Photon Trapping and the Enhancement of Electronic Excitation Energy Transfer Efficiency Caused by Colloidal Crystals

Summary: The efficiency of electronic excitation energy transfer from photoexcited fluorescein to rhodamine 6G is enhanced by 2.26 times in an exhaustively deionized colloidal silica suspension. This enhancement is caused by the photon trapping effects due to the Bragg reflection of colloidal crystals formed in the suspension. The lower enhancement efficiency of 1.41 times observed for rhodamine B as an acceptor is attributed to the inefficient spectral overlap between donor fluorescence and acceptor absorption bands.     

Photon trapping by the internal Bragg reflection of colloidal crystals

Fluorescence light emitted from photoexcited rhodamine 6G (R6G) doped in colloidal crystals of exhaustively deionized colloidal silica suspension is partially trapped within a crystal cage. This photon trapping is caused by Bragg reflection in crystal lattices. The photon trapping efficiencies were quantitatively examined as a function of the thickness of measurement cell. The efficiency increased from about 40 to 60% as the cell thickness increased from 1 to 10 mm for an R6G concentration of 5×10⁻⁶ mol/L. This result is attributed to an increase in the number of crystal layers perpendicular to the observation direction; these are formed in the cell with a large optical path length. On the other hand, the trapping efficiencies were constant irrespective of the angle between the incident and observed light of the cylindrical cells. The constant efficiencies are attributed to the fact that the heterogeneous crystal layers around the inner cell wall have the same thickness.     

CdTe量子点与罗丹明B间的荧光共振能量转移研究

以巯基乙酸为稳定剂, 在水溶液中合成了CdTe量子点. 以发射波长522 nm的量子点为给体, 罗丹明B为受体, 研究了在十六烷基三甲基溴化铵胶束介质中, 量子点与罗丹明B之间的荧光共振能量转移. 实验结果表明, 在pH＝5.00的缓冲溶液中, 当十六烷基三甲基溴化铵的浓度为1.37×10－4 mol/ L时, 量子点与罗丹明B之间的距离为2.65 nm, 1个量子点给体最多可与6个罗丹明B受体发生有效的共振能量转移, 能量转移效率为0.69.     

Large-scale fabrication of wafer-size colloidal crystals, macroporous polymers and nanocomposites by spin-coating

This paper reports a simple spin-coating technique for rapidly fabricating three types of technologically important materials--colloidal crystal, macroporous polymer, and polymeric nanocomposite, each with high crystalline qualities and wafer-scale sizes. Dispersion of monodisperse silica colloids in triacrylate monomers is spin-coated onto a variety of substrates. Shear-induced ordering and subsequent polymerization lead to the formation of three-dimensionally (3D) ordered colloidal crystals trapped inside a polymer matrix. The thickness of as-synthesized colloidal crystal-polymer nanocomposite is highly uniform and can be controlled simply by changing the spin speed and time. Selective removal of the polymer matrix and silica spheres lead to the formation of large-area colloidal crystals and macroporous polymers, respectively. The wafer-scale process is compatible with standard semiconductor microfabrication, as multiple micrometer-sized patterns can be created simultaneously for potential device applications. Normal-incidence transmission spectra in the visible and near-infrared regions show distinct peaks due to Bragg diffraction from 3D ordered structures. The spin-coating process opens a new route to the fundamental studies of shear-induced crystallization, melting and relaxation.     

二氧化硅胶体晶体及其为模板的多孔材料

用Stober法合成了粒径在35～750nm范围内的单分散的SiO₂粒子,考察了投料比对粒径的影响.研究了所制备的SiO₂胶体晶体的结构和反射光谱.利用两种不同粒径的SiO₂粒子作为模板和模板填充物,分别制备了SiO₂和重氮树脂的多孔材料.     

Kinetic analyses of colloidal crystallization in shear flow

Colloidal crystallization kinetics is studied in the shear flow of a suspension of colloidal silica spheres (110 nm in diameter), using a continuously-circulating type of stopped flow cell system. The crystallization rate from a suspension containing a small amount of nuclei and/or single crystals is high compared with that from a suspension containing no nuclei and/or single crystals. Crystal growth takes place at shear rates smaller than 3.4 s^–1 and at sphere concentrations higher than a volume fraction of 0.004.     

Melting temperature of colloidal crystals of monodisperse silica spheres in ethanol-water and ethylene glycol-water mixtures

The melting temperature (T _m) of colloidal crystals of monodisperse silica spheres in ethanol-water and ethylene glycol-water suspensions has been measured by reflection spectroscopy. A sphere of 110 nm in diameter and 0.041 in monodispersity index is used after purification and deionization processes. Transformation from the body-centered cubic lattice to the face-centered cubic lattice subphases is observed as the suspension temperature rises, which is similar to the purely aqueous suspension of the same sphere. A phase diagram including liquid-like and crystal-like structures is obtained in the presence of ion-exchange resins coexisted. The data ofT _m are analyzed successfully with the theory of Williams, Crandall, and Wojtowicz. The heat of melting decreases by the addition of ethanol or ethylene glycol in the mixtures.     

Gravitational compression dynamics of charged colloidal crystals

We examine the compression of charged colloidal crystals under the influence of gravitational force by monitoring the spatiotemporal variations of Bragg diffraction from the crystal lattice. We use the dilute aqueous dispersions of colloidal silica particles (diameter=216 nm, charge number=733, a particle volume fraction φ=0.06) in the presence of 5-15 μM sodium chloride. The sedimentation profiles of the colloidal crystals along the crystal height are determined by in situ fiber optics reflection spectroscopy. The time evolutions of the sedimentation profiles are calculated by numerical simulations based on a phenomenological continuum model that explicitly incorporates the electrostatic interparticle interactions. The simulation results correctly describe the experiments at sufficiently high ionic strength.     

Immobilization of colloidal crystals, formed by polymer-grafted silica in organic solvent, in physical gels

Immobilization of colloidal crystals by gelation of polymer-grafted silica suspension in acetonitrile with alkyl amides derived from amino acids was investigated. Addition of N-benzyloxycarbonyl-l-isoleucylaminooctadecane (Z-Ile-C18) and 1,12-bis(N-benzyloxycarbonyl-l-valylamino)dodecane [Bis(Z-Val)-C12] to poly(maleic anhydride-co-styrene)-grafted silica suspension in acetonitrile resulted in formation of physical gels preserved colloidal crystal structure. From the reflection spectra, intersphere distance and size of crystallite in the gel formed with Bis(Z-Val)-C12 were confirmed to be mostly same as those of colloidal crystals in suspension.     

Close-packed colloidal crystalline arrays composed of silica spheres coated with titania

Titania coated monodisperse silica spheres have been synthesized and fabricated as a close-packed colloidal crystalline array. We have demonstrated that the coated colloidal sphere can be used to control the peak position of the optical stop band through variation of the coating thickness. The titania coated silica spheres were prepared by the layer-by-layer assembly coating process, which reciprocally laminates the cationic polyelectrolyte and the anionic titania nanosheets on a monodisperse silica spheres, and were sintered to change the titania nanosheets to anatase. The Bragg diffraction peak of the colloidal crystalline array shifted to the long wavelength region with an increase of thickness of the titania layer. Angle-resolved reflection spectra measurements clarified that the red shift was caused by increasing of the refractive index with increase of the thickness of the layer. The current work suggests new possibilities for the creation of advanced colloidal crystalline arrays with tunable optical properties from tailored colloidal spheres.     

A Luminescent Dicyanodistyrylbenzene-based Liquid Crystal Polymer Network for Photochemically Patterned Photonic Composite Film

A novel photonic composite film based on a luminescent dicyanodistyrylbenzene-based liquid crystal polymer network (LCN)was fabricated by using a silica colloidal crystal as a template.The upper part of inverse opal structure and the luminescence characteristics of dicyanodistyrylbenzene-based moiety endowed the resulting bilayer photonic film with structural color arising from coherent Bragg reflection and fluorescence properties,respectively.A fluorescence enhancement phenomenon was observed in the photonic film due to the overlap between the reflection band and emission band of the fluorescent LCN.More importantly,the photo-induced irreversible Z/E photoisomerization of dicyanodistyrylbenzene-based moiety in the photonic film led to both a reflection spectral shift and an observable fluorescence variation.On the basis of this effective phototuning process,microscopic patterning ofphotonic film was developed under both fluorescence mode and reflection mode.The work demonstrated here provides a new route to construct photo-responsive photonic film.     

Effects of stretching on microstructures of polymer-immobilized non-close-packed colloidal crystalline array

Non-close-packed silica colloidal crystalline array was immobilized by polymer, and effects of stretching on the change of the optical properties and microstructure of the colloidal crystalline arrays have been demonstrated. The immobilization was a two-step polymerization process: the first step was with hydrophilic polyethylene glycol acrylate (PEGA) polymer gel, and the second step was with 2-hydroxyethyl acrylate polymer matrix. The structure of the three-dimensional array was maintained during the immobilizing process with lock in periodic order. The peak wavelength of Bragg diffraction of the polymer-immobilized colloidal crystalline array shifted to shorter wavelength with stretching. The peak shift was caused by the compression of the polymer proportional to the stretching ratio, and the compression was homogeneous throughout the polymer-immobilized colloidal crystalline arrays. These results show that by using polymer-immobilized non-close-packed colloidal crystalline array, mechanically tunable photonic crystals can be realized, and they open the possibility of tuning the microstructure of colloidal crystalline array for photonic crystal.     

Multimodal coupling of optical transitions and plasmonic oscillations in rhodamine B modified gold nanoparticles

The optical properties of a photoluminescent dye rhodamine B (RhB) interacting with gold nanoparticles (AuNP) have been investigated using plasmonic absorbance, fluorescence, and resonance elastic light scattering (RELS) spectroscopy. We have found that these interactions result in a multimodal coupling that influence optical transitions in RhB. In absorbance measurements, we have observed for the first time the coupling resulting in strong screening of RhB π-π* transitions, likely caused by a contact adsorption of RhB on a conductive surface of AuNP. The nanoparticles quench also very efficiently the RhB fluorescence. We have determined that the static quenching mechanism with a non-F?rster fluorescence resonance energy transfer (FRET) from RhB molecules to AuNP is involved. The Stern-Volmer dependence F(0)/F = f(Q) shows an upward deviation from linearity, attributed to the ultra-high quenching efficiency of AuNP leading to the new extended Stern-Volmer model. A sharp RELS peak of RhB alone (λ(max) = 566 nm) has been observed for the first time and attributed to the resonance fluorescence and enhanced scattering. This peak is completely quenched in the presence of AuNP(22nm). Our quantum mechanical calculations confirm that the distance between AuNP surface and conjugated π-electron system in RhB is well within the range of plasmonic fields extending from AuNP. The optical transition coupling to plasmonic oscillations and the efficient energy transfer due to the interactions of fluorescent dyes with nanoparticles are important for biophysical studies of life processes and applications in nanomedicine.     

Automated preparation method for colloidal crystal arrays of monodisperse and binary colloid mixtures by contact printing with a pintool plotter

Photonic crystals and photonic band gap materials with periodic variation of the dielectric constant in the submicrometer range exhibit unique optical properties such as opalescence, optical stop bands, and photonic band gaps. As such, they represent attractive materials for the active elements in sensor arrays. Colloidal crystals, which are 3D gratings leading to Bragg diffraction, are one potential precursor of such optical materials. They have gained particular interest in many technological areas as a result of their specific properties and ease of fabrication. Although basic techniques for the preparation of regular patterns of colloidal crystals on structured substrates by self-assembly of mesoscopic particles are known, the efficient fabrication of colloidal crystal arrays by simple contact printing has not yet been reported. In this article, we present a spotting technique used to produce a microarray comprising up to 9600 single addressable sensor fields of colloidal crystal structures with dimensions down to 100 mum on a microfabricated substrate in different formats. Both monodisperse colloidal crystals and binary colloidal crystal systems were prepared by contact printing of polystyrene particles in aqueous suspension. The array morphology was characterized by optical light microscopy and scanning electron microscopy, which revealed regularly ordered crystalline structures for both systems. In the case of binary crystals, the influence of the concentration ratio of the large and small particles in the printing suspension on the obtained crystal structure was investigated. The optical properties of the colloidal crystal arrays were characterized by reflection spectroscopy. To examine the stop bands of the colloidal crystal arrays in a high-throughput fashion, an optical setup based on a CCD camera was realized that allowed the simultaneous readout of all of the reflection spectra of several thousand sensor fields per array in parallel. In agreement with Bragg's relation, the investigated arrays exhibited strong opalescence and stop bands in the expected wavelength range, confirming the successful formation of highly ordered colloidal crystals. Furthermore, a narrow distribution of wavelength-dependent stop bands across the sensor array was achieved, demonstrating the capability of producing highly reproducible crystal spots by the contact printing method with a pintool plotter.     

Silica particles coated with zwitterionic polymer brush: formation of colloidal crystals and anti-biofouling properties in aqueous medium

Silica particles (SiP) were modified with 2-bromoisobutyryl group-carrying silane coupling reagent, and a polymer brush of carboxymethylbetaine, poly[1-carboxy-N,N-dimethyl-N-(2'-methacryloyloxyethyl)methanaminium inner salt] (PolyCMB), was introduced onto surface of the particles using surface-initiated atom transfer radical polymerization (ATRP). After purification by simple ultrafiltration, the layer of the PolyCMB brush-carrying silica particle (SiP-PolyCMB) in aqueous medium showed a clear iridescence at the bottom of a quartz cell upon a slow sedimentation, indicating the formation of colloidal crystals due to both electrostatic and steric repulsion between the particles. The peak of the reflection spectra gradually shifted to a smaller wavelength region due to the formation of more densely packed ordered structure of the SiP-PolyCMB. Moreover, SiP-PolyCMBs dispersed in water showed neither salt- nor freeze-thaw cycle-induced coagulation, and were resistant against the non-specific adsorption of proteins such as bovine serum albumin and egg white lysozyme, which is in contrast with the noticeable adsorption of the proteins to the bare silica particles.     

Dye/gelled colloidal photonic crystal composites and their reversible pH-responsive optical behaviors

We introduced dyes, the colors of which are variable by changing the pH of their medium solutions, into gelled colloidal photonic crystals (GCPCs) and investigated their reversible pH-responsive optical behaviors. When the extinction position of the dye overlaps with the Bragg peak of the GCPC, the Bragg-diffracted light can be trapped in the GCPC; when the extinction position of the dye is shifted out of the Bragg peak of the GCPC, the Bragg diffracted light is free and can escape out of the GCPC. The optical behaviors of dye/gelled colloidal photonic crystal composites are reversible to the pH changes of their surrounding medium.     

Electro-optic effects of colloidal crystals of polymer-modified silica spheres immobilized with gelator

Electro-optic responses of colloidal crystals consist of poly(maleic anhydride-co-styrene)-modified silica spheres (P(MA-ST)/SiO₂) in acetonitrile and the crystals immobilized with a gelator, N-benzyloxycarbonyl-L-isoleucilaminooctadecane (Z-L-Ile-C-18), are studied by reflected-light intensity measurements and time-resolved reflection spectroscopy. Application of an alternating electric field deforms P(MA-ST)/SiO₂ crystal lattices reversibly. The response waveforms from the crystals are dependent on the frequency and strength of the applied electric field; similar dependencies have been qualitatively observed for the colloidal crystals consisting of polystyrene or silica spheres in aqueous media in our previous studies. Both gelated and ungelated P(MA-ST)/SiO₂ crystals change the reflection intensity, however, the amplitude is larger for the latter. The small response for the gelated P(MA-ST)/SiO₂ crystals is attributed to the higher elastic modulus (G). The G value of the gelated P(MA-ST)/SiO₂ crystals in acetonitrile is estimated from the change in the inter-sphere distance to be 8.0 Pa, which is about 2.3 and 2.4 times larger than that for ungelated P(MA-ST)/SiO₂ crystals in acetonitrile and colloidal silica crystals in aqueous media, respectively.     

Three-dimensional centimeter-sized colloidal silica crystals formed by addition of base

Three-dimensional (3D) centimeter-sized colloidal crystals can be spontaneously formed simply by dropping a NaOH solution (10 mM, approximately 10 microL) into an aqueous dispersion of dilute charged colloidal silica (particle diameter 110 nm, particle volume fraction phi = 0.023, 3-4 mL). The charge number of the silica particle increases with pH. Upon adding the NaOH solution, first, sub-millimeter-sized polycrystals are formed in the upper part of the sample due to charge-induced crystallization. The local phi value in the crystal region becomes nonuniform. The crystals with a high phi value accumulate at the bottom of the cell and then grow upward as columnar crystals. The crystal widths increase discontinuously with the growth, and in some cases, 3D centimeter-sized crystals are formed. The centimeter-sized crystals are also obtainable by the controlled diffusion of the base from its dilute reservoir. The present findings may prove valuable in the fabrication of large 3D single-crystalline photonic materials.     

pH and ionic strength responsive photonic polymers fabricated by using colloidal crystal templating

In this paper, monodispersed silica particles were synthesized using tetraethoxysiliane hydrolyzing in ethanol by a Stöber–Fink–Bobn method and then self-assembled on cleaning glass slides to form silica colloidal crystals. After photopolymerization of methacrylic acid mixing with ethylene glycol dimethylacrylate and hydrofluoric acid etching, the pH-responsive polymers were obtained with highly 3D-ordered macroporous structures templated by silica colloidal crystals. These polymers films can swell or deswell in response to external stimuli, causing a change of Bragg diffraction to read pH or ionic strength of various solutions by optical signals or electrochemical signals. As an application, they can be used as chemical sensors to detect pH or ionic strength variation of environment.     

Sedimentation and drying dissipative patterns of binary suspensions of colloidal silica spheres having different sizes

The sedimentation and drying dissipative structural patterns were formed during the course of drying binary mixtures among colloidal silica spheres of 183 nm, 305 nm, and 1.205 μm in diameter in aqueous suspension on a watch glass, a glass dish, and a cover glass, respectively. The broad ring-like sedimentation patterns were formed within several hours in suspension state for all the substrates used. Colorful macroscopic broad ring-like drying patterns were formed for the three substrates. In a watch glass, macroscopic drying patterns were composed of the outer and inner layers of small and large spheres, respectively. The two colored layers were ascribed to the Bragg diffractions of light by the dried colloidal crystals of the corresponding spheres. The width ratio of the layers changed in proportion to the mixing ratio of each spheres. In a glass dish, wave-like macroscopic drying patterns were observed in the intermediate areas between the outside edges of the broad ring and the inner wall of the cell. On a cover glass, the sphere mixing ratios were analyzed from the widths of the drying broad rings of the small spheres at the outside edge. High and distinct broad rings of small spheres and the low and vague broad one formed at the outer edges and in the inner area, respectively. Drying dissipative pattern was clarified to be one of the novel analysis techniques of colloidal size in binary colloidal mixtures.