Correlating Aggregation Ability of Polymer Donors with Film Formation Kinetics for Organic Solar Cells with Improved Efficiency and Processability.

Film formation kinetics significantly impact molecular processability and power conversion efficiency (PCE) of organic solar cells. Here, two ternary random copolymerization polymers are reported, D18─N-p and D18─N-m, to modulate the aggregation ability of D18 by introducing trifluoromethyl-substituted pyridine unit at para- and meta-positions, respectively. The introduction of pyridine unit significantly reduces material aggregation ability and adjusts the interactions with acceptor L8-BO, thereby leading to largely changed film formation kinetics with earlier phase separation and longer film formation times, which enlarge fiber sizes in blend films and improve carrier generation and transport. As a result, D18─N-p with moderate aggregation ability delivers a high PCE of 18.82% with L8-BO, which is further improved to 19.45% via interface engineering. Despite the slightly inferior small area device performances, D18─N-m shows improved solubility, which inspires to adjust the ratio of meta-trifluoromethyl pyridine carefully and obtain a polymer donor D18─N-m-10 with good solubility in nonhalogenated solvent o-xylene. High PCEs of 13.07% and 12.43% in 1 cm2 device and 43 cm2 module fabricated with slot-die coating method are achieved based on D18─N-m-10:L8-BO blends. This work emphasizes film formation kinetics optimization in device fabrication via aggregation ability modulation of polymer donors for efficient devices.

A calculation method for optical properties of yolk shell based on deep learning.

The yolk shell is widely used in optoelectronic devices due to its excellent optical properties. Compared to single metal nanostructures, yolk shells have more controllable degrees of freedom, which may make experiments and simulations more complex. Using neural networks can efficiently simplify the computational process of yolk shell. In our work, the relationship between the size and the absorption efficiency of the yolk-shell structure is established using a backpropagation neural network (BPNN), significantly simplifying the calculation process while ensuring accuracy equivalent to discrete dipole scattering (DDSCAT). The absorption efficiency of the yolk shell was comprehensively described through the forward and reverse prediction processes. In forward prediction, the absorption spectrum of yolk shell is obtained through its size parameter. In reverse prediction, the size parameters of yolk shells are predicted through absorption spectra. A comparison with the traditional DDSCAT demonstrated the high precision prediction capability and fast computation of this method, with minimal memory consumption.

Guest Acceptors with Lower Electrostatic Potential in Ternary Organic Solar Cells for Minimizing Voltage Losses.

The ternary strategy, in which one guest component is introduced into one host binary system, is considered to be one of the most effective ways to realize high-efficiency organic solar cells (OSCs). To date, there is no efficient method to predict the effectiveness of guest components in ternary OSCs. Herein, three guest compositions (i.e., ANF-1, ANF-2 and ANF-3) with different electrostatic potential (ESP) are designed and synthesized by modulating the electron-withdrawing ability of the terminal groups through density functional theory simulations. The effects of the introduction of guest component into the host system (D18:N3) on the photovoltaic properties are investigated. The theoretical and experimental studies provide a key rule for guest acceptor in ternary OSCs to improve the open-circuit voltage, that is, the larger ESP difference between the guest and host acceptor, the stronger the intermolecular interactions and the higher the miscibility, which improves the luminescent efficiency of the blend film and the electroluminescence quantum yield (EQEEL) of the device by reducing the aggregation-caused-quenching, thereby effectively decreasing the non-radiative voltage loss of ternary OSCs. This work will greatly contribute to the development of highly efficient guest components, thereby promoting the rapid breakthrough of the 20% efficiency bottleneck for single-junction OSCs.

Bis(benzoselenadiazol)ethane: A π-Extended Acceptor-Dimeric Unit for Ambipolar Polymer Transistors with Hole and Electron Mobilities Exceeding 10†cm2 V-1 s-1.

The lack of ambipolar polymers with balanced hole (µh) and electron mobilities (µe) >10 cm2 V-1 s-1 is the main bottleneck for developing organic integrated circuits. Herein, we show the design and synthesis of a π-extended selenium-containing acceptor-dimeric unit, namely benzo[c][1,2,5]selenadiazol-4-yl)ethane (BBSeE), to address this dilemma. In comparison to its sulfur-counterpart, BBSeE demonstrates enlarged co-planarity, selective noncovalent interactions, polarized Se-N bond, and higher electron affinity. The successful stannylation of BBSeE offers a great opportunity to access acceptor-acceptor copolymer pN-BBSeE, which shows a narrower band gap, lower-lying lowest unoccupied molecular orbital level (-4.05 eV), and a higher degree of backbone planarity. Consequently, the pN-BBSeE-based organic transistors display an ideally balanced ambipolar transporting property with µh and µe of 10.65 and 10.72 cm2 V-1 s-1, respectively. To the best of our knowledge, the simultaneous µh/µe values >10.0 cm2 V-1 s-1 are the best performances ever reported for ambipolar polymers. In addition, pN-BBSeE shows an excellent shelf-storage stability, retaining over 85 % of the initial mobility values after two months storage. Our study demonstrates the π-extended acceptor-dimeric BBSeE is a promising acceptor building block for constructing high-performance ambipolar polymers applied in next-generation organic integrated circuit.

A bromide substituted 2D additive for stable and efficient perovskite photovoltaics.

In this article, a bromide substituted 2D layered perovskite having a repeated vertical orientation and coexisting with the bulk of a 3D perovskite is reported for the first time. This novel structure is obtained through controlled compositional engineering of the perovskite precursor solution. The photovoltaic performance of this novel 2D/3D perovskite was higher than that of 3D MAPbI3 and a maximum photoconversion efficiency (PCE) of 17.4% was achieved. The devices fabricated using this perovskite heterostructure were stable and retained their initial PCE up to 20 days when kept open in a laboratory environment with 40% relative humidity.

Simple-Structured Acceptor with Highly Interconnected Electron-Transport Pathway Enables High-Efficiency Organic Solar Cells.

Achieving desirable charge-transport highway is of vital importance for high-performance organic solar cells (OSCs). Here, it is shown how molecular packing arrangements can be regulated via tuning the alkyl-chain topology, thus resulting in a 3D network stacking and highly interconnected pathway for electron transport in a simple-structured nonfused-ring electron acceptor (NFREA) with branched alkyl side-chains. As a result, a record-breaking power conversion efficiency of 17.38% (certificated 16.59%) is achieved for NFREA-based devices, thus providing an opportunity for constructing low-cost and high-efficiency OSCs.

Regulating the Layered Stacking of a Covalent Triazine Framework Membrane for Aromatic/Aliphatic Separation.

Membrane separation of aromatics and aliphatics is a crucial requirement in chemical and petroleum industries. However, this task presents a significant challenge due to the lack of membrane materials that can endure harsh solvents, exhibit molecular specificity, and facilitate easy processing. Herein, we present a novel approach to fabricate a covalent triazine framework (CTF) membrane by employing a mix-monomer strategy. By incorporating a spatial monomer alongside a planar monomer, we were able to subtly modulate both the pore aperture and membrane affinity, enabling preferential permeation of aromatics over aliphatics with molecular weight below 200 Dalton (Da). Consequently, we achieved successful all-liquid phase separation of aromatic/aliphatic mixtures. Our investigation revealed that the synergistic effects of size sieving and the affinity between the permeating molecules and the membrane played a pivotal role in separating these closely resembling species. Furthermore, the membrane exhibited remarkable robustness under practical operating conditions, including prolonged operation time, various feed compositions, different applied pressure, and multiple feed components. This versatile strategy offers a feasible approach to fabricate membranes with molecule selectivity toward aromatic/aliphatic mixtures, taking a significant step forward in addressing the grand challenge of separating small organic molecules through membrane technology.

Noncovalent Interaction Boosts Performance and Stability of Organic Solar Cells Based on Giant-Molecule Acceptors.

Designing giant-molecule acceptors is deemed as an up-and-coming strategy to construct stable organic solar cells (OSCs) with high performance. Herein, two giant dimeric acceptors, namely, DYV and DYFV, have been designed and synthesized by linking two Y-series derivatives with a vinyl unit. DYFV exhibits more red-shifted absorption, down-shifted energy levels, and enhanced intermolecular packing than DYV because the intramolecular noncovalent interaction (H···F) of DYFV leads to better coplanarity of the backbone. The D18:DYFV film owns a distinct nanofibrous nanophase separation structure, a more dominant face-on orientation, and more balanced carrier mobilities. Therefore, the D18:DYFV OSC achieves a higher photoelectron conversion efficiency of 17.88% and a longer-term stability with a t80 over 45,000 h compared with the D18:DYV device. The study demonstrates that the intramolecular noncovalent interaction is a superior strategy to design giant-molecule acceptors and boost the photovoltaic performance and stability of the OSCs.

High-Performance Organic Narrow Dual-Band Circular Polarized Light Detection for Encrypted Communications and Color Imaging.

Conventional circularly polarized light (CPL) detectors necessitate several optical elements, posing difficulties in achieving miniature and integrated devices. Recently developed organic CPL detectors require no additional optical elements but usually suffer from low detectivity or low asymmetry factor (g-factor). Here, an organic CPL detector with excellent detectivity and a high g-factor is fabricated. By employing an inverted quasi-planar heterojunction (IPHJ) structure and incorporating an additional liquid crystal film, a CPL detector with an outstanding g-factor of 1.62 is developed. Unfavorable charge injection is effectively suppressed by the IPHJ structure, which reduces the dark current of the organic photodetector. Consequently, a left CPL detectivity of 6.16 × 1014 Jones at 640 nm is realized, surpassing all of the latest photodiode-type CPL detectors. Adopting a liquid crystal film with adjustable wavelengths of selectively reflected light, the hybrid device achieves narrow dual-band CPL detection, varying from 530 to 640 nm, with a half-maximum full width below 90 nm. Notably, the device achieves excellent stability of 260 000 on/off cycles without attenuation. To the best of the authors' knowledge, all these features have rarely been reported in previous work. The CPL detector arrays are also demonstrated for encrypted communications and color imaging.

Tailoring the Position of Ester Group on N-Alkyl Chains of Benzotriazole-based Small Molecule Acceptors for High-Performance Organic Solar Cells.

Side chain engineering plays a vital role in exploring high-performance small molecule acceptors (SMAs) for organic solar cells (OSCs). In this work, we designed and synthesized a series of A-DA'D-A type SMAs by introducing different N-substituted alkyl and ester alkyl side chains on benzotriazole (BZ) central unit and aimed to investigate the effect of different ester substitution positions on photovoltaic performances. All the new SMAs with ester groups exhibit lower the lowest unoccupied molecular orbital (LUMO) energy levels and more blue-shifted absorption, but relatively higher absorption coefficients than alkyl chain counterpart. After blending with the donor PM6, the ester side chain-based devices demonstrate enhanced charge mobility, reduced amorphous intermixing domain size and long-lived charge transfer state compared to the alkyl chain counterpart, which are beneficial to achieve higher short-circuit current density (Jsc ) and fill factor (FF), simultaneously. Thereinto, the PM6 : BZ-E31 based device achieves a higher power conversion efficiency (PCE) of 18.33 %, which is the highest PCE among the OSCs based on the SMAs with BZ-core. Our work demonstrated the strategy of ester substituted side chain is a feasible and effective approach to develop more efficient SMAs for 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.

Suppressing Exciton-Vibration Coupling to Prolong Exciton Lifetime of Nonfullerene Acceptors Enables High-Efficiency Organic Solar Cells.

The limited exciton lifetime (τ, generally <1 ns) leads to short exciton diffusion length (LD ) of organic semiconductors, which is the bottleneck issue impeding the further improvement of power conversion efficiencies (PCEs) for organic solar cells (OSCs). However, efficient strategies to prolong intrinsic τ are rare and vague. Herein, we propose a facile method to efficiently reduce vibrational frequency of molecular skeleton and suppress exciton-vibration coupling to decrease non-radiative decay rate and thus prolong τ via deuterating nonfullerene acceptors. The τ remarkably increases from 0.90 ns (non-deuterated L8-BO) to 1.35 ns (deuterated L8-BO-D), which is the record for organic photovoltaic materials. Besides, the inhibited molecular vibration improves molecular planarity of L8-BO-D for enhanced exciton diffusion coefficient. Consequently, the LD increases from 7.9 nm (L8-BO) to 10.7 nm (L8-BO-D). The prolonged LD of L8-BO-D enables PM6 : L8-BO-D-based bulk heterojunction OSCs to acquire higher PCEs of 18.5 % with more efficient exciton dissociation and weaker charge carrier recombination than PM6 : L8-BO-based counterparts. Moreover, benefiting from the prolonged LD , D18/L8-BO-D-based pseudo-planar heterojunction OSCs achieve an impressive PCE of 19.3 %, which is among the highest values. This work provides an efficient strategy to increase the τ and thus LD of organic semiconductors, boosting PCEs of OSCs.

Hedysarumqilianshanense sp. nov. (Fabaceae, Hedysareae), a new species from the Qilianshan Mountains in Gansu, China.

Hedysarumqilianshanensesp. nov. (Fabaceae, Hedysareae) is described and illustrated from the Qilianshan Mountains in Gansu, China. This new species is similar to H.przewalskii, but can be distinguished by its corolla being light purple to purple, standard 15-19 mm long, wings 14-16 mm long, keels 16-19 mm long, and the ovary and legume being glabrous. The new species can be easily distinguished from H.neglectum Ledeb. by its bract being shorter than the pedicel, and the ovary and legume being glabrous. Phylogenetic tree based on the nuclear ITS and ETS sequences shows that H.qilianshanense is sister to H.przewalskii, while the tree based on the plastid psbA-trnH, trnC-petN, trnL-F, trnS-G and petN-psbM sequences shows H.qilianshanense as sister to a clade consisting of H.hedysaroides, H.inundatum, H.americanum and H.neglectum. The new species is a diploid with the chromosome number 2n = 14. Based on morphological, phylogenetic and karyotypic evidence, the new species may originate from an ancient homoploid hybrid speciation event.

Over 18% Efficiency Ternary Organic Solar Cells with 300 nm Thick Active Layer Enabled by an Oligomeric Acceptor.

The development of high-efficiency thickness-insensitive organic solar cells (OSCs) is crucially important for the mass production of solar panels. However, increasing the active layer thickness usually induces a substantial loss in efficiency. Herein, a ternary strategy in which an oligomer DY-TF is incorporated into PM6:L8-BO system as a guest component is adopted to break this dilemma. The S···F intramolecular noncovalent interactions in the backbone endow DY-TF with a high planarity. Upon the addition of DY-TF, the crystallinity of the blend is effectively improved, leading to increased charge carrier mobility, which is highly desirable in the fabrication of thick-film devices. As a result, thin-film PM6:L8-BO:DY-TF-based device (110 nm) shows a power conversion efficiency (PCE) of 19.13%. Impressively, when the active layer thickness increases to 300 nm, an efficiency of 18.23% (certified as 17.8%) is achieved, representing the highest efficiency reported for 300 nm thick OSCs thus far. Additionally, blade-coated thick device (300 nm) delivers a promising PCE of 17.38%. This work brings new insights into the construction of efficient OSCs with high thickness tolerance, showing great potential for roll-to-roll printing of large-area solar cells.

Stereoisomeric Non-Fullerene Acceptors-Based Organic Solar Cells.

Chiral alkyl chains are ubiquitously observed in organic semiconductor materials and can regulate solution processability and active layer morphology, but the effect of stereoisomers on photovoltaic performance has rarely been investigated. For the racemic Y-type acceptors widely used in organic solar cells, it remains unknown if the individual chiral molecules separate into the conglomerate phase or if racemic phase prevails. Here, the photovoltaic performance of enantiomerically pure Y6 derivatives, (S,S)/(R,R)-BTP-4F, and their chiral mixtures are compared. It is found that (S,S) and (R,R)-BTP-4F molecule in the racemic mixtures tends to interact with its enantiomer. The racemic mixtures enable efficient light harvesting, fast hole transfer, and long polaron lifetime, which is conducive to charge generation and suppresses the recombination losses. Moreover, abundant charge diffusion pathways provided by the racemate contribute to efficient charge transport. As a result, the racemate system maximizes the power output and minimizes losses, leading to a higher efficiency of 18.16% and a reduced energy loss of 0.549 eV, as compared to the enantiomerically pure molecules. This study demonstrates that the chirality of non-fullerene acceptors should receive more attention and be designed rationally to enhance the efficiency of organic solar cells.

Strengthening the Hetero-Molecular Interactions in Giant Dimeric Acceptors Enables Efficient Organic Solar Cells.

Giant dimeric acceptor (G-Dimer) is becoming one of the most promising organic solar cell (OSC) materials because of its definite structure, long-term stability, and high efficiency. Strengthening the hetero-molecular interactions by monomer modification greatly influences the morphology and thus the device performance, but lacks investigation. Herein, two novel quinoxaline core-based G-Dimers, Dimer-QX and Dimer-2CF, are synthesized. By comparing trifluoromethyl-substituted Dimer-2CF and non-substituted Dimer-QX, the trifluoromethylation effect on the G-Dimer is investigated and revealed. The trifluoromethyl with strong electronegativity increases electrostatic potential and reduces surface energy of the G-Dimer, weakening the homo-molecular ordered packing but reinforcing the hetero-molecular interaction with the donor. The strong hetero-molecular interaction suppresses the fast assembly during the film formation, facilitating small domains with ordered molecular packing in the blend, which is a trade-off in conventional morphology control. Together with favorable vertical phase separation, efficient charge generation, and reduced bimolecular recombination are concurrently obtained. Hence, the Dimer-2CF-based OSCs obtain a cutting-edge efficiency of 19.02% with fill factor surpassing 80%, and an averaged extrapolated T80 of ≈12 000 h under continuous 80 °C heating. This study emphasizes the importance of hetero-molecular interaction and trifluoromethylation strategy, providing a facile strategy for designing highly efficient and stable OSC materials.

Manipulating Vertical Phase Separation Enables Pseudoplanar Heterojunction Organic Solar Cells Over 19% Efficiency via Ternary Polymerization.

Controlling vertical phase separation of the active layer to enable efficient exciton dissociation and charge carrier transport is crucial to boost power conversion efficiencies (PCEs) of pseudoplanar heterojunction (PPHJ) organic solar cells (OSCs). However, how to optimize the vertical phase separation of PPHJ OSCs via molecule design is rarely reported yet. Herein, ternary polymerization strategy is employed to develop a series of polymer donors, DL1-DL4, and regulate their solubility, molecular aggregation, molecular orientation, and miscibility, thus efficiently manipulating vertical phase separation in PPHJ OSCs. Among them, DL1 not only has enhanced solubility, inhibited molecular aggregation and partial edge-on orientation to facilitate acceptor molecules, Y6, to permeate into polymer layer and increase donor/acceptor interfaces, but also sustains high crystallinity and appropriate miscibility with Y6 to acquire ordered molecular packing, thus achieving optimized vertical phase separation to well juggle exciton dissociation and charge transport in PPHJ devices. Therefore, DL1/Y6 based PPHJ OSCs gain the best exciton dissociation probability, highest charge carrier mobilities and weakest charge recombination, and thus afford an impressive PCE of 19.10%, which is the record value for terpolymer donors. It demonstrates that ternary polymerization is an efficient method to optimize vertical phase separation in PPHJ OSCs for high PCEs.

Higher-order singularities in phase-tracked electromechanical oscillators.

Singularities ubiquitously exist in different fields and play a pivotal role in probing the fundamental laws of physics and developing highly sensitive sensors. Nevertheless, achieving higher-order (≥3) singularities, which exhibit superior performance, typically necessitates meticulous tuning of multiple (≥3) coupled degrees of freedom or additional introduction of nonlinear potential energies. Here we propose theoretically and confirm using mechanics experiments, the existence of an unexplored cusp singularity in the phase-tracked (PhT) steady states of a pair of coherently coupled mechanical modes without the need for multiple (≥3) coupled modes or nonlinear potential energies. By manipulating the PhT singularities in an electrostatically tunable micromechanical system, we demonstrate an enhanced cubic-root response to frequency perturbations. This study introduces a new phase-tracking method for studying interacting systems and sheds new light on building and engineering advanced singular devices with simple and well-controllable elements, with potential applications in precision metrology, portable nonreciprocal devices, and on-chip mechanical computing.

Small Molecule Donors Design Rules for Non-Halogen Solvent Fabricated Organic Solar Cells.

Compared with all-small-molecule (ASM) and other types of organic solar cells (OSCs), the small molecule donor:polymer acceptor (SMD:PA) OSCs develop much slower due to the lack of material matching rules. Herein, by changing the end-cap substituent of the small molecule donor from ethyl (MPhS-C2) to benzyl (MPhS-Ph), the different selection rules of donor properties and thermal annealing (TA) treatment between the ASM and the SMD:PA system under tetrahydrofuran processing are thoroughly investigated. Therefore, MPhS-Ph exhibits more ordered molecular packing, leading to better adaptability in the SMD:PA system without TA; while the inferior molecular packing of MPhS-C2 after spin-coating performs better in the ASM system with TA. Whether spin-coating or TA process dominates morphological optimization also dominates their energy loss. Therefore, the MPhS-Ph:PYF-T-o and MPhS-C2:BTP-eC9 based devices achieve the highest power conversion efficiency (PCE) of 12.1% and 15.7%, respectively, both of which are cutting-edge PCEs in their own type of OSCs fabricated by non-halogen solvent. This result suggests that intrinsic strong crystallization independent of the thermal drive is hoped in SMD:PA-OSCs, while high miscibility after spin-coating and proper assembly under thermal drive is expected in ASM-OSCs, providing deep understanding and guidance in highly efficient materials design rules in both ASM-OSCs and SMD:PA-OSCs.

Macrocyclic Encapsulation in a Non-fused Tetrathiophene Acceptor for Efficient Organic Solar Cells with High Short-Circuit Current Density.

Non-fullerene acceptors have shown great promise for organic solar cells (OSCs). However, challenges in achieving high efficiency molecular system with conformational unicity and effective molecular stacking remain. In this study, we present a new design of non-fused tetrathiophene acceptor R4T-1 via employing the encapsulation of tetrathiophene with macrocyclic ring. The single crystal structure analysis reveals that cyclic alkyl side chains can perfectly encapsulate the central part of molecule and generate a conformational stable and planar molecular backbone. Whereas, the control 4T-5 without the encapsulation restriction displays cis- and twisted conformation. As a result, R4T-1 based OSCs achieved an outstanding power conversion efficiency (PCE) exceeding 15.10 % with a high short-circuit current density (Jsc ) of 25.48 mA/cm2 , which is significantly improved by ≈30 % in relative to that of the control. Our findings demonstrate that the macrocyclic encapsulation strategy could assist fully non-fused electron acceptors (FNEAs) to achieve a high photovoltaic performance and pave a new way for FNEAs design.