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Traditionally, Retarding Potential Analyzers (RPAs) operate exclusively on large satellites due to the size, power, and mass constraints posed by nano-satellites like CubeSats. These sensors take in-situ measurements of Earth's atmospheric ion current during a range of time-varied ``retarding" voltage steps. Curve-fitting the retarding voltage versus collected current data provides derived measurements of ion density, ram velocity, and temperature. In order to successfully miniaturize these instruments and validate their performance prior to launch, thorough calibration and comprehensive end-to-end testing must be performed. This paper discusses the difficulties of performing complete system validation in ground-based vacuum chamber testing for RPAs. A procedure for RPA instrument calibration will be presented along with the calibration results for the Lower Atmosphere/Ionosphere Coupling Experiment (LAICE) CubeSat RPA. This paper presents a user-friendly and robust software control suite developed to read, parse, and interpret the data from the LAICE RPA. Electronics noise testing and analysis defines the performance boundaries of the instrument electronics. End-to-end testing of the LAICE RPA with a hot-filament ion source simulating the space plasma verifies the function of the LAICE RPA sensor and electronics, as well as the software control, thus qualifying the instrument for on-orbit use. / Master of Science

"The development of Retarding Potential Analyzers (RPAs) capable of measuring high-density stationary and flowing plasmas is presented. These new plasma diagnostics address the limitations of existing RPAs and can operate in plasmas with electron densities in excess of 1x1018 m-3. Such plasmas can be produced by high-powered Hall Thrusters, Pulsed Plasma Thrusters (PPTs), and other plasma sources. The Single-Channel micro-Retarding Potential Analyzer (SC-microRPA) developed has a minimum channel diameter of 200 microns, electrode spacing on the sub-millimeter scale and can operate in plasmas with densities of up to 1x1017 m-3. The electrode series consists of 100 micron thick molybdenum electrodes and Teflon insulating spacers. The alignment process of the channel, as well as the design and fabrication of the stainless steel outer housing, the Delrin insulating tube, and all other microRPA components are detailed. To expand the applicability of the SC-microRPA to densities above 1x1018 m-3 a low transparency Microchannel Plate (MCP) has been incorporated in the design of a Multi-Channel micro-Retarding Potential Analyzer (MC-microRPA). The current collection theory for the SC-microRPA and the MC-microRPA is also derived. The theory is applicable to microRPAs with arbitrary channel length to diameter ratios and accounts for the reduction of ion flux due to the microchannel plate in the case of the MC-microRPA, due to absorption of ions by channel walls, and due to the applied potential. Current-voltage curves are obtained for incoming plasma flows that range from near-stationary to hypersonic, with temperatures in the range of 0.1 to 10 eV, and densities in the range of 1x1015 m-3 to 1x1021 m-3. The SC-microRPA current collection theory is validated by comparisons with the classical RPA theory and particle-in-cell simulations. Determination of unknown plasma properties is based on a fuzzy-logic approach that uses the generated current-voltage curves as lookup tables."

Doctor of Philosophy (PhD) / This thesis investigates ion energy distributions (IEDs) during plasma immersion ion implantation (PIII). PIII is a surface modification technique where an object is placed in a plasma and pulse biased with large negative voltages. The energy distribution of implanted ions is important in determining the extent of surface modifications. IED measurements were made during PIII using a pulse biased retarding field energy analyser (RFEA) in a capacitive RF plasma. Experimental results were compared with those obtained from a two dimensional numerical simulation to help explain the origins of features in the IEDs. Time resolved IED measurements were made during PIII of metal and insulator materials and investigated the effects of the use of a metal mesh over the surface and the effects of insulator surface charging. When the pulse was applied to the RFEA, the ion flux rapidly increased above the pulse-off value and then slowly decreased during the pulse. The ion density during the pulse decreased below values measured when no pulse was applied to the RFEA. This indicates that the depletion of ions by the pulsed RFEA is greater than the generation of ions in the plasma. IEDs measured during pulse biasing showed a peak close to the maximum sheath potential energy and a spread of ions with energies between zero and the maximum ion energy. Simulations showed that the peak is produced by ions from the sheath edge directly above the RFEA inlet and that the spread of ions is produced by ions which collide in the sheath and/or arrive at the RFEA with trajectories not perpendicular to the RFEA front surface. The RFEA discriminates ions based only on the component of their velocity perpendicular to the RFEA front surface. To minimise the effects of surface charging during PIII of an insulator, a metal mesh can be placed over the insulator and pulse biased together with the object. Measurements were made with metal mesh cylinders fixed to the metal RFEA front surface. The use of a mesh gave a larger ion flux compared to the use of no mesh. The larger ion flux is attributed to the larger plasma-sheath surface area around the mesh. The measured IEDs showed a low, medium and high energy peak. Simulation results show that the high energy peak is produced by ions from the sheath above the mesh top. The low energy peak is produced by ions trapped by the space charge potential hump which forms inside the mesh. The medium energy peak is produced by ions from the sheath above the mesh corners. Simulations showed that the IED is dependent on measurement position under the mesh. To investigate the effects of insulator surface charging during PIII, IED measurements were made through an orifice cut into a Mylar insulator on the RFEA front surface. With no mesh, during the pulse, an increasing number of lower energy ions were measured. Simulation results show that this is due to the increase in the curvature of the sheath over the orifice region as the insulator potential increases due to surface charging. The surface charging observed at the insulator would reduce the average energy of ions implanted into the insulator during the pulse. Compared to the case with no mesh, the use of a mesh increases the total ion flux and the ion flux during the early stages of the pulse but does not eliminate surface charging. During the pulse, compared to the no mesh case, a larger number of lower energy ions are measured. Simulation results show that this is caused by the potential in the mesh region which affects the trajectories of ions from the sheaths above the mesh top and corners and results in more ions being measured with trajectories less than ninety degrees to the RFEA front surface.

Doctor of Philosophy (PhD) / This thesis investigates ion energy distributions (IEDs) during plasma immersion ion implantation (PIII). PIII is a surface modification technique where an object is placed in a plasma and pulse biased with large negative voltages. The energy distribution of implanted ions is important in determining the extent of surface modifications. IED measurements were made during PIII using a pulse biased retarding field energy analyser (RFEA) in a capacitive RF plasma. Experimental results were compared with those obtained from a two dimensional numerical simulation to help explain the origins of features in the IEDs. Time resolved IED measurements were made during PIII of metal and insulator materials and investigated the effects of the use of a metal mesh over the surface and the effects of insulator surface charging. When the pulse was applied to the RFEA, the ion flux rapidly increased above the pulse-off value and then slowly decreased during the pulse. The ion density during the pulse decreased below values measured when no pulse was applied to the RFEA. This indicates that the depletion of ions by the pulsed RFEA is greater than the generation of ions in the plasma. IEDs measured during pulse biasing showed a peak close to the maximum sheath potential energy and a spread of ions with energies between zero and the maximum ion energy. Simulations showed that the peak is produced by ions from the sheath edge directly above the RFEA inlet and that the spread of ions is produced by ions which collide in the sheath and/or arrive at the RFEA with trajectories not perpendicular to the RFEA front surface. The RFEA discriminates ions based only on the component of their velocity perpendicular to the RFEA front surface. To minimise the effects of surface charging during PIII of an insulator, a metal mesh can be placed over the insulator and pulse biased together with the object. Measurements were made with metal mesh cylinders fixed to the metal RFEA front surface. The use of a mesh gave a larger ion flux compared to the use of no mesh. The larger ion flux is attributed to the larger plasma-sheath surface area around the mesh. The measured IEDs showed a low, medium and high energy peak. Simulation results show that the high energy peak is produced by ions from the sheath above the mesh top. The low energy peak is produced by ions trapped by the space charge potential hump which forms inside the mesh. The medium energy peak is produced by ions from the sheath above the mesh corners. Simulations showed that the IED is dependent on measurement position under the mesh. To investigate the effects of insulator surface charging during PIII, IED measurements were made through an orifice cut into a Mylar insulator on the RFEA front surface. With no mesh, during the pulse, an increasing number of lower energy ions were measured. Simulation results show that this is due to the increase in the curvature of the sheath over the orifice region as the insulator potential increases due to surface charging. The surface charging observed at the insulator would reduce the average energy of ions implanted into the insulator during the pulse. Compared to the case with no mesh, the use of a mesh increases the total ion flux and the ion flux during the early stages of the pulse but does not eliminate surface charging. During the pulse, compared to the no mesh case, a larger number of lower energy ions are measured. Simulation results show that this is caused by the potential in the mesh region which affects the trajectories of ions from the sheaths above the mesh top and corners and results in more ions being measured with trajectories less than ninety degrees to the RFEA front surface.

Plasma enhanced chemical vapor deposition systems are massively deployed to grow numerous thin film coatings including hydrogenated amorphous silicon. A new deposition chamber was designed, procured, and constructed to investigate the plasma properties of a 100% silane (SiH4) glow discharge with varying chamber pressure and inter-electrode spacing. A Hiden EQP1000 ion mass spectrometer sampled the plasma from the substrates point of view. Ion energy distributions were obtained using four different excitation sources +DC, –DC, radio frequency (at 13.56 MHz), and the DC Saddle Field (DCSF) in the tetrode configuration. The shape of the ion energy distributions was constant for the capacitively coupled +DC, –DC, and rf (at higher pressures of 75 and 160 mTorr) glow discharges. The shape of the ion energy distributions for the DCSF plasma exhibited a double peak or saddle structure analogous to radio frequency plasmas. The width between the peaks (peak separation) was controlled by the pressure and the semi-transparent cathode to semi-transparent anode distance. Ion energy distributions from the DCSF plasma concurred with rf and +DC ion energy distributions at specific pressures and inter-electrode distances. This result demonstrates the versatility of the DCSF glow discharge system. Moreover, control of the peak separation is modeled to be iii equivalent to controlling the critical ratio (ion transit time in the sheath to the electron oscillating period), and/or the inferred electron oscillating sheath potential. The DCSF possesses a fusion of rf and +DC methods. The long high energy tail or constant background are indicative of a +DC high voltage sheath in which there is an increasing fraction of collisionless ions as the anode-cathode distance increases. These collisionless ions are provided by the oscillating electrons (or rf nature) of the DCSF method. Higher order silane (silicon containing) ions increase in relative intensity with increasing inter-electrode spacing for the +DC, –DC, and rf plasmas. These higher order silane ions are also detected in the DCSF plasma, and can be reduced at either lower pressure or lower cathode to anode or cathode to substrate distances.

Plasma enhanced chemical vapor deposition systems are massively deployed to grow numerous thin film coatings including hydrogenated amorphous silicon. A new deposition chamber was designed, procured, and constructed to investigate the plasma properties of a 100% silane (SiH4) glow discharge with varying chamber pressure and inter-electrode spacing. A Hiden EQP1000 ion mass spectrometer sampled the plasma from the substrates point of view. Ion energy distributions were obtained using four different excitation sources +DC, –DC, radio frequency (at 13.56 MHz), and the DC Saddle Field (DCSF) in the tetrode configuration. The shape of the ion energy distributions was constant for the capacitively coupled +DC, –DC, and rf (at higher pressures of 75 and 160 mTorr) glow discharges. The shape of the ion energy distributions for the DCSF plasma exhibited a double peak or saddle structure analogous to radio frequency plasmas. The width between the peaks (peak separation) was controlled by the pressure and the semi-transparent cathode to semi-transparent anode distance. Ion energy distributions from the DCSF plasma concurred with rf and +DC ion energy distributions at specific pressures and inter-electrode distances. This result demonstrates the versatility of the DCSF glow discharge system. Moreover, control of the peak separation is modeled to be iii equivalent to controlling the critical ratio (ion transit time in the sheath to the electron oscillating period), and/or the inferred electron oscillating sheath potential. The DCSF possesses a fusion of rf and +DC methods. The long high energy tail or constant background are indicative of a +DC high voltage sheath in which there is an increasing fraction of collisionless ions as the anode-cathode distance increases. These collisionless ions are provided by the oscillating electrons (or rf nature) of the DCSF method. Higher order silane (silicon containing) ions increase in relative intensity with increasing inter-electrode spacing for the +DC, –DC, and rf plasmas. These higher order silane ions are also detected in the DCSF plasma, and can be reduced at either lower pressure or lower cathode to anode or cathode to substrate distances.

Ce manuscrit présente l'étude de la fabrication de couches minces de silicium basée sur des différents types de dépôt chimique en phase vapeur assisté par plasma (PECVD) pour des applications dans le photovoltaïque. Tout d'abord, nous avons combiné une chimie du plasma halogéné en utilisant un mélange de SiF4/H2 et la technique plasmas distributés matriciellement à résonance cyclotronique électronique (MDECR) PECVD pour le dépôt de μc-Si:H à grande vitesse. Nous trouvons que les conditions d'énergie ionique modérée sont bénéfiques pour obtenir une diminution significative de la densité des nano-vides, et ainis nous pouvons obtenir un matériaux de meilleure qualité avec une meilleure stabilité. Une méthode de dépôt en deux étapes a été introduite comme moyen alternatif d'éliminer la formation d'une couche d'incubation amorphe pendant la croissance du film. Ensuite, nous avons exploré la technique d'excitation Tailored Voltage Waveform (TVW) pour les processus plasma radiofréquence capacitivement couplé (RF-CCP). Grâce à l'utilisation de TVW, il est possible d'étudier indépendamment l'influence de l'énergie ionique sur le dépôt de matériaux à une pression de processus relativement élevée. Basé sur ce point, nous avons étudié le dépôt de μc-Si:H et a-Si:H à partir des plasma de SiF4/H2/Ar et de SiH4/H2, respectivement. A partir d'une analyse des propriétés structurelles et électroniques, nous constatons que la variation de l'énergie ionique peut directement traduite dans la qualité du matériaux. Les résultats se sont appliqués aux dispositifs photovoltaïques et ont établi des liens complets entre les paramètres de plasma contrôlables par TVW et les propriétés de matériaux déposé, et finalement, les performances du dispositif photovoltaïque correspondant. Enfin, nous avons trouvé que dans le cas du dépôt de couches minces de silicium à partir du plasma de SiF4/H2/Ar à l'aide de sawtooth TVW, on peut réaliser un processus de dépôt sur une électrode, sans aucun dépôt ou gravure. contre-électrode. Ceci est dû à deux effets: la nature multi-précurseur du processus de surface résultant et la réponse de plasma spatiale asymétrique par l'effet d'asymétrie de pente de la sawtooth TVW. La découverte de tels procédés “electrode-selective” encourage la perspective que l'on puisse choisir un ensemble de conditions de traitement pour obtenir une grande variété de dépôts désirés sur une électrode, tout en laissant l'autre vierge. / This thesis describes the study of silicon thin film materials deposition and the resulting photovoltaic devices fabrication using different types of plasma-enhanced chemical vapour deposition (PECVD) techniques.In the first part, we combine a SiF4/H2 plasma chemistry with the matrix-distributed electron cyclotron resonance (MDECR) PECVD to obtain high growth rate microcrystalline silicon (µc-Si:H). Due to the special design of MDECR system, careful investigation of the impact energy of impinging ions to material deposition can be accessible. We find that moderate ion energy conditions is beneficial to achieve a significant drop in the density of nano-voids, thus a higher quality material with better stability can be obtained. A two-step deposition method is introduced as an alternative way to eliminate the existence of amorphous incubation layer during film growth.The second part of work is dedicate to the exploration of the Tailored Voltage Waveforms (TVWs) excitation technique for capacitively coupled plasmas (CCP) processes. As an advantage over the conventional sinusoidal excitations, TVWs technique provide an elegant solution for the ion flux-energy decoupling in CCP discharges through the electrical asymmetry effect, which makes the independent study of the impact of ion energy for material deposition at relatively high process pressure possible. Based on this insight, we have studied the deposition of µc-Si:H and amorphous silicon (a-Si:H) from the SiF4/H2/Ar and SiH4/H2 plasma chemistry, respectively. From the structural and electronic properties analysis, we find that the variation of ion energy can be directly translated into the material quality. We have further applied these results to photovoltaic applications and established bottom-up links from the controllable plasma parameters via TVWs to the deposited material properties, and eventually to the resulting device quality.In the last part, as a further application of TVWs, an “electrode-selective” effect has been discovered in the CCP processes. In the case of silicon thin film deposition from the SiF4/H2/Ar plasma chemistry, one can achieve a deposition process on one electrode, while at the same time either no deposition or an etching process on the counter electrode. This is due to two effects: the multi-precursor nature of the resulting surface process and the asymmetric plasma response through the utilization of TVWs. Moreover, such deposition/etching balance can be directly controlled through H2 flow rate. From a temporal asymmetry point of view, we have further studied the impact of process pressure and reactor geometry to the asymmetric plasma response for both the single-gas and multi-gas plasmas using the sawtooth waveforms. The product of pressure and inter-electrode distance P·di is deduced to be a crucial parameter in determine the plasma heating mode, so that a more flexible control over the discharge asymmetry as well as the relating “electrode-selective” surface process can be expected.

Constructing dual-ion energy storage devices using anion-intercalation graphite cathodes offers the unique opportunity to simultaneously achieve high energy density and output power density. However, a critical challenge remains in the lack of proper anodes that match with graphite cathodes, particularly in sustainable electrolyte systems using abundant potassium. Here, a surface grafting approach utilizing multifunctional azobenzene sulfonic acid is reported, which transforms V2C MXene into a high-kinetics K+-intercalation anode (denoted ASA-V2C) for dual-ion energy storage devices. Importantly, the grafted azobenzene sulfonic acid offers extra K+-storage centers and fast K+-hopping sites, while concurrently acting as a buffer between V2C layers to mitigate the structural distortion during K+ intercalation/de-intercalation. These functionalities enable the V2C electrode with significantly enhanced specific capacity (173.9 mAh g−1 vs 121.5 mAh g−1 at 0.05 A g−1), rate capability (43.1% vs 12.0% at 20 A g−1), and cycling stability (80.3% vs 45.2% after 900 cycles at 0.05 A g−1). When coupled with an anion-intercalation graphite cathode, the ASA-V2C anode demonstrates its potential in a dual-ion energy storage device. Notably, the device depicts a maximum energy density of 175 Wh kg−1 and a supercapacitor-comparable power density of 6.5 kW kg−1, outperforming recently reported Li+-, Na+-, and K+-based dual-ion devices.