BCZT陶瓷的Nd~(3+)掺杂机制与介电性能研究
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摘要
采用固相合成法制备了(Ba_(0.92-x)Ca_(0.08)Nd_x)(Ti_(0.82)Zr_(0.18))O_3(0≤x≤0.02)陶瓷样品,借助XRD、LCR等手段对该陶瓷的结构和介电性能进行了研究。结果表明:当x=0.015时,陶瓷样品出现第二相。通过GULP软件模拟计算并结合实验数据分析可知:随着Nd~(3+)浓度增加,Ti~(4+)空位补偿机制优先发生,可能伴有少量自我补偿。增大Nd~(3+)掺杂量,介电常数与介电损耗均呈现下降趋势,介电峰值扩展并向低温移动。随着Nd~(3+)掺杂量增加,陶瓷样品呈现弛豫型铁电体特征,这与偏离平衡位置Nd~(3+)和缺陷偶极子[4Nd_(Ba)~·+V_(Ti)~″″]产生的无规场有关。
( Ba_(0.92-x)Ca_(0.08)Nd_x)( Ti_(0.82)Zr_(0.18))O_3( 0≤x≤0. 02) ceramics samples were prepared based on solidstate reaction methods. XRD,LCR and other techniques were utilized to investigated the microstructure and dielectric properties of the samples. The results show that when the doping amount is 0. 015,the second phase occurs. Associated with the experiment date,the analysis indicates that with the increasing Nd~(3+) concentration,the Ti~(4+) vacancies compensation mechanism occurred preferentially by the general utility lattice program( GULP),maybe accompanied by a small amount of self-compensation. With Nd~(3+) content increasing,both dielectric constant and dielectric loss decline,and the dielectric peak temperature shiftes to low temperature and the dielectric peak is broaden. With the increasing Nd~(3+) content,the dielectric relaxation characteristics are obtained. This is attributed to the random field induced by off-center Nd~(3+) ions and defect dipoles [4Nd_(Ba)~·+ V_(Ti)~″″].
( Ba_(0.92-x)Ca_(0.08)Nd_x)( Ti_(0.82)Zr_(0.18))O_3( 0≤x≤0. 02) ceramics samples were prepared based on solidstate reaction methods. XRD,LCR and other techniques were utilized to investigated the microstructure and dielectric properties of the samples. The results show that when the doping amount is 0. 015,the second phase occurs. Associated with the experiment date,the analysis indicates that with the increasing Nd~(3+) concentration,the Ti~(4+) vacancies compensation mechanism occurred preferentially by the general utility lattice program( GULP),maybe accompanied by a small amount of self-compensation. With Nd~(3+) content increasing,both dielectric constant and dielectric loss decline,and the dielectric peak temperature shiftes to low temperature and the dielectric peak is broaden. With the increasing Nd~(3+) content,the dielectric relaxation characteristics are obtained. This is attributed to the random field induced by off-center Nd~(3+) ions and defect dipoles [4Nd_(Ba)~·+ V_(Ti)~″″].
引文
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[24]陈威,曹万强.弛豫铁电体弥散相变的玻璃化特性研究[J].物理学报,2012,61(9):438-441.
[25]GLINCHUK M D,STEPHANOVICH V A.Random fields and their influence on the phase transitions in disordered ferroelectrics[J].Journal of Physics:Condensed Matter,1994,6:6317-6328.
[26]VUGMEISTER B E,GLINCHUK M D.Dipole glass and ferroelectricity in random-site electric dipole systems[J].Reviews of Modern Physics,1990,62:993-1026.
[27]GLAZOUNOV A E,TAGANTSEV A K.BELL A J.Evidence for domain-type dynamics in the ergodic phase of the Pb Mg1/3Nb2/3O3relaxor ferroelectric[J].Physical Review B,1996,53(17):11281-11284
[2]BUSCAGLIA M T,BUSCAGLIA V,VIVIANI M,et al.Influence of forgign ions on the crystal structure of Ba Ti O3[J].Journal of the European Ceramic Society,2000,20(12):1997-2007.
[3]LEWIS G V,CATLOW C R A.Defect studies of doped and undoped barium titanate using computer simulation techniques[J].Journal of Physics and Chemistry of Solids,1986,47(1):89-97.
[4]BUSCAGLIA M T,BUSCAGLIA V,VIVIANI M,et al.Atomistic simulation of dopant incorporation in barium titanate[J].Journal of the European Ceramic Society,2001,84(2):376-384.
[5]ZHANG X W,HAN Y H,LAL M,et al.Defect chemistry of Ba Ti O3with additions of Ca Ti O3[J].Journal of the American Ceramic Society,1987,70(2):100-103.
[6]HENNINGS D,SCHNELL A,SIMON G.Diffuse ferroelectric phase transitions in Ba(Ti1-yZry)O3ceramics[J].Journal of the American Ceramic Society,1982,65(11):539-544.
[7]KE S M,FAN H Q,HUANG H T,et al.Dielectric dispersion behavior of Ba(ZrxTi1-x)O3solid solutions with a quasiferroelectric state[J].Journal of Applied Physics,2008,104:1-7.
[8]MITSUI T,WESTPHAL W B.Dielectric and X-Ray studies of CaxBa1-xTi O3and CaxSr1-xTi O3[J].Physical Review,1961,124(5):1354-1359.
[9]BASKARAN N,CHANG H.Thermo-Raman and dielectric constant studies of CaxBa1-xTi O3ceramics[J].Maerial Chemistry and Physics,2002,77:889-894.
[10]那文菊,丁士华,宋天秀,等.(Ba1-xCax)(Ti0.82Zr0.18)O3陶瓷结构与介电性能研究[J].无机材料学报,2011,26(6):655-658.
[11]ROUT S K,SINHA E,PANIGRAHI S,et al.Phase formation and dielectric phase transition in Ba1-xCaxTi0.6Zr0.4O3solid solutions[J].Journal of Physics and Chemistry of Solids,2006,67:2257-2262.
[12]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.
[13]LEWIS G V,CATLOW C R A.Potential models for ionic oxides[J].Journal of Physics C:Solid State Physics,1985,18:1149-1161.
[14]BUSH T S,GALE J D,CATLOW C R A,et al.Self-consistent interatomic potentials for the simulation of binary and ternary oxides[J].Journal of Materials Chemistry,1994,4(6):831-837.
[15]TSUR Y,HITOMI A,SCRYMGEOUR I,et al.Site occupancy of rare-earth cations in Ba Ti O3[J].Japanese Journal of Applied Physics,2001,40:255-258.
[16]TSUR Y,DUNBAR T D,RANDALL C A.Crystal and defect chemistry of rare earth caations in Ba Ti O3[J].Journal or Electroceramics,2001,7:25-34.
[17]TAKADA K,CHAND E,SMYTH D M.Rare earth additions to Ba Ti O3[J].Advanced Ceramics,1987,19:147-151.
[18]谢道华,RELVA C B.(Ba1-xNdx)Ti O3系陶瓷的电性能[J].天津大学学报,1994,27(2):179-184.
[19]SHAIKH A S,VEST R W.Defect structure and dielectric properties of Nd2O3-modigied Ba Ti O3[J].Journal of the American Ceramic Society,1986,69:689-694.
[20]HIROSE N,SKAKLE J M S,WEST A R.Doping mechanism and permittivity correlations in Nd-doped Ba Ti O3[J].Journal or Electroceramics,1999,3(3):233-238.
[21]OHSATO H.Science of tungstenbronze-type like Ba6-3x R8+2xTi18O54(R=rare earth)microwave dielectric solid solutions[J].Journal of the European Ceramic Society,2001,21:2703-2711.
[22]CHA S H,HAN Y H.Effects of Mn doping on dielectric properties of Mg-doped Ba Ti O3[J].Journal of Applied Physics,2006,100:104102(1)-104102(4).
[23]JEONG J,HAN Y H.Electrical properties of acceptor doped Ba Ti O3[J].Journal or Electroceramics,2004,13:549-553.
[24]陈威,曹万强.弛豫铁电体弥散相变的玻璃化特性研究[J].物理学报,2012,61(9):438-441.
[25]GLINCHUK M D,STEPHANOVICH V A.Random fields and their influence on the phase transitions in disordered ferroelectrics[J].Journal of Physics:Condensed Matter,1994,6:6317-6328.
[26]VUGMEISTER B E,GLINCHUK M D.Dipole glass and ferroelectricity in random-site electric dipole systems[J].Reviews of Modern Physics,1990,62:993-1026.
[27]GLAZOUNOV A E,TAGANTSEV A K.BELL A J.Evidence for domain-type dynamics in the ergodic phase of the Pb Mg1/3Nb2/3O3relaxor ferroelectric[J].Physical Review B,1996,53(17):11281-11284