Oxygen-assisted Molecular Beam Epitaxy Research Articles

Confinement-Induced Isosymmetric Metal-Insulator Transition in Ultrathin Epitaxial V2O3 Films.

Dimensional confinement has shown to be an effective strategy to tune competing degrees of freedom in complex oxides. Here, we achieved atomic layered growth of trigonal vanadium sesquioxide (V2O3) by means of oxygen-assisted molecular beam epitaxy. This led to a series of high-quality epitaxial ultrathin V2O3 films down to unit cell thickness, enabling the study of the intrinsic electron correlations upon confinement. By electrical and optical measurements, we demonstrate a dimensional confinement-induced metal-insulator transition in these ultrathin films. We shed light on the Mott-Hubbard nature of this transition, revealing a vanishing quasiparticle weight as demonstrated by photoemission spectroscopy. Furthermore, we prove that dimensional confinement acts as an effective out-of-plane stress. This highlights the structural component of correlated oxides in a confined architecture, while opening an avenue to control both in-plane and out-of-plane lattice components by epitaxial strain and confinement, respectively.

Motion of magnetic domain walls and vortices in epitaxial magnetite microstructures

We report on the response of magnetic domains in thin magnetite microstructures to weak external magnetic fields. Magnetite islands were grown by high-temperature oxygen-assisted molecular beam epitaxy on Ru(0001). The islands, micrometric wide and tens of nanometers thick are of high structural quality, each having been grown from a single nucleation center. Their magnetic domain structure is dominated by shape anisotropy, i.e., they present Landau flux-closure domain configurations. The magnetic domains of the in situ grown microstructures have been imaged directly by means of x-ray magnetic circular dichroism in photoemission electron microscopy while applying external, in-plane magnetic fields along different directions. Upon application of an external field the Landau state vortex core experiences a displacement along a direction perpendicular to the excitation field. The behavior of the Landau state under the applied magnetic field is quantified and compared with micromagnetic simulations. The results highlight the bulk-like magnetic properties of the nanometer-thick microstructures, opening the way to their possible use in technological applications.

Effect of Ni substitution on the antiferromagnetic domains of cobalt oxide

We present a spatially resolved X-ray magnetic linear dichroism study of high quality micron-sized mixed nickel-cobalt oxide (NCO) crystals. NixCo1−xO was prepared in-situ by high-temperature oxygen-assisted molecular beam epitaxy on a Ru(0001) single crystal substrate. To check the effect of incorporating Ni into the cobalt oxide films, three different compositions were prepared. The element-specific XMLD measurements reveal strong antiferromagnetic contrast at room temperature and magnetic domains up to one micron in size, reflecting the high structural quality of the NCO islands. By means of vectorial magnetometry, the antiferromagnetic spin axis orientation of the domains was determined with nanometer spatial resolution, and found to depend on the stoichiometry of the prepared crystals.

Stoichiometry driven tuning of physical properties in epitaxial Fe3-xCrxO4 thin films

Tuning magnetic and electronic transport properties in spinel oxides requires a faithful description between chemical composition and cation site-occupation. Here this challenge is addressed using Fe3-xCrxO4 thin films grown by oxygen-assisted molecular-beam epitaxy within a wide range of composition (0.0 ≤ x ≤ 1.2). Spectroscopic measurements (e.g., X-ray magnetic circular dichroism), refined by theoretical simulations (e.g., crystal field multiplet), are performed to establish a quantitative link between chromium content, Fe2+/Fe3+ site-occupation and macroscopic physical properties of the layers. It is found that Fe3-xCrxO4 thin films (i) delay the transition from inverse to normal spinel configuration with increasing chromium content and (ii) promote collinear spin structure, at odds with bulk material. As a result, strong antiferromagnetic interactions are preserved between spins in tetrahedral and octahedral spinel sublattices, so that chromium-rich thin films exhibit Curie temperatures above room temperature and higher magnetization. Electron hopping is also favored by this singular cation distribution and electronic band gap is smaller than expected for these thin films. The cation site-occupation is therefore a key feature to consider for applications of Fe3-xCrxO4 thin films in spintronics and photocatalysis, as it enables manipulation of magnetic properties (Curie temperature and magnetization) and band gap engineering.

Size Effects in the Verwey Transition of Nanometer-Thick Micrometer-Wide Magnetite Crystals.

We have monitored the Verwey transition in micrometer-wide, nanometer-thick magnetite islands on epitaxial Ru films on Al2O3(0001) using Raman spectroscopy. The islands have been grown by high-temperature oxygen-assisted molecular beam epitaxy. Below 100 K and for thicknesses above 20 nm, the Raman spectra correspond to those observed in bulk crystals and high-quality thin films for the sub-Verwey magnetite structure. At room temperature, the width of the cubic phase modes is similar to the best reported for bulk crystals, indicating a similar strength of electron–phonon interaction. The evolution of the Raman spectra upon cooling suggests that for islands thicker than 20 nm, structural changes appear first at temperatures starting at 150 K while the Verwey transition itself takes place at around 115 K. However, islands thinner than 20 nm show very different Raman spectra, indicating that while a transition takes place, the charge order of the ultrathin islands differs markedly from their thicker counterparts.

A real-time XAS PEEM study of the growth of cobalt iron oxide on Ru(0001).

The growth of mixed cobalt-iron oxides on Ru(0001) by high-temperature oxygen-assisted molecular beam epitaxy has been monitored in real time and real space by x-ray absorption photoemission microscopy. The initial composition is a mixed Fe-Co(II) oxide wetting layer, reflecting the ratio of the deposited materials. However, as subsequent growth of three dimensional spinel islands nucleating on this wetting layer takes place, the composition of the oxide in the wetting layer changes as iron is transferred into the spinel islands. The composition of the islands themselves also changes during growth.

Different spin axis orientation and large antiferromagnetic domains in Fe-doped NiO/Ru(0001) epitaxial films.

We present a spatially resolved X-ray magnetic dichroism study of high-quality, in situ grown nickel oxide films. NiO thin films were deposited on a Ru(0001) substrate by high temperature oxygen-assisted molecular beam epitaxy. We found that by adding a small amount of Fe, the growth mode can be modified in order to promote the formation of micron-sized, triangular islands. The morphology, shape, crystal structure and composition are determined by low-energy electron microscopy and diffraction, and synchrotron based X-ray absorption spectromicroscopy. The element specific XMLD measurements reveal strong antiferromagnetic contrast at room temperature and domains with up to micron sizes, reflecting the high structural quality of the islands. By means of vectorial magnetometry, the spin axis orientation was determined with nanometer spatial resolution, and found to depend on the relative orientation of the film and substrate lattices.

Tuning the N\xe9el temperature in an antiferromagnet: the case of NixCo1\u2212xO microstructures

We show that it is possible to tune the Néel temperature of nickel(II)-cobalt(II) oxide films by changing the Ni to Co ratio. We grow single crystalline micrometric triangular islands with tens of nanometers thickness on a Ru(0001) substrate using high temperature oxygen-assisted molecular beam epitaxy. Composition is controlled by adjusting the deposition rates of Co and Ni. The morphology, shape, crystal structure and composition are determined by low-energy electron microscopy and diffraction, and synchrotron-based x-ray absorption spectromicroscopy. The antiferromagnetic order is observed by x-ray magnetic linear dichroism. Antiferromagnetic domains up to micrometer width are observed.

Structure and magnetism of ultrathin nickel-iron oxides grown on Ru(0001) by high-temperature oxygen-assisted molecular beam epitaxy

We demonstrate the preparation of ultrathin Fe-rich nickel ferrite (NFO) islands on a metal substrate. Their nucleation and growth are followed in situ by low-energy electron microscopy (LEEM). A comprehensive characterization is performed combining LEEM for structural characterization and PEEM (PhotoEmission Electron Microscopy) with synchrotron radiation for chemical and magnetic analysis via X-ray Absorption Spectroscopy and X-ray Magnetic Circular Dichroism (XAS-PEEM and XMCD-PEEM, respectively). The growth by oxygen-assisted molecular beam epitaxy takes place in two stages. First, islands with the rocksalt structure nucleate and grow until they completely cover the substrate surface. Later three-dimensional islands of spinel phase grow on top of the wetting layer. Only the spinel islands show ferromagnetic contrast, with the same domains being observed in the Fe and Ni XMCD images. The estimated magnetic moments of Fe and Ni close to the islands surface indicate a possible role of the bi-phase reconstruction. A significant out-of-plane magnetization component was detected by means of XMCD-PEEM vector maps.

An all-perovskite p-n junction based on transparent conducting p-La1−xSrxCrO3 epitaxial layers

Transparent, conducting p-La1−xSrxCrO3 epitaxial layers were deposited on Nb-doped SrTiO3(001) by oxygen-assisted molecular beam epitaxy to form structurally coherent p-n junctions. X-ray photoelectron spectroscopy reveals a type II or “staggered” band alignment, with valence and conduction band offsets of 2.0 eV and 0.9 eV, respectively. Diodes fabricated from these heterojunctions exhibit rectifying behavior, and the I-V characteristics are different from those for traditional semiconductor p-n junctions. A rather large ideality factor is ascribed to the complex nature of the interface.

Collapse of the low temperature insulating state in Cr-doped V2O3 thin films

We have grown epitaxial Cr-doped V2O3 thin films with Cr concentrations between 0% and 20% on (0001)-Al2O3 by oxygen-assisted molecular beam epitaxy. For the highly doped samples (>3%), a regular and monotonous increase of the resistance with decreasing temperature is measured. Strikingly, in the low doping samples (between 1% and 3%), a collapse of the insulating state is observed with a reduction of the low temperature resistivity by up to 5 orders of magnitude. A vacuum annealing at high temperature of the films recovers the low temperature insulating state for doping levels below 3% and increases the room temperature resistivity towards the values of Cr-doped V2O3 single crystals. It is well-know that oxygen excess stabilizes a metallic state in V2O3 single crystals. Hence, we propose that Cr doping promotes oxygen excess in our films during deposition, leading to the collapse of the low temperature insulating state at low Cr concentrations. These results suggest that slightly Cr-doped V2O3 films can be interesting candidates for field effect devices.

Ferromagnetic Resonance Study of Magnetic Anisotropy in Epitaxial Fe<sub>3</sub>O<sub>4</sub> Thin Film

Ferromagnetic resonance (FMR) is used to investigate the magnetic anisotropy of a 25.5 nm thin Fe <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> O <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4</sub> film above and below its Verwey transition temperature (TV). Epitaxial smooth film of Fe <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> O <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4</sub> is deposited by oxygen-assisted molecular beam epitaxy. FMR spectra are recorded using a 9.49 GHz Brucker EMX system from 80 K to room temperature with a magnetic field applied along [100] direction. The resonance field (Hr) and linewidth (AH) are extracted by fitting the FMR line with a Lorentzian function. Temperature dependence of H <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">r</sub> and ΔH shows a transition at T <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">V</sub> . Furthermore, the data of in-plane angular dependence of H <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">r</sub> at 300 and 83 K indicated a change in symmetry from fourfold to twofold below TV, consistent with a transformation of Fe <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> O <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4</sub> from cubic (fourfold) to monoclinic (twofold) structure with its easy axis switching from [110] to [100]. Complex symmetry pattern is found in angular dependence of ΔH below TV, which is attributed to the in-plane twinning of Fe <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> O <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4</sub> lattice.

Structure, magnetic ordering, and spin filtering efficiency of NiFe2O4(111) ultrathin films

NiFe2O4(111) ultrathin films (3–5 nm) have been grown by oxygen-assisted molecular beam epitaxy and integrated as effective spin-filter barriers. Structural and magnetic characterizations have been performed in order to investigate the presence of defects that could limit the spin filtering efficiency. These analyses have revealed the full strain relaxation of the layers with a cationic order in agreement with the inverse spinel structure but also the presence of antiphase boundaries. A spin-polarization up to +25% has been directly measured by the Meservey-Tedrow technique in Pt(111)/NiFe2O4(111)/γ-Al2O3(111)/Al tunnel junctions. The unexpected positive sign and relatively small value of the spin-polarization are discussed, in comparison with predictions and previous indirect tunnelling magnetoresistance measurements.

Initial stages of FeO growth on Ru(0001)

We study how FeO wüstite films on Ru(0001) grow by oxygen-assisted molecular beam epitaxy at elevated temperatures (800–900 K). The nucleation and growth of FeO islands are observed in real time by low-energy electron microscopy (LEEM). When the growth is performed in an oxygen pressure of 10−6 Torr, the islands are of bilayer thickness (Fe–O–Fe–O). In contrast, under a pressure of 10−8 Torr, the islands are a single FeO layer thick. We propose that the film thickness is controlled by the concentration of oxygen adsorbed on the Ru. More specifically, when monolayer growth increases the adsorbed oxygen concentration above a limiting value, its growth is suppressed. Increasing the temperature at a fixed oxygen pressure decreases the density of FeO islands. However, the nucleation density is not a monotonic function of oxygen pressure.

Epitaxial growth and ferrimagnetic behavior of MnFe2O4(111) ultrathin layers for room-temperature spin filtering

We report on the epitaxial growth and physical properties of spinel MnFe2O4(111) thin films with thicknesses down to 2 nm. The thin films, grown on alpha-Al2O3(0001) single crystals or Pt(111) buffer layers by oxygen-assisted molecular beam epitaxy, exhibit high structural order with sharp interfaces and low roughness. The electrical and magnetic properties are carefully investigated and it is shown that MnFe2O4(111) ultrathin films keep an insulating and ferrimagnetic behavior at room temperature. Special attention is given to the iron/manganese valence state and the cationic ordering. X-ray absorption spectroscopy and magnetic circular dichroism measurements reveal that thin films contain mainly Fe3+ and Mn2+ cations, distributed predominantly in a normal spinel structure. This study proves the high potential of MnFe2O4 to be used as a magnetic tunnel barrier for spin filtering applications at room temperature.

Interface and electronic characterization of thin epitaxial [formula omitted] films

The interface and electronic structure of thin (∼20–74 nm) Co 3 O 4 (1 1 0) epitaxial films grown by oxygen-assisted molecular beam epitaxy on MgAl 2 O 4 (1 1 0) single crystal substrates have been investigated by means of real and reciprocal space techniques. As-grown film surfaces are found to be relatively disordered and exhibit an oblique low energy electron diffraction (LEED) pattern associated with the O-rich CoO 2 bulk termination of the (1 1 0) surface. Interface and bulk film structure are found to improve significantly with post-growth annealing at 820 K in air and display sharp rectangular LEED patterns, suggesting a surface stoichiometry of the alternative Co 2 O 2 bulk termination of the (1 1 0) surface. Non-contact atomic force microscopy demonstrates the presence of wide terraces separated by atomic steps in the annealed films that are not present in the as-grown structures; the step height of ≈2.7 Å corresponds to two atomic layers and confirms a single termination for the annealed films, consistent with the LEED results. A model of the ( 1 × 1 ) surfaces that allows for compensation of the polar surfaces is presented.

On the spin polarization at the [formula omitted] interface probed by spin-resolved photoemission and spin-dependent tunneling

We report on two independent measurements of the spin polarization at the Fe 3 O 4 / γ - Al 2 O 3 interface. Fe 3 O 4 / γ - Al 2 O 3 (1 1 1) bilayers have been epitaxially grown by oxygen-assisted molecular beam epitaxy onto α - Al 2 O 3 (0 0 0 1) substrates and some were covered ex situ by a cobalt electrode. Spin resolved photoemission yield to a negative spin polarization ( ≃ - 40 %) while transport measurements on Fe 3 O 4 / γ - Al 2 O 3 / Co magnetic tunnel junctions show a positive TMR, which suggest that the tunnel spin polarization at the Fe 3 O 4 / γ - Al 2 O 3 interface is positive.

First-Principles Studies of Vanadia−Titania Catalysts: Beyond the Monolayer

Periodic density functional calculations have been used to investigate the structure and stability of epitaxial vanadium oxide films grown on the TiO(2)(001) anatase surface. The formation energy of films of V(2)O(5) stoichiometry, initially low, is found to rapidly increase with the film thickness, at variance to what is obtained for reduced pseudomorphic VO(2) films. This is in tune with results of oxygen-assisted molecular beam epitaxy. The oxidation of thick, viz. >2 monolayers (ML), VO(2) films yields a c(2 x 2) reconstructed surface, in agreement with low energy electron diffraction. These films are composed by partially reduced inner V atoms in a distorted-octahedral environment, and by isolated surface dioxovanadium centers exhibiting a distorted trigonal-bipyramidal coordination. Single scattering simulations of X-ray photoelectron diffraction patterns have also been performed, taking both 2- and 3-ML surface surface-oxidized films as models. Results are in fair agreement with experiments referring to films grown in oxidizing conditions, which suggests that coherent vanadia ultrathin films could be formed in vanadia-titania catalysts. The electronic structure of the films has been finally studied, finding that the terminal oxygens carried by the surface dioxovanadium species have a strong nucleophilic character, which makes them potential active centers for selective oxidation catalysis.

The (0 0 1) surface and morphology of thin Fe 3O 4 layers grown by O 2-assisted molecular beam epitaxy

We have investigated the termination and the surface reconstruction of Fe 3O 4 prepared by oxygen-assisted molecular beam epitaxy on MgO(0 0 1). The epitaxial Fe 3O 4 layer consists of two structural domains as a result of the fact that its lattice parameter is twice that of MgO. The domains with a lateral size of about 150 nm were observed to be slightly rotated (by an angle of about 1°) around the normal [0 0 1] axis. The surface was investigated with low-energy electron diffraction (LEED) and with low-energy ion scattering (LEIS). We performed 3-D calculations of the ion trajectories in the computer simulations of LEIS, using the program match. The azimuthal scans of scattered and recoiled particles measured in LEIS were compared with computer simulations for many trial structures, including those published in the recent literature. Good agreement was found for a relaxed Fe terminated surface in which every second Fe atom is missing. The topmost layer has an inward relaxation of about 40%. This model explains the symmetry seen in LEED, and it fulfills the criterion of charge neutrality of this polar surface.