SnSe doped a different way: Heat can be converted into electricity by thermoelectric materials. Such materials are promising for use in solid-state cooling devices. A challenge for developing efficient thermoelectric materials is to ensure high electrical but low thermal conductivity. Chang et al. found that bromine doping of tin selenide (SnSe) does just this by maintaining low thermal conductivity in the out-of-plane direction of this layered material. The result is a promising n-type thermoelectric material with electrons as the charge carriers—an important step for developing thermoelectric devices from SnSe. Science , this issue p. 778

Thermoelectric materials allow for direct conversion between heat and electricity, offering the potential for power generation. The average dimensionless figure of merit ZT _ave determines device efficiency. N-type tin selenide crystals exhibit outstanding three-dimensional charge and two-dimensional phonon transport along the out-of-plane direction, contributing to a high maximum figure of merit Z _max of ~3.6 × 10 ⁻³ per kelvin but a moderate ZT _ave of ~1.1. We found an attractive high Z _max of ~4.1 × 10 ⁻³ per kelvin at 748 kelvin and a ZT _ave of ~1.7 at 300 to 773 kelvin in chlorine-doped and lead-alloyed tin selenide crystals by phonon-electron decoupling. The chlorine-induced low deformation potential improved the carrier mobility. The lead-induced mass and strain fluctuations reduced the lattice thermal conductivity. Phonon-electron decoupling plays a critical role to achieve high-performance thermoelectrics.

Thermoelectrics have been limited by the scarcity of their constituent elements, especially telluride. The earth-abundant, wide-bandgap ( E _g ≈ 46 k _B T ) tin sulfide (SnS) has shown promising performance in its crystal form. We improved the thermoelectric efficiency in SnS crystals by promoting the convergence of energy and momentum of four valance bands, termed quadruple-band synglisis. We introduced more Sn vacancies to activate quadruple-band synglisis and facilitate carrier transport by inducing SnS ₂ in selenium (Se)–alloyed SnS, leading to a high dimensionless figure of merit ( ZT ) of ~1.0 at 300 kelvin and an average ZT of ~1.3 at 300 to 773 kelvin in p-type SnS crystals. We further obtained an experimental efficiency of ~6.5%, and our fabricated cooler demonstrated a maximum cooling temperature difference of ~48.4 kelvin at 353 kelvin. Our observations should draw interest to earth-abundant SnS crystals for applications of waste-heat recovery and thermoelectric cooling.

SnSe has emerged as one of the most promising materials for thermoelectric energy conversion due to its extraordinary performance in its single-crystal form and its low-cost constituent elements. However, to achieve an economic impact, the polycrystalline counterpart needs to replicate the performance of the single crystal. Herein, we optimize the thermoelectric performance of polycrystalline SnSe produced by consolidating solution-processed and surface-engineered SnSe particles. In particular, the SnSe particles are coated with CdSe molecular complexes that crystallize during the sintering process, forming CdSe nanoparticles. The presence of CdSe nanoparticles inhibits SnSe grain growth during the consolidation step due to Zener pinning, yielding a material with a high density of grain boundaries. Moreover, the resulting SnSe–CdSe nanocomposites present a large number of defects at different length scales, which significantly reduce the thermal conductivity. The produced SnSe–CdSe nanocomposites exhibit thermoelectric figures of merit up to 2.2 at 786 K, which is among the highest reported for solution-processed SnSe.

High carrier mobility is critical to improving thermoelectric performance over a broad temperature range. However, traditional doping inevitably deteriorates carrier mobility. Herein, we develop a strategy for fine tuning of defects to improve carrier mobility. To begin, n-type PbTe is created by compensating for the intrinsic Pb vacancy in bare PbTe. Excess Pb²⁺ reduces vacancy scattering, resulting in a high carrier mobility of ∼3400 cm² V^-1 s^-1. Then, excess Ag is introduced to compensate for the remaining intrinsic Pb vacancies. We find that excess Ag exhibits a dynamic doping process with increasing temperatures, increasing both the carrier concentration and carrier mobility throughout a wide temperature range; specifically, an ultrahigh carrier mobility ∼7300 cm² V^-1 s^-1 is obtained for Pb_1.01Te + 0.002Ag at 300 K. Moreover, the dynamic doping-induced high carrier concentration suppresses the bipolar thermal conductivity at high temperatures. The final step is using iodine to optimize the carrier concentration to ∼10¹⁹ cm^-3. Ultimately, a maximum ZT value of ∼1.5 and a large average ZT _ave value of ∼1.0 at 300-773 K are obtained for Pb_1.01Te_0.998I_0.002 + 0.002Ag. These findings demonstrate that fine tuning of defects with <0.5% impurities can remarkably enhance carrier mobility and improve thermoelectric performance.