Stable Radical TEMPO Terminated Perylene Bisimide(PBI) Based Small Molecule as Cathode Interlayer for Efficient Organic Solar Cells

By combining stable radical tetramethylpiperidine nitrogen oxide(TEMPO) as end groups and perylene bisimide(PBI) as the core, a small molecular cathode interlayer(CIL) (PBI-TEMPO) was synthesized. Detailed physical-chemical characterizations indicate that PBI-TEMPO can form smooth film, owns low unoccupied molecular orbital(LUMO) level of –3.67 eV and can reduce the work function of silver electrode. When using PBI-TEMPO as CIL in non-fullerene organic solar cells(OSCs), the PM6:BTP-4Cl based OSCs delivered high power conversion efficiencies(PCEs) up to 17.37%, higher than those using commercial PDINO CIL with PCEs of 16.95%. Further device characterizations indicate that PBI-TEMPO can facilitate more efficient exciton dissociation and reduce charge recombination, resulting in enhanced current density and fill factor. Moreover, PBI-TEMPO displays higher thermal stability than PDINO in solution. When PBI-TEMPO and PDINO solution were heated at 150 ℃ for 2 h and then were used as CIL in solar cells, PBI-TEMPO-based OSCs provided a PCE of 15%, while PDINO-based OSCs only showed a PCE of 10%. These results demonstrate that incorporating TEMPO into conjugated materials is a useful strategy to create new organic semiconductors for application in OSCs.     

Diazabicyclic Electroactive Ionenes for Efficient and Stable Organic Solar Cells

Electroactive ionenes combining caged-shaped diazabicyclic cations and aromatic diimides were developed as interlayers in organic solar cells (OSCs). These ionenes reduce the work-function of air-stable metal electrodes (e.g., Ag, Cu and Au) by generating strong interfacial dipoles, and their optoelectronic and morphological characters can be modulated by aromatic diimides, leading to high conductivity and good compatibility with active layers. The optimal ionene exhibits superior charge-transport, desirable crystallinity, and weak visible-absorption, boosting the efficiency of benchmark PM6 : Y6-based OSCs up to 17.44 %. The corresponding normal devices show excellent stability at maximum power point test under one sun illumination for 1000 h. Replacing Y6 with L8-BO promotes the efficiency to 18.43 %, one of the highest in binary OSCs. Notably, high efficiencies >16 % are maintained as the interlayer thickness increasing to 105 nm, the best result with interlayer-thickness over 100 nm.     

Benzotriazole-Based 3D Four-Arm Small Molecules Enable 19.1 % Efficiency for PM6 : Y6-Based Ternary Organic Solar Cells

A third component featuring a planar backbone structure similar to the binary host molecule has been the preferred ingredient for improving the photovoltaic performance of ternary organic solar cells (OSCs). In this work, we explored a new avenue that introduces 3D-structured molecules as guest acceptors. Spirobifluorene (SF) is chosen as the core to combine with three different terminal-modified (rhodanine, thiazolidinedione, and dicyano-substituted rhodanine) benzotriazole (BTA) units, affording three four-arm molecules, SF-BTA1, SF-BTA2, and SF-BTA3, respectively. After adding these three materials to the classical system PM6 : Y6, the resulting ternary devices obtained ultra-high power-conversion efficiencies (PCEs) of 19.1 %, 18.7 %, and 18.8 %, respectively, compared with the binary OSCs (PCE=17.4 %). SF-BTA1-3 can work as energy donors to increase charge generation via energy transfer. In addition, the charge transfer between PM6 and SF-BTA1-3 also acts to enhance charge generation. Introducing SF-BTA1-3 could form acceptor alloys to modify the molecular energy level and inhibit the self-aggregation of Y6, thereby reducing energy loss and balancing charge transport. Our success in 3D multi-arm materials as the third component shows good universality and brings a new perspective. The further functional development of multi-arm materials could make OSCs more stable and efficient.     

High efficiency ternary organic solar cells enabled by compatible dual-donor strategy with planar conjugated structures

Ternary organic solar cells(OSCs) have received extensive attention for improving the power conversion efficiency(PCE) of organic photovoltaics(OPVs). In this work, a novel donor material(ECTBD) consisting of benzodithiophene(BDT) central electron donor unit was developed and synthesized. The small molecular donor has the same central unit as PM6. The addition of ECTBD into PM6:Y6 system could improve the morphology of active blend layer. In addition, ECTBD showed good morphologically compatibility when blending with PM6:Y6 host, resulting in the improvement of fill factor and current density. As a result, the ternary devices based on PM6:ECTBD:Y6 ternary system achieved a highest PCE of 16.51% with fill factor of 76.24%, which was much higher than that of the binary devices(15.7%). Overall, this work provided an effective strategy to fabricate highly efficient ternary organic solar cells through design of the novel small molecular donor as the third component.     

Altering alkyl-chains branching positions for boosting the performance of small-molecule acceptors for highly efficient nonfullerene organic solar cells

The emergence of the latest generation of small-molecule acceptor(SMA) materials,with Y6 as a typical example,accounts for the surge in device performance for organic solar cells(OSCs).This study proposes two new acceptors named Y6-C2 and Y6-C3,from judicious alteration of alkyl-chains branching positions away from the Y6 backbone.Compared to the Y6,the Y6-C2 exhibits similar optical and electrochemical properties,but better molecular packing and enhanced crystallinity.In contrast,the Y6-C3 shows a significant blue-shift absorption in the solid state relative to the Y6 and Y6-C2.The as-cast PM6:Y6-C2-based OSC yields a higher power conversion efficiency(PCE) of 15.89% than those based on the Y6(15.24%) and Y6-C3(13.76%),representing the highest known value for as-cast nonfullerene OSCs.Prominently,the Y6-C2 displays a good compatibility with the PC_(71)BM.Therefore,a ternary OSC device based on PM6:Y6-C2:PC_(71)BM(1.0:1.0:0.2) was produced,and it exhibits an outstanding PCE of 17.06% and an impressive fill factor(FF) of 0.772.Our results improve understanding of the structureproperty relationship for state-of-the-art SMAs and demonstrate that modulating the structure of SMAs via fine-tuning of alkylchains branching positions is an effective method to enhance their performance.     

TFTTP作为阴极缓冲层提高有机薄膜太阳能电池的内建电场和载流子收集效率

采用一种新型的电子传输材料TFTTP作为阴极缓冲层提高基于SubPc/C60异质结的有机薄膜太阳能电池的性能. 通过在有机活性层和金属电极之间加入TFTTP界面层,器件的能量转换效率提高了约30%. 系统研究了器件的二极管特性、光电流特性以及内部的光场分布情况,结果表明,TFTTP阴极缓冲层的引入可以有效地提高器件的内建电场,进而增加电荷转移激子的分离效率. 通过使用TFTTP作为阴极缓冲层,在C60/金属界面形成良好的欧姆接触,降低了界面接触电阻,有利于自由载流子的收集.     

Printable SnO2 cathode interlayer with up to 500 nm thickness-tolerance for high-performance and large-area organic solar cells

The printable electrode interlayer with excellent thickness tolerance is crucial for mass production of organic solar cells(OSCs)by solution-based print techniques. Herein, high-quality printable SnO_2 films are simply fabricated by spin-coating or bladecoating the chemical precipitated SnO_2 colloid precursor with post thermal annealing treatment. The SnO_2 films possess outstanding optical and electrical properties, especially extreme thickness-insensitivity. The interfacial electron trap density of SnO_2 cathode interlayers(CILs) are very low and show negligible increase as the thicknesses increase from 10 to 160 nm,resulting in slight change of the power conversion efficiencies(PCEs) of the PM6:Y6 based OSCs from 16.10% to 13.07%. For blade-coated SnO_2 CIL, the PCE remains high up to 12.08% even the thickness of SnO_2 CIL is high up to 530 nm. More strikingly, the large-area OSCs of 100 mm~2 with printed SnO_2 CILs obtain a high efficiency of 12.74%. To the best of our knowledge, this work presents the first example for the high-performance and large-area OSCs with the thickness-insensitive SnO_2 CIL.     

利用扫描开尔文探针显微镜观察薄膜光电器件能级排布

薄膜光电器件的能级结构直接决定了载流子的产生、分离、传输、复合和收集等微观动力学过程,从而决定了器件性能。因此准确获取器件能级结构,是深入理解器件工作机制、推动器件技术革新的重要科学依据。此专论系统地介绍了本课题组利用扫描开尔文探针显微镜(SKPM)表征薄膜光电器件如有机太阳能电池、有机-无机钙钛矿光探测器等器件中界面能级结构的工作。垂直型薄膜器件中的活性材料层被顶电极与底电极封闭,通常难以直接在器件工况下测量其中的界面能级排布,我们发展了横截面SKPM技术来解决这一难题。研究表明,界面层是调控器件能级结构、决定器件极性、提高器件性能的重要手段。本文介绍的表征技术有望在各种薄膜光电器件,诸如光伏器件、光探测器、发光二极管,尤其是各种叠层构型器件的研究中展现出广阔的应用前景。     

Anisotropic charge carrier transport of optoelectronic functional selenium-containing organic semiconductor materials

Organic semiconductors (OSCs) materials are currently under intense investigation because of their potential applications such as organic field-effect transistors, organic photovoltaic devices, and organic light-emitting diodes. Inspired by the selenization strategy can promote anisotropic charge carrier migration, and selenium-containing compounds have been proved to be promising materials as OSCs both for hole and electron transfer. Herein, we now explore the anisotropic transport properties of the series of selenium-containing compounds. For the compound containing Se Se bond, the Se Se bond will break when attaching an electron, thus those compounds cannot act as n-type OSCs. About the different isomer compounds with conjugated structure, the charge transfer will be affected by the stacking of the conjugated structures. The analysis of chemical structure and charge transfer property indicates that Se-containing materials are promising high-performance OSCs and might be used as p-type, n-type, or ambipolar OSCs. Furthermore, the symmetry of the selenium-containing OSCs will affect the type of OSCs. In addition, there is no direct relationship between the R groups with their performance, whether it or not as p-type OSCs or n-types. This work demonstrates the relationship between the optoelectronic function and structure of selenium-containing OSCs materials and hence paves the way to design and improve optoelectronic function of OSCs materials.     

Unidirectional Sidechain Engineering to Construct Dual-Asymmetric Acceptors for 19.23 % Efficiency Organic Solar Cells with Low Energy Loss and Efficient Charge Transfer

Achieving both high open-circuit voltage (V_oc) and short-circuit current density (J_sc) to boost power-conversion efficiency (PCE) is a major challenge for organic solar cells (OSCs), wherein high energy loss (E_loss) and inefficient charge transfer usually take place. Here, three new Y-series acceptors of mono-asymmetric asy-YC11 and dual-asymmetric bi-asy-YC9 and bi-asy-YC12 are developed. They share the same asymmetric D₁AD₂ (D₁=thieno[3,2-b]thiophene and D₂=selenopheno[3,2-b]thiophene) fused-core but have different unidirectional sidechain on D₁ side, allowing fine-tuned molecular properties, such as intermolecular interaction, packing pattern, and crystallinity. Among the binary blends, the PM6 : bi-asy-YC12 one has better morphology with appropriate phase separation and higher order packing than the PM6 : asy-YC9 and PM6 : bi-asy-YC11 ones. Therefore, the PM6 : bi-asy-YC12-based OSCs offer a higher PCE of 17.16 % with both high V_oc and J_sc, due to the reduced E_loss and efficient charge transfer properties. Inspired by the high V_oc and strong NIR-absorption, bi-asy-YC12 is introduced into efficient binary PM6 : L8-BO to construct ternary OSCs. Thanks to the broadened absorption, optimized morphology, and furtherly minimized E_loss, the PM6 : L8-BO : bi-asy-YC12-based OSCs achieve a champion PCE of 19.23 %, which is one of the highest efficiencies among these annealing-free devices. Our developed unidirectional sidechain engineering for constructing bi-asymmetric Y-series acceptors provides an approach to boost PCE of OSCs.     

Synthesis and Application of Rylene Imide Dyes as Organic Semiconducting Materials

Rylene imide dyes have been among the most promising organic semiconducting materials for several years due to their remarkable optoelectronic properties and high chemical/thermal stability. In the past decades, various excellent rylene imide dyes have been developed for optoelectronic devices, such as organic solar cells (OSCs) and organic field‐effect transistors (OFETs). Recently, tremendous progress of perylene diimides (PDIs) and their analogues for use in OSCs has been achieved, which can be attributed to their ease of functionalization. In this review, we will mainly focus on the synthetic strategies toward to latest PDI dyes and higher rylene imide analogues. A variety of compounds synthesized from different building blocks are summarized, and some properties and applications are discussed.     

Unsymmetrically Chlorinated Non-Fused Electron Acceptor Leads to High-Efficiency and Stable Organic Solar Cells

Searching the cost-effective organic semiconductors is strongly needed in order to facilitate the practice of organic solar cells (OSCs), yet to be fulfilled. Herein, we have succeeded in developing two non-fused ring electron acceptors (NFREAs), leading to the highest efficiency of 16.2 % for the NFREA derived OSCs. These OSCs exhibit the superior operational stabilities under one sun equivalent illumination without ultraviolet (UV) filtration. It is revealed that the modulation of halogen substituents on aromatic side chains, as the new structural tool to tune the intermolecular interaction and optoelectronic properties of acceptors, not only promotes the interlocked tic-tac-toe frame of three-dimensional stacks in solid, but also improves charge dynamics of acceptors to enable high-performance and stable OSCs.     

基于非富勒烯小分子受体Y6的有机太阳能电池

随着给/受体材料的不断发展,有机太阳能电池的器件效率不断取得进展.特别是非富勒受体分子Y6的出现,使单结有机太阳能电池的效率突破了15％.Y6已经应用到了有机太阳能电池各个方面并且极大提升了其性能.本综述主要总结了Y6在二元、三元和四元、逐层印刷、柔性、叠层和半透明等有机太阳能电池方面的研究情况,以及基于Y6三线态的有...     

Performance enhancement in organic solar cells and photodetectors enabled by donor phase optimization at the surface of hole transport layer

The domain purity, material crystallinity and distribution at the interface between the active layer and the transport layer have an important impact on the performance of organic solar cells (OSCs) and organic photodetectors (OPDs), while this focal issue has received less attention in previous studies. From this perspective, a new method to simultaneously enhance the performance of OSC and OPD is proposed, namely, using a sequential deposition method to first construct a compact stacking structure of dual-donor (D18-Cl:PTO2) eutectic in the donor layer, and then induce the ordered deposition of the acceptor (Y6). Compared with the conventional bulk heterojunction (BHJ), the active layer realized by this method not only improves the crystallinity and stacking order of the constituent material on the surface of the transport layer, but also regulates a good vertical distribution, which is conducive to improving the charge transport and extraction efficiency, reducing the leakage current, and enhancing the stability of the device. As a result, the OSC device based on the D18-Cl:PTO2/Y6 structure achieves a power conversion efficiency of up to 17.65% and good light-degradation stability, which is much better than that of BHJ-based OSC (PCE of 16.37%). For the OPD, the dark current at reverse bias is reduced by more than an order of magnitude, and the maximum responsivity is improved to 0.52 A/W through the optimization of the donor phase at the interface. Moreover, the strategy does not require additional post-processing compared to the BHJ preparation, which reduces the device construction cost and process complexity, providing an effective way for developing high-performance organic optoelectronic devices.     

水/醇溶共轭聚合物界面材料及其在光电器件中的应用

相对于传统的无机半导体器件,以有机半导体(特别是聚合物半导体)材料为基础的有机光电器件,可采用与传统印刷技术(例如喷墨打印、卷对卷印刷等)相结合的溶液加工方式制备低成本、大面积、柔性光电器件,因而成为广泛关注的焦点,并得到了快速发展.实现溶液加工的高效有机光电器件的一个关键问题是界面问题——如何避免溶液加工时有机层间的互溶以及如何实现可印刷稳定金属电极的高效电子注入等.水/醇溶性共轭聚合物的迅速发展为解决溶液加工多层有机光电器件所面临的界面问题提供了有效手段.研究发现,水/醇溶共轭聚合物不但可以有效避免溶液加工多层器件中的界面互溶,而且还可与高功函数的稳定金属发生界面偶极相互作用而增强其电子注入,从而解决了高功函数稳定金属电子注入的难题,为实现全溶液加工的高效印刷有机光电器件提供了可行的方案.本文介绍了近年来本课题组在水/醇溶共轭聚合物阴极界面材料及器件应用方面的研究进展,并对水/醇溶共轭聚合物阴极界面材料在聚合物发光二极管和聚合物太阳电池中的工作机理进行了探讨.     

Double Asymmetric Core Optimizes Crystal Packing to Enable Selenophene-based Acceptor with Over 18 % Efficiency in Binary Organic Solar Cells

Side-chain tailoring is a promising method to optimize the performance of organic solar cells (OSCs). However, asymmetric alkyl chain-based small molecular acceptors (SMAs) are still difficult to afford. Herein, we adopted a novel asymmetric n-nonyl/undecyl substitution strategy and synthesized two A-D₁A′D₂-A double asymmetric isomeric SMAs with asymmetric selenophene-based central core for OSCs. Crystallographic analysis indicates that AYT9Se11-Cl forms a more compact and order intermolecular packing compared to AYT11Se9-Cl , which contributed to higher electron mobility in neat AYT9Se11-Cl film. Moreover, the PM6 : AYT9Se11-Cl blend film shows a better morphology with appropriate phase separation and distinct face-on orientation than PM6 : AYT11Se9-Cl . The OSCs with PM6 : AYT9Se11-Cl obtain a superior PCE of 18.12 % compared to PM6 : AYT11Se9-Cl (17.52 %), which is the best efficiency for the selenium-incorporated SMAs in binary BHJ OSCs. Our findings elucidate that the promising double asymmetric strategy with isomeric alkyl chains precisely modulates the crystal packing and enhances the photovoltaic efficiency of selenophene-incorporated SMAs.     

A chlorinated non-fullerene acceptor for efficient polymer solar cells

Improving the performance and reducing the manufacturing costs are the main directions for the development of organic solar cells in the future. Here, the strategy that uses chemical structure modification to optimize the photoelectric properties is reported. A new narrow bandgap (1.30 eV) chlorinated non-fullerene electron acceptor (Y15), based on benzo[d][1,2,3] triazole with two 3-undecyl-thieno[2′,3′:4,5] thieno[3,2-b] pyrrole fused -7-heterocyclic ring, with absorption edge extending to the near-infrared (NIR) region, namely A-DA'D-A type structure, is designed and synthesized. Its electrochemical and optoelectronic properties are systematically investigated. Benefitting from its NIR light harvesting, the fabricated photovoltaic devices based on Y15 deliver a high power conversion efficiency (PCE) of 14.13%, when blending with a wide bandgap polymer donor PM6. Our results show that the A-DA'D-A type molecular design and application of near-infrared electron acceptors have the potential to further improve the PCE of polymer solar cells (PSCs).     

Two star-shaped small molecule donors based on benzodithiophene unit for organic solar cells

Star-shaped small molecules have attracted great attention for organic solar cells(OSCs) because they have three-dimensional charge-transport characteristics, strong light absorption capacities and easily tunable energy levels. Herein, three-and four-armed star-shaped small molecule donors, namely BDT-3 Th and BDT-4 Th, respectively, have been successfully designed and synthesized, which used benzodithiophene(BDT) as the central unit. The two star-shaped intermediates(2 a and 2 b) could be simul...     

A chlorinated non-fullerene acceptor for efficient polymer solar cells

After additive and thermal annealing treatment, the PM6:Y15 based device obtains a high power conversion efficiency of 14.13%.     

Ternary solvent-processed efficient organic solar cells based on a new A-DA'D-A acceptor derivative employing the 3rd-position branching side chains on pyrroles

Recent advances in non-fullerene acceptors(NFAs),typically Y6,have driven power conversion efficiency(PCE) of single-junction orga nic solar cells(OSCs) over 16%.Mea nwhile,it becomes essential to know how to adopt simple strategies to further improve device performance.In this work,a new A-DA'D-A acceptor derivative,Y19-N3 employing 3-ethylheptyl branched at the 3^rd-position instead of 2-ethylhexyl on the pyrroles of Y19 is reported.The selection of an appropriate solvent in casting device is implemented to maximize the photovoltaic performance.PBDB-T:Y19-N3-based OSCs treated with a ternary solvent of CF/CB(1:3,v/v) and 0.8% DIO exhibit the optimal PCE of 13.77% here,with the significantly improved V_oc(0.78 V) and FF(0.72) as well as the high J_sc(24.46 mA/cm²).Further characterizations indicate that this ternary solvent-treated PBDB-T/Y19-N3 film exhibits the more appropriate morphological features with the highly efficient charge generation and collection as well as the more balanced electron and hole mobilities.This work combines molecular design and device engineering to improve the photovoltaic properties,which is important to the development of OSCs.