Inverse Opal Photonic Crystals Research Articles

A Stable Perovskite Sensitized Photonic Crystal P-N Junction with Enhanced Photoelectrochemical Hydrogen Production.

The slow photon effect in inverse opal photonic crystals represents a promising approach to manipulate the interactions between light and matter through the design of material structures. This study introduces a novel ordered inverse opal photonic crystal (IOPC) sensitized with perovskite quantum dots (PQDs), demonstrating its efficacy for efficient visible-light-driven H2 generation via water splitting. The rational structural design contributes to enhanced light harvesting. The sensitization of the IOPC with PQDs improves optical response performance and enhances photocatalytic H2 generation under visible light irradiation compared to the IOPC alone. The designed photoanode exhibits a photocurrent density of 3.42 mA cm-2 at 1.23 V vs RHE. This work advances the rational design of visible light-responsive photocatalytic heterostructure materials based on wide band gap metal oxides for photoelectrochemical applications.

Preparation of Ag@Au core-shell nanoparticles embedded in TiO2 inverse opal for light harvesting and efficiency enhancement in quantum dot sensitized solar cells

In the fabrication of Quantum dot sensitized solar cells (QDSSCs), it is important to fabricate a photoanode with a high ability to trap photons as well as transfer photogenerated electrons. TiO2 inverse opal (TIO) photonic crystals with their organized porous structures, besides their chemical nature, have unique optical features such as the slow-photon effect, photon localization, and photonic bandgap (PBG). Herein, to improve the efficiency of QDSSCs, gold, silver, and silver/gold core-shell (Ag@Au) plasmonic nanoparticles (nps) are loaded on TIO. The plasmonic nanoparticle-decorated inverse opal improves the light scattering process and provides direct charge transfer tunnels, which can effectively prevent the recombination of electron-hole pairs. In this work, fabricated QDSSCs with TIO (double-layer)/ZnS/CdS/CdSe/ZnSe/ZnS photoanode, and a 6 μm total thickness of the TIO multilayer, has an open circuit voltage (Voc) of 0.745 V and short-circuit current density (JSC) of 16.22 mA/cm2. The obtained results are higher than the common anatase TiO2 (TiO2-A)/ rutile TiO2 (TiO2-R)/QD photoanode. Also, the TIO (double-layer)/Ag@Au/QDs photoanode exhibits JSC=20.3283 mA/cm2, Voc= 0.75 V, and a power conversion efficiency (PCE) of ƞ=10.79 %.

Ethanol-responsive structural colors with multi-level information encryption based on the patterned three-layer inverse opal photonic crystal

Stimulus-responsive inverse opal photonic crystals (IOPCs) with tunable structural colors show significant promise in information security. To improve upon the traditional bilayer structure with limited color information and single decoding mode, this work developed an ethanol-responsive structure with multi-level information encryption ability by inserting a functional layer into two shielding layers (red Layer A with a photonic stop band (PSB) at 640 nm and green Layer C with a PSB at 530 nm). The functional layer was composed of colorless Layer B, a quick response (QR) code pattern made of TiO2 nanoparticles, and a dense polymer. Due to the isolation of distinct layers, different reflectance values, and different PSB positions of the three-layer IOPC, the structural color of Layer B could only be “turned on” by wetting the entire structure when its PSB redshifted from 360 nm to 460 nm. Specifically, when either side was individually wetted, the PSB of Layer A or C redshifted to 825 nm or 685 nm, and the color of the QR code was dominated by the unwetted red or green layer. After the entire structure had been soaked, the blue QR code was decoded. Meanwhile, when the detecting angle increased from 5° to 60°, the PSBs of Layers B and C in the wetted three-layer IOPC blueshifted from 460 nm to 365 nm and from 685 nm to 540 nm, respectively, which resulted in a cascade decoding process with a single- or mixed-color output. This structure provides a good foundation for multi-level information encryption.

Bioinspired Colorimetric Double Inverse Opal Photonic Crystal Indicators for Ethanol Concentration Sensing in Fermentation Engineering.

Photonic crystal-based ethanol concentration indicators with rapid response and brilliant structural color output definitely take a place in colorimetric sensors. Here, based on the H-bond-regulated swelling of acrylate shape memory polymers (SMPs) and the solvent-induced structural color change of the double inverse opal photonic crystals (DIOPCs), new-type photonic crystals (PCs) colorimetric indicators were constructed, exhibiting a span of maximum reflection wavelength (λmax) up to ∼166 nm in response to alcohols with concentrations from 0 to 100 vol %. DIOPC indicators (DIOPCIs) show a rapid response to alcohols (<1.5 s) and output different structural colors (covering from blue to red). The colorimetric sensing mechanism includes the solvent-triggered recovery of the inverse opal skeleton, the cosolvency effect and H-bonds induced swelling/shrinkage of the polymer, the phase separation between polystyrene (PS) microsphere and polymer skeleton, and the light diffraction of DIOPCs. While ensuring a larger λmax span by regulating the H-bond interactions in polymer chains through acrylamide (AAm), AAm-modified DIOPCIs are sensitive to some specific ethanol concentrations. The real-time sensing of ethanol concentration during fermentation verified the practicability of DIOPCIs, thus establishing a visual model between structural color and corresponding fermentation kinetics. We envisage that the DIOPCIs will contribute to the intelligentization of the alcoholic fermentation and distillation industry.

Synthesis of silica inverse opal and evaluation of its potential as an optical chemical sensor for detection of metal salts

In this paper, SiO2 inverse opal photonic crystals, made by the co-assembly of SiO2 and polymethylmethacrylate (PMMA) microspheres, were used to detect 20 different metal salts with a concentration of 0.002 mol/L. Surprisingly, two different behaviors were observed. Some metal salts caused a redshift in photonic bandgap (PBG) while the others led to a PBG’s blueshift. The observed different behaviors of salts are due to their distinct influence on the lattice constant of the inverse structures which was precisely investigated by analyzing the field emission scanning electron microscopy (FESEM) images and ultraviolet–visible (UV–Vis) spectroscopy. It has been revealed that the competition between the hydrophilicity of SiO2 and the hygroscopicity of metal salts led to a shift of PBG toward blue or red. The maximum shift in the PBG range was observed for mercury (II) nitrate salt (19 nm), which indicates a sensitivity of 9.5 nm per concentration unit (mM). Furthermore, the lowest displacement of the PBG was observed for the sodium nitrate salt (5 nm), which represents a sensitivity of 2.5 nm/mM. The lowest and highest values of the detection limit (LOD) for mercury (II) nitrate salt and sodium nitrate salt equal 0.193 mmol/L and 0.887 mmol/L, respectively. In addition, according to the calibration curve, with a regression coefficient of R2 > 0.95, there is a linear relationship between the salt concentration and the displacement of the PBG of the structure. Based on the results illustrating the sensitivity of the synthesized inverse opal to the type and concentration of the salts, inverse opal can be regarded as a promising structure to create a new perspective in the field of chemical sensing.

Photon Management Enabled by Opal and Inverse Opal Photonic Crystals: from Photocatalysis to Photoluminescence Regulation.

Light is a promising renewable energy source and can be converted into heat, electricity, and chemical energy. However, the efficiency of light-energy conversion is largely hindered by limited light-absorption coefficients and the low quantum yield of current-generation materials. Photonic crystals (PCs) can adjust the propagation and distribution of photons because of their unique periodic structures, which offers a compelling platform for photon management. The periodicity of materials with an alternating refractive index can be used to manipulate the dispersion of photons to generate the photonic bandgap (PBG), in which light is reflected. The slow photon effect, i. e., photon propagation at a reduced group velocity near the edges of the PBG, is widely regarded as another valuable optical property for manipulating light. Furthermore, multiple light scattering can increase the optical path, which is a vital optical property for PCs. Recently, the light reflected by PBG, the slow photon effect, and multiple light scattering have been exploited to improve light utilization efficiency in photoelectrochemistry, materials chemistry, and biomedicine to enhance light-energy conversion efficiency. In this review, the fabrication of opal or inverse opal PCs and the theory for improving the light utilization efficiency of photocatalysis, solar cells, and photoluminescence regulation are discussed. We envision photon management of opal or inverse opal PCs may provide a promising avenue for light-assisted applications to improve light-energy-conversion efficiency.

The role of pores in structure of polyethylenglycol diacrylate based‐inverse opal photonic crystal in binding protein applicable to optical biosensor

AbstractHere, the role of pores in the structure of inverse opal photonic crystals (IOPC) in binding proteins in comparison with their parent photonic crystal (PC) templates has been investigated. For this purpose, polyethyleneglycol diacrylate (PEGDA) coated with SiO2‐based PC (PEGDA/SiO2‐based PC) and PEGDA‐based IOPC were attached with fluorophore Alexa 488, which is a polyclonal secondary antibody, to investigate their fluorescence emission. Scanning electron microscopy (SEM) images showed face centered cubic (fcc) packing of the PEGDA/SiO2‐based PC. And it remained after the formation of PEGDA‐based IOPC. The presence of 3‐aminopropyl triethoxysilane (APTES) and Alexa 488 that immobilized the PEGDA‐based PC and PEGDA‐based IOPC was recognized by the appearance of bands at 850, 1175, and a dominant increase in the band at 1750 cm−1. Those were attributed to (N─H) wagging, (C─N) stretching, and (C═O) stretching vibrations, respectively. Reflectance spectra showed a blue shift of the Bragg photonic band gap of the PEGDA‐based IOPC in comparison with that of the PEGDA/SiO2‐based PC. The fluorescence images showed a significant increase in the fluorescence intensity of PEGDA‐based IOPC owing to the resonance effect. These obtained results indicated the role of pores in structure of PEGDA‐based IOPC in improvement of the attachment of Alexa 488 protein.

A dual-mode biosensor based on silica inverse opal photonic crystals modulated electrochemiluminescence and dye displacement colorimetry for the sensitive detection of synthetic cathinone in water environment

To address the challenges posed by signal capacity limitations and the reliance of sensing methods on single analytical information, this study developed an electrochemiluminescence (ECL) and colorimetric dual-mode sensing platform for the precise detection of 4-chloroethcathinone (4-CEC) in water environments. Firstly, the accurate alignment of the reflection wavelength of appropriately sized silica inverse opal photonic crystals (SIOPCs) with the ECL emission wavelength of luminescent metal-organic frameworks (PCN-224) has been achieved via diameter modulation. This innovative design, which cleverly utilized the band-edge effect, improved the luminous intensity of the ECL sensor, leading to a significant boost in analytical performance. Secondly, the establishment of a colorimetric detection method for confirming the presence of 4-CEC in samples through visual observation of color changes was achieved by employing an aptamer-based dye displacement reaction, utilizing differential binding affinities between the aptamer and both the sulforhodamine B (SRB) and 4-CEC. Under the optimal experimental conditions, the dual-mode sensor demonstrated ECL detection of limits (LOD) of 2.6 × 10−13 g/L and colorimetric LOD of 6.5 ng/L for 4-CEC. These findings highlighted the tremendous potential of developing streamlined and efficient dual-signal readout platforms using ECL aptamer sensors for the precise determination of other Synthetic cathinones (SCs) in water environments.

The peroxidase-like activity of Au NPs deposited inverse opal CeO2 nanozyme for rapid and sensitive H2O2 sensing

In this study, the hybrid nanozyme gold nanoparticles deposited CeO2 inverse opal photonic crystals (IOPCs) on the glass slide was fabricated by bestowing the hybrid with the beneficial porous morphology with its unique advantages: its surface valence states, high surface area, and copious active sites. The oxidase and peroxidase-mimicking activity was studied by observing the catalytic oxidation of chromogenic substrate 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid (ABTS) in the presence of H2O2, which can be visualized by the eyes. Au NPs and CeO2 IOPCs consisting of Ce3+ and Ce4+ can oxidize ABTS in the presence of H2O2 by mimicking peroxidase enzymes. The peroxidase-like activity of nanozyme was substantially improved by introducing light irradiation due to the photosensitive nature of the hybrid. The peroxidase-like activity of nanozyme enabled H2O2 linear detection over the range 9 to 500 μM, with a LOD of 2.7 µM. The acceptable nanozyme activity is probably owing to the easy access of H2O2 to the active sites of nanozyme. The porous architecture led to the easy channeling of reactants and products. The periodic architecture of the nanozyme also led to decent reproducibility. Without functionalization, the nanozyme can be a promising alternative to peroxidase enzymes for hydrogen peroxide measurements.

Graphene oxide-decorated hyrogel inverse opal photonic crystal improving colorimetric and fluorescent responses for rapid detection of lipocalin-1

In this paper, the colorimetric and fluorescent biosensors prepared from polyethylene glycol diacrylate (PEGDA)-based inverse opal photonic crystal (IOPC) decorated with graphene oxide (GO) (termed as GO-modified PEGDA-based IOPC) have been explored for simple and rapid semi-quantitative and quantitative detections of biomarker lipocaline-1 (LCN1) in tear at low level, respectively. We found that only after the concentration of GO (CGO) was sufficiently high to create a thin GO layer due to intermolecular interactions between neighboring GO molecules on the PEGDA surface, the red-shift of the reflection peak position (λstb) became effective. This widening of the shift in λstb became significant when GO-modified PEGDA-based IOPC was selectively attached with LCN1 via the immunoassay, because the attachment with LCN1 caused a reverse shift in λstb. Correspondingly, the visualizable photonic color could vary in wider range depending on the concentration of LCN1 (CLCN1), from orange color of blank solution to light blue color of solution containing LCN1 at CLCN1 of 0.06 mg/mL using CGO = 2.5 mg/mL. For quantification, CGO and enrichment time of LCN1 were optimized for getting the maximum fluorescence microscopy intensity. The diagram for the relationship between fluorescence intensity and CLCN1 showed various advantages of GO-modified PEGDA-based IOPC over non-GO-modified PEGDA-based IOPC. Those were higher fluorescence intensity, wider linear range and higher detection sensitivity. Thus, our results revealed potential applications of GO-modified PEGDA-based IOPC in screening patients with diabetic retinopathy (DR) in early stage.

Applications of inverse opal photonic crystal hydrogels in the preparation of acid-base color-changing materials.

Hydrogels are three-dimensional (3D) crosslinked network hydrophilic polymers that have structures similar to that of biological protein tissue and can quickly absorb a large amount of water. Opal photonic crystals (OPCs) are a kind of photonic band gap material formed by the periodic arrangement of 3D media, and inverse opal photonic crystals (IOPCs) are their inverse structure. Inverse opal photonic crystal hydrogels (IOPCHs) can produce corresponding visual color responses to a change in acid or alkali in an external humid environment, which has wide applications in chemical sensing, anti-counterfeiting, medical detection, intelligent display, and other fields, and the field has developed rapidly in recent years. In this paper, the research progress on fast acid-base response IOPCHs (pH-IOPCHs) is comprehensively described from the perspective of material synthesis. The technical bottleneck of enhancing the performance of acid-base-responsive IOPCHs and the current practical application limitations are summarized, and the development prospects of acid-base-responsive IOPCHs are described. These comprehensive analyses are expected to provide new ideas for solving problems in the preparation and application of pH-IOPCHs.

(Invited) Tuning and Transferring Slow Photons for Unprecedented Visible Light Photocatalysis

Periodic structures with alternating refractive indices such as inverse opal photonic crystals are capable of reducing the group velocity of light such that this slowed light can be more efficiently harvested for highly enhanced solar energy conversion. However, the generation, the manipulation and, in particular, the practical applications of these slow photons remain highly challenging. Here, we report the first proof of concept on the ability to control, in an inverse opal TiO2-BiVO4 hetero-composite, the transfer of slow photons generated from the inverse opal photonic structure to the photocatalytically active BiVO4 nanoparticles for highly enhanced visible light photoconversion. Tuning the slow photon frequencies, in order to accommodate the electronic band gap of BiVO4 for slow photon transfer and for significantly improved light harvesting, was successfully achieved by varying the structural periodicity (pore size) of inverse opal and the light incidence angle. The photocatalytic activity of BiVO4 in all inverse opal structures, promoted by slow photon effect, reached up to 7 times higher than those in the non-structured compact films. This work opens new avenues for the practical utilization of slow photon effect under visible light in photocatalytic energy-related applications like water splitting and carbon dioxide reduction and in photovoltaics.

Slow photon photocatalytic enhancement of H2 production in TaON inverse opal photonic crystals

In this study, tantalum oxynitride inverse opal (TaON IO) photonic crystals with different macropore diameters (D) were synthesized in a two-step process involving colloidal crystal templating and thermal nitridation, then applied as visible light-driven photocatalysts for hydrogen production. The TaON inverse opals showed photonic band gaps (PBGs) at visible wavelengths, with the PBG position redshifting as the diameter of the macropores increased in accordance with a modified Bragg's law expression. By aligning the electronic absorption edge of TaON (Eg ∼ 2.4 eV) with the blue edge (short-wavelength side) or red edge (long-wavelength side) of the PBGs, slow photon enhancement of photocatalytic H2 generation was realized. H2 production tests conducted in 10 vol% methanol containing H₂PtCl6 under Xe lamp irradiation (150 W) showed that the hydrogen production rate was enhanced by ∼1.3–1.4 times when the TaON absorption edge (∼510 nm) aligned with blue edge of the PBG (0.3421 mmol g−1 h−1) or the red edge of the PBG (0.3254 mmol g−1 h−1) in the inverse opals. The red edge enhancement was due to increased light absorption and charge carrier generation in TaON, whereas the blue edge effect was likely due to suppression of electron-hole pair recombination. Results demonstrate that photonic crystal engineering to exploit slow photon effects is a viable approach for boosting photocatalytic hydrogen production rates.

Carbon dots-based fluorescent molecularly imprinted photonic crystal hydrogel strip: Portable and efficient strategy for selective detection of tetracycline in foods of animal origin

Rapid, portable, and sensitive detection of tetracycline (TC) is crucial for the environment and human health. In this study, we developed carbon dots (CDs)-based fluorescent molecularly imprinted photonic crystal hydrogel (FMIPH) strips for TC detection in animal-derived foods. CDs emit fluorescent signals, and molecularly imprinted polymers provide specific recognition sites for TC. Inverse opal photonic crystals afford stable 3D macroporous mass transfer channels that considerably reduce binding time between TC and the strips. The portable FMIPH strip exhibited a linear fluorescence response to TC in the concentration range of 0.1–50 μg mL−1, with a detection limit of 0.067 μg mL−1. Good recoveries of TC (93.86–112.59%) were observed in TC-spiked commercially available pork, eggs, and milk. A combination of FMIPH strips with a portable fluorescent reading device could achieve sensitive, on-site, and real-time detection of TC in animal-derived foods.

Research and Application Progress of Inverse Opal Photonic Crystals in Photocatalysis

In order to solve the problem of low photocatalytic efficiency in photocatalytic products, researchers proposed a method to use inverse opal photonic crystal structure in photocatalytic materials. This is due to a large specific surface area and a variety of optical properties of the inverse opal photonic crystal, which are great advantages in photocatalytic performance. In this paper, the photocatalytic principle and preparation methods of three-dimensional inverse opal photonic crystals are introduced, including the preparation of basic inverse opal photonic crystals and the photocatalytic modification of inverse opal photonic crystals, and then the application progresses of inverse opal photonic crystal photocatalyst in sewage purification, production of clean energy and waste gas treatment are introduced.

Application of Carbon Nanosphere Templates for Preparation of Inverse Opal Photonic Crystals in Dye‐Sensitized Solar Cells

Carbon nanospheres are successfully synthesized with a particle size of about 140 nm using a two‐step hydrothermal method and used the carbon nanospheres as the deposition template material on the surface of P25(TiO2) by means of vertical deposition method. The antiopaline TiO2 photonic crystal (PC) structure is further prepared via immersed carbon nanospheres in TiO2 precursor solution, and the antiopal PC is used as the scattering layer of the photoanode of dye‐sensitized solar cell (DSSCs). As a comparison, the antiopal PC reflective layer is also prepared on the photoanode of DSSCs using polystyrene nanospheres as the template material. The photoanodes with those PC scattering layers prepared with different template materials are fabricated into complete DSSCs. The final photoelectric conversion efficiency of the DSSCs prepared with carbon nanospheres as the template material reaches 7.02%, which is comparable to the cells prepared with polystyrene nanospheres as the template material. The efficiency of the cell with the scattering layer is increased by about 16% compared with that of the normal DSSC based on P25.

S-scheme Ag/ZnO/CeO2 inverse opal photonic crystals with enhanced photocatalytic properties

Construction of S-scheme heterojunctions and increasing the specific surface area are considered effective strategies to enhance photocatalytic performance. In this work, ZnO and ZnO/CeO2 with inverse opal structure were constructed by the high-temperature template removal method. Then a simple UV photoreduction method was used to construct the photocatalysts with Ag/ZnO/CeO2 inverse opal (Ag/ZnO/CeO2 IO). The degradation behavior of the composite for rhodamine B (RhB) was investigated. Specifically, the photodegradation of RhB by Ag/ZnO/CeO2 exhibited good photostability and the best removal efficiency compared with ZnO inverse opal (ZnO IO) and ZnO/CeO2 inverse opal(ZnO/CeO2 IO), which was 2.7 times higher than that of ZnO IO. The synergetic effect of the composite effectively improves the electron adsorption capacity, and the surface plasmon resonance (SPR) effect of Ag nanoparticles enhances its photo availability, thus improving the photocatalytic activity. This work provides a new strategy for ZnO-based composites in degrading wastewater pollution.

Bioinspired Superwettable Catheters with Tunable Structural Color for Efficient Drug Release Monitoring

AbstractMedical interventional catheters are indispensable medical devices that are continuing to reshape current practice in many specialties of clinical applications. However, there has been rapid development of catheters, it remains many challenges in antibiofilm and effective drug delivering. Inspired by natural creatures, a bioinspired superwettable catheter is developed which is constructed with inverse opal photonic crystals hydrogel. The superwettability property is achieved by creating a slippery liquid‐infused porous surface (SLIPS) where the motion state of droplets changes. The expansion and contraction of the hydrogel endow the catheter with tunable structural color and drug release properties. Thus, the catheter could not only report the variation of the drug release process via SLIPS phenomenon obviously but also quantitatively give feedback on the drug release process through visually structural color variations. The multifunctional superwettable catheter shows good antibacterial performance and can be used for drug release monitoring which has excellent prospects in biomedical applications.

Chalcogenide glass nanospheres with tunable morphology by liquid-phase template approach

Chalcogenide glass (ChG) with unique material properties has been widely used in mid-infrared. Traditional ChG microspheres/nanospheres preparation usually uses a high-temperature melting method, in which it is difficult to accurately control the size and the morphology of the nanospheres. Here, we produce nanoscale-uniform (200-500nm), morphology-tunable, and arrangement-orderly ChG nanospheres from the inverse-opal photonic crystal (IOPC) template by the liquid-phase template (LPT) method. Moreover, we refer to the formation mechanism of nanosphere morphology as the evaporation-driven self-assembly of colloidal dispersion nanodroplets within the immobilized template and find that the concentration of ChG solution and the pore size of IOPC are the key to control the morphology of the nanospheres. The LPT method is also applied to the two-dimensional microstructure/nanostructure. This work provides an efficient and low-cost strategy for the preparation of multisize ChG nanospheres with tunable morphology and is expected to find various applications in mid-infrared, optoelectronic devices.

Inverse Opal Photonic Crystals for Real-Time Identifiable Labels via Ultraviolet and Near-Infrared Light

In this work, we developed inverse opal photonic crystals (IOPCs) for real-time identifiable labels by tuning the structure color and chemical color under ultraviolet (UV) light and near-infrared (NIR) light. We prepared IOPCs by etching a silica photonic crystal template in thermosensitive hydrogel added to 2,2-diphenyl-2H-naphtho [1,2-b] pyran-6-carbaldehyde (NP). In this way, the transparent hydrogel turned red under UV light due to the photochromic naphthopyran. Meanwhile, the green structure color of IOPCs was superimposed with the red chemical color of the hydrogel, so that IOPCs with naphthopyran (IOPCs/NP) appeared yellow. When irradiated by NIR light, the structure color of IOPCs turned blue from green due to the volume contraction of the thermosensitive hydrogel. When irradiated by UV and NIR light simultaneously, the blue structure color of IOPCs was superimposed with the red chemical color of the hydrogel, and the IOPCs/NP would finally appear purple. Thus, we realized the real-time controllable IOPCs by two light sources. Based on this, we designed a series of identifiable labels with multiple colors under UV and NIR light, which expanded the application of information anticounterfeiting and identification.