Chemical Mechanical Planarization (CMP) is one of the most critical processing steps that enables fabrication of multilevel interconnects. The success of CMP process is limited by the implementation of an optimized process and reduction of process generated defects along with post CMP surface characteristics such as dishing and erosion. This thesis investigates to identify various sources of defects and studies the effect of factors that can be used to optimize the process. The major contributions of this work are: Understanding the effect of temperature rise on surface tribology, electrochemistry and post CMP pattern effects during the CMP process; investigating the effect of pad conditioning temperature and slurry flow rate on tribology and post CMP characteristics; development of novel slurries using polymer hybrid particles and improvement in slurry metrology to reduce surface damage during CMP. From the current research, it was shown that the effect of temperature on CMP tribology is predominantly affected by the polishing parameters and the polishing pad characteristics more than the chemical nature of the slurry. The effect of temperature is minimal on the resulting surface roughness but the with-in die non-uniformity is significantly affected by the temperature at the interface. Secondly, in this research it was shown that the effectiveness and aggressiveness of the pad conditioning process is highly influenced by the conditioning temperature. This aspect can be utilized to optimize the parameters for the pad conditioning process. Further, post CMP characteristics such as dishing, erosion and metal loss on patterned samples were shown to decrease with increase in slurry flow rate. This research then concentrates on the development of novel low defect slurry using polymer hybrid abrasive particles. Several varieties of surface functionalized polymer particles were employed to make oxide CMP slurries. These novel slurries proved to be potential candidates to reduce surface damage during CMP as they resulted in low coefficient of friction and much less surface scratches as compared to conventional abrasives. Thus, this research helps to reduce defects and non-planarity issues during CMP process thereby improving yield and reducing the cost of ownership.

This thesis reports the rheological properties of algae slurries as a function of cell concentration for three microalgae species: Nannochloris sp.,Chlorella vulgaris, and Phaeodactylum tricornutum. Rheological properties ofalgae slurries have a direct impact on the agitation and pumping power requirements as well as process design for producing algal biofuels. This study measures the rheological properties of eight diff erent concentrations of each species ranging from 0.5 to 80 kg dry biomass/m³. Strain-controlled steady rate sweep tests were performed for each sample with an ARES-TA rheometer using a double wall couette cup and bob attachment. Shear rates ranged from 5 - 270 s⁻¹, corresponding to typical expected conditions. The results showed that Nannochloris sp. slurry behaved as a Newtonian fluid for concentrations up to 20 kg/m³. Samples with concentrations above 40 kg/m³ behaved as a shear thinning non-Newtonian fluid. The effective viscosity increased with increased biomass concentration for a maximum value of 3.3x10⁻³ Pa-s. Similarly, C. vulgaris slurry behaved as a Newtonian fluid with concentrations of up to 40 kg/m³, above which it displayed a shear thinning non-Newtonianf behavior and a maximum eff ective viscosity of 3.5x10⁻² Pa-s. On the other hand, P. tricornutum slurry demonstrated solely Newtonian fluid behavior, with the dynamic viscosity increasing with increasing biomass concentration for a maximum value of 3.2x10⁻³ Pa-s. The maximum observed e ffective viscosity occurred at a concentration of 80 kg/m³ for all three species. Moreover, an energy analysis was performed where a non-dimensional bioenergy transport e ffectiveness was de termined as the ratio of the energy content of the transported algae biomass to the sum of the required pumping power and the harvesting power. The results show that the increase in major losses due to increase in viscosity was overcompensated by the increase in the transported biomass energy. Also, cultivating a more concentrated slurry requires less dewatering power and is the preferred option. The largest bioenergy transport eff ectiveness was observed for the slurries with the largest initial dry biomass concentrations. Finally, the relative viscosity of algae slurries was modeled using a Kelvin-Voit based model for dilute and concentrated viscoelastic par- ticle suspensions. The model, which depends primarily on the packing factor of the algae species, agrees with the measured viscosity with an average error of 18%, while the concentrated particle suspension model was slightly more accurate than the dilute suspension model. / text

This dissertation presents a series of studies related to the characterization and optimization of consumables during Chemical Mechanical Planarization (CMP). These studies are also evaluated with the purpose of reducing the cost of ownership as well as minimizing the potential environmental impacts. It is well known that pad-wafer contact and pad surface micro-structure have significant impacts on polishing performance. The first study in this dissertation investigates the effect of pad surface contact and topography on polishing performance during copper CMP. Two different types of diamond discs (3M A2810 disc and MMC TRD disc) are used to condition the polishing pad. Pad surface contact area and topography are analyzed using laser confocal microscopy and scanning electron microscopy (SEM) to illustrate how variations in pad surface micro-texture affect the copper removal rate and the coefficient of friction (COF). Polishing results show that the 3M A2810 disc generates significantly higher COF (16%) and removal rate (39%) than the MMC TRD disc. Pad surface analysis results show that the 3M A2810 disc and MMC TRD disc generate similar pad surface height probability density function and pad surface abruptness. On the other hand, the MMC TRD disc generates large flat near contact areas that correspond to fractured and collapsed pore walls while the 3M A2810 disc generates solid contact area and clear pore structures. The fractured and collapsed pore walls generated by the MMC TRD disc partly cover the adjacent pores, making the pad surface more lubricated during wafer polishing and resulting in a significantly lower COF and removal rate. In the next study, the individual "large" pad surface contact areas are differentiated from the "small" contact areas and their role in copper CMP is investigated. Surface topography and the structure of a typical individual large contact area are examined via laser confocal microscopy and SEM. In addition, the Young's Modulus of the pad surface material is simulated. A case study is presented to illustrate the role of the individual large contact area of IC1000 K-groove pad in copper CMP. SEM analysis shows that the individual large pad surface contact areas are induced by fractured pore walls and loosely attached pad debris. Simulation results indicate that individual large contact areas correspond to very low values of the Young's modulus (about 50 MPa). Such low values indicate that the pad material is soft and the summit underlying the individual large contact is not fully supported. As a result, individual large contact area implies low contact pressure and may contribute little to removal rate. Case study results confirm that the individual large contact area has minimal contribution to removal rate and indicate that the removal rate is mainly caused by small individual contact areas. In our case, small contact areas correspond to those smaller than 9 square microns. We believe that this methodology can be also applied for other kinds of pad, although the threshold values that may define "small" and "large" individual contact areas for different pads and processes need to be further investigated. In the third study, the effect of pad surface micro-texture in interlayer dielectric CMP is also investigated. Blanket 200-mm oxide wafers are polished and the polishing pad is conditioned under two different conditioning forces (26.7 and 44.5 N). Results show that when conditioning force is increased from 26.7 to 44.5 N, oxide removal rate increases by 65% while COF increases by only 7%. Pad surface contact area and topography are measured and analyzed to illustrate their effects on the oxide removal rate. While the two conditioning forces generate similar pad surface abruptness, pad surface contact area is significantly lower (by 71%) at the conditioning force of 44.5 N. Such dramatic decrease in pad surface contact area leads to a significant increase in local contact pressure and therefore results in a significant increase in oxide removal rate. The oxide removal rate and local contact pressure exhibits a Prestonian relationship. Besides the above studies on the effect of the pad surface micro-texture during blanket wafer polishing, the fourth study investigates how pad micro-texture affects dishing and erosion during shallow trench isolation (STI) patterned wafer polishing. Two different types of diamond discs (3M A2810 disc and MMC TRD disc) are used to condition the pad during wafer polishing. Dishing and erosion analysis for the patterned wafer polishing is performed using a surface profiler. To illustrate the effect of pad surface micro-texture on dishing and erosion, pad surface abruptness and mean pad summit curvature are analyzed using laser confocal microscopy. Polishing results show that the two discs generate similar blanket wafer removal rates, while the MMC TRD disc generate significantly higher dishing and erosion than the 3M A2810 disc during patterned wafer polishing. Results of pad surface micro-texture analysis show that the MMC TRD disc generates sharper asperities with higher mean pad summit curvature than the 3M A2810 disc, resulting in higher dishing and erosion. Another contribution of this dissertation is the development of a slurry film thickness quantification technique using ultraviolet-enhanced fluorescence. The technique is developed to measure slurry film thickness at any location of interest. In the next study of this dissertation, this new technique is applied to determine how two different slurry application/injection schemes (standard pad center area application method and novel slurry injection system) along with various polishing conditions such as sliding velocity, ring pressure and slurry flow rate affect slurry availability in the bow wave region of the polisher. For the standard pad center area application method, slurry is directly applied onto the pad center area and a large amount of fresh slurry flow directly off the pad surface without flowing to the pad-retaining ring interface due to the centrifugal forces. For the novel slurry injection system, slurry is introduced through an injector that is placed adjacent (<3 cm) to the retaining ring on the pad surface. Such a close distance between the injector and retaining ring allows most of the fresh slurry to be delivered efficiently to the leading edge of the retaining ring after it is injected onto the pad surface. Results show that the novel slurry injection system generates consistently thicker bow waves (up to 104 percent) at different sliding velocities, slurry flow rates and ring pressures, therefore providing more slurry availability for the pad-retaining ring interface and potentials for slurry consumption reduction in CMP processes. First order calculations yield estimates of slurry savings associated with the novel slurry injection system ranging between 8 and 48 percent depending on specific process conditions. In the last study of this dissertation, the effect of retaining ring slot design and polishing conditions on slurry flow dynamics at the bow wave is investigated. The ultraviolet-enhanced fluorescence technique is employed to measure the slurry film thickness at the bow wave for two retaining rings with different slot designs. Multiple sliding velocities, slurry flow rates and ring pressures are investigated. Results show that the retaining ring with the sharp angle slot design (PEEK-1) generates significantly thicker (on average 48%) slurry films at the bow wave than PEEK-2 which has a rounded angle slot design. For PEEK-1, film thickness at the bow wave increases with the increasing of flow rate and ring pressure and decreases with the increasing of sliding velocity. On the other hand, film thickness at bow wave does not change significantly for the PEEK-2 ring at different polishing conditions indicating an apparent robustness of the PEEK-2 design to various operating conditions. With retaining rings having different designs, and all else being the same, a thinner bow wave is preferred since it is indicative of a ring design that allows more slurry to flow into the pad-wafer interface. Therefore, the work underscores the importance of optimizing retaining ring slot design and polishing conditions for efficient slurry utilization.

As a result of the problem of hydrate in multiphase pipelines in offshore production is becoming more and more severe with the increasing of the water depth, the study on oil-gas-water-hydrate has became a hot point of multiphase flow. In this paper, the hydrate particle and liquid phase was treated as pseudo-fluid, the steady hydraulic, thermodynamical and phase equilibrium calculation method of gas-hydrate slurry was developed. Comparison was carried out between calculated data and experimental data from flow loop in our laboratory. With strict flash calculation the following items were determined: the amount of hydrate; phase number; the location that hydrate appeared; flowrate and molar component of gas phase and liquid phase. Then thermodynamic quantities were carried out with proper relational expression. When Compositional model is used to simulate two phase flow, it is required to couple mass, momentum, energy equation and equation of state. In the other word, the parameters in these four equations are interacted. However they are all the functions of p, T and z. In steady condition, it’s assumed that the composition of fluid is unchangeable along the pipeline and the flow can be described by pressure and temperature. In this paper, calculation method of gas-liquid two phase flow which respectively was improved. Liquid holdup and pressure drop were calculated by momentum equation. Enthalpy balance equation was substituted by explicit formulation of temperature calculation which meant that the loop of temperature was not required.

The purpose of this study is to develop the production method of CO2 hydrate-slurry. In this paper, the production process of CO2 hydrates with pure water dissolved antifreeze proteins (AFPs) is discussed. CO2 hydrate-slurry can be transported from a production place to storage one with a small pressure loss. The AFPs have made the hydrate particles be small and well disperse. It is revealed that the Type III AFPs are effective for the inhibition of structure I hydrate production. By the present experiments, the induction time for the hydrate production increases, and moreover the formation rate of the hydrate and the increasing rate of an agitator torque decrease.

North American petroleum refineries use landfarming to dispose of hydrocarbon-containing wastes for bioremediation by indigenous soil microorganisms. In this study, we isolated PAH-degrading bacteria from landfarm soil by enrichment with hydrocarbon-containing effluent. One isolate, Arthrobacter sp. UG50, was capable of using phenanthrene and anthracene as sole carbon sources. The strain degraded phenanthrene (200 mg/L) within 24 h in pure culture at high cell density (10e8 cells/mL). Anthracene (50 mg/L) was slowly degraded, with 29% degraded within 21 days. The strain could not use naphthalene, pyrene, chrysene or benzo(a)pyrene as sole carbon sources, but could degrade pyrene (50 mg/L) cometabolically when phenanthrene was provided. Anthracene degradation (50 mg/L) was enhanced by phenanthrene, with 100% degraded within 6 days. The addition of strain UG50 to petroleum sludge in baffled flasks increased total hydrocarbon degradation and degradation of low concentrations of fluorene, phenanthrene, pyrene and chrysene compared to flasks with limited aeration or containing sludge alone. / NOVA Chemicals and the Ontario Centres of Excellence

Phosphorus (P) pollution has been identified as the most significant agriculture-related threat to water quality impairment in Canada. One approach to reduce P pollution is to identify soils with high P loss potential and develop management strategies to minimize that risk. This thesis contributes towards greater understanding of short- and long- term P dynamics in soils to which different P sources had been applied (Chapters 3 and 4) and improvement in the P measurements for determining long-term P loss potential (Chapter 5). Chapter 3 evaluated immediate and residual effects of swine manure and fertilizer on soil P. Soils were sampled from Brookston clay loam in south-western Ontario, Canada which were treated with liquid (LM), solid (SM), composted (MC) manure and fertilizer, only in the corn phase. Soils were analyzed using a modified Hedley’s fractionation. All P sources influenced soil labile and moderately labile P in the year of application, while MC and SM showed significant residual impacts in the following year. Residual effects of MC and SM are beneficial for crops; however, there may be a P loss potential through leaching and runoff. Chapter 4 considered long-term effects of dairy manure slurry (DMS) and ammonium nitrate (AN) on soil P. Soils were sampled from south coastal region of BC, Canada, which were treated with DMS or AN at 50 or 100 kg NH4-N ha-1, and analyzed using a modified Hedley’s fractionation. DMS significantly increased labile and moderately stable P in surface soil, indicating short- and long-term impacts on P availability and loss potential. Chapter 5 analyzed a new test to predict long-term soil P loss potential. Soils were collected from four agro-ecological areas across Canada, and analyzed using Mehlich-3, Olsen, Resin strips (RMS), FeO-strips, and new procedures: various combinations of NaOH with and without EDTA, with four shaking periods. Statistically significant linear and quadratic relationships between the RMS and NaOH with EDTA-P indicated that the latter provide an efficient basis for predicting long-term soil P loss potential. A highly significant relationship between RMS-P and 0.025M NaOH with EDTA-P indicates this extractant was effective for measuring Total Releasable P. / Agriculture and Agri-Food Canada

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