Coarsening by network restructuring in model nanoporous gold

Using atomistic modeling, we show that restructuring of the network of interconnected ligaments causes coarsening in a model of nanoporous gold. The restructuring arises from the collapse of some ligaments onto neighboring ones and is enabled by localized plasticity at ligaments and nodes. This mechanism may explain the occurrence of enclosed voids and reduction in volume in nanoporous metals during their synthesis. An expression is developed for the critical ligament radius below which coarsening by network restructuring may occur spontaneously, setting a lower limit to the ligament dimensions of nanofoams

Molecular-dynamics simulations of stacking-fault-induced dislocation annihilation in pre-strained ultrathin single-crystalline copper films

We report results of large-scale molecular-dynamics (MD) simulations of dynamic deformation under biaxial tensile strain of pre-strained single-crystalline nanometer-scale-thick face-centered cubic (fcc) copper films. Our results show that stacking faults, which are abundantly present in fcc metals, may play a significant role in the dissociation, cross-slip, and eventual annihilation of dislocations in small-volume structures of fcc metals. The underlying mechanisms are mediated by interactions within and between extended dislocations that lead to annihilation of Shockley partial dislocations or formation of perfect dislocations. Our findings demonstrate dislocation starvation in small-volume structures with ultra-thin film geometry, governed by a mechanism other than dislocation escape to free surfaces, and underline the significant role of geometry in determining the mechanical response of metallic small-volume structures.Comment: 28 pages, 3 figure

Computational design of patterned interfaces using reduced order models

Patterning is a familiar approach for imparting novel functionalities to free surfaces. We extend the patterning paradigm to interfaces between crystalline solids. Many interfaces have non-uniform internal structures comprised of misfit dislocations, which in turn govern interface properties. We develop and validate a computational strategy for designing interfaces with controlled misfit dislocation patterns by tailoring interface crystallography and composition. Our approach relies on a novel method for predicting the internal structure of interfaces: rather than obtaining it from resource-intensive atomistic simulations, we compute it using an efficient reduced order model based on anisotropic elasticity theory. Moreover, our strategy incorporates interface synthesis as a constraint on the design process. As an illustration, we apply our approach to the design of interfaces with rapid, 1-D point defect diffusion. Patterned interfaces may be integrated into the microstructure of composite materials, markedly improving performance.United States. Dept. of Energy. Office of Basic Energy Sciences (Award 2008LANL1026)National Science Foundation (U.S.) (Grant 1150862

Atomic-Scale Analysis of Plastic Deformation in Thin-Film Forms of Electronic Materials

Nanometer-scale-thick films of metals and semiconductor heterostructures are used increasingly in modern technologies, from microelectronics to various areas of nanofabrication. Processing of such ultrathin-film materials generates structural defects, including voids and cracks, and may induce structural transformations. Furthermore, the mechanical behavior of these small-volume structures is very different from that of bulk materials. Improvement of the reliability, functionality, and performance of nano-scale devices requires a fundamental understanding of the atomistic mechanisms that govern the thin-film response to mechanical loading in order to establish links between the films\u27 structural evolution and their mechanical behavior. Toward this end, a significant part of this study is focused on the analysis of atomic-scale mechanisms of plastic deformation in freestanding, ultrathin films of face-centered cubic (fcc) copper (Cu) that are subjected to biaxial tensile strain. The analysis is based on large-scale molecular-dynamics simulations. Elementary mechanisms of dislocation nucleation are studied and several problems involving the structural evolution of the thin films due to the glide of and interactions between dislocations are addressed. These problems include void nucleation, martensitic transformation, and the role of stacking faults in facilitating dislocation depletion in ultrathin films and other small-volume structures of fcc metals. Void nucleation is analyzed as a mechanism of strain relaxation in Cu thin films. The glide of multiple dislocations causes shearing of atomic planes and leads to formation of surface pits, while vacancies are generated due to the glide motion of jogged dislocations. Coalescence of vacancy clusters with surface pits leads to formation of voids. In addition, the phase transformation of fcc Cu films to hexagonal-close packed (hcp) ones is studied. The resulting martensite phase nucleates at the film\u27s free surface and grows into the bulk of the film due to dislocation glide. The role of surface orientation in the strain relaxation of these strained thin films under biaxial tension is discussed and the stability of the fcc crystalline phase is analyzed. Finally, the mechanical response during dynamic tensile straining of pre-treated fcc metallic thin films with varying propensities for formation of stacking faults is analyzed. Interactions between dislocations and stacking faults play a significant role in the cross-slip and eventual annihilation of dislocations in films of fcc metals with low-to-medium values of the stable-to-unstable stacking-fault energy ratio, γs/γu. Stacking-fault-mediated mechanisms of dislocation depletion in these ultrathin fcc metallic films are identified and analyzed. Additionally, a theoretical analysis for the kinetics of strain relaxation in Si 1-x Ge x (0 ≤ x ≤ 1) thin films grown epitaxially on Si(001) substrates is conducted. The analysis is based on a properly parameterized dislocation mean-field theoretical model that describes plastic-deformation dynamics due to threading dislocation propagation; the analysis addresses strain relaxation kinetics during both epitaxial growth and thermal annealing, including post-implantation annealing. The theoretical predictions for strain relaxation as a function of film thickness in Si 0.80 Ge 0.20 /Si(001) samples annealed after growth, either unimplanted or after He + implantation, are in excellent agreement with reported experimental measurements

Formation, migration, and clustering of delocalized vacancies and interstitials at a solid-state semicoherent interface

Atomistic simulations are used to study the formation, migration, and clustering of delocalized vacancies and interstitials at a model fcc-bcc semicoherent interface formed by adjacent layers of Cu and Nb. These defects migrate between interfacial trapping sites through a multistep mechanism that may be described using dislocation mechanics. Similar mechanisms operate in the formation, migration, and dissociation of interfacial point defect clusters. Effective migration rates may be computed using the harmonic approximation of transition state theory with a temperature-dependent prefactor. Our results demonstrate that delocalized vacancies and interstitials at some interfaces may be viewed as genuine defects, albeit governed by mechanisms of higher complexity than conventional point defects in crystalline solids.National Science Foundation (U.S.) (Grant No. OCI-1053575)United States. Dept. of Energy. Office of Basic Energy Sciences (Award No. 2008LANL1026

Dislocation mechanism of interface point defect migration

Vacancies and interstitials absorbed at Cu-Nb interfaces are shown to migrate by a multistage process involving the thermally-activated formation, motion, and annihilation of kinks and jogs on interface misfit dislocations. This mechanism, including the energy along the entire migration path, can be described quantitatively within dislocation theory, suggesting that analysis of misfit dislocation networks may enable prediction of point defect behaviors at semicoherent heterointerfaces.United States. Dept. of Energy. Office of Basic Energy Sciences (award 2008LANL1026

A Hybrid Open-Framework Aluminium Phosphate-Oxalate Possessing Large Circular 12-Membered Channels

A new aluminum phosphate-oxalate, I, [N2C4H12]Al2(PO4) (HPO4)(C2O4)]H2O, has been synthesized hydrothermally in the presence of structure-directing amines. The hybrid structure comprises a vertex-linkage of AlO6 octahedra, PO4 tetrahedra, and C2O4 units leading to three-dimensional connectivity. The connectivity between AlO6 and PO4 units are such that it forms double-six rings that are connected to each other via the oxalate units, thereby leading to the formation of a large circular 12-membered channel of width ~9 Å along the c axis. The structure-directing amine along with one water molecule is situated within this channel. The connectivity also forms two different types of 8-membered channels along the a and b axes. The three-dimensional structure of I, is very similar to the naturally occurring aluminosilicate zeolite, gmelinite. Crystal data for I are: monoclinic, space group Pccm, a = 9.992(1), b = 11.644(1), c = 12.231(1) Å, V = 1423.0(2), M = 438.9, Z = 4, RF = 0.07

Direct Exchange Mechanism for Interlayer Ions in Non-Swelling Clays.

The mobility of radiocesium in the environment is largely mediated by cation exchange in micaceous clays, in particular Illite-a non-swelling clay mineral that naturally contains interlayer K+ and has high affinity for Cs+. Although exchange of interlayer K+ for Cs+ is nearly thermodynamically nonselective, recent experiments show that direct, anhydrous Cs+-K+ exchange is kinetically viable and leads to the formation of phase-separated interlayers through a mechanism that remains unclear. Here, using classical atomistic simulations and density functional theory calculations, we identify a molecular-scale positive feedback mechanism in which exchange of the larger Cs+ for the smaller K+ significantly lowers the migration barrier of neighboring K+, allowing exchange to propagate rapidly once initiated at the clay edge. Barrier lowering upon slight increase in layer spacing (∼0.7 Å) during Cs+ exchange is an example of "chemical-mechanical coupling" that likely explains the observed sharp exchange fronts leading to interstratification. Interestingly, we find that these features are thermodynamically favored even in the absence of a heterogeneous layer charge distribution