Improvement of Photoluminescence of Perovskite CH_3NH_3Pb I_3 by Adding Additional CH_3NH_3I during Grinding

The organic-inorganic hybrid perovskite CH_3NH_3PbI_3 has been a good candidate for many optoelectronic applications such as light-emitting diodes due to its unique properties.Optimizing the optical properties of the CH_3NH_3PbI_3 material to improve the device performance is a hot topic.Herein,a new strategy is proposed to enhance the light emission of CH_3NH_3PbI_3 phosphor effectively.By adding the reactant CH_3NH_3I powder in an appropriate proportion and simply grinding,the emission intensity of CH_3NH_3PbI_3 is greatly improved.The advantages of the proposed method are swiftness,simplicity and reproducibility,and no requirement for a complex organic ligand.The mechanism of this phenomenon is revealed by x-ray diffraction,scanning electron microscopy,energy dispersive spectroscopy,photoluminescence,and temperature-dependent photoluminescence.This study offers a unique insight for optimizing the optical properties of halide perovskite materials.     

Ultrafast Terahertz Probes of Charge Transfer and Recombination Pathway of CH_3NH_3PbI_3 Perovskites

We use transient terahertz photoconductivity measurements to demonstrate that upon optical excitation of CH_3NH_3PbI_3 perovskite, the hole transfer from CH_3NH_3PbI_3 into the organic hole-transporting material(HTM)Spiro-OMe TAD occurs on a sub-picosecond timescale. Second-order recombination is the dominant decay pathway at higher photo-excitation fluences as observed in neat CH_3NH_3PbI_3 films. In contrast, under similar experimental conditions, second-order recombination weakly contributes the relatively slow recombination between the electrons in the perovskite and the injected holes in HTM, as a loss mechanism at the CH_3NH_3PbI_3/Spiro-OMe TAD interface. Our results offer insights into the intrinsic photophysics of CH_3NH_3PbI_3-based perovskites with direct implications for photovoltaic devices and optoelectronic applications.     

CH_3NH_3 Formed by Electron Injection at Heterojunction Inducing Peculiar Properties of CH_3NH_3PbI_3 Material

The effect of formed CH_3NH_3 at the heterojunction on properties of CH_3NH_3PbI_3 material is investigated based on experiment and theoretical calculation. Our calculation results show that the giant dielectric constant, anomalous hysteresis and long-lasting polarization for CH_3NH_3PbI_3 originate from the formed CH_3NH_3 at the heterojunction. It is found that the induced weak EPS by the reorientation of CH_3NH_3 sub-group along the built-in electric field enables us to effectively increase the ordering of entire lead-halide framework. In addition, the heterojunction has an advantage of channel separation between carrier transport and electron diffusion. These properties of the heterojunction are the main origin of the high efficiency of CH_3NH_3PbI_3 solar cells.     

Importance of PbI_2 morphology in two-step deposition of CH_3NH_3PbI_3 for high-performance perovskite solar cells

Controlling the morphology of the perovskite film is an effective way to improve the photoelectric conversion efficiency of solar cell devices. In this work, we study the influence of the crystallization condition on PbI_2 morphology and the performances of resulting perovskite solar cells. The PbI_2 morphologies and coverage rates under different formation conditions such as solvent effect, slow crystallization at room temperature and substrate-preheating, are found to be of crucial importance for preparing high-quality perovskite. The generation of loosely packed disk-like PbI_2 film with interpenetrating nanopores promotes the penetration of methyl ammonium iodide(MAI), leading to a better crystallinity of the perovskite film, and a best repeatable power conversion efficiency of 11.59% is achieved when methyl ammonium lead triiodide(CH_3NH_3PbI_3, MAPbI_3) is employed. In addition, an excellent device is also obtained with an efficiency of more than 93% to remain after working for 43 days.     

The structural,electronic, and optical properties of organic–inorganic mixed halide perovskites CH_3NH_3Pb(I_(1-y)X_y)_3(X = Cl,Br)

Methylammmonium lead iodide perovskites(CH_3NH_3PbI_3) have received wide attention due to their superior optoelectronic properties. We performed first-principles calculations to investigate the structural, electronic, and optical properties of mixed halide perovskites CH_3NH_3Pb(I_(1-y)X_y)_3(X = Cl, Br; y = 0, 0.33, 0.67). Our results reveal the reduction of the lattice constants and dielectric constants and enhancement of band gaps with increasing doping concentration of Cl-/Br-at I-. Electronic structure calculations indicate that the valance band maximum(VBM) is mainly governed by the halide p orbitals and Pb 6 s orbitals, Pb 6 p orbitals contribute the conduction band minimum(CBM) and doping does not change the direct semiconductor material. The organic cation [CH_3NH_3]~+does not take part in the formation of the band and only one electron donates to the considered materials. The increasing trends of the band gap with Cl content from y = 0(0.793 eV) to y = 0.33(0.953 eV) then to y = 0.67(1.126 eV). The optical absorption of the considered structures in the visible spectrum range is decreased but after doping the stability of the material is improving.     

O_3 fast and simple treatment-enhanced p-doped in Spiro-MeOTAD for CH_3NH_3I vapor-assisted processed CH_3NH_3PbI_3 perovskite solar cells

We demonstrate a simple and fast post-deposition treatment with high process compatibility on the hole transport material(HTM) Spiro-MeOTAD in vapor-assisted solution processed methylammonium lead triiodide(CH_3NH_3PbI_3)-based solar cells. The prepared Co-doped p-type Spiro-MeOTAD films are treated by O_3 at room temperature for 5 min,10 min, and 20 min, respectively, prior to the deposition of the metal electrodes. Compared with the traditional oxidation of Spiro-MeOTAD films overnight in dry air, our fast O_3 treatment of HTM at room temperature only needs just 10 min,and a relative 40.3% increment in the power conversion efficiency is observed with respect to the result of without-treated perovskite solar cells. This improvement of efficiency is mainly attributed to the obvious increase of the fill factor and short-circuit current density, despite a slight decrease in the open-circuit voltage. Ultraviolet photoelectron spectroscopy(UPS) and Hall effect measurement method are employed in our study to determine the changes of properties after O_3 treatment in HTM. It is found that after the HTM is exposed to O_3, its p-type doping level is enhanced. The enhancement of conductivity and Hall mobility of the film, resulting from the improvement in p-doping level of HTM, leads to better performances of perovskite solar cells. Best power conversion efficiencies(PCEs) of 13.05% and 16.39% are achieved with most properly optimized HTM via CH_3NH_3I vapor-assisted method and traditional single-step method respectively.     

A Simple Deposition Method for Self-Assembling Single Crystalline Hybrid Perovskite Nanostructures

A sequential deposition method is developed, where the hybrid organic-inorganic halide perovskite(CH_3 NH_3Pb(I_(1-x)Br_x)_3) is synthesized using precursor solutions containing CH_3NH_3I and PbBr_2 with different mole ratios and reaction times. The perovskite achieved here is quite stable in the atmosphere for a relatively long time without noticeable degradation, and the perovskite nanowires are proved to be single crystalline structure, based on transmission electron microscopy. Furthermore, strong red photoluminescence from perovskite is observed in the wavelength range from 746 nm to 770 nm with the increase of the reaction time, on account of the exchanges between I-ions and Br~-ions in the perovskite crystal. Lastly, the influences of concentration and reaction time of the precursor solutions are discussed, which are important for evolution of hybrid perovskite from nanocuboid to nanowire and nanosheet.     

Could two-dimensional perovskites fundamentally solve the instability of perovskite photovoltaics

The high efficiency and low production cost enable the halide perovskite solar cells as a promising technology for the next generation photovoltaics. Nevertheless, the relatively poor stability of the organic-inorganic halide perovskites hinders their commercial applications. In the past few years, two-dimensional (2D) perovskite has emerged as a more stable alternative to the three-dimensional (3D) counterparts and attracted intense research interests. Although many attempts and advances have been made, it is still ambiguous that whether the 2D perovskites could bring closure to the stability issue. To answer this essential question, a systematic study of the nature of 2D halide perovskites is necessary. Here, we focus on the stability investigations of 2D perovskites from different perspectives, especially light, heat, ion migration and strain. Several remaining challenges and opening problems are also discussed. With further material and device engineering, we believe that the 2D perovskites would promote perovskite solar cells to a promising future.     

Recent advances in controlling the crystallization of two-dimensional perovskites for optoelectronic device

Though three-dimensional (3D) organic–inorganic halide perovskites (OIHP) is very promising for low cost and distributed PV generation, the stability issue of 3D OIHP is still a problem for its commercialization. Two-dimensional (2D) perovskites, protected by periodic organic ligands, is promising due to its excellent optoelectronic property and superior stability. However, 2D perovskite is anisotropic in its crystal structure and optoelectronic properties, and the resulted film is often a mixture of different phase. So, methods to manipulate 2D perovskite crystal orientation and its phase separation are vital. In this review, the major advances on the composition engineering, crystal orientation, phase separation, and interfacial capping are summarized. Besides, efforts on understanding the formation process of 2D perovskite crystal are also discussed, which is important for making full use of 2D perovskite in functional optoelectronic devices.     

Improving the performance of perovskite solar cells with glycerol-doped PEDOT:PSS buffer layer

In this paper, we investigate the effects of glycerol doping on transmittance, conductivity and surface morphology of poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate))(PEDOT:PSS) and its influence on the performance of perovskite solar cells.. The conductivity of PEDOT:PSS is improved obviously by doping glycerol. The maximum of the conductivity is 0.89 S/cm when the doping concentration reaches 6 wt%, which increases about 127 times compared with undoped. The perovskite solar cells are fabricated with a configuration of indium tin oxide(ITO)/PEDOT:PSS/CH_3NH_3PbI_3/PC_(61)BM/Al, where PEDOT:PSS and PC_(61)BM are used as hole and electron transport layers, respectively. The results show an improvement of hole charge transport as well as an increase of short-circuit current density and a reduction of series resistance, owing to the higher conductivity of the doped PEDOT:PSS. Consequently, it improves the whole performance of perovskite solar cell. The power conversion efficiency(PCE) of the device is improved from 8.57% to 11.03% under AM 1.5 G(100 mW/cm~2 illumination) after the buffer layer has been modified.     

Adsorption Regularity and Characteristics of sp~3-Hybridized Gas Molecules on Anatase TiO_2(101) Surface

We report the anatase titanium dioxide(101) surface adsorption of sp~3-hybridized gas molecules,including NH_3,H_2O and CH_4,using first-principles plane-wave ultrasoft pseudopotential based on the density functional theory.The results show that it is much easier for a surface with oxygen vacancies to adsorb gas molecules than it is for a surface without oxygen vacancies.The main factor affecting adsorption stability and energy is the polarizability of molecules,and adsorption is induced by surface oxygen vacancies of the negatively charged center.The analyses of state densities and charge population show that charge transfer occurs at the molecule surface upon adsorption and that the number of transferred charge reduces in the order of N,O and C.Moreover,the adsorption method is chemical adsorption,and adsorption stability decreases in the order of NH_3,H_2O and CH_4.Analyses of absorption and reflectance spectra reveal that after absorbed CH_4 and H_2O,compared with the surface with oxygen vacancy,the optical properties of materials surface,including its absorption coefficients and reflectivity index,have slight changes,however,absorption coefficient and reflectivity would greatly increase after NH_3 adsorption.These findings illustrate that anatase titanium dioxide(101) surface is extremely sensitive to NH_3.     

Designing solar-cell absorber materials through computational high-throughput screening

Although the efficiency of CH_3 NH_3 PI_3 has been refreshed to 25.2%,stability and toxicity remain the main challenges for its applications.The search for novel solar-cell absorbers that are highly stable,non-toxic,inexpensive,and highly efficient is now a viable research focus.In this review,we summarize our recent research into the high-throughput screening and materials design of solar-cell absorbers,including single perovskites,double perovskites,and materials beyond Perovskites.BazrS_3(single perovskite),Ba_2 BiNbS_6(double perovskite),HgAl_2 Se_4(spinel),and IrSb_3(skutterudite)were discovered to be potential candidates in terms of their high stabilities,appropriate bandgaps,small carrier effective masses,and strong optical absorption.     

金属卤化物钙钛矿纳米光电材料的研究进展

金属卤化物钙钛矿广泛应用于太阳能电池、发光二极管和纳米激光器等领域,引起了科学家们极大的兴趣.纳米材料由于具有量子约束和较强的各项异性,表现出与普通块体材料不同的光学和电学性质.金属卤化物钙钛矿纳米材料具有可调节带隙、高量子效率、强的光致发光、量子约束效应和长的载流子寿命等优点,并且其成本低、储量丰富、易于合成多种化合物,有很广阔的光电应用前景.但另一方面,钙钛矿由于表面存在陷阱缺陷状态以及晶体边界导致稳定性较差,环境中的水、氧气、紫外线和温度等因素会使其光电性能大幅度降低.本文介绍量子点、纳米线、纳米片钙钛矿纳米材料的合成与生长机制,并且讨论其新奇的光电性能及在各种光电设备中的应用.最后总结了钙钛矿材料新出现的挑战并讨论了下一代金属卤化物钙钛矿光电设备应用.     

The influence of localized states on the optical absorption and carrier transport properties of acylamino hybrid perovskites with tunable electronic structures

Organic-inorganic hybrid perovskite solar cells have excellent optoelectronic properties, but their low thermal and chemical stabilities limit their commercial applications. In this paper, a new type of organic-inorganic hybrid perovskite is proposed. Malondiamide (MA,CH₂(CONH₂)₂) and propionamide (PA, CH₃CH₂CONH₂) were used as organic layers, with Pb-I octahedral inorganic layers to form quasi three-dimensional (3D) perovskites. The crystal structure, stability, electronic structure, and optical properties of MAPbI₄ and PAPbI₄ perovskites were investigated, and the results showed that there were localized states that corresponded to the number of acyl groups in the two perovskites. Energy band calculations showed that the localized states of the two perovskites rose above the bottom of the conduction band. This can be used to regulate the band gap of the two perovskites, which affects the electronic properties and optical absorption characteristics of the two perovskites. Compared with PAPbI₄, MAPbI₄ has a lower formation energy, lower band gap, lower effective mass of electrons and holes, wider energy range, and larger absorption coefficient, which indicates that MAPbI₄ is more suitable for use in solar cells. This study provides guidance for obtaining efficient and stable photovoltaic materials.     

Surface stabilized cubic phase of CsPbI_3 and CsPbBr_3 at room temperature

Inorganic halide perovskites CsPb X_3(X = I, Br) have attracted tremendous attention in solar cell applications. However, the bulk form of the cubic phase CsPb X_3, which offers moderate direct bandgaps, is metastable at room temperature and tends to transform into a tetragonal or orthorhombic phase. Here, our density functional theory calculation results found that the surface energies of the cubic phase are smaller than those of the orthorhombic phase, although the bulk counterpart of the cubic phase is less stable than that of the orthorhombic phase. These results suggest a surface stabilization strategy to maintain the stability of the cubic phase at room temperature that an enlarged portion of surfaces shall change the relative stability of the two phases in nanostructured CsPb X_3. This strategy, which may potentially solve the long-standing stability issue of cubic CsPb X_3, was demonstrated to be feasible by our calculations in zero-, one-, and two-dimensional nanostructures. In particular, confined sizes from few to tens of nanometers could keep the cubic phase as the most thermally favored form at room temperature. Our predicted values in particular cases, such as the zero-dimensional form of CsPbI_3,are highly consistent with experimental values, suggesting that our model is reasonable and our results are reliable. These predicted critical sizes give the upper and lower limits of the confined sizes, which may guide experimentalists to synthesize these nanostructures and promote likely practical applications such as solar cells and flexible displays using CsPb X_3 nanostructures.     

影响杂化钙钛矿太阳能电池稳定性的因素探讨

自从2009年首次报道采用有机-无机杂化钙钛矿作为吸光材料用于太阳能电池以来, 钙钛矿太阳能电池效率的快速提升引起了人们广泛的关注, 这类电池同时具有制备工艺简单、成本低廉等优点, 引发了钙钛矿电池的研究热潮. 目前研究工作大多数集中在如何提高电池的光电转化效率, 但钙钛矿电池要真正实现产业化应用, 急需要解决材料及器件的稳定性问题. 本文探讨影响钙钛矿材料及器件的稳定性因素, 从温度及湿度等方面分析了材料的稳定性, 从传输材料及其界面问题讨论了器件的稳定性.     

Mechanical Properties of Formamidinium Halide Perovskites FABX_3(FA=CH(NH_2)_2; B=Pb,Sn; X=Br,I) by First-Principles Calculations

The mechanical properties of formamidinium halide perovskites FABX_3(FA=CH(NH_2)_2; B=Pb, Sn; X=Br, I)are systematically investigated using first-principles calculations. Our results reveal that FABX_3 perovskites possess excellent mechanical flexibility, ductility and strong anisotropy. We shows that the planar organic cation FA+ has an important effect on the mechanical properties of FABX3 perovskites. In addition, our results indicate that (i) the moduli(bulk modulus B, Young's modulus E, and shear modulus G) of FABBr_3 are larger than those of FABI_3 for the same B atom, and (ii) the moduli of FAPbX_3 are larger than those of FASnX_3 for the same halide atom. The reason for the two trends is demonstrated by carefully analyzing the bond strength between B and X atoms based on the projected crystal orbital Hamilton population method.     

Factors influencing the performance of paintable carbon-based perovskite solar cells fabricated in ambient air

To date, many efforts have been made to improve the performance of paintable carbon-based(PC-based) perovskite solar cells(PSCs). Though great progress has been achieved, their power conversion efficiencies are still relatively low compared with hole-transport-materials-based PSCs. General research on influencing factors of performance in PC-based PSCs is still insufficient. In this work, PC-based PSCs were fabricated in ambient air and four groups of controlled experiments were performed in which the PbI_2 layers were prepared with or without antisolvent extraction treatment. These four groups of experiments were designed to find out the effect of different influencing factors on PC-based PSCs performance,for example, PbI_2 residual, the surface morphology of the perovskite film, the surface roughness of the perovskite film, and the contact status of the perovskite/carbon electrode interface. With a systematic analysis, we demonstrated that the contact status of the perovskite/carbon electrode interface played a vital role in PC-based PSCs, and a flat, smooth perovskite surface could help to improve this contact status significantly. Besides, on the precondition of a poor contact interface, no PbI_2 residual and a good surface morphology only brought limited benefits to the performances of PC-based PSCs.     

MAPbI3-xBrx钙钛矿薄膜中溴梯度对界面电荷转移的促进作用

混合卤素钙钛矿由于具有优异的光物理性质成为了光电子领域应用中的明星材料. 因此,钙钛矿材料中光生载流子动力学的探究和调控对于进一步提升材料的性能具有重要意义. 本文通过表面离子交换法制备了具有溴梯度的MAPbI_3-xBr_x钙钛矿薄膜,并对其内部载流子传输及界面电荷转移动力学过程进行了系统的研究. 在MAPbI_3-xBr_x薄膜中,溴离子梯度分布所导致的能带梯度能有效促进光生空穴在薄膜内部的传输过程及在界面的提取过程. 同时,由于卤素离子交换的后处理方法对薄膜表面起到了修饰作用,薄膜界面处的本征电子转移速率也得到了显著的提升. 研究表明,在通过表面后处理方法制备的混合卤素钙钛矿薄膜中,有可能同时实现界面电子和空穴转移速率的提升,这对于进一步提升钙钛矿太阳能电池的能量转换效率具有一定的启发作用.     

Low‐Temperature‐Processed CdS as the Electron Selective Layer in an Organometal Halide Perovskite Photovoltaic Device

Organic–inorganic halide perovskites have recently been crowned as the leading next‐generation photovoltaic material due to their high efficiency and simple fabrication process. Herein, a low‐temperature‐processed CdS thin film (commonly used as a buffer layer in commercial CdTe or CIGSe solar cells) is reported as an electron selective layer in perovskite devices based on the following reasons: First, the photoelectric property of CdS thin film is investigated, illustrating the possibility of CdS as the electron selective layer in the application of methylammonium lead (II) iodide perovskite devices. More specifically, CdS semiconductor film presents a higher mobility compared with traditional TiO₂ thin film, which benefits the electron extraction and transmission; second, it is found that the perovskite thin film spun‐coating on the CdS substrates grows with an obvious tendency along the direction toward the thickness of thin film, which reduces the chance of recombination of electrons and hole, beneficial to their separation. It is also revealed that the perovskite‐device‐based CdS electron selective layer has a higher stability compared with that of TiO₂ due to the difference of substrates wetting.