High Thermoelectric Performance Realized in a BiCuSeO System by Improving Carrier Mobility through 3D Modulation Doping

We report a greatly enhanced thermoelectric performance in a BiCuSeO system, realized by improving carrier mobility through modulation doping. The heterostructures of the modulation doped sample make charge carriers transport preferentially in the low carrier concentration area, which increases carrier mobility by a factor of 2 while maintaining the carrier concentration similar to that in the uniformly doped sample. The improved electrical conductivity and retained Seebeck coefficient synergistically lead to a broad, high power factor ranging from 5 to 10 μW cm^–1 K^–2. Coupling the extraordinarily high power factor with the extremely low thermal conductivity of ∼0.25 W m^–1 K^–1 at 923 K, a high <i>ZT</i> ≈ 1.4 is achieved in a BiCuSeO system

Origin of the High Performance in GeTe-Based Thermoelectric Materials upon Bi₂Te₃ Doping

As a lead-free material, GeTe has drawn growing attention in thermoelectrics, and a figure of merit (<i>ZT</i>) close to unity was previously obtained via traditional doping/alloying, largely through hole carrier concentration tuning. In this report, we show that a remarkably high <i>ZT</i> of ∼1.9 can be achieved at 773 K in Ge_0.87Pb_0.13Te upon the introduction of 3 mol % Bi₂Te₃. Bismuth telluride promotes the solubility of PbTe in the GeTe matrix, thus leading to a significantly reduced thermal conductivity. At the same time, it enhances the thermopower by activating a much higher fraction of charge transport from the highly degenerate Σ valence band, as evidenced by density functional theory calculations. These mechanisms are incorporated and discussed in a three-band (L + Σ + C) model and are found to explain the experimental results well. Analysis of the detailed microstructure (including rhombohedral twin structures) in Ge_0.87Pb_0.13Te + 3 mol % Bi₂Te₃ was carried out using transmission electron microscopy and crystallographic group theory. The complex microstructure explains the reduced lattice thermal conductivity and electrical conductivity as well