Ti~(4+)掺杂Fe位对CuFeO_2陶瓷材料结构和介电性能的影响
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摘要
以CuO,Fe_2O_3和TiO_2为主要原料,采用固相反应法制备了CuFe_(1-x)Ti_xO_2(0≤x≤0. 08)陶瓷系列样品,对所得样品的结构、形貌和介电性能进行了表征和分析,并利用内部阻挡层模型(IBLC)对样品的微观结构与介电性能的关联规律进行了物理解释.结果表明,掺杂样品均具有单相铜铁矿结构;适量的Ti~(4+)掺杂能够促进铜铁矿CuFeO2陶瓷样品的晶粒生长,而较大浓度的Ti~(4+)掺杂则会对铜铁矿CuFeO_2陶瓷样品的晶粒生长有明显的抑制作用,同时会破坏较为致密的晶体形貌;未掺杂及少量Ti~(4+)掺杂(x=0. 005和0. 01)样品展现出室温巨介电性能,适当掺杂Ti~(4+)可以有效提高体系的介电性能; IBLC模型可以解释Ti~(4+)掺杂CuFeO_2样品的介电机理,即CuFeO2陶瓷体系的微观形貌能明显影响体系的巨介电性能.
CuO,Fe_2O_3 and TiO_2 were used as the main raw materials,and CuFe_(1-x)TixO_2 (0 ≤x ≤0. 08) ceramic series samples were prepared by solid state reaction method. The microstructure,morphology and dielectric properties of the samples obtained were characterized and analyzed. The internal barrier model(IBLC) was used to physically interpret the correlation between the microstructure and dielectric properties of the samples. The results showed that the doped series samples had a single-phase copper iron ore structure. Appropriate amount of Ti~(4+)doping could promote the grain growth of CuFeO_2 ceramic samples,while the larger concentration of Ti~(4+)significantly inhibited the grain growth of CuFeO_2 ceramic samples,and damaged the denser crystal morphology. Undoped and a small amount of Ti~(4+)-doped( x = 0. 005 and 0. 01) CuFeO_2 samples exhibited room temperature giant dielectric properties,and proper doping of Ti~(4+)could effectively improve the dielectric properties of the system; IBLC model could explain the intercalation of Ti~(4+)-doped CuFeO_2 samples.The electrical mechanism,that is,the microscopic morphology of the CuFeO_2 ceramic system could significantly affect the giant dielectric properties of the system.
CuO,Fe_2O_3 and TiO_2 were used as the main raw materials,and CuFe_(1-x)TixO_2 (0 ≤x ≤0. 08) ceramic series samples were prepared by solid state reaction method. The microstructure,morphology and dielectric properties of the samples obtained were characterized and analyzed. The internal barrier model(IBLC) was used to physically interpret the correlation between the microstructure and dielectric properties of the samples. The results showed that the doped series samples had a single-phase copper iron ore structure. Appropriate amount of Ti~(4+)doping could promote the grain growth of CuFeO_2 ceramic samples,while the larger concentration of Ti~(4+)significantly inhibited the grain growth of CuFeO_2 ceramic samples,and damaged the denser crystal morphology. Undoped and a small amount of Ti~(4+)-doped( x = 0. 005 and 0. 01) CuFeO_2 samples exhibited room temperature giant dielectric properties,and proper doping of Ti~(4+)could effectively improve the dielectric properties of the system; IBLC model could explain the intercalation of Ti~(4+)-doped CuFeO_2 samples.The electrical mechanism,that is,the microscopic morphology of the CuFeO_2 ceramic system could significantly affect the giant dielectric properties of the system.
引文
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[2]KUNDYS B,MAIGNAN A,PELLOQUIN D,et al.Magnetoelectric interactions in polycrystalline multiferroic antiferromagnets CuFe1-xRhxO2(x=0.00 and x=0.05)[J].Solid State Sciences,2009,11(5):1035.
[3]GAEWDANG T,WONGCHAROEN N.Electrical conduction mechanisms in n-CdS/p-CuFeO2heterojunction diode[J].Advanced Materials Research,2014,931/932:122.
[4]DONG Y C,CAO C W,CHUI Y S,et al.Facile hydrothermal synthesis of CuFeO2hexagonal platelets/rings and graphene composites as anode material for lithium ion batteries[J].Chemical Communications,2014,50(70):10151.
[5]MITSUDA S,MASE M,PROKES K,et al.Fieldinduced magnetic phase transitions in a triangular lattice antiferromagnet CuFeO2up to 14.5 T[J].Journal of the Physical Society of Japan,2000,69(11):3513.
[6]SEKI S,YAMASAKI Y,SHIOMI Y,et al.Impurity-doping-induced ferroelectricity in the frustrated antiferromagnet CuFeO2[J].Physical Review B,2007,75(10):100403.
[7]SHI L,XIA Z,WEI M,et al.The enhanced spontaneous dielectric polarization in Ga doped CuFeO2[J].Journal of Applied Physics,2014,116(17):173907.
[8]ELKHOUN T,AMAMI M,HLIL E K,et al.Effect of spin dilution on the magnetic state of delafossite CuFeO2with an S=5/2 antiferromagnetic triangular sublattice[J].Journal of Superconductivity and Novel Magnetism,2015,28(5):1439.
[9]宋江,成鹏飞,王秋萍,等.巨介电常数陶瓷CaCu3Ti4O12的研究进展[J].材料导报,2016,30(10):89.
[10]王亚军,王芳芳,冯长根,等.巨介电CCTO及CCTO/聚合物研究[J].化学进展,2013,25(11):1981.
[11]谢新宇,代海洋,陈镇平,等.成型压力对CuFeO2陶瓷材料结构和介电性能的影响[J].电子元件与材料,2017,36(12):16.
[12]LI T,CHEN J,LIU D W,et al.Effect of NiO-doping on the microstructure and the dielectric properties of CaCu3Ti4O12ceramics[J].Ceramics International,2014,40(7):9061.
[13]CHENG H,XIAO J,GAO P,et al.Low and microwave frequency dielectric properties studies on the Ca Cu3-xZnxTi4O12ceramics[J].Piezoelectrics and Acoustooptics,2016,38(6):956.
[14]FANG T T,LIU C P.Evidence of the internal domains for inducing the anomalously high dielectric constant of CaCu3Ti4O12[J].Chemistry of Materials,2005,17(20):5167.
[15]YAN Y,JIN L,FENG L,et al.Decrease of dielectric loss in giant dielectric constant CaCu3Ti4O12ceramics by adding CaTiO3[J].Materials Science Engineering B,2006,130(1/3):146.