Dispelling the Myth of Passivated Codoping in TiO2

Journal article

Williamson, B.A.D., Buckeridge, J., Chadwick, N.P., Sathasivam, S., Carmalt, C.J., Parkin, I.P. and Scanlon, D.O. (2019). Dispelling the Myth of Passivated Codoping in TiO2. Chemistry of Materials. 31, pp. 2577-2589. https://doi.org/10.1021/acs.chemmater.9b00257
AuthorsWilliamson, B.A.D., Buckeridge, J., Chadwick, N.P., Sathasivam, S., Carmalt, C.J., Parkin, I.P. and Scanlon, D.O.
Abstract

Modification of TiO2 to increase its visible light activity and promote higher performance photocatalytic ability has become a key research goal for materials scientists in the past 2 decades. One of the most popular approaches proposed this as “passivated codoping”, whereby an equal number of donor and acceptor dopants are introduced into the lattice, producing a charge neutral system with a reduced band gap. Using the archetypal codoping pairs of [Nb + N]- and [Ta + N]-doped anatase, we demonstrate using hybrid density functional theory that passivated codoping is not achievable in TiO2. Our results indicate that the natural defect chemistry of the host system (in this case n-type anatase TiO2) is dominant, and so concentration parity of dopant types is not achievable under any thermodynamic growth conditions. The implications of passivated codoping for band gap manipulation in general are discussed.

Year2019
JournalChemistry of Materials
Journal citation31, pp. 2577-2589
Digital Object Identifier (DOI)https://doi.org/10.1021/acs.chemmater.9b00257
Web address (URL)https://pubs.acs.org/doi/full/10.1021/acs.chemmater.9b00257
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Print17 Mar 2019
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Accepted15 Mar 2019
Deposited22 Oct 2019
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Buckeridge et al. Reply:
Buckeridge, J., Catlow, C. R. A., Scanlon, D. O., Keal, T. W., Sherwood, P., Miskufova, M., Walsh, A., Woodley, S. M. and Sokol, A. A. (2015). Buckeridge et al. Reply: Physical Review Letters. 115 (2), p. 029702. https://doi.org/10.1103/PhysRevLett.115.029702
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