Origin of soft-mode stiffening and reduced dielectric response inSrTiO3thin films

The problem of the reduced dielectric response in thin films of high-permittivity materials is analyzed by studying the soft-mode response in several ${\mathrm{SrTiO}}_{3}$ thin films by means of Fourier transform far infrared, monochromatic submillimeter, and micro-Raman spectroscopies. A 300-nm-thick metalorganic chemical vapor deposition film, quasiepitaxially grown on a (0001) sapphire substrate with a perfect 〈111〉 orientation, displays a ferroelectric transition near 125 K induced by a tensile residual stress, appearing apparently simultaneously with the antiferrodistortive transition. On the other hand, polycrystalline chemical solution deposition films grown on (0001) sapphire, and also tensile stressed, show a harder soft mode response without the appearance of macroscopic ferroelectricity. This effect, which increases with the film thickness, is explained by a strong depolarizing field induced by the percolated porosity and cracks (in the 10-nm scale) along the boundaries of columnar grains (normal to the probe field direction). Brick-wall model calculations showed that 0.2 vol. % of such a porosity type reduces the permittivity from 30000 to less than 1000. The activation of the forbidden IR modes in the Raman spectra in the whole 80--300-K temperature range studied is explained by the effect of polar grain boundaries, in analogy with the bulk ceramics.