Ultrahigh Average ZT Realized in p‑Type SnSe Crystalline Thermoelectrics through Producing Extrinsic Vacancies

Crystalline SnSe has been revealed as an efficient thermoelectric candidate with outstanding performance. Herein, record-high thermoelectric performance is achieved among SnSe crystals via simply introducing a small amount of SnSe₂ as a kind of extrinsic defect dopant. This excellent performance mainly arises from the largely enhanced power factor by increasing the carrier concentration high as 6.55 × 10¹⁹ cm^–3, which was surprisingly promoted by introducing extrinsic SnSe₂ even though pristine SnSe₂ is an n-type conductor. The optimized carrier concentration promotes a deeper Fermi level and activates more valence bands, leading to an extraordinary room-temperature power factor ∼54 μW cm^–1 K^–2 through enlarging the band effective mass and Seebeck coefficient. As a result, on the basis of simultaneously depressed thermal conductivity induced from both Sn vacancies and SnSe₂ microdomains, maximum ZT values ∼0.9–2.2 and excellent average ZT > 1.7 among the working temperature range are achieved in Na doped SnSe crystals with 2% extrinsic SnSe₂. Our investigation illustrates new approaches on improving thermoelectric performance through introducing defect dopants, which might be well-implemented in other thermoelectric systems.