Loosely Bounded Exciton with Enhanced Delocalization Capability Boosting Efficiency of Organic Solar Cells.

In organic solar cells (OSCs), electron acceptors have undergone multiple updates, from the initial fullerene derivatives, to the later acceptor-donor-acceptor type non-fullerene acceptors (NFAs), and now to Y-series NFAs, based on which efficiencies have reached over 19%. However, the key property responsible for further improved efficiency from molecular structure design is remained unclear. Herein, the material properties are comprehensively scanned by selecting PC71BM, IT-4F, and L8-BO as the representatives for different development stages of acceptors. For comparison, asymmetric acceptor of BTP-H5 with desired loosely bounded excitons is designed and synthesized. It's identified that the reduction of intrinsically exciton binding energy (Eb) and the enhancement of exciton delocalization capability act as the key roles in boosting the performance. Notably, 100 meV reduction in Eb has been observed from PC71BM to BTP-H5, correspondingly, electron-hole pair distance of BTP-H5 is almost two times over PC71BM. As a result, efficiency is improved from 40% of S-Q limit for PC71BM-based OSC to 60% for BTP-H5-based one, which achieves an efficiency of 19.07%, among the highest values for binary OSCs. This work reveals the confirmed function of exciton delocalization capability quantitatively in pushing the efficiency of OSCs, thus providing an enlightenment for future molecular design.

Evaporable Fullerene Indanones with Controlled Amorphous Morphology as Electron Transport Layers for Inverted Perovskite Solar Cells.

Fullerenes are among the most commonly used electron-transporting materials (ETMs) in inverted perovskite solar cells (IPSCs). Although versatile functionalized fullerene derivatives have shown excellent performance in IPSCs, pristine [60]fullerene (C60) is still the most widely used in devices mainly because of its uniform morphology by thermal deposition. However, thermally evaporable fullerene derivatives have not yet been achieved. Herein, we developed a series of evaporable fullerene derivatives, referred to as fullerene indanones (FIDOs), affording IPSCs with high power conversion efficiency (PCE) and long-term storage stability. The FIDOs were designed with a unique architecture in which the fullerene moiety and a benzene ring moiety are linked via a five-membered carbon ring in benzene ring plane. This molecular arrangement affords exceptional thermal stability, allowing the FIDOs to withstand harsh thermal deposition conditions. Moreover, by manipulating the steric bulk of the functional groups, we could control the state of the organic film from crystalline to amorphous. Subsequently, we used FIDOs as an electron transport layer (ETL) in IPSCs. Thanks to the suitable energy level and dual-passivation effect of FIDOs compared with a reference ETL using C60, the device using FIDOs achieved an open-circuit voltage of 1.16 V and a fill factor of 0.77. As a result, the PCE reached 22.11%, which is superior to 20.45% of the best-performing reference device. Most importantly, the FIDO-based IPSC devices exhibited exceptional stability in comparison to the reference device due to the stability of the amorphous ETL films.

Non-Halogenated Solvents Processed Efficient ITO-Free Flexible Organic Solar Cells with Upscaled Area.

Organic solar cells (OSCs) show the potential to harness solar energy at a lower cost and in a greener way with the merits of mechanical flexibility and potential low-cost upscaling production with solution processing. Meanwhile, the common use of toxic halogenated solvents causes pollution to the natural environment, and thus, needs to be avoided. Following the authors' previous work on the design of top-illuminated ultrathin Ag-based device structure highlighting most merits of OSC, herein non-halogen solvent and additive processing OSCs are presented, which exhibit high power conversion efficiency (PCE) of 17.64%, close to the best PCE with the commonly used halogen solvent. Interestingly, it is observed that the additive and the multicomponent strategy (blending third component BTP-S2 into PM6:L8-BO binary blend) synergistically affect the optimal morphology and device performance. Finally, OSC devices featuring green solvent processing, indium tin oxide-free, flexibility, and upscaling merits are fabricated and exhibit the best PCE of 13.76% with high mechanical robustness and good stability against heat or light illumination. This work provides a prospective potential for manufacturing the OSC toward practical applications.

Dithienopicenocarbazole-Based Acceptors for Efficient Organic Solar Cells with Optoelectronic Response Over 1000 nm and an Extremely Low Energy Loss.

Two cheliform non-fullerene acceptors, DTPC-IC and DTPC-DFIC, based on a highly electron-rich core, dithienopicenocarbazole (DTPC), are synthesized, showing ultra-narrow bandgaps (as low as 1.21 eV). The two-dimensional nitrogen-containing conjugated DTPC possesses strong electron-donating capability, which induces intense intramolecular charge transfer and intermolecular π-π stacking in derived acceptors. The solar cell based on DTPC-DFIC and a spectrally complementary polymer donor, PTB7-Th, showed a high power conversion efficiency of 10.21% and an extremely low energy loss of 0.45 eV, which is the lowest among reported efficient OSCs.

Tailoring the Interfacial Chemical Interaction for High-Efficiency Perovskite Solar Cells.

The ionic nature of perovskite photovoltaic materials makes it easy to form various chemical interactions with different functional groups. Here, we demonstrate that interfacial chemical interactions are a critical factor in determining the optoelectronic properties of perovskite solar cells. By depositing different self-assembled monolayers (SAMs), we introduce different functional groups onto the SnO2 surface to form various chemical interactions with the perovskite layer. It is observed that the perovskite solar cell device performance shows an opposite trend to that of the energy level alignment theory, which shows that chemical interactions are the predominant factor governing the interfacial optoelectronic properties. Further analysis verifies that proper interfacial interactions can significantly reduce trap state density and facilitate the interfacial charge transfer. Through use of the 4-pyridinecarboxylic acid SAM, the resulting perovskite solar cell exhibits striking improvements to the reach the highest efficiency of 18.8%, which constitutes an ∼10% enhancement compared to those without SAMs. Our work highlights the importance of chemical interactions at perovskite/electrode interfaces and paves the way for further optimizing performances of perovskite solar cells.

Morphology Evolution of High Efficiency Perovskite Solar Cells via Vapor Induced Intermediate Phases.

Morphology is critical component to achieve high device performance hybrid perovskite solar cells. Here, we develop a vapor induced intermediate phase (VIP) strategy to manipulate the morphology of perovskite films. By exposing the perovskite precursor films to different saturated solvent vapor atmospheres, e.g., dimethylformamide and dimethylsufoxide, dramatic film morphological evolution occurs, associated with the formation of different intermediate phases. We observe that the crystallization kinetics is significantly altered due to the formation of these intermediate phases, yielding highly crystalline perovskite films with less defect states and high carrier lifetimes. The perovskite solar cells with the reconstructed films exhibits the highest power conversion efficiency (PCE) up to 19.2% under 1 sun AM 1.5G irradiance, which is among the highest planar heterojunction perovskite solar cells. Also, the perovskite solar cells with VIP processing shows less hysteresis behavior and a stabilized power output over 18%. Our work opens up a new direction for morphology control through intermediate phase formation, and paves the way toward further enhancing the device performances of perovskite solar cells.

Enhanced photovoltaic performance of CH3NH3PbI3 perovskite solar cells through interfacial engineering using self-assembling monolayer.

Morphology control is critical to achieve high efficiency CH3NH3PbI3 perovskite solar cells (PSC). The surface properties of the substrates on which crystalline perovskite thin films form are expected to affect greatly the crystallization and, thus, the resulting morphology. However, this topic is seldom examined in PSC. Here we developed a facile but efficient method of modifying the ZnO-coated substrates with 3-aminopropanioc acid (C3-SAM) to direct the crystalline evolution and achieve the optimal morphology of CH3NH3PbI3 perovskite film. With incorporation of the C3-SAM, highly crystalline CH3NH3PbI3 films were formed with reduced pin-holes and trap states density. In addition, the work function of the cathode was better aligned with the conduction band minimum of perovskite for efficient charge extraction and electronic coupling. As a result, the PSC performance remarkably increased from 9.81(±0.99)% (best 11.96%) to 14.25(±0.61)% (best 15.67%). We stress the importance of morphology control through substrate surface modification to obtain the optimal morphology and device performance of PSC, which should generate an impact on developing highly efficient PSC and future commercialization.

Self-Assembled Interlayer Enables High-Performance Organic Photovoltaics with Power Conversion Efficiency Exceeding 20.

Interfacial layers (ILs) are prerequisites to form the selective charge transport for high-performance organic photovoltaics (OPVs) but mostly result in considerable parasitic absorption loss. Trimming the ILs down to a mono-molecular level via the self-assembled monolayer is an effective strategy to mitigate parasitic absorption loss. However, such a strategy suffers from inferior electrical contact with low surface coverage on rough surfaces and poor producibility. To address these issues, here, the self-assembled interlayer (SAI) strategy is developed, which involves a thin layer of 2-6 nm to form a full coverage on the substrate via both covalent and van der Waals bonds by using a self-assembled molecule of 2-(9H-carbazol-9-yl) (2PACz). Via the facile spin coating without further rinsing and annealing process, it not only optimizes the electrical and optical properties of OPVs, which enables a world-record efficiency of 20.17% (19.79% certified) but also simplifies the tedious processing procedure. Moreover, the SAI strategy is especially useful in improving the absorbing selectivity for semi-transparent OPVs, which enables a record light utilization efficiency of 5.34%. This work provides an effective strategy of SAI to optimize the optical and electrical properties of OPVs for high-performance and solar window applications.

Delayed Crystallization Kinetics Allowing High-Efficiency All-Polymer Photovoltaics with Superior Upscaled Manufacturing.

Though encouraging performance is achieved in small-area organic photovoltaics (OPVs), reducing efficiency loss when evoluted to large-area modules is an important but unsolved issue. Considering that polymer materials show benefits in film-forming processability and mechanical robustness, a high-efficiency all-polymer OPV module is demonstrated in this work. First, a ternary blend consisting of two polymer donors, PM6 and PBQx-TCl, and one polymer acceptor, PY-IT, is developed, with which triplet state recombination is suppressed for a reduced energy loss, thus allowing a higher voltage; and donor-acceptor miscibility is compromised for enhanced charge transport, thus resulting in improved photocurrent and fill factor; all these contribute to a champion efficiency of 19% for all-polymer OPVs. Second, the delayed crystallization kinetics from solution to film solidification is achieved that gives a longer operation time window for optimized blend morphology in large-area module, thus relieving the loss of fill factor and allowing a record efficiency of 16.26% on an upscaled module with an area of 19.3 cm2 . Besides, this all-polymer system also shows excellent mechanical stability. This work demonstrates that all-polymer ternary systems are capable of solving the upscaled manufacturing issue, thereby enabling high-efficiency OPV modules.

High-Performance Intrinsically Stretchable Organic Photovoltaics Enabled by Robust Silver Nanowires/S-PH1000 Hybrid Transparent Electrodes.

Intrinsically stretchable organic photovoltaics (is-OPVs) hold significant promise for integration into self-powered wearable electronics. However, their potential is hindered by the lack of sufficient consistency between optoelectronic and mechanical properties. This is primarily due to the limited availability of stretchable transparent electrodes (STEs) that possess both high conductivity and stretchability. Here, a hybrid STE with exceptional conductivity, stretchability, and thermal stability is presented. Specifically, STEs are composed of the modified PH1000 (referred to as S-PH1000) and silver nanowires (AgNWs). The S-PH1000 endows the STE with good stretchability and smoothens the surface, while the AgNWs enhance the charge transport. The resulting hybrid STEs enable is-OPVs to a remarkable power conversion efficiency (PCE) of 16.32%, positioning them among the top-performing is-OPVs. With 10% elastomer, the devices retain 82% of the initial PCE after 500 cycles at 20% strain. Additionally, OPVs equipped with these STEs exhibit superior thermal stability compared to those using indium tin oxide electrodes, maintaining 75% of the initial PCE after annealing at 85 °C for 390 h. The findings underscore the suitability of the designed hybrid electrodes for efficient and stable is-OPVs, offering a promising avenue for the future application of OPVs.

On the role of asymmetric molecular geometry in high-performance organic solar cells.

Although asymmetric molecular design has been widely demonstrated effective for organic photovoltaics (OPVs), the correlation between asymmetric molecular geometry and their optoelectronic properties is still unclear. To access this issue, we have designed and synthesized several symmetric-asymmetric non-fullerene acceptors (NFAs) pairs with identical physical and optoelectronic properties. Interestingly, we found that the asymmetric NFAs universally exhibited increased open-circuit voltage compared to their symmetric counterparts, due to the reduced non-radiative charge recombination. From our molecular-dynamic simulations, the asymmetric NFA naturally exhibits more diverse molecular interaction patterns at the donor (D):acceptor (A) interface as compared to the symmetric ones, as well as higher D:A interfacial charge-transfer state energy. Moreover, it is observed that the asymmetric structure can effectively suppress triplet state formation. These advantages enable a best efficiency of 18.80%, which is one of the champion results among binary OPVs. Therefore, this work unambiguously demonstrates the unique advantage of asymmetric molecular geometry, unveils the underlying mechanism, and highlights the manipulation of D:A interface as an important consideration for future molecular design.

Thorough Optimization for Intrinsically Stretchable Organic Photovoltaics.

The development of intrinsically stretchable organic photovoltaics (is-OPVs) with a high efficiency is of significance for practical application. However, their efficiencies lag far behind those of rigid or even flexible counterparts. To address this issue, an advanced top-illuminated OPV is designed and fabricated, which is intrinsically stretchable and has a high performance, through systematic optimizations from material to device. First, the stretchability of the active layer is largely increased by adding a low-elastic-modulus elastomer of styrene-ethylene-propylene-styrene tri-block copolymer (SEPS). Second, the stretchability and conductivity of the opaque electrode are enhanced by a conductive polymer/metal (denoted as M-PH1000@Ag) composite electrode strategy. Third, the optical and electrical properties of a sliver nanowire transparent electrode are improved by a solvent vapor annealing strategy. High-performance is-OPVs are successfully fabricated with a top-illuminated structure, which provides a record-high efficiency of 16.23%. Additionally, by incorporating 5-10% elastomer, a balance between the efficiency and stretchability of the is-OPVs is achieved. This study provides valuable insights into material and device optimizations for high-efficiency is-OPVs, with a low-cost production and excellent stretchability, which indicates a high potential for future applications of OPVs.

Solid Additive-Assisted Layer-by-Layer Processing for 19% Efficiency Binary Organic Solar Cells.

Morphology is of great significance to the performance of organic solar cells (OSCs), since appropriate morphology could not only promote the exciton dissociation, but also reduce the charge recombination. In this work, we have developed a solid additive-assisted layer-by-layer (SAA-LBL) processing to fabricate high-efficiency OSCs. By adding the solid additive of fatty acid (FA) into polymer donor PM6 solution, controllable pre-phase separation forms between PM6 and FA. This intermixed morphology facilitates the diffusion of acceptor Y6 into the donor PM6 during the LBL processing, due to the good miscibility and fast-solvation of the FA with chloroform solution dripping. Interestingly, this results in the desired morphology with refined phase-separated domain and vertical phase-separation structure to better balance the charge transport /collection and exciton dissociation. Consequently, the binary single junction OSCs based on PM6:Y6 blend reach champion power conversion efficiency (PCE) of 18.16% with SAA-LBL processing, which can be generally applicable to diverse systems, e.g., the PM6:L8-BO-based devices and thick-film devices. The efficacy of SAA-LBL is confirmed in binary OSCs based on PM6:L8-BO, where record PCEs of 19.02% and 16.44% are realized for devices with 100 and 250 nm active layers, respectively. The work provides a simple but effective way to control the morphology for high-efficiency OSCs and demonstrates the SAA-LBL processing a promising methodology for boosting the industrial manufacturing of OSCs.

Compromising Charge Generation and Recombination of Organic Photovoltaics with Mixed Diluent Strategy for Certified 19.4% Efficiency.

The ternary blend is demonstrated as an effective strategy to promote the device performance of organic photovoltaics (OPVs) due to the dilution effect. While the compromise between the charge generation and recombination remains a challenge. Here, a mixed diluent strategy for further improving the device efficiency of OPV is proposed. Specifically, the high-performance OPV system with a polymer donor, i.e., PM6, and a nonfullerene acceptor (NFA), i.e., BTP-eC9, is diluted by the mixed diluents, which involve a high bandgap NFA of BTP-S17 and a low bandgap NFA of BTP-S16 (similar with that of the BTP-eC9). The BTP-S17 of better miscibility with BTP-eC9 can dramatically enhance the open-circuit voltage (VOC ), while the BTP-S16 maximizes the charge generation or the short-circuit current density (JSC ). The interplay of BTP-17 and BTP-S16 enables better compromise between charge generation and recombination, thus leading to a high device performance of 19.76% (certified 19.41%), which is the best among single-junction OPVs. Further analysis on carrier dynamics validates the efficacy of mixed diluents for balancing charge generation and recombination, which can be further attributed to the more diverse energetic landscapes and improved morphology. Therefore, this work provides an effective strategy for high-performance OPV for further commercialization.

Balancing the Selective Absorption and Photon-to-Electron Conversion for Semitransparent Organic Photovoltaics with 5.0% Light-Utilization Efficiency.

Efficiently converting invisible light while allowing full visible light transmission is key to achieving high-performance semitransparent organic photovoltaics (ST-OPVs). Here, a detailed balance strategy is explored to optimize the ST-OPV via taking both absorption and carrier dynamics into consideration. Based on this principle, comprehensive optimizations are carried out, including a ternary strategy, donor:acceptor blend ratio, thickness, antireflection, etc., to compromise the invisible energy conversion and visible transmission for high-performance ST-OPVs. As a result, the opaque OPV device exhibits a champion power conversion efficiency of 19.35% (certificated 19.07%), and most strikingly, the best ST-OPV shows a remarkably high light-utilization efficiency of 5.0%, where the efficiency and the average visible transmission are 12.95% and 38.67%, respectively. An efficiency of 12.09% is achieved on the upscaled device with an area of 1.05 cm2 , demonstrating its promise for large-area fabrication. These results are among the best values for ST-OPVs. Besides, it is demonstrated that the ST-OPV exhibits good infrared light-reflection capability for thermal control. This work provides a rational design of balancing the absorbing selectivity and photon-to-electron conversion for high-performance ST-OPVs, and may pave the way toward the practical application of solar windows.

Achieving and Understanding of Highly Efficient Ternary Organic Photovoltaics: From Morphology and Energy Loss to Working Mechanism.

Ternary strategy, adding an additional donor (D) or acceptor (A) into conventional binary D:A blend, has shown great potential in improving photovoltaic performances of organic photovoltaics (OPVs) for practical applications. Herein, this review is presented on how efficient ternary OPVs are realized from the aspects of morphology, energy loss, and working mechanism. As to morphology, the role of third component on the formation of preferred alloy-like-phase and vertical-phase, which are driven by the miscibility tuning, is discussed. For energy loss, the effect of the third component on the luminescence enhancement and energetic disordering suppression, which lead to favorable increase of voltage, is presented. Regarding working mechanism, dilution effect and relationships between two acceptors or donor/acceptor, which explain the observed device parameters variations, are analyzed. Finally, some future directions concerning ternary OPVs are pointed out. Therefore, this review can provide a comprehensive understanding of working principles and effective routes for high-efficiency ternary systems, advancing the commercialization of OPVs.

Flexible Miniaturized Multispectral Detector Derived from Blade-Coated Organic Narrowband Response Unit Array.

Multispectral sensing is extremely desired in intelligent systems, e.g., autonomous vehicles, encrypted information communication, and health biometric monitoring, due to its highly sensitive spectral discrimination ability. Nevertheless, rigid bulky optics and delicate optical paths in devices significantly increase their complexity and size, which subsequently impede their integration in smart optoelectronic chips for universal applications. In this work, a filterless miniaturized multispectral photodetector is realized with an organic narrowband response unit array. With the manipulation of Frenkel exciton dissociation in active layers, a series of narrowband organic sensing units with full-width-at-half-maximum (fwhm) narrowing to ∼50 nm are achieved from 700 to 1050 nm with a laudable performance of responsivity of over 60 mA/W, -3 dB bandwidth over 10 kHz, linear dynamic range (LDR) reaching ∼120 dB, and a low noise current of less than 4 × 10-14 A·Hz-0.5. Furthermore, a 6 × 8 multispectral sensing array on a flexible substrate was fabricated with blade-coating. Assisted by a computational process, we successfully demonstrate the spectral recognition with a resolution of ∼50 nm and a mismatch of ∼10 nm. Finally, the function of matter identification is successfully achieved with our multispectral detector array.

Dilution effect for highly efficient multiple-component organic solar cells.

Although the multiple-component (MC) blend strategy has been frequently used as a very effective way to improve the performance of organic solar cells (OSCs), there is a strong need to understand the fundamental working mechanism and material selection rule for achieving optimal MC-OSCs. Here we present the 'dilution effect' as the mechanism for MC-OSCs, where two highly miscible components are molecularly intermixed. Contrary to the aggregation-induced non-radiative decay, the dilution effect enables higher luminescence quantum efficiencies and open-circuit voltages (VOC) in MC-OSCs via suppressed electron-vibration coupling. The continuously broadened bandgap together with reduced electron-vibration coupling also explains the composition-dependent VOC in ternary blends well. Moreover, we show that electrons can transfer between different acceptors, depending on the energy offset between them, which contributes to the largely unperturbed charge transport and high fill factors in MC-OSCs. The discovery of the dilution effect enables the demonstration of a high power conversion efficiency of 18.31% in an MC-OSC.

Versatile Sequential Casting Processing for Highly Efficient and Stable Binary Organic Photovoltaics.

Forming an ideal bulk heterojunction (BHJ) morphology is a critical issue governing the photon to electron process in organic solar cells (OSCs). Complementary to the widely-used blend casting (BC) method for BHJ construction, sequential casting (SC) can also enable similar or even better morphology and device performance for OSCs. Here, BC and SC methods on three representative donor:acceptor (D:A) blends are utilized, that is, PM6:PC71 BM, PM6:IT-4F and PM6:L8-BO. Higher power conversion efficiencies (PCEs) in all cases by taking advantage of beneficial morphology from SC processing are achieved, and a champion PCE of 18.86% (certified as 18.44%) based on the PM6:L8-BO blend is reached, representing the record value among binary OSCs. The observations on phase separation and vertical distribution inspire the proposal of the swelling-intercalation phase-separation model to interpret the morphology evolution during SC processing. Further, the vertical phase segregation is found to deliver an improvement of device performance via affecting the charge transport and collection processes, as evidenced by the D:A-ratio-dependent photovoltaic properties. Besides, OSCs based on SC processing show advantages on device photostability and upscale fabrication. This work demonstrates the versatility and efficacy of the SC method for BHJ-based OSCs.

High-Efficiency ITO-Free Organic Photovoltaics with Superior Flexibility and Upscalability.

Developing indium-tin-oxide (ITO)-free flexible organic photovoltaics (OPVs) with upscaling capacity is of great significance for practical applications of OPVs. Unfortunately, the efficiencies of the corresponding devices lag far behind those of ITO-based rigid small-area counterparts. To address this issue, an advanced device configuration is designed and fabricated featuring a top-illuminated structure with ultrathin Ag as the transparent electrode. First, a conjugated polyelectrolyte layer, i.e., PCP-Li, is inserted to effectively connect the bottom Ag anode and the hole transport layer, achieving good photon to electron conversion. Second, charge collecting grids are deposited to suppress the increased resistance loss with the upscaling of the device area, realizing almost full retention of device efficiency from 0.06 to 1 cm2 . Third, the designed device delivers the best efficiency of 15.56% with the area of 1 cm2 on polyimide substrate, representing as the record among the ITO-free, large-area, flexible OPVs. Interestingly, the device exhibits no degradation after 100 000 bending cycles with a radius of 4 mm, which is the best result for flexible OPVs. This work provides insight into device structure design and optimization for OPVs with high efficiency, low cost, superior flexibility, and upscaling capacity, indicating the potential for the future commercialization of OPVs.