Improved crystallinity,spatial arrangement and monodispersity of submicron La0.7Ba0.3MnO3 powders: A citrate chelation approach

The perovskite manganite systems have been the materials of tremendous interest due to their strong correlation between structure, transport and magnetism. These materials in their single-crystal form show colossal magneto-resistance (CMR), but the applied fields are very high (∼1–5 T). The polycrystalline samples do show high low-field magneto-resistance (LFMR), but good amount of control over particle sizes and grain-boundary distribution is required, which is well known but less realized in practical approaches. In this context, we report on synthesis and manipulation of polycrystalline La_0.7Ba_0.3MnO₃ (LBMO) submicron powders using citric acid chelation. The Citrate-gel route is used to synthesize poly-dispersed LBMO powders which are subjected to citrate chelation for a duration of 0 (LB0) to 4 h(LB4) . The samples show improved ordering in X-ray diffraction patterns. Raman spectroscopy scans indicate changed mode signatures due to the probable chelating process, which alters the surface morphology. X-ray photoelectron microscopy shows an evidence of fine citrate layer on the grain boundaries. Low temperature B–H curves exhibit fine hysteresis loops for all samples, while room temperature B–H curves shows paramagnetic response. Scanning electron microscopy images showed the formation of well arranged, connected, mono-dispersed grains of LB4 sample, as against polydispered LB0. The magneto-resistance (at H=100 kOe) is seen to enhance for LB4 at its transition temperature (75%, as compared to LB0, where it is 60%), which can be attributed to the well-controlled inter-grain tunneling phenomenon and thin insulating regions in between, created due to citrate chelation, which probably enhances the scattering phenomenon and its susceptibility to applied fields. As citric acid is known to chelate Mn ions, it probably chelates the smaller LB particulate structure and leaves behind citrate-connected submicron grains of LBMO, which are seen to be well engineered.