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SrMnO3 has a rich epitaxial strain-dependent ferroic phase diagram, in which a variety of magnetic orderings, even ferroelectricity, and thus multiferroicity, are accessible by gradually modifying the strain. Different relaxation processes, though, including the presence of strain-induced oxygen vacancies, can severely curtail the possibility of stabilizing these ferroic phases. Here, we report on a thorough investigation of the strain relaxation mechanisms in SrMnO3 films grown on several substrates imposing varying degrees of strain from slightly compressive (−0.39%) to largely tensile ≈+3.8%. First, we determine the strain dependency of the critical thickness (tc) below which pseudomorphic growth is obtained. Second, the mechanisms of stress relaxation are elucidated, revealing that misfit dislocations and stacking faults accommodate the strain above tc. Yet, even for films thicker than tc, the atomic monolayers below tc are proved to remain fully coherent. Therefore, multiferroicity may also emerge even in films that appear to be partially relaxed. Last, we demonstrate that fully coherent films with the same thickness present a lower oxygen content for increasing tensile mismatch with the substrate. This behavior proves the coupling between the formation of oxygen vacancies and epitaxial strain, in agreement with first-principles calculations, enabling the strain control of the Mn3+/Mn4+ ratio, which strongly affects the magnetic and electrical properties. However, the presence of oxygen vacancies/Mn3+ cations reduces the effective epitaxial strain in the SrMnO3 films and, thus, the accessibility to the strain-induced multiferroic phase., This work was financially supported by the Spanish Ministry of Science through project MAT2017-82970-C2-1-R and MAT2017-82970-C2-2-R and the Aragón Regional Government through projects E13_20R and E28_20R (Construyendo Europa desde Aragón). This project received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement no. 823717—ESTEEM3.

Utilizing the magnetostrictive properties of CoFe2O4, we demonstrate reversible room temperature control of the Ti electronic structure in SrTiO3–CoFe2O4 heterostructures, by inducing local and reversible strain in the SrTiO3. By means of X-ray absorption spectroscopy, we have ascertained the changes that take place in the energy levels of the Ti 3d orbitals under the influence of an external magnetic field. The observed Ti electronic state when the sample is subjected to moderately large external magnetic fields and the disappearance of the induced phase upon their removal indicates lattice distortions that are suggestive of the development of a net electric polarization., We show reversible room temperature control of the Ti band structure in SrTiO3–CoFe2O4 heterostructures exploiting CoFe2O4 magnetostriction. Changes as a function of the applied magnetic field suggest the development of a net electric polarization.

In the high spin–orbit-coupled Sr2IrO4, the high sensitivity of the ground state to the details of the local lattice structure shows a large potential for the manipulation of the functional properties by inducing local lattice distortions. We use epitaxial strain to modify the Ir–O bond geometry in Sr2IrO4 and perform momentum-dependent resonant inelastic X-ray scattering (RIXS) at the metal and at the ligand sites to unveil the response of the low-energy elementary excitations. We observe that the pseudospin-wave dispersion for tensile-strained Sr2IrO4 films displays large softening along the [h,0] direction, while along the [h,h] direction it shows hardening. This evolution reveals a renormalization of the magnetic interactions caused by a strain-driven cross-over from anisotropic to isotropic interactions between the magnetic moments. Moreover, we detect dispersive electron–hole pair excitations which shift to lower (higher) energies upon compressive (tensile) strain, manifesting a reduction (increase) in the size of the charge gap. This behavior shows an intimate coupling between charge excitations and lattice distortions in Sr2IrO4, originating from the modified hopping elements between the t2g orbitals. Our work highlights the central role played by the lattice degrees of freedom in determining both the pseudospin and charge excitations of Sr2IrO4 and provides valuable information toward the control of the ground state of complex oxides in the presence of high spin–orbit coupling., Proceedings of the National Academy of Sciences of the United States of America, 117 (40), ISSN:0027-8424, ISSN:1091-6490

Charge mediated magnetoelectric coupling mechanism in artificial multiferroics originates from interfacial charge modulation or ionic movement at a magnetic/dielectric interface. Despite the existence of several dielectric/ferroelectric systems that can be used in charge mediated artificial multiferroic systems, producing suitable systems with fast time responses still remains a challenge. Here we characterize the frequency response of stoichiometric and non-stoichiometric (low strain) Si3N4 thin film membranes, which can potentially be used as the dielectric layer in magnetoelectric devices, to determine the impact of depletion layers, charge traps and defect mobility on the high frequency (up to 100 MHz) interfacial charge modulation via screening. We find that the dielectric/magnetoelectric properties are largely dominated by extrinsic doping due to point defects. In particular, we find that non-stoichiometric Si(3)N4( )has a dielectric behaviour that is dominated by charge traps and/or mobile ions. However, stoichiometric Si3N4 membranes show a reversible response to the applied bias electric field consistent with a doped semiconductor behaviour; at high frequencies, the intrinsic dielectric behaviour is reached, indicating that it may be suitable for high frequency magnetoelectric device applications. Our results show that minimising the impact of defects on the dielectric properties of magnetoelectric heterostructures is an important prerequisite for obtaining a high frequency magnetoelectric response., Journal of Materials Science, 57, ISSN:0022-2461, ISSN:1573-4803

Significance Understanding the relationship between entangled degrees of freedom (DOF) is a central problem in correlated materials and the possibility to influence their balance is promising toward realizing novel functionalities. In Sr2IrO4, the interaction between spin–orbit coupling and electron correlations induces an exotic ground state with magnetotransport properties promising for antiferromagnetic spintronics applications. Moreover, the coupling between orbital and spin DOF renders the magnetic structure sensitive to the Ir–O bond environment. To date, a detailed understanding of the microscopic spin-lattice and electron–phonon interactions is still lacking. Here, we use strain engineering to perturb the local lattice environment and, by tracking the response of the low-energy elementary excitations, we unveil the response of the microscopic spin and charge interactions., In the high spin–orbit-coupled Sr2IrO4, the high sensitivity of the ground state to the details of the local lattice structure shows a large potential for the manipulation of the functional properties by inducing local lattice distortions. We use epitaxial strain to modify the Ir–O bond geometry in Sr2IrO4 and perform momentum-dependent resonant inelastic X-ray scattering (RIXS) at the metal and at the ligand sites to unveil the response of the low-energy elementary excitations. We observe that the pseudospin-wave dispersion for tensile-strained Sr2IrO4 films displays large softening along the [h,0] direction, while along the [h,h] direction it shows hardening. This evolution reveals a renormalization of the magnetic interactions caused by a strain-driven cross-over from anisotropic to isotropic interactions between the magnetic moments. Moreover, we detect dispersive electron–hole pair excitations which shift to lower (higher) energies upon compressive (tensile) strain, manifesting a reduction (increase) in the size of the charge gap. This behavior shows an intimate coupling between charge excitations and lattice distortions in Sr2IrO4, originating from the modified hopping elements between the t2g orbitals. Our work highlights the central role played by the lattice degrees of freedom in determining both the pseudospin and charge excitations of Sr2IrO4 and provides valuable information toward the control of the ground state of complex oxides in the presence of high spin–orbit coupling.

Chemical doping and epitaxy can be used to tailor the magnetoelectric properties of multiferroic thin films, such as SrMnO3. Here, we study the dependence of the magnetic order temperatures of Sr1−xBaxMnO3 thin films on epitaxial strain and Ba content. Combining low-energy muon spin spectroscopy and scanning transmission electron microscopy, the broadness of the magnetic transition is attributed to the presence of a Mn-O-Mn angle gradient along the out-of-plane direction. We also demonstrate that the unit cell volume is the key parameter to determine the Néel temperature in Sr1−xBaxMnO3 thin films showing G-type antiferromagnetic order. The occurrence of a simultaneously ferroelectric and ferromagnetic ground state at high strain levels is suggested for the Sr0.8Ba0.2MnO3 thin film deposited on TbScO3., This work has been supported by the Spanish Ministry of Science through Project Nos. MAT2017-82970-C2-1-R and MAT2017-82970-C2-2-R and by the Aragon Regional Government through Project Nos. E13_17R and E28_17R (Construyendo Europa desde Aragón).

Letter.-- et al., Local perturbations in complex oxides, such as domain walls, strain and defects, are of interest because they can modify the conduction or the dielectric and magnetic response, and can even promote phase transitions. Here, we show that the interaction between different types of local perturbations in oxide thin films is an additional source of functionality. Taking SrMnO 3 as a model system, we use nonlinear optics to verify the theoretical prediction that strain induces a polar phase, and apply density functional theory to show that strain simultaneously increases the concentration of oxygen vacancies. These vacancies couple to the polar domain walls, where they establish an electrostatic barrier to electron migration. The result is a state with locally structured room-temperature conductivity consisting of conducting nanosized polar domains encased by insulating domain boundaries, which we resolve using scanning probe microscopy. Our 'nanocapacitor' domains can be individually charged, suggesting stable capacitance nanobits with a potential for information storage technology., M.F., D.M. and M.L. acknowledge funding from grant ‘ETH-06 12-2’ and from SNF proposal no. 200021-149192. The authors acknowledge funding through the SNF R’equip Program (no. 206021-144988). Financial support from Spanish Ministerio de Economía y Competitividad through projects MAT2011-27553-C02, MAT2012-38213-C02-01, MAT2014-51982-C2 and from Regional Gobierno de Aragón through project E26 is acknowledged.

Spin-phonon coupling is investigated in epitaxially strained $\mathrm{S}{\mathrm{r}}_{1\ensuremath{-}x}\mathrm{B}{\mathrm{a}}_{x}\mathrm{Mn}{\mathrm{O}}_{3}$ thin films with perovskite structure by means of microwave (MW) and infrared (IR) spectroscopy. In this work we focus on the $\mathrm{S}{\mathrm{r}}_{0.6}\mathrm{B}{\mathrm{a}}_{0.4}\mathrm{Mn}{\mathrm{O}}_{3}$ composition grown on ${(\mathrm{LaAl}{\mathrm{O}}_{3})}_{0.3}{(\mathrm{S}{\mathrm{r}}_{2}\mathrm{AlTa}{\mathrm{O}}_{6})}_{0.7}$ substrate. The MW complex electromagnetic response shows a decrease in the real part and a clear anomaly in the imaginary part around 150 K. Moreover, it coincides with a $17%$ hardening of the lowest-frequency polar phonon seen in IR reflectance spectra. In order to further elucidate this phenomenon, low-energy muon-spin spectroscopy was carried out, signaling the emergence of antiferromagnetic order with N\'eel temperature (${T}_{N}$) around 150 K. Thus, our results confirm that epitaxial $\mathrm{S}{\mathrm{r}}_{0.6}\mathrm{B}{\mathrm{a}}_{0.4}\mathrm{Mn}{\mathrm{O}}_{3}$ thin films display strong spin-phonon coupling below ${T}_{N}$, which may stimulate further research on tuning the magnetoelectric coupling by controlling the epitaxial strain and chemical pressure in the $\mathrm{S}{\mathrm{r}}_{1\ensuremath{-}x}\mathrm{B}{\mathrm{a}}_{x}\mathrm{Mn}{\mathrm{O}}_{3}$ system.

Engineering defects and strains in oxides provides a promising route for the quest of thin film materials with coexisting ferroic orders, multiferroics, with efficient magnetoelectric coupling at room temperature. Precise control of the strain gradient would enable custom tailoring of the multiferroic properties but presently remains challenging. Here we explore the existence of a polar-graded state in epitaxially strained antiferromagnetic SrMnO3 thin films, whose polar nature was predicted theoretically and recently demonstrated experimentally. By means of aberration-corrected scanning transmission electron microscopy we map the polar rotation of the ferroelectric polarization with atomic resolution, both far from and near the domain walls, and find flexoelectricity resulting from vertical strain gradients. The origin of this particular strain state is a gradual distribution of oxygen vacancies across the film thickness, according to electron energy loss spectroscopy. Herein we present a chemistry-mediated route to induce polar rotations in oxygen-deficient multiferroic films, resulting in flexoelectric polar rotations and with potentially enhanced piezoelectricity.

Under the terms of the Creative Commons Attribution license.-- et al., High-resolution mapping of electronic transport phenomena plays an increasingly important role for the characterization of ferroic domains and their functionality. At present, spatially resolved electronic transport data are commonly gained from local two-point measurements, collected in line-by-line scans with a conducting nanosized probe. Here, we introduce an innovative experimental approach based on low-energy electron microscopy. As a model case, we study polar domains of varying conductance in strained SrMnO3. By a direct comparison with conductive atomic force and electrostatic force microscopy, we reveal that the applied low-energy electron-microscopy experiment can be considered as an inverse I(V) measurement, providing access to the local electronic conductance with nanoscale resolution and short data-acquisition times in the order of 10-102 ms. Low-energy electrons thus hold yet unexplored application opportunities as a minimal-invasive probe for local electronic transport phenomena, opening a promising route towards spatially resolved, high-throughput sampling at the nanoscale., We thank HZB for the allocation of synchrotron beam time and we thankfully acknowledge financial support by HZB. Research at the ETH was financed in part by the SNF (Proposal No. 200021_149192). L. M., E. L., P. A. A., and J. A. P. acknowledge financial support from Ministerio de Economía y Competitividad under Project No. MAT2014-51982-C2 and Gobierno de Aragón under Project No. E26.

A novel mechanism of ferroelectricity driven by off-centering magnetic Mn4+ ions was proposed in (Sr1–xBax)MnO3, in its ideal perovskite phase, which yields enormous expectations in the search for strong magnetoelectric materials. Still, the desired perovskite phase has never been stabilized in thin films due to its extremely metastable character. Here, we report on a thorough study of the perovskite phase stabilization of (Sr1–xBax)MnO3 thin films, 0.2 ≤ x ≤ 0.5, grown by pulsed laser deposition onto (001)-oriented perovskite substrates. X-ray diffraction measurements and scanning transmission electron microscopy reveal that, under appropriate deposition conditions, the perovskite phase is fully stabilized over the nonferroelectric hexagonal phase, despite the latter being increasingly favored on increasing Ba-content. Moreover, we have managed to grow epitaxial coherent cube-on-cube (Sr1–xBax)MnO3 films upon strains ranging from 0% to 4%. Our results become a milestone in further studying perovskite (Sr1–xBax)MnO3 thin films and pave the way for tailoring ferroic and magnetoelectric properties either by strain engineering or Ba-doping., This work was supported by the Spanish Ministry of Economy and Competitiveness through Projects MAT2012-38213-C02-01 and MAT2014-51982-C2 including FEDER funding, by the Aragon Regional Government through Projects E26 and CTPP4/11 and by the European Union under the Seventh Framework Programme under a contract for an Integrated Infrastructure Initiative Reference 312483-ESTEEM2.

et al., Epitaxial films of SrMnO3 and bilayers of SrMnO3/La0.67Sr0.33MnO3 have been deposited by pulsed laser deposition on different substrates, namely, LaAlO3 (001), (LaAlO3)0.3(Sr2AlTaO6)0.7 (001), and SrTiO3 (001), allowing us to perform an exhaustive study of the dependence of antiferromagnetic order and exchange bias field on epitaxial strain. The Néel temperatures (TN) of the SrMnO3 films have been determined by low-energy muon spin spectroscopy. In agreement with theoretical predictions, TN is reduced as the epitaxial strain increases. From the comparison with first-principles calculations, a crossover from G-type to C-type antiferromagnetic orders is proposed at a critical tensile strain of around 1.6±0.1%. The exchange bias (coercive) field, obtained for the bilayers, increases (decreases) by increasing the epitaxial strain in the SrMnO3 layer, following an exponential dependence with temperature. Our experimental results can be explained by the existence of a spin-glass (SG) state at the interface between the SrMnO3 and La0.67Sr0.33MnO3 films. This SG state is due to the competition between the different exchange interactions present in the bilayer and favored by increasing the strain in the SrMnO3 layer., This work was supported by the Spanish Ministerio de Economía y Competitividad through Project Nos. MAT2011-28532-C03-02, MAT2011-27553-C02, MAT2012- 38213-C02-01, and MAT2014-51982-C2 including FEDER funding, by the Aragon Regional Government through projects E26 and CTPP4/11 and by the European Union under the Seventh Framework Programme under a contract for an Integrated Infrastructure Initiative Reference 312483-ESTEEM2. N. Marcano acknowledges the support of the Centro Universitario de la Defensa en Zaragoza (through Project 2013-03).

The perovskite (Sr,Ba)MnO3 system is an ideal candidate for tailoring electrical and magnetoelectric properties through the accurate control of Ba content and epitaxial strain due to the strong coupling between polar instability, spin order, and lattice. Here, first, the polar order is proved to be induced in Sr1−xBaxMnO3 thin films through lattice expansion either by epitaxial strain or chemical pressure, which correlates with the evolution of the dielectric properties. Second, due to strong spin–phonon coupling, a large magnetoelectric response is found in the (Sr,Ba)MnO3 system, in which the dielectric constant drops up to 50% when the antiferromagnetic order emerges, larger than most magnetoelectric oxides. More important, this coupling between magnetism and dielectric properties can be tuned from ≈18% to ≈50% by appropriately selecting Ba content and epitaxial strain. Third, a clear trend of increasing the band gap energy on increasing the unit cell volume either by epitaxial strain or chemical pressure is found, which opens the way for engineering the semiconducting properties of (Sr,Ba)MnO3 system at will. Thus, this work proves the possibility to design the electrical response and the magnetoelectric coupling in (Sr,Ba)MnO3 system.