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The results of combined experimental and theoretical study of substitutionaland clustering effects in Bi-doped TiO2 hosts (bulk and thin-film morphologies)are presented. Bi-doping of the bulk and thin-film titanium dioxide was madewith help of pulsed ion-implantation (E(Bi+) = 30 keV, D = 1 * 1017 cm-2)without posterior tempering. The X-ray photoelectron spectroscopy (XPS)qualification (core-levels and valence bands) and Density-Functional Theory(DFT) calculations were employed in order to study the electronic structure ofBi-ion implanted TiO2 samples. According to XPS data obtained and DFTcalculations, the Bi -> Ti cation substitution occurs in Bi-implanted bulkTiO2, whereas in the thin-film morphology of TiO2:Bi the Bi-atoms havemetal-like clusters segregation tendency. Based on the combined XPS and DFTconsiderations the possible reasons and mechanism for the observed effects arediscussed. It is believed that established peculiarities of bismuth embeddinginto employed TiO2 hosts are mostly the sequence of pleomorphic origin for theformed "bismuth-oxygen" chemical bonding.

Pleomorphic structural imperfections caused by pulsed Bi-implantation in the bulk and thin-film morphologies of TiO2