Theoretical study on electronic structure and thermoelectric properties of PbS_xTe_(1-x)(x = 0.25, 0.5, and 0.75) solid solution

The electronic structure and thermoelectric(TE) properties of PbS_xTe_(1-x)(x = 0.25, 0.5, and 0.75) solid solution have been studied by combining the first-principles calculations and semi-classical Boltzmann theory. The special quasirandom structure(SQS) method is used to model the solid solutions of PbS_xTe_(1-x), which can produce reasonable electronic structures with respect to experimental results. The maximum zT value can reach 1.67 for p-type PbS0.75Te0.25 and 1.30 for PbS0.5Te0.5 at 800 K, respectively. The performance of p-type PbS_xTe_(1-x) is superior to the n-type ones, mainly attributed to the higher effective mass of the carriers. The z T values for PbS_xTe_(1-x) solid solutions are higher than that of pure Pb Te and Pb S, in which the combination of low thermal conductivity and high power factor play important roles.     

Enhanced thermoelectric performance in p-type Mg_3Sb_2 via lithium doping

The Zintl compound Mg_3Sb_2 has been recently identified as promising thermoelectric material owing to its high thermoelectric performance and cost-effective,nontoxicity and environment friendly characteristics.However,the intrinsically p-type Mg_3Sb_2 shows low figure of merit(z T = 0.23 at 723 K) for its poor electrical conductivity.In this study,a series of Mg_(3-x)Li_xSb2 bulk materials have been prepared by high-energy ball milling and spark plasma sintering(SPS) process.Electrical transport measurements on these materials revealed significant improvement on the power factor with respect to the undoped sample,which can be essentially attributed to the increased carrier concentration,leading to a maximum z T of0.59 at 723 K with the optimum doping level x = 0.01.Additionally,the engineering z T and energy conversion efficiency are calculated to be 0.235 and 4.89%,respectively.To our best knowledge,those are the highest values of all reported p-type Mg_3Sb_2-based compounds with single element doping.     

Zn1-xMgxO薄膜p型导电和光学性能

采用超声喷雾热分解(Ultrasonic Spray Pyrolysis,USP)方法,以醋酸锌、醋酸镁、醋酸铵、氯化铝的混合水溶液为前驱溶液,在单晶Si(100)衬底上制备了ZnO,Zn_0.81Mg_0.19O,N-Al共掺杂ZnO和N-Al共掺杂Zn_0.81Mg_0.19O薄膜。以X射线衍射(XRD)、场发射-扫描电镜(FE-SEM)、霍尔效应(Hall-effect)、光致发光(Photoluminescence,PL)谱等手段研究了薄膜的晶体结构、表面形貌、电学性能、光学性能和带隙变化。电学测试结果表明,未掺杂ZnO及Zn_0.81Mg_0.19O薄膜为n型导电;而N-Al共掺杂ZnO和N-Al共掺杂Zn_0.81Mg_0.19O薄膜呈p型导电。Zn_0.81Mg_0.19O和N-Al共掺杂Zn_0.81Mg_0.19O(p型)薄膜在维持ZnO纤锌矿结构的前提下,光学带隙随Mg掺杂量增加而增大。初步结果显示,优化工艺参数下通过Mg掺杂制备光学带隙可调的p型Zn_0.81Mg_0.19O薄膜,对于试制Zn_1-xMg_xO基同质p-n结、短波长(紫外、深紫外)器件等方面有重要意义。     

Thermoelectric effects and topological insulators

The recent discovery of topological insulators(TIs) offers new opportunities for the development of thermoelectrics,because many TIs(like Bi_2Te_3) are excellent thermoelectric(TE) materials.In this review,we will first describe the general TE properties of TIs and show that the coexistence of the bulk and boundary states in TIs introduces unusual TE properties,including strong size effects and an anomalous Seebeck effect.Importantly,the TE figure of merit zT of TIs is no longer an intrinsic property,but depends strongly on the geometric size.The geometric parameters of twodimensional TIs can be tuned to enhance zT to be significantly greater than 1.Then a few proof-of-principle experiments on three-dimensional TIs will be discussed,which observed unconventional TE phenomena that are closely related to the topological nature of the materials.However,current experiments indicate that the metallic surface states,if their advantage of high mobility is not fully utilized,would be detrimental to TE performance.Finally,we provide an outlook for future work on topological materials,which offers great possibilities to discover exotic TE effects and may lead to significant breakthroughs in improving zT.     

Two-dimensional square-Au_2S monolayer: A promising thermoelectric material with ultralow lattice thermal conductivity and high power factor

The search for new two-dimensional(2 D) harvesting materials that directly convert(waste) heat into electricity has received increasing attention. In this work, thermoelectric(TE) properties of monolayer square-Au_2S are accurately predicted using a parameter-free ab initio Boltzmann transport formalism with fully considering the spin–orbit coupling(SOC),electron–phonon interactions(EPIs), and phonon–phonon scattering. It is found that the square-Au_2S monolayer is a promising room-temperature TE material with an n-type(p-type) figure of merit ZT = 2.2(1.5) and an unexpected high n-type ZT = 3.8 can be obtained at 600 K. The excellent TE performance of monolayer square-Au_2S can be attributed to the ultralow lattice thermal conductivity originating from the strong anharmonic phonon scattering and high power factor due to the highly dispersive band edges around the Fermi level. Additionally, our analyses demonstrate that the explicit treatments of EPIs and SOC are highly important in predicting the TE properties of monolayer square-Au_2S. The present findings will stimulate further the experimental fabrication of monolayer square-Au_2S-based TE materials and offer an in-depth insight into the effect of SOC and EPIs on TE transport properties.     

Convergence of conduction bands as a means of enhancing thermoelectric performance of n-type Mg2Si(1-x)Sn(x) solid solutions

Mg(2)Si and Mg(2)Sn are indirect band gap semiconductors with two low-lying conduction bands (the lower mass and higher mass bands) that have their respective band edges reversed in the two compounds. Consequently, for some composition x, Mg(2)Si(1-x)Sn(x) solid solutions must display a convergence in energy of the two conduction bands. Since Mg(2)Si(1-x)Sn(x) solid solutions are among the most prospective of the novel thermoelectric materials, we aim on exploring the influence of such a band convergence (valley degeneracy) on the Seebeck coefficient and thermoelectric properties in a series of Mg(2)Si(1-x)Sn(x) solid solutions uniformly doped with Sb. Transport measurements carried out from 4 to 800 K reveal a progressively increasing Seebeck coefficient that peaks at x=0.7. At this concentration the thermoelectric figure of merit ZT reaches exceptionally large values of 1.3 near 700 K. Our first principles calculations confirm that at the Sn content x≈0.7 the two conduction bands coincide in energy. We explain the high Seebeck coefficient and ZT values as originating from an enhanced density-of-states effective mass brought about by the increased valley degeneracy as the two conduction bands cross over. We corroborate the increase in the density-of-states effective mass by measurements of the low temperature specific heat. The research suggests that striving to achieve band degeneracy by means of compositional variations is an effective strategy for enhancing the thermoelectric properties of these materials.     

The temperature dependence of thermal expansion for p-type Ce0.9Fe3.5Co0.5Sb12 and n-type Co0.95Pd0.05Te0.05Sb3 skutterudite thermoelectric materials

During waste heat recovery applications, thermoelectric (TE) materials experience thermal gradients and thermal transients, which produce stresses that scale with the TE material's coefficient of thermal expansion (CTE). Thus, the temperature-dependent CTE is an important parameter for the design of mechanically robust TE generators. For three skutterudite thermoelectric compositions, n-type Co_0.95Pd_0.05Te_0.05Sb₃ (with and without 0.1 at. % cerium doping) and p-type Ce_0.9Fe_3.5Co_0.5Sb₁₂, the CTE was measured using two methods, i.e. X-ray diffraction on powder and bulk specimens and dilatometry on bulk specimens. Each bulk specimen was hot pressed using powders milled from cast ingots. Between 300?K and 600?K, the mean CTE values were 9.8–10.3?×?10^?6 K^?1 for the non-cerium-doped n-type, 11.6?×?10^?6 K^?1 for the 0.1 at. % cerium-doped n-type and from 12.7 to 13.3?×?10^?6 K^?1 for the p-type. In the literature, similar CTE values are reported for other Sb-based skutterudites. For temperatures >600?K, an unrecovered dilatational strain (perhaps due to bloating) was observed, which may impact applications. Also, the submicron particle sizes generated by wet milling were pyrophoric; thus, during both processing and characterization, exposure of the powders to oxygen should be limited.     

Structure design for high performance n-type polymer thermoelectric materials

Organic thermoelectric(OTE)materials have been regarded as a potential candidate to harvest waste heat from complex,low temperature surfaces of objects and convert it into electricity.Recently,n-type conjugated polymers as organic thermoelectric materials have aroused intensive research in order to improve their performance to match up with their ptype counterpart.In this review,we discuss aspects that affect the performance of n-type OTEs,and further focus on the effect of planarity of backbone on the doping efficiency and eventually the TE performance.We then summarize strategies such as implementing rigid n-type polymer backbone or modifying conventional polymer building blocks for more planar conformation.In the outlook part,we conclude forementioned devotions and point out new possibility that may promote the future development of this field.     

N-type core-shell heterostructured Bi2S3@Bi nanorods/polyaniline hybrids for stretchable thermoelectric generator

With the growing need on distributed power supply for portable electronics,energy harvesting from environment becomes a promising solution.Organic thermoelectric(TE)materials have advantages in intrinsic flexibility and low thermal conductivity,thus hold great prospect in applications as a flexible power generator from dissipated heat.Nevertheless,the weak electrical transport behaviors of organic TE materials have severely impeded their development.Moreover,compared with p-type organic TE materials,stable and high-performance n-type counterparts are more difficult to obtain.Here,we developed a n-type polyaniline-based hybrid with core-shell heterostructured Bi;S;@Bi nanorods as fillers,showing a Seebeck coefficient-159.4μV/K at room temperature.Further,a couple of n/p legs from the PANI-based hybrids were integrated into an elastomer substrate forming a stretchable thermoelectric generator(TEG),whose function to output stable voltages responding to temperature differences has been demonstrated.The in situ output performance of the TEG under stretching could withstand up to 75%elongation,and stability test showed little degradation over a one-month period in the air.This study provides a promising strategy to develop stable and high thermopower organic TEGs harvesting heat from environment as long-term power supply.     

Excellent thermoelectric performance predicted in Sb2Te with natural superlattice structure

Using first-principles calculations combined with the Boltzmann transport theory, we explore the thermoelectric properties of natural superlattice (SL) structure Sb₂Te. The results show that n-type Sb₂Te possesses larger Seebeck coefficient of 249.59 (318.87) μV/K than p-type Sb₂Te of 219.85 (210.38) μV/K and low lattice thermal conductivity of 1.25 (0.21) W/mK along the in-plane (out-of-plane) direction at 300 K. The excellent electron transport performance is mainly attributed to steeper density of state around the bottom of conduction band. The ultralow lattice thermal conductivity of Sb₂Te is mainly caused by low phonon group velocity and strong anharmonicity. Further analysis shows that the decrease of group velocity comes from flatter dispersion curves which are contributed by the Brillouin-zone folding. The strong anharmonicity is mainly due to the presence of lone-pair electrons in Sb₂Te. Combining such a high Seebeck coefficient with the low lattice thermal conductivity, maximum n-type thermoelectric figure of merit (ZT) of 1.46 and 1.38 could be achieved along the in-plane and out-of-plane directions at room temperature, which is higher than the reported values of Sb₂Te₃. The findings presented here provide insight into the transport property of Sb₂Te and highlight potential applications of thermoelectric materials at room temperature.     

CexZr1-xO2固溶体储氧性能与结构的关系

采用加热回流技术制备了系列CexZr1-xO2(0.25≤x≤1)固溶体,通过N2物理吸附、XRD、Raman光谱、UV-Vis漫反射光谱表征了不同铈锆组成的铈锆复合氧化物结构对储氧性能的影响.结果表明,在铈锆组成比不同的样品之间,结构性质相差较大,随着载体中ZrO2 mol%的增加,载体结构从相对的有序经无序再回到相对的有序.Ce0.4Zr0.6O2样品具有最高的储氧性能,而Ce0.25Zr0.75O2样品具有较高的热稳定性.     

Thermoelectric generator based on a bismuth-telluride alloy fabricated by addition of ethylene glycol

This paper introduces a new method to selectively fabricate n-type and p-type bismuth (Bi)-telluride (Te) thermoelectric materials by the rate of addition of ethylene glycol (EG) in the Bi–Te co-electrodeposition solution. As the amount of added EG is increased, the atomic ratio of Bi in the deposited Bi–Te alloy reached a slope of 0.463 (at.% of Bi/vol.% of EG), and increased in a linear manner. When the EG content reached approximately 20%v/v, the n-type material changed into a p-type. This change implies that adjusting the EG content in the electrodeposition solution affords simple control of the Bi–Te composition. To demonstrate the applicability of the developed thermoelectric materials, thermoelectric generators (TEGs) were fabricated using electrodeposited n-type (using solution without EG) and p-type (using solution with 30%v/v EG) Bi–Te alloys. The Seebeck voltage of the pair of n-type and p-type thermoelectric materials was 140 mV and the power generated from the pair was 24.36 nW at a 10 °C temperature difference.     

Se替代Te对BiCuTeO电热输运性能的影响

层状氧硫族化合物由于其本征的低晶格热导率和可观的热电性能吸引了广泛关注,其中以BiCuSeO化合物的热电性能最为优异.但是,其同晶型化合物BiCuTeO,由于带隙较小且存在大量本征Cu空位,导致载流子浓度较高,热电性能较差,从而研究较少.针对BiCuTeO存在的上述问题,本文利用Se替代部分Te,以期能够展宽带隙并减少Cu空位,提高其热电性能.采用固相反应结合快速热压烧结制备了BiCuTe_(1-x)Se_xO(x=0, 0.1, 0.2, 0.3和0.4)块体热电材料,并系统地研究了该体系的电热输运性能.研究结果表明,利用Se替代Te,可以使BiCuTeO导电层化学键强度增加、带隙增大、载流子有效质量增加以及载流子散射增强,从而导致载流子浓度和迁移率同时降低,进而电导率随着Se含量增加而剧烈降低, Seebeck系数则显著增大.由于综合电输运性能恶化,功率因子随着Se含量增加而减小,导致热电优值zT随着Se含量增加而降低.最终,Se含量为x=0.1的样品,在室温和723 K时的zT值分别达到约0.3和0.7,仍然在较宽温区内保持较高的zT值.由于Se替代Te改变了BiCuTeO的能带结构,通过载流子浓度优化,有望进一步提高其热电性能.     

Mg-Al-Ca合金中三元Laves相的稳定性和电子结构

采用基于密度泛函理论的第一性原理方法,应用VASP (Vienna Ab-initio Simulation Package) 计算软件,研究了Mg-Al-Ca合金中三元Laves相,即Ca(Mg1-x,Alx)2和Al2(Ca1-x,Mgx) (x=0, 0.25, 0.50, 0.75, 1)在不同形态结构(C14, C15和C36)下的相稳定性及电子结构。计算所得的晶格常数和实验值吻合很好,形成能和相关能的计算用来研究三元Laves相的合金化能力和稳定性,结果表明：C14-Ca(Mg0.25,Al0.75)2具有很好的合金化能力,而C15- CaAl2具有很好的结构稳定性。态密度和电荷密度的计算用来研究Mg-Al-Ca合金中三元Laves相稳定性的内在微观机制。     

Hole doped α-MgAgSb as potential low temperature thermoelectric materials

The electronic structures and thermoelectric transport properties of α-MgAgSb were systematically investigated by using the first principles calculations combined with the Boltzmann transport equations. It is found that the thermoelectric properties of p-type α-MgAgSb are much better than those of n-type one, which originates from the steeper slope of the density of states at the edge of the valence band. By analyzing the density of states and partial charge density, we conclude that p-doping at the Mg-site does not modify the electronic states, but can optimize the carrier concentration. The effects of the carrier concentration and temperature on the thermoelectric transport properties of p-type α-MgAgSb are discussed in detail and the calculated results show good agreement with the experimental values. The p-type α-MgAgSb exhibit high thermoelectric performance and is a promising candidate for the low-temperature thermoelectric applications     

Thermoelectric properties in Mn-doped Bi2Se3

Using n-type and p-type Mn-doped Bi₂Se₃ single crystals, a thin-film-type thermoelectric (TE) module was fabricated and the TE characteristics were investigated. The Seebeck coefficient at room temperature was about 100 μV K⁻¹ with different sign for both materials. From the Seebeck coefficient and resistivity values, the electric power of our TE module was evaluated to be 90 μW for a single couple at the temperature difference of 10 K. This value is compared to that (∼21 μW) of commercialized TE device. Nevertheless, the actual power was measured to be quite small around 0.74 μW, which is much higher than other homemade TE power level. This small power is attributed to the high electrical contact resistance between the TE material and the heat source and sink. Assuming the contact resistance level ∼0.1 Ω similar to that of commercialized TE devices, the electric power should be about 41 μW, which is almost 2 times higher than that in commercialized TE devices. These results propose that the Mn-doped Bi₂Se₃ system is another promising TE material, which can be replaced with the commercialized Bi₂Te₃ system.     

Suppression of electron and hole overflow in GaN-based near-ultraviolet laser diodes

In order to suppress the electron leakage to p-type region of near-ultraviolet GaN/In_xGa_(1-x )N/GaN multiple-quantumwell(MQW) laser diode(LD), the Al composition of inserted p-type AlxGa_(1-x)N electron blocking layer(EBL) is optimized in an effective way, but which could only partially enhance the performance of LD. Here, due to the relatively shallow GaN/In_(0.04)Ga_(0.96)N/GaN quantum well, the hole leakage to n-type region is considered in the ultraviolet LD. To reduce the hole leakage, a 10-nm n-type Al_xGa_(1-x)N hole blocking layer(HBL) is inserted between n-type waveguide and the first quantum barrier, and the effect of Al composition of Al_xGa_(1-x)N HBL on LD performance is studied. Numerical simulations by the LASTIP reveal that when an appropriate Al composition of Al_xGa_(1-x)N HBL is chosen, both electron leakage and hole leakage can be reduced dramatically, leading to a lower threshold current and higher output power of LD.     

First principles study of structural,electronic and thermoelectric properties of skutterudite GdFe4As12 compounds

The full potential linearized augmented plane wave (FP-LAPW) method has been used to investigate structural, electronic and thermoelectric properties of Skutterudite GdFe₄As₁₂ compounds in the framework of the density functional theory (DFT) within the generalized gradient approximation (GGA) and (GGA+U). The ground-state properties are determined in the cubic structure (Im-3, space group 204). It is found that the most stable phase structure of GdFe4As12 compounds is the ferromagnetic phase and it shows a semi-metallic behavior with narrow gap. The calculation of the density of states near the Fermi level shows the compound to be suitable for the effective thermoelectric application. In addition, the high Seebeck coefficient value is obtained in the n-type region than p-type, indicating the prominence of n-type doping in filled skutterudite GdFe₄As₁₂.     

Improved 4H-SiC UMOSFET with super-junction shield region

This article investigates an improved 4H-SiC trench gate metal-oxide-semiconductor field-effect transistor (MOSFET) (UMOSFET) fitted with a super-junction (SJ) shielded region. The modified structure is composed of two n-type conductive pillars, three p-type conductive pillars, an oxide trench under the gate, and a light n-type current spreading layer (NCSL) under the p-body. The n-type conductive pillars and the light n-type current spreading layer provide two paths to and promote the diffusion of a transverse current in the epitaxial layer, thus improving the specific on-resistance ($R_{\rm on,sp}$). There are three p-type pillars in the modified structure, with the p-type pillars on both sides playing the same role. The p-type conductive pillars relieve the electric field ($E$-field) in the corner of the trench bottom. Two-dimensional simulation (silvaco TCAD) indicates that $R_{\rm on,sp }$ of the modified structure, and breakdown voltage ($V_{\rm BR}$) are improved by 22.2% and 21.1% respectively, while the maximum figure of merit (${\rm FOM}=V^{2}_{\rm BR}/R_{\rm on,sp}$) is improved by 79.0%. Furthermore, the improved structure achieves a light smaller low gate-to-drain charge ($Q_{\rm gd}$) and when compared with the conventional UMOSFET (conventional-UMOS), it displays great advantages for reducing the switching energy loss. These advantages are due to the fact that the p-type conductive pillars and n-type conductive pillars configured under the gate provide a substantial charge balance, which also enables the charge carriers to be extracted quickly. In the end, under the condition of the same total charge quantity, the simulation comparison of gate charge and OFF-state characteristics between Gauss-doped structure and uniform-doped structure shows that Gauss-doped structure increases the $V_{\rm BR}$ of the device without degradation of dynamic performance.     

Thermoelectric properties of nano-bulk bismuth telluride prepared with spark plasma sintered nano-plates

The pursuit for a high-performance thermoelectric n-type bismuth telluride-based material is significant because n-type materials are inferior to their corresponding p-type materials in highly efficient thermoelectric modules. Herein, to improve the thermoelectric performance of an n-type Bi₂Te₃, we prepared Bi₂Te₃ nano-plates with a homogeneous sub-micron size distribution and thickness range of about a few tens of nanometers. This was achieved using a typical nano-chemical synthetic method, and the prepared materials were then spark plasma sintered to fabricate n-type nano-bulk Bi₂Te₃ samples. We observed a significant enhancement of the anisotropic electrical transport properties for the nano-bulk sample with a higher power factor along the in-plane direction (24.3?μW?cm^?1?K^?2 at 300?K) than that along the out-of-plane direction (8.1?μW?cm^?1?K^?2 at 300?K). However, thermal transport properties were insensitive along the measured direction for the nano-bulk sample. We used a dimensionless figure of merit ZT to calculate the thermoelectric performance. The results showed that the maximum ZT value of 0.69 was achieved along the in-plane direction at 440?K for the nano-bulk n-type Bi₂Te₃ sample, which was however smaller than that of the previously reported n-type samples (ZT of 1.1). We believe that a further enhancement of the ZT value in the fabricated nano-bulk sample could be accomplished by effectively removing the surface organic ligand of the Bi₂Te₃ nano-plate particles and optimizing the spark plasma sintering conditions, maintaining the nano-plate morphology intact.