Ho~(3+)离子在BaTiO_3陶瓷中自补偿模式探索及反常介电性质
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摘要
采用冷压陶瓷技术制备(Ba_(1-x)Ho_x)(Ti_(1-x)Ho_x)O_3(简称BHTH)陶瓷.通过X射线衍射(XRD)、电子顺磁共振(EPR)和介电温谱技术研究了BHTH陶瓷的结构、位占据和介电性质.结果表明:Ho~(3+)离子在BaTiO_3陶瓷中能够形成自补偿模式,且具有轻微的Ba位占据倾向.在BHTH陶瓷中,固溶度为x=0.03.BHTH陶瓷的介电行为表现出一个反常现象:随着x从0.01增至0.03,居里温度T_C向高温移动,即T_C从128℃升到131℃.BHTH晶体结构的四方度(c/a)随着x增加是T_C向高温移动的主要原因.
(Ba_(1-x)Ho_x)(Ti_(1-x)Ho_x)O_3 ceramics( BHTH) were prepared using the cold-pressing ceramic technique.The structure,site occupations,and dielectric properties of BHTH were investigated using X-ray diffraction( XRD),electron paramagnetic resonance(EPR) and dielectric-temperature measuring techniques.The results indicated that Ho~(3+) ions in the BaTiO_3 lattice could form a self-compensation mode with a slight Basite-occupation preference.The solubility limit was determined to be x = 0.03 in BHTH.The dielectric behavior of BHTH showed an abnormal phenomenon,i. e. that the Curie temperature(T_C) shifted towards high temperatures from 128 ℃ at x = 0.01 to 131 ℃ at x = 0.03. The increase in tetragonality( c/a) of the crystal structure of BHTH is the main reason of the increase in T_C.
(Ba_(1-x)Ho_x)(Ti_(1-x)Ho_x)O_3 ceramics( BHTH) were prepared using the cold-pressing ceramic technique.The structure,site occupations,and dielectric properties of BHTH were investigated using X-ray diffraction( XRD),electron paramagnetic resonance(EPR) and dielectric-temperature measuring techniques.The results indicated that Ho~(3+) ions in the BaTiO_3 lattice could form a self-compensation mode with a slight Basite-occupation preference.The solubility limit was determined to be x = 0.03 in BHTH.The dielectric behavior of BHTH showed an abnormal phenomenon,i. e. that the Curie temperature(T_C) shifted towards high temperatures from 128 ℃ at x = 0.01 to 131 ℃ at x = 0.03. The increase in tetragonality( c/a) of the crystal structure of BHTH is the main reason of the increase in T_C.
引文
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[3] Kishi H.,Kohzu N.,Sugino J.,et al.The effect of rareearth(La,Sm,Dy,Ho and Er)and Mg on the microstructure in Ba Ti O3[J].J.Eur.Ceram.Soc.,1999,19(67):1043-1046.
[4]路大勇,李雪翠,孙秀云.锶锆共掺杂对钛酸钡陶瓷结构和介电性质的影响[J].东北师大学报,2011,43(1):72-76.
[5] Kishi H.,Mizuno Y.,Chazono H.. Base-metal electrode-multilayer ceramic capacitors:past,present and future perspectives[J]. Jpn. J. Appl. Phys.,2003,42:1-15.
[6] Kishi H.,Kohzu N.,Mizuno Y.,et al.Effect of occupational sites of rare-earth elements on the microstructure in Ba Ti O3[J].Jpn.J.Appl.Phys.,1999,38:5452-5456.
[7] Lu D.-Y.,Guan D.-X..Photoluminescence associated with the site occupations of Ho3+ ions in BaTiO3[J].Sci Rep.,2017,7:6125.
[8] Lu D.-Y.,Cui S.-Z..Defects characterization of Dydoped Ba TiO3 ceramics via electron paramagnetic resonance[J].J.Eur.Ceram.Soc.,2014,34:2217-2227.
[9] Lu D.-Y.,Sun X.-Y.,Toda M.. A novel high-k‘Y5V’ barium titanate ceramics co-doped with lanthanum and cerium[J]. J. Phys. Chem. Solids.,2007,68:650-664.
[10] Liu Y.,West A.R..Ho-doped Ba TiO3:polymorphism,phase equilibria and dielectric properties of Ba Ti1-xHoxO3-x/2:0≤x≤0.17[J].J.Eur. Ceram. Soc.,2009,29:3249-3257.
[11] Lu D.-Y..Self-adjustable site occupations between Basite Tb3+and Ti-site Tb4+ions in terbium-doped barium titanate ceramics[J]. Solid State Ionics.,2015,276:98-106.
[12] Lu D.-Y.,Peng Y.-Y..Dielectric properties and exploration of self-compensation mode of Tb in BaTiO3 ceramics[J].J.Ceram.Soc.Jpn.,2016,124:455-459.
[13] Makovec D.,Samardzija Z.,Drofenik M.. Solid solubility of holmium,yttrium,and dysprosium in BaTiO3[J].J.Am.Ceram.Soc.,2004,87:1324-1329.
[14] Jeong J.,Lee E.J.,Han Y.H..Effects of Ho2O3 addition on defects of BaTiO3[J]. Mater. Chem. Phys.,2006,100:434-437.
[15] Kolodiazhnyi T.,Petric A..Analysis of point defects in polycrystalline BaTiO3 by electron paramagnetic resonance[J].J.Phys.Chem.Solids.,2003,64:953-960.
[16]关冬雪,路大勇.Ho掺杂BaTiO3陶瓷的拉曼荧光效应[J].吉林化工学院学报,2017,34(1):16-18.
[17] Itoh J.,Haneda H.,Hishita S.,et al.Diffusion and solubility of holmium ions in barium titanate ceramics[J].J.Mater.Res.,2004,19:3512-3520.
[18] Hennings D..Barium titanate based ceramics materials for dielectric use[J].Int.J.High.Tech.Ceram.,1987,3:91-111.
[19]霍伟荣,曲远方,于天来.无铅BaTiO3基PTC陶瓷提高TC的研究[J].稀有金属材料与工程,2006,35(2):291-293.