Structural, Electronic, and Mechanical Properties of Anatase and Rutile Titanium Dioxide Phases using the Density Functional Theory
Received: 14 July 2024 | Revised: 30 July 2024 and 4 August 2024 | Accepted: 11 August 2024 | Online: 17 August 2024
Corresponding author: Omer I. Eid
Abstract
This study investigates the structural and electronic properties of the anatase and rutile TiO2 systems by employing the Quantum Espresso (QE) software using first-principles calculations based on Density Functional Theory (DFT). Optimized lattice constants (a = 3.788, 4.627 a.u. and c = 9.491, 2.979 a.u.) and the internal parameter u (0.209, 0.305), were obtained for anatase and rutile TiO2 phases, respectively. Unit cell volumes were also calculated. Furthermore, the Birch-Murnaghan equation of state was used to obtain the equilibrium volume (937.5, 428.3 a.u.3), the bulk modulus (198.5, 222.5 GPa), and the pressure derivative of the bulk modulus (4.18, 4.37) for both phases. The results are in good agreement with the experimental data and the theoretical results published in other studies. Finally, the energy band gap of both samples was calculated (1.8 and 1.6 eV, respectively) and compared with published results obtained from the Density Of Electron States (DOS).
Keywords:
titanium dioxide, anatase, rutile, DFT, electronic structure, bulk modulus, energy band gapDownloads
References
T. Ji et al., "Effect of Grain Size on Electrical Properties of Anatase TiO2 under High Pressure," The Journal of Physical Chemistry C, vol. 125, no. 6, pp. 3314–3319, Feb. 2021.
J. Reintjes and M. B. Schulz, "Photoelastic Constants of Selected Ultrasonic Delay‐Line Crystals," Journal of Applied Physics, vol. 39, no. 11, pp. 5254–5258, Oct. 1968.
W. Göpel et al., "Surface defects of TiO2(110): A combined XPS, XAES AND ELS study," Surface Science, vol. 139, no. 2, pp. 333–346, Apr. 1984.
A. F. Carley, P. R. Chalker, J. C. Riviere, and M. W. Roberts, "The identification and characterisation of mixed oxidation states at oxidised titanium surfaces by analysis of X-ray photoelectron spectra," Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, vol. 83, no. 2, pp. 351–370, Jan. 1987.
B. W. Veal and A. P. Paulikas, "Final-state screening and chemical shifts in photoelectron spectroscopy," Physical Review B, vol. 31, no. 8, pp. 5399–5416, Apr. 1985.
R. Brydson, H. Sauer, W. Engel, and F. Hofer, "Electron energy-loss near-edge structures at the oxygen K edges of titanium(IV) oxygen compounds," Journal of Physics: Condensed Matter, vol. 4, no. 13, Nov. 1992, Art. no. 3429.
K. M. Glassford and J. R. Chelikowsky, "Electronic structure of TiO2:Ru," Physical Review B, vol. 47, no. 19, pp. 12550–12553, May 1993.
D. Vogtenhuber, R. Podloucky, A. Neckel, S. G. Steinemann, and A. J. Freeman, "Electronic structure and relaxed geometry of the TiO2 rutile (110) surface," Physical Review B, vol. 49, no. 3, pp. 2099–2103, Jan. 1994.
A. Fahmi, C. Minot, B. Silvi, and M. Causá, "Theoretical analysis of the structures of titanium dioxide crystals," Physical Review B, vol. 47, no. 18, pp. 11717–11724, May 1993.
D. Aroussi, B. Aour, and A. S. Bouaziz, "A Comparative Study of 316L Stainless Steel and a Titanium Alloy in an Aggressive Biological Medium," Engineering, Technology & Applied Science Research, vol. 9, no. 6, pp. 5093–5098, Dec. 2019.
A. Boudjemline, M. Boujelbene, and E. Bayraktar, "Surface Quality of Ti-6Al-4V Titanium Alloy Parts Machined by Laser Cutting," Engineering, Technology & Applied Science Research, vol. 10, no. 4, pp. 6062–6067, Aug. 2020.
V. C. Nguyen, T. D. Nguyen, and D. H. Tien, "Cutting Parameter Optimization in Finishing Milling of Ti-6Al-4V Titanium Alloy under MQL Condition using TOPSIS and ANOVA Analysis," Engineering, Technology & Applied Science Research, vol. 11, no. 1, pp. 6775–6780, Feb. 2021.
L. Madani, K. S. Belkhir, and S. Belkhiat, "Experimental Study of Electric and Dielectric Behavior of PVC Composites," Engineering, Technology & Applied Science Research, vol. 10, no. 1, pp. 5233–5236, Feb. 2020.
T. Gegechkori, G. Mamniashvili, T. Gagnidze, M. Nadareishvili, and T. Zedginidze, "Photocatalytic and Magnetic Properties of TiO2 Micro- and Nano- Powders decorated by Magnetic Cocatalysts," Engineering, Technology & Applied Science Research, vol. 13, no. 5, pp. 11924–11931, Oct. 2023.
M. Oproescu, A. G. Schiopu, V. M. Calinescu, V. G. Iana, N. Bizon, and M. Sallah, "Influence of Supplementary Oxide Layer on Solar Cell Performance," Engineering, Technology & Applied Science Research, vol. 14, no. 2, pp. 13274–13282, Apr. 2024.
D. Dash, C. K. Pandey, S. Chaudhary, and S. K. Tripathy, "Structural, electronic, and mechanical properties of anatase titanium dioxide: An ab-initio approach," Multidiscipline Modeling in Materials and Structures, vol. 15, no. 2, pp. 306–316, Jan. 2018.
T. Mahmood et al., "Pressure Induced Structural and Electronic Bandgap properties of Anatase and Rutile TiO2," Sains Malaysiana, vol. 42, no. 2, pp. 231–237, 2013.
W. Zhang, T. Hu, B. Yang, P. Sun, and H. He, "The Effect of Boron Content on Properties of B-TiO2 Photocatalyst Prepared by Sol-gel Method," Journal of Advanced Oxidation Technologies, vol. 16, no. 2, pp. 261–267, Jul. 2013.
D. G. Isaak, J. D. Carnes, O. L. Anderson, H. Cynn, and E. Hake, "Elasticity of TiO2 rutile to 1800 K," Physics and Chemistry of Minerals, vol. 26, no. 1, pp. 31–43, Nov. 1998.
P. Giannozzi et al., "QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials," Journal of Physics: Condensed Matter, vol. 21, no. 39, Jun. 2009, Art. no. 395502.
P. Giannozzi et al., "Quantum ESPRESSO toward the exascale," The Journal of Chemical Physics, vol. 152, no. 15, Apr. 2020, Art. no. 154105.
"Pseudopotentials," Quantum Espresso. https://www.quantum-espresso.org/pseudopotentials/.
T. Iliass, H. Ziani, A. Gueddim, and A. D. Guibadj, "DFT Investigation of the Structual and Optoelectronic Properties of Alkali Metal Hydrides MH (M=Li, Na)," Engineering, Technology & Applied Science Research, vol. 12, no. 1, pp. 8151–8156, Feb. 2022.
H. J. Monkhorst and J. D. Pack, "Special points for Brillouin-zone integrations," Physical Review B, vol. 13, no. 12, pp. 5188–5192, Jun. 1976.
A. Kokalj, "XCrySDen-a new program for displaying crystalline structures and electron densities," Journal of Molecular Graphics and Modelling, vol. 17, no. 3, pp. 176–179, Jun. 1999.
R. Asahi, Y. Taga, W. Mannstadt, and A. J. Freeman, "Electronic and optical properties of anatase TiO2," Physical Review B, vol. 61, no. 11, pp. 7459–7465, Mar. 2000.
J. K. Burdett, T. Hughbanks, G. J. Miller, J. W. Jr. Richardson, and J. V. Smith, "Structural-electronic relationships in inorganic solids: powder neutron diffraction studies of the rutile and anatase polymorphs of titanium dioxide at 15 and 295 K," Journal of the American Chemical Society, vol. 109, no. 12, pp. 3639–3646, Jun. 1987.
F. D. Murnaghan, "The Compressibility of Media under Extreme Pressures," Proceedings of the National Academy of Sciences, vol. 30, no. 9, pp. 244–247, Sep. 1944.
T. Arlt et al., "High-pressure polymorphs of anatase TiO2," Physical Review B, vol. 61, no. 21, pp. 14414–14419, Jun. 2000.
W. J. Yin, S. Chen, J. H. Yang, X. G. Gong, Y. Yan, and S. H. Wei, "Effective band gap narrowing of anatase TiO2 by strain along a soft crystal direction," Applied Physics Letters, vol. 96, no. 22, Jun. 2010, Art. no. 221901.
I. Erdem and H. H. Kart, "Density functional theory study of tin and titanium dioxides: Structural and mechanical properties in the tetragonal rutile phase," Materials Science in Semiconductor Processing, vol. 28, pp. 59–65, Dec. 2014.
D. O. Scanlon et al., "Band alignment of rutile and anatase TiO2," Nature Materials, vol. 12, no. 9, pp. 798–801, Sep. 2013.
A. Jain et al., "A high-throughput infrastructure for density functional theory calculations," Computational Materials Science, vol. 50, no. 8, pp. 2295–2310, Jun. 2011.
A. Jain et al., "Formation enthalpies by mixing GGA and GGA +U calculations," Physical Review B, vol. 84, no. 4, Jul. 2011, Art. no. 045115.
P. Borlido, J. Schmidt, A. W. Huran, F. Tran, M. A. L. Marques, and S. Botti, "Exchange-correlation functionals for band gaps of solids: benchmark, reparametrization and machine learning," npj Computational Materials, vol. 6, no. 1, Jul. 2020, Art. no. 96.
V. P. Zhukov and E. V. Chulkov, "Ab initio approach to the excited electron dynamics in rutile and anatase TiO2," Journal of Physics: Condensed Matter, vol. 22, no. 43, Jul. 2010, Art. no. 435802.
S. D. Mo and W. Y. Ching, "Electronic and optical properties of three phases of titanium dioxide: Rutile, anatase, and brookite," Physical Review B, vol. 51, no. 19, pp. 13023–13032, May 1995.
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