Enhanced Thermoelectric Performance in Black Phosphorus Nanotubes by Band Modulation through Tailoring Nanotube Chirality

Abstract Black phosphorus (BP) has attracted great attention for applications in thermoelectric devices, owing to its unique in‐plane anisotropic electrical and thermal properties. However, its limited conversion efficiency hinders practical application. Here, the thermoelectric properties of 1D BP nanotubes (BPNTs) with different tube chirality are investigated using first‐principles calculations and Boltzmann transport theory. The results reveal that variation of crystallographic orientation has a distinct impact on band dispersions, which provides a wide tunability of electronic transport. It is shown that (1,1)‐oriented BPNT structure can yield an order‐of‐magnitude enhanced thermoelectric figure of merit ZT at room temperature (as high as 1.0), compared with the bulk counterpart. The distinct enhancement is attributed to the favorable multiple band structures that lead to high carrier mobility of 2430 cm² V⁻¹ s⁻¹. Further performance improvement can be realized by suitable doping, such as N‐alloying, reaching an increase of room‐temperature ZT by a factor of 3 over that of pristine BPNT. The work provides an applicable method to achieve band engineering design, and presents a new strategy of designing 1D BPNT that are promising candidates for flexible, eco‐friendly, and high‐performance thermoelectrics.