Pr and Co doped ZnO bicrystals with various types of grain boundaries were fabricated to investigate their current–voltage characteristics. In addition, their grain boundary structures and chemical compositions were investigated using high-resolution transmission electron microscopy and energy-dispersive x-ray spectroscopy. It was found that all the boundaries are atomically joined, but have some precipitates of Pr6O11. Co dopants are distributed over the grain interiors and boundaries, while Pr dopants segregate at the fabricated grain boundaries except for a highly coherent Σ1 boundary. The Σ1 boundary with no Pr segregation shows an almost Ohmic characteristic, and coincidence-site lattice and random boundaries with clear Pr segregations show nonlinear characteristics. The change in the nonlinearity is attributed to the difference of the Pr concentration that is associated with the grain boundary structure.

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