The Effects of Multiphase Formation on Strain Relaxation and Magnetization in Multiferroic BiFeO3 Thin Films

Multiferroic epitaxial Bi‐Fe‐O thin films of different thicknesses (15–500 nm) were grown on SrTiO₃ (001) substrates by pulsed laser deposition under various oxygen partial pressures to investigate the microstructural evolution in the Bi‐Fe‐O system and its effect on misfit strain relaxation and on the magnetic properties of the films. Films grown at low oxygen partial pressure show the canted antiferromagnetic phase α‐Fe₂O₃ embedded in a matrix of BiFeO₃. The ferromagnetic phase, γ‐Fe₂O₃ is found to precipitate inside the α‐Fe₂O₃ grains. The formation of these phases changes the magnetic properties of the films and the misfit strain relaxation mechanism. The multiphase films exhibit both highly strained and fully relaxed BiFeO₃ regions in the same film. The magnetization in the multiphase Bi‐Fe‐O films is controlled by the presence of the γ‐Fe₂O₃ phase rather than heteroepitaxial strain as it is the case in pure single phase BiFeO₃. Also, our results show that this unique accommodation of misfit strain by the formation of α‐Fe₂O₃ gives rise to significant enhancement of the piezo electric properties of BiFeO_3.     

Room Temperature Ferrimagnetism and Ferroelectricity in Strained,Thin Films of BiFe0.5Mn0.5O3

Highly strained films of BiFe_0.5Mn_0.5O₃ (BFMO) grown at very low rates by pulsed laser deposition were demonstrated to exhibit both ferrimagnetism and ferroelectricity at room temperature and above. Magnetisation measurements demonstrated ferrimagnetism (T_C ～ 600K), with a room temperature saturation moment (M_S) of up to 90 emu/cc (～ 0.58 μ_B/f.u) on high quality (001) SrTiO₃. X‐ray magnetic circular dichroism showed that the ferrimagnetism arose from antiferromagnetically coupled Fe³⁺ and Mn³⁺. While scanning transmission electron microscope studies showed there was no long range ordering of Fe and Mn, the magnetic properties were found to be strongly dependent on the strain state in the films. The magnetism is explained to arise from one of three possible mechanisms with Bi polarization playing a key role. A signature of room temperature ferroelectricity in the films was measured by piezoresponse force microscopy and was confirmed using angular dark field scanning transmission electron microscopy. The demonstration of strain induced, high temperature multiferroism is a promising development for future spintronic and memory applications at room temperature and above.     

Anomalous Anisotropic Magnetoresistance of Antiferromagnetic Epitaxial Bimetallic Films: Mn2Au and Mn2Au/Fe Bilayers

Recently intensive efforts have been devoted to the emerging field of antiferromagnetic (AFM) spintronics, where ferromagnetic electrodes are substituted by antiferromagnets. This study investigates the anisotropic magnetoresistance (AMR) of epitaxial tetragonal antiferromagnetic bimetallic films: Mn₂Au and Mn₂Au/Fe bilayers. An anomalous AMR effect with additional peaks is observed. This study theoretically and experimentally demonstrates that the AFM spins of Mn₂Au can be viewed and controlled at room temperature, and this is achievable with a notably relatively small magnetic field of 200 mT. Strong hybridization between Au and Mn, and strong modification of the intrinsic quadratic anisotropy of Mn₂Au from interfacial biquadratic anisotropy result in an additional anomalous AMR component of 1%. The findings suggest that Mn₂Au films can be used in room temperature antiferromagnetic spintronics.     

Growth and characterization of OMVPE grown (In,Mn)As diluted magnetic semiconductor

In_1−xMn_xAs diluted magnetic semiconductor (DMS) thin films with x 0.14 have been grown using organometallic vapor phase epitaxy. Tricarbonyl-(methylcyclopentadienyl)manganese was successfully used as the Mn source. Single phase, epitaxial films were achieved for compositions as high as x=0.14 using growth temperatures ≥475°C. For lower growth temperatures or x>0.14, nanometer scale MnAs precipitates were observed within the In_1−xMn_xAs matrix. Transport properties were investigated using the Hall effect. All Mn doped films were p-type with single phase films exhibiting hole concentrations 2≤×10¹⁹ cm⁻³. Magnetization was measured as a function of temperature and applied field for a single phase film with x=0.1. Ferromagnetic ordering was observed at 5 K with a saturation magnetization of M_s=68 emu/cm³, a remnant magnetization, M_r=10 emu/cm³, and a coercive field H_c=400 Oe.     

Synthesis of Phase‐Pure Ferromagnetic Fe3P Films from Single‐Source Molecular Precursors

A new method for the preparation of phase‐pure ferromagnetic Fe₃P films on quartz substrates is reported. This approach utilizes the thermal decomposition of the single‐source precursors H₂Fe₃(CO)₉PR (R = ^tBu or Ph) at 400 °C. The films are deposited using a simple, home‐built metal‐organic chemical vapor deposition (MOCVD) apparatus and are characterized using a variety of analytical methods. The films exhibit excellent phase purity, as evidenced by X‐ray diffraction, X‐ray photoelectron spectroscopy, and field‐dependent magnetization measurements, the results of which agree well with measurements obtained from bulk Fe₃P. Using scanning electron microscopy and atomic force microscopy techniques, the films are found to have thicknesses between 350 and 500 nm with a granular surface texture. As‐deposited Fe₃P films are amorphous, and little or no magnetic hysteresis is observed in plots of magnetization versus applied field. Annealing the Fe₃P films at 550 °C results in improved crystallinity as well as the observation of magnetic hysteresis.     

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.     

Ferroelectric Materials: Probing Local and Global Ferroelectric Phase Stability and Polarization Switching in Ordered Macroporous PZT (Adv. Funct. Mater. 5/2011)

We describe the characterization, ferroelectric phase stability and polarization switching in strain‐free assemblies of PbZr_0.3Ti_0.7O₃ (PZT) nanostructures. The 3‐dimensionally ordered macroporous structures present uniquely large areas and volumes of PZT where the microstructure is spatially modulated and the composition is homogeneous. Variable temperature powder X‐ray diffraction (XRD) studies show that the global structure is crystalline and tetragonal at room temperature and undergoes a reversible tetragonal to cubic phase transition on heating/cooling. The measured phase‐transition temperature is 50–60 °C lower than bulk PZT of the same composition. The local ferroelectric properties were assessed using piezoresponse force spectroscopy that reveal an enhanced piezoresponse from the nanostructured films and demonstrate that the switching polarization can be spatially mapped across these structures. An enhanced piezoresponse is observed in the nanostructured films which we attribute to the formation of strain free films, thus for the first time we are able to assess the effects of crystallite‐size independently of internal stress. Corresponding polarization distributions have been calculated for the bulk and nanostructured materials using a direct variational method and Landau‐Ginzburg‐Devonshire (LGD) theory. By correlating local and global characterization techniques we have for the first time unambiguously demonstrated the formation of tetragonal and ferroelectric PZT in large volume nanostructured architectures. With the wide range of materials available that can be formed into such controlled architectures we conclude that this study opens a pathway for the effective studies of nanoscale ferroelectrics in uniquely large volumes.     

Probing Local and Global Ferroelectric Phase Stability and Polarization Switching in Ordered Macroporous PZT

We describe the characterization, ferroelectric phase stability and polarization switching in strain‐free assemblies of PbZr_0.3Ti_0.7O₃ (PZT) nanostructures. The 3‐dimensionally ordered macroporous structures present uniquely large areas and volumes of PZT where the microstructure is spatially modulated and the composition is homogeneous. Variable temperature powder X‐ray diffraction (XRD) studies show that the global structure is crystalline and tetragonal at room temperature and undergoes a reversible tetragonal to cubic phase transition on heating/cooling. The measured phase‐transition temperature is 50–60 °C lower than bulk PZT of the same composition. The local ferroelectric properties were assessed using piezoresponse force spectroscopy that reveal an enhanced piezoresponse from the nanostructured films and demonstrate that the switching polarization can be spatially mapped across these structures. An enhanced piezoresponse is observed in the nanostructured films which we attribute to the formation of strain free films, thus for the first time we are able to assess the effects of crystallite‐size independently of internal stress. Corresponding polarization distributions have been calculated for the bulk and nanostructured materials using a direct variational method and Landau‐Ginzburg‐Devonshire (LGD) theory. By correlating local and global characterization techniques we have for the first time unambiguously demonstrated the formation of tetragonal and ferroelectric PZT in large volume nanostructured architectures. With the wide range of materials available that can be formed into such controlled architectures we conclude that this study opens a pathway for the effective studies of nanoscale ferroelectrics in uniquely large volumes.     

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.     

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.     

Intrinsic Half‐Metallicity in 2D Ternary Chalcogenides with High Critical Temperature and Controllable Magnetization Direction

Searching for 2D ferromagnetic materials with a high critical temperature, large spin polarization, and controllable magnetization direction is a key challenge for their broad applications in spintronics. Here, through a systematic study on a series of 2D ternary chalcogenides with first‐principles calculations, it is demonstrated that a family of experimentally available 2D CoGa₂X₄ (X = S, Se, or Te) are half‐metallic ferromagnets, and they exhibit high critical temperature, fully polarized spin state, and strain‐dependent magnetization direction simultaneously. Following the Goodenough–Kanamori rules, the half‐metallic ferromagnetism of CoGa₂X₄ family is caused by superexchange interaction mediated by Co? X? Co bonds. The half‐metal gaps are large enough (>0.5 eV) to ensure that the half‐metallicity is stable against the spin flipping at room temperature. Magnetocrystalline anisotropy energy calculations indicate that CoGa₂X₄ favor easy plane magnetization. Under achievable biaxial tensile strain (2–6%), the magnetization directions of CoGa₂X₄ can change from in‐plane to out‐of‐plane, providing a route to control the efficiency of spin injection/detection. Further, the critical temperatures T_c of ferromagnetic phase transition for CoGa₂X₄ are close to room temperature. Belonging to the big family of layered AB₂X₄ compounds, the proposed CoGa₂X₄ systems will enrich the available 2D candidates and their heterojunctions for various 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.     

Photoinduced Magnetization with a High Curie Temperature and a Large Coercive Field in a Co‐W Bimetallic Assembly

The crystal structure, magnetic properties, and temperature‐ and photoinduced phase transition of [{Co^II(4‐methylpyridine)(pyrimidine)}₂{Co^II(H₂O)₂}{W^V(CN)₈}₂]·4H₂O are described. In this compound, a temperature‐induced phase transition from the Co^II (S = 3/2)‐NC‐W^V(S = 1/2) [high‐temperature (HT)] phase to the Co^III(S = 0)‐NC‐W^IV(S = 0) [low temperature (LT)] phase is observed due to a charge‐transfer‐induced spin transition. When the LT phase is irradiated with 785 nm light, ferromagnetism with a high Curie temperature (T_C) of 48 K and a gigantic magnetic coercive field (H_c) of 27 000 Oe are observed. These T_C and H_c values are the highest in photoinduced magnetization systems. The LT phase is optically converted to the photoinduced phase, which has a similar valence state as the HT phase due to the optically induced charge‐transfer‐induced spin transition.     

Structure and Morphology of PDI8‐CN2 for n‐Type Thin‐Film Transistors

A multiscale investigation of N,N′‐bis(n‐octyl)‐x:y, dicyanoperylene‐3,4:9,10‐bis(dicarboximide), PDI8‐CN2, shows the same molecular arrangement in the bulk and in thin films sublimated on SiO₂/Si wafers. Non‐conventional powder diffraction methods and theoretical calculations concur to provide a coherent picture of the crystalline structure. X‐ray diffraction (XRD) and atomic force microscopy (AFM) analyses of films of different thickness deposited at different substrate temperatures indicate the existence of two temperature‐dependent deposition regimes: a low‐temperature (room temperature) regime and a high‐temperature (80–120 °C) one, each characterized by different growth mechanisms. These mechanisms eventually result in different morphological and structural features of the films, which appear to be highly correlated with the trend of the electrical parameters that are measured in PDI8‐CN2‐based field‐effect transistors.     

Controlling Chiral Spin States of a Triangular‐Lattice Magnet by Cooling in a Magnetic Field

Magnetic materials with a non‐collinear and non‐coplanar arrangement of magnetic moments hosting a nonzero scalar spin‐chirality exhibit unique magnetic and spin‐dependent electronic transport properties. The spin chirality often occurs in materials where competing exchange interactions lead to geometrical frustrations between magnetic moments and to a strong coupling between the crystal lattice and the magnetic structure. These characteristics are particularly strong in Mn‐based antiperovskites where the interactions and chirality can be tuned by substitutional modifications of the crystalline lattice. This study presents evidence for the formation of two unequal chiral spin states in magnetically ordered Mn_3.338Ni_0.651N antiperovskite based on density functional theory calculations and supported by magnetization measurements after cooling in a magnetic field. The existence of two scalar spin‐chiralities of opposite sign and different magnitude is demonstrated by a vertical shift of the magnetic‐field dependent magnetization and Hall effect at low fields and from an asymmetrical magnetoresistivity when the applied magnetic field is oriented parallel or antiparallel to the direction of the cooling field. This opens up the possibility of manipulating the spin chirality for potential use in the emerging field of chiral spintronics.     

Electrical Manipulation of Orbital Occupancy and Magnetic Anisotropy in Manganites

Electrical manipulation of lattice, charge, and spin is realized respectively by the piezoelectric effect, field‐effect transistor, and electric field control of ferromagnetism, bringing about dramatic promotions both in fundamental research and industrial production. However, it is generally accepted that the orbital of materials are impossible to be altered once they have been made. Here, electric field is used to dynamically tune the electronic‐phase transition in (La,Sr)MnO₃ films with different Mn⁴⁺/(Mn³⁺ + Mn⁴⁺) ratios. The orbital occupancy and corresponding magnetic anisotropy of these thin films are manipulated by gate voltage in a reversible and quantitative manner. Positive gate voltage increases the proportion of occupancy of the orbital and magnetic anisotropy that were initially favored by strain (irrespective of tensile and compressive), while negative gate voltage reduces the concomitant preferential orbital occupancy and magnetic anisotropy. Besides its fundamental significance in orbital physics, these findings might advance the process towards practical oxide‐electronics based on orbital.     

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.     

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.     

Self‐Assembly of Nanostructured,Complex, Multication Films via Spontaneous Phase Separation and Strain‐Driven Ordering

Spontaneous self‐assembly of a multication nanophase in another multication matrix phase is a promising bottom‐up approach to fabricate novel, nanocomposite structures for a range of applications. In an effort to understand the mechanisms for such self‐assembly, complimentary experimental and theoretical studies are reported to first understand and then control or guide the self‐assembly of insulating BaZrO₃ (BZO) nanodots within REBa₂Cu₃O_7–δ (RE = rare earth elements including Y, REBCO) superconducting films. The strain field developed around BZO nanodots embedded in the REBCO matrix is a key driving force dictating the self‐assembly of BZO nanodots along REBCO c‐axis. The size selection and spatial ordering of BZO self‐assembly are simulated using thermodynamic and kinetic models. The BZO self‐assembly is controllable by tuning the interphase strain field. REBCO superconducting films with BZO defect arrays self‐assembled to align in both vertical (REBCO c‐axis) and horizontal (REBCO ab‐planes) directions result in the maximized pinning and J_c performance for all field angles with smaller angular J_c anisotropy. The work has broad implications for the fabrication of controlled self‐assembled nanostructures for a range of applications via strain‐tuning.     

Realizing an Epitaxial Decorated Stanene with an Insulating Bandgap

The exploration of intriguing topological quantum physics in stanene has attracted enormous interest but is challenged by lacking desirable material samples. The successful fabrication of monolayer stanene on PbTe(111) films with low‐temperature molecular beam epitaxy and thorough characterizations of its atomic and electronic structures are reported here. In situ angle‐resolved photoemission spectroscopy together with first‐principles calculations identify two hole bands of p _xy orbital with a spin‐orbit coupling induced band splitting and meanwhile reveal an automatic passivation of p _z orbital of stanene. Importantly, material properties are tuned by substrate engineering, realizing a decorated stanene sample with truly insulating bulk on Sr‐doped PbTe. This finding paves a road for studies of stanene‐based topological quantum effects and electronics.