AbstractsChemistry

In this thesis, a low-pressure, capacitively-coupled plasma (CCP) was investigated using the well established techniques of actinometry, two-photon laser-induced fluorescence (TALIF), appearance potential mass spectrometry (APMS), Langmuir and hairpin probes. The behaviour of atomic oxygen density in mixtures of O2/SF6 was investigated using TALIF and a Langmuir probe. A significant five-fold increase of [O] was observed when O2 plasma was diluted with SF6 (5 - 10%). This was attributed to a combination of a change in surface conditions and also due to a shift in the effective electron temperature, Tef f . It was found that Tef f dramatically increased from ≈ 1 to 8 eV as the SF6 content varied from 0 - 60% which consequently resulted in a threefold increase in the atomic oxygen production rate. [O] increased by over a factor of three after fluorinating the walls with SF6 plasma. Electron energy distribution functions, EEDFs, required for calculating excitation rate constants needed for actinometry were measured with a Langmuir probe. When compared to TALIF measurements; actinometry showed excellent quantitative agreement in pure O2 plasma but did not predict the rapid rise of [O] with SF6 addition and grossly overestimated [O] in O2 plasma containing SF6. However, reasonable qualitative agreement was shown for mixtures in the range of 10 to 60% SF6. A Langmuir probe was used to investigate various electron heating phenomena in O2 and Ar plasmas. The so called ‘α − γ’ mode transition in O2 plasma (100 mTorr) was identified from the power evolution (3 - 600 W) of the electron energy probability function (EEPF) electron density (ne) and Tef f . The EEPF evolved from Druyvesteyn to bi-Maxwellian with increasing power which resulted in a rapid decrease and abrupt increase in Tef f and ne respectively. Comparisons were made to the same mode transition for simi-17 ar conditions in Ar plasma. Low energy electrons were effectively heated in Ar plasma when compared to O2 plasma. This was unusual since Ar atoms have an abnormally low momentum transfer cross-section (Ramsauer effect) which does not favour collisional heating of low energy electrons. The pressure evolution of the EEPF, ne, and Tef f was also investigated in O2 plasma operated at 30 and 200 W. The number of high energy electrons decreased with increasing pressure (10 - 70 mTorr), however, high energy electrons were enhanced for pressures above 70 mTorr at 30 W and greater than 400 m Torrat 200 W. This behaviour is contrary to the inverse relationship between the ionization rate and gas density (particle balance). The mechanisms behind such unusual behaviour are still unknown and require further investigation. Although, structure was observed on the EEPFs which could indicate the presence of super-elastic collisions; a process which is known to enhance the tail of the EEPF. Atomic fluorine density was measured in both SF6/Ar (95/5%) and SF6/O2/Ar (85/10/5%) discharges using appearance potential mass spectrometry (APMS). The dissociation fraction, D, increased…