Kinetic arrest of the first-order to R3c Pbnm phase transition in supercooled La(x)MnO(3+δ) (x = 1 and 0.9).

We report the occurrence of kinetic arrest of the first-order phase transition from R3c to Pbnm in supercooled La(x)MnO(3±δ) (x = 1 and 0.9, i.e. δ > 0.125). Structural studies have been done, employing low temperature transmission electron microscopy (LT-TEM) and low temperature x-ray diffraction (LT-XRD) techniques. No phase transformation was observed even in La(x)MnO(3±δ) aged for ~12 h at 98 K. The evidence of the occurrence of kinetic arrest was realized at low temperatures through in situ electron beam triggered nucleation and perpetual devitrification of the R3c phase into a Pbnm phase. It was clearly evidenced that the R3c structure of La(x)MnO(3±δ), below its ferromagnetic transition temperature, is metastable and prone to be transformed to a Pbnm orthorhombic structure following initiation by an electron beam trigger. The electron beam transformed Pbnm phase was found to transform back to the R3c phase through a first-order phase transition occurring close to the ferromagnetic to paramagnetic transition (T(c)) during heating. The glass-like kinetics of the arrested R3c phase has been investigated through resistance relaxation measurements, showing a decreasing logarithmic rate of decay of the arrested R3c phase towards the stable Pbnm phase with decreasing temperature, down to 5 K. On the basis of the correlations observed in the resistance-versus-temperature, magnetization-versus-temperature, magnetization-versus-field, resistance relaxation and LT-XRD measurements, the occurrence of kinetic arrest has been attributed to the suppression of Jahn-Teller distortion by double exchange across the insulator-metal transition.