Processing, dielectric and impedance spectroscopy of lead free BaTiO3-BiFeO3-CaSnO3

doi:10.1016/j.jallcom.2018.06.284

Journal of Alloys and Compounds

Volume 766, 25 October 2018, Pages 25-32

https://doi.org/10.1016/j.jallcom.2018.06.284 Get rights and content

Highlights

•
The cheap cost synthesis of BTO-BFO-CSO and best performance is evaluated.
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Dielectric properties with respect to temperature and frequency is investigated.
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Nyquist plots relate about contributions of grain with NTCR behavior.
•
A well defined relaxation mechanism was identified by modulus analysis.

Abstract

The paper presents the fabrication and characterization of structural and electrical properties of an electronic composite of three perovskites: BaTiO_3, BiFeO₃ and CaSnO₃ in a fixed ratio of 80/13/07 (i.e., 0.80(BaTiO₃)-0.13(BiFeO₃)-0.07(CaSnO₃) (referred as BTO-BFO-CSO-7)) using standard experimental techniques. Analysis of room temperature X-ray diffraction spectra helps to determine the crystal system and unit cell dimensions (lattice parameters) of the sample. The dielectric and impedance spectroscopy was used to study the resistive (impedance, complex electrical modulus and electrical transport properties) and insulating (dielectric) characteristics of the prepared electronic material at various frequencies (10²–10⁶ Hz) and temperatures (20–450 °C). Study of the Nyquist plot confirms the presence of temperature dependent bulk (grain) effect only and negative temperature coefficient resistance in the BTO-BFO-CSO-7 composite. Analysis of conductivity spectra reveals that the charge transfer by hopping contributes to the electrical transport process. The dielectric relaxation of the sample is studied using complex modulus spectra. This study also helps to understand the mechanism of the electrical transport process, which depicts a non-Debye type of conductivity relaxation. The magnetic hysteresis loop (M − H) shows a remanent magnetization of 0.031 emu/g.

Introduction

In the days of modernization, smart materials, including ferro-electro-magnetics, ferroics, piezoelectrics, optical fibers and shape-memory alloys are tailored by external stimuli. The main reason of being smart may be due to its application for specific uses exhibiting certain nature more than its usual properties. Multiferroic materials are a special class of smart materials which contains two or more ferroic domains (ferroelectric, ferromagnetic, ferroelastic, etc.) in a single-phase system. Such type of materials has a great potential for fabrication of devices (i.e., sensors, storage devices, spintronic device, etc.) and diversely in industries, like automotive, defense, aerospace and robotics [[1], [2], [3]]. In an extended meaning, this class of materials is capable of switching the electrical field with the virtue of magnetic field as well as the spontaneous magnetization, switched by means of an applied electric field [4]. One of the promising multiferroic materials at room temperature is bismuth ferrite, BiFeO₃ (BFO). It has a ferroelectric transition temperature of 830 °C and anti-ferromagnetic transition temperature of 370 °C [5]. It is observed that BFO has difficulty in getting proper ferroelectric hysteresis loop due to large leakage current and low resistivity. At room temperature, due to semi-conducting nature of BFO, the experimental data also show low values of dielectric constant, high loss and low spontaneous polarization [6]. In order to resolve these inherent problems of BFO, the fabrication of solid solutions/composites, suitable doping/substitution at the cation sites and the development of new techniques to get single phase of BFO has extensively been attempted [[7], [8], [9]]. It has also been found that the preparation of pure BFO has a significant presence of the secondary phase/impurity (Bi₄₀Fe₂O₆₃ or Bi₃₆Fe₂O₅₇) leading to a controversial composition. For increasing the structural stability of BFO, the fabrication of BFO-ABO₃ (A = mono to -divalence ions, B = tri to hexavalence ions) system has been found very important for scientific as well technological importance. Some of past investigation shows that the BFO-PbTiO₃ [10] composite has enhanced electrical polarization and reduced leakage current, BFO-DyFeO₃ [11] composite reveals enhanced dielectric properties, whereas BFO-BaTiO₃ [12] revels both ferroic order and low loss (less than 3%). Yang et al. fabricated BFO-BTO-YIG composites and reported the basic crystal structure, proper (less leaky) P-E loop and enhanced electrical and magnetic properties [13]. Out of many perovskites, some members of alkaline-earth stannate family have been used to fabricate its composites with bismuth ferrite for the enhancement of dielectrsic properties, manufacturing of thermally stable capacitors and photo-catalysis. In both the states (i.e., doped or pure), such type of materials is considered as a base material for gas detection sensors which involves various gas like H₂, Cl₂, NO₂, CO, HC [14]. Despite such potential applications, some alkaline earth stannate composites have not been examined extensively except a few. Mandal et al. [15] reported the processing and electrical properties of CaSnO₃ porous sample. But, the correlation of such prepared material was not established with BFO-BTO solid solutions. The porous sample prepared by them cannot be a better capacitor material, because the electric charge carriers will sink in the pore leading to a reduced grain to grain connectivity. The availability of pores within the sample will lead to the interaction with humidity. In this context, firstly, we have added a small amount (7 wt %) of CaSnO₃ in the BTO (major)-BFO(minor) system which leads to high reactivity and a reduction in the reaction temperature.

Taking the environmental concerns, the elimination of lead compounds from device engineering leads to focus on the synthesis, and characterization (phase evolution, microstructure, molecular and electrical properties (conductivity, impedance, modulus, and dielectric) of an electronic composite of three perovskites in a 80/13/07 ratio (i.e., 0.8(BaTiO₃)-0.13(BiFeO₃)-0.07(CaSnO₃) = BTO-BFO-CSO-7).

Section snippets

Experimental

The fabrication of BTO-BFO-CSO-7 was carried out by a standard mixed-oxide route using starting materials; BaCO₃ (M/S Loba Chemie Co Ltd, 99% pure), Fe₂O₃ (M/S Loba Chemie Co Ltd, 98% pure), Bi₂O₃ (M/S Central Drug House Pvt Ltd, 99% pure), TiO₂ (M/S Loba Chemie Co Ltd, 98% pure), SnO₂ (M/S Loba Chemie Co Ltd, 99.9% pure), CaCO₃ (M/S Sigma-Aldrich, 99.99% pure). These raw powders of oxides and carbonates were carefully weighed in required stoichiometry. The starting materials were mixed in a

Crystal data and morphology

To check the phase purity, the crystal structure determination, and lattice parameters X-ray diffraction analysis was undertaken. Fig. 1 exhibits the X-ray diffraction (XRD) pattern of BTO-BFO-CSO-7 which analysis confirms the coexistence of BTO-BFO and CSO phases in the fabricated composite. It shows a number of sharp peaks which are totally different from that of raw materials. Analysis of XRD pattern confirms the presence of desirable phases (i.e. both BTO-BFO and CSO) in the composites with

Conclusion

In the present study, the structural, capacitive (dielectric constant, tangent loss) and resistive (impedance, modulus and conductivity) properties of BTO-BFO-CSO-7 were intensively studied. The compound was synthesized by a cheap cost (high-temperature solid-state reaction) route. The room temperature XRD reveals the presence of all BTO, BFO, CSO phases along with some impurity peaks in the prepared composite. Substitution of CSO in BTO-BFO has improved the microstructure, with high density,

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View full text

Processing, dielectric and impedance spectroscopy of lead free BaTiO3-BiFeO3-CaSnO3

Highlights

Abstract

Introduction

Section snippets

Experimental

Crystal data and morphology

Conclusion

Solid State Commun.

Mater. Lett.

Mater. Sci. Eng., B

J. Magn. Magn Mater.

Ceram. Int.

J. Alloy. Comp.

J. Alloy. Comp.

J. Alloy. Comp.

J. Phys. Chem. Solid.

Solid State Ionics

Material Phys. Chem.

J. Alloy. Comp.

Science

Bull. Russ. Acad. Sci. Phys.

Appl. Phys. Lett.

Nature

Appl. Phys. Lett.

Spaldin, Phys. Rev. B

J. Appl. Phys.

Appl. Phys. Lett.

J. Mater. Chem. C

Processing, dielectric and impedance spectroscopy of lead free BaTiO₃-BiFeO₃-CaSnO₃