abstract: In this dissertation, remote plasma interactions with the surfaces of low-k interlayer dielectric (ILD), Cu and Cu adhesion layers are investigated. The first part of the study focuses on the simultaneous plasma treatment of ILD and chemical mechanical polishing (CMP) Cu surfaces using N2/H2 plasma processes. H atoms and radicals in the plasma react with the carbon groups leading to carbon removal for the ILD films. Results indicate that an N2 plasma forms an amide-like layer on the surface which apparently leads to reduced carbon abstraction from an H2 plasma process. In addition, FTIR spectra indicate the formation of hydroxyl (Si-OH) groups following the plasma exposure. Increased temperature (380 °C) processing leads to a reduction of the hydroxyl group formation compared to ambient temperature processes, resulting in reduced changes of the dielectric constant. For CMP Cu surfaces, the carbonate contamination was removed by an H2 plasma process at elevated temperature while the C-C and C-H contamination was removed by an N2 plasma process at elevated temperature. The second part of this study examined oxide stability and cleaning of Ru surfaces as well as consequent Cu film thermal stability with the Ru layers. The ~2 monolayer native Ru oxide was reduced after H-plasma processing. The thermal stability or islanding of the Cu film on the Ru substrate was characterized by in-situ XPS. After plasma cleaning of the Ru adhesion layer, the deposited Cu exhibited full coverage. In contrast, for Cu deposition on the Ru native oxide substrate, Cu islanding was detected and was described in terms of grain boundary grooving and surface and interface energies. The thermal stability of 7 nm Ti, Pt and Ru ii interfacial adhesion layers between a Cu film (10 nm) and a Ta barrier layer (4 nm) have been investigated in the third part. The barrier properties and interfacial stability have been evaluated by Rutherford backscattering spectrometry (RBS). Atomic force microscopy (AFM) was used to measure the surfaces before and after annealing, and all the surfaces are relatively smooth excluding islanding or de-wetting phenomena as a cause of the instability. The RBS showed no discernible diffusion across the adhesion layer/Ta and Ta/Si interfaces which provides a stable underlying layer. For a Ti interfacial layer RBS indicates that during 400 °C annealing Ti interdiffuses through the Cu film and accumulates at the surface. For the Pt/Cu system Pt interdiffuion is detected which is less evident than Ti. Among the three adhesion layer candidates, Ru shows negligible diffusion into the Cu film indicating thermal stability at 400 °C. / Dissertation/Thesis / Ph.D. Physics 2012

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The lunar space environment is shaped by the interaction between the Moon and the solar wind. In the present thesis, we investigate two aspects of this interaction, namely the interaction between solar wind protons and lunar crustal magnetic anomalies, and the interaction between solar wind protons and lunar regolith. We use particle sensors that were carried onboard the Chandrayaan-1 lunar orbiter to analyze solar wind protons that reflect from the Moon, including protons that capture an electron from the lunar regolith and reflect as energetic neutral atoms of hydrogen. We also employ computer simulations and use a hybrid plasma solver to expand on the results from the satellite measurements. The observations from Chandrayaan-1 reveal that the reflection of solar wind protons from magnetic anomalies is a common phenomenon on the Moon, occurring even at relatively small anomalies that have a lateral extent of less than 100 km. At the largest magnetic anomaly cluster (with a diameter of 1000 km), an average of ~10% of the incoming solar wind protons are reflected to space. Our computer simulations show that these reflected proton streams significantly modify the global lunar plasma environment. The reflected protons can enter the lunar wake and impact the lunar nightside surface. They can also reach far upstream of the Moon and disturb the solar wind flow. In the local environment at a 200 km-scale magnetic anomaly, our simulations show a heated and deflected plasma flow and the formation of regions with reduced or increased proton precipitation. We also observe solar wind protons reflected from the lunar regolith. These proton fluxes are generally lower than those from the magnetic anomalies. We find that the proton reflection efficiency from the regolith varies between ~0.01% and ~1%, in correlation with changes in the solar wind speed. We link this to a velocity dependent charge-exchange process occurring when the particles leave the lunar regolith. Further, we investigate how the properties of the reflected neutral hydrogen atoms depend on the solar wind temperature. We develop a model to describe this dependence, and use this model to study the plasma precipitation on the Moon when it is in the terrestrial magnetosheath. We then use the results from these and other studies, to model solar wind reflection from the surface of the planet Mercury. / Rymdmiljön runt månen formas av den växelverkan som sker mellan månen och solvinden. I den föreliggande avhandlingen undersöker vi två aspekter av denna växerverkan, nämligen växelverkan mellan solvindsprotoner och magnetiserade områden i månskorpan, och växelverkan mellan solvindsprotoner och månens ytdamm. Vi använder oss av partikelsensorer på månsatelliten Chandrayaan-1 för att analysera solvindsprotoner som reflekteras från månen, även de protoner som fångar upp en elektron från ytan och reflekteras som neutrala väteatomer. Vi använder oss också av datorsimuleringar för att bygga vidare på de uppmätta resultaten. Observationerna från Chandrayaan-1 visar att reflektion av solvindsprotoner från magnetiserade områden är ett vanligt förekommande fenomen på månen, som inträffar även vid magnetiseringar som är utbredda över mindre än 100 km. Vid det största magnetiserade området på månen (1000 km i diameter), reflekteras i genomsnitt ~10% av de infallande solvindsprotonerna. Våra datorsimuleringar visar att dessa protonflöden har globala effekter på månens plasmamiljö. De reflekterade protonerna kan nå månens nattsida. De kan också nå långt uppströms om månen och störa solvindsflödet. I den lokala plasmamiljön vid ett magnetiserat område av storleken 200 km visar våra simuleringar ett förändrat solvindsflöde, där det skapas områden som delvis skyddas från solvinden, likväl som områden som utsätts för mer solvind. Vi observerar även solvindsprotoner som reflekterats från ytdammet på månen. Dessa protonflöden är lägre än de från de magnetiska fälten. Reflektionen från ytan varierar mellan ~0.01% och 1% av solvindsflödet, i samband med förändringar i solvindshastigheten. Vi förklarar detta med att partiklarnas laddning bestäms av den hastighet de har när de lämnar måndammet. Vidare undersöker vi hur egenskaperna hos de reflekterade neutrala väteatomerna beror på solvindstemperaturen. Vi skapar en modell för att beskriva sambandet och använder sedan denna modell för att studera hur solvinden faller in mot månens yta när den befinner sig i jordens magnetoskikt, där jordens magnetfält orsakar en upphettning av solvindsflödet. Resultaten från dessa och andra studier använder vi sedan för att modellera solvindsreflektion från planeten Merkurius yta, för jämförelse med framtida observationer.

La connaissance de l’énergie transférée aux surfaces en contact avec un plasma basse pression est un paramètre clé pour le contrôle des procédés plasmas basse pression. Sa détermination permet une meilleure compréhension des mécanismes mis en jeu lors du dépôt ou la gravure de couches couches minces. Elle dépend des espèces du plasma (les ions, les électrons et les neutres) ainsi que de nombreux mécanismes physiques ou chimiques (réaction, condensation, émission radiative.). Elle peut être déterminée par la simulation du transport des particules dans le plasma, par des estimations de chaque contribution à partir des paramètres plasma ou tout simplement mesurée. Les études dédiées à sa mesure sont principalement basées sur l’utilisation d’une sonde calorimétrique, dont le principe sur l’interpolation du thermogramme mesuré. Ce type de méthode induit un long temps de mesure (2 min) et est source d’incertitudes. Un outil de diagnostic pour la mesure directe de l’énergie transférée a été développé au GREMI. Il est basé sur l’adaptation d’un capteur à thermopile initialement dédié à des mesures à pression atmosphérique. Cette thèse a donc été dédié à son développement et son utilisation pour l’étude de différents procédés plasmas basse pression : un propulseur spatial à effet Hall, un plasma poudreux, mais surtout de décharges magnétron. Des mesures ont été réalisées lors du dépôt de titane, d’aluminium, de TiO2 et de Al2O3. Les influences de la configuration magnétique de la cathode, du type de décharge, de l’échauffement des cibles, sur les conditions énergétiques à la surface du film en croissance ont été étudiées. / The knowledge of the energy flux during plasma/surface interactions is a key parameter for the control of low pressure plasmas, as sputter deposition or etching processes. The energy flux density at a surface depends on plasma species (ions, electrons, neutrals...) elementary processes (condensation, chemical reaction, radiative transfer). It can be obtained by carring out simulation of particule transport through the plasma, by the calculation of each energetic contribution from plasma parameters or by indirect or direct measurement. Most os works focused on the mesurement of the energy flux is based on the using of a calorimetric probe. This method is based on the calculation of the temporal temperature evolution. The main disadvantages are that this methods can cause error of about 10 % and the acquisition time of the thermogram which is about 2 min. A diagnostic tool which provide a direct measurement of the energy flux, with a good sensitivity and a good time resolution was designed in the GREMI.The aim of this PhD thesis was to developped this tool and use for the study of different plasma processes as capacitiv RF discharge, Hall effect plasma thruster and especially magnetron sputter deposition process. In this last process, the influence of the cathode magnetic configuration, the reactive gas, the dicharge type (HiPIMS, DCMS and pDCMS), the heating of the target was studied on the energy flux at the growing thin film duting the sputtering of a titanium and an aluminum target.

Doctor of Philosophy / Department of Chemistry / Daniel A. Higgins / This dissertation describes the application of wide-field single-molecule fluorescence microscopy techniques to investigations of DNA-surface interactions on chemically graded organosilane surfaces. The adsorption and desorption behaviors of double-stranded (ds) plasmid DNA along the amino-trimethoxysilane and octyl-trichlorosilane gradients were explored as a function of solution pH, solution ionic strength and surface properties. The results provide an improved fundamental understanding of DNA interactions with different surfaces and are certain to aid in the development and advancement of DNA-based biological and biomedical devices. Three distinct experiments were performed in completion of the work for this dissertation. In the first study, total internal reflection fluorescence (TIRF) microscopy was employed to study DNA interactions with aminosilane gradient surfaces under relatively acidic and basic environments. Electrical potentials were applied to assist DNA adsorption and desorption. The single-molecule data clearly showed that DNA capture and release was achieved on the monolayer and submonolayer coated regions of the aminosilane gradient surface under relatively basic pH conditions, with the help of an electrical potential. Meanwhile, DNA adsorption was found to be quasi-reversible on the multilayers at the high aminosilane end of the gradient in the relatively acidic solution. The results of these studies demonstrate the importance of manipulating the electrostatic interactions of DNA with charged surfaces in order to achieve DNA capture and release. The fundamental knowledge of the DNA-surface interactions gained in these studies will be helpful in diverse fields ranging from the layer-by-layer assembly of polyelectrolyte-based thin films to the selective electronic sensing of charged biomolecules. In the second study, the local dielectric properties of the least polar environments in dsDNA were assessed by using the solvatochromic dye, nile red, as a polarity-sensitive probe. TIRF spectroscopic imaging methods were employed in these studies. Although the dielectric constant within the least polar regions of dsDNA was previously predicted by theoretical and computational methods, no experimental measurements of its value had been reported to date. The results provide important knowledge of the factors governing the polarity of DNA microenvironments to which intercalators bind, and provide vital experimental support for the values determined in computational studies. In the third study, TIRF microscopy and single molecule tracking methods were employed to study DNA interactions with an opposed two-component C8-silane and aminosilane gradient surface as a function of solution pH. The mobility of surface-adsorbed DNA molecules was explored and quantified in these studies. The preliminary results further demonstrated the importance of electrostatic interactions over hydrophobic interactions in governing the adsorption of DNA to surfaces. The mobility of surface-adsorbed DNA was found to be largely independent of position along the two-component gradient. These studies were originally undertaken as a route to observation of cooperative effects that are believed to govern DNA-surface binding. Unfortunately, no clear evidence of cooperative effects was observed at the mixed regions of the two-component gradient surface.

Comprehension of reactive chemical dynamics in the gas phase and at the gas/organic-surface interface and non-reactive dynamics at the interface between hydrophobic surfaces and water requires an understanding of the fundamental atomic and molecular interactions that undergird these important phenomena. In an effort to study these regimes of chemical interaction, we have performed computational simulations that probe the dynamics of chemical systems that exemplify each of these domains. To study gas-phase chemical dynamics, we reparametrized semiempirical Hamiltonians so that they can accurately describe the potential energy surfaces for two distinct atom+alkane reactions. In addition to their demonstrated accuracy, these methods possess the attractive quality of being computationally inexpensive enough to afford extensive direct-dynamics trajectory studies. Our results on the dynamics of atom+alkane hydrogen-abstraction reactions have shown good agreement with experimental metrics that are as diverse as product velocity distributions, excitation functions, angular distributions and rovibrational state distributions for diatomic products of the abstraction. We have demonstrated that our reparametrized Hamiltonians are suitable for investigating gas-phase reactions with up to 15 (5 heavy) atoms and that they are appropriate for studying reactions beyond the gas phase, especially gas/surface reactions. By employing our semiempirical methods within a quantum-mechanics/molecular-mechanics hybrid scheme we are able to examine hydrogen-abstraction reactions of fluorine atoms with alkanethiolate self-assembled monolayers. Our simulations reproduce the general trends of experimental results for the cousin F+squalane reaction. Our simulations also probe the role that secondary collisions play in determining the final internal and translational energy of the product HF molecules. For instance, we determined that very few interactions with the SAM surface were required to cool rotational and translational modes of the HF product, while its vibrational energy remains unchanged on the time scale that HF molecules trap on the SAM surface. Moving beyond the gas/organic surface interface, we have also performed molecular-dynamics simulations of thin water films confined between hydrophobic SAM surfaces. These simulations illuminated the structural and dynamics behavior induced in the water films by confinement in hydrophobic environments. While most effects of the surface do not penetrate deep into the water layers we have noted that enhanced lateral diffusion of water molecules can persist in these films with > 1 nm length scales. We have elucidated a possible mechanistic precursor for the attractive forces seen in experimental measurement of the hydrophobic effect. / Ph. D.

Biomass is one of the most promising replacements for fossil fuels as a feedstock for chemical and transportation fuel production. The combination of low vapor pressure and high polarity of most biomass derived molecules makes water the ideal solvent for biomass upgrading reaction schemes. Metal oxide and metal oxide supported catalysts are heavily used in oil refining and petrochemical production, and are capable of upgrading biomass molecules as well. However, the surface chemistries that dictate the behavior of aqueous phase biomass upgrading reactions over metal oxide catalysts are not nearly as well understood as in the case of gas phase hydrocarbon refining systems. This dissertation aims to investigate the surface chemistries of biomass derived oxygenate molecules on metal oxide and metal oxide supported metal catalysts. There are three main objectives in this dissertation: to understand how two and three carbon polyols interact with metal oxide surfaces, to elucidate the role of various surface sites on polyol-metal oxide interactions, and to discover the surface species of kinetic importance in aqueous phase reforming reactions of biomass molecules. Transmission infrared spectroscopy and density functional theory modeling were the major techniques used to demonstrate that polyols with alcohol groups on the first and third carbons, 1,3-propanediol and glycerol, form a multidentate surface species with a bridging alkoxide bond and an acid/base interaction through their two primary alcohol groups with Lewis acid sites of g-Al₂O₃. These interactions occur in the presence of bulk water. Polyols with alcohol groups only on the first and second carbons, ethylene glycol and 1,2-propanediol, only formed alkoxy bonds with the g-Al₂O₃ surface when bulk water was not coadsorbed, and these bonds were removed by re-adsorbing water. Glycerol also forms the same surface species on other metal oxides with strong Lewis acidic character: TiO₂ anatase, ZrO₂, and CeO₂. Glycerol only forms hydrogen bonds with MgO, which lacks strongly Lewis acidic sites. Basic surface hydroxyls and surface oxygen atoms of the metal oxides only played a minor role in interacting with the adsorbed glycerol. In-situ attenuated total reflectance infrared spectroscopy demonstrated that the aqueous phase reforming of glycerol over a 5 wt% Pt on g-Al₂O₃ catalyst is hindered by residual platinum bound hydrogen or oxygen atoms from commonly utilized catalyst reduction or cleaning procedures, respectively. A pretreatment consisting of multiple iterations of dissolved oxygen, dissolved hydrogen, and dissolved helium in water flow periods provides the cleanest Pt surface for monitoring carbon monoxide formation dynamics, and allows for observing the rate limiting step of the aqueous phase reforming reactions water-gas shift removal of Pt bound carbon monoxide. The bridging bound carbon monoxide is preferentially removed over the linearly bound species via water gas shift reactions even at room temperature.