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Volume 18 | Number 19 | 21 May 2008 | Pages 21612284

ISSN 0959-9428

FEATURE ARTICLE Seung-Man Yang, Gi-Ra Yi et al. Synthesis and assembly of structured colloidal particles

PAPER Eduardo Ruiz-Hitzky et al. Poly(3,4-ethylenedioxythiophene) clay nanocomposites

FEATURE ARTICLE

www.rsc.org/materials | Journal of Materials Chemistry

Synthesis and assembly of structured colloidal particles


Seung-Man Yang,*a Shin-Hyun Kim,a Jong-Min Lima and Gi-Ra Yi*b
Received 24th October 2007, Accepted 21st February 2008 First published as an Advance Article on the web 11th March 2008 DOI: 10.1039/b716393b Synthesis and self-assembly of structured colloids is a nascent eld. Recent advances in this area include the development of a variety of practical routes to produce robust photonic band-gap materials, colloidal lithography for nanopatterns, and hierarchically structured porous materials with high surface-to-volume ratios for catalyst supports. To improve their properties, non-conventional suprastructures have been proposed, which could be built up using binary or bimodal mixtures of spherical particles and particles with internal or surface nanostructures. This Feature Article will describe the state-of-the-art in colloidal particles and their assemblies. The paper consists of three main sections categorized by the type of colloid, namely shape-anisotropic particles, chemically patterned particles and internally structured particles. In each section, we will discuss not only synthetic routes to uniform colloids with a range of structures, features and shapes, but also self-organization of these colloids into macrocrystalline structures with varying nanoscopic features and functionalities. Finally, we will outline future perspectives for these colloidal suprastructures.

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I.

Introduction

Following a few pioneering reports in the late 1990s that colloidal crystals can serve as photonic bandgap structures and as templates for functional materials, there has been considerable interest in colloids, and their potential use for nano- and bio-photonic applications, from the materials chemistry community.1,2 To date, a number of colloidal structures for photonic crystals have
a National Creative Research Initiative Center for Integrated Optouidic Systems, Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology, Daejeon, 305-701, Korea. E-mail: smyang@kaist.ac.kr; Fax: +82-42-869-5962; Tel: +82-42869-3922 b Korea Basic Science Institute, Seoul, 136-713, Korea. E-mail: yigira@ kbsi.re.kr

been reported, including opaline face-centered cubic (fcc) assemblies of colloidal spheres and inverse-opal structures of various dielectrics and metals. Recently, non-spherical and non-isotropic spherical particles have been proposed as building blocks for nonconventional structures that may lead to better optical properties. The formation of these colloidal structures has been demonstrated by experimental studies that use controlled aggregation of colloidal particles, controlled synthesis of particles, and other physical methods. Additionally, individual non-spherical particles can have interesting optical properties by themselves. These properties can lead to high-efciency diffusion or strong scattering of light that can be useful in the development of novel optical lms for the at panel display industry. On the other hand, colloidal particles have been used as model systems for the study of molecular interactions and of atomic

Seung-Man Yang received a Ph.D. degree in Chemical Engineering from Caltech in 1985. Following this, he joined the KAIST as a Professor in Chemical and Biomolecular Engineering. He has served the KAIST as a director of the Computing Center, and a Department Chair. Currently, Professor Yang leads the Creative Research Initiative Center for Integrated Optouidic Seung-Man Yang Systems. His principal contributions have been in theories and experimental methods for fabricating ordered macrocrystalline structures, which can be applied as innovative functional nanoscopic materials such as optoelectronic devices and biosensors. He has authored over 160 peer-reviewed papers, and a number of books and patents in related areas.
This journal is The Royal Society of Chemistry 2008

Gi-Ra Yi is a senior researcher of Korea Basic Science Institute (KBSI) in Seoul. He received his B.S. (1997) degree in chemical engineering from Yonsei University, and M.S. (1999) and Ph.D. (2003) degrees in chemical and biomolecular engineering from KAIST. After his postdoctoral research at the University of California, Santa Barbara, he worked briey for the Corporate Gi-Ra Yi R&D Center of LG Chem Research Park as a research scientist. In 2006, Dr. Yi moved to the Nano-Bio System Research Team of KBSI in Seoul. Currently, he is interested in self-assemblies of colloidal particles at micrometre or nanometre scales, as well as multiphase microuidics.
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Fig. 1 Schematic diagram of shape-anisotropic, chemically patterned, and internally structured colloidal particles.

Fig. 2 (a) Schematic diagram of the method of lm stretching for particles with various structures and (b) SEM images of the obtained particles through scheme A and B. Scale bars are 2 mm. Reprinted with permission from ref. 7; copyright 2007 National Academy of Sciences, USA. (c) SEM and (d) TEM images of colloidal crystals composed of hollow titania ellipsoids. From ref. 8. Reprinted with permission from AAAS.

crystals because their dynamic properties of phase behavior can be easily observed with optical microscopy.35 In fact, a number of distinct atomic crystalline phases have been discovered using model colloidal particles, which behave like hard spheres or interact with isotropic interparticle potentials. Recently, some new crystalline phases were observed by the application of an external eld to colloidal crystalline phases. However, the emergence of new model colloidal systems that have nonisotropic directional interactions opens the possibility of exploring molecular interactions and phase behavior in much more complex cases. Fig. 1 illustrates the recent revolution in colloidal particle synthesis and how it has enabled us to control the shape of particles, the internal structures of the systems, and the nature of physically or chemically distinct patches on surfaces. In this article, the key contributions to this eld of research over the past few years will be reviewed and discussed in terms of experimental and theoretical progress in synthesis and assembly of the nanostructured colloids.

II. Shape-anisotropic particles


A. Ellipsoidal particles As nature tends to enforce spherical interfaces to minimize surface energy, it has been fairly challenging to synthesize anisotropic particles directly. Therefore, as an alternative route for the production of anisotropic particles with desirable properties, several clever methods have been developed. One simple anisotropic morphology could be ellipsoids. For example, polymeric ellipsoids were successfully prepared through the uniform deformation of spherical latex beads in a viscous matrix of another polymer. Ho et al. mixed polystyrene (PS) latex and poly(vinyl acetate) (PVA) in water and prepared lms by casting them on substrates. The lms were then stretched above their glass transition temperature and rapidly quenched. The
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ellipsoidal particles were separated from lms by dissolving the PVA in alcoholic solutions.6 By controlling the draw ratio and material composition, a variety of polymeric ellipsoids could be prepared by this technique. Recently, Champion et al. modied the stretching method slightly, as depicted schematically in Fig. 2a, and were able to prepare over 20 types of distinct structures on the micrometre scale, as shown in Fig. 2b.7 They went on to investigate the role of these target geometries in the immune system. Adopting the same technique, Jiang et al. obtained colloidal crystals of ellipsoidal particles. In this case, a polymeric matrix with ellipsoidal voids was prepared initially by stretching the polymeric inverse opal structure. Then, inorganic particles were formed inside the voids of the matrix, and nally removal of the polymer by burn-out left behind well-packed ellipsoids. The SEM and TEM images in Fig. 2c and d, respectively, show the ordered packing of hollow titania ellipsoids.8 Another route to ellipsoidal particles is by the deformation of inorganic particles in high-energy ion beams. As shown in Fig. 3, silica particles were deformed along the perpendicular direction of the ion beam. This beam consisted of Xe ions accelerated to energies of 0.34 MeV.9 In addition, a similar approach was used to produce crystal structures of silica oblates.10

Fig. 3 SEM images of deformed silica particles after Xe ion irradiation at (a) 4 MeV and (b) 1 MeV. Reprinted with permission from ref. 9. Copyright 2003, American Institute of Physics.

This journal is The Royal Society of Chemistry 2008

Both deformation-based methods are limited to relatively small quantities of particles. To produce large quantities of anisotropic colloidal particles, direct synthetic methods have been developed. For example, using spindle-shaped particles of hematite (a-Fe2O3) as core materials, ellipsoidal particles of silica are prepared by seeded solgel polymerization of tetraethoxysilane (TEOS) on the surface of hematite.11 In this case, the aspect ratio can be controlled by adjusting the thickness of the silica coating. Furthermore, dissolving the core and performing additional reactions can lead to the production of hollow ellipsoidal and uorescent particles. Recently, the packing behavior of non-spherical objects have attracted great attention in mathematics, condensed matter physics and materials chemistry. For this, ellipsoidal particles serve as important model systems. When the ellipsoidal objects are packed randomly in a maximally random-jammed (MRJ) state, the packing fraction is much higher than that of spherical objects (0.64). An axis ratio close to 1.25 : 1 : 0.8 induces a packing fraction of the MRJ state as high as that of the densest packing of spheres (0.74 in the fcc lattice). Donev et al. reported these facts based on experimental and simulation results.12 The famous M&Ms milk chocolate candies, which have a narrow size distribution, were used for this experiment. Several different containers were used and the volume fraction was calculated from their weights. In addition, Man et al. used 1.25 : 1 : 0.8 ellipsoids prepared by stereolithography.13 Using medical magnetic resonance imaging (MRI), the nematic order parameters were calculated and the resulting values indicated the absence of orientational order as MRJ states. Simulation with hard-particle molecular dynamics algorithms showed that the packing fraction and number of contacts per particle are functions of the aspect ratio. The increase in packing fraction and number of contacts originated from the additional rotational degrees of freedom associated with ellipsoidal shape. Therefore, mass production of ellipsoidal particles at the submicrometre scale will be essential for constructing low dielectric materials with high void fraction by inverting the structure, as well as unconventional colloidal crystals with unique photonic band gap properties. B. Dumbbell-like particles For the production of polymeric dumbbell particles, the seeded emulsion polymerization scheme was developed. The use of swollen styrene monomers and crosslinking agents with crosslinked seed PS latex resulted in phase separation before polymerization occurred. The acceleration of phase separation during polymerization induced the formation of dumbbell particles.14 The formation of these structures required precise control of the experimental conditions, including the cross-linking density of seed latex, and swelling and polymerization times. The experimental results are in line with a thermodynamic model for monomer swelling that is related to the mixing of the monomer and polymer, the elastic energy of particles and the interfacial tension between particles and water. Then, the Gibbs free energy of mixing is given by:  DG m,p RT [ln(1 vp) + vp + cmpv2 ] + p RTNVm(v1/3 1/2vp) + 2Vmg/a p
This journal is The Royal Society of Chemistry 2008

where R is the gas constant, T is the absolute temperature, vp is the volume fraction of polymer in the swollen particle, cmp is the monomerpolymer interaction parameter, N is the effective number of chains in the network per unit volume, Vm is the monomer molar volume, g is the interfacial tension between the particle and the water, and a is the radius of the swollen particle. At equilibrium, the balance between the positive contribution from the elastic energy and the negative contribution from the mixing force determines the degree of phase separation. For microspheres, the interfacial energy term is negligible compared with the other two terms. Using a seeded emulsion polymerization scheme, Mock et al. reported that the surface afnity of seed latex to the monomer affects the anisotropy of the resulting submicrometre-sized particles.15 Kegel et al. showed that the ratio of fast (initial swelling time scale) to slow (as yet undened) relaxation times determines the separated volume throughout the experiment.16 It is very important to note that the seeded emulsion technique allows the preparation of particles that are anisotropic not only in shape, but also in their chemical and physical properties. Using a different monomer from that of the seed latex, PS/PMMA and PS/PBMA dumbbell particles were synthesized.17 Through a chemical reaction on one bulb of each dumbbell, the bulbs could be endowed with different hydrophilicities. These particles are amphiphilic and therefore can be used for stabilizing emulsion drops, for example, through alignment at the interface like surfactant molecules. Hosein et al. showed that dumbbell-like particles can adopt two-dimensional (2D) in-plane and out-of-plane alignments of particles when they are conned within thin uid layers.18 For 3D structures of dumbbell particles, Mock et al. observed a disorderorder phase transition into a rotator phase where centres of mass are ordered, without any increase in the orientational order of the particles, as the volume fraction of the dimer particles increases.19 Further increases in the volume fraction induced a body-centered tetragonal phase with orientational as well as positional orders. This was conrmed by ultrasmall-angle X-ray scattering and SEM in real-space, as shown in Fig. 4. Interestingly, dumbbell particles have also been prepared by controlled aggregations of two particles. For example, Johnson et al. reported that silica dumbbell particles can be prepared by

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(1)

Fig. 4 SEM image of colloidal crystals composed of homonuclear dicolloids. Reprinted with permission from ref. 19. Copyright 2007 American Chemical Society.

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destabilization of a suspension followed by shell coating.20 Destabilization of a silica suspension was carried out in two different ways: shear-induced aggregation in a high ionic strength, and depletion-induced aggregation driven by micelles. The aggregates were coated with silica shells using an additional reaction. The thickness of the coated shell determined the aspect ratio of the dumbbells. Although doublets coexist with other aggregates, the number fraction of dumbbells at the optimum aging time was as high as 40%. In addition, the use of a centrifugation process can increase the fraction. Labeling of the core and shell with different dye molecules allows us to conrm dumbbell formation. Ibisate et al. have shown that silica particles are constantly colliding with neighboring particles. Furthermore, the particles in silica suspensions of sufciently high concentration are bound together by van der Waals attractions. Also, they showed that the number of doublet particles was increased with increasing aging time, and that the doublet particles could be captured and transformed into dumbbells through subsequent coating with silica under controlled experimental conditions.21 C. Anisotropic particles with complex morphology The seeded emulsion polymerization scheme was developed further, making possible more diverse particle shapes, such as ice cream cone-like or popcorn-like particles. Recently, Kim et al. prepared triple rod, triangle, cone and diamond particles, in a well-controlled manner with high yield (Fig. 5) and also showed, through simple experiments, that non-spherical particles have a higher packing density than spherical particles.22 On the other hand, Chen et al. performed molecular dynamic simulation to study self-assembled structures of cone-shaped particles that can be prepared by sequential use of the seeded method.14,23 To restrict the formation of assemblies to those

desired, specic interactions between building blocks were induced by patches with different chemical or physical properties on each building block. The simulation showed that the conguration of cone packing in small clusters is the same as that for sphere packing in evaporation-induced self-assembly for a wide range of cone angles (sphere packing will be discussed below). Large clusters for some specic numbers (n) of the constituting cones showed unique packing behavior, whereas the packings for n 12, 32, 72, and 132 were structurally similar to those of virus congurations. The swelling and phase separation technique can be used for superparamagnetic coreshell particles with anisotropic shapes, as shown in Fig. 6.24 A polymer shell is formed around an Fe3O4 and silica core, which has acrylic functional groups on its surface, using an emulsion polymerization scheme. By crosslinking the polymer shell, cores can be kept at the center. Without crosslinking, the core particles could move to an eccentric position because of the interfacial tension. Additional swelling processes produced ellipsoidal particles or asymmetric doublets. Particles with high aspect ratios have been synthesized by shear-induced deformation of liquid droplets.25 When mixtures of photocurable resin and solvent were emulsied, the high shear rates associated with stirring led to the deformation and breakup

Fig. 5 SEM images of (a) triple rod particles and (b) triangle particles prepared by monomer swelling and phase separation during polymerization. Schematic illustration of (c) linear growth for triple rod and (d) perpendicular growth for triangle depending on the relative crosslinking density of the mother particles. Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with permission (ref. 22).

Fig. 6 (a) Schematics for various shaped core-shell particles and SEM images of (b) eccentric, (c) concentric, (d) ellipsoidal particles and (e) asymmetric doublets fabricated by emulsion polymerization. All scale bars are 400 nm. Reprinted with permission from ref. 24. Copyright 2007 American Chemical Society.

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of emulsion droplets. The low interfacial tension due to good solubility of the solvent into the continuous phase resulted in a low capillary number and therefore deformation was not severely limited by the minimization of interfacial energy. The deformed shape was maintained for hours or even days owing

to the attrition of shearing that induced weak polymerization. By controlling the shear rate, viscosity ratio, and resin concentration, microrods with narrow size distributions and various aspect ratios were prepared. These rod-like particles could be aligned by dielectrophoretic torque from an alternating current (AC) electric eld. Additionally, assemblies of microrods at an emulsion interface can be induced to form a hairy colloidosome.26 This structure is a permeable capsule composed of colloids that resembles a liposome.

D.
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Lithographically dened particles

Fig. 7 (a) Schematics of lithographic particle fabrication and SEM images of prepared disk particles with aspect ratios (height/diameter) of (b) 1 and (c) 0.33. The scale bars in (b) and (c) are 1 mm. Reprinted with permission from ref. 27. Copyright 2007 American Chemical Society.

Solution-based methods usually result in large yields, but are restricted to simple shapes with rounded surfaces. On the other hand, recently developed lithography-based techniques can lead to particles with complex shapes and sharp edges. Fig. 7 shows that a pattern on a photomask has been transferred to a photoresistant lm and the subsequent removal of unexposed regions and of the sacricial layer from the photoresistant lm will result in the formation of various individual particles. Badarie et al. demonstrated that cylindrical particles can be produced with high yields (Fig. 7) and then dispersed; columnar, parallel, orthogonal, and isotropic aggregates can be achieved by tuning selective interactions between the particles.27 Colloidal

Fig. 8 (a) Schematic diagrams for rst and second step assembly processes using hydrophobic interaction and van der Waals interaction, respectively and (b) corresponding optical and SEM images showing successful binding after rst- and second-step processes. Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with permission (ref. 30).

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alphabet particles with complex geometries have been also prepared by lithography.28 Using double exposure of different photomasks, Janus particles can be produced from photoresistant bilayer lms. More recently, 2D holographic lithography was used to produce monodisperse anisotropic particles without the use of photomasks.29 Interference patterns of laser beams were used to induce cylindrical particles on a substrate. Surface chemistry could then be precisely controlled using physical grafting methods and chemical reactions. The high degree of control over the interference pattern and short exposure times enabled the production, with high yields, of submicrometre-sized particles. Recently, Onoe et al. showed that trapezium- and U-shaped microparticles prepared by lithography with controlled surface properties can assemble into columns or microchain structures, respectively, through a two-step assembly process.30 These microfabricated building blocks have two different patches: a hydrophobic self-assembled monolayer (SAM) on a gold surface (A surface) and hydrophilic hydroxyl groups on a silica surface (B surface). When the particles were dispersed in a weakly acidic solvent, hydrophobic attraction between A surfaces and electrostatic repulsion between B surfaces induced stable AA bonding. A subsequent pH change to an acidic value removed electronic double layers from the B surface and caused BB bonding through van der Waals interactions. This scheme and resulting structures are shown in Fig. 8. Recently, lithography-based particle synthesis has been combined with microuidic techniques, which overcomes limitations associated with the batch process. The microuidic synthesis allows continuous high-throughput production of specically designed microparticles. Fig. 9a shows how the

continuous ow of a photocurable monomer through the channel can be selectively exposed to shuttered UV light.31,32 The UV light can be screened by a photomask. As noted, the intensity and spot size of the light are controlled by an objective lens. Solidication was rapid, taking less than 0.1 s. Oxygen inhibition at the PDMS wall leaves a lubricating layer and allows continuous synthesis without problems resulting from sticking. The resulting particles had the same shape as the photomask, as can be seen in Fig. 9bd. Although the polymerization occurred in a short time (0.1 s), the boundaries of the particles were blunt due to the owing resin. Therefore, the resin stream must be stopped during the exposure with UV to obtain the particles with sharp edges. Fortunately, the pressure-driven laminar ow of the incompressible uid in the microuidic channel can be stopped by the release of pressure within a short delay time of 0.3 s. The use of computer-controlled pressure and exposure systems allows a sequential cycle of stopping, exposure and ow processes to be repeated, as necessary. This method, called stop-ow lithography (SFL), is extremely useful for the synthesis of nanostructured microparticles owing to the high resolution of SFL, especially when combined with the interference lithographic technique.33,34 An alternative to direct lithographic particle synthesis is the production of particles from emulsions in microuidic chips. Dendukuri et al. described how photocurable resin could be broken into droplets in a T-junction of a microuidic chip and then UV-curing could induce non-spherical microparticles that were templated by the uidic channel.35 Depending on the relative size of the droplet in comparison with the channel size in which UV exposure takes place, plug- or disk-type polymeric particles could be continuously generated. Using a similar

Fig. 9 (a) Schematic illustration of ow lithography for isolated particle fabrication and SEM images of (b) triangle, (b) square and (d) triangular rod particles. Insets in (b)(d) represent the feature shapes of photomask for the corresponding cases. Scale bars in (b)(d) are 10 mm. Reprinted with permission from Macmillan Publishers Ltd: Nature Materials (ref. 31), Copyright 2006.

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concept, Xu et al. prepared particles with a variety of shapes using ow-focusing geometry and the nature of the photo- or thermally curable resin.36 In particular, the functionalization of particles with dye molecules, quantum dots, magnetic nanoparticles, or liquid crystals could lead to many practical opportunities in this area. The emulsion-based method for producing biphasic droplets was used to produce non-spherical microparticles.37 Two inlets for the oil phase allowed the use of a photocurable resin stream and a non-curable stream. Single oil droplets containing the two components were generated in a continuous water phase. The photocurable phase could be separated from the biphasic emulsion by selective solidication. Various non-spherical shapes were obtained by controlling the ow ratio of the two inlet streams. In addition, particles with optical as well as structural anisotropy were prepared using the emulsion-based method. In particular, optically bipolar microparticles could be formed by UV exposure of monodisperse emulsion droplets, which contained photopolymerizable liquid crystals, by the breaking off of drops in co-ow systems.38 These particles were rotated using optical trapping by circularly polarized light. Oblate and prolate ellipsoidal particles with high birefringence have also been prepared using a polymer matrix by the stretching and solidication method that was described above for ellipsoidal particles. E. Colloidal clusters Unlike anisotropic particles mentioned in the previous section, colloidal clusters have three-dimensional (3D) complexity. These particles can, therefore, be useful as building blocks for new types of colloidal assemblies or as model particles for understanding the fundamental physics of particulate systems. Recently, the emulsion-based colloidal assembly, which was pioneered by Velev et al., has been further developed for controlled synthesis of colloidal clusters using emulsion drops as conning geometries.3942 In this method, a certain number of particles which are bound to an emulsion interface are assembled spontaneously into colloidal clusters during evaporation of the emulsion phase.41,42 For a given number of particles, the nal congurations are all identical, as shown in Fig. 10. It is worth noting that the congurations of clusters are similar to those that have a minimum second moment of mass distribution for n < 12 (n is the number of the constituent particles), which occurs in many common molecules. Pure clusters of all identical congurations from two-sphere clusters (doublets) to high order clusters can be fractionated by density gradient centrifugation. Lower order clusters from doublets (n 2) to octahedra (n 6) are subelements of the fcc lattice or its stacking variants. However, higher order clusters (n > 6) are not subunits of fcc structures and form an unfamiliar set of packings. Therefore, pure clusters of an identical structure have the potential to form extraordinary crystalline structures through controlled assembly. To understand the clustering process of colloidal particles on emulsion interfaces, Lauga et al. performed numerical calculations using Surface Evolver simulations. As the emulsion drop shrinks, colloidal hard spheres come into contact with neighboring spheres and form a critical packing structure that is unique and forms without deformation of the emulsion interface.
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Fig. 10 (a) Schematic for self-organizing particles conned in emulsion interface and (b) experimental and Surface Evolver simulation results for consolidated colloidal clusters for n 412. For a given n, clusters have all identical congurations. Reprinted with permission from ref. 42. Copyright 2004 American Physical Society.

With further reduction in the drop volume from the critical packing state, the emulsion interface begins to deform and the capillary forces pull the particles inside the emulsion drop. Numerical simulations predict the same congurations that are found in experimental studies, indicating that the detailed physics of these unique congurations was correct. In addition, simulations showed that particles with an identical contact angle formed a unique packing structure, whereas particles with different contact angles from each other can lead to different congurations. Following the developments outlined so far, the emulsionassisted method of colloidal self-organization has been modied for use with other, more general, colloidal materials including polymers, ceramics and metals. This has been achieved by the inclusion of an additional reaction on the surface of the clusters that increases the structural rigidity.43 Moreover, the microuidic technique has been applied in order to prepare monodisperse emulsion droplets and thereby to produce uniform colloidal clusters.44 The uniformity of the resulting aggregations is enhanced compared with those from polydisperse emulsion droplets. For a higher yield, relatively large amounts of uniform emulsions were recently prepared using a Couette cell.45 The production rate of the resulting aggregate was high, and enhanced uniformity was achieved. As for molecules, colloidal clusters with directional interactions can form much more diverse colloidal structures that cannot be expected for crystalline structures of isotropic spheres. Therefore, clusters can be used as new model systems for studying unusual optical or other physical properties if we can create chemically or physically distinct sites in designated positions on a colloidal particle or cluster. For example, Ngo et al. reported that a tetrastack structure composed of tetrahedrons has a full photonic band gap at a refractive index contrast as low as 2.1.46 However their simulation result has not been conrmed experimentally yet owning to difculty in constructing the tetrastack structure of tetrahedrons. Zhang
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et al. showed by simulation that hard spheres with four attractive patches can act as colloidal molecules and be assembled into a diamond structure if seed crystallites are included.47 The diamond structure is a promising candidate for a material with a full and robust photonic band gap, and it still remains challenging to synthesize diamond-like colloidal crystals. In addition, the effect of the number of patches upon the phase diagram was studied by numerical simulation for monodisperse patchy colloidal particles and their mixtures.48 However, experimental studies of the assembly of patchy clusters with specic attractions are limited due to the complex fabrication steps required to create sticky patches. As a rst step for well-coordinated clusters, we reported that binary colloids of different sizes in emulsion drops can lead to coordinated patches on the outer surface of a cluster by encapsulating the larger particle cluster with smaller particles partially.49,50 When the amount of small particles is not enough for complete coverage of the entire cluster, the small particles do not interrupt the process of assembly for the large particles. In addition, we found that the interparticle potential between large and small particles can play a critical role in the control of the morphology in this process. Patchy clusters were prepared successfully from the cocharged particles, while the countercharged particles produced different types of clusters in which small particles covered entirely the clusters of the large particle. Fig. 11 shows the SEM images of partially encapsulated colloidal clusters. Meanwhile, Yin et al. fabricated colloidal clusters using microhole arrays as templates. The cluster congurations are different from those obtained from the emulsion-based technique due to the anisotropic geometrical connement.51 The ratio of particle to hole sizes and the number of stacking layers determine the

conguration of the cluster. In particular, they demonstrated seed-induced crystallization by introducing the square tetramers into spherical particle suspension. Although the resulting crystal had an fcc lattice, it was meaningful in view of controlling the crystal plane using colloidal clusters as seeds. Realization of advanced functional structures by self-assembly of clusters raises many challenging issues. For example, delicate control of interactions between the patches of neighboring particles at optimal strength will be important to avoid severe aggregation before crystallization of the desired structure and to sustain the structure after crystallization under external disturbances.

III.

Chemically patterned colloidal particles

Fig. 11 SEM images of partially encapsulated clusters prepared from emulsion drops containing bimodal silica particles. The clusters of large silica particles have well-coordinated patches which are not covered by small silica particles but exposed to the outside. Reprinted with permission from ref. 49. Copyright 2005 American Chemical Society.

In Roman mythology, Janus (the god of gates, doors, beginnings and endings) was usually pictured with a double-faced head looking in two opposite directions. The face originally represented the sun and the moon. Because of the two different natures that coexisted in the head of Janus, De Gennes used the name of this Roman god to describe a particle containing two different chemical compositions. Fabrication methods to produce such particles have been studied extensively over the past few decades. The 2D-based synthesis has been one of the most widely used methods to fabricate chemically patterned colloidal particles. Casagrande et al. rst demonstrated the partial protection technique, as schematically illustrated in route 1 of Fig. 12a.52 In this work, cellulose lm was used as a partial protection layer for microspheres, and the unprotected regions of particles were treated with the hydrophobic moiety, octadecyltrichlorosilane, in order to synthesize amphiphilic particles. Likewise, Cui et al. used PDMS as a partial protection layer, and the unprotected regions were modied with silver by electroless deposition.53 Also, Bao et al. used a photoresistant protecting layer, and metals and metal oxides were deposited on the exposed parts of the silica particles using an electron-beam evaporator.54 Finally, Paunov et al. used the gel-trapping and replication technique for partial protection of particles.55 A monolayer of polystyrene microspheres was formed at the interface of pre-heated oil and water phases. Here, the water phase contained a gelling agent. The contact angle of the oilwater interface at the particle surface determined the proportion of the polystyrene particles that was exposed. The gelling agent in the water phase immobilized the polystyrene microspheres when the temperature was cooled to 25  C. Subsequently, the oil phase was replaced by PDMS elastomer, and then the particle monolayer was transferred onto the PDMS surface from the gelled water phase when the PDMS elastomer was peeled off. The PDMS layer acted as a partial protection layer during gold sputtering and allowed the fabrication of Janus particles. The Janus particles that were prepared could be detached from the PDMS using sticky tape. If one can manage to keep stable directional ux, the layers for partial protection of colloids are not needed, as schematically illustrated in route 2 of Fig. 12a. Bao et al. demonstrated that gold-capped silica particles can be prepared through the direct deposition of a metal layer on the non-contacting silica monolayer followed by partial etching of the metal layer.54 Also, Hong et al. used the direct deposition of gold using
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Fig. 12 Schematics for fabricating Janus particles. (a) 2D-based synthesis using partial protection, directional ux, and colloidal mask. (b) Solutionbased batch process. (c) Continuous synthesis using microuidics.

electron-beam deposition on the monolayer of carboxylatemodied colloids. The gold-deposited parts were treated with a positively charged monolayer. Therefore, the spherical particles with opposite electric charges could be prepared and assembled into the colloidal clusters.56 Interestingly, Cayre et al. used microcontact printing of insoluble surfactants on a monolayer of polystyrene microspheres to fabricate dipolar colloidal particles without employing partial protection layers.57 First, a monolayer of monodisperse polystyrene microspheres was prepared on a solid substrate. Then, water-insoluble surfactants with opposite charges were deposited on a poly(dimethylsiloxane) (PDMS) elastomer. Finally, the water-insoluble surfactant lm was stamped onto the polystyrene monolayer and the fabricated dipolar colloids were redispersed in water. Recently, colloidal masks have also been used to make exotic Janus particles, as schematically illustrated in route 3 of Fig. 12a. Bae et al. used the contact areas of a multilayer colloidal crystal as a mask for octadecyltrichlorosilane treatment to prepare chemically nanopatterned colloids.58 The hydrophilic protected region of these colloids was used as a site for specic nucleation and growth of titania. Similarly, Zhang et al. used a colloidal mask to make gold-decorated particles.59 Colloidal crystals were assembled using dip coating and upper colloidal crystal layers etched by O2 plasma. The etched upper layers acted as colloidal masks for gold vapor deposition to decorate microspheres. The nal fabricated structures could be controlled by changing the stacking structure (hcp or fcc) of the colloidal crystal or the angle between the vapor ow and the normal to the sample surfaces. While the 2D-based synthesis described above allows the preparation of well-dened Janus particles, it requires a relatively large area and the fabrication procedures are quite complicated. This is particularly the case if one needs to prepare larger quantities of the samples. Most of these techniques require monolayers of microspheres, but none of the methods that have been reported so far were sufciently robust and simple.
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Therefore, a few groups have reported the development of an alternative approach. Perro et al. demonstrated a solution-based batch process capable of fabricating Janus particles in large quantities, as shown in Fig. 12b.60 Snowman-like silicapolystyrene hybrid nanostructures were synthesized using emulsion polymerization in the presence of silica colloids, the surfaces of which had been modied by polymerizable groups. As the polystyrene nodules acted as partial protectors, the functional silane coupling agents could be treated only on unprotected areas of the silica particles. The separation of the Janus silica particles from the polystyrene was achieved in aqueous solution by ultrasonication and ultracentrifugation. The silane coupling agents with different functionality, on the other side of the Janus particle, could then be treated. Hong et al. captured the colloids at the liquidliquid interface between emulsied molten wax and water at 75  C. The particles were locked by cooling to room temperature, and further modied chemically. The emulsions can be prepared by vigorous magnetic stirring, and consequently the method can be applicable to large-scale fabrication of Janus particles.61 More recently, electrohydrodynamic or microuidic devices have been introduced for the continuous production of Janus particles (Fig. 12c). Roh et al. fabricated biphasic Janus particles using electrohydrodynamic co-jetting of distinct polymer solutions with small amounts of additives that had different colors or functional groups, as can be seen in Fig. 13.62,63 Laminar ow streams of different polymer solutions were introduced, with side-by-side geometry, to the modied metal nozzle. When a high voltage was applied between the metal nozzle and the collector, the polymer solutions elongated and formed Taylor cones at the exit tip. This occurs due to the balance between two competing forces of electric Maxwell stress and interfacial tension. An ultrathin thread of polymer solution was ejected from the Taylor cone, and the solvent was evaporated during ight on the way to the collector. The nal polymeric biphasic colloids were left on the collector. The nal
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Fig. 13 (a) Electried co-jetting for Janus nanoparticles. Reprinted from Nature Materials with permission from Macmillan Publishers Ltd (ref. 62); copyright 2005. (b) Schematic for bioconjugation to a single hemisphere of Janus particle and confocal laser scanning microscope images (c) before and (d) after protein binding. Reprinted in part with permission from ref. 63. Copyright 2007 American Chemical Society.

morphologies of the colloids could be controlled by varying the properties of the polymer solution (viscosity, conductivity, and surface tension) and the jetting conditions (applied electric eld strength, ow rate, tip-to-collector distance, etc.). Moreover, triphasic nanocolloids could be prepared using a modied nozzle with three inlets.64 Turning to microuidic devices, Nisisako et al. demonstrated synthesis of Janus particles with color and electrical anisotropy using a microuidic co-ow system, as shown in Fig. 14.65 Carbon black and titanium oxide were dispersed in an acrylic

Fig. 14 Optical microscope images of (a) the junction for Janus drop formation and (b) the whole channel; (c) and (d) electric eld induced color switching for an e-paper application. Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with permission (ref. 65).

monomer for the preparation of black and white pigments, respectively. Both pigment streams were introduced into the co-ow system with the same ow rate to generate bicolored emulsion droplets. The fabricated bicolored pigment droplets were polymerized at 90  C on the outside of the microuidic chip. Because of the difference in charge densities between carbon black and titanium oxide, the resulting Janus particles had electrical anisotropy. Therefore, the Janus particles were able to be actuated or ipped by electrophoretic rotation, as shown in Fig. 14cd. In addition, sixteen-sheath ow geometries were also reported for mass production of Janus particles. Shepherd et al. used in situ UV curing of colloid-lled hydrogels instead of thermal polymerization on the outside of the microuidic chip.66 Two different colored silica-dye coreshell particles were prepared and dispersed in an aqueous solution containing acrylamide, a crosslinker and a photoinitiator. The colored aqueous colloidal dispersions were introduced with a Y-junction, and the laminar ow of the two colored streams was ruptured by a shear ow in order to fabricate Janus drops. When the microuidic channel was high enough, spherical granules were formed. On the other hand, if the channel height was smaller than the drop radius, discoidal granules formed. The acrylamide in the ruptured drops was cured by UV irradiation in the microuidic channel. This photopolymerization led to the anisotropy in shape and chemical composition by immobilizing the colloids in hydrogel network. Millman et al. used a dielectrophoretic force to entrap and transport suspended droplets.67 Here, each suspended droplet acted as a microreactor for the fabrication of, for example, eyeball particles or striped multilayer particles. Janus particles look very promising for use in many applications, such as for functional building blocks, emulsion stabilizers, e-paper, bifunctional carriers for drugs, catalysis, and so on. However, continuing research is still needed for the large-scale production of well-dened Janus particle at low cost.68
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IV. Internally structured colloidal particles


The performance of microspheres and their self-assembled structures is determined by their morphology, as has been described previously. Until this point, we have focused on the control of the external morphology of particles. In this section, we will discuss control of the internal structure of spherical particles. Many research groups have demonstrated the preparation of hollow spheres using templating methodology. As shown in Fig. 15, one of the most widely used approaches has been colloidal particle templating. Here, coreshell particles are rst prepared from colloidal particles such as polymer latex,6973 silica,7477 gold,78,79 ZnS,75 and so on. Typical template particles are coated with various materials to prepare coreshell composite particles by controlled surface precipitation of inorganic materials;70,7274,78 direct surface polymerization using functional groups on the surfaces;76,77 or layer-by-layer adsorption of a polyelectrolyte and of charged nanoparticles.69 The core is subsequently removed by calcination at high temperatures or dissolved in an appropriate solvent. Finally, hollow spheres of various materials such as silica,6971,73,75,78 titania,72 magnetic particlesilica composites,71 gold,74 polymers,76,77,79 ZnS,75 or organicinorganic hybrids69 have been obtained. Additionally, hollow spheres with movable gold cores have been fabricated.80 In this case, gold nanoparticles were coated with silica using tetraethylorthosilicate, and the goldsilica coreshell particles were treated with silane coupling agents, which acted as the initiators for atom transfer radical polymerization of poly(benzyl methacrylate). The silica layer between gold core and the polymer shell was dissolved by aqueous

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hydrouoric acid (HF) solution to produce hollow polymeric spheres with movable gold cores. However, such methods for hollow particles using solid cores as templates are relatively complicated in terms of the conditions required for shell coating and for the removal the solid cores (i.e., a high temperature or a toxic solvent) rather than those needed when liquid cores such as emulsion droplets8184 or vesicles8588 are used. Zoldesi et al. have fabricated highly monodisperse hollow particles with different shapes according to the thickness of their shells, such as hollow spheres, microcapsules, and microballoons. This is shown in Fig. 16. Monodisperse and stable oil-in-water emulsion droplets were prepared by hydrolysis and polymerization of dimethyldiethoxysilane with83 and without82,84 surfactants. The modied Stober method was used to achieve the encapsulation of oil droplets with a solid shell. The thicknesses of the solid shells were controlled by changes in the time interval between the preparation of oil droplets and the addition of a silica precursor. Microphase separation of block copolymers has been widely used to control the internal structure of polymeric lms. Okubo et al. rst used microphase separation of block copolymers to control the internal morphologies of polymeric spheres.89 A diblock copolymer solution was emulsied using a homogenizer to generate oil-in-water emulsions that conne the geometry to that of a sphere. As the volatile organic solvent evaporated, the block copolymer self-assembled into nanostructured spheres due to microphase separation. The morphology of the nanostructured spheres could be controlled by changing the evaporation rate of solvent (toluene), the size of conning emulsion

Fig. 15 Schematic of the method of particle templating for hollow particles and TEM images of hollow silica shells. Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with permission (ref. 70).

Fig. 16 TEM images of: (a) and (d), hollow microspheres; (b) and (e), microcapsules; (c) and (f), microballoons prepared by emulsion droplet templating. Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with permission (ref. 82).

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their potential applications, more efforts and research are required. This research should be aimed at enabling us to control and optimize the morphologies that are produced, as is needed for the development of specic applications.

V. Summary and outlook


Fig. 17 TEM images of nanostructured microspheres for three different ratios of particle size to feature spacing of (a) 2.5, (b) 3.3 and (c) 7.0 prepared by microphase separation of a block copolymerhomopolymer blend in an emulsion droplet. Reprinted in part with permission from ref. 90. Copyright 2007 American Chemical Society.

drops and the molecular weight of the diblock copolymer, as well as by the addition of a homopolymer. We also used an emulsion droplet as a conning geometry for the self-assembly of block copolymerhomopolymer blends.90 The effects of the particle size and the content of homopolymer on the internal morphology of the nanostructured spheres were extensively studied by systematic investigation. Some of the representative internal structures were reproduced in Fig. 17. Yabu et al. have demonstrated the fabrication of spherical particles with well-developed lamellar structures using modied reprecipitation methods.91 In conventional reprecipitation methods, small amounts of polymer solution are dropped onto a large quantity of poor solvent, causing the polymer particles to immediately precipitate from the dropped polymer solution. When the conventional reprecipitation method was applied to the fabrication of block copolymer particles, the lack of time for long-range ordering of the block copolymer meant that copolymer particles with well-developed lamellar phases could not be obtained. Thus, in a modied reprecipitation method, small quantities of poor solvent were slowly dropped into the polymer solution in a good solvent. As the volatile good solvent gradually evaporated, a concentration gradient was formed. In this way, spherical particles with well-developed lamellar structure could be produced owing to the exposure of block copolymer particles to good solvent during reprecipitation. Nanostructured triblock copolymers could also be produced by quenching the dilute polymer solution.92 In a similar manner, the evaporation-induced self-assembly of silica precursor and surfactants inside the droplets, generated from a vibrating orice aerosol generator, produced monodisperse porous silica particles of spherical shape.93 Simply changing the orice diameter or the concentration of the precursor solutions allowed the diameter of the particles to be controlled. Subsequently, inside the aerosol droplets, the surfactants were completely removed by annealing at high temperatures, which produced internal pore structures. The porous silica particles thus produced had uniform periodic pore structures in some regions that were aligned parallel or perpendicular to the surface. The preparation of nanostructured spheres has been the subject of a great deal of attention owing to their potential uses in a variety of applications, including controlled storage and release of functional materials, high-performance catalysts, sensors, and building blocks for functional self-assembled structures. Although there has been some research conducted into
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In this Feature Article, we have discussed the general features in colloidal particles and their assembled structures. In principle, a colloid is a functional building block in itself ranging from several tens of nanometres to micrometre scales for 2D and 3D ordered architectures for photonic nanostructures or as microprobes for high-throughput screening of biomolecules or chemical substances. Depending on the external or internal structures of the particles, they can have unique optical, mechanical, or electrical properties that may be useful for the development of novel photonic crystals, composites, plasmonic materials, or memory devices. For example, as shown in Fig. 18a, mixtures of binary colloids can produce, through selective removal processes, a diamond or pyrochlore structure of spheres.94 Although the experimental realization of this is challenging, it is feasible since a co-crystallization method has already been developed95,96 and their photonic band gaps are wide and robust in spite of a few defects that are inevitable in self-assembling processes. Patchy particles or colloidal clusters allow us to imagine much more diverse structures, such as those formed by molecules. For example, a simple cubic structure can be realized using 6-fold patchy colloidal particles as shown in Fig. 18b, while 4-fold patchy colloidal particles form a dodecahedral structure, as shown in Fig. 18c.97 Extending these, we can design even more diverse systems using non-conventional structured colloidal particles to produce new complex structures, even though the particles themselves would need to be more developed for such complex colloidal suprastructures.

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Fig. 18 (a) MgCu2 structure and pyrochlore structure that could be obtained by crystallization of binary colloidal mixture and selective removal of large particles from MgCu2 structure. Reprinted from Nature Materials with permission from Macmillan Publishers Ltd (ref. 94), copyright 2007. (b) Simple cubic structure and (c) dodecahedral structure composed of 6-fold and 4-fold patchy colloidal particles, respectively. Reproduced by permission of the PCCP Owner Societies (ref. 97).

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Finally, spontaneous formation of well-ordered colloidal arrays provides lithographic masks or scaffolds for creating useful patterns. In this case, modication of the self-assembled mask will improve the versatility of nanosphere lithography in fabricating novel nanopatterns such as nanocups, hollow shells, and multifaceted materials.98101

Acknowledgements
This work was supported by a grant from the Creative Research Initiative Program of the MOST/KOSEF for Complementary Hybridization of Optical and Fluidic Devices for Integrated Optouidic Systems.
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