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In silico modeling: electronic properties of phosphorene monoflakes and biflakes substituted with Al, Si, and S heteroatoms

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Abstract

This contribution explores the systematic substitution of phosphorene monoflakes (Mfs) and biflakes (Bfs) with aluminum, silicon, and sulfur. These systems were investigated using density functional theory employing the TPSS exchange-correlation functional and complete active space self-consistent field (CASSCF) calculations. Al and Si substitution produces significant structural changes in both Mfs and Bfs compared to S-substituted and pristine systems. However, in Mfs, all heteroatoms generate a decrease in band gap and the ionization potentials (IP), and an increase in electron affinity (EA) in comparison with pristine phosphorene. Al doping improves the hole mobility in the phosphorene monoflake, while Si and S substitutions exhibit a similar behavior on EAs and reorganization energies. For Bfs, the presence of Si-Si and Al-P interlaminar interactions causes structural changes and higher binding energies for Si-Bfs and Al-Bfs. Regarding the electronic properties of Bfs, substitution with Si does not produce significant variations in the band gap. Nevertheless, it conduces the formation of hole transport materials, which does not occur in Si-Mfs. The same is observed for Al systems, whereas no correlation was identified between the doping level and reorganization energies for S complexes. The substitution with Al and S leads to an opposite behavior of the band gap and IP values, while the EA variation is similar. In summary, the nature of heteroatom and the doping degree can modify the semiconductor character and electronic properties of phosphorene mono- and biflakes, whose trends are closely related to the atomic properties considered. Overall, these computational calculations provide significant insights into the study of doped phosphorene materials.

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Funding

W.E.V.N. received support from DGAPA of the UNAM under postdoctoral fellowship Grant No. CJIC/CTIC/4732/2O2O. Cesar Gabriel Vera de la Garza received doctoral fellowship grant 859569 from CONACyT. We received financial support from PAPIIT (IN201219/31) and from CONACyT (Grant 251684).

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  1. Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Apartado Postal 70-360, CU, Coyoacán, 04510, México, DF, Mexico

    Cesar Gabriel Vera de la Garza, Luis Daniel Solis Rodriguez, Serguei Fomine & Wilmer E. Vallejo Narváez

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  1. Cesar Gabriel Vera de la Garza
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  2. Luis Daniel Solis Rodriguez
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  3. Serguei Fomine
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  4. Wilmer E. Vallejo Narváez
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All the authors contributed equally to this work, and all agree with the contents of the manuscript.

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Correspondence to Wilmer E. Vallejo Narváez.

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de la Garza, C.G.V., Rodriguez, L.D.S., Fomine, S. et al. In silico modeling: electronic properties of phosphorene monoflakes and biflakes substituted with Al, Si, and S heteroatoms. J Mol Model 27, 171 (2021). https://doi.org/10.1007/s00894-021-04789-y

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  • DOI: https://doi.org/10.1007/s00894-021-04789-y

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