Molecular Dynamics Study of the Effects of Nanopores on the Tensile Mechanical Properties of Crystalline CoSb3

The effects of nanometer-size pores on the uniaxial tensile mechanical properties of single-crystal bulk CoSb₃ were investigated by classical molecular dynamics simulation. The pores were assumed to be cylindrical and uniformly distributed along two vertical principal crystallographic directions of a square lattice. The dependence of the effects of pores on pore diameter and porosity was examined separately, by varying pore diameter and porosity in the ranges a ₀–6a ₀ and 0.1–5%, respectively, where a ₀ is the lattice constant of CoSb₃. The results from simulation indicate that, at constant porosity, Young’s modulus remains almost constant whereas ultimate strength decreases as pore diameter increases. At constant pore diameter, Young’s modulus decreases monotonically as porosity increases exponentially; interestingly, variation of the ultimate strength is negligible. Numerically, the mechanical performance of systems containing nanopores is still desirable, although no better than that of the no-pore system. The results provide useful information for realistic application of skutterudites.     

The Impact of Nanostructuring on the Thermal Conductivity of Thermoelectric CoSb3

The high concentration of grain boundaries provided by nanostructuring is expected to lower the thermal conductivity of thermoelectric materials, which favors an increase in their thermoelectric figure‐of‐merit, ZT. A novel chemical alloying method has been used for the synthesis of nanoengineered‐skutterudite CoSb₃. The CoSb₃ powders were annealed for different durations to obtain a set of samples with different particle sizes. The samples were then compacted into pellets by uniaxial pressing under various conditions and used for the thermoelectric characterization. The transport properties were investigated by measuring the Seebeck coefficient and the electrical and thermal conductivities in the temperature range 300 K to 650 K. A substantial reduction in the thermal conductivity of CoSb₃ was observed with decreasing grain size in the nanometer region. For an average grain size of 140 nm, the thermal conductivity was reduced by almost an order of magnitude compared to that of a single crystalline or highly annealed polycrystalline material. The highest ZT value obtained was 0.17 at 611 K for a sample with an average grain size of 220 nm. The observed decrease in the thermal conductivity with decreasing grain size is quantified using a model that combines the macroscopic effective medium approaches with the concept of the Kapitza resistance. The compacted samples exhibit Kapitza resistances typical of semiconductors and comparable to those of Si–Ge alloys.     

Use of Molecular Dynamics Simulations to Study the Effects of Nanopores and Vacancies on the Mechanical Properties of Bi2Te3

The effects of nanopores and vacancies on the mechanical properties of Bi₂Te₃ have been studied. Cuboid single-crystal bulk Bi₂Te₃ with atoms removed was chosen for molecular dynamics simulations. The mechanisms of action of the two defects can be distinguished by their specific effects on the crystal structure of the bulk Bi₂Te₃. The mechanical properties of the nanoporous Bi₂Te₃ are affected by porosity (?), surface-to-volume ratio (ρ), and minimum cross-section length (L _min). The elastic modulus remains unchanged at 52.86 GPa for constant porosity of 0.7% whereas the ultimate stress and fracture strain gradually decrease with growing ρ or decreasing L _min. The lattice stability of Bi₂Te₃ gradually weakens as the proportion of vacancies increases; this leads to increasing potential energy and poorer mechanical properties of Bi₂Te₃. When the proportion of Bi vacancies is increased from 0% to 8%, the elastic modulus decreases from 57.17 GPa to 36.32 GPa, a reduction of 36.47%, the ultimate stress decreases from 6.40 GPa to 3.61 GPa, a reduction of 43.59%, and the fracture strain decreases from 22.4% to 13.8%, a reduction of 38.39%.     

A Nonequilibrium Molecular Dynamics Study of In-Plane Thermal Conductivity of Silicon Thin Films

We employed a nonequilibrium molecular dynamics (NEMD) simulator to calculate the in-plane thermal conductivity of silicon thin films. To avoid contamination of the temperature nonlinearity due to artificial heat addition/rejection, the selection of a proper linear range was investigated. It was found that the contaminated range was larger for thicker films and longer simulation lengths. To perform the quantum correction that is necessary when the MD simulation temperature is lower than the Debye temperature, we also attempted to obtain the confined phonon densities of states via equilibrium MD (EMD) simulations. The investigation showed that the thermal conductivities corrected by the thin-film density of states (DOS) agree excellently with theoretical predictions based on the phonon Boltzmann transport equation. A relationship between the surface roughness measurable in the laboratory and the specular fraction usually employed in the analysis was thus constructed.     

Ni掺杂CoSb_3化合物的热电性能及机理研究

采用机械合金化结合冷等静压的方法制备了CoSb3和Co3.5Ni0.5Sb12化合物,并测量了其热电性能。利用基于密度泛函理论赝势平面波的方法对Ni掺杂前后的CoSb3的能带结构和态密度进行了计算,实验和理论计算结果表明:CoSb3的费密面位于导带和价带之间,其电阻率随温度的升高而降低,为非简并半导体;Co3.5Ni0.5Sb12的费密面进入导带,其电阻率随温度的升高而增大,为n型简并半导体;本实验条件下,Co3.5Ni0.5Sb12化合物的功率因子在550 K时出现最大值2 292.92μW/(m.K2),是未掺杂CoSb3化合物最大值的12倍。     

Effect of High-Pressure Torsion on Texture,Microstructure, and Raman Spectroscopy: Case Study of Fe- and Te-Substituted CoSb3

Fe_0.05Co_0.95Sb_2.875Te_0.125, a double-element-substituted skutterudite, was prepared by induction melting, annealing, and hot pressing (HP). The hot-pressed sample was subjected to high-pressure torsion (HPT) with 4 GPa pressure at 673 K. X-ray diffraction was performed before and after HPT processing of the sample; the skutterudite phase was observed as a main phase, but an additional impurity phase (CoSb₂) was observed in the HPT-processed sample. Surface morphology was determined by high-resolution scanning electron microscopy. In the HP sample, coarse grains with sizes in the range of approximately 100 nm to 300 nm were obtained. They changed to fine grains with a reduction in grain size to 75 nm to 125 nm after HPT due to severe plastic deformation. Crystallographic texture, as measured by x-ray diffraction, indicated strengthening of (112), (102) poles and weakening of the (123) pole of the HPT-processed sample. Raman-active vibrational modes showed a peak position shift towards the lower energy side, indicating softening of the modes after HPT. The distortion of the rectangular Sb–Sb rings leads to broadening of Sb–Sb vibrational modes due to local strain fluctuation. In the HPT process, a significant effect on the shorter Sb–Sb bond was observed as compared with the longer Sb–Sb bond.     

Thermal Decomposition of Thermoelectric Material CoSb3: A Thermogravimetry Kinetic Analysis

The thermal decomposition of the thermoelectric CoSb₃ alloy was investigated using thermogravimetry (TG). TG curves obtained in inert gas flow with different heating rates were used to perform kinetic analysis based on the Arrhenius equation. Kinetic parameters, such as the effective activation energy, the pre-exponential factor, and the kinetic model function $ f(\alpha ) $ , were obtained using the Freeman–Carroll method, the multiheating rates method, and the Coats–Redfern equation. The activation energy was found to be around 200 kJ/mol, and the reaction mechanism for the decomposition of CoSb₃ alloy mostly obeys the second-order chemical decomposition process $ f(\alpha ) = (1 - \alpha )^{2} $ .     

C-Si模型分子动力学三维并行仿真算法

对于单晶硅磨削过程模拟的并行算法,依据C-Si系统的分子动力学模型及其特殊模型的特性,通过分析负载均衡和消息通信,利用"最小表面"原则,给出了一种空间分解并行方案。仿真实验证明算法可以缓解负载失衡并且降低通信开销,收集的对比实验数据证实了算法的高效性。     

Polymeric Giant Unilamellar Vesicles with Integrated DNA-Origami Nanopores: An Efficient Platform for Tuning Bioreaction Dynamics Through Controlled Molecular Diffusion

Giant unilamellar vesicles (GUVs) are microcompartments serving to confine reactions, allow signaling pathways, or design synthetic cells. Polymer GUVs are composed of copolymer membranes mimicking cell membranes, and present advantages over lipid-based GUVs, such as higher mechanical stability and chemical versatility. Such microcompartments are essential for understanding reactions/signaling occurring in cells, which are difficult to study by in vivo approaches due to the cell's complexity. However, the lack of control over their production, stability, and membrane diffusion properties is still limiting their use for bio-related applications. Here, polymer GUVs produced by microfluidics and permeabilized with DNA-origami nanopores (DoNs) that present a high level of control over these essential properties are introduced. After systematic optimization of conditions, DoN-GUVs reveal a narrow size distribution, allow for high encapsulation efficiencies, and are stable for weeks, protecting encapsulated biomolecules. The kinetics of diffusion of molecules through the GUV's membrane is tuned by insertion of DoNs with a controlled 3D- structure. DNA polymerase I, encapsulated as model for bioreactions, successfully produced DNA duplex strands with spatiotemporal control. DoN-GUVs loaded with active molecules open new avenues in bioreactions, from the detection of biomolecules, over the tuning of molecular transport rates, to the investigation of cellular processes/signaling.     

Search for Resonant-Like Impurity in Ag-Doped CoSb3 Skutterudite: Theoretical and Experimental Study

Korringa–Kohn–Rostoker coherent potential approximation (KKR-CPA) calculations of Ag-doped CoSb₃ point to the presence of either an extra sharp peak of s-symmetry Ag density of states near the valence-band edge when filling the void (2a) or to conventional p-type doping when substituting Sb site (24g). These results suggest a resonant-like impurity level in the former or nearly rigid-band behavior in the latter. To confirm the theoretical predictions, a series of samples with nominal composition Co₈Sb₂₄:Ag _x (x = 0, 0.1, 0.3, 0.4, 0.5) were prepared. Structural and phase composition analyses were carried out by x-ray diffraction, scanning electron microscopy, and scanning thermoelectric microprobe. Investigations of the influence of Ag impurity on the electrical conductivity and Seebeck coefficient were performed over the temperature range from 300 K to 560 K. It was found that doping CoSb₃ with Ag leads to an increase of the thermoelectric power factor α ² σ in the temperature range from 300 K to 475 K of about an order of magnitude for all doped samples. However, electron probe microanalysis revealed accumulation of Ag mainly in grain boundaries while the presence of Ag in CoSb₃ crystallites was not confirmed. This observation corroborates the results of KKR-CPA calculations concerning the formation energy of the Ag _x Co₄Sb₁₂ system, which is much lower than values calculated for A _x Co₄Sb₁₂ (A = Ca, Ba).     

Influence of ZnO Inclusions on the Low-Temperature Thermoelectric Properties of CoSb3

CoSb₃ composites with different amounts of ZnO nanoparticles (2?wt.% to 12?wt.%) were prepared from nanosized ZnO (commercial) and micron-sized CoSb₃ (obtained via solid-state reaction) particles mixed in solution and freeze dried. The resulting powders were densified by spark plasma sintering. The samples were characterized by x-ray diffraction and scanning electron microscopy. It was found that ZnO forms micron-sized clusters at the grain boundaries of the matrix material. The thermoelectric properties (electrical resistivity, thermopower, and thermal conductivity) were measured in the 2?K to 300?K temperature range. Both the electrical and thermal conductivities were observed to decrease with increasing ZnO content. The dimensionless figure of merit ZT was improved by up to 30% at 300?K for the sample containing 2?wt.% ZnO.     

Use of Atomistic Phonon Dispersion and Boltzmann Transport Formalism to Study the Thermal Conductivity of Narrow Si Nanowires

We study the thermal properties of ultra-narrow silicon nanowires (NW) with diameters from 3 nm to 12 nm. We use the modified valence-force-field method for computation of phononic dispersion and the Boltzmann transport equation for calculation of phonon transport. Phonon dispersion in ultra-narrow 1D structures differs from dispersion in the bulk and dispersion in thicker NWs, which leads to different thermal properties. We show that as the diameter of the NW is reduced the density of long-wavelength phonons per cross section area increases, which increases their relative importance in carrying heat compared with the rest of the phonon spectrum. This effect, together with the fact that low-frequency, low-wavevector phonons are affected less by scattering and have longer mean-free-paths than phonons in the rest of the spectrum, leads to a counter-intuitive increase in thermal conductivity as the diameter is reduced to the sub-ten-nanometers range. This behavior is retained in the presence of moderate boundary scattering.     

Molecular Dynamics Study of the Structural and Mechanical Properties of Skutterudite CoSb<Subscript>3</Subscript>: Surface Effect

Molecular dynamics simulations of the structural and mechanical properties of single-crystalline CoSb₃ have been carried out at room temperature. Special emphasis was given to the surface effect. Four different boundary conditions were applied to represent a wide range of surface-atom fractions. The LAMMPS program in conjunction with a multibody potential was employed. First, free relaxation was performed to obtain the corresponding stable configurations. The atomic rearrangements and energy distributions were observed. Then, uniaxial tensile deformation was simulated at a constant strain rate. The stress–strain responses and structural evolutions were examined during the process. Comparison of simulation results between different boundary conditions was carefully made. It was found that, when the scale of the single-crystalline CoSb₃ model becomes nanometric and the fraction of the surface atoms increases, the mechanical performance becomes substantially worse. Nonetheless, the deformation mechanism and intrinsic mechanical nature are very similar.     

改性钙钛酸铅陶瓷的电导性能研究

当掺钙钛酸铅(PCT)用作为压电、热释电材料时,除介电性能外,电导性能也是重要的性能参数。采用传统固相法制备掺钙钛酸铅系陶瓷,研究了不同掺杂量的Sb2/3Mn1/3及烧结助剂NiO、Bi2O3对陶瓷相结构、介电损耗和电导性能的影响。结果表明,在1 180℃下烧结2h,得到纯钙钛矿结构的改性陶瓷,陶瓷介电损耗降低;Sb2/3Mn1/3掺杂量对PCT系陶瓷在20~40℃的电阻温度稳定性有明显影响,随Sb2/3Mn1/3含量增加电阻温度系数(TCR)增大;在Pb0.80Ca0.20(Sb2/3Mn1/3)0.05Ti0.95O3中加入NiO、Bi2O3后有效降低了陶瓷在20~40℃的电阻温度系数;掺杂元素种类和掺杂量对陶瓷在20~80℃的TCR值基本没有影响,TCR值约为-0.15μ℃-1。     

Nanoscratching of Metallic Thin Films on Silicon Substrate: a Molecular Dynamics Study

By using a molecular dynamics method, a computer simulation of a scratch test on a nanometer scale has been performed. The specimen is composed of four atomic layers of metallic atoms deposited on a substrate of 864 silicon atoms. The thin-film materials chosen were Al, Cu, Ti, and W. The critical load had a similar tendency to the interface energy of a heterogeneous junction, and the maximum friction constant coincided fairly well with adhesion strength. On the basis of our simulation results we propose methods for detecting the critical load of scratching and for estimating the bonding of the film–substrate interface.     

InSb晶片表面有机物沾污清洗的分子动力学研究

清洗是混成式探测器芯片器件制造过程中的一道关键工序。探测器芯片表面所吸附的有机物沾污是清洗的主要目标。使用第一性原理与分子动力学相结合的方法研究了丙酮、乙酸乙酯对InSb晶面有机物沾污(主要成分为502)的清洗机理。第一性原理计算结果表明,丙酮与乙酸乙酯的分子反应活性位点均离域在杂原子上,两者可通过杂原子对吸附在InSb表面的502解吸附以达到清洗的目的。分子动力学模拟结果表明,乙酸乙酯可以促进丙酮分子在502膜层中的扩散能力,以此加强丙酮对502的去除作用。     

Vacancy and Temperature Effects on Mechanical Properties of Single-Crystal Bulk Mg2Si: A Molecular Dynamics Study

The mechanical properties of single-crystal bulk Mg₂Si have been investigated using the molecular dynamics simulation method, in which a many-body potential energy function including bond and angle interactions is adopted to predict the mechanical properties. Virtual tension tests of specimens under different conditions, including Mg vacancy and temperature effects, were carried out by controlling the strain along the principal crystallographic direction. The simulation results show that single-crystal bulk Mg₂Si exhibits a nonlinear elastic stress–strain response and the mechanical properties degrade significantly with increasing vacancy content. Moreover, the effect of temperature on the mechanical properties of single-crystal bulk Mg₂Si is also discussed in detail.     

Effects of Annealing on Microstructure and Thermoelectric Properties of Nanostructured CoSb3

Nanocrystallization of thermoelectric materials is an effective way to reduce their thermal conductivity, but so far the thermal stability of nanostructured thermoelectric materials has been little studied. Effects of annealing treatment on the microstructure and the thermoelectric properties of nanostructured CoSb₃ were investigated in this work. Samples with average grain size of 300 nm were prepared by spark plasma sintering of high-energy ball-milled nanosized CoSb₃ powders. The study shows that annealing has a very significant impact on the grain size of the samples. The grain size of the sample with 100 h annealing is three times greater than before annealing. The major phase in the 150-h-annealed sample is still skutterudite, except for a trace amount of Sb phase. With increasing annealing time, the density reduces slightly. In addition, the power factor of the sample decreases, thus resulting in a decrease of the thermoelectric figure of merit.