an Yu

Unique Bond Breaking in Crystalline Phase Change Materials and the Quest for Metavalent Bonding

Laser-assisted field evaporation is studied in a large number of compounds, including amorphous and crystalline phase change materials employing atom probe tomography. This study reveals significant differences in field evaporation between amorphous and crystalline phase change materials. High probabilities for multiple events with more than a single ion detected per laser pulse are only found for crystalline phase change materials. The specifics of this unusual field evaporation are unlike any other mechanism shown previously to lead to high probabilities of multiple events. On the contrary, amorphous phase change materials as well as other covalently bonded compounds and metals possess much lower probabilities for multiple events. Hence, laser-assisted field evaporation in amorphous and crystalline phase change materials reveals striking differences in bond rupture. This is indicative for pronounced differences in bonding. These findings imply that the bonding mechanism in crystalline phase change materials differs substantially from conventional bonding mechanisms such as metallic, ionic, and covalent bonding. Instead, the data reported here confirm a recently developed conjecture, namely that metavalent bonding is a novel bonding mechanism besides those mentioned previously.

Role of Nanostructuring and Microstructuring in Silver Antimony Telluride Compounds for Thermoelectric Applications

Thermoelectric (TE) materials are of utmost significance for conversion of heat flux into electrical power in the low-power regime. Their conversion efficiency depends strongly on the microstructure. AgSbTe2-based compounds are high-efficiency TE materials suitable for the mid-temperature range. Herein, we explore an Ag16.7Sb30Te53.3 alloy (at %) subjected to heat treatments at 380 °C for different durations aimed at nucleation and coarsening of Sb2Te3-precipitates. To characterize the Sb2Te3-precipitation, we use a set of methods combining thermal and electrical measurements in concert with transmission electron microscopy and atom probe tomography. We find correlations between the measured TE transport coefficients and the applied heat treatments. Specifically, the lowest electrical and thermal conductivity values are obtained for the as-quenched state, whereas the highest values are observed for alloys aged for 8 h. In turn, long-term heat treatments result in intermediate values of transport coefficients. We explain these findings in terms of interplay between precipitate formation and variations in the matrix composition, highlighting the importance of thermal stability of the material under service conditions.

Ag-Segregation to Dislocations in PbTe-Based Thermoelectric Materials

Dislocations have been considered to be an efficient source for scattering midfrequency phonons, contributing to the enhancement of thermoelectric performance. The structure of dislocations can be resolved by electron microscopy whereas their chemical composition and decoration state are scarcely known. Here, we correlate transmission Kikuchi diffraction and (scanning) transmission electron microscopy in conjunction with atom probe tomography to investigate the local structure and chemical composition of dislocations in a thermoelectric Ag-doped PbTe compound. Our investigations indicate that Ag atoms segregate to dislocations with a 10-fold excess of Ag compared with its average concentration in the matrix. Yet the Ag concentration along the dislocation line is not constant but fluctuates from ∼0.8 to ∼10 atom % with a period of about 5 nm. Thermal conductivity is evaluated applying laser flash analysis, and is correlated with theoretical calculations based on the Debye-Callaway model, demonstrating that these Ag-decorated dislocations yield stronger phonon scatterings. These findings reduce the knowledge gap regarding the composition of dislocations needed for theoretical calculations of phonon scattering and pave the way for extending the concept of defect engineering to thermoelectric materials.

The Effect of SbI3 Doping on the Structure and Electrical Properties of n-Type Bi1.8Sb0.2Te2.85Se0.15 Alloy Prepared by the Free Growth Method

Thermoelectric technology is regarded as one of the most promising direct power generation techniques via thermoelectric materials. However, the batch production and scale-up application are hindered because of the high-cost and poor performance. In this work, we adopt the free growth method to synthesize a series of the bulk materials of SbI3-doped Bi1.8Sb0.2Te2.85Se0.15 alloys. The structural and component investigations as well as the electrical properties characterization are carried out. The results show that SbI3 promotes the formation of Te-rich regions in the matrix. In addition, the synergistically optimized electrical conductivity and Seebeck coefficient are attained by controlling the SbI3 doping concentration. Thus, the sample with 0.30xa0wt.% SbI3 displays a highly increased power factor of ∼xa013.57xa0μWxa0cm−1xa0K−2, which is nearly 21 times higher than that of the undoped one. Moreover, the free growth method is reproducible, convenient and economical. Therefore, it has great potential as a promising technology for the batch synthesis.

Dependence of Solidification for Bi 2 Te 3−x Se x Alloys on Their Liquid States

The resistivity versus temperature (ρ-T) behaviours of liquid n-type Bi2Te3−xSex (xu2009=u20090.3, 0.45 and 0.6) alloys are explored up to 1050u2009°C. A clear hump is observed on all ρ-T curves of the three studied Bi2Te3−xSex melts during the heating process, which suggests that a temperature-induced liquid-liquid structural transition takes place in the melts. Based on this information, the solidification behaviours and microstructures of the alloys with different liquid states are investigated. The samples that experienced liquid structural transition show that the nucleation and growth undercooling degrees are conspicuously enlarged and the solidification time is shortened. As a result, the solidified lamellae are refined and homogenized, the prevalence of low-angle grain boundaries between these lamellae is increased, and the Vicker Hardness is enhanced. Atom probe tomography analyses prove that there is no segregation or nanoprecipitation within the grains, but the Te-rich eutectic structure and the evolution of composition near the Te-matrix phase boundary are investigated in a sample that experienced liquid structural transition. Our work implies that the solidification behaviours of Bi2Te3−xSex alloys are strongly related to their parent liquid states, providing an alternative approach to tailor the thermoelectric and mechanical properties even when only a simple solidification process is performed.

High Performance n-type PbSe-Cu2Se Thermoelectrics through Conduction Band Engineering and Phonon Softening

From a structural and economic perspective, tellurium-free PbSe can be an attractive alternative to its more expensive isostructural analogue of PbTe for intermediate temperature power generation. Here we report that PbSe0.998Br0.002-2%Cu2Se exhibits record high peak ZT 1.8 at 723 K and average ZTxa01.1 between 300 and 823 K to date for all previously reported n- and p-type PbSe-based materials as well as tellurium-free n-type polycrystalline materials. These even rival the highest reported values for n-type PbTe-based materials. Cu2Sexa0doping not only enhance charge transport properties but also depress thermal conductivity of n-type PbSe. It flattens the edge of the conduction band of PbSe, increases the effective mass of charge carriers, and enlarges the energy band gap, which collectively improve the Seebeck coefficient markedly. This is the first example of manipulating the electronic conduction band to enhance the thermoelectric properties of n-type PbSe. Concurrently, Cu2Se increases the carrier concentration with nearly no loss in carrier mobility, even increasing the electrical conductivity above ∼423 K. The resulting power factor is ultrahigh, reaching ∼21-26 μW cm-1 K-2 over a wide range of temperature from ∼423 to 723 K. Cu2Se doping substantially reduces the lattice thermal conductivity to ∼0.4 W m-1 K-1 at 773 K, approaching its theoretical amorphous limit. According to first-principles calculations, the achieved ultralow value can be attributed to remarkable acoustic phonon softening at the low-frequency region.

Thermoelectric Performance of Sb2Te3-Based Alloys is Improved by Introducing PN Junctions

Interface engineering has been demonstrated to be an effective strategy for enhancing the thermoelectric (TE) performance of materials. However, a very typical interface in semiconductors, that is, the PN junction (PNJ), is scarcely adopted by the thermoelectrical community because of the coexistence of holes and electrons. Interestingly, our explorative results provide a definitively positive case that appropriate PNJs are able to enhance the TE performance of p-type Sb2Te3-based alloys. Specifically, owing to the formation of the charge-depletion layer and built-in electric field, the carrier concentration and transport can be optimized and thus the power factor is improved and the electronic thermal conductivity is decreased. Meanwhile, PNJs provide scattering centers for phonons, leading to a reduced lattice thermal conductivity. Consequently, the p-type (Bi2Te3)0.15-(Sb2Te3)0.85 composites comprising PNJs achieve a ∼131% improvement of the ZT value compared with the pure Sb2Te3. The increased ZT demonstrates the feasibility of improving the TE properties by introducing PNJs, which will open a new and effective avenue for designing TE alloys with high performance.

Tailoring Thermoelectric Transport Properties of Ag-Alloyed PbTe: Effects of Microstructure Evolution

Capturing and converting waste heat into electrical power through thermoelectric generators based on the Seebeck effect is a promising alternative energy source. Among thermoelectric compounds, PbTe can be alloyed and form precipitates by aging at elevated temperatures, thus reducing thermal conductivity by phonon scattering. Here, PbTe is alloyed with Ag to form Ag-rich precipitates having a number density controlled by heat treatments. We employ complementary scanning transmission electron microscopy and atom probe tomography to analyze the precipitate number density and the PbTe-matrix composition. We measure the temperature-dependent transport coefficients and correlate them with the microstructure. The thermal and electrical conductivities, as well as the Seebeck coefficients, are found to be highly sensitive to the microstructure and its temporal evolution, e.g., the number density of Ag-rich precipitates increases by ca. 3 orders of magnitude and reaches (1.68 ± 0.92) × 1024 m-3 upon aging at 380 °C for 6 h, which is pronounced by reduction in thermal conductivity to a value as low as 0.85 W m-1 K-1 at 300 °C. Our findings will help to guide predictive tools for further design of materials for energy harvesting.