Human activities involving subsurface reservoirs—resource extraction, carbon and nuclear waste storage—alter thermal, mechanical, and chemical steady-state conditions in these systems. Because these systems exist at lithostatic pressures, even minor chemical changes can cause chemically assisted deformation. Therefore, understanding how chemical effects control geomechanical properties is critical to optimizing engineering activities. The grand challenge in predicting the effect of chemical processes on mechanical properties lays in the fact that these phenomena take place at molecular scales, while they manifest all the way to reservoir scales. To address this fundamental challenge, we investigated chemical effects on deformation in model and real systems spanning molecular- to centimeter scales. We used theory, experiment, molecular dynamics simulation, and statistical analysis to (1) identify the effect of simple reactions, such as hydrolysis, on molecular structures in interfacial regions of stressed geomaterials; (2) quantify chemical effects on the bulk mechanical properties, fracture and displacement for granular rocks and single crystals; (3) develop initial understanding of universal scaling for individual displacement events in layered geomaterials; and (4) develop analytic approximations for the single-chain mechanical response utilizing asymptotically correct statistical thermodynamic theory. Taken together, these findings advance the challenging field of chemo-mechanics.
In this project, we demonstrated stable nanoscale fracture in single-crystal silicon using an in-situ wedge-loaded double cantilever beam (DCB) specimen. The fracture toughness KIC was calculated directly from instrumented measurement of force and displacement via finite element analysis with frictional corrections. Measurements on multiple test specimens were used to show KIC = 0.72 ± 0.07 MPa m1/2 on {111} planes and observe the crack-growth resistance curve in <500 nm increments. The exquisite stability of crack growth, instrumented measurement of material response, and direct visual access to observe nanoscale fracture processes in an ideally brittle material differentiate this approach from prior DCB methods.
Product designs from a wide range of industries such as aerospace, automotive, biomedical, and others can benefit from new metamaterials for mechanical energy dissipation. In this study, we explore a novel new class of metamaterials with unit cells that absorb energy via sliding Coulombic friction. Remarkably, even materials such as metals and ceramics, which typically have no intrinsic reversible energy dissipation, can be architected to provide dissipation akin to elastomers. The concept is demonstrated at different scales (centimeter to micrometer), with different materials (metal and polymer), and in different operating environments (high and low temperatures), all showing substantial dissipative improvements over conventional non-contacting lattice unit cells. Further, as with other ‘programmable’ metamaterials, the degree of Coulombic absorption can be tailored for a given application. An analytic expression is derived to allow rapid first-order optimization. This new class of Coulombic friction energy absorbers can apply broadly to many industrial sectors such as transportation (e.g. monolithic shock absorbers), biomedical (e.g. prosthetics), athletic equipment (e.g. skis, bicycles, etc.), defense (e.g. vibration tolerant structures), and energy (e.g. survivable electrical grid components).
A major challenge in gallium nitride (GaN) vertical power devices and other large bandgap materials is the high defect density that compromises the performance, reliability, and yield. Defects are typically nucleated at the heterointerface where there are both lattice and thermal mismatches. Here, we report the selective area growth (SAG) of thick GaN on Si and on the newly available Qromis Substrate Technology™ (QST) substrates that lead to a significant reduction of the defect densities to a level that is nearly comparable to that on native substrates by defect annihilation. We performed a parametric study of the electrical properties of the SAG GaN layers by fabricating and characterizing Schottky barrier diodes for SAG GaN layer thicknesses of 5, 10, 15, and 20 μm for GaN-on-Si, GaN-on-QST, and GaN-on-GaN diodes. While thicker layers led to a significant reduction in defect densities and improvement in the diode forward current characteristics, the GaN-on-QST diodes exhibited nearly similar characteristics to the GaN-on-GaN diodes. Further improvement in the device structure and/or SAG growth for GaN-on-Si is needed to achieve a comparable performance as the defect densities in the GaN-on-Si are comparable to that of GaN-on-QST substrates.
Alloyed and compound contacts between metal and semiconductor transistor channels enable self-aligned gate processes which play a significant role in transistor scaling. At nanoscale dimensions and for nanowire channels, prior experiments focused on reactions along the channel length, but the early stage of reaction in their cross sections remains unknown. Here, we report on the dynamics of the solid-state reaction between metal (Ni) and semiconductor (In0.53Ga0.47As), along the cross-section of nanowires that are 15 nm in width. Unlike planar structures where crystalline nickelide readily forms at conventional, low alloying temperatures, nanowires exhibit a solid-state amorphization step that can undergo a crystal regrowth step at elevated temperatures. In this study, we capture the layer-by-layer reaction mechanism and growth rate anisotropy using in situ transmission electron microscopy (TEM). Our kinetic model depicts this new, in-plane contact formation which could pave the way for engineered nanoscale transistors.
One of the most common causes of structural failure in metals is fatigue induced by cyclic loading. Historically, microstructure-level analysis of fatigue cracks has primarily been performed post mortem. However, such investigations do not directly reveal the internal structural processes at work near micro- and nanoscale fatigue cracks and thus do not provide direct evidence of active microstructural mechanisms. In this study, the tension-tension fatigue behavior of nanocrystalline Cu was monitored in real time at the nanoscale by utilizing a new capability for quantitative cyclic mechanical loading performed in situ in a transmission electron microscope (TEM). Controllable loads were applied at frequencies from one to several hundred hertz, enabling accumulations of 106 cycles within 1 h. The nanometer-scale spatial resolution of the TEM allows quantitative fatigue crack growth studies at very slow crack growth rates, measured here at ∼10-12 m·cycle-1. This represents an incipient threshold regime that is well below the tensile yield stress and near the minimum conditions for fatigue crack growth. Evidence of localized deformation and grain growth within 150 nm of the crack tip was observed by both standard imaging and precession electron diffraction orientation mapping. These observations begin to reveal with unprecedented detail the local microstructural processes that govern damage accumulation, crack nucleation, and crack propagation during fatigue loading in nanocrystalline Cu.
Aerosol deposition (AD) is a solid-state deposition technology that has been developed to fabricate ceramic coatings nominally at room temperature. Sub-micron ceramic particles accelerated by pressurized gas impact, deform, and consolidate on substrates under vacuum. Ceramic particle consolidation in AD coatings is highly dependent on particle deformation and bonding; these behaviors are not well understood. In this work, atomistic simulations and in situ micro-compressions in the scanning electron microscope, and the transmission electron microscope (TEM) were utilized to investigate fundamental mechanisms responsible for plastic deformation/fracture of particles under applied compression. Results showed that highly defective micron-sized alumina particles, initially containing numerous dislocations or a grain boundary, exhibited no observable shape change before fracture/fragmentation. Simulations and experimental results indicated that particles containing a grain boundary only accommodate low strain energy per unit volume before crack nucleation and propagation. In contrast, nearly defect-free, sub-micron, single crystal alumina particles exhibited plastic deformation and fracture without fragmentation. Dislocation nucleation/motion, significant plastic deformation, and shape change were observed. Simulation and TEM in situ micro-compression results indicated that nearly defect-free particles accommodate high strain energy per unit volume associated with dislocation plasticity before fracture. The identified deformation mechanisms provide insight into feedstock design for AD.
We employed an in situ electrochemical cell in the transmission electron microscope (TEM) together with ex situ time-of-flight, secondary-ion mass spectrometry (TOF-SIMS) depth profiling, and FIB-helium ion scanning microscope (HIM) imaging to detail the structural and compositional changes associated with Na/Na+ charging/discharging of 50 and 100 nm thin films of Sb. TOF-SIMS on a partially sodiated 100 nm Sb film gives a Na signal that progressively decreases toward the current collector, indicating that sodiation does not proceed uniformly. This heterogeneity will lead to local volumetric expansion gradients that would in turn serve as a major source of intrinsic stress in the microstructure. In situ TEM shows time-dependent buckling and localized separation of the sodiated films from their TiN-Ge nanowire support, which is a mechanism of stress-relaxation. Localized horizontal fracture does not occur directly at the interface, but rather at a short distance away within the bulk of the Sb. HIM images of FIB cross sections taken from sodiated half-cells, electrically disconnected, and aged at room temperature, demonstrate nonuniform film swelling and the onset of analogous through-bulk separation. TOF-SIMS highlights time-dependent segregation of Na within the structure, both to the film-current collector interface and to the film surface where a solid electrolyte interphase (SEI) exists, agreeing with the electrochemical impedance results that show time-dependent increase of the films' charge transfer resistance. We propose that Na segregation serves as a secondary source of stress relief, which occurs over somewhat longer time scales.
Thin tantalum films have been studied during in situ heating in a transmission electron microscope. Diffraction patterns from the as-deposited films were typical of amorphous materials. Crystalline grains were observed to form when the specimen was annealed in situ at 450 °C. Particular attention was addressed to the formation and growth of grains with the face-centered cubic (fcc) crystal structure. These observations are discussed in relation to prior work on the formation of fcc Ta by deformation and during thin film deposition.
The ability to integrate ceramics with other materials has been limited due to high temperature (>800°C) ceramic processing. Recently, researchers demonstrated a novel process, aerosol deposition (AD), to fabricate ceramic films at room temperature (RT). In this process, sub-micron sized ceramic particles are accelerated by pressurized gas, impacted on the substrate, plastically deformed, and form a dense film under vacuum. This AD process eliminates high temperature processing thereby enabling new coatings and device integration, in which ceramics can be deposited on metals, plastics, and glass. However, knowledge in fundamental mechanisms for ceramic particles to deform and form a dense ceramic film is still needed and is essential in advancing this novel RT technology. In this work, a combination of experimentation and atomistic simulation was used to determine the deformation behavior of sub-micron sized ceramic particles; this is the first fundamental step needed to explain coating formation in the AD process. High purity, single crystal, alpha alumina particles with nominal sizes of 0.3 µm and 3.0 µm were examined. Particle characterization, using transmission electron microscopy (TEM), showed that the 0.3 µm particles were relatively defect-free single crystals whereas 3.0 µm particles were highly defective single crystals or particles contained low angle grain boundaries. Sub-micron sized Al2O3 particles exhibited ductile failure in compression. In situ compression experiments showed 0.3µm particles deformed plastically, fractured, and became polycrystalline. Moreover, dislocation activity was observed within these particles during compression. These sub-micron sized Al2O3 particles exhibited large accumulated strain (2-3 times those of micron-sized particles) before first fracture. In agreement with the findings from experimentation, atomistic simulations of nano-Al2O3 particles showed dislocation slip and significant plastic deformation during compression. On the other hand, the micron sized Al2O3 particles exhibited brittle fracture in compression. In situ compression experiments showed 3µm Al2O3 particles fractured into pieces without observable plastic deformation in compression. Particle deformation behaviors will be used to inform Al2O3 coating deposition parameters and particle-particle bonding in the consolidated Al2O3 coatings.