大尺寸高质量CH3NH3PbCl3钙钛矿单晶的生长机理、相转变与光学性能

在传统逆温差结晶法基础上,通过引入高质量籽晶,采用籽晶诱导逆温差结晶法生长出尺寸为11mm×11mm×2mm的CH₃NH₃PbCl₃钙钛矿单晶.X射线衍射和Rietveld精修结果表明,室温下CH₃NH₃PbCl₃单晶是立方相,其空间群为Pm■m,晶格常数a=0.56877 nm.偏光显微镜研究结果表明,CH₃NH3PbCl₃单晶的生长机理遵循光滑界面的台阶横向长大机制,并沿着台阶的外法线方向长大.变温拉曼光谱研究表明CH₃NH₃PbCl₃单晶在温度160 K发生了正交-四方相转变,但四方相结构不稳定,存在的温度区间非常狭窄,故再次转变为立方相(Pm■m).紫外-可见-近红外吸收光谱和光致发光谱研究表明,CH₃NH₃PbCl₃单晶的吸收截止边约在波长442 nm,光致发光峰为450 ...     

阳极界面修饰对钙钛矿太阳能电池性能的影响

采用在聚(3,4-乙撑二氧噻吩)∶聚苯乙烯磺酸(Poly(3,4-ethylenedioxythiophene)∶Poly(styrenesulfonate),PEDOT∶PSS)阳极界面层上直接旋涂二甲基亚砜(Dimethyl Sulfoxide,DMSO)的方法,对PEDOT∶PSS薄膜进行修饰,以提高所制得的钙钛矿太阳能电池器件性能.在5000rpm转速条件下旋涂DMSO后,器件的能量转换效率达到11.43%,与PEDOT∶PSS阳极界面层未做任何修饰的器件相比,效率提高了29.15%.测试表征了修饰前后PEDOT∶PSS薄膜的透光性、表面形貌、电导率、器件的外量子效率曲线以及器件在光照和暗态下的J-V特性曲线,分析了器件性能提高的原因.结果表明:经过修饰的PEDOT∶PSS薄膜导电性显著增强,从而更加有利于器件阳极对空穴的抽取和收集;较未修饰时,器件的短路电流密度得到了大幅度提升,进而使得器件获得更高的能量转换效率.     

CH3 NH3 PbBr3表面修饰对SnO2基光电探测器性能的影响

SnO_2基紫外探测器具有较高的光响应度,但由于材料存在持续光电导效应,其响应时间较长,限制了其在光电探测领域的应用。为此,我们研究了表面修饰对SnO_2基光电探测器件的性能影响。采用化学气相沉积的方法制备了高结晶质量的SnO_2微米线,并在此基础上制备了基于单根SnO_2微米线的光电探测器。同时制备了高质量的钙钛矿CH_3NH_3PbBr_3材料,并与SnO_2微米线结合制备出经过修饰的SnO_2基器件。两种器件在紫外波段都呈现出明显的光响应,响应峰值位于250 nm处。相比单根SnO_2微米线器件,经过修饰后的SnO_2微米线探测器的响应度提高了10倍,响应时间由单根SnO_2微米线器件的几百乃至上千秒缩短为0.9 s。这一研究结果说明我们所采用的方法非常有望应用到高性能SnO_2光电探测器的制备中。     

无机钙钛矿太阳能电池Cs2SnI6的电子结构和光学性质的第一性原理研究

近年来,Cs2SnI6作为一种无毒性、稳定性好的新型钙钛矿材料应用于太阳能电池中,其电池的光电转换效率由最初不到1%增长到现在的8.5%,使之成为有可能替代铅基钙钛矿太阳能电池的新型太阳能电池。本文采用基于广义密度泛函和杂化密度泛函的第一性原理方法研究了Cs2SnI6的电子结构、光学特性和钙钛矿太阳能电池的光电性能参数。研究结果表明,导带底和价带顶位于同一高对称点Γ而属于直接跃迁型半导体,且电子态主要来自于I-5p轨道和Sn-5s轨道。在近红外和可见光波长范围内有较高的吸收系数,当Cs2SnI6钙钛矿厚度达到10μm时,吸收率在311~989 nm之间接近100%,不考虑潜在损失的情况下,理论上太阳能电池可获得短路电流为32.86 mA/cm2、开路电压0.91 V、填充因子87.4%、光电转换效率26.1%。为实验上制备高效Cs2SnI6钙钛矿太阳能电池提供了参考。     

胆甾液晶掺杂活性层对有机太阳能电池性能的影响

以poly(3-hexylthiophene)(P3HT)为电子给体,indene-C60bisadduct(ICBA)为电子受体,通过掺杂不同浓度胆甾液晶氯化胆甾醇制备了有机体异质结太阳能电池.结果表明,适当浓度掺杂使器件的开路电压提高到了0.78 V,但短路电流密度却有所降低,填充因子几乎不变,能量转换效率提高了10%.利用X射线、光致发光、原子力显微镜及紫外-可见吸收光谱进行表征,发现液晶掺杂对活性层的结晶度、分子内部排列情况、薄膜表面形貌和光吸收特性等都有明显影响.     

基底温度对喷涂技术制备大面积有机太阳能电池性能的影响

以聚3-己基噻吩（P3HT）和富勒烯衍生物（PCBM）体系的有机太阳能电池器件为基础,采用喷涂法制备了有机太阳能电池的空穴传输层和有机功能层,研究了基底温度对薄膜的形貌和器件性能的影响,并采用喷涂技术制备了一面积为11.2 cm²的大面积有机太阳能电池器件。研究发现,随着基底温度的升高,薄膜的粗糙度下降,吸收率提高,当基底温度为130 ℃时器件的性能最优,面积为25 mm²的器件的能量转换效率为2.09%。将多个独立的小面积电池进行串联和并联,制备了有效面积为11.2 cm²的大面积有机太阳能电池组件,其能量转换效率为1.83%,在面积增大44.8倍的情况下,效率仅损失不到13%。     

钙钛矿结构ZrBeO3稳定性的第一性原理研究

基于密度泛函理论构建了钙钛矿结构ZrBeO3晶体模型,计算了该晶体模型结合能,表明了该构型热力学稳定性;计算出该结构在不同压力下的弹性常数,并据此计算了ZrBeO3的体积模量、剪切模量、杨氏模量、泊松比、BH/GH(体模量/剪切模量)等参数,结果表明该材料具有机械稳定性,随着等静压力增加,材料由脆性向韧性转变;计算了零压下ZrBeO3的硬度,为34.5 GPa,表明该结构晶体应为超硬材料;计算了ZrBeO3的声子能谱,结果表明ZrBeO3在低温零压下热动力学不稳定,为此分析比较了不同压力下的声子能谱、不同原子轨道及化学键布居值,研究表明随着压力增加,Be原子sp杂化后形成的Be-O共价键成分增强、Zr-O键离子键成分增强,晶格动力学趋于稳定。     

Ag纳米颗粒对有机小分子太阳能电池性能的改善

在有机小分子太阳能电池CuPc/C60和TiOPc/C60的阳极ITO表面分别制备了一层Ag纳米颗粒,并采用MoO3作为阳极缓冲层,器件的性能均得到有效改善.Ag纳米颗粒的引入所形成的表面等离子激元共振可显著提高有机光活性层的吸收效率和光生激子的分解效率;而MoO3有效抑制了光生激子在有机/金属界面处发生的猝灭,提高了...     

NH3分子在LiH(100)表面吸附的第一性原理研究

采用第一性原理方法研究了NH3分子在LiH(100)晶面的表面吸附情况. 通过研究LiH(100) /NH3体系的吸附位置、吸附能和电子结构,发现NH3分子在Li3N (100)晶面主要是化学吸附,初始位置为NH3分子中N-H键在Li顶位时失去一个H原子,并在LiH(110)面形成NH2基,其吸附能为0.511 eV,属于强化学吸附,吸附作用最强. 此时NH2基与附近H原子和Li原子之间为离子键作用,NH2基中N—H键为共价键;NH3分子中另一个H原子与LiH表面的一个H原子形成一个H2分子逸出表面. H2分子中H-Ｈ键为明显的共价键.     

NH3分子在LiH（100）表面吸附的第一性原理研究

采用第一性原理方法研究了NH₃分子在LiH（100）晶面的表面吸附情况.通过研究LiH（100）/NH₃体系的吸附位置、吸附能和电子结构,发现NH₃分子在LiH（100）晶面主要是化学吸附,初始位置为NH₃分子中N-H键在Li顶住时失去一个H原子,并在LiH（100）面形成NH₂基,其吸附能为0.511 eV,属于强化学吸附,吸附作用最强.此时NH₂基与附近H原子和Li原子之间为离子键作用,NH₂基中N—H键为共价键;NH₃分子中另一个H原子与LiH表面的一个H原子形成一个H₂分子逸出表面.H₂分子中H-H键为明显的共价键.     

Humidity controlled crystallization of thin CH3NH3PbI3 films for high performance perovskite solar cell

Control of crystallization of a solution‐processed perovskite layer is of prime importance for high performance solar cells. In spite of the negative effect of water on perovskite solar energy conversion in several previous works, we observed that humidity plays a critical role to develop a thin uniform, dense perovskite film with preferred crystals, in particular, in a device with architecture of ITO/PEDOT:PSS/CH₃NH₃PbI₃/ PC₇₁BM/LiF/Al fabricated by two‐step sequential spin‐coating process. Humidity controlled spin‐coating of CH₃NH₃I on the pre‐formed PbI₂ layer was the most influential process and systematic structural investigation as a function of humidity revealed that grains of CH₃NH₃PbI₃ perovskite crystals increase in size with their preferred orientation while film surface becomes roughened as the humidity increases. The performance of a device was closely related to the humidity dependent film morphology and in 40% relative humidity, the device exhibited the maximum power conversion efficiency of approximately 12% more than 10 times greater than that of a device fabricated at 20% humidity. The results suggest that our process with controlled humidity can be another efficient route for high performance and reliable perovskite solar cells. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Hole‐extraction layer dependence of defect formation and operation of planar CH3NH3PbI3 perovskite solar cells

Three planar CH₃NH₃PbI₃ (MAPbI₃) solar cells having the same structure except a hole‐extraction layer (HEL) showed distinctive difference in operation characteristics. Analysis of frequency‐dependent capacitance and dielectric‐loss spectra of the three MAPbI₃ devices showed two types of recombination‐loss channels with different time constants that we attributed respectively to interface and bulk defects. Discrepancy in defect formation among the three devices with a HEL of PEDOT:PSS, NiO_x, or Cu‐doped NiO_x was not surprising because grain‐size distribution and crystalline quality of MAPbI₃ can be affected by surface energy and morphology of underlying HELs. We were able to quantify interface and bulk defects in these MAPbI₃solar cells based on systematic and simultaneous simulations of capacitance and dielectric‐loss spectra, and current–voltage characteristics by using the device simulator SCAPS.

     

CH3NH3PbI3/poly‐3‐hexylthiophen perovskite mesoscopic solar cells: Performance enhancement by Li‐assisted hole conduction

To address if the non‐triphenylamine derivative hole transporting materials such as P3HT (poly‐3‐hexylthiophene) could also exhibit high device efficiency in mesoscopic MAPbI₃ perovskite solar cells, we examined the effect of Li‐TFSI (Li‐bis(trifluoromethanesulfonyl) imide) and t‐BP (4‐tert‐butylpyridine) additives added in P3HT on device performance. Unlike the triphenylamine HTMs, the P3HT thiophene HTM without amine moiety was not doped by the additives but its conductivity was significantly improved by the Li‐TFSI/t‐BP mediated additional hole conduction. By inclusion of Li‐TFSI/t‐BP additive, we could fabricate more efficient mesoscopic MAPbI₃ perovskite solar cells with smaller hysteresis with respect to scan direction due to Li mediated additional hole conduction. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Nonhydrogenic exciton spectrum in perovskite CH3NH3PbI3

The excitons in the orthorhombic phase of the perovskite CH₃NH₃PbI₃ are studied using the effective mass approximation. The electron–hole interaction is screened by a distance‐dependent dielectric function, as described by the Haken potential or the Pollmann–Büttner potential. The energy spectrum and the eigenfunctions are calculated for both cases. The results show that the Pollmann–Büttner model, using the corresponding parameters obtained from ab initio calculations, provides better agreement with the experimental results.

     

Hole blocking PbI2/CH3NH3PbI3 interface

Modulated charge separation across (MO)/CH₃NH₃PbI₃ and (MO)/PbI₂/CH₃NH₃PbI₃ (MO = TiO₂, MoO₃) interfaces was investigated by surface photovoltage (SPV) spectroscopy. Perovskite layers were deposited by solution‐based one‐step preparation and two‐step preparation methods. An unreacted PbI₂ layer remained at the interface between the metal oxide and CH₃NH₃PbI₃ for two‐step preparation. For the two‐step preparation on TiO₂, the SPV signal related to absorption in CH₃NH₃PbI₃ increased in comparison to the one‐step preparation due to electron transfer from CH₃NH₃PbI₃ via PbI₂ into TiO₂ whereas the SPV signal related to defect transitions decreased. For the one‐step preparation on MoO₃, holes photogenerated in CH₃NH₃PbI₃ recombined with electrons in MoO₃. In contrast, a hole transfer from CH₃NH₃PbI₃ towards MoO₃ was blocked by the PbI₂ interlayer for the two‐step preparation on MoO₃. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

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.     

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.     

CH3NH3I在制备CH3NH3PbI(3-x)Clx钙钛矿太阳能电池中的作用

利用具有钙钛矿结构的有机-无机杂化卤化物制备的太阳能电池, 由于具有溶液可加工性和高光电转换效率, 受到了广泛关注. 在目前报道的最高光电转换效率的器件中, 采用了CH₃NH₃PbI_(3-x)Cl_x碘氯混合钙钛矿作为吸光层, 据报道在这种材料中光电子的扩散长度可以超过1 μm. 本文综述了在CH₃NH₃PbI_(3-x)Cl_x方面现有的研究工作, 指出了薄膜制备条件的重要性, 并研究了CH₃NH₃I在PbCl₂/CH₃NH₃I热解法制备CH₃NH₃PbI_(3-x)Cl_x吸光层中的作用. 扫描电子显微镜研究表明CH₃NH₃I加入量为PbCl₂的2倍到2.75倍时, CH₃NH₃I加入量的增加可以提高CH₃NH₃PbI_(3-x)Cl_x吸光层的覆盖度和结晶度, CH₃NH₃I加入量进一步增加到3倍时, 形貌变化不大. X射线光电子能谱的数据证实了CH₃NH₃I加入量对覆盖度的影响, 并显示在CH₃NH₃I加入量大于PbCl₂的2.5倍以后, CH₃NH₃PbI_(3-x)Cl_x中氯的掺入量急剧下降. 光电测试表明器件性能随CH₃NH₃I加入量增加而增加, 在CH₃NH₃I/PbCl₂为3/1时达到最高, 加入量略小于3/1对性能影响不大.     

Efficient design of perovskite solar cell using mixed halide and copper oxide

Solar cells based on perovskites have emerged as a transpiring technology in the field of photovoltaic. These cells exhibit high power conversion efficiency. The perovskite material is observed to have good absorption in the entire visible spectrum which can be well illustrated by the quantum efficiency curve. In this paper, theoretical analysis has been done through device simulation for designing solar cell based on mixed halide perovskite. Various parameters have efficacy on the solar cell efficiency such as defect density, layer thickness, doping concentration, band offsets, etc. The use of copper oxide as the hole transport material has been analyzed. The analysis divulges that due to its mobility of charge carriers, it can be used as an alternative to spiro-OMeTAD. With the help of simulations, reasonable materials have been employed for the optimal design of solar cell based on perovskite material. With the integration of copper oxide into the solar cell structure, the results obtained are competent enough. The simulations have shown that with the use of copper oxide as hole transport material with mixed halide perovskite as absorber, the power conversion efficiency has improved by 6%.The open circuit voltage has shown an increase of 0.09 V, short circuit current density has increased by 2.32 m A/cm~2, and improvement in fill factor is 8.75%.     

Exceptional elastic anisotropy of hybrid organic–inorganic perovskite CH3NH3PbBr3 measured by laser ultrasonic technique

The results of the direct experimental evaluation of all elastic constants of single crystal hybrid organic–inorganic perovskite (HOIP) methylammonium lead bromide, a material known due to its possible solar‐energy, optoelectronics, X‐ray detector and thermoelectricity applications, are reported. The measurements of anisotropic elasticity of CH₃NH₃PbBr₃by the technique of laser ultrasonics demonstrate that properties of HOIPs can be even more remarkable than the theoretical expectations: the extracted shear modulus is more than twice smaller, the universal anisotropy is more than twice higher, while the Debye temperature is more than 50° lower. Thus HOIPs can exhibit extremely low shear rigidity and extremely high anisotropy, both strongly overrunning the parameters which have been expected based on earlier first principles theoretical predictions. A simple theoretical model of granular crystal indicates that these observations could be related to the contributions of rotations/tilts of PbBr₆octahedra to elastic response of cubic CH₃NH₃PbBr₃. Another experimental observation is strong stiffening of shear rigidity with temperature increase from its room value up to 120 °C. Discovered elastic properties of HOIPs characterize them as exceptionally ductile/flexible/adaptive materials which could be deposited on corrugated/structured surfaces. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)