Raman scattering from PbTiO3 thin films prepared on silicon substrates by radio frequency sputtering and thermal treatment

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Abstract
Raman scattering has been carried out on PbTiO3 thin films prepared on platinum-coated (100) silicon by radio-frequency (rf)-magnetron sputtering without substrate heating and a post-deposition thermal treatment. The Raman spectra obtained from the thin film are characteristic of powder Raman spectra: In comparison with the single crystal spectra, the intensity of the background is relatively high at low frequencies and the Raman lines are broad. The lattice phonon modes corresponding to the observed lines are identified by comparison with the data on single crystals and powder. The Raman frequencies for the thin film remarkably shift to low frequencies compared with single-crystal data. It is shown that the phenomenon of the frequency shifts is similar with the hydrostatic pressure effect on single crystals of PbTiO3. The result indicates that the thin films are composed of grains that are stressed depending on the grain size by neighboring grains of different orientations when they are split up into ferroelectric domains at the paraelectric-to-ferroelectric transition. This stress effect is significant even for a grain size of ∼0.5 μm. It is found that the lowest frequency E transverse optical (TO) mode in the thin film shows softening with increasing temperature as was reported in previous studies on single crystals.