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Register a new userStrain controlled oxygen vacancy formation and ordering in CaMnO$_3$
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We use first-principles calculations to investigate the stability of bi-axially strained textit{Pnma} perovskite CaMnO$_3$ towards the formation of oxygen vacancies. Our motivation is provided by promising indications that novel material properties can be engineered by application of strain through coherent heteroepitaxy in thin films. While it is usually assumed that such epitaxial strain is accommodated primarily by changes in intrinsic lattice constants, point defect formation is also a likely strain relaxation mechanism. This is particularly true at the large strain magnitudes ($>$4%) which first-principles calculations often suggest are required to induce new functionalities. We find a strong dependence of oxygen vacancy defect formation energy on strain, with tensile strain lowering the formation energy consistent with the increasing molar volume with increasing oxygen deficiency. In addition, we find that strain differentiates the formation energy for different lattice sites, suggesting its use as a route to engineering vacancy ordering in epitaxial thin films.
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Oxygen vacancy formation energy is an important quantity for enabling fast oxygen diffusion and oxygen catalysis in technologies like solid oxide fuel cells. Both previous literature in various systems and our calculations in LaMnO3, La0.75Sr0.25MnO3, LaFeO3, and La0.75Sr0.25FeO3, show mixed results for the direction and magnitude of the change in vacancy formation energy with strain. This paper develops a model to make sense of the different trend shapes in vacancy formation energy versus strain. We model strain effects using a set of consistent ab initio calculations, and demonstrate that our calculated results may be simply explained in terms of vacancy formation volume and changes in elastic constants between the bulk and defected states. A positive vacancy formation volume contributes to decreased vacancy formation energy under tensile strain, and an increase in elastic constants contributes to increases in vacancy formation energy with compressive and tensile strains, and vice versa. The vacancy formation volume dominates the linear portion of the vacancy formation energy strain response, while its curvature is governed by the vacancy-induced change in elastic constants. We show results sensitive to B-site cation, A-site doping, tilt system, and vacancy placement, which contributions may be averaged under thermally averaged conditions. In general, vacancy formation energies for most systems calculated here decreased with tensile strain, with about a 30-100 meV/% strain decrease with biaxial strain for those systems which showed a decrease in vacancy formation energy. Experimental verification is necessary to confirm the model outside of calculation.
The effect of high tensile strain and low dimensionality on the magnetic and electronic properties of CaMnO$_3$ ultrathin films, epitaxially grown on SrTiO$_3$ substrates, are experimentally studied and theoretically analyzed. By means of ab initio calculations, we find that, both, the high strain produced by the substrate and the presence of the free surface contribute to the stabilization of an in-plane ferromagnetic coupling, giving rise to a non-zero net magnetic moment in the ultrathin films. Coupled with this change in the magnetic order we find an insulator-metal transition triggered by the quantum confinement and the tensile epitaxial strain. Accordingly, our magnetic measurements in 3nm ultrathin films show a ferromagnetic hysteresis loop, absent in the bulk compound due to its G-type antiferromagnetic structure.
Reversible topotactic transitions between oxygen-vacancy-ordered structures in transition metal oxides provide a promising strategy for active manipulation of material properties. While transformations between various oxygen-deficient phases have been attained in bulk ABO$_{3-delta}$ perovskites, substrate clamping restricts the formation of distinct ordering patterns in epitaxial films. Using in-situ scanning transmission electron microscopy (STEM), we image a thermally driven reversible transition in La$_{0.5}$Sr$_{0.5}$CoO$_{3-delta}$ films on SrTiO$_3$ from a multidomain brownmillerite (BM) structure to a uniform phase wherein oxygen vacancies order in every third CoO$_x$ plane. Because temperature cycling is performed over a limited temperature range (25 {deg}C - 385 {deg}C), the oxygen deficiency parameter $delta$ does not vary measurably. Under constant $delta$, the topotactic transition proceeds via local reordering of oxygen vacancies driven by thermal strain. Atomic-resolution imaging reveals a two-step process whereby alternating vertically and horizontally oriented BM domains first scale in size to accommodate the strain induced by different thermal expansions of La$_{0.5}$Sr$_{0.5}$CoO$_{3-delta}$ and SrTiO$_3$, before the new phase nucleates and quickly grows above 360 {deg}C. Upon cooling, the film transform back to the mixed BM phase. As the structural transition is fully reversible and $delta$ does not change upon temperature cycling, we rule out electron-beam irradiation during STEM as the driving mechanism. Instead, our findings demonstrate that thermal strain can solely drive topotactic phase transitions in perovskite oxide films, presenting opportunities for switchable ionic devices.
The observation of metallic interface between band insulators LaAlO$_3$ and SrTiO$_3$ has led to massive efforts to understand the origin of the phenomenon as well as to search for other systems hosting such two dimensional electron gases (2-DEG). However, the understanding of the origin of the 2-DEG is very often hindered as several possible mechanisms such as polar catastrophe, cationic intermixing and oxygen vacancy (OV) etc. can be operative simultaneously. The presence of a heavy element makes KTaO$_3$ (KTO) based 2-DEG a potential platform to investigate spin orbit coupling driven novel electronic and magnetic phenomena. In this work, we investigate the sole effect of the OV, which makes KTO metallic. Our detailed textit{ab initio} calculations not only find partially filled conduction bands in the presence of an OV but also predict a highly localized mid-gap state due to the linear clustering of OVs around Ta. Photoluminescence measurements indeed reveal the existence of such mid-gap state and O $K$-edge X-ray absorption spectroscopy finds electron doping in Ta $t_{2g}^*$ antibonding states. This present work suggests that one should be cautious about the possible presence of OVs within KTO substrate in interpreting metallic behavior of KTO based 2-DEG.
The infrared (IR) reflectivity spectra of orthorhombic manganese perovskites PrMnO$_3$ and CaMnO$_3$ are studied in the frequency range of optical phonon modes at temperatures varying from 300 to 4 K. The IR phonon spectra of these two materials are analyzed by a fitting procedure based on a Lorentz model, and assigned to definite vibrational modes of $Pnma$ structures by comparison with the results of lattice dynamical calculations. The calculations have been performed in the framework of a shell model using short range Born-Mayer-Buckingham and long range Coulomb potentials, whose parameters have been optimized in order that the calculated Raman and IR active phonon frequencies, and lattice parameters match with their experimental values. We find a close correspondence between the values of the IR phonon frequencies of PrMnO$_3$ and CaMnO$_3$, which shows that the substitution of the Pr$^{3+}$ ions with Ca$^{2+}$ results in a reduction of the frequency of medium- and high-energy IR phonons, and an increase of the frequency of those of low-energy. Nevertheless, the experimentally obtained IR phonon amplitudes of the two materials appear to be unrelated. A comparative study of the vibrational patterns of these modes reveals that most of them correspond to complex atomic vibrations significantly different from PrMnO$_3$ to CaMnO$_3$ which cannot be assigned only to a given type of vibration (external, bending, or stretching modes). In particular, these results confirm that the structure of CaMnO$_3$ is quite far from the ideal (cubic) perovskite structure.
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