Preparation and Physical Property of BTO-based Multiferroic Ceramics

doi:10.15541/jim20210212

Abstract

Abstract:

Multiferroic material is one of hot spots in the materials research area which can be widely used in many new functional devices. Barium titanate (BaTiO₃, BTO) has attracted many interests for its multiferroic properties, such as ferroelectricity, high dielectric constant and electro-optical properties at room temperature. The BaTi_0.94(TM_1/2Nb_1/2)_0.06O₃ (TM=Mn/Ni/Co) ceramic samples were prepared by solid state reaction method, and their structure, electrical, magnetic, and optical properties were systematically studied. The crystal structure of all doped samples changes from tetragonal to cubic phase without any hexagonal phase depending on ionic radius. Weakening of Raman scattering peaks of BTO tetragonal phase further proves the phase transition to cubic phase caused by doping. The Curie temperature (T_C) has a dramatic decrease with the dopant as the phase transition from tetragonal phase to cubic phase. Although the ferroelectricity is weakened, it is still existed. The magnetic measurement suggests that Ni-Nb doped sample has the strongest ferromagnetism among different dopants which can be deduced by the F-center exchange (FCE) theory. Furthermore, energy gaps of BaTi_0.94(TM_1/2Nb_1/2)_0.06O₃ are obviously reduced compared to that of BTO, which can be reasonably explained by impurity level and band theory. These results indicate that BTO based multiferroic ceramics with ferroelectric and ferromagnetic coexisting at room temperature can be obtained by B-site co-doping, which can be expected to be widely used in multiferroic functional devices.

Key words: BaTiO₃, ferroelectric, multiferroic, doping

CLC Number:

TQ174

LI Sheng, SONG Guoqiang, ZHANG Yuanyuan, TANG Xiaodong. Preparation and Physical Property of BTO-based Multiferroic Ceramics[J]. Journal of Inorganic Materials, 2022, 37(1): 79-85.

Figures/Tables 7

Fig. 1 XRD patterns (a) of BTO series ceramics and magnified patterns (b) at around 2θ=45°

Fig. 2 Raman scattering spectra of BTO series ceramics

Fig. 3 Temperature dependence of dielectric constant (a-d) and loss (e) of BTO series ceramics in the frequency range from 1 kHz to 1 MHz

Fig. 4 P-E hysteresis loops of BTO series ceramics at room temperature under an electric field of 25 kV/cm

Table 1 Physical parameters in the electric hysteresis loop

Sample	E_C/(kV·cm^-1)	P_r/(μC·cm^-2)	P_s/(μC·cm^-2)
BTO	4.3	13.24	28.7
BTMNO	1.22	5.85	19.1
BTNNO	0.67	0.55	15.5
BTCNO	1.85	6.02	19.9

Fig. 5 Isothermal magnetization of BTO series ceramics at 300 K (a-d) and isothermal magnetization loops after subtracting the paramagnetic contributions of samples (e) Colourful figures are available on website

Fig. 6 Plots of (ahv)2 vs photon energy for estimation of optical band gap energy Colourful figures are available on website

References 37

[1]	DONG S, LIU J M, CHEONG S W, et al. Multiferroic materials and magnetoelectric physics: symmetry, entanglement, excitation, and topology. Advances in Physics, 2015, 64(5/6):519-626. DOI URL
[2]	EERENSTEIN W, MATHUR N D, SCOTT J F. Multiferroic and magnetoelectric materials. Nature, 2006, 442(7104):759-765. DOI URL
[3]	KIMURA T, GOTO T, SHINTANI H, et al. Magnetic control of ferroelectric polarization. Nature, 2003, 426(6962):55-58. DOI URL
[4]	CORASANITI M, BARONE P, NUCARA A, et al. Electronic bands and optical conductivity of the Dzyaloshinsky-Moriya multiferroic Ba₂CuGe₂O₇. Physical Review B, 2017, 96(8):085115. DOI URL
[5]	CHEN L, JIA Y, ZHAO J, et al. Strong piezoelectric-catalysis in barium titanate/carbon hybrid nanocomposites for dye wastewater decomposition. Journal of Colloid & Interface Science, 2021, 586:758-765.
[6]	XU X, WU Z, XIAO L, et al. Strong pieo-electro-chemical effect of piezoelectric BaTiO₃ nanofibers for vibration-catalysis. Journal of Alloys and Compounds, 2018, 762:915-921. DOI URL
[7]	XIA Y, JIA Y, QIAN W, et al. Pyroelectrically induced pyro- electro-chemical catalytic activity of BaTiO₃ nanofibers under room-temperature cold-hot cycle excitations. Metals, 2017, 7(4):122. DOI URL
[8]	WANG K F, LIU J M, REN Z F. Multiferroicity: the coupling between magnetic and polarization orders. Advances in Physics, 2009, 58(4):321-448. DOI URL
[9]	BENEDEK N A, FENNIE C J. Why are there so few perovskite ferroelectrics? The Journal of Physical Chemistry C, 2013, 117(26):13339-13349. DOI URL
[10]	HILL N A. Why are there so few magnetic ferroelectrics? The Journal of Physical Chemistry B, 2000, 104(29):6694-6709. DOI URL
[11]	HIROYUKI N, KATAYAMA-YOSHIDA H. Theoretical prediction of magnetic properties of Ba(Ti_1-_xM_x)O₃ (M=Sc,V,Cr,Mn,Fe,Co, Ni,Cu). Japanese Journal of Applied Physics, 2001, 40(Part 2, 12B):L1355-L1358. DOI URL
[12]	SONG C, WANG C, LIU X, et al. Room temperature ferromagnetism in cobalt-doped LiNbO₃ single crystalline films. Crystal Growth & Design, 2009, 9(2):1235-1239. DOI URL
[13]	REN Z, XU G, WEI X, et al. Room-temperature ferromagnetism in Fe-doped PbTiO₃ nanocrystals. Applied Physics Letters, 2007, 91(6):063106. DOI URL
[14]	KUMAR M, YADAV K L. Observation of room temperature magnetoelectric coupling in a Ni substituted Pb_1-_xNi_xTiO₃ system. Journal of Applied Physics, 2007, 102(7):076107. DOI URL
[15]	DANG N V, THE-LONG P, THANH T D, et al. Structural phase separation and optical and magnetic properties of BaTi₁-_xMn_xO₃ multiferroics. Journal of Applied Physics, 2012, 111(11):113913. DOI URL
[16]	ZHOU L, ZHANG Y, LI S, et al. Fe doping effect on the structural, ferroelectric and magnetic properties of polycrystalline BaTi₁-_xFe_xO₃ ceramics. Journal of Materials Science: Materials in Electronics, 2020, 31(17):14487-14493. DOI URL
[17]	RUBAVATHI P E, VENKIDU L, BABU M V G, et al. Structure, morphology and magnetodielectric investigations of BaTi₁-_xFe_xO₃-_δ ceramics. Journal of Materials Science-Materials in Electronics, 2019, 30(6):5706-5717. DOI URL
[18]	RANI A, KOLTE J, VADLA S S, et al. Structural, electrical, magnetic and magnetoelectric properties of Fe doped BaTiO₃ ceramics. Ceramics International, 2016, 42(7):8010-8016. DOI URL
[19]	GHEORGHIU F, CIOMAGA C E, SIMENAS M, et al. Preparation and functional characterization of magnetoelectric Ba(Ti₁-_xFe_x)O₃-_x_/2 ceramics. Application for a miniaturized resonator antenna. Ceramics International, 2018, 44(17):20862-20870. DOI URL
[20]	PHAN T L, THANG P D, HO T A, et al. et al. Local geometric and electronic structures and origin of magnetism in Co-doped BaTiO₃ multiferroics. Journal of Applied Physics, 2015, 117(17): 17D904.
[21]	PHONG P T, HUY B T, LEE Y I, et al. Polymorphs and dielectric properties of BaTi₁-_xNi_xO₃. Journal of Alloys and Compounds, 2014, 583:237-243. DOI URL
[22]	DAS S, GHARA S, MAHADEVAN P, et al. Designing a lower band gap bulk ferroelectric material with a sizable polarization at room temperature. ACS Energy Letters, 2018, 3(5):1176-1182. DOI URL
[23]	ZHENG D, DENG H, SI S, et al. Modified structural, optical, magnetic and ferroelectric properties in (1-x)BaTiO₃- xBaCo_0.5Nb_0.5O₃-_δ ceramics. Ceramics International, 2020, 46(5):6073-6078. DOI URL
[24]	N V, DUNG N T, PHONG P T, et al. Effect of Fe³⁺ substitution on structural, optical and magnetic properties of barium titanate ceramics. Physica B: Condensed Matter, 2015, 457:103-107. DOI URL
[25]	ZHENG D, DENG H, PAN Y, et al. Modified multiferroic properties in narrow bandgap (1-x)BaTiO₃-xBaNb_1/3Cr_2/3O₃-_δ ceramics. Ceramics International, 2020, 46(17):26823-26828. DOI URL
[26]	DAS S K, MISHRA R N, ROUL B K. Magnetic and ferroelectric properties of Ni doped BaTiO₃. Solid State Communications, 2014, 191:19-24. DOI URL
[27]	VENKATESWARAN U D, NAIK V M, NAIK R. High-pressure Raman studies of polycrystalline BaTiO₃. Physical Review B, 1998, 58(21):14256-14260. DOI URL
[28]	ROBINS L H, KAISER D L, ROTTER L D, et al. Investigation of the structure of barium titanate thin films by Raman spectroscopy. Journal of Applied Physics, 1994, 76(11):7487-7498. DOI URL
[29]	POKORNÝ J, PASHA U M, BEN L, et al. Use of Raman spectroscopy to determine the site occupancy of dopants in BaTiO₃. Journal of Applied Physics, 2011, 109(11):114110. DOI URL
[30]	ZAYTSEVA I V, PUGACHEV A M, OKOTRUB K A, et al. Residual mechanical stresses in pressure treated BaTiO₃ powder. Ceramics International, 2019, 45(9):12455-12460. DOI URL
[31]	SHUAI Y, ZHOU S, BÜRGER D, et al. Decisive role of oxygen vacancy in ferroelectric versus ferromagnetic Mn-doped BaTiO₃ thin films. Journal of Applied Physics, 2011, 109(8):084105. DOI URL
[32]	COEY J M D, VENKATESAN M, FITZGERALD C B. Donor impurity band exchange in dilute ferromagnetic oxides. Nature Materials, 2005, 4(2):173-179. DOI URL
[33]	COEY J M D, DOUVALIS A P, FITZGERALD C B, et al. Ferromagnetism in Fe-doped SnO₂ thin films. Applied Physics Letters, 2004, 84(8):1332-1334. DOI URL
[34]	MOSTARI M S, HAQUE M J, RAHMAN ANKUR S, et al. Effect of mono-dopants (Mg²⁺) and co-dopants (Mg²⁺, Zr⁴⁺) on the dielectric, ferroelectric and optical properties of BaTiO₃ ceramics. Materials Research Express, 2020, 7(6):066302. DOI URL
[35]	WENG B, XIAO Z, MENG W, et al. Bandgap engineering of barium bismuth niobate double perovskite for photoelectronchemical water oxidation. Advanced Energy Materals, 2017, 7(9):1602260.
[36]	YANG F, YANG L, AI C, et al. Tailoring bandgap of perovskite BaTiO₃ by transition metals Co-doping for visible-light photoelectrical applications: a first-principles study. Nanomaterials, 2018, 8(7):455. DOI URL
[37]	YIN J, ZOU Z, YE J. A novel series of the new visible-light- driven photocatalysts MCo_1/3Nb_2/3O₃ (M=Ca, Sr, and Ba) with special electronic structures. The Journal of Physical Chemistry B, 2003, 107(21):4936-4941. DOI URL