Molecular Engineering Regulation Achieving Out-of-Plane Polarization in Rare-Earth Hybrid Double Perovskites for Ferroelectrics and Circularly Polarized Luminescence.

Out-of-plane polarization is a highly desired property of two-dimensional (2D) ferroelectrics for application in vertical sandwich-type photoferroelectric devices, especially in ultrathin ferroelectronic devices. Nevertheless, despite great advances that have been made in recent years, out-of-plane polarization remains unrealized in the 2D hybrid double perovskite ferroelectric family. Here, from our previous work 2D hybrid double perovskite HQERN ((S3HQ)4EuRb(NO3)8, S3HQ = S-3-hydroxylquinuclidinium), we designed a molecular strategy of F-substitution on organic component to successfully obtain FQERN ((S3FQ)4EuRb(NO3)8, S3FQ = S-3-fluoroquinuclidinium) showing circularly polarized luminescence (CPL) response. Remarkably, compared to the monopolar axis ferroelectric HQERN, FQERN not only shows multiferroicity with the coexistence of multipolar axis ferroelectricity and ferroelasticity but also realizes out-of-plane ferroelectric polarization and a dramatic enhancement of Curie temperature of 94 K. This is mainly due to the introduction of F-substituted organic cations, which leads to a change in orientation and a reduction in crystal lattice void occupancy. Our study demonstrates that F-substitution is an efficient strategy to realize and optimize ferroelectric functional characteristics, giving more possibility of 2D ferroelectric materials for applications in micro-nano optoelectronic devices.

Halogen-Regulated Tc and X-ray Radiation Detection in 2D Hybrid Perovskite Ferroelastic Semiconductor.

Organic-inorganic hybrid perovskites (OIHPs) have received particular attention due to their characteristic structural tunability and flexibility. These features make OIHPs behave with excellent modifications on macroscopic properties, such as ferroicity or semiconductor performances, etc. Herein, we report two 2D hybrid stibium-based halide perovskite (C3H7N)3Sb2X9 (X = Br, 1; Cl, 2) ferroelastic semiconductor possessing dual switching properties of dielectric and second harmonic generation (SHG). Notably, these two hybrids exhibit halogen-regulated ferroelasticity and semiconductor properties. There is a significant difference in Curie temperature (Tc) and X-ray radiation detection sensitivity (S), i.e., the ΔTc and ΔS are 38 K and 87 µC Gyair-1 cm-2, respectively. Meanwhile, crystals 1 and 2 do not show dark current drift in cyclic measurements of different radiation doses with stable switching ratios of 30 and 10, separately. Meanwhile, these results were proven by scientific experimental results and density functional theory (DFT) calculations. Our work presents a facile and practical method to regulate macroproperties on the molecular level, providing a new vision to develop hybrid perovskite ferroic-photoelectric materials.

Ferroelectricity and Related Properties of Nitratecadmate(II) Hybrid with Metal-Vacancy.

All crystals are not ideal, and many of their properties are often determined not by the regular arrangement of atoms, but by the irregular arrangement of crystal defects. Many properties of materials can be controlled effectively by proper use of solid defects. By substitution of NH4 + ion of a hexagonal perovskite structure (H2 dabco)(NH4 )(NO3 )3 (dabco=1,4-diazabicyclo[2.2.2]octane, 1) with Cd2+ ion, we obtained a new metal-vacancy compound (H2 dabco)2 Cd(H2 O)2 (NO3 )6 (2). It exhibits a ferroelectric-paraelectric phase transition at 261 K. A comparison of the various-temperature single-crystal structures indicates that the coordination twist of Cd2+ ion leads to instability of the lattices and excellent ferroelectricity. These findings reveal that the vacancy can be utilized as an element to produce ferroelectricity and may start the chemistry of metal-vacancy coordination compounds. These findings reveals that the vacancy can be utilized as an effective means to tune the symmetry and produce ferroelectricity.

Large Enhancement of Polarization in a Layered Hybrid Perovskite Ferroelectric Semiconductor via Molecular Engineering.

Switchable spontaneous polarization is the vital property of ferroelectrics, which leads to other key physical properties such as piezoelectricity, pyroelectricity, and nonlinear optical effects, etc. Recently, organic-inorganic hybrid perovskites with 2D layered structure have become an emerging branch of ferroelectric materials. However, most of the 2D hybrid ferroelectrics own relatively low polarizations (<15 µC cm-2 ). Here, a strategy to enhance the polarization of these hybrid perovskites by using ortho-, meta-, para-halogen substitution is developed. Based on (benzylammonium)2 PbCl4 (BZACL), the para-chlorine substituted (4-chlorobenzylammonium)2 PbCl4 (4-CBZACL) ferroelectric semiconductor shows a large spontaneous polarization (23.3 µC cm-2 ), which is 79% larger than the polarization of BZACL. This large enhancement of polarization is successfully explained via ab initio calculations. The study provides a convenient and efficient strategy to promote the ferroelectric property in the hybrid perovskite family.

Crystal Sponge Behavior in a Two-Dimensional Rare-Earth Hybrid Coordinate Polymer.

Stimuli-responsive multifunctional materials (SRMMs) have attracted tremendous attention due to their dynamic responses to external stimuli. However, it remains challenging to simultaneously achieve solvent-induced single-crystal to single-crystal (SCSC) transformation and structural phase transition after desolvation. Here, we report a two-dimensional (2D) rare-earth organic-inorganic hybrid coordinate polymer [(CH3)3NCH2Cl]2[Eu·H2O]2[CH2(SO3)2]4·2H2O (1) that exhibits a reversible SCSC transformation by changing to 2 ([(CH3)3NCH2Cl][Eu·H2O][CH2(SO3)2]2). Impressively, the SCSC transformation process couples with large changes in quantum efficiency dropped from 33.68% of 1 to 20.07% that of 2. Furthermore, polymer 2 shows an isomorphic structural phase transition associated with switching dielectric. Notably, the distance of the 2D layers shows reversible change during the two successive transition processes displaying a crystal sponge behavior. This work reveals the potential of rare-earth 2D hybrid coordination polymers in the design of multifunctional responsive materials and opens a new prospect to explore the construction of novel SRMMs.

Uncovering the Indium Filament Revolution in Transparent Bipolar ITO/SiOx/ITO Resistive Switching Memories.

Transparent resistive switching random access memory (ReRAM) is of interest for the future integrated invisible circuitry. However, poor understanding of its working mechanism in transparent ReRAMs with the indium tin oxide (ITO) electrode is still a critical problem and will hinder its widespread applications. To reveal the actual working mechanism in transparent ReRAMs with the ITO electrode, we investigate the transparent ITO/SiOx/ITO memory devices (∼82% transmittance in the visible region) and compare it with ITO/SiOx/Au memory devices, which both can exhibit reproducible bipolar switching. The indium (In) filament evolution, which accounts for the bipolar switching behaviors in the ITO/SiOx/ITO (or Au) memories, is directly observed using transmission electron microscopy on samples with different memory states (electroformed, ON, and OFF). These studies uncover the microscopic mechanism behind the bipolar switching in SiOx-based ReRAM devices with the ITO electrode, providing a general guidance for the design of high-performance ReRAMs with large scalability and high endurance.

Resonant scattering of green light enabled by Ag@TiO2 and its application in a green light projection screen.

The ability to selectively scatter green light is essential for an RGB transparent projection display, and this can be achieved by a silver-core, titania-shell nanostructure (Ag@TiO2), based on the metallic nanoparticle's localized surface plasmon resonance. The ability to selectively scatter green light is shown in a theoretical design, in which structural optimization is included, and is then experimentally verified by characterization of a transparent film produced by dispersing such nanoparticles in a polymer matrix. A visual assessesment indicates that a high-quality green image can be clearly displayed on the transparent film. For completeness, a theoretical design for selective scattering of red light based on Ag@TiO2 is also shown.

Direct Observation of Indium Conductive Filaments in Transparent, Flexible, and Transferable Resistive Switching Memory.

Electronics with multifunctionalities such as transparency, portability, and flexibility are anticipated for future circuitry development. Flexible memory is one of the indispensable elements in a hybrid electronic integrated circuit as the information storage device. Herein, we demonstrate a transparent, flexible, and transferable hexagonal boron nitride (hBN)-based resistive switching memory with indium tin oxide (ITO) and graphene electrodes on soft polydimethylsiloxane (PDMS) substrate. The ITO/hBN/graphene/PDMS memory device not only exhibits excellent performance in terms of optical transmittance (∼85% in the visible wavelength), ON/OFF ratio (∼480), retention time (∼5 × 104 s) but also shows robust flexibility under bending conditions and stable operation on arbitrary substrates. More importantly, direct observation of indium filaments in an ITO/hBN/graphene device is found via ex situ transmission electron microscopy, which provides critical insight on the complex resistive switching mechanisms.