Effects of Mn doping on ferroelectric, ferromagnetic and optical properties of BiFeO3 thin films

doi:10.1016/j.physb.2020.412317

Physica B: Condensed Matter

Volume 594, 1 October 2020, 412317

https://doi.org/10.1016/j.physb.2020.412317 Get rights and content

Highlights

•
The increase of Mn doping leads to the change in surface microstructure.
•
Mn-doping restrains the change of Fe3+ valency.
•
A high remnant polarization of 27 μC/cm2 was obtained in the BiFe0.95Mn0.05O3 thin film.
•
Mn doped BiFeO3 thin films showed an enhanced saturation magnetization than.

Abstract

Mn-doped BiFeO₃ films were prepared by chemical solution deposition method on fluorine doped tin oxide conductive glass via spin-coating technique. XRD pattern reveals the presence of the impurity phase of Bi₂Fe₄O₉ in BiFeO₃ films, while no impurity phase is found in the Mn-doped thin films. XPS spectrum demonstrates the purity of prepared thin films by exhibiting the desired elements alone and it also shows that Mn-doping restrains the change of Fe³⁺ valency. The leakage current result shows that Mn-doping causes the change of conduction mechanism led by the change of microstructure and the restraint of Fe ions valence. BiFe_0.95Mn_0.05O₃ thin film has a good ferroelectric performance with high remnant polarization (P_r) value of 27 μC/cm². Mn doped BiFeO₃ films have stronger saturation magnetization than the BiFeO₃ thin films. UV vis NIR transmittance spectra depicts the optical property, which shows the optical band gap decreases with the concentration of Mn increases.

Introduction

Due to the simultaneous existence of two or more ferroic properties, for instance, ferroelectricity, ferroelasticity and ferromagnetism, multiferroic materials have attracted enormous attention [1,2]. During the last decade, multiferroics have been extensively studied because they can provide various characteristic in response to external electric and/or magnetic fields, which have been expected to be applied to various kinds of electronic devices such as data storage media, multi-state memories and magnetoelectric sensors [[3], [4], [5]]. Several materials such as BiFeO₃ (BFO), BiMnO₃ and some perovskite materials are considered to be common multiferroic materials [6,7]. Single-phase BiFeO₃ exhibits ferromagnetism and ferroelectricity above room temperature, making it an attractive multiferroic material [[8], [9], [10]]. Meanwhile, BFO is also regards as a kind of photocatalytic or photovoltaic material and has been studied extensively because of its relatively narrow band gap [11,12], and the narrow band gap also provides a direction for the application in photocatalysis and photovoltaics. However, the weak multiferroic properties of BFO film restrain its practical applications. The weak multiferroic properties may attribute to non-stoichiometry and defects because Bi is volatile at high temperature [[13], [14], [15]] and the valence of Fe ions is easily changed [16]. Also, it has been certified that the residual magnetic moment generated by spin structure of the Fe³⁺ (B-site) could lead to poor ferromagnetism [2,17].

In order to overcome these problems, a common method of enhancing polarization and magnetization is A-site and/or B-site doping. The substitution of Fe ions (B-site) is an effective way to restrain the variation of the valence of Fe ions, reduce oxygen vacancy and enhance ferromagnetism. Therefore by doping at B-site, the BFO's spiral spin structures can be destroyed to improve its multiferroic properties [18]. As for the selection of doping elements, considering that BiMnO₃ is also a kind of multiferroic material [7]. Mn-doping can inhibit the change of valence of Fe and reduce the vacancy caused by Fe²⁺ [19]. Some investigations [20] have certified that Mn-doping also has certain effects on the optical properties. Hence, the comprehensive effect of Mn-doping on the ferromagnetism, ferroelectricity and optical properties of BFO films needs to be further investigated.

Thus, in this paper, the effects of Mn doping only at the B-site on the properties of BFO films were studied. BiFe_1-xMn_xO₃ (x = 0, 0.03, 0.05 and 0.10) [19] solution were made by chemical solution deposition method, and the films were deposited on fluorine doped tin oxide substrates by spin-coating technique, followed by annealing on a hot plate at 500 °C for 10 min [[21], [22], [23]]. The structure and morphologies varied with the concentration of Mn doping as well as the changes on electrical, magnetic and optical properties of BFO thin films after Mn doping were systematically investigated.

Section snippets

Experimental procedure

BiFe_1-xMn_xO₃ (x = 0, 0.03, 0.05 and 0.10, referred as BFM0, BFM3, BFM5, BFM10, respectively) films were deposited on fluorine doped tin oxide (FTO) substrates by spin-coating technique. Bismuth nitrate pentahydrate Bi(NO₃)₃·5H₂O, iron nitrate nonahydrate Fe(NO₃)₃·9H₂O and manganese acetate tetrahydrate Mn(CH₃COO)₂·4H₂O were used as raw materials for preparing precursor solutions. Bi(NO₃)₃·5H₂O amount is 5% more than the normal composition to make up for the loss of Bi evaporation in annealing

Results and discussion

Fig. 1(a) shows the XRD patterns of BFM0, BFM3, BFM5 and BFM10 films. The diffraction peaks are matched well with those of the distorted perovskite structure. There is no any peak pertaining to secondary or impurity phase in the XRD patterns of thin films doped with Mn, while BFM0 thin film shows a small peak at around 29°, which could be ascribed to the impurity phase of Bi₂Fe₄O₉. With the increase of Mn doping, the diffraction peak becomes weaker, indicating that Mn doping impedes the process

Conclusions

In summary, the Mn-doped BFO films have been successfully deposited on FTO glass substrates. The XRD pattern shows that Mn element is successfully incorporated into the B-site. The AFM image shows that the roughness of the film gradually decreases as the Mn content increase. The effects of Mn-doping on ferroelectric, magnetic, and optical properties have been investigated. BiFe_0.95Mn_0.05O₃ film has good ferroelectric performance with high remnant polarization (P_r) value of 27 μC/cm². M − H

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.

CRediT authorship contribution statement

X.W. Wang: Conceptualization, Writing - review & editing, Supervision. Y.F. Liang: Data curation, Writing - original draft, Visualization. L.Y. Sun: Investigation, Data curation, Writing - review & editing. S.Q. Guo: Investigation, Resources, Writing - original draft. K.S. Venkatesh: Writing - review & editing, Visualization. X.E. Wang: Resources. M.Z. Hou: Writing - review & editing. S.Y. Shang: Writing - review & editing. J. Shang: Writing - review & editing. Y.C. Hu: Writing - review &

Acknowledgments

This work has been supported by the National Natural Science Foundation of China (Nos. 51402091, 61901161, 11847136), the key scientific research foundation in Henan Province (No. 19B430005), the special scientific research foundation in Henan Normal University (No. 20180543, 5101029170307), and the National University Student Innovation Program (No. 20160098).

References (46)

S.U. Lee et al.
Effects of co-substitution on the electrical properties of BiFeO₃ thin films prepared by chemical solution deposition
Appl. Surf. Sci.
(2007)
G. Dong et al.
Charge defects and highly enhanced multiferroic properties in Mn and Cu co-doped BiFeO₃ thin films
Appl. Surf. Sci.
(2014)
X. Yan et al.
Structural, electric and magnetic properties of Dy and Mn co-doped BiFeO₃ thin films
Ceram. Int.
(2015)
W. Zhou et al.
Effects of Sm and Mn co-doping on structural, optical and magnetic properties of BiFeO₃ films prepared by a sol–gel technique
Mater. Lett.
(2015)
N. Dai et al.
A new family of barium-doped Sr₂Fe_1.5Mo_0.5O_6−δ perovskites for application in intermediate temperature solid oxide fuel cells
J. Power Sources
(2014)
T. Yamashita et al.
Analysis of XPS spectra of Fe²⁺ and Fe³⁺ ions in oxide materials
Appl. Surf. Sci.
(2008)
C. Feng et al.
Substrate-dependent ferroelectric and dielectric properties of Mn doped Na_0.5Bi_0.5TiO₃ thin films derived by chemical solution decomposition
J. Alloys Compd.
(2016)
Y. Chen et al.
Enhanced dielectric and piezoelectric properties in Na_0.5Bi_4.5Ti₄O₁₅ ceramics with Pr-doping
Ceram. Int.
(2018)
S. Hussain et al.
Correlation between structure, oxygen content and the multiferroic properties of Sr doped BiFeO₃
J. Alloys Compd.
(2015)
H.B. Sharma et al.
Structural and optical properties of manganese substituted nanocrystalline bismuth ferrite thin films by sol–gel process
J. Alloys Compd.
(2014)

R. Ramesh et al.

Multiferroics: progress and prospects in thin films

Nat. Mater.

(2007)

W. Ye et al.

Structural and multiferroic properties of Bi_0.92−xHo_0.08Ca_xFe_0.97Mn_0.03O₃ thin film

Ceram. Int.

(2015)

H. Sun et al.

Study of multiferroic properties in Bi₅Fe_0.5Co_0.5Ti₃O₁₅ thin films

J. Appl. Phys.

(2012)

Y.C. Huang et al.

Giant enhancement of ferroelectric retention in BiFeO₃ mixed-phase boundary

Adv. Mater.

(2014)

B. Lorenz et al.

Large magnetodielectric effects in orthorhombic HoMnO₃ and YMnO₃

Phys. Rev. B

(2004)

R. Seshadri et al.

Visualizing the role of Bi 6s “Lone Pairs” in the off-center distortion in ferromagnetic BiMnO₃

Chem. Mater.

(2001)

K.G. Yang et al.

Structural, electrical, and magnetic properties of multiferroic Bi_1−xLa_xFe_1−yCo_yO₃ thin films

J. Appl. Phys.

(2010)

W. Ye et al.

Influence of Mn dopants on the structure and multiferroic properties of a Bi_0.90Ho_0.10FeO₃ thin film

RSC Adv.

(2015)

T. Choi et al.

Switchable ferroelectric diode and photovoltaic effect in BiFeO₃

Science

(2009)

F. Gao et al.

Visible-light photocatalytic properties of weak magnetic BiFeO₃ nanoparticles

Adv. Mater.

(2007)

H. Uchida et al.

Crystal structure and ferroelectric properties of rare-earth substituted BiFeO₃ thin films

J. Appl. Phys.

(2006)

S.T. Zhang et al.

Larger polarization and weak ferromagnetism in quenched BiFeO₃ ceramics with a distorted rhombohedral crystal structure

Appl. Phys. Lett.

(2005)

Y.H. Chu et al.

Nanoscale domain controlin multiferroic BiFeO₃ thin films

Adv. Mater.

(2006)

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¹: The four authors contribute equally to this work.

View full text

Effects of Mn doping on ferroelectric, ferromagnetic and optical properties of BiFeO3 thin films

Highlights

Abstract

Introduction

Section snippets

Experimental procedure

Results and discussion

Conclusions

Declaration of competing interest

CRediT authorship contribution statement

Acknowledgments

Appl. Surf. Sci.

Appl. Surf. Sci.

Ceram. Int.

Mater. Lett.

J. Power Sources

Appl. Surf. Sci.

J. Alloys Compd.

Ceram. Int.

J. Alloys Compd.

J. Alloys Compd.

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Nat. Mater.

Structural and multiferroic properties of Bi0.92−xHo0.08CaxFe0.97Mn0.03O3 thin film

Ceram. Int.

Study of multiferroic properties in Bi5Fe0.5Co0.5Ti3O15 thin films

J. Appl. Phys.

Giant enhancement of ferroelectric retention in BiFeO3 mixed-phase boundary

Adv. Mater.

Large magnetodielectric effects in orthorhombic HoMnO3 and YMnO3

Phys. Rev. B

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Structural, electrical, and magnetic properties of multiferroic Bi1−xLaxFe1−yCoyO3 thin films

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Influence of Mn dopants on the structure and multiferroic properties of a Bi0.90Ho0.10FeO3 thin film

RSC Adv.

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Science

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Adv. Mater.

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J. Appl. Phys.

Larger polarization and weak ferromagnetism in quenched BiFeO3 ceramics with a distorted rhombohedral crystal structure

Appl. Phys. Lett.

Nanoscale domain controlin multiferroic BiFeO3 thin films

Adv. Mater.

Effects of Mn doping on ferroelectric, ferromagnetic and optical properties of BiFeO₃ thin films

Structural and multiferroic properties of Bi_0.92−xHo_0.08Ca_xFe_0.97Mn_0.03O₃ thin film

Study of multiferroic properties in Bi₅Fe_0.5Co_0.5Ti₃O₁₅ thin films

Giant enhancement of ferroelectric retention in BiFeO₃ mixed-phase boundary

Large magnetodielectric effects in orthorhombic HoMnO₃ and YMnO₃

Visualizing the role of Bi 6s “Lone Pairs” in the off-center distortion in ferromagnetic BiMnO₃

Structural, electrical, and magnetic properties of multiferroic Bi_1−xLa_xFe_1−yCo_yO₃ thin films

Influence of Mn dopants on the structure and multiferroic properties of a Bi_0.90Ho_0.10FeO₃ thin film

Switchable ferroelectric diode and photovoltaic effect in BiFeO₃

Visible-light photocatalytic properties of weak magnetic BiFeO₃ nanoparticles

Crystal structure and ferroelectric properties of rare-earth substituted BiFeO₃ thin films

Larger polarization and weak ferromagnetism in quenched BiFeO₃ ceramics with a distorted rhombohedral crystal structure

Nanoscale domain controlin multiferroic BiFeO₃ thin films