Magnetically tunable nonlinear current–voltage characteristics in oxygen deficient manganite perovskites

La0.667Ca0.333Mn1−xMxO3−δ (M=Mg, Li or Re) exhibit insulating behaviour and nonlinear current–voltage (J–E) relationship with voltage-limiting characteristics at temperatures below the ferromagnetic transition (Tc). The high current region is set in at field strengths <60 V/cm. Nonlinearity exponent, α in the relation J=kEα increases inversely with temperature. In presence of an external magnetic field, the J–E curves show higher current density at lower field strengths. Microstructural studies indicate that there is no segregation of secondary phases in the grain boundary regions. There is remarkable changes in ρ(T) as well as J–E curves with the grain size. Annealing studies in lower pO2 atmospheres indicate that there is significant out-diffusion of oxygen ions through the grain boundary layer (GBL) regions creating oxygen vacancies in the GBL regions. The concentration of Mn4+ ions is lowered at the GBL due to oxygen vacancies, reducing the probability of hopping and resulting in insulating behaviour. Therefore an insulating barrier is introduced between two conducting grains and the carrier motion between the grains is inhibited. Thus below Tc, where sufficient increase in resistivity is observed the conduction may be arising as a result of spin dependent tunneling across the barrier. External electric field lowers the barrier height and establishes carrier transport across the barrier. Above certain field strength, barrier height diminishes significantly and thereby allowing large number of carriers for conduction, giving rise to highly nonlinear conductivity.