High Thermoelectric Performance of ZnO by Coherent Phonon Scattering and Optimized Charge Transport

ZnO is identified as a potentially attractive n-type oxide thermoelectric material due to its abundance, nontoxicity, and a high degree of stability. However, working with ZnO is challenging due to its high thermal conductivity from its strong ionic bonds and low electrical conductivity due to its low charge concentrations. Here, it is demonstrated that the electrical and thermal transport properties of ZnO can be simultaneously improved via the successful doping of Al and ZnS coating. The ZnS coating in Al-doped ZnO is observed and analyzed through microstructure and spectroscopic studies. The power factor for 1% ZnS-coated Zn_0.98Al_0.02O is increased to ≈0.75 mW m⁻¹ K⁻² at 1073 K, 161% higher than pure ZnO. This enhancement in the power factor can be explained by the aliovalent Al³⁺ doping and modifications in intrinsic defects, leading to an increased carrier concentration. Interestingly, ZnS coating significantly reduces lattice thermal conductivity to ≈2.31 W m⁻¹ K⁻¹ at 1073 K for 2% ZnS-coated Zn_0.98Al_0.02O, a 62% decrease over pure ZnO. This large reduction in lattice thermal conductivity can be elucidated based on coherent phonon scattering via Callaway's model. Overall, the figure of merit, zT, increases to 0.2 in 2% ZnS-coated Zn_0.98Al_0.02O, which is 272% higher than pure ZnO at 1073 K.     

Evaluation of Half‐Heusler Compounds as Thermoelectric Materials Based on the Calculated Electrical Transport Properties

A theoretical evaluation of the thermoelectric‐related electrical transport properties of 36 half‐Heusler (HH) compounds, selected from more than 100 HHs, is carried out in this paper. The electronic structures and electrical transport properties are studied using ab initio calculations and the Boltzmann transport equation under the constant relaxation time approximation for charge carriers. The electronic structure results predict the band gaps of these HH compounds, and show that many HHs are narrow‐band‐gap semiconductors and, therefore, are potentially good thermoelectric materials. The dependence of Seebeck coefficient, electrical conductivity, and power factor on the Fermi level is investigated. Maximum power factors and the corresponding optimal p‐ or n‐type doping levels, related to the thermoelectric performance of materials, are calculated for all HH compounds investigated, which certainly provide guidance to experimental work. The estimated optimal doping levels and Seebeck coefficients show reasonable agreement with the measured results for some HH systems. A few HHs are recommended to be potentially good thermoelectric materials based on our calculations.     

Energy Filtering of Charge Carriers: Current Trends,Challenges, and Prospects for Thermoelectric Materials

Exhaustive attempts are made in recent decades to improve the performance of thermoelectric materials that are utilized for waste heat‐to‐electricity conversion. Energy filtering of charge carriers is directed toward enhancing the material thermopower. This paper focuses on the theoretical concepts, experimental evidence, and the authors' view of energy filtering in the context of thermoelectric materials. Recent studies suggest that not all materials experience this effect with the same intensity. Although this effect theoretically demonstrates improvement of the thermopower, applying it poses certain constraints, which demands further research. Predicated on data documented in literature, the unusual dependence of the thermopower and conductivity upon charge carrier concentrations can be altered through the energy filtering approach. Upon surmounting the physical constraints discussed in this article, thermoelectric materials research may gain a new direction to enhance the power factor and thermoelectric figure of merit.     

制备工艺对新型热电材料制冷性能的影响

通过取点法得到了由Ingot法、BM法、S-MS法和Te-MS法制备的四种新型p型热电材料(Bi0.5Sb1.5)Te3的变物性参数拟合公式,分析了温度对不同方法制备的热电材料的影响,得到了热电材料无量纲优值与绝对温度的关系曲线.从热力学方面研究了制备工艺对基于新型热电材料的热电制冷器最大制冷系数的影响.结果表明:由Te-MS法制备的新型p型热电材料(Bi0.5Sb1.5)Te3具有最大的优值系数,基于该材料的热电制冷器最大制冷系数可达2.49,较其他三种方法制备的热电材料分别提升了 34.59％,37.57％和25.76％.     

The Role of Ionized Impurity Scattering on the Thermoelectric Performances of Rock Salt AgPbmSnSe2+m

This study reports on the successful synthesis and on the properties of polycrystalline AgPb_mSnSe_2+m (m = ∞, 100, 50, 25) samples with a rock salt structure. Between ≈160 and ≈400 K, the dominant scattering process of the carriers in this system changes from acoustic phonon scattering in PbSe to ionized impurity scattering in AgPb_mSnSe_2+m, which synergistically optimizes electrical and thermal transport properties. Thanks to the faint amount of AgSnSe₂, the Seebeck coefficient is enhanced by boosting the scattering factor, the electric conductivity is improved by the increase of the concentration of holes coupled to a limited degradation of their mobility, and the total thermal conductivity is reduced by suppressing bipolar thermal conductivity. Therefore, ZT of AgPb_mSnSe_2+m (m = 50) reaches 1.3 at 889 K. The mechanism suggested in this study opens new paths to improve the thermoelectric performances of other families of materials.     

弛豫时间对双势垒结构电子输运性质的影响

利用对双势垒器件非平衡态电子输运性质的含时动力学模拟计算,分析了弛豫时间对这类低维器件电子输运特性的影响.结果表明,由于电子-声子、电子-杂质和电子-缺陷等相互作用导致的弛豫时间对器件Ⅰ-Ⅴ曲线产生很大的影响,即电流滞后类平台结构的倾斜度以及电流滞后区的宽度.     

Effect of Relaxation Time on Electron Transport Properties in Double-Barrier Structures

利用对双势垒器件非平衡态电子输运性质的含时动力学模拟计算,分析了弛豫时间对这类低维器件电子输运特性的影响.结果表明,由于电子-声子、电子-杂质和电子-缺陷等相互作用导致的弛豫时间对器件Ⅰ-Ⅴ曲线产生很大的影响,即电流滞后类平台结构的倾斜度以及电流滞后区的宽度.     

Nanoscale Organic Thermoelectric Materials: Measurement,Theoretical Models,and Optimization Strategies

The demands for waste heat energy recovery from industrial production, solar energy, and electronic devices have resulted in increasing attention being focused on thermoelectric materials. Over the past two decades, significant progress is achieved in inorganic thermoelectric materials. In addition, with the proliferation of wireless mobile devices, economical, efficient, lightweight, and bio‐friendly organic thermoelectric (OTE) materials have gradually become promising candidates for thermoelectric devices used in room‐temperature environments. With the development of experimental measurement techniques, the manufacturing for nanoscale thermoelectric devices has become possible. A large number of studies have demonstrated the excellent performance of nanoscale thermoelectric devices, and further improvement of their thermoelectric conversion efficiency is expected to have a significant impact on global energy consumption. Here, the development of experimental measurement methods, theoretical models, and performance modulation for nanoscale OTE materials are summarized. Suggestions and prospects for the future development of these devices are also provided.     

Effect of MBE Growth Conditions on Multiple Electron Transport in InN

A quantitative mobility spectrum analysis (QMSA) of multiple magnetic field data has been used to determine the transport properties of bulk and surface electron species in InN films, grown by plasma-assisted molecular beam epitaxy (PAMBE) with varying substrate temperatures and In/N flux ratios. While all films have similar bulk electron densities, ∼4 × 10¹⁷ cm⁻³, the highest mobility was obtained in the highest growth temperature film (3100 cm²/V s at 150 K), while In-rich growth also gave good mobility values even at a much lower growth temperature. The surface sheet electron concentration increased with surface roughness, which increased with N-flux during growth.     

模式耦合对量子线电子输运性质的影响

利用一般传输矩阵方法 (Transfer matrix method)和耦合模传输矩阵方法 (Coupledmode transfer matrix method) ,分别计算了几种处于弹道区的非均匀边界形状量子线的电导 ,研究量子线通道相邻分段区域电子传输模式之间的耦合对电导的影响。结果表明 ,这种耦合对空腔结构量子线电子输运性质有重要影响 ,是研究非均匀边界形状量子线电导必须考虑的关键因素。     

垂直电场作用下的钎锌矿相GaN电子输运特性的Monte Carlo研究

在GaN NMOSFET中,沟道电子由于受垂直于其运动方向电场的作用而产生界面散射,从而影响MOSFET特性.研究采用Monte Carlo体模拟方法计算钎锌矿相GaN材料在界面散射下的电子输运特性.模拟中在电子漂移方向加一个水平电场,同时在与其垂直的方向加另外一个电场,在垂直电场作用下,电子发生界面散射.采用基于指数...     

Origin of Phonon Glass–Electron Crystal Behavior in Thermoelectric Layered Cobaltate

Measurement of local disorder and lattice vibrations is of great importance for understanding the mechanisms whereby thermoelectric materials efficiently convert heat to electricity. Attaining high thermoelectric power requires minimizing thermal conductivity while keeping electric conductivity high. This situation is achievable by enhancing phonon scattering through specific structural disorder (phonon glass) that also retains sufficient electron mobility (electron crystal). It is demonstrated that the quantitative acquisition of multiple annular‐dark‐field images via scanning transmission electron microscopy at different scattering‐angles simultaneously allows not only the separation but also the accurate determination of static and thermal atomic displacements in crystals. Applying the unique method to the layered thermoelectric material (Ca₂CoO₃)_0.62CoO₂ discloses the presence of large incommensurate displacive modulation and enhanced local vibration of atoms, largely confined within its Ca₂CoO₃ sublayers. Relating the refined disorder to ab initio calculations of scattering rates is a tremendeous challenge. Based on an approximate calculation of scattering rates, it is suggested that this well‐defined deterministic disorder engenders static displacement‐induced scattering and vibrational‐induced resonance scattering of phonons as the origin of the phonon glass. Concurrently, the crystalline CoO₂ sublayers provide pathways for highly conducting electrons and large thermal voltages.     

Nb-Mediated Grain Growth and Grain-Boundary Engineering in Mg3Sb2-Based Thermoelectric Materials

The poor carrier mobility of polycrystalline Mg₃Sb₂ at low temperatures strongly degrades the thermoelectric performance. Ionized impurities are initially thought to dominate charge carrier scattering at low temperatures. Accordingly, the increased electrical conductivity by replacing Mg with metals such as Nb is also attributed to reduced ionized impurity scattering. Recent experimental and theoretical studies challenge this view and favor the grain boundary (GB) scattering mechanism. A reduction of GB scattering improves the low-temperature performance of Mg₃(Sb, Bi)₂ alloys. However, it is still elusive how these metal additions reduce the GB resistivity. In this study, Nb-free and Nb-added Mg₃Sb₂ are studied through diffraction, X-ray absorption spectroscopy, solid-state nuclear magnetic resonance spectroscopy, and atom probe tomography. It is shown that Nb does not enter the Mg₃Sb₂ matrix and remains in the metallic state. Besides, Nb diffuses along the GB forming a wetting layer, which modifies the interfacial energy and accelerates grain growth. The GB resistivity appears to be reduced by Nb-enrichment, as evidenced by modeling the electrical transport properties. This study not only confirms the GB scattering in Mg₃Sb₂ but also reveals the hitherto hidden role of metallic additives on enhancing grain growth and reducing the GB resistivity.     

热电材料的研究进展

随着热电材料与薄膜制备技术和性能研究手段的发展,具有高热电性能的热电薄膜和低维结构受到人们关注。目前,国内外研究主要集中在如何提高热电材料的能量转换率等核心技术问题上。介绍了热电材料的理论背景、材料分类、制备手段和热电性质的表征,其中,制备手段及热电性质表征主要以Bi2Te3基热电材料展开论述。最后,对热电材料的发展和未来研究方向进行总结。     

热电Ca3Co4O9薄膜的一致取向生长及其激光感生电压效应

利用脉冲激光沉积(PLD)法,在蓝宝石(0001)平衬底上成功制备了c轴一致取向的Ca3Co4O9薄膜。利用X射线衍射(XRD)分析测定了薄膜的相结构和生长取向。研究了不同衬底温度与不同原位氧压对Ca3Co4O9薄膜结晶质量与生长取向的影响,确定了最佳生长条件。利用这一条件在倾斜Al2O3(0001)衬底上制备了Ca3Co4O9薄膜。研究发现,当Ca3Co4O9薄膜被波长248nm,脉冲宽度20ns的脉冲激光照射时,在薄膜两端存在较大的激光感生热电电压(LITV)信号,峰值电压达到4.4V,其上升沿为36ns,半峰全宽(FWHM)为131ns。可以认为这种激光感生热电电压信号是由于Ca3Co4O9薄膜面内与面间泽贝克(Seebeck)系数张量的各向异性引起的。     

Positive Effect of Ge Vacancies on Facilitating Band Convergence and Suppressing Bipolar Transport in GeTe‐Based Alloys for High Thermoelectric Performance

Because the intrinsic Ge vacancies in GeTe usually lead to high hole concentration beyond the optimal range, many previous studies tend to consider Ge vacancies as negative effects on increasing the figure of merit ZT of GeTe‐based alloys, and consequently have proposed various approaches to suppress Ge vacancies. However, in this work, it is demonstrated that the Ge vacancies can have great positive effects on enhancing the ZT of GeTe‐based alloys when the hole concentration falls into the optimal range. First, hole concentration of GeTe is reduced close to the optimal range by co‐alloying of Pb and Bi, and then the Ge vacancies are increased by adding excess Te into the Ge_0.8Pb_0.1Bi_0.1Te_1+x. The Ge vacancies can cause lattice shrinkage and promote rhombohedral‐to‐cubic phase transition. As revealed by first‐principle calculations, theoretical simulations, and experimental tests, Ge vacancies can facilitate the band convergence, suppress the bipolar transport at higher temperature range, and reduce the lattice thermal conductivity. Combining these effects, a peak ZT of 1.92 at 637 K and an average ZT of 1.34 within 300–773 K in Ge_0.8Pb_0.1Bi_0.1Te_1.06 can be obtained, demonstrating the great significance of utilizing vacancy‐type defects for enhancing ZT.     

Thermoelectric Effect Spectroscopy and Photoluminescence of High-Resistivity CdTe:In

Thermoelectric effect spectroscopy and photoluminescence techniques were used to study the defect levels in samples from three crystals of CdTe:In grown by the vertical gradient freeze method. The main goal of the investigation was to study defects, which strongly trap charge carriers or act as recombination centers in order to eliminate them from the technological process. The main difference among detecting and non-detecting samples was the absence of electron traps with a very high capture cross-section and energy 0.6 eV to 0.7 eV, which act as lifetime killers even at low concentrations. Recently published ab initio calculations show a complex of Te antisite and Cd vacancy within this energy range.