Elucidating Synergies of Single-Atom Catalysts in a Model Thin Film Photoelectrocatalyst to Maximize Hydrogen Evolution Reaction.

Realization of the full potential of single-atom photoelectrocatalysts in sustainable energy generation requires careful consideration of the design of the host material. Here, a comprehensive methodology for the rational design of photoelectrocatalysts using anodic titanium dioxide (TiO2) nanofilm as a model platform is presented. The properties of these nanofilms are precisely engineered to elucidate synergies across structural, chemical, optoelectronic, and electrochemical properties to maximize the efficiency of the hydrogen evolution reaction (HER). These findings clearly demonstrate that thicker TiO2 nanofilms in anatase phase with pits on the surface can accommodate single-atom platinum catalysts in an optimal configuration to increase HER performance. It is also evident that the electrolyte temperature can further enhance HER output through thermochemical effect. A judicious design incorporating all these factors into one system gives rise to a ten-fold HER enhancement. However, the reusability of the host photoelectrocatalyst is limited by the leaching of the Pt atom, worsening HER. Density-functional theory calculations have provided insights into the mechanism underlying the experimental observations in terms of moderate hydrogen adsorption and enhanced gas generation. This improved understanding of the critical factors determining HER performance in a model photoelectrocatalyst paves the way for future advances in scalable and translatable photoelectrocatalyst technologies.

Detection of Volatile Organic Compounds through Spectroscopic Signatures in Nanoporous Fabry-Pérot Optical Microcavities.

Increasingly complex modern gas-monitoring scenarios necessitate advanced sensing capabilities to detect and identify a diverse range of gases under varying conditions. There is a rising demand for individual sensors with multiple responses capable of recognizing gases, identifying components in mixtures, and providing stable responses. Inspired by gas sensors employing multivariable response principles, we develop a nanoporous anodic alumina high-order microcavity (NAA-HOµCV) gas sensor with multiple optical outputs for discriminative gas detection. The NAA-HOµCV architecture, formed by a Fabry-Pérot microcavity with distributed Bragg reflector (DBR) mirrors and an extended-length microcavity layer supporting multiple resonant modes, serves as an effective solid-state fingerprint platform for distinguishing volatile organic compound (VOC) gases. Our research reveals that the coupling strength of light into resonant modes and their evolution depend on the thickness of the DBR mirrors and the dimension of the microcavity layer, which allows us to optimize the discriminative sensing capability of the NAA-HOµCV sensor through structural engineering of the microcavity and photonic crystal mirrors. Gas-sensing experiments conducted on the NAA-HOµCV sensor demonstrate real-time discrimination between physiosorbed VOC gases (isopropanol, ethanol, or acetone) in reversible gas sensing. It also achieves superior ppb-level sensing in irreversible gas sensing of model silane molecules. Our study presents promising avenues for designing compact, cost-effective, and highly efficient gas sensors with tailored properties for discriminative gas detection.

Engineering of Solid-State Nanoporous Laser through Dendrimer-Encapsulated Fluorophores.

Dendrimers─nanosized macromolecules that can function as hosts for encapsulation of guest molecules─provide new avenues to engineer gain media for lasing systems. In this context, this study investigates the interplay between the geometric features of a model porous scattering medium, nanoporous anodic alumina (NAA), and the chemical features of a model fluorophore-dendrimer encapsulation system to maximize random lasing. The inner surface of the NAA platforms is functionalized with fluorophore molecules encapsulated within dendrimers via an electrostatic interaction. The resulting solid-state composite structures emit well-resolved, intense random lasing when subjected to optical pumping. By engineering fluorophore-dendrimer and geometric features of scattering medium, we can precisely tune the characteristics of random lasing emissions. It is found that lasing structures with low porosity and thickness functionalized with fluorophore molecules encapsulated in second-generation dendrimers provide the best platforms for lasing generation, resulting in a strongly polarized laser at ∼594 nm that has a high quality-gain product of ∼1588 au, a polarization quality of ∼0.86, and a lasing threshold of ∼0.05 mJ pulse-1. Comparative analysis indicates that dendrimers achieve 2.5 times better random lasing than conventional surfactants due to improved encapsulation and minimization of photobleaching. Our results reveal the importance of the fluorophore encapsulation method and design of scattering media in the engineering of random lasing platforms for applications in optical and optoelectrical systems.

Tailoring Tamm Plasmon Resonances in Dielectric Nanoporous Photonic Crystals.

The fields of plasmonics and photonic crystals (PCs) have been combined to generate model light-confining Tamm plasmon (TMM) cavities. This approach effectively overcomes the intrinsic limit of diffraction faced by dielectric cavities and mitigates losses associated with the inherent properties of plasmonic materials. In this study, nanoporous anodic alumina PCs, produced by two-step sinusoidal pulse anodization, are used as a model dielectric platform to establish the methodology for tailoring light confinement through TMM resonances. These model dielectric mirrors feature highly organized nanopores and narrow bandwidth photonic stopbands (PSBs) across different positions of the spectrum. Different types of metallic films (gold, silver, and aluminum) were coated on the top of these model dielectric mirrors. By structuring the features of the plasmonic and photonic components of these hybrid structures, the characteristics of TMM resonances were studied to elucidate effective approaches to optimize the light-confining capability of this hybrid TMM model system. Our findings indicate that the coupling of photonic and plasmonic modes is maximized when the PSB of the model dielectric mirror is broad and located within the midvisible region. It was also found that thicker metal films enhance the quality of the confined light. Gas sensing experiments were performed on optimized TMM systems, and their sensitivity was assessed in real time to demonstrate their applicability. Ag films provide superior performance in achieving the highest sensitivity (S = 0.038 ± 0.001 nm ppm-1) based on specific binding interactions between thiol-containing molecules and metal films.

Understanding the Intrinsic Rectification Properties of Nanoporous Anodic Alumina by Selective Chemical Etching.

The distribution of oxygen and aluminum vacancies across the hemispherical barrier oxide layer (BOL) of nanoporous anodic alumina (NAA) relies intrinsically on the electric field-driven flow of electrolytic species and the incorporation of electrolyte impurities during the growth of anodic oxide through anodization. This phenomenon provides new opportunities to engineer BOL's inherited ionic current rectification (ICR) fingerprints. NAA's characteristic ICR signals are associated with the space charge density gradient across BOL and electric field-induced ion migration through hopping from vacancy to vacancy. In this study, we engineer the intrinsic space charge density gradient of the BOL of NAA under a range of anodizing potentials in hard and mild anodization regimes. Real-time characterization of the ICR fingerprints of NAA during selective etching of the BOL makes it possible to unravel the distribution pattern of vacancies through rectification signals as a function of etching direction and time. Our analysis demonstrates that the space charge density gradient varies across the BOL of NAA, where the magnitude and distribution of the space charge density gradient are revealed to be critically determined by anodizing the electrolyte, regime, and potential. This study provides a comprehensive understanding of the engineering of ion transport behavior across blind-hole NAA membranes by tuning the distribution of defects across BOL through anodization conditions. This method has the potential to be harnessed for developing nanofluidic devices with tailored ionic rectification properties for energy generation and storage and sensing applications.

Structural Engineering of the Barrier Oxide Layer of Nanoporous Anodic Alumina for Iontronic Sensing.

The hemispherical barrier oxide layer (BOL) closing the bottom tips of hexagonally distributed arrays of cylindrical nanochannels in nanoporous anodic alumina (NAA) membranes is structurally engineered by anodizing aluminum substrates in three distinct acid electrolytes at their corresponding self-ordering anodizing potentials. These nanochannels display a characteristic ionic current rectification (ICR) signal between high and low ionic conduction states, which is determined by the thickness and chemical composition of the BOL and the pH of the ionic electrolyte solution. The rectification efficiency of the ionic current associated with the flow of ions across the anodic BOL increases with its thickness, under optimal pH conditions. The inner surface of the nanopores in NAA membranes was chemically modified with thiol-terminated functional molecules. The resultant NAA-based iontronic system provides a model platform to selectively detect gold metal ions (Au3+) by harnessing dynamic ICR signal shifts as the core sensing principle. The sensitivity of the system is proportional to the thickness of the barrier oxide layer, where NAA membranes produced in phosphoric acid at 195 V with a BOL thickness of 232 ± 6 nm achieve the highest sensitivity and low limit of detection in the sub-picomolar range. This study provides exciting opportunities to engineer NAA structures with tailorable ICR signals for specific applications across iontronic sensing and other nanofluidic disciplines.

Spectral Engineering of Tamm Plasmon Resonances in Dielectric Nanoporous Photonic Crystal Sensors.

Model light-confining Tamm plasmon cavities based on gold-coated nanoporous anodic alumina photonic crystals (TMM-NAA-PCs) with spectrally tunable resonance bands were engineered. Laplacian and Lorentzian NAA-PCs produced by a modified Gaussian-like pulse anodization approach showed well-resolved, high-quality photonic stopbands, the position of which was precisely controlled across the visible spectrum by the periodicity in the input anodization profile. These PC structures were used as a platform material to develop highly reflective distributed Bragg mirrors, the top sides of which were coated with a thin gold film. The resulting nanoporous hybrid plasmonic-photonic crystals showed strong light-confining properties attributed to Tamm plasmon resonances at three specific positions of the visible spectrum. These structures achieved high sensitivity to changes in refractive index, with a sensitivity of ∼106 nm RIU-1. The optical sensitivity of TMM-NAA-PCs was assessed in real time, using a model chemically selective binding interaction between thiol-containing molecules and gold. The optical sensitivity was found to rely linearly on the spectral position of the Tamm resonance band, for both Laplacian and Lorentzian TMM-NAA-PCs. The density of self-assembled monolayers of thiol-containing analyte molecules formed on the surface of the metallic film directly contributes to the dependence of sensitivity on TMM resonance position in these optical transducers. Our findings provide opportunities to integrate TMM modes in NAA-based photonic crystal structures, with promising potential for optical technologies and applications requiring high-quality surface plasmon resonance bands.

Role of Spectral Resonance Features and Surface Chemistry in the Optical Sensitivity of Light-Confining Nanoporous Photonic Crystals.

Nanoporous anodic alumina optical microcavities (NAA-µQVs) with spectrally tunable resonance band and surface chemistry are used as model light-confining photonic crystal (PC) platforms to elucidate the combined effect of spectral light confinement features and surface chemistry on optical sensitivity. These model nanoporous PCs show well-resolved, spectrally tunable resonance bands (RBs), the central wavelength of which is engineered from ∼400 to 800 nm by the period of the input anodization profile. The optical sensitivity of the as-produced (hydrophilic) and dichlorodimethylsilane-functionalized (hydrophobic) NAA-µQVs is studied by monitoring dynamic spectral shifts of their RB upon infiltration with organic- and aqueous-based analytical solutions of equally varying refractive index, from 1.333 to 1.345 RIU. Our findings demonstrate that hydrophilic NAA-µQVs show ∼81 and 35% superior sensitivity to their hydrophobic counterparts for organic- and aqueous-based analytical solutions, respectively. Interestingly, the sensitivity of hydrophilic NAA-µQVs per unit of spectral shift is more than 3-fold higher in organic than in aqueous matrices upon equal change of refractive index, with values of 0.347 ± 0.002 and 0.109 ± 0.001 (nm RIU-1) nm-1, respectively. Conversely, hydrophobic NAA-µQVs are found to be slightly more sensitive toward changes of refractive index in aqueous medium, with sensitivities of 0.072 ± 0.002 and 0.066 ± 0.006 (nm RIU-1) nm-1 in water- and organic-based analytical solutions, respectively. Our advances provide insights into critical factors determining optical sensitivity in light-confining nanoporous PC structures, with implications across optical sensing applications, and other photonic technologies.

Engineering of Broadband Nanoporous Semiconductor Photonic Crystals for Visible-Light-Driven Photocatalysis.

A new class of semiconductor photonic crystals composed of titanium dioxide (TiO2)-functionalized nanoporous anodic alumina (NAA) broadband-distributed Bragg reflectors (BDBRs) for visible-light-driven photocatalysis is presented. NAA-BDBRs produced by double exponential pulse anodization (DEPA) show well-resolved, spectrally tunable, broad photonic stop bands (PSBs), the width of which can be precisely tuned from 70 ± 6 to 153 ± 9 nm (in air) by progressive modification of the anodization period in the input DEPA profile. Photocatalytic efficiency of TiO2-NAA-BDBRs with tunable PSB width upon visible-NIR illumination is studied using three model photodegradation reactions of organics with absorbance bands across the visible spectral regions. Analysis of these reactions allows us to elucidate the interplay of spectral distance between red edge of TiO2-NAA-BDBRs' PSB, electronic bandgap, and absorbance band of model organics in harnessing visible photons for photocatalysis. Photodegradation reaction efficiency is optimal when the PSB's red edge is spectrally close to the electronic bandgap of the functional semiconductor coating. Photocatalytic performance decreases dramatically when the red edge of the PSB is shifted toward visible wavelengths. However, a photocatalytic recovery is observed when the PSB's red edge is judiciously positioned within the proximity of the absorption band of model organics, indicating that TiO2-NAA-BDBRs can harness visible electromagnetic waves to speed up photocatalytic reactions by drastically slowing the group velocity of incident photons at specific spectral regions. Our advances provide new opportunities to better understand and engineer light-matter interactions for photocatalysis, using TiO2-NAA-BDBRs as model nanoporous semiconductor platforms. These high-performing photocatalysts could find broad applicability in visible-NIR light harvesting for environmental remediation, green energy generation, and chemical synthesis.

Tunable Nanoporous Anodic Alumina Photonic Crystals by Gaussian Pulse Anodization.

This study presents a Gaussian pulse anodization approach to generate nanoporous photonic crystals with highly tunable and controllable optical properties across the visible-NIR spectrum. Nanoporous anodic alumina Gaussian photonic crystals (NAA-GPCs) are fabricated in oxalic acid electrolyte by Gaussian pulse anodization, a novel form of pulse-like anodization. The effect of the Gaussian pulse width in the anodization profile on the optical properties of these photonic crystals is assessed by systematically varying this fabrication parameter from 5 to 60 s. The optical features of the characteristic photonic stopband (PSB) of NAA-GPCs-the position of the central wavelength, full width at half-maximum, and intensity-are found to be highly dependent on the Gaussian pulse width, the angle of incidence of incoming photons, and the nanopore diameter of NAA-GPCs. The effective medium of NAA-GPCs is assessed by monitoring spectral shifts in their characteristic PSB upon infiltration of their nanoporous structure with analytical solutions of d-glucose of varying concentration (0.0125-1 M). Experimental results are validated and mechanistically described by theoretical simulations, using the Looyenga-Landau-Lifshitz effective medium approximation model. Our findings demonstrate that Gaussian pulse anodization is an effective nanofabrication approach to producing highly sensitive NAA-based PC structures with versatile and tunable PSBs across the spectral regions. The findings provide new exiting opportunities to integrate these unique PC structures into photonic sensors and other platform materials for light-based technologies.

Realization of high-quality optical nanoporous gradient-index filters by optimal combination of anodization conditions.

High-quality nanoporous anodic alumina gradient-index filters (NAA-GIFs) are realized by sinusoidal pulse anodisation (SPA) of aluminum. A three-level factorial design of experiments is used to determine the effect of three critical anodization parameters -electrolyte temperature, concentration of the electrolyte and anodization time- on the quality of light control in these photonic crystal (PC) structures. Quantitative analysis of the effect of these anodization parameters on the quality of the characteristic photonic stopband (PSB) of NAA-GIFs reveals that all three anodization parameters and their respective combinations have statistically significant effects. However, anodization time is found to have the highest impact on the quality of light control in NAA-GIFs, followed by the electrolyte concentration and its temperature. Our findings demonstrate that NAA-GIFs fabricated under optimal conditions achieve an outstanding quality factor of ∼86 (i.e.∼18% superior to that of other NAA-based PCs reported in the literature). This study provides new insight into optimal anodization conditions to fabricate high-quality NAA-based PC structures, opening new exciting opportunities to integrate these nanoporous PCs as platform materials for light-based technologies requiring a precise control over photons such as ultra-sensitive optical sensors and biosensors, photocatalysts for green energy generation and environmental remediation, optical encoding and lasing.

Environmental Copper Sensor Based on Polyethylenimine-Functionalized Nanoporous Anodic Alumina Interferometers.

Anthropogenic copper pollution of environmental waters from sources such as acid mine drainage, antifouling paints, and industrial waste discharge is a major threat to our environment and human health. This study presents an optical sensing system that combines self-assembled glutaraldehyde-cross-linked double-layered polyethylenimine (PEI-GA-PEI)-modified nanoporous anodic alumina (NAA) interferometers with reflectometric interference spectroscopy (RIfS) for label-free, selective monitoring of ionic copper in environmental waters. Calibration of the sensing system with analytical solutions of copper shows a linear working range between 1 and 100 mg L-1, and a low limit of detection of 0.007 ± 0.001 mg L-1 (i.e., ∼0.007 ppm). Changes in the effective optical thickness (ΔOTeff) of PEI-GA-PEI-functionalized NAA interferometers are monitored in real-time by RIfS, and correlated with the amount of ionic copper present in aqueous solutions. The system performance is validated through X-ray photoelectron spectroscopy (XPS) and the spatial distribution of copper within the nanoporous films is characterized by time-of-flight-secondary ion mass spectroscopy (TOF-SIMS). The specificity and chemical selectivity of the PEI-GA-PEI-NAA sensor to Cu2+ ions is verified by screening six different metal ion solutions containing potentially interfering ions such as Al3+, Cd2+, Fe3+, Pb2+, Ni2+, and Zn2+. Finally, the performance of the PEI-GA-PEI-NAA sensor for real-life applications is demonstrated using legacy acid mine drainage liquid and tap water for qualitative and quantitative detection of copper ions. This study provides new opportunities to develop portable, cost-competitive, and ultrasensitive sensing systems for real-life environmental applications.

Nanoporous Anodic Alumina Photonic Crystals for Optical Chemo- and Biosensing: Fundamentals, Advances, and Perspectives.

Optical sensors are a class of devices that enable the identification and/or quantification of analyte molecules across multiple fields and disciplines such as environmental protection, medical diagnosis, security, food technology, biotechnology, and animal welfare. Nanoporous photonic crystal (PC) structures provide excellent platforms to develop such systems for a plethora of applications since these engineered materials enable precise and versatile control of light⁻matter interactions at the nanoscale. Nanoporous PCs provide both high sensitivity to monitor in real-time molecular binding events and a nanoporous matrix for selective immobilization of molecules of interest over increased surface areas. Nanoporous anodic alumina (NAA), a nanomaterial long envisaged as a PC, is an outstanding platform material to develop optical sensing systems in combination with multiple photonic technologies. Nanoporous anodic alumina photonic crystals (NAA-PCs) provide a versatile nanoporous structure that can be engineered in a multidimensional fashion to create unique PC sensing platforms such as Fabry⁻Pérot interferometers, distributed Bragg reflectors, gradient-index filters, optical microcavities, and others. The effective medium of NAA-PCs undergoes changes upon interactions with analyte molecules. These changes modify the NAA-PCs' spectral fingerprints, which can be readily quantified to develop different sensing systems. This review introduces the fundamental development of NAA-PCs, compiling the most significant advances in the use of these optical materials for chemo- and biosensing applications, with a final prospective outlook about this exciting and dynamic field.

Structural tailoring of nanoporous anodic alumina optical microcavities for enhanced resonant recirculation of light.

A comprehensive study about the structural engineering of high quality nanoporous anodic alumina optical microcavities (NAA-µCVs) fabricated by rationally designed anodisation strategies to enhance the light-confining capabilities of these photonic crystal (PC) structures is presented. Two types of NAA-µCV architectures are produced: (i) GIF-NAA-µCVs composed of a cavity layer featuring straight nanopores that is sandwiched between two gradient-index filters (GIFs) with sinusoidally modulated porosity in depth, and (ii) DBR-NAA-µCVs formed by sandwiching a cavity layer with straight nanopores between two distributed Bragg reflectors (DBRs), in which the porosity is engineered in a stepwise fashion. The geometric features of GIF-NAA-µCVs and DBR-NAA-µCVs are engineered and optimised through a systematic modification of the anodisation parameters (i.e. cavity anodisation time, cavity anodisation current density, anodisation period and number of anodisation pulses, and pore widening time). This methodology enables fine-tuning of the optical properties of GIF-NAA-µCVs and DBR-NAA-µCVs, such as quality factor and position and width of resonance band, to generate NAA-µCVs with unprecedented quality factors (i.e. 170 ± 8 and 206 ± 10 for the first and second order resonance bands - threefold and fourfold quality enhancement as compared to previous studies). Our results demonstrate that an optimal design of the geometric features and the nanoporous architecture of NAA-µCVs can significantly enhance resonant recirculation of light within these PC structures, creating new opportunities to develop ultrasensitive optical platforms, highly selective optical filters, and other photonic devices.

Real-Time Binding Monitoring between Human Blood Proteins and Heavy Metal Ions in Nanoporous Anodic Alumina Photonic Crystals.

This study reports on the real-time binding assessment between heavy metal ions and blood proteins immobilized onto nanoporous anodic alumina photonic crystals (NAA-PCs) by reflectometric interference spectroscopy (RIfS). The surface of NAA-PCs is chemically functionalized with γ-globulin (GG), transferrin (TFN), and serum albumin (HSA), the major proteins present in human blood plasma. Protein-modified NAA-PC platforms are exposed to analytical solutions of mercury ions of different concentrations. Dynamic changes in the effective optical thickness of protein-modified NAA-PCs in response to heavy metal ions are assessed in real time to evaluate the binding kinetics, affinity, and mechanism. Protein molecules undergo conformational changes upon exposure to mercury ions, with HSA exhibiting the strongest affinity. The combination of protein-modified NAA-PCs with RIfS allows real-time monitoring of protein-heavy metal ions interactions under dynamic flow conditions. This system is capable of detecting dynamic conformational changes in these proteins upon exposure to heavy metal ions. Our results provide new insights into these binding events, which could enable new methodologies to study the toxicity of heavy metal ions and other biomolecular interactions.

Engineering the Slow Photon Effect in Photoactive Nanoporous Anodic Alumina Gradient-Index Filters for Photocatalysis.

In this study, we explore for the first time the capabilities of nanoporous anodic alumina gradient-index filters (NAA-GIFs) functionalized with titanium dioxide (TiO2) photoactive layers to enhance photon-to-electron conversion rates and improve the efficiency of photocatalytic reactions by "slow photon" effect. A set of NAA-GIFs was fabricated by sinusoidal pulse anodization, in which a systematic modification of various anodization parameters (i.e., pore widening time, anodization period, and anodization time) enables the fine-tuning of the photonic stopband (PSB) of these nanoporous photonic crystals (PCs) across the spectral regions. The surface of NAA-GIFs was chemically modified with photoactive layers of TiO2 to create a composite photoactive material with precisely engineered optical properties. The photocatalytic performance of TiO2-functionalized NAA-GIFs was assessed by studying the photodegradation of three model organic dyes (i.e., methyl orange, Rhodamine B, and methylene blue) with well-defined absorption bands across different spectral regions under simulated irradiation conditions. Our study demonstrates that when the edges of characteristic PSB of TiO2-modified NAA-GIFs are completely or partially aligned with the absorption band of the organic dyes, the photodegradation rate is enhanced due to "slow photon" effect. A rational design of the photocatalyst material with respect to the organic dye is demonstrated to be optimal to speed up photocatalytic reactions by an efficient management of photons from high-irradiance spectral regions. This provides new opportunities to develop high-performing photocatalytic materials for efficient photocatalysis with broad applicability.

Engineering of Hybrid Nanoporous Anodic Alumina Photonic Crystals by Heterogeneous Pulse Anodization.

In this study, we present an advanced nanofabrication approach, so-called 'heterogeneous pulse anodization' (HPA), in which galvanostatic stepwise and apodized sinusoidal pulse anodizations are combined in a single process. This novel anodization method enables the precise optical engineering of the characteristic photonic stopbands (PSBs) of nanoporous anodic alumina photonic crystals (NAA-PCs). The resulting structures are hybrid PCs (Hy-NAA-PCs) composed of distributed Bragg reflectors (DBRs) and apodized gradient-index filters (APO-GIFs) embedded within the same PC structure. The modification of various anodization parameters such as anodization period, relative and total anodization time, structural arrangement of PCs within Hy-NAA-PCs, and pore widening time allows the fine-tuning of the PSBs' features (i.e. number, position and bandwidth of central wavelength) across the spectral regions. The effects of these fabrication parameters are systematically assessed, revealing that the positions of the characteristic transmission bands of Hy-NAA-PCs are highly controllable. Our study provides a comprehensive rationale towards the development of unique Hy-NAA-PCs with controllable optical properties, which could open new opportunities for a plethora of applications.

On the Precise Tuning of Optical Filtering Features in Nanoporous Anodic Alumina Distributed Bragg Reflectors.

This study presents a nanofabrication approach that enables the production of nanoporous anodic alumina distributed Bragg reflectors (NAA-DBRs) with finely engineered light filtering features across the spectral regions. The photonic stopband (PSB) of these NAA-based photonic crystal (PC) structures is precisely tuned by an apodization strategy applied during stepwise pulse anodization with the aim of engineering the effective medium of NAA-DBRs in depth. We systematically assess the effect of different fabrication parameters such as apodization function (i.e. linear positive, linear negative, logarithmic positive and logarithmic negative), amplitude difference (from 0.105 to 0.420 mA cm-2), current density offset (from 0.140 to 0.560 mA cm-2), anodization period (from 1100 to 1700 s), and pore widening time (from 0 to 6 min) on the quality and central wavelength of the PSB of NAA-DBRs. The PSB's features these PC structures are demonstrated to be highly tunable with the fabrication parameters, where a logarithmic negative apodization is found to be the most effective function to produce NAA-DBRs with high quality PSBs across the UV-visible-NIR spectrum. Our study establishes that apodized NAA-DBRs are more sensitive to changes in their effective medium than non-apodized NAA-DBRs, making them more suitable sensing platforms to develop advanced optical sensing systems.

Realisation and optical engineering of linear variable bandpass filters in nanoporous anodic alumina photonic crystals.

We present the first realisation of linear variable bandpass filters in nanoporous anodic alumina (NAA-LVBPFs) photonic crystal structures. NAA gradient-index filters (NAA-GIFs) are produced by sinusoidal pulse anodisation and used as photonic crystal platforms to generate NAA-LVBPFs. The anodisation period of NAA-GIFs is modified from 650 to 850 s to systematically tune the characteristic photonic stopband of these photonic crystals across the UV-visible-NIR spectrum. Then, the nanoporous structure of NAA-GIFs is gradually widened along the surface under controlled conditions by wet chemical etching using a dip coating approach aiming to create NAA-LVBPFs with finely engineered optical properties. We demonstrate that the characteristic photonic stopband and the iridescent interferometric colour displayed by these photonic crystals can be tuned with precision across the surface of NAA-LVBPFs by adjusting the fabrication and etching conditions. Here, we envisage for the first time the combination of the anodisation period and etching conditions as a cost-competitive, facile, and versatile nanofabrication approach that enables the generation of a broad range of unique LVBPFs covering the spectral regions. These photonic crystal structures open new opportunities for multiple applications, including adaptive optics, hyperspectral imaging, fluorescence diagnostics, spectroscopy, and sensing.

Engineering of Surface Chemistry for Enhanced Sensitivity in Nanoporous Interferometric Sensing Platforms.

We explore new approaches to engineering the surface chemistry of interferometric sensing platforms based on nanoporous anodic alumina (NAA) and reflectometric interference spectroscopy (RIfS). Two surface engineering strategies are presented, namely (i) selective chemical functionalization of the inner surface of NAA pores with amine-terminated thiol molecules and (ii) selective chemical functionalization of the top surface of NAA with dithiol molecules. The strong molecular interaction of Au3+ ions with thiol-containing functional molecules of alkane chain or peptide character provides a model sensing system with which to assess the sensitivity of these NAA platforms by both molecular feature and surface engineering. Changes in the effective optical thickness of the functionalized NAA photonic films (i.e., sensing principle), in response to gold ions, are monitored in real-time by RIfS. 6-Amino-1-hexanethiol (inner surface) and 1,6-hexanedithiol (top surface), the most sensitive functional molecules from approaches i and ii, respectively, were combined into a third sensing strategy whereby the NAA platforms are functionalized on both the top and inner surfaces concurrently. Engineering of the surface according to this approach resulted in an additive enhancement in sensitivity of up to 5-fold compared to previously reported systems. This study advances the rational engineering of surface chemistry for interferometric sensing on nanoporous platforms with potential applications for real-time monitoring of multiple analytes in dynamic environments.