Thermoelectric materials transfer heat and electrical energy, being useful for power generation or cooling applications. Many of these materials have narrow bandgaps, especially for cooling applications where this property has been seen as particularly important for enhancing the thermoelectric properties. We developed SnSe crystals with a wide bandgap Eg ~ 33 kBT with attractive thermoelectric properties through Pb alloying. The momentum and energy multiband alignment promoted by Pb alloying resulted in an ultra-high power factor ~75 μWcm–1K–2 at 300 K, and a ZTave ~ 1.90. We show that a 31-pair thermoelectric device can produce a power generation efficiency ~4.4% and a cooling ΔTmax ~ 45.7 K. These results demonstrate that wide bandgap compounds can be used for thermoelectric cooling applications.

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.

Thermoelectric technology has been widely used for key areas, including waste-heat recovery and solid-state cooling. We discovered tin selenide (SnSe) crystals with potential power generation and Peltier cooling performance. The extensive off-stoichiometric defects have a larger impact on the transport properties of SnSe, which motivated us to develop a lattice plainification strategy for defects engineering. We demonstrated that Cu can fill Sn vacancies to weaken defects scattering and boost carrier mobility, facilitating a power factor exceeding ~100 microwatts per centimeter per square kelvin and a dimensionless figure of merit ( ZT ) of ~1.5 at 300 kelvin, with an average ZT of ~2.2 at 300 to 773 kelvin. We further realized a single-leg efficiency of ~12.2% under a temperature difference (Δ T ) of ~300 kelvin and a seven-pair Peltier cooling Δ T max of ~61.2 kelvin at ambient temperature. Our observations are important for practical applications of SnSe crystals in power generation as well as electronic cooling.

Due to the intrinsically plentiful Sn vacancies, developing n-type SnTe thermoelectric materials is a big challenge. Herein, n-type SnTe thermoelectric materials with remarkable performance were successfully synthesized through suppressing Sn vacancies, followed by electron-doping. Pb alloying notably depressed the Sn vacancies via populating Sn vacancies in SnTe (supported by transmission electron microscopy), and the electrical transports were shifted from p-type to n-type through introducing electrons using I doping. In the n-type SnTe, we found that the electrical conductivity could be enhanced by increased carrier mobility through sharpening conduction bands after alloying Pb, while the lattice thermal conductivity could be reduced via strong phonon scattering after introducing defects by Pb alloying and I doping. Resulting from these enhancements, the n-type Sn0.6Pb0.4Te0.98I0.02 achieves a notably high ZT max ∼ 0.8 at 573 K and a remarkable ZT ave ∼ 0.51 at 300–823 K, which can match many excellent p-type SnTe. This work indicates that n-type SnTe could be experimentally acquired and is a promising candidate for thermoelectric generation, which will stimulate further research on n-type SnTe thermoelectric materials and even devices on the basis of both n- and p-type SnTe legs.

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