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.     

Intrinsic Instability of the Hybrid Halide Perovskite Semiconductor CH_3NH_3PbI_3

The organic-inorganic hybrid perovskite CH_3NH_3PbI_3 has attracted significant interest for its high performance in converting solar light into electrical power with an efficiency exceeding 20%. Unfortunately, chemical stability is one major challenge in the development of CH_3NH_3PbI_3 solar cells. It was commonly assumed that moisture or oxygen in the environment causes the poor stability of hybrid halide perovskites, however, here we show from the first-principles calculations that the room-temperature tetragonal phase of CH_3NH_3PbI_3 is thermodynamically unstable with respect to the phase separation into CH_3NH_3I + PbI_2, i.e., the disproportionation is exothermic,independent of the humidity or oxygen in the atmosphere. When the structure is distorted to the low-temperature orthorhombic phase, the energetic cost of separation increases, but remains small. Contributions from vibrational and configurational entropy at room temperature have been considered, but the instability of CH_3NH_3PbI_3 is unchanged. When I is replaced by Br or Cl, Pb by Sn, or the organic cation CH_3NH_3 by inorganic Cs, the perovskites become more stable and do not phase-separate spontaneously. Our study highlights that the poor chemical stability is intrinsic to CH_3NH_3PbI_3 and suggests that element-substitution may solve the chemical stability problem in hybrid halide perovskite solar cells.     

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.     

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.     

A periodic DFT study on adsorption of small molecules(CH_4,CO,H_2O,H_2S,NH_3)on the WO_3(001) surface-supported Au

Gas molecules(such as CH4,CO,H2O,H2S,NH_3)adsorption on the pure and Au-doped WO3(001)surface have been studied by Density functional theory calculations with generalized gradient approximation.Based on the the calculation of adsorption energy,we found the most stable adsorption site for gas molecules by comparing the adsorption energies of different gas molecules on the WO3(001)surface.We have also compared the adsorption energy of five different gas molecules on the WO3(001)surface,our calculation results show that when the five kinds of gases are adsorbed on the pure WO3(001)surface,the order of the surface adsorption energy is CO>H2S>CH4>H2O>NH3.And the results show that NH3 is the most easily adsorbed gas among the other four gases adsorbed on the surface of pure WO3(001)surface.We also calculated the five different gases on the Au-doped WO3(001)surface.The order of adsorption energy was found to be different from the previous calculation:CO>CH4>H2S>H2O>NH3.These results provide a new route for the potential applications of Au-doped WO3 in gas molecules adsorption.     

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.     

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.     

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.     

Generation of high-energy-resolved NH_3 molecular beam by a Stark decelerator with 179 stages

We demonstrate the production of cold, slow NH_3 molecules from a supersonic NH_3 molecular beam using our electrostatic Stark decelerator consisting of 179 slowing stages. By using this long Stark decelerator, a supersonic NH_3 molecular beam can be easily decelerated to trappable velocities. Here we present two modes for operating the Stark decelerator to slow the supersonic NH_3 molecules. The first is the normal mode, where all 179 stages are used to decelerate molecules, and it allows decelerating the NH_3 molecular beam from 333 m/s to 18 m/s, with a final temperature of 29.2 mK.The second is the deceleration-bunch mode, which allows us to decelerate the supersonic NH_3 beam from 333 m/s to 24 m/s,with a final temperature of 2.9 m K. It is clear that the second mode promises to produce colder(high-energy-resolution)molecular samples than the normal mode. Three-dimensional Monte Carlo simulations are also performed for the experiments and they show a good agreement with the observed results. The deceleration-bunch operation mode presented here can find applications in the fields of cold collisions, high-resolution spectroscopy, and precision measurements.     

一种新型稀土配合物Eu(TTA)(2NH_2-Phen)_3的发光特性研究

合成了一种新型的稀土配合物Eu(TTA)(2NH_2-Phen)_3,将其作为掺杂物与基质聚乙烯基咔唑(PVK)按照不同质量比混合共溶,旋涂成膜.测量了混合薄膜的光致发光光谱,确认了所合成的Eu(TTA)(2NH_2H-Phen)_3具有发射荧光的能力,进而将其应用于电致发光器件中.还制备了以PVK:Eu(TTA)(2NH_2-Phen)_3为发光层,器件结构为ITO/PVK:Eu(TTA)(2NH_2-Phen)3/2,9-dimethy1-4,-diphenyl-1,10-plaenan thmline(BCP)/8-hydroxyquinoline aluminum(Alq_3)/Al的多层器件,得到了 Eu~(3+)的红色电敛发光.研究不同掺杂浓度时器件发光光谱的变化及PVK的发射光谱与Eu(TTA)(2NH_2-Phen)_3的吸收光谱的交叠情况,证明了混合薄膜中Eu~(3+)电致发光机理主要足载流子的直接俘获.     

一种新型的NH_3气敏光纤传感器

本文作者成功地研究一种二氧化锡与氧化锌混合物薄膜,用作光纤传感器,对氨气具有气敏特性,在一定的浓度范围内,具有良好的线性灵敏度。     

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.     

In-plane oriented CH_3NH_3PbI_3 nanowire suppression of the interface electron transfer to PCBM

One-dimensional nanowire is an important candidate for lead-halide perovskite-based photonic detectors and solar cells. Its surface population, diameter, and growth direction, etc., are critical for device performance. In this research,we carried out a detailed study on electron transfer process at the interface of nanowire CH_3 NH_3 PbI_3(N-MAPbI_3)/Phenyl C61 butyric acid methyl-ester synonym(PCBM), as well as the interface of compact CH_3 NH_3 PbI_3(C-MAPbI_3)/PCBM by transient absorption spectroscopy. By comparing the carrier recombination dynamics of N-MAPbI_3, N-MAPbI_3/PCBM,C-MAPbI_3, and C-MAPbI_3/PCBM from picosecond(ps) to hundred nanosecond(ns) time scale, it is demonstrated that electron transfer at N-MAPbI_3/PCBM interface is less efficient than that at C-MAPbI_3/PCBM interface. In addition, electron transfer efficiency at C-MAPbI_3/PCBM interface was found to be excitation density-dependent, and it reduces with photo-generation carrier concentration increasing in a range from 1.0 × 1018 cm~(-3)–4.0 × 1018 cm~(-3). Hot electron transfer,which leads to acceleration of electron transfer between the interfaces, was also visualized as carrier concentration increases from 1.0 × 10~(18) cm~(-3)–2.2 × 10~(18) cm~(-3).     

CH3CH2+N(4S)反应机理的理论研究

利用abinitio方法对CH3CH2+N(4S)反应进行了理论研究,在MP2/6-311+G(d,p)水平上优化得到了反应途径上的反应物、中间体、过渡态和产物的几何构型和谐振频率,并在QCISD(T)/6-311+G(d,p)水平上进行单点能计算.计算结果表明,CH2CH2+3NH和H2CN+CH3是此反应主要产物,CH3CHN+H是此反应次要产物.产物CH2CH2+3NH主要来自直接氢抽提反应通道,H2CN+CH3来自加成-解离反应通道,CH3CHN+H来自加成-解离反应通道.     

PbO对V_2O_5/TiO_2催化剂NH_3选择性催化还原NO的影响

基于铅在中国燃煤和MSW焚烧烟气中的特点,采用静态N_2物理吸附、NH_3化学吸附、程序升温表面反应、傅里叶变换红外光谱和催化剂活性评价的方法,研究了PbO对1 wt.%V_2O_5/TiO_2催化剂NH_3选择性催化还原NO的影响.结果表明,PbO使SCR催化剂活性降低.对于燃煤锅炉,PbO对V_2O_5/TiO_2催化剂的影响可以忽略不计;对于MSW焚烧炉,PbO是使V_2O_5/TiO_2催化剂失活的重要铅化合物.Pb覆盖在TiO_2表面上,与V活性位覆盖在TiO_2表面上的方式类似.催化剂的失活主要是由于PbO中和了催化剂表面Brφnsted酸性位的酸性,Brφnsted酸性位对于NH_3的吸附和活化起重要作用.     

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.     

Effect of defects on the electronic structure of a PbI_2/MoS_2 van der Waals heterostructure: A first-principles study

PbI_2/MoS_2, as a typical van der Waals(vdW) heterostructure, has attracted intensive attention owing to its remarkable electronic and optoelectronic properties. In this work, the effect of defects on the electronic structures of a PbI_2/MoS_2 heterointerface has been systematically investigated. The manner in which the defects modulate the band structure of PbI_2/MoS_2, including the band gap, band edge, band alignment, and defect energy-level density within the band gap is discussed herein. It is shown that sulfur defects tune the band gaps, iodine defects shift the positions of the band edge and Fermi level, and lead defects realize the conversions between the straddling-gap band alignment and valence-band-aligned gap, thus enhancing the light-absorption ability of the material.     

Fluorescence Enhancement of Metal-Capped Perovskite CH_3NH_3PbI_3 Thin Films

We fabricate nano-structural metal films to improve photoluminescence of perovskite films. When the perovskite film is placed on an ammonia-treated alumina film, stronger photoluminescence is found due to local field enhancement effects. In addition, the oxide spacer layer between the metal(e.g.,Al, Ag and Au) substrate and the perovskite film plays an important role. The simulations and experiments imply that the enhancement is related to surface plasmons of nano-structural metals.     

First-principles hybrid functional study of the electronic structure and charge carrier mobility in perovskite CH_3NH_3SnI_3

We calculate the electronic properties and carrier mobility of perovskite CH_3NH_3SnI_3 as a solar cell absorber by using the hybrid functional method. The calculated result shows that the electron and hole mobilities have anisotropies with a large magnitude of 1.4 × 10~4cm~2·V~(-1)·s~(-1) along the y direction. In view of the huge difference between hole and electron mobilities, the perovskite CH3NH3 Sn I3can be considered as a p-type semiconductor. We also discover a relationship between the effective mass anisotropy and electronic occupation anisotropy. The above results can provide reliable guidance for its experimental applications in electronics and optoelectronics.