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.     

Development of n-type Te-doped GaSb substrates with low carrier concentration for FPA applications

Undoped GaSb is p-type with the residual acceptor concentration of about 1e17 cm⁻³ due to the gallium vacancies and gallium in antimony site. Counter-doping of GaSb with low level of Te can reduce the net carrier concentration resulting in higher optical transparency in a broad IR spectral range. In this work, the carrier concentration, mobility and sheet resistance of n-type and p-type Te-doped GaSb substrates were measured using Hall method at 300 K and 77 K. The Hall carrier concentration data at 300 K were correlated with the absorption coefficients of GaSb in the IR spectral range. An empirical relationship between these values was established. Based on this correlation, we discuss application of FTIR spectroscopy for non-destructive optical screening of the substrates that allows construction of the carrier concentration distribution map across GaSb wafers. Investigations of the electronic properties of the low-doped p-type and n-type GaSb substrates upon cooling down to 77 K indicate the reduction of the hole carrier concentration background for both GaSb types. This is evident from the decrease in the Hall-measured carrier concentration for p-type GaSb. For n-type GaSb, an increase in the carrier concentration is observed due to the reduction of the hole carrier concentration background.     

(Sb2Te3)0.75(1－x)(Bi2Te3)0.25(1－x)(Sb2Se3)x机械合金化粉体的制备及其冷压烧结样品的热电性能研究

采用机械合金化法制备了p型赝三元(Sb₂Te₃-Bi₂Te₃-Sb₂Se₃)合金粉体，对其进行XRD分析表明Te，Bi，Sb，Se单质粉末，经100h球磨后实现了合金化；SEM分析表明所得机械合金化粉体材料颗粒均匀、细小，颗粒尺寸在10nm到100nm量级.使用这种粉体制备了冷压烧结块体样品，在室温下测量了温差电动势率(α)和电导率(σ)，研究了烧结温度对材料热电性能的影响，结果表明在低于300℃的烧结温区，样品室温下的热电性能随烧结温度的升高不断提高，功率因子(α²σ)由未烧结样品的0.59μW cm^-1K^-2升高到在300℃下烧结样品的15.9μW cm^-1K^-2，这一结果对确定材料的最佳烧结温度具有重要意义. 关键词： 赝三元热电材料 机械合金化 冷压 烧结     

Electronic and thermoelectric properties of Mg_2Ge_xSn-_(1-x)(x=0.25,0.50,0.75) solid solutions by first-principles calculations

The electronic structure and thermoelectric(TE) properties of Mg_2Ge_xSn_(1-x)(x = 0.25, 0.50, 0.75) solid solutions are investigated by first-principles calculations and semi-classical Boltzmann theory. The special quasi-random structure(SQS) is used to model the solid solutions, which can produce reasonable band gaps with respect to experimental results.The n-type solid solutions have an excellent thermoelectric performance with maximum zT values exceeding 2.0, where the combination of low lattice thermal conductivity and high power factor(PF) plays an important role. These values are higher than those of pure Mg_2Sn and Mg_2Ge. The p-type solid solutions are inferior to the n-type ones, mainly due to the much lower PF. The maximum zT value of 0.62 is predicted for p-type Mg_2Ge_(0.25)Sn_(0.75) at 800K. The results suggest that the n-type Mg_2Ge_xSn_(1-x) solid solutions are promising mid-temperature TE materials.     

纳米结构碲化铋合金的制备及电热输运特性

采用惰性气体保护蒸发-冷凝法制备了纳米Bi及Te粉末, 结合机械合金化和放电等离子烧结技术, 在不同烧结温度下制备出了单一物相且具有纳米层状结构及孪晶亚结构的n型Bi₂Te₃块体材料, 并系统研究了块体材料的晶粒尺度、微结构及其对电热传输特性的影响. SEM, TEM分析结果表明, 以纳米粉末为原料, 通过有效控制工艺条件, 可以制备出具有纳米层状结构Bi₂Te₃合金块体材料, 同时纳米层状结构中存在孪晶亚结构; 热电性能测试结果表明, 具有纳米层状结构及孪晶亚结构的块体试样与粗晶材料相比, 热导率大幅度降低, 在423 K附近, 热导率由粗晶材料的1.80 W/mK降至1.19 W/mK, 晶格热导率从1.16 W/mK降至0.61 W/mK, 表明纳米层状结构与孪晶亚结构共存, 有利于进一步提高声子散射, 降低晶格热导率. 其中在693 K放电等离子烧结后的试样于423K附近取得最大值的无量纲热电优值(ZT), 达到0.74.     

Optimization and fabrication of a planar thermoelectric generator for a high-performance solar thermoelectric generator

A planar thermoelectric generator (TEG) could be used as an energy harvester for wireless sensor networks (WSNs). Its planar configuration offers the advantages of miniaturization and low-cost fabrication. Herein, we report the fabrication of a device based on a co-evaporated thick film of Bi–Te. Before fabrication we studied quantitative optimization dimensions for the planar TEG via finite element method (FEM) simulations. The planar TEG was also used in a high-performance solar thermoelectric generator (STEG) that concentrated heat from solar radiation via a solar absorber to generate a temperature difference (ΔT) between two thermoelectric and electrode junctions. When exposed to a solar simulator, the STEG produced a ΔT of about 6 °C and generated 2.3 μW of power. The demonstrated high flexibility and mechanical stability of this device suggests applications in wearable electronics.     

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.     

P–n junction characteristics of graphene oxide and reduced graphene oxide on n-type Si(111)

The semiconductor behavior of graphene oxide (GO) and reduced graphene oxide (RGO) synthesized by the Hummers method on n-type Si(111) were investigated. Graphene oxide is a product of the oxidation of graphite, during which numerous oxygen functional groups bond to the carbon plane during oxidation. RGO was prepared by adding excess hydrazine to the GO showing p-type semiconductor material behavior. In the C–O bond, the O atom tends to pull electrons from the C atom, leaving a hole in the carbon network. This results in p-type semiconductor behavior of GO, with the carrier concentration dependent upon the degree of oxidation. The RGO was obtained by removing most of the oxygen-containing functionalities from the GO using hydrazine. However, oxygen remaining on the carbon plane caused the RGO to exhibit p-type behavior. The I–V characteristics of GO and RGO deposited on n-type Si(111) forming p–n junctions exhibited different turn-on voltages and slope values.     

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.     

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.     

First-principles study on the structural,electronic and optical properties of BiOX (X=Cl,Br, I) crystals

In order to investigate systematically the structural, electronic and optical properties of bismuth oxyhalides BiOX (X=Cl, Br, I) semiconductors, the lattice constants, structural characteristics, band structures, densities of states, atomic charge populations and optical properties of BiOX crystals have been calculated using first-principles based on DFT. The calculated indirect band gaps of BiOCl, BiOBr and BiOI crystals are 2.50, 2.10 and 1.59 eV, respectively. The analysis of densities of states and atomic charge populations for BiOX crystals indicates that, (a) the valance band maximum is mainly contributed to O 2p and X np states and the Bi 6p states dominate the conduction band minimum; (b) the contribution of X ns states obviously increases with the increase of X atomic numbers, and the dispersive energy level becomes more and more significant and (c) the sequence of covalent bonding strength between atoms is Bi–O >Bi–I>Bi–Br>Bi–Cl. In addition, the calculated absorption edges of the absorption coefficients I(ω) for BiOCl, BiOBr and BiOI crystals are 355, 448 and 645 nm, respectively, which agree well with our experimental measurements of 376, 442 and 628 nm and the previous reported results of 370, 440 and 670 nm.     

Synergistically Enhancing Thermoelectric Performance of n-Type PbTe with Indium Doping and Sulfur Alloying

To achieve high-performance n-type PbTe-based thermoelectric materials, this work provides a synergetic strategy to improve electrical transport property with indium (In) element doping and reduces thermal conductivity with sulfur (S) element alloying. In n-type PbTe, In doping can tune the carrier density in the whole working temperature range, causing the carrier density to increase from 2.18 × 10¹⁹ cm⁻³ at 300 K to 4.84 × 10¹⁹ cm⁻³ at 823 K in Pb_0.98In_0.005Sb_0.015Te. The optimized carrier density can further modulate electrical conductivity and Seebeck coefficient, finally contributing to a substantial increase of power factor, and a maximum power factor increase from 19.7 µW cm⁻¹ K⁻² in Pb_0.985Sb_0.015Te to 28.2 µW cm⁻¹ K⁻² in Pb_0.9775In_0.0075Sb_0.015Te. Based on the optimally In-doped PbTe, S alloying is introduced to suppress phonon propagation by forming a complete solid solution, which could effectively reduce lattice thermal conductivity and simultaneously benefit carrier mobility to maintain high power factor. With S alloying, the minimum lattice thermal conductivity decreases from 0.76 Wm⁻¹ K⁻¹ in Pb_0.985Sb_0.015Te to 0.42 Wm⁻¹ K⁻¹ in Pb_0.98In_0.005Sb_0.015Te_0.88S_0.12. Combining the advantages of both In doping and S alloying, the peak ZT value and averaged ZT (ZT_ave) (300–873 K) are boosted from 1.0 and 0.60 in Pb_0.985Sb_0.015Te to 1.4 and 0.87 in Pb_0.98In_0.005Sb_0.015Te_0.94S_0.06.     

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     

First-principles study of intrinsic defect properties in hexagonal BN bilayer and monolayer

The formation energies and transition energy levels of intrinsic defects in hexagonal BN (h-BN) bilayer and monolayer have been studied by first-principles calculations based on density functional theory. Our calculated results predict that excellent intrinsic p-type and n-type conductivities are very difficult to be realized in h-BN bilayer and monolayer. This is because of the high formation energies of acceptor-like defects (≥4.6 eV ) and the rather deep transition energy levels of donor-like defects (≥2.0 eV ). In order to obtain h-BN layers with more efficient p-type and n-type conductivity, extrinsic doping using foreign impurities is necessary.     

Study on the thermoelectric properties of porous Bi-Te films deposited using thermal evaporation on AAO template

The application of thermoelectric films is limited to retain the temperature gradient. In this study, the Bi-Te films are deposited on the AAO template with a pore size of 100 nm using thermal evaporation. The results show that the conductive types of the Bi-Te film are tuned by source temperature. The power factor of the p-type porous film decreases 36% by comparing to that of the p-type nonporous film (1020 μW/mK² at 250 °C). Meanwhile, the temperature difference in the porous device is maintained and is approximately 5.0 °C. Thus, the maximum output power is achieved in the porous device (about 25 pW), which is 5 times higher than that of the nonporous device. This provides a method to improve the conversion efficiency of thermoelectric film device by maintaining the temperature difference by using porous structure.     

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.     

Tuneability of Sm(1 − x)CexFeO3 ± λ perovskites: Thermal stability and electrical conductivity

Trimetallic perovskite oxides, Sm_(1 ? x)Ce_xFeO_3 ± λ (x = 0–0.05), were prepared by thermal decomposition of amorphous citrate precursors followed by calcinations. The material properties of the substituted perovskites were characterized by X-ray diffraction (XRD), X-ray florescence spectroscopy (XRF), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The doped materials exhibited a single perovskite phase in air up to 1350 °C and have specific surface areas in the range of 2.696–8.665 m²/g. In reducing atmosphere (5%v/vH₂/N₂), the unsubstituted perovskite (x = 0) decomposed into two phases while the ceria stabilized materials (x = 0.01, x = 0.03, x = 0.05) remained in a single phase as revealed by XRD analysis. Their conductivities were measured by the four point probe method in air and in dilute hydrogen (5%v/vH₂/N₂) separately. The ceria substituted materials show increased stability versus reduction and phase separation for a wide temperature range (up to 1000 °C). Although undoped SmFeO₃ has higher conductivity under oxidizing conditions than ceria doped SmFeO₃ due its p-type nature, the situation is reversed under reducing conditions. The ceria substituted perovskites (Sm_(1 ? x)Ce_xFeO_3 ± λ, x = 0–0.05) showed higher conductivity in reducing than in oxidizing conditions, suggesting that ceria doping at the A-site has changed the SmFeO₃ from p-type to n-type semi-conducting behavior.     

Changes in the electronic properties of Bi2X3 (X: Se, Te) single crystals due to intercalation

Bi₂Se₃ and Bi₂Te₃ are layered semiconductors n-type and p-type, respectively, which belong to the family of thermoelectric materials. In this work we examine the insertion of Cu in Bi₂Te₃ and Bi₂Se₃ single crystals through an intercalation reaction. The inserted Cu acting as donor enhances the n-type character of Bi₂Se₃ while changing the native p-type character of Bi₂Te₃ to n-type. The spatial distribution of the intercalated species was monitoring by X-ray microanalysis and microscopic IR reflectivity measurements. Paper presented at the 4th Euroconference on Solid State Ionics, Renvyle, Galway, Ireland, Sept. 13–19, 1997     

块体热电材料的研究进展

文章重点介绍了现役热电材料（Bi2Te3,PbTe,SiGe）、常见结构类型（方钴矿型,笼合物型,Half-Heusler合金型,钠钴氧型和Zn4Sb3型）热电材料及新颖晶体结构类型的热电材料的晶体结构、热电性能、热电性能优化等方面的最新研究进展.     

Combined effects of donor and acceptor impurities on the thermoelectric properties of cadmium antimonide

A study was made of the effect of the simultaneous doping with donor (Te) and acceptor (Cu, Ag, Au) elements on the thermoelectric properties of CdSb. Doping with tellurium changes the p-type conductivity of the CdSb crystals to an n-type conductivity with an impurity (Te) activation energy of E_d = (0. 11 ± 0. 01) eV. Doping with an acceptor impurity changes the energy of the donor level, by E_d = 0. 14 eV for doping with silver, by E_d = 0. 10 eV for doping with gold and by E_d = 0. 095 eV for doping with copper. It is shown that the type of conductivity and the thermoelectric properties of CdSb can be adjusted in the desired direction through simultaneous doping with two impurities.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii Fizika, No. 6, pp. 90–94, June, 1970.