Hybrid Improper Ferroelectricity Research Articles

Effect of Ca2MnO4 on the magnetic and electric properties in Ca3Mn2O7 ceramics prepared with different sintering temperature

Hybrid improper ferroelectricity Ca3Mn2O7 is the promising multiferroic materials, which has attracted considerable attention due to their potential applications in areas such as electronic devices and storage media. The magnetic and electric properties of the layered perovskite Ca3Mn2O7 ceramics with different proportions of single-layer Ca2MnO4 phase synthesized by solid state reaction within adjusting the sintering temperature have been investigated. The x-ray diffraction patterns and the characteristic of magnetic transition from magnetization curves show that the ratio of Ca2MnO4 is reduced from 22.9 % of sintering at 1200 °C to 0 % of sintering at 1300 °C, which implies that the narrow suitable sintering temperature is the most factor for preparation of pure Ca3Mn2O7 ceramic samples. The ferroelectricity of all samples was investigated and the ferroelectricity decreased with the increase of Ca2MnO4 content due to the presence of non-ferroelectric Ca2MnO4 phase. The magnetoelectric coupling effect was discussed by the magnetization induced from the electric field. The results speculated that a small amount of Ca2MnO4 can improve the magnetoelectric coupling effect due to the interface effect in multiphase materials, which suggests that a new method to enhance the magnetoelectric coupling effect in Ca3Mn2O7 system.

La2SrSc2O7: A-Site Cation Disorder Induces Ferroelectricity in Ruddlesden-Popper Layered Perovskite Oxide.

Rational design of ferroelectrics in layered perovskites, like n = 2 Ruddlesden-Popper (RP) phase A3B2O7, has been achieved by the hybrid-improper ferroelectric (HIF) mechanism, in which an electric polarization is induced via a trilinear coupling to nonpolar BO6 octahedral rotation and tilt distortions around crystallographic axes. In the present work, hybrid improper ferroelectricity in n = 2 RP-type La2SrSc2O7 induced by the disordering of Sr2+/La3+ cations on the A-sites in rocksalt ([Sr/La]Rs = 25/75) and perovskite ([Sr/La]Pv = 50/50) layers is demonstrated through experimental and theoretical investigations. The ferroelectric A21am structure (a-a-c+ in Glazer notation) at room temperature and the second-order phase transition to paraelectric Amam structure (a-a-c0) at TC ∼ 600 K are determined by a combination of X-ray and neutron diffraction and optical second harmonic generation. The ferroelectric hysteresis loop measurements prove the switchable electric polarization indicative of ferroelectricity. These results represent an unprecedented example of ferroelectricity in the n = 2 RP family of Ln2AB2O7 with inequivalent Ln3+ and A2+ cations. Combining the abovementioned experimental results with the first-principles calculations, we verify the role of Sr/La distributions in regulating the interlayer rumpling, which, in addition to the structural tolerance factor, is key to controlling the structural distortions of RP phases. The stabilization of the ferroelectric, a-a-c+ distorted structure is a consequence of the disordered Sr/La distribution on the A-sites, which suppresses the rumpling-induced octahedral deformations in competition with the octahedral rotations and thus enables the concurrence of a0a0c+ rotations and a-a-c0 tilts required for the HIF mechanism. This work demonstrates the possibility of altering the crystal symmetry of RP phases through the A-site cation disorder and provides a complementary approach to the rational design of new HIF materials.

Optimized hybrid improper ferroelectricity of (Ca1-xNdx)3Ti2O7 ceramics based on soft doping effects

Low remnant polarization and high coercive field are the main factors limiting the practical application of Ca3Ti2O7-based hybrid improper ferroelectric ceramics. Based on sol-gel method and soft doping effect, (Ca1-xNdx)3Ti2O7 (x=0.003) ceramics with higher remnant polarization of ∼3.53 μC/cm2 and lower coercive field of ∼91 kV/cm were obtained. More interestingly, thanks to the large distortion amplitude of TiO6 octahedron and effective suppression of defects such as oxygen vacancies caused by Nd3+ as a donor dopant, the remnant polarization of (Ca1-xNdx)3Ti2O7 (x = 0.003 and 0.006) ceramics measured at 10 Hz using the DHM mode were as high as 7.33 μC/cm2 and 5.85 μC/cm2. These findings prove that the soft doping at A sites of Ca3Ti2O7 material is a simple and effective strategy to enhance its hybrid improper ferroelectricity.

The novel electrical properties in quasi‐2D hybrid improper ferroelectric Sr3Sn2O7 ceramic and the structural modulation

AbstractThe quasi‐two‐dimensional Ruddlesden–Popper material, Sr3Sn2O7 with hybrid improper ferroelectricity, has gained significant scientific interest owing to its unique ferroelectric phase transition mechanism. However, its electrical behaviors near the phase transition temperature necessitate further investigation. In this study, high‐quality Sr3Sn2O7 ceramic was successfully prepared, and its temperature‐dependent electrical properties were systematically studied. The phase transition from ferroelectric to paraelectric of Sr3Sn2O7 ceramic near 160°C was evidenced by the varying electrical properties dependence of temperature. It is found that the space‐charge‐limited bulk conduction with deep traps is identified as dominant conduction mechanism for Sr3Sn2O7 ceramic that has high resistivity. An abnormal increasing trend of coercive field with temperature was observed and is discussed with trap‐filling process and octahedral rotation distortion. Interestingly, Sr3Sn2O7 ceramic exhibits negative piezoelectric effect and negative electrostriction responded to biased electric field, which is dramatically influenced by ferroelectric polarization. Overall, this study serves as a reference for exploring the electrical properties of other hybrid improper ferroelectrics, particularly near their Curie temperature.

Switching of Hybrid Improper Ferroelectricity in Oxide Double Perovskites

Switching of Hybrid Improper Ferroelectricity in Oxide Double Perovskites

The optical and ferroelectric properties of Fe-doped hybrid improper ferroelectricity Ca3Ti2O7 via experimental and density functional theory study

The magnetoelectric multiferroic materials with ferroelectric and magnetic orders have great attributed attention in the field of magnetoelectric memories and magnetic resonance devices. Here, we systematically investigated the optical and multiferroic properties of Fe-doped hybrid improper ferroelectricity Ca3Ti2O7 prepared by sol-gel method. The distortion of TiO6 octahedron changes with the content of oxygen vacancy introduced by Fe doping, thus realizing the adjustment of remnant ferroelectric polarization of the samples. The slight blue shift of the Raman band at 667 cm−1 reflected the introduces of oxygen vacancies by Fe doping. The optical bandgaps of the doped samples were reduced after doping, agreeing with the results of the first-principles calculations. With the introduction of Fe3+, the magnetism increases gradually. The first-principles calculation shows that magnetism origins from the Fe-3d and their surrounding O-2p orbitals. The Fe-doping Ca3Ti2O7 materials realizing the introduction of magnetic properties while regulating its ferroelectric properties are expected to be applied in magnetoelectric memories, optoelectronic devices spintronics and magnetic response devices.

Hybrid Improper Ferroelectricity in Columnar (NaY)MnMnTi4 O12.

We show that cation ordering on A site columns, oppositely displaced via coupling to B site octahedral tilts, results in a polar phase of the columnar perovskite (NaY)MnMnTi4 O12 . This scheme is similar to hybrid improper ferroelectricity found in layered perovskites, and can be considered a realisation of hybrid improper ferroelectricity in columnar perovskites. The cation ordering is controlled by annealing temperature and when present it also polarises the local dipoles associated with pseudo-Jahn-Teller active Mn2+ ions to establish an additional ferroelectric order out of an otherwise disordered dipolar glass. Below TN ≈12 K, Mn2+ spins order, making the columnar perovskites rare systems in which ordered electric and magnetic dipoles may reside on the same transition metal sublattice.

Hybrid Improper Ferroelectricity in Columnar (NaY)MnMnTi4O12

AbstractWe show that cation ordering on A site columns, oppositely displaced via coupling to B site octahedral tilts, results in a polar phase of the columnar perovskite (NaY)MnMnTi4O12. This scheme is similar to hybrid improper ferroelectricity found in layered perovskites, and can be considered a realisation of hybrid improper ferroelectricity in columnar perovskites. The cation ordering is controlled by annealing temperature and when present it also polarises the local dipoles associated with pseudo‐Jahn–Teller active Mn2+ ions to establish an additional ferroelectric order out of an otherwise disordered dipolar glass. Below TN≈12 K, Mn2+ spins order, making the columnar perovskites rare systems in which ordered electric and magnetic dipoles may reside on the same transition metal sublattice.

Hybrid improper ferroelectricity and phase transition behavior of Li2Nd2Ti3O10 ceramics with A-site ordered triple-layer Ruddlesden-Popper structure

Hybrid improper ferroelectricity has been extensively reported through theoretical prediction and experimental investigation in the oxides with Ruddlesden-Popper (R–P) structures. However, the experimentally reported ferroelectric materials based on triple-layer R–P structures are rare, and the weak ferroelectricity impedes its practical application. In the present work, the single-phase Li2Nd2Ti3O10 ceramics with A-site cation ordered triple-layer R–P structure was obtained by spark plasma sintering technique, and the crystal structure of P21ab symmetry was revealed by neutron powder diffraction and transmission electron microscope analysis. Furthermore, the switchable ferroelectricity in Li2Nd2Ti3O10 ceramics has been observed at room temperature, and the saturated polarization-electric field hysteresis loop was obtained with Pr = 0.4 μC/cm2 under the electric field of 250 kV/cm. The phase transition behavior of Li2Nd2Ti3O10 oxides was revealed by the temperature-dependence Raman and dielectric spectra combined with the piezoelectric property.

Ca2FeOsO6/Sr2FeOsO6 superlattice: Multiferroicity above room temperature with giant hybrid-improper ferroelectric polarization and high photovoltaic efficiency

Using first-principles calculations, the structure and electronic properties of the room-temperature ferrimagnetic ${\mathrm{Ca}}_{2}{\mathrm{FeOsO}}_{6}/{\mathrm{Sr}}_{2}{\mathrm{FeOsO}}_{6}$ superlattice are investigated. We show that the superlattice hosts hybrid-improper ferroelectricity despite the fact that bulk ${\mathrm{Sr}}_{2}{\mathrm{FeOsO}}_{6}$ realizes an ${a}^{0}{a}^{0}{c}^{\ensuremath{-}}$ tilting pattern of the O octahedra. The magnitude is comparable to that of conventional ferroelectric materials and is found to increase under both compressive and tensile strain. In contrast to competing superlattices, a ferrimagnetic critical temperature above room temperature is realized. An indirect-to-direct band-gap transition is observed between $+$1% and $+$2% strain, coming along with localization of the valence and conduction states on different transition-metal sublattices, which enables efficient electron-hole separation upon photoexcitation. The potential gradient due to the ferroelectric polarization supports the electron-hole separation and a spectroscopic limited maximum efficiency of 27% confirms excellent potential in solar cell applications. The tunable room-temperature ferroelectricity, high critical temperature of the ferrimagnetic ordering with high magnetization, and favorable photoabsorption properties of the ${\mathrm{Ca}}_{2}{\mathrm{FeOsO}}_{6}/{\mathrm{Sr}}_{2}{\mathrm{FeOsO}}_{6}$ superlattice open up a broad range of technological applications.

Design of high polarization low switching barrier hybrid improper ferroelectric perovskite oxide superlattices.

Hybrid improper ferroelectricity is a useful tool to design ABO3/A'BO3 polar superlattices from non polar building blocks. In this study, we have designed high polarization-low switching barrier hybrid improper ferroelectric superlattices with efficient polarization, and polarization-magnetization switching properties above room temperature, using density functional theory and ab initio molecular dynamics simulations. Superlattices with a chemical formula of (AAlO3)m/(A'AlO3)n, where m/n = 1/1, 1/3, 3/1, 1/5 and 5/1, A, A' = Lanthanide and Y cations are considered to outline the design principles behind polarization switching and (LaFeO3)3/(CeFeO3)1 is investigated for polarization-magnetization switching. We find that the unconventional switching paths via out-of-phase rotation QR- (a0a0c-) and tilt precession QTP always yield lower switching barrier compared to those via in-phase rotation QR+ (a0a0c+) and tilt QT (a-a-c0) of BO6 octahedra. Results from ab initio molecular dynamics simulations estimate the temperature at which the lowest energy barrier can be overcome. It is possible to tune the polarization switching barrier by tuning the tolerance factor, A,A' cation radius mismatch and super lattice periodicity. For switching via QR-, the switching barrier varies exponentially with rotation angle, indicating how high switching barrier is expected for systems, away from cubic symmetry. We provide a recipe to overcome such a bottleneck by tuning superlattice periodicity. Finally, we have proposed the multiferroic device application concept through a proposed polarization-temperature hysteresis loop and magnetization switching.

Significantly enhanced hybrid improper ferroelectricity of Ca3Ti2O7 ceramics by the oxygen vacancy engineering

Ca3Ti2O7 materials with hybrid improper ferroelectricity call tremendous interest due to their great potential in designing novel room-temperature single-phase multiferroics with a strong magnetoelectric coupling effect. However, achieving Ca3Ti2O7-based ceramics with superior room-temperature ferroelectricity remains a crucial challenge. Herein, Ca3Ti2O7 ceramics were prepared by a tartaric acid sol–gel method and sintered in air and oxygen atmospheres, respectively. It was found that the long-time high-temperature sintering in air could lead to the formation of CaTiO3/Ca3Ti2O7/CaTiO3 sandwich structure, and oxygen-enriched sintering could effectively avoid the formation of CaTiO3 phase on the surface. The superior hybrid improper ferroelectricity is attained in Ca3Ti2O7 ceramics sintered in oxygen atmosphere with a higher remnant polarization (3.63 μC/cm2) and lower coercive electric field (72.6 kV/cm) obtained by positive-up and negative-down method, which is better than the ceramic sample sintered in air. The significantly better ferroelectricity is benefited from the synergistic effects of its larger distortion of oxygen octahedron, larger grain size, and lower oxygen vacancy concentration. Due to its low leakage current density, Ca3Ti2O7 ceramics sintered in oxygen atmosphere exhibit the remanent polarization as high as 7.40 μC/cm2 under the conditions of 1 Hz and 200 kV/cm obtained by dynamic hysteresis measurement mode. Furthermore, there are obvious stripe ferroelectric domains, which provide direct evidence for the excellent hybrid improper ferroelectricity of Ca3Ti2O7 ceramics. These findings demonstrate that the oxygen vacancy engineering is an effective strategy to improve hybrid improper ferroelectricity of Ca3Ti2O7 materials.

Superior hybrid improper ferroelectricity and enhanced ferromagnetism of Ca3(Ti1-xCox)2O7 ceramics through the superexchange interaction

Ca3(Ti1-xCox)2O7 ceramics were prepared by a tartaric acid sol-gel method and sintered in an oxygen atmosphere. The introduction of Co2+/Co3+ as acceptor dopants leads to the formation of more oxygen vacancies and defect dipoles in Ca3(Ti1-xCox)2O7 ceramics. Oxygen vacancy and defect dipoles lead to the transition of dielectric, leakage, and ferroelectric behaviors of Ca3(Ti1-xCox)2O7 ceramics. The coexistence of hybrid improper ferroelectricity and ferromagnetism at room temperature in Ca3(Ti1-xCox)2O7 ceramics has been successfully realized through the superexchange interaction of Co–O–Co. Ca3(Ti1-xCox)2O7 ceramics exhibit superior ferroelectricity (the remnant polarization is 3.29 μC/cm2) and enhanced ferromagnetism (the remnant magnetization reaches 6.4×10−3 emu/g). This strategy based on the introduction of transition metal ions with unfilled 3d shells at B sites is an important approach to realize novel room-temperature single-phase multiferroic materials for Ca3Ti2O7-based materials.

Hybrid Improper Ferroelectricity: A Theoretical, Computational, and Synthetic Perspective

We review the theoretical, computational, and synthetic literature on hybrid improper ferroelectricity in layered perovskite oxides. Different ferroelectric mechanisms are described and compared, and their elucidation using theory and first-principles calculations is discussed. We also highlight the connections between crystal chemistry and the physical mechanisms of ferroelectricity. The experimental literature on hybrid improper ferroelectrics is surveyed, with a particular emphasis on cation-ordered double perovskites, Ruddlesden–Popper and Dion–Jacobson phases. We discuss preparative routes for synthesizing hybrid improper ferroelectrics in all three families and the conditions under which different phases can be stabilized. Finally, we survey some synthetic opportunities for expanding the family of hybrid improper ferroelectrics.

Distortion modes and ferroelectric properties in hybrid improper ferroelectric Sr3(Sn,Zr)2O7 ceramics

In the present work, the distortion modes and ferroelectric properties of Sr3(Sn1−xZrx)2O7 (x = 0.0, 0.25, 0.5, 0.75, 1.0) ceramics with double-layered Ruddlesden–Popper structures were investigated. The amplitudes of three distortion modes for the ferroelectric phase deviated from the aristotype one were quantified using the symmetry-mode approach adopted in Rietveld refinement against x-ray diffraction patterns. The remanent polarization and the coercive field decreased with increasing the content of Zr4+ cations. The decline of polarization should attribute to the nonpolar secondary phase, while the suppression of a coercive field may connect with the decreased amplitude of the rotation mode. The Curie temperatures increased linearly with increasing x value in Sr3(Sn1−xZrx)2O7 ceramics, inducing from the decline of a tolerance factor. A typical first-order improper ferroelectric phase transition was determined using a differential scanning calorimetry measurement and dielectric characterization. From the present work, a straightforward way to quantify the amplitude of a distortion mode for the ferroelectric phase was given, and the ferroelectric properties could be effectively tuned by substituting the cations at the B site in the Sr-based hybrid improper ferroelectrics.

Hybrid improper dipolar density wave in NaLaCoWO6

Hybrid improper ferroelectricity (HIF) allows the generation of an electrical polarization in the AA${}^{\ensuremath{'}}$BB${}^{\ensuremath{'}}{\mathrm{O}}_{6}$ double perovskite materials thanks to the combination of two nonpolar octahedral distortions. Nevertheless, for selected combination of the A/A${}^{\ensuremath{'}}$ cations a nonpolar incommensurate phase is observed with average symmetry $C2/m$. Thanks to a detailed crystallographic description of the incommensurate phase, based on electron, neutron, and x-ray diffraction data, we show that the incommensurate modulation is related to an abrupt change of the out-of-phase tilting along the $a$ and $c$ axis, whereas the tilting along the $b$ axis remains constant across the structure. By using group theory and symmetry analysis we show that we observe an incommensurate analog of HIF, which induces a hybrid improper dipolar density wave in ${\mathrm{NaLaCoWO}}_{6}$. The dipolar ordering is due also in this case to a trilinear invariant involving the commensurate and incommensurate octahedra tilting.

Two-dimensional ferroelectricity induced by octahedral rotation distortion in perovskite oxides

Two-dimensional (2D) ferroelectricity has attracted extensive attention since its discovery in the monolayers of van der Waals materials. Here we show that 2D ferroelectricity induced by octahedral rotation distortion is widely present in the perovskite bilayer system through first-principles calculations. The perovskite tolerance factor plays a crucial role in the lattice dynamics and ground-state structure of the perovskite monolayers and bilayers, thus providing an important indicator for screening this hybrid improper ferroelectricity. Generally, the ferroelectric switching via an orthorhombic twin state has the lowest energy barrier. Epitaxial strain can effectively tune the ferroelectric polarization and ferroelectric switching by changing the amplitude of octahedral rotation and tilt distortion. The increasing compressive strain causes a polar to nonpolar phase transition by suppressing the tilt distortion. The cooperative effect of octahedral distortion at the interface with the substrate can reduce the energy barrier of the reversing rotation mode and can even change the lowest-energy ferroelectric switching path.

Local symmetry breaking and magnetic properties of acceptor-donor codoped Ca3Mn2O7 hybrid improper ferroelectrics

Layered hybrid improper ferroelectrics are very important for multiferroic devices; however, it has been very challenging to obtain multiferroic properties at room temperature. In this study we report that acceptor-donor codoping can be used to realize ferromagnetism in ${\mathrm{Ca}}_{3}{\mathrm{Mn}}_{2}{\mathrm{O}}_{7}$ improper ferroelectric ceramics at room temperature. The transmission electron microscope observation and first-principles calculation revealed that the obtained ferromagnetic properties result from the ${\mathrm{MnO}}_{6}$ octahedron tilt caused by the large lattice distortion near the acceptor-donor pair. At the same time, an obvious magnetoimpedance effect was observed.

Stabilization of layered perovskite structures via strontium substitution in Ca3Ti2O7 revealed via elemental mapping

Extensive studies have been performed on layered compounds, ranging from layered cuprates to van der Waals materials with critical issues of intergrowths and stacking faults. However, such structures have been studied less because of experimental difficulty. We present characteristic defect structures of intergrowths in the Ruddlesden–Popper Ca2.46Sr0.54Ti2O7, which is known to exhibit hybrid improper ferroelectricity. Transmission electron microscopy reveals that numerous intergrowths composed of 7 and 15 layers are introduced in the ferroelectric domains. Elemental maps demonstrate that Sr ions are selectively substituted into the perovskite layers of intergrowths. Density functional theory calculations support the site-selective substitution of Sr ions, favorably located in the intergrowths. The stabilization of the Ruddlesden–Popper phase and intergrowths via Sr substitution can be explained by the ionic-radius difference between Ca and Sr ions. The study reveals detailed defect structures originating from the layered perovskite structure of Ca2.46Sr0.54Ti2O7 and shows the usefulness of elemental mapping in probing the substitution effects in oxides.

Hybrid Improper Ferroelectricity in Highly Cleavable Single Crystals of Dion‐Jacobson‐Compound CsBiNb2O7

AbstractDion‐Jacobson compound CsBiNb2O7 exhibits supposedly hybrid improper ferroelectricity (HIF), resulting from two different structural distortions. The highly‐cleavable single crystal of CsBiNb2O7 has been successfully grown and found large ferroelectric polarization as large as 30 μC cm‐2 with the coercivity of 310 kV cm‐1 from polarization‐electric field measurements on the crystals. Using piezoelectric force microscopy, a systematic study is on the ferroelectric domain structure and dynamics of CsBiNb2O7, unveiling the rich nature of its domain/domain wall evolution upon poling. The record large switchable polarization in CsBiNb2O7 among HIF compounds brings HIF closer to the real Pb‐free ferroelectric applications and the high cleavability of CsBiNb2O7 crystals provides a unique opportunity to explore ultrathin ferroelectrics with in‐plane polarization.