Ultrahigh Thermoelectric Performance Realized in Black Phosphorus System by Favorable Band Engineering through Group VA Doping

Black phosphorus (BP) has emerged as a promising thermoelectric candidate because of its strong electronic and thermal anisotropy, suggesting a large σ/κ ratio can be realized by controlling carrier transport orientation for a potentially high ZT. Nevertheless, to date, low conversion efficiency (ZT ≈0.08, 300 K) and poor stability of BP remain the major issues that have hampered its practical applications. This work reports a material family in simple composition XP7, XP3, and XP (X = N, As, Sb, Bi) with high‐performance thermoelectric properties by first‐principles calculations. Strikingly, an ultrahigh ZT up to 1.21 at 300 K is achieved in p‐type BiP7 with an optimal carrier concentration of 5.48 × 1019 cm−3 and ZT in n‐type NP3 can reach up to ≈0.87 at the electron concentration of 3.67 × 1019 cm−3 along the zigzag direction, owing to their enhanced density of states and multivalley band structures around the Fermi level through the resonant effects of VA guest and host atoms. Additionally, the calculations demonstrate further improvement in thermoelectric performance of pristine BP by ≈4.8 and 4.5 times at 800 K in p‐type NP and n‐type NP3, respectively. Considering the high stability, current results indicate that N–P based systems are highly promising for novel metal‐free, nontoxic, and ultralight thermoelectrics. Ultrahigh thermoelectric performance in black phosphorus is predicted through group VA doping by resonant band manipulation. Strikingly, ZT values can reach up to 1.21 and 0.87 at 300 K in p‐type BiP7 and n‐type NP3, respectively. Further significant enhancement is also found in N–P systems at 800 K, indicating promising candidates for nontoxic, metal‐free, and ultralight thermoelectrics.