Colloidal Quasicrystals Research Articles

Colloidal quasicrystals engineered with DNA.

In principle, designing and synthesizing almost any class of colloidal crystal is possible. Nonetheless, the deliberate and rational formation of colloidal quasicrystals has been difficult to achieve. Here we describe the assembly of colloidal quasicrystals by exploiting the geometry of nanoscale decahedra and the programmable bonding characteristics of DNA immobilized on their facets. This process is enthalpy-driven, works over a range of particle sizes and DNA lengths, and is made possible by the energetic preference of the system to maximize DNA duplex formation and favour facet alignment, generating local five- and six-coordinated motifs. This class of axial structures is defined by a square-triangle tiling with rhombus defects and successive on-average quasiperiodic layers exhibiting stacking disorder which provides the entropy necessary for thermodynamic stability. Taken together, these results establish an engineering milestone in the deliberate design of programmable matter.

Self-assembly of dodecagonal and octagonal quasicrystals in hard spheres on a plane.

Hard spheres are one of the most fundamental model systems in soft matter physics, and have been instrumental in shedding light on nearly every aspect of classical condensed matter. Here, we add one more important phase to the list that hard spheres form: quasicrystals. Specifically, we use simulations to show that an extremely simple, purely entropic model system, consisting of two sizes of hard spheres resting on a flat plane, can spontaneously self-assemble into two distinct random-tiling quasicrystal phases. The first quasicrystal is a dodecagonal square-triangle tiling, commonly observed in a large variety of colloidal systems. The second quasicrystal has, to our knowledge, never been observed in either experiments or simulations. It exhibits octagonal symmetry, and consists of three types of tiles: triangles, small squares, and large squares, whose relative concentration can be continuously varied by tuning the number of smaller spheres present in the system. The observed tile composition of the self-assembled quasicrystals agrees very well with the theoretical prediction we obtain by considering the four-dimensional (lifted) representation of the quasicrystal. Both quasicrystal phases form reliably and rapidly over a significant part of parameter space. Our results demonstrate that entropy combined with a set of geometrically compatible, densely packed tiles can be sufficient ingredients for the self-assembly of colloidal quasicrystals.

Entropic formation of a thermodynamically stable colloidal quasicrystal with negligible phason strain

Quasicrystals have been discovered in a variety of materials ranging from metals to polymers. Yet, why and how they form is incompletely understood. In situ transmission electron microscopy of alloy quasicrystal formation in metals suggests an error-and-repair mechanism, whereby quasiperiodic crystals grow imperfectly with phason strain present, and only perfect themselves later into a high-quality quasicrystal with negligible phason strain. The growth mechanism has not been investigated for other types of quasicrystals, such as dendrimeric, polymeric, or colloidal quasicrystals. Soft-matter quasicrystals typically result from entropic, rather than energetic, interactions, and are not usually grown (either in laboratories or in silico) into large-volume quasicrystals. Consequently, it is unknown whether soft-matter quasicrystals form with the high degree of structural quality found in metal alloy quasicrystals. Here, we investigate the entropically driven growth of colloidal dodecagonal quasicrystals (DQCs) via computer simulation of systems of hard tetrahedra, which are simple models for anisotropic colloidal particles that form a quasicrystal. Using a pattern recognition algorithm applied to particle trajectories during DQC growth, we analyze phason strain to follow the evolution of quasiperiodic order. As in alloys, we observe high structural quality; DQCs with low phason strain crystallize directly from the melt and only require minimal further reduction of phason strain. We also observe transformation from a denser approximant to the DQC via continuous phason strain relaxation. Our results demonstrate that soft-matter quasicrystals dominated by entropy can be thermodynamically stable and grown with high structural quality--just like their alloy quasicrystal counterparts.

Phasonic Diffusion and Self-confinement of Decagonal Quasicrystals in Hyperspace

We introduce a novel simulation method that is designed to explore fluctuations of the phasonic degrees of freedom in decagonal colloidal quasicrystals. Specifically, we attain and characterise thermal equilibrium of the phason ensemble via Monte Carlo simulations with particle motions restricted to elementary phasonic flips. We find that, at any temperature, the random tiling ensemble is strongly preferred over the minimum phason-strain quasicrystal. Phasonic flips are the dominant carriers of diffusive mass transport in physical space. Sub- diffusive transients suggest cooperative flip behaviour on short time scales. In complementary space, particle mobility is geometrically restricted to a thin ring around the acceptance domain, resulting in self-confinement and persistent phasonic order.

Event-chain Monte Carlo simulations of the liquid to solid transition of two-dimensional decagonal colloidal quasicrystals

In event-chain Monte Carlo simulations, we model colloidal particles in two dimensions that interact according to an isotropic short-ranged pair potential which supports the two typical length scales present in decagonal quasicrystals. We investigate the assembled structures as we vary the density and temperature. Our special interest is related to the transition from quasicrystal to liquid. In contrast to the KTHNY melting theory for quasicrystals which predicts an intermediate pentahedratic phase, we find a one-step first-order melting transition. However, we discover that the slow relaxation of phasonic flips, i.e. rearrangements of the particles due to additional degrees of freedom in quasicrystals, changes the positional correlation functions, to the extent that structures with long-range orientational correlations, but exponentially decaying positional correlations, are observed.

Colloidal quasicrystals based on hybrid nanoparticles

We used laser ablation approach for the synthesis of PbTe nanoparticles (NPs) that allows for the control of the mean size of NPs. The addition of gold particles to the solution results in the formation of hybrid NPs characterized by the amplification and broadening of the near-field photoluminescence spectra compared to initial NPs.

Growth of two-dimensional dodecagonal colloidal quasicrystals: Particles with isotropic pair interactions with two length scales vs. patchy colloids with preferred binding angles.

We explore the growth of colloidal quasicrystals with dodecagonal symmetry in two dimensions by employing Brownian dynamics simulations. On the one hand, we study the growth behavior of structures obtained in a system of particles that interact according to an isotropic pair potential with two typical length scales. On the other hand, we consider patchy colloids that possess only one typical interaction length scale but prefer given binding angles. In case of the isotropic particles, we show that an imbalance in the competition between the two distances might lead to defects with wrong nearest-neighbor distances in the resulting structure. In contrast, during the growth of quasicrystals with patchy colloids such defects do not occur due to the lack of a second interaction length scale. However, as a downside, the diffusion of patchy particles along a surface typically is slower such that domains occur where the particles possess different phononic and phasonic offsets. Our results are important to understand how soft matter quasicrystals can be grown as perfectly as possible and to obtain a deeper insight into the mechanisms of the growth of quasicrystals in general.

Growth of two-dimensional decagonal colloidal quasicrystals

The growth of quasicrystals, i.e. structures with long-range positional order but no periodic translational symmetry, is more complex than the growth of periodic crystals. By employing Brownian dynamics simulations in two dimensions for colloidal particles that interact according to an isotropic pair potential with two incommensurate lengths, we study the growth of quasicrystalline structures by sequentially depositing particles at their surface. We quantify the occurrence of quasicrystalline order as a function of the temperature and the rate of added particles. In addition, we explore defects like local triangular order or gaps within the quasicrystalline structure. Furthermore, we analyze the shapes of the surfaces in grown structures which tend to build straight lines along the symmetry axes of the quasicrystal. Finally, we identify phasonic flips which are rearrangements of the particles due to additional degrees of freedom. The number of phasonic flips decreases with the distance to the surface.

Detection of phonon and phason modes in intrinsic colloidal quasicrystals by reconstructing their structure in hyperspace

Phasons are additional degrees of freedom which occur in quasicrystals alongside the phonons known from conventional periodic crystals. The rearrangements of particles that are associated with a phason mode are hard to interpret in physical space. We reconstruct the quasicrystal structure by an embedding into extended higher-dimensional space, where phasons correspond to displacements perpendicular to the physical space. In dislocation-free decagonal colloidal quasicrystals annealed with Brownian dynamics simulations, we identify thermal phonon and phason modes. Finite phononic strain is pinned by phasonic excitations even after cooling down to zero temperature. For the phasonic displacements underlying the flip pattern, the reconstruction method gives an approximation within the limits of a multi-mode harmonic ansatz, and points to fundamental limitations of a harmonic picture for phasonic excitations in intrinsic colloidal quasicrystals.

Molecular dynamics study of colloidal quasicrystals.

Colloidal quasicrystals have received increased interest recently due to new insight in exploring their potential for photonic materials as well as for optical devices [Vardeny et al., Nat. Photonics, 2013, 7, 177]. Colloidal quasicrystals in aqueous solutions have been found in systems of micelles with impenetrable cores [Fischer et al., Proc. Natl. Acad. Sci. U. S. A., 2011, 108, 1810]. A simple model potential for micelle-micelle interaction is the step potential, which is infinite for core overlaps and constant for shell overlaps. Dotera et al. performed Monte Carlo simulations of the step potential model and found quasicrystals for specific values of the packing fraction η and the shell-core ratio λ [Dotera et al., Nature, 2014, 506, 208 ]. However, the overlap of real micelles causes repulsive forces, which increase with decreasing core distance. We consider this by introducing a novel model potential with repulsive forces depending on a third parameter α. In a systematic manner we study this more realistic potential with two-dimensional molecular dynamics simulations. For α = 0 the model is similar to the step potential model. For the first time, we provide a comprehensive overview of crystalline, quasicrystalline, and disordered structures as a function of η and λ. Simulations performed with α > 0 show the impact of the repulsive forces. We find that quasicrystalline structures at high densities vanish while new quasicrystalline structures appear at intermediate densities. Our results help to tailor colloidal systems for today's advanced applications in photonics and optical devices.

Course of dislocation lines in templated three-dimensional colloidal quasicrystals

We present an approach based on colloidal epitaxy to obtain three-dimensional colloidal quasicrystals, i.e., structures with long-range order but no periodicity. In contrast to other attempts to obtain soft-matter quasicrystals by design, no fine tuning of the colloid-colloid interactions is required. By using Monte Carlo simulations, we explore the development of multiple layers with the desired quasicrystalline symmetry when the colloidal particles sediment onto suitable quasicrystalline substrates. In addition, well-defined defect lines can be induced in the grown colloidal quasicrystal by constructing substrates with well-chosen defects that lead to induced defect lines. We present a study of the three-dimensional course of such dislocation lines by inducing and analyzing stable lines that bend, unstable ones that split up, or defect lines that merge with other defects. Dislocations are characterized by Burgers vectors that are composed of a phononic part as in a periodic crystal and an additional phasonic part that is unique to quasicrystals. As in a periodic crystal, the sum of all Burgers vectors is conserved along defect lines and at all forks. However, unlike in a periodic crystal, the course of a dislocation line in a quasicrystal depends on its position. Furthermore, although in a quasicrystal all Burgers vectors can always be written as sum of Burgers vectors with a smaller phononic part, we find dislocations that do not decompose into dislocations with smaller phononic Burgers vectors. For quasicrystals with eightfold and twelvefold rotational symmetry, we identify basis Burgers vectors that denote stable dislocations. Our results can be verified in experiments and are important for applications of colloidal quasicrystals, e.g., for the development of photonic quasicrystals.

Periodic average structures of colloidal quasicrystals.

We experimentally study the phase behaviour of a charge-stabilized two-dimensional colloidal monolayer which is subjected to a one-dimensional quasiperiodic substrate potential. Upon increasing the laser intensity, we observe a transition from a periodic to a quasiperiodic state. It proceeds via the formation of an intermediate periodic average structure (PAS) which is related to the quasiperiodic lattice by a bounded 1-1 mapping. Because PAS can transform to crystals and quasicrystals by minute particle displacements, they provide a mechanism to allow for interesting insights into the relationship between periodic and quasiperiodic order.

Comparing light-induced colloidal quasicrystals with different rotational symmetries

Quasicrystals are aperiodic structures with long-range orientational order. Unlike crystals, quasicrystals can, in principle, possess any non-crystallographic rotational symmetry. However, only a few of these rotational symmetries have been observed. By using Monte Carlo simulations of colloidal particles in laser interference patterns with quasicrystalline symmetry, we compare the onset of quasicrystalline order for different rotational symmetries in two dimensions. We find that quasicrystals with 5-, 8-, 10-, and 12-fold rotational axes can be induced with lower laser intensities than quasicrystals with other non-crystallographic rotational symmetries. We relate this finding to the number of local symmetry centers in the respective interference patterns.

What Phasons Look Like: Particle Trajectories in a Quasicrystalline Potential

Among the distinctive features of quasicrystals-structures with long-range order but without periodicity-are phasons. Phasons are hydrodynamic modes that, like phonons, do not cost free energy in the long-wavelength limit. For light-induced colloidal quasicrystals, we analyze the collective rearrangements of the colloids that occur when the phasonic displacement of the light field is changed. The colloidal model system is employed to study the link between the continuous description of phasonic modes in quasicrystals and collective phasonic flips of atoms. We introduce characteristic areas of reduced phononic and phasonic displacements and use them to predict individual colloidal trajectories. In principle, our method can be employed with all quasicrystalline systems in order to derive collective rearrangements of particles from the continuous description of phasons.

Colloidal quasicrystals with 12-fold and 18-fold diffraction symmetry

Micelles are the simplest example of self-assembly found in nature. As many other colloids, they can self-assemble in aqueous solution to form ordered periodic structures. These structures so far all exhibited classical crystallographic symmetries. Here we report that micelles in solution can self-assemble into quasicrystalline phases. We observe phases with 12-fold and 18-fold diffraction symmetry. Colloidal water-based quasicrystals are physically and chemically very simple systems. Macroscopic monodomain samples of centimeter dimension can be easily prepared. Phase transitions between the fcc phase and the two quasicrystalline phases can be easily followed in situ by time-resolved diffraction experiments. The discovery of quasicrystalline colloidal solutions advances the theoretical understanding of quasicrystals considerably, as for these systems the stability of quasicrystalline states has been theoretically predicted for the concentration and temperature range, where they are experimentally observed. Also for the use of quasicrystals in advanced materials this discovery is of particular importance, as it opens the route to quasicrystalline photonic band gap materials via established water-based colloidal self-assembly techniques.

Proliferation of anomalous symmetries in colloidal monolayers subjected to quasiperiodic light fields

Quasicrystals provide a fascinating class of materials with intriguing properties. Despite a strong potential for numerous technical applications, the conditions under which quasicrystals form are still poorly understood. Currently, it is not clear why most quasicrystals hold 5- or 10-fold symmetry but no single example with 7- or 9-fold symmetry has ever been observed. Here we report on geometrical constraints which impede the formation of quasicrystals with certain symmetries in a colloidal model system. Experimentally, colloidal quasicrystals are created by subjecting micron-sized particles to two-dimensional quasiperiodic potential landscapes created by n = 5 or seven laser beams. Our results clearly demonstrate that quasicrystalline order is much easier established for n = 5 compared to n = 7. With increasing laser intensity we observe that the colloids first adopt quasiperiodic order at local areas which then laterally grow until an extended quasicrystalline layer forms. As nucleation sites where quasiperiodicity originates, we identify highly symmetric motifs in the laser pattern. We find that their density strongly varies with n and surprisingly is smallest exactly for those quasicrystalline symmetries which have never been observed in atomic systems. Since such high-symmetry motifs also exist in atomic quasicrystals where they act as preferential adsorption sites, this suggests that it is indeed the deficiency of such motifs which accounts for the absence of materials with e.g., 7-fold symmetry.

Stability of Colloidal Quasicrystals

Freezing of charge-stabilized colloidal suspensions and relative stabilities of crystals and quasicrystals are studied using thermodynamic perturbation theory. Macroion interactions are modelled by effective pair potentials combining electrostatic repulsion with polymer-depletion or van der Waals attraction. Comparing free energies -- counterion terms included -- for elementary crystals and rational approximants to icosahedral quasicrystals, parameters are identified for which one-component quasicrystals are stabilized by a compromise between packing entropy and cohesive energy.