Tunable multiferroic properties of Mn substituted BiFeO3 thin films

The current study explored the influence of Mn substitution on the electrical and magnetic properties of BiFeO₃ (BFO) thin films synthesized using low cost chemical solution deposition technique. X-ray diffraction analysis revealed that pure rhombohedral phase of BiFeO₃ was transformed to the tetragonal structure with P4mm symmetry on Mn substitution. A leakage current density of 5.7×10⁻⁴ A/cm² which is about two orders of magnitude lower than pure BFO was observed in 3% Mn doped BFO thin film at an external electric field >400 kV/cm. A well saturated (p-E) loops with saturation polarization (P_sat) and remanent polarization (2P_r) as high as 60.34 µC/cm² and 25.06 µC/cm² were observed in 10% Mn substituted BFO thin films. An escalation in dielectric tunability (n_r), figure of merit (K) and quality factor (Q) were observed in suitable Mn doped BFO thin films. The magnetic measurement revealed that Mn substituted BFO thin films showed a large saturation magnetization compared to pure BFO thin film. The highest saturation ~31 emu/cc was observed for 3% Mn substituted BFO thin films.     

Effect of (Zn,Mn) co-doping on the structure and ferroelectric properties of BiFeO3 thin films

BiFe_1-2xZn_xMn_xO₃ (BFZMO, with x = 0–0.05) thin films were synthesized via sol–gel method. Effects of (Zn, Mn) co-doping on the structure, ferroelectric, dielectric, and optical properties of BiFeO₃ (BFO) films were investigated. BFZMO thin films exhibit rhombohedral structure. Scanning electron microscopy (SEM) images indicate that co-doping leads to a decrease in grain size and number of defects. Leakage current density (4.60 × 10^?6 A/cm²) of BFZMO film with x = 0.02 was found to be two orders of magnitude lower than that of pristine BFO film. Owing to decreased leakage current density, saturated P–E curves were obtained. Maximum double remnant polarization of 413.2 μC/cm² was observed for BFZMO thin film with x = 0.02, while that for the BFO film was found to be 199.68 μC/cm². The reason for improved ferroelectric properties is partial substitution of Fe ions with Zn and Mn ions, which resulted in a reduction in the effect of oxygen vacancy defects. In addition, co-doping was found to decrease optical bandgap of BFO film, opening several possible routes for novel applications of these (Zn, Mn) co-doped BFO thin films.     

Phase‐dependent radiation‐resistant behavior of BaTiO3: An in situ X‐ray diffraction study

The radiation‐resistant response of BaTiO₃ in the tetragonal and rhombohedral phases on exposure to 100 MeV Ag⁷⁺ ion irradiation was investigated by in situ X‐ray diffraction (XRD) at room temperature (300 K) and low temperature (25 K), respectively. This study revealed that the BaTiO₃ in rhombohedral phase retained crystallinity up to an ion fluence of 1×10¹⁴ ions/cm², whereas tetragonal phase amorphized at much lower fluence viz. 1×10¹³ ions/cm². The in situ XRD along with Raman spectroscopy studies revealed that BaTiO₃ in rhombohedral phase is more radiation resistant than that of tetragonal phase. The density functional theory (DFT) calculations confirmed higher bond strength of rhombohedral phase as compared to tetragonal phase, which supported the experimental result of higher radiation stability of rhombohedral phase. The theoretical predictions on high‐temperature phase will be of relevance to the nuclear waste applications.     

The influence of processing methods on the dielectric properties of BaTi1-xGdxO3-x/2 - Based materials

In this study, the intermediate rare-earth oxide Gd₂O₃ (Gd) was substituted in different amounts (x = 0.2–2 mol%) for the formulation of BaTi_1-xGd_xO_3-x/2 (BTG_x) dielectric materials. The effect of B-site substitution was confirmed by the additional Raman active A_1g octahedral peak at ~835cm^-1 strengthened at x ≥ 0.4 mol%. Additionally, properties of 0.9BTG_0.007-0.1BA dielectric ceramics were analysed based on the influence of various processing methods as a function of sintering temperature. The focal samples were labelled Method-A (direct-mix) and Method-B (indirect-mix). As the sintering temperature (1075–1200 °C) increased, the 1 kHz response of the ε–T curves of Method-A samples transformed from a single peak to broad-narrow double peaks of high dielectric loss tangent (tan δ). Nonetheless, samples of Method-B possessed a clearly defined transmission electron microscopy (TEM) core-shell structure, flattened double-peak ε-T curves, optimised dielectric properties (ε = ~1563–1851 and tan δ < 1.5% at room temperature), and a wide-ranging temperature behaviour that meets the X8R dielectric standards (ΔC/C_25°C < ±15%). The maximum dielectric breakdown strength of Method-B samples reached ~131 kVcm, while the energy storage density was ~0.726 J/cm³ at a maximum efficiency of ~80% at 1100 °C. Thus, exhibiting good potentials for balancing temperature stability with energy storage applications.     

Comparative studies by X-ray diffraction,Raman, vibrating sample magnetometer and Mössbauer spectroscopy of pure,Sr doped and Sr,Co co-doped BiFeO3 ceramic synthesized via tartaric acid-assisted technique

Pure BiFeO₃ (BFO), Sr-doped Bi_0.97Sr_0.03FeO₃ (BSFO) and Sr, Co co-doped Bi_0.97Sr_0.03Fe_0.8Co_0.2O₃ (BSFCO) samples have been prepared via a tartaric acid-assisted sol-gel technique. Investigation of the structure, lattice dynamics, magnetization and hyperfine interaction have been performed through X–ray diffraction (XRD), transmission electron microscope (TEM), Raman spectroscopy (RS), vibrating sample magnetometer (VSM) and Mössbauer spectroscopy (MS). The TEM images show that the particle sizes <D> of BFO, BSFO and BSFCO are respectively 11.4, 12.1 and 8.8 nm. The XRD analysis reflects a structural phase transition from rhombohedral R3c structure in case of BFO and BSFO samples to two phase coexistence (rhombohedral R3c and trigonal R–3m:R) in case of BSFCO sample. This structural phase transition has been strongly confirmed by the alterations in the vibration modes observed in Raman spectra (expansion, shift, merge, and reduced intensity). Second order vibration modes, corresponding to the two-phonon scattering in the range 650–1000 cm⁻¹, have been recorded for all samples. Investigation of magnetic properties reveals that pure and Sr doped samples possess considerably high magnetic saturations (Ms = 5.61 and 5.79 emu/g respectively). Additionally, BSFCO sample shows enhancement in Ms (Ms rises to 8.26 emu/g). Suppression of spiral spin structure caused by the small nano-size has been assumed. The destruction of the spiral spin has been also suggested through M össbauer studies. The hyperfine parameters reveal that only Fe³⁺ is observed in two different nonequivalent trigonal distorted octahedral environments. The outcome of this work suggests the potentiality of Sr, Co co-doping to improve the structure and ferromagnetism of BiFeO₃ ceramic making it feasible to be employed in enormous applications.     

Solvent-deficient method lowers grain-boundary resistivity of doped ceria

Nanoparticles of gadolinium-doped cerium oxide (GDC) were synthesized using solvent-deficient method and their sinterability and electrical properties were investigated using the powder and cold sintering process. The GDC powder was uniaxially pressed into cylindrically-shaped pellets with a mixture of nitric acid and hydrogen peroxide at 200°C to encourage particle arrangement during forming process. These bulk samples were annealed using two different temperature profiles: at 800°C for 5 hours and at 1300°C for 1 minute—800°C for 5 hours. The samples produced using HNO₃/H₂O₂ mixture showed higher relative density than ones without it. Ionic conductivity of the sample sintered through the two-step profile was obtained from electrochemical impedance spectroscopy. Although the grain conductivity for the samples (8.0 × 10⁻³ S cm⁻¹ at 500°C, and 3.3 × 10⁻² S cm⁻¹ at 700°C) is on par with a conventionally sintered sample, the measured total conductivity (3.9 × 10⁻³ S cm⁻¹ at 500°C, and 2.5 × 10⁻² S cm⁻¹ at 700°C) is about 10 times higher than the conventionally sintered one and is comparable to the values seen in the previous studies for GDC which employed higher sintering temperature, pointing to the effectively lower grain-boundary impedance. This result could be attributed to no significant phase segregation along grain boundaries due to the low-temperature processing.     

Reaction,densification, and mechanical properties of Ti2AlCx ceramics at low applied pressure and temperature

Ti₂AlC_x ceramic was produced by reactive hot pressing (RHP) of Ti:Al:C powder mixtures with a molar ratio of 2:1:1–.5 at 10–20 MPa, 1200–1300°C for 60 min. X-ray diffraction analysis confirmed the Ti₂AlC with TiC, Ti₃Al as minor phases in samples produced at 10–20 MPa, 1200°C. The samples RHPed at 10 MPa, 1300°C exhibited ≥95 vol.% Ti₂AlC with TiC as a minor phase. The density of samples increased from 3.69 to 4.04 g/cm³ at 10 MPa, 1200°C, whereas an increase of pressure to 20 MPa resulted from 3.84 to 4.07 g/cm³ (2:1:1 to 2:1:.5). The samples made at 10 MPa, 1300°C exhibited a density from 3.95 to 4.07 g/cm³. Reaction and densification were studied for 2Ti–Al–.67C composition at 10 MPa, 700–1300°C for 5 min showed the formation of Ti–Al intermetallic and TiC phases up to 900°C with Ti, Al, and carbon. The appearance of the Ti₂AlC phase was ≥1000°C; further, as the temperature increased, Ti₂AlC peak intensity was raised, and other phase intensities were reduced. The sample made at 700°C showed a density of 2.87 g/cm³, whereas at 1300°C it exhibited 3.98 g/cm³; further, soaking for 60 min resulted in a density of 4.07 g/cm³. Microhardness and flexural strength of Ti₂AlC_0.8 sample were 5.81 ± .21 GPa and 445 ± 35 MPa.     

Dielectric and Raman Spectroscopic Studies of Na0.5Bi0.5TiO3–BaSnO3 Ferroelectric System

A series of lead‐free perovskite solid solutions of (1 ? x) Na_0.5Bi_0.5TiO₃(NBT)—x BaSnO₃(BSN), for 0.0 ≤ x ≤ 0.15 have been synthesized using a high‐temperature solid‐state reaction route. The phase transition behaviors are studied using dielectric and Raman spectroscopic techniques. The ferroelectric to relaxor phase transition temperature (T_FR) and the temperature corresponding to maximum dielectric permittivity (T_m) are estimated from the temperature‐dependent dielectric data. Dielectric studies show diffuse phase transition around ~335°C in pure NBT and this transition temperature decreases with increase in x. The disappearance of x‐dependence of A₁ mode frequency at ~134 cm^?1 for x ≥ 0.1 is consistent with rhombohedral‐orthorhombic transition. In situ temperature dependence Raman spectroscopic studies show disappearance and discontinuous changes in the phonon mode frequencies across rhombohedral (x < 0.1)/orthorhombic (x ≥ 0.1) to tetragonal transition.     

Structures and pyroelectric properties for [111]-oriented Mn-doped rhombohedral 0.36PIN-0.36PMN-0.28PT crystal

The crystal structures, pyroelectric properties, and thermal stability of [111]-oriented 0.5 mol% Mn-doped 0.36Pb(In_1/2Nb_1/2)O₃-0.36Pb(Mg_1/3Nb_2/3)O₃-0.28PbTiO₃ (Mn-0.36PIN-0.36PMN-0.28PT) ternary single crystal were investigated. The temperature dependence of the Raman spectra and dielectric properties revealed that the crystal exhibited a rhombohedral (R) structure at room temperature, and ferroelectric R → tetragonal (T) and ferroelectric T to paraelectric cubic (C) phase transitions at 130 and 175°C respectively. The single crystal had a high remnant polarization of P_r = 38 μC cm^–2 and coercive field of E_C = 12 kV cm^–1 at room temperature and a frequency of f = 100 Hz. The values of P_r and E_C decreased with increasing temperature, exhibiting anomalies near their phase-transition temperatures, which coincided with changes in the Raman spectra and dielectric properties. Furthermore, at 25°C and f = 100 Hz, the single crystal had high pyroelectric coefficients of p = 8.7 × 10⁻⁴ C m⁻² K⁻¹, figures of merit for the current responsivity of F_i = 3.5 × 10⁻¹⁰ m V⁻¹, the voltage responsivity of F_v = 0.08 m² C⁻¹, and the detectivity of F_d = 30.1 × 10⁻⁵ Pa^−1/2. These values were weakly dependent on temperature below 120°C. In addition, the room-temperature pyroelectric coefficients of the ternary single crystal maintain over 83% of the original value at thermal annealing temperatures below 120°C. These outstanding pyroelectric properties, together with high thermal stability, indicate that [111]-oriented rhombohedral Mn-0.36PIN-0.36PMN-0.28PT ternary single crystal is a new potential candidate for infrared detection applications.     

Substantial reduction of leakage currents in La/Er/Zn/Ti multielement-doped BiFeO3 multiferroic thin films

Multi-element doping is an effective method to suppress the leakage of BiFeO₃ (BFO). A systematic study on the effect of various elements (La, Er, Zn, Ti) doping on the leakage performance, mechanism and other electrical properties of BFO films was performed As the kinds of doping elements increases, the leakage current density of the BFO film gradually decreases. The leakage current density is gradually reduced from 5.78 × 10^?2 A/cm² doped with one element (La) to 1.25 × 10^?2 A/cm² doped with two elements (La, Ti), 4.13 × 10^?3 A/cm² doped with three elements (La, Ti, Zn), and 4.53 × 10^?4 A/cm² doped with four elements (La, Er, Zn, Ti). Finally, compared with pure BFO films, the leakage current density in doped BFO films is reduced by two orders of magnitude. Moreover, the conduction mechanism in doped BFO films is gradually changed from space charge limited current to ohmic conduction. This work provides an effective method to ameliorate the leakage of ferroelectric materials and lays a foundation for the practical application of BFO-based films.     

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.     

Effect of Nd-doping on structural,thermal and electrochemical properties of LaFe0.5Cr0.5O3 perovskites

The structural, thermal and electrochemical properties of the perovskite-type compound La_1−xNd_xFe_0.5Cr_0.5O₃ (x=0.10, 0.15, 0.20) are investigated by X-ray diffraction, thermal expansion, thermal diffusion, thermal conductivity and impedance spectroscopy measurements. Rietveld refinement shows that the compounds crystallize with orthorhombic symmetry in the space group Pbnm. The average thermal expansion coefficient decreases as the content of Nd increases. The average coefficient of thermal expansion in the temperature range of 30–850 °C is 10.12×10⁻⁶, 9.48×10⁻⁶ and 7.51×10⁻⁶ °C⁻¹ for samples with x=0.1, 0.15 and 0.2, respectively. Thermogravimetric analyses show small weight gain at high temperatures which correspond to filling up of oxygen vacancies as well as the valence change of the transition metals. The electrical conductivity measured by four-probe method shows that the conductivity increases with the content of Nd; the electrical conductivity at 520 °C is about 4.71×10⁻³, 6.59×10⁻³ and 9.62×10⁻³ S cm⁻¹ for samples with x=0.10, 0.15 and 0.20, respectively. The thermal diffusivity of the samples decreases monotonically as temperature increases. At 600 °C, the thermal diffusivity is 0.00425, 0.00455 and 0.00485 cm² s⁻¹ for samples with x=0.10, 0.15 and 0.20, respectively. Impedance measurements in symmetrical cell arrangement in air reveal that the polarization resistance decreases from 55 Ω cm⁻² to 22.5 Ω cm⁻² for increasing temperature from 800 °C to 900 °C, respectively.     

Structural,dielectric and ferroelectric properties of lead-free Ba0.85Ca0.15Zr0.10Ti0.90O3 ceramics prepared by Plasma Activated Sintering

Lead-free Ba_0.85Ca_0.15Zr_0.10Ti_0.90O₃ (BCZT) ceramics were prepared by Plasma Activated Sintering (PAS). The influence of PAS sintering temperature on the crystalline phase, microstructure, and, dielectric and ferroelectric properties of BCZT ceramics were studied. The phase structure of BCZT ceramics first changed from rhombohedral phase to the coexistence of rhombohedral and tetragonal phases and then to tetragonal phase as the sintering temperature increased. Microstructural characterization of BCZT ceramics indicated that PAS can obtain a compact microstructure at lower temperatures of 1150–1300 °C compared with that from common pressureless sintering. The BCZT ceramics showed different degrees of diffuseness with increased temperature, and the diffuseness exponents C are all approximately on the order of 10⁵ °C. The dielectric and ferroelectric properties of BCZT ceramics were enhanced with increased sintering temperature. BCZT ceramics sintered at 1250 °C exhibited optimum properties of room-temperature ε_r=2863, ε_m=6650, and 2P_r=25.24 μC/cm², resulting from the relatively higher tetragonal phase content of the MPB between tetragonal and rhombohedral phases together with a compact microstructure.     

A Novel Approach to Improve Properties of BiFeO3 Nanomultiferroics

In this study we report the synthesis of Bi_1?xIn_xFe_1?yTi_yO₃ (0 ≤ x ≤ 0.1, 0 ≤ y ≤ 0.05) nanoparticles by a simple cost effective solution combustion method. Pure BFO samples shows distorted rhombohedral perovskite structure with space group R3c which is also supported by Fourier transform infrared spectra study. The codoping of In and Ti at A–B sites of BFO (BIFTO) partially distorts the crystal structure, increases the lattice strain, reduces the average particle size (14 nm), and increases the Fe³⁺/Fe²⁺ ratio which significantly affect the observed results. The saturation magnetization increases significantly upon codoping (4.60 emu/gm) by about 12 times than that of pure BFO (0.4 emu/gm). The improved ferromagnetic properties upon codoping is further manifestated in large value of linear magnetoelectric coupling coefficient (4.8 mV/cmOe) which further provides an indirect evidence for the collapse of space modulated spin structure. The activation energy increases with codoping (0.68 eV), although less than 1 eV which indicates that the conduction is still dominated by charged defects.     

Investigation of structural,optical, dielectric and magnetic studies of Mn substituted BiFeO3 multiferroics

A series of Mn doped BiFeO₃ with composition BiMn_xFe_1−xO₃ (x = 0.0, 0.025, 0.05, 0.075, 0.1) was synthesized via a citrate precursor method. Structural, morphological, optical, electrical and magnetic properties were investigated by using various measurement techniques. XRD patterns confirmed that the materials possess distorted rhombohedral structure with space group R3c. Average crystallite size was found to be in the range 18–36 nm. A decrease in the value of lattice parameters has been observed due to contraction of unit cell volume with Mn doping. Higher tensile strain for the prepared nanoparticles was observed in Hall-Williamson Plot. Field Emission Scanning Microscopy (FESEM) showed the spherical, uniform, dense nanoparticles in the range 80–200 nm. Reduction in grain size was observed which may be due to suppression of grain growth with Mn doping. FTIR studies reported two strong peaks at 552 cm⁻¹ and 449 cm^-1 which confirmed the pervoskite structure. Dielectric properties were studied by measuring the dielectric constant and loss in the frequency range 1 kHz to 1 MHz. Magnetic hysteresis loop showed the retentivity (M_r) increasing from 0.0514 emu/g of BFO to 0.0931 emu/g of 10% Mn doping. Coercivity was found to increase upto 0.0582 T for 5% Mn doping and then reduced to 0.0344 T for 7.5% Mn doping. Saturation magnetization was observed to increase from 0.6791 emu/g for BFO to 0.8025 emu/g for 7.5% and then reduced to 0.6725 emu/g for 10% Mn doping in BFO. Improvement in dielectric and magnetic properties makes this material as a promising candidate for multifunctional device applications.     

High‐temperature piezoelectric properties of 0‐3 type CaBi4Ti4O15:x wt%BiFeO3 composites

The 0‐3 type CaBi₄Ti₄O₁₅:30 wt%BiFeO₃ composite shows much better high‐temperature piezoelectric properties than the single‐phase CaBi₄Ti₄O₁₅ or BiFeO₃ ceramics. The composite with 0‐3 type connectivity exhibits a high density of 7.01 g/cm³, a saturated polarization of 21.5 μC/cm² and an enhanced piezoelectric d₃₃ of 25 pC/N. After the poled composite was annealed at 600°C, its d₃₃ is 21 pC/N at room temperature. Resistance of the composite decreases slowly from 10⁹ ohm at 20°C to ~10⁵ ohm at 500°C. Furthermore, the poled composite shows strong radial and thickness dielectric resonances at 20°C‐500°C.     

Processing of high-performance Co doped Y2O3 as a single-phase electrolyte for low temperature solid oxide fuel cell (LT-SOFC)

The high-performance single-phase semiconductor materials with higher ionic conductivity have drawn substantial attention in fuel cell applications. Semiconductor materials play a key role to enhance ionic conductivity subsequently promoting low temperature solid oxide fuel cell (LT-SOFC) research. Herein, we proposed a semiconductor Co doped Y₂O₃ (YCO) samples with different molar ratios, which may easily access the high ionic conductivity and electrochemical performances at low operating temperatures. The resulting fabricated fuel cell 10% Co doped Y₂O₃ (YCO-10) device exhibits high ionic conductivity of ∼0.16 S cm⁻¹ and a feasible peak power density of 856 mW cm⁻² along with 1.09 OCV at 530 °C under H₂/air conditions. The electrochemical impedance spectroscopy (EIS) reveals that YCO-10 electrolyte based SOFC device delivers the least ohmic resistance of 0.11–0.16 Ω cm² at 530-450 °C. Electrode polarization resistance of the constructed fuel cell device noticed from 0.59 Ω cm² to 0.28 Ω cm² in H₂/air environment at different elevated temperatures (450 °C to 530 °C). This work suggests that YCO-10 can be a promising alternative electrolyte, owing to its high fuel cell performance and enhanced ionic conductivity for LT-SOFC.     

Enhanced dielectric,thermal stability,and energy storage properties in compositionally engineered lead-free ceramics at morphotropic phase boundary

Structural inhomogeneity at morphotropic phase boundary (MPB) offers a novel paradigm to explore and modulate the physical properties of dielectric materials to design next-generation multifunctional devices. In this work, two lead free materials at MPB; Ba_0.85Ca_0.15Zr_0.1Ti_0.9O₃ (BCZT) and (Bi_0.5Na_0.5)TiO₃-0.06BaTiO₃ (BNTBT), are combined together to synthesize polycrystalline composite samples of (1-x) BCZT-xBNTBT with x = 0.0, 0.25, 0.50, 0.75, and 1.0. Structural investigations using XRD show the coexistence of double phases for pristine BCZT (tetragonal (P4mm) + rhombohedral (R3m)), and for pristine BNTBT (tetragonal (P4bm) + rhombohedral (R3c)). However, all the doped samples with x = 0.25, 0.5, and 0.75 display a coexistence of triple phases with P4mm, P4bm, and R3c symmetries. Detailed dielectric study reveals a normal ferroelectric to macroscopic ergodic relaxor crossover for samples with x = 0.25 and 0.75. Intriguingly, sample x = 0.25 displays a coexistence of high dielectric constant (4050), ultralow dielectric loss (≤0.02), high temperature thermal stability of permittivity (variation ≤ ±15%) in a temperature range 135 °C–450 °C, large recoverable energy density (W_rec = 423 mJ/cm³) with ultrahigh energy storage efficiency (η = 95.4%) at low applied electric field - 23 kV/cm. Nevertheless, at similar applied field strength, the obtained values of W_rec and η exceed most of the selected lead-free energy storage materials. This work may pave a new path to design superior high-temperature dielectrics, through intermixing of MPBs, for energy storage applications.     

Structural,dielectric, vibrational and magnetic properties of Sm doped BiFeO3 multiferroic ceramics prepared by a rapid liquid phase sintering method

Rare earth Sm substituted Bi_1−xSm_xFeO₃ with x=0, 0.025, 0.05, 0.075 and 0.10 polycrystalline ceramics were synthesized by a rapid liquid phase sintering method. The effect of varying composition of Sm substitution on the structural, dielectric, vibrational, optical and magnetic properties of doped BiFeO₃ (BFO) ceramics have been investigated. X-ray diffraction patterns of the synthesized rare earth substituted multiferroic ceramics showed the pure phase formation with distorted rhombohedral structure with space group R3c. Good agreement between the observed and calculated diffraction patterns of Sm doped BFO ceramics in Rietveld refinement analysis of the X-ray diffraction patterns and Raman spectroscopy also confirmed the distorted rhombohedral perovskite structure with R3c symmetry. Dielectric measurements showed improved dielectric properties and magnetoelectric coupling around Néel temperature in all the doped samples. FTIR analysis establishes O–Fe–O and Fe–O stretching vibrations in BiFeO₃ and Sm-doped BiFeO₃. Photoluminescence (PL) spectra showed visible range emissions in modified BiFeO₃ ceramics. The magnetic hysteresis measurements at room temperature and 5 K showed the increase in the magnetization with the increase in doping concentration of Sm which is due to the structural distortion and partial destruction of spin cycloid caused by Sm doping in BFO ceramics.     

Enhancement of Al-N co-dopant solubility in ZnO by high temperature thermal annealing

In this paper, we have developed a method to enhance the Al-N co-dopant solubility in bulk ZnO prepared by solid state reaction method. Reactive donor Al and acceptor N were mobilized by annealing the samples at various temperatures from 650 to 850?°C with a step of 50?°C in a programmable furnace. The solubility enhancement argument was verified by the conductivity measurements which showed that the conductivity of annealed films increases as the annealing temperature increases. The activation energy was calculated by the Arrhenius plot and was found to be (0.08?eV) very close to activation energy of shallow acceptor (nitrogen). To further strengthened our argument, we have also performed XRD, FTIR, Raman Spectroscopy and SEM measurements. XRD data suggested that only ZnO phases were present and no evidence for the presence of AlN, Al₂O₃ or Zn₃N₂ phases. We have also observed weakening and peak shifting of (002) with annealing temperature that suggested the incorporation of more acceptor defects in the crystal of ZnO. FTIR results verified the presence of Zn-O bond (437?cm^?1) along with week vibration of Al-N bond at 917?cm^?1. Raman spectroscopy data consists of 2E₂, A₁ (LO) and E_2(high) modes of ZnO but sample annealed at 800?°C has additional nitrogen related mode at 507?cm^?1. SEM images demonstrated the crystalline nature of samples having smooth surface but sample annealed at 800?°C has rough surface which indicated the enhancement of acceptor defects density.