Abstract

Resistivity measurements on a La0.67Ca0.33MnO3 film are reported for a series of argon anneals at successively higher temperatures. Tc, the ferromagnetic ordering temperature, increases uniformly with increasing annealing temperature and annealing time. Hence, Tc can be tuned by appropriate annealing. In order to fully anneal these samples, i.e., achieve bulk properties, it proves sufficient to anneal them in argon. Further annealing in oxygen produces only minor changes in the resistivity. Data from Tc up to 1200 K show activated conduction with ρ=BTeEa/kT, the temperature dependence predicted by the Emin–Holstein theory of adiabatic polaron hopping. Their model fits both data from the partially annealed and fully annealed samples better than the variable range hopping or semiconductor models which have been used by previous workers. The activation energy Ea and resistivity coefficient B decrease with increasing maximum anneal temperature. These changes, together with the increase in Tc, are consistent with an anneal induced relaxation of the Mn–O–Mn bond angle. The time dependent resistivity during annealing at a fixed temperature follows the equation ρ=ρ0{1−D ln[1+(t−t0)/τ]}, making it possible to acquire data in a reversible regime, and also to obtain an estimate of the annealing activation energy.

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