Electromechanics of Ferroelectric‐Like Behavior of LaAlO3 Thin Films

Electromechanical coupling in complex oxide heterostructures opens new possibilities for the development of a broad range of novel electronic devices with enhanced functionality. In this article, the switchable hysteretic electro­mechanical behavior of crystalline epitaxial LaAlO₃ (LAO) thin films associated with polarization induced by electrical and mechanical stimuli is investigated. The field–time‐dependent testing of the induced polarization states along with transport measurements and theoretical modeling suggests that the ferroelectric‐like response of the LAO thin films is mediated by the field‐induced ion migration in the bulk of the film. Comparative analysis of the dynamics of polarization reversal under the electrical field and mechanical stress applied via a tip of a scanning probe microscope demonstrates that both electrical and mechanical stimulus can be used to effectively control polarization at least at the submillisecond timescale. However, the mechanical writing is more localized than the electrical one. A combined electrical/mechanical approach for tuning the physical properties of oxide hetero­structures may potentially facilitate novel memory and logic devices, in which the data bits are written mechanically and read electrically.     

Fabrication and Electrochemical Properties of Epitaxial Samarium‐Doped Ceria Films on SrTiO3‐Buffered MgO Substrates

Thin films of samarium‐oxide‐doped (20 mol%) ceria (SDC) are grown by pulsed‐laser deposition (PLD) on (001) MgO single‐crystal substrates. SrTiO₃ (STO) prepared by PLD is used as a buffer layer on the MgO substrates to enable epitaxial growth of the fluorite‐structured SDC film; the STO layer provides a proper crystalline match between SDC and MgO, resulting in highly crystalline, epitaxial SDC films grown in the (001) orientation. Film conductivity is evaluated by electrochemical impedance spectroscopy measurements, which are performed at various temperatures (400–775 °C) in a wide range of oxygen partial pressure (pO₂) values (10^?25?1 atm) in order to separate ionic and electronic conductivity contributions. At 700 °C, SDC/STO films on (100) MgO exhibit a dominant ionic conductivity of about 7 × 10^?2 S cm^?1, down to pO₂ values of about 10^?15 atm. The absence of grain boundaries make the SDC/STO/MgO heterostructures stable to oxidation‐reduction cycles at high temperatures, in contrast to that observed for the more disordered SDC/STO films, which degraded after hydrogen exposure.     

Relaxor Behavior in Ordered Lead Magnesium Niobate (PbMg1/3Nb2/3O3) Thin Films

The local compositional heterogeneity associated with the short‐range ordering of Mg and Nb in PbMg_1/3Nb_2/3O₃ (PMN) is correlated with its characteristic relaxor ferroelectric behavior. Fully ordered PMN is not prepared as a bulk material. This work examines the relaxor behavior in PMN thin films grown at temperatures below 1073 K by artificially reducing the degree of disorder via synthesis of heterostructures with alternate layers of Pb(Mg_2/3Nb_1/3)O₃ and PbNbO₃, as suggested by the random‐site model. 100 nm thick, phase‐pure films are grown epitaxially on (111) SrTiO₃ substrates using alternate target timed pulsed‐laser deposition of Pb(Mg_2/3Nb_1/3)O₃ and PbNbO₃ targets with 20% excess Pb. Selected area electron diffraction confirms the emergence of (1/2, 1/2, 1/2) superlattice spots with randomly distributed ordered domains as large as ≈150 nm. These heterostructures exhibit a dielectric constant of 800, loss tangents of ≈0.03 and 2× remanent polarization of ≈11 µC cm^?2 at room temperature. Polarization–electric field hysteresis loops, Rayleigh data, and optical second‐harmonic generation measurements are consistent with the development of ferroelectric domains below 140 K. Temperature‐dependent permittivity measurements demonstrate reduced frequency dispersion compared to short range ordered PMN films. This work suggests a continuum between normal and relaxor ferroelectric behavior in the engineered PMN thin films.     

X‐Ray Writing of Metallic Conductivity and Oxygen Vacancies at Silicon/SrTiO3 Interfaces

Tunable electronic properties of transition metal oxides and their interfaces offer remarkable functionalities for future devices. The interest in these materials has been boosted with the discovery of a 2D electron gas (2DEG) at SrTiO₃ (STO)‐based interfaces. For the majority of these systems, oxygen vacancies play a crucial role in the emergence of interface conductivity, ferromagnetism, and high electron mobility. Despite its great importance, controlling the density and spatial distribution of oxygen vacancies in a dynamic way remains extremely challenging. Here, lithography‐like writing of a metallic state at the interface between SrTiO₃ and amorphous Si using X‐ray irradiation is reported. Using a combination of transport techniques and in operando photoemission spectroscopy, it is revealed in real time that the X‐ray radiation induces transfer of oxygen across the interface leading to the on‐demand formation of oxygen vacancies and a 2DEG in STO. The formed 2DEG stays stable in ambient conditions as the interface oxygen vacancies are stabilized by the capping of Si. The study provides a fundamental understanding of X‐ray‐induced redox reactions at the SrTiO₃‐based interfaces and in addition shows the potential of X‐ray radiation for patterning stabile conductive pathways for future oxide‐based electronic devices.     

Ultrahigh Tunability of Room Temperature Electronic Transport and Ferromagnetism in Dilute Magnetic Semiconductor and PMN‐PT Single‐Crystal‐Based Field Effect Transistors via Electric Charge Mediation

Multiferroic heterostructures composed of complex oxide thin films and ferroelectric single crystals have aroused considerable interest due to the electrically switchable strain and charge elements of oxide films by the polarization reversal of ferroelectrics. Previous studies have demonstrated that the electric‐field‐control of physical properties of such heterostructures is exclusively due to the ferroelectric domain switching‐induced lattice strain effects. Here, the first successful integration of the hexagonal ZnO:Mn dilute magnetic semiconductor thin films with high performance (111)‐oriented perovskite Pb(Mg_1/3Nb_2/3)O₃‐PbTiO₃ (PMN‐PT) single crystals is reported, and unprecedented charge‐mediated electric‐field control of both electronic transport and ferromagnetism at room temperature for PMN‐PT single crystal‐based oxide heterostructures is realized. A significant carrier concentration‐tunability of resistance and magnetization by ≈400% and ≈257% is achieved at room temperature. The electric‐field controlled bistable resistance and ferromagnetism switching at room temperature via interfacial electric charge presents a potential strategy for designing prototype devices for information storage. The results also disclose that the relative importance of the strain effect and interfacial charge effect in oxide film/ferroelectric crystal heterostructures can be tuned by appropriately adjusting the charge carrier density of oxide films.     

Nonvolatile Ferroelectric Memory Effect in Ultrathin α‐In2Se3

High‐density memory is integral in solid‐state electronics. 2D ferroelectrics offer a new platform for developing ultrathin electronic devices with nonvolatile functionality. Recent experiments on layered α‐In₂Se₃ confirm its room‐temperature out‐of‐plane ferroelectricity under ambient conditions. Here, a nonvolatile memory effect in a hybrid 2D ferroelectric field‐effect transistor (FeFET) made of ultrathin α‐In₂Se₃ and graphene is demonstrated. The resistance of the graphene channel in the FeFET is effectively controllable and retentive due to the electrostatic doping, which stems from the electric polarization of the ferroelectric α‐In₂Se₃. The electronic logic bit can be represented and stored with different orientations of electric dipoles in the top‐gate ferroelectric. The 2D FeFET can be randomly rewritten over more than 10⁵ cycles without losing the nonvolatility. The approach demonstrates a prototype of rewritable nonvolatile memory with ferroelectricity in van der Waals 2D materials.     

Strain‐Mediated Inverse Photoresistivity in SrRuO3/La0.7Sr0.3MnO3 Superlattices

In the pursuit of novel functionalities by utilizing the lattice degree of freedom in complex oxide heterostructure, the control mechanism through direct strain manipulation across the interfaces is still under development, especially with various stimuli, such as electric field, magnetic field, light, etc. In this study, the superlattices consisting of colossal‐magnetoresistive manganites La_0.7Sr_0.3MnO₃ (LSMO) and photostrictive SrRuO₃ (SRO) have been designed to investigate the light‐dependent controllability of lattice order in the corresponding functionalities and rich interface physics. Two substrates, SrTiO₃ (STO) and LaAlO₃ (LAO), have been employed to provide the different strain environments to the superlattice system, in which the LSMO sublayers exhibit different orbital occupations. Subsequently, by introducing light, we can modulate the strain state and orbital preference of LSMO sublayers through light‐induced expansion of SRO sublayers, leading to surprisingly opposite changes in photoresistivity. The observed photoresistivity decreases in the superlattice grown on STO substrate while increases in the superlattice grown on LAO substrate under light illumination. This work has presented a model system that demonstrates the manipulation of orbital–lattice coupling and the resultant functionalities in artificial oxide superlattices via light stimulus.     

Blocking of Conducting Channels Widens Window for Ferroelectric Resistive Switching in Interface‐Engineered Hf0.5Zr0.5O2 Tunnel Devices

Films of Hf_0.5Z_0.5O₂ (HZO) contain a network of grain boundaries. In (111) HZO epitaxial films on (001) SrTiO₃, for instance, twinned orthorhombic (o‐HZO) ferroelectric crystallites coexist with grain boundaries between o‐HZO and a residual paraelectric monoclinic (m‐HZO) phase. These grain boundaries contribute to the resistive switching response in addition to the genuine ferroelectric polarization switching and have detrimental effects on device performance. Here, it is shown that, by using suitable nanometric capping layer deposited on HZO film, a radical improvement of the operation window of the tunnel device can be achieved. Crystalline SrTiO₃ and amorphous AlO_x are explored as capping layers. It is observed that these layers conformally coat the HZO surface and allow to increase the yield and homogeneity of ferroelectric junctions while strengthening endurance. Data show that the capping layers block ionic‐like transport channels across grain boundaries. It is suggested that they act as oxygen suppliers to the oxygen‐getters grain boundaries in HZO. In this scenario it could be envisaged that these and other oxides could also be explored and tested for fully compatible CMOS technologies.     

Nanoscale Resistive Switching in Amorphous Perovskite Oxide (a‐SrTiO3) Memristors

Memristive devices are the precursors to high density nanoscale memories and the building blocks for neuromorphic computing. In this work, a unique room temperature synthesized perovskite oxide (amorphous SrTiO₃: a‐STO) thin film platform with engineered oxygen deficiencies is shown to realize high performance and scalable metal‐oxide‐metal (MIM) memristive arrays demonstrating excellent uniformity of the key resistive switching parameters. a‐STO memristors exhibit nonvolatile bipolar resistive switching with significantly high (10³–10⁴) switching ratios, good endurance (>10⁶I–V sweep cycles), and retention with less than 1% change in resistance over repeated 10⁵ s long READ cycles. Nano‐contact studies utilizing in situ electrical nanoindentation technique reveal nanoionics driven switching processes that rely on isolatedly controllable nano‐switches uniformly distributed over the device area. Furthermore, in situ electrical nanoindentation studies on ultrathin a‐STO/metal stacks highlight the impact of mechanical stress on the modulation of non‐linear ionic transport mechanisms in perovskite oxides while confirming the ultimate scalability of these devices. These results highlight the promise of amorphous perovskite memristors for high performance CMOS/CMOL compatible memristive systems.     

High‐Temperature Photochromism of Fe‐Doped SrTiO3 Caused by UV‐Induced Bulk Stoichiometry Changes

The impact of UV irradiation on Fe‐doped SrTiO₃ (Fe:STO) single crystals is investigated at elevated temperatures. Illumination leads to incorporation of oxygen into the single crystals and thus to a decreasing oxygen vacancy concentration and oxidation of Fe³⁺ to Fe⁴⁺. The Fe⁴⁺ ions cause a color change from transparent/brownish to black. This photochromic blackening due to stoichiometry changes at elevated temperatures is irreversible at room temperature, but annealing at high temperatures, for example at 700 °C, can restore the original stoichiometry and color. Absorbance changes due to UV irradiation are monitored by ex situ and in situ UV–vis spectroscopy experiments and changes in electrical properties are measured by van der Pauw measurements and in‐plane electrochemical impedance spectroscopy. After 1140 min of illumination at 440 °C, for example, electrical measurements reveal a conductivity increase by more than a factor of 5 due to the enhanced hole concentration in blackened Fe:STO. In addition, UV illumination increases the oxygen chemical potential up to a calculated p(O₂) of more than 10⁹ Pa in Fe:STO. Hence, UV light can be used to tune the color, but also electrical properties of Fe:STO by directly impacting the bulk defect concentrations.     

Examination of LiNbO3/nitride heterostructures

Oxides such as LiNbO₃, PbTiO₃, etc. have large polarization effects arising from the ferroelectric and piezoelectric effects. Recent work on nitride heterostructures has shown that polar charge can be used to substitute for dopant charge and controlled to create a two-dimensional electron (and hole) gas, resulting in ohmic contacts and diode like current–voltage characteristics. In this paper, we examine the potential of using ferroelectrics with traditional semiconductors for applications in novel electronic devices. In particular, we examine their use in creating very high sheet charge densities of mobile charge and tailorable current–voltage characteristics. It is seen that owing to hysteresis based effects in the ferroelectric layer, the direction of variation of voltage has a marked effect on the charge induced as well as the variation of that charge with voltage.     

Epitaxial Ferroelectric Heterostructures with Nanocolumn‐Enhanced Dynamic Properties

The possibility to tailor ferroelectricity by controlling epitaxial strain in thin films and heterostructures of complex metal oxides is well established. Here it is demonstrated that apart from this mechanism, 3D film growth during heteroepitaxy can be used to favor specific domain configurations that lead to step‐like polarization switching and a giant nonlinear dielectric response in sub‐switching ac electric fields. A combination of cube‐on‐cube epitaxial growth and the formation of columnar structures during pulsed laser deposition of Pb_0.5Sr_0.5TiO₃ films on La_0.5Sr_0.5CoO₃ bottom electrode layers and MgO (001) substrates stabilizes ferroelectric nanodomains with enhanced dynamic properties. In the Pb_0.5Sr_0.5TiO₃ films, a‐ and c‐oriented epitaxial columns grow from the bottom to the top of the film leading to random polydomain architectures with strong associations between the ferroelectric domains and the nanocolumns. Polarization switching in the two domain populations is initiated at distinctive fields due to domain wall pinning on column boundaries. Moreover, piezoelectric coupling between ferroelectric domains leads to strong interdomain elastic interactions, which result in an enhanced Rayleigh‐type dielectric nonlinearity. The growth of epitaxial films with 3D columnar structures opens up new routes towards the engineering of enhanced ferroelectric and electromechanical functions in a broad class of complex oxide materials.     

Epitaxial TiOx Surface in Ferroelectric BaTiO3: Native Structure and Dynamic Patterning at the Atomic Scale

Surfaces and interfaces of ferroelectric oxides exhibit enhanced functionality, and therefore serve as a platform for novel nano and quantum technologies. Experimental and theoretical challenges associated with examining the subtle electro‐chemo‐mechanical balance at metal‐oxide surfaces have hindered the understanding and control of their structure and behavior. Here, combined are advanced electron‐microscopy and first‐principles thermodynamics methods to reveal the atomic‐scale chemical and crystallographic structure of the surface of the seminal ferroelectric BaTiO₃. It is shown that the surface is composed of a native <2 nm thick TiO_x rock‐salt layer in epitaxial registry with the BaTiO₃. Using electron‐beam irradiation, artificial TiO_x sites with sub‐nanometer resolution are successfully patterned, by inducing Ba escape. Therefore, this work offers electro‐chemo‐mechanical insights into ferroelectric surface behavior in addition to a method for scalable high‐resolution beam‐induced chemical lithography for selectively driving surface phase transitions, and thereby functionalizing metal‐oxide surfaces.     

Graphene/Strontium Titanate: Approaching Single Crystal–Like Charge Transport in Polycrystalline Oxide Perovskite Nanocomposites through Grain Boundary Engineering

Grain boundaries critically limit the electronic performance of oxide perovskites. These interfaces lower the carrier mobilities of polycrystalline materials by several orders of magnitude compared to single crystals. Despite extensive effort, improving the mobility of polycrystalline materials (to meet the performance of single crystals) is still a severe challenge. In this work, the grain boundary effect is eliminated in perovskite strontium titanate (STO) by incorporating graphene into the polycrystalline microstructure. An effective mass model provides strong evidence that polycrystalline graphene/strontium titanate (G/STO) nanocomposites approach single crystal‐like charge transport. This phenomenological model reduces the complexity of analyzing charge transport properties so that a quantitative comparison can be made between the nanocomposites and STO single crystals. In other related works, graphene composites also optimize the thermal transport properties of thermoelectric materials. Therefore, decorating grain boundaries with graphene appears to be a robust strategy to achieve “phonon glass–electron crystal” behavior in oxide perovskites.     

Thickness Dependent Properties in Oxide Heterostructures Driven by Structurally Induced Metal–Oxygen Hybridization Variations

Thickness‐driven electronic phase transitions are broadly observed in different types of functional perovskite heterostructures. However, uncertainty remains whether these effects are solely due to spatial confinement, broken symmetry, or rather to a change of structure with varying film thickness. Here, this study presents direct evidence for the relaxation of oxygen‐2p and Mn‐3d orbital (p–d) hybridization coupled to the layer‐dependent octahedral tilts within a La_2/3Sr_1/3MnO₃ film driven by interfacial octahedral coupling. An enhanced Curie temperature is achieved by reducing the octahedral tilting via interface structure engineering. Atomically resolved lattice, electronic, and magnetic structures together with X‐ray absorption spectroscopy demonstrate the central role of thickness‐dependent p–d hybridization in the widely observed dimensionality effects present in correlated oxide heterostructures.     

Nonvolatile Electrical Control and Heterointerface‐Induced Half‐Metallicity of 2D Ferromagnets

Electrical control of atom‐thick van der Waals (vdW) ferromagnets is a key toward future magnetoelectric nanodevices; however, state‐of‐the‐art control approaches are volatile. In this work, introducing ferroelectric switching as an aided layer is demonstrated to be an effective approach toward achieving nonvolatile electrical control of 2D ferromagnets. For example, when a ferromagnetic monolayer CrI₃ and ferroelectric MXene Sc₂CO₂ come together into multiferroic heterostructures, CrI₃ is controlled by polarized states P↑ and P↓ of Sc₂CO₂. P↑ Sc₂CO₂ does not change the semiconducting nature of CrI₃, but surprisingly P↓ Sc₂CO₂ makes CrI₃ half‐metallic. Nonvolatility of the electrical switching between two oppositely ferroelectric polarized states, therefore, indirectly enables nonvolatile electrical control of CrI₃ between ferromagnetic semiconductor and half‐metal. The heterointerface‐induced half‐metallicity in CrI₃ is intrinsic without resorting to any chemical functionalization or external physical modification, which is rather beneficial to the practical application. This work paves the way for nonvolatile electrical control of 2D vdW ferromagnets and applications of CrI₃ in half‐metal‐based nanospintronics.     

Submicrometric SrTiO3-δ based devices realized by an atomic force microscope

SrTiO₃ (STO) is one of the key compounds in the emerging field of oxide electronics. Because of the low carrier concentration needed to turn it into the conducting state (10¹⁸ e/cm³) and to its high bulk mobility (10⁴ cm²/Vs @ 4.2 K), we consider STO suitable as functional conducting element in future oxide based devices.In this work we show how by applying a negative voltage to the conducting tip of an atomic force microscope it is possible to modify on sub-micron scale structural and electrical properties of conducting SrTiO_3-δ thin films grown on insulating LaAlO₃ substrates, thus realizing sub-micrometric STO electrical circuits. After discussing the mechanisms of the process, we present the fabrication of a SrTiO_3-δ based side gate field effect transistor.     

Electrode Dependence of Tunneling Electroresistance and Switching Stability in Organic Ferroelectric P(VDF‐TrFE)‐Based Tunnel Junctions

Ferroelectric tunnel junctions (FTJs) are promising candidates for nonvolatile memories and memristor‐based computing circuits. Thus far, most research has focused on FTJs with a perovskite oxide ferroelectric tunnel barrier. As the need for high‐temperature epitaxial film growth challenges the technological application of such inorganic junctions, more easily processable organic ferroelectrics can serve as alternative if large tunneling electroresistance (TER) and good switching durability would persist. This study reports on the performance of FTJs with a spin‐coated ferroelectric P(VDF‐TrFE) copolymer tunnel barrier. The use of three different bottom electrodes, indium tin oxide (ITO), La_0.67Sr_0.33MnO₃, (LSMO), and Nb‐doped SrTiO₃ (STO) are compared and it is shown that the polarity and magnitude of the TER effect depend on their conductivity. The largest TER of up to 10⁷% at room temperature is measured on FTJs with a semiconducting Nb‐doped STO electrode. This large switching effect is attributed to the formation of an extra barrier over the space charge region in the substrate. The organic FTJs exhibit good resistance retention and switching endurance up to 380 K, which is just below the ferroelectric Curie temperature of the P(VDF‐TrFE) barrier.     

Modulating the Ferromagnet/Molecule Spin Hybridization Using an Artificial Magnetoelectric

Spin‐polarized charge transfer at the interface between a ferromagnetic (FM) metal and a molecule can lead to ferromagnetic coupling and to a high spin polarization at room temperature. The magnetic properties of these interfaces can not only alter those of the ferromagnet but can also stabilize molecular spin chains with interesting opportunities toward quantum computing. With the aim to enhance an organic spintronic device's functionality, external control over this spin polarization may thus be achieved by altering the ferromagnet/molecule interface's magnetic properties. To do so, the magnetoelectric properties of an underlying ferroelectric/ferromagnetic interface are utilized. Switching the ferroelectric polarization state of a PbZr_0.2Ti_0.8O₃ (PZT) bottom layer within a PZT/Co/FePc‐based (Pc ‐ phthalocyanine) device alters the X‐ray magnetic circular dichroism of the Fe site within the phthalocyanine molecular top layer. Thus, how to electrically alter the magnetic properties of an interface with high spin polarization at room temperature is demonstrated. This expands electrical control over spin‐polarized FM/molecule interfaces, which is first demonstrated using ferroelectric molecules, to all molecular classes.     

The Polar/Antipolar Phase Boundary of BiMnO3–BiFeO3–PbTiO3: Interplay among Crystal Structure,Point Defects,and Multiferroism

The ferromagnetic perovskite oxide BiMnO₃ is a highly topical material, and the solid solutions it forms with antiferromagnetic/ferroelectric BiFeO₃ and with ferroelectric PbTiO₃ result in distinctive polar/nonpolar morphotropic phase boundaries (MPBs). The exploitation of such a type of MPBs could be a novel approach to engineer novel multiferroics with phase‐change magnetoelectric responses, in addition to ferroelectrics with enhanced electromechanical performance. Here, the interplay among crystal structure, point defects, and multiferroic properties of the BiMnO₃–BiFeO₃–PbTiO₃ ternary system at its line of MPBs between polymorphs of tetragonal P4mm (polar) and orthorhombic Pnma (antipolar) symmetries is reported. A strong dependence of the phase coexistence on thermal history is found: phase percentage significantly changes whether the material is quenched or slowly cooled from high temperature. The origin of this phenomenon is investigated with temperature‐dependent structural and physical property characterizations. A major role of the complex defect chemistry, where a Bi/Pb‐deficiency allows Mn and Fe ions to have a mixed‐valence state, in the delicate balance between polymorphs is proposed, and its influence in the magnetic and electric ferroic orders is defined.