Rotation Of Oxygen Octahedra Research Articles

Strain Programming of Oxygen Octahedral Symmetry in Perovskite Oxide Thin Films

AbstractThe collective rotations of oxygen octahedra play an important role in determining the physical properties of functional perovskite oxides. The epitaxial strain can serve as an effective means to modify the oxygen octahedral symmetry (OOS), i.e., oxygen octahedral rotation or tilt (OOR/OOT). However, the strain‐OOS coupling that may alter the details of the OOS, thereby the physical properties, has not been fully understood. In this work, it is demonstrated that epitaxial strain can not only induce a structural phase transition but also precisely tune the degree of OOR. The correlated metal CaNbO3, which is orthorhombic, is studied by growing as epitaxial thin films. By imposing epitaxial strain, it is found that the film undergoes a structural phase transition from orthorhombic to tetragonal upon fully straining (i.e., from a+b−b− to a0a0c−). In unstrained films, the octahedral rotation along the c‐axis is as large as 15.7° that can be tuned to 6.6° by strain. This finding offers a general approach to manipulating OOR/OOT via strain engineering in complex oxide heterostructures.

Low-frequency dynamics of 0.45PMN-0.55PSN solid solution

Lead magnoniobate-scandoniobate (PMN-PSN) solid solutions are important functional materials for transducer/actuator devices due to their extraordinary dielectric and electromechanical properties. These unique properties are related to the unusual low-frequency relaxation dynamics, which has not been sufficiently understood until now. In our paper the low-frequency relaxation dynamics of 0.45Pb(Mg1/3Nb2/3)O3–0.55Pb(Sc1/2Nb1/2)O3 single crystal is studied in frequency range 10 mHz–1 MHz at temperatures near the dielectric permittivity maximum. Four relaxation processes are identified. Low-frequency mode demonstrating the critical divergence around 306 K is revealed. However, the phase transition into ferroelectric phase at this temperature does not occur. Near 306 K, the appearance of M-type superstructure is found related to the combination of oxygen octahedral rotation and anti-parallel shifts of lead ions. The appearance of the additional order parameter suppresses the slowing down of the ferroelectric mode and the phase transition into the ferroelectric phase occurs only below 295 K. In addition, two relaxation processes, similar to reorientation and “breathing” polar nanoregion (PNR) modes reported for PMN, are found. The sharp softening of “reorientation mode” is observed on cooling from 315 to 295 K with Tf ∼288 K. The fourth relaxation process is the Debye process, and we assume that it is associated with defects relaxation. Below 295 K, all four relaxation processes still exist, but their parameters are practically temperature independent. The low-temperature phase is not exactly a “normal” ferroelectric phase, the PNRs persist in the FE phase.

On the Emergence of Ferromagnetism in LaCoO3 Ultrathin Films

AbstractIt is well known that the properties of a crystal evolve as it increases in size from a single atomic plane to that of the bulk. Such size‐dependent transitions can stem from many different origins and depend on minute changes to crystal bonding and composition. A model example is that of LaCoO3, which is non‐magnetic in the bulk but can display ferromagnetism at the nanoscale. Here, the evolution of structure‐property relationships is studied in the LaCoO3−δ/SrTiO3 (001) system as the thickness of LaCoO3−δ is increased from a single plane to 10 unit cells. In situ synchrotron X‐ray studies are performed during and post‐deposition to probe changes in the interactions between structure, stoichiometry, and magnetic behavior. Structural quantification indicates that the oxygen octahedral rotation pattern evolves with thickness, due to inherent differences in crystal symmetry between the film and substrate. The change in rotation modifies the required energy barrier for the spin state transition via the Co–O bond length and Co–O–Co bond angle, affecting the appearance of ferromagnetism. Our results highlight the contributions of high spin Co2+ and/or high spin Co3+ to respective weak and robust ferromagnetism and the evolution of properties with size in ultrathin LaCoO3−δ heterostructures.

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.

Optical pulse-induced ultrafast antiferrodistortive transition in SrTiO3

The ultrafast dynamics of the antiferrodistortive phase transition in perovskite SrTiO3 is monitored via time-domain Brillouin scattering. Using femtosecond optical pulses, we initiate a thermally driven tetragonal-to-cubic structural transformation and detect the crystal phase through changes in the frequency of Brillouin oscillations (BO) induced by propagating acoustic phonons. Coupling the measured BO frequency with a spatiotemporal heat diffusion model, we demonstrate that, for a sample kept in the tetragonal phase, deposition of sufficient thermal energy induces a rapid transformation of the heat-affected region to the cubic phase. The initial phase change is followed by a slower reverse cubic-to-tetragonal phase transformation occurring on a timescale of hundreds of picoseconds. We attribute this ultrafast phase transformation in the perovskite to a structural resemblance between atomic displacements of the R-point soft optic mode of the cubic phase and the tetragonal phase, both characterized by anti-phase rotation of oxygen octahedra. The structural relaxation time exhibits a strong temperature dependence consistent with the prediction of the equation of motion describing collective oxygen octahedra rotation based on the energy landscape of the phenomenological Landau theory of phase transitions. Evidence of such a fast structural transition in perovskites can open up new avenues in information processing and energy storage sectors.

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.

Ultrafast Optically Induced Perturbation of Oxygen Octahedral Rotations in Multiferroic BiFeO3 Thin Films.

The functional properties of complex oxides, including magnetism and ferroelectricity, are closely linked to subtle structural distortions. Ultrafast optical excitations provide the means to manipulate structural features and ultimately to affect the functional properties of complex oxides with picosecond-scale precision. We report that the lattice expansion of multiferroic BiFeO3 following above-bandgap optical excitation leads to distortion of the oxygen octahedral rotation (OOR) pattern. The continuous coupling between OOR and strain was probed using time-resolved X-ray free-electron laser diffraction with femtosecond time resolution. Density functional theory calculations predict a relationship between the OOR and the elastic strain consistent with the experiment, demonstrating a route to employing this approach in a wider range of systems. Ultrafast control of the functional properties of BiFeO3 thin films is enabled by this approach because the OOR phenomena are related to ferroelectricity, and via the Fe-O-Fe bond angles, the superexchange interaction between Fe atoms.

Emergent ultrasmall multiferroics in paraelectric perovskite oxide by hole polarons.

Ultimately small multiferroics with coupled ferroelectric and ferromagnetic order parameters have drawn considerable attention for their tremendous technological potential. Nevertheless, these ferroic orders inevitably disappear below the critical size of several nanometers in conventional ferroelectrics or multiferroics. Here, based on first-principles calculations, we propose a new strategy to overcome this limitation and create ultrasmall multiferroic elements in otherwise nonferroelectric CaTiO3 by engineering the interplay of oxygen octahedral rotations and hole polarons, though both of them are generally believed to be detrimental to ferroelectricity. It is found that the hole doped in CaTiO3 spontaneously forms a localized polaronic state. The lattice distortions associated with a hole polaron interacting with the intrinsic oxygen octahedral rotations in CaTiO3 effectively break the inversion symmetry and create atomic-scale ferroelectricity beyond the critical size limitation. The hole polaron also causes highly localized magnetism attributed to the associated spin-polarized electric state and thus manifests as a multiferroic polaron. Moreover, the hole polaron exhibits high hopping mobility accompanied by rich switching of polarization and magnetic directions, indicating strong magnetoelectric coupling with a mechanism dissimilar from that of conventional multiferroics. The present work provides a new mechanism to engineer inversion symmetry and opens avenues for designing unusual multifunctional materials.

Local phase structure evolution and ferroelectric response in novel Bi-layered structure relaxor BaBi2Ta2O9 ceramic

It is of importance to discover new type ferroelectric materials with enhanced functionalities to meet various demand of applications, here we prepared the BaBi2Ta2O9 ceramic with orthogonal structure and oxygen octahedral rotation. This type of material had been screened out to be a candidate ferroelectric previously based on high-throughput first-principles density functional theory (DFT) calculations. The relationship between local phase structure and ferroelectric properties of this system is investigated by dielectric spectrum. Low-temperature relaxor behavior is described by using the Curie-Weiss law and the Vogel-Fulcher relationship. The polarization response and size of Polar nanoregions (PNRs) are described using the phenomenological statistical model. The P(E) loops imply that long-range-order ferroelectric is destroyed formation frozen randomly interacting PNRs. Element segregation and lattice distortion are directly observed using TEM, which is associated with the substitution of multiple atoms for the one cation occupation.

Signatures of orbital selective Mott state in doped Sr3Ru2O7

Bilayer Strontium Ruthenate ${\mathrm{Sr}}_{3}{\mathrm{Ru}}_{2}{\mathrm{O}}_{7}$ is a strongly correlated electronic system that shows diverse electronic and structural phases. Upon doping with Mn, an orbital selective Mott phase is observed before the material transitions to a Mott insulating state. Additionally, Mn doping leads to the emergence of an antiferromagnetic state with ${\mathbit{q}}_{\mathbit{AFM}}=(\ensuremath{\pi}/2,\ensuremath{\pi}/2)$ ordering wave vector. Quasiparticle interference (QPI) experiments find a sharp but highly dispersive peak at the AFM wave vector. Another set of QPI peaks is observed at ${\mathbit{q}}^{*}=(\ensuremath{\pi},0),$ possibly due to a charge order effect. In this work we utilize a tight binding model relevant to Mn doped ${\mathrm{Sr}}_{3}{\mathrm{Ru}}_{2}{\mathrm{O}}_{7}$, and show that the origin of observed orbital selective Mott phase is inherently dependent upon the presence of a strong onsite exchange interaction and oxygen octahedral rotation suppression induced by the Mn doping. We further find that the experimentally observed QPI spectra, including the peaks at ${\mathbit{q}}_{\mathbit{AFM}}$, and ${\mathbit{q}}^{*}$ wave vectors can be concomitantly explained within this formalism.

Dimensionality-driven in-plane antiferromagnetism in two-dimensional SrRuO3

Control of dimensionality is a powerful tool to unlock hidden electronic and magnetic phases. In particular, reduced dimensionality in strongly correlated oxides leads to an intriguing ``dead-layer'' behavior that a transition from (ferromagnetic) metal to (antiferromagnetic) insulator occurs as the thickness approaches the two-dimensional limit. However, the origin of such transition has been a subject of debate that both the intrinsic dimensionality effect and the extrinsic disorder effect are proposed to be the driving force. Here, we reveal a transition from ferromagnetic metal with perpendicular magnetic anisotropy to antiferromagnetic insulator with in-plane magnetic anisotropy in ${\mathrm{SrRuO}}_{3}$ epitaxial films down to the monolayer limit. Experimentally, we demonstrate that ${\mathrm{SrRuO}}_{3}$ films below 3 unit cells become magnetic insulators and the spin easy axis changes to the in-plane ⟨110⟩ directions. First-principles calculations reveal that the interplay of the orbital-selective quantum confinement on Ru $4d$ orbitals and the oxygen octahedral rotation drives the ultrathin films from ferromagnetic metal to antiferromagnetic insulator, reorienting Ru spins from the perpendicular to the ⟨110⟩ directions. Our findings demonstrate how reduced dimensionality can tailor the magnetic state and provide significant advances in one of the debated topics in complex oxide heterostructures that dimensionality effect alone can be the driving force of dead-layer phenomenon in two-dimensional systems.

Gradient Strain-Induced Room-Temperature Ferroelectricity in Magnetic Double-Perovskite Superlattices.

Single-phase multiferroics suffer from a fundamental contradiction between polarity and magnetism in d0 electronic configuration, motivating studies of unconventional ferroelectricity in magnetic oxides. However, low critical temperature and polarization still need to be overcome. Here, it is reported that the switchable polarization behavior at room temperature in [(La2 NiMnO6 )/(La2 CoMnO6 )]n double-perovskite magnetic superlattice films is achieved by engineering a microstructure with gradient strains, and the ferromagnetic Curie temperature did not show a rapid decrease. The synergy of gradient strains and superlattice components plays a decisive role in inducing ferroelectricity via the tilting or rotation of various oxygen octahedra. Such distortion responses to gradient strains are accompanied by slight magnetic fluctuations, maximizing the preservation of the initial magnetic exchange interactions, which alleviates the contradiction of multiferroic coexistence to a certain extent. This work confirms the room-temperature ferroelectricity in double-perovskite superlattices and provides a preferred strategy for confronting the difficulty of multiferroic coexistence in single-phase materials.

Controlled properties of perovskite oxide films by engineering oxygen octahedral rotation

Complex perovskite oxides exhibit extremely rich physical properties in terms of magnetism, electrical transport, and electrical polarization characteristics due to the competition and coupling of many degrees of freedom. The B-site ions and O ions in perovskite form six-coordinated octahedral units, which are connected at a common vertex toward the basic framework of the perovskite oxide, providing a crucial platform to tailor physical properties. The rotation or distortion of the oxygen octahedra will tip the competing balance, leading to many emergent ground states. To further clarify the subtle relationship between emergent properties and oxide octahedral behavior, this article reviews the structure of perovskite oxides, the characterization methods of oxygen octahedral rotation and the response of transport, electrical polarization and magnetism of several typical perovskite heterostructures to oxygen octahedral rotation modes. With knowledge of how to manipulate the octahedral rotation behavior and regulate the physical properties of perovskite oxides, rationally designing the sample manufacturing process can effectively guide the development and application of novel electronic functional materials and devices.

Interfacial Oxygen Octahedral Coupling-Driven Robust Ferroelectricity in Epitaxial Na0.5Bi0.5TiO3 Thin Films.

The oxygen octahedral rotation (OOR) forms fundamental atomic distortions and symmetries in perovskite oxides and definitely determines their properties and functionalities. Therefore, epitaxial strain and interfacial structural coupling engineering have been developed to modulate the OOR patterns and explore novel properties, but it is difficult to distinguish the 2 mechanisms. Here, different symmetries are induced in Na0.5Bi0.5TiO3 (NBT) epitaxial films by interfacial oxygen octahedral coupling rather than epitaxial strain. The NBT film grown on the Nb:SrTiO3 substrate exhibits a paraelectric tetragonal phase, while with La0.5Sr0.5MnO3 as a buffer layer, a monoclinic phase and robust ferroelectricity are obtained, with a remanent polarization of 42 μC cm-2 and a breakdown strength of 7.89 MV cm-1, which are the highest record among NBT-based films. Moreover, the interfacial oxygen octahedral coupling effect is demonstrated to propagate to the entire thickness of the film, suggesting an intriguing long-range effect. This work provides a deep insight into understanding the structure modulation in perovskite heterostructures and an important avenue for achieving unique functionalities.

Evolution of electronic band reconstruction in thickness-controlled perovskite SrRuO$$_3$$ thin films

Transition metal perovskite oxides display a variety of emergent phenomena which are tunable by tailoring the oxygen octahedral rotation. SrRuO$_3$, a ferromagnetic perovskite oxide, is well-known to have various atomic structures and octahedral rotations when grown as thin films. However, how the electronic structure changes with the film thickness has been hardly studied. Here, by using angle-resolved photoemission spectroscopy and electron diffraction techniques, we study the electronic structure of SrRuO$_3$ thin films as a function of the film thickness. Different reconstructed electronic structures and spectral weights are observed for films with various thicknesses. We suggest that octahedral rotations on the surface can be qualitatively estimated via comparison of intensities of different bands. Our observation and methodology shed light on how structural variation and transition may be understood in terms of photoemission spectroscopy data.

Strain tuning of Néel temperature in YCrO3 epitaxial thin films

Epitaxial strain is a useful handle to engineer the physical properties of perovskite oxide materials. Here, we apply it to orthorhombic chromites that are a family of antiferromagnets showing fruitful functionalities as well as strong spin–lattice coupling via antisymmetric exchange interaction along Cr–O–Cr bonds. Using pulsed laser deposition, we grow YCrO3 thin films on various substrates imposing strain levels in the range from −1.8% to +0.3%. The films are stoichiometric with a 3+ valence for Cr both within the films and at their surface. They display an antiferromagnetic spin order below their Néel temperature, which we show can be strongly tuned by epitaxial strain with a slope of −8.54 K/%. A dimensionless figure of merit (defined as the slope normalized by the Néel temperature of bulk) is determined to be 6.1, which is larger than that of other perovskites, such as manganites (5.5), ferrites (2.3), or nickelates (4.6). Density functional theory simulations bring insight into the role of Cr–O bond lengths and oxygen octahedral rotations on the observed behavior. Our results shed light on orthorhombic chromites that may offer an energy-efficient piezo-spintronic operation.

Interplay between Oxygen Octahedral Rotation and Deformation in the Acentric ARTiO4 Series toward Negative Thermal Expansion

Interplay between Oxygen Octahedral Rotation and Deformation in the Acentric <i>AR</i>TiO₄ Series toward Negative Thermal Expansion

Phase transitions and ferroelectricity of perovskite layered Sr2Nb2O7 ceramics

Spontaneous polarization (Ps) is the fundamental for ferroelectrics. Compared with the relative explicit origin of Ps of perovskite ferroelectrics and bismuth layer structured ferroelectrics, that of the perovskite layer structured ferroelectrics (PLSFs) is still unclear and controversial due to their unique layer structures. Sr2Nb2O7 compound with a high Curie temperature of 1342 °C is a typical representative in the family of PLSFs. Here, we report our investigations about the phase transitions and the mechanism of ferroelectricity of Sr2Nb2O7 ceramics from the viewpoint of layered crystal structure experimentally and theoretically. Sr2Nb2O7 has two phase transitions at about 215 °C and 1340 °C. Selected area electron diffraction (SAED) images show superlattice along the [001] zone axis related to an incommensurate modulation and confirm it's incommensurate-commensurate phase transition at around 215 °C. The latter on at 1340 °C corresponds to the paraelectric-ferroelectric phase transition which is originated from oxygen octahedral rotation along c-axis, named a0b0c+ in Glazer's notation. Phonon spectra shows the origin of Ps for Sr2Nb2O7 is from mainly the oxygen octahedral rotations and partially the displacement of Sr2+ ions. This study not only demonstrates the rotation of oxygen octahedron is the domination that affects ferroelectric polarization but also opens up a new direction to design high ferroelectric and piezoelectric PLSF ceramics.

Enhanced strain of (Ba, Ca)(Ti, Zr, Sn)O3 ferroelectrics with multiphase polar nanoregions coexistence and BO6 octahedral rotation

The cation displacement closely related to the local symmetry and corner-connected oxygen octahedral rotation are the structural origin of macroscopic properties in ABO3 perovskite oxides. This work describes in detail the relationship between microstructure and macroscopic properties in 0.78BT-0.12CT-0.1BZS ceramic, which achieves the enhanced strain of 0.19 % with a hysteresis of 6.56 %. The atomic level structure is revealed by aberration corrected scanning transmission electron microscope (AC-STEM). The AC-STEM HAADF images reveal the coexisting of polar nanoregions with O and T symmetries. Such a microstructure has a lower energy barrier, facilitating dynamic polarization rotation flexibly under external stimuli. The AC-STEM ABF image reveals the existence of the BO6 octahedral rotation, with rotation patterns of the a0b0c0 and a-b+c-, and rotation angles are quantitatively measured. The BO6 octahedral rotation and cation displacement are found to be consistent, the greater octahedral rotation with greater cation displacements. These results have important implications for understanding the structural origin of the excellent properties in ferroelectrics.

Dynamic control of octahedral rotation in perovskites by defect engineering

Engineering oxygen octahedra rotation patterns in $ABO_3$ perovskites is a powerful route to design functional materials. Here we propose a strategy that exploits point defects that create local electric dipoles and couple to the oxygen sublattice, enabling direct actuation on the rotational degrees of freedom. This approach, which relies on substituting an $A$ site with a smaller ion, paves a way to couple dynamically octahedra rotations to external electric fields. A common antisite defect, $\mathrm{Al_{La}}$ in rhombohedral LaAlO$_3$ is taken as a prototype to validate the idea, with atomistic density functional theory calculations supported with an effective lattice model to simulate the dynamics of switching of the local rotational degrees of freedom to long distances. Our simulations provide an insight of the main parameters that govern the operation of the proposed mechanism, and allow to define guidelines for screening other systems where this approach could be used for tuning the properties of the host material.