Template-directed colloidal crystallization
TL;DR: In this article, the slow sedimentation of colloidal particles onto a patterned substrate (or template) can direct the crystallization of bulk colloidal crystals, and so permit tailoring of the lattice structure, orientation and size of the resulting crystals.
Abstract: Colloidal crystals are three-dimensional periodic structures formed from small particles suspended in solution. They have important technological uses as optical filters1–3, switches4 and materials with photonic band gaps5,6, and they also provide convenient model systems for fundamental studies of crystallization and melting7–10. Unfortunately, applications of colloidal crystals are greatly restricted by practical difficulties encountered in synthesizing large single crystals with adjustable crystal orientation11. Here we show that the slow sedimentation of colloidal particles onto a patterned substrate (or template) can direct the crystallization of bulk colloidal crystals, and so permit tailoring of the lattice structure, orientation and size of the resulting crystals: we refer to this process as 'colloidal epitaxy'. We also show that, by using silica spheres synthesized with a fluorescent core12,13, the defect structures in the colloidal crystals that result from an intentional lattice mismatch of the template can be studied by confocal microscopy14. We suggest that colloidal epitaxy will open new ways to design and fabricate materials based on colloidal crystals and also allow quantitative studies of heterogeneous crystallization in real space.
Citations
More filters
TL;DR: The interest in nanoscale materials stems from the fact that new properties are acquired at this length scale and, equally important, that these properties are equally important.
Abstract: The interest in nanoscale materials stems from the fact that new properties are acquired at this length scale and, equally important, that these properties * To whom correspondence should be addressed. Phone, 404-8940292; fax, 404-894-0294; e-mail, mostafa.el-sayed@ chemistry.gatech.edu. † Case Western Reserve UniversitysMillis 2258. ‡ Phone, 216-368-5918; fax, 216-368-3006; e-mail, burda@case.edu. § Georgia Institute of Technology. 1025 Chem. Rev. 2005, 105, 1025−1102
6,852 citations
TL;DR: Self-assembling processes are common throughout nature and technology and involve components from the molecular to the planetary scale and many different kinds of interactions.
Abstract: Self-assembly is the autonomous organization of components into patterns or structures without human intervention. Self-assembling processes are common throughout nature and technology. They involve components from the molecular (crystals) to the planetary (weather systems) scale and many different kinds of interactions. The concept of self-assembly is used increasingly in many disciplines, with a different flavor and emphasis in each.
6,491 citations
TL;DR: In this article, solution phase syntheses and size-selective separation methods to prepare semiconductor and metal nanocrystals, tunable in size from ∼1 to 20 nm and monodisperse to ≤ 5%, are presented.
Abstract: ▪ Abstract Solution phase syntheses and size-selective separation methods to prepare semiconductor and metal nanocrystals, tunable in size from ∼1 to 20 nm and monodisperse to ≤5%, are presented. Preparation of monodisperse samples enables systematic characterization of the structural, electronic, and optical properties of materials as they evolve from molecular to bulk in the nanometer size range. Sample uniformity makes it possible to manipulate nanocrystals into close-packed, glassy, and ordered nanocrystal assemblies (superlattices, colloidal crystals, supercrystals). Rigorous structural characterization is critical to understanding the electronic and optical properties of both nanocrystals and their assemblies. At inter-particle separations 5–100 A, dipole-dipole interactions lead to energy transfer between neighboring nanocrystals, and electronic tunneling between proximal nanocrystals gives rise to dark and photoconductivity. At separations <5 A, exchange interactions cause otherwise insulating ass...
4,116 citations
TL;DR: In this paper, the authors describe the appearance of complex, ordered structures induced by the buckling of thin metal films owing to thermal contraction of an underlying substrate, and account qualitatively for the size and form of the patterned features in terms of the nonuniform stresses developed in the film near steps on the polymer substrate.
Abstract: Spontaneous generation of complex order in apparently simple systems is both arresting and potentially useful1,2,3,4,5,6,7,8,9,10,11. Here we describe the appearance of complex, ordered structures induced by the buckling of thin metal films owing to thermal contraction of an underlying substrate. We deposit the films from the vapour phase on a thermally expanded polymer (polydimethylsiloxane, PDMS). Subsequent cooling of the polymer creates compressive stress in the metal film that is relieved by buckling with a uniform wavelength of 20–50 micrometres. The waves can be controlled and orientated by relief structures in the surface of the polymer, which can set up intricate, ordered patterns over large areas. We can account qualitatively for the size and form of the patterned features in terms of the non-uniform stresses developed in the film near steps on the polymer substrate. This patterning process may find applications in optical devices such as diffraction gratings and optical sensors, and as the basis for methods of strain analysis in materials.
2,158 citations
TL;DR: This work describes a technique—three-dimensional holographic lithography—that is well suited to the production of three-dimensional structures with sub-micrometre periodicity, and has made microperiodic polymeric structures, and used these as templates to create complementary structures with higher refractive-index contrast.
Abstract: The term 'photonics' describes a technology whereby data transmission and processing occurs largely or entirely by means of photons. Photonic crystals are microstructured materials in which the dielectric constant is periodically modulated on a length scale comparable to the desired wavelength of operation. Multiple interference between waves scattered from each unit cell of the structure may open a 'photonic bandgap'--a range of frequencies, analogous to the electronic bandgap of a semiconductor, within which no propagating electromagnetic modes exist. Numerous device principles that exploit this property have been identified. Considerable progress has now been made in constructing two-dimensional structures using conventional lithography, but the fabrication of three-dimensional photonic crystal structures for the visible spectrum remains a considerable challenge. Here we describe a technique--three-dimensional holographic lithography--that is well suited to the production of three-dimensional structures with sub-micrometre periodicity. With this technique we have made microperiodic polymeric structures, and we have used these as templates to create complementary structures with higher refractive-index contrast.
1,737 citations
Cites background from "Template-directed colloidal crystal..."
..., but the use of close-packed spheres severely restricts the range of lattices that may be produce...
[...]
References
More filters
TL;DR: In this paper, a high-throughput lithographic method with 25-nanometer resolution and smooth vertical sidewalls is proposed and demonstrated, which uses compression molding to create a thickness contrast pattern in a thin resist film carried on a substrate, followed by anisotropic etching to transfer the pattern through the entire resist thickness.
Abstract: A high-throughput lithographic method with 25-nanometer resolution and smooth vertical sidewalls is proposed and demonstrated. The technique uses compression molding to create a thickness contrast pattern in a thin resist film carried on a substrate, followed by anisotropic etching to transfer the pattern through the entire resist thickness. Metal patterns with a feature size of 25 nanometers and a period of 70 nanometers were fabricated with the use of resist templates created by imprint lithography in combination with a lift-off process. With further development, imprint lithography should allow fabrication of sub-10-nanometer structures and may become a commercially viable technique for manufacturing integrated circuits and other nanodevices.
2,396 citations
TL;DR: In this paper, a detailed study of the phase diagram of suspensions of colloidal spheres which interact through a steep repulsive potential is presented. But it is not a detailed analysis of the colloidal glass phase.
Abstract: Suspensions of spherical colloidal particles in a liquid show a fascinating variety of phase behaviour which can mimic that of simple atomic liquids and solids. ‘Colloidal fluids’1–4, in which there are significant short-range correlations between the positions of neighbouring particles, and ‘colloidal crystals’5–7, which have long-range spatial order, have been investigated extensively. We report here a detailed study of the phase diagram of suspensions of colloidal spheres which interact through a steep repulsive potential. With increasing particle concentration we observed a progression from colloidal fluid, to fluid and crystal phases in coexistence, to fully crystallized samples. At the highest concentrations we obtained very viscous samples in which full crystallization had not occurred after several months and in which the particles appeared to be arranged as an amorphous ‘colloidal glass’. The empirical phase diagram can be reproduced reasonably well by an effective hard-sphere model. The observation of the colloidal glass phase is interesting both in itself and because of possible relevance to the manufacture of high-strength ceramics8.
1,881 citations
TL;DR: In this article, the authors presented a method to compute the absolute free energy of arbitrary solid phases by Monte Carlo simulation based on the construction of a reversible path from the solid phase under consideration to an Einstein crystal with the same crystallographic structure.
Abstract: We present a new method to compute the absolute free energy of arbitrary solid phases by Monte Carlo simulation. The method is based on the construction of a reversible path from the solid phase under consideration to an Einstein crystal with the same crystallographic structure. As an application of the method we have recomputed the free energy of the fcc hard‐sphere solid at melting. Our results agree well with the single occupancy cell results of Hoover and Ree. The major source of error is the nature of the extrapolation procedure to the thermodynamic limit. We have also computed the free energy difference between hcp and fcc hard‐sphere solids at densities close to melting. We find that this free energy difference is not significantly different from zero: −0.001<ΔF<0.002.
1,025 citations
TL;DR: In this article, stable dispersions of colloidal colloidal silica spheres containing a dye or fluorophore have been synthesized according to a general procedure and dispersed in polar and apolar liquids.
Abstract: Stable dispersions of monodisperse colloidal silica spheres containing a dye or fluorophore have been synthesized according to a general procedure and dispersed in polar and apolar liquids. The procedure consists of the coupling of the dye to a silane coupling agent, (3++minopropyl)triethoxysilane, and the controllable incorporation of the reaction product into the silica sphere. The silica spheres are prepared from tetraethoxysilane in mixtures of ammonia, water, and ethanol. The composition of the silica spheres can be controlled in such a way that the organic groups can be placed on the surface, in a thin shell inside the particle or distributed through the volume of an inner core. Fluorescein isothiocyanate was used to make easily bleachable, fluorescent silica spheres. Hydrophilic charge stabilized and organophilic sterically stabilized 1-octadecanol-coated dyed silica systems were synthesized and dispersed in several solvents. All the particles were characterized after the several reaction steps by static and dynamic light scattering and transmission electron microscopy. The fluorescent spheres were further characterized by fluorescence spectroscopy and confocal scanning laser fluorescence microscopy. Great effort was taken to prepare monodisperse dispersions free of clusters of particles. Such model dispersions are required for (scattering) studies of interparticle interactions in (concentrated) systems. Therefore, the several steps of the synthesis and optical characterization are described in detail.
707 citations