| 1. |
- Ahmed, Shahbaz, et al.
(författare)
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Accurate First-Principles Evaluation of Structural, Electronic, Optical and Photocatalytic Properties of BaHfO3 and SrHfO3 Perovskites
- 2022
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Ingår i: Journal of Alloys and Compounds. - : Elsevier. - 0925-8388 .- 1873-4669. ; 892
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Tidskriftsartikel (refereegranskat)abstract
- A reliable first-principles account of experimentally observed physical properties of perovskite oxides is crucial for realizing their employment in electronic and optical devices. In this context, SCAN meta-GGA functional of DFT offers good approximation for the exchange-correlation energy; facilitating accurate determination of structural and energetic properties. However, SCAN is unable to reproduce electronic and optical properties of wide bad gap materials. In the present study, we report systematic DFT calculations to show that structural, energetic, electronic and optical properties of hafnium based BaHfO3 and SrHfO3 perovskite oxides can be accurately determined through a combine application of SCAN and Tran-Blaha modified Becke-Johnson (TB-mBJ) meta-GGAs. The structural and energetic properties computed using SCAN functional for both BaHfO3 and SrHfO3 are found to be in good agreement with experimental data; achieving a level of accuracy comparable to computationally expansive hybrid DFT calculations. On the other hand, TB-mBJ calculated band gaps computed using the SCAN optimized lattice parameters provide better agreement with experimental data at a low computational cost. The optical properties, band edge potentials and effective masses of the charge carriers in BaHfO3 and SrHfO3 are also computed to examine the combined application of SCAN and TB-mBJ meta-GGAs in predicting the photocatalytic performance of these wide band gap materials. Our results clearly show that the combination of the two meta-GGAs provide a computationally economical route for evaluating the photocatalytic performance of alkaline-earth metal hafnates.
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| 2. |
- Alay-e-Abbas, Syed Muhammad, 1983-, et al.
(författare)
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Structure inversion asymmetry enhanced electronic structure and electrical transport in 2D A3SnO (A = Ca, Sr, and Ba) anti-perovskite monolayers
- 2023
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Ingår i: Nano Reseach. - : Springer Nature. - 1998-0124 .- 1998-0000. ; 16:1, s. 1779-1791
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Tidskriftsartikel (refereegranskat)abstract
- Anti-perovskites A3SnO (A = Ca, Sr, and Ba) are an important class of materials due to the emergence of Dirac cones and tiny mass gaps in their band structures originating from an intricate interplay of crystal symmetry, spin-orbit coupling, and band overlap. This provides an exciting playground for modulating their electronic properties in the two-dimensional (2D) limit. Herein, we employ first-principles density functional theory (DFT) calculations by combining dispersion-corrected SCAN + rVV10 and mBJ functionals for a comprehensive side-by-side comparison of the structural, thermodynamic, dynamical, mechanical, electronic, and thermoelectric properties of bulk and monolayer (one unit cell thick) A3SnO anti-perovskites. Our results show that 2D monolayers derived from bulk A3SnO anti-perovskites are structurally and energetically stable. Moreover, Rashba-type splitting in the electronic structure of Ca3SnO and Sr3SnO monolayers is observed owing to strong spin-orbit coupling and inversion asymmetry. On the other hand, monolayer Ba3SnO exhibits Dirac cone at the high-symmetry Γ point due to the domination of band overlap. Based on the predicted electronic transport properties, it is shown that inversion asymmetry plays an essential character such that the monolayers Ca3SnO and Sr3SnO outperform thermoelectric performance of their bulk counterparts.
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| 3. |
- Batool, Javaria, et al.
(författare)
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Oxygen-vacancy-induced magnetism in anti-perovskite topological Dirac semimetal Ba3SnO
- 2021
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 23:43, s. 24878-24891
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Tidskriftsartikel (refereegranskat)abstract
- The thermodynamic, structural, magnetic and electronic properties of the pristine and intrinsic vacancy-defect-containing topological Dirac semimetal Ba3SnO are studied using first-principles density functional theory calculations. The thermodynamic stability of Ba3SnO has been evaluated with reference to its competing binary phases Ba2Sn, BaSn and BaO. Subsequently, valid limits of the atomic chemical potentials derived from the thermodynamic stability were used for assessing the formation of Ba, Sn and O vacancy defects in Ba3SnO under different synthesis environments. Based on the calculated defect-formation energies, we find that the charge-neutral oxygen vacancies are the most favourable type of vacancy defect under most chemical environments. The calculated electronic properties of pristine Ba3SnO show that inclusion of spin–orbit coupling in exchange–correlation potentials computed using generalized gradient approximation yields a semimetallic band structure exhibiting twin Dirac cones along the Γ–X path of the Brillouin zone. The effect of spin–polarization and spin–orbit coupling on the physical properties of intrinsic vacancy defects containing Ba3SnO has been examined in detail. Using Bader charges, electron localization function (ELF), electronic density of states (DOS) and spin density, we show that the isolated oxygen vacancy is a magnetic defect in anti-perovskite Ba3SnO. Our results show that the origin of magnetism in Ba3SnO is the accumulation of unpaired charges at the oxygen vacancy sites, which couple strongly with the 5d states of the Ba atom. Owing to the metastability observed in earlier theoretically predicted magnetic topological semimetals, the present study reveals the important role of intrinsic vacancy defects in giving rise to magnetism and also provides opportunities for engineering the electronic structure of a Dirac semimetal.
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| 4. |
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| 5. |
- Zulfiqar, Waqas, et al.
(författare)
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Improved Thermodynamic Stability and Visible Light Absorption in Zr+X Codoped (X = S, Se and Te) BaTiO3 Photocatalysts: A First-Principles Study
- 2022
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Ingår i: Materials Today Communications. - : Elsevier. - 2352-4928. ; 32
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Tidskriftsartikel (refereegranskat)abstract
- Band gap tuning of titanium based perovskite oxides through chalcogen doping is an attractive avenue for realizing visible light driven photocatalysis for hydrogen production. Unfortunately, accommodating a chalcogen atom at an O-site of BaTiO3 is thermodynamically challenging owing to large differences in the atomic radii and electronegativities of oxygen and chalcogen atoms. In the present study we employ first-principles density functional theory calculations to examine the influence of Zr codoping on the structural, thermodynamic, opto-electronic properties and photocatalytic performance of X-doped (X = S, Se and Te) BaTiO3 systems. The atomic structure and energetic properties are computed using SCAN meta-GGA functional of density functional theory, while the electronic and optical properties are computed using the TB-mBJ meta-GGA potential functional. Within the valid limits of the atomic chemical potentials, we find that chalcogen doping in BaTiO3 lattice would be experimentally difficult despite a clear reduction in the electronic band gap of this system useful for application in visible light driven photocatalysis. In order to improve the synthesis feasibility of X-doped BaTiO3 under oxygen-rich as well as oxygen-poor chemical environments, we propose Zr as a codopant at a Ti-site in X-doped BaTiO3 which improves the thermodynamic stability and also retains the reduction in the electronic band gap of BaTiO3 caused by the presence of chalcogen atom. Our results suggest that Zr+X (X = S, Se and Te) codoped BaTiO3 offers great opportunities as a practical photocatalysts for hydrogen production through overall splitting of the water molecule.
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| 6. |
- Zulfiqar, Waqas, et al.
(författare)
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Revisiting the structural, electronic and photocatalytic properties of Ti and Zr based perovskites with meta-GGA functionals of DFT
- 2021
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Ingår i: Journal of Materials Chemistry C. - UK : Royal Society of Chemistry. - 2050-7526 .- 2050-7534. ; 9:14, s. 4862-4876
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Tidskriftsartikel (refereegranskat)abstract
- The strongly constrained and appropriately normed (SCAN) functional of density functional theory (DFT) conforms to all possible exact constraints required of a meta-GGA functional and offers good approximations for structural and energetic properties of solids in comparison to experiments. However, SCAN is unable to fully overcome the underestimation of band gap for perovskite oxide materials suitable for photocatalysis. In the present work, we use a combination of meta-GGAs SCAN and modified Becke–Johnson local density approximation (mBJ-LDA) potential functional to accurately compute the structural, energetic, mechanical, vibrational and optoelectronic properties of Ti and Zr based ABO3 (A = Sr, Ba and B = Ti and Zr) perovskite oxides. In addition to evaluating their physical properties, the potential applications of these materials as photocatalyst operating in the UV region of the electromagnetic spectrum are also examined. We show that the structural, energetic, mechanical and vibrational properties calculated using SCAN are in better agreement with experimental data as compared to the commonly used semi-local functionals of DFT. However, the optoelectronic properties of the large band gap Ti and Zr based perovskite oxides are further improved if computed with the mBJ-LDA potential functional, whereby an even higher level of accuracy than with SCAN is achieved, with results that are comparable to the computationally expensive hybrid DFT functionals. On the whole, our DFT calculations indicate that a combination of SCAN and mBJ-LDA functionals for exploring the physical properties of large band gap perovskite oxides provide the means for identifying photocatalysts suitable for hydrogen production at low computational costs.
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| 7. |
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