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We investigate magnetization-reversal processes in half-metallic epitaxial films of La0.67Sr0.33MnO3 on SrTiO3 (110) substrates. At 150 K, major loop magnetization reversal (MLMR) occurs beyond minor-loop switching fields, implying that MLMR is limited by domain nucleation. At 280 K, MLMR overlaps with minor-loop switching fields if there are deliberately introduced precipitates, implying that the precipitates limit MLMR by pinning domain walls. To confirm that the precipitates pin domain walls at 280 K, we use a two-dimensional analogue of the Gaunt pinning model to show that pinning limited switching occurs at fields consistent with the observed precipitate density of 0.3 2.0 μm 2. Our work demonstrates that comparing major and minor loops at any temperature of interest represents a simple way to check whether spintronic electrode materials show nucleation-limited MLMR, as circumstantially required for single-domain switching in micron-scale elements of La0.67Sr0.33MnO3 that represent spintronic electrodes [Phys. Rev. Appl. 4, 064004 (2015)].

We identify room-temperature converse magnetoelectric effects (CMEs) that are non-volatile by using a single-crystal substrate of PMN-PT (001)pc (pc denotes pseudocubic) to impart voltage-driven strain to a polycrystalline film of Ni. An appropriate magnetic-field history enhances the magnetoelectric coefficient to a near-record peak of ∼10-6 s m-1 and permits electrically driven magnetization reversal of substantial net magnetization. In zero magnetic field, electrically driven ferroelectric domain switching produces large changes of in-plane magnetization that are non-volatile. Microscopically, these changes are accompanied by the creation and destruction of magnetic stripe domains, implying the electrical control of perpendicular magnetic anisotropy. Moreover, the stripe direction can be rotated by a magnetic field or an electric field, the latter yielding the first example of electrically driven rotatable magnetic anisotropy. The observed CMEs are associated with repeatable ferroelectric domain switching that yields a memory effect. This memory effect is well known for PMN-PT (110)pc but not PMN-PT (001)pc. Given that close control of the applied field is not required as for PMN-PT (110)pc, this memory effect could lead the way to magnetoelectric memories based on PMN-PT (001)pc membranes that switch at low voltage.

We identify room-temperature converse magnetoelectric effects (CMEs) that are non-volatile by using a single-crystal substrate of PMN-PT (001)pc (pc denotes pseudocubic) to impart voltage-driven strain to a polycrystalline film of Ni. An appropriate magnetic-field history enhances the magnetoelectric coefficient to a near-record peak of ∼10-6 s m-1 and permits electrically driven magnetization reversal of substantial net magnetization. In zero magnetic field, electrically driven ferroelectric domain switching produces large changes of in-plane magnetization that are non-volatile. Microscopically, these changes are accompanied by the creation and destruction of magnetic stripe domains, implying the electrical control of perpendicular magnetic anisotropy. Moreover, the stripe direction can be rotated by a magnetic field or an electric field, the latter yielding the first example of electrically driven rotatable magnetic anisotropy. The observed CMEs are associated with repeatable ferroelectric domain switching that yields a memory effect. This memory effect is well known for PMN-PT (110)pc but not PMN-PT (001)pc. Given that close control of the applied field is not required as for PMN-PT (110)pc, this memory effect could lead the way to magnetoelectric memories based on PMN-PT (001)pc membranes that switch at low voltage.

One century after the discovery of ferroelectricity, and two decades after ferroelectric random access memories were first commercialized, this Special Issue of Advanced Electronic Materials demonstrates that the field of ferroelectricity is in robust health. First, ferroelectricity arises in very different types of material via different mechanisms. Second, ferroelectric domains in each type of material are liable to switch differently, for both intrinsic reasons (chemical formula) and extrinsic reasons (microstructure/strain). Third, an electrical polarization can display complex topologies. Fourth, ferroelectric order parameters can couple to other order parameters, e.g. magnetic order parameters. Fifth, ferroelectrics can be modified using light. Sixth, there continue to be improvements in techniques that measure ferroelectric and other ferroic materials. Seventh, ferroelectrics continue to attract the attention of experimentalists and theorists alike. We thank all of these people for their wonderful contributions, and below we identify papers via the name of the person invited. Last, we thank Dr Gaia Tomasello for suggesting the topic and inviting us to be Guest Editors. It has been a pleasure working with her.

Electrocaloric cooling devices are traditionally based on sub-millimetre-thick ceramic working bodies. Using instead a flexible polymer that is one order-of-magnitude thinner yields lightweight devices that have now been stacked to pump heat across a relatively wide temperature span.

We review our work on continuous Ni films coupled via strain to ferroelectric substrates of BaTiO3 (BTO) and 0.68Pb(Mg1/3Nb2/3)O3–0.32PbTiO3 (PMN-PT). We show that magnetic force microscopy (MFM) and photoemission electron microscopy (PEEM) of the Ni films (during or after electrical treatment) permit to reveal nanoscale converse magnetoelectric effects (CMEs) that are novel and elude macroscopic measurements. As examples, we discuss magnetization reversal without applied field in multilayer capacitors (MLCs), shear-strain-mediated CMEs in thin Ni films on PMN-PT and reversible switching of perpendicular magnetization from out-of-plane to in-plane in Ni films on BTO. In this latter case, we show that PEEM can be used to measure both magnetic and ferroelectric domains, thus providing key mechanistic insight in the magnetoelectric coupling mechanism.

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.

Uniaxial magnetic anisotropy was imposed on a CoFeB film by applying an in-plane magnetic field during growth. Electrically driven strain from a ferroelectric 0.68Pb(Mg1/3Nb2/3)O3-0.32PbTiO3 (011) substrate resulted in giant magnetoelectric effects, whose coupling constant peaked at a record value of ∼8.0 × 10−6 s m−1. These large magnetoelectric effects arose due to non-volatile 90° rotations of the magnetic easy axis, reflecting a competition between the fixed growth anisotropy and the voltage-controlled magnetoelastic anisotropy. In contrast to previous work, our non-volatile rotations did not require the assistance of an applied magnetic field or the setting of an in-plane substrate polarization prior to deposition.

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.

For 1 μm diameter Ni discs on a BaTiO3 substrate, the local magnetization direction is determined by ferroelectric domain orientation as a consequence of growth strain, such that single domain discs lie on single ferroelectric domains. On applying a voltage across the substrate, ferroelectric domain switching yields non volatile magnetization rotations of 90°, while piezoelectric effects that are small and continuous yield non volatile magnetization reversals that are non-deterministic. This demonstration of magnetization reversal without ferroelectric domain switching implies reduced fatigue, and therefore represents a step towards applications.

Heat pumps based on magnetocaloric and electrocaloric working bodies-in which entropic phase transitions are driven by changes of magnetic and electric field, respectively-use displaceable fluids to establish relatively large temperature spans between loads to be cooled and heat sinks1,2. However, the performance of prototypes is limited because practical magnetocaloric working bodies driven by permanent magnets3-5 and electrocaloric working bodies driven by voltage6-16 display temperature changes of less than 3 kelvin. Here we show that high-quality multilayer capacitors of PbSc0.5Ta0.5O3 display large electrocaloric effects over a wide range of starting temperatures when the first-order ferroelectric phase transition is driven supercritically (as verified by Landau theory) above the Curie temperature of 290 kelvin by electric fields of 29.0 volts per micrometre. Changes of temperature in the large central area of the capacitor peak at 5.5 kelvin near room temperature and exceed 3 kelvin for starting temperatures that span 176 kelvin (complete thermalization would reduce these values from 5.5 to 3.3 kelvin and from 176 to 73 kelvin). If magnetocaloric working bodies were to be replaced with multilayer capacitors of PbSc0.5Ta0.5O3, then the established design principles behind magnetocaloric heat pumps could be repurposed for better performance without bulky and expensive permanent magnets.

A characteristic feature of spin ice is its apparent violation of the third law of thermodynamics. This leads to a number of interesting properties including the emergence of an effective vacuum for magnetic monopoles and their currents – magnetricity. Here we add a new dimension to the experimental study of spin ice by fabricating thin epitaxial films of Dy2Ti2O7, varying between 5 and 60 monolayers on an inert substrate. The films show the distinctive characteristics of spin ice at temperatures >2 K, but at lower temperature we find evidence of a zero entropy state. This restoration of the third law in spin ice thin films is consistent with a predicted strain-induced ordering of a very unusual type, previously discussed for analogous electrical systems. Our results show how the physics of frustrated pyrochlore magnets such as spin ice may be significantly modified in thin-film samples., In bulk, the spin ice Dy2Ti2O7 has posed an enigma because – due to its slow dynamics – it is unclear whether and how the material will reach a zero entropy state at zero temperature. Here, the authors show that in thin films of Dy2Ti2O7 a zero entropy state is induced at 0.4 K, plausibly by lattice strain.

A novel experimental technique, resonant piezoelectric spectroscopy (RPS), has been applied to investigate polar precursor effects in highly (65%) B-site ordered PbSc0.5Ta0.5O3 (PST), which undergoes a ferroelectric phase transition near 300 K. The cubic-rhombohedral transition is weakly first order, with a coexistence interval of ∼4 K, and is accompanied by a significant elastic anomaly over a wide temperature interval. Precursor polarity in the cubic phase was detected as elastic vibrations generated by local piezoelectric excitations in the frequency range 250–710 kHz. The RPS resonance frequencies follow exactly the frequencies of elastic resonances generated by conventional resonant ultrasound spectroscopy (RUS) but RPS signals disappear on heating beyond an onset temperature, Tonset, of 425 K. Differences between the RPS and RUS responses can be understood if the PST structure in the precursor regime between Tonset and the transition point, Ttrans=300 K, has locally polar symmetry even while it remains macroscopically cubic. It is proposed that this precursor behavior could involve the development of a tweed microstructure arising by coupling between strain and multiple order parameters, which can be understood from the perspective of Landau theory. As a function of temperature the transition is driven by the polar displacement P and the order parameter for cation ordering on the crystallographic B site Qod. Results in the literature show that, as a function of pressure, there is a separate instability driven by octahedral tilting for which the assigned order parameter is Q. The two mainly displacive order parameters, P and Q, are unfavorably coupled via a biquadratic term Q2P2, and complex tweedlike fluctuations in the precursor regime would be expected to combine aspects of all the order parameters. This would be different from the development of polar nanoregions, which are more usually evoked to explain relaxor ferroelectric behavior, such as occurs in PST with a lower degree of B-site order.

Scanning tunneling spectroscopy measurements were performed on an epitaxial thin film of $La_{0.7}Ca_{0.3}MnO_{3}$ grown on a $NdGaO_{3}$ substrate. The temperature variation of the density of states (DOS) close to the ferromagnetic transition temperature $(T_c)$ was investigated. The strain-free film exhibiting a sharp metal-insulator transition at $T_p$ approximate to $T_c$ approximate to 268 K shows no phase separation as seen by the conductivity map, allowing unambiguous determination of the tunneling spectra as a function of T. The temperature dependence of the conductance (dI/dV) curves and the normalized DOS clearly indicate a depletion in DOS near $T_c$, which fills up as the sample is cooled below $T_c$. The metal-insulator transition at $T_c$ also shows up in the bias dependence of the tunneling curve as the temperature is changed across the transition. In the metallic phase we find that the DOS is similar to what is expected in a correlated metal.

We report investigation of non-linear electronic transport through artificial grain-boundary junctions made on epitaxial films of La0.7Ca0.3MnO3 on bicrystal SrTiO3 substrates. The experiments carried out over the temperature range 4.2 K–300 K in magnetic field up to 3 T allow us to identify some of the conduction mechanisms that may give rise to nonlinear transport in these grain boundary junctions. The nonlinear transport is associated with multistep inelastic processes in the grain-boundary region, which is moderately affected by the applied magnetic field. However the primary effect of the magnetic field is to enhance the zero-bias conductance [G0 = (dI/dV)V = 0]. The dominant voltage dependent contribution to the dynamic conductance (G = dI/dV) comes from a term of the type V4/3 at lower temperatures. Other voltage dependent contributions to G, which are of higher order in V, appear only for T>75 K. In addition we found a contribution to G arising from a V0.5 term, which is likely to arise from the disordered region around the grain boundary (GB). The magnetoresistance in the GB depends on the bias used and it decreases at higher bias. The bias dependence is found to be reduced as temperature is increased. We discuss the physical origins of the various contributions to the nonlinear conduction.

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., Beatriu de Pinós postdoctoral fellowship (2014 BP-A 00079) from the Catalan government via the Agència de Gestió d’Ajuts Universitaris i de Recerca (AGAUR); Ministry of Science and Higher Education of Russian Federation, goszadanie no. 2019-1246; the Royal Society; EPSRC (Grant EP/P009050/1, EP/M010619/1 and the NoWNano DTC); European Research Council (ERC) (ERC-2016-STG-EvoluTEM-715502 and ERC Synergy HETERO2D); “la Caixa” Foundation (ID 100010434).

Multilayer capacitors (MLCs) represent promising electrocaloric (EC) cooling elements because they operate at low voltages, they possess large breakdown fields, they contain inner electrodes that facilitate heat transfer, and they exhibit a macroscopic volume of active EC material. However, almost ten years after they were first suggested as EC elements, the internal heat flow has not been well studied. In this paper, we use an infrared camera to investigate heat flow within representative MLCs of Pb(Mg,Nb)O3, and we achieve good agreement with the results of finite element modelling (FEM) by identifying for the inner electrodes an effective thermal conductivity that represents the limiting factor for heat flow. Increasing the inner electrode thickness by a factor of five would increase heat flow by a factor of 2.6. Our work therefore shows that FEM can play an important role in MLC design for EC applications.

There is currently great interest in replacing the harmful volatile hydrofluorocarbon fluids used in refrigeration and air-conditioning with solid materials that display magnetocaloric, electrocaloric or mechanocaloric effects. However, the field-driven thermal changes in all of these caloric materials fall short with respect to their fluid counterparts. Here we show that plastic crystals of neopentylglycol (CH3)2C(CH2OH)2 display extremely large pressure-driven thermal changes near room temperature due to molecular reconfiguration, that these changes outperform those observed in any type of caloric material, and that these changes are comparable with those exploited commercially in hydrofluorocarbons. Our discovery of colossal barocaloric effects in a plastic crystal should bring barocaloric materials to the forefront of research and development in order to achieve safe environmentally friendly cooling without compromising performance.

Elastic and anelastic properties of ceramic samples of multiferroic perovskites with nominal compositions across the binary join PbZr$_{0.53}$Ti$_{0.47}$O$_3$–PbFe$_{0.5}$Ta$_{0.5}$O$_3$ (PZT–PFT) have been assembled to create a binary phase diagram and to address the role of strain relaxation associated with their phase transitions. Structural relationships are similar to those observed previously for PbZr$_{0.53}$Ti$_{0.47}$O$_3$–PbFe$_{0.5}$Nb$_{0.5}$O$_3$ (PZT–PFN), but the magnitude of the tetragonal shear strain associated with the ferroelectric order parameter appears to be much smaller. This leads to relaxor character for the development of ferroelectric properties in the end member PbFe$_{0.5}$Ta$_{0.5}$O$_3$. As for PZT–PFN, there appear to be two discrete instabilities rather than simply a reorientation of the electric dipole in the transition sequence cubic–tetragonal–monoclinic, and the second transition has characteristics typical of an improper ferroelastic. At intermediate compositions, the ferroelastic microstructure has strain heterogeneities on a mesoscopic length scale and, probably, also on a microscopic scale. This results in a wide anelastic freezing interval for strain-related defects rather than the freezing of discrete twin walls that would occur in a conventional ferroelastic material. In PFT, however, the acoustic loss behaviour more nearly resembles that due to freezing of conventional ferroelastic twin walls. Precursor softening of the shear modulus in both PFT and PFN does not fit with a Vogel–Fulcher description, but in PFT there is a temperature interval where the softening conforms to a power law suggestive of the role of fluctuations of the order parameter with dispersion along one branch of the Brillouin zone. Magnetic ordering appears to be coupled only weakly with a volume strain and not with shear strain but, as with multiferroic PZT–PFN perovskites, takes place within crystals which have significant strain heterogeneities on different length scales.

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., Key properties of transition metal perovskite oxides are degraded after epitaxial growth on ferroelectric substrates due to lattice-mismatch strain. Here, the authors use epitaxial lift-off and transfer to overcome this problem and demonstrate electric field control of a bulk-like magnetization.

Materials that show large and reversible electrically driven thermal changes near phase transitions have been proposed for cooling applications, but energy efficiency has barely been explored. Here we reveal that most of the work done to drive representative electrocaloric cycles does not pump heat and may therefore be recovered. Initially, we recover 75–80% of the work done each time BaTiO3-based multilayer capacitors drive electrocaloric effects in each other via an inductor (diodes prevent electrical resonance while heat flows after each charge transfer). For a prototype refrigerator with 24 such capacitors, recovering 65% of the work done to drive electrocaloric effects increases the coefficient of performance by a factor of 2.9. The coefficient of performance is subsequently increased by reducing the pumped heat and recovering more work. Our strategy mitigates the advantage held by magnetocaloric prototypes that exploit automatic energy recovery, and should be mandatory in future electrocaloric cooling devices., Electrocaloric materials can be electrically driven to pump heat and hold promise for use in efficient solid-state refrigeration. Here, the authors demonstrate an approach to recycle recoverable energy from electrocaloric cycles, offering a method to enhance performance in electrocaloric refrigeration systems.