Cation Distribution and Structural Instability in Pr-Doped Bi₄Ti₃O₁₂

Pr-doped bismuth titanate (BixPryTi3O12: BPT) thin films with random orientation were fabricated on Pt/Ti/SiO2/Si substrates by rf magnetron sputtering technique, and the structures and Raman spectra of the films were investigated. XRD studies indicated that all of the BPT films consist of single phase of a bismuth-layered structure, showing a highly (117) oriented preferential growth with a minor fraction of (00l) orientation. For an increasing degree of Pr doping, Raman spectra studies revealed a substantial hardening of the vibration involving Bi atoms at the perovskite A site, whereas the Bi mode at the Bi2O2 layer is negligibly changed. From a comparison with a simple mass consideration, we identify a precise cation distribution, indicating a pronounced site selectivity of Pr ions for the A site for y ~ 1.2.