Influence of transition metal element (Co,Ni, Cu) doping on structural,electrical and magnetic properties of Bi<Subscript>0.9</Subscript>Ca<Subscript>0.1</Subscript>FeO<Subscript>3</Subscript> nanoparticles

The multiferroic Bi_0.9Ca_0.1FeO₃, Bi_0.9Ca_0.1Fe_0.9Co_0.1O₃, Bi_0.9Ca_0.1Fe_0.9Ni_0.1O₃, Bi_0.9Ca_0.1Fe_0.9Cu_0.1O₃ samples were prepared by a simple sol–gel method. Rietveld refinement of X-ray diffraction data and Raman spectra reflect a structural phase transition from single phase (rhombohedral, pure BiFeO₃) to two phase coexistence (rhombohedral R3c and cubic Fm-3 m). The structural distortion of Bi_0.9Ca_0.1Fe_0.9Ni_0.1O₃ is very marked. SEM images show the co-doped nanoparticles having an average size of 50 nm. A contribution from the leakage current have been observed in the P–E loops. XPS results reveal that the concentration of Fe²⁺ and oxygen vacancy decreased after transition metal elements (Co, Ni, Cu) doped into Bi_0.9Ca_0.1FeO₃. Moreover Co, Ni doping can enhance the saturation magnetization, while Cu doping can enhance the coercive field in Bi_0.9Ca_0.1FeO₃.     

The Multiferroic Properties of (Bi<Subscript>0.9</Subscript>Ba<Subscript>0.1</Subscript>)(Fe<Subscript>0.95</Subscript>Mn<Subscript>0.05</Subscript>)O<Subscript>3</Subscript> Films

(Bi_0.9Ba_0.1)(Fe_0.95Mn_0.05)O₃ films were prepared on LaNiO₃-coated surface oxidized Si substrates. XRD and Raman measurements confirm that the (Bi_0.9Ba_0.1)(Fe_0.95Mn_0.05)O₃ film has pure R3c structure. Clear ferromagnetism with saturated magnetization of about 25 emu/cm³ has been observed at room temperature. The ferroelectric properties of the (Bi_0.9Ba_0.1)(Fe_0.95Mn_0.05)O₃ film was confirmed by the observation of the ferroelectric domains and the converse piezoelectric coefficient d ₃₃ versus applied voltage hysteresis loops by piezoelectric force microscopy (PFM). The observation of ferromagnetism and ferroelectricity in (Bi_0.9Ba_0.1)(Fe_0.95Mn_0.05)O₃ films indicates the potential multiferroic applications.     

Influence of isovalent and heterovalent substitution for Bi<Superscript>3+</Superscript> and Fe<Superscript>3+</Superscript> on the properties of Bi<Subscript>2</Subscript>Fe<Subscript>4</Subscript>O<Subscript>9</Subscript>-based solid solutions

Bi_2–хLa_хFe₄O₉ and Bi₂Fe_4–2xTi_xCo_xO₉ ferrites have been prepared by solid-state reactions at a temperature of 1073 K. X-ray diffraction data indicate that, in the Bi_2–хLa_хFe₄O₉ system, the limiting degree of La³⁺ substitution for Bi³⁺ ions in Bi₂Fe₄O₉ does not exceed 0.05 and that the limiting degree of substitution in the Bi₂Fe_4–2xTi_xCo_xO₉ system lies in the range 0.05 < x < 0.1. The specific magnetization and specific magnetic susceptibility of the samples have been measured at temperatures from 5 to 300 K in a magnetic field of 0.86 T. The field dependences of magnetization obtained for the Bi_2–хLa_хFe₄O₉ and Bi₂Fe_4–2xTi_xCo_xO₉ ferrites at temperatures of 300 and 5 K demonstrate that partial isovalent substitution of La³⁺ for Bi³⁺ ions in Bi₂Fe₄O₉ and heterovalent substitution of Ti⁴⁺ and Co²⁺ ions for two Fe³⁺ ions leads to partial breakdown of the antiferromagnetic state and nucleation of a ferromagnetic state.     

Effects of Nd concentration on structural and magnetic properties of ZnFe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles

Zinc ferrite nanomaterials have been received significant attention in recent years on account of their potential applications in the fields of electronics, optoelectronics and magnetics. To enhance the magnetic properties of zinc ferrites, Nd-doped zinc ferrites (ZnFe_2?xNd_xO₄, x?=?0, 0.01, 0.02, 0.03) nanoparticles (NPs) have been prepared by the sol–gel method. The effects of Nd doping concentration on the structural and magnetic properties of zinc ferrites were studied. The results of X-ray diffraction, scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy indicated that the Nd ions were incorporated into the crystal lattice of ZnFe₂O₄ and substituted for the Fe³⁺ sites. Unlike pure zinc ferrites with paramagnetism, Nd doped ZnFe₂O₄ NPs were superparamagnetic at room temperature. Vibrating sample magnetometry results showed, with the increase of Nd content, the saturation magnetization of Nd doped ZnFe₂O₄ NPs increased.     

Synthesis and characterization of M<Subscript>3</Subscript>V<Subscript>2</Subscript>O<Subscript>8</Subscript> (M = Ca,Sr and Ba) by a solid-state metathesis approach

A solid-state metathesis approach initiated by microwave energy has been successfully applied for the synthesis of orthovanadates, M₃V₂O₈ (M = Ca, Sr, and Ba). The structural, vibrational, thermal, optical and chemical properties of synthesized powders are determined by powder X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, magnetic property measurements and diffused reflectance spectra in the UV-VIS range. The direct bandgap of the synthesized materials was found to be 3·55 ± 0·2 eV, 3·75 ± 0·2 eV and 3·57 ± 0·2 eV for Ca₃V₂O₈, Sr₃V₂O₈ and Ba₃V₂O₈, respectively.     

Luminescence properties of Bi codoped and P codoped Ca<Subscript>3</Subscript>(VO<Subscript>4</Subscript>)<Subscript>2</Subscript>:Eu<Superscript>3+</Superscript>

New red emitting phosphors, Ca₃(VO₄)₂:Eu³⁺,Bi³⁺, Ca₃((P,V)O₄)₂:Eu³⁺ were synthesized by low temperature solid-state reaction and characterized by X-ray diffraction, scanning electron microscopy, photoluminescence spectra and Fourier transform infrared spectroscopy. The results show that the red emission located at about 613 nm was ascribed to ⁵ D ₀-⁷ F ₂ transition of Eu³⁺. The effect of by Bi doping and by P doping was also investigated systematically.     

Phase developments and dielectric responses of barium substituted four-layer CaBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> Aurivillius

In this paper, mixed Ca–Ba oxide Ca_1 − x Ba _x Bi₄Ti₄O₁₅ (CBBT) ceramics, fabricated by the improved traditional ceramics process were investigated by doping concentrations of Ba ion up to x =\emph{x} {=} 0·9 (in steps of 0·1). At room temperature, an orthorhombic crystal system was confirmed using XRD, and their parameter was obtained using the Rietveld method. Dielectric properties and phase transitions were studied and are explained in terms of lattice response of these ceramics. A shift in ferroelectric–paraelectric phase transition (T_C\emph{T}_{C}) to lower temperatures and a corresponding decrease in permittivity peak with increasing concentration of Ba^2 + are also observed. The ferroelectric–paraelectric phase transition of CBBT compounds is of normal type in nature, differing from the relaxor characteristic of BBT. The decrease of orthorhombicity in the lattice structure by the larger Ba^2 + ion incorporation, indicating an approach of a and b, results in lower Curie temperature. Appearance of anomalous loss peaks of Ba-rich compounds at 530°C reveals a phase transition development trend from ferroelectric orthorhombic structure to the paraelectric orthorhombic structure. Relationship of polarization with lattice response is discussed.     

Effects of sodium oleate on synthesis and photocatalytic activity of Bi<Subscript>2</Subscript>WO<Subscript>6</Subscript>/Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>@RGO

In this study, the effects of sodium oleate on synthesis of Bi₂WO₆/Bi₂O₃ loaded reduced graphene oxide photocatalyst was studied. The as-prepared composites were characterized by X-ray diffraction, Fourier transform infrared, X-ray photoelectron spectroscopy, UV–visible diffuse reflectance and photoluminescence spectroscopy. The results suggested that addition of sodium oleate not only promoted synthesis of Bi₂O₃, but also enhanced the reduction of GO to graphene. When the amount of sodium oleate was 4 mol (Bi:SO?=?1:1), Bi₂WO₆/Bi₂O₃@RGO to the best visible-light photocatalytic activity can be synthesized by a facile one-step solvothermal process without further reduction reaction. Hence, it indicated that sodium oleate could affect the synthesis of the as-prepared composites and the photocatalytic activity for degradation of RhB. This study did provide not only a facile method to synthesize Bi₂WO₆/Bi₂O₃@RGO, but also a method to reduce graphene oxide to graphene.     

Diffusion phase transition and impedance spectroscopy of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>/CuO co-doped BCZT lead-free ceramics

Perovskite type (Ba_0.85Ca_0.15?2x Bi_2x )(Zr_0.1Ti_0.9?x Cu _x )O₃ lead-free ceramics were prepared via a conventional solid-state reaction method. The phase structure, dielectric, ferroelectric properties and complex impedance were investigated in detail. XRD and dielectric measurements determined that single orthorhombic phase displayed in (Ba_0.85Ca_0.15)(Zr_0.1Ti_0.9)O₃ at room temperature. With the introduction of Bi₂O₃/CuO, the phase structure exhibited the mixture of orthorhombic and tetragonal phases, and then turned to single tetragonal phase. In contrast to the sharp dielectric transition of (Ba_0.85Ca_0.15)(Zr_0.1Ti_0.9)O₃ ceramics, a broad dielectric peak coupled with a slight decrease in Curie temperature was observed in (Ba_0.85Ca_0.15?2x Bi_2x )(Zr_0.1Ti_0.9?x Cu _x )O₃ ceramics with increasing x. The observed diffuse phase transition behavior was further confirmed by a couple of measurements with polarization loops and polarization current density curves. The structural and the composition fluctuations induced by ions doping should be responsible for the diffuse phase transition behavior. Furthermore, physical mechanisms of the conduction and relaxation processes were revealed by using impedance spectroscopy analyses. It was concluded that the conduction and relaxation processes were thermally activated, which was closely linked with the singly and doubly ionized oxygen vacancies.     

Co-precipitation method for the preparation of ferroelectric CaBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript>

A simple co-precipitation technique has been successfully applied for the preparation of pure single phase CaBi₄Ti₄O₁₅ (CBT) powders. Ammonium oxalate and ammonium hydroxide were used to precipitate Ca²⁺, Bi³⁺ and Ti⁴⁺ cations simultaneously. No pyrochlore phase was found while heating powder at 600 C and pure CBT phase was found to be formed by X-ray diffraction. Particle size and morphology was studied by transmission electron microscopy (TEM). The room temperature dielectric constant at 1 kHz is 400. The ferroelectric hysteresis loop parameters of these samples were also studied.     

Combustion synthesis and characterization of Ba<Subscript>2</Subscript>NdSbO<Subscript>6</Subscript> nanocrystals

Nanocrystalline Ba₂NdSbO₆, a complex cubic perovskite metal oxide, powders were synthesized by a self-sustained combustion method employing citric acid. The product was characterized by X-ray diffraction, differential thermal analysis, thermogravimetric analysis, Fourier transform infrared spectroscopy, transmission electron microscopy and scanning electron microscopy. The as-prepared powders were single phase Ba₂NdSbO₆ and a mixture of polycrystalline spheroidal particles and single crystalline nanorods. The Ba₂NdSbO₆ sample sintered at 1500°C for 4 h has high density (∼ 95% of theoretical density). Sintered nanocrystalline Ba₂NdSbO₆ had a dielectric constant of ∼ 21; and dielectric loss = 8 × 10⁻³ at 5 MHz.     

Effect of La substitution on structural and electrical properties of Ba(Fe<Subscript>2/3</Subscript>W<Subscript>1/3</Subscript>)O<Subscript>3</Subscript> nanoceramics

The nanocrystalline fine powders (∼80 nm) of (Ba_1−x La _x )(Fe_2/3W_1/3)_1−x/4O₃, (BLFW) (x = 0.0, 0.05, 0.10 and 0.15) were synthesized with a combined mechanical activation and conventional high-temperature solid-state reaction methods. Preliminary X-ray structural analysis of pellet samples (prepared from fine powders) showed formation of a single-phase tetragonal system. Detailed studies of dielectric properties (ε_r and tan δ) exhibit that these parameters are strongly dependent on frequency, temperature and La composition. The La-substitution increases the dielectric constant and decreases the tan δ up to 10% substitutions of La at the Ba-site, and then reversed the variation, and hence this composition is considered as a critical composition. This observation was found valid for structure, microstructures, dielectric constant, electrical conductivity, J–E characteristics and impedance parameters also. Like in other perovskites (PZT, BZT), La substitution plays an important role in tailoring the properties of Ba(Fe_2/3W_1/3)O₃ ceramics.     

Synthesis and microwave absorption property of ternary composites: polyaniline/CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/Ba<Subscript>3</Subscript>Co<Subscript>2</Subscript>Fe<Subscript>24</Subscript>O<Subscript>41</Subscript>

Polyaniline (PANI)/CoFe₂O₄/Ba₃Co₂Fe₂₄O₄₁ composite was prepared by an in-situ polymerization method. The phase structure, morphology and magnetic properties of the as-prepared PANI/CoFe₂O₄/Ba₃Co₂Fe₂₄O₄₁ composite were characterized by XRD, FT-IR, SEM, TEM, and VSM, respectively. The microwave absorption properties of the composite were investigated by using a vector network analyzer in the 2–18 GHz frequency range. The results show that the maximum reflection loss value of the PANI/CoFe₂O₄/Ba₃Co₂Fe₂₄O₄₁ composite reaches ?30.5 dB at 10.5 GHz with a thickness of 3 mm and the bandwidth of reflection loss below ?10 dB reaches up to 1.2 GHz. The excellent microwave absorption properties of the as-prepared PANI/CoFe₂O₄/Ba₃Co₂Fe₂₄O₄₁ composite due to the enhanced impedance match between dielectric loss and magnetic loss.     

Structural,optical and magnetic properties of Cr doped In<Subscript>2</Subscript>O<Subscript>3</Subscript> powders and thin films

The (In_1?xCr_x)₂O₃ powders as well as thin films of x = 0.03, 0.05 and 0.07 were synthesized using a solid state reaction and an electron beam evaporation technique (on glass substrate), respectively. The influence of Cr doping concentration on structural, optical and magnetic properties of the In₂O₃ samples was systematically studied. The X-ray diffraction results confirmed that all the Cr doped In₂O₃ samples exist cubic structure of In₂O₃ without any secondary phases presence. The chemical composition analyses showed that all the Cr doped In₂O₃ compounds were nearly stoichiometric. The X-ray photoelectron spectroscopy analysis of the Cr doped In₂O₃ thin films showed an increase of oxygen vacancies with Cr concentration and the existence of Cr as Cr³⁺ state in the host In₂O₃ lattice. A small blue shift in the optical band gap was observed in the powder compounds, when the dopant concentration increased from x = 0.03 to x = 0.07. In thin films, the band gap found to increase from 3.63 to 3.74 eV, with an increase of Cr concentration. The magnetic measurements show that the undoped In₂O₃ bulk powder sample has the diamagnetic property at room temperature. And a trace of paramagnetism was observed in Cr doped In₂O₃ powders. However (In_1?xCr_x)₂O₃ thin films (x = 0.00, 0.03, 0.05 and 0.07) samples shows soft ferromagnetism. The observed ferromagnetism in thin films are attributed to oxygen vacancies created during film prepared in vacuum conditions. The ferromagnetic exchange interactions are established between metal cations via free electrons trapped in oxygen vacancies (F-centers).     

Characterization and magnetic studies of Sr<Subscript>2</Subscript>Fe<Subscript>x</Subscript>Mo<Subscript>2−x</Subscript>O<Subscript>6</Subscript> (0.8 ≤ x ≤ 1.5) double perovskites prepared by sonochemical method

Synthesis of Sr₂Fe_xMo_2?xO₆ (x?=?0.8 to 1.5 with a step increment of 0.1) (SFMO) double perovskite oxides were done by sonochemical method at relatively low preparation temperature (950 °C). Purity and existence of all elements (Sr, Fe, Mo, and O) in SFMO compound have been analyzed by energy dispersive X-ray spectroscopy (EDS). Lattice parameters and unit cell volume were studied by X-ray powder diffraction (XRD). The structural transition from tetragonal to cubic occurs around composition x?=?1.1 has been noticed from XRD data. Scanning electron microscopy (SEM) confirmed grain sizes of SFMO series, which are found to be in the range of 75–185 nm. Perovskite formation has been confirmed by Fourier transform infrared spectroscopy (FTIR) spectrum analysis. Investigations of Magnetic properties have been carried out using Vibrating Sample Magnetometer (VSM) at applied magnetic field from ??20 to +?20 kOe. Saturation magnetization is found to increase from x?=?0.8 to 1 and then decreases from x?=?1 to 1.5, the behavior is correlated with degree of Fe/Mo ordering.     

Temperature-stable and low loss Fe-containing dielectrics in BaO-Ln<Subscript>2</Subscript>O<Subscript>3</Subscript>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> system

Polycrystalline samples of Ba₄Ln₂Fe₂Ta₈O₃₀ (Ln = La and Nd) were prepared by a high temperature solid-state reaction technique. The formation, structure, dielectric and ferroelectric properties of the compounds were studied. Both compounds are found to be paraelectrics with filled tetragonal tungsten bronze (TB) structure at room temperature. Dielectric measurements revealed that the present ceramics have exceptional temperature stability, a relatively small temperature coefficient of dielectric constant (τ _ε ) of −25 and −58 ppm/°C, with a high dielectric constant of 118 and 96 together with a low dielectric loss of 1.2 × 10⁻³ and 2.8 × 10⁻³ (at 1 MHz) for Ba₄La₂Fe₂Ta₈O₃₀ and Ba₄Nd₂Fe₂Ta₈O₃₀, respectively. The measured dielectric properties indicate that both materials are possible candidates for the fabrication of discrete multilayer capacitors in microelectronic technology.     

Optical properties of Eu<Superscript>3+</Superscript> activated SrLa<Subscript>2</Subscript>O<Subscript>4</Subscript> red-emitting phosphors for WLED applications

The SrLa_2?xO₄:xEu³⁺ phosphors are synthesized through high-temperature solid-state reaction method at 1473 K with various doping concentration. Their phase structures, absorption spectra, and luminescence properties are investigated by X-ray diffraction (XRD), UV–Vis spectrophotometer and photoluminescence spectrometry. The intense absorption of SrLa_2?xO₄:xEu³⁺ phosphors have occurred around 400 nm. The prominent luminescence spectra of the prepared phosphors exhibited bright red emission at 626 nm. The doping concentration 0.12 mol% of Eu³⁺ is shown to be optimal for prominent red emission and chromaticity coordinates are x?=?0.692, y?=?0.3072. Considering the high colour purity and appropriate emission intensity of Eu³⁺ doped SrLa₂O₄ can be used as red phosphors for white light emitting diodes (WLEDs).     

Low-temperature synthesis of Sr<Subscript>0.3</Subscript>Ba<Subscript>0.7</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript> ultrafine powder and its characteristics

Ultrafine strontium barium niobate (Sr_0.3Ba_0.7Nb₂O₆, SBN30) powders were prepared by urea method starting from a precursor solution constituting of Sr (NO₃)₂, Ba (NO₃)₂, NbF₅, urea and polyvinyl alcohol (PVA) as surfactant. Their structural behavior and morphology were examined by means of X-ray diffractometry (XRD) and Scanning electron microscopy (SEM). The results showed that the SBN30 powders crystallized to a pure tetragonal phase at annealing temperatures as low as 750 °C. The average particle size of SBN powders subjected to 750 °C was of the order of 150–300 nm. With increasing calcination temperature,however, the average particle size of the calcined powders increased. The SBN30 ceramic prepared from urea method can be sintered at temperature as low as 1,225 °C. The transition temperature from the ferroelectric phase to the paraelectric phase and the relative dielectric permittivity of the SBN30 powder were less than the corresponding values of the bulk ceramic. The permittivity and loss tangent (tan δ) at room temperature (1 kHz) was found to be 930 and below 0.025.     

Structural evolution of the intergrowth bismuth-layered Bi<Subscript>7</Subscript>Ti<Subscript>4</Subscript>NbO<Subscript>21</Subscript>

A series of intergrowth bismuth-layered ferroelectric Bi₇Ti₄NbO₂₁ materials are reactive-sintered at 1050 to 1150 °C from Bi₃TiNbO₉ and Bi₄Ti₃O₁₂ parent phases to infer their structural characters and microstructure relations. Various types of stacking faults are revealed in the intergrowth structure with extra Bi₃TiNbO₉ or Bi₄Ti₃O₁₂ layer(s) by high-resolution transmission electron microscopy; some faults with even spacing form locally new intergrowths of Bi₁₀Ti₅Nb₂O₃₀ and Bi₁₁Ti₇NbO₃₃. Co-growth of Bi₇Ti₄NbO₂₁ epitaxially grown onto the remaining Bi₄Ti₃O₁₂ grains is found in the low temperature sintered samples, while the Bi₄Ti₃O₁₂ co-growth onto the intergrowth grains is also found in the high temperature samples. Both co-growths are created from intergranular melts during a solution-precipitation process, which is consistent with the anisotropic growth of the intergrowth structure and the presence of a Bi-rich intergranular phase. The populations of different stacking faults are found to decrease with the increase of their thickness and also with the increase of sintering temperature, indicating that they are remnants survived from dissolution to imbed via precipitation into the intergrowth structure, which should be created from the smaller but much abundant one-layered remnants of the parent phases. This leads to a new model of structural reorganization by such one-layered units to form the intergrowth structure in this solution-precipitation process. Such incomplete dissolution is initiated by the preferential melting of interleaved [Bi₂O₂]²⁺ sheets to enable the exfoliation of perovskite layers to re-order into the intergrowth structure. This reorganization model re-defines the reactive sintering as an evolution process of Bismuth-layered structures.     

Electrical and oxygen sensing properties of Nd<Subscript>1−x</Subscript>Ba<Subscript>x</Subscript>CoO<Subscript>3</Subscript> ceramics

Nd_1?xBa_xCoO₃ (0?≤?x?≤?0.2) ceramics was synthesized by solid state reaction. All the samples have an orthorhombic perovskite structure (Space group P n m a). The electrical transport property indicates that Ba doped NdCoO₃ ceramics goes through semiconductor–metal phase transition. The electrical resistivity of Nd_1?xBa_xCoO₃ (0?≤?x?≤?0.15) ceramics decreases, while the electrical resistivity of Nd_0.8Ba_0.2CoO₃ ceramics increases with the increase of temperature. The chemical-sensing property shows that Nd_1?xBa_xCoO₃ ceramics is very sensitive to oxygen. Also, increasing Ba²⁺ doping concentration can reduce the oxygen desorption rate and increase the sensitivity of resistivity. These results indicate that Ba²⁺ doped NdCoO₃ ceramics is not only the good candidate of the cathode materials of solid fuel cells but also the good materials of gas sensor devices.