Effect of nano -size on magnetostriction of BiFeO 3 and exceptional magnetoelectric coupling properties of BiFeO 3_PVDF -TrFE polymer

2025-08-18 1 0 1.03MB 29 页 10玖币

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Effect of nano-size on magnetostriction of BiFeO3 and exceptional

magnetoelectric coupling properties of BiFeO3_P(VDF-TrFE) polymer

composite films for magnetic field sensor application

Sonali Pradhan1,2*, Pratik P. Deshmukh1, Rahul C. Kambale3, Tulshidas C. Darvade3,4,

Shovan Kumar Majumder1 and S. Satapathy1*

1Laser Biomedical Applications Division, Raja Ramanna Centre for Advanced Technology,

Indore, 452 013, Madhya Pradesh, India.

2Homi Bhabha National Institute, Training School Complex, Anushakti Nagar, Mumbai, 400

094, Maharashtra, India.

3Department of Physics, Savitribai Phule Pune University, Pune, 411 007, Maharashtra,

India.

4Department of Physics, Sir Parashurambhau College, Pune, 411 030, Maharashtra, India.

*Address for Correspondence:

E-mail Address: srinu73@rrcat.gov.in;sonalipra8@gmail.com;

Abstract

The existence of magnetostriction in bulk BiFeO3 is still a matter of investigation and it is also

an issue to investigate the magnetostriction effect in nano BiFeO3. Present work demonstrates

the existence of magnetostrictive strain in superparamagnetic BiFeO3 nanoparticles at room

temperature and the magnetoelectric coupling properties in composite form with P(VDF-

TrFE). Despite few reports on the magnetostriction effect in bulk BiFeO3 evidenced by the

indirect method, the direct method (strain gauge) was employed in this work to examine the

magnetostriction of superparamagnetic BiFeO3. In addition, a high magnetoelectric coupling

coefficient was observed by the lock-in technique for optimized BiFeO3_P(VDF-TrFE)

nanocomposite film. These nanocomposite films also exhibit room-temperature multiferroic

properties. These results provide aspects of material with immense potential for practical

applications in spintronics and magneto-electronics applications. We report a magnetoelectric

sensor using superparamagnetic BiFeO3_P(VDF-TrFE) nanocomposite film for detection of ac

magnetic field.

Keywords: Composite materials; Magnetostriction; Magnetic measurement; Transmission

electron microscopy (TEM); Scanning electron microscopy (SEM); Nanostructured materials

1. Introduction

Magnetoelectric multiferroic materials are remarkable for strong coupling of electric,

magnetic, and structural degrees of freedom, which provides ferroelectricity, ferromagnetism,

and ferroelasticity simultaneously [1]. The magnetoelectric (ME) effect contributes to intensive

scientific explorations in the field of sensors, actuators, memories, spintronics and transducers,

which have potentially huge commercial values [2–5]. However, the magnitude and operating

temperatures of observed ME coupling have been too low for practical applications. Most

single-phase materials show ME coupling at extreme conditions (high magnetic field and low

temperature). Therefore, the fabrication of single-phase magnetoelectric materials at room

temperature is a challenge for current active research. Among several multiferroics, the only

known room-temperature multiferroic material for potential practical interest is bismuth ferrite

(BiFeO3) which is ferroelectric (TC~1100 K) and antiferromagnetic (TN~ 640 K) [6]. It exhibits

a weak net magnetization due to G- type magnetic ordering via Dzyaloshinskii-Moriya (D-M)

interaction among nearest neighbor Fe3+ spins with an incommensurate cycloid spin structure

having a periodicity of 62 nm [7]. Bismuth ferrite shows quadratic and higher-order ME

coupling at room temperature, while linear ME coupling is observed at high electric and

magnetic fields [8,9]. The presence of the spin cycloid nullifies linear ME coupling between

electric polarization and magnetization. However, it is important to note that bulk BiFeO3

(BFO) shows negative magnetostrictive magnetoelectric coupling which was reported by Park

et al [10]. According to the report, the magnetostrictive origin suppresses the electric

polarization at the Fe site below TN outweighing the inverse D-M interaction. In 2010

Tokunaga et al observed field-induced polarization change with magnitudes of approximately

200 µC/m2 along with one of the principal axes in single-domain crystals of BFO [11]. The

suitability of the BFO becomes constrained in many fields because of its spiral-modulated spin

structure.

Despite intense study on BFO over the past decades a fundamental understanding of structure-

property correlations in BFO is still lacking, specifically the nature of the magnetic response

on the size. Moreover, low dimension (< 62 nm) is expected to lead to linear ME coupling due

to modification in long-range spiral modulated spin structure [12,13]. To overcome this

hindrance, we have considered low dimensional confinement. Moreover, BFO displays novel

physical properties with a decrease in size due to an increased surface-to-volume ratio [14].

Recently, it has been shown that BFO nanoparticles exhibit strong size-dependent magnetic

properties: (1) suppression of the spiral spin structure increases with decreasing nanoparticle

size, (2) uncompensated spins with spin pinning and strain anisotropies at the surface and (3)

presence of oxygen vacancies and impurities [15]. BFO below a critical size affords single-

domain magnetic nanoparticles exhibiting superparamagnetic (SPM) behavior. In the current

work, we studied the magnetic properties of BFO nanopowders with a single domain, obtained

by the auto combustion technique. The existence of magnetostrictive properties in

superparamagnetic BFO is a matter of investigation. Therefore, a study on magnetostrictive

properties of super paramagnet BFO has been highlighted here. Further, the use of

magnetostrictive properties of superparamagnetic BFO has been explored in ferroelectric

polymer composite films.

To utilize the superparamagnetic BFO nanoparticles for high performance ME coupling effect,

a perfect flexible ferroelectric matrix is required. In these circumstances, P(VDF-TrFE)

(poly(vinylidene fluoride-trifluoroethylene)) copolymer is an ultimate candidate for

ferroelectric matrix because of its high energy density, high insulating property and good

piezoelectric properties [16,17]. Moreover, among the five crystalline phases of PVDF, the β-

phase is the best ferroelectric phase to implement [18]. Among the ME composites, polymer-

based composites have advantages over ceramic-based composites because of non-

deterioration during operation and are compatible with industrial requirements without large

leakage current [19]. Nevertheless, the ME coupling effect of superparamagnetic BFO

embedded in the P(VDF-TrFE) matrix has not yet been reported. In the current work, the

structural, magnetic and magnetostrictive properties of superparamagnetic BFO and

magnetoelectric coupling properties in BFO_P(VDF-TrFE) nanocomposite films are

investigated.

In general, the ME coupling in composite systems appears due to elastic interaction between

the ferroelectric and magnetic phases [20,21]. The direct ME coupling in magnetoelectric

composite has been noticed to happen mainly through strain [22]. The strain induced in the

magnetic phase by an external magnetic field due to magnetostriction. Magnetostriction is

defined as a change in dimensions of the material in regards to an external applied magnetic

field [23,24]. It is computed as λ = Δl/l [25,26]. The magnetostriction of a material can be

examined by direct and indirect methods. In the direct method, magnetostrictive strain is

measured as a function of the externally applied DC magnetic field, which is employed here.

Due to the superparamagnetic behavior of BFO nanoparticles, the magnetic moment of

nanoparticles can be more easily flipped in the polymer under an applied magnetic field at

room temperature, which might create strain in the polymer matrix. Moreover, the interface

effect between nanoparticles and the polymer matrix is a prominent factor for ME coupling

properties, which was easily achieved through small-size BFO nanoparticles due to the

increasing ratio of the interface area to volume. According to surface elasticity theory, it was

found that the interfacial stress due to the inclusion of nanoparticles in polymer shows a short-

range effect, which introduces internal stresses in the matrix resulting in output voltage [27,28].

Different volume % of superparamagnetic BFO nanoparticles in polymer matrix influence the

dielectric, ferroelectric and magnetic properties of the nanocomposite films. Therefore,

BFO_P(VDF-TrFE) nanocomposite films with different volume % (0.2, 0.5, 1, 1.5, 3 and 5%)

of BFO nanoparticles were prepared to examine the room temperature multiferroic properties

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Effectofnano-sizeonmagnetostrictionofBiFeO3andexceptionalmagnetoelectriccouplingpropertiesofBiFeO3_P(VDF-TrFE)polymercompositefilmsformagneticfieldsensorapplicationSonaliPradhan1,2*,PratikP.Deshmukh1,RahulC.Kambale3,TulshidasC.Darvade3,4,ShovanKumarMajumder1andS.Satapathy1*1LaserBiomedicalApplicatio...

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Effect of nano -size on magnetostriction of BiFeO 3 and exceptional magnetoelectric coupling properties of BiFeO 3_PVDF -TrFE polymer

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