Effect of Substrate on Structure and Multiferrocity of (La,Mn) CoSubstituted BiFeO3 Thin Films

In this article, we report the substrate effect on ferroelectric and magnetic properties of epitaxial BiFeO₃‐based thin films at room temperature. (La, Mn) cosubstituted BiFeO₃ (BFOLM) thin films were deposited on differently lattice mismatched single‐crystal substrates to manipulate the strain states in the as‐deposited films. All the films with 30‐nm thick CaRuO₃ bottom electrodes exhibited highly epitaxial growth behavior with a slightly monoclinic distorted lattice structure while their strain states are drastically different as confirmed by X‐ray reciprocal space mapping. These films possessed significantly different macroscopic ferroelectric properties with giant remanent polarization of 101 ± 2, 65 ± 2, and 48 ± 2 μC/cm² for the films grown on SrTiO₃, (La, Sr)(Al, Ta)O₃, and LaAlO₃, respectively. It is found that the room‐temperature magnetic properties are also in accordance with their strain state, having a reciprocal relationship with polarization. For example, the enhanced magnetization is associated with the suppressed polarization and vice versa. The stain tunability of multiferroic properties in BFOLM thin films are presumably ascribed to the polarization rotation and oxygen octahedral tilts.     

Growth process approaches for improved properties of tunable ferroelectric thin films

Two approaches are shown for property control of tunable Ba_xSr_1−xTiO₃ (BST) films: (i) two-step growth and (ii) self-selective epitaxial growth. Both processes are based on the deposition of an amorphous ultra thin BST layer prior to the growth of an epitaxial BST film. In the first approach, the mechanical strain in the epitaxial films is controlled by employing a two-step growth process, where the very thin amorphous layer deposited first acts as an absorption layer for the misfit strain through its crystallization. Two-step grown films on LaAlO₃ substrates showed effective relaxation of the compressive misfit strain, which resulted in higher in-plane permittivity and tunability of the film. In the second approach, self-selective epitaxial growth, epitaxial/amorphous BST composite structures are achieved where the two phases are electrically inter-connected in parallel. Having a low permittivity, the amorphous component efficiently suppressed the effective permittivity of the composite capacitor, while the epitaxial component helps keep the tunability as large as that of a purely epitaxial BST film. The resultant composite film demonstrated a low permittivity having a high tunability, which is the contradictory phenomenon for a pure tunable ferroelectric.     

Electric‐Field‐Induced Domain Switching and Domain Texture Relaxations in Bulk Bismuth Ferrite

Bismuth ferrite, BiFeO₃, is an important multiferroic material that has attracted remarkable attention for potential applications in functional devices. While thin films of BiFeO₃ are attractive for applications in nanoelectronics, bulk polycrystalline BiFeO₃ has great potential as a lead‐free and/or high‐temperature actuator material. However, the actuation mechanisms in bulk BiFeO₃ are still to be resolved. Here we report the microscopic origin of electric‐field‐induced strain in bulk BiFeO₃ ceramic by means of in situ high‐energy X‐ray diffraction. Quantification of intrinsic lattice strain and extrinsic domain switching strain from diffraction data showed that the strain response in rhombohedral bulk BiFeO₃ is primarily due to non‐180° ferroelectric domain switching, with no observable change in the phase symmetry, up to the maximum field used in the study. The origin of strain thus differs from the strain mechanism previously shown in thin film BiFeO₃, which gives a similar strain/field ratio as rhombohedral bulk BiFeO₃. A strong post‐poling relaxation of switched non‐180° ferroelectric domains has been observed and hypothesized to be due to intergranular residual stresses with a possible contribution from the conductive nature of the domain walls in BiFeO₃ ceramics.     

First principle study on structural,elastic and electronic properties of cubic BiFeO3

We present the first principle studies of the structural and electronic properties in high temperature cubic phase (Pm3m) of BiFeO₃ based on Density Functional Theory (DFT). All calculations are performed within Local Density Approximation (LDA) functional and Generalized Gradient Approximation (GGA) functional with Ultrasoft Pseudopotentials (USP). It shows that the calculated structural parameters of cubic BiFeO₃ are in a good agreement with previous literatures. Based on the calculated of elastic properties of cubic BiFeO₃, this material shows a stable mechanical structure. In electronic band structure, the electron wave propagates through Brillouin zone X–R–M–G–R points where the highest valence band overlap with the lowest conduction band to give zero energy band gaps. The Density of States (DOS) demonstrated the significant hybridization between Bi6p, Fe3d and O2p in the range of ?5 eV–5 eV. Thus, it can be implied that multiferroic BiFeO₃ are metallic at cubic phase and the metal–insulator transition in this material obeys the band theory.     

Optical properties of epitaxial BiFeO3 thin film grown on SrRuO3-buffered SrTiO3 substrate

The BiFeO₃ (BFO) thin film was deposited by pulsed-laser deposition on SrRuO₃ (SRO)-buffered (111) SrTiO₃ (STO) substrate. X-ray diffraction pattern reveals a well-grown epitaxial BFO thin film. Atomic force microscopy study indicates that the BFO film is rather dense with a smooth surface. The ellipsometric spectra of the STO substrate, the SRO buffer layer, and the BFO thin film were measured, respectively, in the photon energy range 1.55 to 5.40 eV. Following the dielectric functions of STO and SRO, the ones of BFO described by the Lorentz model are received by fitting the spectra data to a five-medium optical model consisting of a semi-infinite STO substrate/SRO layer/BFO film/surface roughness/air ambient structure. The thickness and the optical constants of the BFO film are obtained. Then a direct bandgap is calculated at 2.68 eV, which is believed to be influenced by near-bandgap transitions. Compared to BFO films on other substrates, the dependence of the bandgap for the BFO thin film on in-plane compressive strain from epitaxial structure is received. Moreover, the bandgap and the transition revealed by the Lorentz model also provide a ground for the assessment of the bandgap for BFO single crystals.     

Structural distortion and photoconductive modulation of La1-xYxCoO3 epitaxial films

In this work, we successfully prepared epitaxial La_1-xY_xCoO₃ (x = 0, 0.05, 0.1, 0.15) films on (100) SrTiO₃ by polymer assisted deposition. The synergistic effect of biaxially tensile strain and doping yttrium on the structural distortion and photoconductive process of the films has been investigated. Due to lattice mismatch, the epitaxial strain along c-axis as well as the strain-induced tetragonal distortion of La_1-xY_xCoO₃ films increase with the content of doping yttrium. As-prepared films have higher degree of CoO₆ octahedral distortion, i.e., Jahn-Teller-like tetragonal distortion, which result in lower crystal field splitting energy and narrower band gap energy, thereby elevating the charge transition. Additionally, increase of epitaxial strain leads to lower adsorption free energy in La_1-xY_xCoO₃ films, and results in the increase of chemisorbed oxygen, which is beneficial to electron transport in the process of light response. The introduction of new oxygen vacancy defect sites by doping Y³⁺ ions and the proper amount of oxygen vacancy can effectively inhibit the recombination of the photo-induced electron-hole pairs, thus improving the activity for photoconductive response. The results reveal that the photoconductive properties of the as-prepared films are largely related to the synergistic effect of biaxially tensile-strained tetragonal distortion of CoO₆ and doping yttrium.     

Photoresponse of high quality epitaxial BiFeO3 films grown through hydrothermal method and rapid microwave assisted method

High quality BiFeO₃ film with enhanced remanent polarization and magnetization attracts much interest for its great application potential in information storage and photoelectric devices. Here we grew single-crystal epitaxial BiFeO₃ film on SrTiO₃ substrate through hydrothermal method at low temperature, the film has a quality higher than any reported BiFeO₃ films grown through hydrothermal method. Furthermore, BiFeO₃ film was grown through a 25 min rapid microwave-assisted hydrothermal process. The two BiFeO₃ films exhibited obvious light response to periodically switching on and off of a LED light, and the film grown through microwave-assisted hydrothermal method produced a 4.7V open-circuit voltage exceeding the band gap of BiFeO₃ originating from the ferroelectric photovoltaic effect. These results demonstrate that hydrothermal and microwave-assisted hydrothermal method are simple, inexpensive and rapid to grow high quality epitaxial BiFeO₃ film with potential application in photoelectric detection and photovoltaic.     

Uniaxial compressive stress and temperature dependent mechanical behavior of (1-x)BiFeO3-xBaTiO3 lead-free piezoelectric ceramics

The mechanical behavior of polycrystalline lead-free (1-x)BiFeO₃-xBaTiO₃ (BF-BT) piezoelectric ceramics was investigated under uniaxial compressive stress from room temperature up to 400 °C with macroscopic stress-strain measurements and in situ stress-dependent neutron diffraction. Stress-strain curves revealed a changing mechanical response with BaTiO₃ content and temperature. With decreasing BaTiO₃ content there was an increase in the coercive stress, which reduced the remanent strain and hysteresis. Full pattern structural refinement of the neutron data reveals both rhombohedral distortion and magnetic moment decreases with increasing BaTiO₃ content. In situ stress-dependent neutron diffraction experiments showed that accommodation of external stress occurs through the changes in tilt magnitude and anisotropy of oxygen octahedra at room temperature. The origin of stress-induced strain at room temperature is a lattice deformation without any apparent change in average crystallographic symmetry or domain switching. Temperature-dependent in situ stress-induced measurement of BF-30BT showed maximum strain close to the rhombohedral - pseudocubic transition temperature, which has been proposed to be due to the lattice deformation as well as to the differing degree of tilting of the (Fe/Ti)O₆ octahedra.     

Growth and characterisation of multiferroic BiFeO3 films with fully saturated ferroelectric hysteresis loops and large remanent polarisations

Multiferroic BiFeO₃ films have been deposited on a number of substrates by RF magnetron sputtering. Two routes were adopted in order to obtain the films of high phase purity and accurate stoichiometry. The first was to sputter films at room temperature and then the BiFeO₃ phase was formed after sintering at various temperatures under controlled ambient atmosphere. The second was to grow BiFeO₃ in-situ at high temperature during sputtering. Although the sintered films grown on SrTiO₃ substrates were epitaxial and showed better texture than the in-situ films, they had much poorer ferroelectric properties, due to the residual traces of intermediate phases formed during heating. Under right growth parameters, the in-situ films grown on the LaNiO_3?x buffered SrTiO₃ showed fully saturated ferroelectric hysteresis loops with large remanent polarisation of 64 μC/cm². Piezoresponse force microscopy (PFM) was used to examine the ferroelectric domain structures. When scanned without DC bias, fine spontaneous domains were observed. Under ±10 V DC bias, PFM confirmed that the domains could be poled and switched.     

Crystalline texture analyses of sputtered BiFeO3 thick films on Si with a large polarization

In our work last year (H. Zhu et al., Rhombohedral BiFeO₃ thick films integrated on Si with a giant electric polarization and prominent piezoelectricity, Acta Materialia 200 (2020) 305–314), it was demonstrated that the rhombohedral-like, (110)-textured BiFeO₃ thick films (～2 μm) sputter-deposited at 450 °C and 500 °C exhibited ultrahigh polarizations of P_r ～ 115 μC/cm² and 135 μC/cm², respectively. However, it is not sufficient to explain these ultra-high polarizations by a preferential growth mechanism and the effect of a moderate compressive strain. To further clarify the polarization enhancement of the films, the texture characteristics of these BFO thick films were quantitatively analyzed by fitting the rocking curves and pole figures to the March-Dollase model. The results showed that, in addition to the (110)-textured growth of a BFO thick film under a moderate compressive strain, the minority non-(110)-textured grains also contributed to the enhancement of the total polarization. Our study demonstrates that, the ultra-high polarizations of our BFO thick films can be well explained by adding the contribution from non-textured grains to the preferential growth of the film under a compressive strain.     

Enhancement of ferromagnetic and ferroelectric properties in calcium doped BiFeO3 by chemical synthesis

Calcium (Ca)-doped bismuth ferrite (BiFeO₃) thin films prepared by using the polymeric precursor method (PPM) were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), polarization and magnetic measurements. Structural studies by XRD and Rietveld refinement reveal the co-existence of distorted rhombohedral and tetragonal phases in the highest doped BiFeO₃ (BFO) where enhanced ferroelectric and magnetic properties are produced by internal strain. A high coercive field in the hysteresis loop is observed for the BiFeO₃ film. Fatigue and retention free characteristics are improved in the highest Ca-doped sample due to changes in the crystal structure of BFO for a primitive cubic perovskite lattice with four-fold symmetry and a large tetragonal distortion within the crystal domain.     

Microstructure and properties of Co-, Ni-, Zn-, Nb- and W-modified multiferroic BiFeO3 ceramics

BiFeO₃ polycrystalline ceramics were prepared by the mixed oxide route and a chemical route, using additions of Co, ZnO, NiO, Nb₂O₅ and WO₃. The powders were calcined at 700 °C and then pressed and sintered at 800–880 °C for 4 h. High density products up to 96% theoretical were obtained by the use of CoO, ZnO or NiO additions. X-ray diffraction, SEM and TEM confirmed the formation of the primary BiFeO₃ and a spinel secondary phase (CoFe₂O₄, ZnFe₂O₄ or NiFe₂O₄ depending on additive). Minor parasitic phases Bi₂Fe₄O₉ and Bi₂₅FeO₃₉ reduced in the presence of CoO, ZnO or NiO. Additions of Nb₂O₅ and WO₃ did not give rise to any grain boundary phases but dissolved in BiFeO₃ lattice. HRTEM revealed the presence of domain structures with stripe configurations having widths of typically 200 nm. In samples prepared with additives the activation energy for conduction was in the range 0.78–0.95 eV compared to 0.72 eV in the undoped specimens. In co-doped specimens (Co/Nb or Co/W) the room temperature relative permittivity was ～110 and the high frequency dielectric loss peaks were suppressed. Undoped ceramics were antiferromagnetic but samples prepared with Co or Ni additions were ferromagnetic; for 1% CoO addition the remanent magnetization (M_R) values were 1.08 and 0.35 emu/g at temperatures of 5 and 300 K, respectively.     

BiFeO3 Ceramics: Processing,Electrical, and Electromechanical Properties

Bismuth ferrite (BiFeO₃), a perovskite material, rich in properties and with wide functionality, has had a marked impact on the field of multiferroics, as evidenced by the hundreds of articles published annually over the past 10 years. Studies from the very early stages and particularly those on polycrystalline BiFeO₃ ceramics have been faced with difficulties in the preparation of the perovskite free of secondary phases. In this review, we begin by summarizing the major processing issues and clarifying the thermodynamic and kinetic origins of the formation and stabilization of the frequently observed secondary, nonperovskite phases, such as Bi₂₅FeO₃₉ and Bi₂Fe₄O₉. The second part then focuses on the electrical and electromechanical properties of BiFeO₃, including the electrical conductivity, dielectric permittivity, high‐field polarization, and strain response, as well as the weak‐field piezoelectric properties. We attempt to establish a link between these properties and address, in particular, the macroscopic response of the ceramics under an external field in terms of the dynamic interaction between the pinning centers (e.g., charged defects) and the ferroelectric/ferroelastic domain walls.     

Strain effects in epitaxial La-doped SrSnO3 films on lattice-matched PMN-PT substrates

Here we report the effect of the strain states on the structure, optical and electrical transport properties of the La_0.05Sr_0.95SnO₃ (LSSO) thin films grown epitaxially on (001)-oriented 0.70 Pb(Mg_1/3Nb_2/3)O₃-0.30PbTiO₃ (PMN-PT) substrates by pulsed laser deposition. X-ray diffraction results indicate that the films are fully strained up to at least 100 nm thickness, and the in-plane compressive strain gradually releases in thicker films. High-resolution transmission electron microscopy characterizations demonstrate that the LSSO films were grown coherently on PMN-PT(001) substrates. With varying the thicknesses of the fully strained films from 20 to 100 nm, the electrical transport properties are improved significantly. A lowest room-temperature resistivity of 1.88 mΩcm and the highest mobility of 28.1 cm²/Vs are obtained in the 100 nm film. The optical band gap determined from spectroscopic ellipsometry is found to increase from 4.58 to 4.88 eV with the film thicknesses varying from 20 to 500 nm. The results imply that the LSSO epitaxial films exhibit tunable electrical performances and optical band gaps through strain, which may have potential applications in optoelectrical devices.     

Polymorphism of M3AlX Phases (M = Ti,Zr, Hf; X = C,N) and Thermomechanical Properties of Ti3AlN Polymorphs

M₃AlX (M = Ti/Zr/Hf, X = C/N) compounds are promising high‐temperature structural ceramics. However, their interesting polymorphism, thermomechanical stabilities, and thermal and mechanical properties were not fully understood. In this work, the polymorphisms of M₃AX phases are investigated by combining first‐principles and lattice dynamics calculations. Only Ti₃AlN shows polymorphic transition between the cubic and orthorhombic phases at around 1105 K; but other M₃AlX phases do not display similar polymorphic phase transition. Furthermore, the temperature‐dependent heat capacity, thermal expansion, and elastic stiffness of Ti₃AlN polymorphic phases are reported for the first time to explore the relationship between crystal structures, and mechanical and thermal properties. Ti₃AlN polymorphs show anisotropic thermal expansion and elastic stiffness; and the orthorhombic Ti₃AlN is suggested as a promising damage tolerant nitride, which has similar properties with the previously reported Zr₃AlN and Hf₃AlN.     

Origin of Different Growth Modes for Epitaxial Manganite Films

The microstructures of the Bi_0.4Ca_0.6MnO₃ (BCMO) and La_0.67Ca_0.33MnO₃ (LCMO) epitaxial films are investigated by transmission electron microscopy in detail. BCMO epitaxial films (~ 10 and ~ 40 nm) exhibit an island growth mode whereas the LCMO films (~ 6 and ~ 30 nm) follow a layer by layer growth mode. Combined with the critical thickness models for the expected onset of the misfit dislocations in epitaxial films, an atomic collapse model is introduced to explain their mechanism of formation in manganite films. At the beginning of deposition, the strain caused by the lattice mismatch between the epitaxial film and substrate can be accommodated by elastic deformation. With the increase of film thickness, the strain becomes larger and larger. When the film thickness reaches the critical thickness, the strain can only be relaxed by the formation of misfit dislocations. Meanwhile, the atomic configuration of the epitaxial film will reorganize and some atoms begin to collapse, thus an island morphology will be formed. Once the collapse morphology is formed, maintenance of this wave‐like morphology depends on atomic diffusion length of the deposited atoms. If the diffusion length of the deposited atoms is long, the island morphology will not be maintained. If the diffusion length of the deposited atoms is short, the island morphology will keep until the epitaxial film is thick enough. The results could shed light on the growth modes for other perovskite epitaxial films.     

Piezoelectric properties of mechanochemically processed 0.67BiFeO3-0.33BaTiO3 ceramics

Solid solutions of BiFeO₃ and BaTiO₃ are promising lead-free piezoelectric materials, especially around the morphotropic phase boundary at 0.67BiFeO₃-0.33BaTiO₃. Still, these materials are challenged by phase instability and limited understanding of the processing-properties relationship. Here, we investigate mechanochemical activation and the use of BaTiO₃ as seed particles for the 0.67BiFeO₃-0.33BaTiO₃ phase. Contrary to expectations from seeding in lead-based perovskites, the BaTiO₃ seeds do not promote the 0.67BiFeO₃-0.33BaTiO₃ perovskite phase neither during the mechanochemical activation nor the subsequent sintering, but cause an inhomogeneous structure with remnant BaTiO₃. This results in ceramics with weaker low-field piezoelectric response than that of the unseeded route, but with higher field-induced strain, even up to 150 °C. Both routes produce ceramics of high density and without significant secondary phases visible by X-ray diffraction. This demonstrates the advantage of mechanochemical activation and the possibility to tailor the piezoelectric response of 0.67BiFeO₃-0.33BaTiO₃ through the processing route.     

Relationship between distortion of crystal structure and dielectric properties of complex perovskite oxide Ba(Co,Zn)1/3Nb2/3O3 thin films

The oxygen octahedral can be distorted by epitaxial strain due to the lattice mismatch. The epitaxial strain (ε_yy) linearly decreases from ? 0.244% to ? 0.445% with the growth temperature. Thin films grow along c axis on the SrTiO₃ substrate and exhibit the epitaxial relationship of Ba(Co,Zn)_1/3Nb_2/3O₃ (001) // SrTiO₃ (001). The superlattice reflections arising from in-phase tilting of the oxygen octahedra are clearly visible along [010] and [111] zone axis. The IR modes at 330 cm^?1 and 390 cm^?1 related to in-phase tilting are observed in far-infrared reflectivity spectroscopy. The calculated Q×f values from far-infrared reflectivity spectra of films grown at 550 °C to 700 °C increases from 51,000 GHz to 91,000 GHz mainly due to the enhancement of crystalline quality. The intrinsic quality factor (Q) is mainly contributed by O-(Co, Nb)-O and O-(Zn, Nb)-O bonding modes, while in-phase tilting in BCZN films may result in enhanced dielectric constants.     

Local Structure Investigation in Multiferroic BiFeO3–BaTiO3 Ceramics by XAS Technique and Their Relevant Properties

The (1?x)BiFeO₃‐xBaTiO₃ (with x = 0.1, 0.2, 0.3, and 0.4) ceramics were fabricated successfully by solid‐state reaction method. Single‐phase perovskite was obtained in all ceramics, as confirmed by XRD technique. It was observed that 0.7BiFeO₃–0.3BaTiO₃ was the morphotropic phase boundary (MPB) between rhombohedral and cubic phases, as also revealed from ferroelectric and magnetic properties. The simulated and experimental X‐Ray Absorption Spectroscopy (XAS) study revealed that BT in 0.75BF‐0.25BT is possibly taken a rhombohedral structure. Furthermore, the rounded ferroelectric hysteresis loops observed for 0.9BiFeO₃–0.1BaTiO₃ and 0.8BiFeO₃–0.2BaTiO₃ compositions could be attributed to their microstructure and surface charge effects and electron transfer between Fe³⁺ and Fe²⁺ ions. It was also found that high dielectric constant of 0.9BiFeO₃–0.1BaTiO₃ composition was a result of grain and grain‐boundary effects, as observed in SEM micrographs. In addition, a strong signature of dielectric relaxation behavior was observed in this ceramic system with the activation energy 0.467 eV obtained from the Arrhenius' law. Finally, the local structure investigation with XAS technique provided additional information to better understand the electric and magnetic properties in the BF‐BT ceramic system.     

Tailoring the multiferroic properties of BiFeO3 by co-doping Er at Bi site with aliovalent Nb,Mn and Mo at Fe site

Single phase multiferroic undoped BiFeO₃ notoriously suffers due to the poor spin–charge coupling resulting in limitations to device applications. The present work focuses on the tailoring of its multiferroic and magnetoelectric coupling properties by synthesizing multiferroic Bi_0.95Er_0.05Fe_0.98TM_0.02O₃ (TM = Nb, Mn and Mo) ceramics. The ferroelectric, magnetic, current leakage measurements and magnetoelectric effect were investigated. XRD along with the Reitveld refinement results confirms that all the samples possess perovskite based rhombohedral structure and reveals that doping of (Er, Nb), (Er, Mn) and (Er, Mo) induced the crystallographic distortion in the BFO lattice and hence induced a variation in the bond lengths and bond angle. Dual doping significantly enhanced the electrical, magnetic properties and magnetoelectric coupling as compared to BiFeO₃. Doping has lowered the leakage current by three to four orders compared to BFO. The lattice distortion, reduced leakage current and destruction of spin–cycloidal structure could be the origin for these improved features. The (Er, Nb) doped BiFeO₃ yields enhanced ferroelectric character with the maximum polarization value of 0.46 µC/cm², maximum ME coupling of 0.22 mV/cm at a magnetic field of 130 G, an improved magnetization with a remanance value of 0.0903 emu/g and the lowest leakage current density.