Thermal conductivity of Si-Ge quantum dot superlattices

Quantum dot superlattices (QDSLs) have been proposed for thermoelectric applications as a means of increasing thermal conductivity, σ, and reducing the lattice thermal conductivity, κ(l), to increase the dimensionless thermoelectric figure of merit, ZT. To fully exploit the thermoelectric potential of Si-Ge quantum dot superlattices (QDSLs), we performed a thorough study of the structural interplay of QDSLs with κ(l) using Green-Kubo theory and molecular dynamics. It was found that the resulting κ(l) has less dependence on the arrangement of the dots than to dot size and spacing. In fact, regardless of arrangement or concentration, QDSLs show a minimum κ(l) at a dot diameter of 1.4-1.6 nm and can reach values as low as 0.8-1.0 W mK?1, increasing ZT by orders of magnitude over bulk Si and Ge. The drastic reduction of thermal conductivity in such a crystalline system is shown to be the result of both the stress caused by the dots as well as the quality of the Si-Ge interface.     

Effect of silicon and sodium on thermoelectric properties of thallium-doped lead telluride-based materials

Thallium (Tl)-doped lead telluride (Tl(0.02)Pb(0.98)Te) thermoelectric materials fabricated by ball milling and hot pressing have decent thermoelectric properties but weak mechanical strength. Addition of silicon (Si) nanoparticles strengthened the mechanical property by reducing the grain size and defect density but resulted in low electrical conductivity that was not desired for any thermoelectric materials. Fortunately, doping of sodium (Na) into the Si added Tl(0.02)Pb(0.98)Te brings back the high electrical conductivity and yields higher figure-of-merit ZT values of ～1.7 at 770 K. The ZT improvement by Si addition and Na doping in Tl(0.02)Pb(0.98)Te sample is the direct result of concurrent electron and phonon engineering by improving the power factor and lowering the thermal conductivity, respectively.     

Ge取代P型高锰硅合金的晶粒细化及其热电性能

采取悬浮熔炼法制备Ge取代的高锰硅试样Mn(Si1-xGex1).733(x取0.004,0.006,0.008,0.010,0.012),采用甩带法得到快凝高锰硅合金粉末,XRD分析表明快速凝固能够减少MnSi金属相的含量,Ge对Si位的取代产生晶格畸变,使得衍射峰向低角区偏移;将悬浮熔炼和快速凝固所得试样进行放电等离子烧结,测试并比较其热电性能。结果显示,快速凝固有效地降低了材料的热导率,Ge取代则使得有效载流子浓度增加,提高了电导率,从而提高材料的热电性能。实验范围内,当Ge取代量x=0.010时,ZT值最高,悬浮熔炼试样在850K时ZT值为0.53,快速凝固试样在750K时ZT值达到0.55。     

高锰硅热电材料的微观结构及电热输运性能

采用熔炼、退火结合放电等离子烧结的方法制备了名义成分为MnSi_x ( x=1.60、1.65、1.68、1.73、1.81、1.85 )的高锰硅(HMS, Higher Manganese Silicide)块体材料. 物相分析结果表明, 随着Si初始用量x的增加, HMS (Mn₁₅Si₂₆)相各衍射峰强度先增强后减弱. 当x<1.73时, 样品物相组成为HMS相和少量MnSi相, 当x≥1.73时, 样品物相组成为HMS相和少量Si相. 体系的热电性能受MnSi相和Si相的影响, 热电性能分析结果表明: 随着Si名义含量x的增大, 试样电导率逐渐降低, 赛贝克系数逐渐增大, 热导率先降低后增高. 其中, 名义成分为MnSi_1.68的试样由于具有最高的电性能(功率因子)和较低的热导率, 从而具有最好的热电性能, 在400℃时其无量纲ZT值达到0.36.     

Phonon Transport of Rough Si/Ge Superlattice Nanotubes

Nanostructuring of thermoelectric materials bears promise for manipulating physical parameters to improve the energy conversion efficiency of thermoelectrics. In this paper the thermal transport in Si/Ge superlattice nanotubes is investigated by performing nonequilibrium molecular dynamics simulations aiming at realizing low thermal conductivity by surface roughening. Our calculations revealed that the thermal conductivity of Si/Ge superlattice nanotubes depends nonmonotonically on periodic length and increases as the wall thickness increases. However, the thermal conductivity is not sensitive to the inner diameters due to the strong surface scattering at thin wall thickness. In addition, introducing roughness onto the superlattice nanotubes surface can destroy the phonon tunneling in superlattice nanotubes, which results in thermal conductivity even surpassing amorphous limit. Furthermore, a nonmonotonic dependence of the thermal conductivity of rough Si/Ge superlattice nanotubes with thicker wall thickness is found, while for thinner wall the thermal conductivity of rough Si/Ge superlattice nanotubes decreases monotonically with surface roughness increasing. Our results provide guidance for designing high performance thermoelectrics using superlattice nanotube.     

Nanoporous Si as an efficient thermoelectric material

Room-temperature thermoelectric properties of n-type crystalline Si with periodically arranged nanometer-sized pores are computed using a combination of classical molecular dynamics for lattice thermal conductivity and ab initio density functional theory for electrical conductivity, Seebeck coefficient, and electronic contribution to the thermal conductivity. The electrical conductivity is found to decrease by a factor of 2-4, depending on doping levels, compared to that of bulk due to confinement. The Seebeck coefficient S yields a 2-fold increase for carrier concentrations less than 2 x 10(19) cm(-3), above which S remains closer to the bulk value. Combining these results with our calculations of lattice thermal conductivity, we predict the figure of merit ZT to increase by 2 orders of magnitude over that of bulk. This enhancement is due to the combination of the nanometer size of pores which greatly reduces the thermal conductivity and the ordered arrangement of pores which allows for only a moderate reduction in the power factor. We find that while alignment of pores is necessary to preserve power factor values comparable to those of bulk Si, a symmetric arrangement is not required. These findings indicate that nanoporous semiconductors with aligned pores may be highly attractive materials for thermoelectric applications.     

几种Si、Ge纳米线导热系数的原子模拟

采用非平衡分子动力学方法模拟了Si纳米线、Ge纳米线、核-壳结构的Si/Ge纳米线及超晶格结构的Si/Ge纳米线的导热系数,给出了纳米线的温度与导热系数关系曲线,对比了几种纳米线导热特性的差异,研究结果表明,随着温度的升高,各纳米线的导热系数降低;相同温度下,纳米线导热系数的大小顺序为：核-壳结构的Si/Ge纳米线、超晶格结构的Si/Ge纳米线、Si纳米线、Ge纳米线。     

Solid State Synthesis and Thermoelectric Properties of Mg-Si-Ge System

1.IntroductionMuch attention has been paid to thermoelectric mate-rials for manufacturing thermoelectric energy conversiondevices by utilizing temperature change from waste heatand geothermal sources[1~5].The performance of ther-moelectric materials is usually expressed by the figure ofmerit z,z=α2σ/k,whereαis the Seebeck coefficient,σis the electrical conductivity and k is the thermal con-ductivity.The higher the z,the higher the effectivenessof a material for thermoelectric applications[…     

Preparation of In2O3-Sr2RuErO6 Composite Ceramics by the Spark Plasma Sintering and Their Thermoelectric Performance

In1.94Zn0.03Ge0.03O3 and Sr2RuErO6 composite ceramics have been prepared by the spark plasma sintering (SPS) technique. Microstructure studies show that the Sr2RuErO6 phases are randomly dispersed in the In1.94Zn0.03Ge0.03O3 matrix. The results show that the Seebeck coeffcient increases with increasing the amount of Sr2RuErO6, while the thermal conductivity of the composite samples is lower than that of the In1.94Zn0.03Ge0.03O3 ceramic. The thermal conductivity of the 7 vol.% Sr2RuErO6 sample can decrease to 2.15 W·m-1·K-1 at 973 K, and the evaluated maximum ZT value is 0.23 for 3 vol.% Sr2RuErO6 samples at 973 K, which makes them promising materials for the thermoelectric devices.     

Significant reduction of thermal conductivity in Si/Ge core-shell nanowires

We report on the effect of germanium (Ge) coatings on the thermal transport properties of silicon (Si) nanowires using nonequilibrium molecular dynamics simulations. Our results show that a simple deposition of a Ge shell of only 1 to 2 unit cells in thickness on a single crystalline Si nanowire can lead to a dramatic 75% decrease in thermal conductivity at room temperature compared to an uncoated Si nanowire. By analyzing the vibrational density states of phonons and the participation ratio of each specific mode, we demonstrate that the reduction in the thermal conductivity of Si/Ge core-shell nanowire stems from the depression and localization of long-wavelength phonon modes at the Si/Ge interface and of high frequency nonpropagating diffusive modes.     

Manipulating the Ge Vacancies and Ge Precipitates through Cr Doping for Realizing the High‐Performance GeTe Thermoelectric Material

GeTe alloy is a promising medium‐temperature thermoelectric material but with highly intrinsic hole carrier concentration by thermodynamics, making this system to be intrinsically off‐stoichiometric with Ge vacancies and Ge precipitations. Generally, an intentional increase of formation energy of Ge vacancy by element substitution will lead to an effective dissolution of Ge precipitates for reduction in hole concentration. Here, an opposite direction of decreasing the formation energy of Ge vacancies is demonstrated by substituting Cr at Ge site. This strategy produces more but nearly homogenously distributed Ge precipitations and Ge vacancies, which provides enhanced phonon scattering and effectively reduces the lattice thermal conductivity. Furthermore, Cr atom carries one more electron than Ge and serves as an electron donor for decreasing the hole carrier concentrations. Further optimization incorporates the effect of Bi substitution for facilitating band convergence. A maximum figure of merit (ZT) of 2.0 at 600 K with average ZT of over 1.2 is achieved in the sample of Ge_0.92Cr_0.03Bi_0.05Te, making it one of the best thermoelectric materials for medium‐temperature application.     

硼掺杂球磨SiGe合金的热电性能

SiGe合金热电材料作为一种传统的高温热电材料一直以来受到广泛关注。本研究通过B在球磨SiGe合金中的P型掺杂,有效增加了材料的载流子浓度,优化材料的电学性能。通过球磨降低材料的晶粒尺寸,增强晶界对声子的散射,降低材料的晶格热导率。另外,B掺杂使点缺陷散射和载流子-声子散射得到增强,材料的晶格热导率进一步降低。在室温时,Si_(0.8)Ge_(0.2)B_(0.04)的晶格热导率为~4Wm~(-1) K~(-1)。由于掺杂后电导率提高,热导率降低,因此热电优值zT得到了提高。在850K时,Si_(0.8)Ge_(0.2)B_(0.04)的最大热电优值为0.42,与Si_(0.8)Ge_(0.2)B_(0.002)的样品相比,其优值提高了2.5倍左右。     

Nanostructure design for drastic reduction of thermal conductivity while preserving high electrical conductivity

The design and fabrication of nanostructured materials to control both thermal and electrical properties are demonstrated for high-performance thermoelectric conversion. We have focused on silicon (Si) because it is an environmentally friendly and ubiquitous element. High bulk thermal conductivity of Si limits its potential as a thermoelectric material. The thermal conductivity of Si has been reduced by introducing grains, or wires, yet a further reduction is required while retaining a high electrical conductivity. We have designed two different nanostructures for this purpose. One structure is connected Si nanodots (NDs) with the same crystal orientation. The phonons scattering at the interfaces of these NDs occurred and it depended on the ND size. As a result of phonon scattering, the thermal conductivity of this nanostructured material was below/close to the amorphous limit. The other structure is Si films containing epitaxially grown Ge NDs. The Si layer imparted high electrical conductivity, while the Ge NDs served as phonon scattering bodies reducing thermal conductivity drastically. This work gives a methodology for the independent control of electron and phonon transport using nanostructured materials. This can bring the realization of thermoelectric Si-based materials that are compatible with large scale integrated circuit processing technologies.     

Lattice Distortions and Multiple Valence Band Convergence Contributing to High Thermoelectric Performance in MnTe

Here, a new route is proposed for the minimization of lattice thermal conductivity in MnTe through considerable increasing phonon scattering by introducing dense lattice distortions. Dense lattice distortions can be induced by Cu and Ag dopants possessing large differences in atom radius with host elements, which causes strong phonon scattering and results in extremely low lattice thermal conductivity. Density functional theory (DFT) calculations reveal that Cu and Ag codoping enables multiple valence band convergence and produces a high density of state values in the electronic structure of MnTe, contributing to the large Seebeck coefficient. Cu and Ag codoping not only optimizes the Seebeck coefficient but also substantially increases the carrier concentration and electrical conductivity, resulting in the significant enhancement of power factor. The maximum power factor reaches 11.36 µW cm⁻¹K⁻² in Mn_0.98Cu_0.04Ag_0.04Te. Consequently, an outstanding ZT of 1.3 is achieved for Mn_0.98Cu_0.04Ag_0.04Te by these synergistic effects. This study provides guidelines for developing high-performance thermoelectric materials through the rational design of effective dopants.     

Nanostructures in high-performance (GeTe)(x)(AgSbTe(2))(100-x) thermoelectric materials

The thermoelectric properties of (GeTe)(x)(AgSbTe(2))(100-x) compounds (x = 75, 80, 85 and 90; TAGS-x) have been studied as a function of temperature from 300 to 720?K. At 720?K the dimensionless figure of merit ZT reaches the state-of-the-art value of 1.53 for TAGS-75 and 1.50 for TAGS-80 and TAGS-85 samples, respectively. But the ZT value of the TAGS-90 sample is only 0.50 at 720?K due to the high carrier concentration. Utilizing high-resolution transmission electron microscope and selected area electron diffraction techniques, we identify a considerable number of nanoscale domains with typical size ～10?nm in the samples that show high ZT values. It is suggested that the presence of nanoscale domains, like the situation in PbTe-AgSbTe(2) compounds, should make a slight contribution to the low lattice thermal conductivity of TAGS compounds due to the enhanced mid-frequency phonon scattering.     

Enhanced thermoelectric performance in Cl-doped BiSbSe3 with optimal carrier concentration and effective mass

Possessing inherently low thermal conductivity,BiSbSe3 is a promising thermoelectric material for medium temperature.Therefore,to substantially optimize the thermoelectric performance of BiSbSe3,researchers mainly focus on the strategies to improve its electrical transport properties.Among these strongly coupled thermoelectric parameters,carrier concentration and effective mass are two intrinsic variables to decisively affect the electrical transport properties.In this work,Cl as a donor dopant is effec-tive to provide extra electrons in n-type BiSbSe3,and the carrier concentration and effective mass can be well optimized simultaneously with increasing Cl content owing to the multiple conduction bands in BiSbSe3.What's more,maximum weighted mobility～53 cm2 V-1 s-1 is obtained in Cl-doped BiSbSe3,which contributes to a largely enhanced power factor～4.8 μW cm-1 K-2 at room temperature and out-performs other halogen-doped BiSbSe3 samples.Finally,combining the significantly enhanced power factor and maintained low thermal conductivity,a maximum ZT～1.0 is achieved in Cl-doped BiSbSe3 at 800 K.     

Atomistic design of thermoelectric properties of silicon nanowires

We present predictions of the thermoelectric figure of merit ( ZT) of Si nanowires with diameter up to 3 nm, based upon the Boltzman transport equation and ab initio electronic structure calculations. We find that ZT depends significantly on the wire growth direction and surface reconstruction, and we discuss how these properties can be tuned to select silicon based nanostructures with combined n-type and p-type optimal ZT. Our calculations show that only by reducing the ionic thermal conductivity by about 2 or 3 orders of magnitudes with respect to bulk values, one may attain ZT larger than 1, for 1 or 3 nm wires, respectively. We also find that ZT of p-doped wires is considerably smaller than that of their n-doped counterparts with the same size and geometry.     

La、Nb掺杂固相反应法合成SrTiO3热电性能的优化

SrTiO₃作为钛矿型金属氧化物半导体,具有环境友好、原料来源丰富等优点。本研究发现了一种制备高新热电性能SrTiO₃材料的新工艺,对比固相反应法直接烧制的SrTiO₃陶瓷,采用本工艺的PAS+埋烧热处理方法可以降低制备反应温度,并且所得材料的功率因子得到显著提高。该项发现主要研究了在此工艺下制备的不同La、Nb掺杂比(5%-15%)的样品性能变化情况。结果表明,该工艺下制备的SrTiO₃样品中La15Nb15样品在873K时的最大功率因子可达1.279mW·m^-1·K^-1。但是部分样品热导率也会出现一定程度的增加。综合效果是材料热电优值ZT得以提升,在873K时La10Nb5样品的ZT值达到了0.28。     

Anisotropic thermal conductivity of Ge quantum-dot and symmetrically strained Si/Ge superlattices

We report the first experimental results on the temperature dependent in-plane and cross-plane thermal conductivities of a symmetrically strained Si/Ge superlattice and a Ge quantum-dot superlattice measured by the two-wire 3 omega method. The measured thermal conductivity values are highly anisotropic and are significantly reduced compared to the bulk thermal conductivity of the structures. The results can be explained by using heat transport models based on the Boltzmann transport equation with partially diffusive scattering of the phonons at the superlattice interfaces.     

Spark plasma sintering and thermoelectric evaluation of nanocrystalline magnesium silicide (Mg2Si)

Recently magnesium silicide (Mg₂Si) has received great interest from thermoelectric (TE) society because of its non-toxicity, environmental friendliness, comparatively high abundance, and low production material cost as compared to other TE systems. It also exhibited promising transport properties, including high electrical conductivity and low thermal conductivity, which improved the overall TE performance (ZT). In this work, Mg₂Si powder was obtained through high energy ball milling under inert atmosphere, starting from commercial magnesium silicide pieces (99.99 %, Alfa Aesar). To maintain fine microstructure of the powder, spark plasma sintering (SPS) process has been used for consolidation. The Mg₂Si powder was filled in a graphite die to perform SPS and the influence of process parameters as temperature, heating rate, holding time and applied pressure on the microstructure, and densification of compacts were studied in detail. The aim of this study is to optimize SPS consolidation parameters for Mg₂Si powder to achieve high density of compacts while maintaining the nanostructure. X-Ray diffraction (XRD) was utilized to investigate the crystalline phase of compacted samples and scanning and transmission electron microscopy (SEM & TEM) coupled with Energy-Dispersive X-ray Analysis (EDX) was used to evaluate the detailed microstructural and chemical composition, respectively. All sintered samples showed compaction density up to 98 %. Temperature dependent TE characteristics of SPS compacted Mg₂Si as thermal conductivity, electrical resistivity, and Seebeck coefficient were measured over the temperature range of RT 600 °C for samples processed at 750 °C, reaching a final ZT of 0.14 at 600 °C.