Highly reversible extrinsic electrocaloric effects over a wide temperature range in epitaxially strained SrTiO3 films.

Electrocaloric effects have been experimentally studied in ferroelectrics and incipient ferroelectrics, but not incipient ferroelectrics driven ferroelectric using strain. Here we use optimally oriented interdigitated surface electrodes to investigate extrinsic electrocaloric effects in low-loss epitaxial SrTiO3 films near the broad second-order 243 K ferroelectric phase transition created by biaxial in-plane coherent tensile strain from DyScO3 substrates. Our extrinsic electrocaloric effects are an order of magnitude larger than the corresponding effects in bulk SrTiO3 over a wide range of temperatures including room temperature, and unlike electrocaloric effects associated with first-order transitions they are highly reversible in unipolar applied fields. Additionally, the canonical Landau description for strained SrTiO3 films works well if we set the low-temperature zero-field polarization along one of the in-plane pseudocubic <100> directions. In future, similar strain engineering could be exploited for other films, multilayers and bulk samples to increase the range of electrocaloric materials for energy efficient cooling.

Enabling ultra-low-voltage switching in BaTiO3.

Single crystals of BaTiO3 exhibit small switching fields and energies, but thin-film performance is considerably worse, thus precluding their use in next-generation devices. Here, we demonstrate high-quality BaTiO3 thin films with nearly bulk-like properties. Thickness scaling provides access to the coercive voltages (<100 mV) and fields (<10 kV cm-1) required for future applications and results in a switching energy of <2 J cm-3 (corresponding to <2 aJ per bit in a 10 × 10 × 10 nm3 device). While reduction in film thickness reduces coercive voltage, it does so at the expense of remanent polarization. Depolarization fields impact polar state stability in thicker films but fortunately suppress the coercive field, thus driving a deviation from Janovec-Kay-Dunn scaling and enabling a constant coercive field for films <150 nm in thickness. Switching studies reveal fast speeds (switching times of ~2 ns for 25-nm-thick films with 5-µm-diameter capacitors) and a pathway to subnanosecond switching. Finally, integration of BaTiO3 thin films onto silicon substrates is shown. We also discuss what remains to be demonstrated to enable the use of these materials for next-generation devices.

Shear-strain-mediated magnetoelectric effects revealed by imaging.

Large changes in the magnetization of ferromagnetic films can be electrically driven by non-180° ferroelectric domain switching in underlying substrates, but the shear components of the strains that mediate these magnetoelectric effects have not been considered so far. Here we reveal the presence of these shear strains in a polycrystalline film of Ni on a 0.68Pb(Mg1/3Nb2/3)O3-0.32PbTiO3 substrate in the pseudo-cubic (011)pc orientation. Although vibrating sample magnetometry records giant magnetoelectric effects that are consistent with the hitherto expected 90° rotations of a global magnetic easy axis, high-resolution vector maps of magnetization (constructed from photoemission electron microscopy data, with contrast from X-ray magnetic circular dichroism) reveal that the local magnetization typically rotates through smaller angles of 62-84°. This shortfall with respect to 90° is a consequence of the shear strain associated with ferroelectric domain switching. The non-orthogonality represents both a challenge and an opportunity for the development and miniaturization of magnetoelectric devices.

Evidence of a minority monoclinic LaNiO2.5 phase in lanthanum nickelate thin films.

LaNiO3 (LNO) thin films of 14 nm and 35 nm thicknesses grown epitaxially on LaAlO3 (LAO) and (LaAlO3)0.3(Sr2TaAlO6)0.7 (LSAT) substrates are studied using High Resolution Transmission Electron Microscopy (HRTEM) and High Angle Annular Dark Field (HAADF) imaging. The strain state of the films is studied using Geometric Phase Analysis (GPA). Results show the successful in-plane adaptation of the films to the substrates, both in the compressive (LAO) and tensile (LSAT) cases. Through the systematic analysis of HRTEM superstructure contrast modulation along different crystal orientations, localized regions of the monoclinic LaNiO2.5 phase are detected in the 35 nm films.

Two-dimensional electron gases at LaAlO3/SrTiO3 interfaces: orbital symmetry and hierarchy engineered by crystal orientation.

Recent findings show the emergence of two-dimensional electron gases (2DEGs) at LaAlO(3)/SrTiO(3) interfaces along different orientations; yet details on band reconstructions have remained so far unknown. Via x-ray linear dichroism spectroscopy, we demonstrate that crystal symmetry imposes distinctive 2DEG orbital hierarchies on (001)-and (110)-oriented quantum wells, allowing selective occupancy of states of different symmetry. Such orientational tuning expands the possibilities for electronic engineering of 2DEGs and opens up enticing opportunities to understand the link between orbital symmetry and complex correlated states at LaAlO(3)/SrTiO(3) quantum wells.

Strain relaxation dynamics of multiferroic orthorhombic manganites.

Resonant ultrasound spectroscopy has been used to characterise strain coupling and relaxation behavior associated with magnetic/magnetoelectric phase transitions in GdMnO3, TbMnO3and TbMn0.98Fe0.02O3through their influence on elastic/anelastic properties. Acoustic attenuation ahead of the paramagnetic to colinear-sinusoidal incommensurate antiferromagnetic transition at ∼41 K correlates with anomalies in dielectric properties and is interpreted in terms of Debye-like freezing processes. A loss peak at ∼150 K is related to a steep increase in electrical conductivity with a polaron mechanism. The activation energy,Ea, of ≳0.04 eV from a loss peak at ∼80 K is consistent with the existence of a well-defined temperature interval in which the paramagnetic structure is stabilised by local, dynamic correlations of electric and magnetic polarisation that couple with strain and have relaxation times in the vicinity of ∼10-6s. Comparison with previously published data for Sm0.6Y0.4MnO3confirms that this pattern may be typical for multiferroic orthorhombicRMnO3perovskites (R= Gd, Tb, Dy). A frequency-dependent loss peak near 10 K observed for TbMnO3and TbMn0.98Fe0.02O3, but not for GdMnO3, yieldedEa⩾ ∼0.002 eV and is interpreted as freezing of some magnetoelastic component of the cycloid structure. Small anomalies in elastic properties associated with the incommensurate and cycloidal magnetic transitions confirm results from thermal expansion data that the magnetic order parameters have weak but significant coupling with strain. Even at strain magnitudes of ∼0.1-1‰, polaron-like strain effects are clearly important in defining the development and evolution of magnetoelectric properties in these materials. Strains associated with the cubic-orthorhombic transition due to the combined Jahn-Teller/octahedral tilting transition in the vicinity of 1500 K are 2-3 orders of magnitude greater. It is inevitable that ferroelastic twin walls due to this transition would have significantly different magnetoelectric properties from homogeneous domains due to magnetoelastic coupling with steep strain gradients.

Voltage-driven annihilation and creation of magnetic vortices in Ni discs.

Using photoemission electron microscopy (PEEM) to image ferromagnetism in polycrystalline Ni disks, and ferroelectricity in their single-crystal BaTiO3 substrates, we find that voltage-driven 90° ferroelectric domain switching serves to reversibly annihilate each magnetic vortex via uniaxial compressive strain, and that the orientation of the resulting bi-domain reveals the chirality of the annihilated vortex. Micromagnetic simulations reveal that only 60% of this strain is required for annihilation. Voltage control of magnetic vortices is novel, and should be energetically favourable with respect to the use of a magnetic field or an electrical current. In future, stray field from bi-domains could be exploited to read vortex chirality. Given that core polarity can already be read via stray field, our work represents a step towards four-state low-power memory applications.

Large magnetoelectric coupling in multiferroic oxide heterostructures assembled via epitaxial lift-off.

Epitaxial films may be released from growth substrates and transferred to structurally and chemically incompatible substrates, but epitaxial films of transition metal perovskite oxides have not been transferred to electroactive substrates for voltage control of their myriad functional properties. Here we demonstrate good strain transmission at the incoherent interface between a strain-released film of epitaxially grown ferromagnetic La0.7Sr0.3MnO3 and an electroactive substrate of ferroelectric 0.68Pb(Mg1/3Nb2/3)O3-0.32PbTiO3 in a different crystallographic orientation. Our strain-mediated magnetoelectric coupling compares well with respect to epitaxial heterostructures, where the epitaxy responsible for strong coupling can degrade film magnetization via strain and dislocations. Moreover, the electrical switching of magnetic anisotropy is repeatable and non-volatile. High-resolution magnetic vector maps reveal that micromagnetic behaviour is governed by electrically controlled strain and cracks in the film. Our demonstration should inspire others to control the physical/chemical properties in strain-released epitaxial oxide films by using electroactive substrates to impart strain via non-epitaxial interfaces.

Surface symmetry-breaking and strain effects on orbital occupancy in transition metal perovskite epitaxial films.

The electron occupancy of 3d-orbitals determines the properties of transition metal oxides. This can be achieved, for example, through thin-film heterostructure engineering of ABO(3) oxides, enabling emerging properties at interfaces. Interestingly, epitaxial strain may break the degeneracy of 3d-e(g) and t(2g) orbitals, thus favoring a particular orbital filling with consequences for functional properties. Here we disclose the effects of symmetry breaking at free surfaces of ABO(3) perovskite epitaxial films and show that it can be combined with substrate-induced epitaxial strain to tailor at will the electron occupancy of in-plane and out-of-plane surface electronic orbitals. We use X-ray linear dichroism to monitor the relative contributions of surface, strain and atomic terminations to the occupancy of 3z(2)-r(2) and x(2)-y(2) orbitals in La(2/3)Sr(1/3)MnO(3) films. These findings open the possibility of an active tuning of surface electronic and magnetic properties as well as chemical properties (catalytic reactivity, wettability and so on).