High-Efficiency (16.93%) Pseudo-Planar Heterojunction Organic Solar Cells Enabled by Binary Additives Strategy

Acquiring precision adjustable morphology of the blend films to improve the efficiency of charge separation and collection is a constant goal of organic solar cells (OSCs). Here, the above problem is improved by synergistically combining the sequential deposition (SD) method and the additive general strategy. By adding one additive 1,10-decanediol (DDO) into PM6 and another 1-chloronaphthalene (CN) into Y6, the molecule orientation of PM6 and the crystallite texture of the Y6 all become order. During the SD processing, a vertical phase separation OSCs device is formed where the donor enrichment at the anode and acceptor enrichment at the cathode. In comparison, the SD OSCs device with only CN additive still displays the bulk-heterojunction morphology similar to PM6:Y6 blend film. The morphology with vertical phase distribution can not only inhibit charge recombination but also facilitate charge collection, finally enhancing the fill factor (FF) and photocurrent in binary additives SD-type OSCs. As a result, the binary additives SD-type OSCs with blend film PM6 + DDO/Y6 + CN exhibit a high FF of 77.45%, enabling a power conversion efficiency as high as 16.93%. This work reveals a simple but effective approach for boosting high-efficiency OSCs with ideal morphologies and demonstrates that the additive is a promising processing alternative.     

High‐Performance Pseudoplanar Heterojunction Ternary Organic Solar Cells with Nonfullerene Alloyed Acceptor

The vast majority of ternary organic solar cells are obtained by simply fabricating bulk heterojunction (BHJ) active layers. Due to the inappropriate distribution of donors and acceptors in the vertical direction, a new method by fabricating pseudoplanar heterojunction (PPHJ) ternary organic solar cells is proposed to better modulate the morphology of active layer. The pseudoplanar heterojunction ternary organic solar cells (P‐ternary) are fabricated by a sequential solution treatment technique, in which the donor and acceptor mixture blends are sequentially spin‐coated. As a consequence, a higher power conversion efficiency (PCE) of 14.2% is achieved with a V_oc of 0.79 V, J_sc of 25.6 mA cm^?2, and fill factor (FF) of 69.8% compared with the ternary BHJ system of 13.8%. At the same time, the alloyed acceptor is likely formed between two the acceptors through a series of in‐depth explorations. This work suggests that nonfullerene alloyed acceptor may have great potential to realize effective P‐ternary organic solar cells.     

High-Performance Green Thick-Film Ternary Organic Solar Cells Enabled by Crystallinity Regulation

The power conversion efficiency (PCE) of organic solar cells (OSCs) has reached high values of over 19%. However, most of the high-efficiency OSCs are fabricated by spin-coating with toxic solvents and the optimal photoactive layer thickness is limited to 100 nm, limiting practical development of OSCs. It is a great challenge to obtain ideal morphology for high-efficiency thick-film OSCs when using non-halogenated solvents due to the unfavorable film formation kinetics. Herein, high-efficiency ternary thick-film (300 nm) OSCs with PCE of 15.4% based on PM6:BTR-Cl:CH1007 are fabricated by hot slot-die coating using non-halogenated solvent (o-xylene) in the air. Compared to PM6:BTR-Cl:Y6 blends, the stronger pre-aggregation of CH1007 in solution induces the earlier aggregation of CH1007 molecules and longer aggregation time, and thus results in high and balanced crystallinity of donors and acceptor in CH1007-based ternary film, which led to high-carrier mobility and suppressed charge recombination. The ternary strategy is further used to fabricate high-efficiency, thick-film, large-area, and flexible devices processed from non-halogenated solvents, paving the way for industrial development of OSCs.     

Ternary Blend Strategy for Achieving High‐Efficiency Organic Solar Cells with Nonfullerene Acceptors Involved

Nonfullerene acceptors have recently drawn considerable attention in bulk heterojunction organic solar cells (OSCs). The power conversion efficiency (PCE) over 14% is achieved in single‐junction fullerene‐free OSCs, which has surpassed that of fullerene‐based counterparts. For future commercial applications, however, a high and stable PCE > 15% is required, which entails rational material design and device optimization. In this context, three approaches are generally utilized—the synthesis of novel nonfullerene acceptors and the selection of suitable polymer donors to pair with them, the tandem or multijunction device architecture, and the ternary blend strategy. Compared to the former two methods, the ternary strategy allows to employ the existing photovoltaic materials and the single‐junction device. Therefore, an exploration of nonfullerene acceptor–based ternary blend OSCs (NFTSCs) has shown unprecedented progress since 2016. This review summarizes and classifies the photovoltaic materials utilized in NFTSCs, aiming to not only exhibit the recent development of NFTSCs but also elucidate the correlation among donor/acceptor materials, film morphology, transport dynamics, and device fabrication toward high‐efficiency OSCs. Lastly, the above key advances are highlighted along with the existing issues and insights into the viable path for the further research thrusts are offered.     

18.9% Efficiency Ternary Organic Solar Cells Enabled by Isomerization Engineering of Chlorine-Substitution on Small Molecule Donors

Ternary organic solar cells (OSCs) represent an efficient and facile strategy to further boost the device performance. However, the selection criteria and rational design of the third guest small molecule (SM) material still remain less understood. In this study, two new SM donor isomers, with α-chlorinated thiophene (αBTCl) and β-chlorinated thiophene (βBTCl) as side chains, are systematically designed, synthesized and incorporated as a third component in PM6:L8-BO binary blends. It is noticed that introducing the SM donors guest has extended the absorption of photo-active layer, induced desired component distribution vertically with enhanced crystallinity and reduced recombination process, leading to increased short-circuit current (J_SC) and improved fill factor. Moreover, due to the synergetic suppressed nonradiative loss and preferable morphology, the ternary OSCs feature improves open-circuit voltage (V_OC). Consequently, an impressive champion power conversion efficiency of 18.96% and 18.55% is achieved by αBTCl-based and βBTCl-based ternary OSCs, respectively. Furthermore, a record efficiency of 17.46% is obtained with a 330 nm thickness of αBTCl-based ternary OSCs. This study demonstrates that molecular isomerization can be a promising design approach for SM donors to construct high-performance ternary OSCs with simultaneous enhancement of all photovoltaic parameters.     

High-Performance Ternary Organic Solar Cells Enabled by Integrating a 3D-Shaped Guest Acceptor Derived from Perylene Diimide

Integrating a third component into the binary system is considered to be one of the most effective strategies to further enhance the power conversion efficiency (PCE) in organic solar cells (OSCs). Here, a novel perylene diimide (PDI) derivative featuring 3D structure, TPA-4PDI, with tetraphenyladamantane central core is developed as a guest electron acceptor to be incorporated into the PM6:Y6 binary system. The champion PCE of ternary OSC is recorded to be 18.29% by adding 7.5 wt.% of TPA-4PDI in the ternary blend, which photovoltaic performance is enhanced with synergistically increased open-circuit voltage (V_oc) of 0.849 V, short-circuit current density (J_sc) of 27.55 mA cm⁻², and fill factor (FF) of 78.21%. TPA-4PDI exhibits a complementary absorption band with PM6 and Y6 while its lowest unoccupied molecular orbital (LUMO) energy level falls between the two host materials. The addition of TPA-4PDI can effectively suppress the recombination behavior, inhibit the excessive aggregation of Y6 and improve the morphology of PM6:Y6 blend. All these effects function synergistically and then lead to the enhancement of V_oc, J_sc, and FF in ternary OSCs. This study suggests that developing PDI derivatives as the third component is an effective method to further improve the performance of ternary OSCs.     

Efficient Ternary Organic Solar Cells Enabled by the Integration of Nonfullerene and Fullerene Acceptors with a Broad Composition Tolerance

The ternary structure that combines fullerene and nonfullerene acceptors in a photoactive layer is demonstrated as an effective approach for boosting the power conversion efficiencies (PCEs) of organic solar cells (OSCs). Here, highly efficient ternary OSCs comprising a wide‐bandgap polymer donor (PBT1‐C), a narrow‐bandgap nonfullerene acceptor (IT‐2F), and a typical fullerene derivative (PC₇₁BM) are reported. It is found that the addition of PC₇₁BM into the PBT1‐C:IT‐2F blend not only increases the device efficiency up to 12.2%, but also improves the ambient stability of the OSCs. Detailed investigations indicate that the improvement in photovoltaic performance benefits from synergistic effects of increased photon‐harvesting, enhanced charge separation and transport, suppressed trap‐assisted recombination, and optimized film morphology. Moreover, it is noticed that such a ternary system exhibits excellent tolerance to the PC₇₁BM component, for which PCEs over 11.2% can be maintained throughout the whole blend ratios, higher than that (11.0%) of PBT1‐C:IT‐2F binary reference device.     

Identifying a Threshold Impurity Level for Organic Solar Cells: Enhanced First‐Order Recombination Via Well‐Defined PC84BM Traps in Organic Bulk Heterojunction Solar Cells

Small amounts of impurity, even one part in one thousand, in polymer bulk heterojunction solar cells can alter the electronic properties of the device, including reducing the open circuit voltage, the short circuit current and the fill factor. Steady state studies show a dramatic increase in the trap‐assisted recombination rate when [6,6]‐phenyl C₈₄ butyric acid methyl ester (PC₈₄BM) is introduced as a trap site in polymer bulk heterojunction solar cells made of a blend of the copolymer poly[N‐9″‐hepta‐decanyl‐2,7‐carbazole‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole) (PCDTBT) and the fullerene derivative [6,6]‐phenyl C₆₁ butyric acid methyl ester (PC₆₀BM). The trap density dependent recombination studied here can be described as a combination of bimolecular and Shockley–Read–Hall recombination; the latter is dramatically enhanced by the addition of the PC₈₄BM traps. This study reveals the importance of impurities in limiting the efficiency of organic solar cell devices and gives insight into the mechanism of the trap‐induced recombination loss.     

High‐Performance Inverted Planar Heterojunction Perovskite Solar Cells Based on Lead Acetate Precursor with Efficiency Exceeding 18%

Organic–inorganic lead halide perovskites are emerging materials for the next‐generation photovoltaics. Lead halides are the most commonly used lead precursors for perovskite active layers. Recently, lead acetate (Pb(Ac)₂) has shown its superiority as the potential replacement for traditional lead halides. Here, we demonstrate a strategy to improve the efficiency for the perovskite solar cell based on lead acetate precursor. We utilized methylammonium bromide as an additive in the Pb(Ac)₂ and methylammonium iodide precursor solution, resulting in uniform, compact and pinhole‐free perovskite films. We observed enhanced charge carrier extraction between the perovskite layer and charge collection layers and delivered a champion power conversion efficiency of 18.3% with a stabilized output efficiency of 17.6% at the maximum power point. The optimized devices also exhibited negligible current density–voltage (J–V) hysteresis under the scanning conditions.     

Green-Solvent-Processed High-Performance Ternary Organic Solar Cells Comprising a Highly Soluble and Fluorescent Third Component

Nowadays, it is still a great challenge to obtain high-performance green-solvent-processed organic solar cells (OSCs). In this study, a ternary blend strategy (one donor and two acceptors, 1D/2A) is developed to solve the difficulty of film morphology modulation during the fabrication of high-performance green-solvent-processed OSCs. A typical high-performance halogenated-solvent processable binary system D18:BTP-eC9-4F is selected as the host, its green-solvents-processed devices show an inferior power conversion efficiency (PCE) of ≈16%. SM16 with two 3D shape persistent end groups is selected as the third component due to its high fluorescence quantum yield, reduced intermolecular interaction, good solubility, and moderate crystallinity. As a result, the ternary devices display bicontinuous interpenetrating networks, reduced energy loss, and suppressed charge carrier recombination losses. Hence, an excellent PCE of 18.20% is achieved for the D18:BTP-eC9-4F:SM16 ternary devices, which is much higher than D18:BTP-eC9-4F-based binary ones and also one of the highest PCEs for the green-solvents-processed OSCs. Besides, this strategy also demonstrates a good universality for other binary systems and becomes an effective pathway for the development of green-solvent processable high-performance OSCs.     

Merocyanine/C60 Planar Heterojunction Solar Cells: Effect of Dye Orientation on Exciton Dissociation and Solar Cell Performance

In this study the charge dissociation at the donor/acceptor heterointerface of thermally evaporated planar heterojunction merocyanine/C₆₀ organic solar cells is investigated. Deposition of the donor material on a heated substrate as well as post‐annealing of the complete devices at temperatures above the glass transition temperature of the donor material results in a twofold increase of the fill factor. An analytical model employing an electric‐field‐dependent exciton dissociation mechanism reveals that geminate recombination is limiting the performance of as‐deposited cells. Fourier‐transform infrared ellipsometry shows that, at temperatures above the glass transition temperature of the donor material, the orientation of the dye molecules in the donor films undergoes changes upon annealing. Based on this finding, the influence of the dye molecules’ orientations on the charge‐transfer state energies is calculated by quantum mechanical/molecular mechanics methods. The results of these detailed studies provide new insight into the exciton dissociation process in organic photovoltaic devices, and thus valuable guidelines for designing new donor materials.     

Accurate Measurement and Characterization of Organic Solar Cells

Methods to accurately measure the current–voltage characteristics of organic solar cells under standard reporting conditions are presented. Four types of organic test cells and two types of silicon reference cells (unfiltered and with a KG5 color filter) are selected to calculate spectral‐mismatch factors for different test‐cell/reference‐cell combinations. The test devices include both polymer/fullerene‐based bulk‐heterojunction solar cells and small‐molecule‐based heterojunction solar cells. The spectral responsivities of test cells are measured as per American Society for Testing and Materials Standard E1021, and their dependence on light‐bias intensity is reported. The current–voltage curves are measured under 100 mW cm^–2 standard AM 1.5 G (AM: air mass) spectrum (International Electrotechnical Commission 69094‐1) generated from a source set with a reference cell and corrected for spectral error.     

Improved Performance of Molecular Bulk‐Heterojunction Photovoltaic Cells through Predictable Selection of Solvent Additives

Solvent additives provide an effective means to alter the morphology and thereby improve the performance of organic bulk‐heterojunction photovoltaics, although guidelines for selecting an appropriate solvent additive remain relatively unclear. Here, a family of solvent additives spanning a wide range of Hansen solubility parameters is applied to a molecular bulk‐heterojunction system consisting of an isoindigo and thiophene containing oligomer as the electron donor and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) as the electron acceptor. Hansen solubility parameters are calculated using the group contribution method and compared with the measured solubilities for use as a screening method in solvent additive selection. The additives are shown to alter the morphologies in a semipredictable manner, with the poorer solvents generally resulting in decreased domain sizes, increased hole mobilities, and improved photovoltaic performance. The additives with larger hydrogen bonding parameters, namely triethylene glycol (TEG) and N‐methyl‐2‐pyrrolidone (NMP), are demonstrated to increase the open circuit voltage by ~0.2 V. Combining a solvent additive observed to increase short circuit current, poly(dimethylsiloxane), with TEG results in an increase in power conversion efficiency from 1.4 to 3.3%.     

Rational Mutual Interactions in Ternary Systems Enable High-Performance Organic Solar Cells

Ternary organic solar cells (TOSCs) offer a facile and efficient approach to increase the power conversion efficiencies (PCEs). However, the critical roles that guest components play in complicated ternary systems remain poorly understood. Herein, two acceptors named LA1 and LA9 with differing crystallinity are investigated. The overly crystalline LA9 induces large self-aggregates in PM6:LA9 binary system, resulting in a lower PCE (13.12%) compared to PM6:LA1 device (13.89%). Encouragingly, both acceptors are verified as efficient guest candidates into the host binary PM6:NCBDT-4Cl (PCE = 13.48%) and afford markedly improved PCEs up to 15.39% and 15.75% in LA1 and LA9 ternary devices, respectively. Interestingly, the higher crystallinity LA9 reveals smaller interaction energies with both the host acceptor and donor PM6. Compared to LA1, the appropriate mutual interactions in the LA9 ternary system not only induces the orderly crystallinity of PM6 but also better compatibility with the host acceptor, generating further optimized molecular orientations and ternary morphology. Therefore, enhanced charge transport and minimized recombination loss are detected in LA9 ternary devices, affording the most competitive performance among Y6-sbsent TOSCs. This work suggests that complicated intermolecular interactions should be seriously considered when fabricating state-of-the-art multiple components OSCs.     

Spin‐ and Spray‐Deposited Single‐Walled Carbon‐Nanotube Electrodes for Organic Solar Cells

Organic bulk‐heterojunction solar cells using thin‐film single‐walled carbon‐nanotube (SWCNT) anodes deposited on glass are reported. Two types of SWCNT films are investigated: spin‐coated films from dichloroethane (DCE), and spray‐coated films from deionized water using sodium dodecyl sulphate (SDS) or sodium dodecyl benzene sulphonate (SDBS) as the surfactant. All of the films are found to be mechanically robust, with no tendency to delaminate from the underlying substrate during handling. Acid treatment with HNO₃ yields high conductivities >1000 S cm^?1 for all of the films, with values of up to 7694 ± 800 S cm^?1 being obtained when using SDS as the surfactant. Sheet resistances of around 100 Ω sq^?1 are obtained at reasonable transmission, for example, 128 ± 2 Ω sq^?1 at 90% for DCE, 57 ± 3 Ω sq^?1 at 65% for H₂O:SDS, and 68 ± 5 Ω sq^?1 at 70% for H₂O:SDBS. Solar cells are fabricated by successively coating the SWCNT films with poly(3,4‐ethylenedioxythiophene):poly(styrene sulphonate) (PEDOT:PSS), a blend of regioregular poly(3‐hexylthiophene) (P3HT) and 1‐(3‐methoxy‐carbonyl)‐propyl‐1‐phenyl‐(6,6)C₆₁ (PCBM), and LiF/Al. The resultant devices have respective power conversions of 2.3, 2.2 and 1.2% for DCE, H₂O:SDS and H₂O:SDBS, with the first two being at a virtual parity with reference devices using ITO‐coated glass as the anode (2.3%).     

Evaporation-Free Organic Solar Cells with High Efficiency Enabled by Dry and Nonimmersive Sintering Strategy

A solution-processed top electrode is critical to unlock the full potential of all-solution-processed organic solar cells (OSCs) for practical applications. However, the enabled devices suffer from low efficiency (<12%) mainly because of the irreversible damages induced by the top-electrode deposition process. Herein, a strategy of dry and nonimmersive sintering is demonstrated by introducing a hydrogen-intercalated molybdenum oxide layer to sinter isolated Ag nanoparticles into the top electrode (all from solution process) with little influences/issues on underlying device structures. Fundamentally, it is unveiled that the intercalated hydrogen will bond with the amino group of the ligands around Ag nanoparticles, which promotes the exposed nanoparticles to merge along a certain crystal orientation (≈45°) and form a conductive electrode (8.6 Ω sq⁻¹). Importantly, the sintered electrode offers 70% optical reflection in the 700–1050 nm wavelength region, which is essential to enhance the light absorption of high-performance nonfullerene acceptors. Consequently, a record efficiency of 15% is achieved, driving all-solution processed OSCs toward commercial applications.     

An Effective Method for Recovering Nonradiative Recombination Loss in Scalable Organic Solar Cells

Regarded as a critical step in commercial applications, scalable printing technology has become a research frontier in the field of organic solar cells. However, inevitable efficiency loss always occurs in the lab‐to‐manufacturing translation due to the different fabrication processes. In fact, the decline of photovoltaic performance is mainly related to voltage loss, which is mainly affected by the diversity of phase separation morphology and the chemical structures of photoactive materials. Fullerene derivative indene‐C₆₀ bisadduct (ICBA) is introduced into a PBDB‐T‐2F:IT‐4F system to control the active layer morphology during blade‐coating process. Accordingly, as a symmetrical fullerene derivative, ICBA can regulate the crystallization tendency and molecular packing orientation and suppress charge carrier recombination. This ternary strategy overcomes the morphology issues caused by weaker shear impulse in blade‐coating process. Benefiting from the reduced nonradiative recombination loss, 1.05 cm² devices are fabricated by blade coating with a power conversion efficiency of 13.70%. This approach provides an effective support for recovering the voltage loss during scalable printing approaches.     

Enhanced Thermal Stability and Efficiency of Polymer Bulk‐Heterojunction Solar Cells by Low‐Temperature Drying of the Active Layer

This study addresses two key issues, stability and efficiency, of polymer solar cells based on blended poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) by demonstrating a film‐forming process that involves low‐temperature drying (?5 °C) and subsequent annealing of the active layer. The low‐temperature process achieves 4.70% power conversion efficiency (PCE) and ～1250 h storage half‐life at 65 °C, which are significant improvements over the 3.39% PCE and ～143 h half‐life of the regular room‐temperature process. The improvements are attributed to the enhanced nucleation of P3HT crystallites as well as the minimized separation of the P3HT and PCBM phases at the low drying temperature, which upon post‐drying annealing results in a morphology consisting of small PCBM‐rich domains interspersed within a densely interconnected P3HT crystal network. This morphology provides ample bulk‐heterojunction area for charge generation while allowing for facile charge transport; moreover, the P3HT crystal network serves as an immobile frame at heating temperatures less than the melting point (T_m) of P3HT, thus preventing PCBM/P3HT phase separation and the corresponding device degradation.     

Fluorenone‐Based Molecules for Bulk‐Heterojunction Solar Cells: Synthesis,Characterization, and Photovoltaic Properties

A series of four conjugated molecules consisting of a fluorenone central unit symmetrically coupled to different oligothiophene segments are conceptually designed and synthesized to provide new electroactive materials for application in photovoltaic devices. The combination of electron‐donating oligothiophene building blocks with an electron‐accepting fluorenone unit results in the emergence of a new band assigned to an intramolecular charge transfer transition that gives rise to the extension of the absorption spectral range of the resulting molecules. Detailed spectroscopic and voltammetric investigations show that all studied molecules have highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) level positions, which make them good candidates for the application as electron‐donors in bulk‐heterojunction photovoltaic cells, with (6,6)‐phenyl‐C61‐butyric acid methyl ester (PCBM)‐C₆₀ as electron acceptor component. Moderate device performances, with power conversion efficiencies (PCEs) comprised between 0.3 and 0.6%, were obtained with rigid molecules, containing either the bridging units between the thiophene rings, i.e., (2,7‐bis(4,4′‐dioctyl‐cyclopenta[2,1‐b:3,4‐b′]dithiophen‐2‐yl)‐fluoren‐9‐one (SCPTF) and 2,7‐bis(4‐(dioctylmethylene)‐cyclopenta[2,1‐b:3,4‐b′]dithiophen‐5‐yl)‐fluoren‐9‐one (MCPTF) or a vinylene unit 2,7‐bis(5‐[(E)‐1,2‐bis(3‐octylthien‐2‐yl)ethylene])‐fluoren‐9‐one (TVF), whereas with (2,7‐bis‐(3,3?‐dioctyl‐[2,2′;5′,2″;5″,2?]quaterthiophen‐5‐yl)‐fluoren‐9‐one (QTF) PCE up to 1.2% (under AM 1.5 illumination, 100 mW cm^?2, active area 0.28 cm²) was obtained. The strong π‐stacking interactions in the solid state for this oligomer leading to improved morphology could explain the good performances of QTF‐based devices, which rank among the highest recorded for non‐polymeric materials. Consequently, fluorenone‐based non‐polymeric molecules constitute highly attractive materials for solution‐processable solar cell applications.