Large particles (tens of nm to tens of &mgr;m in diameter) are problematic in low‐pressure (<1 Torr) plasma processing (etching, deposition) discharges because they can contaminate the product and can perturb electron transport. Although the source of these particles has been studied by a number of groups, a definitive explanation is still lacking. In this paper, we theoretically investigate the role of negative ions in the formation of large clusters, the precursors to particles, in low‐pressure plasmas. We find that the formation of particles requires a critically large cluster. Forming the critically large cluster requires longer residence times in the plasma than is usually possible if clustering involves only neutral particles. We propose that negatively charged intermediates, which are trapped in electropositive plasmas, increase the average residence time of clusters to allow the growth of critically large clusters.