Dielectric, piezoelectric and magnetic behavior of CoFe2O4/BNT–BT0.08 monolayer thin films composites

https://doi.org/10.1016/j.mseb.2022.115770Get rights and content

Highlights

  • BNT-BT0.08/CoFe2O4 composite thin films monolayer with different molar ratios were prepared.

  • These thin films showed good dielectric, piezoelectric and magnetic properties.

  • These macroscopic properties depend on the BNT-BT0.08/CoFe2O4 molar ratio.

Abstract

We report in this paper on the monolayer composites thin films that have the magnetic spinel CoFe2O4 and the piezoelectric perovskite BNT-BT0.08 as constituent phases. Composite thin films of CoFe2O4 and BNT-BT0.08, with molar ratios of 0.5:1, 1:1 and 1.5:1, have been deposited by spin coating method from a sol precursor, mixture type, of CoFe2O4 and BNT-BT0.08. The monolayer thin films, deposited on Si/SiO2/TiO2/Pt substrate, were characterized using selected methods, such as: X-ray diffraction, scanning electron microscopy, atomic force microscopy/piezoelectric force microscopy, dielectric spectroscopy, and vibrating sample magnetometer. X-ray diffraction demonstrated the two phases: cubic CoFe2O4 and rhombohedral BNT-BT0.08. Furthermore, the Si/SiO2/TiO2/Pt/BNT-BT0.08/CoFe2O4 monolayers show a simultaneous enhancement of both the magnetization and coercivity with the increase of the magnetic phase, accompanied by a decrease of the dielectric constant. The obtained results reveal that the investigated monolayer structures present superior properties compared to those of bilayer composites.

Introduction

The composites are important materials considering they exhibit improved specific properties for each component and/or new properties or functionalities compared to the constituent phases. For example, in a composite of a metal and an insulator, one could control the electrical resistivity by controlling the volume fraction and distribution of the two phases [1]. Also, an example for the composites with new properties is the electric field-to-magnetic field conversion (or vice versa) that could be realized in a magnetostrictive-piezoelectric composite [2], [3], [4], [5], [6], [7], [8]. There are many reports on composites with electrical, ferroelectric and ferromagnetic behaviors, for example: multiferroic-ferrimagnetic (BiFeO3-CoFe2O4) composites [9], ferromagnetic-piezoelectric oxide (nickel ferrite (NiFe)- Pb0.92La0.08Zr0.52Ti0.48O3 (PLZT)) composites [10], ferroelectric-ferrimagnetic (BaTiO3-CoFe2O4) composites [11] and (La0.7Sr0.3MnO3-PbZr0.2Ti0.8O3 heterostructures [12]), and ferrimagnetic-piezoelectric CoFe2O4–PZT [13]). These composites were fabricated in the form of bulk, thin films and tubes, by using various methods. For bulk composites with core–shell structure various techniques were used, such as: the coprecipitation method [14], sol–gel method [15], sonochemical technique [16], conventional solid-state sintering method [17], two-step hydrothermal method [18], etc. Bilayer composite films were prepared using magnetron sputtering [19], combining method of sol–gel and electrophoretic deposition [11], chemical solution deposition [20], sol–gel deposition [21] and, pulsed laser deposition (PLD) [13]. CoFe2O4/BNT-BT0.08 core–shell nanotubes were prepared by using a preformed removable polycarbonate membrane template-assisted sol–gel process [22], [23], [24] and electrospinning [25]. The present reports on the ferrimagnetic-ferroelectric monolayer composites thin films CoFe2O4-BNT-BT0.08, with molar ratios of 0.5:1, 1:1 and 1.5:1, (samples S1, S2 and S3), respectively. Ferrites and perovskites are two important classes of metal oxides, as ferrites have high resistivity (i.e. low dielectric constant), while perovskites have diverse applications such as cathode material in solid oxide fuel cells, catalytic applications, and can also be magnetic in nature depending upon the presence of iron contents. It was already demonstrated that by combining the magnetic spinel CoFe2O4 phase with the piezoelectric perovskite (Bi0.5Na0.5)0.92Ba0.08TiO3, abbreviated as BNT-BT0.08 [21] or (Bi0.5Na0.5)0.65Ba0.35TiO3, (BT–BNT0.35) [17] it results in composite materials with magnetic, piezoelectric and magnetoelectric properties.

Furthermore, we have already reported on the ferrite (CoFe2O4)-ferroelectric (BNT-BT0.08) composites with various architectures, such as: core–shell nanoparticles [26], bilayer ferrite–piezoelectric composites of CoFe2O4 and BNT-BT0.08 [21] and, core–shell nanotubes [22], prepared by sol–gel route. Thus, compared to the previous report on bilayer ferrite–piezoelectric composites of CoFe2O4 and BNT-BT0.08 [21], this work has as a novelty, the preparation procedure to obtain a monolayer film (samples S1, S2 and S3) that consists in the use of a sol precursor mixture of CoFe2O4 and BNT-BT0.08. As a result, their structural, microstructural, dielectric, piezoelectric and magnetic properties are investigated and discussed here, while a comprehensive comparison between the properties of these monolayer composites thin films and those of bilayer composites thin films is also displayed.

Section snippets

Experimental section

Composites thin films of BNT–BT0.08 and CoFe2O4, with different molar ratios: 0.5:1 (sample S1), 1:1 (sample S2) and 1.5:1 (sample S3) were prepared by sol–gel method. Bismuth (III) acetate ((CH3COO)3Bi, 99.99%), sodium acetate (CH3COONa, 99.995%), barium acetate ((CH3COO)2Ba, 99%), titanium (IV) isopropoxide (Ti{OCH(CH3)2}4) in isopropanol, acetic acid, acetylacetone and dimethylformamide were used as starting reagents in order to prepare BNT–BT0.08 precursor sol. Cobalt acetate (Co(CH3CO2)2·4H

Structural and morphological aspects

Fig. 1 shows the XRD patterns of the CoFe2O4/BNT–BT0.08 = 0.5:1; 1:1; 1.5:1 composite thin films, annealed at 700 °C, 1 h in air.

As can be seen in Fig. 1, there are peaks of the cubic phase of CoFe2O4 (JCPDS card No.05-7078 [27]), peaks of the rhombohedral phase of Na0.5Bi0.5TiO3 (JCPDS card No. 70-9850 [28]) and, peaks of the Si-Pt substrate. The amplitude of the peaks attributed to the cubic CoFe2O4 phase increases with the increase of the CoFe2O4/BNT–BT0.08 ratio while, the intensity of the

Conclusions

In conclusion, the monolayer CoFe2O4/BNT-BT0.08 composites ferrimagnetic–piezoelectric thin films, with molar ratios of 0.5:1, 1:1 and 1.5:1, were synthesized by sol–gel synthesis and deposited by spin coating methods. The XRD analysis evidenced the existence of the two phases: cubic CoFe2O4 and rhombohedral BNT–BT0.08; the peaks intensity increases for the magnetic phase and decreases for the piezoelectric phase from the sample S1 to S3. Through SEM and EDS, it has been shown that the chemical

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

The authors gratefully acknowledge the funding through Core Program PN18–11 from Romanian Ministry of Research and Innovation.

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