Hybrid Improper Ferroelectricity Research Articles

Imaging Ferroelastic Domain Walls in Hybrid Improper Ferroelectric Sr3Sn2O7.

We combined synchrotron-based near field infrared spectroscopy and atomic force microscopy to image the properties of ferroelastic domain walls in Sr3Sn2O7. Although frequency shifts at the walls are near the limit of our sensitivity, we can confirm semiconducting rather than metallic character and widths between 20 and 60 nm. The latter is significantly narrower than in other hybrid improper ferroelectrics like Ca3Ti2O7. We attribute this trend to the softer lattice in Sr3Sn2O7, which may enable the octahedral tilt and rotation order parameters to evolve more quickly across the wall without significantly increased strain. These findings are crucial for the understanding of phononic properties at interfaces and the development of domain wall-based devices.

Robust resistance switching performance in a Ca3Ti2O7/La0.67Sr0.33MnO3 heterostructure induced by the interface

Ruddlesden–Popper phase oxides, such as Ca3Ti2O7, have been established as hybrid improper ferroelectrics. However, investigations into Ca3Ti2O7 have primarily concentrated on their structural and ferroelectric properties. In this study, we prepared epitaxial Ca3Ti2O7 thin films via magnetron sputtering. Conducting atomic force microscopy was employed to characterize local current variations under an applied bias voltage. Electron paramagnetic resonance measurements of the Ca3Ti2O7/La0.67Sr0.33MnO3 film were conducted to assess its defect characteristics. Interestingly, the Ca3Ti2O7/La0.67Sr0.33MnO3 stacks exhibited remarkable macroscopic resistance switching, with a resistance on/off ratio reaching 100, alongside robust retention (∼2500 s) and endurance (∼2000 cycles) features. Additionally, density functional theory calculations suggest that the resistance switching is attributable to the interface barrier of the Ca3Ti2O7/La0.67Sr0.33MnO3 interface and the efficacy of space charge limitation. This work proposes an avenue for the utilization of Ruddlesden–Popper phase Ca3Ti2O7 in various applications.

Atomic Layer Engineering of Ferroelectricity in Dion-Jacobson Perovskites.

Recent advances in "hybrid-improper" ferroelectricity in Dion-Jacobson (DJ)-type layered perovskites have caused renewed interest in the search for new ferroelectrics. Here, we present an approach for the tailored synthesis of a new homologous series of DJ-type layered perovskites Cs(Bi2Srn-3)(Tin-1Nb)O3n+1. Starting from CsBi2Ti2NbO10 (n = 3), higher-order homologous phases with n = 4 and 5 were successfully synthesized by repeated solid-state calcination with SrTiO3. Characterizations by X-ray diffraction, electron diffraction, transmission electron microscopy, Raman scattering, and second harmonic generation showed the detailed structural features in Cs(Bi2Srn-3)(Tin-1Nb)O3n+1, and the polar structures could be stabilized by proper or hybrid-improper ferroelectricity, depending on the odd or even number of the perovskite layers. Our results provide important insights into the competition between the different mechanisms and the consequences of the ferroelectric properties in homologous layered perovskites.

Effects of doping with magnetic cations on the hybrid improper ferroelectricity in Sr3Sn2O7

We here report the structural, magnetic and electrical properties of Sr2.9La0.1Sn1.9M0.1O7 (M= Cr, Mn or Fe) compounds. This La/M codoping of the hybrid improper ferroelectric Sr3Sn2O7, allows introducing magnetic cations into the perovskite layers of this Ruddlesden-Popper phase. The doping induces minor structural changes, preserving the polar structure with space group A21am of the undoped compound. The perovskite tolerance factor of all doped samples is slightly lower than in Sr3Sn2O7, which preserves the tilts and rotations of SnO6 octahedra. Doped samples exhibit a paramagnetic behavior down to 5 K and obey the Curie-Weiss law above 200 K. The effective paramagnetic moments agree with the expected spin-only values of the respective magnetic M3+ cations. All samples show a ferroelectric hysteresis loop at room temperature, but the doped samples show larger coercive fields. Additionally, the doping with magnetic cations has important effects on the dielectric properties: a strong decrease of the temperature of the ferroelectric transition together with a smoothing of the anomaly in the dielectric permittivity. These results suggest that the disorder produced by the two aliovalent substitutions is detrimental for the ferroelectric properties due to point charge defects but, at the same time, the prevalence of the structural distortion (tilts and rotations) preserves the ferroelectricity in the investigated doping regime.

Hybrid improper ferroelectricity in La2Sr (Sc1−xFex)2O7 ceramics with double-layered Ruddlesden–Popper structures

Numerous hybrid improper ferroelectrics have been discovered in bulk oxides with layered perovskite structures. In contrast, the competition between the interlayer rumpling and oxygen octahedral rotation suppresses the ferroelectricity in layered perovskite material with trivalent cation at the B-site. In the present work, single-phase dense La2Sr(Sc1−xFex)2O7 ceramics with double-layered Ruddlesden–Popper structures have been prepared, and room-temperature ferroelectricity is discovered in the ceramics with x ≤ 0.10. The ferroelectric polarization and coercive field decrease with increasing content of Fe3+ cations, consistent with the decline of oxygen octahedral rotation and tilting angles. Although the linear relationship between the Curie temperature and the tolerance factor for La2Sr(Sc1−xFex)2O7 ceramics is established, the line is far away from that for A2+3B4+2O7 ceramics due to the large interlayer rumpling in the present ceramics. Although no single-phase multiferroic has been discovered in this work, an effective way to introduce magnetism into hybrid improper ferroelectric is provided.

Experimental demonstration of tunable hybrid improper ferroelectricity in double-perovskite superlattice films

Hybrid improper ferroelectricity can effectively avoid the intrinsic chemical incompatibility of electronic mechanism for multiferroics. Perovskite superlattices, as theoretically proposed hybrid improper ferroelectrics with simple structure and high technological compatibility, are conducive to device integration and miniaturization, but the experimental realization remains elusive. Here, we report a strain-driven oxygen octahedral distortion strategy for hybrid improper ferroelectricity in La2NiMnO6/La2CoMnO6 double-perovskite superlattices. The epitaxial growth mode with mixed crystalline orientations maintains a large strain transfer distance more than 90 nm in the superlattice films with lattice mismatch less than 1%. Such epitaxial strain permits sustainable long-range modulation of oxygen octahedral rotation and tilting, thereby inducing and regulating hybrid improper ferroelectricity. A robust room-temperature ferroelectricity with remnant polarization of ~ 0.16 μC cm−2 and piezoelectric coefficient of 2.0 pm V−1 is obtained, and the density functional theory calculations and Landau-Ginsburg-Devonshire theory reveal the constitutive correlations between ferroelectricity, octahedral distortions, and strain. This work addresses the gap in experimental studies of hybrid improper ferroelectricity for perovskite superlattices and provides a promising research platform and idea for designing and exploring hybrid improper ferroelectricity.

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.

Pressure-dependent phase transitions in hybrid improper ferroelectric Ruddlesden-Popper oxides

The temperature-dependent phase transitions in Ruddlesden-Popper oxides with perovskite bilayers have been under increased scrutiny in recent years due to the so-called hybrid improper ferroelectricity that some chemical compositions exhibit. However, little is currently understood about the hydrostatic pressure dependence of these phase transitions. Herein we present the results of a combined high-pressure powder synchrotron x-ray diffraction experiment and abinitio study on the bilayered Ruddlesden-Popper phases Ca3Mn2O7 and Ca3Ti2O7. In both compounds we observe a first-order phase transition, that in combination with our density functional theory calculations, we can confidently assign as being between polar A21am and nonpolar Acaa structures. Interestingly, we show that while the application of pressure ultimately favors a nonpolar phase, as is commonly observed for proper ferroelectrics, regions of response exist where pressure actually acts to increase the polar mode amplitudes. The reason for this can be untangled by considering the varied response of octahedral tilts and rotations to hydrostatic pressure and their trilinear coupling with the polar instability. Published by the American Physical Society 2024

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.

Physical mechanism of Ge doping enhanced Ruddlesden-Popper structure quasi-2D Sr<sub>3</sub>Sn<sub>2</sub>O<sub>7</sub> ceramic hybrid improper ferroelectricity

Hybrid improper ferroelectricity with quasi-two-dimensional (quasi-2D) structure has attracted much attention recently due to its great potential in realizing strong magnetoelectric coupling and room-temperature multiferroicity in a single phase. However, recent studies show that there appears high coercive field and low remnant polarization in ceramics, which severely hinders the applications of this material. In this work, high-quality Sr<sub>3</sub>Sn<sub>2</sub>O<sub>7</sub> and Sr<sub>3</sub>Sn<sub>1.99</sub>Ge<sub>0.01</sub>O<sub>7</sub> ceramics with a Ruddlesden-Popper (R-P) structure are successfully prepared, and their crystal structures and electrical properties are investigated in detail. It is found that the Sr<sub>3</sub>Sn<sub>2</sub>O<sub>7</sub> ceramic exhibits a lower coercive field that is close to that of Sr<sub>3</sub>Sn<sub>2</sub>O<sub>7</sub> single crystal. Moreover, via a small amount of Ge doping, the polarization reaches 0.34 μC/cm<sup>2</sup> for Sr<sub>3</sub>Sn<sub>2</sub>O<sub>7</sub> and 0.61 μC/cm<sup>2</sup> for Sr<sub>3</sub>Sn<sub>1.99</sub>Ge<sub>0.01</sub>O<sub>7</sub>. Combining crystal lattice dynamic studies, we analyze the Raman and infrared responses of the samples, showing the information about the tilting and rotation of the oxygen octahedra in the samples. The improved ferroelectricity after doping may be attributed to the increased amplitude of the tilt mode and the reduced amplitude of rotation mode. Besides, the enhanced ferroelectric properties through Ge doping and its mechanism are further investigated by the Berry phase approach and the Born effective charge method. Furthermore, via the UV-visible spectra, the optical bandgap is determined to be 3.91 eV for Sr<sub>3</sub>Sn<sub>2</sub>O<sub>7</sub> ceramic and 3.95 eV for Sr<sub>3</sub>Sn<sub>1.99</sub>Ge<sub>0.01</sub>O<sub>7</sub> ceramic. Using the Becke-Johnson potential combined with the local density approximation correlation, the bandgap is calculated and is found to be in close agreement with the experimental result. And the electronic excitations can be assigned to the charge transfer excitation from O 2p to Sn 5s (Ge 4s). The effects of Ge doping on the ability of Sr<sub>3</sub>Sn<sub>2</sub>O<sub>7</sub> to gain and lose electrons and the bonding strength of Sn-O bond are analyzed via two-dimensional charge density difference. In conclusion, this study provides insights into the synthesis method and modulation of ferroelectric properties of hybrid improper ferroelectrics Sr<sub>3</sub>Sn<sub>2</sub>O<sub>7</sub>, potentially facilitating their widespread applications in various capacitors and non-volatile memory devices.

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.