基于吡嗪空穴传输层的合成及在p -i-n型钙钛矿太阳能电池中的应用

钙钛矿太阳能电池由于具有高的光电转换效率,简单的溶液加工工艺,较低的成本等优势因而拥有广阔的应用前景。有机小分子空穴传输层材料在钙钛矿太阳能电池中扮演着极其重要的角色。在本工作中,我们设计和合成了基于吡嗪为分子中心核,三苯胺为分枝的X型空穴传输层材料PT-TPA。与Si-OMeTPA对比,吡嗪的引入不仅不会影响其结晶性,并且能够改善其电荷转移特性和分子中心共平面性,从而显著提升了PT-TPA的空穴迁移率。在非掺杂的情况之下,基于PT-TPA空穴传输层的p-i-n型钙钛矿太阳能电池展现出17.52%的光电转换效率,与相同条件下基于Si-OMeTPA空穴传输层的器件相比,效率提高了近15%。     

基于WOx/PEDOT:PSS复合空穴传输层的高效稳定平面异质结钙钛矿太阳电池

在基于钙钛矿/富勒烯平面异质结的钙钛矿太阳电池中,PEDOT:PSS是最常使用的空穴传输材料. 但PEDOT:PSS呈酸性,会腐蚀金属氧化物透明电极,使器件的电极界面稳定性欠佳. 本文将高功函的氧化钨（WO_x）插入到PEDOT:PSS和FTO之间,形成WO_x/PEDOT:PSS复合空穴传输层,这样既可以避免PEDOT:PSS与FTO直接接触,提高器件的稳定性,又可以进一步降低电极界面的接触势垒,从而提升器件的性能. 作者研究了复合传输层对透光率、钙钛矿形貌、钙钛矿结晶、光伏性能及器件稳定性的影响. 基于WO_x/PEDOT:PSS复合空穴传输层的电池效率可以达到12.96%,比单纯的PEDOT:PSS的电池效率(10.56%)提升了22.7%,同时器件的稳定性也得到大幅改善.     

界面修饰策略在钙钛矿太阳能电池中的应用

目前钙钛矿太阳能电池的认证效率已达25.2%,被认为是下一代最有希望的薄膜太阳能电池候选者。但通过溶液加工方法制备的钙钛矿薄膜不可控的形貌与较差的结晶性是制约器件稳定性提升和大面积生产的主要原因。为了有效解决这一难题,研究者们通常在电荷传输层与钙钛矿层之间进行界面修饰。本文从界面修饰的角度出发,总结了不同界面修饰策略在钙钛矿太阳能电池中的应用,并展望了界面修饰在低成本和大面积钙钛矿太阳能电池的应用前景。     

钙钛矿太阳能电池电子传输层的制备及应用

目前,有机-无机杂化钙钛矿太阳能电池(PSC)的器件效率已经超过25％.电子传输层作为PSC中的重要组成部分在提取和传输光生电子,阻挡空穴,修饰界面,调节界面能级和减少电荷复合等方面起着关键作用.无机n型材料,例如TiO2、ZnO、SnO2和其他金属氧化物材料具有成本低和稳定性好的特点,经常在传统PSC中被用作电子传输...     

左旋多巴和N,N-二甲基亚砜共掺杂PEDOT:PSS作为空穴传输层的高性能p-i-n型钙钛矿太阳能电池

在p-i-n型的钙钛矿太阳能电池中,聚3, 4-乙烯二氧噻吩：聚苯乙烯磺酸盐(PEDOT:PSS)作为最常用的空穴传输层(HTL)材料之一,由于其存在着吸湿性强以及能级与钙钛矿层不匹配等缺点,限制了它的应用。基于此,本文拟采用将左旋多巴(DOPA)和N, N-二甲基亚砜(DMSO)共同掺杂于PEDOT:PSS作为HTL的简单方法制备高性能p-i-n型钙钛矿太阳能电池。研究结果表明,DOPA和DMSO共掺杂PEDOT:PSS可以有效的调节HTL的能级并提高其导电性,器件的能量转化效率由13.35%显著提高到了17.54%。进一步研究发现,相比于未掺杂或单一掺杂的PEDOT:PSS,在DOPA和DMSO共掺杂的PEDOT:PSS上更有利于生长大尺寸、高结晶度的钙钛矿晶体;同时稳态/瞬态荧光和交流阻抗测试表明器件的内部载流子分离和传输更加有效。     

反式钙钛矿电池超薄空穴传输层研究进展

空穴传输层(HTLs)厚度对反式钙钛矿太阳能电池(PSCs)性能具有重大影响,因其显著影响太阳光透过和HTLs的空穴传输性能。几个纳米至十几个纳米厚度的超薄HTLs在减少伴生吸收、电荷传输损失和材料消耗等方面具有明显优势。目前,有许多成熟的制备超薄无机HTLs的方法,并在反式和叠层PSCs中得到广泛研究与应用。最近,一些关于有机超薄HTLs的新型制备方法也展现出良好的性能并逐渐引起相关领域研究者关注。在此,本文主要总结反式PSCs中超薄HTLs的研究进展与应用,关注其未来发展的挑战和方向,为该领域进一步的研究提供参考。     

低成本富勒烯衍生物电子传输层在钙钛矿太阳能电池的应用

Organic-inorganic hybrid perovskite solar cells (PSCs) have attracted significant attention owing to their high absorption coefficient and ambipolar charge transport properties. With only several years of development, the power conversion efficiency (PCE) has increased from 3.8% to 22.7%. In general, PSCs have two types of structural architecture: mesoporous and planar. The latter possesses higher potential for commercialization due to its simpler structure and fabrication process, especially the inverted planar structure, which possesses negligible hysteresis. In an inverted PSC, the electron transport materials (ETM) are deposited on a perovskite film. Only a few ETMs can be used for inverted PSCs as the perovskite film is easily damaged by the solvent used to dissolve the ETM. Furthermore, the energy levels of the ETM should be well aligned with that of the perovskites. Normally it is difficult to use inorganic ETMs as they require high temperatures for the annealing process to improve the electron conductivity; the perovskite film cannot sustain these high temperatures. To date, the fullerene derivative, [6, 6]-phenyl-C61-butyric acid methyl ester (PCBM), is the most commonly used organic ETM for high efficiency inverted planar PSCs. However, the high manufacturing cost due to its complex synthesis retards the industrialization of the PSCs. Here, we introduce a fullerene pyrrolidine derivative, N-methyl-2-pentyl-[60]fullerene pyrrolidine (NMPFP), synthesized via the Prato reaction of C₆₀ directly with cheap hexanal and sarcosine. Then the NMPFP electron transport layer (ETL) was prepared by a simple solution process. The properties of the resulting NMPFP ETLs were characterized using UV-Vis absorption spectroscopy, cyclic voltammetry measurements, atomic force microscopy, and conductivity test. From the results of the UV-Vis absorption spectroscopy and cyclic voltammetry measurements, the LUMO level of NMPFP ETL was calculated to be 0.2 eV higher than that of the PCBM ETL. This contributes to a higher open-circuit photovoltage. In addition, the NMPFP film presented higher conductivity than the PCBM film. Thus, the photo-generated charge carriers in the perovskite films should be transported more efficiently to the NMPFP electron transport layer (ETL) than to the PCBM ETL. This was confirmed by the results of the steady-state photoluminescence spectroscopy. Finally, the NMPFP as an alternative low-cost ETL was employed in an inverted planar PSC to evaluate the device performance. The device made with the NMPFP ETL yielded an efficiency of 13.83% with negligible hysteresis, which is comparable to the PCBM counterpart devices. Moreover, since stability is another important parameter retarding the commercialization of PSCs, the stability of the PCBM and NMPFP base PSCs were investigated and compared. It was found that the NMPFP devices possessed significantly improved stability due to the higher hydrophobicity of the NMPFP. In conclusion, this research demonstrates that NMPFP is a promising ETL to replace PCBM for the industrialization of cheap, efficient and stable inverted planar PSCs.     

自组装单分子空穴传输层在反式钙钛矿太阳电池的研究进展

空穴传输层在钙钛矿太阳电池(Perovskite solar cell, PSC)中起着抽取和传输钙钛矿层产生的光生空穴、抑制电子回流等重要作用,是构成高性能器件的重要组成部分.经典的空穴传输材料,如2,2’,7,7’-四[N,N-二(4-甲氧基苯基)氨基]-9,9’-螺二芴(spiro-OMe TAD)、聚[双(4-苯基)(2,4,6-三甲基苯基)胺](PTAA)等,空穴迁移率低、价格昂贵等缺点限制了其规模化应用.近年来,在反式PSC中自组装单分子层(self-assembledmonolayers,SAM)作为空穴传输层广泛应用,提升了器件性能.SAM分子结构中含有锚定官能团,可以在衬底上形成单分子薄膜,有着材料消耗小、无需添加剂、寄生吸收低、能够兼容叠层器件和有利于大面积制造等优点,已成为PSC领域的研究热点.本综述结合PSC发展,按照SAM分子结构中锚定基团的不同,对近年来基于SAM的空穴传输层的研究进行了分类和归纳,结合分子骨架变化分析了结构变化对其特性及器件性能的影响.最后,对SAM作为空穴传输层的发展做了总结和展望.     

低成本、高性能钙钛矿电池有机小分子空穴传输材料

钙钛矿太阳能电池由于其高能量转换效率(最高报道认证效率为25.2％)、低成本和易于制造等特点,成为下一代光伏技术的关注焦点.虽然钙钛矿材料本身可以传导空穴,但其效率比较低.空穴传输材料的使用成为有效提取电荷和提高钙钛矿型太阳能电池效率的关键因素.总结了近期报道的低成本、高性能有机小分子空穴传输材料(效率大于19％),从...     

通过对螺二芴的掺杂有效抑制非辐射复合制备高性能钙钛矿太阳能电池

金属卤素钙钛矿太阳能电池由于非辐射复合的损失,导致光电转换效率仍远低于肖克利-奎瑟尔极限. 本工作对安赛蜜分子作为空穴传输材料螺二芴的掺杂剂进行了研究. 研究发现相对于双三氟甲基磺酰亚胺锂12% 摩尔比的安赛蜜掺杂时,非辐射复合从86.05%降到了69.23%,电池的开路电压平均增长了0.08伏,最好的电池光电转换效率增长到了21.9%. 并且,在相对湿度20%~30%的干燥空气环境下老化720小时后电池的光电转换效率仍大于最初值的84%.     

High-performance fullerene-free polymer solar cells with solution-processed conjugated polymers as anode interfacial layer

A series of conjugated polymers based on PFS derivatives with π-conjugated 5-(9H-fluoren-2-yl)-2,2′-bithiophene(fluorene-alt-bithiophene) backbones, namely PFS-3C, PFS-4C and PFS-6C, were synthesized for their use as the anode interfacial layers(AILs) in the efficient fullerene-free polymer solar cells(PSCs). Alkyl sulfonate pendants with different lengths of alkyl side chains were introduced in the three polymers in order to investigate the effect of the alkyl chain length on the anode modification. The obtained three polymers exhibited similar absorption bands and energy levels, indicating that changing the length of the alkyl side chains did not affect the optoelectronic properties of the conjugated polymers. Based on the PBDB-T:ITIC active layer, we fabricated the fullerene-free PSCs using the three polymers as the AILs. The superior performance of the fullerene-free PSC device was achieved when PFS-4C was used as the AIL, showing a power conversion efficiency(PCE) of 10.54%. The high performance of the PFS-4C-modified device could be ascribed to the high transmittance, suitable work-function(WF) and smooth surface of PFS-4C. To the best of our knowledge, the PCE obtained in the PFS-4C-modified device is among the highest PCE values in the fullerene-free PSCs at present. These results demonstrate that the PFS derivatives are promising candidates in serving as the AIL materials for high-performance fullerene-free PSCs.     

ZnO电极修饰层在钙钛矿太阳能电池中的应用

ZnO电极修饰层具有高电子迁移率、高透光率、可低温制备且环境友好等优点在钙钛矿太阳能电池上获得了广泛应用。本文针对传统电极修饰层需要高温退火、透光率较低、制备过程繁琐,不利于高性能柔性钙钛矿电池器件制备等问题,系统综述了以ZnO材料作为电极修饰层的制备方法,综合分析了ZnO构筑的电极修饰层形貌、厚度、掺杂及复合对钙钛矿太阳能电池性能（如开路电压、电流密度、填充因子、光电转换效率等）的影响,展望了ZnO电极修饰层材料的未来发展趋势与其在钙钛矿太阳能电池中的应用前景。     

Efficient hole transport material formed by atmospheric pressure plasma functionalization of Spiro-OMeTAD

A technique to increase the conductivity of Spiro-OMeTAD using an easily scalable, non-thermal atmospheric pressure plasma jet (APPJ) is reported. An investigation of plasma functionalization demonstrated an enhancement in hole conductivity by over an order of magnitude from 9.4 × 10^?7 S cm^?1 for the pristine film to 1.15 × 10^?5 S cm^?1 for films after 5 minutes of plasma treatment. The conductivity value after plasma functionalization was comparable to that reported for 10–25% Li-TFSI-doped Spiro-OMeTAD. The increase in conductivity was correlated with a reduction in phase value observed using electrostatic force microscopy. Kelvin probe force microscopy showed an increase in work function after plasma exposure corresponding to the p-type nature of the doping. X-ray photoelectron spectroscopy revealed surface oxidation of plasma-functionalized films, as well as variation in nitrogen chemistry, with the formation of a higher binding energy quaternary nitrogen tail. Oxidation of Spiro-OMeTAD was also confirmed by the appearance of the 500 nm absorption peak using UV–vis spectroscopy. The synergistic contribution of increase in charge density in Spiro-OMeTAD due to the energetic species in the plasma jet coupled with improvement in π-π stacking of the molecules is thought to underlie the conductivity enhancement. The enhancement in positive charges can also be attributed to the formation of quinoid structures with quaternary nitrogen +N=C formed due to loss of methyl groups during plasma surface interaction. This work opens up the possibility of using an atmospheric pressure plasma jet as a simple and effective technique for doping and functionalizing Spiro-OMeTAD thin films to circumvent the detrimental issues associated with chemical dopants.     

High-efficiency,solution-processable,multilayer triple cation perovskite light-emitting diodes with copper sulfide–gallium–tin oxide hole transport layer and aluminum-zinc oxide–doped cesium electron injection layer

Light-emitting diodes with perovskite luminophores have great potential in next-generation displays because of their exceptional color purity with narrow emission bandwidth, broadband color tunability, and solution processability. However, their low luminescent efficiency is a critical drawback. Here, we report the first demonstration of a multicolor, large-area, perovskite display, which can be made flexible by using an optimized perovskite emissive layer sandwiched between inorganic metal oxide charge transport layers, all of which are coated via a facile solution process. We show that advanced interfacial engineering, especially the energy level alignment at the interface, plays a vital role in determining the device performance because of its effects on charge injection, transport, and recombination. These devices exhibit maximum current and power efficiencies of 74.25 cd A^?1 and 89.72 lm/w for green emission, 21.40 cd A^?1 and 25.84 lm/w for red emission, and 15.21 cd A^?1 and 15.84 lm/w for blue emission, respectively. Furthermore, with the introduction of inorganic charge transport layers, these devices exhibit high environmental stability, and the encapsulated devices have operating lifetimes exceeding 450 h with an initial brightness of 1000 cd/m².