Chemical doping is one of the major methods by which the properties of BaTiO3 are modified to induce various device characteristics. Doping strategies are generally separated into iso- and alio-valent (donors and acceptors) and into A- and B-site species within the perovskite structure. The A1g octahedral breathing mode at ∼800 cm−1 in BaTiO3 is Raman inactive for compositions with single B-site species. However, this mode becomes Raman active if more than one B-site species is present, including titanium vacancies, VT′′′′. Moreover, the relative intensity of the A1g breathing mode is qualitatively related to the concentration of the species replacing Ti in the B-site. This article illustrates some clear cases where the A1g octahedral breathing mode can be utilized to verify the site occupancy of dopants in BaTiO3 when used in conjunction with more conventional indirect methods such as x-ray diffraction (Vegard’s Law) and dielectric measurements as a function of temperature.

The Ba(Ti1−xZrx)O3 (BTZ) system with x≤0.35 has been studied using a combination of x-ray diffraction, dielectric measurements, Raman spectroscopy, and electron diffraction with a view to better understand the changes in structure and correlation length of polar order as a function of composition and temperature. Careful fitting of Raman spectra has confirmed stabilization of the orthorhombic phase at room temperature in x=0.05 with mixed phase (orthorhombic and rhombohedral) present at 80 K. Raman data suggest that the rhombohedral phase is most likely to be present at low temperature for x=0.15 and 0.25 and that only short range polar order evolves in x=0.35. Interpretation of the Raman spectra is in broad agreement with the dielectric data as a function of composition and temperature. Diffuse scatter at room temperature in high order zone axis electron diffraction remains essentially identical for all compositions irrespective of structure and correlation length of polar order. The diffuse maxima are therefore considered not to relate directly to the correlation length of polar order in the BTZ system and therefore do not contribute to the dielectric behavior.

Raman spectroscopy has been used to study the ferroelectric tetragonal to paraelectric cubic phase transition Tc in undoped BaTiO3 (BT) and (Ba0.92A0.08)TiO3 [where A=Ca (BCT), Sr (BST), and Pb (BPT)]. In BT and BPT, mode characteristic of the tetragonal phase at 303 and 710cm−1 persisted until >50°C above Tc, indicating the presence of local dynamic polar clusters well above the displacive phase transitions, ∼120 and ∼149°C, respectively. However, in BCT and BST, the Raman spectra exhibited only broad second order bands above Tc, suggesting that Ca and Sr, A-site dopants supress local dynamic polar clusters.

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