Ferro-ionic States and Domains Morphology in Hf$_x$Zr$_{1-x}$O$_2$ Nanoparticles
Eugene A. Eliseev, Sergei V. Kalinin, Anna N. Morozovska
备注：
28 pages, 7 figures and Appendixes, Invited by the Journal of Applied Physics to the "Special Topic on Ferroic Materials, Domains, and Domain Walls: Bridging Fundamentals with Next-Generation Technology"
发表信息：
Journal of Applied Physics, 137 (3), 034103 (2025)
Unique polar properties of nanoscale hafnia-zirconia oxides (Hf$_x$Zr$_{1-x}$O$_2$) are of great interest for condensed matter physics, nanophysics and advanced applications. These properties are connected (at least partially) to the ionic-electronic and electrochemical phenomena at the hafnia surface, interfaces and/or internal grain boundaries. Here we calculated the phase diagrams, dielectric permittivity, spontaneous polar and antipolar ordering, and domain structure morphology in Hf$_x$Zr$_{1-x}$O$_2$ nanoparticles covered by ionic-electronic charge, originated from the surface electrochemical adsorption. We revealed that the ferro-ionic coupling supports the polar long-range order in the nanoscale Hf$_x$Zr$_{1-x}$O$_2$, induces and/or enlarges the stability region of the labyrinthine domains towards smaller sizes and smaller environmental dielectric constant at low concentrations of the surface ions, and causes the transition to the single-domain ferro-ionic state at high concentrations of the surface ions. We predict that the labyrinthine domain states, being multiple-degenerated, may significantly affect the emergence of the negative differential capacitance state in the nanograined/nanocrystalline Hf$_x$Zr$_{1-x}$O$_2$ films.
Non-equilibrium synthesis methods allow to alloy bulk-immiscible elements into multinary nanoparticles, which broadens the design space for new materials. Whereas sputtering onto solid substrates can combine immiscible elements into thin film solid solutions, this is not clear for sputtering of nanoparticles in ionic liquids. Thus, the suitability of sputtering in ionic liquids for producing nanoparticles of immiscible elements is investigated by co-sputtering the systems Au-Cu (miscible), Au-Ru and Cu-Ru (both immiscible), and Au-Cu-Ru on the surface of the ionic liquid 1-butyl-3-methylimidaz…
Occurrence of surface ferromagnetism in inorganic nanoprticles as a universal property not only explains many of the unusual magnetic features of oxidic thin films, but also suggests its possible use in creating new materials, as exemplified by multiferroic BaTiO3 nanoparticles. While the use of Mn-doped ZnO and such materials in spintronics appears doubtful, it is possible to have materials exhibiting coexistence of (bulk) superconductivity with (surface) ferromagnetism.
Analytical description of domain structure morphology and phase diagrams of ferroelectric nanoparticles is developed in the framework of Landau Ginzburg Devonshire approach. To model realistic conditions of incomplete screening of spontaneous polarization at the particle surface, it was considered covered by an ultra-thin layer of screening charge with finite screening length. The phase diagrams, calculated for spherical Sn2P2S6 nanoparticles in coordinates "temperature vs surface screening length" by finite element modeling, demonstrate the emergence of polydomain region at the tricritical po…
Nonlinear electrostatic interaction between the surface ions of electrochemical nature and ferroelectric dipoles gives rise to the coupled ferroionic states in nanoscale ferroelectrics. Here, we investigated the role of the surface ions formation energy value on the polarization states and polarization reversal mechanisms, domain structure and corresponding phase diagrams of ferroelectric thin films. Using 3D finite elements modeling we analyze the distribution and hysteresis loops of ferroelectric polarization and ionic charge, and dynamics of the domain states. These calculations performed o…
Light-matter strong coupling in the vacuum limit has been shown to enhance material properties over the past decade. Oxide nanoparticles are known to exhibit weak ferromagnetism due to vacancies in the lattice. Here we report the 700-fold enhancement of the ferromagnetism of YBa$_2$Cu$_3$O$_{7-x}$ nanoparticles under cooperative strong coupling at room temperature. The magnetic moment reaches 0.90 $μ_{\rm B}$/mol, and with such a high value, it competes with YBa$_2$Cu$_3$O$_{7-x}$ superconductivity at low temperature. This strong ferromagnetism at room temperature suggest that strong coupling …
The influence of a transverse static magnetic field on the magnetic hyperthermia properties is studied on a system of large-losses ferromagnetic FeCo nanoparticles. The simultaneous measurement of the high-frequency hysteresis loops and of the temperature rise provides an interesting insight into the losses and heating mechanisms. A static magnetic field of only 40 mT is enough to cancel the heating properties of the nanoparticles, a result reproduced using numerical simulations of hysteresis loops. These results cast doubt on the possibility to perform someday magnetic hyperthermia inside a m…
The possibility of controlling the domain structure in spherical nanoparticles of uniaxial and multiaxial ferroelectrics using a shell with tunable dielectric properties is studied in the framework of Landau-Ginzburg-Devonshire theory. Finite element modeling and analytical calculations are performed for Sn2P2S6 and BaTiO3 nanoparticles covered with high-k polymer, temperature dependent isotropic paraelectric strontium titanate, or anisotropic liquid crystal shells with a strongly temperature dependent dielectric permittivity tensor. It appeared that the tunable paraelectric shell with a tempe…
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In the framework of the Landau-Ginzburg-Devonshire (LGD) approach we studied finite size effects of the phase diagram and domain structure evolution in spherical nanoparticles of uniaxial ferroelectric. The particle surface is covered by a layer of screening charge characterized by finite screening length. The phase diagram, calculated in coordinates "particle radius vs. screening length" has a wide region of versatile poly-domain structures separating single-domain ferroelectric and nonpolar paraelectric phases. Unexpectedly, we revealed a region of stable irregular labyrinthine domains in th…
Pure phase and mixed phase TiO$_2$ nanoparticles have been produced using a pyrolytic method from a non-aqueous carboxylate precursor. The precursor was prepared by a multiphase cation exchange using pentanoic acid (C$_4$H$_9$COOH). The thermal stability, polymorph content, morphology, size distribution and surface region of the produced nanoparticles were studied by TGA/DSC, XRD, FTIR and TEM. High quality monodisperse nanoparticles have been produced in the size range from 7 to 27 nm. The nanoparticles showed room temperature ferromagnetism revealed by VSM within bound polaron model. The car…
A detailed investigation of the electronic - and magneto - transport properties of Nd0.8Sr0.2MnO3 with the variation of grain size (down to 42 nm) is presented here. Interestingly, we observe that the ferromagnetic insulating state is suppressed and a metallic state is stabilized as the grain size of the sample is reduced. As a result, metal insulator transition is observed in this low doped manganite which is insulating in nature in its bulk form. Destabilization of polaronic order in the ferromagnetic insulating state due to enhanced surface disorder on grain size reduction has been attribut…
Thermodynamic theory is developed for the ferroelectric phase transition of an ultrathin film in equilibrium with a chemical environment that supplies ionic species to compensate its surface. Equations of state and free energy expressions are developed based on Landau-Ginzburg-Devonshire theory, using electrochemical equilibria to provide ionic compensation boundary conditions. Calculations are presented for a monodomain PbTiO$_3$ (001) film coherently strained to SrTiO$_3$ with its exposed surface and its electronically conducting bottom electrode in equilibrium with a controlled oxygen parti…
The polar states of uniaxial ferroelectric nanoparticles interacting with a surface system of electronic and ionic charges with a broad distribution of mobilities is explored, which corresponds to the experimental case of nanoparticles in solution or ambient conditions. The nonlinear interactions between the ferroelectric dipoles and surface charges with slow relaxation dynamics in an external field lead to the emergence of a broad range of paraelectric-like, antiferroelectric-like ionic, and ferroelectric-like ferroionic states. The crossover between these states can be controlled not only by…
Bismuth ferrite (BiFeO3) is one of the most promising multiferroics with a sufficiently high ferroelectric (FE) and antiferromagnetic transition temperatures, and magnetoelectric (ME) coupling coefficient at room temperature, and thus it is highly sensitive to the impact of cross-influence of applied electric and magnetic fields. According to the urgent demands of nanotechnology miniaturization for ultra-high density data storage in advanced nonvolatile memory cells, it is very important to reduce the sizes of multiferroic nanoparticles in the self-assembled arrays without serious deterioratio…
Homogeneous single phase GdCrO3 nanoparticles are synthesized by a modified-hydrothermal synthesis. The sample shows a compensation temperature at 128 K, below which the DC magnetization becomes negative and positive at low temperatures due to the competition between the two sublattice magnetization. At Néel temperature (168K), the line width and the intensity show an abrupt transition, revealed from electron paramagnetic resonance spectroscopy.
For advanced applications in modern industry it is very important to reduce the volume of ferroelectric nanoparticles without serious deterioration of their polar properties. In many practically important cases fixed volume (rather than fixed size) corresponds to realistic technological conditions of nanoparticles fabrication. The letter is focused on the theoretical study of the behavior of ferroelectric polarization, paramagnetoelectric coefficient and phase diagrams of semi-ellipsoidal nanoparticles with fixed volume V. Our approach combines the Landau-Ginzburg-Devonshire phenomenology, cla…
Large Enhancements in Optical and Piezoelectric Properties in Ferroelectric Zn1-xMgxO Thin Films through Engineering Electronic and Ionic Anharmonicities
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We consider a model of a nanocomposite based on non-interacting spherical single-domain ferroelectric nanoparticles of various sizes embedded in a dielectric matrix. The size distribution function of these nanoparticles is selected as a part of the Gaussian distribution from minimum to maximum radius (truncated normal distribution). For such nanocomposites, we calculate the dependences of the reversible part of the electric polarization, the electrocaloric temperature change, and the dielectric permittivity on the external electric field, which have the characteristic form of hysteresis loops.…
Influence of BaTiO_3 nanoparticles on the anisotropy of the dielectric properties of nematic liquid crystal 5CB
Institute of Physics of the National Academy of Sciences of Ukraine（乌克兰国家科学院物理研究所）；Frantsevich Institute of Materials Science, the National Academy of Sciences of Ukraine（乌克兰国家科学院弗兰采维奇材料科学研究所）
In the framework of the thermodynamic approach Landau-Ginzburg-Devonshire (LGD) combined with the equations of electrostatics, we investigated the effect of polarization surface screening on finite size effects of the phase diagrams, polar and dielectric properties of ferroelectric nanoparticles of different shapes. We obtained and analyzed the analytical results for the dependences of the ferroelectric phase transition temperature, critical size, spontaneous polarization and thermodynamic coercive field on the shape and size of nanoparticles. The pronounced size effect of these characteristic…
In this paper we show that the ionic conduction through surface chemisorbed ambient moisture leads to the remarkably high room temperature selective response towards hydrogen gas. The surface adsorbed moisture acts as surface states and shows ionic conduction, as a result of smaller size of ZnO nanoparticles of 20 +/- 5 nm. This response is enhanced remarkably i.e. from 10% to 190% for 1200 ppm H2 gas when p-type NiO quasi-nanowires (width ~50 nm) are mixed with these n-type ZnO nanoparticles to form a homogenous NiO/ZnO nano-bulk p-n heterostructure. The maximum response is obtained for about…
The Casimir pressure is investigated in three-layer systems where the intervening stratum possesses magnetic properties. This subject is gaining in importance in connection with ferrofluids and their use in various microelectromechanical devices. We present general formalism of the Lifshitz theory adapted to the case of ferrofluid sandwiched between two dielectric walls. The Casimir pressure is computed for the cases of kerosene- and water-based ferrofluids containing a 5% fraction of magnetite nanoparticles with different diameters between silica glass walls. For this purpose, we have found t…
