Sacrificial‐Layer Atomic Layer Deposition for Fabrication of Non‐Close‐Packed Inverse‐Opal Photonic Crystals

A method is presented for predicting and precisely controlling the structure of photonic crystals fabricated using sacrificial‐layer atomic layer deposition. This technique provides a reliable method for fabrication of high‐quality non‐close‐packed inverse shell opals with large static tunability and precise structural control. By using a sacrificial layer during opal infiltration, the inverse‐opal pore size can be increased with sub‐nanometer resolution and without distorting the lattice to allow for a high degree of dielectric backfilling and increased optical tunability. For a 10 % sacrificial layer, static tunability of 80 % is predicted for the inverse opal. To illustrate this technique, SiO₂ opal templates were infiltrated using atomic layer deposition of ZnS, Al₂O₃, and TiO₂. Experimentally, a static tunability of over 600 nm, or 58 %, was achieved and is well described by both a geometrical model and a numerical‐simulation algorithm. When extended to materials of higher refractive index, this method will allow the facile fabrication of 3D photonic crystals with optimized photonic bandgaps.     

Artificial Defect Engineering in Three‐Dimensional Colloidal Photonic Crystals

Artificial defect engineering in 3D colloidal photonic crystals is of paramount importance in terms of device applications. Over the past few years, we have carried out a great deal of research on introducing artificial defects, including point, line, and planar defects, in 3D colloidal photonic crystals by using “bottom‐up” self‐assembly in combination with “top‐down” micromachining techniques. In this Feature Article, we summarize our research results regarding the engineering of artificial defects in self‐assembled 3D photonic crystals, along with other important research breakthroughs in the literature. The significant advancements in the engineering of defects as reviewed here together with the encouraging reports on the fabrication of perfect colloidal crystals without unwanted defects will collectively lead to technological applications of self‐assembled 3D photonic crystals in the near future.     

Photoinduced Tuning of Optical Stop Bands in Azopolymer Based Inverse Opal Photonic Crystals

Photo‐tunable photonic crystals were prepared from three dimensional (3D) colloidal crystal templates using a photoresponsive azopolymer. For the preparation of azopolymer infiltrated photonic crystals, silica colloidal crystals were fabricated by gravity sedimentation, a self‐assembly technique. The interstitial voids between colloidal particles were filled with azopolymer and azopolymer inverse opals were produced by treatment with aqueous hydrofluoric acid. These photonic crystals exhibited stop bands in their transmission spectra measured in the normal incidence to the (111) plane of face centered cubic (fcc). The photonic bandgap of the azopolymer infiltrated opal and inverse opal could be controlled by the refractive index change due to the photoinduced orientation of azobenzene chromophores. When the azopolymer photonic crystals were irradiated with linearly polarized light, their bandgap positions were shifted to shorter wavelength regions with increasing irradiation time. This behavior experimentally produced a photoinduced orientation of the azobenzene groups in parallel with the incidence of the excitation light. Through such an out‐of‐plane orientation of azo chromophores, parallel to the [111] fcc crystallographic axis, the effective refractive index of the photonic crystal medium was decreased. Therefore, a blue‐shift in bandgap positions was consequently induced with 20–40 nm tuning ranges. The out‐of‐plane orientation was confirmed by angular resolved absorption spectral measurements.     

Colloidal Photonic Crystals Doped with Gold Nanoparticles: Spectroscopy and Optical Switching Properties

Polystyrene artificial opals with few gold nanoparticles (AuNp) embedded in the interstices (doping) are grown by using the meniscus technique starting from a mixed suspension of microspheres and AuNp. Samples having different sphere diameters and nanoparticle loads have been prepared. Their reflectance spectra clearly show a dramatic bathochromic shift of the photonic stop band (up to 1400 cm^–1) and a reduction of its full width half maximum, due to an increase of the effective refractive index of about 8 % with respect to bare opals, which is accounted for by analytical theoretical models. Reflectance spectra do not show any direct evidence of AuNp absorption even at the higher AuNp doping level. Nanosecond transient absorption measurements on these systems indicate that a variation of transmission (optical switching) of about 150 % is observed for AuNp doped opals upon photoexcitation with 9 ns laser pulses at 532 nm. No switching is instead observed for bare opals.     

Tunable,Gap‐State Lasing in Switchable Directions for Opal Photonic Crystals

A photonic crystal laser that is tunable throughout the visible in three‐dimensionally switchable directions is demonstrated. This photo‐pumped laser utilizes a dye‐infiltrated, single‐crystal SiO₂ opal having incomplete bandgaps. Our results support a gap‐state‐enhanced distributed feedback mechanism for lasing. Three different types of wavelength tunability are demonstrated, each applicable over a different frequency range and involving either single or multiple bandgaps. The many independent laser cavities that exist in one photonic crystal are demonstrated by simultaneously obtaining lasing in various colors and directions from an opal crystal. The observation of characteristic laser emission lines provides a new spectroscopy for characterizing intra‐gap photonic states, which may be useful for developing the photonic crystal analogues of electronic circuitry.     

二维Kagome格子光子晶体禁带的数值模拟

采用平面波展开法模拟计算了由空气背景中的介质柱构成的二维Kagome格子光子晶体的能带结构，得到了使完全光子禁带最大化的结构参量．计算结果表明：由圆形、正六边形和正四边形三种不同形状锗介质柱构成的Kagome格子光子晶体都出现了完全光子禁带，最大禁带分别为△=0．014(ωa／2πc)、△=0．013(ωa／2πc)、△=0．011(ωa／2πc)．发现由圆形和正六边形两种介质柱构成的Kagome格子光子晶体在填充比连续变化的较大的范围内都有宽度较为稳定的完全禁带，且它们具有非常相似的能带结构．     

复周期结构光子晶体的光子能带特性研究

本文构思了一种每个周期内部有几个不同的小单元的复周期结构光子晶体，并利用光学传输矩阵法对这种光子晶体进行了数值模拟计算。计算结果表明，这种复周期结构光子晶体比普通结构的光子晶体多出1个大的光子禁带区。适当调整参数还可以分别获得多通道窄带滤波特性、带通滤液特性和窄带透过特性。     

Site‐Selective Self‐Assembly of Colloidal Photonic Crystals

A scalable method for site‐selective, directed self‐assembly of colloidal opals on topologically patterned substrates is presented. Here, such substrate contains optical waveguides which couple to the colloidal crystal. The site‐selectivity is achieved by a capillary network, whereas the self‐assembly process is based on controlled solvent evaporation. In the deposition process, a suspension of colloidal microspheres is dispensed on the substrate and driven into the desired crystallization sites by capillary flow. The method has been applied to realize colloidal crystals from monodisperse dielectric spheres with diameters ranging from 290 to 890 nm. The method can be implemented in an industrial wafer‐scale process.     

Photoswitchable Spirobenzopyran‐ Based Photochemically Controlled Photonic Crystals

We have developed a photochemically controlled photonic‐crystal material by covalently attaching spiropyran derivatives to polymerized crystalline colloidal arrays (PCCAs). These PCCAs consist of colloidal particles that self‐assemble into crystalline colloidal arrays (CCAs), which are embedded in crosslinked hydrogels. Photoresponsive PCCAs were made two ways: 1) by functionalizing the hydrogel network with spiropyran derivatives, and 2) by functionalizing the colloidal particles with spiropyran derivatives. These materials can diffract light in the UV, visible, or near‐IR spectral regions. The diffraction of the PCCAs is red‐shifted by exciting the spiropyran with UV light. Alternatively, the diffraction is blue‐shifted by exciting the spiropyran with visible irradiation. Thus, this material acts as a memory storage material where information is recorded by illuminating the PCCA and information is read out by measuring the photonic‐crystal diffraction wavelength. UV excitation forms the open spiropyran form while visible excitation forms the closed spiropyran form. The diffraction shifts result from changes in the free energy of mixing of the PCCA system as the spiropyran is photoexcited to its different stable forms.     

High‐Quality Photonic Crystals Infiltrated with Quantum Dots

We report a method for producing colloidal crystals heavily loaded with PbS quantum dots (QDs). The approach employed uses capillary forces to load the QDs in the interstitial voids of the colloid crystals and yields highly ordered structures with a high loading of QDs. The infiltration process is qualitatively monitored using confocal fluorescence microscopy and scanning electron microscopy. The optical properties of the resulting composite structure are examined using optical spectroscopy. The shift in the stopband resulting from the infiltration of the colloid crystal shows that the PbS QDs occupy nearly 100 % of the volume of the interstitial space.     

Photonic Crystals from Ordered Mesoporous Thin‐Film Functional Building Blocks

Environment‐sensitive Bragg reflectors are built using functional mesoporous thin films as building blocks. Tuning of optical properties is achieved by changing the composition or porosity of the slabs or the introduction of planar defects. Sorption or capillary condensation of molecules into the pore system results in a 10–40 nm photonic bandgap (PBG) shift. Organic functions added to the pore surface change the response, permitting tailoring of the selectivity towards small‐size molecules.     

Assembly of Wiseana Iridovirus: Viruses for Colloidal Photonic Crystals

In vitro assembly of Wiseana iridescent virus (WIV) yields iridescent pellets and films with structural color more vivid than in the native insect. WIV is icosahedral in shape, 140 nm in diameter, with 30 nm long fibrils attached to the outer surface, and exhibits a surface charge ca. 1/6th that of a comparable polymer colloid. The low surface charge and tethered chains on the virus surface allow the facile modification of the interparticle distance. Directed sedimentation yields predominantly an amorphous liquid‐like packing of the virus. Such samples exhibit a broad reflection band that is angle independent and for which the broad maximum can be reversibly shifted from blue towards red with increased hydration. Slow sedimentation and flow‐assisted assembly methods produce thin films with a polycrystalline morphology that exhibit narrower, more intense reflectivity peaks, which are hydration and angle dependent. This study points toward the potential of viral particles for photonic crystals where their unique structural features (icosahedral symmetry, extreme monodispersity, precise surface functionalization, and tethered surface chains of low surface‐charge density) may lead to superior control of optical properties of their assembled arrays.     

From Hybrid Microgels to Photonic Crystals

We have synthesized semiconductor and metal nanoparticles (NPs) in the constrained geometry of polymer microgels. We used electrostatically driven attraction between the ionic groups of the microgels and the precursor cations in the bulk liquid medium to introduce the cations in the interior of the microgel. In the second step, the cations in the microgel interior reacted with the anion (to obtain semiconductor NPs) or they were treated with a reducing agent (to obtain metal NPs). Good control over the size and the concentration of the NPs in the microgel particles was achieved by changing the composition of the corresponding microgel. The doped microgel spheres were heated at pH 4 above the volume‐transition temperature of the polymer to expel the water from the microsphere interior; then the polymer was encapsulated with a hydrophobic polymeric shell. Hybrid core–shell particles were used as the building blocks of the nanostructured material with properties of a photonic crystal.     

Air‐Pulse‐Drive Fabrication of Photonic Crystal Films of Colloids with High Spectral Quality

A fast and highly controllable method of fabricating large films of photonic crystals of colloids is reported. A charge‐stabilized colloidal suspension was run in a flat capillary driven by a pressure‐regulated air pulse. The colloidal crystal texture formed in the capillary was a sensitive function of air pressure. Above a critical pressure, the entire capillary was filled with a uniform single‐domain texture whose transmittance spectrum showed a high quality as a photonic crystal, i.e., excellent opacity at a photonic bandgap and high transparency at other wavelengths. The present method is easily applicable to industrial processes for mass production.     

Inverse‐Woodpile Photonic Band Gap Crystals with a Cubic Diamond‐like Structure Made from Single‐Crystalline Silicon

Three dimensional photonic band gap crystals with a cubic diamond‐like symmetry are fabricated. These so‐called inverse‐woodpile nanostructures consist of two perpendicular sets of pores in single‐crystal silicon wafers and are made by means of complementary metal oxide–semiconductor (CMOS)‐compatible methods. Both sets of pores have high aspect ratios and are made by deep reactive‐ion etching. The mask for the first set of pores is defined in chromium by means of deep UV scan‐and‐step technology. The mask for the second set of pores is patterned using an ion beam and carefully placed at an angle of 90° with an alignment precision of better than 30 nm. Crystals are made with pore radii between 135–186 nm with lattice parameters a = 686 and c = 488 nm such that a/c = √2; hence the structure is cubic. The crystals are characterized using scanning electron microscopy and X‐ray diffraction. By milling away slices of crystal, the pores are analyzed in detail in both directions regarding depth, radius, tapering, shape, and alignment. Using optical reflectivity it is demonstrated that the crystals have broad reflectivity peaks in the near‐infrared frequency range, which includes the telecommunication range. The strong reflectivity confirms the high quality of the photonic crystals. Furthermore the width of the reflectivity peaks agrees well with gaps in calculated photonic band structures.     

High Quality Factor Metallodielectric Hybrid Plasmonic–Photonic Crystals

A 2D polystyrene colloidal crystal self‐assembled on a flat gold surface supports multiple photonic and plasmonic propagating resonance modes. For both classes of modes, the quality factors can exceed 100, higher than the quality factor of surface plasmons (SP) at a polymer–gold interface. The spatial energy distribution of those resonance modes are carefully studied by measuring the optical response of the hybrid plasmonic–photonic crystal after coating with dielectric materials under different coating profiles. Computer simulations with results closely matching those of experiments provide a clear picture of the field distribution of each resonance mode. For the SP modes, there is strong confinement of electromagnetic energy near the metal surface, while for optical modes, the field is confined inside the spherical particles, far away from the metal. Coating of dielectric material on the crystal results in a large shift in optical features. A surface sensor based on the hybrid plasmonic–photonic crystal is proposed, and it is shown to have atomic layer sensitivity. An example of ethanol vapor sensing based on physisorption of ethanol onto the sensor surface is demonstrated.     

Cover Picture: Assembly of Wiseana Iridovirus: Viruses for Colloidal Photonic Crystals (Adv. Funct. Mater. 8/2006)

Assembly of colloids is a versatile tool for micro‐ and nanofabrication. Natural and artificially engineered viruses offer the opportunity to expand the functionality and versatility of such assemblies. The cover shows optically iridescent, thin polycrystalline arrays (background) as well as bulk pellets (inset right) that exhibit reversible hydration‐dependent reflection spectra, as reported by Vaia and co‐workers on p. 1086. The films and pellets were created in vitro with classical colloid‐assembly techniques from Wiseana iridescent virus (inset, center) harvested from infected Wiseana spp larvae (inset, left). In vitro assembly of Wiseana iridescent virus (WIV) yields iridescent pellets and films with structural color more vivid than in the native insect. WIV is icosahedral in shape, 140 nm in diameter, with 30 nm long fibrils attached to the outer surface, and exhibits a surface charge ca. 1/6th that of a comparable polymer colloid. The low surface charge and tethered chains on the virus surface allow the facile modification of the interparticle distance. Directed sedimentation yields predominantly an amorphous liquid‐like packing of the virus. Such samples exhibit a broad reflection band that is angle independent and for which the broad maximum can be reversibly shifted from blue towards red with increased hydration. Slow sedimentation and flow‐assisted assembly methods produce thin films with a polycrystalline morphology that exhibit narrower, more intense reflectivity peaks, which are hydration and angle dependent. This study points toward the potential of viral particles for photonic crystals where their unique structural features (icosahedral symmetry, extreme monodispersity, precise surface functionalization, and tethered surface chains of low surface‐charge density) may lead to superior control of optical properties of their assembled arrays.     

Multicolor Printing Using Electric‐Field‐Responsive and Photocurable Photonic Crystals

Efficient and large scale printing of photonic crystal patterns with multicolor, multigrayscale, and fine resolution is highly desired due to its application in smart prints, sensors, and photonic devices. Here, an electric‐field‐assisted multicolor printing is reported based on electrically responsive and photocurable colloidal photonic crystal, which is prepared by supersaturation‐induced self‐assembly of SiO₂ particles in the mixture of propylene carbonate (PC) and trimethylolpropane ethoxylate triacrylate (ETPTA). This colloidal crystal suspension, named as E‐ink, has tunable structural color, controllable grayscale, and instantly fixable characteristics at the same time because the SiO₂/ETPTA‐PC photonic crystal has metastable and reversible assembly as well as polymerizable features. Lithographical printing with photomask and maskless pixel printing techniques are developed respectively to efficiently prepare multicolor and high‐resolution photonic patterns using a single‐component E‐ink.     

Fabrication and Characterization of Two‐Photon Polymerized Features in Colloidal Crystals

The fabrication and characterization of two‐photon polymerized features written within and outside of colloidal crystals is presented. Two‐photon polymerization (TPP) response diagrams are introduced and developed to map the polymerization and damage thresholds for features written via modulated beam rastering. The use of tris[4‐(7‐benzothiazol‐2‐yl‐9,9‐diethylfluoren‐2‐yl)phenyl]amine (AF‐350) as an initiator for TPP is demonstrated for the first time and TPP response diagrams illustrate the polymerization window. These diagrams also demonstrate that the polymerization behavior within and outside of colloidal crystals is similar and electron microscopy reveals nearly identical resolution. Fluorescence confocal microscopy further enables visualization of non‐self‐supporting, three‐dimensional TPP features within self‐assembled photonic crystals. Finally, microspot spectroscopy is collected from a two‐photon feature written within a colloidal crystal and this is compared with simulation.     

Exploiting Nanoroughness on Holographically Patterned Three‐Dimensional Photonic Crystals

The fabrication of three‐dimensional (3D) diamond photonic crystals with controllable nanoroughness (≤120 nm) on the surface from epoxy‐functionalized cyclohexyl polyhedral oligomeric silsesquioxanes (POSS) is reported. The nanoroughness is generated on the 3D network due to microphase separation of the polymer chain segments in a nonsolvent during the rinsing step in holographic lithography process. The degree of roughness can be tuned by the crosslinking density of the polymer network, which is dependent on the loading of photoacid generators, the exposure dosage, and the choice of developer and rinsing solvent. Because the nanoroughness size is small, it does not affect the photonic band gap position of the photonic crystal in the infrared region. The combination of periodic microstructure and nanoroughness, however, offers new opportunities to realize superhydrophobicity and enhanced dye adsorption in addition to the photon management in the 3D photonic crystal.