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A NIR strong absorbing molecule was constructed by taking the structural advantages of a quinoid and diketopyrrolopyrrole, with an absorption maximum of up to 1039 nm and hole and electron mobilities up to 0.19 and 0.2 cm2 V−1 s−1, respectively.

Energy loss caused by exciton binding energy (

Among the three A–D–A-type nonfullerene acceptors, MQ7-i has improved molecular planarity, compact packing motifs, and the largest charge transfer integrals and the highest electron mobilities thereby yielding the highest efficiency of 16.23%.

Our work presents a study on the working mechanism of ternary organic photovoltaic devices based on non-fullerene acceptors, focusing on the composition-dependent optoelectronic property variations in blend films and devices.

Low energy loss is a prerequisite for organic solar cells to achieve high photovoltaic efficiency. Electron-vibration coupling (i.e., intramolecular reorganization energy) plays a crucial role in the photoelectrical conversion and energy loss processes. In this concept article, we summarize our recent theoretical advances on revealing the energy loss mechanisms at the molecular level of A-D-A electron acceptors. We underline the importance of electron-vibration couplings on reducing the energy loss and describe the effective molecular design strategies towards low energy loss through decreasing the electron-vibration couplings.

An electron collection layer (ECL) between a photoactive overlay and an electrode plays a crucial role in optimizing the light field and charge extraction in bulk-heterojunction (BHJ) polymer solar...

Reducing the exciton binding energy

In contrast to the inorganic and perovskite solar cells, organic photovoltaics (OPV) depend on a series of charge generation and recombination processes, which complicates molecular design to improve the power conversion efficiencies (PCEs). Herein, we first propose the singlet-triplet energy gap (ΔE

Inorganic cesium lead halide perovskites offer a pathway towards thermally stable photovoltaics. However, moisture-induced phase degradation restricts the application of hole transport layers (HTLs) with hygroscopic dopants. Dopant-free HTLs fail to realize efficient photovoltaics due to severe electrical loss. Herein, we developed an electrical loss management strategy by manipulating poly(3-hexylthiophene) with a small molecule, i.e., SMe-TATPyr. The developed P3HT/SMe-TATPyr HTL shows a three-time increase of carrier mobility owing to breaking the long-range ordering of "edge-on" P3HT and inducing the formation of "face-on" clusters, over 50 % decrease of the perovskite surface defect density, and a reduced voltage loss at the perovskite/HTL interface because of favorable energy level alignment. The CsPbI2 Br perovskite solar cell demonstrates a record-high efficiency of 16.93 % for dopant-free HTL, and superior moisture and thermal stability by maintaining 96 % efficiency at low-humidity condition (10-25 % R. H.) for 1500 hours and over 95 % efficiency after annealing at 85 °C for 1000 hours.

Organic solar cells (OSCs) with nonfullerene acceptors (NFAs) exhibit efficient charge generation under small interfacial energy offsets, leading to over 18% efficiency for the single-junction devices based on the state-of-the-art NFA of Y6. Herein, to reveal the underlying charge generation mechanisms, we have investigated the exciton binding energy ( E b ) in Y6 by a joint theoretical and experimental study. The results show that owing to strong charge polarization effects, Y6 has remarkable small E b of -0.11~0.15 eV, which is even lower than perovskites in many cases. Moreover, it is peculiar that the photoluminescence is enhanced with temperature, and the energy barrier for separating excitons into charges is evidently lower than the thermal energy according to the temperature dependence of photoluminescence, manifesting direct photogeneration of charge carriers enabled by weak E b in Y6. Thus, charge generation in NFA-based OSCs shows little dependence on interfacial driving forces.

Temperature-insensitive properties are attractive for most electronics, including polymeric semiconducting devices. Especially, polymeric field-effect transistors (FETs) with high mobility have been important research targets due to their broad applications. However, polymeric FETs with stable charge transport operating at extremely cold or hot zones are faced with enormous challenges. In this study, the polyacrylonitrile was found to significantly tune the sizes of pre-aggregates of polymers in solutions and the crystallinity of the polymeric films. The orientation of 5–25 μm linear grains in the films were prepared through the bar-coating process with polyacrylonitrile as an additive, which stabilized the electron mobility over a wide range of temperatures. The linear-grain morphology of the film contributed to reducing the holes and grain boundaries in the transport paths of carriers. Typically, the top-gate FETs based on P(NDI2OD-T2) displayed a stable electron transporting behavior from 200 to 460 K, with mobility greater than 3.5 cm2V−1s−1.

Funder: Ministry of Science and Technology of the People’s Republic of China (Chinese Ministry of Science and Technology), The cornerstones of emerging high-performance organic photovoltaic devices are bulk heterojunctions, which usually contain both structure disorders and bicontinuous interpenetrating grain boundaries with interfacial defects. This feature complicates fundamental understanding of their working mechanism. Highly-ordered crystalline organic p–n heterojunctions with well-defined interface and tailored layer thickness, are highly desirable to understand the nature of organic heterojunctions. However, direct growth of such a crystalline organic p–n heterojunction remains a huge challenge. In this work, we report a design rationale to fabricate monolayer molecular crystals based p–n heterojunctions. In an organic field-effect transistor configuration, we achieved a well-balanced ambipolar charge transport, comparable to single component monolayer molecular crystals devices, demonstrating the high-quality interface in the heterojunctions. In an organic solar cell device based on the p–n junction, we show the device exhibits gate-tunable open-circuit voltage up to 1.04 V, a record-high value in organic single crystalline photovoltaics.

To unveil the underlying mechanisms of high-efficiency near-infrared (NIR) organic thermally activated delayed fluorescence (TADF), we investigated the transition natures of the low-lying excited s...

Ultrathin two-dimensional (2D) semiconductors exhibit outstanding properties, but it remains challenging to obtain monolayer-structured inorganic semiconductors naturally occurring as nonlayered crystals. Copper sulfides are a class of widely studied nonlayered metal chalcogenide semiconductors. Although 2D copper sulfides can provide extraordinary physical and chemical applications, investigations of 2D copper sulfides in the extreme quantum limit are constrained by the difficulty in preparing monolayered copper sulfides. Here, we report a subnanometer-thin quasi-copper-sulfide (q-CS) semiconductor formed upon self-assembly of copper(I)-dodecanethiol complexes. Extended X-ray absorption fine structure analysis revealed that the existence of Cu-Cu bonding endowed the layer-structured q-CS with semiconductor properties, such as appreciable interband photoluminescence. Theoretical studies on the band structure demonstrated that the optical properties of copper-dodecanethiol assemblies were dominated by the q-CS layer and the photoluminescence originated from exciton radiative recombination across an indirect band gap, borne out by experimental observation at higher temperatures, but with the onset of a direct emission process at cryogenic temperatures. The following studies revealed that the metal-metal bonding occurred not only in copper-alkanethiolate complex assemblies with variable alkyl chain length but also in silver-alkanethiolate and cadmium-alkanethiolate assemblies. Therefore, the current studies may herald a class of 2D semiconductors with extremely thin thickness out of nonlayered metal sulfides to bridge the gap between conventional inorganic semiconductors and organic semiconductors.

To understand the dominance of 2,2′-((2Z,2′Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2′′,3′′:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2-g]thieno[2′,3′:4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile (Y6) and its derivatives leading to the rapid efficiency rise of organic solar cells (OSCs), solid film structures are of significant importance. Here, we employ cryo-transmission electron microscopy (Cryo-TEM) to resolve the landscape of Y6 packing in neat films (unlike single crystals) in relation to device performance, and reveal how processing with carbon disulfide and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) influences its molecular packing, prominently the backbone ordering. We show that Y6 prefers a face-on dominant packing structure with an in-plane long-range conjugated backbone packing in films. The long-range backbone ordering is beneficial for reducing disorders on the energy distribution of the electron transport level, thereby improving the carrier lifetime in heterojunctions. We confirm that long-range energy transfer assists poly[(2,6-(4,8-bis(5-(2-ethylhexyl)-4-fluorothiophen-2-yl)-benzo[1,2-b:4,5-b′]dithiophene))-alt-(5,5-(1′,3′-di-2-thienyl-5′,7′-bis(2-ethylhexyl)benzo[1′,2′-c:4′,5′-c′]dithiophene-4,8-dione))] (PM6) excitons to reach the preferred Y6/PM6 interfaces without being quenched by PC71BM clusters, yielding no signs of bimolecular recombination and a high power conversion efficiency of 16.8%. Our results suggest an effective molecular packing structure in solid films, and the prominent role of backbone ordering in photoelectric conversion processes, which will outline the future development of OSCs.

Because of the emergence of small-molecule acceptors with acceptor–donor–acceptor (A–D–A) structures, organic solar cells (OSCs) have developed rapidly in recent years. Currently, the power conversion efficiencies (PCEs) of the OSCs based on A–D–A acceptors exceed 18%, much higher than those of the fullerene-based OSCs. Nonetheless, the photovoltaic performances of OSCs still lag behind inorganic and perovskite solar cells due to more serious energy losses. Herein, in order to reveal the energy loss mechanisms at the molecular level, we have investigated the geometric structures of the ground (S0), excited (S1), and anionic (A−) states as well as the mutual transitions among these electronic states for a series of A–D–A acceptors with fully fused rigid or non-fused flexible donor units. The results show that the fully fused molecules have planar backbones in all the electronic states, while the non-fused molecules are much distorted at S0, and become less twisted at S1 and A−. Consequently, compared with the non-fused A–D–A acceptors, the fused ones generally have smaller reorganization energies for each electronic transition, leading to reduced voltage and current losses. In addition, extending the donor unit lengths is beneficial for reducing charge recombination and facilitating charge transport. These results indicate that design and optimization of large fused A–D–A acceptors would be an effective way to further improve the organic photovoltaic performance.

Rare studies of cocrystal engineering have focused on improving carrier mobility of organic semiconductors mainly because of the generation of ambipolarity, the alteration of the charge carrier polarity or the reduction of electronic couplings. Herein, we utilize indolo[2,3-a]carbazole (IC) as the model compound and 2,6-diphenylanthraquinone (DPAO) and 9-fluorenone (FO) as the coformers to construct IC2-DPAO and IC-FO cocrystals with 2 : 1 or 1 : 1 ratios, respectively, through hydrogen bonds and donor-acceptor interactions. Interestingly, the more appropriate packing structure, possessing not only enhanced electronic couplings but also increased intermolecular distances, is achieved in IC2-DPAO, which shows an improved carrier mobility of 0.11 cm

The A-DA'D-A fused-ring electron acceptors with an angular fusion mode and electron-deficient core has significantly boosted organic photovoltaic efficiency. Here, the intrinsic role of the peculiar structure is revealed by comparing representative A-DA'D-A acceptor Y6 with its A-D-A counterparts having different fusion modes. Owing to the more delocalized HOMO and deeper LUMO level, Y6 exhibits stronger and red-shifted absorption relative to the linear and angular fused A-D-A acceptors, respectively. Moreover, the change from linear to angular fusion substantially reduces the electron-vibration couplings, which is responsible for the faster exciton diffusion, exciton dissociation, and electron transport for Y6 than the linear fused A-D-A acceptor. Notably, the electron-vibration coupling for exciton dissociation is further decreased by introducing the electron-deficient core, thus contributing to the efficient charge generation under low driving forces in the Y6-based devices.

Polar materials attract wide research interest due to their unique properties, such as ferroelectricity and the bulk photovoltaic effect (BPVE), which are not accessible with nonpolar materials. However, in general, rationally designing polar materials is difficult because nonpolar materials are more favorable in terms of dipole-dipole interactions. Here, we report a rational strategy to form polar assemblies with bowl-shaped π-conjugated molecules and a molecular design principle for this strategy. We synthesized and thoroughly characterized 12 single crystals with the help of various theoretical calculations. Furthermore, we demonstrated that it can be possible to predict whether polar assemblies become more favorable or not by estimating their lattice energies. We believe that this study contributes to the development of organic polar materials and their related studies.

Three donor–acceptor–donor molecular emitters have been designed by taking triphenylamine or N-phenylcarbazole as the donor and maleimide or phenyl maleimide as the acceptor, in which the highest o...

Benefiting from near-infrared persistent luminescence, chromium-doped zinc gallate nanoparticles have become appealing for background-free biomedical imaging applications, where autofluorescence from adjacent tissues no longer poses a problem. Nevertheless, the synthesis of persistent luminescent nanoparticles with controllable and biologically appropriate size, high luminescence intensity, and long persistent duration remains very challenging. Herein, we report a solvothermal synthetic route for preparing differently sized ZnGa2O4:Cr nanoparticles with a particle size tunable from 4 to 31 nm and afterglow duration longer than 20 h. The route involves lower reaction temperatures and involves no reworking of the particles postsynthesis, providing materials that have far fewer unwanted defects and much higher luminescence yields (up to 51%). It was found that methanol played a paramount role in obtaining the Cr3+-doped ZnGa2O4 nanoparticles. The effects of methanol were discussed in combination with NMR spectroscopy studies and theoretical calculations, and the underlying alcohol-mediated growth and doping mechanisms were elucidated, which will be beneficial for developing highly persistent luminescent nanoparticles.

Triplet acceptors have been developed to construct high‐performance organic solar cells (OSCs) as the long lifetime and diffusion range of triplet excitons may dissociate into free charges instead of net recombination when the energy levels of the lowest triplet state (T1) are close to those of charge‐transfer states (3CT). The current triplet acceptors were designed by introducing heavy atoms to enhance the intersystem crossing, limiting their applications. Herein, two twisted acceptors without heavy atoms, analogues of Y6, constructed with large π‐conjugated core and D‐A structure, were confirmed to be triplet materials, leading to high‐performance OSCs. The mechanism of triplet excitons were investigated to show that the twisted and D‐A structures result in large spin–orbit coupling (SOC) and small energy gap between the singlet and triplet states, and thus efficient intersystem crossing. Moreover, the energy level of T1 is close to 3CT, facilitating the split of triplet exciton to free charges., Triplet materials are designed by introducing heavy atoms to enhance spin–orbit coupling or constructing donor and acceptor units with a twisted conformation to reduce ΔE ST. However, the twisted materials have not been applied in solar cells due to weak absorption and low charge‐transport mobilities. Now two nonplanar acceptors with large π‐conjugated core were constructed that achieved over 15 % efficiency.

The separation of charge-transfer states into free charges at the donor/acceptor (D/A) interfaces plays a central role in organic solar cells (OSCs). Because of strong Coulomb attraction, the separation mechanisms are elusive, particularly for the high-efficiency non-fullerene (NF) OSCs with low exciton-dissociation driving forces. Here, we demonstrate that the Coulomb barriers can be substantially overcome by electronic polarization for OSCs based on a series of A-D-A acceptors (ITIC, IT-4F, and Y6). In contrast to fullerene-based D/A heterojunctions, the polarization energies for both donor holes and acceptor electrons are remarkably increased from the interfaces to pure regions in the NF heterojunctions because of strong stabilization on electrons but destabilization on holes by electrostatic interactions in the A-D-A acceptors. In particular, upon incorporation of fluorine substituents and electron-poor cores into ITIC, the increased polarization energies can completely compensate for the Coulomb attraction in the IT-4F- and Y6-based heterojunctions, leading to barrierless charge separation.

Both the efficiency and stability of low-cost organic solar cells are central components for meeting the requirements of commercialization for organic photovoltaics (OPV). Furthermore, the relation...