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.     

Fe3O4-carbon spheres core–shell supported palladium nanoparticles: A robust and recyclable catalyst for suzuki coupling reaction

Suzuki-Miyaura (S-M) is regarded the most powerful way for synthesis biaryls, triaryls, or incorporating of substituted aryl moieties in organic preparation by the cross-coupling of aryl boronic acid with aryl halides using the Pd catalyst. This work reports the combining of the hydrothermal and microwave-assisted protocol to convert the glucose to magnetic carbon spheres (Fe₃O₄-CSPs) decorated with Pd nanoparticles (NPs) as the catalyst for Suzuki-Miyaura cross-coupling reactions. The physicochemical properties in the produced composite were examined using FESEM, HRTEM, nitrogen isotherms, Raman spectroscopy, FTIR, XPS, and XRD. The as-fabricated composite Pd/Fe₃O₄-CSPs is mostly spherical with a core–shell structure and possesses a great surface area of 253.2 m²·g^-1. Its catalytic performance demonstrates that the composite has excellent stability and high tolerance Suzuki-Miyaura cross-coupling reactions in 30 min at 80 ℃. Both activated and deactivated aryl halides provided excellent yield. The as-fabricated catalyst was recycled for up to four catalytic cycles without a substantial decline in performance. Moreover, this research offers a facile roadmap for synthesizing Pd/Fe₃O₄-CSPs composites and promoting the practical implementation of Pd/Fe₃O₄-CSPs catalysts for organic transformation processes.     

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.     

Revealing Nanomechanical Domains and Their Transient Behavior in Mixed-Halide Perovskite Films

Halide perovskites are a versatile class of semiconductors employed for high performance emerging optoelectronic devices, including flexoelectric systems, yet the influence of their ionic nature on their mechanical behavior is still to be understood. Here, a combination of atomic-force, optical, and compositional X-ray microscopy techniques is employed to shed light on the mechanical properties of halide perovskite films at the nanoscale. Mechanical domains within and between morphological grains, enclosed by mechanical boundaries of higher Young's Modulus (YM) than the bulk parent material, are revealed. These mechanical boundaries are associated with the presence of bromide-rich clusters as visualized by nano-X-ray fluorescence mapping. Stiffer regions are specifically selectively modified upon light soaking the sample, resulting in an overall homogenization of the mechanical properties toward the bulk YM. This behavior is attributed to light-induced ion migration processes that homogenize the local chemical distribution, which is accompanied by photobrightening of the photoluminescence within the same region. This work highlights critical links between mechanical, chemical, and optoelectronic characteristics in this family of perovskites, and demonstrates the potential of combinational imaging studies to understand and design halide perovskite films for emerging applications such as photoflexoelectricity.     

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.     

Grain size influence on the flexibility and luminous intensity of inorganic CaTiO3:Pr3+ crystal nanofibers

Traditional inorganic materials exhibit rigidity owing to the lack of polymer chains in polymer materials or atom slipping in metals. However, nanometerization has been recently proposed for the conversion of inorganic oxide materials into flexible materials. Herein, the flexible inorganic luminescent material, CaTiO₃:0.2%Pr³⁺, was synthesized through electrospinning, and the macroscopic flexibility of pure inorganic CaTiO₃:0.2%Pr³⁺ was achieved. The flexible membrane was characterized via X-ray diffraction, thermogravimetry, scanning electron microscopy (SEM), and photoluminescence analyses. The grain size was analyzed at various calcination temperatures via SEM, and the results suggested that the increase in the calcination temperature resulted in the growth of crystal grains. Studies have reported that the growth of crystal grains is beneficial for improving the luminescence performance; however, to obtain better flexibility, smaller crystal grains are required. This study provides an important reference for the design of flexible inorganic materials.