Defect and solvent engineering of optoelectronic response in 2D materials: A DFT study on graphene, silicon carbide, and boron nitride for solar cell sensitizers

In the present investigation, the geometrical, electronic, photovoltaic parameters, and optical properties of graphene (G), silicon carbide (SiC), and boron nitride (BN) nanostructures were studied using density functional theory (DFT) and time-dependent DFT (TD-DFT) methods. Dimethyl sulfoxide (DMS...

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Main Authors: Mohammed A. Al-Seady, Lina Abd Oun AL-Jamal, Eman Ahmed, Mousumi Upadhyay Kahaly
Format: Article
Language:English
Published: Elsevier 2025-08-01
Series:Results in Physics
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Online Access:http://www.sciencedirect.com/science/article/pii/S221137972500213X
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author Mohammed A. Al-Seady
Lina Abd Oun AL-Jamal
Eman Ahmed
Mousumi Upadhyay Kahaly
author_facet Mohammed A. Al-Seady
Lina Abd Oun AL-Jamal
Eman Ahmed
Mousumi Upadhyay Kahaly
author_sort Mohammed A. Al-Seady
collection DOAJ
description In the present investigation, the geometrical, electronic, photovoltaic parameters, and optical properties of graphene (G), silicon carbide (SiC), and boron nitride (BN) nanostructures were studied using density functional theory (DFT) and time-dependent DFT (TD-DFT) methods. Dimethyl sulfoxide (DMSO) solvent was utilized to enhance the properties of the nanostructures under investigation. Solar cell parameters such as the free energy of electron injection (ΔGInj.), regeneration (ΔGReg.), open-circuit voltage (VOC), and light-harvesting efficiency (LHE) were calculated. The results of the photovoltaic parameters indicated that G, SiC, and BN have a high ability to inject electrons into the conduction band minimum (CBM) of titanium dioxide (TiO2) semiconductor. DFT calculations revealed that the HOMO energy levels of the G and SiC nanostructures were localized above the iodine/tri-iodide (I/I3-) electrolyte, which prevents electrons from regenerating in the ground state. While pristine h-BN exhibits a wide band gap (>6 eV) that limits its utility as a solar sensitizer, our findings reveal that introducing structural defects such as double vacancies or substitutional doping (e.g., h-BN–C) significantly reduces the band gap to values as low as ∼2.0 eV. This band gap narrowing enhances the material’s ability to absorb visible light and participate in photoinduced charge transfer. Molecular orbital analyses show that the LUMO levels of all defected nanostructures (except h-BN–C in isolated form) lie above the conduction band minimum (CBM) of TiO2, enabling efficient electron injection. Furthermore, in the dissolved phase, the HOMO levels of SiC and BN nanostructures shift below the I−/I3− redox potential, supporting ground-state electron regeneration. TD-DFT results demonstrate pronounced redshift in the UV–Vis absorption spectra of defected and solvated nanostructures, especially for BN-based systems, indicating improved light-harvesting. Overall, this study establishes that through defect engineering and solvent modulation, the optoelectronic performance of 2D materials such as graphene, SiC, and BN can be significantly enhanced, and that defected BN derivatives, once considered unsuitable, emerge as viable sensitizer candidates.
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spelling doaj-art-959132c0dfe04afa8983f6af876e79ba2025-08-20T03:02:26ZengElsevierResults in Physics2211-37972025-08-017510831910.1016/j.rinp.2025.108319Defect and solvent engineering of optoelectronic response in 2D materials: A DFT study on graphene, silicon carbide, and boron nitride for solar cell sensitizersMohammed A. Al-Seady0Lina Abd Oun AL-Jamal1Eman Ahmed2Mousumi Upadhyay Kahaly3Department of Theoretical Physics, University of Szeged, Tisza Lajos krt. 84-86, Szeged 6720, Hungary; Environmental Research and Studies Center, University of Babylon, Babylon, Iraq; Corresponding authors.Department of Physics, College of Education for Pure Sciences, University of Babylon, Babylon, IraqDepartment of Physics, College of Education for Pure Sciences, University of Babylon, Babylon, IraqDepartment of Theoretical Physics, University of Szeged, Tisza Lajos krt. 84-86, Szeged 6720, Hungary; ELI-ALPS, ELI-HU Non-Profit Ltd., Wolfgang Sandner Utca 3, Szeged, Hungary; Corresponding authors.In the present investigation, the geometrical, electronic, photovoltaic parameters, and optical properties of graphene (G), silicon carbide (SiC), and boron nitride (BN) nanostructures were studied using density functional theory (DFT) and time-dependent DFT (TD-DFT) methods. Dimethyl sulfoxide (DMSO) solvent was utilized to enhance the properties of the nanostructures under investigation. Solar cell parameters such as the free energy of electron injection (ΔGInj.), regeneration (ΔGReg.), open-circuit voltage (VOC), and light-harvesting efficiency (LHE) were calculated. The results of the photovoltaic parameters indicated that G, SiC, and BN have a high ability to inject electrons into the conduction band minimum (CBM) of titanium dioxide (TiO2) semiconductor. DFT calculations revealed that the HOMO energy levels of the G and SiC nanostructures were localized above the iodine/tri-iodide (I/I3-) electrolyte, which prevents electrons from regenerating in the ground state. While pristine h-BN exhibits a wide band gap (>6 eV) that limits its utility as a solar sensitizer, our findings reveal that introducing structural defects such as double vacancies or substitutional doping (e.g., h-BN–C) significantly reduces the band gap to values as low as ∼2.0 eV. This band gap narrowing enhances the material’s ability to absorb visible light and participate in photoinduced charge transfer. Molecular orbital analyses show that the LUMO levels of all defected nanostructures (except h-BN–C in isolated form) lie above the conduction band minimum (CBM) of TiO2, enabling efficient electron injection. Furthermore, in the dissolved phase, the HOMO levels of SiC and BN nanostructures shift below the I−/I3− redox potential, supporting ground-state electron regeneration. TD-DFT results demonstrate pronounced redshift in the UV–Vis absorption spectra of defected and solvated nanostructures, especially for BN-based systems, indicating improved light-harvesting. Overall, this study establishes that through defect engineering and solvent modulation, the optoelectronic performance of 2D materials such as graphene, SiC, and BN can be significantly enhanced, and that defected BN derivatives, once considered unsuitable, emerge as viable sensitizer candidates.http://www.sciencedirect.com/science/article/pii/S221137972500213XGrapheneSilicon-carbideBoron-nitrideDFTDSSCs
spellingShingle Mohammed A. Al-Seady
Lina Abd Oun AL-Jamal
Eman Ahmed
Mousumi Upadhyay Kahaly
Defect and solvent engineering of optoelectronic response in 2D materials: A DFT study on graphene, silicon carbide, and boron nitride for solar cell sensitizers
Results in Physics
Graphene
Silicon-carbide
Boron-nitride
DFT
DSSCs
title Defect and solvent engineering of optoelectronic response in 2D materials: A DFT study on graphene, silicon carbide, and boron nitride for solar cell sensitizers
title_full Defect and solvent engineering of optoelectronic response in 2D materials: A DFT study on graphene, silicon carbide, and boron nitride for solar cell sensitizers
title_fullStr Defect and solvent engineering of optoelectronic response in 2D materials: A DFT study on graphene, silicon carbide, and boron nitride for solar cell sensitizers
title_full_unstemmed Defect and solvent engineering of optoelectronic response in 2D materials: A DFT study on graphene, silicon carbide, and boron nitride for solar cell sensitizers
title_short Defect and solvent engineering of optoelectronic response in 2D materials: A DFT study on graphene, silicon carbide, and boron nitride for solar cell sensitizers
title_sort defect and solvent engineering of optoelectronic response in 2d materials a dft study on graphene silicon carbide and boron nitride for solar cell sensitizers
topic Graphene
Silicon-carbide
Boron-nitride
DFT
DSSCs
url http://www.sciencedirect.com/science/article/pii/S221137972500213X
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