Room Temperature Ferroelectric Polarization Research Articles

Room-temperature electric field-induced out-of-plane ferroelectric polarization in strain-free freestanding 2D SrTiO3 membranes

SrTiO3 (STO), a room-temperature paraelectric material in bulk form, has been a rich playground for emergent phenomena for decades. As an emerging material, great attention has been paid to freestanding 2D STO thin films. Recently, the room-temperature ferroelectricity has been unveiled in strained STO thin films; however, it remains an open question whether the strain-free freestanding 2D STO thin film is room-temperature ferroelectric or not. Here, we report the electric field-induced out-of-plane ferroelectric polarization in large-scale, freestanding, and strain-free 2D STO membranes at room temperature. High-resolution piezoresponse force microscopy measurements show that polarization in freestanding strain-free STO membranes can be switched by electric field and persist for an hour. The first-principles calculations suggest that the intrinsic defects such as oxygen vacancies could be linked to the observed spontaneous out-of-plane polarization in 2D STO membranes, which could be further enhanced by external electric field due to the induced symmetry breaking. Our work reports the unprecedented room-temperature ferroelectric polarization in strain-free freestanding 2D STO membranes, unlocking the great potential of freestanding 2D STO for the applications in novel electronic and logic-in-memory devices.

Room-Temperature Ferroelectricity of Paraelectric Oxides Tailored by Nano-Engineering

Inducing clear ferroelectricity in the quantum paraelectric SrTiO3 is important for triggering methods to discover hidden phases in condensed matter physics. Several methods such as isotope substitution and freestanding membranes could introduce ferroelectricity in SrTiO3 toward nonvolatile memory applications. However, the stable transformation from quantum paraelectric SrTiO3 to ferroelectricity SrTiO3 at room temperature still remains challenging. Here, we used multiple nano-engineering in (SrTiO3)0.65/(CeO2)0.35 films to achieve an emergent room-temperature ferroelectricity. It is shown that the CeO2 nanocolumns impose large out-of-plane strains and induce Sr/O deficiency in the SrTiO3 matrix to form a clear tetragonal structure, which leads to an apparent room-temperature ferroelectric polarization up to 2.5 μC/cm2. In collaboration with density functional theory calculations, it is proposed that the compressive strains combined with elemental deficiency give rise to local redistribution of charge density and orbital order, which induce emergent tetragonality of the strained SrTiO3. Our work thus paves a pathway for architecting functional systems in perovskite oxides using a multiple nano-design.

Anion-induced robust ferroelectricity in sulfurized pseudo-rhombohedral epitaxial BiFeO3 thin films via polarization rotation.

Polarization rotation caused by various strains, such as substrate and/or chemical strain, is essential to control the electronic structure and properties of ferroelectric materials. This study proposes anion-induced polarization rotation with chemical strain, which effectively improves ferroelectricity. A method for the sulfurization of BiFeO3 thin films by introducing sulfur anions is presented. The sulfurized films exhibited substantial enhancement in room-temperature ferroelectric polarization through polarization rotation and distortion, with a 170% increase in the remnant polarization from 58 to 100.7 μC cm-2. According to first-principles calculations and the results of X-ray absorption spectroscopy and high-angle annular dark-field scanning transmission electron microscopy, this enhancement arose from the introduction of S atoms driving the re-distribution of the lone-pair electrons of Bi, resulting in the rotation of the polarization state from the [001] direction to the [110] or [111] one. The presented method of anion-driven polarization rotation might enable the improvement of the properties of oxide materials.

Colossal Room-Temperature Ferroelectric Polarizations in SrTiO3/SrRuO3 Superlattices Induced by Oxygen Vacancies.

Artificial superlattices have demonstrated many unique phenomena not found in bulk materials. For this investigation, SrTiO3/SrRuO3 paraelectric/metallic superlattices with various stacking periods were synthesized via pulsed laser deposition. A robust room-temperature ferroelectric polarization (∼46 μC/cm2) was found in the superlattices with 2 unit cell (u.c.) thick SrRuO3 layers, despite the fact that neither SrTiO3 nor SrRuO3 is inherently ferroelectric. Results obtained from atomically resolved elemental mapping and X-ray photoelectron spectroscopy verified that oxygen vacancies accumulated at the SrTiO3/SrRuO3 interfaces, causing lattice distortions and increased tetragonality (c/a). The observed ferroelectric responses can be mainly attributed to the broken spatial inversion symmetry induced by the ordered distribution of oxygen vacancies at the SrTiO3/SrRuO3 interfaces, coupled with the triggering of external electric field. The resulting polarization mechanism induced by oxygen vacancies suggests viable ways for improving the electrical properties of ferroelectric materials, with the goal of expanding the functionality of a range of electronic devices.

Strong Room-Temperature Ferroelectricity in Strained SrTiO3 Homoepitaxial Film.

Although the discovery of exceptional ferroelectricity in paraelectrics offers great opportunities to enrich the diversity of the ferroelectric family and promote the development of novel functionalities, transformation of paraelectric phases into ferroelectric phases remains challenging. Herein, a method is presented for driving paraelectrics into ferroelectric states via the introduction of M/O-deficient (M for metal) perovskite nanoregions. Using this method, strong ferroelectricity, equivalent to that of classic ferroelectrics, is achieved in a prototype paraelectric strontium titanate (SrTiO3 ) homoepitaxial film embedded with Ti/O-deficient perovskite nanoregions. It is shown that these unique nanoregions impose large out-of-plane tensile strain and electron-doping effects on the matrix to form a tetragonal structure (tetragonality = 1.038), driving the off-center movements of Ti and Sr atoms. This leads to a significant room-temperature ferroelectric polarization (maximum polarization = 41.6 µC cm-2 and spontaneous polarization = 25.2 µC cm-2 at 1.60 MV cm-1 ) with a high thermal stability (Tstable ≈ 1098 K). The proposed approach can be applied to various paraelectrics for creating ferroelectricity and generating emergent physical properties, opening the door to a new realm of materials design.

Structure-property relationships in the lanthanide-substituted PbBi2Nb2O9 Aurivillius phase synthesized by the molten salt method

Samples of PbBi2Nb2O9, PbBi1.5La0.5Nb2O9, and PbBi1.5Nd0.5Nb2O9 have been prepared by the molten salt method. The structure, morphology, and electrical properties were investigated. All samples are single-phase and crystallize in an orthorhombic structure with A21am symmetry. Neutron diffraction data indicate that the Ln3+ cations prefer to occupy the perovskite A-site, whereas Pb/Bi occupy the perovskite A-site and the Bi2O2 layer. Changes in unit cell volume are observed on substitution and are attributed to the ionic radii of the Ln3+ cations and also correlated to changes in the B-O bond distances in the BO6 octahedra, which are also observed in IR spectra. SEM images reveal anisotropic plate-like grains, which increase in size with the presence of Ln3+ ions. The ferroelectric transition temperature (Tc) decreases with decreasing degree of BO6 distortion as the influence of the 6s2 lone pair of Bi3+ is diminished. Relaxor ferroelectric behavior is observed with Ln3+ substitution, driven by the disorder of the A-site cations. The room temperature ferroelectric polarization increases with Ln3+ substitution, ascribed to the decreased dielectric loss.

Improved ferroelectric response of pulsed laser deposited BiFeO3-PbTiO3 thin films around morphotropic phase boundary with interfacial PbTiO3 buffer layer

(1 − x)BiFeO3-xPbTiO3 (BF-xPT) is an interesting material for sensing and actuating devices with large polarization near the morphotropic phase boundary (MPB) (x = 0.30) in the bulk form. However, pulsed laser deposition (PLD) grown (BF-xPT) thin films usually show high electrical leakage and, hence, saturated ferroelectric hysteresis loops are only obtained at subzero temperatures. In this article, we report on high room temperature ferroelectric polarization with saturated hysteresis loops in pulsed laser deposited (BF-xPT) polycrystalline thin films of compositions near the MPB with the use of a thin buffer layer of PbTiO3 (PT). The thin films possessed a perovskite structure with excellent crystallinity and exhibit the presence of a monoclinic (Cm) phase (MA-type) for x = 0.20–0.25 and a mixture of a monoclinic (Cm) phase and a tetragonal (P4mm) phase for x = 0.30–0.35 compositions. The thin films with composition x = 0.25 exhibit a monoclinic phase and yield very large room temperature ferroelectric polarization (2Pr > 80μC/cm2), perhaps the highest room temperature ferroelectric polarization and excellent piezoelectric properties in PLD deposited (BF-xPT) thin films of near-MPB composition. Furthermore, the evolution of ferroelectricity with PT content, studied using room temperature Raman spectroscopy, reveals a correlation with lattice dynamics and stereochemical activity of Bi. Piezoforce domain analysis of the thin films reveals that ferroelectric polarization and electrical leakage in the thin films are intricately related to the type of domains present in the samples, viz., 180°, 109°, 90°, and 71° due to differences in the nature of the domain walls.

The structural and electrical properties modulated by excessive Ti substitution in SrTiO3 films

Ti-rich nonstoichiometric SrTiO3 (STO) films are fabricated on (111) Pt/Ti/SiO2/Si substrates by metal organic deposition. X-ray diffraction reveals the structure of the samples. The effect of nonstoichiometry on the electrical properties of the STO films is investigated by leakage current measurements and dielectric and ferroelectric characterizations. They reveal that the direct current (dc) leakage behavior is greatly improved with increasing Ti content, while the Ti = 1.1 and 1.2 samples show an obvious dielectric relaxation behavior related to the variable valence of the excess Ti ions. More importantly, the nonstoichiometric STO exhibits the room temperature ferroelectric polarization that can be explained mainly by the Ti antisitelike defects and the change of crystal lattice structure of the sample.

Study of structural and magnetoelectric properties of 1−x(Ba0.96Ca0.04TiO3)–x(ZnFe2O4) ceramic composites

Multiferroic ceramic composites of (1−x)Ba0.96Ca0.04TiO3–(x)ZnFe2O4 (BCT-ZF) were prepared from ferroelectric (FE) barium calcium titanate (BCT) and ferromagnetic (FM) zinc ferrite (ZF) by using the solid state reaction method with different mol% fractions of x (x = 0.1 and 0.2). The preliminary structural studies carried out by X-ray diffraction at room temperature reveals that the samples have a tetragonal structure along with the cubic spinel ferrite phase. Raman spectra of the composites also confirm the existence of BCT phase and ZF phase. The room temperature ferroelectric polarization measurements as a function of magnetic field show the existence strong magnetoelectric coupling of 10.85 (mV/(cm.Oe).

Novel multiferroic (Pb1 − 3x/2Ndx)(Ti0.98 − yFeyMn0.02)O3 ceramics with coexisting ferroelectricity and ferromagnetism at ambient temperature

We report the evolution of structural, dielectric, ferroelectric and ferromagnetic properties in novel (Pb1−3x/2Ndx)(Ti0.98−yFeyMn0.02)O3 perovskite ceramics(x=0.08, 0<y<0.05). We found room-temperature ferroelectric polarization and ferromagnetism for higher amount of iron ions(y≥0.04). The paraelectric-ferroelectric phase transition occurred between 650 and 670K for 0≤y≤0.05. Ferromagnetic hysteresis was measured at different temperatures on samples with y≥0.04. Detailed structural analysis evidenced the variation of unit cell parameters with y increasing, confirming the substitution of the iron element in the lattice. 57Fe Mössbauer spectroscopy evidenced that iron ions occupy Ti positions in the perovskite lattice, with the oxidation state Fe3+ and two coordination types. X-ray photoelectron spectroscopy confirmed the presence of iron only as Fe3+ and, moreover, evidenced the presence of a substantial amount of Ti3+ ions in the structure. The presence of both Fe3+ (spin 5/2) in different coordinations as well as Ti3+ (spin 1/2) magnetic ions in B-site positions drives the occurrence of magnetic properties from low temperature to above room temperature, through superexchange Fe3+-O-Fe3+, Fe3+-O-Ti3+ and Ti3+-O-Ti3+ interactions. The finding of coexistent ferroelectric and ferromagnetic properties in these compounds ground the route to facile synthesis of multiferroics by simply doping a classical perovskite ferroelectric material like PbTiO3 with an adequate amount of transition magnetic ions.

Structure and Dielectric Properties of a New Solid Solution (1−x)PbTiO3−xDyFeO3

A solid solution system of novel ferroelectric (1−x)PbTiO3-xDyFeO3 ceramics with 0 ≤ x ≤ 0.50 has been synthesized using the solid state reaction method. The X-ray diffraction data at room temperature indicate a composition-induced structural transition from the tetragonal P4mm phase for 0 ≤ x < 0.25 to the cubic Pm-3m phase for x ≥ 0.25. Both the unit cell volume and the tetragonality gradually decrease with increasing x. The grain size of the ceramics is found by Scanning Electron Microscopy to increase first and then decrease with increasing x. The Curie point moves to low temperatures with increasing DyFeO3 concentration and a composition-induced crossover from a normal ferroelectric phase to a ferroelectric state with diffuse phase transition has been observed. Two Havriliak-Negami relaxation processes and a significant contribution from dc conductance were found at high temperature above the temperature of dielectric maximum, Tm. The room temperature ferroelectric polarization shows a decrease with the increase of x. A partial phase diagram of the solid solution system is constructed based on the dielectric, ferroelectric and structural analyses.

Defect-related room-temperature ferroelectricity in tensile-strained SrTiO3 thin films on GdScO3 (110) substrates

We investigate room-temperature (RT) ferroelectricity in tensile-strained SrTiO3 (STO) thin films grown on GdScO3 (110) substrates. To separate the strain and the defect dipole effect, we apply an electric field to measure the polarization in the direction perpendicular to the elongation axis, and the RT ferroelectric polarization is found to be perpendicular to that axis. These results clearly demonstrate the importance of the contribution of defect dipoles to the RT ferroelectricity observed in STO thin films.

Ferroelectric BaTiO&lt;SUB&gt;3&lt;/SUB&gt; Thin Films on Ti Substrate Fabricated Using Pulsed-Laser Deposition

We report on the fabrication of ferroelectric BaTiO3 thin films on titanium substrates using pulsed laser deposition and their microstructures and properties. Electron microscopy studies reveal that BaTiO3 films are composed of crystalline assemblage of nanopillars with average cross sections from 100 nm to 200 nm. The BaTiO3 films have good interface structures and strong adhesion with respect to Ti substrates by forming a rutile TiO2 intermediate layer with a gradient microstructure. The room temperature ferroelectric polarization measurements show that the as-deposited BTO films possess nearly the same spontaneous polarization as the bulk BTO ceramics indicating formation of ferroelectric domains in the films. Successful fabrication of such ferroelectric films on Ti has significant importance for the development of new applications such as structural health monitoring spanning from aerospace to civil infrastructure. The work can be extended to integrate other ferroelectric oxide films with various promising properties to monitor the structural health of materials.