Sr掺杂对CaMnO3基氧化物电子性质及热电输运性能的影响

张飞鹏; 张静文; 张久兴; 杨新宇; 路清梅; 张忻

doi:10.7498/aps.66.247202

摘要

采用密度泛函理论计算分析的方法研究了Ca位Sr掺杂的CaMnO3基氧化物的电子性质和电性能；采用柠檬酸溶胶-凝胶法结合陶瓷烧结制备工艺制备了Ca位Sr掺杂的CaMnO3基氧化物块体试样，分析研究了所得试样的热电传输性能.结果表明，Sr掺杂CaMnO3氧化物仍然呈间接带隙型能带结构，带隙宽度由0.756 eV减小到0.711 eV.Sr掺杂CaMnO3氧化物费米能级附近的载流子有效质量均得到调控，载流子浓度也有所增大.Sr比Ca具有更强的释放电子能力，其掺杂在CaMnO3氧化物中表现为n型.Sr掺杂的CaMnO3基氧化物材料电阻率大幅度降低，Seebeck系数绝对值较本征CaMnO3基氧化物材料有一定程度的增大，Sr掺杂量为0.06和0.12的Ca1-xSrxMnO3（x=0.06，0.12）试样，其373 K的电阻率分别降低至本征CaMnO3基氧化物材料的25%和21%，其373 K的Seebeck系数绝对值分别是本征CaMnO3基氧化物材料的112.9%和111.1%，Sr掺杂有效提高了CaMnO3基氧化物材料的热电性能.

关键词:

CaMnO3 /
Sr掺杂 /
电子性质 /
热电性能

Abstract

The electronic and the electrical properties of the Sr doped CaMnO3 oxide for Ca site are studied by the density funtional theory calculation method. The Sr doped CaMnO3 oxide bulk samples are prepared by the citrate acid sol-gel method as well as the ceramic preparation method, and the thermoelectric transport properties are analyzed. The results show that the Sr doped CaMnO3 oxide still has the indirect band gap yet with the band gap energy slightly decreasing from 0.756 eV to 0.711 eV. The effective mass of carrier near Fermi level is modified and the carrier density near Fermi level is also increased. The ability to release electrons of Sr is stronger than that of the Ca, and the Sr acts as n-type donor doping specy within the CaMnO3 compound. The electrical resistivity values remarkably decrease for the Sr doped CaMnO3 oxide materials. The Seebeck coefficient increases slightly to a certain extent compared with that of the intrinsic CaMnO3. The resistivity values for the Ca1-xSrxMnO3 (x=0.06, 0.12) samples at 373 K decrease to 25% and 21% of the un-doped intrinsic CaMnO3 sample, respectively. The Seebeck coefficients for the Ca1-xSrxMnO3 (x=0.06, 0.12) samples at 373 K increase to as high as 112.9% and 111.1% of the Seebeck coefficient for un-doped intrinsic sample, respectively. The thermoelectric performance is effectively enhanced by Sr doping for the CaMnO3 oxide material.

Keywords:

作者及机构信息

1.
河南城建学院数理学院, 建筑光伏一体化河南省工程实验室, 平顶山 467036;

2.
合肥工业大学材料科学与工程学院, 新型功能材料与器件安徽省重点实验室, 合肥 230009;

3.
北京工业大学材料科学与工程学院, 新型功能材料教育部重点实验室, 北京 100124

通信作者: 张飞鹏, zhfp@emails.bjut.edu.cn,zhfp163@163.com

基金项目: 国家自然科学基金（批准号：51572066）和河南省自然科学基金（批准号：162300410007）资助的课题.

Authors and contacts

1.
Henan Provincial Engineering Laboratory of Building-Photovoltaics, Institute of Sciences, Henan University of Urban Construction, Pingdingshan 467036, China;

2.
Anhui Provincial Key Laboratory of Advanced Functional Materials and Devices, College of Materials Science and Engineering, Hefei University of Technology, Hefei 230009, China;

3.
National Key Laboratory of Advanced Functional Materials, College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, China

Corresponding author: Zhang Fei-Peng, zhfp@emails.bjut.edu.cn,zhfp163@163.com

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 51572066) and the Natural Science Foundation of Henan Province, China (Grant No. 162300410007).

参考文献

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[2]	Xu G, Funahashi R, Pu Q, Liu B, Tao R, Wang G, Ding Z 2004 Solid State Ionics 171 147
[3]	Zhang C, Wang C L, Li J C, Yang K, Zhang Y F, Wu Q Z 2008 Mater. Chem. Phys. 107 215
[4]	Zhang F P, Lu Q M, Zhang X, Zhang J X 2011 J. Alloys Compd. 509 542
[5]	Zhang F P, Zhang X, Lu Q M, Zhang J X, Liu Y Q, Fan R F, Zhang G Z 2011 Physica B 406 1258
[6]	Zhang F P, Zhang X, Lu Q M, Zhang J X, Liu Y Q 2011 J. Alloys Compd. 509 4171
[7]	Zhang R Z, Hu X Y, Guo P, Wang C L 2012 Physica B 407 1114
[8]	Wang Y, Sui Y, Wang X J, Su W H 2011 Appl. Phys. A 104 135
[9]	Zhang X H, Li J C, Du Y L, Wang F N, Liu H Z, Zhu Y H, Liu J, Su W B, Wang C L, Mei L M 2015 J. Alloys Compd. 634 1
[10]	Zhang F P, Zhang X, Lu Q M, Liu Y Q, Zhang J X 2011 Acta Phys. Sin. 60 087205 (in Chinese) [张飞鹏, 张忻, 路清梅, 刘燕琴, 张久兴 2011 物理学报 60 087205]
[11]	Zhang F P, Lu Q M, Zhang X, Zhang J X 2013 J. Phys. Chem. Solids 74 1859
[12]	Cao D, Liu B, Yu H L, Hu W Y, Cai M Q 2013 Eur. Phys. J. B 86 504
[13]	Liu B, Wu L J, Zhao Y Q, Wang L Z, Cai M Q 2016 J. Magn. Magn. Mater. 420 218
[14]	Liu B, Wu L J, Zhao Y Q, Wang L Z, Cai M Q 2016 Phys. Chem. Chem. Phys. 18 19918
[15]	Liu B, Wu L J, Zhao Y Q, Wang L Z, Cai M Q 2016 RSC Adv. 6 92473
[16]	Zhao Y Q, Liu B, Yu Z L, Ma J M, Wan Q, He P B, Cai M Q 2017 J. Mater. Chem. C 5 5356
[17]	Zhao Y Q, Wu L J, Liu B, Wang L Z, He P B, Cai M Q 2016 J. Power Sources 313 96
[18]	Wu L J, Zhao Y Q, Chen C W, Wang L Z, Liu B, Cai M Q 2016 Chin. Phys. B 25 107202
[19]	Wang L Z, Zhao Y Q, Liu B, Wu L J, Cai M Q 2016 Phys. Chem. Chem. Phys. 18 22188
[20]	Li J C, Wang C L, Wang M X, Peng H, Zhang R Z, Zhao M L, Liu J, Zhang J L, Mei L M 2009 J. Appl. Phys. 105 043503
[21]	Zhu T J, Xiao K, Yu C, Shen J J, Yang S H, Zhou A J, Zhao X B, He J 2010 J. Appl. Phys. 108 044903
[22]	Peng J Y, Liu X Y, Fu L W, Xu W, Liu Q Z, Yang J Y 2012 J. Alloys Compd. 521 141

施引文献

[1]	Poeppelmeier K R, Leonowicz M E, Scanlon J C, Longo J M 1982 J. Solid State Chem. 45 71
[2]	Xu G, Funahashi R, Pu Q, Liu B, Tao R, Wang G, Ding Z 2004 Solid State Ionics 171 147
[3]	Zhang C, Wang C L, Li J C, Yang K, Zhang Y F, Wu Q Z 2008 Mater. Chem. Phys. 107 215
[4]	Zhang F P, Lu Q M, Zhang X, Zhang J X 2011 J. Alloys Compd. 509 542
[5]	Zhang F P, Zhang X, Lu Q M, Zhang J X, Liu Y Q, Fan R F, Zhang G Z 2011 Physica B 406 1258
[6]	Zhang F P, Zhang X, Lu Q M, Zhang J X, Liu Y Q 2011 J. Alloys Compd. 509 4171
[7]	Zhang R Z, Hu X Y, Guo P, Wang C L 2012 Physica B 407 1114
[8]	Wang Y, Sui Y, Wang X J, Su W H 2011 Appl. Phys. A 104 135
[9]	Zhang X H, Li J C, Du Y L, Wang F N, Liu H Z, Zhu Y H, Liu J, Su W B, Wang C L, Mei L M 2015 J. Alloys Compd. 634 1
[10]	Zhang F P, Zhang X, Lu Q M, Liu Y Q, Zhang J X 2011 Acta Phys. Sin. 60 087205 (in Chinese) [张飞鹏, 张忻, 路清梅, 刘燕琴, 张久兴 2011 物理学报 60 087205]
[11]	Zhang F P, Lu Q M, Zhang X, Zhang J X 2013 J. Phys. Chem. Solids 74 1859
[12]	Cao D, Liu B, Yu H L, Hu W Y, Cai M Q 2013 Eur. Phys. J. B 86 504
[13]	Liu B, Wu L J, Zhao Y Q, Wang L Z, Cai M Q 2016 J. Magn. Magn. Mater. 420 218
[14]	Liu B, Wu L J, Zhao Y Q, Wang L Z, Cai M Q 2016 Phys. Chem. Chem. Phys. 18 19918
[15]	Liu B, Wu L J, Zhao Y Q, Wang L Z, Cai M Q 2016 RSC Adv. 6 92473
[16]	Zhao Y Q, Liu B, Yu Z L, Ma J M, Wan Q, He P B, Cai M Q 2017 J. Mater. Chem. C 5 5356
[17]	Zhao Y Q, Wu L J, Liu B, Wang L Z, He P B, Cai M Q 2016 J. Power Sources 313 96
[18]	Wu L J, Zhao Y Q, Chen C W, Wang L Z, Liu B, Cai M Q 2016 Chin. Phys. B 25 107202
[19]	Wang L Z, Zhao Y Q, Liu B, Wu L J, Cai M Q 2016 Phys. Chem. Chem. Phys. 18 22188
[20]	Li J C, Wang C L, Wang M X, Peng H, Zhang R Z, Zhao M L, Liu J, Zhang J L, Mei L M 2009 J. Appl. Phys. 105 043503
[21]	Zhu T J, Xiao K, Yu C, Shen J J, Yang S H, Zhou A J, Zhao X B, He J 2010 J. Appl. Phys. 108 044903
[22]	Peng J Y, Liu X Y, Fu L W, Xu W, Liu Q Z, Yang J Y 2012 J. Alloys Compd. 521 141

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