n型SnS热电材料的制备与性能研究
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摘要
SnS由低毒、廉价、高丰度的元素组成,在热电研究领域受到广泛关注。采用机械合金化(MA)结合放电等离子烧结(SPS)工艺制备了n型SnS_(1-x)Cl_x(x=0,0.02,0.03,0.04,0.05,0.06)多晶块体热电样品,并研究了Cl~-掺杂量对SnS物相、微观结构以及电热输运性能的影响。结果表明:Cl~-的引入会提高电子浓度,使SnS由本征p型转变为n型半导体。随着Cl~-掺杂量的增加,n型SnS半导体室温下的霍尔载流子浓度从6.31×10~(14) cm~(-3)(x=0.03)增加到7.27×10~(15 )cm~(-3)(x=0.06)。x=0.05样品在823 K取得最大的电导率为408 S·m~(-1),同时具有较高的泽贝克系数为-553μV?K~(-1),使其获得最大功率因子为1.2μW·cm~(-1)·K~(-2)。Cl~-的掺入会引入点缺陷,散射声子,使晶格热导率κ_(lat)由0.67 W·m~(-1)·K~(-1)(x=0)降至0.5 W·m~(-1)·K~(-1)(x=0.02)。x=0.04样品在823 K获得了最大ZT为0.17,相比于x=0样品(ZT～0.1)提高了70%。
SnS composed of low toxicity,low-cost and earth-abundant elements,has extensive attention in the field of thermoelectric research.The n-type SnS_(1-x)Cl_x(x=0,0.02,0.03,0.04,0.05,0.06)polycrystalline bulk thermoelectric samples were prepared by mechanical alloying(MA)combined with Spark Plasma Sintering(SPS).Effect of Clamounts on the phase structure,microstructure and thermoelectric transport properties were systematically studied.Results show that introduction of Cl~-enhances electron concentration which makes intrinsic p-type SnS change to n-type.With the amount of Cl~-increasing,the Hall carrier concentration of n-type SnS semiconductor increases from6.31×10~(14) cm~(-3)(x=0.03)to 7.27×10~(15) cm~(-3)(x=0.06)at room temperature.The maximum electrical conductivity of 408 S?m~(-1)and the relatively high Seebeck coefficient of-553μV?K~(-1) are obtained at 823 K for x=0.05 sample,which produces the maximum power factor of 1.2μW·cm~(-1)·K~(-2).Addition of Cl~-can introduce point defects to scatter phonons,which makes the lattice thermal conductivity reduce from 0.67 W·m~(-1)·K~(-1)(x=0)to 0.5 W·m~(-1)·K~(-1)(x=0.02).The highest ZT～0.17 is obtained at 823 K for x=0.04 sample,which is 70%higher than that(ZT～0.1)of the pristine SnS.
SnS composed of low toxicity,low-cost and earth-abundant elements,has extensive attention in the field of thermoelectric research.The n-type SnS_(1-x)Cl_x(x=0,0.02,0.03,0.04,0.05,0.06)polycrystalline bulk thermoelectric samples were prepared by mechanical alloying(MA)combined with Spark Plasma Sintering(SPS).Effect of Clamounts on the phase structure,microstructure and thermoelectric transport properties were systematically studied.Results show that introduction of Cl~-enhances electron concentration which makes intrinsic p-type SnS change to n-type.With the amount of Cl~-increasing,the Hall carrier concentration of n-type SnS semiconductor increases from6.31×10~(14) cm~(-3)(x=0.03)to 7.27×10~(15) cm~(-3)(x=0.06)at room temperature.The maximum electrical conductivity of 408 S?m~(-1)and the relatively high Seebeck coefficient of-553μV?K~(-1) are obtained at 823 K for x=0.05 sample,which produces the maximum power factor of 1.2μW·cm~(-1)·K~(-2).Addition of Cl~-can introduce point defects to scatter phonons,which makes the lattice thermal conductivity reduce from 0.67 W·m~(-1)·K~(-1)(x=0)to 0.5 W·m~(-1)·K~(-1)(x=0.02).The highest ZT～0.17 is obtained at 823 K for x=0.04 sample,which is 70%higher than that(ZT～0.1)of the pristine SnS.
引文
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[2]SNYDER G J,TOBERER E S.Complex Thermoelectric Materials.Materials For Sustainable Energy:A Collection of Peer-Reviewed Research and Review Articles from Nature Publishing Group,World Sueutific,2011:101-110.
[3]TAN QING,ZHAO LI-DONG,LI JING-FENG,et al.Thermoelectrics with earth abundant elements:low thermal conductivity and high thermopower In doped SnS.Journal of Materials Chemistry A,2014,2(41):17302-17306.
[4]ZHOU BIN-QIANG,LI SHUAI,LI WEN,et al.Thermoelectric properties of SnS with Na-doping.ACS Applied Materials&Interfaces,2017,9(39):34033-34041.
[5]WU HONG,LU XU,WANG GUO-YU,et al.Sodium-doped tin sulfide single crystal:a nontoxic earth-abundant material with high thermoelectric performance.Advanced Energy Materials,2018,8(20):1800087-1-8.
[6]HE WEN-KE,WANG DONG-YANG,DONG JIN-FENG,et al.Remarkable electron and phonon band structures lead to a high thermoelectric performance ZT>1 in earth-abundant and ecofriendly SnS crystals.Journal of Materials Chemistry A,2018,6(21):10048-10056.
[7]GUO RUI-QIANG,WANG XIN-JIANG,KUANG YOU-DI,et al.First-principles study of anisotropic thermoelectric transport properties of IV-VI semiconductor compounds SnSe and SnS.Physical Review B,2015,92(11):115202-1-13.
[8]WANG XUE,XU JING-TAO,LIU GUO-QIANG,et al.Optimization of thermoelectric properties in n-type SnSe doped with BiCl3.Applied Physics Letters,2016,108(8):083902-1-5.
[9]CHANG CHENG,TAN QING,PEI YAN-LING,et al.Raising thermoelectric performance of n-type SnSe via Br doping and Pb alloying.RSC Advances,2016,6(100):98216-98220.
[10]ZHANG QIAN,CHERE E K,SUN JING-YING,et al.Studies on thermoelectric properties of n-type polycrystalline SnSe1-xSx by iodine doping.Advanced Energy Materials,2015,5(12):1500360-1-8.
[11]TAN QING,LI JING-FENG.Thermoelectric properties of Sn-Sbulk materials prepared by mechanical alloying and spark plasma sintering.Journal of Electronic Materials,2014,43(6):2435-2439.
[12]SITUMORANG M,GOLDSMID H J.Anisotropy of the Seebeck coefficient in bismuth telluride.Physica Status Solidi(b),1986,134(1):K83-K88.
[13]GE ZHEN-HUA,ZHANG BO-PING,LI JING-FENG.Microstructure composite-like Bi2S3 polycrystals with enhanced thermoelectric properties.Journal of Materials Chemistry,2012,22(34):17589-17594.
[14]NEUBRONNER M,BODMER T,HüBNER C,et al.D6 Properties of Solids and Solid materials.VDI Heat Atlas.Springer,Berlin,Heidelberg,2010:551-614.