Progress of Relaxor Multiferroic Materials

doi:10.15541/jim20160644

Abstract

Abstract:

The multiferroic material, which shows the coexistences of multi ferroic orders (ferroelectricity, ferromagnetism or ferroelasticity), can realize the mutual control of the electric and magnetic signals, and becomes one of the hottest research topics. The long-range ferroelectric or ferromagnetic order may be broken in compositionally disordered systems. In this situation, it is posssible that materials display relaxor behavior. Multiferroic materials possessiong at least one ferroic relaxor character can be named as relaxor multiferroics. The polarization (or magnetization) is very sensitive to the applied electric field (or magnetic field). Besides, the magnetoelectric coupling effect of relaxor multiferroics is different from that of multiferroics with long ferroic orders. In this paper, the most recent and important theoretical and experimental advances in this new research field are reviewed. Firstly, basic physical concepts of the relaxor ferroic orders and the different mechanism of the magnetoelectric coupling effect on materials are introduced with the coexistence of relaxor ferroelectric ordering and relaxor magnetic ordering. Then, the recent researches on two sorts of the relaxor multiferroics, including perovskite (PbB₁B₂O₃based and BiFeO₃ based) and non-perovskite (Bi-layered based and improperly ferroelectric based) structural materials, are reviewed. Finally, the further development of relaxor multiferroics is prospected.

Key words: relaxor behavior, multiferroics, magnetoelectric coupling effect, nano memory device

CLC Number:

TQ174

WEI Yong-Xing, JIN Chang-Qing, ZENG Yi-Ming. Progress of Relaxor Multiferroic Materials[J]. Journal of Inorganic Materials, 2017, 32(10): 1009-1017.

Figures/Tables 10

Fig. 1 Temperature dependence of dielectric constant for classical relaxor ferroelectrics Pb(Nb2/3Mg1/3)O3 at various frequencies[13]The classical relaxor ferroelectrics display the broad, frequency-dependent dielectric anomalies. The value of the maximum dielectric constant εm could reach above 10,000. The relation between the Tm and frequency could be described by V-F function

Fig. 2 Schematic representation of paramagnetic state, long- ranged magnetic state (ferromagnetic, ferrimagnetic, antiferromagnetic) and spin glass state

Table 1 Polar and magnetic orderings of the PbB1B2O3 based multiferroic materials

Compositions	Polar ordering	Magnetic ordering
PbFe_2/3W_1/3O₃ crystals^[31]	Ferroelectric relaxor T_m= 210 K @0.1 MHz T_f = 164 K	Anti-ferromagnetic T_N = 350 K Magnetic glass state T_g= 10 K
PbFe_0.5Nb_0.5O₃ceramics^{[23, 29]}	Ferroelectric T_m=373 K	Anti-ferromagnetic T_N = 153 K Magnetic glass state T_g= 10.6 K
PbFe_0.5Ta_0.5O₃ceramics^{[27, 30]}	Ferroelectric T_m = 259 K	Anti-ferromagnetic T_N = 153 K Magnetic glass state T_g< 10 K
0.8PbFe_1/2Nb_1/2O₃-0.2PbMg_1/2W_1/2O₃ceramics^[32]	Ferroelectric relaxor T_m = 280 K @0.1 MHz T_f= 245 K	Magnetic glass state T_g= 25K
Pb(Fe_0.66W_0.33)_0.8 Ti_0.2O₃ thin films^[33]	Ferroelectric relaxor T_m = 350 K @10 kHz T_f = 238 K	Ferrimagnetic
Pb(Fe_0.66W_0.33)_0.2 (Zr_0.53Ti_0.47)_0.8O₃thin film^[36]	Ferroelectric relaxor T_m < 600 K @1 MHz	Ferrimagnetic
Pb(Zr_0.53Ti_0.47)_0.60(Fe_0.5Ta₀.₅)_0.4O₃ thin films^[37]	Ferroelectric relaxor T_m = 390 K @1 MHz T_f= 305 K	Ferrimagnetic

Table 2 Polar and magnetic orderings of the BiFeO3 based multiferroic materials

Compositions	Polar ordering	Magnetic ordering
Bi(Fe_0.5Mn_0.5)O₃thin films^[45]	Ferroelectric relaxor T_m = 440 K @1 MHz T_f = 314 K	Magnetic glass state T_f2=122 K
0.65BiFeO₃- 0.35BaTiO₃ceramics^[47]	Ferroelectric relaxor T_m= 687 K @1 MHz	Ferrimagnetic
0.67BiFeO₃- 0.33BaTiO₃ single crystal^[50]	Ferroelectric relaxor T_m = 650 K @0.1 MHz	Magnetic glass state
0.5Bi(Fe_0.5La_0.5)O₃- 0.5PbTiO₃ ceramics^[54]	Ferroelectric relaxor T_m = 520 K @0.1 MHz	Ferrimagnetic
0.6BiFeO₃- 0.4Bi_1/2K_1/2TiO₃ceramics^[55-56]	Ferroelectric relaxor T_m= 703 K @0.1 MHz	Ferrimagnetic T_N< 500 K
0.4BiFe_0.9Co_0.1O₃- 0.6Bi_1/2K_1/2TiO₃ceramics^[59]	Ferroelectric relaxor T_m= 693 K @0.1 MHz T_f < 573 K	Ferrimagnetic T_N= 670 K

Fig. 3 Schematic representation of Fe3+ spins arrangement for PbFe2/3W1/3O3, The frustrated Fe3+ spins appear in AFM sublattices[31]

Fig. 4 (a) The P-E loops and (b) the real and imaginary part of dielectric constant as a function of frequencies with various magnetic fields for Pb(Fe0.66 W0.33)0.2(Zr0.53Ti0.47)0.8O3[35]Increase of the magnetic field H leads to decrease in Pr. Pr is nearly zero when H reaches 0.5 T. This effect disappears after magnetic field being removed. Correspondingly, the anomaly peak of the imaginary part for dielectric constant shifts to the low frequency side with H increasing, which reveals the increase of the relaxation time

Fig. 5 Relaxor multiferroics for multi-states memory device

Fig. 6 (a) Contour plots of the diffuse intensities at 600 K around the (112) reflection and (b) M-H loops at various temperatures for the single crystal of 0.67BiFeO3-0.33BaTiO3[50] The crystal shows the strong nuclear diffuse scattering, with a correlation length of 8 nm. It demonstrates the existence of the PNR. The M-H loops display the character of super-paramagnetism. The super-paramagnetism could be related to the short magnetic state. The fitting of Langevin function reveals the size of the short magnetic state is in the range of 8-9 nm

Fig. 7 In situ PFM under magnetic field experiments[60]The polarization switches obviously in the regions marked by blue and red rectangles

Fig. 8 (a) Crystal structure, (b) STEM pattern and (c) schematic illustration of atom position information of Bi5Ti3FeO15[68-69]The crystal structure is obtained from ref [68]. Between the two [Bi2O2]2- layers, there are four Ti(Fe)O6 octahedra. The STEM measurement demonstrates Ti/Fe atoms shift from ideal position along [110]

References 75

[1]	EERENSTEIN W, MATHUR N D, SCOTT J F.Multiferroic and magnetoelectric materials.Nature, 2006, 442(44): 759-765.
[2]	SCOTT J F.Data storage. Multiferroic memories.Nature, 2007, 6(4): 256-257.
[3]	SPALDIN N A, FIEBIG M.The renaissance of magnetoelectric multiferroics.Science, 2005, 309(5733): 391-392.
[4]	NAN C W.Research progress and future directions of multiferroic materials.Scientia Sinica Technologica, 2015, 45(4): 339-357.
[5]	WANG J, NEATON J B, ZHENG H, et al.Epitaxial BiFeO3 multiferroic thin film heterostructures.Science, 2003, 299(5673): 1719-1722.
[6]	KLMURA T, GOTO T, SHINTAL H, et al.Magnetic control of ferroelectric polarization.Nature, 2003, 426(6962): 55-58.
[7]	LIU J M, NAN C W.Decade of multiferroic researches.Physics, 2014, 43(02): 88-98.
[8]	WANG K F, LIU J M, WANG Y.Single phase multiferroic materials- coupling and adjusting between polar and magnetic order parameters.Chin. Sci. Bull, 2008, 53(10): 1098-1135.
[9]	CHI Z H, JIN C Q.Recent advances in single-phase magnetoelectric multiferroics.Prog. Phys., 2007, 27(2): 225-238.
[10]	DUAN C G.Progress in the study of magnetoelectric effect.Prog. Phys., 2009, 29(3): 215-238.
[11]	DONG S, LIU J M.Multiferroic materials: past, present and future.Physics, 2010, 39(10): 714-715.
[12]	PIRC R, BLINC R, SCOTT J F.Mesoscopic model of a system possessing both relaxor ferroelectric and relaxor ferromagnetic properties.Phys. Rev. B, 2009, 79(21): 214114.
[13]	BOKOV A A, YE Z G.Recent progress in relaxor ferroelectrics with perovskite structure.J. Mater. Sci., 2006, 41(1): 31-52.
[14]	YAO X, CHEN Z L, CROSS L E.Polarization and depolarization behavior of hot pressed lead lanthanum zirconate titanate ceramics,J. Appl. Phys., 1983, 54(6): 3399-3403.
[15]	CROSS L E.Relaxor ferroelectrics.Ferroelectrics, 1987, 76(1): 241-267.
[16]	SETTER N, CROSS L E.The contribution of structural disorder to diffuse phase transitions in ferroelectrics.J. Mater. Sci., 1980, 15(10): 2478-2482.
[17]	TAGANTSEV A K.Vogel-Fulcher relationship for the dielectric permittivity of relaxor ferroelectrics.Phys. Rev. Lett., 1994, 72(7): 1110-1113.
[18]	KIMURA T, TOMIOKA Y, KUMAI R, et al.Diffuse phase separation and phase transition in Cr-doped Nd1/2Ca1/2MnO3: A relaxor ferromagnet.Phys. Rev. Lett., 1999, 83(19): 3940-3943.
[19]	OKIMOTO Y, OGIMOTO Y, Matsubara M, et al.Direct observation of photoinduced magnetization in a relaxor ferromagnet.Appl. Phys. Lett., 2002, 80(6): 1031-1033.
[20]	KAMZIN A S, BOKOV V A.Mössbauer studies of PbFe2/3W1/3O3 multiferroics.Phys. Solid State, 2013, 55(6): 1191-1197.
[21]	MITOSERIU L, CARNASCIALI M M, PIAGGIO P, et al.Evidence of the relaxor-paraelectric phase transition in Pb(Fe2/3 W1/3)O3 ceramics.Appl. Phys. Lett., 2002, 81(26): 5006-5008.
[22]	YE Z, TODA K, SATO M, et al.Synthesis, structure and properties of the magnetic relaxor ferroelectric Pb(Fe2/3W1/3)O3 [PFW].J. Korean Phys. Soc., 1998, 32(3): S1028-S1031 .
[23]	PAVLENKO A V, TURIKA A V, Reznichenko L A, et al.Dielectric relaxation in the PbFe1/2Nb1/2O3 ceramics.Phys. Solid State, 2011, 53(9): 1872-1875.
[24]	CARPENTER M A, SCHIEMER J A, LASCU I, et al.Elastic and magnetoelastic relaxation behaviour of multiferroic (ferromagnetic + ferroelectric + ferroelastic) Pb(Fe0.5Nb0.5)O3 perovskite.J. Phys.: Condens. Matter, 2015, 27(28): 285901.
[25]	BOCHENEK D, GUZDEK P.Ferroelectric and magnetic properties of ferroelectromagnetic PbFe1/2Nb1/2O3 type ceramics.J. Magn. Magn. Mater., 2011, 323(3): 369-374.
[26]	LAMPIS N, SCIAU P, LEHMANN A G.Rietveld refinements of the paraelectric and ferroelectric structures of PbFe0.5Ta0.5O3.J. Phys.: Condens. Matter, 2000, 12(17): 2367-2378.
[27]	DULKIN E, GRUSZKA I, KANIA A, et al.Electric field dependences of Curie and Néel phase transition temperatures in magnetoelectric relaxor multiferroic Pb(Fe0.5Ta0.5)O3 crystals seen via acoustic emission.Phys. Status Solidi B, 2016, 253(4): 738-743.
[28]	FALQUI A, LAMPIS N, GEDDOLEHMANN A, et al.Low- temperature magnetic behavior of perovskite compounds PbFe1/2Ta1/2O3 and PbFe1/2Nb1/2O3.J. Phys. Chem. B, 2005, 109(48): 22967-22970.
[29]	KLEEMANN W, SHVARTSMAN V V, BORISOV P, et al.Coexistence of antiferromagnetic and spin cluster glass order in the magnetoelectric relaxor multiferroic PbFe0.5Nb0.5O3.Phys. Rev. Lett., 2010, 105(25): 257202.
[30]	CHILLAL S, GVASALIYA S N, ZHELUDEV A, et al.Magnetic short-and long-range order in PbFe0.5Ta0.5O3.Phys. Rev. B, 2014, 89(17): 174418.
[31]	CHEN L, BOKOV A A, ZHU W M, et al.Magnetoelectric relaxor and reentrant behaviours in multiferroic Pb(Fe2/3W1/3)O3 crystal.Sci. Rep., 2016, 6: 22327.
[32]	LEVSTIK A, BOBNAR V, FILIPIČ C, et al.Magnetoelectric relaxor.Appl. Phys. Lett., 2007, 91(1): 012905.
[33]	KUMAR A, RIVERA I, KATIYAR R S, et al.Multiferroic Pb(Fe0.66W0.33)0.80Ti0.20O3 thin films: a room-temperature relaxor ferroelectric and weak ferromagnetic.Appl. Phys. Lett., 2008, 92(13): 132913.
[34]	CHENG Z X, WANG X L, ALVAREV G, et al. Magnetic glassy behavior in ferroelectric relaxor type solid solutions: magnetoelectric relaxor. J. Appl. Phys., 2009, 105(7): 07D902.
[35]	KUMAR A, SHARMA G L, KATIYAR R S, et al.Magnetic control of large room-temperature polarization.J. Phys.: Condens. Matter, 2009, 21(38): 382204.
[36]	KUMAR A, KATIYAR R S, SCOTT J F, et al.Fabrication and characterization of the multiferroic birelaxor lead-iron-tungstate/ lead-zirconate-titanate.J. Appl. Phys., 2010, 108(6): 064105.
[37]	SANCHEZ D A, KUMAR A, ORTEGA N, et al.Near-room temperature relaxor multiferroic. Appl. Phys. Lett., 2010, 97(20): 202910.
[38]	KEMPA M, KAMBA S, SAVINOV M, et al.Bulk dielectric and magnetic properties of PFW? PZT ceramics: absence of magnetically switched-off polarization.J. Phys.: Condens. Matter, 2010, 22(44): 445902.
[39]	CATALAN G, SCOTT J F.Physics and application of bismuth ferrite.Adv. Mater., 2009, 21: 2463-2485.
[40]	PALEWICZ A, PRZENIOSLO R, SOSNOWSKA I, et al.Atomic displacements in BiFeO3 as a function of temperature: neutron diffraction study. Acta Crystallogr. B, 2007, 63(4): 537-544.
[41]	NEATON J, EDERER C, WAGHMARE U, et al.First-principles study of spontaneous polarization in multiferroic BiFeO3.Phys. Rev. B, 2005, 71(1): 014113.
[42]	LEBEUGLE D, COLSON D, FORGET A, et al.Room-temperature coexistence of large electric polarization and magnetic order in BiFeO3 single crystals.Phys. Rev. B, 2007, 76(2): 024116.
[43]	ZHANG ST, LU M H, WU D, et al.Larger polarization and weak ferromagnetism in quenched BiFeO3 ceramics with a distorted rhombohedral crystal structure.Appl. Phys. Lett, 2005, 87(26): 262907.
[44]	ARNOLD D C, KNIGHT K S, CATALAN G, et al.The β-to-γ transition in BiFeO3: a powder neutron diffraction study.Adv. Fun. Mater., 2010, 20(13): 2116-2123.
[45]	MIAO J, ZHANG X, ZHAN Q, et al.Bi-relaxation behaviors in epitaxial multiferroic double-perovskite BiFe0.5Mn0.5O3/CaRuO3 heterostructures.Appl. Phys. Lett., 2011, 99(6): 062905.
[46]	WEI Y X, WANG X T, ZHU J T, et al.Dielectric, ferroelectric and piezoelectric properties of BiFeO3-BaTiO3 ceramics.J. Am. Ceram. Soc., 2013, 96(10): 3163-3168.
[47]	WEI Y X, WANG X T, JIA J J, et al.Multiferroic and piezoelectric properties of 0.65BiFeO3-0.35BaTiO3 ceramic with pseudo-cubic symmetry.Ceram. Int., 2013, 38(4): 3499-3502.
[48]	VERMA K C, KOTNALA R K.Multiferroic magnetoelectric coupling and relaxor ferroelectric behavior in 0.7BiFeO3- 0.3BaTiO3 nanocrystals.Solid State Commun., 2011, 151(13): 920-923.
[49]	OZAKI T, KITAGAWA S, NISHIHARA S, et al.Ferroelectric properties and nano-scaled domain structures in (1-x)BiFeO3- xBaTiO3 (0.33 < x < 0.50).Ferroelectrics, 2009, 385: 155-161.
[50]	SODA M, MATSUURA M, WAKABAYASHI W, et al.Superparamagnetism induced by polar nanoregions in relaxor ferroelectric (1-x)BiFeO3-xBaTiO3. J. Phys. Soc. Jpn., 2011, 80(4): 043705.
[51]	BHATTACHAEJEE S, TRIPATHI S, PANDEY D.Morphotropic phase boundary in (1-x)BiFeO3-xPbTiO3: phase coexistence region and unusually large tetragonality.Appl. Phys. Lett., 2007, 91(4): 042903.
[52]	ZHU W M, GUO H Y, YE Z G.Structural and magnetic characterization of multiferroic (BiFeO3)(1-x)(PbTiO3)x solid solutions.Phys. Rev. B, 2008, 78(1): 014401.
[53]	AMORÍN H, CORREAS C, RAMOS P, et al. Very high remnant polarization and phase-change electromechanical response of BiFeO3-PbTiO3 at the multiferroic morphotropic phase boundary.Appl. Phys. Lett., 2012, 101(17): 172908.
[54]	SINGH A, GUPTA A, CHATTERJEE R.Enhanced magnetoelectric coefficient(α) in the modified BiFeO3-PbTiO3 system with large La substitution. Appl. Phys. Lett., 2008, 93(2): 022902.
[55]	MATSUO H, NOGUCHI Y, MIYAYAMA M, et al.Structural and piezoelectric properties of high-density (Bi0.5K0.5)TiO3-BiFeO3 ceramics.J. Appl. Phys., 2010, 108(10): 104103.
[56]	BENNETT J, BELL A J, STEVENSON T, et al.Multiferroic properties of BiFeO3-(K0.5Bi0.5)TiO3 ceramics.Mater. Lett., 2013, 94(3): 172-175.
[57]	MOROZOV M I, EINARSRUD M, GRANDE T.Polarization and strain response in Bi0.5K0.5TiO3-BiFeO3 ceramics.Appl. Phys. Lett., 2012, 101(25): 252904.
[58]	DORCET V, MARCHET P, TROLLIARD G, et al.Structural and dielectric studies of the Na0.5Bi0.5TiO3-BiFeO3 system.J. Eur. Ceram. Soc., 2007, 27(13/14/15): 4371-4374.
[59]	RAMANA E V, SURYANARAYANA S V, SANKARAM T B, et al.Synthesis and magnetoelectric studies on Na0.5Bi0.5TiO3-BiFeO3 solid solution ceramics.Solid State Sci., 2010, 12(5): 956-962.
[60]	HENRICHS L F, CESPEDES O, BENNETT J, et al.Multiferroic clusters: a new perspective for relaxor-type room-temperature multiferroics.Adv. Fun. Mater., 2016, 26(13): 2111-2121.
[61]	SHVARTSMAN V V, BEDANTA S, BORISOV P, et al.SrMnTiO3: a magnetoelectric multiglass.Phys. Rev. Lett., 2008, 101(16): 165704.
[62]	MULLER K A, BURKARD H.SrTiO3: an intrinsic quantum paraelectric below 4 K.Phys. Rev. B, 1979, 19(7): 3593-3602.
[63]	BEDNORZ J G, MULLER K A.Sr1-xCaxTiO3: an XY quantum ferroelectric with transitions to randomness. Phys. Rev. Lett., 1984, 52(25): 2289-2292.
[64]	TKACH A, VILARINHO P M, KHOLKIN A L.Polar behavior in Mn- doped SrTiO3 ceramics.Appl. Phys. Lett., 2005, 86(17): 172902.
[65]	TKACH A, VILARINHO P M, KHOLKIN A L, et al.Structure- microstructure-dielectric tunability relationship in Mn-doped strontium titanate ceramics.Acta Mater., 2005, 53(19): 5061-5069.
[66]	LI J B, HUANG Y P, RAO G H, et al.Ferroelectric transition of Aurivillius compounds Bi5Ti3FeO15 and Bi6Ti3Fe2O18.Appl. Phys. Lett., 2010, 96(22): 222903.
[67]	BAI W, YIN W B, YANG J, et al.Cryogenic temperature relaxor-like dielectric responses and magnetodielectric coupling in Aurivillius Bi5Ti3FeO15 multiferroic thin films.J. Appl. Phys., 2014, 116(8): 084103.
[68]	HERVOCHES C H, SNEDDEN A, RIGGS R, et al.Structural behavior of the four-layer Aurivillius-phase ferroelectrics SrBi4Ti4O15 and Bi5T i3FeO15. J. Solid State Chem., 2002, 164(2): 280-291.
[69]	ZHAO H Y, KIMURA H, CHENG Z X, et al.Large magnetoelectric coupling in magnetically short-range ordered Bi5Ti3FeO15 film.Sci. Rep., 2014, 4: 5255.
[70]	HEMBERGER J, LUNKENHEIMER P, FICHTL R, et al.Relaxor ferroelectricity and colossal magnetocapacitive coupling in ferromagnetic CdCr2S4.Nature, 2005, 434(7031): 364-367.
[71]	CATALAN G, SCOTT J F.Magnetoelectrics: is CdCr2S4 a multiferroic relaxor?Nature, 2007, 448(7156): E4-E5.
[72]	WALZ F.The Verwey transition—a topical review.J. Phys.: Condens. Matter, 2002, 14(12): R285-R340.
[73]	KATO K, IIDA S, YANAI K, et al. Ferrimagnetic ferroelectricity of Fe3O4. J. Magn. Magn. Mater., 1983, 31-34(6): 783-784.
[74]	ZIESE M, ESQUINAZI P D, PANTEL D, et al.Magnetite (Fe3O4): a new variant of relaxor multiferroic? J. Phys.: Condens. Matter, 2012, 24(8): 086007.
[75]	FIER I, WALMSLEY L, SOUZA J A.Relaxor behavior in multiferroic BiMn2O5 ceramics.J. Appl. Phys., 2011, 110(8): 084101.