Inconsistencies in the Electronic Properties of Phosphorene Nanotubes: New Insights from Large-Scale DFT Calculations

TL;DR

This study reveals that phosphorene nanotubes exhibit a complex, size-dependent transition from direct to indirect band gaps, resolving previous conflicting reports through large-scale DFT calculations and detailed orbital analysis.

Contribution

The paper demonstrates a universal direct-to-indirect bandgap transition in phosphorene nanotubes as diameter decreases, clarifying prior inconsistent findings.

Findings

All nanotubes show a direct-to-indirect bandgap transition with decreasing diameter.

Large-scale DFT calculations confirm the transition across multiple exchange-correlation functionals.

The transition is caused by strain-induced orbital interactions.

Abstract

Contrary to recent reports, we show that the electronic properties of phosphorene nanotubes are surprisingly rich and much more complex than previously assumed. We find that all phosphorene nanotubes exhibit an intricate direct-to-indirect bandgap transition as the nanotube diameter decreases - a unique property not identified in any prior studies (which claimed either direct or indirect band gaps only) that we uncover with large-scale DFT calculations. We address these previous inconsistencies by detailed analyses of orbital interactions, which reveal that the strain associated with decreasing the nanotube diameter causes a transition from a direct to an indirect band gap for all of the phosphorene nanotubes. We show that our findings are completely general, and extensive calculations across several exchange-correlation functionals verify our conclusions. Most importantly, our results and analyses resolve a long-standing question on the electronic properties of phosphorus nanotubes and brings closure to previously conflicting findings in these unique nanostructures.