Cordierite was adhered to molybdenum using various metallic interlayers of copper, nickel, and chromium. The development of a coating adhesion test methodology was required to choose between interface designs. An indentation method was chosen because of ease in testing and availability of fracture mechanics interpretations of test data. The interfacial fracture toughness was determined from indentation load vs. crack length data by examining the residual stress and critical buckling load of the ceramic coatings. The interfacial fracture toughness values obtained using a slightly different indentation analysis agree with those in the literature. Quantitative chemical analysis of the interface microstructure was used to explain differences in interfacial fracture toughness values for samples with different metallic interlayer designs. The best interface design for adhering cordierite glass-ceramic coatings to molybdenum was found to be molybdenum / 2 μm copper / 4 μm chromium / cordierite. / Master of Science

The development of organic photovoltaics (OPVs) has attracted a lot of attention due to their potential to create a low cost flexible solar cell platform. In general, an OPV is comprised of a number of layers of thin films that include the electrodes, active layers and barrier films. Thus, with all of the interfaces within OPV devices, the potential for failure exists in numerous locations if adhesion at the interface between layers is inherently low or if a loss of adhesion due to device aging is encountered. To date, few studies have focused on the basic properties of adhesion in organic photovoltaics and its implications on device reliability. In this dissertation, we investigated the adhesion between interfaces for a model multilayer barrier film (SiNx/PMMA) used to encapsulate OPVs. The barrier films were manufactured using plasma enhanced chemical vapor deposition (PECVD) and the interfacial fracture toughness (Gc, J/m2) between the SiNx and PMMA were quantified. The fundamentals of the adhesion at these interfaces and methods to increase the adhesion were investigated. In addition, we investigated the adhesive/cohesive behavior of inverted OPVs with different electrode materials and interface treatments. Inverted OPVs were fabricated incorporating different interface modification techniques to understand their impact on adhesion determined through the interfacial fracture toughness (Gc, J/m2). Overall, the goal of this study is to quantify the adhesion at typical interfaces used in inverted OPVs and barrier films, to understand methods that influence the adhesion, and to determine methods to improve the adhesion for the long term mechanical reliability of OPV devices.

Recently there has been an increased focus on the use of microfluidics for the synthesis of different products. One of the products proposed for synthesis is quantum dots. Microfluidics often uses Polydimethylsiloxane for structure in microfluidic chips, but quantum dots use octadecene in several synthesis steps. The purpose of this work was to create a lab setup capable of anodically bonding 4” diameter wafers, and to characterize the bond formed using the Plaza test chip so that microfluidic devices using glass and silicon as substrates could be created. Two stainless steel electrodes placed on top of a hot plate were attached to a high power voltage supply to perform anodic bonding. A Plaza test mask was created and used to pattern P type silicon wafers. The channels etched were between 300 and 500nm deep and ranged between 1000µm and 50µm. These wafers were then anodically bonded to Corning 7740 glass wafers. Bonding stopped once the entire surface of the wafer was bonded, determined by visual inspection. All bonds were formed at 400°C and the bond strength and toughness between wafers bonded at 400V and 700V was compared. A beam model was used to predict the interfacial fracture toughness, and the stress at the bond was calculated with a parallel spring model. By measuring the crack length of the test structures under a light microscope the load conditions of the beam could be found. It was concluded that the electrostatic forces between the wafers give the best indication of what the bond quality will be. This was seen by the large difference in crack length between samples that were bonded using a thick glass wafer (1 mm) and a thin glass wafer (500µm). The observed crack lengths for the thick glass wafers were between 40 and 60µm. Thin glass wafers had a crack length between 20 and 40µm. The fracture toughness was calculated using the beam model approximation. Fracture toughness of the thin glass wafers was 7MPa m1/2, and of the thick glass wafers was 30 MPa m1/2. The fracture toughness of the thick glass wafers agreed with results found through the use of the double cantilever beam samples in literature. The maximum observed interfacial stress was 70 MPa. Finally, to measure the change in the size of the sodium depletion zone formed during bonding, samples were placed under a scanning electron microscope (SEM). Depletion zones were found to be between 1.1 and 1.4µm for thin glass samples that were bonded at 400 and 700 volts. This difference was not found to have a significant effect on the strength or fracture toughness observed. Thicker glass samples could not have their depletion zone measured due to SEM chuck size.

An experimental investigation was undertaken to analyze the behavior of sandwich composite structures exposed to one-sided heating where a debond exists between the unexposed facesheet and core material. Sandwich composites of plain weave E-glass/epoxy facesheets and an end-grain balsa wood core manufactured using the Vacuum Assisted Resin Transfer Molding (VARTM) technique were the only materials analyzed. These were selected due to their current use in naval vessels and the heightened interest in the fire response properties of balsa wood and its utility as a core material. In order to better understand the interfacial behavior, Mode I Double Cantilever Beam (DCB) fracture tests were performed at ambient, 60 C, and 80 C to determine the influence of the decreased Mode I fracture toughness. While ambient testing showed that stable crack growth could be obtained, high temperature tests resulted in considerable damage occurring to the core at the crack-front preventing stable crack growth. This can be attributed to the significant decrease in the balsa core strength and material properties even for small increases in temperature. Additionally, Mode II Cracked Split Beam (CSB) tests were performed at ambient temperature to examine the sliding dominant crack-growth. Again, the occurrence of balsa core damage prevented stable crack-growth and an accurate measurement of Mode II fracture toughness was not obtained. Intermediate-scale compression testing with one-sided heating at two heat flux levels was performed with a custom designed load frame on sandwich composite columns. This enabled the influence of the debond to be measured using a 3D-Digital Image Correlation (DIC) technique spatially linked with a thermographic camera. The DIC allowed for a detailed observation of debond growth and buckling prior to global failure of the test article. A behavior similar to that observed in the Mode I DCB fracture tests occurred: as the interfacial temperature increased, the amount of crack growth decreased. This crack growth was followed by a core failure at the crack-front, triggering a global failure of the test article. This global failure for test articles containing a debond manifested itself primarily as an anti-symmetric post-buckling shape. Test articles with no debond exhibited the typical progression of the out-of-plane displacement profile for a fixed-fixed column. As the out-of-plane displacement increased, core failure ultimately occurred near the gripped region where the zero-slope condition is required, triggering global failure of the no debond test article. These tests highlight that the reduction in strength and material properties of the end-grain balsa wood core significantly outweigh the reduction in interfacial fracture toughness due to the increased temperatures. / Master of Science

In this study, a test technique, referred to as the probe test, has been developed as a quantitative tool for measuring the adhesion in thin adhesive films and coatings. The technique was initially developed as a qualitative test by the Hewlett-Packard Company for measuring adhesion of thin film microelectronic coatings. In the probe test method, an inclined needle-like probe with a conical tip is advanced underneath the free edge of a thin polymeric coating bonded to a substrate, causing the edge to lift-up from the surface of the substrate. A debond is thus initiated at the loading point and propagates as a semi-circular crack at the interface as the probe slides under the coating. A standard test procedure has been developed for testing thin adhesive coating/substrate systems. The sample system used is a thin film epoxy polymer coated silicon system. The interfacial fracture energy (Gc) (or critical strain energy release rate) has been used as a quantitative measure of adhesion for the given adhesive coating/substrate system. The probe test experiments were conducted using an optical microscope and a WYKO optical profiler. Using the optical microscope, the debond radius was measured for different debond sizes. Using the WYKO optical profiler, the three-dimensional surface topography of the debonded coating around the crack front was measured for different debond sizes. Using the experimental data from the probe test, analytical and numerical (finite element-based) techniques have been developed to determine the interfacial fracture energy (Gc) for the given adhesive coating/substrate system. The analytical techniques were developed based on different plate theory formulations (thin/thick plate - small/large deflection) of the probe test geometry and local curvature measurement at the crack tip. The finite element based techniques were developed using a hybrid numerical-experimental approach and surface-based contact interaction analysis in ABAQUS. The results obtained using thick plate-large deflection formulation correlated with finite element contact interaction analysis results. The probe test can be used with transparent or opaque coatings and thus offers a promising alternative to indentation and other tests methods for characterizing thin film and coating adhesion. / Master of Science

The development of organic photovoltaics (OPVs) has attracted a lot of attention due to their potential to create a low cost flexible solar cell platform. In general, an OPV is comprised of a number of layers of thin films that include the electrodes, active layers and barrier films. Thus, with all of the interfaces within OPV devices, the potential for failure exists in numerous locations if adhesion at the interface between layers is inherently low or if a loss of adhesion due to device aging is encountered. To date, few studies have focused on the basic properties of adhesion in organic photovoltaics and its implications on device reliability. In this dissertation, we investigated the adhesion between interfaces for a model multilayer barrier film (SiNx/PMMA) used to encapsulate OPVs. The barrier films were manufactured using plasma enhanced chemical vapor deposition (PECVD) and the interfacial fracture toughness (Gc, J/m2) between the SiNx and PMMA were quantified. The fundamentals of the adhesion at these interfaces and methods to increase the adhesion were investigated. In addition, we investigated the adhesive/cohesive behavior of inverted OPVs with different electrode materials and interface treatments. Inverted OPVs were fabricated incorporating different interface modification techniques to understand their impact on adhesion determined through the interfacial fracture toughness (Gc, J/m2). Overall, the goal of this study is to quantify the adhesion at typical interfaces used in inverted OPVs and barrier films, to understand methods that influence the adhesion, and to determine methods to improve the adhesion for the long term mechanical reliability of OPV devices.

Microelectronic devices are multilayered structures with many different interfaces. Their mechanical reliability is of utmost importance when considering the implementation of new materials. Linear elastic fracture mechanics (LEFM) is a common approach that has been used for interfacial fracture analyses in the microelectronics industry where the energy release rate parameter is considered to be the driving force for delamination and the failure criterion is established by comparing this with the interface toughness. However this approach has been unable to model crack-nucleation, which plays an important part in analyzing the mechanical reliability of chip-package systems. The cohesive interface modeling approach, which is considered here, has the capability to model crack nucleation and growth, provided interfacial parameters such as strength and toughness of the system are available. These parameters are obtained through the extraction of traction-separation relations, which can be obtained through indirect hybrid numerical/experimental methods or direct experimental methods. All methods of extracting traction-separation relations require some local feature of the crack-tip region to be measured. The focus in this doctoral work has been on the comparison of the two methods for a mode-I DCB experiment and on the development of a universal loading device to extract mixed-mode traction-separation relations at different mode-mix values. The techniques that have been adopted for the local measurements are infrared crack opening interferometry (IR-COI) and digital image correlation (DIC). Apart from the global measurements of load-displacement (P-[delta]), local crack-tip parameters were measured using IR-COI or DIC. The combination of global and local measurements gave the relations between the fracture driving force (energy release rate or J-integral, J) and crack opening displacements, which were used to obtain the local tractions. IR-COI is an extremely useful technique to image and measure local crack-tip parameters. However, as IR-COI is restricted to normal measurements, the loading device was configured to accommodate a DIC system in order to make both normal and tangential measurements. In addition to measurements, fracture surface characterization techniques such as atomic force microscopy (AFM), profilometry and X-ray photoelectron spectroscopy were used to observe the fracture mechanisms. / text

The interfacial fracture performance of dicyandiamide cured epoxy/steel adhesive systems was thoroughly investigated. Fracture mechanics based testing was utilized to study several variables which were believed to influence the epoxy/steel interphase region, specifically the elasomeric toughener concentration, the dicyandiamide concentration, and the cure temperature. Bulk mechanical measurements were conducted to provide background information for comparison with the fracture data, and surface analyses were carried out on the neat adhesives and failed fracture specimens to provide insight into the locus and causes of failure. The addition of toughener drastically impacted the morphological, bulk mechanical, and adhesive properties in these latent cure systems. Modulus values decreased and bulk fracture toughness values increased with increasing toughener content. Static double cantilever beam (DCB), fatigue DCB, and notched coating adhesion (NCA) interfacial fracture performances all increased. X-ray photoelectron spectroscopy (XPS) and tunneling electron microscopy (TEM) analyses of the failed specimens revealed that chemical changes were more prominent at the epoxy/steel interphase than in the bulk of the materials. Morphological variations were also apparent with toughener level variations, but for a single formulation no differences between the bulk and intephase morphologies were seen. Evaluations were conducted on a series of elastomer modified model epoxy formulations cured with varying amounts of dicyandiamide. The modulus and bulk fracture toughness values were shown to be independent of dicyandiamide concentration, whereas the adhesive performance was greatly influenced. For increases in the concentration of dicyandiamide, single lap shear (SLS) failure strength values increased while quasi-static DCB and NCA test performances decreased. Fatigue DCB results showed improved adhesive performance at both high and low levels of dicyandiamide content. The results of the failure surface evaluations suggest that dicyandiamide variations produce significant chemical changes only in the epoxy/steel interphase region, and not in the bulk. Analyses were conducted on all of the above systems using two additional cure temperatures. The purpose of this work was to alter the dicyandiamide solubility, and possibly the dicy/epoxy reaction mechanisms, and to determine what influence these changes had on the interfacial fracture performance. In general it was found that performance increased as the cure temperature was increased. / Ph. D.

The goal of this research was to develop new experimental techniques to quantitatively study the interfacial fracture of micro-contact thin film interconnects used in microelectronic applications under monotonic and cyclic loadings. The micro-contact spring is a new technology that is based on physical vapor deposited thin film cantilevers with a purposely-imposed stress gradient through the thickness of the film. These "springs" have the promise of being the solution to address near-term wafer level probing and long-term high-density chip-to-next level microelectronic packaging challenges, as outlined by the International Technology Roadmap for Semiconductors. The success of this technology is, in part, dependent on the ability to understand the failure mechanism under monotonic and cyclic loadings. This research proposes two experimental methods to understand the interfacial fracture under such monotonic and fatigue loading conditions. To understand interfacial fracture under monotonic loading, a fixtureless superlayer-based delamination test has been developed. Using stress-engineered Cr layer and a release layer with varying width, this test can be used to measure interfacial fracture toughness under a wide range of mode mixity. This test uses common IC fabrication techniques and overcomes the shortcomings of available methods. The developed test has been used to measure the interfacial fracture toughness for Ti/Si interface. It was found that for low mode mixity Ti/Si thin film interfaces, the fracture toughness approaches the work of adhesion which is essentially the Ti-Si bond energy for a given bond density. In addition to the monotonic decohesion test, a fixtureless fatigue test is developed to investigate the interfacial crack propagation. Using a ferromagnetic material deposited on the micro-contact spring, this test employs an external magnetic field to be able to drive the interfacial crack. Fatigue crack growth can be monitored by E-beam lithography patterned metal traces that are 10 to 40nm wide and 1 to a few µm in spacing. The crack initiation and propagation can be monitored through electrical resistance measurement. In the conducted experiments, it is seen that the interfacial delamination does not occur under fatigue loading, and that the micro-contact springs are robust against interfacial fracture for probing and packaging applications.

Original analytical theories are developed for partitioning mixed-mode fractures on rigid interfaces in laminated orthotropic double cantilever beams (DCBs) based on 2D elasticity by using some novel methods. Note that although the DCB represents a simplified case, it provides a deep understanding and predictive capability for real applications and does not restrict the analysis to a simple class of fracture problems. The developed theories are generally applicable to so-called 1D fracture consisting of opening (mode I) and shearing (mode II) action only with no tearing (mode III) action, for example, straight edge cracks, circular blisters in plates and shells, etc. A salient point of the methods is to first derive one loading condition that causes one pure fracture mode. It is conveniently called the first pure mode. Then, all other pure fracture modes can be determined by using this pure mode and the property of orthogonality between pure mode I modes and pure mode II modes. Finally, these 2D-elasticity-based pure modes are used to partition mixed-mode fractures into contributions from the mode I and mode II fracture modes by considering a mixed-mode fracture as the superposition of pure mode I and mode II fractures. The partition is made in terms of the energy release rate (ERR) or the stress intensity factor (SIF). An analytical partition theory is developed first for a DCB composed of two identical linear elastic layers. The first pure mode is obtained by introducing correction factors into the beam-theory-based mechanical conditions. The property of orthogonality is then used to determine all other pure modes in the absence of through-thickness-shear forces. To accommodate through-thickness shear forces, first two pure through-thickness-shear-force pure modes (one pure mode I and one pure mode II) are discovered by extending a Timoshenko beam partition theory. Partition of mixed-mode fractures under pure through-thickness shear forces is then achieved by using these two pure modes in conjunction with two thickness-ratio-dependent correction factors: (1) a shear correction factor, and (2) a pure-mode-II ERR correction factor. Both correction factors closely follow a normal distribution around a symmetric DCB geometry. The property of orthogonality between all pure mode I and all pure mode II fracture modes is then used to complete the mixed-mode fracture partition theory for a DCB with bending moments, axial forces and through-thickness shear forces. Fracture on bimaterial interfaces is an important consideration in the design and application of composite materials and structures. It has, however, proved an extremely challenging problem for many decades to obtain an analytical solution for the complex SIFs and the crack extension size-dependent ERRs, based on 2D elasticity. Such an analytical solution for a brittle interfacial crack between two dissimilar elastic layers is obtained in two stages. In the first stage the bimaterial DCB is under tip bending moments and axial forces and has a mismatch in Young s modulus; however, the Poisson s ratios of the top and bottom layers are the same. The solution is achieved by developing two types of pure fracture modes and two powerful mathematical techniques. The two types of pure fracture modes are a SIF-type and a load-type. The two mathematical techniques are a shifting technique and an orthogonal pure mode technique. In the second stage, the theory is extended to accommodate a Poisson s ratio mismatch. Equivalent material properties are derived for each layer, namely, an equivalent elastic modulus and an equivalent Poisson s ratio, such that both the total ERR and the bimaterial mismatch coefficient are maintained in an alternative equivalent case. Cases for which no analytical solution for the SIFs and ERRs currently exist can therefore be transformed into cases for which the analytical solution does exist. It is now possible to use a completely analytical 2D-elasticity-based theory to calculate the complex SIFs and crack extension size-dependent ERRs. The original partition theories presented have been validated by comparison with numerical simulations. Excellent agreement has been observed. Moreover, one partition theory is further extended to consider the blister test and the adhesion energy of mono- and multi-layered graphene membranes on a silicon oxide substrate. Use of the partition theory presented in this work allows the correct critical mode I and mode II adhesion energy to be obtained and all the experimentally observed behaviour is explained.