Kondoju, Siddartha (The University of Arizona., 2007)
In copper chemical mechanical planarization (CMP), in situ detection of barrier to dielectric layer transition is typically done using an optical reflectance technique. The introduction of carbon doped oxides (CDOs) as low-dielectric constant (k) materials for dielectric layers has opened up the possibility of using spectroscopic techniques for detecting such transitions more efficiently. The vibrational frequencies of the bonds between C, H, O, and Si in these low-k materials may be readily detected by spectroscopic techniques such as Raman and infrared (IR) spectroscopies. Since CMP is carried out in aqueous media, IR spectroscopy is not very desirable due to strong absorption of water in the same region as C-H vibrations (2800 cm⁻¹ to 3300 cm⁻¹). In contrast, Raman spectroscopy shows minimal water interference and can be used to efficiently monitor the signal from CDO films even in aqueous environments that prevail under CMP conditions. The research reported in this dissertation concerns the use of Raman spectroscopy in detecting the transition from tantalum (Ta) barrier layer to CDO dielectric layer, insitu. Intensities of Raman peaks characteristic of Si-Si vibrations from silicon substrates and C-H vibrations from low-k materials were used for monitoring CDO thickness and detecting removal of Ta layer. An abrasion cell was integrated with a Raman spectrometer to demonstrate the feasibility of Raman monitoring in-situ. Additionally, an alternative method was investigated for monitoring transitions in highly fluorescent low-k materials where Raman can not be used. The fluorescence intensity was used to effectively monitor Ta to low-k transitions. As a secondary objective, the Raman technique was used to monitor the composition of polishing slurries, which in the case of copper CMP, have a rich chemistry, which may change during the course of polishing due to consumption and decomposition of certain constituents. Various aspects, such as small layer thickness (<50 μm), continuous flow of the slurry, and dynamics of the film removal process pose a great challenge to the monitoring of slurry components between the pad and the wafer. The slurry constituents such as oxidants and corrosion inhibitors have unique signatures that can be detected using spectroscopic techniques. In this study Raman spectroscopy was used to detect and quantify chemical species such as hydroxylamine, benzotriazole and hydrogen peroxide in-situ. A more detailed study pertaining to the protonation of hydroxylamine with respect to the pH was also performed. Finally, surface enhanced Raman spectroscopy (SERS) was also investigated to improve the detection of pyridine and benzotriazole at low concentrations (<100 ppm).
In hydrometallurgical copper production plants, titanium-based electrodes coated with a conductive layer of IrO2-Ta2O5 are widely used as anodes in acidic copper electrowinning baths because of their long service life and low overpotential for oxygen evolution. The presence of trace amounts of ions such as fluoride, aluminum, and iron in sulfate-based electrowinning baths is believed to affect the stability of IrO2-Ta2O5 coated anodes. Hence, in this study, the effect of fluoride and metallic cations on the lifetime of IrO2-Ta2O5 coated Ti electrodes in sulfuric acid solutions has been investigated, and a degradation mechanism for IrO2-Ta2O5 coatings in the presence of fluoride has been proposed. Typical lifetime of the conductive ceramic coated anodes is 1 to 2 years. In order to predict electrode performance over this long period, an accelerated laboratory test that can be carried out in a few weeks is often used. This test, known as accelerated lifetime test (ALT), is conducted by electrically stressing the anodes at a current density that is much higher than the current density used for electrowinning while monitoring the change in the cell potential. The time required for the cell voltage to increase by 5 V is taken as the accelerated lifetime of the oxide electrode. In this research, titanium mesh samples coated with mixed iridium oxide-tantalum oxide layers were tested as anodes in 2 M sulfuric solution a constant current density of 0.54 A/cm2. A two-electrode cell with a bare titanium mesh serving as the cathode was used for experiments. In addition to ALTs, anodic polarization measurements were also carried out to study the changes in overpotential for oxygen evolution on electrodes before and after ALTs. Additionally, morphology and chemical composition analyses were performed on electrodes before and after ALTs using various techniques such as scanning electron microscopy (SEM) analysis, energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Chemical species that are likely to be present in the electrowinning bath were predicted using the computer software STABCAL and presented in distribution-pH and Pourbaix diagrams. The results of multiple ALTs in the absence and presence of various levels of fluoride indicate that the anode lifetime was greatly reduced by the presence of fluoride in sulfuric acid solutions. The greater the amount of fluoride added, the shorter the anode lifetime. Additionally, both in the absence and presence of fluoride, the molar ratio of IrO2 to Ta2O5 in the coating did not change during dissolution. In studying strategies to prolong the lifetime of the electrode in a fluoride-containing solution, a method of complexing fluoride ions using metallic cations such as Al3+ and Fe3+ was developed and demonstrated. The anode lifetime was successfully prolonged from 200 to over 500 hours with the addition of aluminum ions to a fluoride-containing solution. Compared with ferric ions, aluminum ions are more efficient in complexing with fluoride to extend the lifetime of electrodes.
Balachandran, Rajesh (The University of Arizona., 2015)
Over the years, megasonic energy has been widely used in the semiconductor industry for effective particle removal from surfaces after chemical mechanical planarization (CMP) processes. As a sound wave propagates through a liquid medium, it generates two effects, namely, acoustic streaming and acoustic cavitation. Acoustic streaming refers to time independent motion of liquid due to viscous attenuation, while cavitation arises from the bubble activity generated due to the difference in the pressure field of the propagating wave. Cavitation can be classified into two categories, (1) stable and (2) transient cavitation. When a bubble undergoes continuous oscillations over repeated cycles it is known to exhibit stable cavitation, while a sudden collapse is referred to as transient cavitation. Due to the rapid implosion of the transient cavity, drastic conditions of temperature (5,000-10,000 K) and pressure (hundreds of bars) are generated within and surrounding the bubble. If this phenomenon occurs close to the substrate, it causes damage to the sub-micron features. In this study, emphasis has been laid on understanding acoustic cavitation as it is critical to achieving high cleaning efficiency without any feature damage. The research work described in this dissertation has been divided into three sections. In the first part of the dissertation, the development of a novel sono-electrochemical technique for removal of sub-micron (300 nm) silica particles from conductive surfaces (Ta) has been discussed. The technique employs megasonic field at low pulse time and duty cycle in conjunction with an applied electrical field for achieving superior particle removal efficiency (PRE). In order to demonstrate the effectiveness of the sono-electrochemical technique, cleaning studies were conducted using 300 nm silica particles both in the presence and absence of an applied electrical field in air and argon saturated solutions. In the presence of the megasonic field (0.5 W/cm², 10% duty cycle, 5ms pulse time) alone, about 55% PRE was observed in Ar saturated DI water, while in the presence of the sono-electrochemical field (-1.5V vs Ag/AgCl (sat. KCl)), about 80% PRE was measured. The enhancement in particle removal efficiency was attributed to oscillating hydrogen bubbles formed from water reduction in close vicinity of the tantalum surface, that grow to a resonant size under suitable acoustic conditions and likely cause removal of particles. Interestingly, increasing the applied potential to -2V (vs Ag/AgCl (sat. KCl)) enhanced the particle removal efficiency to about 100%. Investigations were also performed in solutions containing 10 mM potassium chloride (KCl). The results revealed that even at low applied potentials of -1.5V, almost complete particle removal was achieved. This improvement in PRE was attributed to a combined effect of microstreaming and electro-acoustic forces. The results revealed that almost complete removal of particles could be achieved at low power density and duty cycle when a sound field at 1 MHz is used in conjunction with electrochemistry. The second study focuses on the effect of acoustic frequency and transducer power density for the development of a damage-free megasonic cleaning process. Here, an effort was made to characterize cavitation activity at acoustic frequencies of 1, 2 and 3 MHz by means of electrochemical, acoustic emission and fluorescence spectroscopy techniques. Studies conducted with a microelectrode using ferricyanide as an electroactive species showed that at 1 MHz and 2 W/cm², current peaks with a rise and fall time of about 30-50 ms and 80-120 ms were observed, respectively, which were indicative of transient cavitation behavior. Interestingly at higher frequencies (3 MHz), symmetric and oscillatory behavior in the current was observed. The rise and fall times were about 3 orders of magnitude lower at about 50 µs. This oscillatory behavior in the current at 3 MHz was attributed to the presence of stable cavities. Furthermore, hydrophone studies supported the microelectrode studies as they showed a reduction of about two orders of magnitude in the intensity of transient cavitation as frequency was increased from 1 to 3 MHz. Hydroxyl radical (OH*) capture measurements using terephthalate dosimetry corroborated the above results as they illustrated an order of magnitude decrease in OH* generation rate at 3 MHz compared to 1 MHz. These studies suggest that the use of higher megasonic frequencies may be more suitable for damage-free and effective cleaning of patterned surfaces in the semiconductor industry. In the last part of the dissertation, we investigate the effect of solution parameters on cavitation characteristics using a bicarbonate based alkaline chemical cleaning formulation that has been previously demonstrated to be beneficial in achieving effective megasonic cleaning and low damage. The results of this study revealed that in the presence of ammonia (NH₃) or carbonate/bicarbonate ions at concentrations greater than 75 mM or 200 mM respectively, the measured rate of generation of hydroxyl radicals at 1 MHz and 2 W/cm² was significantly reduced. The lower rate of OH· was attributed to scavenging of radicals in these solutions and additionally due to reduced transient cavitation in ammonia solutions. Hydroxyl radical measurements at higher power density of 8 W/cm² showed that carbonate ions were better scavengers of hydroxyl radicals than bicarbonate ions. The study on the effect of bulk solution temperature illustrated that the rate of generation of OH· increased with increase in temperature from 10 to 30 °C suggesting enhanced transient cavitation at higher temperatures (in the investigated range). The use of optimum concentration of ammonia or carbonates ions in cleaning formulation and bulk solution temperature would likely provide desired cleaning with minimum damage.
Schnittker, Kimberlin (The University of Arizona., 2017)
Four silicon nitride powder blends vary in starting powder characteristics, glass chemistry, and phase composition. This work focuses on how these properties influence densification behavior, microstructural development, and the resulting mechanical performance of dense ceramics. Previous work completed on alpha-rich, low oxide containing (8 wt%), and fine silicon nitride powder (GS-44) showed high hardness equiaxed with grained ceramic. GS-44 served as an excellent precursor for the matrix phase material in graphene reinforced composites, which resulted in 235% increase in toughness and high hardness retention  with the addition of 1.5 vol% graphene. As the GS-44 powder is no longer in production, investigative work into other commercial powders and customization of powder blends was initiated. Commercial blends were selected based on availability, high alpha content, fine particle size, and additive chemistry (Al2O3, MgO, and Y2O3). The objective was to understand which powder characteristics led to a ceramic design that contained high hardness, strength, and toughness properties in order to increase the use of silicon nitride in extreme temperature environments. One such example is aerospace and structural applications that require a high-performance material that is lightweight and good thermal stability. Strong covalent bonding in silicon nitride make densification of powders extremely difficult; thereby, sintering additives are necessary to promote liquid phase sintering processes. Compaction of ceramic powders was carried out using a spark plasma sintering (SPS) furnace by utilizing a pulsed direct current through a conductive graphite die that encapsulates the sample powder. SPS was preferred over other conventional sintering methods owing to its high heating rate and short dwell times at the sintering target temperature. Thus, SPS provides superior control for tailoring the final silicon nitride properties by producing a hard alpha-phase and tough beta-phase microstructures. The custom blend developed had an appreciable amount of media wear included during the milling process that increased the additive content. Development of the custom blend was used to understand the effect of a larger additive content. Commercial GS-44 blend was used as the control to track the effect of adjusting specific surface area and oxide content in silicon nitride powder systems (HCS-M, C-R3, and UA-SN). The mechanical results for the four matrix systems, showed that toughness increased with grain coarsening and minimization of alumina content in beta silicon nitride. Based on these findings it is important to determine tradeoffs (i.e. balance of high hardness, toughness, and strength) to engineer an optimal ceramic that can be used for structural and aerospace applications.
Microtubules (MTs), whose basic units are a and ß tubulin proteins, are self-assembled proteinaceous filaments with nanometer scale diameters and micrometer scale lengths. Their aspect ratio, directionality, the reversibility of their assembly and their ability to be metallized by electroless plating make them good candidates to serve as templates for the fabrication of nanowires and other nanoscale devices. In addition, tubulin proteins can provide biological interactions with a naturally high specificity.Toward the goal of manufacturing MT-based metallic nanowires and networks of nanowires on a silicon wafer, I studied the influence of pH, temperature, and several biomolecules on the stability of MTs in solutions, as well as the surface effect on the dynamics of disassembly of microtubules. Secondly, I demonstrated the metallization of MTs by electroless nickel plating both in solution and on hydrophilic oxidized Si surface. After being activated by Pt, nickel coated MT surfaces during the electroless plating, with a thickness of several nanometers. Due to the different kinetics of the process, MTs metallized on the oxidized Si wafer are slightly different from MTs metallized in solutions. Finally, we explored controlled nucleation and growth of microtubules directly from a collection of g-tubulin monomers. g-tubulins bind to modified gold electrodes on a silicon wafer through an organic linker, Glutathione s-transferase, creating a g-tubulin layer for MT growth. MTs unambiguously originated from the surface-bound g-tubulin layer on the gold electrode, proving that the surface-bound g-tubulin retains its biological ability of nucleating MT growth.
Fuel cells are one of most environmental friendly energy sources; they have many advantages and may be used in many applications from portable electronic devices to automotive components. Proton exchange membrane (PEM) fuel cells are one of most reliable fuel cells and have advantage such as rapid-startup and ease of operation. This dissertation focuses on PEM fuel cell stack optimization based on operation experimental research and numerical modeling study. This dissertation presents three major research activities and the obtained results by the Ph.D candidate. A novel stack architecture design is introduced in order to decrease mal-distribution and non-uniform output performance between individual cells in order to improve the stack performance. Novel stack architecture includes a novel external bifurcation flow distribution delivery system. One major issue of uniform distribution of reactants inside individual fuel cells and between fuel cells in a fuel cell stack is solved by the novel stack architecture design. A novel method for uniform flow distribution was proposed, in which multiple levels of flow channel bifurcations were considered to uniformly distribute a flow into 2ⁿ flow channels at the final stage, after n levels of bifurcation. Some detailed parameters such as the flow channel length and width at each level of bifurcation as well as the curvature of the turning area of flow channels were particularly investigated. Computational fluid dynamics (CFD) based analysis and experimental tests were conducted to study the effect of the flow channel bifurcation structure and dimensions on the flow distribution uniformity. Optimization design and factors influential to the flow distribution uniformity were also delineated through the study. The flow field with the novel flow distribution was then considered to be used in a cooling plate for large fuel cell stacks and a possible method for cooling electronic devices. Details of the heat transfer performance, particularly the temperature distributions, on the heating surface as well as the pressure losses in the operation were obtained. In the second part of the research, experimental testing, analytical modeling, and CFD methods were employed for the study and optimization of flow fields and flow channel geometry in order to improve fuel cell performance. Based on the experimental results, a serpentine flow field is chosen for CFD and modeling analysis. Serpentine flow channel optimization is based on the parametrical study of many combinations of total channel width and rib ratio. Modeling analysis and in-house made computational code was used to optimize the dimensions of flow channels and channel walls. It is recommended that cell channel design should use a small total channel width and rib ratio. Proton exchange membrane fuel cells were fabricated based on the optimization results. Experimental tests were conducted and the results coincided with the numerical analysis; therefore, small total width and rib ratio design could significantly improve the fuel cell performance. Three dimensional (3D) CFD simulations for various PEM fuel cells were conducted to investigate information such as water and reactants distribution. The direct simulation results of current density distribution proclaim how the channel design influences the performance. The final section of research is stack bipolar plate flow field optimization. Optimized channel geometries are applied to the serpentine channel design for the stack. This serpentine channel design evolved to parallel-serpentine channel and symmetric serpentine channel design. Experimental tests of the stacks using the above flow fields are compared to one another and the results recommend use of the novel symmetric serpentine flow channel for stack bipolar design to achieve best performance.
Padmanabhan Ramalekshmi Thanu, Dinesh (The University of Arizona., 2011)
Fabrication of current generation integrated circuits involves the creation of multilevel copper/low-k dielectric structures during the back end of line processing. This is done by plasma etching of low-k dielectric layers to form vias and trenches, and this process typically leaves behind polymer-like post etch residues (PER) containing copper oxides, copper fluorides and fluoro carbons, on underlying copper and sidewalls of low-k dielectrics. Effective removal of PER is crucial for achieving good adhesion and low contact resistance in the interconnect structure, and this is accomplished using wet cleaning and rinsing steps. Currently, the removal of PER is carried out using semi-aqueous fluoride based formulations. To reduce the environmental burden and meet the semiconductor industry's environmental health and safety requirements, there is a desire to completely eliminate solvents in the cleaning formulations and explore the use of organic solvent-free formulations.The main objective of this work is to investigate the selective removal of PER over copper and low-k (Coral and Black Diamond®) dielectrics using all-aqueous dilute HF (DHF) solutions and choline chloride (CC) - urea (U) based deep eutectic solvent (DES) system. Initial investigations were performed on plasma oxidized copper films. Copper oxide and copper fluoride based PER films representative of etch products were prepared by ashing g-line and deep UV photoresist films coated on copper in CF4/O2 plasma. PER removal process was characterized using scanning electron microscopy and X-ray photoelectron spectroscopy and verified using electrochemical impedance spectroscopy measurements.A PER removal rate of ~60 Å/min was obtained using a 0.2 vol% HF (pH 2.8). Deaeration of DHF solutions improved the selectivity of PER over Cu mainly due to reduced Cu removal rate. A PER/Cu selectivity of ~20:1 was observed in a 0.05 vol% deaerated HF (pH 3). DES systems containing 2:1 U/CC removed PER at a rate of ~10 and ~20 Å/min at 40 and 70oC respectively. A mixture of 10-90 vol% de-ionized water (W) with 2:1 U/CC in the temperature range of 20 to 40oC also effectively removed PER. Importantly, etch rate of copper and low-k dielectric in DES formulations were lower than that in conventional DHF cleaning solutions.
Lowalekar, Viral Pradeep (The University of Arizona., 2006)
In an ECMP process, a wafer is anodically baised during polishing. The electrical potential is the driving force to oxidize copper metal to ions. Copper ions then react with chemistry in the electrolyte to go in solution or form a passivation layer on the surface. The passivation layer is removed by a very low downforce (0.5-1 psi), causing copper to electrochemically dissolve in solution. Passive film formation during copper ECMP is key to the success of this process, since passivation reduces dissolution in the recessed areas, while elevations on the copper surface in direct contact with the ECMP pad are electrochemically planarized. If no passive film forms, then copper removal will be conformal from the elevated and recessed areas, and planarity will be lost. Chemical formulations for the electrochemical mechanical planarization (ECMP) of copper must contain constituents that are stable at anodic potentials. A key component of the formulation is a corrosion inhibitor, which is required to protect low lying areas while higher areas are selectively removed. Organic compounds, which adsorb on copper at low overpotentials and form a film by oxidation at higher overpotentials, may be particularly useful for ECMP. The main goal of the research reported in this dissertation is to understand and develop oxalic acid-based chemical systems suitable for ECMP of copper through electrochemical and surface investigations. Special attention was paid to the development of an inhibitor, which can function under applied potential conditions. Physical methods such as profilometry and four point probe were used to obtain copper removal rates. An organic compound, thiosalicylic acid (TSA), was identified and tested as a potential corrosion inhibitor for copper. TSA offers better protection than the conventionally used benzotriazole (BTA) by oxidizing at high anodic potentials to form a passive film on the copper surface. The passive film formed on the copper surface by addition of TSA was characterized by X-ray photoelectron spectroscopy. The oxidation potential of TSA was characterized using cyclic voltammetry. The passivation and repassivation kinetics was investigated in detail and a passivation mechanism of copper in oxalic acid in the presence of TSA is proposed. Copper removal experiments were performed on a specially designed electrochemical abrasion cell (EC-AC) in both the presence and absence of inhibitors. The effect of anodic potentials on the dissolution of copper was studied to identify suitable conditions for the electro-chemical mechanical planarization process.
Muthukumaran, Ashok Kumar (The University of Arizona., 2008)
Electro-Chemical Mechanical Planarization (ECMP) is a new and highly promising technology just reaching industrial application; investigation of chemistries, consumables, and tool/control approaches are needed to overcome technological limitations. Development of chemical formulations for ECMP presents several challenges. Unlike conventional CMP, formulations for ECMP may not need an oxidant. Organic additives, especially inhibitors used to control planarity (i.e. to protect recessed regions), need to be stable under applied anodic potential. To have a high current efficiency, the applied current should not induce decomposition of the formulations. In addition, to enable clearing of the copper film, the interactions between multiple exposed materials (barrier material as well as copper) must be considered. Development of a full sequence ECMP process would require the removal of the barrier layer as well. Chemical systems that exhibit a 1:1 selectivity between the barrier layer and copper would be ideal for the barrier removal step of ECMP. The main goal of this research is to investigate the chemistries suitable for ECMP of copper and tantalum films. Copper was electroplated onto the gold electrode of quartz crystals, and its dissolution/passivation behavior in hydroxylamine solutions was studied at different applied potential values. The dissolution rate of copper is pH dependent and exhibits a maximum in the vicinity of pH 6. Copper dissolution increases with respect to overpotential (η) and dissolution rates as high as 6000 Å/min have been obtained at overpotential of 750mV. While both benzotriazole (BTA) and salicylhydroxamic acid (SHA) serve as good inhibitors at lower overpotentials, their effectiveness decreases at higher overpotentials. A fundamental study was undertaken to evaluate the usefulness of a sulfonic acid based chemical system for the removal of tantalum under ECMP conditions. Tantalum as well as copper samples were polished at low pressures (~0.5 psi) under galvanostatic conditions in dihydroxy benzene sulfonic acid (DBSA) solutions maintained at different pH values. At a current density of 0.5 mA/cm² and a pH of 10, tantalum removal rate of 200 Å/min with a 1:1 selectivity to copper was obtained in 0.3M DBSA solutions containing 1.2M H₂O₂. The presence of a small amount (~ 0.1%) of colloidal silica particles was required to obtain good removal rates. A comparison of DBSA and methane sulfonic acid (MSA) based chemical system was studied for the removal of tantalum. The performance of DBSA is better than that of MSA. Additionally, DBSA solution has been used for tantalum nitride removal under ECMP conditions. However, DBSA is not as effective for tantalum nitride as it is for tantalum. Polishing of the patterned test structure in optimized solution containing 0.01M BTA results in complete removal of barrier layer and surface planarity is achieved.
Fabrication and synthesis of nanostructured materials are essential aspects of nanoscience and nanotechnology. Although researchers are now able to create and tailor different nanostructured materials, the ability to precisely control the materials' sizes, shapes, and properties at the nanoscale level remains challenging. The aim of this dissertation was to develop new methods to aid researchers in overcoming these challenges. The study investigated two different methods used to create one-dimensional carbon nanostructures, i.e. carbon nanotubes and carbon nanopillars.In the first section, chemical vapor deposition method was used to grow carbon nanotubes (CNTs). Studies examining the effects of methane and hydrogen flow rates on the growth of CNTs were conducted. Results indicated that multi-walled CNTs with metallic properties could be obtained at a methane flow rates as low as 300 cc/min. At higher methane flow rates, i.e. 600-700 cc/min, semiconducting single-walled CNTs and double-walled CNTs were produced. Another phase of this section developed a new and simple CNT growth method using a solid carbon source and indicated polyacrylonitrile and nanosized SiO₂ were effective in producing MWCNTs. In the second part, a new nanoimprint technique was developed to enable printing of nanostructures at sub-100nm level using various polymers. This technique inherited its high-resolution feature from traditional nanoimprint lithography, but without the use of pressure. To demonstrate, PAN nanopillar structures were printed and converted to carbon. In another phase of the part, the use of our imprint technique resulted in the creation and conversion of polysilazane nanostructures to ceramic for the first time.The final section of this dissertation is devoted to study the impact of porosity in gas diffusion layers (GDLs) on the performance of fuel cells. In one study, a new technique using SEM images to determine GDL porosity was developed. The difference between SEM calculated porosities and mercury intrusion porosimetry measurements were less than 2%. The second study characterized fuel cell performances using GDLs constructed with additional micro porous layers (MPLs) and treated with different wet proofing treatments (WPT). Results showed that when MPL is added, cell performance decreases. However, the increase in WPT in the MPL improved cell performance.
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