巧妙的稀掺杂策略实现高性能GeTe热电材料

In thermoelectrics,doping is essential to augment the figure of merit.Traditional strategy,predomina ntly heavy doping,aims to optimize carrier concentration and restrain lattice thermal conductivity.However,this tactic can severely hamper carrier transport due to pronounced point defect scattering,particularly in materials with inherently low carrier mean-free-path.Conversely,dilute doping,although minimally affecting carrier mobility,frequently fails to optimize other vital thermoelectric parameters.Herein,we present a more nuanced dilute doping strategy in GeTe,leveraging the multifaceted roles of small-size metal atoms.A mere 4%CuPbSbTe_(3)introduction into GeTe swiftly suppresses rhombohedral distortion and optimizes carrier concentration through the aid of Cu interstitials.Additionally,the formation of multiscale microstructures,including zero-dimensional Cu interstitials,one-dimensional dislocations,two-dimensional planar defects,and three-dimensional nanoscale amorphous GeO_(2)and Cu_(2)GeTe_(3)precipitates,along with the ensuing lattice softening,contributes to an ultralow lattice thermal conductivity.Intriguingly,dilute CuPbSbTe_(3)doping incurs only a marginal decrease in carrier mobility.Subsequent trace Cd doping,employed to alleviate the bipolar effect and align the valence bands,yields an impressive figure-of-merit of 2.03 at 623 K in(Ge_(0.97)Cd_(0.03)Te)_(0.96)(CuPbSbTe_(3))_(0.04).This leads to a high energyconversion efficiency of 7.9%and a significant power density of 3.44 W cm^(-2)at a temperature difference of 500 K.These results underscore the invaluable insights gained into the constructive role of nuanced dilute doping in the concurrent tuning of carrier and phonon transport in GeTe and other thermoelectric materials.

Inhibiting the bipolar effect via band gap engineering to improve the thermoelectric performance in n-type Bi_(2-x)Sb_(x)Te_(3)for solid-state refrigeration

To date,the benchmark Bi_(2)Te_(3)-based alloys are still the only commercial material system used for ther-moelectric solid-state refrigeration.Nonetheless,the conspicuous performance imbalance between the p-type Bi_(2-x)Sb_(x)Te_(3)and n-type Bi_(2)Te_(3-x)Se_(x) legs has become a major obstacle for the improvement of cooling devices to achieve higher efficiency.In our previous study,novel n-type Bi_(2-x)Sb_(x)Te_(3)alloy has been pro-posed via manipulating donor-like effect as an alternative to mainstream n-type Bi_(2)Te_(3-x)Se_(x).However,the narrow bandgap of Bi_(2-x)Sb_(x)Te_(3)provoked severe bipolar effect that constrained the further improvement of zT near room temperature.Herein,we have implemented band gap engineering in n-type Bi_(1.5)Sb_(0.5)Te_(3)by employing isovalent Se substitution to inhibit the undesired intrinsic excitation and achieve the dis-tinguished room-temperature zT.First,the preferential occupancy of Se at Te^(2)site appropriately enlarges the band gap,thereby concurrently improving the Seebeck coefficient and depressing the bipolar thermal conductivity.In addition,the Se alloying mildly suppresses the compensation mechanism and essentially preserves the already optimized carrier concentration,which maintains the peak zT near room tempera-ture.Moreover,the large strain field and mass fluctuation generated by Se alloying leads to the remark-able reduction of lattice thermal conductivity.Accordingly,the zT value of Bi_(1.5)Sb_(0.5)Te_(2.8)Se_(0.2)reaches 1.0 at 300 K and peaks 1.1 at 360 K,which surpasses that of most well-known room-temperature n-type thermoelectric materials.These results pave the way for n-type Bi_(2-x)Sb_(x)Te_(3)alloys to become a new and promising top candidate for large-scale solid-state cooling applications.

Two-step phase manipulation by tailoring chemical bonds results in high-performance GeSe thermoelectrics

In thermoelectrics,phase engineering serves a crucial function in deter-mining the power factor by affecting the band degeneracy.However,for low-symmetry compounds,the mainstream one-step phase manipulation strategy,depending solely on the valley or orbital degeneracy,is inadequate to attain a high density-of-states effective mass and exceptional zT.Here,we employ a distinctive two-step phase manipulation strategy through stepwise tailoring chemical bonds in GeSe.Initially,we amplify the valley degeneracy via CdTe alloying,which elevates the crystal symmetry from a covalently bonded orthorhombic to a metavalently bonded rhombohedral phase by significantly suppressing the Peierls distortion.Subsequently,we incorporate Pb to trigger the convergence of multivalence bands and further enhance the density-of-states effective mass by moderately restraining the Peierls distortion.Additionally,the atypical metavalent bonding in rhombohedral GeSe enables a high Ge vacancy concentration and a small band effective mass,leading to increased carrier concentration and mobility.This weak chemical bond along with strong lattice anharmonicity also reduces lattice thermal conductivity.Consequently,this unique property ensemble contributes to an outstanding zT of 0.9 at 773 K for Geo.8oPbo.2oSe(CdTe)o.25.This work underscores the pivotal role of the two-step phase manipulation by stepwise tailoring of chemical bonds in improving the thermoelectric performance of p-bonded chalcogenides.