Spontaneous Polarization in an Ultrathin Improper-Ferroelectric/Dielectric Bilayer in a Capacitor Structure at Cryogenic Temperatures

To determine the effect of depolarization and the critical thickness in improper-ferroelectric hexagonal-ferrite thin films, we investigate the polarization switching of a ferroelectric/dielectric bilayer in capacitor structures at 20 K. Experimentally, we show that the spontaneous polarization persists throughout the studied thickness range (3 to 80 unit cell), even with a thick (10-nm) dielectric layer, suggesting no practical thickness limit for applications. By fitting the effect of depolarization using the phenomenological theory, we show that the spontaneous polarization remains finite when the thickness of the ferroelectric layer approaches zero, providing a hint for the absence of critical thickness. We also find that the interfacial effects limit the multidomain formation and govern the polarization switching mechanisms

Duality of switching mechanisms and transient negative capacitance in improper ferroelectrics

The recent discovery of transient negative capacitance has sparked an intense debate on the role of homogeneous and inhomogeneous mechanisms in polarizations switching. In this work, we report observation of transient negative capacitance in improper ferroelectric h-YbFeO3 films in a resistor-capacitor circuit, and a concaved shape of anomaly in the voltage wave form, in the early and late stage of the polarizations switching respectively. Using a phenomenological model, we show that the early-stage negative capacitance is likely due to the inhomogeneous switching involving nucleation and domain wall motion, while the anomaly at the late stage, which appears to be a reminiscent negative capacitance is the manifestation of the thermodynamically unstable part of the free-energy landscape in the homogeneous switching. The complex free-energy landscape in hexagonal ferrites may be the key to cause the abrupt change in polarization switching speed and the corresponding anomaly. These results reconcile the two seemingly conflicting mechanisms in the polarization switching and highlight their different roles at different stages. The unique energy-landscape in hexagonal ferrites that reveals the dual switching mechanism suggests the promising application potential in terms of negative capacitance.Comment: 14 pages,5 figure

Domain‑wall magnetoelectric coupling in multiferroic hexagonal YbFeO\u3csub\u3e3\u3c/sub\u3e films

Electrical modulation of magnetic states in single-phase multiferroic materials, using domain-wall magnetoelectric (ME) coupling, can be enhanced substantially by controlling the population density of the ferroelectric (FE) domain walls during polarization switching. In this work, we investigate the domain-wall ME coupling in multiferroic h-YbFeO3 thin films, in which the FE domain walls induce clamped antiferromagnetic (AFM) domain walls with reduced magnetization magnitude. Simulation according to the phenomenological theory indicates that the domain-wall ME effect is dramatically enhanced when the separation between the FE domain walls shrinks below the characteristic width of the clamped AFM domain walls during the ferroelectric switching. Experimentally, we show that while the magnetization magnitude remains same for both the positive and the negative saturation polarization states, there is evidence of magnetization reduction at the coercive voltages. These results suggest that the domain-wall ME effect is viable for electrical control of magnetization

Colossal optical anisotropy from atomic-scale modulations

In modern optics, materials with large birefringence ({\Delta}n, where n is the refractive index) are sought after for polarization control (e.g. in wave plates, polarizing beam splitters, etc.), nonlinear optics and quantum optics (e.g. for phase matching and production of entangled photons), micromanipulation, and as a platform for unconventional light-matter coupling, such as Dyakonov-like surface polaritons and hyperbolic phonon polaritons. Layered "van der Waals" materials, with strong intra-layer bonding and weak inter-layer bonding, can feature some of the largest optical anisotropy; however, their use in most optical systems is limited because their optic axis is out of the plane of the layers and the layers are weakly attached, making the anisotropy hard to access. Here, we demonstrate that a bulk crystal with subtle periodic modulations in its structure -- Sr9/8TiS3 -- is transparent and positive-uniaxial, with extraordinary index n_e = 4.5 and ordinary index n_o = 2.4 in the mid- to far-infrared. The excess Sr, compared to stoichiometric SrTiS3, results in the formation of TiS6 trigonal-prismatic units that break the infinite chains of face-shared TiS6 octahedra in SrTiS3 into periodic blocks of five TiS6 octahedral units. The additional electrons introduced by the excess Sr subsequently occupy the TiS6 octahedral blocks to form highly oriented and polarizable electron clouds, which selectively boost the extraordinary index n_e and result in record birefringence ({\Delta}n > 2.1 with low loss). The connection between subtle structural modulations and large changes in refractive index suggests new categories of anisotropic materials and also tunable optical materials with large refractive-index modulation and low optical losses.Comment: Main text + supplementar

Giant Modulation of Refractive Index from Correlated Disorder

Correlated disorder has been shown to enhance and modulate magnetic, electrical, dipolar, electrochemical and mechanical properties of materials. However, the possibility of obtaining novel optical and opto-electronic properties from such correlated disorder remains an open question. Here, we show unambiguous evidence of correlated disorder in the form of anisotropic, sub-angstrom-scale atomic displacements modulating the refractive index tensor and resulting in the giant optical anisotropy observed in BaTiS3, a quasi-one-dimensional hexagonal chalcogenide. Single crystal X-ray diffraction studies reveal the presence of antipolar displacements of Ti atoms within adjacent TiS6 chains along the c-axis, and three-fold degenerate Ti displacements in the a-b plane. 47/49Ti solid-state NMR provides additional evidence for those Ti displacements in the form of a three-horned NMR lineshape resulting from low symmetry local environment around Ti atoms. We used scanning transmission electron microscopy to directly observe the globally disordered Ti a-b plane displacements and find them to be ordered locally over a few unit cells. First-principles calculations show that the Ti a-b plane displacements selectively reduce the refractive index along the ab-plane, while having minimal impact on the refractive index along the chain direction, thus resulting in a giant enhancement in the optical anisotropy. By showing a strong connection between correlated disorder and the optical response in BaTiS3, this study opens a pathway for designing optical materials with high refractive index and functionalities such as a large optical anisotropy and nonlinearity.Comment: 24 pages, 3 figure

First-Principles Prediction of a Stable Hexagonal Phase of CH₃NH₃PbI₃

Methylammonium lead iodide (CH₃NH₃PbI₃ or MAPbI₃) perovskite is a promising new photovoltaic material with high power conversion efficiency. However, its perovskite phase with corner-connected PbI₆ octahedra shows poor environmental stability. More recently, MAPbI₃ has been shown to be thermodynamically unstable with a positive formation enthalpy. Here, using first-principles density functional theory calculations, we predict a layered hexagonal phase of MAPbI₃ consisting of infinite chains of face-shared PbI₆ octahedra with <i>P</i>6₃<i>mc</i> space-group symmetry to be thermodynamically the most stable phase for a wide range of volume and temperature compared to any of the experimentally observed perovskite phases with a different tilt pattern of the corner-connected octahedra. The predicted hexagonal phase is also dynamically stable without any soft phonon modes. The change from corner to face-shared connectivity in the hexagonal phase leads to a predicted band gap of 2.6 eV and a band structure that favors highly anisotropic charge transport

Enabling selective zinc-ion intercalation by a eutectic electrolyte for practical anodeless zinc batteries.

Two major challenges hinder the advance of aqueous zinc metal batteries for sustainable stationary storage: (1) achieving predominant Zn-ion (de)intercalation at the oxide cathode by suppressing adventitious proton co-intercalation and dissolution, and (2) simultaneously overcoming Zn dendrite growth at the anode that triggers parasitic electrolyte reactions. Here, we reveal the competition between Zn2+ vs proton intercalation chemistry of a typical oxide cathode using ex-situ/operando techniques, and alleviate side reactions by developing a cost-effective and non-flammable hybrid eutectic electrolyte. A fully hydrated Zn2+ solvation structure facilitates fast charge transfer at the solid/electrolyte interface, enabling dendrite-free Zn plating/stripping with a remarkably high average coulombic efficiency of 99.8% at commercially relevant areal capacities of 4 mAh cm-2 and function up to 1600 h at 8 mAh cm-2. By concurrently stabilizing Zn redox at both electrodes, we achieve a new benchmark in Zn-ion battery performance of 4 mAh cm-2 anode-free cells that retain 85% capacity over 100 cycles at 25 °C. Using this eutectic-design electrolyte, Zn | |Iodine full cells are further realized with 86% capacity retention over 2500 cycles. The approach represents a new avenue for long-duration energy storage

Domain-wall magnetoelectric coupling in multiferroic hexagonal YbFeO3 films

Electrical modulation of magnetic states in single-phase multiferroic materials, using domain-wall magnetoelectric (ME) coupling, can be enhanced substantially by controlling the population density of the ferroelectric (FE) domain walls during polarization switching. In this work, we investigate the domain-wall ME coupling in multiferroic h-YbFeO3 thin films, in which the FE domain walls induce clamped antiferromagnetic (AFM) domain walls with reduced magnetization magnitude. Simulation according to the phenomenological theory indicates that the domain-wall ME effect is dramatically enhanced when the separation between the FE domain walls shrinks below the characteristic width of the clamped AFM domain walls during the ferroelectric switching. Experimentally, we show that while the magnetization magnitude remains same for both the positive and the negative saturation polarization states, there is evidence of magnetization reduction at the coercive voltages. These results suggest that the domain-wall ME effect is viable for electrical control of magnetization