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《材料导报》期刊社  2018, Vol. 32 Issue (2): 184-188    https://doi.org/10.11896/j.issn.1005-023X.2018.02.005
  物理   材料研究 ｜材料 |
La0.67Ca0.33-0.5xLixMnO3多晶陶瓷结构及电学性能研究
李迪,陈清明,陈晓慧,李之昱,张亚林,张辉
昆明理工大学材料科学与工程学院,昆明 650093
Structure and Electrical Properties of La0.67Ca0.33-0.5xLixMnO3 Polycrystalline Ceramic
Di LI,Qingming CHEN,Xiaohui CHEN,Zhiyu LI,Yalin ZHANG,Hui ZHANG
College of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 690093
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摘要 

用溶胶-凝胶法制备La0.67Ca0.33-0.5xLixMnO3(x=0.00,0.05,0.10,0.20)多晶陶瓷,用XRD分析多晶陶瓷的晶体结构,用SEM对多晶陶瓷的微观形貌进行分析,用标准四探针法测量电阻率-温度关系。结果表明,随着Li掺杂量的增加,所有样品均为斜方晶系,晶胞体积不断减小,金属-绝缘体转变温度(TP)降低,电阻率不断增加,电阻率温度系数(TCR)不断减小。低温区域(TP)的电阻率数据可以用ρ(T)= ρ0+ρ2T 2+ρ4.5T 4 . 5进行拟合;高温区域(T>TP)的电阻率数据可以用小极化子跃迁(SPH)模型和变程跳跃(VRH)模型进行拟合。整个温度区域(100300 K)可以使用渗透模型对电阻率进行拟合。从拟合数据可知极化子激活能Ea随Li掺杂量的增加而增大,这是由于Li的加入减小了Mn 3+-O 2--Mn 4+的键角,增大了有效带宽的间隙,因此也减弱了双交换作用,增大了电阻率。

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李迪
陈清明
陈晓慧
李之昱
张亚林
张辉
关键词:  La0.67Ca0.33-0.5xLixMnO3多晶  电阻率拟合  金属-绝缘体转变    
Abstract: 

A series of La0.67Ca0.33-0.5xLixMnO3 ceramic (x=0.00, 0.05, 0.10, 0.15, 0.20) were prepared by sol-gel technique. The crystal structures were analyzed by X-ray diffraction (XRD), the surface morphology and grain boundaries were investigated by scanning electron microscope (SEM), and the temperature dependence of the resistivity (R-T) of the bulk samples were studied by the standard four-probe method. It can be indexed with an orthorhombic structure for all of La0.67Ca0.33-0.5xLixMnO3 polycrystalline ceramics. The results showed that with the increase of the content of Li element, the unit cell volume decrease and the resistance increases. The insulator-metal transition temperature TP shifts to lower temperature and the temperature coefficient of resistivity (TCR) decrease continually. The data of resistivity on low-temperature (TP) have been fitted with the relation ρ(T)=ρ0+ρ2T 2+ρ4.5T 4 . 5, the high-temperature (T>TP) resistivity data were explained using small-polaron hopping (SPH) and variable-range hopping (VRH) models. The resistivity data in whole temperature range (100—300 K) can be fitted by percolation model. Polaron activation energy Ea is found to increases with increasing the contant of Li (x), which suggests that Li doping decrease bond angle of Mn 3+-O 2--Mn 4+, thereby the increase of effective band gap and the decrease of double exchange coupling, this is the reason of the increase of resistivity.

Key words:  La0.67Ca0.33-0.5xLixMnO3 polycrystalline    resistivity fitting    metal-insulator transition
出版日期:  2018-01-25      发布日期:  2018-01-25
ZTFLH:  TQ174  
基金资助: 国家自然科学基金(11564021)
引用本文:    
李迪,陈清明,陈晓慧,李之昱,张亚林,张辉. La0.67Ca0.33-0.5xLixMnO3多晶陶瓷结构及电学性能研究[J]. 《材料导报》期刊社, 2018, 32(2): 184-188.
Di LI,Qingming CHEN,Xiaohui CHEN,Zhiyu LI,Yalin ZHANG,Hui ZHANG. Structure and Electrical Properties of La0.67Ca0.33-0.5xLixMnO3 Polycrystalline Ceramic. Materials Reports, 2018, 32(2): 184-188.
链接本文:  
https://www.mater-rep.com/CN/10.11896/j.issn.1005-023X.2018.02.005  或          https://www.mater-rep.com/CN/Y2018/V32/I2/184
x Lattice constant Cell
volume
V/?3		 TP
K		 TCR/(%·
K-1)
a/? b/? c/?
0.00 5.454 7.709 5.460 229.557 264 51.9
0.05 5.449 7.721 5.462 229.814 258 12.6
0.10 5.487 7.774 5.477 233.599 255 8.7
0.15 5.485 7.734 5.480 232.464 249 4.0
0.20 5.413 7.717 5.487 229.216 232 3.7
表1  La0.67Ca0.33-0.5xLixMnO3的晶格常数、Tp、TCR
图1  不同Li含量La0.67Ca0.33-0.5xLixMnO3(x=0.00,0.05,0.10,0.20)的XRD衍射谱
图2  La0.67Ca0.33-0.5xLixMnO3多晶陶瓷的SEM照片: (a)x=0.00,(b)x=0.10,(c)x=0.15,(d)x=0.20
图3  La0.67Ca0.33-0.5xLixMnO3多晶陶瓷的(a)温度-电阻率曲线,(b)温度-电阻系数曲线
x ρ0
10-4Ω·cm		 ρ2/(10-9Ω·
cm·K-1)		 ρ4.5/(10-13Ω·
cm·K-1)		 R2
0.00 5.77 9.812 27 0. 521 11 0.996 9
0.05 46.00 308.573 3.216 02 0.999 9
0.10 73.60 462.456 19.894 8 0.999 5
0.15 105.00 195.023 20.760 5 0.999 3
0.20 131.58 6 422.78 354.654 0.999 9
表2  低温区域拟合式(1)的拟合参数(T<TP)
x Ea
meV		 θD
K		 J
meV		 Jφ γP R2
0.00 83.68 559 27.63 1.16 3.47 0.999 6
0.05 129.03 533 26.65 1.03 5.62 0.999 9
0.10 167.06 540 26.92 0.97 7.18 0.999 4
0.15 164.44 526 26.38 0.97 7.26 0.999 8
0.20 154.13 499 25.37 0.97 7.17 0.999 2
表3  小极化子跳跃模型拟合式(2)、式(3)的拟合参数(T>θ/2)
图4  不同温度区间的电阻率拟合曲线:(a)T<TP,(b)TP<T<Tθ/2,(c)T>Tθ/2
x T0/K N(EF)/(eV-1·cm-3) R2
0.00 1 954 1.04×1024 0.985 2
0.05 3 284 6.19×1023 0.978 1
0.10 4 713 4.31×1023 0.977 2
0.15 3 166 6.42×1023 0.945 4
0.20 3 009 6.75×1023 0.956 8
表4  变程跳跃模型拟合式(5)的拟合参数(TP<T<θ/2)
x U0kB/104K Tc-mod/ K R2
0.00 6.16 258 0.998 9
0.05 3.27 253 0.999 8
0.10 1.76 251 0.997 4
0.15 1.45 249 0.998 7
0.20 0.74 232 0.994 2
表5  渗透模型拟合式(8)的拟合参数(100300 K)
图5  渗透模型的电阻率拟合曲线(100300 K)
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