Inverse Opal Photonic Crystals as an Optofluidic Platform for Fast Analysis of Hydrocarbon Mixtures.

Most of the reported optofluidic devices analyze liquid by measuring its refractive index. Recently, the wettability of liquid on various substrates has also been used as a key sensing parameter in optofluidic sensors. However, the above-mentioned techniques face challenges in the analysis of the relative concentration of components in an alkane hydrocarbon mixture, as both refractive indices and wettabilities of alkane hydrocarbons are very close. Here, we propose to apply volatility of liquid as the key sensing parameter, correlate it to the optical property of liquid inside inverse opal photonic crystals, and construct powerful optofluidic sensors for alkane hydrocarbon identification and analysis. We have demonstrated that via evaporation of hydrocarbons inside the periodic structure of inverse opal photonic crystals and observation of their reflection spectra, an inverse opal film could be used as a fast-response optofluidic sensor to accurately differentiate pure hydrocarbon liquids and relative concentrations of their binary and ternary mixtures in tens of seconds. In these 3D photonic crystals, pure chemicals with different volatilities would have different evaporation rates and can be easily identified via the total drying time. For multicomponent mixtures, the same strategy is applied to determine the relative concentration of each component simply by measuring drying time under different temperatures. Using this optofluidic sensing platform, we have determined the relative concentrations of ternary hydrocarbon mixtures with the difference of only one carbon between alkane hydrocarbons, which is a big step toward detailed hydrocarbon analysis for practical use.

Bioinspired Artificial Melanosomes As Colorimetric Indicators of Oxygen Exposure.

Many industries require irreversibly responsive materials for use as sensors or detectors of environmental exposure. We describe the synthesis and fabrication of a nontoxic surface coating that reports oxygen exposure of the substrate material through irreversible formation of colored spots. The coating consists of a selectively permeable rubber film that contains the colorless organic precursors to darkly pigmented synthetic melanin. Melanin synthesis within the film is triggered by exposure to molecular oxygen. The selectively permeable rubber film regulates the rate of oxygen diffusion, enabling independent control of the sensitivity and response time of the artificial melanosome, while preventing leaching of melanin or its precursors.

Tuning and Freezing Disorder in Photonic Crystals using Percolation Lithography.

Although common in biological systems, synthetic self-assembly routes to complex 3D photonic structures with tailored degrees of disorder remain elusive. Here we show how liquids can be used to finely control disorder in porous 3D photonic crystals, leading to complex and hierarchical geometries. In these optofluidic crystals, dynamically tunable disorder is superimposed onto the periodic optical structure through partial wetting or evaporation. In both cases, macroscopic symmetry breaking is driven by subtle sub-wavelength variations in the pore geometry. These variations direct site-selective infiltration of liquids through capillary interactions. Incorporating cross-linkable resins into our liquids, we developed methods to freeze in place the filling patterns at arbitrary degrees of partial wetting and intermediate stages of drying. These percolation lithography techniques produced permanent photonic structures with adjustable disorder. By coupling strong changes in optical properties to subtle differences in fluid behavior, optofluidic crystals may also prove useful in rapid analysis of liquids.

Color from hierarchy: Diverse optical properties of micron-sized spherical colloidal assemblies.

Materials in nature are characterized by structural order over multiple length scales have evolved for maximum performance and multifunctionality, and are often produced by self-assembly processes. A striking example of this design principle is structural coloration, where interference, diffraction, and absorption effects result in vivid colors. Mimicking this emergence of complex effects from simple building blocks is a key challenge for man-made materials. Here, we show that a simple confined self-assembly process leads to a complex hierarchical geometry that displays a variety of optical effects. Colloidal crystallization in an emulsion droplet creates micron-sized superstructures, termed photonic balls. The curvature imposed by the emulsion droplet leads to frustrated crystallization. We observe spherical colloidal crystals with ordered, crystalline layers and a disordered core. This geometry produces multiple optical effects. The ordered layers give rise to structural color from Bragg diffraction with limited angular dependence and unusual transmission due to the curved nature of the individual crystals. The disordered core contributes nonresonant scattering that induces a macroscopically whitish appearance, which we mitigate by incorporating absorbing gold nanoparticles that suppress scattering and macroscopically purify the color. With increasing size of the constituent colloidal particles, grating diffraction effects dominate, which result from order along the crystal's curved surface and induce a vivid polychromatic appearance. The control of multiple optical effects induced by the hierarchical morphology in photonic balls paves the way to use them as building blocks for complex optical assemblies--potentially as more efficient mimics of structural color as it occurs in nature.

Ultrasensitive visual read-out of nucleic acids using electrocatalytic fluid displacement.

Diagnosis of disease outside of sophisticated laboratories urgently requires low-cost, user-friendly devices. Disposable, instrument-free testing devices are used for home and physician office testing, but are limited in applicability to a small class of highly abundant analytes. Direct, unambiguous visual read-out is an ideal way to deliver a result on a disposable device; however, existing strategies that deliver appropriate sensitivity produce only subtle colour changes. Here we report a new approach, which we term electrocatalytic fluid displacement, where a molecular binding event is transduced into an electrochemical current, which drives the electrodeposition of a metal catalyst. The catalyst promotes bubble formation that displaces a fluid to reveal a high contrast change. We couple the read-out system to a nanostructured microelectrode and demonstrate direct visual detection of 100 fM DNA in 10 min. This represents the lowest limit of detection of nucleic acids reported using high contrast visual read-out.

Hierarchical structural control of visual properties in self-assembled photonic-plasmonic pigments.

We present a simple one-pot co-assembly method for the synthesis of hierarchically structured pigment particles consisting of silica inverse-opal bricks that are doped with plasmonic absorbers. We study the interplay between the plasmonic and photonic resonances and their effect on the visual appearance of macroscopic collections of photonic bricks that are distributed in randomized orientations. Manipulating the pore geometry tunes the wavelength- and angle-dependence of the scattering profile, which can be engineered to produce angle-dependent Bragg resonances that can either enhance or contrast with the color produced by the plasmonic absorber. By controlling the overall dimensions of the photonic bricks and their aspect ratios, their preferential alignment can either be encouraged or suppressed. This causes the Bragg resonance to appear either as uniform color travel in the former case or as sparse iridescent sparkle in the latter case. By manipulating the surface chemistry of these photonic bricks, which introduces a fourth length-scale (molecular) of independent tuning into our design, we can further engineer interactions between liquids and the pores. This allows the structural color to be maintained in oil-based formulations, and enables the creation of dynamic liquid-responsive images from the pigment.

Directional wetting in anisotropic inverse opals.

Porous materials display interesting transport phenomena due to restricted motion of fluids within the nano- to microscale voids. Here, we investigate how liquid wetting in highly ordered inverse opals is affected by anisotropy in pore geometry. We compare samples with different degrees of pore asphericity and find different wetting patterns depending on the pore shape. Highly anisotropic structures are infiltrated more easily than their isotropic counterparts. Further, the wetting of anisotropic inverse opals is directional, with liquids filling from the side more easily. This effect is supported by percolation simulations as well as direct observations of wetting using time-resolved optical microscopy.

Photo-tuning of highly selective wetting in inverse opals.

Crack-free inverse opals exhibit a sharply defined threshold wettability for infiltration that has enabled their use as colourimetric indicators for liquid identification. Here we demonstrate direct and continuous photo-tuning of this wetting threshold in inverse opals whose surfaces are functionalized with a polymer doped with azobenzene chromophores.

Creating bio-inspired hierarchical 3D-2D photonic stacks via planar lithography on self-assembled inverse opals.

Structural hierarchy and complex 3D architecture are characteristics of biological photonic designs that are challenging to reproduce in synthetic materials. Top-down lithography allows for designer patterning of arbitrary shapes, but is largely restricted to planar 2D structures. Self-assembly techniques facilitate easy fabrication of 3D photonic crystals, but controllable defect-integration is difficult. In this paper we combine the advantages of top-down and bottom-up fabrication, developing two techniques to deposit 2D-lithographically-patterned planar layers on top of or in between inverse-opal 3D photonic crystals and creating hierarchical structures that resemble the architecture of the bright green wing scales of the butterfly, Parides sesostris. These fabrication procedures, combining advantages of both top-down and bottom-up fabrication, may prove useful in the development of omnidirectional coloration elements and 3D-2D photonic crystal devices.

Single particle detection in CMOS compatible photonic crystal nanobeam cavities.

We report the label-free detection of single particles using photonic crystal nanobeam cavities fabricated in silicon-on-insulator platform, and embedded inside microfluidic channels fabricated in poly-dimethylsiloxane (PDMS). Our system operates in the telecommunication wavelength band, thus leveraging the widely available, robust and tunable telecom laser sources. Using this approach, we demonstrated the detection of polystyrene nanoparticles with dimensions down to 12.5nm in radius. Furthermore, binding events of a single streptavidin molecule have been observed.

Combinatorial wetting in colour: an optofluidic nose.

We present a colourimetric litmus test for simple differentiation of organic liquids based on wetting, which achieves chemical specificity without a significant sacrifice in portability or ease-of-use. Chemical specificity is derived from the combination of colourimetric wetting patterns produced by liquids in an array of inverse opal films, each having a graded wettability, but using different surface groups to define that gradient.

Integrated TiO2 resonators for visible photonics.

We demonstrate waveguide-coupled titanium dioxide (TiO(2) racetrack resonators with loaded quality factors of 2.2×10(4) for the visible wavelengths. The structures were fabricated in sputtered TiO(2) thin films on oxidized silicon substrates using standard top-down nanofabrication techniques, and passively probed in transmission measurements using a tunable red laser.

Wetting in color: colorimetric differentiation of organic liquids with high selectivity.

Colorimetric litmus tests such as pH paper have enjoyed wide commercial success due to their inexpensive production and exceptional ease of use. Expansion of colorimetry to new sensing paradigms is challenging because macroscopic color changes are seldom coupled to arbitrary differences in the physical/chemical properties of a system. Here we present in detail the design of a "Wetting In Color Kit" (WICK), an inexpensive and highly selective colorimetric indicator for organic liquids that exploits chemically encoded inverse-opal photonic crystals to project minute differences in liquids' wettability to macroscopically distinct, easy-to-visualize structural color patterns. We show experimentally and corroborate with theoretical modeling using percolation theory that the highly symmetric structure of our large-area, defect-free SiO(2) inverse-opal films leads to sharply defined threshold wettability for liquid infiltration, occurring at intrinsic contact angles near 20° with an estimated resolution smaller than 5°. The regular structure also produces a bright iridescent color, which disappears when infiltrated with liquid, naturally coupling the optical and fluidic responses. To deterministically design a WICK that differentiates a broad range of liquids, we introduced a nondestructive quality control procedure to regulate the pore structure and developed two new surface modification protocols, both requiring only silanization and selective oxidation. The resulting tunable, built-in horizontal and vertical chemistry gradients let us tailor the wettability threshold to specific liquids across a continuous range. With patterned oxidation as a final step, we control the shape of the liquid-specific patterns displayed, making WICK easier to read. Using these techniques, we demonstrate the applicability of WICKs in several exemplary systems that colorimetrically distinguish (i) ethanol-water mixtures varying by only 2.5% in concentration; (ii) methanol, ethanol, and isopropyl alcohol; (iii) hexane, heptane, octane, nonane, and decane; and (iv) samples of gasoline (regular unleaded) and diesel. As wetting is a generic fluidic phenomenon, we envision that WICK could be suitable for applications in authentication or identification of unknown liquids across a broad range of industries.

High-Q, low index-contrast polymeric photonic crystal nanobeam cavities.

We present the design, fabrication and characterization of high-Q (Q=36,000) polymeric photonic crystal nanobeam cavities made of two polymers that have an ultra-low index contrast (ratio=1.15) and observed thermo-optical bistability at hundred microwatt power level. Due to the extended evanescent field and small mode volumes, polymeric nanobeam cavities are ideal platform for ultra-sensitive biochemical sensing. We demonstrate that these sensors have figures of merit (FOM=9190) two orders of magnitude greater than surface plasmon resonance based sensors, and outperform the commercial Biacore(TM) sensors. The demonstration of high-Q cavity in low-index-contrast polymers can open up versatile applications using a broad range of functional and flexible polymeric materials.

Encoding complex wettability patterns in chemically functionalized 3D photonic crystals.

Much of modern technology--from data encryption to environmental sensors to templates for device fabrication--relies on encoding complex chemical information in a single material platform. Here we develop a technique for patterning multiple chemical functionalities throughout the inner surfaces of three-dimensional (3D) porous structures. Using a highly ordered 3D photonic crystal as a regionally functionalized porous carrier, we generate complex wettability patterns. Immersion of the sample in a particular fluid induces its localized infiltration and disappearance of the bright color in a unique spatial pattern dictated by the surface chemistry. We use this platform to illustrate multilevel message encryption, with selective decoding by specific solvents. Due to the highly symmetric geometry of inverse opal photonic crystals used as carriers, a remarkable selectivity of wetting is observed over a very broad range of fluids' surface tensions. These properties, combined with the easily detectable optical response, suggest that such a system could also find use as a colorimetric indicator for liquids based on wettability.

Space-time bullet trains via modulation instability and nonlocal solitons.

We introduce the generation of dense trains of light-bullets in nonlocal nonlinear dielectrics. We exploit stable spatio-temporal self-trapped optical packets stemming from the interplay between local electronic and nonlocal reorientational nonlinearities, considering a seeded temporal modulation instability by specifically referring to nematic liquid crystals.

Design of an efficient terahertz source using triply resonant nonlinear photonic crystal cavities.

We propose a scheme for efficient cavity-enhanced nonlinear THz generation via difference-frequency generation (DFG) processes using a triply resonant system based on photonic crystal cavities. We show that high nonlinear overlap can be achieved by coupling a THz cavity to a doubly-resonant, dual-polarization near-infrared (e.g. telecom band) photonic-crystal nanobeam cavity, allowing the mixing of three mutually orthogonal fundamental cavity modes through a chi((2)) nonlinearity. We demonstrate through coupled-mode theory that complete depletion of the pump frequency - i.e., quantum-limited conversion - is possible. We show that the output power at the point of optimal total conversion efficiency is adjustable by varying the mode quality (Q) factors.

Ultra-high-Q TE/TM dual-polarized photonic crystal nanocavities.

We demonstrate photonic crystal nanobeam cavities that support both TE- and TM-polarized modes, each with a Q factor greater than one million and a mode volume on the order of the cubic wavelength. We show that these orthogonally polarized modes have a tunable frequency separation and a high nonlinear spatial overlap. We expect these cavities to have a variety of applications in resonance-enhanced nonlinear optics.

Accessible light bullets via synergetic nonlinearities.

We introduce a new form of stable spatiotemporal self-trapped optical packets stemming from the interplay of local and nonlocal nonlinearities. Pulsed self-trapped light beams in media with both electronic and molecular nonlinear responses are addressed to prove that spatial and temporal effects can be decoupled, allowing for independent tuning. We numerically demonstrate that (3 + 1)D light bullets and antibullets, i.e., bright and dark temporal solitons embedded in stable (2 + 1)D nonlocal spatial solitons, can be generated in reorientational media under experimentally feasible conditions.

Difference-frequency generation with quantum-limited efficiency in triply-resonant nonlinear cavities.

We present a comprehensive study of second-order nonlinear difference frequency generation in triply resonant cavities using a theoretical framework based on coupled-mode theory. We show that optimal "quantum-limited" conversion efficiency can be achieved at any pump power when the powers at the pump and idler frequencies satisfy a critical relationship. We demonstrate the existence of a broad parameter range in which all triply-resonant DFG processes exhibit monostable conversion. We also demonstrate the existence of a geometry-dependent bistable region.