Structural changes in the homologous series of the Aurivillius phases Bin+1Fen−3Ti3O3n+3

► The Aurivillius phases Bin+1Fen−3Ti3O3n+3 (3 ≤ n ≤ 9) have been synthesized. ► Structural parameters of a perovskite-like block undergo sharp changes when n > 5. ► Bin+1Fen−3Ti3O3n+3 become unstable when n ≈ 9.