Plasma Polymerization Of Tetrafluoroethylene. I. Inductive Radio Frequency Discharge

The plasma polymerization of tetrafluoroethylene in an inductively coupled radio frequency glow discharge, using a flow system, was studied. A simple long tube reactor, with the coupling coil placed at the middle of the tube and gas entrance and exit at the respective ends, was used. Deposition rates and the chemical nature of the polymer (as revealed by ESCA spectra and surface energy studies) are obtained as a function of location in the reactor tube with respect to the coupling coil and of applied energy per unit mass of tetrafluoroethylene (W/FM). It was found that a fluorine poor polymer, containing considerable carbon–oxygen bonds (after contact with air), is obtained at all locations at high W/FM. When a low W/FM is utilized, such a fluorine‐poor polymer is also obtained at locations downstream from the coupling coil (the location of the highest energy density) in the reactor. In the latter case a fluorine‐rich polymer containing very little oxygen is formed upstream from the coil. The polymer deposition rate distribution is also considerably broader in a high W/FM plasma than when low W/FM is used. These results are in agreement with earlier studies indicating that fluorine abstraction and decomposition due to fluorine etching occur when the energy density, as expressed by W/FM, is high. Copyright © 1979 John Wiley & Sons, Inc

Plasma Polymerization Of Tetrafluoroethylene. II. Capacitive Radio Frequency Discharge

The plasma polymerization of tetrafluoroethylene (TFE) is studied in a capacitively coupled system with internal electrodes using radio frequency (13.56 MHz) power. The emphasis is on identifying conditions that are compatible with continuous coating of plasma polymer on a substrate moving through the center of the interelectrode gap. At high pressure (500 mTorr), deposition of plasma polymer is primarily on the electrodes rather than on a substrate placed midway between electrodes. Glow is observed in only part of the interelectrode gap at low powers and fills the gap only at high power levels. The use of a magnetic field effects barely discernible changes. Low‐pressure (below 100 mTorr) operation is more favorable for deposition of a substantial portion of the plasma polymer on a substrate placed midway between electrodes. The plasma polymer deposited at low pressure is characterized by ESCA and deposition rate data and compared to that deposited in an inductively coupled system. The polymers formed in both systems are broadly similar and completely different from conventional poly(TFE). Subtle system‐dependent differences are identified. The known susceptibility of fluorine‐containing polymers (including plasma polymer) to a high‐power plasma has been used as a probe of plasma power density within the interelectrode gap in the capacitively coupled system. Without magnets the most active zone of the plasma is in the center of the interelectrode gap. The use of a magnetic field moves this active zone closer to the electrodes and leads to a more efficient coupling of energy to a polymerizing glow discharge. Copyright © 1979 John Wiley & Sons, Inc