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Anomalous behavior of B1g
mode in highly transparent anatase nano-crystalline Nb-doped Titanium Dioxide (NTO) thin films
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The effect of Niobiumdoping and size of crystallites on highly transparent nano-crystalline NiobiumdopedTitanium Dioxide (NTO) thin films with stable anatase phase are reported. The Nbdoping concentration is varied within the solubility limit in TiO2 lattice. Films were annealed in controlled environment for improving the crystallinity and size of crystallites. Elemental and thickness analysis were carried out using Rutherford backscattering spectrometry and cross sectional field emission scanning electron microscopy. Structural characteristics reveal a substitutional incorporation of Nb+5 in the TiO2 lattice which inhibits the anatase crystallites growth with increasing the doping percentage. The micro-Raman (MR) spectra of films with small size crystallites shows stiffening of about 4 cm−1 for the Eg(1) mode and is ascribed to phonon confinement and non-stoichiometry. In contrast, B1g mode exhibits a large anomalous softening of 20 cm−1 with asymmetrical broadening; which was not reported for the case of pure TiO2 crystallites. This anomalous behaviour is explained by contraction of the apical Ti-O bonds at the surface upon substitutional Nb5+doping induced reduction of Ti4+ ions also known as hetero-coordination effect. The proposed hypotheses is manifested through studying the electronic structure and phonon dynamics by performing the near edge x-ray absorption fine structure(NEXAFS) and temperature dependent MR down to liquid nitrogen temperature on pure and 2.5 at.% doped NTO films, respectively.
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