Structural modification and evaluation of Dielectric, Magnetic and Ferroelectric Properties o f Nd- modified BiFeO3– PbTiO3 Multiferroic Ceramics

doi:10.21203/rs.3.rs-515033/v1

0.9Bi_1 − xNd_xFeO₃ – 0.1PbTiO₃ solid solution where x = 0.05, 0.10, 0.15 and 0.20 were success fully synthesized by the standard solid-state reaction method. The effect of Nd³⁺ion substitution on structural, micro structural, ferroelectric, magnetic, dielectric and magneto-electric properties of 0.9BiFeO₃-0.1PbTiO₃ have been investigated. The XRD analysis for the samples under study revealed distorted rhombohedral structure with R3C space group. 0.9Bi_1 − xNd_xFeO₃ – 0.1PbTiO₃ where x = 0.05, 0.10, 0.15 and 0.20 i.e.(BNFPT)x compounds crystallised as single-phase materials with the same structure as the parent BiFeO3 compound.. The SEM study revealed the uniform grain scattering for all prepared samples. Raman spectroscopy showed disappearance of some Raman modes indicated a structural phase transition with substitution of Nd dopants at Bi site and also confirmed the distorted rhombohedral perovskite structure of (BNFPT)_x compounds with R3c symmetry. Dielectric measurements showed magnetoelectric coupling around Neel temperature in all the samples and also improved dielectric properties with addition of dopants in BiFeO₃(BFO) compound. All the prepared samples exhibit weak ferro-magnetic character at room temperature. However, the variation in linear behavior and enhancement in magnetization is found at 5 K which shows gradual increase in remnant magnetization from 0.00785 emu/g to 0.37513 emu/g with increase in Nd doping for all (BNFPT)_x samples. Nd doping reduces leakage current by three orders of magnitude, from 10^− 4 to 10^− 7. Ferroelectric study revealed the pinning effect in hysteresis loops with low remnant polarization.

Ceramics

BiFeO¬3

(BNFPT)x

Rhombohedral

Raman Spectroscopy

Magnetoelectric

Remnant magnetization.

Multiferroics is a class of materials which show coexistence of at least two ferroic orders (ferroelectricity, ferromagnetism, and Ferro elasticity) in a single phase. The majority of recent research has concentrated on materials that combine magnetic order (ferromagnetic and antiferromagnetic) with ferroelectricity. [1-3]. These magnetic ferroelectric materials are fascinating as they not only possess the parent properties but also there is a possibility of coupling between them. This coupling between the two orders is called Magneto-electric (ME) effect, which is the property whereby a magnetic field causes an electric polarization and vice versa. The search for these materials is increasing day by day due to the combination of magneto electric properties, with eventual cross-coupling between these properties, and has enormous potential for new multifunctional devices such as tunneling magneto resistance sensors, tunable devices, and memory devices[4].

To incorporate ferroelectricity and magnetism, the simplest conceptual approach is to synthesize materials with distinct functional units. Ferroelectricity, strong dielectric response and ferromagnetism are provided with aid of non centro-symmetric units, in conjunction with magnetic ion units. The possible way is attributed to perovskite oxides of ABO₃ type, in which A-sites are generally occupied by cations of a Valencia electronic configuration (ns)²,such asBi³⁺, Ba²⁺that promote the stability of deformed ferroelectric structures and magnetic ion-bearing B-sites [5,6].This approach avoids the ferroelectricity and magnetism mutually exclusive on the same site since ferroelectricity derives from A-site ions and magnetism generated from B-site magnetic ions. It offers an efficient combination of electrical and magnetic controls as well as mutual control of each other.

The A-site ions such as Bi³⁺ in ABO₃perovskite structure allows magnetic transition metal ions to occupy B-site which permit the mutually exclusive condition to induced both magnetism and ferroelectricity [7,8]. One of the most popular material of this class is BiFeO₃, where Bi³⁺ ions on A-site produce the ferroelectricity and Fe³⁺ ions on B-site create magnetism. The displacement of Bi³⁺ ions from central-symmetric positions with respect to surrounding oxygen ions instigate ferroelectricity, whereas magnetic spins of unpaired Fe³⁺ ions contribute magnetism. BiFeO₃(BFO) is most studied substance for all single phase multiferroics [9].

Bismuth ferrite (BFO) is an antiferromagnetic-ferroelectric multiferroic. It has antiferromagnetic Neel temperature (T_N~643 K) and ferroelectric Curie temperature (T_C ~1103 K) in bulk shape. The composition of BFO is twisted rhombohedral perovskite with space group R3c [10]. Inside the pseudo cubic (111) plane, Fe3+ ions' magnetic moments are arranged in a ferromagnetic pattern., whereas it is linked antiferromagnetically between adjacent planes which is known as G-type antiferromagnetic ordering. If Fe spins are oriented perpendicular to[111] axis, symmetry-driven canting of the antiferromagnetic sub lattices enables detection of a weak ferromagnetism[11]. However, due to a overlying spiral spin structure in which the antiferromagnetic axis rotates through the crystal with an incommensurate long wavelength duration of 62nm, detection of macroscopic magnetization and linear magneto electric effect is forbidden [12].

Furthermore, due to the high likelihood of impurity phase formation and the strong dependency of physical properties on oxygen stoichiometry and crystal perfection, the synthesis of the BFO single phase is complicated. Apart from that, BFO has some disadvantages, such as a high leakage current, a lack of structural distortion, and low spontaneous saturation magnetization caused by spin helical ordering of magnetic moments [13,14].For the practical application of BFO, low leakage current and the existence of magnetic moments in the crystal are required; thus, improving the dielectric properties and suppressing the antiferromagnetic cycloidal spiral spin order of BFO has received special attention. Several studies on substitution of rare earth materials such as Nd, Dy, Sm on A-site and ferroelectric materials like PbTiO₃, BaTiO₃ on B-site of BFO are carried out to improve dielectric and magnetic properties [15-17].The structural parameters of bulk BFO and thin films have been modulated by the substitution of Nd³⁺ for Bi³⁺, resulting in the degradation of spin cycloid and poor ferromagnetism[18]. Increased Sm³⁺ doping in0.8BiFeO₃–0.2PbTiO₃ solid solutions improved dielectric behavior, according to Sahu et al. [19]. Therefore, rare earth element substitution has clearly influenced the structural, dielectric, ferroelectric, and ferromagnetic properties of BFO and BiFeO₃–PbTiO₃ (BF–PT) ceramics. This prompted us to look into the impact of Nd³⁺ substitution in the0.9BiFeO₃–0.1PbTiO₃multiferroic frame work. In this paper structural properties, dielectric properties and magnetic properties of 0.9Bi_1-xNd_xFe₃ – 0.1PbTiO₃solid solution with x=0.05, 0.10, 0.15 and 0.20 have been investigated.

The regular solid-state reaction method was used to render crystalline solid solution samples of 0.9Bi_1-xNd_xFeO₃–0.1PbTiO₃ with x =0.05,0.10,0.15, and 0.20. Analytical grade reagents Bi₂O₃, Nd₂O₃, Fe₂O₃, PbO and TiO₂ in stoichiometric proportions were weighed and mixed thoroughly in agate mortar in acetone medium for 4 h. The finely ground powder was calcined at an oven temperature of 800^oC. Pellets with a diameter of 7mm and thickness of 1mm were made and sediment at 820^oC in an air atmosphere using an organic binder. The samples crystal structure was studied using an X-ray diffraction technique recorded on a Bruker D8 Advance X-ray diffractometer using CuK radiation with a wavelength of 1.5406 Å. Scanning electron microscopy (Carl ZeissMA15/EVO18) was used for morphology examination of the surfaces. In order to conduct the Raman Spectroscopy measurements, a Renishaw micro Raman microscope with an Argon 514.5 nm laser as an excitation source was used. The ceramic samples' dielectric properties were measured using an HIOKI 3532-50 LCR meter. It efficiently operates in the frequency range 100Hz to 1Mhz and the temperature range 35-400^oC with a phase increase of 5^oC. The magnetization-hysteresis (M-H) measurements and the variation of magnetization from 5 K to room temperature, were carried out using a superconducting quantum interference device (SQUID). Furthermore, silver electrodes were applied to the sintered and polished pellets in order to conduct polarization hysteresis loop and leakage current versus voltage characterization (Radiant Technologies).

3.1. XRD Studies: Fig.1 shows the XRD spectra of 0.9Bi_1-xNd_xFeO₃–0.1PbTiO₃i.e. (BNFPT)_x with x= 0.05, 0.10, 0.15, 0.20 in 2θ range of 20°-60°.It can be seen that all (BNFPT)x compounds crystallized as single-phase materials with the same structure as the parent BiFeO3 compound [20,39]. Impurities and secondary phases were not observed in the diffraction profiles, which indicates in corporation of Nd⁺³in (BNFPT)_x crystal framework and confirms crystallinity of the compositions. The (104) and (110) peaks at 2θ of 32° became closer with increasing the doping content of Nd. This was also found at 2θ of 38° and 57°. The structure change in (BNFPT)_xindicates that Nd³⁺ enters into lattice and affects the structure and properties consequently [21].

The lattice parameters (equivalent hexagonal) of (BNFPT)_xwith x=0.05, 0.10, 0.15, and 0.20 are obtained using the formula

and miller indices of two highest intensity peaks of the XRD pattern {namely (104) and (110)} are taken, which are given in Table.1.The variations in lattice parameters clearly show that Nd3+ intrusion has a significant effect at the Bi³⁺ site. The findings are consistent with previous reports on doped BT-PT binary systems. [22,35].

Table. 1

Lattice Parameters, cell volume and grain size of (BNFPT)_xceramics with x= 0.05, 0.10, 0.15 and x=0.20.

Composition Lattice Parameter(A⁰) Cell Volume Average grain (A³) Size (μm)
X a(A⁰) b(A⁰) c(A⁰)
0.05 5.5800 5.5800 13.8127 372.4582 1.20
0.10 5.5782 5.5782 13.7964 371.7787 1.00
0.15 5.5750 5.5750 13.7720 370.6955 0.88
0.20 5.5718 5.5718 13.7580 369.8937 0.75

3.2. Morphological Studies: Fig. 2(a–d) shows surface morphology of (BNFPT)_x ceramics. From the micrograph, it has been observed that all of the ceramics exhibit uniformity in dense grain distribution on the material's surface..For qualitative analysis of compositions, energy dispersion X-ray spectroscopy (EDX) of (BNFPT)_xare also displayed in Fig.3. The average grain size [Table.1] of (BNFPT)_x ceramics decreases from 3.0μm to 0.75 μm with increase of Nd content, which were also reported in other similar compositions [23].

Table 2. Comparison of Raman mode positions (cm^-1) from (BNFPT)_xsamples with x=0.05,0.10,0.15 and 0.20, Reported data on bulk polycrystalline BiFeO3 Kothari et al.

Raman

modes Literature

(cm^-1) Kothari et al. Present study

(BNFPT)_0.05 (BNFPT)_0.10 (BNFPT)_0.15 (BNFPT)_0.20

A₁-1 135.15 141.15 136.73 138.68 136.73

A₁-2 167.08 169.50 171.25 169.50 -

A₁- 3 218.11 212.44 206.84 219.78 205.62

A₁-4 430.95 442.83 452.84 465.38 456.40

E 71.39 - - - -

E 98.36 - - - -

E 255.38 - - - -

E 283.0 285.54 286.05 285.54 284.84

E 321.47 324.25 334.41 333.90 328.38

E 351.55 - - - -

E 467.60 503.22 502.55 506.76 500.19

E 526.22 - - 539.71 -

E 598.84 613.33 605.68 617.98 597.52

E - 742.50 729.25 737.93 717.79

3.4. Dielectric properties: Fig.5 shows the variation of dielectric constant(Ɛ) and dielectric loss tangent (tanδ) of (BNFPT)_x samples with x=0.05,0.10,0.15, and 0.20 compositions in the frequency range 100Hz to 1MHz..It is observed that for all of the prepared samples, the dielectric constant decreases as the frequency increases from 100Hz to 1Mhz. The dielectric constant is much higher at lower frequencies and decreases as the frequency of the applied alternating field increases, due to the electric dipoles' inadequacy to switch with the applied electric field frequency at high frequencies. The variation of Ɛ can be explained on the basis of interfacial space charge relaxation process[28,29].The oxygen (O^-2) and bismuth(Bi⁺³) vacancies on A- site of composition originate the space charges that are in sync with the applied electric field at low frequencies and help to preserve the dielectric constant. Furthermore dielectric constant increases with the increase in Nd doping for all prepared samples, as shown in Fig.5, owing to the formation of oxygen vacancies caused by the volatile nature of the Bi³⁺ ion and the transition from Fe³⁺ to Fe²⁺[30].Dielectric losses are proportional to the amount of energy dissipated in the device due to domain wall resonance and space charge polarization. It has been observed that dielectric loss tangent decreases with increase in frequency for all (BNFPT)_xceramics. It is high at lower frequencies due to energy dissipation of accumulated space charge polarization at grain boundary and low at higher frequencies as the result of inhibition of domain wall motion. Furthermore, at higher frequencies the redirection of the space charge stops following the frequency of the applied electric field E. The small peaks in the dielectric loss tangent are observed at 10Khz-1Mhz frequencies range which is in agreement with Debye relaxation process.

The temperature dependent of dielectric constant(Ɛ) and dielectric loss tangent (tanδ) for all (BNFPT)_xcompositions with x=0.05,0.10,0.15 and 0.20 at frequencies 1kHz, 10kHz, 100kHz and 1MHz are shown in Fig.6. No dielectric anomalies have been observed at lower temperature with Nd content x≥0.15 which may be attributed to suppression of point defects and oxygen vacancies due to increasing Nd concentration. However, for x = 0.10, 0.15 and0.20 (BNFPT)_xsamples, dielectric anomalies have been observed at temperatures320⁰C,360⁰C and 340⁰C at 100kHz frequency respectively. These observed anomalies in the dielectric constant can be correlated to AFM Neel temperature (T_N) and phase transitions of BiFeO₃ and PbTiO₃compounds which attributed to multiferroic behavior of prepared samples. For rare earth doped BFO, similar anomalies in the dielectric constant have been reported near Néel temperature[31,32].The dielectric anomaly corresponding to Neel temperature shifts towards higher temperature with increase in Nd⁺³doping composition. The shift in Neel temperature (T_N) is correlated to the variation of Fe–O–Fe angle due to the structural modification by the replacement of Bi⁺³ ions by Nd⁺³ ions according to relation, T_N= JZS(1+CosƟ), where J is exchange constant, S (= 5/2) is spin of Fe⁺³ ion and Z = 6 is the average number of nearest neighbors per Fe⁺³ ion and Ɵ corresponds to Fe–O–Fe bond angle [33].With increasing doping Nd⁺³concentration, the Fe–O–Fe bond angle increases continuously, which may be attributed to the enhancement in T_N. In addition, as doping increases, the value of the dielectric constant rises, indicating that dielectric ordering improves. Furthermore, in all of the (BNFPT)x compounds, the dielectric loss tangent increases at higher temperatures while decreasing at lower temperatures due to imperfections and thermally eminent charge carriers. The observed anomaly in dielectric loss near Neel temperature (T_N) is accordance with Landau–Devonshire phase transition theory, which is attributed to vanishing magnetic order on electric order in magneto electrically ordered system. It has been also observed that the dielectric loss tangent [Fig.6] decreases with increasing Nd⁺³ ions doping for all (BNFPT)_xsamples which indicate stability and charge carrier movement, implying an increase in sample resistivity. In addition, the sharp increase in dielectric loss tangent after 300⁰C for all (BNFPT)_x samples at 1Mhz frequency indicates the activation of thermal process that enhance space charge polarization linked to oxygen vacancies at higher temperature, resulting in increased conductivity [34].

3.5. Magnetic properties: Fig. 7 shows the magnetization(M) versus magnetic field(H) plots for prepared (BNFPT)x (with x=0.05,0.10,0.15, and0.20) samples at room temperature and 5 K. It is observed from M(H) plots that at room temperature, all the prepared samples exhibit weak ferromagnetism. The linear dependence of magnetization in wide range of magnetic field indicates a G-type antiferromagnetic ordering. At 5 K, the increase in magnetization and variation in linear behavior of magnetization is noticed as the Nd-doping content increases. The value of remnant magnetization for (BNFPT)_x(with x = 0.05, 0.10, 0.15 and 0.20) is found 0.00785 emu/g, 0.2317emu/g,0.14577emu/g and 0.37513 emu/g respectively. The similar reports have been observed for Nd⁺³ions substitution in BF-PT system[35,36].The structural distortion induced by the doping of Nd³⁺ ions in BF-PT solid solution ceramics, as well as the exchange interaction between Nd³⁺-Fe³⁺ ions, may be responsible for the increase in magnetization in Nd-doped BF-PT ceramics. Furthermore, withNd doping, the change in O-Fe-O bond angle due to contraction of unit cell volume (Table.1) may unlock the latent magnetization trapped in the cycloidal spiral structure, resulting in an increase in magnetization [37].

The temperature versus magnetization plots of all (BNFPT)_xcompositions with x=0.05, 0.10, 0.15 and 0.20 under zero field cooling (ZFC) and on cooling in a constant magnetic field of 500Oe (FC) in temperature range 300K to 5K is shown in Fig.8. (BNFPT)_x solid solution is a magnetically diluted BiFeO3 system that is supposed to have similar magnetic interactions as BiFeO3, which is antiferromagnetically ordered with weak ferromagnetism below its Néel temperature T_N=643K. It has been observed that the magnetization of all (BNFPT)_xcompositions decrease with increase in the temperature and show weak ferromagnetism which is also confirmed with magnetization vs magnetic field plots at room temperature(Fig.6).With increasing Nd concentration, all (BNFPT)x compounds display a splitting of the ZFC and FC curves below 300K. The enhancement of magnetization is obtained with the decrease in temperature which indicates a frustration increase between Nd+3 and Fe+3 magnetically activated ions due to the Fe–O–Fe angle bending. The similar reports is observed by Mishra at al. [38]. It has been observed that the degree of magnetization is found to be influenced by the extent of Nd doping and increases continuously with increase Nd doping at low temperature. The values of magnetization of ZFC plots at low temperature are found to be 0.00841emu/g, 0.01292emu/g, 0.031.29emu/g and 0.089.41emu/g for(BNFPT)_x compound with x = 0.05, 0.10, 0.15 and 0.20 respectively. We found the better result of magnetization with Nd doping as compared to other reports on rare earth doped or undoped BF-PT compounds [39,40]. The enhancement in magnetization demonstrates that Nd doped bismuth ferrite, of course, affects the Fe-O-Fe angles and thus has a major effect on its magnetic ordering. In addition, the effect of non-magnetic Ti⁺⁴ ions of PbTiO₃ at the B-site of BFO dilutes the impact of magnetically active Fe⁺³ ions, causing Fe ions to fluctuate in the lattice and enhancing ferromagnetic activity over micro-regions. [41].

3.6. Leakage Current and Ferroelectric Properties: Fig. 9 shows the leakage current (I) versus applied voltage (V) plots of the prepared (BNFPT)_x (with x=0.05,0.10,0.15, and0.20) samples at room temperature. The main drawback of BFO compound is high leakage current. It has been observed that as Nd doping increases, leakage current decreases. As shown in Fig.8, the value of leakage current is reduced by three orders of magnitude, from 10^-4 (for x=0.05 composition) to 10^-7 (for x=0.20 composition). Yongyuan Zang et al. reported the similar reduction in leakage current for rare-earth element doped BFO compound [42]. The decrease in leakage density is due to the suppression of charge defects caused by valence fluctuations of Fe+ 3ions to Fe+2 ions, as well as oxygen vacancies, as Nd doping increases. Furthermore, as shown in the morphological study, due to the smaller average grain size, current density will be suppressed by local space charge near grain boundaries due to grain boundary limited conduction [43,44].

The ferroelectric hysteresis loops (Polarization versus Electric field) at room temperature of (BNFPT)_x samples with x=0.05,0.10, 0.15 and 0.20 are shown in Fig.10. Ferroelectricity is produced in (BNFPT)_x samples as a result of the hybridization of the Bi(6s²) lone pair and the O(2p) BiFeO3 crystal orbital, as well as the Ti(3d) orbital and the O(2p) PbTiO₃ ferroelectric distortion. It has been observed that as Nd doping increases, the remnant polarization (2Pr) decreases. The values of remnant polarization are found to be 1.05539µc/cm², 0.47927 µc/cm²,0.2903 µc/cm²and 0.03148 µc/cm² for x=0.05,0.10,0.15 and 0.20 compositions of (BNFPT)_x samples. This reduction in remnant polarization could be attributed to structural distortions in prepared compounds as well as differences in the ionic radii of Nd⁺³ ions and Fe⁺³ions. The similar reduction in values of remnant polarization are reported for Sm doped BF-PT compounds [45]. In addition oxygen vacancies produced during sintering process are also responsible for low polarization. These oxygen vacancies forms defect dipoles with Pb ions. The induced polarization vector caused by these dipoles requires more energy to reorient in the field direction, causing a pinning effect in hysteresis loops. Several reports on oxygen vacancies are available for reduction of polarization [46-47]. The values of coercive fields (negative values) are found to be 8.0567 kv/cm, 6.3756 kv/cm, 5.6881 kv/cm and 1.3158 kv/cm for x=0.05,0.10,0.15 and 0.20 compositions of (BNFPT)_x samples.

In summary, 0.9Bi_1-xNd_xFeO₃ – 0.1PbTiO₃solid solution with x=0.05, 0.10, 0.15 and 0.20 were successfully synthesized by the standard solid-state reaction method. The XRD pattern and Raman analysis revealed the existence of rhombohedral structure with space group R3c for (BNFPT)x samples. The changes in crystal structure are attributed to the Bi-site disorder created by Nd substitution, which leads to the shifting of Raman modes with sudden disappearance of some E modes at low frequency. The dielectric anomaly has been observed near Neel temperature. This dielectric anomaly becomes more prominent with increasing Nd doping which indicates the enhancement of magnetic and electric interactions. With increasing Nd doping, temperature dependent dielectric loss decreases, suggesting that the samples' thermal stability has improved due to increased resistivity. The enhancement in magnetization indicated that Fe-O-Fe angles are influenced by Nd doped BF-PT, which improve its the magnetic properties. The better result of magnetization with Nd doping was found as compared to other rare earth doped BiFeO₃-PbTiO₃ compounds. The improvement of leakage current may be a potential candidate for a variety of applications. With increasing Nd doping, a ferroelectric study indicated low residual polarization.

Author’s Contribution: The manuscript was written with the help of all of the contributors. The final draught of the manuscript has been authorized by all contributors.

Declaration: There is no conflict of interest declared by the authors.

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Structural modification and evaluation of Dielectric, Magnetic and Ferroelectric Properties o f Nd- modified BiFeO₃– PbTiO₃ Multiferroic Ceramics

Status:

Version 1

Abstract

Figures

1. Introduction

2. Materials And Methods

3. Results And Discussion

4. Conclusions

Declarations

References

Status:

Version 1