Rietveld-refined room temperature structural parameters, important bond lengths, and bond angles for Bi2Fe4O9 ceramic from XRD.
Abstract
This work reports the structure, electrical and magnetic properties of the orthorhombic (Pbam) structured bulk Bi2Fe4O9 synthesized by the solid-state reaction process. Bi2Fe4O9 has been studied using several experimental techniques such as X-ray diffraction, scanning electron microscopy, Raman spectroscopy, dielectric spectroscopy, and magnetometry. Rietveld-refined X-ray diffraction data and Raman spectroscopy results clearly reveal the formation of Bi2Fe4O9 perovskite structure and all the peaks of Bi2Fe4O9 perfectly indexed in the orthorhombic (Pbam) structure. It has been established that the Raman spectrum identified Ag, B2g, and B3g active optical phonon modes, and that the Raman peak at 470 cm−1 may have a magnetic origin. As a result, the coexistence of weak ferromagnetic and antiferromagnetic orders in Bi2Fe4O9 ceramic was established. The remanent magnetization (2Mr) and coercivity (2Hc) are 8.74 × 10−4 emu/g and 478.8 Oe, respectively. We report a remarkable multiferroic effects in polycrystalline Bi2Fe4O9 ceramic. These characteristics make this material very useful in technology and practical applications.
Keywords
- multiferroic
- Bi2Fe4O9
- Raman spectroscopy
- ferroelectric
- magnetic measurement
1. Introduction
Multiferroic materials exhibit more than one primary ferroic order parameters (i.e. ferroelectricity, ferroelasticity and ferromagnetism) in same phase which was first proposed by Schmid in 1994 [1]. In recent years, there has been a strong interest in systems that exhibit convergence between magnetic degrees of freedom, electronic degrees of freedom, and orbital degrees of freedom. Perovskite based oxides have attracted much attention due to their interesting structural, magnetic, optical and electronic properties [2]. A large number of publications have been devoted to multiferroic materials working with theory, experimentation and application features. Bismuth-based complex oxides (Bi2Fe4O9) with mullite-type structure, as an important active material, has a wide application prospect in the fields of magnetic recording media, sensor, magnetoresistive devices, solid oxide fuel cell, scintillators and photocatalyst [3, 4, 5, 6, 7].
The crystallographic structure of Bi2Fe4O9 is orthorhombic with space group
Although, due to search of new multifunctional materials, the recent work carried out is the very important and needed [12, 13, 14, 15]. Rao et al. reported the multifunctional properties of mullite-type structured Nd-doped Bi2Fe4O9 and the spin-orbital coupling by D-M interactions enhances the ferromagnetic (FM) behavior of the Nd-doping Bi2Fe4O9 [12]. Ameer et al. studied the structural, electronic, and magnetic properties of Bi2Fe4O9 with different magnetic ordering using the projector augmented wave (PAW) method based on density functional theory (DFT). They proposed that the FM Bi2Fe4O9 is a semiconductor with an indirect optical bandgap of 1.732 eV and the exchange mechanism started to work, resulting in the exchange splitting in Bi2Fe4O9, while the antiferromagnetic (AFM) Bi2Fe4O9 is a multiband semiconductor without splitting of the majority and minority spin states [13]. In another study, the researchers believed that Zn substitution in Bi2Fe4O9 would induce
Various chemical methods such as solid-state reaction route, chemical co-precipitation, sol-gel and hydrothermal have been used to produce Bi2Fe4O9 [14, 15, 16]. The properties of materials are highly dependent on structural, microstructural properties and methods of synthesis. In this regard, it is of interest to develop controlled methods for making materials in oxide forms for further functional applications. Thermal heating in the oxygen atmosphere at high temperatures contributes to the oxidation process and formation of oxide forms, which has a significant impact on physical, chemical and magnetic properties of compounds [17, 18, 19, 20, 21]. Zdorovets et al. reported the systematic study of the effect of thermal annealing on changes in the structural properties and phase compositions of metallic cobalt based nanostructures [17]. Rusakov et al. described the effect of thermal annealing on structural and magnetic characteristics, as well as phase transformations in Fe▬Ni/Fe▬Ni▬O nanoparticles. They found that the initial nanoparticles were a three-phase system consisting of Fe▬Ni▬O oxide with spinel structure and a Fe▬Ni alloy with face-centered and body-centered cubic lattices. As a result of thermal annealing, the decrease in the Fe▬Ni phase is associated with the subsequent ordering of the Fe▬Ni▬O phase with a decrease in the crystal lattice parameter and an increase in the degree of crystallinity [19]. If annealing is carried out in air, the phase transition related to the structural transformation of iron oxide is in the range of 600–1000°C due to the change of thermal vibration of atoms in the lattice node, the annealing of point defects and the introduction of oxygen at high temperature [20].
Although Bi2Fe4O9 has obvious importance as a functional material, there are few reports in the literature. Here, we present the structural and physical properties of bulk Bi2Fe4O9 ceramic synthesized by a solid-state reaction route. One needs detailed knowledge of the crystal structure to understand the physical properties. Therefore, we aimed to understand the crystal structure by X-ray powder diffraction followed by Rietveld refinement using FullPROF program [22]. In addition, Bi2Fe4O9 was subsequently characterized using several experimental techniques, such as Raman spectroscopy, SEM, dielectric and ferroelectric spectroscopy, and magnetometry, which are discussed in detail.
2. Experimental details
Bulk Bi2Fe4O9 ceramic was synthesized through solid-state reaction route (SSR). The SSR is a commonly used synthesis method for obtaining polycrystalline bulk materials from solid reagents. This method provides a great deal of choices for starting materials like oxides, carbonates, etc. Since solids do not react with each other at room temperature, very high temperatures are usually employed to allow appropriate reaction to occur at a significant rate. Therefore, both thermodynamic and kinetic factors are important in SSR. In the SSR method, the solid reactants undergo a chemical reaction at high temperature in the absence of any solvent, thereby producing a stable product. High purity Bi2O3, Fe2O3 were carefully weighed and stoichiometrically mixed in an agate mortar for 5 hours. The powder was doubly thermally calcined consecutively at 650°C for 1 hour and 850°C for 6 hours with intermediate grinding in oxygen-containing medium. Finally, pellets were sintered at 850°C for 6 hours, resulting in good densification. Thermal heating (i.e. calcination and annealing) is a mean of controlling the structural changes, properties, and phase compositions [23]. In this case, introduction of oxygen leads to the formation of oxide compounds. For crystallinity and phase identification X-ray diffraction (XRD) pattern were taken using CuKα1 radiation (λ = 1.5406 Å) of a Bruker D8 Advance X-ray diffractometer. Crystal structure characterization of synthesized sample was performed by employing Rietveld whole profile fitting method using FullPROF software [22].
The sample quality, morphology, grain distribution, density/voids in the samples were studied with scanning electron microscope (JEOL, JSM-5600). Raman measurements on as synthesized sample was carried out on Jobin-Yovn Horiba LABRAM (System HR800) spectrometer with a 632.8 nm excitation source equipped with a Peltier cooled CCD detector. Dielectric measurements were made as a function of frequency in the range of 100 Hz–1 MHz on Novocontrol alpha-ANB impedance analyzer at room temperature. Ferroelectric measurement was carried out using a ferroelectric loop tracer based on Sawyer-Tower circuit. The
3. Results and discussion
3.1 Crystal structure analysis
The room temperature XRD pattern of bulk Bi2Fe4O9 sample is shown in Figure 1(a). From the XRD pattern we can index the data in orthorhombic phase as shown in Figure 1(a). The present XRD patterns matches with JCPDS #01-74-1098 (Bi2Fe4O9) [24]. In order to further confirm structural data, Rietveld refinement of the XRD pattern for Bi2Fe4O9 sample was performed using FullPROF program and shown in Figure 1(b). The composition of phase and its concentration in the structure have been determined using the Rietveld method, which is based on the estimation of the diffraction peak area and the analysis of their contributions to the entire X-ray diffraction. It should be noted here that XRD pattern having a small secondary phase peaks corresponding to the Fe2O3 and its phase concentration is less than 2%, which does not affect the measured properties of studied ceramic. The XRD pattern of parent Bi2Fe4O9 was refined with orthorhombic (
V = 400.31(2) Å3 | ||||
---|---|---|---|---|
Atoms | ||||
Bi | 0.3230 | 0.1745 | 0.0000 | |
Fe1 | 0.0000 | 0.0000 | 0.2582 | |
Fe2 | 0.1465 | 0.3360 | 0.5000 | |
O1 | 0.3485 | 0.4292 | 0.0000 | χ2 = 4.65% |
O2 | 0.3671 | 0.4047 | 0.5000 | |
O3 | 0.1312 | 0.2054 | 0.2413 | |
O4 | 0.0000 | 0.5000 | 0.5000 | |
Bi▬O1 | 2.153 | O1▬Bi▬O1 | 151.93 | |
Bi▬O3 | 3.017 | O3▬Bi▬O3 | 86.06 | |
Fe1▬O1 | 2.047 | Bi▬O1▬Bi | 141.13 | |
Fe1▬O2 | 1.962 | O2▬Fe2▬O3 | 103.98 | |
Fe1▬O3 | 2.022 | O3▬Fe2▬O3 | 108.93 | |
Fe2▬O1 | 3.485 | O3▬Fe2▬O4 | 113.59 | |
Fe2▬O2 | 1.846 | Fe1▬O1▬Fe1 | 98.02 | |
Fe2▬O3 | 1.901 | Fe1▬O2▬Fe1 | 94.99 | |
Fe2▬O4 | 1.805 | Fe1▬O2▬Fe2 | 129.72 | |
Fe1▬O3▬Fe2 | 119.09 | |||
Fe2▬O4▬Fe2 | 172.00 |
The symmetric pseudo-Voigt functions are used to calculate the degree of crystallinity based on the estimation of the diffraction width and shapes. We have measured the full width half maxima (FWHM) of the recorded diffraction lines, which allowed us to characterize the perfection of the crystal structure and evaluate the degree of crystallinity [21]. The value of % of crystallinity for Bi2Fe4O9 = 81.3% was calculated using the formula:
The
Here,
We used the Williamson-Hall plot to observed the effect of the phase composition on distortions and deformation of the crystal structure of Bi2Fe4O9 ceramic, based on estimating the angular dependence of the full width at half maximum (FWHM) of diffraction lines (Figure 2). We obtained the strain (ε) value for Bi2Fe4O9 ceramic is 0.00412 ± 0.0016. Thermal heating at high temperature helps to reduce the distortion value [19].
3.2 SEM analysis
The surface morphological and microstructural properties of Bi2Fe4O9 compound was investigated using scanning electron microscopy (SEM). Figure 3 (upper part) shows the SEM micrograph of Bi2Fe4O9 thermally sintered at 850°C for 10 hours. Typical SEM image shows that microstructures comprising of non-uniform distribution of grains with an estimated average grain size of 1.5 μm indicating polycrystalline nature. Even though the SEM image shows that there are some pores between loosely connected grains in the sample. The surface area of a catalyst is a key aspect to determine the adsorption capacity of reactants on the catalyst surface [26]. We have measured the active surface area using a Brunauer-Emmett-Teller (BET) measurement system at 77 K through nitrogen adsorption-desorption isotherm method. The BET active surface area of Bi2Fe4O9 is 1.2 m2/g, which is in good agreement with the values reported in the literature [27]. In order to obtain photocatalytic efficiency, it is necessary to increase the specific surface area by doping or reducing grain sizes. In addition, we have measured the material’s apparent density which is defined as the mass per unit volume of the material in absolute dense condition [28]. The obtained density of the present calcined Bi2Fe4O9 ceramic is 6.51 g/cm3 which match well with the density for the Bi2Fe4O9 (ρ = 6.48 g/cm3) from reference file: JCPDS card number 74-1098.
3.3 Raman scattering analysis
Raman scattering spectroscopy has been extensively utilized to study the crystal lattice vibrations. Raman scattering spectroscopy would also offer a distinctive potential as a sensitive probe for the spin dynamics and studying the effect of magnetic ordering. Raman spectrum of Bi2Fe4O9 at room temperature is depicted in lower part of Figure 3. The Raman active modes of the structure can be summarized using the irreducible representation 12
3.4 Dielectric and P-E loop studies
The real part of permittivity (ε′) and loss tangent (tanδ) as a function of frequency of Bi2Fe4O9 ceramics near at surrounding temperature is shown in Figure 4(a) and (b). The value of ε′ and tanδ for Bi2Fe4O9 are about 21.57 and 0.05, respectively at frequency 10 Hz. At higher frequency (~1 MHz) the value of ε′ and tanδ are 18.59 and 0.006, respectively. Dielectric behavior (i.e. ε′ and tanδ) decreases with increase in frequency and it is constant at higher frequency region. From Figure 4(a) and (b) we have found that the value of dielectric constant in the whole frequency range (10 Hz–1 MHz) is nearly constant representing the low loss in the prepared ceramic. This result appears to be consistent with previous empirical analysis using the Maxwell-Wagner model with thermal activation across multiple band gaps in isolated impurities [15, 33]. Figure 4(c) shows the semilog plot of conductivity (
Ferroelectric hysteresis
3.5 Magnetic analysis (M-H curve)
From the measured
4. Conclusions
We have successfully synthesized polycrystalline Bi2Fe4O9 through solid-state reaction route. X-ray diffraction pattern confirmed the formation of Bi2Fe4O9 with the orthorhombic structure (space group
Acknowledgments
We acknowledge the financial support from National Natural Science Foundation of China under grant numbers 11774276 and 51074131. The authors are grateful to Dr. S. Satapathy for their long-term collaboration and numerous fruitful discussions.
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