Docente
UFABC
Jeverson T. Arantes
Publicações
2024
Portugal, Guilherme Ribeiro; Arantes, Jeverson Teodoro
Dimensionality and strain-dependent properties of Orthorhombic (100) NaTaO3 thin films: A comprehensive DFT investigation Journal Article
Em: Computational Materials Science, vol. 245, 2024, ISSN: 0927-0256.
@article{Portugal2024,
title = {Dimensionality and strain-dependent properties of Orthorhombic (100) NaTaO3 thin films: A comprehensive DFT investigation},
author = {Guilherme Ribeiro Portugal and Jeverson Teodoro Arantes},
url = {https://www.sciencedirect.com/science/article/pii/S0927025624005561},
doi = {10.1016/j.commatsci.2024.113335},
issn = {0927-0256},
year = {2024},
date = {2024-10-01},
journal = {Computational Materials Science},
volume = {245},
publisher = {Elsevier BV},
abstract = {The modulation of perovskite oxide thin films’ properties, through both intrinsic and extrinsic methods, has been extensively studied to enhance their photocatalytic performance. We employed ab initio density functional theory calculations to investigate the layer-dependent structural and electronic properties of orthorhombic NaTaO
thin films. Our findings reveal that slabs comprising five, four, and three layers retain the non-magnetic and semiconducting characteristics of the bulk material, with their properties progressively converging towards those of an infinite-surface slab as the number of layers increases. Biaxial in-plane strain induces a linear change in the structure of surface TaO
tetrahedra, thereby altering the film’s band gap. Notably, the two-layer slab exhibits a transitional behavior between the bulk-like nature of thicker films and the unique features of a NaTaO
monolayer, showing heightened sensitivity to strain. Under compression, this bilayered system acquires bulk-like properties, whereas its strain-free state is magnetic and metallic akin to the monolayer. Similar transitions are observed in the latter, though under higher compression values. We provide an in-depth discussion of the structural and electronic mechanisms underlying these transitions. Additionally, the relative band-edge alignment with water-splitting photocatalytic potentials underscores the complex interplay between strain and dimensionality. This work offers valuable insights towards the design of more efficient photocatalysts, highlighting the potential of engineered NaTaO
thin-film structures for advancing photocatalytic applications.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The modulation of perovskite oxide thin films’ properties, through both intrinsic and extrinsic methods, has been extensively studied to enhance their photocatalytic performance. We employed ab initio density functional theory calculations to investigate the layer-dependent structural and electronic properties of orthorhombic NaTaO
thin films. Our findings reveal that slabs comprising five, four, and three layers retain the non-magnetic and semiconducting characteristics of the bulk material, with their properties progressively converging towards those of an infinite-surface slab as the number of layers increases. Biaxial in-plane strain induces a linear change in the structure of surface TaO
tetrahedra, thereby altering the film’s band gap. Notably, the two-layer slab exhibits a transitional behavior between the bulk-like nature of thicker films and the unique features of a NaTaO
monolayer, showing heightened sensitivity to strain. Under compression, this bilayered system acquires bulk-like properties, whereas its strain-free state is magnetic and metallic akin to the monolayer. Similar transitions are observed in the latter, though under higher compression values. We provide an in-depth discussion of the structural and electronic mechanisms underlying these transitions. Additionally, the relative band-edge alignment with water-splitting photocatalytic potentials underscores the complex interplay between strain and dimensionality. This work offers valuable insights towards the design of more efficient photocatalysts, highlighting the potential of engineered NaTaO
thin-film structures for advancing photocatalytic applications.
thin films. Our findings reveal that slabs comprising five, four, and three layers retain the non-magnetic and semiconducting characteristics of the bulk material, with their properties progressively converging towards those of an infinite-surface slab as the number of layers increases. Biaxial in-plane strain induces a linear change in the structure of surface TaO
tetrahedra, thereby altering the film’s band gap. Notably, the two-layer slab exhibits a transitional behavior between the bulk-like nature of thicker films and the unique features of a NaTaO
monolayer, showing heightened sensitivity to strain. Under compression, this bilayered system acquires bulk-like properties, whereas its strain-free state is magnetic and metallic akin to the monolayer. Similar transitions are observed in the latter, though under higher compression values. We provide an in-depth discussion of the structural and electronic mechanisms underlying these transitions. Additionally, the relative band-edge alignment with water-splitting photocatalytic potentials underscores the complex interplay between strain and dimensionality. This work offers valuable insights towards the design of more efficient photocatalysts, highlighting the potential of engineered NaTaO
thin-film structures for advancing photocatalytic applications.
2023
Portugal, Guilherme Ribeiro; Arantes, Jeverson Teodoro
Polar NaTaO3/LaAlO3 (001) superlattices: A comparison of PBEsol and PBEsol+U first-principles calculations Journal Article
Em: Computational Materials Science, vol. 233, pp. 112747, 2023, ISSN: 0927-0256.
@article{PORTUGAL2024112747,
title = {Polar NaTaO3/LaAlO3 (001) superlattices: A comparison of PBEsol and PBEsol+U first-principles calculations},
author = {Guilherme Ribeiro Portugal and Jeverson Teodoro Arantes},
url = {https://www.sciencedirect.com/science/article/pii/S0927025623007413},
doi = {https://doi.org/10.1016/j.commatsci.2023.112747},
issn = {0927-0256},
year = {2023},
date = {2023-12-21},
urldate = {2024-01-01},
journal = {Computational Materials Science},
volume = {233},
pages = {112747},
abstract = {The increasing experimental and theoretical interest in two-dimensional charge carrier gases formed at the interfaces of heterostructured perovskite oxide systems has led to a demand for a deeper understanding regarding the influence of exchange–correlation functionals and associated corrections on the systems’ properties. Herein, we investigate the impact of implementing additive Hubbard corrections compared to standard DFT routines using the PBEsol functional in polar NaTaO3/LaAlO3 (001) superlattices. Structural analysis reveals that the qualitative assessment remains consistent regardless of the approach, with slight variations observed for the NaTaO3 phase due to more pronounced polar distortions. Electronically, standard PBEsol fails to accurately describe the electronic structure of the superlattice below the system’s critical thickness, whereas the inclusion of on-site Coulomb interactions through PBEsol+U routines provides the correct semiconductor character of the superlattice, emphasizing the role of strong correlation effects on d and f electrons at the material’s interface. Additionally, our investigation reveals the spatial charge separation in the semiconductor heterostructure, with potential implications for photocatalytic devices. This work not only contributes to demonstrate the importance of the chosen methodology when studying such systems but also sheds light on important electronic and structural properties of NaTaO3/LaAlO3 (001) superlattices, enabling new avenues for future applications.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The increasing experimental and theoretical interest in two-dimensional charge carrier gases formed at the interfaces of heterostructured perovskite oxide systems has led to a demand for a deeper understanding regarding the influence of exchange–correlation functionals and associated corrections on the systems’ properties. Herein, we investigate the impact of implementing additive Hubbard corrections compared to standard DFT routines using the PBEsol functional in polar NaTaO3/LaAlO3 (001) superlattices. Structural analysis reveals that the qualitative assessment remains consistent regardless of the approach, with slight variations observed for the NaTaO3 phase due to more pronounced polar distortions. Electronically, standard PBEsol fails to accurately describe the electronic structure of the superlattice below the system’s critical thickness, whereas the inclusion of on-site Coulomb interactions through PBEsol+U routines provides the correct semiconductor character of the superlattice, emphasizing the role of strong correlation effects on d and f electrons at the material’s interface. Additionally, our investigation reveals the spatial charge separation in the semiconductor heterostructure, with potential implications for photocatalytic devices. This work not only contributes to demonstrate the importance of the chosen methodology when studying such systems but also sheds light on important electronic and structural properties of NaTaO3/LaAlO3 (001) superlattices, enabling new avenues for future applications.
Portugal, Guilherme Ribeiro; Ronchi, Rodrigo Mantovani; Santos, Sydney Ferreira; Arantes, Jeverson Teodoro
Composition-dependent photocatalytic activity and high-mobility carrier gas in NaTaO3/BaBiO3 heterojunctions Journal Article
Em: Surfaces and Interfaces, vol. 36, pp. 102486, 2023, ISSN: 2468-0230.
@article{PORTUGAL2023102486,
title = {Composition-dependent photocatalytic activity and high-mobility carrier gas in NaTaO3/BaBiO3 heterojunctions},
author = {Guilherme Ribeiro Portugal and Rodrigo Mantovani Ronchi and Sydney Ferreira Santos and Jeverson Teodoro Arantes},
url = {https://www.sciencedirect.com/science/article/pii/S2468023022007453},
doi = {https://doi.org/10.1016/j.surfin.2022.102486},
issn = {2468-0230},
year = {2023},
date = {2023-01-01},
journal = {Surfaces and Interfaces},
volume = {36},
pages = {102486},
abstract = {Perovskite oxide heterostructures have been extensively investigated for their excellent nanoelectronics and photocatalytic properties. Herein, the general features of monoclinic (001) NaTaO3/BaBiO3 heterojunctions are theoretically investigated, exploring how the interface creation affects their physicochemical properties. Density functional theory results reveal that a superlattice with 24 wt.% of BaBiO3 displays a typically desired electronic structure for photocatalytic reactions, with an intermediate band gap and highly dispersive energy levels. Hybrid functional calculations provide a band gap of 1.85 eV, with optical absorption peaks inside the visible light spectrum and band-edge potentials better aligned with water splitting levels when compared with the pristine NaTaO3 phase. Upon increasing the number of BaBiO3 layers a semiconductor-to-metal transition is observed and described based on electrostatic and polarization arguments, leading to the formation of a high-mobility two-dimensional electron gas (2DEG) at the interface. The presented results highlight the importance of such nanojunctions not only for photocatalytic but also for nanoelectronics applications.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Perovskite oxide heterostructures have been extensively investigated for their excellent nanoelectronics and photocatalytic properties. Herein, the general features of monoclinic (001) NaTaO3/BaBiO3 heterojunctions are theoretically investigated, exploring how the interface creation affects their physicochemical properties. Density functional theory results reveal that a superlattice with 24 wt.% of BaBiO3 displays a typically desired electronic structure for photocatalytic reactions, with an intermediate band gap and highly dispersive energy levels. Hybrid functional calculations provide a band gap of 1.85 eV, with optical absorption peaks inside the visible light spectrum and band-edge potentials better aligned with water splitting levels when compared with the pristine NaTaO3 phase. Upon increasing the number of BaBiO3 layers a semiconductor-to-metal transition is observed and described based on electrostatic and polarization arguments, leading to the formation of a high-mobility two-dimensional electron gas (2DEG) at the interface. The presented results highlight the importance of such nanojunctions not only for photocatalytic but also for nanoelectronics applications.
Portugal, Guilherme Ribeiro; Arantes, Jeverson Teodoro
Hybrid Functional-Based Scissors Operator for Perovskite Oxide Nanostructures: A NaTaO3 Case Study Journal Article
Em: The Journal of Physical Chemistry C, vol. 127, não 11, pp. 5604-5612, 2023.
@article{doi:10.1021/acs.jpcc.2c08986,
title = {Hybrid Functional-Based Scissors Operator for Perovskite Oxide Nanostructures: A NaTaO3 Case Study},
author = {Guilherme Ribeiro Portugal and Jeverson Teodoro Arantes},
url = {https://doi.org/10.1021/acs.jpcc.2c08986},
doi = {10.1021/acs.jpcc.2c08986},
year = {2023},
date = {2023-01-01},
journal = {The Journal of Physical Chemistry C},
volume = {127},
number = {11},
pages = {5604-5612},
abstract = {Accurately predicting the bandgap as well as valence and conduction band positions through theoretical methods is crucial when investigating perovskite oxide nanostructures for a range of applications. Owing mainly to the high computational cost of state-of-the-art electronic structure techniques, using bulk-based scissors operator corrections has become a popular approach. Nonetheless, rigorous analysis concerning its accuracy is of fundamental importance, especially when intrinsic defect states are observed. Through range-separated hybrid functional calculations within the density functional theory framework, the effectiveness of bulk-based scissors operators in correcting both band-edge positions and the bandgap of different NaTaO3 orthorhombic nanostructures has been systematically investigated. Moreover, four distinct approaches were implemented in order to deal with surface-related defect states. The subsequent alignment of each nanostructure’s band-edges with water-splitting photocatalytic potentials shows the consistency of bulk-based scissors operators and the importance of a rational method to coherently tackle intrinsic defect levels.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Accurately predicting the bandgap as well as valence and conduction band positions through theoretical methods is crucial when investigating perovskite oxide nanostructures for a range of applications. Owing mainly to the high computational cost of state-of-the-art electronic structure techniques, using bulk-based scissors operator corrections has become a popular approach. Nonetheless, rigorous analysis concerning its accuracy is of fundamental importance, especially when intrinsic defect states are observed. Through range-separated hybrid functional calculations within the density functional theory framework, the effectiveness of bulk-based scissors operators in correcting both band-edge positions and the bandgap of different NaTaO3 orthorhombic nanostructures has been systematically investigated. Moreover, four distinct approaches were implemented in order to deal with surface-related defect states. The subsequent alignment of each nanostructure’s band-edges with water-splitting photocatalytic potentials shows the consistency of bulk-based scissors operators and the importance of a rational method to coherently tackle intrinsic defect levels.