Giant Electric Field Tuning of Magnetic Properties in Multiferroic Ferrite/Ferroelectric Heterostructures

Multiferroic heterostructures of Fe₃O₄/PZT (lead zirconium titanate), Fe₃O₄/PMN‐PT (lead magnesium niobate‐lead titanate) and Fe₃O₄/PZN‐PT (lead zinc niobate‐lead titanate) are prepared by spin‐spray depositing Fe₃O₄ ferrite film on ferroelectric PZT, PMN‐PT and PZN‐PT substrates at a low temperature of 90 °C. Strong magnetoelectric coupling (ME) and giant microwave tunability are demonstrated by a electrostatic field induced magnetic anisotropic field change in these heterostructures. A high electrostatically tunable ferromagnetic resonance (FMR) field shift up to 600 Oe, corresponding to a large microwave ME coefficient of 67 Oe cm kV^?1, is observed in Fe₃O₄/PMN‐PT heterostructures. A record‐high electrostatically tunable FMR field range of 860 Oe with a linewidth of 330–380 Oe is demonstrated in Fe₃O₄/PZN‐PT heterostructure, corresponding to a ME coefficient of 108 Oe cm kV^?1. Static ME interaction is also investigated and a maximum electric field induced squareness ratio change of 40% is observed in Fe₃O₄/PZN‐PT. In addition, a new concept that the external magnetic orientation and the electric field cooperate to determine microwave magnetic tunability is brought forth to significantly enhance the microwave tunable range up to 1000 Oe. These low temperature synthesized multiferroic heterostructures exhibiting giant electrostatically induced tunable magnetic resonance field at microwave frequencies provide great opportunities for electrostatically tunable microwave multiferroic devices.     

Highly Flexible and Twistable Freestanding Single Crystalline Magnetite Film with Robust Magnetism

Magnetic materials and devices that can be folded and twisted without sacrificing their functional properties are highly desirable for flexible electronic applications in wearable products and implantable systems. In this work, a high‐quality single crystalline freestanding Fe₃O₄ thin film with strong magnetism has been synthesized by pulsed laser deposition using a water‐dissolvable Sr₃Al₂O₆ sacrificial layer, and the resulting freestanding film, with magnetism confirmed at multiple length scales, is highly flexible with a bending radius as small as 7.18 µm and twist angle as large as 122°, in sharp contrast with bulk magnetite that is quite brittle. When transferred to a polydimethylsiloxane support layer, the Fe₃O₄ film can be bent with large deformation without affecting its magnetization, demonstrating its robust magnetism. The work thus offers a viable solution for flexible magnetic materials that can be utilized in a range of applications.     

Substrate‐Dependent Spin–Orbit Coupling in Hybrid Perovskite Thin Films

Solution‐processing hybrid metal halide perovskites are promising materials for developing flexible thin‐film devices. This work reports the substrate effects on the spin–orbit coupling (SOC) in perovskite films through thermal expansion under thermal annealing. X‐ray diffraction (XRD) measurements show that using a flexible polyethylene naphthalate (PEN) substrate introduces a smaller mechanical strain in perovskite MAPbI_3?xCl_x films, as compared to conventional glass substrates. Interestingly, the linear/circular photoexcitation‐modulated photocurrent studies find that decreasing mechanical strain gives rise to a weaker orbit–orbit interaction toward decreasing the SOC in the MAPbI_3?xCl_x films prepared on flexible PEN substrates relative to rigid glass substrates. Simultaneously, decreasing the mechanical strain causes a reduction in the internal magnetic parameter inside the MAPbI_3?xCl_x films, providing further evidence to show that introducing mechanical strain can affect the SOC in hybrid perovskite films upon using flexible substrates toward developing flexible perovskite thin‐film devices. Furthermore, thermal admittance spectroscopy indicates that the trap states are increased in the perovskite films prepared on flexible PEN substrates as compared to glass substrates. Consequently, PEN and rigid glass substrates lead to shorter and longer photoluminescence lifetimes, respectively. Clearly, these findings provide an insightful understanding on substrate effects on optoelectronic properties in flexible perovskite thin‐film devices.     

High Mobility WS2 Transistors Realized by Multilayer Graphene Electrodes and Application to High Responsivity Flexible Photodetectors

The electrical contact is one of the main issues preventing semiconducting 2D materials to fulfill their potential in electronic and optoelectronic devices. To overcome this problem, a new approach is developed here that uses chemical vapor deposition grown multilayer graphene (MLG) sheets as flexible electrodes for WS₂ field‐effect transistors. The gate‐tunable Fermi level, van der Waals interaction with the WS₂, and the high electrical conductivity of MLG significantly improve the overall performance of the devices. The carrier mobility of single‐layer WS₂ increases about a tenfold (50 cm² V^?1 s^?1 at room temperature) by replacing conventional Ti/Au metal electrodes (5 cm² V^?1 s^?1) with the MLG electrodes. Further, by replacing the conventional SiO₂ substrate with a thin (1 µm) parylene‐C flexible film as insulator, flexible WS₂ photodetectors that are able to sustain multiple bending stress tests without significant performance degradation are realized. The flexible photodetectors exhibited extraordinarily high gate‐tunable photoresponsivities, reaching values of 4500 A W^?1, and with very short (<2 ms) response time. The work of the heterostacked structure combining WS₂, graphene, and the very thin polymer film will find applications in various flexible electronics, such as wearable high‐performance optoelectronics devices.     

Neutron Diffraction Investigations of Magnetism in BiFeO3 Epitaxial Films

The recovery of a modulated magnetic structure in epitaxial BiFeO₃ thin films as revealed by neutron diffraction is reported. The magnetic structure in thin films is found to strongly depend on substrate orientation. The substrate orientation causes different strain–relaxation processes resulting in different thin‐film crystal structures. The (110) oriented film with a monoclinic structural phase has a single‐domain modulated magnetic structure where the magnetic moment lies in the HHL plane. For the (111) oriented film that has a rhombohedral structure, a modulated structure superimposed on the G‐type antiferromagnetic order is found. These results indicate that slight structural modifications in the BiFeO₃ thin film cause drastic changes in the magnetic structure.     

Origami NdFeB Flexible Magnetic Membranes with Enhanced Magnetism and Programmable Sequences of Polarities

Permanent magnets are essential components for many biomedical systems and electromechanical devices, which may be made into flexible formats to achieve wearable monitoring and effective integration with biological tissues. However, the development of high‐performance flexible permanent magnets is challenging due to their ultrathin geometries, which contradict with the thickness‐dependent magnetic properties. In addition, magnetic membranes with controllable sequences of polarities are difficult to achieve. Here, origami techniques to achieve flexible permanent magnetic membranes with enhanced magnetic field strength and programmable sequences of polarities are presented. Linear Halbach arrays, circular Halbach arrays, and concentric magnets with thicknesses ranging from 130 to 500 µm and bending curvatures ranging from 0.039 to 0.0043 µm^?1 are achieved through different folding mechanisms. The origami membranes offer a maximum field intensity of 72 mT and extremely strong magnetic force of 0.21 N cm^?2, allowing various novel applications demonstrated through electronics interfacing, cell manipulations, and soft robotics. The origami techniques offer large magnetism and complex spatial field distribution, and enable practical use of thin flexible magnetic membranes in constructing miniaturized or even flexible electromechanical systems and biomedical instruments for magnetic resonance imaging, targeted drug delivery, health monitoring, and cancer therapy.     

Fully Flexible Electromagnetic Vibration Sensors with Annular Field Confinement Origami Magnetic Membranes

Sensing of mechanical motion based on flexible electromagnetic sensors is challenging due to the complexity of obtaining flexible magnetic membranes with confined and enhanced magnetic fields. A fully flexible electromechanical system (MEMS) sensor is developed to conduct wearable monitoring of mechanical displacement with excellent adaptability to complex surface morphology through a suspended flexible magnet enclosed within a novel setup formed by a multi‐layer flexible coil and annular origami magnetic membranes. The annular membranes not only regulate the overall distribution of the magnetic field and enhance the overall magnetism by 291%, but also greatly increase the range of the magnetic field to cover the entire region of the coil. The sensor offers a broad frequency response ranging from 1 Hz to 10 kHz and a sensitivity of 0.59 mV µm^?1 at 1.7 kHz. The fully flexible format of the sensor enables various applications demonstrated by biophysical sensing, motion detection, voice recognition, and machine diagnostics through direct attachment on soft and curvilinear surfaces. Similar sensors can combine multiple sensing and energy harvesting modalities to achieve battery‐less and self‐sustainable operation, and can be deployed in large numbers to conduct distributed sensing for machine status assessment, health monitoring, rehabilitation, and speech aid.     

Influence of substrate on the high-frequency permeability of thin iron films

The ferromagnetic resonance (FMR) spectra of thin metallic films obtained by magnetron deposition on polymeric and ceramic substrates are investigated in the strip line at frequencies of 0.13–12 GHz via frequency and external magnetic field sweeping. The influence of mechanical stresses on the FMR spectra of films deposited on an elastic (polyethylene rephthalate) substrate is discussed. The magnetostriction contribution to the anisotropy field of a film, as well as the influence of tensile stresses on the quasi-static permeability and FMR frequency, is estimated. It is demonstrated that the microwave properties of a thin metallic film are also specified by the properties of the substrate with such a film. A distinction in the magnetic properties of films with the same composition, which are deposited on different substrates, is explained in terms of the magnetostriction effect.     

Room Temperature Electric‐Field Control of Magnetism in Layered Oxides with Cation Order

Searching for materials with room‐temperature electric‐field control of magnetism has interested researchers for many years with three‐dimensional perovskite BiFeO₃‐based compounds as the main focus. Here we choose the layered hybrid improper ferroelectric Ruddlesden‐Popper oxides as a platform from which to realize electric field controllable magnetism, leveraging a recently identified strain tunable polar‐to‐nonpolar (P‐NP) transition. We first propose a design principle for selecting the required A and B cation chemistries that will ensure (001) A₃B₂O₇ films exhibit P‐NP transitions, which we substantiate with density functional calculations. By extending the guideline to B‐site ordered A₃BB′O₇ oxides, we identify more compounds exhibiting P‐NP transitions marked by the disappearance of an in‐plane polarization that can be functionalized. We then demonstrate that weak ferromagnetism can be tuned by an electric field at the boundary of the P‐NP transition in B‐site ordered (001) A₃BB′O₇ magnetic films, based on which we predict that cation ordered Ca₃TcTiO₇ may be a viable candidate for room‐temperature electric‐field control of magnetism.     

High-Performance Flexible Schottky DC Generator via Metal/Conducting Polymer Sliding Contacts

Dynamic Schottky direct-current (DC) generators hold great promise for ambient mechanical energy harvesting as it overcomes the low-current output limitation in conventional approaches. However, the lack of a fundamental understanding of DC generation in conducting polymer-based Schottky generators has hindered their application for self-powered wearable and implantable electronics. Here, a high-performance, flexible Schottky DC generator with metal/conducting polymer sliding contact system is demonstrated, which exhibits a large current density (J) up to 20 A m^–2 for single contact geometry and a scaled-up DC output reaching 200 µA (J = 0.73 A m^–2) and 0.8 V. The design of flexibility in such a Schottky DC generator is inherited from the long-chain polymer concept, leading to the demonstration of a variety of device configuration of free-standing thin film, supported thin film and nanocomposite prototype toward practical applications. It is revealed that the sliding junctions may exhibit a different mechanical energy conversion mechanism compared to the compressive conducting polymer Schottky junctions. It is also proven that the magnitude and polarity of DC generation is determined by the Schottky contact formation and interfacial electric field. The concept of a flexible Schottky generator not only shows great promise for next-generation, self-powered wearable devices, but also provides potential mechanisms for developing novel wearable sensors.     

Long‐Range Nonvolatile Electric Field Effect in Epitaxial Fe/Pb(Mg1/3Nb2/3)0.7Ti0.3O3 Heterostructures

One of the ideal candidates of using electric field to manipulate magnetism is the recently developed multiferroics with emergent coupling of magnetism and electricity, particularly in synthesizing artificial nanoscale ferroelectric and ferromagnetic materials. Here, a long‐range nonvolatile electric field effect is investigated in Fe/Pb(Mg_1/3Nb_2/3)_0.7Ti_0.3O₃ heterostructure using the dependence of the magnon‐driven magnetoelectric coupling on the epitaxial Fe thin film (4–30 nm) thickness at room temperature using measurements based on the ferromagnetic resonance. The magnon‐driven magnetoelectric coupling tuning of the ferromagnetic resonance field shows a linear response to the electric field, with a resonance field shift that occurs under both positive and negative remanent polarizations, and demonstrates nonvolatile behavior. Moreover, the spin diffusion length of the epitaxial Fe thin film of ≈9 nm is obtained from the results that the change of the cubic magnetocrystalline anisotropy field under different electric fields varies with Fe thickness. These results are promising for the design of future multiferroic devices.     

An Electrical Switch‐Driven Flexible Electromagnetic Absorber

The development of a thin, tunable, and high‐performance flexible electromagnetic (EM) absorbing device that aims to solve signal interference or EM pollution is highly desirable but remains a great challenge. Herein, demonstrated is a flexible electrical‐driven device constructed by an insulated organic‐polymer substrate, carrier transmission layer, and core–shell structured absorber, enabling a narrow and tunable effective absorption region (f_E < 2.0 GHz) by controlling the external voltage toward this challenge. As a key design element, the selected absorber consists of an Sn/SnS/SnO₂ core and C shell, which exhibits an exceptional dielectric‐response ability at a small voltage, which is attributed to desirable carrier mobility and excitable carriers. Multiple f_E‐tuning regions (maximum up to 7.0), covering 90% of C‐band can be achieved for Sn/SnS/SnO₂@C‐based flexible device by selecting a low voltage (2–12 V). The strategy developed here may open a new avenue toward the design of flexible intelligent EM device for practical applications.     

CoFe2O4 and CoFe2O4‐SiO2 Nanoparticle Thin Films with Perpendicular Magnetic Anisotropy for Magnetic and Magneto‐Optical Applications

This paper presents an efficient colloidal approach to process CoFe₂O₄ and SiO₂ nanoparticles into thin films for magnetic and magneto‐optical applications. Thin films of varying CoFe₂O₄‐to‐SiO₂ ratios (from 0 to 90 wt%) are obtained by sequential spin coating‐calcination cycles from the corresponding nanoparticle dispersions. Scanning electron microscopy analysis reveals a crack free and nanoparticulate structure of the sintered films with thicknesses of 480–1200 nm. Results from the optical characterization indicate a direct band gap ranging from 2.6 to 3.9 eV depending on the SiO₂ content. Similarly, the refractive indices and absorption coefficients are tunable upon SiO₂ incorporation. In‐plane measurements of the magnetic properties of the CoFe₂O₄ films reveal a superparamagnetic behavior with both Co²⁺ and Fe³⁺ contributing to the magnetism. Polar Kerr measurements show the presence of a spontaneous magnetization in the CoFe₂O₄ and CoFe₂O₄‐SiO₂ (with SiO₂ < 50 wt%) films, pointing to magnetic anisotropy perpendicular to the substrate. The origin of this effect is attributed to the constrained sintering conditions of the nano­particulate film and the negative magnetostriction of CoFe₂O₄.     

Low‐Symmetry Monoclinic Phases and Polarization Rotation Path Mediated by Epitaxial Strain in Multiferroic BiFeO3 Thin Films

A morphotropic phase boundary driven by epitaxial strain has been observed in lead‐free multiferroic BiFeO₃ thin films and the strain‐driven phase transitions have been widely reported as iso‐symmetric Cc‐Cc by recent works. In this paper, it is suggested that the tetragonal‐like BiFeO₃ phase identified in epitaxial films on (001) LaAlO₃ single crystal substrates is monoclinic M_C. This M_C phase is different from the M_A type monoclinic phase reported in BiFeO₃ films grown on low mismatch substrates, such as SrTiO₃. This is confirmed not only by synchrotron X‐ray studies but also by piezoresponse force microscopy measurements. The polarization vectors of the tetragonal‐like phase lie in the (100) plane, not the (11 0) plane as previously reported. A phenomenological analysis is proposed to explain the formation of M_C Phase. Such a low‐symmetry M_C phase, with its linkage to M_A phase and the multiphase coexistence open an avenue for large piezoelectric response in BiFeO₃ films and shed light on a complete understanding of possible polarization rotation paths and enhanced multiferroicity in BiFeO₃ films mediated by epitaxial strain. This work may also aid the understanding of developing new lead‐free strain‐driven morphotropic phase boundary in other ferroic systems.     

Anisotropic In Situ Strain-Engineered Halide Perovskites for High Mechanical Flexibility

Even though halide perovskite materials have been increasingly investigated as flexible devices, mechanical properties under flexible environments have rarely been reported on. Herein, a nonconventional deposition technique that can generate extra compressive or tensile stress in representative inorganic CsPbBr₃ and hybrid MAPbI₃ (methylammonium lead iodide) halide perovskites is proposed for higher mechanical flexibility. As an impressive result of bending fracture evaluation, fracture energy is substantially improved by ≈260% for CsPbBr₃ and ≈161% for MAPbI₃ with the maximum compressive strain of −1.33%. Origin of the flexibility enhancements by the in situ strain is verified with structural simulation where the anisotropic lattice distortion, that is, contraction in the ab plane and elongation along the c-axis, is evident with changes in atomic bond lengths and angles in the halide perovskites. Other mechanical properties such as hardness, film strength, and fracture toughness are also discussed with direct comparisons between the inorganic and hybrid halides. Beyond the successful adjustment of this in situ deposition technique, the strain-dependent mechanical properties are expected to be extensively useful for designing halides-based flexible devices.     

Fabrication Method,Ferromagnetic Resonance Spectroscopy and Spintronics Devices Based on the Organic-Based Ferrimagnet Vanadium Tetracyanoethylene

Organic-based magnetic materials have been used for spintronic device applications as electrodes of spin aligned carriers and spin-pumping substrates. Their advantages over more traditional inorganic magnets include reduced magnetic damping and lower fabrication costs. Vanadium tetracyanoethylene, V[TCNE]_x (x ≈ 2), is an organic-based ferrimagnet with an above room-temperature magnetic order temperature (T_c ≈ 400 K). V[TCNE]_x has deposition flexibility and can be grown on a variety of substrates via low-temperature chemical vapor deposition (CVD). A systematic study of V[TCNE]_x thin-film CVD parameters to achieve optimal film quality, reproducibility, and excellent magnetic properties is reported. This is assessed by broadband ferromagnetic resonance (FMR) that shows most narrow linewidth of ≈1.5 Gauss and an extremely low Gilbert damping coefficient. The neat V[TCNE]_x films are shown to be efficient spin injectors via spin pumping into an adjacent platinum layer. Also, under an optimized FMR linewidth, the V[TCNE]_x films exhibit Fano-type resonance with a continuum broadband absorption in the microwave range, which can be readily tuned by the microwave frequency.     

Thickness‐Dependent Structure–Property Relationships in Strained (110) SrRuO3 Thin Films

Thickness‐dependent structure–property relationships in strained SrRuO₃ thin films on GdScO₃ (GSO) substrates are reported. The film is found to have epitaxially stabilized crystal structures that vary with the film thickness. Below 16 nm, the √2a_pc × √2a_pc × 2a_pc monoclinic structure is stabilized while above 16 nm the film has the a_pc × 2a_pc × a_pc tetragonal structure. The thickness‐dependent structural changes are ascribed to the substrate‐induced modification in the RuO₆ octahedral rotation pattern, which highlights the significance of the octahedral rotations for the epitaxial strain accommodation in the coherently‐grown films. Close relationships between the structural and physical properties of the films are also found. The monoclinic film has the uniaxial magnetic easy axis 45° away from the [110]_GSO direction while the tetragonal film has the one that lies along the in‐plane [1–10]_GSO direction. The results demonstrate that the octahedral rotations in the strained perovskite oxide thin films are a key factor for determining their structure phases and physical properties.     

Interfacial Strain‐Induced Oxygen Disorder as the Cause of Enhanced Critical Current Density in Superconducting Thin Films

To understand the origin of the increase in critical current density of rare earth barium cuprate superconductor thin films with decreasing thickness, a series of sub‐300‐nm EuBa₂Cu₃O_7?δ thin films deposited on SrTiO₃ substrates are studied by X‐ray diffraction and electrical transport measurements. The out‐of‐plane crystallographic mosaic tilt and the out‐of‐plane microstrain both increase with decreasing film thickness. The calculated density of c‐axis threading dislocations matches the extent of the observed low‐field enhancement in critical current density for fields applied parallel to c. The in‐plane mosaic twist and in‐plane microstrain are both around twice the magnitude of the out‐of‐plane values, and both increase with decreasing film thickness. The results are consistent with the observed stronger field enhancement in critical current density for fields applied parallel to ab. The lattice parameter variation with thickness is not as expected from consideration of the biaxial strain with the substrate, indicative of in‐plane microstrain accommodation by oxygen disorder. Collectively, the results point to an enhancement of critical current by interfacial strain induced oxygen disorder which is greatest closest to the film‐substrate interface. The findings of this study have important implications for other thin functional oxide perovskite films and nanostructures where surface and interfacial strains dominate the properties.     

Orthorhombic Ti2O3: A Polymorph‐Dependent Narrow‐Bandgap Ferromagnetic Oxide

Magnetic semiconductors are highly sought in spintronics, which allow not only the control of charge carriers like in traditional electronics, but also the control of spin states. However, almost all known magnetic semiconductors are featured with bandgaps larger than 1 eV, which limits their applications in long‐wavelength regimes. In this work, the discovery of orthorhombic‐structured Ti₂O₃ films is reported as a unique narrow‐bandgap (≈0.1 eV) ferromagnetic oxide semiconductor. In contrast, the well‐known corundum‐structured Ti₂O₃ polymorph has an antiferromagnetic ground state. This comprehensive study on epitaxial Ti₂O₃ thin films reveals strong correlations between structure, electrical, and magnetic properties. The new orthorhombic Ti₂O₃ polymorph is found to be n‐type with a very high electron concentration, while the bulk‐type trigonal‐structured Ti₂O₃ is p‐type. More interestingly, in contrast to the antiferromagnetic ground state of trigonal bulk Ti₂O₃, unexpected ferromagnetism with a transition temperature well above room temperature is observed in the orthorhombic Ti₂O₃, which is confirmed by X‐ray magnetic circular dichroism measurements. Using first‐principles calculations, the ferromagnetism is attributed to a particular type of oxygen vacancies in the orthorhombic Ti₂O₃. The room‐temperature ferromagnetism observed in orthorhombic‐structured Ti₂O₃, demonstrates a new route toward controlling magnetism in epitaxial oxide films through selective stabilization of polymorph phases.     

Single‐Crystalline Films of the Homologous Series InGaO3(ZnO)m Grown by Reactive Solid‐Phase Epitaxy

Single‐crystalline thin films of the homologous series InGaO₃(ZnO)_m (where m is an integer) are fabricated by the reactive solid‐phase epitaxy (R‐SPE) method. Specifically, the role of ZnO as epitaxial initiator layer for the growth mechanism is clarified. High‐temperature annealing of bilayer films consisting of an amorphous InGaO₃(ZnO)₅ layer deposited at room temperature and an epitaxial ZnO layer on yttria‐stabilized zirconia (YSZ) substrate allows for the growth of single‐crystalline film with controlled chemical composition. The epitaxial ZnO thin layer plays an essential role in determining the crystallographic orientation, while the ratio of the thickness of both layers controls the film composition.