Y~(3+)掺杂对Ba_(0.99)La_(0.01)TiO_3陶瓷介电性能的影响
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摘要
以Ba_(0.99)La_(0.01)TiO_3陶瓷为基体,采用传统固相反应法制备Ba_(0.99)La_(0.01)Ti_(1-x)Y_xO_3(0≤x≤0.04)陶瓷样品。通过XRD、SEM、LCR分析仪对陶瓷样品的晶体结构、微观形貌、介电性能进行了分析。结果表明:随着掺杂量增加,晶胞体积逐渐增大,在x=0.04时由四方相转变为立方相,当x≥0.01时,陶瓷样品出现了第二相。结合GULP代码模拟计算和实验数据可知陶瓷中Y~(3+)取代Ti位,主要存在Y~(3+)与La~(3+)相互补偿和氧空位补偿。在x=0.02时,陶瓷发生了半导化,介电常数较大。介电常数峰值温度随着掺杂量的增大向低温方向移动,介电峰被展宽并呈现弛豫铁电体特征。
The Ba_(0.99)La_(0.01)Ti_(1-x)Y_xO_3(0≤x≤0.04)ceramics were prepared by conventional solid state reaction processing using Ba_(0.99)La_(0.01)TiO_3 ceramics as matrix.The crystal structure,micro-morphology and dielectric properties of ceramic samples were studied by XRD,SEM,LCR analyser respectively.The results show that with the increasing of doping amount,the cell volume increases gradually.At x=0.04,the tetragonal phase is transformed into cubic phase.When x≥0.01,the second phase appears in the ceramic sample.Combined with GULP code simulated calculation and experimental datas,Y~(3+)substitute at Ti site compensating with La~(3+)and oxygen vacancy.When x=0.02,the ceramics turn into semiconducting ceramics,exhibiting a large dielectric constant.The dielectric peak temperature shifts to low temperature with the increasing of doping content,and the dielectric peak is broadened.With the increasing of doping content,the ceramic samples show relaxor ferroelectric behavior.
The Ba_(0.99)La_(0.01)Ti_(1-x)Y_xO_3(0≤x≤0.04)ceramics were prepared by conventional solid state reaction processing using Ba_(0.99)La_(0.01)TiO_3 ceramics as matrix.The crystal structure,micro-morphology and dielectric properties of ceramic samples were studied by XRD,SEM,LCR analyser respectively.The results show that with the increasing of doping amount,the cell volume increases gradually.At x=0.04,the tetragonal phase is transformed into cubic phase.When x≥0.01,the second phase appears in the ceramic sample.Combined with GULP code simulated calculation and experimental datas,Y~(3+)substitute at Ti site compensating with La~(3+)and oxygen vacancy.When x=0.02,the ceramics turn into semiconducting ceramics,exhibiting a large dielectric constant.The dielectric peak temperature shifts to low temperature with the increasing of doping content,and the dielectric peak is broadened.With the increasing of doping content,the ceramic samples show relaxor ferroelectric behavior.
引文
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[21]徐家跃,金敏.新型弛豫铁电晶体-生长、性能及应用[M].北京:化学工业出版社,2007.
[2]Moulson A J,Herbert J M.Electroceramics:materials,properties,applications[M].London:John Wiley&Sons,2003:69-79.
[3]肖鹏.Y掺杂对Ba(Sn0.1Ti0.9)O3陶瓷物理性能的影响[D].哈尔滨:哈尔滨工业大学,2006.
[4]梁月,路大勇.Tm3+离子在BaT iO 3介电陶瓷中的位占据研究[J].吉林化工学院学报,2018,35(01):44-46.
[5]王见华,刘雪晨,马凯鑫,等.稀土La元素掺杂BaT iO 3的晶格调控及铁电性[J].材料导报,2016(S1):256-259.
[6]Tsur Y,Dunbar T D,Randall C A.Crystal and defect chemistry of rare earth cations in BaTiO3[J].Journal of Electroceramics,2001,7(1):25-34.
[7]Shannon R D T,Prewitt C T.Effective ionic radii in oxides and fluorides[J].Acta Crystallographica Section B:Structural Crystallography and Crystal Chemistry,1969,25(5):925-946.
[8]Wang X,Ren P,Wang Q,et al.Dielectric,piezoelectric and conduction properties of yttrium acceptordoped BaTiO3 ceramics[J].Journal of Materials Science Materials in Electronics,2016,27(11):11762-11769..
[9]Tsur Y,Hitomi A,Scrymgeour I,et al.Site occupancy of rare-earth cations in BaTiO3[J].Japanese Journal of Applied Physics,2001,40(1):255-258.
[10]唐超群,喻力华.La掺杂BaT iO 3陶瓷的介电性随掺La量及频率的变化[J].华中理工大学学报,1995(09):116-119.
[11]杨公安,蒲永平,王瑾菲,等.La2O3掺杂对BaTiO3-N2O5-Fe2O3陶瓷的晶体结构和介电性能的影响[J].人工晶体学报,2009,38(04):908-912.
[12]杨斌,刘敬肖,史非,等.Y3+掺杂量对BaT iO 3基热敏陶瓷性能的影响[J].大连工业大学学报,2017,36(04):283-286.
[13]骆春媛,刘敬肖,史非,等.Y、La及Nb掺杂的BaTiO3半导体陶瓷的研究[J].中国陶瓷,2013,49(07):28-30.
[14]Gale J D.GULP:A computer program for the symmetry-adapted simulation of solids[J].Journal of the Chemical Society,Faraday Transactions,1997,93(4):629-637.
[15]Lewis G V,Catlow C R A.Defect studies of doped and undoped barium titanate using computer simulation techniques[J].Journal of Physics&Chemistry of Solids,1986,47(1):89-97.
[16]Dick J B G,Overhauser A W.Theory of the dielectric constants of alkali halide crystals[J].Physical Review,1958,112(1):90-103.
[17]Lewis G V,Catlow C R A.Potential models for ionic oxides[J].Journal of Physics C:Solid State Physics,1985,18(6):1149-1161.
[18]Buscaglia M T,Buscaglia V,Viviani M,et al.Atomistic simulation of dopant incorporation in barium titanate[J].Journal of the American Ceramic Society,2001,84(2):376-84.
[19]Peng Y,Ding S H,Song T X,et al.Dielectric Properties,Relaxor Behavior and Crystal Chemistry Properties of Ba0.98Bi0.02(Ti0.9Zr0.1)1-xCuxO3 Ceramics[J].Chinese Journal of Inorganic Chemistry,2013,29(7):1400-1406.
[20]Rout S K,Sinha E,Panigrahi S.Dielectric properties and diffuse phase transition in Ba1-xMgxTi0.6Zr0.4O3 solid solutions[J].Materials chemistry and physics,2007,101(2-3):428-432.
[21]徐家跃,金敏.新型弛豫铁电晶体-生长、性能及应用[M].北京:化学工业出版社,2007.