RESUMO
Through systematic control of the Nd concentration, we show that the carrier density of the two-dimensional electron gas (2DEG) in SrTiO_{3}/NdTiO_{3}/SrTiO_{3}(001) can be modulated over a wide range. We also demonstrate that the NdTiO_{3} in heterojunctions without a SrTiO_{3} cap is degraded by oxygen absorption from air, resulting in the immobilization of donor electrons that could otherwise contribute to the 2DEG. This system is, thus, an ideal model to understand and control the insulator-to-metal transition in a 2DEG based on both environmental conditions and film-growth processing parameters.
RESUMO
The oxides of platinum group metals are promising for future electronics and spintronics due to the delicate interplay of spin-orbit coupling and electron correlation energies. However, their synthesis as thin films remains challenging due to their low vapour pressures and low oxidation potentials. Here we show how epitaxial strain can be used as a control knob to enhance metal oxidation. Using Ir as an example, we demonstrate the use of epitaxial strain in engineering its oxidation chemistry, enabling phase-pure Ir or IrO2 films despite using identical growth conditions. The observations are explained using a density-functional-theory-based modified formation enthalpy framework, which highlights the important role of metal-substrate epitaxial strain in governing the oxide formation enthalpy. We also validate the generality of this principle by demonstrating epitaxial strain effect on Ru oxidation. The IrO2 films studied in our work further revealed quantum oscillations, attesting to the excellent film quality. The epitaxial strain approach we present could enable growth of oxide films of hard-to-oxidize elements using strain engineering.
RESUMO
Recent investigations on spinel CoMn2O4 have shown its potential for applications in water splitting and fuel cell technologies as it exhibits strong catalytic behavior through oxygen reduction reactivity. To further understand this material, we report for the first time the synthesis of single-crystalline Co1+x Mn2-x O4 thin films using molecular beam epitaxy. By varying sample composition, we establish links between cation stoichiometry and material properties using in-situ x-ray photoelectron spectroscopy, x-ray diffraction, scanning transmission electron microscopy, x-ray absorption spectroscopy, and spectroscopic ellipsometry. Our results indicate that excess Co ions occupy tetrahedral interstitial sites at lower excess Co stoichiometries, and become substitutional for octahedrally-coordinated Mn at higher Co levels. We compare these results with density functional theory models of stoichiometric CoMn2O4 to understand how the Jahn-Teller distortion and hybridization in Mn-O bonds impact the ability to hole dope the material with excess Co. The findings provide important insights into CoMn2O4 and related spinel oxides that are promising candidates for inexpensive oxygen reduction reaction catalysts.
RESUMO
The titanomagnetites (Fe2-xTixO4,x⩽ 1) are a family of reducible spinel-structure oxides of interest for their favorable magnetic, catalytic, and electrical transport properties. To understand the stability of the system during low temperature deposition, epitaxial thin films of Fe2TiO4were deposited by molecular beam epitaxy (MBE) on MgO(001) at 250-375 °C. The homogeneous incorporation of Ti, Fe valence state, and film morphology were all found to be strongly dependent on the oxidation conditions at the low substrate temperatures employed. More oxidizing conditions led to phase separation into epitaxial, faceted Fe3O4and rutile TiO2. Less oxidizing conditions resulted in polycrystalline films that exhibited Ti segregation to the film surface, as well as mixed Fe valence (Fe3+, Fe2+, Fe0). A narrow window of intermediate oxygen partial pressure during deposition yielded nearly homogeneous Ti incorporation and a large fraction of Fe2+. However, these films were poorly crystallized, and no occupation of tetrahedral sites in the spinel lattice by Fe2+was detected by x-ray magnetic circular dichroism at the Fe L-edge. After vacuum annealing, a small fraction of Fe2+was found to occupy tetrahedral sites. Comparison of these results with previous work suggests that the low temperature deposition conditions imposed by use of MgO substrates limits the incorporation of Ti into the spinel lattice. This work suggests a path towards obtaining stoichiometric, well-crystallized Fe2TiO4by MBE by utilizing high substrate temperature and low oxygen partial pressure during deposition on thermally stable substrates.
RESUMO
Current piezoelectric sensors and actuators are limited to operating temperatures less than ~200 °C due to the low Curie temperature of the piezoelectric material. Strengthening the piezoelectric coupling of high-temperature piezoelectric materials, such as La2Ti2O7 (LTO), would allow sensors to operate across a broad temperature range. The crystalline orientation and piezoelectric coupling direction of LTO thin films can be controlled by epitaxial matching to SrTiO3(001), SrTiO3(110), and rutile TiO2(110) substrates via pulsed laser deposition. The structure and phase purity of the films are investigated by x-ray diffraction and scanning transmission electron microscopy. Piezoresponse force microscopy is used to measure the in-plane and out-of-plane piezoelectric coupling in the films. The strength of the out-of-plane piezoelectric coupling can be increased when the piezoelectric direction is rotated partially out-of-plane via epitaxy. The strongest out-of-plane coupling is observed for LTO/STO(001). Deposition on TiO2(110) results in epitaxial La2/3TiO3, an orthorhombic perovskite of interest as a microwave dielectric material and an ion conductor. La2/3TiO3 can be difficult to stabilize in bulk form, and epitaxial stabilization on TiO2(110) is a promising route to realize La2/3TiO3 for both fundamental studies and device applications. Overall, these results confirm that control of the crystalline orientation of epitaxial LTO-based materials can govern the resulting functional properties.
RESUMO
Band gap engineering in SrTiO3 and related titanate perovskites has long been explored due to the intriguing properties of the materials for photocatalysis and photovoltaic applications. A popular approach in the materials chemistry community is to substitutionally dope aliovalent transition metal ions onto the B site in the lattice to alter the valence band. However, in such a scheme there is limited control over the dopant valence, and compensating defects often form. Here we demonstrate a novel technique to controllably synthesize Fe(2+)- and Fe(3+)-doped SrTiO3 thin films without formation of compensating defects by co-doping with La(3+) ions on the A site. We stabilize Fe(2+)-doped films by doping with two La ions for every Fe dopant, and find that the Fe ions exhibit a low-spin electronic configuration, producing optical transitions in the near infrared regime and degenerate doping. The novel electronic states observed here offer a new avenue for band gap engineering in perovskites for photocatalytic and photovoltaic applications.