The generation and annihilation of defects upon electron irradiation and subsequent annealing has been studied by high-resolution deep level transient spectroscopy (Laplace DLTS) in phosphorus-doped silicon crystals which were grown by the vacuum float zone technique. It was found that the disappearance of phosphorus–vacancy pairs in the temperature range of 125–175°C is accompanied by a significant reduction in the concentration of Ci–Cs complexes and formation of a defect with an acceptor level at Ec−0.21eV. The level was assigned to a pair of substitutional carbon atoms (Cs–Cs), which is formed when the free vacancy released upon E-centre annealing is captured by the Ci–Cs complex.