TiO2/SnO2 electron transport double layers with ultrathin SnO2 for efficient planar perovskite solar cells

The electron transport layer (ETL) plays an important role on the performance and stability of perovskite solar cells (PSCs). Developing double ETL is a promising strategy to take the advantages of different ETL materials and avoid their drawbacks. Here, an ultrathin SnO₂ layer of ～ 5 nm deposited by atomic layer deposit (ALD) was used to construct a TiO₂/SnO₂ double ETL, improving the power conversion efficiency (PCE) from 18.02% to 21.13%. The ultrathin SnO₂ layer enhances the electrical conductivity of the double layer ETLs and improves band alignment at the ETL/perovskite interface, promoting charge extraction and transfer. The ultrathin SnO₂ layer also passivates the ETL/perovskite interface, suppressing nonradiative recombination. The double ETL achieves outstanding stability compared with PSCs with TiO₂ only ETL. The PSCs with double ETL retains 85% of its initial PCE after 900 hours illumination. Our work demonstrates the prospects of using ultrathin metal oxide to construct double ETL for high-performance PSCs.     

Reveal the large open-circuit voltage deficit of all-inorganicCsPbIBr2 perovskite solar cells

Due to excellent thermal stability and optoelectronic properties, all-inorganic perovskite is one of the promising candidates to solve the thermal decomposition problem of conventional organic—inorganic hybrid perovskite solar cells (PSCs), but the larger voltage loss (V_loss) cannot be ignored, especially CsPbIBr₂, which limits the improvement of efficiency. To reduce V_loss, one promising solution is the modification of the energy level alignment between the perovskite layer and adjacent charge transport layer (CTL), which can facilitate charge extraction and reduce carrier recombination rate at the perovskite/CTL interface. Therefore, the key issues of minimum V_loss and high efficiency of CsPbIBr₂-based PSCs were studied in terms of the perovskite layer thickness, the effects of band offset of the CTL/perovskite layer, the doping concentration of the CTL, and the electrode work function in this study based on device simulations. The open-circuit voltage (V_oc) is increased from 1.37 V to 1.52 V by replacing SnO₂ with ZnO as the electron transport layer (ETL) due to more matching conduction band with the CsPbIBr₂ layer.     

Ferroelectric Ba0.75Sr0.25TiO3 tunable charge transfer in perovskite devices

Interfacial charge recombination is a main issue causing the efficiency loss of the perovskite solar cells (PSCs). Here, ferroelectric Ba_0.75Sr_0.25TiO₃ (BST) is introduced as a polarization tunable layer to promote the interfacial charge transfer of the PSCs. The coexistence of ferroelectric polarization and charge carriers in BST is confirmed by density functional theory (DFT) calculations. Experimental characterization demonstrates the polarization reversal and the existence of domain in BST film. The BST film conductivity is tested as 2.98×10^-4 S/cm, which is comparable to the TiO₂ being used as the electron transporting layer (ETL) in PSCs. The calculations results prove that BST can be introduced into the PSCs and the interfacial charge transfer can be tuned by ferroelectric polarization. Thus, we fabricated the BST-based PSCs with a champion power conversion efficiency (PCE) of 19.05% after poling.     

DPVBi空穴阻挡层对OLED性能的优化

研究了宽带隙有机小分子材料DPVBi作为空穴阻挡层对OLED器件效率和亮度的优化作用.DPVBi的引入有效地改善了以PEDOT:PSS做空穴注入层的OLED器件的空穴过剩问题.实验结果表明:通过优化DPVBi的厚度,插入30 nm厚的DPVBi空穴阻拦层可以有效地平衡OLED器件的电子和空穴浓度,降低器件的工作电压,优...     

新型碳材料在钙钛矿太阳电池中的应用研究进展

新型碳材料如石墨烯及其氧化物、碳纳米管、富勒烯及石墨炔等因其优异的热学、力学、电学、光学性能成为了钙钛矿太阳电池研究的又一亮点. 本文总结了新型碳材料在钙钛矿太阳电池对电极、电子传输材料及空穴传输材料中的研究进展, 新型碳材料的引入有效地提高了钙钛矿电池的性能, 为下一步新型碳材料的应用开发以及钙钛矿电池器件的研究提供了新的思路.     

溶剂对钙钛矿薄膜形貌和结晶性的影响研究

溶剂对钙钛矿太阳能电池器件有着至关重要的影响. 基于目前常用的N, N-二甲基甲酰胺(DMF)和丁内酯(GBL)溶剂, 一步溶液旋涂技术和介孔电池结构, 制备的钙钛矿薄膜的形貌、结晶性, 以及最终的器件光电转化效率存在较大的差异, 利用DMF作为溶剂, 效率仅为2.8%, 而基于GBL的电池效率可以达到10.1%. 结合SEM, HRTEM, XRD和UV等表征手段, 分析了钙钛矿从DMF溶液和GBL溶液中结晶析出的不同机理, 明确了溶剂跟PbI₂的配位作用对钙钛矿的溶解、析出过程的制约作用, 揭示了造成器件效率差异的本质原因.     

硒化锑薄膜太阳电池的模拟与结构优化研究

采用wx-AMPS模拟软件对硒化锑(Sb_2Se_3)薄膜太阳电池进行建模仿真,将CdS, ZnO和Sn02的模型应用到Sb_2Se_3太阳电池的电子传输层中.结果显示,应用CdS和ZnO都能实现较高的器件性能,并发现电子传输层电子亲和势(Xe-ETL)的变化能够调节Sb_2Se_3太阳电池内部的电场分布,是影响器件性能的关键参数之一.过高或者过低的Xe-ETL都会使电池的填充因子降低,导致电池性能劣化.当Xe-ETL为4.2eV时,厚度为0.6μm的Sb_2Se_3太阳电池取得了最优的7.87%的转换效率.应用优化好的器件模型,在不考虑Sb_2Se_3层缺陷态的理想情况下,厚度为3μm的Sb_2Se_3太阳电池的转换效率可以达到16.55%(短路电流密度J_(SC)=34.88 mA/cm~2、开路电压V_(OC)=0.59 V、填充因子FF=80.40%).以上模拟结果表明,Sb_2Se_3薄膜太阳电池在简单的器件结构下就能够获得优异的光电性能,具有较高的应用潜力.     

双电子传输层对有机发光二极管效率及其衰减的改善

采用Bphen和BCP制成双电子传输层(Doubleelectrontransportlayers, DETLs)的有机发光二极管器件, 与Bphen单独作ETL的器件相比, DETLs器件具有较小的空穴漏电流, 效率提升10%。与BCP独自作ETL的器件相比, 更多的电子注入使DETLs器件的效率在50~600mA/cm²的电流范围内没有衰减。BCP作ETL的器件的效率从50mA/cm²时的2.5cd/A衰减至300mA/cm²的2.1cd/A, 衰减了16%。Cs₂CO₃:BCP独自作ETL的器件效率在50~300mA/cm²的电流范围内衰减了30%, 而Bphen/Cs₂CO₃:BCP作DETLs的器件效率在50~600mA/cm²的电流范围内衰减幅度为0, 原因是Bphen阻挡了Cs原子扩散至发光层。     

高效无空穴传输层碳基钙钛矿太阳能电池的制备与性能研究

碳基钙钛矿太阳能电池因稳定性高、成本低廉而备受关注,但由于钙钛矿与碳电极之间能级匹配度不高,界面阻力大而导致效率不及金属基钙钛矿太阳能电池.本文制备了碳基无空穴传输层FTO/c-TiO₂/m-TiO₂/CH₃NH₃PbI₃/Carbon电池结构.通过对介孔二氧化钛层、钙钛矿层厚度进行优化,并对钙钛矿的薄膜形貌及钙钛矿激发电子寿命、可见光吸收度、载流子的提取与分离等进行深度分析,讨论了电池效率提升的内在机理.当介孔氧化钛层和钙钛矿层达到最优厚度时,钙钛矿太阳能电池获得了开路电压（V_oc）为0.93 V、电流密度（J_sc）为21.75 mA/cm²、填充因子为55%、光电转化效率达到11.11%.同时对电池进行了稳定性研究,在室温湿度为40%–50%的条件下放置15 d电池性能依旧稳定保持原来的95%,优于金属基钙钛矿太阳能电池,从而为碳电极钙钛矿太阳能电池的商业化发展提供了可能.     

Electron transport layer engineering with rubidium chloride alkali halide to boost the performance of perovskite absorber layer

The mesoscopic perovskite solar cells (PSCs) based on titanium oxide (TiO₂) with a certified 25.2% efficiency are the forefront devices in the PSCs field. Hence, it can conclude the mesoporous titanium oxide (mp-TiO₂) is one of the most promising candidates to use as an electron transport layer (ETL) in PSCs. Improving the conductivity of mp-TiO₂ can consider as a simple route to motivate the electron extraction ability of this layer and increase the efficiency of PSCs. Herein, rubidium chloride (RbCl) was introduced as an additive source to boost the optoelectronic properties of mp-TiO₂ ETL. It was observed through ETL modification with RbCl, the optical transmittance of mp-TiO₂ remains constant but increases its electro-conductivity. Results showed that the morphology and crystalline properties of the perovskite layer with a modified ETL substrate is improved. It indicates a perovskite layer with enlarger grains and lower lead iodide (PbI₂) surplus. Altogether, ETL modification brings a champion efficiency of 11.10% for hole transport layer (HTL)-free PSCs higher than that of 8.65% for the HTL-free PSCs based on pristine ETL. Besides, Modified PSCs compared to pristine PSCs showed higher stability response as a result of lower grain boundaries in the modified perovskite layer.     

钙钛矿太阳能电池中电子传输材料的研究进展

有机-无机杂化的卤素钙钛矿材料在2009年首次应用在光伏器件中, 而后有关此类型太阳能电池的报道数量呈井喷式增长. 至2014年5月钙钛矿电池光电转化效率已接近20%, 已超过有机及染料敏化太阳能电池的效率, 且有望达到单晶硅太阳能的水平, 成为光伏发电领域中的希望之星. 在钙钛矿电池中, 电子传输材料与吸收层的电子选择性接触对提高光电转化效率起到重要作用, 尤其在正置结构器件中, 电子传输层的介观结构直接影响钙钛矿的生长情况. 同时, 电子传输层的化学性质及其界面也会对电池的稳定性和寿命产生影响. 本文总结了电子传输材料在该类电池中的研究现状和热点, 并按材料的化学组分不同, 将电子传输材料分为三类: 金属氧化物、有机小分子和复合材料, 详细地介绍了电子传输材料在钙钛矿太阳能电池中的作用和近来的最新进展.     

Non-peripherally octaalkyl-substituted nickel phthalocyanines used as non-dopant hole transport materials in perovskite solar cells

This report presents two non-perihperally octaalkyl-substituted nickel phthalocyanines (NiPcs), namely, NiEt₂Pc and NiPr₂Pc, for use as dopant-free hole transport materials in perovskite solar cells (PSCs). The length extension of the alkyl chains from ethyl to propyl significantly tunes the NiPcs' energy levels, thus reducing charge carrier recombination at the perovskite/hole transport layer (HTL) interface and leading to higher open-circuit voltage (V_OC) and short-circuit current density (J_SC) observed for the NiPr₂Pc-based PSC. And higher charge carrier mobility, higher thin film crystallinity, and lower surface roughness of the NiPr₂Pc HTL compared with that of the NiEt₂Pc one also lead to higher J_SC and fill factor (FF) observed for the NiPr₂Pc-based device. Consequently, the NiPr₂Pc-based PSC exhibits a higher power conversion efficiency (PCE) of 14.07% than that of the NiEt₂Pc-based device (8.63%).     

有机金属卤化物钙钛矿薄膜中的光诱导载流子动力学和动态带重整效应

近年来有机-无机金属卤化物钙钛矿太阳能电池因具有光电能量转换效率高、制备工艺简单等优点,引起了学术界和产业界的广泛关注,其优异的光电特性逐渐在能源领域展现出独特的优越特性.在短短几年内,有机-无机混合物钙钛矿太阳能电池的能量转换效率已经高达23%,发展速度逐步赶上甚至超越了成熟的硅太阳能电池.本文利用飞秒瞬态吸收光谱,对二步法制备的(5-AVA)_(0.05)(MA)_(0.95)PbI_3和(5-AVA)_(0.05)(MA)_(0.95)PbI_3/Spiro-OMeTAD有机-无机卤化物钙钛矿薄膜材料的激发态动力学进行了对比研究,详细讨论了两种薄膜样品中的电荷载流子产生与复合机制.通过紫外-可见吸收光谱测得钙钛矿薄膜(5-AVA)_(0.05)(MA)_(0.95)PbI_3和(5-AVA)_(0.05)(MA)_(0.95)PbI_3/Spiro-OMeTAD的吸收光谱与CH_3NH_3PbI_3钙钛矿薄膜材料的双价带结构相对应.从瞬态吸收光谱中,观察到760 nm附近的光致漂白信号,此时的载流子复合过程符合二阶动力学过程,而在约550—700 nm光谱范围内则是光诱导激发态吸收信号.实验结果表明,(5-AVA)_(0.05)(MA)_(0.95)PbI_3钙钛矿薄膜样品中光生载流子主要的弛豫途径是自由电子和空穴的复合.抽运光激发样品使价带中的电子跃迁到导带,随着延迟时间的增加,电子和空穴复合,光谱发生红移现象.所观察到的带重整效应可以根据Moss-Burstein效应解释.相比较而言,(5-AVA)_(0.05)(MA)_(0.95)PbI_3/Spiro-OMeTAD钙钛矿薄膜样品在光激发后电子和空穴分离,空穴迅速转移到空穴传输层,这将导致样品吸收度增加,漂白信号快速恢复,电子-空穴的复合不再对漂白信号的弛豫动力学起主导作用,同时也削弱了带重整现象.本文的实验结果对半导体有机-无机金属卤化物钙钛矿薄膜在光伏领域的应用具有重要意义,为今后高效、稳定的钙钛矿太阳电池的研究提供了参考.     

钙钛矿太阳电池综述

基于有机-无机杂化钙钛矿材料(CH₃NH₃PbX₃)制备的太阳电池效率自2009年从3.8%增长到19.6%, 因其较高的光吸收系数, 较低的成本及易于制备等优势获得了广泛关注. 钙钛矿材料不仅可以作为光吸收层, 还可用作电子和空穴传输层, 以此制备出不同结构的钙钛矿太阳电池: 介孔结构、介观超结构、平面结构、无HTM层结构和有机结构. 除此之外, 钙钛矿材料制备方法的多样性使其更具吸引力, 目前已有一步溶液法、两步连续沉积法、双源共蒸发法和溶液-气相沉积法. 本文主要介绍了钙钛矿太阳电池的发展历程、工作原理及钙钛矿薄膜的制备方法等. 详细阐述了电池每一层的具体作用和针对现有的钙钛矿结构各层材料的优化, 最后介绍了钙钛矿太阳电池所面临的问题和发展前景, 以期对钙钛矿太阳电池有进一步的了解, 为制备新型高效的钙钛矿太阳电池打下坚实的基础.     

Device simulation of lead-free CH_3NH_3SnI_3 perovskite solar cells with high efficiency

The lead-free perovskite solar cells(PSCs) have drawn a great deal of research interest due to the Pb toxicity of the lead halide perovskite.CH_3NH_3SnI_3 is a viable alternative to CH_3NH_3PbX_3,because it has a narrower band gap of 1.3 eV and a wider visible absorption spectrum than the lead halide perovskite.The progress of fabricating tin iodide PSCs with good stability has stimulated the studies of these CH_3NH_3SnI_3 based cells greatly.In the paper,we study the influences of various parameters on the solar cell performance through theoretical analysis and device simulation.It is found in the simulation that the solar cell performance can be improved to some extent by adjusting the doping concentration of the perovskite absorption layer and the electron affinity of the buffer and HTM,while the reduction of the defect density of the perovskite absorption layer significantly improves the cell performance.By further optimizing the parameters of the doping concentration(1.3 × 10~(16) cm~3) and the defect density(1 × 10~(15) cm~3) of perovskite absorption layer,and the electron affinity of buffer(4.0 eV) and HTM(2.6 eV),we finally obtain some encouraging results of the J_(sc) of 31.59 mA/cm~2,V_(oc) of 0.92 V,FF of 79.99%,and PCE of 23.36%.The results show that the lead-free CH_3NH_3SnI_3 PSC is a potential environmentally friendly solar cell with high efficiency.Improving the Sn~(2+) stability and reducing the defect density of CH_3NH_3SnI_3 are key issues for the future research,which can be solved by improving the fabrication and encapsulation process of the cell.     

SnO_2/p~+-Si异质结器件的电致发光:利用TiO_2盖层提高发光强度

通过在重掺硼硅(p+-Si)衬底上溅射SnO2薄膜并在O2气氛下800℃热处理形成SnO2/p+-Si异质结.基于该异质结的器件可在低电压(电流)驱动下电致发光.进一步地,通过在SnO2薄膜上增加TiO2盖层,使器件的电致发光获得显著增强.这是由于TiO2盖层的引入,一方面使SnO2薄膜更加致密,减少了非辐射复合中心;另一方面TiO2较大的折射率和合适的厚度使SnO2薄膜电致发光的出光效率得到提高.     

PTCDI-C8作为阴极修饰层提高钙钛矿太阳能电池的性能

采用N,N'-二正辛烷基-3,4,9,10-苝四甲酰二亚胺（PTCDI-C₈）对钙钛矿电池电子传输层（PCBM）进行界面修饰以减少PCBM与Al电极之间的漏电流,提高阴极的电子收集效率。通过调节PTCDI-C₈薄膜的厚度优化界面接触和电子传输性能。实验结果表明：当PTCDI-C₈薄膜的厚度为20 nm时得到的器件性能最优。光电转换效率（PCE）由5.26%提高到了8.65%,开路电压（V_oc）为0.92 V,短路电流（J_sc）为15.68 mA/cm²,填充因子（FF）为60%。PTCDI-C₈能够有效阻挡空穴向阴极传输,同时PTCDI-C₈具有较高的电子迁移率以及较高的稳定性,在增加电子传输的同时,可减少环境对PCBM的侵蚀,提高了器件的稳定性。     

Improved efficiency and stability of perovskite solar cells with molecular ameliorating of ZnO nanorod/perovskite interface and Mg-doping ZnO

Despite the advanced efficiency of perovskite solar cells(PSCs),electron transportation is still a pending issue.Here the polymer polyvinylpyrrolidone(PVP)is used to enhance the electron injection,which is thanks to the passivation of the defects at the interface between the ZnO electron transporting layer(ETL)and the perovskite.The application of the PVP layer inhibits the device degradation,and 80%of the primary efficiency is kept after 30 d storage in air condition.Additionally,the efficiency of the device is further enhanced by improving the conductivity and crystallinity of the ZnO ETL via Magnesium(Mg)doping in the ZnO nanorods(ZnO NRs).Moreover,the preparation parameters of the ZnO NRs are optimized.By employing the high-crystallinity ZnO ETL and the PVP layer,the power conversion efficiency(PCE)of the champion device is increased from 16.29%to 19.63%.These results demonstrate the advantages of combining mesoscale manipulation with interface modification and doping together.     

新型硒化锑材料及其光伏器件研究进展

硒化锑(Sb₂Se₃)是一种二元单相化合物, 原料储量大、毒性低、价格便宜; 同时其禁带宽度合适(～1.15 eV), 吸光系数大(>10⁵ cm^-1), 长晶温度低, 非常适合制作新型低成本低毒的薄膜太阳能电池, 理论光电转换效率可达30%以上. 目前文献报道的Sb₂Se₃薄膜太阳能电池效率已达3.7%, 初步证明了Sb₂Se₃材料在薄膜太阳能电池应用方面的巨大潜力. 本文综述了近年来Sb₂Se₃太阳能电池的研究进展, 着重介绍了Sb₂Se₃的材料特性和薄膜制备及相关理论研究, 阐述了不同结构电池器件的研究进展, 并对其发展趋势进行了展望.     

Enhancing the photo-luminescence stability of CH3NH3PbI3 film with ionic liquids

The methylammonium lead triiodide (CH₃NH₃PbI₃)-based perovskite shows a great alluring prospect in areas of solar cells, lasers, photodetectors, and light emitting diodes owing to their excellent optical and electrical advantages. However, it is very sensitive to the surrounding oxygen and moisture, which limits its development seriously. It is urgent to spare no effort to enhance its optical and electrical stability for further application. In this paper, we synthesize the MAPbI₃ perovskite film on the glass substrate with/without the ionic liquid (IL) of 1-Butyl-3-methylimidazolium tetrafluoroborate (BMIMBF₄) by a simple two-step sequential solution method. The additive of BMIMBF₄ can improve the quality of crystal structure. Moreover, the photo-luminescence (PL) intensity of MAPbI₃ film with BMIMBF₄ is much stronger than the pure MAPbI₃ film after a week in the air, which is almost ten-fold of the pure one. Meanwhile, under the illumination of 405-nm continuous wave (CW) laser, the fluorescent duration of the MAPbI₃ film with BMIMBF₄ is approximately 2.75 min, while the pure MAPbI₃ film is only about 6 s. In fact, ionic liquid of BMIMBF₄ in the perovskite film plays a role of passivation, which prevents the dissolution of MAPbI₃ into CH₃NH₃ and PbI₂ and thus enhances the stability of environment. In addition, the ionic liquid of BMIMBF₄ possesses high ionic conductivity, which accelerates the electron transport, so it is beneficial for the perovskite film in the areas of solar cells, photodetectors, and lasers. This interesting experiment provides a promising way to develop the perovskite's further application.