Exploiting Symmetry Mismatch to Control Magnetism in a Ferroelastic Heterostructure.

In the bulk, LaCoO_{3} (LCO) is a paramagnet, yet the low-temperature ferromagnetism (FM) is observed in tensile strained thin films, and its origin remains unresolved. Here, we quantitatively measured the distribution of atomic density and magnetization in LCO films by polarized neutron reflectometry (PNR) and found that the LCO layers near the heterointerfaces exhibit a reduced magnetization but an enhanced atomic density, whereas the film's interior (i.e., its film bulk) shows the opposite trend. We attribute the nonuniformity to the symmetry mismatch at the interface, which induces a structural distortion related to the ferroelasticity of LCO. This assertion is tested by systematic application of hydrostatic pressure during the PNR experiments. The magnetization can be controlled at a rate of -20.4% per GPa. These results provide unique insights into mechanisms driving FM in strained LCO films while offering a tantalizing observation that tunable deformation of the CoO_{6} octahedra in combination with the ferroelastic order parameter.

Nanoscale ferroelastic twins formed in strained LaCoO3 films.

The coexistence and coupling of ferroelasticity and magnetic ordering in a single material offers a great opportunity to realize novel devices with multiple tuning knobs. Complex oxides are a particularly promising class of materials to find multiferroic interactions due to their rich phase diagrams, and are sensitive to external perturbations. Still, there are very few examples of these systems. Here, we report the observation of twin domains in ferroelastic LaCoO3 epitaxial films and their geometric control of structural symmetry intimately linked to the material's electronic and magnetic states. A unidirectional structural modulation is achieved by selective choice of substrates having twofold rotational symmetry. This modulation perturbs the crystal field-splitting energy, leading to unexpected in-plane anisotropy of orbital configuration and magnetization. These findings demonstrate the use of structural modulation to control multiferroic interactions and may enable a great potential for stimulation of exotic phenomena through artificial domain engineering.

Designing Morphotropic Phase Composition in BiFeO3.

In classical morphotropic piezoelectric materials, rhombohedral and tetragonal phase variants can energetically compete to form a mixed phase regime with improved functional properties. While the discovery of morphotropic-like phases in multiferroic BiFeO3 films has broadened this definition, accessing these phase spaces is still typically accomplished through isovalent substitution or heteroepitaxial strain which do not allow for continuous modification of phase composition postsynthesis. Here, we show that it is possible to use low-energy helium implantation to tailor morphotropic phases of epitaxial BiFeO3 films postsynthesis in a continuous and iterative manner. Applying this strain doping approach to morphotropic films creates a new phase space based on internal and external lattice stress that can be seen as an analogue to temperature-composition phase diagrams of classical morphotropic ferroelectric systems.

Designing Magnetic Anisotropy through Strain Doping.

The coupling between a material's lattice and its underlying spin state links structural deformation to magnetic properties; however, traditional strain engineering does not allow the continuous, post-synthesis control of lattice symmetry needed to fully utilize this fundamental coupling in device design. Uniaxial lattice expansion induced by post-synthesis low energy helium ion implantation is shown to provide a means of bypassing these limitations. Magnetocrystalline energy calculations can be used a priori to estimate the predictive design of a material's preferred magnetic spin orientation. The efficacy of this approach is experimentally confirmed in a spinel CoFe2O4 model system where the epitaxial film's magnetic easy axis is continuously manipulated between the out-of-plane (oop) and in-plane (ip) directions as lattice tetragonality moves from ip to oop with increasing strain doping. Macroscopically gradual and microscopically abrupt changes to preferential spin orientation are demonstrated by combining ion irradiation with simple beam masking and lithographic procedures. The ability to design magnetic spin orientations across multiple length scales in a single crystal wafer using only crystal symmetry considerations provides a clear path toward the rational design of spin transfer, magnetoelectric, and skyrmion-based applications where magnetocrystalline energy must be dictated across multiple length scales.

Ba3Fe1.56Ir1.44O9: A Polar Semiconducting Triple Perovskite with Near Room Temperature Magnetic Ordering.

The crystal chemistry and magnetic properties for two triple perovskites, Ba3Fe1.56Ir1.44O9 and Ba3NiIr2O9, grown as large, highly faceted single crystals from a molten strontium carbonate flux, are reported. Unlike the idealized A3MM2'O9 hexagonal symmetry characteristic of most triple perovskites, including Ba3NiIr2O9, Ba3Fe1.56Ir1.44O9 possesses significant site-disorder, resulting in a noncentrosymmetric polar structure with trigonal symmetry. The valence of iron and iridium in the heavily distorted Fe/Ir sites was determined to be Fe(III) and Ir(V) by X-ray absorption near edge spectroscopy (XANES). Density functional theory calculations were conducted to understand the effect of the trigonal distortion on the local Fe(III)O6 electronic structure, and the spin state of iron was determined to be S = 5/2 by Mössbauer spectroscopy. Conductivity measurements indicate thermally activated semiconducting behavior in the trigonal perovskite. Magnetic properties were measured and near room temperature magnetic ordering (TN = 270 K) was observed for Ba3Fe1.56Ir1.44O9.

Oxygen Diode Formed in Nickelate Heterostructures by Chemical Potential Mismatch.

Deliberate control of oxygen vacancy formation and migration in perovskite oxide thin films is important for developing novel electronic and iontronic devices. Here, it is found that the concentration of oxygen vacancies (VO ) formed in LaNiO3 (LNO) during pulsed laser deposition is strongly affected by the chemical potential mismatch between the LNO film and its proximal layers. Increasing the VO concentration in LNO significantly modifies the degree of orbital polarization and drives the metal-insulator transition. Changes in the nickel oxidization state and carrier concentration in the films are confirmed by soft X-ray absorption spectroscopy and optical spectroscopy. The ability to unidirectional-control the oxygen flow across the heterointerface, e.g., a so-called "oxygen diode", by exploiting chemical potential mismatch at interfaces provides a new avenue to tune the physical and electrochemical properties of complex oxides.

Local low rank denoising for enhanced atomic resolution imaging.

Atomic resolution imaging and spectroscopy suffers from inherently low signal to noise ratios often prohibiting the interpretation of single pixels or spectra. We introduce local low rank (LLR) denoising as tool for efficient noise removal in scanning transmission electron microscopy (STEM) images and electron energy-loss (EEL) spectrum images. LLR denoising utilizes tensor decomposition techniques, in particular the multilinear singular value decomposition (MLSVD), to achieve a denoising in a general setting largely independent of the signal features and data dimension, by assuming that the signal of interest is of low rank in segments of appropriately chosen size. When applied to STEM images of graphene, LLR denoising suppresses statistical noise while retaining fine image features such as scan row-wise distortions, possibly related to rippling of the graphene sheet and consequent motion of atoms. When applied to EEL spectra, LLR denoising reveals fine structures distinguishing different lattice sites in the spinel system CoFe2O4.

Strain coupling of oxygen non-stoichiometry in perovskite thin films.

The effects of strain and oxygen vacancies on perovskite thin films have been studied in great detail over the past decades and have been treated separately from each other. While epitaxial strain has been realized as a tuning knob to tailor the functional properties of correlated oxides, oxygen vacancies are usually regarded as undesirable and detrimental. In transition metal oxides, oxygen defects strongly modify the properties and functionalities via changes in oxidation states of the transition metals. However, such coupling is not well understood in epitaxial films, but rather deemed as cumbersome or experimental artifact. Only recently it has been recognized that lattice strain and oxygen non-stoichiometry are strongly correlated in a vast number of perovskite systems and that this coupling can be beneficial for information and energy technologies. Recent experimental and theoretical studies have focused on understanding the correlated phenomena between strain and oxygen vacancies for a wide range of perovskite systems. These correlations not only include the direct relationship between elastic strain and the formation energy of oxygen vacancies, but also comprise highly complex interactions such as strain-induced phase transitions due to oxygen vacancy ordering. Therefore, we aim in this review to give a comprehensive overview on the coupling between strain and oxygen vacancies in perovskite oxides and point out the potential applications of the emergent functionalities strongly coupled to oxygen vacancies.

Designing functionality in perovskite thin films using ion implantation techniques: Assessment and insights from first-principles calculations.

Recent experimental findings have demonstrated that low doses of low energy helium ions can be used to tailor the structural and electronic properties of single crystal films. These initial studies have shown that changes to lattice expansion were proposed to be the direct result of chemical pressure originating predominantly from the implanted He applying chemical pressure at interstitial sites. However, the influence of possible secondary knock-on damage arising from the He atoms transferring energy to the lattice through nuclear-nuclear collision with the crystal lattice remains largely unaddressed. Here, we study SrRuO3 to provide a comprehensive examination of the impact of common defects on structural and electronic properties. We found that, while interstitial He can modify the properties, a dose significantly larger than those reported in experimental studies would be required. Our study suggests that true origin of the observed changes is from combination of secondary defects created during He implantation. Of particular importance, we observe that different defect types can generate greatly varied local electronic structures and that the formation energies and migration energy barriers vary by defect type. Thus, we may have identified a new method of selectively inducing controlled defect complexes into single crystal materials.

Spatially Resolved Large Magnetization in Ultrathin BiFeO3.

Here, a quantitative magnetic depth profile across the planar interfaces in BiFeO3 /La0.7 Sr0.3 MnO3 (BFO/LSMO) superlattices using polarized neutron reflectometry is obtained. An enhanced magnetization of 1.83 ± 0.16 µB /Fe in BFO layers is observed when they are interleaved between two manganite layers. The enhanced magnetic order in BFO persists up to 200 K. The depth dependence of magnetic moments in BFO/LSMO superlattices as a function of the BFO layer thickness is also explored. The results show the enhanced net magnetic moment in BFO from the LSMO/BFO interface extends 3-4 unit cells into BFO. The interior part of a thicker BFO layer has a much smaller magnetization, suggesting it still keeps the small canted AFM state. The results exclude charge transfer, intermixing, epitaxial strain, and octahedral rotations/tilts as dominating mechanisms for the large net magnetization in BFO. An explanation-one suggested by others previously and consistent with the observations-attributes the temperature dependence of the net magnetization of BFO to strong orbital hybridization between Fe and Mn across the interfaces. Such orbital reconstruction would establish an upper temperature limit for magnetic ordering of BFO.

Interface-induced multiferroism by design in complex oxide superlattices.

Interfaces between materials present unique opportunities for the discovery of intriguing quantum phenomena. Here, we explore the possibility that, in the case of superlattices, if one of the layers is made ultrathin, unexpected properties can be induced between the two bracketing interfaces. We pursue this objective by combining advanced growth and characterization techniques with theoretical calculations. Using prototype La2/3Sr1/3MnO3 (LSMO)/BaTiO3 (BTO) superlattices, we observe a structural evolution in the LSMO layers as a function of thickness. Atomic-resolution EM and spectroscopy reveal an unusual polar structure phase in ultrathin LSMO at a critical thickness caused by interfacing with the adjacent BTO layers, which is confirmed by first principles calculations. Most important is the fact that this polar phase is accompanied by reemergent ferromagnetism, making this system a potential candidate for ultrathin ferroelectrics with ferromagnetic ordering. Monte Carlo simulations illustrate the important role of spin-lattice coupling in LSMO. These results open up a conceptually intriguing recipe for developing functional ultrathin materials via interface-induced spin-lattice coupling.

Reversible Control of Interfacial Magnetism through Ionic-Liquid-Assisted Polarization Switching.

The ability to control magnetism of materials via electric field enables a myriad of technological innovations in information storage, sensing, and computing. We use ionic-liquid-assisted ferroelectric switching to demonstrate reversible modulation of interfacial magnetism in a multiferroic heterostructure composed of ferromagnetic (FM) La0.8Sr0.2MnO3 and ferroelectric (FE) PbZr0.2Ti0.8O3. It is shown that ionic liquids can be used to persistently and reversibly switch a large area of a FE film. This is a prerequisite for polarized neutron reflectometry (PNR) studies that are conducted to directly probe magnetoelectric coupling of the FE polarization to the interfacial magnetization.

Emerging magnetism and anomalous Hall effect in iridate-manganite heterostructures.

Strong Coulomb repulsion and spin-orbit coupling are known to give rise to exotic physical phenomena in transition metal oxides. Initial attempts to investigate systems, where both of these fundamental interactions are comparably strong, such as 3d and 5d complex oxide superlattices, have revealed properties that only slightly differ from the bulk ones of the constituent materials. Here we observe that the interfacial coupling between the 3d antiferromagnetic insulator SrMnO3 and the 5d paramagnetic metal SrIrO3 is enormously strong, yielding an anomalous Hall response as the result of charge transfer driven interfacial ferromagnetism. These findings show that low dimensional spin-orbit entangled 3d-5d interfaces provide an avenue to uncover technologically relevant physical phenomena unattainable in bulk materials.

Dynamic defect correlations dominate activated electronic transport in SrTiO3.

Strontium titanate (SrTiO3, STO) is a critically important material for the study of emergent electronic phases in complex oxides, as well as for the development of applications based on their heterostructures. Despite the large body of knowledge on STO, there are still many uncertainties regarding the role of defects in the properties of STO, including their influence on ferroelectricity in bulk STO and ferromagnetism in STO-based heterostructures. We present a detailed analysis of the decay of persistent photoconductivity in STO single crystals with defect concentrations that are relatively low but significantly affect their electronic properties. The results show that photo-activated electron transport cannot be described by a superposition of the properties due to independent point defects as current models suggest but is, instead, governed by defect complexes that interact through dynamic correlations. These results emphasize the importance of defect correlations for activated electronic transport properties of semiconducting and insulating perovskite oxides.

Continuously Controlled Optical Band Gap in Oxide Semiconductor Thin Films.

The optical band gap of the prototypical semiconducting oxide SnO2 is shown to be continuously controlled through single axis lattice expansion of nanometric films induced by low-energy helium implantation. While traditional epitaxy-induced strain results in Poisson driven multidirectional lattice changes shown to only allow discrete increases in bandgap, we find that a downward shift in the band gap can be linearly dictated as a function of out-of-plane lattice expansion. Our experimental observations closely match density functional theory that demonstrates that uniaxial strain provides a fundamentally different effect on the band structure than traditional epitaxy-induced multiaxes strain effects. Charge density calculations further support these findings and provide evidence that uniaxial strain can be used to drive orbital hybridization inaccessible with traditional strain engineering techniques.

Strain Doping: Reversible Single-Axis Control of a Complex Oxide Lattice via Helium Implantation.

We report on the use of helium ion implantation to independently control the out-of-plane lattice constant in epitaxial La(0.7)Sr(0.3)MnO(3) thin films without changing the in-plane lattice constants. The process is reversible by a vacuum anneal. Resistance and magnetization measurements show that even a small increase in the out-of-plane lattice constant of less than 1% can shift the metal-insulator transition and Curie temperatures by more than 100 °C. Unlike conventional epitaxy-based strain tuning methods which are constrained not only by the Poisson effect but by the limited set of available substrates, the present study shows that strain can be independently and continuously controlled along a single axis. This permits novel control over orbital populations through Jahn-Teller effects, as shown by Monte Carlo simulations on a double-exchange model. The ability to reversibly control a single lattice parameter substantially broadens the phase space for experimental exploration of predictive models and leads to new possibilities for control over materials' functional properties.

Differentiating Ferroelectric and Nonferroelectric Electromechanical Effects with Scanning Probe Microscopy.

Ferroelectricity in functional materials remains one of the most fascinating areas of modern science in the past several decades. In the last several years, the rapid development of piezoresponse force microscopy (PFM) and spectroscopy revealed the presence of electromechanical hysteresis loops and bias-induced remnant polar states in a broad variety of materials including many inorganic oxides, polymers, and biosystems. In many cases, this behavior was interpreted as the ample evidence for ferroelectric nature of the system. Here, we systematically analyze PFM responses on ferroelectric and nonferroelectric materials and demonstrate that mechanisms unrelated to ferroelectricity can induce ferroelectric-like characteristics through charge injection and electrostatic forces on the tip. We will focus on similarities and differences in various PFM measurement characteristics to provide an experimental guideline to differentiate between ferroelectric material properties and charge injection. In the end, we apply the developed measurement protocols to an unknown ferroelectric material.

Ferroelectric 180° domain wall motion controlled by biaxial strain.

180° domain wall motion in a tetragonal ferroelectric oxide is accelerated by an order of magnitude using in situ strain in a force microscope. Single-domain PbZr0.2 Ti0.8 O3 films on piezoelectric (001)-oriented 0.72PbMg1/3 Nb2/3 O3 -0.28PbTiO3 substrates allow for direct investigation of strain-dependent domain dynamics. The strain effect depends on the sign of applied field through strain-dependent electrode built-in potentials and a suggested charging of tilted walls.