In this work the resonance hairpin probe technique has been used for detection of photoelectrons generated during photodetachment experiments performed to determine negative ion density in an inductively coupled oxygen plasma. An investigation of the temporal development of the photoelectron population was recorded with the hairpin probe located inside the laser beam region and at various points outside the beam. Varying the external microwave frequency used to drive the probe resonator allowed the local increase in electron density resulting from photoelectrons to be determined. At a fixed probe frequency, we observed two resonance peaks in the photodetachment signal as the photoelectron density evolved as a function of time. Inside the laser beam the resonance peaks were asymmetric, the first peak rising sharply as compared with the second peak. Outside the laser beam region the peaks were symmetric. As the external frequency was tuned the resonance peaks merge at the maximum electron density. The resonance peak corresponding to maximum density outside the beam occurs at a delay of typically 1-2 s as compared with the centre of the beam allowing an estimate of the negative ion velocity. Using this method, negative ion densities were measured under a range of operating conditions inside and outside the beam.

We describe a versatile bottom-up approach to covalently and rapidly graft hydroxyl terminated poly (2-vinyl pyridine) (P2VP-OH) polymers in 60 seconds that can subsequently be used to fabricate high quality TiO2 films on silicon substrates. A facile strategy based upon room temperature titanium vapor phase infiltration of the grafted P2VP-OH polymer brushes produces TiO2 nanofilms of 2-4 nm thickness. In order to fabricate coherent inorganic films with precise thickness control, it is critical to generate a high-quality polymer brush film i.e. a complete monolayer. Definition of precise and regular polymer monolayers is straightforwardly achieved for polymers which are weakly interacting with one another and the substrate (apart from the reactive terminal group used for grafting). However this is much more challenging for reactive systems. Crucial parameters are explored including molecular weight and solution concentration for grafting dense P2VP-OH monolayers from the liquid phase with very high coverage and uniformity across wafer scale areas. Additionally, we compare the P2VP-OH polymer system with another reactive polymer PMMA-OH and a relatively non-reactive polymer PS-OH, the latter we prove to be extremely effective for surface blocking and deactivation. Our methodology provides new insight into the grafting of polymer brushes and their ability to form dense TiO2 films. We believe the results described herein are important for further expanding the use of reactive and unreactive polymers for fields including area selective deposition, solar cell absorber layers and antimicrobial surface coatings.

Actinometry is a non-invasive optical technique that can be used to quantitatively monitor atomic oxygen number densities [O] in gas discharges under certain operating conditions. However, careless application of the technique can lead to erroneous conclusions regarding the behaviour of atomic oxygen in plasma. One limitation on this technique is an accurate knowledge of the various rate constants required, which in turn is hampered by an insufficiently precise knowledge of the Electron Energy Distribution Function (EEDF) in the plasma. In this work Particle in Cell (PIC) simulations have been used to generate theoretical EEDFs. To validate a simulation the electron density n e produced by the PIC code is compared to experimental n e values measured using a hairpin probe. The PIC input parameters are adjusted to optimise agreement between the PIC and experimental n e results. This approach should in principle yield an EEDF that more accurately reflects the true EEDF in the plasma. The PIC EEDF is then used to generate rate constants for the actinometry model which should improve the accuracy of the quantitative [O] result for that particular set of plasma conditions. The actinometry [O] results are then compared to [O] results obtained using Two-photon Absorption Laser Induced Fluorescence (TALIF) to validate the approach.

A floating emissive probe is applied in conjunction with pulsed laser photo-detachment of O − ions to enable measurement of the dynamic evolution in a plasma potential resulting from the presence of photoelectrons in a 13.56 MHz inductive radio-frequency oxygen discharge. The emissive probe emits thermionic electrons, allowing it to reach a saturation potential which is characterized as the local space potential of the plasma. After the photo-detachment pulse, the local space plasma potential in the illuminated region shoots up to a higher positive value and then relaxes to equilibrium in microsecond time scales. Using the relaxation time of the space potential, the negative ion temperature of O − is estimated over a 10-50 mTorr range and is found to be in the 0.19-0.03 eV range. The negative ion temperature measured by this method is found to be lower than that calculated from the time evolution in electron density resulting from photo-detachment which is independently measured using a resonance hairpin probe.

Two-photon absorption laser-induced fluorescence (TALIF) spectroscopy was used for detection of absolute atomic oxygen density in a low-pressure capacitively coupled plasma source. We investigated the variation of atomic oxygen density for various mixtures of O 2 /SF 6 and report a significant five-fold increase of [O] when oxygen plasma was diluted with SF 6 by only 5%. We attribute this increase in [O] to a combination of a change in surface conditions caused by constituents of SF 6 plasma reacting with the reactor walls and also due to an increase in the electron temperature. Atomic oxygen production rates were determined using electron-energy distribution functions obtained with a cylindrical Langmuir probe. It was found that the effective electron temperature dramatically increased from approximately 1-8 eV as the SF 6 content varied from 0% to 60% which consequently resulted in a three-fold increase in the atomic oxygen production rate. TALIF was also used to investigate the variation of [O] due to fluorination of the reactor walls and also after etching resist-coated wafers. It was found that [O] increased by over a factor of three after fluorinating the walls with SF 6 plasma; on the other hand a coating formed on the reactor walls after a resist etch process resulted in a reduction of [O] by only 20%.