Band Modification and Localized Lattice Engineering Leads to High Thermoelectric Performance in Ge and Bi Codoped SnTe-AgBiTe2 Alloys.

SnTe, emerging as an environment-friendly alternative to conventional PbTe thermoelectrics, has drawn significant attention for clean energy conversion. Here, a high peak figure of merit (ZT) of 1.45 at 873 K in Ge/Bi codoped SnTe-AgBiTe2 alloys is reported. It is demonstrated that the existence of Ge, Bi, and Ag facilitate band convergence in SnTe, resulting in remarkable enhancement of Seebeck coefficient and power factor. Simultaneously, localized lattice imperfections including dislocations, point defects, and micro/nanopore structures are caused by incorporation of Ge, Bi, and Ag, which can effectively scatter heat carrying phonons with different wavelengths and contribute to an extremely low κL of 0.61 W m-1  K-1 in Sn0.92 Ge0.04 Bi0.04 Te-10%AgBiTe2 . Such high peak ZT is achieved by decouples electron and phonon transport through band modification and localized lattice engineering, highlighting promising solutions for advancing thermoelectrics.

Enhanced Density of States Facilitates High Thermoelectric Performance in Solution-Grown Ge- and In-Codoped SnSe Nanoplates.

SnSe single crystals have gained great interest due to their excellent thermoelectric performance. However, polycrystalline SnSe is greatly desired due to facile processing, machinability, and scale-up application. Here, we report an outstanding high average ZT of 0.88 as well as a high peak ZT of 1.92 in solution-processed SnSe nanoplates. Nanosized boundaries formed by nanoplates and lattice strain created by lattice dislocations and stacking faults effectively scatter heat-carrying phonons, resulting in an ultralow lattice thermal conductivity of 0.19 W m-1 K-1 at 873 K. Ultraviolet photoelectron spectroscopy reveals that Ge and In incorporation produces an enhanced density of states in the electronic structure of SnSe, resulting in a large Seebeck coefficient. Ge and In codoping not only optimizes the Seebeck coefficient but also substantially increases the carrier concentration and electrical conductivity, helping to maintain a high power factor over a wide temperature range. Benefiting from an enhanced power factor and markedly reduced lattice thermal conductivity, high average ZT and peak ZT are achieved in Ge- and In-codoped SnSe nanoplates. This work achieves an ultrahigh average ZT of 0.88 in polycrystalline SnSe by adopting nontoxic element doping, potentially expanding its usefulness for various thermoelectric generator applications.

Realizing High Thermoelectric Performance in p-Type SnSe Crystals via Convergence of Multiple Electronic Valence Bands.

SnSe crystals have gained considerable interest for their outstanding thermoelectric performance. Here, we achieve excellent thermoelectric properties in Sn0.99-xPbxZn0.01Se crystals via valence band convergence and point-defect engineering strategies. We demonstrate that Pb and Zn codoping converges the energy offset between multiple valence bands by significantly modifying the band structure, contributing to the enhancement of the Seebeck coefficient. The carrier concentration and electrical conductivity can be optimized, leading to an enhanced power factor. The dual-atom point-defect effect created by the substitution of Pb and Zn in the SnSe lattice introduces strong phonon scattering, significantly reducing the lattice thermal conductivity to as low as 0.284 W m-1 K-1. As a result, a maximum ZT value of 1.9 at 773 K is achieved in Sn0.93Pb0.06Zn0.01Se crystals along the bc-plane direction. This study highlights the crucial role of manipulating multiple electronic valence bands in further improving SnSe thermoelectrics.

Achieving Ultralow Lattice Thermal Conductivity and High Thermoelectric Performance in GeTe Alloys via Introducing Cu2Te Nanocrystals and Resonant Level Doping.

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.