Strain heterogeneity and magnetoelastic behaviour of nanocrystalline half-doped La, Ca manganite, La0.5Ca0.5MnO3

Elastic and anelastic properties of La0.5Ca0.5MnO3 determined by resonant ultrasound spectroscopy in the frequency range ∼100-1200 kHz have been used to evaluate the role of grain size in determining the competition between ferromagnetism and Jahn-Teller/charge order of manganites which show colossal magneto resistance. At crystallite sizes of ∼75 and ∼135 nm the dominant feature is softening of the shear modulus as the charge order transition point, Tco (∼225 K), is approached from above and below, matching the form of softening seen previously in samples with 'bulk' properties. This is consistent with a bilinear dominant strain/order parameter coupling, which occurs between the tetragonal shear strain and the Jahn-Teller (Γ3(+)) order parameter. At crystallite sizes of ∼34 and ∼42 nm the charge ordered phase is suppressed but there is still softening of the shear modulus, with a minimum near Tco. This indicates that some degree of pseudoproper ferroelastic behaviour is retained. The primary cause of the suppresion of the charge ordered structure in nanocrystalline samples is therefore considered to be due to suppression of macroscopic strain, even though MnO6 octahedra must develop some Jahn-Teller distortions on a local length scale. This mechanism for stabilizing ferromagnetism differs from imposition of either an external magnetic field or a homogeneous external strain field (from a substrate), and is likely to lead both to local strain heterogeneity within the nanocrystallites and to different tilting of octahedra within the orthorhombic structure. An additional first order transition occurs near 40 K in all samples and appears to involve some very small strain contrast between two ferromagnetic structures.