Study of Pb-based and Pb-free perovskite solar cells using Cu-doped Ni1-xO thin films as hole transport material

SCAPS solar cell simulation program was applied to model an inverted structure of perovskite solar cells using Cu-doped Ni_1-xO thin films as hole transport layer. The Cu-doped Ni_1-xO film were made by co-sputtering deposition under different deposition conditions. By increasing the amount of the Cu-dopant, the film crystallinity enhanced whereas the bandgap energy decreased. The transmittance of the thin films decreased significantly by increasing the sputtering power of copper. High quality, uniform, compact, and pin-hole free films with low surface roughness were achieved. The structural, chemical, surface morphology, optical, electrical, and electronic properties of the Cu doped Ni_1-xO films were used as input parameters in the simulation of Pb-based (MAPbI_3-xCl_x) and Pb-free (MAGeI₃) perovskite solar cells. Simulation results showed that the performance of both Pb-based and Pb-free perovskite solar cell devices significantly enhanced with Cu-doped Ni_1-xO film. The highest power conversion efficiency (PCE) for the Pb-free perovskite solar cell is 8.9% which is lower than the highest PCE of 17.5% for the Pb-based perovskite solar cell.     

The phosphorescence emission in undoped lead-halide Cs4PbBr6 single crystals at low temperature

Recently, all-inorganic cesium lead-halide perovskites have shown their promise for light emission applications, due to the excellent optical performance. Herein, we report that the initially nonphosphorescent undoped lead-halide Cs₄PbBr₆ single crystals (SCs) exhibit an ultralong phosphorescence emission under X-ray excitation at low temperatures. It is shown that the dramatic change has been taken place in radioluminescence spectra and the broad-band emission gradually appeared with the decrease of temperature. Below 210 K, the radioluminescence spectra can be deconvoluted into one narrow peak located at 530 nm and two broad peaks centered at 595 nm and 672 nm respectively. Subsequently, the time-dependent radioluminescence spectra in undoped lead-halide Cs₄PbBr₆ SCs were investigated. The ultralong phosphorescence emission can persist over 120 min at 70 K. We consider that ultralong phosphorescence originates from defect-related emission. To the best of our knowledge, our finding is the first time that undoped Cs₄PbBr₆ SCs exhibit the phosphorescence emission, which will offer a paradigm to motivate revolutionary applications on perovskite.     

Surface Reconstruction Engineering with Synergistic Effect of Mixed-Salt Passivation Treatment toward Efficient and Stable Perovskite Solar Cells

Surface passivation treatment is a widely used strategy to resolve trap-mediated nonradiative recombination toward high-efficiency metal-halide perovskite photovoltaics. However, a lack of passivation with mixture treatment has been investigated, as well as an in-depth understanding of its passivation mechanism. Here, a systematic study on a mixed-salt passivation strategy of formamidinium bromide (FABr) coupled with different F-substituted alkyl lengths of ammonium iodide is demonstrated. It is obtained better device performance with decreasing chain length of the F-substituted alkyl ammonium iodide in the presence of FABr. Moreover, they unraveled a synergistic passivation mechanism of the mixed-salt treatment through surface reconstruction engineering, where FABr dominates the reformation of the perovskite surface via reacting with the excess PbI₂. Meanwhile, ammonium iodide passivates the perovskite grain boundaries both on the surface and top perovskite bulk through penetration. This synergistic passivation engineer results in a high-quality perovskite surface with fewer defects and suppressed ion migration, leading to a champion efficiency of 23.5% with mixed-salt treatment. In addition, the introduction of the moisture resisted F-substituted groups presents a more hydrophobic perovskite surface, thus enabling the decorated devices with excellent long-term stability under a high humid atmosphere as well as operational conditions.     

Symmetric and asymmetric membranes based on La0.5Sr0.5Fe0.7Ga0.3O3-δ perovskite with high oxygen semipermeation flux performances and identification of the rate-determining step of oxygen transport

This work focuses on identifying the rate-determining step of oxygen transport through La_0.5Sr_0.5Fe_0.7Ga_0.3O_3-δ membranes with symmetric and asymmetric architectures. The best oxygen semipermeation fluxes are 3.4 10⁻³ mol. m^-2.s^-1 and 6.3 10⁻³ mol. m^-2.s^-1 at 900 °C for the symmetric membrane and asymmetric membrane with a modified surface. The asymmetric membrane with a modified surface leads to an increase of approximately 7 times the oxygen flux compared to that obtained with the La_0.5Sr_0.5Fe_0.7Ga_0.3O_3-δ dense membrane without surface modification. This work also shows that the oxygen flux is mainly governed by gaseous oxygen diffusion through the porous support of asymmetric La_0.5Sr_0.5Fe_0.7Ga_0.3O_3-δ membranes.     

Electrical and magnetic properties of double perovskite: Y2CoMnO6

In this communication, the structural, micro-structural, dielectric, electrical, magnetic, and leakage-current characteristics of a double perovskite (Y₂CoMnO₆) ceramic material have been reported. The material was synthesized via a high-temperature mixed-oxide route. The compound crystallizes in a monoclinic structure which is confirmed from preliminary X-ray structural study. The morphological study by using scanning electron micrograph reveals the almost homogeneous distribution of grains throughout the surface of the sample. The nature of frequency-dependence of dielectric constant has been described by the Maxwell-Wagner model. The occurrence of a dielectric anomaly in the temperature dependence of dielectric permittivity study demonstrates the ferroelectric-paraelectric phase transition in the material. From the Nyquist plots, we found the existence of both grain and grain boundary effects. The frequency dependence of conductivity was studied by the Jonscher’s Power law, and the conduction phenomenon obeys the large overlapping polaron tunneling model. By using the Arrhenius equation, the activation energy has been calculated which is nearly equal to the energy required for the hoping of the electron. Both impedance and conductivity analysis demonstrate that the sample exhibits negative temperature coefficient of resistance (NTCR) properties indicating the semiconducting type of material at high temperatures. The anti-ferromagnetic character of the material is observed from the nature of magnetic hysteresis loop. The leakage current analysis suggests that the conduction process in the material follows the space charge limited conduction phenomenon. Such material will be helpful for modern electronic devices and spintronic applications.     

Effects of the film thickness and poling electric field on photovoltaic performances of (Pb,La)(Zr,Ti)O3 ferroelectric thin film-based devices

The ferroelectric photovoltaic (FPV) effect obtained in inorganic perovskite ferroelectric materials has received much attention because of its large potential in preparing FPV devices with superior stability, high open-circuit voltage (V_oc) and large short-circuit current density (J_sc). In order to obtain suitable thickness for the ferroelectric thin film as light absorption layer, in which, the sunlight can be fully absorbed and the photo-generated electrons and holes are recombined as few as possible, we prepare Pb_0.93La_0.07(Zr_0.6Ti_0.4)_0.9825O₃ (PLZT) ferroelectric thin films with different layer numbers by the sol-gel method and based on these thin films, obtain FPV devices with FTO/PLZT/Au structure. By measuring photovoltaic properties, it is found that the device with 4 layer-PLZT thin film (~300 nm thickness) exhibits the largest V_oc and J_sc and the photovoltaic effect obviously depends on the value and direction of the poling electric field. When the device is applied a negative poling electric field, both the V_oc and J_sc are significantly higher than those of the device applied the positive poling electric field, due to the depolarization field resulting from the remnant polarization in the same direction with the built-in electric field induced by the Schottky barrier, and the higher the negative poling electric field, the larger the V_oc and J_sc. At a -333 kV/cm poling electric field, the FPV device exhibits the most superior photovoltaic properties with a V_oc of as high as 0.73 V and J_sc of as large as 2.11 μA/cm². This work opens a new way for developing ferroelectric photovoltaic devices with good properties.     

Synthesis,structure, CO oxidation,and H2 production activities of CaCu3−xMnxTi4−xMnxO12 (x = 0, 0.5, and 1.0)

Synthesis of nanocrystalline pristine and Mn-doped calcium copper titanate quadruple perovskites, CaCu_3?xMn_xTi_4?xMn_xO₁₂ (x = 0, 0.5, and 1.0) by modified citrate solution combustion method has been reported. Powder X-ray diffraction patterns attest the phase purity of the perovskite materials. Average particle sizes of all the materials obtained from the Scherrer's formula are in the range of 55–70 nm. The specific surface areas for all the perovskites obtained from BET isotherms are found to be low as expected for the condensed oxide systems and fall in the range of 13–17 m² g^?1. Transmission electron microscopy studies show a reduction in particle size of CaCu₃Ti₄O₁₂ with increase in Mn doping. Ca and Ti are present in +2 and +4 oxidation states in all the materials as demonstrated by X-ray photoelectron spectroscopy analyses. Cu²⁺ gets reduced in CaCu₃Ti₄O₁₂ with higher Mn content. Mn is observed to be present only in +3 oxidation state. All the materials have been examined to be active in CO oxidation as well as H₂ production from methanol steam reforming. CaCu₃Ti₄O₁₂ with ~14 at.% Mn is found to show best catalytic activities among these materials. A comprehensive analysis of the catalytic activities of these perovskites toward CO oxidation and H₂ production from MSR reveal the cooperative activity of copper-manganese in the doped perovskites and it is more effective at lower manganese content.     

Electrocatalytic activity of LaSr3Fe3O10 and LaSr3Fe3O10-GO towards oxygen reduction reaction in alkaline medium

Oxygen reduction reaction(ORR) plays a critical role in many energy conversion and storage processes.Therein, a comparative study of the electrocatalytic activity for ORR in 0.1 mol/L KOH solution was conducted using layered perovskite-like LaSr_3 Fe_3 O_(10) and LaSr3 Fe_3 O_(10)-graphene oxide(GO) composite as electrodes. Linear sweep voltammetry(LSV) results show that the LaSr3 Fe_3 O_(10)-GO hybrid exhibits higher current density, a more positive onset potential(-0.15 V vs. Hg/HgO) in comparison with LaSr_3 Fe_3 O_(10).The value of the overall transferred electrons for both catalysts implies a dominant two electron process for ORR. Both catalysts under alkalic conditions exhibit a two-step Tafel slope, suggesting a change in the reaction mechanism for ORR. The composite electrode exhibits a higher ORR current density, but inferior durability performances in relative to the LaSr_3 Fe_3 O_(10) electrode.     

从PZT体系看无铅压电陶瓷的可能应用

总结了主要以(Bi0.5Na0.5)TiO3和NaNbO3为基的无铅压电陶瓷的性能，以Pb(Ti，Zr)TiO3基二元系、三元系压电陶瓷的性能与应用为参考，分析了无铅压电陶瓷可能的器件应用。此外，还对拓宽无铅压电陶瓷应用需要改进的性能提出了建议。     

Ca掺杂钨镁酸铅陶瓷材料的制备及其介电性能

研究了Ca掺杂钨镁酸铅(PMW)陶瓷材料的合成、结构、烧结以及介电性能。结果发现：在Ca^2 摩尔分数小于15％时，能形成单相的PCMW钙铁矿相，结构由原来的斜方相向立方相转变。用二步合成法制备的样品容易致密烧结，气孔率比一步法制备的样品小。Ca的加入降低了材料的介电损耗，在频率为1MHz时，介质损耗达到了10^-4。当Ca^2 摩尔分数大于10％时，材料的Curie峰宽化显著，介电常数温度系数降低。