Ultralow Lattice Thermal Conductivity and High Thermoelectric Performance in Ge_1-x-yBi_xCa_yTe with Ultrafine Ferroelectric Domain Structure

GeTe and its derivatives emerging as a promising lead-free thermoelectric candidate have received extensive attention. Here, a new route was proposed that the minimization of κ_L in GeTe through considerable enhancement of acoustic phonon scattering by introducing ultrafine ferroelectric domain structure. We found that Bi and Ca dopants induce strong atomic strain disturbance in the GeTe matrix because of large differences in atom radius with host elements, leading to the formation of ultrafine ferroelectric domain structure. Furthermore, large strain field and mass fluctuation induced by Bi and Ca codoping result in further reduced κ_L by effectively shortening the phonon relaxation time. The co-existence of ultrafine ferroelectric domain structure, large strain field, and mass fluctuation contribute to an ultralow lattice thermal conductivity of 0.48 W m^-1 K^-1 at 823 K. Bi and Ca codoping significantly enhances the Seebeck coefficient and power factor through reducing the energy offset between light and heavy valence bands of GeTe. The modified band structure boosts the power factor up to 47 μW cm^-1 K^-2 in Ge_0.85Bi_0.09Ca_0.06Te. Ultimately, a high ZT of ∼2.2 can be attained. This work demonstrates a new design paradigm for developing high-performance thermoelectric materials.