Structural Coloration with Nonclose‐Packed Array of Bidisperse Colloidal Particles

Colloidal crystals and glasses have their own photonic effects. Colloidal crystals show high reflectivity at narrowband, whereas colloidal glasses show low reflectivity at broadband. To compromise the opposite optical properties, a simple means is suggested to control the colloidal arrangement between crystal and glass by employing two different sizes of silica particles with repulsive interparticle potential. Monodisperse silica particles with repulsive potential spontaneously form crystalline structure at volume fraction far below 0.74. When two different sizes of silica particles coexist, the arrangement of silica particles is significantly influenced by two parameters: size contrast and mixing ratio. When the size contrast is small, a long‐range order is partially conserved in the entire mixing ratio, resulting in a pronounced reflectance peak and brilliant structural color. When the size contrast is large, the long‐range order is rapidly reduced along with mixing ratio. Nevertheless, a short‐range order survives, which causes low reflectivity at a broad wavelength, developing faint structural colors. These findings offer an insight into controlling the colloidal arrangements and provide a simple way to tune the optical property of colloidal arrays for structural coloration.     

Growth of Large Colloidal Crystals with Their (100) Planes Orientated Parallel to the Surfaces of Supporting Substrates

Templating against two‐dimensional (2D) regular arrays of square pyramidal pits etched in Si(100) wafers has been exploited to fabricate colloidal crystals with their (100) planes oriented parallel to the substrates (see Figure for an SEM image). The capability and feasibility of this method have been demonstrated by crystallizing 1.0, 0.48, and 0.25 μm polystyrene beads into 3D opaline lattices having such an orientation over areas as large as several square centimeters. Like their (111)‐oriented cousins, these long‐range ordered lattices of spherical colloids are useful in many areas such as photonics and porous materials. In particular, the ability to generate large colloidal crystals with adjustable spatial orientations will allow one to systematically investigate their photonic band structures in an effort to elucidate the structure–property relationship.     

Stabilization of Colloidal Crystals Engineered with DNA

A postsynthetic method for stabilizing colloidal crystals programmed from DNA is developed. The method relies on Ag⁺ ions to stabilize the particle‐connecting DNA duplexes within the crystal lattice, essentially transforming them from loosely bound structures to ones with very strong interparticle links. Such crystals do not dissociate as a function of temperature like normal DNA or DNA‐interconnected superlattices, and they can be moved from water to organic media or the solid state, and stay intact. The Ag⁺‐stabilization of the DNA bonds is accompanied by a nondestructive ≈25% contraction of the lattice, and both the stabilization and contraction are reversible with the chemical extraction of the Ag⁺ ions, by AgCl precipitation with NaCl. This synthetic tool is important, since it allows scientists and engineers to study such crystals in environments that are incompatible with structures made by conventional DNA programmable methods and without the influence of a matrix such as silica.     

Cover Picture: Functionalization of Crystalline Colloidal Arrays through Click Chemistry (Adv. Mater. 21/2007)

Photonic crystals based on electrostatically‐stabilized colloidal arrays dispersed in a liquid medium are of interest to materials scientists partly because of the optical tuning afforded to theses systems with a variation in interparticle distance. On p. 3507, Stephen Foulger and co‐workers from Clemson University, USA report on a general strategy for the preparation of well‐defined and regioselectively functionalized ordered colloidal particles through the exploitation of “click” chemistry. Click transformations have found utility in the synthesis and/or functionalization of a range of systems. In addition, the solvochromic tuning of the ordered arrays is employed to modify the emission spectra of the surface‐attached photoluminescent dyes.     

The Control of Colloidal Grain Boundaries through Evaporative Vertical Self‐Assembly

Self‐assembly continuously gains attention as an excellent method to create novel nanoscale structures with a wide range of applications in photonics, optoelectronics, biomedical engineering, and heat transfer applications. However, self‐assembly is governed by a diversity of complex interparticle forces that cause fabricating defectless large scale (>1 cm) colloidal crystals, or opals, to be a daunting challenge. Despite numerous efforts to find an optimal method that offers the perfect colloidal crystal by minimizing defects, it has been difficult to provide physical interpretations that govern the development of defects such as grain boundaries. This study reports the control over grain domains and intentional defect characteristics that develop during evaporative vertical deposition. The degree of particle crystallinity and evaporation conditions is shown to govern the grain domain characteristics, such as shapes and sizes. In particular, the grains fabricated with 300 and 600 nm sphere diameters can be tuned into single‐column structures exceeding ≈1 mm by elevating heating temperature up to 93 °C. The understanding of self‐assembly physics presented in this work will enable the fabrication of novel self‐assembled structures with high periodicity and offer fundamental groundworks for developing large‐scale crack‐free structures.     

Ptychographic X‐Ray Imaging of Colloidal Crystals

Ptychographic coherent X‐ray imaging is applied to obtain a projection of the electron density of colloidal crystals, which are promising nanoscale materials for optoelectronic applications and important model systems. Using the incident X‐ray wavefield reconstructed by mixed states approach, a high resolution and high contrast image of the colloidal crystal structure is obtained by ptychography. The reconstructed colloidal crystal reveals domain structure with an average domain size of about 2 µm. Comparison of the domains formed by the basic close‐packed structures, allows us to conclude on the absence of pure hexagonal close‐packed domains and confirms the presence of random hexagonal close‐packed layers with predominantly face‐centered cubic structure within the analyzed part of the colloidal crystal film. The ptychography reconstruction shows that the final structure is complicated and may contain partial dislocations leading to a variation of the stacking sequence in the lateral direction. As such in this work, X‐ray ptychography is extended to high resolution imaging of crystalline samples.     

Real‐Time Monitoring of Colloidal Crystallization in Electrostatically‐Levitated Drops

Colloidal crystallization is analogous to the crystallization in bulk atomic systems in various aspects, which has been explored as a model system. However, a real‐time probing of the phenomenon still remains challenging. Here, a levitation system for a study of colloidal crystallization is demonstrated. Colloidal particles in a levitated droplet are gradually concentrated by isotropic evaporation of water from the surface of the droplet, resulting in crystallization. The structural change of the colloidal array during crystallization is investigated by simultaneously measuring the volume and reflectance spectra of the droplet. The crystal nucleates from the surface of the droplet at which the volume fraction exceeds the threshold and then the growth proceeds. The crystal growth behavior depends on the initial concentrations of colloidal particles and salts which determine the overall direction of crystal growth and interparticle spacing, respectively. The results show that a levitating bulk droplet has a great potential as a tool for in situ investigation of colloidal crystallization.     

Inside Front Cover: Line Defects Embedded in Three‐Dimensional Photonic Crystals (Adv. Mater. 15/2005)

The inside cover illustrates an approach to creating line defects embedded in the interior of a self‐assembled photonic crystal, as reported by Zhao and co‐workers on p. 1917. Photoresist patterns are first constructed on the surface of a silica opal film by conventional optical photolithography. After regrowth of the silica colloidal crystal, photoresist line defects are successfully introduced into the self‐assembled silica colloidal crystal. Further processing results in an inverse opal with air‐core line defects embedded in its interior, which provides a prototype for future optical waveguide devices based on self‐assembled three‐dimensional photonic crystals.     

Inside Front Cover: Redox‐Tunable Defects in Colloidal Photonic Crystals (Adv. Mater. 20/2005)

The inside front cover illustrates reversible tuning of an intragap transmitting state induced by redox cycling, accomplished using a redox‐active polyferrocenylsilane polyelectrolyte multilayer planar defect embedded in a colloidal photonic crystal (CPC) synthesized by a bottom–up method combining colloidal self‐assembly and microcontact printing. In work reported on p. 2455 by Manners, Ozin, and co‐workers, the wavelength position of the defect state can be changed by changing the oxidation state of the ferrocene moieties in the polymer backbone. This could find applications in electrochemically tunable microcavities, and—if light emitters are incorporated—electrochemically tunable CPC‐based laser sources. Cover design by Ludovic Cademartiri.     

DNA-controlled assembly of a NaTl lattice structure from gold nanoparticles and protein nanoparticles

The formation of diamond structures from tailorable building blocks is an important goal in colloidal crystallization because the non-compact diamond lattice is an essential component of photonic crystals for the visible-light range. However, designing nanoparticle systems that self-assemble into non-compact structures has proved difficult. Although several methods have been proposed, single-component nanoparticle assembly of a diamond structure has not been reported. Binary systems, in which at least one component is arranged in a diamond lattice, provide alternatives, but control of interparticle interactions is critical to this approach. DNA has been used for this purpose in a number of systems. Here we show the creation of a non-compact lattice by DNA-programmed crystallization using surface-modified Qβ phage capsid particles and gold nanoparticles, engineered to have similar effective radii. When combined with the proper connecting oligonucleotides, these components form NaTl-type colloidal crystalline structures containing interpenetrating organic and inorganic diamond lattices, as determined by small-angle X-ray scattering. DNA control of assembly is therefore shown to be compatible with particles possessing very different properties, as long as they are amenable to surface modification.     

Inside Front Cover: Experimental Evidence for Superprism Effects in Three‐Dimensional Polymer Photonic Crystals (Adv. Mater. 2/2006)

The inside cover illustrates the highly dispersive propagation of light in a three‐dimensional polymer photonic crystal. White light is coupled into a woodpile structure and split into its wavelength components due to the frequency‐dependent dispersion properties of the structure. This superprism effect is orders of magnitudes higher than in a conventional glass prism and is caused by the strong anisotropy of the dispersion surface at frequencies slightly above the photonic bandgap. In work reported on p. 221, Serbin and Gu fabricated these woodpile structures operating in the near‐infrared wavelength range by means of two‐photon polymerization and give theoretical and experimental evidence for the superprism effect in these low‐index photonic‐crystal structures.     

Colloidal Self‐Assembly Meets Nanofabrication: From Two‐Dimensional Colloidal Crystals to Nanostructure Arrays

Self‐assembly of colloidal microspheres or nanospheres is an effective strategy for fabrication of ordered nanostructures. By combination of colloidal self‐assembly with nanofabrication techniques, two‐dimensional (2D) colloidal crystals have been employed as masks or templates for evaporation, deposition, etching, and imprinting, etc. These methods are defined as “colloidal lithography”, which is now recognized as a facile, inexpensive, and repeatable nanofabrication technique. This paper presents an overview of 2D colloidal crystals and nanostructure arrays fabricated by colloidal lithography. First, different methods for fabricating self‐assembled 2D colloidal crystals and complex 2D colloidal crystal structures are summarized. After that, according to the nanofabrication strategy employed in colloidal lithography, related works are reviewed as colloidal‐crystal‐assisted evaporation, deposition, etching, imprinting, and dewetting, respectively.     

Guiding the Dewetting of Thin Polymer Films by Colloidal Imprinting

Micropatterned surfaces are important in many biomedical and bioengineering applications, such as the development of biosensors. An approach for the creation of ordered surface patterns, fabricated combining colloidal crystals, consisting of ordered layers of micrometric particles, with dewetting of bilayers of thin polymer films is introduced. The produced patterns are both topographical and chemical in nature, consisting of ordered arrays of microscale holes imprinted in a polymer film, with tunable size. The spontaneous dewetting of the polymer film enables this tunability, with a maximum sevenfold increase in lateral size of the holes and sixfold increase in depth from imprinting to coalescence with neighboring holes. Polymer dewetting and layer inversion are seen to compete during the annealing of the polymer bilayers, and the optimal conditions for hole growth are identified. An in‐depth investigation highlights the effects of UV‐ozone treatment on the long‐range ordering of the colloidal crystals and on preventing the dewetting of the imprinted bilayers. Ordered patterns of different size and depth are produced over large areas by tuning of the colloidal crystal assembly, UV surface treatment and dewetting conditions. Potential applications of the micropatterns produced in the present work include microarrays for single cell studies and biosensors.     

Pressure‐Responsive Hierarchical Chiral Photonic Aerogels

Pressure‐responsive chiral photonic aerogels are fabricated by combining liquid crystal self‐assembly and ice‐templating processes. The aerogels have a hierarchical structure in which the primary 2D chiral nematic structured walls of cellulose nanocrystals form ribbons that support a secondary 3D cellular network. Owing to the flexibility of the aerogels in solvent, the 3D structure of the aerogel can easily be transformed to a 2D structure by pressure‐induced rearrangement. The aerogels vary from white in color, which arises from light scattering, to a reflective photonic crystal displaying bright iridescent colors that depend on the immersed solvent. A solvent‐sensitive ink that shows quick color response to different solvents is designed using the pressure‐responsive photonic aerogel. This material demonstrates a new response mechanism for the design of smart and mechanoresponsive photonic materials.     

Unconventional Atomic Structure of Graphene Sheets on Solid Substrates

The atomic structure of free‐standing graphene comprises flat hexagonal rings with a 2.5 Å period, which is conventionally considered the only atomic period and determines the unique properties of graphene. Here, an unexpected highly ordered orthorhombic structure of graphene is directly observed with a lattice constant of ≈5 Å, spontaneously formed on various substrates. First‐principles computations show that this unconventional structure can be attributed to the dipole between the graphene surface and substrates, which produces an interfacial electric field and induces atomic rearrangement on the graphene surface. Further, the formation of the orthorhombic structure can be controlled by an artificially generated interfacial electric field. Importantly, the 5 Å crystal can be manipulated and transformed in a continuous and reversible manner. Notably, the orthorhombic lattice can control the epitaxial self‐assembly of amyloids. The findings reveal new insights about the atomic structure of graphene, and open up new avenues to manipulate graphene lattices.     

An Unprecedented Stimuli‐Controlled Single‐Crystal Reversible Phase Transition of a Metal–Organic Framework and Its Application to a Novel Method of Guest Encapsulation

The flexibility and unexpected dynamic behavior of a third‐generation metal–organic framework are described for the first time. The synthetic strategy is based on the flexibility and spherical shape of dipyridyl‐based carborane linkers that act as pillars between rigid Co/BTB (BTB: 1,3,5‐benzenetricarboxylate) layers, providing a 3D porous structure ( 1 ). A phase transition of the solid can be induced to generate a new, nonporous 2D structure ( 2 ) without any loss of the carborane linkers. The structural transformation is visualized by snapshots of the multistep single‐crystal‐to‐single‐crystal transformation by single‐crystal and powder X‐ray diffraction. Poor hydrogen bond acceptors such as MeOH, CHCl₃ or supercritical CO₂ induce such a 3D to 2D transformation. Remarkably, the transformation is reversible and the 2D phase 2 is further converted back into 1 by heating in dimethylformamide. The energy requirements involved in such processes are investigated using periodic density functional theory calculations. As a proof of concept for potential applications, encapsulation of C₆₀ is achieved by trapping this molecule during the reversible 2D to 3D phase transition, whereas no adsorption is observed by straight solvent diffusion into the pores of the 3D phase.     

A controlled formation of cage-like nanoporous hollow silica microspheres

Cage-like hollow silica microspheres composed of mesoporous silica nanoparticles and macroporous interparticle voids were fabricated via the latex-surfactant dual templates route, simply by controlling the surfactant additions below its critical micelle concentration. The surface area, pore volume increase, and both the mesopore and macropore sizes decrease with the increase in surfactant amount. The surfactant cations preferentially assemble with negatively charged silica species generated by the hydrolysis and condensation of tetraethyl orthosilicate to form composite silica-surfactant nanoparticles. The electrostatic repulsion between the silica-surfactant composite nanoparticles and negatively charged polystyrene (PS) beads is smaller than that between surfactant-free silica and PS, favoring the deposition of composite nanoparticles on the surface of PS template. In the meantime, the deposited nanoparticles also have reduced repulsion from their neighbors, favoring their bridging to form silica shells. The more the surfactant is used, the less the repulsion exists among the composite particles and the smaller the interparticle macroporous voids are.     

How the Molecular Packing Affects the Room Temperature Phosphorescence in Pure Organic Compounds: Ingenious Molecular Design,Detailed Crystal Analysis,and Rational Theoretical Calculations

Long‐lived phosphorescence at room temperature (RTP) from pure organic molecules is rare. Recent research reveals various crystalline organic molecules can realize RTP with lifetimes extending to the magnitude of second. There is little research on how molecular packing affecting RTP. Three compounds are designed with similar optical properties in solution, but tremendously different solid emission characteristics. By investigating the molecular packing arrangement in single crystals, it is found that the packing style of the compact face to face favors of long phosphorescence lifetime and high photoluminescence efficiency, with the lifetime up to 748 ms observed in the crystal of CPM ((9H‐carbazol‐9‐yl)(phenyl)methanone). Theoretical calculation analysis also reveals this kind of packing style can remarkably reduce the singlet excited energy level and prompt electron communication between dimers. Surprisingly, CPM has two very similar single crystals, labeled as CPM and CPM‐A, with almost identical crystal data, and the only difference is that molecules in CPM‐A crystal take a little looser packing arrangement. X‐ray diffraction and cross‐polarization under magic spinning ¹³C NMR spectra double confirm that they are different crystals. Interestingly, CPM‐A crystal shows negligible RTP compared to the CPM crystal, once again proving that the packing style is critical to the RTP property.     

Tunable Fluorescence from Dye‐Modified DNA‐Assembled Plasmonic Nanocube Arrays

Colloidal crystal engineering with DNA on template‐confined surfaces is used to prepare arrays of nanocube‐based plasmonic antennas and deliberately place dyes with sub‐nm precision into their hotspots, on the DNA bonds that confine the cubes to the underlying gold substrate. This combined top‐down and bottom‐up approach provides independent control over both the plasmonic gap and photonic lattice modes of the surface‐confined particle assemblies and allows for the tuning of the interactions between the excited dyes and plasmonically active antennas. Furthermore, the gap mode of the antennas can be modified in situ by utilizing the solvent‐dependent structure of the DNA bonds. This is studied by placing two dyes, with different emission wavelengths, under the nanocubes and recording their solvent‐dependent emission. It is shown that dye emission not only depends upon the in‐plane structure of the antennas but also the size of the gap, which is regulated with solvent. Importantly, this approach allows for the systematic understanding of the relationship between nanoscale architecture and plasmonically coupled dye emission, and points toward the use of colloidal crystal engineering with DNA to create stimuli responsive architectures, which can find use in chemical sensing and tunable light sources.     

Preparation of Macroscopic Block‐Copolymer‐Based Gyroidal Mesoscale Single Crystals by Solvent Evaporation

Properties arising from ordered periodic mesostructures are often obscured by small, randomly oriented domains and grain boundaries. Bulk macroscopic single crystals with mesoscale periodicity are needed to establish fundamental structure–property correlations for materials ordered at this length scale (10–100 nm). A solvent‐evaporation‐induced crystallization method providing access to large (millimeter to centimeter) single‐crystal mesostructures, specifically bicontinuous gyroids, in thick films (>100 µm) derived from block copolymers is reported. After in‐depth crystallographic characterization of single‐crystal block copolymer–preceramic nanocomposite films, the structures are converted into mesoporous ceramic monoliths, with retention of mesoscale crystallinity. When fractured, these monoliths display single‐crystal‐like cleavage along mesoscale facets. The method can prepare macroscopic bulk single crystals with other block copolymer systems, suggesting that the method is broadly applicable to block copolymer materials assembled by solvent evaporation. It is expected that such bulk single crystals will enable fundamental understanding and control of emergent mesostructure‐based properties in block‐copolymer‐directed metal, semiconductor, and superconductor materials.