Crystalline Conjugated Polymers for Organic Solar Cells: From Donor,Acceptor to Single‐Component

Organic solar cells have made rapid progress in the last two decades due to the innovation of conjugated materials and photovoltaic devices. Microphase separation that connects with materials and devices plays a crucial role in the charge generation process. In this account, we summary our recent works of developing new crystalline conjugated polymers to control the microphase separation in thin films in order to realize high performance in solar cells, including crystalline diketopyrrolopyrrole‐based donor polymers, perylene bisimide‐based electron acceptors, and “double‐cable” conjugated polymers that contain covalently‐linked crystalline donor and acceptor in one material for single‐component organic solar cells.     

Recent Advances in Mechanically Robust and Stretchable Bulk Heterojunction Polymer Solar Cells

Organic bulk heterojunction solar cells are promising candidates as future photovoltaic technologies for large‐scale and low‐cost energy production. It is, therefore, not surprising that research on the design and preparation of these types of organic photovoltaics has attracted a lot of attention since the last two decades, leading to constantly growing values of energy conversion and efficiency. Combined with the possibility of a large‐scale production via roll‐to‐roll printing techniques, bulk heterojunction solar cells enable the fabrication of conformable, light‐weight and flexible light‐harvesting devices for point‐of‐use applications. This perspective review will highlight the recent advances toward mechanically robust and intrinsically stretchable bulk heterojunction solar cells. Mechanically robust fullerene‐based and all‐polymer devices will be presented, as well as a comprehensive overview of the recent challenges and characterization techniques recently developed to overcome some of the challenges of this research area, which is still in its infancy.     

有机染料敏化纳米晶太阳能电池

本文综述了有机染料敏化纳米晶太阳能电池的研究现状,简要介绍了有机染料敏化纳米晶太阳能电池的结构和工作原理以及氧化物电极、对电极和电解质的设计思路和制备情况。重点介绍了有机染料的研究现状,包括香豆素类染料、多烯类染料、噻吩类染料、天然染料、半花菁类染料、卟啉类染料、三苯胺类染料、苝类染料等。同时讨论了若干影响有机染料敏化太阳能电池性能的因素,提出了提高光电转换效率的设想与对策,对未来的发展进行了展望。     

Benzothiadiazole-based Conjugated Polymers for Organic Solar Cells

Benzothiadiazole(BT) is an electron-deficient unit with fused aromatic core, which can be used to construct conjugated polymers for application in organic solar cells(OSCs). In the past twenty years, huge numbers of conjugated polymers based on BT unit have been developed,focusing on the backbone engineering(such as by using different copolymerized building blocks), side chain engineering(such as by using linear or branch side units), using heteroatoms(such as F, O and S atoms, and CN group), etc. These modifications enable BT-polymers to exhibit distinct absorption spectra(with onset varied from 600 nm to 1000 nm), different frontier energy levels and crystallinities. As a consequence, BT-polymers have gained much attention in recent years, and can be simultaneously used as electron donor and electron acceptor in OSCs, providing the power conversion efficiencies(PCEs) over 18% and 14% in non-fullerene and all-polymer OSCs. In this article, we provide an overview of BTpolymers for OSCs, from donor to acceptor, via selecting some typical BT-polymers in different periods. We hope that the summary in this article can invoke the interest to study the BT-polymers toward high performance OSCs, especially with thick active layers that can be potentially used in large-area devices.     

Naphthalene-Diimide-Based Ionenes as Universal Interlayers for Efficient Organic Solar Cells

Self-doping ionene polymers were efficiently synthesized by reacting functional naphthalene diimide (NDI) with 1,3-dibromopropane ( NDI-NI ) or trans-1,4-dibromo-2-butene ( NDI-CI ) via quaternization polymerization. These NDI-based ionene polymers are universal interlayers with random molecular orientation, boosting the efficiencies of fullerene-based, non-fullerene-based, and ternary organic solar cells (OSCs) over a wide range of interlayer thicknesses, with a maximum efficiency of 16.9 %. NDI-NI showed a higher interfacial dipole (Δ), conductivity, and electron mobility than NDI-CI , affording solar cells with higher efficiencies. These polymers proved to efficiently lower the work function (WF) of air-stable metals and optimize the contact between metal electrode and organic semiconductor, highlighting their power to overcome energy barriers of electron injection and extraction processes for efficient organic electronics.     

苯并噻二唑单元在聚合物光伏材料设计中的应用

聚合物太阳能电池因其易于加工、可制备成柔性器件、材料来源广泛等优点得到材料界和能源界的广泛关注。有机太阳能电池效率的不断提高主要得益于材料的发展和电池器件结构的优化。从材料设计角度考虑,种类众多的给体和受体单元被开发用来构建有机共轭分子,其中,苯并噻二唑单元由于共轭平面较大和吸电子性较强的特性被广泛用于构建高性能的有机太阳能电池材料。基于此,本文首先介绍了苯并二噻吩单元及其衍生物常见的合成方法,随后总结了其在构建聚合物给体方面的应用,最后对其后续发展方向和前景提出了展望。     

Benzodithiophene-Fused Perylene Bisimides as Electron Acceptors for Non-Fullerene Organic Solar Cells with High Open-Circuit Voltage

Tandem-junction organic solar cells require solar cells with visible light photo-response as front cells, in which an open-circuit voltage (V_oc) above 1.0 V is highly demanded. In this work, we are able to develop electron acceptors to fabricate non-fullerene organic solar cells (NFOSCs) with a very high V_oc of 1.14 V. This was realized by designing perylene bisimide (PBI)-based conjugated materials fused with benzodithiophene, in which Cl and S atom were introduced into the molecules in order to lower the frontier energy levels. The fused structures can reduce the aggregation of PBI unit and meanwhile maintain a good charge transport property. The new electron acceptors were applied into NFOSCs by using Cl and S substituted conjugated polymers as electron donor, in which an initial power conversion efficiency of 6.63 % and a high V_oc of 1.14 V could be obtained. The results demonstrate that the molecular design by incorporating Cl and S atom into electron acceptors has great potential to realize high performance NFOSCs.     

Improving the Efficiency of Organic Solar Cells with Methionine as Electron Transport Layer

Interface modification is an important way to get better performance from organic solar cells (OSCs). A natural biomolecular material methionine was successfully applied as the electron transport layer (ETL) to the inverted OSCs in this work. A series of optical, morphological, and electrical characterizations of thin films and devices were used to analyze the surface modification effects of methionine on zinc oxide (ZnO). The analysis results show that the surface modification of ZnO with methionine can cause significantly reduced surface defects for ZnO, optimized surface morphology of ZnO, improved compatibility between ETL and the active layer, better-matched energy levels between ETL and the acceptor, reduced interface resistance, reduced charge recombination, and enhanced charge transport and collection. The power conversion efficiency (PCE) of OSCs based on PM6:BTP-ec9 was improved to 15.34% from 14.25% by modifying ZnO with methionine. This work shows the great application potential of natural biomolecule methionine in OSCs.     

Side-chains Engineering of Conjugated Polymers toward Additive-free Non-fullerene Organic Solar Cells

Side-chain engineering plays a significant role in the design of conjugated materials. In this work, a series of conjugated polymers PBDB-T-R with functionalized groups at the end of side units were developed as electron donor for organic solar cells(OSCs). The donor polymers PBDB-T-I and PBDB-T-OAc with iodine and acetate end groups exhibited similar absorption and energy levels, but showed much improved PCEs in OSCs compared to the polymer PBDB-T-H without substitutions at the end groups. Additionally, we found that PBDB-T-I and PBDB-T-OAc based cells exhibited optimized performance when using chloroform as solution-processed solvent without any additives. These results indicate that these conjugated polymers can act as self-additive to fabricate photoactive layers via solution process in OSCs.     

有机太阳能电池简介与展望

太阳能是一种非常重要的可再生能源。将太阳能转化为电能的有机太阳能电池,因其具有重量轻,柔韧性好,可以进行大面积、低成本的柔性制备等优点,为解决未来全球的能源问题提供了一种选择。简要介绍了有机太阳能电池的发展、性能参数、工作机理和应用实例。     

Advanced Acceptor-Substituted S,N-Heteropentacenes for Application in Organic Solar Cells

Ambifunctional heterpentacenes with the heteroatom sequence SSNSS in the ladder-type backbone were used either as donor or as nonfullerenic acceptor in solution-processed bulk-heterojunction solar cells. Different acceptor moieties and side chains were inserted. Synthesis and characterization of the systematically varied structural motifs provided insight in structure-property relationships. Moreover, a dimeric heteroacene was synthesized, and the optoelectronic properties were compared to those of its monomeric counterpart.     

无机材料在有机太阳能电池中的应用

无机材料电子迁移率高、光谱响应范围与太阳光谱匹配,而有机材料价格低廉、合成方法简单、容易制作在基底上,因此在太阳能电池中具有更广阔的应用前景。 目前,阻碍有机太阳能电池发展的主要原因是材料的载流子迁移率低、器件稳定性差、吸收光谱与太阳光谱不匹配,导致光电转换效率较低。 若能将有机、无机材料二者的优点相结合,将可提高有机太阳能电池的能量转换效率。 目前的研究已经取得了一定进展,无机材料在受体层、阴极缓冲层、阳极缓冲层中的应用均不同程度地提高了有机太阳能电池的能量转换效率。 本文综述了目前该领域的研究现状,并对今后的研究提出了展望。     

Recent Progress in Organic Solar Cells: A Review on Materials from Acceptor to Donor

In the last few decades, organic solar cells (OSCs) have drawn broad interest owing to their advantages such as being low cost, flexible, semitransparent, non-toxic, and ideal for roll-to-roll large-scale processing. Significant advances have been made in the field of OSCs containing high-performance active layer materials, electrodes, and interlayers, as well as novel device structures. Particularly, the innovation of active layer materials, including novel acceptors and donors, has contributed significantly to the power conversion efficiency (PCE) improvement in OSCs. In this review, high-performance acceptors, containing fullerene derivatives, small molecular, and polymeric non-fullerene acceptors (NFAs), are discussed in detail. Meanwhile, highly efficient donor materials designed for fullerene- and NFA-based OSCs are also presented. Additionally, motivated by the incessant developments of donor and acceptor materials, recent advances in the field of ternary and tandem OSCs are reviewed as well.     

Electronic Structure and Interface Properties of a Model Molecule for Organic Solar Cells

We study the electronic structure of 4,7‐bis(5‐methylthiophen‐2‐yl)benzo[c][1,2,5]thiadiazole (MTBT) and its interface properties with gold using X‐ray photoemission spectroscopy (XPS), valence‐band ultraviolet photoemission spectroscopy (UPS), X‐ray absorption spectroscopy (XAS), as well as resonant photoemission (ResPES). MTBT can be regarded as a model molecule for PCPDTBT, a promising candidate for efficient bulk heterojunction solar cells. Almost no contribution of sulfur and only a weak contribution of nitrogen to the HOMO level is found. At the interface with gold, a strong chemical interaction between the sulfur of the benzothiadiazole and gold occurs, which may have consequences for interface properties in devices.     

聚合物太阳能电池材料的研究进展

有机光伏技术为太阳能的有效利用提供了一条重要途径。有机太阳能电池因制造成本低廉、材料质量轻、加工性能好、易于携带等优势而备受关注。提高有机太阳能电池的光电转换效率是目前乃至未来的研究重点。设计和合成适合的窄带隙的共轭聚合物是提高有机太阳能电池光电转化效率的核心。综述了近年来基于窄带隙的共轭聚合物的太阳能电池材料的设计、制备和器件性能研究进展,探讨了目前存在的亟待解决的关键基础问题和未来发展方向。     

Triplet Tellurophene‐Based Acceptors for Organic Solar Cells

Triplet materials have been employed to achieve high‐performing organic solar cells (OSCs) by extending the exciton lifetime and diffusion distances, while the triplet non‐fullerene acceptor materials have never been reported for bulk heterojunction OSCs. Herein, for the first time, three triplet molecular acceptors based on tellurophene with different degrees of ring fusing were designed and synthesized for OSCs. Significantly, these molecules have long exciton lifetime and diffusion lengths, leading to efficient power conversion efficiency (7.52 %), which is the highest value for tellurophene‐based OSCs. The influence of the extent of ring fusing on molecular geometry and OSCs performance was investigated to show the power conversion efficiencies (PCEs) continuously increased along with increasing the extent of ring fusing.     

Naphthalene‐Diimide‐Based Ionenes as Universal Interlayers for Efficient Organic Solar Cells

Self‐doping ionene polymers were efficiently synthesized by reacting functional naphthalene diimide (NDI) with 1,3‐dibromopropane ( NDI‐NI ) or trans‐1,4‐dibromo‐2‐butene ( NDI‐CI ) via quaternization polymerization. These NDI‐based ionene polymers are universal interlayers with random molecular orientation, boosting the efficiencies of fullerene‐based, non‐fullerene‐based, and ternary organic solar cells (OSCs) over a wide range of interlayer thicknesses, with a maximum efficiency of 16.9 %. NDI‐NI showed a higher interfacial dipole (Δ), conductivity, and electron mobility than NDI‐CI , affording solar cells with higher efficiencies. These polymers proved to efficiently lower the work function (WF) of air‐stable metals and optimize the contact between metal electrode and organic semiconductor, highlighting their power to overcome energy barriers of electron injection and extraction processes for efficient organic electronics.     

高性能的二维层状材料硫化钨界面层的有机太阳能电池

化学剥离的硫化钨二维层状材料在经过紫外臭氧处理后用作有机太阳能电池的空穴传输层, 可以显著提高电池器件的光电转化效率至8.37%; 作为空穴传输层, 硫化钨二维层状材料可以与经典的空穴传输材料PEDOT:PSS相媲美. 利用X射线光电子能谱(XPS)、拉曼光谱(Raman)、原子力显微镜(AFM)对硫化钨的结构和形貌进行分析. 结果表明, 紫外臭氧处理过后, 氧原子能填充硫化钨因锂插层剥离而产生的硫空位, 减少它的缺陷, 并且使其部分被氧化, 从而改善硫化钨的电学性能.     

有机染料及其在染料敏化太阳电池中的应用

在染料敏化太阳电池中,染料敏化剂分成无机染料与有机染料两大类。无机染料受稀有金属钌的制约而成本较高,开发有机染料是降低染料敏化太阳电池成本的有效手段,成为目前研究的热点。本文从有机染料敏化剂的分子设计入手,简述了染料敏化太阳电池中有机染料敏化剂的基本结构,将有机染料敏化剂分为吲哚啉类染料、香豆素类染料、三苯胺类染料、菁...     

Towards Green Synthesis and Processing of Organic Solar Cells

In 2018, several major breakthroughs have been achieved in organic solar cells (OSCs) with the record power conversion efficiency (PCE) reaching over 17 %. With this increased efficiency, it is time to take a step forward to consider how to convert this technology into large scale production. For this, the economic and environmental profile of OSCs should be taken seriously‐simplified synthetic routes and green chemistry methods should be applied. According to previous studies, OSCs are competitive and profitable in the commercial market. However, toxic and/or hazardous chemicals are currently used in materials synthesis and device fabrication of OSCs. In this account, we will talk about contributions and efforts we have made to minimize the economic and environmental disadvantages in the production of OSCs. We will start with the background on how our projects were conceived and will specifically discuss our work on direct arylation and green solvent. Developments of direct arylation for synthesizing conjugated polymers will be illustrated along with our recent finding regarding the effect of green solvents on device performance and stability.