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.

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.

Lithiophilic Covalent Organic Framework as Anode Coating for High-Performance Lithium Metal Batteries.

The growth of disorganized lithium dendrites and weak solid electrolyte interphase greatly impede the practical application of lithium metal batteries. Herein, we designed and synthesized a new kind of stable polyimide covalent organic frameworks (COFs), which have a high density of well-aligned lithiophilic quinoxaline and phthalimide units anchored within the uniform one-dimensional channels. The COFs can serve as an artificial solid electrolyte interphase on lithium metal anode, effectively guiding the uniform deposition of lithium ions and inhibiting the growth of lithium dendrites. The unsymmetrical Li||COF-Cu battery exhibits a Coulombic efficiency of 99 % at a current density of 0.5 mA cm-2 , which can be well retained up to 400 cycles. Meanwhile, the Li-COF||LFP full cell shows a Coulombic efficiency over 99 % at a charge of 0.3 C. And its capacity can be well maintained up to 91 % even after 150 cycles. Therefore, the significant electrochemical cycling stability illustrates the feasibility of employing COFs in solving the disordered deposition of lithium ions in lithium metal batteries.

Selectively Modulating Componential Morphologies of Bulk Heterojunction Organic Solar Cells.

Achieving precise control over the nanoscale morphology of bulk heterojunction films presents a significant challenge for the conventional post-treatments employed in organic solar cells (OSCs). In this study, a near-infrared photon-assisted annealing (NPA) strategy is developed for fabricating high-performance OSCs under mild processing conditions. It is revealed a top NIR light illumination, together with the bottom heating, enables the selective tuning of the molecular arrangement and assembly of narrow bandgap acceptors in polymer networks to achieve optimal morphologies, as well as the acceptor-rich top surface of active layers. The derived OSCs exhibit a remarkable power conversion efficiency (PCE) of 19.25%, representing one of the highest PCEs for the reported binary OSCs so far. Moreover, via the NPA strategy, it has succeeded in accessing top-illuminated flexible OSCs using thermolabile polyethylene terephthalate from mineral water bottles, displaying excellent mechanical stabilities. Overall, this work will hold the potential to develop organic solar cells under mild processing with various substrates.

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.

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.

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.

Visible-Blind Narrowband Near-Infrared Photodetector for Precise Real-Time Photoplethysmography Measurement.

The visible-blind narrowband photodetector (NPD) with spectral selective sensitivity to near-infrared (NIR) light is an important technology in the field of cardiovascular health assessment. However, the biological information carried by NIR light constantly changes signals with small amplitude and fast speed, which puts high requirements on the performance of detectors. Herein, visible-blind NIR NPDs were constructed by integrating solution-processable films of perovskite, CuSCN, and organic semiconductors. The NIR response was provided by the organic bulk heterojunction (OBHJ) film with a narrow band gap. A thick perovskite layer was applied to screen the incident visible light and suppress the leakage current in the dark state. CuSCN with a high LUMO level blocked the extraction of the visible-light-induced free electrons. The width of the response window was restricted by adjusting the band gap of the perovskite and the donor/acceptor ratio of the OBHJ film. The optimized NIR NPD exhibits a comprehensive performance including visible-blind response, a tunable response spectrum, a high responsivity/detectivity, and a short response time. In practical photoplethysmography measurements, the detector can record the human heart rate in real time through a noninvasive technique and precisely monitor the whole cardiac cycle, which provides an effective method for early detection of cardiovascular symptoms for timely diagnosis and treatment.

Carborane-Based Three-Dimensional Covalent Organic Frameworks.

The predesignable porous structure and high structural flexibility of covalent organic frameworks (COFs) render this material desirable as a platform for addressing various cutting-edge issues. Precise control over their composition, topological structure, porosity, and stability to realize tailor-made functionality still remains a great challenge. In this work, we developed a new kind of three-dimensional (3D) carborane-based COF with a 7-fold interpenetrating dia topological diagram. The resulting COFs exhibited high crystallinity, exceptional porosity, and strong robustness. The slightly lower electronegativity of boron (2.04) than that of hydrogen (2.20) can lead to the polarization of the B-H bond into a Bδ+-Hδ- mode, which renders these COFs as high-performance materials for the adsorption and separation of hexane isomers through the B-Hδ-···Hδ+-C interaction. Significantly, the carborane content of obtained COFs reached up to 54.2 wt %, which gets the highest rank among all the reported porous materials. Combining high surface area, strong robustness, and high content of carborane, the obtained COFs can work as efficient adsorbents for the separation of the five hexane isomers with high separation factors. This work not only enhances the diversity of 3D functional COFs but also constitutes a further step toward the efficient separation of alkane isomers.

Robust and Sustainable Indium Anode Leading to Efficient and Stable Organic Solar Cells.

The fast degradation of the charge-extraction interface at indium tin oxide (ITO) poses a significant obstacle to achieving long-term stability for organic solar cells (OSCs). Herein, a sustainable approach for recycling non-sustainable indium to construct efficient and stable OSCs and scale-up modules is developed. It is revealed that the recovered indium chloride (InCl3 ) from indium oxide waste can be applied as an effective hole-selective interfacial layer for the ITO electrode (noted as InCl3 -ITO anode) through simple aqueous fabrication, facilitating not only energy level alignment to photoactive blends but also mitigating parasitic absorption and charge recombination losses of the corresponding OSCs. As a result, OSCs and modules consisting of InCl3 -ITO anodes achieve remarkable power conversion efficiencies (PCEs) of 18.92% and 15.20% (active area of 18.73 cm2 ), respectively. More importantly, the InCl3 -ITO anode can significantly extend the thermal stability of derived OSCs, with an extrapolated T80 lifetime of ≈10 000 h.

Pore partition in two-dimensional covalent organic frameworks.

Covalent organic frameworks (COFs) have emerged as a kind of crystalline polymeric materials with high compositional and geometric tunability. Most COFs are currently designed and synthesized as mesoporous (2-50 nm) and microporous (1-2 nm) materials, while the development of ultramicroporous (<1 nm) COFs remains a daunting challenge. Here, we develop a pore partition strategy into COF chemistry, which allows for the segmentation of a mesopore into multiple uniform ultramicroporous domains. The pore partition is implemented by inserting an additional rigid building block with suitable symmetries and dimensions into a prebuilt parent framework, leading to the partitioning of one mesopore into six ultramicropores. The resulting framework features a wedge-shaped pore with a diameter down to 6.5 Å, which constitutes the smallest pore among COFs. The wedgy and ultramicroporous one-dimensional channels enable the COF to be highly efficient for the separation of five hexane isomers based on the sieving effect. The obtained average research octane number (RON) values of those isomer blends reach up to 99, which is among the highest records for zeolites and other porous materials. Therefore, this strategy constitutes an important step in the pore functional exploitation of COFs to implement pre-designed compositions, components, and functions.

High-Precision and Rapid Direct Laser Writing Using a Liquid Two-Photon Polymerization Initiator.

Two-photon polymerization based direct laser writing (DLW) is an emerging micronano 3D fabrication technology wherein two-photon initiators (TPIs) are a key component in photoresists. Upon exposure to a femtosecond laser, TPIs can trigger the polymerization reaction, leading to the solidification of photoresists. In other words, TPIs directly determine the rate of polymerization, physicochemical properties of polymers, and even the photolithography feature size. However, they generally exhibit extremely poor solubility in photoresist systems, severely inhibiting their application in DLW. To break through this bottleneck, we propose a strategy to prepare TPIs as liquids via molecular design. The maximum weight fraction of the as-prepared liquid TPI in photoresist significantly increases to 2.0 wt %, which is several times higher than that of commercial 7-diethylamino-3-thenoylcoumarin (DETC). Meanwhile, this liquid TPI also exhibits an excellent absorption cross section (64 GM), allowing it to absorb femtosecond laser efficiently and generate abundant active species to initiate polymerization. Remarkably, the respective minimum feature sizes of line arrays and suspended lines are 47 and 20 nm, which are comparable to that of the-state-of-the-art electron beam lithography. Besides, the liquid TPI can be utilized to fabricate various high-quality 3D microstructures and manufacture large-area 2D devices at a considerable writing speed (1.045 m s-1). Therefore, the liquid TPI would be one of the promising initiators for micronano fabrication technology and pave the way for future development of DLW.

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.

Multifunctional Hybrid Interfacial Layers for High-Performance Inverted Perovskite Solar Cells.

Challenges remain hindering the performance and stability of inverted perovskite solar cells (PSCs), particularly for the nonstable interface between lead halide perovskite and charge extraction metal oxide layer. Herein, a simple yet scalable interfacial strategy to facilitate the assemble of high-performance inverted PSCs and scale-up modules is reported. The hybrid interfacial layer containing self-assembly triphenylamine and conjugated poly(arylamine) simultaneously improves the chemical stability, charge extraction, and energy level alignment of hole-selective interface, meanwhile promoting perovskite crystallization. Consequently, the correspondent inverted PSCs and modules achieve remarkable power conversion efficiencies (PCEs) of 24.5% and 20.7% (aperture area of 19.4 cm2 ), respectively. The PSCs maintain over 80% of its initial efficiency under one-sun equivalent illumination of 1200 h. This strategy is also effective to perovskite with various bandgaps, demonstrating the highest PCE of 19.6% for the 1.76-eV bandgap PSCs. Overall, this work provides a simple yet scalable interfacial strategy for obtaining state-of-the-art inverted PSCs and modules.

Janus Dione-Based Conjugated Covalent Organic Frameworks with High Conductivity as Superior Cathode Materials.

The development of conductive covalent organic frameworks (COFs) with high stability is desirable for the practical applications in optoelectronics and energy storage. Herein, we developed a new kind of Janus dione-based COF, which is fully sp2 carbon-conjugated through the connection by olefin units. The electrical conductivity and carrier mobility reached up to 10-3 S cm-1 and 7.8 cm2 V-1 s-1, respectively. In addition, these COFs are strongly robust against various harsh conditions. The well-ordered two-dimensional crystalline structures, excellent porosity, high conductivity, and abundant redox-active carbonyl units render these COFs serviceable as high-performance cathode materials in lithium-ion batteries. It is worth noting that TFPPy-ICTO-COF exhibits a capacity of up to 338 mAh g-1 at a discharge rate of 0.1 C, which sets a new capacity record among COF-based lithium-ion batteries. Its capacity retention was as high as 100% even after 1000 cycles, demonstrating the remarkable stability of these Janus dione-based COF materials. This work not only expands the diversity of olefin-linked COFs but also makes a new breakthrough in energy storage.

Multiphase Morphology with Enhanced Carrier Lifetime via Quaternary Strategy Enables High-Efficiency, Thick-Film, and Large-Area Organic Photovoltaics.

With the continuous breakthrough of the efficiency of organic photovoltaics (OPVs), their practical applications are on the agenda. However, the thickness tolerance and upscaling in recently reported high-efficiency devices remains challenging. In this work, the multiphase morphology and desired carrier behaviors are realized by utilizing a quaternary strategy. Notably, the exciton separation, carrier mobility, and carrier lifetime are enhanced significantly, the carrier recombination and the energy loss (Eloss ) are reduced, thus beneficial for a higher short-circuit density (JSC ), fill factor (FF), and open-circuit voltage (VOC ) of the quaternary system. Moreover, the intermixing-phase size is optimized, which is favorable for constructing the thick-film and large-area devices. Finally, the device with a 110 nm-thick active layer shows an outstanding power conversion efficiency (PCE) of 19.32% (certified 19.35%). Furthermore, the large-area (1.05 and 72.25 cm2 ) devices with 110 nm thickness present PCEs of 18.25% and 12.20%, and the device with a 305 nm-thick film (0.0473 cm2 ) delivers a PCE of 17.55%, which are among the highest values reported. The work demonstrates the potential of the quaternary strategy for large-area and thick-film OPVs and promotes the practical application of OPVs in the future.

Three-Dimensional Covalent Organic Frameworks with she Topology.

Reticular chemistry allows the control of crystalline frameworks at atomic precision according to the predesigned topological structures. However, only a limited number of topological structures of three-dimensional (3D) covalent organic frameworks (COFs) have been established. In this work, we developed a series of 3D COFs with an unprecedented she topology, which were constructed with D3d- and D4h-symmetric building blocks. The resulting COFs crystallize in a space group of Im3̅m, in which each D3d unit connects with six D4h units to form a noninterpenetrated network with a uniform pore size of 2.0 nm. In addition, these COFs exhibited high crystallinity, excellent porosity, and good chemical and thermal stability. The crystalline structures, composition, and physicochemical properties of these networks were unambiguously characterized. Notably, the inbuilt porphyrin units render these COFs as efficient catalysts for photoredox C-C bond forming and photocatalytic carbon dioxide reduction reactions. Thus, this work constitutes a new approach for the construction of 3D she-net COFs and also enhances the structural diversity and complexity of COFs.

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.