基于非富勒烯受体的溶液加工型全小分子太阳能电池研究进展

有机太阳能电池(OPV),具有质量轻、可成本低制备等优势,是一种具有实际应用潜力的光伏技术。有机太阳能电池活性层可以由共轭聚合物或溶液可加工的小分子材料(给体与受体)共混组成。由于小分子材料具有明确的分子结构,纯度可控及无批次差别影响的特点;并结合近年来非富勒烯小分子受体的快速发展,使得非富勒烯全小分子(NF-SM-OPV)电池研究受到广泛关注。由于大部分A-D-A型非富勒烯受体分子具有各向异性的特点,这使激子解离和电荷传输,很大程度上受分子间堆积方式的影响,导致非富勒烯全小分子电池活性层形貌调控更加复杂。虽然非富勒烯小分子太阳能电池具有非富勒烯受体材料和小分子材料的双重优势,但高效率非富勒烯小分子太阳能电池的制备,仍具有很大挑战。因此,本文总结近年来高性能非富勒烯小分子太阳能电池的相关进展。着重介绍针对非富勒烯受体的给体小分子材料设计工作,并在此基础上近一步讨论非富勒烯小分子太阳能电池面临的挑战与展望。     

基于非共价相互作用的非富勒烯受体光伏材料研究进展

有机太阳能电池由于制备简单、成本低,而且易于制备大面积柔性电池,因而受到了研究人员的广泛关注.非富勒烯受体材料因具有合成相对简单、易于纯化、能级和带隙可调等优点,极大地促进了有机太阳能电池效率的提高.基于非富勒烯受体材料的太阳能电池已经成为目前有机太阳能电池的研究热点之一,而具有分子内非共价键相互作用的受体材料是非富勒烯受体体系的重要组成部分.通过引入O、F、N、Se等杂原子,形成分子内非共价键相互作用,可以有效提高非富勒烯受体材料的平面性和电荷迁移率,降低光学带隙并拓宽吸收光谱,从而进一步提高太阳能电池的光伏性能.本文介绍了近几年来基于分子内非共价键相互作用的聚合物和小分子非富勒烯受体材料的研究进展,并展望了其发展趋势和应用前景.     

非富勒烯小分子有机太阳能电池电子受体材料的研究进展

富勒烯及其衍生物是一类重要的n-型电子受体材料,在有机太阳能电池器件中发挥了至关重要的作用. 但由于富勒烯材料吸光波长较窄、亲和能高、溶解性差等,严重限制了富勒烯作为有机太阳能电池n-型电子受体材料的更广泛应用和器件性能的进一步提升. 非富勒烯n-型电子受体材料具有能级可调、合成简便、加工成本低、溶解性能优异等特点,更重要的是,此类材料在可见太阳光光谱中比富勒烯及其衍生物材料有更加宽广的吸收范围;近年来,受到越来越多的关注和研究. 本文较为系统地阐述了非富勒烯小分子材料作为有机太阳能电池n-型电子受体材料的研究进展,并对其发展前景作了展望.     

稠环电子受体光伏材料

基于非富勒烯受体的有机太阳能电池是化学和材料领域的热点前沿之一,中国领跑这个热点前沿.中国学者在非富勒烯受体材料方面取得了一系列重要的创新成果.我们提出了"稠环电子受体(FREA)"这一新概念,构建了高性能稠环电子受体新体系,发明了明星分子ITIC.我们的原创性工作引起了国内外同行的广泛关注和跟进.目前,基于稠环电子受体的有机太阳能电池效率已达到13%~14%,超过富勒烯体系.ITIC等稠环电子受体的出现颠覆了富勒烯受体在有机太阳能电池领域的统治地位,开创了有机太阳能电池的非富勒烯时代.本文简要评述了我们在高性能稠环电子受体设计与器件应用中的研究进展,并展望稠环电子受体的未来发展.     

十年磨一剑：专访非富勒烯受体的先驱者占肖卫教授

<正>自从1995年首次报道本体异质结有机太阳能电池以来,在近二十年时间里,富勒烯衍生物已成为最广泛使用的电子受体,非富勒烯受体的器件效率远远低于富勒烯衍生物。而富勒烯太阳光吸收弱、能级调控难、生产成本高、形貌稳定性差的缺点,限制了有机太阳能电池领域的可持续发展。2015年以来,非富勒烯受体领域不断取得突破,器件效率从低于7%快速提升到高于17%,并大大超过富勒烯受体,使人们看到了有机太阳能电池的巨大潜力,吸引了国际学术界越来越多的研究力量投入到非富勒烯     

高性能有机稠环电子受体光伏材料

正聚合物太阳能电池一般由氧化铟锡(ITO)透明正极、金属负极和夹在两电极之间的共混活性层所构成,具有结构和制备过程简单、成本低、重量轻、可制备成柔性和半透明器件等突出优点,近年来成为国内外研究热点.活性层是聚合物太阳能电池最重要的组成部分,通常由p-型共轭聚合物给体和n-型半导体受体材料组成.富勒烯衍生物是最为广泛使用的n-型受体材料.然而,富勒烯受体存在一些缺点,如     

有机硼小分子受体材料

<正>有机太阳能电池具有柔性、重量轻、溶液加工、成本低的突出优势,适合未来在便携式能源中应用,是当前的国际科学研究热点~(1–4)。有机太阳能电池以有机/高分子给体材料和受体材料的共混物作为光电活性层。受益于稠环芳烃类小分子受体材料的开发,近几年来有机太阳能电池领域迅速发展,其单结器件的效率已经超过了14%,展现了巨大的应用潜力~3。     

基于聚合物给体与非富勒烯有机小分子受体材料的有机太阳能电池研究进展

在本体异质结有机太阳能电池的研究中,富勒烯及其衍生物是一类重要的n-型电子受体材料,然而基于富勒烯的材料有一些难以克服的弱点,例如在可见光范围内较弱且窄的吸收、很难调节的带隙、溶解性较差等,这些都严重限制了富勒烯类材料在有机太阳能电池中作为n-型受体材料更广泛的应用。而非富勒烯n-型电子受体材料比富勒烯类材料拥有在可见光光谱中更加宽广的吸收范围、能级更易调节、合成简便、加工成本更低、溶解性能更加优异等重要特点,目前基于非富勒烯类材料的本体异质结有机太阳能电池的能量转换效率超过了4%。本文综述了几类非富勒烯类有机小分子受体材料的研究进展,讨论了提高基于非富勒烯类有机小分子材料的有机太阳能电池器件性能的关键因素,并对其发展前景作了展望。     

非富勒烯类有机小分子受体材料

在本体异质结太阳能电池的研究过程中,异质结活性层材料的发展一直是最基本最核心的部分,活性层材料包括给体材料和受体材料,其中给体材料的研究一直占据着主导地位,很多课题组报道的器件效率已经超过8%;而受体材料的研究却相对单一,大部分研究都围绕富勒烯及其衍生物.近年来非富勒烯类的有机小分子受体材料由于其易于合成与纯化、通过分子设计使能级更方便调节等优点引起了人们的广泛关注并且取得了很大进展,目前以它作为受体材料的电池效率可以达到4%.综述了近年来几类非富勒烯类有机小分子受体材料的研究进展,包括它们的分子设计及其在光伏器件中的应用,最后我们讨论了提高非富勒烯类的有机小分子受体材料器件性能的关键因素及其研究前景.     

有机太阳能电池性能衰减机理研究进展

近年来随着非富勒烯Y系列明星分子受体的出现, 单结有机太阳能电池的光电转换效率已经突破19%, 但是器件在运行条件下缺乏良好的稳定性, 严重制约了其商业化发展. 因此越来越多的研究聚焦于造成有机太阳能电池性能衰减的原因以及如何提高有机太阳能电池的稳定性. 由于有机太阳能电池复杂的器件结构、不尽相同的活性层材料以及在稳定性研究中条件的差异, 造成了对有机太阳能电池器件衰减研究的困难. 为了更全面地了解有机太阳能电池的衰减过程, 对近些年有机太阳能电池器件衰减过程的研究成果进行综述, 总结了由于给受体材料化学分解、活性层形貌变化、传输层和电极腐蚀以及界面反应等原因造成的器件性能衰减, 并介绍了近些年关于提高器件稳定性的一些策略, 最后对有机太阳能电池的未来发展进行了展望.     

带有噻吩侧基的有机硼小分子电子受体光伏材料

有机小分子电子受体材料的侧基能够影响异质结有机太阳能电池的给体/受体匹配和器件性能。我们设计并合成了一个硼原子带有噻吩侧基的有机硼小分子(MBN-Th)。该分子的LUMO离域在整个骨架上,HOMO定域在中心核上,其独特的电子结构使该分子具有两个强的吸收峰(波长分别为490和726nm),因此分子具有宽的吸收光谱和强的太阳光吸收能力。与苯基侧基相比,噻吩侧基使分子的HOMO能级下移0.1 eV,LUMO能级保持不变,进而引起分子带隙减小和吸收光谱蓝移20nm。基于该有机硼小分子受体材料的异质结有机太阳能电池,实现了4.21%的能量转化效率和300–850nm的宽响应光谱。实验结果表明,硼原子上的噻吩侧基是调控有机硼小分子光电性质的有效方法,可以用于有机硼小分子受体材料的设计。     

Fluorination-substitution effect on all-small-molecule organic solar cells

Due to the strong crystallinity and anisotropy of small molecules, matched molecular photoelectric properties and morphologies between small molecules and non-fullerene acceptors are especially important in all-small-molecule organic solar cells(OSCs).Introducing fluorine atoms has been proved as an effective strategy to achieve a high device performance through tuning molecular energy levels, absorption and assembly properties. Herein, we designed a novel benzodithiophene-based small molecule donor BDTF-CA with deep highest occupied molecular orbital(HOMO) energy level. All-small-molecule OSCs were fabricated by combing non-fullerene acceptor IDIC with different fluorine-atom numbers. Two or four fluorine atoms were introduced to the end-capped acceptor of IDIC, which are named as IDIC-2 F and IDIC-4 F, respectively. With the increase of fluorination from IDIC to IDIC-4 F, the open circuit voltage(V_(oc)) of the devices decreased, while hole and electron mobilities of the active layers increased by one order of magnitude. Contributed to the most balanced V_(oc), short-circuit current(J_(sc)) and fill factor(FF), the device based on BDTF-CA/IDIC-2 F achieved the highest power conversion efficiency of 9.11%.     

Semitransparent Flexible Organic Solar Cells

The semitransparent flexible organic solar cell takes advantages of flexibility, transparency, color adjustment property, which is more conducive to integrate on buildings and mobile terminals. Ascribing to the developments of narrow band gap donors and the new non-fullerene acceptors, the power conversion efficiency of semitransparent flexible organic solar cells has been achieved 10% to 12% with average visible transmittance of 17% to 21%. This review summarizes the molecular design of the most representative active layer materials, and discusses the characterization of semitransparent parameters paradigms, then we discuss how to optimize the device in combination with optical simulation, and finally list the recent development of semitransparent flexible electrodes of ITO-free organic solar cells, and give our perspectives on the next step direction.     

Small molecule semiconductors for high-efficiency organic photovoltaics

Organic photovoltaic cells (OPVs) are a promising cost-effective alternative to silicon-based solar cells, and possess light-weight, low-cost, and flexibility advantages. Significant progress has been achieved in the development of novel photovoltaic materials and device structures in the last decade. Nowadays small molecular semiconductors for OPVs have attracted considerable attention, due to their advantages over their polymer counterparts, including well-defined molecular structure, definite molecular weight, and high purity without batch to batch variations. The highest power conversion efficiencies of OPVs based on small molecular donor/fullerene acceptors or polymeric donor/fullerene acceptors are up to 6.7% and 8.3%, respectively, and meanwhile nonfullerene acceptors have also exhibited some promising results. In this review we summarize the developments in small molecular donors, acceptors (fullerene derivatives and nonfullerene molecules), and donor-acceptor dyad systems for high-performance multilayer, bulk heterojunction, and single-component OPVs. We focus on correlations of molecular chemical structures with properties, such as absorption, energy levels, charge mobilities, and photovoltaic performances. This structure-property relationship analysis may guide rational structural design and evaluation of photovoltaic materials (253 references).     

萘酰亚胺-卟啉星型电子受体分子的构筑及其在非富勒烯太阳能电池中的应用

非富勒烯太阳能电池目前已经成为有机太阳能电池的研究热点,大量的共轭电子受体分子被开发,并成功应用到高性能光伏器件中。共轭分子作为非富勒烯电子受体,需要综合考虑吸收、能级、电子传输以及结晶性等,其中宽吸收光谱可以提高对太阳光谱的利用,是分子设计中重要因素之一。本工作中,我们设计一种新型电子受体分子,以卟啉为核、萘酰亚胺为端基以及炔为桥连基团。这种新型分子具有近红外的吸收光谱以及合适的能级。将一种具有吸收互补的共轭聚合物为电子给体,星型分子为电子受体应用到电池的活性层中,我们获得了1.8%的能量转换效率,电池的光谱响应为300–900 nm。实验结果证明了这种以卟啉为核的分子设计在实现近红外吸收的电子受体方面具有重要应用前景。     

Small Molecule Based Non‐Fullerene Acceptors: A Comparative Study

Organic solar cells (OSCs) have gained attention of the scientific community from the last decade and are now considered as one of the most important source for low‐cost power production. The recent rapid progress in non‐fullerene acceptors in BHJ indicates that they have potential to compete with fullerene‐based BHJ OSCs. The present review addressed the systematic comparison among various acceptors (diketopyrrolopyrrole (DPP), benzothiadiazole (BTD) and perylenediimide (PDI) based acceptors) in order to design and improve the performance of small molecules based non‐fullerene acceptors. This review focuses on the performance of small molecule non‐fullerene acceptors based on DPP, BTD and PDI for OSCs with respect to the change in molecular structures, energy levels, and PCE. A systematic comparison on the effect of molecular architecture, side chains on their performance is provided with the intention of evaluating the challenge to make highly efficient acceptors for the next generation organic photovoltaics.     

Conformationally constrained macrocyclic diporphyrin-fullerene artificial photosynthetic reaction center

Photosynthetic reaction centers convert excitation energy from absorbed sunlight into chemical potential energy in the form of a charge-separated state. The rates of the electron transfer reactions necessary to achieve long-lived, high-energy charge-separated states with high quantum yields are determined in part by precise control of the electronic coupling among the chromophores, donors, and acceptors and of the reaction energetics. Successful artificial photosynthetic reaction centers for solar energy conversion have similar requirements. Control of electronic coupling in particular necessitates chemical linkages between active component moieties that both mediate coupling and restrict conformational mobility so that only spatial arrangements that promote favorable coupling are populated. Toward this end, we report the synthesis, structure, and photochemical properties of an artificial reaction center containing two porphyrin electron donor moieties and a fullerene electron acceptor in a macrocyclic arrangement involving a ring of 42 atoms. The two porphyrins are closely spaced, in an arrangement reminiscent of that of the special pair in bacterial reaction centers. The molecule is produced by an unusual cyclization reaction that yields mainly a product with C(2) symmetry and trans-2 disubstitution at the fullerene. The macrocycle maintains a rigid, highly constrained structure that was determined by UV-vis spectroscopy, NMR, mass spectrometry, and molecular modeling at the semiempirical PM6 and DFT (B3LYP/6-31G**) levels. Transient absorption results for the macrocycle in 2-methyltetrahydrofuran reveal photoinduced electron transfer from the porphyrin first excited singlet state to the fullerene to form a P(?+)-C(60)(?-)-P charge separated state with a time constant of 1.1 ps. Photoinduced electron transfer to the fullerene excited singlet state to form the same charge-separated state has a time constant of 15 ps. The charge-separated state is formed with a quantum yield of essentially unity and has a lifetime of 2.7 ns. The ultrafast charge separation coupled with charge recombination that is over 2000 times slower is consistent with a very rigid molecular structure having a small reorganization energy for electron transfer, relative to related porphyrin-fullerene molecules.     

有机太阳能电池中基于苝二酰亚胺结构小分子受体进展

最近几年,有机太阳能电池中的非富勒烯小分子受体研究引起了人们的兴趣。其中,苝二酰亚胺(PDI)类分子因具有良好的电子传输能力,较强的电子亲和力,稳定的光、热、化学性能以及化学结构的可设计性带来的性能可调控性而得到广泛的关注。本文总结了近三年来在体异质结有机太阳能电池应用方面PDI小分子受体的研究进展,重点关注了PDI分子结构对其性能的影响,希望为以后PDI类受体分子的设计思路起到一定的启发作用。     

Synthesis and photovoltaic properties of low bandgap dimeric perylene diimide based non-fullerene acceptors

Non-fullerene organic acceptors have attracted increasing attention in recent years. One of the challenges in the synthesis of non-fullerene organic acceptors is to tune the absorption spectrum and molecular frontier orbitals, affording low bandgap molecules with improved absorption of the near-infrared solar photons. In this paper, we present the synthesis, optoelectronic and photovoltaic properties of a series of dimeric perylene diimide(PDI) based non-fullerene acceptors. These PDI dimers are bridged by oligothiophene(T) from 1T to 6T. With the increase of the oligothienyl size, the highest occupied molecular orbital(HOMO) energy is raised from ?5.65 to ?5.10 e V, while that of the lowest unoccupied molecular orbit(LUMO) is kept constant at ?3.84 e V, affording narrow bandgap from 1.81 to 1.26 e V. The absorption from the oligothiophene occurs between 350 and 500 nm, which is complementary to that from its bridged PDI units, leading to a wide spectral coverage from 350 to 850 nm. The optimal dihedral angle between the bridged two perylene planes is dependent on the oligothienyl size, varying from 5° to 30°. The solubility of the dimers depends on the oligothienyl size and can be tuned by the alkyl chains on the bridged thienyl units. The possible applications as the solution-processable non-fullerene organic acceptor is primarily studied using commercial P3 HT as the blend donor. The photovoltaic results indicate that 1T, 4T and 6T all yield a higher efficiency of ?1.2%, whereas 2T, 3T and 5T all give a lower efficiency of 0.5%. The difference in the cell performance is related with the tradeoff between the differences of absorption, HOMO level and film-morphology between these dimers.