多铁材料SmFe_(1-x)Cr_xO_3陶瓷的介电特性及磁相变的研究
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摘要
采用溶胶-凝胶法制备SmFe_(1-x)Cr_xO_3(x=0～0.3)样品,研究Cr~(3+)掺杂对SmFeO_3的晶体结构、介电特性及磁相变温度的影响。研究表明,所有样品的主衍射峰与SmFeO_3标准图谱相吻合且具有良好的晶体结构,Cr~(3+)掺杂使其晶胞体积收缩,导致主衍射峰向衍射角(θ)较大的方向移动。SmFeO_3的介电常数(ε_r)随着掺杂量(x)的增加逐渐减小,介电损耗(tanδ)随着Cr~(3+)的增加而增大,介电常数(ε_r)随频率(f)和掺杂量(x)的增加而逐渐减小的原因是由IBLC微观机制和偶极子取向极化机制两者共同作用的结果,其介电损耗主要是电导电流产生的损耗起主导作用,并发现SmFe_(1-x)Cr_xO_3的介电损耗峰随掺杂量的增加向高频方向迁移。SmFeO_3的蜂腰状M-H随着Cr~(3+)的掺杂而消失且磁性也有所减弱,其自旋重组相变温度(T_(SR))和反铁磁相变温度(T_N)随着Cr~(3+)的增加由原来的462,687 K降低到428和536 K。这主要是Cr~(3+)掺杂使SmFeO_3晶格发生畸变,形成Fe~(3+)-O~(2-)-Cr~(3+)磁交换作用,破坏了原有Fe~(3+)-O~(2-)-Fe~(3+)反铁磁有序排列,降低了其G型反铁磁结构的稳定性,在宏观上表现为其铁磁性的减弱和磁相变温度T_(SR)和T_N的降低,进一步探讨了Cr~(3+)掺杂对SFO的介电性及铁磁性影响的微观机理,使其在自旋电子器件、磁制冷领域及磁性开关器件等方面的应用成为可能。
Sm_(1-x)Cr_xFeO_3(x=0-0.3) ceramics were prepared by the sol-gel method. Effects of Cr doping on the crystal structure, dielectric properties and high temperature magnetic phase transitions of SFO were investigated. XRD pattern analysis shows that the main diffraction peaks of all the samples were agree with the standard SFO spectra and had a fine crystal structure. Cr~(3+) doping resulted in the cell volume to shrink, causing its main diffraction peak to move in the direction of the larger diffraction angle(θ). The dielectric constant(ε_r) and dielectric loss(tanδ) of SmFeO_3 gradually decreased with the increase of Cr~(3+). The variation of ε_r with f and x was mainly the result of both the IBLC microscopic mechanism and the dipole oriented polarization mechanism, and the dielectric loss(tanδ) was mainly caused by the electric conduction current. And found that the dielectric loss peak of SmFe_(1-x)Cr_xO_3 migrated to the high frequency direction with the increase of doping amount. The M-H of SmFeO_3 at room temperature showed a butterfly-shaped hysteresis loop. The butterfly-shaped hysteresis loop disappeared with the increase of x and the magnetic properties also gradually weakened. In a M-T relationship with an applied magnetic field of 79 600 A/m, T_(SR) and T_N decreased from 462 and 687 K to 428 and 536 K with increasing x, respectively. This was mainly due to Cr~(3+) doping to distort the lattice of SmFeO_3, forming Fe~(3+)-O~(2-)-Cr~(3+) exchange, destroying the antiferromagnetic ordering of Fe~(3+)-O~(2-)-Fe~(3+) and leading to the weakening of the stability of the G-type antiferromagnetic structure of SFO. Macroscopically, the ferromagnetism of SFO decreased and the magnetic transition temperatures T_(SR) and T_N decreased.
Sm_(1-x)Cr_xFeO_3(x=0-0.3) ceramics were prepared by the sol-gel method. Effects of Cr doping on the crystal structure, dielectric properties and high temperature magnetic phase transitions of SFO were investigated. XRD pattern analysis shows that the main diffraction peaks of all the samples were agree with the standard SFO spectra and had a fine crystal structure. Cr~(3+) doping resulted in the cell volume to shrink, causing its main diffraction peak to move in the direction of the larger diffraction angle(θ). The dielectric constant(ε_r) and dielectric loss(tanδ) of SmFeO_3 gradually decreased with the increase of Cr~(3+). The variation of ε_r with f and x was mainly the result of both the IBLC microscopic mechanism and the dipole oriented polarization mechanism, and the dielectric loss(tanδ) was mainly caused by the electric conduction current. And found that the dielectric loss peak of SmFe_(1-x)Cr_xO_3 migrated to the high frequency direction with the increase of doping amount. The M-H of SmFeO_3 at room temperature showed a butterfly-shaped hysteresis loop. The butterfly-shaped hysteresis loop disappeared with the increase of x and the magnetic properties also gradually weakened. In a M-T relationship with an applied magnetic field of 79 600 A/m, T_(SR) and T_N decreased from 462 and 687 K to 428 and 536 K with increasing x, respectively. This was mainly due to Cr~(3+) doping to distort the lattice of SmFeO_3, forming Fe~(3+)-O~(2-)-Cr~(3+) exchange, destroying the antiferromagnetic ordering of Fe~(3+)-O~(2-)-Fe~(3+) and leading to the weakening of the stability of the G-type antiferromagnetic structure of SFO. Macroscopically, the ferromagnetism of SFO decreased and the magnetic transition temperatures T_(SR) and T_N decreased.
引文
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[25] Babu P R,Bhaumik I,Gupta P K.Growth,mechanical,and magnetic study of SmFeO3 single crystal grown by optical floating zone technique[J].Journal of Alloys and Compounds,2016,676:313-319.
[26] Zhang C Y,Shang M Y,Feng S H.Multiferroicity in SmFeO3 synthesized by hydrothermal method[J].Journal of Alloys and Compounds,2016,665:152-157.
[27] Song G L,Su J,Chang F G.Crystal structure refinement,ferroelectric and ferromagnetic properties of Ho3+ modified BiFeO3 multiferroic material[J].Journal of Alloys and Compounds,2017,696:503-508.
[28] Li Deming,Fang Songke,Song Guilin.Effects of Ca2+ doping on dielectric,ferromagnetic properties and magnetic phase transition of SmFeO3 ceramics[J].Acta Physica Sinica,2018,67(6):501-510 (in Chinese).李德铭,方松科,宋桂林.Ca2+掺杂对SmFeO3的介电、铁磁特性及磁相变温度的影响[J].物理学报,2018,67(6):501-510.
[2] Tokunaga Y,Furukawa N,Sakai H,et al.Composite domain walls in a multiferroic perovskite ferrite[J].Nature Materials,2009,8(7):558-562.
[3] Yuan X P,Tang Y K,Sun Y,et al.Structure and magnetic properties of Y1-xLuxFeO3 (0≤x≤1) ceramics[J].Journal of Applied Physics,2012,111(5):053911-053916.
[4] Steele B C,Heinzel A.Materials for fuel-cell technologies[J].Nature,2001,414:345-352.
[5] Kuo C Y,Drees Y,Fernández-Díaz M T,et al.K=0 magnetic structure and absence of ferroelectricity in SmFeO3 [J].Physical Review Letters,2014,113(21):217203-217207.
[6] Berini B,Fouchet A,Popova E.High temperature phase transitions and critical exponents of Samarium orthoferrite determined by in situ optical ellipsometry[J].Journal of Applied Physics,2012,111(5):053923-053927.
[7] Marshall L G,Cheng J G,Zhou J S.Magnetic coupling between Sm3+ and the canted spin in an antiferromagnetic SmFeO3 single crystal [J].Physical Review B,2012,86(6):064417-064421.
[8] Prasad B V,Narsinga Rao G,Chen J W.Abnormal high dielectric constant in SmFeO3 semiconductor ceramics[J].Materials Research Bulletin,2011 46:1670-1673.
[9] Lee J H,Young K J,Park J H,et al.Scott spin-canting-induced improper ferroelectricity and spontaneous magnetization reversal in SmFeO3[J].Physical Review Letters,2011,107(11):117201-117205.
[10] Yuvaraja S,Layekb S,Vidyavathyc S M.Electrical and magnetic properties of spherical SmFeO3 synthesized by aspartic acid assisted combustion method [J].Materials Research Bulletin,2015,72:77-82.
[11] Sahoo S,Mahapatra P K,Choudhary R N P.The structural,electrical and magnetoelectric properties of soft-chemically-synthesized SmFeO3 ceramics[J].Journal of Physics:D applied Physics,2016,49:035302 -035314.
[12] Xu K,Zhao W Y,Xing J J,et al.Hetero-seed and hetero-feed single crystal growth of SmxDy1-xFeO3 perovskites based on optical floating zone method[J].Journal of Crystal Growth,2017,467:111-115.
[13] Zhao X Y,Zhang L K,Xu K,et al.Crystal growth and spin reorientation transitionin Sm0.4Er0.6FeO3 orthoferrite[J].Solid State Communications,2016,231-232:43-47.
[14] Silva-Santana M C,DaSilva C A,Barrozo P,et al.Magnetocaloric and magnetic properties of SmFe0.5Mn0.5O3 complex perovskite[J].Journal of Magnetism and Magnetic Materials,2016,401:612-617.
[15] Kang J,Cui X P,Fang Y F,et al.Magnetic properties and spin reorientation of perovskite SmFe0.5Mn0.5O3 single crystal[J].Solid State Communications,2016,248:101-104.
[16] Praveena K,Bharathi P,Liu H L,et al.Structural,multiferroic properties and enhanced magnetoelectric coupling in Sm1-xCaxFeO3 [J].Ceramics International,2016,42:13572-13585.
[17] Yin L H,Liu Y,Tan S G,et al.Multiple temperature-induced magnetization reversals in SmCr1-xFexO3 system[J].Materials Research Bulletin,2013,48:4016-4021.
[18] Schmidt R,Pandey S,Fiorenza P,et al.Nonstoichiometry in‘CaCu3Ti4O12’(CCTO) ceramics[J].Rsc Advances,2013,34:14580-14587.
[19] Wu H,Lin Y B,Gong J J,et al.Significant enhancements of dielectric and magnetic properties in Bi(Fe1-xMgx)O3-x/2 induced by oxygen vacancies [J].Journal of Physics:D Applied Physics,2013,46:145001-5.
[20] Sinclair D C,Adams T B,Morrison F D.CaCu3TiO12:one-step internal barried layer capacitor[J].Applied Physics Letter,2002.80(12):2153-2155.
[21] Cao S,Zhao H,Ren W.Temperature induced spin switching in SmFeO3 single crysta[J].Scientific Reports,2014,4:5960-5965.
[22] Ahmedl M A,Imam N G,Saeid Y A.Magnetic transitions and butterfly-shaped hysteresis of Sm-Fe-Al-based perovskite-type orthoferrite[J].Journal of rare earths,2015,33(9):965-971.
[23] Zhao H Z,Cao S X,Zhang J C.Enhanced 4f-3d interaction by Ti-doping on the magnetic properties of perovskite SmFe1-xTixO3[J].Journal of Applied Physics,2013,114 (11):113907-113912.
[24] Zhang Y J,Zhang H G,Wu G H.Structural and magnetic properties in Bi1-xRxFeO3(x=0-1,R=La,Nd,Sm,Eu and Tb) polycrystalline ceramics[J].Journal of Magnetism and Magnetic Materials,2010,322(15):2251-2255.
[25] Babu P R,Bhaumik I,Gupta P K.Growth,mechanical,and magnetic study of SmFeO3 single crystal grown by optical floating zone technique[J].Journal of Alloys and Compounds,2016,676:313-319.
[26] Zhang C Y,Shang M Y,Feng S H.Multiferroicity in SmFeO3 synthesized by hydrothermal method[J].Journal of Alloys and Compounds,2016,665:152-157.
[27] Song G L,Su J,Chang F G.Crystal structure refinement,ferroelectric and ferromagnetic properties of Ho3+ modified BiFeO3 multiferroic material[J].Journal of Alloys and Compounds,2017,696:503-508.
[28] Li Deming,Fang Songke,Song Guilin.Effects of Ca2+ doping on dielectric,ferromagnetic properties and magnetic phase transition of SmFeO3 ceramics[J].Acta Physica Sinica,2018,67(6):501-510 (in Chinese).李德铭,方松科,宋桂林.Ca2+掺杂对SmFeO3的介电、铁磁特性及磁相变温度的影响[J].物理学报,2018,67(6):501-510.