This work demonstrates a capable reverse pulse deposition methodology to influence gap fill behavior inside microvia along with a uniform deposit in the fine line patterned regions for substrate packaging applications. Interconnect circuitry in IC substrate packages comprises of stacked microvia that varies in depth from 20µm to 100µm with an aspect ratio of 0.5 to 1.5 and fine line patterns defined by photolithography. Photolithography defined pattern regions incorporate a wide variety of feature sizes including large circular pad structures with diameter of 20µm - 200µm, fine traces with varying widths of 3µm - 30µm and additional planar regions to define a IC substrate package. Electrodeposition of copper is performed to establish the desired circuit. Electrodeposition of copper in IC substrate applications holds certain unique challenges in that they require a low cost manufacturing process that enables a void-free gap fill inside the microvia along with uniform deposition of copper on exposed patterned regions. Deposition time scales to establish the desired metal thickness for such packages could range from several minutes to few hours. This work showcases a reverse pulse electrodeposition methodology that achieves void-free gap fill inside the microvia and uniform plating in FLS (Fine Lines and Spaces) regions with significantly higher deposition rates than traditional approaches. In order to achieve this capability, systematic experimental and simulation studies were performed. A strong correlation of independent parameters that govern the electrodeposition process such as bath temperature, reverse pulse plating parameters and the ratio of electrolyte concentrations is shown to the deposition kinetics and deposition uniformity in fine patterned regions and gap fill rate inside the microvia. Additionally, insight into the physics of via fill process is presented with secondary and tertiary current simulation efforts. Such efforts lead to show “smart” control of deposition rate at the top and bottom of via to avoid void formation. Finally, a parametric effect on grain size and the ensuing copper metallurgical characteristics of bulk copper is also shown to enable high reliability substrate packages for the IC packaging industry.

Honeywell is currently extending the reach of additive manufacturing (AM) in its product line and expects to produce as much as 40% of its inventory through AM in five years. Additive manufacturing itself is expected to grow into a $3.1 billion dollar industry in the next 5 to 10 years. Reusing IN 718 powder, a nickel-based super alloy metal powder, is an ideal option to reduce costs as well as reduce waste because it can be used with additive manufacturing, but the main obstacles are lack of procedure standardization and product quality assurances from this process. The goal of the capstone project, "Effect of Powder Reuse on DMLS (Direct Metal Laser Sintering) Product Integrity," is to create a powder characterization protocol in order to determine if the IN 718 powder can be reused and what effect the IN 718 reused powder has on the mechanical properties of the products Honeywell fabricates. To provide context and impact of this capstone project, this paper serves to identify the benefits of AM for Honeywell and the cost effectiveness of reusing the powder versus using virgin powder every time. It was found that Honeywell's investment in AM is due to the cost effectiveness of AM, versatility in product design, and to ensure Honeywell remains competitive in the future. In terms of reducing expenses, reusing powder enables costs to be approximately 45% less than using virgin powder. With these key pieces of information, the motivations for this capstone project are understood to a fuller and more profound degree.

The purpose of this honors project is to analyze the difference between different powder separation techniques, and their suitability for my capstone project – ‘Effect of Powder Reuse on DMLS (Direct Metal Laser Sintering) Product Integrity’. Due to the nature of my capstone project, my group needs to characterize foreign contaminants in IN 718 (Ni-based superalloy) powder with a mean diameter around 40um. In order to clearly analyze the contaminants and recycle useful IN 718 powders, powder separation is favorable since the filtered samples will be much easier to characterize rather than inspect all the powders at once under microscope. By conducting literature review, I found that powder separation is commonly used in Geology, and Chemistry department. To screen which combination of techniques could be the best for my project, I have consulted several research specialists, obtained adequate knowledge about powder separation. Accordingly, I will summarize the pros and cons of each method with regard the specific project that I am working on, and further explore the impacts of each method under economical, societal, and environmental considerations. Several powder separation techniques will be discussed in details in the following sections, including water elutriation, settling column, magnetic separation and centrifugation. In addition to these methods, sieving, water tabling and panning will be briefly introduced. After detailed comparison, I found that water elutriation is the most efficient way to purity IN718 powder for reuse purpose, and recovery rate is as high as 70%, which could result in a significant reduction in the manufacturing cost for Honeywell since currently Honeywell only use virgin powders to build parts, and 90% of the leftover powders are discarded.

This project sought to analyze the effects of recycling Inconel 718 powder for Direct Metal Laser Sintering (DMSL) for additive manufacturing by testing low cycle fatigue tensile samples ranging from virgin to ten times recycled. Fracture generally occurs at the sample surface where persistent slip planes form and accumulate to cause a sudden fracture leading to signature markings for various phases of crack growth. Effects caused by contamination would be found in the first region of crack growth at the initiation site as the cause stress concentration. Tensile strength and fatigue life were compared to initiation site size found from fracture images obtained using scanning electron microscope imaging which found no significant deviations from the expected surface cracking and LCF region of slip plane buildups. Contamination was not found at any initiation site indicating that fracture life was not impacted by the amount of powder recycling. LCF life ranged from 60,000 to 250,000 which the majority experiencing fractures near 120,000 cyclic loadings. If defect effects were to be found than the low fatigue life sample would exhibit them however its fracture surface did not exhibit contamination but a slight increase in porosity found in the phase III cracking region. The In 718 powders were also analyzed to determine that the primary powder contaminates were brush fibers used to sweep away unused powders during processing however these were not seen in the final DMLS samples.

The work for this thesis was done in conjunction to that of my capstone project, which focused on understanding the effects of powder re-use on products built via Direct Metal Laser Sintering (DMLS), a specific additive manufacturing (AM) technique where powder particles are sintered together to form final parts. Honeywell Aerospace helped support this research by providing materials and mentorship; this work will play a key role in their decision to implement DMLS and other AM methods on a larger scale. Whereas the capstone focuses on the technical details of constructing characterization equipment, analyzing data, and formulating a concluding recommendation on whether the powder can be re-used, the thesis attempts to put this body of work in its greater context, surveying the economic and environmental effects of additive manufacturing technologies with a slant towards the aerospace industry. Shifts in the supply chain with aircraft parts and how this affects costs are explored, as well as how the quality and reliability of additively manufactured parts differs from their traditionally manufactured counterparts and the effects of this on related industries and purchasers.

The microstructure development of Inconel alloy 718 (IN718) during conventional processing has been extensively studied and much has been discovered as to the mechanisms behind the exceptional creep resistance that the alloy exhibits. More recently with the development of large scale 3D printing of alloys such as IN718 a new dimension of complexity has emerged in the understanding of alloy microstructure development, hence, potential alloy development opportunity for IN718.

This study is a broad stroke at discovering possible alternate microstructures developing in Direct-Metal-Laser-Sintering (DMLS) processed IN718 compared to those in conventional wrought IN718. The main inspiration for this study came from creep test results from several DMLS IN718 samples at Honeywell that showed a significant

improvement in creep capabilities for DMLS718 compared to cast and wrought IN718 (Honeywell).

From this data the steady-state creep rates were evaluated and fitted to current creep models in order to identify active creep mechanisms in conventional and DMLS IN718 and illuminate the potential factors responsible for the improved creep behavior in DMSL processed IN718.

Because rapid heating and cooling can introduce high internal stress and impact microstructural development, such as gamma double prime formations (Oblak et al.), leading to differences in material behavior, DMLS and conventional IN718 materials are studied using SEM and TEM characterization to investigate sub-micron and/or nano-scale

microstructural differences developed in the DMLS samples as a result of their complex thermal history and internal stress.

The preliminary analysis presented in this body of work is an attempt to better understand the effect of DMLS processing in quest for development of optimization techniques for DMLS as a whole. A historical sketch of nickel alloys and the development of IN718 is given. A literature review detailing the microstructure of IN718 is presented. Creep data analysis and identification of active creep mechanisms are evaluated. High-resolution microstructural characterization of DMLS and wrought IN718 are discussed in detail throughout various chapters of this thesis. Finally, an initial effort in developing a processing model that would allow for parameter optimization is presented.

ABSTRACT



Large-pore metal-organic framework (MOF) membranes offer potential in a number of gas and liquid separations due to their wide and selective adsorption capacities. A key characteristic of a number of MOF and zeolitic imidazolate framework (ZIF) membranes is their highly selective adsorption capacities for CO2. These membranes offer very tangible potential to separate CO2 in a wide array of industrially relevant separation processes, such as the separation from CO2 in flue gas emissions, as well as the sweetening of methane.

By virtue of this, the purpose of this dissertation is to synthesize and characterize two linear large-pore MOF membranes, MOF-5 and ZIF-68, and to study their gas separation properties in binary mixtures of CO¬2/N2 and CO2/CH4. The three main objectives researched are as follows. The first is to study the pervaporation behavior and stability of MOF-5; this is imperative because although MOF-5 exhibits desirable adsorption and separation characteristics, it is very unstable in atmospheric conditions. In determining its stability and behavior in pervaporation, this material can be utilized in conditions wherein atmospheric levels of moisture can be avoided. The second objective is to synthesize, optimize and characterize a linear, more stable MOF membrane, ZIF-68. The final objective is to study in tandem the high-pressure gas separation behavior of MOF-5 and ZIF-68 in binary gas systems of both CO2/N2 and CO2/CH4.

Continuous ZIF-68 membranes were synthesized via the reactive seeding method and the modified reactive seeding method. These membranes, as with the MOF-5 membranes synthesized herein, both showed adherence to Knudsen diffusion, indicating limited defects. Organic solvent experiments indicated that MOF-5 and ZIF-68 were stable in a variety of organic solvents, but both showed reductions in permeation flux of the tested molecules. These reductions were attributed to fouling and found to be cumulative up until a saturation of available bonding sites for molecules was reached and stable pervaporation permeances were reached for both. Gas separation behavior for MOF-5 showed direct dependence on the CO2 partial pressure and the overall feed pressure, while ZIF-68 did not show similar behavior. Differences in separation behavior are attributable to orientation of the ZIF-68 membranes.

Microelectronic industry is continuously moving in a trend requiring smaller and smaller devices and reduced form factors with time, resulting in new challenges. Reduction in device and interconnect solder bump sizes has led to increased current density in these small solders. Higher level of electromigration occurring due to increased current density is of great concern affecting the reliability of the entire microelectronics systems. This paper reviews electromigration in Pb- free solders, focusing specifically on Sn0.7wt.% Cu solder joints. Effect of texture, grain orientation, and grain-boundary misorientation angle on electromigration and intermetallic compound (IMC) formation is studied through EBSD analysis performed on actual C4 bumps.

Ball Grid Array (BGA) using lead-free or lead-rich solder materials are widely used as Second Level Interconnects (SLI) in mounting packaged components to the printed circuit board (PCB). The reliability of these solder joints is of significant importance to the performance of microelectronics components and systems. Product design/form-factor, solder material, manufacturing process, use condition, as well as, the inherent variabilities present in the system, greatly influence product reliability. Accurate reliability analysis requires an integrated approach to concurrently account for all these factors and their synergistic effects. Such an integrated and robust methodology can be used in design and development of new and advanced microelectronics systems and can provide significant improvement in cycle-time, cost, and reliability. IMPRPK approach is based on a probabilistic methodology, focusing on three major tasks of (1) Characterization of BGA solder joints to identify failure mechanisms and obtain statistical data, (2) Finite Element analysis (FEM) to predict system response needed for life prediction, and (3) development of a probabilistic methodology to predict the reliability, as well as, the sensitivity of the system to various parameters and the variabilities. These tasks and the predictive capabilities of IMPRPK in microelectronic reliability analysis are discussed.

This thesis elaborates the application of carbon nanotubes (CNTs) and it is discussed in two parts. In the first part of the thesis, two types of CNTs inks for inkjet materials printer are prepared. They are both chemical stable and printable, effective and easily made. The sheet resistance of printed films decreases exponentially as the number of layers increases. In the second part of this study, CNTs/ZnO composite structures are fabricated to understand the electronic and optical properties. The materials were deposited by two different methods: drop-drying and RF magnetic sputtering system on flexible polymer substrates. To further increase the conductivity of the various layers of deposited CNTs films, electrical and optical characterizations are also done. This study establishes CNTs as a multi-functional semitransparent conductor, which can be deposited at room-temperature with other transparent conductive oxide (TCO) composites for application in flexible electronics and printed circuit and sensors.