# Composition Patterning in Systems Driven by Competing Dynamics

## Abstract

We study an alloy system where short-ranged, thermally-driven diffusion competes with externally imposed, finite-ranged, athermal atomic exchanges, as is the case in alloys under irradiation. Using a Cahn-Hilliard-type approach, we show that when the range of these exchanges exceeds a critical value, labyrinthine concentration patterns at a mesoscopic scale can be stabilized. Furthermore, these steady-state patterns appear only for a window of the frequency of forced exchanges. Our results suggest that ion beams may provide a novel route to stabilize and tune the size of nanoscale structural features in materials.

The spontaneous formation of steady-state patterns have been extensively observed in many equilibrium and nonequilibrium systems . While for equilibrium systems (e.g. ferrofluids, block copolymer melts, etc.) patterning is a result of the competition between repulsive and attractive interactions of different length scales, in nonequilibrium systems (e.g. reaction-diffusion systems, etc.), steady-state patterning is often the result of the competition between several dynamical mechanisms. A conceptual connection between the two classes of systems can sometimes be realized with the construction of Lyapunov functionals and effective Hamiltonians, by which steady-state pattern formation in dynamical systems is interpreted as resulting from the competition between different types of effective interactions.

The kinetic Ising-type model with competing dynamics, and its continuum mean field counterpart, are instruments by which we hope to understand a whole class of nonequilibrium driven systems , ranging from fast ionic conductors to alloys under irradiation. The main ingredient of this model is the competition between two dynamics: one one hand, a thermally-driven mechanism trying to bring the system to thermodynamical equilibrium; on the other hand, externally imposed particle exchanges of a nature essentially athermal. The usual attempt has been to express the steady state of the system in terms of effective Hamiltonians and effective thermodynamic potentials. P. Garrido, J. Marro, and collaborators , were able to derive effective Hamiltonians for several types of 1D Ising models with competing dynamics. Z. Rácz and collaborators , studied the relation between the range of the externally imposed exchanges and the range of the effective interactions. In the context of alloys under irradiation, using a kinetic Ising-type model, Vaks and Kamyshenko  derived a formal expression for the steady state probability distribution in terms of effective interactions, while from a continuum perspective, Martin  studied the corresponding dynamical phase diagram by an effective free energy. The possibility of patterning as a result of the competing dynamics has not been considered in these works. However, in the limiting case of arbitrary length external exchanges, patterning has been recently observed in mean field and Monte Carlo simulations . In this situation, the coarsening of segregated phases (magnetic domains in the Ising case) saturates, leading to a steady-state labyrinthine patterning at a mesoscopic length scale. This microstructure is rationalized in terms of a competition between the attractive nearest neighbors interactions, and a repulsive electrostatic-like effective interaction. These patterns do not appear if the external exchanges are short range, e.g. when they occur between nearest neighbors . The behavior difference between these two limiting regimes raises the question of whether there exists a critical value for the range of external exchanges for patterning to occur. The main objective of this Letter is to address this question, which besides having its own theoretical interest, is relevant to alloys under irradiation. Indeed, forced relocation of atoms in displacement cascades may extend beyond nearest-neighbor distances, especially in the case of dense cascades or for open crystal structures .

To render the problem more concrete, let us consider a binary alloy with a positive heat of mixing, under irradiation. Each time an external particle collides with the solid, a local atomic rearrangement is produced. These rearrangements have a ballistic component that mixes the atoms regardless of their chemical identity, trying to bring the system to a random solid solution. Due to its local nature, the ballistic mixing will relocate atoms in a region of characteristic radius $`R`$. The case $`R\mathrm{}`$, or arbitrary-length ballistic exchanges, has already been studied: The macroscopic governing equation is identical to that describing a binary alloy undergoing a chemical reaction $`AB`$ , and the one describing a block copolymer (BCP) melt . From the studies of these systems, the physics of this case is well understood. In terms of the frequency of forced exchanges $`\mathrm{\Gamma }`$, it has been shown that while high values bring the system to a random solid solution, there is a critical value below which the homogeneous concentration profile becomes unstable towards phase separation. As in spinodal decomposition, enriched regions form and coarsen. However, the characteristic length of the domains $`l`$, instead of growing indefinitely towards a macroscopic phase separation, saturates at a mesoscopic scale, $`l_{\mathrm{}}`$. For $`\mathrm{\Gamma }`$ values close to the critical value, the steady-state concentration profile has a sinusoidal-wave appearance, with diffuse interfaces, what is referred to as the weak-segregation regime. For smaller $`\mathrm{\Gamma }`$ values, the concentration profile presents sharper interfaces, with a square-wave-like appearance, what is referred to as the strong-segregation regime. In each regime, the characteristic length has been shown to follow a power law with the exchange frequency $`l_{\mathrm{}}\mathrm{\Gamma }^\varphi `$, with an exponent $`\varphi `$ of 1/4 for the weak and 1/3 for the strong-segregation regime .

In the case of ballistic exchanges of a finite range $`R`$, there should still be a critical value $`\mathrm{\Gamma }(R)`$ below which the system phase separates. The question is whether phase coexistence takes place at a macroscopic or mesoscopic scale. In principle, we can predict that if certain $`\mathrm{\Gamma }`$ equilibrates a wavelength $`l`$ for arbitrary length exchanges, finite range exchanges must also generate patterns when $`Rl`$. It is, however, difficult to determine a priori the exact conditions under which coarsening will saturate as a function of $`R`$ and $`\mathrm{\Gamma }`$. In this Letter we show that given a certain $`R`$, there is an interval $`[\mathrm{\Gamma }_1(R),\mathrm{\Gamma }_2(R)]`$ for the stabilization of patterns. Above $`\mathrm{\Gamma }_2`$ the homogeneous concentration profile is stable, and below $`\mathrm{\Gamma }_1`$ coarsening continues with the time, with the system separating into macroscopic phases. The extent of this interval for patterning decreases with $`R`$, reaching a zero value at a critical, nonzero value $`R_c`$, when $`\mathrm{\Gamma }_1(R_c)=\mathrm{\Gamma }_2(R_c)=\mathrm{\Gamma }_c`$. For ballistic mixing with a radius smaller than $`R_c`$, patterning is not possible. We also show that, given a mixing distance $`R`$, there is an upper bound for the wavelengths attainable as $`\mathrm{\Gamma }\mathrm{\Gamma }_1^+(R)`$. These conclusions are in agreement with recent Kinetic Monte Carlo simulations of binary alloys under finite-range ballistic exchanges .

We study the problem using a Cahn-Hilliard-type description of one-dimensional fronts, simulating the walls of the labyrinthine patterns, and we construct a variational formulation to investigate the solution. The equation describing the temporal evolution is composed of two terms, one for thermal diffusion and another one for ballistic mixing :

$$\frac{\psi }{t}=\frac{\psi ^{\text{th}}}{t}+\frac{\psi ^{\text{bal}}}{t}.$$
(1)   
Here we have chosen to represent the concentration field by a globally conserved order parameter $`\psi (𝐱)`$ so that the homogeneous concentration profile (solid solution) corresponds to $`\psi =0`$. In the previous equation, the first term is simply given by $`M^2(\frac{\delta F}{\delta \psi })`$, where $`F`$ is the global free energy, and we have assumed a constant mobility $`M`$. As for the second term, we actually need to perform a derivation. For that purpose, let us consider first ballistic mixing occurring one dimensionally between planes along a crystallographic direction. The rate of change of concentration in the plane $`i`$ due to interchange of atoms with the planes labeled $`j`$ is given by 

$$\frac{\psi _i^{\text{bal}}}{t}=\mathrm{\Gamma }\underset{j}{}w_j(\psi _i\psi _{i+j})=\mathrm{\Gamma }(\psi _i\psi ),$$
(2)   
where $`w_j`$ is a normalized weight function describing the distribution of ballistic exchange distances, and the brackets denote the corresponding (discrete) weighted spatial average. The extension to the continuum is immediate, and we write the governing equation as:

$$\frac{\psi }{t}=M^2(\frac{\delta F}{\delta \psi })\mathrm{\Gamma }(\psi \psi _R).$$
(3)   
$`w_R(𝐱)`$ is now a continuous function peaked around the origin with a width proportional to $`R`$, and the average denoted by the brackets is defined as:

$$\psi _R=w_R(𝐱𝐱^{})\psi (𝐱^{})𝑑𝐱^{}.$$
(4)   
In the limit $`R0`$, the ballistic term reduces to a Laplacian term, expressing diffusion. In limit $`R\mathrm{}`$, we recover the governing equation for the case of arbitrary-length ballistic exchanges.

In analogy to what was done in the case of arbitrary-length exchanges, we seek to find a Lyapunov functional for this problem, which we shall refer to as the free energy functional of the system . This idea actually traces back to the work of Leibler , and Ohta and Kawasaki , on block copolymer melts. This functional is given by $`E=F+\gamma G`$, and it is built so as to determine the kinetics: $`\frac{\psi }{t}=M^2(\frac{\delta E}{\delta \psi })`$. $`G`$ is a new term describing effective interactions related to the ballistic term, and to simplify the notation, we use $`\gamma =\mathrm{\Gamma }/M`$ for the rest of this paper.

For $`F`$, we use a Ginzburg-Landau free energy

$$F=(A\psi ^2+B\psi ^4+C|\psi |^2)𝑑𝐱,$$
(5)   
while $`G`$ is expressed by a self-interaction of the form

$$G=\frac{1}{2}\psi (𝐱)g(𝐱𝐱^{})\psi (𝐱^{})𝑑𝐱𝑑𝐱^{},$$
(6)   
with $`g`$ a kernel satisfying

$$^2g(𝐱𝐱^{})=(\delta (𝐱𝐱^{})w_R(𝐱𝐱^{})).$$
(7)   
To proceed further, at this point we need to make a choice of the weight function $`w_R`$. A Yukawa-type potential has been proposed by N. Goldenfeld . This form fits the observed distribution distances of ballistic exchanges for crystals under irradiation , while allowing us to handle part of the minimization problem analytically. In one dimension, $`w_R(u)=R/2\mathrm{exp}(|u|/R)`$.

Having stated the problem, we start by performing a stability analysis of Eq. 3. For small perturbations of the form $`e^{\omega t+ikx}`$ around a constant profile $`\psi =0`$, it is straightforward to find the dispersion relation:

$$\frac{\omega (k)}{M}=2Ak^22Ck^4\frac{\gamma R^2k^2}{1+R^2k^2}.$$
(8)   
A series of plots of this dispersion relationship for different values of $`\gamma `$ is shown in Fig. 1. As in the case of arbitrary length ballistic exchanges, there is a critical value $`\gamma _2`$ below which the homogeneous concentration profile becomes unstable. Below this value, there is a window of $`k`$ values $`(k_1,k_2)`$ for which the homogeneous solution is locally unstable, suggesting a wavelength selection. For smaller values of $`\gamma `$, the dispersion relation resembles the one of spinodal decomposition, suggesting macroscopic phase separation. 

To confirm these predictions, we use a variational approach, based in minimizing the free energy functional $`E`$. Let us consider first the weak-segregation regime, where the choice of $`w_R`$ allows us to solve the problem analytically, and then consider the strong-segregation regime, where we need to appeal to a numerical treatment.

In the weak-segregation regime, we can perform the minimization of $`E`$ by considering a sine family of parametric functions, $`\psi (x)=\alpha \mathrm{sin}(kx)`$. We obtain the energy per unit length:

$$E(\alpha ,k)=\alpha ^2\frac{A}{2}+\alpha ^4\frac{3B}{8}+\alpha ^2k^2\frac{C}{2}+\alpha ^2\frac{\gamma L^2}{4(1+k^2L^2)}.$$
(9)   
Minimization of this energy is performed analytically, and concentration patterning, indicated by solutions with nonzero values of $`k`$ and $`\alpha `$ are found for an interval in $`\gamma `$. In reality, the value of $`\gamma _1`$ predicted by this parametric functions is an underestimation. Before that value is reached, the energy per unit length for the macroscopically separated system becomes lower than the energy per unit length for the sine profile. The crossover point determines the actual value of $`\gamma _1`$ in the weak segregation regime approximation, where patterning occurs in the interval given by:

$`\gamma _1`$ $`=`$ $`\sqrt{({\displaystyle \frac{2\sqrt{3C}+\sqrt{6[(3\sqrt{6})AR^2(\sqrt{6}2)C]}}{3R^2}})},`$ (10)   
$`\gamma _2`$ $`=`$ $`(A+C/R^2)^2/2C.`$ (11)   
This interval shrinks to zero at a critical value of $`R_c=\sqrt{C/A}`$, corresponding to $`\gamma _c=2A^2/C`$. As a consequence of $`\gamma _1`$ being determined by a crossover of energies, a transition towards macroscopic phase separation occurs at a finite value of $`k`$. As a result, there is a bound in the wavelength of the patterns for a given $`R`$.

In the strong-segregation regime, we need to improve over the approximation of sine waves for a proper evaluation of $`\gamma _1`$ away from the critical point. To this purpose, we propose to minimize the free energy functional using the tanh-sine family of parametric functions $`\psi (x)=\alpha \mathrm{tanh}(m/k\mathrm{sin}(kx))`$. The parameter $`m`$ serves to change the wave profile continuously from a sinusoidal type, to a tanh-like type with sharp interfaces, matching the concentration profile of an equilibrium interface.

It is easy to minimize first with respect to the parameter $`\alpha `$. We obtain the expression, for $`\alpha >0`$,

$$E=\frac{(A\epsilon _1C\epsilon _3+\gamma \epsilon _4)^2}{4B\epsilon _2},$$
(12)   
where the $`\epsilon _i`$ quantities denote the energy per unit length associated with each one of the terms in the free energy functional. Here we can see that the values of $`\gamma `$ and $`k`$ that minimize the free energy are independent of the parameter $`B`$, which only relates to the amplitude $`\alpha `$.

The energy per unit length (the $`\epsilon `$ terms) cannot be obtained analytically for these functions, so we proceed with a numerical strategy. The free energy per unit length is computed by numerical integration, and the actual minimization is performed by means of the subroutine MNFB from NETLIB , based on a secant Hessian approximation. Figure 2 shows $`k`$ versus $`\gamma `$ plots for a series of values of $`R`$. The physical parameters $`A`$ and $`C`$ are set to unity. From this plot we obtain the dependency of $`\gamma _1`$ and the corresponding wave vector $`k_1`$ (related to the maximum attainable wavelength) as a function of $`R`$. Figure 3 is a double-log plot of these quantities for large values of $`R`$, showing a power law dependency. A fit of the data with the power laws $`\gamma _1=pR^\theta `$ and $`k_1=qR^\sigma `$ yield the quantities $`p=2.26\pm 0.03`$, $`\theta =3.039\pm 0.006`$ and $`q=0.54\pm 0.02`$, $`\sigma =1.03\pm 0.01`$. Still, an almost perfect fit is obtained by the simple laws: $`\gamma _1=2/R^3`$ and $`k_1=1/(2R)`$, as shown in the figure. The latter relationship has the physical interpretation that $`R`$ is the parameter determining the maximum wavelength. Furthermore, the combination of these two relationships yield the power law for the $`R\mathrm{}`$ case: $`k\gamma ^{1/3}`$. For values of $`A`$ and $`C`$ not equal to one, the corresponding dependencies can be derived by dimensional analysis, giving: $`\gamma _1=2\sqrt{AC}/R^3`$ and $`k_1=1/(2R)`$. Figure 4 summarizes the steady-state regimes in the $`\gamma `$-$`R`$ space. Patterning may occur in the present model when the range of the forced exchanges exceeds a critical value, with a maximum wavelength proportional to that range. In the case of alloys under irradiation, typical $`R`$ values range from 2 to 10 $`\AA `$, suggesting that patterns up to 100 $`\AA `$ could be stabilized. Experimental work to test these predictions is under progress.

We are very grateful to Nigel Goldenfeld for his clever suggestions and enlighting discussions. We also want to thank the MRL Center for Computation at the University of Illinois for their assistance. This work was partly supported by the US Department of Energy grant DOFG02-96ER45439 through the University of Illinois Materials Research Laboratory.