Manipulating Berry curvature of SrRuO3 thin films via epitaxial strain.

Berry curvature plays a crucial role in exotic electronic states of quantum materials, such as the intrinsic anomalous Hall effect. As Berry curvature is highly sensitive to subtle changes of electronic band structures, it can be finely tuned via external stimulus. Here, we demonstrate in SrRuO3 thin films that both the magnitude and sign of anomalous Hall resistivity can be effectively controlled with epitaxial strain. Our first-principles calculations reveal that epitaxial strain induces an additional crystal field splitting and changes the order of Ru d orbital energies, which alters the Berry curvature and leads to the sign and magnitude change of anomalous Hall conductivity. Furthermore, we show that the rotation of the Ru magnetic moment in real space of a tensile-strained sample can result in an exotic nonmonotonic change of anomalous Hall resistivity with the sweeping of magnetic field, resembling the topological Hall effect observed in noncoplanar spin systems. These findings not only deepen our understanding of anomalous Hall effect in SrRuO3 systems but also provide an effective tuning knob to manipulate Berry curvature and related physical properties in a wide range of quantum materials.

Strain-Induced Robust Exchange Bias Effect in Epitaxial La0.7Sr0.3MnO3/LaFeO3 Bilayers.

The ground state of correlated electrons in complex oxide films can be controlled by applying epitaxial strain, offering the potential to produce unexpected phenomena applicable to modern spintronic devices. In this study, we demonstrate that substrate-induced strain strongly affects the coupling mode of interfacial magnetic moments in a ferromagnetic (FM)/antiferromagnetic (AFM) system. In an epitaxial bilayer comprising AFM LaFeO3 (LFO) and FM La0.7Sr0.3MnO3 (LSMO), samples grown on a LaAlO3 (LAO) substrate exhibit a larger exchange bias field than those grown on a SrTiO3 substrate. Our results indicate a transition in the alignment of magnetic moments from perpendicular to collinear due to the large compressive strain exerted by the LAO substrate. Collinear magnetic moments at the LSMO/LFO interface generate strong exchange coupling, leading to a considerable exchange bias effect. Thus, our findings provide a method for tailoring and manipulating the orientations of magnetic moments at the FM/AFM heterogeneous interface using strain engineering, thereby augmenting methods for exchange bias generation.

Tunable Magnetic Properties in Sr2FeReO6 Double-Perovskite.

Double-perovskite oxides have attracted recent attention due to their attractive functionalities and application potential. In this paper, we demonstrate the effect of dual controls, i.e., the deposition pressure of oxygen (PO2) and lattice mismatch (ε), on tuning magnetic properties in epitaxial double-perovskite Sr2FeReO6 films. In a nearly lattice matched Sr2FeReO6/SrTiO3 film, the ferrimagnetic-to-paramagnetic phase transition occurs when PO2 is reduced to 30 mTorr, probably due to the formation of Re4+ ions that replace the stoichiometric Re5+ to cause disorders of B-site ions. On the other hand, a large compressive strain or tensile strain shifts this critical PO2 to below 1 mTorr or above 40 mTorr, respectively. The observations can be attributed to the modulation of B-site ordering by epitaxial strain through affecting elemental valence. Our results provide a feasible way to expand the functional tunability of magnetic double-perovskite oxides that hold great promise for spintronic devices.

Dynamics of Anisotropic Oxygen-Ion Migration in Strained Cobaltites.

Orientation control of the oxygen vacancy channel (OVC) is highly desirable for tailoring oxygen diffusion as it serves as a fast transport channel in ion conductors, which is widely exploited in solid-state fuel cells, catalysts, and ion-batteries. Direct observation of oxygen-ion hopping toward preferential vacant sites is a key to clarifying migration pathways. Here we report anisotropic oxygen-ion migration mediated by strain in ultrathin cobaltites via in situ thermal activation in atomic-resolved transmission electron microscopy. Oxygen migration pathways are constructed on the basis of the atomic structure during the OVC switching, which is manifested as the vertical-to-horizontal OVC switching under tensile strain but the horizontal-to-diagonal switching under compression. We evaluate the topotactic structural changes to the OVC, determine the crucial role of the tolerance factor for OVC stability, and establish the strain-dependent phase diagram. Our work provides a practical guide for engineering OVC orientation that is applicable to ionic-oxide electronics.

Ferroelectric Domain Walls in PbTiO3 Are Effective Regulators of Heat Flow at Room Temperature.

Achieving efficient spatial modulation of phonon transmission is an essential step on the path to phononic circuits using "phonon currents". With their intrinsic and reconfigurable interfaces, domain walls (DWs), ferroelectrics are alluring candidates to be harnessed as dynamic heat modulators. This paper reports the thermal conductivity of single-crystal PbTiO3 thin films over a wide variety of epitaxial-strain-engineered ferroelectric domain configurations. The phonon transport is proved to be strongly affected by the density and type of DWs, achieving a 61% reduction of the room-temperature thermal conductivity compared to the single-domain scenario. The thermal resistance across the ferroelectric DWs is obtained, revealing a very high value (≈5.0 × 10-9 K m2 W-1), comparable to grain boundaries in oxides, explaining the strong modulation of the thermal conductivity in PbTiO3. This low thermal conductance of the DWs is ascribed to the structural mismatch and polarization gradient found between the different types of domains in the PbTiO3 films, resulting in a structural inhomogeneity that extends several unit cells around the DWs. These findings demonstrate the potential of ferroelectric DWs as efficient regulators of heat flow in one single material, overcoming the complexity of multilayers systems and the uncontrolled distribution of grain boundaries, paving the way for applications in phononics.

Magnetic Properties of Epitaxially Grown SrRuO3 Nanodots.

We present the fabrication and exploration of arrays of nanodots of SrRuO3 with dot sizes between 500 and 15 nm. Down to the smallest dot size explored, the samples were found to be magnetic with a maximum Curie temperature TC achieved by dots of 30 nm diameter. This peak in TC is associated with a dot-size-induced relief of the epitaxial strain, as evidenced by scanning transmission electron microscopy.

Room-temperature negative capacitance in a ferroelectric-dielectric superlattice heterostructure.

We demonstrate room-temperature negative capacitance in a ferroelectric-dielectric superlattice heterostructure. In epitaxially grown superlattice of ferroelectric BSTO (Ba0.8Sr0.2TiO3) and dielectric LAO (LaAlO3), capacitance was found to be larger compared to the constituent LAO (dielectric) capacitance. This enhancement of capacitance in a series combination of two capacitors indicates that the ferroelectric was stabilized in a state of negative capacitance. Negative capacitance was observed for superlattices grown on three different substrates (SrTiO3 (001), DyScO3 (110), and GdScO3 (110)) covering a large range of substrate strain. This demonstrates the robustness of the effect as well as potential for controlling the negative capacitance effect using epitaxial strain. Room-temperature demonstration of negative capacitance is an important step toward lowering the subthreshold swing in a transistor below the intrinsic thermodynamic limit of 60 mV/decade and thereby improving energy efficiency.

Structure and stability of La- and hole-doped hafnia with/without epitaxial strain.

The significance of hafnia in the semiconductor industry has been amplified following the unearthing of its ferroelectric properties. We investigated the structure and electrical properties of La- and hole-doped HfO2with/without epitaxial strain by first-principles calculations. It is found that the charge compensated defect with oxygen vacancy (LaHfVO) and uncompensated defect (LaHf), compared to the undoped case, make the ferroelectric orthorhombicPca21phase (ophase) more stable. Conversely, the electrons compensated defect (LaHf+e) makes the nonpolar monoclinicP21/cphase (mphase) more stable. Furthermore, both pure hole doping (without ions substituent) and compressive strain can stabilize theophase. Our work offers a new perspective on enhancing the ferroelectricity of hafnia.

Polar Metallicity Controlled by Epitaxial Strain Engineering.

The discovery of polar metal opens the door to incorporating electric polarization into electronics with the potential to invigorate next-generation multifunctional electronic devices. Especially, electric polarization can be induced by geometric design in non-polar perovskite oxides. Here, the epitaxial strain exerted on the deposited single-crystalline NdNiO3 thin films is systematically varied in both sign and amplitude by choosing substrates with different lattice mismatch. The pseudocubic NdNiO3(111) film, which is non-polar in its bulk state, is induced to be polar under both compressive and tensile strain. The fine-tuning of epitaxial strain is realized by continuously varying the film thickness using the "thickness-wedge" growth technique, and from the elucidated thickness dependence, the electric polarization and metallicity can be further optimized. Moreover, transitioning from isotropic to anisotropic epitaxial strain gives rise to an ideal polar metal state in the pseudocubic NdNiO3(102) film on an orthorhombic substrate, achieving a remarkably low resistivity of 173 µΩ cm at room temperature. The metal-insulator transition in NdNiO3 is completely suppressed and the polar metal state becomes the ground state at all temperatures. These results demonstrate alluring possibilities of induction and manipulation of both electric polarization and electric transport properties in functional perovskite oxides by epitaxial strain engineering.

Epitaxial Strain Enhanced Ferroelectric Polarization toward a Giant Tunneling Electroresistance.

A substantial ferroelectric polarization is the key for designing high-performance ferroelectric nonvolatile memories. As a promising candidate system, the BaTiO3/La0.67Sr0.33MnO3 (BTO/LSMO) ferroelectric/ferromagnetic heterostructure has attracted a lot of attention thanks to the merits of high Curie temperature, large spin polarization, and low ferroelectric coercivity. Nevertheless, the BTO/LSMO heterostructure suffers from a moderate FE polarization, primarily due to the quick film-thickness-driven strain relaxation. In response to this challenge, we propose an approach for enhancing the FE properties of BTO films by using a Sr3Al2O6 (SAO) buffering layer to mitigate the interfacial strain relaxation. The continuously tunable strain allows us to illustrate the linear dependence of polarization on epitaxial strain with a large strain-sensitive coefficient of ∼27 µC/cm2 per percent strain. This results in a giant polarization of ∼80 µC/cm2 on the BTO/LSMO interface. Leveraging this large polarization, we achieved a giant tunneling electroresistance (TER) of ∼105 in SAO-buffered Pt/BTO/LSMO ferroelectric tunnel junctions (FTJs). Our research uncovers the fundamental interplay between strain, polarization magnitude, and device performance, such as on/off ratio, thereby advancing the potential of FTJs for next-generation information storage applications.

Band Gaps and Optical Properties of RENiO3 upon Strain: Combining First-Principles Calculations and Machine Learning.

Rare earth nickel-based perovskite oxides (RENiO3) have been widely studied over recent decades because of their unique properties. In the synthesis of RENiO3 thin films, a lattice mismatch frequently exists between the substrates and the thin films, which may affect the optical properties of RENiO3. In this paper, the first-principles calculations were employed to study the electronic and optical properties of RENiO3 under strain. The results showed that with the increase in tensile strength, the band gap generally shows a widening trend. For optical properties, the absorption coefficients increase with the enhancement of photon energies in the far-infrared range. The compressive strain increases the light absorption, while the tensile strain suppresses it. For the reflectivity spectrum in the far-infrared range, a minimum reflectivity displays around the photon energy of 0.3 eV. The tensile strain enhances the reflectivity in the range of 0.05-0.3 eV, whereas it decreases it when the photon energies are larger than 0.3 eV. Furthermore, machine learning algorithms were applied and found that the planar epitaxial strain, electronegativity, volume of supercells, and rare earth element ion radius play key roles in the band gaps. Photon energy, electronegativity, band gap, the ionic radius of the rare earth element, and the tolerance factor are key parameters significantly influencing the optical properties.

Spin State Disproportionation in Insulating Ferromagnetic LaCoO3 Epitaxial Thin Films.

The origin of insulating ferromagnetism in epitaxial LaCoO3 films under tensile strain remains elusive despite extensive research efforts are devoted. Surprisingly, the spin state of its Co ions, the main parameter of its ferromagnetism, is still to be determined. Here, the spin state in epitaxial LaCoO3 thin films is systematically investigated to clarify the mechanism of strain-induced ferromagnetism using element-specific X-ray absorption spectroscopy and dichroism. Combining with the configuration interaction cluster calculations, it is unambiguously demonstrated that Co3+ in LaCoO3 films under compressive strain (on LaAlO3 substrate) is practically a low-spin state, whereas Co3+ in LaCoO3 films under tensile strain (on SrTiO3 substrate) have mixed high-spin and low-spin states with a ratio close to 1:3. From the identification of this spin state ratio, it is inferred that the dark strips observed by high-resolution scanning transmission electron microscopy indicate the position of Co3+ high-spin state, i.e., an observation of a spin state disproportionation in tensile-strained LaCoO3 films. This consequently explains the nature of ferromagnetism in LaCoO3 films. The study highlights the importance of spin state degrees of freedom, along with thin-film strain engineering, in creating new physical properties that do not exist in bulk materials.

Direct Epitaxial Growth of Polar Hf0.5Zr0.5O2 Films on Corundum.

Single-phase epitaxial Hf0.5Zr0.5O2 films with non-centrosymmetric orthorhombic structure have been grown directly on electrode-free corundum (α-Al2O3) substrates by pulsed laser deposition. A combination of high-resolution X-ray diffraction and X-ray absorption spectroscopy confirms the epitaxial growth of high-quality films belonging to the Pca21 space group, with [111] out-of-plane orientation. The surface of a 7-nm-thick sample exhibits an atomic step-terrace structure with a corrugation of the order of one atomic layer, as proved by atomic force microscopy. Scanning transmission electron microscopy reveals that it consists of grains with around 10 nm lateral size. The polar nature of this film has been corroborated by pyroelectric measurements. These results shed light on the mechanisms of the epitaxial stabilization of the ferroelectric phase of hafnia.

Remanent Polarization and Strong Photoluminescence Modulation by an External Electric Field in Epitaxial CsPbBr3 Nanowires.

Metal halide perovskites (MHPs) have unique characteristics and hold great potential for next-generation optoelectronic technologies. Recently, the importance of lattice strain in MHPs has been gaining recognition as a significant optimization parameter for device performance. While the effect of strain on the fundamental properties of MHPs has been at the center of interest, its combined effect with an external electric field has been largely overlooked. Here we perform an electric-field-dependent photoluminescence study on heteroepitaxially strained surface-guided CsPbBr3 nanowires. We reveal an unexpected strong linear dependence of the photoluminescence intensity on the alternating field amplitude, stemming from an induced internal dipole. Using low-frequency polarized-Raman spectroscopy, we reveal structural modifications in the nanowires under an external field, associated with the observed polarity. These results reflect the important interplay between strain and an external field in MHPs and offer opportunities for the design of MHP-based optoelectronic nanodevices.

Strong Magnetic Anisotropy of Epitaxial PrVO3 Thin Films on SrTiO3 Substrates with Different Orientations.

We have probed the structural and magnetic properties of PrVO3 (PVO) thin films grown on the (001)-, (110)-, and (111)-oriented SrTiO3 (STO) substrates. By changing the substrate orientation, the film out-of-plane orientation can be tuned to [110], [100]/[010], and [011]/[311], with different in-plane crystallographic variants. Accommodation of these variants on the different substrates implies different strain states, which have direct influence on the magnetic properties of PVO films. The magnetic moment of PVO films radically enhances from 0.4 µB/f.u. for STO(001) to 2.3 µB/f.u. for STO(111). While films on the (001)-oriented STO substrate display out-of-plane anisotropy, an in-plane anisotropy is observed for films grown on the (110)- and (111)-oriented STO substrates. In addition, a strong uniaxial magnetic anisotropy is also extracted for a partially relaxed film on the (110)-oriented STO substrate. Such findings can help oxide community for the better understanding of magnetic anisotropy in vanadate thin films, a subject that still suffer from significant lack of scientific investigations.

Strain Engineering at Heterointerfaces: Application to an Iron Pnictide Superconductor, Cobalt-Doped BaFe2As2.

We propose a unique strategy to apply stronger strain at heterointerfaces than conventional epitaxial strain methods to extract hidden attractive physical/chemical properties in materials. This strategy involves precisely accounting for the epitaxial strain induced by lattice mismatch as well as the differences in the thermal expansion coefficients and compressibilities of epitaxial films and substrates. We selected optimally cobalt-doped BaFe2As2(Ba122:Co), an iron-based superconductor with a bulk critical temperature (Tc) of 22 K, as a model material and four types of single-crystal substrates. Ba122:Co was selected because its Tc is robust to hydrostatic pressure but sensitive to epitaxial strain (i.e., one of the anisotropic strains), and the selected substrates entirely cover the positive/negative lattice mismatches, thermal expansion coefficients, and compressibilities with respect to Ba122:Co. With strong anisotropic strain successfully induced by film growth, external hydrostatic pressurizing, and cooling processes, we observed unique carrier transport properties in Ba122:Co epitaxial films on CaF2 and BaF2 substrates including (i) upturn behavior in the temperature dependence of the longitudinal resistivity, (ii) negative magnetoresistance, (iii) large enhancement of anomalous Hall effects in the epitaxial films on CaF2, and (iv) enhancement of Tc to 27 K in the epitaxial films on BaF2. These results demonstrate the effectiveness of our strategy, and this approach can be further extended to other inorganic materials in thin-film form.

Strain Control of Giant Magnetic Anisotropy in Metallic Perovskite SrCoO3-δ Thin Films.

Magnetic materials with large magnetic anisotropy are essential for workaday applications such as permanent magnets and magnetic data storage. There is widespread interest in finding efficient ways of controlling magnetic anisotropy, among which strain control has proven to be a very powerful technique. Here, we demonstrate the strain-mediated magnetic anisotropy in SrCoO3-δ thin film, a perovskite oxide that is metallic and adopts a cubic structure at δ ≤ 0.25. We find that the easy-magnetization axis in SrCoO3-δ can be rotated by 90° upon application of moderate epitaxial strains ranging from -1.2 to +1.8%. The magnetic anisotropy in compressive SrCoO3-δ thin films is huge, as shown by magnetic hysteresis loops rendering an anisotropy energy density of ∼106 erg/cm3. The local variance in magnetic force microscopy upon temperature and magnetic field reveals that the evolution of magnetic domains in the SCO thin film is strongly dependent on magnetic anisotropy.

Manipulating the Structural and Electronic Properties of Epitaxial SrCoO2.5 Thin Films by Tuning the Epitaxial Strain.

Structure determines material's functionality, and strain tunes the structure. Tuning the coherent epitaxial strain by varying the thickness of the films is a precise route to manipulate the functional properties in the low-dimensional oxide materials. Here, to explore the effects of the coherent epitaxial strain on the properties of SrCoO2.5 thin films, thickness-dependent evolutions of the structural properties and electronic structures were investigated by X-ray diffraction, Raman spectra, optical absorption spectra, scanning transmission electron microscopy (STEM), and first-principles calculations. By increasing the thickness of the SrCoO2.5 films, the c-axis lattice constant decreases, indicating the relaxation of the coherent epitaxial strain. The energy band gap increases and the Raman spectra undergo a substantial softening with the relaxation of the coherent epitaxial strain. From the STEM results, it can be concluded that the strain causes the variation of the oxygen content in the BM-SCO2.5 films, which results in the variation of band gaps with varying the strain. First-principles calculations show that strain-induced changes in bond lengths and angles of the octahedral CoO6 and tetrahedral CoO4 cannot explain the variation band gap. Our findings offer an alternative strategy to manipulate structural and electronic properties by tuning the coherent epitaxial strain in transition-metal oxide thin films.

Ambiguous Role of Growth-Induced Defects on the Semiconductor-to-Metal Characteristics in Epitaxial VO2/TiO2 Thin Films.

Controlling the semiconductor-to-metal transition temperature in epitaxial VO2 thin films remains an unresolved question both at the fundamental as well as the application level. Within the scope of this work, the effects of growth temperature on the structure, chemical composition, interface coherency and electrical characteristics of rutile VO2 epitaxial thin films grown on TiO2 substrates are investigated. It is hereby deduced that the transition temperature is lower than the bulk value of 340 K. However, it is found to approach this value as a function of increased growth temperature even though it is accompanied by a contraction along the V4+-V4+ bond direction, the crystallographic c-axis lattice parameter. Additionally, it is demonstrated that films grown at low substrate temperatures exhibit a relaxed state and a strongly reduced transition temperature. It is suggested that, besides thermal and epitaxial strain, growth-induced defects may strongly affect the electronic phase transition. The results of this work reveal the difficulty in extracting the intrinsic material response to strain, when the exact contribution of all strain sources cannot be effectively determined. The findings also bear implications on the limitations in obtaining the recently predicted novel semi-Dirac point phase in VO2/TiO2 multilayer structures.

Coupled Lattice Polarization and Ferromagnetism in Multiferroic NiTiO3 Thin Films.

Polarization-induced weak ferromagnetism (WFM) was demonstrated a few years back in LiNbO3-type compounds, MTiO3 (M = Fe, Mn, Ni). Although the coexistence of ferroelectric polarization and ferromagnetism has been demonstrated in this rare multiferroic family before, first in bulk FeTiO3, then in thin-film NiTiO3, the coupling of the two order parameters has not been confirmed. Here, we report the stabilization of polar, ferromagnetic NiTiO3 by oxide epitaxy on a LiNbO3 substrate utilizing tensile strain and demonstrate the theoretically predicted coupling between its polarization and ferromagnetism by X-ray magnetic circular dichroism under applied fields. The experimentally observed direction of ferroic ordering in the film is supported by simulations using the phase-field approach. Our work validates symmetry-based criteria and first-principles calculations of the coexistence of ferroelectricity and WFM in MTiO3 transition metal titanates crystallizing in the LiNbO3 structure. It also demonstrates the applicability of epitaxial strain as a viable alternative to high-pressure crystal growth to stabilize metastable materials and a valuable tuning parameter to simultaneously control two ferroic order parameters to create a multiferroic. Multiferroic NiTiO3 has potential applications in spintronics where ferroic switching is used, such as new four-stage memories and electromagnetic switches.