Polar Metal Research Articles

Observation of Quasi-Two-Dimensional Polar Domains and Ferroelastic Switching in a Metal, Ca3Ru2O7

Polar domains arise in insulating ferroelectrics when free carriers are unable to fully screen surface-bound charges. Recently discovered binary and ternary polar metals exhibit broken inversion symmetry coexisting with free electrons that might be expected to suppress the electrostatic driving force for domain formation. Contrary to this expectation, we report the first direct observation of polar domains in single crystals of the polar metal Ca3Ru2O7. By a combination of mesoscale optical second-harmonic imaging and atomic-resolution scanning transmission electron microscopy, the polar domains are found to possess a quasi-two-dimensional slab geometry with a lateral size of ∼100 μm and thickness of ∼10 nm. Electronic structure calculations show that the coexistence of electronic and parity-lifting orders arise from anharmonic lattice interactions, which support 90° and 180° polar domains in a metal. Using in situ transmission electron microscopy, we also demonstrate a strain-tuning route to achieve ferroelastic switching of polar metal domains.

TiN synergetic with micro-/mesoporous carbon for enhanced performance lithium–sulfur batteries

Porous carbon has high specific area and total pore volume but weak interaction with dissolved polysulfides. Conductive polar metal compound has strong chemical adsorption of polysulfides but difficult to attain high porosity to encapsulate sulfur series. Instead of efforts on the cathode, we prepared a composite made up of titanium nitride and three-dimensional micro-/mesoporous carbon by a facile and economic way. This composite was coated on the commercial Celgard separator as a polysulfide interceptor to enhance the performances of lithium–sulfur battery. The strategy exerts the synergetic merits of porosity, chemical adsorption, physical interception, and benign conductivity. The hierarchical carbon possesses a high specific surface area of 1571 m2/g and total pore volume of 1.56 cm3/g with the pore size centered at 1.27 and 5.30 nm. TiN can immobilize sulfur intermediates by strong chemical interaction. In addition, excellent electrical conductivity of TiN facilitates redox kinetics. The pure sulfur cathode with the modified separator delivers high initial capacity of 1130 mAh/g at 1 C (1 C = 1675 mAh/g) and retains 500 mAh/g after 400 cycles, demonstrating superior cycling stability, rate capabilities. Discharge-charge profiles, electrochemical impedance spectrum, and cyclic voltammetry curves of batteries were investigated to support the prominent electrochemistry of the material. Further analysis and observation on the modified separator disassembled from the coin cells after cycling were conducted to probe the evolution and reaction mechanism of the coating.

Strain-engineering stabilization of BaTiO3 -based polar metals

Polar metals, which possess ferroelectriclike polar structure and conductivity simultaneously, have attracted wide interest since the first solid example, $\mathrm{LiOs}{\mathrm{O}}_{3}$ (below 140 K), was discovered. However, the lack of room-temperature polar metals hinders further research and applications. Thus abundant properties of polar metals are unexplored. Here, with first-principles calculations, we report that the polar metal phase can be stabilized in the strain-engineered $\mathrm{BaTi}{\mathrm{O}}_{3}$ with electron doping. The mechanism relates to the competition between the shifting of the ${t}_{2g}$ energy levels and the narrowing of their bandwidth. Surprisingly, it is predicted that the ferroelectric-to-paraelectric transition temperature can be increased by electron doping when the strain is large enough, which holds potential for room-temperature polar metals. Our results indicate that strain engineering is a promising way to achieve $\mathrm{BaTi}{\mathrm{O}}_{3}$-based polar metals, and they should have practical significance for obtaining easily accessible, ecofriendly, and potential room-temperature polar metals.

Meta-screening and permanence of polar distortion in metallized ferroelectrics

Ferroelectric materials are characterized by a spontaneous polar distortion. The behavior of such distortion in the presence of free charge is the key to the physics of metallized ferroelectrics in particular, and of structurally polar metals more generally. Using first-principles simulations, here we show that a polar distortion resists metallization and the attendant suppression of long-range dipolar interactions in the vast majority of a sample of 11 representative ferroelectrics. We identify a meta-screening effect, occurring in the doped compounds as a consequence of the charge rearrangements associated to electrostatic screening, as the main factor determining the survival of a noncentrosymmetric phase. Our findings advance greatly our understanding of the essentials of structurally polar metals, and offer guidelines on the behavior of ferroelectrics upon field-effect charge injection or proximity to conductive device elements.

Benchmarking lithium amide versus amine bonding by charge density and energy decomposition analysis arguments.

Lithium amides are versatile C-H metallation reagents with vast industrial demand because of their high basicity combined with their weak nucleophilicity, and they are applied in kilotons worldwide annually. The nuclearity of lithium amides, however, modifies and steers reactivity, region- and stereo-selectivity and product diversification in organic syntheses. In this regard, it is vital to understand Li-N bonding as it causes the aggregation of lithium amides to form cubes or ladders from the polar Li-N covalent metal amide bond along the ring stacking and laddering principle. Deaggregation, however, is more governed by the Li←N donor bond to form amine adducts. The geometry of the solid state structures already suggests that there is σ- and π-contribution to the covalent bond. To quantify the mutual influence, we investigated [{(Me2NCH2)2(C4H2N)}Li]2 (1) by means of experimental charge density calculations based on the quantum theory of atoms in molecules (QTAIM) and DFT calculations using energy decomposition analysis (EDA). This new approach allows for the grading of electrostatic Li+N-, covalent Li-N and donating Li←N bonding, and provides a way to modify traditional widely-used heuristic concepts such as the -I and +I inductive effects. The electron density ρ(r) and its second derivative, the Laplacian ∇2ρ(r), mirror the various types of bonding. Most remarkably, from the topological descriptors, there is no clear separation of the lithium amide bonds from the lithium amine donor bonds. The computed natural partial charges for lithium are only +0.58, indicating an optimal density supply from the four nitrogen atoms, while the Wiberg bond orders of about 0.14 au suggest very weak bonding. The interaction energy between the two pincer molecules, (C4H2N)22-, with the Li22+ moiety is very strong (ca. -628 kcal mol-1), followed by the bond dissociation energy (-420.9 kcal mol-1). Partitioning the interaction energy into the Pauli (ΔEPauli), dispersion (ΔEdisp), electrostatic (ΔEelstat) and orbital (ΔEorb) terms gives a 71-72% ionic and 25-26% covalent character of the Li-N bond, different to the old dichotomy of 95 to 5%. In this regard, there is much more potential to steer the reactivity with various substituents and donor solvents than has been anticipated so far.

Engineering an Insulating Ferroelectric Superlattice with a Tunable Band Gap from Metallic Components.

The recent discovery of "polar metals" with ferroelectriclike displacements offers the promise of designing ferroelectrics with tunable energy gaps by inducing controlled metal-insulator transitions. Here we employ first-principles calculations to design a metallic polar superlattice from nonpolar metal components and show that controlled intermixing can lead to a true insulating ferroelectric with a tunable band gap. We consider a 2/2 superlattice made of two centrosymmetric metallic oxides, La_{0.75}Sr_{0.25}MnO_{3} and LaNiO_{3}, and show that ferroelectriclike displacements are induced. The ferroelectriclike distortion is found to be strongly dependent on the carrier concentration (Sr content). Further, we show that a metal-to-insulator (MI) transition is feasible in this system via disproportionation of the Ni sites. Such a disproportionation and, hence, a MI transition can be driven by intermixing of transition metal ions between Mn and Ni layers. As a result, the energy gap of the resulting ferroelectric can be tuned by varying the degree of intermixing in the experimental fabrication method.

In-situ probing of coupled atomic restructuring and metallicity of oxide heterointerfaces induced by polar adsorbates

Microscopic understanding of the surface-controlled conductivity of the two dimensional electron gas at complex oxide interfaces is crucial for developing functional interfaces. We observe conductivity and structural modification using in-situ synchrotron surface x-ray diffraction as the surface of a model LaAlO3/SrTiO3 (001) heterostructure is changed by polar adsorbates. We find that polar adsorbate-induced interfacial metallicity reduces polar distortions in the LaAlO3 layer. First-principles density functional theory calculations show that surface dipoles introduced by polar adsorbates lead to additional charge transfer and the reduction of polar displacements in the LaAlO3 layer, consistent with the experimental observations. Our study supports that internal structural deformations controlling functionalities can be driven without the application of direct electrical or thermal bias and offers a route to tuning interfacial properties. These results also highlight the important role of in-situ x-ray scattering with atomic resolution in capturing and exploring structural distortions and charge density changes caused by external perturbations such as chemical adsorption, redox reaction, and generation and/or annihilation of surface defects.

Dielectric properties of SrBi1.8RE0.2Nb2O9 (RE = Yb, Tm, Tb, Gd, Er, Sm and Ce) ceramics

The structure, electrical and dielectric properties of SrBi1.8RE0.2Nb2O9 doped with one of seven lanthanide ions (RE = Yb, Tm, Tb, Dy, Er, Sm and Ce) are investigated. The samples are prepared by solid-state reaction method. The single crystals are confirmed as being in a single phase with SrBi2Nb2O9 by X-ray diffraction. Scanning electron microscopy micrographs revealed a remarkable change in the shaped grains. At room temperature, the dielectric loss is found to decrease by substitution of bismuth with lanthanides and the dielectric constant remains essentially constant at higher frequency. Curie temperature, dielectric constant peak at Curie temperature and activation energy decrease with RE-doping. The conductivity results obtained for the samples is explained taking into account the polarization process and metal binding energies.

The impact of coulombic interactions among polar molecules and metal substrates on flow and lubrication properties

In the current work we present an extensive study on the impact of short- and long-range interactions between solids and liquids on the hydrodynamic and lubrication behaviour of a tribological system. We have implemented a coarse grain molecular dynamics description of two ionic liquids (ILs) as lubricants which are confined by two infinitely long flat iron solids and which are subjected to a shearing flow. The impact of surface polarizability and molecule geometry on the ion arrangement under shearing has been studied in detail. The results have revealed two regimes of lubrication, with a liquid phase being present under low normal loads, while solidification of the ILs, accompanied by a steep rise of normal forces and significant wall slip is observed at small plate-to-plate distances.

Polar instability under electrostatic doping in tetragonal SnTiO3

How to make the metallicity compatible with a polar structure for forming a ``polar metal'' has been an interesting and important topic since the polar structure was discovered in metallic $\mathrm{LiOs}{\mathrm{O}}_{3}$. Here, we present robust polar instability under electrostatic doping in tetragonal $\mathrm{SnTi}{\mathrm{O}}_{3}$ based on our first-principles calculations. The mechanism for polar distortion surviving free carriers is investigated from the ``weak-coupling'' perspective. The contributions of different interactions between two polar modes in a ``ferroelectric'' phase transition are also studied. We found that the short-range interaction contributes the most for lowering the total energy during the ferroelectricphase transition. Moreover, the dipole-dipole interaction between two polar modes of oxygen atoms provides the largest energy gain among local interactions, which cannot be screened out by doping. We propose that the promising candidates for noncentrosymmetric metals obtained by doping are ferroelectrics with bonding states responsible for polar distortions away from the Fermi level. We believe that this mechanism sheds light on a method to obtain noncentrosymmetric metals from a large amount of ferroelectric perovskite oxides by doping.

Polar metal phase stabilized in strained La-doped BaTiO3films

Ferroelectric polarization and metallic conduction are two seemingly irreconcilable properties that cannot normally coexist in a single system, as the latter tends to screen the former. Polar metals, however, defy this rule and have thus attracted considerable attention as a new class of ferroelectrics exhibiting novel properties. Here, we fabricate a new polar metal film based on the typical ferroelectric material BaTiO3by combining chemical doping and epitaxial strain induced by a substrate. The temperature dependences of the c-axis lattice constant and the second harmonic generation intensity of La-doped BaTiO3films indicate the existence of polar transitions. In addition, through La doping, films become metallic at the polar phase, and metallicity enhancement at the polar state occurs in low-La-doped films. This intriguing behaviour is effectively explained by our first-principles calculations. Our demonstration suggests that the carrier doping to ferroelectric material with epitaxial strain serves as a new way to explore polar metals.

(LaTiO3)n/(LaVO3)n as a model system for unconventional charge transfer and polar metallicity

At interfaces between oxide materials, lattice and electronic reconstructions always play important roles in exotic phenomena. In this study, the density functional theory and maximally localized Wannier functions are employed to investigate the (LaTiO$_3$)$_n$/(LaVO$_3$)$_n$ magnetic superlattices. The electron transfer from Ti$^{3+}$ to V$^{3+}$ is predicted, which violates the intuitive band alignment based on the electronic structures of LaTiO$_3$ and LaVO$_3$. Such unconventional charge transfer quenches the magnetism of LaTiO$_3$ layer mostly and leads to metal-insulator transition in the $n=1$ superlattice when the stacking orientation is altered. In addition, the compatibility among the polar structure, ferrimagnetism, and metallicity is predicted in the $n=2$ superlattice.

Polar Ketone-Functionalized Metal-Organic Framework Showing a High CO2 Adsorption Performance.

The incorporation of various functionalities into porous metal-organic frameworks (MOFs) represents an efficacious strategy to improving their gas adsorption properties. In this work, a carbonylated tetracarboxylic acid ligand (5,5'-carbonyldiisophthalic acid) was synthesized, and a ketone-functionalized MOF with exposed metal sites based on this ligand was formed successfully. Structural analysis reveals that the new MOF possesses channels decorated by the carbonyl groups and rhombicuboctahedral cages, with open CuII sites pointing toward the cage center. The framework exhibits exceptionally high CO2 (46.7 wt % at 273 K and 1 bar) and H2 (2.8 wt % at 77 K and 1 bar) uptake. Furthermore, it displays high selectivities of CO2 adsorption over N2 and CH4 at 298 K.

Hollow cobalt sulfide polyhedra-enabled long-life, high areal-capacity lithium-sulfur batteries

Improving the electron and ion transport in sulfur electrodes and suppressing the lithium polysulfide shuttle have been the two major challenges with lithium-sulfur (Li-S) batteries. Here, we present a composite paper electrode consisting of hollow Co3S4 polyhedra, activated carbon nanofibers (ACNF), and pure sulfur powder for Li-S batteries. The hollow Co3S4 polyhedra with a porous shell structure provide large spaces to accommodate the polysulfides, possess ideal polar chemisorptive capability for immobilizing the polysulfide species, and have a higher conductivity than many polar metal oxides, facilitating fast reaction kinetics with the Li-S batteries. The composite electrode exhibits high sulfur utilization and maintains superior cycling stability in Li-S batteries with a high sulfur areal mass. A high capacity of 953mAh g−1 at 1C rate could be achieved with a sulfur loading of 2.5mgcm−2, and the capacity remains at 610mAh g−1 after 450 cycles. Even with a high sulfur loading of 13.5mgcm−2, the composite electrode delivers a high areal capacity of 13mAhcm−2 at 0.3C rate.

Thermal Effect and its Predominant Property of Resonite developed by using Polar Crystal Metals on Human Body

Thermal Effect and its Predominant Property of Resonite developed by using Polar Crystal Metals on Human Body

トルマリン系極性結晶体から発するe<sup>-</sup>イオン及び遠赤外線レゾナンス波長を用いた熟成肉の加工に関する研究

Experiments have been carried out to reveal the mechanism on processing of aging meats by means of e-ion and resonance frequencies in the regime of far infrared rays emitting from polar crystal metals of tourmaline. The e-ion is operated as the reducing agent on the surface of aging meats, and resonance frequency in the regime of far infrared ray can be determined from Wein's displacement law. The processing technique about aging meats developed in the study shows that the resonance frequency may contribute to promote the aging speed of meats caused by vibration mode and it is possible to achieve the completion of aging meats without destruction of molecular elements of meats, that is, no drip and keeping the umami, bitterness and sweetness. The yield rate after completion of aging meats may be 70% to 80% in weight.

A Studies for Effect of Resonite produced from Polar Crystal Metals on Thermogenesis of Human Body and Blood Fluidity caused by e-Ion Clusters ejected from Resonite.

A Studies for Effect of Resonite produced from Polar Crystal Metals on Thermogenesis of Human Body and Blood Fluidity caused by e-Ion Clusters ejected from Resonite.

First-Eutectic Features of Polar Metals in Double Systems

It is known that the dense part of any liquid metal consists of ramified clusters of almost regular tetrahedrons (triangular pyramids with atoms in their vertexes) that are connected into chains by faces. Any metal additive as a second component of liquid alloy can be both beyond these clusters as separated atoms and into them as inherent clusters. The liquid-metal alloy transfers into the second state, at the first eutectic of the solvent. This polymorphic transition of liquid matrix is discovered in the systems, Pb-K and Na-Pb, by molecular-dynamic simulating their microstructure and in experiments on scattering slow neutrons by these alloys of different compositions. In the first system, the obtained results identify both the homogeneous alloy at low concentrations of potassium in liquid lead and the alloy clustering, (Pb4K)n, at potassium concentrations following the eutectic, Pb0.91K0.09. In the second one at the concentrations of lead more than 2%, just the second state is discovered with the clusters, (Na4Pb)n. One can expect the same polymorphic transition in the eutectic, Na0.93Tl0.07, with the micro-inhomogeneity, (Na6Tl)n, and with the melting point of 64 C. This eutectic maintained by the oxygen-free technology and enriched by the isotope, 205Tl, can become the best coolant for fast nuclear reactors due to the depressed chemical activity of sodium and composition stability.

Persistence of polar distortion with electron doping in lone-pair driven ferroelectrics

Free electrons can screen out long-range Coulomb interaction and destroy the polar distortion in some ferroelectric materials, whereas the coexistence of polar distortion and metallicity were found in several non-central-symmetric metals (NCSMs). Therefore, the mechanisms and designing of NCSMs have attracted great interests. In this work, by first-principles calculation, we found the polar distortion in the lone-pair driven ferroelectric material PbTiO$_3$ can not only persist, but also increase with electron doping. We further analyzed the mechanisms of the persisting of the polar distortion. We found that the Ti site polar instability is suppressed but the Pb site polar instability is intact with the electron doping. The Pb-site instability is due to the lone-pair mechanism which can be viewed as a pseudo-Jahn-Teller effect, a mix of the ground state and the excited state by ion displacement from the central symmetric position. The lone-pair mechanism is not strongly affected by the electron doping because neither the ground state or the excited state involved is at the Fermi energy. The enhancement of the polar distortion is related to the increasing of the Ti ion size by doping. These results show the lone-pair stereoactive ions can be used in designing NCSMs.

Dynamical Piezoelectric and Magnetopiezoelectric Effects in Polar Metals from Berry Phases and Orbital Moments.

The polarization of a material and its response to applied electric and magnetic fields are key solid-state properties with a long history in insulators, although a satisfactory theory required new concepts such as Berry-phase gauge fields. In metals, quantities such as static polarization and the magnetoelectric θ term cease to be well defined. In polar metals, there can be analogous dynamical current responses, which we study in a common theoretical framework. We find that current responses to dynamical strain in polar metals depend on both the first and second Chern forms, related to polarization and magnetoelectricity in insulators as well as the orbital magnetization on the Fermi surface. We provide realistic estimates that predict that the latter contribution will dominate, and we investigate the feasibility of experimental detection of this effect.