Sb Te Research Articles

Metalloid Chalcogen–pnictogen σ-hole bonding competition in stibanyl telluranes

In this manuscript a curious behavior observed in the solid state of several X-ray structures retrieved from the Cambridge structural database (CSD) is described and analyzed. These structures have in common the presence of a metalloid–metalloid pnictogen (Pn)–chalcogen (Ch) covalent bond (i.e., Sb–Te bond) in the structure. The Sb–Te bond presents different σ-holes at both ends of the bond in terms of size and intensity. These compounds have a tendency to form short intermolecular Sb•••Te interactions in the solid state. The aim of this work is to investigate, by using dispersion-corrected density functional theory (DFT-D3) calculations, whether the Sb•••Te contacts observed in the solid state correspond to PnB (Sb is the Lewis acid) or ChB (Te is the Lewis acid). Moreover, using two model stibanyl telluranes, the interaction energies with a series of Lewis bases and anions using both ends of the Sb–Te covalent bond have been computed to investigate which side (PnB or ChB donor) is able to establish stronger interactions with common electron rich atoms. Finally, several computational tools such as the quantum theory of atoms-in-molecules (QTAIM), noncovalent interaction plot (NCIPlot) index and electron localization (ELF) function (2D and 3D maps) have been used to further characterize the physical nature of the Sb•••Te interactions. The results reported herein suggest that in the Sb•••Te contacts the Te atom acts as σ-hole donor and the Sb as electron density donor.

Constructing multi-type defects in In0.1Sb1.9Te3-(MgB2)x composites: Simultaneously enhancing the thermoelectric and mechanical properties

Nanostructure technologies promote Sb2Te3 based alloys as powerful candidates for mid-temperature thermoelectric materials, but their actual application needs further breakthrough on both zT value and mechanical properties. Here, we prepare nanostructured In0.1Sb1.9Te3 with MgB2 addition, obtaining a high zT value of 1.01 at 673 K with significantly enhanced mechanical strength. It is found that the magnesium dissolves into the matrix lattice, while the boron (B) mainly precipitates out or enters into the van der Waal gaps. Combining with the occurrence of twin and domain boundaries, multi-type defects are constructed to simultaneously adjust the carrier and phonon transport, leading to enhanced power factor and reduced lattice/bipolar thermal conductivity. Meanwhile, the B interstitials and B-rich nanoprecipitates could effectively strengthen the materials. Especially at 673 K, the compressive strength is increased over 600% from < 1 MPa for In0.1Sb1.9Te3 to 7.5 MPa for In0.1Sb1.9Te3-(MgB2)0.015, overcoming the high-temperature softening problem and guaranteeing the service stability. Ultimately, a segmented leg composing of this material and low-temperature ternary alloy (Bi, Sb)2Te3 is fabricated through simple one-step sintering with a high conversion of 7% under a temperature difference of 375 K.

Intrinsic vacancy suppression and band convergence to enhance thermoelectric performance of (Ge, Bi, Sb)Te crystals

GeTe-based alloys have drawn increasing attention because of the excellent thermoelectric (TE) performance and potential applications in mid-temperature range. Although reducing carrier concentration by aliovalent doping plays an important role in maximizing the TE performance of GeTe alloys, modulating the intrinsic Ge vacancies is also indispensable. In this work, the intrinsic Ge vacancies of GeTe crystals were suppressed by the synthesis process of temperature gradient cooling technique (TGCT) and Bi-Sb co-doping. The later aliovalent doping also derives a facilitated band convergence, enhanced density-of-state effective mass, and maintained carrier mobility with optimized carrier concentration, along with enhanced phonon scattering from the fluctuations of mass and strain. Benefiting from enhanced electrical properties and reduced thermal conductivity, Ge0.91Bi0.06Sb0.03Te achieved a maximum ZT of 1.9 at 753 K, together with a comparable average ZT of 1.14 at 300–773 K. The results reveal the potential of the TGCT fabrication and Bi-Sb co-doping on enhancing TE performance of GeTe-based alloys with a strengthened suppression of Ge vacancies.

Regulation of exciton for high thermoelectric performance in (Bi, Sb)2Te3 alloys via doping with Pb and multi-scale microstructure

Herein, we report a reproducible improvement of the thermoelectric performance in BiSbTe alloy via kinetically and dynamically regulating excitation behavior in the intrinsic excitation regime. Doping with Pb increases the carrier concentration to the optimal value, kinetically pushing the onset temperature for the intrinsic excitation from 350 K for Bi0.46Sb1.54Te3 sample to 450 K for Pb0.01(Bi0.46Sb1.54)0.995Te3 sample. Moreover, the refined grains, nanostructures as well as dense dislocations induced by the melt-spinning process not only lower the lattice thermal conductivity via intensifying the interfacial phonon scattering but also selectively block the migration of minority carrier, modifying the dynamic process of the charge carrier and resulting in a smaller ratio of (μe/μh). This improves the power factor in the measured temperature range and suppresses the bipolar thermal conductivity in the intrinsic excitation regime. Thus, a maximum power factor of 4.44 mW m−1 K−2 and the lowest thermal conductivity of 1.06 W m−1 K−1 are attained for the sample with refined grains and nanostructures. All these contribute to the highest ZT value of 1.31 at 380 K and the highest average ZT value of 1.17 from 300 K to 500 K for Pb0.002(Bi0.46Sb1.54)0.999Te3 sample. This improved thermoelectric property was further verified in a thermoelectric module with the conversion efficiency of 4.38 % under a temperature gradient of 175 K, which is 20 % higher than that of the commercial ZM-based module under the same temperature gradient.

Twisted magnetic topological insulators

Motivated by the discovery of the quantum anomalous Hall effect in Cr-doped \ce{(Bi,Sb)2Te3} thin films, we study the generic states for magnetic topological insulators and explore the physical properties for both magnetism and itinerant electrons. First-principles calculations are exploited to investigate the magnetic interactions between magnetic Co atoms adsorbed on the \ce{Bi2Se3} (111) surface. Due to the absence of inversion symmetry on the surface, there are Dzyaloshinskii-Moriya-like twisted spin interactions between the local moments of Co ions. These nonferromagnetic interactions twist the collinear spin configuration of the ferromagnet and generate various magnetic orders beyond a simple ferromagnet. Among them, the spin spiral state generates alternating counterpropagating modes across each period of spin states, and the skyrmion lattice even supports a chiral mode around the core of each skyrmion. The skyrmion lattice opens a gap at the surface Dirac point, resulting in the anomalous Hall effect. These results may inspire further experimental investigation of magnetic topological insulators.

Unraveling the Atomic Structure of Bulk Binary Ga-Te Glasses with Surprising Nanotectonic Features for Phase-Change Memory Applications.

Binary Ge-Te and ternary Ge-Sb-Te systems belong to flagship phase-change materials (PCMs) and are used in nonvolatile memory applications and neuromorphic computing. The working temperatures of these PCMs are limited by low-T glass transition and crystallization phenomena. Promising high-T PCMs may include gallium tellurides; however, the atomic structure and transformation processes for amorphous Ga-Te binaries are simply missing. Using high-energy X-ray diffraction and Raman spectroscopy supported by first-principles simulations, we elucidate the short- and intermediate-range order in bulk glassy GaxTe1-x, 0.17 ≤ x ≤ 0.25, following their thermal, electric, and optical properties, revealing a semiconductor-metal transition above melting. We also show that a phase change in binary Ga-Te is characterized by a very unusual nanotectonic compression with the high internal transition pressure reaching 4-8 GPa, which appears to be beneficial for PCM applications increasing optical and electrical contrast between the SET and RESET states and decreasing power consumption.

Current-induced magnetization switching at charge-transferred interface between topological insulator (Bi,Sb)2Te3 and van der Waals ferromagnet Fe3GeTe2

Ferromagnetic two-dimensional van der Waals materials attract enormous interest as a platform to explore spin-related quantum phenomena, especially in conjunction with other quantum materials. Topological insulator is one such candidate to form the junction, because the spin-polarized nature of the surface or interface Dirac states enables the highly efficient spin-charge conversion. Here, we report the current-driven magnetization switching in the bilayer film of a van der Waals ferromagnetic semimetal Fe3GeTe2 (FGT) and a topological insulator (Bi1−xSbx)2Te3 (BST). We observed the current-induced magnetization switching via the Edelstein effect in a wide temperature range, whose threshold current density is as small as that reported for the heterostructure of FGT with a Pt layer. By analyzing the transport properties in heterostructures with different Fermi level (EF) positions in the BST layer, we found that the EF position of the charge-transferred interface Dirac states causes the significant variation of the threshold current density with a Bi/Sb ratio. The present result may promise spintronic phenomena in heterostructures of 2D van der Waals ferromagnets with topological insulators/semimetals.

Ab initio study on the fast reversible phase transitions of Ge2Sb2Te5

Ge2Sb2Te5 (GST) alloy has the ability to quickly transform between the amorphous phase and the crystalline phase; therefore, it can be used in non-volatile phase change storage. First-principles molecular dynamics was used to simulate the reversible phase change process of GST alloy, namely, amorphization and crystallization. The amorphous state was obtained by melting (∼3000 K) and cooling, and the amorphization process was characterized by the pair correlation function and bond angle distribution. The bond angles of amorphous GST were mainly distributed around 60°, 90°, and 110°, indicating the existence of octahedral and tetrahedral bonding configurations. The crystalline state was obtained by annealing at a temperature of 600 K, and the crystallization process was characterized by the pair correlation function, component disordered number, bond angle distribution, and dynamic atomic structure change. The results show that the bond angle of GST in crystallization is mainly distributed around 90°, and the structure mainly contains four-membered rings formed by Ge–Te and Sb–Te. By analyzing the optical properties, with the growth of crystallization time, the absorption coefficient, reflectivity, and conductivity of GST were significantly improved.

Lattice Deformation-Induced Enhancement in Thermoelectric Properties ofp-Type Bismuth Telluride-Based Alloys

ABSTRACTThe properties of a thermoelectric device depend on the thermoelectric material. Bi-Te-based thermoelectric materials consist ofp-type andn-type semiconductors are characterized by an excellent dimensionless figure of merit (ZT). In this study, we investigated the effect of the Bi/Sb compositional ratio on the thermoelectric properties inp-type Bi–Sb–Te alloys. Bi–Sb–Te powders were prepared by melting-grinding process. The sintered bodies were fabricated by the spark plasma sintering method, which allows short time sintering for controlling the growth of particles. By controlling the Bi/Sb ratio, the carrier concentration could be optimized. An increase in the Bi concentration led to a decrease in the carrier concentration and thermal conductivity, whereas the See-beck coefficient and specific resistance were increased due to phonon scattering. The thermoelectricZTvalue was found to be dependent on changes in the thermal and electrical properties. The best carrier concentration value (2.46 x 1019/cm2) and the highestZTvalue (1.3) were achieved forx= 0.4 in BixSb2−xTe3.

Cumulative defect structures for experimentally attainable low thermal conductivity in thermoelectric (Bi,Sb)2Te3 alloys

Manipulation of thermal transport properties by defect engineering is an important but yet unresolved issue in thermoelectrics, since rational design strategies of multiple defect structures for minimizing lattice thermal conductivity are lacking. The key is to comprehend complex interaction between different frequency-dependent phonon scattering processes by multiple defect structures. Herein, individual contributions in lattice thermal conductivity reduction from each defect structure—point defects (0-dimensional, 0D), dislocations (1D), grain boundaries (2D), and nanoparticles (3D)—are characterized based on experimental results of commercial (Bi,Sb)2Te3-based alloys fitted to Debye-Callaway model. Then, the cumulative contributions by multiple defect structures are investigated interactively by estimating total phonon relaxation time. Therefore, the interactive role of multiple defect structures in reducing lattice thermal conductivity is elucidated. To extend the approach to other thermoelectric materials, PbTe-based alloys with multiple defect structures of point defects and grain boundaries were modeled as well. This approach enables to provide a thorough design of defect structures for realizing the experimentally attainable low lattice thermal conductivity in thermoelectric materials.

Critical role of tellurium self-compensation in enhancing the thermoelectric performance of p-Type Bi0.4Sb1.6Te3 alloy

Traditionally, preparing p-type (Bi,Sb)2Te3 based materials by the combination of ball milling and hot pressing is regarded effective to reduce the lattice thermal conductivity and obtain high zT value. However, the deteriorated electrical transport properties and poor reproducibility restrict the further promotion of such technology. In this work, we prepare Bi0.4Sb1.6Te3 materials with Te self-compensation method, which leads to a high average zT value of 1.39 from 30 to 200 ℃ with significantly enhanced reproducibility. The Te self-compensation is found to be effective in manipulating the Bi(Sb)Te- and VTe2+ native defects in Bi0.4Sb1.6Te3 and thus suppress the “donor-like” effect caused by ball milling. The resulting enhanced carrier concentration further brings about a convergence of multi-valley bands, which leads to an increase in the density of states (DOS) near Fermi level and delays the onset of bipolar effect, in favor of improving electrical properties meanwhile reducing the bipolar thermal conductivity. Moreover, in the melting process, the excess Te facilitates the formation of Te-rich precipitates which remain in the ball-milled powders and then volatilize during the spark plasma sintering (SPS) process, thus leaving dispersedly distributed submicron pores and concequently reduced the lattice thermal conductivity. Taken together, the peak zT value reaches 1.55 at 100 ℃ and shows excellent reproducibility in three repeated measurements, which can promote the widespread application of the ball-milled (Bi,Sb)2Te3 based materials in solid-state refrigeration.

Absence of long-range magnetic order in lithium-containing honeycombs in the Li–Cr–Sb(Te)–O phases

Li3((LiCr)(Te/Sb))O6 compounds where Cr atoms along with Li and Te or Sb are part of a honeycomb and are studied using magnetic susceptibility, specific heat, x-ray photoelectron spectroscopy and neutron diffraction. The oxides stoichiometries as determined from the neutron diffraction studies are Li4.47Cr0.53TeO6 and Li3.88Cr1.12SbO6 with a stable oxidation state of +3 for Cr. Both the compounds crystallize in space group C2/m with intermixing of cations at the 4g sites leaving the 2a sites preferentially for Te or Sb. Again, the Li+ ions alone predominantly occur in the interlayer sites. Both the compounds show a broad anomaly in specific heat at 8 K, which is robust against 8 T. A corresponding anomaly is absent in the magnetic susceptibility but recovers from its derivative, dχ(T)/dT. We ascertain the magnetic anomaly temperatures (T a ) of Li4.47Cr0.53TeO6 and Li3.88Cr1.12SbO6 as 5.9 K and 6.7 K respectively from specific heat. Although the physical properties indicated a low temperature anomaly, neutron diffraction data did not reveal a magnetic signal or a structural anomaly down to 1.5 K. This rules out a conventional long-range ordered magnetic ground state in either compounds. Combining the results from specific heat, neutron diffraction and electron paramagnetic resonance, we put forth a scenario of depleted honeycomb lattice of Cr3+ with predominant short-range magnetic correlations as the magnetic ground states of the title compounds.

(Bi,Sb)2Te3/SiC nanocomposites with enhanced thermoelectric performance: Effect of SiC nanoparticle size and compositional modulation

Fabrication of nanoparticle-dispersed composites is an effective strategy for enhancing the performance of thermoelectric materials, and in particular SiC nanoparticles have been often used to create composites with Bi2Te3-based applied thermoelectric materials. However, the effect of particle size on the thermoelectric performance is unclear. This work systematically investigated the electrical and thermal properties of a series of (Bi,Sb)2Te3-based nanocomposites containing dispersed SiC nanoparticles of different sizes. It was found that particle size has a significant impact on the electrical properties with smaller SiC nanoparticles giving rise to higher electrical conductivity. Even though the dispersed SiC nanoparticles enhanced the Seebeck coefficient, no apparent dependence of the enhancement on the particle size was observed. It was also found that smaller SiC nanoparticles scatter phonons to some extent while the larger nanoparticles contribute to increased thermal conductivity. Eventually, the highest ZT value of 1.12 was obtained in 30 nm-SiC dispersed sample, corresponding to an increase by 18% from 0.95 for the matrix made from commercial scraps, and then the ZT was further boosted to 1.33 by optimizing the matrix composition and expelling excess Te during the optimized spark plasma sintering process. This work proves that the dispersion of smaller SiC nanoparticles in p-type (Bi,Sb)2Te3 materials is more effective than the dispersion of larger nanoparticles. In addition, it is revealed that additional compositional and/or processing optimization is vital and effective for obtaining further performance enhancement for nanocomposites of SiC nanoparticles dispersed in (Bi,Sb)2Te3.

Kinetic analysis of the reduction of a ternary system of Bi, Sb and Te oxides by hydrogen for BiSbTe3 synthesis

Reduction in a hydrogen atmosphere of Bi2O3, Sb2O3 and TeO2 mixes oxides for the synthesis of BiSbTe3 was analysed. The reduction reactions of Sb2O3 and Sb2O4 oxides, as well as Bi2O3+Sb2O3 and Sb2O3+3TeO2 mixtures, were also evaluated. The reduction of Sb2O4 is investigated for the first time. The reactions of the mixed oxides systems also were not the subject of research so far despite being used for synthesis of the (Bi,Sb)2Te3 material. The study comprised of kinetic analysis of TGA curves performed with non-parametric and isoconversional methods. Insight into powders’ structure during the process was taken to identify processes taking place. The results show, that Sb2O3 present in the reduced oxidizes to Sb2O4. This redox process between Sb oxide and another oxide takes place directly. The self-heating effect caused by elemental tellurium is diminished in the presence of Bi, because Bi-Te phases decrease the content of the elemental Te.

Magnetic Proximity Effect in an Antiferromagnetic Insulator/Topological Insulator Heterostructure with Sharp InterfaceSupported by the National Key Research and Development Program of China (Grant No. 2016YFA0300600), the National Natural Science Foundation of China (Grant No. 11961141011), and the Strategic Priority Research Program of Chinese Academy of Sciences (Grant No. XDB28000000).

We report an experimental study of electron transport properties of MnSe/(Bi,Sb)2Te3 heterostructures, in which MnSe is an antiferromagnetic insulator, and (Bi,Sb)2Te3 is a three-dimensional topological insulator (TI). Strong magnetic proximity effect is manifested in the measurements of the Hall effect and longitudinal resistances. Our analysis shows that the gate voltage can substantially modify the anomalous Hall conductance, which exceeds 0.1 e 2/h at temperature T = 1.6 K and magnetic field μ 0 H = 5 T, even though only the top TI surface is in proximity to MnSe. This work suggests that heterostructures based on antiferromagnetic insulators provide a promising platform for investigating a wide range of topological spintronic phenomena.

Weak-ferromagnetism for room temperature thermoelectric performance enhancement in p-type (Bi,Sb)2Te3

Unceasing efforts have been devoted to performance enhancement of thermoelectric (TE) materials, and recently reports suggested a new approach by utilizing magnetism to increase power factor. This work investigated the doping effect of Fe on the TE properties of Bi2Te3-based materials. A series of Fex(Bi,Sb)2-xTe3 bulk samples were synthesized via mechanical alloying combined with spark plasma sintering. XRD results and DFT calculations indicate that Fe2+ and Fe3+ would coexist and substitute Bi3+ site firstly and shrink lattice. The co-doped Fe2+/Fe3+ in (Bi,Sb)2Te3 is helpful to reduce carrier concentration (nH), band gap (Eg) and increase effective mass (m∗). With further increase of x, ferromagnetic FeTe2 second phase was precipitated from (Bi,Sb)2Te3 matrix. A weak-ferromagnetism was observed in all Fe-doped samples via M-H curve, which could scatter low energy carriers along with little effect on high-energy carriers, whereby the mobility was enhanced effectively. Owing to the synergistic effect of weak-ferromagnetism and optimized band structure, the maximum power factor reaches up to 45 μWcm−1K−2 as x = 0.05, which is 28.5% higher than that at x = 0. The peak ZT value reaches up to 1.2 at 323 K along with a theoretical ηmax of 7.6% in the range of 303–473 K were achieved in x = 0.05 sample. The results suggest that introducing weak-ferromagnetism is an effective way to enhance room temperature TE performance of Bi–Sb–Te based materials.

First-principles study of the liquid and amorphous phases of Sb2Te phase change memory material

We have investigated the local structure of liquid and amorphous phases of Sb2Te phase change memory material by the means of density functional theory-molecular dynamics simulations. The models of liquid and amorphous states were generated by quenching from the melt. The results show that the local environment of liquid Sb2Te is a mixed bonding geometry, where the average coordination numbers (CNs) of Sb and Te atoms are 4.93 and 4.23, respectively. Compared with crystalline state, there are more Sb–Sb bonds (∼53%) and less Sb–Te bonds (∼42%) with the presence of Te–Te bonds (∼5%) in liquid Sb2Te. Therefore, the formation of homopolar bonds and the breaking of heteropolar bonds are important structural transformations in melt process. For amorphous Sb2Te, the average CNs of Sb and Te atoms are 4.54 and 3.57, respectively. They are mostly in an octahedral environment, similar to the case in crystalline phase. The fractions of Sb–Sb, Te–Te, and Sb–Te bonds are ∼52%, ∼2%, and ∼46%, respectively. Thus, the increase in the fraction of octahedron accompanied with the decrease in average CN is the major structural changes in quenching process. Furthermore, the octahedral geometry in both the crystalline and amorphous Sb2Te increases the local structural similarity, facilitating the rapid low-energy crystallization.

Obtaining glasses in the extremely crystallizing Ge–Sb–Te phase change material

Using thermal co-evaporation techniques, we show that various glassy compositions can be obtained along the GexSbxTe100-2x join in the ternary Ge–Sb–Te system which is known to display dramatic crystallization tendencies. Earlier attempts to produce bulk glasses have been limited to Sb-poor compositions close to the eutectic GeTe6. Results indicate a weak variation of Tg with composition x and also a thermal stability that is weak for most systems, and especially for compositions close to the domain where Ge2Sb2Te5 can be formed. Our results are put in perspective with other network-forming chalcogenides and the Tg variation suggests the preferential formation of Te–Sb–Te, at variance with isochemical compounds such as Ge–Sb–Se. Data are discussed within the framework of topological based approaches which not only indicate that optimal glass formation is achieved for compositions satisfying the Maxwell stability criterion but also predict a flexible to rigid transition at x=8.5%. Most of our glasses could be formed around this composition.

Change in Structure of Amorphous Sb–Te Phase‐Change Materials as a Function of Stoichiometry

Chalcogenide phase‐change materials (PCMs) are a leading candidate for non‐volatile memory and neuro‐inspired computing applications. Antimony telluride alloys can be made into fast and robust PCMs by proper doping. Depending on the compositional ratio, the amorphous state of these alloys shows either nucleation‐ or growth‐driven crystallization dynamics at elevated temperatures. In this work, thorough ab initio simulations are carried out to study the structural properties and bonding nature of six Sb–Te alloys with varied composition from 2:3 to 4:1. Despite all of the compounds showing similar local structural motifs consisting of defective octahedral configurations, a gradual change in medium range order and cavity concentration is observed as the Sb content increases. This trend is responsible for the reduction in the nucleation rate, thus leading to growth‐driven crystallization. In addition, the degree of charge transfer decreases as the composition approaches the Sb end, reducing the driving force for long‐term mass transport and phase separation upon extensive cycling in devices.

Weighted Mobility Ratio Engineering for High-Performance Bi-Te-Based Thermoelectric Materials via Suppression of Minority Carrier Transport.

Thermoelectrics, which can generate electricity from a temperature difference, or vice versa, is a key technology for solid-state cooling and energy harvesting; however, its applications are constrained owing to low efficiency. Since the conversion efficiency of thermoelectric devices is directly obtained via a figure of merit of materials, zT, which is related to the electronic and thermal transport characteristics, the aim here is to elucidate physical parameters that should be considered to understand transport phenomena in semiconducting materials. It is found that the weighted mobility ratio of the majority and minority carrier bands is an important parameter that determines zT. For nanograined Bi-Sb-Te alloy, the unremarked role of this parameter on temperature-dependent electronic transport properties is demonstrated. This analysis shows that the control of the weighted mobility ratio is a promising way to enhance zT of narrow bandgap thermoelectric materials.