Solid Additive Engineering for Next-generation Organic Photovoltaics.

Solution-processed bulk heterojunction (BHJ) organic solar cells (OSCs) have emerged as a promising next-generation photovoltaic technology. In this emerging field, there is a growing trend of employing solid additives (SAs) to fine-tune the BHJ morphology and unlock the full potential of OSCs. SA engineering offers several significant benefits for commercialization, including the ability to i) control film-forming kinetics to expedite high-throughput fabrication, ii) leverage weak noncovalent interactions between SA and BHJ materials to enhance the efficiency and stability of OSCs, and iii) simplify procedures to facilitate cost-effective production and scaling-up. These features make SA engineering a key catalyst for accelerating the development of OSCs. Recent breakthroughs have shown that SA engineering can achieve an efficiency of 19.67% in single-junction OSCs, demonstrating its effectiveness in promoting the commercialization of organic photovoltaic devices. This review provides a comprehensive overview of significant breakthroughs and pivotal contributions of emerging SAs, focusing on their roles in governing film-forming dynamics, stabilizing phase separation, and addressing other crucial aspects. The rationale and design rules for SAs in highly efficient and stable OSCs are also discussed. Finally, the remaining challenges are summarized, and perspectives on future advances in SA engineering are offered.

Polymer Fiber Rigid Network with High Glass Transition Temperature Reinforces Stability of Organic Photovoltaics.

Organic photovoltaics (OPVs) need to overcome limitations such as insufficient thermal stability to be commercialized. The reported approaches to improve stability either rely on the development of new materials or on tailoring the donor/acceptor morphology, however, exhibiting limited applicability. Therefore, it is timely to develop an easy method to enhance thermal stability without having to develop new donor/acceptor materials or donor-acceptor compatibilizers, or by introducing another third component. Herein, a unique approach is presented, based on constructing a polymer fiber rigid network with a high glass transition temperature (Tg) to impede the movement of acceptor and donor molecules, to immobilize the active layer morphology, and thereby to improve thermal stability. A high-Tg one-dimensional aramid nanofiber (ANF) is utilized for network construction. Inverted OPVs with ANF network yield superior thermal stability compared to the ANF-free counterpart. The ANF network-incorporated active layer demonstrates significantly more stable morphology than the ANF-free counterpart, thereby leaving fundamental processes such as charge separation, transport, and collection, determining the device efficiency, largely unaltered. This strategy is also successfully applied to other photovoltaic systems. The strategy of incorporating a polymer fiber rigid network with high Tg offers a distinct perspective addressing the challenge of thermal instability with simplicity and universality.

Stabilizing Top Interface by Molecular Locking Strategy with Polydentate Chelating Biomaterials toward Efficient and Stable Perovskite Solar Cells in Ambient Air.

The instability of top interface induced by interfacial defects and residual tensile strain hinders the realization of long-term stable n-i-p regular perovskite solar cells (PSCs). Herein, one molecular locking strategy is reported to stabilize top interface by adopting polydentate ligand green biomaterial 2-deoxy-2,2-difluoro-d-erythro-pentafuranous-1-ulose-3,5-dibenzoate (DDPUD) to manipulate the surface and grain boundaries of perovskite films. Both experimental and theoretical evidence collectively uncover that the uncoordinated Pb2+ ions, halide vacancy, and/or I─Pb antisite defects can be effectively healed and locked by firm chemical anchoring on the surface of perovskite films. The ingenious polydentate ligand chelating is translated into reduced interfacial defects, increased carrier lifetimes, released interfacial stress, and enhanced moisture resistance, which should be liable for strengthened top interface stability and inhibited interfacial nonradiative recombination. The universality of the molecular locking strategy is certified by employing different perovskite compositions. The DDPUD modification achieves an enhanced power conversion efficiency (PCE) of 23.17-24.47%, which is one of the highest PCEs ever reported for the devices prepared in ambient air. The unsealed DDPUD-modified devices maintain 98.18% and 88.10% of their initial PCEs after more than 3000 h under a relative humidity of 10-20% and after 1728 h at 65 °C, respectively.

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.

Polydentate Ligand Reinforced Chelating to Stabilize Buried Interface toward High-Performance Perovskite Solar Cells.

The instability of the buried interface poses a serious challenge for commercializing perovskite photovoltaic technology. Herein, we report a polydentate ligand reinforced chelating strategy to strengthen the stability of buried interface by managing interfacial defects and stress. The bis(2,2,2-trifluoroethyl) (methoxycarbonylmethyl)phosphonate (BTP) is employed to manipulate the buried interface. The C=O, P=O and two -CF3 functional groups in BTP synergistically passivate the defects from the surface of SnO2 and the bottom surface of the perovskite layer. Moreover, The BTP modification contributes to mitigated interfacial residual tensile stress, promoted perovskite crystallization, and reduced interfacial energy barrier. The multidentate ligand modulation strategy is appropriate for different perovskite compositions. Due to much reduced nonradiative recombination and heightened interface contact, the device with BTP yields a promising power conversion efficiency (PCE) of 24.63 %, which is one of the highest efficiencies ever reported for devices fabricated in the air environment. The unencapsulated BTP-modified devices degrade to 98.6 % and 84.2 % of their initial PCE values after over 3000 h of aging in the ambient environment and after 1728 h of thermal stress, respectively. This work provides insights into strengthening the stability of the buried interface by engineering multidentate chelating ligand molecules.

Advances in chloride additives for high-efficiency perovskite solar cells: multiple points of view.

Chloride (Cl) additives are rather effective in improving the performance of perovskite solar cells (PSCs) through the modulation of crystallization process and surface morphology. After incorporating Cl-containing additives, the optoelectrical properties of perovskite films, such as the electron/hole diffusion length and carrier lifetime, are greatly enhanced. However, only a trace amount of Cl has been identified in the resultant perovskite film, and the mechanism of efficiency improvement induced by Cl remains unclear. In this review, we discuss organic and inorganic Cl additives systematically from the perspective of their solubility, volatility, cation size and chemical groups. In addition, the roles of residual Cl anions and cations are analyzed in detail. Finally, some valuable future perspectives of Cl additives are proposed.

Electronic Configuration Tuning of Centrally Extended Non-Fullerene Acceptors Enabling Organic Solar Cells with Efficiency Approaching 19 .

In the molecular optimizations of non-fullerene acceptors (NFAs), extending the central core can tune the energy levels, reduce nonradiative energy loss, enhance the intramolecular (donor-acceptor and acceptor-acceptor) packing, facilitate the charge transport, and improve device performance. In this study, a new strategy was employed to synthesize acceptors featuring conjugation-extended electron-deficient cores. Among these, the acceptor CH-BBQ, embedded with benzobisthiadiazole, exhibited an optimal fibrillar network morphology, enhanced crystallinity, and improved charge generation/transport in blend films, leading to a power conversion efficiency of 18.94 % for CH-BBQ-based ternary organic solar cells (OSCs; 18.19 % for binary OSCs) owing to its delicate structure design and electronic configuration tuning. Both experimental and theoretical approaches were used to systematically investigate the influence of the central electron-deficient core on the properties of the acceptor and device performance. The electron-deficient core modulation paves a new pathway in the molecular engineering of NFAs, propelling relevant research forward.

Solvent-Free Grinding Synthesis of Hybrid Copper Halides for White Light Emission.

Lead-free metal halides (LMHs) have recently attracted numerous attention in solid-state lighting due to their unique structures and outstanding optoelectronic properties. However, conventional preparation processes with the utilization of toxic organic solvents and high temperatures seem to impede commercial applications of LMHs. In this work, we successfully synthesize Cu+-based metal halides (TMA)3Cu2Br5-xClx (TMA: tetramethylammonium) with high photoluminescence quantum yields (PLQYs) via a solvent-free mechanical grinding method. By changing the ratio of halide ions (Cl- and Br-) in precursors, the emission wavelength of the prepared (TMA)3Cu2Br5-xClx can be tuned from 535 to 587 nm, which are employed as emitters in the fabrication of white-light-emitting diodes (WLEDs). The achieved WLEDs exhibit a high color rendering index value of 84 and standard Commission Internationale de l'Éclairage (CIE) coordinates of (0.324, 0.333). This feasible and solvent-free preparation strategy not only promotes the mass production of LMHs but also highlights the promising potential for efficient solid-state illumination.

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.

Low-Temperature Solution Synthesis of Stable Cs3Cu2Br5 Single Crystals for Visible Light Communications.

Inorganic perovskites CsPbX3 (X = Cl, Br, I) have shown great potential as luminescent materials for a wide range of photoelectric devices. However, the practical use of these materials is limited due to the toxicity of lead and poor stability. Here, we present a facile low-temperature, solution-based method to synthesize lead-free and highly stable Cs3Cu2Br5 single crystals (SCs) without the use of organic solvents. Owing to the self-trapped exciton emissions, Cs3Cu2Br5 SCs exhibit a strong broadband blue emission with a high photoluminescence quantum yield (PLQY) upon 254 nm ultraviolet light excitation. In addition, the Cs3Cu2Br5 SCs show a high stability against heat, humidity, and UV light. Therefore, the Cs3Cu2Br5 SCs are utilized as emitters in white light emitting diodes (WLEDs), demonstrating a high color rendering index of 81 and a decent commission internationale de l'Eclairage coordinate of (0.30, 0.34). Furthermore, the prepared WLEDs are used in wireless visible light communications, showing a -3 dB bandwidth of 6.7 MHz and an achievable data rate of 45 Mbps. Our study provides a novel organic-solvent-free, low-temperature method to synthesize Cs3Cu2Br5 SCs and could promote the development of Cu-based metal halides in visible light communications.

Application of Natural Molecules in Efficient and Stable Perovskite Solar Cells.

Perovskite solar cells (PSCs), one of the most promising photovoltaic technologies, have been widely studied due to their high power conversion efficiency (PCE), low cost, and solution processability. The architecture of PSCs determines that high PCE and stability are highly dependent on each layer and the related interface, where nonradiative recombination occurs. Conventional synthetic chemical materials as modifiers have disadvantages of being toxic and costly. Natural molecules with advantages of low cost, biocompatibility, and being eco-friendly, and have improved PCE and stability by modifying both functional layers and interface. In this review, we discuss the roles of natural molecules on PSCs devices in terms of the perovskite active layer, interface, carrier transport layers (CTLs), and substrate. Finally, the summary and outlook for the future development of natural molecule-modified PSCs are also addressed.

19.31% binary organic solar cell and low non-radiative recombination enabled by non-monotonic intermediate state transition.

Non-fullerene acceptors based organic solar cells represent the frontier of the field, owing to both the materials and morphology manipulation innovations. Non-radiative recombination loss suppression and performance boosting are in the center of organic solar cell research. Here, we developed a non-monotonic intermediate state manipulation strategy for state-of-the-art organic solar cells by employing 1,3,5-trichlorobenzene as crystallization regulator, which optimizes the film crystallization process, regulates the self-organization of bulk-heterojunction in a non-monotonic manner, i.e., first enhancing and then relaxing the molecular aggregation. As a result, the excessive aggregation of non-fullerene acceptors is avoided and we have achieved efficient organic solar cells with reduced non-radiative recombination loss. In PM6:BTP-eC9 organic solar cell, our strategy successfully offers a record binary organic solar cell efficiency of 19.31% (18.93% certified) with very low non-radiative recombination loss of 0.190 eV. And lower non-radiative recombination loss of 0.168 eV is further achieved in PM1:BTP-eC9 organic solar cell (19.10% efficiency), giving great promise to future organic solar cell research.

1-Adamantanamine Hydrochloride Resists Environmental Corrosion to Obtain Highly Efficient and Stable Perovskite Solar Cells.

Passivating the defective surface of perovskite film is a promising strategy to improve the stability and efficiency of perovskite solar cells (PSCs). Herein, 1-adamantanamine hydrochloride (ATH) is introduced to the upper surface of the perovskite film to heal the defects of the perovskite surface. The best-performance ATH-modified device has a higher efficiency (23.45%) than the champion control device (21.53%). The defects are passivated, interfacial nonradiative recombination is suppressed, and interface stress is released by the ATH deposited on the perovskite film, leading to longer carrier lifetimes and enhancement in open-circuit voltage (VOC) and fill factor (FF) of the PSCs. With obvious improvement, VOC and FF of 1.159 V and 0.796 for the control device are raised to 1.178 V and 0.826 for the ATH-modified device, respectively. Finally, during an operational stability measurement of more than 1000 h, the ATH-treated PSC exhibited better moisture resistance, thermal persistence, and light stability.

Architecturally simple organic photodiodes with highly competitive figures of merit via a facile self-assembly strategy.

Photodetectors (PDs) based on organic materials exhibit potential advantages such as low-temperature processing, and superior mechanical properties and form factors. They have seen rapid strides toward achieving performance metrics comparable to inorganic counterparts. Here, a simplified device architecture is employed to realize stable and high-performance organic PDs (OPDs) while further easing the device fabrication process. In contrast to the sequential deposition of the hole blocking layer (HBL) and active layer (conventional 'two-step' processing), the proposed strategy forms a self-assembled HBL and active layer in a 'single-step' process. A high-performance UV-Vis-NIR OPD based on the PM6:BTP-eC9 system is demonstrated using this cost-effective processing strategy. The green solvent processed proof-of-concept device exhibits remarkable responsivity of ∼0.5 A W-1, lower noise current than conventional two-step OPD, ultrafast rise/fall times of 1.4/1.6 µs (comparable to commercial silicon diode), and a broad linear dynamic range of 140 dB. Importantly, highly stable (light and heat) devices compared to those processed by the conventional method are realized. The broad application potential of this elegant strategy is proven by demonstrating the concept in three representative systems with broadband sensing competence.

Highly efficient copper-based halide single crystals with violet emission for visible light communication.

K2CuBr3 single crystals (SCs) are synthesized using a cooling-induced crystallization method with violet emission due to self-trapped excitons (STEs) under photoexcitation. The prepared K2CuBr3 SCs exhibit a high photoluminescence quantum yield (PLQY, 79.2%) and excellent stability against moisture, heat and UV light. When the K2CuBr3 SCs are used as a light source for visible light communication the data transmission rate reaches a striking 248 Mbps, which is more than 33-fold the -3 dB bandwidth.

Printable high-efficiency organic ionic photovoltaic materials discovered by high-throughput first-principle calculations.

Printable solar cells are promising for low cost and large-scale production. As the two main classes of printable solar cells, organic and perovskite solar cells show distinct advantages and apparent drawbacks. The latter stand as major obstacle toward their commercialization. It is amazing if the advantages of organic and perovskite solar cells are integrated since some of them are complementary. Here, we report ionic-type high-efficiency photovoltaic materials which achieve this goal. We explore 46,388 organic materials from the Crystallography Open Database by extensive quantum mechanical calculations. Through photovoltaic-functionality-directed materials screening, we identify 5 organic ionic-type photovoltaic materials. They show the merits of nontoxic, high dielectric constant (27.03), high theoretical efficiency (28.7%), and superior thermal stability. Our findings propose ionic-type photovoltaic materials, which may surpass traditional organic and perovskite materials and open the door to next-generation printable solar cells.

Flexible perovskite scintillators and detectors for X-ray detection.

X-ray detection and imaging technology has been rapidly developed for various fields since 1895, offering great opportunities to scientific and industrial communities. Particularly, flexible X-ray detectors have drawn numerous attention in medical-related applications, solving the uniform issues of traditional rigid X-ray detectors. Out of all the potential materials, metal halide perovskites (MHPs) have been emerged as excellent candidates as flexible X-ray scintillators and detectors owing to the advantages including low temperature solution processable, strong X-ray absorption coefficient, large mobility lifetime product and tunable bandgap. In this review, the recent advances of MHP-based flexible X-ray detectors are comprehensively summarized, focusing on the scalable synthesis technologies of materials and diverse device architectures, and covering both direct and indirect X-ray detection. A brief outlook that highlights the current challenges impeding the commercialization of flexible MHP-based X-ray detectors is also included with possible solutions to those problem being provided.

Flexible and stable copper-based halide scintillator for high-performance X-ray imaging.

Rb2CuBr3 nanocrystals with a high photoluminescence quantum yield (PLQY) of 75% were synthesized and then further mixed with polymethyl methacrylate to form flexible scintillators. The scintillators maintain a high PLQY, even after bending for 2000 cycles and storing in air for 28 days. X-Ray imaging of targeted objects was demonstrated based on the flexible scintillators, which exhibits a detection limit of 63 nGyair s-1 and a spatial resolution of 27.9 lp mm-1.

Semiconducting Copolymers with Naphthalene Imide/Amide π-Conjugated Units: Synthesis, Crystallography, and Systematic Structure-Property-Mobility Correlations.

In a series of n-type semiconducting naphthalene tetracarboxydiimide (NDI)-dithiophene (T2) copolymers, structural and electronic properties trends are systematically evaluated as the number of NDI carbonyl groups is reduced from 4 in NDI to 3 in NBL (1-amino-4,5-8-naphthalene-tricarboxylic acid-1,8-lactam-4,5-imide) to 2 in NBA (naphthalene-bis(4,8-diamino-1,5-dicarboxyl)-amide). As the NDI-T2 backbone torsional angle falls the LUMO energy rises. However, the thienyl attachment regiochemistry also plays an important role in less symmetric NBL and NBA. Electron mobility is greatest for N2200 (0.17 cm2  V-1 s-1 ) followed by PNBL-3,8-T2 and PNBA-2,6-T2 (0.11 cm2  V-1 s-1 ), 0.02 cm2  V-1 s-1 in PNBL-4,8-T2, and negligible in PNBA-3,7-T2. Charge transport reflects a delicate balance between electronic backbone communication (optimum for N2200 and PNBL-4,8-T2), backbone planarity (optimum for PNBA-2,6-T2 and PNBL-3,8-T2), LUMO energy (optimum for N2200), π-π stacking distance (optimum for PNBA-2,6-T2), and film crystallinity (optimum for PNBA-2,6-T2 and N2200). These results offer generalizable insight into semiconducting copolymer design.

Symmetrically Fluorinated Benzo[1,2-b:4,5-b']dithiophene-Cored Donor for High-Performance All-Small-Molecule Organic Solar Cells with Improved Active Layer Morphology and Crystallinity.

Side-chain engineering is an efficient molecular design strategy for morphology optimization and performance improvement of organic solar cells (OSCs). Herein, a novel small-molecule donor C-2F, which owns a benzo[1,2-b:4,5-b']dithiophene (BDT) central unit with a symmetrically difluorinated benzene ring as a conjugated side chain, has been synthesized. The conjugated side chain possesses both the symmetry and halogenation effect in novel small molecular donor material. The photovoltaic devices were fabricated with N3 as an acceptor. C-2F:N3 based devices achieved an outstanding power conversion efficiency of 14.64% with a Jsc of 24.87 mA/cm2, a Voc of 0.85 V, and an FF of 69.33%. Then, we investigated the basic material properties, photovoltaic mechanism, and active layer morphology, and the results show that this molecular design strategy of the symmetrically difluorinated moiety as the conjugated side chain provides an effective method for fine-tuning the molecular stacking pattern and active layer phase separation morphology, to improve the all-small-molecule (ASM) OSCs' performances.