Enhanced thermoelectric performance of spark plasma sintered copper-deficient nanostructured copper selenide

We report the thermoelectric properties of nanostructured Cu-deficient Cu₂Se, which was synthesized by high energy ball milling followed by spark plasma sintering. Our method obtained a significant enhancement in the thermoelectric figure of merit (ZT), i.e., ~1.4 at 973 K, which was ~30% higher than its bulk counterpart. This enhancement in the thermoelectric performance was due mainly to a significant reduction in the lattice thermal conductivity, which was attributed to enhanced phonon scattering at various length scales by nanoscale defects as well as abundant nanograin boundaries. The nanoscale defects were characterized by transmission electron microscopy of the nanostructured Cu_2−xSe samples, which formed the basis of the ZT enhancement.     

p-型层状氧化锌的热电性质研究

采用第一性原理和玻尔兹曼输运理论,我们系统的研究了p-型二层氧化锌的热电性质.基于对单层氧化锌的晶格优化,计算得到其无虚频的声子谱,证明了它的热力学稳定性.由此构建了热力学性质稳定的二层氧化锌.采用实空间有限差分法生成了二层氧化锌的二阶和三阶力常数,然后得到了其声子散射和晶格热导率,使用两种计算方法得到了其晶格热导率在室温下分别为κ_ι~(BTE)=2.65 W/m·K和κ_ι~(RTA)=2.38 W/m·K.并且得到了p-型二层氧化锌在300 K至900 K等差温度下的热电优值为0.052～0.601,证明通过调节温度可以获得较高的热电优值.     

Ca2+掺杂对CdO多晶热电性能的影响

以CaCO₃作为Ca²⁺源, 利用传统固相烧结法制备了Cd_1-xCa_xO (x=0, 0.01, 0.03, 0.05) 多晶块体样品并研究了Ca²⁺掺杂对CdO高温热电性能的影响. CaCO₃的掺入会导致CdO多晶载流子浓度降低, 使Cd_1-xCa_xO的电阻率ρ和塞贝克系数的绝对值|S|增大、电子热导率κ_e减小. 同时, 在CdO中掺入CaCO₃会引入点缺陷和气孔并可抑制CdO晶粒长大、晶界增多, 从而增加了对声子的散射, 使样品的声子热导率κ_p减小. 由于总热导率的大幅降低, Cd_0.99Ca_0.01O多晶样品在1000 K时的热电优值ZT可达0.42, 比本征CdO提高了约27%, 为迄今n型氧化物热电材料报道的最好结果之一.     

Ag-ZnO纳米复合热电材料的制备及其性能研究

ZnO是一类具有潜力的热电材料, 但其较大声子热导率影响了热电性能的进一步提高. 纳米复合是降低热导率的有效途径. 本文以醋酸盐为前驱体, 溶胶-凝胶法制备了Ag-ZnO纳米复合热电材料. 扫描电镜照片显示ZnO颗粒呈现多孔结构, Ag纳米颗粒分布于ZnO的晶粒之间. Ag-ZnO纳米复合材料的电导率比未复合ZnO材料高出100倍以上, 而热导率是未复合ZnO材料的1/2. 同时, 随着Ag添加量的增加, 赛贝克系数的绝对值逐渐减小. 综合以上原因, 添加7.5%mol Ag的Ag-ZnO纳米复合材料在700 K时的热电优值达到0.062, 是未复合ZnO材料的约25倍. 在ZnO基体中添加导电金属颗粒有利于产生导电逾渗通道, 提高材料体系的电导率, 但同时导致赛贝克系数的绝对值减小. 总热导率的差异来源于声子热导率的差异. 位于ZnO晶界的纳米Ag颗粒, 有利于降低声子热导率. 关键词： 热电材料 ZnO 纳米复合 热导率     

The effect of the long-range order in a quantum dot array on the in-plane lattice thermal conductivity

Semiconductor quantum dot superlattices consisting of arrays of quantum dots have shown great promise for a variety of device applications, including thermoelectric power generation and cooling. In this paper we theoretically investigate the effect of long-range order in a quantum dot array on its in-plane lattice thermal conductivity. It is demonstrated that the long-range order in a quantum dot array enhances acoustic phonon scattering and, thus leads to a decrease of its lattice thermal conductivity. The decrease in the ordered quantum dot array, which acts as a phonon grating, is stronger than that in the disordered one due to the contribution of the coherent scattering term. The numerical calculations were carried out for a structure that consists of multiple layers of Si with layers of ordered Ge quantum dots separated by wetting layers and spacers.     

Effect of pressure on electronic and thermoelectric properties of magnesium silicide: A density functional theory study

We study the effect of pressure on electronic and thermoelectric properties of Mg_2Si using the density functional theory and Boltzmann transport equations. The variation of lattice constant, band gap, bulk modulus with pressure is also analyzed. Further, the thermoelectric properties(Seebeck coefficient, electrical conductivity, electronic thermal conductivity) have been studied as a function of temperature and pressure up to 1200 K. The results show that Mg_2Si is an n-type semiconductor with a band gap of 0.21 eV. The negative value of the Seebeck coefficient at all pressures indicates that the conduction is due to electrons. With the increase in pressure, the Seebeck coefficient decreases and electrical conductivity increases. It is also seen that, there is practically no effect of pressure on the electronic contribution of thermal conductivity.The paper describes the calculation of the lattice thermal conductivity and figure of merit of Mg_2Si at zero pressure. The maximum value of figure of merit is attained 1.83 × 10~(-3) at 1000 K. The obtained results are in good agreement with the available experimental and theoretical results.     

基于第一性原理分子动力学的填充方钴矿热输运性质及微观过程的研究

对于重要热电材料之一的填充方钴矿材料,其低热导率的成因存在两种观点:1)填充原子的局域振动引起共振散射降低热导率;2)填充原子的引入加强了三声子倒逆过程来降低热导率.本文采用含有限温度效应的第一性原理分子动力学方法模拟了YbFe_4Sb_(12)的动力学过程,并通过温度相关有效势场方法得到了充分包含非线性作用的等效非谐力常数,研究了微扰近似下的声子输运性质.结果显示,在填充原子振动全部参与三声子倒逆散射过程的近似下,相比于纯方钴矿体系,声子寿命大幅地降低,填充原子的振动是热阻的重要来源.但即便如此,理论计算结果与实验的晶格热导率之间仍存在明显偏离.不同填充原子振动之间的较弱关联性质也揭示其明显偏离经典的声子图像,表现为一种强烈的局域特征振动模式,并以此散射其他晶格声子,因而对热阻的贡献也超出了传统三声子的理论框架.通过将填充原子Yb振动模式的寿命进行共振散射形式的修正,可以使晶格热导率与实验结果符合较好.以上结果表明,YbFe_4Sb_(12)的低晶格热导率是由声子间相互作用以及具有局域振动特征的共振散射两方面因素导致.     

β型锑烯热电输运性质的第一性原理研究

利用第一性原理与半经典玻尔兹曼方程，计算并分析β型锑烯的声子色散、声子群速度、声子弛豫时间、晶格热导率及不同温度下的塞贝克系数、电导率和电子热导率随化学势的变化；结果表明：β型锑烯由于非平面六角结构，三支声学声子在Γ点附近均呈线性变化；声学声子对整个晶格热导率的贡献高达96.68%，而光学声子仅仅占到3.32%；由于较大的声光带隙（a-o gap）导致LA支在声子群速度和弛豫时间中占据主导地位，从而增大了LA支声子对整个热导的贡献；热电优值随温度的升高而增大，在费米面附近其绝对值最大可达0.275.     

Influence of Ir substitution on the thermoelectric properties of Ba0.3(IrxCo1-x)4Sb12 solid solutions

Polycrystalline skutterudite solid solutions, Ba_0.3 (Ir_xCo_1-x)₄Sb₁₂ (x from 0 to 0.11), have been synthesized by a two-step solid state reaction method and sintered by a spark plasma sintering (SPS) technique. The influence of Ir substitution on electrical and thermal transport properties has been investigated in the temperature range of 300–850 K. Through Ir substitution, the lattice thermal conductivity was depressed due to the phonon scattering by point defects. The thermopower and thermoelectric power factor increased because of the enhancement of carrier acoustic lattice scattering especially at lower temperatures. Both the dimensionless figure of merit (ZT) and the thermoelectric compatibility factor (C_F), which play very important roles for applications, were improved over the whole temperature region. PACS 72.15.Eb; 72.15.Jf; 72.20.Pa; 63.20.Mt; 74.25.Fy An erratum to this article can be found at     

PbSe-MnSe纳米复合热电材料的微结构和电热输运性能

相比于常见的热电材料PbTe, 另一种硫族铅化合物PbSe具有熔点高、Se储量更丰富等优势, 从而越来越受到科学界的关注. 本文采用熔融淬火结合快速热压烧结工艺制备了Pb_0.98-xMn_xNa_0.02Se(0 ≤x ≤ 0.12)纳米复合热电材料, 系统地研究了不同Mn含量对材料微纳结构、机械性能和热电性能的影响规律. 发现纳米复合样品中有面心立方结构的MnSe球状和薄层状析出物, 显微硬度得到显著增强. 少量固溶的Mn增加了能带简并度, 使功率因子提高, 球状析出物使声子散射增强、热导率降低, 体系的热电优值ZT得到优化; 但是当Mn含量更高时, 赛贝克系数趋于饱和, 连续析出物使晶格热导率反常增大, ZT 没有得到进一步改善. 通过进一步调节Na含量优化了载流子浓度, 获得了ZT=0.65的PbSe-MnSe纳米复合热电材料.     

Thermoelectric transport and spin density of graphene nanoribbons with Rashba spin–orbit interaction

In the present paper, we have theoretically investigated thermoelectric transport properties of armchair and zigzag graphene nanoribbons with Rashba spin–orbit interaction, as well as dephasing scattering processes by applying the nonequilibrium Green function method. Behaviors of electronic and thermal currents, as well as thermoelectric coefficients are studied. It is found that both electronic and thermal currents decrease, and thermoelectric properties been suppressed, with increasing strength of Rashba spin–orbit interaction. We have also studied spin split and spin density induced by Rashba spin–orbit interaction in the graphene nanoribbons.     

TeI4掺杂量对n型Bi2Te3基烧结材料热电性能的影响

采用区熔法结合放电等离子体快速烧结(SPS)技术制备了n型Bi₂Te₃基热电材料.在300—500K的温度范围内测量了各热电性能参数，包括电导率(σ)、塞贝克系数(α)和热导率(κ)，研究了掺杂剂TeI₄的含量(质量百分比分别为0，0.05，0.08，0.10，0.13和0.15wt%)对热电性能的影响.结果表明：试样的载流子浓度(n)随TeI₄含量增加而增大，使电导率增大、塞贝克系数的绝对值先增大而后减小，从而导致品质因子(α²σ)呈先增加后降低的变化趋势；同时，由于异质离子(I^-)以及载流子对声子的散射作用增强，可显著降低其晶格热导率.烧结材料的性能优值(ZT=α²σT/κ)对应于TeI₄含量为0.08wt%有其最大值，约为0.92.此外，烧结材料的抗弯强度增加至80MPa左右，从而可以显著改善材料的可加工性以及元器件的使用可靠性. 关键词： 2Te₃')" href="#">Bi₂Te₃ 放电等离子体快速烧结 热电性能     

Effect of carbon nanotubes addition on thermoelectric properties of Ca3Co4O9 ceramics

Increasing the phonon scattering center by adding nanoparticles to thermoelectric materials is an effective method of regulating the thermal conductivity. In this study, a series of Ca$_{3}$Co$_{4}$O$_{9}/x$ wt.% CNTs ($x=0$, 3, 5, 7, 10) polycrystalline ceramic thermoelectric materials by adding carbon nanotubes (CNTs) were prepared with sol-gel method and cold-pressing sintering technology. The results of x-ray diffraction and field emission scanning electron microscopy show that the materials have a single-phase structure with high orientation and sheet like microstructure. The effect of adding carbon nanotubes to the thermoelectric properties of Ca$_{3}$Co$_{4}$O$_{9}$ was systematically measured. The test results of thermoelectric properties show that the addition of carbon nanotubes reduces the electrical conductivity and Seebeck coefficient of the material. Nevertheless, the thermal conductivity of the samples with carbon nanotubes addition is lower than that of the samples without carbon nanotubes. At 625 K, the thermal conductivity of Ca$_{3}$Co$_{4}$O$_{9}$/10 wt.% CNTs sample is reduced to 0.408 W$\cdot$m$^{-1}\cdot$K$^{-1}$, which is about 73% lower than that of the original sample. When the three parameters are coupled, the figure of merit of Ca$_{3}$Co$_{4}$O$_{9}$/3 wt.% CNTs sample reaches 0.052, which is 29% higher than that of the original sample. This shows that an appropriate amount of carbon nanotubes addition can reduce the thermal conductivity of Ca$_{3}$Co$_{4}$O$_{9}$ ceramic samples and improve their thermoelectric properties.     

Effect of phonon scattering mechanisms on the lattice thermal conductivity of skutterudite-related compound

We have prepared the skutterudite-related compounds FeCo_3Sb_{12} and La_{0.75}Fe_3CoSb_{12} with different average grain sizes (about 0.8 and 3.9μm) by hot pressing. Samples were characterized by XRD, EPMA and SEM. The lattice thermal conductivity was investigated in the temperature range from room temperature to 200℃. Based on the Debye model, we analyse the change in lattice thermal conductivity due to various phonon scattering mechanisms by examining the relationship between the weighted phonon relaxation time τ(ω/ω_D)^2 and the reduced phonon frequency ω/ω_D. The effect of grain boundary scattering to phonon is negligible within the range of grain sizes considered in this study. The large reduction in lattice thermal conductivity of FeCo_3Sb_{12} compound contributes to the electron－phonon scattering. As for La_{0.75}Fe_3CoSb_{12} compound, the atoms of La filled into the large voids in the structure of the skutterudite produce more significant electron－phonon scattering as well as more substitute of Fe at Co site at the same time. Moreover, the point-defect scattering appears due to the difference between the atoms of La and the void. In addition, the scattering by the rattling of the rare-earth atoms in the void is another major contribution to the reduced lattice thermal conductivity. Introducing the coupling of the electron－phonon scattering with the point-defect scattering and the scattering by the rattling of the rare-earth atom is an effective method to reduce the lattice thermal conductivity of the skutterudite-related compounds by substitution of Fe for Co and the atoms of La filled in the large voids in the skutterudite structure.     

Ga掺杂对Cu_3SbSe_4热电性能的影响

采用熔融-淬火方法制备了Cu_(2.95)Ga_xSb_(1-x)Se_4(x=0,0.01,0.02和0.04)样品,系统地研究了Ga在Sb位掺杂对Cu_3SbSe_4热电性能的影响.研究结果表明,少量的Ga掺杂(x=0.01)可以有效提高空穴浓度,抑制本征激发,改善样品的电输运性能.掺Ga样品在625 K时功率因子达到最大值10μW/cm·K~2,比未掺Ga的Cu_(2.95)SbSe_4样品提高了约一倍.但是随着Ga掺杂浓度的进一步提高,缺陷对载流子的散射增强,同时载流子有效质量增大,导致载流子迁移率急剧下降.因此Ga含量增加反而使样品的电性能恶化.在热输运方面,Ga掺杂可以有效降低双极扩散对热导率的贡献,同时掺杂引入的点缺陷对高频声子有较强的散射作用,因此高温区的热导率明显降低.最终该体系在664 K时获得最大ZT值0.53,比未掺Ga的样品提高了近50%.     

Enhanced thermoelectric properties in two-dimensional monolayer Si2BN by adsorbing halogen atoms

Using the first principles calculation and Boltzmann transport theory, we study the thermoelectric properties of Si2BNadsorbing halogen atoms (Si2BN-4X, X = F, Cl, Br, and I). The results show that the adsorption of halogen atoms cansignificantly regulate the energy band structure and lattice thermal conductivity of Si2BN. Among them, Si2BN-4I has thebest thermoelectric performance, the figure of merit can reach 0.50 K at 300 K, which is about 16 times greater than that ofSi2BN. This is because the adsorption of iodine atoms not only significantly increases the Seebeck coefficient due to banddegeneracy, but also rapidly reduces the phonon thermal conductivity by enhancing phonon scattering. Our work proves theapplication potential of Si2BN-based crystals in the field of thermoelectricity and the effective method for metal crystals toopen bandgaps by adsorbing halogens.     

Phonon-mediated heat dissipation in a monatomic lattice: case study on Ni

The recently introduced analytical model for the heat current autocorrelation function of a crystal with a monatomic lattice [Evteev et al., Phil. Mag. 94 (2014) p. 731 and 94 (2014) p. 3992] is employed in conjunction with the Green–Kubo formalism to investigate in detail the results of an equilibrium molecular dynamics calculations of the temperature dependence of the lattice thermal conductivity and phonon dynamics in f.c.c. Ni. Only the contribution to the lattice thermal conductivity determined by the phonon–phonon scattering processes is considered, while the contribution due to phonon–electron scattering processes is intentionally ignored. Nonetheless, during comparison of our data with experiment an estimation of the second contribution is made. Furthermore, by comparing the results obtained for f.c.c. Ni model to those for other models of elemental crystals with the f.c.c. lattice, we give an estimation of the scaling relations of the lattice thermal conductivity with other lattice properties such as the coefficient of thermal expansion and the bulk modulus. Moreover, within the framework of linear response theory and the fluctuation-dissipation theorem, we extend our analysis in this paper into the frequency domain to predict the power spectra of equilibrium fluctuations associated with the phonon-mediated heat dissipation in a monatomic lattice. The practical importance of the analytical treatment lies in the fact that it has the potential to be used in the future to efficiently decode the generic information on the lattice thermal conductivity and phonon dynamics from a power spectrum of the acoustic excitations in a monatomic crystal measured by a spectroscopic technique in the frequency range of about 1–20 THz.     

Thermoelectric properties of Cr1−xMoxSi2

The thermoelectric properties of Mo-substituted CrSi₂ were studied. Dense polycrystalline samples of Mo-substituted hexagonal C40 phase Cr_1−xMo_xSi₂ (x=0–0.30) were fabricated by arc melting followed by spark plasma sintering. Mo substitution substantially increases the carrier concentration. The lattice thermal conductivity of CrSi₂ at room temperature was reduced from 9.0 to 4.5 W m⁻¹ K⁻¹ by Mo substitution due to enhanced phonon–impurity scattering. The thermoelectric figure of merit, ZT, increases with increasing Mo content because of the reduced lattice thermal conductivity. The maximum ZT value obtained in the present study was 0.23 at 800 K, which was observed for the sample with x=0.30. This value is significantly greater than that of undoped CrSi₂ (ZT=0.13).     

Intrinsically minimal thermal conductivity in cubic I-V-VI2 semiconductors

We report measurements of the thermal conductivity of high-quality crystals of the cubic I-V-VI2 semiconductors AgSbTe2 and AgBiSe2. The thermal conductivity is temperature independent from 80 to 300 K at a value of approximately 0.70 W/mK. Heat conduction is dominated by the lattice term, which we show is limited by umklapp and normal phonon-phonon scattering processes to a value that corresponds to the minimum possible, where the phonon mean free path equals the interatomic distance. Minimum thermal conductivity in cubic I-V-VI2 semiconductors is due to an extreme anharmonicity of the lattice vibrational spectrum that gives rise to a high Grüneisen parameter and strong phonon-phonon interactions. Members of this family of compounds are therefore most promising for thermoelectric applications, particularly as p-type materials.     

Nonlinear thermoelectric response due to energy-dependent transport properties of a quantum dot

Quantum dots are useful model systems for studying quantum thermoelectric behavior because of their highly energy-dependent electron transport properties, which are tunable by electrostatic gating. As a result of this strong energy dependence, the thermoelectric response of quantum dots is expected to be nonlinear with respect to an applied thermal bias. However, until now this effect has been challenging to observe because, first, it is experimentally difficult to apply a sufficiently large thermal bias at the nanoscale and, second, it is difficult to distinguish thermal bias effects from purely temperature-dependent effects due to overall heating of a device. Here we take advantage of a novel thermal biasing technique and demonstrate a nonlinear thermoelectric response in a quantum dot which is defined in a heterostructured semiconductor nanowire. We also show that a theoretical model based on the Master equations fully explains the observed nonlinear thermoelectric response given the energy-dependent transport properties of the quantum dot.