Octahedral Rotations Research Articles

Thermally Controlled A-site Cation Ordering and Coupled Polarity in Double Perovskite NaLaZr2O6.

A-site cation ordering in double perovskites is crucially important for their physical properties. In this study, polycrystalline samples of Zr-based double perovskite NaLaZr2O6 were synthesized via high-temperature solid-state reactions, and the influence of the heating temperature and cooling rate on their crystal structures was investigated using synchrotron X-ray diffractometry and optical second harmonic generation. The samples prepared at 1200 °C, followed by slow cooling to room temperature, crystallize in a polar P21am structure, exhibiting partial A-site cation ordering, with Na- and La-rich A-site layers alternately stacked along the c axis. Remarkably, this structure transforms to a previously reported nonpolar Pnam phase with a disordered A-site cation arrangement when the slow-cooled samples are reheated at 1300 °C or higher and then rapidly quenched to room temperature. Theoretical analyses reveal that in the P21am phase, the a-a-c+ octahedral rotations trigger antiparallel displacements of the A-site cations in the Na- and La-rich A-site layers to induce spontaneous polarization. This is in contrast to the case of the Pnam phase, in which the rotation-induced antiparallel displacements of the equivalent A-site cations are antipolar. This work represents a rare example of AA'B2O6 perovskites exhibiting layered A-site ordering and polarity and also demonstrates a novel mechanism for reversible thermal switching from polar to nonpolar states in perovskites.

Structure-Tailored Superlattice Bi7Ti4NbO21: Coupling Octahedral Tilting and Rotation Induced High Ferroelectric Polarization for Efficient Piezo-photocatalytic CO2 Reduction

Structure-Tailored Superlattice Bi7Ti4NbO21: Coupling Octahedral Tilting and Rotation Induced High Ferroelectric Polarization for Efficient Piezo-photocatalytic CO2 Reduction

Structural frustration effects by mixed alkali ions in ferroelectric Dion–Jacobson layered perovskites (Cs,Rb)NdNb2O7

Dion–Jacobson phases CsNdNb2O7 and RbNdNb2O7 adopt two types of polar structures with different octahedral tilts. In their solid solutions, the competition between the two phases causes structural frustration effects on ferroelectric transitions.

Suppression of Ferroelectric Transitions by Symmetry Trapping in Dion-Jacobson-Layered Perovskites Cs(La,Nd)Nb2O7.

CsNdNb2O7 is a hybrid improper ferroelectric (HIF) where oxygen octahedral rotation modes induce spontaneous polarization. While CsLaNb2O7 is also believed to be an HIF, its polar structure and ferroelectric properties remain poorly understood. This study investigates their solid solution, CsLa1-xNdxNb2O7, by constructing a temperature-composition phase diagram using synchrotron X-ray diffractometry, first-principles calculations, and dielectric measurements. Upon cooling, the Nd-rich compositions (x = 0.5, 0.75, and 1) undergo phase transitions from a P4/mmm to a C2/m and then to a polar P21am phase. Both transition temperatures decrease as x decreases. The polar P21am phase, accompanied by ferroelectric polarization switching, is stabilized at room temperature only when x = 0.75 and 1. For La-rich compositions, the nonpolar C2/m phase remains down to room temperature without exhibiting any indication of transformation into the polar P21am phase. Theoretical calculations suggest that a symmetry trapping effect hinders the nonpolar (C2/m)-to-polar (P21am) phase transition.

Strain-Induced Antiferroelectric-Ferroelectric-Antiferroelectric Phase Transitions in Epitaxial LaTaO4 Films.

We employed first-principles to delve into the strain-induced structural phase transitions in epitaxial LaTaO4 films. The ground state of bulk LaTaO4 adopts a monoclinic antiferroelectric phase, characterized by the antiphase rotation of two adjacent oxygen octahedra layers. Under epitaxial tensile strain, LaTaO4 thin films undergo a consecutive phase transition, namely, antiferroelectric-ferroelectric-antiferroelectric phase transitions. The ferroelectricity in the orthorhombic phase under tensile strain originates from the in-phase rotation of two adjacent oxygen octahedra layers, in contrast to the case of perovskite systems, in which octahedra rotation suppresses the conventional proper ferroelectricity. With spin-orbit coupling effects, a pronounced Rashba effect at the Brillouin zone center naturally leads to the formation of opposite directions of spin texture. Moreover, the tensile strain also synergistically enhances the corresponding Rashba parameters. Our findings may provide novel insights for controlling oxygen octahedra rotation to achieve control over the ferroelectricity and Rashba effect, which holds promising implications for applications in electronics and spintronics.

Continuously tunable negative pressure for engineering high-symmetry nanocrystalline phases

In this work, the phenomenon of strain induced by a mismatch in thermal expansion coefficients between a thin film and its substrate is harnessed in a new context, replacing the canonical planar support with a three-dimensional (3-D), nanoconfining scaffold in which we embed a material of interest. In this manner, we demonstrate a general approach to exert a continuously tunable, triaxial, tensile strain, defying the Poisson ratio of the embedded material and achieving the exotic condition of "negative pressure." This approach is hypothetically generalizable to materials of low modulus and high thermal expansion coefficient, and we use it here to achieve negative pressure in perovskite-phase CsPbI3 embedded within the cylindrical pores of anodic aluminum oxide membranes. Through controlled thermal hysteresis, the perovskite crystal structure can be continuously tuned toward higher symmetry when confined in a scaffold with pore size <40 nm, in contrast with the symmetry-reducing action of any other mechanical perturbation. We use this effect to control the octahedral rotation angle that is critical to the remarkable photovoltaic attributes of halide perovskites. Under hundreds of megapascals of apparent negative pressure, the bandgap tunability is observed to follow the same quantitative trend observed for hydrostatic positive pressure, exploring the negative pressure region and demonstrating the relative dominance of bond stretching effects over average octahedral rotation angle on electronic structure. This study reveals and quantifies the structural and electronic consequences of 3D tensile strain present by design and provides a framework for understanding adventitious strain present in all nanocomposite materials.

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.

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.

Imprinted atomic displacements drive spin–orbital order in a vanadate perovskite

AbstractPerovskites with the generic composition ABO3 exhibit an enormous variety of quantum states, such as orbital order, magnetism and superconductivity. Their flexible and comparatively simple structure allows for straightforward chemical substitution and cube-on-cube combination of different compounds in atomically sharp epitaxial heterostructures. Many of the diverse physical properties of perovskites are determined by small deviations from the ideal cubic perovskite structure, which are challenging to control. Here we show that directional imprinting of atomic displacements in the antiferromagnetic Mott insulator YVO3 can be achieved by depositing epitaxial films on different facets of the same isostructural substrate. These facets were chosen such that other well-known control parameters, including lattice and polarity mismatch with the overlayer, remain nearly unchanged. We observe signatures of staggered orbital and magnetic order and demonstrate distinct spin–orbital ordering patterns on different facets. We attribute these results to the influence of specific octahedral rotation and cation displacement patterns, which are imprinted by the substrate facet, on the covalency of the bonds and the superexchange interactions in YVO3. Our results show that substrate-induced templating of lattice distortion patterns constitutes a pathway for materials design beyond established strain-engineering strategies.

Magic angle of Sr2RuO4 : Optimizing correlation-driven superconductivity

Understanding of unconventional superconductivity is crucial for engineering materials with specific order parameters or elevated superconducting transition temperatures. However, for many materials, the pairing mechanism and symmetry of the order parameter remain unclear: reliable and efficient methods of predicting the order parameter and its response to tuning parameters are lacking. Here, we investigate the response of superconductivity in Sr2RuO4 to structural distortions via the random phase approximation (RPA) and functional renormalization group (FRG), starting from realistic models of the electronic structure. Our results suggest that RPA misses the interplay of competing fluctuation channels. FRG reproduces key experimental findings. We predict a magic octahedral rotation angle, maximizing the superconducting Tc and a dominant dx2−y2 pairing symmetry. To enable experimental verification, we provide calculations of the phase-referenced Bogoliubov Quasiparticle Interference imaging. Our work demonstrates a designer approach to tuning unconventional superconductivity with relevance and applicability for a wide range of quantum materials. Published by the American Physical Society 2024

The 4-Octahedra model

This work comprises a generalization of a simple geometric model originally developed to describe coupled rotations of corner-sharing octahedra in the surface layer of Sr2RuO4 under uniaxial compression. The main objective of the model is to establish a link between the experimental global strain configuration and the possible microscopic mechanisms and compatible geometries by which the octahedra accommodate the applied strain. In achieving this, a useful and intuitive parametrization of four-site two-dimensional systems of corner-sharing octahedra has been established, which can be readily extended to three dimensions and N&gt;4 inequivalent sites or directly employed to analyze the octahedral configuration of many perovskites, transition metal oxides (TMOs), and layered compounds.

Why scanning tunneling spectroscopy of Sr2RuO4 sometimes doesn’t see the superconducting gap

Scanning tunneling spectroscopy (STS) and scanning tunneling microscopy (STM) are perhaps the most promising ways to detect the superconducting gap size and structure in the canonical unconventional superconductor Sr2RuO4 directly. However, in many cases, researchers have reported being unable to detect the gap at all in STM conductance measurements. Recently, an investigation of this issue on various local topographic structures on a Sr-terminated surface found that superconducting spectra appeared only in the region of small nanoscale canyons, corresponding to the removal of one RuO surface layer. Here, we analyze the electronic structure of various possible surface structures using first principles methods, and argue that bulk conditions favorable for superconductivity can be achieved when removal of the RuO layer suppresses the RuO4 octahedral rotation locally. We further propose alternative terminations to the most frequently reported Sr termination where superconductivity surfaces should be observed.

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.

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.

Orthorhombic Polar Phase in Sodium Niobate Nanoribbons.

Ferroelectric materials exhibit switchable spontaneous polarization below Curie's temperature, driven by octahedral distortions and rotations, as well as ionic displacements. The ability to manipulate polarization coupled with persistent remanence, drives diverse applications, including piezoelectric devices. In the last two decades, nanoscale exploration has unveiled unique material properties influenced by morphology, including the capability to manipulate polarization, patterns, and domains. This paper focuses on the characterization of nanometric sodium niobate (SN) synthesized from metallic niobium through alkali hydrothermal treatment, utilizing electron microscopy techniques, including high-resolution differential phase contrast (DPC) in scanning transmission electron microscopy (STEM). The material exhibits a nanoribbon structure forming a tree root-like network. The study identifies crystallographic phase, atomic columns displacement directions, and surface features, such as exposed planes and the absence of particular atomic columns. The high sensitivity of integrated DPC images proves crucial in overcoming observational challenges in other STEM modes. These observations are essential for potential applications in electronic, photocatalytic, and chemical reaction contexts.

Role of Covalency on the Metal‐Insulator Behavior of BaPbO3${\rm BaPbO}_3$ and Ba2PbO4${\rm Ba}_2{\rm PbO}_4$

Abstract (BPO) and (B2PO) are two sister compounds with identical valence configuration. However, BPO is reported to be metallic, B2PO is known to be gapped. The metallic nature of BPO itself is debated in the literature. A previous combinatorial experimental and theoretical study had claimed octahedral rotations as the reason for metallicity. On the contrary, a recent theoretical study has attributed the octahedral distortions for the gapped behavior. Motivated by these conflicting conclusions, the electronic structure of these two compounds is probed within the framework of density functional theory. It is shown that B2PO has a larger semi conducting gap of 1.4 eV compared to BPO, eventhough there are no octahedral distortions. Using maximally localized Wannier function (MLWF) calculations, it is divulged that the reduction of Pb‐O covalency is the key to opening of bandgap in these systems. It is shown that the cubic phase of BPO is metallic and that the covalency is reduced by the octahedral rotations in non‐cubic phases leading to the opening of pseudo‐gap. Whereas in B2PO the confinement of covalency to 2D layers leads to a semi‐conducting behavior.

Phonon dispersion of quantum paraelectric SrTiO3 in electric fields

Here we report on an elastic and inelastic neutron scattering study addressing the effect of electric fields on quantum paraelectric SrTiO3. Our elastic scattering results find small changes as a function of field in a superlattice reflection that sample the octahedral rotations, which is indicative of only weak coupling of octahedral rotation and electric polarization. Using inelastic neutron scattering, we measured the dispersion of the transverse acoustic and transverse optic phonon in SrTiO3 as a function of applied electric fields. By collecting not only the change in gap, but also of the dispersion, we can better quantify the changes in the lattice dynamics. The findings are put in context to recent DFT calculations predicting the E-field effect on the atomic motions of the lowest lying transverse optical (soft) mode. We find hints of nonlinear coupling to the acoustic mode and to the phonon with polarization perpendicular to the E field, which shows the nonlinearity in the chemical potential that is also relevant when SrTiO3 is excited by strong E-field (THz) pulses. Published by the American Physical Society 2024

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.

Chemical pressure induced spin reorientation in the magnetic structure of Ca3Mn2−xSnxO7 ( x=0,0.03,0.05 )

The effect of partially substituting Tin (Sn) at the Manganese (Mn) site of Ca3Mn2O7 , viz. Ca3Mn2−xSnxO7 with x=0.03,0.05 , on its structural and magnetic properties have been investigated using synchrotron diffraction, neutron diffraction, and bulk magnetization measurements. It is observed that with a substitution of x=0.03 , the minor (≈8%) tetragonal ( I4/mmm ) structural phase that is present in the predominantly orthorhombic ( Cmc21 ) undoped Ca3Mn2O7 , completely disappears. The compounds order antiferromagnetically, the ordering temperature decreases with increasing Sn-content, indicating a weakening of the antiferromagnetic exchange interactions. Interestingly, in the ordered state, the spin magnetic moments which were aligned along the a-axis of the unit cell in the undoped compound, are observed to have reoriented with their major components lying in the b − c plane in the Sn-doped compounds. The above influence of Sn-doping is seen to be stemming from a significant modification of the octahedral rotation and tilt mode geometry in the unit cell, that is known to be responsible for driving ferroelectricity in these compounds.

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.