铅基卤素钙钛矿阻变式存储器研究进展

随着数字通信在大数据以及物联网等领域的应用,推动了下一代存储设备的发展。阻变式存储器因其功耗低、尺寸可调、操作速度快等优点被认为是最有前景的信息存储器件之一。近年来,兼具成本低、带隙可调、载流子扩散长度长、离子迁移速率快、载流子迁移率高等优点的铅基卤素钙钛矿,在阻变式存储器领域引起了广泛关注。主要对铅基卤素钙钛矿阻变式存储器最新研究进展进行了概述,就铅基卤素钙钛矿阻变式存储器结构、阻变性能、阻变机理等方面进行了综述。最后,对铅基卤素钙钛矿阻变式存储器当前面临的挑战进行了讨论,并对其未来的发展前景进行了展望。     

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.     

Defect control and ionic conductivity of oxynitride perovskite Sr0.83Li0.17Ta0.83O1.88N0.74

Perovskite lattice was tailored by introducing site vacancies and mixed anion composition, to produce Sr_0.83Li_0.17Ta_0.83O_1.88N_0.74 (Li02N). Further, Li02N was converted to a defect oxide Sr_0.83Li_0.17Ta_0.83O₃ (Li02O) by applying an optimized treatment: heating in air at 1173 K for 2 h. According to the neutron Rietveld refinement, Li02N and Li02O are tetragonal and orthorhombic, respectively, where the lattice volume of Li02O is significantly smaller than that of Li02N. The ionic conductivity (σ_ion) of Li02N and Li02O was evaluated by the ac impedance spectroscopy and the equivalent circuit analysis. Both Li02N (σ_ion = 10^?5.5 S/cm at 671 K) and Li02O (σ_ion = 10^?6.2 S/cm at 667 K) exhibited an Arrhenius behavior of ionic conductivity with activation energies of 0.87 eV and 0.75 eV, respectively. It is interpreted that the nitride component enhances the ionic conduction of Li02N, while the vacancy of the anion lattice makes an opposite effect.     

TiI4-doping induced bulk defects passivation in halide perovskites for high efficient photovoltaic devices

Power conversion efficiency (PCE) and stability are two important properties of perovskite solar cells (PSCs). Particularly, defects in the perovskite films could cause the generation of trap states, thereby increasing the nonradiative recombination. To address this issue, suitable dopants can be incorporated to react with non-bonded atoms or surface dangling bonds to passivate the defects. Herein, we introduced TiI₄ into CH₃NH₃PbI₃ (MAPbI₃) film and obtained a dense and uniform morphology with large crystal grains and low defect density. The champion cell based on 0.5% TiI₄-doped MAPbI₃ achieved a PCE as high as 20.55%, which is superior to those based on pristine MAPbI₃ (17.64%). Moreover, the optimal solar cell showed remarkable stability without encapsulation. It retained 88.03% of its initial PCE after 300 h of storage in ambient. This work demonstrates TiI₄ as a new and effective passivator for MAPbI₃ film.     

Suppressed Lattice Disorder for Large Emission Enhancement and Structural Robustness in Hybrid Lead Iodide Perovskite Discovered by High-Pressure Isotope Effect

The soft nature of organic–inorganic halide perovskites renders their lattice particularly tunable to external stimuli such as pressure, undoubtedly offering an effective way to modify their structure for extraordinary optoelectronic properties. Here, using the methylammonium lead iodide as a representative exploratory platform, it is observed that the pressure-driven lattice disorder can be significantly suppressed via hydrogen isotope effect, which is crucial for better optical and mechanical properties previously unattainable. By a comprehensive in situ neutron/synchrotron-based analysis and optical characterizations, a remarkable photoluminescence (PL) enhancement by threefold is convinced in deuterated CD₃ND₃PbI₃, which also shows much greater structural robustness with retainable PL after high peak-pressure compression–decompression cycle. With the first-principles calculations, an atomic level understanding of the strong correlation among the organic sublattice and lead iodide octahedral framework and structural photonics is proposed, where the less dynamic CD₃ND₃⁺ cations are vital to maintain the long-range crystalline order through steric and Coulombic interactions. These results also show that CD₃ND₃PbI₃-based solar cell has comparable photovoltaic performance as CH₃NH₃PbI₃-based device but exhibits considerably slower degradation behavior, thus representing a paradigm by suggesting isotope-functionalized perovskite materials for better materials-by-design and more stable photovoltaic application.     

Construction of CaTiO3 nanosheets with boron nitride quantum dots as effective photogenerated hole extractor for boosting photocatalytic performance under simulated sunlight

Herein, titanate-based perovskite CaTiO₃ nanosheets were successfully designed via boron nitride quantum dots (BNQDs) to fabricate CaTiO₃/BNQDs catalyst. The as-fabricated composite catalysts were analysed by transmission electron microscope (TEM), scanning electron microscopy coupled with energy dispersive spectrometry (SEM-EDS), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR), X-ray diffraction (XRD), UV–vis spectroscopy (UV-DRS), photoluminescence (PL) and electrochemical impedance spectroscopy (EIS) techniques. SEM-Mapping analysis showed that the boron and nitrogen elements dispersed well over the CaTiO₃ surface which was useful for building electronic channels for rapid transport of photo-induced charge pairs. TEM images verified the attachment of BNQDs around the surface of host CaTiO₃ forming intimate interface while the distribution of chemical states was observed by XPS analysis demonstrating strong coupling effect between BNQDs and CaTiO₃ through Ti–O–N and Ti–O–B bonds. Moreover, PL and light absorption properties enhanced with the quantum confinement effect of BNQDs. As expected, the photocatalytic degradation rate of CaTiO₃/BNQDs was increased to k_app = 0.015 min^{? 1} with optimum BNQDs loading, which was 2.31 times folder than that of bare CaTiO₃ (0.006 min^{? 1}). The enhanced photocatalytic efficiency was observed for CaTiO₃/BNQDs than pristine perovskite on account of formation of electron tapping sites, decreased band gap energy and hindered recombination rate. On the other hand, in the presence of H₂O₂, the degradation percentage increased from 88.5% to 92.1% at the end of 120 min of irradiation while 96.8% of TC was quickly degraded within 60 min after activating with peroxymonosulfate which created strong sulphate radicals. Radical trapping tests indicated that the photo-generated holes were the primary active species in the photocatalytic mechanism. Moreover, CaTiO₃/BNQDs catalyst showed excellent stability in recycling tests. Besides, the possible degradation mechanism was proposed. This study shed light on the significance of BNQDs in the enhancement of the photocatalytic activities of titanate-based perovskite for effective degradation of tetracycline antibiotic in contaminated water.     

Inter-Sample and Intra-Sample Variability in Electronic Properties of Methylammonium Lead Iodide

While the challenges associated with the stability of metal halide perovskites are well known and intensely studied, variability in electronic properties represents an equally significant, yet seldom studied, challenge that could potentially slow or inhibit the commercial viability of these systems. In this work, the contactless characterization technique time-resolved microwave conductivity (TRMC) is used to quantify the variability in electronic properties of the prototypical perovskite, methylammonium lead iodide (MAPbI₃) both between different samples, and at different locations within the same sample. Using scanning electron microscopy (SEM) and a quasi-automated image-analysis strategy, it is possible to evaluate the metrics of heterogeneity in surface microstructure and correlate them with the electronic properties as obtained by TRMC. Substantial intra-sample and inter-sample variation is observed in the mobility-yield product in samples prepared following differing protocols, and in samples prepared following identical protocols.     

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.     

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.