Zuhuang Chen

Enhancement of Ferroelectric Curie Temperature in BaTiO3 Films via Strain‐Induced Defect Dipole Alignment

The combination of epitaxial strain and defect engineering facilitates the tuning of the transition temperature of BaTiO3 to >800 °C. Advances in thin-film deposition enable the utilization of both the electric and elastic dipoles of defects to extend the epitaxial strain to new levels, inducing unprecedented functionality and temperature stability in ferroelectrics.

New modalities of strain-control of ferroelectric thin films.

Ferroelectrics, with their spontaneous switchable electric polarization and strong coupling between their electrical, mechanical, thermal, and optical responses, provide functionalities crucial for a diverse range of applications. Over the past decade, there has been significant progress in epitaxial strain engineering of oxide ferroelectric thin films to control and enhance the nature of ferroelectric order, alter ferroelectric susceptibilities, and to create new modes of response which can be harnessed for various applications. This review aims to cover some of the most important discoveries in strain engineering over the past decade and highlight some of the new and emerging approaches for strain control of ferroelectrics. We discuss how these new approaches to strain engineering provide promising routes to control and decouple ferroelectric susceptibilities and create new modes of response not possible in the confines of conventional strain engineering. To conclude, we will provide an overview and prospectus of these new and interesting modalities of strain engineering helping to accelerate their widespread development and implementation in future functional devices.

Effects of Nonequilibrium Growth, Nonstoichiometry, and Film Orientation on the Metal-to-Insulator Transition in NdNiO3 Thin Films

Next-generation devices will rely on exotic functional properties not found in traditional systems. One class of materials of particular interest for applications are those possessing metal-to-insulator transitions (MITs). In this work, we probe the relationship between variations in the growth process, subsequent variations in cation stoichiometry, and the MIT in NdNiO3 thin films. Slight variations in the growth conditions, in particular the laser fluence, during pulsed-laser deposition growth of NdNiO3 produces films that are both single-phase and coherently strained to a range of substrates despite possessing as much as 15% Nd-excess. Subsequent study of the temperature-dependence of the electronic transport reveals dramatic changes in both the onset and magnitude of the resistivity change at the MIT with increasing cation nonstoichiometry giving rise to a decrease (and ultimately a suppression) of the transition and the magnitude of the resistivity change. From there, the electronic transport of nearly ideal NdNiO3 thin films are studied as a function of epitaxial strain, thickness, and orientation. Overall, transitioning from tensile to compressive strain results in a systematic reduction of the onset and magnitude of the resistivity change across the MIT, thinner films are found to possess sharper MITs with larger changes in the resistivity at the transition, and (001)-oriented films exhibit sharper and larger MITs as compared to (110)- and (111)-oriented films as a result of highly anisotropic in-plane transport in the latter.

180° Ferroelectric Stripe Nanodomains in BiFeO3 Thin Films.

There is growing evidence that domain walls in ferroics can possess emergent properties that are absent in the bulk. For example, 180° ferroelectric domain walls in the ferroelectric-antiferromagnetic BiFeO3 are particularly interesting because they have been predicted to possess a range of intriguing behaviors, including electronic conduction and enhanced magnetization. To date, however, ordered arrays of such domain structures have not been reported. Here, we report the observation of 180° stripe nanodomains in (110)-oriented BiFeO3 thin films grown on orthorhombic GdScO3 (010)O substrates and their impact on exchange coupling to metallic ferromagnets. Nanoscale ferroelectric 180° stripe domains with {112̅} domain walls were observed in films <32 nm thick. With increasing film thickness, we observed a domain structure crossover from the depolarization field-driven 180° stripe nanodomains to 71° ferroelastic domains determined by the elastic energy. These 180° domain walls (which are typically cylindrical or meandering in nature due to a lack of strong anisotropy associated with the energy of such walls) are found to be highly ordered. Additional studies of Co0.9Fe0.1/BiFeO3 heterostructures reveal exchange bias and exchange enhancement in heterostructures based on BiFeO3 with 180° domain walls and an absence of exchange bias in heterostructures based on BiFeO3 with 71° domain walls; suggesting that the 180° domain walls could be the possible source for pinned uncompensated spins that give rise to exchange bias. This is further confirmed by X-ray circular magnetic dichroism studies, which demonstrate that films with predominantly 180° domain walls have larger magnetization than those with primarily 71° domain walls. Our results could be useful to extract the structure of domain walls and to explore domain wall functionalities in BiFeO3.

Enhanced Electrical Resistivity and Properties via Ion Bombardment of Ferroelectric Thin Films.

A novel approach to on-demand improvement of electronic properties in complex-oxide ferroelectrics is demonstrated whereby ion bombardment - commonly used in classic semiconductor materials - is applied to the PbTiO3 system. The result is deterministic reduction in leakage currents by 5 orders of magnitude, improved ferroelectric switching, and unprecedented insights into the nature of defects and intergap state evolution in these materials.

Atomic-scale control of magnetic anisotropy via novel spin-orbit coupling effect in La2/3Sr1/3MnO3/SrIrO3 superlattices.

Significance Interfaces of transition-metal oxides (TMOs) offer a fertile platform to uncover emergent states, which has been extensively explored in 3d TMOs with strong electron correlations. Recently research on 5d TMOs with pronounced spin–orbit coupling (SOC) is flourishing due to the emergence of new topological states and potential application in spintronics. Interfaces between 3d and 5d TMOs provide a unique test bed to combine the merits of these two fundamental interactions. However, so far research is limited. Here we present results on one model system comprising the ferromagnet La2/3Sr1/3MnO3 and the strong SOC paramagnet SrIrO3. We observe a manipulation of the magnetic anisotropy by tuning the SrIrO3 dimensionality, which is accompanied by a novel SOC state in SrIrO3. Magnetic anisotropy (MA) is one of the most important material properties for modern spintronic devices. Conventional manipulation of the intrinsic MA, i.e., magnetocrystalline anisotropy (MCA), typically depends upon crystal symmetry. Extrinsic control over the MA is usually achieved by introducing shape anisotropy or exchange bias from another magnetically ordered material. Here we demonstrate a pathway to manipulate MA of 3d transition-metal oxides (TMOs) by digitally inserting nonmagnetic 5d TMOs with pronounced spin–orbit coupling (SOC). High-quality superlattices comprising ferromagnetic La2/3Sr1/3MnO3 (LSMO) and paramagnetic SrIrO3 (SIO) are synthesized with the precise control of thickness at the atomic scale. Magnetic easy-axis reorientation is observed by controlling the dimensionality of SIO, mediated through the emergence of a novel spin–orbit state within the nominally paramagnetic SIO.

Self-Assembled, Nanostructured, Tunable Metamaterials via Spinodal Decomposition.

Self-assembly via nanoscale phase separation offers an elegant route to fabricate nanocomposites with physical properties unattainable in single-component systems. One important class of nanocomposites are optical metamaterials which exhibit exotic properties and lead to opportunities for agile control of light propagation. Such metamaterials are typically fabricated via expensive and hard-to-scale top-down processes requiring precise integration of dissimilar materials. In turn, there is a need for alternative, more efficient routes to fabricate large-scale metamaterials for practical applications with deep-subwavelength resolution. Here, we demonstrate a bottom-up approach to fabricate scalable nanostructured metamaterials via spinodal decomposition. To demonstrate the potential of such an approach, we leverage the innate spinodal decomposition of the VO2-TiO2 system, the metal-to-insulator transition in VO2, and thin-film epitaxy, to produce self-organized nanostructures with coherent interfaces and a structural unit cell down to 15 nm (tunable between horizontally and vertically aligned lamellae) wherein the iso-frequency surface is temperature-tunable from elliptic to hyperbolic dispersion producing metamaterial behavior. These results provide an efficient route for the fabrication of nanostructured metamaterials and other nanocomposites for desired functionalities.

Interfacial Octahedral Rotation Mismatch Control of the Symmetry and Properties of SrRuO3.

Epitaxial strain can be used to tune the properties of complex oxides with perovskite structure. Beyond just lattice mismatch, the use of octahedral rotation mismatch at heterointerfaces could also provide an effective route to manipulate material properties. Here, we examine the evolution of the structural motif (i.e., lattice parameters, symmetry, and octahedral rotations) of SrRuO3 films grown on substrates engineered to have the same lattice parameters, but different octahedral rotations. SrRuO3 films grown on SrTiO3 (001) (no octahedral rotations) and GdScO3-buffered SrTiO3 (001) (with octahedral rotations) substrates are found to exhibit monoclinic and tetragonal symmetry, respectively. Electrical transport and magnetic measurements reveal that the tetragonal films exhibit higher resistivity, lower magnetic Curie temperatures, and more isotropic magnetism as compared to those with monoclinic structure. Synchrotron-based quantification of the octahedral rotation network reveals that the tilting pattern in both film variants is the same (albeit with slightly different magnitudes of in-plane rotation angles). The abnormal rotation pattern observed in tetragonal SrRuO3 indicates a possible decoupling between the internal octahedral rotation and lattice symmetry, which could provide new opportunities to engineer thin-film structure and properties.

Electron Accumulation and Emergent Magnetism in LaMnO3/SrTiO3 Heterostructures

Emergent phenomena at polar-nonpolar oxide interfaces have been studied intensely in pursuit of next-generation oxide electronics and spintronics. Here we report the disentanglement of critical thicknesses for electron reconstruction and the emergence of ferromagnetism in polar-mismatched LaMnO_{3}/SrTiO_{3} (001) heterostructures. Using a combination of element-specific x-ray absorption spectroscopy and dichroism, and first-principles calculations, interfacial electron accumulation, and ferromagnetism have been observed within the polar, antiferromagnetic insulator LaMnO_{3}. Our results show that the critical thickness for the onset of electron accumulation is as thin as 2 unit cells (UC), significantly thinner than the observed critical thickness for ferromagnetism of 5 UC. The absence of ferromagnetism below 5 UC is likely induced by electron overaccumulation. In turn, by controlling the doping of the LaMnO_{3}, we are able to neutralize the excessive electrons from the polar mismatch in ultrathin LaMnO_{3} films and thus enable ferromagnetism in films as thin as 3 UC, extending the limits of our ability to synthesize and tailor emergent phenomena at interfaces and demonstrating manipulation of the electronic and magnetic structures of materials at the shortest length scales.

Epitaxial growth of intermetallic MnPt films on oxides and large exchange bias

High-quality epitaxial growth of inter-metallic MnPt films on oxides is achieved, with potential for multiferroic heterostructure applications. Antisite-stabilized spin-flipping induces ferromagnetism in MnPt films, although it is robustly antiferromagnetic in bulk. Moreover, highly ordered antiferromagnetic MnPt films exhibit superiorly large exchange coupling with a ferromagnetic layer.