Achieving Over 15% Efficiency in Organic Photovoltaic Cells via Copolymer Design

Ternary blending and copolymerization strategies have proven advantageous in boosting the photovoltaic performance of organic solar cells. Here, 15% efficiency solar cells using copolymerization donors are demonstrated, where the electron‐withdrawing unit, ester‐substituted thiophene, is incorporated into a PBDB‐TF polymer to downshift the molecular energy and broaden the absorption. Copolymer‐based solar cells suitable for large‐area devices can be fabricated by a blade‐coating method from a nonhalogen and nonaromatic solvent mixture. Although ternary solar cells can achieve comparable efficiencies, they are not suitable for environment‐friendly processing conditions and show relatively low photostability compared to copolymer‐based devices. These results not only demonstrate high‐efficiency organic photovoltaic cells via copolymerization strategies but also provide important insights into their applications in practical production.     

Single-Junction Organic Photovoltaic Cells with Approaching 18% Efficiency

Optimizing the molecular structures of organic photovoltaic (OPV) materials is one of the most effective methods to boost power conversion efficiencies (PCEs). For an excellent molecular system with a certain conjugated skeleton, fine tuning the alky chains is of considerable significance to fully explore its photovoltaic potential. In this work, the optimization of alkyl chains is performed on a chlorinated nonfullerene acceptor (NFA) named BTP-4Cl-BO (a Y6 derivative) and very impressive photovoltaic parameters in OPV cells are obtained. To get more ordered intermolecular packing, the n-undecyl is shortened at the edge of BTP-eC11 to n-nonyl and n-heptyl. As a result, the NFAs of BTP-eC9 and BTP-eC7 are synthesized. The BTP-eC7 shows relatively poor solubility and thus limits its application in device fabrication. Fortunately, the BTP-eC9 possesses good solubility and, at the same time, enhanced electron transport property than BTP-eC11. Significantly, due to the simultaneously enhanced short-circuit current density and fill factor, the BTP-eC9-based single-junction OPV cells record a maximum PCE of 17.8% and get a certified value of 17.3%. These results demonstrate that minimizing the alkyl chains to get suitable solubility and enhanced intermolecular packing has a great potential in further improving its photovoltaic performance.     

Eco‐Compatible Solvent‐Processed Organic Photovoltaic Cells with Over 16% Efficiency

Recent advances in nonfullerene acceptors (NFAs) have enabled the rapid increase in power conversion efficiencies (PCEs) of organic photovoltaic (OPV) cells. However, this progress is achieved using highly toxic solvents, which are not suitable for the scalable large‐area processing method, becoming one of the biggest factors hindering the mass production and commercial applications of OPVs. Therefore, it is of great importance to get good eco‐compatible processability when designing efficient OPV materials. Here, to achieve high efficiency and good processability of the NFAs in eco‐compatible solvents, the flexible alkyl chains of the highly efficient NFA BTP‐4F‐8 (also known as Y6) are modified and BTP‐4F‐12 is synthesized. Combining with the polymer donor PBDB‐TF, BTP‐4F‐12 shows the best PCE of 16.4%. Importantly, when the polymer donor PBDB‐TF is replaced by T1 with better solubility, various eco‐compatible solvents can be applied to fabricate OPV cells. Finally, over 14% efficiency is obtained with tetrahydrofuran (THF) as the processing solvent for 1.07 cm² OPV cells by the blade‐coating method. These results indicate that the simple modification of the side chain can be used to tune the processability of active layer materials and thus make it more applicable for the mass production with environmentally benign solvents.     

Subtle Molecular Tailoring Induces Significant Morphology Optimization Enabling over 16% Efficiency Organic Solar Cells with Efficient Charge Generation

Manipulating charge generation in a broad spectral region has proved to be crucial for nonfullerene-electron-acceptor-based organic solar cells (OSCs). 16.64% high efficiency binary OSCs are achieved through the use of a novel electron acceptor AQx-2 with quinoxaline-containing fused core and PBDB-TF as donor. The significant increase in photovoltaic performance of AQx-2 based devices is obtained merely by a subtle tailoring in molecular structure of its analogue AQx-1. Combining the detailed morphology and transient absorption spectroscopy analyses, a good structure–morphology–property relationship is established. The stronger π–π interaction results in efficient electron hopping and balanced electron and hole mobilities attributed to good charge transport. Moreover, the reduced phase separation morphology of AQx-2-based bulk heterojunction blend boosts hole transfer and suppresses geminate recombination. Such success in molecule design and precise morphology optimization may lead to next-generation high-performance OSCs.     

Thermally Stable MAPbI3 Perovskite Solar Cells with Efficiency of 19.19% and Area over 1 cm2 achieved by Additive Engineering

Solution‐processed perovskite (PSC) solar cells have achieved extremely high power conversion efficiencies (PCEs) over 20%, but practical application of this photovoltaic technology requires further advancements on both long‐term stability and large‐area device demonstration. Here, an additive‐engineering strategy is developed to realize a facile and convenient fabrication method of large‐area uniform perovskite films composed of large crystal size and low density of defects. The high crystalline quality of the perovskite is found to simultaneously enhance the PCE and the durability of PSCs. By using the simple and widely used methylammonium lead iodide (MAPbI₃), a certified PCE of 19.19% is achieved for devices with an aperture area of 1.025 cm², and the high‐performing devices can sustain over 80% of the initial PCE after 500 h of thermal aging at 85 °C, which are among the best results of MAPbI₃‐based PSCs so far.     

高温后退火处理对聚合物光伏电池阴极界面层的影响

分别采用LiF和2,9-二甲基-4,7-二苯基-1,10-菲咯啉(BCP)作为聚3-己基噻吩(P3HT)/[6,6]-苯基-C61-丁酸甲脂(PCBM)体系聚合物光伏电池阴极界面层,研究了高温后退火处理对不同界面层器件性能的影响。研究发现,LiF界面层的引入,在活性层和阴极界面之间形成了较强的偶极作用,从而改善了电池的性能,进一步高温热退火处理后仍能保持良好的界面作用,使器件的能量转换效率得到了进一步的提高。然而BCP界面层的引入,虽然阻挡了金属电极Al到PCBM的电子转移,导致复合减小,提高了器件的开路电压,但是在进一步高温后退火之后,BCP界面层的完整性遭到破坏,因此使得器件的能量转换效率降低。     

Cosensitized Quantum Dot Solar Cells with Conversion Efficiency over 12%

The improvement of sunlight utilization is a fundamental approach for the construction of high‐efficiency quantum‐dot‐based solar cells (QDSCs). To boost light harvesting, cosensitized photoanodes are fabricated in this work by a sequential deposition of presynthesized Zn–Cu–In–Se (ZCISe) and CdSe quantum dots (QDs) on mesoporous TiO₂ films via the control of the interactions between QDs and TiO₂ films using 3‐mercaptopropionic acid bifunctional linkers. By the synergistic effect of ZCISe‐alloyed QDs with a wide light absorption range and CdSe QDs with a high extinction coefficient, the incident photon‐to‐electron conversion efficiency is significantly improved over single QD‐based QDSCs. It is found that the performance of cosensitized photoanodes can be optimized by adjusting the size of CdSe QDs introduced. In combination with titanium mesh supported mesoporous carbon as a counterelectrode and a modified polysulfide solution as an electrolyte, a champion power conversion efficiency up to 12.75% (V_oc = 0.752 V, J_sc = 27.39 mA cm^?2, FF = 0.619) is achieved, which is, as far as it is known, the highest efficiency for liquid‐junction QD‐based solar cells reported.     

Nonfullerene Tandem Organic Solar Cells with High Performance of 14.11%

Fabricating solar cells with tandem structure is an efficient way to broaden the photon response range without further increasing the thermalization loss in the system. In this work, a tandem organic solar cell (TOSC) based on highly efficient nonfullerene acceptors (NFAs) with series connection type is demonstrated. To meet the different demands of front and rear sub‐cells, two NFAs named F‐M and NOBDT with a whole absorption range from 300 to 900 nm are designed, when blended with wide bandgap polymer poly[(2,6‐(4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)‐benzo[1,2‐b:4,5‐b′]dithiophene))‐alt‐(5,5‐(1′,3′‐di‐2‐thienyl‐5′,7′‐bis(2‐ethylhexyl)benzo[1′,2′‐c:4′,5′‐c′]dithiophene‐4,8‐dione))] (PBDB‐T) and narrow bandgap polymer PTB7‐Th, respectively, the PBDB‐T: F‐M system exhibits a high V_oc of 0.98 V and the PTB7‐Th: NOBDT system shows a remarkable J_sc of 19.16 mA cm^?2, which demonstrate their potential in the TOSCs. With the guidance of optical simulation, by systematically optimizing the thickness of each layer in the TOSC, an outstanding power conversion efficiency of 14.11%, with a V_oc of 1.71 V, a J_sc of 11.72 mA cm^?2, and a satisfactory fill factor of 0.70 is achieved; this result is one of the top efficiencies reported to date in the field of organic solar cells.     

Achieving 12.8% Efficiency by Simultaneously Improving Open‐Circuit Voltage and Short‐Circuit Current Density in Tandem Organic Solar Cells

Tandem organic solar cells (TOSCs), which integrate multiple organic photovoltaic layers with complementary absorption in series, have been proved to be a strong contender in organic photovoltaic depending on their advantages in harvesting a greater part of the solar spectrum and more efficient photon utilization than traditional single‐junction organic solar cells. However, simultaneously improving open circuit voltage (V_oc) and short current density (J_sc) is a still particularly tricky issue for highly efficient TOSCs. In this work, by employing the low‐bandgap nonfullerene acceptor, IEICO, into the rear cell to extend absorption, and meanwhile introducing PBDD4T‐2F into the front cell for improving V_oc, an impressive efficiency of 12.8% has been achieved in well‐designed TOSC. This result is also one of the highest efficiencies reported in state‐of‐the‐art organic solar cells.     

Ternary Organic Solar Cells with Efficiency >16.5% Based on Two Compatible Nonfullerene Acceptors

A ternary structure has been demonstrated as being an effective strategy to realize high power conversion efficiency (PCE) in organic solar cells (OSCs); however, general materials selection rules still remain incompletely understood. In this work, two nonfullerene small‐molecule acceptors 3TP3T‐4F and 3TP3T‐IC are synthesized and incorporated as a third component in PM6:Y6 binary blends. The photovoltaic behaviors in the resultant ternary OSCs differ significantly, despite the comparable energy levels. It is found that incorporation of 15% 3TP3T‐4F into the PM6:Y6 blend results in facilitating exciton dissociation, increasing charge transport, and reducing trap‐assisted recombination. All these features are responsible for the enlarged PCE of 16.7% (certified as 16.2%) in the PM6:Y6:3TP3T‐4F ternary OSCs, higher than that (15.6%) in the 3TP3T‐IC containing ternary devices. The performance differences are mainly ascribed to the compatibility between the third component and the host materials. The 3TP3T‐4F guest acceptor exhibits an excellent compatibility with Y6, tending to form well‐mixed phases in the ternary blend without disrupting the favored bicontinuous transport networks, whereas 3TP3T‐IC displays a morphological incompatibility with Y6. This work highlights the importance of considering the compatibility for materials selection toward high‐efficiency ternary organic OSCs.     

Graphdiyne Derivative as Multifunctional Solid Additive in Binary Organic Solar Cells with 17.3% Efficiency and High Reproductivity

Morphology tuning of the blend film in organic solar cells (OSCs) is a key approach to improve device efficiencies. Among various strategies, solid additive is proposed as a simple and new way to enable morphology tuning. However, there exist few solid additives reported to meet such expectations. Herein, chlorine-functionalized graphdiyne (GCl) is successfully applied as a multifunctional solid additive to fine-tune the morphology and improve device efficiency as well as reproductivity for the first time. Compared with 15.6% efficiency for control devices, a record high efficiency of 17.3% with the certified one of 17.1% is obtained along with the simultaneous increase of short-circuit current (J_sc) and fill factor (FF), displaying the state-of-the-art binary organic solar cells at present. The redshift of the film absorption, enhanced crystallinity, prominent phase separation, improved mobility, and decreased charge recombination synergistically account for the increase of J_sc and FF after introducing GCl into the blend film. Moreover, the addition of GCl dramatically reduces batch-to-batch variations benefiting mass production owing to the nonvolatile property of GCl. All these results confirm the efficacy of GCl to enhance device performance, demonstrating a promising application of GCl as a multifunctional solid additive in the field of OSCs.     

Recent Progress in All-Small-Molecule Organic Solar Cells

Active layer material plays a critical role in promoting the performance of an organic solar cell (OSC). Small-molecule (SM) materials have the merits of well-defined chemical structures, few batch-to-batch variations, facile synthesis and purification procedures, and easily tuned properties. SM-donor and non-fullerene acceptor (NFA) innovations have recently produced all-small-molecule (ASM) devices with power conversion efficiencies that exceed 17% and approach those of their polymer-based counterparts, thereby demonstrating their great future commercialization potential. In this review, recent progress in both SM donors and NFAs to illustrate structure–property relationships and various morphology-regulation strategies are summarized. Finally, ASM-OSC challenges and outlook are discussed.     

Organic Photovoltaic Cells: From Performance Improvement to Manufacturing Processes

Organic photovoltaics (OPVs) have been pursued as a next generation power source due to their light weight, thin, flexible, and simple fabrication advantages. Improvements in OPV efficiency have attracted great attention in the past decade. Because the functional layers in OPVs can be dissolved in common solvents, they can be manufactured by eco‐friendly and scalable printing or coating technologies. In this review article, the focus is on recent efforts to control nanomorphologies of photoactive layer and discussion of various solution‐processed charge transport and extraction materials, to maximize the performance of OPV cells. Next, recent works on printing and coating technologies for OPVs to realize solution processing are reviewed. The review concludes with a discussion of recent advances in the development of non‐traditional lamination and transfer method towards highly efficient and fully solution‐processed OPV.