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Register a new userGrowth and characterization of thin epitaxial Co3O4(111) films
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The growth and characterization of epitaxial Co3O4(111) films grown by oxygen plasma-assisted molecular beam epitaxy on single crystalline a-Al2O3(0001) is reported. The Co3O4(111) grows single crystalline with the epitaxial relation Co3O4(111)[-12-1]||a-Al2O3(0001)[10-10], as determined from in situ electron diffraction. Film stoichiometry is confirmed by x-ray photoelectron spectroscopy, while ex situ x-ray diffraction measurements show that the Co3O4 films are fully relaxed. Post-growth annealing induces significant modifications in the film morphology, including a sharper Co3O4/a-Al2O3 interface and improved surface crystallinity, as shown by x-ray reflectometry, atomic force microscopy and electron diffraction measurements. Despite being polar, the surface of both as-grown and annealed Co3O4(111) films are (1 * 1), which can be explained in terms of inversion in the surface spinel structure.
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The interface and electronic structure of thin (~20-74 nm) Co3O4(110) epitaxial films grown by oxygen-assisted molecular beam epitaxy on MgAl2O4(110) 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 CoO2 bulk termination of the (110) 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 Co2O2 bulk termination of the (110) 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 A 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.
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The metastable orthorhombic phase of hafnia is generally obtained in polycrystalline films, whereas in epitaxial films, its formation has been much less investigated. We have grown Hf0.5Zr0.5O2 films by pulsed laser deposition, and the growth window (temperature and oxygen pressure during deposition and film thickness) for epitaxial stabilization of the ferroelectric phase is mapped. The remnant ferroelectric polarization, up to around 24 uC/cm2, depends on the amount of orthorhombic phase and interplanar spacing and increases with temperature and pressure for a fixed film thickness. The leakage current decreases with an increase in thickness or temperature, or when decreasing oxygen pressure. The coercive electric field (EC) depends on thickness (t) according to the coercive electric field (Ec) - thickness (t)-2/3 scaling, which is observed for the first time in ferroelectric hafnia, and the scaling extends to thicknesses down to around 5 nm. The proven ability to tailor the functional properties of high-quality epitaxial ferroelectric Hf0.5Zr0.5O2 films paves the way toward understanding their ferroelectric properties and prototyping devices.
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