Fluorination or Not in Small Molecule Solar Cells: Achieving a Higher Efficiency with Halogen-free End Group.

Fluorination is an efficient strategy for improving organic solar cells (OSCs) efficiency, particularly by fluorinating the end group of emerging nonfullerene acceptors. Here, the fluorination effect was investigated by using small molecule donors with fluorine-free (SBz) and fluorinated (SBz-F) end groups, paired with the emerging nonfullerene acceptor Y6. Interestingly and unexpectedly, fluorination of the end group negatively affects OSCs efficiency, with fluorine-free SBz:Y6 OSCs achieving a higher power conversion efficiency (PCE) of 11.05% compared to the fluorine-containing SBz-F:Y6 blends (PCE = 9.61%). Analysis of space-charge limited currents reveals lower and unbalanced hole/electron mobility in SBz-F:Y6 compared to the SBz:Y6 blends. These findings are further supported by charge recombination dynamics and donor-acceptor miscibility analyses.

Electron Transporting Polymeric Materials with Partial Quaternization for High-Performance Organic Solar Cells.

Efficient cathode interfacial layers (CILs) have become a crucial component of organic solar cells (OSCs). Charge extraction barriers, interfacial trap states, and significant transport resistance may be induced due to the unfavorable cathode interlayer, limiting the device performance. In this study, poly(4-vinylpyridine) is used as the CIL for OSCs, and a new type of CIL named P4VP-I is synthesized through the quaternization strategy. Compared to P4VP, P4VP-I CIL exhibits enhanced conductivity and optimized work function. OSCs employing the P4VP-I ETL demonstrate prolonged carrier lifetime, suppressed charge recombination, and achieve higher power conversion efficiencies (PCE) than the commonly used ETLs such as PFN-Br and Phen-NaDPO.

Fully Fused Indacenodithiophene-Centered Small-Molecule n-Type Semiconductors for High-Performance Organic Electronics.

Developing novel n-type organic semiconductors is an on-going research endeavour, given their pivotal roles in organic electronics and their relative scarcity compared to p-type counterparts. In this study, a new strategy was employed to synthesize n-type organic semiconductors featuring a fully fused conjugated backbone. By attaching two sets of adjacent amino and formyl groups to the indacenodithiophene-based central cores and triggering a tandem reaction sequence of a Knoevenagel condensation-intramolecular cyclization, DFA1 and DFA2 were realized. The solution-processed organic field effect transistors based on DFA1 exhibited unipolar n-type transport character with a decent electron mobility of ca. 0.10 cm2 V-1 s-1 (ca. 0.038 cm2 V-1 s-1 for DFA2 based devices). When employing DFA1 as a third component in organic solar cells, a high power conversion efficiency of 19.2 % can be achieved in ternary devices fabricated with PM6 : L8-BO : DFA1. This work provides a new pathway in the molecular engineering of n-type organic semiconductors, propelling relevant research forward.

Triggered and Tunable Hydrogen Sulfide Release from Photogenerated Thiobenzaldehydes.

Hydrogen sulfide (H2 S) has been identified as an important cell-signaling mediator and has a number of biological functions, such as vascular smooth muscle relaxation, neurotransmission, and regulation of inflammation. A facile and versatile approach for H2 S production initiated by light irradiation and controlled by reaction with an amine or an amino acid was developed. The donor was synthesized in a one-pot reaction, and simple crystallization led to a yield of approximately 90 %. The synthetic strategy is scalable and versatile, and the H2 S donors can be expressed ina number of different molecular and macromolecular forms, including crystalline small-molecule compounds, water-soluble polymers, polystyrene films, and hydrogels. The H2 S donors based on polystyrene film and hydrogel were used as cell-culture scaffolds. The H2 S donor based on water-soluble polymer was applied in photocontrolled inhibition of P-selectin expression on human platelets and subsequent regulation of platelet aggregation. This study provides the simplest controllable H2 S source to study its biological functions. The developed materials are also new therapeutic platforms to deliver H2 S, as there is no accumulation of toxic byproducts, and the donor materials from polystyrene films and hydrogels can be readily removed after releasing H2 S.

Versatile Synthesis of Amino Acid Functional Polymers without Protection Group Chemistry.

The copolymerization of N-isopropylacrylamide (NiPAm) with aldehyde functional monomers facilitates postpolymerization functionalization with amino acids via reductive amination, negating the need for protecting groups. In reductive amination, the imine formed from the condensation reaction between an amine and an aldehyde is reduced to an amine. In this work, we categorize amino acids into four classes based on the functionality of their side chains (acidic, polar neutral, neutral, and basic) and use their amine groups in condensation reactions with aldehyde functional polymers. The dynamic nature of the imine as well as the versatility of reductive amination to functionalize a polymer with a range of amino acids is highlighted. In this manner, amino acid functional polymers are synthesized without the use of protecting groups with high yields, demonstrating the high functional group tolerance of carbonyl condensation chemistry and the subsequent reduction of the imine. Prior to the reduction of the imine bond, transimination reactions are used to demonstrate dynamic polymers that shuffle from a glycine- to a histidine-functional polymer.

Doubly Dynamic Self-Healing Materials Based on Oxime Click Chemistry and Boronic Acids.

The dynamic covalent characteristics of oxime and boronate ester bonds have been explored. A small excess of a competing aldehyde under acidic conditions resulted in oxime polymer degradation from high molecular weights (30 kDa) to low molecular weight oligomers (2.2 kDa). The dynamic nature of oxime bonds imparts oxime cross-linked hydrogels with self-healing properties and the incorporation of phenyl boronic acid groups into the hydrogel network provides a platform for hydrogel functionalization. The addition of a polyphenol (tannic acid) proves a facile means to incorporate a second, dynamic covalent cross-linking network through boronate ester formation which, owing to the increase in the degree of cross-linking, is found to be nearly double the hydrogel strength (storage modulus increased from 4.6 to 8.5 kPa). Finally, the tannic acid cross-linking network is selectively degraded returning the hydrogel storage modulus to its initial value and providing a means for the synthesis of materials with tunable mechanical properties.

Manipulation of Molecular Weight Distribution Shape as a New Strategy to Control Processing Parameters.

Molecular weight and dispersity (Ð) influence physical and rheological properties of polymers, which are of significant importance in polymer processing technologies. However, these parameters provide only partial information about the precise composition of polymers, which is reflected by the shape and symmetry of molecular weight distribution (MWD). In this work, the effect of MWD symmetry on thermal and rheological properties of polymers with identical molecular weights and Ð is demonstrated. Remarkably, when the MWD is skewed to higher molecular weight, a higher glass transition temperature (Tg ), increased stiffness, increased thermal stability, and higher apparent viscosities are observed. These observed differences are attributed to the chain length composition of the polymers, easily controlled by the synthetic strategy. This work demonstrates a versatile approach to engineer the properties of polymers using controlled synthesis to skew the shape of MWD.

The Electrical Behaviors of Grain Boundaries in Polycrystalline Optoelectronic Materials.

Polycrystalline optoelectronic materials are widely used for photoelectric signal conversion and energy harvesting and play an irreplaceable role in the semiconductor field. As an important factor in determining the optoelectronic properties of polycrystalline materials, grain boundaries (GBs) are the focus of research. Particular emphases are placed on the generation and height of GB barriers, how carriers move at GBs, whether GBs act as carrier transport channels or recombination sites, and how to change the device performance by altering the electrical behaviors of GBs. This review introduces the evolution of GB theory and experimental observation history, classifies GB electrical behaviors from the perspective of carrier dynamics, and summarizes carrier transport state under external conditions such as bias and illumination and the related band bending. Then the carrier scattering at GBs and the electrical differences between GBs and twin boundaries are discussed. Last, the review describes how the electrical behaviors of GBs can be influenced and modified by treatments such as passivation or by consciously adjusting the distribution of grain boundary elements. By studying the carrier dynamics and the relevant electrical behaviors of GBs in polycrystalline materials, researchers can develop optoelectronics with higher performance.

Rational molecular and device design enables organic solar cells approaching 20% efficiency.

For organic solar cells to be competitive, the light-absorbing molecules should simultaneously satisfy multiple key requirements, including weak-absorption charge transfer state, high dielectric constant, suitable surface energy, proper crystallinity, etc. However, the systematic design rule in molecules to achieve the abovementioned goals is rarely studied. In this work, guided by theoretical calculation, we present a rational design of non-fullerene acceptor o-BTP-eC9, with distinct photoelectric properties compared to benchmark BTP-eC9. o-BTP-eC9 based device has uplifted charge transfer state, therefore significantly reducing the energy loss by 41 meV and showing excellent power conversion efficiency of 18.7%. Moreover, the new guest acceptor o-BTP-eC9 has excellent miscibility, crystallinity, and energy level compatibility with BTP-eC9, which enables an efficiency of 19.9% (19.5% certified) in PM6:BTP-C9:o-BTP-eC9 based ternary system with enhanced operational stability.

Insights Into Preaggregation Control of Y-Series Nonfullerene Acceptors in Liquid State for Highly Efficient Binary Organic Solar Cells.

Leveraging breakthroughs in Y-series nonfullerene acceptors (NFAs), organic solar cells (OSCs) have achieved impressive power conversion efficiencies (PCEs) exceeding 19%. However, progress in advancing OSCs has decelerated due to constraints in realizing the full potential of the Y-series NFAs. Herein, a simple yet effective solid additive-induced preaggregation control method employing 2-chloro-5-iodopyridine (PDCI) is reported to unlock the full potential of the Y-series NFAs. Specifically, PDCI interacts predominantly with Y-series NFAs enabling enhanced and ordered phase-aggregation in solution. This method leads to a notable improvement and a redshifted absorption of the acceptor phase during film formation, along with improved crystallinity. Moreover, the PDCI-induced preaggregation of NFAs in the solution enables ordered molecule packing during the film-formation process through delicate intermediate states transition. Consequently, the PDCI-induced preaggregated significantly improves the PCE of PM6:Y6 OSCs from 16.12% to 18.12%, among the best values reported for PM6:Y6 OSCs. Importantly, this approach is universally applicable to other Y-series NFA-based OSCs, achieving a champion PCE of 19.02% for the PM6:BTP-eC9 system. Thus, the preaggregation control strategy further unlocks the potential of Y-series NFAs, offering a promising avenue for enhancing the photovoltaic performance of Y-series NFA-based OSCs.

Electrospun Polymeric Fibers Decorated with Silk Microcapsules via Encapsulation and Surface Immobilization for Drug Delivery.

Hollow polymer microcapsules as drug carriers have the advantages of drug protection, storage, and controlled release. Microcapsules combined with tissue engineering scaffolds such as electrospun microfibers can enhance long-term local drug retention. However, the combination methods of microcapsules and fibers still need to be further explored. Here, different technical approaches to functionalize electrospun polycaprolactone (PCL) microfibers with silk fibroin (SF) microcapsules through encapsulation and surface immobilization are developed, including direct blending and emulsion electrospinning for encapsulation, as well as covalent and cleavable disulfide-linkage for surface immobilization. The results of "blending" approach show that silk microcapsules with different sizes could be uniformly encapsulated inside electrospun fibers without aggregation. To further reduce the use of organic solvents, the microcapsules in the aqueous phase can be uniformly distributed in the PCL organic phase and successfully electrospun into fibers using surfactant span-80. For surface immobilization, silk microcapsules are efficiently covalent binding to the surface of electrospun PCL fibers via click chemistry and exhibited noncytotoxic. Based on this method, with the incorporation of a disulfide bond, the linkages between microcapsule and fiber could be cleaved under reducing conditions. These microcapsule-electrospun fiber combination methods provide sufficient options for different drug delivery requirements.

Catalytic Asymmetric Diels-Alder Reaction of 2'-Hydroxychalcone as a Dienophile with a VANOL-Borate Ester Complex.

Numerous flavonoid Diels-Alder-type natural products have been isolated and received great attention from the synthetic community. Herein, we reported a catalytic strategy for an asymmetric Diels-Alder reaction of 2'-hydroxychalcone with a range of diene substrates using a chiral ligand-boron Lewis acid complex. This method enables the convenient synthesis of a wide range of cyclohexene skeletons in excellent yields with moderate to good enantioselectivities, which is critical to prepare natural product congeners for further biological studies.

Balancing the Efficiency and Synthetic Accessibility of Organic Solar Cells with Isomeric Acceptor Engineering.

With the continuous development of organic semiconductor materials and on-going improvement of device technology, the power conversion efficiencies (PCEs) of organic solar cells (OSCs) have surpassed the threshold of 19%. Now, the low production cost of organic photovoltaic materials and devices have become an imperative demand for its practical application and future commercialization. Herein, the feasibility of simplified synthesis for cost-effective small-molecule acceptors via end-cap isomeric engineering is demonstrated, and two constitutional isomers, BTP-m-4Cl and BTP-o-4Cl, are synthesized and compared in parallel. These two non-fullerene acceptors (NFAs) have very similar optoelectronic properties but nonuniform morphological and crystallographic characteristics. Consequently, the OSCs composed of PM6:BTP-m-4Cl realize PCE of 17.2%, higher than that of the OSCs with PM6:BTP-o-4Cl (≈16%). When ternary OSCs are fabricated with PM6:BTP-m-4Cl:BTP-o-4Cl, the averaged PCE value reaches 17.95%, presenting outstanding photovoltaic performance. Most excitingly, the figure of merit (FOM) values of PM6:BTP-m-4Cl, PM6:BTP-o-4Cl, and PM6:BTP-m-4Cl:BTP-o-4Cl based devices are 0.190, 0.178, and 0.202 respectively. The FOM values of these systems are all among the top ones of the current high-efficiency OSC systems, revealing high cost-effectiveness of the two NFAs. This work provides a general but accessible strategy to minimize the efficiency-cost gap and promises the economic prospects of OSCs.

15.3% Efficiency All-Small-Molecule Organic Solar Cells Achieved by a Locally Asymmetric F, Cl Disubstitution Strategy.

Single junction binary all-small-molecule (ASM) organic solar cells (OSCs) with power conversion efficiency (PCE) beyond 14% are achieved by using non-fullerene acceptor Y6 as the electron acceptor, but still lag behind that of polymer OSCs. Herein, an asymmetric Y6-like acceptor, BTP-FCl-FCl, is designed and synthesized to match the recently reported high performance small molecule donor BTR-Cl, and a record efficiency of 15.3% for single-junction binary ASM OSCs is achieved. BTP-FCl-FCl features a F,Cl disubstitution on the same end group affording locally asymmetric structures, and so has a lower total dipole moment, larger average electronic static potential, and lower distribution disorder than those of the globally asymmetric isomer BTP-2F-2Cl, resulting in improved charge generation and extraction. In addition, BTP-FCl-FCl based active layer presents more favorable domain size and finer phase separation contributing to the faster charge extraction, longer charge carrier lifetime, and much lower recombination rate. Therefore, compared with BTP-2F-2Cl, BTP-FCl-FCl based devices provide better performance with FF enhanced from 71.41% to 75.36% and J sc increased from 22.35 to 24.58 mA cm-2, leading to a higher PCE of 15.3%. The locally asymmetric F, Cl disubstitution on the same end group is a new strategy to achieve high performance ASM OSCs.

Artificial Intelligence Designer for Highly-Efficient Organic Photovoltaic Materials.

Designing efficient organic photovoltaic (OPV) materials purposefully is still challenging and time-consuming. It is of paramount importance in material development to identify basic functional units that play the key roles in material performance and subsequently establish the substructure-property relationship. Herein, we describe an automatic design framework based on an in-house designed La FREMD Fingerprint and machine learning (ML) algorithms for highly efficient OPV donor molecules. The key building blocks are identified, and a library consisting of 18 960 new molecules is generated within this framework. Through investigating the chemical structures of materials with different performance, a guidance on designing efficient OPV materials is proposed. Furthermore, the most promising candidates exhibit a predicted power conversion efficiency (PCE) value of over 15% when combined with acceptor Y6. Density functional theory (DFT) studies show these candidate materials possess exceptional potential for efficient charge carrier transport. The proposed framework demonstrates the ability to design new materials based on the substructure-property relationship built by ML, which provides an alternative methodology for applying ML in new material discovery.

Construction of microbelts through the coassembly of a disclike molecule and primary alkyl ammoniums: a noncovalent strategy to mimic covalently bonded pi-core alkyl chain structure.

In this letter, we report the fabrication of microbelts through the coassembly of hexa-2-pyridyl-hexaazatriphenylen (HPHAT), a disklike pi-conjugated molecule, with primary alkyl ammonium triflate. The strategy is first to construct hydrogen-bonded complexes between HPHAT and primary alkyl ammoniums to mimic covalently bonded pi-core alkyl chain structures, and then the complexes self-assemble into microbelts driven by pi-pi stacking in the pi core and van der Waals interactions between the peripheral alkyl chains. The morphology of as-prepared microbelts has been characterized with scanning electron microscopy (SEM), optical microscopy, polarizing microscopy, and transmission electron microscopy (TEM). Spectroscopic and crystallographic investigations were also carried out to reveal the formation mechanism of the microbelts, through which a sequential self-assembly process has been proposed.

An asymmetric end-capping strategy enables a new non-fullerene acceptor for organic solar cells with efficiency over 10.

Two different terminal groups, rhodanine-flanked benzo[c][1,2,5]thiadiazole (BR) and 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (IM2F), were connected to an indaceno[1,2-b:5,6-b']dithiophene (IDT) core to construct a new non-fullerene acceptor (IDTBF). Solar cells based on this acceptor exhibited promising photovoltaic performances with a power conversion efficiency (PCE) of up to 10.43%.

A "σ-Hole"-Containing Volatile Solid Additive Enabling 16.5% Efficiency Organic Solar Cells.

Here we introduce a σ-hole-containing volatile solid additive, 1, 4-diiodotetrafluorobenzene (A3), in PM6:Y6-based OSCs. Aside from the appropriate volatility of A3 additive, the synergetic halogen interactions between A3 and photoactive matrix contribute to more condensed and ordered molecular arrangement in the favorable interpenetrating donor/acceptor domains. As a result, greatly accelerated charge transport process with suppressed charge recombination possibility is observed and ultimately a champion PCE value of 16.5% is achieved. Notably, the A3 treated OSCs can maintain a high efficiency of over 16.0% in a wide concentration range of A3 additive between 10 and 35 mg/mL. The A3-treated device shows excellent stability with an efficiency of 15.9% after 360-h storage. This work demonstrates that the σ-hole interaction can be applied to enhance the OSC performance and highlights the importance of non-covalent interactions in the optoelectronic materials.

Molecular Lock Induced by Chloroplatinic Acid Doping of PEDOT:PSS for High-Performance Organic Photovoltaics.

In organic photovoltaics (OPVs), the mechanical contact between charge transport layers and photoactive layer can influence the electrical contact that facilitates carrier collection. Unfortunately, the mechanical contact at the interface is rarely discussed in the OPV context. Herein, we report a distinct molecular locking effect that occurs between the donor molecules in the photoactive layer and the hole transport layer (HTL). This is achieved by doping chloroplatinic acid into poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate). The "molecular lock" at the interface leads to denser distribution and more ordered assembling of PM6 donor molecules close to the HTL. Consequently, the trap-assisted recombination in the cell is greatly suppressed, and the carrier lifetime is prolonged by more than 2 times. Together with the elevated charge carrier collection probability, a high fill factor of 77% and a power conversion efficiency of 16.5% are achieved in the PM6:Y6-based OPVs. This study provides a feasible way to boost the device performance by reinforcing the interfacial interaction between the HTL and photoactive layer.

A multifunctional surfactant catalyst inspired by hydrolases.

The remarkable power of enzymes to undertake catalysis frequently stems from their grouping of multiple, complementary chemical units within close proximity around the enzyme active site. Motivated by this, we report here a bioinspired surfactant catalyst that incorporates a variety of chemical functionalities common to hydrolytic enzymes. The textbook hydrolase active site, the catalytic triad, is modeled by positioning the three groups of the triad (-OH, -imidazole, and -CO2H) on a single, trifunctional surfactant molecule. To support this, we recreate the hydrogen bond donating arrangement of the oxyanion hole by imparting surfactant functionality to a guanidinium headgroup. Self-assembly of these amphiphiles in solution drives the collection of functional headgroups into close proximity around a hydrophobic nano-environment, affording hydrolysis of a model ester at rates that challenge α-chymotrypsin. Structural assessment via NMR and XRD, paired with MD simulation and QM calculation, reveals marked similarities of the co-micelle catalyst to native enzymes.