An Ortho-Bisalkyloxylated Benzene-Based Fully Non-fused Electron Acceptor for Efficient Organic Photovoltaic Cells.

To develop the low-cost nonfullerene acceptors (NFAs), two fully non-fused NFAs (TBT-2 and TBT-6) with ortho-bis((2-ethylhexyl)oxy)benzene unit and different side chains onto thiophene-bridges are synthesized through highly efficient synthetic procedures. Both acceptors show good planarity, low optical gaps (≈1.51 eV), and deep highest occupied molecular orbital levels (≤-5.77 eV). More importantly, the single-crystal structure of TBT-2 shows compact molecular arrangement due to the existence of intramolecular interactions between adjacent aromatic units and strong π-π stacking between intermolecular terminal groups. When the two acceptors are fabricated organic photovoltaic (OPV) cells by combining with a wide optical gap polymer donor, the TBT-6 with strong crystallization forms large domain sizes in bulk heterojunction (BHJ) blend. As a result, the TBT-6-based OPV cell shows a low power conversion efficiency (PCE) of 9.53%. In contrast, the TBT-2 with proper crystallization facilitates morphological optimization in the BHJ blend. Consequently, the TBT-2-based OPV cell gives an outstanding PCE of 13.25%, which is one of the best values among OPV cells with similar optical gaps. Overall, this work provides a practical molecular design strategy for developing high-performance and low-cost electron acceptors.

Morphology Control for Efficient Nonfused Acceptor-Based Organic Photovoltaic Cells.

Non-fused electron acceptors have huge advantages in fabricating low-cost organic photovoltaic (OPV) cells. However, morphology control is a challenge as non-fused C─C single bonds bring more molecular conformations. Here, by selecting two typical polymer donors, PBDB-TF and PBQx-TF, the blend morphologies and its impacts on the power conversion efficiencies (PCEs) of non-fused acceptor-based OPV cells are studied. A selenium-containing non-fused acceptor named ASe-5 is designed. The results suggest that PBQx-TF has a lower miscibility with ASe-5 when compared with PBDB-TF. Additionally, the polymer networks may form earlier in the PBQx-TF:ASe-5 blend film due to stronger preaggregation performance, leading to a more obvious phase separation. The PBQx-TF:ASe-5 blend film shows faster charge transfer and suppressed charge recombination. As a result, the PBQx-TF:ASe-5-based device records a good PCE of 14.7% with a higher fill factor (FF) of 0.744, while the PBDB-TF:ASe-5-based device only obtains a moderate PCE of 12.3% with a relatively low FF of 0.662. The work demonstrates that the selection of donors plays a crucial role in controlling the blend morphology and thus improving the PCEs of non-fused acceptor-based OPV cells.

RPBP: Deep Retrosynthesis Reaction Prediction Based on Byproducts.

Retrosynthesis prediction is crucial in organic synthesis and drug discovery, aiding chemists in designing efficient synthetic routes for target molecules. Data-driven deep retrosynthesis prediction has gained importance due to new algorithms and enhanced computing power. Although existing models show certain predictive power on the USPTO-50K benchmark data set, no one considers the effects of byproducts during the prediction process, which may be due to the lack of byproduct information in the benchmark data set. Here, we propose a novel two-stage retrosynthesis reaction prediction framework based on byproducts called RPBP. First, RPBP predicts the byproduct involved in the reaction based on the product molecule. Then, it handles an end-to-end prediction problem based on the prediction of reactants by product and byproduct. Unlike other methods that first identify the potential reaction center and then predict reactant molecules, RPBP considers additional information from byproducts, such as reaction reagents, conditions, and sites. Interestingly, adding byproducts reduces model learning complexity in natural language processing (NLP). Our RPBP model achieves 54.7% and 66.6% top-1 retrosynthesis prediction accuracy when the reaction class is unknown and known, respectively. It outperforms existing methods for known-class reactions, thanks to the rich chemical information in byproducts. The prediction of four kinase drugs from the literature demonstrates the model's practicality and potential to accelerate drug discovery.

A Wide Bandgap Acceptor with Large Dielectric Constant and High Electrostatic Potential Values for Efficient Organic Photovoltaic Cells.

Low-bandgap materials have achieved rapid development and promoted the enhancement of power conversion efficiencies (PCEs) of organic photovoltaic (OPV) cells. However, the design of wide-bandgap non-fullerene acceptors (WBG-NFAs), required by indoor applications and tandem cells, has been lagging far behind the development of OPV technologies. Here, we designed and synthesized two NFAs named ITCC-Cl and TIDC-Cl by finely optimizing ITCC. In contrast with ITCC and ITCC-Cl, TIDC-Cl can maintain a wider bandgap and a higher electrostatic potential simultaneously. When blending with the donor PB2, the highest dielectric constant is also obtained in TIDC-Cl-based films, enabling efficient charge generation. Therefore, the PB2:TIDC-Cl-based cell possessed a high PCE of 13.8% with an excellent fill factor (FF) of 78.2% under the air mass 1.5G (AM 1.5G) condition. Furthermore, an exciting PCE of 27.1% can be accomplished in the PB2:TIDC-Cl system under the illumination of 500 lux (2700 K light-emitting diode). Combined with the theoretical simulation, the tandem OPV cell based on TIDC-Cl was fabricated and exhibited an excellent PCE of 20.0%.

Large Steric Hindrance Enhanced Molecular Planarity for Low-Cost Non-Fused Electron Acceptors.

Designing efficient non-fused ring electron acceptors is of great importance in decreasing the material cost of organic photovoltaic cells (OPVs). It is a challenge to construct a planar molecular skeleton in non-fused molecules as there are many torsions between adjacent units. Here, we design two non-fused electron acceptors based on bithieno[3,2-b]thiophene units as core structures and study the impact of steric hindrance of substituents on molecular planarity. We use 2,4,6-triisopropylphenyl and 4-hexylphenyl groups to prepare ATTP-1 and ATTP-2, respectively. Our results suggest that the enhanced steric hindrance is beneficial for obtaining a more planar molecular configuration, which significantly increases the optical absorption and charge transport properties. The power conversion efficiency (PCE) of PBDB-TF:ATTP-1 combination (11.3%) is superior to that of PBDB-TF:ATTP-2 combination (3.7%). In addition, an impressive PCE of 10.7% is recorded in ATTP-1-based devices when a low-cost polythiophene donor PDCBT is used, which is an outstanding value in OPVs fabricated by non-fused donor/acceptor combinations. Our work demonstrates that modulation of the steric hindrance effect is of great significance to control the molecular planarity and thus obtain excellent photovoltaic performance of low-cost non-fused electron acceptors.

Trans-Reflective Structural Color Filters Assisting Multifunctional-Integrated Semitransparent Photovoltaic Window.

Multifunction-integrated semitransparent organic photovoltaic cells (STOPVs), with high power generation, colorful transmittance/reflectance, excellent ultraviolet (UV) protection, and thermal insulation, are fully in line with the concept of architectural aesthetics and photoprotection characteristics for building-integrated photovoltaic-window. For the indelible rainbow color photovoltaic window, one crucial issue is to realize the integration of these photons- and photoelectric-related multifunction. Herein, dynamic transmissive and reflective structural color controllable filters, with asymmetrical metal-insulator-metal (MIM) configurations (20 nm-Ag-HATCN-30 nm-Ag) through machine learning, are deliberately designed for colorful STOPV devices. This endows the resultant integrated devices with ≈5% enhanced power conversion efficiency (PCE) than the bare-STOPVs, gifted UV (300-400 nm) blocking rates as high as 93.5, 94.1, 90.2, and 94.5%, as well as a superior infrared radiation (IR) (700-1400 nm) rejection approaching 100% for transparent purple-, blue-, green- and red-STOPV cells, respectively. Most importantly, benefiting from the photonic recycling effect beyond microcavity resonance wavelength, a reported quantum utilization efficiency (QUE) as high as 80%, is first presented for the transparent-green-STOPVs with an ultra-narrow bandgap of 1.2 eV. These asymmetrical Febry-Pérot transmissive and reflective structural color filters can also be extended to silicon- and perovskite-based optoelectric devices and make it possible to integrate additional target optical functions for multi-purpose optoelectric devices.

Design of a Fully Non-Fused Bulk Heterojunction toward Efficient and Low-Cost Organic Photovoltaics.

To modulate the miscibility between donor and acceptor materials both possessing fully non-fused ring structures, a series of electron acceptors (A4T-16, A4T-31 and A4T-32) with different polar functional substituents were synthesized and investigated. The three acceptors show good planarity, high conformational stability, complementary absorption and energy levels with the non-fused polymer donor (PTVT-BT). Among them, A4T-32 possesses the strongest polar functional group and shows the highest surface energy, which facilitates morphological modulation in the bulk heterojunction (BHJ) blend. Benefiting from the proper morphology control method, an impressive power conversion efficiency (PCE) of approaching 16.0 % and a superior fill factor over 0.795 are achieved in the PTVT-BT : A4T-32-based organic photovoltaic cells with superior photoactive materials price advantage, which represent the highest value for the cells based on the non-fused blend films. Notably, this cell maintains ≈84 % of its initial PCE after nearly 2000 h under the continuous simulated 1-sun-illumination. In addition, the flexible PTVT-BT : A4T-32-based cells were fabricated and delivered a decent PCE of 14.6 %. This work provides an effective molecular design strategy for the non-fused non-fullerene acceptors (NFAs) from the aspect of bulk morphology control in fully non-fused BHJ layers, which is crucial for their practical applications.

High-Efficiency and Mechanically Robust All-Polymer Organic Photovoltaic Cells Enabled by Optimized Fibril Network Morphology.

All-polymer organic photovoltaic (OPV) cells possessing high photovoltaic performance and mechanical robustness are promising candidates for flexible wearable devices. However, developing photoactive materials with good mechanical properties and photovoltaic performance so far remains challenging. In this work, a polymer donor PBDB-TF with a high weight-average molecular weight (Mw ) is introduced to enable highly efficient all-polymer OPV cells featuring excellent mechanical reliability. By incorporating the high-Mw PBDB-TF as a third component into the PBQx-TF:PY-IT blend, the bulk heterojunction morphology is finely tuned with a more compact π-π stacking distance, affording efficient pathways for charge transport as well as mechanical stress dissipation. Hence, all-polymer OPV cells based on the ternary blend film demonstrate a maximum power conversion efficiency (PCE) of 18.2% with an outstanding fill factor of 0.796. The flexible OPV cell delivers a decent PCE of 16.5% with high mechanical stability. These results present a promising strategy to address the mechanical properties and boost the photovoltaic performance of all-polymer OPV cells.

A Medium-Bandgap Nonfullerene Acceptor Enabling Organic Photovoltaic Cells with 30% Efficiency under Indoor Artificial Light.

The correlation between molecular structure and photovoltaic performance is lagging for constructing high-performance indoor organic photovoltaic (OPV) cells. Herein, this relationship is investigated in depth by employing two medium-bandgap nonfullerene acceptors (NFAs). The newly synthesized NFA of FTCCBr exhibits a similar bandgap and molecular energy level, but a much stronger dipole moment and larger average electrostatic potential (ESP) compared with ITCC. After blending with the polymer donor PB2, the PB2:ITCC and PB2:FTCCBr blends exhibit favorable bulk-heterojunction morphologies and the same driving force, but the PB2:FTCCBr blend exhibits a large ESP difference. In OPV cells, the PB2:ITCC-based device produces a power conversion efficiency (PCE) of 11.0%, whereas the PB2:FTCCBr-based device gives an excellent PCE of 14.8% with an open-circuit voltage (VOC ) of 1.05 V, which is the highest value among OPV cells with VOC values above 1.0 V. When both acceptor-based devices work under a 1000 lux of 3000 K light-emitting diode, the PB2:ITCC-based 1 cm2 device yields a good PCE of 25.4%; in contrast, the PB2:FTCCBr-based 1 cm2 device outputs a record PCE of 30.2%. These results suggest that a large ESP offset in photovoltaic materials is important for achieving high-performance OPV cells.

Recent Advances in Single-Junction Organic Solar Cells.

Single-junction organic solar cells (OSCs) have made significant progress in recent years. Innovations in material design and device optimization have improved the power conversion efficiencies to over 19 %. In this Minireview, based on recent advances, we discuss molecular design strategies to tune the absorption spectrum, energy level, and intermolecular aggregation as well as highlight the role of molecular electrostatic potential in decreasing energy loss. Then, we introduce the latest progress in four types of OSCs composed of different donor:acceptor combinations: polymer donor:small-molecule acceptor, all-polymer, all-small-molecule, and small-molecule donor:polymer acceptor. Finally, the challenges of OSCs in practical applications, including material cost, stability, and multi-function integration, are discussed.

A New Polymer Donor Enables Binary All-Polymer Organic Photovoltaic Cells with 18% Efficiency and Excellent Mechanical Robustness.

The development of polymerized small-molecule acceptors has boosted the power conversion efficiencies (PCEs) of all-polymer organic photovoltaic (OPV) cells to 17%. However, the polymer donors suitable for all-polymer OPV cells are still lacking, restricting the further improvement of their PCEs. Herein, a new polymer donor named PQM-Cl is designed and its photovoltaic performance is explored. The negative electrostatic potential and low average local ionization energy distribution of the PQM-Cl surface enable efficient charge generation and transfer process. When blending with a well-used polymer acceptor, PY-IT, the PQM-Cl-based devices deliver an impressive PCE of 18.0% with a superior fill factor of 80.7%, both of which are the highest values for all-polymer OPV cells. The relevant measurements demonstrate that PQM-Cl-based films possess excellent mechanical and flexible properties. As such, PQM-Cl-based flexible photovoltaic cells are fabricated and an excellent PCE of 16.5% with high mechanical stability is displayed. These results demonstrate that PQM-Cl is a potential candidate for all-polymer OPV cells and provide insights into the design of polymer donors for high-efficient all-polymer OPV cells.

Design of ultra-high luminescent polymers for organic photovoltaic cells with low energy loss.

Here, new polymers named PBTT-Cn (n = 3, 4, or 5) have been designed based on carboxylate-functionalized thieno[3,2-b]thiophene units. The electroluminescence external quantum efficiencies (EQEEL) of pristine PBTT-C4 and C5 films are over 1 × 10-2, which are among the highest results for OPV materials. Through combination with BTP-eC9, the PBTT-C4-based film showed a high EQEEL of 6 × 10-4 and the Vnon-radloss is 0.19 eV. As a result, a high open-circuit voltage of 0.89 V and a satisfactory PCE of 15% were recorded in the PBTT-C4-based OPV cells.

18.5% Efficiency Organic Solar Cells with a Hybrid Planar/Bulk Heterojunction.

The donor:acceptor heterojunction has proved as the most successful approach to split strongly bound excitons in organic solar cells (OSCs). Establishing an ideal architecture with selective carrier transport and suppressed recombination is of great importance to improve the photovoltaic efficiency while remains a challenge. Herein, via tailoring a hybrid planar/bulk structure, highly efficient OSCs with reduced energy losses (Eloss s) are fabricated. A p-type benzodithiophene-thiophene alternating polymer and an n-type naphthalene imide are inserted on both sides of a mixed donor:acceptor active layer to construct the hybrid heterojunction, respectively. The tailored structure with the donor near the anode and the acceptor near the cathode is beneficial for obtaining enhanced charge transport, extraction, and suppressed charge recombination. As a result, the photovoltaic characterizations suggest a reduced nonradiative Eloss by 25 meV, and the best OSC records a high efficiency of 18.5% (certified as 18.2%). This study highlights that precisely regulating the structure of donor:acceptor heterojunction has the potential to further improve the efficiencies of OSCs.

Single-Junction Organic Photovoltaic Cell with 19% Efficiency.

Improving power conversion efficiency (PCE) is important for broadening the applications of organic photovoltaic (OPV) cells. Here, a maximum PCE of 19.0% (certified value of 18.7%) is achieved in single-junction OPV cells by combining material design with a ternary blending strategy. An active layer comprising a new wide-bandgap polymer donor named PBQx-TF and a new low-bandgap non-fullerene acceptor (NFA) named eC9-2Cl is rationally designed. With optimized light utilization, the resulting binary cell exhibits a good PCE of 17.7%. An NFA F-BTA3 is then added to the active layer as a third component to simultaneously improve the photovoltaic parameters. The improved light unitization, cascaded energy level alignment, and enhanced intermolecular packing result in open-circuit voltage of 0.879 V, short-circuit current density of 26.7 mA cm-2 , and fill factor of 0.809. This study demonstrates that further improvement of PCEs of high-performance OPV cells requires fine tuning of the electronic structures and morphologies of the active layers.

Simultaneous Improvement of Efficiency and Stability of Organic Photovoltaic Cells by using a Cross-Linkable Fullerene Derivative.

Improving power conversion efficiencies (PCEs) and stability are two main tasks for organic photovoltaic (OPV) cells. In the past few years, although the PCE of the OPV cells has been considerably improved, the research on device stability is limited. Herein, a cross-linkable material, cross-linked [6,6]-phenyl-C61-butyric styryl dendron ester (c-PCBSD), is applied as an interfacial modification layer on the surface of zinc oxide and as the third component into the PBDB-TF:Y6-based OPV cells to enhance photovoltaic performance and long-term stability. The PCE of the OPV cells that underwent the two-step modification increased from 15.1 to 16.1%. In particular, such OPV cells exhibited much better stability under both thermal and air conditions because of the decreased number of interfacial defects and stable interfacial and active layer morphologies. The results demonstrated that the introduction of a cross-linkable fullerene derivative into the interfacial and active layers is a feasible method to improve the PCE and stability of OPV cells.

Elucidating End-Group Modifications of Carbazole-Based Nonfullerene Acceptors in Indoor Applications for Achieving a PCE of over 20.

In this work, two DTSiC-based nonfullerene acceptors (NFAs), (2,2'-((2Z,2'Z)-((12-(heptadecan-9-yl)-4,4,7,7-tetraoctyl-7,12-dihydro-4H-thieno[2',3':4,5]silolo[3,2-b]thieno[2',3':4,5]silolo[2,3-h]carbazole-2,9-diyl)bis(methaneylylidene))bis(3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile) (DTSiC-IC) and (2,2'-((5Z,5'Z)-((12-(heptadecan-9-yl)-4,4,7,7-tetraoctyl-7,12-dihydro-4H-thieno[2',3':4,5]silolo[3,2-b]thieno[2',3':4,5]silolo[2,3-h]carbazole-2,9-diyl)bis(methaneylylidene))bis(6-oxo-5,6-dihydro-4H-cyclopenta[c]thiophene-5,4-diylidene))dimalononitrile) (DTSiC-TC), are designed with various end groups (IC and TC). To explore the effect of end-group modifications, photovoltaic performance under AM 1.5G and indoor conditions are comprehensively studied. Compared with DTSiC-IC, DTSiC-TC manifests red-shifted and stronger absorption, downshifted lowest unoccupied molecular orbital (LUMO), and pronounced face-on packing characteristics. As we envisaged, the PM7:DTSiC-TC-based devices outperform the PM7:DTSiC-IC-based devices in both AM 1.5G and indoor (light-emitting diode (LED) 3000 K 1000 lux) conditions with overall higher JSC, FF, and power conversion efficiency (PCE). Furthermore, the PM7:DTSiC-TC-based devices achieve an outstanding PCE of 20.73% with a VOC of 0.87 V, a JSC of 0.095 mA/cm2, and an FF of 70.86%.

Impact of Electrostatic Interaction on Bulk Morphology in Efficient Donor-Acceptor Photovoltaic Blends.

Bulk heterojunctions comprising mixed donor (D) and acceptor (A) materials have proven to be the most efficient device structures for organic photovoltaic (OPV) cells. The bulk morphology of such cells plays a key role in charge generation, recombination, and transport, thus determining the device performance. Although numerous studies have discussed the morphology-performance relationship of these cells, the method of designing OPV materials with the desired morphology remains unclear. Herein, guided by molecular electrostatic potential distributions, we have established a connection between the chemical structure and bulk morphology. We show that the molecular orientation at the D-A interface and the domain purity in the blend can be effectively modulated by modifying the functional groups. Enhancing the D-A interaction is beneficial for charge generation. However, the resulting low domain purity and increased charge transfer ratio in its hybridization with the local excitation states lead to severe charge recombination. Fine-tuning the bulk morphology can give balanced charge generation and recombination, which is crucial for further boosting the efficiency of the OPV cells.

A New Conjugated Polymer that Enables the Integration of Photovoltaic and Light-Emitting Functions in One Device.

Exploring the intriguing bifunctional nature of organic semiconductors and investigating the feasibility of fabricating bifunctional devices are of great significance in realizing various applications with one device. Here, the design of a new wide-bandgap polymer named PBQx-TCl (optical bandgap of 2.05 eV) is reported, and its applications in photovoltaic and light-emitting devices are studied. By fabricating devices with nonfullerene acceptors BTA3 and BTP-eC9, it is shown that the devices exhibit a high power conversion efficiency (PCE) of 18.0% under air mass 1.5G illumination conditions and an outstanding PCE of 28.5% for a 1 cm2 device and 26.0% for a 10 cm2 device under illumination from a 1000 lux light-emitting diode. In addition, the PBQx-TCl:BTA3-based device also demonstrates a moderate organic light-emitting diode performance with an electroluminescence external quantum efficiency approaching 0.2% and a broad emission range of 630-1000 nm. These results suggest that the polymer PBQx-TCl-based devices exhibit outstanding photovoltaic performance and potential light-emitting functions.

Synergistic effect, kinetic and thermodynamics parameters analyses of co-gasification of municipal solid waste and bituminous coal with CO2.

Co-gasification of municipal solid waste (MSW) with bituminous coal (BC) is an attractive alternative to realize the harmless disposal and energy harvesting of MSW. In this work, co-gasification characteristics and synergistic interaction of MSW and BC with CO2 atmosphere are studied by thermogravimetric method, including analyses of thermodynamics, kinetic parameters and reaction mechanism function. Results indicate that MSW gasification process can be divided into four main stages, and that of BC has only three main stages. Gasification temperature of coal char is much higher than that of MSW char, and addition of MSW can significantly improve the gasification reactivity of BC. Besides, a significant synergistic effect is observed for all the blends in char gasification stage. Based on three kinetic methods of Flynn-Wall-Ozawa (Xie et al., 2018), Starink (Zhang et al., 2019a) and Friedman, the minimum average activation energy Ea (184.13 kJ/mol) is obtained when the blend ratio of BC is 40% which might be an optimal option for co-gasification of the blends. The average values of the enthalpy, the Gibbs function and the entropy changes for sample 60MSW40BC are 176.82 kJ/mol, 257.89 kJ/mol and -89.16 J/mol·K, respectively. According to the Malek method, F6, A1 and D7 models are probably more suitable to describe three main stages of sample 60MSW40BC CO2 co-gasification.

Toward Visibly Transparent Organic Photovoltaic Cells Based on a Near-Infrared Harvesting Bulk Heterojunction Blend.

Wavelength-selective harvesting by organic solar cells (OSCs) has attracted significant research attention due to the unique potential of these materials for smart photovoltaic window applications. Here, a visibly transparent OSC is demonstrated by utilizing both near-infrared (NIR)-absorbing polymer donor and nonfullerene acceptor (NFA) materials with narrow optical band gaps of less than 1.4 eV. Despite the substantial overlap in absorption spectra between the donor and acceptor, sufficient lowest unoccupied molecular orbital (LUMO) and highest occupied molecule orbital (HOMO) energy offsets for efficient charge separation with concurrent very low voltage losses yield a power conversion efficiency (PCE) of 9.13%. Moreover, with the introduction of an ultrathin Ag film (8 nm) as a transparent top electrode, semitransparent OSCs exhibit an excellent dual-side photovoltaic performance of 5.7 and 3.9% under bottom and top illumination, respectively, with high transmittance reaching 60% at wavelengths from 400 to 600 nm. This approach is expected to provide a new perspective in developing the highly efficient and transparent OSCs.