Processing of SiO2 layers with atomic scale control is one of the main requirements to achieve nanoscale device fabrication. In this thesis, a novel (multi-frequency) Capacitively-Coupled-Plasma (CCP) system with a Very-High-Frequency (VHF) multi-tile electrode is investigated for the application to cyclic fluorocarbon-based etching of SiO2, based on a two-step Atomic-Layer-Etch process. This system (Starchief ) is a modification of an industrial wafer-processing tool, originally com- prised of a lower powered (2+27 MHz) and upper grounded electrode. For this research, the upper grounded electrode is replaced with a multi-tile-array excited at 162MHz. The unique plasma chemistry and low energy sheath of high-VHF limits ion-driven surface mixing; this in turn promotes an etch plateau resulting in a broader ALE pro- cess window with a self-limiting removal half-cycle. Investigation into the unique plasma physics of high-VHF excitation and power coupling mechanisms of a multi-tile electrode is conducted in a single-frequency powered plasma source, called PASTIS. In a nitrogen discharge, op- tical emission spectroscopy results show large differences between vi- brational (∼6200-9400K) and rotational gas (∼350-450K) tempera- tures, which suggest highly non-equilibrium conditions. The ratio of stochastic to ohmic heating is determined, and even at high operat- ing pressures (> 500 mTorr), the VHF plasma is driven dominantly by stochastic electron heating. Ion energy distributions (IEDs), mea- sured using an energy-resolved mass spectrometer, exhibit symmet- ric narrow distributions due to very-high-frequency plasma operation. Negative ion densities are inferred from measured electron density and ion flux using resonance hairpin probe and planar probe respectively. In a low-pressure electronegative discharge, measured electrode volt- age and current, charged particle density, including negative ions, and ion energy distributions exhibit a mode transition versus RF power. The results conclude that the observed mode transition is caused by the change in current coupling mechanisms and modification in the discharge impedance, including the presence of negative ions. In elec- tropositive, and high-pressure electronegative discharges, the ion en- ergy distribution trends versus RF power provide evidence of electrical asymmetry; the push-pull power delivery to the multi-tile electrode result in floating electrode tiles that develop a DC bias such that ion energy delivered to the substrate-holding electrode is substantially reduced. The significance of this is that the solution of a multi-tile electrode CCP driven at VHF facilitates independent control of flux densities and low-ion-energy driven sheaths. In the Starchief system, a Phase-Modulated Spectroscopic Ellipsometer (PMSE) is used for in- situ monitoring of the surface changes at each half-cycle of the ALE process. The atomic composition and chemical bonding structure of the fluorocarbon modified layers are analysed by x-ray photoelectron spectroscopy (XPS). This research highlights the potential of combin- ing existing atomic-layer-process technology, with a large-scale VHF CCP which enables unique plasma and surface chemistry necessary for next generation processing.