Optimization of Mechanical and Thermoelectric Properties of SnTe-Based Semiconductors by Mn Alloying Modulated Precipitation Evolution.

Multiscale defects engineering offers a promising strategy for synergistically enhancing the thermoelectric and mechanical properties of thermoelectric semiconductors. However, the specific impact of individual defects, in particular precipitation, on mechanical properties remains ambiguous. In this work, the mechanical and thermoelectric properties of Sn1.03- xMnxTe (x = 0-0.30) semiconductors are systematically studied. Mn-alloying induces dense dislocations and Mn nano-precipitates, resulting in an enhanced compressive strength with x increased to 0.15. Quantitative calculations are performed to assess the strengthening contributions including grain boundary, solid solution, dislocation, and precipitation strengthening. Due to the dominant contribution of precipitation strengthening, the yield strength of the x = 0.10 sample is improved by ≈74.5% in comparison to the Mn-free Sn1.03Te. For x ≥ 0.15, numerous MnTe precipitates lead to a synergistic enhancement of strength-ductility. In addition, multiscale defects induced by Mn alloying can scatter phonons over a wide frequency spectrum. The peak figure of merit ZT of ≈1.3 and an ultralow lattice thermal conductivity of ≈0.35 Wm-1 K-1 are obtained at 873 K for x = 0.10 and x = 0.30 samples respectively. This work reveals tha precipitation evolution optimizes the mechanical and thermoelectric properties of Sn1.03- xMnxTe semiconductors, which may hold potential implications for other thermoelectric systems.

Enhanced Strength Through Nanotwinning in the Thermoelectric Semiconductor InSb.

The conversion efficiency (zT) of thermoelectric (TE) materials has been enhanced over the last two decades, but their engineering applications are hindered by the poor mechanical properties, especially the low strength at working conditions. Here we used density functional theory (DFT) to show a strength enhancement in the TE semiconductor InSb arising from the twin boundaries (TBs). This strengthening effect leads to an 11% enhancement of the ideal shear strength in flawless crystalline InSb where this theoretical strength is considered as an upper bound on the attainable strength for a realistic material. DFT calculations reveal that the directional covalent bond rearrangements at the TB accommodating the structural mismatch lead to the anisotropic resistance against the deformation combined with the enhanced TB rigidity. This produces a strong stress response in the nanotwinned InSb. This work provides a fundamental insight for understanding the deformation mechanism of nanotwinned TE semiconductors, which is beneficial for developing reliable TE devices.

Superstrengthening Bi_{2}Te_{3} through Nanotwinning.

Bismuth telluride (Bi_{2}Te_{3}) based thermoelectric (TE) materials have been commercialized successfully as solid-state power generators, but their low mechanical strength suggests that these materials may not be reliable for long-term use in TE devices. Here we use density functional theory to show that the ideal shear strength of Bi_{2}Te_{3} can be significantly enhanced up to 215% by imposing nanoscale twins. We reveal that the origin of the low strength in single crystalline Bi_{2}Te_{3} is the weak van der Waals interaction between the Te1 coupling two Te1─Bi─Te2─Bi─Te1 five-layer quint substructures. However, we demonstrate here a surprising result that forming twin boundaries between the Te1 atoms of adjacent quints greatly strengthens the interaction between them, leading to a tripling of the ideal shear strength in nanotwinned Bi_{2}Te_{3} (0.6 GPa) compared to that in the single crystalline material (0.19 GPa). This grain boundary engineering strategy opens a new pathway for designing robust Bi_{2}Te_{3} TE semiconductors for high-performance TE devices.

Combining 27Al Solid-State NMR and First-Principles Simulations To Explore Crystal Structure in Disordered Aluminum Oxynitride.

The nuclear magnetic resonance (NMR) technique gives insight into the local information in a crystal structure, while Rietveld refinement of powder X-ray diffraction (PXRD) sketches out the framework of a crystal lattice. In this work, first-principles calculations were combined with the solid-state NMR technique and Rietveld refinement to explore the crystal structure of a disordered aluminum oxynitride (γ-alon). The theoretical NMR parameters (chemical shift, δiso, quadrupolar coupling constants, CQ, and asymmetry parameter, η) of Al22.5O28.5N3.5, predicted by the gauge-including projector augmented wave (GIPAW) algorithm, were used to facilitate the analytical investigation of the 27Al magic-angle spinning (MAS) NMR spectra of the as-prepared sample, whose formula was confirmed to be Al2.811O3.565N0.435 by quantitative analysis. The experimental δiso, CQ, and η of 27Al showed a small discrepancy compared with theoretical models. The ratio of aluminum located at the 8a to 16d sites was calculated to be 0.531 from the relative integration of peaks in the 27Al NMR spectra. The occupancies of aluminum at the 8a and 16d positions were determined through NMR investigations to be 0.9755 and 0.9178, respectively, and were used in the Rietveld refinement to obtain the lattice parameter and anion parameter of Al2.811O3.565N0.435. The results from 27Al NMR investigations and PXRD structural refinement complemented each other. This work provides a powerful and accessible strategy to precisely understand the crystal structure of novel oxynitride materials with multiple disorder.

Deformation and Failure Mechanisms of Element-Substituted Thermoelectric Type-I and Type-VIII Clathrates.

Clathrates are potential "phonon-glass, electron-crystal" thermoelectric semiconductors, whose structure of polyhedron stacks is very attractive. However, their mechanical properties have not yet met the requirements of industrial applications. Here, we report the ideal strength of element-substituted type-I and type-VIII clathrates and the shear deformation mechanism by using density functional theory. The results show that the framework element is the determinant of the intrinsic mechanical properties of the clathrates and is affected by sequential weakening of Si-Ge-Sn. The highest ideal shear strength is 8.71 GPa for I-Ba8Au6Si40 along the (110)/[001] slip system, which is attributed to the formation of higher-energy Si-Si covalent bonds. Meanwhile, the ideal shear strength of Ba-filled I/VIII clathrates (4.51/2.65 GPa) is higher than that of Sr-filled clathrates (3.64 GPa/1.91 GPa). In addition, the strength and ultimate strain of VIII-Ba8Ga16Sn30 can be significantly increased by the structural coordination accommodating with the stiffness of the Ga-Ge bond to achieve simultaneous bond breaking. Our findings demonstrate that the element substitution strategy is an effective approach for designing highly robust clathrates.

Synergetic Enhancement of Strength-Ductility and Thermoelectric Properties of Ag2 Te by Domain Boundaries.

Simultaneously improving the mechanical and thermoelectric (TE) properties is significant for the engineering applications of inorganic TE materials. In this work, a novel nanodomain strategy is developed for Ag2 Te compounds to yield 40% and 200% improved compressive strength (160 MPa) and fracture strain (16%) when compared to domain-free samples (115 MPa and 5.5%, respectively). The domained samples also achieve a 45% improvement in average ZT value. The domain boundaries (DBs) provide extra sites for dislocation nucleation while pinning the dislocation movement, resulting in superior strength and ductility. In addition, phonon scattering induced by DBs suppresses the lattice thermal conductivity of Ag2 Te and also reduces the weighted mobility. These findings provide new insights into grain and DB engineering for high-performance inorganic semiconductors with robust mechanical properties.

Strain-Induced Defect Evolution for the Construction of Porous Cu2-xSe with Enhanced Thermoelectric Performance.

Superionic Cu2-xSe, with disordered and even liquid-like Cu ions, has been extensively studied as a high efficiency thermoelectric material. However, the relationship between lattice stability and microstructure evolution in Cu2-xSe under strain, which is crucial for its application, has seldom been explored in previous research. In this study, we investigate the impacts of hydrostatic compression strain on the microstructural evolution and, consequently, its implications for thermoelectric performance. Molecular dynamics (MD) simulations show that high hydrostatic compression strain could induce local diffusion of Cu ions and Se twin evolution, resulting in the breaking and reforming of Cu-Se dynamic bonds and the unstable Se sublattice. The subsequent annealing process of the destabilized structure promoted Se evaporation from the sublattice and resulted in lotus-seedpod-like pores. The reduced sound velocity and intensified phonon scattering, due to pores, lead to a reduction in the lattice thermal conductivity from 0.44 W m-1 K-1 to 0.24 W m-1 K-1 at 800 K, a decrease of approximately 45%, in the porous Cu1.92Se sample. These findings reveal the relationship between stability and defect evolution in Cu2-xSe under high hydrostatic compression, offering a straightforward strategy of defect engineering for designing unique microstructures by leveraging the instability in superionic conductor materials.

Compression Induced Deformation Twinning Evolution in Liquid-Like Cu2Se.

For practical applications of copper selenide (Cu2Se) thermoelectric (TE) materials with liquid-like behavior, it is essential to determine the structure-property relations as a function of temperature. Here, we investigate ß-Cu2Se structure evolution during uniaxial compression over the temperature range of 400-1000 K using molecular dynamics simulations. We find that at temperatures above 800 K, Cu2Se exhibits poor stability with breaking order that is described as a liquid-like or hybrid structure comprising a rigid Se sublattice and mobile Cu ions. A uniaxial load causes accumulated structural heterogeneity that is alleviated by diffusion-induced accommodation of local deformations. With increasing strain, the deformation mode changes into a combination of compression and shear, accompanied by restructuring in terms of twinning. Interestingly, in addition to a plastic behavior rarely found in inorganic semiconductors, we find that higher temperature promotes deformation twinning in liquid-like Cu2Se, showing the role of thermal instability, including Cu diffusion, in structural adaptation and mechanical modulation. These findings reveal the micromechanism of hybrid structural evolution as well as performance tuning through twinning, which provides a theoretical guide toward advanced Cu2Se TE materials design.

Electronic Localization Derived Excellent Stability of Li Metal Anode with Ultrathin Alloy.

Lithium metal is an ideal anode for next-generation high-energy-density batteries. However, lithium dendrite growth has impeded its commercial application. Herein, fabricating Li-based ultrathin alloys with electronic localization and high surface work function via depositing Bi, Al, or Au metals on the surface of copper foil for in situ alloying with lithium is proposed. It is discovered that the electronic localization can induce self-smoothing effect of Li ions, as a result, significantly suppressing the growth of dendritic lithium. Meanwhile, the high surface work function can effectively alleviate side reactions between the electrolyte and lithium. With the as-obtained ultrathin alloys as anodes, excellent cycling performance is achieved. The half cells run stably after more than 120 cycles under high capacity of 4 mAh cm-2 . The S||Bi/Cu-Li full cell delivers a specific capacity of 736 mAh g-1 after 200 cycles. This work provides a new strategy for fabricating long-life and high-capacity lithium batteries.

Deformation and Failure Mechanisms of Thermoelectric Type-I Clathrate Ba8Au6Ge40.

Type-I clathrate Ba8Au6Ge40, possessing an interesting structure stacked by polyhedrons, is a potential "phonon-glass, electron-crystal" thermoelectric material. However, the mechanical properties of Ba8Au6Ge40 vital for industrial applications have not been clarified. Here, we report the first density functional theory calculations of the intrinsic mechanical properties of thermoelectric clathrate Ba8Au6Ge40. Among the different loading directions, the {110}/⟨001⟩ shearing and ⟨110⟩ tension are the weakest, with strengths of 4.51 and 6.64 GPa, respectively. Under {110}/⟨001⟩ shearing, the Ge-Ge bonds undergo significant stretching and twisting, leading to a severe distortion of the tetrakaidecahedral cage, giving rise to the fast softening of the flank Au-Ge bonds. At a strain of 0.2655, the Au-Ge bonds suddenly break, resulting in the collapse of the cage and the failure of the material. Under a ⟨110⟩ tension, the stretching of the Ge-Ge bonds keeps accelerating the softening of the Au-Ge bonds in the top/bottom hexagons, which releases the stress and disables the structure. The Au-Ge bonds are more rigid, contributing two-thirds of the structural deformation resistance. This work provides a new insight to understand the failure mechanisms of type-I clathrates with varied framework constitutions, which should help inform the design of robust thermoelectric clathrate materials.

Experimental Investigation on the Effect of Graphene Oxide Additive on the Steady-State and Dynamic Shear Properties of PDMS-Based Magnetorheological Elastomer.

Isotropic polydimethylsiloxane (PDMS)-based magnetorheological elastomers (MREs) filled with various contents of graphene oxide (GO) additive were fabricated by the solution blending-casting method in this work. The morphologies of the produced MREs were characterized, and the results indicate that the uniform distribution of GO sheets and carbonyl iron particles (CIPs) becomes difficult with the increase of GO content. The steady-state and dynamic shear properties of the MREs under different magnetic field strengths were evaluated using parallel plate rheometer. It was found that the physical stiffness effect of GO sheets leads to the increase of the zero-field shear modulus with increasing GO content under both the steady-state and dynamic shear loads. The chemical crosslinking density of PDMS matrix decreases with the GO content due to the strong physical crosslinking between GO and the PDMS matrix. Thus, the MREs filled with higher GO content exhibit more fluid-like behavior. Under the dynamic shear load, the absolute MR effect increases with the GO content due to the increased flexibility of the PDMS matrix and the dynamic self-stiffening effect occurring in the physical crosslinking interfaces around GO sheets. The highest relative MR effect was achieved by the MREs filled with 0.1 wt.% GO sheets. Then, the relative MR effect decreases with the further increase of GO content due to the improved zero-field modulus and the increased agglomerations of GO and CIPs. This study shows that the addition of GO sheets is a possible way to prepare new MREs with high MR effect, while simultaneously possessing high zero-field stiffness and load bearing capability.

Order-Tuned Deformability of Bismuth Telluride Semiconductors: An Energy-Dissipation Strategy for Large Fracture Strain.

In addition to thermoelectric (TE) performance tuning through defect or strain engineering, progress in mechanical research is of increasing importance to wearable applications of bismuth telluride (Bi2Te3) TE semiconductors, which are limited by poor deformability. For improving dislocation-controlled deformability, we clarify an order-tuned energy-dissipation strategy that facilitates large deformation through multilayer alternating slippage and stacking fault destabilization. Given that energy dissipation and dislocation motions are governed by van der Waals sacrificial bond (SB) behavior, molecular dynamics simulation is implemented to reveal the relation between the shear deformability and lattice order changes in Bi2Te3 crystals. Using the disorder parameter (D) that is defined according to the configurational energy distribution, the results of strain rates and initial crack effects show how the proper design of the initial structure and external conditions can suppress strain localization that would cause structural failure from the lack of energy dissipation, resulting in large homogeneous deformation of Bi2Te3 nanocrystals. This study uncovers the essence of the tuning mechanism in which highly deformable Bi2Te3 crystals should become disordered as slowly as possible until fracture. This highlights the role of the substructure evolution of SB-defect synergy that facilitates energy dissipation and performance stability during slipping. The disorder parameter D provides a bridge between micro/local mechanics and fracture strain, hinting at the possible mechanical improvement of Bi2Te3 semiconductors for designing flexible TE devices through order tuning and energy dissipation.

Rapid collagen-directed mineralization of calcium fluoride nanocrystals with periodically patterned nanostructures.

Collagen fibrils present periodic structures, which provide space for intrafibrillar growth of oriented hydroxyapatite nanocrystals in bone and contribute to the good mechanical properties of bone. However, there are not many reports focused on bioprocess-inspired synthesis of non-native inorganic materials inside collagen fibrils and detailed forming processes of crystals inside collagen fibrils remain poorly understood. Herein, the rapid intrafibrillar mineralization of calcium fluoride nanocrystals with a periodically patterned nanostructure is demonstrated. The negatively charged calcium fluoride precursor phase infiltrates collagen fibrils through the gap zones creating an intricate periodic mineralization pattern. Later, the nanocrystals initially filling the gap zones only expand gradually into the remaining space within the collagen fibrils. Mineralized tendons with organized calcium fluoride nanocrystals acquire mechanical properties (indentation elastic modulus ∼25.1 GPa and hardness ∼1.5 GPa) comparable or even superior to those of native human dentin and lamellar bone. Understanding the mineral growth processes in collagen may facilitate the development of tissue engineering and repairing.

A Magneto-Hyperelastic Model for Silicone Rubber-Based Isotropic Magnetorheological Elastomer under Quasi-Static Compressive Loading.

A new magneto-hyperelastic model was developed to describe the quasi-static compression behavior of silicone rubber-based isotropic magnetorheological elastomer (MRE) in this work. The magnetization property of MRE was characterized by a vibrating sample magnetometer (VSM), and the quasi-static compression property under different magnetic fields was tested by using a universal testing machine equipped with a magnetic field accessory. Experimental results suggested that the stiffness of the isotropic MRE increased with the magnetic flux density within the tested range. Based on experimental results, a new magneto-hyperelastic model was established by coupling the Ogden hyperelastic model, the magnetization model and the magneto-induced modulus model based on a magnetic dipole theory. The results show that the proposed new model can accurately predict the quasi-static compression property of the isotropic MRE under the tested magnetic flux density and strain ranges using only three model parameters.

Synthesis of monodisperse rod-shaped silica particles through biotemplating of surface-functionalized bacteria.

Mesoporous silica particles of controlled size and shape are potentially beneficial for many applications, but their usage may be limited by the complex procedure of fabrication. Biotemplating provides a facile approach to synthesize materials with desired shapes. Herein, a bioinspired design principle is adopted through displaying silaffin-derived 5R5 proteins on the surface of Escherichia coli by genetic manipulations. The genetically modified Escherichia coli provides a three-dimensional template to regulate the synthesis of rod-shaped silica. The silicification is initiated on the cell surface under the functionality of 5R5 proteins and subsequentially the inner space is gradually filled. Density functional theory simulation reveals the interfacial interactions between silica precursors and R5 peptides at the atomic scale. There is a large conformation change of this protein during biosilicification. Electrostatic interactions contribute to the high affinity between positively charged residues (Lys4, Arg16, Arg17) and negatively charged tetraethyl orthosilicate. Hydrogen bonds develop between Arg16 (OH), Arg17 (OH and NH), Leu19 (OH) residues and the forming silica agglomerates. In addition, the resulting rod-shaped silica copy of the bacteria can transform into mesoporous SiOx nanorods composed of carbon-coated nanoparticles after carbonization, which is shown to allow superior lithium storage performance.

Effects of calcination temperatures on photocatalytic activity of SnO2/TiO2 composite films prepared by an EPD method.

SnO2/TiO2 composite films were fabricated on transparent electro-conductive glass substrates (F-doped SnO2-coated glass:FTO glass) via an electrophoretic deposition (EPD) method using Degussa P25 as raw materials, and were further characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscope (FESEM), UV-vis diffuse reflectance spectra and Photoluminescence spectra (PL). XRD and XPS results confirmed that the films were composed of TiO2 and SnO2. FESEM images indicated that the as-prepared TiO2 films had roughness surfaces, which consisted of nano-sized particles. The effects of calcination temperatures on the surface morphology, microstructures and photocatalytic activity of SnO2/TiO2 composite films were further investigated. All the prepared SnO2/TiO2 composite films exhibited high photocatalytic activities for photocatalytic decolorization of Rhodamine-B aqueous solution. At 400 degrees C, the SnO2/TiO2 composite films showed the highest photocatalytic activity due to synergetic effects of low sodium content, good crystallization, appropriate phase composition and slower recombination rate of photogenerated charge carriers.

Grain Boundaries Softening Thermoelectric Oxide BiCuSeO.

Engineering grain boundaries (GBs) are effective in tuning the thermoelectric (TE) properties of TE materials, but the role of GB on mechanical properties, which is important for their commercial applications, remains unexplored. In this paper, we apply ab initio method to examine the ideal shear strength and failure mechanism of GBs in TE oxide BiCuSeO. We find that the ideal shear strength of the GB is much lower than that of the ideal single crystal. The atomic rearrangements accommodating the lattice and neighbor structure mismatch between different grains leads to the much weaker GB stiffness compared with grains. Failure of the GBs arises from either the distortion of the Cu-Se layers or the relative slip between Bi-O and Cu-Se layers. This work is crucial to illustrate the deformation of GBs, laying the basis for the development and design of mechanically robust polycrystalline TE materials.

Micro- and Macromechanical Properties of Thermoelectric Lead Chalcogenides.

Both n- and p-type lead telluride (PbTe)-based thermoelectric (TE) materials display high TE efficiency, but the low fracture strength may limit their commercial applications. To find ways to improve these macroscopic mechanical properties, we report here the ideal strength and deformation mechanism of PbTe using density functional theory calculations. This provides structure-property relationships at the atomic scale that can be applied to estimate macroscopic mechanical properties such as fracture toughness. Among all the shear and tensile paths that are examined here, we find that the lowest ideal strength of PbTe is 3.46 GPa along the (001)/⟨100⟩ slip system. This leads to an estimated fracture toughness of 0.28 MPa m1/2 based on its ideal stress-strain relation, which is in good agreement with our experimental measurement of 0.59 MPa m1/2. We find that softening and breaking of the ionic Pb-Te bond leads to the structural collapse. To improve the mechanical strength of PbTe, we suggest strengthening the structural stiffness of the ionic Pb-Te framework through an alloying strategy, such as alloying PbTe with isotypic PbSe or PbS. This point defect strategy has a great potential to develop high-performance PbTe-based materials with robust mechanical properties, which may also be applied to other materials and applications.

Multi-Scale Microstructural Thermoelectric Materials: Transport Behavior, Non-Equilibrium Preparation, and Applications.

Considering only about one third of the world's energy consumption is effectively utilized for functional uses, and the remaining is dissipated as waste heat, thermoelectric (TE) materials, which offer a direct and clean thermal-to-electric conversion pathway, have generated a tremendous worldwide interest. The last two decades have witnessed a remarkable development in TE materials. This Review summarizes the efforts devoted to the study of non-equilibrium synthesis of TE materials with multi-scale structures, their transport behavior, and areas of applications. Studies that work towards the ultimate goal of developing highly efficient TE materials possessing multi-scale architectures are highlighted, encompassing the optimization of TE performance via engineering the structures with different dimensional aspects spanning from the atomic and molecular scales, to nanometer sizes, and to the mesoscale. In consideration of the practical applications of high-performance TE materials, the non-equilibrium approaches offer a fast and controllable fabrication of multi-scale microstructures, and their scale up to industrial-size manufacturing is emphasized here. Finally, the design of two integrated power generating TE systems are described-a solar thermoelectric-photovoltaic hybrid system and a vehicle waste heat harvesting system-that represent perhaps the most important applications of thermoelectricity in the energy conversion area.

Structure and Failure Mechanism of the Thermoelectric CoSb3/TiCoSb Interface.

The brittle behavior and low strength of CoSb3/TiCoSb interface are serious issues concerning the engineering applications of CoSb3 based or CoSb3/TiCoSb segmented thermoelectric devices. To illustrate the failure mechanism of the CoSb3/TiCoSb interface, we apply density functional theory to investigate the interfacial behavior and examine the response during tensile deformations. We find that both CoSb3(100)/TiCoSb(111) and CoSb3(100)/TiCoSb(110) are energetically favorable interfacial structures. Failure of the CoSb3/TiCoSb interface occurs in CoSb3 since the structural stiffness of CoSb3 is much weaker than that of TiCoSb. This failure within CoSb3 can be explained through the softening of the Sb-Sb bond along with the cleavage of the Co-Sb bond in the interface. The failure mechanism of the CoSb3/TiCoSb interface is similar to that of bulk CoSb3, but the ideal tensile strength and failure strain of the CoSb3/TiCoSb interface are much lower than those of bulk CoSb3. This can be attributed to the weakened stiffness of the Co-Sb framework because of structural rearrangement near the interfacial region.