The Physics of Plasma Ion Chemistry: A Case Study of Plasma Polymerization of Ethyl Acetate.

Deposition chemistry from plasma is highly dependent on both the chemistry of the ions arriving at surfaces and the ion energy. Typically, when measuring the energy distribution of ions arriving at surfaces from plasma, it is assumed that the distributions are the same for all ionic species. Using ethyl acetate as a representative organic precursor molecule, we have measured the ion chemistry and ion energy as a function of pressure and power. We show that at low pressure (<2 Pa) this assumption is valid; however, at elevated pressures ion-molecule collisions close to the deposition surface affect both the energy and chemistry of these ions. Smaller ions are formed close to the surface and have lower energy than larger ionic species which are formed in the bulk of the plasma. The changes in plasma chemistry therefore are closely linked to the physics of the plasma-surface interface.