Recent progress of 2-dimensional layered thermoelectric materials

Yu Ze-Hao; Zhang Li-Fa; Wu Jing; Zhao Yun-Shan

doi:10.7498/aps.72.20222095

Abstract

Nowadays, there are enormous amounts of energy wasted in the world, most of which is in the form of wasted heat. Thermoelectric effect, by converting heat energy into electricity without releasing dangerous substances, has aroused more and more interest from researchers. Since the discovery of graphene, more and more two-dimensional layered materials have been reported, which typically own superior electrical, optical and other physical properties over the bulk materials, and the development of the new theory and experimental technologies stimulates further research for them as well. In this work, first we introduce the measurement methods and techniques that are suitable for characterizing the thermoelectric properties of two-dimensional materials, and then discuss the relevant current challenging issues. Subsequently, graphene, transition metal disulfides, black phosphorus and other 2-dimensional materials in thermoelectric applications are introduced. Finally, we discuss the various strategies to improve the thermoelectric performance and the problems that need solving urgently.

Keywords:

Authors and contacts

1.
Phonon Engineering Research Center of Jiangsu Province, Center for Quantum Transport and Thermal Energy Science, Institute of Physics Frontiers and Interdisciplinary Sciences, School of Physics and Technology, Nanjing Normal University, Nanjing 210023, China
2.
Institute of Materials Research and Engineering, Agency for Science, Technology and Research, Singapore 138634, Singapore

Corresponding author: Zhang Li-Fa, phyzlf@njnu.edu.cn ; Wu Jing, wujing@imre.a-star.edu.sg ; Zhao Yun-Shan, phyzys@njnu.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 12204244), the Natural Science Foundation of Jiangsu Province, China (Grant No. BK20210556), and the Jiangsu Specially-Appointed Professor Program, China.

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Cited By

图 1 (a) 塞贝克系数、电导率、功率因数随载流子浓度的相互依赖关系和电子热导率与晶格热导率随载流子浓度的依赖关系^[10]; (b) 不同维度材料的电子态密度随能量的变化关系^[13]

Figure 1. (a) The interdependence of Seebeck coefficient, conductivity, power factor for different carrier concentration and electron thermal conductivity and lattice thermal conductivity as a function of carrier concentration^[10]; (b) electronic DOS of different dimensional materials as a function of energy^[13].

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图 2 (a) 基于场效应晶体管对二维半导体热电性质测量器件示意图^[24]; (b) 利用电子双层结构离子液体晶体管对二维材料的热电性质测量器件示意图^[25]; (c) 悬空热桥法器件示意图^[26]; (d) 利用H型方法测量样品的塞贝克系数示意图^[27]

Figure 2. (a) Schematic image of device for measuring thermoelectric property based on field effect transistor (FET)^[24]; (b) schematic image of device for thermoelectric property measurement based on electronic double-layer structure ionic liquid transistor^[25]; (c) schematic image of suspended thermal bridge device^[26]; (d) schematic image of H-type method device^[27].

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图 3 (a) 石墨烯中不同声子模式对热导率的贡献^[59]; (b) 石墨烯热导率与样品长度关系的不同结果汇总^[38]; (c) 石墨烯的电导率和塞贝克系数随栅极电压的变化关系(上方插图为石墨烯器件的扫描电子显微镜图像, 下方插图为${V_{\rm{g}}}$ = –5, –30 V时塞贝克系数随温度的变化)^[15]; (d) 在290 K下, G/hBN和G/SiO₂的PFT随栅极电压的变化关系^[10]

Figure 3. (a) Contribution of different phonon modes to thermal conductivity in graphene^[59]; (b) summary of thermal conductivity of graphene as a function of sample length^[38]; (c) conductivity and Seebeck coefficient of graphene as a function of gate voltage (Upper inset: SEM image of a graphene device, the scale bar is 2 μm. Lower inset: Seebeck coefficient of graphene as a function of temperature at ${V_{\rm{g}}}$ = –5, –30 V) ^[15]; (d) PFT as a function of gate voltage in both devices at 290 K^[10].

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图 4 (a) 单层二硫化钼的示意图(其中紫色为Mo原子、黄色为S原子)^[84]; (b) 室温下关于MoS₂的热导率研究结果的汇总^[38]; (c) 不同${V_{\rm{g}}} - {V_{\rm th}}$下, 四端法测得的MoS₂的电导率和塞贝克系数随样品厚度(层数)的变化关系^[28]; (d) 不同${V_{\rm{g}}} - {V_{\rm th}}$下, MoS₂的功率因数随样品厚度(层数)的变化关系^[28]; (e) 不同厚度(1—3层)的MoS₂的功率因数随${V_g}$的变化关系^[35]

Figure 4. (a) Schematic image of monolayer MoS₂ (Where purple is Mo atom and yellow is S atom) ^[84]; (b) summary of thermal conductivity of MoS₂ at room temperature^[38]; (c) four-probe conductivity and Seebeck coefficient of MoS₂ as a function of the thickness (number of layers) measured at different ${V_{\rm{g}}} - {V_{\rm th}}$ values; (d) PF of MoS₂ as a function of the thickness (number of layers) measured at different ${V_{\rm{g}}} - {V_{\rm th}}$ values^[28]; (e) PF of MoS₂ with different thick (monolayer-three layers) as a function of the ${V_{\rm{g}}}$^[35].

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图 5 (a) 300 K下, 极薄单晶WSe₂的电导率(两端法)、塞贝克系数和功率因数随${V_{\rm{g}}}$的变化关系^[106]; (b) 厚度为5和9 nm的PdSe₂薄片的功率因数^[107]; (c) 室温下不同厚度的InSe薄膜的功率因数随载流子浓度的变化关系^[108]

Figure 5. (a) ${\sigma _{{\text{2D}}}}$, $S$ and ${S^2}\sigma $ of ultrathin WSe₂ single crystals as a function of the ${V_{\text{g}}}$ at T = 300 K^[106]; (b) power factor of PdSe₂ flakes with thickness of 5 and 9 nm^[107]; (c) power factor of InSe film with different thickness as a function of carrier concentration at room temperature^[108].

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图 6 (a) 黑磷晶体结构的示意图^[125]; (b) 黑磷纳米带在AC和ZZ方向的热导率和杨氏模量测量值, 其中热导率和杨氏模量有着相似的各向异性比值(分别为2.24和2.05)^[126]; (c) AC方向和ZZ方向的黑磷纳米带电导率(c)和塞贝克系数(d)随温度的变化关系^[127]; (e) 黑磷塞贝克系数的少层实验数据和体块理论计算数值(实线为${S_x}$, 虚线为${S_y}$)的比较^[25]; (f) 210 K下, 少层黑磷的功率因数随栅极电压的变化关系^[25]

Figure 6. (a) Schematic image of BP reproduced with permission^[125]; (b) thermal conductivity and Young’s modulus values of the BP nanoribbons. The thermal conductivity anisotropy ratio (≈2.24) between ZZ and AC is similar to that of Young’s modulus (≈2.05)^[126]; temperature dependence of electrical conductivity (c) and Seebeck coefficient (d) of BP nanoribbons along the AC and ZZ directions^[127]; (e) comparison between experimental data and bulk values of theoretical calculation (${S_x}$, solid line; ${S_y}$ dashed line) of Seebeck coefficient of BP^[25]; (f) power factor of few layer BP as a function of gate voltage at 210 K^[25].

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图 7 (a) 少层Bi₂O₂Se晶体的功率因数随着栅极电压和温度的变化关系^[24]; (b) 单层GeAs₂(n型或p型)在不同温度下的热电优值的最大值^[141]

Figure 7. (a) PF of few-layer Bi₂O₂Se as a function of gate voltage and temperature^[24]; (b) maximum ZT of monolayer GeAs₂ at different temperature (including n type and p type)^[141].

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图 8 (a) MoS₂/hBN器件的四端法电导率随温度和栅极电压的变化关系(低温下电导率出现异常的峰值用红色虚线标出)^[159]; (b) MoS₂/SiO₂和MoS₂/hBN器件的塞贝克系数与温度的变化关系(其中MoS₂/hBN器件${V_{\rm{g}}}$ = 70 V以圆形表示, ${V_g}$ = 50 V以方形表示, ${V_{\rm{g}}}$= 30 V以钻石形状表示)^[159]; (c) 氦离子辐射同时增加Bi₂Te₃塞贝克系数和载流子浓度(虚线为不同散射弛豫时间指数下塞贝克系数的计算结果)^[45]; (d) 不同厚度的Bi₂Te₃的功率因数随辐射剂量的变化关系^[45]

Figure 8. (a) Four-probe electrical conductivity of MoS₂/hBN devices as a function of Temperature and back gate voltage^[159]; (b) temperature dependent Seebeck coefficient of MoS₂/SiO₂ and MoS₂/hBN device at ${V_{\rm{g}}}$ = 70 V (circle), 50 V (square), and 30 V (diamond) ^[159]; (c) the simultaneous increase of Seebeck coefficient and carrier concentration of helium ion irradiated Bi₂Te₃^[45]; (d) irradiation dose dependent power factor of Bi₂Te₃ with different thicknesses^[45].

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图 9 (a) 在SiO₂/Si基底上, 真空退火3次Li_xMoS₂的拉曼光谱图^[173]; (b) 经过每次退火后的Li_xMoS₂的塞贝克系数、电导率和功率因数^[173]; (c) 沿各个方向的本征MoS₂和氧原子掺杂MoS₂的PF随温度的变化^[176]; (d) 沿各个方向的本征MoS₂和氧原子掺杂MoS₂的热导率随温度的变化^[176]

Figure 9. (a) Raman spectra of a Li_xMoS₂ flake on SiO₂/Si substrate across three separate annealing cycles performed in vacuum^[173]; (b) Seebeck coefficient, electrical conductivity, and power factor of Li_xMoS₂ device across all annealing cycles^[173]; (c) power factor of the pristine MoS₂ and oxygen-doped MoS₂ along both directions^[176]; (d) thermal conductivity of the pristine MoS₂ and oxygen-doped MoS₂ along both directions^[176].

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图 10 (a) Bi₂Te₃/Sb₂Te₃超晶格、PbSnSeTe/PbTe量子点超晶格、PbTe_0.02Se_0.98/PbTe量子点超晶格的热电优值^[178]; (b) 计算获得的不同周期厚度的横向超晶格晶格热导率随温度的关系^[183]; (c) TiS₂[(HA)_x(H₂O)_y(DMSO)_z]超晶格材料的HAADF-STEM 图像(展示了褶皱的晶格结构)^[10]; (d) 放大的TiS₂[(HA)_x(H₂O)_y(DMSO)_z]超晶格材料的HAADF-STEM 图像^[10]; (e) 本征TaS₂和SCCM-TaS₂的电导率^[185]; (f) 本征TaS₂和SCCM-TaS₂的塞贝克系数^[185]

Figure 10. (a) Thermoelectric figure of merit for Bi₂Te₃/Sb₂Te₃ superlattices, PbSnSeTe/PbTe quantum dot superlattices, and PbTe_0.02Se_0.98/PbTe quantum dot superlattices^[178]; (b) temperature dependence of calculated lattice thermal conductivity of lateral superlattices with different periodic thicknesses^[183]; (c) HAADF-STEM (high-angle annular dark field scanning transmission electron microscope) image of the TiS₂[(HA)_x(H₂O)_y(DMSO)_z] hybrid superlattice showing a wavy structure^[10]. (d) magnified HAADF-STEM image of TiS₂[(HA)_x(H₂O)_y(DMSO)_z]^[10]; (e) electrical conductivity of the pristine TaS₂ crystals and SCCM-TaS₂ hybrid structure^[185]; (f) seebeck coefficient of the pristine TaS₂ crystals and SCCM-TaS₂ hybrid structure^[185].

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图 11 (a) 利用AFM对悬空单层MoS₂施加应力的示意图^[85]; (b) 褶皱的单层MoS₂的构造过程示意图^[193]; (c) 利用三点弯曲法对MoS₂进行延伸示意图^[194]; (d) 黑磷的热电优值随温度和应变的变化关系^[199]; (e) 在300, 600和900 K下施加双向压缩和拉伸应变的n型或p型WS₂的${{{S^2}\sigma } \mathord{\left/ {\vphantom {{{S^2}\sigma } \tau }} \right. } \tau }$值^[201]; (f) 不同厚度(层数)的平坦和褶皱的MoS₂的功率因数随载流子浓度的变化关系^[195]

Figure 11. (a) Schematic image of inducing strain to the suspended monolayer MoS₂ by AFM^[85]; (b) schematic image of the fabrication process of wrinkled MoS₂ nanolayers^[193]; (c) schematic image of the extension of MoS₂ by the three-point bending apparatus^[194]; (d) ZT of BP as a function of temperature and strain^[199]; (e)${{{S^2}\sigma } \mathord{\left/ {\vphantom {{{S^2}\sigma } \tau }} \right. } \tau }$ of WS₂ with applied both biaxial compressive and tensile strain for n-type and p-type doping at 300, 600 and 900 K^[201]; (f) PF of flat and ripped MoS₂ as a function of carrier concentration with different thickness^[195].

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