Theoretical study of the electronic and optical properties of Cu-doped anatase TiO2 using DFT
Abstract
Using density functional theory (GGA-PBE) as implemented in CASTEP, we present a first-principles study of Cu-doped anatase TiO2. Changes in electronic structure and optical response were investigated using a primitive unit cell model with one Ti atom replaced by Cu (at about 5% of doping). Our calculations show that the corresponding charge-density isosurfaces show strong localization around the dopant site, and that Cu incorporation introduces well-defined impurity states around mid-gap, arising mostly due to Cu-3d orbitals. An examination of the complex dielectric function shows that the transitions involving the Cu-induced mid-gap levels are responsible for the noticeable redshift of the optical absorption edge. By extending its photoresponse into the visible spectrum, Cu doping may significantly improve the photocatalytic performance of anatase TiO2, according to this visible-light activation.
About the Authors
List of references
Akira Fujishima and Kenichi Honda. Electrochemical photolysis of water at a semiconductor electrode. nature, 238(5358):37–38, 1972.
Stefano Lettieri, Michele Pavone, Ambra Fioravanti, Luigi Santamaria Amato, and Pasqualino Maddalena. Charge carrier processes and optical properties in tio2 and tio2-based heterojunction photocatalysts: A review. Materials, 14(7):1645, 2021.
Brian O’regan and Michael Gr¨atzel. A low-cost, high-efficiency solar cell based on dye-sensitized colloidal tio2 films. nature, 353(6346):737–740, 1991.
Xiaobo Chen and Samuel S Mao. Titanium dioxide nanomaterials: synthesis, properties, modifications, and applications. Chemical reviews, 107(7):2891–2959, 2007.
Yaqin Wang, Ruirui Zhang, Jianbao Li, Liangliang Li, and Shiwei Lin. First-principles study on transition metal-doped anatase tio2. Nanoscale research letters, 9(1):46, 2014.
Biswajit Choudhury, Munmun Dey, and Amarjyoti Choudhury. Defect generation, d-d transition, and band gap reduction in cu-doped tio2 nanoparticles. International Nano Letters, 3(1):25, 2013.
Javier Navas, Antonio S´anchez-Coronilla, Teresa Aguilar, Norge C Hern´andez, Desire´e M de los Santos, Jes´us S´anchez-M´arquez, David Zorrilla, Concha Fern´andez-Lorenzo, Rodrigo Alc´antara, and Joaqu´ın Mart´ın-Calleja. Experimental and theoretical study of the electronic properties of cu-doped anatase tio 2. Physical Chemistry Chemical Physics, 16(8):3835–3845, 2014.
Abdullah M Alotaibi, Benjamin AD Williamson, Sanjayan Sathasivam, Andreas Kafizas, Mahdi Alqahtani, Carlos Sotelo-Vazquez, John Buckeridge, Jiang Wu, Sean P Nair, David O Scanlon, et al. Enhanced photocatalytic and antibacterial ability of cu-doped anatase tio2 thin films: theory and experiment. ACS applied materials interfaces, 12(13):15348–15361, 2020.
M Ikram, E Umar, A Raza, A Haider, S Naz, d A Ul-Hamid, J Haider, I Shahzadi, J Hassan, and S Ali. Dye degradation performance, bactericidal behavior and molecular docking analysis of cu-doped tio2 nanoparticles. RSC advances, 10(41):24215–24233, 2020.
Meili Guo and Jiulin Du. First-principles study of electronic structures and optical properties of cu, ag, and au-doped anatase tio2. Physica B: Condensed Matter, 407(6):1003–1007, 2012.
MD Segall, Philip JD Lindan, MJ al Probert, Christopher James Pickard, Philip James Hasnip, SJ Clark, and MC Payne. First-principles simulation: ideas, illustrations and the castepcode. Journal of physics: condensed matter, 14(11):2717, 2002.
John P Perdew and Alex Zunger. Self-interaction correction to density-functional approximations for many-electron systems. Physical review B, 23(10):5048, 1981.
John P Perdew. Generalized gradient approximation made simple. Phys. Rev. Lett., 77:3868, 1997.
R Asahi, Y Taga, W Mannstadt, and Arthur J Freeman. Electronic and optical properties of anatase tio 2. Physical Review B, 61(11):7459, 2000.
oshio Nosaka and Atsuko Y Nosaka. Reconsideration of intrinsic band alignments within anatase and rutile tio2, 2016.
R Jaiswal, J Bharambe, N Patel, Alpa Dashora, DC Kothari, and Antonio Miotello. Copper and nitrogen co-doped tio2 photocatalyst with enhanced optical absorption and catalytic activity. Applied Catalysis B: Environmental, 168:333–341, 2015.
Paruchai Pongwan, Khatcharin Wetchakun, Sukon Phanichphant, and Natda Wetchakun. Enhancement of visible-light photocatalytic activity of cu-doped tio2 nanoparticles. Research on Chemical Intermediates, 42(4):2815–2830, 2016.
Vanaraj Solanki, Shalik Ram Joshi, Indrani Mishra, D Kanjilal, and Shikha Varma. Formation of anisotropic nanostructures on rutile tio2 (110) surfaces and their photo-absorption properties. Metallurgi- cal and materials transactions A, 49(7):3117–3121, 2018.
This work is licensed under a Creative Commons Attribution 4.0 International License.