Perovskite Oxide Superlattices Research Articles

Correlated Quantum Phenomena of Spin–Orbit Coupled Perovskite Oxide Heterostructures: Cases of SrRuO3 and SrIrO3 Based Artificial Superlattices

AbstractUnexpected, yet useful functionalities emerge when two or more materials merge coherently. Artificial oxide superlattices realize atomic and crystal structures that are not available in nature, thus providing controllable correlated quantum phenomena. This review focuses on 4d and 5d perovskite oxide superlattices, in which the spin–orbit coupling plays a significant role compared with conventional 3d oxide superlattices. Modulations in crystal structures with octahedral distortion, phonon engineering, electronic structures, spin orderings, and dimensionality control are discussed for 4d oxide superlattices. Atomic and magnetic structures, Jeff = 1/2 pseudospin and charge fluctuations, and the integration of topology and correlation are discussed for 5d oxide superlattices. This review provides insights into how correlated quantum phenomena arise from the deliberate design of superlattice structures that give birth to novel functionalities.

Atomic and electronic structures of correlated SrRuO3/SrTiO3 superlattices

Atomic-scale precision epitaxy of perovskite oxide superlattices provides unique opportunities for controlling the correlated electronic structures, activating effective control knobs for intriguing functionalities including electromagnetic, thermoelectric, and electrocatalytic behaviors. In this study, we investigated the close interplay between the atomic and electronic structures of correlated superlattices synthesized by atomic-scale precision epitaxy. In particular, we employ superlattices composed of correlated magnetic SrRuO3 (SRO) and quantum paraelectric SrTiO3 (STO) layers. In those superlattices, RuO6 octahedral distortion is systematically controlled from 167 to 175 degrees depending on the thickness of the STO layers, also affecting the TiO6 octahedral distortion within the STO layer. Customized octahedral distortion within SRO/STO superlattices in turn modifies the electronic structures of both the Ti and Ru compounds, observed by X-ray absorption spectroscopy. Our results identify the close correlation between atomic lattice and electronic structures enabled by the facile controllability of atomic-scale epitaxy, which would be useful for designing future correlated oxide devices.

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.

Atomic‐Scale Control of Electronic Structure and Ferromagnetic Insulating State in Perovskite Oxide Superlattices by Long‐Range Tuning of BO6 Octahedra

AbstractControl of BO6 octahedral rotations at the heterointerfaces of dissimilar ABO3 perovskites has emerged as a powerful route for engineering novel physical properties. However, its impact length scale is constrained at 2–6 unit cells close to the interface and the octahedral rotations relax quickly into bulk tilt angles away from interface. Here, a long‐range (up to 12 unit cells) suppression of MnO6 octahedral rotations in La0.9Ba0.1MnO3 through the formation of superlattices with SrTiO3 can be achieved. The suppressed MnO6 octahedral rotations strongly modify the magnetic and electronic properties of La0.9Ba0.1MnO3 and hence create a new ferromagnetic insulating state with enhanced Curie temperature of 235 K. The emergent properties in La0.9Ba0.1MnO3 arise from a preferential occupation of the out‐of‐plane Mn d3z2−r2 orbital and a reduced Mn eg bandwidth, induced by the suppressed octahedral rotations. The realization of long‐range tuning of BO6 octahedra via superlattices can be applicable to other strongly correlated perovskites for exploring new emergent quantum phenomena.

Evidence for Interfacial Octahedral Coupling as a Route to Enhance Magnetoresistance in Perovskite Oxide Superlattices

AbstractEngineering octahedral rotations in oxide heterostructures is a promising route for controlling magnetic properties in perovskites, with recent work focusing on magnetic‐ordering temperatures and magnetic anisotropies. Here the effects of interfacial octahedral coupling on magnetoresistance are demonstrated in a series of (La0.7Sr0.3MnO3)n/(LaFeO3)10 superlattices grown on (001)‐ and (111)‐oriented SrTiO3 substrates. The different crystallographic orientations allow for the interfacial octahedral connectivity to be tuned, with weaker interfacial coupling present at the (001)‐oriented than the (111)‐oriented structures as revealed by density functional theory calculations. In n = 14 superlattices, the effect of orientation on the physical properties is minimal with both (001)‐ and (111)‐oriented samples exhibiting similar magnetoresistance. As the fraction of interfacial volume within the LSMO layers is increased by decreasing n, the magnetoresistive behavior of the samples diverges with significantly larger magnetoresistance magnitudes present in the (111)‐oriented superlattices. The results are consistent with octahedral coupling playing a greater role in the functional properties at (111)‐heterointerfaces and demonstrate a structure‐driven approach to tuning interfacial magnetoresistance in complex‐oxide heterostructures.

First-principles bulk-layer model for dielectric and piezoelectric responses in superlattices

In the first-principles bulk-layer model the superlattice structure and polarization are determined by first-principles computation of the bulk responses of the constituents to the electrical and mechanical boundary conditions in an insulating superlattice. In this work the model is extended to predict functional properties, specifically dielectric permittivity and piezoelectric response. A detailed comparison between the bulk-layer model and full first-principles calculations for three sets of perovskite oxide superlattices, PbTiO$_3$/BaTiO$_3$, BaTiO$_3$/SrTiO$_3$ and PbTiO$_3$/SrTiO$_3$, is presented. The bulk-layer model is shown to give an excellent first approximation to these important functional properties, and to allow for the identification and investigation of additional physics, including interface reconstruction and finite size effects. Technical issues in the generation of the necessary data for constituent compounds are addressed. These results form the foundation for a powerful data-driven method to facilitate discovery and design of superlattice systems with enhanced and tunable polarization, dielectric permittivity, and piezoelectric response.

Effect of charge ordering on crossplane thermal conductivity in correlated perovskite oxide superlattices

Effect of charge ordering on crossplane thermal conductivity in correlated perovskite oxide superlattices

Overlapping growth windows to build complex oxide superlattices

Perovskite oxide superlattices are of particular interest due to novel phenomena emerging at interfaces which are beyond the bulk properties of the constituent layers. However, building perovskite superlattices comprised of stoichiometric layers with sharp interfaces has proven challenging. Here, the synthesis of a series of high quality (SrTiO3)n/(CaTiO3)n superlattice structures grown on LSAT substrates is demonstrated by employing hybrid molecular beam epitaxy, where Ti was supplied using metal-organic titanium tetraisopropoxide (TTIP), and Sr and Ca were supplied using conventional effusion cells. By careful adjustment of the cation fluxes of Sr and Ca with respect to the TTIP flux, the growth windows of SrTiO3 and CaTiO3 were overlapped, allowing us to grow the individual superlattice layers with self-regulated stoichiometry. Stable and repeatable reflection high-energy electron diffraction oscillations during the entire ∼2.5 h growth period indicated good source flux stability. The structural quality of the superlattice films were determined by scanning transmission electron microscopy and synchrotron-based X-ray diffraction, revealing periodic, phase pure, homogenous superlattice structures with abrupt interfaces. Utilization of perovskite stoichiometric growth windows offers great potential for accessing and realizing interface driven phenomena in versatile perovskite superlattice materials with chemistries beyond titanates.

Dimensional control of defect dynamics in perovskite oxide superlattices

Point defects play a critical role in the structural, physical, and interfacial properties of perovskite oxide superlattices. However, understanding of the fundamental properties of point defects in superlattices, especially their transport properties, is rather limited. Here, we report predictions of the stability and dynamics of oxygen vacancies in $\mathrm{SrTi}{\mathrm{O}}_{3}\text{/}\mathrm{PbTi}{\mathrm{O}}_{3}$ oxide superlattices using first-principles calculations in combination with the kinetic Monte Carlo method. By varying the stacking period, i.e., changing of $n$ in $n\mathrm{STO}\text{/}n\mathrm{PTO}$, we discover a crossover from three-dimensional diffusion to primarily two-dimensional planar diffusion. Such planar diffusion may lead to novel designs of ionic conductors. We show that the dominant vacancy position may vary in the superlattices, depending on the superlattice structure and stacking period, contradicting the common assumption that point defects reside at interfaces. Moreover, we predict a significant increase in room-temperature ionic conductivity for 3STO/3PTO relative to the bulk phases. Considering the variety of cations that can be accommodated in perovskite superlattices and the potential mismatch of spin, charge, and orbitals at the interfaces, this paper identifies a pathway to control defect dynamics for technological applications.

Thickness dependence of exchange coupling in (111)-oriented perovskite oxide superlattices

Epitaxial La0.7Sr0.3MnO3 (LSMO)/La0.7Sr0.3FeO3 (LSFO) superlattices on (111)-oriented SrTiO3 substrates with sublayer thicknesses ranging from 3 to 60 unit cells (u.c.) were synthesized and characterized. Detailed analysis of their structural, electronic, and magnetic properties were performed to explore the effect of sublayer thickness on the magnetic structure and exchange coupling at (111)-oriented perovskite oxide interfaces. In the ultrathin limit (3-6 u.c.), we find that the antiferromagnetic (AF) properties of the LSFO sublayers are preserved with an out-of-plane canting of the AF spin axis, while the ferromagnetic (FM) properties of the LSMO sublayers are significantly depressed. For thicker LSFO layers (>9 u.c.), the out-of-plane canting of the AF spin axis is only present in superlattices with thick LSMO sublayers. In conclusion, exchange coupling in the form of spin-flop coupling exists only in superlattices which display both robust ferromagnetism and out-of-plane canting of the AF spin axis.

Polarization enhancement in perovskite superlattices by oxygen octahedral tilts

Interface engineering in perovskite oxide superlattices has developed into a flourishing field, enabling not only further tuning of the exceptional properties, but also giving access to emergent physical phenomena. Here, we reveal a new mechanism for enhancing the electric polarization by the interface-induced oxygen octahedral tilts in BaTiO3/CaTiO3 superlattices. By combining a novel genetic algorithm with density functional theory (DFT), we predict that the true ground states in 1:1 and 2:2 BaTiO3/CaTiO3 superlattices grown on SrTiO3 adopt Pc symmetry with a large proper electric polarization (32.8μC/cm2 for 1:1 and 35.8μC/cm2 for 2:2 superlattices), which is even larger than that of bulk BaTiO3. The tilt of oxygen octahedron is found to play a key role for the enhancement of out-of-plane polarization in 1:1 superlattices because it reduces greatly the rotation of oxygen octahedron (out-of-phase) which significantly suppresses the out-of-plane polarization.

Electric control of the magnetization in BiFeO3/LaFeO3superlattices

First-principles techniques are used to investigate the behavior of BiFeO$_{3}$/LaFeO$_{3}$ perovskite oxide superlattices epitaxially grown on a (001)-SrTiO$_3$ substrate. The calculations show that 1/1 superlattices exhibit a $Pmc2_1$ ground state combining a trilinear coupling of one polar and two oxygen rotational lattice modes, and weak ferromagnetism. The microscopic mechanism allowing one to manipulate the magnetization with an electric field in such systems is presented and its dependence on strain and chemical substitution is discussed. BiFeO$_{3}$/LaFeO$_{3}$ artificial superlattices appear to be good candidates to achieve electric switching of magnetization at room temperature.

Charge-spin-coupled electrical transport properties in EuMoO3/SrTiO3superlattices

We investigate the structural and electrical properties of perovskite oxide superlattices composed of a ferromagnetic metal, EuMoO${}_{3}$, and a paramagnetic insulator, SrTiO${}_{3}$, grown on GdScO${}_{3}$ (110) substrates by pulsed laser deposition. The results of x-ray diffraction show that the superlattices are formed as designed, while considerable interface roughening is recognized by high-resolution scanning transmission electron microscopy. In the transport properties, the temperature dependence of resistivity changes from metallic to insulating behaviors on reducing the thickness of EuMoO${}_{3}$. An anomalous Hall effect emerges in metallic superlattices, and its amplitude clearly corresponds to conductivity. Negative magnetoresistance is observed in all superlattices and is more pronounced in the insulating superlattices. These results indicate the existence of spin-canted and low-conductivity dead layers near the heterointerfaces due to the suppressed exchange coupling between electrons and local Eu 4${f}^{7}$ spins.

Strain relaxation defects in perovskite oxide superlattices

Abstract

The effect of interfacial charge transfer on ferromagnetism in perovskite oxide superlattices

The structural, magnetic, and electrical properties of superlattices composed of the ferromagnetic/metal La0.7Sr0.3MnO3 and non-magnetic/metal La0.5Sr0.5TiO3 grown on (001)-oriented SrTiO3 substrates have been investigated. Using a combination of bulk magnetometry, soft x-ray magnetic spectroscopy, and scanning transmission electron microscopy, we demonstrate that robust ferromagnetic properties can be maintained in this superlattice system where charge transfer at the interfaces is minimized. Therefore, ferromagnetism can be controlled effectively through the chemical identity and the thickness of the individual superlattice layers.

Resonant x-ray reflectivity study of perovskite oxide superlattices

Resonant x-ray reflectivity (XRR) is utilized to characterize the structural properties of La0.7Sr0.3MnO3/La0.7Sr0.3FeO3 superlattices. XRR spectra at the Mn and Fe absorption edges provide additional structural information compared to spectra obtained with a conventional Cu x-ray source. We demonstrate that this technique provides individual layer thicknesses and intermixing behavior of perovskite superlattices with small density contrast in a non-destructive manner. These results are consistent with scanning transmission electron microscopy and electron energy loss spectroscopy.

Correlated domain structure in perovskite oxide superlattices exhibiting spin-flop coupling

We synthesized epitaxial perovskite oxide superlattices consisting of alternating ferromagnetic and antiferromagnetic sublayers with a six-unit-cell sublayer thickness. This sublayer thickness corresponds to the maximum in interfacial spin-flop coupling for this system. Soft x-ray photoemission electron microscopy was used to observe the temperature dependence of the correlation between the ferromagnetic and antiferromagnetic domain structure in each sublayer. We confirm the local perpendicular alignment between the ferromagnetic and antiferromagnet moments and find that the strength of the spin-flop coupling dominates over the pinning effect of the structural domains that typically define the location of the antiferromagnetic domains.

Substrate coherency driven octahedral rotations in perovskite oxide films

We perform first-principles density functional calculations to explore the role of substrate proximity effects on the octahedral rotation patterns in perovskite oxide superlattices. With cubic perovskite SrFeO$_3$ as our model film and tetragonal SrTiO$_3$ as the substrate, we show that in most cases the substrate octahedral rotation patterns propagate into the film across the heterointerface. We also identify elastic boundary conditions for which the enforced structural coherence induces atomic displacement patterns that are not found in the bulk phase diagram of either individual constituent. We suggest that such substrate coherency-induced octahedral texturing of thin film oxides is a promising approach for tuning the electronic structure of functional oxide thin films.

Competing interactions in ferromagnetic/antiferromagnetic perovskite superlattices

Soft x-ray magnetic dichroism, magnetization, and magnetotransport measurements demonstrate that the competition between different magnetic interactions (exchange coupling, electronic reconstruction, and long-range interactions) in ${\text{La}}_{0.7}{\text{Sr}}_{0.3}{\text{FeO}}_{3}(\text{LSFO})/{\text{La}}_{0.7}{\text{Sr}}_{0.3}{\text{MnO}}_{3}(\text{LSMO})$ perovskite oxide superlattices leads to unexpected functional properties. The antiferromagnetic order parameter in LSFO and ferromagnetic order parameter in LSMO show a dissimilar dependence on sublayer thickness and temperature, illustrating the high degree of tunability in these artificially layered materials.

First-principles effective Hamiltonian for ferroelectric polarization inBaTiO3/SrTiO3 superlattices

We present an effective Hamiltonian for the description of ferroelectric polarizations in perovskite oxide superlattices. To understand the ferroelectric behavior of (BaTiO3)n/(SrTiO3)m superlattices, we constrained the local distortion modes along the c direction only and set up the effective Hamiltonian based on the local modes that capture the physics of long-wavelength acoustic modes (strain) and lowest energy transverse optical phonon modes (soft modes) as prescribed by the localized Wannier functions. All the parameters in this effective Hamiltonian were predetermined from the first-principles density-functional theory calculations of each BaTiO3 and SrTiO3 components. As an application of the model parameters, we calculated the polarizations of (BaTiO3)n/(SrTiO3)m with n+m=5, the results of which are in good agreement with those of the previous first-principles calculations of average polarizations as well as local polarizations. This effective Hamiltonian procedure can provide guidance for developing ferroelectric model of other kinds of oxide superlattices.