Depth sensing indentation of organic-inorganic hybrid coatings deposited onto a polymeric substrate

PEO-Si/SiO2 hybrid coatings deposited onto a PVC substrate were micromechanically characterized using depth sensing indentation. The effect of curing time and coating thickness was investigated. Elastic moduli of coated systems determined by the Oliver–Pharr approach displayed a continuous decreasing trend with increasing indentation depth, reflecting that the hybrids are stiffer than the substrate. Aiming to extract coating-only elastic modulus a simple method based on FE simulations was developed. The method was applied to evaluate the moduli of the hybrid coatings and the values were compared with those obtained by applying different approaches available in literature. The elastic modulus of PEO-Si/SiO2 hybrids was proven to be practically independent of curing time after 24 h. However, large curing times resulted in coatings being more prone to failure.Fil: Fasce, Laura Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Seltzer, Rocío. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Frontini, Patricia Maria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentin

Size Dependence of Nanoscale Wear of Silicon Carbide

Nanoscale, single-asperity wear of single-crystal silicon carbide (sc-SiC) and nanocrystalline silicon carbide (nc-SiC) is investigated using single-crystal diamond nanoindenter tips and nanocrystalline diamond atomic force microscopy (AFM) tips under dry conditions, and the wear behavior is compared to that of single-crystal silicon with both thin and thick native oxide layers. We discovered a transition in the relative wear resistance of the SiC samples compared to that of Si as a function of contact size. With larger nanoindenter tips (tip radius around 370 nm), the wear resistances of both sc-SiC and nc-SiC are higher than that of Si. This result is expected from the Archard's equation because SiC is harder than Si. However, with the smaller AFM tips (tip radius around 20 nm), the wear resistances of sc-SiC and nc-SiC are lower than that of Si, despite the fact that the contact pressures are comparable to those applied with the nanoindenter tips, and the plastic zones are well-developed in both sets of wear experiments. We attribute the decrease in the relative wear resistance of SiC compared to that of Si to a transition from a wear regime dominated by the materials' resistance to plastic deformation (i.e., hardness) to a regime dominated by the materials' resistance to interfacial shear. This conclusion is supported by our AFM studies of wearless friction, which reveal that the interfacial shear strength of SiC is higher than that of Si. The contributions of surface roughness and surface chemistry to differences in interfacial shear strength are also discussed

A Review on Mechanics and Mechanical Properties of 2D Materials - Graphene and Beyond

Since the first successful synthesis of graphene just over a decade ago, a variety of two-dimensional (2D) materials (e.g., transition metal-dichalcogenides, hexagonal boron-nitride, etc.) have been discovered. Among the many unique and attractive properties of 2D materials, mechanical properties play important roles in manufacturing, integration and performance for their potential applications. Mechanics is indispensable in the study of mechanical properties, both experimentally and theoretically. The coupling between the mechanical and other physical properties (thermal, electronic, optical) is also of great interest in exploring novel applications, where mechanics has to be combined with condensed matter physics to establish a scalable theoretical framework. Moreover, mechanical interactions between 2D materials and various substrate materials are essential for integrated device applications of 2D materials, for which the mechanics of interfaces (adhesion and friction) has to be developed for the 2D materials. Here we review recent theoretical and experimental works related to mechanics and mechanical properties of 2D materials. While graphene is the most studied 2D material to date, we expect continual growth of interest in the mechanics of other 2D materials beyond graphene

MULTIFUNCTIONAL BEHAVIORS OF TWO-DIMENSIONAL MATERIALS AND THEIR COMPOSITES

Two-dimensional (2D) materials, including graphene, transition metal carbides or nitrides (TMC/Ns), have rich surface chemistry, superb electrical and mechanical properties. These unique properties make them ideal for multifunctional devices. Among them, we focused on graphene and TMC/Ns (i.e., MXenes), as well as their composites. Unlike the well-known graphene, MXenes, are relatively new and typically synthesized by the selective etching of the “A” layers from the layered carbides and /or nitrides known as MAX phases, which introduce MXenes with rich terminal groups (e.g. -O-, -OH, -F). During my Ph.D. study, firstly, the adhesive and frictional behaviors, which are related to successful film transfer and shear force transmission of 2D materials, respectively, were studied. Secondly, in-plane mechanical behaviors of 2D materials, were characterized using in situ experimental tools for micro-scale samples. At last, the high surface affinity and versatile chemical binding capabilities for 2D materials were applied in virus sensing. Results show that the increase of AgNWs reduces the adhesion of AgNWs-GN. Long-range interaction, high adhesion and friction forces were observed for MXene/MXene interface, which is due to interactions between MXene terminating groups. The dependence of Young’s modulus and strength on the number of stacked MXene monolayers is much weaker than multilayer graphene and MoS2 stacks due to -O- atom bridging. Highly nonlinear responses and large residual deformations were observed under cyclic compression of MXene microparticles. At last, a wireless, flexible on-mask immunosensing-based COVID-19 breath sensor was developed to detect air-borne viruses --Abstract, p. ii

Mechanical adhesion of SIO2 thin film on a polymeric substrate under compressive stress

International audienceTo ensure good adhesion between a 200 nm silicon dioxide layer and a 4.5 μm thick hardcoat polymeric coating, a better understanding of mechanisms of adhesion at this interface is needed. To reach this purpose, quantification of adhesion is performed by analyzing SiO2 buckle morphologies generated under compressive stress. This adhesion test was chosen for its representativeness of defects observed in real life. Interfacial toughness can be determined by applying Hutchinson & Suo model. This analytical model involves accurate value of elastic modulus Ef of SiO2 thin film. Small dimensions at stake make characterization of elastic modulus challenging. First part of the study focuses on using both nano-indentation and AFM to attempt assessment of SiO2 thin film elastic modulus. Results showed significant influence of substrate for both techniques. Impact on mechanical properties between SiO2 thin films with different intrinsic stresses was also investigated and suggests that higher density of SiO2 thin film leads to higher elastic modulus. Compression tests resulted in formation of straight-sided buckles that evolve into telephone cords upon unloading. Numerical simulation and Digital Image Correlation were implemented to ensure homogeneous strain of substrate and favor regular distribution of buckles. Values of energy release rates of SiO2 / Hardcoat range from 2.7 J/m² to 8.9 J/m², depending on moduli values found on wafer or lens substrate

Adhesion in a Copper-Ruthenium Multilayer Nano-scale Structure and the Use of a Miedema Plot to Select a Diffusion Barrier Metal for Copper Metallization

abstract: Miedema's plot is used to select the Cu/metal barrier for Cu metallization.The Cu/metal barrier system selected should have positive heat of formation (Hf) so that there is no intermixing between the two layers. In this case, Ru is chosen as a potential candidate, and then the barrier properties of sputtered Cu/Ru thin films on thermally grown SiO2 substrates are investigated by Rutherford backscattering spectrometry (RBS), X-ray diffractometry (XRD), and electrical resistivity measurement. The Cu/Ru/SiO2 samples are analyzed prior to and after vacuum annealing at various temperatures of 400, 500, and 600 oC and at different interval of times of 0.5, 1 and 2 hrs for each temperature. Backscattering analysis indicate that both the copper and ruthenium thin films are thermally stable at high temperature of 600 oC, without any interdiffusion and chemical reaction between Cu and Ru thin films. No new phase formation is observed in any of the Cu/Ru/SiO2 samples. The XRD data indicate no new phase formation in any of the annealed Cu/Ru/SiO2 samples and confirmed excellent thermal stability of Cu on Ru layer. The electrical resistivity measurement indicated that the electrical resistivity value of the copper thin films annealed at 400, 500, and 600 oC is essentially constant and the copper films are thermally stable on Ru, no reaction occurs between copper films and Ru the layer. Cu/Ru/SiO2 multilayered thin film samples have been shown to possess good mechanical strength and adhesion between the Cu and Ru layers compared to the Cu/SiO2 thin film samples. The strength evaluation is carried out under static loading conditions such as nanoindentation testing. In this study, evaluation and comparison is donebased on the dynamic deformation behavior of Cu/Ru/SiO2 and Cu/SiO2 samples under scratch loading condition as a measure of tribological properties. Finally, the deformation behavior under static and dynamic loading conditions is understood using the scanning electron microscope (SEM) and the focused ionbeam imaging microscope (FIB) for topographical and cross-sectional imaging respectively.Dissertation/ThesisM.S. Materials Science and Engineering 201

Developing Metrology for Nondestructive Characterization of Buried Polymer Interfaces in Situ.

Polymers are widely used in modern microelectronics as adhesives, organic substrates, chip passivation layers, insulating dielectric materials, and photoresists in microlithography. The interfacial structures of polymer materials determine the interfacial properties of the materials. Weak adhesion or delamination at interfaces involving polymer materials can lead to failure of microelectronic devices. Therefore, it is important to investigate the molecular structures of such interfaces. However, it is difficult to study molecular structures of buried interfaces due to a lack of appropriate analytical techniques. This dissertation presents the development of the nonlinear optical technique sum frequency generation (SFG) vibrational spectroscopy into a metrology tool for nondestructive characterization of molecular structures at buried polymer interfaces in microelectronic packages in situ and the elucidation of relationships between buried molecular structures and interfacial properties such as adhesion strength. Buried polymer/epoxy, copper/epoxy, and silicon/organosilicate dielectric interfaces were investigated. SFG was used to directly probe molecular structures at buried adhesive interface in situ. Plasma treatment of polymer surfaces was found to alter the molecular structure at corresponding buried interfaces prepared using the plasma treated surfaces. Hygrothermal aging treatment was found to influence hydrophobic polymer/polymer interfaces less than hydrophilic interfaces, showing that hydrophobic materials can better resist delamination during qualification testing in high humidity environments. Copper/epoxy interfaces were found to delaminate near, but not exactly at, the metal/polymer interface and silane adhesion promoters were found to modify the interfacial region near the copper surface which suggests that the interfacial layer near copper needs to be modified to improve adhesion. Quantitative data analysis methodology was developed to simultaneously characterize the surface and buried interface of silicon-supported thin low-k polymer films nondestructively before and after microelectronic processing steps which provided a molecular level understanding of the effects of the processing. The general nature of the methodology enables it to be directly utilized to elucidate structure-property relationships at buried interfaces by correlating interfacial structures to interfacial properties. Structure-property relationships elucidated using this methodology can be used to guide the rational engineering of buried polymer interfaces with optimized properties in many practical applications such as polymer composites, optical fibers, paints, and anticorrosion coatings.PhDChemistryUniversity of Michigan, Horace H. Rackham School of Graduate Studieshttp://deepblue.lib.umich.edu/bitstream/2027.42/133179/1/myersjn_1.pd

Theoretical and numerical study on adhesive interactions between graphene and substrate

This dissertation presents a set of theoretical and numerical studies on adhesive interactions between monolayer graphene membranes and their substrates. Both continuum mechanics models and molecular dynamics simulations are developed to investigate deformation of graphene membranes depending on the adhesive interactions with the substrates. First, a numerical study on snap transitions of gas-filled graphene blisters is presented, based on a continuum model combining a nonlinear plate theory with a nonlinear traction–separation relation. The numerical results may be used in conjunction with experiments for quantitative characterization of the interfacial properties of graphene and other two-dimensional (2D) membrane materials. Next, a statistical mechanics analysis on thermal rippling of monolayer graphene supported on a rigid substrate is presented and compared with molecular dynamics simulations to reveal the entropic effects of thermal rippling on van der Waals interactions between graphene and the substrate. While the amplitude of thermal rippling is reduced by the adhesive interactions, the entropic contribution of thermal rippling leads to an effective repulsion, thus reducing the effective adhesion. Moreover, the effect of a biaxial pre-strain in graphene is considered, and a buckling instability is predicted at a critical compressive strain that depends on both the temperature and the adhesive interactions. This motivates a systematic study on morphological transitions of monolayer graphene on a substrate under uniaxial compressive strain, from rippling to wrinkling/buckling and to folding. The presence of water at the interface has significant influence on the adhesive interactions between graphene and its substrate. Molecular dynamics simulations are performed to study the interactions between graphene and a wet substrate that is covered by a thin layer of water. Four stages of the traction-separation relations are identified and they are analyzed approximately by simple continuum models. When the thickness of water layer is below 1 nm, the water molecules form discrete monolayer or bilayer structures, leading to different traction-separation behaviors. Finally, with a finite number of water molecules trapped between a monolayer graphene and its substrate, water-filled graphene blisters form spontaneously. Based on molecular dynamics simulations and a simple theoretical model, the work of adhesion for the graphene/substrate interface may be estimated by measuring the aspect ratios of the graphene blisters. Unlike gas-filled graphene blisters in previous studies, the shape and size of the water-filled graphene blister depend on the wetting properties of graphene and the substrate. The results on wet adhesion and water-filled blisters can be readily extended to other 2D materials.Engineering Mechanic

Contributions to the performance of thin film capacitors for high reliability applications

Capacitors are critical devices in microelectronic assemblies that must be incorporated into electronic systems through a variety of ways such as integrated or discrete devices. This work has developed new thin film capacitors deposited directly onto multichip module or printed circuit board surfaces to benefit from closer integration that enhances system performance for use in high reliability applications. The capacitors serve as filters or provide tuning and energy storage functions. Unexpected performance was observed during development that included low adhesion of the films to the substrates, higher effective dielectric constants than reported in literature, and low yields. Three publications resulted from this work with Paper I presenting a study of thin films on low temperature cofired ceramic (LTCC) and their reliability for multiple functions. The thin film and LTCC system are modeled with results suggesting a mechanism of enhancing thin film adhesion to the LTCC through a combination film composition and surface modification. Paper II presents measurements of dielectric properties of thin film capacitors on LTCC. Multiple mechanisms are detailed that contribute to the measured dielectric constant values of the capacitors. One case is modeled to determine the extent of dielectric constant enhancement from fringe fields related to capacitor dimensions. Paper III describes the behavior of thin film capacitors with varying electrode compositions and configurations. Trends are observed that suggest energy band overlap and electrode work functions are influential in dielectric properties and yield of the capacitors. A preferred electrode composition and configuration is suggested based on the capacitor performance --Abstract, page iii

Morphologic Instability of Graphene and its Potential Applications

Graphene is a monolayer of graphite. The surge of interest in graphene, as epitomized by the Nobel Prize in Physics in 2010, is largely attributed to its exceptional properties. Ultra thin, mechanically tough, electrically conductive, and transparent graphene films promise to enable a wealth of possible applications ranging from thin-film solar cells, flexible displays, to biochemical sensing arrays. However, significant gaps remain to realize these potential applications, largely due to the difficulty of precisely controlling graphene properties. Graphene is intrinsically non-flat and tends to be randomly corrugated. The random graphene morphology can lead to unstable performance of graphene devices as the corrugating physics of graphene is closely tied to its electronic properties. Future success of graphene-based applications hinges upon precise control of the graphene morphology, a significant challenge largely unexplored so far. This dissertation aims to explore viable pathways to tailoring graphene morphology and leverage possible morphologic instability of graphene for novel nano-device applications. Inspired by recent experiments, we propose and benchmark a strategy to precisely control the graphene morphology via extrinsic regulation (e.g., substrate surface features, patterned nanowires and nanoparticles). A general energetic framework is delineated to quantitatively determine the extrinsically regulated graphene morphology through energy minimization. Such a framework is benchmarked by determining the graphene morphology regulated by various types and dimensions of nanoscale extrinsic scafffolds, including two dimensional herringbone and checkerboard corrugations on substrate surfaces and one dimensional substrate surface grooves and patterned nanowires. The results reveal a snap-through instability of the graphene morphology, that is, depending on interfacial bonding energy and substrate surface roughness, the graphene morphology exhibits a sharp transition between two distinct states: (1) closely conforming to the substrate surface and (2) remaining nearly flat on the substrate surface. This snap-through instability of graphene holds potential to enable graphene-based functional nano-devices (e.g., ultrasensitive nano-switches). Another type of morphologic instability of graphene is the spontaneous scrolling of graphene into a carbon nanoscroll (CNS). The spiral multilayer nanostructure of CNSs is topologically open and thus distinct from that of carbon nanotubes (CNTs). The unique topological structure of CNSs can enable an array of novel applications, e.g., hydrogen storage, water channels and ultrafast nano-oscillators. However, the realization of CNS-based applications is hindered by the lack of reliable approach to fabricating high quality CNSs. We propose a simple physical approach to fabricating CNSs via CNT-initiated scrolling of graphene on a substrate. The successful formation of a CNS depends on the CNT diameter, the carbon-carbon interaction strength and the graphene-substrate interaction strength. We further demonstrate that the resulting CNS/CNT nanostructure can be used as an ultrafast axial nano-oscillator that operates at 10s GHz. Such CNS-based nano-oscillators can be excited and driven by an external AC electric field, further illustrating their potential to enable nano-scale energy transduction, harnessing and storage