Small Molecule Acceptors Research Articles

Asymmetric Alkyl Chain Engineering for Efficient and Eco-Friendly Organic Photovoltaic Cells.

Recent advancements in organic photovoltaic (OPV) cells have resulted in power conversion efficiencies (PCEs) surpassing 20%. However, the use of halogen solvents in the fabrication of OPV cells raises concerns due to their potential environmental and health impacts. In this work, a novel non-fullerene small molecule acceptor BO-AM-4F, featuring an asymmetric alkyl chain design that includes a 2-butyloctyl and a unique 6-(hexylamino)-6-oxohexyl chain is synthesized. This design significantly improves molecular packing, crystallinity, and electrostatic potential distribution compared to the controlled acceptor DBO-4F, which possesses symmetric 2-butyloctyl chains. When combined with the polymer donor PBDB-TF and processed using the non-halogen solvent o-xylene, the BO-AM-4F-based OPV cell achieves an impressive PCE of 18.0%, surpassing the 16.6% PCE observed in the PBDB-TF:DBO-4F device. Furthermore, the PBDB-TF:BO-AM-4F system demonstrates enhanced photostability and thermal stability compared to its DBO-4F counterpart. These findings emphasize asymmetric alkyl chain engineering as an effective strategy for developing high-performance, environmentally friendly OPV materials. This represents a significant step towards sustainable OPV technology.

Efficient All‐Polymer Solar Cells Enabled by a Novel Medium Bandgap Guest Acceptor

Comprehensive SummaryNear‐infrared (NIR)‐absorbing polymerized small molecule acceptors (PSMAs) based on a Y‐series backbone (such as PY‐IT) have been widely developed to fabricate efficient all‐polymer solar cells (all‐PSCs). However, medium‐bandgap PSMAs are often overlooked, while they as the third component can be expected to boost power conversion efficiencies (PCEs) of all‐PSCs, mainly due to their up‐shifted lowest unoccupied molecular orbital (LUMO) energy level, complimentary absorption, and diverse intermolecular interaction compared to the NIR‐absorbing host acceptor. Herein, an IDIC‐series medium‐bandgap PSMA (P‐ITTC) is developed and introduced as the third component into D18/PY‐IT host, which can not only form complementary absorption and cascade energy level, but also finely optimize active layer morphology. Therefore, compared to the D18/PY‐IT based parental all‐PSCs, the ternary all‐PSCs based on D18/PY‐IT:P‐ITTC obtain an increased exciton dissociation, charge transport, carrier lifetime, as well as suppressed charge recombination and energy loss. As a result, the ternary all‐PSCs achieve a high PCE of 17.64% with a photovoltage of 0.96 V, both of which are among the top values in layer‐by‐layer typed all‐PSCs. This work provides a method for the design and selection of the medium‐bandgap third component to fabricate efficient all‐PSCs.

Exciton Diffusion to Low Energy Sites of the Acceptor Drives Charge Photogeneration in D18:Y6 Solar Cells.

We have investigated charge generation pathways in efficient organic photovoltaic blends of the polymer donor D18 and the small-molecule acceptor Y6 using transient absorption and time-resolved fluorescence spectroscopies. We find that energy transfer from D18 to Y6 outcompetes electron transfer and is followed by exciton diffusion from regions of the disordered Y6 phase to Y6 aggregates before hole transfer to D18. Aggregation of Y6 molecules increases their ionization energy by ∼0.3 eV and provides a driving force for hole transfer from Y6 excitons and spontaneously generated charge pairs to D18. We observed ultrafast depolarization of the Y6 ground-state bleaching in <200 fs, which indicates delocalization of primary excitons in Y6 aggregates. This delocalization can explain the spontaneous generation of charge pairs in neat Y6 films and Y6-rich blends. Our results show that subtle aggregation control of the low-energy absorber can be used for balancing photocurrent generation with low voltage loss in photovoltaic blends.

Designing a Highly Crystalline Polymer Donor with Alkylsilyl and Fluorine Substitution to Achieve Efficient Ternary Organic Solar Cells.

Adopting a ternary strategy is an effective approach to enhance the power conversion efficiency (PCE) in organic solar cells (OSCs). Previous research on highly efficient ternary systems has predominantly focused on those based on highly crystalline dual small molecule acceptors. However, limited attention has been given to ternary systems utilizing dual polymer donors. Herein, by incorporating the fluorine and alkylsilyl substitution, a new polymer donor named PX1 is developed, which demonstrates strong crystallinity and excellent miscibility with polymer PM6. Moreover, PX1 broadens and enhances the absorption properties of the PM6:L8-BO blends, and its molecular orbital energy level is situated between those of PM6 and L8-BO, highlighting its suitability as a third component. Introducing 20% PX1 into the PM6:L8-BO system resulted in a high PCE of 18.82%. PX1 effectively suppresses charge recombination and reduces energy losses, while also serving as a morphology modulator that enhances the crystallization and improves the molecular packing order of the active layer by shortening the π-π stacking distance and extending crystalline coherence length. These factors collectively contribute to the performance improvements in ternary devices. This study demonstrates that employing a dual polymer donor strategy is a promising approach for achieving high-performance ternary OSCs.

Medium bandgap A-DA’D-A type small molecule acceptors prepared by synergetic modification strategy for efficient indoor organic photovoltaic devices

Medium bandgap A-DA’D-A type small molecule acceptors prepared by synergetic modification strategy for efficient indoor organic photovoltaic devices

Numerical investigation of graphene derivatives as HTL in PBDB-T:NCBDT bulk heterojunction organic solar cell

The damaging effects of the most widely used PEDOT:PSS have led researchers to search for an alternative hole transport layer (HTL) in non-fullerene acceptor (NFA) based bulk heterojunction organic solar cells (BHJOSC’s). This work highlights the numerical simulation study of possible new approach of utilizing graphene, graphene oxide (GO), reduced graphene oxide (rGO), and p type doped graphene (p-graphene), as an alternative to PEDOT:PSS in non-fullerene acceptor based bulk heterojunction organic solar cell (NFABHJOSC) with PBDB-T as donor and NCBDT as acceptor using SCAPS1D. NCBDT is an emerging small-molecule non-fullerene acceptor (SM-NFA) whose bandgap can be tuned and reduced, making it a better option as an acceptor. Validation of the software is done by matching simulation results with experimental results. Diverse electron transport layers (ETL’s), including PDINO, ZnO, IGZO, TiO2, TiO2:gr (20%) composite, and TiO2:gr (10%) composite, are introduced, and device performance of various configurations is analysed. Optimization of the best device configuration ITO (4.8 eV)/rGO/PBDB-T:NCBDT/PDINO/Al gave an improved efficiency of 17.47%, fill factor (FF) of 77.45%, short circuit current density (Jsc) of 25.407 mA/cm2, and an open circuit voltage (Voc) of 0.8878 V.

Impact of Alkoxy Side Chains on the Quinoxaline-Based Electron Acceptors for Efficient Organic Solar Cells.

In this work, three alkoxy-substituted quinoxaline core-based small-molecule acceptors (BQO-F, BQDO-F, and BQDO-Cl) are developed to elucidate the impact of ethoxy substituents on the physicochemical and photoelectric properties. Comparative analysis reveals that dialkoxy-substituted BQDO-F has a more planar molecular skeleton, a red-shifted absorption spectrum, upshifted energy levels, stronger crystallinity, and reduced energetic disorder compared to the monoalkoxy-substituted BQO-F. Although the replacement of fluorine atoms with chlorine atoms on the end-capped units of BQDO-F leads to a bathochromically shifted absorption spectrum, the resulting molecule BQDO-Cl shows worse π-π packing order compared to BQDO-F. Benefiting from the more favorable active layer morphology and improved carrier dynamics, the PBDB-T:BQDO-F-based organic solar cell achieves a much higher power conversion efficiency (PCE) of 16.41% compared to that of 14.48% obtained in the BQO-F-based device. In comparison with the BQDO-F-based device, the higher voltage loss of the BQDO-Cl-based device results in a lower PCE of 15.89%. The results clarify the effects of ethoxy substituents and end-capped substitutions of quinoxaline core-based small-molecule acceptors on efficient organic solar cells.

Inner Side Chain Modification of Small Molecule Acceptors Enables Lower Energy Loss and High Efficiency of Organic Solar Cells Processed with Non-halogenated Solvents.

Organic solar cells (OSCs) processed with non-halogenated solvents usually suffer from excessive self-aggregation of small molecule acceptors (SMAs), severe phase separation and higher energy loss (Eloss), leading to reduced open-circuit voltage (Voc) and power conversion efficiency (PCE). Regulating the intermolecular interaction to disperse the aggregation and further improve the molecular packing order of SMAs would be an effective strategy to solve this problem. Here, we designed and synthesized two SMAs L8-PhF and L8-PhMe by introducing different substituents (fluorine for L8-PhF and methyl for L8-PhMe) on the phenyl end group of the inner side chains of L8-Ph, and investigated the effect of the substituents on the intermolecular interaction of SMAs, Eloss and performance of OSCs processed with non-halogenated solvents. Through single crystal analysis and theoretical calculations, it is found that compared with L8-PhF, which possesses strong and abundant intermolecular interactions but downgraded molecular packing order, L8-PhMe with the methyl substituent possesses more effective non-covalent interactions, which improves the tightness and order of molecular packing. When blending the SMAs with polymer donor PM6, the differences in intermolecular interactions of the SMAs influenced the film formation process and phase separation of the blend films. The L8-PhMe based blend film exhibits shorten film formation and more homogeneous phase separation than those of the L8-PhF and L8-Ph based ones. Especially, the OSCs based on L8-PhMe show reduced non-radiative energy loss and enhanced Voc than the devices based on the other two SMAs. Consequently, the L8-PhMe based device processed with o-xylene (o-XY) and using 2PACz as the hole transport layer (HTL) shows an outstanding PCE of 19.27 %. This study highlights that the Eloss of OSCs processed with non-halogenated solvents could be decreased through regulating the intermolecular interactions of SMAs by inner side chain modification, and also emphasize the importance of effectivity rather than intensity of non-covalent interactions introduced in SMAs on the molecular packing, morphology and PCE of OSCs.

3-Methylthiophene: A Sustainable Solvent for High-Performance Organic Solar Cells.

The use of harmful halogenated or aromatic solvents such as chloroform (CF), chlorobenzene (CB), and o-xylene (o-XY) is one of the greatest barriers to the industrial-scale manufacturing of high-performance organic solar cells (OSCs). Therefore, it is necessary to eliminate the effects of these solvents to ensure practical feasibility of OSCs. We found that the anthracene-terminated polymer donor and small-molecule acceptor BO-4Cl had good solubility in 3-methylthiophene (3-MeT). There were no toxicity labels in the SDS and exposure control limits for 3-MeT. An overall power conversion efficiency of 16.87% was achieved by using 3-MeT as the solvent for solar cell fabrication, which was higher than that of the cells made from CF (16.18%) and o-XY (15.69%). The best OSC based on PM6:D18:L8-BO and fabricated with 3-MeT exhibited a high PCE of 18.13%, which is one of the highest values for cells fabricated from halogen-free solvents. These results indicate that 3-MeT is an eco-friendly and low-toxicity solvent for the sustainable fabrication of the OSC active layer.

Exploring the Impact of 1,8-Diioodoctane on the Photostability of Organic Photovoltaics.

Improving the photostability of the light-harvesting blend film in organic photovoltaics is crucial to achieving long-term operational lifetimes that are required for commercialization. However, understanding the degradation factors which drive instabilities is complex, with many variables such as film morphology, residual solvents, and acceptor or donor design all influencing how light and oxygen interact with the blend film. In this work, we show how blend films comprising a donor polymer (PBDB-T) and small molecule acceptor (PC71BM or ITIC) processed with solvent additive (DIO) yield very different film morphologies, device performance, and photostability. We show that DIO is retained approximately 10 times more effectively in ITIC based films compared to PC71BM. Unexpectedly, we see that while high volumes of DIO reduce photostability for encapsulated ITIC devices, when oxygen is introduced DIO can improve the lifetime of PBDB-T:ITIC based cells. Here, the addition of 3% DIO doubles the T 80 compared to ITIC based devices without DIO, suggesting that DIO-induced morphological changes interfere with or reduce photo-oxidative reactions.

Dimeric Small Molecule Acceptors via Terminal-End Connections: Effect of Flexible Linker Length on Photovoltaic Performance.

The dimerization of small molecule acceptors (SMAs) holds significant potential by combining the advantages of both SMAs and polymer acceptors in realizing high power conversion efficiency (PCE) and operational stability in organic solar cells (OSCs). However, advancements in the selection and innovation of dimeric linkers are still challenging in enhancing their performance. In this study, three new dimeric acceptors, namely DY-Ar-4, DY-Ar-5, and DY-Ar-6 are synthesized, by linking two Y-series SMA subunits via an "end-to-end" strategy using flexible spacers (octyl, decyl, and dodecyl, respectively). The influence of spacer lengths on device performance is systematically investigated. The results indicate that DY-Ar-5 exhibits more compact and ordered packing, leading to an optimal morphology. OSCs based on PM6: DY-Ar-5 achieves a maximum PCE of 15.76%, attributes to enhance and balance carrier mobility, and reduce carrier recombination. This dimerization strategy using suitable non-conjugated linking units provides a rational principle for designing high-performance non-fullerene acceptors.

Unveiling the Influence of Linkers on Conformations of Oligomeric Acceptors for High-Performance Polymer Solar Cells.

Conformational isomerism of organic photovoltaic materials has a profound impact on their molecular packing and therefore performance of polymer solar cells (PSCs). However, the conformations of oligomeric acceptors (OAs) are mostly predicted by simulations rather than experimental determinations. Herein, the stereochemical S-shaped structure of two dimeric-type acceptor molecules, V-DYIC and V-DYIC-4F, is first confirmed with different end groups (IC for V-DYIC and IC-2F for V-DYIC-4F), incorporating vinylene linkage for connecting the distinct state-of-the-art small molecule acceptor Y-segments. Through the synthetic control of fluorination sites adjacent to the vinyl-linker, S-shaped the conformation by NMR experiments is validated. Compared to the O-shaped dimer, S-shaped conformation results in enhanced lamellar order and reduced nonradiative recombination losses. The optimal acceptor, V-DYIC-4F, achieved a champion efficiency of 18.10% with the lowest energy loss of 0.556eV in its devices paired with PM6 due to their efficient carrier transport, and suppressed recombination compared to other devices, being attributed to the synergistic effect of conformation and end group fluorination. The insights gained in this work contribute valuable knowledge of both synthetic control and structural determination of OAs, providing strategic design guidelines for the future development of dimeric acceptors toward high-efficiency PSCs.

Polyfluoride Acceptor with Limited Molecular Diffusion Enables Efficient and Stable Ternary Organic Solar Cells.

Due to the slow diffusion of photovoltaic molecules, in particular, small-molecule acceptors (SMAs), under light and heating, the morphology of the active layer in organic solar cells (OSCs) prefers to deviate from the favorably metastable status, leading to the challenge of stability during long-term operation. Employing materials with a high glass transition temperature (Tg) as the third component to suppress molecular diffusion is an efficient method to achieve the balance of efficiency and stability of OSCs. Herein, a dimerized small-molecule acceptor denoted as F6D is synthesized by introducing a polyfluoride moiety as the linker to enhance the Tg. Benefitting from a rational molecular design, F6D not only exhibits a higher Tg, complementary absorption, and cascade energy levels with the host materials of the polymer donor PM6 and the SMA Y6 but also has excellent miscibility and multiple intermolecular interactions with Y6. As a result, a champion power conversion efficiency of 17.52% is achieved in the optimal PM6:Y6:F6D-based device. More importantly, the ternary device exhibits superior stability under continuous heating and lighting compared with the binary device.

Dimerized M‐series Acceptors with Low Diffusion Coefficients for Efficient and Stable Polymer Solar Cells

As the simplest oligomeric acceptors, dimerized acceptors (DAs) are easier to synthesize, and more importantly, they can retain good intermolecular interaction and photovoltaic properties of their parent small‐molecule acceptors (SMAs). Nevertheless, currently most efficient DAs are derived from banana‐shaped acceptors and they might suffer from inferior device stability with high diffusion coefficients. Herein, we design and synthesize two planar DAs (DMT‐FH and DMT‐HF) by bridging two linear‐shaped M‐series SMAs with a thiophene unit. The effects of fluorination position on the diffusion coefficients, power conversion efficiencies (PCEs) and stability of the DAs are systematically studied. Our results suggest that DMT‐HF with fluorination on the ending indanone groups shows enhanced intermolecular interactions, improved PCE and stability compared with the counterpart (DMT‐FH) with fluorination on the central indanone groups. Further optimization on the DMT‐HF‐based devices yields an outstanding PCE of 17.17%, which is the highest among all linear‐shaped SMA‐based DAs. Notably, with the low diffusion coefficient (3.36×10‐24 cm2 s‐1) of DMT‐HF, the resulting device retains over 93% of the initial PCE after 5000 h of continuous heating at 85 oC, suggesting its excellent thermal stability. The results highlight the importance of intermolecular interaction and fluorination for achieving efficient and stable polymer solar cells.

Dimerized M-Series Acceptors with Low Diffusion Coefficients for Efficient and Stable Polymer Solar Cells.

As the simplest oligomeric acceptors, dimerized acceptors (DAs) are easier to synthesize, and more importantly, they can retain good intermolecular interaction and photovoltaic properties of their parent small-molecule acceptors (SMAs). Nevertheless, currently most efficient DAs are derived from banana-shaped acceptors and they might suffer from inferior device stability with high diffusion coefficients. Herein, we design and synthesize two planar DAs (DMT-FH and DMT-HF) by bridging two linear-shaped M-series SMAs with a thiophene unit. The effects of fluorination position on the diffusion coefficients, power conversion efficiencies (PCEs) and stability of the DAs are systematically studied. Our results suggest that DMT-HF with fluorination on the ending indanone groups shows enhanced intermolecular interactions, improved PCE and stability compared with the counterpart (DMT-FH) with fluorination on the central indanone groups. Further optimization on the DMT-HF-based devices yields an outstanding PCE of 17.17 %, which is the highest among all linear-shaped SMA-based DAs. Notably, with the low diffusion coefficient (3.36×10-24 cm2 s-1) of DMT-HF, the resulting device retains over 93 % of the initial PCE after 5000 h of continuous heating at 85 °C, suggesting its excellent thermal stability. The results highlight the importance of intermolecular interaction and fluorination for achieving efficient and stable polymer solar cells.

Accelerating the discovery of acceptor materials for organic solar cells by deep learning

It is a time-consuming and costly process to develop affordable and high-performance organic photovoltaic materials. Computational methods are essential for accelerating the material discovery process by predicting power conversion efficiencies (PCE). In this study, we propose a deep learning-based framework (DeepAcceptor) to design and discover highly efficient small molecule acceptor materials. Specifically, an experimental dataset is constructed by collecting acceptor data from publications. Then, a deep learning-based model is customized to predict PCEs by applying graph representation learning to Bidirectional Encoder Representations from Transformers (BERT), with the atom, bond, and connection information in acceptor molecular structures as the input (abcBERT). The computational dataset derived from density functional theory (DFT) calculations and the experimental dataset from literature are used to pre-train and fine-tune the model, respectively. The abcBERT model outperforms other state-of-the-art models for the PCE prediction with MAE = 1.78 and R2 = 0.67 on the test set. A molecular generation and screening process is built to find new high-performance acceptors for PM6. Three discovered candidates are further validated by experiment, and the best PCE reaches 14.61%. The released user-friendly interface of DeepAcceptor greatly boosts the accessibility and efficiency of designing and discovering high-performance acceptors. Altogether, the DeepAcceptor framework with abcBERT is promising to predict the PCE and accelerate the discovery of high-performance acceptor materials.

Approaching 20% Efficiency in Ortho-Xylene Processed Organic Solar Cells by a Benzo[a]phenazine-Core-Based 3D Network Acceptor with Large Electronic Coupling and Long Exciton Diffusion Length.

High-performance organic solar cells often rely on halogen-containing solvents, which restrict the photovoltaic industry. Therefore, it is imperative to develop efficient organic photovoltaic materials compatible with halogen-free solvents. Herein, a series of benzo[a]phenazine (BP)-core-based small-molecule acceptors (SMAs) achieved through an isomerization chlorination strategy is presented, comprising unchlorinated NA1, 10-chlorine substituted NA2, 8-chlorine substituted NA3, and 7-chlorine substituted NA4. Theoretical simulations highlight NA3's superior orbit overlap length and tight molecular packing, attributed to interactions between the end group and BP unit. Furthermore, NA3 demonstrates dense 3D network structures and a record electronic coupling of 104.5 meV. These characteristics empower the ortho-xylene (o-XY) processed PM6:NA3 device with superior power conversion efficiency (PCE) of 18.94%, surpassing PM6:NA1 (15.34%), PM6:NA2 (7.18%), and PM6:NA4 (16.02%). Notably, the significantly lower PCE in the PM6:NA2 device is attributed to excessive self-aggregation characteristics of NA2 in o-XY. Importantly, the incorporation of D18-Cl into the PM6:NA3 binary blend enhances crystallographic ordering and increases the exciton diffusion length of the donor phase, resulting in a ternary device efficiency of 19.75% (certified as 19.39%). These findings underscore the significance of incorporating new electron-deficient units in the design of efficient SMAs tailored for environmentally benign solvent processing of OSCs.

Development of cross-linked donor polymers for polymer solar cells with improved efficiency and thermal stability

Due to low glass-transition temperature and high diffusion coefficient of small molecule acceptors (SMAs), the bi-continuous interpenetrating morphology of SMA-based polymer solar cells (PSCs) are metastable and therefore most SMA-based PSCs exhibit poor operational and thermal stability. Cross-linked donor polymers have been proposed because the cross-linked behavior can “freeze” the initial morphology and avoid its further evolution. In this work, two new cross-linked donor polymers P1 and P2 were designed for application in PSCs with a non-fullerene acceptor Y6, in which the photovoltaic performance and thermal stability of PSCs were significantly improved. The P1-based PSCs achieved a superior power conversion efficiency (PCE) of 17.29 % with a Jsc of 25.99 mA cm−2, a Voc of 0.860 V and a FF of 77.35 %, which surpassed 9 % for PM6-based PSCs (15.86 %). Furthermore, the P1-based PSCs exhibited better thermal stability with a 17 % efficiency loss under continuous 60 °C for 210 h due to the fixation of active layer morphology, while PM6-based PSCs suffered from a serve PCE reduction of over 26 %. These results demonstrate that cross-linked donor polymer has a great application prospect to improve the PCE and thermal stability of PSCs.

Machine learning assisted designing of Y-series small molecule acceptors: Library generation and property prediction

The designing of new small molecule acceptors (SMAs) for organic solar cells has been a prominent area of research for many decades. It is challenging to find unique materials due to expensive experimentation. Machine learning emerges as a promising tool for rapid and cost-effective prediction of properties. In the current study, electron affinity is predicted using machine learning models. Molecular descriptors are calculated for model training. Four machine learning models are used. A reasonably high predictive capability is obtained for random forest model (r-squared values of 0.92 and 0.82 for training and test set, respectively). Furthermore, the chemical database of small molecule acceptors is generated. Generated virtual space is anticipated by exploiting the t-distributed stochastic neighbor embedding (t-SNE) method. Structure Activity Landscape Index (SALI) analysis is conducted to examine how properties change with structural variations. A minimal change in electron affinity resulted from structural modifications. Additionally, clustering analysis is performed on selected small molecule acceptors for structural grouping of SMAs. Five SMAs with lowest synthetic accessibility (SA) score are selected for density functional theory (DFT) calculations. The introduced multiple dimensional framework has potential screened the materials in short-time and efficient way.

All‐Small‐Molecule Ternary Organic Solar Cell with 16.35% Efficiency Enabled by Chlorinated Terminal Units

In the last few years, there have been notable developments in organic solar cells using both small molecule donor and acceptor. It has been noted that adding halogens to the end groups of small molecules could enhance the film structure and, consequently, the performance of the devices. In this study, three novel small molecule donors are created. The molecules include a vinyl‐CPDT oligomer with three units, with end‐caps made up of indanedione groups and containing four H, four Cl, and four F substituents. The purpose of the study is to investigate how the halogen substituent affects the photovoltaic characteristics of binary devices made with the non‐fullerene acceptor (NFA) TOCR2 as the acceptor. Having the halogen in the device enhances its effectiveness, and FG5, which has 4‐Cl substituents in the end groups, shows the highest efficiency among all devices with a PCE of 14.39%. Incredibly, the ternary device that is created in normal atmospheric conditions with chloro‐substituted FG5 as the donor, TOCR2 as the acceptor, and the wide band gap NFA DICTF as the third element shows significantly improved efficiency, achieving PCE values of up to 16.35%.