Improved magnetic and piezoresponse behavior of cobalt substituted BiFeO3 thin film

Piezoresponse force microscopy (PFM) technique has been utilized to characterize the nanoscale electromechanical properties of chemical solution deposited pristine (BiFeO₃, BFO) and 5% Cobalt-substituted bismuth ferrite (BiFe_0.95Co_0.05O_3, BFCO) thin films. Distinct PFM contrast was observed on the films' surface both in out-of-plane and in-plane modes. Piezoresponse signal was larger in BFCO film than BFO and the former film also exhibited negative self polarization. The calculated self polarization factor was − 0.94. Lateral signal (in-plane) changed its sign upon 180° sample rotation which ruled out spurious electrostatic contribution and confirmed piezoelectric nature of the effect. Square patterns were written by local poling and reversible nature of the piezoresponse behavior was established. Well saturated piezoelectric hysteresis loops were acquired with improved piezoelectric coefficient value in case of Co-substituted BFO film. The effect has been described on the basis of polarization rotation with doping. Magnetization of BFO film also increases with Co-substitution. The enhancement in magnetic and ferro/piezoelectric properties should be useful for multiferroic applications.     

Unipolar resistive switching behavior of BiFeO3 thin films prepared by chemical solution deposition

Bismuth ferrite (BiFeO₃, BFO) thin films were spin-coated on Pt/Ti/SiO₂/Si substrates by a chemical solution deposition method. The ferroelectric BFO films annealed at 500 °C and 550 °C were found to possess unipolar resistive switching behaviors. The resistance ratio of the high resistance state (HRS) to the low resistance state (LRS) of the unipolar resistance switching is about 10³ for the ferroelectric BFO films. The conduction mechanisms are concluded to be space charge-limited conduction for the initial state and Ohmic conduction for the LRS. As for the HRS, the Poole-Frenkel emission fits well in the whole voltage region. Traps composed of oxygen vacancies are considered to play a key role in forming conducting paths. The relaxation time of electronic carriers is much shorter than that of ionic oxygen vacancies; therefore, the resistance switching is considered more probably due to carrier injection and emission through the Poole-Frenkel model after forming.     

Intermediate structural phases in rare-earth substituted BiFeO3

The room-temperature crystal structure and local ferroelectric properties of Bi_0.85RE_0.15FeO₃ (RE = Sm, Gd, Dy) polycrystalline samples have been investigated by X-ray diffraction (XRD) and piezoresponse force microscopy (PFM) techniques. XRD measurements show that the rare-earth substitution causes the transformation of R3c structure typical of BiFeO₃ to yield orthorhombic phases with √2a × 2√2a × 2a and √2a × 2a × √2a superlattices (a is the parameter of the cubic perovskite subcell). Results of PFM investigations imply that both the orthorhombic phases are polar. The models describing crystal structure of the phases are discussed.     

Hydrogen-induced degradation in multiferroic BiFeO3 ceramics

Chemical stability of multiferroic BiFeO₃ (BFO) ceramics has been studied through electrochemical hydrogen charging, in which BFO ceramic pellets were placed in 0.01 M NaOH solution with hydrogen deposited on their electrodes from the electrolysis of water. The properties of the samples were greatly degraded after the treatment: The leakage current was increased by orders of magnitude, the capacitance and the dielectric loss were dramatically increased in low frequency region. It was proposed that hydrogen entered into BFO lattice and existed at interstitial sites and the degradation was explained by hydrogen's reduction of some Fe³⁺ to Fe²⁺ in BFO. Hydrogen-induced degradation occurs relatively easily in BFO and much attention should be paid to it for BFO-based devices.     

BiFeO3 thin films prepared using metalorganic chemical vapor deposition

BiFeO₃ thin films were grown on (001) SrTiO₃ and (001) ZrO₂(Y₂O₃) substrates by single source metalorganic chemical vapor deposition in the temperature range T = 500 ÷ 800 °C using Fe(thd)₃ and Bi(C₆H₅)₃ as volatile precursors. X-ray diffraction analysis shows cube-on-cube epitaxial growth of BiFeO₃ on (001) SrTiO₃. The strongly reduced bismuth transfer into the film due to the high thermal stability of Bi(C₆H₅)₃ was counterbalanced by the increase of the total pressure as well as of the residence time of the precursor flow in the reactor; the Bi/Fe ratio in the film thus becomes close to that in the precursor mixture. Optical second harmonic generation measurements have evidenced the ferroelectric ordering in BiFeO₃ films and the apparent decrease of the Curie temperature of the strained films as compared to BiFeO₃ single crystal.     

Enhancement on effective piezoelectric coefficient of Bi3.25Eu0.75Ti3O12 ferroelectric thin films under moderate annealing temperature

Bi_3.25Eu_0.75Ti₃O₁₂ (BET) thin films were deposited on Pt/Ti/SiO₂/Si(111) substrates by a metal-organic decomposition method. The effects of annealing temperatures 600-800 °C on microstructure, ferroelectric, dielectric and piezoelectric properties of BET thin films were studied in detail. The spontaneous polarization (87.4 × 10^− 6 C/cm² under 300 kV/cm), remnant polarization (65.7 × 10^− 6 C/cm² under 300 kV/cm), the dielectric constant (992.9 at 100 kHz) and the effective piezoelectric coefficient d₃₃ (67.3 pm/V under 260 kV/cm) of BET thin film annealed at 700 °C are better than those of the others. The mechanisms concerning the dependence of the enhancement d₃₃ are discussed according to the phenomenological equation, and the improved piezoelectric performance could make the BET thin film a promising candidate for piezoelectric thin film devices.     

Enhanced multiferroic properties and tunable magnetic behavior in multiferroic BiFeO3-Bi0.5Na0.5TiO3 solid solutions

A series of multiferroic (1−x)BiFeO₃−x(Bi_0.5Na_0.5)TiO₃ (BF-BNT) (x = 0 − 0.6) solid solution ceramics were prepared by a sol-gel method. The XRD results show that increasing BNT content induce a gradual phase transformation from rhombohedral to pseudocubic structure near x = 0.4. Compared with pure BiFeO₃, superior multiferroic properties are obtained for x = 0.3 with remnant polarization P_r = 1.49 μC/cm² and saturated magnetization M_s = 0.51 emu/g. Importantly, the paramagnetic (PM) to ferromagnetic (FM) transition is observed for the solutions, and the Curie temperature (T_C) can be tuned by varying the content of BNT. This observed FM ordering is discussed in terms of the possible existence of the long-range superexchange interaction of Fe³⁺-O-Ti-O-Fe³⁺ in the chemically ordered regions.     

Microwave-hydrothermal synthesis of the multiferroic BiFeO3

In this work, three different methods for preparing BiFeO₃ polycrystals are compared: hydrothermal synthesis, microwave heating in the solid state and the combination of both, that is a hydrothermal method using microwave heating. The best materials, without high purity reactants, are obtained in few minutes by the last procedure, a new, very fast, reproducible and environment-friendly method of synthesis, which is described and discussed here.     

BiFeO3 films on steel substrate by the citrate method

We deposited BiFeO₃ films on stainless steel substrates using a simple low-temperature wet-chemical route. Bismuth and iron nitrates were used as metal source and citric acid as chelating agent to prepare a water solution and deposit the film by dipping the steel substrate in the viscous solution. We have investigated the composition, crystallinity and structure of the BiFeO₃ film on steel by X-ray diffraction, X-ray photoelectron spectroscopy, high resolution scanning electron microscopy, conventional and high resolution transmission electron microscopy, and energy dispersive spectroscopy techniques. The film deposited on the steel substrate has two sublayers: a very thin (about 100 nm) nanocrystalline layer, with crystallite size of few nanometers, and a thicker (below 1 μm) crystalline layer.     

Microwave absorption properties of multiferroic BiFeO3 nanoparticles

Multiferroic BiFeO₃ (BFO) nanoparticles ranging from 60 nm to 120 nm were synthesized successfully by a sol-gel method, and the microwave absorption properties of BFO nanoparticles were investigated in the range of 12.4 GHz to 18 GHz. The reflection loss of BFO nanoparticles is more than 10 dB (or more than 90%) in the 13.1 GHz-18 GHz range and reaches to 26 dB at 16.3 GHz, which indicated that the BFO is a good candidate for microwave absorption application. The excellent microwave absorption properties of BFO nanoparticles could be attributed to the good electromagnetic match as a consequence of the coexistence of ferroelectric and weak ferromagnetic order in BFO nanoparticles, which has been confirmed by electric and magnetic measurement. Moreover, the nanosize-confinement effect may also have contribution to the high reflection loss of BFO nanoparticles.     

Structural and dielectric properties of ferroelectric Sr1−xBaxBi2(Nb0.5Ta0.5)2O9 and Sr0.5Ba0.5Bi2(Nb1−yTay)2O9 ceramics

Ferroelectric Sr_1−xBa_xBi₂(Nb_0.5Ta_0.5)₂O₉ and Sr_0.5Ba_0.5Bi₂(Nb_1−yTa_y)₂O₉ were synthesized by solid state reaction route. X-ray diffraction studies confirm the formation of single phase layered perovskite solid solutions over a wide range of compositions (x=y=0.0, 0.25, 0.50, 0.75 and 1). The lattice parameters and the Curie temperature (T_c) have been found to have linear dependence on x and y. Transmission electron microscopy (TEM) suggest the lowering of orthorhombic distortion with increasing Ba²⁺ substitution. Variations in microstructural features as a function of x and y were monitored by scanning electron microscopy (SEM). The dielectric constant at room temperature increases with increase in both x and y. Interestingly Ba²⁺ substitution on Sr²⁺ site induces diffused phase transition and diffuseness increases with increasing Ba²⁺ concentration.     

Grain dependence of ferroelectric domain switching on SrBi2Ta2O9 thin films observed by Kelvin probe force microscope

We have studied grain-shape dependence of Kelvin probe force microscopy of SrBi₂Ta₂O₉ thin films on epitaxial La_0.5Sr_0.5CoO₃/LaAlO₃ substrates. By changing the growth condition in pulsed laser deposition, we have grown the SrBi₂Ta₂O₉ thin films with various grain shapes. The shape and the orientation of SrBi₂Ta₂O₉ the thin films with various growth conditions have been analyzed by X-ray diffraction and scanning electron microscope. The large number of the long rectangular grains was observed accompanied with relatively larger (220) peaks than other peaks. From the Kelvin probe force microscope study, it has been observed that the long rectangular grains showed characteristics of easy ferroelectric domain switching at a low writing bias and weaker influence of surface charges.     

Improved dielectric and ferroelectric properties in Ti-doped BiFeO3-PbTiO3 thin films prepared by pulsed laser deposition

Ti-modified thin films of multiferroic 0.72Bi(Fe_1 − xTi_x)O₃-0.28PbTiO₃ (BFPT, x = 0 and 0.02) solid solution were prepared by pulsed laser deposition. The BFPT (x = 0 and 0.02) films possess a tetragonal structure with highly preferential (001) orientation. The effects of the ionic substitution on the properties of BFPT (x = 0 and 0.02) films have been investigated. The leakage current of the BFPT (x = 0.02) thin film is significantly reduced, and the dielectric and ferroelectric properties greatly improved by the aliovalent ionic substitution of Ti⁴⁺ for Fe³⁺. The BFPT (x = 0.02) thin film exhibits a reasonably high remnant polarization P_r with 2P_r up to 90 μC/cm² at 312 kV/cm and a switchable polarization up to 92 μC/cm² at 417 kV/cm.     

Enhanced dielectric,ferroelectric and optical properties of lead free (K0.17Na0.83)NbO3 ceramic with WO3 addition

Polycrystalline lead-free ceramics (K_0.17Na_0.83)NbO₃ + x wt.% WO₃; (x = 0, 1, 3 and 5) have been synthesized via solid state reaction method. X-ray diffraction pattern at room temperature indicates the formation of pure perovskite phase with monoclinic structure for all samples. Dielectric constant versus temperature measurements shows an increase in dielectric constant with a shift in Curie temperature (T_C) toward higher temperature side. Remnant polarization (P_r) is found to be enhanced and reached upto 24 μC/cm² for x = 5 wt.% WO₃ from 12.5 μC/cm² for pure (K_0.17Na_0.83)NbO₃ ceramic. The value of coercive field (E_c) decreases with increasing wt.% of WO₃. From optical band gap study, we found blue shift in the band gap of (K_0.17Na_0.83)NbO₃ with increasing concentration of WO₃.     

Investigation of BiFeO3 modified PbTiO3-Bi(MgZr)O3-based complex perovskite ceramics

Bismuth containing crystalline solutions of (1 − x)Bi(MgZr)_0.5O₃-xPbTiO₃ (BMZ-PT) and [(BiFeO₃)_y − (BiMg_0.5Zr_0.5)_1−y]_x − [PbTiO₃]_1−x (BMZ-BF-PT) have been developed using conventional ceramic technology. X-ray diffraction analysis reveals that both the systems possess a perovskite structure, in which tetragonal to rhombohedral phase transformation appears for x = 0.55 in BMZ-PT and y = 0.20 in BMZ-BF-PT systems. SEM photographs reveal a uniform grain size distribution in the solid solution matrix with the presence of ferroelectric domains in few of the compositions. Ferroelectric hysteresis (polarization-electric field, P-E) loops reveal that increase in BiFeO₃ in BMZ-PT systems results in a decrease in residual polarization of the system with change and distortion in the shape of the (P-E) loops.     

Structural, dielectric, magnetic, magnetodielectric and impedance spectroscopic studies of multiferroic BiFeO3-BaTiO3 ceramics

Polycrystalline (1−x)BiFeO₃-xBaTiO₃ (x = 0.00, 0.10, 0.20 and 0.30) ceramics have been prepared via mixed oxide route. The effect of BaTiO₃ substitution on the dielectric, ferroelectric and magnetic properties of the BiFeO₃ multiferroic perovskite was studied. From XRD analysis it revealed that BaTiO₃ substitution does not affect the crystal structure of the (1−x)BiFeO₃-xBaTiO₃ system up to x = 0.30. Improved dielectric properties were observed in the prepared system. An anomaly in the dielectric constant (?) was observed in the vicinity of the antiferromagnetic transition temperature. Experimental results suggest that in the (1−x)BiFeO₃-xBaTiO₃ system, the increase of BaTiO₃ concentration leads to the effective suppression of the spiral spin structure of BiFeO₃, resulting in the appearance of net magnetization. The dependence of dielectric constant and loss tangent on the magnetic field is a evidence of magnetoelectric coupling in (1−x)BiFeO₃-xBaTiO₃ system. The impedance analysis suggests the presence of a temperature dependent electrical relaxation process in the material, which is almost similar for all the concentrations in the present studies. The electrical conductivity has been observed to increase with rise in temperature showing a typical negative temperature coefficient of the resistance (NTCR) behaviors analogous to a semiconductor and suggests a non-Debye type of electrical relaxation.     

The influence of epitaxial strain on magnetic and electrical properties of BiFeO3 thin films

Strained epitaxial BiFeO₃ films deposited on (001) SrTiO₃ substrates by metal organic chemical vapor deposition were studied by optical second harmonic generation (SHG) and SQUID magnetometry. The observed SHG intensity vs temperature dependencies indicate that for less strained films (σ < 0.6 GPa) a strong interplay between the ferroelectric and magnetic subsystems exists, while for the films with larger σ-values strain-induced destruction of the magnetic cycloidal ordering takes place.     

Ferroelectric and piezoelectric properties of tungsten substituted SrBi2Ta2O9 ferroelectric ceramics

Tungsten substituted samples of compositions SrBi₂(W_xTa_1−x)₂O₉ (x = 0.0, 0.025, 0.050, 0.075, 0.10 and 0.20) were synthesized by solid-state reaction method and studied for their microstructural, electrical conductivity, ferroelectric and piezoelectric properties. The X-ray diffractograms confirm the formation of single phase layered perovskite structure in the samples with x up to 0.05. The temperature dependence of dc conductivity vis-à-vis tungsten content shows a decrease in conductivity, which is attributed to the suppression of oxygen vacancies. The ferroelectric and piezoelectric studies of the W-substituted SBT ceramics show that the remanent polarization and d₃₃ values increases with increasing concentration of tungsten up to x ≤ 0.05. Such compositions with low conductivity and high P_r values should be excellent materials for highly stable ferroelectric memory devices.     

Effect of thermal stress on magnetic domain patterns of multiferroic Bi1-xDyxFeO3 thin films

Effect of temperature on magnetic domain structure of Bi_0.7Dy_0.3FeO₃ (BDFO) multiferroic thin films is studied in situ using magnetic force microscopy (MFM). Initially, as the temperature increases the domains start aligning from irregular to more distinct stripe pattern. However, above 250 °C, the domain alignment is disturbed. The systematic change in the domain configuration with temperature, suggests a strong thermal history of the system. The randomness in domain alignment caused above 250 °C is correlated to internal stress developed during ferromagnetic to paramagnetic phase transition occurring in BDFO. Indirect experimental evidence is given to support the explanation based on stress.     

Initial stages of WO3 growth on silicon substrates

Ultrathin films (5 nm, 10 nm and 20 nm effective thickness) of WO₃ have been deposited in high vacuum (10^− 6 Torr) onto single crystal Si(100) substrates and studied with X-ray diffraction, atomic force microscopy, scanning tunneling microscopy and spectroscopy. The experiments have been carried out on “as-deposited” thin films or after 1 h post-deposition annealing at various temperatures (ranging from 300 °C to 500 °C). A size induced increase of the amorphous to crystalline (monoclinic) phase transition has been observed for the 5 nm and 10 nm films, with a critical crystallite size of 25 ± 5 nm and a critical temperature of 345 ± 5 °C. All the experimental evidences show that, upon annealing, there is a diffusion limited aggregation growth of WO₃ that forms large flat two-dimensional islands composed by aggregates of individual crystallites approximately uniform in size and shape. These islands are isolated in the 5 nm thin films, are connected in the 10 nm case and form a uniform patchwork in the 20 nm thin films. Scanning tunneling spectroscopy shows the opening of a large surface band gap (2.7 eV) in the 500 °C annealed films and the significant presence of in gap states for thin films prepared with a lower (below 400 °C) annealing temperature. These findings are discussed in view of the optimization of the best morphological, structural and electronic parameters to fabricate WO₃ gas sensing devices at the sub-micrometer length scale.