Rationally optimized carrier effective mass and carrier density leads to high average ZT value in n-type PbSe

Among the intricately coupled thermoelectric parameters, carrier effective mass (m*) and carrier density (n) are two key parameters to determine the electrical transport properties. To enhance the broad-temperature thermoelectric performance in n-type PbSe, this work elaborately optimizes its power factor with the intrinsically proportional relationship between carrier effective mass and carrier density, n ∼ (m*)3/2. Herein, the carrier effective mass in n-type PbSe is first optimized with Sn alloying and undergoes a decrease from ∼0.34me in PbSe to ∼0.25me in Pb0.77Sn0.23Se because of band sharpening. This reduced carrier effective mass contributes to an obvious enhancement of carrier mobility, thereby boosting the maximum power factor from ∼16.8 μW cm−1 K−2 in PbSe to ∼20.5 μW cm−1 K−2 in Pb0.85Sn0.15Se. Moreover, to match the reduced carrier effective mass in n-type Pb0.85Sn0.15Se, its carrier density is well tuned with Ag counter doping, which further facilitates a high average power factor in the whole working temperature range. The average power factor in Pb0.85Sn0.15Se systems increases from ∼15.6 μW cm−1 K−2 with a carrier density of ∼6.21 × 1019 cm−3 to ∼17.6 μW cm−1 K−2 with a carrier density of ∼2.12 × 1019 cm−3 at 300–873 K. Finally, an average ZT (ZTave) of ∼0.95 is achieved in the n-type Pb0.85Sn0.15Se sample at 300–873 K, and the sample outperforms most other n-type PbSe-based thermoelectric materials.