Enhanced grain surface effect on magnetic properties of nanometric La0.7Ca0.3MnO3 manganite : Evidence of surface spin freezing of manganite nanoparticles

We have investigated the effect of nanometric grain size on magnetic properties of single phase, nanocrystalline, granular La0.7Ca0.3MnO3 (LCMO) sample. We have considered core-shell structure of our LCMO nanoparticles, which can explain its magnetic properties. From the temperature dependence of field cooled (FC) and zero-field cooled (ZFC) dc magnetization (DCM), the magnetic properties could be distinguished into two regimes: a relatively high temperature regime T > 40 K where the broad maximum of ZFC curve (at T = Tmax) is associated with the blocking of core particle moments, whereas the sharp maximum (at T = TS) is related to the freezing of surface (shell) spins. The unusual shape of M (H) loop at T = 1.5 K, temperature dependent feature of coercive field and remanent magnetization give a strong support of surface spin freezing that are occurring at lower temperature regime (T < 40 K) in this LCMO nanoparticles. Additionally, waiting time (tw) dependence of ZFC relaxation measurements at T = 50 K show weak dependence of relaxation rate [S(t)] on tw and dM/dln(t) following a logarithmic variation on time. Both of these features strongly support the high temperature regime to be associated with the blocking of core moments. At T = 20 K, ZFC relaxation measurements indicates the existence of two different types of relaxation processes in the sample with S(t) attaining a maximum at the elapsed time very close to the wait time tw = 1000 sec, which is an unequivocal sign of glassy behavior. This age-dependent effect convincingly establish the surface spin freezing of our LCMO nanoparticles associated with a background of superparamagnetic (SPM) phase of core moments.