异层等价离子双掺杂策略优化BiCuSeO的热电性能
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摘要
选取BiCuSeO双亚层超晶格热电材料为研究对象,通过La、Ag单掺杂和双掺杂两种方式等价取代[Bi2O2]2+亚层和[Cu2Se2]2–亚层中的Bi、Cu位点,并对其热电输运性能和缺陷调控机理进行研究,结果发现:La-Ag双掺杂可以结合两种单掺杂的优势,在适度提升载流子浓度的同时保持与纯样相当的载流子迁移率,从而使电导率得到大幅度的提升。与此同时,La-Ag双掺杂可以引发能带收敛效应,有助于同步获得较高的载流子迁移率和Seebeck系数,最终使PF得到了优化;另一方面,由于点缺陷对载热声子的强烈散射作用,样品的晶格热导率和总热导率进一步降低,使最终ZT值也得到了优化。结果,La-Ag双掺杂样品的ZT值在755K下达到0.46,高于原始纯样(ZT=0.27)和单掺杂样品。该项研究表明La、Ag异层等价双掺杂策略可以实现BiCuSeO热电输运参数的协同调控与优化。
Taking the dual-sublayer BiCuSeO superlattice thermoelectric material as an object, equivalent mono-and dual-doped samples were prepared by substitution of Bi and Cu atoms in the corresponding [Bi2 O2]2+ sublayer and[Cu2 Se2]2– sublayer with isovalent La and Ag atoms. Their thermoelectric properties and the defect modulation mechanism were studied. The results showed that La-Ag dual-doped sample could combine the advantages of mono-doped samples to achieve an relative high carrier mobility while moderately increasing the carrier concentration, thereby maximizing the electrical conductivity. At the same time, it can also induce a potential band convergence effect,achieving the low average band effective mass and high density of states effective mass at the same time, which finally endowed Bi0.98 La0.02 Cu0.98 Ag0.02 SeO with simultaneous high carrier mobility and Seebeck coefficient, as well as the optimized power factor(PF=σS2). On the other hand, due to the strong point defect scattering on the heat-carrying phonons, the lattice and total thermal conductivities of these isovalent doped samples were further reduced, which finally optimized the figure of merit(ZT). As a result, a high ZT value of 0.46 was achieved at 755 K in the La-Ag dual-doped sample, which was superior to that of the pristine sample(0.27 at 755 K) as well as the mono-doped counterparts. Present work demonstrates that heterolayer-isovalent dual-doping with La/Ag equivalent atoms in BiCuSeO can synergistically modulate its thermoelectric transport parameters with significantly improved thermoelectric performance.
Taking the dual-sublayer BiCuSeO superlattice thermoelectric material as an object, equivalent mono-and dual-doped samples were prepared by substitution of Bi and Cu atoms in the corresponding [Bi2 O2]2+ sublayer and[Cu2 Se2]2– sublayer with isovalent La and Ag atoms. Their thermoelectric properties and the defect modulation mechanism were studied. The results showed that La-Ag dual-doped sample could combine the advantages of mono-doped samples to achieve an relative high carrier mobility while moderately increasing the carrier concentration, thereby maximizing the electrical conductivity. At the same time, it can also induce a potential band convergence effect,achieving the low average band effective mass and high density of states effective mass at the same time, which finally endowed Bi0.98 La0.02 Cu0.98 Ag0.02 SeO with simultaneous high carrier mobility and Seebeck coefficient, as well as the optimized power factor(PF=σS2). On the other hand, due to the strong point defect scattering on the heat-carrying phonons, the lattice and total thermal conductivities of these isovalent doped samples were further reduced, which finally optimized the figure of merit(ZT). As a result, a high ZT value of 0.46 was achieved at 755 K in the La-Ag dual-doped sample, which was superior to that of the pristine sample(0.27 at 755 K) as well as the mono-doped counterparts. Present work demonstrates that heterolayer-isovalent dual-doping with La/Ag equivalent atoms in BiCuSeO can synergistically modulate its thermoelectric transport parameters with significantly improved thermoelectric performance.
引文
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[2]CHU S, MAJUMDAR A. Opportunities and challenges for a sustainable energy future. Nature, 2012, 488(7411):294–303.
[3]ARMSTRONGRC,WOLFRAMC,DEJONGKP,etal.The frontiers of energy. Nat. Energy, 2016, 1(1):15020.
[4]ZEIERWG,SCHMITTJ,HAUTIERG,etal.Engineering half-HeuslerthermoelectricmaterialsusingZintlchemistry.Nat.Rev. Mater., 2016, 1(6):16032–1–10.
[5]RULL-BRAVO M, MOURE A, FERNANDEZ J F, et al. Skutterudites as thermoelectric materials:revisited. RSC Adv., 2015, 5(52):41653–41667.
[6]FITRIANI, OVIK R, LONG B D, et al. A review on nanostructures of high-temperature thermoelectricmaterials for waste heat recovery. Renewable Sustainable Energy Rev., 2016, 64:635–659.
[7]SOOTSMANJR,CHUNGDY,KANATZIDIS·MG.Newand oldconceptsinthermoelectricmaterials.Angew.Chem.Int.Ed.,2009, 48(46):8616–8639.
[8]XIAO C, LI Z, LI K, et al. Decoupling interrelated parameters for designing high performance thermoelectric materials. Acc. Chem.Res., 2014, 47(4):1287–1295.
[9]URBAN J J. Prospects for thermoelectricity in quantum dot hybrid arrays. Nat. Nanotechnol., 2015, 10(12):997–1001.
[10]BEEKMAN M, MORELLI D T, NOLAS G S. Better thermoelectrics through glass-like crystals. Nat. Mater., 2015, 14(12):1182–1185.
[11]SNYDER G J, TOBERER E S. Complex thermoelectric materials.Nat. Mater., 2008, 7(2):105–114.
[12]TANG,ZHAOLD,KANATZIDIS·MG.Rationallydesigning high-performance bulk thermoelectric materials. Chem. Rev., 2016,116(19):12123–12149.
[13]HICKSLD,DRESSELHAUS·MS.Effectofquantum-well structures on the thermoelectric figure of merit. Phys. Rev. B, 1993,47(19):12727–12731.
[14]OHTA H, KIM S W, MUNE Y, et al. Giant thermoelectric Seebeck coefficientofatwo-dimensionalelectrongasinSrTiO3.Nat.Mater., 2007, 6(2):129–134.
[15]SUN Y, CHENG H, GAO S, et al. Atomically thick bismuth selenide freestanding single layers achieving enhanced thermoelectric energy harvesting. J. Am. Chem. Soc., 2012, 134(50):20294–20297.
[16]LIUY,ZHAOLD,LIUY,etal.Remarkableenhancementin thermoelectric performance of BiCuSeO by Cu deficiencies. J. Am.Chem. Soc., 2011, 133(50):20112–20115.
[17]ZHANG X, CHANG C, ZHOU Y, et al. BiCuSeO thermoelectrics:anupdateonrecentprogressandperspective.Materials,2017,10(2):198.
[18]ZHAO L D, HE J, BERARDAN D, et al. BiCuSeO oxyselenides:newpromisingthermoelectricmaterials.EnergyEnviron.Sci.,2014, 7(9):2900–2924.
[19]LIJ,SUIJ,PEIY,etal.Ahighthermoelectricfigureofmerit ZT>1 in Ba heavily doped BiCuSeO oxyselenides. Energy Environ.Sci., 2012, 5(9):8543–8547.
[20]LI Z, XIAO C, FAN S, et al. Dual vacancies:an effective strategy realizingsynergisticoptimizationofthermoelectricpropertyin BiCuSeO. J. Am. Chem. Soc., 2015, 137(20):6587–6593.
[21]LIU Y, ZHAO L D, ZHU Y, et al. Synergistically optimizing electricalandthermaltransportpropertiesofBiCuSeOviaadualdoping approach. Adv. Energy Mater., 2016, 6(9):1502423–1–9.
[22]HEREMANS J P, JOVOVIC V, TOBERER E S, et al. Enhancement of thermoelectric efficiency in PbTe by distortion of the electronic density of states. Science, 2008, 321(5888):554–557.
[23]XIAOC,XUJ,CAOB,etal.Solid-solutionedhomojunction nanoplateswithdisorderedlattice:apromisingapproachtoward“phononglasselectroncrystal”thermoelectricmaterials.J.Am.Chem. Soc., 2012, 134(18):7971–7977.
[24]WU H J, ZHAO L D, ZHENG F S, et al. Broad temperature plateauforthermoelectricfigureofmeritZT>2inphase-separated PbTe0.7S0.3. Nat. Commun., 2014, 5:4515–1–9.
[25]ZHAOLD,ZHANGX,WUH,etal.Enhancedthermoelectric properties in the counter-doped SnTe systemwith strained endotaxial SrTe. J. Am. Chem. Soc., 2016, 138(7):2366–2373.
[26]MAHANGD,BARTKOWIAKM.Wiedemann–Franzlawat boundaries. Appl. Phys. Lett., 1999, 74(7):953–954.
[27]LIU Y, DING J, XU B, et al. Enhanced thermoelectric performance of La-doped BiCuSeO by tuning band structure. Appl. Phys. Lett.,2015, 106(23):233903–1–5.
[28]PEIY,SHIX,LALONDEA,etal.Convergenceofelectronic bandsforhighperformancebulkthermoelectrics.Nature,2011,473(7345):66–69.
[29]BANIK A, SHENOY U S, ANAND S, et al. Mg alloying in SnTe facilitates valence band convergence and optimizes thermoelectric properties. Chem. Mater., 2015, 27(2):581–587.
[30]TAN G, SHI F, HAO S, et al. Codoping in SnTe:enhancement of thermoelectricperformancethroughsynergyofresonancelevels and band convergence. J. Am. Chem. Soc., 2015, 137(15):5100–5112.