High thermoelectric performance and low thermal conductivity in K-doped SnSe polycrystalline compounds

SnSe single crystal showed a high thermoelectric zT of 2.6 at 923 K mainly due to an extremely low thermal conductivity 0.23 W m⁻¹ K⁻¹. It has anisotropic crystal structure resulting in deterioration of thermoelectric performance in polycrystalline SnSe, providing a low zT of 0.6 and 0.8 for Ag and Na-doped SnSe, respectively. Here, we presented the thermoelectric properties on the K-doped K_xSn_1−xSe (x = 0, 0.1, 0.3, 0.5, 1.5, and 2.0%) polycrystals, synthesized by a high-temperature melting and hot-press sintering with annealing process. The K-doping in SnSe efficiently enhances the hole carrier concentration without significant degradation of carrier mobility. We find that there exist widespread Se-rich precipitates, inducing strong phonon scattering and thus resulting in a very low thermal conductivity. Due to low thermal conductivity and moderate power factor, the K_0.001Sn_0.999Se sample shows an exceptionally high zT of 1.11 at 823 K which is significantly enhanced value in polycrystalline compounds.     

Synthesis and thermoelectric properties of Bi-doped SnSe thin films

Bi doped n-type SnSe thin films were prepared by chemical vapor deposition (CVD) and their structure and thermoelectric properties were studied. The x-ray diffraction patterns, x-ray photoelectron spectroscopy, and microscopic images show that the prepared SnSe thin films were composed of pure SnSe crystals. The Seebeck coefficients of the Bi-doped SnSe were greatly improved compared to that of undoped SnSe thin films. Specifically, Sn_0.99Bi_0.01Se thin film exhibited a Seebeck coefficient of -905.8μV·K^-1 at 600 K, much higher than 285.5 μV·K^-1 of undoped SnSe thin film. Further first-principles calculations reveal that the enhancement of the thermoelectric properties can be explained mainly by the Fermi level lifting and the carrier pockets increasing near the Fermi level due to Bi doping in the SnSe samples. Our results suggest the potentials of the Bi-doped SnSe thin films in thermoelectric applications.     

Graphene-enhanced thermoelectric properties of p-type skutterudites

Nanocomposite is proved to be an effective method to improve thermoelectric performance.In the present study,graphene is introduced into p-type skutterudite La_(0.8)Ti_(0.1)Ga_(0.1)Fe_3CoSb_(12)by plasma-enhanced chemical vapor deposition(PECVD)method to form skutterudite/graphene nanocomposites.It is demonstrated that the graphene has no obvious effect on the electrical conductivity of La_(0.8)Ti_(0.1)Ga_(0.1)Fe_3CoSb_(12),but the Seebeck coefficient is slightly improved at high temperature,thereby leading to high power factor.Furthermore,due to the enhancement of phonon scattering by the graphene,the lattice thermal conductivity is reduced significantly.Ultimately,the maximum z T value of La_(0.8)Ti_(0.1)Ga_(0.1)Fe_3CoSb_(12)/graphene is higher than that of graphene-free alloy and reaches to 1.0 at 723 K.Such an approach raised by us enriches prospects for future practical application.     

Ag掺杂对p型Pb0.5Sn0.5Te化合物热电性能的影响规律

采用熔融缓冷技术制备了不同Ag掺杂量的p型Ag_x(Pb_0.5Sn_0.5)_1-xTe化合物,系统地研究了Ag掺杂对所得材料的相组成、微结构及其热电传输性能.Ag的掺入显著增加了材料的空穴浓度,但是材料的空穴浓度远小于Ag作为单电子受主时理论空穴浓度,且在掺杂量为5%时未出现任何第二相,这表明Ag在可能进入晶格间隙位置而作为电子施主,起到补偿作用.随着Ag掺杂量的增加,样品的电导率逐渐增加,而Seebeck系数表现出复杂的变化趋势:在低于450 K时逐渐增加,而在温度大于450 K时逐渐降低,这主要源于材料复杂的价带结构.由于空穴浓度的优化和重空穴带的主导作用,1%Ag掺杂样品获得最大的功率因子,在750 K可达2.1 mW.m^-1.K^-2.此外,Ag的掺入引入的点缺陷大幅散射了传热声子,使得晶格热导率随着Ag掺量的增加逐渐降低.结果1%Ag掺杂样品在750 K时获得了最大的热电优值ZT=1.05,相比未掺样品提高了近50%,这一数值同商业应用的p型PbTe材料的性能相当.但是Sn取代显著降低了有毒重金属Pb的用量,这对PbTe基材料的商业化应用及其环境相适性具有重要意义.     

Self-consistent calculations of deep Sn and Se vacancy levels in SnSe by the Green’s function method

In the context of the Green’s function theory, the electronic structure of local defects-vacancies is considered self-consistently in the basis of localized orbitals. The origin and orbital structure of the electronic states in the gap, resonances and antiresonances in the valence band, and defect-induced changes in the electron density are discussed.     

Understanding the role of defects in influencing the thermoelectric properties of SnSe

As compared to single crystals, polycrystalline SnSe shows a considerable decline in its ZT value. Optimization of carrier concentration by the way of chemical doping is useful but creates point defect and vacancies that are often overlooked. Here we study polycrystalline Sn_0.95M_0.05Se (M = Co, Ni, In) with an aim to understand the role of defects. The overall crystal structure and microstructure of SnSe is not much affected with substitution as evident from X-ray diffraction and scanning electron microscopy study. Rietveld refinement confirms the single phase nature of the all compositions and provides unit cell parameters. Analysis of the stoichiometry reveals the presence of cation vacancies. Optical spectroscopy indicates a degradation of the in-direct gap and Urbach band tail-width fitting confirms the presence of localized states within the gap. Electrical resistivity and Seebeck coefficient are adversely affected by defects, but thermal conductivity decreases by almost 50% of SnSe value.     

Synthesis and thermoelectric properties of Nd-single filled p-type skutterudites

We report the synthesis of Nd-filled and Fe substituted p-type Ndx Fe_(3.2)Co_(0.8)Fe_(3.2)Co_(0.8)Sb_(12)(x=0.5,0.6,0.7,0.8,and 0.9)skutterudites by the solid-state reaction method.The influences of Nd filler on the electrical and thermal transport prop-erties are investigated in a temperature range from room temperature to 850 K.A lowest lattice thermal conductivity of 0.88 W·m~(-1)·K~(-1)is obtained in Nd0.8Fe_(3.2)Co_(0.8)Fe_(3.2)Co_(0.8)Sb_(12)at 673 K,which results from the localized vibration modes of fillers and the increase of grains boundaries.Meanwhile,the maximum power factor is 2.77 m W·m~(-1)·K~(-2)for the Nd_(0.9)Fe_(3.2)Co_(0.8)Fe_(3.2)Co_(0.8)Sb_(12)sample at 668 K.Overall,the highest dimensionless figure of merit z T=0.87 is achieved at 714 Kfor Nd_(0.9)Fe_(3.2)Co_(0.8)Fe_(3.2)Co_(0.8)Sb_(12).     

The effect of Te doping on the electronic structure and thermoelectric properties of SnSe

SnSe_1−xTe_x (x=0, 0.0625) bulk materials were fabricated by melting Sn, Se and Te powders and then hot pressing them at various temperatures. The phase compositions of the materials were determined by X-ray diffraction (XRD) and the crystal lattice parameters were refined by the Rietveld method performed with DBWS. XRD analysis revealed that the grains in the materials preferentially grew along the (l 0 0) directions. The structural behavior of SnSe_1−xTe_x (x=0, 0.0625) was calculated using CASTEP package provided by Materials Studio. We found that the band gap of SnSe reduced from 0.643 to 0.608 eV after Te doping. The calculated results were in good agreement with experimental results. The electrical conductivity and the Seebeck coefficient of the as-prepared materials were measured from room temperature to 673 K. The maximum power factor of SnSe is ∼0.7 μW cm⁻¹K⁻² at 673 K.     

YB48 the metal rich boundary of YB66; crystal growth and thermoelectric properties

It was discovered that the well-known higher boride YB₆₆, one of the first reported phonon glass electron crystals (PGEC), could be obtained in a much more metal-rich composition than previously thought possible. Using the floating zone growth method, YB₄₈ single crystals with YB₆₆ crystal structure could be obtained, and their thermoelectric properties measured. This expansion of the homogeneity range of the well-known YB₆₆ compound is surprising and a new Y atomic site was discovered. YB₄₈ exhibits much higher power factors than YB₆₆ which increase rapidly with increasing temperature. The obtained dimensionless figure of merit of this compound at 990 K is approximately 30 times higher than that of previously reported YB₆₆ samples, and higher than any other pristine higher boride. This discovery reveals YB₄₈ as a promising high temperature thermoelectric material.     

Excellent thermal stability and thermoelectric properties of Pnma-phase SnSe in middle temperature aerobic environment

SnSe is considered to be a promising thermoelectric material due to a high ZT value and abundant and non-toxic composition elements. However, the thermal stability is an important issue for commercial application. In particular,thermoelectric materials are in the high temperature for a long time due to the working condition. The present work investigates the thermal stability and oxidation resistance of single crystal SnSe thermoelectric materials. The scanning electron microscopy(SEM) and transmission electron microscopy(TEM) results show that the internal of SnSe crystal is not easily oxidized, while the x-ray photoelectron spectroscopy(XPS) results indicate that the surface of SnSe is slight oxidized to SnO_2. Even if the surface is oxidized, the SnSe crystal still exhibits stable thermoelectric properties. Meanwhile,the crystallization quality of SnSe samples can be improved after the appropriate heat treatment in the air, which is in favor of the carrier mobility and can improve the electrical conduction properties of SnSe. Moreover, the decrease of defect density after heat treatment can further improve the Seebeck coefficient and electrical transport properties of SnSe. The density functional theory(DFT) calculation verifies the important role of defect on the electrical conductivity and electron configuration. In summary, appropriate temperature annealing is an effective way to improve the transmission properties of SnSe single crystal thermoelectric materials.     

Faceting transitions in crystal growth and heteroepitaxial growth in the anisotropic phase-field crystal model

We modify the anisotropic phase-field crystal model(APFC),and present a semi-implicit spectral method to numerically solve the dynamic equation of the APFC model.The process results in the acceleration of computations by orders of magnitude relative to the conventional explicit finite-difference scheme,thereby,allowing us to work on a large system and for a long time.The faceting transitions introduced by the increasing anisotropy in crystal growth are then discussed.In particular,we investigate the morphological evolution in heteroepitaxial growth of our model.A new formation mechanism of misfit dislocations caused by vacancy trapping is found.The regular array of misfit dislocations produces a small-angle grain boundary under the right conditions,and it could significantly change the growth orientation of epitaxial layers.     

Ca和Ce双原子复合填充p型CamCenFexCo4－xSb12化合物的合成及热电性能

用高温熔融法合成了Ca和Ce复合填充的单相p型Ca_mCe_nFe_{xCo4-xSb12化合物，探索了两种原子复合填充对其热电性能的影 响规律.研究结果表明，填充分数相同时，Ca和Ce两种原子复合填充的p型CamCe nFexCo4-xSb12化合物的载流子浓度和电 导率介于Ca或Ce一种原子单独填充的化合物之间，且随两种原子填充分数m+n的增加而降低 ；赛贝克系数随两种原子填充总量，尤其是Ce填充分数m的增加以及温度的上升而增加；在 相同填充分数时，两种原子复合填充的p型CamCenFexC o4-xSb12化合物的晶格热导率较Ca或Ce一种原子单独填充的化合物 的晶格热导率低，当总填充分数m+n为0.3左右，且Ca和Ce的填充量大致相等时，化合物的晶 格热导率最低.p型Ca0.18Ce0.12Fe1.45Co2.55Sb12.21化合物的最大热电性能指数ZT值在750K时达到1.17. 关键词： skutterudite化合物 双原子复合填充 合成 热电性能}     

Zn掺杂p型Ba8Ga16ZnxGe30－x笼合物的合成及热电性能

用熔融法结合放电等离子烧结方法合成了Zn掺杂单相p型Ge基Ⅰ型笼合物Ba₈Ga₁₆Zn_xGe_30-x(x=3, 4, 5, 6)，探索Zn取代Ge对其热电性能的影响规律，结果表明：所制备的Ba₈Ga₁₆Zn_xGe_30-x化合物为p型传导，随Zn取代量x关键词： p型笼合物 合成 热电性能     

Zn掺杂P型Ba8Ga16ZnxGe30-x笼合物的合成及热电性能

用熔融法结合放电等离子烧结方法合成了Zn掺杂单相p型Ge基Ⅰ型笼合物Ba8Ga16ZnxGe30-x(x=3,4,5,6),探索Zn取代Ge对其热电性能的影响规律,结果表明:所制备的Ba8Ga16ZnxGe30-x化合物为p型传导,随Zn取代量x的增加,化合物室温载流子浓度Np逐渐增加,室温载流子迁移率μH和电导率逐渐降低.在所有试样中,Ba8Ga16Zn3Ge27化合物的Seebeck系数α在300—870K内始终最大,温度为300K时Seebeck系数为234μV/K,在700K附近达295μV/K.化合物的热导率随Zn取代量x的增加而降低.Ba8Ga16Zn3Ge27化合物在806K最大ZT值达0.38.     

Anisotropic thermoelectric and superconducting properties of the bulk misfit-layered (SnSe)1.17(TaSe2) compound

We present the thermoelectric and superconducting properties of the bulk misfit-layered (SnSe)_1.17(TaSe₂) compound with the critical temperature (T_c ~ 3.8 K). From XRD and electrical resistivity, the anisotropic properties of the misfit-layered compound by the preferred orientation were observed. The zero-temperature-limit upper critical field H_c2(0) and coherence length ξ are obtained by H_c2(0) = 8.94 T and ξ = 6.1 nm. The electron-phonon coupling constant (λ_e-p = 0.735) and the specific heat jump (ΔC_e/γT_c ~ 1.4) imply that the (SnSe)_1.17(TaSe₂) compound is a weak coupled conventional s-wave superconductor. Density functional theory (DFT) calculation results show that some electronic charge transfers from the SnSe layers into the TaSe₂ layers. In addition, the thermoelectric properties of the bulk misfit-layered (SnSe)_1.17(TaSe₂) compound show significant anisotropic properties.     

含铅空位的PbWO4晶体光学性质及其偏振特性的研究

利用完全势缀加平面波局域密度泛函近似,计算了含铅空位的PbWO4(PWO)晶体的电子结构,模拟计算了复数折射率、介电函数及吸收光谱的偏振特性.比较含铅空位的PWO晶体与完整的PWO晶体的吸收光谱及其偏振特性,得到与铅空位相关的吸收光谱及其偏振特性,计算结果与实验结果基本相符.计算得到的含铅空位的PWO晶体的光学偏振特性反映了PWO晶体的结构对称性.计算结果表明PWO晶体中350,420,550和680 nm的吸收带的出现与PWO晶体中铅空位的存在直接相关.     

The properties and structures of the mono- and the di- vacancy in Cu crystal

The structures and energies of formation and migration of the mono- and di-vacancy in Cu crystal have been described and calculated with modified analytical embedded atom method (MAEAM). The lattice relaxation is considered with molecular dynamics (MD) method at T=0 K. The results show the FN di-vacancy is the most stable and likely occurs in practice from the energy minimization. Compared with the mono-vacancy, the formation energy of the FN di-vacancy is higher than that of a mono-vacancy, but lower than that of two isolated mono-vacancy. The preferred migration mechanism of the FN di-vacancy is multi-jump of either vacancy (rotating the di-vacancy). The calculated migration energy of the FN di-vacancy is lower than that of a mono-vacancy, so the FN di-vacancy is easier to migrate. All of the calculated results are in good agreement with the experimental values.