Eun Ju Moon

Effect of interfacial octahedral behavior in ultrathin manganite films.

We investigate structural coupling of the MnO6 octahedra across a film/substrate interface and the resultant changes of the physical properties of ultrathin La2/3Sr1/3MnO3 (LSMO) films. In order to isolate the effect of interfacial MnO6 octahedral behavior from that of epitaxial strain, LSMO films are grown on substrates with different symmetry and similar lattice parameters. Ultrathin LSMO films show an increased magnetization and electrical conductivity on cubic (LaAlO3)0.3(Sr2AlTaO6)0.7 (LSAT) compared to those grown on orthorhombic NdGaO3 (NGO) substrates, an effect that subsides as the thickness of the films is increased. This study demonstrates that interfacial structural coupling can play a critical role in the functional properties of oxide heterostructures.

Experimental and theoretical characterization of ordered MAX phases Mo2TiAlC2 and Mo2Ti2AlC3

Herein, we report on the phase stabilities and crystal structures of two newly discovered ordered, quaternary MAX phases—Mo2TiAlC2 and Mo2Ti2AlC3—synthesized by mixing and heating different elemental powder mixtures of mMo:(3-m)Ti:1.1Al:2C with 1.5 ≤ m ≤ 2.2 and 2Mo: 2Ti:1.1Al:2.7C to 1600 °C for 4 h under Ar flow. In general, for m ≥ 2 an ordered 312 phase, (Mo2Ti)AlC2, was the majority phase; for m < 2, an ordered 413 phase (Mo2Ti2)AlC3, was the major product. The actual chemistries determined from X-ray photoelectron spectroscopy (XPS) are Mo2TiAlC1.7 and Mo2Ti1.9Al0.9C2.5, respectively. High resolution scanning transmission microscopy, XPS and Rietveld analysis of powder X-ray diffraction confirmed the general ordered stacking sequence to be Mo-Ti-Mo-Al-Mo-Ti-Mo for Mo2TiAlC2 and Mo-Ti-Ti-Mo-Al-Mo-Ti-Ti-Mo for Mo2Ti2AlC3, with the carbon atoms occupying the octahedral sites between the transition metal layers. Consistent with the experimental results, the theoretical calculations clearly show that M l...

Towards 3D Mapping of BO6 Octahedron Rotations at Perovskite Heterointerfaces, Unit Cell by Unit Cell

The rich functionalities in the ABO3 perovskite oxides originate, at least in part, from the ability of the corner-connected BO6 octahedral network to host a large variety of cations through distortions and rotations. Characterizing these rotations, which have significant impact on both fundamental aspects of materials behavior and possible applications, remains a major challenge at heterointerfaces. In this work, we have developed a unique method to investigate BO6 rotation patterns in complex oxides ABO3 with unit cell resolution at heterointerfaces, where novel properties often emerge. Our method involves column shape analysis in ABF-STEM images of the ABO3 heterointerfaces taken in specific orientations. The rotating phase of BO6 octahedra can be identified for all three spatial dimensions without the need of case-by-case simulation. In several common rotation systems, quantitative measurements of all three rotation angles are now possible. Using this method, we examined interfaces between perovskites with distinct tilt systems as well as interfaces between tilted and untilted perovskites, identifying an unusual coupling behavior at the CaTiO3/LSAT interface. We believe this method will significantly improve our knowledge of complex oxide heterointerfaces.

Spatial control of functional properties via octahedral modulations in complex oxide superlattices

Control of atomic structure, namely the topology of the corner-connected metal-oxygen octahedra, has emerged as an important route to tune the functional properties at oxide interfaces. Here we investigate isovalent manganite superlattices (SLs), [(La(0.7)Sr(0.3)MnO(3))n/(Eu(0.7)Sr(0.3)MnO(3))n] × m, as a route to spatial control over electronic bandwidth and ferromagnetism through the creation of octahedral superstructures. Electron energy loss spectroscopy confirms a uniform Mn valence state throughout the SLs. In contrast, the presence of modulations of the MnO(6) octahedral rotations along the growth direction commensurate with the SL period is revealed by scanning transmission electron microscopy and X-ray diffraction. We show that the Curie temperatures of the constituent materials can be systematically engineered via the octahedral superstructures leading to a modulated magnetization in samples where the SL period is larger than the interfacial octahedral coupling length scale, whereas a single magnetic transition is observed in the short-period SLs.

Fluorination of Epitaxial Oxides: Synthesis of Perovskite Oxyfluoride Thin Films

While the synthesis of ABO3 perovskite films has enabled new strategies to control the functionality of this material class, the chemistries that have been realized in thin film form constitute only a fraction of those accessible to bulk chemists. Here, we report the synthesis of oxyfluoride films, where the incorporation of F may provide a new means to tune physical properties in thin films by modifying electronic structure. Fluorination is achieved by spin coating a poly(vinylidene fluoride) (PVDF) solution onto oxygen-deficient films. The film/polymer bilayer is then annealed, promoting the diffusion of F into the film. We have used this method to synthesize SrFeO(3-α)Fγ films, as confirmed by X-ray photoemission spectroscopy and X-ray absorption spectroscopy.

Solid Solubility and Magnetism upon Mn Incorporation in the Bulk Ternary Carbides Cr2AlC and Cr2GaC

Herein, we report on the bulk synthesis of (Cr 1−xMn x)2AlC and (Cr1−yMny)2GaC MAX phases. Scanning electron and transmission electron microscopy, in combination with energy-dispersive X-ray spectroscopy performed locally on MAX phase grains, revealed x and y to be 0.06 (3 at%) and 0.3 (15 at%), respectively. The introduction of Mn into the structure did not result in appreciable changes in the c-lattice constants. Vibrating sample magnetometry measurements suggest that bulk (Cr0.7Mn0.3)2GaC may be magnetic.

Electronic phase diagram of epitaxial La1−xSrxFeO3 films

The electronic phase diagram of epitaxial La1−xSrxFeO3 films is presented. The films were grown on SrTiO3 using molecular beam epitaxy with post-growth annealing to minimize oxygen vacancies. Insulating behavior is observed from x = 0–0.9, with metallic conduction only present for x = 1.0. While the La-rich compounds exhibit polaron conduction over all temperatures measured, the Sr-rich films exhibit an electronic phase transition within the compositional window of x = 0.49–0.9 as revealed by temperature-dependent resistivity measurements. The transition temperatures are found to decrease with increasing Sr content. The constructed phase diagram is discussed in the context of other 3d eg perovskite systems including manganites and cobaltites.

Polar Oxides without Inversion Symmetry through Vacancy and Chemical Order

One synthetic modality for materials discovery proceeds by forming mixtures of two or more compounds. In transition metal oxides (TMOs), chemical substitution often obeys Vegards principle, and the resulting structure and properties of the derived phase follow from its components. A change in the assembly of the components into a digital nanostructure, however, can stabilize new polymorphs and properties not observed in the constituents. Here we formulate and demonstrate a crystal-chemistry design approach for realizing digital TMOs without inversion symmetry by combining two centrosymmetric compounds, utilizing periodic anion-vacancy order to generate multiple polyhedra that together with cation order produce a polar structure. We next apply this strategy to two brownmillerite-structured TMOs known to display centrosymmetric crystal structures in their bulk, Ca2Fe2O5 and Sr2Fe2O5. We then realize epitaxial (SrFeO2.5)1/(CaFeO2.5)1 thin film superlattices possessing both anion-vacancy order and Sr and Ca chemical order at the subnanometer scale, confirmed through synchrotron-based diffraction and aberration corrected electron microscopy. Through a detailed symmetry analysis and density functional theory calculations, we show that A-site cation ordering lifts inversion symmetry in the superlattice and produces a polar compound. Our results demonstrate how control of anion and cation order at the nanoscale can be utilized to produce acentric structures markedly different than their constituents and open a path toward novel structure-based property design.

Epitaxial growth of (111)-oriented LaAlO3/LaNiO3 ultra-thin superlattices

The epitaxial stabilization of a single layer or superlattice structures composed of complex oxide materials on polar (111) surfaces is severely burdened by the reconstructions at the interface that commonly arise to neutralize the polarity. We report on the synthesis of high quality LaNiO3/mLaAlO3 pseudo cubic (111) superlattices on polar (111)-oriented LaAlO3, the proposed complex oxide candidate for a topological insulating behavior. Comprehensive X-Ray diffraction measurements, reflection high energy electron diffraction, and element specific resonant X-ray absorption spectroscopy affirm their high structural and chemical quality. The study offers an opportunity to fabricate interesting interface and topology controlled (111)-oriented superlattices based on ortho-nickelates.

Field-effect diode based on electron-induced Mott transition in NdNiO3

We studied an electron-induced metal-insulator transition in a two-terminal device based on oxide NdNiO3. In our device, the NdNiO3 is electrostatically doped by the voltage applied between the terminals, resulting in an asymmetric conductivity with respect to the bias polarity. The asymmetry is temperature-dependent and is most significant near the metal-insulator transition. The I-V characteristics exhibit a strong dependence both on the thermal history and the history of the applied voltage bias. Our two-terminal device represents a simple and efficient route for studies of the effect of electron doping on the metal-insulator transition.