Symmetry Modulation and Enhanced Multiferroic Characteristics in Bi1‐xNdxFeO3 Ceramics

BiFeO₃ is recognized as the most important room temperature single phase multiferroic material. However, the weak magnetoelectric (ME) coupling remains as a key issue, which obstructs its applications. Since the magnetoelectric coupling in BiFeO₃ is essentially hindered by the cycloidal spin structure, here efforts to improve the magnetoelectric coupling by destroying the cycloidal state and switching to the weak ferromagnetic state through symmetry modulation are reported. The structure is tuned from polar R3c to polar Pna2₁, and finally to nonpolar Pbnm by forming Bi_1‐xNd_xFeO₃ solid solutions, where two morphotropic phase boundaries (MPBs) are detected. Greatly enhanced ferroelectric polarization is obtained together with the desired weak ferromagnetic characteristics in Bi_1‐xNd_xFeO₃ ceramics at the compositions near MPBs. The change of magnetic state from antiferromagnetic (cycloidal state) to ferromagnetic (canted antiferromagnetic) is confirmed by the observation of magnetic domains using magnetic force microscopy. More interestingly, combining experiments and first‐principles‐based simulations, an electric field‐induced structural and magnetic transition from Pna2₁ back to R3c is demonstrated, providing a great opportunity for electric field‐controlled magnetism, and this transition is shown to be reversible with additional thermal treatment.     

Self‐Assembled Room Temperature Multiferroic BiFeO3‐LiFe5O8 Nanocomposites

Multiferroic materials have driven significant research interest due to their promising technological potential. Developing new room‐temperature multiferroics and understanding their fundamental properties are important to reveal unanticipated physical phenomena and potential applications. Here, a new room temperature multiferroic nanocomposite comprised of an ordered ferrimagnetic spinel α‐LiFe₅O₈ (LFO) and a ferroelectric perovskite BiFeO₃ (BFO) is presented. It is observed that lithium (Li)‐doping in BFO favors the formation of LFO spinel as a secondary phase during the synthesis of Li_xBi_1?xFeO₃ ceramics. Multimodal functional and chemical imaging methods are used to map the relationship between doping‐induced phase separation and local ferroic properties in both the BFO‐LFO composite ceramics and self‐assembled nanocomposite thin films. The energetics of phase separation in Li doped BFO and the formation of BFO‐LFO composites are supported by first principles calculations. These findings shed light on Li's role in the formation of a functionally important room temperature multiferroic and open a new approach in the synthesis of light element doped nanocomposites for future energy, sensing, and memory applications.     

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.     

Ti‐Doping to Reduce Conductivity in Bi0.85Nd0.15FeO3 Ceramics

In 2009, Karimi et al. reported that Bi_1‐xNd_xFeO₃ 0.15 ≤ x ≤ 0.25 exhibited a PbZrO₃ (PZ)‐like structure. These authors presented some preliminary electrical data for the PZ‐like composition but noted that the conductivity was too high to obtain radio‐frequency measurements representative of the intrinsic properties. In this study, Bi_0.85Nd_0.15Fe_1‐yTi_yO₃ (0 ≤ y ≤ 0.1) were investigated, in which Ti acted as a donor dopant on the B‐site. In contrast to the original study of Karimi et al., X‐ray diffraction (XRD) of Bi_0.85Nd_0.15FeO₃ revealed peaks which were attributed to a mixture of PZ‐like and rhombohedral structures. However, as the Ti (0 < y ≤ 0.05) concentration increased, the rhombohedral peaks disappeared and all intensities were attributed to the PZ‐like phase. For y = 0.1, broad XRD peaks indicated a significant decrease in effective diffracting volume. Electron diffraction confirmed that the PZ‐like phase was dominant for y ≤ 0.05, but for y = 0.1, an incommensurate structure was present, consistent with the broadened XRD peaks. The substitution of Fe³⁺ by Ti⁴⁺ decreased the dielectric loss at room temperature from >0.3 to <0.04 for all doped compositions, with a minimum (0.015) observed for y = 0.03. The decrease in dielectric loss was accompanied by a decrease in the room temperature bulk conductivity from ～1 mS cm^?1 to <1 μS cm^?1 and an increase in bulk activation energy from 0.29 to >1 eV. Plots of permittivity (?_r) versus temperature for 0.01 ≤ y ≤ 0.05 revealed a step rather than a peak in ?_r on heating at the same temperature determined for the antiferroelectric–paraelectric phase transition by differential scanning calorimetry. Finally, large electric fields were applied to all doped samples which resulted in a linear dependence of polarisation on the electric field similar to that obtained for PbZrO₃ ceramics under equivalent experimental conditions.     

Controlling Phase Assemblage in a Complex Multi‐Cation System: Phase‐Pure Room Temperature Multiferroic (1−x)BiTi(1−y)/2FeyMg(1−y)/2O3–xCaTiO3

A room temperature magnetoelectric multiferroic is of interest as, e.g., magnetoelectric random access memory. Bulk samples of the perovskite (1?x)BiTi_(1?y)/2Fe_yMg_(1?y)/2O₃–xCaTiO₃ (BTFM–CTO) are simultaneously ferroelectric, weakly ferromagnetic, and magnetoelectric at room temperature. In BTFM–CTO, the volatility of bismuth oxide, and the complex subsolidus reaction kinetics, cause the formation of a microscopic amount of ferrimagnetic spinel impurity, which complicates the quantitative characterization of their intrinsic magnetic and magnetoelectric properties. Here, a controlled synthesis route to single‐phase bulk samples of BTFM–CTO is devised and their intrinsic properties are determined. For example, the composition x = 0.15, y = 0.75 shows a saturated magnetization of 0.0097μ_B per Fe, a linear magnetoelectric susceptibility of 0.19(1) ps m^?1, and a polarization of 66 μC cm^?2 at room temperature. The onset of weak ferromagnetism and linear magnetoelectric coupling are shown to coincide with the onset of bulk long‐range magnetic order by neutron diffraction. The synthesis strategy developed here will be invaluable as the phase diagram of BTFM–CTO is explored further, and as an example for the synthesis of other compositionally complex BiFeO₃‐related materials.     

The Formation of Performance Enhancing Pseudo‐Composites in the Highly Active La1–xCaxFe0.8Ni0.2O3 System for IT‐SOFC Application

The La_1–xCa_xFe_0.8Ni_0.2O_3–δ (0 ≤ x ≤ 0.9) system is investigated for potential application as a cathode material for intermediate temperature solid oxide fuel cells (IT‐SOFCs). A broad range of experimental techniques have been utilized in order to elucidate the characteristics of the entire compositional range. Low A‐site Ca content compositions (x ≤ 0.4) feature a single perovskite solid solution. Compositions with 40% Ca content (x = 0.4) exhibit the highest electrical and ionic conductivities of these single phase materials (250 and 1.9 × 10^?3 S cm^?1 at 800 °C, respectively), a level competitive with state‐of‐the‐art (La,Sr)(Fe,Co)O₃. Between 40 and 50% Ca content (0.4 > x > 0.5) a solubility limit is reached and a secondary, brownmillerite‐type phase appears for all higher Ca content compositions (0.5 ≤ x ≤ 0.9). While typically seen as detrimental to electrochemical performance in cathode materials, this phase brings with it ionic conductivity at operational temperatures. This gives rise to the effective formation of pseudo‐composite materials which feature significantly enhanced performance characteristics, while also providing the closest match in thermal expansion behavior to typical electrolyte materials. This all comes with the advantage of being produced through a simple, single‐step, low‐cost production route without the issues associated with typical composite materials. The highest performing pseudo‐composite material (x = 0.5) exhibits electronic conductivity of 300–350 S cm^?1 in the 600–800 °C temperature range while the best polarisation resistance (R_p) values of approximately 0.2 Ω cm² are found in the 0.5 ≤ x ≤ 0.7 range.     

Synthesis,Crystal Structure,and Magnetic Properties of ϵ‐InxFe2–xO3 Nanorod‐Shaped Magnets

A series of ?‐In_xFe_2–xO₃ nanorods are prepared by combining the reverse‐micelle and the sol–gel methods. Metal replacement was achieved in the region of 0 ≤ x ≤ 0.24. The crystal structures are orthorhombic structures (space group: Pna2₁), which are pyroelectric with an electric polarization along the c axis. The transmission electron microscopy images show that the particle sizes are (80 ± 40) × (23 ± 5) nm (x = 0), (65 ± 30) × (30 ± 10) nm (x = 0.12), and (80 ± 40) × (35 ± 15) nm (x = 0.24). The magnetization versus temperature curves of the samples with x = 0, x = 0.12, and x = 0.24 show spontaneous magnetization with Curie temperatures of 495 K, 456 K, and 414 K, respectively. Their coercive fields at 300 K are 20 kOe (x = 0), 14 kOe (x = 0.12), and 9 kOe (x = 0.24). These samples show a spin reorientation with reorientation temperatures (T_p) of 102 K (x = 0), 149 K (x = 0.12), and 180 K (x = 0.24). In particular, the samples with x = 0.12 and x = 0.24 show antiferromagnetic behavior below T_p. This series of ?‐In_xFe_2–xO₃ is the first example of a pyroelectric material that exhibits a phase transition between ferrimagnetism and antiferromagnetism.     

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.     

Impact of Bi Deficiencies on Ferroelectric Resistive Switching Characteristics Observed at p‐Type Schottky‐Like Pt/Bi1–δFeO3 Interfaces

This work reports a resistive switching effect observed at rectifying Pt/Bi_1–δFeO₃ interfaces and the impact of Bi deficiencies on its characteristics. Since Bi deficiencies provide hole carriers in BiFeO₃, Bi‐deficient Bi_1–δFeO₃ films act as a p‐type semiconductor. As the Bi deficiency increased, a leakage current at Pt/Bi_1–δFeO₃ interfaces tended to increase, and finally, rectifying and hysteretic current–voltage (I–V) characteristics were observed. In I–V characteristics measured at a voltage‐sweep frequency of 1 kHz, positive and negative current peaks originating from ferroelectric displacement current were observed under forward and reverse bias prior to set and reset switching processes, respectively, suggesting that polarization reversal is involved in the resistive switching effect. The resistive switching measurements in a pulse‐voltage mode revealed that the switching speed and switching ratio can be improved by controlling the Bi deficiency. The resistive switching devices showed endurance of >10⁵ cycles and data retention of >10⁵ s at room temperature. Moreover, unlike conventional resistive switching devices made of metal oxides, no forming process is needed to obtain a stable resistive switching effect in the ferroelectric resistive switching devices. These results demonstrate promising prospects for application of the ferroelectric resistive switching effect at Pt/Bi_1–δFeO₃ interfaces to nonvolatile memory.     

A Giant Electrocaloric Effect in Nanoscale Antiferroelectric and Ferroelectric Phases Coexisting in a Relaxor Pb0.8Ba0.2ZrO3 Thin Film at Room Temperature

Recently, large electrocaloric effects (ECE) in antiferroelectric sol‐gel PbZr_0.95Ti_0.05O₃ thin films and in ferroelectric polymer P(VDF‐TrFE)55/45 thin films were observed near the ferroelectric Curie temperatures of these materials (495 K and 353 K, respectively). Here a giant ECE (ΔT = 45.3 K and ΔS = 46.9 J K^?1 kg^?1 at 598 kV cm^?1) is obtained in relaxor ferroelectric Pb_0.8Ba_0.2ZrO₃ (PBZ) thin films fabricated on Pt(111)/TiO_x/SiO₂/Si substrates using a sol‐gel method. Nanoscale antiferroelectric (AFE) and ferroelectric (FE) phases coexist at room temperature (290 K) rather than at the Curie temperature (408 K) of the material. The giant ECE in such a system is attributed to the coexistence of AFE and FE phases and a field‐induced nanoscale AFE to FE phase transition. The giant ECE of the thin film makes this a promising material for applications in cooling systems near room temperature.     

Effect of Zr4+ Content on the Grain Growth,Dielectric Relaxation Behavior,and Ferroelectric Properties of Ba0.4Sr0.6Ti1−x Zr x O3 Nano-Ceramics Prepared by Different Methods Assisted by Fast Microwave Sintering

The effect of Zr⁴⁺ content on the grain growth, dielectric relaxation, and piezoelectric properties of Ba_0.4Sr_0.6Ti_1?x Zr _x O₃ (BSTZ; x = 0, 0.02, 0.04, 0.06) ceramics prepared by solid-state (SS) and sol–gel modified hydrothermal (SH) methods assisted by fast microwave sintering was investigated in this study. A combination of x-ray diffraction (XRD), scanning electron microscopy (SEM), impedance analysis, and ferroelectric analysis was used. All the ceramics had pure perovskite structures at room temperature, as seen from XRD patterns, indicating that Zr⁴⁺ was incorporated into Ba_0.4Sr_0.6TiO₃ lattices to form a solid solution. In the SEM micrographs, SH samples had higher densities and smaller and more homogeneous grain size than SS samples, which was in agreement with density measurements. Nano-ceramics were obtained by this method. When the temperature dependence of dielectric constant and dielectric loss was studied, SH samples had higher permittivity, better thermally activated relaxation, and lower dielectric loss at high temperature. Ferroelectric characteristics can still be detected in Ba_0.4Sr_0.6Ti_1?x Zr _x O₃ ceramics and residual polarization (P _r) decreased with increasing Zr⁴⁺ content.     

E‐Field Control of Exchange Bias and Deterministic Magnetization Switching in AFM/FM/FE Multiferroic Heterostructures

The coexistence of electrical polarization and magnetization in multiferroic materials provides great opportunities for novel information storage systems. In particular, magnetoelectric (ME) effect can be realized in multi­ferroic composites consisting of both ferromagnetic and ferroelectric phases through a strain mediated interaction, which offers the possibility of electric field (E‐field) manipulation of magnetic properties or vice versa, and enables novel multiferroic devices such as magnetoelectric random access memories (MERAMs). These MERAMs combine the advantages of FeRAMs (ferroelectric random access memories) and MRAMs (magnetic random access memories), which are non‐volatile magnetic bits switchable by electric field (E‐field). However, it has been challenging to realize 180° deterministic switching of magnetization by E‐field, on which most magnetic memories are based. Here we show E‐field modulating exchange bias and for the first time realization of near 180° dynamic magnetization switching at room temperature in novel AFM (antiferromagnetic)/FM (ferromagnetic)/FE (ferroelectric) multiferroic heterostructures of FeMn/Ni₈₀Fe₂₀/FeGaB/PZN‐PT (lead zinc niobate–lead titanate). Through competition between the E‐field induced uniaxial anisotropy and unidirectional anisotropy, large E‐field‐induced exchange bias field‐shift up to $ {{{\Delta H_{ex}}}\over{{H_{ex}}}} = 218\%$ and near 180° deterministic magnetization switching were demonstrated in the exchange‐coupled multiferroic system of FeMn/Ni₈₀Fe₂₀/FeGaB/PZN‐PT. This E‐field tunable exchange bias and near 180° deterministic magnetization switching at room temperature in AFM/FM/FE multiferroic heterostructures paves a new way for MERAMs and other memory technologies.     

Continuous Control of Charge Transport in Bi‐Deficient BiFeO3 Films Through Local Ferroelectric Switching

It is demonstrated that electric transport in Bi‐deficient Bi_1‐δFeO₃ ferroelectric thin films, which act as a p‐type semiconductor, can be continuously and reversibly controlled by manipulating ferroelectric domains. Ferroelectric domain configuration is modified by applying a weak voltage stress to Pt/Bi_1‐δFeO₃/SrRuO₃ thin‐film capacitors. This results in diode behavior in macroscopic charge‐transport properties as well as shrinkage of polarization‐voltage hysteresis loops. The forward current density depends on the voltage stress time controlling the domain configuration in the Bi_1‐δFeO₃ film. Piezoresponse force microscopy shows that the density of head‐to‐head/tail‐to‐tail unpenetrating local domains created by the voltage stress is directly related to the continuous modification of the charge transport and the diode effect. The control of charge transport is discussed in conjunction with polarization‐dependent interfacial barriers and charge trapping at the non‐neutral domain walls of unpenetrating tail‐to‐tail domains. Because domain walls in Bi_1‐δFeO₃ act as local conducting paths for charge transport, the domain‐wall‐mediated charge transport can be extended to ferroelectric resistive nonvolatile memories and nanochannel field‐effect transistors with high performances conceptually.     

Multiferroic Clusters: A New Perspective for Relaxor‐Type Room‐Temperature Multiferroics

Multiferroics are promising for sensor and memory applications, but despite all efforts invested in their research no single‐phase material displaying both ferroelectricity and large magnetization at room‐temperature has hitherto been reported. This situation has substantially been improved in the novel relaxor ferroelectric single‐phase (BiFe_0.9Co_0.1O₃)_0.4–(Bi_1/2K_1/2TiO₃)_0.6, where polar nanoregions (PNR) transform into static‐PNR as evidenced by piezoresponse force microscopy (PFM) and simultaneously enable congruent multiferroic clusters (MFC) to emerge from inherent strongly magnetic Bi(Fe,Co)O₃ rich regions as verified by magnetic force microscopy (MFM) and secondary ion mass spectrometry. The material's exceptionally large Néel temperature T_N = 670 ± 10 K, as found by neutron diffraction, is proposed to be a consequence of ferrimagnetic order in MFC. On these MFC, exceptionally large direct and converse magnetoelectric (ME) coupling coefficients, α ≈ 1.0 × 10^?5 s m^?1 at room‐temperature, are measured by PFM and MFM, respectively. It is expected that the non‐ergodic relaxor properties which are governed by the Bi_1/2K_1/2TiO₃ component to play a vital role in the strong ME coupling, by providing an electrically and mechanically flexible environment to MFC. This new class of non‐ergodic relaxor multiferroics bears great potential for applications. Especially the prospect of a ME nanodot storage device seems appealing.     

Dielectric properties of Fe-doped BaxSr1−xTiO3 thin films on polycrystalline substrates at temperatures between −35 and +85 °C

Large-area Ba_xSr_1−xTiO₃ (BSTO-x) thin films, partially Fe-doped, have been grown by pulsed laser deposition (PLD) on technically relevant polycrystalline alumina based ceramics. The capacity (dielectric constant _r) and Q-factor of planar Pt/BTO:Fe/Pt capacitors were investigated within a temperature range from −35 to +85 °C. The applied DC-bias voltages were up to 10 V and the measurement frequency was 1 kHz.Although operating in the ferroelectric state below the Curie temperature, pure BaTiO₃ (BTO) thin films showed the smallest variation of _r within the temperature range from −35 to +85 °C compared to BSTO-0.6 and BSTO-0.8. The temperature dependence of _r below the Curie temperature (ferroelectric state) seems to be smaller than above the Curie temperature (paraelectric state) for the BSTO-x system. A homogeneous tunability of the capacity of about 60% was achieved for applied electrical DC voltages resulting in electrical field strengths between 0 and 5 V/μm within the whole temperature range. The Q-factor of 2 μm thick BTO films increases with increasing DC bias voltage. Furthermore, by Fe-doping of BTO films Q-factors could be increased by a factor of three up to about 70 compared to the not doped films. In addition, the temperature dependence of capacity is considerably influenced by Fe-doping.At a microwave frequency of 30 GHz high _r values of about 1500 were measured for large-area BSTO-0.45 films at room temperature deposited directly on microwave ceramic substrates. Low values of tanδ of about 0.003 were measured for the PLD-BSTO-0.45 films which corresponds to a Q-factor of more than 300. The results show the potential of ferroelectric BTO thin films for applications as tunable electronic devices in a wide temperature range.     

High‐Performance [001]c‐Textured PNN‐PZT Relaxor Ferroelectric Ceramics for Electromechanical Coupling Devices

[001]_C‐Textured 0.55Pb(Ni_1/3Nb_2/3)O₃–0.15PbZrO₃–0.3PbTiO₃ (PNN‐PZT) ceramics are prepared by the templated grain‐growth method using BaTiO₃ (BT) platelet templates. Samples with different template contents are fabricated and compared in terms of texture fraction, microstructure, and piezoelectric, ferroelectric and dielectric properties. High piezoelectric performance (d₃₃ = 1210 pC N^?1, d₃₃* = 1773 pm V^?1 at 5 kV cm^?1) and high figure of merit g₃₃?d₃₃ (21.92 × 10^?12 m² N^?1) are achieved in the [001]_C‐textured PNN‐PZT ceramic with 2 vol% BaTiO₃ template, for which the texture fraction is 82%. In addition, domain structures of textured PNN‐PZT ceramics are observed and analyzed, which provide clues to the origin of the giant piezoelectric and electromechanical coupling properties of PNN‐PZT ceramics.     

Photoluminescence studies on InGaAlP layers grown by low-pressure metalorganic chemical vapor deposition

The optical properties for In_0.5(Ga_1-x Al _x )_0.5P (0 <x < 0.4) layers, grown by low-pressure Metalorganic Chemical Vapor Deposition, have been studied with photolominescence (PL) measurement. The PL intensity decreases with the increase of the Al composition (0 <x < 0.4). This dependence could not be accounted for only by the electron overflow from theΓ band to the X band. And the PL intensity is directly proportional to the excitation power at low temperature, below 50 K. On the other hand, the PL intensity is proportional to the second power of the excitation power at a high temperature range (>200 K). These results indicate that non-radiative recombination centers bound to theΓ band in In_0.5(Ga_1-x Al _x )_0.5P play a very important role in the radiation mechanism. PL dependence also shows these non-radiative recombination centers are thought to have strong relation to the aluminum substitution for In_0.5(Ga_1-x Al _x )_0.5P.     

Nanocasting of Mesoporous In‐TM (TM = Co,Fe, Mn) Oxides: Towards 3D Diluted‐Oxide Magnetic Semiconductor Architectures

Transition metal (Co, Fe, Mn)‐doped In₂O_3?y mesoporous oxides are synthesized by nanocasting using mesoporous silica as hard templates. 3D ordered mesoporous replicas are obtained after silica removal in the case of the In‐Co and In‐Fe oxide powders. During the conversion of metal nitrates into the target mixed oxides, Co, Fe, and Mn ions enter the lattice of the In₂O₃ bixbyite phase via isovalent or heterovalent cation substitution, leading to a reduction in the cell parameter. In turn, non‐negligible amounts of oxygen vacancies are also present, as evidenced from Rietveld refinements of the X‐ray diffraction patterns. In addition to (In_1?xTM_x)₂O_3?y, minor amounts of Co₃O₄, α‐Fe₂O₃, and Mn_xO_y phases are also detected, which originate from the remaining TM cations not forming part of the bixbyite lattice. The resulting TM‐doped In₂O_3?y mesoporous materials show a ferromagnetic response at room temperature, superimposed on a paramagnetic background. Conversely, undoped In₂O_3?y exhibits a mixed diamagnetic‐ferromagnetic behavior with much smaller magnetization. The influence of the oxygen vacancies and the doping elements on the magnetic properties of these materials is discussed. Due to their 3D mesostructural geometrical arrangement and their room‐temperature ferromagnetic behavior, mesoporous oxide‐diluted magnetic semiconductors may become smart materials for the implementation of advanced components in spintronic nanodevices.     

Low Voltage and Ferroelectric 2D Electron Devices Using Lead‐Free BaxSr1‐xTiO3 and MoS2 Channel

Coupling between non‐toxic lead‐free high‐k materials and 2D semiconductors is achieved to develop low voltage field effect transistors (FETs) and ferroelectric non‐volatile memory transistors as well. In fact, low voltage switching ferroelectric memory devices are extremely rare in 2D electronics. Now, both low voltage operation and ferroelectric memory function have been successfully demonstrated in 2D‐like thin MoS₂ channel FET with lead‐free high‐k dielectric Ba_xSr_1‐xTiO₃ (BST) oxides. When the BST surface is coated with a 5.5‐nm‐ultrathin poly(methyl methacrylate) (PMMA)‐brush for improved roughness, the MoS₂ FET with BST (x = 0.5) dielectric results in an extremely low voltage operation at 0.5 V. Moreover, the BST with an increased Ba composition (x = 0.8) induces quite good ferroelectric memory properties despite the existence of the ultrathin PMMA layer, well switching the MoS₂ FET channel states in a non‐volatile manner with a ±3 V low voltage pulse. Since the employed high‐k dielectric and ferroelectric oxides are lead‐free in particular, the approaches for applying high‐k BST gate oxide for 2D MoS₂ FET are not only novel but also practical towards future low voltage nanoelectronics and green technology.     

Charge‐Carrier Dynamics,Mobilities, and Diffusion Lengths of 2D–3D Hybrid Butylammonium–Cesium–Formamidinium Lead Halide Perovskites

Perovskite solar cells (PSCs) have improved dramatically over the past decade, increasing in efficiency and gradually overcoming hurdles of temperature‐ and humidity‐induced instability. Materials that combine high charge‐carrier lifetimes and mobilities, strong absorption, and good crystallinity of 3D perovskites with the hydrophobic properties of 2D perovskites have become particularly promising candidates for use in solar cells. In order to fully understand the optoelectronic properties of these 2D–3D hybrid systems, the hybrid perovskite BA_x(FA_0.83Cs_0.17)_1‐xPb(I_0.6Br_0.4)₃ is investigated across the composition range 0 ≤ x ≤ 0.8. Small amounts of butylammonium (BA) are found that help to improve crystallinity and appear to passivate grain boundaries, thus reducing trap‐mediated charge‐carrier recombination and enhancing charge‐carrier mobilities. Excessive amounts of BA lead to poor crystallinity and inhomogeneous film formation, greatly reducing effective charge‐carrier mobility. For low amounts of BA, the benevolent effects of reduced recombination and enhanced mobilities lead to charge‐carrier diffusion lengths up to 7.7 µm for x = 0.167. These measurements pave the way for highly efficient, highly stable PSCs and other optoelectronic devices based on 2D–3D hybrid materials.