Traveling waves of the solidification and melting of cubic crystal lattices.

Using the phase field crystal model (PFC model), an analysis of slow and fast dynamics of solid-liquid interfaces in solidification and melting processes is presented. Dynamical regimes for cubic lattices invading metastable liquids (solidification) and liquids propagating into metastable crystals (melting) are described in terms of the evolving amplitudes of the density field. Dynamical equations are obtained for body-centered cubic (bcc) and face-centered cubic (fcc) crystal lattices in one- and two-mode approximations. A universal form of the amplitude equations is obtained for the three-dimensional dynamics for different crystal lattices and crystallographic directions. Dynamics of the amplitude's propagation for different lattices and PFC mode's approximations is qualitatively compared. The traveling-wave velocity is quantitatively compared with data of molecular dynamics simulation previously obtained by Mendelev et al. [Modell. Simul. Mater. Sci. Eng. 18, 074002 (2010)MSMEEU0965-039310.1088/0965-0393/18/7/074002] for solidification and melting of the aluminum fcc lattice.

Controlling Grain Boundaries by Magnetic Fields.

The ability to use external magnetic fields to influence the microstructure in polycrystalline materials has potential applications in microstructural engineering. To explore this potential and to understand the complex interactions between electromagnetic fields and solid-state matter transport we consider a phase-field-crystal model. Together with efficient and scalable numerical algorithms this allows the examination of the role that external magnetic fields play on the evolution of defect structures and grain boundaries, on diffusive timescales. Examples for planar and circular grain boundaries explain the essential atomistic processes and large scale simulations in 2D are used to obtain statistical data on grain growth under the influence of external fields.

Grain Boundary Structures and Collective Dynamics of Inversion Domains in Binary Two-Dimensional Materials.

Understanding and controlling the properties and dynamics of topological defects is a lasting challenge in the study of two-dimensional materials, and is crucial to achieve high-quality films required for technological applications. Here grain boundary structures, energies, and dynamics of binary two-dimensional materials are investigated through the development of a phase field crystal model that is parametrized to match the ordering, symmetry, energy, and length scales of hexagonal boron nitride. Our studies reveal some new dislocation core structures for various symmetrically and asymmetrically tilted grain boundaries, in addition to those obtained in previous experiments and first-principles calculations. We also identify a defect-mediated growth dynamics for inversion domains governed by the collective atomic migration and defect core transformation at grain boundaries and junctions, a process that is related to inversion symmetry breaking in binary lattice.

Phase-field-crystal model for ordered crystals.

We describe a general method to model multicomponent ordered crystals using the phase-field-crystal (PFC) formalism. As a test case, a generic B2 compound is investigated. We are able to produce a line of either first-order or second-order order-disorder phase transitions, features that have not been incorporated in existing PFC approaches. Further, it is found that the only elastic constant for B2 that depends on ordering is C_{11}. This B2 model is then used to study antiphase boundaries (APBs). The APBs are shown to reproduce classical mean-field results. Dynamical simulations of ordering across small-angle grain boundaries predict that dislocation cores pin the evolution of APBs.

Emergence of Chirality from Isotropic Interactions of Three Length Scales.

Chirality is known to play a pivotal role in determining material properties and functionalities. However, it remains a great challenge to understand and control the emergence of chirality and the related enantioselective process particularly when the building components of the system are achiral. Here we explore the generic mechanisms driving the formation of two-dimensional chiral structures in systems characterized by isotropic interactions and three competing length scales. We demonstrate that starting from isotropic and rotationally invariant interactions, a variety of chiral ordered patterns and superlattices with anisotropic but achiral units can self-assemble. The mechanisms for selecting specific states are related to the length-scale coupling and the selection of resonant density wave vectors. Sample phase diagrams and chiral elastic properties are identified. These findings provide a viable route for predicting chiral phases and selecting the desired handedness.

Honeycomb and triangular domain wall networks in heteroepitaxial systems.

A comprehensive study is presented for the influence of misfit strain, adhesion strength, and lattice symmetry on the complex Moiré patterns that form in ultrathin films of honeycomb symmetry adsorbed on compact triangular or honeycomb substrates. The method used is based on a complex Ginzburg-Landau model of the film that incorporates elastic strain energy and dislocations. The results indicate that different symmetries of the heteroepitaxial systems lead to distinct types of domain wall networks and phase transitions among various surface Moiré patterns and superstructures. More specifically, the results show a dramatic difference between the phase diagrams that emerge when a honeycomb film is adsorbed on substrates of honeycomb versus triangular symmetry. It is also shown that in the small deformation limit, the complex Ginzburg-Landau model reduces to a two-dimensional sine-Gordon free energy form. This free energy can be solved exactly for one dimensional patterns and reveals the role of domains walls and their crossings in determining the nature of the phase diagrams.

Phase-field-crystal models and mechanical equilibrium.

Phase-field-crystal (PFC) models constitute a field theoretical approach to solidification, melting, and related phenomena at atomic length and diffusive time scales. One of the advantages of these models is that they naturally contain elastic excitations associated with strain in crystalline bodies. However, instabilities that are diffusively driven towards equilibrium are often orders of magnitude slower than the dynamics of the elastic excitations, and are thus not included in the standard PFC model dynamics. We derive a method to isolate the time evolution of the elastic excitations from the diffusive dynamics in the PFC approach and set up a two-stage process, in which elastic excitations are equilibrated separately. This ensures mechanical equilibrium at all times. We show concrete examples demonstrating the necessity of the separation of the elastic and diffusive time scales. In the small-deformation limit this approach is shown to agree with the theory of linear elasticity.

Microphase separation in comblike liquid-crystalline diblock copolymers.

The interplay between liquid crystallinity and microphase separation in comblike liquid-crystalline diblock copolymers is examined via a Brazovskii-type phenomenological model using both analytical and numerical calculations. For symmetric diblock copolymers we determine a critical electric field that is required to tilt the orientation of the constituent liquid crystals of the polymer side chains in the microphase-separated lamellar state. Such electrically induced reorientation of the liquid-crystal molecules can lead to substantially large changes of lamellar periodicity. Our numerical results show that highly aligned polymer lamellar domains can self-assemble when the liquid-crystal ordering precedes microphase separation, and that weak electric fields can be used to direct the self-assembly process due to the dielectric anisotropy of the liquid-crystal side chains. We also find that phase separation of asymmetric diblock copolymers can coexist with a network of liquid-crystal nematic orientations, with domain morphology depending on the details of copolymer and liquid-crystal coupling.

Phase-field-crystal model for magnetocrystalline interactions in isotropic ferromagnetic solids.

An isotropic magnetoelastic phase-field-crystal model to study the relation between morphological structure and magnetic properties of pure ferromagnetic solids is introduced. Analytic calculations in two dimensions were used to determine the phase diagram and obtain the relationship between elastic strains and magnetization. Time-dependent numerical simulations in two dimensions were used to demonstrate the effect of grain boundaries on the formation of magnetic domains. It was shown that the grain boundaries act as nucleating sites for domains of reverse magnetization. Finally, we derive a relation for coercivity versus grain misorientation in the isotropic limit.

Anomalous fast dynamics of adsorbate overlayers near an incommensurate structural transition.

We investigate the dynamics of a compressively strained adsorbed layer on a periodic substrate via a simple two-dimensional model that admits striped and hexagonal incommensurate phases. We show that the mass transport is superfast near the striped-hexagonal phase boundary and in the hexagonal phase. For an initial step profile separating a bare substrate region (or "hole") from the rest of a striped incommensurate phase, the superfast domain wall dynamics leads to a bifurcation of the initial step profile into two interfaces or profiles propagating in opposite directions with a hexagonal phase in between. This yields a theoretical understanding of the recent experiments for the Pb/Si(111) system.

Unconditionally stable method and numerical solution of the hyperbolic phase-field crystal equation.

The phase-field crystal model (PFC model) resolves systems on atomic length scales and diffusive time scales and lies in between standard phase-field modeling and atomistic methods. More recently a hyperbolic or modified PFC model was introduced to describe fast (propagative) and slow (diffusive) dynamics. We present a finite-element method for solving the hyperbolic PFC equation, introducing an unconditionally stable time integration algorithm. A spatial discretization is used with the traditional C^{0}-continuous Lagrange elements with quadratic shape functions. The space-time discretization of the PFC equation is second-order accurate in time and is shown analytically to be unconditionally stable. Numerical simulations are used to show a monotonic decrease of the free energy during the transition from the homogeneous state to stripes. Benchmarks on modeling patterns in two-dimensional space are carried out. The benchmarks show the applicability of the proposed algorithm for determining equilibrium states. Quantitatively, the proposed algorithm is verified for the problem of lattice parameter and velocity selection when a crystal invades a homogeneous unstable liquid.

Exploring the complex world of two-dimensional ordering with three modes.

The world of two-dimensional crystals is of great significance for the design and study of structural and functional materials with novel properties. Here we examine the mechanisms governing the formation and dynamics of these crystalline or polycrystalline states and their elastic and plastic properties by constructing a generic multimode phase field crystal model. Our results demonstrate that a system with three competing length scales can order into all five Bravais lattices, and other more complex structures including honeycomb, kagome, and other hybrid phases. In addition, nonequilibrium phase transitions are examined to illustrate the complex phase behavior described by the model. This model provides a systematic path to predict the influence of lattice symmetry on both the structure and dynamics of crystalline and defected systems.

Patterning of heteroepitaxial overlayers from nano to micron scales.

Thin heteroepitaxial overlayers have been proposed as templates to generate stable, self-organized nanostructures at large length scales, with a variety of important technological applications. However, modeling strain-driven self-organization is a formidable challenge due to different length scales involved. In this Letter, we present a method for predicting the patterning of ultrathin films on micron length scales with atomic resolution. We make quantitative predictions for the type of superstructures (stripes, honeycomb, triangular) and length scale of pattern formation of two metal-metal systems, Cu on Ru(0001) and Cu on Pd(111). Our findings are in excellent agreement with previous experiments and call for future experimental investigations of such systems.

Glassy phases and driven response of the phase-field-crystal model with random pinning.

We study the structural correlations and the nonlinear response to a driving force of a two-dimensional phase-field-crystal model with random pinning. The model provides an effective continuous description of lattice systems in the presence of disordered external pinning centers, allowing for both elastic and plastic deformations. We find that the phase-field crystal with disorder assumes an amorphous glassy ground state, with only short-ranged positional and orientational correlations, even in the limit of weak disorder. Under increasing driving force, the pinned amorphous-glass phase evolves into a moving plastic-flow phase and then, finally, a moving smectic phase. The transverse response of the moving smectic phase shows a vanishing transverse critical force for increasing system sizes.

Phase-field-crystal dynamics for binary systems: Derivation from dynamical density functional theory, amplitude equation formalism, and applications to alloy heterostructures.

The dynamics of phase field crystal (PFC) modeling is derived from dynamical density functional theory (DDFT), for both single-component and binary systems. The derivation is based on a truncation up to the three-point direct correlation functions in DDFT, and the lowest order approximation using scale analysis. The complete amplitude equation formalism for binary PFC is developed to describe the coupled dynamics of slowly varying complex amplitudes of structural profile, zeroth-mode average atomic density, and system concentration field. Effects of noise (corresponding to stochastic amplitude equations) and species-dependent atomic mobilities are also incorporated in this formalism. Results of a sample application to the study of surface segregation and interface intermixing in alloy heterostructures and strained layer growth are presented, showing the effects of different atomic sizes and mobilities of alloy components. A phenomenon of composition overshooting at the interface is found, which can be connected to the surface segregation and enrichment of one of the atomic components observed in recent experiments of alloying heterostructures.

Novel mechanical properties in lamellar phases of liquid-crystalline diblock copolymers.

Structural properties of flexible nematic diblock copolymers in the lamellar phase are investigated using a mean-field model. We address two complementary questions on the mechanics of the system: 1) How does the nematic order affect the elasticity of the one-dimensional solid? 2) What effect does the block copolymer microstructure has on the orientation of the nematic director? In the limit when the microstructure does not influence the nematic director orientation we predict a soft lamellar compression mode. When the microstructure does influence the nematic director orientation, small compressions lead to conventional elasticity, until a critical strain is reached, where there is then a transition to a softer response. On the other hand, we show that an identifiable lamellar symmetry provides a direction along which the nematic director prefers to align. Our model provides avenues to explore nonlinear properties of flexible diblock copolymers in which the monomers on both sides have mesogenic side groups.

Dynamical transitions and sliding friction of the phase-field-crystal model with pinning.

We study the nonlinear driven response and sliding friction behavior of the phase-field-crystal (PFC) model with pinning including both thermal fluctuations and inertial effects. The model provides a continuous description of adsorbed layers on a substrate under the action of an external driving force at finite temperatures, allowing for both elastic and plastic deformations. We derive general stochastic dynamical equations for the particle and momentum densities including both thermal fluctuations and inertial effects. The resulting coupled equations for the PFC model are studied numerically. At sufficiently low temperatures, we find that the velocity response of an initially pinned commensurate layer shows hysteresis with dynamical melting and freezing transitions for increasing and decreasing applied forces at different critical values. The main features of the nonlinear response in the PFC model are similar to the results obtained previously with molecular dynamics simulations of particle models for adsorbed layers.

Amplitude expansion of the binary phase-field-crystal model.

Amplitude representations of a binary phase-field-crystal model are developed for a two-dimensional triangular lattice and three-dimensional bcc and fcc crystal structures. The relationship between these amplitude equations and the standard phase-field models for binary-alloy solidification with elasticity are derived, providing an explicit connection between phase-field-crystal and phase-field models. Sample simulations of solute migration at grain boundaries, eutectic solidification, and quantum dot formation on nanomembranes are also presented.

A phase field crystal study of epitaxial island formation on nanomembranes.

In this paper the liquid phase heteroepitaxial growth of two-dimensional strained islands on nanomembranes is examined via an amplitude expansion of a binary phase field crystal model. The maximum size that the islands can grow to coherently is shown to be strongly dependent on the nanomembrane thickness and to a lesser extent on the flux rate. For a large membrane-island misfit of about 10%, islands were found to be able to grow coherently with the membrane to almost twice as large as those grown on thick membranes (or infinite substrates). It was also found that when islands are growing on both sides of the membrane, strain relaxation in the membrane leads to more and less favorable growth regions. For thinner membranes this effect increases the degree of ordering of the islands, a result consistent with recent experimental findings.

Thermodynamics of bcc metals in phase-field-crystal models.

We examine the influence of different forms of the free-energy functionals used in the phase-field-crystal (PFC) model, and compare them with the second-order density-functional theory (DFT) of freezing, by using bcc iron as an example case. We show that there are large differences between the PFC and the DFT and it is difficult to obtain reasonable parameters for existing PFC models directly from the DFT. Therefore, we propose a way of expanding the correlation function in terms of gradients that allows us to incorporate the bulk modulus of the liquid as an additional parameter in the theory. We show that this functional reproduces reasonable values for both bulk and surface properties of bcc iron, and therefore it should be useful in modeling bcc materials. As a further demonstration, we also calculate the grain boundary energy as a function of misorientation for a symmetric tilt boundary close to the melting transition.