salts into PDINN, in which a superior PCE and stability are all obtained compared to the reference device.

π-Extended Nonfullerene Acceptor for Compressed Molecular Packing in Organic Solar Cells To Achieve over 20% Efficiency.

Organic photovoltaics (OPVs) suffer from a trade-off between efficient charge transport and suppressed nonradiative recombination due to the aggregation-induced luminance quenching of organic semiconductors. To resolve this grand challenge, a π-extended nonfullerene acceptor (NFA) B6Cl with large voids among the honeycomb network is designed and introduced into photovoltaic systems. We find that the presence of a small amount of (i.e., 0.5 or 1 wt %) B6Cl can compress the molecular packing of the host acceptor L8-BO, leading to shortened π-π stacking distance from 3.59 to 3.50 Å (that will improve charge transport) together with ordered alkyl chain packing (that will inhibit nonradiative energy loss due to the suppressed C-C and C-H bonds vibrations), as validated by high-energy X-ray scattering measurements. This morphology transformation ultimately results in simultaneously improved JSC, FF, and VOC of OPVs. As a result, the maximum PCEs of PM6:L8-BO and D18:L8-BO are increased from 19.1 and 19.3% to 19.8 and 20.2%, respectively, which are among the highest values for single-junction OPVs. The university of B6Cl to increase the performance of OPVs is further evidenced in a range of polymer:NFA OPVs.

Electrostatic Potential Design of Solid Additives for Enhanced Molecular Order of Polymer Donor in Efficient Organic Solar Cells.

Polymeric semiconducting materials struggle to achieve fast charge mobility due to low structural order. In this work, five 1H-indene-1,3(2H)dione-benzene structured halogenated solid additives namely INB-5F, INB-3F, INB-1F, INB-1Cl, and INB-1Br with gradually varied electrostatic potential are designed and utilized to regulate the structural order of polymer donor PM6. Molecular dynamics simulations demonstrate that although the dione unit of these additives tends to adsorb on the backbone of PM6, the reduced electrostatic potential of the halogen-substituted benzene can shift the benzene interacting site from alkyl side chains to the conjugated backbone of PM6, not only leading to enhanced π-π stacking in out-of-plane but also arising new π-π stacking in in-plane together with the appearance of multiple backbone stacking in out-of-plane, consequent to the co-existence of face-on and edge-on molecular orientations. This molecular packing transformation further translates to enhanced charge transport and suppressed carrier recombination in their photovoltaics, with a maximum power conversion efficiency of 19.4% received in PM6/L8-BO layer-by-layer deposited organic solar cells.

Dual Interface Modification Using Potassium Aspartic Acid to Realize Low Dark Current, High-Speed Nonfullerene Photodetectors.

Organic photodetectors (OPDs) have attracted tremendous interest due to their potential applications in wearable electronics. However, due to the nonideal contacts between the electrodes and organic semiconductors, OPDs still suffer from high dark current and slow frequency response. Herein, by inserting potassium aspartic acid (PAA) interlayers between ITO/metal oxides and the metal oxides/active layer, the shunts and hole injections are blocked and the energy levels of the electrodes are aligned. As a result, our dual-interface modified OPDs (ITO/PAA/ZnO/PAA/PTB7-Th:ITIC/MoO3/Ag) exhibit suppressed dark current 550 times lower than the reference device, corresponding to specific detectivity of 2.1 × 1012 Jones, broad linear dynamic range of 113 dB, and quick response time to the nanosecond level. PAA interlayers have also been demonstrated to improve the storage stability of OPDs, leading to 10 times slower degradation for the on/off ratio when compared with the reference and conventional polyethylenimine-modified OPDs.

Alkoxythiophene-Directed Fibrillization of Polymer Donor for Efficient Organic Solar Cells.

Realizing fibrillar molecular framework is highly encouraged in organic solar cells (OSCs) due to the merit of efficient charge carrier transport. This is however mainly achieved via the chemical structural design of photovoltaic semiconductors. In this work, through the utilization of three alkoxythiophene additives, T-2OMe, T-OEH, and T-2OEH, the intermolecular interactions among a series of BDT-type polymer donors, i.e., PM6, D18, PBDB-T, and PTB7-Th, are tuned to self-assemble into nanofibrils during solution casting. X-ray technique and molecular dynamics simulation reveal that the alkoxythiophene with (2-ethylhexyl)oxy (─OEH) chains can attach on the 2-ethylhexyl (EH) chains of these polymer donors and promote their self-assembly into 1D nanofibrils, in their neat films as well as photovoltaic blends with L8-BO. By adapting these fibrillar polymer donors to construct pseudo-bulk heterojunction (P-BHJ) OSCs via layer-by-layer deposition, generally improved device performance is seen, with power conversion efficiencies enhanced from 18.2% to 19.2% (certified 18.96%) and from 17.9% to 18.7% for the PM6/L8-BO and D18/L8-BO devices, respectively. This work provides a physical approach to promote the fibrillar charge transport channels for efficient photovoltaics.

Electrostatic force promoted intermolecular stacking of polymer donors toward 19.4% efficiency binary organic solar cells.

Conjugated polymers are generally featured with low structural order due to their aromatic and irregular structural units, which limits their light absorption and charge mobility in organic solar cells. In this work, we report a conjugated molecule INMB-F that can act as a molecular bridge via electrostatic force to enhance the intermolecular stacking of BDT-based polymer donors toward efficient and stable organic solar cells. Molecular dynamics simulations and synchrotron X-ray measurements reveal that the electronegative INMB-F adsorb on the electropositive main chain of polymer donors to increase the donor-donor interactions, leading to enhanced structural order with shortened π-π stacking distance and consequently enhanced charge transport ability. Casting the non-fullerene acceptor layer on top of the INMB-F modified donor layer to fabricate solar cells via layer-by-layer deposition evidences significant power conversion efficiency boosts in a range of photovoltaic systems. A power conversion efficiency of 19.4% (certified 18.96%) is realized in PM6/L8-BO binary devices, which is one of the highest reported efficiencies of this material system. The enhanced structural order of polymer donors by INMB-F also leads to a six-fold enhancement of the operational stability of PM6/L8-BO organic solar cells.

Reexamining the Role of Solution-Cast Ferroelectric Polymer Interlayer toward Enhanced Efficiency and Stability in Conventional Organic Solar Cells.

Interfacial modification is crucial for achieving efficient and stable organic solar cells (OSCs). Herein, an N,N-dimethylformamide (DMF) solution-cast poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)) interlayer was applied to enhance the efficiency and stability of a range of OSCs, and the underlying mechanism was revealed via morphological and device physics studies. DMF rinse during the P(VDF-TrFE) interlayer casting process strengthens π-π stacking of the active layer with fibril aggregation, optimized phase separation, and vertical component distribution, while the P(VDF-TrFE) interlayer with rich diploes contributes to increased surface potential and internal electric field. The synergistic effect of the P(VDF-TrFE) interlayer and DMF rinse increases the PCEs of PM6:IT-4F, PM6:C5-16, and PM6:L8-BO OSCs from 12.7, 17.9, and 18.2% to 13.1, 18.7, and 18.8%, respectively. Additionally, OSCs containing the P(VDF-TrFE) interlayer also showed improved storage stability.

A Polycrystalline Polymer Donor as Pre-Aggregate toward Ordered Molecular Aggregation for 19.3% Efficiency Binary Organic Solar Cells.

Organic semiconductors are generally featured with low structure order in solid-state films, which leads to low charge-transport mobility and strong charge recombination in their photovoltaic devices. In this work, a "polycrystal-induced aggregation" strategy orders the polymer donor (PM6) and non-fullerene acceptor (L8-BO) molecules during solution casting with the assistance of PM6 polycrystals that are incubated through a vapor diffusion method, toward improved solar cell efficiency with either thin or thick photoactive layers. These PM6 polycrystals are redissolved in chloroform to prepare PM6 pre-aggregates (PM6-PA), and further incorporated into the conventional PM6:L8-BO blend solutions, which is found to prolong the molecular organization process and enhance the aggregation of both the PM6 and the L8-BO components. As the results, with the assistance of 10% PM6-PA, PM6:L8-BO solar cell devices obtain power conversion efficiencies (PCEs) from 18.0% and 16.2% to 19.3% and 17.2% with a 100 nm-thick and 300 nm-thick photoactive layer, respectively.

Fibrillization of Non-Fullerene Acceptors Enables 19% Efficiency Pseudo-Bulk Heterojunction Organic Solar Cells.

The structural order and aggregation of non-fullerene acceptors (NFA) are critical toward light absorption, phase separation, and charge transport properties of their photovoltaic blends with electron donors, and determine the power conversion efficiency (PCE) of the corresponding organic solar cells (OSCs). In this work, the fibrillization of small molecular NFA L8-BO with the assistance of fused-ring solvent additive 1-fluoronaphthalene (FN) to substantially improve device PCE is demonstrated. Molecular dynamics simulations show that FN attaches to the backbone of L8-BO as the molecular bridge to enhance the intermolecular packing , inducing 1D self-assembly of L8-BO into fine fibrils with a compact polycrystal structure. The L8-BO fibrils are incorporated into a pseudo-bulk heterojunction (P-BHJ) active layer with D18 as a donor, and show enhanced light absorption, charge transport, and collection properties, leading to enhanced PCE from 16.0% to an unprecedented 19.0% in the D18/L8-BO binary P-BHJ OSC, featuring a high fill factor of 80%. This work demonstrates a strategy for fibrillating NFAs toward the enhanced performance of OSCs.

Tuning of the Interconnecting Layer for Monolithic Perovskite/Organic Tandem Solar Cells with Record Efficiency Exceeding 21.

The photovoltaic performance of inorganic perovskite solar cells (PSCs) still lags behind the organic-inorganic hybrid PSCs due to limited light absorption of wide bandgap CsPbI3-xBrx under solar illumination. Constructing tandem devices with organic solar cells can effectively extend light absorption toward the long-wavelength region and reduce radiative photovoltage loss. Herein, we utilize wide-bandgap CsPbI2Br semiconductor and narrow-bandgap PM6:Y6-BO blend to fabricate perovskite/organic tandem solar cells with an efficiency of 21.1% and a very small tandem open-circuit voltage loss of 0.06 V. We demonstrate that the hole transport material of the interconnecting layers plays a critical role in determining efficiency, with polyTPD being superior to PBDB-T-Si and D18 due to its low parasitic absorption, sufficient hole mobility and quasi-Ohmic contact to suppress charge accumulation and voltage loss within the tandem device. These perovskite/organic tandem devices also display superior storage, thermal and ultraviolet stabilities.

Simultaneously Enhanced Efficiency and Operational Stability of Nonfullerene Organic Solar Cells via Solid-Additive-Mediated Aggregation Control.

The additive strategy is widely used in optimizing the morphology of organic solar cells (OSCs). The majority of additives are liquid with high boiling points, which will be trapped within device and consequently deteriorate performance during operation. In this work, solid but volatile additives 2-(4-fluorobenzylidene)-1H-indene-1,3(2H)-dione (INB-F) and 2-(4-chlorobenzylidene)-1H-indene-1,3(2H)-dione (INB-Cl) are designed to replace the common 1,8-diiodooctane (DIO) in nonfullerene OSCs. These additives present during solution casting but evaporate after moderate heating. Molecular dynamics simulations show that they can reduce the adsorption energy to improve π-π stacking among nonfullerene acceptor (NFA) molecules, an effect that enhances light absorption and electron mobility. Both INB-F and INB-Cl enhance efficiency, with INB-F achieving a maximum efficiency of 16.7% from 15.1% of the reference PBDB-T-2F (PM6):BTP-BO-4F (Y6-BO) cell, and outperforming DIO. Remarkably, they can simultaneously enhance the operational stability, with the INB-F-treated OSC maintaining over 60% of the initial efficiency after 1000 h operation, demonstrating a T80 lifetime of 523 h, which is a significant improvement over T80 values of 66.2 h for the reference and 6.6 h for DIO-treated OSC. The simultaneously enhanced efficiency and operational lifetime are also effective in PM6:BTP-BO-4Cl (Y7-BO) OSCs, demonstrating a universal strategy to improve the performance of OSCs.

Molecular Ordering and Performance of Ternary Nonfullerene Organic Solar Cells via Bar-Coating in Air with an Efficiency over 13.

An in situ spectroscopy ellipsometry technique is utilized to probe the molecular ordering sequences of PBDB-T-2F/IT-4F/COi8DFIC ternary photovoltaic blends fabricated by bar-coating in air. The time-resolved dynamics show that the primary electron acceptor IT-4F aggregates ahead of the secondary acceptor COi8DFIC in the bar-coated photoactive layer, although the latter has much stronger crystallization ability. Wetting coefficient analysis supports that COi8DFIC locates at the interface between the host components PBDB-T-2F and IT-4F. We demonstrate that the suitable degree of phase separation with the presence of 20 wt % COi8DFIC facilitates exciton dissociation and charge transfer, leading to a remarkable power conversion efficiency of 13.2% as well as excellent stability of ternary organic solar cells (OSCs), which is among the highest reported efficiency for OSCs that were fabricated by scalable solution-casting in ambient conditions.

Agar/gelatin bilayer gel matrix fabricated by simple thermo-responsive sol-gel transition method.

We present a simple and environmentally-friendly method to generate an agar/gelatin bilayer gel matrix for further biomedical applications. In this method, the thermally responsive sol-gel transitions of agar and gelatin combined with the different transition temperatures are exquisitely employed to fabricate the agar/gelatin bilayer gel matrix and achieve separate loading for various materials (e.g., drugs, fluorescent materials, and nanoparticles). Importantly, the resulting bilayer gel matrix provides two different biopolymer environments (a polysaccharide environment vs a protein environment) with a well-defined border, which allows the loaded materials in different layers to retain their original properties (e.g., magnetism and fluorescence) and reduce mutual interference. In addition, the loaded materials in the bilayer gel matrix exhibit an interesting release behavior under the control of thermal stimuli. Consequently, the resulting agar/gelatin bilayer gel matrix is a promising candidate for biomedical applications in drug delivery, controlled release, fluorescence labeling, and bio-imaging.