Ion emission from lead-zirconium-titanate ferroelectrics under the application of voltage pulses has been observed and analyzed by a time-of-flight mass spectrometer. Mass spectra and relative timing of negative and positive ions and electron emission processes have been determined. The ion spectra are compared with time-of-flight secondary ion mass spectroscopy data obtained in situ. Based on the experimental results, possible microscopic mechanisms of ion formation are discussed. (C) 2000 American Institute of Physics. [S0021-8979(00)01820-X].