Near-surface generation of negative ions in low-pressure discharges

Formation processes of negative ions in low-pressure plasmas are not yet fully understood: as a rule experiments reveal higher negative ion density than predicted by the models. In this work we report near-surface generation of negative ions. This hitherto neglected formation mechanism appears to be important in low-pressure discharges and can have large impacts on the bulk plasma chemistry. We monitor energy-resolved positive and negative ion fluxes arriving at the electrodes in an oxygen parallel-plate radio-frequency ~rf, 13.56 MHz! and dc glow plasmas by means of a quadrupole mass spectrometer. Negative ions formed in the plasma volume are observed by extracting them through an orifice in the anode of a dc glow discharge. Unexpectedly, we record large negative ion signals at the cathode of a dc discharge and at the grounded electrode of an rf discharge. These ions are formed in the plasma sheath, in collision processes involving high-energy species. We propose an efficient mechanism of negative ion generation due to ion pair formation in the sheath.