Direct evidence of the existence of Mn3+ ions in MnTiO3

We investigate the room temperature electronic properties of MnTiO3 synthesised by different preparation conditions. For this purpose, we prepared MnTiO3 under two different cooling rates, one is naturally cooled while the other is quenched in liq.nitrogen. The samples were studied using optical absorbance, photoemission spectroscopy and band structure calculations.We observe significant changes in the structural parameters as a result of quenching. Interestingly, in the parent compound, our combined core level, valence band and optical absorbance studies show the evidence of Mn existing in both 2+ and 3+ states. The fraction of Mn3+ ions has been found to increase on quenching. The increase in the fraction of the Mn3+ ions has been manifested (a) as slight enhancement in the intensity of the optical absorbance in the visible region.There occurs persistent photo-resistance when the incident light is terminated after shining; (b) in the behaviour of the features (close to fermi level) in the valence band spectra. Hence, the combined analysis of the core level, valence band and optical absorbance spectra suggest the charge carriers are hole like which further leads to the increase in the electrical conductivity of the quenched sample. The present results provide recipe to tune the optical absorption in the visible range for its applications in optical sensors, solar cell, etc.