Ricardo Egoavil

Extreme mobility enhancement of two-dimensional electron gases at oxide interfaces by charge-transfer-induced modulation doping.

Two-dimensional electron gases (2DEGs) formed at the interface of insulating complex oxides promise the development of all-oxide electronic devices. These 2DEGs involve many-body interactions that give rise to a variety of physical phenomena such as superconductivity, magnetism, tunable metal-insulator transitions and phase separation. Increasing the mobility of the 2DEG, however, remains a major challenge. Here, we show that the electron mobility is enhanced by more than two orders of magnitude by inserting a single-unit-cell insulating layer of polar La(1-x)Sr(x)MnO3 (x = 0, 1/8, and 1/3) at the interface between disordered LaAlO3 and crystalline SrTiO3 produced at room temperature. Resonant X-ray spectroscopy and transmission electron microscopy show that the manganite layer undergoes unambiguous electronic reconstruction, leading to modulation doping of such atomically engineered complex oxide heterointerfaces. At low temperatures, the modulation-doped 2DEG exhibits Shubnikov-de Haas oscillations and fingerprints of the quantum Hall effect, demonstrating unprecedented high mobility and low electron density.

Perovskite-like Mn2O3: a path to new manganites.

Among complex oxides, perovskite-based manganites play a special role in science and technology. They demonstrate colossal magnetoresistance, and can be employed as memory and resistive switching elements or multiferroics. The perovskite structure ABO3 has two different cation sites: B-sites that are octahedrally coordinated by oxygen, and cuboctahedrally-coordinated (often heavily distorted) Asites. The magnetic and transport properties of perovskite manganites are largely determined by the Mn O Mn interactions in the perovskite framework of corner-sharing MnO6 octahedra. Although the A cations do not directly participate in these interactions, they control the Mn valence and the geometry of the Mn O Mn bonds. Complex phenomena, such as charge and orbital ordering, often accompany chemical substitutions on the A-site. Requirements on formal charge and ionic radius are usually different for cations adopting theA or B positions and prevent A/B mixing. Small and often highly charged transition-metal B-cations are unfavorable for the large 12coordinated A-site. Partial filling of the A-position with transition metals is, nevertheless, possible in a unique class of A-site ordered perovskites AA’3B4O12 (where A= alkali, alkali-earth, rare-earth, Pb, or Bi cations, A’=Cu or Mn, and B= transition metals, Ga, Ge, Sb, or Sn). A key ingredient of such compounds is the A’ cation that should be prone to a first-order Jahn–Teller effect (Cu or Mn). An oxygen environment suitable for such transition-metal cations at the A’ position is created by the aaa octahedral tilt system (in Glazer s notation) with a notably large magnitude of the tilt (for example, in CaCu3Ti4O12 the Ti O Ti bond angle is only 140.78). The tilt creates a square-planar anion coordination, favorable for Jahn–Teller-active A’ cations. The ap= ffiffiffi

Preventing the Reconstruction of the Polar Discontinuity at Oxide Heterointerfaces

When comparing a set of La0.67Sr0.33MnO3 (LSMO) samples, the Curie temperature (TC) of the samples is an important figure of merit for the sample quality. Therefore, a reliable method to determine TC is required. Here, a method based on the analysis of the magnetization loops is proposed.

Chemical insight into electroforming of resistive switching manganite heterostructures

We have investigated the role of the electroforming process in the establishment of resistive switching behaviour for Pt/Ti/Pr0.5Ca0.5MnO3/SrRuO3 layered heterostructures (Pt/Ti/PCMO/SRO) acting as non-volatile Resistance Random Access Memories (RRAMs). Electron spectroscopy measurements demonstrate that the higher resistance state resulting from electroforming of as-prepared devices is strictly correlated with the oxidation of the top electrode Ti layer through field-induced electromigration of oxygen ions. Conversely, PCMO exhibits oxygen depletion and downward change of the chemical potential for both resistive states. Impedance spectroscopy analysis, supported by the detailed knowledge of these effects, provides an accurate model description of the device resistive behaviour. The main contributions to the change of resistance from the as-prepared (low resistance) to the electroformed (high resistance) states are respectively due to reduced PCMO at the boundary with the Ti electrode and to the formation of an anisotropic n-p junction between the Ti and the PCMO layers.

Pulsed laser deposition of SrTiO3 on a H-terminated Si substrate

Interfacing oxides with silicon is a long-standing problem related to the integration of multifunctional oxides with semiconductor devices and the replacement of SiO2 with high-k gate oxides. In our study, pulsed laser deposition was used to prepare a SrTiO3 (STO) thin film on a H-terminated Si substrate. The main purpose of our work was to verify the ability of H-termination against the oxidation of Si during the PLD process and to analyze the resulting interfaces. In the first part of the study, the STO was deposited directly on the Si, leading to the formation of a preferentially textured STO film with a (100) orientation. In the second part, SrO was used as a buffer layer, which enabled the partial epitaxial growth of STO with STO(110)‖Si(100) and STO[001]‖Si[001]. The change in the growth direction induced by the application of a SrO buffer was governed by the formation of a SrO(111) intermediate layer and subsequently by the minimization of the lattice misfit between the STO and the SrO. Under the investigated conditions, approximately 10 nm thick interfacial layers formed between the STO and the Si due to reactions between the deposited material and the underlying H-terminated Si. In the case of direct STO deposition, SiOx formed at the interface with the silicon, while in the case when SrO was used as a buffer, strontium silicate grew directly on the silicon, which improves the growth quality of the uppermost STO.

Homogeneity and composition of AlInGaN: A multiprobe nanostructure study

The electronic properties of quaternary AlInGaN devices significantly depend on the homogeneity of the alloy. The identification of compositional fluctuations or verification of random-alloy distribution is hence of grave importance. Here, a comprehensive multiprobe study of composition and compositional homogeneity is presented, investigating AlInGaN layers with indium concentrations ranging from 0 to 17at% and aluminium concentrations between 0 and 39 at% employing high-angle annular dark field scanning electron microscopy (HAADF STEM), energy dispersive X-ray spectroscopy (EDX) and atom probe tomography (APT). EDX mappings reveal distributions of local concentrations which are in good agreement with random alloy atomic distributions. This was hence investigated with HAADF STEM by comparison with theoretical random alloy expectations using statistical tests. To validate the performance of these tests, HAADF STEM image simulations were carried out for the case of a random-alloy distribution of atoms and for the case of In-rich clusters with nanometer dimensions. The investigated samples, which were grown by metal-organic vapor phase epitaxy (MOVPE), were thereby found to be homogeneous on this nanometer scale. Analysis of reconstructions obtained from APT measurements yielded matching results. Though HAADF STEM only allows for the reduction of possible combinations of indium and aluminium concentrations to the proximity of isolines in the two-dimensional composition space. The observed ranges of composition are in good agreement with the EDX and APT results within the respective precisions.

Interlayer structure in YBCO-coated conductors prepared by chemical solution deposition

The functionality of YBa2Cu3O7 (YBCO)-coated conductor technology depends on the reliability and microstructural properties of a given tape or wire architecture. Particularly, the interface to the metal tape is of interest since it determines the adhesion, mechanical stability of the film and thermal contact of the film to the substrate. A trifluoroacetate (TFA)—metal organic deposition (MOD) prepared YBCO film deposited on a chemical solution-derived buffer layer architecture based on CeO2=La2Zr2O7 and grown on a flexible Ni5 at.%W substrate with af100gh001i biaxial texture was investigated. The YBCO film had a thickness was 440 nm and a jc of 1:02 MA cm 2 was determined at 77 K and zero external field. We present a sub-nanoscale analysis of a fully processed solution-derived YBCO-coated conductor by aberration-corrected scanning transmission electron microscopy (STEM) combined with electron energy-loss spectroscopy (EELS). For the first time, structural and chemical analysis of the valence has been carried out on the sub-nm scale. Intermixing of Ni, La, Ce, O and Ba takes place at these interfaces and gives rise to nanometer-sized interlayers which are a by-product of the sequential annealing process. Two distinct interfacial regions were analyzed in detail: (i) the YBCO=CeO2=La2Zr2O7 region (10 nm interlayer) and (ii) the La2Zr2O7=Ni‐5 at.%W substrate interface region (20 nm NiO). This is of particular significance for the functionality of these YBCO-coated conductor architectures grown by chemical solution deposition. (Some figures may appear in colour only in the online journal)

Site-specific mapping of transition metal oxygen coordination in complex oxides

We demonstrate site-specific mapping of the oxygen coordination number for transition metals in complex oxides using atomically resolved electron energy-loss spectroscopy in an aberration-corrected scanning transmission electron microscope. Pb2Sr2Bi2Fe6O16 contains iron with a constant Fe3+ valency in both octahedral and tetragonal pyramidal coordination and is selected to demonstrate the principle of site-specific coordination mapping. Analysis of the site-specific Fe-L2,3 data reveals distinct variations in the fine structure that are attributed to Fe in a six-fold (octahedron) or five-fold (distorted tetragonal pyramid) oxygen coordination. Using these variations, atomic resolution coordination maps are generated that are in excellent agreement with simulations.

Mapping electronic reconstruction at the metal-insulator interface in LaVO3/SrVO3 heterostructures

A \ce{(LaVO_3)_6/(SrVO_3)_3} superlattice is studied with a combination of sub-{\AA} resolved scanning transmission electron microscopy and monochromated electron energy-loss spectroscopy. The V oxidation state is mapped with atomic spatial resolution enabling to investigate electronic reconstruction at the \ce{LaVO_3}/\ce{SrVO_3} interfaces. Surprisingly, asymmetric charge distribution is found at adjacent chemically symmetric interfaces. The local structure is proposed and simulated with double channeling calculation which agrees qualitatively with our experiment. We demonstrate that local strain asymmetry is the likely cause of the electronic asymmetry of the interfaces. The electronic reconstruction at the interfaces extends much further than the chemical composition, varying from 0.5 to 1.2 nm. This distance corresponds to the length of charge transfer previously found in the \ce{(LaVO_3)_m}/\ce{(SrVO_3)_n} metal/insulating and the \ce{(LaAlO_3)_m}/\ce{(SrTiO_3)_n} insulating/insulating interfaces.

Atomic resolution mapping of phonon excitations in STEM-EELS experiments

Atomically resolved electron energy-loss spectroscopy experiments are commonplace in modern aberration-corrected transmission electron microscopes. Energy resolution has also been increasing steadily with the continuous improvement of electron monochromators. Electronic excitations however are known to be delocalized due to the long range interaction of the charged accelerated electrons with the electrons in a sample. This has made several scientists question the value of combined high spatial and energy resolution for mapping interband transitions and possibly phonon excitation in crystals. In this paper we demonstrate experimentally that atomic resolution information is indeed available at very low energy losses around 100meV expressed as a modulation of the broadening of the zero loss peak. Careful data analysis allows us to get a glimpse of what are likely phonon excitations with both an energy loss and gain part. These experiments confirm recent theoretical predictions on the strong localization of phonon excitations as opposed to electronic excitations and show that a combination of atomic resolution and recent developments in increased energy resolution will offer great benefit for mapping phonon modes in real space.