Nano Research

Article Title

Anomalously enhanced thermal stability of phosphorene via metal adatom doping: An experimental and first-principles study


phosphorene, black phosphorus, adatom doping, transition metals, thermal stability


Atomically thin black phosphorus, also known as phosphorene, is an emergingtwo-dimensional (2D) material, which has attracted increasing attention due toits unique electronic and optoelectronic properties. However, the reduced thermalstability of phosphorene limits its suitability for high-temperature fabricationprocesses, which could be detrimental for the performance of phosphorenebaseddevices. Here, we investigate the impact of doping by Al and Hf transitionmetal adatoms on the thermal stability of phosphorene. The formation of Al–Pcovalent bonds was found to significantly improve the thermal coefficients ofthe A1g, B2g, and A2g phonon modes to 0.00044, 0.00081, and 0.00012 cm–1·°C–1,respectively, which are two orders of magnitude lower than those observed forpristine P–P bonds (~0.01 cm–1·°C–1). First-principles calculations within thedensity functional theory framework reveal that the observed thermal stabilityenhancement in the Al-doped material reflects a significantly higher Al bindingenergy, due to the stronger Al–P bonds compared to the weak van der Waalsinteractions between adjacent P atoms in the undoped material. The present workthus paves the way towards phosphorene materials with improved structuralstability, which could be promising candidates for potential nanoelectronic andoptoelectronic applications.

Graphical Abstract


Tsinghua University Press