Bismuth ferrite, BiFeO3, is a multiferroic solid that is attracting increasing attention as a potential photocatalytic material, because the ferroelectric polarisation enhances the separation of photogenerated carriers. With the motivation of finding routes to engineer the band gap and the band alignment, while conserving or enhancing the ferroelectric properties, we have investigated the thermodynamic, electronic and ferroelectric properties of BiCoxFe1 xO3 solid solutions, with 0 < x < 0.13, using density functional theory. We show that the band gap can be reduced from 2.9 eV to 2.1 eV by cobalt substitution, while simultaneously increasing the spontaneous polarisation, which is associated with a notably larger Born effective charge of Co compared to Fe cations. We discuss the interaction between Co impurities, which is strongly attractive and would drive the aggregation of Co, as evidenced by Monte Carlo simulations. Phase separation into a Co-rich phase is therefore predicted to be thermodynamically preferred, and the homogeneous solid solution can only exist in metastable form, protected by slow cation diffusion kinetics. Finally, we discuss the band alignment of pure and Co-substituted BiFeO3 with relevant redox potentials, in the context of its applicability in photocatalysis.
We present first-principles supercell calculations on BaTi0.74Zr0.26O3, a prototype material for relaxors with a homovalent substitution. From a statistical analysis of relaxed structures, we give evidence for four types of Ti-atom polar displacements: along the < 1 1 1 >, < 1 1 0 >, or < 1 0 0 > directions of the cubic unit cell, or almost cancelled. The type of a Ti displacement is entirely determined by the Ti/Zr distribution in the adjacent unit cells. The underlying mechanism involves local strain effects that ensue from the difference in size between the Ti4+ and Zr4+ cations. These resu…
Titanates with the perovskite structure, including ferroelectrics (e.g., BaTiO$_3$) and ferromagnetic ones (e.g., YTiO$_3$), are important functional materials. Recent theoretical studies predicted multiferroic states in strained EuTiO$_3$ and titanate superlattices, the former of which has already been experimental confirmed. Here, a first-principles calculation is performed to investigate the structural, magnetic, and electronic properties of Y half-substituted LaTiO3. Our results reveal that the magnetism of Y$_{0.5}$La$_{0.5}$TiO$_3$ sensitively depends on its structural details because of…
The synthesis of layered ferrite-lead titanate zirconate (PZT) and lanthanum nanganite-PZT and the observation of giant magneto-electric interactions are discussed. The ferrites used in our studies included pure and Zn substituted cobalt-, nickel- and lithium ferrites. Ferromagnetic manganites used included both calcium and strontium substituted systems. The samples were prepared from 10-40 mm thick films obtained by tape-casting. Our studies showed strong ME coupling in manganite-PZT and cobalt zinc ferrite-PZT, and a giant ME effect in nickel zinc ferrite-PZT. We found evidence for Zn assist…
Ba{[Gax,Tax]Ti(1-2x)}O3 ceramics with x equal to 0, 0.0025, 0.005, 0.01, 0.025 and 0.05 have been prepared by conventional solid-state reaction. Structural and dielectric characterization have been performed to investigate the effect of dipole-pair substitution concentration on the macroscopic dielectric properties. Ba{[Gax,Tax]Ti(1-2x)}O3 evolves from a classic ferroelectric to a diffuse phase transition (DPT) as x increases. Ba{[Gax,Tax]Ti(1-2x)}O3 for x > or = 0.01 possesses diffuseness parameters comparable to Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT) and recently reported (Ba0.97Pr0.03)(Ti0.9425Ce…
Structural, magnetic and ferromagnetic resonance characterization studies have been performed on lay-ered ferromagnetic-ferroelectric oxides that show strong magnetoelectric coupling. The samples contained thick films of ferrites or substituted lanthanum manganites for the ferromagnetic phase and lead zirconate titanate for the ferroelectric phase, and were sintered high temperatures. Results indicate defect free ferrites, but deterioration of manganite parameters due to diffusion at the interface and accounts for poor magnetoelectric coupling in manganite-PZT samples.
Metal-organic frameworks (MOFs) have emerged as promising materials for carbon capture applications due to their high CO2 capacities and tunable properties. Amongst the many possible MOFs, metal-substituted compounds based on M-DOBDC and M-HKUST-1 have demonstrated amongst the highest CO2 capacities at the low pressures typical of flue gasses. Here we explore the possibility for additional performance tuning of these compounds by computationally screening 36 metal-substituted variants (M = Be, Mg, Ca, Sr, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, W, Sn, and Pb) with respect to their CO2 adsor…
Phase, microstructural, dielectric and ferroelectric properties investigation clearly reveal that the charge imbalance created due to alio-valent Gd3+-ion substitution at Pb2+ site in lead magnesium niobate should be compensated by changing B-site cation ratio instead of creating A-site or B-site vacancies. Microstructure analysis along with elemental mapping exhibit segregation of magnesium oxide (MgO) and gadolinium niobate (GdNbO4) phase, which is observed to remain invariant to the charge compensation mechanism. Fitting of frequency dependent temperature of dielectric constant maximum Tm (…
In this work, the potential to exploit Aurivillius higher order composition (n=6) given by Bi4Ti3O12-3BiFeO3 as single phase and high temperature magnetoelectric materials are well explored by elaborately studying the concerned structure and physical properties. Bi4Ti3O12-3Bi1-xLaxFeO3 (x=0, 0.01, 0.05, 0.1, 0.2) was synthesized via solid-state reaction route and X-ray diffraction data revealed that the lattice parameters associated with orthorhombic cell (space group P21am) decrease with increase in La3+ content confirming the incorporation of La. In the frequency dependent dielectric measure…
Formation of phases during the solid state synthesis of the barium-modified NBT solid solutions, with substitutions of zirconium and tin ions for titanium are investigated. The synthesis is a multi-step process which is accompanied by the formation of a number of intermediate phases (depending on the solid solution composition and the synthesis temperature). Single phase solid solutions have been manufactured when the sintering temperature was increased to 1000-1100 C. An increase of the concentration of the substituting ions results in a linear increase in the size of the crystal cell. As a c…
The equilibrium domain structure and its evolution under an electric field in ferroelectric bilayers and graded multilayers are considered. The equilibrium bilayer is self-poled and contains a single-domain and a polydomain (with 180 domains) layers. The polarization of a graded multilayer proceeds by movement of wedge-like domains as a result of progressive transformation of polydomain layers to a single-domain state. The theory provides the principal explanation of peculiarities of dielectric behavior of graded ferroelectric films and can be applied to graded ferromagnetics and ferroelastics…
We fabricated ferroelectric Bi4Ti3O12 (BiT) single crystalline thin films site-specifically substituted with LaTMO3 (TM = Al, Ti, V, Cr, Mn, Co, and Ni) on SrTiO3 substrates by pulsed laser epitaxy. When transition metals are incorporated into a certain site of the BiT, some of BiT-LaTMO3 showed a substantially decreased band gap, coming from the additional optical transition between oxygen 2p and TM 3d states. Specifically, all alloys with Mott insulators revealed a possibility of band gap reduction. Among them, BiT-LaCoO3 showed the largest band gap reduction by ~1 eV, positioning itself as …
Ba(Zr,Ti)O$_3$ is a lead-free relaxor ferroelectric. Using the first-principles method, the ferroelectric dipole moments for pure BaTiO$_3$ and Ba(Zr,Ti)O$_3$ supercells have been studied. All possible ion configurations of BaZr$_{0.5}$Ti$_{0.5}$O$_3$ and BaZr$_{0.25}$Ti$_{0.75}$O$_3$ are constructed in a $2\times2\times2$ supercell. For the half-substituted case, divergence of ferroelectric properties has been found among these structures, which seriously depends on the arrangement of Ti and Zr ions. Thus our results provide a reasonable explanation to the relaxor behavior of Ba(Zr,Ti)O$_3$. …
We report the evolution of structural, magnetic and dielectric properties due to partial substitution of Ba by Sr in the high temperature multiferroic YBaCuFeO5. This compound exhibits ferroelectric and antiferromagnetic transitions around 200 K and these two phenomena are presumed to be coupled with each other. Our studies on magnetic and dielectric properties of the YBa1-xSrxCuFeO5 (x = 0.0, 0.25 and 0.5) show that substitution of Sr shifts magnetic transition towards higher temperature whereas dielectric transition to lower temperature. These results points to the fact that magnetic and die…
Within the modified model of proton ordering of one-dimensional ferroelectric having hydrogen bonds of PbHPO$_4$-type, their thermodynamic and dynamic characteristics are studied and calculated taking into account the linear (by crystal deformations $\varepsilon_i$ ($i=1,3$) and $\varepsilon_4$) contributions into the energy of a proton system but without taking into account the tunneling in the two-particle cluster approximation. There has been obtained a good quantitative description of the temperature dependence of polarization, static dielectric permittivity, heat capacity and frequency de…
A long standing problem of domain switching process - how domains nucleate - is examined in ultrathin ferroelectric films. We demonstrate that the large depolarization fields in ultrathin films could significantly lower the nucleation energy barrier (U*) to a level comparable to thermal energy (kBT), resulting in power-law like polarization decay behaviors. The "Landauer's paradox": U* is thermally insurmountable is not a critical issue in the polarization switching of ultrathin ferroelectric films. We empirically find a universal relation between the polarization decay behavior and U*/kBT.
Within the modified four-sublattice model of RbHSO$_{4}$ with taking into account the piezoelectric coupling to the strains $\varepsilon_i$, $\varepsilon_4$, $\varepsilon_5$, and $\varepsilon_6$, the polarization components, static and dynamic dielectric permittivity of clamped and free crystal are calculated in the mean field approximation. At the proper choice of the values of the theory parameters, a satisfactory quantitative description of the available experimental data is obtained.
The antiferrodistortive (AFD) structural transitions of calcium titanate (CaTiO3) at ambient pressure have been extensively studied during the last few years. It is found none of the AFD polymorphs is polar or ferroelectric. However, it was recently shown theoretically and later experimentally confirmed that a ferroelectric transition in CaTiO3 can be induced by tensile strains. The ferroelectric instability is believed to be strongly coupled to the AFD soft modes. In this article, we present a complete thermodynamic potential for describing the coupling between the AFD and ferroelectric phase…
A Landau-Ginsburg-Devonshire-type nonlinear phenomenological theory is presented, which enables the thermodynamic description of dense laminar polydomain states in epitaxial ferroelectric thin films. The theory explicitly takes into account the mechanical substrate effect on the polarizations and lattice strains in dissimilar elastic domains (twins). Numerical calculations are performed for PbTiO3 and BaTiO3 films grown on (001)-oriented cubic substrates. The "misfit strain-temperature" phase diagrams are developed for these films, showing stability ranges of various possible polydomain and si…
The interaction of ferroelectric 180 degree domain wall with a strongly inhomogeneous electric field of biased Scanning Probe Microscope tip is analyzed within continuous Landau-Ginzburg-Devonshire theory. Equilibrium shape of the initially flat domain wall boundary bends, attracts or repulses from the probe apex, depending on the sign and value of the applied bias. For large tip-wall separations, the probe-induced domain nucleation is possible. The approximate analytical expressions for the polarization distribution are derived using direct variational method. The expressions provide insight …
We propose the thermodynamical theory of nanodomain tailoring with the help of atomic force microscope electric field in thin ferroelectric-semiconductor films. We modified the existing thermodynamical models of domain formation allowing for the Debye screening, recharging of sluggish surface charge layers caused by emission current between the tip apex and sample surface.For the first time we calculated the realistic sizes of nanodomains recorded in BaTiO3, PbZrxTi1-xO3 and LiTaO3 ferroelectric-semiconductor thin films in contrast to the over-estimated ones obtained in the evolved approaches.…
Modeling ferroelectric materials from first principles is one of the successes of density-functional theory, and the driver of much development effort, requiring an accurate description of the electronic processes and the thermodynamic equilibrium that drive the spontaneous symmetry breaking and the emergence of macroscopic polarization. We demonstrate the development and application of an integrated machine learning model that describes on the same footing structural, energetic and functional properties of barium titanate ($\text{BaTiO}_3$), a prototypical ferroelectric. The model uses ab ini…
Coexistence of Ferroelectric and Relaxor-like Phases in a Multiferroic Solid Solution (1-x)Pb(Fe$_{1/2}$Nb$_{1/2}$)O$_3$-xPbMnO$_3$
Institute of Physics, 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, National Academy of Sciences of Ukraine（乌克兰国家科学院弗兰采维奇材料科学问题研究所）；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）
We review existing manifestations and prospects for ferroelectricity in electronically and optically active carbon-based materials. The focus point is the proposal for the electronic ferroelectricity in conjugated polymers from the family of substituted polyacetylenes. The attractive feature of synthetic organic ferroelectrics is a very high polarizability coming from redistribution of the electronic density, rather than from conventional displacements of ions. Next fortunate peculiarity is the symmetry determined predictable design of perspective materials. The macroscopic electric polarizati…
We propose a two-sublattice proton ordering model for the quasione-dimensional CsH$_2$PO$_4$ ferroelectric with hydrogen bonds, which takes into account linear on lattice strains $u_1$, $u_2$, $u_3$ and $u_5$ contribution to the energy of proton subsystem. The model also takes into account the dependence of effective dipole moments of pseudospins on the order parameters, which enables one to agree the effective dipole moments in paraelectric and ferroelectric phases. Within this model in two-particle cluster approximation on short-range interactions and in the mean field approximation on long-…
The model of NH$_3$CH$_2$COOH$\cdot$H$_2$PO$_3$, modified by taking into account the piezoelectric coupling between the ordering structure elements and the strains $\varepsilon_i$, $\varepsilon_j$, is used for investigation of the effects that appear under external pressures. Within two-particle cluster approximation, the components of polarization vector and static dielectric permittivity tensor of the mechanically clamped and free crystals, their piezoelectric and thermal characteristics are calculated. The effect of hydrostatic pressure on the phase transition and the calculated physical ch…
Using Molecular Dynamics simulations based on the effective hamiltonian developed by Zhong, Vanderbilt and Rabe [Phys. Rev. Lett. {\bf 73}, 1861 (1994)] (and fitted on first-principles calculations only), the technique of the thermodynamic integration is applied to barium titanate. It allows to compute the difference of free energy between macroscopic states with different polarizations, from the thermal averages of the forces acting on the local modes. This is achieved by performing molecular dynamics under the constraint of fixed polarization. The Landau free energy is thus interpreted as a …
We present a thermodynamic analysis of the recently discovered nitride ferroelectric materials using the classic Landau-Devonshire approach. The electrostrictive and dielectric stiffness coefficients of Al1-xScxN with wurtzite structure (6mm) are determined using a free energy density function assuming a hexagonal parent phase (6/mmm), with the first order phase transition based on the dielectric stiffness relationships. The results of this analysis show that the strain sensitivity of the energy barrier is one order of magnitude larger than that of the spontaneous polarization in these novel w…
Atomic-scale control of spins by electric fields is highly desirable for future technological applications. Magnetically-doped Aurivillius-phase oxides present one route to achieve this, with magnetic ions substituted into the ferroelectric structure at dilute concentrations, resulting in spin-charge coupling. However, there has been minimal exploration of the ferroelectric switching pathways in this materials class, limiting predictions of the influence of an electric field on the magnetic spins in the structure. Here, we determine the ferroelectric switching pathways of the end member of the…
Ca$_3$Ti$_2$O$_7$ is an experimentally confirmed hybrid improper ferroelectric material, in which the electric polarization is induced by a combination of the coherent TiO$_6$ octahedral rotation and tilting. In this work, we investigate the tuning of ferroelectricity of Ca$_3$Ti$_2$O$_7$ using iso-valent substitutions on Ca-sites. Due to the size mismatch, larger/smaller alkaline earths prefer $A$'/$A$ sites respectively, allowing the possibility for site-selective substitutions. Without extra carriers, such site-selected iso-valent substitutions can significantly tune the TiO$_6$ octahedral …
We present a theoretical description of the influence of misfit strain on mobile defects dynamics in thin strained ferroelectric films. Self-consistent solutions obtained by coupling the Poissons equation for electric potential with continuity equations for mobile donor and electron concentrations and time-dependent Landau-Ginzburg-Devonshire equations reveal that the Vegard mechanism (chemical pressure) leads to the redistribution of both charged and electro-neutral defects in order to decrease the effective stress in the film. Internal electric fields, both built-in and depolarization ones, …
In the paper, the description of the dielectric and ferroelectric properties of BaTiO_3 single crystals using Landau thermodynamic potential is addressed. Our results suggest that when using the sixth-power free energy expansion of the thermodynamic potential, remarkably different values of the fourth-power coefficient, β(the coefficient of P^4_i terms), are required to adequately reproduce the nonlinear dielectric behavior of the paraelectric phase and the electric field induced ferroelectric phase, respectively. In contrast, the eighth-power expansion with a common set of coefficients enable…
We present the results of the thermodynamic theory of piezoelectric ferroelectrics and of the phenomenological theory of thermodynamic characteristics of the KH$_{2}$PO$_{4}$ type ferroelectrics. Available experimental data for the dielectric, piezoelectric, and elastic characteristics of the KH$_{2}$PO$_{4}$ type ferroelectrics and NH$_4$H$_{2}$PO$_{4}$ type antiferroelectrics are described using the proposed microscopic theory of these crystals. Using the results of the thermodynamic theory and experimental data we calculate the dielectric, piezoelectric, and elastic characteristics of the K…
Enhanced room-temperature electromechanical coupling in the lead-free ferroelectric system $(1-x)$BaZr$_{0.2}$Ti$_{0.8}$O$_{3}$ - $x$Ba$_{0.7}$Ca$_{0.3}$TiO$_{3}$ (abbreviated as BZCT) at $x=0.5$ is attributed to the existence of a morphotropic phase region (MPR) containing an intermediate orthorhombic ($O$) phase between terminal rhombohedral ($R$) BZT and tetragonal ($T$) BCT phases. However, there is ambiguity regarding the morphotropic phase transition in BZCT at room temperature - while some experiments suggest a single $O$ phase within the MPR, others indicate coexistence of three polar …
Fabricating complex transition metal oxides with a tuneable band gap without compromising their intriguing physical properties is a longstanding challenge. Here we examine the layered ferroelectric bismuth titanate and demonstrate that, by site-specific substitution with the Mott insulator lanthanum cobaltite, its band gap can be narrowed as much as one electron volt, while remaining strongly ferroelectric. We find that when a specific site in the host material is preferentially substituted, a split-off state responsible for the band gap reduction is created just below the conduction band of b…
We have investigated the effect of transition metal dopants on the local structure of the prototypical 0.75 Pb(Mg$_{1/3}$Nb$_{2/3}$)O$_3$-0.25 PbTiO$_3$ relaxor ferroelectric. We find that these dopants give rise to very different local structure and other physical properties. For example, when Mg is partially substituted by Cu or Zn, the displacement of Cu or Zn is much larger than that of Mg, and is even comparable to that of Nb. The polarization of these systems is also increased, especially for the Cu-doped solution, due to the large polarizability of Cu and Zn. As a result, the predicted …
We describe ferroelectric thin films with circular electrodes and develop a thermodynamic theory that explains previously mysterious experiments. It is found to be especially useful for restricted geometries such as microstructures for which boundary conditions are well known to play an important role in ferroelectric properties. We have explored a new switching mechanism, which consists of an inhomogeneous rotational motion of the polarization and leads to an extended vortex state. The vortex appearance exhibits characteristic properties of a first-order field-induced phase transition: three …
We investigated the crystal and electronic structures of ferroelectric Bi4Ti3O12 (BiT) single crystalline thin films site-specifically substituted with LaCoO3 (LCO). The epitaxial films were grown by pulsed laser epitaxy on NdGaO3 and SrTiO3 substrates to vary the degree of strain. With increasing the LCO substitution, we observed a systematic increase in the c-axis lattice constant of the Aurivillius phase related with the modification of pseudo-orthorhombic unit cells. These compositional and structural changes resulted in a systematic decrease in the band gap, i.e., the optical transition e…
Comprehensive review of investigations of substances with a small difference in the energies of the ferroelectric and antiferroelectric types of dipole ordering is presented. Detailed analysis of the stability of homogeneous phases and conditions for existence of the inhomogeneous state of the substance containing domains of the coexisting ferroelectric and antiferroelectric phases is presented. It is shown that the interaction of locally separated domains of the ferroelectric and antiferroelectric phases stabilizes an inhomogeneous state of these materials. The analysis of physical phenomena …
A thermodynamic theory is developed for dense laminar domain structures in epitaxial ferrolectric films. It is found that, at some critical misfit strain between the film and substrate, the 90 degrees c/a/c/a domain structure becomes unstable with respect to the appearance of the polarization component parallel to domain walls, which results in the formation of a heterophase structure. For PbTiO_3 and BaTiO_3 films, the stability ranges of polydomain and heterophase states are determined using "misfit strain - temperature" diagrams. Dielectric anomalies accompanying misfit-strain-driven struct…
A spin model of quasi-one dimensional LiCu$_{2}$O$_{2}$ compound with ground state of ellipsoidal helical structure in which the helical axis is along the diagonal of CuO$_{4}$ squares has been adopted. By taking into account the interchain coupling and exchange anisotropy, the exotic magnetic properties and ferroelectricity induced by spiral spin order have been studied by performing Monte Carlo simulation. The simulation results qualitatively reproduce the main characters of ferroelectric and magnetic behaviors of LiCu$_{2}$O$_{2}$ compound and confirm the low-temperature incollinear spiral …
Low-dimensional multiferroic materials hold great promises in miniaturized device applications such as nanoscale transducers, actuators, sensors, photovoltaics, and nonvolatile memories. Here, using first-principles theory we predict that two-dimensional (2D) monolayer Group IV monochalcogenides including GeS, GeSe, SnS, and SnSe are a class of 2D semiconducting multiferroics with strongly coupled giant in-plane spontaneous ferroelectric polarization and spontaneous ferroelastic lattice strain that are thermodynamically stable at room temperature and beyond, and can be effectively modulated by…
Using modified microscopic model of GPI by taking into account the piezoelectric coupling with strains $\varepsilon_i$ in the frames of two-particle cluster approximation, the components of polarization vector and static dielectric permittivity tensor of the crystal at applying the external transverse electric fields $E_1$ and $E_3$ are calculated. An analysis of the influence of these fields on thermodynamic characteristics of GPI is carried out. A satisfactory quantitative description of the available experimental data for these characteristics has been obtained at a proper choice of the mod…
In the framework of Landau--Ginzburg--Devonshire (LGD) phenomenological theory, the influence of misfit strains, surface energy, and finite-size effects on phase diagrams, polar properties, and hysteresis loops has been calculated for multilayered thin films of the type ferroelectric/virtual ferroelectric. The influence of elastic deformations that arise at the interface thin film--substrate owing to a mismatch between the lattice constants in the film and the substrate on the phase diagrams of multilayered thin films virtual ferroelectric SrTiO$_{3}$/ferroelectric BaTiO$_{3}$ has been studied…
