Robust multiferroicity and magnetic modulation of the ferroelectric imprint field in heterostructures comprising epitaxial Hf0.5Zr0.5O2 and Co.

Magnetoelectric multiferroics, either single-phase or composites comprising ferroelectric/ferromagnetic coupled films, are promising candidates for energy efficient memory computing. However, most of the multiferroic magnetoelectric systems studied so far are based on materials that are not compatible with industrial processes. Doped hafnia is emerging as one of the few CMOS-compatible ferroelectric materials. Thus, it is highly relevant to study the integration of ferroelectric hafnia into multiferroic systems. In particular, ferroelectricity in hafnia, and the eventual magnetoelectric coupling when ferromagnetic layers are grown atop of it, are very much dependent on quality of interfaces. Since magnetic metals frequently exhibit noticeable reactivity when grown onto oxides, it is expected that ferroelectricity and magnetoelectricity might be reduced in multiferroic hafnia-based structures. In this article, we present excellent ferroelectric endurance and retention in epitaxial Hf0.5Zr0.5O2 films grown on buffered silicon using Co as the top electrode. The crucial influence of a thin Pt capping layer grown on top of Co on the ferroelectric functional characteristics is revealed by contrasting the utilization of Pt-capped Co, non-capped Co and Pt. Magnetic control of the imprint electric field (up to 40% modulation) is achieved in Pt-capped Co/Hf0.5Zr0.5O2 structures, although this does not lead to appreciable tuning of the ferroelectric polarization, as a result of its high stability. Computation of piezoelectric and flexoelectric strain-mediated mechanisms of the observed magnetoelectric coupling reveal that flexoelectric contributions are likely to be at the origin of the large imprint electric field variation.

Reversible optical control of magnetism in engineered artificial multiferroics.

Optical means instead of electric fields may offer a new pathway for low-power and wireless control of magnetism, holding great potential to design next-generation memory and spintronic devices. Artificial multiferroic materials have shown remarkable suitability as platforms towards the optical control of magnetic properties. However, the practical use of magnetic modulation should be both stable and reversible and, particularly, it should occur at room temperature. Here we show an unprecedented reversible modulation of magnetism using low-intensity visible-light in Fe75Al25/BaTiO3 heterostructures, at room temperature. This is enabled by the existence of highly oriented charged domain walls arranged in arrays of alternating in-plane and out-of-plane ferroelectric domains with stripe morphology. Light actuation yields a net anisotropic stress caused by ferroelectric domain switching, which leads to a 90-degree reorientation of the magnetic easy axis. Significant changes in the coercivity and squareness ratio of the hysteresis loops can be light-modulated, encouraging the development of novel low energy-consumption wireless magneto-optical devices.

Robust Antiferromagnetic FeRh Films on Mica.

FeRh shows an antiferromagnetic to ferromagnetic phase transition above room temperature, which permits its use as an antiferromagnetic memory element. However, its antiferromagnetic order is sensitive to small variations in crystallinity and composition, challenging its integration into flexible devices. Here, we show that flexible FeRh films of high crystalline quality can be synthesized by using mica as a substrate, followed by a mechanical exfoliation of the mica. The magnetic and transport data indicate that the FeRh films display a sharp antiferromagnetic to ferromagnetic phase transition. Magnetotransport data allow for the observation of two distinguishable resistance states, which are written after a field-cooling procedure. It is shown that the memory states are robust under the application of magnetic fields of up to 10 kOe.

Ferroelectric Electroresistance after a Breakdown in Epitaxial Hf0.5Zr0.5O2 Tunnel Junctions.

The recent discovery of ferroelectricity in doped HfO2 has opened perspectives on the development of memristors based on ferroelectric switching, including ferroelectric tunnel junctions. In these devices, conductive channels are formed in a similar manner to junctions based on nonferroelectric oxides. The formation of the conductive channels does not preclude the presence of ferroelectric switching, but little is known about the device ferroelectric properties after conduction path formation or their impact on the electric modulation of the resistance state. Here, we show that ferroelectricity and related sizable electroresistance are observed in pristine 4.6 nm epitaxial Hf0.5Zr0.5O2 (HZO) tunnel junctions grown on Si. After a soft breakdown induced by the application of suitable voltage, the resistance decreases by about five orders of magnitude, but signatures of ferroelectricity and electroresistance are still observed. Impedance spectroscopy allows us to conclude that the effective ferroelectric device area after the breakdown is reduced, most likely by the formation of conducting paths at the edge.

Ferroelectric Hf0.5Zr0.5O2 films with improved endurance obtained through low temperature epitaxial growth on seed layers.

Crystallization temperature is a critical parameter in the stabilization of the metastable ferroelectric phase of HfO2. The optimal crystallization temperature used for polycrystalline films is too low to grow epitaxial films. We have developed a new growth strategy, based on the use of an ultrathin seed layer, to obtain high-quality epitaxial films of orthorhombic Hf0.5Zr0.5O2 at a lower temperature. The threshold temperature for epitaxy is reduced from about 750 °C to about 550 °C using a seed layer. Epitaxial films deposited at low temperatures exhibit highly enhanced endurance, and films grown at 550-600 °C show high polarization, no wake-up effect, and greatly reduced fatigue and improved endurance in comparison with the films deposited at high temperatures without a seed layer. We propose that the endurance enhancement is due to a positive effect of the defects, which limits the propagation of pinned ferroelectric domains.

Control of up-to-down/down-to-up light-induced ferroelectric polarization reversal.

Light control of ferroelectric polarization is of interest for the exploitation of ferroelectric thin films in ultrafast data storage and logic functionalities. The rapidly oscillating electric field of light absorbed in a ferroelectric layer can suppress its polarization but cannot selectively reverse its direction. Here we take advantage of the built-in asymmetry at ferroelectric/electrode interfaces to break the up/down symmetry in uniaxial ferroelectrics to promote polarization reversal under illumination. It is shown that appropriate ferroelectric/metal structures allow the direction of the imprint electric field to be selected, which is instrumental for polarization reversal. This ability is further exploited by demonstrating the optical control of the resistance states in a ferroelectric capacitor.

Bendable Polycrystalline and Magnetic CoFe2O4 Membranes by Chemical Methods.

The preparation and manipulation of crystalline yet bendable functional complex oxide membranes has been a long-standing issue for a myriad of applications, in particular, for flexible electronics. Here, we investigate the viability to prepare magnetic and crystalline CoFe2O4 (CFO) membranes by means of the Sr3Al2O6 (SAO) sacrificial layer approach using chemical deposition techniques. Meticulous chemical and structural study of the SAO surface and SAO/CFO interface properties have allowed us to identify the formation of an amorphous SAO capping layer and carbonates upon air exposure, which dictate the crystalline quality of the subsequent CFO film growth. Vacuum annealing at 800 °C of SAO films promotes the elimination of the surface carbonates and the reconstruction of the SAO surface crystallinity. Ex-situ atomic layer deposition of CFO films at 250 °C on air-exposed SAO offers the opportunity to avoid high-temperature growth while achieving polycrystalline CFO films that can be successfully transferred to a polymer support preserving the magnetic properties under bending. Float on and transfer provides an alternative route to prepare freestanding and wrinkle-free CFO membrane films. The advances and challenges presented in this work are expected to help increase the capabilities to grow different oxide compositions and heterostructures of freestanding films and their range of functional properties.

Improved polarization and endurance in ferroelectric Hf0.5Zr0.5O2 films on SrTiO3(110).

The metastable orthorhombic phase of Hf0.5Zr0.5O2 (HZO) can be stabilized in thin films on La0.67Sr0.33MnO3 (LSMO) buffered (001)-oriented SrTiO3 (STO) by intriguing epitaxy that results in (111)-HZO oriented growth and robust ferroelectric properties. Here, we show that the orthorhombic phase can also be epitaxially stabilized on LSMO/STO(110), presenting the same out-of-plane (111) orientation but a different distribution of the in-plane crystalline domains. The remanent polarization of HZO films with a thickness of less than 7 nm on LSMO/STO(110) is 33 µC cm-3, which corresponds to a 50% improvement over equivalent films on LSMO/STO(001). Furthermore, HZO on LSMO/STO(110) presents higher endurance, switchable polarization is still observed up to 4 × 1010 cycles, and retention of more than 10 years. These results demonstrate that tuning the epitaxial growth of ferroelectric HfO2, here using STO(110) substrates, allows the improvement of functional properties of relevance for memory applications.

Impact of La Concentration on Ferroelectricity of La-Doped HfO2 Epitaxial Thin Films.

Epitaxial thin films of HfO2 doped with La have been grown on SrTiO3(001) and Si(001), and the impact of the La concentration on the stabilization of the ferroelectric phase has been determined. Films with 2-5 at. % La doping present the least amount of paraelectric monoclinic and cubic phases and exhibit the highest polarization, having a remanent polarization above 20 µC/cm2. The dopant concentration results in an important effect on the coercive field, which is reduced with increasing La content. Combined high polarization, high retention, and high endurance of at least 1010 cycles is obtained in 5 at. % La-doped films.

High-Temperature Synthesis and Dielectric Properties of LaTaON2.

The development of new synthetic methodologies of perovskite oxynitrides is challenging but necessary for the search of new compounds and the investigation of new properties. Here, we report a new method of preparation of the perovskite LaTaON2 that has been investigated as a pigment and photocatalyst for water splitting. The synthesis proceeds through the solid-state reactions under N2 at 1500 °C between La2O3, LaN, and Ta3N5 or between LaN and TaON, which are completed after 3 h and lead to sintered, highly crystalline samples with particle sizes up to 1 µm. Nitrogen-deficient samples LaTaO1+xN2-x with x ≤ 0.35 are prepared by changing the N/O ratio in the mixture of reactants. Electron diffraction, synchrotron diffraction, and neutron diffraction studies on stoichiometric and nitrogen-deficient compounds indicate that they crystallize in the monoclinic space group I2/m with lattice parameters for LaTaON2 of a = 5.71458(7), b = 8.05987(10), c = 5.74772(6) Å, and ß = 89.982(3)°. The three anion sites of the I2/m structure are partially occupied by oxygen and nitrogen, with a preference of nitride for two positions with occupancies of 77 and 88%. This anion distribution is different from that reported in previous studies of samples prepared by ammonolysis at lower temperature, suggesting that the synthesis conditions affect the anion order of this perovskite. Optical measurements indicate a band gap of about 1.9 eV, which is close to that observed in samples prepared by other methods. The determined dielectric permittivity for LaTaON2 εr ≈ 200, reported for the first time for a highly nitrided pseudocubic perovskite, is similar to that observed in perovskites with one nitrogen per formula.

Non-volatile optical switch of resistance in photoferroelectric tunnel junctions.

In the quest for energy efficient and fast memory elements, optically controlled ferroelectric memories are promising candidates. Here, we show that, by taking advantage of the imprint electric field existing in the nanometric BaTiO3 films and their photovoltaic response at visible light, the polarization of suitably written domains can be reversed under illumination. We exploit this effect to trigger and measure the associate change of resistance in tunnel devices. We show that engineering the device structure by inserting an auxiliary dielectric layer, the electroresistance increases by a factor near 2 × 103%, and a robust electric and optic cycling of the device can be obtained mimicking the operation of a memory device under dual control of light and electric fields.

Engineering Polar Oxynitrides: Hexagonal Perovskite BaWON2.

Non-centrosymmetric polar compounds have important technological properties. Reported perovskite oxynitrides show centrosymmetric structures, and for some of them high permittivities have been observed and ascribed to local dipoles induced by partial order of nitride and oxide. Reported here is the first hexagonal perovskite oxynitride BaWON2 , which shows a polar 6H polytype. Synchrotron X-ray and neutron powder diffraction, and annular bright-field in scanning transmission electron microscopy indicate that it crystalizes in the non-centrosymmetric space group P63 mc, with a total order of nitride and oxide at two distinct coordination environments in cubic and hexagonal packed BaX3 layers. A synergetic second-order Jahn-Teller effect, supported by first principle calculations, anion order, and electrostatic repulsions between W6+ cations, induce large distortions at two inequivalent face-sharing octahedra that lead to long-range ordered dipoles and spontaneous polarization along the c axis. The new oxynitride is a semiconductor with a band gap of 1.1 eV and a large permittivity.

High polarization, endurance and retention in sub-5 nm Hf0.5Zr0.5O2 films.

Ferroelectric HfO2 is a promising material for new memory devices, but significant improvement of its important properties is necessary for practical application. However, previous literature shows that a dilemma exists between polarization, endurance and retention. Since all these properties should be simultaneously high, overcoming this issue is of the highest relevance. Here, we demonstrate that high crystalline quality sub-5 nm Hf0.5Zr0.5O2 capacitors, integrated epitaxially with Si(001), present combined high polarization (2Pr of 27 µC cm-2 in the pristine state), endurance (2Pr > 6 µC cm-2 after 1011 cycles) and retention (2Pr > 12 µC cm-2 extrapolated at 10 years) using the same poling conditions (2.5 V). This achievement is demonstrated in films thinner than 5 nm, thus opening bright possibilities in ferroelectric tunnel junctions and other devices.

Flexible Antiferromagnetic FeRh Tapes as Memory Elements.

The antiferromagnetic to ferromagnetic transition occurring above room temperature in FeRh is attracting interest for applications in spintronics, with perspectives for robust and untraceable data storage. Here, we show that FeRh films can be grown on a flexible metallic substrate (tape shaped), coated with a textured rock-salt MgO layer, suitable for large-scale applications. The FeRh tape displays a sharp antiferromagnetic to ferromagnetic transition at about 90 °C. Its magnetic properties are preserved by bending (radii of 300 mm), and their anisotropic magnetoresistance (up to 0.05%) is used to illustrate data writing/reading capability.

Band Gap Tuning of Solution-Processed Ferroelectric Perovskite BiFe1-x Co x O3 Thin Films.

Ferroelectric perovskite oxides are emerging as a promising photoactive layer for photovoltaic applications because of their very high stability and their alternative ferroelectricity-related mechanism for solar energy conversion that could lead to extraordinarily high efficiencies. One of the biggest challenges so far is to reduce their band gap toward the visible region while simultaneously retaining ferroelectricity. To address these two issues, herein an elemental composition engineering of BiFeO3 is performed by substituting Fe by Co cations, as a means to tune the characteristics of the transition metal-oxygen bond. We demonstrate by solution processing the formation of epitaxial, pure phase, and stable BiFe1-x Co x O3 thin films for x ≤ 0.3 and film thickness up to 100 nm. Importantly, the band gap can be tuned from 2.7 to 2.3 eV upon cobalt substitution while simultaneously enhancing ferroelectricity. As a proof of concept, nonoptimized vertical devices have been fabricated and, reassuringly, the electrical photoresponse in the visible region of the Co-substituted phase is improved with respect to the unsubstituted oxide.

Complementary Resistive Switching Using Metal-Ferroelectric-Metal Tunnel Junctions.

Complementary resistive switching (CRS) devices are receiving attention because they can potentially solve the current-sneak and current-leakage problems of memory arrays based on resistive switching (RS) elements. It is shown here that a simple anti-serial connection of two ferroelectric tunnel junctions, based on BaTiO3 , with symmetric top metallic electrodes and a common, floating bottom nanometric film electrode, constitute a CRS memory element. It allows nonvolatile storage of binary states ("1" = "HRS+LRS" and "0" = "LRS+HRS"), where HRS (LRS) indicate the high (low) resistance state of each ferroelectric tunnel junction. Remarkably, these states have an identical and large resistance in the remanent state, characteristic of CRS. Here, protocols for writing information are reported and it is shown that non-destructive or destructive reading schemes can be chosen by selecting the appropriate reading voltage amplitude. Moreover, this dual-tunnel device has a significantly lower power consumption than a single ferroelectric tunnel junction to perform writing/reading functions, as is experimentally demonstrated. These findings illustrate that the recent impressive development of ferroelectric tunnel junctions can be further exploited to contribute to solving critical bottlenecks in data storage and logic functions implemented using RS elements.

Epitaxial Integration on Si(001) of Ferroelectric Hf0.5Zr0.5O2 Capacitors with High Retention and Endurance.

Epitaxial ferroelectric Hf0.5Zr0.5O2 films have been successfully integrated in a capacitor heterostructure on Si(001). The orthorhombic Hf0.5Zr0.5O2 phase, [111] out-of-plane oriented, is stabilized in the films. The films present high remnant polarization Pr close to 20 µC/cm2, rivaling with equivalent epitaxial films on single crystalline oxide substrates. Retention time is longer than 10 years for a writing field of around 5 MV/cm, and the capacitors show endurance up to 109 cycles for a writing voltage of around 4 MV/cm. It is found that the formation of the orthorhombic ferroelectric phase depends critically on the bottom electrode, being achieved on La0.67Sr0.33MnO3 but not on LaNiO3. The demonstration of excellent ferroelectric properties in epitaxial films of Hf0.5Zr0.5O2 on Si(001) is relevant toward fabrication of devices that require homogeneity in the nanometer scale, as well as for better understanding of the intrinsic properties of this promising ferroelectric oxide.

Disclosing odd symmetry, strain driven magnetic response of Co on Pt/PMN-PT (0 1 1).

An odd-symmetry magnetic response of multiferroic composites comprising ultrathin Co layers on Pt electrodes on [Pb(Mg0.33Nb0.67)O3](1-x)[PbTiO3] x (PMN-PT) (0 1 1) piezoelectric substrates is observed upon electrical poling of the PMN-PT substrates: the magnetic easy axis of the Co rotates by 90° in-plane between oppositely poled ferroelectric states, mimicking the signature of a surface polarization charge driven effect, which however can be excluded from the presence of the thick Pt interlayer. The origin for this unexpected behavior is as an odd symmetry piezoelectric response of the PMN-PT substrate, as indicated by x-ray diffraction with applied poling, in combination with conventional magnetoelastic coupling. Ferroelectric characterization reveals corresponding features, possibly related to an unswitchable polarization component.

Control of Polar Orientation and Lattice Strain in Epitaxial BaTiO3 Films on Silicon.

Conventional strain engineering of epitaxial ferroelectric oxide thin films is based on the selection of substrates with a suitable lattice parameter. Here, we show that the variation of oxygen pressure during pulsed laser deposition is a flexible strain engineering method for epitaxial ferroelectric BaTiO3 films either on perovskite substrates or on Si(001) wafers. This unconventional growth strategy permits continuous tuning of strain up to high levels (ε > 0.8%) in films greater than one hundred nanometers thick, as well as selecting the polar axis orientation to be either parallel or perpendicular to the substrate surface plane.

Control of the Polarization of Ferroelectric Capacitors by the Concurrent Action of Light and Adsorbates.

Ferroelectric perovskites hold promise of enhanced photovoltaic efficiency and photocatalytic activity. Consequently, the photoresponse of oxide ferroelectric thin films is an active field of research. In electrode/ferroelectric/electrode devices, internal charge in the ferroelectric, free charge in the electrodes, and buried adsorbates at interfaces combine to screen the ferroelectric polarization and to stabilize the polar state. Under illumination, photoinduced carriers and photodissociated adsorbates may disrupt the screening equilibrium, modifying the switchable polarization and altering its expected benefits. Here, we explore the photoresponse of BaTiO3 thin films in a capacitor geometry, focusing on the effects of visible illumination on the remanent polarization. By combining ferroelectric and X-ray photoelectron spectroscopy, we discover that photoreaction of charge-screening H2O-derived adsorbates at the buried metal-ferroelectric Pt/BaTiO3 interface plays an unexpected pivotal role, enabling a substantial modulation (up to 75%) of the switchable remanent polarization by light. These findings illustrate that the synergy between photochemistry and photovoltaic activity at the surface of a ferroelectric material can be exploited to tune photoferroelectric activity.