Effect of epitaxial strain on ferroelectric polarization in multiferroic BiFeO3 films

Multiferroic BiFeO3 epitaxial films with thickness ranging from 40 nm to 960 nm were grown by pulsed laser deposition on SrTiO3 (001) substrates with SrRuO3 bottom electrodes. X-ray characterization shows that the structure evolves from angularly-distorted tetragonal with c/a ~ 1.04 to more bulk-like distorted rhombohedral (c/a ~ 1.01) as the strain relaxes with increasing thickness. Despite this significant structural evolution, the ferroelectric polarization along the body diagonal of the distorted pseudo-cubic unit cells, as calculated from measurements along the normal direction, barely changes.Comment: Legend in Fig.3 corrected and et

Wide-range strain tunability provided by epitaxial LaAl1−xScxO3 template films

The dielectric diamagnetic LaAl1− xScxO3 (LASO) (x=0–1) is proposed for adjusting of the biaxial in-plane lattice parameter of oxide substrates in the wide range from 3.79 to 4.05 Å (6.5%). This range includes the pseudocubic lattice parameters of most of the currently investigated complex oxides. The in-plane lattice parameter of strain-relaxed LASO films depends linearly on the composition, and these films grow with a smooth surface. On several different LASO-buffered substrates, ferromagnetic La0.7Sr0.3MnO3 (LSMO) films have been grown in predetermined strain states. A series of 30 nm thick LSMO films on LASO-buffered LaSrAlO4(001) demonstrates that continuously controlled coherent strains in a wide range, in this case from − 1 to +0.6%, can be obtained for the functional oxide films grown on LASO

Temperature Driven Structural Phase Transition in Tetragonal-Like BiFeO3

Highly-strained BiFeO3 exhibits a "tetragonal-like, monoclinic" crystal structure found only in epitaxial films (with an out-of-plane lattice parameter exceeding the in-plane value by >20%). Previous work has shown that this phase is properly described as a M$_{C}$ monoclinic structure at room temperature [with a (010)$_{pc}$ symmetry plane, which contains the ferroelectric polarization]. Here we show detailed temperature-dependent x-ray diffraction data that evidence a structural phase transition at ~100C to a high-temperature M$_{A}$ phase ["tetragonal-like" but with a (1-10)$_{pc}$ symmetry plane]. These results indicate that the ferroelectric properties and domain structures of strained BiFeO$_3$ will be strongly temperature dependent.Comment: 10 pages, 3 figure

Impact of Symmetry on the Ferroelectric Properties of CaTiO₃ Thin Films

Epitaxial strain is a powerful tool to induce functional properties such as ferroelectricity in thin films of materials that do not possess ferroelectricity in bulk form. In this work, a ferroelectric state was stabilized in thin films of the incipient ferroelectric, CaTiO3, through the careful control of the biaxial strain state and TiO6 octahedral rotations. Detailed structural characterization was carried out by synchrotron x-ray diffraction and scanning transmission electron microscopy. CaTiO3 films grown on La0.18Sr0.82Al0.59Ta0.41O3 (LSAT) and NdGaO3 (NGO) substrates experienced a 1.1% biaxial strain state but differed in their octahedral tilt structures. A suppression of the out-of-plane rotations of the TiO6 octahedral in films grown on LSAT substrates resulted in a robust ferroelectric 14 mm phase with remnant polarization ~5 µC/cm2 at 10K and Tc near 140 K. In contrast, films grown on NGO substrates with significant octahedral tilting showed reduced polarization and Tc. These results highlight the key role played by symmetry in controlling the ferroelectric properties of perovskite oxide thin films

Erratum: Impact of Symmetry on the Ferroelectric Properties of CaTiO₃ Thin Films (Applied Physics Letters 106:162904 (2015))

There is a typo of the space group. All the Pnmb should be Pbnm (or Pnma). So the Glazer notation should be changed to (a-a-c+) for Pbnm space group on page 4 of the article. We have also noticed that the thermodynamic analysis of CaTiO3 thin film is not correct. The films are (001)PC-oriented or (101)-oriented. Therefore, there is no need to rotate the coordinate system (on page 4 of the article). By applying the thin film boundary condition, i.e., ε11 = ε22 = εs, ε21 = ε12 = 0; σ13 = σ23 = σ33 = σ31 = σ32 = 0, and minimizing the total free energy with respect to epitaxial strain, εs, a temperature-strain phase diagram is determined. All the strain and stress components should be in the original coordinate system. The corrected phase diagrams are shown in the figures below. For LSAT phase diagrams (Figs. 5(a) and 5(b)), the ferroelectric transition is better described using the Fmm2 phase because the calculated phase boundary is much closer to the experimental value than using the Aba2 phase. The NGO phase diagram, as shown in Fig. 5(c), is essentially the same as Gu’s orthorhombic Pbnm CaTiO3 film calculation, which is also (001)PC-oriented. All the other analysis and conclusions in the article are not affected. We apologize to the readers for the confusion that might have been caused. The authors would like to thank Ryan Haislmaier for pointing out the mistake

Reactivity of Perovskites with Water: Role of Hydroxylation in Wetting and Implications for Oxygen Electrocatalysis

Oxides are instrumental to applications such as catalysis, sensing, and wetting, where the reactivity with water can greatly influence their functionalities. We find that the coverage of hydroxyls (*OH) measured at fixed relative humidity trends with the electron-donor (basic) character of wetted perovskite oxide surfaces. Using ambient pressure X-ray photoelectron spectroscopy, we report that the affinity toward hydroxylation, coincident with strong adsorption energies calculated for dissociated water and hydroxyl groups, leads to strong H bonding that is favorable for wetting while detrimental to catalysis of the oxygen reduction reaction (ORR). Our findings provide novel insights into the coupling between wetting and catalytic activity and suggest that catalyst hydrophobicity should be considered in aqueous oxygen electrocatalysis.National Science Foundation (U.S.). Materials Research Science and Engineering Centers (Program) (Award DMR-0819762)National Science Foundation (U.S.). Graduate Research Fellowship (Grant DGE-1122374)National Science Foundation (U.S.) (Career Award (0952564

Nanostructured complex oxides as a route towards thermal behavior in artificial spin ice systems

We have used soft x-ray photoemission electron microscopy to image the magnetization of single domain La$_{0.7}$Sr$_{0.3}$MnO$_{3}$ nano-islands arranged in geometrically frustrated configurations such as square ice and kagome ice geometries. Upon thermal randomization, ensembles of nano-islands with strong inter-island magnetic coupling relax towards low-energy configurations. Statistical analysis shows that the likelihood of ensembles falling into low-energy configurations depends strongly on the annealing temperature. Annealing to just below the Curie temperature of the ferromagnetic film (T$_{C}$ = 338 K) allows for a much greater probability of achieving low energy configurations as compared to annealing above the Curie temperature. At this thermally active temperature of 325 K, the ensemble of ferromagnetic nano-islands explore their energy landscape over time and eventually transition to lower energy states as compared to the frozen-in configurations obtained upon cooling from above the Curie temperature. Thus, this materials system allows for a facile method to systematically study thermal evolution of artificial spin ice arrays of nano-islands at temperatures modestly above room temperature.Comment: 4 figures and 9 supplemental figure

Thickness dependence of exchange coupling in (111)-oriented perovskite oxide superlattices

Epitaxial La0.7Sr0.3MnO3(LSMO)/La0.7Sr0.3FeO3 (LSFO) superlattices on (111)-oriented SrTiO3 substrates with sublayer thicknesses ranging from 3 to 60 unit cells (u.c.) were synthesized and characterized. Detailed analysis of their structural, electronic, and magnetic properties were performed to explore the effect of sublayer thickness on the magnetic structure and exchange coupling at (111)-oriented perovskite oxide interfaces. In the ultrathin limit (3-6 u.c.), we find that the antiferromagnetic (AF) properties of the LSFO sublayers are preserved with an out-of-plane canting of the AF spin axis, while the ferromagnetic (FM) properties of the LSMO sublayers are significantly depressed. For thicker LSFO layers (>9 u.c.), the out-of-plane canting of the AF spin axis is only present in superlattices with thick LSMO sublayers. As a result, exchange coupling in the form of spin-flop coupling exists only in superlattices which display both robust ferromagnetism and out-of-plane canting of the AF spin axis

In situ observation of oxygen vacancy dynamics and ordering in the epitaxial LaCoO3 system

Vacancy dynamics and ordering underpin the electrochemical functionality of complex oxides and strongly couple to their physical properties. In the field of the epitaxial thin films, where connection between chemistry and film properties can be most clearly revealed, the effects related to oxygen vacancies are attracting increasing attention. In this article, we report a direct, real-time, atomic level observation of the formation of oxygen vacancies in the epitaxial LaCoO3 thin films and heterostructures under the influence of the electron beam utilizing scanning transmission electron microscopy (STEM). In the case of LaCoO3/SrTiO3 superlattice, the formation of the oxygen vacancies is shown to produce quantifiable changes in the interatomic distances, as well as qualitative changes in the symmetry of the Co sites manifested as off-center displacements. The onset of these changes was observed in both the [100]pc and [110]pc orientations in real time. Additionally, annular bright field images directly show the formation of oxygen vacancy channels along [110]pc direction. In the case of 15 u.c. LaCoO3 thin film, we observe the sequence of events during beam-induced formation of oxygen vacancy ordered phases and find them consistent with similar processes in the bulk. Moreover, we record the dynamics of the nucleation, growth, and defect interaction at the atomic scale as these transformations happen. These results demonstrate that we can track dynamic oxygen vacancy behavior with STEM, generating atomic-level quantitative information on phase transformation and oxygen diffusion