Mapping Orthorhombic Domains with Geometrical Phase Analysis in Rare-Earth Nickelate Heterostructures

Most perovskite oxides belong to the Pbnm space group, composed by an anisotropic unit cell, A-site antipolar displacements and oxygen octahedral tilts. Mapping the orientation of the orthorhombic unit cell in epitaxial heterostructures that consist of at least one Pbnm compound is often required to understand and control the different degrees of coupling established at their coherent interfaces and, therefore, their resulting physical properties. However, retrieving this information from the strain maps generated with high-resolution scanning transmission electron microscopy can be challenging, because the three pseudocubic lattice parameters are very similar in these systems. Here, we present a novel methodology for mapping the crystallographic orientation in Pbnm systems. It makes use of the geometrical phase analysis algorithm, as applied to aberration-corrected scanning transition electron microscopy images, but in an unconventional way. The method is fast and robust, giving real-space maps of the lattice orientations in Pbnm systems, from both cross-sectional and plan-view geometries and across large fields of view. As an example, we apply our methodology to rare-earth nickelate heterostructures, in order to investigate how the crystallographic orientation of these films depends on various structural constraints that are imposed by the underlying single crystal substrates. We observe that the resulting domain distributions and associated defect landscapes mainly depend on a competition between the epitaxial compressive/tensile and shear strains, together with the matching of atomic displacements at the substrate/film interface. The results point towards strategies for controlling these characteristics by appropriate substrate choice.Comment: 32 pages, 5 figures, 2 table

Anomalous T-dependence of phonon lifetimes in metallic VO2

We investigate phonon lifetimes in VO2 single crystals. We do so in the metallic state above the metal-insulator transition (MIT), where strong structural fluctuations are known to take place. By combining inelastic X-ray scattering and Raman spectroscopy, we track the temperature dependence of several acoustic and optical phonon modes up to 1000 K. Contrary to what is commonly observed, we find that phonon lifetimes decrease with decreasing temperature. Our results show that pre-transitional fluctuations in the metallic state give rise to strong electron-phonon scattering that onsets hundreds of degrees above the transition and increases as the MIT is approached. Notably, this effect is not limited to specific points of reciprocal space that could be associated with the structural transition

Electronic coupling of metal-to-insulator transitions in nickelate-based heterostructures

AbstractRaw resistance and x-ray diffraction data related to the Advanced Electronic Material paper titled "Electronic coupling of metal-to-insulator transitions in nickelate-based heterostructures" (2023

Stress Analysis and Q-Factor of Free-Standing (La,Sr)MnO3 Oxide Resonators

High-sensitivity nanomechanical sensors are mostly based on silicon technology and related materials. The use of functional materials, such as complex oxides having strong interplay between structural, electronic, and magnetic properties, may open possibilities for developing new mechanical transduction schemes and for further enhancement of the device performances. The integration of these materials into micro/nano-electro-mechanical systems (MEMS/NEMS) is still at its very beginning and critical basic aspects related to the stress state and the quality factors of mechanical resonators made from epitaxial oxide thin films need to be investigated. Here, suspended micro-bridges are realized from single-crystal thin films of (La-0.7,Sr-0.3)MnO3 (LSMO), a prototypical complex oxide showing ferromagnetic ground state at room temperature. These devices are characterized in terms of resonance frequency, stress state, and Q-factor. LSMO resonators are highly stressed, with a maximum value of approximate to 260 MPa. The temperature dependence of their mechanical resonance is discussed considering both thermal strain and the temperature-dependent Young's modulus. The measured Q-factors reach few tens of thousands at room temperature, with indications of further improvements by optimizing the fabrication protocols. These results demonstrate that complex oxides are suitable to realize high Q-factor mechanical resonators, paving the way toward the development of full-oxide MEMS/NEMS sensors

Mapping orthorhombic domains with geometrical phase analysis in rare-earth nickelate heterostructures

Most perovskite oxides belong to the Pbnm space group, composed of an anisotropic unit cell, A-site antipolar displacements, and oxygen octahedral tilts. Mapping the orientation of the orthorhombic unit cell in epitaxial heterostructures that consist of at least one Pbnm compound is often needed for understanding and controlling the different degrees of coupling established at their coherent interfaces and, therefore, their resulting physical properties. However, retrieving this information from the strain maps generated with high-resolution scanning transmission electron microscopy can be challenging, because the three pseudocubic lattice parameters are very similar in these systems. Here, we present a novel methodology for mapping the crystallographic orientation in Pbnm systems. It makes use of the geometrical phase analysis algorithm, as applied to aberration-corrected scanning transition electron microscopy images, but in an unconventional way. The method is fast and robust, giving real-space maps of the lattice orientations in Pbnm systems, from both cross section and plan-view geometries, and across large fields of view. As an example, we apply our methodology to rare-earth nickelate heterostructures, in order to investigate how the crystallographic orientation of these films depends on various structural constraints that are imposed by the underlying single crystal substrates. We observe that the resulting domain distributions and associated defect landscapes mainly depend on a competition between the epitaxial compressive/tensile and shear strains, together with the matching of atomic displacements at the substrate/film interface. The results point toward strategies for controlling these characteristics by appropriate substrate choice

Structural study of nickelate based heterostructures

Heterostructures consisting of SmNiO3 and NdNiO3 alternating layers with additional LaAlO3 spacer layers were grown and fully characterized by means of x-ray diffraction, atomic force microscopy, and scanning transmission electron microscopy. A change in the orientation of the orthorhombic long-axis of the nickelate layers is observed when a single unit cell of LaAlO3 is inserted between SmNiO3 and NdNiO3, in agreement with density functional theory calculations. At the same time, the structure of the ultra-thin rhombohedral LaAlO3 layers is affected by their proximity to orthorhombic nickelate layers, with both scanning transmission electron microscopy studies and density functional theory calculations revealing a weak antipolar motion of the La-cation in the LaAlO3 layers that is not present in the bulk rhombohedral structure of this compound.</p

Valence-Ordered Thin-Film Nickelate with Tricomponent Nickel Coordination Prepared by Topochemical Reduction

International audienceThe metal-hydride-based "topochemical reduc-tion" process has produced several thermodynamically unstable phases across various transition metal oxide series with unusual crystal structures and nontrivial ground states. Here, by such an oxygen (de-)intercalation method we synthesis a samarium nickelate with ordered nickel valences associated with tri-component coordination configurations. This structure, with a formula of Sm 9 Ni 9 O 22 as revealed by four-dimensional scanning transmission electron microscopy (4D-STEM), emerges from the intricate planes of {303} pc ordered apical oxygen vacancies. X-ray spectroscopy measurements and ab initio calculations show the coexistence of square planar, pyramidal, and octahedral Ni sites with mono-, bi-, and tri-valences. It leads to an intense orbital polarization, charge-ordering, and a ground state with a strong electron localization marked by the disappearance of ligand-hole configuration at low temperature. This nickelate compound provides another example of previously inaccessible materials enabled by topotactic transformations and presents an interesting platform where mixed Ni valence can give rise to exotic phenomena

Emergent electronic landscapes in a novel valence-ordered nickelate with tri-component nickel coordination

The metal-hydride-based topochemical reduction process has produced novel thermodynamically unstable phases across various transition metal oxide series with unusual crystal structures and non-trivial ground states. Here, by such an oxygen (de-) intercalation method we synthesis a novel samarium nickelate with ordered nickel valences associated with tri-component coordination configurations. This structure, with a formula of Sm$_{9}$Ni$_{9}$O$_{22}$ as revealed by four-dimensional scanning transmission electron microscopy, emerges from the intricate planes of {303}$_{\text{pc}}$ ordered apical oxygen vacancies. X-ray spectroscopy measurements and ab-initio calculations show the coexistence of square-planar, pyramidal and octahedral Ni sites with mono-, bi- and tri-valences. It leads to an intense orbital polarization, charge-ordering, and a ground state with a strong electron localization marked by the disappearance of ligand-hole configuration at low-temperature. This new nickelate compound provides another example of previously inaccessible materials enabled by topotactic transformations and presents a unique platform where mixed Ni valence can give rise to exotic phenomena