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A correlative study of the electrically active grain boundary structure of ZnO polycrystals has been carried out using a scanning electron microscope/scanning tunneling microscope (SEM/STM) combined instrument. Current imaging tunneling spectroscopy (CITS) measurements reveal reduced surface band gaps, as compared with grain interiors, at the charged boundaries imaged by SEM-based remote electron beam induced current (REBIC). ZnO grain boundaries were also imaged in the STM-REBIC mode with a resolution of up to 20 nm. The contrast differences observed in the SEM-REBIC and STM-REBIC images are discussed in terms of the different experimental conditions used in both techniques. © 1999 American Institute of Physics.