Chemical pressure effect in Sm and La substituted ferroelectric BiFeO3 thin films: Insights from infrared spectroscopy

Abstract

We investigate the effects of Sm and La substitution in ferroelectric BiFeO3 thin films on the lattice dynamics by infrared reflection measurements at room temperature. The frequencies of the infrared-active phonon modes are studied as a function of Sm and La content in Bi1–x(Sm,La)xFeO3 composition spread films in the range from x = 0 up to x = 0.25, grown on SrTiO3 substrates by pulsed laser deposition. Substitution of the Bi3+ ions with small Sm3+ ions leads to the appearance of a new phase above x ≈ 0.09 coexisting with the ferroelectric BiFeO3 phase up to x ≈ 0.19. In contrast, for the substitution of Bi3+ ions with La3+ ions of similar size a continuous transition from the original BiFeO3 phase to a new phase takes place. In both cases, we assign the new phase to the paraelectric, orthorhombic phase. These findings are discussed in terms of the morphotropic phase boundary in Sm-doped BiFeO3 around x = 0.14 with a phase coexistence, which was suggested as the origin for enhanced piezoelectric properties.