RESUMEN
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 κL 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 κL 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 Ge0.85Bi0.09Ca0.06Te. Ultimately, a high ZT of â¼2.2 can be attained. This work demonstrates a new design paradigm for developing high-performance thermoelectric materials.
RESUMEN
The binary compound of GeTe emerging as a potential medium-temperature thermoelectric material has drawn a great deal of attention. Here, we achieve ultralow lattice thermal conductivity and high thermoelectric performance in In and a heavy content of Cu codoped GeTe thermoelectrics. In dopants improve the density of state near the surface of Femi of GeTe by introducing resonant levels, producing a sharp increase of the Seebeck coefficient. In and Cu codoping not only optimizes carrier concentration but also substantially increases carrier mobility to a high value of 87 cm2 V-1 s-1 due to the diminution of Ge vacancies. The enhanced Seebeck coefficient coupled with dramatically enhanced carrier mobility results in significant enhancement of PF in Ge1.04-x-yInxCuyTe series. Moreover, we introduce Cu2Te nanocrystals' secondary phase into GeTe by alloying a heavy content of Cu. Cu2Te nanocrystals and a high density of dislocations cause strong phonon scattering, significantly diminishing lattice thermal conductivity. The lattice thermal conductivity reduced as low as 0.31 W m-1 K-1 at 823 K, which is not only lower than the amorphous limit of GeTe but also competitive with those of thermoelectric materials with strong lattice anharmonicity or complex crystal structures. Consequently, a high ZT of 2.0 was achieved for Ge0.9In0.015Cu0.125Te by decoupling electron and phonon transport of GeTe. This work highlights the importance of phonon engineering in advancing high-performance GeTe thermoelectrics.
