Plasma-surface reactions at a spinning wall.

We report a new method for studying surface reactions and kinetics at moderately high pressures (<10 Torr) in near real time. A cylindrical substrate in a reactor wall is rotated at up to 200,000 rpm, allowing the surface to be periodically exposed to a reactive environment and then analyzed by a triple-differentially pumped mass spectrometer in as little as 150 micros thereafter. We used this method to study oxygen plasma reactions on anodized aluminum. When the substrate is spun with the plasma on, a large increase in O2 signal at m/e = 32 is observed with increasing rotation frequency, due to O atoms that impinge and stick on the surface when it is in the plasma, and then recombine over the approximately 0.7 to 40 ms period probed by changing the rotation frequency. Simulations of O2 signal versus rotation frequency indicate a wide range of recombination rate constants, ascribed to a range of O-binding energies.

Recombination reactions of oxygen atoms on an anodized aluminum plasma reactor wall, studied by a spinning wall method.

We have studied the recombination of O atoms on an anodized Al surface in an oxygen plasma, using a new "spinning wall" technique. With this method, a cylindrical section of the wall of the plasma reactor is rotated and the surface is periodically exposed to an oxygen plasma and then to a differentially pumped mass spectrometer (MS). By varying the substrate rotation frequency (r), we vary the reaction time (t(r)), that is, the time between exposure of the surface to O atoms in the plasma and MS detection of desorbing O(2) (t(r) = 1/2r). As t(r) is increased from 0.7 to 40 ms, the O(2) desorption signal decreases by a factor of 2 for an O-atom flux of 1 x 10(16) cm(-2) s(-1) and by a factor of 6 when the O flux is 1 x 10(17) cm(-2) s(-1). The O(2) signal decay is highly nonexponential, slowing at longer times and reaching zero signal as r --> 0. A model of O-atom recombination is compared with these time-dependent results. The model assumes adsorption occurs at surface sites with a range of binding energies. O can detach from these sites, become mobile, and diffuse along the surface. This leads to desorption of O, reattachment at free adsorption sites, and recombination to form O(2) that promptly desorbs. With several adjustable parameters, the model reproduces the observed shapes of the O(2) desorption decay curves and the lack of detectable desorption of O and predicts a high O-atom recombination coefficient on anodized aluminum.