High-Performance All-Polymer Solar Cells Enabled by n-Type Polymers with an Ultranarrow Bandgap Down to 1.28 eV

Compared to organic solar cells based on narrow-bandgap nonfullerene small-molecule acceptors, the performance of all-polymer solar cells (all-PSCs) lags much behind due to the lack of high-performance n-type polymers, which should have low-aligned frontier molecular orbital levels and narrow bandgap with broad and intense absorption extended to the near-infrared region. Herein, two novel polymer acceptors, DCNBT-TPC and DCNBT-TPIC, are synthesized with ultranarrow bandgaps (ultra-NBG) of 1.38 and 1.28 eV, respectively. When applied in transistors, both polymers show efficient charge transport with a highest electron mobility of 1.72 cm² V⁻¹ s⁻¹ obtained for DCNBT-TPC. Blended with a polymer donor, PBDTTT-E-T, the resultant all-PSCs based on DCNBT-TPC and DCNBT-TPIC achieve remarkable power conversion efficiencies (PCEs) of 9.26% and 10.22% with short-circuit currents up to 19.44 and 22.52 mA cm⁻², respectively. This is the first example that a PCE of over 10% can be achieved using ultra-NBG polymer acceptors with a photoresponse reaching 950 nm in all-PSCs. These results demonstrate that ultra-NBG polymer acceptors, in line with nonfullerene small-molecule acceptors, are also available as a highly promising class of electron acceptors for maximizing device performance in all-PSCs.     

A Narrow-Bandgap n-Type Polymer with an Acceptor–Acceptor Backbone Enabling Efficient All-Polymer Solar Cells

Narrow-bandgap polymer semiconductors are essential for advancing the development of organic solar cells. Here, a new narrow-bandgap polymer acceptor L14, featuring an acceptor–acceptor (A–A) type backbone, is synthesized by copolymerizing a dibrominated fused-ring electron acceptor (FREA) with distannylated bithiophene imide. Combining the advantages of both the FREA and the A–A polymer, L14 not only shows a narrow bandgap and high absorption coefficient, but also low-lying frontier molecular orbital (FMO) levels. Such FMO levels yield improved electron transfer character, but unexpectedly, without sacrificing open-circuit voltage (V_oc), which is attributed to a small nonradiative recombination loss (E_loss,nr) of 0.22 eV. Benefiting from the improved photocurrent along with the high fill factor and V_oc, an excellent efficiency of 14.3% is achieved, which is among the highest values for all-polymer solar cells (all-PSCs). The results demonstrate the superiority of narrow-bandgap A–A type polymers for improving all-PSC performance and pave a way toward developing high-performance polymer acceptors for all-PSCs.     

Optimized Fibril Network Morphology by Precise Side‐Chain Engineering to Achieve High‐Performance Bulk‐Heterojunction Organic Solar Cells

A polymer fibril assembly can dictate the morphology framework, in forming a network structure, which is highly advantageous in bulk heterojunction (BHJ) organic solar cells (OSCs). A fundamental understanding of how to manipulate such a fibril assembly and its influence on the BHJ morphology and device performance is crucially important. Here, a series of donor–acceptor polymers, PBT1‐O, PBT1‐S, and PBT1‐C, is used to systematically investigate the relationship between molecular structure, morphology, and photovoltaic performance. The subtle atom change in side chains is found to have profound effect on regulating electronic structure and self‐assembly of conjugated polymers. Compared with PBT1‐O and PBT1‐S, PBT1‐C‐based OSCs show much higher photovoltaic performance with a record fill factor (FF) of 80.5%, due to the formation of optimal interpenetrating network morphology. Such a fibril network strategy is further extended to nonfullerene OSCs using a small‐molecular acceptor, which shows a high efficiency of 12.7% and an FF of 78.5%. The results indicate the formation of well‐defined fibrillar structure is a promising approach to achieving a favorable morphology in BHJ OSCs.     

1 cm2 Organic Photovoltaic Cells for Indoor Application with over 20% Efficiency

Organic photovoltaic (OPV) technologies have the advantages of fabricating larger‐area and light‐weight solar panels on flexible substrates by low‐cost roll‐to‐toll production. Recently, OPV cells have achieved many significant advances with power conversion efficiency (PCE) increasing rapidly. However, large‐scale solar farms using OPV modules still face great challenges, such as device stability. Herein, the applications of OPV cells in indoor light environments are studied. Via optimizing the active layers to have a good match with the indoor light source, 1 cm² OPV cells are fabricated and a top PCE of 22% under 1000 lux light‐emitting diode (2700 K) illumination is demonstrated. In this work, the light intensities are measured carefully. Incorporated with the external quantum efficiency and photon flux spectrum, the integral current densities of the cells are calculated to confirm the reliability of the photovoltaic measurement. In addition, the devices show much better stability under continuous indoor light illumination. The results suggest that designing wide‐bandgap active materials to meet the requirements for the indoor OPV cells has a great potential in achieving higher photovoltaic performance.     

Ternary System with Controlled Structure: A New Strategy toward Efficient Organic Photovoltaics

Recently, a new type of active layer with a ternary system has been developed to further enhance the performance of binary system organic photovoltaics (OPV). In the ternary OPV, almost all active layers are formed by simple ternary blend in solution, which eventually leads to the disordered bulk heterojunction (BHJ) structure after a spin‐coating process. There are two main restrictions in this disordered BHJ structure to obtain higher performance OPV. One is the isolated second donor or acceptor domains. The other is the invalid metal–semiconductor contact. Herein, the concept and design of donor/acceptor/acceptor ternary OPV with more controlled structure (C‐ternary) is reported. The C‐ternary OPV is fabricated by a sequential solution process, in which the second acceptor and donor/acceptor binary blend are sequentially spin‐coated. After the device optimization, the power conversion efficiencies (PCEs) of all OPV with C‐ternary are enhanced by 14–21% relative to those with the simple ternary blend; the best PCEs are 10.7 and 11.0% for fullerene‐based and fullerene‐free solar cells, respectively. Moreover, the averaged PCE value of 10.4% for fullerene‐free solar cell measured in this study is in great agreement with the certified one of 10.32% obtained from Newport Corporation.     

Formation of organic crystalline nanopillar arrays and their application to organic photovoltaic cells

To enhance the performance of organic photovoltaic (OPV) cells, preparation of organic nanometer-sized pillar arrays is fascinating because a significantly large area of a donor/acceptor heterointerface having continuous conduction path to both anode and cathode electrodes can be realized. In this study, we grew cupper phthalocyanine (CuPc) crystalline nanopillar arrays by conventional thermal gradient sublimation technique using a few-nanometer-sized trigger seeds composed of a CuPc and 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) stacked layer. We optimized the pillar density by tuning crystal growth condition in order to apply it to OPV cells.     

Improving Cooperative Interactions Between Halogenated Aromatic Additives and Aromatic Side Chain Acceptors for Realizing 19.22% Efficiency Polymer Solar Cells

Processing additive plays an important role in the standard operation procedures for fabricating top performing polymer solar cells (PSCs) through efficient interactions with key photovoltaic materials. However, improving interaction study of acceptor materials to high performance halogenated aromatic additives such as diiodobenzene (DIB) is a widely neglected route for molecular engineering toward more efficient device performances. In this work, two novel Y-type acceptor molecules of BTP-TT and BTP-TTS with different aromatic side chains on the outer positions are designed and synthesized. The resulting aromatic side chains significantly enhanced the interactions between the acceptor molecules and DIB through an arene/halogenated arene interaction, which improved the crystallinity of the acceptor molecules and induced a polymorph with better photovoltaic performances. Thus, high power conversion efficiencies (PCEs) of 18.04% and 19.22% are achieved in binary and ternary blend devices using BTP-TTS as acceptor and DIB as additive. Aromatic side chain engineering for improving additive interactions is proved to be an effective strategy for achieving much higher performance photovoltaic materials and devices.     

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.     

Power from plastic

Solar power is the most abundant renewable resource on our planet. In spite of this abundance, only 0.04% of the basic power used by humans comes directly from solar sources because harvesting solar energy using a photovoltaic (PV) panel costs more than burning fossil fuels. Solution-processable organic materials have recently been intensively studied for PV applications, not because they show a possibility for harvesting the sun’s power more efficiently, but because power generation from organic photovoltaic (OPV) materials will cost considerably less than other PV technologies. The cost/Watt savings comes from the possibility of using flexible substrates, using printable organic inks for the active layers, light-weight transport, low temperature and ambient pressure fabrication, and reduced materials costs. The ability to use solution processes for deposition is particularly exciting because products such as automobiles, freight containers, and building materials could be painted with photovoltaic coatings. This article gives an overview of the current state-of-the-art for OPV technology and discusses scientific issues that need to be addressed to facilitate scale-up of OPV.     

The Importance of Quantifying the Composition of the Amorphous Intermixed Phase in Organic Solar Cells

The relation of phase morphology and solid-state microstructure with organic photovoltaic (OPV) device performance has intensely been investigated over the last twenty years. While it has been established that a combination of donor:acceptor intermixing and presence of relatively phase-pure donor and acceptor domains is needed to get an optimum compromise between charge generation and charge transport/charge extraction, a quantitative picture of how much intermixing is needed is still lacking. This is mainly due to the difficulty in quantitatively analyzing the intermixed phase, which generally is amorphous. Here, fast scanning calorimetry, which allows measurement of device-relevant thin films (<200 nm thickness), is exploited to deduce the precise composition of the intermixed phase in bulk-heterojunction structures. The power of fast scanning calorimetry is illustrated by considering two polymer:fullerene model systems. Somewhat surprisingly, it is found that a relatively small fraction (<15 wt%) of an acceptor in the intermixed amorphous phase leads to efficient charge generation. In contrast, charge transport can only be sustained in blends with a significant amount of the acceptor in the intermixed phase (in this case: ≈58 wt%). This example shows that fast scanning calorimetry is an important tool for establishing a complete compositional characterization of organic bulk heterojunctions. Hence, it will be critical in advancing quantitative morphology–function models that allow for the rational design of these devices, and in delivering insights in, for example, solar cell degradation mechanisms via phase separation, especially for more complex high-performing systems such as nonfullerene acceptor:polymer bulk heterojunctions.     

Recent Advances in Organic Photovoltaics: Device Structure and Optical Engineering Optimization on the Nanoscale

Organic photovoltaic (OPV) devices, which can directly convert absorbed sunlight to electricity, are stacked thin films of tens to hundreds of nanometers. They have emerged as a promising candidate for affordable, clean, and renewable energy. In the past few years, a rapid increase has been seen in the power conversion efficiency of OPV devices toward 10% and above, through comprehensive optimizations via novel photoactive donor and acceptor materials, control of thin‐film morphology on the nanoscale, device structure developments, and interfacial and optical engineering. The intrinsic problems of short exciton diffusion length and low carrier mobility in organic semiconductors creates a challenge for OPV designs for achieving optically thick and electrically thin device structures to achieve sufficient light absorption and efficient electron/hole extraction. Recent advances in the field of OPV devices are reviewed, with a focus on the progress in device architecture and optical engineering approaches that lead to improved electrical and optical characteristics in OPV devices. Successful strategies are highlighted for light wave distribution, modulation, and absorption promotion inside the active layer of OPV devices by incorporating periodic nanopatterns/nanostructures or incorporating metallic nanomaterials and nanostructures.     

Developments of Diketopyrrolopyrrole-Dye-Based Organic Semiconductors for a Wide Range of Applications in Electronics

In recent times, fused aromatic diketopyrrolopyrrole (DPP)-based functional semiconductors have attracted considerable attention in the developing field of organic electronics. Over the past few years, DPP-based semiconductors have demonstrated remarkable improvements in the performance of both organic field-effect transistor (OFET) and organic photovoltaic (OPV) devices due to the favorable features of the DPP unit, such as excellent planarity and better electron-withdrawing ability. Driven by this success, DPP-based materials are now being exploited in various other electronic devices including complementary circuits, memory devices, chemical sensors, photodetectors, perovskite solar cells, organic light-emitting diodes, and more. Recent developments in the use of DPP-based materials for a wide range of electronic devices are summarized, focusing on OFET, OPV, and newly developed devices with a discussion of device performance in terms of molecular engineering. Useful guidance for the design of future DPP-based materials and the exploration of more advanced applications is provided.     

体相异质结型有机太阳能电池的研究进展

基于电子给/受体共混体系制备的体相异质结型有机太阳能电池是一种低耗、高效的有机光伏器件.作为器件核心,光电转化共混活性层的质量优劣会直接影响器件的能量转换效率.研究发现,不同的给/受体材料组成、2种材料的共混比例、共溶剂的选择以及器件的热退火处理等因素都可影响到活性层质量.结合上述研究热点,综述了体相异质结型有机太阳能电池近年来的研究进展,阐述了该研究领域下一步发展的重点、趋势及前景.     

The significance of fullerene electron acceptors in organic solar cell photo-oxidation

Stability of organic solar cells requires development before their commercialisation is possible. This review will give a brief overview of organic solar cells and their stability, before focussing on the photochemical stability of the active layer. The photo-oxidation of the donor polymers will be looked at first which has been studied quite extensively and then fullerene electron acceptors, such as widely used phenyl-C61-butyric acid methyl ester, which has been considerably less studied. It has been shown that oxidation of the fullerene cage on phenyl-C61-butyric acid methyl ester results in oxides with a deeper lowest unoccupied molecular orbital (LUMO) level than the fresh electron acceptor. These oxides act as electron traps, leading to deterioration of the blend photoconductivity. The significance of fullerene photo-oxidation on device stability has been indirectly shown via research on: photoconductivity; organic solar cells made with an oxidised fullerene derivative and organic field effect transistors. Techniques that could be developed to increase photochemical stability of fullerene electron acceptor resistance to photo-oxidation include: reducing its LUMO level; increasing its crystallinity or aggregation and changing its chemical structure. Improving the photochemical stability of organic solar cells would move us one step closer to a more accessible solar power.     

Morphological control of CuPc and its application in organic solar cells

We have prepared organic photovoltaic (OPV) cells possessing an ideal bulk heterojunction (BHJ) structure using the self-assembly of copper phthalocyanine (CuPc) as the donor material and fullerene (C(60)) as the acceptor. The variable self-assembly behavior of CuPc on a diverse range of substrates (surface energies) allowed us to control the morphology of the interface and the degree of carrier transportation within the active layer. We observed rod-like CuPc structures on indium-tin oxide (ITO), poly(3,4-ethylenedioxythiophene)-poly(4-styrenesulfonate) (PEDOT:PSS) and Au substrates. Accordingly, the interfaces and continuing transport path between CuPc and fullerene domains could be greatly improved due to the ideal BHJ structure. In this paper, we discuss the mechanisms of producing CuPc rod-like films on ITO, PEDOT:PSS and Au. The OPV cell performance was greatly enhanced when a mixture of horizontal and vertical CuPc rods was present on the PEDOT:PSS surfaces, i.e.?the power conversion efficiency was 50 times greater than that of the corresponding device featuring a planar CuPc structure.     

A Benzo[1,2-b:4,5-c′]Dithiophene-4,8-Dione-Based Polymer Donor Achieving an Efficiency Over 16%

It is of great significance to develop efficient donor polymers during the rapid development of acceptor materials for nonfullerene bulk-heterojunction (BHJ) polymer solar cells. Herein, a new donor polymer, named PBTT-F, based on a strongly electron-deficient core (5,7-dibromo-2,3-bis(2-ethylhexyl)benzo[1,2-b:4,5-c′]dithiophene-4,8-dione, TTDO), is developed through the design of cyclohexane-1,4-dione embedded into a thieno[3,4-b]thiophene (TT) unit. When blended with the acceptor Y6, the PBTT-F-based photovoltaic device exhibits an outstanding power conversion efficiency (PCE) of 16.1% with a very high fill factor (FF) of 77.1%. This polymer also shows high efficiency for a thick-film device, with a PCE of ≈14.2% being realized for an active layer thickness of 190 nm. In addition, the PBTT-F-based polymer solar cells also show good stability after storage for ≈700 h in a glove box, with a high PCE of ≈14.8%, which obviously shows that this kind of polymer is very promising for future commercial applications. This work provides a unique strategy for the molecular synthesis of donor polymers, and these results demonstrate that PBTT-F is a very promising donor polymer for use in polymer solar cells, providing an alternative choice for a variety of fullerene-free acceptor materials for the research community.     

Controlled growth of a molecular bulk heterojunction photovoltaic cell.

The power conversion efficiency of organic photovoltaic cells has increased with the introduction of the donor-acceptor heterojunction that serves to dissociate strongly bound photogenerated excitons. Further efficiency increases have been achieved in both polymer and small-molecular-mass organic photovoltaic cells through the use of the bulk heterojunction (BHJ), where the distance an exciton must diffuse from its generation to its dissociation site is reduced in an interpenetrating network of the donor and acceptor materials. However, the random distribution of donor and acceptor materials in such structures can lead to charge trapping at bottlenecks and cul-de-sacs in the conducting pathways to the electrodes. Here, we present a method for growing crystalline organic films into a controlled bulk heterojunction; that is, the positions and orientations of donor and acceptor materials are determined during growth by organic vapour-phase deposition (OVPD), eliminating contorted and resistive conducting pathways while maximizing the interface area. This results in a substantial increase in power conversion efficiency compared with the best values obtained by 'random' small-molecular-weight BHJ solar cells formed by high-temperature annealing, or planar double heterojunction photovoltaic cells using the same archetypal materials systems.     

Investigation of post-thermal annealing-induced enhancement in photovoltaic performance for squaraine-based organic solar cells

In this work, we have systematically investigated the post-thermal annealing-induced enhancement in photovoltaic performance of a 2,4-bis[4-(N, N-diisobutylamino)-2,6-dihydroxyphenyl] squaraine (DIBSQ)/C₆₀ planar heterojunction (PHJ) organic solar cells (OSCs). An increased power conversion efficiency (PCE) of 3.28% has been realized from a DIBSQ/C₆₀ device with thermal annealing at 100 °C for 4 min, which is about 33% enhancement compared with that of the as-cast device. The improvement of the device performance may be mainly ascribed to the crystallinity of the DIBSQ film with post-thermal annealing, which will change the DIBSQ donor and C₆₀ acceptor interface from PHJ to hybrid planar-mixed heterojunction. This new donor–acceptor heterojunction structure will significantly improve the charge separation and charge collection efficiency, as well as the open circuit voltage (V_oc) of the device, leading to an enhanced PCE. This work provides an effective strategy to improve the photovoltaic performance of SQ-based OSCs.     

Hierarchical nanomorphologies promote exciton dissociation in polymer/fullerene bulk heterojunction solar cells

PTB7 semiconducting copolymer comprising thieno[3,4-b]thiophene and benzodithiophene alternating repeat units set a historic record of solar energy conversion efficiency (7.4%) in polymer/fullerene bulk heterojunction solar cells. To further improve solar cell performance, a thorough understanding of structure-property relationships associated with PTB7/fullerene and related organic photovoltaic (OPV) devices is crucial. Traditionally, OPV active layers are viewed as an interpenetrating network of pure polymers and fullerenes with discrete interfaces. Here we show that the active layer of PTB7/fullerene OPV devices in fact involves hierarchical nanomorphologies ranging from several nanometers of crystallites to tens of nanometers of nanocrystallite aggregates in PTB7-rich and fullerene-rich domains, themselves hundreds of nanometers in size. These hierarchical nanomorphologies are coupled to significantly enhanced exciton dissociation, which consequently contribute to photocurrent, indicating that the nanostructural characteristics at multiple length scales is one of the key factors determining the performance of PTB7 copolymer, and likely most polymer/fullerene systems, in OPV devices.     

Recent Advances in Wide‐Bandgap Photovoltaic Polymers

The past decade has witnessed significant advances in the field of organic solar cells (OSCs). Ongoing improvements in the power conversion efficiency of OSCs have been achieved, which were mainly attributed to the design and synthesis of novel conjugated polymers with different architectures and functional moieties. Among various conjugated polymers, the development of wide‐bandgap (WBG) polymers has received less attention than that of low‐bandgap and medium‐bandgap polymers. Here, we briefly summarize recent advances in WBG polymers and their applications in organic photovoltaic (PV) devices, such as tandem, ternary, and non‐fullerene solar cells. Addtionally, we also dissuss the application of high open‐circuit voltage tandem solar cells in PV‐driven electrochemical water dissociation. We mainly focus on the molecular design strategies, the structure‐property correlations, and the photovoltaic performance of these WBG polymers. Finally, we extract empirical regularities and provide invigorating perspectives on the future development of WBG photovoltaic materials.