Ferroelectric and Magnetic Properties in Room‐Temperature Multiferroic GaxFe2−xO3 Epitaxial Thin Films

GaFeO₃‐type iron oxide is a promising room‐temperature multiferroic material due to its large magnetization. To expand its usability, controlling the ferroelectric and magnetic properties is crucial. In this study, high‐quality Ga_xFe_2–xO₃ (x = 0–1) epitaxial films are fabricated and their properties are systematically investigated. All films exhibit room‐temperature out‐of‐plane ferroelectricity, showing that the coercive electric field (E_c) decreases monotonically with x. Additionally, the films show in‐plane ferrimagnetism with a Curie temperature (T_C) >350 K at x = 0–0.6. The coercive magnetic field (H_c) decreases with x at x ≤ 0.6, but shows a constant value at x > 0.6, whereas the saturated magnetization (M_s) increases with x at x ≤ 0.6, but decreases with x at x > 0.6. X‐ray magnetic circular dichroism reveals that the large magnetization at x = 0.6 is derived from Fe³⁺ (3d⁵) at octahedral sites. The controllable range of the E_c, H_c, and M_s values at room temperature (400–800 kV cm^?1, 1–8 kOe, and 0.2–0.6 µ_B/f.u.) is very wide and differs from those of well‐known multiferroic BiFeO₃. Furthermore, the Ga_xFe_2?xO₃ films exhibit room‐temperature magnetocapacitance effects, indicating that adjusting T_C near room temperature is useful to achieve large room‐temperature magnetocapacitance behavior.     

Voltage‐Controlled Nonstoichiometry in Oxide Thin Films: Pr0.1Ce0.9O2−δ Case Study

While the properties of functional oxide thin films often depend strongly on oxygen stoichiometry, there have been few means available for its control in a reliable and in situ fashion. This work describes the use of DC bias as a means of systematically controlling the stoichiometry of oxide thin films deposited onto yttria‐stabilized zirconia substrates. Impedance spectroscopy is performed on the electrochemical cell Pr_0.1Ce_0.9O_2?δ (PCO)/YSZ/Ag for conditions: T = 550 to 700 °C, pO ₂ = 10^?4 to 1 atm, and ΔE = ‐100 to 100 mV. The DC bias ΔE is used to control the effective pO ₂ or oxygen activity at the PCO/YSZ interface. The non‐stoichiometry (δ) of the PCO films is calculated from the measured chemical capacitance (C_chem ). These δ values, when plotted isothermally as a function of effective pO ₂, established, either by the surrounding gas composition alone, or in combination with applied bias, agree well with each other and to predictions based on a previously determined defect model. These results confirm the suitability of using bias to precisely control δ of thin films in an in situ fashion and simultaneously monitor these changes by measurement of C_chem . Of further interest is the ability to reach effective pO ₂s as high as 280 atm.     

Integration of Self‐Assembled Epitaxial BiFeO3–CoFe2O4 Multiferroic Nanocomposites on Silicon Substrates

Perovskite‐spinel epitaxial nanocomposite thin films are commonly grown on single crystal perovskite substrates, but integration onto a Si substrate can greatly increase their usefulness in devices. Epitaxial BiFeO₃–CoFe₂O₄ nanocomposites consisting of CoFe₂O₄ pillars in a BiFeO₃ matrix are grown on (001) Si with two types of buffer layers: molecular beam epitaxy (MBE)‐grown SrTiO₃‐coated Si and pulsed‐laser‐deposited (PLD) Sr(Ti_0.65Fe_0.35)O₃/CeO₂/yttria‐stabilized ZrO₂/Si. The nanocomposite grows with the same crystallographic orientation and morphology as that observed on single crystal SrTiO₃ when the buffered Si substrates are smooth, but roughness of the Sr(Ti_0.65Fe_0.35)O₃ promoted additional CoFe₂O₄ pillar orientations with 45° rotation. The nanocomposites on MBE‐buffered Si show very high magnetic anisotropy resulting from magnetoelastic effects, whereas the hysteresis of nanocomposites on PLD‐buffered Si can be understood as a combination of the hysteresis of the Sr(Ti_0.65Fe_0.35)O₃ film and the CoFe₂O₄ pillars.     

Novel Method of Preparation of Gold‐Nanoparticle‐Doped TiO2 and SiO2 Plasmonic Thin Films: Optical Characterization and Comparison with Maxwell–Garnett Modeling

SiO₂ and TiO₂ thin films with gold nanoparticles (NPs) are of particular interest as photovoltaic materials. A novel method for the preparation of spin‐coated SiO₂–Au and TiO₂–Au nanocomposites is presented. This fast and inexpensive method, which includes three separate stages, is based on the in situ synthesis of both the metal‐oxide matrix and the Au NPs during a baking process at relatively low temperature. It allows the formation of nanocomposite thin films with a higher concentration of Au NPs than other methods. High‐resolution transmission electron microscopy studies revealed a homogeneous distribution of NPs over the film volume along with their narrow size distribution. The optical manifestation of localized surface plasmon resonance was studied in more detail for TiO₂‐based Au‐doped nanocomposite films deposited on glass (in absorption and transmittance) and silicon (in specular reflectance). Maxwell–Garnett effective‐medium theory applied to such metal‐doped nanocomposite films describes the peculiarities of the experimental spectra, including modification of the antireflective properties of bare TiO₂ films deposited on silicon by varying the concentration of metal NPs. The antireflective capabilities of the film are increased after a wet etching process.     

Properties of Flame Sprayed Ce0.8Gd0.2O1.9‐δ Electrolyte Thin Films

Thin films of Ce_0.8Gd_0.2O_1.9‐δ (CGO) are deposited by flame spray deposition with a deposition rate of about 30 nm min^?1. The films (deposited at 200 °C) are dense, smooth, and particle‐free and show a biphasic amorphous/nanocrystalline microstructure. Isothermal grain growth and microstrain are determined as a function of dwell time and temperature and correlated to the electrical conductivity. CGO films annealed for 10 h at 600 °C present the best electrical conductivity of 0.46 S m^?1 measured at 550 °C. Reasons for the superior performance of films annealed at low temperature over higher‐temperature‐treated samples are discussed and include grain‐size evolution, microstrain relaxation, and chemical decomposition. Nanoindentation measurements are conducted on the CGO thin films as a function of annealing temperature to determine the hardness and elastic modulus of the films for potential application as free‐standing electrolyte membranes in low‐temperature micro‐SOFCs (solid oxide fuel cells).     

Photoferroelectric Thin Films for Flexible Systems by a Three‐in‐One Solution‐Based Approach

The effective incorporation of (multi)functional oxides into next‐generation flexible electronics systems requires novel fabrication technologies that enable the direct integration of crystalline oxide layers in them. Unfortunately, this is considerably challenging due to the thermal incompatibility between the crystallization temperatures of metal oxides (>600 °C) and the thermal stability of the flexible polymer substrates conventionally used (<400 °C). Here, it is shown that BiFeO₃ thin films can be grown on flexible plastic by solution processing involving three different but complementary strategies to induce the crystallization of the perovskite phase at a lower temperature limit of 325 °C. This “three‐in‐one” approach is based on the synthesis of tailored metal precursors i) with a molecular structure resembling the crystalline structure of the oxide phase, which additionally allows both ii) photochemical and iii) internal combustion reactions taking place in the thin films. The flexible BiFeO₃ thin films obtained from a specifically designed molecular complex with N‐methyldiethanolamine yield a large remnant polarization of 17.5 µC cm^?2, also showing photovoltaic and photocatalytic effects. This result paves the way for the direct integration of an interesting class of oxides with photoferroelectric properties in flexible devices with multiple applications in information and communication technology, and energy.     

溶胶pH值对CoFe_2O_4/SiO_2复合薄膜结构和磁性能的影响

采用sol-gel法制备了纳米CoFe2O4/SiO2复合薄膜(样品)。利用X射线衍射仪、原子力显微镜、振动样品磁强计对样品的结构、形貌和磁性能进行了研究。结果表明:随着溶胶pH值的减小,样品中CoFe2O4的平均晶粒尺寸变小,CoFe2O4晶粒沿(111)晶面择优取向生长。样品的矫顽力随着平均晶粒尺寸的减小明显变大,当溶胶pH值为0.29时,垂直和平行膜面的矫顽力分别为290 kA.m–1和250 kA.m–1,样品具有较明显的垂直磁各向异性。当溶胶pH值为0.59时,样品垂直和平行膜面的剩磁比(Mr/Ms)分别为53.2%和51.5%。     

Ultrathin Epitaxial Ferromagnetic γ‐Fe2O3 Layer as High Efficiency Spin Filtering Materials for Spintronics Device Based on Semiconductors

In spintronics, identifying an effective technique for generating spin‐polarized current has fundamental importance. The spin‐filtering effect across a ferromagnetic insulating layer originates from unequal tunneling barrier heights for spin‐up and spin‐down electrons, which has shown great promise for use in different ferromagnetic materials. However, the low spin‐filtering efficiency in some materials can be ascribed partially to the difficulty in fabricating high‐quality thin film with high Curie temperature and/or partially to the improper model used to extract the spin‐filtering efficiency. In this work, a new technique is successfully developed to fabricate high quality, ferrimagnetic insulating γ‐Fe₂O₃ films as spin filter. To extract the spin‐filtering effect of γ‐Fe₂O₃ films more accurately, a new model is proposed based on Fowler–Nordheim tunneling and Zeeman effect to obtain the spin polarization of the tunneling currents. Spin polarization of the tunneled current can be as high as ?94.3% at 2 K in γ‐Fe₂O₃ layer with 6.5 nm thick, and the spin polarization decays monotonically with temperature. Although the spin‐filter effect is not very high at room temperature, this work demonstrates that spinel ferrites are very promising materials for spin injection into semiconductors at low temperature, which is important for development of novel spintronics devices.     

Mechanism of Crystallization and Implications for Charge Transport in Poly(3‐ethylhexylthiophene) Thin Films

In this work, crystallization kinetics and aggregate growth of poly(3‐ethylhexylthiophene) (P3EHT) thin films are studied as a function of film thickness. X‐ray diffraction and optical absorption show that individual aggregates and crystallites grow anisotropically and mostly along only two packing directions: the alkyl stacking and the polymer chain backbone direction. Further, it is also determined that crystallization kinetics is limited by the reorganization of polymer chains and depends strongly on the film thickness and average molecular weight. Time‐dependent, field‐effect hole mobilities in thin films reveal a percolation threshold for both low and high molecular weight P3EHT. Structural analysis reveals that charge percolation requires bridged aggregates separated by a distance of ≈2–3 nm, which is on the order of the polymer persistence length. These results thus highlight the importance of tie molecules and inter‐aggregate distance in supporting charge percolation in semiconducting polymer thin films. The study as a whole also demonstrates that P3EHT is an ideal model system for polythiophenes and should prove to be useful for future investigations into crystallization kinetics.     

Well‐Defined Pillararene‐Based Azobenzene Liquid Crystalline Photoresponsive Materials and Their Thin Films with Photomodulated Surfaces

Photoresponsive materials (PRMs) have long been a hot topic and photo‐modulated smart surface is very appealing. Particularly, liquid crystalline PRMs are able to amplify and stabilize photoinduced orientation thanks to their self‐assembling and ordering characteristics. Herein, the first pillararene‐based azobenzene liquid crystalline PRM with well‐defined structure is presented, which can avoid the usually ill‐defined composition drawback of polymer PRMs and prevent the severe H‐aggregation from suppressing or even completely blocking photoresponse in simple azobenzene derivatives. The pillar[5]arene‐based macrocyclic azobenzenes with variant length spacers show wide temperature range smectic liquid crystalline mesophases and excellent film‐formation property. The tubular pillar[5]arene macrocyclic framework provides sufficient free volume for azobenzene moieties to achieve reversible photoisomerization and photoalignment; thus, their thin films demonstrate excellent light‐triggered modulation of surface free energy, wettability, and even photoalignment‐mediated orientation of an upper layer discotic liquid crystal columnar mesophase. Such pillararene‐based azobenzene liquid crystals represent novel and promising PRMs with extensive fascinating applications.     

Sodium-Sulfur Batteries with Unprecedented Capacity,Cycling Stability and Operation Temperature Range Enabled by a CoFe2O4 Catalytic Additive Under an External Magnetic Field

The electrochemical performance of room-temperature sodium-sulfur batteries (SSBs) is limited by slow reaction kinetics and sulfur loss in the form of sodium polysulfides (SPSs). Here, it is demonstrated that through electron spin polarization, at no additional energy cost, an external magnetic field (M on) generated by a permanent magnet can significantly improve the SPSs adsorption capacity and reaction dynamics of a ferrimagnetic sulfur host. More specifically, the preparation of a carbon nanofiber/CoFe₂O₄/S (CNF/CoFe₂O₄/S) cathode with unprecedented performance and stability at ambient temperature is detailed when M on. It is experimentally and theoretically demonstrated that the magnetic field polarizes the electrons of Co ions, enhancing the adsorption of SPSs and their catalytic conversion. CNF/CoFe₂O₄/S cathodes with spin polarization provide unprecedented decay rates down to 0.0039% per cycle at 1.0 C for 2700 cycles. The performance of SSBs is further tested, which has 248 mAh g⁻¹ under 1.0 C after 100 cycles when M on.  Furthermore, it is evidenced that even when removing the external magnetic field, the magnetic polarization effect persists, opening the door for practical applications. This study not only demonstrates an effective strategy to improve electrochemical performance in SSBs, but also contributes to the enrichments of spin effects in the fields of electrocatalysis.     

Magnetic‐Core/Porous‐Shell CoFe2O4/SiO2 Composite Nanoparticles as Immobilized Affinity Supports for Clinical Immunoassays

This study demonstrates a novel approach towards the development of advanced protein assay systems based on physically functionalized, magnetic‐core/porous‐shell CoFe₂O₄/SiO₂ composite nanoparticles. The preparation, characterization, and measurement of the relevant properties of the protein assay system is discussed, and the system is used for the detection of cancer antigen 15‐3 (CA 15‐3, used as a model here) in clinical immunoassays. The protein assay system, based on nanometer‐sized magnetic cores and silica shells, shows good adsorption properties for the selective attachment of CA 15‐3 antibodies specific to CA 15‐3. The core/shell nanostructures exhibit good magnetic properties, which enables their integration into a quartz crystal microbalance (QCM) detection cell with the help of a permanent magnet. Under optimal conditions, the resulting immunoassay system presents a good QCM response for the detection of CA 15‐3, and allows the detection of CA 15‐3 at concentrations as low as 1.5 U mL^–1 (U: units). Importantly, the proposed protein assay system can be extended to the detection of other antigens and biological compounds.     

Palladium Nanoparticles Supported on Magnetic Carbon‐Coated Cobalt Nanobeads: Highly Active and Recyclable Catalysts for Alkene Hydrogenation

Palladium nanoparticles are deposited on the surface of highly magnetic carbon‐coated cobalt nanoparticles. In contrast to the established synthesis of Pd nanoparticles via reduction of Pd(II) precursors, the microwave decomposition of a Pd(0) source leads to a more efficient Pd deposition, resulting in a material with considerably higher activity in the hydrogenation of alkenes. Systematic variation of the Pd loading on the carbon‐coated cobalt nanoparticle surface reveals a distinct trend to higher activities with decreased loading of Pd. The activity of the catalyst is further improved by the addition of 10 vol% Et₂O to iso‐propanol that is found to be the solvent of choice. With respect to activity (turnover frequencies up to 11 095 h^?1), handling, recyclability through magnetic decantation, and leaching of Pd (≤6 ppm/cycle), this novel magnetic hybrid material compares favorably to conventional Pd/C or Pd@CNT catalysts.     

Molten‐Salt‐Assisted Self‐Assembly (MASA)‐Synthesis of Mesoporous Metal Titanate‐Titania,Metal Sulfide‐Titania,and Metal Selenide‐Titania Thin Films

New synthetic strategies are needed for the assembly of porous metal titanates and metal chalcogenite‐titania thin films for various energy applications. Here, a new synthetic approach is introduced in which two solvents and two surfactants are used. Both surfactants are necessary to accommodate the desired amount of salt species in the hydrophilic domains of the mesophase. The process is called a molten‐salt‐assisted self‐assembly (MASA) because the salt species are in the molten phase and act as a solvent to assemble the ingredients into a mesostructure and they react with titania to form mesoporous metal titanates during the annealing step. The mesoporous metal titanate (meso‐Zn₂TiO₄ and meso‐CdTiO₃) thin films are reacted under H₂S or H₂Se gas at room temperature to yield high quality transparent mesoporous metal chalcogenides. The H₂Se reaction produces rutile and brookite titania phases together with nanocrystalline metal selenides and H₂S reaction of meso‐CdTiO₃ yields nanocrystalline anatase and CdS in the spatially confined pore walls. Two different metal salts (zinc nitrate hexahydrate and cadmium nitrate tetrahydrate) are tested to demonstrate the generality of the new assembly process. The meso‐TiO₂‐CdSe film shows photoactivity under sunlight.     

Precise Tuning of (YBa2Cu3O7‐δ)1‐x:(BaZrO3)x Thin Film Nanocomposite Structures

Self‐assembled nanocomposite films and coatings have huge potential for many functional and structural applications. However, control and manipulation of the nanostructures is still at very early stage. Here, guidelines are established for manipulating the types of composite structures that can be achieved. In order to do this, a well studied (YBa₂Cu₃O_7‐δ)_1‐x:(BaZrO₃)_x ‘model’ system is used. A switch from BaZrO₃ nanorods in YBa₂Cu₃O_7‐δ matrix to planar, horizontal layered plates is found with increasing x, with a transitional cross‐ply structure forming between these states at x = 0.4. The switch is related to a release in strain energy which builds up in the YBa₂Cu₃O_7‐δ with increasing x. At x = 0.5, an unusually low strain state is observed in the planar composite structure, which is postulated to arise from a pseudo‐spinodal mechanism.     

Mechanical Strain‐Tunable Microwave Magnetism in Flexible CuFe2O4 Epitaxial Thin Film for Wearable Sensors

Purely mechanical strain‐tunable microwave magnetism device with lightweight, flexible, and wearable is crucial for passive sensing systems and spintronic devices (noncontact), such as flexible microwave detectors, flexible microwave signal processing devices, and wearable mechanics‐magnetic sensors. Here, a flexible microwave magnetic CuFe₂O₄ (CuFO) epitaxial thin film with tunable ferromagnetic resonance (FMR) spectra is demonstrated by purely mechanical strains, including tensile and compressive strains, on flexible fluorophlogopite (Mica) substrates. Tensile and compressive strains show remarkable tuning effects of up‐regulation and down‐regulation on in‐plane FMR resonance field (H_r), which can be used for flexible tunable resonators and filters. The out‐of‐plane FMR spectra can also be tuned by mechanical bending, including H_r and absorption peak. The change of out‐of‐plane FMR spectra has great potential for flexible mechanics‐magnetic deformation sensors. Furthermore, a superior microwave magnetic stability and mechanical antifatigue character are obtained in the CuFO/Mica thin films. These flexible epitaxial CuFO thin films with tunable microwave magnetism and excellent mechanical durability are promising for the applications in flexible spintronics, microwave detectors, and oscillators.     

Supercritical‐Fluid‐Assisted One‐Pot Synthesis of Biocompatible Core(γ‐Fe2O3)/Shell(SiO2) Nanoparticles as High Relaxivity T2‐Contrast Agents for Magnetic Resonance Imaging

Monodisperse iron oxide/microporous silica core/shell composite nanoparticles, core(γ‐Fe₂O₃)/shell(SiO₂), with a diameter of approximately 100 nm and a high magnetization are synthesized by combining sol–gel chemistry and supercritical fluid technology. This one‐step processing method, which is easily scalable, allows quick fabrication of materials with controlled properties and in high yield. The particles have a specific magnetic moment (per kg of iron) comparable to that of the bulk maghemite and show superparamagnetic behavior at room temperature. The nanocomposites are proven to be useful as T₂ MRI imaging agent. They also have potential to be used in NMR proximity sensing, theranostic drug delivery, and bioseparation.     

Assessing Antisite Defect and Impurity Concentrations in Bi2Te3 Based Thin Films by High‐Accuracy Chemical Analysis

In Bi₂Te₃‐based materials charge‐carrier densities are determined by antisite defects and controlling these defects is a key issue for thermoelectric and topological insulator materials. Bi‐Te thin films with high‐quality thermoelectric properties are deposited using a nano‐alloying approach by molecular beam epitaxy (MBE) and sputtering. The in‐plane transport properties are measured at room temperature as a function of charge‐carrier density. High‐accuracy chemical analysis by wavelength‐dispersive X‐ray spectrometry (WDX) is applied for the first time to these Bi₂Te₃‐based thin films. The acquisition conditions for WDX spectrometry are established using Monte Carlo simulations for the electron trajectories, which guarantees a high lateral resolution and rules out stray radiation generated in the substrate of the films. In contrast to energy‐dispersive X‐ray spectrometry (EDX), which is usually applied, WDX offers unprecedented accuracy for measuring antisite defect concentrations and thus has a high impact on improving the quality of thin films. The charge‐carrier densities are calculated from the WDX results according to the point‐defect model of Miller and Li and the thermopower and electrical conductivity are calculated for different charge‐carrier densities by solving the linearized Boltzmann transport equation. A good quantitative agreement is found for the dependence of the thermopower on stoichiometry, whereas the electrical conductivity is sensitively affected by contaminants.     

Periodically Ordered Meso‐ and Macroporous SiO2 Thin Films and Their Induced Electrochemical Activity as a Function of Pore Hierarchy

Silica thin films with variable pore hierarchy (different combinations of small meso‐, large meso‐, and macropores) were produced via evaporation induced self‐assembly in a one‐pot synthesis. A suitable block copolymer and an ionic liquid served as porogens for the generation of different types of mesopores whereas polymethylmethacrylate particles were used as macrotemplate. The silica architectures were characterized by various state‐of‐the‐art techniques, such as 2D‐SAXS, TEM, SEM, AFM, krypton and nitrogen sorption. Moreover, electrochemical functionalization was utilized as a tool to study the hierarchy‐property relationship. Thus, hierarchically porous films prepared on FTO‐coated glass were post‐synthetically silylated and electrochemically active ferrocene groups subsequently grafted onto the pore walls. Cyclic voltammetry was used to monitor the induced electrochemical activity as a function of variations in the pore hierarchy. It turned out that multimodal pore systems possess a relatively higher electrochemical response due to better connection between the pores and higher surface area.