Phosphorus Doping Effects on the Optoelectronic Properties of K₂AgAsBr₆ Double Perovskites for Photovoltaic Applications

Abdelmounaim Laassouli; Lhouceine Moulaoui; Abdelhafid Najim; Hamza Errahoui; Khalid Rahmani; Youssef  Lachtioui; Omar Bajjou Omar Bajjou

doi:10.51646/jsesd.v14iSI_MSMS2E.407

Authors

Abdelmounaim Laassouli Laboratory of Engineering in Chemistry and Physics of Matter (LICPM), Faculty of Sciences and Technics, Sultan Moulay Slimane University, BP 523, 23000 Beni Mellal, Morocco.
Lhouceine Moulaoui Research Laboratory in Physics and Sciences for Engineers (LRPSI), Poly-disciplinary Faculty, Sultan Moulay Slimane University, BP 592, 23000 Beni Mellal, Morocco.
Abdelhafid Najim Research Laboratory in Physics and Sciences for Engineers (LRPSI), Poly-disciplinary Faculty, Sultan Moulay Slimane University, BP 592, 23000 Beni Mellal, Morocco.
Hamza Errahoui Research Laboratory in Physics and Sciences for Engineers (LRPSI), Poly-disciplinary Faculty, Sultan Moulay Slimane University, BP 592, 23000 Beni Mellal, Morocco.
Khalid Rahmani PSES, ERC, Ecole Normale Supérieure, Mohammed V University in Rabat P. O. Box: BP5118 Takkadoum Rabat-10000, Morocco.
Youssef Lachtioui PSES, ERC, Ecole Normale Supérieure, Mohammed V University in Rabat P. O. Box: BP5118 Takkadoum Rabat-10000, Morocco.
Omar Bajjou UNESCO UNISA Africa Chair in Nanosciences & Nanotechnology (U2ACN2), College of Graduate Studies, University of South Africa (UNISA), Pretoria, South Africa.

DOI:

https://doi.org/10.51646/jsesd.v14iSI_MSMS2E.407

Keywords:

Double perovskites, phosphorus doping, photoelectric devices, DFT calculations, band gap.

Abstract

This work explores the modifications of optoelectronic properties in K₂AgAsBr₆ double perovskites induced by phosphorus doping. First-principles calculations using the CASTEP code with the PBE functional were carried out based on density functional theory (DFT). Our research investigates the electronic structure and optical behavior of the cubic Fm-3m phase of K₂AgAsBr₆, K₂AgAs₀.₈P₀.₂Br₆, and K₂AgAs₀.₆P₀.₄Br₆ to elucidate the impact of progressive phosphorus (P) substitution. P was chosen for its potential to modify the electronic structure due to its smaller atomic radius and different valence orbital energies compared to As. Our results reveal a systematic narrowing of the band gap with increasing P content, from 0.749 eV for the undoped compound to 0.587 eV for K₂AgAs₀.₈P₀.₂Br₆ and 0.424 eV for K₂AgAs₀.₆P₀.₄Br₆. This trend is attributed to the upward shift of the valence band maximum due to the higher energy of P 3p orbitals compared to As 4p orbitals. Analysis of the density of states confirms increased hybridization between P-p and As-p states at the valence band edge. Optical properties, including absorption coefficient, dielectric function, refractive index, and extinction coefficient, demonstrate a consistent red-shift and broadening of spectral features with P doping. Notably, P-substituted compounds exhibit enhanced absorption in the visible light region, with up to a 20% increase in the absorption coefficient at 550 nm for K₂AgAs₀.₆P₀.₄Br₆ compared to the undoped compound. This study reveals that elemental substitution offers a viable route to tailor optical and electronic properties of double perovskites, paving the way for the design of novel materials for next-generation photovoltaic and photoelectric devices.

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