Experimental and ab initio infrared study of χ-, κ- and α-aluminas formed from gibbsite

χ-, κ- and α-alumina phases formed by dehydration of micro-grained gibbsite between 773 and 1573 K are studied using infrared spectroscopy (IR). The structural transitions evidenced by X-ray diffraction (XRD) were interpreted by comparing IR measurements with ab initio simulations (except for the χ form whose complexity does not allow a reliable simulation). For each phase, IR spectrum presents specific bands corresponding to transverse optical (TO) modes of Al-O stretching and bending under 900 cm-1. The very complex χ phase, obtained at 773 K, provides a distinctive XRD pattern in contrast with the IR absorbance appearing as a broad structure extending between 200 and 900 cm-1 resembling the equivalent spectra for γ-alumina phase. κ-alumina is forming at 1173 K and its rich IR spectrum is in good qualitative agreement with ab initio simulations. This complexity reflects the large number of atoms in the κ-alumina unit cell and the wide range of internuclear distances as well as the various coordinances of both Al and O atoms. Ab initio simulations suggest that this form of transition alumina demonstrates a strong departure from the simple pattern observed for other transition alumina. At 1573 K, the stable α-Αl2Ο3 develops. Its IR spectra extends in a narrower energy range as compared to transition alumina and presents characteristics features similar to model α-Αl2Ο3{dot operator} Ab initio calculations show again a very good general agreement with the observed IR spectra for this phase. In addition, for both κ- and α-Αl2Ο3, extra modes, measured at high energy (above 790 cm-1 for κ and above 650 cm-1 for α), can originate from either remnant χ-alumina or from surface mode

Room-temperature soft mode and ferroelectric like polarization in SrTiO3 ultrathin films: Infrared and ab initio study

International audienceDue to the remarkable possibilities of epitaxially growing strontium titanate (SrTiO 3 or STO) on silicon, this oxide is widely used as a buffer layer for integrating other perovskite oxides which allows for the development of various functional electronic devices on silicon. Moreover, STO is known to be an incipient ferroelectric in bulk but may become ferroelectric when in the form of strained ultrathin films. Given the importance of the potential applications for electronics if this property is demonstrated, we performed a spectroscopic study of STO on Si(001) templates coupling experimental and ab initio investigations. We selected six samples of ultrathin films: three strained samples (of thickness 4, 9 and 48 nm) and three relaxed samples (of equivalent thickness). Their infrared spectra show that both the mechanical stress and the thickness play major roles: higher energy modes evolve as soft modes in thinner strained films. In order to support these observations, the dynamical ab initio calculations allowed deriving the conditions for STO films to become ferroelectric at room temperature as shown by the development of a soft mode and the divergence of the in-plane dielectric constant