Xiaomi Zhang

Non-equilibrium processing leads to record high thermoelectric figure of merit in PbTe-SrTe.

The broad-based implementation of thermoelectric materials in converting heat to electricity hinges on the achievement of high conversion efficiency. Here we demonstrate a thermoelectric figure of merit ZT of 2.5 at 923u2009K by the cumulative integration of several performance-enhancing concepts in a single material system. Using non-equilibrium processing we show that hole-doped samples of PbTe can be heavily alloyed with SrTe well beyond its thermodynamic solubility limit of <1u2009mol%. The much higher levels of Sr alloyed into the PbTe matrix widen the bandgap and create convergence of the two valence bands of PbTe, greatly boosting the power factors with maximal values over 30u2009μWu2009cm−1u2009K−2. Exceeding the 5u2009mol% solubility limit leads to endotaxial SrTe nanostructures which produce extremely low lattice thermal conductivity of 0.5u2009Wu2009m−1u2009K−1 but preserve high hole mobilities because of the matrix/precipitate valence band alignment. The best composition is hole-doped PbTe–8%SrTe.

Distinct Impact of Alkali-Ion Doping on Electrical Transport Properties of Thermoelectric p-Type Polycrystalline SnSe

Recent findings about ultrahigh thermoelectric performance in SnSe single crystals have stimulated related research on this simple binary compound, which is focused mostly on its polycrystalline counterparts, and particularly on electrical property enhancement by effective doping. This work systematically investigated the thermoelectric properties of polycrystalline SnSe doped with three alkali metals (Li, Na, and K). It is found that Na has the best doping efficiency, leading to an increase in hole concentration from 3.2 × 10(17) to 4.4 × 10(19) cm(-3) at room temperature, accompanied by a drop in Seebeck coefficient from 480 to 142 μV/K. An equivalent single parabolic band model was found adequate to capture the variation tendency of Seebeck coefficient with doping levels within a wide range. A mixed scattering of carriers by acoustic phonons and grain boundaries is suitable for numerically understanding the temperature-dependence of carrier mobility. A maximum ZT of ∼0.8 was achieved in 1% Na- or K-doped SnSe at 800 K. Possible strategies to improve the mobility and ZT of polycrystals were also proposed.

Soft phonon modes from off-center Ge atoms lead to ultralow thermal conductivity and superior thermoelectric performance in n-type PbSe–GeSe

Historically PbSe has underperformed PbTe in thermoelectric efficiency and has been regarded as an inferior relative to its telluride congener. However, the fifty-fold greater natural abundance of Se relative to Te makes PbSe appealing as a thermoelectric material. We report that the n-type GeSe-alloyed PbSe system achieves a peak figure of merit, ZT, of ∼1.54 at 773 K and maintains ZT values above 1.2 over a broad temperature range from 623 K to 923 K. The highest performing composition is Sb-doped PbSe–12%GeSe, which exhibits an ultralow lattice thermal conductivity of ∼0.36 W m−1 K−1 at 573 K, close to the limit of amorphous PbSe. Theoretical studies reveal that the alloyed Ge2+ atoms prefer to stay at off-center lattice positions, inducing low frequency modes. The Ge atoms also cause the unexpected behavior where the next nearest atom neighbors (6 Pb atoms) oscillate at lower frequencies than in pure PbSe leading to a large reduction of the Debye temperature and acoustic phonon velocity. The Pb0.9955Sb0.0045Se–12%GeSe system also shows Ge-rich precipitates and many aligned dislocations within its microstructure which also contribute to phonon scattering. The resultant average ZT (ZTavg), a broad measure of the materials potential for functional thermoelectric modules, is 1.06 from 400 K to 800 K, the highest among all previously reported n- and p-type PbSe. This value matches or exceeds even those of the best n-type PbTe-based thermoelectric materials.

Abrupt Thermal Shock of (NH4)2Mo3S13 Leads to Ultrafast Synthesis of Porous Ensembles of MoS2 Nanocrystals for High Gain Photodetectors

Ultrafast synthesis of high-quality transition-metal dichalcogenide nanocrystals, such as molybdenum disulfide (MoS2), is technologically relevant for large-scale production of electronic and optoelectronic devices. Here, we report a rapid solid-state synthesis route for MoS2 using the chemically homogeneous molecular precursor, (NH4)2Mo3S13·H2O, resulting in nanoparticles with estimated size down to 25 nm only in 10 s at 1000 °C. Despite the extreme nonequilibrium conditions, the resulting porous MoS2 nanoparticles remain aggregated to preserve the form of the original rod shape bulk morphology of the molecular precursor. This ultrafast synthesis proceeds through the rapid decomposition of the precursor and rearrangement of Mo and S atoms coupled with simultaneous efficient release of massive gaseous species, to create nanoscale porosity in the resulting isomorphic pseudocrystals, which are composed of the MoS2 nanoparticles. Despite the very rapid escape of massive amounts of NH3, H2O, H2S, and S gases from the (NH4)2Mo3S13·H2O mm sized crystals, they retain their original shape as they convert to MoS2 rather than undergo explosive destruction from the rapid escape process of the gases. The obtained pseudocrystals are made of aggregated MoS2 nanocrystals exhibit a Brunauer-Emmett-Teller surface area of ∼35 m2/g with an adsorption average pore width of ∼160 Å. The nanoporous MoS2 crystals are solution processable by dispersing in ethanol and water and can be cast into large-area uniform composite films. Photodetectors fabricated from these films show more than 2 orders of magnitude higher conductivity (∼6.25 × 10-6 S/cm) and photoconductive gain (20 mA/W) than previous reports of MoS2 composite films. The optoelectronic properties of this nanoporous MoS2 imply that the shallow defects that originate from the ultrafast synthesis act as sensitizing centers that increase the photocurrent gain via two-level recombination kinetics.

Microstructure Evolution in Nanostructured High-Performance Thermoelectrics: The case of p-type Pb 1-x Na x Te-SrTe

Thermoelectric (TE) materials, which convert waste heat to useful electricity, have had their widespread deployment limited by low energy conversion efficiencies. Recent collaborative work has introduced an innovative all-scale hierarchical architecturing approach. In this approach, structural features across multiple length scales are introduced, ranging from point defects to nanoscale precipitates to microscale grain boundaries, which effectively scatter phonons across these disparate length-scales to achieve low thermal conductivity without significantly increasing charge carrier scattering. However, predictive control over synthesis and processing is required to control the microstructural constituents, especially the size, number and distribution of nanoscale precipitates, to achieve the targeted TE performance.