Conceptualization of Doped Black P Thin Films for Potential Use in Photovoltaics with Validation from First Principle Calculations

Black Phosphorus was recently discovered as a 2D material and it exemplified huge prospects for application in electronics, optoelectronics, photonics and catalysis. It is a direct band semiconductor with tunable band gap varying from 0.35 eV (bulk) to 2 eV (single layer). But the layer dependent band gap of black phosphorus restricts it to make use of the full spectra of sunlight for absorption. First principle calculations were performed using ‘Quantum Wise Atomistic Toolkit’ package with Perdew-Burke-Ernzerhof (PBE) exchange-correlation for black phosphorus doped with non-metallic dopants of B, S and Se and metallic dopants of Ti, Mg and In. It has been found that doping with non-metallic impurities result in a small diminution of the band edges (0.96–0.57 eV), whereas doping with metallic impurities decrease the band edge drastically (0.85–0.025 eV). Moreover, it was also observed that dopants with an even number of valence electrons incorporated a metallic nature of black phosphorus, whereas dopants with odd number of valence electrons further attributed to its semiconducting features. Thus in a holistic discernment, black phosphorus with the incorporation of some dopants in appropriate amounts can absorb more visible range of the optical spectra, making it ideal for use in photovoltaics.