For the first time we predict the conditions of superparaelectric phase appearance in the ensemble of non-interacting spherical ferroelectric nanoparticles. The superparaelectricity in nanoparticle was defined by analogy with superparamagnetism, obtained earlier in small nanoparticles made of paramagnetic material. Calculations of correlation radius, energetic barriers of polarization reorientation and polarization response to external electric field, were performed within Landau-Ginzburg phenomenological approach for perovskites Pb(Zr,Ti)O3, BiFeO3 and uniaxial ferroelectrics rochelle salt and triglycine sulfate.
A comparative study of the dielectric properties and electric polarization of multiferroics GdMn2O5 and Gd0.8Ce0.2Mn2O5 has been carried out in the temperature range from 5 up to 300 K. The polarization properties in the ferroelectric state that forms due to a charge ordering and exchange striction have been studied at T less than 30 K. The properties of the restricted polar phase separation domains formed in the crystals containing ions Mn3+ and Mn4+ have been studied, too. These domains exhibit the electric polarization in the temperature range from 5 K to some temperatures Tf lager than TC.…
(00l)-Oriented LiNbO3 ultra-thin film was fabricated on Pt/Ti/SiO2/Si substrate using pulsed laser deposition. The film shrunk into crystalline state nanoparticles that still kept (00l) preferential orientation as being annealed in the oxygen atmosphere at 500 oC for 2 hours. These LiNbO3 nanoparticles exhibited the ferroelectricity, showing asymmetrical hysteresis loop which might originate from the large internal field at the interface. These nanoparticles could be used for further studying on the size effects and the ferroelectricity of nanocrystal.
Piezoresponse force microscopy (PFM) was used to investigate the ferroelectric properties of sol-gel derived LiNbO$_3$ nanoparticles. To determine the degree of ferroelectricity we took large-area images and performed statistical image-analysis. The ferroelectric behavior of single nanoparticles was verified by poling experiments using the PFM tip. Finally we carried out simultaneous measurements of the in-plane and the out-of-plane piezoresponse of the nanoparticles, followed by measurements of the same area after rotation of the sample by 90$^{\circ}$ and 180$^{\circ}$. Such measurements bas…
The electric polarization hysteresis loops and remanent polarization were revealed in multiferroics RMn$_2$O$_5$ with $R = Gd$ and $Bi$ at wide temperature interval from 5 K up to 330 K. Until recently, the long-range ferroelectric order having an exchange-striction magnetic nature had been observed in RMn$_2$O$_5$ only at low temperatures ($T\leq T_C = 30$ -- 35 K). We believe that the polarization we observed was caused by the frozen superparaelectric state which was formed by the restricted polar domains resulting from phase separation and charge carriers self-organization. At some sufficie…
The size effect on pyroelectric response of ferroelectric nanowires and nanotubes is analyzed. The pyroelectric coefficient strongly increases with the wire radius decrease and diverges at critical radius Rcr corresponding to the size-driven transition into paraelectric phase. Size-driven enhancement of pyroelectric coupling leads to the giant pyroelectric current and voltage generation by the polarized ferroelectric nanoparticles in response to the temperature fluctuation. The maximum efficiency of the pyroelectric energy harvesting and bolometric detection is derived, and is shown to approac…
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…
Ferroelectric nanoparticles of different shape and their nanocomposites are actively studied in modern physics. Because of their applications in many fields of nanotechnology, the size effects and the possible disappearance of ferroelectricity at a critical particle volume attract a growing scientific interest. In this paper we study the size effects of the cylindrical nanoparticle phase diagrams allowing for effective surface tension and depolarization field influence. The Euler-Lagrange equations were solved by direct variational method. The approximate analytical expression for the paraelec…
We report from first-principles-based atomistic simulations that ferroelectricity can be sustained in PbTiO3 nanoparticles of only a few lattice constants in size as a result of a toroidal ordering. We found that size-induced topological transformations lead to the stabilization of a ferroelectric bubble by the alignment of vortex cores along a closed path. These transformations, which are driven by the aspect ratio of the nanostructure, change the topology of the polarization field, producing a rich variety of polar configurations. For sufficiently flat nanostructures, a multi-bubble state br…
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…
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…
General approach for consideration of primary ferroic (ferroelectric, ferromagnetic, ferroelastic) nanoparticles phase transitions was proposed in phenomenological theory framework. The surface stress, order parameter gradient, striction as well as depolarization and demagnetization effects were included into the free energy. The strong intrinsic surface stress under the curved nanoparticle surface was shown to play the important role in the shift of transition temperature (if any) up to the appearance of new ordered phase absent in the bulk ferroic. The approximate analytical expression for t…
Interest in epitaxial ferroelectric nanoislands was growing rapidly in recent years driven by their potential for devices, especially ultradense memories. Recent advances in the "bottom- up" (self-assembly) nanometer scale techniques have opened up the opportunities of fabricating high-quality epitaxial ferroelectric nanoislands with extremely small thickness and lateral size on the order of 1 nm and 20 nm, respectively. On the other hand, recent emergence of powerful probes, such as piezoresponse force microscopy (PFM), has enabled imaging of a local domain structure with sub-10 nm resolution…
Nanoscale BaTiO3 particles (approximately 10 nm) prepared by ball-milling a mixture of oleic acid and heptane have been reported to have an electric polarization several times larger than that for bulk BaTiO3. In this work, detailed local, intermediate, and long-range structural studies are combined with spectroscopic measurements to develop a model structure of these materials. The X-ray spectroscopic measurements reveal large Ti off-centering as the key factor producing the large spontaneous polarization in the nanoparticles. Temperature-dependent lattice parameter changes reveal the sharpen…
Based on our analytical results [http://arxiv.org/abs/1006.3670], we predict that undoped nanoparticles (size <10-100nm) of incipient ferroelectrics without any magnetic ions can become ferromagnetic even at room temperatures due to the inherent presence of a new type of magnetic defects with spin S=1, namely oxygen vacancies, where the magnetic triplet state is the ground state in the vicinity of the surface (magnetic shell), while the nonmagnetic singlet is the ground state in the bulk material (nonmagnetic core). Consideration of randomly distributed magnetic spins (S=1) had shown that magn…
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…
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…
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.
The orthorhombically distorted perovskite NaMnF$_{3}$ has been predicted to become ferroelectric if an $a=c$ distortion of the bulk $Pnma$ structure is imposed. In order to test this prediction, NaMnF$_{3}$ thin films were grown on SrTiO$_{3}$ (001) single crystal substrates via molecular beam epitaxy. The best films were smooth and single phase with four different twin domains. In-plane magnetization measurements revealed the presence of antiferromagnetic ordering with weak ferromagnetism below the Néel temperature $T_N=66$ K. For the dielectric studies, NaMnF$_{3}$ films were grown on a 30 n…
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…
Phase transformation in finite-size ferroelectrics is of fundamental relevance for understanding collective behaviors and balance of competing interactions in low-dimensional systems. We report a first-principles effective Hamiltonian study of vortex-to-polarization transformation in Pb(Zr$_{0.5}$Ti$_{0.5}$)O$_3$ nanoparticles, caused by homogeneous electric fields normal to the vortex plane. The transformation is shown to (1) follow an unusual {\it macroscopic} path that is symmetry non-conforming and characterized by the occurrence of a previously unknown structure as the bridging phase; (2)…
A theoretical study of a dielectrophoretic force, i.e. the force acting on an electrically neutral particle in the inhomogeneous electric field, which is produced by a ferroelectric domain pattern, is presented. It has been shown by several researchers that artificially prepared domain patterns with given geometry in ferroelectric single crystals represent an easy and flexible method for patterning dielectric nanoobjects using dielectrophoretic forces. The source of the dielectrophoretic force is a strong and highly inhomogeneous (stray) electric field, which exists in the vicinity of the ferr…
Stress-Induced Ferroelectricity in Hafnium Oxide Core-Shell Nanoparticles
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 for Problems in Materials Science of the National Academy of Sciences of Ukraine（乌克兰国家科学院弗拉特谢维奇材料科学问题研究所）；Department of Materials Science and Engineering, University of Tennessee, Knoxville（田纳西大学诺克斯维尔分校材料科学与工程系）；Zone 5 Technologies（第五区技术公司）
Using Landau-Ginzburg-Devonshire theory and effective medium approximation, we analytically calculate typical dependences of the pyroelectric and electrocaloric coefficients on external electric field, temperature and radius for spherical single-domain ferroelectric nanoparticles. The considered physical model corresponds to the nanocomposite with small fraction of ferroelectric nanoparticles. Within the framework of the analytical model we establish how the size changes determine the temperature and field behavior pyroelectric and electrocaloric coefficients on example of BaTiO3 nanoparticles…
When decreasing the size of nanoscale magnetic particles their magnetization becomes vulnerable to thermal fluctuations as approaching the superparamgnetic limit, hindering thus applications relying on a stable magnetization. Here, we show theoretically that a magnetoelectric coupling to a ferroelectric substrate renders possible the realization of substantially smaller nano clusters with thermally stable magnetization. For an estimate of cluster size we perform calculations with realistic material parameters for iron nano particles on ferroelectric BaTiO3 substrate. We find, steering the pola…
Role of Oxygen Vacancies in Stabilizing the Orthorhombic Phases of Hf0.5Zr0.5O2 Nanoparticles
Frantsevich Institute for Problems in Materials Science of the National Academy of Sciences of Ukraine（乌克兰国家科学院弗伦采维奇材料科学问题研究所）；Institute of Physics of the Czech Academy of Sciences（捷克科学院物理研究所）；Stockholm University, Department of Chemistry（斯德哥尔摩大学化学系）；Ye. O. Paton Institute of Materials Science and Welding, National Technical University of Ukraine “Igor Sikorsky Kyiv Polytechnic Institute”（乌克兰国立技术大学“伊戈尔·西科尔斯基基辅理工学院”叶·奥·帕顿材料科学与焊接研究所）；Oles Honchar Dnipro National University（阿列斯·洪恰尔第聂伯罗国立大学）；Institute of Physics of the National Academy of Sciences of Ukraine（乌克兰国家科学院物理研究所）；Zone 5 Technologies, Special Projects（Zone 5 Technologies特殊项目部）
A microscopic model for describing ferroelectric nanoparticles is proposed which allows us to calculate the polarization as a function of an external electric field, the temperature, the defect concentration and the particle size. The interaction of the constituents of the material, arranged in layers, depends on both the coupling strength at the surface and that of defect shells in addition to the bulk values. The analysis is based on an Ising model in a transverse field, modified in such a manner to study the influence of size and doping effects on the hysteresis loop of the nanoparticles. U…
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.…
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…
Hydrogen is a promising fossil-fuel alternative fuel owing to its environmentally neutral emissions and high energy density. However, the need for purified water and external power are critical hindrances to implementation of hydrogen production. The present work reveals the potential to overcome these shortcomings through piezo-photocatalysis of seawater using BaTiO3-x (BTO) nanoparticles. This material was made piezoelectrically active by annealing under different atmospheres, including O2, N2, Ar, and H2, the latter of which caused Ti4+ to Ti(4-x)+ multiple reductions and structural expansi…
The coexistence and coupling of magnetic and ferroelectric orderings in single phase multiferroics has evinced enormous scientific interest as it involves breaking of time reversal and space inversion symmetries in the same material. The mutual controllability of the two diverse orderings in multiferroics has potential for developing new generation multifunctional sensor, actuator and data storage devices. We present here evidence for a new exotic facet of multiferroicity, whereby one can raise the strength of antiferromagnetic (AFM) superexchange interaction and hence tune the Néel temperatur…
Within the framework of the Landau-Ginzburg-Devonshire approach we explore the impact of elastic anisotropy, electrostriction, flexoelectric couplings, and mismatch strain on the domain structure morphology in ferroelectric core-shell nanoparticles of spherical shape. We perform finite element modelling (FEM) for multiaxial ferroelectric nanoparticle cores covered with an elastically-isotropic soft or elastically-anisotropic rigid paraelectric shell, with and without mismatch strains. In the case of a core covered with a soft shell, the FEM results show that at room temperature a single polari…
In this paper we study the size effects of the ferroelectric nanotube and nanowire phase diagrams and polar properties allowing for radial stress and depolarization field influence. The approximate analytical expression for the paraelectric-ferroelectric transition temperature dependence on the radii of nanotube, polarization gradient coefficient, extrapolation length, radial stress (surface tension) and electrostriction coefficient was derived. It was shown that the transition temperature could be higher than the one of the bulk material for negative electrostriction coefficient and small dep…
In the framework of the Landau-Ginzburg-Devonshire (LGD) approach, we studied the possibility of controlling the polarity and chirality of equilibrium domain structures by a homogeneous external electric field in a nanosized ferroelectric core covered with an ultra-thin shell of screening charge. Under certain screening lengths and core sizes, the minimum of the LGD energy, which consists of Landau-Devonshire energy, Ginzburg polarization gradient energy, and electrostatic terms, leads to the spontaneous appearance of stable labyrinth domain structures in the core. The labyrinths evolve from a…
We fabricated Pb(Zr0.52Ti0.48)O3-NiFe2O4 composite films consisting of randomly dispersed NiFe2O4 nanoparticles in the Pb(Zr0.52Ti0.48)O3 matrix. The structural analysis revealed that the crystal axes of the NiFe2O4 nanoparticles are aligned with those of the ferroelectric matrix. The composite has good ferroelectric and magnetic properties. We measured the transverse and longitudinal components of the magnetoelectric voltage coefficient, which supports the postulate that the magnetoelectric effect comes from direct stress coupling between magnetostrictive NiFe2O4 and piezoelectric Pb(Zr0.52Ti…
Most multiferroic materials with coexisting ferroelectric and magnetic order exhibit cycloidal antiferromagnetism with wavelength of several nanometers. The prototypical example is bismuth ferrite (BiFeO$_3$ or BFO), a room-temperature multiferroic considered for a number of technological applications. While most applications require small sizes such as nanoparticles, little is known about the state of these materials when their sizes are comparable to the cycloid wavelength. This work describes a microscopic theory of cycloidal magnetism in nanoparticles based on Hamiltonian calculations. It …
We report on the fabrication of organic multiferroic tunnel junction (OMFTJ) based on an organic barrier of Poly(vinylidene fluoride) (PVDF):Fe3O4 nanocomposite. By adding Fe3O4 nanoparticles into the PVDF barrier, we found that the ferroelectric properties of the OMFTJ are considerably improved compared to that with pure PVDF barrier. It can lead to a tunneling electroresistance (TER) of about 450% at 10K and 100% at room temperature (RT), which is much higher than that of the pure PVDF based device (70% at 10K and 7% at RT). OMFTJs based on the PVDF:Fe3O4 nanocomposite could open new functio…
After decades of searching for robust nanoscale ferroelectricity that could enable integration into the next generation memory and logic devices, hafnia-based thin films have appeared as the ultimate candidate because their ferroelectric (FE) polarization becomes more robust as the size is reduced. This exposes a new kind of ferroelectricity, whose mechanism still needs to be understood. Towards this end, thin films with increased crystal quality are needed. We report the epitaxial growth of Hf0.5Zr0.5O2 (HZO) thin films on (001)-oriented La0.7Sr0.3MnO3/SrTiO3 (STO) substrates. The films, whic…
In the framework of the Landau-Ginzburg-Devonshire approach coupled with electrostatic equations, we performed finite element modeling of the polarization behavior in a ferroelectric barium titanate core covered with a tunable paraelectric strontium titanate shell placed in a polymer or liquid medium. A stable two-dimensional vortex is formed in the core after a zero-field relaxation of an initial random or poly-domain distribution of the polarization, where the vortex axis is directed along one of the core crystallographic axes. Subsequently, sinusoidal pulses of a homogeneous electric field …
Small Distortions, Big Polarization: Tetragonal BaTiO3 Nanoparticles for High-Performance Piezoelectric Nanogenerators
Savitribai Phule Pune University（萨维特里拜·普莱·浦那大学）；Indian Institute of Science Education and Research, Pune（印度科学教育与研究学院（浦那））；Advanced Bio-Agro Tech Pvt. Ltd（高级生物农业科技有限公司）；Norel Nutrient Bio-Agro Tech Pvt. Ltd（诺瑞尔营养生物农业科技有限公司）
We explore the impact of the flexoelectric effect and Vegard effect (chemical pressure) on the phase diagrams, long-range polar order and related physical properties of the spherical ferroelectric nanoparticles using Landau-Ginzburg-Devonshire phenomenological approach. The synergy of these effects can lead to the remarkable changes of the nanoparticles' phase diagrams. In particular, a commonly expected transition from ferroelectric to paraelectric phase at some small critical size is absent; so that the critical size loses its sense. Contrary, the stabilization of the ferroelectric phase man…
Polar chiral structures have recently attracted much interest within the scientific community, as they pave the way towards innovative device concepts similar to the developments achieved in nanomagnetism. Despite the growing interest, many fundamental questions related to the mechanisms controlling the appearance and stability of ferroelectric topological structures remain open. In this context, ferroelectric nanoparticles provide a flexible playground for such investigations. Here, we present a theoretical study of ferroelectric polar textures in a cylindrical core-shell nanoparticle. The ca…
Vortices consisting of $90^\circ$ quadrant domains are rarely observed in ferroelectrics. Although experiments show polarization flux closures with stripe domains, it is as yet unclear why pure single vortices are not commonly observed. Here we model and explore the energy of polarization patterns with vortex and stripe domains, formed on the square cross-section of a barium titanate nanowire. Using phase-field simulations, we calculate the associated energy of polarization patterns as a function of nanowire width. Further, we demonstrate the effects of surface energy and electrical boundary c…
In a nanocomposite of reduced graphene oxide (RGO) and BiFeO$_3$ (BFO), the remanent ferroelectric polarization is found to follow nonmonotonic magnetic field dependence at room temperature as the applied magnetic field is swept across 0-20 kOe on a pristine sample. The remanent ferroelectric polarization is determined both from direct electrical measurements on an assembly of nanoparticles and powder neutron diffraction patterns recorded under 0-20 kOe field. The nanosized ($\sim$20 nm) particles of BFO are anchored onto the graphene sheets of RGO via Fe-C bonds with concomitant rise in coval…
