In a systematic study we investigate the effect of dopant level and hydration on the short-range structure of the proton conducting perovskite-type oxide BaInxZr1−xO 3−x/2 (x = 0 − 0.75), using infrared and Raman spectroscopy. The results show that doping leads to significant local distortions of the average cubic structure of these materials. By increasing the In concentration from x = 0 to x = 0.75 new bands appear and grow in intensity in both the IR and Raman spectra, showing that the local distortions become successively more and more pronounced. The structural distortions are largely uncorrelated to the presence of oxygen vacancies, but instead are mainly driven by the size difference between the In 3+ and Zr 4+ ions, which leads to displacements of the cations and to tilting of the (In/Zr)O6 octahedra. Based on our results, we suggest that there is a threshold between x = 0.10 and x = 0.25 where the local structural distortions propagate throughout the whole perovskite structure. Comparison of our spectroscopic data with the proton conductivity reported for the same materials indicates that the presence of extended structural distortions are favorable for fast proton transport.

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