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

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Abstract

Atomically thin black phosphorus, also known as phosphorene, is an emerging two-dimensional (2D) material, which has attracted increasing attention due to its unique electronic and optoelectronic properties. However, the reduced thermal stability of phosphorene limits its suitability for high-temperature fabrication processes, which could be detrimental for the performance of phosphorenebased devices. Here, we investigate the impact of doping by Al and Hf transition metal adatoms on the thermal stability of phosphorene. The formation of Al–P covalent bonds was found to significantly improve the thermal coefficients of the A 1g , B2g, and A 2g 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 for pristine P–P bonds (~0.01 cm–1·°C–1). First-principles calculations within the density functional theory framework reveal that the observed thermal stability enhancement in the Al-doped material reflects a significantly higher Al binding energy, due to the stronger Al–P bonds compared to the weak van der Waals interactions between adjacent P atoms in the undoped material. The present work thus paves the way towards phosphorene materials with improved structural stability, which could be promising candidates for potential nanoelectronic and optoelectronic applications.

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Authors and Affiliations

  1. Department of Electrical and Computer Engineering, National University of Singapore, 4 Engineering Drive 3, Singapore, 117583, Singapore

    Xuewei Feng & Kah-Wee Ang

  2. Entropic Interface Group (EIG), Engineering Product Development, Singapore University of Technology and Design (SUTD), 8 Somapah Road, Singapore, 487372, Singapore

    Vadym V. Kulish & Ping Wu

  3. College of Materials Science and Engineering, Shenzhen Engineering Laboratory for Advanced Technology of Ceramics, Nanshan District Key Lab for Biopolymer and Safety Evaluation, Shenzhen University, 3688 Nanhai Avenue, Shenzhen, 518060, China

    Xinke Liu

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  1. Xuewei Feng
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  2. Vadym V. Kulish
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Correspondence to Kah-Wee Ang.

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Feng, X., Kulish, V.V., Wu, P. et al. Anomalously enhanced thermal stability of phosphorene via metal adatom doping: An experimental and first-principles study. Nano Res. 9, 2687–2695 (2016). https://doi.org/10.1007/s12274-016-1156-0

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