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Interface segregation of boron at Si(111) surfaces has been studied at the atomic scale using a scanning tunnelling microscope (STM). During the segregation process (produced by thermal annealing), strong cooperative effects take place which cannot be explained by a simple nearest-neighbour pair interaction model. Although average surface concentrations of boron in the investigated temperature range could be calculated in terms of a Fowler's model, the comparison between STM and simulated images suggests that one must introduce longer-range interactions to describe the atomic-scale configurations.